Berichte der

58 W. Auer and H. J. Grabke: The Kinetics of Hydrogen Absorption etc. Bunsen-GesellschaR

The Kinetics of Hydrogen Absorption in Palladium (a- and P-phase)

and Palladium-Silver-Alloys
By W. Auer and H. J. Grabke

Institut fur Werkstoffwissenschaften IV, Erlangen, and Max-Planck-Institut fur Eisenforschung, Diisseldorf *)

Gase 1 Metalle / Reaktionskinetik 1 Thermodynamik 1 Heterogene Kinetik

The reaction H2 + 2 H (dissolved) on thin Pd and Pd - Ag foils (2.5 - 5 pm) was studied, with the aid of resistance measurements, in a
flow apparatus at temperatures in the range 20- 150°C. The rate determining step is the dissociation of the H2-molecule on the metal surface.
It is assumed that in the formation of the activated complex one atom (proton) already enters an interstitial site in the lattice. For very low
hydrogen concentrations xH in a-phase Pd and in Pd-Ag alloys, where Sieverts law applies, the following rate law is valid

The rate law shows that there is a segregation equilibrium between dissolved atoms and atoms in the interstitial reaction sites. For a-phase
Pd the enthalpy of this segregation is - 1.9 kcal/mol H, the activation energy of the forward reaction is 6.8 kcal and of the backward reaction
11.5 kcal, which yields the reaction enthalpy -4.7 kcal/mol H.
In a range of higher hydrogen concentrations the forward reaction rate is accelerated by a factor exp(yxH).This leads to the decreased
slope of the isotherm p i : vs. xH, that is known from thermodynamic studies. The acceleration is ascribed to the lattice expansion caused
by the dissolved atoms. After the d-band of the metal phase is tilled by electrons from hydrogen (and silver),the forward reaction rate decreases
with increasing xHand the backward reaction rate increases exponentially. This leads to the known steep rise of the isotherm p i : vs. xH
in the @phase region or in the Pd - Ag alloys after d-band filling.
Die Reaktion H2 + 2H (gelost) wurde an diinnen Pd- und Pd- Ag-Folien mit Hilfe von Widerstandsmessungen im Temperaturbereich
20 - 150°C untersucht. Der geschwindigkeitsbestimmende Schritt ist die Dissoziation des H,-Molekuls an der Metalloberflache. Es wird
angenommen, daR bei der Bildung des aktivierten Ubergangszustands ein Atom (Proton) bereits in einen Zwischengitterplatz im Gitter
eintritt. Im Bereich sehr kleiner Wasserstoffkonzentrationen xH in a-Pd und in Pd - Ag-Legierungen, in dem Sieverts Gesetz gilt, wird das
folgende Geschwindigkeitsgesetz gefunden
1 Kxi
u = k-------
1 + KXH - 'IflYxH.
Das Geschwindigkeitsgesetz zeigt, daR ein Anreicherungsgleichgewicht zwischen gelosten Atomen und Atomen in den interstitiellen Reak-
tionsplatzen besteht. Fur a-Pd ist die Enthalpie dieser Oberflachenanreicherung - 1,9 kcal/mol H. Die Aktivierungsenergie der Hinreaktion
ist 6,8 kcal, die der Riickreaktion 11,5 kcal, hieraus ergibt sich die Reaktionsenthalpie -4,7 kcal/mol H.
Im Bereich hoherer Wasserstofkonzentrationen ist die Geschwindigkeit der Hinreaktion gemal3 einem Faktor exp (yx,) beschleunigt. Dies
fuhrt zu der aus thermodynamischen Untersuchungen bekannten verringerten Steigung der Isotherme p#: vs. xHin diesem Bereich. Die
Beschleunigung wird zuruckgefuhrt auf die Ausdehnung des Gitters durch die bereits gelosten Atome. Nachdem das d-Band des Metalls
durch Elektronen des Wasserstoffs (oder Silbers) aufgefullt ist, nimmt die Geschwindigkeit der Hinreaktion mit steigender Losungskonzen-
tration x, ab, wahrend die Geschwindigkeit der Riickreaktion exponentiell mit xH zunimmt. Hierdurch ist der bekannte starke Anstieg der
Isotherme p,!f vs. xH im Bereich der P-Phase oder der Pd- Ag-Legierungen nach Auffillung des d-Bandes bedingt.

Numerous studies have been published on the thermo-
dynamics of the systems Pd-H and Pd-Ag-H [I - 71 and on
the hydrogen diffusion in Pd and Pd-Ag alloys (IS, 91. The
chemical kinetics of the reaction
H2 = 2 H (dissolved in Pd or Pd-Ag)
(1)
as yet only has been studied in an early investigation [lo]
which gave no definite results. A new investigation on the
kinetics of reaction (1) seemed to be very interesting for several
reasons.
At low temperatures the permeation of hydrogen through
Pd or Pd-Ag membranes can be determined by the surface
reaction [Il, 121. Also the attainment of equilibrium in the
system Pd-H is determined by the surface reaction at low
temperatures ( 120 "C); several investigators used hydrogen
transfer catalysts to obtain equilibration [2-4, 11, 121. In
*) Gorrespondence should be sent to the latter address.
recent studies in a UHV system equilibrium was quickly
obtained even at -78°C [ 7 ] . Exact information on the rate
of reaction (1) on pure surfaces should be of value.
In recent investigations on the dissociative dissolution of
diatomic gases in metals e.g. of N, in iron [13] and 0, in
silver [14] very interesting rate laws have been obtained,
which were explained by certain atomistic mechanisms. The
study of reaction (1) gives an important possibility for com-
parison and confirmation.
Hydrogen is dissolved in Pd in the form of protons and
electrons [I] and the chemical potentials of the protons and
electrons change with the hydrogen content [5, 61. The lattice
constant of the metal phase increases with the hydrogen
content. Thus the study of reaction (1) on Pd and Pd-Ag
alloys gives the possibility of studying a heterogeneous reac-
tion in dependence on the properties of the solid phase, which
are changed by the reaction product H (dissolved) itself in a
well known way.
Bd. 78, Nr. 1
1974 W. Auer and H. 3. Grabke: The Kinetics of Hydrogen Absorption etc.
Thermodynamics
First a short introduction will be given in the thermodynamics
of the system Pd - H [1 - 71.
The chemical potential of hydrogen dissolved in Pd at the con-
centration xH[mol H/mol Pdlcan be represented by
where p,?,is the standard potential, RTln(x,/l - xH)is the ideal
solution configurational term and dpH is an excess potential term
which results from deviations from ideal behaviour. The excess
potential term can be split into two terms resulting from the chemical
potentials of the protons and of the electrons [l]
A ~ = H APH* +Ape- (3)
since it is generally accepted that in the dissolution a dissociation
into protons and electrons occurs. The chemical potential of the
dissolved hydrogen is related to that of the gas H2 by
From the Equations (2), (3), and (4) the following expression is ob-
tained for the isotherm
.exp(dpH+ /R T )exp (Ape- /R T ).
This theoretical expression can be compared with empirical equa-
tions for the isotherms obtained by N e r n s t and Wicke [2] and
Poeschel and B r o d o w s k y [4].
rrrmfi
XH lmol H /mol Pd)
Fig. 1
Schematic drawing of two hydrogen absorption isotherms. In
region I Sieverts law is valid, in region I1 absorption becomes more
exothermic with hydrogen content and in region 111 the exothermicity
of absorption decreases according to d-band filling [7]
59
Equations (5) and (7) contain three expressions which are dependent
on xH.The first term is the ideal configurational term which yields
Si ev er t s law.
(7)
Sieverts law is valid at very low hydrogen concentrations in Pd
(region I in the schematic drawing of the isotherm, Fig. 1). The
second term exp(dpH+/RT)= exp(ExH/RT)is ascribed to the excess
chemical potential of the protons. By Lach er [15] and later by
Brodowsky [3-61 this term has been explained in terms of an
H - H attractive interaction. W ag n er [16] has shown that this
term results from carrying out the studies at constant pressure rather
than at constant volume. The dissolution of a solute atom becomes
easier when the lattice spacing of the host metal becomes greater
with increasing concentration. When the change of the chemical
potential is calculated for the introduction of hydrogen in Pd at
constant volume the system shows ideal behaviour and no attraction
between H-atoms. Thus the increased hydrogen solubility expressed
by the term exp(ExH/RT) is caused by the increasing size of the
interstices. This term becomes significant near the heterogeneous
region before the transformation of the a- to the P-phase. In this
region I1 the isotherm is approximately given by
p$: = K . X H . exp(ExH/RT). (8)
The third term exp (AfiL,-/RT)= exp {F(xH- 0.52)/RT} is ascribed
to a steep rise in the Fermi energy which occurs after the 4d-band
of the metal is filled by electrons from the dissolved hydrogen, and
additional electrons enter the 5s-band. For palladium the steep rise
in the Fermi energy and of the isotherm occurs in the 0-phase range
at about xH = 0.6. For Pd-Ag-alloys the beginning of the rise in
Fermi energy and of the'isotherm is shifted to lower values of xH,
since the valence electron concentration of the metal phase is
increased by Ag-addition. In the 0-phase range (region 111 in Fig. 1)
the isotherm can be represented by the complete Equation (6) or
by an empirical law
lnp,, = -A(T) + B(T).x,. (9)
Experimental
Foils of Pd (99.9%) and of Pd-Ag alloys with the compositions
Pd/Ag: 90/10, 80/20, 70/30, and 60/40 (supplied by Degussa) with
thicknesses of 2.5 p n and 5 p n have been used. The hydrogen ab-
sorption and -desorption was studied in a flow apparatus by meas-
urements of the electrical resistance of the foils. By establishing
constant pressures of helium and hydrogen through capillary flow
meters and then mixing the gas flows, defined hydrogen pressures
could be obtained for the hydrogenation. The dehydrogenation was
performed in pure helium. The gases, high purity H2 and He from
gas cylinders, were passed successively over pellets of active copper
to remove traces of oxygen and over magnesium perchlorate to
remove water vapor. After that, both gases were passed through
traps of silicagel, cooled with liquid nitrogen, in which all other
impurities, gases and vapors should be condensed. In two parallel
quartz tubes two foils were placed in the same furnace. The reference
sample was in a continuous flow of helium, while over the other
sample a helium or a hydrogen-helium mixture was alternatively
passed. Each of the samples was connected with four leads to a
Thomson bridge. In the d.c. circuit established, a microvolt recorder
registered the resistance changes of the sample, which were caused
by the absorption and desorption of hydrogen. Resistance changes
caused by temperature fluctuations were not measured since the
reference sample was also subject to them. Before an experiment
both samples were in a helium atmosphere. By addition of hydrogen
to the gas flow a defined hydrogen pressure was abruptly established
over the sample (Fig. 2). The absorption of hydrogen was measured
by recording the resistance change. After stoppage of the hydrogen
addition the hydrogen pressure over the sample decreased abruptly
and the desorption of hydrogen was observed. The surface reaction
was rate determining for absorption and desorption since in the
 Berichte der
60 W. Auer and H. J. Grabke: The Kinetics of Hydrogen Absorption etc. Bunsen-Geselischah

Fig. 2
Hydrogen absorption and desorption on a-Pd ( 6 0 ° C 20.8 Torr); change in resistance ( A R K xH)of a 2.5 pm foil; change in hydrogen pressure
(dashed line) and calculated change in resistance for the case of diffusion controlled reaction

very thin foils the diffusion equilibrium was established during the
experiments, as was calculated with the known diffusion coefficient
of hydrogen in Pd and in the PdAg alloys [8,9]. Rate control by gas
transport was avoided by using high gas velocities. 2000
The resistance change in the a-phase is proportional to the hydrogen
concentration (Fig. 3a). For the P-Phase and for high hydrogen k
concentrations in PdAg alloys a calibration had to be performed in v
order to obtain the relationship between the resistance change A R
and the hydrogen content xH. In these systems complicated rela- ->
1)
1500
tionships between resistance change and composition occur (Fig. 3 b). I
A
The calibration was possible by imposing different hydrogen pres- a
sures, measuring A R and relating A R to x,, with the aid of the
pH2- x,, relationsships measured by Wicke and Nernst [2] and by
Poeschel [4]. 1 loo0

500

0 0.1 0.2 03
Emm
X, h o l H / mol Me 1

b) Nonlinear relation between resistance change and hydrogen

concentration in Pd-Ag 80/20

In order to obtain reproducible measurements a common pre-

treatment was applied on all samples. In a flow of helium with
0.01% hydrogen the samples were kept at 500°C for two hours.
By this treatment cracks, deformations and dislocations were
removed and primary recrystallisation occured forming small
grains. After this pretreatment reproducible measuremc,its could
be obtained for several days and weeks. This would suggest that the
-
1 2 3 L 5 6 7 8 9 10 11 12 I3 U 15 16xIU’
XH ImolHlmolPdl purification of the gases has been very effective. In contrast to
previous studies [2, 11, 12) the reaction was sufficiently fast for
Fig. 3 measurement at room temperature also.
a) Lipear relation between resistance change and hydrogen concen- Mpst experiments were performed within the homogeneity range
tration in u-Pd. of the u-phase to avoid great lattice expansions. In the experiments
Bd. 78. Nr. 1
1974 W. Auer and H. J. Grabke: The Kinetics of Hydrogen Absorption etc. 61

on the P-phase the sample was hydrided into the homogeneity range
of the P-phase. After that it was kept in that homogeneity range by
always maintaining a minimum hydrogen pressure in the dehydro-
genation experiments also.
The relaxation curves for the hydrogenation and dehydrogenation
(Fig. 2) were approximated by a polynom
xH(t)= a, + a , t + a z t 2 + a 3 t 3 + a4t4 + a s t 5 . (10)
In the dehydrogenation experiments a fast flow of helium is
passed over the sample so that the hydrogen pressure is virtually
zero and only the backward reaction occurs. The backward reaction
rate is measured.
From the measured rates the forward reaction rate is obtained,
the evaluation is demonstrated in Fig. 4.
From the extrapolation of the net reaction rate or of the forward
reaction rate to xH = 0 the initial forward reaction rate 6, is obtained.

..;
The calculation of the constants was performed by the Gauss'
method of least squares with the aid of a computer. The values ai
may be positive or negative. The polynom was differentiated with
respect to time and in that way reaction rates in dependence on the
concentration were obtained.

Results I = 0bC
General Results

._;I'
From the evaluation of the resistance-relaxation curves (Fig. 2)
reaction rates are obtained as a function of the concentration of 6-
m
hydrogen in the solid xH [mol H/mol Pd], of the hydrogen pressure s
and of the temperature. The reaction rate will be given as u [mol
H/cm2 sec) and is calculated from :
1l. 5 -

where A is the surface area, V is the volume and 6 is the thickness of

1 L-
0 L I = 6O'C

the sample, V,, is the molar volume of the solid phase. 3

The rate of the hydrogenation is given by the difference of the
rates of the forward and backward reaction. The forward reaction
rate is a function of the hydrogen pressure and of the hydrogen
concentration, the backward reaction rate is only a function of the
hydrogen concentration
= C(pH,, XH) - 6(xH), (12)
In the hydrogenation the forward and the backward reaction occur
simultaneously and lead to the attainment of equilibrium. The net
rate u is measured. IE2151.51 P H ~ ITorrl

-V = V + I i 7 Fig. 5
Plot of the initial forward reaction rate vs. hydrogen pressures for
'\ measurements on a-Pd

C
0
.-
c
U

L
c

-e
0
0

3 150 200 300 400 500 600

m
P,? [Torrl
Fig. 4
Schematic plot of the net reaction rate u, and the forward and back- Fig. 6
ward reaction rates 17 and I7 vs. the hydrogen concentration (for a Double-logarithmic plot of the forward reaction rate vs. the hydrogen
rate law of the form u = kp,, - k'x;) pressure for measurements on P-PdH
 Berichte der
62 W. Auer and H. J. Grabke: The Kinetics of Hydrogen Absorption etc. Bunsen-Gesellschaft

This initial rate shows the dependence on the hydrogen pressure

uninfluenced by the dependence on the hydrogen concentration.
A common result was obtained from all measurements on Pd in
the a-phase and 0-phase ranges and also for the Pd-Ag alloys: The
forward reaction rate is always exactly proportional to pH2.
This is demonstrated in Fig. 5 for measurements in the a-phase
and in Fig. 6 for measurements in the j3-phase.

Kinetics at Low Hydrogen Concentration (Ideal Kinetics)

In the following the results are reported, that were obtained for
the range of hydrogen concentrations, where Sieverts law is ap-
proximately valid (region I, Fig. 1).

\ r.5dc '

\ \
Fig. 8
Plot of the forward reaction rate on a-Pd vs. the hydrogen concen-
tration. Dashed lines were calculated using Equation (21)

- /

\ -m 3 4
7

I =aonc
NE 3.2 -

3
.-
-
0
13
Fig. 7
Rate of the hydrogen desorption from a-Pd plotted vs. the hydrogen e
-2.8 -
concentration 4)

b -
2.6

Backward reaction rates obtained from dehydrogenation measure-

.
t k
7

2.L -
ments in a-Pd are shown in Fig. 7. At low hydrogen concentrations
the curves are parabolic and at somewhat higher concentrations the t 2,2-

2l
dependence on the hydrogen concentration Becomes linear. This
behaviour can be represented by the equation

1.8

By adapting the values of k' and K , the experimental curves in Fig. 7 0 0,005 0.01
could be approximated by curves calculated from Equation (1 3). m 1, [mol HlmolPdl
In the same range of reaction conditions the forward reaction rate
shows a retardation with increasing hydrogen concentration (Fig. 8). Fig. 9
The expression for the forward reaction rate can be derived from Plot of the reciprocal of the forward reaction rate vs. xH. This is a
Equation (13) with the condition that at equilibrium I3 = 6 and test on Equation (14)
Sieverts law (7) should be fulfilled. The expression is obtained

Up to about this value the expressions (13) and (14) can be used
Equation (14) can be tested by plotting the measurements according to describe the kinetics of reaction (1) and the following rate law is
to the reciprocal equation obtained
1 Kx i
U = kpH2------- - k'- (16)
l+KxH ~ + K x " '
This plot (Fig. 9) is given for an experiment at 80°C also shown in This rate law is valid in the range of hydrogen concentrations and
Figs. 7 and 8. It can be seen that the plot is only linear up to the temperatures, in which Sieverts law can be applied for the relation
hydrogen concentration 2.5. mol H/mol Pd. of hydrogen pressure to composition, as well for the palladium
 Bd. 78, Nr. 1
1974 W. Auer and H. J. Grabke: The Kinetics of Hydrogen Absorption etc. 63

a-phase as for Pd-Ag alloys. Thus this rate law is representing the This value is in excellent agreement with values obtained from
“ideal kinetics”. thermodynamic studies, -4620 + 150cal/mol H2 [7] and -4500
cal/mol H, [8].
Activation energies of the forward reaction have also been deter-
-
L
mined from permeation experiments [12, 17). On Pd activated with
finely divided Pd-black the value 7.7 kcal/mol has been obtained

$
,u
-225
[12], and on Pd-sheets activated by mechanical polishing a value
of 6.8 kcal/mol [17], in exact agreement with our value in Equa-
tion (17). The constant K can be considered as an equilibrium
I0, constant for the adsorption equilibrium
-23
c H (dissolved) H (adsorbed). (20)
-
C
\ The adsorbed hydrogen retards the forward reaction rate and plays
a role in the backward reaction (see discussion). From the evaluation

\Q,
of the dependences of the forward and backward reaction on the
-23.5 -
hydrogen concentration, values of K have been obtained and were
plotted in a diagram In K vs. 1/T (Fig. 12). The plot yields a value
of AH = -1.9 kcal/mol H for the enthalpy of the adsorption
, equilibrium (20) in a-Pd.

to Equation (21)

The rate constant of the backward reaction is obtained from the

1/
evaluation of the dehydrogenation measurements according to 5’6
Equation (13) and its temperature dependence is given by (Fig. 11) 5,5
k‘ = 6.5.exp(-11500cal mol-’/RT)[molPd/cm2sec]. (18)
5.4

AH = -E = -4700cal/mol H 2 . (19) Fig. 12

Temperature dependence of the equilibrium constant K. 0 from
backward reaction rate. + from forward reaction rate on a-Pd

- -lL -2c

%Y
a
5 -15
-
L

E %b -21
-t “E
-
C ,o
I
0
-1 6 5
c
c -2;

-1 7

-2

-1 8
2.9 3 33 32 3.3
L

EBm I I T x103 K-’ 2.3 2.L 2.5 2.6 2.7

rn I I / T lo3 K-I
Fig. 11 Fie. 13
1

Arrhenius diagram for the rate constant of the backward reaction Arrhenius diagram for the rate constant of the forward reaction on
on a-Pd Pd-Ag alloys
 Berchte der
64 W. Auer and H. J. Grabke: The Kinetics of Hydrogen Absorption etc. Bunsen-Gesellschaft

In Fig. 9 it has been shown that Equation (14) can be applied for
the forward reaction rate, but only up to a rather low hydrogen
concentration. At higher hydrogen concentrations the forward reac-
tion rate decreases less strongly than expected according to Equa-
tion (14). In contrast the backward reaction rate obeys expression
(1 3) also at higher hydrogen concentrations. Obviously a supple-
mentary factor must be introduced in Equation (14) for the descrip-
tion of the forward reaction rate at higher hydrogen concentrations
PdlAg 80120
whereas the Equation (13) is still valid at higher hydrogen concentra-
tions. With a side look at the equilibrium condition Equation (S),
which applies in this range of reaction conditions, we have intro-
duced a factor comprising an exponential dependence on the
hydrogen concentration

(21)

Combined with Equation (13) for the backward reaction rate this
expression yields the condition (8) for equilibrium (with g R T =
- 2 E ) . Equation (21) was tested by calculation of the curves in Fig. 8.
The values for k and K which were known from the measurements
at lower hydrogen concentration have been used and values of g
have been adapted to the experimental results. The value of g is
I =125'C P H ~= 4 , 0 5 Torr
related to the thermodynamic quantities used in Equations (5) and (6)
by

-gRT = 2
dXH
k 1 xH-o
=2E. r =roo' c P H =~1,95 lorr

The values for g from a lot of experiments at P d in the temperature

range 0 - 80 "C show a wide scatter. The average value corresponds
to E -25 _+ 10kcal/mol H, which is in agreement with the
evaluation of work of G i l l e s p i e et al. [18] by M o o n [19]. Wicke
and Nernst [7] obtained lower values in the range - 10 to - 12 kcal/
I
E ]
0
-1lo*

Fig. 15
mol H. The curves for the forward reaction rates measured on the
Pd-Ag 80/20, dependence of the forward reaction rate on xH.
Pd-Ag alloys could be described similarly. In Figs. 14, 15, and 16
Dashed lines were calculated using Equation (21)
the plots are given for the measured and calculated dependence of
the forward reaction rate on the hydrogen concentration.
In the curves obtained for Pd-Ag 9Ojl0 (Fig. 14) the effects of the
retarding factor l/(l +
K x , ) and of the accelerating factor exp(gx,)
can be seen distinctly. For the kinetics on the alloy Pd-Ag 80/20 (Fig.
15) the effects seem to compensate one another, while for the alloy
Pd-Ag 60/40 the acceleration by the exponential term is pre-
, 8 r = iso'c

Pd IAg 60/40

Q
!
I

_I
I = 125'C PH2 = 9,98Torr

--____ ~

r = im' c pH2 '1012 iorr

0 5x10"
- 1x104
XH [ mol H l m l Me1
0
ITl'isT;ml
1 -2 3 [ mol.4H lmol5Me
xH.io2 1
~

Fig. 14 Fig. 16
Pd-Ag 90/10, dependence of the forward reaction rate on xH. Pd-Ag 60/40, dependence of the forward reaction rate on x,.
Dashed lines were calculated using Equation_(21) Dashed lines were calculated using Equation (21)
Ed. 78. Nr. 1
1974 W. Auer and H. J. Grabke: The Kinetics of Hydrogen Absorption etc. 65

ponderating (Fig. 16). In the measurements on the alloy Pd-Ag
60/40 the initial rates as measured are somewhat too low since the
change in the gas atmosphere was not performed fast enough.
The value of - f g R T = E in the case of Pd-Ag 80/20 and Pd-Ag
60/40is about - 11 kcal/mol H. Thermodynamic studies [S] yielded
lower values of about - 5 kcal/mol H.
For the backward reaction rate Equation (13) could be applied in
all cases. From the evaluation of the backward and forward reaction
rates values are obtained for the constant K which are given in
Fig. 17. It can be seen that the values of K are decreasing considerably
with increasing Ag content. Accordingly, no retardation of the
forward reaction rate can be seen in the curves 6 vs. xH measured on
Pd-Ag 60/40, and the curves for the backward reaction rate are
approximately parabolic.
In the first experiments the dehydrogenation curves were not
reproducible, but after performing hydrogenations with pressures
up to 1 atm the subsequent experiments at lower pressures were
reproducible. Dehydrogenation experiments starting from different
initial concentrations then yielded identical dependences of the rate
on xH (Fig. 18). Apparently the exposure to a high HZ pressure has
resulted in extensive irreversible deformation of the sample by the
lattice expansion and after that the sample may be regarded to be
in a stationary state.
The rate of the hydrogen desorption increases strongly with the
hydrogen concentration in the P-phase. The curves cannot be
described by the formerly used parabolic or linear dependence on
xH but approximately by an exponential law
13 = k , exp (Dx,) . (22)

'i3- F

__-_
-__
- mimum
n-phe

1 -

I J
2.2 23 2l. 2.5 26 27 0
m 1/rx103 K-I
Fig. 17
Temperature dependence of the equilibrium constant K for Pd-Ag
80/20 and Pd-Ag 60/40 alloys

Kinetics in the Range of the Steep Rise of the Isotherm

(Effect of dBand Filling)
In the system Pd-H the steep rise of the isotherm p ~ vs., xH which
is caused by d-band filling [1 - 71 occurs in the homogeneity range
of the P-phase. Measurements on the P-phase have been performed
at 40°C where the dissociation pressure of P-PdH is 13.5 Torr [2].
In the hydrogenation experiments hydrogen pressures in the range
60-760 Torr HZ have been used. The dehydrogenations were
performed in a mixture of helium with 60 Torr H2. Thus trans-
formation into the a-phase was avoided.

7
0.7
I

m
0.65 0.66
-
467 068
X,,~~VIH/~OIW~

XH Lmol Hlmol Me1

Fig. 18
Logarithmic plot of the hydrogen desorption rate on P-PdH vs. the Fig. 20
hydrogen concentration Forward reaction rate on Pd-Ag- 6 0 / 4 vs. hydrogen concentration

66 W. Auer and H. J. Grabke: The Kinetics of Hydrogen Absorption etc.
Fig. 18 gives a plot of log ii vs. xH,beginning at the value for the
hydrogen desorption rate at 60Torr H2 (xH= 0.643).
The rate of the forward reaction again was obtained by addition
of the hydrogenation and dehydrogenation rates (considering the
rate at xH = 0.643). Fig. 19 shows forward reaction rates at different
hydrogen pressures. After a maximum at about x$ = 0.658 the rate
is decreasing with increasing hydrogen concentration. The for-
ward reaction rate was described by
The rate is proportional to pH2, the dependence on the hydrogen
concentration being mainly determined by the two exponential
terms. The increase of the rate with increasing xH caused by the
first exponential term is stopped in the 0-phase region when the
concentration xg is exceeded. The decrease can be described by
the newly introduced exponential term which was formulated in
analogy to the Fermi law, with the idea in mind that at xH > xg a
strong increase in the chemical potential of the electrons A p e - takes
place.
A similar steep rise of the isotherm pHI = f’(xH)occurs in the
Pd-Ag alloys, when the d-band is filled by electrons from hydrogen
und from silver.
This is the case in Pd-Ag 60/40 at about xH = 0.1 and accordingly
a maximum of the forward reaction rate is observed in that range
(Fig. 20).
Thus forward and backward reaction rates are essentially deter-
mined by exponential dependences on the hydrogen concentration,
Equation (22) and (23). In agreement with these kinetic results the
isotherm in the 0-phase range can be described by a linear relation
of lnp,, and xH,Equation (9), in which several terms and effects
are comprised. The steep rise of the isotherm is mainly caused by
the exponential increase of the hydrogen desorption rate with the
concentration,but also by the decrease of the forward reaction rate.
Discussion
The studies on the kinetics of reaction (1) on Pd and Pd-Ag
alloys rendered a consistent description of the kinetics which
can be related to the thermodynamics of the system and also
be explained by an atomistic mechanism. The relation to the
thermodynamics already has been demonstrated, now some
hypothesis on the mechanism is presented.
The kinetics could be described by rate Equation (16) for
the range of conditions where Sieverts law (7) is valid. This
rate law is analogous to the rate equation which has been
observed for the dissolution of nitrogen in iron N2 S 2 N
(dissolved) [13]. The forward reaction rate is proportional to
pH2and the backward reaction rate (at very low xH) is pro-
portional to x i . Therefore in any case the rate determining
elementary steps must be the dissociation of the molecule H2
for the forward reaction and the recombination of two
hydrogen atoms for the backward reaction. The transition
state must be a complex of two hydrogen atoms H . H *
(possibly ionized).
In the range of very low hydrogen concentrations the for-
ward reaction rate is retarded by the reaction product, the
dissolved hydrogen. The retardation which is expressed by
the factor 1/(1 + K x , ) must be explained by a segregation
equilibrium (20). Hydrogen atoms at the metal surface are
blocking the reaction sites for the forward reaction. The
fraction of free sites, which may be derived from the Langmuir
+
isotherm according to 1 - 0, = 1/(1 K x , ) shows up in
the expression for the forward reaction rate. The factor
1/(1 + K x , ) also shows that the rate determining elementary
Berichte der
Bunsen-Gesekchdft
step occurs at one site only, since the reaction site can be
blocked by one hydrogen atom.
Deviation from ideality occurs in the Pd - H system at rather
low hydrogen contents, the absorption becomes more exo-
thermic with increasing hydrogen content; the concentration
x, becomes higher than expected according to Sieverts law.
The effect has been ascribed to an increased solubility caused
by the lattice expansion [I71 or to an attractive H - H inter-
action in the lattice [3 - 61. In the kinetics the deviation from
ideality and from the rate law (16)shows up in an acceleration
of the forward reaction rate with increasing hydrogen content,
described by a factor exp(gxH)in Equation (21). This accelera-
tion of the forward reaction rate can be well connected with
the lattice expansion. It may be assumed that in the formation
of the activated complex (H...H)* one of the hydrogen atoms
already enters the lattice. The larger the interstices are, the
easier this step can occur. Therefore the acceleration of the
forward reaction with increasing xH can be related to the
lattice expansion caused by increasing x H .
An acceleration of the forward reaction rate also occurs,
when the lattice parameter is increased by addition of silver
(Fig. 13) and also when the lattice is strained elastically. The
latter effect had been observed by K u s s n e r , and was ascribed
to the formation of “rifts of molecular dimension” [113, we
suggest that the rate of hydrogen absorption was enhanced
by the lattice expansion.
The facts which can be derived from the previous discussion
are:
1. the dissociation of the molecule H2 is the rate determining
step for the hydrogen absorption;
2. this reaction step occurs at one reaction site which may
be blocked by one hydrogen atom;
3. at least one of the hydrogen atoms formed in the disso-
ciation enters the lattice.
Considering the fact that the reaction takes place at one
site, it is obvious that only one of the hydrogen atoms can enter
the lattice whereas at first the other one stays adsorbed.
Accordingly the rate determining elementary step can be
formulated
H2(ads) [H,(ads) ... H, (in the lattice)]* $ 2 H (dissolved).
(24)
The transition state* is a vertically adsorbed dissociating
molecule, of which one atom (or proton) already sticks in an
interstice directly beneath the metal surface.
The most plausible assumption is, that the hydrogen atoms
which may block the reaction are adsorbed in the interstices
directly below the surface. For the equilibrium (20) may be
written
H (dissolved) = H, (in an interstice immediately
(25)
beneath the surface).
This surface segregation can be easily understood since the
elastic energy of dilatation is less for interstitial sites at the
surface than in the bulk. The tendency for surface segregation
decreases with increasing lattice parameter of the metal phase.
Upon addition of Ag the lattice spacing of Pd-Ag alloys
increases, hence the surface segregation of hydrogen should
Bd. 78. Nr. 1
1974 G. Wedler und D. Borgmann: Untersuchung der Adsorptionszustande des Wasserstoffs usw. 61

be decreasing. In agreement with these considerations no
retardation of the forward reaction rate with increasing xH
was observed in the case of Pd-Ag 80/20 (Fig. 15) and even
an increase of the rate in the case of Pd-Ag 60/40 Fig. 16)
was observed. In these cases the effect of the retarding factor
+
1/(1 KxH) is outweighted by the effect of the factor exp (gxH).
Equilibrium constants have been determined for the segre-
gation equilibrium (20). These decrease with increasing Ag
content of the alloys (Fig. 17).
Thus at least three different states of the hydrogen atom
play a role in the mechanism of reaction (1). (The term atom
is used regardless of the ionization)
H (diss.) atoms, in interstices in the bulk of the metal phase;
H, atoms, adsorbed at metal atoms on the outer surface;
Hp atoms, adsorbed in interstices in the inner surface.
All states of the atomic hydrogen are in equilibrium during the
absorption or desorption of hydrogen. Only the above formu-
lated dissociation-recombination reaction is rate controlling.
The surface concentrations of the adsorbed states He and H,
are established by equilibria with the dissolved hydrogen.
For the equilibrium H (dissolved) H, low surface coverage
and a linear relation between xH and the degree of coverage
6, is assumed
e, =K~.X" 1 - e, 2 I.
For the equilibrium H (dissolved) = H, a Langmuir isotherm
is assumed
For the rate controlling step (24) the following rate law
applies
u = k.pH2(1- e,) - veeO,.
By introduction of the expressions (26)and (27)in Equation (28)
the experimental rate law (16) is obtained
It can be seen from the comparison-with Equation (16) that
the constant K which has been determined above is equivalent
to the adsorption constant Kp.
The same derivation and model can be applied on the
reaction N2 = 2 N (in iron) [13, 201. The mechanism of the
reaction O2 = 2 0 (in silver) is similar but in this case con-
siderable adsorption of O2 molecules occurs [I41 and there-
fore the formal kinetics are different.
The work was performed in the Max-Planck-Institut fur Metall-
forschung, Stuttgart, and is part of the Dissertation W. Auer,
Universitat Stuttgart 1973.
W. Auer would like to thank for a stipendium from the Max-
Buchner-Gesellschaft.
References
[I] C. Wagner, 2 . physik. Chem. A 193, 386, 407 (1944).
121 E. Wicke and G. Nernst, Ber. Bunsenges. physik. Chem. 68,
224 (1964).
[3] H. Brodowsky, 2. physik. Chem. N F . 44, 129 (1965).
[4] H. Brodowsky and E. Poeschel, Z. physik. Chem. NF. 44,
143 (1965).
[5JH. Brodowsky and E. Wicke, Solubility and Diffusion of
Hydrogen in Palladium and Palladium Alloys, in: Engelhard
Industries Technical Bulletin VII 1966, Newark.
[6] H. Brodowsky, Ber. Bunsenges. physik. Chem. 76, 740 (1972).
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(26) [8] H. K. Birnbaum and C. A. Wert, Ber. Bunsenges. physik. Chem.
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[lo] C . Wagner, Z. physik. Chem. A 159, 459 (1932).
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1131 H. J . Grabke, Ber. Bunsenges. physik. Chem. 72,533,541 (1968).
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(Eingegangen am 28. August 1973) E 2751

Untersuchung der Adsorptionszustande des Wasserstoffs

an polykristallinen Eisenfilmen mit Hilfe der thermischen Desorption
Von G . Wedler und D. Borgmann
Aus dem Institut fur Physikalische Chemie I1 der Universitat Erlangen-Nurnberg

Adsorption f Oberfachenerscheinungen / Desorption

Durch Messungen der thermischen Desorption kann gezeigt werden, daR der Wasserstoff an polykristallinen Eisenfilmen in drei verschie-
denen Zustanden vorliegt. Der Vergleich dieser Resultate mit den Ergebnissen anderer MeRmethoden wie Widerstandsmessungen, Austritts-
potentialmessungen und Messungen der Adsorptionswarme ergibt, daR es sich dabei urn einen Physisorptions- und zwei Chemisorptions-
zustande handelt. Hochstwahrscheinlich bildet sich der bei hoherer Belegung stabile Chemisorptionszustand aus dem bei niedrigerer Be-
legung stabilen durch eine Strukturumwandlung in der Adsorptionsphase.