SURFACE PHENOMENA 2

adsorption
Adsorption

surface of liquids : molecular forces

the same is true for solid surfaces
* as a result of this unsaturation
- attracting onto and retaining on their surfaces gases or dissolved substances
phenomenon
= is called adsorption

adsorption

adsorption

adsorbed phase
adsorbent
* adsorption = surface only
* absorption = distributed into the body
- when doubt exists
= the term sorption is sometimes used

adsorption
Adsorption of Gases by Solids

effective adsorbing agents : silica gel, charcoals

amount of gas adsorbed by a solid depends on = natures of the adsorbent and gas being adsorbed
= area of adsorbent
= temperature and pressure of the gas

surface area of adsorbents cannot always be

determined readily, commonly employed,
= the mass of adsorbent
= expressed as amount of adsorption per unit mass of
adsorbing agent

adsorption
in adsorption, true equilibrium is established

i.e. for a given gas and adsorbent

the extent of adsorption under any
conditions of T and P
is definite and reproducible
adsorption of gas by a solid
by evolution of heat
= heat of adsorption

types of adsorption
Physisorption : physical or van der Waals
adsorption
Characteristics:
= low heats of adsorption
= adsorption equilibrium is reversible, established
rapidly
= van der Waals forces are involved

* adsorption of gases on charcoal

types of adsorption
Chemisorption : chemical or activated adsorption

Characteristics:
= higher heat changes

= firmer attachment of gas to surface

@ many cases - adsorption are neither one type or the

other, but a combination of both
some - physical adsorption at low T and
chemical adsorption at higher T

adsorption
Adsorption Isotherms
- relation between the amount of substance adsorbed
by an adsorbent and the equilibrium pressure or
concentration at constant T is called
= adsorption isotherm
- 5 general types of isotherms have been observed in
the adsorption of gases on solid

adsorption

adsorption
Type I isotherms

amount of gas adsorbed per given quantity of

adsorbent increases relatively rapid with
pressure then, slows down
@ Variation of the amount of adsorption per unit area
(or unit mass) with pressure given by the
Freundlich equation

y kP1/n

adsorption
taking logarithm,
ln y = ln k + (1/n) ln P
plot log y against ln P :
= straight line
slope = m = 1/n
y-intercept = b = ln k

adsorption
another variation is given by the Langmuir equation
- assumptions:
(a) gases adsorbed by a solid surface
- mono-molecular layer only

(b) adsorption process

- consists of two opposing actions,
condensation
evaporation
(c) when adsorption starts, every molecule colliding
with the surface may condense on it, however, as
adsorption proceeds surface fills up

adsorption
results :
initial rate of condensation is highest and
= falls off as the area of surface available for
adsorption is decreased
by thermal agitation
= rate of desorption
- depend on the amount of surface covered
- increase as the surface becomes fully saturated
@ eventually, the two rates become equal
= equilibrium is established
adsorption equilibrium

adsorption
mathematically,

let = fraction of the total surface covered by

adsorbed molecules at any instant
(1 ) = the fraction bare and available for
adsorption
- from kinetic theory:
= the rate at which molecules strike unit area of
surface pressure of the gas

adsorption
the rate of condensation of molecules should be
determined both pressure
fraction of surface bare

d
rate of condensation k1 N(1)P
* let dt
k2 rate of evaporation
= surface is fully covered

d
rate of evaporation k2 N
*at adsorption
dt equilibrium,
(N-total number of sites)

k1 N(1)P k2 N

adsorption
solving for ,
- if

k1 P
k 2 k1 P

k
1
then,
K
k2

@ K = equilibrium constant

use of vant Hoff equation

o

lnK

ads H

T RT2

KP

1 KP

adsorption

KP

rearranges to
1 KP

- at constant :

KP
1

ln K + ln P = constant

- from the vant Hoff equation, it follows

lnP

lnK

ads H

2
T T
RT

adsorption
with d 1 dT 1
2
T
T
eqn
* rearranges to

lnP

lnK

ads H

2
T T
RT

lnP

ads H
R
1

T

plot of ln P vs 1/T

adsorption
if y = amount of gas adsorbed per unit area or per unit
mass of adsorbent
then,
y
kKP

y k
1 KP
if a = kK
aP
y
1 KP
Langmuir adsorption isotherm
a and K = are constants
= are evaluated experimentally

adsorption
dividing both sides of eqn by P will give,

y
aP

P P(1 KP)
- taking reciprocals :

P P(1 KP)
P 1 K
giving

P
y
aP
y a a
- plot (P/y) against P
slope
= K/a
y-intercept
= 1/a

adsorption
another way of expressing this relation
- using volume
= expanding equation

KP

1 KP

gives KP + = KP
= since

Vthen,

= plotting (P/V) against P

slope
y-intercept

P P
1

V V KV
= 1/V
= (1/KV)

adsorption
for adsorption with dissociation

= the rate of adsorption is proportional to the

pressure, and to the probability that both atoms
will find sites
d
2
k1 P[N(1)]
dt
= the rate of desorption is proportional to the
frequency of encounters
d
2
k2 N
dt
1/2

KP

1/2
= at adsorption equilibrium
1 KP

adsorption
Types II and III isotherms
= the adsorption is multimolecular
@ Brunauer, Emmett, and Teller (BET) derived the
relationship : BET isotherms
P(equil)
P
1 c 1 P
Po(sat)

V P P V c V c P
o

where:

c e

ElEL

RT

El = heat of adsorption of the first layer

EL = heat of liquefaction of the gas

* isotherm Type II follow when E1 > EL

* isotherm Type III follow when E1 < EL

adsorption
= the BET isotherm may be used by plotting:

P
o

V P P
slope

against

P
o

y-intercept

c 1
Vm c
1
Vm c

adsorption
Types IV and V isotherms
= not only multilayer adsorption but also
condensation of gases in the pores and
capillaries of the adsorbent
= the difference arises from the relative
magnitudes of El and EL

* isotherm Type IV
* isotherm Type V

follow when El > EL

follow when El < EL

more complex types

adsorption
Application

Heterogenous Catalysis
* characteristic all such systems
proceed not in the gas phase but at the surface
of the solid catalyst

process frequently referred to as contact catalyst

adsorption
Catalytic reaction involves 4 steps:
(1) adsorption of the reacting gases on the surface
of the catalyst

(2) activation of the adsorbed reactants

(3) reaction of the activated gases in the adsorbed
phase
(4) diffusion of the products of the reaction from the
surface into the gas phase

adsorption
Catalytic Activity at Surfaces

= action of a catalyst
an alternative reaction path with lower
activation energy
does not disturb the final equilibrium
composition of the system
= catalyst and reagents = different phases
= we will only consider gas/solid systems :
(solid = mainly metals)

adsorption
LANGMUIR-HINSHELWOOD Mechanism

= the LH mechanism of surface catalyzed reactions :

- the reaction takes place by encounters between
molecular fragments and atoms adsorbed
on the surface
- expect a second order rate in the extent of
surface coverage
@ consider the reaction : A + B P
- if A and B follows
the Langmuirs isotherms and
adsorbs without dissociation

adsorption
the rate
to the probability that A & B are adsorbed on
neighboring sites, which is

to the product of the fractions of the surface A

and B covered by A & B
rate = kAB

adsorption
then,
and

K
A PA
A
1 KA PA KB PB
B

KB PB
1 KA PA KB PB

and the rate of the reaction becomes :

rate

kKA KB PA PB
1 K APA KBPB 2

kK
A KB PA PB
rate
2
1 K APA KBPB

adsorption

if PB is held constant and PA is varied:

at very low concentrations of A and B

= predicts a second order kinetics
a special case of interest :
when one reactant (A) is weakly adsorbed and
other is strongly adsorbed (B)

means: KBPB >> 1 + KAPA

then eqn becomes

kK
A PA
rate
KB PB

the

adsorption
LANGMUIR-RIDEAL Mechanism

= an alternative mechanism for a bimolecular surface

process
reaction occurs between a molecule that is not
adsorbed (A) and an adsorbed molecule (B)
= the rate
to the pressure (or concentration) of A
to the fraction of the surface that is covered
by B,
then, rate = kPAB
kK
B PA PB
rate
and
1 KA PA KB PB

adsorption
not many ordinary chemical reactions occur by the
LR mechanism
- evidence show that radical combinations on
surfaces sometimes occur in this way
- combination of hydrogen atoms is sometimes a
first order reaction :

adsorption
considering the reaction:
- the fraction of the surface covered by hydrogen
atoms is
K
P
H

1 K PH
- the rate of combination is,
2
H

kK
P
rate kPH
1 K PH

kK
P
H
rate kPH
adsorption
1 K PH
@ at lower temperatures the surface may be fully
covered
thus, KPH >> 1 and
rate = kPH

first order kinetics

@ at higher temperatures the surface coverage

decreases
thus, 1 >> KPH and

rate kK PH2
second order kinetics

adsorption
ELEY-RIDEAL Mechanism
= a gas-phase molecule collides with another molecule
adsorbed on the surface
- the rate of formation of the product is expected
to be
to the partial pressure (PB) of the nonadsorbed gas
to the extent of surface coverage (A) of the
adsorbed gas
A + B P

rate = kPBA

adsorption
the rate constant (k) might be larger than the
uncatalyzed gas-phase reaction because:
(a) the reaction on the surface has a low activation
energy,
(b) the adsorption itself, is often not activated
- adsorption isotherm for A can be expressed in terms
of its partial pressure, PA
= if it follows the Langmuir isotherm then,
KP
A
rate kPB
1/2
1 KPA

adsorption
if A = diatomic molecules
and,
1/2
KP 1/2
1 KP

then, the rate will be,

kKP
A PB
rate
1 KPA

adsorption

kKP
A PB
rate
1 KPA

if the partial pressure of A is high

then, KPA >> 1 almost complete coverage
and,
rate = kPB
means: the rate determining step is the
collision of B with the adsorbed species
if the partial pressure of A if low
then, KPA << 1
and,
rate = kKPAPB
means: the extent of surface coverage is
important in the rate determination

ELEY-RIDEAL

LANGMUIR-HINSHELWOOD

LANGMUIR-RIDEAL-

thank you!
jose s. solis, ph.d.
imee s. martinez, ph. d.
institute of chemistry
university of the philippines
diliman, quezon city