06 bt-42 biochemical thermodynamics
TRANSCRIPT
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VISVESVARAYA TECHNOLOGICAL UNIVERSITY
Biochemical Thermodynamics (06BT-42)
Subject Code:
06BT-42 IA Marks: 25
Hrs/Week: 04 Exam Hours: 03
Total Hrs: 52 Exam Marks: 100
Class Chapter / Reference 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.
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.
2
Class Chapter / Reference Blown Up Syllabus Topics to be covered
T1 pp 23 -41
T1 pp 79-114
T2 pp 18-57
T2 pp 148-185
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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7
8
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10
11
12
13
14
3
Class Chapter / Reference Blown Up Syllabus Topics to be covered
15 UNIT 3:
PVT BEHAVIOUR
T1 pp 42-62
T2 pp 58-115
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.
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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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23
4
Class Chapter / Reference Blown Up Syllabus Topics to be covered
24
25
26
27 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
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31
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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.
5
Class Chapter / Reference Blown Up Syllabus Topics to be covered
T1 pp 254-308
T2 pp 352-449
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.
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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.
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43
44
45
46
47 UNIT 8: Explain energy coupling of reactions.
6
Class Chapter / Reference Blown Up Syllabus Topics to be covered
BIOCHEMICAL
ENERGETICS
T1 pp 398-450
T2 pp 450-506
T3 pp 145-207
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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52
7
BOOKS
S.
No.
Type
/Code
Name Author(s) Pulisher Edn/Year
1 Text Book
(T1)
A Textbook of Chemical
Engineering Thermodynamics
K. V. Narayanan PHI 1st Edn /
2001
2 Text Book
(T2)
Introduction to Chemical
Engineering Thermodynamics
J. M. Smith, H. C. Van
Ness, M. M. Abbott
TMH 6th Edn /
2003
3 Text Book
(T3)
Biochemical Calculations Irwin H. Segel JWS 2nd Edn /
1976
4 Reference
(R1)
Chemical Engineering
Thermodynamics
Y. V. C. Rao New Age
Intl.
5 Reference
(R2)
Chemical Engineering
Thermodynamics [through
Examples]
Y. V. C. Rao New Age
Intl.
6 Reference
(R3)
Chemical and Biochemical
Thermodynamics
Sandler
7 Reference
(R4)
Engineering Thermodynamics Dr. S. Sundaram
8
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)
(b)
(c)
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)
What is the Zeroth Law of Thermodynamics? Explain briefly.
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?
(ii) What is the pressure of the gas in kPa?
(10)
(04)
(04)
(02)
2. (a)
(b)
(c)
Derive the First Law of Thermodynamics for a flow process.
Briefly explain the concepts of (i) Internal Energy and (ii) Entropy
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.
(08)
(06)
(06)
3. (a)
(b)
(c)
What is lost work? Derive an expression for it. Explain the engineering significance of
the result.
Derive the parameters (a and b) in the Van der Waals equation of state in terms of the
critical temperature (Tc) and pressure (Pc)
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.
.(08)
(06)
(06)
4. (a)
(b)
(c)
State Hess's Law of Constant Heat Summation. Define (i) Standard Heat of Reaction (ii)
Standard Heat of Formation
Derive the equation showing the effect of temperature on the heat of reaction.
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.
(07)
(07)
(06)
PART B
5. (a)
What are the steps inCpvolved in the calculation of the entropy and enthalpy of a pure
fluid at temperature T and pressure P? What additional data are required for this
calculation?
(08)
9
(b)
(c)
Define fugacity and show that fugacity and pressure are identical for ideal gases. What is
the standard state for fugacity of a real gas?
Calculate the fugacity of liquid water at 303K and 10bar if the saturation pressure at
303K is 4.241kPa and specific volume of liquid water is 1.004×10-3 m
3/kg.
(07)
(05)
6. (a)
(b)
(c)
Explain Lewis Randall rule and Henry's law.
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.
With a neat sketch explain the boiling point diagram.
(08)
(07)
(05)
7. (a)
(b)
(c)
Using van Laar constants and the vapour pressures of pure substances how would you
prove whether a given binary system would form an azeotrope or not?
A mixture contains 45 mol % methanol (A), 30 mol % ethanol (B) and the rest n-
propanol (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) 333 343 353 363
PA, kPa 81.97 133.29 186.61 266.58
PB, kPa 49.32 73.31 106.63 166.61
PC, kPa 39.32 62.65 93.30 133.29
Briefly discuss the effect of temperature, pressure and inerts on the equilibrium constant
of a reaction.
(04)
(10)
(06)
8. (a)
(b)
(c)
Five moles of steam reacts with one mole methane according to the following reaction at
850K and 1 bar. CH 4�H 2O�CO�3H 2 ; K 1= 0.574
CO�H 2O�CO2�H 2 ; K 2= 2.21 Calculate the composition at equilibrium assuming ideal gas behaviour.
Discuss the phase rule for reacting systems. Determine the degrees of freedom in a
gaseous system consisting of CH4, CO, CO2, H2, H2O in chemical equilibrium.
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
Glucose + 6O2 → 6CO2 + 6H2O ∇G'2 = -686,000 cal/mole
(08)
(06)
(06)
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10
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)
(b)
(c)
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.
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.
Using thermodynamics can you determine the rate of a chemical reaction? Why?
(05)
(10)
(05)
2 (a)
(b)
(c)
What do you mean by a cyclic process? State and explain the first law for a cyclic
process.
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.
Explain the concept of entropy and why it is necessary. Show that entropy is a
thermodynamic function.
(04)
(06)
(10)
3 (a)
(b)
(c)
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.
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
law and (ii) Van der Waal's equation (a = 0.4233 Nm4/mol
2 ; b = 3.73 × 10
-5 m
3/mol)
Discuss briefly (i) acentric factor (ii) compressibility factor (iii) Redlich-Kwong equation
(10)
(04)
(06)
4 (a)
(b)
(c)
Explain briefly the principle of corresponding states and generalized compressibility
charts.
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.
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
H2O (g).
(06)
(08)
(06)
11
PART B 5 (a)
(b)
(c)
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.
Derive the general relationship between CP and CV and hence show that CP - CV = R for
ideal gases.
Calculate (∂U/∂P)T, (∂Η/∂P)T and µ 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 m
3/kmol K
and (∂V/∂P)T = - 9.0 × 10-9
m3/kmol K
(06)
(06)
(08)
6 (a)
(b)
(c)
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.
Discuss the following (i) one consistency test for VLE data (ii) binary liquid liquid
equilibrium diagrams
Discuss non-ideal solutions in detail – including azeotropes.
(04)
(06)
(10)
7 (a)
(b)
(c)
Briefly describe about the phase equilibria and criterion of stability
Explain P-x-y and T-x-y diagram
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
(08)
(06)
(06)
8 (a)
(b)
(b)
Briefly discuss about the feasibility of a chemical reaction
Derive van't Hoff's equation
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
constant in the temperature range 298K to 500K.
(05)
(08)
(07)
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