E L E C T R O L Y T I C C O N C E N T R A T I O N OF A Q U E O U S

S O L U T I O N S OF N I T R I C ACID. I.*
BY
HENRY JERMAIN MAUDE CREIGHTON.
Department of Chemistry, Swarthmore College.
Member of the Institute.

THE nitric acid produced in the arc processes for the fixation
of atmospheric nitrogen 1 usually has a concentration of 33 to 35
per cent. A dilute acid is also produced in its f o r m a t i o n by the
oxidation of ammonia, 2 while in the ordinary method of manu-
facture f r o m Chili saltpetre a dilute acid (3 80 B~. or less) is
obtained f r o m the final towers Or tourilles of the condensing
system. On account of the m a n y uses for concentrated nitric
acid, the problem of concentrating its dilute aqueous solutions is
an important one and one which has received much attention.
As is well known, dilute aqueous solutions of nitric acid can only
be concentrated to about 68 per cent. H N O 3 by distillation at
atmospheric pressure, due to the f o r m a t i o n of a m i x t u r e of
m a x i m u m boiling point ; and by distillation with concentrated snl-
phuric acid aqueous solutions containing 68 per cent. nitric acid
( m i x t u r e of m a x i m u m boiling point) can be concentrated to over
9 ° per cent. a Attempts have been made to concentrate dilute
nitric acid electrolytically, 4 but, as Molinari points out, ~ these
have not yielded practical results.
W h e n an aqueous solution of nitric acid is electrolyzed between
platinum electrodes, the NO:cions and the H - i o n s migrate, respec-
tively, to the anode and the cathode and are there discharged, the
resulting NO~-radicals reacting with the water of the solution in
accordance with the equation:
2NO3 ~- H20 = 2HNOa + O.

* Communicated by Professor Creighton.

i Creighton, H. J. M., This Journal, I87, 379-399 (I919).
2Creighton, H. J. M., Ibid., I87, 7o5-714 (I919).
~Cf. Creighton, H. J. M., and J. H. Githens, ibid., I79, I6I (I915);
Creighton, H. J. M., and H. G. Smith, ibid., x8o, 7o3 (I915).
'German Patent, No. I8o,o5z; English Patent, No. I8,6o3 0f I9o6.
" General and Industrial Chemistry (Inorganic)," p. 396, second edition.
P. Blakiston's Son and Co., Philadelphia, i92o.
VOL. I93, No. II53--7 89
90 H.J.M. CREIGHTON. [J. F. I.

This oxygen and the hydrogen set free at the cathode escape from
the electrolyte in the proportions in which they are present in
water. The net result of electrolysis is, therefore, the decomposi-
tion of some of the water and a consequent increase in the con-
centration of the nitric acid which remains in the solution. If,
however, the dilute nitric acid is electrolyzed in a cell which is
divided into an anodic and cathodic section by means of a porous
diaphragm and F faradays of electricity are passed through the
electrolyte, the following changes occur: At the cathode F gram-
ions of hydrogen discharge and escape from the solution, but, since
the transport number of the NO3-ion in nitric acid is c a . o.I 5, this
loss is partially compensated by migration into the cathodic sec-
tion of o.85 F gram-ions of hydrogen from the anodic section of
the cell. At the same time o.I 5 F gram-ions of NO3 pass from
the cathodic to the anodic section. There occurs, therefore, during
the passage of the current, a loss of o.15 F grarn-molecules of
nitric acid in the cathodic section. At the anode F gram-ions of
NO3 discharge. The nitrate radicals which result do not leave
the solution, but react with the water to form F gram-ions of
hydrogen, F gram-ions of NO3 and o. 5 F gram-atoms of oxygen,
the latter escaping from the electrolyte. Since the anodic section
gains F gram-ions of hydrogen through the NOa-ion discharge
and o.15 F gram-ions of NO 3 by migration from the cathodic
section, and loses o.85 F gram-ions of hydrogen by migration to
the cathodic section, there results a gain of o. 15 F gram-molecules
of nitric acid in the anolyte. Thus, the concentration of the acid
in the anolyte is increased at the expense of that in the catholyte,
the gain in the former being equal to the loss in the latter.
Some of the hydrogen set free in the nascent state at the
cathode reduces part of the nitric acid in the vicinity of the elec-
trode, say through the stages :
HNO8 ~ NO, • HNO, • NO - - • It2N.OH ~ NH3.
The nature of the reduction product formed depends on the tern-
perature, current-density, concentration of the acid and the mate-
rial of the cathode. As early as 1839 Sch6nbein 6 observed that
nitric acid was reduced at the cathode when the acid was concen-
trated, and that current-density played a r61e, while later Brester 7
~Pogg. Ann., 47, 563 (1839).
*Archiv. de Gen~ve (N. S.), 28, 6o (1866).
Jan., 1922. ] ELECTROLYTIC CONCENTRATION. 91

found that during the electrolysis of dilute nitric acid ammonia

was formed at the cathode. More recently, IhleS has shown that,
for a given concentration of nitric acid, ammonia and hydroxyla-
mine are formed at a smooth platinum cathode when the current-
density is above a definite value, and that this value increases with
the concentration of the acid. Thus, at different acid concentra-
tions the minimum current-density at which ammonia is formed is :
Concentration of nitric acid.. 14.67 28.73 43.34 85.37 per cent.
Current-density . . . . . . . . . . . . o.15 I.i22 5.64 860.0 a m p / d i n . 2

In studying the influence of the material of the cathode on the

nature of the reduction product, Tafel 9 has found that while nitric
acid (in the presence of 50 per cent. sulphuric acid) is reduced
only to hydroxylamine at a mercury or well-amalgamated cathode,
it is reduced at a copper cathode to ammonia; with a lead cathode
40 per cent. of the nitric acid is reduced to hydroxylamine, and
with a platinum cathode there is no reduction when the acid is
very dilute. Electrolysis of 40 per cent. nitric acid containing a
small quantity of oxides of nitrogen has been found to yield pure
nitric oxide at a carbon, graphite, gold or platinum cathode. 1°
it is evident from the foregoing that during electrolysis in a
diat;hragrn cell not only will the concentration of the nitric acid in
the catholyte be decreased by loss of hydrogen and migration of
NO:j-ions to the anolyte, but also by partial conversion of the acid
to the oxides of nitrogen (which escape from the solution), am-
monia, etc. If, however, electrolysis is carried out under such con-
ditions that the acid is reduced to the oxides of nitrogen, loss of
the acid by reduction may be overcome, partially at least, by lead-
ing the gases formed in the cathode section into the anolyte where,
in the presence of water and nascent oxygen, the oxides of nitrogen
are converted to nitric acid, thus further concentrating the acid in
the anodic section of the cell.
Some years ago the writer carried out a few experiments on
concentrating aqueous solutions of nitric acid by electrolytic
means. This work was unavoidably interrupted but has recently
been resumed. In this paper a brief account of the results of
these preliminary experiments is given.
A few experiments were first carried out in which 70-71 per
~Z. physik. Chc~*.. 19, 572 (1895).
9Z. anorg. Chem., 3x, 289 (1902).
~0Meister, Lucius and Brfining, English Patent, No. I0,522 of I911.
92 H.J.M. CREIGHTON. [J. F. I.

cent. nitric acid was electrolyzed in a cell without a diaphragm

between the following electrodes : ( i ) A carbon anode and cathode,
(2) a smooth platinum anode and a lead cathode, and (3) a smooth
platinum anode and a carbon cathode. With the first combina-
tion of electrodes it was found that with an anodic current-density
of 4-5 amp./dm3 fragments of the anode began to break off with
a loud cracking sound within a few seconds after the current had
been turned on. In one instance a large piece of the anode was
shot off with such violence that it cracked the glass beaker contain-
ing the electrolyte. After electrolysis had proceeded for a short
time the anode had disintegrated to such an extent as to render
it useless. 11 The cathode did not undergo this disintegration. It was
found on repeating the electrolysis with the second combination of
electrodes, using a cathodic current-density of 5-8 amp./dm. 2,
that the cathode gradually lost its brightness and malleability
and was transformed into a soft, powdery, allotropie modification
of lead. 12 Accordingly, in the concentration experiments which
follow platinum electrodes were employed, although a car-
bon cathode could have been used with a platinum anode.
The electrolysis cell used for the concentration experiments
consisted of a glass cylinder in which was placed a porous, un-
glazed, porcelain cylinder closed at the bottom. The former con-
tained the anolyte and the latter the catholyte. The top of the
porous cylinder was closed by a stopper through which passed the
cathode. A glass tube also passed through th.is stopper and car-
ried the nitrous gases and hydrogen evolved in the cathodic section
into the anolyte immediately below the anode. The stopper
contained a third opening through which electrolyte could be re-
moved or introduced. The acid used for the anolyte and catholyte
was c. p. nitric acid (sp. g. = x.4 2) containing about 71 per cent.
HNO3. The electrolyses were carried out in an open room in
winter weather at a temperature of from 5 to Io ° C. The increase
in the concentration of nitric acid in the anolyte (or the decrease in
concentration in the catholyte) was followed by removing Iocc. of
the electrolyte, diluting to Iooo cc. and neutralizing Io cc. of this
dilute solution with a standard solution of barium hydroxide.
11This phenomenon of the disintegration of carbon anodes in nitric acid
is being studied further.
12Creighton, H. J. M., lour..,'truer. Chem. Soc., 37, 2o64 (I9~5).
J a n . , 1922.] ]LLECTROLYTIC CONCENTRAT;ON. 93

I n all e x p e r i m e n t s the final c o n c e n t r a t i o n o f the acid w a s d e t e r -

m i n e d by a n a l y z i n g a k n o w n w e i g h t o f the a n o l y t e .
I n T a b l e I are g i v e n the results o f a c o n c e n t r a t i o n e x p e r i m e n t

TABLE I.

Concentration of HN0~ in
Time Current- Potential Quantity of Energy
strength difference electricity Consumed
Hours consumed Ano!yte Catholyte
Amperes Volts Amp. -hrs. Kw. -hrs.
% %

O 3.5 0 o 71.7 o 71.7 o

2 3.5 I2 0.042 74.35 ....
4 3.5 24 0.084 76.44 ....
6 3.5 36 0.126 78.88 ....
8 3.5 48 o.168 81.35 ....
II* 3.5 66 o.23t 84.oo 50.36
II 2.0 66 0.231 84.oo 5o.36
22 2.0 88 0.275
22 3.5 88 0.275
25 3.5 lO6 0.338 88.40 ....
27 3-5 II8 o.38o 92.22 ....
34 3.5 I6O o.507 94.4° 14.04

* The color of the catholyte ~ras blue-green.

TABLE I I .

Time Current- Potential Quantity of Energy Concentration of

strength difference electricity consumed HN0s in anolyte
consumed
Hours Amperes Volts Amp. -hrs. Kw. -hrs. %

o 3.4 0 0 71.4
4 3.4 28 0.0952 73.5
8 3-4 56 o.I9O4 76.7
12 3-4 84 0.2856 77.2
21" 3.4 147 o.499~ 8o.6
25 3.4 I75 0.5950 83.0
29 3.4 203 0.6902 84.5
29 3.0 203 0.6902 84.5
35~ 3.0 239 o.7982
46 3.0 305 0.9962 9o.1
46 4.0 305 o.9962 9o.1
48 4..5 321 1.o642
49 5.5 329 1.1o42
5o 6.0 337 1.1502
51 6.5 345 1.2002

*a5o cc. catholy~e removed and 25o cc. 71.4% HNO~ added to cathode section.
~2oo cc. catholyte removed and ~oo cc. 7 ~.4% HNOs added to cathodic.section•

i n w h i c h the v o l u m e s o f a n o l y t e a n d c a t h o l y t e used were, respec-

tively, 2 5 o cc. a n d I5O cc. o f 7 I . 7 per cent. n i t r i c acid. In a
s e c o n d e x p e r i m e n t , the r e s u l t s o f w h i c h a r e r e c o r d e d i n T a b l e I I ,
94 H. J. M. CREIGHTON. [J. F. I.

the volume of anolyte was 975 cc. (I385 grams) and the volume
of catholyte was 55 ° cc. (780 grams). In this experiment 345
ampere-hours of current were passed through the cell and the
concentration of the anolyte raised from 71.4 to 92.2 per cent.
H N O 3 (d~o° = 1.4987). The weight of the anolyte at the end
of the experiment was I 2 I o grams. That this weight was not
greater was due to losses by evaporation, to the removal during
the experiment of I5O cc. for titration, and probably to loss by
diffusion into the cathodic section. In another experiment an
attempt was made to increase further the concentration of the
92.2 per cent. acid obtained in the preceding experiment. Three
hundred grams of the 92.2 per cent. acid were placed in the anodic
section and 285 grams of 71.4 per cent. acid were placed in the
cathodic section of a small concentrating cell. As it was desired
to obtain as pure an acid as possible, the nitrous gases formed in
the cathodic section were not led into the anolyte and t h e tem-
perature of the electrolyte was not allowed to rise above 8 ° C.
The acid was electrolyzed for seven hours, during which time 48
ampere-hours of current were passed through the cell and 0.300
kw.-hr, of energy consumed. At the conclusion of electrolysis
there were 35 ° grams of anolyte containing 99.65 per cent. H N O 3
(d 's°-1.5193)
4 o- On being removed from the cell at the con-
clusion of electrolysis this acid was almost colorless; but after
standing for twenty-four hours in a room at ordinary temperature
it became lemon yellow in color.
In each of the foregoing experiments the porous cylinder
underwent considerable disintegration and could not be used for
a second experiment. This difficulty can probably be overcome,
however, by using an aluminum cylinder, since it has been found
that a cylinder of this material undergoes but little change in
weight on being immersed in 7° per cent. nitric acid for six weeks.
In order to determine to what extent " spent a c i d " (i.e., a
mixture of nitric and sulphuric acids diluted and partially deprived
of the former acid by use in nitrating organic substances, e.g.,
glycerine) could be concentrated electrolytically, a spent acid con-
taining 70.03 per cent. H2SO4, IO.O6 per cent. H N O 3 and I9.9 I
per cent. H 2 0 was electrolyzed, the gases evolved in the cathodic
section of the electrolysis cell being led into the anolyte immediately
below the anode. Four hundred and fifty-five grams of the spent
acid were placed in the anodic section of the cell and 37 ° grams in
Jan., 1922.] ELECTROLYTICCONCENTRATION. 95

the cathodic section. T h e acid was electrolyzed for ten hours with
a current of eight amperes, the mean potential difference being
6.75 volts. At the conclusion of electrolysis the weight of anolyte
was 440 grams. T h e anolyte was analyzed and found to contain
74.4 p e r cent. H 2 S O , , 21.32 per cent. H N O a and 4.28 per
cent. H,_,O.
SUMMARY.

I. A number of preliminary experiments on concentrating

aqueous solutions of nitric acid by electrolytic means have been
carried out.
2. T h e concentration of nitric acid has been increased f r o m
71 to over 99 per cent. H N O a by electrolysis in a diaphragm cell.
3. T h e concentrations of nitric and sulphuric acids in " spent
a c i d " have been materially increased and the amount of water
decreased by electrolysis.
DEPARTMENT OF CHEMISTRY,
SWARTHMORE COLLEGE,
S WARTHMORE, PENNA.,
December IO, 1921.

An Acoustical Galvanometer for the Measurement of Srna11

Alternating Currents. F. R. WATSON and L. B. HAM. ( P h y s .
R e v . , September, 1921.)---Ordinarily the word galvanometer calls up
the image of a moving part actuated by the action of one magnetic
field upon another. In the acoustical gMvanometer there is one mag-
netic field, because there is a current of electricity, but there is not a
second one. The alternating current to be measured passes through
a Western Electric No. II7"W loud-speaking telephone receiver.
The plate of this is set in vibratior~ and sound waves are produced
in an enclosed mass of air. This closed chamber consists of two
cylinders joined by a tube. The receiver forms the end of one cylin-
der and the other is closed by a platte of glass. Wi4thin this double
resonator standing waves are formed. In the connecting tube
is suspended by a quartz thread a Rayleigh disc, a microscope cover
glass in fact, wkh its plane at an angle to the axis of the tube. When
standing waves develop this disc turns through an angle. A ray of
light enters through the glass end, is reflected from the suspended
disc and is received upon a scale. "When the disc turns this reflected
ray is deviated. When the sound wave had a frequency of 51o
vibrations per sec., 5.7 x IO-s amperes produced a deflection of one
ram. on a scale one metre distant from the deflected disc. The sen-
sitivity varies with the frequency.