SURFACE CHEMISTRY 1- Define adsorption. How it is different from absorption? Give an example of each.

Adsorption: The phenomenon of attracting and retaining the molecules of a substance by a solid ( or a liquid ) on its surface resulting into a higher concentration of the molecules on the surface is known as adsorption. Adsorption is a surface phenomena while absorption is a bulk phenomena. In adsorption the molecules of a substance are present in higher concentration on the surface of the adsorbent while in absorption the molecules of a substance are uniformly distributed through out the body of a solid or a liquid. Ex. Water vapours are adsorbed by silica gel while water vapours are absorbed by anhydrous calcium chloride. 2- Differentiate between chemisorption & physisorption under the

following headsa- interparticle forces b- heat of adsorption c- reversibility d- specificity adsorbate / adsorbent. Physical adsorption Chemical adsorption The adsorbate is The adsorbate is held on the held on the surface surface by chemical forces. due 2.Heat of adsorption: to Van der of Enthalpy of adsorption is of the Waals forces Enthalpy

1.Interparticle forces:

adsorption is of the order of 200 kj mol-1 3. Reversibility: 4.Specificity adsorbate/ adsorbent: 3- What are the factors, which influence the adsorption of a gas on a solid? The extent of adsorption of a gas on a solid depends upon the following order of 20 kj mol-1 Reversible . It is irreversible . It is not very specific . It is highly specific .

factors: i) Nature of adsorbate: Gas which is more easily liquefiable or is more soluble in water is more readily adsorbed. ii) Nature of adsorbent : Same gas is adsorbed to different extents by different solids at the same temperature. Greater the surface area greater is the adsorption. Charcoal , silica gel are highly porous substances and hence are excellent adsorbent. iii) Temperature : Adsorption decreases with the increase in temperature. iv) Pressure :At constant temperature the rate of adsorption of gas increases with increase in pressure. 4- Why silica gel is used as dehumidizer? Silica gel has stronger adsorption for humidity i.e. moisture of the air because it is a porous substance. 5- A small amount of silica gel and that of anhydrous CaCl2 are placed separately in two vessels containing water vapour . What phenomena will occur? Silica gel adsorb water (adsorption) while anhydrous CaCl2 absorb water (absorption) 6- Why adsorption is always exothermic? Adsorption is accompanied by decrease of randomness i.e. this factor opposes the process i.e. S is ve . For the process to be spontaneous, G must be ve. Hence, according to equ. G = H - T S, G can be ve only if H is ve.

7- What is an adsorption isotherm ? How can the constants K and n the Freundtich adsorption equation be calculated ? Adsorption isotherm: It represents the variation of the mass of the gas adsorbed per gram of the adsorbent with pressure at constant temperature. According to Freundlich equation x/m = kp1/n log (x/m) = log k + 1/n log p Thus, if a graph is plotted between log (x/m) and log p, a straight line is obtained. The slope of the line is equal to 1/n and intercept on y axis = log k . Hence, the constants n and k can be determined. 8- How does chemical adsorption of a gas on a solid vary with temperature? How is the isobar of chemisorption different from that of physisorption? Chemical adsorption of gas on solids first increases with the increase in temperature and then decreases. The physical adsorption isobar shows a decrease in x/m throughout with rise in temperature, the chemisorption isobar shows an initial increase with temperature and then the expected decrease. 9- What is the role of adsorption in heterogeneous catalysis? The process of chemisorption on a catalyst can alter the structure and activity of a reactant . A heterogeneous catalysed reaction occurs in the following steps: a) Reactant diffuses from the fluid state towards the surface (active sites) of the solid catalyst. b) Reactants are chemisorbed at the active sites. c) A reactant is dissociated into atoms followed by reaction with the other reactant. d) Products are desorbed from the surface. Products diffuse back into the fluid phase.

10- A gas was adsorbed by activated charcoal when 20kj heat was evolved. What type adsorption it could be? Give two characteristics of this type of adsorption .what is the effect of a- pressure Physical adsorption. Two characteristics are: In physical adsorption the adsorbate is held on the surface due to Van der Waals forces. It is reversible and not very specific. Variation of physical adsorption with pressure . The amount of the gas adsorbed varies with pressure at constant temperature is given by the expression x/m = kp1/n Where n>1 b- temperature on the extent of adsorption of gas? Variation of physical adsorption with temperature Since adsorption is exothermic increase in temperature decreases the amount of gas adsorbed. 11- What is catalyst ? How does the phenomenon of adsorption explain the role played by catalyst? Catalyst is a substance which can change the speed of a chemical reaction without being used up in that reaction and the phenomenon is known as catalysis. If a catalyst increases the speed of the reaction it is called positive catalyst while if it decreases the rate of the reaction it is called negative catalyst. a)Reactant diffuses from the fluid state towards the surface (active sites) of the solid catalyst. b)Reactants are chemisorbed at the active sites. c)A reactant is dissociated into atoms followed by reaction with the other reactant. d)Products are desorbed from the surface. e)Products diffuse back into the fluid phase.

11-Differentiate between homogeneous & heterogeneous catalysis with one example each. Homogeneous Catalysis Heterogeneous Catalysis The catalyst and the reactants are The catalyst and the reactants are in in the same phase. Eg: 2SO2 (g)+ O2(g)
NO (g)

the different phase. SO3(g) 4NH3 +5O2

Pt

4NO + 6H2O

13- What are enzymes? Give the mechanism of enzyme catalysis. Enzymes are defined as biological catalysts. They are globular proteins with high molar mass ranging from 15,000 to 1000,000. The enzyme catalysed reaction takes place as given below: E+S ES EP EP E + P Where E is enzyme,S is substrate,ES and EP are the intermediates and P is product. The enzyme is regenerated. 14- How does catalyst effecta- rate constant b- equilibrium constant c- free enery d- enthalpy of reaction. a) increases b) remains unaffected c) remains unaffected d) remains unaffected ES

15- Differentiate between lyophobic and lyophilic sols. Lyophilic sols Lyophobic sols 1. They are prepared easily by shaking They are prepared by chemical methods. or warming the substances with the solvent. 2. They are quite stable and are not They are comparatively less stable and easily coagulated. 3. The particles are true molecules (molecular colloids) due to their large size. 4. Their particles are heavily The particles are usually not hydrated. Eg. Gold sol. hydrated. Eg. Starch sol. particles can be re dispersed. are easily precipitated by the addition of small amount of electrolyte. The particles consist of aggregate of molecules (associated colloids) .

5. They are reversible i.e. coagulated They are irreversible .

16- What is the dispersion phase & dispersed phase in butter, milk, smoke. Give an example of the following colloidal systemsAerosol, Gel, aquasol. Butter: Dispersed phase is liquid and dispersion medium is solid. Milk: Dispersed phase is liquid and dispersion medium is liquid. Smoke: Dispersed phase is solid and dispersion medium is gas. Aerosol: Smoke, Dust etc. Gel: Butter, Cheese etc. Aqua sol: Fe(OH)3 Sol, Al(OH)3 Sol .

17- Explain-

i- 0.1 M AlCl3 solution is more effective than 0.1M NaCl solution coagulating As2O3 solution while 0.1M AlCl3 is less effective . 0.1M Na3PO4 in coagulating Fe2O3 solution. As2S3 is vely charged sol . According to Hardy Schulze rule greater is the charge on the oppositely charged ion of the electrolyte added , more effective it is in bringing about coagulation .Hence AlCl3 (Al+3) ions is more effective. Fe(OH)3 is +vely charged sol . Hence Na 3PO4 (PO4-3) ions is more effective in bringing about coagulation. ii- alum is added to purify muddy water. Muddy water is colloidal solution of soil in water. Alum acts as an electrolyte, which neutralizes the charge on colloidal particles and cause coagulation. iii- Rivers meet oceans to form deltas. River water is colloidal solution of vely charged silicates dispersed in water. Ocean water contains Ca+2, Mg+2ions .Thus where river water meet ocean the precipitation takes place leading to the formation of deltas. iv- A negatively charged yellow sol of As2S3 on mixing with a positively charged Fe(OH)3 red sol in equivalent amount produces colourless solution Their charges are neutralized on mixing. Hence their mutual precipitation occurs, called mutual coagulation.. v- Bleeding caused by a nick from a razor during shaving can be stopped by rubbing alum. Alum contains K+, Al+3ions which causes coagulation of blood. 18- Explain the following observationsi- On passing H2S in cold , dilute solution in II group analysis sometimes yellow turbid solution. is obtained instead of precipitate. Due to the formation of colloidal sulphur. ii- During II group analysis passage of H2S sometimes brings in pale turbidity in solution. When the medium is sufficiently acidic and the acidic radical is nitrate then nitric acid is formed , which oxidizes H2S to S hence pale turbidity appears iii- The colour of KMnO4 discharges slowly in the beginning during its reaction with oxalic acid but quickly after sometime. 7

Decolourisation of oxalic acid becomes faster because of the formation of Mn+2ions which act as a catalyst. (Autocatalyst) 19-The conductance of an emulsion increases on adding common salt. What type of emulsion is this ? Oil-in-water type. 20-Why are medicines are more effective in colloidal state ? Medicines are more effective in colloidal state i.e. emulsions because in this form ,they have more surface area which makes them easily assimilated. 21- Sodium chloride can act both as crystalloid as well as colloid . explain . Sodium chloride acts as crystalloid in aqueous medium, while in non aqueous non polar medium like benzene it acts as a colloid. 22- Give a chemical and a physical method to prepare a- sulphur sol By solvent exchange: Addition of alcoholic solution of sulphur in water gives colloidal solution of sulphur in water. By Oxidation : Sulphur is obtained in colloidal form when H2S is bubbled through the solution of an oxidizing agent like HNO3, Br2water etc. H2S + Br2 H2S + 2HNO3 b- silver sol: By Bredigs method or by electro disintegration: An electric arc is set up between two silver electrodes suspended in a trough of water. The intense heat of arc converts silver into vapours which are condensed immediately in the ice cold water bath resulting in the formation of colloidal solution of silver in water. By Reduction:Very dilute solution of silver salt is treated with suitable reducing agent. 6AgCl + 3HCHO + 3H2O 6Ag + 3HCOOH + 6HCl 23- Give two tests to distinguish between two types of emulsions? 8 2HBr +S 2H2O + 2 NO2 + S

The following tests are used to distinguished between the two types of emulsions: Dye Test: A small amount of an oil soluble dye is added to the emulsion. If it is water in oil type, the background becomes colored. If colored droplets are seen , the emulsion is of oil- in -water type. Dilution Test: Add small amount of water to an emulsion. The water will mix completely if the emulsion is of oil- in -water type. In case the added water forms separate layer, the emulsion is of water-in-oil type. 24- Explain what is observed whenc- electric current is passed trough As2S3 sol. As2S3 is vely charged sol .On passing electric current the particles move towards +vely charged electrode(anode)where they lose their charge and get coagulated. d- A freshly precipitated Fe(OH)3 is shaken with a little amount of dilute solution of FeCl3. Peptization takes place forming a positively charged colloidal sol of Fe(OH)3 25- What is demulsification? Name two ways of demulsification. The separation of an emulsion into its constituent liquids is known as demulsification. Emulsions can be demulsified by separating or destroying the emulsifier. The following techniques are used for demulsification: i)Freezing ii)boiling iii)centrifugation and iv)electrostatic precipitation. 26- What happens when to ferric hydroxide sol e- sodium chloride is added The colloidal particles get precipitated, i.e. Fe(OH)3 is precipitated. f- a beam of light is passed through it.

The path of light becomes visible. This is due to the scattering of light by colloidal particles. 27-a- Why is gelatin added to ice-creams ? Ice cream is an emulsion of milk or cream in water i.e. oil-in-water. Gelatin acts as emulsifier i.e. it helps to stabilize the emulsion. b- why is artificial rain caused by throwing common salt on the clouds? Clouds are colloidal dispersion of water particles in air . The colloidal water particles carry charge. On throwing salt in the clouds coagulation of water particles takes place. 28- How can industrial smoke be minimised ? Smoke is a dispersion of vely charged carbon particles in air. Air can be made free from these particles by passing it through Cottrell precipitator attached to the chimney of an industrial plant. The precipitator consists of two metal plates charged to a high potential. When the gas comes out of the chimney , the charged carbon particles get precipitated. 29-What is dialysis? How the process of dialysis quickened? Give one practical application of dialysis. The process of separating a soluble crystalloid from a colloid is called dialysis. The process of dialysis is fastened by a) Suspending the bag in warm water. b) Applying electric field during dialysis by placing two electrodes in water outside the membrane. Artificial purification of blood (by artificial kidneys)

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30- Explain the following with reference to enzyme catalysisWhat is the optimum temperature and pH for an enzyme catalysed reaction? Enzyme catalysed reactions have maximum rate at physiological pH of around 7.4 and temperature of 37C(310K) under one atmospheric pressure. 31- With reference to heterogeneous catalyst explain the following terms with suitable exampleg- selectivity The selectivity of catalyst is its ability to direct a reaction to yield a particular product.. It means a substance which acts as a catalyst in one reaction may not catalyse other reactions. For Eg: we get different products when we use different catalysts in the reaction between H 2 and CO as shown below: CO(g) + 3H2(g)pt CH4(g) + H2O(g) CO(g) + 2H2(g) CO(g) + H2(g) b- activity. The activity of catalyst is its ability to accelerate chemical reactions. It depends upon the strength of chemisorption to a large extent. The catalytic activity increases as we move from group 5 metals to group 11.The maximum activity is shown by metals of groups 7-9. 32- What is Hardy-Schulz Rule ? Arrange the following ions to coagulate Fe(OH)3 and As2S3 sol separatelyi- Cl- , ii- Al3+, PO43-, Na+, SO42Ba2+
Cu/ZnO Cr O 2 3

CH3OH(g)

Cu

HCHO(g)

According to Hardy Schulze rule greater is the charge on the oppositely charged ion of the electrolyte added, more effective it is in bringing about coagulation. Fe(OH)3 is a +vely charged sol Coagulation power of the ion is of the order: PO4-3 > SO4-2 > ClAs2S3 is vely charged sol Coagulation power of the ion is of the order: Al+3 > Ba+2 > Na+

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33-Compare true solution with colloidal solution on the basis 1. particle size. 2. Visibility of particles 3. setting of particles 4. scattering of light S.No. Property 1. Particle size True solutions Colloidal solutions Less than 10-9m. or 1nm Between 10-9m. to 10 (i.e.< 10A) 2. Visibility of particles Particles are invisible.
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m or 1nm to 100nm

(i.e. 10A to 1000A) Particles are visible only 3. 4. Settling of particles Scattering of light Do not settle. Do not scatter light under ultra microscope. Do not settle. Scattering of light by the particles is observed under ultra microscope.

34- Point out differences between macromolecular and multi molecular colloids . Give one example of each. Multi molecular colloids consists of large aggregates of atoms or small molecules with diameters of less than 1nm, e.g. gold sol, sulphur sol etc. in which the dispersed particles consist of aggregates of atoms or molecules. These are held together by van der Waals forces. In macro molecular colloids the dispersed particles are large molecules usually polymers e.g. nylon, synthetic rubber, Dacron etc .The size of particles lie within the colloidal range. Thus their dispersion behaves like colloidal solutions and is called macromolecular colloids.

35- What is Brownian movement? How it is caused? Explain the stability of

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colloids? The colloidal particles constantly move in a zigzag motion. This is due to the collision of the colloidal particles with the moving molecules of the dispersion medium. The random and zigzag motion of the colloidal particles is called Brownian movement. Brownian movement opposes the force of gravity and does not allow the colloidal molecules to settle down. Thus it is responsible for the stability of colloidal solution. 36- Are adsorption and sorption synonymous? If not then explain each term. No, they are not synonymous. The phenomenon of attracting and retaining the molecules of a substance by a solid (or a liquid ) on its surface resulting into a higher concentration of the molecules on the surface is known as adsorption, while a process in which both adsorption and absorption take place simultaneously is called sorption. 37- Answer the following questions with respect to physisorption and Chemisorption a- Which adsorption has higher value of enthalpy and why ? Chemisorption has higher value of enthalpy because chemical bond formation takes place between adsorbate and adsorbent which results in the formation of surface compound. b- Which adsorption forms multimolecular layers? Physisorption c- Which adsorption is highly specific? Chemisorption

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d- Which adsorption decreases with increase in temperature and why? Physisorption of gas on solids decreases with the increase in temperature . Adsorbate and adsorbent are held together by weak van der waals forces so the gas adsorbed at low temperature can be freed again by heating. 38- What does the graph given below depict ?

x/M P Mark the graph where x/M P1/n The graph above shows the variation of the extent of adsorption (x/m) with pressure at constant temperature (adsorption isotherm) 39- How does lock and key model differ from induced fit model of enzyme action? Lock and key model : According to this theory, a reaction takes place when the key (substrate) fits the lock (active site) of the enzyme. If the substrate (key) does not fit into the active site (lock), no reaction takes place. Induced fit model: According to this theory, the enzyme changes shape upon binding the substrate. The enzyme and the substrate fit each other only after binding. 40- Classify the following sols as lyophobic / lyophilic and also multimolecular/ macromolecular/ associated colloids. a- Gold sol b- Starch

a- Gold sol -Multimolecular colloid.

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b- Starch Macromolecular 41- Explain the following terms with respect to Associated colloids: Kraft temperature and critical micelle concentration . Kraft temperature :The temperature above which formation of micelles ( an electrolyte behaves as colloid ) is called Kraft temperature(Tk). Critical micelle concentration: The concentration above which formation of micelles takes place is called Critical micelle concentration (CMC). 42- Describe one chemical and one physical method of preparing each of the following sols: a Sulphur sol a Sulphur sol: b) Gold sol

By solvent exchange: Addition of alcoholic solution of sulphur in water gives colloidal solution of sulphur in water. By Oxidation : Sulphur is obtained in colloidal form when H2S is bubbled through the solution of an oxidizing agent like HNO3, Br2water etc. H2S + Br2 H2S + 2HNO3 b) Gold sol: By Bredigs method or by electro disintegration: An electric arc is set up between two Gold electrodes suspended in a trough of water. The intense heat of arc converts Gold into vapours which are condensed immediately in the ice cold water bath resulting in the formation of colloidal solution of Gold in water. By Reduction:Very dilute solution of Gold salt is treated with suitable reducing agent. 2AuCl3 + 3HCHO + 3H2O 2Au + 3HCOOH + 6HCl 2HBr +S 2H2O + 2 NO2 + S

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43- What happens when an arsenious sulphide sol and ferric hydroxide sol are separately subjected to electrophoresis? Arsenious sulphide sol ,when subjected to electrophoresis , the colloidal particles move towards positively charged plate. This shows that it is negatively charged. Ferric hydroxide sol: when subjected to electrophoresis , the colloidal particles move towards negatively charged plate. This shows that it is positively charged. 44- What is the difference between a) Flocculation and coagulation? b) Peptisation and coagulation . a) Flocculation and coagulation coagulation is a process of aggregating together the colloidal particles so as to change them into large sized particles, which ultimately settle as precipitate. When a small amount of the electrolyte is added i.e. when the concentration of the electrolyte added is low, the process is called Flocculation. It can be reversed on shaking. However, at higher concentration, coagulation takes place and simply shaking cannot reverse the process. b) Peptisation and coagulation : The process of converting freshly precipitated substance into a colloidal sol is called peptisation. Adding small amount of electrolyte does this while the process of converting colloidal sol into precipitate by adding small amount of an electrolyte is called coagulation. 45-Write two tests to distinguish between vanishing cream and cold cream. Vanishing cream is oil in water emulsion while cold cream is water in-oilemulsion. Two tests are: Dye Test: A small amount of an oil soluble dye is added to the emulsion. If it is water in oil type, the background becomes colored. If colored droplets are seen, the emulsion is of oil- in -water type.

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Dilution Test: Add small amount of water to an emulsion. The water will mix completely if the emulsion is of oil- in -water type. In case the added water forms separate layer, the emulsion is of water-in-oil type. 2. Which characteristic of colloid as displayed in the following uses: a) Rubber plating and Cottrell smoke precipitate It is based on the principle of electrophoresis. b) In medicines and metallurgical operations: Adsorption and formation of emulsion.

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