National Academy of

Sciences National Research CounciI NUCLEAR SCIENCE SERIES

The- Radiochemistry of Zinc

_____ .- j.

COMMITTEE
L. F. CURTISS, Chairman National Bureau of standards

ON NUCLEAR
ROBLEY

SCIENCE
D. EVANS, Vice Ckubn.un Institute of Technology

Maamchuaett@ Secretiy Corpratlon J. W. IRV~, Massachusetts E. D. KLEMA Northwestern W. WAYNE University

J. A. DeJUREN, Westtnghouae C. J. BORKOWSKI oak Ridge National bbomtory ROBERT G. COCHRAN Texas Agricultural and Mechanioa.1 College SAMUEL EP8TELN Callfornta Institute of Teduology U. FANO National Bureau of Standamla HERBERT GOLDSTELN Corpofition

Electric

JR. Institute of Teohucdogy

University

MEINKE of Mlchlgan

J. J. NICKBON Memorial Hospital, New York

ROBERT L. PLATZMAN Lsktomtoire da Chide Physique

Nuolear Development Anertca

of

D. M. VAN PATTER Ba.rtol Reaearoh Foundntlon

LIAISON MEMBERS
PAUL C. AEBERSOLD Atomlo Ene~ Commiaslon J. HOWARD McMILLEN National Science Foundation CHARLES K. REED U. S. Air Force WILLL4M E. WRIGHT Office of Naval Reeearoh

SUBCOMMITTEE ON RADIOCHEMISTRY
W. WAYNE University GREGORY MEINKE, Chdnnon HAROLD kmBY Mound Lahorstcmy GEORGE LEDDICOTTE Oak Ridge National Lahoratcuy JULIAN NIELSEN Laboratory Hanford Lalxmatories ELLIS P. STE~BERG Argonne National Laboratory PETI?R C. STEVENSON Universl@ of California (Livermore)

of Mtohigan R. CHOPPIN

Florida State Univeral~ GEORGE A. COWAN Los Alsmos gclentlflo

ARTHUR W. FAIRHALL UnIverai~ of Waahtngbn JEROME HUDIS Brookhaven National Labcmtory EARL HYDE Universl@ of California

(Berkeley)

LEO YAFFE Mc@.11 Urdveralty

CONSULTANTS
NATHAN BA LLOU Centre dEtuda de lEnergle Mol-Donk, Belgium Nuoleshe JAMES DeVOE University of Miohigan wILLIAM MARLOW

National Bureau of Stadards

The Radiochemistry
By HARRY G. HICK9
Lawrence lhiver8ity Livermore,
June 1960

of Zinc

Rdiation

Laboratory

of Calijbrnia California

Subcommittee Natiunal Academy

on Radlochemietry Natimal

of Sciences

Re8earch Cwncfl

Printed in USA. Pr~

80.76. Anllabla

from the -e

of Tdmtcm.1

~eom

25, Dqmnmemt of Conmarca, WMhiB@OO D. C.

FOREWORD
The Suboommlttee on Radiochemistry Is one of a number of subcommittees working under the Committee on Nuclear Science within the, National Academy of Sciences - National Research Council. Its members represent government, Industrial, and. .unlverslty labomtorlea In theareas of nuclear chemistry and analytical chemistry.

The Subcommittee.has concerned Itself with th,ose areas of , such as the dollecnuclear science which Involve the chemist tlon and distribution of ~dlochemlcal procedures, the estab,llshment of epeclflcatlons for radlochemlcally pure reagents, availability of cyclotron time for service irradiations, the place of radiochemlstry in the undergraduate college, program, etc..

This series ofmonographs has grown out of the, need for up-to-date compilations of radiochemical Information and procedures.. The Subc.ommlttee has endeavored ho present a, series which will be of msxlmum u6e to the worklngjsclentlst emd which contains the, lated available Information. Each monograph collects In one volume the pertinent information required for radlochemicaI work with an individual element or a group of closely related elements.

@as byt~ the

An expert In the mdlochemlstry of the particular written the monograph, followlng a standard format, The.Atomic Energy. Commieslon has Subc,omlttee. prifiting of the series.

element developed sponsored

The Subcommittee is confident these publications .useful.not only to the radlochemlst but also to the worker In other fields such as physics, biochemistry who wishes to use radlo~hemlcal techniques.to solve problem.

will be research or medicine a specific

.. ,.

W. Wayne Melnke; Chairman Subcommittee on.Radlochemlstry

ill

,. TO: MS-P362 :i

~ThlsSpawfor,lJhrary Use

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1. t
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CONTENTS

I.

General Chemistry

Reviews ,of Zinc Review of Isotopes of those Interest zinc salts salts

of the .

Inoi ganic . .

and Analytical . . . .

. . . . . . . . . . . .
. .

.
. .

1 2 2

n. III. IV.

Gener& Table Review of Chief 1. 2. 3. 4. 5. 6. 7. 8. 9. 10.

of the Radiochemistry of Zinc Features . of Zinc .

of Zinc . . .

Chemistry

to Radiochemists . of zinc of zinc . . . . . . .

. . . . .. . . . .
. . .

. . . . . . . . .
. .

. . . . . . . . .
. .

. . . . . . . . . . . . . .

2 2 3 3 7 13 17 20 28 39 40 41 43

Metallic Soluble Insoluble Analytical Complex Chelate Solvent

determination ionn of zinc compounds extraction of zinc of zinc

of zinc . . . .

Ion exchange Izotopic Paper

behatior

of zinc

exchange

of zinc . Containing . .

chromatography of Samples

v. VI. VII.

Dis solution Counting Collected for Zinc

Compounds . . .

of Zinc . .

Techniques Radiochemical . . .

Separations . . .

Procedures . . . . 43

INTRODUCTION

This volume which deals with the radiochemlstry of zinc is one of a series of. monographs on radlochemistry of the elements. There is Included a review of the nuclear and chemical features of particular Interest to the radlochemlst, a discussion of problems of dissolution of a,sample and counting techniques, and finally, a collection of radlochemical procedures for the element as found In the literature.

The series of monographs will cover all elements for which Flans Include revision radlochemlcal procedures are pertinent. of. the monograph periodically ati new techniques and procedures warrant. The readerls therefore encouraged to call to the attention of the author, any published or unpublished material on the radlochemistry of zinc which might be Included.in a revised version of the monograph.

..

The Radiochemistry

of Zinc

--G.H1Iavrence Radiation Laboratory Univprsi@ of California Livezmme, CaMforDIa June 1s60

I.

GENERAL

REVIEWS

OF THE

INORGMWC OF ZINC

AND

ANUYTICU M. C. vol. IV (Van Sneed and. R. C.

CHEMISTRY Braoted, 1%5), of Chemical New York, Hoffman;

Cornprehenaive pp. 9-63.

bcm ganic

Chemiotry4

Nostrand,

~inceton, Methods

ScottB o &andard Ed. , Fifth G. Analysis W. E. Edition F. (Van

~yoia, 1939), Outline

Vol.

1,

N.

H., Furrnen,

Noeitrand, and. J. I.

pp. 1054-1092. o of Methods of Chemic&

Lund@ New

(Wiley, F.

York, G-

1951). E. F. Lundell, Edition H. A. Bright, New and J. York, L Hoffman,

HiLlebrand, Amlyais, &d

Ap plied Inorg-ic A. .E. Edition G. York, E.

Second M. Calvin, York,

(Wiley,

1953). Com-

Mart&ll

Chemistry 1952). Determhaation 1959).

of the Metal

Chelate

(Prentice-Hall, B. Sandell,

New

Calorimetric New York,

of Tracee

of Metale~

Third

(Inter science, Charlot

and D.

B&ier,

Quantitative

Inorganic

Analysis

(Wiley, ..

N&w

1957). E. Lederer =d ~. Lederer, Chromaitography (Eloevier,

New York,

,1957). J. G. Chenxietry C. 1953). ,, ~.

A.
H.

Kitchener, Morkition (Wiley, New Inorgan @

Ion-Exchange EL Freioor, Yo+k, ic .1957).

Reaina Solvent

(Wiley,

New York, b

1957).

Etiraction

WWical

Duval,

Thermogravime6ic

Analyoio

(El~evier,

New

York,

II.

GENERti

REVIEW

OF

THE

R~IOCHEMISTRY

OF

ZINC

1% L. .,

Finston

and J.

MiskeI,

Am.

Rev.

Nuclear

Sci.

~,

269

(1955).

III.

T~LE

OF

ISOTOPES

OF

ZINC

Isotope

T. l~z 2.1

- Type

of decay

Method

of preparation

Znbc zn6

mip

B+, EC.
+
p

Ni58 Ni5s

( a# Zn) (a, n) (p, 2n) or ?Ti60 (a, 2n) (p, n)or Ni60 (a, n)

1.48min 9.33 38.3min Stable 4s. 89% 245 day hr

zk62 zn63
%64

EC, p+,

~: 90%; EC, 10%

cub CU63

zn65
%66 2k67 ~68

EC,

9974; ~+,

17.

Zn64

(n, y),

Zn 66 (n, Zn)

Stable 27.817. Stable 4.11% Stable 18, 56% 13.8 lir 1. T. Pzn68 b, y]

~691q zn69 Zn ~7 zn71 &z lm

57 min Stable 0.62$ 3 hr. 2.2 min

49. ohr

PPP,.

Zn b,.lf) Zn (n, y)
Fid aion

..

For and for

more

complete

information

on the radiation nee D.

of the Strominger,

aikc

imotopea,. J. M. ~,

references and G.

to tie original T. Seaborg,

literature, Table

Holland@r, 585 (1958).

of Isotopeo,

Revn.

Modern

Phya.

IV.

REVIEW

OF

THOSE

FEATURES

OF

ZINC

CHEMISTRY

OF C-F

~TEREST

TO RADIOCHEMISTS

1. Zinc of the metal in eaoily

Metallic in very

Zinc pure form; usu+ly by distillation ductfie and

obtained

impure

metal

produced into

by electrolyeio. Buitable for

E is rnoderateIY targets.

can eanily

be formed

ohapes

The. melting

point,

420C, ments.

is rather

low

and may

pose

a problem

in high-intensity

bombard-

Metallic acids as well Oxidation

zinc

is. a good

reducing thus are

agent, showing given

dissolving its

readily

in mineral character.

as in strong potentials Zn . = = = =

bases, of zinc 2,-

amphoteric

below: E EO = = = 0.762 -1.245 1.216

V V
V

zn+++ Zn(OH)2

Zn+20HZn+40HZn+4NH3 Zn+4CNIn general, zinc, although

+ 2 6-

ZnO~+2H20+2C +++2c Zn(NH3)4 Zn(CN)~ + 2 ~-

E E E

=1.03V = 1.26
V

no difficulty very pure zinc of will

ia encountered ia attacked Nit+ remain or only Co+ bright

in the dissolution elowly ctiyzes for long

of metallic acid.

by hydrochloric the dissolution. periods of time

Addition Surfaces absence

of a u mall of metallic of water

amount zinc

in the

vapor. electroplated are and can be used described 10 ml below. for a final counting sample.

Zinc Two methods 1. in NaOH, to a glass

is easily

of electrolysis zinc

Purified and cell 1 ml

is ,put into KCN

of 5 ~. with

is added. anode for

of a solution that is O. 20 to O. 25M -. 1 The solution is then transferred and cathode. Electrolysis ie carried

fitted

platinum

out at O. 1 to O. 2 amp, 2. .mlfonic solutions. Soluble acids 2 salts

or more, of EDTA

1 to 2 hours. acid), to zinc or poly cyanide from is O. 5 to 20 to bath sodium

(ethylenediaminetetraacetic are added

of anthracene With

or anthroquinone, the current is 95 to 98%. is

the se solutions, cathode NaOH 25 g/l; yield

density The

can vary ztic

15 amp/dm2 70 g/1,

and the

content A typical 46 g/l;

and the total is: Zn,

concentration totaI cyanide,

15 to 80 g/1. 46 g/l; NaOH,

composition anthracene Other

trisulfonate, methods

15 to 25 g/l; of electrolysis 2. Soluble ordy with

and solubilized are described of Zinc

starch,

in the literature.

2 to 5 g/1. 3-9

Salts

Zinc its chemistry The acetate, alkali

exists

in solution

+2 oxidation reactions chloride,

state, need bromide,

which

s irnplifies

in that oxidation-reduction salts of zinc include

not be considered. iodide, nitrate, formate, cyanide,

soluble sulfate,

thioc yanate, and 3.

percblorate,

fluo silicate, complex.

metal

zincates,

zinc -ammonia Insoluble compounds

Salte. of Zinc of zinc are listed below in TabIe I.

The FolIowing

common Table

insoluble

I is a discussion of many of these

of the precipitation compounds.

and coprecipitation

characteristics

Table

I.

Insoluble

compounds

of zinc.

Compound

Volubility, g/100 ml H20

znNH4P04 znco3 Zn3~ -2 Zn(OH)2 a(m3)2 zn(Io4)2 ZnHg(SCN)4 Zn(CZ04)* Zns H20 [Fe(cN)6]2

innol.
O. 0206, v. 01. el. sol. at 25-C sol.

O. 000042 0.87, inool. 0.24, at 15-C at 26-C at 18*C , pH 7.5-8.6 , pH >3.09 at 25C

0.000715, O. 0007, )hydra%ine quant. innol. insol. inool. insol. insol. inool. qwmt. quant. -5-ml fonic acid quant. insol. qwmt. tiol. innol.
q

Zn - 1, 2- di (allylthiocarbarnyl
Zn--thrdate Zn-5-bromo-anthranilate Zn-5-iodo-anthraailate Zn- 5 -methylZn-3, anthranilate

5-dibromo-anthranilate

Zn-N-methyl-amthraAlate Zn-O(2-amko - l-naphthyla~o)benzoate

, pH 5.5-7 , pH 4.6-13.4 , pH >3.6

Zn-8-hydroxqukolate Zn-8-hydrnxyquinoLine Zn-2-hydroxy Zn-mercaptoben~ Zn-pyrid@e Zn-qukaldate Zn-5, 6-ben=oquinaldate H20

- 1 -naphthaldehyde othia801e

, pH >7

tiiocyanate

qwit. , @
inaol.

2.85

Zn-aalicylaldoxime Zn-tartrate, (ooluble C4H406 Zn- H20

, pH 8.5 at 25C

0.036,

in excen o ~rtrate) insol.

Zn-tetramethylamtiodiphenylantiPyrinylcarbinolthiocyanate 39 &-methyl xtmthate 39 &-ethyl xantbate 39 Zn-n-butyl xanthate Zu borneol glycuronate

O. 36 0.15 0.12 irlool.

Zinc

ammonium endpoint Cd,

phosphate.

The

precipitation expect etc.

iq carried elements

out at the phenolwould coprecipi-

phthalein tate, Zinc sho~d Zinc carry In(III), SC(III), Ru(III), l% EDTA,

and one would Fe, AU rare

that many

Euch as carbonate.

earths, with

elements

ins olubl e carbonat

qs and hydroxides

coprecipitate. potassium dIr(I~), Ag(I), Te (IV), only ferrocyanide. Bi(IJ.1), La(III), Ti{IV),. .U(VI), lAn(H), Fe (II), Zn3KZ Cd(II), [Fe(CN)6]2 Co(II), Hg(II), precipitated CU(H), at pH 1

will
Ge(IV),

Sb(III), Fe(II), Th(IV),

Ce(III), Mn(ll), and

Gd(?II), Ni(~),

Ga(III), Sm(HI),

Pb(I.1), Y(III),

Nd(III), Fe(III), 10

Zr.(IV),

while

Mo(VI),

Pd(II), of

W (VI), Fe(II), acid,

end V(V) Ag(I), Mn(II),

do not Zr(IV) and and

carry.

In the presence

and Ag(I),

coprecipitate. Zr (IV) Zr(IV) carry. does not

In the presence Ag(I) does not

of nitriloacetic coprecipitate from does Zinc fluoride not carry,

in the presence evolutions.

of thiosulfate

coprecipitate lM HC1, Cd(II)

If the precipitation

and the precipitation Zbic hydroxide salts. will The

is quantitative. precipitate solubili~

iB carried out in 11

hydroxide.

in the &I range product 1.8 of Zn(OH)2 X 10-14.

7 to 13 in in water Feitknect

the absence at 20 C has and Haberli13 variety The

of ammonium been reported the

by Richard volubility and anions

et al. , 12 to be of Zn(OH)2 frorp

report

product

of ionic

strengths

to range

with solutions of a -17 -16 5 x 10 to 6x10 .

reaction Zn(H20)30H 14 6 to 12, except zti.c does not form radiocolloide forms. paper and does not 15 Kvamme, at pH!s of + H+= Zn(H2@~,
PK =

9.36

was

studied

by Achenza.

In the pH range plate out on platinum hand,

by precipitation the adsorption of zinc The M

of hydroxy of zinc on filter

16

on the other 3.5 (2.7 zinc The to 10.5. x 10-6

studied

Mzimum ~) was90%

adsorption at pH 6.5.-4

in trace

concentration decreaaes constant with increashg

adsorption and remaks

concentration zinc also

to 10~0 at 3 X 10 well on glass

thereafter.

adsorbs alBo

and Fe(OH)3, Fe(OH)3 and

in this Cr (OH)3

pH range. to some ions. 17 extent h

Ztic will nearly neutral

coprecipitate even

solution

in the presence

of ammonium on Al (OH) with

Kovalenko18 NH cl ~+ 1 +

studied

the carrying Adsorption with with

of zinc &creased

- 4QH O1utiOne 9 concentration, and decreased Adsorption very little increased

precipitated from 3 increasing initial and .NH40H Zn++ con-

increastig increastig

NH4C1 initial

centrations. There was

concentration. was at

adsorption

at pH 4; the maximum

adsorption

pH 6. mintiize Ztic

High

concentrations

of

~4Cl

and low

cone entrations

of

NH40H

coprecipitation. Zinc will coprecipitate and zinc the lower Cu(Il), Ag(I), K+, Fe(m) 19 with I?e (104)3

periodate.

2~e203

- 7H20
M . The

to the extent
higher Zinc W(3X, clo~, (small interfere. Mn(lI) Zinc
will

of O. 4%

at pH 3.5

concentration

of. 7 X 10-3

the

zkc

concentration,

the coprecipitation. (in large are Mg++, Sb(~), amounts), with Bat+, Co(II)r zinc, Ni(II), while

mercurithiocyanate. Bi(lIO, Cl-, NO;, Cd(~),. SO:, Pb(II), According the precipitate Ca, Sr, with Ba, zinc

and Hg(D) Na+, NH:, As (V),

coprecipitated Cat+, Sr++,

l?e+~+ do not and

~~~ts),

As (III), to Rulfs

Sb(V),

and Sri(W) Ni(II),

and I&by,

21 Fe(III), weight. Ni, acid Cd,

CU(H),

color
oxzlate.

but are Fe(lI), oxalate of zinc

of negligible Mn(lI), from Co, acetic

Pb,

coprecipitate sulfide. the elements

solutions.

and rare 22

earths

Zinc half

Precipitation

sulfide (see

by ammonium ref. 23, p.

sulfide 6 1). The

can carry sulfide elements can

in the periodic under a wide

table

be precipitated coprecipitated With pH 2 to 3, lh(DI),

=riety

of conditions scheme

(the following has

imply

that the classical formate,

of =alysis

been

us cd). T1 (I), Mn@),

and with Cd(~), 24

citrate, carry,

or cbloroacetate but there buffer, is is

btier, from 20% nickel with

Ga(HI), Fe(lI), there

and Ni(II) With sulfate

separation pH 2, and

and Al(IH). is separation conditions:

-bisulfate There NH40H

NH4SCN, under the

from

Co(,II). with

25

separation

from

following arnide, grey

buffer

NH4C1,

precipitate

thioacetto turn

heat, cool quickly and centrifuge as soon as precipitate 26 Zinc sulfide may also be precipitated from basic 27. s olut ions. @iS). Ca&nium can be separated 28 3 ~, H2S04. can be carried lower than .0.5 from zinc by precipitation

starts cyanide

of the

cadmium

sulfide

from Ztic

sulfide at pHfs

copper.

sulfide

precipitated less than

with 80C.

thio29..

acetamide Zinc

and temperature Zinc solution as

didlyldithiocarbamido pH 7.5 dried and Pb(II) for and 8.6 at .105-C, may

hydrazine. by an alcohol and weighed

is pr ec ipitatbd of the reagent, 30 them

quantitatively washed Ni(II) at lower with interfere, pHJs --

between acetone, CU(II) 2.5 Zinc zinc CU(II)

Zn(C8H12N4S2). precipitatbig

be removed

by first Pb.

to 3.5

Cu,

and 5 to 6 for Below

anthranilate.. completely does not

pH 3.09,

in .one-hslf carry.
32

anthranilic acidin excess will precipitate 31 31 to one hour. Hg(II) and Cd (II) coprecipitate,

Zinc - 8-hydroxyq all metals p. 115). except

uinolate. alkali

This

precipitate earths

is far are

from

specific, (see

since ref.

nearly 23,

and alkaline

coprecipitated

Zinc - 2-hydroxy Be(II), Zinc Pd(II),

-1 -naphthaldehyde. Mn(II), Ni(ll),

Cu(ll),

Mg(II),

and Co(II)

coprecipitate. zinc,

Ca(II), 40

Sr (H),

Ba(J.1),

mercaptothiazole.

quantitatively zinc will tion, ture. p yridine carry

Precipitates 33 at pH 8 or above. CU(LI),

aluminum,

thorium,

and bismuth

thiocyanate.

Cd(II),. is lowered

and Ni(II)

pyridine the

thiocyemates zinc concentra-

zinc;

the zinc-carrying the concentration CO(D), Ni(ll),

by lowering

lowering 34

of other and Fe(II)

metal, will

or increasing coprecipitate with

the temperazinc pyridine

CU(II), 35 thiocyanate. Zinc quinaldate.

Fe(III)

and Ni(II)

coprecipitate.

36 37

Zinc-5,

6 -benzoquinaldate.

Co (II),

Mn (II),

and Ni (II) coprecipitateo

Zinc

methyl

xanthate.

Ni(II),

As(III),

Cd(II),

CO(H), from does

and Cu(Il) an acid not form The

coprecipitate. solution com corre -

38

Borneol

glycuronic

acid.

with borneol pounde sponde with to

glycuronic other

acid.

Zinc is precipitated 38a The reagent except

or neutral insoluble

common

metals 2H20.

cadmium.

precipitate

Zn(C16H2507)2c

4.
A general by Beamish Gravimetric zinc review

Analytical

Determinations

of Zinc is presented listed below.

of gravimetric and volumetric analyses 41 The more common methods are and Wedland. Determination phosphate. phosphate method for According followed zinc. to, Hillebrand by ignition The a tenfold conditions excess

ammonium zmrnonium

et al. , 20 the precipitation is the

of zinc best

to the pyrophosphate for

grav-imetric

pH 6.5,

temperature

80-90C,

precipitation are 42 and a ratio of pho~phate,

of about 200 to 143; tartrate below lN and citrate 4-4 The precipitate is ZnNH4P0 H O which below O. 25N do not interfere. 4242. may be dried at 100-105 C (see ref. 20). Vance and Borup. recommend 45 recommends ignition at 6 IO C or above. ignition at 500 C. ~val Zinc mercurithiocyanate. 03 or HC104 Zinc mercurithiocyanate temperature cai be precipitated of 31.5 from g

of ammonium

ion to zinc

5~0 H2S04,

at room

by a solution

NH4S.CN filtered

and after

27.1

g HgC12

in 1000 and should

ml

of water.

The

reagent

should

be The

preparation

precipitate ZnHg(SCN)4. Zinc oxalate.

can be dried 21, 46

from

710-2700C,

be renewed every year or SO. 45 and hae the composition

The

procedure solution

for

precipitating

zinc

oxalate zinc, Add

.is as follows: add 85 ml 4 ml diethylfor

to 10 to 12 ml glacial oxalate, an hour Zinc after ZnO acetic stir

aqueous acid

containing 1 g -monium to about

O. 5 to 50 mg oxalate. Keep 47

containing quickly

and heat

100 C.

at this

temperature

and a half; Zinc

Mter sulfide

washing,

ignite

to ZnO from The

at 900 C. H2S04 solutions is then at pH 2 to 3 ignited to

Eulfide. fuming

at 1000C.

off chlorides 45

is precipitated 20 and nitrates.

precipitate

Zinc -1, basic, with heat

ffiter.

2 -di (allylthiocarbamyl add dilute HZS04 until

)hydrazine. some

30

Add

ammonia

until

solution solution

ia

precipitate Add

remains, excess

clarify

citric

acid,

and dilute bath. Add

to 200. ml. sodium

a slight and sodium

of reagent, digest, as

and and

in a water Wash

acetate

hydrotide, and weigh

wifi

hot water

and acetone,

dry

at 105 C,

nc8Hl2N4s2Zinc anthranilate. erid point) then with Precipitation at about alcohol. 100 C. Dry is carried Digest out in neutral 15 to 20 minutes, weigh as solution(methyl wash with diluted 42, 48, 49

orange reagent,

at 105 0-1 10C,

ZnC7H602N.

Zinc-O-

(2-amino5.5

1 -naphthylto 7. The

azo)benzoate. conversion

Precipitation factor to zinc

is quantitative is O. 1012. High saIts.

50

in the pH range resulte are

obtained

in the presence ~filer

of large

amounts

of ammonium

Zinc -8 -hydroxyq for

uinolate. Adjust Heat heat dry

and Hmter,51 red

give

the foIIowing and buffer

procedure ammonium in

the precipitation: acetic acetic with will acid. acid,

to methyl

end point

with

acetate O. 8N wash pound

to 60C,

add. slowly bo~ing for

a 27. excess 2 to 3 minutes,

of reagent cool

to nearly

30 minutes, This com-

water, sublime

at 160 C, 4245

in vacuum

and weigh as 52 at 275- 325C. Zinc is precipitated aa Zn(C7H4NS2)2. by the reagent

Zn(C9H6NO)2.

Zinc -mercaptobenzothiazole. dried Zinc dried at 105 - 120C, quinaldate. at 105C,

by the reagent 33 at pH 7 36 and

at pH 8,

and weighed

Zinc

is precipitated as

100C,

and weighed

Zn(C,loH602N)2

H20.

Zinc-5,

6, benzoquinaldate.

Zinc

is precipitated contains

by the reagent one molecule

at pH 2.85, of water of

and dried

at 110 - 115 C; the precipitate 37 crystallization. Zinc salicylaldoxime. 10 minutes at 90-100 a mixture

for

Precipitation is complete 52a The conditions C. of monoform. to ZnO

at pH 8.5, must

and is digested carefully mono

be controlled The

or one obtaim (ZnC7H502N) and Flagg, weight. Zinc plete 53

and di - tialicylaldoximes. According at about to Duval,

is the weighable one muEt ignite

45 and Rynasiewicz a reproducible

950 C to obtain

tetramethyldiarninodiphenylantipy in HC1 or H2S04 the 1, from

rinyl

carbinol. The is

Precipitation is dried 45

is com from

O. 5 to 1. 5N. factor to zinc

precipitate

105 -11oC; Figures

conversion 2, and

O. 0556. from Duval.

3 and Table

~ are taken

Volumetric Zinc

Determinations yanate. standard The precipitate is dissolved end point in 4M to 73 HC1 of

mercurithioc

and is titrated the iodine Zinc color

with

in chloroform. The with precipitate KMn04.

The iodate. 49, 55

is the

disappearance

oxalate. titrated Zinc

is dissolved 47

in dilute

sulfuric

acid

and the

oxalate Versene.

can be titiated T end point.

at pH 6.5 56 Pribi157

with

disodium Ag(I), being

versenate CU(II),

to the Mn(II), by reaction

Eriochrorne Ni(~), with

black

masks

Co,(II),, chloral,

and Hg(II) with CN-, the 57 61 or formaldehyde.

Zn(C,N)~

destroyed

Colortietric

Determinations

Dithizone. plex Azo in carbon dyes*

Zinc

may

be. determined

a solution

of the

zinc -dithizone density complex

com49

tetrachloride and Guha

or, chloroform Sircar 58 used the

by the optical red-brown

at ~ 30 m~. formed at

Das

pH 3.4 length Zincon. and 9.5 620 m~.

to 7 by zinc was given. Rush with

8-hydroxyqutiolate

and m-~ino

benzoic

acid.

No wave

and Yoe

59

determtied

zinc

colorirnetrically

between

pH 8.5 at

zincon

(2-carboxy-2

l-hydroxy-5

l-sulfoformazylbenzene)

3
54 ~ ~

-- ____ ___ ___ ___ ___

347

---

_ 10,

100 ~ 1 lm, Ll
W9 q

. x? =.

272 ~ ? , lgi 2s9

520 , 296

, 811 94s

f m

Fig.

1.

Pyrolysis

curves

of zinc

derivatives.

1. Electrolytic zinc. 2. Hydroxide via aqueous ammonia.. 3. Hydroxide via mercury (II) oxide. 4. Hydroxide via dirnethylamjne. 5. Hydroxide via morpholine. 6. Hydroxide via pipe ridtie. 7. Mphide. 8. Sulphate. 9. Zinc ammonium pho 6phate.

10

9
132 Z& S&

, ma

I
Fig. 2. Pyrolysis curves

590

946

of zinc an.rnotium

derivative.

Zinc cyanamide. carbonate. 11. 10. Basic carbonate via 12. Basic carbonate via guanidinium carbonate. 13. Basic carbonate 14. Dipyridinozinc (II) via trimethylphenylammonim carbonate. Tetrathiocyanatomer curate (II). 16. Oxalate. thiocyanate. 15.

11

42

127

284

9s5

f026

B ma ~ , 47 so 1 2ss

@ 62 w

20$

, W24

w m
100 q 972 ma

407

f024

Fig. 17. 20.

22.

3.

Pyrolysis

curves

of zinc

derivatives.

24.

bthranitate. 18. 8-Hydroxyqukaldtie Dithizone complex. Quinaldine complex.

Oxine complex. 5- Bromo-anthr-ilate. 19. complex21. Salcylaldcxdme complex. 2. 7-- Diamtiofluorene complex. 23.

12

Table

II.

Thermogra-etric

data

of zinc

compounds.

45

Precipitating

reagent

Form

weighed

Temperature

limits

Electrolysis Aqueous ammonia Mercury (II) otide Dimethylamine Morpholine Fiperidine Hydrogen Eulphide W%lphuric acid Sulphuric acid *~onim phosphate Ammonium phosphate Sodium pyrophosphate #unrnoniurn carbonate Ammonium carbonate *Cyanamide Cyanamide GwmMinium carbonate ammonium T rirnethylphenyl carbonate Tbiocyanate + pyridine Thiocyan.ate + pyridine *Th.iocyanatomercurate (~) Thiocyanatomercurate *oxalic acid Oxalic acid A.nthran.ilic acid *5-Bromo-~thranflic 5-Bromo-znthranilic Oxine *Ofine 8-hydroxyquinzldine Salicylaldoxime Dithizone 2. 7-Diarninofluorene *Quinaldic d (It)

Zn ZnO ZnO ZnO ZnO ZnO ZnO znso4 ZnO ZnNH4P04 Zn2P207 Zn2P207 5ZnO 2C02 ZnO ZnCN2 ZnO None ZnO [

< 54 >1010 > 970 >1000 > 910 > 920 > 943 300-788 > 950 Between 500 and 167 > 610 > 610 370-879 >looo~ 105-152 > 812D None > 247 < 71 > 780 50-270 > 820 < 75 > 590 > 500 < 123 > 955 < 65 127-284. 100-220 None < 68 .> 972 < 126

Z4C5H5N2]

(CW2

:~Hg(CNS)4] ZnO ~~~24 2H20

acid acid

ZnO Zn(NH20 C6H3BrC02)2 ZnO Zn(C9H60N)2 1-1/2 H20 Zn(C9H60N)2 Zn(C10H80N)2 None ;::13%ON4S ~c10H602~2 H20

Taken dir tly from by C. DuvA.$g * Suitable for gravimet

the table

on page

284

of The- ogravimetnc

Xumlysis

ric

determination

of zinc.

4-chlororesorcinol. from solutions

Stewart of diethyl-dithio-

and Barlett60 c=bmate after

extracted at pH 8.5. extraction. of Zinc for

zinc

into

chloroform

4-chlororesorcinol

wam ueed

as a calorimetric 5.

reagent Complex

Ions

Zinc, number

with

the

4s and 4p orbitals ione and chelate

available

bonding, are

forms of great

alar impor

ge -

of complex

compounds.

These

1~

tance ions

in the understanding are listed below given

of the chemistry Ill. &e Lag K

of zinc. is reported one less

Some

of the

complex for

in Table ion from

as the ligand.

constant The

formation

of the

ion with aa A.

ligand

is sometimes

referred

to in the table

TabIe

HI.

Complex

ions

of zinc.

Completing

agent

Reaction ZnNH. ++

product

Log

Ref.

NH3

>

2.37

62 62 62 62 62 63 63 63 63 63 63 80 79 64 64 65 65 66 67 69 67 68 62 70 71 62 69 62 72 73

zn(NH3)2++ zn(NH3)3++ zn(NH3)4 overall ethylene diamine znA++

znA2++ znA3++

++

2.44 2.50 2.15 9.4 5.77 5.06 3.28 5.73 6.24 6.11 11.9 15.4 10.92 17.8

cis - 1, tramtram

2-cyclo-hexane ~, 2-cyclo-hexane

diamine diarnine diamine

z~t+
znA++ ZIA++ znA++ Zm%++

-1,

2-c yclo-heptane jne

Triethylene-tetram tetraethylene-pentamine catechol disulfonic

acid

(tiron)

ZIA= z+ znA=(p= Znwi-{p= o) o)

11.68 4.58 4.71 4.25 3.55 1,91 9.4 19.0 17.0 2.3 -0.2 4.69 1,9 0.73 0.77

citric

acid

Zn CitZn CitZn CitZn (Cit)~4

Zn(OH) Cit, pH 7 to 12.5 CNZn(CN)~ Zn(CN)~ Zti;

zti~

glutaric acetic
S20;

acid acid

Zn(S203)j

pyridine F-

Znq+
znF zriF+ +

14

Table

IL

(Cent d

Completing

agent

Reaction

product

Log

Ref. 74 74 74 62,75 74 76 74 76 74 76 76 62 74 62 62 78 78 78 78 62 66 66 66 66 .

cl-

ZnCl+ ZnC12 ZnCl~ ZnC1

0.19 0.60 0.71 1.0 t -0.60 0.0 >0.1 -0.15 >0.1 -0.30 -0.52 -2.6 Zn12, ZnI~ >0.05 -5.4 15.4 see ref 77 0.5 0.8 0.0 1.3 4.2 + 1.72 1.40 3.12 3.88 4.85 2.35 5.0 6.23 7.12 1.95 5.64 3.7 2,5 $ 4067 8.97

Br-

ZnBr

ZxiBr + ZnBr ~ ZnBr2 ZnBr~ ZnBr ~ ZnBr~ ZnBr~ I ZnI+, Zd: OHSCNZnO~ Zn(SCN)+ Zn(SCN)2 Zn(SCN)~ SCNZn(SCN)~ Zn(SCN)= bioxalate znHc204

Zn(HC2Q4)2 overall oxalate Zn(C204) Zn(C204)= Zn(C204)2 Zn(C204)~ overall overall glycolic tartaric succinic malonic valine acid acid acid acid Z& Zruk; znA; Znll= 2A znA2

70 66
71 66 69 66 69 71 71 81 81

15

No quantitative Zn(SCNH2CH3)2++, postulate ring. and relative Mg >Ca

date

are

available

on the zinc -thioacetamide Shinigawa involve formation

complex,

82 .83

or the phosphate phosphate

complexes.

and Kobayaehl of a chelate atoms. >Co,

that the ortho strong strengths >Sr >Ba.

complexes

dissociation

of ordinarily-weak are: Fe

terminal >Pb >Zn

hydrogen >Cu >Ni

The Cd >

of the complexes >K >Na.

A qualitative sidering MX~ and separation MX~

discus using M

Bion of the halide an anion is Zn++, in favor resin Cd++, of the

complexes column. or Hg++, complex For

is of value the higher X is Cl-,

when

con-

complexes Br-, or number are fiat

where

and ion,

1- the equilibrium of the the cation

is more The of zinc

a~ the atomic data 85, 86,87

increaBen. strengths

conclusions and cadmium

from

various

relative

complexes

are

The

ZnCl~ Relative

and

CdCl~

complexes

appear

to be of nearly complexes are:

the 2n

same

strength, >Co >

88

strengths

of the bromide

> Cu >Ga

Ni.

89
Figure 4 shows species in hydrochloric acid solution. 138

1 1

I o

1 I

+2

~ a E < Zo :
a K w
>

+1

a
-2

Ill
0.05 0.
I

I
0.5

I
I

1
5

.0

MO LALITY

OF

HCI

Fig.

4.

Average

charge

of Zn(LI)

in HC1

(anion

exchange

Elope

method).

16

6.
Zinc cur sory other forms

Chelate

Compounds array

of Zinc, compounds, of chelate evident compounds from a

a bewildering of Table found Table IV.

of chelate

inspection are

(Compilations

of many

elements

in references IT. Chelate

90 and 91. ) compounds of zinc,

Ligand

Log K

Ref.

amino a-amino proline glutamic

acetic

acid acid

9.72 9.56 10.2

91 91 91
91 91 91 91 91 91 91 91 91 101 91 91 91 91 91 91 101 91 91 91 91 91 91 91 91 91 91 91

propionic

acid acetic acid acid acid acid

9.46 9.19 ,7.30 10.4 7.6 7.8. 12.73 17.56 13.69 17.52 acid acid 16.2

a-N-propylamino a-S-amino 2-amino valeric hexanoic

2, 6-diarnino ar gtiine

hexanoic

8-hydroxycinnoline 8 -hydroxyquinoline 8-hydroxy 8-hydroxy - 4-methylcinnoline - 2 -phenylquinoline - 5- aulfonic - 2 -carboxylic

8-hydroxyquinoline 8-hydroxyquinoline 8-hydroxy 8 -hydr

9.7
20.24 18.72 14.78

- 4-methylquinoline

oxy - 2 -methylquinoline - 2, 4-methylquinazoline

8-hydroxy tyroaine

9.1
)-benzimidazole acid etic acid acid 15.24 7.5 14.36 8.93 10.87 10.43 13.9 -0-monomethyl acid

2- (o-hydroxyphenyl pt e r oylglutamic a-isopropylaminoac 2-amino-

4-methylpentanoic propane

1, 2-diamino ethylene

diamine

difiethylglyoxixne dimethylglyoxime

ether

14.36 11.5 17.5 13.2

G @-diamino
tropolone koj ic acid a-bromo

propionic

tropolone

12.7

17

Table

IV.

(Contld

Ligand a-methyl tropolone

Log 15.7 15.2 16.2 19.3 12.5 7.36 3.3

Ref.

91
91 91 91 91 91 90 90 90 90 90 90 90 91

~-methyltropolone a-isopropyltropolone ~-isopropyltropolone O, O-dimethyl oxalic malonic ethyl diethyl dhnethyl di-n-propyl methyl n-propyl acid acid acid acid acid acid purpurogallin

malonic malonic

3.04 3.24 2.74 3.15 3.10 3.12 18.90 acid 18.2 9.0 20.93 acid 5.68 19.65 15.07 methane methane methane methane 14.42 15.28 15.64 15.07 8.81 8.10 mlfonic acid 5.4 10.3 9.56 9.28 9.02 10.50

.malonic

malonic acid

malonic malonic

acid

2-mercaptoethylamine a-aminoquinoline anthranilic. &mercaptopropionic -8carboxylic acid. acid

9i
91 92 92 91 99 99 99 99 99 91 91 91 90 90 90 91 91 91 91 91 91 ,

5-bromoanthranilic dibenzoyl dibenzoyl p-chloro p-methyl p-methoxy m-methoxy acetylacetone salicylaldehyde salicylaldehyde-5benzoylacetone 2-fur oyl-benzoylmethane methane methane dibenzoyl diben~oyl dibenzoyl dibenzoyl

2-thenoyl.-2-fur

oylmethane 2-ol

1, 3-diarninopropanhietamine 1, 3-diamino-2,

2-dirnethylpropane

10.41 13.66 7.03

2-o-hydro~henylbenzothiazol~ irnidoacetic amino acid acid

euccinic

5.84

18

Table

IV.

(Centd

Ligand & carboxymethylaminopropionic methyl irninodiacetic acid acid )-irnidodiacetic acid acid

Log

Ref. 91 91 91 91 91 91 91 91 91 91 91 91 91 91 91 91 91 91 91 91 91 91 91 91 91 91 91 91 91 91 91 91 91 90 90

6.17
7.66 5.8 7.03 3.80

cyanomethyliminodiacetic N- (carbamoylmethyl glycylglycine glycylglycylgly cine

3.33 etic acetic etic acid acid acid 8.33 5.36 7.7 8.43 8.28 acid 6.86 5.34 7.92 11.93 acid etic acid acid acid 9.8 7.9 4.6 7.6 5.3 acid N, Nl, N1-tetraacetic ethylenediarnine N-triacetic N!-diacetic-N, )-amino-] acid(EDTA} 3.22 16.26 14; 5 acid 14.5 13.17 7.8 16.24 10.45 8.9 5.31 14.65 diamine 12.1 15.92 12.0 14.6

N- Z-hydroxyethyliminodiac di- (2-hydroxyethyl 3-hydroxy )amino

propylirninodiac

2-methoxyethylirninodiacetic 2-methylthioethyliminodiacetic

acid acid

2- ethoxycarbamylaminoethyliminodiacetic 2- (dicarboxylmethyl )-amino

ethyltrtiethylammonium cation etic acid

3, 31 -dirnethylbutyliminodiac ethylenediaminediacetic 2-carboxyethylirninodiacetic carbo~ethyliminodiac 2 -hydroxyethyliminodipr ethyl enediamine nitrilopropionic phenyliminodiacetic ethylene diamine-N, -N, acid acid

opionic N! -dipropionic

N!- 2- (hydroxyethyl)-

-N, N!, acid Ni-dipropionic diethyl

ethylenediamine-N, 2, 2 t-his

[di(carbo~ethyl

sulfide acid diarnine

ethylenediamine-N, N, N, Nr, Nl -tetrakis nitrflo 2.2 acetic acid

N, N!, N1-tetrapropionic - (2-aminoethyl)ethylene

-diamino-diethylarnine sulfide iethylamtie ethyl )- ethylene

2, 21 -diarninodiethyl 2, 2 I, 2 I I-triaminotr N, N - di- (2 -amino

2-mercaptoethylirninodiacetic diethylene triethylene triamine tetrarnine

acid

19

Table

IV.

(Cent id )

Ligand

Log

Ref.

propylene

diarnine

12.57 6.7 6.43 9.52 8.7

90 90

1, 2, 3-triamhopropane O-phenanthroltie alanke aaparagine aspartic histidine leucine proline t ryptophan val ine aminobarbituric ammonia glycine tiron N-hydroxyethyl ethylenediamine diacetic cine sulfonate acid tetraacetic acid acid triacetic -N-propionic acid-N, acid acid N-diacetic acid acid

90 90 90 90 90 90 90 90 90 90
90 90

10.0 12.88 8.93 10.2 9.3 8.10 3.2 13.4 10.1

14.5 8.6 5.4 11.07 18.67 9.42

94 96 97 93 100 102

N.hydroxyethyli.mino N, N-dihydroxyethylgly pyrocatechol-3,

5 -dis odi&n

1, 2-diaminocyclohexane picolinic acid

tetraacetic

7.

Solvent

Extraction

of Zinc extraction has been written

A good by Morrieon Dithizone The

reference 102a and Freiser. Solvents of zinc been

general

work

on solvent

in Or mnic extraction has long

by Holutions used for

of dithizone

in chloroform

or carbon

tetrachloride ence of zinc

analyaie.

extraction

in the pre eence Fig. 5 that

of tartrate. extracts

Figure 5 shows 103 quantitatively When large

the pH depend-

It is apparent to pH Ag, The this 10, with

from

zinc

from amounts

pH 8

two minutes present,

mixing they may

of the layers. be removed with

and Hg are zinc may

first

by extraction

of Cu, 104 at pH 1. acid. k

be recovered Pb, Cd,

by extraction and some

O. 1 to O. OIN mineral the zinc.

procedure,

Bi accompany

20

,
100 -

80 -

60 -

40

-,

Id

20 0

a
2
4 6

10

pH
Fig. 5. Extraction of zinc by dithizone.

Various to prevent extraction Warburton,

complextig

agents

may

be added Cyanide,

to the for

initial inntance,

aqueous

phase

extraction

of other

metals.

prevents of Crowther, solution of

of Ni and Co. and Bracewell

Apparently the beet procedure 105 who first extract Ni with they extract citrate with 10 pg of zinc solution, water.

ia that

a chloroform from one gram

of dirnethylglyoxime. uranium in 5 ml

Then

of 40~0 ammonium solution

~.

pH 8.0 The

to 9.0, layer

and wash is then

the chloroform washed phase. Co, Pb,

of dithizone of

dithizone

with .a O. 05 This Cu,

solution

Na2S, from

and the Tl, Hg,

zinc Bi,

remains Au, Pt,

in the organic Pd, Cd, Ni,

procedure and Mn.

separates 106

Schweitzer with

and Honaker Their

have

investigated in Table V.

anions The

which initiaI

interfere zinc concen-

tration

the extraction. -5 ~ was 10 3~,

data

appear

, the dithizone

concentration O. 10. They

in the organic define the

solvent extraction

1.8x1O coefficient

and the ionic as follows:

strength

~ .

(HD)2
(H+)2

The of zinc

range

of conditions

shown

in Table procedure

VI makes indeed.

the

solvent

extraction for norrn~

with

dithizone

an attractive *L --ULCL~
Lm

However,

radio chemical volubility carrier-free

procedure dithizone

- -- ---a u erluuu dithizonate

--- -uravfDacK -*- Decause in the above

. me .. 01 solvents. For

of both

and zinc such

applications,

volubility

considerations

vanish.

Table

V.

Effects

of varioua into

anions

upon

dithizone

molutiong.

the extraction 106

of, zinc

Organic solvent

Anion aqueous

in phase

Anion molarity.

pH for 50~0 extraction

chloroform

perchlorate iodide bromide tbioc yanate acetate

0.10
0.10 0.10 0.10 0.01 0.10

3.5 .3.5 3.5 3.6 3.6 3.6 3.9 5.9 6.7 4.3 5.3 4.2 7.0 no extn. no extn. 2.7

0.03 -0.03 0.03 0.02 0.02 0.02 0.005 5 x 10-7 -8 1X1O 8 X 10-4 8 X 10-6 0.001 3X1 --1 O-9

chloride citrate

0.10 0.01 0.10 1.00

oxalate

0.01 0.20

nitrilo

acetite

0.001 0.01

EDTA

0.001 0.01

phthalate carbon tetrachloride

0.01

perchlorate bromide citrate

0.10 0.10 0.01 0.10

1.9 1.9 2.0 2.0 no extn. 2.3 2.4 2, 1 2.7 5

50 50 30 30 -8

EDTA benzene perch.lorate citrate chloro-benzene dichloro-methane percblorate perchlorate

0.001 0.10 0.01 0.10 0.10

20 1

Methyl-

dioctylarnine MahIman,

in Organic

Solvents 107 showed that in hydrochloric dioctylarnine acid in organic

Ledicotte, extracts weIl

and Moore into

s olutiona, solvents. into

zinc

solutions

of methylbehavior

Figure

6 shows

the extraction of methyl

of a number The

of eIements solvent seems

dichloroethylene

solutions.

-dioctylarnine.

22

Table

VI.

Volubility in varioue

of zinc organic

dithizonate solvents.

and dithizone 106

Solvent

Volubility, Dith izone

g/1 Zinc dlthizonate

CHC1 ~ CH2C12 C6H6 C6H5C1 CC14

0.03 1 8 20 50

20.3 12.6 3.6 2.5 0.74

0.03

21.0 16.4 2.3 4.6 0.72

0.8

+0.5 +0.1 +0.1

q

*0.3 +0.3 *0.3 * 0.06

0.02

to play

a significant solutions

role

here,

in that

extraction

of zinc

into

dichloroethylene

and xylene into from

chloroform Hf, Zr,

solutions. Pa,

2M HC1 is quantitative, while only 75~0 is extracted lo7 Moore108 showed that zinc .is easily separated 109 and Th by this extraction. Scroggie and Deal extract from 5 ml with 2y HC1. into 10 ml 87. methyl-dioctyltime with a non-

above

completely amine

100

pg of zinc

in methyl-is organic 108 for

obut yl ketone, phase.

u

3-minute

mixing

equilibrated Moore conditions

point

out that

the extraction

condition

are

very

s tiiiar type.

to

adsorption uranium

on anion extracta

,re sin of. the quaternary dilute sulfate

ammonium and zinc

For instance, not 110 . According

from

solutions

doe H

. ZnC14,

to Sc+oggie probably

and Dean, through 111

109

zinc

extracte bonding

as

ZnCl~

or

proceed~g ion.

hydrogen found

and ion association of the extraction with a and

with the amine coefficient slope of +2. has waa

Schtidewolf with

that the logarithm of the amine

linear

the logarithm of one zinc

concentration amine

The

extraction

atom

takes for

two the

molecules

pr~bably ion. )

the form

(RH)2 ZnC14.

(RH+

stands

substituted

ammonium

The i. e. , and

zinc in

species 2~ HC1.

is consistent Schindewolf

with used

that found HC1,

by Kraus

and Neleon, solutions of the b

138

ZnCl~

LiCl,

and Cs Cl

showed

that the change in the organic The reaction

in extraction phase

coefficient therefore

is independent have its

concentration aqueous phaee.

and must

cause

the

is then:

(1)

2RH+C1-

+ ZnCl~

= (RH)ZZnC14

+ 2 Cl-

23

The extraction

slope

of

+2 at lower

chloride by

concentrations

suggests

that

the

of zinc

can be deecribed

(2) (3)

Zn++ ZnC12

+ 2 Cl-

ZnC12

+ 2RH+C1-

= (RH)2ZnC14

The

lowering

of the extraction by the reverse

coefficient (1).

at high

chloride the This

concentrations sIope effect occurs of the is seen with

can be described curve clearly LiC1. at high with

of reaction should

Therefore -.L.

chloride CsC1.

concentrations Maxima occur

approach 1~ CSC1,

at 2M HC1,

but none

Tribut yl Phosphate 112 extracted of tributyl (extraction Co(lI), zinc into kerosene, from benzene, hydrochloric = 34) occurred while and acid from U{VI),

Irving carbon solutions.

and Edgington

tetrachloride Maximum Ni(II),

solutions extraction Mn(ll),

phosphate

coefficient.

2M to .3M HC1. In(II.I),

and CU(II)

did not extract, acid concentrations,

and Fe(HI)

did.

At higher decreased.

hydrochloric The

the extract is acid: hydro-

extraction in roughly used

coefficient the same

chloro-complexes on anion formed

apparently resin.

order there

as the adsorption three phasek

If kerosene

as a diluent,

are

above

5M hydrochloric saturated with

the upper chloric

is kerosene,,

the middle

is tributyl

phosphate

acid,

and the lower this rather

is aqueoue. inconvenient

Benzene phenomenon. extracted

and carbon

tetrachloride

did not exhibit Peppard, phosphate presented which is

Gray,

and Marcus13

zinc

with

undiluted Their

tributyl data are

purified in Fig. salted

fr Orn monobutyl 7. They conclude chloride

and dibutyl that

phosphates.

H2 ZnC14

is the extracting

species

out at higher

concentrations.

Thenoyltrifluor

oacetone

A good dibutyl of zinc pH 4.5 minutes buffered buffered ether

separation solutions into

from

cadmium

is effected

by extraction (TTA). 114

of zinc

into

of thenoylt>tiluoroacetone 40 ml O. 4M TTA acid layer from and 1~

First, solution with with

10 mg of two

is extracted (buffered mixing. solution, solution

20 n-d aqueous sodium four

with Then

O. 1~ the

formic organic zinc

formate) times

is washed with

the

and the (O. 6~

back-extracted acid

two portions sodium is

of a pH 3.0

chloroacetic

and ,0. 4~ from

chloroacetate). 105.

Zimc recovery

is. 92%

and the

separation

cadmium

100

nn

90

Te=

eo

7a

60

n
~ a u 1x ~

w
50

40

1v of w L

Z w

3(

2C

1(

,
1

.l__L
6 0

10

12

Cl

CONCENTRATION

H Cl CONCENTRATION

Fig. Fig. 6. Extraction of zinc from HC1 solutions into

7.

Extraction from

of zinc

into pure

tributyl

phosphate

HC1 eolutions.

5% methyl

dioctylamine

in dichloromethane.

Methyl

-Isobutyl Zinc

Ketone into and methyl -isobutyl ketone 114 acid. (hexone) Zinc from a solution 1~

extracts acid three

in hydroiodic phase Pd(lI), zinc. Zinc with

6M in m-lfuric with

return acid. is not

O to &e Cd(II), separated

aqueous Ag(I), from

equilibrations stay

6M hydrochloric but pb(~)

CU(II),

and Hg(lI)

in the hexone

Thiocyanate Zinc extracts

Extraction into diethyl ether from 115 solutions Varying 0. 5M in hydrochloric the proportion as shown of in

acid

containing

ammonium

thiocyanate. e the

ammonium Table VII. Table

thiocyanate

change

extraction

coefficient,

VII.

Extraction

of zinc

thiocyanate

into

diethyl

ether.

115

Zn cone.

NH4SCN IM 3M 5M 7M

cone.

HC1 cone.

Extn.

coeff.

O. lM O. lM O. lM O. IM

o. 5M O. !5M 0.5M 0. 5M

23.7 37.8 18.3 12.9

Cadmium Rosenheim alcohol -diethyl

does

not extract

and Huldschinsky ether mixtures. and have isopropyl -diethyl

under 117

these

conditions. zinc

116

extracted,

Kinnunen extracted ketone, ether ketone zinc The

thiocyanate into arnyl 118 and Wenner strand investigated thiocyanate n-propyl Amyl solvents. complex acid is hexone. concentration corresponding of 125 mg 118 Extracbe complex ketone, alcohol,
n.butyl

a number

of solvents methyl

zinc me~yl solutions.

quantitatively phos acetate,

into hexone, phate, diethyl

and amyl ether, The best

alcohol

ethyl

and diisopropyl solvent are for the

are

poorer

thiocyanate hydrochloric

tion less least from

conditions than O. 5~,

as follows:

should

and an excess is necessary solution volme

of ammonium for the

thiocyanate

to at zinc

a 47. solution an aqueous

complete

extraction

of 50 ml. zinc may

In neutral

or alkaline

medium,

extraction with dilute

is incomplete, .amrnonium

and the hydroxide.

be back-extracted Ag(I), and CU(II) and

quantitatively also extract,

Fe(III), with fluoride,

although thiourea.

Fe (ILI) can be masked H fluoride Fe is present,

and Ag(I)

Cu (II) with k the presence

Pb(lI) with

and Ca(II) sodium

interfere.

of Ca and Pb, brge salt

can be masked aid

pyrophosphate

or tartrate.

concentrations

extraction

of zinc.

26

Zinc

Pyridine The

Thiocyanate

into

Chloroform to the methyl and 1 ml

119

solution add 5 ml

is adjusted 2M NH4SCN

red

endpoint. Then also

For 10 ml extract,

80 ml

of

solution, extracts In(III),

pyr idine. and CU(II)

of chloroform but Ga(III),

95~o of the zinc. Pb(II), Ti(IV),

Fe(lI),

Mn(LI),

Bi(IH),

Sb(HI),

and U(VI)

do not extract.

Cvclohexanone Hartkamp O. lM in KI or and Specker NH41 and 120 extract cadmium Zinc with
c yclohexanone

solutions while

O. 25M in

NH40H.

doe8

not extract,

99. 4% d

the cadmium

extracts

in one equilibration.

Oxine

Derivative A solution of 7[ a(o -carbomethoxyanilino) extracts CU(II), Zn(II), Cd(II), benzyl] -8 -hydroxyquinoline at

in chloroform

and Hg(H)

pH 6.121

Naphthyl Zinc

Thiocarbazone (50 Kg) extract~ in chloroform 122 to 10.5. quantitatively from 30 ml into 10 ml of a e olution buffered of naphthyl with citrate

thiocarbazone of pH 8.25

of a solution

Zinc

Dithiocarbamate Zinc and lead ditbiocarbamates are extracted zinc from fluoride solutions 123 lead.

by ethyl Zinc

acetate

or chloroform are brought back

at pH 3 for into

and pH O. 3 for phase with

and lead

the aqueous

8M HN03.

Zinc

Diethyldithiocarbamate Zinc and cadmium buffered once are extracted with and the into chloroform 60 buffer. from dithiocarbamate layer

solutions is washed phase Bi@U), Ni(Il),

to pH 8.5

a citrate zinc

TIM chloroform returned separates Mg(II),

with water

and cadmium This procedure

to the aqueous from Pb(lI), Ca(H),

with

O. 16 Mhydrochloric T1(I.H), Na(I), Sb(ILI), -d K(I).

acid. Ag(I),

Co(II), CU(II),

Cr (III), Fe (III),

Al(III),

But-o] Zinc coefficients perchlorate for some extracts other into butanol are from listed water. 124 The VIII. extraction

perchlorates

in TabIe

27

TabIe

VHI.

Extraction

of metal

per chlorates

into butanol.

124

Element

Extraction

coeff.

Element

Extraction

coeff.

co Ni Mn Zn

7.2

Mg

9.4 9.5 12.9 6.9

7.7 7.6 8.3

Ca Sr Cu

8. The intent of this

Ion Exchange section

Behavior

of Zinc of zinc on various and

is to present different

the behavior as possible.

ion exchange Marcus125 resins, Cation

reeins present

in as many

media

Coryell

a comprehensive

review

of ion exchange

mechanisms,

and techniques. Exchange Meyer, Argersinger, and Davidson 50 x 8 system. 126 have studied activity the coefficients

in the

ZnC12-HCl-Dowex

They

consider

reaction

Zn+++2~=ZnR2+2
where Rrepresents the active resin
2

H+,

group.

They

define

K as

a~+ K=~-= Zn++

aznR2 2 am

mH+ Zn++

Y:cl - lnC12

ZnRZ #m ~

fzfiz

where ience,

f = resin they

activity define

coefficient

on a mole

fraction

basis.

For

conven-

further

2 mH+

NznR2 ,and N~ Ka=K m

Km=~ Zn++

Y:cl 3 ZnC12

fzfiz
so that K=K a~ FIR

Data

from

their

study

appear

in Table

IX.

28

Table

IX.

Activity

coefficients

in the

ZnCIZ-HCl-Dowex

50 x 8 system.

126

Mole fraction ZnRZ

p=o.5 fznRz

K=lO. f

p=l. f ZnRZ

K=ll.7 f

o 0.1 0.2 0.3 0.4

0.5 0.6 0.7 0.8 0.9 1.0

0.818 0.855 0.891 0.921 0.947 0.968 0.989 1.008 1.013 1.009 1.000

1.000 0.998 0.991 0.980 0.965 0.947 0.924 0.891 0.881 0.901

0.855 0.897 0.933 0.962 0.985 1.003 1.017 1.025 1.025 1.015 1.000

1.000 0.998 0.991 0.981 0.969 0.954 0.939 0.924 0.927 0.987

Soldano heteroionic Zn++ being for

and Boyd

127

have

studied They x 10-8

the self -diffus

ion of cations

in for energy -7 cm2/sec

cation

exchangers. of 1.16

report cm2/~ec

a self-diffusion at 25 C, tie

coefficient activation of 4.1 X 10

on Dowex 8520

50 X8

cal/rnol.

Spiegler

and Coryell

128 report

a value

the

self-diffusion

Bonmer cations

coefficient. 129 present and Smith 50 (Table X).

data

on the adsorption

of a Iar ge number

of

on Dowex The data

in Table at be Et,

.x show a group

that the

separation The

of

Zn++

from

other zinc

cations is not

on Dowex vastly pleting the

50 is ,

separation. one.

group

containing

differ

ent from

the classical resin ions,

However, a much

in the. presence versatile compIex

of comIn

agents,

a cation

becomes it is evident The

more

reagent. is much and

section

on complex than the ZnI~

that the has

CdI~

stronger zinc

complex.

author

separated sulfuric total

cadmium acid

on Dowex 0. 05M;

50 X 8 under hydroiodic

the following acid

conditions:

concen10 mI.

tration, The

concentration, w~e the zinc

O. 00 lM; remains Zinc may 20 ml

volume., on a

cadmium

does

not adsorb, and O. 6 cm solution

completely be recovered, of 3~

column washing or 10 ml

4 cm long with

in diameter. by elution

after acid

the iodide

with

perckdoric

of 2M hydrochloric 130 Brown and Hayes

acid. separate blue zinc and magnesium Pas sing by completing the solution ztic

with

cyanide

at the br omthymol

endpoint.

through

29

Table

X.

Relative

adsorption

of metal

ions

on Dowex

50.

129

Metal

ion

Percent 4$

croes-Iinlcage 8 y. 12%

Li+ H+. Na+

1.00
1.32 1.58 1.90 2.27

1.00
1.27

1.00
1.47 2.37 3.34 4.50 4.62 4.66 22.9 28.5 3.34 3.51 3.78 3.81 4.% 4.95 4.06 7.27 10.1 18.0 20.8

1.98 2.55 2.90 3.16 3.25 8.15 12.4 2.45 3.29 3.47 3.74 3.85 3.88 3.93 5.16 6.51 9.91 11.5

Rb+ Cs+ Ag+ Tl+

2.46 2.67 4.73 6.71 2.36 2.95 3.13 3.23 3.29 3.37 3.45 4.15 4.70 6.56 7.47

Uo++
M$+ Zn++ co++

cut+
Cd++ Ni++ C.++ ~r++ Pb++ Ba++

the

sodium

form the

of amberlite anionic

IR- 120 removes complex

the magnesium is not adsorbed. manner. 55 ml EDTA

from

the

solution

while

Fritz is 4 cm through use at pH Fe(lJl), not long the

and Umbreit containing resin, and

zinc cyanide 131 use EDTA 5 g Dowex

in a similar They

Their

column

50 X 4. with

pass

of soItition solution. They

30 ml

of wash wi@

the b~fered acid. should Sm(III),

a gly.ctie 1.,2,

buffer

acidified with Zr(IY),

hydrocliloric

Adsorption separate ~(~) -d

of the zinc ZfiC from but

wash,

elution CU(H),

PH 2. 1 and wash, SC(III), Y(m),

Bi(ILI),

u(~);

Th(IV), Oliver

Yb(III),

or Hg(II). 132 They have worked in a munber of systems system, a negative employing one to two a

and Fritz agents.

completing positive the other.

add hvo

reagents

to a binary to form

form.

complex The

with solution

one

component, passed

another through

complex resin

with

is then

an ion exchange

column

30

Table

XI.

Adsorption

of zinc

on Dowex

50 X 4 from

O. 02~

EDTA

solutions.

131

pH

Zinc

adeorbed

102 1.5 1.8 2.1

100 83.5 39.4 0.0

where of zinc with

one component and uranium

adsorbs

while

the other

elutes.

They charged

report complex of zinc

a separation of uranium ethylene 1 X 8 of

at pH 9 by forming acid, and a positively solution the uranium

a negatively charged through and the system are

sulfosalicylic The

complex a column zinc at pH Fe, U,

with

diamine. anion zinc

resulting resin; may

is passed adsorbs same acid

of Dowex

exchange and iron

elutes. 10. Al,

Separation Elements

be effected with

in the

forming and Y; condi-

negative those tions

complexes

sulfosalicylic with

Th,

Zr, the

forming are Cu,

positive Ni, Zn,

complexes and Cd. of each

ethylene

diamine

under

same mixtures

Quanti~tive group was

separation performed

of binary at pH1s 8,

containing using

one element

9, and

10

Dowex Kraus,

50 X 12 and Amberlite Michelson, by cation

IRA-401. 133 report and Nelson exchange r e sins. are

a strong strange

adsorption behavior adsorbed

of some appears by anion 10M in than of the show to

anionic

species

This very

be confined exchange LiCl 105. order and

to those resins from

complexes

which

strongly

concentrated AuCl~, acid, case, while

chloride

solutions. have

In a solution KD!s

O. lM in HC1, hydrochloric In either to adsorb, could and prove Thomas

FeCl~, AuCl~, Zn(LI),

and GaCl~ FeCl~, Mn(H), T1 (~)

of greater KDs

In 12~ of 100.

and GaCl~ Co(n), adsorb one. Bi(III), only

have

and Sn(IV) slightly.

no tendency phenomenon Davies the resin of miscible Kember, mixtures system

Sb (V) and

This

to be a rather useful 134 pointed out that than in tie liquid

the concentration This effect ions suggests upon from

of water that

in addition

phase

is higher

phase.

organic McDonald, of methyl

solvents

and Wells, ethyl

should have a large 135 eluting metal water, E they concluded

re sin behavior. cation resins that with this gas,

ketone,

and hydrochloric used anhydrous

acid, ketone

found

did improve eluted

reparations. quickly. They

and HC1

everythtig phase must

that the

re a in phase

and the liquid

be in water equilibrium but need not be in acid equilibrium. 136 investigated the methyl n-propyl ketone-hydrochloric Carleson He separated Zn(H), the metal Cd(II), ions CU(II), were CO(H), Mn(lI), on Dowex Ba(II), 50;

acid Bi(UI),

system. and Ni(II)

as follows:

adsorbed

with

ketone

31

plus Cd(II) with

2~0 10M together, ketone

HC1,

the order

of elution with

and separation ketone plus

was, 15% 8M

Bi(I.11), HC1,

Zn(II), Mn(II)

and

CU(II), 30~0 8~

and Co(II); HC1, Ni(H) and

eluted;

plus

eIuted; Topor

Ionescu, KU-2 acetone, separation ~ion or R-21 l%

Constantinescu, with

with 8M HC1, 137 eluted zinc HC1,

Ba(II) from

eIuted. cation resins

79. 5~o acetone, HC1, 40~. water

O. 5~0 cone. (volume

20~0 water,

or 597. a good

cone.

percentages)

and obtained

from

copper.

Exchange Kraus and Nelson acid 138 have studied The acid the behavior of zinc on Dowex is shown .1 X 8 in Fig. 8

in hydrochloric as a function Behavior

solutions.

distribution

of hydrochloric

concentration.

coefficient 138

of other elements is shown in Fig. 9, taken from earlier work 88 by Kraus and Nelson. 139 140 Home, and Pier son and Schindewolf have shown that the species adsorbing present on Dowex in solution The As in chloride Kraus, ions those Zn(II), in Dowex in 12~ 1 is ZnCl~ which with the species 138 by Kraus and Nelson and shown in Fig. 146 of the adsorption process is small. increases, the KD for zinc increases agrees very well

as determined coefficient

4.

temperature the

cross-linking 141 solutions. Nelson,

of the resin

Clough,

znd

Carlston than they

142

reported

KDIs b

of many

metal over Co(II),

1 to be increased HC1. Some

more

a hundredfold mention are

12M LiCl

of the metals

Sc(llI)~

Mn (II),

Au(III),

Fe(m),

and Gz(~~). coefficients Horne139 was show

The

difference phase

is probably when

due to large is immersed of two +

d~erences

in activity

in the resin that

the resin

in the s.e two media. molar, Kraus b Fig. the KD

noted

at the chloride >H+ >Na+

concentration >NH~ >K+ >Ca.

and Nelson 10. The

of zinc 143

highest the effect

for

Li+

of the cation

of the

supporting

electrolyte

half-time

mesh

Dowex with

adsorption 144 1 at 25 C is 5 minutes. zinc on the resin is 146

of either

or resorption

of ZnCl~ for

on 50-100 of zinc in

solution

The half-time 145 13 * 2 minutes. the effect Their of some

exchange

Yoshino KD of zinc 11 and increases suggest mation 12.

and Kurimura

studied

of org-ic dati org-ic acid are

solvents presented

on the in Figs.

on Dowex They

1 X 8 in HC1

solutions.

showed

that the addition of zinc effects in low may

solvents

markedly They

the adsorption that these of negatively solvent

hydrochloric be explained complexes

concentrations.

by the increase of zinc as

in the forof

charged

chloride

a consequence in mixed solvents. on

the deer ease Huber Dowex

and Irtie

in the tendency for hydration 89 adsorbed CU(II), hydrobromic acid

of the zinc Co(II),

ions

Zn(II), Ni(II)

and Ga(III)

1 in strong

solutions.

did not adsorb,

CO(H)

32

./
I 1 I 111111 1 1 11[1.11

10.OO1
Fig. 8.

0.01

0.1
of HCI

111111
1.0

I 111111

10

Molality
Adsorption functions

of Cd(II)

and

Zn(II)

in HC1.

eluted with

with

5~

HBr,

CZ(III),

with

3~HBr,

CU(II)

with

1~ HBr,

and

Zn(II)

water. Faris147 studied 1 X 10, Zinc from 5M HF. and Meyers 148 studied the adsorption of zinc on Dowex up or permedia region are to 18 at con. the adsorption 200 does mesh, of many elements from range hydrofluoric from lM to be s ep. and

acid 2%

on Dowex (Fig. 13).

in the

concentration

not adsorb Te(IV),

at any Sb(V),

concentration, Sn(IV), Zr (IV),

and may Nb(V),

arated

easily

Mo(VI),

Pd(II),

As (V) with Home,

Helm,

1 X 8 in a variety to 8M in acetic ahloric acid,

of media.

They

found

no adsorption

in concentration acid other 3M

acid, and 13M

2. 5M in sulfuric in HN03. acid, at higher to 4000 acid,

acid,

5M in hydrofluoric coefficients in the cy-ide, lM for to

Adsorption increases

as follows: and remains O. 5~ NaCN,

pho spheric constant drops oxalic constant

rapidly

concentration~; NaCN

~=~.8x105 constant drops at higher to

at 2~ .

and remains H2C204, ZnO~

centrations; and staye Meyer

KD

1000

at O. O1y

10 at O, 2~,
well.

B and Home

at higher concentrations; 140 report good adsorption of zinc from lM to

does

not admorb

of zinc 7M.

from

hydroxylamine

hydrochloric

solutions

33

w 4=

EHHEEIMMIM
Fig. 9. Adsorption of the elements from hydrochloric acid.

10
o

1 4

I
6 Molority

I e of

I 10 Chlorido

I 12

I 14

Molarity of HC1

Fig. (-10

10. per

Adsorption cent loading

of zinc

(II) from

chloride

solutions

Fig. 1. 2. 3.

11.

Anion

exchange

ads orption

of Zn(lI).

of resin).

in HC1 solution in HCl - 30 ~. (v/v) in HC1 - 60% (v/v)

methanol methanol

mixutre mixture

Organic Fig. 12. Effects

solvent of various

added, organic

wt ~~ solvents on the

anion exchange adsorption of Zn(lI) in O. 1 M HC1. Acetone 1. 2. E*o1 3. Methanol 4. n- Pr opanol Methanol (Dowex 1-X4) RN03 +Cr , ~ .0. 003, (NaCl) Methanol :: Methaol 7. RN03 +Cr , p = O. 1, (KN03)

Ltidenbaum, Starnex higher lithium S-44, KD!s

Boyd,

and Myers anion than

149

a sulfonitun on Starnex

exchanger.

have studied 150 They 1 for both

a new type report that

of r es in, zinc has and

S -44

on Dowex

hydrochloric

acid

chloride Table XII

soluti~ns. s urnmarizes the data of Jentzck acid and Frotscher 151 obtained

with

Wolfatit

L- 150 and hydrochloric

solutions.

36

ml-mm-n

Ht!ji!l ~:~--~-=-.
NO A05. - NO 40 SORPTION ,lR FROM IM - 24

M HF

AO!%- STRC4AG AOSORPIION: IDG OIST. COEFF >2

WiilJJ:,

m
F u .1 1

ROMAN NUMERALS REFER IN INITIAL SOLUTION.

TO OXl OATION STATE

E!?!
W, h
I

c,

i. ----

Fig. acid

13.
with

Removal of elements from solution ZOO-mesh anion exchange reBfi.

h 1 M to 24 M hydrofluoric

Table

XII.

Elution

of various with

metal

ions acid.

from

Wolfatit

L- 150

hydrochloric

Hydrochloric Element 12.5 11-10 7.5

acid 6.5

concentration 5 4 1.5

(rnolarity) 1 0.5 0.05 0.005

M hag Li Na K As (III) Ca Ni Fe(H) co Mn(II) Fe (III) Cu sn(Iv) In Zn Cd Pb

x x x x x x x x x x x x x x x x x x

Kraus Fe(lII) column appeared eluted

and Moore

152

separated 12M

zinc

from

Ni(ll), acid

CO(II), through

CU(II), a Dowex-

and 1

by passing

a iolution

in hydrochloric concentrated aucces sively

p r eviou d y conditioned in the eluate. Eluting with

with with

hydr ochlor ic acid. more 2. 5~ dilute HC1, acid, Fe(III)

Ni (Ii) Mn(H) with

with

6M HC1, and &d Zn(II)

Co(It)

4M HC1,

CU(II)

with

O. 5MHC1, Miller 2M HC1,

with O. O05MHC1. 153 Hunter adsorbed zinc 2M HC1, Al(UI), U(VI), with and eluted Mg(II), Be(~), 20%

on IRA-400, with either CO(H),

chloride water Ni(H), or

form

in

washed

wih from Ti(IV),

O. 25N HN03 Cr(lII), and k(ILI) of Sb (III), remains

as a separation Th(IV), are Zr (IV),

Ca(II),

Mn(JI), Cd(II), amounts

and CU(II).

Zn(II), and smaII Bi (III),

eluted and

together Pb (H).

along The

of the Sn (IV) ~f Sn(IV),

Bi(IH), adsorbed.

majority

Sb (III),

and Pb(II)

38

Freegarde on Dowex was eluted

154

separated HC1 with 2MNaOH

zinc

and copper per

as follows: liter or

zinc

was

adsorbed and 1NHN03. 1

1 in O. 12~ with either

100 g NaCl with 155

(the copper O. 005 NHC1,

eluted), or

20 g/1 adsorbed Zinc

NaCl ztic

Kallmann, with with O. 12NHC1 IMHN03. Berg Dowex 1,

Steele, containing

and Chu

and cadmium with

on Dowex

10% NaC1.

was

eluted

2M NaOH,

cadmium

and .Truemper 60 to 100 mesh

156

separated 1.16 was

zinc, cm 1.5 id.

cadmium, and 6 cm per

and mercury long

on a up

column rate

in quantities The was metals eluted

to 100 mg were

of each. from

The flow

to 2 ml with

minute. Zinc

adsorbed

O. 5M HC1 and washed 757.0. OINHC1 was 157 a dilute 158

2M HC1.

with

180 ml fraction urea

of a solution 200-500 ml;

25~0 methanol, eluted with

cadmium O. OIMHC1

eluted

in the

mercury

then

O. lMthio-

solution. Baggott and Willcocks from separated solution zinc and cadmium while zinc on Dowex passed 1 by

adsorbing the column.

cadmium

of IU,

through

Hunter 2M HC1, HN03.

and Miller

adsorbed then 159

zinc

and cadmium The zinc

on lR&400 was eluted

from with O. 25N

and washed

with

5M HI,

water.

Kallmann, ing the CdI~ zinc

Oberthin,

and Liu

separated with

zinc

and cadmium solutions with for and 3~

by adsorbwhile HN03. is, the

on Dowex

1 from Cadmium

O. 75~ was

H2S04 recovered

5~0 KI

did not adsorb. The use

by elution

of iodide

as a preferential the most and cadmium. Ieotopic of zinc chelates exchange

completing convenient,

agent easiest,

cadmium most

in the opinion method

of the author, zinc 9.

effective

of separating

Exchange tracer show in less

of Zinc with zinc compounds Leventhal (at 25 C) acetylacetone, are and

In general, too rapid

the rates even

exchange this

to measure; found zinc

rapid

exchange.

Garner160 dipyridine

complete acetate

than 30 seconds complexes:

of traced

and the followtig benzoylac Atkins

zinc etone

ac etylacetone and dipyridine not exckge zinc acid, complexed

ethyl enediamine, thiocymate. with zinc

and Oarner

ammoniate, ,nicotinyl, ac etone, 161 found that Zn65 tracer did but did exchange with

in the phthalocpmine

complex,

with

diphenylthiocarbazone,

8-hydroxyquinoline,

anthranilic

and salicylaldehyde. Ionescue, Negoes CU, and Gainar162 at 00, 15, 25, studied and the 35*C S1OW exchange but no further between data were

Zn65S04 given. -

solution 163

and ZnO

Miyagaki zinc in solution

has

evidence with

that

the zinc

sphalerite

will

exchange

with

in contact

the ore.

39

Barriera64 with zinc metal

reports sheet with carefully interior He also for

that

Zn

65

.ti

sulfate

solutions

exchange

.sIowly

a half-time and found of zinc found

of the order

of 10 days.

Matmmra165 occurs with of

studied uniformly ~65S0

this

system &e .

that heterogeneous been left

exchsnge in contact .s at the

within solution 4 are the

dumt that has

that a few

thousand

layer

surface

zinc

foil

available solid,

exchange.

Apparently of the The zinc

the diffueion metal

of zinc atoms of

through solution, 10- 3~

or recrystallization the rate of exchange. of Zn++

in the presence step below.

limited

rate-determining surface. The

in ZinC is the adsorption is given approximately

on the

fraction,

F;

of exchange

by the expression -krt -kst + ABe ,

F~l

Are

where

k~

= (0.20

q/v)

(1 0.5p

1/2

),

inhr-l.

For solution, is another

Zn-Zn++ ~ i; the

exchange, ionic strength,

q/v

is the ratio t is time, Ar

of surface and As are

area

to volume

of r

constants,

and k

constant

similar

to k~. Paper Chromatography by Lederer and Lederer Little, has been 166 is an excellent more Sepaof the

10.
Chapter review recent rations capacity a eparate

43 of Chromatography of inorganic behavior are paper in paper for

of the field data on zinc type

chromatography. chromatography microgram quantities

if any, found.

of this

excellent

qutitities, of metals

but-because cannot

of papefimilligram d conveniently. can be made

or larger

as yet be

Ions

to migrate

through

the liquid

entrained

in the paper .

by impressing Lederer groups

a potential gradient parallel to the direction of migration 168 have separated. metaI ions into rather interesting and Ward means. Their data book are shown in Table XIII, 167 gives

by this Chapter

18 of Lederers of the field theory Na4P207 below from with used agent and allows with

Paper

Electrophoresis

an up-

to-date chapters and

review review using

respect

to inorganic Maki169 than 2,

separations, separated Ni(II),

earlier CO(H), pH 1.7,

and techniques. at pH!s pH 5.6 Ni(II), less

Zn(II)

metaphosphate electrophoresis. with

below

and trirnetaphosphate also separated Zn(II) acidified

using CO(II),

paper

Maki170 of acetone

and Mn(lI) acid. called of his

a mixture

and methanol

hydrochloric a similar to one

Schnacher171 He adds potential a complextig gradient,

technique electrode

focus

sing

ion exchange. a the

system,

impresses along

the ions

to migrate.

At the point

40

Table

XIII. 50

Movement, under

of metal a potential

ions

in O. 5~hydrochloric of 3.6 v/cm.

minutes

gradient

acid 168

in

Anionic 2. 5-1.5 Hg(II), cm Pd(II) 1. 5-0.5 cm

Iso electric

Cationic 0. 5-1.5 Mo(VI), Rh(lII; Sri(n), Pb(II) cm Zr(IV), , As(m), Sb(m), 1. 5-2.5 Cr(HI), Ti(IV), Fe(llI), Ni(II); CU(H), Sr (II), cm U(VI), Be (II), Co(II), Al (III), Zn(H), Ba(lI)

Au(III), Bi(IH),

Ir (IV), T1(III)

Cd(II)

paper this

where technique, Al(HI),

the metal

complex

is uncharged,

the migration 10 pg added each

ceases. of Fe (III), center

Using Ni(II),

he and Streiff U(VI), of Co(II),

172 have separated

Zn(lI), paper chloric

Cr(III),
5.

and Mn(II) anode sodium

at the

of the

in a solution acid, the

pH about

The O. 5M

solution

contained

O. 5M hydro sodium com-

cathode

solution flow

hydroxide v.

and O. 5M was

nitriloacetate, plete in five

the current minutes.

was

100 ma

at 500

Separation

v.

DISSOLUTION

OF

SAMPLES

CONT~lNG

COMPOUNDS

OF

ZINC

According no cliff iculties acid,

to Hillebrand and can usually acid which

et al. ,

20

the

solution

of zinc

minerals

offers

be accomplished by nitric acid,

by attack or nitric

with acid

hydrochloric alone. The

hydrochloric residue, with

followed ordinarily

insoluble by fusion Soils

contains followed

no zinc, by solution

can then

be decomposed in acid.

sodium

carbonate,

of the melt

In general, of the soil.

zinc

analysis digests then

of soils the soil

does with

not require a mtiure

complete

dissolution nitric, C. in

Martin173 acids, with Mart& the filtrate a solution for

of hydrochloric,

and perchloric Mter leaching

evaporates

to dryness is then with Shaw cooling,

and igpites extracted acid,

at 300 -350e with dithizone

dlf17:te acid, also with

the filtrate soil

chloroform. and extracted heating. with with

digested dithizone. to 8.5,

sulfuric

diluted; leached

filtered, soils by

and De-174 then

of pH 7.0

extracting the easily

the mixture soluble ztic

dithizone

1 to 2 hours.

Baron175

determined

41

in soils sulfate, aqueous Plants

by extracting and acetic phase

ztic acid

with

a solution followed

of ammonium by extraction

acetate, of zinc

ammonium from the

at plil 4,

by dithizone

in chloroform.

Heinen finely of ground,

and Benne76 air -dried solution,

ashed plant

plant

materials into with bath

.as follows:

weigh

2 g of Add 10 ml for

material

a porcelain the sample. until most

crucible. Include

1N H2S04

mix Heat oven

thoroughly on a steam

crucibles

blank then muffle

determinations. dry in a hot-air

of the water water. Remove

is removed, in a the

at 105 C C until

to remove ashing a little materials

remaining

Heat from

furnace cool,

at 5000-550 moisten for

is complete. water.

furnace, (more

the ash with some until plant all

Then add an acid

10 ml ash into

of lN HC1 extract),

if necessary on a stean 3 to 5 ml @

to insure

and heat (Adding Add trate. &alyze Organic

bath cone.

soluble

material for

is brought

solution. alternative. the filred indicator. )

HC1 and boiling filter

two minutes matter acid

is a good

a few

of hot water, the filter zinc using until

off the insoluble are no longer

and collect to methyl

Wash for

washings

the dithizone

procedure.

Materials ashes the sample in a ,platinum acid, method. Marcali, through with but leaches a column with O. lN hydro resin and phosby filters, crucible washes, at 500 -550 C, the

Marcali177 leaches filtrate

the ash with and wash Hamm178

lN hydrochloric

and analyzes

by the dithizone ashes tissue passes

as does

chloric (Lewatit phate.

acid.

He then

the leach the column

of cation iron

S- 100), Zinc

and washes with 5~

water acid

to remove eluate

is eluted method.

hydrochloric

and the

analyzed

the dithizone .Saredo filter,

and Lerni179

digest

tissue

with

30~. nitric sulfuric Pb, Bar Fe,

acid acid, Cu, Co,

for

3 to 4 hours, and distill off

concentrate The

to a syrup, residue

add concentrated e-mined for

the mercury. Helwig, neutron-irradiated with nitric acid,

is then and Smith ash

As, and

or

Zn.

Aahikawa,

180

separatedP,

Zn from

biological convert.

as follows: with

evaporate hydrochloric

the ash acid,

to dryness make the and

to the

chlorides and paes acid.

solution wash with

12M

in hydrochloric

acid

,firough

a Dowex

1 column

with

concentrated

hydrochloric acid, Fe wi~

Phosphorous

elutes.

Co is eluted

4M hydrochloric Banks, Tupper,

and Wormal for 182 zinc split

O. 5M, and Zn with O. 005M. 181 . digested tissue with acid, filtered, method. proteins with 6M hydro

and

analyzed

the filtrate

by the dithizone the zinc from

Rechenberger

blood

42

chloric dithizone

acid

and 20~0 trichloroacetic

acid,

then

analyzed

the

solution

by the

method. VI. COUNTING TECEUWQUES

All can well this

zinc

isotopes

have

an abundance iodide

of electromagnetic

radiation tube.

and At

be counted

by a sodium that more

crystal the than

and photomultiplier radiation, The of the

laboratory,

we find is far with

counting precise counting in the

electromagnetic counting

or even main itof

bremsstrahlung, source self, of error and the

electrons.

electron error

is the nonuniformity self -scattertig and

sample

the counting 16

sample.

concomitant 183

self-absorption

Gamma-ray 184

. spectra .

from

IDO-16408

are

shown

in FiRs.

14,

15,

and

:2 F=ill#Mii

I&
6

I 1 II

I I

_.

1 .- a
I
e

L . L . 1-.. ..4. ... - .1

1.

Fig.

14.

Gamma-ray

spectrum

of Zn.

65

VII.

COLLECTED Leddicotte

RADIOCHEMICAL et al. 185 have They given list

SEPARATIONS a review sample

PROCEDURES activation of analysis,

FOR analyses the

ZINC

of neutron method

for

most

of the elements. involved, observed

type,

nuclide Many

concentration, are

and sensitivity applicable to this

of the method. type of work.

of the procedures

that follow

43

10

,43SMW 7
i

I
14hr Zffg

I
I

GAMMAS

fl

ti q
t

3X3 aI N
S-SO-56 ABsoRBER-7nom9/clr? SOURCE
I

5 ,e3Mwy

14.1 Hr Ga72 GAMMAS SX3n Na I

SOURU DIST- Iocnl

9-13-56 ABSCFER-2.O g cmz

=

DIST. - IOCM
I I

ENERGY S~E

2 kw/ PHU

1
WITH roR II

ENERGY

SCALE=

kov /PHU

(, I 02 !A I

[1 n 1

i=
\

\ I

5 k

BACKS SPE(

kTTER RUM

2 al E
o
2(

400

600

800
spectrum

1000

200

I
o

I
1

PULSE
1

HEIGHT
1

I I
1000

I I
1200

2(XI
Fig. 16.

4cm

600

000
spectrum

Fig.

15.

Gamm a-ray

of Zn.

69

Gamma-ray

of Ga.

72

PROCEDURE

1 Separation

of Zinc

from

Fission

Products

Source:

H.

G.

Hicks,

W.

E.

Nervik,

P.

C.

Stevenson,

and D.

R.

Nethaway. 1. Add zinc carrier and cadmium HC1, holdback HN03, to the active solution and adjust are

to lN in acid suitable.

or less.

HC104,

and H SO 24

solutions

2. Cool

in an ice

bath, HC104

add 5 ml to start

zinc

reagent

(see stir,

note

1),

stir. ten

Add minutes,

2 drops cen-

concentrated trifuge, wash

precipitation, 1~ HC104. HN03, lM in OH Add

digest

ZnHg(SCN)4

with

3. Dis solve
Y, Zr, centrifuge,

in 1/2

ml hot concentrated Make

dilute with each Discard with diam,

to 20 ml,

add

3 drops NaOH,

and Cd holdbacks. discard solution, supernatant

carbonate-free of Fe

precipitate. stir, liquid

2 drops

and Cd to the

u pernatzmt
4. Adjust
column been O. 5~ boiling the

and centrifuge. to 2~ long, in acid 6 mm

precipitate. pass through a resin

HC1,

of Dowex

21 K (10 cm with

50-100

mesh) with

that has 10 ml 20 ml

pre-equilibrated HC1 containing

2yHCl,

Zn is adsorbed. Elute

Wash

3 drops

of 4~0 KI solution. of 4~. KI solution. of Dowex columns, 3~ 50

Zn with

water

containing onto mesh).

3 drops a resin

5. Direct
in diam, with

the eluate 50-100

column

(5 to 6 cm long, wash cation

6 mm

Discard Elute

anion

column

10 ml

lM HC104. NaOH and

Zn with Cd

20 ml

HC104. and repeat steps 2 through

6. Add 5 rrd 6~
5.

3 drops

to the

eluate

7. Neutralize
3 ml twice as (NH4)2 with

to green HP04 dilute

endpoint buffer

of bromthymol 2), digest once with

blue

with

NaOH

and HAc. Wash

Add

(note (note 3),

in hot bath acetone,

10 minutes. dry at 110 C,

buffer

weigh

ZnNH4P04. Note 1. Dis solve filter. Note 64 g NH4SCN This solution and 54 g HgC12 should be relatively in some water. indicator, in one liter fre Hh. Neutralize dilute careto 140 ml. of water,

2. 3.

Dissolve fully with

15 g (NH4)2HP04 W40H

to phenolphthalein of buffer from E.

Note
PROCEDURE

Two

or three

drops

in 30 ml water. Fission Products Procedure for Isolation The of

2 Separation J. M. Siegel Activities

of Zinc and L.

Source:

Glendenin,

Zinc

in Fission, Book p. 3,

in Radio chemical C. D. Coryell,

Studies: Ed.

Fission New 1. To a suitable add 10 mg

Products, 1951),

(McGraw-Hill,

York,

1432. uranyl sat. nitrate solution and (notes sufficient 1 and 2) HN03

volume carrier,

of irradiated 1 to 2 ml

zinc

oxalic

acid,

45

PRocEDuRE to make and add for the

2 (CONTINUED)

uolution

lM in HTf03.

Cool

in running Stir

tap water solution discard

or ice

bath,

3 ml

of HgCL2-KsCN (note 3),

reagent. the

the cold

occaeionalIy the supernatant

3 to 5 min

centrifuge

ZnHg(SCN)4,

solution. Alternative 10 mg uranyl extraction carrier (note ,9tep (note and 2)0 Add to a suitable with volume about of sample gram

of zinc nitrate

sufficient

2M Na2C03 the uranium with 5 ml

2 ml per ZnC03. Dissolve acid and

4) to complex the precipitate cool,

and precipitate O. 2M Na2C03. sat. oxalic for

Centrifuge

and wash

ZI-LC03 in 10 ml HgC12-KSCN centrifuge

2.

of 1MHN03, Stir

and add solution the

1 ml

3 ml

reagent. the

the cold

occasionally supernatant and for 3 ml

3 to 5 rein,

ZnHg(SCN)4,

and discard to the

solution. HZO. Boil until the -

Add

1.5

ml

of 6M HN03 dissolves,

ZnHg(SCN)4 boiling and cool sat.

precipitate position bath. reagent. ZnHg(SCN)4

3. 4.

and continue Dilute to 10 ml add

1 to 2 min

to remove

decom

products. To the cold Stir

in running acid

tap water and 3 ml

or ice HgC12-KSCN the

solution,

1 ml

oxalic for solution.

the cold and discard

solution the

occasionally

3 to 5 rein,

centrifuge

supernatant

Repeat To the

step

2. add 1.5 ml 6M HN03 and 3 ml for 5). water. Boil until the

ZnHg(SCN)4 dissolves cool, and

precipitate to 10 ml, HgS.

and continue saturate supernatsnt with

the boiling H2S (note add with &ice - 5), supernatant

1 to 2 minutes. Centrtiuge

Dilute

and discard (note 6) and the and

TO the

clear

liquid

1 ml H2S. with

of 6M NaOH Centrifuge 5 mg

5 mg bismuth i2s3 H2S. Repeat

carrier,

and saturate scavenging

and discard carrier

the Bi2S3

bismuth with H2S,

Add2rnlof6MNHCH0 ZnS,

out the white

5.

4232(PH and discard the 5 ml cone.HBr twice

eaturate

centrifuge

solution. to dryness of cone-HBr. and heat 2 mg Digest over an open Take to boiling. +++ up

Dis solve flame. residue Keeping carrier solution Repeat

the

ZnS with

and evaporate 5 ml portions

Repeat in 10 ml the

evaporation

with add

of O. 5M NaOH, under

1 ml

2MNa2C03, add about by drop. the Fe twice

solution

constant

agitation, drop

of Fe

and about for 1 rein,

5 mg

barium

carrier

the hot precipitate. +++ Fe

centrifuge,

and discard scavenging

(OH)3-BaC03 with about 2 mg

the hydroxide-carbonate barium carriers. solution the

and 5 mg

6. To the clear
sat. add oxalic 3 ml

supernatant acid. Cool

carefully

add

4 ml

of 6~

HC1 and

1 ml bath, Cen-

solution and

in running stir the

tap water for

or in an ice 3 to 5 min.

HgC12-KSCN ZnHg(SCN)4 ZnHg(SCN)4

reagent,

occasionally eupernatant tr-sfer,

trifuge

the the

and discard in about

liquid. with the aid of a

7. Suspend

5 ml

of H20;

46

PRocEDuRE wash funnel; absolute the paper vacuum evacuate and mount Note 1. bottle,

2 (CONTDHJED) to a weighed with filter-paper Wash disc (note 7) in a small with Hirsch of

and filter alcohol with

suction.

the precipitate ethyl glass, the as

3 portions

and three

portions

of anhydrous watch release

ether. and place suction,

Transfer in a and then (note 8)

the precipitate Evacuate more.

to a small for 2 rein,

desiccator. for for 5 min

Weigh

the precipitate

ZnHg(SCN)4

counting. after the addition be as much cannot oxidizing of the as reagents, should be at

The volume, least 10 ml mercuric

and may

25 ml. in the preeence ie present, may been be

Note

2.

Zinc

thiocyanate strong

be precipitated agents. Jf HN02 the

of IIN02

or other

or if the IIN03 evaporated added) may

concentration dryness

is umlmown, (after of the zinc

solution has

to near

carrier These

and taken

up in 10 ml

1MHN03.

difficulties step in step cone 1.

be c ircu-rnvented be neceseary etirring acid

by the alternative to scratch rod to start the wall

extraction of the

Note Note

3. 4.

It may with

centrifuge

a glass free

the crystallization. volume is greater heating

If much than may

is present

or if the initial Na2C03

10 ml,

the addition to effect

of solid the

and the soIution

gentle

be required sulfur may

complete

of the. uranimn.

Note

5.

Some

be formed,

but is removed

in subsequent

scavengingsa

Note 6. 7.

The

acid

concentration

should

be about

O. 3M after

the addition

of the Note

NaOH. paper under must the be washed with H20, as ethanol, and ether, before

The filter and dried

same

conditions

in the procedure

the weighing.

Note
PROCEDURE

8.

The

zinc

carrier

solution Design

should

be

standardized from

as ZpHg(SCN)4. of Z < 30

3 Cu Spallation,

ed to Separate

Elements

Source: 1. The HZ02 copper . Zinc

R.

E.

Batzel, target

Univ.

of Calif.

Rad.

Lab.

Report HN03

UCRL-432. or HC1 and

metal

is dis solved

in concentrated are added.

carrier is removed the

and holdback

agents

2. The copper
added precipitation.

as CUS from alkaline,

a lM acid and H2S

solution.

NH40H to complete

ie then ZnS

to make

solution

is added

3. Wash 4. After
stirred

precipitate

with

dilute

NH40H

containing of 5~

H2S. the precipitate (after about

the centrifugation, well, and the

2 to 3 ml solution

HC1 is added, almost

centrifuged

immediately

47

PRocEDuRE one minute). slowly 5. The .

3 (CONTI.NUED) ZnS and MnS are dissolved, while COS and NiS are attacked

.mpernatant is added acetic with

liquid

is boiled

to remove then

H2S,

snd

about volume almost

1 ml

concentrated of

NH40H glacial saturated 6. The

to neutralize is added.

the HC1; The

an equal is heated

(3 to 4 ml) to boiling

acid

solution Z&.

and

H2S to precipitated is dissolved

precipitate Two

in l~HCl, of NaOH ae zincate. with

the H2S boiled are added

off,

and 2 mg

Fe+++

added. leaving 7. The added

or three

pellets

snd the Fe (OH)3

removed,

the zinc

in solution

solution

is made

lM in acid ZnHg(SCN)4. reagent was

HC1,

and zinc ly

reagent

(note dry,

1 ) is weigh. and 54 g

to precipitate 1. The zinc

Wash made

with

HC1 twice,

Note

by dissolving and filtering.

64 g NH4SCN

HgC12

in one liter

of water

PROCEDURE Source: 1. Dissolve with 2. H2S,

4 Copper G. Carleeon,

Spallation Acts target

Target Chem Stand. ~, 1673-1700 (1954], precipitate the Cu

the copper centrifuge, supernatant stream.

metal save

in hot HC1 and H202, liquid. volume

supernatsnt to a small amounts

Evaporate warm air

liquid equal After

on a steam of filter

bath with paper

a a

Add

to two

strips

with

calibrated chambers, by eluting the other on the

micropipet. the complete one with strip the with same

15 minutes

equilibration cation plus

in chromatography species 15% 8~ is attained HC1, and

separation methyl ketone

of different ketone 10~ Each

-n-propyl plus 15~.

HC1.

The

exact

positions

strips

determined

by scanning.

ion species,

Mn and Ni from

Table

XIV.

Rf values.

Element

Ketone

+ 157. 8M HC1

Ketone

+ 157.

10M HC1

acid Zn Cu Ni co Fe Mn Cd

front

0.68 0.67-0.80 0.40-0.87 0.03 - 0.06

-0.75 0.65 0.04 0.69 0.95 0.26 0.86

0.30-0.40 0.83-0.90 0.08-0.12

--

4a

PROCEDURE the second

4 (CONTINUED) solvent mixture, and Co, Zn, Fe, and Cu contaminations and gently ashed into from a smalI

the first, platinum 3. The

ia completely dish.

cut out of the

strips

GuS is washed,

dissolved

in cone.

HN03,

diluted

to Imown

volume,

and an aliquot Table XIV

counted. liets some of Carlesonls Rf determinations.

PROCEDURE Source:

Scheme

of halysis

T.

H.

Handley,

Identification Quarterly

of Radioelements, Progress Report,

in Analytical 0RNL-955,

Chemistry Jan. & in a glass Fe, Co, aliquot 1951,

Division p. 47.

containing cone.

an adequate Add about

number 5 mg

of counts

per

minute carriers: that

is placed Ag, Cu,

centrifuge Sr, for and Na. that

of the following

In most which

instances, constitutes upon which XV. make

it is recommended the product, group

the carrier one of falls k.

be added the above Groupings Group I.

element

eliminating element

carriers, are given

depending in Table are

the product

If chlorides mixing several of Ag

present,

the

solution Make the

alkaline with

with cone.

NH40H HC1 and retaining

to ensure boil it, add for for

carrier

and activity.

acid

minutes.

Centrifuge twice with

and decant 5 to 10 ml

supernatant, HZO.

and wash 1 ml

the precipitate H20

distilled

FinalIy and mount

distflled

and make

a slurry.

Evaporate

to dryness

counting. L To the slowly supernatant from Group be gins through retaining I of about to form, the soln. it, 15 ml add volume, 1 ml add 3N HC1 Cenwith

Group NH40H

until

a precipitate Pass H2S

then for

of cone.

and heat trifuge

to boiling. and decant HZO,

several

minutes. Nice

supernatant, mount

wash

the precipitate

5 to 10 ml Group 2 or

and count. to 50-ml again. beaker, Add cone. boil to remove until H2S, add

ILL Transfer 3 drops then 307.

supernatant H202, and boil

NH40H

precipitation it; wash

begins,

1 ml more. twice with

Centrifuge 5 to 10 ml H20,

and decant mount from snd

supernatant, count. III for

saving

precipitate Group IV.

Pass save Acidify

H2S through super natant, supernatant

supernatant wash from

Group

several

minutes,

centrifuge, Group make V. just

and count Group

precipitate. HC1, boil to remove 204. H2S, Let

IV with

alkaline

to phenolphthalein

and add 2 to 3 ml

(NH4)2C

49

PRocEDuRE stand Wash Group take for

5 (CONTINUED) several minutes, precipitate. supernatant mount to dryness, flame to remove NH; salts, and centrifuge.. Decant supernatant and save.

and count VI.

Evaporate HC1,

up in dilute Each group

and count. be eeparated into its components by varioue

now must

meane.

Table

XV.

Distribution

of radioelements Lundell

in the

scheme. 23,

(Adapted

by Handle y from

and Hoffman.

Possiblv Au,
GTOUD

lost: Hg, I: Sir Nb, P, II: Hg, Te, Pb, Re, Fe, Bi, 0s, Co, Po, Ir, Ni, Cu, Pt, Zn, Ge, Au. In, W, T1. As, Se, MO) Ru, Rh, Pd, Cd, Sn, Sb, S, Ag, Cl, Br, Ta, W. Zr, I, Re, Hf, Tl, Pb, Ru, Th, Pa. Ce, Si, P, Cl, Ge, As, Se, Br, Ru, Sn, Sb, Te, I, Re, 0s, Ir.

(a)* (b)* Group (a)*

(b)* Group (a)* (b) Grouu (a)* (b)* Group (a)* Group (a)* VI: V: IV: III:

V,

Be, Si,

Sc, P,

Cr, V, Co,

Fe, Zn,

Ga, Nb,

Y,

Re, Hf, W,

Zr, Ir.

In,

Re,

Hf,

Au,

Th,

Ac,

Pa,

U.

Mn, v)

Co, w.

Zn,

Ni,

T1.

Ca,

Sr,

Ba,

Ra.

Na,

(Si)**

(Cl)**,

K,

(V)**,

Rb,

Cs,

(W)**.

After

(a),

precipitated

more

or less

completely;

after

(b),

sometimes

precipitated entirely or partially. ** Elements in parentheses unlikely.

PROCEDURE

6 Carrier-Free with Deuterons Mellish,

Separation

of Zn

65

from

Copp er Bombarded

Sour ce: 1. Dissolve target

C.

E.

AERE-I/M-39. face of the spectroscopically and dissolve (diam) the pure residue copper in 2M HC1.

only

the bombarded evaporate through with water. 20 mC

in ElN03, the solution

to dryness, a lCi-cm a few ml

2.

Pass FF

X 1. 5-cm 2~HCl

column all

of De Acidite

resin,

and wash with run,

to remove

the copper.

3. Elute of 10 c/g.

the zinc

In a typical

of zn6

waB separated

with

a specific

activity

PROCEDURE

7 Carrier-Free Irradiated with &ml.

Separation Deuterone Chim. regia,

of Zn

65

from

Copp er

Targets

Source: 1. 20 g copper solved

M.

Lederer,

Acts

~,

134

(1953). to dryness, and dis-

ia dissolved

in aqua

evaporated

in O. lNHC1. or the solution placed directly with on sheets shaken of with

2. CUS may be precipitated,

filter IMHC1. paper. The

chromatogram

is developed

butanol

.3. After

20 hours

the

sheete

are

air

dried.

A green

band

is visible

in the

Rf O. 1 region.

4. The band of zinc

the Cu band

can be detected front

with

an x-ray

counter

2 to 3 cm

ahead

of

(the liquid

is at 27 cm).

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