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The following compounds were found to give colored are probably isomers or mixtures of isomers, a point that
oxidation products, but the color changes are not striking will be studied in the continuation of this effort to find new
enough to warrant the use of the materials as oxidation- and possibly better indicators for use with dichromate.
reduction indicators: N , "-dimethyl benzidine (Q),benzidine
monosulfonic acid (8), and dinaphthocarbazol ( 5 ) . Literature Cited
The very excellent indicator prepared by Straka and (1) Barkenbus and Owen, J . Am. Chem. Soc., 56, 1204 (1934).
(2) Bayer, Friedrich, and Co., German patent. 38,664 (February 17,
Oesper from the reaction of ethyl sulfate on acetyl diphenyl-
amine has now been purified by the procedure described
. ,
1886) : Friedldnder. 1. 500 (1888).
(3) Fieser,' "Experiments~in Organic Chemistry," p. 140, Chicago,
above. Analysis shows it to be a monosulfonate of diphenyl- D. C. Heath & Co., 1935.
amine: sodium found, 8.46 per cent; calculated, 8.49. KO (4) Kolthoff and Sarver, J . Am. Chem. Soc., 53, 2902 (1931).
less than three monosulfonated derivatives of diphenylamine (5) Nietski and Goll, Ber., 18, 298, 3252 (1885).
(6) Sarver and Johnson, J . Am. Chem. Soc., 57, 329 (1935).
have now been recommended for use as oxidation-reduction (7) Straka, Leora, Ph.D. thesis, University of Cincinnati, 1934.
indicators: (1) that of Kolthoff and Sarver (4); (2) that of (8) Straka and Oesper, IND.ENQ.CHEM.,Anal. Ed., 6, 465 (1934).
Straka and Oesper; and (3) that produced by aged ethyl (9) Willstatter and Kolb, Ber., 37, 3772 (1904).
sulfate or, better, butyl sulfate and diphenylamine. They RECEIVED June 17, 1936
o-$44
We may then expect t h a t a t low acidities the end point will
come too soon, giving low values in the titration. Evidence
.-.-0'
S--K
supporting these statements is given below.
O = N l/ o o H *
o s - s / Materials and Solutions
I 1
H H
Light yellow
A Potassium Chloride. The recrystallized material was used in
preparing a standard 0.1 Nsolution.
Diphenyl Carbazide and Diphenyl Carbazone. Colorless
01-i 1-0- + H+
Eastman Kodak diphenyl carbazide (m. p., 167.5", cor.) was
used directly. Diphenyl carbazone was prepared by the method
of Heller (4) and showed after three recrystallizations from
acetone and water a melting point of 149.5' to 150' (cor.).
O
yd Although this melting point is 8" lower than that of Heller or of
Slotta and Jacobi (a), further recrystallizations from benzene
or from benzene and petroleum ether failed to raise it. (This
H is of little significance, since the indicator solution used prob-
Orange ably contains both the carbazide and the carbazone.)
366 INDUSTRIAL AND ENGINEERING CHEMISTRY VOL. 8 , NO. 5
A saturated solution of diphenyl carbazide in 95 per cent Nos. 4 to 8, to the 5 cc. of potassium chloride were added 2 drops
ethyl alcohol, which gradually turns red after standing for of bromophenol blue, the specified amount of nitric acid, and 5
several days, was used as the indicator. No difference in action drops of diphenyl carbazide. The solution was then titrated
could be detected between this solution, a fresh solution of the with mercuric nitrate.
carbazide, and a diphenyl carbazone solution in alcohol.
Sodium Hydroxide. Standard 0.1 N and 0.025 N solutions An accurate determination of the acidity of a mercuric
were prepared and stored by the usual methods. nitrate solution may be made by the sodium hydroxide titra-
Hydrochloric Acid. A standard 0.1 N solution was prepared
from constant-boiling hydrochloric acid. tion mentioned just above. Mercuric oxide will not pre-
0.20 N Nitric Acid. cipitate during the titration with alkali if an excess of chlo-
Mercuric Oxide. c. P. mercuric oxide was dissolved in 1 to 1 ride ion is present and if the solution is dilute.
nitric acid and filtered. To the filtrate was added 8 M sodium
hydroxide until precipitation was complete. The precipitate
was filtered and washed free from alkali (phenolphthalein). Discussion of Results
The yellow mercixic oxide was then dried over phosphorus pen-
toxide for 10 days, during which period it was powdered from The accuracy obtainable by this method is shown by com-
time to time. parative results obtained by titration of 0.1 N hydrochloric
Mercuric Nitrate Solutions. In preparing the 0.1 N and acid and 0.1 N potassium chloride with 0.10742 N mercuric
0.025 N solutions, as little nitric acid as possible was used. nitrate, and by other methods. The accuracy is never poorer
After the required amount of mercuric oxide was weighed ac-
curately and suspended in water, the calculated equivalent than 0.3 per cent.
amount of nitric acid was added. Then to the well-stirred mix- Concentration of KC1
ture, concentrated nitric acid was added drop by drop until From weight of KCl used 0,10524 N
complete solution took place. After making up to volume, the -
From He(iV0dz titration 0.10509 N
solutions were no more than 0.01 Nwith respect to nitric acid. Concentration of HC1
From NaOH titration 0 10420 N
From Hg(N0a)z titration 0 1043s N
Titration Procedures
The effect of acidity on the titration can be seen in Table I.
With 0.1 N mercuric nitrate the following procedure has The titer given in the third column is the mean of two values
been found satisfactory: never deviating by more than 0.04 cc. except in No. 8.
The final volume of the solution being titrated should be The blank was determined for the total amount of nitric acid
about 80 to 100 cc. If th’e chloride solution to be titrated is from the two sources. It is obvious, upon comparison of the
acid, it should first be neutralized with sodium hydroxide. If final corrected titer with the calculated value of 21.52 cc.,
the acid titer is also required, 5 drops of diphenyl carbazide are that above p H 2.0 the titers are all too low, as expected from
added and the solution is titrated with standard sodium hy- the discussion above. The agreement is good in the range
droxide to the orange color. Four cubic centimeters of 0.2 N
nitric acid are added and the solution is then titrated with 0.1 N 1.5 to 2.0. Below p H 1.5, the sensitivity and the precision
mercuric nitrate. About 5 drops before the end point, a pink- are both lowered; the results, however, are invariably correct
violet color begins to develop; at the end point, one drop changes within the reduced precision a t these acidities, when the
the color from a light violet to a deep blue-violet. blank correction is applied. I n the p H range 1.5 to 7.0, the
end point is sharp whether or not the absolute value of the
Theoretically the blank should correct not only for the 4 titer is correct.
cc. of nitric acid added, but also for the amount of nitric
acid present in the mercuric nitrate used in the titration. TABLEI. EFFECTOF ACIDITYON TITRATION
Actually the error involved in neglecting this last factor is (Titration of 5.020 cc. of 0.10524 N KCL with 0.02455 N Hg(N0a)g;a
less than 0.02 cc. of 0.1 N mercuric nitrate, if the amount of calculated titer = 21.52 cc.)
nitric acid in the mercuric nitrate solution is less than 0.01 N . N HNOa
No. 0.2 Added pHb Titer HXOa
Blank (Cor.)
Titer
With 0.025 N mercuric nitrate additional precautions must cc. Cc. .
cc
be taken: 1 0.35 2.9 20.76 0.01 20.75
2 0.70 2.6 21.11 0.01 21.10
The final volume of the solution being titrated in this case 3 1.2 2.4 21.30 0.02 21.28
should be 65 * 10 cc. If the chloride solution to be titrated is 4
5
2.0
3.0
2.0
1.9
21.53
21.60
0.06
0.10
21.47
21.50
acid, 2 drops of 0.2 per cent bromophenol blue are added, and 6 4.0 1.8 21.66 0.15 21.51
the solution is titrated with standard sodium hydroxide to the 7 6.0 1.7 21.76 0.22 21.54
full blue color. Four cubic centimeters of 0.2 N nitric acid are 8 10.0 1.5 21.90 0.36 21.54
added, then 5 drops of diphenyl carbazide indicator, and the a This mercuric nitrate solution was 0.0078 N with respect t o nitric acid,
b Calculated from the nitric acid added to the titration mixture from the
solution is titrated with 0.025 N mercuric nitrate to a definite two sources.
pink color, which can be reproduced to 10.02 cc., with the aid
of a daylight lamp. The yellow color imparted by the bromo-
phenol blue in no way interferes with the mercuric nitrate end These p H values are significant only for the titration
point, and to make conditions uniform for all experiments pre- conditions described here. Variation in the volume of the
sented here, 2 drops of bromophenol blue are added to all titra- solution being titrated and in the amount of indicator used
tion mixtures where 0.025 N mercuric nitrate is used. will probably shift the optimum p H range through displace-
ment of the various equilibria described above.
The blank correction is determined not only with 2 drops According to the theory of the titration presented here, a n
of 0.2 per cent bromophenol blue and 4 cc. of nitric acid, but increase in the concentration of mercuric chloride present
also with nitric acid equivalent to the amount of acid in the should probably decrease the titer. This has been found to
mercuric nitrate used in the titration. Neglecting the latter be true, but titration of varying amounts of potassium chlo-
may cause as much as 0.07 cc. error in the blank. ride (1 to 10 cc. of 0.1 N potassium chloride) using from 5 to
The experiments listed in Table I, where the acidity 45 cc. of mercuric nitrate (0.025 N ) on the buret, shows a
was being varied, may be divided into 2 groups : maximum error of 0.2 per cent due to this effect.
In Nos. 1 to 3, most of the mercuric nitrate used had to be The titration has already been applied successfully in
first neutralized, while in Nos. 4 to 8 no such neutralization was determination of iodide (2)and silver ( 3 ) . It has been used in
necessary. Nos. 1 to 3 were performed by pipetting 5.020 =t this laboratory to determine mercuric ion in dilute solution.
0.005 cc. of 0.10524 N potassium chloride and running in 20.00 cc. This is done by adding a known amount of chloride (excess),
of 0.02455 N mercuric nitrate. The acid was then titrated with titrating the acid to a bromophenol blue end point, adjusting
0.025 N sodium hydroxide to bromophenol blue, the specified
amount of nitric acid and 5 drops of diphenyl carbazide were the acidity, and titrating with mercuric nitrate to a diphenyl
added, and t h e mercuric nitrate titration was completed. In carbazide end point.
SEPTEMBER 15, 1936 ANALYTICAL EDITION 367
FIQURE1. MODIFIED
KJELDAHL
DISTILLATION
APPARATUS