Brje Steenberg

Adsorption and Exchange of Ions on Activated Charcoal

ALMQVIST & WIKSELLS BOKTRYCKERI AKTIEBOLAG UPPSALA 1 9 4 4

Adsorption and Exchang of Ions on Activated Charcoal

AKADEMISK AVHANDLING
SOM MED TILLSTND AV MATEMATJSK-NATURVETENSKAPLIGA FAKULTETEN VID STOCKHOLMS HGSKOLA FR FILOSOFIE DOKTORSGRADS VINNANDE TILL OFFENTLIG GRANSKNING FRAMLGGES HGSKOLANS LROSAL 2, LRDAGEN D E N 2 DECEMBER 1944 KL. 10 F. M. AV

BRJE STEENBERG
FILOSOFIK LICENTIAT

UPPSALA 1944
ALMQVIST & W I K SELLS BOKTRYCKERI AB

Brje Steenberg

Adsorption and Exchange of Ions on Activated Charcoal

ALMQVIST & WIKSELLS BOKTRYCKERI AKTIEBOLAG UPPSALA 1944

CONTENTS.

Page

Preface I . Introduction. Scope of Investigation I I . Production and Nature of Activated Charcoals. The Surface of Charcoals I I I . The Principal Qualitative Observations of Electrolyte Adsorption on Charcoal IV. Earlier Theories on Adsorption of Electrolytes on Charcoal A. B. C. D. The Theory of Bartell and Miller, 1924 The Miller "Hydrolytic" Theory The Oxide Theory of Electrolyte Adsorption Frumkin's Electrochemical Theory

5 7 11 18 26 26 28 31 37 41 44 61 71

V. Plan of the Present Investigation VI. Preparation of Gas-Activated Charcoals Low in Ash, and a Study of their Adsorption Properties VII. On the Nature of the Steady State Obtained when Electrolyte Adsorption on Charcoal is Completed.... VIII. On the Nature of the Forces Coming into Play in the Adsorption of Electrolytes on H-Charcoal I X . Primary and Secondary Adsorption of Ions on H-Charcoal

88

Pag

X . The Applicability of the Donnan Theory t o Second arily Adsorbed Ions on H-Charcoal. A. General Considerations 96 B. H-Charcoal with Adsorbed Electrolytes Function ing as Acidoids 98 C. H-Charcoal with Adsorbed Organic Electrolytes Functioning as Basoids 110 D. Experiments with Adsorbed Inorganic Acids 113 E. Summary of Chapter and Conclusion 129 X I . A Theory on the Hydrolytic Adsorption of Salts on H-Charcoal 132 X I I . The Primary Adsorption of Ions as a Function of the Ionic Compositon of the System 144 Appendix Summary Bibliography 173 177 182

PREFACE.

There is probably no aspect of the problem concerning the adsorptive capacity of active charcoal t h a t has received so much attention as t h a t dealing with the adsorption of electrolytes. The points of view expressed on the subject a t different times have gone from one extreme t o the other, and there is no generally accepted theory of electrolyte adsorption on active charcoal. No comprehensive monograph has appeared in print, and for this reason some diffidence must be felt in approaching the subject. Furthermore, the literature is full of contradictions, this being in large part due t o the fact t h a t active charcoal is a poorly defined substance. Workers making a study of this substance are well advised t o bear in mind the words of 0 . Ruff (1928) concerning the research in this field. Ruff speaks of "Wiedersprchen, die nur durch erneute Prfung, Erweiterung und Sichtung lterer Beobachtungen und Vorstellungen behoben werden knnen. So undenkbar eine solche Arbeit ist, muss sie doch geleistet werden; denn lohnend ist der Aufbau von Neuem immer nur auf gesicherten Grund." The investigations and theories regarding electrolyte adsorption on active charcoal, presented b y the author in this thesis, make no claim t o interpret the deeper causes underlying the phenomena in question; they are rather t o be regarded as an attempt t o syste matize the different phenomena. These investigations are chiefly confined, also, t o active charcoals gas-activated a t tempera tures of about 800 C. The writer considers t h a t the apparent inconsistencies in the phenomena can be explained on the basis of a few chemical laws, chief among which are the Donnan laws. I t is also demonstrated t h a t a parallelism exists between the adsorption of electrolytes on the active charcoal used here and electrolyte adsorption a t a water/air interface.

For the reason mentioned above, a fairly exhaustive review of the literature has been appended. I t was thought that, b y includ ing in the bibliography the complete titles of the publications t o which reference is made, the author might contribute in some measure towards increasing the value of the thesis t o future in vestigators. Besides being of great interest from the theoretical point of view, the problems treated in the thesis are of significance both t o technicians making use of active charcoal in decolorization processes, and t o medical men who use charcoal for therapeutic purposes. The investigations reported were for the most part carried out a t The Swedish State Pharmaceutical Laboratory. I am very pleased t o have the opportunity of expressing my gratitude t o the past and present staff of the laboratory, Mr. H . Nilsson, Ph. Lie., Dr. H . Rydin, M. D., and Mr. E . Bengtsson, P h . Lie., for their interest, encouragement, and help in the work. I should like particularly t o tender them m y thanks for the obliging way in which they placed pupils a t m y disposal for the routine work. My grateful acknowledgement is also due t o these pupils, num bering about twenty, for the never-failing thoroughness and patience they displayed during the long and tedious series of tests without which it would have been impossible for me t o systematize the phenomena into an ordered theory. I am also indebted t o my teacher, Professor A. Westgren, and t o Professor A. lnder and Mr. H . Arnfelt, Ph. Lie., Mr. U. Trgrdh, Ph. Lic., and Mr. C. O. Gabrielson, for many valuable discussions. Mrs. G. Lundberg, B. A. has kindly helped t o correct my English and read the proofs, and Mr. D. Cheesman, Ph. D. has also been good enough t o look over the English from the chemist's point of view. The Royal Technical University, Stockholm, June 1944. Brje Sternberg,

I. Introduction. Scope of Investigation.

The property of charcoal of adsorbing gases and dissolved substances seems t o have been observed a very long time ago. The discovery of the adsorptive power of charcoal from solutions is generally accredited t o Lowitz (128), who observed in 1785 t h a t several dissolved organic substances were ' 'prcipitai e d " b y charcoal. The technical importance of this discovery soon became evident and even as early as 1791 Gadolin (72) proposed the use of charcoal for the purification of crude saltpetre. Lowitz, too, tried this method with a certain success. The use of charcoal as a decolorizing agent in the manufacture of sugar has been known since 1794 (126). Even this application of charcoal was sug gested b y Lowitz. As early as 1833, Berzelius, in his "Lehrbuch der Chemie" (25) discussed several investigations on the adsorp tion of gases and solutes. By this time it was known t h a t the activity of carbonaceous materials varied widely, and further that only those kinds of carbons which exhibited no metallic lustre had any adsorptive power. I n 1811, Figuier observed t h a t charcoals made from animal substances were especially effective, and from t h a t time until about 1915 most adsorption experiments with charcoal were made with animal charcoal. Bancroft (14) made a comprehensive review of the use of charcoal in adsorption before the 191418 war. Owing t o the introduction of chemical warfare, large amounts of charcoals were required for gas-masks, and both the scarcity of animal products and economy made it necessary t o use char coals produced from other raw materials. The major part of the activated charcoals commercially used nowadays is made from vegetable substances and coal. The term "activated charcoals" is used t o denote all substances consisting chiefly of elementary carbon and which exhibit a pro

nounced .adsorptive power. Those treatments which increase the adsorptive capacity of the material are called activation processes. I n order t o reveal the laws governing adsorption on charcoal from solutions experiments have been carried out comprising a very large number of different solutes. I n the early days of the study of adsorption it was thought t h a t charcoal exhibited affinity only towards organic substances, especially colouring matters and olfactory substances. Graham (75) was the first to demonstrate t h a t inorganic substances were also adsorbed on charcoal. He found t h a t adsorption occurred of iodine which was dissolved in a solution of potassium iodide in water. I n addition he found t h a t calcium ions were adsorbed from a slaked lime solution and lead ions from lead nitrate. Several inorganic compounds in neutral aqueous solutions, however, were found not t o be adsorbable. The adsorbability of inorganic and organic strong electrolytes has later been repeatedly confirmed, although the qualitative results of different investigators have been rather divergent. The aim of this thesis is t o make a critical review of the results of previous investigators, and t o attempt t o establish a quanti tative theory of some of the phenomena of electrolyte adsorption on charcoal. I t must be kept in mind t h a t adsorption is a phenomenon occurring a t all interfaces. The theoretical interpretation of the disappearance of solutes or gases from the bulk of a solution or a gas cannot be made from a single point of view. I t is thought t h a t adsorption can be caused either b y physical surface-forcs (physical adsorption, adsorption proper), a solvent action (ab sorption), or chemical reactions with the adsorbent (chemisorption). Only in extreme cases can the observed phenomenon be adequat ely interpreted as the action of one of the mentioned processes. I n many instances the effects must be supposed t o be much more complicated. I n order t o study adsorption it is of great assistance t o know the structure of the adsorbing surface. The surface of liquids can be made plane and thus well defined geometrically. The area of t h e surface can also be changed a t will; this cannot be done with solids. The properties of single surfaces of crystals are consequently much more difficult t o study. Furthermore, the surface of a real

solid body cannot be considered t o consist of ideal crystal planes. To a considerable extent fissures occur in the planes and capillary cavities of different dimensions penetrate into the surface. The knowledge of the properties of defined surfaces is therefore prin cipally derived from a study of the liquid/gas and the liquid/liquid interfaces. I n the special case of charcoal as an adsorbent it has repeatedly been asserted t h a t the adsorption of gases and solutes is a chemical interaction between the charcoal and the substances adsorbed. As it has been established t h a t even inert gases can be adsorbed on charcoal, this theory cannot be held t o be universally valid. The generally accepted conception of adsorption on charcoal of gases and organic non-electrolytes from solutions is founded on a theory of physical surface action (van der Waals' forces), and not on chemical reactions. This is not the case, however, when the adsorbed substances are strong electrolytes. I n several of the theories pro pounded in recent years it is assumed t h a t adsorption of ions on charcoal is caused b y chemical reactions with impurities organic or inorganic on the surface of the carbon. The theory of the process of adsorption of gases on charcoal has advanced f a r beyond t h a t of adsorption from solutions on charcoal. The general theory of adsorption from solutions is derived chiefly from observations on liquid/liquid and liquid/gas interfaces, while most experimental data, on the other hand, are recorded with char coal as the adsorbent. The reason for this is the importance of charcoal as an adsorbent for technical and commercial purposes, and the extreme complexity of the adsorption on charcoals. The discrepancies in the observations from experiments with charcoal as adsorbent are so great t h a t it has been seriously proposed t o abstain from using charcoal for theoretical studies. Adam (6) con siders it unlikely t h a t the fundamental laws of adsorption will ever be discovered b y using such a complex surface. I n order t o attack the special problem of adsorption of electro lytes on charcoal, it will be necessary t o discuss the mode of pre paration of activated charcoals, and the prevailing conception regarding the nature of its surface (Chapter 2). The findings and the important conclusions of previous investig ators in regard to electrolyte adsorption on charcoal will be reported

in the following section (Chapter 3), together with references t o t h e theoretical considerations which they have animated (Chap ter 4). I t will be seen t h a t the observed phenomena are very complex, and t h a t charcoal is a very poorly defined product. I t has con sequently been considered expedient t o restrict the investigation chiefly t o those types of charcoals which are supposed t o exhibit a surface t h a t can be ascribed t o elementary carbon. The general plan of the present investigation is discussed in Chapter 5, t o which the reader is referred.

II. Production and Nature of Activated Charcoals. The Surface of Charcoals.

I n the manufacture of activated charcoals we may distinguish between two stages, a pre-carbonization process and the activation process. I t is possible t o combine both stages in a direct process. Theoretically any kind of carbonaceous material can be used as raw material for activated charcoals. As it is desirable t o obtain a high dispersity of the product, organic materials are chiefly used, and not mineral coal. The vegetable substances commonly used are wood, peat, cocoa-nut shells, cottonseed, olive and other fruit kernels. Animal materials are nowadays of less importance, although some charcoals are still made from blood and especially from bones. Activation is carried out according to two different kinds of processes. "Chemical'' activation is a carbonization process regulated in order t o retain and enlarge the surface of the organic raw material. A lamellar or cellular structure of the raw material is necessary. I n the "chemical" process, the organic substance is impregnated with solutions of chemicals and heated without admission of oxygen. The inorganic substances often used for impregnation are zinc chloride, phosphoric or sulphuric acid. These chemicals are known t o be dehydrating agents. If bones are used as raw material, no addition of chemicals is necessary, as the bones contain a large amount of calcium phosphate. "Gas activation" consists in slow partial combustion of the precharred raw material, causing an enlargement of the surface of the carbon. As a source of oxygen for the combustion, air, steam or carbon dioxide may be used. The structure of the raw material is of less importance in the gas activation process, and mineral coal may also be used.

Both processes are carried out a t a temperature of 4001000 C. Activated charcoal, especially "chemically" activated, will contain large amounts of inorganic substances. I n order t o purify the pro duct the charcoal is boiled with acids, washed and dried. The last traces of ash are very difficult t o remove. Most technical charcoals contain 525% ash. Some technical charcoals are first activated "chemically", then washed, and subsequently gas-activated. The literature on the manufacture of activated charcoals is copious, and comprises a large number of descriptions of patented methods. Reviews on the subject have been published by, among others, Kausch ( 9 0 ) and Wohryzek ( 1 8 9 ) . The production of activated charcoals is a very difficult technical process if uniform products are t o be obtained on a commercial scale. Variations in the raw material and the activation tempera ture and other such factors will influence the character of the char coal obtained, and make it unsuitable for some purposes. The grouping of charcoals into several classes, generally made according t o the recommendation of Mecklenburg (131) and used in technology, is of little interest in the present investigation. Charcoal has been assumed t o be amorphous carbon, which idea could not, however, be confirmed b y the X-ray investigations b y Debye and Scherrer (49) and b y Hofmann (82). These authors observed an X-ray pattern of the graphite type, with very broad interferences in the powder diagrams. The diffuseness of the interferences was assumed to be caused b y the dimunitive size of the graphite crystallites. Later Arnfelt (12), and Berl, Andress, Reinhardt and Herbert (23) observed simultaneously t h a t all reflexes were not equally diffuse. The diagrams were found t o correspond t o a two-dimensional graphite lattice. The close relation between the graphite and activated charcoal has later been con firmed not only b y X-ray analysis (24, 80, 82, 83, 84, 187) b u t also b y studies on the electron diffraction (183) b y charcoal. The surface of active charcoals in technical use is coated t o a considerable extent with organic and inorganic substances. If the charcoal after its activation has not been kept perfectly isolated, its surface will contain also an amount of adsorbed molecules, the nature of which are in general unknown.

These impurities will not only quantitatively but also quali tatively influence the adsorptive power of the charcoal. This fact will probably explain some of the discrepancies in the adsorption results obtained b y different investigators. I t is known, for in stance, t h a t the ash content of charcoals has a pronounced in fluence on the adsorption of electrolytes, as will be discussed later. I n addition t o the ash, the amount of oxygen in the surface will be of especial importance with regard t o the theory of electrolyte adsorption, as it is assumed t h a t part of this oxygen is present in the form of oxides capable of electrolytic dissociation. From the investigation of Dewar (50), i t is known t h a t oxygen is adsorbed on charcoal a t temperatures below 0 C followed by a liberation of an adsorption heat which has the same order of magnitude as t h a t liberated by nitrogen adsorption. The adsorbed oxygen can be desorbed as molecular oxygen on evacuation. At higher temperatures the oxygen leaves the charcoal combined with carbon as oxides. I n this case the heat of adsorption, according t o Blench and Garner (27) is of the same order as t h a t occurring in the formation of carbon oxides. Baker (13) found t h a t carbon dioxide was formed on admission of oxygen t o wet charcoal a t room temperature. Dried charcoal adsorbed oxygen, which could be liberated a t 500 C as carbon monoxide. Most charcoals used in adsorption experiments have been in some contact with air. I t is known from several investigations t h a t slow combustion of carbon takes place even a t room tempera ture. This phenomenon, inappropriately named "auto-oxidation", has been studied b y Lowry and Hulett (130), Rideal and Wright (165, 166), and other investigators. Lowry and Hulett in this connection made a complete review of the investigations on the adsorption of oxygen on charcoal carried out since 1814. I t has been ascertained t h a t the weight of the charcoal increases on free admission of air. Gradually, however, gases are liberated, especially a t elevated temperature, every molecule of adsorbed oxygen giving a molecule of carbon dioxide. I t is suggested t h a t this process of oxidation occurs only a t comparatively few points of the surface of the charcoal (active centres). The nature of the chemisorbed oxygen has been discussed b y several in vestigators.

Rhead and Wheeler (164) believed t h a t the formation of carbon oxides from oxygen and charcoal was initiated by a formation of a surface complex between the charcoal and the adsorbed oxygen. This surface oxide was given the general formula CxOy. Later Blench and Garner (27) and Garner (73) suggested the existence of three different surface oxides, because adsorbed oxygen was found t o be liberated in three different forms, namely as oxygen, carbon monoxide or carbon dioxide. I n 1915, Langmuir (120) had already suggested a formula (Table 1, Formula A) for a surface oxide which could be used t o interpret the expulsion of carbon monoxide on heating. His theory was extended b y Garner and Mc Kie (74), who considered t h a t the oxide of Langmuir was only formed a t temperatures above 200 C. Between 100 C and 200 C another oxide (Table 1, For mula B) was formed. I t was thought t h a t below 100 C two further Table 1. Hypothetical carbon surface oxides.
A:
1

B:

C:

D:

C= o

I c=o I I c=o c=o

I/Oc< I 0 0 c<f| I 0 I/ O c< I 1

r \0

I =c \/ O ) =c I I =c =c
yO

I =c x o/O =c
N

I /O CN I < i vo
E: F:

=c /O =c

> 0

G:

= C= 0 = C= O

= 0 C

^>0
C = 0

c = o
N o

=c=o =c=o

c = o \ ^>0 c = o

- c \ o c /= o

types of adsorption complexes could exist. These assumptions were based on studies of the adsorption heat of oxygen on charcoal, measured a t different temperatures. The importance t h a t might be attached t o the existence of sur face oxides in adsorption of electrolytes on charcoal was first mentioned b y Schilow and Tschmutow (175, 176). Later, Schilow, Schatunowskaja and Tschmutow (173) assumed a group of sur face oxides t o exist, which were assumed t o be stable a t different temperatures and different pressures of oxygen, in order t o account for the adsorption of electrolytes. Two of these oxides (Table 1, Formulae CE) were expected t o be alkaline oxides and a third (Formula F) t o be acid. I n the same connection, the possible ex istence of an inner salt between two of these oxides was suggested (Formula G). These authors thought it possible t o make a quali tative picture of the different behaviours of different specimens of charcoal when acids or alkalis were adsorbed, basing their opinion on the assumption of the existence of the mentioned oxides on the surface of the charcoal. The theory of Schilow and co-workers will be discussed later on. The existence of surface oxides of the mentioned type is still hypothetical. Allmand and Chaplin (7, 8) found it possible t o expel the ad sorbed oxygen with gaseous chlorinated hydrocarbons. However, they only obtained carbon monoxide and carbon dioxide as desorption products. Several investigations on the extraction of oxidized charcoals with liquids have been reported. I t is of course possible t o extract tars from inadequately carbonized products. Kolthoff (104) however, was able t o show t h a t even charcoals thoroughly activ ated a t 800 C contained acid substances, when subjected t o pro longed oxidation a t 4 0 0 C. King ( 9 3 , 9 4 , 9 8 ) found it possible t o extract an acid substance with sulphuric acid from ash-free charcoal activated with steam and oxygen. King and Lawson (97, 98) believed this substance t o be oxalic acid, as it could reduce permanganate. King (94) assumed that the presence of chemisorbed water was necessary for the formation of oxalic acid on charcoal. The amount of liberated acid in these experiments was found t o be surprisingly independent of the activation temperature, which varied between c. 200 and 900 C. When highly desiccated

charcoal activated with dry oxygen was used, no acid was de tected. The amount of acid liberated was very small, equivalent t o only about 60 y oxalic acid per gramme of charcoal. Bunte and Brckner (39) also observed a formation of oxalic acid on pit coal. Peters and Cremer (159) could extract an acid substance from oxidized charcoal which reduced permanganate, b u t in their opinion the substance in question was not oxalic acid. Among the substances extracted from charcoal are also included peroxides. Lamb and Elder J r . (116) extracted a peroxide from steam-activated charcoal using sulphuric acid as extraction medium. This peroxide was considered t o be responsible for the catalytic properties of carbon in processes of oxidation. King and Lawson (97, 98) have estimated the peroxide in extracts from charcoals b y its reaction with permanganate. The peroxide, calculated as hydrogen peroxide, was found never t o exceed 3 10~4 % of the charcoal. They considered i t improbable t h a t the catalytic properties of the charcoal could be ascribed t o this sub stance. The amount of peroxides was found t o increase with in creasing amounts of impurities in the charcoal. Kolthoff (104) has also estimated the peroxide in charcoal. He found larger amounts of peroxide in charcoals activated a t 900 C t h a n in those activated a t 400 C. I t is practically impossible t o obtain two charcoals completely identical as regards their quantitative adsorption properties. This observation can be inferred from the previous discussion of how different methods of activation, varying raw materials, etc. will influence not only the area of the charcoal per unit weight, but also the nature of the surface. These facts will immensely com plicate the theoretical treatment of adsorption on charcoals. As the matter now stands, the nature of the charcoal used for scientific investigation can only be indirectly described b y giving a detailed account of the method used for its manufacture, and the source of the raw material, together with the results of the ad sorption experiments. Only if such a plan is adopted universally will it be possible t o compare the findings of different invest igators, and thereby obtain a means for establishing with greater

certainty a true conception of the nature of the surface of different charcoals. I t is t o be regretted t h a t many contributions t o the theory of adsorption on charcoal are still published without giving accounts of the origin and history of the charcoals used in the experiments on which the theoretical considerations are founded.

2 4 4 5 9 3 Brje Sleenberg

17

III. The Principal Qualitative Observations of Electro lyte Adsorption on Charcoal.

The investigations of electrolyte adsorption on charcoal may be divided into three epochs. Early investigators used charcoal chiefly of animal origin which generally contained 550 % ash. Owing t o the use of such con taminated products the investigators obtained very contradictory results. Using charcoals with a high content of ash, it was impossible t o ascertain with any degree of definiteness whether the adsorp tion of ions depended on the carbon or on the inorganic impurities in the material. The latter contingency has been suspected even in the findings of comparatively recent years (45, 99). The art of manufacturing gas-activated charcoals very low in ash from pure organic materials was unknown in the times of these early investigators. Methods for making ash-free charcoals were published in about 1920 b y Lamb, Wilson and Chaney (117) and by Winter and Barker (188). By the use of gas-activated char coals, produced in strict accordance with established methods, qualitative agreement between the observations on electrolyte adsorption could be obtained b y different investigators. I n the period from about 1920 t o 1930 it was thought t h a t low-ash gasactivated charcoals were essentially identical in their adsorption character. About 1930 the problem was again becoming complicated. I t was observed t h a t the activation temperature of the charcoal had a profound influence on the adsorptive character of the charcoal towards electrolytes, not only in quantitative but also in qualita tive respects. The influence of the activation temperature on the nature of the charcoal has not been systematically investigated until lately, and these results have not yet met with universal acceptance.

The great profusion of the literature concerning electrolyte adsorption on charcoal, comprising over 500 papers in the last 30 years, together with the absence of critical reviews of the whole field of investigation, affords perhaps an explanation of why many papers on the subject are still being published without proper regard t o earlier experiences. I n a critical review of the publications it is almost impossible t o refrain from testing many of the published experiments, in order t o check the methods employed, and t o t r y t o find out, if possible, with which general type of charcoal the experiments have been carried out. As pointed out, information in the latter respect is very often lacking or incomplete. The writer has carried out a large number of experiments in order t o check these earlier results. Not only was this slow and laborious work deemed necessary for a review of the literature on the subject, but it was in the author's opinion impossible, without the experience gained from such a course of procedure, t o organize the supplementary experiments t h a t were t o serve as a foundation for a theory on electrolyte adsorption. (Compare ( 1 7 1 ) . ) The workers who used charcoal with large contents of ash, were generally able t o observe adsorption of inorganic acids and alkali hydroxides on the same charcoal. Very contradictory results, on the other hand, were reported from experiments on the adsorption of inorganic neulral salts. I t was claimed t h a t neutral salts were not adsorbed, and even t h a t they were negatively ad sorbed ( 1 1 5 ) ; others noted t h a t positive adsorption had taken place (77). When positive adsorption of the salt was observed, i t was thought b y some investigators t h a t the ions of the salt were adsorbed in equivalent amounts (molecular adsorption) (98, 134), and b y others t h a t only one of the ions was adsorbed. I n the latter case, some investigators found t h a t the neutrality of the solution was maintained, others noted changes in the p H of the solution either in an acid or an alkaline direction (hydrolytic adsorption). (Early publications in ( 1 7 1 ) . ) Before using the charcoal for adsorption experiments, these investigators generally purified the material b y digestion with concentrated hydrochloric acid, and subsequently washed the

product with conductivity water until the chloride reaction of the water disappeared. Although it was known t h a t the ash con tent of the charcoal could only be very imperfectly reduced b y this treatment, part of the ash being silicates, i t was thought t h a t the charcoals were completely freed from soluble impurities. Miller (137, 138, 139) proved t h a t this assumption also was in correct. Miller demonstrated t h a t on boiling HCl-treated and washed charcoal with sodium hydroxide, considerable amounts of chloride could still be liberated. Although the ash content of the charcoal was reduced b y the washing, chlorine, which could not be washed away with water, was introduced in the product instead. Miller tried several methods t o purify charcoals. He found only hydrofluoric acid t o be an effective agent. I n order t o obtain an ash-free, active charcoal the raw charcoal had t o be treated with this acid, washed, treated afresh with nitric acid, washed and thereafter activated with oxygen. This process, as f a r as is known, has only been practised a few times, as it is easier t o obtain ash-free charcoal direct from pure organic chemicals b y means of gas activation. I t is of little interest t o review the various investigations on adsorption of electrolytes on high-ash charcoals, since the different investigators do not agree even in the qualitative respect in regard t o their principal observations. The first investigation of the adsorption of electrolytes on ashfree charcoals was carried out b y Bartell and Miller (18) in 1922. Although the method of preparation of the charcoal was very primitive, t h e results published b y Miller and his co-workers in the course of the subsequent decade must be considered t o be of fundamental importance t o modern research on adsorption of electrolytes on charcoal. The charcoal used in these investigations was made from pure sugar, which, after carbonization, was activ ated with air a t comparatively high temperatures (c. 900 C). The activation was carried out in a heated crucible not completely covered, in order t o allow air t o come into contact with the raw charcoal in the crucible. The experimental results of Miller and co-workers with respect t o electrolyte adsorption on ash-free char coals activated a t about 900 C, although they were for some time doubted (101), have been confirmed on the major points b y later

investigations (103). The method of preparing charcoal described b y Bartell and Miller was the first one enabling uniform results t o be obtained, a t least qualitatively, with different samples of char coal. The observations of Bartell, Miller and co-workers (18, 19, 20, 135, 136, 137, 138, 139, 140, 141) must be considered, for the reasons stated, t o be of special interest in this paper. When these in vestigators used charcoals made from pure sugar, gas-activated a t about 900 C and rapidly cooled, they found t h a t inorganic acids were adsorbed in remarkably large amounts. The adsorption of hydrogen ions increased upon addition of an alkali salt of the acid. No adsorption of alkali hydroxides could, on the other hand, be observed during these experiments. I n some cases even a "negative" adsorption was noted. If small amounts of sodium hydroxide were dissolved in concentrated solutions of alkali halogenides and the solutions treated with large amounts of dry charcoal, the concentration of the hydroxyl ions was found t o increase. I t was thought t h a t water was adsorbed preferentially t o the electrolyte (136). The negative adsorption of hydroxyl ions was not found t o be stable, as it decreased and was found t o be zero after approximately 24 hours of contact between the solution and the charcoal. Positive adsorption could not be ob tained on prolonged contact (140). On adding solutions of salt t o the charcoal the qualitative re sults varied with the composition of the salt, and t o some degree with its concentration. Neutral solutions of inorganic salts, especially alkali salts, became in the experiments of Miller and co-workers distinctly alkaline after contact with the charcoal. I t was ascertained analytically t h a t the ions of the alkali metals were not adsorbed b y the char coal. The inorganic anions, however, were slightly adsorbed. I t was always found t h a t the amount of liberated hydroxide was equivalent t o the adsorbed amount of anions (136). The adsorption of inorganic salts was considered t o be entirely hydrolytic in nature. The adsorption of alkali ions from organic salts was found t o proceed in different directions, depending upon the nature of the anion. From solutions of potassium oxalate no potassium ions were adsorbed. On the other hand, adsorption of potassium ions

was observed if solutions of potassium benzoate or salicylate were placed in contact with the charcoal. From alkali salts of organic acid dye-stuffs alkali ions were always found t o be adsorbed, but generally in smaller amounts t h a n the organic anions. The solution was found t o increase its p H during the adsorption. The largest change in p H was observed when only small amounts of the dyestuffo were present in the system (19). Inorganic salts of basic dye-stuffs were adsorbed on the charcoal upon decreasing the p H of the solution. I t was observed t h a t after the adsorption the solution contained an excess of the in organic anion over the organic cation. A certain amount of the anions was, however, always adsorbed. A further decrease in p H was observed with increasing amounts of adsorbed dye-stuff (18). From these experiments Miller and co-workers concluded t h a t the adsorption of organic salts was partly hydrolytic and partly molecular in nature. The following principal observations of Miller and co-workers have later been confirmed when experiments have been performed using charcoals activated by Miller's method: 1. Non-adsorbability of alkali metal ions from inorganic salts. 2. Adsorbability of alkali metal ions from most organic salts. 3. Non-adsorbability of alkali hydroxides. 4. Adsorbability of all anions, except the hydroxyl ion in alkali hydroxides. 5. Adsorbability of hydrogen ions and organic cations. 6. Exclusively hydrolytic adsorption of inorganic salts of the alkali metals, giving increased p H t o the solution. The p H in creased with increasing concentration of the salt t o a n upper limit. 7. Partly hydrolytic adsorption of salts with larger organic anions, giving increasing p H t o the solution. The alkalinity of the solution after adsorption became smaller in relation t o its p H before the process when the concentration of the organic salt increased, b u t the solution was never more acid after than before the process. 8. Partly hydrolytic adsorption of salts with organic cations, giving decreased p H t o the solution. The acidity of the equilibrium solution became smaller with increasing concentration of the salt.

Note: I t has been reported b y one investigator (47) t h a t the p H of the equilibrium solution was higher than the p H of the initial solution on using a solution of a salt with an organic cation (methy lene blue chloride). The quantitative results of the different effects observed b y Miller and co-workers cannot be reproduced. Miller used an ex perimental technique b y which the adsorption was determined from analysis of the filtrate of the charcoal suspension. Before analysis the charcoal was frequently washed, and the washings were added t o the original filtrate. The volume of the solution, for example, is not stated. Qualitatively identical phenomena are also observed, however, when analysis is carried out on a solution which has been in contact with the charcoal for a time sufficiently long t o establish a steady state. The inconsistent results with electrolyte adsorption obtained prior t o Miller were interpreted b y him as a consequence of the presence of ash in earlier used charcoals. Great interest was aroused when in about 1930 it was found possible t o obtain ash-free gas-activated charcoals capable of adsorbing alkali hydrox ides but not, or only t o a slight extent, inorganic acids. These charcoals were activated a t a temperature considerably below the activation temperature used b y Miller. Ash-free charcoals were also observed which adsorbed inorganic alkali salts hydrolytically on decreasing the p H of the solution. The first observations on charcoals of this type were published b y Kruyt and de K a d t (108) and Dubinin (57). I t was soon found t h a t on increasing the activ ation temperature above about 500 C, the hydrolytic adsorption of inorganic alkali salts reversed in sign. This phenomenon was, however, not systematically studied until a few years ago. These experiments were carried out b y King and his co-worker (93, 94,
95, 96, 47).

King (96) activated raw charcoal made from pure sugar in a slow flow of moist oxygen a t temperatures varying between 350 and 1000 C. After as rapid cooling as possible, the adsorptive power of the charcoal was determined. The adsorptions of hydro chloric, acetic and benzoic acids, of sodium and ammonium hydrox ide and of iodine from an unspecified solution were studied. The initial concentrations of all these substances are not reported but

seem t o have been the same in all cases. The adsorptive power of the charcoal was found t o vary considerably with the activation temperature. Charcoals activated a t low temperatures (380 420 C) did not adsorb hydrochloric acid, as was the case with charcoals activated a t higher temperatures. The adsorption of hydrochloric acid and the weak organic acids increased with in creasing activation temperatures u p t o about 900 C; a t still higher activation temperatures the adsorbed amount of these substances was observed t o decrease slightly. Sodium hydroxide was found t o be adsorbed very markedly on all charcoals heated between 380500 C, but the adsorbed amount decreased on increasing the activation temperature, and was found t o be zero on charcoal activated a t 810 C. King found t h a t the adsorbability of sodium hydroxide reappeared on charcoals activated a t still higher tem peratures. The last-mentioned observation is unique. Most of the charcoals used b y Miller were activated a t 8001000 C, and were not found capable of adsorbing alkali hydroxides. Neither could Kolthoff (104) observe any adsorption of alkali hydroxides on charcoals activated a t these temperatures. King considered t h a t his experiments showed t h a t the adsorptive property of an ash-free charcoal was principally determined b y the temperature of the gas-activation, provided the product was rapidly chilled. H e found t h a t a charcoal originally activated a t a high temperature, and again a t a lower temperature, took on the characteristics of the low-temperature activated char coal. Kolthoff (104) has demonstrated t h a t heat treatment in vacuum a t a n arbitrary temperature does not change the charac ter of a charcoal activated a t 800 C. On the contrary a charcoal activated a t a very low temperature and heated in vacuum a t a temperature above 600 C will resemble in its adsorptive charac teristics a charcoal gas-activated a t a higher temperature. Chambers and King (47) have also carried out an investigation on the change in hydrolytic adsorption of salts on varying the activation temperature of the charcoal. I t was found t h a t neutral solutions of potassium chloride, in contact with charcoals activated a t temperatures below 500 C, always became acidified. If the charcoal was activated a t a higher temperature, potassium hydrox ide was set free. Sodium benzoate was found t o be hydrolytically

adsorbed only on charcoals activated a t temperatures above 500 C L I n these cases the p H of the solution increased. For convenience's sake, charcoal prepared according t o the method of Miller will henceforth be called "H-charcoal" in this paper. The term H-charcoal will be used for all gas-activated charcoals t h a t do not adsorb alkali hydroxides. Charcoals of the H-type can only be prepared b y gas-activation a t temperatures above 750 C, as far as is known. All charcoals able t o adsorb alkali hydroxides will be designated as "L-charcoals". Typical L-charcoals may be produced b y using activation temperatures of less t h a n 600 C. L-charcoals are obtained irrespective of the activation temperature if the charcoal is cooled slowly after the activation in the presence of oxygen. The majority of the published experiments on electrolyte ad sorption on charcoals have been qualitative or semi-quantitative; very rarely have complete adsorption isotherms, for instance, been reported. I t has consequently been thought advisable in this connection not t o discuss the more detailed quantitative results of earlier investigators but t o proceed a t once t o the theoret ical considerations on electrolyte adsorption on charcoal made since 1920.

IV.

Earlier Theories on Adsorption of Electrolytes on Charcoal.

A.

The theory of Bartell and Miller, 1924.

Because of their observation t h a t t h e reaction of a salt solution could be displaced in t h e acid or t h e alkaline direction when t h e solution was p u t into contact with samples of the same charcoal, Bartell a n d Miller (20) found i t necessary t o assume t h e simul taneous existence of both acid and alkaline groups on t h e surface of t h e charcoal. They rejected t h e hypothesis t h a t these groups originated from undecomposed organic substances in t h e charcoal, on t h e ground t h a t t h e presence of such substances was not con ceivable with t h e method of activation used. The ash content was f a r too low t o explain t h e observations. The suggestion was made t h a t t h e hydrogen and hydroxyl groups on t h e charcoal originated from t h e water adsorbed on t h e surface, which was believed t o consist of pure carbon. The theory applied only t o H-charcoals, t o which t h e investigations of Bartell a n d Miller h a d been confined. Bartell a n d Miller postulated t h e existence of several kinds of active centres on t h e surface of t h e charcoal. The residual forces of some of these centres were thought t o show preferential attraction either for electropositive or for electronegative substances. Water was assumed t o be adsorbed a t these centres. The majority of t h e water molecules were bound b y non-polar forces b u t some of them were adsorbed with t h e hydroxyl ions of t h e water molecules attached t o t h e charcoal, t h e hydrogen ion facing t h e water phase. Another p a r t of t h e adsorbed water molecules were oriented with t h e hydroxyl ions towards t h e water phase, t h e hydrogen ions being primarily adsorbed. According t o their theory those ions from t h e water which were primarily adsorbed could be exchanged for ions from t h e solution.

The adsorption of acids was interpreted as an exchange of the anion of the acid b y the primarily adsorbed hydroxyl ions. The expelled hydroxyl ions formed undissociated water with the hydrogen ions from the acid. A consequence of this theory was the increase in adsorption of an acid on addition of its salt. Inorganic cations of metals more noble than hydrogen were, according t o their theory, incapable of being exchanged for t h e primarily adsorbed hydrogen ions when the solution contained only salts of inorganic acids. Some of the anions from these salts, however, were believed t o be exchangeable for hydroxyl ions on t h e charcoal surface, thus rendering the solution alkaline. If the solution of the salt contained organic anions, irrespectively of the strength of their acids, the metal ions could be adsorbed, although t o a slightly lesser degree than the anions, thus rendering t h e solution slightly alkaline. Organic cations were adsorbed, expelling an equivalent amount of hydrogen ions from the charcoal. As in this case the cation exchange was thought to be more pronounced than the anion ex change, the solution was expected t o be acidified; this had, in fact, been observed in the experiments of Bartell and Miller. I t was observed t h a t the liberation of acid on adsorption of a salt, when only the cation was organic, was largest when only a small amount of the organic salt had been added. I t was believed t h a t this depended on the difference in the rate of exchange of ions of different signs. The anion was thought t o displace the hydroxyl ions from the charcoal a t a slower rate than t h a t a t which the organic cation was exchanged for the hydrogen ion. Thus, the solution was distinctly acid after the addition of a small quantity of the organic salt, but gradually, as the adsorption of the anion proceeded, the solution became less acid until finally, a t the close of the experiment, it again became neutral. This explanation seems t o imply t h a t equilibrium was not supposed t o be obtained i n the experiments. Bartell and Miller were of the opinion t h a t every anion could be exchanged for the primarily adsorbed hydroxyl ions. Charcoal i n contact with pure water was supposed t o be saturated with iydroxyl ions. According t o their belief, therefore, no adsorption

of alkali hydroxides is possible, a n d t h e results of their experi ments confirmed this view. The weakest point in t h e theory of Bartell and Miller is t h e prim ary adsorption of hydroxyl ions. If i t be assumed t h a t t h e charcoal has such a strong affinity for hydroxyl ions, i t is surprising t h a t n o further hydroxyl ions can be adsorbed from a solution of a n alkali hydroxide. If, on t h e other hand, t h e affinity of t h e char coal towards t h e hydroxyl ions is so strong t h a t t h e surface layer becomes saturated with hydroxyl ions a t t h e mere contact with pure water, i t is difficult t o understand why, in some cases, t h e hydroxyl ions can be exchanged for other anions in neutral a n d even slightly alkaline solutions, as was observed b y Miller. The behaviour of t h e alkali ion in being adsorbed when organic anions are present is difficult t o understand on t h e basis of their theory. I t is, moreover, inconceivable, a s pointed out b y Kolthoff (102, 103) and Mukherjse (142), t h a t t h e exchange should occur with t h e primarily adsorbed ions, a n d not with t h e ions in t h e p a r t of t h e electrical double layer facing t h e water phase. Kolthoff (103) in this connection gives some empirical rules for t h e adsorption of electrolytes. H e believes, for instance, t h a t hydrolytic adsorption of salts of surface active acids only occurs when t h e anion is not adsorbed in a n oriented manner. On account of t h e objections raised, t h e theory of Bartell a n d Miller is not discussed b y Miller in his last review of electrolyte adsorption on charcoal published in 1932 (140).

B.

The Miller "Hydrolytic"

Theory.

Miller h a d observed t h a t i t was impossible quantitatively t o desorb acids from charcoals b y washing with finite amounts of pure water. H e considered t h a t t h e acid initially adsorbed b y t h e charcoal was retained b y very strong forces of adsorption, and t h a t t h i s adsorbed acid could not t o a n y appreciable extent be desorbed with a moderate quantity of washing water (141). This electrolyte was regarded as irreversibly held b y t h e charcoal. H e found t h a t

t h e only way t o desorb this acid was t o treat the charcoal with alkali hydroxides. The charcoal was, however, according t o Miller, also capable of adsorbing acids in a reversible manner. If the free solution was neutral after adsorption, the acid was thought t o be adsorbed only irreversibly. If the solution remained acid on the other hand both reversible and irreversible adsorption of the acid were assumed t o occur. Miller thought it probable t h a t the strong forces of adsorption changed the character of the electrolyte; some of the adsorbed acid was assumed t o be present in a molecular state. He considered this t o be the case irrespective of the nature of the acid. The increase in adsorption of, for instance, hydrochloric and benzoic acid on addition of a chloride or a benzoate respectively was interpreted as a consequence of a depression of the ionization of the acids. Miller and Bandemar (141) observed t h a t small amounts of adsorbed acid were not able t o invert cane-sugar a t 80 C. Hydro chloric acid and some organic acids were used in these experiments. I t was demonstrated t h a t the charcoal simultaneously adsorbed acid and sugar. Inversion occurred only if the free solution after adsorption of the acid was still distinctly acid. The amount of sugar inverted in this case was found t o be a function only of the time of contact and the concentration of the acid in the free solu tion. These observations were considered t o constitute a proof of the theory t h a t the acid adsorbed was present in a molecular state. The increase of the p H of a neutral solution of an inorganic salt in contact with charcoal (hydrolytic adsorption) was explained in an analogous manner. Miller thought t h a t a solution of sodium chloride, for instance, was slightly hydrolyzed. The charcoal adsorbed the molecular hydrochloric acid, thus disturbing the hydrolytic equilibrium of the solution. The amount of adsorbed chloride ions was shown t o be equivalent t o the liberated hydroxyl ions. The change in p H when organic salts were used was explained in an analogous manner. On hydrolysis, which was thought t o occur also in solutions of salts of strong acids and strong bases, those molecules which liberated the largest heat of adsorption

were preferentially adsorbed, thereby leaving the solution enriched in hydroxyl or hydrogen ions. The greatest difficulty in Miller's theory was the interpretation of the adsorption of sodium ions from organic sodium salts. On hydrolysis of a solution of such a salt, an organic acid and sodium hydroxide were t o be expected. But Miller had observed t h a t sodium hydroxide was never adsorbed by his charcoals, which were all activated a t 8001000 C. Nor were sodium ions found t o be adsorbed from inorganic sodium salts. Miller was forced t o assume t h a t simultaneously with the hydrolytic adsorption there occurred an equivalent adsorption of the ions of the salt in the solution. This phenomenon was called "mole cular adsorption", although Miller did not discuss the state of the adsorbed salt. Angelescu and Cismaru(ll) later assumed t h a t "molecularly" adsorbed salts are present on the charcoal surface as acid and base which are formed b y a complete hydrolysis of the salt. Miller's explanation seems difficult t o understand when one compares the adsorption of sodium chloride, where only chloride ions are adsorbed from the salt, and t h a t of sodium benzoate, where both ions are adsorbed in large amounts, although the sodium is adsorbed t o a slightly lesser extent. Considering the strength of hydrochloric and benzoic acid, the latter being a weak acid, one is forced t o the conclusion t h a t according t o Miller's theory the hydrolytic adsorption of sodium benzoate must be much greater than t h a t of sodium chloride. This is not found t o be the case. Miller's theory is consequently not in accordance with the theory of the dissociation of electrolytes. I t cannot even qualitatively explain all the phenomena of adsorption on char coals activated a t high temperatures, e.g. the change in hydrolytic adsorption of an organic salt on changing the concentration of the salt. Notwithstanding the objections mentioned here, and because no other earlier published theory can provide a more acceptable interpretation of the phenomena in question, this theory has gained the support of several investigators, among others Kott hoff (103) and Fromageot (64).

C.

The oxide theory of electrolyte adsorption.

Bartell and Miller only investigated H-charcoals. I n 1929 K r u y t and de K a d t (108) made t h e first report on L-charcoals. Soon afterwards, Burstein and Frumkin (42) described experiments with charcoals gassed out a t 1000 C on which no adsorption of electrolytes could be observed. These results could not be con firmed b y Schilow and Tschmutow (175), who noted adsorption of hydrochloric acid even after t h e gassing out. These authors were unable t o obtain a n y hydrolytic adsorption of inorganic salts on this gassed-out charcoal, unless small amounts of carbon dioxide were present. Subsequently, t h e same authors (176) came t o t h e conclusion t h a t t h e adsorption of hydrochloric acid depended on t h e oxygen pressure in t h e system. A reduction in t h e oxygen pressure caused n o change in t h e adsorption of this acid until t h e pressure was reduced t o about 2 mm. Hg, when t h e adsorption of t h e acid rapidly decreased. No change in adsorption was ob served upon reducing t h e pressure still further. These experimental results will be discussed further on. I n order t o interpret their observations Schilow and Tschmutow ventured t h e explanation t h a t oxides were formed on t h e surface of t h e charcoal in t h e presence of oxygen. These oxides were assumed t o be stable within different ranges of oxygen pressure and capable of electrolytic dissociation in contact with water, functioning a s bases. The adsorption of hydrochloric acid was interpreted a s a neu tralization of t h e alkaline oxides on t h e surface of t h e charcoal. Schilow and Tschmutow mentioned t h a t this theory explains t h e hydrolytic adsorption of solutions of inorganic salts on H-charcoals. These authors seem t o have been unaware of t h e fact t h a t hydro lytic adsorption of organic salts m a y proceed in t h e opposite direction on these charcoals. I n a later paper, Schilow et al. (173) assumed t h e existence of a n acid carbon oxide which was supposed t o bring about ad sorption of hydroxides on L-charcoals. This acid was believed t o account for t h e hydrolytic adsorption of inorganic neutral salts on L-charcoals. A formula for a salt between a n alkaline and a n acid carbon oxide which would account for t h e behaviour of those

charcoals which were able t o adsorb both acids and alkali hydroxides was also given. The formulae of these oxides are shown in Table 1. The theory advanced b y Schilow et al. evoked considerable interest, especially as de K a d t (88), a t Kruyt's laboratory in U t recht, simultaneously reported his observation t h a t ash-free H charcoals behaved as positively charged particles when suspended in water. If these charcoals were heated in oxygen a t 400 C, the charge changed its sign t o negative. Kruyt and de K a d t (108) found t h a t the electrical charge of ash-free charcoal suspended i n water could be changed a t will on heating the charcoal a t differ e n t temperatures. This observation was of great importance because the earlier investigations on the electrical charge of charcoal suspended in water had yielded very varying results. From the experiments of Perrin (157) it was for some time believed t h a t the iso-electric point of charcoal was very near p H 7. This conclusion was later doubted, and there was much discussion, for instance, concerning the iso-electric point of blood-charcoal, a type of charcoal commonly employed for scientific use. Different investigators found the iso electric point of this material t o be anywhere between p H 3.0 and 7.6 (29, 76, 91, 106, 127, 132, 177, 185). Later, positively charged commercial charcoals were also observed (152). Kruyt and de K a d t (108) found t h a t only negatively charged charcoals were able t o adsorb sodium hydroxide. The reversal in the charge of the charcoal particles was ascribed t o a formation of carbonyl groups b y heating the H-charcoal in the presence of oxygen a t low temperatures. A transformation of the surface of the charcoal into mellitic acid was suggested as a possible mechanism. A more complete theory regarding t h e adsorption of electro lytes on all types of charcoals was later presented b y Kruyt and de Kadt (109) along the same lines as t h a t of Schilow and his co workers. The presence of either acid or alkaline carbon oxides was suggested in order t o explain the adsorption of inorganic electrolytes on different types of charcoals. Kruyt and de K a d t did not, however, exclude the possibility t h a t the adsorption of acids depends on a specific property of the charcoal t o adsorb

hydrogen ions. The behaviour peculiar t o organic salts in adsorp tion is not discussed b y these investigators. I t might be mentioned t h a t Syrkin and Potapew(181) have suggested t h a t the presence of carbon nitrides on the surface of the charcoal may explain the ability of certain charcoals t o adsorb acids. As most sugar charcoals are free from nitrogen this ex planation cannot be universally valid. The theory of the presence of surface electrolytes as the origin of adsorption of electrolytes on charcoals has obtained some support from Acharya's experiments (4, 5). This investigator observed t h a t if charcoals are treated with alcoholic solutions of organic aliphatic acids insoluble in water, and dried, a coating which increases the negative charge of the charcoal is formed. The acid-coated charcoal produced in this way exhibits less ad sorption power towards benzoic acid than the untreated charcoal. Strong inorganic acids were not used as adsorbates b y this in vestigator. Acid-coated charcoals were found t o liberate acid on contact with solutions of neutral inorganic salts. After gas activa tion of the coated charcoal the ability t o adsorb salts hydrolytically was found t o decrease. After coating the charcoal with organic water-insoluble amines the adsorption of organic acids was found t o increase. Several indirect attempts t o obtain information in regard t o the nature of the hypothetic acid and alkaline oxides on the sur face of the charcoal have been carried out. Bruns, Maximowa and Pos (35) have investigated the formation of acid oxides on the surface of the charcoal, assuming the ad sorption of hydroxides t o be a measure of the amount of these oxides. They found the amount of oxides estimated b y this method t o be very dependent on the nature of the raw material of the char coal, especially if the charcoal was activated a t low temperatures. If large amounts of unburnt organic substances were present, the adsorption of sodium hydroxide was large. They considered the surface oxides t o be very stable, because they were not reducible with hydrogen, even in the presence of platinum as catalyst. These results are not in accordance with the observations of Schilow and Tschmutow, who found it possible t o decompose some of t h e surface oxides merely b y reducing the pressure. Bruns, Maxi3 44593 Brje Steenberg

33

mowa and Pos support Frumkin's theory of electrolyte adsorption (vide infra). King (95) has studied electrometrically the p H of charcoals suspended in water, using a glass electrode, in order t o obtain information regarding the possible existence of acid or alkaline oxides on the charcoal. The technique employed b y King had not previously been applied t o pH-measurements in charcoal suspen sions (28, 29, 178). King observed t h a t the p H of the suspensions was a linear function of the activation temperature of the charcoal. H e believed the observations t o be in accordance with the oxide theory of electrolyte adsorption, but mentioned t h a t other ex planations were also possible, e.g. the preferential adsorption of hydrogen or hydroxyl ions from water. King does not state how he connected the calomel electrode with the cell used for the pH-determinations. This is known t o be of importance in colloidal suspensions. I t is possible t h a t King measured the p H resulting from a hydrolytic adsorption of potas sium chloride emanating from the calomel electrode. The experiments of Schilow and Tschmutow on the adsorption of inorganic acids a t low pressures of oxygen in the system have been repeated b y Frumkin, Burstein and Lewina (67), and by Bretschneider (30). Frumkin and his co-workers found t h a t the adsorption of hydrochloric acid decreased continuously with a decreasing pressure of the gas. Bretschneider also observed a decrease in the adsorption of hydrochloric acid on the charcoal after gassing-out. After aeration of the gassed-out charcoal the adsorptive power was restored t o t h a t of the original charcoal. Bretschneider compared the adsorption isotherms of hydrochloric acid on aerated and gassed-out charcoal. The graphically compared isotherms were found t o be parallel, except a t very low equi librium concentrations of the acid. Bretschneider suggested as a possible explanation t h a t a part of the adsorbed acid was adsorbed b y oxides on the surface of the charcoal, this part being independent of the equilibrium concentration of the acid. Lepin (121), working in the laboratory of Schilow, has inves tigated the adsorption of homologous aliphatic carboxylic acids on aerated and gassed-out charcoals. This investigator observed no influence of varying oxygen pressure on the adsorption,

provided t h a t the organic acid contained five or more carbon atoms. Lepin believed the higher homologues, being very weak acids, t o be adsorbed b y the charcoal with the hydrophobic part of the molecule. Objections t o the oxide theory of electrolyte adsorption have been raised b y Ockrent and Frumkin et al. Ockrent (151) has criticized the oxide theory from a chemical point of view. If adsorption of electrolytes is assumed t o be caused b y surface oxides, Ockrent found it necessary for the H-charcoal t o contain 1525 % oxygen, supposing the oxygen t o be equi valent t o the number of active centres on the surface, these having been calculated from, his experiments on the adsorption of weak organic acids (149, 150). Ockrent thought t h a t if an H-charcoal is transformed into the L-type, an increase in the amount of oxygen in the charcoal, large enough t o be determinable b y analytical means, must occur. From his analytical data, however, he found the amounts of hydrogen and oxygen t o be equivalent, irrespective of whether the charcoal had been activated a t a high or a low tem perature. These results are in accordance with the earlier analysis of charcoals carried out b y Ogawa (153) and Barker (15). Ockrent consequently did not consider himself obliged t o accept the oxide theory. Ockrent observed t h a t on heating the charcoal the largest part of the water was given off a t definite temperatures. From Lcharcoals the last traces of the water were not liberated until the temperature rose t o approximately 500 C. From H-charcoal the water could be completely desorbed a t lower temperatures. Ockrent thought the discontinuities in the desorption isobar t o be evidence of the existence of several activation energies for the adsorption of water. The presence of activated adsorbed water only desorbable a t 500 C in the L-charcoals was, in a manner not discussed, thought t o be the origin of the power of the L-charcoal t o adsorb alkali hydroxides. Ockrent further noticed t h a t on washing H-charcoals with pure water the material acquired the characteristics of the L-charcoal. This observation is contrary t o the findings of Mukherjee, Roychoudhury and Majumdar (143), who found it possible t o obtain electropositive H-charcoals from negative L-charcoals on continuous

washing. These authors believed the characteristics of the Lcharcoal t o be dependent on the presence of organic acids on the surface of the charcoal. The divergence in the results of experiments concerning the change in adsorption of inorganic acids with the pressure of gaseous oxygen in the system, form the starting point in the criti cism submitted b y Frumkin and his co-workers. These authors do not even accept the idea t h a t acids and alkalis are adsorbed b y a neutralization process, which is the leading point in the theories of Schilow and of Kruyt and de Kadt. Kuchinsky, Burstein and Frumkin ( i l l ) assert t h a t if the adsorption of an acid b y an H charcoal were a process of neutralization, the adsorption of an acid would a t a certain p H pass <per saltum from the zero value t o the maximum point. If the oxide theory were correct the adsorption should take place, according t o these investigators, in a comparatively narrow interval, which is in complete contra diction t o all experimental data in regard t o adsorption of acids. If i t were assumed t h a t the ionization constant of the surface oxide decreased with an increase in the number of dissociated groups, a smoother adsorption isotherm might be obtained, they suggest, b u t this picture is not considered relevant in the present case. Apart from these objections, the oxide theory of adsorption is the theory which has obtained the most general support during recent years. Thus Kling and his co-worker (47) believe this t o be the view which best interprets the observations. I n the opinion of the present writer, the chief qualitative obstacle t o an acceptance of the oxide theory is the hypothesis regarding the existence of the alkaline carbon oxides, since substances of a corresponding nature and stability are not known in organic chemistry. Further, it seems t h a t most investigators who have supported the oxide theory have failed t o take into account the earlier observations t o the effect t h a t inorganic salts of organic bases are adsorbed hydrolytically on H-charcoals giving decreased p H t o t h e solutions. This established observation can definitely not be interpreted on the basis of the presence of alkaline surface oxides on the charcoal. Furthermore, with the oxide theory, there seems no possibility of accounting for the decrease in the

hydrolytic adsorption of organic salts which is observed in connec tion with increasing concentration of t h e salt. On t h e other hand, t h e oxide theory seems plausible t o t h e writer i n t h e case of electrolyte adsorption on charcoals activated a t low temperatures. The electrolyte adsorption on L-charcoals seems t o be qualitatively of t h e same nature a s t h e adsorption of electrolytes on several substances, such as peat a n d graphitic acid, where acid groups are known t o be t h e origin of t h e ionic adsorption.

D.

Frumkin^s electrochemical theory.

I n 1903, Billitzer (26) noticed t h a t on t h e addition of platinum black saturated with hydrogen, t h e p H increased in solutions of inorganic alkali salts. This experiment was repeated in 1926 b y Frumkin a n d Obrutschewa (70). These authors were able t o obtain such large amounts of liberated acid from hydrogen-saturated platinum black treated with sodium sulphate t h a t t h e amount of acid could be determined b y titration. I t was suggested b y these investigators t h a t t h e hydrolytic adsorption of neutral inorganic salts on charcoal was a phenomenon of similar origin. With t h e classical electrochemical theory a s a starting point, Frum kin a n d his co-workers (66) assumed t h a t charcoals suspended in solutions of electrolytes behaved as reversible gas electrodes. The charge on t h e charcoal was thought t o depend upon t h e concentra tion of t h e ions i n t h e solution and t h e nature a n d t h e pressure of t h e gas which was in equilibrium with t h e system. A charcoal in contact with hydrogen was believed t o be negatively charged, t h e charge being due t o ionization of adsorbed hydrogen atoms. The hydrogen ions were emitted into t h e solution in t h e same way a s from a platinum-hydrogen electrode. The hydrogen ions were supposed t o be capable of neutralizing added alkalis. The negative charge on t h e carbon surface was assumed t o attract cations from t h e electrolyte, thus causing adsorption. This mechanism was believed t o explain t h e behaviour of those L-charcoals which adsorb alkali b u t not inorganic acids, a n d hydrolytically split inorganic neutral salts with a resulting decrease i n t h e p H of t h e solution. I n t h e presence of oxygen t h e charcoal was believed t o be posi

tively charged, emitting hydroxy! ions into the solution and being able t o adsorb anions from the solution. An oxygen-saturated charcoal would consequently behave as a n H-charcoal. The first results of experiments on slightly platinized charcoal were published in 1927 b y Frumkin and Donde (68). I n numerous papers (3237, 4044, 6671, 111, 125, 160, 162), Frumkin and his co-workers have reported details of this theory, including many modifications. Ingenious and intricate devices have been designed in order t o test the theory experiment ally. I t is impossible t o give a condensed account of these papers, partly because some have only been published in Russian (not included in the list above) and are not a t the present time available, and partly because the theory is modified in almost all of the papers. The last available paper on the subject was published in 1941. Only on a few, although fundamental, points has the theory been tested b y workers not belonging t o the school of Frumkin. The results were contradictory t o those of Frumkin and were found inconsistent with his theory. Some aspects of the theory may be pointed out. One consequence of the theory is t h a t a completely gassed-out charcoal must be incapable of adsorbing any electrolyte. This has not been found t o be true. Experiments b y investigators outside the school of Frumkin cover only concentrations above 0.02 N . Frumkin and his co-workers have in later papers restricted their theory t o cover only concentrations below 0.02 N. The reversibility of the carbon electrode, postulated b y Frum kin, may be doubted. The adsorption of oxygen on charcoal is definitely not reversible. Barrer and Rideal(16, 17) have come t o the conclusion, from a thermodynamic study of the adsorption of hydrogen on charcoal, t h a t carbon cannot function as a hydrogen electrode. If the theory of Frumkin is valid, a n exponential relation must be expected t o prevail between the pressure of oxygen and the adsorption of acids, and a similar relation must exist which relates the pressure of hydrogen and the adsorption of acids. Neither qualitative nor quantitative agreement with the theory could be observed by Frumkin. If the charcoal was platinized, some qua

litative agreement was obtained. The action of the platinum was supposed t o be t h a t of a catalyst, transferring its potential t o the complete carbon surface. The effect of the added platinum was held t o be of such minor importance t h a t its presence was some times mentioned only in the title and the summary of a paper (160). As a consequence of some experiments with platinized charcoals, an additional molecular adsorption was later assumed b y Frumkin (44). The existence of this type of adsorption was said t o be outside the scope of the theory but believed not t o be con tradictory t o it. The observation t h a t charcoals even without any treatment with gaseous hydrogen can adsorb alkali hydroxides has been discussed b y Burstein (40). He believed t h a t on activation t h e hydrogen, always present in charcoals, was transformed into an activated form, and then able t o behave as elementary hydrogen (sic!). I n support of his theory, Burstein refers t o the observation t h a t hydrogen in hydrocarbons can be exchanged for deuterium on treatment with deuterium oxide. I n a similar way, chemically combined oxygen was believed b y Frumkin t o act a s adsorbed oxygen. The theory has lost much of its original simplicity through these modifications. Barrer and Rideal(16, 17) found i t impossible from thermo dynamic studies t o believe in any formation of hydrogen from hydrocarbons in the manner suggested b y Burstein. Roychoudhury and Mukherjee (170) have called attention t o the fact t h a t chemically combined hydrogen and oxygen, dissociable as hydrogen or hydroxyl ions, function as reservoirs of these ions irrespectively of the presence of gaseous hydrogen or oxygen. These investigators have also pointed out that, according t o the electrochemical theory of Frumkin, the adsorption of a n acid must be a function of the p H of the solution but must be independent of the nature of the anion of the acid. This is definitely not the case with the adsorption of different inorganic acids on charcoal. The charge of charcoals suspended in water in equilibrium with atmospheres of known composition has not been studied b y Frum kin, who believed the charge t o be in accordance with his theory. The influence of the possible presence of inorganic impurities in the charcoal has not been investigated. Frumkin (67) preferred

not t o investigate or discuss the influence of the ash, although he admits t h a t this point may be of some interest. If i t be granted t h a t the theory of Frumkin may possibly be valid when platinized charcoals are used, i t affords no better ex planation of electrolyte adsorption on pure charcoals than any of the other theories previously discussed in this paper. This is also the belief of many authors. Finally, the theory of Frumkin cannot explain the p H changes observed when solutions of organic salts are treated with H-charcoals.

V. Plan of the Present Investigation.

None of the theories discussed seems able t o explain all t h e observations of electrolyte adsorption on charcoals. I n the author's opinion, i t is likely t h a t no single theory will be found t o apply t o all cases. I t seems indeed very plausible t h a t the different behaviours of the H - and the L-charcoals cannot be explained from a single point of view. I t would be of great value if in the study of electrolyte adsorption on charcoals analogies could be drawn from the know ledge gained in investigations of adsorption of electrolytes and nonelectrolytes a t the interfaces water/gas and water/organic liquid. I t seemed reasonable t o the present author t h a t the closest resemblance t o the air /water interface in regard t o the laws govern ing adsorption was t o be expected a t the interface H-charcoal/ water and not a t the interface L-charcoal/water. The non-adsorbability of the surface inactive alkali hydroxides and the adsorbability of surface active inorganic acids on H-charcoals in dicate, in the author's opinion, t h a t this assumption is acceptable as a working hypothesis. Although the phenomena of electrolyte adsorption on H-charcoal are more varied and intricate than in the case of L-charcoals, this assumption, if true, was held t o be of such great use in the theoretical treatment, t h a t it was decided t o restrict the study principally t o charcoal of the H-type. The theory of adsorption of electrolytes a t the air/water inter face has chiefly been worked out from experiments with organic electrolytes. I n order t o make the largest possible use of the knowledge gained from the discussed theory, organic electrolytes have also been included in the writer's investigation. I t is re markable t h a t since the experiments of Bartell and Miller pract ically only inorganic electrolytes have been used in the study of the causes and laws of electrolyte adsorption on charcoal.

I t was thought b y the author t h a t a theoretical interpretation of the phenomena in question could most easily be obtained from studies confined t o systems in equilibrium. Such conditions are generally dependent on fewer parameters t h a n kinetic phenomena. Electrokinetic studies have been excluded on account of the difficulties in the theoretical interpretation of the results. If the steady state obtained when the adsorption of an electro lyte had come t o an end is a true equilibrium, this fact must be a great aid in the theoretical interpretation, as in such a case thermodynamics may successfully be applied t o the phenomena. On reviewing the literature the author came t o the conclusion t h a t hardly any investigations have been published which discuss whether ash-free charcoal contain active centres, specific in regard t o the adsorption of electrolytes. The existence of such special centres for electrolyte adsorption is postulated in several of the discussed theories, but no definite proof of their existence has been submitted. A solution of this fundamental question must be of special interest in deducing the nature of the forces t h a t take part in electrolyte adsorption. If a theoretical interpretation of electrolyte adsorption is t o be proposed, it is also necessary t o conceive an idea of the relation ships in the vicinity of the adsorbent, where the adsorbed ions prevail. I t seemed plausible t o the author t h a t these ions form an electrical double layer. The idea was held t h a t the result of a study of this double layer in regard t o its electrical orientation might be used as a foundation for an interpretation of the various phe nomena referred t o b y the term hydrolytic adsorption. Most of the older theories of electrolyte adsorption suffer from a dualism in the theoretical interpretation of the observations, constituted b y the distinction between hydrolytic and molecular adsorption. The writer thought t h a t it would be of interest t o study the adsorption on charcoal from solutions composed of solutions of both acids and salts. Very few such experiments have been systematically carried out with the use of ash-free charcoals well-defined with regard t o their adsorptive character. I t seemed plausible t h a t b y a study of the systems mentioned the different views regarding the nature of the hydrolytic and the molecular adsorption could be brought into harmony.

On the basis of the points discussed, th author's investigation has been planned. Raw charcoals have been made from sugar and activated in oxygen a t various temperatures. The absorptive properties of t h e products have been investigated in order t o check the results obtained b y earlier investigators (Chapter 6). Further, the rate of adsorption has been investigated and a study has been carried out in regard t o the nature of the steady state obtained when the adsorption process has ended (Chapter 7). I n order t o investigate the nature of the adsorption forces effective in adsorption of ions, the author has carried out some experiments in which the amount of adsorbed electrolyte from a solution has been studied as a function of the amount of adsorbable non-electrolyte simultaneously present (Chapter 8). The author's intention t o study the orientation of the double layer of adsorbed ions on the charcoal surface has been carried out b y means of ionic exchange (Chapters 910). From the results obtained it was found possible t o present an outline of a theory of hyclrolytic adsorption on H-charcoal. Several aspects of this theory have been subjected t o experimental tests (Chapter 11). The study of the conditions in the adsorbed layer of ions on t h e surface of the charcoal has u p t o this point mainly been re stricted t o a study of the composition of the part of the double layer facing the water. I n the subsequent section of the thesis t h e amount of ions adsorbed in the part of the double layer facing t h e charcoal is studied as a function of the ionic composition of t h e solution. I t has been found possible t o give a theoretical interpretation of the observed phenomena, mainly employing the same conceptions as were used i q the earlier parts of the thesis (Chapter 12).

VI. Preparation of Gas-Activated Charcoals Low i n Ash, and a Study of their Adsorption Properties.

The charcoals used b y the writer in his adsorption experiments were prepared from sugar and activated with air. The method of preparation was essentially the same as t h a t employed b y Dubinin (57) and b y King (96). Sugar (Swedish Sugar Refineries Co.'s Grade " K 5, strsocker") was caramelized in a porcelain bowl and the heating continued until a brown cake was formed. This was broken into small lumps, and again heated a t about 400 C until no more fumes were evolved. After crushing, the charcoal was heated for about an hour in a crucible with an asbestos cover, and after cooling again crushed. This procedure was repeated until the powder was pure black. This raw charcoal was ground in a porcelain ball mill for two days, and the sieved fraction below 0.2 mm. used as the raw material for the activation. The activation was carried out in a porcelain tube heated in a n electric furnace. The temperature was measured with a thermocouple. The charcoal was distributed freely in the tube. Each batch of raw charcoal weighed 3040 g. During the activation process the tube was often rotated in order t o mix the charcoal. A flow of air a t the rate of a few millilitres per minute was passed through the tube during the activation. At the be ginning of the process the air was humified with water. At the end of each activation period the air was dried with sulphuric acid. The flow of air was turned off a t least half an hour before t h e charcoal was removed from the tube. A t the end of this time the furnace, still hot, was tilted over, the tube opened, and the charcoal allowed t o fall directly into a small glass flask, which was. immediately sealed with a ground stopper. The glowing charcoal very seldom heated the glass so rapidly t h a t it broke. The charcoal was dropped out through the opening in the tube used as air

inlet. The first part of the charcoal was rejected, because its ash content was fairly high. Immediately after being filled, the flask was placed over phosphorus pentoxide in a desiccator, which was evacuated. This method is necessary t o prevent air from pene trating into the flask during the cooling. Some charcoal always adhered t o the ground part of the neck of the flask, and the fit of the stopper was therefore not perfect. The method of cooling the charcoal was found t o be of great importance. If a hot charcoal activated a t a temperature of about 800 C was left t o cool in the presence of air, the charcoal exhibited a different adsorption character than if it had been rapidly cooled without the presence of much air. This transformation was al ready noticeable when the hot charcoal had been exposed for half a minute t o the air during the cooling. If the charcoal was slowly cooled in the presence of air, the capacity of the charcoal t o adsorb sodium hydroxide increased. When the charcoal was a t room temperature the contact with air had no measurable effect on its adsorption character. I n some experiments the activated charcoal was cooled in the tube. During the cooling a slow flow of nitrogen was passed through the tube. The ash content of the raw charcoal used in the activation pro cess was 0.210.24 % before the grinding. After grinding in the ball mill the ash had increased t o 0.50.7 %. The ash content in the activated charcoal depended upon how much of the charcoal was burned during the activation. I n the charcoals used for the experiments described in this paper the ash content never exceeded 1.3 %. Of the ashes in this charcoal about 60% consists of por celain from the porcelain balls in the mill. Experiments were also made with charcoal prepared from recrystallized sugar which, after the charring, was ground in an agate mortar and activated b y the method already mentioned. The ash content of these activated charcoals was 0.110.15 %. Their adsorbing properties were the same as those of a similarly activated charcoal made from t h e original sugar and ground in the ball mill, but its adsorption capacity was slightly lower. I t was therefore thought unnecessary t o recrystallize all the sugar used for preparing the charcoal.

The yield of activated charcoal varied between 0.3 and 0.6 of the raw charcoal. The colour of the charcoal produced was pure black but it did not have the deep velvety colour of many com mercial charcoals made from vegetable materials. I t had a slightly metallic lustre, less than most bone charcoals, but more t h a n many charcoals of vegetable origin. Charcoals from two different batches, activated a t the same temperature for the same length of time, were never quite identical as regards their adsorbent characteristics. When the adsorption of hydrochloric acid and sodium hydroxide from specified solutions was studied, slight variations in the amounts adsorbed were always observed. I t was especially difficult t o reproduce charcoals activ ated a t temperatures below 600 C. The following standard method was adopted for studying the adsorption of electrolytes on charcoal, and was employed in most of the experiments. When another method was used this is expressly stated. The charcoal was transferred from the flask in which it had been cooled into a stoppered weighing flask. The charcoal was mixed b y shaking and rolling the flask, in order t o eliminate any differences in adsorption character or capacity t h a t might have existed between charcoals originating from different parts of the activation tube. The charcoal was then weighed in equal amounts into a series of wide-mouthed glass flasks with an accuracy of + 0.5 mg. Greater accuracy can hardly be obtained because of the great hygroscopicity of the charcoal. For most experiments one gram of charcoal was p u t into each flask. Consequently, in these experiments, the error in the amount of charcoal was 0.5 /00. The charcoal was then moistened with a small quantity of water before the addition of the electrolyte solution. Charcoal always contains adsorbed gases, including carbon dioxide. When it is wetted these gases are t o some extent liberated and partly dissolved in the liquid. The author is of the opinion t h a t wetting the char coal with a small volume of water facilitates the escape of carbon dioxide from the system. After the electrolyte solution had been added t o the flask, this

was closed with a ground glass stopper, vigorously shaken b y hand and then placed in a rocking machine. Generally all experiments reported in a single series were carried out simultaneously. The flasks belonging t o a single series were kept together during t h e experiment. The temperature in all flasks was consequently the same. Most of the experiments were carried out a t room tem perature. Some were made in thermostats. After the lapse of a t least 48 hours, or longer the time is stated in each specific case the mixture was filtered through a glass funnel with a sintered glass filter (Schott & Genossen, Jena, type " 3 G 4"). The filtration of low-temperature activated charcoals from alkaline solutions was very difficult. I n order t o obtain a clear filtrate the mixture had t o be filtered three times, first through a glass filter " 3 G 3", then through " 3 G 4", and finally through " 3 G 5 auf 3". Aliquot parts of the filtrates were subjected t o chemical ana lysis, from which the amount of the electrolyte (or ion) adsorbed was calculated. The methods of analysis employed are stated in the appendix a t the end of the paper. The experiments reported in a single table or figure were generally carried out with charcoal from the same activation batch. If more charcoal was needed for a series of experiments than could be pro duced in a single batch, two or more batches of charcoal activated in the same way were intimately mixed and passed through a sieve. The batches mixed in this way were always selected so t h a t their adsorption properties were very much the same. As the writer found i t impossible t o produce two batches of charcoal with identical adsorption properties, the results from ex periments given in a single table or figure cannot be compared with the results of experiments reported in another table. Activation experiments were carried out with raw charcoal a t different temperatures during different lengths of time, in order t o study the influence of these factors on the adsorption properties of the charcoal. The main object of these experiments was t o test the results published b y King (96), and b y Chambers and King (47) with regard t o charcoal activation. These authors

claim t h a t the adsorption character of a charcoal is determined b y the activation temperature. The writer's raw charcoals were activated a t temperatures varying between 350 and 950 C in different experiments. The length of the activation period was varied between 2 and 25 hours. Some batches of activated charcoal were chilled b y pouring the hot charcoal from the activation tube into a flask, in the way already described. Others were cooled in the presence of nitrogen i n the activation tube. From each activation batch, samples of 1.000 g. of charcoal were poured into two flasks and moistened with 10.00 ml. of water. Two hours later 20.00 ml. of 0.0200 N hydrochloric acid and sodium hydroxide respectively were added t o the flasks. After 48 hours' shaking, the mixtures were filtered a n d the concentrations in the filtrates of the acid and the hydroxide respectively were estimated. The results obtained in these ex periments are shown in Table 2 and Figure 1. I t was found t h a t the amount of hydrochloric acid adsorbed b y t h e charcoal increased with its activation temperature, passed a maximum a t 800 C, and was slightly smaller if the activation temperature was still higher. An increase in the period of activation increased the amount of hydrochloric acid which the charcoals adsorbed from the solution in question. As a rule, slightly larger amounts of hydrochloric acid were adsorbed b y the charcoals which were cooled in the activation tube, t h a n b y those cooled outside the tube. Zero adsorption of hydrochloric acid was never observed. The amount of sodium hydroxide adsorbed was lower when charcoals activated a t higher temperatures were used for the ad sorption experiments. No measurable adsorption of sodium hydroxide was observed when charcoals activated a t 800 C were used. The charcoals activated a t a still higher temperature and cooled outside the activation tube showed a capacity t o adsorb small amounts of sodium hydroxide. On the other hand, charcoals activated a t a temperature above 800 C and cooled in the tube had no capacity for adsorbing sodium hydroxide in measurable amounts. The results obtained when the charcoal was chilled outside the activation tube are in the main in agreement with those obtained

Activation of sugar charcoal a t various temperatures with air.

Adsorption of HCl, 0.01333 N 1.000 g. charcoal: Temp, Time of of acti acti vation vation Adsorption of NaOH, 0.01667 N 1.000 g. charcoal: Cooled in furnace

Chilled outside Chilled outside Cooled in furnace furnace furnace 10.00 ml. H 2 0 + 20.00 ml. HCl, 0.02000 N

10.00 ml. H 2 0 + 50.00 ml. NaOH, 0.02000 N

C 15C 350 350 400 400 450 450 500 500 550 550 600 600 650 650 700 700 700 750 750 800 800 800 800 850 850 900 900 950 950

hrs. 20 8 14 2 14 8 14 6 14 8 14 8 14 7 20 14 7 14 10 25 20 14 8 14 6 14 4 14 6

Equil. Equil. Equil. Equil. Ads. Ads. Ads. Ads. concn. concn. concn. concn. HCl NaOH HCl NaOH NaOH NaOH HCl HCl [lequiv. m N m N jiequiv. m N jiequiv. mN [lequiv. 13.15 12.25 13.25 12.49 12.76 12.86 12.71 12.87 11.91 12.00 10.62 13.00 8.76 10.10 7.72 7.98 8.32 5.77 5.89 3.31 3.22

5 32 2 25 - 17 14 19 14 43 40 81 9 137 97 168 161 150 227 223 301 303

10.89 13.03 13.08 12.65 11.87 10.79 8.59 9 8 20 44 76 142 4.90 6.30 12.14 13.55 15.44 15.61

347 706 622 272 187 74 64 4.61

723

7.69 5.60
.

169 232

16.12 16.56 16.68 16.67 16.69 16.54 16.65 15.61 16.04

33 6 0 0 0 8 0 64 38

16.61

3.12

306

16.68

0 0 0 0

5.15 4.25 5.27 5.51 5.05 5.59 6.13

245 272 242 235 248 232 216

3.49 4.53 3.64

295 264 291

16.70 16.65 16.68

4 4 4 5 9 3 Brje Steenberg

49

by King (96). This writer also observed t h a t charcoals activated a t a temperature of about 800 C did not adsorb sodium hydroxide, as all charcoals activated a t lower or higher temperatures did.

-700

300-

-600

250-

-500

200-

-40O

150-

-300 ^

100-

-200

50-

-10Q

400"

600

700

QcHvaHon

temperature

Fig. 1. Adsorption of HCl and NaOH on charcoals gas-activated a t different temperatures. (Data from Table 2.)

Experiments in which the charcoal was cooled in the activation tube were not carried out b y Chambers and King. The results of the experiments on the adsorbing capacity of charcoals activated a t temperatures above 800 C and cooled in the activation tube are in agreement with those obtained b y Miller (136). Miller found t h a t charcoals activated a t a temperature of about 9001000 C did not adsorb sodium hydroxide.

The difference in the adsorption properties of charcoal activated a t a temperature above 800 C and cooled b y different methods can probably be explained in the following way. As has been mentioned earlier, i t is necessary t h a t the charcoal, when poured from the activation tube into the flask, should be in contact with air (oxygen) for as short a time as possible. Any hot charcoal left in contact with air for a period exceeding half a minute will be able t o adsorb measurable amounts of sodium hydroxide, whatever the activation temperature employed. When the charcoal is a t room temperature the adsorption properties of the product are not changed b y contact with air. There is ob viously a temperature interval within which the charcoal is very sensitive t o oxygen. I n all probability, this interval lies between 400 and 600 C. A charcoal activated a t a temperature above 800 C must pass this temperature interval rapidly, when oxygen is present, in order t h a t it may not acquire a capacity t o adsorb measurable amounts of sodium hydroxide. This temperature interval is more rapidly passed when the temperature of the char coal is 800 C, t h a n if the charcoal is still hotter when it is trans ferred from the activation tube t o the flask. I n the latter case, oxygen will react with the charcoal in such amounts t h a t t h e product will acquire a measurable capacity t o adsorb sodium hydroxide. With few exceptions, stated later on, the writer has only used H-charcoal for his investigation on electrolyte adsorption. The charcoals used b y the writer, which are named H-charcoals, have passed the following tests: Standard specifications for the writer's H-charcoal. A. 1.000 g. of charcoal is wetted with 10.00 ml. of distilled water free from carbon dioxide. Two hours later 20.00 ml. of 0.02000 N NaOH is added. After two days' shaking a t room temperature (1720 C), the mixture is filtered. 20.00 ml. of the filtrate should need not less than 13.25 ml. of 0.02000 N hydrochloric acid for its neutralization, methyl orange being used as indi cator.

B. 1.000 g. of charcoal is wetted with 10.00 ml. of distilled water free from carbon dioxide. Two hours later 20.00 ml. of 0.02000 N HCl is added. After two days' shaking a t room temperature, the mixture is filtered. 20.00 ml. of the filtrate should need not more than 7.50 ml. of 0.02000 N sodium hydroxide for its neutralization, methyl red being used as indicator. C. 0.200 g. of charcoal is mixed with 25 ml. of methylene blue chloride solution, 3.00 g. per litre of water. The mixture is shaken b y hand in a bottle for five minutes and then rapidly filtered. The filtrate should be colourless. D. 0.300 g. of charcoal wetted with ethyl alcohol and ignited in an electric furnace must yield not more than 5.0 mg. of ash. The fulfilment of the requirements in the first of the abovementioned tests ensures t h a t the ability of the charcoal t o adsorb sodium hydroxide is negligible. By employing the second and the third test it is ensured t h a t the activation process is carried out in such a way t h a t a good "adsorption activity" of the charcoal is obtained. The adsorption test with methylene blue gives an indication t h a t the adsorption process is relatively rapid. Finally, the ashing test is employed t o exclude charcoals high in ash from the experiments. The limits set in the above specification have been chosen arbitrarily. They are conditioned by the limitations of the method employed in the production of activated H-charcoals. 1 A batch of charcoals which does not fulfil the specifications for
I t may be worth mentioning that i t is possible t o prepare H-charcoal b y using commercial charcoals in a simple way. The writer found charcoal from E . Merck, Darmstadt (Carbo activatus siccus, pro analysi) especially suitable for this procedure. The nature of this charcoal varied slightly in different batches but charcoal from all batches had a pronounced capacity t o adsorb sodium hydrox ide. If this charcoal was ignited in an electric furnace for about 4 hours a t 800 C and cooled b y rapidly pouring the hot charcoal into a glass flask in the way pre viously described, the product satisfied tests AC in the above specification for the preparation of the writer's H-charcoal. The amount of ash was generally about 2 per cent. The ignition was carried out in a quartz crucible, imperfectly covered with a quartz lid. If the heating is not performed slowly, the charcoal will be ejected from the tube a s the adsorbed gases are liberated. Charcoal from Merck, activated b y the above method, was used b y the writer for many preliminary experiments.
1

Adsorption isotherm for hydrochloric acid. 1.000 g. H-charcoal. Time of contact: 48 hours. Temp. 22 C.
HCl, 0.02000 N added ml. 5.00 10.00 12.00 15.00 17.00 20.00 22.00 24.00 25.00 27.00 30.00 40.00 50.00 60.00 Total volume ml. 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 40.00 50.00 60.00 Excess acid 0.02000 N ml. 0.00 0.01 0.48 1.69 2.80 4.92 6.49 8.00 8.94 11.62 13.12 23.00 32.80 42.42 Ads. HCl per g. Equil. concn. charcoal HCl mequiv. 0.1000 0.1998 0.2304 0.2662 0.2840 0.3016 0.3102 0.3200 0.3212 0.3076 0.3376 0.3400 0.3440 0.3516 mN 0.000 0.007 0.320 1.13 1.87 3.28 4.33 5.33 5.96 7.75 8.75 11.50 13.12 14.14

an H-charcoal can be used for re-activation, if its ash content is not too large. I n order t o study the adsorption of some strong electrolytes on the writer's H-charcoal, the adsorption isotherms of some mineral acids were investigated. For these experiments hydrochloric, nitric, perchloric, and sulphuric acids were used. Each experiment was carried out with 1.000 g. of H-charcoal and the time of contact between the solution and the charcoal was 48 hours. The volume of the liquid in contact with the charcoal varied between 30.00 and 60.00 ml. The results of these experi ments are shown in Tables 3, 4, 5 and 6. There was much variation in the adsorption of the different acids from solutions of equal volume and containing equivalent amounts of the acids. If the ad sorptions of the univalent acids are compared, their adsorbabilities can be arranged in the following series: HC1<HN03<HC104.

Adsorption isotherm for nitric acid. 1.000 g. H-charcoal. Time of contact: 48 hours. Temp. 22 C.
HNOg, 0.02000 N Total volume added ml. 10.00 12.00 15.00 17.00 20.00 22.00 25.00 27.00 30.00 35.00 40.00 50.00 60.00 ml. 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 35.00 40.00 50.00 60.00 Excess acid 0.02000 N ml. 0.01 0.18 0.56 1.16 2.53 3.82 6.37 7.75 10.01 14.33 19.07 28.62 38.31 Ads. H N 0 3 per g. charcoal mmole. 0.1998 0.2364 0.2888 0.3168 0.3494 0.3636 0.3726 0.3850 0.3998 0.4134 0.4186 0.4276 0.4338 Equil. concn. HNO 3 mN 0.007 0.120 0.373 0.773 1.69 2.55 4.25 5.17 6.67 8.19 9.54 11.45 12.77

Table 5. Adsorption isotherm for perchloric acid. 1.000 g. H-charcoal. Time of contact: 48 hours. Temp. 22 C.
HC104, 0.02000 N Total volume added ml. 5.00 10.00 12.00 15.00 17.00 20.00 22.00 25.00 27.00 30.00 35.00 40.00 ml. 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 35.00 40.00 Excess acid 0.02000 N ml. 0.00 0.00 0.02 0.28 0.68 2.05 3.16 4.95 6.36 8.07 12.67 17.42 Ads. HC10 4 Equil. concn. per g. charcoal HCIO4 mequiv. 0.1000 0.2000 0.2396 0.2944 0.3264 0.3590 0.3768 0.4010 0.4128 0.4386 0.4466 0.4516 mN 0.000 0.000 0.013 0.87 0.453 1.37 2.11 3.30 4.24 5.38 7.24 8.72

Adsorption isotherm for sulphuric acid. H-charcoal. Time of contact: 48 hours. Temp. 22 C.
H 2 S0 4 , 0.02000 N Total volume added ml. 1 5.00 10.00 12.00 15.00 17.00 20.00 22.00 25.00 27.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 0.07 0.16 0.22 1.05 1.99 3.74 5.34 7.44 9.03 11.28 0.0986 0.1968 0.2356 0.2790 0.3002 0.3252 0.3332 0.3512 0.3594 0.3744 0.047 0.107 0.147 0.700 1.33 2.49 3.56 4.96 6.02 7.52 ml. Excess acid 0.02000 N ml. Ads. H 2 S 0 4 per g. charcoal mequiv. Equil. concn. H 2 SO 4 mN

The writer has studied the hydrolytic adsorption of salts on H charcoal. Experiments were carried out in the first place with a few inorganic alkali metal salts, namely KCNS, NaCNS, K N 0 3 , NaN0 3 , KBr, NaBr, KCl, NaCl, RbCl and NaF. For these experiments, a series of flasks each containing 1.000 g. of H-charcoal was used. To each flask was added 30.00 ml. of a solution containing varying amounts of the mentioned salts dissolved in water. The flasks were shaken for four days a t room, temperature. After this lapse of time the mixtures were filtered and aliquot parts of the filtrates titrated with 0.0200 N nitric acid. All filtrates were found t o be alkaline. The amount of hydrox ide ions liberated varied with the nature of the salt. The nature of the metal cation of the salts had no observable influence on the results. When the hydrolytic adsorptions of salts with a com mon cation but different anions were compared, a difference in the amounts of liberated hydroxide ions was observed. The results of the experiments are shown in Table 7. The results of some experiments with sodium fluoride are not included in the table. The amount of hydroxide ions liberated b y this salt was smaller

Hydrolytic adsorption of inorganic alkali metal salts. 1.000 g. H-charcoal. Volume of liquid: 30.00 ml. Time of contact: 4 days.
Normality of salt Concentration of hydroxyl ions in millinormality: KONS NaCNS KNO 3 N a N 0 3 KBr 1.33 1.85 1.97 2.20 2.37 2.64 2.90 2.92 3.14 3.22 3.33 3.46 3.62 1.46 1.83 1.78 2.24 2.33 2.63 2.96 3.00 3.12 3.22 3.36 3.51 3.60 NaBr KCl NaCl RbCl

0.0033 0.0067 0.0133 0.0200 0.0333 0.0667 0.200 0.333 0.467 0.667 1.333 2.000 3.000

1.42 1.50 1.61 1.73 1.95 2.22 2.38 2.51 2.81 2.87 3.00

1.57 1.61 1.76 1.92 2.22

2.46

2.90 3.03

1.12 1.21 1.26 1.38 1.47 1.67 1.83 1.89 2.00 2.11 2.23

1.17 1.24 1.28 1.36 1.47 1.68 1.90 1.93 2.06 2.12 2.26

0.77

0.96 1.04 1.24 1.24 1.29 1.28 1.56 1.60

0.92 1.10 1.15 1.27 1.32 1.40 1.52 1.63

0.84 0.90 1.08 1.17

Table 8. Hydrolytic adsorption of potassium sulfocyanate. 1.000 g. H-charcoal. Volume of liquid: 30.00 ml. Time of contact: 4 days.
Microequivalents : KCNS N 0.01022 0.01022 0.01533 0.01533 0.02044 0.02044 0.02044 Liberated OH55.8 57.0 62.1 60.6 65.4 67.8 64.5 Adsorbed CNS~ 54.6 56.3 58.8 61.2 66.0 72.3 66.0 j

than t h a t observed in the experiments with any of the other tested salts in the same concentration. Analysis of salt solutions containing KCNS, before and after contact with the H-charcoal, showed t h a t the amount of liberated hydroxyl ions was equivalent, within the experimental error, t o the amount of anions adsorbed from the salt (Table 8). When the hydrolytic adsorption on H-charcoal from solutions of inorganic alkali metal salts was compared, the following order of the salts was found: CNS~~ > NCT > B r - > CI" > F ~ . The hydrolytic adsorption of a few organic salts on the writer's H-charcoal has also been studied. As suitable salts for these ex periments sodium phenyl-dimethyl-pyrazoloiie-methyl-amido-methane sulphonate (Novalgin sodium) and cotarnine chloride were selected. According t o Miller, essentially different results are t o be expected from adsorption experiments with salts containing a n organic cation or an organic anion. The two mentioned salts are representatives of these groups. They are derived from strong acids and strong bases. Both are highly adsorbable on H-charcoal from solutions in water. The substances are very soluble in water and b y their use i t is consequently possible t o study the hydrolytic adsorption of organic salts even from more concentrated solutions. The results of these experiments were in the main in agreement with those obtained when using other less soluble salts containing either an organic anion or an organic cation. The experiments with Novalgin sodium were carried out in the following way. Samples of 1.000 g. of H-charcoal, in a series of flasks, were mixed with 60.00 ml. of a solution containing 0.010 30.0 g. of Novalgin sodium. After four days' shaking a t room temperature the mixtures were filtered. All filtrates were found t o be alkaline, although t o different extents. Aliquot parts of the filtrates were titrated with 0.0200 N HCl and in some filtrates the amount of Novalgin was determined. From the latter value t h e amount of Novalgin adsorbed was calculated. The results are shown in Table 9.

Hydrolytic adsorption of phenyl-dimethyl-pyrazolone-methylamido-methane-sulfonate sodium (Novalgin sodium) C 11 H 11 N 2 0 - NCH 3 CH2 . S0 3 Na, H 2 0 . 1.000 g. H-charcoal. Volume of liquid: 60 ml. Time of contact: 4 days.
Novalgin sodium g./60 ml. 0.010 0.020 0.040 0.060 0.080 0.100 0.200 0.300 0.400 0.500 0.600 0.700 0.800 0.900 1.00 2.00 5.00 8.00 10.0 10.0 12.0 15.0 20.0 25.0 30.0 mmole./l. 0.5 1.0 1.9 2.9 3.8 4.8 9.5 14.3 19.0 23.7 28.5 33.2 38.0 42.7 47.5 95.0 237 380 475 475 570 712 950 1 187 1 425 Novalgin adsorbed mg. 10 20 40 60 80 96 176 232 273 302 313 352 337 368

OHmN 0.326 0.682 1.566 1.673 1.826 2.286 1.099 0.729 0.566 0.596 0.549 0.516 0.523 0.489 0.483 0.379 0.266 0.203 0.167 0.129 0.090 <0.10 <0.10 <0.10 <0.10

j i-

The findings can be summarized as follows: When the amount of Novalgin sodium increases in the system, the amount of liberated hydroxyl ions first increases, then passes a maximum, and finally decreases. The maximum amount of hydroxyl ions liberated is

Hydrolytic adsorption of cotarnine chloride C12H1403NC1. 2.000 g. H-charcoal. Volume of liquid: 100 ml. Time of contact: 5 days.
Cotarnine chloride Cotarnine adsorbed mg. mg. 100 200 300 400 450 500 600 750 800 1 000 3 000 5 000 100 200 300 380 420 450 490 530

H+ mN < 0.10 < 0.10 < 0.10 0.146 0.132 0.193 0.231 0.217 0.173 0.10 < 0.10 < 0.10

550 600

found when so much Novalgin is present in the system t h a t it cannot be completely adsorbed b y the H-charcoal present, but is also found in small amounts in the filtrate. The experiments with cotarnine chloride were carried out according t o the same method as t h a t used with Novalgin sodium. When solutions of cotarnine chloride in water were put in contact with H-charcoal they always became more or less acid, irrespective of the amounts of cotarnine present. The amount of acid in the filtrates was determined b y titration with 0.0200 N NaOH and t h e amount of cotarnine by colorimetric analysis. The results are shown in Table 10. I t was found t h a t the amount of liberated hydrogen ions a t first increased with increasing amounts of cotar nine chloride in the system, passed a maximum, and then slowly decreased when the amount of cotarnine chloride in the system was further increased. The maximum amount of liberated hydrogen ions was observed when so much cotarnine chloride was added t h a t it could no longer be completely adsorbed by the H-charcoal. The observations on hydrolytic adsorption of salts made in

experiments with the writer's H-charcoal, agree essentially with those made b y Miller.1 The adsorption experiments described in this chapter demon strate t h a t i t is possible t o obtain qualitatively similar results as regards electrolyte adsorption on low-ash charcoals, when the charcoals are prepared in a strictly standardized manner.
The hydrolytic adsorption of methylene blue chloride generally proceeded, on the writer's H-charcoals, in the same w a y as that of cotarnine chloride. On a few occasions, however, i t was observed that the filtrates were slightly alkaline when the concentration of the methylene blue chloride in the filtrate was high. The discrepancy is in all probability due t o the degree of activation. I t may be worth noting that Chambers and King (47) observed that H-charcoal adsorbs methylene blue chloride from concentrated solutions while hydroxyl ions are being liberated. Miller (135) and Sastri (172) only found that acid was liberated.
1

VII. On the Nature of the Steady State Obtained When Electrolyte Adsorption on Charcoal is Completed.

It must be of fundamental importance in constituting a theory of electrolyte adsorption on charcoal t o know whether the ad sorption process can be reversed or not, and consequently whether or not the concentration of an electrolyte in the solution after the adsorption is complete is an equilibrium concentration. I t is often maintained in the literature t h a t the state obtained when the adsorption of electrolytes on charcoal is brought t o a standstill is not a true equilibrium state. This has especially been believed t o be the case when only small amounts of the electro lyte are adsorbed from dilute solutions on large amounts of charcoal. Before taking u p this question, i t is necessary t o investigate whether reproducible results can be obtained a t all from experi ments on the adsorption of electrolytes, and how long i t wi)l take t o complete the process, making use of the charcoals pro duced b y the writer. Several authors affirm t h a t the time of contact between an electrolyte solution and a charcoal, necessary t o bring the ad sorption t o an end, is very short. Freundlich (62) states in one of his classical papers on adsorption on charcoal from solutions t h a t the adsorption of acetic acid was completed in less than an hour. This result has been confirmed by Lepin and Strachowa (123). From experiments with strong inorganic acids, several investig ators have concluded t h a t a 1 t o 4 hours' contact time is sufficient t o bring the process of adsorption t o an end (56, 119, 123, 160). The idea seems t o be widely held t h a t the adsorption of these sub stances is completed almost instantaneously. This may be the reason why, in many papers, the time of contact before determina tion of the amount adsorbed is not reported (55, 103).

I n only a few cases is there mention of the fact t h a t the adsorp tion of electrolytes requires a considerable time for completion. Krestinskaja (105) found the adsorption of acetic acid, of benzoic acid, and of crystal violet t o be very slow reactions, taking months t o reach steady states. I n her opinion, the rate of adsorption is determined primarily b y the rate of diffusion into the capillaries of the charcoal. Dubinin (58) observed a very slow rate of ad sorption of inorganic acids on some sugar charcoals. The rate of adsorption was believed t o be a function of the porosity of the charcoal. No determinations of the porosity are reported b y this author, however. There have not as yet been any publications dealing with the rate of adsorption of electrolytes on charcoal from the theoretical viewpoint. The writer's experiments show t h a t a considerable time of con tact between the charcoal and a solution ot electrolyte is necessary before the adsorption is completed. The adsorption of organic electrolytes such as acids or basic dye-stuffs from water was found t o continue even after a solution had been shaken together with the charcoal for several weeks, although the rate of adsorption a t the end of this period was very slow. The adsorption of inorganic acids was also found t o proceed much more slowly t h a n is generally claimed. I n order t o obtain reproducible results the charcoal must be left in contact with the acid and shaken for a t least 48 hours. The rate of adsorption of hydrochloric acid on an H-charcoal was determined in the following manner. Samples of 1.000 g. of the charcoal were wetted with 10 ml. of water in glass-stoppered, conical flasks. After an hour, 20 ml. of 0.02 N hydrochloric acid was added t o each flask. After intense shaking of the mixture b y hand for 10 seconds the bottle was shaken in a thermostat a t 20 C, a t a rate fast enough t o give uniform distribution of the charcoal in the solution. A t the end of definite periods the solution was filtered through Jena glass filters and 20 ml. of the filtrate titrated with 0.02 N sodium hydroxide. The time of contact between the charcoal and the acid was measured from the time when the acid was added till one-half of the solution had been

Rate of adsorption of HCl. 1.000 g. H-charcoal. Volume of liquid: 30.00 ml. 20.00 ml. 0.02000 N HCl. 10.00 ml. H 2 0 . Temp. 22 C.
Time of contact days min. 0 17 28 37 48 68 86 107 132 157 207 1 2 3 5 6 8 12 20 HCl free 0.02 N ml. 20.00 11.70 10.65 9.91 9.37 8.71 8.42 8.13 7.87 7.61 6.83 6.17 5.96 5.84 5.88 5.78 5.90 5.87 5.83 Adsorbed HCl mequiv./g. [HCl] f r e e mN 13.33 7.80 7.10 6.61 6.25 5.81 5.61 5.42 5.25 5.07 4.55 4.11 3.97 3.89 3.92 3.85 3.93 3.91 3.89

0.166 0.187 0.202 0.213 0.226 0.232 0.237 0.243 0.248 0.263 0.277 0.281 0.283 0.282 0.284 0.282 0.283 0.283

passed through the glass filter. The results of these experiments are given in Table 11 and Figure 2. I t will be noted t h a t about 50 hours were needed t o complete the adsorption under these con ditions. After this time no change in the adsorption was observed. Experiments with other inorganic acids gave the same result. I t was also found t h a t a time of the same length was required t o bring the adsorption process t o an end when commercial charcoal from E . Merck, Darmstadt (Carbo activatus siccus, pro analysi), was used in the experiments. The author feels there is justification for assuming t h a t in general the time required for this process t o reach completion is more t h a n one day. Although it is outside the scope of this investigation i t was of interest t o test whether these data for the adsorption rate of

hydrochloric acid could be fitted into any of the simpler formulae for reaction velocity. If the process of adsorption of hydrochloric acid can be described b y the formula: H + - Cl~~ = HCl ads h me^uiu.
(1)

Time of coniaci. Fig. 2. The adsorption of hydrochloric acid on H-charcoal. (Data from Table 9.)

the particles in the adsorption process are present in equivalentamounts in the reported experiment. The testing of the order of reaction will consequently be simple. I t was found t h a t the data from Table 11 did not correspond t o a uni-, bi-, or tri-molecular reaction. Attempts t o describe the rate of adsorption as a reversible reaction were not successful. I t is especially interesting t o note t h a t in the investigated case the rate of adsorption is not chiefly determined by a process of diffusion over constant cross section, since in t h a t case the process would be found t o be of the first order. The kinetic theory used b y Langmuir (120) when deducing his adsorption isotherm cannot be applied t o the present instance. Langmuir assumed t h a t adsorption and desorption could be de scribed by a first order rate equation. As the adsorption equi librium of hydrochloric acid has been found t o depend on the

concentration of both the anion and the cation (see page 21) this process is very probably of a higher order. Data regarding the reversibility of adsorption on pure char coals of electrolytes or mixtures of electrolytes and non-electrolytes in water are very scarce in the literature. Among experi ments of an older date, when blood charcoal was used, those of Freundlich (62) and of Michaelis and Rona (133) may be men tioned. Freundlich found the adsorptions of acetic and of benzoic acid t o be reversible. Michaelis and Rona came t o the same con clusion from experiments with mixtures of acetic acid and acetone in water. Two ways are available for investigating whether the steady state obtained when the adsorption process is finished is a thermo dynamic equilibrium. Firstly, the adsorption and desorption isotherms may be compared, and secondly, the variations in the amounts adsorbed a t cdfferent temperatures may be studied. Recent experiments along both lines have been carried out by Lepin and Strachowa. These authors (123) graphically compared the adsorption and the desorption isotherms for hydrochloric acid on charcoal, and found t h a t the desorption terminated a t a lower concentration in the solution than the adsorption. On account of this observation, the authors considered the adsorption of the acid t o be identical with a neutralization of an alkaline surface oxide on the charcoal, and were able t o calculate an ionization constant of the hypothetical basic carbon oxide from their experimental data. I n the case of weak acids, such as acetic acid, no hysteresis between the adsorp tion and the desorption isotherms was observed, and in this par ticular instance the authors assumed the adsorption t o be revers ible, and exclusively effected b y van der Waals' forces. Lepin and Strachowa assumed t h a t the process of adsorption of hydrochloric acid was completed in 3 t o 4 hours, and t h a t the desorption was practically a t an end in 24 hours. The writer, however, believes t h a t the time of contact between the hydrochloric acid and the charcoal employed by Lepin and Strachowa was far too short. If a longer contact time had been used, the experimental results would probably have been different (see page 63).
5 44593 Brje Steenberg

65

Apart from this objection t o the experimental method used b y Lepin and Strachowa, their deductions may be criticized from a theoretical point of view. I t will be shown later on t h a t it is impossible t o deduce, from the trend of the adsorption and desorption isotherms, t h a t the adsorption of a n acid is caused b y a reaction between the acid and surface oxides on the charcoal. If it be assumed t h a t the process of adsorption of hydrochloric acid is a reversible reaction, in which both the ions of the electro lyte are adsorbed in equivalent amounts, then in a system com posed of charcoal with adsorbed acid in equilibrium with a solution of the acid in water, desorption of some hydrogen and chloride ions must occur if the solution phase of the system is enlarged b y the addition of pure water. Let us assume, on the other hand, t h a t the adsorption of the acid is identical with a formation of a surface salt from a carbon surface oxide with weak basic properties. I n this case also, on the addition of water t o the system, the amounts of hydrogen and chloride ions in the solution increase, on account .of hydrolysis of the surface salt. Consequently, it is impossible t o trace the origin of an increased number of hydrogen ions appearing in the solution during the process of desorption. The theory of Lepin and Strachowa must therefore be considered, if not invalid, a t least incomplete. The only paper dealing with the dependence of the temperature on electrolyte adsorption has also been published b y Lepin and Strachowa (122). These authors determined the temperature coefficient of the adsorbed amount of some organic and inorganic acids. They found, for acetic acid, a pronounced decrease in the amount of adsorbed substance with an increasing temperature. For the adsorption of hydrochloric and sulphuric acid, on the other hand, it was observed t h a t the adsorbed amount was in creased with increasing temperature. These mineral acids were found t o have a temperature coefficient of the order of + 0.0005 moles adsorbed acid per gram of charcoal and C. As intimated earlier, these experiments were also probably carried out over too short a time t o allow the adsorption process to be completed. The observation of a positive temperature coefficient, which appears t o be unique in adsorption processes,

might possibly be explained in the following way. The rate of adsorption increases rapidly with increasing temperature, but the equilibrium amount simultaneously decreases slowly. If insuffici ent time is allowed for the process t o be completed an increase with temperature in the amount adsorbed will be observed. Because of the objections raised against the experimental tech nique of Lepin and Strachowa, the present writer thought i t ad visable t o repeat some of their experiments. This study was limited t o the question of whether the process of adsorption of mineral acids proceeds towards a true thermodynamic equilibrium or not. I n order t o do this, two cyclic processes, in the main identical with those in Lepin and Strachowa's experiments, were studied. The first series of experiments was carried out in the following way. A known amount of an inorganic acid was diluted with a fixed volume of water and then shaken with 1 g. of H-charcoal, and the adsorption of the acid was determined b y analysis of the super natant liquid four days later. The same amount of acid was shaken with the same amount of the charcoal, and t o this suspen sion the same amount of water was added in portions a t intervals of a few days. Four days after the last addition, this mixture was analyzed and the amount of adsorbed acid calculated. All samples were kept a t the same temperature throughout the experiments. The details of the experimental results with hydrochloric and nitric acid are given in Table 12. From the table i t will be seen t h a t the amount adsorbed, a t a definite temperature, is determined only b y the composition of t h e system, showing t h a t sufficient time has been allowed t o bring the adsorption and the desorption t o an end. This observation seems t o confirm fairly well the assumption t h a t the adsorption of mineral acids may be regarded as a reversible process, and t h a t the results obtained represent true equilibrium conditions. The influence of a variation in temperature on the adsorption equilibrium was also investigated. I t was ascertained in preliminary experiments t h a t the temperature coefficient of adsorption equi librium was negative. The test of the reversibility of the adsorption was carried out according t o the following method. A solution of both hydrochloric acid and potassium chloride in

Comparison of adsorption and desorption of mineral acids on H-charcoal. 1.000 g. H-charcoal. Volume of liquid: 30.00 ml. Mineral acids 0.0200 N . Temp. 23 C.
D a y of addition, and analysis No. 1. Solution HCl H20 HCl H20 HCl H2O HCl H2O HCl H2O HCl H2O HNO 3 H2O HNO 3 H2O HNO G H2O 1 jst Added ml. 20.00 10.00 10.00 10.00 10.00 3rd Added ml. 5th Added ml.

9th

Free acid in ml. 0.0200 N 6.46

2.

6.52

3.

10.00 10.00 30.00 20.00 10.00 20.00 30.00 10.00 20.00 10.00 20.00 10.00 20.00 5.00

10.00

6.48

4.

13.22

5.

20.00

13.41

6.

10.00

13.17

7.

2.61

8.

2.52

9.

5.00

2.56 i

water was mixed with charcoal, in different flasks, which were shaken in three thermostats a t 4, 20, and 40 C for four days. After this time some of the flasks were transferred from one thermo stat t o another. After four more days another change from one thermostat t o another was made. At the end of still another period of four days, all samples were filtered and the acid in the

Influence of temperature on adsorption of HCl. 2.000 g. H-charcoal. Volume of liquid: 50.00 ml. 40.00 ml. HCl, 0.02000 N . 10.00 ml. KCl, 0.080 N .
40.00 ml. filtrate requires for Analyzed neutr. ml. NaOH, 0.0200 N Seque nee: after no. (4 days a t each temp.) of days Series I Series I I Average 4 1 4 25
o o o

j Equil. Adsorbed concn. ! HCl HCl mequiv. mN I 3.07 3.05 3.06 3.02 3.97 3.98 4.03 3.94 0.647 0.648 0.647 0.649 0.602 0.601 0.599 0.603 0.567 j 0.560 0.570 S 0.563

4 25
o

4 4 4

4
12

; I

12
12

6.10 6.08 6.12 6.07 8.03 7.85 8.02 7.86 9.34 9.75 9.19 9.34

6.15 6.11 6.10 6.03 7.82 8.05 8.07 7.92 9.28 9.45 9.23 9.61

6.13 6.10 6.11 6.05 7.93 7.95 8.05 7.89 9.31 9.60 9.21 9.48

filtrate titrated. The results are given in Table 13. The addition of the salt t o the acid was found not only t o increase the amount of acid adsorbed, b u t also t o increase the reproducibility of the results. The table shows t h a t within the experimental error the same amount of acid is adsorbed irrespective of the way in which each sample has been pre-treated. If the adsorption process is allowed t o proceed over a sufficiently long period the result is only affected b y the amount of charcoal, the volume of the solution, the amount of electrolyte in the solution, and the final tempera ture. From the results of these experiments i t can be deduced t h a t the steady state obtained after a few days' contact between a n H-charcoal and a solution of an inorganic acid is a true equilibrium. Although the experiments were restricted t o inorganic electro lytes there is no indication t h a t the same result would not have been obtained if organic electrolytes had been used. The difference between the behaviour of organic and inorganic electrolytes in

O T* O t*

25 J 25 1 25 4 4 1 40 o O

O T*

25 25 25 i j

4
12 12 12

j ; j ;

4 25

25 4

4 12 12 12

4.66 j 4.80 1 4.61 4.74

o O

o o o O O O

this respect seems t o be chiefly qualitative, depending upon 1 he much slower rate of adsorption and desorption of the former substances. The knowledge gained from the experiments described in this chapter is of importance in the later treatment of the phenomena of electrolyte adsorption on H-charcoal. Apart from the im portance of these observations in deciding the future experimental technique, a foundation is laid for the application of thermodyna mics t o the process of electrolyte adsorption on H-charcoal.

VIII. On the Nature of the Forces Coining into Play in the Adsorption of Electrolytes on H-charcoal.

Adsorption can be brought about by forces of any degree of strength, from covalent bonds t o very weak forces. I n con sidering the adsorption of ions on charcoal we must make a survey of the forces which may bring about the attraction of the ions t o the adsorbent. Any kind of ion is attracted t o charcoal b y mirror image forces. The mirror image forces are comparatively weak and are of the same strength for anions and cations. I t seems improbable t o the writer t h a t image forces alone can interpret the adsorption of ions on charcoal. Adsorption of ions on charcoal may also depend on van der Waals' forces. 1 Such forces act on both ions and molecules. If the adsorption of ions depends on such kinds of forces all surface atoms have some adsorptive power. Differences between different surface atoms may be quantitative but not qualitative. I t is commonly believed t h a t adsorption of dissolved gases and nonelectrolytes on charcoal is caused by vali der Waals' forces. Finally, there may exist special kinds of surface atoms which adsorb, b y some other mechanism, only ions but not molecules. Most of the reported theories of electrolyte adsorption take for granted t h a t such special types of surface atoms are present on the charcoal. I n the oxide theory of electrolyte adsorption, for instance, the adsorption of ions is thought t o be brought about b y t h e formation of a salt between a charcoal surface base or acid and the adsorbed ion. No definite proofs t h a t adsorption of electro lytes depends on such kinds of forces on H-charcoal have been submitted.
1 The term van der Waals' forces is used throughout this paper with the same meaning as that employed b y Briegleb (31).

I t seems difficult t o form any definite idea of electrolyte ad sorption on charcoal before some knowledge is obtained concerning the strength of t h e forces effective in this process. An approach t o a solution of this problem may, in the author's opinion, be made through a study of the simultaneous adsorption of electrolytes and non-electrolytes. If the adsorption of acids is, say, a kind of salt formation, this ionic equilibrium cannot be disturbed b y any non-electrolytes present, except in so far as they influence the activity of the electrolytes. This follows from the fact t h a t the forces between ions are so much stronger than the van der Waals' forces effective in adsorption of the non-electrolyte. If, on the other hand, ions are adsorbed b y charcoal b y van der Waals' forces, adsorbable non-electrolytes simultaneously present in the system must have a considerable effect on the amount of ions adsorbed. Consequently, if a decrease in the adsorbed amount of an electrolyte is observed on addition of a non-electrolyte t o the system, one is tempted t o conclude t h a t the forces which adsorb electrolytes and non-electrolytes are essentially of the same nature, and t h a t there exist no special active centres for electrolytes. I n the history of the study of electrolyte adsorption on charcoals this fundamental problem does not appear t o have been discussed. Although several papers have been published on adsorption from ternary systems composed of electrolytes and non-electrolytes in water, no conclusions regarding this problem are drawn from the results, as f a r as is known t o the present author. Freundlich, even a t the time of his classical paper on adsorption from solutions (62), discussed the influence of neutral inorganic salts on the adsorption of non-electrolytes. Because neutral inorganic salts in water do not exhibit pronounced surface action, he believed the adsorption, of a surface active organic substance t o be uninfluenced, or perhaps slightly increased, b y the presence of an inorganic electrolyte. I n accordance with this theory Freund lich could find no influence on the adsorption on charcoal of benzoic acid resulting from the addition of sodium sulphate. He mentions, however, the influence of neutral salts on the adsorp tion of dye-stuffs on fibres, a phenomenon well known t o the dyer. Lachs and Michaelis (112114) distinguished between the ad sorption of electrolytes and of non-electrolytes, because they

had observed t h a t the amount of a n electrolyte adsorbed was not influenced b y non-electrolytes present. Changes in the amount of non-electrolytes adsorbed were observed, however, on the addition of another non-electrolyte. The adsorption of any one electrolyte was also influenced b y the presence of another electro lyte. This theory was later modified and stated in the following terms (167): "Nichtelektrolyte und Elektrolyte verdrngen sich gegenseitig aber in viel geringerem Grade, als es bei der Verdrngung innerhalb der Gruppe der Nichtelektrolyte und innerhalb der Gruppe der Elektrolyte der Fall ist." Wiegner, Magasanik and Virtanen (186) were able t o confirm the theory of Freundlich as regards a number of substances. These authors found t h a t the amount of hydrogen ions adsorbed on charcoal from carboxylic acids increased if the acid was present in a 2N solution of a neutral inorganic salt. They observed also t h a t the amount adsorbed changed with the nature of the salt. The adsorbed amount of hydrogen ions increased, according t o their results, with increasing atomic weights of the cation of the dissolved salt, the experiment being made with ions of the same valency. Sulphates caused a greater increase in the adsorbed amount of hydrogen ions t h a n chlorides, if the experiments were carried out a t room temperature. With boiling solutions the reverse was found. Several investigations on adsorption from solutions composed of mixtures of weak electrolytes and non-electrolytes in water have been published. Freundlich and Masius (63) reported on the adsorption from solutions in water of succinic acid and oxalic acid. Michaelis and Rona (133) and Dubinin (56) studied mixtures of acetone and acetic acid, and Rona and von Tth (169) the ad sorption of mixtures of sugar and aliphatic acids and an homo logous series of urethanes. An investigation on the influence of ethyl alcohol on the adsorption of mono- and dicarboxylic acids, saturated and unsaturated hydroxy acids, and some aromatic acids has been carried out b y Reif and von der Heide J r . (163). I n all the reported cases, a decrease in the adsorbed amount of a substance was observed when the second substance was added. Mixtures of non-electrolytes or weak electrolytes and neutral inorganic salts have been investigated b y Michaelis and Rona (133)

 acetic acid; K r a y t and van Duin (107) phenol; and Abder halden and Fodor (1) leucine and other amino acids. I n most oases an increase in the adsorbed amount of the organic substance was observed after the addition of a neutral salt; for leucine, how ever, a decrease in the adsorbed amount was caused b y the addition of neutral potassium salts, the thiocyanate having the greatest and the sulphate the least action. Among other investigations of a similar nature those of Hayashi (79), Ockrent (149), Amiot (9, 10), Jones, Hudson and Jones (86), Yermolenko and Lewina(191), and Yermolenko and Bochwala (190) may be mentioned. Nearly all these cited experiments were carried out with char coals of high ash content or of unknown origin. The next part of this chapter deals with some more modern investigations carried out with ash-free charcoal activated a t high temperatures. Kolthoff (103) observed a strong decrease in the adsorbed amount of hydrochloric acid on addition of phenol or amyl alcohol t o a system containing H-charcoal. Practically no change was ob served on addition of sugar or chloral hydrate. Quantitative studies of simultaneous adsorption on ash-free charcoals have also been reported b y Dubinin (56), and b y Landt and Knop (119). The latter authors investigated the first 5 homologous monocarboxylic aliphatic acids, finding t h a t the amounts adsorbed decreased on addition of hydrochloric acid. For dibasic carboxylic acids the results were more complicated. After the addition of hydrochloric acid the adsorption of oxalic or malonic acid was increased, but with succinic, glutaric and adipic acids the amounts adsorbed were decreased, a t least a s regards dilute solutions of the organic acids. Dubinin (56) successfully expressed his results with regard t o simultaneous adsorption in a simple mathematical form. Com paring the amount of adsorbed hydrochloric acid, when this was t h e single solute, and the adsorption of the acid from a solution t o which, for instance, acetone had been added, he found the following equation t o be approximately satisfied: number of expelled HCl molecules number of entering organic molecules

K being a constant. This rule was later studied for a number of substances b y Landt and Knop (119). They found t h a t the con stant in Durbinin's formula was almost independent of the con centration of the dissolved substances. These authors observed t h a t the constant in question, when mixtures of aliphatic acids and hydrochloric acid were used, increased in a regular manner with the number of carbon atoms in the organic acid. From these observations it was concluded t h a t the hydrocarbon chain lies flat on the surface of the charcoal. From this review i t is seen t h a t the assumption of Lachs and Michaelis t h a t the adsorptions of ions and of molecules proceed independently, is not applicable t o the experimental results obtained with ash-free charcoals. I t might be considered as settled, b y the modern investigations reported, t h a t non-electrolytes have a pronounced influence on the adsorption of strong inorganic acids. This fact is in agreement with the suggestion by the present writer, t h a t there are no special active centres for electrolytes. The experiments mentioned cover, however, only a compara tively small proportion of the exchange between the inorganic ions and the organic molecules in the adsorption layer. The author thought it of interest t o study whether i t would be possible com pletely t o inhibit the adsorption of an inorganic acid on an H charcoal and the adsorption of an alkali hydroxide on an L-charcoal, b y the addition of an adsorbable non-electrolyte. Experiments with this aim in view were carried out using the highly adsorbable phenyl-dimethyl-pyrazolone (antipyrine) as the non-electrolyte. This substance has a high solubility in water and its ionization constant is only K b = 4.10~~13 (100). I t was found t h a t the presence of antipyrine in the system strongly decreased the adsorption of hydrochloric acid (Table 14). On the other hand no influence on the adsorption of sodium hydroxide on L-charcoal could be observed from the presence of antipyrine (Tables 15 and 16). These experiments were repeated using several organic nonelectrolytes such as acetone or ethyl alcohol and i t was always found possible t o desorb mineral acids, but never alkali metal hydroxides.

Table 14. Expulsion of adsorbed HCl with antipyrine.

1.000 g. H-charcoal t o which had been added 20.00 ml. HCl, 0.0200 N , and 2 days later 10 ml. of antipyrine solution of varying strengths. The mixture was filtered a t the end of 4 days and the HCl in the filtrate determined b y means of titration with NaOH and H g (N0 3 ) 2 . (Average of these results tabulated.) Free HCl
!

Conen, of antipyrine solution in molality

Adsorbed HCl

Expelled HCl %
i

in ml. 0.02 N solution 5.25 5.25 6.35 7.49 8.56 10.58 13.08 15.12 16.53 19.23 14.75 14.75 13.65 12.51 11.44 9.42 6.92 4.88 3.47 0.77

0.000
0.005 0.025 0.050 0.10 0.25 0.50 1.00 1.25 2.50

0.00 1.10 2.24 3.31 5.33 7.83 9.87 11.28 13.98

0.0 7.5 15.2 22.4 36.1 53.1 66.9 76.5 94.8

Table 15. Adsorption of sodium hydroxide on L-charcoal in t h e presence of 1,5-dimethy 1-2-phenyl-3-pyrazolone. 1.000 g. L-charcoal activated a t 450 C., 14 hours. ( 30.00 ml. Volume of liquid:} ^ m , Time of contact: 4 days.
Composition of solution: NaOH, 0.0200 N Antipyrine, 2.5 m. ml. ml. 20.00 20.00 20.00 30.00 30.00 30.00 i 5.00 10.00 1 5.00 10.00
!

H2O ml.

Equil. conen. NaOH mN 1 1 j I 0.40 0.33 0.42 3.42 3.47 2.98

10.00
5.00

10.00
5.00

Adsorption of l,5-dimethyl-2-phenyl-3-pyrazolone in the presence of sodium hydroxide. 1.000 g. L-charcoal activated a t 450 C., 14 hours. Volume of liquid: 30.00 ml. Time of contact: 4 days. 0.3000 g. Antipyrine.
NaOH mN Adsorbed Anti pyrine mg. 186 194 201 193 206 190

3.33 6.67 13.33 16.66

3 4 QnHpyrine.

5 mmole.

Fig. 3. Influence of antipyrine on the adsorbed amount of malachite green. 1.00 g. H-charcoal. Volume of liquid: 100 ml. Time of contact: 4 days. The ordinate shows the amount of malachite green not adsorbed.

I n addition, a study was made of the influence exercised by antipyrine on the amounts of organic electrolytes adsorbed from water solutions. I t was found possible t o expel both acid and basic dye-stuff ions from an H-charcoal b y the addition of a

solution of antipyrine t o the system. The results with malachite green and antipyrine are represented graphically in Figure 3. An attempt has also been made t o carry out adsorption experi ments in a system consisting of three phases, using a liquid nonelectrolyte immiscible with water, a solution of an electrolyte in water, and H-charcoal. I t was found t h a t the addition of organic water-insoluble liquids such as benzene, ethyl ether, carbon disulphide and chloroform t o a system of charcoal with adsorbed strong electrolytes suspended in water, did really bring about desorption of electrolytes from the charcoal. This was possible, however, only if the adsorbed electrolyte was insoluble in the organic solvent (179), as m a y b e judged from the experiments t o be reported. For the preliminary qualitative experiments organic electro lytes (dye-stuff salts) were used. To a solution of methylene blue chloride in water were added small amounts of H-charcoal until the solution was completely decolorized. The suspension was filtered through a glass filter b y suction, without exposing the charcoal layer t o the air. On addition of excess water t o the char coal residue on the filter, the filtrate did not become coloured. After this test, the funnel was filled with pure chloroform, which had previously been freed from hydrochloric acid and alcohol. When drawn through the charcoal b y suction the chloroform was not coloured. Methylene blue chloride is insoluble in this liquid. When water was added t o the chloroform-wetted charcoal, the water was coloured deep blue after passing through the charcoal layer. The amount of methylene blue chloride liberated per unit volume of passing water slowly decreased. On making a fresh addition of chloroform and water more dye-stuff could be desorbed. The same experiment could be made using ethyl ether, toluol and carbon disulphide as organic solvents. Benzene could not be used with equal success, especially if the reaction of the washing water was alkaline. After the addition of benzene and 0.01 N sodium hydroxide no methylene blue could be water-extracted from charcoals with small amounts of adsorbed dye-stuff. Judging from these experiments it seemed possible t h a t an electrolyte could be completely desorbed b y the method under discussion. As examples of quantitative experiments with organic

Desorption of picric acid from H-chareoal with carbon tetrachloride and water. 1.00 g. H-charcoal. Rate of filtration: circ. 5 ml. per min.
Adsorbed picric Sum of added acid CC14 mequiv. 0.7845 0.7845 0.7845 0.7845 0.5230 0.5230 0.2615 0.2615 0.1569 0.1569 ml. Volume of aqueous filtrate ml. 2 000 1 960 2 325 2 430 2 165 2 040 1 800 2 010 1 600 1 340 Desorbed picric acid mequiv. trace 0.731 0.738 0.713 0.490 0.467 0.226 0.203 0.112 0.100 Per cent desorbed picric acid

75 75 100 75 75 75 75 75 100

93 94 91 94 89 86 78 71 64

electrolytes an account will be given of the desorption experi ments with picrate and methylene blue ions. H-charcoal suspended in water was allowed t o adsorb picric acid in amounts so t h a t the concentration of the picrate ions, after shaking, was not colorimetrically determinable in the solution. Carbon tetrachloride was added after the adsorption. Picric acid is known t o be insoluble in this solvent. When the mixture was shaken, the water phase was immediately coloured yellow. The mixture was filtered through a glass filter, and the charcoal washed with distilled water. During this washing process another part of carbon tetrachloride was added when the picrate ion concentration in the effluent filtrate had decreased considerably. After this addition the rate of desorption b y water was again increased. The addition of fluids and the washing procedure was repeated until the concentration of the picrate ions in the filtrate was too low for reliable colorimetric analysis. The total amount of picric acid desorbed was estimated colorimetrically. Similar experiments were also carried out using washing fluids having different pH. The same results were obtained in acid and alkaline solutions. The results are shown in Tables 17 and 18.

Desorption of picric acid from H-charcoal with carbon tetra chloride and hydrochloric acid, 0.02 N or sodium hydroxide, 0.02 N . 1.00 g. H-charcoal. Rate of filtration: circ. 5 ml. per min.
Adsorbed picric Sum of added CC14 acid mequiv. ml. Volume of aqueous filtrate ml. Desorbed picric acid mequiv. Per cent desorbed picric acid

Washing fluid: Carbon tetrachloride a n d HCl, 0.02 N

i

0.7845 0.7845 0.5230 0.2615

75 75 75

2 000 2 210 1 860 2 180

trace 0.726 0.461 0.198

93 88 76

Washing fluid: Carbon tetrachloride and N aO H, 0.02 N 0.7845 0.7845 0.5230 0.2615 2 000 2 020 1 940 2 110 trace 0.741 0.473 0.210

75 75 75

94 90 80

Table 19. Desorption of methylene blue chloride from H-charcoal with chloroforpa and water. 1.00 g. H-charcoal. Rate of filtration: circ. 5 ml. per min.
Adsorbed methylene blue mequiv. 550 550 550 504 420 336 210 Sum of added CHCI3 ml. Volume of aqueous filtrate ml. 1 500 1 200 1 640 1 320 1 460 1 200 1 170 Desorbed methylene blue mequiv. trace 490 510 465 395 295 170 Per cent desorbed methylene blue

75 100 75 75 75 75

89 93 92 94 88 81

Desorption of methylene blue chloride from H-charcoal with chloroform and 0.02 N HCl. 1.00 g. H-charcoal. Rate of filtration: circ. 5 ml. per min.
i Sum of added Adsorbed methylene blue CHClg mequiv. 550 550 504 420 210 ml. Volume of aqueous fiJtrte ml. 1 470 1 310 1 030 1 130 980 Desorbed methylene blue mequiv. 0 500 460 375 155 Per cent desorbed methylene blue

100 75 75 75

91 91 89 74

If another identical sample of charcoal with the same amount of adsorbed picric acid was washed with pure water only, in the same way and the same amount as in the described experiment, no colorimetrically determinable amounts of picric acid were desorbed. Analogous experiments were carried out with methylene blue chloride. As organic solvent chloroform was used. Because of the low solubility of methylene blue hydroxide, only distilled water and 0.01 N hydrochloric acid were used as washing agents in these experiments. The results are t o be found in Tables 19 and 20. The expulsion of adsorbed mineral acids was also found t o be possible b y the described method. The desorption of hydrochloric acid was carried out in static experiments. I n these, fixed amounts of hydrochloric acid were added t o 1.0 g. of charcoal, and the mixtures shaken in stoppered bottles in a shaking machine for two days. After this time an organic water-immiscible solvent was added, and the mixture replaced in the shaking machine for a further four days. The mixture was then filtered and the water phase separated, an aliquot part of the latter being subjected t o analysis. The chloride and hydrogen ion concentrations in the filtrates were identical within the experimental error. I t was found t h a t all organic solvents used caused a pronounced decrease in the adsorption of the inorganic acid. Some experimental results 644593
Brje Steenberg

81

Adsorption of HCl on H-charcoal in the presence of organic solvents. 1.000 g. H-charcoal + 30 ml. HCl, 0.0200 N . 25 ml. organic water-immiscible solvent added 2 days later. Analysis on 6 t h day.
Organic solvent Adsorbed HCl mequiv.
i

Equil. concn.HCl mN 8.013 19.887 15.413 17.200 18.253 17.773 18.273 14.213 12.107

Expelled HCl %

Diethyl ether Chloroform Carbon tetrachloride Carbon disulfide Benzene . . Toluene Petroleum ether . . . . Pentane

0.3596 0.0034 0.1376 0.0840 0.0524 0.0668 0.0518 0.1736 0.2368

99 62 77 85 81 86 52 34

are given in Table 21. I t was interesting t o note t h a t the liquids whose vapours are known t o be adsorbed on charcoal with the liberation of very great heats of adsorption are those which are most effective in causing desorption of the acid. The lower aliphatic hydrocarbons have the least ability t o cause desorption. I t was found t h a t desorption in all cases was very slow, and it is not claimed t h a t equilibrium was obtained in the reported experiments. Analogous experiments were carried out with an L-charcoal activated a t 400 C and a water solution of sodium hydroxide. I n this case it was impossible t o desorb hydroxide from the char coal b y the use of any tested organic solvent (Table 22). As a result of the reported experiments i t has been ascertained that the adsorption of strong electrolytes on H-charcoal is influenced by non-electrolytes dissolved in water. If the concentration of the non-electrolyte is sufficiently large, the adsorption of, for instance, mineral acid on H-charcoal is greatly reduced, and i t seems possible completely t o inhibit such an adsorption. On the other hand, it has not been found possible t o influence the amount of an alkali metal hydroxide adsorbed on an L-charcoal b y the addition of a water-soluble non-electrolyte t o the system.

Adsorption of sodium hydroxide on L-charcoal in the presence of organic solvents. 0.500 g. L-charcoal activated a t 400 C., 10 hours. 30.00 ml. NaOH, 0.02000 N. 25.0 ml. organic solvent added after 2 days' contact between L-charcoal and solution of sodium hydroxide. Analysis of water phase on 6 t h day.
Solvent Equil. concn. NaOH N 0.00833 0.00842 0.00836 0.00861 0.00830 0.00683 0.00782 0.00807

Ethyl ether Benzene Toluene Chloroform Carbon tetrachloride Petroleum ether

This result seems t o indicate t h a t there is a fundamental dif ference in the nature of the forces which adsorb mineral acids on H-charcoal and of those which adsorb alkali metal hydroxides on L-charcoal. Since non-electrolytes do not affect the adsorption of alkali metal hydroxides on L-charcoals, it must be concluded t h a t these sub stances are adsorbed by forces of greater strength t h a n those operating in the adsorption of non-electrolytes on this type of charcoal. Since it has been found t h a t an L-charcoal can adsorb, besides alkali metal hydroxides, large amounts of non-electrolytes, without the adsorption of the alkali metal hydroxide being affected, it must be inferred t h a t these substances are not adsorbed on the same points of the charcoal. I t seems reasonable t o the writer t h a t the oxide theory of electrolyte adsorption on charcoal is valid when L-charcoals are adsorbing, and consequently t h a t the sur face of this carbon is, a t least partially, coated with acid carbon oxides. On the other hand, the adsorption of, for instance, mineral acids and non-electrolytes on H-charcoal proceeds with forces of

the same order of magnitude. I t does not seem necessary t o conclude from the experimental results t h a t the adsorptions of mineral acids and of non-electrolytes on H-charcoal are different i n nature. I t is, however, possible to explain the results in another way. I t is conceivable that the decrease in the adsorbed amount of an electrolyte, noted after the addition of a non-electrolyte, can be ascribed t o changes in the activity of the ions. Such changes do occur on addition of a non-electrolyte t o a solution of an electro lyte. These changes are especially difficult t o evaluate for ad sorbed ions, since t h e concentrations of the ions in the vicinity of the charcoal surface are unknown. Consequently, if a decrease in the adsorbed amount of the strong electrolyte is observed after addition of a non-electrolyte, this cannot be taken as a definite proof t h a t the adsorptions of electrolytes and non-electrolytes are similar in nature. I n order t o minimize the effect of the non-electrolyte on the activity of the electrolyte, experiments were performed in which firstly the non-electrolyte chosen was a liquid not miscible with water, and secondly the electrolyte was insoluble in the liquid in question. The results obtained in this case were in principle not different from those which were carried out with non-electrolytes soluble in water. Although generally not more than 90 per cent of the adsorbed ions were liberated in the reported experiments with the H-char coal, there is justification for assuming t h a t all or almost all the adsorbed organic ions are desorbable b y the discussed method. I t must be remembered t h a t the washing water a t the end of each experiment still liberated organic ions, but t h a t the concentrations of these were too low t o be reliably estimated. I t thus seems fairly safe t o conclude t h a t the adsorption of both substances takes place on the same areas of the H-charcoal. These experiments submit further proof of the difference in the nature of the adsorption forces operating in the adsorption of inorganic acids on H-charcoal and of those operating in the ad sorption of inorganic alkalis on L-charcoal. Before discussing this matter, it will be of interest t o consider the somewhat startling observation that it is possible t o desorb

electrolytes from H-charcoal by means of water-immiscible organic solvents in which the desorbed electrolyte is insoluble. Charcoal may be considered a hydrophobic rather t h a n a hydrophilic substance. This is especially the case with charcoals activated a t high temperatures (88). When water is added t o H-charcoal, the charcoal powder will float for hours on the surface of the water, without being wetted. L-charcoals are more easily wetted b y water. This observation, which has been confirmed b y many investigators (21, 97, 109, 118) is rather peculiar, if the high hygroscopicity of all activated charcoals is considered. Organic solvents generally possess a high ability to wet charcoal. The difference in this respect between H-charcoal and water, and H-charcoal and organic solvents, is easily demonstrated. If a suspension of charcoal in water is added t o an organic solvent immiscible with water, and the mixture is shaken, the charcoal will leave the water phase and enter the organic solvent. The water phase is left almost completely clear. I t is also possible t o observe a differential wetting heat when the H-charcoal leaves the water and enters the organic solvent. The reaction is, how ever, too slow to be recordable calorimetrically without appreciable error. H-charcoal is found t o be preferentially wetted by most organic solvents irrespective of the p H of the water phase. Excep tions are pentane and hexane. I t is of interest t o note t h a t ozo kerite, coal-tars and petroleum pitch are only feebly dissolved b y these fluids (2). L-charcoals suspended in an alkaline aqueous solution are found, after shaking with chloroform, to remain chiefly in the interface between the fluids. The desorption of the strong electrolyte, methylene blue chloride, b y the chloroform may be ascribed to the expulsion of the water from the surface of the wet charcoal. As the dye-stuff is insoluble in chloroform, but soluble in water, it will be desorbed together with the water. The negative results from the use of benzene and alkaline washing water will be understood from the fact t h a t methylene blue hydroxide is slightly soluble in benzene. The necessity of using an organic solvent in which the substance t o be desorbed is insoluble can be demonstrated b y the following illustrative experiment. To a green solution composed of the blue dye-stuff Nile blue

sulphate (diethylamino-pheno-amino-naphthazonium sulphate) and the yellow dye-stuff atabrin (2-methoxy-6-chloro-9-diethylaminoa-methyl-butylamino-acridine hydrochloride) in water, charcoal was added until the solution was completely decolorized. The mixture was filtered and the charcoal on the filter treated with benzene. The effluent benzene was colourless. If after this pretreatment water was filtered through the charcoal, the filtrate was coloured deep blue without any green hue, and consequently contained no atabrin. Without pre-treatment with benzene it was found impossible t o desorb measurable amounts of the dyestuffs with water. These observations can be interpreted in the manner indic ated, if it be borne in mind t h a t the yellow atabrin is soluble in benzene, while Nile blue, on the other hand, is insoluble in this liquid. After treating the desorption process in some detail we will now turn our attention to the impossiblity of desorbing alkali metal hydroxides from L-charcoal. If the oxide theory of electrolyte adsorption be accepted, there seems t o be no essential difference between the treatment of a salt of an L-charcoal acid in an alkaline medium, and a salt of an H-charcoal base in an acid medium, with a water-immiscible organic solvent. The process described may formally be regarded as an extraction of charcoal b y means of an organic solvent. Taking the theory of surface oxides as a basis, the desorption process is consequently analogous t o the quantitative extraction of a char coal base, or a charcoal acid, from a salt of one of these performed a t a p H a t which the acid or base must be supposed t o be com pletely dissociated. Processes of this type are not known t o the author. Ionic exchangers of the resin type seem t o be suitable as models for charcoal with surface oxides, assuming the latter substance t o be built u p in the manner conceived b y the supporters of the oxide theory. An anionic exchanger in the hydroxylic state may be used as a model for the H-charcoal, and a cationic ex changer in the acid state for the L-charcoal. The author carried out experiments according t o the method described with sub stances of these types, and found it impossible to desorb ad-

sorbed acids or bases from these ionic exchangers b y means of organic solvents. 1 I t must be concluded from the foregoing t h a t the impossibility of desorbing alkali hydroxides from L-charcoals furnishes an argu ment in favour of the oxide theory as regards this type of charcoal. On the other hand, the fact t h a t i t is possible t o desorb inorganic acids from H-charcoal, as has been demonstrated, cannot be explained b y the oxide theory of electrolyte adsorption. To sum up, it has been shown in this chapter t h a t the adsorp tion of all kinds of strong electrolytes is influenced by the presence of non-electrolytes in the system when H-charcoals are used. I n all cases studied, the adsorbability of the electrolyte decreased when non-electrolytes were added t o the system. The desorption of ions was found possible also when the liquid non-electrolyte was not miscible with water, provided the electrolyte was insoluble in the organic solvent. This new method of desorption seems applicable t o the scientific and technical isolation and concentration of substances from very dilute solutions (179). Judging b y the results of the investigation it seems plausible t o the writer that ions of all kinds adsorbed on H-charcoal are held b y forces of the same strength as those in action in the ad sorption of non-electrolytes, and consequently t h a t these are, apart from the surface mirror image forces, of the type known as van der Waals' forces. I n the writer's opinion, it therefore seems unnecessary t o make use of the idea of special active centres in order t o explain the adsorption of ions on H-charcoal. On the other hand, the experimental results with L-charcoals were found t o conform t o the hypothesis t h a t the adsorption of ions on this charcoal may be interpreted as an ionic exchange, if the charcoal be regarded as a cationic exchanger. The theory t h a t ions are adsorbed on H-charcoal b y forces t h a t are essentially of the same nature as those effective in the adsorption of non-electrolytes will be used as a starting point in the following treatment of electrolyte adsorption on H-charcoal.
The exchangers were of the same type as the "Wofatites" of the I. G. Farben industrie.
1

IX. Primary and Secondary Adsorption of Ions on H-charcoal.

The van der Waals' forces acting between a surface atom of the charcoal and an ion are dependent upon characteristic properties of both the particles. If an ion is placed in a definite position with respect to a surface atom of the charcoal, the force between these particles will generally not be identical with the force ob tained if the ion in question is replaced b y an ion of a different kind. This implies t h a t the adsorbabilities of the positive and negative ions of a n electrolyte are not generally identical. From experimental observations on the adsorption of electrolytes on H-charcoal it can be concluded t h a t the adsorption force between H-charcoal and a large organic ion is very large in comparison with the force between the charcoal and most inorganic ions. Alkali metal ions, for example, are not measurably adsorbed b y Hcharcoal. Among the strong inorganic electrolytes, only mineral acids are adsorbed in amounts of the same magnitude as strong electrolytes containing larger organic ions. Consider a solution of an organic salt, composed of a large organic ion and an inorganic ion1, in contact with H-charcoal. The char coal attracts the organic ions strongly b u t the inorganic ions only weakly. I n the coming discussion we may assume t h a t the latter attraction is so small t h a t it can be completely neglected. Irrespec tive of the non-existence of adsorption forces between the inorga nic ion and the charcoal, the inorganic ion must be adsorbed. The adsorbed organic ion will, in fact, b y virtue of its electrical charge, attract the inorganic ion which has the opposite electrical sign. The result will be an equivalent adsorption of positive and negative ions. I n the following discussion, those ions which are held by the
1 A strong electrolyte composed of an organic and an inorganic ion will hence forth be called an organic-inorganic electrolyte.

charcoal by the short range van der Waals' forces will be named "primarily" adsorbed ions, and the ions attracted to the primarily adsorbed ions by means of the long range electrical forces will be called the "secondarily" adsorbed ions. If the charcoal surface is completely covered by primarily adsorbed ions, the secondarily adsorbed ions will form a Helmholtz-Gouy double layer. Even if the charcoal is not completely covered b y primarily adsorbed ions, there will exist a locally in creased concentration of counter-ions in the vicinity of the primarily adsorbed ions, having the same total electrical charge as the primarily adsorbed ions. Some conception of the distribution of these ions may be obtained b y applying the same ideas as those used b y Debye and Hckel in their theory of strong electrolytes. I n the preceding chapter it was made probable t h a t H charcoal is a non-polar adsorbent. Consequently the above picture can be applied irrespective of the electrical sign of the primarily adsorbed ion. The proposed relationships on the surface of an H-charcoal in contact with a solution of an electrolyte bear a strong resemblance t o those a t the air/water interface, when surface active electroly es are present in the water. On the water surface organic ions are known t o be adsorbed with their hydrophobic hydrocarbon groups extending into the gas phase, and dipping their polar groups into the water. This orientation occurs irrespective of the sign of the electrical charge of the adsorbed ion. The charge of the sur face ions is compensated by attracted ions of the opposite sign. Although the results of the adsorption of surface active ions on the water/air surface and t h a t of organic ions on the water/charcoal interface are the same, the processes are not identical in origin. The forces which expel the hydrocarbon chains from the water phase are certainly not identical with those which attract an organic ion t o an H-charcoal. The similarity between the cases is found in the fact t h a t forces tend t o pull an ion from the bulk of solution into the surface, and t h a t these forces act t o different extents on the two ions of a dissolved electrolyte. ft One of the main consequences of the theory on the adsorption of ions on H-charcoal presented b y the writer is t h a t the surface

surplus of ions of each electrical sign must be equivalent. I t follows from the law of electrical neutrality t h a t the condition for the diffusion of an ion into or from the transitional region between the bulk of solution and the charcoal surface is t h a t one or more ions of the opposite charge, totalling the same electrical charge, can accompany the ion. A corollary t o this statement is that diffusion from the transitional region of a single ion can occur only if ions of the same total valency and the same sign pass the fictitious boundary between the transition region and the bulk of solution in the reverse direction. The greatest possibility for a n ionic exchange of the indicated type exists as regards the secondarily adsorbed ions. This discussion directs attention t o a n experimental method for the study of the orientation of the adsorbed electrolyte on the surface of the charcoal. If, after the adsorption of an electrolyte, another electrolyte be added t o the free solution, an exchange may occur between secondarily ad sorbed ions and ions of the same electrical sign from the second electrolyte. B y observing whether anions or cations are exchange able it can be concluded which ions are primarily and which sec ondarily adsorbed. Experimental data presented subsequently (Chapter 10) show t h a t H-charcoal with adsorbed ions can behave as an ionic ex changer. I t has been found possible t o produce both anionic and cationic exchangers b y adsorbing different electrolytes on Hcharcoal. The exchange capacity of these ionic exchangers is determined b y the number of adsorbed ions per unit weight of charcoal. Their practical durability as exchange materials depends on the possibility of washing out the primarily adsorbed ions. The ionic exchange materials built up from H-charcoal and adsorbed electrolytes are of special interest from a theoretical point of view. I t is possible, for instance, t o vary continuously the exchange capacity per unit weight of carrier. I t is well known t h a t the Donnan membrane theory is applicable t o a system composed of electrolytes and an ionic exchanger of, for instance, the zeolite type. The writer has found t h a t the Donnan law also furnishes a basis for the interpretation of the relations a t equilibrium in a system composed of H-charcoals and a solution of electrolytes in water.

Before applying the Donnan theory to the problem of interest in this paper, it is of value to recapitulate the theory in question. The original Donnan theory deals with ionic equilibria in systems divided b y a semipermeable membrane which prevents the diffusion of one ion through the system. I t was found by Donnan and Harris t h a t those ions simultaneously present, which can diffuse throughout the complete system a t equilibrium, distribute them selves unequally in the two parts of the system. The phenomenon was treated thermodynamically b y Donnan (51) in 1911, and in a more complete manner b y Donnan and Guggenheim in 193234 (53, 52). The reader is referred to their papers for a complete deduction. Let us consider a system containing two liquid phases separated by a semipermeable membrane. One of these phases (denoted b y a single dash) is assumed t o contain an ion (X) which cannot pass the membrane and diffuse into the second phase (denoted b y a double dash). Besides this ion the system contains several electrolytes, the ions of which can freely pass from one phase into the other. I t is demonstrated by these authors t h a t the con dition for equilibrium in this system is t h a t the ions A, B, C, . . . of the valencies a, b, c, . . . and of the opposite sign t o the X-ions distribute themselves between the two phases according t o the following formula, a denoting activity:

From this formula it is obvious t h a t a t a low ionic strength in the system, multivalent, freely diffusible ions will concentrate in the phase containing the X-ions. If the total concentration of ions in the system is high in comparison with the concentration of the X-ions, the ions A, B, O, . . . will distribute themselves almost equally over the complete system. The treatment used in the deduction f formula (2) does not include any definite postulate regarding the reason why the X-ions cannot pass from one phase t o another. The formula is con sequently valid even in systems in which the phases are not se parated b y a semipermeable membrane, but it is necessary t h a t

the X-ions should be restrained in some way from diffusing t o all parts of the system. We may consider a system consisting of an H-charcoal and a solution containing several species of positive and negative ions in water. I t is anticipated t h a t a t equilibrium only one of the species of the ions (denoted X) will be primarily adsorbed b y the charcoal, and t h a t the equilibrium concentration of the X-ions in the bulk of solution will be negligible. The electrical charge of the more or less complete layer of primar ily adsorbed X-ions is compensated b y counter-ions, the secondarily adsorbed ions. The primarily adsorbed ions are held b y forces having a considerably shorter range of action than the forces which attract the counter-ions t o the primarily adsorbed ions. The ionic double layer on the charcoal is consequently diffuse in the direction of the bulk of solution. I n order t o treat the adsorption process thermodynamically it is now necessary t o divide the system into two parts. This is done in a purely formal way b y drawing a mathematical surface parallel t o the charcoal surface, in such a manner t h a t it encloses the charcoal and runs just inside the homogeneous bulk of solution near the fictitious boundary of the physically inhomogeneous transition region between the solution and the charcoal. The surface is so described t h a t electrical neutrality is maintained in each part of the system. One of the parts of the system (part 2) defined in this way is physically homogeneous, and the concen tration of the ions in this space is identical with t h a t in the bulk of solution far from the charcoal surface. The other p a r t (part 1) contains the charcoal and the transition region between the charcoal and the bulk of solution. The difference between the volume of the charcoal and the volume of part 1 has been given a definite magnitude, by the method employed in the division, and we are justified in speaking in a thermodynamical sense of a concentration of ions in this space. I n the following text this space (V) will be called the adsorption space or volume (indicated by a single dash), in contradistinction t o part 2 of the system (F"), named the free solution (indicated b y a double dash). I t will now be demonstrated t h a t the Donnan law can be applied t o the distribution of secondarily adsorbable ions between the

adsorption space and the free solution in the system under con sideration. Firstly, it is observed t h a t the X-ions are all present in the adsorption space, which they cannot leave because of the forces acting between these ions and the charcoal. This fact is t h e primary condition necessary for the application of the Donnan law. I n deducing the Donnan law, the chemical and the electro chemical potentials of a substance present in two phases are compa red. I n order t h a t the deduction may be valid, however, it is not necessary t h a t the two parts of the system should be phases, in the meaning of Gibbs. I t is a method commonly employed in chemical thermodynamics, for the study of equilibria, t o compare t h e chemical potential of a substance in different parts of a system. These parts are generally phases, in the meaning of Gibbs, but because the chemical potential a t equilibrium must acquire the same value in every part of the system the comparison in question may be made between any two elements of the system. The divi sion of a system into phases has a meaning only when a phase boundary has developed. Such a boundary is never a mathematical surface, but has always a certain vagueness of outline. Because the extension of the adsorption space normal to the charcoal surface is very small it seems questionable whether the adsorption space and the free solution can be called phases. I n any case, this is not necessary for the application of the Donnan law t o the system. From this discussion i t is seen t h a t there can be no objections t o applying the Donnan law t o the system under consideration. If the adsorbed X-ions have the valency x and the system contains A, B, C, . . . species of ions of the opposite sign t o X , and having the valencies a, b, c . . . the Donnan equation can be written:

fr-fr--

The activity of the X-ions in the adsorption space is unknown. The total amount of adsorbed X-ions can, however, be determined analytically. From this estimation the total electrical charge of the excess ions of each sign in the adsorption space can be calculated,

as i t was assumed t h a t n o other species of ions t h a n X-ions could be primarily adsorbed. From t h e condition of electrical neutrality, thus: x[X]' = a[A]' 4- b [B]' + = (4) where S will be called t h e exchange capacity. From analytical d a t a i t is possible t o determine t h e adsorbed amount of ions of different species present in t h e adsorption space. On introducing this amounts, expressed in moles, into formula (3), t h e following formula will be obtained when only two ions of t h e opposite sign t o X are present: (n = moles)

5 < >
The ratio of t h e activity coefficients of t h e ions in t h e adsorption space cannot be independently determined. If the average ionic strength in t h e adsorption space is constant t h e activity coefficient ratio is also constant, or nearly so. This condition probably nearly obtains in a series of experiments where t h e amount of X-ions per unit weight of charcoal is constant, and t h e concentrations of ions in t h e free solution do not differ too widely. Introducing (ni/g-(/*)i/6 _ (V'y' b (f' A ) lla ~
K , B

,6) ( )

where K B will be called the constant of distribution, into formula (5) we arrive at:
(ri)Va-(<iB)llb

(n'B)1/6 (aa) 1/a

&A, B

(*)

With t h e aid of this formula, and analytical data, including t h e knowledge of t h e activity coefficients of t h e secondarily adsorbable ions in t h e free solution, K B can be computed. If only t h e univalent ions A and B are secondarily adsorbable, t h e formula will only contain fractions of concentrations, and the unit in which these are expressed will be of no importance: B' [A"~\ f' '
B ( )

A' and jB' are here the number of adsorbed A and B ions. If the concentration of the ions in the free solution is very low, the activities of the secondarily adsorbable ions can be replaced b y their concentrations:
A

&'W\~

'

[ B

"

- k

,B

( m )

I n the following chapter the author reports on experiments carried out in order t o test this application of the Donnan theory t o electrolyte adsorption on H-charcoal.

X. The Applicability of the Donnan Theory to Secon darily Adsorbed Ions on H-charcoal.

A.

General considerations.

The central point in the theory of electrolyte adsorption on H-charcoal proposed b y t h e writer is the distinction made between primary and secondary adsorption of ions. I t has been shown theoretically t h a t t h e principles of t h e Donnan theory can be applied t o a system composed of a n electrolyte solution and a charcoal. The system considered in this treatment was idealized. I t was assumed, for instance, t h a t of all ions present only ions of one kind (X) could be primarily adsorbed. I t was thus assumed t h a t t h e v a n der Waals' forces between t h e charcoal and all the other species of ions present in t h e system were too small t o bring about adsorption. Further it was assumed t h a t , a t equilibrium, all t h e X-ions present in t h e system were adsorbed b y t h e charcoal. I t must now be discussed whether it is possible t o produce a real system which fulfils t h e requirements now mentioned. The closest agreement with t h e requirements of t h e author's theory must be found when in adsorption experiments a n electro lyte is used, t h e anion of which is attracted t o t h e charcoal b y forces of much greater magnitude t h a n those attracting the cation. I n order t o test t h e theory exhaustively, experiments must also be carried out using electrolytes chosen so t h a t t h e cations are strongly attracted t o t h e charcoal, while t h e anions are only feebly attracted. I t has been found b y several investigators t h a t alkali metal ions are not measurably adsorbed b y H-charcoal from solutions containing only inorganic salts. This indicates t h a t t h e attraction forces between t h e charcoal and t h e alkali metal ions are very weak. On t h e other hand, i t has been found t h a t organic ions, especially large organic ions containing cyclic hydrocarbons, are adsorbed in large amounts on H-charcoal. Thus, i t can be

assumed t h a t from an electrolyte composed of a large organic anion and an alkali metal ion only the anion is primarily adsorbed. This has also been found to be the case. When electrolytes composed of an organic cation and an in organic anion are used for the adsorption it has been found t h a t in this case also the organic ion is the primarily adsorbed ion. This is somewhat astonishing, as the common inorganic anions are adsorbed in measurable amounts from both inorganic salts (hydrolytic adsorption) and inorganic acids. For an experimental test of the applicability of the Donnan theory t o electrolyte adsorption on H-charcoal it is preferable t h a t the primarily adsorbed ions a t equilibrium should not be present in the free solution. An H-charcoal with primarily ad sorbed cations or anions will in this case function as the commerci ally used anionic or cationic exchangers, respectively. I t is well known t h a t several organic dye-stuffs can be adsorbed in appreciable amounts per unit weight of charcoal in such a way t h a t the free solution, after the adsorption process, is completely decolorized, and t h a t it is impossible t o wash out measurable amounts of the dye-stuff even with considerable quantities of water. I t is consequently not impossible t o obtain a system in which the organic ion is adsorbed t o such a great extent t h a t its concentration in the free solution is negligible a t equilibrium. Such a system corresponds closely t o the idealized system used in the theoretical discussion on the applicability of the Donnan theory t o electrolyte adsorption on H-charcoal. I n order t o investigate which of the ions of an adsorbed electro lyte is the primarily, and which the secondarily adsorbed one, the exchangeability of the ions must be studied. For such a n experiment i t is necessary t o add a second electrolyte t o the system. This latter electrolyte must be chosen so t h a t none of its ions is primarily adsorbable t o a measurable extent. Any inorganic salt can be chosen t o serve as an electrolyte of this kind, because it has been found in experiments t o be reported later t h a t neither the metal ions nor the common inorganic anions are primarily adsorbable in measurable amounts. The hydrogen (hydronium) ion is found capable of both primary and secondary adsorption. The kind of adsorption occurring in a
7 44593 Brje Steenberg

97

special case is determined b y t h e composition of t h e electrolyte solution. The test regarding t h e exchangeability of a n ion can be carried out b y t h e following method: A n H-charcoal is p u t in contact with a solution of a n adsorbable organic-inorganic electrolyte. The concentration of t h e ions in t h e free solution is estimated when t h e adsorption process has proceeded t o equilibrium. An inorganic substance composed of ions other t h a n those of t h e adsorbed electrolytes is then added t o t h e system, a n d t h e concentration of this electrolyte is made u p t o a t least 1 N . After equilibrium has been reached again t h e free solution is subjected t o another analysis. The amount of t h e ions originally adsorbed and present in t h e diffuse p a r t of t h e electrical double layer on t h e surface of the charcoal will, according t o t h e Donnan theory, be expelled into t h e free solution t o give t h e concentration prevailing before t h e initial adsorption process. I t is required b y t h e author's theory t h a t n o organic ions should be desorbed on t h e addition of t h e inorganic electrolyte. Experiments according t o t h e suggested method were made with electrolytes having either a n organic anion or a n organic cation. Later, t h e experiments were also extended t o strong inorganic acids. B. H-charcoal with adsorbed electrolytes functioning as acidoids.

I t is of great value in t h e testing of t h e theory of primary and secondary ionic adsorption of ions t o find, if possible, a n electro lyte with a n organic anion which, when adsorbed on H-charcoal, will allow cationic exchange t o proceed between as many ions as possible a n d in different environments. When adsorbed weak organic acids are used cationic exchange cannot proceed in acid solutions. Furthermore, weak organic acids are not suitable because t h e adsorbability of t h e unionized molecule is generally greater t h a n t h a t of t h e corresponding anion. Easily interpreted results would be obtained b y t h e use of strong organic acids, since p H changes do not affect their state of dissocia tion, and t h e exchange capacity is consequently always numerically identical with t h e amount of adsorbed acid. The use of anions of

strong organic acids in building u p a cationic exchanger with H-charcoal will permit the exchange t o proceed in both alkaline and acid solutions. I n order t o make this possible, and t o allow for ionic exchange not only with univalent but also with bivalent ions, the organic acid building u p the ionic exchanger must be soluble in a t least slightly acid and alkaline media. I t must also form soluble salts with some uni- and bivalent cations. I n order t o facilitate the investigation the organic ion must be adsorbable in such large quantities t h a t the adsorbed amount can be estimated without too large a percentage of error. I t is well known t h a t cyclic organic substances are generally adsorbed on H-charcoal in larger amounts than saturated aliphatic substances a t identical equilibrium concentrations. I t is further known t h a t the presence of nitrogen in azo-groups or nitro-groups increases the adsorbability of a substance. On the other hand the presence of oxygen in the organic molecule, especially as hydroxy-groups, decreases the adsorbability of the substance. As will be shown in Chapter 12, the amount of ions primarily adsorbed from a solution of a strong electrolyte depends also on the concentration of secondarily adsorbable ions, and t o some extent also on the special nature of these ions. This phenomenon complicates the calculations. The most easily interpretable case will be t h a t in which the organic ion is adsorbed t o a fairly high degree, while a t equilibrium the free solution is practically devoid of this ion. I n the search for a substance with the desired properties it has finally t o be borne in mind t h a t the substance must be available in a pure state and capable of being analyzed in minute amounts in very dilute solutions. The author determined t o use colorimetric analysis, which method is very suitable for problems of this type. The substance sought for must then be coloured itself or capable of being reproducibly transformed into a coloured substance. I t seemed a t the outset most likely t h a t a substance with the desired properties would be found among the sulphonic acids of the organic azo-dyes. The ideal substance was not found in this class. I n the end, picric acid was chosen as the substance most nearly fulfilling the desired qualifications.

Expulsion of hydrogen ions from adsorbed picric acid b y potassium ions. 1.000 g. H-charcoal. Volume of liquid: 30.00 ml. Time of contact: 2 days.
Titration value in ml. 0.02000 N NaOH Picric acid, 0.03550 N ml. 4.00 4.00 4.00 4.00 5.00 5.00 5.00 5.00 7.00 7.00 10.00 10.00 12.00 15.00 15.00 17.00 20.00 20.00 20.00 KNO3, 2 N H2O Observed H-charcoal Carbo activatus (E. Merck) Calculated

ml. 15.00 10.00 5.00 1.00 15.00 10.00 5.00 3.00 10.00 5.00 15.00 10.00 10.00 15.00 10.00 10.00 10.00 10.00 8.00

ml. 11.00 16.00 21.00 25.00 10.00 15.00 20.00 22.00 13.00 18.00 5.00 10.00 8.00

5.00 3.00

2.00

1.96 2.26 3.00 2.12 3.72 3.91 4.02 3.78 10.42 11.21 17.41 17.63 21.23 26.57 26.48 30.11 35.67 35.68 35.40

2.96

5.90

14.06

19.37

28.57

7.10 7.10 7.10 7.10 8.88 8.88 8.88 8.88 12.43 12.43 17.75 17.75 21.30 26.63 26.63 30.18 35.50 35.50 35.50

The experiments with this substance will be discussed in some detail. To samples of 1.000 g. of H-charcoal in flasks were added definite volumes of 0.03550 N picric acid. The maximum amount of picric acid added was fixed a t very near the largest amount which the charcoal in question was found capable of adsorbing without leaving traceable amounts of picric acid in the free solution after shaking. After intensive shaking of the mixtures the solutions were neutral. Ten ml. of a 2 N solution of potassium nitrate were then added

t o each mixture, and the liquid volumes made u p t o 30.0 mL The mixtures were rocked for 24 hours. After this time the mixtures were filtered, and a n aliquot part of each filtrate titrated with 0.02 N sodium hydroxide. The filtrates were found t o be distinctly acid, and the liberated acid was found equivalent t o the amount of picric acid adsorbed. When only small amounts of picric acid m<i e^
0,70,60,50,4X

0,30,20,1 0,2 0,3 0,4 H-charcoal * Carbo ad* (Merck) 0,5 0,6 me^uiv

Qdsorbed picric acid Fig. 4. Expulsion of hydrogen ions from adsorbed picric acid by means of potas sium nitrate. (Data from Table 23.)

are adsorbed per unit weight of charcoal the number of equivalents of liberated acid is smaller t h a n t h a t of adsorbed acid. This fact indicates t h a t the power of the H-charcoal t o adsorb inorganic acids rapidly decreases as the amount of adsorbed picric acid increases (cf. Chapter 12). The filtrates were in all cases colour less, and did not contain organic substances. The results are shown in Table 23 and Figure 4. The same results were obtained when the potassium nitrate was replaced b y other inorganic alkali salts. When the concentration of the salt in the system was increased i t was found t h a t the amount of liberated acid did not increase. From the charcoal left on the funnel after its separation from the liquid phase, picric acid could be liberated b y treating with carbon

tetrachloride and water. The picric acid on the surface of the charcoal seems consequently not t o have been chemically de composed b y the process. The acid liberated b y the potassium nitrate must have arisen from ionic exchange between the sodium ions and the hydrogen ions of the adsorbed picric acid. I t may be worth noting t h a t on the addition of a solution of potassium nitrate t o a pure H-charcoal, an increase in p H of the free solution is found (hydrolytic adsorption). L-charcoal resembles in this respect H-charcoals coated with picric acid as, when L-charcoals are used, the p H of the solution decreases on the addition of an inorganic salt. Some samples of commercially procured charcoals, after ad sorption of picric acid and addition of inorganic alkali salts, were found t o liberate hydrogen ions in amounts which were less than those calculated from the adsorbed amount of picric acid. The liberation of hydrogen ions on these charcoals proceeded according t o the following equation: H+=HP
a d s

-A

(10)

where indicates the number of equivalents of hydrogen ions liberated b y the salt, HP a d s the number of equivalents of adsorbed picric acid, and A is a constant depending on the nature of the charcoal. The results of experiments with a charcoal of this type are also given in Table 23 and Figure 4. The observation can be assumed to depend on the presence on these charcoals of small amounts of an alkaline impurity, forming an insoluble salt with t h e picrate ions. Another interpretation of the observation is t h a t the picric acid is adsorbed, b u t partly present in a state in capable of taking part in the ionic exchange. At the present stage the writer finds it impossible t o decide whether either of these assumptions correctly interprets these observations. With some other samples of charcoal, activated a t a temperature between 650 and 750 C, the solution after adsorption of the picric acid was not neutral but slightly acid, although the free solution was completely decolorized. The amount of acid liberated from a given sample of charcoal was found t o be almost the same irrespective of the quantity of picric acid adsorbed, even when

this was only a small fraction of the saturation value. For samples of charcoal activated a t different times, the quantity of acid liberated was found t o be different. The maximum amount liber ated in any experiment was 0.92 mequiv. per g. of charcoal. The nature of the acid could not be determined. I t is likely t h a t the charcoal on which this observation was made was not pure, but prior t o the addition of the picric acid had been able t o adsorb small quantities of an acid substance or, for instance, oxygen, forming mellitic acid or oxalic acid, which was expelled by the picric acid. Experiments have also been made with picric acid and Hcharcoal, in order t o investigate the possibility of ionic exchange occurring between hydrogen ions and copper or barium ions. Picric acid forms soluble salts with copper and barium. These experiments were carried out using a wet filter of Hcharcoal, which was allowed t o adsorb known amounts of picric acid. Dilute solutions of copper sulphate were poured through the filter in order t o allow a quantitative ionic exchange between the secondarily adsorbed hydrogen ions and the cupric ions. The charcoal was afterwards washed with distilled water until the filtrate was free from copper ions. Without allowing the filter cake t o be broken, 2 N nitric acid was added and slowly percolated through the charcoal. The filtrate was analyzed and found t o contain copper in an amount as nearly equivalent t o the amount of picric acid adsorbed on the charcoal as the experimental error would permit. Analogous experiments were carried out with solutions containing barium ions. These experiments gave the same result. No picrate ions could be detected in the filtrates during any of these processes. Some experimental results are given in Table 24. When charcoal without any adsorbed picric acid was treated with copper sulphate or barium chloride and washed in the way mentioned, a solution of nitric acid was found incapable of liberating any copper or barium ions. Nor could copper or barium be found in the ash of the charcoal. I n these experiments, however, it was necessary t o wash the charcoal with pure water before the addition of any electrolyte solution. If this procedure was not thoroughly carried out, some "adsorption" of the metal ions was observed.

Determination of the eationic exchange capacity of H-charcoal with adsorbed picric acid b y ionic exchange of Cu + + and B a + + for H + . 1.000 g. H-charcoal. (All values multiplied b y 10.)
Picric acid ads. mequiv. 7.41 7.41 7.41 5.27 '5.27 Picric acid ads. mequiv. 6.94 6.94 5.27 5.27 3.47 1 Cu+ + recovered mequiv. 7.40 7.43 7.42 5.24 5.26 Ba++ recovered mequiv. 6.92 6.97 5.30 5.28 3.43 Picric acid ads. mequiv. 5.27 4.21 4.21 4.21 2.64 Picric acid ads. mequiv. 3.47 4.21 2.31 2.31 1.74 Cu+ + recovered mequiv. 5.26 4.21 4.22 4.21 2.60 Ba + + recovered mequiv. 3.47 4.23 2.30 2.33 1.80 Picric acid ads. mequiv. 2.64 2.64 1.58 1.58 1.58 Picric acid ads. mequiv. 1.74 1.74 Cu+ + recovered mequiv. 2.63 2.65 1.63 1.60 1.61 Ba + + recovered mequiv. 1.70 1.60

The effect of the washing can very probably be interpreted as an elution of carbon dioxide, which is always present in a dry char coal. This impurity would form insoluble carbonates with some copper and barium ions in the filter cake, and these would again be dissolved by the nitric acid. The reported experiments were successful only if carried out with very dilute solutions of the metal salts. At higher concentrations of the salt a measurable hydrolytic adsorption of the salt is found when only small amounts of picric acid are adsorbed per unit weight of charcoal. The hydrolytic adsorption results in a precipitation of copper hydroxide, which is retained b y the filter cake. No "adsorption" of copper and barium was found even from more concentrated solutions, if the reaction of the solution was slightly acid. The reported experiments show t h a t the picrate ions are adsorbed primarily while the inorganic cations are secondarily

adsorbed. The experiments further demonstrate t h a t all the adsorbed picrate ions are primarily adsorbed, as the cationic exchange capacity of the H-charcoal-acid complex is identical with the amount of adsorbed picric acid, if the charcoal is pure, and if not too small amounts of picric acid are adsorbed per unit weight of charcoal. I n order to subject the applicability of the Donnan theory t o the adsorption of picrates on H-eharcoal t o a more rigorous test, the exchange constant was determined between hydrogen and silver ions on an H-charcoal with adsorbed picric acid. To simplify this test, the experiments were carried out a t a constant ionic strength. I n this case the ratio between the activity coefficients of the exchangeable ions in the free solution is constant and can be included in the exchange constant. The experiments were carried out on the lines described below. Samples of 1.000 g. of H-charcoal were mixed with 20.00 ml. of a solution of picric acid containing 0.540 mequiv. of picric acid. This amount was chosen because it was very near the maximum amount which the charcoal in question could adsorb without leaving a t equilibrium a traceable concentration of picrate ions in the free solution. To this mixture 50.00 ml. of a solution of nitric acid and silver nitrate were added. The concentration of the nitrate ions in this solution was always 0.0200 N, but the relative concentrations of the hydrogen and the silver ions varied. These mixtures were rocked for four days. At the end of this time t h e mixtures were filtered, and the hydrogen and the silver ions were determined volumetrically in a n aliquot part of the filtrate. I n order t o increase the accuracy of this analysis, the hydrogen and the silver ions were estimated one after the other in the same volume of the filtrate, the latter being taken as large as possible. The filtrates were in all cases free from picrate ions. From the analytical data the amounts of adsorbed silver and hydrogen ions were determined. I t was supposed in this calculation t h a t the hydrogen ions of the adsorbed picric acid were totally exchangeable for silver ions. I t was analytically ascertained t h a t the charcoal with the adsorbed picric acid did not adsorb any nitric acid. The exchange capacity of the charcoal was consequently identical with the adsorbed equivalents of picric acid. From the data thus

obtained the exchange constant between the hydrogen and the silver ions was calculated from the formula: h - ^ [Agtr = Ag+' ' [H + ]"
r Zh+ A8+

m (1

The experimental results, together with the calculated exchange constant, are given in Table 25. The experiments cover from 12.4 t o 84.4 per cent exchange of the hydrogen ion. K n > A g was found to be constant within the experimental error, and the Donnan law is consequently applicable t o the studied exchange. I t is obvious from formula (11) t h a t the accuracy in the calculated exchange constant is lowest when determined from compositions of those systems which represent very low or very high percentages of ionic exchange. During this investigation it was observed t h a t the initial rate of ionic exchange was very high, but t h a t reproducible results could not be obtained within 24 hours. I t was experimentally ascertained, however, t h a t the exchange proceeds to an equilibrium after 3 t o 4 days. As i t was of interest t o investigate the stability of the picric acid in the adsorption layer, the following experiment was carried out. H-charcoal was added t o a solution of picric acid till the solution was completely decolorized. The charcoal with the adsorbed picric acid was filtered off and dried for 14 hours a t 80 C, and over sulphuric acid in vacuum for four days. No decomposition of the picric acid was observed. Picric acid could be desorbed from t h e dried charcoal b y means of carbon tetrachloride and water, but not with water alone. The charcoal with adsorbed picric acid exhibited no adsorptive capacity towards hydrochloric acid. The exchange capacity of the product was determined b y titration of the hydrogen ions liberated on treating the charcoal with 2 N potassium chloride. The exchange capacity was found t o be approximately equal t o the value calculated from the amount of picric acid adsorbed on the charcoal. Exact agreement was not t o be expected, because of the unknown water content in the char coal, which for obvious reasons could not be estimated. This dried charcoal was used for exchange experiments between hydrogen and silver ions, carried out according t o the method

gq

c 7 3 c O o M " c
-+3

w M

1 0 0 M OC N C ( M < lMO < MM < 0 0 0 0 O

0 5 J 0 1 0 0 5 ^ 0 0 1 0 W 0 ~ "~ IQ

M <

M
D + < a c O O o c

o c 4 3 O O S S < q .N I ^ o in O l> 3 + T s b O
_L

N <

00

C O I N O O Nh ( C "i O I Q T f * C D C O O J

OOtD^CO(M00 >-HC<iiooo*o<NCico w 1 H *$ - < i D+ b

I(THCOil CO C C i ^ 00

O i + c 8 e M P Xo n > < 0 s _ c g 4 ^ S o> O [

< ^ 5 ( N

rJJOOQOrHT^^C51> t NlOtOTjiwdlOH > ^

C i t *

M < 1

O^^QOOOO(M>h(M cod^>C(?idflii>ii! M ( < N r H

C O C O O O C O ( N C O C i C < l rH P H rH

* 0
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K " * -1 o S
+

P h S o o

5 D )M O l 0 C O W H<M >O O O .O 0 C t ( i O C M Q 5 C d C H i i O b' o H N C i (

>> A 4 .S 2 " o O X C o - cg ' n + bo D -+3 o i < c Ml< 4 > ^ 4 g) 3 "3 O w +=> c H M O H h o ? w O fl ti) o o o
PH

+ fc < K 1

0 C t- 0 OM 0 O C 0 i i O i C i i C i CCO( COC i ci ci ci H O O ci 0 O ci ci O lOT 10t o h T l 2 > 0 l

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.

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w t + w 4& C < 5 1 fl oc W < O -p o 1 0 Q 0 a O o w O c M D O < SP' > o o l ,-fl Ph o rs *3 S 1 J "! 4 3 * Q c > O w o H

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f-l cm

< a < N ^ Ht o * e n (> r o i oiooodooiooioooo r-lffOI>(MOOO(MOCOOO MH^OHTtfONC'^Oi

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0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 *o*oo IO^T(IP5WN!NHH

-f O 0 M _4 t ^ < O ? >- fl H H < W 1

mentioned earlier (page 105). The data of these experiments are collected in Table 26. Judging from t h e results, the Donnan law is also valid for the cationic exchange on this material. Using another sample of dried H-charcoal with adsorbed picric acid the exchange constant between the hydrogen and the copper ions was determined. I t was in this case practically impossible t o obtain a constant ionic strength of the free solution a t equilibrium throughout a series of experiments. Consequently, the activity coefficients of the exchangeable cations in the free solution in such experiments cannot be included in the exchange constant. I t was found, however, t h a t the experimental uncertainty was so large t h a t the comparatively small changes in ionic strength during a series of experiments were not apparent in the results. The experiments were carried out by the same method as t h a t previously described. The details and results can be seen in Table 27. For the calculation of the exchange constant the following formula was used: jr
H + . Cu

_ _

H +

y-

'

C u + +

- *

K[Cu + +]"
[ H +y

Charcoals with adsorbed sulphonic salts of azo-dyes did not behave as perfect cationic exchangers. When charcoals with ad sorbed sodium salts of some azo-dyes were used it was found possible t o expel the sodium ions by treating the charcoal with ammonium salts, especially if the solution was slightly alkaline. The sodium ions could also be exchanged for hydrogen ions, but the reverse reaction did not proceed quantitatively when dilute neutral solutions of alkali salts were used. Nor did an exchange of alkali metal ions for copper ions proceed quantitatively. The free solution of a system containing H-charcoal with adsorbed alkali metal salts of an organic acid is slightly alkaline. This phenomenon is the hydrolytic adsorption mentioned earlier. I n order t o avoid precipitation of copper hydroxide some added acid must always be present. If the reaction of the solution was only slightly acid, however, it was found t h a t very little copper was adsorbed, even if the concentration of the copper ions was comparatively high. This observation can be understood b y assum ing t h a t inner salts of the dye-stuffs are formed in acid solutions.

Determination of the exchange constant K H Cu on a picric acidcoated H-charcoal. 2.000 g. H-charcoal. Total fluid volume: 50.00 ml. Time of contact: 4 days. Exchange capacity: S = 0.912 mequiv. Ads. equiv. H + = S ads. equiv. Cu + + . H + ads K /[C++], =
H,Cu

Th+T'

Added solutions CuCl2, HCl, 0.02000 N 0.01892 N ml. ml. 50.00 45.00 40.00 35.00 30.00 25.00 20.00 15.00 10.00 5.00

Equil.eoncn. Equil. concn. expressed in in free solution ml. 0.0200 per litre N/50 ml. H
+

Cu

++

[H+] mole, 3 x 10
!

[Cu + + ] mole, 4 x 10

ex chang ed Cu ++ H+ H+ mole, mole, 5 5 x 10 x 10 0.0 9.8 19.3 29.5 38.3 47.1 54.8 61.8 67.5 71.8 76.8 Mean

Adsorbed ions

/o

H , Cu

x 102

5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00

50.08 49.88 49.32 48.43 47.56 46.41 45.06 43.26 41.58 39.30 36.51

* 0.25 0.66 0.75 1.44 2.16 3.39 4.95 7.06 9.82 12.27

19.95 0.50 19.73 1.32 19.37 1.50 2.88 19.02 18.56 4.32 18.02 6.78 17.30 9.90 14.12 16.63 19.64 15.72 14.60 1 24.54 i

82.24 73.60 64.32 56.24 48.22 41.22 34.88 29.64 25.70 21.14

4.48 8.80 13.44 17.48 21.49 24.99 28.16 30.78 32.75 35.03

4.36 4.57 3.50 3.80 3.69 3.77 3.79 3.82 4.01 3.84 3.92

All the azo'-dyes used in these studies contained amino groups. I n no case, however, did an increase in the concentration of the inorganic ion in the free solution diminish the adsorption of the dye-stuff ion. Only in some respects, therefore, is the theory sup ported b y the experiments with these substances. C. H-charcoals with adsorbed organic electrolytes functioning as basoids.

I n this section details of a number of experiments will be sub mitted which show t h a t if inorganic salts of some strong organic

Expulsion of chloride ions from adsorbed methylene blue chloride by sodium nitrate. 3.0 g. H-charcoal. Volume of liquid: 215 ml. Time of contact: 4 days. Methylene blue chloride 8.40 mN. 15.0 ml. NaN0 3 , 2.5 N .
Methylene blue chloride Blind ml. 25.0 50.0 75.0 80.0 100.0 110.0 125.0 130.0 150.0 175.0 180.0 200.0 [Xequiv. 210 420 630 672 840 924 1 050 1 092 1 260 1 470 1 512 1 680 [Xequiv. c r free After addition of NaNO s (Jiequiv. 229 417 654 672 862 950 997 1 062 1 192 1 473 1 497 1 672

120

210

257

314

bases are adsorbed on H-charcoal the organic cation will be prim arily adsorbed. The inorganic anion of the salt is found t o be secondarily adsorbed, and consequently liable t o ionic exchange. Suitable electrolytes for these experiments were found among those organic quaternary ammonium salts which are dye-stuffs. The experiments with methylene blue chloride will be reported in some detail. Samples of 1.000 g. of H-charcoal were treated with various volumes of a solution of methylene blue chloride of known strength. I n all cases the H-charcoal was able t o adsorb all the added methy lene blue ions. The solution was in every instance found t o be slightly acid (hydrochloric acid). The amount of chloride in the free solution was determined and was found t o be equivalent t o 1/61/3 of the added dye-stuff. The methylene blue chloride was free from inorganic chlorides. The charcoal was also free from chloride. The liberation of hydrochloric acid thus follows from

hydrolytic adsorption. The feature of chief interest in the present investigation is t h a t the greater part of the added chloride ions were adsorbed. The cause of the hydrolytic adsorption will be discussed in Chapter 11. To each of the mixtures of charcoal and methylene blue chloride solution, 15 ml. of a 2.5 N solution of sodium nitrate were added and the liquid volume in all cases made

1400T200-

1000-

^ ^

800500400200-

600 800 1000 1200 Qdsorhed methylene blue

1boyUeyUi

Fig. 5. Expulsion of chloride ions from adsorbed methylene blue chloride by means of sodium nitrate. (Data from Table 28.)

u p t o 215 ml. After 4 days' shaking the charcoal was separated from the solution b y filtration. No methylene blue ions could be detected in the filtrate. The chloride was determined in an aliquot part of the filtrate and was found t o be equivalent t o the added methylene blue within the experimental error. The results are found in Table 28 and Figure 5. I t seems t o be proved b y this experiment t h a t the chloride ions are secondarily adsorbed and t h a t the methylene blue ions are primarily adsorbed. Analogous experiments, with the same result, were carried out with several other basic organic dye-stuffs. The results with crystal violet chloride are given in Table 29.

Expulsion of chloride ions from adsorbed crystal violet chloride b y sodium nitrate. 2.0 g H-charcoal. Time of contact: 2 days. 15 ml. N a N 0 3 , 2.5 N added t o each test.
Volume of liquid ml. Crystal violet chloride ad sorbed (Xequiv.1 115 230 345 460 460 460 550 575 690 Free CI" Xequiv. 87.2 236 343 458 471 462 558 573 694

75 100 100 115 150 200 150 150 175

Determined from analysis of chloride.

No determinations of t h e exchange constant between inorganic anions were carried out for t h e following reasons. I t was found t h a t t h e ionic exchange in neutral and alkaline solutions was also influenced materially b y t h e presence of t h e hydroxyl ion. I n acid solutions, on t h e other hand, t h e exchange capacity of t h e charcoal will depend on t h e amount not only of adsorbed organic ions, b u t also of t h e hydrogen ions primarily adsorbed simul taneously. These facts will complicate t h e analysis, since either t h e exchange proceeds between more t h a n two ions (alkaline solutions), or t h e exchange capacity is variable (acid solutions). I n t h e writer's opinion, t h e reported experiments demonstrate t h a t H-charcoal can also adsorb cations primarily. D. Experiments with adsorbed inorganic acids

I n connection with t h e reported experiments i t was of interest t o study t h e behaviour of adsorbed inorganic electrolytes, in order
8 4 4 5 9 3 Brje Sternberg

113

t o determine whether the cations or the anions were primarily adsorbed. On H-charcoal, alkali metal ions are not adsorbed from inorganic salts. This is obvious from the observed non-adsorption of alkali metal ions from inorganic alkali salts seen when H-charcoal is used as adsorbent. Hydrogen ions, however, are adsorbed t o an appreciable extent b y H-charcoal. With the exception of the hydroxyl ions, all tested anions were found t o be adsorbable on

[+ H]

P]

[OH] H,0

' " T " volume of woshinqs OH - ^ NaN0 3

Fig. 6. Composition of washings from H-charcoal w i t h adsorbed hydrochloric acid. Washing agents: H 2 0 and a solution of N a N 0 3 . (Schematically.)

H-charcoal. This was the case whether the anion was added t o the liquid in contact with t h e charcoal in the form of a neutral salt or as an acid. When the anion was added in the form of a neutral inorganic salt hydrolytic adsorption was observed (the p H of the solution was increased). The amount of the inorganic anion adsorbed from the neutral salt is much less than the amount of the same anion adsorbed from the same concentration of its acid. From this survey it can be concluded t h a t anions are always adsorbed together with hydrogen ions (hydronium ions), if no organic cation is present. The type of adsorption of inorganic anions occurring on H-charcoal can consequently most easily be studied b y using H-charcoal and inorganic acids. The following experiment may be reported.

A solution of hydrochloric acid was treated with H-charcoal, and after equilibrium was attained it was filtered through a glass filter b y suction. (The subsequent observations are schemat ically recorded in Figure 6.) Without allowing the filter cake t o break, the charcoal was washed continuously with distilled water in the manner described by Kapsenberg (89). The suction was adjusted in order t o allow approximately the same amount of filtrate t o pass the charcoal for each unit of time. The filtrate was collected in parts of 15 ml. The filtrates were found b y analysis t o contain hydrogen and chloride ions in equivalent amounts. On prolonged washing, the concentration of the acid per volume of filtrate decreased exponentially. A t a certain time t h e water used for the washing was replaced b y a solution of 2 N sodium nitrate. From now on, the filtrate exhibited a slightly alkaline reaction and the amount of chloride per unit volume of filtrate increased rapidly. With continued filtration the alkalinity of t h e filtrate rapidly decreased and the filtrate was soon found t o be neutral. Chloride ions still appeared in the filtrate, but the concen tration of these also decreased rapidly. On analysis of the collected filtrates, when no more chloride could be washed out, the amount of the chloride eluted was found t o be approximately equivalent to the total amount of added hydrochloric acid. Some experimental results are given in Table 30. The observations may be interpreted b y the following line of reasoning. When the washing water is replaced b y the solution of sodium nitrate this salt is t o some extent hydrolytically adsorbed b y the charcoal. The reaction of the filtrate is in consequence changed in the direction of increasing p H . The p H change can also be interpreted as an increase in the adsorption of the hydrogen ion when the ionic strength of the solution is increased. This phenomenon has been mentioned earlier in this paper, and will again be treated in more detail in Chapter 12. As the reaction of the solution before the addition of the nitrate was only slightly acid, t h e increase in p H was large enough t o make the filtrate not only neutral but also alkaline. Simultaneously with this process t h e anions of the adsorbed hydrochloric acid are exchanged for nitrate ions. According t o the experimental results, this ex change can easily be carried out quantitatively. This experiment

Washing of H-charcoal with adsorbed HCl with water and a solution of NaN0 3 .
1.00 g. H-charcoal + 20.0 ml. 0.0200 N HCl + 10 ml. water shaken for 4 hours in a conical flask and poured in one throw into a glass filter funnel, without washing the flask. 25 ml. filtrate collected. Water continuously added t o the charcoal and t h e filtrate collected in portions of 20 ml. Water a s washing agent later replaced b y 2 N N a N 0 3 (indicated in table b y solid horizontal line). H + and Cl~ determined titrimetrically in t h e filtrates. Negative sign for amount of H + indicates alkaline solution. Velocity of filtration: circ. 1 ml. per min. I Volume of filtrate H+ , 25 20 20 20 20 20 20 20 20 4.82 1.46 0.87 0.12 0.03 0.00 0.00 i I II III

Titration values in ml. 0.0200 N solution c r 4.83 1.41 0.87 5.50 1.12 0.36 0.21 0.17 1
H +

c r 5.07 1.82 1.12 0.82 4.62 1.08 0.43 0.30 0.21 1

H+

c r 4.68 1.80 1.06 0.74 0.52 4.78 0.96 0.46 0.23

5.11 1.78 1.12 0.80 0.16 0.08

4.72 1.86 0.97 0.74 0.50 0.24 0.10

0.00

has demonstrated the possibility of exchanging the adsorbed anions. From the reported experiment i t seems plausible t h a t the hydrogen ions are the primarily adsorbed ions, when inorganic acids are adsorbed on H-charcoal. This is slightly perplexing, since in the experiments reported earlier, with picric acid, the hydro gen ion was found t o be adsorbed in the diffuse part of the electrical double layer facing the water phase. The anionic exchange on H-charcoal coated with hydrogen ions was also studied in some static experiments, in order t o find out whether any noticeable variations in the exchangeabilities of different anions could be observed. These semi-quantitative ex periments were carried out using samples of one gram of H-charcoal t o which had been added 20 ml. of 0.02 N hydrochloric acid and i n addition 10 ml. of one of a number of solutions of various salts

Expulsion of adsorbed chloride ions b y means of potassium nitrate. 1.000 g. H-charcoal. Volume of liquid: 30.00 ml. 20.00 ml. HCl, 0.02000 N . 10.00 ml. K N 0 3 , varying concentrations. Time of contact: 2 days.
N071 c r c r H+ free free ml. 0.02000 N ml. 0.02000 N 6.44 6.59 6.16 6.16 5.52 5.92 4.65 4.70 3.29

H+ ads. mequiv. 0.271 0.268 0.277 0.277 0.290 0.282 0.307 0.306 0.334

Cl~ ads. mequiv. 0.273 0.267 0.237 0.237 0.207 0.202 0.122 0.120 0.045 0.045 0.018 0.021 0.000 0.006 0.004 0.004 0.000

c r expelled 1 mequiv.

0.000 0.000 0.100 0.100 0.200 0.200 0.500 0.500 1.00 1.00 2.00 2.00 3.00 3.00 4.00 4.00 oo 2
1 2

2.42 2.58 2.27

2.00 1.92 0.69

6.36 6.66 8.16 8.16 9.64 9.92 13.90 14.00 17.75 17.75 19.12 18.95 20.10 19.70 19.80 19.80 20.03

0.001 0.040 0.040 0.083 0.080 0.185 0.186 0.289

0.352 0.348 0.355

0.334 0.327 0.355

0.360 0.362 0.386

0.356 0.358 0.386

Relation between nitrate and chloride ions in the system. 10 ml. 3 N KNO3.

in different concentrations. After four days' shaking the mixtures were filtered and the hydrogen and chloride ion concentrations in the filtrates determined. I n each experiment i t was found t h a t the concentration of the hydrogen ion in the solution was lower if a salt was present, as compared with the cases in which the acid was the only solute. The decrease in the equilibrium concentration of the hydrogen ion was found t o change with the concentration of the salt, and also t o be dependent on the composition of the added salt. This effect will be treated in Chapter 12. On the other hand, the equilibrium concentration of the chloride ion in the solution increased with an increasing concentration of the salt.

Expulsion of adsorbed chloride ions b y means of potassium iodide. 1.000 g. H-charcoal. Volume of liquid: 30.00 ml. 20.00 ml. HCl, 0.0200 N . 10.00 ml. K I , varying concentrations. Time of contact: 2 days.
I~l c r c r H+ r free free free ml. 0.0200 N ml. 0.0200 N ml. 0.0200 N 6.72 6.25 6.32 5.44 4.23 4.17 3.65 2.70 1.85 0.03 0.15 2 6.74 8.31 8.28 9.27 12.36 12.30 16.00 18.54 19.72

H+ ads. mequiv. 0.266 0.275 0.274 0.291 0.315 0.317 0.327 0.346 0.363 0.399 0.403

c r ads. mequiv. 0.265 0.234 0.234 0.215 0.153 0.154 0.080 0.029 0.006

c r expelled mequiv.

0.000
0.100 0.100 0.200 0.400 1 0.400 0.600 0.800 1.00 2.00 4.00 !
1 2

0
0 0 0 0 0 trace 0.03

0.041 0.040 0.076 0.162 0.163 0.247 0.317 0.357

.

Relation between iodide and chloride ions in the system. The filtrate was alkaline.

I t was found possible t o inhibit any adsorption of chloride ions from hydrochloric acid b y a sufficient addition of any neutral inorganic salt. The experimental results were identical irrespective of the order in which the solutions were added t o the charcoal, if sufficient time was allowed t o elapse before analyzing. This indicates t h a t the ionic exchange proceeds towards a true equi librium. The results of a few experiments are shown in Tables 31 34 and Figure 7. I t is observed from these results t h a t the secondary adsorbabilities of inorganic ions are very different. I t was further of interest t o investigate whether the Donnan theory could be applied quantitatively t o the ionic exchange between anions. The experimental test was originally planned t o include a large part of the common anions. This plan could not be carried out, however, because of analytical difficulties. I t was found in preliminary experiments t h a t the exchange constants between the inorganic anions differed widely, and t h a t they

could reach values f a r from unity. Consequently, in order t o obtain any great degree of adsorption of a given slightly adsorbable anion, i t was necessary to use a very high relative concentration of this ion. The analytical determination of the initial and equi librium concentrations could not in this case be carried out with sufficient accuracy t o estimate the small difference caused b y t h e adsorption. On the other hand, the more strongly adsorbable anions had in this case too low a concentration in the free solution
XKNO3

O NCO oJ i f
0,2+ KI

0,5

me^uiu

Fig. 7. Expulsion of chloride ions from adsorbed hydrochloric acid by means of salt solutions. (Data from Tables 3134.)

t o allow them t o be determined with sufficient accuracy. Experi ments in which the adsorbed amounts of the anions were determined b y analysis of the separated charcoal were not successful owing t o the difficulty of separating the charcoal quantitatively from the free solution without disturbing t h e equilibrium. I n con sequence of the mentioned analytical difficulties the experiments later t o be reported were restricted t o a few anions. For the anion pairs which were studied the experiments cover only a small part of the exchange between these ions. Furthermore the in vestigation was confined t o univalent anions, because of the difficulty in obtaining any definite knowledge of the ionization of the polybasic acids in the adsorption space. H-charcoal and a mixture of two inorganic acids or an acid and a salt were used in these experiments. The original concentra
i s

Expulsion of adsorbed chloride ions b y means of sodium fluoride. 1 1.000 g. H-charcoal. Volume of liquid: 30.00 ml. 20.00 ml. HCl, 0.0200 N. 10.00 ml. NaF, varying concentrations. Time of contact: 24 hours. 2
F - 3 c r c r H+ free free ml. 0.0200 N ml. 0.0200 N 7.84 7.94 7.93 7.60 7.26 7.34 7.02 7.84 8.01 9.04 11.69 13.27 14.37 15.79 H+ ads. mequiv. 0.243 0.241 0;241 0.248 0.255 0.253 0.260 c r ads. mequiv. j 0.000 0.100 0.250 1.00 2.00 3.00 5.00
1 2

c r expelled mequiv.

0.243 0.240 0.219 0.166 0.135 0.113 0.084

0.001 0.022 0.082 0.120 0.140 0.176

Brand-new bottles used for the experiments. The solution of sodium fluoride added 2 hours after the addition of hy drochloric acid. 3 Relation betwen fluoride and chloride ions in the system.

tion of the electrolyte solution was made identical throughout a single series of experiments. I n every case the exchange capacity of the charcoal was determined b y acidimetric titration of the filtrate when the adsorption process had terminated. The exchange capacity was taken as equal t o the equivalents of adsorbed hydrogen ion per gram of charcoal. I t has been mentioned earlier t h a t the equilibrium concentration of the hydrogen ion in the free solution is a function of the initial concentrations of both the hydrogen ion and the anions in the solution. Although the same initial ionic strength was used in every series of experiments, the ex change capacities in the different tests were not found t o be ident ical, since i t was observed t h a t the special nature of the added salt (e.g. its anion) also influenced the primary adsorption of the hydrogen ion. This involves t h a t the equilibrium ionic strengths of the solutions in a series are not identical. The small variations in the equilibrium concentrations, however, exhibited no detectable influence on the activity coefficients of the anions. Consequently, the test of the applicability of the Donnan law t o the anionic

Expulsion of adsorbed chloride ions b y means of sodium Perchlorate. 1.000 g. H-charcoal. Volume of liquid: 30.00 ml. 20.00 ml. HCl, 0.02000 N . 10.00 ml. NaC104, varying concentrations. Time of contact: 2 days.
CIO 4 c r
1

c r H+ free free ml. 0.02000 N ml. 0.02000 N 6.84 6.73 6.51 5.74 4.69 3.89 3.07 2.40 2.46 1.31 0.28 6.80 6.83 8.49 9.74 12.98 15.92 17.81 19.50 19.62 20.02 19.90

H+ ads. mequiv. 0.263 0.265 0.270 0.285 0.306 0.322 0.339 0.352 0.351 0.374 0.394

c r ads. mequiv. 0.264 0.263 0.230 0.205 0.140 0.082 0.044 0.010 0.008 0.000 0.002

c r expelled mequiv.

0.000 0.000 0.100 0.200 0.400 0.600 0.800 1.000 1.000 2.000 4.000
1

0.040 0.080 0.166 0.240 0.295 0.342 0.343 0.374 0.392

Relation between Perchlorate and chloride ions in the system.

exchange can be carried out without too large an error b y use of the approximation in formula (9). The results of experiments with the anion pairs Cl~N03~~, Br - N0 3 ~", Cl~C104~, and Br~~C104~ are given in Tables 3539. Judging from the results and the calculations given in these tables the Donnan law seems t o be fulfilled in the in vestigated cases of anionic exchange. I n the experiments in which nitrate ions were involved the nitrate was estimated colorimetrically, but for the calculation of the exchange constant the calculated concentrations of the nitrate ion were used. The differ ences between the calculated and the observed concentrations of nitrate ion were small and irregular as t o sign. I n the experi ments using the Perchlorate ion the concentrations of this ion were calculated from the experimentally observed adsorption of the hydrogen ion and the chloride or the bromide ion.

o
o

OOhNOOOHXl s o o o o o o o o o 0 0 0 0 0 0 0 0

CiOi 1 OfMOOO^CO S 0

O O O O0( M H ^ D ffl 1 1 0 0 0 H t( O<-Hi-Hi-HpHqc4 ^TjJ<MrHQOOOCOCOI>l> 050ilOiOQo6oQl>l> fHr 1C I < C C - i ( ( ( <C 1 0 0

OOCOCOI>XOIOFFOVOO >OOOr|(5NNOOWH

" S ' o s p 'u rG a t H W

GOQ6I>OQOO5Q6O6I>O M ( M M N M N M M N ( N ( ! ( (

H 1 i( -

O N 0 H O M FLI 0 ( rI - rI < ii i j M H O H C < i

ffO N O * < 0

O O l

O w
< N

10"<M<NOOW50 0

fc ^O O MoS

1 0

0 0

0 o 0

<1

s 0 s 5O 6o w
o

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0

O M

o >It- > t-O o t O C OS o F i C Gi i rit- O 1 <

II I-H ( N

O Oi Q O t* O S I C 1 N NOn O ^ O 0 0 M O (C > O
O T * t

O ( o t - Oq 0 S N il c

ro M QO P M^
? O & D S. g c 8 H o + ^

o *

T T 0 ^ ^ lO * * o
'

o 0

c q

O ^ W M C (

3 + i ^ , O ! O o o

? c

1 s 1

rf H > I- > t- o > l > 1 t w

ii

a H b ? O (5 O O

c o 8 S e H 3 .2 rd * -O 4 3 c d w

rf

* O iO io 0

OS fc o wg w2
U o o o o o o o o o o o o o

* 3 i

io H r

x o Md c o M M C m > C <

II

The exchange constants between the iodide ion on the one hand, and the nitrate or the chloride ion on the other, were too small t o be accurately estimated. The same was the case with the thiocyanate ion on the one h aad and the chloride or the nitrate ion on the other. This observation implied t h a t it should be possible t o extract small amounts of iodides or thiocyanates from comparatively concentrated solutions of chlorides or nitrates b y means of H-charcoal in acid solutions. This was found t o be the case. As may be seen from the following experiment iodide ions could be quantitatively extracted and concentrated from solutions containing a thousand times larger amounts of chloride ions t h a n iodide ions. A solution of 200 g. of sodium chloride, 0.0096 g. of potassium iodide, and 100 ml. of 2 N hydrochloric acid in 20 litres of water was run through a filter containing 1 g. of H-charcoal with some adsorbed hydrochloric acid. The charcoal was washed with water and a concentrated solution of sodium nitrate passed through the filter. I n the filtrate, amounting t o 53 ml., the iodide was estimated. This was equivalent t o 93 per cent of the added potas sium iodide. I t was found possible t o carry out similar experi ments with thiocyanates, which could be readily concentrated from dilute solutions containing very large amounts of nitrate or chlor ides. I t was farther observed b y means of tests t h a t the thiocyanate was adsorbed preferentially t o the iodide ion from a solution containing equivalent amounts of iodide and thiocyanate ions. The exchange constant calculated in the reported experiments from formula (6) may formally be interpreted as (13) / ' and / " being the single ion activity coefficients of the ions in the free solution and in the adsorption space. For the compara tively dilute solutions which were used we may write approximately, for the sake of the present discussion:

O M
O Q , 0 0 < D S-. +H

O M 0D O H >t*^ t* H 0 t C Q C t)I 0 | rl I r C
o o o o o o o o o

Q P

O c o c d

TH c d

Oi
c d

q i > ii

00 0 0 rH o i

(M

g I o S d S P Q O C ^ OM < O 2 < * 3 C X o o
c h c

o IO X

<*J

g 9

<N o CO r(

Oi a
i d

o o c d

T1
o o CO <M

T* q t >

CO IO l > 1 1

CO q

0 0 <N 0 0 PH

00 IO 00

l >

GC

0 0

+ <H

>
i <> X a O 4-> ' S O o a *

0 D T* 03

Oi
0 0 CO <N

CO

O (M

Oi
<N

r c<i <M q c q <M

<N l > fH <M

<M T* <M

CO

(N

. > > C
<*

Q Q 1

t > 0 0 r h

CO <M 0

T* c d

Oi
00 c d I >

CO 0 0

t 0 0 o

CO CO o i

Oi
l > o i

II II O
(X)

free

m CO c o iO rH l > o i i1 CO 0 0 CO q 0 0 <N

OiOi
<N <* M CO q c d CO

CO l-H rH

t > q i d rH

IO

i o * T? c + w O CO 00* t o i <M rH c o o i <N TH q o i <N 0 0 CO 0 0 CO CO

Oi
* o O CO

o i > * CO

(M

-{ i C
o

S H

Oi
CO

M
O 5 O O
1 o "-5
#

IO CO

CO l >

CO CO 1 1

CO O

0 0 o i

t-,

q o i

rJH o i

IO o i

00 q o i

( I

o o <M

O IO t~rH

o o i d ii

O IO c 4

o o

IO i >

q i d

IO c<i

i 1

KBr

0400

O o

O o c<i ii

' o C G T J J 2 S <

o q o

o IO l >

o o 6 <N

IO <N

*d

i q i >

CO

o M

g o o o Tt< o q TH o o o o o O O Tt< T* " rH Tfi

OOOOO 6 0 0 0 0 M N MN C (J ( C X H ( i T C O | O T 0 0 0 0 0

H H H O H

o
o

M ^
-+3

5 o

r 9
rH r-H 1I < M < M

00 1 00 00 h I-H1 0 (M 0

WWM

O C

O C

3 O C a r^S ^ e O o ^ O o ? S c eS 13 " o X o ^ J 4 ^
>i t CD . .

5
0 M Q N ^ 0 I I O C O C O C L < I C

0 rtiO^ 01 N > e C *0 ct o
( ^ C OO 0O 0T N D CC 0 0 c c cC c C c C O O O O O C C
o

b s & H W

S H 'S

a
c o

O ^ H O O C 0 W ( H 0 5 N cd D cd cd . cd C

? & t 0 D ) O (5 O O
+->

o H
ca

0 0 0 0 o o o o o > > N t 0 <

O O O O10Oo O O * d M NN N > 6 ( <N * i

o

2o Q o W

OOOOO OOOOO H o f T J r

and the exchange constant may approximately be taken as the ratio between the single ion activity coefficients of the exchangeable ions in the adsorption space. The values of the exchange constant calculated from the experiments are far above the ratio of the acti vity coefficients of these ions in moderately concentrated solutions. This indicates t h a t the solution in the space of adsorption is very far from being ideal. However, the large concentration in the ad sorption space alone does not seem t o furnish an adequate ex planation of the results. I t is a probability t h a t the differences in the exchange constants between different pairs of ions are due t o van der* Waals' forces acting t o different degrees on different ions in the vicinity of the charcoal. If this assumptioji is correct the adsorption of the inorganic anions is not exclusively determined b y electrostatic attraction between this ion and the primarily adsorbed ion. I t must be concluded, however, t h a t the van der Waals' forces mentioned are much smaller than the electrostatic forces between the anion and the primarily adsorbed ion, as they are not strong enough t o be manifested as a measurable primary adsorption of the inorganic anions. This experimental fact is, however, also interpretable b y the assumption t h a t these forces act also between the anion and the primarily adsorbed ion, and not only between the anion and the charcoal. I t was observed b y the writer t h a t the exchangeabilities of the norganic anions show the following order: C m ~ I " C10 4 - NO - B r " C T F - , 3 where the first-mentioned ion is preferentially adsorbed t o the last. This series is identical with the lyotropic series of anions first observed b y Hofmeister. The origin of the lyotropic series is still a subject of discussion, but it is commonly believed t h a t the varying effects of the ions are a consequence of the differences in their polarisability. The polarisability is a factor partly determining the strength of van der Waals' forces. I t is also connected with the hydration of the ions. I t is a consequence of Gouy's theory of the double layer t h a t the secondarily adsorbed ions are hydrated. Differences in t h e size and hydration of the ions must have a strong in fluence on their exchangeability.

N 0 S 1~ u

O H< M( ^ M T ( f t N M M < N < < O O O O O O O o

N <

N <

T 0 O H J t T j
H 0 5

(M

0 0

ai d

ci a

o O C

OO S

o S

N <

M <

N <

O C

O C

O C

O C

o* o

W
O C O

< 0

w j g
o
02

o O ol oo o O O O o o l \ ci > < d < i d n o

* + 3

T * <

Ho &O Q P WS o

o o

o o o o o o o .o o o * o o

2 Q o

o o

o o

o o

o o

o o

o o

o o

w o

The exchange constant can be used as a relative measure of the lyotropic effects of the anions. This seems a t the present time t o b e the only method known which will allow a quantitative comparison of lyotropic effects, except for the purely empirical "lyotropic numbers" of Bchner (38). I n order t o be strictly comparable, the exchange constants between the anion pairs must be determined using the same exchange capacity of the charcoal. I n practice this is rather an intricate procedure. The exchange constant for univalent ions, being the relation between the single ion activity coefficients of the exchangeable ions in the adsorption space, can, in fact, be assumed t o change with the concentration in the adsorption space. Many types of cationic exchangers are known and have been submitted t o intensive study both from the theoretical and the practical points of view. On the other hand, only a few materials are known which exhibit a pronounced anionic exchange capacity. The materials which have aroused the greatest interest for technical purposes consist of polymerized aromatic amines. These substances are technically used as "neutralizers" of slightly acid solutions. The ionic exchange is theoretically considered t o be a neutralization process, or an adsorption of the acid ( 1 4 7 ) . The adsorption of acids b y anionic commercial exchangers is sometimes expressed b y means of the Freundlich adsorption isotherm ( 1 4 8 ) . The Donnan equilibrium has not, to the writer's knowledge, been applied quantitatively t o the commercial anionic exchangers. As far as is known, the experiments reported are the first t o confirm the general validity of the Donnan theory for a typical anionic exchange material also. E. Summary of chapter and conclusion.

The results of the experiments reported were found t o be in good agreement with the conception introduced b y the writer regarding primary and secondary adsorption of ions onH-charcoal. I t has been ascertained b y experiment t h a t secondarily adsorbable ions in a system distribute themselves between the 944593
Brje Steeriberg

129

adsorption space and the free solution in the way predicted b y the author's application of the Donnan theory t o electrolyte adsorption on H-charcoal. I n the course of the experimental investigation large organic ions were seen t o be primarily adsorbed b y H-charcoal irrespective of their electrical sign. Among the inorganic ions, the hydrogen (hydronium) ion was found t o have special properties, as it was capable of being both primarily and secondarily adsorbed. The attraction between the charcoal and the hydrogen ion seems t o be less than t h a t between charcoal and the organic ions tested, but considerably larger than the attraction of metal cations or the common inorganic anions t o the surface of the charcoal. Metal cations and inorganic anions are secondarily adsorbable only. One of the main difficulties in the earlier theories regarding electrolyte adsorption on H-charcoal is the interpretation of the different behaviour of the alkali metal ions, which were adsorbed on H-charcoal only when an. organic anion was present in the system. This observation is easily understandable from the results of the author's experimental investigation, without it being necess ary t o assume the existence of different properties of the alkali metal ions in different electrolytes, as has earlier been suggested. Alkali metal ions are only capable of secondary adsorption. These ions can consequently only be adsorbed if they are present in a system containing primarily adsorbable anions. Since organic anions, a t least the larger ones, are primarily adsorbable, while the inorganic anions are not primarily adsorbable, measurable adsorption of alkali metal ions can be brought about only from solutions of organic alkali salts, but not from solutions of inorganic alkali salts. The fact demonstrated by experiment, t h a t alkali metal hydroxides are not adsorbed on H-charcoal, is also under standable from the same line of reasoning. Neither the alkali metal ion nor the hydroxyl ion is, in fact, capable of primary adsorption.

H-charcoals with primarily adsorbed ions must be considered t o constitute a new class of ionic exchangers. The commercially used and synthetically produced ionic ex changers may be regarded as being built u p of an electrically charged molecule and a macrodisperse medium ("carrier") com bined by a c ovalent bond. I n the exchanger material obtained b y primary adsorption of ions on H-charcoal the forces between the "carrier" and the charged molecule are of definitely weaker nature than in the other cases.

XI. A Theory on the Hydrolytic Adsorption of Salts on H-charcoal.

I t has been shown in the preceding chapter that the secondary adsorption of ions on H-charcoal can be regarded as being governed by the same laws as those determining the Donnan equilibrium. This fact has provided a means for a thermodynamic treatment of the hydrolytic adsorption of salts on H-charcoal. I n the cases mentioned in Chapter 9, in which the Donnan law was used t o compute the distribution of ions in a system composed of H-charcoal and a solution of electrolytes, the concentrations of the secondarily adsorbable ions were large in the adsorption space as well as in the free solution. The ionization of the water could consequently be neglected. If, however, the concentration of ions in one part of the system a t equilibrium is very small, the part played b y the hydrogen and hydroxyl ions from the water in the process is measurable. The influence of water on membrane equilibria was also studied b y Donnan and Harris (54), who found t h a t i t took an active part in the process. These authors placed a solution of Congo red sodium on one side of a semipermeable membrane in contact with water on the other side. They found t h a t a t equilibrium the p H of the water phase was raised, and t h a t this solution contained some sodium hydroxide. Donnan and Harris were able t o inter pret these observations according t o the general theory of mem brane equilibria. The membrane used was permeable t o sodium ions. The electrical neutrality of the two parts of the system could only be maintained if diffusion of sodium ions from the phase containing the Congo red sodium was accompanied b y an equivalent diffusion of hydrogen ions from the pure water phase in the opposite direction. A mathematical expression for the distribution of these ions a t equilibrium could be obtained. Because

of the similarity of the phenomenon t o ordinary hydrolysis of salts of weak electrolytes, it was named b y Donnan and Harris "membrane hydrolysis" (later, "Donnan hydrolysis"). Salt adsorption on charcoal is commonly accompanied by a change in p H of the free solution. I n the following pages i t will be shown t h a t it is possible to interpret this p H change, generally called hydrolytic adsorption, as a special case of Donnan hydro lysis. A review of the various "hydrolytic" effects occurring when salts are adsorbed on H-charcoal has been given in Chapter 3. Some typical cases of hydrolytic adsorption of salts have been studied b y the writer, using H-charcoal produced b y himself. The results of these studies have been described in Chapter 6. I n the following text, the p H changes observed when solutions of organic-inorganic salts in water are treated with H-charcoal are first considered. Thereafter, hydrolytic adsorption from solu tions of inorganic salts is discussed. For the sake of brevity, the ions in the free solution will be referred t o as free ions. Let us consider a case in which a definite amount of H-charcoal with a small amount {a moles) of a strongly adsorbed organicinorganic salt is p u t into contact with pure water. The probability t h a t a primarily adsorbed ion will leave the charcoal surface is assumed t o be practically nil. The secondarily adsorbed inorganic ions are, however, able t o enter the free solution b y means of ionic exchange. As the free solution originally contains only water, the only ionic exchange which can occur must involve hydrogen or hydroxyl ions. This ionic exchange will decrease or increase the p H of the free solution, depending upon the sign of the electrical charge or the secondarily adsorbed ion. If the secondarily ad sorbed ions are anions they will be partly exchanged for hydroxyl ions, and the p H of the free solution will decrease; if the secondarily adsorbed ions are cations, the p H of the free solution will increase. The equilibrium state which is eventually obtained must be the same as t h a t obtained if the same amount of H-charcoal be treated with a solution containing a moles of the organic-inorganic electro lyte in question. The p H changes observed in experiments when solutions of organic-inorganic salts are treated with charcoal under such

circumstances t h a t the equilibrium concentration of the free organic ion is very small, are in qualitative agreement with the theory now proposed. They can be understood as a result of ionic ex change between secondarily adsorbable ions. The treatment used in presenting the above theory is analogous t o t h a t used b y Donnan and Harris t o interpret membrane hydrolysis. I n order t o find a mathematical relation for the concentration of the free acid or alkali arising from hydrolytic adsorption, we may consider the following case. A solution containing the salt NaY, where Y~~ denotes a large organic anion, is brought into contact with H-charcoal. Equi librium is obtained when the free Y~~ ion concentration is very small. We presume t h a t only Y ~ ions are primarily adsorbed. A t equilibrium we find the following distribution of secondarily adsorbable ions, b y applying the Donnan theory: <%a+ ^H+ 0Na+ ^H+ (15)

For the acid H Y and the solvent H 2 0 the following equations must be simultaneously satisfied: H+ * Cy7 = K CY H + * H = K v H o
/lX (16)

(17)

Finally, electrical neutrality must be maintained in the system, and thus: Cos- V" = CNa^ V" = Cky V (18) From these equations we find, if the Donnan hydrolysis has not gone too far (e%+ < %a+): (COH~)3 = (CNa+)3 = ~T * fCa V Y~ ' +n /Na * /OH~ (19)

Analogously it can be deduced for the case in which a salt XC1 (containing the large organic cation X + ) , is adsorbed on IEcharcoal under such circumstances t h a t the concentration of free organic ions a t equilibrium is negligible:

Let us now consider systems composed of a definite amount of H-charcoal and a definite volume of water but varying amounts of an organic-inorganic salt. I t is obvious from formulae (19) and (20) t h a t the concentration of free hydrogen ions or hydroxyl ions increases with increasing amounts of primarily adsorbed ions. This rise in the concentration of free hydrogen ions or hydrox yl ions cannot proceed indefinitely. When the amount of primarily adsorbed ions increases, the equilibrium concentration of these ions must increase also in the free solution. Finally, the con centration of these free ions cannot be neglected as was done in deducing formulae (19) and (20). I t is obvious from the Donnan law that, when the concentration of the free organic-inorganic salt increases, the amount of free hydrogen ions or hydroxyl ions must continuously decrease. The free solution must finally be neutral if this theory is correct. The theory of hydrolytic adsorption of organic-inorganic salts now given is in qualitative agreement with the experimental result. When salts with organic cations are adsorbed on H-charcoal the acidity of the free solution increases initially, passes a maximum, and again decreases when the equilibrium concentration of free salt increases. The alkalinity observed in the free solution after adsorption of salts with organic anions is observed t o decrease with an increasing equilibrium concentration of the free salt. If we want to test any of the above formulae for the case when the equilibrium concentration of the organic ions is very small, we must obtain a value for the volume of the adsorption space. The division of the liquid part of the system into an adsorption space and a free volume, as has been made in this paper, is purely formal. The estimation of the adsorption volume can thus be made only formally. I t may, for instance, be assumed t h a t the adsorption volume is proportional t o the amount of charcoal and the amount of ad sorbed substance, but independent of the volume of the free solu tion, and also of the concentration of ions in this part of the system. The adsorption volume is then: r = Q mY(21)

where Q depends on the amount of charcoal and mY- is the number of adsorbed ions. This approximation (case A) is probably not very good, because the adsorption space must be dependent on the thickness of the ion-atmosphere around the primarily adsorbed ion. The thickness (r) of an ion-atmosphere has been calculated b y Debye and Hiickel in their theory on strong electro lytes, and is a t a definite temperature: r = -y1I" = (22)> y

whereI " is the ionic strength in the free solution and R a constant ( 1 4 5 ) . For our purpose we might write: ' = y 4 =

y COH-

(23)

when NaY is adsorbed, because the ionic strength in the free solu tion is equal t o the concentration of the hydrolysis products which are uni-univalent electrolytes. We must now consider t h a t the primarily adsorbed ion a t the surface of the H-charcoal can, geometrically speaking, be arranged in several ways. I n one extreme case, the primarily adsorbed ions are clustered together monomoleeularly on the surface of the charcoal (case B); in the other extreme case the ions are distributed on the charcoal surface far away from each other (case C). I n the case B the adsorption volume is equal t o the product of the area (a) covered b y the primar ily adsorbed ions and the thickness (r) of the ion-atmosphere. I n the second case the volume of t h e adsorption space is con stituted b y (m) hemispheres, each of the radius (r), where (m) denotes the number of primarily adsorbed ions. Between these extreme cases many other arrangements may be imagined. I n case B the volume of the adsorption space is: V = a p4= v COHI n case C this volume is: 2 R3 <24)

Introducing these values of V' into formula (19) we obtain, if we p u t the activity coefficients equal t o one and notice that: CY-= ^ (case A) (case B) (case C) (cH-)3 = (coH-)5/* = (cou-fl> = f f " f ~y (26) (27) (28) (29)

Similar formulae can be deduced from formula (20). Any of these formulae can be experimentally tested, if t h e volume of the free solution is identified with the total liquid volume of the system, an approximation which must be very good. If a system composed of H-charcoal and a solution of an organicinorganic salt is studied, under such conditions that all the organic ions are adsorbed, all these formulae demand t h a t the logarithm of the concentration of the free inorganic ions shall vary rectilinearly with the logarithm of the volume of the liquid. The slope of this line is, however, different in cases AC, and varies between 0.33 and 0.67. The theory has been tested employing methylene blue chloride, crystal violet chloride and sodium picrate. The general procedure was the same in all these experiments. Into a series of flasks definite amounts of H-charcoal were in troduced together with definite volumes of the solution of the salts in question. Water was then added in different amounts t o each flask.. After an interval of four days a t a constant temperature, with intermittent shaking, the mixtures were filtered and the free acid or alkali determined. I n each case the filtrate was com pletely decolorized, and the concentration of the organic ions in the filtrate was consequently very small. I n the series in which the hydrolytic adsorption of methylene blue chloride and crystal violet chloride was studied, the filtrates were found t o be acid. They were neutralized and an appropriate

Hydrolytic adsorption of methylene blue chloride as a function of the volume of the liquid. 1.000 g. H-charcoal + 100 ml. 0.3 % methylene blue chloride.
A g NO s , 0.0200 N , Total volume cr consumed in titrat in filtrate Vy ing the filtrate jiequiv. ml. 1 . 0.100 0.200 0.400 0.500 0.800 1.000 1.500 2.000 3.000 4.000 5.000 5.95 6.80 8.89 9.18 11.09 14.3 12.6 13.7 14.6 16.0 17.8 119.0 136.0 177.8 183.6 221.8 286 252 274 292 320 356 [CT] \i N 1 190 680 445 367 277 286 168 137 97 80 71 3.076 2.832 2.648 2.565 2.443 2.456 2.225 2.137 1.987 1.903 1.851 1.000 0.699 0.398 0.301 0.097 0.000 0.176 0.301 0.477 0.602 0.699

log [CP]

log Vy

0,6-

Q4020.0-

-0,2-

-0.6 -

-1,0 -

Fig. 8. Hydrolytic adsorption of methylene blue chloride. (Data from Table 40.)

volume of the filtrate evaporated down t o 1015 ml. Thereafter, t h e chloride ions in the solution were determined. These determina tions gave more reliable results than determinations of the p H in the original filtrate. The results of these experiments are given in Tables 4041 and are graphically represented in Figures 89. tof Q

Fig. 9. Hydrolytic adsorption of crystal violet chloride. O 75 ml., x 50 ml., + 25 ml., dye-stuff solution. (Data from Table 41.)

I n the experiments with sodium picrate the concentration of sodium hydroxide in the filtrates was determined b y means of alkalimetric titration. The presence of carbon dioxide made the results somewhat inaccurate. The variations of the volume of water were not extended beyond a single power of ten in these experiments, because of analytical difficulties. The concentration of the sodium hydroxide in the filtrate was in all cases very small. The results from these experiments are assembled in Table 42 and Figure 10. The experiments show the expected rectilinear relation between the logarithm of the concentration of the free inorganic ions and

Hydrolytic adsorption of crystal violet chloride as a function of the volume of the liquid. 1.000 g. H-charcoal. 2.00 g. crystal violet chloride/1. Time of contact: 4 days.
Volume of Total fluid crystal violet chloride solu volume V tion added ml. J . 75.0 0.075 0.225 0.375 0.575 0.875 1.075 1.575 2.075 5.000 0.050 0.100 0.150 0.200 0.400 0.500 0.800 0.025 0.050 0.100 0.200 0.300 0.400 0.500 Titration value in ml. A g N 0 3 0.0200 N CI
free

[Cl~] free N 984 i 388 j 250 j 211 140 108 91.3 78.6 50.0 1 212 568 432 337 192
155

log [CP] fre

log V

jiequiv. 73.8 87.2 93.8 121.2 122.6 115.6 143.8 163.0 250.0 60.6 56.8 64.8 67.4 76.8 77.6 91.0 40.0 48.8 50.6 62.2 61.8 63.6 65.4

50.0

25.0

i ! ;

3.69 4.36 4.69 6.06 6.13 5.78 7.19 8.15 12.50 3.03 2.84 3.24 3.37 3.84 3.88 4.55 2.00 2.44 2.53 3.11 3.09 3.18 3.27

114 1 600 976 506 311 206 159 131

2.993 2.589 2.398 2.324 2.146 2.033 1.960 1.895 1.699 3.083 2.754 2.635 2.528 2.284 2.190 2.057 3.204 2.989 2.704 2.493 2.314 2.201 2.117

1.125 0.648 10.426 10.241 0.058 + 0.031 + 0.197 + 0.317 + 0.699 1.301 1.000 0.824 0.699 0.398 ! 0.301 j 0.097 1.602 1.301 1.000 0.699 J 0.523 0.398 j 0.301

the logarithm of the volume of the liquid. The slope of the curve is 0.62 in the experiments with methylene blue chloride, 0.72 0.79 in those with crystal violet chloride, and 0.72 for sodium picrate. These values are all in the vicinity of 0.67, the value required b y formula (29) (Case C), although an exact agree ment is not found. Case C is the most likely one, because in none of the reported experiments is the charcoal saturated with

Hydrolytic adsorption of sodium picrate a s a function of the volume of the liquid. 2.000 g. H-charcoal. 1.706 mequiv. sodium picrate. Time of contact: 4 days.
Volume of liquid
V

log V

1 .

Titration value ml. HCl, 0.0200 N ml. 7.62 7.59 8.53 8.32 10.17 10.30 11.07 11.28 12.60 12.71 12.44 13.00 13.38 13.38 15.30 16.09 16.05 15.84

OH" mequiv. 0.152 0.152 0.171 0.166 0.203 0.206 0.221 0.226 0.252 0.254 0.249 0.260 0.268 0.268 0.306 0.322 0.321 0.317

[OH-]
mN

log [ O H - ] + 1

0.075 0.075 0.100 0.100 0.200 0.200 0.250 0.250 0.300 0.300 0.400 0.400 0.500 0.500 0.750 0.750 1.000 1.000

1.125 1.125 1.000 1.000 0.699 0.699 0.602 0.602 0.523 0.523 0.398 0.398 0.301 0.301 0.125 0.125 0.000 0.000

2.032 2.024 1.706 1.664 1.017 1.030 0.886 0.902 . 0.840 0.847 0.622 0.650 0.535 0.535 0.408 0.429 0.321 0.317

1.308 1.306 1.232 1.221 1.007 1.013 0.947 0.955 0.924 0.928 0.794 0.813 0.729 0.729 0.611 0.633 0.507 0.501

primarily adsorbed ions. I t is further of interest t o note t h a t the slope of the curve decreases when the adsorbed amount increases, a feature which is required b y the theory. The results thus seem to make the presented theory likely. The differences between the theory and the experiments may be attributed t o the approximations introduced in the mathematics employed, and the difficulties in carrying out experiments which in a perfect way will allow these formulae t o be tested in their given form. I n the following paragraphs the hydrolytic adsorption of in organic alkali metal salts will be dealt with. The writer has found t h a t the hydrolytic adsorption from

solutions of these salts is a consequence of the facts described in Chapter 9. I n a solution composed of water and an inorganic alkali metal salt there is only one kind of primarily adsorbable ion present, namely the hydrogen ion. The alkali metal ions cannot even be secondarily adsorbed from the system concerned, as i t contains no primarily adsorbable anion. The anions, however, can be secondarily adsorbed together with hydrogen ions. The

lo -

0,5-

00-

Fig. 10. Hydrolytic adsorption of sodium picrate. (Data from Table 42.)

non-adsorbability of the alkali metal ions on H-charcoal provides the necessary ground for applying the principles of the Donnan theory t o this system. For a mathematical treatment we may take a system composed of a solution of sodium chloride in contact with H-charcoal. A t equilibrium the activity of the hydrochloric acid must be the same throughout the system. For hydrochloric acid we can consequently write: an* #ci~ & + #ci~ H (30) From the electrical neutrality of the free solution it follows that:
Cci- =
"

CtfA+ + CH+

fr

ft

COH~

ft

/oi\

(31)

From these formulae we obtain: 0>B.+ ' dci~ C + (CNa+ + C + COH~) H H

/ f ff i ff . ff ff \ /new

(>*)

I t follows from this formula, t h a t when the H-charcoal has a pronounced power t o adsorb hydrogen ions primarily, the p H of a sodium chloride solution is raised when i t is brought into contact with the charcoal. The rise in p H will be more marked when the solution is more concentrated. This theory is in qualitative agreement with the observations on hydrolytic adsorption on H-charcoal of solutions containing inorganic alkali metal salts. Quantitative tests of formula (32) will be postponed until the following chapter and will then be treated in connection with the adsorption of inorganic acids on H-charcoal from solutions com posed of the acid in question and an inorganic alkali metal salt. The theory of hydrolytic adsorption now given has certain points in common with Miller's theory (see Chapter 3, 1). Miller assumed, for instance, t h a t the rise in p H of a solution of an alkali salt of a strong acid, when i t was brought into contact with H charcoal, depended upon adsorption of unionized acid molecules. These molecules were assumed t o originate in hydrolysis of the salt. This free application of the theory of hydrolysis has been used as a central point in the criticism of Miller's theory. The writer has found t h a t the concept of primary and secondary adsorption of ions and the applicability of the Donnan theory t o ion adsorption form a sufficient basis for an interpretation of all cases of hydrolytic adsorption on H-charcoal described in this thesis.

XII. The Primary Adsorption of Ions as a Function of the Ionic Composition of the System.

I t is intended t o devote this chapter t o a description of the primary adsorption of ions on H-charcoal from solutions containing two strong electrolytes. I n solutions of this type one or more species of primarily adsorbable ions may be present. I t has been shown in Chapter 10 t h a t only large organic ions and hydrogen ions are capable of being primarily adsorbed. The effects under consideration may be classified as follows. a) The reciprocal influence of mineral acids and organic-inorganic electrolytes on the primary adsorption of hydrogen ions and organic ions. b) The reciprocal influence of two organic-inorganic electro lytes on the primary adsorption of the two organic ions. c) The influence of inorganic neutral salts and alkali metal hydroxides on the primary adsorption of organic ions from organic-inorganic electrolytes. d) The influence of inorganic neutral salts on the primary adsorption of hydrogen ions from mineral acids. The writer has investigated all effects except those falling in Group b. This exception was made for the following reasons. The adsorbability of a large organic ion is great but so varied t h a t an effect on its adsorption, due t o the presence of another organic ion of the same sign, ought not t o become apparent until the relative amounts of the ions are far from equal. Considerable analytical difficulties attend such a study. Similar difficulties would be met with if the two organic ions were oppositely charged, a s the water-solubility of a salt composed of a large organic anion and a large organic cation is generally very small.

Desorption of hydrochloric acid with picric acid. 1.000 g. H-charcoal. Volume of liquid: 70.00 ml. 20.00 ml. HCl, 0.0200 N . Time of contact: 3 days. Picric acid added 2 hours after the addition of hydrochloric acid.
Picric acid i added mequiv. Picric acid ads. mequiv. free mequiv. free

H+

free

cr

ml. 0.0200 N 6.80 18.23 19.42 20.18 19.87 20.03 20.13 20.31 6.84 18.41 19.46 19.82 20.04 20.06 19.86 20.06

0.20 0.30 0.40 0.50 0.60 0.70 0.80

0.20 0.30 0.40 0.50 0.60 0.70 0.80

0 0 0 0 0 trace trace

The adsorption of hydrochloric acid from solutions containing varying amounts of organic-inorganic electrolytes were studied in some experiments. Picric acid and methylene blue chloride were used as electrolytes. The experiments with hydrochloric acid and picric acid were carried out in the following manner: To a series of flasks containing 1.000 g. of H-charcoal and 0.4 mequiv. of hydrochloric acid different volumes of a solution of picric acid were added. The total volume of each solution was 50.0 ml. After 48 hours' shaking, the mixtures were filtered and the amounts of hydrogen ions and chloride ions determined in aliquot parts of the filtrates. The results are collected in Table 43 and represented in Figure 11. I t was found t h a t the presence of picric acid strongly depressed the adsorption of the mineral acid. When the system contained the same amounts of picric and hydrochloric acid no measurable adsorption of hydrochloric acid was observed, but all the picric acid present was adsorbed, as the free solution was colourless. A measurable equilibrium con centration of free picric acid was found only when 0.7 mequiv.
1 0 4 4 5 9 3 Brje Steeriberg

145

or more of picric acid was added t o the system. The fact t h a t the presence of picric acid, even in amounts so small t h a t they are completely adsorbed, prevents the adsorption of mineral acid has already been stated on page 105. The adsorption experiments with mixtures of hydrochloric acid and methylene blue chloride were carried out in the same way as those described above. The amount of methylene blue chloride added t o the system in these experiments was in all cases so small

Q2-

mequiu.
Qdsorbed Rcric Qcid

Fig. 11. Desorption of hydrochloric acid b y means of picric acid. (Data from Table 43.)

t h a t the free solution a t equilibrium was colourless. The free solu tion became acid, even when no hydrochloric acid had originally been added, because of the hydrolytic adsorption of methylene blue chloride. The results of the experiments are given in Table 44. I t will be seen t h a t the amount of mineral acid adsorbed is strongly decreased b y the presence of methylene blue chloride. Considering the results of the studies on the simultaneous adsorption of strong electrolytes and non-electrolytes on H-charcoal, described in Chapter 8, the above observations are compre hensible. The presence of two primarily adsorbable substances in a system must have a reciprocal influence on the amount of each substance adsorbed, because the adsorption capacity of the charcoal is limited. Some adsorbed molecules of the first substance must

Influence of methylene blue chloride on adsorption of HCl on H-charcoal. 1.000 g. H-charcoal. Volume of liquid: 75.00 ml. Methylene blue chloride 0.00846 N. Hydrochloric acid 0.02000 N . The methylene blue ion was quantitatively adsorbed in all experiments. Time of contact: 48 hours.
Methylene blue chloride ml. HCl ml. 25.00 25.00 25.00 25.00 25.00 25.00 20.00 20.00 15.00 15.00 10.00 10.00 5.00 5.00 H2O ml. 50.00 40.00 30.00 20.00 10.00

Free HCl ml. 0.02 N 16.88 17.85 19.21 20.37 21.58 22.97 12.21 18.27 7.76 14.07 3.96 10.12 1.03 5.48

Adsorbed HCl ml. 0.02 N + + + + + + 8.12 7.15 5.79 4.63 3.42 2.03

10.00 20.00 30.00 40.00 50.00

50.00

55.00 5.00 60.00 10.00 65.00 15.00 70.00 20.00

+ 7.79 + 1.73 + 7.24 + 0.93 + 6.04 0.12 1 + 3.97 0.48

50.00
..

50.00

50.00

1 Negative adsorption of HCl = hydrolytic adsorption of methylene blue chloride.

be expelled b y the addition of another adsorbable substance. This holds true even if the adsorbable particles are electrically charged. Since hydrogen ions can be so easily expelled from the charcoal surface i t follows t h a t the forces between the charcoal and the hydrogen ion are much smaller than those between the charcoal and the competing organic ions. Hitherto, only the influence of the organic ions on t h e adsorption of the hydrogen ions has been considered. We may now consider the converse case.

The writer observed t h a t the amount of primarily adsorbed organic ions on H-charcoal was increased b y the addition of mineral acids t o the system. Such a n increase was found for both organic anions and cations. I t was found, too, t h a t the amount of ad sorbed organic ions was increased by the addition of neutral inorganic salts and alkali metal hydroxides. I t will thus be appropriate t o report simultaneously the results of the experiments in which the influence on the adsorbed amount of organic ions, not only of mineral acid but also of neutral in organic salts and alkali metal hydroxides, was studied. The experiments were carried out in the following way. Equal amounts of H-charcoal were placed in a series of flasks, and an appropriate amount of a solution of an organic-inorganic electro lyte was added together with strong inorganic electrolytes in vary ing amounts. The liquid in each flask was made up t o the same volume with water* After a contact period of not less than a week between the charcoal and the solution, the charcoal was filtered off and the concentration of the free organic ions determined analytically. I n order t o obtain observable changes in the adsorbed amount of organic ions even when the amounts of inorganic electrolytes present are small, preliminary experiments are usually necessary. I n these experiments adsorption equilibria are studied, when the organic-inorganic electrolyte in question is the only solute. On the basis of the information provided b y these tests, an appropriate amount of organic-inorganic electrolyte is selected for the main experiments. This amount must be such t h a t the adsorption equilibrium obtained when the organic-inorganic electrolyte is the only solute will result in a concentration of the free organic ions, high enough for accurate estimation, but not so high t h a t the charcoal will be saturated or nearly saturated with the organic ion. If the charcoal is nearly saturated with the organic ion an effect on its adsorption can only be observed a t high concentrations of the inorganic electrolytes. As already pointed out (Chapter 7), i t is very difficult t o obtain reproducible results from adsorption experiments with organic electrolytes, because the equilibrium is attained so slowly. I n all experiments of the type described the time of contact between

the charcoal and the solution should not be under one week. Even though all possible precautions were taken as regards constant temperature and other such actors, it was found very difficult t o obtain reproducible results. All the experiments performed b y the writer and grouped together in a single table were carried out simultaneously. All flasks belonging t o a single series of experi ments were kept together and shaken in the same way. I t is not * Hi C KO N3 + N H #CoCi2 0 O O NCl *M^S04 aJ
LO(N03)3

,(>002

0.002

0,02

Qc/cfec/ so//
Fig. 12. Influence of inorganic e< llectrolytes on the adsorption of picrate ions. 1.000 g. H-charcoal. 0.175 g. sodr picrate. Volume of liquid: 75 inl. Time of con. i.tact: 12 days.

claimed t h a t true equilibrium conditions were reached in any of these series. Smaller series of tests in which the time of contact between the charcoal and the solution was extended over several months gave the same quaalitative result. The results of four serie of experiments using the method es outlined above, with sodium picrate, sodium methyl orange and methylene blue chloride as organic-inorganic electrolytes, and various strong inorganic electrolytes (mineral acids, salts, and alkali hydroxides), are given in Figures 1215. I t can be concluded from these results t h a t the presence of any inorganic electrolyte increases the amount adsorbed of an organic ion. If the concentration of the inorganic electrolyte is raised,

the amount of the organic ions adsorbed increases continuously. I t must also be observed, however, t h a t different strong inorganic electrolytes present in the same concentration do not influence the adsorption of an organic ion t o the same extent. The ex periments with methylene blue chloride (Figure 15) show t h a t two chlorides of equal concentration cause equal increases in the adsorbed amounts of the organic ion. On the other hand, the
KJ Ct
ANoN03 Na2S04 O t Mj 2 C

+ Lf l js aK J O

X C1 O 1S 4

0,0005

normality 0/ so//
Fig. 13. Influence of inorganic salts on the adsorption of methylorange. 0.200 g. H-charcoal. 100 mg. methylorange sod iam. Volume of solution: 100 ml. Time of contact: 8 days.

results show t h a t the influence of sodium fluoride is not appreciable a t concentrations in which sodium thiocyanate has already de pressed the equilibrium concentration of the free dye-stuff ion t o a n immeasurably small value. I t is evident from these observa tions t h a t the adsorption of methylene blue is only influenced b y the nature of the anion of the inorganic electrolyte. If the anions are arranged in order of decreasing influence on the adsorption of methylene blue, the lyotropic series is found: c m >j > n o 3 - > Br~ >c r > so4 >f~.

From the results of the experiments with organic anions (Figures 1214) i t follows t h a t the amount of organic anions adsorbed

depends on the concentration and the nature of the cation of the added inorganic electrolyte. The higher the valency of the cation added, the greater is the increase in the adsorbed amount of t h e organic anion. I n plotting the figures the concentrations in equi valents per litre of the cations were used as abscissae. If molarities Aii LC x oJ NCt + K* C oRIC! CCi

0,005

0,01

florma/f-fy of saft
Fig. 14. Influence of alkali metal chlorides o n the adsorption of methylorange. 0.200 g. H-charcoal. 100 m g . methylorange sodium. Volume of solution: 100 ml. Time of contact: 3 weeks.

had been used, the difference between the action of cations of different valencies would have been still more conspicuous. With small concentrations of the inorganic electrolytes, no measurable difference in the action of the different cations of the same valency is observed. With higher cationic concentrations also different cations of the same valency exercise varying influences on the adsorption of the organic anions. For the alkali metal ions, the increase in the adsorbed amount of the organic anion increases with the atomic number (Fig. 14). The order of the alkali metal ions in this respect is identical with the lyotropic series.

The interesting observation is made from Figures 12 and 15 that the effect produced by alkali metal hydroxides and mineral acids is essentially of the same nature as that produced by the inorganic salts. At first sight, this observation may appear peculiar.

0x~-

HCi sor er

00 0 00 2 00 , 0 2 ,0 ,2 rior/na/j-fy of S a/f

02 ,

Fig. 15. Influence of inorganic electrolytes on the adsorption of methylene blue. 1.000 g. H-charcoal. 0.200 g. methylene blue chloride. Volume of solution: 100 ml. Time of contact: 14 days.

Solutions containing as solutes an organic-inorganic electrolyte on the one hand, and an alkali metal hydroxide or an inorganic salt on the other, contain only one primarily adsorbable ion, namely the organic ion. Solutions composed of an organic-in organic electrolyte and a mineral acid, on the other hand, contain two primarily adsorbable ions, the organic ion and the hydrogen ioij. I t would seem that the presence of the hydrogen ions would decrease the adsorbed amount of the organic ion in essentially the same way as the adsorbed amount of a mineral acid was de

creased b y the presence of picric acid or methylene blue chloride (Tables 43 and 44). I n the last-mentioned experiments it was found, however, t h a t the organic ions were adsorbed b y much stronger forces t h a n was the hydrogen ion. Even in the presence of comparatively small amounts of the organic-inorganic electro lytes in question, the amount of mineral acid adsorbed was strongly depressed. The mineral acid can obviously be regarded, in t h e experiments shown in Figures 12 and 15, as an electrolyte con taining no primarily adsorbable ion. Thus, no essential difference is t o be expected between mineral acids and other inorganic electro lytes with respect t o their influence on the adsorption of large organic ions. The influence on the adsorption of organic ions exercised b y hydrogen ions has been studied b y many investigators (48, 78? 182, 184). Systematic studies of the influence of ions other t h a n the hydrogen ion on t h e adsorption of organic ions are not known t o the writer. The investigation on the influence of p H on t h e adsorption of organic ions t h a t has received most attention (81y 90) is t h a t carried out by Hauge and Willaman (78). These authors found t h a t the adsorption of organic anions originating in strong acids decreased with increasing pH, but t h a t the adsorption of organic cations from strong bases increased with increasing pH. The discrepancy between the results of Hauge and Willaman and the observations made b y the present writer might be due t o the fact t h a t Hauge and Willaman used com mercial charcoals for their experiments. 1 I t might be of interest t o find out why the influence of the hydrogen ion, b u t not t h a t of other inorganic ions, on the adsorp tion of organic ions has been the subject of enquiry b y other in vestigators. The following line of reasoning may provide an explanation. The adsorption of weak electrolytes is very slightly affected b y the presence of neutral salts (Chapter 8, page 72)*
Making use of "Darco" charcoal, Hang and Willaman found that the ad sorbed amount of methylene blue chloride increased both when a mineral acid and when an alkali metal hydroxide was added. The adsorbed amount was least from a solution which was only slightly alkaline (Figure 5, page 949). This obser vation, which is in the main i n agreement with the present writer's findings, i s not discussed b y the authors.
1

On the other hand, it has been found t o be a general rule t h a t undissociated molecules are more easily adsorbed on charcoal than the corresponding ions (64, 65, 161). I t is obvious t h a t when t h e adsorption of a weak organic acid or base is considered, the p H of the solution is of great importance, and t h a t the hydrogen ions cannot be treated in the same way as other inorganic ions. When the adsorption of strong organic acids or bases is studied, on the other hand, there is no essential difference between different inorganic ions. Earlier investigators do not seem t o have made a clear distinction between the adsorption of strong and weak organic electrolytes. The often observed impossibility of applying the results ob tained from decolorization experiments with charcoal made on a laboratory scale t o industrial decolorization may in some measure be explained by the above line of reasoning. I n the laboratory experiments, synthetic dye-stuffs are often used. From these experiments conclusions are drawn regarding the decolorization of natural dye-stuffs. The synthetic dyes are generally strong electrolytes, while the natural dyes are often weak electrolytes. The following section deals with the adsorption on H-charcoal of mineral acids from solutions containing inorganic salts in addi tion t o the acid. I t was observed even b y Lachs and Michaelis (113) t h a t the adsorption of mineral acids on blood charcoal increased when an inorganic salt was added t o the system. Miller (136), employing H-charcoal, also obtained an increase in the amount of hydro chloric acid adsorbed from a solution, b y adding potassium chloride t o the system. A more detailed investigation of the influence of neutral salts on the adsorption of inorganic strong acids has been carried out by Parks and Bartlett (155). These authors found an increase in the adsorbed amount of hydrochloric and nitric acid, on adding potassium chloride and potassium nitrate respectively, but a decrease in the adsorption of sulphuric acid on adding potassium sulphate. The highest concentration of salts used b y these in vestigators was 4.5 N. The surprising observation was made t h a t increases in the concentration of the salts led t o increases in the

amounts of hydrochloric and nitric acid adsorbed, b u t no upper limit was reached in the experiments. The authors in question found no trace of hydrolytic adsorption of inorganic salts on their charcoal. This latter was not an H-charcoal, as i t was capable of adsorbing sodium hydroxide. Parks and Bartlett suggested as a possible explanation of their observations t h a t the diffusibility of the adsorbed anion is strongly diminished in a solution with a high salt concentration. The decrease in

m^ i . e uv

0,3-

Qdded soIt.
Fig. 16. Influence of inorganic salts on the adsorption of hydrogen ions from hydrochloric acid. 1.000 g. H-charcoal. 0.4 mequiv. HCl. Volume of solution: 30.00 ml. Time of contact: 2 days. (Data partly from Tables 3134.)

the amount of sulphuric acid adsorbed, observed after the addi tion of sulphates, was thought t o be due t o the formation of bisulphate ions. The present writer has carried out a number of adsorption ex periments with H-charcoal, in which the solution in contact with the charcoal contained mineral acids and inorganic salts. I n some of these experiments the amount of mineral acid, the charcoal, and t h e volume of the solution were kept constant, while the concentration and nature of the salts were varied. I n other tests the amount of charcoal and the volume of the solution were kept constant and the amounts both of the mineral acid and the inorganic

Adsorption of H N 0 3 from solutions 1.000 g. H-charcoal. Time of contact:

HNO

0.02000 N ml. 0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00 28.00 30.00 32.00 34.00 36.00 38.00
1 2 3

0 . 0 0 1N K N O 3

0.005 N K N O 3 0 . 0 1 0 N K N O 3 0 . 0 2 0 N K N O 3
/

A1
0.02 3

a.2

/.

a.

a. 0.17 2.12 4.09 6.00 8.00 9.79 11.94 13.42 14.65 15.44 16.19 16.61 16.93 17.27 17.71 18.12 18.56 18.56 19.79 19.58

a.

/.

a.

2.02

8.00
.

1.05

10.95

0.58 1.70 3.02 3.77 5.40 6.98 8.90 10.48 12.03

13.42 14.30 14.98 16.23 16.60 17.02 17.10 17.52 17.97

1.32

14.68

3.56

16.44

6.57

17.43

9.45

18.55

12.85

19.15

16.10

19.90

0.17 0.12 0.09 0 0 + 0.21 0.06 0.56 1.35 2.56 3.81 5.39 7.07 8.73 10.29 11.88 13.44 15.44 16.21 18.42

0.12 2.12 0.10 4.10 0.03 6.03 8.00 0 + 0.02 9.98 0.08 11.92 0.38 13.62 1.04 14.96 2.18 15.82 3.65 16.35 5.03 16.97 6.57 17.43 8.20 17.80 9.78 18.22 11.34 18.66 12.75 19.25

I I

8.53 9.98 11.43

19.47 20.02 20.57

18.00

20.00

ml. 0.02 N HNO3 in free solution. " ml. 0.02 N HNO3 adsorbed. " Negative sign indicates that the filtrate was alkaline.

salt were varied. For the last-named experiments the salt was so chosen t h a t i t contained the same anion as the acid. The experiments were carried out by the same method as t h a t employed when the influence of inorganic electrolytes on the adsorption of organic ions was studied, the only difference being that the duration of contact between the solution and the charcoal was only two days. This contact time is sufficient for an adsorp tion equilibrium t o be established, when inorganic electrolytes are used.

containing H N 0 3 and K N 0 3 . Volume of solution: 40.00 ml. 48 hours. Temp. 22 C.

0.030 N K N O 3 0 . 0 5 0 N K N O 3 0 . 1 1 0N K N O 3 1 0 . 2 0 0 N K N O 3 0 . 3 0 N K N O 3 1.0 N K N O s

/.

a.

/
0.21

a.
!

/ -

a.

a.

a.

/
0.29 0.17

a.

_ _

0.21

0.17 0.15 0.08 0.03

0.01 0.01

8.03 9.50 10.79

t i

0 + 0.23 0.69 1.65 2.78 4.13 5.43 19.97 6.93 20.50 8.36 21.21 9.84 11.48 13.05 1 14.78

2.17 0.23 4.15 0.17 6.08 0.05 8.03 0.03 10.01 0 12.01 0 14.00 0 15.77 + 0.08 17.31 0.45 18.35 1.20 19.22 2.04 19.87 3.33 20.57 4.74 21.07 I 6.35 21.64 7.34 22.16 8.91 22.52 10.41 22.95 11.78 23.22 13.35

2.23 0.14 2.14 4.17 0 . 2 0 4.20 6.05 0.12 6.12 8.03 8.11 0.11 10.00 0.06 10.06 12.00 0.03 12.03 12.00 0 14.00 0 14.00 15.92 + 0.08 15.92 + 0.07 15.93 17.55 0.33 17.67 18.80 0.98 19.02 + 1.02 18.98 19.96 1.71 20.29 20.67 3.26 20.74 3.05 20.95 21.26 4.17 21.83 21.65 5.55 22.45 5.12 22.88 22.66 6.84 23.16 23.09 8.40 23.60 8.13 23.87 23.59 9.54 24.46 24.22 11.30 24.70 10.95 25.05 24.65 12.45 25.55

0.29 2.17 0.11 4.11 0.08 6.08 0.06 8.06 0.03 10.03 0.02 12.02 0 14.00 + 0.30 15.70 0.23 17.77 0.65 19.35 1.47 20.53 2.31 21.69 3.45 22.55 4.64 23.36 6.17 23.83 7.07 24.93 8.40 25.60 9.61 26.39 11.14 26.86

The results of a series of determinations of the adsorption of hydrogen ions from solutions containing the same amount of hydrochloric acid but varying amounts of some inorganic salts are shown in Figure 16. The salts employed in these experiments were KCl, NaCl, CaCl2, Na 2 S0 4 , KBr, NaN0 3 , KNO a , K I , Cal 2 , KONS. I t was found t h a t the adsorbed amount of hydrogen ions increased on the addition of any inorganic salt. The sul phates constituted no exception t o this rule. Two salts a t equal concentrations with a common anion but a different cation showed the same effect on the hydrogen ion adsorption. With salts having common cations but different anions, on the other hand, the influence exercised on the hydrogen ion adsorption differed.

If the anions were arranged in order of decreasing actions on the hydrogen ion adsorption the following series was found: CNS~ > I " > N O 3 - > Br~ > CI" > S 0 4 This series is identical with the lyotropic series of the anions. I t is of interest t o note t h a t the influence of the inorganic salts on the hydrogen ion adsorption was analogous to t h a t observed

0,5-

1,00 N
0,11 N 0.O5N

0,4-

0,3-

Q 0 1

In/fiol co/?ce/?/ro//o/7

0,015

N HNO3

Fig. 17. Adsorption of nitric acid from solutions containing potassium nitrate. (Data from Table 45.)

when the primarily adsorbable ion was the methylene blue ion (Fig. 15). I n the latter case also only the nature of the anion of a salt in the solution had an influence on the adsorption of the positive ion. As it seemed likely t h a t a study of the influence exercised b y inorganic salts on a considerable part of the adsorption isotherm for mineral acids might yield interesting results, experiments with nitric acid and sodium nitrate in varying concentrations were carried out. The results of these experiments are given in Table 45 and Figure 17. No upper limit relative t o the amount of hydrogen ions adsorbed was obtained in these tests. The hydrogen ion

adsorption was in some cases strong enough t o render the free solution not only neiitral but even alkaline. I n Figure 17 t h e amount of adsorbed acid is plotted against the initial concentration of the acid in the free solution. The broken line in the graph indicates total adsorption of the added mineral acid (neutrality of the free solution). I t is obviously rather unsuitable t o take a s abscissae the equilibrium concentrations of mineral acid in plotting the results of these experiments. If this were done i t would some times be necessary t o speak of a concentration of acid in an alkaline solution. The present writer considers t h a t the effect of strong inorganic electrolytes on the adsorption of organic-inorganic electrolytes, and the effect of inorganic salts on the adsorption of mineral acids have the same cause. A theory t o account for this "salt effect" may be arrived a t if the author's concept of primary and secondary adsorption is used. For a theoretical interpretation, however, i t is necessary t o introduce supplementary assumptions regarding the distribution of the ions in the vicinity of the charcoal surface, in addition t o those used in the preceding text. 1 Let us study a system composed of H-charcoal and a solution containing an adsorbable solute in the form of unionized molecules. We will assume t h a t a t adsorption equilibrium the concentration (cs) of the solute in the bulk of solution is so small t h a t we can write for its chemical potential: [x = [i -f kTki cs (33) On the surface of the charcoal the substance in question has the activity (aa). The work of adsorption is then: =
1

C>S

(34)

THE PRINCIPLES O THE THEORY T BE OUTLINED IN THE FOLLOWING PAGES A E ESSENT F O R

IALLY THE SAME AS THOSE USED BY CASSIE AND PALMER (46) IN 1 9 4 1 T INTERPRET THE O CHANGE IN SURFACE TENSION O A SOLUTION O A PARAFFIN CHAIN S L ON ADDITION O A F F AT F NEUTRAL SALT. CASSIE AND PALMER'S THEORY IS FOUNDED ON A THEORY O ELECTROKINETIC F PHENOMENA DEVELOPED BY MLLER AND ABRAMSON (3, 144, 145, 146). UNAWARE O F THE WORK O CASSIE AND PALMER, THE WRITER (180) SUGGESTED IN 1 9 4 1 TH PRINCIPLES F O A THEORY T EXPLAIN ELECTROLYTE ADSORPTION ON CHARCOAL, BASED ON THE SAME IDEA F O AS THE THEORY O THESE WORKERS. THEIR PAPER SHOULD BE CONSULTED F R DETAILS O THE F O F MATHEMATICS EMPLOYED.

If the adsorbable substance is an ion, the work of adsorption de pends not only on the change in chemical potential but also on t h e electrical work t o be done in the transportation of the ion from the bulk of the solution t o the surface. If we assume t h a t the electrical potential in the bulk of solution is (ip"), and t h a t a t t h e surface is (\pf), this electrical work is then z e (t// \p")9 where (z) is the valency of the ion and (e) the charge of an electron. In t h e formula (33) the concentration of the adsorbable union ized molecule was so small in the bulk of solution t h a t its activity coefficient could be put equal t o unity. If the adsorbable particle is an ion, such an assumption will involve appreciable errors even a t very low concentrations of the ion. Ions diverge from ideal behaviour much more than do unionized molecules. The difference from the ideal behaviour of ions in dilute solutions depends chiefly on the electrical potential due t o the ionic atmosphere in the solution. Debye and Hckel have obtained a value for the activity coefficient of an ion in a dilute solution by a consideration of the electrical potential We may consequently remove the term (z. \p") if we introduce the activity of the ion in the bulk of the solution instead of its concentration. For the adsorption of ions we can consequently write: Ja = kTln + z sxp' &s or: 5 = g ~Tt~~ a8
J z s ip'

(35)

(36)

I t has been experimentally ascertained (64, 65, 161) t h a t the ionization of a substance has a profound effect on its adsorption. I t must be concluded from these observations t h a t the non-electrical work of adsorption and the electrical work of adsorption are in many cases of the same order of magnitude. Of these two factors, the electrical one is independent of the chemical nature of the ion adsorbed. As the adsorbabilities of different ions have greatly differing values, it seems justifiable t o assume t h a t these variations depend on different values of the non-electrical work of adsorption for the different ions. I n the case in which the non-electrical work of adsorption for one kind of ion is much larger than t h a t of

the other of ions present in the system, the surface of the charcoal must be supposed t o be covered almost exclusively b y ions of the kind with the largest non-electrical work of adsorption. These ions are named the primarily adsorbed ions. The electrical work of adsorption would be very large/however, if only one kind of ion were present a t the charcoal surface, because then (\pf) is large in comparison with (ty"). When adsorption is really observed there must be present, in the vicinity of the prim arily adsorbed ions, ions of the sign opposite t o t h a t of the primarily adsorbed ions which decrease (tp'). These are the secondarily adsorbable ions. The distribution of these ions in the system must have a strong influence on (xp') and consequently also on the ad sorption equilibrium. I n order t o calculate the potential we introduce some sim plifications, namely that: 1) the surface of the charcoal is plane, 2) the charcoal with the point charges of the primarily ad sorbed ions can be treated as a uniformly charged surface. Poisson's equation describes the change in potential with an increasing distance normal t o a plane charged surface element:

I n this equation (D) is the dielectric constant of the medium, () the charge density, and (x) the distance normal t o the plane surface element. Introducing the Boltzmann principle we arrive a t the well-known Poisson-Boltzmann equation: d2xfj ____ 4TV ^
Z { Ex p

ZiUiS e

kT

(38)

where (z) is the valency of the ions, including their sign, and (n) the number of ions per unit volume of the solution. The summation should be carried out over all the ions in the system. Mller (658) has integrated the above formula for the case of a uniformly charged plane surface, using the boundary condition:
(39)
1 1 44593 Brje Steenberg

161

The result is: 1 (d\p\2 jrkT^ / Hty' = e Adi) - g - 2 ' " ( " 1

,in. <40>

From Gauss's law we obtain for the surface charge density (8): IdjA [dxj^o _ 47td D
1

>

From these two formulae we obtain a formula for d: DkTS? l-zllil (0%== ^ - 2 j ^ ( e 0
1

<42>

No direct method for measuring the surface charge density of a charcoal in an electrolyte solution is known t o the writer. Clearly (d) cannot be identified with the surface excess of ions multiplied b y their charges, because in formula (42) only the component of the field of force normal t o a plane element of the charcoal is considered. As a first approximation, however, (d) may be con sidered as a function only of the adsorbed amount of ions per unit of charcoal. This hypothesis provides a possibility of inter preting formula (42). The convention used in deducing this formula is t h a t the approach of ions of identical sign increases the energy of the system; hence (d) and (ip) have the same sign. If the prim arily adsorbed ions are cations, (\fj) will be positive and ( z e tp) will be positive for anions and negative for cations. I t may now be recalled t h a t experiments have shown t h a t only the nature of the ions of sign opposite t o t h a t of the primarily adsorbed ions has an influence on their adsorption. This implies t h a t (ifj) appreciably differs from zero, because only then will the value of the exponential term:
' ;

e TT c

zstp

(43)

be small for ions of the same sign as the primarily adsorbed ions in comparison with its value for ions of the opposite sign. We m a y assume in accordance with the experimental observations t h a t the value of (ifj) is so large t h a t we may neglect the contribution of the ions of the same sign as the primarily adsorbed ions t o t h e

right-hand side of formula (42). If the value of (%p) is far from zero we may also neglect the term \2n^) in the formula. For the above ease we obtain approximately: 2 C T (44)

where (n^ is now the number of ions per unit volume having the opposite sign t o (d) and consequently also the opposite sign t o the primarily adsorbed ions. Consider a system composed of an H-charcoal and a solution of a uni-univalent electrolyte, one of its ions being primarily ad sorb able, and a neutral inorganic salt containing r-valent ions of the sign opposite t o t h a t of the primarily adsorbed ions. For this system formula (44) can be written: y^-c,-e j e y/ l j l I I r y>' 1 +nrelTrl <)

if (c5) and (nr) are t h e concentrations a t adsorption equilibrium of the uni-univalent adsorbable electrolyte and of the neutral inorganic salt, respectively, in the bulk of solution. The above equation may be combined with, formula (36) in order t o eliminate the potential (x/j'). The substitution gives:

This formula cannot be tested in the given form, as neither the surface concentration of the primarily adsorbed ions, nor, the surface charge density is known. According t o the previous treatment, however, a certain amount of adsorbed ions from a solution per unit weight of charcoal gives a definite surface concen tration and also a definite surface charge density. We assume t h a t the activity of the primarily adsorbed ions is independent of the ionic strength of the solution j n contact with the charcoal. The right-hand side of formula (46) is then constant. Writing: " a e A <47)

and

we find for the case considered: 1 + nr . Cs <'-2> Air i) (49)

Similarly we find for the case when the secondarily adsorbed ions are univalent: (50) fs ' (ps ^l) ^ These formulae give the relation between the concentrations of the primarily adsorbable free ions and the concentration of the secondarily adsorbable free ions in the solution, when the solution is in equilibrium with a given amount of primarily adsorbed ions. If the above-mentioned theory is compared with the experi mental results given in Figs. 1217, a good qualitative agree ment will be found. The theory predicts an increase in the amount of ions primarily adsorbed when ions which are only secondarily adsorbable are added t o the system. Such a n effect has been observed for all types of primarily adsorbable ions, viz. for both organic ions and the hydrogen ion. The theory also requires, for instance, t h a t the amount of primarily adsorbed organic anions shall be greater if the system contains a metal cation of higher valency than one of lower valency a t an equal concentration. This effect has also been observed (Fig. 13). According t o this theory the same effect on the primary ad sorption should be found a t a certain concentration of secondarily adsorbable ions of equal valencies, irrespective of the nature of this ion. Experiments proved, however, t h a t secondarily adsorbable ions of the same valency differed in their influence on the primary adsorption. This was especially noticeable when the secondarily adsorbable ion was an anion. This effect is obviously beyond the scope of the theory. I t is possible t h a t secondarily adsorbable ions which are little hydrated may have a greater influence on the primary adsorption than those which are more hydrated. The less hydrated ions can approach the primarily adsorbed ions more closely, and decrease the electrical potential a t the charcoal sur

face t o a greater extent than ions with a thicker shell of hydration. I t was observed in the experiments t h a t the secondarily adsorbable ions could be arranged, as regards their influence on the primary adsorption, in the lyotropic series. The ions which are least hydrated were, in fact, observed t o have the strongest action on the primary adsorption. I t is of some interest t o note t h a t partially analogous results, as regards the influence on the primary adsorption of secondarily adsorbable ions, can be found when the Donnan theory is applied t o the systems under consideration. Let us, for instance, study the adsorption of the organic-inorganic salt XC1 from a solution containing, in addition t o XC1, sodium chloride in water. The condition for adsorption equilibrium is:
/ f tr dx+ #ci~ = Q>x+ tt ci' / eft \

(^/

The sodium ions cannot enter the adsorption space either as primarily adsorbable or secondarily adsorbable ions, and the concentration of free chloride ions is consequently: CCI- = c'x+ + C a N+ (52)

B y introducing c^V- from this formula into formula (51) the following formula will be obtained: c'x+ C1- (f)2 = c'x+ - fx+ [Cx+ + CNa+] * fci~ I t is noted from this formula t h a t the amount of XC1 adsorbed must increase when sodium chloride is added t o the system, if the charcoal is not already saturated with XC1. The above formula, where X+ is replaced b y H+, shows the influence of sodium chloride on the adsorption of hydrochloric acid. I n the latter case it will be observed from the formula that, if sufficient salt is present in the system, the free solution a t adsorption equilibrium will pass the neutral point and become alkaline. Such cases have also been observed by the writer. The two methods used t o obtain a formula showing the influence of univalent secondarily adsorbable ions on the primary adsorp tion of ions give results which are very similar. If we assume t h a t a certain amount of Y+ ions are primarily adsorbed, the first (53)

theory requires t h a t a t adsorption equilibrium the free ions satisfy the following formula: Cy+ - fy+ ' [c'r+ + c'A-} = K (54)

where c'A-is the concentration of the free secondarily adsorbable anions of the added salt and K is a constant. The formula derived from the application of the Donnan theory requires that, when the activity of the adsorbed electrolyte is fixed,
C'Y+ ' FY+ \C'Y+

C'M+}

IA- = K1

(55)

where cM+ is the concentration of the non-adsorbable ions in the free solution and Kx is a constant. I n both cases c'a = Cm+. (56) Formula (54) contains the activity coefficient of the primarily adsorbable ions but not the activity coefficient of the secondarily adsorbable ions. I n formula (55) the activity coefficients of both the primarily and the secondarily adsorbable free ions appear in the formula. B y the use of the latter formula the specific proper ties of the secondarily adsorbable ions also can consequently be interpreted; this is not the case for formula (54). The writer has not been able t o test any of t h e above-mentioned formulae quantitatively, using organic ions as primarily adsorbed ions, because of the earlier mentioned difficulties in obtaining reproducible results from adsorption experiments with organicinorganic electrolytes. The testing of the above formulae has there fore been confined t o adsorption on H-charcoal from solutions of monobasic mineral acids and inorganic salts in water. The rate of adsorption of mineral acids on H-charcoal is relatively high and reproducible results can easily be obtained from adsorp tion experiments using these substances. I n testing formulae (54, 55) approximations were introduced. I t was assumed a) t h a t the activity coefficients of all ions in the free solution are all unity; b) t h a t the surface concentration of the primarily adsorbed ion and the activity of the adsorbed electrolyte were dependent on the amount of adsorbed acid per unit weight of charcoal b u t independent of the concentration of ions in the free solution. Thus, if from a series of solutions the

same amount of mineral acid is adsorbed per unit weight of char coal, the compositions of the free solution a t equilibrium are de termined according t o the theory b y the formula: '[H+]"([H+T + [B]") = K (57)

where B is the concentration of the inorganic uni-univalent salt and K is a constant. The above formula also covers zero concen tration of the salt B. The experiments with hydrochloric acid and sodium chloride were carried out in the following way. A sample of 1.000 g. of H-charcoal was mixed with 10.00 ml. of water and 20.00 ml. of 0.0200 N hydrochloric acid. After four days' shaking, the con centration of free hydrochloric acid was determined. The con stant K in formula (57) was calculated from these results. By using this value of K and an arbitrary concentration of sodium chloride the concentration of hydrochloric acid which would satisfy the equation (57) was calculated. 30.00 ml. of a solution was prepared which contained the calculated amount of sodium chloride and an amount of hydrochloric acid large enough t o ensure that, if the same amount of hydrochloric acid as in the first experiment was adsorbed from this solution, the equilibrium concentration of the acid would be equal t o t h a t calculated from K and the concentration of the sodium chloride. To this solution 1.000 g. of H-charcoal was added. After four days' shaking the free hydro chloric acid was estimated, and the amount of hydrochloric acid calculated. According to formula (57), the same amount of hydro chloric acid should be adsorbed in this experiment. The results of a series of experiments carried out in this way are given in Table 46. The results of a series of experiments with nitric acid and potassium nitrate are shown in Table 47. The agreement with formula (57) is good. The good agreement between the experimental results and for mula (57) found in the above experiments is somewhat astonishing, when i t is remembered t h a t in formula (57) all activity coefficients are taken as unity. The following explanation is suggested t o account for the fact t h a t formula (57) can interpret the observa tions. The activity coefficients of the free ions are chiefly deter mined b y electrostatic forces. The activity coefficients of the

Adsorption of hydrochloric acid from solutions containing HCl + NaCl. 1.000 g. H-charcoal. Volume of liquid: 30.00 ml. HCl 0.02000 N. Time of contact: 48 hours. Temp. 22 C.
Equil. concn. Na C I in ml. 0.02 N Added HCl in ml. 0.02 N
(JI

in ml. 0.02 N Obs. Cal.

Ads. HCl in ml. 0.02 N

_
1.00 2.00 5.00 10.00 15.00 20.00 20.00 30.00 30.00

20.00 19.51 19.08 17.96 16.69 15.90 15.38 15.38 14.79 14.79

6.60 6.09 5.80 4.75 3.20 2.39 1.86 1.97 1.27 1.34

13.40

6.11 5.68 4.56 3.29 2.50 1.98 1.98 1.39 1.39

13.42 13.28 13.21 13.49 13.51 13.52 13.41 13.52 13.45

adsorbed ions depend on electrostatic forces, but are also af fected especially in the case of the primarily adsorbed ion by van der Waals' forces between the charcoal and the adsorbed ion. If we assume that the electrostatic effect on the adsorbed ions is determined b y the ionic composition of the solution far from the charcoal surface, the electrostatic influences on the free and on the adsorbed ions are the same. The van der Waals' forces acting between the charcoal and the adsorbed ions are probably different for different adsorbed ions. The non-electrical works of adsorption of an ion on different surface atoms of the adsorbent are certainly not identical. However, if the adsorption is compared in two experiments where the same amount of electrolyte is adsorbed on the same amount of charcoal of a certain type, the van der Waals' forces between the electrolyte and the charcoal can be assumed t o be the same. Such comparisons are made in the above experiments. If the above assumptions are correct it is obvious t h a t the variations in the activity coefficients of the free ions are

Adsorption of nitric acid from solutions containing HNO3 + KNO3. 1.000 g. H-charcoal. Volume of liquid: 40.00 ml. HNO3 0.02000 N . Time of contact: 48 hours. Temp. 22 C.
Added HNO3 i n ml. 0.02 N 30.00 30.00 30.00 29.04 28.15 27.74 26.61 25.92 24.49 23.38 22.49 21.81 20.80 20.12 20.12 Equil. concn. HNO3 i n ml. 0.02 N Obs. 13.10 13.14 13.11 12.26 11.35 10.83 9.77 9.00 7.48 6.43 5.63 4.88 3.96 3.22 3.25 Cal.

KNO3 in ml. 0.02 N

Ads. HNO3 i n ml. 0.02 N

13.12

16.88

2.00 4.00 5.00 8.00 10.00 15.00 20.00 25.00 30.00 40.00 50.00 50.00

12.16 11.27 10.86 9.73 9.04 7.61 6.50 5.61 4.93 3.92 3.24 3.24

16.78 16.80 16.91 16.84 16.92 17.01 16.95 16.86 16.93 16.84 16.90 16.87

not manifested in such adsorption experiments. If, however, t h e amount of adsorbed ions per unit weight of charcoal increases, the adsorption occurs also on less active points of the charcoal, and the increase in the adsorbed amount is not proportional t o the increase in concentration. If this hypothesis is correct, t h e trend of a n adsorption isotherm gives a picture of the relative number of surface patches with different "surface activities".

The observations regarding the adsorption of strong electro lytes on H-charcoal dealt with in this paper are in many respects analogous t o the phenomena observed when strong electrolytes are adsorbed a t the air/water interface. The existence of such a

parallel Avas, in fact, used as a starting point when the writer made a working hypothesis regarding the adsorption of organic electro lytes on H-charcoal. Just as i t is known t h a t paraffin chain salts are adsorbed a t t h e air/water interface, with their organic ions primarily adsorbed and their inorganic ions secondarily adsorbed, so picrates, for instance, are adsorbed on H-charcoal, the organic ion primarily, and the inorganic ion secondarily. The parallel is especially in teresting as the forces which drive the paraffin chain ion into the air/water interface and those which force the picrate ion t o the H-charcoal surface are not the same. (Paraffin chain ions are, in fact, very feebly adsorbed on H-charcoal.) Some further analogies between the interfaces may be worth mentioning. The hydrolytic adsorption of organic-inorganic salts a t the H-charcoal/water interface has its analogue in the fact t h a t the p H of soap solutions is smaller a t the surface of the solution t h a n in its interior ( 1 5 8 ) . The p H values of solutions of invert soaps, on the other hand, are larger a t the air/water interface t h a n in the bulk of the solution (59). I t h$.s further been shown t h a t the decrease in surface tension of a paraffin chain salt solution observed on the addition of an inorganic salt can be treated in the same way as the increase in the adsorption of an organic ion on H-charcoal when inorganic salts are added. When the surface tension of a solution of a paraffin chain salt was studied as a function of the concentration of the salt, it was found t h a t after a n initial decrease in the surface tension, a mini mum point was obtained, and the surface tension of the solution then again increased. The existence of a minimum point in the curve is interpreted as being due t o the formation of paraffin chain ion micelles. The writer has found a parallel even t o this phenomenon a t the H-charcoal/water interface. When the amount of adsorbed methy lene blue was studied as a function of the concentration of the methylene blue ions in the bulk of the solution a maximum was observed in the adsorbed amounts of the methylene blue ions. The equilibrium concentration of the methylene blue ions corre sponding t o the maximum adsorption was as far as the preli-

minary experiments showed identical with t h e critical micelle concentration of t h e methylene blue ions. The equilibrium con centration of methylene blue ions corresponding t o t h e maxi m u m i n t h e adsorbed amount w a s changed i n the direction of a smaller methylene blue ion concentration when inorganic salts were present i n t h e system. I t is well known that t h e critical micelle concentration of a paraffin chain salt is changed i n t h e direction of smaller concentrations when inorganic salts are pre sent. The above-mentioned phenomenon, which is of great theo retical interest, will be subjected t o a more detailed study a t a later date. The parallel between t h e H-charcoal/water and t h e air/water interface is, however, not restricted t o t h e adsorption of organic electrolytes. I t is well known that alkali metal hydroxides increase t h e surface tension of water. Inorganic salts a t concentrations above about 0.002 N increase t h e surface tension of water. Weaker solu tions of inorganic salts decrease its surface tension (87). Mineral acids i n moderate concentrations decrease t h e surface tension of water. The increase i n t h e surface tension of water caused b y alkali metal hydroxides and inorganic salts has only been explained as a n adsorption of water at t h e air/water interface. According t o all recent theories with regard t o the surface tension of electrolyte solutions, all inorganic ions tend t o increase the surface tension of water (154). The change i n the surface tension of water, observed when mineral acids or small amounts of inorganic salts are added, cannot b e explained b y these theories. I t seems possible, however, t o interpret the above observations if it be assumed t h a t from solutions of inorganic electrolytes both water and hydrogen ions can be adsorbed a t t h e air/water interface. The surface tension of a solution of a n inorganic electrolyte m a y be a resultant of t h e adsorption of water, which increases with increasing ionic strength, and t h e adsorption of mineral acids, which increases with t h e increasing activity of the acid i n t h e bulk of t h e solution. The rise i n t h e surface tension of water o n the addition of a n alkali metal hydroxide is then caused b y adsorption of water, and is a pure electrostatic effect of the ions.

The decrease i n surface tension of mineral acids i n moderate concentrations is caused b y adsorption of t h e acid (primary ad sorption of hydrogen ions). The adsorption of water a t t h e air/water interface must simultaneously be considered. This hypothesis being correct, t h e addition of a mineral acid i n small concentrations t o a concentrated solution of a n inorganic salt must decrease t h e surface tension of t h e salt solution t o a greater extent than if t h e acid were t h e only solvent in t h e same concentration. Such effects have been observed (22). Belton found t h a t 0.1 N hydrochloric acid, which decreased t h e surface tension of pure water b y only 0.02 dyne/cm., decreased t h e surface tension of a solution of 4 N sodium chloride b y 0.6 dyne/cm. The adsorption of t h e mineral acids i s obviously increased b y t h e presence of the salt. This phenomenon seems t o be analogous t o the increase in t h e adsorp tion of mineral acids o n H-charcoal observed when inorganic salts are added. The observation that inorganic salts i n small concentrations decrease the surface tension of water can th en be treated i n a manner analogous t o t h a t applied t o t h e hydrolytic adsorptibn of inorganic salts o n H-charcoal. A decrease i n t h e surface ten sion of water can only b e expected a t low concentrations of t h e salt, because a t higher concentrations the adsorption of water a t t h e interface will b e dominant, resulting i n a rise i n t h e surface tension. The above hypothesis i s t o be submitted t o experi mental test b y the writer. The reason w h y t h e hydrogen ions should be primarily adsorbed a t the H-charcoal/water interface, a s proved b y t h e writer, and a t t h e water/air surface, as suggested above, is not y e t clear. I t seems probable that t h e effect depends on characteristic properties of the water. The hydrogen ions are certainly adsorbed a s hydronium ions.

Appendix.

Methods o f analysis employed. Barium. Barium was estimated titrimetrically b y the following method. The solution containing barium ions was neutralized, and again made acid against methyl red with 2 drops of hydro chloric acid, 0.02 N . Into this solution a standardized solution of N a 2 H P 0 4 was dropped from a burette. Each drop of the phos phate solution temporarily changed the colour of the test solution t o yellow. When the solution was shaken the colour again turned red, because the phosphate was precipitated as B a H P 0 4 . When the colour of the test solution n o longer turned red, the burette was read. The solution of N a 2 H P 0 4 was standardized against a solution of BaCl 2 , the concentration of which was calculated b y gravimetric determination of barium as barium sulphate. The method employed is accurate t o within 3 per cent. Bromide. See chloride. Chloride. Chlorides and bromides were determined titrimetric ally according t o Volhard. The silver nitrate and the ammonium thiocyanate solutions were 0.02 N . Nitrobenzene was added after the addition of the silver nitrate in order t o cluster the silver halogenide. The nitrobenzene addition proved very useful i n the cases i n which the test solution before the estimation of the halogenides had been used for acidimetric titration. The methyl red used as indicator was, in fact, extracted b y the nitrobenzene and i t was thus easy t o recognize the colour change when sufficient ammonium thiocyanate had been added. The chloride determinations which are given i n Table 14 were made b y means of Votocek's and Trtilek's chlorometric method using mercury nitrate and diphenylcarbazone as indicator. The modification suggested b y Bohm and Sturz was employed. 1
1

Sturz, O., Chemiker-Ztg., 67, 57, 1943.

Copper. Cupric ions were estimated iodometrically. A b o u t 1 g . of solid potassium iodide w a s added t o t h e acid sample a n d t h e liberated iodine titrated w i t h 0.02 N sodium thiosulphate. W h e n t h e yellow colour of t h e solution w a s v e r y faint a f e w grams of solid potassium thiocyanate and starch solution were added a n d t h e solution titrated until i t w a s colourless. 1 Cotarnine. A preparation of cot a m i n e chloride which w a s slightly acid w a s used for t h e experiments. Cotarnine base w a s added t o t h e chloride solution until t h e p H of t h e solution w a s 6.2. Cotarnine w a s estimated colorimetrically according t o Steenberg 2 . T h e principle of t h e m e t h o d i s t h a t a decomposition product of cotarnine, obtained b y heating t h e substance i n a n alkaline solution, c a n b e reproducibly coupled w i t h a diazonium salt, a n d t h e dye-stuff t h u s obtained colorimetrically determined. F o r t h e details of t h e m e t h o d see Steenberg's paper. T h e calibra t i o n curves for t h e colorimetric estimations were m ade b y using a recrystallized preparation of cotarnine base, which, according t o nitrogen analysis, contained 98 % cotarnine. Iodide. F r o m t h e iodides iodine w a s liberated b y t h e addition of small amounts of sodium nitrite t o t h e acid sample; t h e iodine w a s extracted b y chloroform a n d estimated colorimetrically i n a Pulfrich photometer using filter S 53. T h e concentration^ of t h e iodine i n t h e solutions were 0.0050.04 weight/volume per cent. T h e calibration curve w a s m a d e b y using potassium iodide, pro analysi. Methylene blue chloride. T h e substance used w a s obtained f r om Kahlbaum, Berlin, a n d w a s labelled " M e t h y l e n b l a u , M, reinst, fr medizinische Zwecke". This substance w a s dissolved i n e t h y l alcohol a n d precipitated with e t h y l ether, filtered off, a n d . dried a t 105 C after washing w i t h ether. T h e chloride content i n t h e recrystallized substance w a s determined b y combustion i n a Grote-Krekeler furnace a n d t h e a s h content b y ignition of 1 g . of dye-stuff i n a crucible i n a n electric furnace. T h e nitrogen i n t h e substance w a s estimated b y t h e Kjeldahl method. T h e results were: ,
1 2

Foote, H. W., and Vance, J . E., J . Amer. Chem. Soc., 57, 845, 1935. Steenberg, B., Svensk farmac. Tidskr., 44r 309, 1940. '

N calc. 13.14% obs. 13.16%

Cl 11.09% 11.07%

The substance was determined colorimetrically b y use of t h e Pulfrich filter S 61. For the estimations the concentration of the methylene blue chloride was 0.00200.010 mg. per ml. Mineral acids. The solutions of mineral acids used in the e x periments were prepared b y dilution of 0.1 N solutions of the acids. The acids were estimated titrimetrically with sodium hydroxide, 0.02 N . A s indicator an isohydric solution of methyl red sodium was used. Nitrate. A method for the colorimetric estimation of nitrate b y the use of -methyl-umbelliferone has recently been published b y the Russian investigators Wassiljew and Duchinowa. 1 The details of their method are not known t o the writer, as only a short review is available. I t was observed b y the writer that -methyl-um belliferone with bromates, chlorates, iodates, and nitrates, when heated i n hydrochloric acid, was transformed into a yellow sub stance. The colour of the solution was strongly increased when the solution was made alkaline. The following standard method for nitrate estimation using this reaction has been emplyoed: A 1.00 ml. sample was mixed with 0.5 ml. reagent solution containing 0.5 g. -methyl-umbelliferone i n 100 ml. hydrochloric acid (sp.gr. 1.19). The mixture was heated in a test tube in boiling water for t e n minutes. The sample was transferred with 25 ml. water into a 50 ml. graduated flask. Five ml. of 5 N ammonium hydroxide were added and the volume made u p t o the mark. This solution was used for colorimetric estimation using the Pulfrich filter S 47. The calibration curve was obtained from solutions of potassium nitrate, pro analysi. The results are shown in Table 48. Halogenides did not disturb the reaction. Especially interesting is the observation that it is possible b y this method t o estimate nitrates in the presence of large amounts of nitrites, as the latter give no reaction with the reagent. The colour is stable for many hours. The above method is the most accurate colorimetric method for nitrate estimation
1

Wassiljew, A. S. and Duchinowa, M. M., C. Z. 1942, I, 647.

Colorimetric analysis of nitrate.

mg./ml.
0.100 0.150 0.150 0.200 0.250 0.250 0.300
1

NO3

E1
0.095 0.131 0.127 0.162 0.200 0.204 0.240

mg./ml.
0.400 0.500 0.600 0.700 0.750 0.900

NO!

E
0.322 0.389 0.468 0.542 0.587 0.685 0.761

1.000

Extinction coefficient.

k n o w n t o t h e writer a n d i t i s far superior t o t h e methods stated i n text-books o n colorimetric analysis.

Novalgin sodium. Novalgin sodium was obtained from I. G. Earbenindustrie, and used without any further purification. The solution in water (10 g./100 ml.) had a p H of 7.6. The substance was analyzed in the same way as phenyl-dimethyl-pyrazolone. Phenyl-dimethyl-pyrazolone (Antipyrine). Antipyrine Ph. Su. Ed. X was used for the experiments. Antipyrine was estimated iodometrically by Bougault's method, using the Kolthoff modi fication. 1
Picric acid. Picric acid pro analysi, f r om E . Merck, Darmstadt, w a s u s e d for t h e experiments. T h e substance w a s estimated colorimetrically i n a n alkaline solution ( p H c. 10) w i t h a Pulfrich filter S 43. T h e concentrations of t h e picrate i o n in t h e solutions used for estimations were 0.000070.0002 N .
1

Kolthoff, I . M., Pharm. Weekblad, 60, 194, 1923.

Summary.

When solutions of electrolytes are treated with active carbon a series of phenomena arise which h a v e been the object of intensive study. Since t h e investigations of Bartell and Miller (192232) i t has been known t h a t low-ash charcoals gas-activated a t about 8001000 C cannot adsorb alkali hydroxides, but can adsorb mineral acids, from aqueous solutions. If such a n active charcoal is added t o t h e solution of a n inorganic alkali metal salt t h e solution becomes alkaline. The alkalinity of t h e solution increases with rising salt concentration. On such treatment with charcoal, solu tions of organic salts become either acid or alkaline, t h e acidity or alkalinity decreasing with increasing concentration of t h e salt solution. Such changes i n t h e reaction of a solution brought about b y treatment with charcoal are termed "hydrolytic adsorption". If t h e charcoal i s activated a t temperatures below 600 700 C i t adsorbs both mineral acids and alkali hydroxides. Solutions of inorganic salts treated with such charcoal become acid. A review is given of recent theories concerning t h e adsorption of electrolytes o n active charcoal. I t includes Bartell and Miller's theory of 1924, Miller's hydrolytic theory, t h e so-called oxide theory and finally Frumkin's electrochemical theory. None of these theories is capable of explaining all t h e experimental obser vations. The author h a s gas-activated active charcoals prepared from commercial sugar. I t has been possible t o confirm i n principle t h e experimental results of King and co-workers (193738) con cerning t h e influence of t h e activation temperature and t h e mode of cooling upon t h e adsorptive properties of t h e charcoal. Charcoals prepared b y gas-activation a t 800 C, which have not t h e power of adsorbing alkali hydroxides from aqueous solu tions, are termed b y t h e author "H-charcoals". The charcoals activated a t lower temperatures which d o adsorb alkali hydroxides
1 2 4 4 5 9 3 Brje Steenberg

177

are called "L-charcoals". The present investigation i s i n t h e main limited t o the study of electrolyte adsorption on H-charcoals. I t i s shown t h a t t h e adsorptive properties of t h e author's H-charcoals with respect t o solutions of electrolytes are the same i n principle a s those of Bartell and Miller's charcoals. The rate a t which t h e present author's H-charcoals adsorb mineral acids is considerably lower t h a n t h e values given i n the literature. I t is shown that a standstill is reached i n t h e adsorp tion only after about 50 hours contact between the charcoal and t h e acid. The amount of mineral acid adsorbed from a solution decreases w i t h rising temperature. B y a comparison between t h e adsorption and desorption of mineral acids o n H-charcoals, and b y investigations of t h e effect of temperature o n t h e adsorption, i t i s shown t h a t a thermodynamic equilibrium can be attained. Adsorption from solutions of organic electrolytes proved t o continue after months of contact between H-charcoal and t h e solutions. The author demonstrates t h a t t h e presence of non-electrolytes i n a system consisting of H-charcoal and a n adsorbable electrolyte i n aqueous solution h a s a n effect upon the state of equilibrium, with t h e result t h a t t h e amount of adsorbed electrolyte decreases. I t is of interest t o observe t h a t it is possible t o desorb a n electro lyte from a n H-charcoal b y adding t o t h e system a n organic liquid immiscible with water, provided t h a t the adsorbed electrolyte i s not soluble i n t h a t liquid. The phenomenon is shown t o arise from t h e greater ease with which charcoal is wetted b y organic liquids than b y water (contact angle). I t is also shown that i t is not possible t o desorb alkali hydroxides from L-charcoals b y t h e addition of non-electrolytes. The researches mentioned above are significant i n t h a t t h e y render i t conceivable t h a t the forces acting i n the adsorption of electrolytes on H-charcoal are of t h e same t y p e a s those i n t h e adsorption of non-electrolytes o n charcoal. The latter forces are generally assumed t o be t h e so-called v a n der Waals' forces. The conditions prevailing i n t h e adsorption of alkali hydroxides on L-charcoal make i t feasible t h a t this adsorption is brought about b y electrovalent forces, as is assumed i n t h e so-called oxide theory of electrolyte adsorption on charcoal.

A comparison is made between the oriented adsorption of, for example, paraffin chain salts at the water/air interface with the electrolyte adsorption at the H-charcoal/water interface, and it is assumed that electrolytes are, in fact, oriented in the latter case. It is supposed that, from aqueous solutions of a strong electrolyte consisting of an organic and an inorganic ion, the organic ion is primarily adsorbed by the charcoal, i. e. is bound by van der Waals' forces. The adsorption of the inorganic ion is termed sec ondary, since this ion is supposed to be bound by electrostatic forces to the primarily adsorbed ion. A consequence of these suppositions is that it should be possible to exchange a secondarily adsorbed ion for another secondarily adsorbable ion with the same electrical sign. The author demon strates that it is possible to apply the Donnan theory to a system consisting of an H-charcoal and a solution of an electrolyte. The applicability of the presented theory is shown by experi ments in the adsorption of organic electrolytes with either organic anions or organic cations, and by adsorption experiments with mineral acids. By a series of experiments with H-charcoal and picric acid solu tions the possibility is shown of exchanging the hydrogen ion of the adsorbed picric acid against other cations by the addition of inorganic electrolytes. The primarily adsorbed picrate ion is not desorbed by this procedure. The exchange constants for secondarily adsorbed hydrogen and silver ions, and for hydrogen and copper ions, on an H-charcoal with primarily adsorbed picrate ions have been determined. In the adsorption of basic dye-stuff salts, such as methylene blue chloride and crystal violet chloride, the inorganic anion, but not the primarily adsorbed organic cation, was found to be expellable by the addition of inorganic electrolytes. From solutions of mineral acids the hydrogen ion is adsorbed primarily and the anion secondarily. It is shown that the Donnan theory can also be applied to a system in equilibrium containing H-charcoal and two mineral acids or one mineral acid and one alkali salt. The exchange constants for a number of inorganic ions in such systems have been determined. It is found that the inorganic anions can be arranged, with respect to their secondary

adsorb abilities, in a series corresponding to Hofmeister's lyotropic series, the thiocyanate ion being the most readily adsorbable. The fluoride ion, on the other hand, is very easy to expel from the charcoal. The differences between the adsorbabilities of the anions investigated are very striking. It is, for example, possible with the aid of an H-charcoal to separate iodide ions from chloride ions in an acid solution of sodium iodide and sodium chloride, even when the ratio of chloride to iodide is very great. The investigation has thus demonstrated that after the adsorp tion of an electrolyte on an H-charcoal the latter functions as an ionoid. According as whether the cation or anion of the electro lyte is primarily adsorbed, an anion- or a cation-exchanger is obtained. On the basis of the applicability of the Donnan theory t o the adsorption of electrolytes on H-charcoal the author has presented a theory of hydrolytic adsorption. The phenomena included under this term are interpreted as analogues to the so-called Donnan hydrolysis. It is shown that all observations concerning the hydro lytic adsorption of inorganic and organic salts on H-charcoal may be interpreted with ease in accordance with this theory. In a study of the hydrolytic adsorption of a dye-stuff salt, the organic ion of which is completely adsorbed on H-charcoal, the hydrolysis was found to be dependent upon the volume of the solution. This effect is predicted by the Donnan theory. It is sup posed by the present author that if the effect is to be quantitatively interpreted, a theory of the density of ions on the charcoal must also be introduced. The investigation finally treats the primary adsorption of a given kind of ion and its dependence upon the presence of other primarily and secondarily adsorbable ions. It is shown that the primary adsorbability of hydrogen ions is greatly reduced by the presence of organic dye-stuff ions, irrespective of their electrical charge. Conversely the quantity of organic ions adsorbed from a solution is increased by addition of mineral acids. This effect is not characteristic of hydrogen ions alone, but is shown by all in organic cations, those of higher valencies having the greatest in fluence. The kinds of inorganic anions present have no effect upon the adsorption of the organic anion. The quantity of organic

cations primarily adsorbed from a solution is increased by the presence of secondarily adsorbable inorganic anions, the order of influence of the latter being identical with the lyotropic series. The primary adsorption of hydrogen ions from a solution of mineral acid is increased by the addition of inorganic salts. The magnitude of the effect is conditioned by the nature of the anion of the salt. Here also the ions act in accordance with their positions in the lyotropic series.
On t h e basis of t h e Donnan theory a theory for t h e observed salt effects m a y be developed. This theory is tested i n t h e quan titative respect. I t is shown t h a t t h e theory presented b y Cassie a n d Palmer i n 1940 concerning t h e influence of salts o n t h e surface tensions of paraffin chain salt solutions i s also applicable t o t h e systems under consideration, and that this latter theory leads t o results corresponding i n principle t o those derived from t h e Donnan theory.

The present author's theory of the adsorption of electrolytes on H-charcoal is not founded on the assumption of adsorption forces specific for H-charcoal, or on hypothetical chemical compounds on the charcoal surface, as is the case with a number of earlier theories. The experimental results of the present investigation indicate a striking parallelism between electrolyte adsorption on H-charcoal and electrolyte adsorption at the water/air interface. The existence of this similarity seems to be of importance in the continued study of both these phenomena.

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