Set No. Code No. NR-210801 II B.Tech.

I Semester Supplementary Examination November, 2003 PHYSICAL CHEMISTRY (Chemical Engineering) Time: 3 hours Max. Marks:80 Answer any Five questions All question carry equal marks --Derive an equation for distribution coefficient when solute undergoes association What are the limitations of distribution law? What are the general concepts of Chromatography? Explain the classification of Chromatography. Derive the relation between elevation of boiling point and molality of the solution. Discuss the significance and ebullioscopic constant. Discuss the phenomenon of osmosis and its origin. Explain how osmosis is a colligative property? Derive a relationship between molecular weight and elevation in boiling point. The following data were obtained in a colorimetric study of the concentration of CuSO4 :[CuSO4] x 104 moles/litre 0.4 0.8 1.2 2.0 2.4 2.8 3.2 Absorbance 0.11 0.21 0.33 0.54 0.65 0.75 0.86 Verify, graphically that the data is consistent with Beer’s law. Write briefly on the factors affecting the fluorescence phenomena. What are the advantages of conductometeric titrations? Discuss the curve obtained in the titration of weak acid with a weak base. Explain the term parachor and discuss its utility in the elucidation of structure of molecules. The density of acetone is 0.791 g/cc at 20oC. Calculate its surface tension, given that its parachor is 162. Obtain a relation between Van’t Hoff factor and degree of dissociation of solute. An aqueous solution of K4 Fe(CN)6 freezes at – 0.0620C. Calculate the percentage of dissociation. (Kf = 1.86). -x-

1

1.a) b) 2.a) b) 3.a) b) 4.a) b) c) 5.a)

b) 6.a) b) 7.a) b) 8.a) b)

Set No. Code No. NR-210801 II B.Tech. I Semester Supplementary Examination November, 2003 PHYSICAL CHEMISTRY (Chemical Engineering) Time: 3 hours Max. Marks:80 Answer any Five questions All question carry equal marks --1.a) State Nernst distribution law and its limitations. b) Explain its applications in de silverisation of lead. c) 12 grams of an organic substance A is present in 100 grams of its aqueous solution. How much of it would be left behind after extracting the solution with two successive applications of 50 ml of each other. The distribution coefficient of A between water and ether is 2 in favour of ether. 2.a) b) 3.a) b) 4.a) b) 5.a) Explain Ion exchange Chromatography What are the techniques used to carry out the Chromatographic development, explain Describe the experimental method for the determination of elevation of boiling point. Explain why elevation of boiling point is a colligative property. Derive a relation between osmotic pressure and concentration of solutions. Describe how osmotic pressure is determined experimentally. In an experiment involving estimation of ferric iron in a sample of cement by colorimetry using ammonium thiocyanate, the following data was obtained: Conc. In mg 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 Optical density 0.10 0.21 0.31 0.42 0.51 0.62 0.71 0.83 Prove, graphically that the date is in accordance with Beer’s law. A sample of acetone absorbs monochromatic radiation at a rate of 9 x 1020 quanta per sec. Calculate the quantum efficiency of the photolysis of acetone if 1.80 x10 –2 moles of acetone are decomposed per minute. What is activity? Explain the relation between activity, mean activity, activity coefficient and mean activity coefficient of ions in an electrolyte? Illustrate with examples. Discuss the effect of temperature on the viscosity of a liquid. The dipole moment of chloro- and nitrobenzene are 1.55 D and 3.8 D. Calculate the dipole moment of m-di-chlorobenzene and o-di-nitrobenzene. Obtain a relation between Van’t Hoff factor and degree of association. 20.27gm of benzene containing 0.2965gm of benzene acid (MW = 122) freezes at 0.317oC below the freezing point of pure benzene. If benzoic acid exists as a dimmer in benzene, find its degree of association, given Kf of benzene is. 512oC/m. -x-

2

b)

6. 7.a) b) 8.a) b)

Set No. Code No. NR-210801 II B.Tech. I Semester Supplementary Examination November, 2003 PHYSICAL CHEMISTRY (Chemical Engineering) Time: 3 hours Max. Marks:80 Answer any Five questions All question carry equal marks --Explain the limitations of distribution law. Illustrate the modification of distribution law for the change of molecular weight of solute in one of the solvents. Explain the principle and theory of GLC. What are the factors that affect the separation? Derive a relationship between molecular weight of the solute and elevation of boiling point. Define ebullioscopic constant. Discuss the factors which influence the constant. Discuss the mechanism of osmosis and the relation between laws of dilute solutions and Raoult’s law. Discuss critically the theories of osmosis. What is fluorescence and what are the factors affecting it? The following data were obtained in a colorimetric study of the concentration of Nickel nitrate;[Ni(NO3)2 x 103 mole/litre 0.3 0.6 0.9 0.12 1.5 1.8 Absorbance 0.05 0.10 0.16 0.21 0.24 0.29 Prove graphically that the data obeys Beer’s law. Write an expression for the activity and mean activity coefficient of an electrolyte. Illustrate your answer taking AlCl3 as example and write an expression for the activity of AlCl3 in terms of molality and mean activity coefficient. What is meant by dipole moment? Name two molecules that show a dipole moment and two molecules which do not show it. Calculate the density of naphthalene decahydride (C10H18) from its refractive index value of 1.4804 at 18 oC. Explain the Van’t Hoff factor and derive an equation for the same. A decimolar solution of potassium ferrocy anide is 50% dissociated at 300K. Calculate the osmotic pressure. -x-

3

1.a) b) 2.a) b) 3.a) b) 4.a) b) 5.a) b)

6.

7.a) b) 8.a) b)

Set No. Code No. NR-210801 II B.Tech. I Semester Supplementary Examination November, 2003 PHYSICAL CHEMISTRY (Chemical Engineering) Time: 3 hours Max. Marks:80 Answer any Five questions All question carry equal marks --What are the limitations of distribution law? Discuss the determination of relative molecular weight of the solute distributed between two immiscible solvents. What are the differences between partition Chromatography and adsorption Chromatography. Write briefly about the components present in GLC. Derive Rault’s law. In a solvent, n simple molecules of solute combine to form an associated molecule and x is the degree of association. Obtain an expression for Van’t Hoff factor. Derive relation between osmotic pressure and vapor pressure. Obtain a relation between depression of freezing point and molality of the solution. A sample of 2-propanone absorbs UV light at the rate of 6 x 1020 photons per second. Calculate the quantum yield of the reaction if 3.60 x 10–2 moles of 2-propanone are decomposed per hour. In an experiment involving colorimetric estimation of Co+3 ion, the following observations were obtained:Conc. In mg 0.04 0.08 0.12 0.16 0.20 0.24 0.28 Optical density 0.11 0.22 0.34 0.42 0.52 0.68 0.75 Show that the observations are in agreement with Beer’s law. What is the relationship between ionic product of water (Kw), hydrolysis constant (Kh), ionisation constant of an acid (Ka) and ionisation constant of a base (Kb). The dipole moment of H2S is 0.95 D. If the bond angle is 97 oC, calculate S-H bond moment. Explain the working of Abbe refractometer. Define Van’t Hoff factor and obtain an equation for the factor and elevation of boiling point. A solution containing 0.2563 gm of naphthalene (MW = 128) in 50gm of CCl4 gives a boiling point elevation of 0.201oC, while a solution of 0.621gm of unknown solute in the same mass of solvent gives a boiling point elevation of 0.647 oC. Calculate the molecular weight of unknown solute. -x-

4

1.a) b) 2.a) b) 3.a) b) 4.a) b) 5.a) b)

6. 7.a) b) 8.a) b)

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