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Covered Surface
Adsorbate( g ) + Adsorbent ( s )
adsorption
desorption
Class of adsorption:
Physisorption Physical adsorption van der Waals forces are forces of adsorption.
Strong forces
Molecules may fragment
Adsorption occurs at active sites
Only a monolayer is formed, then surface becomes saturated
H chem ~ 200 kJ / mol
Kinetics IV
Page 1 of 8
Adsorption Isotherm:
d
= ka [ A] (1 )
dt
This rate law is bimolecular in terms of the concentration (pressure) of gas particles and the
concentration of free sites, with an adsorption rate constant of ka . The corresponding
desorption process depends only on the concentration of occupied sites (since unoccupied
sites will obviously not exhibit desorption):
rated =
d (1 )
= kd
dt
Since there is a dynamic equilibrium between the adsorption and desorption processes, these
two rates are equal:
ka [ A] (1 ) = kd
Kinetics IV
Page 2 of 8
We can define an equilibrium constant between adsorption and desorption, then rearrange the
above expression to obtain surface coverage as a function of [A]:
K=
ka
=
kd [ A] (1 )
so
K [ A]
1 + K [ A]
To analyze adsorption data a plot of 1/ vs. 1/[ A] gives a slope equal to 1/ K and an
intercept of unity.
Dissociation upon absorption:
In some instances, after absorption of a substance, dissociation occurs on the surface. One
example of this is when H2(g) adsorbs, then dissociates into hydrogen atoms.
If we think about this qualitatively, we expect that the rate of adsorption will change because
we now need 2 sites for the molecule to adsorb. The rate of desorption will also be affected
by the new stoichiometry of desorbing particles (i.e.: we do not desorb an H2, we desorb two
hydrogen atoms to retain the original number of free sites.)
The new rates of adsorption and desorption become:
ratea =
d (1 )
d
2
= k d 2
= ka [ A2 ] (1 ) and rated =
dt
dt
At equilibrium:
Chem 162 Spring 2005
Kinetics IV
Page 3 of 8
1/ 2
ka [ A2 ] (1 ) = kd so
= a [ A2 ]
(1 ) kd
= ( K [ A2 ])
1/ 2
K 1/ 2 [ A2 ]1/ 2
=
1 + K 1/ 2 [ A2 ]1/ 2
Consider this graphically:
To analyze this type of adsorption data a plot of 1/ vs. 1/[ A]1/ 2 gives a slope equal to
1/ K 1/ 2 with a slope of unity.
In general, if you have adsorption followed by dissociation into n particles, the adsorption
isotherm becomes:
K 1/ n [ A2 ]1/ n
1 + K 1/ n [ A2 ]1/ n
Competitive adsorption:
Now consider the adsorption isotherm when two distinct species (A and B) are competing for
the same sites on the surface. There are two sets of parallel reactions:
Kinetics IV
Page 4 of 8
In this case, A is the fraction of sites occupied by A, B is the fraction of sites occupied by
B and (1 A B ) is the fraction of unoccupied sites available for A or B. The rates of
adsorption and desorption for each species simply take into account these new fractions.
Species A:
The rate of adsorption for A is:
rateA, a = k A, a [ A] (1 A B )
rateA, d = k A, d A
(note that the desorption rate is not different than the non-competitive case)
These rates are equivalent at equilibrium, and K A = k A,a / k A,d , so:
K A [ A] =
A
1 A B
[1]
Species B:
The rate of adsorption for B is:
rateB , a = k B , a [ B] (1 A B )
rateB , d = k B , d B
K B [ B] =
B
1 A B
[2]
Between equations [1] and [2], we have two unknowns. Solving this system of equations
yields the isotherms for each component:
A =
K A [ A]
1 + K A [ A] + K B [ B]
and
B =
K B [ B]
1 + K A [ A] + K B [ B]
To analyze this type of adsorption data a double plot of 1/ vs. 1/[ X ] (where X is an
arbitrary component) gives two lines with slopes equal to 1/ K X and a common intercept of
unity.
Kinetics IV
Page 5 of 8
Reactions at surfaces:
The first consideration we need to address surface reactions is the molecularity of the
reaction, i.e.: the number of particles (adsorbed or not) that undergo a reaction at a solid
surface. Additional vacant sites needed for adsorption of products are not counted.
Unimolecular reactions at surfaces:
In unimolecular reactions, the reactant is adsorbed to the surface, then undergoes a reaction
(typically a dissociation):
The key assumption is that the first step (absorption) forms a fast equilibrium, so the total
rate of the mechanism is only dependent on the rate of the reaction step. Furthermore, the
reaction is an irreversible unimolecular reaction.
The rate of the reaction is expected to be first order in [A], but the reaction will only occur
when A is adsorbed to the surface, so:
rate = k
We already know the fraction of sites occupied by A during the (fast, equilibrium) absorption
process, so we can express the rate as:
rate =
d [ A]
kK [ A]
=
dt
1 + K [ A]
Note that this result is equivalent to the Mechaelis-Menten mechanism of enzyme catalysis.
Consider this result graphically:
At low [A] (when K[A] << 1), the reaction
rate appears first order in [A]. At high [A]
(when K[A]>>1), the reaction appears zeroorder in [A] because the concentration of A
is effectively constant at high surface
coverage (similar to a pseudo-zero order
reaction!)
Kinetics IV
Page 6 of 8
If there is an inhibitor present on the surface (competing for sites), the reaction rate is
expected to decrease as A decreases. This is actually easy to take into account by changing
the term in the reaction rate to A :
rate = k A =
kK A [ A]
1 + K A [ A] + K I [ I ]
where [I] is the concentration of inhibitor. From this expression, qualitatively, we see that
for low [I], this expression reduces to the ideal case above, while at high [I] it reduces to:
rate =
kK A [ A]
KI [I ]
which is first order in [A], but the rate decreases with [I], which is to be expected.
Bimolecular reactions:
We now consider reactions where there are two species that react together. The
absorption/reaction processes can occur either independently or competitively.
Case 1 the Langmuir-Hinshelwood mechanism:
In this mechanism, there is competitive adsorption, then the reaction rate between A and B is
proportional to the probability that A and B are on adjacent sites:
rate = k A B
kK A K B [ A][ B]
(1 + K A[ A] + K B [ B])
Consider this graphically, when [B] is held constant and [A] is varied:
Kinetics IV
Page 7 of 8
rate = k[ A] B
kK B [ A][ B ]
1 + K A [ A] + K B [ B]
This expression assumes there is competition between A and B for sites, even though bound
B reacts with unbound A. If A never binds, the KA[A] term vanishes in the denominator.
Consider this graphically:
Again, [A] is varied with constant [B]. At
low concentrations of [A], the reaction is first
order in [A]. At large concentrations of [A],
the surface becomes saturated with [A] and
the rate becomes zero order in [A].
Kinetics IV
Page 8 of 8