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KINETICS OF ELECTROLYTIC HYDROGEN EVOLUTION

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AND THE ADSORPTIQN OF HYDROGEN BY B'IETALS

BY J. G. N. THOMAS
Dept. of Chemistry, University College of Swansc:: *
Receiwd 6th Jidy, 1960
For metals where the electrolytic hydrogen evolution reaction gives a Tafcl line of
low slope, e.g., 2.3 RT/2F or 2.3 RUF, the formulation of the reaction kinetics oil the
assumption that the adsorbed hydrogen atoms obey a Lzngmuir isotherm is not in good
agreenient with espcriniental data on surfxe coverage and reaction rates. A more con-
sistent kinetic scheme is obtained by taking into account the variation with coierage of
the heat of adsorption and activation energies for adsorption and desorption of hydrogen
011 metals. A Tafel slope of 2.3 RT/2F corresponds to a fast discharge reactloii fdhwed
by a ratedetermining combination reaction, where the chemisorption of hydrogeir by tile
metal is not activated. A Tafel slope of 2.3 RTIF corresponds to a fast discharge reaction
followed by either a rate-deterrninii2g combiiiation reaction, where the chemisorption
of hydrogen by the metal is activated, or by a rate-deiermining ioniatom reaction. It
is possible to distinguish these alternatives by considering the change in Tafel slope at
high current densities.

A detailed analysis of the kinetics of the electrolytic hydrogcn-evolution re-

action based on the assumption that the adsorbed hydrogen awms obey a Langmuir
isotherm, has recently been given by Bockris.1 In acid solutions, three reactions
are assumed to predominate :
the discharge reaction,
H3O++e-M +H-M H20 ;+
the combination reaction,
2H-M$H2-M+ M; (2)
the ion+ atom reaction,
H3O++H-M+e-M+H2--M+M+H20, (3)
where e-M represents an electron bound in the metal and H-M and H2-M
represent a hydrogen atom and molecule respectively, adsorbed to a surface
metal atom. The energy barriers for reactions (1) and (3) are assumed to be
symmetrical.
When the discharge reaction is fast and the combination reaction is rate-
determining, the slope of the Tafel line was derived to be 2.3 RT/2F, i.e., 0.029 at
25'. This value is experimentally well established on platinum 2 and palladium.3
However, the theoretical derivation of this Tafel slope assumcs that the surface
coverage 8 with adsorbed hydrogen atoms is <0.1. This is not in agreement with
the results of Ershler and Fi-umkin 4 who showed by the study of charging C U T V ~ S
that the coverage of the surface with adsorbed hydrogen was fairly high at the
reversible potential. This has been confirmed by the a.c. impedance measurements
of Breiter, Knorr and Volkl.5 However, Schuldiner has recently derived very
low values, 8<0-1 for the adsorbed hydrogen coverage on platinam, bascd on th:
application of the Langmuir isotherm and the assumption that the observcd
linlitiiig anodic currents for the ionization of hydrogen correspond to 0 0. L=

* present address: National Chemical Lab., Teddington, Middlesex.

103
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1604 ELECTROLYTlC HYDROGEN EVOLUTION AND ADSORPTION

This assumption does not seem justified since it has not been proved that diffusion
effccts are absent in the limiting anodic currents. The assumption of a Langmuir
isotherm, i.e., the heat of adsorption independent of coverage, is also not con-
sistent with the results of D o h , Ershler and Frumkin 7 who found that the rate
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of the discharge process was independent of potential. They showed this could
be explained by taking into account a linear fall in the heat of adsorption of
hydrogen with coverage.
When the discharge reaction is fast and followed by a slow ion+ atom reaction,
then a Tafel slope of 4*6RT/3F,i.e., 0.038 at 25", is obtained, provided that the
surface coverage with adsorbed hydrogen atoms is lo^, i.e., 0<0.1. A Tafel
slope close to this value seems to have been observed only for palladium, where
Hoare and Schuldiner 8 found a Tafd slope of 0.042 at 39". However, the
palladium used by Hoare and Schuldiner contained hydrogen in a ratio of Pd : H
of at least 0-6. The heat of absorption of hydrogen by palladium is less than the
heat of adsorptioiQ so the surface coverage with hydrogen atoms is unlikely to
be less than 0.6, and so much greater than the assumed value.
The kinetic treatment in terms of the Langmuir isotherm is more satisfactory
when applied to cases where the surface coverage is very small, as when thc dis-
charge reaction is rate-determining, or where the surface coverage tends to one in
the cases where the discharge reaction is very fast and followed by either the slow
combination or ion+ atom reaction. In all these cases the Tafel slope is 4.6 RTIF,
i.e., 0.116 at 25".
In recent years it has become apparent that Tafel slopes other than the three
values discussed above are obtained in very pure solution. Some of these values
are listed in table 1.
TABLEINTERMEDIATE VALUES OF SLOPES OF TAFEL LINES

metal solution temp., "C Tafel slope ref.

Ag 0.1-0.4 N HCl 23 0-058 8

As 2 N H2SO4 6-26 0.059 9
W 0.1 N HC1 23 0.060 8
Pt 1.0 N HC1 23 0.053 8
(prep. in air)
Rh 0.01 N HC1 room 0.055 10, 11
Mo 0.001-0.1 N HC1 room 0-079 10
Au 0*001-0.1N HC1 room 0.073 10

Two explanations 10 have been proposed for these intermediate values of the
Tafel slope. First, it was suggested that for silver and tungsten, since the potential
of the electrode is near the electro-capillary maximum, thc slope of the Tafel line
is affected by ion adsorption. This was discounted by Parsons,14 who pointed
out this effect was insufficient to explain the observed magnitude of the change in
slope. The other suggestion was that the rate-controlling process in the hydrogen
evolution reaction was the migration of adsorbed hydrogen atoms over the electrode
surface to react with immobile adsorbed hydrogen atoms forming hydrogen
molecules. However, to obtain a Taf'el slope of 2.3 RT/F on this basis, it must
be assumed that the coverage of the electrode surface with adsorbed hydrogen
atoms is small, i.e., less than 0.1. Since this value of the slope of the Tafel line
is observed on metals such as tungsten, platinum and rhodium which adsorb
hydrogen well, this assumption seems unlikely to be correct.
It is clear that if a Langmuir isotherm is used to describe the condition of
hydrogen atoms adsorbed on an electrode, Tafel slopes less than 4.6RT/F can
only be explained on the assumption that the surface coverage with hydrogen
atoms is small. These low Tafel slopes are observed on metals with moderate to
good adsorptive capacity for hydrogen where it would seem more probable that
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J . G . N. T H O M A S 1605
the surface coverage with hydrogen is appreciable. It is the purpose of this paper
to show that thesc Tafd slopes can be accounted for in terms of a moderate surface
coverage of hydrogen atoms, if the variation with coverage of the heat of adsorption
and the activation energies for adsorption and desorption of hydrogen are taken
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into considere tion.

REACTION KINETICS WHEN THE HEAT OF ADSORPTION OF HYDROGEN FALLS LINEARLY

WITH COVERAGE
Some relevant characteristics of hydrogen adsorption on metals from the gas
and aqueous phases will now be briefly reviewed and applied to the kinetics of
electrolytic hydrogen evolution. The adsorption of hydrogen from the gas phase
by metals can be represented by the potential energy curves 15 of fig. 1. ABC

FIG. 1.

is the potential energy curve for van der Waals adsorption. For most metals
the chemisorption of hydrogen as atoms does not require any activation energy.
Then the potential energy curve for chemisorbed hydrogen atoms will be as shown
by DEF, and the point of intersection X with ABC lies below the zero of potential
energy 00. Non-activated chemisorption of this type from the gas phase normally
leads to a large coverage with hydrogen atoms. In aqueous solution, hydrogen
adsorption on metal electrodes must compete with the adsorption of ions and
water molecules. Ion adsorption will be small provided that specifically adsorbed
anions are abssnt and the electrode potential is not highly negative. Unfortunately
very little quantitative information is available for the adsorption of water.
Kemball 16 found the heat of adsorption of water on to mercury from the vapour
phase to be 17-6kcal/mole. Mercury forms very weak adsorption bonds and
on more strongly adsorbing metals such as the transition elements, it would be
expected that water would be much more strongiy bound. Therefore the surface
coverage by adsorbed hydrogen will be reduced in aqueous solution by an amount
depending on the relative heats of adsorption of hydrogen and water. Thus, in
aqueous solution, non-activated adsorption of hydrogen may lead to only a
moderate surface coverage with adsorbed hydrogen atoms.
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1606 ELECTROLYTIC H Y D R O G E N E V O L U T I O N A N D A D S O R P T I O N

In general, the heat of adsorption of hydrogen from the gas phase decreases
with coverage and between 0 = 0-1 and 0.9 the variation is best represented by a
linear function.17 Similar behaviour has been observed in the adsorption of
hydrogen from aqueous solution by the platinum metals.39 23 According to
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recent illccries,15*18 this decrease of adsorption heat with coverage is caused by

the change in work function of the metal due to the bond dipoles of the adsorbate.
For the simultaneous adsorption of two species,ls if the bond dipoles of both
species are directed in the same sense, then the heats of adsorption of both species
are decreased; if the dipoles of the two species are directed in opposite senses,
the heats of adsorption of both species are increased. Hydrogen is adsorbed
by metals from the gas phase 19 or aqueous solution 20 to give a dipole with the
negative side outwards. Electron emission 21 and conductivity 22 results for
mercury, platinum and nickel show that water adsorbed from the gas phase forms
a co-ordinate adsovtion bond between the oxygen and the metal, i.e., the dipole
is positive outwards. In aqueous solution, it appears possible that on weakly
adsorbing metals such as mercury this orientation of adsorbed water molecules
can be altered by interaction with bulk water molecules, giving a dipole layer with
the negative side outwards.23 On more strongly adsorbing metals, it seems un-
likely that solvent interactions would be strong enough to alter the co-ordinate
oxygen-bond orientation. Thus, compared to the gas phase the heat of adsorption
of hydrogen by metals in aqueous solution may be somewhat increased or de-
creased by the adsorption of water, according to its orientation. However, the
relative heats of adsorption of hydrogen by metals in solution would probably
be much the same as in the gas phase.
As the surface coverage with hydrogen atoms increases, the decreasing heat of
adsorption results in a vertical shift of the potential energy curve DEF in fig. 1.
If the intersection point with ABC moves above the zero energy line OO, as with
GHI intersecting at Y,an activation energy E, is required for chemisorption of
hydrogen as atoms. Due to the work function effect, Ea in aqueous solution will
be affected by the adsorption of water molecules. E, will be increased or decreased,
according to whether adsorbed hydrogm and water form similarly or differently
orientated dipoles.
Considering now the kinetics of electrolytic hydrogen evolution, the linear
decrease of the heat of adsorption of hydrogen with coverage has been taken into
account by Dolin, Ershler and Frumkin,4 L~ikovtsev,24and more recently by
Parsons.25 Following these treatments, it is assumed that the heat of adsorption
of hydrogen from aqueous solution on an electrode varies according to

where r is a constant, Qe and Qo are the heats of adsorption at coverages 8 and

zero respectively. Then provided the surface coverage with hydrogen is moderate,
i.e., 6 = 0.2 to 0.8, the rates of the discharge process in the forward and reverse
directions are given by
- ? - ? -?

ul = kluH+exp - [AGi +a&/2 +a4F]/RT,

c c c
ul = k , exp -[AG~-(I-a)Or/2-(1-ci)$F]jRT, (3)
--* t
where kl and kl are rate constants representing the products of transmission
coefficients and frequency factors, and ~ZH+is the hydrogen ion activity in solution.
4 is the inner potential differencebetween the metal and the solution, and is related
to the overpotential q and the equilibrium potential 4* by
4 = q+#)*.
3 t
AG? and AG; are standard free energies of activation-forthe forward and reverse
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J . G . N. T H O M A S 1607
directions at 4 c= 0 and 8 = 0, and Q is the rdativc slope of the potential encrgy
curves of thc initial and final statcs at their yoifit of intersection. 'It is i:ow ns-
sumed that the discharge reactio:i is fast compared t!, thc subscqueilt ccnibinatim,
or ion-t-atom, reaction so that in the steady state tlie coverage of the surface uith
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hydrogen atoms is controlled by the discharge reaction. Ihe variation of coverage

with potential is then obtained by equating (2) arid (3) and a linear rzlationship
is found with (-d@dt$) = 2F/r. Experimentally, a nearly linear variatior, of
coverage with potential has been observed for the reversible desorption of hydrogen
from platinum on anodic polarization.20
When the formation of molecular hydrogen occurs by the combiiiation reaction,
the kinetics depend on the potential energy relationships between the chemisorkd
and van der Waals' adsorbed states, as discussed above. If the adsorption of
hydrogen from aqueous solution by the metal is not activated, the potential energy
curve for chemisorbed hydrogen atoms is as shown by DEF in fig. 1 arid the inter-
section X with ABC lies below 00'. Then the activation energy for foimation of
hydrogen molecules from adsorbed atoms is equal to the energy of the overall
reaction. This is the heat of adsorption, so that the variation of the aclivation
cnergy for desorption with coverage is, as assumed in (1) above,
Eo = Eo - rO. (4)
In the middle range of coverage, the rate of the combination reaction is then given
bY
4 + +
v2 = k2 exp -(AG$-rB)lRT, (5)
+
where AG; is the free energy of activation at zero coverage.
If the combination reaction is rate determining for the formation of hydrogen
molecules and its rate in the reverse direction is negligible, substituting for 0 the
--t
value in terms of 4 obtained from (2) and (3) above gives t'2 in terms of &. Since
+
the current is i = 2Fu2,

i=
-. k7)
U.(
+
laH+ * 4

exp -[AG$-2(A&AGi)+2@]1RT.
+
(6)

Taking logs and differentiating gives the slope of the Tafel line as (-d&d logloi) =
2.303 RT/2f', i.e., 0.029 at 25'. The above derivation of the Tafel slope of 0.029
has not previously been described. For comparison, the relation to hydrogen
adsorption of previous treatments of the combination and ion+ atom reactions
will be outlined.
If the chemisorption of hydrogen from aqueous solution by the metal requires
an activation energy E,, then the potential energy curve for adsorbed hydrogen
atoms will be similar to GHI in fig. 1. The activation energy for formation of
molecular hydrogen from adsorbed atoms is then the energy required to pass
over the energy barrier at Y. As the heat of adsorption decreases with coverage,
the curve GHI shifts vertically and ABC remains essentially fixed, so that the
activation energy for desorption decreases with coverage according to
EO = Eo-prO, (7)
where rO is the variation of the heat of adsorption with coverage and p is the rela-
tive slope of GHI and ABC at the intersection point Y. Then the rate of the
combination reaction is given in the middle range of coverage by
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1608 ELECTROLYTIC HYDROGEN EVOLUTION A N D ADSORPTION

Substituting for 0 as above gives the slope of the Tafel lirie a s

(- ~ ! i ) / d10gl oi) - - 2.303 RT/2/jF,
Considering now the ion+ atom reaction for the foimation of molecular
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hydrogen, nothing is known of the potential energy curves for this process. If
the ionfatom reaction is rate determining, it would appear probable that the
potential energy curve3 of the initial and final states will intersect where the potential
energy is positive. Then the relative slope y of the potential energy curves will
determine the variation of the free energy of activation with coverage,

where rO is the variation of the heat of adsorption of hydrogen with coverage

and the factor 1/2 arises because only one adsorbed hydrogen atom is involved in
the reaction. The rate of the ion+atoni reaction is then

+
v 3 = k3nH+ exp - (AG: - yrt?/2 ySF)/RT.
If the rate of this reaction in the reverse direction is negligible, the Tafel slope for
hydrogen evolution is (- d4/d loglo i) = 2.303 RT/2yF.

APPLICATIONS TO EXPERIMENTAL RESULTS

The above kinetic scheme shows that when the fall in th? heat of adsorption
of hydrogen with coverage is taken into account, a fast discharge reaction followed
by a rate-determining combination reaction gives a Tafel slope of 0.029 at 25,
for an electrode surface moderately covered with hydrogen atoms. The essential
condition is that chemisorption of hydrogen from aqueous solution is non-activated.
In view of the adsorption of water, it seems reasonable that this would be the case
at moderate surface coverages of hydrogen atoms. It is proposed that this is
the correct interpretation of the Tafel slope of 0.029 observed on platinum. This
explanation is consistent with the adsorption of hydrogen on platinum and with
the charging curve results on the surface coverage with hydrogcn atoms. It forms
a logical extension of the results of D o h , El-shler and Frumkin,7 who showed
the rates of the discharge reaction in the forward and reverse directions are given
by expressions of the form of (2) and (3). This view of the reaction is also con-
sistent with the known data on palladium.
In the adsorption cf hydrogen from the gas phase by metals, an activation
energy for adsorption may arise at high coverage, e.g., on Fe,26 Ni,27 Pt,28 Pd,29
or because of contamination of the sur.face,;O e.g., by adsorbed oxygen. On th::
group IB metals, Cu, Ag and Au, chemisorption of hydrogen as atoms irom
molecules appears to require an activation energy at all coverages.31 As discussed
above, similar general behaviour is to be expected in aqueous solution. Therefore
if the combination reaction is desorptive under these conditions, the Tafel slope
will be 2.303 XT/2/3F. The factor p corresponds to the ratio of the variation of
the activation energy of desorption of hydrogen with coverage to the variation of
the heat of adsorption with coverage. Hydrogen adsorption data giving values
of fl are scarce, but calculations based on the results of Gundry and Tompkins 27
for nickel show that in this case p is about 0.5. This might be expected to be a
probable value for fl, representing a symmetrica1:energy barrier for the combination
reaction. If is 0.5, the Tafel slope is 0.058 at 25. Activated adsorption of
hydrogen has been found30 on all the metals in table 1 which give Tafel slopes
of 0.058, and so this mechanism could be operative. The behaviour of phtinum
prepared in air agrees well with this mechanism, as a change in the slope of the
Tafel line from 0-028 to 0.05 is observed, corresponding to the appearance of a n
activation energy for hydrogen adsorption due to iccreasing surface coverage
with hydrogen atoms and adsorbed oxygen. The case of gold is interesting since
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J . G. N . T H O M A S 1609
it Tafel slope of 0.029 has been observed 3' i n contradiction of the gas-phase
adsorption results. However, Eley and Rossington -33 have found the para-
hydrogen conversion on gold wires to proceed at 1O'C with an apparent activation
energy of about 5 kcal/mole. This indicates that the chemisorption of hydrogen
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from &hegas phase requires only a small activation energy. It seems probable
that, due to the work function effect, the activation energy for adsorption of hydro-
gen from aqueous solution by gold is reduced to zero through the adsorption of
water molecules. However, the surface coverage with hydrogen atoms remains
small.5 The Tafel slope of 0-073 observed on gold by Sheldon, Pentland and
Bockris 12 would correspond to a less active specimen giving activated hydrogen
adsorption.
If a fast hydrogen ion discharge reaction is followed by a rate determining
ionfatom reaction then, as shown above, the Tafel slope in the intermediate
region of coverage is 2.303 RT/2yF. Assuming that y = 0.5, the Tafel slope is
0.058 at 25". This mechanism can therefore provide an explanation for the
Tafel slopes of 0.058 listed in table 1.
It is possible to distinguish between these alternative mechanisms by con-
sidering the change in kinetics at high current densities. Substitution in (2) of
the value of 8 in terms of 4 obtained from (2) and (3) shows that the rate of the
discharge reaction is independent of potential, though the surface cokerage with
hydrogen atoms increases with increasing negative potentials. The rates of the
subsequent combination or ion+ atom reactions increase with potential according
to exp- (2P4F/RT) or exp - (2?4F/RT). Therefore as the potential increases,
two cases may arise. The surface coverage may increase until 0 = 1 and the
kinetics remain unchanged, i.e., the discharge reaction remains faster than the
following reaction. Alternatively, the rate of the following reaction, whether
the combination or the ion+atom reaction, may increase until it equals and
surpasses that of the discharge reaction.
For the combination reaction, as 0 tends to one, then the Langmuir isotherm
treatment 1 can be applied to show that the Tafel slope tends to co,corresponding
to a limiting current. If the rate of the combination reaction becomes equal to
that of the discharge reaction in the steady state at moderate coverage then
equating the rate equations (2) and ( 5 ) gives 0 in terms of 4 and substituting for
6 in (2) leads to a Tafel slope of 2.303 (RT/F)[(2+x)/2x]. If a is 0.5, this is 2.303 x
5RT/2F, i.e., 0.145 at 25". Alternatively, if the rate of the combination reaction
is given by (8), the corresponding Tafel slope is 2.303 (RT/F)[(a+2P)/2@]. If
a = p = 0.5, the value is 2.303 x 3 RT/F, i.e., 0.174 at 25". Therefore, if the
fast discharge reaction is followed by a slow combination reaction, at high current
density the Tafel slope should increase to 0.145, or 0.174 or co. The existence of
a Tafel slope of co has been experimentally demonstrated on platinum and pallad-
ium,z confirming that the combination reaction is rate determining.
If the discharge reaction is followed by the ion+atom reaction then as 8 tends
to one, the Langmuir isotherm treatment 1 shows that the Tafel slope is 2.303 RT/yF.
If y = 0.5, this is 0.116 at 25". In the alternative case, the rate of the ion+atom
reaction with increasing potential may attain that of the discharge reaction in the
coverage region where the rate equations ( 2 ) and (10) are applicable, then at the
steady state, equating ( 3 ) and (10) to obtain 8 and substituting for 6 in (2) gives a
Tafel slope of 2.303 (RT/F)[(a+ y ) / 2 a y ] . If o! ='y = 0-5,this gives 2.303 x 2 RT/F,
i.e., 0.116 at 25C. Therefore, if at low overpotential, the reaction path is fast
discharge reaction followed by slow ion+ atom reaction, then at high overpotential,
a transition to a Tafel slope of 0.116 should be observed. This is the case for
silver,lov 11 tungsten,lo and rhodium 13 indicating that in the region where the
Tafel slope is 0.058, the ionfatom reaction is desorptive on these metals.
In the discussion above of the combination and ion+atom reactions for
hydrogen molecule formation, it was assumed that the slopes of the potential
energy curves for the initial and final states of the reactions are equal, i.e., p = y =
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1610 ELECTROLYTIC HYDROGEN E,VOLUTION AND ADSORPTION

0.5. There seems no reason whyp and y should not have values other than this or
why p and y shodci not vary with coverage. There is no direct evidence about
y values for the ion+ atom reaction. Iwever, gas adsorption studies comparing
the activation mergies for desoiptioli or L^;dsoiptimwith heats of adsorption show
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that fl values other than 0.5 are observed for the combi~iationreaction. Cal-
culations based c;n the results of Porter and Tompklns26 suggest that for the
adsorption of hydrogen on iron, the value ~ f lisj about 0.1. Analogies may also
be drawn with the adsorption of nitrogen where the excellent data of Scholten,
Zwictering, Konvalinka 2nd de Boer 34 show that F is 0.27 on a singly-promoted
iron catalyst. Values of the factor /3 for nitrogen may also be derived from the
kinetics cf gas phase heterogeneous decomposition of ammctnia on metals, where
the Ternkin 35 treatment shows that the rate of reaction is related to the ammonia
pressure E.)NH~and the hydrogen pressure p~~ by

Data from this source 36 indicate that p can be smaller or greater than 0.5,
e.g., according to conditions and purity, p values for iron range from 0.5 to 0.25,
and for platinum from 0.5 to 0.73. A correlation of these values with the /?values
for an electrode reaction has rcceiitly been observed in a study 37 of the kinetics
of electrodeposition of azide ions on platinum and iron. The reaction kinetics
can be described by a fast discharge reaction followed by a rate-determining
combination reaction,
2N3-hf2+3N2f 2M.
Depending on the pretreatment of the electrode surface, the slopes of the
Tafel line for platinum range from 0.056 to 0.043 corresponding to p values of
0.5 to 0.68. For iron, Tafei slopes varying between 0.070 and 0.055 have been
observed corresponding to /?values of 0.41 to 0.52.
It is therefore suggested that intermediate values of the dope of the Tafel line
in the electrolytic hydrogen evolution reaction, e.g., 0.073 on gold, 0.079 on molyb-
denum and 0.040 on palladium, are associated with reaction paths of the type
discussed above with p, or possibly y, factors other than 0-5. The determination
of p values for these metals from hydrogen adsorptkn studies would provide
valuable evidence regarding the reaction kinetics.

The author wishes to thank Prof. 17. C. Tompkins, F.R.S., and Dr. F. W.
Salt, for valuable discussions, and the University of Wales for the award of an
I.C.I. Research Fellowship.

1 Bockris, Modern Aspects of Electrochemisfr~,(Butterworths, 1954), p. 180.

2 Bockris and Azzarn, Trans.Faraday SOC., 1952, 48, 145.
3 Frumkin and Aladjalova, Acta physicochini., 1944, 19, 1.
4 Ershler and Frumkin, Trans.Faradwy SOC., 1939, 35, 464.
5 Breiter, Knorr and Volkl, 2. Elektrochem., 1955, 59, 681.
6 Schuldiner, J. Electroclze?ti.Soc., 1959, 106, 891.
7 Dolin, Ershler and Frumkin, Acta physicochini., 1940, 13, 779.
8 Hoare and Schuldiner, J . Electrochem. Soc., 1955, 102, 485.
9 Carson, Flanagan and Lewis, Trans.Fnraday Soc., 1960, 56, 371.
10 Bockris, Ammar and Huq, J. Physic. Chem., 1957, 61, 879.
11 Antoniou and Whetmore, Can. J . Chem., 1959, 37, 222.
12 Pentland, Bockris and Sheldon, J, Electrochem. Soc., 1957, 104, 182.
13 Hoare and Schuldiner, J. Cheni. Phjwks, 1956, 25, 786.
14 see Conway, Can. J. Chem., 1959, 37, 120.
15 De Boer, Adu. in Catalysis (Academic Press, 1956), 8: 17.
16 Kernball, Proc. Roy. SOC.A , 1947, 190, 117.
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J . G . N. T H O M A S 161 1
17 De Boer, Chen~isorption(Butterworths, 1956), p. 27.
18 Higuchi, Ree and Eyring, J . Amer. Chenz. Soc., 1957, 79, 1330.
19 Culver and Tompkins, Adv. iiz Catalysis (Academic Press, 1959), 11, 67.
20 Frumkin ar,d Slygin, Actaphysicochirn., 1925, 3, 781 ; 1936, 5, 819.
21 Hales, Physic. Rev., 1928, 32, 950. Schaaf, 2.physik. Chem. B, 1934, 26, 413.
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22 Suhrman and Schulz, Z. plzysik. Chem., 1954, 1, 69.

23 Parsons, Modern Aspects of Electroclzemist~y(Eutterworths, 19.59, p. 169.
24 Lukovtsev, Zhrrr. Fiz. Khiin., 1947, 21, 589.
25 Parsons, Trans. Faraday Soc., 1958, 54, 1053.
26 Porter and Tompkins, Proc. Roy. SOC.A , 1953, 217, 529, 543.
27 Gundry and Tompkins, Trans. Faraday Soc., 1956, 52, 1609; 1957,53, 218.
28 Maxted and Moon, J . Chem. Soc., 1936, 1542.
29 Matsuda and Nakata, J. Res. h s t . Catalysis Hokknido Univ., 1958, 6, 88.
30 Low, Chem. Rev., 1960, 60, 267.
31 Trapnell, Proc. Roy. SOC.A , 1953, 218, 566. Pritchard and Tompkins, Trans.
Faraday Soc., 1960, 56, 540.
32 Schuldiner and Hoare, J . Physic. Chem., 1957, 61, 705.
33 Eley and Rossington, Chemisorption (Butterworths, 1956), p. 137.
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37 Thomas, to be published.

NOTE ADDED IN PROoF.-Krishtalik (Zhur. Fiz. Khini., 1959, 33, 2729 ; 1960, 34, 117)
has also recently proposed that the Tafel slope of 2.3 RT/2F for electrolytic hydrogen
evolution on platinum corresponds to the mechanism described above.