SURFACE CHEMISTRY

Subramanyam Kalugotla
(PGT Chemistry – JNV Chittoor)
Introduction:
Surface Chemistry is concerned with phenomena that occur at
the surfaces or interfaces
 The surface is represented by separating the bulk phases by a hyphen or a
slash
For example, the interface between a solid and a gas is represented by
solid-gas or solid/gas

Examples–
• Corrosion, Electrode Processes, crystallization, dissolution and many more
• Have many uses in real life situations, industry and analytical work
Topics to be discussed:
• Adsorption
• Catalysis
• Colloids
• Emulsions
Adsorption:
• The accumulation of molecular species at the surface rather
than in the bulk of a solid or liquid is called Adsorption
• Adsorbate – The substance which accumulates on the surface
• Adsorbent – The material on which adsorption takes place

Solids (Charcoal, silica gel, clay etc.) have

larger surface area in finely divided state, which
makes them good adsorbents.
 Adsorption vs Absorption:

• In Adsorption – Substance does not

penetrate through the surface to the
bulk of the adsorbent

• In Absorption – Substance is
uniformly distributed throughout the
bulk of the solid
Interesting Fact – Both above said processes can occur
simultaneously, called sorption
 Types of Adsorption:
• Two types of adsorption of gases on solids:
• Physisorption - accumulation of gas on the surface of a solid occurs on
account of weak van der Waals’ forces
• Chemisorption - gas molecules or atoms are held to the solid surface
by chemical bonds
• Physical adsorption at low temperature may pass into chemisorption as
the temperature is increased
• 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
 Physisorption vs Chemisorption
Physisorption Chemisorption
• Not specific in nature • Specific in nature
• Reversible • Irreversible
• Enthalpy of adsorption is low (20- • Enthalpy of adsorption is high (80-
40 kJ mol-1) 240 kJ mol-1)
• It depends on the nature of • It also depends on the nature of
gas. More easily liquefiable gas. Gases which can react with
gases are adsorbed readily. the adsorbent show chemiso
rption.
• Low temperatures are favorable
• No appreciable activation energy • High temperatures are favorable
is required • High activation energy is required
• Results into multimolecular layers for this process
on adsorbent surface under high • Results into unimolecular layer
pressure

Note – Both processes depend on the surface area. Both increase with an
increase in surface area
Freundlich Adsorption
Isotherms:

• Adsorption Isotherm – It is a curve

that expresses the variation in the
amount of gas adsorbed by the
adsorbent with pressure at
constant temperature
Equation: Freundlich (1909) gave a
relation between quantity of gas
absorbed by unit mass of solid
adsorbent and pressure at a
temperature

 
(n>1)

 
x = mass of adsorbate
m = mass of adsorbent
  
(n>1)
 
• can have values between 0 and 1 (probable
range of 0.1 to 0.5)
• When = 0, constant, the adsorption is
independent of pressure
• When = 1, kP, i.e., P, the adsorption varies
directly with pressure

Important Note – Experimental isotherms always approach saturation at

high pressure, so Freundlich Isotherm fails at high pressure
  
(n>1)

•  Applying log on both sides for previous equation:

y = mx + c
Adsorption isobars:
• The curves drawn at constant pressure are known as isobars.

• The adsorption isobar can be used to distinguish between physical and

chemical adsorptions. In physical adsorption, there is a regular decrease
as temperature increases. However, in chemisorption, there is initial
increase and then it decreases.
• This is due to the reason that like ordinary chemical reactions adsorption
also requires some activation energy
Applications of Adsorption:
• 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

• 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

• Heterogeneous Catalysis - Adsorption of reactants on the solid surface of the

catalysts increases the rate of reaction

• Curing Diseases - A lot of drugs are used to kill germs by getting adsorbed on
them
 Catalysis:
The substance that alters the rate of chemical reaction and
itself remains chemically unchanged is called catalyst and the
phenomenon is known as catalysis
 Example – Potassium Chlorate, when heated strongly,
decomposes to give dioxygen which occurs in the temperature
range of 653-873K

2KClO3 → 2KCl + 3O2

But, when a little manganese dioxide is added,

decomposition takes place at lower temperature range i.e., 473-
633K, and even the rate of the process is accelerated
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.

F e(s)
N2(g) + 3H2(g) 2NH3 (g)
M o (s)
 Homogeneous and Heterogenous Catalysis:
• 
•Homogeneous Catalysis – When both reactants and catalysts are in same phase

(i.e., liquid or gas

•Example - Oxidation of sulphur dioxide into sulphur trioxide with dioxygen in the

presence of oxides of nitrogen as the catalyst in the lead chamber process. All

are in same phase.

2SO2(g) + O2(g) 2SO3(g)
 
• Heterogeneous Catalysis – When both reactants and catalysts are in
different phases

• Example - Oxidation of sulphur dioxide into sulphur trioxide in the

presence of Pt. Reactant is in gaseous state and catalyst is in solid
state.
2SO2(g) + O2(g) 2SO3(g)
Adsorption Theory of Heterogeneous Catalysis:
 
The mechanism involves five steps:
(i) Diffusion of reactants to the surface of the catalyst.
(ii) Adsorption of reactant molecules on the surface of the catalyst.
(iii) Occurrence of chemical reaction on the catalyst’s surface through
formation of an intermediate
(iv) Desorption of reaction products from the catalyst surface, and
thereby,
making the surface available again for more reaction to occur.
(v) Diffusion of reaction products away from the catalyst’s surface
Important features of Solid Catalysts:
••  
Activity - Activity of a catalyst refers to the capacity of the catalyst to
increase the speed of the chemical reaction
• The activity depends upon the extent of chemisorption

• Example - for hydrogenation reaction, the catalytic activity increases from

Group 5 to Group 11 metals with maximum activity being shown by groups
7-9 elements of the periodic table

2H2(g) + O2(g) 2H2O(l)

 
• Selectivity - The selectivity of a catalyst is its ability to direct a reaction to yield a
product
• Example - starting with H2 and CO, and using different catalysts, we get different
products

CO(g) + 3H2(g) CH4(g) + H2O(g)

CO(g) + 2H2 CH3OH(g)

CO(g) + H2 HCHO(g)
Enzyme Catalysis:
••  
Enzymes – Complex nitrogenous organic compounds which are produced
by living organisms (plants and animals)

• Examples:

• Inversion of cane sugar - invertase enzyme converts cane sugar into

glucose and fructose

C12H22O11(aq) + H2O(l) C6H12O6(aq) + C6H12O6(aq)

 
• Conversion of glucose into ethyl alcohol: The zymase enzyme converts
glucose into ethyl alcohol and carbon dioxide
C6H12O6(aq) 2C2H5OH(aq) + 2CO2(g)
• In stomach, the pepsin enzyme converts proteins into peptides
while in intestine, the pancreatic trypsin converts proteins into
amino acids by hydrolysis

• Conversion of milk into curd: It is an enzymatic reaction brought

about by lacto-bacilli enzyme present in curd
Characteristics of Enzyme Catalysis:

→ Most highly efficient - One molecule of an enzyme may

transform one million molecules of the reactant per minute

→ Highly specific nature - Each enzyme is specific for a given

reaction, i.e., one catalyst cannot catalyse more than one
reaction
→ Highly active under optimum temperature - The rate of an
enzyme reaction becomes maximum at a definite temperature,
called the optimum temperature. The optimum temperature range
for enzymatic activity is 298-310K

→ Highly active under optimum pH - The rate of an enzyme-

catalysed reaction is maximum at a particular pH called optimum

pH, which is between pH values 5-7
 Mechanism of enzyme catalysis:
 
The enzyme-catalysed reactions may be considered to proceed in two
steps.
Step 1: Binding of enzyme to substrate to form an activated complex.
E + S → ES*
Step 2: Decomposition of the activated complex to form product.
ES* → E + P
 Colloids:
• Colloid: It is a heterogeneous system in which one substance is
dispersed (dispersed phase) as very fine particles in another
substance called dispersion medium

• Difference between colloid and solution is the particle size

Note: Colloidal particle diameters range from 1 to 1000 nm

Classification based on Physical state of Dispersed
phase and Dispersion medium:
Dispersed Phase Dispersion Medium Type of Colloid Examples
Solid Solid Solid Sol Coloured glasses, gems
Solid Liquid Sol Paints, cell fluids
Solid Gas Aerosol Smoke, dust
Liquid Solid Gel Cheese, butter, jellies
Liquid Liquid Emulsion Milk, hair cream
Liquid Gas Aerosol Fog, mist, cloud
Gas Solid Solid Sol Pumice stone, foam rubber
Gas Liquid Foam Whipped cream, soap lather

Note – Most common colloids are sols and emulsions, which will be discussed in this chapter
Classification on nature of interaction between
Dispersed Phase and Dispersion Medium:
Lyophilic Colloids
• Lyophilic means liquid-loving
• These are formed by mixing
substances like gum, gelatin, starch,
etc., with a suitable liquid
• If dispersion medium is separated
from dispersed phase, sol can be re-
achieved by remixing with dispersion
medium
• Very Stable
Lyophobic Colloids
• Lyophobic means liquid-hating
• These are formed by using specific
methods, not when metals are simply
mixed with dispersion medium
• If dispersion medium is separated
from dispersed phase, sol cannot be
re-achieved by remixing with
dispersion medium
• Very Unstable, need stabilizing agents
for preservation
 Classification based on Type of Particles of Dispersed
Phase:
• Multimolecular Colloids - On dissolution, many atoms or smaller
molecules of a substance aggregate together to form species
having size in the colloidal range (diameter<1nm), called
Multimolecular Colloids

• For example, a gold sol may contain particles of various sizes

having many atoms.

Classification based on Type of
Particles of Dispersed Phase:

• Multimolecular Colloids - On dissolution, many atoms or smaller

molecules (diameter<1nm) of a substance aggregate together to
form species having size in the colloidal range(1 – 1000nm) called
Multimolecular Colloids

• For example, a gold sol may contain particles of various sizes having

many atoms.
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
Examples of naturally occurring macromolecules are starch,
cellulose, proteins and enzymes; and those of man-made
macromolecules are polythene, nylon, polystyrene, synthetic rubber,
etc.
Associated Colloids - 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, called Associated
Colloids(Micelles).

The aggregated particles thus formed are called micelles

or associated colloids.
The formation of micelles takes place only above a
particular temperature called Kraft temperature (Tk).
The formation of micelles takes place only above a
particular concentration called critical micelle concentration
(CMC).
 Preparation of Colloids:
•  Chemical Methods
• Colloidal solutions can be prepared by chemical reactions leading
to formation of molecules by double decomposition, oxidation,
reduction or hydrolysis
• These molecules then aggregate leading to formation of sols

As2O3 + 3 H2S As2S3(sol) +3 H2O

SO2 + 2 H2S 3 S(sol) + 2H2O
2 AuCl3 + 3 HCHO + 3 H2O 2 Au(sol) + 3 HCOOH + 6 HCl
FeCl3 + 3 H2O Fe(OH)3 (sol) + 3 HCl
• Peptization
• The process of converting a precipitate into colloidal sol by
shaking it with dispersion medium in the presence of small amount
of electrolyte

• Electrolyte in this process is called Peptizing Agent

• During this process, the precipitate adsorbs one of the ions of the
electrolyte on surface, which causes the development of positive
or negative charges on precipitates, which ultimately breaks into
smaller particles of the size of the colloid
• Electrical disintegration or
Bredig’s Arc method

• This process involves

dispersion as well as
condensation
• In this method, electric arc is
struck between electrodes of
the metal immersed in the Dispersion
dispersion medium medium

• The intense heat produced

vaporises the metal, which Ice-bath
then condenses to form
particles of colloidal size
• Colloidal sols of metals such
as gold, silver, platinum, etc.,
can be prepared by this
method
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:
• process of removing a dissolved
substance from a colloidal solution by
means of diffusion through a suitable
membrane
• The apparatus used for this purpose is
called dialyser
• Animal Membrane or Parchment Paper is
used as the membrane for this process as
the particles (ions or smaller particles) can
pass through, but colloidal particles
cannot Crystalloid
• Electro-dialysis:

• As the process of dialysis is quite slow, it

can be made faster by applying an electric
field if the dissolved substance in the
impure colloidal solution is only an
electrolyte, which is called Electro-dialysis
• The colloidal solution is placed in a bag of
suitable membrane while pure water is
taken outside
• The ions present in the colloidal solution
migrate out to the oppositely charged
electrodes
Note: Ultrafiltration is a slow process. To speed up the process, pressure or suction is applied.
• Ultrafiltration:
• Ultrafiltration 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
• The usual collodion is a 4% solution of nitrocellulose in a mixture of alcohol and
ether
• An ultra-filter paper may be prepared by soaking the filter paper in a collodion
solution, hardening by formaldehyde and then finally drying it
 Properties of Colloidal Solutions:
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.
• Tyndall Effect:

 Scattering of light by colloidal particles due to which path of beam in colloidal

solution is illuminated is called Tyndall effect.
 This effect was first observed by Faraday and later studied in detail by
Tyndall.
 Tyndall effect is observed only when the
following two conditions are satisfied.
o The diameter of the dispersed
particles is not much smaller than the
wavelength of the light used
o The refractive indices of the dispersed
phase and the dispersion medium
differ greatly in magnitude
Colour:
 
 The colour of colloidal solution depends on the wavelength of light
scattered by the dispersed particles.
 The wavelength of light further depends on the size and nature of
the particles. For example, finest gold sol is red in colour, as the
size of particles increases, it appears purple, then blue and finally
golden.
 The colour of colloidal solution also changes with the manner in
which the observer receives the light. For example, a mixture of
milk and water appears blue when viewed by the reflected light and
red when viewed by the transmitted light.
 • Brownian Movement:

 The zig-zag motion of colloidal particles is known as Brownian

movement.
 This motion is independent of the nature of the colloid but depends
on the size of the particles and viscosity of the solution.
 Smaller the size and lesser the
viscosity, faster is the motion.
• Charge on Colloidal Particles:

• Colloidal particles always carry an electric charge

Positively Charged Sols Negatively Charged Sols

Hydrated Metallic Oxides (Al2O3.xH2O, Metals

CrO3.xH2O, Fe2O3.xH2O) (e.g., copper, silver, gold sols )

Basic dye stuff Metallic Sulphides

(e.g., methylene blue sol) (e.g., As2S3, Sb2S3, CdS cols)

Hemoglobin (blood) Acid Dye Stuff

(e.g., eosin, congo red sols)

Oxides Sols of starch, gum, Gelatin

(e.g., TiO2 sol)
 The charge on the sol particles is due to one or more
reasons,
(i) due to electron capture by sol particles during electro
dispersion of metals,
(ii) due to preferential adsorption of ions from solution.
(iii) due to formulation of electrical double layer
When two or more ions are present in the dispersion medium,
preferential adsorption of the ion common to the colloidal particle
usually takes place

When silver nitrate solution is added to potassium iodide solution,

the precipitated silver iodide adsorbs iodide ions from the
dispersion medium and negatively charged colloidal solution
results. However, when KI solution is added to AgNO3 solution,
positively charged sol results due to adsorption of Ag+ ions from
dispersion medium

AgI/I- (Negatively Charged) AgI/I+(Positively Charged)

When silver nitrate solution is added to potassium iodide solution, the
precipitated silver iodide adsorbs iodide ions from the dispersion
medium and negatively charged colloidal solution results. However,
when KI solution is added to AgNO3 solution, positively charged sol
results due to adsorption of Ag+ ions from dispersion medium

AgI/I- (Negatively Charged) AgI/ Ag+ (Positively Charged)

KI(aq)
AgNO3(aq)

KI(aq) AgNO3(aq)
AgI(s) AgI(s)
• If FeCl3 is added to excess of hot water, a positively charged sol of hydrated
ferric oxide is formed due to adsorption of Fe3+ ions. However, when ferric
chloride is added to NaOH a negatively charged sol is obtained with
adsorption of OH- ions
Fe2O3.xH2O/Fe3+(Positively Charged) Fe2O3.xH2O/OH-(Negatively
Charged)

• Having acquired a positive or a negative charge by selective adsorption on

the surface of a colloidal particle as stated above, this layer attracts
counter ions from the medium forming a second layer.
AgI/I- K+ AgI/Ag+I-
• The combination of the two layers of opposite charges around the colloidal
particle is called Helmholtz electrical double layer.
• Electrophoresis:
• The existence of the charge on the
colloids is confirmed by this experiment
Cathode Anode
• 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 move towards anode
During electrophoresis, i.e., 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
• Coagulation:
• The process of settling of colloidal particles to form aggregates, when the
charge is removed from them, is called Coagulation
• Coagulation is carried out by:

• By Electrophoresis: The colloidal particles move towards oppositely

charged electrodes, get discharged and precipitated

• By mixing two oppositely charged sols: 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, which reduces
the charge on particles and eventually they settle down

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
Hardy Schulz Rule:
It states that greater the valence of flocculating ion added,
the greater is its power to cause coagulation. For
example
 In the coagulation of a negative sol, the flocculating power
is in the order:
Na+<Ba2+<Al3+
 In the coagulation of a positive sol, the flocculating power
is in the order:
Cl–<SO42–<PO43–<[Fe(CN)6]4–
 
• Coagulation of lyophilic sols:

• If the factors responsible for stability of lyophilic sols are removed, by adding

an electrolyte or by adding a suitable solvent, a lyophilic sol can be

coagulated

• 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 because hey are
extensively solvated, i.e., colloidal particles are covered by a sheath of
the liquid in which they are dispersed

• 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
 Emulsions:
An emulsion is a colloid in which both dispersed
phase and dispersion medium are liquids, i.e.,
liquid-liquid colloidal system.
 
• In the first system (O/W), water acts as
dispersion medium. Examples of this type of
emulsion are milk and vanishing cream
• In the second system (W/O), oil acts as
dispersion medium. Common examples of this
type are butter and cream
• Emulsions of oil in water are unstable and sometimes they
separate into two layers on standing. For stabilisation of an
emulsion, a third component called Emulsifying Agent is usually
added

• The emulsifying agent forms an interfacial film between

suspended particles and the medium. The principal emulsifying
agents for O/W emulsions are proteins, gums, natural and
synthetic soaps, etc., and for W/O, heavy metal salts of fatty
acids, long chain alcohols, lampblack, etc.,
Thank You