THE SILVER COULOMETER.

By K. E. GuTHE.

1. According to Faraday's law of electrolysis, a strict proportion-

ality exists between the quantity of electricity passing through an
electrolyte and the electrochemical reaction produced by it. The lat-
ter may therefore serve for the measurement of quantity of electricity.
We call the instruments employed for this purpose '"voltameters" or
"coulometers."
A good many different types of coulometers have been used; for
example, the gas coulometer, in which the volume of the liberated
gases is measured, or the iodine and the iron coulometers, in which
the electrochemical change is measured by titration. The usual
method, however, is the determination of the mass of a substance
deposited at one of the electrodes by an electric current." Of the last
the copper coulometer and the silver coulometer are the best-known
types.
The investigations of F. and W. Kohlrausch,* Rayleigh and Sidg-
wick,^ Gray,^ Schuster and Crossley,^ and Glazebrook and Skinner,^
have proved that the silver coulometer is by far the most reliable
instrument of this sort and that it will give results accurate to 1 in
5,000 if certain specifications as to its construction and treatment are
closely followed.

«A description of some unusual types is given by Danneel: ZS. f. Electroch., 4,

p. 154; 1897.
^Fr. and W. Kohlrausch: Wied. Ann., 27, p. 1; 1886.
cKayleighand Sidgwick: Phil. Trans., 175, p. Ill; 1884.
^Gray: Phil. Mag., 22, p. 389; 1886.
e Schuster and Crossley: Proc. Roy. Soc,
50, p. 344; 1892.
/Glazebrook and Skinner: Phil. Trans., 183, p. 567; 1892.
349
350 BULLETIN OF THE BUKEAU OF STANDARDS. [vol.i.no.S.

2. For this reason the International Electrical Congress, held at

Chicago in 1893, adopted the silver coulometer as a standard for the
measurement of electric current. Though the ampere was defined as
one-tenth of the unit of current of the c. s. system of electromag-
g.
netic units, it was added that it ''is represented sufficiently well for
practical use b}^ the unvar3'ing current which, when passed through a
solution of nitrate of silver in water in accordance with standard speci-
fications, deposits silver at the rate of 0.001118 gram per second."
This value is called the electrochemical equivalent of silver.
Specifications, as referred to above, were prepared by the National
Academy of Sciences and legalized in the United States in 1894. They
are practically in conformity with the earlier specifications of the
British Board of Trade and read as follows:
In employing the silver voltameter to measure currents of about one ampere the
following arrangements shall be adopted:
The cathode on which the silver is to be deposited shall take the form of a plati-
num bowl not than 10 cm. in diameter and from 4 to 5 cm. in depth.
less
The anode shall be a disk or plate of pure silver some 30 sq. cm. in area and 2 or
3 mm. in thickness.
This shall be supported horizontally in the liquid near the top of the solution by
a silver rod riveted through its center. To prevent the disintegrated silver which is
formed on the anode from falling upon the cathode, the anode shall be wrapped
around wT.th pure filter paper, secured at the back by suitable folding.
The liquid shall consist of a neutral solution of pure silver nitrate containing about
15 parts, by w^eight, of the nitrate to 85 parts of water.
The resistance of the voltameter changes somewhat as the current passes. To
prevent these changes having too great an effect on the current, some resistance
besides that of the voltameter should be inserted in the circuit. The total metallic
resistance of the circuit should not be less than 10 ohms.
—
Method of making a measurement. The platinum bowl is to be washed consecutively
with nitric acid, distilled water, and absolute alcohol. It is then to be dried at 160°
C. and left to cool in a desiccator. When thoroughly cool it is to be weighed carefully.
It is to be nearly filled with the solution and connected to the rest of the circuit
by being placed on a clean insulated copper support to which a binding screw is
attached.
The anode is then to be immersed in the solution so as to be well covered by it
and supported in that position. The connections to the rest of the circuit are then
to be made.
Contact isbe made at the key, noting the time. The current is to be allowed to
to
pass for not less than half an hour and the time of breaking contact observed.
The solution is now to be removed from the bowl and the deposit washed with
distilled water and left to soak for at least six hours. It is then to be rinsed suc-
cessively with distilled water and absolute alcohol and dried in a hot-air bath at a
temperature of about 160° C. After cooling in a desiccator it is to be weighed again.
The gain in mass gives the silver deposited.
To find the time average of the current in amperes this mass, expressed in grams,
must be divided by the number of seconds during which the current has passed and
by 0.001118.
GUTHE.] THE SILVER COULOMETER. 851

In determining the constant of an instrument by this method the current should

be kept as nearly uniform as possible and the readings of the instrument observed at
frequent intervals of time. These observations give a curve from which the reading
corresponding to the mean current (time average of the current) can be found. The
current, as calculated from the voltameter results, corresponds to this reading.
The current used in this experiment must be obtained from a battery and not from
a dynamo, especially when the instrument to be calibrated is an electrodynamometer.

Other countries in which the silver coulometer has been legalized

have adopted similar rules.
3. The minute description of the form and treatment of the silver

coulometer implies that a slight departure from the specifications may

result in a deposit of silver not in accordance with the definition of
the ampere. It was apparent that there are in the instrument disturb-
ing factors which required a further study.
Novak,^ who worked with the Kohlrausch form i. e., a coulometer —
in which a small glass bowl is suspended below the anode in order to
prevent any particles from falling upon the cathode bowl describes —
some of the difficulties encountered and strongly emphasizes the
necessity for a thorough study of the side reactions, such as the for-
mation of the anode slime and the possible existence of a complex sil-
ver salt in the electrolyte.
Kahle^ has shown that the electrolyte becomes acid by electrolysis
and that on repeated use the deposits are too large. The Reichsan-
stalt recommends, therefore, that not more than 3 grams of silver
should be deposited from 100 cm^ of the solution.
Leduc hopes to overcome all trouble by employing a large silver
'^

anode, consisting of granulated silver. He keeps the anodic current

density below 0.02 ampere per cm^ and recommends that the amount of
silver collected at the cathode should be large, say about 30 grams.
Patterson and Guthe^ obtained concordant results by keeping the
solution in contact with silver oxide. Leduc speaks in favor of this
method, but Richards's results with the same type show great varia-
tions in the amount of silver deposited by the same quantity of elec-
tricity.

«The Electrician, 27, p. 325; 1891. ZS. f. Instrk., 21, p. 180; 1901.
^Novdk: Studie o voltametru na stribro, Proc. Roy. Bohemian Ac. Sci., Prague, 1,
pp. 387-432; 1892. This paper seems to have been published in the Bohemian lan-
guage only, and I failed to find any reference to it in the literature on the subject.
I am indebted to Mr. C. M. Jan sky for a translation of it.
cKahle: ZS. f. Instrk., 18, pp. 229 and 267; 1898.
c^Leduc: J. dePhys., 1, p. 561; 1902.
« Patterson and Guthe: Phys. Rev., 7, p. 257; 1898.
352 BULLETIN OF THE BUREAU OF STANDARDS. [vol.1,no.3.

4. The greatest advance in our knowledge of the subject is due to

the excellent researches of Richards^ and his collaborators who have
shown that the main formation of a heavy anode
difficulty lies in the
solution containing a complex silver ion, the existence of which had
already been suggested by Novak and Kodger and Watson.* The
anode solution, which in the ordinary type of coulometer sinks to the
bottom of the vessel, producing there a star-shaped figure, will yield
on electrolj^sis more silver than corresponds to the normal ion. The
substance formed at the anode must be a reducing agent since oxygen
tends to eliminate it. The exact chemical constitution of the substance
is not known.
Novak had obtainedresults which at first seemed to me strong proofs
of the above. In his experiments in which the coulometer forms by
far the greater part of the total resistance of the circuit, he observed
regularly a decrease of the current with the time, pointing to an
increase of the resistance of the solution. Moreover, he found the
silver loss at the anode to be greater than the gain at the cathode,
while the concentration of the electrolyte seemed to have decreased.
The latter was determined b}^ precipitating the silver by means of
hj^drochloric acid and a careful weighing of the silver chloride. The
conclusion was drawn that some of the silver in the solution was in
such a form that it would not be precipitated b}^ hydrochloric acid.
Novak states that Dr. Sulc actually found silver in the filtrate after
such precipitation. Such a direct proof of the presence of a complex
silver salt in the electrol3^zed solution seemed to call for corroboration,
and the author therefore repeated the experiments. Two coulometers
were used, one with a platinum bowl as cathode and a silver plate as
anode, the other with a platinum crucible and a silver rod as electrodes.^
The current and the potential difference at the terminals of each coul-
ometer were read simultaneously at short intervals and the tempera-
tures noted. At first the resistance decreased with increasing temper-
ature, but after a while remained constant, though the temperature
still rose somewhat. Apparentl}^ an effect was obtained similar to,
though considerably less pronounced than, that in Novak's experi-
ments, in which the change in the resistance amounted to as much as
4 per cent.
The following two experiments show the reason for the increase of
resistance: In the one case (A) we used the bowl 10 cm in diameter

« Richards, Collins and Heimrod: Proc. Am. Acad., 35, p. 123; 1899. Richards
and Heimrod: Proc. Am. Acad., 37, p. 415; 1902.
& Rodger and Watson: Phil. Trans., 186, p. 631; 1895.

c The silver used was obtained from the United States Mint and is very pure.
GUTHE.] THE SILVER COULOMETER. 353

and covered the bottom with a large watch glass. The anode was a rod
1 cm thick, the lower end of which touched the glass. The depth
of the solution above the glass was 1.5 cm. In the second case (B) the
crucible was used and a small glass bowl placed at the bottom under
the rod which formed the anode. In both cases the concentration of
the solution was 5 per cent.

TIME IN MINTUES
10 20 30 40 50 60 70

Fig. 1. —Variation of resistance of the eoulometer. (See Table 1.)

The following table shows that in the first case there is a constant
decrease of resistance corresponding to the rise of the temperature.
In the second the pronounced increase in the resistance can only be
attributed to the collection of the heavy anode solution in the beaker,
and the corresponding decrease in the concentration in the remaining
electrolyte through which the current had to pass. Novak attributed
the increase of the resistance partly to the formation of the anode
slime and the presence of gas bubbles, but experiment (A) clearl}^
demonstrated that this is not the case.
To test the second part of Novak's results two experiments were
made with a 13 per cent solution, one with a bowl eoulometer and
another with a crucible as cathode. The anodes were not protected.
The weighed amount of the original electrolyte was precipitated by
means of pure hydrochloric acid, filtered through a Gooch crucible,
and carefully weighed to 0.01 mg. After having passed a current of
1 ampere for 1.5 hours through the coulometers, the silver in the two

2214— No. 3—05 5

354 BULLETIN OF THE BUREAU OF STANDARDS. [VOL. 1, NO. 3.

Table I.

EXPERIMENT A.

Current, Pot. diff., Kesistance,

Time. Temperature.
in amperes. in volts. in ohms.

h. m.
1 15 21.2 0. 378 1.860 4.921
16 21.2 .380 1.854 4.879
17 21. 2 .381 1.845 4. 843
18 21.4 .3775 1.820 4.821
20 21.6 .393 1.885 4.797
22 21.8 .395 1.882 4.765
25 22.0 .3975 1.882 4.735
28 22.2 .3995 1.880 4.706
33 22.7 .401 1.880 4.688
42 23.2 .404 1.880 4.654
53 23.6 .406 1.878 4.625
2 02 24.0 .4075 L876 4.604
14 24.3 .409 1.874 4.582

EXPERIMENT B.

2 47 22.8 0.350 1.36 3.886

48 23.0 .353 L346 3.818
49 23.0 .353 1.341 3.803
50 23.0 .3525 1.341 3.804
51 23.0 .352 1.341 3.809
52 23.05 .351 1.342 3.823
53 23.1 .3505 1.343 3.831
54 23.1 .350 1.344 3.840
55 23.15 .3495 1.346 3.851
57 23.2 .348 L348 3.873
3 00 23.25 .347 L350 3.890
03 23.4 .3455 1.352 3.913
07 23.5 .344 1.356 3.942
14 23.6 .341 1.359 3.985
18 23.7 .340 1.361 4.003
25 24.0 .3365 1.37 4.071
35 24.0 .333 1.378 4.138
41 24.2 .331 1.38 4.169
50 24.2 .3275 1.383 4.223
56 24.2 .326 1.385 4.248
GUTHE.] THE SILVER COULOMETER. 355

solutions was again determined as before, care being taken to mix the
electrolyzed solution from each vessel thoroughly before taking out
the sample.
Calculation showed that in both cases the concentration had slightly
increased, probably owing to the evaporation of the liquid during elec-
trolysis. The remaining electrolyte in each instrument was then
treated with hydrochloric acid, filtered, and the filtrate evaporated to
dryness in a porcelain dish. There was a slight residue of a light-
greenish color, which, when heated, disintegrated and became black.
It was then dissolved in nitric acid, but in the solution no silver chlo-
ride was formed on the addition of hydrochloric acid. A surplus of
ammonia colored the solution slighth^ blue, showing that some copper
was present, which was probably contained in the original electrolyte.
The same test was applied to the heavy anode solution which had
collected in the beaker during the experiment (B), but in this case
also no silver that had escaped precipitation by the hydrochloric acid
was found in the filtrate.
5. The main problem is either to prevent the formation of com-

plex ions or to hinder the anode solution from reaching the cathode.
Attempts in the first direction by adding an oxidizing agent, for
example, hydrogen peroxide, to the solution, have been unsuccessful
so far, while the second problem has to a certain extent been solved.
Richards places the silver rod, which forms the anode, in a fine-grained
porous cup and removes from time to time the solution collecting at
the bottom.
The author fully corroborated Richards's results, but proposed a
differentform of the anode. The bottom of a wide porous cup is filled
with granulated silver, and upon this a large silver plate is pressed.
In this type the rather inconvenient frequent removal of the solution
was found to be unnecessary. The heavy solution is prevented by
the porous cup from rapid diffusion and breaks up to a large extent
when it remains in contact with silver (see figs. 1 and 2). This sec-
ondary reaction, he believes, gives rise to the formation of the well-
known dark anode slime, which is pure silver when the anode is pure.
Formerly this was thought to be peroxide of silver. Novak believes
he has found two distinct modifications, according to the current
density employed. Investigations at the Reichsanstalt have shown,
however, that if pure silver is used at the anode no peroxide is formed.
The black powder at the anode is, in the main, silver in a form similar
to platinum black. It is, however, not impossible that some oxygen
may be present.
The phenomenon reminds us of the appearance of finely divided
356 BULLETIN OF THE BUREAU OF STANDARDS. [vol.1,no.3.

copper on a copper anode, in a copper sulphate solution. As Fischer^

has shown, the copper goes into solution partly as cuprous ions, the
amount sometimes reaching 50 per cent of the total anodic copper
loss. On reaching the cooler body of the electrolyte, the cuprous
sulphate breaks up into cupric sulphate and pure copper; similarly
the silver may go into solution as an ion, in a lower state of oxidation,
and be broken up again in the immediate neighborhood of the anode.
While the usual anodes were very soon covered with anode slime
after the current of one ampere was started through the coulometer,
silver, freshly deposited on the rods and left in the solution, did not
show the tendency to blacken, and this suggests a decrease in the sec-
ondary chemical reaction. Possibly this is due simply to the increase
in the size of the electrode. Experiments with anodes of electrol^^tic
silver will be made.
Other arrangements may be adopted to prevent the anode solution
from reaching the cathode. The latter may, for instance, be suspended
above the anode, or the cathode may be in form of a plate suspended
in a glass vessel as Gray has done, or the two electrodes be placed in
different vessels connected by a siphon. From a practical point of
view the latter types are, however, less convenient than the two
described above. Moreover Van Dijk^ has lately shown that when a
siphon is employed the deposit is still a little larger than in the porous
cup coulometer.
6. Preliminary experiments have shown that Bancroft's proposi-

tion,* that rotating electrodes be used, promises good results. A con-

stant stirring of the solution in the neighborhood of the anode reduces
the formation of the anode slime, or, as I believe, decreases the number
of ions of lower oxidation than the normal. Thus, three methods,
either separately or combined, will be tried in our future work on the
subject: (a) addition of oxidizing agent to the solution; {h) electrolyzed
silver as anode; (c) rotating electrodes. It is hoped that some means
may be found to avoid the porous cup altogether, or at least allow the
use of cups of loose texture. Another source of trouble may arise
from the contact of the solution with filter paper. The organic sub-
stances contained in the latter may act chemically upon neutral silver
nitrate solution. Filter paper should therefore not be used in the
preparation of the electrolyte nor in the coulometer.
7. The following table shows a comparison between different types.

In the first column the description of the instrument is given, and in

« Fischer: ZS. anorg. Chem., 48, p. 177; 1904.

& Van Dijk: Arch, neerl. Sci. exactes et nat., 9, p. 442; 1904.
c Trans. Intern. Electr. Congr., St. Louis, 2, p. 106; 1905.
GUTHE.] THE SILVEK COULOMETER. 357

the following column the differences between the mass of the deposit
and that in the porous cup coulometer, if in the latter one gram of
silver were deposited. The filter paper type includes the one used
by Van Dijk and Kunst," who surrounded the anode by a thimble
of filter paper, as used in Soxhlet's extraction apparatus. On the
average the filter paper coulometer yields 1.00045 grams to one gram
in the standard or porous cup type. Kahle compared the siphon
type and the silver oxide type with the ordinary form. In order to
include his results in this table, the average difference between the
filter paper coulometer and the standard have been added to the

numerical values found by him.

Table II.

Kahle. Richards. Guthe.

Van
Dijk.
Aver-
No. Type.

1898. 1899. 1902, 1904. 1904.

mg mg mg mg mg mg
Anode surrounded by filter pa-
per 0.82 0.34 0.48 0.28 0.45
Anode surrounded by granulated
silver and filter paper 0.57 0.57
Anode surrounded by filter pa-
per; solution saturated with
Ag^O 0.95 2.03 1.12 1.2
Anode surrounded by porous
cup; solution saturated with
Ag^O 0.55 0.55 0.55
Glass dish under anode 0.45 0.12 0.3
Anode and kathode in different
vessels, connected by a siphon. —0.05 0.11 0.03

We see that the usual filter-paper type (No. 1 in the above table)
with a silver nitrate solution gives a deposit 1 part in 2,000 larger than
the standard porous cup coulometer. It should, however, be remarked
that the porous cup does not entirely prevent the diffusion of the com-
plex ion into the kathode space, and this will become the more appar-
ent the longer the time of electrolysis. It would therefore be a
decided advantage if a method could be devised in which the use of

a Van Dijk and Kunst: Proc. Roy. Ac. Amsterdam, Jan. 21, 1904, and Ann. Phys.,
14, p. 569; 1904.
358 BULLETIN OF THE BUREAU OF STANDARDS. [vol.1, no. 3.

a porous cup is unnecessary. The low values obtained by Van Dijk

may possibly be due to a looser texture of the cups, but it is difficult

on account of the unreliability shown by two

to decide this question
ordinary coulometers put in series and treated in exactly the same
way. Kohlrausch's form gives intermediate results, as was to be
expected.
As the investigations referred to show, we can rely upon the porous
cup coulometer to at least within 1 part in 10,000, even for inde-
pendent series of experiments. It would therefore be a decided step
in advance if one of these types was substituted for the one now in
common use. This would necessitate a change in the accepted value
of the electrochemical equivalent of silver, as will be shown later
i. e. if in the future the unit of electric current should still be defined
,

on the basis of the c. g. s. system.

8. Whether or not there are other disturbing factors of minor

importance only an extended research with the porous cup coulome-

ter will show. Some of the earlier experiments are not conclusive in
this respect; they were made with the usual type, and often the dif-
ferences observed amount to less than what we may expect. Besides,
different investigators frequently contradict each other.
In the silver coulometer a neutral solution of silver nitrate is recom-
mended. To test the neutrality it seems best to precipitate the silver
by means of neutral sodium chloride solution and test the filtrate with
methylorange. If the crystals contain acid it may be well to melt
them in a silver or platinum crucible.
As Kahle has shown, a neutral solution becomes acid on being used.
Richards explains this by a deionization of hydroxyl ions with the
formation of silver oxide, and a consequent excess of ionized hydrogen
in solution. That the mere presence of acid can not be held responsi-
ble for the trouble follows from Rodgers and Watson's and Leduc's
investigations with an originally acid solution. The latter found the
deposits 1 part in 5,000 lighter than without the addition of the acid
to the electrolyte. In fact, if the original amount of free acid sur-
passes a definite percentage, then on electrolysis the amount decreases.
I believe that the addition of acid or some other oxidizing agent to
the anode side of a porous cup coulometer will be of help in either
preventing the formation of the complex ion or in breaking it up.
Experiments in this direction are in progress.
The Reichsanstalt recommends that acid be not used, lest impuri-
ties of the anode pass into solution. The influence of impurities in
the solution seems, however, to be of little importance, as shown by
Rayleigh and Mrs. Sidgwick, who added a large proportion of copper
6UTHE.) THE SILVEE COULOMETEE. 359

sulphate to the solution, and by Leduc, who added copper sulphate and
also potassium nitrate. The deposits did not contain any of these
impurities. If the current is not too large, it may be stated as a gen-
eral rule that metals which require a higher cathodic dijfference of
potential than silver will not be found in the deposits. The presence
of a small amount of nitrite does not influence the result, but in a sil-
ver-nitrate solution saturated with nitrite the deposit becomes too
heav3^
The presence of rarer metals would seem to be more serious, but
they are hardly ever found in appreciable quantities in commercial
silver, and, moreover, their electrochemical equivalents are not very
different from that of silver. Extreme care in the selection of mate-
rial for the electrolyte as well as the anode seems, therefore, to be
unnecessary. We may even use a soluble electrode of a metal like
zinc and still obtain satisfactory results, as Richards and Heimrod
proved.
9. One great objection is found in the tendency to looseness which

the silver obtained from nitrate solution frequently shows. The

addition of a small proportion of silver acetate greatly improves the
texture of the deposit, but, as was shown by Rayleigh and Mrs. Sidg-
wick, the deposit is always too heavy, possibly owing to an inclusion
of liquid.
Richards suggests that in this case the concentration of the oxide-
complex is larger than in the nitrate solution, and therefore the deposit
heavier. Lord Rayleigh employed silver chlorate as electrolyte and
obtained results closely agreeing with those given by a silver nitrate
coulometer. Deposits from cyanide solution are pure white and show
no tendency to looseness. Leduc * has made some experiments with
potassium silver cyanide, but the amount of silver collected was
entirely too small, which he attributed to a simultaneous development
of hydrogen and silver at the kathode and to an occlusion of the for-
mer in the silver. Farup,* however, has shown that hydrogen is not
produced, but that the silver is dissolved by potassium cyanide if air
is present in the solution. He employs, therefore, a silver coulometer
with potassium silver cyanide as electrolyte, but saturates the solution
with hydrogen. The results obtained by him are quite satisfactory,
though I believe that with larger deposits trouble may arise due to
occlusion of the liquid in the deposits. For small currents, however,
this form seems to be very useful.
It is claimed that deposits from pure silver nitrate solution keep
some of the liquid included. This will show itself in a deqrease of
« Leduc: Eapports Congr. Internat. de Phys., 1900, 2, p. 440.
&Farup: ZS. I. Electroch., 8, p. 569; 1902.
360 BULLETIN OF THE BUREAU OF STANDARDS. [vol.1,no.3.

weight when the deposit is heated to nearly red heat, the nitrate being
decomposed. According to Rayleigh and Mrs. Sidgwick, there was
sometimes no loss on heating, but perhaps more often a slight decrease.
Kahle advises a treatment for ten to twenty minutes with water at a
temperature of 70° to 90° C, to insure the complete removal of the
mother liquid. Richards also found a slight amount included; but
Gray claims that with proper washing the plates may be heated with-
out any sensible loss of weight. This statement has been recently
corroborated by Van Dijk," who, after washing and drying at 150°,
heated the deposits in an electric furnace to 500° and 600° C. without
noticing a loss in weight. The silver may either be freshly formed on
a platinum surface or on another former silver deposit. Only in the
case that a new deposit is formed on an old one which had been heated to
500° C. a decrease could be noticed, but this is explained by the crack-
ing of the old crystals, due to the heating and consequent inclusion of
liquid in the fissures. It seems, therefore, unnecessary to correct for
included mother liquid in a deposit properly washed and dried.
10. The question of the solubility of silver in different liquids is

one of great importance.

According to Richards and Heimrod, pure silver when boiled with
a silver-nitrate solution will produce nitrite of silver in small quanti-
ties, but the Reichsanstalt makes the statement that this is not the

case, and that therefore, under normal conditions, a reduction to

nitrite can not be observed in a silver coulometer. Kahle, Myers,
and Merrill ^ observed a decrease of the weight of silver when it was
treated with warm water, but Richards, Collins and Heimrod, Leduc,
and Guthe could not detect any change when the deposit was left
standing under water for hours, while Van Dijk asserts that in water
of 80° C. not more than 0.1 mg is dissolved in several hours for each
gram of silver deposited.
The concentration of the silver nitrate solution seems to affect only
the texture of the deposit, which has a tendency to looseness if the
solution is too weak in relation to the current. Though Gray con-
siders it a mistake to use solutions containing more or even as much
as 10 per cent of silver nitrate, all other observers deny any influence
of concentration, and generally recommend high concentration, i. e.,
from 15 per cent to 30 per cent.
The Reichsanstalt has found that silver oxide is almost insoluble in
concentrated nitrate solution, but the experiments referred to above
show that solutions treated with the oxide are favorable to the forma-
tion of the complex ion and will yield too much silver.

aVan Dijk, Arch, neerl, 10, p. 287, 1905.

& Merrill: Phys. Rev., 10, p. 67, 1900.
GUTHE.] THE SILVER COULOMETER. 361

Schuster and Crossley stated that the deposits of silver in vacuo

11.
were about 1 part in 1,000 larger than those obtained from solutions
surrounded by air, and these again larger than those formed in an
atmosphere of oxygen. The former result was verified by Kahle,
Richards, and Myers. ^ The latter also found an increase when the
liquid was saturated with nitrogen, but a decrease when the dissolved
gas was carbon dioxide. It is reasonable to suppose that the increased
weight of the deposit is due to the removal of oxygen from the solu-
tion and not to a change in pressure. In addition, Merrill shovved
that an increase of pressure to 103 atmospheres has no appreciable
effect.
Rayleigh and Mrs. Sidgwick observed an increase of deposit with
increase of temperature; Leduc a decrease; Richards, Collins, and Heim-
rod obtained as well at 60° C. as at 0° C. a larger deposit than at 20° C.
12. Almost all observers agree that the size of the cathode makes
no difference as long as the current density is kept within about 1
ampere per 50 to 500 cm'^ of cathode surface. An objection has been
made to the use of the ampere as one of the fundamental electrical
standards, because the ordinary size of silver coulometer allows only
currents of the magnitude of one ampere to be measured. An increase
in the current limit may possibly be obtained by the use of rotating
cathodes, as now employed so successfully in chemical analysis. With
a rotating cathode a considerably larger current can be allowed than
with a stationary cathode. According to Schuster and Crossley too
great a current density at the anode is accompanied by a smaller
deposit; according to Leduc just the opposite is the case, while Merrill
could find no measurable effect due to a variation in the size of the
electrodes. The author's experiments lead to the conclusion that in
the porous-cup coulometers the size of the anode does not come into
account. It is, however, well to keep in mind that the drop of poten-
tial should not be large enough to allow a decomposition of water. In
all ordinary forms of silver coulometers the potential difference is suf-
ficiently small.
With the usual type of coulometer Kahle as well as Van Dijk
obtained a somewhat larger deposit on a silver cathode than on plati-
num, and considers, therefore, as normal deposits those obtained on
silver. Richards and Heimrod confirm this observation, but find that
with a porous-cup coulometer no such difference appears. The author
also obtained identical resultswhen the cathode was platinum as when
silver had been previously deposited on it. The explanation of
Kahle's results is to be sought in the action of silver upon the heavy
anode liquid mentioned above.

« Myers: Wied. Ann., 55, p. 288, 1895.

362 BULLETIN OF THE BUEEAU OF STAND AEDS. [vol.1,no.3.

The Electrochemical Equivalent of Silver.

13. The electrochemical equivalent of silver has been determined

repeatedly by absolute measurements, i. e., by means of instruments

which allow a calculation of the current in terms of the fundamental

units of mass, length, and time. Among the earlier investigations
only those of Rajdeigh and Mrs. Sidgwick and of Fr. and W. Kohl-
rausch can be considered accurate. In order to express all measure-
ments in terms of the same standard, the different values found have
been reduced to those given by tTie porous-cup coulometer, and these
are given in the last columns of the following table. Since in most
cases the exact conditions of the experiments are unknown, these cor-
rected values will simply give a general idea of the agreement between
different observers.
As be seen, Richards's and Van Dijk's corrections differ consid-
will
erably. In deciding upon my own corrections I have taken the
average of these two and those proposed by myself elsewhere."
It was thought unnecessary to take into account the possible effect
of included mother liquid.
From this list we see that the results obtained so far are not very
satisfactory.
The most reliable experiments made in the United States, England,
Germany, and the Netherlands lead to an average of 1.1178 mg for
the electrochemical equivalent of silver, while the last two French
determinations give a value of about 1 in 1,000 higher than this.
Redeterminations in absolute measure with the use of a reliable form
of coulometer are highly desirable.
The electrochemical equivalent of silver may also be expressed
14.
in terms of the electromotive force of a standard cell, i. e., by
comparing the electromotive force of the cell with the potential differ-
ence produced by the current at the terminals of a known resistance.
The electrochemical equivalent will depend upon the value chosen
for the electromotive force of the standard cell. The legalized value
for the Clark cell is 1.434 volts. But this is probably too high. In
Germany the electromotive force of the Clark cell is derived from
silver-coulometric measurements, and the Reichsanstalt has chosen
as the working value 1.4328 volts at 15° C. In the following table
the electrochemical equivalent of silver is calculated as well for an
electromotive force =1.434 as for 1.433 volts.

«Tran8actions of the International Electrical Congress, St. Louis, II, p. 104, 1905.
GUTHE.] THE SILVER COULOMETER. 363

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364 BULLETIN OF THE BUEEAU OF STANDARDS, [VOL. 1, NO. 3.

Table IV.

Electrochemical equivalent.

Observer. Year. E= 1.434 volts. E= 1.433 volts.

Usual Porous Usual Porous
type. cupC. type. cup C.

my mg mg mg
Carhart« 1882 1.1172 1. 1167 1. 1180 1. 1175
Rayleigh and Sidgwick 1884 1. 1183 1.1178 1.1192 1. 1187
Von Ettinghausen ^ 1884 1. 1180 1. 1175 1. 1188 1. 1183
Glazebrook and Skinner 1892 1. 1183 1. 1178 1. 1191 1. 1186
Perot and Fabry c 1898 1. 1193 1. 1188 1. 1120 1. 1196
Kahle 1898 1. 1173 1. 1167 1. 1180 1. 1175
Guthe 1904 1. 1174 1. 1168 1.1181 1. 1176

«Carhart: Am. Jour. Sci., 28, p. 374; 1884.

?>Von Ettinghausen: ZS. f. Electrotechnik, 2, p. 484; 1884.
c Perot and Fabry: Ann. Fac. des Sci. Marseille, 8, p. 201; 1898.

In the case of Perot and Fabry, who used a Clark cell at 0^ C. and
found its electromotive force to be 1.4522 volts, using 1.118 mg as the
electrochemical equivalent, the difference of 0.0164 volt given by the
Reichsanstalt has been used to reduce to 15° C, instead of the ratio
given by them. The latter would give 1.1180 mg in the first column
and corresponding values in the others and make the agreement with
the earlier experiments a very close one.
The large differences between the earlier and the more recent com-
parisons can hardly be due to the silver coulometer alone. Doubtless
the Clark cell comes in for its share.
Wolff and Carhart and Hulett have latel}^ discovered an electrolytic
method of preparing mercurous sulphate. Cadmium standard cells,
in which this substance is used, show, according to preliminary
reports, an excellent agreement among themselves, and no variation
in their electromotive force in course of time as far as can be ascer-
tained during a relatively short period.
With the improvement of our standard of electromotive force and
the construction of a reliable silver coulometer, a wide and interesting
field for research has been opened, and it is to be expected that the
new determination of the volt and the ampere, which are in progress
in the different countries, will show an agreement considerably better
than the older ones.
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