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# VISVESVARAYA TECHNOLOGICAL UNIVERSITY Biochemical Thermodynamics (06BT-42) Subject Code: Hrs/Week: Total Hrs: 06BT-42 04 52 IA Marks: Exam Hours:

Exam Marks: Blown Up Syllabus Topics to be covered PART A 1 UNIT 1: BASIC CONCEPTS T1 pp 1-23 T2 pp 1-17 Explain the scope and limitations of thermodynamics Define the terms system, surrounding and process with examples Define and differentiate between closed/open systems and homogeneous / heterogeneous systems with examples. Identify the system and surrounding given a situation. Classify a given system as closed or open. Define what is meant by state of a system with examples Define what is meant by property of a system with examples Define and differentiate between intensive and extensive properties with examples. Identify a given property as intensive or extensive Define and differentiate between state and path functions with examples Define/Give the defining equations for force, pressure, work, energy (potential, kinetic) and power. Derive the expression for work of expansion or compression in a cylinder. Solve simple substitution problems based on the above defining equations. Define and differentiate between steady state and equilibrium states. State the phase rule for non-reacting systems State the Zeroth Law of Thermodynamics Define temperature. List common thermometric properties. Discuss the setup of the ideal gas temperature scale. Define heat reservoir, heat engines and heat pumps with examples Explain reversible and irreversible processes using gas in cylinder example. List the characteristics of a reversible process. 25 03 100

## Class Chapter / Reference

2 3 4 5 UNIT 2: LAWS OF THERMODYNAMIC S State the First Law Explain what a perpetual motion machine of the first kind is. State the First Law for Cyclic processes and hence define J the mechanical/electrical equivalent of heat. 1

## Class Chapter / Reference T1 pp 23 -41 T1 pp 79-114 T2 pp 18-57 T2 pp 148-185

Blown Up Syllabus Topics to be covered Define internal energy and explain why it is a thermodynamic property. Derive the First Law for a non-flow process. Define enthalpy and show its value for constant P and V processes. Derive the First Law for flow processes. Define heat capacity at constant P and V Solve simple problems based on above laws and definitions. (from T1 and R2) Discuss the limitations of the First Law. Give the Kelvin-Planck and Clausius statements of the Second Law as well as a statement in terms of spontaneous processes. Demonstrate the equivalence of Kelvin-Planck and Clausius statements Define entropy Explain why the concept of entropy is necessitated. Discuss the relation between entropy and heat, entropy and temperature, entropy and nature of the process. Explain the Carnot cycle and state Carnot's theorem. Prove Carnot's theorem and derive an expression for efficiency of a Carnot engine. Show how Carnot's cycle/engine allows us to set up a thermodynamic temperature scale. Show that the ideal gas temperature scale is a true thermodynamic scale of temperature. Show that entropy is a state function. Calculate entropy changes involved in (a) phase change (b) processes involving ideal gases in general and for constant P, V, T (c) adiabatic mixing processes (d)isothermal mixing of ideal gases (e) chemical reactions. Derive Clausius inequality and use it to differentiate reversible and irreversible processes. Derive a mathematical statement of the Second Law. State the Third Law of thermodynamics and its use. Solve problems based on the above concepts and equations. (From T1 and R2)

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## Class Chapter / Reference 15 UNIT 3: PVT BEHAVIOUR T1 pp 42-62 T2 pp 58-115

Blown Up Syllabus Topics to be covered Explain the general behavior of pure fluids using P-V and P-T diagrams. Define critical point. Define the term equation of state. List the characteristics of an ideal gas and give its EOS. Apply the First Law to various processes involving ideal gases constant P, V, and T, adiabatic and polytrophic processes. List/State the various EOS for real gases Van der Waal's, Redlich-Kwong, Peng-Robinson and Virial Equation. Use above EOS to calculate various properties of ideal and real gases. Show how the constants in the EOS for real gases are linked to measurable quantities such as Tc, Pc and Vc for Van der Waal's equation only. Derive the relation between constants in the two forms of the virial equation (B and B', C and C') Show relation between van der Waal' s and virial equation.

16 17 18 19 20 21 UNIT 4: COMPRESSIBILITY CHARTS T1 pp 63-78 T2 pp 116-147 Define compressibility. Define an ideal gas in terms of compressibility. State the principle of corresponding states in words and mathematically. Explain what is a generalized compressibility chart. Explain when, for what and how to use a generalized compressibility chart. Define standard heat of reaction, combustion and formation. State the standard states for gases, liquids, solids and solutions. State Hess's Law of Heat Summation and give its mathematical form. Derive the equation showing the effect of temperature on heat of reaction. Calculate heat of formation given heat of combustion data. Calculate heat of reaction from heats of formation/combustion data. Define adiabatic temperature of reaction and calculate it for a given system. Problems from T1 and R2.

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## UNIT 5: PROPERTIES OF PURE FLUIDS T1 pp 188-254 T2 pp 186-234

Define reference, energy and derived properties. Define work function / Helmholtz free energy Define Gibbs' free energy. Explain what is an exact differential. List the fundamental property relations. Derive Maxwell's equations. Derive Clapeyron equation and Clausius-Clapeyron equation. Derive relation between entropy and heat capacities. Derive differenial equations for entropy. Derive modified equations for U and H. Discuss the effect of T and P on U, H and S with equations. Derive relationships between CP and CV. (differences and ratio) Discuss the effect of P and V on CP and CV Derive / State Gibbs - Helmholtz equation. Define fugacity and explain State the standard states for fugacity. Define fugacity coefficient Derive the effect of P and T on f Determination of fugacity of pure gases using (a) compressibility factor (b) EOS Discuss fugacities of solids and liquids with simple examples. (no equations) Define activity and activity coefficient Derive equations for effect of T and P on activity

28 29 30 31 32 33 34 35 36 37 UNIT 6: PROPERTIES OF SOLUTIONS Define partial molar properties and explain their physical meaning. Determination of partial molar properties by tangent-intercept method. 4

## Class Chapter / Reference T1 pp 254-308 T2 pp 352-449

Blown Up Syllabus Topics to be covered Define Chemical potential Derive a relation relating chemical potential and free energy change. Derive the effect of T and P on chemical potential. Derive equations for measuring fugacities in solutions and gases. State and discuss Lewis-Randall rule and conditions under which it is valid. Define ideal solutions based on Raoult's Law. State Henry's law for dilute solutions. Establish the connections between LR Rule, Raoult's and Henry's law. Discuss activity and activity coefficient in solutions Derive Gibbs-Duhem equation and state its uses. Discuss property changes of mixing (no numerical) Define excess properties with example of excess Gibbs free energy Problems on above topics from T1 and R2 except where explicitly omitted.

38 39 40 41 UNIT 7: PHASE EQUILIRIA T1 pp 309-397 T2 pp 314-351 T2 pp 400-449 State the criteria of phase equilibrium and stability (no derivation) Calculations of phase equilibria in single component and binary systems. State phase rule for non-reacting systems. Use phase rule to calculate the degrees of freedom. Generation and calculation of VLE data for ideal gases and ideal liquid solutions. Low pressure VLE calculations using van Laar equation Explain P-x-y and T-x-y diagrams. Discuss non-ideal solutions (including azeotropes) Explain one test for consistency of VLE data (slope of ln gamma curves) List steps in bubble point and dew point calculations (no iterative problems to be given) Explain binary Liquid- Liquid equilibrium diagrams. Explain tie-line concept.

## Class Chapter / Reference BIOCHEMICAL ENERGETICS T1 pp 398-450 T2 pp 450-506 T3 pp 145-207

Blown Up Syllabus Topics to be covered List the energy rich compounds. State the criteria of reaction equilibrium Define equilibrium constant. Relate K to free energy Derive effect of T and P on K. Evaluation of K from thermal data. Discuss factors affecting equilibrium conversions - T, P, inerts, excess reactants and products. Discuss heterogeneous reaction equilibrium pure solids and liquids; decompositions. State the phase rule for reacting systems.

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BOOKS S. Type No. /Code 1 2 3 4 5 Name Author(s) K. V. Narayanan Pulisher Edn/Year PHI 1st Edn / 2001 6th Edn / 2003 2nd Edn / 1976

Text Book A Textbook of Chemical (T1) Engineering Thermodynamics Text Book Introduction to Chemical (T2) Engineering Thermodynamics Text Book Biochemical Calculations (T3) Reference (R1) Reference (R2) Reference (R3) Reference (R4) Chemical Engineering Thermodynamics Chemical Engineering Thermodynamics [through Examples] Chemical and Biochemical Thermodynamics Engineering Thermodynamics

J. M. Smith, H. C. Van TMH Ness, M. M. Abbott Irwin H. Segel Y. V. C. Rao Y. V. C. Rao JWS New Age Intl. New Age Intl.

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## Sandler Dr. S. Sundaram

BIOCHEMICAL THERMODYNAMICS MODEL QUESTION PAPER 1 Answer any FIVE full questions out of the EIGHT. At least TWO questions must be answered from each part. All questions carry equal marks Time: 3 hours Max. Marks: 100

PART A
1. (a) Define the following terms and give one example for each (i) Process (ii) State (iii) Intensive Property (iv) Thermodynamic Equilibrium (v) Heat Engine (5 x 2) (10) (b) What is the Zeroth Law of Thermodynamics? Explain briefly. (04)

(c) A gas is confined in a 0.47m diameter cylinder by a piston, on which rests a weight. The mass of the piston and weight together is 150kg. The local acceleration due to gravity is 9.813 ms-2, and atmospheric pressure is 101.57kPa. (i) What is the force in newtons exerted on the gas by the atmosphere, the piston and the weight, assuming no friction between the piston and the cylinder? (04) (ii) What is the pressure of the gas in kPa? (02) 2. (a) Derive the First Law of Thermodynamics for a flow process. (b) Briefly explain the concepts of (i) Internal Energy and (ii) Entropy (08) (06)

(c) A balloon which is initially of 0.5m radius is filled with hydrogen very quickly at 60.67 kPa so as to make it to a radius of 2m. Find the change in internal energy if the process of filling may be approximated as an adiabatic process. (06) 3. (a) What is lost work? Derive an expression for it. Explain the engineering significance of.(08) the result. (b) Derive the parameters (a and b) in the Van der Waals equation of state in terms of the critical temperature (Tc) and pressure (Pc) (06) (c) Estimate the molar volume of CO2 at 500K and 100bar using Van der Waal's equation. The Tc and Pc of CO2 are 304.2K and 73.83bar respectively. (06) 4. (a) State Hess's Law of Constant Heat Summation. Define (i) Standard Heat of Reaction (ii) Standard Heat of Formation (07) (b) Derive the equation showing the effect of temperature on the heat of reaction. (07)

(c) Calculate the theoretical flame temperature for carbon monoxide when burnt with 100% excess air when both reactants are at 373K. The heat capacities (J/mol K) may be assumed to be constant at 29.23 for CO, 34.83 for O2, 33.03 for N2 and 53.59 for CO2. The standard heat of combustion at 298K is -283.178 kJ/mol CO. (06)

PART B
5. (a) What are the steps inCpvolved in the calculation of the entropy and enthalpy of a pure (08) fluid at temperature T and pressure P? What additional data are required for this calculation? 8

(b) Define fugacity and show that fugacity and pressure are identical for ideal gases. What is the standard state for fugacity of a real gas? (07) (c) Calculate the fugacity of liquid water at 303K and 10bar if the saturation pressure at (05) 303K is 4.241kPa and specific volume of liquid water is 1.00410-3 m3/kg. 6. (a) Explain Lewis Randall rule and Henry's law. (08) (b) For a mixture of acetic acid and toluene containing 0.486 mole fraction toluene, the partial pressures of acetic acid and toluene are found to be 0.118bar and 0.174bar, respectively at 343K. The vapour pressures of the pure components at this temperature are 0.269bar and 0.181bar respectively. The Henry's law constant for acetic acid is 0.55bar. Calculate the activity and activity coefficient for acetic acid in the mixture by (i) Lewis-Randall rule and (ii) by Henry's law. (07) (c) With a neat sketch explain the boiling point diagram. (05) 7. (a) Using van Laar constants and the vapour pressures of pure substances how would you (04) prove whether a given binary system would form an azeotrope or not? (b) A mixture contains 45 mol % methanol (A), 30 mol % ethanol (B) and the rest npropanol (C). The liquid solution may be assumed to be ideal and perfect gas law is valid for the vapour phase. Calculate at a total pressure of 101.3 kPa (i) the bubble point and vapour composition (ii) dew point and liquid composition. The vapour pressures of the pure liquids are given below Temperature (K) PA, kPa PB, kPa PC, kPa 333 81.97 49.32 39.32 343 133.29 73.31 62.65 353 186.61 106.63 93.30 363 266.58 166.61 133.29

(10)

(c) Briefly discuss the effect of temperature, pressure and inerts on the equilibrium constant of a reaction. (06) 8. (a) Five moles of steam reacts with one mole methane according to the following reaction at 850K and 1 bar.
CH 4 H 2 O CO 3 H 2 ; K 1= 0.574 CO H 2 O CO 2 H 2 ; K 2= 2.21

## Calculate the composition at equilibrium assuming ideal gas behaviour.

(08)

(b) Discuss the phase rule for reacting systems. Determine the degrees of freedom in a (06) gaseous system consisting of CH4, CO, CO2, H2, H2O in chemical equilibrium. (c) Calculate G' for the complete oxidation of lactic acid to CO2 and H2O given the information below. Glucose 2 Lactic acid G'1 = -52,000 cal/mole (06) Glucose + 6O2 6CO2 + 6H2O G'2 = -686,000 cal/mole %%% END %%%

BIOCHEMICAL THERMODYNAMICS MODELQUESTION PAPER 2 Answer any FIVE full questions out of the EIGHT. At least TWO questions must be answered from each part. All questions carry equal marks Time: 3 hours Max. Marks: 100

PART A
1 (a) Distinguish between closed and open systems. Say whether the following systems are closed or open (i) a tubular reactor (ii) a batch reactor (iii) individual phases in a multiphase system. (05) (b) Five kilograms of CO2 gas is contained in piston cylinder assembly at a pressure of 7.5 bar and temperature 300K. The piston has a mass of 6000kg and a surface area of 1 m2. The friction of the piston on the walls is significant and cannot be ignored. The atmospheric pressure is 1.01325bar. The latch holding the piston in place is removed and the gas is allowed to expand. The expansion is arrested when the volume is double the original volume. Determine the work done in the surroundings. (10) (c) Using thermodynamics can you determine the rate of a chemical reaction? Why? (05)

2 (a) What do you mean by a cyclic process? State and explain the first law for a cyclic process. (04) (b) Oil flows at a rate of 1000kg/min from an open reservoir at the top of a hill 400m in height to another reservoir at the bottom of the hill. Heat is supplied to the oil on its way at the rate of 1800 kJ/min and work is supplied by a 1 hp pump. Take the mean specific heat of oil to be 3.35 kL/kg. Determine the temperature change of the oil. (06) (c) Explain the concept of entropy and why it is necessary. Show that entropy is a thermodynamic function. (10) 3 (a) Discuss the virial equation of state and its use to calculate molar volume. Derive the relationship between van der Waal's constants and virial coefficients. (10) (b) Calculate the pressure developed by 1 kmol gaseous ammonia contained in a vessel of 0.6 m3 capacity at a constant temperature of 473K by the following methods (i) ideal gas (04) law and (ii) Van der Waal's equation (a = 0.4233 Nm4/mol2 ; b = 3.73 10-5 m3/mol) (c) Discuss briefly (i) acentric factor (ii) compressibility factor (iii) Redlich-Kwong equation (06) 4 (a) Explain briefly the principle of corresponding states and generalized compressibility charts. (06) (b) If the heat of reaction at one temperature is known then derive an equation that will help us determine the heat of reaction at another temperature. (08) (c) Calculate the standard heat of reaction at 298K for the following reaction 4HCl (g) + O2 (g) 2H2O (g) + 2Cl2 (g) The standard heats of formation are -92.307 kJ/mol for HCl (g) and -241.818kJ/mol for (06) H2O (g). 10

PART B
5 (a) Develop equations for evaluating the change in internal energy and change in enthalpy for processes involving ideal gases starting from the modified equations for U and H. (06) (b) Derive the general relationship between CP and CV and hence show that CP - CV = R for (06) ideal gases. (c) Calculate (U/P)T, (/P)T and of a substance at 298K and 1 bar, if the following data are given: CP =138 kJ/mol K, V = 0.09 m3/kmol, (V/T)P = 9.0 10-8 m3/kmol K (08) and (V/P)T = - 9.0 10-9 m3/kmol K 6 (a) Liquids A and B form an azeotrope containing 46.1 mole% A at 101.3kPa and 345K. At 345K the vapour pressure of A is 84.8kPa and that of B is 78.2kPa. Calculate the van Laar constants. (04) (b) Discuss the following (i) one consistency test for VLE data (ii) binary liquid liquid equilibrium diagrams (06) (c) Discuss non-ideal solutions in detail including azeotropes. 7 (a) Briefly describe about the phase equilibria and criterion of stability (b) Explain P-x-y and T-x-y diagram (10) (08) (06)

(c) The azeotrope of the ethanol and benzene system has a composition of 44.8% (mol) ethanol with a boiling point of 341.4 K at 101.3 kpa. At this temperature the vapour pressure of the benzene is 68.9 kPa and 67.4 kPa. What are the activity coefficients in a solution containing 10 % alcohol (06) 8 (a) Briefly discuss about the feasibility of a chemical reaction (b) Derive van't Hoff's equation (05) (08)

(b) The standard heat of formation and standard free energy of formation of ammonia at 298K are -46100 J/mol and -16500 J/mol respectively. Calculate the equilibrium constant for the reaction N2(g) + 3H2(g) 2NH3 at 500K assuming that the heat of reaction is (07) constant in the temperature range 298K to 500K.

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