Subject Index

Note: Page numbers followed by ‘‘f’’ and ‘‘t’’ indicate figures and tables respectively.

A for hydrocarbons, 668

Acentric factor, 37 for inorganic compounds, 669
conceptual basis of, 38 for organic compounds, 669
of elements, 660 Apparent equilibrium constant,
of hydrocarbons, 660 625
of inorganic compounds, 661 of carbon deposition reactions, 628
of organic compounds, 661 Area test, 320
Activity, definition, 278, 561 Azeotrope, 412–413
Activity coefficient breaking of, 417–418
asymmetric, 459 formation criteria, 419
calculation of maximum boiling, 413–414
from solid-liquid equilibrium minimum boiling, 413–414
measurements, 517
from vapor-liquid equilibrium B
(VLE) measurements, 281 Benedict-Webb-Rubin equation of state,
definition, 279 83, 671
and Henry’s law, 459 Binary interaction parameter, 164
standard states used, 460 Binodal curve, 483–484
infinite dilution, 280, 312 Boiling point elevation, 524
for multicomponent mixtures, 325 Bubble point curve, 353–355
variation of Bubble point pressure, 354–355
with pressure, 285 calculation of
with temperature, 285 for ideal liquid mixtures, 363–365
Activity coefficient models for nonideal liquid mixtures,
Margules 397–399
three-suffix (two-constant), 291 Bubble point temperature, 356–357
two-suffix (one-constant), 288 calculation of
multicomponent, 325 for ideal liquid mixtures, 367
NRTL, 302 for nonideal liquid mixtures,
regular mixture, 303 401–403
selection, 325
UNIFAC, 306 C
van Laar, 297 Carbon formation, 627
Wilson, 300 Boudouard reaction, 627
Antoine equation, 140, 353 equilibrium constants of, 627
constants of heterogeneous water-gas reaction, 627
for elements, 668 methane cracking reaction, 627

703
704
Chemical potential, 109, 226
Chemical reaction
endothermic, 565
exothermic, 565
extent of, molar, 556
feasibility of, 623
heat of, 562, 623
standard enthalpy change of, 562
standard Gibbs energy change of
562
stoichiometry of, 551
Chemical reaction equilibrium
criteria for, 560
equilibrium constant evaluation, 562
gas phase reactions, 571
heterogeneous reactions, 603
liquid phase reactions, 588
multiple reactions
independent reactions, 611
Clapeyron equation, 138
Clausius statement, 10
schematic representation of, 11
Clausius-Clapeyron equation, 139
Closed system
definition, 1
equilibrium criteria for, 105
first law, 9
second law, 12
Coefficient of thermal expansion, 22
Cohesive energy density, 341
and solubility parameter, 342
Colligative
definition, 517, 523
properties
boiling point elevation, 524
freezing point depression, 517
osmotic pressure, 529–300
Common tangent rule, 481–482
Compressibility factor, 35–36
Concave function, 477–478
Conservation of energy. See First law of
thermodynamics
Conservation of mass, 552
Subject Index
Conservative force, 4
Consolute temperature. See Critical
solution temperature
Convex function, 477–478
Critical constants
of elements, 660
of hydrocarbons, 660
of inorganic compounds, 661
of organic compounds, 661
Critical solution temperature (CST), 483
Cubic equations of state,
39–43, 169–171
D
Degrees of freedom, 2, 230, 357
Departure functions, 83, 178
definition, 83–84
for mixture enthalpy
from Peng-Robinson equation of
state, 179
from Redlich-Kwong equation of
state, 179
from van der waals equation of
state, 178
for mixture entropy
from Peng-Robinson equation of
state, 179
from Redlich-Kwong equation of
state, 179
from van der Waals equation of
state, 178
for mixture internal energy
from Peng-Robinson equation of
state, 179
from Redlich-Kwong equation of
state, 179
from van der Waals equation of
state, 179
for pure component enthalpy
from Peng-Robinson equation of
state, 86
from Redlich-Kwong equation of
state, 85
Subject Index
from van der Waals equation of
state, 85
for pure component entropy
from Peng-Robinson equation of
state, 86
from Redlich-Kwong equation of
state, 86
from van der Waals equation of
state, 85
for pure component internal energy
from Peng-Robinson equation of
state, 86
from Redlich-Kwong equation of
state, 86
from van der Waals equation of
state, 85
from principle of corresponding
states
DePriester chart, 374–375
Dew point curve, 353–355
Dew point pressure, 355
calculation of
for ideal liquid mixtures, 366–367
for nonideal liquid mixtures,
399–400
Dew point temperature, 357
calculation of
for ideal liquid mixtures, 368–370
for nonideal liquid mixtures,
403–406
Distribution coefficient. See K-value
E Entropy change
Element-by-species matrix, 553
Elements
acentric factors of, 660
Antoine constants of, 668
critical constants of, 660
heat capacity of ideal gases, 664
Enthalpy
definition, 15
differential expression for, 17, 60
of formation
705
for hydrocarbons, 676
for inorganic compounds, 677
for organic compounds, 678
of mixing. See Excess enthalpy
Enthalpy change
from departure functions, 84, 178
for liquids and solids, 60
for gas mixtures
from Peng-Robinson equation of
state, 175
from Redlich-Kwong equation of
state, 174
from van der Waals equation of
state, 174
for pure gases
from Peng-Robinson equation of
state, 68
from Redlich-Kwong equation of
state, 68
from van der Waals equation of
state, 67
on mixing. See Isothermal enthalpy
change on mixing
between two states, 62
Entropy
balance, 11–12
for a closed system, 12
for an open system, 12
for a steady-state flow system, 12
definition, 10
differential expression for, 18–19, 72
of mixing, See Excess entropy
from departure functions, 84, 178
for liquids and solids, 72
for gas mixtures
from Peng-Robinson equation of
state, 175
from Redlich-Kwong equation of
state, 175
from van der Waals equation of
state, 175
for pure gases
706
from Peng-Robinson equation of
state, 77
from Redlich-Kwong equation of
state, 77
from van der Waals equation of
state, 76
on mixing, 79
between two states, 74
Equations of state, 35
Benedict-Webb-Rubin, 83, 671
cubic, 39, 169
fugacity from, 124, 132
ideal gas, 35
Peng-Robinson, 40, 170
Redlich-Kwong, 40, 170
selection, 92, 184
Soave-Redlich-Kwong, 40, 170
van der waals, 40, 170
virial, 36, 163
VLE calculations from, 422
Equilibrium, 3
chemical, 109, 229–230, 560
criteria for, 105–110
liquid-liquid, 477
mechanical, 109, 230
solid-liquid, 509
thermal, 109, 230
vapor-liquid, 351
Equilibrium constant
evaluation of, 562
gas phase reactions, 571
heterogeneous reactions, 603
liquid phase reactions, 588
Equilibrium stage, 351–352
Euler’s theorem, 193, 228
Eutectic point, 519–520
Exact differential, 4, 16
and state functions, 4–5, 16
Excess enthalpy, 274
Excess Gibbs energy, 274
partial molar, 285, 279
as generating function, 284
Excess mixture properties
Subject Index
and activity coefficient, 279
estimation of, 281
relations between, 275
Exothermic mixing, 481
Extensive property, 2, 194
Extent of reaction, molar, 556
See also Molar extent of reaction
F
First law of thermodynamics, 7, 9
energy balance, simplification
closed system, 9
isolated system, 9
steady-state flow system, 9
equilibrium criteria
for closed system, 105
for open system, 107
First-order transition, 160
Flash calculation, 359
graphical techniques for, 382
for ideal liquid mixtures, 370
for nonideal liquid mixtures, 406
Fractional conversion, 556
Freezing point depression, 517
Fugacity
of component in mixture
gas mixture, 236
liquid mixture, 244
criteria for chemical equilibrium, 229
definition of, 120, 232
in phase equilibrium calculations, 249
solid-liquid equilibrium, 256
solid-vapor equilibrium, 257
vapor-liquid equilibrium, 249
of pure gas, 122
from cubic equation of state, 124
from principle of corresponding
states, 126
from property tables, 123
from virial equation of state, 124
from volume-explicit equations of
state, 122
of pure liquid, 126
Subject Index 707

from cubic equations of state, 132 H

of pure solid, 134 Heat
variation of, with pressure and of fusion, 141
temperature, 148 of mixing, 195, 199
Fugacity coefficient, 120, 233 of reaction, 562, 623
Fundamental excess-property relation, of solution, 466
275 of sublimation, 145
Fundamental property relations, 15 of vaporization, 139
Heat capacity
G constant pressure, 18
c-u model, 352 constant volume, 18
Gas ideal gas, 663
heat capacity, 18 Helmholtz energy, 13–14
ideal, 35 Henry’s law, 448
solubility. See Solubility of gases in and activity coefficient, 459
liquids application of, 468
vs. vapor, 136 bends, 469
Gas phase reactions, 571 carbonated beverages, 468
Gibbs-Duhem equation knuckle cracking, 472
at constant T & P, 208 Lake Nyos, natural disaster at,
for excess properties, 317–318 471
generalized, 222–223 and Lewis-Randall rule, relation
Gibbs energy between, 451
change of Henry’s law constant, 449
with pressure, 110 Conversion of units, 451
with temperature, 112 and infinite dilution activity
definition, 14 coefficient, relationship between,
and equilibrium, 107, 109, 120, 230, 455
560 pressure dependence, 461
excess, 280 temperature dependence, 465
of formation Heterogeneous reactions, 603
for hydrocarbons, 676 Homogeneous functions, 193–194
for inorganic compounds, 677 Homogeneous reactions
for organic compounds, 678 gas phase, 571
as generating function, 30 liquid phase, 588
minimization, 642 Hydrocarbons
of mixing, 480 acentric factors of, 660
Gibbs phase rule, 2, 230 Antoine constants of, 668
for reactive components, 620 critical constants of, 660
Gibbs-Helmholtz equation, 146 enthalpy of formation, 676
Group contribution method, 156 Gibbs energy of formation, 676
Group contribution models, 287–288 heat capacity of ideal gases, 664
708
I from Redlich-Kwong equation of
Ideal gas
definition, 35–36
heat capacity of, 663
molar Gibbs energy of, 119
Ideal gas mixture
definition, 231
vs. ideal mixture, 236–237
partial molar Gibbs energy of, 232
Ideal mixture
definition, 235
fugacity of a component in, 236
property changes on mixing for, 271
Ideal solubility, 513
Ideal solution. See Ideal mixture
Independent reactions, determination of,
611
Infinite dilution activity coefficients, 280,
312
Inorganic compounds
acentric factors of, 661
Antoine constants of, 669
critical constants of, 661
enthalpy of formation, 677
Gibbs energy of formation, 677
Intensive extent of the reaction, 558
Intensive property, 2, 194
Internal energy
definition, 8
differential expression for, 17, 47
Internal energy change
for departure functions, 84, 178
for liquids and solids, 47
for gas mixtures
from Peng-Robinson equation of
state, 173–174
from Redlich-Kwong equation of
state, 173
from van der Waals equation of
state, 173
for pure gases
from Peng-Robinson equation of
state, 50–51
Subject Index
state, 50
from van der Waals equation of
state, 50
between two states, 48–49
Inversion temperature, 27
Isolated system
definition, 1
equilibrium criterion for, 109
first law, 9
second law, 12
Isothermal compressibility, 22
Isothermal enthalpy change on mixing,
195
Isothermal process, 7
Isothermal volume change on mixing.
See Volume change on mixing
J
Jouguet’s method, 622
Joule-Thomson coefficient, 27, 93, 211
K
Kelvin-Planck statement, 10
schematic representation of, 11
Krichevsky-Ilinskaya equation, 465
Krichevsky-Kasarnovsky equation, 462
K-value, 373
L
Lagrange multiplier, 641
Lagrange three-point formula, 312–313
in calculating infinite-dilution activity
coefficient, 313
Law of combining proportions, 555
Law of corresponding states. See
Principle of corresponding states
Le Chatelier’s principle, 585
exceptions to, 587, 609
Lever rule, 373, 493, 497, 520
Lewis-Randall rule, 235
Liquid(s)
enthalpy change for, 60
entropy change for, 72
Subject Index
fugacity of, 126
internal energy change for, 47
solubility of a gas in, 447
solubility of a liquid in, 488
Liquid-liquid equilibrium
applications of, 500
octanol-water partition coefficient,
500
steam distillation, 501
binodal curve, 483–484
calculations, 488
spinodal curve, 483–484
Liquid mixture(s)
component fugacity calculation
from Peng-Robinson equation of
state, 245
from Redlich-Kwong equation of
state, 245
from Soave-Redlich-Kwong
equation of state, 245
from van der Waals equation of
state, 245
solubility diagram, 484–485
stability of, 480
Liquid-liquid extraction, 495
single-stage extraction, graphical
calculation procedure for, 498
triangular diagram, 497
Liquid phase reactions, 588
Liquidus curve, 519–520, 523
Local composition models, 287
NRTL equation, 302
Wilson equation, 300
Lower critical solution temperature
(LCST), 484
M partial molar property, 184
Margules equation
three-suffix (two constant), 291
two-suffix (one-constant), 288
Matrix
algebra, 681
addition and subtraction, 681
709
multiplication, 682
cofactor of, 684
definition, 679
determinant of, 683
properties of, 685
properties of, 683
skew-symmetric matrices, 686
symmetric matrices, 686
transpose of, 686
types of, 680
column matrix, 679
null matrix, 681
row matrix, 679
singular matrix, 681
sparse matrix, 681
square matrix, 680
triangular matrix, 680
Maxwell equal area rule, 41
Maxwell relations, 16
Melting temperature, 142
Methane cracking reaction, 627
equilibrium constant of, 627
Minimization of Gibbs energy, 642
Mixing rule for equations of state, 169
Mixture(s)
azeotropic, 412–413
cubic equations of state, 169–170
enthalpy change, calculation, 174
entropy change, calculation, 175
internal energy change, calculation,
173
departure functions, 178
excess property, 273
fugacity of a component, 232
ideal gas, 231
ideal mixture, 235
property changes on mixing, 194
virial equation of state, 163
Modified Rackett equation, 129
Molality, 188, 517
Molar enthalpy of mixture, 200
Molar excess Gibbs energy, 274
710
Molar extent of reaction, 556
change of
with addition of inerts, 584
with pressure, 583
with temperature, 583
Molar properties, 2
Mole fraction solubility, 512
Multiple chemical reactions, 611
independent reactions, 611
stoichiometric matrix, 611
minimization of Gibbs energy, 642
N volume, 286
Newton’s method for nonlinear systems,
387
Newton-Raphson method, 377–380,
426–427
Normal boiling point, 141
Normal melting (freezing) point, 138
NRTL equation, 302
O infinite dilution, 190
Objective function, 291, 333, 335
Octanol-water partition coefficient, 500
of various substances, 501
Open system
definition, 1
equilibrium criteria for, 107
first law, 8
second law, 12
Operating line, 385–386
Organic compounds
acentric factors of, 661
Antoine constants of, 669
critical constants of, 661
enthalpy of formation, 678
Gibbs energy of formation, 678
heat capacity of ideal gases, 665
Osmometer, 532–533
Osmosis, 528
applications of, 534
biology, 534
osmotic power plant, 535
Subject Index
osmotic pump, 535–536
Osmotic pressure, 529
P
Partial differentials, relationship
between, 19
inverse rule, 19
triple product rule, 19–20
cyclic relation for, 20
Partial molar excess property
definition, 275
enthalpy, 285
Gibbs energy, 279
Partial molar Gibbs energy, 226
Partial molar property, 184
determination of, 187
method of tangent intercepts, 188–
189
method of tangent slope, 187
equation for calculation of, 190
and homogeneous functions, 193
Partition coefficient. See K-value
Path function, 4
Peng-Robinson equation of state
mixtures, 170
departure functions, 179
enthalpy change for, 175
entropy change for, 175
fugacity coefficient from, 243
internal energy change for,
173–174
pure substances, 40
departure functions, 86
enthalpy change for, 68
entropy change for, 77
fugacity coefficient from, 124–125
internal energy change for, 50–51
Phase diagrams, 136
lever rule, 373, 493, 497, 520
liquid-liquid, 485
for a pure species, 136–137
solid-liquid, 519–523
Subject Index 711

vapor-liquid negative deviation, 411–412

Pxy, 353
Txy, 355
xy, 357
Phase equilibrium
criteria for, 120, 229–230
liquid-liquid, 477
solid-liquid, 509
solubility of gases in liquids, 447
vapor-liquid, 351
Phase rule. See Gibbs phase rule
Phase stability, 110
Phase transition
and equilibrium criteria, 136
Clapeyron equation, 138
solid-liquid equilibrium, 141
solid-vapor equilibrium, 145
vapor-liquid equilibrium, 139
u-u model, 353, 422
Plait point, 497
Poynting correction factor (PCF), 128
Pressure swing distillation, 417–418
Pressure-composition diagram. See Pxy
diagram
Principle of corresponding states, 81
Pseudo-component, 184
Process,
adiabatic, 7
definition, 3
irreversible, 5
isobaric, 7
isometric/isochoric, 7
isothermal, 7
reversible, 7
Pxy diagram, 353, 382
R Shaft work, 6
Rachford-Rice equation, 376
Rackett equation. See Modified Rackett
equation
Rackett parameter, 129
Raoult’s law, 359
deviations from, 410
positive deviation, 411
Redlich-Kister type expansion, 204
Redlich-Kwong equation of state
mixtures, 170
departure functions, 179
enthalpy change for, 174
entropy change for, 175
fugacity coefficient from, 241
internal energy change for 173
pure substances, 40
departure functions, 85–86
enthalpy change for, 68
entropy change for, 77
fugacity coefficient from, 124–125
internal energy change for, 50
Reduced pressure, 37
Reduced row echelon form, of matrix,
691
Reduced temperature, 37
Regular mixture, 303
Relative volatility, 415
Reverse osmosis, 529
Reversible process, 5
S
Salting-in, 467
Salting-out, 467
Scatchard-Hildebrand theory, 304, 341
Schröder equation, 513
Second law of thermodynamics, 10
entropy balance, simplification
closed system, 12
isolated system, 12
steady-state flow system, 12
Second order transition, 161
Shomate equation, 605
Soave-Redlich-Kwong equation of state
mixtures, 170
fugacity coefficient from, 243
pure substances, 40
fugacity coefficient from, 124–125
712
Solid-liquid equilibrium (SLE), 141, 509
Solid solution, 523
Solidus curve, 519–520, 523
Solid-vapor equilibrium, 145
Solubility of gases in liquids, 447
effect of pressure on, 461
effect of temperature on, 465
Solubility parameter, 304
Solvent extraction. See Liquid-liquid
extraction,
Specific properties, 2
Spinodal curve, 483–484
State function, 4
Steady-state, 3
Stoichiometry of a chemical reaction,
551
Supercritical fluids, 136–137
Surroundings, definition, 1
T azeotrope, 412
Tait equation, 32
Temperature-composition diagram. See
Txy diagram
Temperature-pressure diagram, 136–137
Thermodynamic consistency, 317
Three-suffix Margules equation, 291
Tie line, 353–357
Total differential, 4–5
Triangular diagram, 497
Triple point, 136
Triple product rule, 19
Trouton’s rule, 154
Trouton-Hildebrand-Everett rule, 154
Tsonopoulos correlation, 92
Two-suffix Margules equation, 288
Txy diagram, 355, 382
U Work functions, 13
UNIFAC model, 306
Uniform, 3
Universe, definition, 1
Upper critical solution temperature
(UCST), 483, 488–489
Subject Index
V
van der Waals equation of state, 40
mixtures
departure functions, 178
enthalpy change for, 174
entropy change for, 175
fugacity coefficient from, 239
internal energy change for, 173
pure substances
departure functions, 85
enthalpy change for, 67
entropy change for, 77
fugacity coefficient from, 124–125
internal energy change for, 50
van Laar equation, 297
van’t Hoff equation, 527, 565
van’t Hoff factor, 517–518, 527
Vapor-liquid equilibrium (VLE), 139,
351
calculations, 352
for ideal liquid mixtures, 363
for nonideal liquid mixtures, 392
using equation of state, 422
Raoult’s law, 359
deviations from, 410–411
relative volatility, 415
azeotrope formation criteria, 419
solubility of gases in liquids, 447
Virial equation of state, 36, 163
fugacity coefficient for
mixtures, 237
pure substances, 124
Volume change, on mixing, 195–199
W
Wilson equation, 300
See also Helmholtz energy; Gibbs
energy
X
x-y diagram, 357–358, 385–386