SURFACE CHEMISTRY

Surface chemistry deals with phenomena that occur at the surfaces or

interfaces.

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.

*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.
*The process of removing an adsorbed substance from a surface on
which it is adsorbed is called desorption.

*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.
*Both adsorption and absorption can take place simultaneously also. The
term sorption is used to describe both the processes.

*Adsorption increases with the increase of surface area per unit mass of
the adsorbent at a given temperature and pressure. there is decrease in
surface energy which appears as heat.

*Exothermic process. In other words, ∆H is negative. ∆S is negative.

*It is a Spontaneous Process.

*If accumulation of gas on the surface of a solid occurs on account of

weak van der Waals’ forces, 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.
 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.

FRUENDLICH ADSORPTION ISOTHERM:

x /m = k.p 1/n (n > 1)

*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.

*There is a decrease in physical adsorption with increase in temperature.

These curves always seem to approach saturation at high pressure.
 log x/m = log k + 1/n log p

* The extent of adsorption decreases with an increase in temperature.

* The extent of adsorption increases with an increase of surface area of
the adsorbent.
* The extent of adsorption depends on the concentration of the solute in
solution.
* The extent of adsorption depends on the nature of the adsorbent and
the adsorbate.

CATALYST: Which accelerate the rate of a chemical reaction and

themselves remain chemically and quantitatively unchanged after the reaction.
PROMOTERS AND POISONS: Promoters are substances that
enhance the activity of a catalyst while poisons decrease the activity of a
catalyst. For example, in Haber’s process for manufacture of ammonia,
molybdenum acts as a promoter for iron which is used as a catalyst.

N2 (g) + 3H2 (g) Fe(s) Mo(s) 2NH3 (g)

*Heterogeneous catalysis: In heterogeneous catalysis, the catalyst and
the reactants are in different phases. For example, a solid catalyst may be used
to catalyze a reaction between gas-phase reactants.

*Homogeneous catalysis: In homogeneous catalysis, the catalyst and

the reactants are in the same phase. For example, a dissolved catalyst may be
used to catalyze a reaction between dissolved reactants.

APPLICATIONS OF CATALYSIS:
*Industrial chemistry: Catalysts are used in a variety of industrial
processes, such as the production of fertilizers, plastics, and pharmaceuticals.

*Environmental chemistry: Catalysts are used to remove

pollutants from the environment, such as catalytic converters in
automobiles.

*Energy production: Catalysts are used in fuel cells and other

energy-conversion devices.

*Biocatalysis: Catalysts are used in biological systems to facilitate

biochemical reactions.

ENZYME CATAYSIS: Enzymes are complex nitrogenous organic

compounds which are produced by living plants and animals.
 APPLICATIONS OF ENZYMES:

COLLOIDS: A colloidal solution, also known as a colloidal system or

colloidal dispersion, is a mixture in which one substance (the dispersed
phase) is distributed throughout another substance (the dispersion
medium) in the form of very fine particles. The dispersed phase particles
have a diameter of between 1 and 1000 (nm). Colloidal solutions are often
cloudy or translucent due to the scattering of light by the dispersed
particles.

PROPERTIES OF COLLOIDAL SOLUTIONS:

* Tyndall effect: This is the scattering of light by the dispersed particles
in a colloidal solution. The Tyndall effect can be observed by shining a beam
of light through a colloidal solution. The light will be scattered in all
directions, making the solution appear cloudy or translucent.

*Brownian motion: This is the random motion of the dispersed

particles in a colloidal solution. Brownian motion is caused by the
collision of the dispersed particles with the molecules of the dispersion
medium.

*Sedimentation: This is the settling of the dispersed particles in a

colloidal solution. Sedimentation occurs when the gravitational force
acting on the dispersed particles is greater than the Brownian motion.

*Coagulation: This is the clumping together of the dispersed particles

in a colloidal solution. Coagulation can be caused by several factors,
including the addition of electrolytes, heating, or freezing.

EMULSIONS: An emulsion is a mixture of two immiscible liquids,

one of which is dispersed in the other in the form of small droplets. The
dispersed phase is usually the minority component, and the continuous
phase is the majority component. Emulsions are stabilized by emulsifiers,
which are molecules that adsorb to the interface between the two
liquids and prevent them from coalescing.

TYPES OF EMULSIONS:
*Oil-in-water (O/W) emulsions: In an O/W emulsion, the oil phase
is dispersed in the water phase. This type of emulsion is typically formed
when oil is added to water in the presence of an emulsifier.

*Water-in-oil (W/O) emulsions: In a W/O emulsion, the water

phase is dispersed in the oil phase. This type of emulsion is typically
formed when water is added to oil in the presence of an emulsifier.

* Emulsifiers are molecules that adsorb to the interface between two

immiscible liquids and prevent them from coalescing. Emulsifiers can be
either hydrophilic (water-loving) or liyophilic (oil-loving). Hydrophilic
emulsifiers have a polar head group and a nonpolar tail group, while
lipophilic emulsifiers have a nonpolar head group and a polar tail group.

*The type of emulsifier used to stabilize an emulsion depends on the

nature of the two liquids being emulsified. For example, an O/W
emulsion would be stabilized by a hydrophilic emulsifier, while a W/O
emulsion would be stabilized by a lipophilic emulsifier.

* Multimolecular colloids: On dissolution, a large number of

atoms or smaller molecules of a substance aggregate together to form
species having size in the colloidal range (1–1000 nm). The species thus
formed are called multimolecular colloids.
* Macromolecular colloids: Macromolecules in suitable solvents
form solutions in which the size of the macromolecules may be in the
colloidal range. Such systems are called macromolecular colloids. These
colloids are quite stable and resemble true solutions in many respects.
EXAMPLES: Starch, cellulose, proteins and enzymes; and those of
man-made macromolecules are polythene, nylon, polystyrene, synthetic
rubber, etc.

* Associated colloids (Micelles): There are some substances

which at low concentrations behave as normal strong electrolytes, but at
higher concentrations exhibit colloidal behaviour due to the formation
of aggregates. The aggregated particles thus formed are called micelles.
These are also known as associated colloids.
*The formation of micelles takes place only above a particular
temperature called Kraft temperature (Tk) and above a particular
concentration called critical micelle concentration (CMC).

PREPARATION OF COLLOIDS:
 PURIFICATION OF COLLOIDAL SOLUTIONS
* The process used for reducing the amount of impurities to a requisite
minimum is known as purification of colloidal solution.
*DIALYSIS: It is a process of removing a dissolved substance from a colloidal
solution by means of diffusion through a suitable membrane.

*Since particles (ions or smaller molecules) in a true solution can pass through
animal membrane (bladder) or parchment paper or cellophane sheet but not
the colloidal particles, the membrane can be used for dialysis. The apparatus
used for this purpose is called dialyser. A bag of suitable membrane containing
the colloidal solution is suspended in a vessel through which fresh water is
continuously flowing. The molecules and ions diffuse through membrane into
the outer water and pure colloidal solution is left behind.
* ELECTRO-DIALYSIS: The process of dialysis is slow. It can be made
faster by applying an electric field if the dissolved substance in the impure
colloidal solution is only an electrolyte.
* The colloidal solution is placed in a bag of suitable membrane while pure
water is taken outside. Electrodes are fitted in the compartment. The ions
present in the colloidal solution migrate out to the oppositely charged
electrodes.

*ULTRA
FILTRATION: It is the process of separating the colloidal particles from
the solvent and soluble solutes present in the colloidal solution by specially
prepared filters, which are permeable to all substances except the colloidal
particles.
* Colloidal particles can pass through ordinary filter paper because the pores
are too large. However, the pores of filter paper can be reduced in size by
impregnating with collodion solution to stop the flow of colloidal particles.
Ultrafiltration is a slow process. To speed up the process, pressure or suction is
applied. The colloidal particles left on the ultra-filter paper are then stirred with
fresh dispersion medium (solvent) to get a pure colloidal solution.

COLLIGATIVE PROPERTIES: Colloidal particles being bigger

aggregates, the number of particles in a colloidal solution is comparatively
small as compared to a true solution. Hence, the values of colligative properties
(osmotic pressure, lowering in vapour pressure, depression in freezing point
and elevation in boiling point) are of small order as compared to values shown
by true solutions at same concentrations.

CHARGE ON COLLIODAL PARTICLES: Colloidal particles always

carry an electric charge. The nature of this charge is the same on all the
particles in a given colloidal solution and may be either positive or negative.

* The combination of the two layers of opposite charges around the colloidal
particle is called Helmholtz electrical double layer.

* According to modern views, the first layer of ions is firmly held and is termed
fixed layer while the second layer is mobile which is termed diffused layer.
Since separation of charge is a seat of potential, the charges of opposite signs
on the fixed and diffused parts of the double layer results in a difference in
potential between these layers. This potential difference between the fixed
layer and the diffused layer of opposite charges is called the electrokinetic
potential or zeta potential.

ELECTROPHORESIS: The existence of charge on colloidal particles is

confirmed by electrophoresis experiment. 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.
* The process of settling of colloidal particles is called coagulation precipitation
of the soln.

By electrophoresis: The colloidal particles move towards oppositely

charged electrodes, get discharged and precipitated.

By mixing two oppositely charged sols: Oppositely

charged sols when mixed in almost equal proportions, neutralise their charges
and get partially or completely precipitated. Mixing of hydrated ferric oxide
(+ve sol) and arsenious sulphide (–ve sol) bring them in the precipitated forms.
This type of coagulation is called mutual coagulation.

By boiling: When a sol is boiled, the adsorbed layer is disturbed due to

increased collisions with the molecules of dispersion medium. This reduces the
charge on the particles and ultimately leads to settling down in the form of a
precipitate.

By persistent dialysis: On prolonged dialysis, traces of the

electrolyte present in the sol are removed almost completely and the colloids
become unstable and ultimately coagulate.

By addition of electrolytes: When excess of an electrolyte is

added, the colloidal particles are precipitated. The reason is that colloids
interact with ions carrying charge opposite to that present on themselves.
This causes neutralisation leading to their coagulation. The ion responsible for
neutralisation of charge on the particles is called the coagulating ion. A
negative ion causes the precipitation of positively charged sol and vice versa.

*Greater the valence of the flocculating ion added, the greater is its power to
cause precipitation. This is known as Hardy-Schulze rule. In the coagulation of a
negative sol, the flocculating power is in the order: Al3+ >Ba2+ >Na+

*Similarly, in the coagulation of a positive sol, the flocculating power is in the

order: [Fe(CN)6] 4– > PO4 3– > SO4 2– > Cl –

* The minimum concentration of an electrolyte in millimoles per litre required

to cause precipitation of a sol in two hours is called coagulating value. The
smaller the quantity needed, the higher will be the coagulating power of an
ion.

*Coagulation of lyophilic sols: There are two factors which are

responsible for the stability of lyophilic sols. These factors are the charge and
solvation of the colloidal particles. When these two factors are removed, a
lyophilic sol can be coagulated.
(1) by adding an electrolyte
(2) by adding a suitable solvent.
When solvents such as alcohol and acetone are added to hydrophilic sols, the
dehydration of dispersed phase occurs. Under this condition, a small quantity
of electrolyte can bring about coagulation.
*Protection of colloids: Lyophilic sols are more stable than
lyophobic sols. This is due to the fact that lyophilic colloids are extensively
solvated, i.e., colloidal particles are covered by a sheath of the liquid in which
they are dispersed. Lyophilic colloids have a unique property of protecting
lyophobic colloids. When a lyophilic sol is added to the lyophobic sol, the
lyophilic particles form a layer around lyophobic particles and thus protect the
latter from electrolytes. Lyophilic colloids used for this purpose are called
protective colloids.