Significance of effects of pressure on electrode reactions. Part 111.

Equilibrium processes at
reference electrodes and the volume of H in Pd

C h e r ~ r i sDepcrrtnler~t,
t~~ University ~ r O t t o \ r wOttn~vn,
, Or~t.,Cc~rroclo
Received June 30, 1977

BRIANE. CONWAY and J. C. CURRIE.Can. J. Chem. 56,915 (1978).

For studies on effects of pressure on kinetics of electrode processes (Parts I, II), reversible
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reference electrodes suitable for use in a conipletely enclosed high-pressure bomb are re-
quired. The electrodes must exhibit reversible behaviour over the pressure range employed i n
the experiments, i.e., their changes of emf with increasing and decreasing changes of pressure
must be reproducible and correspond to the respective volume changes in the reactions.
A series of reversible reference electrodes is examined over a range of pressures LIPto ca.
2500 bars. The Pd-H/H+ and Ag,AgCI/CI- reference electrodes are found to behave very
satisfactorily at elevated pressures; the Pt,H2/H+ electrode is, however, less satisfactory, d u e
to problems associated with dissolved H z .
The results enable the volume of Pd-H and of H sorbed into Pd to be evaluated, together
with estimates of the partial molar volume of H2 in aqueous HCI. These data enable the
pressure-coefficients of metal-solution potential differences at individual reference electrodes
to be evaluated. Such information is rcquired for interpretation of effects of pressure o n
kinetics of electrode processes.
I BRIANE. CONWAY et J. C. CURRIE. Can. J. Chem. 56,915 (1978).
Dans le cadre de nos etudes sur I'effet de la pression sur la cinetique des processus aux
For personal use only.

electrodes (partie I, 11), on devait disposer d'electrodes de reference rkversibles pouvant Etre
utilises dans une bombe a haute pression completement isolee. Les electrodes doivent posseder
tin comportement reversible a toutes les pressions utilisees au cours des experiences; entre
autre on doit &trecapable de reproduire des changements de force electromotrice avec des
augmentations et des diminutions de pression et ces changements doivent correspondre aux
changements de volume respectif des reactions.
On a etudie une serie d'electrodes de reference reversibles i diverses pressions allant jusqu'k
environ 2500 bars. On a trouve que les electrodes de reference Pd-H/H et Ag,AgCI/CI- s e
+

conlportent d'une fagon satisfaisante a des pressions elevees; toi~tefoisI'electrode Pt,H2/Hf

est moins satisfaisante a cause des problemes associts avec I'hydrogene dissous.
Les resultats permettent d'evaluer le volume de Pd-H et de H absorbe dans du Pd e t
d'tvaluer les volumes molaires partiels de Hz dans HCI aqueux. Ces donnees permettent
d'evaluer les coefficients de pression des differences de potentiel metal-solution a des electrodes
dc reference individuelles. De telles informations sont necessaires pour interpreter les effets d e
pression sur les cinetiques des processus ailx electrodes.
[Traduit par le journal]

evaluation by satisfactory nonthermodynamic means

In Parts I and 112 we considered the effect of
pressure on the kinetics of cathodic hydrogen evolu-
tion and of the F e ( c ~ ) , ~ - / F e ( c N ) , ~redox
- re-
action in order to evaluate volumes of activation and
examine electrostriction effects in the hydration shell
reorganization process. Such studies (1-5) require
reference electrodes (1, 2, 4, 5 ) which (a) can be used
reliably in an enclosed vessel at high pressure up to
say 3000 bars and (b) have well-defined and nleasur-
able pressure-coefficients of emf when used in appro-
I
priate combination with suitable electrolytes. Also,
the individual half-cell pressure coefficients of metal/
1I solution potential-difference should be susceptible to
I
in order that interpretation (3, 6) of pressure effects
on the kinetics of electrode processes can be made.
Reference electrodes reliable at high pressure (2) are
also required for evaluation of battery electrode
behaviour at high hydrostatic pressures, e.g. in deep
marine environments. There has been little previous
work on this kind of problem but the papers of Hills
and Kinnibrugh (I) and of Valeriote and Gallop (2)
provide an important background f o r the present
work, especially with regard to experimental
techniques.
In this paper, we report investigations on the
behaviour of three well-known reference electrode
systems, Pt,H2/H.&, Pd-H/H&, and Ag,AgCl/CI,,

'Present address: Department of Chemistry, Queen's Univer- under conditions of elevated pressure up to ca.
sity, Kingston, Ont. 3000 bars. Special attention was given to the
'For Parts I and 11, see ref. 3. Pd-H/H+ electrode, which has a potential of 0.050 V
 916 C A N . J. C H E M . VOL. 56. 1978

vs. H 2 / H f at 1 bar with standard H z pressure, as this
electrode is particularly suitable for studies of
electrode processes at elevated pressures since no
added gas is required in the high-pressure cell. Also,
the pressure-dependence of the ~ d - H / H f electrode
potential enables the molar volume of H sorbed in
Pd, as the P-PdH phase, to be derived.
The pressure dependence of the potential of a
reversible electrode reaction is related t o the volume
change occurring in the half-cell reaction. Thus, the
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T h e bottom of the cell is a glass cup with a threaded opening
for introducing the electrolyte. A screw c a p with a Teflon plug
insert and Teflon-covered O-ring was used to make a high-
pressure seal. Both the top and bottom of the cell had ridges
which allowed a positive Teflon-to-glass seal to be made when
the two pieces are joined with theshrinkable Teflon tubing. T h i s
type of cell can easily tolerate a 3 0 x volunle change without
undue strain being generated.
The cell for high-pressure emf measurements consists of 3
reversible electrodes, two of which are o f the same type. T h i s
provides a reliable check o n the behaviour of each electrode
while inside the high-pressure bomb. F o r example, if the cell

pressure coefficient of emf, E, can be written in terms is Pt,H21HCI/Pd-H,Pd, the potential of the palladium-
hydrogen electrode c a n be measured, in turn, against the t w o
of the appropriate partial molar volumes Vp of Pt,H2 electrodes. T h e potential between the two Pt,H2 refer-
products and VR of reactants as ence electrodes was also measured periodically. Thus, three
emf measurements a r e obtained at each pressure. This type o f
cell is illustrated in Fig. 1.
3. Cell Preporotio~l
Since single electrode potentials cannot be experi- a n All electrochemical cells, including those used at ambient
d high pressures, were washed in concentrated sulfuric acid
mentally evaluated, the electrochen~icalcell is com- for several hours, followed by thorough rinsing in doubly-
prised of two reversible electrodes, whose emf is distilled H 2 0 . The cells were then filled with pyro-distilled
nleasured as a function of pressure. The evaluation H 2 0 and allowed t o soak overnight. T h e electrochemical cells
of the behaviour of certain reversible electrodes for for high-pressure measurements were placed in a glove b a g
which was under a positive pressure of nitrogen. The solutions
possible use as reference electrodes in high-pressure y e r e degassed (to remove 0 2 ) with pre-purified N 2 in the glove
For personal use only.

electrode kinetic studies was performed by measure- bag. The cells were then filled with the appropriate solution
ments on a combination of two different reversible and allowed to soak for 30 min. The cell was then emptied,
electrodes (e.g. Ag,AgCl and Pt,H,) in a single high- rinsed a second time, and filled with the solution required f o r
the experiment. The cell was then sealed with the lower screw
pressure cell. If the measured cell emf is reproducible cap.
in the modes of compression and deco~npressionof In the case of equilibriuni emf measi~rementsinvolving a
the solution, then the pressure coefficient of emf Pt,H2 reference electrode, the electrolyte was presaturated
should be correctly given by ( - l/:F)(C Vp - C VR). with the H z gas at ambient pressure. T h e cell was then filled
Alternatively, the partial 111olar volume of one of the with electrolyte and HZ gas was again passed through it f o r
15 min. Several small bubbles of H 2 gas were allowed t o
components of the reaction can be evaluated if we remain in the cell after the cell had been sealed, in order t o
have precise knowledge of (BEIaP), and the partial ensure that the Pt, H 2 electrode remained in a well-defined
molar volumes of the remaining constituents of the state at elevated pressures.
cell reaction. If the determination of such a partial 4. Reference Elec~rodes
molar volume is consistent with the v o l ~ ~ ~reported
nes T h e Pt,H2 (1 b a r ) / H f , Ag,AgCI, a n d Pd,Pd-H reversible
in the literature, then it can be assumed that the two electrodes were chosen as being the most convenient f o r
reversible electrodes forming the cell are functioning electrochemical studies at high pressures in the present work.
(0) Tlle PI,H2 Electrode
in a ther~~iodynamicallywell-defined manner and
T h e hydrogen electrode was prepared by first cleaning t w o
therefore can be used as reference electrodes at high Pt wires (in the high-pressure cell cap) in warm aqua-regia
pressures. solution, followed by thorough washing in pyro-distilled
water. The wires were then platinized together by the standard
Experimental procedure with n o addition of P b 2 + ions. The electrodes were
then repeatedly washed with water, followed by several
I. High-pressifre Syste111 washings in pyro-distilled water.
Details of the high-pressure system, including the thermo-
statted bomb for containing the electrolytic cells, were given (b) Tlre Pd,Pd-H Electrode
in Part I1 (3). All measurements in this system were made at A palladium electrode was built into the high-pressure cell
298.06 k 0.02 K. by welding a piece of palladium wire t o a platinum wire. T h e
platinum was then sealed into the high-pressure cell c a p with
2. Electrocl~e~i~icnl
Cells for Use nt HigI7 Pressll~.e care being taken to expose only the Pd wire. The electrode w a s
Cells consisted of two Pyrex end-pieces joined by 2 x heat cleaned thoroughly with concentrated sulfuric acid a n d
shrinkable Teflon tubing. The top of the cell contains the washed with pyro-distilled water. T h e Pd-H electrode w a s
electrodes varying in number from 2 t o 4, depending o n the prepared by constant current cathodic electrolysis i n 0.5 M
type of system under examination. All the electrode leads are H 2 S 0 4 for a controlled time. The electrode was oxidized f o r
made of platinum wire of initial diameter 0.025 cm, which is 1 min, followed by a 90-s reduction, b o t h at a current density
hammered flat and sealed into the Pyrex glass tops of the cells. of 200 mA ~ m - T~h .i s cycling procedure was continued f o r
This type of metal-glass seal was found to withstand repeated approximately 10 nlin with termination of the electrolysis i n
elevation of pressure up to 2500 bars without development of the cathodic direction. The electrode w a s then washed with
a n y leaks o r cracks. pyro-distilled water. This electrode w a s activated i n this
 CONWAY AND CURRlE 9 17

decompressed in steps of 276 bars, and the emf values were

again measured after the normal equilibration period at each
pressure.
The pressure coefficient of emf, (BAEIaP),., at 1 bar for each
pair of reference electrodes was determined graphically from
plots of the measured emf values vs. pressure.

Results and Discussion

1. The Pt,H210.5 M aq. H2S0,1Pd-H,Pcl Cell
The emf data, AE, for this cell as a function of
pressure are listed in Table I. The cell reaction is
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[21 Pd + +Hz $ PdH

As mentioned earlier, 'PdH' is used t o represent the
2-phase a + P PdH system at equilibrium which
gives (17) the 50 mV potential wrt the Pt,H2(l
bar)JH+ electrode. The variation of A E as a function
of pressure is illustrated in Fig. 2. The reversibility of
the pressure effects is good with some small degree
of hysteresis occurring only with regard to the final
readings at low pressure. The slope at 1 bar is (8.6 f
0.5) x V bar-'. At pressures above 800 bars,
the AE vs. P plot is linear with a slope of (6.8 +
0.2) x V bar-'. The hysteresis is probably due
For personal use only.

to the loss of n~olecularhydrogen during the course

of the run by diffusion through the Teflon walls of
Frc;. I. High-pressure cell for emf measurements. The cell is the high pressure cell (see below).
fabricated from heat-shrinkable Teflon tubing and glass. The The pressure coefficient of emf, (aAE/aP), for the
cell contains three reversible electrodes of which two are of cell reaction 2 is related to the accompanying volume
the same kind. change by
manner at the beginning of each experiment and gave a
reproducible +50 mV potential (17) vs. a Pt,H, electrode in
the same solution at P = 1 bar. This potential corresponds to
an equilibrium of H in co-existing a and B phases of PdH with
H + in solution, and H content ica. 57 at.%. For convenience, where V H Zis the partial molar volulne of Hz, and
in most of the material which follows, the a + B PdH system V,, and VpdPH are the molar volulnes of Pd and
will be referred to simply as 'Pd-H'. Pd-H, respectively. Therefore, at 1 bar, the volu~ne
( c ) Tile Ag,AgCl Electrorle change for reaction 2 is -8.3 f 0.5 c m 3 mol-I and
The silver, silver chloride reference electrode was prepared
at pressures above 800 bars, the volulne change tends
from a piece of silver wire welded to a platinum wire which
was then sealed into the high-pressure cell exposing only the towards a value of -6.6 +
0.2 cm3 mol-'. The in-
Ag wire. The electrode was cleaned with concentrated sulfuric crease of the reaction volume as the pressure is en-
acid, followed by repeated washings with pyro-distilled water. hanced is due to the pressure dependence of the par-
Anodic deposition of AgCl on the silver wire was carried out
(17) by electrolysis from a 1 M aqueous HCI solution at a
current density of 1.0 mA cm-2 for 30 min. TABLEI . The emf data for the cell Pt,H2(0.5M aq. HzSOII
Pd-H,Pd at 298 K
5. E q l ~ i l i b r i ~
EMF
t ~ ~ ~Mcnsrtre~llerlfsnl High Presslnes
After the cell had been assembled and connected electrically
to the leads in the head of the bomb, i t was placed in the high P (bars)
pressure bomb. The cell was then allowed to come to thermal
equilibrium before any emf measurements were made. The
emf measurements were monitored with a calibrated digital
voltmeter (Dana Laboratory, Inc. Model 4300). Elevated
pressures were then applied only if the cell emf at ambient
pressure had varied less than 100 pV during the last I h of the
3 h equilibration period. If this condition was met, the pressure
was slowly increased in increments of 276 bars, up to a
maximum of 2500 bars. The appreciable heat of compression
which is generated was allowed to dissipate for a period of 3 h
at each pressure before the emf values were measured. After
the maximum pressure had been reached, the system was
 918 CAN. J . C H E M . VOL. 56, 1978

2. The emf data for the cell: P t , H 2 1 M

TABLE
HCIPd-H,Pd at 298 K obtained in two runs

AE (V)
P (bars) Run 1 Run 2
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FIG. 2. The variation of emf as a function of pressure at

298.06 K for the cell: Pt,H20.5M H2S04/Pd-H,Pd.
tial inolar volume of H, in water. [t was found that
the Pd-H/H+ electrode, with Ag,AgCI (see below),
provides a stable reference electrode in acid solutions
at pressures up to 2500 bars. The Pt,H, electrode is
stable to within 1 mV during the course of the
For personal use only.

experiments, but the problems associated with a

gaseous reference electrode in a plastic or Teflon cell
are always present.
2. Tlie Pf,H211 M HCIIPd-H,Pd Cell
The behaviour of this cell, with HCI as the electro-
lyte, was studied in order to provide a basis for use
of the Pd-H/Ht electrode in conjunction with the
Ag,AgCI/CI- electrode which will be discussed in
the following subsection.
The emf data for this Pt,H,/Pd-H cell as a function
of pressure are listed in Table 2 for two separate
experiments. The results are also shown graphically
in Fig. 3. The behaviour is, as expected, similar to
that of the cell described in subsection 1 above. The
slope at 1 bar, (BAEIBP),., is (8.4 $. 0.5) x V The pressure coefficient of emf for this cell was
bar-'; at pressures above SO0 bars the pressure co-
efficient is constant at a value of (6.9 f 0.2) x
V bar-'. The volume change for the reaction 2 is
found to be - 8.1 i 0.4 cin3 mol-' and - 6.7 0.2 + Pd--H,H+and Ag,AgCI reference electrodes as a func-
cm3 mol-' at 1 bar and above 800 bars, respectively,
using the above cell with aq. HC1 as electrolyte. The
volume data are in quite good agreement with those
derived above for the same cell with aq. H2S0, as
electrolyte.
The measured cell emf at 1 bar of 0.0502 V is in
excellent agreement with the value of 0.0495 V
reported by Schuldiner and co-workers (7). The value
of AE measured after the high-pressure readings,
0.0490 V, is 1 mV less than the initial value at 1 bar.
This behaviour is quite similar to that for 0.5 M
H2S04 and therefore can be rationalized in the same
FIG.3. The variation of emf as a function of pressure a t
298.06 K for the cell: Pt,H, 1.0 M HCIPd-H,Pd.
manner, viz. through effects associated with loss of
Hz through the Teflon.
3. Tlze Pd, Pd-H 1 M HCI I AgC1,Ag Cell
measured at a series of HCI concentrations at the
following molarities 0.01,0.25, 0.50, 0.75, and 1.0 (at
P = 1 bar) in order to evaluate the behaviour of the
tion of electrolyte concentration over a range of pres-
sures. This cell enables the apparent value of the
molar volume of Pd-H to be evaluated at each HCl
concentration from the appropriate pressure coeffi-
cient of emf and known values of the partial molar
volume of aq. HC1, and the molar volumes of AgC1,
Ag, and Pd. A true value for V,+, can then be ob-
tained for infinite dilution of electrolyte by appro-
priate extrapolation.
The experimental emf data are listed in Table 3
for each HC1 concentration, C, and pressure. T h e
emf data as a function of pressure are also illustrated
 CONWAY AND CURRIE

TABLE
3. The emf data in volts for the cell Pd,Pd-Hlaq. HCI, niolarity MIAgCI,Ag at 298 K

Emf at concentration of HCI (M), C =

Pressure -

P (bars) 0.01 0.25 0.50 0.75 1 .O

- - -

I 0.40084* 0.24846 0.21301 0.19210 0.17432

276 0.40064 0.24800 0.21238 0.19142 0.17368
552 0.40025 0.24750 0.21 180 0.19069 0.17296
828 0.39978 0.24696 0.21118 0.19004 0.17228
1105 0.39937 0.24641 0.21061 0.18935 0.17162
1376 0.39891 0.24583 0.20994 0.18868 0.17089
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1656 0.39842 0.24524 0.20931 0.18800 0.17023

1930 0.39796 0.24468 0.20868 0.18731 0.16952
2210 0.39746 0.2441 2 0.20806 0.18667 0.16884
I 0.40080 0.24865 0.21314 0.19208 0.17449
*Due to the high stability o f the e m f o f this cell n '5.k' digit digital voltmeter was used for these niensurements.

i n - ~ i4,~ where
. the differences of emf, AEp - AE,, reaction
at pressures P and 1 bar are plotted against pressure. Pd-H + AgCl* Pd + Ag + HCI
[41
The slopes are constant with increasing pressure for
the three highest concentrations over the complete are also included in Table 4.
pressure range. At 0.01 and 0.25 M, the pressure The pressure coefficient is related to the appro-
coefficient decreases (becomes Inore negative) with priate volume quantities for the cell reaction 4 by
increasing pressure up to 500 bars; at pressures above the equation
For personal use only.

500 bars, the pressure coefficient of the emf becomes

independent of P. The values of (aE/aP), at P = 1
bar and P 2 500 bars are listed in Table 4. The
volume changes at each concentration for the cell

where V,,, Vpd-,, VA,, and VAgCIare the molar

volumes of Pd, Pd-H, Ag, and AgC1, respectively.
The molar volumes of Pd, Ag, and AgCl are deter-
mined from the appropriate molecular weights and
densities of the solid phases in their standard states.
VHcl is the partial molar volume of HC1 but, for the
purpose of this calculation, the partial lnolal volulne
of HC1 at infinite dilution, V,",,, is utilized. From
the experimentally determined values of (CJAEIBP),
apparent values of the voluine VPd-, can be evaluated
from [5] for each concentration of HCl employed.
The values of Vpd_,, are 'apparent' because VHc, in
[5] is concentration-dependent according to the
Debye-Hiickel law. Inserting the appropriate nu-
merical data (8) in [5] gives

P (bars)
The apparent values of Vpd-, calculated from the
FIG.4. The variation of emf as a function of pressure at data for each HCl concentration and [6] are listed in
298.06 K relative to the value at 1 bar for the cell: Pd,Pd-
HIHCIIAgC1,Ag at HCI concentrations: (1)0.01 M, (2) 0.25 M, 5. V ~ d - are
~ then plotted
(3) 0.50 M , (4) 0.75 M, (5) 1.00 M. vs. C ' I 2 and extrapolated to zero ionic strength of
 920 C A N . J. CHEM. VOL. 56. 1978

4. Pressure coefficients of emf for the cell: Pd,Pd-HM HCIIAgCI,Ag at 298 K and the corresponding
TABLE
volume changes A V, or A V , at pressure = I or P bars

P = l bar P 2 500 bars

C(HCI) -
-- -
molarity (BAE/BP), ( p V bar-') AV, (cm3 niol-') (BAE/BP)T ( p V bar-') AV, (cm3 niol-')
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*Estimated errors are evaluated from standard deviations, duplicate ernfmeasuremenls in the compression and decompression modes
and the intrinsic error in the pressure measurement.

TABLE5. Apparent values of the molar

volume of Pd-H* at 298 K

C (M) HCI VPd-!, (cm3 nlol- ')

0.01 11.2
0.25 10.2
0.50 9.55 -
0.75 9.15
1 .OO 9.19
100
0 (extrapolated) 11.3+0.1
For personal use only.

'The significance o f this volume deduced from the

emf measurements is examined in section 5.

HCI giving a true value of V,,-,, as shown in Fig. 5. 90 I

The best-fit straight line by the method of the least
squares gives an intercept at C = 0 of Vpd-,., =
f O.l cm3 mO1-'. The
effect considered in kinetic experiments (3) need not
be taken into account here since ~nolalitiesare em-
ployed in the Nernst equation for emf's so that (cf.
ref. 2) co~npressioneffects are included in the activity
coefficients giving a nonideal volume contribution
which is eliminated on extrapolation to infinite
dilution.
The emf data in Table 4 are satisfactorily repro-
ducible over the pressure range 1 to 2210 bars. The
~naximu~n variation of AE at I bar recorded before
and after the high-pressure measurements was
1.7 x V ( C = 1.0 M HCI). The minimum
variation was 2 x V ( C = 0.75 M HCI). There-
fore the electrodes Pd-H/H+ and Ag,AgCl/CI- can
be used as reliable reference electrodes at elevated
pressures, with an uncertainty in the measured emf
not greater than 1.7 x V.
4. The Pt, H, 11 M HCI I AgC1,Ag Cell
The emf of this cell was found to be relatively
unstable in comparison with that of the other cells
referred to above. It was initially thought that a
time-dependent mixed-potential was set up at the
Ag,AgCI electrode in the presence of H,. Another
possible explanation is that reduction of traces of
dissolved Ag+ by molecular hydrogen occurs at the
Pt,H, electrode. A separator between the Ag,AgCl
0.50 1.0
c~.l / ~( ~ O Idm-'I4
FIG.5. The variation of the molar volume of Pd-H, Vpd-,,
with C,,a'lZ. The best-fit straight line obtained by the method
of least squares is shown.
and the Pt,H, electrodes was therefore introduced in
the cell, but the cell emf again proved to be unstable.
Significant diffusion of H, through the Teflon walls
of the high-pressure cell appears to be a more
realistic explanation for the time-dependent emf of
this cell. Earlier experiments with the Pt,H, vs.
Pd-H,Pd system referred to in subsection 1 gave,
however, much more stable potentials in the
ascending and descending direction of pressure
change. In the later experiments, the cells used were
made of Teflon from a source different from that
e~nployedin the earlier measurements. Therefore,
it seems that the two Teflon samples have a different
structure, the more recently obtained being perme-
able to molecular hydrogen.
Heusler and Gaiser (4)also observed instabilitv
and systematic errors of ;bout 2 mV for the equilc
brium emf of the cell Pt,H,IHCI, NaClIAgC1,Ag a t
atmospheric pressure. The errors were attributed to
irreversible reduction of AgCl and to the fact that
the H, partial pressure became less than 1 bar. The
loss of hydrogen was attributed t o diffusion through
their Teflon cell into the hydraulic oil i n the high-
pressure vessel. Valeriote and Gallop (2) also
observed similar drifts of cell potentials when a
 CONWAY A N D CURRlE
6. Pressure coefficients of emf for cells 1, 2, and 3 at 298 K
TABLE
P
(bar) C(rno1 HCI) (aAE,/aP)T(pV bar-I)
1 1 .O 5.85
> 800 1.O 4.35
hydrogen electrode is used in a Teflon, Lexan, or
nylon high-pressure cell. The effects were again
attributed to diffusion of H z through the walls of
the cell.
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In order to obtain a more reliable estimate of the
pressure-dependence of emf of the cell Pt,HzIHC1l
AgC1,Ag (cell l), an indirect approach must there-
fore be taken. The two cell systems treated in sub-
sections 2 and 3 are considered:
Ag,AgCI/1 M HCl Pd-H,Pd (cell 2)
and
Pt,H,11 M HCIPd-H,Pd (cell 3)
The (aAE,/aP), for the Pt,H,(l M HCl(AgC1,Ag
system, i.e., for the cell reaction
171 +HZ + AgCl s Ag + HCI
For personal use only.
for which
is obtained from the pressure dependence of the
emf's of cells designated 2 and 3.
The (aAE/aP), values for cells 1, 2, and 3, and the
volume change, AV,, for the cell reaction 7 are listed
in Table 6. The partial molar volume of Hz in 1 M
HCI at P = 1 bar, as calculated from [8], is also
given in Table 6.
5. T l ~ eVolurne of H Sorbed into P d rrnd the
SigniJicance of tlze Quantity V,,I,I
From the data given above, it is seen that evalua-
tion of the pressure coefficient of emf for the cell
can provide a convenient method for the determina-
tion of the molar volume, Vpd-,,, of Pd-H. The
significance of Vpd-, can best be visualized if the
processes involved in the Pd-H,H+ reference elec-
trode reaction are considered.
The behaviour of the Pd-H,H+ reference electrode
has been studied by Schuldiner et al. (7), Flanagan
and Lewis (9), and by Aben and Burgers (10) with
varying opinions on the actual mechanisms involved
in the functioning of such an electrode. However, the
mechanism described below appears to be the most
consistent with the experimental facts. It is known
that a palladium wire charged with hydrogen
electrolytically or under hydrogen atmosphere will
92 1
(aAE,/aP), (aAE3/aP), AV, (cm3 mol-') V,,2 (cm3 mol-')
8.40 -2.55 -5.65 17.6
6.90 -2.55 -4.20 14.1
achieve a potential of about +0.050 V with respect
to a standard Pt,H, reference electrode. Hydrogen
is absorbed initially by palladium in t h e a-phase up
to a limiting composition of H/Pd = 0.03 at 298 K.
Further H absorption produces a second phase, P,
with an H/Pd ratio of 0.60. The stable, well defined
electrode potential is due to the siinultaneous pres-
ence at the electrode surface of the two phases in
thermodynamic equilibrium, with the H also in
equilibrium with HTq and electrons. Electroche~nical
equilibrium thus exists between the a + P Pd-H
electrode and the electrolyte as represented formally
by the equation
[lofl] Pd + H + + e*Pd-H
More specifically, when the electrode exhibits the
'50 mV' potential (7, 9, lo), a and P-PdH phases
co-exist with the a-PdH phase saturated (3 at.% H).
Reaction Ion should hence be written
[lob] a-PdH (satd.) + H + + e =2( a + P)-PdH
The absorption of H into Pd to form, initially, the
a-phase is known (10) to occur with very little
expansion of the Pd lattice. Hence, in [ 5 ]for reaction
4, Vpd strictly refers t o V,-pdH(,,,,j, a n d is almost
equal to this quantity while Vp,,, refers t o the volume
of a-PdH + P-PdH formed froin t h e saturated
a-phase by reaction 106. On the other hand, the
formation of the P-phase occurs with considerable
increase of the lattice parameters, a. Values of the
latter, obtained by Aben and Burgers (lo), using
X-ray diffraction, are listed in Table 7.
The value of the measured molar volume of 'PdH'
in an a + P-PdH system is therefore associated with
the production of H in the P-phase, since it is only
this phase that forms with a relatively large expan-
sion of the Pd lattice and a corresponding positive
volume change. Hence the value Vpd-,, = I I .3 cm3
mol-' given in Table 5 is the molar volume of for-
mation of H in the P-phase. The apparent voluine of
H itself, V,, can then be evaluated by taking the
difference of 'Vpd-,' and the inolar volume of a-PdH
TABLE
7. Lattice parameters for the Pd,Pd-H system (10)
a-Phase a-Phase +H (a + P) Phase +H
N = 0.3882 nm tr = 0.3886 nm cr, = 0.3886 nm
cr, = 0.4017nnl
 922 C A N . J . CHEM. VOL. 56. 1978
,
assuming V,-,,,, (,,, = V,,. This approach gives a
value for V,, = 2.0 cm3 mol-' which is the net
volun~echange of a-PdH (satd) upon absorption of
1 ~ n o of
l H atoms to produce P-PdH.
Direct evaluation3 of the quantities V,,-,, and V,,
for H in palladium does not seem to have been
previously reported in the literature, although V,, in
pure iron and in Pd-Ag alloys has been evaluated
by measuring the uptake of H, under uni-axial stress.
This type of measurement is based on the fact that
when a tensile stress is applied to a metal it causes
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 50.192.93.133 on 01/05/17
an increase in the solubility of H while a compressive
stress decreases the quantity of absorbed H-atoms.
The change of solubility of H is related to the
applied stress by
where c is the solubility of hydrogen (moles of H / C I
~ ~
of substrate) when the applied uniaxial stress is o and
c, is the solubility when the applied stress is zero.
Utilizing this approach, Bockris and co-workers (1 I)
have determined V,, for H in pure Fe as 2.6 cm3
For personal use only.
mol-'. Wriedt and Oriani (12) have determined the
value to be 1.90 cm3 mol-I in a 75% P d - 25% Ag
alloy which is in good agreement with the value
obtained in this work: V,, = 2.0 cn13 mol-'. It is of
interest that this value is appreciably smaller than
the volume of adsorbed H at Pt, which we recently
determined (22).
The behaviour of the Pd,Pd-HIM HCI(AgC1,Ag
cell a t pressures up t o 2500 bars appears to be
sufficiently reliable and reversible with respect to
increasing and decreasing changes of pressure, that
F times the pressure-coefficient of the cell emf can
be equated with certainty to the known molar volume
differences of the respective components in the cell
reaction. This being the case, the Pd-H,H+ electrode
can be utilized as a satisfactory reference electrode
in high-pressure electrochemical studies in acid
media, as were described in Part 11. The Ag,AgCl
electrode can be adopted for use in Cl- salt solutions
at elevated pressures.
6. Tlze Partial Molar Volume of H , itz Aqueous
Solution
From measurements at various hydrostatic pres-
sures on cells involving the Pt-H2/HTq electrode,
the partial molar volume of H z in aqueous solution
can be derived. Previous data in the literature for
V,, derived from emf measurements (1, 2) are
3The 'partial molar volume' of H in Pd and various Pd
alloys was evaluated by Baranowsky et ol. (23) from changes
of lattice parameters as a function of uptake of H from Hz at
high pressures.
apparently discrepant and differ from a value
obtained by Tiepel and Gubbins (13) using a dilato-
metric technique. The differences appear to be d u e
to ionic strength effects on the apparent molar
volume of H,.
For the cell Pt,H,IO.I M HCIIAgCI,Ag, Valeriote
and Gallop's (2) results give a partial molar v o l u ~ n e
of H, in 0.1 M HCI as 17.9 cm3 mol-'. Hills a n d
Kinnibrugh (I), using the cell Pt,H,IO.I N HCll
Hg2CI2,Hg, quote V,,2 = 15 cm3 mol-' for 0.1 M
HCI. Heusler and Gaiser (4), using cell I (eq. 8),
obtained emf values over a range of HCI concentra-
tion and evaluated the infinite dilution volume
V z = 24 cm3 mol-' from the pressure effect on t h e
emf of this cell.
It has been mentioned in subsection 4 that t h e
pressure-coefficient of emf of the cell Pt,H,I I M
HCIIAgC1,Ag could not, for various possible
reasons,
be measured experimentally in a reliable
manner (cf. ref. 4) but could be satisfactorily derived
from emf measurements on t h e cells Pt,H,(I M
HCIIPd-H,Pd and Pd,Pd-H I 1 M HCIIAgC1,Ag.
The pressure-coefficient of emf obtained in this
manner can be used to determine the partial molar
volume of H, in 1 M HCI.
The partial molar volume of H, obtained by this
procedure in the present work for 1 M HCI is
V,,, = 17.6 cm3 mol-' and agrees quite well with
the value of Heusler and Gaiser (4): V,,, = 17.7 cm3
mol-' for 0.80 M HCI. The V,,, values of Heusler
and Gaiser are plotted as a function of C1I2in Fig. 6.
The best-fit straight line has a slope of -6.3 a n d
gives an intercept V,": of 24 cm3 mol-I. The value
of V,,, obtained in the-present work IS within 0.2 cm3
mol-' of the corresponding value of Heusler a n d
Ciaiser on their V , , ~ - C " ~plot a t C = 1.0 M HC1.
This would give V:,= 24 cm3 mol-' (using their
FIG.6 . The variation of the partial molar volume o f H Z ,
VH2,with CIIz from the data of Heusler and Gaiser (4).
 CONWAY A N D CURRIE
slope). T h ~ svalue is in good agreement with the
previously reported (13) value V< = 25.2 cm3
mol-', based on dilatometric measuremeiits in pure
water.
Apparent discrepancies in the l i t e r a t ~ ~ rfor
e VkI1
values are evidently due to dependence of the
apparent values of V,,, on ionic strength (saltingout
effect). Table 8 summarizes the values of V,,,
obtained from the literature and from the present
work.
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 50.192.93.133 on 01/05/17
It is seen that introduction of a small molecule
such as H, into an aqueous solution results in a
surprisingly large volume increase (-24 cm3 11101- I ) .
This observation is consistent with the earlier work
of Frank and Evans (14) on the effect of dissolved
nonelectrolytes on the structure of water. The intro-
duction of nonpolar gases such as H,, Ar, He, and
Rn into aqueous solutions was found by these
authors in a large decrease in entropy of the system
( - 105-170 J K - ' mol-I). This behaviour was re-
lated to the ability of these solutes to promote so-
called structure building of water around nonpolar
For personal use only.
solute molecules. .The larger solute molecules, such
as Rn, promote a greater degree of structure making.
The formation of aggregates of structured water will
result in expansionof the solvent as reflected in the
relatively large values of the observed apparent or
partial molar volume of nonpolar solutes.
The partial molar volume of H, in 1 M aqueous
HCI at I bar is 17.6 cm3 mol-'; however, as the
pressure is increased, Vkl1decreases steadily until
about 800 bars. Above this pressure, the value of V,,,
becomes constant at 14.1 cm3 ~ n o l - ' (Table 6). The
decrease of Vl,, with pressure is due to the pressure-
induced destruction of part of the expanded water
structure around the H, solute. Above 800 bars, local
structure promoted by the introduction of H, into
the aqueous electrolyte has evidently been 'regelated'.
This behaviour is analogous to the observations
made by Frank and Evans (14) on the increase of
8. Part~nlmolar
TABLL vol~~mes
of H Z in aq. HCI
L halide salt ions (20), methods which give values for
(mol
HCI) Ref. 4
' Ref. 2 l Ref. I!: Ref. 138
* P t , H 2 M HCIIAgCI.Ag.
t P t , H 2 0.1 M HCIIAgC1,As.
tPt.H20.1 h4 HCIIHg?Cl2,Hg.
IDilatometer method 111 aqucous KOH.
923
entropy with increasing temperature for nonpolar
gases in water. This variation was attributed to the
'melting' of the so-called 'iceberg' structures sur-
rounding the solute molecules.
The large concentration dependence of apparent
values of VH2observed in this work and that of
Heusler and Gaiser (4) (S, = -6.3) can be explained
in terms of the salting-out effect. In solutions of
inoderate electrolyte concentration (0.01 -> I M),
increasing mole fractions of the solvent will be
involved in solvation of the respective ions as their
concentration increases. Therefore, a solute molecule
such as H, when introduced into an ionic solution
sees a smaller voluliie o f 'free' solvent ~noleculesthan
would be the case in pure water. T h e activity co-
efficient of the H, gas is therefore i n ~ ~ - e a s ecorre-
d
sponding to reduction of its solubility (salting-out
effect) (I 5, 16). Therefore the volume change accom-
panying the dissolution of H z will be less than the
V,", value due to the effect of pressure on the
activity coefficient associated with the influence of
the ions present.
7. Pressure Coeficient.~of Indivih~alEkectrode -
Solution Potential Dlfereizces
In studies of kinetics of electrode processes as a
function of pressure, a n apparent volume of activa-
tion A V;,* is obtained (3) which differs (6, 18) from the
true, kinetically significant value AV,' by /3 times
the volume change, AVO, for the same overall
electrode process at equilibrium: AV,* = AV;,' +
PAVo o r AV* = AVi,* - (1 - P)AVo, where P is
the symmetry coefficient for the electron-transfer
process. The term PA Vo enters (6) into the expression
for AV,* due to the pressure-dependence of the
potential difference a t the reversible reference
electrode used to make the kinetic measurements at
well-defined electrode potentials.
The present results enable the individual pressure
coefficients of the metal-solutioli potential differences
for the Pd-H/Ht and Pt-H2/Ht reference electrodes
to be estimated, taking a value for V,;". = -5.4
cm3 mol-' based on ([I) ultrasonic vibration poten-
tials (19) and (b) extrapolation of volurnes of R,Nt
This
v,;"+in very good agreement (21). T h e individual
work
pressure-coefficients and corresponding volume
changes AVO are given in Table 9. T h e AVO values
depend on the assignment of a value V, for the
volume of electrons in a metal. The figure of 3 c1n3
Faraday-' from ref. 4 has been used for the data
given in Table 9.
The individual pressure coefficients of potential
differences in Table 9 d o not take account of the
(unknown) pressure dependence of surface-potential
 924 C A N . J. CHEM. VOL. 56, 1978

TABLE9. Pressure coefficient of metal-solution potential W. R. HAINSWORTH, H. J. ROWLEY, and D. A. MACINNES.

differences at individual reference electrodes J . Am. Chem. Soc. 46, 1437 (1924).
B. E. C O N W A Y111 . Chemical physics of ionic solutions.
AV (dE/dP), Editeri by B. E. Conway and R. G. Barradas. John Wiley
Electrode (cm3 rnol-') (WV bar-') and Sons Inc., New York, NY. 1966. pp. 577-578.
S. S C H U L D I N EJR. ,P. HOARE,and G. W. CASTELLAN. J.
Hf + e + : H z 14.4 - 14.9 Chem. Phys. 28, 16 (1958): 28,22 (1958).
Hf e+ + PdePdH 4.4 -4.6 F. J . MILLERO. 111 Water and aqueous solutions. Editeci by
AgCl +
e e Ag CI- + 4.7 -4.9 R. A. Horne. Wiley Interscience, N e w York, NY. 1972.
R. B. FLANAGAN and F . A. LEWIS.Trans. Fal-aday Soc. 55,
1409(1959).
differences, dx/dP. However, the corresponding P. C. ABENand W. G. BURGERS. Trans. Faraday Soc. 58,
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 50.192.93.133 on 01/05/17

effects of varying temperature indicate that dx/dT is 1989 (1962).

not appreciable. Hence it is reasonable to assume W. BECK,J . O'M. BOCKRIS. J . MCBREEN, and L. NANIS.
Proc. R. Soc. London, A, 290,220 ( 1966).
that any pressure dependence of x up to ca. 3000 bars H. A. WRIEDTand R. A. O R I A N IActa . Metall. 18, 753
will not seriously affect the values of the pressure (1970).
coefficient of individual electrode potentials evalu- E. W. TIEPELand K. E. GUBBINS. J . P h y s Chem. 76,3044
ated from V data, and hence of the derived true (1972).
activation volulnes in kinetic studies. H. S. F R A N Kand M. W. EVANS.J . Chem. Phys. 13, 507
(1945).
Acknowledgements 15. P. DEB YE^^^ J . MACAULAY. Z. Phys. Chem. 26,22 (1925).
16. B. E. C O N W A Yand D. M. NOVAK.III Chemistry and
Grateful acknowledge~nentis made to the Defence physics of aqueous gas solulions. The Electrochemical
Research Board for support of this work in its early Society, Princeton. 1975. p. 115.
17. D. J . G. IVES and G. J . JANZ. Reference electrodes.
stages and t o the National Research Council of Academic Press, New York, NY. 1961. pp. 112-1 15,
Canada for its support over the past two years. We 203-218.
For personal use only.

also acknowledge useful discussions with Drs. W. 18. B. E. C O N W A YJ .. Electrochem. S o c . 113, 1118(1966).
A d a m and J. Valeriote. 19. R. Z A N Aand E. YEAGER. J . Phys. Chem. 70,954 (1966); 71,
52 1 (1967).
1. G. J . HILLSand D. R. K I N N I B R U GJH. Electrochem.
. Soc. 20. B. E. CONWAY, J . E. DESNOYERS, and R. E. VERRALL. J.
113, 11 11 (1966). Phys. Chem. T ~ a n sFaraday
. Soc. 62,2738(1966).
2. E. M. L. VALERIOTE and L . D. GALLOP.J . Elect~.ochem. 21. B. E. C O N W A YJ ,. E. DESNOYERS, and R. E. VERRALL. J.
SOC.121. 1245 (1974). Phys. Chem. 75,3031 (1971).
3. B. E . C O N W A aYn d J . C . CURRIE.J . Electrochem. Soc. 125, 22. B. E. CONWAY and J . C. C U R R I EJ .. Chem. Soc. Faraday
252 (1978); 125,257 (1978). Trans. I. In press.
4. K. E. HEUSLERand L . GAISER.Ber. Bunsenges. Phys. 23. B. BARANOWSKI, S. MAJCHRZAK, a n d T. B. FLANAGAN. J.
Chem. 72, 1059(1969). Phys. F , 1,258 (1971).