SURFACE CHEMISTRY
• Surface chemistry is the study of phenomenon occurring at
the surface/interface.
• Corrosion, electrode processes, heterogeneous catalysis, dis-
solution, crystallization all are surface phenomenon.
• Very low pressure is required for surface study so that the
surface remains very clean.
ADSORPTION
• the accumulation of molecular species at the surface rather
than in the bulk of solid or liquid is called adsorption.
• Adsorbate - Substance that is accumulated.
• Adsorbent - Material on the surface of which adsorption
takes place.
• Finely divided solids act as good adsorbent. e.g. Charcoal,
silica gel, alumina gel, clay, colloids, finely divided metals.
• Examples of adsorption
1. Decrease in pressure of gases in presence of powdered
charcoal.
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2. Decolouration of organic dye in charcoal.
3. Raw sugar becomes colorless in presence of animal
charcoal.
4. Air becomes dry over silica due to adsorption of mois-
ture.
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• Desorption - The process of removal of adrorbate from ad-
sorbent is called desorption.
• Difference between adsorption and absorption is that ac-
cumulation takes place throughout the bulk of material in
solids while it only takes place at the surface in case of ad-
sorption.
• Adsorption and absorption can take place simultaneously
and they are together called sorption.
MECHANISM OF ADSORPTION
• Inside the adsorbent molecules experience zero net force,
but molecules on the surface experience unbalanced forces.
These residual forces attract adsorbate particles on its sur-
face.
• Adsorption is an exothermic process (∆H < 0). Decrease
in surface energy appears as heat.
• Freesom of movement of adsorbate particles decreases hence
(∆S < 0).
• ∆G = ∆H − T ∆S < 0 for adsorption. ∆H must be more
negative than T ∆S.
• As adsorption proceeds, value of ∆H decreases and ulti-
mately becomes equal to T ∆S. At this point (∆G = 0),
and adsorption stops. Equilibrium is attained.
TYPES OF ADSORPTION
• Physiosorption - When adsorbate gaseous particles are held
to the surface by weak van der Walls forces, adsorption is
called physiosorption/ physical adsorption.
• Chemisorption - When adsorbate gaseous particles are held
to the surface by chemical bond, then adsorption is called
chemisorption/ chemical adsorption. High activation energy
is needed hence sometimes called activated adsorption.
• These processes can occur together. Physiosorption at low
temperature may pass into chemisorption at high tempera-
ture.
• Difference between physisorption and chemisorption
1. Van der Walls forces | Chemical bond formation
2. Lack of specificity due to global nature of Van der Walls
forces |Highly specific in nature.
3. Reversible on changing pressure | Irreversible.
4. Depends on nature of gas. More easily liquefiable gases
are readily adsorbed | Depends on chemical nature
of gas. Gases which can react with adsorbent show
chemisorption.
5. Low enthalpy change | High enthalpy change.
ADSORPTION ISOTHERM
• A curve that shows the variation of gas adsorbed by adsor-
bent with pressure at constant temperature is called adsorp-
tion isotherm.
• Freundlich adsorption isotherm - Empirical relationship be-
tween amount of gas adsorbed by per unit mass of adsorbent.
x 1
= Kp n ; n > 1
m
x = mass of gas adsorbed.
• At fixed pressure amount of gas adsorbed decreases with
increase in temperature.
• Experimentally at high pressure the curve approaches satu-
ration. And this can’t be explained by Freundlich isotherm.
ADSORPTION FROM SOLUTION PHASE
• Extent of adsorption decreases with increase in tempera-
ture. Adsorption increases with increase in surface area of
adsorbent.
 • Adsorption depends on concentration of solution. • Old Theory - The increase in concentration of reactants over
the surface increases the rate of reaction. Adsorption being
• It depends on nature of adsorbate and adsorbent. exothermic releases heat that enhances the rate of reaction.
• Exact mechanism not known. Behavior is described by Fre- Catalytic action is explained by intermediate complex the-
undlich isotherm when pressure is replaced by concentra- ory.
tion.
x 1
• MODERN ADSORPTION THEORY
= Kc n
m – Diffusion of reactants to the surface of the catalyst.
x 1 – Adsorption of the reactant molecules on the surface of
⇒ log = log K + log c
m n the catalyst.
APPLICATION OF ADSORPTION – Chemical reaction occur at the surface of the catalyst
through formation of intermediate.
• Production of high vacuum.
– Desorption of reactant products from catalyst’s surface
• Gas masks: activated charcoal to adsorb poisonous gases. making surface available for further reaction.
• Control humidity using silica and alumina gel. – Diffusion of reaction products away from surface. First
reactants are bonded loosely to surface. These re-
• Adsorption for removal of dye from solution. actants may react to form new molecules. These
molecules then free the surface for further reaction.See
• Heterogeneous catalysis - F e catalyst for manufacturing
pic at the end.
N H3 (Born Haber process), finely divided N i for manu-
facturing H2 SO4 (Contact process), N i in Hydrogenation
i
reaction.
• Separation of inert gases - Different inert gases can be ad- FEATURES OF SOLID CATALYSIS

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sorbed by different adsorbent and thus can be separated.
• Many germs can be adsorbed and killed on the surface and
the disease can be cured.
• Froth flotation method.
• Adsorption indicators.
• Activity - It depends on strength of chemisorption.
Reactants must be adsorbed strongly enough for so that
they can react but must not be very strongly adsorbed so
that other reactants are left out. Maximum activity is shown
by group 7-9 elements.
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Pt
2H2 (g) + O2 (g) −−→ 2H2 O(l)
• Chromatographic analysis.
• Selectivity - Action of catalyst is highly selective i.e. a cat-
CATALYSIS
alyst catalyzing one reaction may fail to catalyze another
• Substances that accelerates the rate of chemical reactions reaction.
while themselves remaining chemically and quantitatively
• The selectivity of a catalyst is its ability to direct a reaction
unchanged are called catalyst and this phenomenon is
to yield a particular product.
known as catalysis. M nO2 increases the rate of formation
of oxygen at much lower temperature. Ni
CO(g) + 3H2 O −−→ CH4 (g) + H2 O(l)
M nO
2
2KClO3 −−−−→ 2KCl + O2 Cu/ZnO/Cr2 O3
CO(g) + 2H2 O −−−−−−−−−−−→ Ch3 OH(g)
• PROMOTERS increases the activity of catalyst while POI- Cu
SONS reduce the activity of catalyst. M o acts as promoter CO(g) + H2 (g) −−→ HCHO(g)
for F e in Haber process.
SHAPE SELECTIVE CATALYSIS
Fe
N2 (g) + 3H2 (g) −−→ 2N H3
• The catalytic reactions that depends up on the pore struc-
ture of catalyst and size of reactants and products are called
Homogeneous catalysis and Heterogeneous catalysis
shape selective catalysis.
• When reactants and catalyst are in same phase then the • Geolytes (−(Al − O − Si)− 3d network called alumino sili-
catalysis is called homogeneous catalysis. cates) are good shape selective catalysts due to their micro
N O(g) pores.
2SO2 (g) + O2 (g) −−−−→ 2SO3 (g)
• ZSM-5 catalyst used in petroleum industry.
• Heterogeneous catalysis - Reactants and catalyst are not in
same state. ENZYME CATALYSIS
2SO2 (g) + O2 (g) →
−
• Enzymes are nitrogenous organic compounds which are pro-
duced by living plants and animals. Hence enzymes are
ADSORPTION THEORY OF HETEROGENEOUS CATALYSIS called bio-catalysts.
 Dn medium Dd phase Name Example
Enzyme Source Enzymatic action Gas Liquid Aerosol Fog,mist,clouds
Invertase Yeast Sucrose → Glucose + fructose Gas Solid Aerosol Smoke, dust
Zymase Yeast Glucose → Ethyl alcohol + CO2 Liquid Gas Foam Froth,Whipped cream
Diastace Malt Starch → Maltose Liquid Liquid Emulsion Milk, hair cream
Liquid Solid Sol Paint, cell fluids
Maltose Yeast Maltose → Glucose
Solid Gas Foam Pumice, plastic foams
Urease Soyabean Urea → N H3 + CO2
Solid Liquid Gel Jelly, cheese, butter
Pepsin Stomach Proteins → Amino acids Solid solid solid sol Ruby, glass(dd metal)
If medium is water, it is called aquasol. If medium is alcohol,
CHARACTERISTICS OF ENZYME CATALYSIS it is called alcosol.
• Based on interaction between phase and medium particles
• Most highly effective
1. Lyophillic colloids (Solvent loving) - Can be prepared
• Highly specific in nature readily by mixing phase with medium, Hence called
reversible sols. Quite stable. Can not be coagulated.
• Highly active under optimum temperature(298K - 310K) e.g. sols of gum, gelatine, starch, proteins in organic
solvents.
• Highly active under optimum pH range (5-7)
2. Lyophobic sols(solvent repelling, liquid hating) - Cant
be prepared by simply mixing phase with medium
• Activity increases in presence of co-enzymes (vitamins)and
hence called irreversible sols. Unstable. Can be pre-
activators (metal ions such as N a+ , M g 2+ , M n2+ etc.).
cipitated by adding small electrolyte, heating or simply
shaking. They require stabilizing agents for preserva-
• Activity is reduced in presence of inhibitors and poisons.
tion. e.g. As2 O3 , F e(OH)3 etc.
• Mechanism • Based on type of particles of dispersed phase

−N H2 − COOH.

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– There are number of cavities present on surface of par-
ticles of enzymes contain highly active groups such as

– This fits into substrate (reactants) to form enzyme sub-

strate complex.
1. Multimolecular colloids - A larger number of atoms or
smaller molecules aggregate to form species having size
in colloidal range. (diameter < 1 mm are called multi-
molecular colloids. e.g- gold sol, sulphur sol.
2. Macromolecular colloids - Macromolecules in suitable
solvents form solution in which particle size fall in col-
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– This complex breaks down to give products. loidal range. Quite stable and resemble solution in
many aspects.
E + S ) [E − S] *
* )E+ P Naturally occurring Macromolescules are starch, cellu-
Enzyme Substrate Complex P roduct
lose, proteins, enzymes etc. Man made ones are poly-
mers such as nylon, polythene etc.
3. Associated colloids (micelles) - Some electrolytes at
higher concentration aggregate together to form big-
ger particles called micelle which fall in colloidal range.
Also known as associated colloids.
• Formation of micells take place only above a specific tem-
perature called Kraft Temperature(Tk ) and above a partic-
ular concentration known as critical micelle concentration
(CMC). On dilution colloids revert back to original ions.
COLLOIDS
• Mechanism of micelle formation - Soap is a sodium or potas-
• A colloid is a heterogeneous system in which one substance is sium salt of higher fatty acids (RCOO− Na+ ) such as sodium
dispersed(dispersed phase) as very fine particles in another stearate (CH3 (CH2 )16 COO− Na+ ).
substance(dispersion medium). • When dissolved in water it breaks down into ions
RCOO− andNa+ .
• Difference between solution (Molecular sized particles) and
colloid (large sized single particle called macro-molecule or • RCOO− has long non-polar hydrocarbon tail which is re-
aggregate of 100-1000 molecules) is due to particle size. pelled by water (Hydrophobic tail) and (COO− ), a polar
head which is attracted by water (hydrophillic tail).
• Colloidal particles are bigger than solution particles but
• At lower concentration, RCOO− are present at the surface
small enough to remain suspended (10−9 − 10−6 m in size).
with polar heads into the water and tail pointing out of the
water.
• Due to smaller size they have very large surface area.
• At critical micelle temperature, These are pulled inside.
CLASSIFICATION OF COLLOIDS They aggregate to form spherical shape with heads at sur-
face. Such an aggregate is called micelle. INSERT PIC-
• Based on dispersed phase and dispersion medium TURE.
 • In case of detergent, such as sodium lauryl sulphate
(CH3 (CH2 )11 SO− + −
4 Na ), the polar group is SO4 along with
the long hydrocarbon chain. They are non bio degradable.
• Cleansing action of soap - Cleansing action is due
to the fact that that micelles are formed with hy-
drophobic tail inside the oil (dirt), and hydrophillic
head inside the water. Thus the dirt surrounded by
stearate ion is pulled in water and are removed from
the surface. Negatively charged surface prevent the
micelles from coming together and forming aggregates.
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PREPARATION OF COLLOIDS
• Chemical method
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doubledisplacement
As2 O3 + 3H2 S −−−−−−−−−−−−−→ As2 S3 (sol) + H2 O
oxidation
SO2 + H2 S −−−−−−→ 3S(sol) + 2H2 O
2 When viewed under ultra microscope, focus of a beam when
reduction
2AuCl3 + 3HCHO −−−−−−→ 2Au(sol) + 3HCOOH + 6HCl
hydrolysis
FeCl3 + 3H2 O −−−−−−−→ Fe(OH)3 (sol) + HCl
The product molecules form aggregate that lead to forma-
tion of sols.
• Electrical disintegration or Bredig’s arc method -Colloidal
sols of metals such as Au, Ag can be formed using this
method. An lectric arc is a struck between two metal elec-
trodes immersed in dispersion medium. Intense heat gener-
ated vaporizes the metal which condense to form colloidal
sized particles. These molecules disperse to form sols. IN-
SERT PICTURE.
• Peptization - process of converting a precipitate into col-
loidal sol by shaking it with dispersion medium in the pres-
ence of a small amount of electrolyte. The electrolyte is
called peptizing agent. One of the ion of electrolyte is ad-
sorbed on the surface of precipitate and break it into parti-
cles of colloidal size to form sols.
PURIFICATION OF COLLOIDAL SOLS
The process used to reduce the amount of impurity to minimum
level so that colloidal solution remains stable is known as purifi-
cation of colloidal sol.
• Dialysis - A process of removing dissolved substance from a
colloidal solution by means of diffusion through a suitable
membrane. Smaller impurities can move through membrane
but larger colloidal particles can’t. INSERT PICTURE.
• Electrodialysis - The process of dialysing by application of
electric field to quicken up the purification process. INSERT
PICTURE.
• Ultrapurification - 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.
A 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.
Being slow process, pressure or suction is applied. Leftover
colloidal particles can be mixed with dispersion phase to
obtain colloidal sol.
PROPERTIES OF COLLOIDAL SOLUTION
• Colligative properties - Values of colligative properties are
less than those for solution. This is because number of col-
loidal particles in sol is less than those present in solution
due to formation of aggregates.
• TYNDALL EFFECT - When viewed the path of light at
right angle, colloids show stong to mild apalescene (Illumi-
nation of path of beam of light). This effect is called Tyndall
effect. This happens because colloidal particles scatter beam
of light in all direction.
INSERT FIGURE
Tyndall effect is used to distinguish between true solution
and colloids (True solutions do not show apalescene).
viewed normally, appears as twinkling stars in dark back-
ground. It does not give any information about shape and
size of colloidal particles.
Conditions for tyndall effect
– Size of dispersed phase particles is not much smaller
than wavelength of light.
– Refractive indices of medium and phase must differ
greatly.
• Colour -The colour of colloidal solution depends upon the
wavelengths of light scattered by colloidal particles. It also
depends on the direction from which light is observed.
• Brownian movement - Colloidal particles are in a state of
continuous zigzag motion. This motion is called Brownian
motion.
It depends on particles size and viscosity and not on the na-
ture of colloidal particles. Smaller size and lesser viscosity,
faster is the Brownian motion.
This is due to unbalanced bombardment of colloidal parti-
cles by the particles of medium. This prevents paricles from
settling down and is responsible for stability of sols.
• Charge on colloids - They always carry some charge which
is same on all the particles.
 – Negatively charged sol - Metal sol (Au,Ag, Si etc.),
As2 O3 , CdS, Sb2 O3 , Sols of starch, gum, gelatin, clay,
charcoal, etc.,Acid dye stuffs, eosin, congo red sols etc.
v. By addition of electrolyte - In excess of electrolyte, colloidal
– Positively charged sol - Hydrated metal-
lic oxides, e.g., Al2 O3 .xH2 O, CrO3 .xH2 O and
F e2 O3 .xH2 O.Haemoglobin (blood), Oxides, e.g., T iO2
sol.
• Charge on colloidal particles can be due to -
i. Electron capture during electro dispersion.
ii. Preferential adsorption of charges.
iii. Formation of electrical double layer
• Preferential adsorption of ions - When two or more ions are
present in the dispersion medium, preferential adsorption
of that ion which is common to the colloidal particles take
place. Or that ion which is chemically similar.
AgNO3 is added to KI to obtain negatively charged sol
(AgI/I − ).
When KI is added to AgNO3 to obtain positively charged
sol (AgI/Ag + ).
Having acquired the charge, particles attract the counter
(AgI/Ag+ NO−
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ions from the medium forming a second layer. For example,
− +
3 ) and (AgI/I K ).
• The combination of the two layers of opposite charges
around the colloidal particle is called Helmholtz electrical
double layer. The first layer of ions is firmly held and is
termed fixed layer while the second layer is mobile which is
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termed diffused layer.
• This potential difference between the fixed layer and the
diffused layer of opposite charges is called the electrokinetic
potential or zeta potential.
• The presence of equal and similar charges on particles pre-
vent them from coming together and hence responsible for
stability sols.
• Electrophoresis -The movement of colloidal particles under
electric field towards one of the electrode is called elec-
trophoresis.
When movement of colloidal particles is stopped, then the
particles of dispersion medium begin to move in under elec-
tric field. This is called electro-osmosis.
COAGULATION
The process of settling of colloidal particles is called coagulation
or precipitation of the sol.If charges on the colloidal particles re-
moved, they will come together become heavy and precipitate out.
i. By electrophoresis - Particles move towards opposite elec-
trode, lose their charges and precipitates out.
ii. By mixing two oppositely charged sols: Oppositely charged
sols when mixed in almost equal proportions, neutralise
their charges and get partially or completely precipitated.
This is called mutual coagulation.
iii. By boiling - On boiling, adsorbed charged layer is disturbed
due to increased collisions with dispersion medium particles.
Charge is reduced and they are settled down as precipitate.
iv. On persistent dialysis - Every trace of electrolyte is remove.
This makes the colloids unstable. Ultimately they coagu-
late.
particles get neutralized by oppositely charged ions 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 Schulze Law - Greater the valency of coagulating
ions, greater is its power to cause precipitation.
For negative sol, flocculating power order: Al3+ > Ba2+ > Na+
For positive sol, flocculating power order:
−
[Fe(CN)6 ]4− > PO3− 2−
4 > SO4 > 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 - Stabilised by charge
and solvation. Coagulated by first adding suitable solvent
to reduce solvation followed by addition of electrolyte to
remove charges. In aquasol, alcohol or acetone is added to
dehydrate dispersed phase particles.
Protection of colloids - Lyophobic colloids being un-
stable can be protected by adding lyophilic sol. Lyophilic
sol forms a protective layer around lyophobic sol. Sols used
for protection of sols are called protective colloids.
EMULSIONS
• If a mixture of two immiscible or partially miscible liquids
is shaken, a coarse dispersion of one liquid in the other is
obtained which is called emulsion. They are liquid-liquid
colloidal systems.
• Two types
i) Oil dispersed in water (O/W type)- Oil is phase and
water is medium. e.g- milk, vanishing cream
ii) Water dispersed in oil (W/O type)- water is phase and
oil is medium. e.g. - butter and cream.
• Emulsions are unstable and separate into layers if left alone.
Emulsifying agents are added to stabilize the emulsions.
The principal emulsifying agents for O/W emulsions are pro-
teins, gums, natural and synthetic soaps, etc., and for W/O,
heavy metal salts of fatty acids, long chain alcohols, lamp-
black, etc.
• When dispersed liquid is added, it forms separate layer.
• Droplets are liquids are generally negatively charged and
hence can be precipitated by electrolytes.
• SHows Brownian motion and Tyndall effect.
• Can be broken into constituent liquids by heating, freezing,
centrifugation etc. INSERT PICTURE.
COLLOIDS AROUND US
i. Blue colour of sky - Scattering of light by dust particles and
water droplets.
ii. Fog, mist and rain - When large mass of air is cooled below
its dew point, moisture in air condenses around dust par-
ticles to form mist or fog. Clouds are aerosols containing
suspended water droplets in air. Due to condensation water
droplets grow bigger and bigger till they fall down as rain.
Sometimes oppositely charged clouds colloid to make rain
happen.
iii. Food articles: Milk, butter, halwa, ice creams, fruit juices,
etc.
iv. Blood:Colloidal solution of an albuminoid substance. The
styptic action of alum and ferric chloride solution is due
to coagulation of blood forming a clot which stops further
bleeding.
v. Soils- humus protect colloidal soil.
vi. Formation of delta - Sea water contains a number of elec-
trolytes. River water when reaches sea, colloidal solution of
clay is coagulated. resulting deposition is delta.
APPLICATION OF COLLOIDS
• Electrical precipitation of smoke - Smoke is a colloidal so-
lution of solid particles such as carbon, arsenic compounds,
dust, etc., in air. The smoke, before it comes out from the
chimney, is led through a chamber containing plates having
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a charge opposite to that carried by smoke particles. The
particles on coming in contact with these plates lose their
charge and get precipitated. The particles thus settle down
on the floor of the chamber. The precipitator is called Cot-
trell precipitator. INSERT PICTURE.
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• Purification of drinking water: Alum is added to coagulate
impurities.
• Medicines - Argyrol is a silver sol used as an eye lo-
tion.Colloidal antimony is used in curing kalaazar. Colloidal
gold is used for intramuscular injection. Milk of magne-
sia, an emulsion, is used for stomach disorders. Colloidal
medicines are more effective because they have large surface
area and are therefore easily assimilated.
• When a hide, which has positively charged particles, is
soaked in tannin, which contains negatively charged col-
loidal particles, mutual coagulation takes place. This re-
sults in the hardening of leather. This process is termed as
tanning. Chromium salts are also used in place of tannin.
• Cleansing action of soaps and detergents
• Photographic plates and films: Photographic plates or films
are prepared by coating an emulsion of the light sensitive
silver bromide in gelatin over glass plates or celluloid films.
• Rubber industry: Latex is a colloidal solution of rubber par-
ticles which are negatively charged. Rubber is obtained by
coagulation of latex.
• Industrial products: Paints, inks, synthetic plastics, rubber,
graphite lubricants, cement, etc., are all colloidal solutions.
End