314 EUGENE P. S C H O C H A N D AI.

CAX HIRSCI-I

water in sealed tubes filled with carbon dioxide for 1 2 hours at 180'.
The solid product contained large quantities of galena and lead sulphate,
the latter being decomposed and its SO, extracted by treatment with
sodium carbonate solution.
The reaction is therefore presumably :
4FeS, + +
7PbC1, 4H,O -=7PbS - 4FeC1, H,SO, 6HC1.+ +
From these experiments it would seem that the formation of free sul-
phuric acid through the action of neutral, air-free copper and lead solu-
tions on pyrite and marcasite is a factor which can not be neglected.
Note on the Idenfzj5cafion of Chalcocife.
Chalcocite is readily attacked by ferric salts thus :
Cu,S 4-2FeC1, = CuS f CuCl, 2FeC1,. +
The CuS thus formed shows the blue color of covellite. A fragment
of chalcocite boiled for a moment with I O per cent. ferric chloride so-
lution acidified with hydrochloric acid becomes blue. The color appears
to particular advantage on compact smooth chalcocite, but the rough min-
eral also becomes decidedly blue. A gray coating on chalcopyrite took on
a deep indigo-blue color. The same effect is produced, but not as satis-
factorily, by boiling with 1-1 hydrochloric acid or allowing to stand a short
time with concentrated hydrochloric acid, but this is apt to dissolve the
coating completely. Enargite is entirely unaltered in appearance by the
above treatment'.
BVRE.4c OF STANDARDS
Washington, D. C.

THE ELECTROLYTIC DEPOSITION OF NICKEL-ZINC ALLOYS.

BY EUGENEP. SCHOCH
A K D XLCAS HIRSCX.

Received December IO, 1906.

Some time ago, while making some general experiments on the electro-
lytic deposition of alloys, we were surprised to find that, although zinc
has a greater electrolytic solution tension than nickel, yet a bath which
contains much more nickel than zinc yields an alloy which contains
much more zinc than nickel. This fact appeared worthy of study and
the paper presented below embodies the results which have been obtained
SO far.
The apparatus and arrangement used were as follows .- a paraffined
wooden trough 49 x 13 x I O cm. was filled with the electrolyte to a depth
of about 7 cm. T h e anodes were placed at the ends of the trough, the
active surface of each anode being 13 x 7 cm. The cathode was a cylin-
der of thin sheet metal with its axis vertical ; it was placed approxi-
mately midway between the anodes. Its active surface was as nearly I
Knop. li. J'b. 1861,S. 533.
 E L E C T R O L Y T I C D E P O S I T I O N O F N I C K E L - Z I N C ALLOYS 31.5

sq. dcm. as it could be made, which with a height of 7 cm., gives a

diameter of 4.4 cm. The distance of the nearest point of the cathode
from either anode was 2 2 . 5 cin., hence the distribution of the current
over the cathode surface was assumed to be uniform.
T h e cathode was clasped around a paraffined wooden cylinder of about
the same diameter, This wooden cylinder was suitably fastened to a
vertical brass shaft supplied with pulleys. By this means the cathode
was rotated at a rate of 160 revolutions per minute.
I n order to investigate the electrolytic deposition of these nickel-zinc
alloys four series of alloys were made. For the four series the ratios of
nickel to zinc in the electrolyte were radically different, but during each
series the ratio was kept practically constant by running nickel and zinc
anodes the necessary ampere hours. At one end of the bath was placed
a zinc anode and at the other end both a nickel and a zinc anode. The
current from each side was half of the total required ; and the distribu-
tion of the total current over the nickel and zinc anodes respectively
was such as to re-supply the nickel and the zinc in the solution in ap-
proximately the same amount as deposited. T h e common source of cur-
rent (storage cells) was connected to each of the three anodes through
separate circuits, each circuit supplied with ammeter and rheostat, and all
three connected through the common cathode. The temperature of the solu-
tion was maintained at about 25' and was not allowed to vary more than
a degree or two. T h e results are tabulated below.
T h e first difficulty encountered was in the choice of a suitable metal
to be used as cathode. Since it was desirable to determine the ratio that
the amount of alloy obtained bears to the theoretical current yield, cop-
per could not be used because it is impossible to dissolve the alloy from
the copper surface without dissolving some of the copper, and the alloys
did not peel completely from the copper sheeting even when the latter
had been coated with a thin layer of graphite. Aluminum was tried be-
cause the alloys could be dissolved in nitric acid leaving the aluminum
practically unattacked. However, it changes weight owing to oxidation,
and hence could not be used. Platinum could not be employed because
the alloys were all high in zinc, and the well known effect of platinum
upon zinc soon showed itself. The most suitable metal for the purpose
was found to be lead ; the cathodes used were of thin sheet lead. They
were thoroughly cleaned by treatment with concentrated hydrochloric
acid, washed with tap and distilled water, alcohol and ether. Finally
the cathode was dried in a desiccator and weighed. T h e back of the
lead plate was covered with a thin layer of low melting paraffin. When
the plate with the deposited alloy was taken from the bath the paraffin
was removed with petroleum ether. T h e plate and alloy were washed,
dried and weighed and then placed in dilute sulphuric acid and heated
316 EUGEn'E P. SCI-IOCH AXD A L C A N H I R S C H

until all the alloy was dissolved. T h e lead plate \vas then washed, dried
and re-weighed. This weight \\-as compared with the weight of the
cathode before the alloy was deposited upon it ; the difference between
the two weights was never more than a few milligrams. and the average
error was within o. I per cent. Therefore, the use of lead a s cathode niater-
ial was deemed sufficiently accurate. T h e solution in which the alloy had
been dissolved was diluted to a definite vol~iineaiid aliquot portions were
taken for analysis.
Various methods of analytical separation were tried, but abandoned as
unsuitable. Among these may be mentioned precipitating the zinc as
sulphide in the presence of gallic acid, and precipitating the nickel as
hydroxide with caustic soda. I t is well known that zinc sulphide is not
easily washed and filtered, and as all the alloys were very high in zinc,
it was impracticable to use the hydrogen sulphide method. T h e precipi-
tate of nickelous hydroxide contained zinc hydroxide which was not
completely removed by re-solution and re-precipitation. Furthermore it
was very difficult to wash the precipitate free from alkali. Hence this
method left much to be desired. T h e following method n-as finally
adopted as the most reliable and expeditious :
T h e determination of nickel depends upon the fact that in a weak am-
moniacal solution, nickel nia)- be titrated with potassium cyanide, silver
iodide being used as an indicator. The method is well known and is de-
scribed in Sutton's X'olunietric Analysis ( 1896) p. 243. I n the presence
of sodium pyrophosphate, zinc exercises no influence. T h e accuracy of
this method is confirmed by the following results :-
2 5 0 cc. contain 1.9981 grams electrolytic nickel dissolved in dilute sul-
phuric acid. 2 j cc. of this solution were taken for each trial.
cc. K C S cc. AgNO,; ICC KCN
KO. of ( . I 8 2 j K.) I I O 3;. cc. KCN used = prams
trial used used by nickel nickel
I 37.25 2.45 35.95 0.00556
2 37.3 2. s 3j.S 0.wjjS
3 39.5 6. I 36. I O.Wi54
NOTE :-The concentration of the potassium cyanide solution was de-
termined by titration with the silver nitrate solution. By calculation
1cc.KCN=o.o0558 gms. nickel. I n the third trial some zinc chloride and
sodium pyrophosphate were added to the solution.
T h e precautions which should be taken in this volumetric determina-
tion of nickel are : the solution should be distinctly, but not strongly,
alkaline, and the temperature should be kept below 20'.
T h e zinc was determined froin another sample of the alloy after first
removing the nickel by precipitating with sodium hydroxide, dissolving
and re-precipitating, and subsequently titrating the zinc in acetic acid
solution by means of potassiuni ferrocyanide. T h e end-point was deter-
 E L E C T R O L Y T I C D E P O S I T I O N O F N I C K E L - Z I N C ALLOYS 317

mined colorimetrically with uranium acetate as an indicator. This

method was not very accurate owing to the difficulty of determining the
end-point, and because some of the zinc was invariably carried down with
the nickelous hydroxide as already stated. This method was found to
be accurate only to I per cent. As the nickel determination was SO much
more accurate, the zinc was mostly found by difference.
I n the four series of alloys described below, only the good plates that
were obtained have been presented. T h e reasons for this are the follow-
ing : powdery and warty deposits favor the evolution of hydrogen in an
irregular manner as shown by the fact that results could not be duplicated.
Such deposits also showed not the least regularity in the variation of
their composition as compared with the variation of the compositions
of the solutions.
I n each series, the limiting current-densities were first determined with
great care. T h e plates obtained with these current-densities were made
in duplicate, and each was analyzed several times. I n each series the
highest and lowest current-densities are the critical current-densities. I n
the first series with the stationary cathodes, the limits within which satis-
factory plates were obtained are closer together than with the rotating
cathodes, as was to be expected.
I n the first series two methods of operation were employed : first, the
cathodes were stationary, but the liquid was stirred vigorously except in
one case especially noted ; second, the cathodes were simply rotated.
I n the second, third, and fourth series only the latter method of operation
was employed.
Series r .
Composition of electrolyte :
Zinc sulphate ............................................. .143 grams
Nickel sulphate ............................................ ?35
Aluminum sulphate ........................................ 75 ( I
Volume of solution ...................................... .5- C.C.
Ratio of nickel equivalents to zinc equivalents, 1.68 : I
A . With sfationary cathodes.-In making this series the anodes were
placed in the center of the bath with one cathode at each end connecting
with two separate sources of electromotive forceso that two different alloys
could be made simultaneously, The liquid was stirred vigorously by
means of rotating glass stirrers just in front of each cathode.
TABLE rA.
No. C. D. Wt. Alloy Amp. Hrs. Percent. of Theoret- Percent. Nickel
ical Yield
I 0.5 4.2989 gm. 3% 100 15.1
21 0.5 4.4344 " 3% IO0 16.6
3 0.5 3.6560 ' I 3% 91 15.7
4 1.0 4.9786 ' I 4 I00 12.8
5 1.5 6.5764 '( 534 I00 12.2
In (2) the liquid was not stirred.
3'8 EUGENE P. SCHOCH A r j D A L C A N H I R S C H

B. with ~otntin,gcathodes.-In making this series the revolving cath-

odes were placed in the center of the bath with the anodes at the ends.
TABLE IB.
h-0. C. D. Wt. Alloy Amp. ~ r s .Per cent, of 'I'heo- Percent. Sickel
retical Yield
6 2.6570 gm. 2 9' so 20.6
-
/
0.2

0.4 5.9'34 ' I j "10

IO
92 16.4
S 2.0 6.0920 " 6', 76.2 12.0
9l 2.5 11.5
IO 4.0 6.0890 " 5 ;4 98 9.3
' Plate g peeled from the cathode.
Series a .
Composition of electrolyte :
Zinc sulphate ............................................. 7 1 , j gratns
Nickel sulphate .......................................... 235. I'

Aluminum sulphate ...................................... 100. ''

Volume of solution. ...................................... 5000. cc.
Ratio of nickel equivalents to zinc equivalents, 0.336 : I .

TABLE 2.

3-0. c. D. Wt. Alloy Amp, HIS. Per cent. of Theo- Per cent. Sickel
retical Yield
I1 0.5 3.715; g U 1 . 3 :h 93 8.4
I2 1.5 5.4042 " 6 rr
/ I 6.S
1.3 4.0 5.4662 ( ' 4Y IO0 6.6

Series 3 ,
Composition of electrolyte :
Zinc sulphate.. .......................................... 71.5 grants
Nickel sulphate.. ..................................... 23.5 "
Aluminum Sulphate.. ................................... 75. ''
Volume of Solution ...................................... 5000 CC.
Ratio of nickel equivalents to zinc equivalents, 3.36 : I .
TABLE 3.
h-0. C. D. Wt. Alloy Amp, Hrs. Per cent. of Theo- Per cent. Nickel
retical Yield
14 0.5 1.0895 gm. 3% 30 32.2
15 1.5 6.7526 ( ' 6 95 1s.g
Series 4 .
Composition of electrolyte
Zinc sulphate ............................................. S34 grams
Nickel sulphate.. ......................................... 235 "
Aluminum sulphate ...................................... 110 "

Ammonia alum ........................................... 25 "

Volume of solution.. ..................................... 5000 CC.

Ratio of nickel equivalents to zinc equivalents, 0.29 : I .
 ELECTROLYTIC DEPOSITION O F NICKEL-ZINC ALLOYS 3'9
TABLE 4.
No. C. D. Wt. Alloy Amp. Hrs. Per cent. of Theo- Per cent. NickeI
retical Yield
16 0.5 4.0052 gm. 3 7/19 Io0 4.3
I7 1.0 7.0860 ( ' 6 IO0 3.9
18 2.0 15.4422 " I3 IO0 3.8
I9 4.0 7.4031 ' ( 5 IO0 3.6
The foregoing results are plotted as follows :

0 . 5 /,O L.5- 2.0 t.5 3.0 2.J 4.0

PLOTA
I n plot A each series is represented by a curve. T h e different current-
densities are plotted a s abscissas, and the percents of nickel as ordinates.
I n plot B the abscissas are the ratios of equivalents of nickel to equiv-
alents of zinc in the electrolyte; the ordinates are the ratios of the
percents of nickel to zinc (in equivalents) in the alloy.
I n connection with the foregoing results it should be mentioned that
the relative amount of hydrogen discharged varies in an irregular man-
ner from plate to plate, especially at the beginning of the formation of
the alloy. Hence the current yield of the alloys obtained varies consider-
ably. Yet it may be stated as the result of general observation, that in
320 EUGENE P. SCIIOCH A N D ALCAN KIRSCH

05

0.4

0.3
0.2
0.1

0.65- / 2 c7 4
I’m r li

deposition of all alloys containing less than 20 per cent of nickel and which
present a bright, smooth surface, the evolution of hydrogen is compara-
tively slight.
On inspection, the tables and curves show three general results : -
( I ) T h e proportion of zinc in the deposit is greater with a greater pro-
portion of zinc in the electrolyte.
( 2 ) T h e proportion of zinc in the deposit increases with the current-
density and approaches “asymptotically” to a maximum ; in series 2 and
4 the maximum is practically reached.
(3) T h e ratio of zinc to nickel (by equivalents) in the alloy is from4.g
to 14 times their ratio in the electrolyte, according to the concentrations
of the latter.
T h e first two results may be passed as being in accordance with es-
tablished principles ; they present nothing new. We shall pass, then, to
the consideration of the third, which is really the main point of this
paper. In order that this result may show itself properly, all influences
that would help or hinder it should be excluded. T h e main, and per-
haps the only influence that affects it is changes in concentration which
 E L E C T R O L Y T I C P R E P A R A T I O N O F AMALGAMS 321

influence the relation between the degrees of dissociation of the zinc and
the nickel salts respectively. Accordingly, two solutions were prepared,
both fairly dilute, and differing not too extensively in the relative con-
centrations of the nickel and the zinc salts. T h e data for these solutions
are : -
( a ) Solution same as for Series 4, except that the total volume of the
solution is fifteen liters (i.e. three times as much as before). Witb cur-
rent densities above two amperes the alloys obtained were practically of
constant composition. T h e alloy obtained with C.D. = 3 amp. contained
4.6 per cent. nickel. Hence the ratio of zinc to nickel (by equivalents)
in the alloy equals 5.4 times their ratio in the electrolyte.
( b ) Nickel sulphate .................................... 131.5 grams
...................................... 182
Zinc sulphate.. "

Ammoniaalum ...................................... 100 "

Volume of solution ................................. .5000 cc.

.................. 0.74:r
Ratio of nickel to zinc equivalents..
With current-densities above two amperes, the alloys obtained were
practically of constant composition. T h e alloy obtained with C.D. = 3
amp. contained I I . 2 per cent. nickel. Hence, ratio of zinc to nickel (by
equivalents) in the alloy equals 5 . 3 times their ratio in the electrolyte.
This indicates that the cause produces a constant factor.
We are not ready to say anything as to the nature of the cause itself.
We thought it might be due to a possible difference in the rates of mi-
gration of the nickel and zinc ions, but we have since learned that the
equivalent conductivities of the sulphates and of the chlorides of these
metals at corresponding concentrations are practically the same, and
hence have given up this explanation.
Further work on this problem is in progress.
CHEMICAL LABORATORY,
THEUNIVERSITY O F TEXAS.

THE ELECTROLYTIC PREPARATION O F AMALGAMS.

BY GEORGEMcP. SMITHA N D JAMES R. WITHROW.
Received December 28, 1906.
T h e older methods of preparing amalgams with the help of the electric
current' require much time and somewhat complicated apparatus. Con-
siderable labor is also frequently involved. E. s. Shepherd,' however,
has proposed, as a lecture experiment, the electrolytic preparation of
sodium amalgam. He points out that the amalgam formed is not so
heavy as the mercury itself, and therefore serves to retard action by rising
to the surface and thus separating the mercury from the electrolyte to
Nernst, 2. Electrochem., 3, 308 (1897) ;Kerp, 2. anorg. Chem. 17, 300 (1898);
Reuter, 2. Electrochem, 8, Sor (1902).
J. Phys. Chem. 7, 29, (1903).