Unit-III Surface Chemistry

3. 1 UNIT III SURFACE CHEMISTRY

Adsorption: The presence of a higher concentration of a gas or liquid at the solid surface than in the bulk is adsorption. Adsorbent: The material providing the surface on which adsorption occurs is adsorbent. E.g., charcoal Absorption Absorption is the process in which molecules of a substance are uniformly distributed throughout the body of the solid or liquid. E.g., absorption of ammonia in water Differences between adsorption and absorption: S.No. Adsorption 1 2 3 Absorption

It is a surface phenomenon It is a slow process Equilibrium is attained easily Equilibrium is attained slowly The concentration of molecules is more on the surface and less in the Distribution is uniform bulk

Physical Adsorption (or) physisorption Physical adsorption is the one, where the adsorbed molecules are held on the surface of the adsorbent by weak physical (or) Vander Waalss forces of attraction. Example: Adsorption of H2 (or) O2 on charcoal. Chemical Adsorption (or) chemisorptions Chemical adsorption is the one, where the adsorbed molecules are held on the surface of the adsorbent by chemical bonds. Example: Adsorption of H2 on Ni

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Unit-III Surface Chemistry

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Differences between Physical Adsorption (or) physisorption and Chemical Adsorption (or) chemisorptions S. No. 1 2 3 4 5 6 7 8 9 Physisorption It is caused by intermolecular Vander Waalss forces (weak). Heat of adsorption is low (0-40 k.cal/mol) It is completely reversible. It decreases with increase in temperature. Multilayer adsorption occurs. The rate of adsorption increases with the increase of pressure and concentration. Equilibrium is established rapidly It involves very small activation energy. It is not specific in nature Chemisorption It is caused by chemical bond formation (strong) Heat of adsorption is high (40-400 k.cal/mol)` It is irreversible It increase with temperature. Only monolayer adsorption occurs. The rate of adsorption decreases with increase of pressure and concentration. It requires time It involves appreciable activation energy. But it is highly specific nature.

The factors that influence the adsorption of gases on solids. 1. Nature of the gas: Easily liquefiable gases (like HCl, NH3, Cl2, etc.) are adsorbed more easily than the permanent gases (like H2, N2, and O2 etc.). The higher the critical temperature (T), the more easily the gas is liquefied and consequently, more readily it is adsorbed. 2. Nature of adsorbent: Greater the surface area of the adsorbent, greater is its absorption capacity. Larger pores on the adsorbent, larger are the adsorption. 3. Effect of pressure: Adsorption increases with pressure of the gas 4. Effect of temperature: Since adsorption is an exothermic reaction, with an increase in temperature, the amount adsorbed (x/m) decreases, for physical adsorption. For chemical adsorption, it increases with temperature and then decreases. 5. Activation of adsorbent: In order to increase the rate of adsorption, activation is very necessary. Creation of rough surface: By mechanical rubbing of the solid adsorbents. Increasing effective area of the surface: By sub-dividing the solid adsorbent into finer particles. 6. Enthalpy of adsorption: Adsorption is invariably an exothermic (i.e., liberation of heat) process. In physical adsorption, the attraction between gas molecules and solid surfaces are due to relatively weak Vander Waals forces. The heat of adsorption is small (about 5 k.cal/mol).

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Unit-III Surface Chemistry III

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In chemical adsorption, the attractive forces are due to the formation of chemical bonds. The heat of adsorption is large (about 100 k.cal/mol). 7. Reversible nature of adsorption: Physical adsorption is a reversible process, so the adsorbed gas can be easi easily desorbed (or) removed / under reverse conditions of temperature and pressure). Chemical adsorption: It is not a reversible process, because a surface compound is formed. 8. Thickness of adsorbed layer of gas: In physical adsorption above a certain pressure, multimolecular thick layer is formed. pressure, In chemisorptions only unimolecular thick layer is formed. Freundlichs Adsorption Isotherm The relationship between the magnitude of adsorption (x/m) and pressure (P) can be expressed mathematically by an empirical equation known as Freundlich adsorption isotherm. (x/m)=kP1/n k=constant n=integer Derivation of Freundlichs Adsorption isotherm The equation for freundlichs adsorption isotherm may be derived from the result observed from the graph shown below.

(i)

At low pressure: Adsorption increases with pressure x P (or) x = kP m m At high pressure: Adsorption is independent of pressure. x = constant (or) x = k m m

(ii)

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(iii)

At intermediate (normal) pressure: Adsorption depends on 0 to 1 power of pressure (ie., fraction a power pressure) x P1/n (or) x = kP1/n m m where, n = whole number.

This equation (1) is called Freundlichs adsorption isotherm. Taking logarithm on both sides, the above equation becomes Log x/m = logk + 1/n log P On ploting log x/m Vs log P, a straight line is obtained with a slope of 1/n and intercepts log k Disadvantages (or) limitations of Freundlichs adsorption isotherm Freundlich equation is purely empirical and has no theoretical basis. The equation is valid only upto a certain pressure and invalid at higher pressure. The constants k and n are not temperature independents, they vary with temperature. Freundlichs adsorption isotherm fails, when the concertration of adsorbate is very high.

Langmuirs Adsorption Isotherm Postulates (or) assumptions 1. Valencies of the adsorbent atoms at the surface are not fully satisfied. As a result the surface has a fixed number of adsorption sites. 2. The adsorbed gas layer is only one molecule thick 3. Each site can adsorb a single molecule. 4. Adsorption consists of two opposing processes. 5. Condensation of gas molecules on the adsorbent surface. 6. Evaporation of adsorbed molecules from the surface of the adsorbent. 7. After sufficient time, there is a dynamic equilibrium. The rate of condensation is equal to the rate of evaporation. 8. The surface of the solid is homogeneous, so the adsorbed layer is uniform all over the surface. 9. There is no interaction between the adsorbed molecules. 10. Adsorbed gas behaves ideally. 11. The adsorbed gas molecules do not move around the surface.

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Unit-III Surface Chemistry

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Derivation of Langmuir adsorption isotherm: According to Langmuirs assumptions, when the gas molecules strike a solid surface, some of the molecules are adsorbed and some of these are desorbed. Thereby dynamic equilibrium is established between adsorption and desorption. If A is gas molecule and M is surface then,

ka A(g) + M (surface) kd Let, Fraction of the total surface covered by the adsorbed molecule Fraction of uncovered area (vacant area) The rate of desorption is proportional to number of adsorbed molecules where kd = Rate constant for desorption. Thus, the rate of adsorption is proportional to available uncovered area = Ra = ka (1 )P = AM

= (1 )

R d = kd

At equilibrium Rate of desorption = Rate of adsorption kd = ka ( 1 -)P = kaP ka P kd + kaP = kaP (kd + kaP) = kaP = kaP /(kd + kaP)

(1)

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Unit-III Surface Chemistry

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Dividing the equation (1) by kd it becomes = (ka / kd) P 1+(ka/kd)P =

KP 1+KP (2) Where ka / kd = K = equilibrium constant, called adsorption coefficient. But the amount of gas adsorbed per gram of the adsorbent, x, is proportional to . On comparing equation (2) and (3), it becomes x KP 1+KP x = K KP 1+KP Where, K = new constant. The equation (4) gives the relation between the amount of gas adsorbed to the pressure of the gas at constant temperature. It is known as Langmuirs Adsorption Isotherm. The above equation (4) may be re-written as 1+ KP = K KP x 1 + KK
1

(4)

KP K1K

= P x

(5)

The equation (5) is similar to an equation for a straight line (ie., y = c+ mx). If the graph is plotted between P/X Vs P, we should get a straight line with slope K/KK and the intercept 1/KK This equation is found valid in all cases. Case (i) at low pressure If the pressure (P) is very low KP term is negligible, KK >> K 1 KK KK Hence equation (5) becomes = P (or) x = PKK 1 KK x i.e.,

(6)

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Unit-III Surface Chemistry

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(or)

x P

ie., amount of adsorption per unit weight of adsorbent directly proportional to the P at low P. case (ii): At high pressure If the pressure (P) is high 1 K K >> 1 i.e., KP KK KK

term is negligible,

Hence equation (5) becomes = P (or) X= K (Constant) KP x KK (or) x = K P0

(7)

i.e., extent of adsorption is independent of pressure of the gas, because the surface becomes completely covered at high pressure. Case (iii) : at normal pressure If the pressure (P) is normal (intermediate) the equation (7) becomes x = K1Pn
(8)

Where, n lies between 0 and 1. Equation (8) is similar to Freundlichs adsoreption isotherm. Merits and Demerits of Langmuirs adsorption isotherm Merits; 1. Plot of P/x versus P gives a straight line only at low pressures. 2. It qualitatively explains the adsorption at various pressures. Demerits: 1. The gases do not behave ideally. 2. It fails at high temperatures. 3. Multilayer adsorption of gases is possible. 4. The adsorbent surface is not uniform throughout. 5. The adsorbent and adsorbate may chemically interact in a few cases. Applications of adsorption 1. Activated Charcoal a. It is used in gas-masks, which adsorb all undersirable (toxic) gases, while purified air passes through its pores. b. It is also used for removing colouring matter form the sugar solution and the decolaration in vinegar.

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Unit-III Surface Chemistry

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2. Silica and alumina gels These are used as adsorbent for removing moisture and for controlling humidities of room. 3. In heterogeneous catalysis In heterogeneous catalysis, the molecules are adsorbed on the surface of catalyst which form adsorption complex. Then it decomposes to form product. Examples: (i) Manufacture of SO3 by contact process. (ii) Hydrogenation of oils. 4. Fullers earth It is used in large quantities for refining petroleum and vegetables oils, which adsorb unwanted materials. 5. Ion-exchange resins Softening of hard water can be done based on the principle of competing adsorption using ion-exchange resins. 6. Froth Flotation process The sulphide ores (PbS, ZnS, Cu2S) are freed from silica and other earthly matter by froth flotation process. (oil adsorbs sulphide ores only, but not others). 7. Arsenic poisoning Colloidal ferric hydroxide is administered, which adsorbs arsenic poision and is removed from the body by vomiting. 8. Lake test for A13+ It is based on the adsorption of litmus colour by A1(OH)3 precipitate. 9. Mordants These are used in dyeing industry, which adsorb the colouring matter without attaching to the fabrics. 10. Production of High Vacua If the partially evacuated vessel is connected to a container of activated charcoal (or) silica gel cooled with liquid air, it will adsorb all the gas molecules in the vessel. This results in a very high vacuum. 11. Chromatographic analysis Selective adsorption by alumina, magnesia, etc., can be used for separating different pigments and also mixtures of small quantities of organic substances with the help of adsorption chromatography. Adsorption of solutes from solution: Solid surfaces adsorb solutes from solutions. (e.g.) Activated animal charcoal adsorbs colouring matter from sugar solution and makes the solution colorless. 1. Positive adsorption When the solute is taken by an adsorbent, it is called positive adsorption. In this case concentration of the solution decreases after the treatment with adsorbing agent. E.g.,From a concentrated solution of KCl, charcoal adsorbs KCl only and not water.

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Unit-III Surface Chemistry

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2. Negative adsorption When the solvent is adsorbed in preference to the solute, the concentration of the solution actually increases after treatment with the adsorbing agent. This phenomenon is known as negative adsorption. From a dilute solution of KCl, charcoal adsorbs water only and not KCl Factors influencing adsorption of solutes from solutions 1. The nature of the adsorbent Some adsorbents are specifically more effective in attracting certain substances to their surface than others. Example Activated carbon is more effective in adsorbing non-electrlytes from a solution than electrolytes while inorganic solids adsorb electrolytes more readily than non-electrolytes. a. The area of the adsorbent An increase in the surface area of adsorbent increases the total amount of solute adsorbed. b. The nature of solute adsorbed The extent of adsorption is usually greater when the molecular weight of the solute is high. c. Effect of temperature An increase in temperature decreases the extent of absorption and vice versa. A rise in temperature increases the kinetic energies of solute particles and hence these particles leave the surface and thereby lowering the extent of adsorption. d. The concertration of the solids Adsorption of solutes also involves the establishment of equilibrium between the amount adsorbed and the concentration of solute in solution. In the Freundlich adsorption isotherm, using concentration instead of pressure obeyed by adsorption from solution. w =kc1/n m where w = mass of solute adsorbed on a mass m c = equilibrium concentration of the solution K & n are constants. Log w m = log (k) + 1 log c n

This implied that a plot of log w/m against log c should be a straight line. The validity of Freundlich isotherm has been tested by plotting the experimental values of log w/m Vs log c determined for adsorptions of acetic acid on charcoal at 250C.

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Unit-III Surface Chemistry

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Role of Adsorbents Role of Adsorbent in Catalysis (or) Adsorption (or) Contact Theory 1. Action of heterogeneous catalyst Various steps involved in heterogeneous catalysis. Step:I adsorption of reactant molecules The surface of the solid catalyst possesses some isolated active centres, which adsorbs gasous reactants either physisorption or chemisorptions. Step II: Formation of Activated complex The adsorbed molecules adjacent to one another join to form an intermediate complex. The activated complex is unstable. Step III: Decomposition of Activated complex The activated complex breaks to from the products. The separated particles of the products bound to the catalysts surface by partial chemical bonds. Step IV: Desorption of products The products are desorbed (or) released from the surface. They are stable. Example: Hydrogenation of ethylene using Ni catalyst

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2. Finely divided state of catalyst is more efficient When the fineness of the catalyst increases, the free surface area gets increased. Thereby free valencies (or) active centres, which are responsible for the adsorption, increase. Consequently the activity of the catalyst is also enhanced. 3. Enhanced activity of a rough surfaced catalyst Generally rough surface of a catalyst possesses Cracks Peaks, Corners etc., and consequently have larger number of active centres. These active centres increase the rate of reaction. 4. Action of promoters Promoters are defined as the substances which increase the activity of a catalyst. Explanation: the action of promoter is explained as follows a. Promoters change the lattice spacing b. Promoters increase the peaks and cracks Promoters increase the peaks and cracks on the catalyst surface. E.g. molybdenum acts as a promoter in the hydrogenation process using nickel catalyst. 5. Action of catalytic poisons A substance which destroys the activity of a catalyst is known as catalytic poisoning Explanation: preferential adsorption of poisons on the catalytic surfaces Number of free valancies or active centers of the catalysts are reduced by the preferential adsorption of the poisons. So rate of reaction decreases 6. Specific action of the catalyst The adsorption depends on the nature of both the adsorbent (catalyst) and the adsorbate (reactants). So, different catalysts can not possess the same affinity for the same reactions. Thus, the action of the catalyst is specific Role of Adsorbents in Ion-exchange adsorption Nowadays synthetic resins are used mainly as ion-exchange resins or ion exchangers. These ion exchangers possess one adsorbed ion on it. Ion exchangers release this ion and adsorb another like ion. This process as called ion exchanger adsorption Definition Ion exchange adsorption is defined as, The process of releasing the ion and adsorbing another like ion Classification of ion exchangers Ion exchangers are classified into two types, 1. Cation exchanger 2. Anion Exchanger Cation exchanger Resins containing acidic functional groups (-COOH, -SO3H) are capable of exchanging their H+ ions with other cations of hard water. Cation exchange resin is represented as RH2 RH2 + CaCl2 RCa + 2HCl

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Examples: 1. Sulphonated coals. 2. Sulphonated polystyrene R SO3H ; R COOH = RH2 Anion Exchanger Resins containing basic functional groups (-NH2, -OH) are capable of exchanging their anions with other anions of hard water. Anion exchange resin is represented as R (OH)2. R(OH)2 + H2SO4 RSO4 + 2H2O Examples: 1. Cross linked quaternary ammonium salts. 2. Urea-formaldehyde resin. R NR3OH ; R OH ; R-NH2 = R(OH)2 Applications of Ion exchange adsorption a. Ion exchange adsorption has many applications in industry and medicine b. Deionization of water c. Weakly basic anionic exchange resins are used to remove acidity in stomach d. Excess nations from body fluids can be removed by giving the patient a suitable ion exchange resins to eat Ion exchange adsorption Use of ion-exchange adsorption in demineralisation of water.

The hard water first passed through a cation exchange folumn, (fig. ) which adsorbs all the cations like Ca2+ , Mg2+ , Na+, K+, etc., present in the hard water

Department of Chemistry, Annapoorana Engineering College, Salem

Unit-III Surface Chemistry

3. 13 RCa + 2HCl RMg + H2SO4 RNa + HCl

RH2 + CaCl2 RH2 + MgSO4 RH + NaCl

The cation free water is then passed through an anion exchange column, which adsorbs all the anions like Cl-, SO42-, HCO3- etc., present in the water. R(OH)2 + 2HCl R(OH)2 + H2SO4 R Cl2 +2H2O RSO4 + 2H2O

The water coming out of the anion exchanger is completely free from cations and anions. This water is known as demineralised water or deionised water. Regeneration The cation exchange resin is regenerated by passing dilute acid RCa +2HCl RH2
+

CaCl2

Similarly, the anion exchange resin is regenerated by passing dilute alkali R(OH)2 + 2NaCl RCl2 + 2NaOH Water softening (Zeolite process) Hard water contains Ca2+and Mg2+ ions. These ions form hard soap (insoluble compound) with soap which does not produce lather with water. Process Hard water is softened by passing it through a column packed with sodium cation exchange resin (RNa+). The Ca2+ and Mg2+ ions in hard water are replaced by Na+ ions. 2R- - Na+ + Ca2+ Sodium exchanger R2Ca + 2Na Exhausted resin

Regeneration The exhausted resin is again regenerated by treating it with sodium ion (Na+) solution. R2Ca + 2Na+Cl2R-Na+ + CaCl2

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Unit-III Surface Chemistry

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Pollution abatement of water and air In the pollution abatement of air and waste water, activated carbon is a commonly used adsorbent because it has a large surface area per unit volume of solid. Treatment of Polluted Water and Air Polluted water and air can be treated by using the following two types of activated carbons. 1. Granular Activated Carbon (GAC) 2. Powdered Activated Carbon (PAC) 1. Using Granular Activated Carbon (GAC) A fixed bed activated-carbon contactors is used for contacting polluted water (or) air with GAC. It can be operated singly, in series (or) in parallel. Several types of fixed-bed activated carbon contactors are used in the treatment of polluted water (or) air. The following models are important. a. Down flow fixed-bed carbon contactors. b. Upflow fixed-bed carbon contactors. a. Down flow fixed-bed carbon contactors. Down flow fixed-bed carbon contactors consist of two (or) three columns operated in series (or) in parallel as shown in the fig.

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The water (or) air is applied to the top of the column and withdrawn at the bottom. The activated carbon is held in place with an under drain system at the bottom of the column. Advantages Adsorption of organic materials and filtration of suspended solids take place in single step. Disadvantages 1. Down flow filters require frequent back washing because of the accumulation of suspended material on the surface of the contactor. 2. Plugging of carbon pores may require premature removal of the carbon for regeneration. This decreases useful life of the carbon. b. Upflow fixed-bed Carbon Contactors In the upflow fixed bed columns, the polluted water (or) air moves upward from from the base of the column as shown in the fig.

Advantages: As the carbon adsorbs organic materials, the apparent density of the carbon particles increases. This encourages migration of the heavier or spent carbon downward. Disadvantages: Upflow columns may have more carbon fines in the effluent than downflow columns, because upflow tends to expand, the carbon. Bed expansion allows the fines to escape through passage ways created by the expanded bed. 2. Using Powdered Activated Carbon (PAC) In this method powdered activated carbon (PAC) is added directly into the effluent coming out from the various biological treatment processes. The effluent from the biological treatment plant, is mixed with PAC and a coagulant (polyelectroyte) in a contact-aeration tank.

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Unit-III Surface Chemistry

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After some time, the effluent is allowed to store in a clarification tank. The carbon particles get settled at the bottom of the tank. Since the carbon particles are very fine, a coagulant such as polyelectrolyte is added to aid the removal of the carbon particles. The spent carbon is regenerated by passing it into the regenerating column and is used again for the process. Finally the water (effluent) is filtered by passing it through the filtration column. Applications of Activated Carbon There is no particular activated carbon that is effective for all purposes. 1. In odour Control: Activated carbon adsorbers are commonly used for odour control. Activated carbon has different rates of adsorption for different substances. It is effective in removing hydrogen sulfide. The removal of odours depends on the concentration of the hydrocarbons in the odorous gas. Hydrocarbons are adsorbed preferentially before the compounds like H2S are removed. 2. As a Decolourant: Activated carbon, with its very great surface area and pore volume, removes colour from the solutions. 3. In Solution Purification: Activated carbon is also used in cleaning sugar solution and for the removal of tastes from water supplies, vegetable and animal fats and oils, alcoholic beverages, chemicals and pharmaceuticals. 4. In Gas Masks: The vapour adsorbent type of activated carbon is used in gas masks, because of its ability to adsorb poisonous gases. It is now employed in both military and industrial gas masks. 5. In Air Conditioning Activated carbon is used in air conditioning systems to control odours in large restaurants, auditoriums, etc., Department of Chemistry, Annapoorana Engineering College, Salem

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6. In Industrial Recovery Activated carbon adsorbs practically any organic solvent at about 350C and releases it when heated to 1200C or higher for solvent recovery. 7. In Cigarette Filters Specially impregnated grades are used in cigarette filters. 8. In the Removal of Organic and Inorganic Compounds Activated carbon is generally used for the removal of the refractory organic compounds as well as residual amounts of inorganic compounds such as nitrogen, sulfides and heavy metals. Activated carbon is also effective in adsorbing organic molecules even from humid gas and stream.

PART-A 2 mark question & answers 1. Define adsorption and adsorbate Adsorption: The phenomenon of a higher concentration of molecules of a gas or liquid at a solid surface than in the bulk is called adsorption. The adsorption of a gas on a solid is sometimes called occlusion. Adsorbate: The substance which is held on the surface of the solid is called adsorbate 2. What is sorption? Sorption is the process in which both adsorption and absorption take place simultaneously 3. Define the terms adsorbent and adsorbate giving suitable examples Adsorbate: The substance which is held on the surface of the solid is called adsorbate Example: H2 gas Adsorbent: The solid that takes up a gas or a solute from the solution is called the adsorbent. Example: Ni (Solid) 4. What is chemisorption? Give an example Chemical adsorption is the one, in which the adsorbed molecules are held on the surface of the adsorbent by chemical bonds (Covalent bond or ionic bond) Example: Adsorption of H2 on Ni 5. What is physical adsorption or physisorption.Give an example? Physical adsorption or physisorption is the one, in which the adsorbed molecules are held on the surface of the adsorbent by weak physical or van der Waals forces. Example: Adsorption of H2 or O2 on charcoal

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6. Mention some important characteristics of adsorption Adsorption on surface of a solid is always spontaneous Adsorption is always accompanied by evolution of heat Adsorption is accompanied both by decrease in enthalpy and entropy of the system Adsorption is a selective process 7. Explain the effects of temperature on adsorption Physical adsorption: It occurs rapidly at lower temperature and decreases with increase in temperature Chemical adsorption: It increases with increase of temperature and then decreases 8. What are the differences between absorption and adsorption? S.No 1 2 3 4 Adsorption Adsorption is a surface phenomenon It is a rapid process Equilibrium is attained easily The concentration of the molecules are more on the surface and less in the bulk Absorption Absorption is a bulk phenomenon It is a slow process Equilibrium is attained slowly But, distribution is uniform

9. How does chemisorption differs from physisorption (or) Write any two differences between chemisorption and physisorption

S.No 1 2 3 4 5

Physisorption It is caused by intermolecular Vander waals forces(Weak) Heat of adsorption is low(20-40 k.cal/mol) Adsorption is completely reversible Multilayer adsorption occurs Adsorption decreases with increase in temperature

Chemisorption It is caused by chemical bond formation(Strong) Heat of adsorption is high (40-400 k.cal/mol Adsorption is completely Irreversible Only monolayer adsorption occurs Adsorption increases with temperature

10. How will you increase the activity of an adsorbent? Activation leads to increase in the surface area of the adsorbent, which increases adsorption. Activation is achieved by the following ways Creation of rough surface

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By mechanical rubbing of the solid adsorbents By subjecting to some chemical reactions on the solid adsorbent.

Increasing effective area of the surface By sub-dividing the solid adsorbent into finer particles By heating of solid adsorbent in superheated steam, now its pores are opened and adsorption increases 11. Explain the function of activated charcoal with example It adsorbs coloring matter present in sugar solution It also adsorbs out NH3 from the solution of NH4OH and phenolphthalein It also adsorbs certain acids like CH3COOHand (COOH)2 present in water, thereby acid concentration in water decreases 12. Define adsorption? What is an adsorption isotherm? Adsorption: The phenomenon of a higher concentration of molecules of a gas or liquid at a solid surface than the bulk is called adsorption. Adsorption isotherm: Adsorption isotherm is a relationship between magnitudes of adsorption with pressure. x/m =KP1/n 13. What is Freundlichs adsorption isotherm? The relationship between the magnitude of adsorption (X/m) and pressure (P) can be expressed mathematically by an equation known as Freundlichs adsorption isotherm. x/m =KP1/n 14. Write a suitable equation commonly applied to the adsorption of liquids on Solids. x/m =KC1/n log x/m = log K + 1/n log C Where, K & n = Constants x= mass of adsorbate m= mass of adsorbent 15. Explain the limitations of Freundlichs adsorption isotherm? Freundlich equation is purely empirical and has no theoretical basis The equation is valid only up to a certain pressure and invalid at high pressure. The constants K and n are not temperature independents, they vary with temperature Freundlichs adsorption isotherm fails, when the concentration of adsorbate is very high

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Unit-III Surface Chemistry

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16. What is Langmuirs adsorption isotherm? How it is mathematically represented? The relationship between the amounts of gas adsorbed to the pressure of the gas at constant temperature is known as Langmuirs adsorption isotherm. It is represented mathematically as x = K KP/ 1+ KP 17. What is a demerit of Langmuirs adsorption isotherm? Langmuirs adsorption isotherm holds good at lower pressure but fails at higher pressure. 18. What are promoters? Promoters are defined as, the substances which increase the activity of a catalyst. 19. What is catalytic poisoning? A substance which destroys the activity of the catalyst is called catalytic poisoning. 20. What is the effect of temperature and pressure on the adsorption of hydrogen gas on charcoal ? Adsorption of hydrogen gas on charcoal is rapid at lower temperature and decrease with increase in temperature, but the rate of adsorption increases with increase of pressure. 21. What is the effect of increase in temperature and increase in pressure on the adsorption of gas on a solid? Effect of increase in pressure: Adsorption generally increases with increase of pressure Effect of increase in temperature: Physical adsorption: It increases with increase in temperature Chemical adsorption: It increases with increase in temperature and then decreases 22. How arsenic poisoning is removed from the body? Colloidal ferric hydroxide is administered, which adsorbs arsenic poison and is removed from the body by vomiting 23. Define ion-exchange adsorption (or) what do you understand by ion-exchange adsorption. Give one example Ion-exchange adsorption is the process of releasing the ion and adsorbing another like ion. Example: Water softening using zeolite When water containing Ca2+ and Mg2+ ions are allowed to pass over a zeolite bed, Ca2+ and Mg2+ ions are replaced by Na+ ions.

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Unit-III Surface Chemistry

3. 21 R2Ca +2 Na+

2R-Na+ +Ca2+

24. How is evaporation of water in lake minimized? Due to scarcity of water during summer , layers of stearic acid is spread over water lakes and reservoirs. The adsorbed stearic acid on the surface of water minimizes evaporation of water 25. What is the role of adsorbent in catalysis? The catalyst (adsorbent) adsorbs the reactant molecules on its surface and brings them in close proximity for the reaction to occur. It helps in the formation of activated complex. Reactants are easily broken and the products are easily formed. 26. Where is ion exchange adsorption applied? Ion exchange adsorption applied, where the dissolved ions are exchanged with the ions of the adsorbents. Example: In water softening Ca2+,Mg2+,SO42- ions are removed by ion exchange resin. R-Ca + 2 HCl R-SO4 + 2NaOH RH2 + CaCl2 R (OH)2 + Na2SO4

27. What is activated carbon? Activated carbon is a form of carbon that is processed to make it extremely porous and this have a very large surface area 28. What is the use of activated carbon? It is used to filter the harmful chemicals from the polluted air &water 29. What are the merits of activated carbon treatment of water? Activated carbon treatment of water filters a wide range of chemicals like fuels, dioxin PCBs and radioactive wastes It can also remove some types of metals, if present in small amounts 30. What are the demerits of activated carbon treatment of water? Activated carbon treatment does not destroy the chemicals Activated carbon treatment does not bind well to certain chemicals including alcohols, glycols, ammonia, strong acid and bases

PART-B 1. Explain the classification and functions of ion-exchangers Cation exchanger Anion exchanger

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2. Define the term adsorption and list its application Activated charcoal Silica and alumina gels In heterogeneous catalysis Fullers earth Ion-exchange resin Froth flotation process Arsenic poisoning Lake test for Al 3+ Mortants Production of high vaccua 3. Explain the role of adsorption in demineralization of water Cation exchanger Anion exchanger Demineralization process Zeolite process Electrical demineralization process 4. Derive freundlichs adsorption isotherm. Give the condition in which it fails 5. Derive an expression for Langmuirs adsorption isotherm. Show that at normal pressure Langmuirs adsorption isotherm becomes identical with freundlichs adsorption isotherm 6. Explain the role of adsorbents in pollution abatement 7. Explain the role of adsorption in catalysis. Give examples Finely divided state of catalyst ins more efficient Activity of a rough surfaced catalyst Action of promoters Action of catalytic poison Specific action of the catalyst Action of heterogeneous catalysis 8. Distinguish between physisportion and chemisorption 9. What are the factors that influence the adsorption of gases on solids? Discuss in details Nature of gases Nature and surface area of adsorbent Heat or Enthalpy of adsorption Reversible character of adsorbed gases Effect of pressure of gas Effect of temperature of gas Thickness of adsorbed layer of gas

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Unit-III Surface Chemistry

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Activation of adsorbent 10. Explain the role of activated carbon in pollution abatement? Treatment of polluted water and air Using granular activated carbon (GAC) i) Down flow fixed-bed carbon contactors ii) Up flow fixed-bed carbon contactors b) Using powdered activated carbon (PAC) 11. Write the applications of activated carbon? In odour control As a decolourant In solution purification In gas masks In air conditioning In industrial recovery In cigarette filters 12. What are the factors that influence the adsorption of solutes from solutions? Discuss in detail Effect of temperature and concentration i) Negative adsorption ii) Positive adsorption Effect of surface area The nature of the solute adsorbed

Department of Chemistry, Annapoorana Engineering College, Salem