VACUUM

Thermal Desorption of Gases

P. A. R E D H E A D
Radio and Electrical Engineering Division, National Research Council, Ottawa, Canada
(Received 11 June 1962 ; accepted 16 July 1962)
Methods for determining the activation energy, rate constant and order o f reaction from
"flash-filament " desorption experiments are examined. Two heating schedules are considered : (a) a linear variation o f sample temperature with time (T = To + fit), and (b) a
reciprocal temperature variation (1/T = I/To --at). The activation energy o f desorption is
estimated from the temperature (Tp) at which the desorption rate is a maximum (for first-order
reactions) and from the change o f Tp with surface coverage (for second-order reactions). The
order o f the reaction is determined from the shape o f the desorption rate versus time curve, or
the variation o f Tp with coverage. Applications o f these methods to experiments on chemisorption and the desorption o f ionically trapped gases are discussed. The effbct o f finite
pumping speed in the system is analysed and the necessary corrections derived.

I. I n t r o d u c t i o n
The "flash-filament " method has been widely used to
study the kinetics of desorption of chemisorbed gases from
the surface of refractory metals (principally tungsten) 1-11.
The sample, in the form of a ribbon or wire, is rigorously
cleaned in vacuum, a known gas is then introduced at a
constant input rate, and allowed to adsorb on the sample.
The gas is then desorbed by heating the sample while the
pressure in the system is recorded ; the resulting pressuretime curve will be referred to as a " desorption spectrum ".
If the temperature-time relation for sample heating is suitably
controlled the desorption spectra can be analysed to yield
information on various adsorption parameters.
This
information includes : (a) the number of the various desorbing
phases and the population of the individual phases ; (b) the
activation energy of desorption of the various phases, and
(c) the order of the desorption reaction.
Recently the same technique has been used to study the
desorption of rare gases from metals12 ; in this case the
gases are ionized and driven into the metal surface before
desorption.
Methods of analysing the desorption spectra have been
described by Smith 13 and Ehrlich 14. Here we shall consider
two heating schedules : a linear variation of sample temperature with time (T = To + /~t), and a reciprocal variation
(1/T = 1/To --at). It is first shown how the various adsorption parameters may be derived from the curve of desorption
rate as a function of sample temperature. The second part
of the paper is concerned with the derivation of the desorption
rate from measured pressure-time curves.
We will consider a system into which gas is being leaked
at a constant rate (L molecules/second) and is being pumped
away at a constant speed (S 1./sec). At equilibrium, when
adsorption on the sample has ceased, p ~_ Peq and
L = KSpeq

where K = 3.27 10 t9 molecules/l, at p ~ 1 torr, and

T ~ 295 K.
During the desorption cycle it will be assumed that no
adsorption occurs, then,
AN(t) + L = KSp + KVdp/dt

(2)

where A is the sample area (cmZ),

N is the desorption rate (molecules/cmZ/sec)
and

V is the volume of the system (1.).

The assumption of no re-adsorption on the sample during

the desorption cycle is valid for the desorption of ionically
trapped rare gases. For chemisorbed gases, re-adsorption
depends on the population of the various adsorbed phases,
the pumping speed, and the time duration of the desorption
cycle. The amount of re-adsorption is usually trivial unless
the pumping speed is very slow and the desorption cycle
long. The separate chemisorbed phases are usually observed
to fill up in decreasing order of their energies, i.e. the phase
of highest activation energy of desorption fills first, followed
in order by the phases of lower energy. These phases are
desorbed in increasing order of their energies. As one
particular phase is desorbing, the higher energy phases,
which have not yet desorbed, are almost fully populated
and thus re-adsorption into these phases is unlikely.
Adsorption on the walls of the system has also been
ignored. With a glass system at room temperature, adsorption on the walls is significant for hydrogen and carbon
monoxide. (This problem has been discussed by Ehrlicht4).
Combining (1) and (2) and putting p* = p --Peq, we obtain
dp*/dt + p*/T :

aN(t)

(3)

where a = A / K V
and

T:

V/S, the characteristic pumping time.

From (3) it can be seen that for small pumping speeds

(1)
203

204

P . A . REDHEAD

( r - , c~) the desorption rate is proportional to the first

derivative of pressure with time. This condition can be
approximated in practice when the duration of desorption
sweep is made short compared with the characteristic
pumping time T. With chemically active gases this condition
can be approached with very fast sweep rates ( > 103 K/sec).
When observing the desorption of rare gases this condition
can be achieved readily, since can be made as large as
103 sec.
Alternatively, for very high pumping speeds (3 ~ 0), we
see that p* --+ arN(t), thus the desorption rate is proportional
to pressure.

where the pumping speed was made large so that T ~ ts (is

is the duration of the temperature sweep). These spectra
show the desorption of chemisorbed hydrogen from tungsten

I I . T h e desorption rate curves

The desorption rate as a function of sample temperature
may be obtained directly when either one of the two conditions discussed above can be approximated experimentally.
Figure 1 shows the desorption spectra of argon from

iI

j}'

I
i

i-.

,,! 4o0o

><~
{22

i i

I--

t :14 MIN - - ' ~~-8 6

I
i
i
9

a~
<~

I ',

Ld
F<Z
0~
Z

5oo

l i 600

Q_
0
(.,')
Ld
Q

008

05

I0
T [K]
103

15

20

FIG. 2. Desorption rates of hydrogen adsorbed on polycrystalline

tungsten at 80~'K for various values of the a d s o r p t i o n time (te).

as a function of the amount adsorbed on the surface. These

spectra were obtained by directly recording the pressure
signal.
This section is concerned with methods for estimating
various adsorption parameters from data of the type exemplified by Fig. 1 and 2.
II.1. The maximum desorption rate
The rate of desorption from unit surface area may be
written as

/.' .....<~oo
I

N(t)

:= -- dcr/dt = v,,d, exp( -- E/R T)

(4)

T [_K]
I0 3

where n is the order of the desorption reaction,

is the surface coverage (molecules/cm2),

FItJ. I. Desorption rate of argon from tungsten for various values of

the b o m b a r d i n g ion energy. All curves for 5 x 1012 ions/cm 2.

tungsten12 as a function of the incident ion energy. Here

the pumping speed was reduced to about 10- 3 1./sec (T -- 103
sec). These spectra were obtained by electrical differentiation
of the pressure signal with respect to time during the desorption cycle. Figure 2 shows an example of the other extreme,

vn is the rate constant,

and

E the activation energy of desorption (cal/mole).

We will first consider a linear change of sample temperature

with time (T == T O + fit) and assume that E is independent
of ~. Equation (4) is solved to find the temperature (Tp) at
which the desorption rate is a maximum, then

205

Thermal Desorption of Gases

E/RTp 2

(vl/[~)exp(--E/RTp)

:forn

(2~pV2/fl) exp ( - - E / R T p )

)
?forn-2

~r0v2 exp (

--

(5a)

E/RTp)

(5b)

where % is the initial surface coverage

crp is the coverage at T = Tp.

and

It is shown later than %/~rp ~ 2 for a second-order reaction.

E q u a t i o n (5a) shows that Tp is independent of coverage
for a first-order reaction with constant E and thus E can be
found directly f r o m a measurement of Tp provided a value
of vt is assumed. The relation between E and Tp is very
nearly linear and, for 10 t3 > vl/{~ > 108 ( K - l ) , is given to
1.5 per cent by
,

VlTp

E/RTp -- in fi

l
. . . . .

--3.64.

(6)

i . . . . . .

r
-

Equation (5a). F o r reasonable accuracy # must be varied

by at least two orders of magnitude.
Returning to the second-order case, it can be seen f r o m
Equation (5b) that Tp now depends on the surface coverage.
~r0 may be found from the area under the curve of desorption
rate as a function of time and log (%T2p) plotted against
1/Tp, a straight line is obtained of slope E/R. v2 is then
found by substitution in E q u a t i o n (5b). Thus the order of
the desorption reaction can be determined f r o m the behaviour
of the m a x i m u m in the desorption rate curves with coverage.
A first-order reaction with a fixed activation energy of
desorption gives rise to a peak in the desorption rate curve
which does not change in temperature with coverage. If
the temperature of the peak decreases with increasing
coverage, the reaction may be second-order with fixed
activation energy, or first-order with an activation energy
dependent on coverage. These two cases can be distinguished
by plotting log (~r0TZp) against 1/Tp; as noted above, a
second-order reaction with fixed activation energy yields a
straight line.
W h e n the sample temperature is varied in a reciprocal
fashion with time (1/T = 1~To --at) the relationships between
E and Tp are given by,

E/R

= (vl/a) e x p ( - - E / R T p )

: for n = 1

(8a)

= (vzcro/a) exp ( - - E / R T p )

: for n = 2.

(8b)

120

140
I00

--

----

bJ
J

120
8o

CD
5~

I ....

4.76 I0 -~

I00

2,86

....

40

I0 - 4

80

60
Ld

4C
0

0.5

]5

1.0

2,0

2.5

T. EK]
i0 3
FiG. 3. Activation energy of desorption (E) as a function of Tp for a
first-order reaction and a linear temperature sweep (T = To k~ fit)
taking vl = 1013 sec-l.
0

Figure 3 is a plot of E q u a t i o n (5a) and shows E as a

function of Tp for various values of fl, taking Vl = 1013 s e c %
The activation energy can be determined without assuming
a value of the rate constant by varying /~ and plotting log Tp
against log /3 ; E can then be obtained from the relation,

E/RTp + 2 = d ( l o g / 3 ) / d ( l o g T p ) .

(7)

The rate constant can then be found by substituting E in

0,5

10

1.5

2,0

25

ro EOK]
F~6. 4. Activation energy of desorption (E) as a function of 72p for a
first-order reaction and a reciprocal temperature sweep (I/T = I ]To -- o~t)
taking vl ~ 10L3 sec-l.
Figure 4 shows E as a function of Tp for n = 1 and various
values of a, taking vl = 1013 sec -1. The relation between

P. a . REDHEAD

206

E and Tv is almost linear for the first-order case, and is

given, to ~ 0 . 5 per cent, by

E = in ( v , ' ~ - - 3 . 5 1 .
R Tp
\ Tp

(9)

F o r a temperature sweep from 300 K to 2400 K the values

of a given in Fig. 4 correspond to the following total sweep
times (ts) :

ln(ao/ap)

I (To/Tp)2exp[--E/R(I/To-I/Tp)]

where % is the coverage at the start of the temperature

sweep,
and
ap is the coverage at temperature Tp.
Thus at the temperature where the desorption rate is maximum, the coverage is a0/e.
By substituting Equation (12) and Equation (10) in
Equation (4) we obtain the equation describing the shape of
the desorption rate curve,

,)

ts (sec)
In(Np/N) ~= R
2.86 10 3
2.86 x 10 -4
4.76 10-5

1
l0
60

11.2. Peak shapes

The shape of the experimental curve of desorption rate as a
function of sample temperature can be used to determine (a)
the order of the desorption reaction, and (b) whether the
activation energy is constant or, alternatively, a function of
surface coverage. Frequently the measured curve consists of
several overlapping curves caused by the presence of several
desorbing phases of different activation energy. In such
cases the methods of the previous section must be applied,
since the only parameter that can be accurately measured
is Tp. This section is concerned with those cases where
the desorption rate curve of one desorbing phase can be
clearly distinguished.
For the case of a linear temperature sweep we integrate
Equation (4) to obtain
c%
T.

__ f de = (vn/[3) f exp(-- E/RT)dT

,] an
%

2"i

-~ l n c q / a 2

: f o r n -- 1

= l/cr2 -- l/a1

: for n = 2.

Taking only the first two terms in the expansion of H(u), i.e,
E/2RT> 1, one obtains
pbT_,
v,RfI'/l
] e x p ( - E/RT) d r
[;ELT22exp(-- EIRT2) -f
Tx

Then for the ilrst-order case (n

obtain

TT2exp(--E/RTO].

[
[

kTp]

E (I T

I )]

" R

Tp

- 1.

(14)

It can be seen that the desorption rate curve is asymmetric

about the m a x i m u m at Tp.
Similarly for the second-order case it can be shown that

%/~p = 2,
Np

1 !exp

(;)2exp

and

[_

2E(IT -

;p)]}2

('Sa)

Tpl)] .

(15b)

When (T/Tn)2--> I. then

Np~_,N csh2 E . .2RE(IT

. .

Thus the desorptiou rate curve is symmetric about the

m a x i m u m at Tp for I T -- Tpl small. Figure 5 shows the
theoretical desorption rate curves for a first-order desorption
with E = 91.5 kcal/mole, and a second-order reaction with
E = 87 kcal/mole. The cosh approximation for the secondorder case is shown by the circles in Fig. 5.
With a reciprocal temperature sweep ( I / T - 1~To--at),
the surface coverage is given by
t~
E 7 f
F~tE7
~'
:
f o r n ::: 1
v,,exp - - e T 0 j ) e x p L R
=~: lgcr2
tl

J"

(10)

The integral may be evaluated by using the substitution

tt ~ --E/RT, integrating by parts, and using the identity
u
( e x p ( t ) dt = exp (u) X H ( u ) ; for lul >>1,
U
d t
--co
w h e r e H ( u ) = 1 q- ( l ! / u ) q- (2!/u2) + . . .
(11)

Tp

(T'~2exp

By comparing Figs. 3 and 4 it will be seen that for the same

total sweep time the value of Tp for a given E is slightly
higher with the reciprocal sweep than with the linear sweep.

~ I (13)

(12)

1), using Equation (5a), we

0"2

(fl

fort/

:: 2.

The integration can be performed without approximation

to give

-}- exp

N"
N

--

;)
')]

-- R

Tp

cosh2 [ E ( 1
- ~)]
2R Tp

forn

(16a)

forn=~2.

(16b)

These equations are similar to the linear sweep case except

for the factor (T/Tp)Z. Similarly to the linear sweep case,
it can be shown that
0

o"0

t' n = 1

2,, = 2

(17)

207

Thermal Desorption of Gases

,0

! ,b/

06

'

II

t!i

"

'
o.

lIll/
?

13

. . . . .

%%1
]

~.-,,~2nd ORDER

~1

/PI

,>

__

/ [

I2

'

% ',

tst ORDER~

14

[oK]

15

~x

'

I
i

16

17

iO s
F r o . 5. Normalized desorption rate as a function of temperature for a
first-order (E .= 91.5 kcal/mole) and a second-order (E 87 kcall.nole)
reaction, for a linear temperature sweep. The circles show the cosh~
approximation (Equation 15b). The 's indicate experimental points
for the desorption of the E-phase of N2 from W, adsorbed at 300K.

The above relationships can be used to determine independently the activation energy and rate constant from the
desorption rate curves. The initial surface coverage can be
obtained by measuring the area under the desorption rate
versus time curves, since
co

f N dt = ~o.
0

F r o m Equations (4), (5) and (8), and using the approximation for ~p/ao, it can be shown for the linear sweep case that

E = croflRT2p

for n =

= 4NPRT2p

for n =

2.

croft

,Up
v, =

4Np
and

v2 ---- cr20expt--~-0/3 ) .

Similarly for the reciprocal sweep,

:

a~
vl
and

vz =

goeXp

forn

forn

2.
(17)

csoTp

4Np
(
4 Np
~20 exp \~oclTpj

curves

(a) W h e n S--->0, or the sweep duration (ts) is short

compared with the characteristic pumping time of the
system (r), the desorption rate curves can be obtained
directly f r o m the apparatus by differentiation of the
pressure signal during the desorption cycle.

W e now examine the case where neither of the above

conditions applies and corrections must be used to allow for
the effects of finite pumping speed.

dp*
p*
dt + ~ = aN(t).

(YOfX

4NpR

pressure-time

III.1. The effects of finite pumping speed

The relation between pressure and desorption rate for a
system with a constant input leak rate is given by

it 4NpTp'~

E = NpeR

The

So far it has been assumed that the desorption rate curves

are available for analysis. As mentioned earlier, there are
two experimental conditions when the desorption rate-time
curves are directly available :

(b) W h e n S is large and the sweep duration is long

compared with characteristic pumping time, the
desorption rate is then proportional to pressure.

(18)

/%Upr/~

<,o exPt,

III.

(3)

If ~ is known, then the N(t) curve can be obtained f r o m the

measured p(t) curve by solving E q u a t i o n (3). This can be
done most effectively by using operational amplifiers operating directly on the p(t) signal during the experimental
measurement, a N(t) can then be directly recorded.
E q u a t i o n (3) m a y be normalized by noting that when
S = 0, (r--+ Do) then dp*/dt = aN(t) and integrating to
obtain

208

P. A. REDHEAD
t
t~

p* ~ m a x

-- a I N(t) dt,
J
co
fJ

a (70.

which has a m a x i m u m value of p* ma x = a I N(t) dt

mJ

0
Here P*~max is the m a x i m u m pressure change that occurs
in a system of zero pumping speed. Then if we put
P -~ P*/P*o~maxand substitute in Equation (3), we obtain

dP
dt

P
-t-

N (t)
=

(10

(20)

g(T).

F o r simplicity we will consider only the first-order case.

F o r the linear temperature sweep, from Equations (4), (10)
and (12) we obtain

g(T) = vl e x p - -

( E

RT +

VlR T2 exp -- [-T~

fie

'

(21)

neglecting T20 exp (--E/RTo) in comparison with T2 exp

(--E/RT).
Similarly for the reciprocal sweep, from Equations (4),
(8a) and (16a), we obtain (for T >>To)

g(T) = v1 exp --

RT + aE exp -- R

"

(22)

These equations have been solved numerically and Fig. 6

shows P as a function of T for various values of the characteristic pumping time ~ for a linear temperature sweep and
an activation energy of 35 kcal/mole. Figure 7 shows the
P(T) curves for the same activation energy and a reciprocal

temperature sweep. It can be seen that a straight line drawn

through the maxima of the P(T) curves intercepts the axis
at the temperature of the m a x i m u m in the normalized
desorption-rate curve, g ( T ) ; this straight-line fit has been
observed for all values of E and T for which this calculation
has been made. As the pumping speed is increased ( r
decreased), the temperature of the maxima in the P(T)
curves approaches the temperature of the m a x i m u m in the
desorption-rate curves, Tp. As the pumping speed is
decreased, the temperature at which dP/dt is a m a x i m u m
approaches Tp.
Equations (20), (21) and (22) have been solved numerically
to yield values of the temperature, Tin, at which the pressure
is a m a x i m u m for various values of E and 7. The relative
displacement of Tm from Tp,

[
t
s

5_

r=l.Osec

08

0.6

g(T) x
04

[ .....

55

60

was then

plotted as a function of log r for various values of E, straight

lines were obtained for each value of E. It was then found
that if AT/Tp were plotted against log fIAT, where At is the
approximate time duration of the pressure peak, a single
straight line was obtained for all values of E. F r o m Equation
(14) it can be shown that At is proportional to E for a linear
temperature sweep. Figure 8 shows AT/Tp as a function of
log r/E for a linear temperature sweep. Similarly, for a
reciprocal temperature sweep the duration of the pressure
peak is inversely proportional to E. Figure 9 shows AT/Tp
as a function of log r E for a reciprocal temperature sweep.
F o r both cases a reasonable fit to a straight line is obtained.
F r o m this type of plot the displacement of the measured
value of Tm from Tp can be estimated for any value of the
pumping speed.

I0

02

(At
rm-r,)
Tp -Tp ]

65

7'0

7.5

rEK]
i2
FIG. 6. Normalized pressure (P) as a function of temperature for a
linear temperature sweep (fl = 2 103~K/sec). First-order reaction
with E =.= 35 kcal/mole, vI = 1013 sec-I and To -- 300 'K.

Thermal Desorption of Gases

1.0

209

t
I

0.8

06

p
04

5 .5

6 0

0 I5

7,0

7IS

80

T [K]

I0 2
FR]. 7. Normalized pressure (P) as a function of temperature for a
linear t e m p e r a t u r e sweep (~ -- 2.86 x 10-3 sec I OK-]). First-order
reaction with E -- 35 kcal/mole, Vl
1013 sec-I and T 0 = 3 0 0 K .

I0

iO s

/
/

o'

~j

.w

0
if?
_A

_J
0
:m

09

i0-1

10 2
E ( K CALS/MOLE)

k)
UA

~l"'

13
o

//

35

I0

iO -3

AT

{3 5O

I
i0-~

80

Q)
w

(%)

Tp
FIG. 8. Relative d i s p l a c e m e n t o f t e m p e r a t u r e o f the pressure m a x i m u m
as a function o f ,r/E. F i r s t - o r d e r reaction with linear t e m p e r a t u r e
sweep (/~
5 0 K sec-]).

E(K CALS/MOLE)
o

I00

A 80

,A

X 6O
n 40
+

20

r
L
,

2
AT

i
6

(%)

Tp
FIG, 9. Relative displacement o f t e m p e r a t u r e o f the pressure m a x i m u m
as a function o f E r . First-order reaction with reciprocal t e m p e r a t u r e
sweep (g -- 4,76 10-5 se-I K-1 and T o = 300K).

P. A. REDHEAD

210

111.2. Areas and reaction order

The order of the desorption reaction can be estimated
from the p(t) curves by a measurement of areas under the
curve and knowledge of the pumping speed. Integrating
Equation (3) we obtain

Ndt

~0

--

cr

(p*dt).

l/a(p* + I/T

--

Then

~P =

( Ndt

o'0

Ndt

:= A2 - rP*max
A1 T A2

tz

where A t a n d

A2 are the areas on either side of the

maximum of the p*(t) v. t curve,
tl is the time at which p*(t) is a maximum,
and t2 the time when desorption is essentially
complete.
The surface coverage at the time that the pressure is a maximum has been approximated to ,~p; the error introduced
here is small.
Thus, Az

-- 1

- - C~p

A2

2.72Tp*max
1.72 . . . . . . . . . .
A2
=

1 --

2 rP*max
A2

: forn

--: 1

(23)

: f o r n = 2.

When T,~(t2--ta) then the second terms in the above

expressions can be neglected.
The comparison of areas under the p*(t) curves is a simple
and rapid way of determining the order of the desorption
reaction, but can only be used when the activation energy of
desorption is independent of surface coverage. The p(t)
curves for a second-order reaction and a first-order with
variable activation energy both exhibit maxima at a temperature that decreases with increasing coverage, The two
cases can be distinguished by observing the temperature at

which desorption is essentially complete. This temperature

is independent of initial coverage for first-order reactions
whether the activation energy is variable or not.

IV. Apparatus for generating the temperature

sweep
To obtain accurate measurements of activation energies
and to compare the desorption rate curves with the theoretical
curves, it is necessary to control accurately the temperature
variation of the sample during desorption.
A simple circuit has been developed to control the temperature sweep of tungsten wire samples having a resistance,
at 300K, of about 20fL The circuit is shown schematically
in Fig. 10. The resistance of the sample is monitored by
passing a small radio-frequency current through the sample
from a constant current source. The frequency used was
262 kc/s and the current maintained sufficiently small that
heating effects were negligible. The radio-frequency voltage
across the sample, which is proportional to sample resistance,
is amplified and detected. The resultant signal is compared
with a reference sweep voltage, and the error signal used to
control the direct-current heating supply to the sample.
The reference sweep voltage may be varied linearly or reciprocally with time, and shaped to compensate for the small
non-linearity of the resistance-temperature characteristics
of the tungsten sample.
Circuits of this type have been operated with total sweep
times (300K to 2400K) varying from I sec to 10 rain.

V. Discussion
Desorption-rate curves, using controlled temperature
variation of the sample, can be readily analysed to yield
considerable data on the kinetics of desorption. Desorptionrate curves can be most readily obtained by satisfying one
of two limiting conditions :
(I) total sweep time much shorter than the characteristic
pumping time of the system ;

20 mh

SAMPLE

0.1 mF+

OSCILLATOR

I SERIES }
CONTROL
TUBE

560mmF

r80 k
~N'.-

-1 HEAT
csuP
TO
Ll
SAMPLE

6800 mmF

"

47mine

I(

L ~
DC ~
I. F
AMPLIFIER .I ~]COMPARATORI
LINEAR
bOOk
DETECTOR

FIG, 10, Block dia~gram of temperature control unit

SWEEP
I GENERATOR]

Thermal Desorption of Gases

(2)

total sweep time m u c h longer t h a n the characteristic

p u m p i n g time.
C o n d i t i o n (1) c a n be achieved easily for the d e s o r p t i o n of
rare gases and, w i t h m o r e difficulty, for m o s t of the chemically
active gases. C o n d i t i o n (2) is m o r e suitable for use with
gases such as h y d r o g e n where it is difficult to reduce the p u m p ing speed o f the system to a sufficiently small value. I f
c o n d i t i o n (1) is satisfied, it is n o t necessary to m e a s u r e
p u m p i n g speed to i n t e r p r e t the e x p e r i m e n t a l data. Analysis
of d a t a w h e n n e i t h e r o f the a b o v e c o n d i t i o n s is satisfied is
m o r e complex ; h o w e v e r a c t i v a t i o n energies c a n still be
e s t i m a t e d with r e a s o n a b l e accuracy.
T h e p o p u l a t i o n o f the various d e s o r b i n g phases c a n be
d e t e r m i n e d f r o m the d e s o r p t i o n spectra. These p o p u l a t i o n s
can b e e q u a t e d to the p o p u l a t i o n s o f the various a d s o r b e d
p h a s e s (states o f different b i n d i n g energy) only if r e d i s t r i b u t i o n
a m o n g s t the a d s o r b e d phases does n o t occur d u r i n g the
d e s o r p t i o n cycle.

211

Acknowledgements
T h e a u t h o r is i n d e b t e d to Drs. S. D. Baxter a n d D. C.
Baxter for assistance with the n u m e r i c a l c o m p u t a t i o n s .

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