TO THE EDITOR
COMMUNICATIONS
Langmuir-Hinshelwood Mechanism as
Revealed by Thermal Desorption Study.
The Catalytic Decomposition of Methyl
Formate on Copper Surface
Xir: Recently the thermal desorption method (tdm)
has been applied to the study of adsorbed species and it
has been found that various adsorbed states show dif-
ferent reactivities. However, these species observed by
tdm are not necessarily identical with those of real
intermediates during reactions catalyzed by solid sur-
faces.
I n the present work we have applied this method to
the study of the decomposition of methyl formate over
copper surface.2 We have succeeded in revealing the
details of this reaction which obeys the Langmuir-
Hinshelwood mechanism by comparing the kinetic
parameters determined by tdm with those obtained
from conventional kinetics.
The study of decomposition kinetics was carried out
in a pressure range 5-25 mm a t temperatures between
100 and 170". The copper catalyst was prepared from
cupric hydroxide by reducing with hydrogen a t 180"
and was evacuated at 300". The products were found
to be CO, H,, and traces of COz. The initial rate TO is
expressed as
ro = kKP/(l + KP)
where P is the initial pressure of methyl formate and k
and K are constants. From the temperature depen-
dences shown in Figure 1, k and K are found to be 5.4 X
loz7exp(-27,200/RT) molecules ern+ sec-l and 5.4 X
10-lO exp(14,300/RT) mm-l, respectively.
When adsorption equilibrium is established for the
reactant, it follows that K corresponds to the equilib-
rium constant, and the heat of "reactive" adsorption,
&, is 14.3 kcal/mol. Accordingly, the constant k has
the physical meaning of the rate constant of surface
reaction with the activation energy Zr of 27.2 kcal/mol.
I 1
I I I
'e2- i3 2.4 2.5
I/T x 103
Figure 1 . Temperature dependence of k and K .
1179
The study on thermal desorption was carried out on
the same catalyst as was used for the kinetic study.
After a known amount of methyl formate was adsorbed
on the catalyst, the temperature of the catalyst was
raised a t various rates (p) under evacuation of a constant
speed (S). The pressure change due to desorbed gas
was followed by means of a Pirani gauge. The com-
position of the gas phase was continuously analyzed by
a mass spectrometer which was directly connected to
the system. Large values of the S / p ratio were chosen
to hold the condition under which the partial pressures
of desorbed species are proportional to their respective
rates of desorption.3
The desorption spectra shown in Figure 2 exhibit that
there are several states in adsorbed methyl formate;
since CO and Hz were generated simultaneously in peak
B, adsorbed methyl formate corresponding to this peak
is likely responsible to the decomposition which gives
CO and H,.
50 100 150 *C
Temperature
Figure 2. The desorption spectra of methyl formate
(6 = 0.13 deg sec-1).
Both results of kinetics and of separated studies on
thermal desorption of CO and Hz adsorbed on Cu show
that the desorption rates of CO and Hz are much larger
than that, of decomposition of adsorbed methyl formate.
Therefore on raising the temperature, methyl formate
adsorbed at room temperature is supposed to change
in the following way
HCOOCH,(g) +HCOOCH3(a) --t
kd kr
CO(g) + Hz(g)
where k d and k, are the rate constants of the desorption
and of the surface reaction, respectively. They are ex-
pressed in the forms k d = Vd exp(-Ed/RT) and k, =
v, exp(-&/RT), where v's and E's are frequency fac-
tors and activation energies, respectively. When the
adsorption of methyl formate is in a partial equilibrium
( k d >> kr), the following equations hold a t temperatures
(1) Y. Amenomiya and R. J. Cvetanovic, J. Catal., 9, 28 (1967).
(2) E. Miyazaki and I. Yasumori, Bull. Chem. Soc. Jap., 40, 2012
(1967).
(3) P. A. Redhead, Trans. F U T U ~Soc.,
U ~ 57, 641 (1961).
Volume 73,Number 4 April 1969
1180 TO THE EDITOR
COMMUNICATIONS

Table I

6.0 - - 6.0 Kinetics Thermal desorption

9 T E,, kcal/mol 2 7 . 2 =t 0 . 6 27.8 =t 1 . 3
cn 0)
s
0 0
L
Q or Ed, kcal/mol 14.3 f 1.0 14.8 f 0 . 7 (eq 1)

-
1 I 14.6 =k 1 . 0 (eq 2)
5.8- - 5.8 f Ud, sec-l ... 1 . 6 X lo6
-0 8
d
ur, molecules cmm2sec-1 5 . 4 x 1027 ...
N
N

5.6 - - 5.6 the reaction scheme assumed above. The coincidence

2.4 2.5 2.6 of a Q value with those of Ed suggests that the activa-
i/-rRor ( ~ 1 0 ~ 1 tion energy of adsorption for methyl formate is negli-
gible.
Figure 3. Plots of eq 1 and 2 for peak B.
It is therefore concluded that the adsorbed state cor-
responding to peak B is the true intermediate in the
TRand Tp, which correspond to peak maxima of methyl catalytic decomposition of methyl formate to CO and
formate and carbon monoxide, respectively. * Hz and that the surface reaction is the rate-determining
step. Details and more general discussions for the case
2 log T R - log p = Ed/RTR -k log (Ed/VdR) ( 1 )
where the adsorption equilibrium is not established will
2 log TP - log fi = Ed/RTp f log (E,/VdR) ( 2 ) be published later.
By measuring TR and Tp for various p(0.13 - 0.31°/ (4) Reference 3, p 655.
sec), the left-hand side of eq 1 (or 2) is plotted against
~/TR (or l / T p ) , as shown in Figure 3. From the slopes DEPARTMENT
O F CHEXISTRY NAOHIROMOMMA
and the intercepts of these plots Ed, E,, and V d were TOKYO
INSTITUTE OF TECHNOLOGY IWAOYASUMORI
OOKAYAMA,
MEGURO, TOKYO,
JAPAN
estimated, and these values are summarized in Table I.
There is good agreement with corresponding values in RECEIVED
JUNE7, 1968

The Journal of Physical Chemistry