Surface chemistry

Surface chemistry deals with phenomena that occur at the surfaces or interfaces.
The interface or surface is represented by separating the bulk phases by a hyphen
or a slash. For example, the interface between a solid and a gas may be represented
by solid-gas or solid/gas. Due to complete miscibility, there is no interface between
the gases. The bulk phases that we come across in surface chemistry may be pure
compounds or solutions. The interface is normally a few molecules thick but its
area depends on the size of the particles of bulk phases. Many important
phenomena, noticeable amongst these being corrosion, electrode processes,
heterogeneous catalysis, dissolution and crystallisation occur at interfaces. The
subject of surface chemistry finds many applications in industry, analytical work
and daily life situations.
To accomplish surface studies meticulously, it becomes imperative to have a really
clean surface. Under very high vacuum of the order of 10 –8 to 10–9pascal, it is now
possible to obtain ultra clean surface of the metals. Solid materials with such clean
surfaces need to be stored in vacuum otherwise these will be covered by molecules
of the major components of air namely oxygen and nitrogen.

Adsorption
There are several examples, which reveal that the surface of a solid has the
tendency to attract and retain the molecules of the phase with which it comes into
contact. These molecules remain only at the surface and do not go deeper into the
bulk. 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. Adsorption is essentially a surface phenomenon. Solids, particularly in
finely divided state, have large surface area and therefore, charcoal, silica gel,
alumina gel, clay, colloids, metals in finely divided state, etc. act as good
adsorbents.

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Adsorption in action
(i) If a gas like O2, H2, CO, Cl2, NH3 or SO2 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.
It is clear from the above examples that solid surfaces can hold the gas or liquid
molecules by virtue of adsorption. The process of removing an adsorbed
substance from a surface on which it is adsorbed is called desorption.

Distinction between Adsorption 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. For example,
when a chalk stick is dipped in ink, the surface retains the colour of the ink due to
adsorption of coloured molecules while the solvent of the ink goes deeper into the
stick due to absorption. On breaking the chalk stick, it is found to be white from
inside. 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.

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Mechanism of Adsorption
Adsorption arises due to the fact that the surface particles of the adsorbent are not
in the same environment as the particles inside the bulk. 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
becomes restricted. This amount 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.

The extent of adsorption

The extent of surface coverage is normally expressed as the fractional coverage,
θ:

number of adsorption sites occupied

θ = number of adsorption sites available (eq.1)

The fractional coverage is often expressed in terms of the volume of adsorbate

adsorbed by θ = V/V∞, where V∞ is the volume of adsorbate corresponding to
complete monolayer coverage. The rate of adsorption, dθ/dt, is the rate of change

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of surface coverage, and can be determined by observing the change of fractional
coverage with time.

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, hydrogen gas 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. Some of the
important characteristics of both types of adsorption are described below:

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 vander Waals’ forces are
stronger near the critical temperatures. Thus, 1g of activated charcoal
adsorbs more sulphur dioxide (critical temperature 630K), than methane
(critical temperature 190K) which is still more than 4.5mL of dihydrogen
(critical temperature 33K).
(iii) Reversible nature: Physical adsorption of a gas by a solid is generally
reversible. Thus,
Solid + Gas = Gas/Solid + Heat
More of gas is adsorbed when pressure is increased as the volume of the
gas decreases (Le–Chateliers’s principle) and the gas can be removed by
decreasing pressure. Since the adsorption process is exothermic, the

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 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. For example, oxygen is adsorbed on metals by virtue of oxide
formation and hydrogen is adsorbed by transition metals due to hydride
formation.
(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.

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 Comparison of Physisorption and Chemisorption
Physisorption Chemisorption
1. It arises because of van der Waals’ 1. It is caused by chemical bond
forces. formation.
2. It is not specific in nature. 2. It is highly specific in nature.
3. It is reversible in nature. 3. It is irreversible.
4. It depends on the nature of gas. 4. It also depends on the nature of gas.
More easily liquefiable gases are Gases which can react with the
adsorbed readily. adsorbent show chemisorption.
5. Enthalpy of adsorption is low (20-40 5. Enthalpy of adsorption is high (80-
kJmol–1) in this case. 240 kJ mol–1) in this case.
6. Low temperature is favourable for 6. High temperature is favourable for
adsorption. It decreases with increase adsorption. It increases with the
of temperature. increase of temperature.
7. No appreciable activation energy is 7. High activation energy is sometimes
needed. needed.
8. It depends on the surface area. It 8. It also depends on the surface area. It
increases with an increase of surface too increases with an increase of
area. surface area.
9. It results into multimolecular layers 9. It results into unimolecular layer.
on adsorbent surface under high
pressure.

Adsorption Isotherms
The free gas and the adsorbed gas are in dynamic equilibrium, and the fractional
coverage of the surface depends on the pressure of the overlying gas. The variation
in the amount of gas adsorbed by the adsorbent or the fractional coverage, θ with
pressure at constant temperature can be expressed by means of a curve termed as
adsorption isotherm.

The Langmuir adsorption isotherm:

The simplest physically plausible isotherm is based on three assumptions:
1. Adsorption cannot proceed beyond monolayer coverage.

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 2. All sites are equivalent and the surface is uniform (that is, the surface is
perfectly flat on a microscopic scale).
3. The ability of a molecule to adsorb at a given site is independent of the
occupation of neighbouring sites (that is, there are no interactions between
adsorbed molecules).

The dynamic equilibrium is

A(g) + M(surface) = AM(surface)
with rate constants ka for adsorption and kd for desorption. The rate of change of
surface coverage due to adsorption is proportional to the partial pressure p of A
and the number of vacant sites N(1 − θ ), where N is the total number of sites:
dθ
= kapN(1 − θ ) (eq.2)
dt
The rate of change of θ due to desorption is proportional to the number of adsorbed
species, Nθ:
dθ
= −kdNθ (eq.3)
dt
At equilibrium there is no net change (that is, the sum of these two rates is zero),
and solving for θ gives the Langmuir isotherm:
Kp ka
θ = 1+ K p (eq.4) NB: K = k d

Example 1 Using the Langmuir isotherm

The data given below are for the adsorption of CO on charcoal at 273 K. Confirm
that they fit the Langmuir isotherm, and find the constant K and the volume
corresponding to complete coverage. In each case V has been corrected to 1.00 atm
(101.325 kPa).
P (kPa) 13.3 26.7 40.0 53.3 66.7 80.0 93.3
V (cm3) 10.2 18.6 25.5 31.5 36.9 41.6 46.1

Method From eq 4,
Kpθ + θ = Kp

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With θ = V/V∞, where V∞ is the volume corresponding to complete coverage, this
expression can be rearranged into
p p 1
= +
V V∞ KV∞

Hence, a plot of p/V against p should give a straight line of slope 1/V∞ and intercept
1/KV∞.

Answer The data for the plot are as follows:

p (kPa) 13.3 26.7 40.0 53.3 66.7 80.0 93.3
p/V (kPa/cm3) 1.30 1.44 1.57 1.69 1.81 1.92 2.02

R² = 0
Langmuir Isotherm

2.5

2
p/V (kPa/cm3)

1.5

0.5

0
0 10 20 30 40 50 60 70 80 90 100
p (kPa)

Fig. 1: The plot of the data in Example 1. As illustrated here, the Langmuir
isotherm predicts that a straight line should be obtained when p/V is plotted against
p.

The points are plotted in Fig. 1. The (least squares) slope is 0.00900, so
V∞ = 111cm3. The intercept at p = 0 is 1.20, so

1
K= ( 111cm 3 ) x (1.20 kPacm−3) =7.51 × 10−3kPa−1

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Freundlich adsorption isotherm: The Langmuir isotherm (The word “isotherm”
is used to emphasize constant-temperature condition in these types of studies) is a
common way of modeling gas- or liquid-phase molecules adsorbing on surfaces,
but it isn’t the only way. Another way to model the coverage versus the
concentration of the adsorbing species is the Freundlich 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:

x
= k .p1/n (n > 1) (eq.5)
m

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.
Taking logarithm of eq. (5)

x I
Log m = logk + n log p (6)

x
The validity of Freundlich isotherm can be verified by plotting log 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
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value of n .The intercept on the y-axis gives the value of log k.

Freundlich isotherm explains the behavior of adsorption in an approximate manner.

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The factor n can have values between 0 and 1(probable range 0.1 to 0.5). Thus,
equation (6) holds well over a limited range of pressure.
I x
When n = 0, m = constant, the adsorption is independent of pressure.
I x x
When n = 1, m = k p, i.e. m ∝ p, the adsorption varies directly with pressure.

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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
water is shaken with charcoal, a part of the acid is adsorbed by the charcoal and the
concentration of the acid decreases in the solution. Similarly, the litmus solution
when shaken with charcoal becomes colourless. The precipitate of Mg(OH) 2 attains
blue colour when precipitated in presence of magneson reagent. The colour is due
to adsorption of magneson. 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.
The precise mechanism of adsorption from solution is not known.
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.,
x
= kC1/n (7)
m
(C is the equilibrium concentration, i.e., when adsorption is complete).
On taking logarithm of the above equation, we have

x I
Log m = logk + n log C (8)
x
Plotting log 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

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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
The phenomenon of adsorption finds a number of applications.
Important ones are listed here:
(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 coalmines 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. Manufacture
of ammonia using iron as a catalyst, manufacture of H 2SO4 by contact
process and use of finely divided nickel in the hydrogenation of oils are
excellent examples of heterogeneous catalysis.
(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 (see Unit 6).
(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.

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(x) Chromatographic analysis: Chromatographic analysis based on the
phenomenon of adsorption finds a number of applications in analytical
and industrial fields.

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