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Effect of Pressure On PH
Effect of Pressure On PH
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
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
+
'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 T h e bottom of the cell is a glass cup with a threaded opening
electrode is particularly suitable for studies of 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-
electrode processes at elevated pressures since no pressure seal. Both the top and bottom of the cell had ridges
added gas is required in the high-pressure cell. Also, which allowed a positive Teflon-to-glass seal to be made when
the pressure-dependence of the ~ d - H / H f electrode the two pieces are joined with theshrinkable Teflon tubing. T h i s
potential enables the molar volume of H sorbed in type of cell can easily tolerate a 3 0 x volunle change without
undue strain being generated.
Pd, as the P-PdH phase, to be derived. The cell for high-pressure emf measurements consists of 3
The pressure dependence of the potential of a reversible electrodes, two of which are o f the same type. T h i s
reversible electrode reaction is related t o the volume provides a reliable check o n the behaviour of each electrode
change occurring in the half-cell reaction. Thus, the while inside the high-pressure bomb. F o r example, if the cell
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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
AE (V)
P (bars) Run 1 Run 2
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TABLE
3. The emf data in volts for the cell Pd,Pd-Hlaq. HCI, niolarity MIAgCI,Ag at 298 K
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.
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
*Estimated errors are evaluated from standard deviations, duplicate ernfmeasuremenls in the compression and decompression modes
and the intrinsic error in the pressure measurement.
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.
P
(bar) C(rno1 HCI) (aAE,/aP)T(pV bar-I) (aAE,/aP), (aAE3/aP), AV, (cm3 mol-') V,,2 (cm3 mol-')
1 1 .O 5.85 8.40 -2.55 -5.65 17.6
> 800 1.O 4.35 6.90 -2.55 -4.20 14.1
hydrogen electrode is used in a Teflon, Lexan, or achieve a potential of about +0.050 V with respect
nylon high-pressure cell. The effects were again to a standard Pt,H, reference electrode. Hydrogen
attributed to diffusion of H z through the walls of is absorbed initially by palladium in t h e a-phase up
the cell.
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for which 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
is obtained from the pressure dependence of the The absorption of H into Pd to form, initially, the
emf's of cells designated 2 and 3. a-phase is known (10) to occur with very little
The (aAE/aP), values for cells 1, 2, and 3, and the expansion of the Pd lattice. Hence, in [ 5 ]for reaction
volume change, AV,, for the cell reaction 7 are listed 4, Vpd strictly refers t o V,-pdH(,,,,j, a n d is almost
in Table 6. The partial molar volume of Hz in 1 M equal to this quantity while Vp,,, refers t o the volume
HCI at P = 1 bar, as calculated from [8], is also of a-PdH + P-PdH formed froin t h e saturated
given in Table 6. a-phase by reaction 106. On the other hand, the
formation of the P-phase occurs with considerable
5. T l ~ eVolurne of H Sorbed into P d rrnd the increase of the lattice parameters, a. Values of the
SigniJicance of tlze Quantity V,,I,I latter, obtained by Aben and Burgers (lo), using
From the data given above, it is seen that evalua- X-ray diffraction, are listed in Table 7.
tion of the pressure coefficient of emf for the cell 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
can provide a convenient method for the determina- this phase that forms with a relatively large expan-
tion of the molar volume, Vpd-,,, of Pd-H. The sion of the Pd lattice and a corresponding positive
significance of Vpd-, can best be visualized if the volume change. Hence the value Vpd-,, = I I .3 cm3
processes involved in the Pd-H,H+ reference elec- mol-' given in Table 5 is the molar volume of for-
trode reaction are considered. mation of H in the P-phase. The apparent voluine of
The behaviour of the Pd-H,H+ reference electrode H itself, V,, can then be evaluated by taking the
has been studied by Schuldiner et al. (7), Flanagan difference of 'Vpd-,' and the inolar volume of a-PdH
and Lewis (9), and by Aben and Burgers (10) with
varying opinions on the actual mechanisms involved TABLE
7. Lattice parameters for the Pd,Pd-H system (10)
in the functioning of such an electrode. However, the
mechanism described below appears to be the most a-Phase a-Phase +H (a + P) Phase +H
consistent with the experimental facts. It is known N = 0.3882 nm tr = 0.3886 nm cr, = 0.3886 nm
that a palladium wire charged with hydrogen cr, = 0.4017nnl
electrolytically or under hydrogen atmosphere will
922 C A N . J . CHEM. VOL. 56. 1978
,
assuming V,-,,,, (,,, = V,,. This approach gives a apparently discrepant and differ from a value
value for V,, = 2.0 cm3 mol-' which is the net obtained by Tiepel and Gubbins (13) using a dilato-
volun~echange of a-PdH (satd) upon absorption of metric technique. The differences appear to be d u e
1 ~ n o of
l H atoms to produce P-PdH. to ionic strength effects on the apparent molar
Direct evaluation3 of the quantities V,,-,, and V,, volume of H,.
for H in palladium does not seem to have been For the cell Pt,H,IO.I M HCIIAgCI,Ag, Valeriote
previously reported in the literature, although V,, in and Gallop's (2) results give a partial molar v o l u ~ n e
pure iron and in Pd-Ag alloys has been evaluated of H, in 0.1 M HCI as 17.9 cm3 mol-'. Hills a n d
by measuring the uptake of H, under uni-axial stress. Kinnibrugh (I), using the cell Pt,H,IO.I N HCll
This type of measurement is based on the fact that Hg2CI2,Hg, quote V,,2 = 15 cm3 mol-' for 0.1 M
when a tensile stress is applied to a metal it causes HCI. Heusler and Gaiser (4), using cell I (eq. 8),
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an increase in the solubility of H while a compressive obtained emf values over a range of HCI concentra-
stress decreases the quantity of absorbed H-atoms. tion and evaluated the infinite dilution volume
The change of solubility of H is related to the V z = 24 cm3 mol-' from the pressure effect on t h e
applied stress by 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
where c is the solubility of hydrogen (moles of H / C I reasons,
~ ~ be measured experimentally in a reliable
of substrate) when the applied uniaxial stress is o and manner (cf. ref. 4) but could be satisfactorily derived
c, is the solubility when the applied stress is zero. from emf measurements on t h e cells Pt,H,(I M
Utilizing this approach, Bockris and co-workers (1 I) HCIIPd-H,Pd and Pd,Pd-H I 1 M HCIIAgC1,Ag.
have determined V,, for H in pure Fe as 2.6 cm3 The pressure-coefficient of emf obtained in this
manner can be used to determine the partial molar
For personal use only.
slope). T h ~ svalue is in good agreement with the entropy with increasing temperature for nonpolar
previously reported (13) value V< = 25.2 cm3 gases in water. This variation was attributed to the
mol-', based on dilatometric measuremeiits in pure 'melting' of the so-called 'iceberg' structures sur-
water. rounding the solute molecules.
Apparent discrepancies in the l i t e r a t ~ ~ rfor
e VkI1 The large concentration dependence of apparent
values are evidently due to dependence of the values of VH2observed in this work and that of
apparent values of V,,, on ionic strength (saltingout Heusler and Gaiser (4) (S, = -6.3) can be explained
effect). Table 8 summarizes the values of V,,, in terms of the salting-out effect. In solutions of
obtained from the literature and from the present inoderate electrolyte concentration (0.01 -> I M),
work. increasing mole fractions of the solvent will be
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It is seen that introduction of a small molecule involved in solvation of the respective ions as their
such as H, into an aqueous solution results in a concentration increases. Therefore, a solute molecule
surprisingly large volume increase (-24 cm3 11101- I ) . such as H, when introduced into an ionic solution
This observation is consistent with the earlier work sees a smaller voluliie o f 'free' solvent ~noleculesthan
of Frank and Evans (14) on the effect of dissolved would be the case in pure water. T h e activity co-
nonelectrolytes on the structure of water. The intro- efficient of the H, gas is therefore i n ~ ~ - e a s ecorre-
d
duction of nonpolar gases such as H,, Ar, He, and sponding to reduction of its solubility (salting-out
Rn into aqueous solutions was found by these effect) (I 5, 16). Therefore the volume change accom-
authors in a large decrease in entropy of the system panying the dissolution of H z will be less than the
( - 105-170 J K - ' mol-I). This behaviour was re- V,", value due to the effect of pressure on the
lated to the ability of these solutes to promote so- activity coefficient associated with the influence of
called structure building of water around nonpolar the ions present.
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).