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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 Subject Index

Chemical potential, 109, 226 Conservative force, 4


Chemical reaction Consolute temperature. See Critical
endothermic, 565 solution temperature
exothermic, 565 Convex function, 477–478
extent of, molar, 556 Critical constants
feasibility of, 623 of elements, 660
heat of, 562, 623 of hydrocarbons, 660
standard enthalpy change of, 562 of inorganic compounds, 661
standard Gibbs energy change of of organic compounds, 661
562 Critical solution temperature (CST), 483
stoichiometry of, 551 Cubic equations of state,
Chemical reaction equilibrium 39–43, 169–171
criteria for, 560
equilibrium constant evaluation, 562 D
gas phase reactions, 571 Degrees of freedom, 2, 230, 357
heterogeneous reactions, 603 Departure functions, 83, 178
liquid phase reactions, 588 definition, 83–84
multiple reactions for mixture enthalpy
independent reactions, 611 from Peng-Robinson equation of
Clapeyron equation, 138 state, 179
Clausius statement, 10 from Redlich-Kwong equation of
schematic representation of, 11 state, 179
Clausius-Clapeyron equation, 139 from van der waals equation of
Closed system state, 178
definition, 1 for mixture entropy
equilibrium criteria for, 105 from Peng-Robinson equation of
first law, 9 state, 179
second law, 12 from Redlich-Kwong equation of
Coefficient of thermal expansion, 22 state, 179
Cohesive energy density, 341 from van der Waals equation of
and solubility parameter, 342 state, 178
Colligative for mixture internal energy
definition, 517, 523 from Peng-Robinson equation of
properties state, 179
boiling point elevation, 524 from Redlich-Kwong equation of
freezing point depression, 517 state, 179
osmotic pressure, 529–300 from van der Waals equation of
Common tangent rule, 481–482 state, 179
Compressibility factor, 35–36 for pure component enthalpy
Concave function, 477–478 from Peng-Robinson equation of
Conservation of energy. See First law of state, 86
thermodynamics from Redlich-Kwong equation of
Conservation of mass, 552 state, 85
Subject Index 705

from van der Waals equation of for hydrocarbons, 676


state, 85 for inorganic compounds, 677
for pure component entropy for organic compounds, 678
from Peng-Robinson equation of of mixing. See Excess enthalpy
state, 86 Enthalpy change
from Redlich-Kwong equation of from departure functions, 84, 178
state, 86 for liquids and solids, 60
from van der Waals equation of for gas mixtures
state, 85 from Peng-Robinson equation of
for pure component internal energy state, 175
from Peng-Robinson equation of from Redlich-Kwong equation of
state, 86 state, 174
from Redlich-Kwong equation of from van der Waals equation of
state, 86 state, 174
from van der Waals equation of for pure gases
state, 85 from Peng-Robinson equation of
from principle of corresponding state, 68
states from Redlich-Kwong equation of
DePriester chart, 374–375 state, 68
Dew point curve, 353–355 from van der Waals equation of
Dew point pressure, 355 state, 67
calculation of on mixing. See Isothermal enthalpy
for ideal liquid mixtures, 366–367 change on mixing
for nonideal liquid mixtures, between two states, 62
399–400 Entropy
Dew point temperature, 357 balance, 11–12
calculation of for a closed system, 12
for ideal liquid mixtures, 368–370 for an open system, 12
for nonideal liquid mixtures, for a steady-state flow system, 12
403–406 definition, 10
Distribution coefficient. See K-value differential expression for, 18–19, 72
of mixing, See Excess entropy
E Entropy change
Element-by-species matrix, 553 from departure functions, 84, 178
Elements for liquids and solids, 72
acentric factors of, 660 for gas mixtures
Antoine constants of, 668 from Peng-Robinson equation of
critical constants of, 660 state, 175
heat capacity of ideal gases, 664 from Redlich-Kwong equation of
Enthalpy state, 175
definition, 15 from van der Waals equation of
differential expression for, 17, 60 state, 175
of formation for pure gases
706 Subject Index

from Peng-Robinson equation of and activity coefficient, 279


state, 77 estimation of, 281
from Redlich-Kwong equation of relations between, 275
state, 77 Exothermic mixing, 481
from van der Waals equation of Extensive property, 2, 194
state, 76 Extent of reaction, molar, 556
on mixing, 79 See also Molar extent of reaction
between two states, 74
Equations of state, 35 F
Benedict-Webb-Rubin, 83, 671 First law of thermodynamics, 7, 9
cubic, 39, 169 energy balance, simplification
fugacity from, 124, 132 closed system, 9
ideal gas, 35 isolated system, 9
Peng-Robinson, 40, 170 steady-state flow system, 9
Redlich-Kwong, 40, 170 equilibrium criteria
selection, 92, 184 for closed system, 105
Soave-Redlich-Kwong, 40, 170 for open system, 107
van der waals, 40, 170 First-order transition, 160
virial, 36, 163 Flash calculation, 359
VLE calculations from, 422 graphical techniques for, 382
Equilibrium, 3 for ideal liquid mixtures, 370
chemical, 109, 229–230, 560 for nonideal liquid mixtures, 406
criteria for, 105–110 Fractional conversion, 556
liquid-liquid, 477 Freezing point depression, 517
mechanical, 109, 230 Fugacity
solid-liquid, 509 of component in mixture
thermal, 109, 230 gas mixture, 236
vapor-liquid, 351 liquid mixture, 244
Equilibrium constant criteria for chemical equilibrium, 229
evaluation of, 562 definition of, 120, 232
gas phase reactions, 571 in phase equilibrium calculations, 249
heterogeneous reactions, 603 solid-liquid equilibrium, 256
liquid phase reactions, 588 solid-vapor equilibrium, 257
Equilibrium stage, 351–352 vapor-liquid equilibrium, 249
Euler’s theorem, 193, 228 of pure gas, 122
Eutectic point, 519–520 from cubic equation of state, 124
Exact differential, 4, 16 from principle of corresponding
and state functions, 4–5, 16 states, 126
Excess enthalpy, 274 from property tables, 123
Excess Gibbs energy, 274 from virial equation of state, 124
partial molar, 285, 279 from volume-explicit equations of
as generating function, 284 state, 122
Excess mixture properties 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 Subject Index

I from Redlich-Kwong equation of


Ideal gas state, 50
definition, 35–36 from van der Waals equation of
heat capacity of, 663 state, 50
molar Gibbs energy of, 119 between two states, 48–49
Ideal gas mixture Inversion temperature, 27
definition, 231 Isolated system
vs. ideal mixture, 236–237 definition, 1
partial molar Gibbs energy of, 232 equilibrium criterion for, 109
Ideal mixture first law, 9
definition, 235 second law, 12
fugacity of a component in, 236 Isothermal compressibility, 22
property changes on mixing for, 271 Isothermal enthalpy change on mixing,
Ideal solubility, 513 195
Ideal solution. See Ideal mixture Isothermal process, 7
Independent reactions, determination of, Isothermal volume change on mixing.
611 See Volume change on mixing
Infinite dilution activity coefficients, 280,
J
312
Jouguet’s method, 622
Inorganic compounds Joule-Thomson coefficient, 27, 93, 211
acentric factors of, 661
Antoine constants of, 669 K
critical constants of, 661 Kelvin-Planck statement, 10
enthalpy of formation, 677 schematic representation of, 11
Gibbs energy of formation, 677 Krichevsky-Ilinskaya equation, 465
Intensive extent of the reaction, 558 Krichevsky-Kasarnovsky equation, 462
Intensive property, 2, 194 K-value, 373
Internal energy
definition, 8 L
differential expression for, 17, 47 Lagrange multiplier, 641
Internal energy change Lagrange three-point formula, 312–313
for departure functions, 84, 178 in calculating infinite-dilution activity
for liquids and solids, 47 coefficient, 313
for gas mixtures Law of combining proportions, 555
from Peng-Robinson equation of Law of corresponding states. See
state, 173–174 Principle of corresponding states
from Redlich-Kwong equation of Le Chatelier’s principle, 585
state, 173 exceptions to, 587, 609
from van der Waals equation of Lever rule, 373, 493, 497, 520
state, 173 Lewis-Randall rule, 235
for pure gases Liquid(s)
from Peng-Robinson equation of enthalpy change for, 60
state, 50–51 entropy change for, 72
Subject Index 709

fugacity of, 126 multiplication, 682


internal energy change for, 47 cofactor of, 684
solubility of a gas in, 447 definition, 679
solubility of a liquid in, 488 determinant of, 683
Liquid-liquid equilibrium properties of, 685
applications of, 500 properties of, 683
octanol-water partition coefficient, skew-symmetric matrices, 686
500 symmetric matrices, 686
steam distillation, 501 transpose of, 686
binodal curve, 483–484 types of, 680
calculations, 488 column matrix, 679
spinodal curve, 483–484 null matrix, 681
Liquid mixture(s) row matrix, 679
component fugacity calculation singular matrix, 681
from Peng-Robinson equation of sparse matrix, 681
state, 245 square matrix, 680
from Redlich-Kwong equation of triangular matrix, 680
state, 245 Maxwell equal area rule, 41
from Soave-Redlich-Kwong Maxwell relations, 16
equation of state, 245 Melting temperature, 142
from van der Waals equation of Methane cracking reaction, 627
state, 245 equilibrium constant of, 627
solubility diagram, 484–485 Minimization of Gibbs energy, 642
stability of, 480 Mixing rule for equations of state, 169
Liquid-liquid extraction, 495 Mixture(s)
single-stage extraction, graphical azeotropic, 412–413
calculation procedure for, 498 cubic equations of state, 169–170
triangular diagram, 497 enthalpy change, calculation, 174
Liquid phase reactions, 588 entropy change, calculation, 175
Liquidus curve, 519–520, 523 internal energy change, calculation,
Local composition models, 287 173
NRTL equation, 302 departure functions, 178
Wilson equation, 300 excess property, 273
Lower critical solution temperature fugacity of a component, 232
(LCST), 484 ideal gas, 231
ideal mixture, 235
M partial molar property, 184
Margules equation property changes on mixing, 194
three-suffix (two constant), 291 virial equation of state, 163
two-suffix (one-constant), 288 Modified Rackett equation, 129
Matrix Molality, 188, 517
algebra, 681 Molar enthalpy of mixture, 200
addition and subtraction, 681 Molar excess Gibbs energy, 274
710 Subject Index

Molar extent of reaction, 556 osmotic pump, 535–536


change of Osmotic pressure, 529
with addition of inerts, 584
with pressure, 583 P
with temperature, 583 Partial differentials, relationship
Molar properties, 2 between, 19
Mole fraction solubility, 512 inverse rule, 19
Multiple chemical reactions, 611 triple product rule, 19–20
independent reactions, 611 cyclic relation for, 20
stoichiometric matrix, 611 Partial molar excess property
minimization of Gibbs energy, 642 definition, 275
enthalpy, 285
Gibbs energy, 279
N volume, 286
Newton’s method for nonlinear systems, Partial molar Gibbs energy, 226
387 Partial molar property, 184
Newton-Raphson method, 377–380, determination of, 187
426–427 method of tangent intercepts, 188–
Normal boiling point, 141 189
Normal melting (freezing) point, 138 method of tangent slope, 187
NRTL equation, 302 equation for calculation of, 190
and homogeneous functions, 193
O infinite dilution, 190
Objective function, 291, 333, 335 Partition coefficient. See K-value
Octanol-water partition coefficient, 500 Path function, 4
of various substances, 501 Peng-Robinson equation of state
Open system mixtures, 170
definition, 1 departure functions, 179
equilibrium criteria for, 107 enthalpy change for, 175
first law, 8 entropy change for, 175
second law, 12 fugacity coefficient from, 243
Operating line, 385–386 internal energy change for,
Organic compounds 173–174
acentric factors of, 661 pure substances, 40
Antoine constants of, 669 departure functions, 86
critical constants of, 661 enthalpy change for, 68
enthalpy of formation, 678 entropy change for, 77
Gibbs energy of formation, 678 fugacity coefficient from, 124–125
heat capacity of ideal gases, 665 internal energy change for, 50–51
Osmometer, 532–533 Phase diagrams, 136
Osmosis, 528 lever rule, 373, 493, 497, 520
applications of, 534 liquid-liquid, 485
biology, 534 for a pure species, 136–137
osmotic power plant, 535 solid-liquid, 519–523
Subject Index 711

vapor-liquid negative deviation, 411–412


Pxy, 353 positive deviation, 411
Txy, 355 Redlich-Kister type expansion, 204
xy, 357 Redlich-Kwong equation of state
Phase equilibrium mixtures, 170
criteria for, 120, 229–230 departure functions, 179
liquid-liquid, 477 enthalpy change for, 174
solid-liquid, 509 entropy change for, 175
solubility of gases in liquids, 447 fugacity coefficient from, 241
vapor-liquid, 351 internal energy change for 173
Phase rule. See Gibbs phase rule pure substances, 40
Phase stability, 110 departure functions, 85–86
Phase transition enthalpy change for, 68
and equilibrium criteria, 136 entropy change for, 77
Clapeyron equation, 138 fugacity coefficient from, 124–125
solid-liquid equilibrium, 141 internal energy change for, 50
solid-vapor equilibrium, 145 Reduced pressure, 37
vapor-liquid equilibrium, 139 Reduced row echelon form, of matrix,
u-u model, 353, 422 691
Plait point, 497 Reduced temperature, 37
Poynting correction factor (PCF), 128 Regular mixture, 303
Pressure swing distillation, 417–418 Relative volatility, 415
Pressure-composition diagram. See Pxy Reverse osmosis, 529
diagram Reversible process, 5
Principle of corresponding states, 81
Pseudo-component, 184 S
Process, Salting-in, 467
adiabatic, 7 Salting-out, 467
definition, 3 Scatchard-Hildebrand theory, 304, 341
irreversible, 5 Schröder equation, 513
isobaric, 7 Second law of thermodynamics, 10
isometric/isochoric, 7 entropy balance, simplification
isothermal, 7 closed system, 12
reversible, 7 isolated system, 12
Pxy diagram, 353, 382 steady-state flow system, 12
Second order transition, 161
R Shaft work, 6
Rachford-Rice equation, 376 Shomate equation, 605
Rackett equation. See Modified Rackett Soave-Redlich-Kwong equation of state
equation mixtures, 170
Rackett parameter, 129 fugacity coefficient from, 243
Raoult’s law, 359 pure substances, 40
deviations from, 410 fugacity coefficient from, 124–125
712 Subject Index

Solid-liquid equilibrium (SLE), 141, 509 V


Solid solution, 523 van der Waals equation of state, 40
Solidus curve, 519–520, 523 mixtures
Solid-vapor equilibrium, 145 departure functions, 178
Solubility of gases in liquids, 447 enthalpy change for, 174
effect of pressure on, 461 entropy change for, 175
effect of temperature on, 465 fugacity coefficient from, 239
Solubility parameter, 304 internal energy change for, 173
Solvent extraction. See Liquid-liquid pure substances
extraction, departure functions, 85
Specific properties, 2 enthalpy change for, 67
Spinodal curve, 483–484 entropy change for, 77
State function, 4 fugacity coefficient from, 124–125
Steady-state, 3 internal energy change for, 50
Stoichiometry of a chemical reaction, van Laar equation, 297
551 van’t Hoff equation, 527, 565
Supercritical fluids, 136–137 van’t Hoff factor, 517–518, 527
Surroundings, definition, 1 Vapor-liquid equilibrium (VLE), 139,
351
T azeotrope, 412
Tait equation, 32 calculations, 352
Temperature-composition diagram. See for ideal liquid mixtures, 363
Txy diagram for nonideal liquid mixtures, 392
Temperature-pressure diagram, 136–137 using equation of state, 422
Thermodynamic consistency, 317 Raoult’s law, 359
Three-suffix Margules equation, 291 deviations from, 410–411
Tie line, 353–357 relative volatility, 415
Total differential, 4–5 azeotrope formation criteria, 419
Triangular diagram, 497 solubility of gases in liquids, 447
Triple point, 136 Virial equation of state, 36, 163
Triple product rule, 19 fugacity coefficient for
Trouton’s rule, 154 mixtures, 237
Trouton-Hildebrand-Everett rule, 154 pure substances, 124
Tsonopoulos correlation, 92 Volume change, on mixing, 195–199
Two-suffix Margules equation, 288
Txy diagram, 355, 382 W
Wilson equation, 300
U Work functions, 13
UNIFAC model, 306 See also Helmholtz energy; Gibbs
Uniform, 3 energy
Universe, definition, 1
Upper critical solution temperature X
(UCST), 483, 488–489 x-y diagram, 357–358, 385–386