preface

nomenclature
1. introduction
a. importance, significance and limitations
b. limitations of thermodynamics
1. review
a. system and boundary
b. simple system
c. constraints and restraints
d. composite system
e. phase
f. homogeneous
g. pure substance
h. amount of matter and avogadro number
i. mixture
j. property
k. state
l. equation of state
m. standard temperature and pressure
n. partial pressure
o. process
p. vapor�liquid phase equilibrium
c. mathematical background
1. explicit and implicit functions and total differentiation
2. exact (perfect) and inexact (imperfect) differentials
a. mathematical criteria for an exact differential
3. conversion from inexact to exact form
4. relevance to thermodynamics
a. work and heat
b. integral over a closed path (thermodynamic cycle)
5. homogeneous functions
a. relevance of homogeneous functions to thermodynamics
6. taylor series
7. lagrange multipliers
8. composite function
9. stokes and gauss theorems
a. stokes theorem
b. gauss�ostrogradskii divergence theorem
c. the leibnitz formula
d. overview of microscopic thermodynamics
1. matter
2. intermolecular forces and potential energy
3. internal energy, temperature, collision number and mean free path
a. internal energy and temperature
b. collision number and mean free path
4. pressure
a. relation between pressure and temperature
5. gas, liquid, and solid
6. work
7. heat
8. chemical potential
a. multicomponent into multicomponent
b. single component into multicomponent
9. boiling/phase equilibrium
a. single component fluid
b. multiple components
10. entropy
11. properties in mixtures � partial molal property
e. summary
f. appendix
1. air composition
2. proof of the euler equation
3. brief overview of vector calculus
a. scalar or dot product
b. vector or cross product
c. gradient of a scalar
d. curl of a vector
2. first law of thermodynamics
a. introduction
1. zeroth law
2. first law for a closed system
a. mass conservation
b. energy conservation
c. systems with internal motion
d. cyclical work and poincare theorem
e. quasiequilibrium work
f. nonquasiequilibrium work
g. first law in enthalpy form
3. first law for an open system
a. conservation of mass
b. conservation of energy
c. multiple inlets and exits
d. nonreacting multicomponent system
4. illustrations
a. heating of a residence in winter
b. thermodynamics of the human body
c. charging of gas into a cylinder
d. discharging gas from cylinders
e. systems involving boundary work
f. charging of a composite system
b. integral and differential forms of conservation equations
1. mass conservation
a. integral form
b. differential form
2. energy conservation
a. integral form
b. differential form
c. deformable boundary
c. summary
d. appendix
1. conservation relations for a deformable control volume
3. second law and entropy
a. introduction
1. thermal and mechanical energy reservoirs
a. heat engine
b. heat pump and refrigeration cycle
b. statements of the second law
1. informal statements
a. kelvin (1824-1907) � planck (1858-1947) statement
b. clausius (1822-1888) statement
c. consequences of the second law
1. reversible and irreversible processes
2. cyclical integral for a reversible heat engine
3. clausius theorem
4. clausius inequality
5. external and internal reversibility
6. entropy
a. mathematical definition
b. characteristics of entropy
7. relation between ds, ?q and t during an irreversible process
a. caratheodary axiom ii
d. entropy balance equation for a closed system
1. infinitesimal form
a. uniform temperature within a system
b. nonuniform properties within a system
2. integrated form
3. rate form
4. cyclical form
5. irreversibility and entropy of an isolated system
6. degradation and quality of energy
a. adiabatic reversible processes
e. entropy evaluation
1. ideal gases
a. constant specific heats
b. variable specific heats
2. incompressible liquids
3. solids
4. entropy during phase change
a. t�s diagram
5. entropy of a mixture of ideal gases
a. gibbs�dalton�s law
b. reversible path method
f. local and global equilibrium
g. single�component incompressible fluids
h. third law
i. entropy balance equation for an open system
1. general expression
2. evaluation of entropy for a control volume
3. internally reversible work for an open system
4. irreversible processes and efficiencies
5. entropy balance in integral and differential form
a. integral form
b. differential form
6. application to open systems
a. steady flow
b. solids
j. maximum entropy and minimum energy
1. maxima and minima principles
a. entropy maximum (for specified u, v, m)
b. internal energy minimum (for specified s, v, m)
c. enthalpy minimum (for specified s, p, m)
d. helmholtz free energy minimum (for specified t, v, m)
e. gibbs free energy minimum (for specified t, p, m)
2. generalized derivation for a single phase
a. special cases
k. summary
l. appendix
1. proof for additive nature of entropy
2. relative pressures and volumes
3. lagrange multiplier method for equilibrium
a. u, v, m system
b. t, p, m system
4. availability
a. introduction
b. optimum work and irreversibility in a closed system
1. internally reversible process
2. useful or external work
3. internally irreversible process with no external irreversibility
a. irreversibility or gouy�stodola theorem
4. nonuniform boundary temperature in a system
c. availability analyses for a closed system
1. absolute and relative availability under interactions with ambient
2. irreversibility or lost work
a. comments
d. generalized availability analysis
1. optimum work
2. lost work rate, irreversibility rate, availability loss
3. availability balance equation in terms of actual work
a. irreversibility due to heat transfer
4. applications of the availability balance equation
5. gibbs function
6. closed system (non�flow systems)
a. multiple reservoirs
b. interaction with the ambient only
c. mixtures
7. helmholtz function
e. availability efficiency
1. heat engines
a. efficiency
b. availability or exergetic (work potential) efficiency
2. heat pumps and refrigerators
a. coefficient of performance
3. work producing and consumption devices
a. open systems:
b. closed systems
4. graphical illustration of lost, isentropic, and optimum work
5. flow processes or heat exchangers
a. significance of the availability or exergetic efficiency
b. relation between ?avail,f and ?avail,0 for work producing devices
f. chemical availability
1. closed system
2. open system
a. ideal gas mixtures
b. vapor or wet mixture as the medium in a turbine
c. vapor�gas mixtures
d. psychometry and cooling towers
g. integral and differential forms
1. integral form
2. differential form
3. some applications
h. summary
5. postulatory (gibbsian) thermodynamics
a. introduction
b. classical rationale for postulatory approach
1. simple compressible substance
c. legendre transform
1. simple legendre transform
a. relevance to thermodynamics
2. generalized legendre transform
3. application of legendre transform
d. generalized relation for all work modes
1. electrical work
2. elastic work
3. surface tension effects
4. torsional work
5. work involving gravitational field
6. general considerations
e. thermodynamic postulates for simple systems
1. postulate i
2. postulate ii
3. postulate iii
4. postulate iv
f. entropy fundamental equation
g. energy fundamental equation
h. intensive and extensive properties
i. summary
6. state relationships for real gases and liquids
a. introduction
b. equations of state
c. real gases
1. virial equation of state
a. exact virial equation
b. approximate virial equation
2. van der waals (vw) equation of state
a. clausius�i equation of state
b. vw equation
3. redlich�Kwong equation of state
4. other two�parameter equations of state
5. compressibility charts (principle of corresponding states)
6. boyle temperature and boyle curves
a. boyle temperature
b. boyle curve
c. the z = 1 island
7. deviation function
8. three parameter equations of state
a. critical compressibility factor (zc) based equations
b. pitzer factor
c. evaluation of pitzer factor,?
9. other three parameter equations of state
a. one parameter approximate virial equation
b. redlich�kwong�soave (rks) equation
c. peng�robinson (pr) equation
10. generalized equation of state
11. empirical equations of state
a. benedict�webb�rubin equation
b. beatie � bridgemann (bb) equation of state
c. modified bwr equation
d. lee�kesler equation of state
e. martin�hou
12. state equations for liquids/solids
a. generalized state equation
b. murnaghan equation of state
c. racket equation for saturated liquids
d. relation for densities of saturated liquids and vapors
e. lyderson charts (for liquids)
f. incompressible approximation
d. summary
e. appendix
1. cubic equation
a. case i: ??> 0
b. case ii: ??< 0
2. another explanation for the attractive force
3. critical temperature and attraction force constant
7. thermodynamic properties of pure fluids
a. introduction
b. ideal gas properties
c. james clark maxwell (1831�1879) relations
1. first maxwell relation
a. remarks
2. second maxwell relation
a. remarks
3. third maxwell relation
a. remarks
4. fourth maxwell relation
a. remarks
5. summary of relations
d. generalized relations
1. entropy ds relation
a. remarks
2. internal energy (du) relation
a. remarks
3. enthalpy (dh) relation
a. remarks
4. relation for (cp�cv)
a. remarks
e. evaluation of thermodynamic properties
1. helmholtz function
2. entropy
3. pressure
4. internal energy
a. remarks
5. enthalpy
a. remarks
6. gibbs free energy or chemical potential
7. fugacity coefficient
f. pitzer effect
1. generalized z relation
g. kesler equation of state (kes) and kesler tables
h. fugacity
1. fugacity coefficient
a. rk equation
b. generalized state equation
2. physical meaning
a. phase equilibrium
b. subcooled liquid
c. supercooled vapor
i. experiments to measure (uo � u)
j. vapor/liquid equilibrium curve
1. minimization of potentials
a. helmholtz free energy a at specified t, v and m
b. g at specified t, p and m
2. real gas equations
a. graphical solution
b. approximate solution
3. heat of vaporization
4. vapor pressure and the clapeyron equation
a. remarks
5. empirical relations
a. saturation pressures
b. enthalpy of vaporization
6. saturation relations with surface tension effects
a. remarks
b. pitzer factor from saturation relations
k. throttling processes
1. joule thomson coefficient
a. evaluation of ?jt
b. remarks
2. temperature change during throttling
a. incompressible fluid
b. ideal gas
c. real gas
3. enthalpy correction charts
4. inversion curves
a. state equations
b. enthalpy charts
c. empirical relations
5. throttling of saturated or subcooled liquids
6. throttling in closed systems
7. euken coefficient � throttling at constant volume
a. physical interpretation
l. development of thermodynamic tables
1. procedure for determining thermodynamic properties
2. entropy
m. summary
8. thermodynamic properties of mixtures
a. partial molal property
1. introduction
a. mole fraction
b. mass fraction
c. molality
d. molecular weight of a mixture
2. generalized relations
a. remarks
3. euler and gibbs�duhem equations
a. characteristics of partial molal properties
b. physical interpretation
4. relationship between molal and pure properties
a. binary mixture
b. multicomponent mixture
5. relations between partial molal and pure properties
a. partial molal enthalpy and gibbs function
b. differentials of partial molal properties
6. ideal gas mixture
a. volume
b. pressure
c. internal energy
d. enthalpy
e. entropy
f. gibbs free energy
7. ideal solution
a. volume
b. internal energy and enthalpy
c. gibbs function
d. entropy
8. fugacity
a. fugacity and activity
b. approximate solutions for �gk
c. standard states
d. evaluation of the activity of a component in a mixture
e. activity coefficient
f. fugacity coefficient relation in terms of state equation for p
g. duhem� margules relation
h. ideal mixture of real gases
i. mixture of ideal gases
j. relation between gibbs function and enthalpy
k. excess property
l. osmotic pressure
b. molal properties using the equations of state
1. mixing rules for equations of state
a. general rule
b. kay�s rule
c. empirical mixing rules 25
d. peng robinson equation of state
e. martin hou equation of state
f. virial equation of state for mixtures
2. dalton�s law of additive pressures (lap)
3. law of additive volumes (lav)
4. pitzer factor for a mixture
5. partial molal properties using mixture state equations
a. kay�s rule
b. rk equation of state
c. summary
9. phase equilibrium for a mixture
a. introduction
1. miscible, immiscible and partially miscible mixture
2. phase equilibrium
a. two phase system
b. multiphase systems
c. gibbs phase rule
b. simplified criteria for phase equilibrium
1. general criteria for any solution
2. ideal solution and raoult�s law
a. vapor as real gas mixture
b. vapor as ideal gas mixture
c. pressure and temperature diagrams
1. completely miscible mixtures
a. liquid�vapor mixtures
b. relative volatility
c. p�t diagram for a binary mixture
d. p�xk(l)�t diagram
e. azeotropic behavior
2. immiscible mixture
a. immiscible liquids and miscible gas phase
b. miscible liquids and immiscible solid phase
3. partially miscible liquids
a. liquid and gas mixtures
b. liquid and solid mixtures
d. dissolved gases in liquids
1. single component gas
2. mixture of gases
3. approximate solution�henry�s law
e. deviations from raoult�s law
1. evaluation of the activity coefficient
f. summary
g. appendix
1. phase rule for single component
a. single phase
b. two phases
c. three phases
d. theory
2. general phase rule for multicomponent fluids
3. raoult�s law for the vapor phase of a real gas
10. stability
a. introduction
b. stability criteria
1. isolated system
a. single component
2. mathematical criterion for stability
a. perturbation of volume
b. perturbation of energy
c. perturbation with energy and volume
d. multicomponent mixture
e. system with specified values of s, v, and m
f. perturbation in entropy at specified volume
g. perturbation in entropy and volume
h. system with specified values of s, p, and m
i. system with specified values of t, v, and m
j. system with specified values of t, p, and m
k. multicomponent systems
c. application to boiling and condensation
1. physical processes and stability
a. physical explanation
2. constant temperature and volume
3. specified values of s, p, and m
4. specified values of s (or u), v, and m
d. entropy generation during irreversible transformation
e. spinodal curves
1. single component
2. multicomponent mixtures
f. determination of vapor bubble and drop sizes
g. universe and stability
h. summary
11. chemically reacting systems
a. introduction
b. chemical reactions and combustion
1. stoichiometric or theoretical reaction
2. reaction with excess air (lean combustion)
3. reaction with excess fuel (rich combustion)
4. equivalence ratio, stoichiometric ratio
5. dry gas analysis
c. thermochemistry
1. enthalpy of formation (chemical enthalpy)
2. thermal or sensible enthalpy
3. total enthalpy
4. enthalpy of reaction
5. heating value
6. entropy, gibbs function, and gibbs function of formation
d. first law analyses for chemically reacting systems
1. first law
2. adiabatic flame temperature
a. steady state steady flow processes in open systems
b. closed systems
e. combustion analyses in the case of nonideal behavior
1. pure component
2. mixture
f. second law analysis of chemically reacting systems
1. entropy generated during an adiabatic chemical reaction
2. entropy generated during an isothermal chemical reaction
g. mass conservation and mole balance equations
1. steady state system
h. summary
12. reaction direction and chemical equilibrium
a. introduction
b. reaction direction and chemical equilibrium
1. direction of heat transfer
2. direction of reaction
3. mathematical criteria for a closed system
4. evaluation of properties during an irreversible chemical reaction
a. nonreacting closed system
b. reacting closed system
c. reacting open system
5. criteria in terms of chemical force potential
6. generalized relation for the chemical potential
c. chemical equilibrium relations
1. nonideal mixtures and solutions
a. standard state of an ideal gas at 1 bar
b. standard state of a nonideal gas at 1 bar
2. reactions involving ideal mixtures of liquids and solids
3. ideal mixture of real gases
4. ideal gases
a. partial pressure
b. mole fraction
5. gas, liquid and solid mixtures
6. van�t hoff equation
a. effect of temperature on ko(t)
b. effect of pressure
7. equilibrium for multiple reactions
8. adiabatic flame temperature with chemical equilibrium
a. steady state steady flow process
b. closed systems
9. gibbs minimization method
a. general criteria for equilibrium
b. multiple components
d. summary
e. appendix
13. availability analysis for reacting systems
a. introduction
b. entropy generation through chemical reactions
c. availability
1. availability balance equation
2. adiabatic combustion
3. maximum work using heat exchanger and adiabatic combustor
4. isothermal combustion
5. fuel cells
a. oxidation states and electrons
b. h2-o2 fuel cell
d. fuel availability
e. summary