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The Journal of Physical Chemistry, Vol. 82, No.

21, 1978 2323

Hydrogenation of Ethylene in Granular Copper

tronic polarization is neglected on the grounds that the


electronic polarizability of the complex is equal to the sum
of the electronic polarizabilities of the individual molec u l e ~ . ~As
J ~can be seen from the above data and figures,
wherever there is any interaction between the two nonpolar
molecules, the electronic polarizability exceeds the additive
values. Therefore the contribution of the electronic polarizability cannot be neglected if one wants to determine
the exact dipole moment of the complex.
Thus, the refractive index measurement method can be
used for detecting the formation of a complex and to
determine its equilibrium constant, even for a weak
complex.

2.04

2 03

-4
2.02

Acknowledgment. The authors are thankful to Dr. C.


M. Pathak, Department of Physics, for allowing us to use
his laboratory facilities and to Professor 0. P. Malhotra,
I

or

0.2

03

Co

04

Head, Chemistry Department, for providing the facilities


and to U.G.C. for financial support.

MI1

Flgure 1. Plot of na2 against the concentration of benzene: (1) 0.5


mol L-' total concentration; (2) 0.3 mol L-' total concentration.

References and Notes


R. Foster, "Organic Charge Transfer Complexes", Academic Press,
New York, N.Y., 1969.
P. H. Emsiie, R. Foster, C. A. Fyfe, and I. Hormann, Tetrahedron,
21, 2843 (1964).
A. K. Colter and E. Grunwaid, J . Phys. Chem., 74, 3637 (1970).
M. E. Baur, D. A. Horsma, C. M. Knobier, and P. Perez, J . Phys.
Chem., 73, 641 (1969).
(a) E. H. Lane, S. D. Christian, and J. D. Childs, J . Am. Chem. Soc.,
96, 38 (1974); (b) S. D. Christian, J. D. Chiids, and E. H. Lane, ibM.,
94, 6861 (1972).
H. C. Tse and M. Tamres, J . Phys. Chem., 81, 1367, 1376 (1977).
M. Tamres, "Molecular Complexes", Vol. I, R. Foster, Ed., Elek.
Science, London, 1973.
J. A. Riddlck and W. B. Bunger, "Techniques of Chemistry", Voi. 11,
"Organic Solvents", A. Weissberger, Ed., Wiiey-Interscience, New
York, N.Y., 1970.
R. Foster and N. Kulevsky, J . Chem. Sm.,
Faraday Trans., 69, 1427
(1973).
2 . Yoshida and E. Osawa, Bull. Chem. SOC. Jpn., 38, 140 (1965).
N. B. Jurinski and P. A. D. de Maine, J . Am. Chem. Soc., 86, 3217
( 1964).
M. Muanda, J. B. Nagy, and 0. B. Nagy, Tetrahedron Lett., 38,3421
(1974).
N. Kulevsky, "Molecubr Association", Vol. I, R. Foster, Ed., Academic
Press, New York, N.Y., 1975.

only a 1:l complex is formed in HMB-TCNE, is much


lower than the value of K , which includes other types of
complexe~.~
Here it must be noted that the literature data
are under different sets of conditions;'J2 the value of K ,
depends on the experimental conditions such as whether
A >> D, D >> A, or A = D, and also on the nature of the
solvent.
A change in electron cloud density in the neutral atom
or molecule will lead to a change in the polarizability.
Since the complex is generally more polar than the
components, the electronic polarizability or the refractive
index increases and the deviation depends upon the extent
of interaction between the donor and acceptor. Therefore
the stronger the complex, the larger the deviation in the
refractive index values.
The dipole moment of a complex depends on the total
polarizability of the complex. However in the calculation
of the dipole moment of the complexes, so far, the elec-

Hydrogenation of Ethylene in Granular Copper. Promoter Effect of Hydrogen


P. Gajardo," M. C. Lartiga, and S. C. Droguett
Depatiamento de 06mica, Facuffadde Ciencias &&as y MatemCiticas, Universidad de Chile, Casiiia 2777, Santiago, Chile
(Received October 26, 1977; Revised Manuscript Rqceived May 31, 1978)

The promoter effect of hydrogen, in granular copper, on the hydrogenation of ethylene has been studied at
0 and 252 "C. The promoter effect observed at 252 "C is due to the presence of hydrogen occluded in the metal
bulk, probably located near the reaction surface. At 0 "C, an increase in the catalytic activity of the copper
is also observed after hydrogen pretreatment of Cu at 150 "C. The nature of this phenomenon is discussed
in both cases. The effect of ethylene on copper is studied at both temperatures and self-hydrogenation of this
gas is observed. The role of hydrogen adsorbed on the metal is discussed in relation to the reaction mechanism.
The activation energy was determined at temperatures ranging from -21 to 0 "C for samples freshly pretreated

with hydrogen and for samples without treatment.


Introduction
The promoter effect of dissolved gases on the activity
of metallic catalysts has been studied since 1935.1 Several
*Address comeswndence
to
authorat theuniveniG
Catholique
de Louvain, Groupe de Physic0 Chimie Minikaleet de Catalyse, Plaee
Croix du Sud, 1, B-1348Louvain-la-Neuve, Belgium.

0022-3654/78/2082-2323$01
.OO/O

investigations designed to clarify the nature of the active


sites and the catalytic role of the dissolved gases within
the metal have been carried
Some interesting
phenomena have been observed such as the existence of
a narrow maximum in the curve of activity vs. concentration of gas in the metal.6 Attempts have been made to
specify the step in the total process where the promoter
0 1978 American Chemical Society

2324

The Journal of Physical Chemistry, Vol. 82, No. 21, 1978

gas exerts its a ~ t i 0 n . l l - l ~


Interest in this problem persists because of its relation
to the basic theory of catalysis16and its possible effect on
data reproductibility and measured rate constants.
Furthermore, it is important to know the influence of
hydrogen occluded in metallic membrane catalysts1' upon
their activities. Hydrogen has received the most attention
as a promoter gas probably because this phenomenon has
been observed on repeated occasions in hydrogenation
reactions and because of the ease with which hydrogen is
sorbed by many metals.
The hydrogenation of ethylene at low temperatures and
the promoter effect produced by sorption of hydrogen in
metals of group 1B contradicts the d-character theory.ls
According to this theory, these metals (Cu, Ag, and Au)
should neither adsorb hydrogen nor hydrogenate ethylene
since they do not have d-band vacancies indispensable in
hydrogenation reactions. Experimental evidence has been
r e p ~ r t e d for
'~~
hydrogenation
~~
of ethylene on copper even
at 0 "C. In addition, Mc Cabe and Halseyll observed that
hydrogen adsorbed at 120 "C produces an enhancing effect
on the hydrogenation of ethylene at 0 "C. Hall and
HasselP have shown that this phenomenon also occurs
when the reaction is carried out at temperatures of 27-50
"C, but Hall et al.I5 did not detect it between 75 and 125
"C. It was postulated that at higher temperatures the
hydrogen responsible for the promoter effect is desorbed
from the reaction surface. However, we have shown21that
the effect occurs in copper membranes when ethylene is
hydrogenated between 180 and 256 "C.
It is necessary to know the location of the promoter
hydrogen within the metal in order to determine the
mechanism of this phenomenon. Some result^^-^ indicate
that in the case of nickel the hydrogen is located in the
bulk of the metal. We also determinedz1that in copper
membranes, at high temperatures, the hydrogen is located
in the bulk of the metal near the reaction surface. Other
authors have pointed out that for nickello and coppernickel alloys13this promoter hydrogen would be adsorbed
on the metal surface.
The goal of this work is to study the promoter phenomenon in granular copper a t 0 and 252 "C. We also
intend to clarify the existing contradictions about the
location of the promoter hydrogen in the metal. Finally,
some experimental results have allowed us to shed some
light a t the role played by sorbed hydrogen in the hydrogenation of ethylene on copper.

Experimental Section
The experiments were carried out under static conditions. Product analysis was done by chromatography. The
reactor volume was 26 cm3, Liquid nitrogen and turnings
of gold were used as traps to avoid poisoning the catalyst
by mercury vapors. In the high temperature region, the
temperature was controlled by means of a thermostated
oven with a variation of f0.25 "C. For experiments below
0 "C, baths of alkaline salts solutions were used. The
maximum temperature variation in this range was f0.15
"C during the time of the experiment.
The molar composition of the reacting mixture was
always constant at C2H4:H2= 1:l.
Gases. The hydrogen was produced electrolitically and
later purified. The purification train included copper
turnings at 400 "C, silica gel, phosphorus pentoxide and
liquid nitrogen traps, and a commercial purifier DEOXO.
The ethylene employed (Matheson Gas Product, Research grade) contained 10 ppm of N2, 5 ppm of 0 2 , and
5 ppm of CH4.
Catalyst. The granular copper was prepared as de-

P. Gajardo, M. C. Lartiga, and S. C. Droguett

scribed by Best and Russellz2 starting from nitrate trihydrated (Analar) and ammonium carbonate (Analar).
The copper oxide obtained was reduced for 17 h at 400 "C
with a hydrogen flow rate of 30 cm3/min at atmospheric
pressure. Afterward, the 28-35 mesh fraction was separated and used for the experiments. The area of the
catalyst, determined23by argon adsorption (15.2 A2), was
5 m2/g.
Because the copper surface oxidizes rapidly in contact
with air at room temperature, each sample was reduced
again in situ when placed in the reactor (24 h under the
same conditions). The amount of catalyst employed in the
high temperature experiments was 0.2 g while at low
temperatures (below 0 "C) it was 10.8 g.
Method. Before starting each series of experiments, the
catalyst was evacuated for 10 min and then the reactant
mixture was introduced at a selected pressure. After the
desired reaction time, the products were extracted and
analyzed. Between experiments the reactor was evacuated
for 5-10 min.

Results
Separate experiments, designed to detect the enhancing
effect of hydrogen and the effect of ethylene on the catalyst, were performed at 0 and 252 "C. In some experiments a mixture of CzH4 + H2 (PH2= PC2H4= 90 Torr) was
diluted with helium to 1atm. The reaction rate was found
to be independent of the concentration of He at both
temperatures indicating that the reaction rate is not
controlled by diffusion of the reactants.
Promoter E f f e c t of Hydrogen and Effect of Ethylene
at 0 "C. To verify the existence of the promoter effect at
0 "C, a treatment with hydrogen was performed. The
catalyst was heated for 30 min at 150 "C at a hydrogen
pressure of 200 Torr. After cooling to 0 "C, the reactor
was evacuated for 5 min. The reaction was carried out by
introducing the reaction mixture into the reactor at 104
Torr. After 2 min, the gas was removed and analyzed.
The activity, A , is defined as the number of moles of
ethylene converted per gram of catalyst per minute. It
thus corresponds practically to the initial reaction velocity.
Due to the slow rate, after 2 min there is still a linear
relationship between the amount of ethane produced and
the time of reaction.
The temperature of this treatment (150 "C) was selected
by taking into account the results obtained by Mc Cabe
and Ha1sey.l' These authors reported that the promoter
hydrogen is adsorbed above 120 "C. A higher temperature
was not employed in order to avoid the penetration of the
hydrogen into the copper bulk which starts to be observed
around 190 0C.24
It should be noted that since the Cu was heated at 400
"C for 24 h during its previous reduction, hydrogen is
occluded in the Cu bulk. Since this hydrogen can escape
from the bulk only at a high degasification temperature,21*
its concentration in the Cu bulk must remain constant in
the experiments carried out at 150 "C. Therefore, if a
change in the catalytic activity is observed after hydrogen
treatment at 150 "C, it must be connected to the action
of hydrogen occurring only on the Cu surface.
In general, the results were reproducible within experimental error. Nevertheless, as observed by Mc Cabe
and Halsey,'l in the first experiment carried out with a
freshly prepared sample, the catalyst has a high activity
that decreases abruptly in the next experiments and
cannot be restored to the original value with hydrogen.
After several experiments, the catalyst activity reaches a
steady state.
In Figure la, only before experiment 1was the catalyst

The Journal of Physical Chemistry, Vol. 82, No. 21, 1978 2325

Hydrogenation of Ethylene in Granular Copper


,

TABLE I: Effect of Ethylene on the Catalytic Activity


of Copper at 0 Oca

P c ~ H ~ Pmix,
!
A , molk
Torr
Torr
treact
x 106
105
2 min
1.29
44
l h
1.49
105
2 min
0.97
44
l h
1.26
105
2 min
0.85
6
44
l h
1.14
7
150
over night
1.30
Pc2H, is the pressure of ethylene; Pmix the pressure
of the ethylene-hydrogen mixture (C,H,:H, = l:l),
treact, the reaction time, and A , the number of moles
of ethane produced per gram of catalyst.
no.
1
2
3
4
5

't
O

10

Number of experiment

Figure 1. Dependence of the catalytic activity on the number of


experiments at 0 "C (PH1= Pep, = 52 Torr).

given the preliminary treatment with hydrogen at 150 "C.


Experiments 2-7 were carried out successively, the reactor
being evacuated for 5 min at the reaction temperature (0
"C) prior to each experiment. The activity decreases
strongly during the first two experiments, reaching a steady
state after a few experiments. These results show that the
catalyst treated with hydrogen possesses effectively a
higher activity probably due to the existence of hydrogen
chemically adsorbed on the reaction surface.
In order to elucidate the role of ethylene in this phenomenon, later experiments were carried out with the same
sample (Figure lb). The same method as employed for
curve a was used, except that in this case the catalyst was
treated with ethylene a t 0 "C and a pressure of 44 Torr
for 1h, after the previous treatment with hydrogen (before
experiment 1,curve b). The results show that the ethylene
produces a strong decrease in the catalytic activity (experiment 1). The activity is increased in experiment 2
reaching a steady value slightly lower than that in curve
a (experiments 3-6).
The reactor was then filled with ethylene (150 Torr) and
held at 0 "C overnight. Experiments 7 and 8 (curve c) were
performed successively without previous treatment with
hydrogen. A new decrease in the catalytic activity is
observed in experiment 7 (compared to that of experiment
1,curve b) followed by an increase in experiment 8. The
catalyst was then treated with hydrogen at 150 "C and as
usual an increase in the catalytic activity was observed
(experiment 9). The activity level obtained was the same
as that in experiment 3, curve a. The reactor was then
evacuated for 71 h at 150 "C and experiment 10 was
performed under conditions similar to those of the previous
experiments. As shown in Figure IC,the activity in this
case reaches a value similar to that in experiment 8,
creating a new lower stationary state curve c.
Table I shows the results of a series of experiments
designed to study in more detail the action of ethylene over
copper. Initially, the catalyst was exposed to the Hz
CzH4 mixture (104 Torr) for 2 days at 0 "C to allow the
surface of the catalyst to reach the most stable working
condition. Each experiment in Table I was performed after
evacuation for 5 rnin at 0 "C with the exception of the first
where the catalyst was held for 39 h under vacuum at room
temperature. Experiments 1-6 were alternately carried
out with a mixture of hydrogen + ethylene and ethylene
alone. The amount of ethane (the only detected product)
formed per gram of catalyst, Al, is shown in the fifth
column. In order to see if the activity is constant when
the copper is treated with ethylene for longer times, ex-

periment 7 was conducted after exposing the catalyst to


ethylene overnight at 0 "C and 150 Torr. The results of
this experimental series show the existence of so-called
(C2H2)ads+ CzHs), also
self-hydrogenation (2C2H4
observed with other metals,25~26,~30
except that in this case
this phenomenon produces an irreversible poisoning of only
a small part of the copper surface. The subsequent addition of Hz a t 0 "C to this catalyst (after experiment 7)
resulted in the formation of a considerable amount of
ethane. This type of experiment was repeated on the other
granular copper samples and the same phenomenon was
observed.
It is important to point out that the amount of ethane
produced by self-hydrogenation is independent of both the
exposure time and the pressure of ethylene (experiments
2 and 7 in Table I) which may indicate that the surface
where the reaction takes place is approximately the same
in both cases.
Activation Energy. The activation energy of the reaction was determined between 0 and -21 "C. The results
of these experiments are shown in Figure 2. The apparent
activation energies found for samples freshly treated with
hydrogen (curve 1) and for samples without treatment
(curve 2) were 7 and 11 kcal/mol, respectively.
Hydrogen Promoter Effect and the Action of Ethylene
ut 252 "C. As already mentioned, when the catalyst is
placed under a hydrogen atmosphere at 252 "C the hydrogen can penetrate into the bulk of the ~ o p p e rbut
~~i~~
any hydrogen chemisorbed at the surface desorbs quickly
when the reactor is evacuated. It is then possible to obtain
working conditions such that the copper surface has no
chemisorbed hydrogen but hydrogen is dissolved in the
bulk of the metal. If any enhancing effect is observed
under these conditions, it must be due to the action of the
hydrogen in the copper bulk.
The first experiments at this temperature were performed to determine if it is possible to obtain reproductibility with a fresh catalyst previously treated with hydrogen. The pressure of the ethylene-hydrogen mixture
was 180 Torr and the reaction time was 2 min. The results
are shown in Table 11. Listed in the second column are
the times employed for the treatment with hydrogen
carried out before some of the experiments. During this
treatment, the catalyst was placed under hydrogen at 282
Torr and 252 "C. Before each experiment and after the
hydrogen treatments, the reactor was evacuated for 10 min
at the same temperature. The decrease in the activity can
be better viewed by the use of the relation ( A ' - A'?/A'
X 100,i.e., the percentage decrease in the activity, as shown
in the fourth column; A' being the activity of one experiment and A" that of the next experiment.
In contrast to the experiments carried out a t 0 "C, a
continuous decrease in the catalytic activity was observed

2326

P. Gajardo, M. C. Lartiga, and S. C. Droguett

The Journal of Physical Chemistry, Vol. 82, No. 21, 1978

TABLE 11: Influence of Hydrogen Treatment on the Activity of a Freshly Prepared Samplea
no.

t, min

104A
mol/g min

(A' - A")/A'
x 100

t, min

no.

104A
mol/g min

(A' - A " ) / A '


x 100

15
0
3.37
2.5
16
1020
3.45
- 2.5
17
0
3.41
1.2
18
0
3.19
6.3
0
3.19
0
19
20
90
2.89
9.5
21
0
2.76
4.5
22
0
2.68
3.1
23
1072
2.76
3.2
24
0
2.72
1.6
11
25
0
2.68
1.6
12
26
90
2.42
9.6
13
27
0
2.33
3.6
14
28
0
1.80
1.8
The reaction temperature was 252 C. t is the time of previous hydrogen treatment at 282 Torr and 252 C; A , the
catalytic activity, ((A' - A " ) / A ' )X 100, the percentage decrease of the catalytic activity (see text); and Pc,H, = PH, =
90 Torr.
1
2
3
4
5
6
7
8
9
10

273
0
0
0
90
0
0
0
0
0
0
90
0
0

6.99
5.87
5.35
5.01
5.70
4.49
4.68
4.58
4.58
4.32
4.14
3.63
3.54
3.45

16.0
7.1
6.4
-13.8
21.2
-4.3
0.2
0.0
5.7
4.0
12.5
2.4
2.5

TABLE 111: Effect of Hydrogen Treatment on the Catalytic Activity of the Sample Used in Obtaining Table I1 after Its
Torra
Degasification at 413 "C and
104~
(A' - A")/A'
t, min
mol/g min
x 100
29
0
0.43
39
0
0.34
8.7
30
0
0.39
8.7
40
0
0.33
2.9
31
0
0.37
5.7
41
60
0.39
-13.1
32
5
0.37
0
42
0
0.37
5.7
33
0
0.35
4.4
43
1200
0.44
- 20.7
34
0
0.34
1.7
44
0
0.40
9.9
35
10
0.40
- 12.7
45
0
0.41
- 2.8
0.84
- 105.4
36
0
2.5
46b
900
0.39
9.0
37
0
0.37
47
0
0.77
1.8
38
15
0.38
0.73
4.8
- 1.6
48
0
a The reaction temperature was 252 "C. t is the hydrogen treatment time at 282 Torr and 252 "C;A, the catalytic
activity, ((A' - A " ) / A ' )x 100, the percentage decrease of the catalytic activity (see text);PHz = Pc,H, = 90 Torr.
The temperature of hydrogen treatment was 413 "C.
no.

t, min

104A
mol/g min

(A' - A")/A'
x 100

at 252 "C. This was probably due to the poisoning effect


of the CzH4which could be decreased only slightly by
hydrogen treatments.
It is knowna that sorbed hydrogen is removed with great
difficulty from the bulk of the copper. At 250 'C, only
46% of the total is eliminated by evacuation. It is likely,
therefore, that during the experiments in Table I1 the
copper still retained some occluded hydrogen in its bulk
from the initial reduction. For this reason, a previous
elimination of occluded hydrogen is necessary to detect the
promoter effect at 250 "C. This operation was carried out
after experiment 28 (Table 11) by evacuating the reactor
for 14 h at 413 "C.
Table I11 shows the results obtained at 252 "C under
conditions similar to those of Table 11. The hydrogen
treatments were performed at 252 "C except for experiment 46 in which the catalyst was treated at 413 "C. A
continuous decrease in the catalyst activity was observed
but under these conditions it was enhanced by the hydrogen treatment. It appears, however, that in these
experiments the activity depends on the time and temperature of the treatment with hydrogen.
Using the same sample as before, experiments similar
to those of Table I at 0 "C were carried out at 252 "C to
study the effect of ethylene on the activity of the catalyst.
This time the catalyst was treated for only 2 rnin with
ethylene. Self-hydrogenation of ethylene was observed
(Table IV, experiments 4 and 5), together with a decrease
in the activity for the next reactions. The ethane produced
in this case could not have come from the interaction of
ethylene with hydrogen left on the surface from the

no.

TABLE IV: Effect of Ethylene on the Catalytic


Activity of Copper at 252 "Ca
no.

PClH4>

Pmix*

Torr

Torr
170
170
170

1
2
3

4
5
6
7

186
186
170
170

1 0 5 ,~
mol/g
4.15
4.15
4.19
3.55
1.74
3.62
3.65

a Pc,H,is the pressure of the ethylene; Pmix is the pressure of the ethylene-hydrogen mixture (C,H,:H, = 1:l).
The reaction time was 2 min. A , is the number of moles
of ethane produced per gram of catalyst.

previous experiment because the surface hydrogen desorbes on evacuating the reactor at 252 "C for 10 min.
Ethane formation was also observed when hydrogen was
added to the reactor after ethylene had been introduced
and the reactor had then been evacuated for 15 min at the
same temperature (252 "C).
Discussion
Results of Experiments at 0 "C. These results (Figure
1) show that the hydrogen pretreatment enhances the
catalytic activity (experiment 1, curve a) as has been
observed by other authors.ll The decrease of the catalytic
activity with the experiment number could be explained
assuming that the "promoter" hydrogen is desorbed into
the gaseous phase or it reacts with ethylene. However this

Hydrogenation of Ethylene in Granular Copper

effect can be associated not only with the physicochemical


changes of the catalyst produced by the sorption of hydrogen in the metal (Le., the promoter effect of the hydrogen), but it may be also be linked to other phenomena.
For example, the subsequent decrease of the catalytic
activity with the experiment number suggests that the
promoter effect of hydrogen involves removal of a carbonaceous residue from the surface by hydrogen as is
observed with other metals.25
Moreover, this promoter effect may result from the
reaction of ethylene with the hydrogen that is chemisorbed
at 150 "C. Indeed, supposing that each cm2of Cu contains
1.4 X 1015active sites on the
in 10.8 g of catalyst
the number of hydrogen atoms chemisorbed in order to
form a monolayer is about 7.6 X lozo. If this hydrogen
reacts with ethylene, 6.3 X
mol of ethane should be
formed which is an amount greater than those shown in
the Figure 1.
The nature of hydrogen adsorption on copper and its
reaction with ethylene at room and lower temperatures has
not been satisfactorily explained.
As pointed out by Beek,26it is not enough for a catalyst
to have optimal geometrical conditions in order to adsorb
hydrogen or hydrogenate ethylene, but a suitable electronic
configuration is also required. Thus, this author has
reported that pure copper films, for instance, neither
adsorb hydrogen a t -183 "C nor hydrogenate ethylene at
room temperature even though the crystal parameters are
near to those of nickel. Nevertheless, in a study carried
out with spectroscopically pure copper films,27it has been
shown that hydrogen and ethylene are adsorbed reversibly
at low temperatures and hydrogen reacts with ethylene at
0 "C.
Attempts to explain the activity of the copper are based
on the assumption that some oxygen or nickel impurities
are present on the surface, thus allowing the adsorption
of hydrogen; but it has been s h o ~ nthat
~ ~ the
* ~con~
tamination of a copper surface with oxygen does not alter
its ability to adsorb hydrogen. The absence of the irreversible adsorption of ethylene on the catalyst under study
(which is a characteristic of nickel metal) shows that the
surface of the copper catalyst does not contain any trace
of nickel. In fact, the behavior of our catalyst toward
ethylene (Table I) differs from that known for nickeLZ5
A possible explanation of the mechanism for the adsorption of hydrogen and hydrogenation comes from our
results. The existence of self-hydrogenation (Table I) and
the irreversible poisoning of only a small part of the surface
by ethylene gives us the basis to assume that the mechanism of the hydrogenation occurs via formation of the
radicals C2H3 and/or CzH2 adsorbed on the metallic
surface:
CZH4

(CZH3)ads

+ (H)ads

The hydrogen adsorbed on the catalyst would increase


the rate of adsorption of new hydrogen molecules, the step
that is assumed to be rate-limiting in the hydrogenation
of ethylene on copper.26 The enhancing effect of pretreatment with hydrogen at 150 "C in the reaction carried
out at 0 "C is probably due to the increase in the number
of atoms adsorbed on the surface and thus the reaction
rate.
The preexponential factor of the rate constant decreases
by a factor of -700 as a result of hydrogen pretreatment
of the catalyst, but this is more than compensated for by

The Journal of Physical Chemistty, Vol. 82, No. 21, 1978 2327
I

\ i
3.7

3.8

3.9

I ~ T lo3

Figure 2. Temperature dependence of the reaction rate: A , InRial rate


of reaction; pressure of reaction mixture, 104 Torr. Conditions of the
hydrogen pretreatment were as follows: hydrogen pressure; 200 Torr;
temperature; 150 "C; time; 1 h: (0)with H2 pretreatment: (0)
without
H2 pretreatment.

a decrease in the activation energy (Figure 2). Consequently, the promoter effect of hydrogen is not due to the
formation of new active sites, but to a decrease in the
energy barrier of the reaction pathway.
Sato and M i ~ a h a r ahave
~ ~ reported that the hydrogenation of ethylene on copper films occurs via associative
adsorption of ethylene according to the Horiuti-Polanyi
mechanism. The self-hydrogenation of ethylene (e.g., via
dissociative adsorption) was considered to be a side reaction in the hydrogenation of ethylene on Ni, Pt, and Rh.
In the case of copper films, self-hydrogenation was not
considered at all. From the results in Table I we can
assume that the self-hydrogenation of ethylene on granular
copper can neither be ignored nor considered as a side
reaction in hydrogenation at 0 "C. In fact, it takes place
on the "carbide" surface of the catalystm i.e., a catalyst that
has been in contact with a CzH4 H2mixture and/or C2H4
alone for a long time at the same temperature. Moreover,
the formation of a considerable amount of ethane upon
the introduction of Hzinto the evacuated reactor where
the self-hydrogenation took place indicates that the adsorbed species on copper do not behave like a poison, but
rather like active species in relation to hydrogen. Along
this line, it is interesting to note that Franken and Ponec31
pointed out a reversible character of the adsorption of
ethylene on copper film at room temperature.
The hydrogen sorbed by the metal has been reported
to influence the rates of adsorption of hydrogen and
ethylene and of other reactions on other metals. Thus,
Ablesova et alS5pointed out that hydrogen and also oxygen
sorbed in nickel cause an increase in the rate of adsorption
of hydrogen and ethylene. Wood32 observed that the
presence of small amounts of hydrogen atoms on the
surface of Pd-Ag alloys is necessary for the dehydrogenation of cyclohexane. The hydrogen sorbed by the metal
seems to be essential in the dehydrogenation of some
hydrocarbons at high t e m ~ e r a t u r e . ~ ~
Results of Experiments at 252 "C. The hydrogen
promoter effect cannot be explained by the removal of the
carbonaceous residue from the surface of the catalyst.
Indeed the results shown in Table I1 demonstrate that
hydrogen pretreatment cannot counteract the continuous
drop in catalytic activity.
In contrast, the catalytic activity of copper which has
a smaller amount of hydrogen in the bulk, is increased by
the hydrogen occluded in the bulk of the metal. The
location of the hydrogen in the metal is concluded from
the following facts, deduced from Table 111.

2328

The Journal of Physical Chemistry, Vol. 82, No. 21, 1978

(i) The experiments were carried out a t 252 "C, a


temperature where the hydrogen is rapidly desorbed from
the surface when the reactor is evacuated, leaving a small
probability that significant amounts of hydrogen atoms
remained adsorbed on the surface at the start of each
experiment.
(ii) The activity increases with increasing contact time
during the hydrogen pretreatment indicating that this
process is slow. Hydrogen diffusion in copper has already
been reported to be a slow process.34 The fact that even
after 10 min of contact of the hydrogen with copper (Table
111, experiment 35) there is a considerable increase in the
reaction rate indicates that the hydrogen responsible for
this effect is near the catalyst surface.
(iii) This effect is higher the higher the hydrogen
treatment temperature (Table 111, experiment 46) which
shows that the process, like the diffusion of H2 in copper,
is also activated.
The conclusions concerning the location of hydrogen in
the metal are in agreement with those obtained with
copper membranes at the same temperature.21 The
elimination of occluded hydrogen from the bulk by
evacuation of the catalyst at 413 " C explains the abrupt
decay of the catalytic activity between experiment 28,
Table I1 and experiment 29, Table 111. As the catalyst was
treated at 400 "C for a long time before activity measurements, we feel that the sintering of copper is not
responsible for this phenomenon.
The existence of the self-hydrogenation of ethylene on
copper a t 252 "C and subsequent ethane formation by
addition of hydrogen into the evacuated reactor suggests
that dissociative adsorption of ethylene takes place during
the hydrogenation reaction, as was indicated at 0 "C.
Along this line, it is interesting to note that Alexander et
al.27 pointed out that the adsorption of hydrogen and
ethylene in the catalytic reaction on copper has the same
characteristics at low and high temperature. However, in
contrast to the study carried out at 0 "C, it is not possible
to preclude the hypothesis which considers the dissociative
adsorption of ethylene as a side reaction in the hydrogenation process. Indeed, the experimental results shown
in Tables 11-IV were obtained on a copper surface which
had not reached its steady ("carbide") state. Its catalytic
activity continuously dropped, probably due to the poisoning effect of the ethylene.

P. Gajardo,

M.C. Lartiga, and S. C.

Droguett

Finally, considering that the location of the promoter


hydrogen is different for low temperature and high
temperature hydrogenation, the mechanisms which bring
about the enhancement of catalytic activity must also be
different in these two cases.

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