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2003 Course Catalysis (Elective I)

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Total No. of Questions : 12] P1315 [Total No. of Pages :4 [3664] - 280 B.E. (Chemical) CATALYSIS (2003 Course) (Elective - I) Time : 3 Hours] [Max. Marks:100 Instructions to the candidates: 1) Answers to the two sections should be written in separate answer books. 2) Neat diagrams must be drawn wherever necessary. 3) Figures to the right indicate full marks. 4) Use of logarithmic tables, slide rule, Mollier charts, electronic pocket calculator and steam tables is allowed. 5) Assume suitable data, if necessary. SECTION - I Q1) a) Explain the mechanism of homogeneous catalysis with suitable examples. [10] b) Explain the significance of catalyst activity and turnover number in heterogeneous catalysis. [8] OR Q2) a) Give a brief account of reaction feasibility with respect to activation energy and temperature in catalysis. [8] b) Write a note on various processes in petroleum refining explaining the role of catalysts. [10] Q3) a) b) Derive Langmuir - Hinshelwood model in engineering kinetics. [6] Kinetic experiments on the solid catalyzed reaction A 3R are conducted at 8 atm and 700 C in a basket type mixed reactor of 960 cm3 volume and containing 1 g of catalyst of diameter dp = 3 mm. Feed consisting of pure A is introduced at various rates into the reactor. Partial pressure of A in the exit stream is measured for each feed rate. Find a rate equation to represent the rate of reaction on catalyst of this size, using the following results : [10] P.T.O. Feed rate liter/hr PA,out / PA,in 100 22 4 1 0.6 0.8 0.5 0.2 0.1 0.05 OR Q4) a) Explain each term in detail : i) Film resistance as rate controlling step ii) Pore diffusion controlling the reaction. [6] b) The catalytic reaction A 4R is run at 4 atm and 215 C in a plug flow reactor which contains 12 g of catalyst and uses a feed consisting of the partially converted product of 0.4 liter/min of pure unreacted A. Assuming the reactor to be a differential reactor, find a rate equation to represent this reaction, using the following results : [10] Run 1 2 3 4 CA,in (mol/liter) 0.100 0.080 0.060 0.040 CA,out (mol/liter) 0.084 0.070 0.055 0.038 Q5) a) Compare and contrast alumina and silica as catalyst support/carrier. [6] b) The following kinetic data on the reaction A R are obtained in an experimental packed bed reactor using various amounts of catalyst and a fixed feed rate FAo = 10 kmol/hr. W (kg catalyst) 1 2 3 4 5 6 7 XA 0.12 0.20 0.27 0.33 0.37 0.41 0.44 i) ii) iii) Find the reaction rate at 35% conversion. In designing a large packed bed reactor with feed rate FAo = 400 kmol/hr, how much catalyst would be needed for 35% conversion? How much catalyst would be needed in part (ii) if the reactor employed a very large recycle of product stream? [10] OR Q6) a) b) Write a brief note on adsorption on catalysts. [6] The second order reaction A R is studied in a recycle reactor with very large recycle ratio. Following data are recorded : Void volume of reactor = 1 liter Weight of catalyst used = 3 g Feed to the reactor: CAo = 2 mol/liter, Vo = 1 liter/hr Exit stream condition: CA,out = 0.5 mol/liter [3664]-280 2 i) ii) Find the rate constant for this reaction. How much catalyst is needed in a packed bed reactor for 80% conversion of 1000 liter/hr of feed of concentration CAo= 1mol/liter?[10] SECTION - II Q7) a) b) Derive mathematical equation for determining catalyst surface area by BET method. [8] Outline the method of preparation of metal catalysts. State the role of each step in influencing the properties of catalyst. [8] OR Q8) a) Outline the impregnation method of catalyst preparation. State the role of each step in influencing the properties of catalyst. [8] b) Experimental findings of a solid porous catalyst indicate following data : Solid density = 3.567 g/cc, apparent density = 1.745 g/cc, bulk density = 0.823 g/cc. BET method carried out with oxygen at 183 C suggest that the intercept of BET plot is 0.40 10-3 cm-3 and the slope is 13.2 10-3cm-3. If density of liquid oxygen at 183 C is 1.14 g/cc, find [8] i) Surface area per g of catalyst. ii) Pore volume per g of catalyst. iii) Mean pore radius. Q9) a) Give a full account of Zeolites and their importance as catalysts in various chemical reactions. [8] b) What is the relative activity and the degree of inhibition caused by a competitive inhibitor when [S] = Km and [I] = Ki? [10] OR Q10)a) Discuss shape selectivity of Zeolites in chemical reactions and otherwise. [8] b) Estimate k , the first order rate constant for an enzyme preparation with a Vmax of 4.6 mol/(lit.min) under the given experimental conditions. Km = 2 x 10-6 M. [10] Q11)An enzyme has a Km of 4.7x10-5 M. If the Vmax of the preparation is 22 moles / (lit.min), what velocity would be observed in the presence of 2xl0-4 M substrate and 5x10-4 M of (i) a competitive inhibitor, (ii) a noncompetitive inhibitor. What is the degree of inhibition in these cases? Ki is 3x10-4 M. [16] [3664]-280 3 OR Q12)An enzyme was assayed at an initial substrate concentration of 10-5 M. The Km for the substrate is 2xl0-5 M. At the end of 1 min, 2% of the substrate has been converted to the product. (i) What percent of the substrate will be converted to the product at the end of 3 min? What would be the product and substrate concentrations after 3 min? (ii) If the initial substrate concentration were 10-6 M, what percent of the substrate will be converted to the product after 3 min? (iii) What is the maximum attainable velocity Vmax with the enzyme concentration used? (iv) At about what substrate concentration will Vmax be observed? [16] kbkb [3664]-280 4

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