SEPTEMBER 15, 1936 ANALYTICAL EDITION
The following compounds were found to give colored
oxidation products, but the color changes are not striking
enough to warrant the use of the materials as oxidation-
reduction indicators: N , "-dimethyl benzidine (Q),benzidine
monosulfonic acid (8), and dinaphthocarbazol ( 5 ) .
The very excellent indicator prepared by Straka and
Oesper from the reaction of ethyl sulfate on acetyl diphenyl-
amine has now been purified by the procedure described
above. Analysis shows it to be a monosulfonate of diphenyl-
amine: sodium found, 8.46 per cent; calculated, 8.49. KO
less than three monosulfonated derivatives of diphenylamine
have now been recommended for use as oxidation-reduction
indicators: (1) that of Kolthoff and Sarver (4); (2) that of
Straka and Oesper; and (3) that produced by aged ethyl
sulfate or, better, butyl sulfate and diphenylamine. They
Titration of Chloride Ion with Mercuric Nitrate
Solutions
Using Diphenyl Carbazide Indicator
IRVING ROBERTS, Columbia University, New York, N. Y.
D IPHENYL carbazide and diphenyl carbazone have
been suggested as indicators in the titration of chlo-
ride with mercuric nitrate solutions by Dubsky and Trtilek
(1, 2, 3, 10) and by Slotta and Muller (9) in place of the
inaccurate Mohr and inconvenient Volhard methods (6).
The method depends upon the formation, from mercuric
ion and the indicator, of a deep blue-violet complex, after
the chloride ions have combined to form slightly ionized
mercuric chloride. Unexplained anomalous effects of acidity
on the sensitivity and absolute values given by the titra-
tion were found, which make their results unreproducible.
The author has found that both precision and accuracy can be
obtained if the proper precautions are taken, and that
mercuric oxide, first used as a primary standard in alkalimetry
(6, 7), may be conveniently used as a primary standard in pre-
paring mercuric nitrate solutions.
The probable mechanism of this titration may be seen
from a few qualitative observations. Diphenyl carbazide
is an acid-base indicator, changing from a light yellow in acid
solution to a deep orange in alkaline solution, in the pH range
6.6 to 7.4 (determined with phosphate-citrate buffers).
The equilibrium is probably of the following type:
H H H H
o-$44
.-.-0'
S--K
O = N l/ o o H *
o s - s /
I 1
H H
Light yellow
A Potassium Chloride. The recrystallized material was used in
01-i 1-0- + H+
O
yd
H is of little significance, since the indicator solution used prob-
Orange
365
are probably isomers or mixtures of isomers, a point that
will be studied in the continuation of this effort to find new
and possibly better indicators for use with dichromate.
Literature Cited
(1) Barkenbus and Owen, J . Am. Chem. Soc., 56, 1204 (1934).
(2) Bayer, Friedrich, and Co., German patent. 38,664 (February 17,
. ,
1886) : Friedldnder. 1. 500 (1888).
(3) Fieser,' "Experiments~in Organic Chemistry," p. 140, Chicago,
D. C. Heath & Co., 1935.
(4) Kolthoff and Sarver, J . Am. Chem. Soc., 53, 2902 (1931).
(5) Nietski and Goll, Ber., 18, 298, 3252 (1885).
(6) Sarver and Johnson, J . Am. Chem. Soc., 57, 329 (1935).
(7) Straka, Leora, Ph.D. thesis, University of Cincinnati, 1934.
(8) Straka and Oesper, IND.ENQ.CHEM.,Anal. Ed., 6, 465 (1934).
(9) Willstatter and Kolb, Ber., 37, 3772 (1904).
RECEIVED June 17, 1936
In alkaline, neutral, or slightly acid solution, dilute mer-
curic chloride gives the deep blue-violet color with the indi-
cator. If a solution containing both mercuric chloride and
diphenyl carbazide is just above pH 7, the addition of large
amounts of potassium chloride will not remove the color,
whereas a drop of nitric acid will. On the other hand, with a
highly acid solution containing the indicator, such as 1 to 1
nitric acid, a large amount of mercuric nitrate must be added
before any color is seen.
These observations seem to indicate that it is only the alka-
line form of the indicator which forms the deep blue-violet
complex with mercuric ion. As the acidity of the solution
increases, the above equilibrium is driven to the left and the
concentration of the alkaline form decreases, so that beyond a
certain acidity we may expect the sensitivity of the titration
to be too low for great precision. Also, that mercuric chlo-
ride itself gives the blue-violet color with the indicator in
weakly acid solution is probably due to the fact that, a t low
acidity, the concentration of the alkaline form of the indica-
tor is great enough to give appreciable reaction with mer-
curic ion from the dissociation of mercuric chloride :
HgCL $ Hg++ + 2 C1-
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
supporting these statements is given below.
Materials and Solutions
preparing a standard 0.1 Nsolution.
Diphenyl Carbazide and Diphenyl Carbazone. Colorless
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.).
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
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

Acknowledgment Literature Cited

The author is grateful to L. P. Hammett for his interest
and helpful suggestions throughout this research.
Summary
The titration of chloride ion with mercuric nitrate solution
using diphenyl carbazide indicator has been found to give
accurate results in a definite range of acidity. A probable ex-
planation is given. Mercuric oxide may be used as a primary
standard in the preparation of mercuric nitrate solutions.
With the method given above, the accuracy of the method is
better than 0.3 per cent with ordinary volumetric apparatus.
(1) Dubsky and Trtilek, Mikrochemie, 12, 315 (1933).
(2) Ibid., 15, 302 (1934).
(3) Dubsky and Trtilek, 2. anal. Chem., 93,345 (1933).
(4) Heller, Ann., 263,274 (1891).
(5) Incze, 2. anal. Chem., 56, 177 (1917).
(6) Kolthoff and Sandell, "Textbook of Quantitative Inorganic
Analysis," pp. 449-56, New York, Macmillan Co., 1936.
(7) Kolthoff and Van Berk, 2. anal. Chem., 71,339 (1927).
(8) Slotta and Jacobi, Ibid., 77, 344 (1929).
(9) Slotta and Muller, Chem. Fabrik, 7,380 (1934).
(10) Trtilek, Collection Czechoslov. Chem. Communications, 5, 302
(1933).
RECEIVED
June 18, 1936.

Special Head for Iijeldahl Distillation Apparatus

CHAS. E. WEAKLEY, JR.
West Virginia Agricultural Experiment Station, Morgantown, W. Va.

U NITS for Kjeldahl distillations usually are so constructed

as to require a glass connecting bulb of some descrip-
tion to connect the flask with the condensing apparatus.
Theoretically this setup is all that can be desired, since the
connecting bulb holds back any spray from the boiling liquid
and breaks up any foaming which may occur. However, the
flasks have nothing to hold them securely in place other than
a rubber connection a t the top, and most distillations of this
kind do some bumping.
Figure 1 shows a modified Kjeldahl distillation apparatus
which has been successfully used in this laboratory. It con-
sists of a well-known manufactured unit with the addition
of special metal heads to take the place of the usual glass
connecting bulbs. Figure 2 is a cross section of the head and
is self-explanatory. The block-tin condenser tube which
comes with this particular apparatus is the right length to
be soldered into the head and should extend to within 2 or 3
mm. of the top (soldered cap). These heads are held se-
curely in place by a strip of wood 32 mm. (1.25 inches) wide,
sawed off longitudinally through the centers of the 32-mm.
(1.25-inch) holes in which the heads are placed. A long screw
between each two heads and a t the ends holds them securely
in position after they are adjusted properly for height. The
wire gauze and glass beads completely break up and return
to the flask any spray or foam which may occur.
The operation of the unit is very simple: The rubber
FIQURE2. KJELDAHL
DISTILLATION
HEAD
(All dimensions in millimeters)

stopper is pushed t o the top of the lower tube, the 800-cc.

Kjeldahl flask put in position, and the stopper pushed down
with a twist into the neck of the flask, holding,it tightly.
Figure 1 also shows supports for the receiving flasks which
are very convenient, especially in adjusting the delivery tubes
to the proper depth in the acid. If these tubes are made suf-
ficiently large (inverted filter tubes serve nicely) and are kept
just under the surface of the acid, there will be no danger of
acid sucking up into the condensers because of uneven heat-
ing.
R E C ~ I V EMay
D 21, 1936. Published with the approval of the Director,
West Virginia Agricultural Experiment Station, as Scientific Paper 168.

FIQURE1. MODIFIED
KJELDAHL
DISTILLATION
APPARATUS