Gold-Plated Electrode for Measurement of Conductance

of Electrolytes'
SIDNEY BARNARTT

Westinghouse Research Laboratories, East Pittsburgh, Pennsylvania

ABSTRACT
Electrodes for c o n d u c t a n c e m e a s u r e m e n t s b y the K o h l r a u s c h m e t h o d were p r e p a r e d
b y electrodepositing finely divided gold over a layer of s m o o t h gold. T h e i r b e h a v i o r
was studied over t h e frequency range 1 to 10 kilocycles/sec. P o l a r i z a t i o n resistance a t
these electrodes was found to be relatively small a n d in c o n f o r m i t y w i t h t h e War-
b u r g relationship.

For careful measurements of the conductance of made, e.g., Lorch (4). The writer was faced with this
electrolytes by the Kohlrausch method (1), elec- choice for determining the cell constant of an elec-
trodes least subject to polarization errors are used. trolytic cell whose predetermined electrodes were
They are selected from those suitable for revers- relatively massive and of unusual shape. Machining
these electrodes from precious metals was impracti-
T A B L E I. Performance of the apparatus with pure resistance cal; electrodeposited coatings were decided upon.
in place of the cell Since the electrodeposition of gold in either the
Frequency Rp Cp smooth or the finely divided state was simple and
cycles/sec ohms microfarad
convenient, electrodes composed of finely divided
gold on a gold-plated base metal were considered
1,000 19.41 0.003~ worthy of investigation. Miller (5) studied smooth
3,000 19.41 0.0035 gold-plated electrodes, using a frequency of 3,400
5,000 19.41 0. 0035
cycles/sec, and found definite polarization resist-
10,000 19.41 0. 0035
ance. Finely divided gold surfaces, however, have

T A B L E II. Conductance measurements at 25.0~

0.01N KCl 0.02N KCI
]
Rp = Rs Cp Cs AR Rp = Rs Cp C~ AR

cycles/seo ohms microfarad microfarads ohm ohms microfarad microfarads ohm

1,000 43.16 0.033 410 0.13 21.99 0.105 500 0.09
2,000 43.13 0.010 340 0.10 21.96 0.033 400 0.06
4,000 43.10 0.0033 250 0.07 21.94 0.011 300 0.04
6,000 43.08 0.001s 210 0.05 21.93 0.0060 240 0.03
8,000 43.O8 0.0015 140 0.05 21.93 0.0045 180 0.03
10,000 43.08 0.0010 140 0.05 21.93 0.003G 150 0.03

RT 43.03 21.90
A* 141.30 138.37
Cell c o n s t a n t 0.0608o 0. 06061

* D a t a of Shedlovsky, Brown, a n d M a c I n n e s (6) increased b y 0.02 per cent to c o r r e s p o n d w i t h t h e J o n e s and P r e n d e r g a s t

(7) s t a n d a r d s [see G u n n i n g a n d G o r d o n (8)].

ible hydrogen electrodes. The latter may be com- not been employed previously in conductance meas-
posed of finely divided platinum, palladium, or irid- urements, to the writer's knowledge.
ium, electrodeposited in~a thin layer on one of these
metals or on gold (2, 3). The choice of electrode de- EXPERIMENTAL PROCEDURE AND RESULTS
pends upon the composition of the solution in con- The electrodeposition of gold was carried out at
tact with it, and various recommendations have been 60~ without agitation from the following solution:
1 M a n u s c r i p t received F e b r u a r y 14, 1950. T h i s p a p e r pre-
KAu(CN) 2--0.050 mole/liter
p a r e d for delivery before the Cleveland Meeting, April 19 KCN, free--0.20 mole/liter
to 22, 1950. K~CO~--0.10 mole/liter
235

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 236 J O U R N A L OF T H E E L E C T R O C H E M I C A L
The cathodic current density was 0.5 a m p / d m 2 for
the adherent smooth deposit and 3.0 a m p / d m 2 for
the finely divided deposit. The cathodic current ef-
ficiency was 100 per cent at the lower current, but
hydrogen was codeposited at the higher current.
The electrodes, which were machined out of copper,
were first plated at 0.5 a m p / d i n 2 to a thickness of
10 microns; then an additional weight of gold, equal
to half t h a t already on, was deposited in the finely
divided state b y raising the current.
The cell geometry, too complicated to be de-
scribed in this short report, was predetermined b y
considerations other t h a n conductance measure-
ments. Very roughly, the electrodes consisted of a
solid cylinder, 1.5 cm diameter, concentrically situ-
ated in a tube, 3.5 cm diameter. The conductance
measurements were made b y the usual Wheatstone
bridge technique, employing a cathode r a y oscillo-
graph as detector and an oscillator, equipped with
22.00
J tion resistance increases to 0.3-9.4 per cent as the
21.96 of
21,92
71.88
~'t.84 J
21.80(~ OOl 0.02 0.03
_J..]
FI(~. 1
an electrostatieally shielded transformer at the out-
put, as the variable frequency source. When the
bridge was balanced with a pure resistance in place
of the electrolytic cell, the resistance, Rv, and ca-
pacitance, C~,, in parallel with it in the adjacent
a r m of the bridge did not vary with frequency, f,
within the limit of sensitivity of the detector (Ta-
ble I).
Table I I presents the conductance measurements
using 0.01N and 0.02N potassium chloride solutions.
R~ and C, are the resistance and capacitance of the
cell, which in series are equivalent to the parallel
combination Rp and C~, The former were computed
from the measured quantities b y the well-known re-
lationships R~ = R S [ 1 + (2rrfRvCv) 2] and C, =
1/R,RvCp (2~rf) 2. Actually the q u a n t i t y (2rfRvCv) 2
was negligible in comparison with unity, so t h a t
R , = Rp in all eases.
Duplicate measurements of Rv at a given fre-
quency agreed to the nearest 0.01 ohm. The true
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SOCIETY July 1950
resistance of the electrolyte, Rr, was obtained using
the W a r b u r g relationship R , = R r + k/~c/f, where
]c is a constant. The validity of this equation has
been confirmed b y Jones and Christian (9) for var-
ious electrodes and electrolytes. Fig. 1 shows the
data of Table I I plotted according to the Warburg
equation, which is in agreement with the data within
experimental error.
F r o m R r the cell constant was calculated as 10-3
cARt, where c and A are the normality and equiv-
alent conductance of the solution, respectively. The
values of the cell constant for the two solutions agree
to 0.3 per cent, which is considered to be within the
possible variation in the physical arrangement of this
particular cell when reassembling it to change solu-
tion. For this reason, and also because the cell has
an extremely low cell constant and is, therefore, un-
suitable for accurate conductance measurements, the
gold electrodes must be evaluated from the magni-
tude of the polarization resistance, AR = R~ --
4320 RT = k/~v/f. As seen from Table II, the polariza-
4336 frequency is reduced to 1000 cycles/see. With more
favorable cells, such as those of Jones and Bollin-
43.12 ger (10), gold electrodes plated as described herein
-1-
o m a y exhibit sufficiently less error due to polariza-
43,oss tion t h a t no correction need be applied to the meas-
ured results for relatively accurate data. I t would
43.04 be of interest to determine the o p t i m u m conditions
of gold plating, as Jones and Bollinger ( l l ) did for
4:5.00 platinization, and to compare these gold electrodes
with platinized platinum electrodes in accurate con-
ductanee measurements.
Any discussion of this paper will appear in a Discus-
sion Section, to bc published in the ,June 1951 issue of the
JOURNAL.
REFERENCES
1. F. KOHLRAUSCHAND L. HOLBORN, "Leitverm6gen der
Electrolyte," 2nd Ed., Leipzig (1916).
2. W. M. CLANK, "The Determination of Hydrogen Ions,"
3rd Ed., pp. 286-290, Williams and Wilkins Co. , Bal-
timore (1928).
3. H. W. S. BRITTON, "Hydrogen Ions," 3rd Ed., Vol. I,
pp. 40-48, Chapman and Hall Ltd., London (1942).
4. A. E. LORCH, Ind. Eng. Chem., Anal. Ed., 6, 164 (1934).
5. C. W. MILLER, Phys. Rev. (2), 22, 622 (1923).
6. T. SHEI)I.OVSKY,A. S. BROWN, AND D. A. MACINNES,
Trans. Electrochem. Sou., 66, 165 (1934).
7. G. JONES AND M. J. PRENDERGAST, J. Am. Chem. Sou.,
59, 731 (1937).
8. H. E. GUNNING AND A. R. GORDON, J. Chem. Phys., 10,
126 (1942).
9. G. JONES AND S. M. CHRISTIAN, J. Ant. Chem. Sou., 57,
272 (1935).
10. G. JONES AND G. M. BOLLINGER, J. Am. Chem. Sou.,
53, 411 (1931).
11. G. JONES AND D. M. BOLLINGER, J. Am. Chem. Sou.,
57, 280 (1935).