Surface Chemistry and Adsorption Processes
SURFACE
CHEMISTRY
INTRODUCTION
Surface
chemistry
is
the
study
of
processes
that
occur
at
the
interface
of
two
bulk
phases.
The
bulk
phases
can
be
of
the
type
:
L
i
q
u
i
d
-
l
i
q
u
i
d
T
Y
PES
•
ADSORPTION:
is
the
adhesion
of
atoms, ions,
biomolecules
or
molecules
of
gas,
liquid,
or
dissolved solids
to
a
surface.
•
ABSORPTION:
is
a
physical
or
chemical
phenomenon
or
a
process
in
which
atoms,
molecules,
or
ions
enter
some
bulk
phase
-
gas,
liquid,
or
solid
material.
Adsorption
on
activated
charcoal.
A
bs
o
r
p
t
i
on
through
a
membrane
Ads
o
r
p
t
i
o
n
Absorption
(“partitioning”)
PHASE
I
PHASE
2
Adsorbate
Adsorbent
Adsorption
The
accumulation
of
molecular
species
at
the
surface
rather
than
in
the
bulk
of
a
solid
or
liquid
is
termed
adsorption
.
The
molecular
species
or
substance,
which
concentrates
or
accumulates
at
the
surface
is
termed
adsorbate
and
the
material
on
the
surface
of
which
the
adsorption
takes
place
is
called
adsorbent.
Action
of
adsorption
(i)
If
a
gas
like
O
2
,
H
2
,
CO,
Cl
2
,
NH
3
or
SO
2
is
taken in
a
closed
vessel
containing
powdered
charcoal,
it
is
observed
that
the
pressure
of
the
gas
in
the
enclosed
vessel
decreases.
The
gas
molecules
concentrate
at the
surface
of
the
charcoal, i.e.,
gases
are
adsorbed
at
the
surface.
(ii)
In
a
solution
of
an
organic
dye,
say
methylene
blue,
when
animal charcoal
is
added
and
the
solution
is
well
shaken,
it
is
observed
that
the
filtrate
turns
colourless.
The
molecules
of
the
dye,
thus,
accumulate
on
the
surface
of
charcoal, i.e.,
are
adsorbed.
(iii)
Aqueous
solution
of
raw
sugar,
when
passed
over
beds
of
animal
charcoal,
becomes
colourless
as
the
colouring
substances
are
adsorbed
by
the
charcoal.
(iv)
The
air
becomes
dry
in
the
presence
of
silica
gel
because
the
water
molecules
get
adsorbed
on
the
surface
of
the
gel.
The
process
of
removing
an
adsorbed
substance
from
a
surface
on
which
it
is
adsorbed
is
called
desorption.
Difference between
adsoprtion
and
absorption
In
adsorption,
the
substance
is
concentrated
only
at
the
surface
and
does
not
penetrate
through
the
surface
to
the
bulk
of
the
adsorbent,
while
in
absorption
the
substance
is
uniformly
distributed
throughout
the
bulk
of
the
solid.
A
distinction
can
be
made
between
absorption
and
adsorption
by
taking
an
example
of
water
vapour.
Water
vapours
are
absorbed
by
anhydrous
calcium
chloride
but
adsorbed
by
silica
gel.
In
other
words,
in
adsorption
the
concentration
of
the
adsorbate
increases
only
at
the
surface
of
the
adsorbent,
while
in
absorption
the
concentration
is
uniform
throughout
the
bulk
of
the
solid.
Both
adsorption
and
absorption
can
take
place
simultaneously
also.
The
term
sorption
is
used
to
describe
both
the
processes.
Mechanism
of
adsoprtion
Inside
the
adsorbent
all
the
forces
acting
between
the
particles
are
mutually
balanced
but
on
the
surface
the
particles
are
not
surrounded
by
atoms
or
molecules
of
their
kind
on
all
sides,
and
hence
they
possess
unbalanced
or
residual
attractive
forces.
These
forces
of
the
adsorbent
are
responsible
for
attracting
the
adsorbate
particles
on
its
surface.
The
extent
of
adsorption
increases
with
the
increase
of
surface
area
per
unit
mass
of
the
adsorbent
at
a
given
temperature
and
pressure.
Another
important
factor
featuring
adsorption
is
the
heat
of
adsorption.
During
adsorption,
there
is
always
a
decrease
in
residual
forces
of
the
surface,
i.e.,
there
is
decrease
in
surface
energy
which
appears
as
heat.
Adsorption,
therefore,
is
invariably
an
exothermic
process.
In
other
words,
∆H
of
adsorption
is
always
negative.
When
a
gas
is
adsorbed,
the
freedom
of
movement
of
its
molecules
become
restricted.
This
amounts
to
decrease
in
the
entropy
of
the
gas
after
adsorption,
i.e.,
∆S
is
negative.
Adsorption
is
thus
accompanied
by
decrease
in
enthalpy
as
well
as
decrease
in
entropy
of
the
system.
For
a
process
to
be spontaneous,
the
thermodynamic
requirement
is
that,
at
constant
temperature
and
pressure,
∆G
must
be
negative,
i.e.,
there
is
a
decrease
in
Gibbs
energy.
On
the
basis
of
equation,
∆G
=
∆H
–
T∆S,
∆G
can
be
negative
if
∆H
has
sufficiently
high
negative
value
as
–
T∆S
is
positive.
Thus,
in
an
adsorption
process,
which
is
spontaneous,
a
combination
of
these
two
factors
makes
∆G
negative.
As
the
adsorption
proceeds,
∆H
becomes
less
and
less
negative
ultimately
∆H
becomes
equal
to
T∆S
and
∆G
becomes
zero.
At
this
state
equilibrium
is
attained.
Types
of
adsorption
There
are
mainly
two
types
of
adsorption
of
gases
on
solids.
If
accumulation
of
gas
on
the
surface
of
a
solid
occurs
on
account
of
weak
van
der
Waals’
forces,
the
adsorption
is
termed
as
physical
adsorption
or
physisorption
.
When
the
gas
molecules
or
atoms
are
held
to
the
solid
surface
by
chemical
bonds,
the
adsorption
is
termed
chemical
adsorption
or
chemisorption
.
The
chemical
bonds
may
be
covalent
or
ionic
in
nature.
Chemisorption
involves
a
high
energy
of
activation
and
is,
therefore,
often
referred
to
as
activated
adsorption.
Sometimes
these
two
processes
occur
simultaneously
and
it
is
not
easy
to
ascertain
the
type
of
adsorption.
A
physical
adsorption
at
low
temperature
may
pass
into
chemisorption
as
the
temperature
is
increased.
For
example,
dihydrogen
is
first
adsorbed
on
nickel
by
van
der
Waals’
forces.
Molecules
of
hydrogen
then
dissociate
to
form
hydrogen
atoms
which
are
held
on
the
surface
by
chemisorption.
Characteristics
of
physisorption
(i)
Lack
of
specificity:
A
given
surface
of
an
adsorbent
does
not
show
any
preference
for
a
particular
gas
as
the
van
der
Waals’
forces
are
universal.
(ii)
Nature
of
adsorbate:
The
amount
of
gas
adsorbed
by
a
solid
depends
on
the
nature
of
gas.
In
general,
easily
liquefiable
gases
(i.e.,
with
higher
critical
temperatures)
are
readily
adsorbed
as
van
der
Waals’
forces
are
stronger
near
the
critical
temperatures.
(iii)
Reversible
nature:
Physical
adsorption
of
a
gas
by
a
solid
is
generally reversible.
Thus,
More
of
gas
is
adsorbed
when
pressure
is
increased
as
the
volume
of
the
gas
decreases
and
the
gas
can
be
removed
by
decreasing
pressure.
Since
the
adsorption
process
is
exothermic,
the
physical
adsorption
occurs
readily
at
low
temperature
and
decreases
with
increasing
temperature
(Le-Chatelier’s
principle).
(iv)
Surface
area
of
adsorbent:
The
extent
of
adsorption
increases
with
the
increase
of
surface
area
of
the
adsorbent.
Thus,
finely
divided
metals
and
porous
substances
having
large
surface
areas
are
good
adsorbents.
(v)
Enthalpy
of
adsorption:
No
doubt,
physical
adsorption
is
an
exothermic
process
but
its
enthalpy
of
adsorption
is
quite
low
(20–
40
kJ
mol
-1
).
This
is
because
the
attraction
between
gas
molecules
and
solid
surface
is
only
due
to
weak
van
der
Waals’
forces.
Characteristics
of
chemisorption
(i)
High
specificity:
Chemisorption
is
highly
specific
and
it
will
only
occur
if
there
is
some
possibility
of
chemical
bonding
between
adsorbent
and
adsorbate.
(ii)
Irreversibility:
As
chemisorption
involves
compound
formation,
it
is
usually
irreversible
in
nature.
-
Chemisorption
is
also
an
exothermic
process
but
the
process
is
very
slow
at
low
temperatures
on
account
of
high
energy
of
activation.
Like
most
chemical
changes,
adsorption
often
increases
with
rise
of
temperature.
-Physisorption
of
a
gas
adsorbed
at
low
temperature
may
change
into
chemisorption
at
a
high
temperature.
Usually
high
pressure
is
also
favourable
for
chemisorption.
(iii)
Surface
area:
Like
physical
adsorption,
chemisorption
also
increases
with
increase
of
surface
area
of
the
adsorbent.
(iv)
Enthalpy
of
adsorption:
Enthalpy
of
chemisorption
is
high
(80-240
kJ
mol-1)
as
it
involves
chemical
bond
formation.
Adsorption
isotherms
The
variation
in
the
amount
of
gas
adsorbed
by
the
adsorbent
with
pressure
at
constant
temperature
can
be
expressed
by
means
of
a
curve
termed
as
adsorption
isotherm.
Freundlich
adsorption
isotherm:
Freundlich,
in
1909,
gave
an
empirical
relationship
between
the
quantity
of
gas
adsorbed
by
unit
mass
of
solid
adsorbent
and
pressure
at
a
particular
temperature.
The
relationship
can
be
expressed
by
the
following
equation:
where
x
is
the
mass
of
the
gas
adsorbed
on
mass
m
of
the
adsorbent
at
pressure
P,
k
and
n
are
constants
which
depend
on
the
nature
of
the
adsorbent
and
the
gas
at
a
particular
temperature.
The
relationship
is
generally
represented
in
the
form
of
a
curve
where
mass
of
the
gas
adsorbed
per
gram
of
the
adsorbent
is
plotted
against
pressure
.
These
curves
indicate
that
at
a
fixed
pressure,
there
is
a
decrease
in
physical
adsorption
with
increase
in
temperature.
These
curves
always
seem
to
approach
saturation
at
high
pressure.
Taking
log
on
both
sides
of
equation
we
get
The
validity
of
Freundlich
isotherm
can
be
verified
by
plotting
log
x/m
on
y-axis
(ordinate
)
and
log
p
on
x-axis
(abscissa).
If
it
comes
to
be
a
straight
line,
the
Freundlich
isotherm
is
valid,
otherwise
not
.
The
slope
of
the
straight
line
gives
the
value
of
1/n
.
The
intercept
on
the
y-
axis
gives
the
value
of
log
k.
Freundlich
isotherm
explains
the
behaviour
of
adsorption in
an
approximate
manner.
The
factor
1
can
have
values
between
0
and
1
.
Thus,
above
equation
holds
good
over
a
limited
range
of
pressure.
When1/n
=
0,
x/m
=
constant,
the
adsorption
is
independent
of
pressure.
nm
When
1/n
=
1,
x/m
=
k
p,
i.e.
x
∝
p,
the
adsorption
varies
directly
with
pressure.
Both
the
conditions
are
supported
by
experimental
results.
The
experimental
isotherms
always
seem
to
approach
saturation
at
high
pressure.
This
cannot
be
explained
by
Freundlich
isotherm.
Thus,
it
fails
at
high
pressure.
Adsorption
from
solution
phase
Solids can
adsorb
solutes
from
solutions
also. When
a
solution
of
acetic
acid
in
acetic
acid
is
shaken
with
charcoal
a
part
of
it
is
adsorbed
by
charcoal
and
the
concentration
of
the
acid
decreases
in
the
solution.
.
The
following
observations
have
been
made
in
the
case
of
adsorption
from
solution
phase:
(i)
The
extent
of
adsorption
decreases
with
an
increase
in
temperature.
(ii)
The
extent
of
adsorption
increases
with
an
increase
of
surface
area
of
the
adsorbent.
(iii)
The
extent
of
adsorption
depends
on
the
concentration
of
the
solute
in
solution.
(iv)
The
extent
of
adsorption
depends
on
the
nature
of
the
adsorbent
and
the
adsorbate.
Freundlich’s
equation approximately
describes
the
behaviour
of
adsorption
from
solution
with
a
difference
that
instead
of
pressure,
concentration
of
the
solution
is
taken
into
account,
i.e.
Where
C
is
the
equilibrium
concentration,
i.e.,
when
adsorption
is
complete.
On
taking
logarithm
of
the
above
equation,
we
have
Plotting
log
x/m
against
log
C
a
straight
line
is
obtained
which
shows
the
validity
of
Freundlich
isotherm.
This
can
be
tested
experimentally
by
taking
solutions
of
different
concentrations
of
acetic
acid.
Equal
volumes
of
solutions
are
added
to
equal
amounts
of
charcoal
in
different
flasks.
The
final
concentration
is
determined in
each
flask
after
adsorption.
The
difference
in
the
initial
and
final
concentrations
give
the
value
of
x.
Using
the
above
equation,
validity
of
Freundlich
isotherm
can
be
established.
Applications
of
adsorption
(i)
Production
of
high
vacuum:
The
remaining
traces
of
air
can
be
adsorbed
by
charcoal
from
a
vessel
evacuated
by
a
vacuum
pump
to
give
a
very
high
vacuum.
(ii)
Gas
masks:
Gas
mask
(a
device
which
consists
of
activated
charcoal
or
mixture
of
adsorbents)
is
usually
used
for
breathing
in
coal
mines
to
adsorb
poisonous
gases.
(iii)
Control
of
humidity:
Silica
and
aluminium
gels
are
used
as
adsorbents
for
removing
moisture
and
controlling
humidity.
(iv)
Removal
of
colouring
matter
from
solutions
:
Animal
charcoal
removes
colours
of
solutions
by
adsorbing
coloured
impurities.
(v)
Heterogeneous
catalysis
:
Adsorption
of
reactants
on
the
solid
surface
of
the
catalysts
increases
the
rate
of
reaction.
There
are
many
gaseous
reactions
of
industrial
importance
involving
solid
catalysts.
(vi)
Separation
of
inert
gases:
Due
to
the
difference
in
degree
of
adsorption
of
gases
by
charcoal,
a
mixture
of
noble
gases
can
be
separated
by
adsorption
on
coconut
charcoal
at
different
temperatures.
(vii)
In
curing
diseases:
A
number
of
drugs
are
used
to
kill
germs
by
getting
adsorbed
on
them.
(viii)
Froth
floatation
process
:
A
low
grade
sulphide
ore
is
concentrated
by
separating
it
from
silica
and
other
earthy
matter
by
this
method
using
pine
oil
and
frothing
agent
.
(ix)
Adsorption
indicators
:
Surfaces
of
certain
precipitates
such
as
silver
halides
have
the
property
of
adsorbing
some
dyes
like
eosin,
fluorescein,
etc.
and
thereby
producing
a
characteristic
colour
at
the
end
point.
(x)
Chromatographic
analysis:
Chromatographic
analysis
based
on
the
phenomenon
of
adsorption
finds
a
number
of
applications
in
analytical
and
industrial
fields.
Electrophoresis
When
electric
potential
is
applied
across
two
platinum
electrodes
dipping in
a
colloidal
solution,
the
colloidal
particles
move
towards
one
or
the
other
electrode.
The
movement
of
colloidal
particles
under
an
applied
electric
potential
is
called
electrophoresis.
Positively
charged
particles
move
towards
the
cathode
while
negatively
charged
particles
move
towards
the
anode
When
electrophoresis
that
is.,movement
of
particles
is
prevented
by
some
suitable
means,
it
is
observed
that
the
dispersion
medium
begins
to
move
in
an
electric
field.
This
phenomenon
is
termed
electroosmosis.
Surface chemistry is the study of processes at the interface of two bulk phases, such as liquid-liquid interactions. Adsorption and absorption are key phenomena where atoms, ions, or molecules adhere to surfaces or enter bulk phases. The accumulation of molecular species at the surface, known as adsorption, has various practical applications like gas purification and dye removal. This content explores the differences between adsorption and absorption, highlighting examples and the action of adsorption in various scenarios.
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Presentation Transcript
INTRODUCTION Surface chemistry is the study of processes that occur at the interface of two bulk phases. The bulk phases can be of the type: Liquid -liquid
TYPES ADSORPTION: is the adhesion of atoms, ions, biomolecules or molecules of dissolvedsolidsto asurface. gas, liquid, or ABSORPTION: is a physical or phenomenon or a process in which atoms, molecules, or ions enter some bulk phase - gas,liquid, or solidmaterial. chemical
Adsorption onactivated charcoal.
Absorption through a membrane
Adsorption Adsorbate Adsorbent Absorption( partitioning ) PHASEI PHASE2
Adsorption Theaccumulation of molecular speciesat the surfacerather than in the bulk of asolid or liquid istermed adsorption . The molecular species or substance, which concentrates or accumulatesat the surfaceistermed adsorbateandthe material on the surface of which the adsorption takes place is called adsorbent.
Action ofadsorption (i) If a gas like O2, H2, CO, Cl2, NH3 or SO2is taken in a closed vessel containing powdered charcoal,it isobservedthat the pressure of the gasin the enclosedvessel decreases. The gas molecules concentrate at the surface of the charcoal, i.e., gases areadsorbedat the surface. (ii) In a solution of an organic dye, say methylene blue, when animal charcoal is addedandthe solution iswell shaken,it isobservedthat the filtrate turns colourless. The molecules of the dye, thus, accumulate on the surface of charcoal, i.e., are adsorbed. (iii) Aqueous solution of raw sugar,when passedover bedsof animalcharcoal, becomescolourless asthe colouringsubstancesareadsorbedbythe charcoal. (iv) Theair becomesdry in the presenceof silicagel becausethe water molecules get adsorbedon the surfaceof the gel. Theprocessof removing anadsorbedsubstancefrom asurfaceon which it is adsorbed is calleddesorption.
Difference between adsoprtion andabsorption In adsorption, the substanceisconcentrated only at the surfaceand doesnot penetrate through the surfaceto the bulk of the adsorbent, while in absorption the substance is uniformly distributed throughout the bulk of the solid. A distinction can be made between absorption and adsorption by takinganexample of water vapour.Watervapoursareabsorbedby anhydrous calciumchloridebut adsorbed bysilicagel. In other words, in adsorption the concentration of the adsorbate increasesonly at the surfaceof the adsorbent, while in absorption the concentrationisuniform throughout the bulk of the solid. Both adsorption andabsorptioncantake placesimultaneouslyalso. Theterm sorption isusedto describeboth the processes.
Mechanism of adsoprtion Inside the adsorbent all the forces acting between the particles are mutually balanced but on the surface the particles are not surrounded by atoms or molecules of their kind on all sides, and hence they possess unbalanced or residual attractive forces. These forces of the adsorbent are responsible for attracting the adsorbate particles on its surface.Theextent of adsorption increaseswith the increaseof surfaceareaper unit massof the adsorbent at agiventemperatureandpressure.
Another important factor featuring adsorption isthe heat of adsorption. During adsorption, there is always a decrease in residual forces of the surface,i.e.,thereisdecreasein surfaceenergywhich appearsasheat. Adsorption, therefore, is invariably an exothermic process. In other words, H of adsorption is always negative. When a gas is adsorbed, the freedom of movement of its molecules become restricted. Thisamounts to decrease in the entropyof the gasafter adsorption,i.e., Sisnegative. Adsorption isthus accompaniedby decreasein enthalpy aswell asdecrease in entropy of the system. For a process to be spontaneous, the thermodynamic requirementisthat, at constant temperatureandpressure, Gmustbenegative,i.e.,there isadecreasein Gibbsenergy. On the basis of equation, G = H T S, G can be negative if H has sufficiently high negative value as T Sispositive. Thus,in anadsorption process,which isspontaneous, acombination of these two factors makes G negative.As the adsorption proceeds, H becomes less and less negative ultimately H becomes equal to T S and G becomes zero. At this stateequilibrium is attained.
Types ofadsorption There are mainly two types of adsorption of gases on solids. If accumulationof gason the surfaceof asolid occurson accountof weak vanderWaals forces,the adsorptionistermedasphysicaladsorptionor physisorption. Whenthe gasmolecules or atomsareheld to the solidsurfacebychemical bonds,the adsorptionistermedchemicaladsorptionorchemisorption. The chemical bonds may be covalent or ionic in nature. Chemisorption involvesahigh energyof activationandis,therefore, often referredto as activated adsorption. Sometimes these two processes occur simultaneously and it is not easyto ascertain the type of adsorption. Aphysical adsorption at low temperature maypassinto chemisorption asthe temperature isincreased. Forexample, dihydrogenisfirst adsorbedon nickelbyvanderWaals forces. Molecules of hydrogen then dissociate to form hydrogen atoms which are heldon the surfacebychemisorption.
Characteristics ofphysisorption (i) Lackofspecificity: Agivensurface of anadsorbent doesnot showanypreference for a particulargasasthe vander Waals forces areuniversal. (ii) Natureofadsorbate:Theamount of gasadsorbedbya soliddependson the nature of gas.In general,easilyliquefiablegases(i.e., with higher criticaltemperatures)are readilyadsorbedasvander Waals forces arestronger nearthe criticaltemperatures. (iii) Reversible nature:Physical adsorption of a gas by a solid is generally reversible. Thus, More of gas is adsorbed when pressure is increased as the volume of the gas decreasesandthe gascanberemoved bydecreasing pressure.Sincethe adsorption processisexothermic,the physical adsorption occursreadily at low temperatureand decreaseswith increasingtemperature(Le-Chatelier sprinciple). (iv) Surface area of adsorbent:The extent of adsorption increases with the increase of surface areaof the adsorbent.Thus,finely dividedmetalsandporous substanceshaving largesurfaceareasaregood adsorbents. (v) Enthalpyofadsorption:Nodoubt, physical adsorption isanexothermic processbut its enthalpy of adsorption isquite low (20 40kJmol-1).Thisisbecausethe attraction between gasmoleculesandsolid surface isonlydueto weakvanderWaals forces.
Characteristicsof chemisorption (i)Highspecificity:Chemisorption ishighlyspecific andit will only occur if there is some possibility of chemical bonding between adsorbent andadsorbate. (ii) Irreversibility:As chemisorption involves compound formation, it isusuallyirreversibleinnature. -Chemisorption is also an exothermic process but the process is very slow at low temperatures on accountof highenergy of activation. Like most chemical changes, adsorption often increases with rise of temperature. -Physisorption of agasadsorbed at low temperature maychangeinto chemisorption at a high temperature. Usually high pressure is also favourable forchemisorption.
(iii) Surfacearea:Likephysicaladsorption, chemisorption also increaseswith increaseof surfaceareaof the adsorbent. (iv) Enthalpyof adsorption:Enthalpy of chemisorption ishigh (80-240kJmol-1)asit involves chemicalbond formation.
Adsorptionisotherms Thevariation in the amount of gasadsorbed by the adsorbent with pressure at constant temperature can be expressed by meansof acurve termed asadsorption isotherm. Freundlichadsorption isotherm: Freundlich,in 1909,gavean empirical relationship between the quantity of gasadsorbed by unit mass of solid adsorbent and pressure at a particular temperature. The relationship can be expressed by the following equation:
where x is the mass of the gas adsorbed on mass m of the adsorbent at pressure P, k and n areconstantswhich dependon the nature of the adsorbent and the gas at a particulartemperature. The relationship is generally representedin the form of acurve where mass of the gas adsorbed per gram of the adsorbent is plotted against pressure. These curves indicate that at a fixed pressure, thereis a decrease in physical adsorption with increase in temperature. These curves always seem to approach saturation at highpressure.
Takinglogon both sidesof equation we get Thevalidityof Freundlichisothermcanbe verified by plotting log x/m on y-axis (ordinate) andlogp on x-axis(abscissa). If it comes to be a straight line, the Freundlich isotherm is valid, otherwise not .Theslopeof the straight linegives the valueof 1/n.Theintercept on the y- axisgivesthe valueof logk. Freundlich isotherm explains the behaviour of adsorption in an approximate manner. The factor 1 can have values between 0 and 1 . Thus, aboveequation holdsgood overalimited range ofpressure.
When1/n=0,x/m=constant,the adsorption isindependent of pressure.nm When1/n=1,x/m=k p, i.e.x p, the adsorptionvariesdirectly with pressure. Both the conditions aresupported by experimental results. The experimental isotherms always seem to approach saturation at highpressure. Thiscannot beexplained by Freundlich isotherm.Thus,it fails at highpressure.
Adsorption fromsolution phase Solids can adsorb solutes from solutions also. When a solution of acetic acid in acetic acid is shaken with charcoal a part of it is adsorbed by charcoalandthe concentrationof the aciddecreasesin the solution. .The following observations have been made in the case of adsorption from solution phase: (i) Theextent of adsorptiondecreaseswith anincreasein temperature. (ii) Theextent of adsorptionincreaseswith anincreaseof surfaceareaof the adsorbent. (iii) Theextent of adsorptiondependson the concentrationof the solute in solution. (iv) Theextent of adsorptiondependson the natureof the adsorbentand the adsorbate.
Freundlichs equation approximately describes the behaviour of adsorptionfrom solution with adifferencethat insteadof pressure, concentrationof the solution istakeninto account,i.e. WhereCisthe equilibrium concentration,i.e.,when adsorptionis complete.Ontakinglogarithmof the aboveequation,we have Plotting log x/magainstlog Castraight line isobtainedwhich showsthe validity of Freundlichisotherm. This can be tested experimentally by taking solutions of different concentrations of aceticacid.Equalvolumesof solutions areaddedto equalamountsof charcoalin differentflasks. The final concentration is determined in each flask after adsorption. The differencein the initial andfinal concentrationsgivethe valueof x.Using the aboveequation,validity of Freundlich isothermcanbeestablished.
Applications ofadsorption (i) Production of high vacuum: Theremaining traces of air can beadsorbedby charcoalfrom avesselevacuatedby avacuum pump to give averyhigh vacuum. (ii) Gas masks:Gas mask (a device which consists ofactivated charcoal or mixture of adsorbents) is usually used for breathing in coalmines to adsorb poisonous gases. (iii) Control of humidity: Silicaandaluminium gelsareusedas adsorbents for removing moisture andcontrolling humidity.
(iv) Removalof colouring matter from solutions:Animalcharcoalremoves coloursof solutions byadsorbingcolouredimpurities. (v) Heterogeneouscatalysis:Adsorptionof reactants on the solidsurfaceof the catalysts increases the rate of reaction. There are many gaseous reactionsof industrial importanceinvolving solidcatalysts. (vi) Separation of inert gases:Dueto the differencein degreeof adsorption of gases by charcoal, a mixture of noble gases can be separated by adsorptionon coconutcharcoalat different temperatures. (vii) In curing diseases:Anumberof drugsareusedto kill germsbygetting adsorbed onthem. (viii) Froth floatation process: Alow grade sulphide ore is concentrated by separating it from silica and other earthy matter by this method using pine oil and frothingagent . (ix) Adsorption indicators: Surfaces of certain precipitates such as silver halideshavethe property of adsorbing somedyeslike eosin, fluorescein, etc.andtherebyproducingacharacteristiccolour at the endpoint.
(x) Chromatographic analysis: Chromatographicanalysis based on the phenomenon of adsorption finds a number of applicationsin analytical andindustrial fields.
Electrophoresis When electric potential is applied across two platinum electrodes dipping in a colloidal solution, the colloidal particles movetowardsoneor the other electrode. The movement of colloidal particles under an applied electric potential is called electrophoresis. Positively charged particles movetowardsthe cathode while negatively charged particles move towards theanode When electrophoresis that is.,movement of particles ispreventedbysomesuitable means, it is observed that the dispersion medium begins to move in an electric field. This phenomenon is termed electroosmosis.
