183101 ENGINEERING CHEMISTRY UNIT 3 SURFACE CHEMISTRY

TERMS AND DEFINITIONS: 1. Adsorption: Concentration of liquid or gaseous molecules over the surface of a solid material is known as adsorption. It is a surface phenomenon. (e.g.) H2 adsorption over nickel. The solid material is known as adsorbent. (e.g.) Nickel The gaseous or liquid molecules are adsorbate (e.g.) H2 gas 2.If the concentration is of bulk phenomenon, it is absorption. (e.g) Absorption of Ink on the surface of a chalk . TYPES OF ADSORPTION 1. If the adsorbent and adsorbate are bonded by weak Vanderwalls forces, it is known as Physisorption. (e.g) H2 on charcoal. 2.If they are bonded by strong chemical covalent bonds, it is chemisorption. (e.g) H2 on nickel. No PHYSISORPTION 1 Adsorption is due to weak Vanderwalls forces. 2 3 4 5 6 7 8 9 10 11 They form multi layer. Reversible Equilibrium is easy Intermediate surface compound formation does not take place. Energy of activation (Ea) is low. Heat of formation and enthalpy (H) is low Inversely proportional to temperature Directly proportional to pressure, concentration Non specific and non selective e.g - H2 on charcoal. CHEMISORPTION Due to strong covalent bonding. Monolayer Irreversible Not easy Takes place High High Direct proportion Inversely proportion Selective and specific H2 on nickel.

FACTORS AFFECTING ADSORPTION a) Adsorption of gases on solids: (e.g) H2 on Charcoal (Physisorption). H2 on nickel. (Chemisorption) i. Nature of gases ii. Nature of solid iii. Activation iv. Reversible nature v. Thermodynamic quantities. (H , Ea , T, P , C)

1. Nature of gases: There are two types of gases. Permanent (e.g. - N2, H2, O2) and easily liquefiable (e.g.- HCl, NH3, SO2) gases. Easily liquefiable gases are more adsorbed than the permanent gases. Because they are having very high critical temperature (Tc) and great Vander walls forces. E.g H2 -- Tc = 33K Adsorption = 4.5ml / 1g charcoal SO2 -- Tc = 430K , Adsorption = 380ml / 1g charcoal 2. Nature of solids: For greater adsorption, the solid adsorbent must have i) High porosity ii) More surface area (e.g) powdered alumina and charcoals are having greater adsorption capacity. 3. Activation: For adsorbents, porosity is increased by rubbing, scratching and passing super heated steam. Their surface area is increased by subdividing and powdering. The entire process is known as activation of adsorbents. (e.g) Charcoal steam / Activated charcoal

4. Reversible nature: Gas + Adsorbent solid Gas Solid For Physisorption, reversibility is possible. For Chemisorption, reversibility is very least possible. 5. a) Enthalpy, Heat of absorption , Energy of activations are low for Physisorption and high for chemisorption. b) Multilayer is favoured by Physisorption and monolayer is favoured by chemisorption. c) Pressure is directly proportional to Physisorption and inversely proportional to chemisorption. d) Temperature is inversely proportional to Physisorption. In chemisorption, it is increasing with temperature, attains a maximum value and again it is coming down. Physisorption Chemisorption

Absorption

Absorption

Temperature

Temperature

b)Factors affecting adsorption of solutes from solution: 1. Nature of solutes 2. Nature of adsorbent 1. Nature of solute: High molecular weight solutes are easily adsorbed. 2. Nature of adsorbent: Adsorbent should have high porosity and surface area.

ADSORPTION ISOTHERMS AND 5 MODELS The relation between adsorption and pressure at constant temperature is known as adsorption isotherm. It may be mathematical relationship or of graphical.

(x / m) =

k .P

1/n

(at constant T)

Where, x = amount of Adsorbate m = amount of adsorbent x/m= extent of adsorption P= pressure n = whole number k = adsorption coefficient

x/m

Pressure To convert the equation as y = mx + C form, taking log on both sides, log (x / m) = log k + (1/n) log P (at constant T) Where y = log (x / m) : m = (1/n) : C = log k so, the plot will be a line with slope 1/n and intercept log k. 5 models of adsorption isotherms: ( Ps = Saturation pressure) x/m x/m x/m

P x/m

Ps Type I

P Ps Type II x/m

P Type -III

Ps

P Type IV Model I II III IV V Adsorbate Nitrogen Nitrogen Bromine Benzene

Ps

P Type - V Adsorbent Charcoal Iron / Nickel Silica Silica gel Carbon Temp -1800C -1950C 800C 500C 1000C

Ps

Water vapour

Characteristics Chemisorption (monolayer) Physisorption (Multilayer) Physisorption (Multilayer) Capillary Condensed state Physisorption Capillary Condensed state Physisorption

FREUNDLICH ADSORPTION ISOTHERM: The relation between adsorption and pressure at constant temperarute is known as adsorption isotherm. It may be mathematical relationship or of graphical. (x / m) = k . P
1/n

(at constant T)

To convert the equation as y = mx + C form, taking log on both sides, log (x / m) = log k + (1/n) log P where y = log (x / m) (at constant T) C = log k

m = (1/n)

so, the plot will be a line with slope 1/n and intercept log k. From the above graph, there may be three cases: Case 1- At low pressure, adsorption is proportional to pressure. (x/m) P (or) (x/m) = k . P1 Case 2 - At high pressure, adsorption is almost constant. (x/m) = k (or) (x/m) = k . P0 Case 3 - At Intermediate pressure. (x/m) = k . P 0 -- 1 (or) (x/m) = k . P 1/n, where n is an integer. This is known as Freundlich adsorption isotherm. Limitations of Freundlich isotherm: 1. It is only empirical formula and no theoretical evidences. 2. It is deviated at high pressure. 3. It is not good at high concentration. 4. n and k are temperature dependent.

LANGMUIR ADSORPTION ISOTHERM Postulates: 1. In adsorbent, surface valencies are not fulfilled. 2. Adsorbates are of mono layer thickness. 3. Adsorbates are of uniform distribution. 4. No interaction between adjacent gas molecules. 5. The gas molecules do not move around on the surface. Derivation: 1. As per dynamic equilibrium, ka Gas + Solid GS where, ka = Adsorption rate constant kd kd = Desorption rate constant 2. Let us consider, Total area of adsorbent = 1 Gas covered area = Then, uncovered area =(1-) 3. Rate of adsorption, Ra = Ka (1-) P Rate of desorption, Rd = kd . 4. At equilibrium, Rd = Ra kd . = Ka (1-) P kd . = Ka P - Ka P kd . + Ka P = Ka P ( kd + ka P ) = ka P = ka P _____ ( kd + ka P ) (dividing by kd)

= ( ka / kd) .P________ (kd / kd) + (ka / kd).P

AS, ( ka / kd) = K, another constant, known as Adsorption co-efficient, = K . P__ 1 + K.P

5.But, amount of gas adsorbed (x) is proportional to .

x x 1 + KP = 1 + KP K.K1 P x y

and x = K1 = K1 K P 1 + KP K1 K P x P x 1 __ KK1 C + + K.P KK1 m . x, , which is in the form of

= = =

where, intercept C = 1 / KK1 and slope m = K / KK1

P x

1 __ KK1

K.P KK1

Case 1 -, At low pressure, P is negligible. So, 1 __ >> K.P 1 KK KK1 Hence, P x = 1 __ KK1 (or) x = KK1.P = K P1

Case 2 - At high pressure, P is very big. So, 1 __ << K.P 1 KK KK1 Hence, P x = K.P (or) x = constant (or) x=KP0 KK1 ,

Case 3, At normal pressure, x = K P 0 1 (or) x = K Pn , where n= 0 1 This proves that at normal pressure, Langmuir adsorption resembles Freundlich isotherm. But still, Langmuir adsorption holds good at low pressure but fails at high pressure.

ROLE OF ADSORBENTS IN CATALYSIS A substance used to alter the rate of a reaction is called catalyst. But it should not involve in the reaction. The process is known as Catalysis. If it increases the rate of reaction, it is positive catalyst. If it decreases the rate of a reaction, it is negative catalyst. If reactants and catalyst are in same phase it is homogeneous catalysis. If they are in different phases, it is heterogeneous catalysis. E.g. N2 + 3 H2 Fe 2 NH3 . Fe is Positive / Heterogeneous catalyst . H2O2 Dil. H2SO4 H2O + O2 ,. Dil. H2SO4 is negative / Homogenous catalyst. Adsorption is mainly used in Heterogeneous catalysis. Steps involved in Heterogeneous Catalysis Contact theory. 1. Adsorption - Here the reactant molecules (A, B) are adsorbed on the solid adsorbent(C).by strong chemical bond or weak Vander walls bond. 2. Activated complex formation - The adjacent adsorbate molecules are forming weak bond (A-B) and the activated complex is formed. 3. Decomposition The bond between A and B is getting strengthen while the bond between A-B and C is getting weaken. This is called decomposition. 4. Desorption From the decomposed activated complex, the final product is released. This is known as desorption. A B A-----------B A B A B + C C C C C C C C

Step I Adsorption E.g CH2 = CH2 + H2

Step-II Activated complex

step III Decomposition

Step -IV Desorption

Nickel CH3 - CH3 (Ethylene to Ehtene)

Where A = Ethylene B = Hydrogen C= Nickel and A-B = Ethene Factors affecting heterogeneous catalysis: 1. Finely divided catalyst 2. Rough surface 3. Promoters 1. In finely divided catalysts, active centre increases. So, adsorption increases.

E.g -

N i

N i

N i

Finely divided
N i N i N i

N i

Free valencies in combined state = 10

Divided state valencies = (6 x 4)=24

2. Rough surfaces may have cracks, peaks and corners. So, number of active centre increases and adsorption increases. 3. Promoters are the substances increasing the activity of catalyst. (e.g) Mo increases Ni activity in Habers process. They increase the peaks and cracks and also the spaces between the catalyst, so adsorbed molecules bonds are further weaken and cleaved. ADSORPTION AND ION EXCHANGE PROCESS Ion exchange method ( Demineralisation) Ion exchange process depends on the concept of adsorption of Ca and Mg ions on resins. Working: Here all the cations and anions are completely removed. It uses two cylinders of cation exchange cylinder and anion exchange cylinder filled with resins.Resins are linear, insoluble, cross linked, organic polymers. There are 2 types. i) Cation exchange resins RH2 (e.g) Sulphonated coals , RSO3H ii) Anion exchange resins. R(OH)2 (e.g)Ureaformaldehyde,Amines R-NH2 The water is fed into cylinder I where all the cations are replaced by RH2 Resins. The cation free water is fed to cylinder II, where all the anions are replaced. So, the resultant water is free from all types of ions. RH2 + CaCl2 R Ca + 2 HCl R(OH)2 + 2 HCl RCl2 + 2H2O Regeneration: On prolonged use, as all the resins are exhausted, there will be + no H orOH ions to exchange the unwanted ions. So, they have to be regenerated. Cation resins are regenerated by HCl and anion resins by NaOH. R Ca + 2 HCl RH2 + CaCl2 RCl2 + 2NaOH R(OH)2 + 2NaCl

APPLICATION IN POLLUTION ABATEMENT: 1.When wood or coconut shell is heated in absence of air, charcoal is obtained. This is called carbonization. The charcoal is activated by passing steam and heated with Phosphoric acid as dehydrating agent at 5000C to make it more porous. 2. There are two types of activated charcoal. GAC(Granular activated Charcoal) and PAC( Powdered Activated charcoal.

No 1 2 3 4

GAC For long term use Dia is greater than 0.1mm Used for gases and liquids Regeneration is possible

PAC Short term use Less than 0.1mm Mainly for liquids Not possible

WATER POLLUTION TREATMENT ( USING GAC) 1. Down flow contactors: The polluted water is fed at the top of the columns containing GAC. The impurities are adsorbed on GAC. If higher degree of purity is needed, then numbers of columns are increased. The clogging in GAC is removed by backwashing. There are two types of down flow contactors. A) Parallel type b) Series type No 1 2 3 4 5 Series model High degree of purity Low volume only purified Backwash is frequently needed Low life time of GAC Out put of one column will be in put for another column. Parallel model Low degree of purity High volume can be purified Not frequently needed. High life time Single source and single terminus.