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SAINT FRANCIS DE SALES COLLEGE ,

SEMINARY HILLS , NAGPUR.

DEPARTMENT OF CHEMISTRY
TOPIC : SURFACE PHENOMENA

PRESENTED BY: GUIDED BY :

SHIVANI C. NAMJOSHI MS. PRIYA YADAV
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CONTENTS

INTRODUCTION
RECAPITULATION OF SURFACE TENSION
ADSORPTION
ADSORPTION ISOTHERMS
FREUNDLICH ADSORPTION ISOTHERM
LANGMUIR THEORY
GIBBS ADSORPTION ISOTHERM
BET THEORY AND ESTIMATION OF SURFACE AREA

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INTRODUCTION
Surface chemistry deals with the study of phenomena that occur at
the surfaces or interfaces of substances, like adsorption,
heterogeneous catalysis, formation of colloids, corrosion,
crystallization, dissolution, electrode processes, chromatography etc.
Surface chemistry finds its applications in industry as well as in daily
life.

What is surface?

 A boundary separating two phases is called a surface or

interface.
 The physical boundary of any condensed phase like liquid or
solid is considered as surface.
 It separates one phase from the other.
 It can be considered as series of points which make a plane or
layer where one phase ends and the other begins.
 The surface may be uni-layered or multi-layered.

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RECAPITULATION OF SURFACE TENSION

• Surface tension is defined as force acting per unit length
perpendicular to the line drawn on the surface of liquid.

• Its SI unit is N/m and CGS unit is dyne/cm.

Molecules at the
surface
Molecules in the bulk

• Surface tension is characteristic property of liquid state.

Gaseous and state do not exhibit this property.

• As given above , in the beaker, the molecules in the bulk of

liquid is surrounded by other neighbouring molecules of the
liquid. Hence, the molecule in the bulk experiences equal forces
of attraction from all the sides exerted by surrounding
molecules. Hence, all the equal and opposite forces are
cancelled and there is no resultant force of attraction acting on
the molecule.

• However in the case of the molecules at the surface of the

liquid there are molecules of the liquid below it . but there are
no molecules of the liquid above it.
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• Hence on the surface liquid molecules experiences force of

attraction in downward direction towards the bulk of the liquid.

• There are no forces of attraction in upward direction therefore

surface of liquid is always under tension and behaves as a
stretched membrane and tends to contract.

Adsorption
It is defined as the phenomenon of accumulation of higher
concentration of one substance on the surface of another than in
bulk.

The phenomenon of attracting and retaining the molecules of the

substance on the surface of a liquid or solid is known as adsorption.

Adsorbate

adsorbent

• The substance adsorbed on the surface of another is called as

adsorbate or adsorbed phase.
• A substance which adsorbs another substance on its surface is
called adsorbent.

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• Desorption : The process removal of adsorbed from the surface

is known as desorption. It is the reverse of adsorption.

CHARACTERISTICS OF ADSORPTION AND ABSORPTION

ADSORPTION

• It is a surface phenomenon.
• It is a rapid process.
• It is affected by surface area of the adsorbent.
• Rate steadily increases and reaches equilibrium.
• Concentration on the surface of adsorbent is different
from that in the bulk.

ABSORPTION

• It is a bulk phenomenon.
• It is a slow process.
• There is negligible effect of surface area.
• Rate occurs at a uniform rate.
• Concentration is same throughout the material

TYPES OF ADSORPTION

1.Physical adsorption
2.Chemical adsorption
1.Physical adsorption : - In this type of adsorption the
forces between particles of adsorbate and adsorbent are
physical in nature.
• These forces, called Van der Waals forces , are similar to
the forces that cause the condensation of gas into liquid.
Example : 1. Adsorption of various gases on charcoal .
2. Adsorption of acetic acid or oxalic acid in
solution by charcoal.

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2.Chemical adsorption : In this type of adsorption, the

adsorbed molecules are attached to the surface of
adsorbent by chemical bonds of the same type as the
covalent bonds between atoms in a molecule.
Example : 1. The adsorption of CO on tungsten .
Adsorption isotherms
The process of Adsorption is usually studied through graphs know as
adsorption isotherm. It is the graph between the amounts of
adsorbate .

What is Adsorption Isotherm?

The process of Adsorption is usually studied through graphs know as

adsorption isotherm. It is the graph between the amounts of
adsorbate (x) adsorbed on the surface of adsorbent (m) and pressure
at constant temperature. Different adsorption isotherms are
Freundlich, Langmuir and BET theory.

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Freundlich Adsorption Isotherm

• In 1909, freundlich gave an emperical expression representing
the isothermal variation of adsorption of a quantity of gas
adsorbed by a unit mass of solid adsorbent with pressure.

x/m α p¹/n

x/m = k p¹/n

This equation is FREUNDLICH ADSORBTION ISOTHERM .

where m = mass of adsorbent

x = mass of adsorbate

x/m = amount of adsorption

K,n = constant at particular T for given adsorbent and

adsorbate

At low pressure , extent of adsorption is directly proportional to

pressure.

x/m α p

x/m = k p (n=1)

• At high pressure, extent of adsorption is independant of

pressure.

x/m = k p° (n=∞)

• At moderate pressure, n>1

x/m = k p ¹/n

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• As per freundlich adsorption equation ,

x/m = kp¹/n

Taking log of both sides

log x/m =log k + ¹/n log p

• The above equation is comparable with the equation of line

y= mx+c

Where m= slope of line and

c = intercept on y axis

• Plotting a graph between log (x/m) and log p , we get a straight

line with value of slope = ¹/n and log k is the y axis intercept.

• It is applicable within certain limits of pressure. At high

pressure it shows deviation.

• The values of constants k and n changes with temperature.

• The freundlich adsorbtion isotherm is an emperical expression ,

it does not have any therotical basis.

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Langmuir theory
Assumptions
• Surface uniform

• Monolayer adsorbtion

• No interaction between adsorbed molecules and adsorbed molecules

immobile.

• Adsorbed molecule and desorbed molecule are in equilibrium as well as

exhibit ideal gas behaviour.

Derivation
• Langmuir Equation which depicts a relationship between the number of
active sites of the surface undergoing adsorption (i.e. extent of
adsorption) and pressure.

• To derive langmuir equation a new parameter Ɵ is introduced.

• Let Ɵ be the number of sites of the surface covered by gaseous

molecules.

• Therefore, fraction of surface which is unoccupied by gaseous molecules

is 1-Ɵ

• Rate of forward direction depends upon two factors: Number of sited

available on the surface of adsorbent, (1 – θ) and Pressure, P.

• Therefore rate of forward reaction is directly proportional to both

mentioned factors.

Rate of forward reaction α P (1-Ɵ)

Rate of adsorption α P (1-Ɵ)

Or Rate of adsorption = k₁ P (1-Ɵ)

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• Similarly, Rate of backward reaction or Rate of Desorption depends upon

number of sites occupied by the gaseous molecules on the surface of
adsorbent.

Rate of desorption α Ɵ

Or Rate of desorption = k₂Ɵ

• At equilibrium, rate of adsorption is equal to rate of desorption.

K₁ P (1 – θ) = K₂ θ

• We can solve the above equation to write it in terms of θ.

K1P – K1P θ = K2 θ

K1P = K2 θ + K1P θ

K1P = (K2 + K1P) θ

• We can solve the above equation to write it in terms of θ

Ɵ = k₁ p

K2 + K1P

• Divide numerator and denominator on RHS by K2, we get

Ɵ= k₁/k₂ p
k₂/k₂ + k₁/k₂ p

• Now put k₁/k₂ = k

Ɵ = kp

1+ k p

• This is known as Langmuir adsorption isotherm

Limitations
• The adsorbed gas has to behave ideally in the vapor phase. This
condition can be fulfilled at low pressure conditions only and monolayer
formation is only possible.
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GIBBS ADSORPTION ISOTHERM

The equation represents the exact relationship between adsorption and
change in surface tension of a solvent due to prescence of a solute which is the
eqation derived by J.W. Gibbs.

DERIVATION

For a system containing two components gibbs free energy is given as

G = n₁ u₁ + n₂ u₂ 1

Where = n₁, n₂ are no. of moles of two components.

u₁ , u₂ are chemical potential of two components.

Since there is surface activity , there is surface free energy .

Therefore equation is given as :

G = n₁ u₁ + n₂ u₂ +ƴ σ 2

Where ƴ is surface energy numerically equal to surface tension

σ is surface area

Taking complete differential of this equation

We get ,

dG = n₁ d u₁ + u₁ d n₁+ n₂ d u₂ + u₂ d n₂ +ƴ d σ + σ d ƴ 3

The total gibbs free energy depends on five vairiables and it is function of
them.

G = f ( T, P, n ₁, n₂, σ )

dG = ∂G dT + ∂G dP + ∂G dn1 + ∂G dn₂ + ∂G dσ

∂T p, n₁, n₂, σ ∂p t, n₁, n₂, σ ∂n₁ t, p, n₂, σ ∂n₂ t, p, n₁, σ ∂σ p, n₁, n₂,t

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But according to thermodynamics ,

∂G / ∂T p, n1. n2, σ = -s ∂G / ∂P t,, n1, n2 σ = v ∂G / ∂n₁ t, p, n2 , σ = u₁

∂G/ ∂n₂ t, p, n₁, σ = u₂ ∂G/ ∂σ t, p, n₁, n₂ =ƴ

Therefore , change in gibbs energy i s

dG = -sdT + vdP + u₁dn₁ + u₂dn₂ + ƴdσ 5

If we consider that system is at constant temperature and pressure then, dT , dP = 0

dG = u₁dn₁ + u₂dn₂ + ƴdσ 6

compairing equation 3 and equation 6 we get ,

n₁ d u₁ + n₂ d u₂ +ƴ d σ = 0 7

EQUATION No. 7 is the equation for SURFACE ACTIVITY.

Thus for bulk of liquid the corresponding will be

n₁° d u₁ + n₂° d u₂ = 0 8

du₁ = - n₂°/ n₁° du₂

Substitute this value in equation 7

n₁ ₋n₂°∕n₁° du₂ + n₂ du₂ + σdƴ = 0

n₂ ₋ n₁n₂° du₂ +σdƴ = 0

n₁°

-dƴ = n₂ ₋ n₁n₂° / n₁° 9

du₂ σ

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The RHS equation gives excess concentration of solute per unit area of surface is

denoted by ᴦ₂

ᴦ₂ = - dƴ / du₂ 10

The chemical potential of solute two is given by

u₂ = u₁* + RT ln a₂

where u₁* = is the chemical potential of pure solute in liquid phase. It is constant

its differential is zero

Taking diffrentail of above equation we get,

du₂ = RT d ln a₂

Substituting this value in equation no. 10

ᴦ₂ = - dƴ / RT d ln a₂

= - a₂ dƴ

RT da₂ T

When solution is very dilute activity is replaced by concentration

ᴦ₂ = - c₂ dƴ

RT dc₂ T

ᴦ₂ = -c dƴ

RT dc T

This Equation is called as GIBBS ADSORPTION ISOTHERM.

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BET THEORY
Brunauer–Emmett–Teller (BET) theory aims to explain the
physical adsorption of gas molecules on a solid surface and serves as the basis
for an important analysis technique for the measurement of the specific
surface area of materials.

In 1938, Stephen Brunauer, Paul Hugh Emmett, and Edward Teller published
the first article about the BET theory in the Journal of the American Chemical
Society.

The BET theory applies to systems of multilayer adsorption and usually utilizes
probing gases that do not chemically react with material surfaces as
adsorbates to quantify specific surface area.

Nitrogen is the most commonly employed gaseous adsorbate used for surface
probing by BET methods. For this reason, standard BET analysis is most often
conducted at the boiling temperature of N2 (77 K). Further probing adsorbates
are also utilized, albeit with lower frequency, allowing the measurement of
surface area at different temperatures and measurement scales.

These have included argon, carbon dioxide, and water.

Specific surface area is a scale-dependent property, with no single true value of

specific surface area definable, and thus quantities of specific surface area
determined through BET theory may depend on the adsorbate molecule
utilized and its adsorption cross section.

BET MODEL OF MULTILAYER ADSORPTION

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DERIVATION

p = 1 + c- 1 p

v (p - p°) vc vm c p°

Where p° = vapour pressure of liquified gas

p = pressure of gas

v = total volume of gas adsorbed

vm = volume of gas adsorbed when surface is covered

with monolayer

c = constant depending on nature of gas

• Energy of adsorption in first layer is E₁ and n layer is El

Thus BET equation can be written as :

c= exp E₁ - El

RT

The following equation can be written as :

v = vmcf 1

1-f 1 + (c – 1) f

Where v = total volume of gas adsorbed

vm = volume of gas adsorbed when surface is covered

with monolayer.

c = constant depending on nature and f = p / p°

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Verification of BET equation :

• For a given gas, the value of c and vm are constant.

considering equation 1 , graph is plotted between

p and p

v (p - p°) p°

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REFERENCE

• J.N. Gurtu

• Puri Sharma and Pathania

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THANK YOU

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