coefficient and molality, 392, 539

coefficient in the concentration scale, 393

coefficient of a species in a real solution, 375

coefficient using convention I, 379, 539

coefficient using convention II, 386, 539

effect of temperature and pressure on the –– coefficient, 377

of a condensed phase, 332

of a pure condensed phase, 331

of a species in a real solution, 375

relation between convention I and II in solutions, 388

Adiabatic

change of a van der Waals gas, 174

closed –– system, 38, 254

enclosure, 4, 23

irreversible –– process, 176

open –– system, 176

process, 23, 173, 189

reversible process of an ideal gas, 51, 108, 193

reversible process, 33

Affinity

definition, 327

of a reaction, 327

Air conditioner, 56

Auxiliary

functions, 65, 217

state variable, 4

Avogadro's number, 19, 31

Azeotropy, 381-384

Batteries

lead storage ––, 315

––, 314

Beau de Rochas cycle, 58

Binary

mixture, 361, 364, 366, 503, 505, 510, 536

system, 380, 536, 537

Boiling

elevation of the –– point of a solvent in the presence of a solute, 371, 509

point curve, 364, 503, 505

Boltzmann constant, 30

Boltzons

 ––, 404

corrected ––, 406

thermodynamic functions for a system of corrected ––, 410

Bose-Einstein Statistics, 403, 404

Bosons, 404

Canonical

ensemble, 420-423

partition function, 422, 425, 561

Carbon monoxide

reduction of iron oxides by ––, 352

Carnot

cycle, 32, 50

reverse –– cycle, 34

Change

isothermal reversible –– of a gas, 17

of a state variable, 7

of the Gibbs energy in a mixture of chemical species, 324, 461

of the Gibbs energy with the extent of reaction, 324, 326, 461

Characteristic variables, 68-73, 592

Châtelier

Le ––'s principle, 345-350, 462

Chemical

condition for –– equilibrium, 298

conversion of –– energy into work, 312, 313, 439

equilibrium, 323-359, See also Chemical equilibrium

independent –– reactions, 334

reaction, 295

spontaneous –– reaction, 323

Chemical equilibrium

effect of an inert gas on a ––, 347, 460

effect of pressure on a ––, 346

effect of species in excess on a ––, 348

effect of temperature on a ––, 345

effect of volume on a ––, 347

reduction of iron oxides, 351

––, 298, 323-359, 455

Chemical potential

definition, 70

intensive property, 92

of a multiphase system at equilibrium, 135

of a pure condensed phase, 331

of a pure real gas, 118

of a real gas in a mixture, 127

of a species in a real solution, 375

of an ideal gas in a mixture, 113-114

of an ideal species, 362

of ions in solution, 396

relations, 72

standard ––, 106

Chemical reaction

isothermal and isobaric ––, 297

system with several ––s, 298

volume work for a ––, 17

Chloroform

liquid state study of ––, 220

Choice

of the standard state pressure, 317

Clapeyron equation, 139, 276

Clausius inequality, 42

Clausius-Clapeyron equation, 142

Closed

adiabatic system, 40, 43, 254

system with one chemical reaction, 295

system, 2

Coefficient

activity –– and molality, 392, 539

activity –– and the concentration scale, 393

fugacity –– of a pure real gas, 119, 255

fugacity –– of a real gas in a mixture, 128

fugacity ––, 118, 255

isobaric –– of thermal expansion, 7

isothermal compressibility ––, 6, 7, 156

Joule-Thomson ––, 125

of performance, 55, 57

partition ––, 390

stoichiometric ––s, 295, 456, 457, 463

thermal expansion ––, 6

van der Waals ––, 121

Combustion

internal –– engine, 58

variables of ––, 321

Complex

van der Waals ––, 118

Components

number of ––s in a system, 342

Composition

molality and ––, 391

mole fraction scale, 375

of the vapor phase of a binary solution, 364, 366, 385, 386, 505

Compressibility

factor, 119, 254

isothermal –– coefficient of an ideal gas, 157

isothermal –– coefficient, 6, 7, 156

Compression

isothermal –– of an ideal gas, 47

monothermal –– of an ideal gas, 47

of a gas, 9, 16

ratio, 60, 64

Concentration

and composition, 393

scale, 393

Condensation

curve, 364, 366, 383, 385, 505

––, 141

Condensed phase

choice of the standard state of a ––, 320

Constant

critical ––s, 122, 253

Henry's ––, 388, 389

Raoult's ––, 363, 389

standard equilibrium ––, 329, 539

thermodynamic equilibrium ––, 329

volume thermal expansion coefficient, 7

Constant pressure

process at ––, 67, 166

Constant volume

process at ––, 66

Continuity of the fluid state, 148

Convention

for aqueous systems, 398

I for the standard state and activity coefficient, 378, 536

II for the standard state and activity coefficient, 386, 539

relation between –– I and II, 388

relation between –– II and the molality scale, 392, 539

sign –– for energy exchanges, 13

––s for activity coefficients in solutions, 376-393, 535

Conversion of chemical energy into work, 312-313, 439

Corrected boltzons, 406

Corresponding states of real gases, 123

Creation of entropy, 41

Critical

constants, 122, 253

point, 122, 148, 253

temperature, 121

Crystallization, 141

Curve

condensation ––, 366

inversion ––, 126

vaporization ––, 364, 366, 503, 505

Cycle

Beau de Rochas ––, 58

Carnot –– of an ideal gas, 50

Carnot ––, 32

dithermal ––, 32

engine ––, 33

Joule ––, 63

Otto ––, 58

reverse Carnot ––, 34

reversible –– of two systems, 33

Stirling ––, 60

Cyclic

process of a gas, 219

process, 8, 24, 193

Dalton's law, 110

Debye

model, 427

temperature, 428

Debye-Hückel theory, 397

Degrees of freedom

number of ––, 138

––, 415

Delay

phase change ––s, 150

Depression

of the freezing point in the presence of a solute, 369, 507

Dew point curve, 364, 366, 383, 385, 505

Diagram

isobaric –– for a perfect binary solution, 366, 505

isothermal –– for a perfect binary solution, 364

phase ––, 146

Diamond

equilibrium of –– and graphite, 461

Diathermal enclosure, 4

Differential

exact ––, 9-10

Differential expression

for state functions (multiple phases), 134

for the enthalpy, 70

for the entropy, 218

for the free energy, 71

for the free enthalpy, 71

for the Gibbs energy, 71

for the Gibbs function, 71

for the Helmholtz function, 71

for the internal energy, 69

––, 155

––s for open systems, 72

Dilute solutions, 379, 387, 392, 393

Dilute systems, 406

Dissociation equilibrium, 397

Distribution

laws in statistical mechanics, 403

most probable ––, 421

Dithermal cycle, 32

Dulong and Petit's law, 425

Effect

Joule–Thomson ––, 124, 256

of an inert gas on chemical equilibria, 347, 460

of an inert gas on vapor pressure, 144, 277

of pressure on chemical equilibria, 346, 462

of pressure on phase equilibrium, 276

of species in excess on chemical equilibria, 348, 463

of temperature and pressure on the activity coefficient, 377

of temperature on chemical equilibria, 345, 455, 461

of temperature on the entropy of reaction, 310, 437, 438

of temperature on the Gibbs energy of reaction, 310, 437, 438

of temperature on the latent heat, 145, 277

of temperature on vapor pressure, 145, 276, 277

of volume on chemical equilibria, 347

Efficiency of an engine, 55, 59

Einstein

model, 425

temperature, 426

Electrical work, 18

Electrode potential

and standard entropy, 400

definition, 400

Electrolyte

chemical potential of ions in solution, 396

dissociation, 395

Electroneutrality of a solution, 395

Electronic partition function, 419

Elevation of the boiling point of solvent in the presence of a solute, 371, 509

Enclosure

adiabatic ––, 4, 23

diathermal ––, 4

Endothermic reaction, 307

Energetics of chemical reactions, 295-321, 435

Energy

free ––, 70

Gibbs ––, 66

Helmholtz ––, 66

internal ––, 22, 69

levels for a particle in a box, 413

sign convention for –– exchanges, 13

various forms of ––, 19

Engine cycle, 33

Ensemble

canonical ––, 420-423

microcanonical ––, 408, 420

Enthalpy

explicit expression for the ––, 94

free –– of reaction, 297

of a phase change, 279

of an ideal mixture of gases, 131

of mixing, 112, 129, 368

of phase change, 141

of reaction, 300

standard –– of formation, 303

––, 6, 65

Entropy

a first glance at ––, 29

and irreversible adiabatic process of an ideal gas, 193

and probability, 402

change during freezing, 190

change of –– of an ideal gas due to a change of state, 107, 251

created, 41

definition, 35

effect of temperature on the –– of reaction, 310, 437, 438

evaluating ––, 429

global –– , 42, 81, 82, 112, 190, 218, 219, 280, 312, 314

of a gas mixture and statistical mechanics, 563

of an ideal gas, 106, 218

of mixing, 110, 251, 368, 377, 565

of reaction, 300, 400

standard ––, 303, 565

state function, 36-38

variation at 0 K with volume and pressure, 431

Equation

Clapeyron ––, 139, 276

Clausius-Clapeyron ––, 142

Gibbs-Duhem ––, 95

Kirchhoff's ––, 308-310, 438, 471

van der Waals –– of state, 120, 253

van't Hoff's ––, 344

virial ––, 119, 252

Equation of state

for a gas when internal energy is independent of volume, 218

of a pure liquid, 156, 331

thermodynamic, 75-77

van der Waals ––, 120, 253

–– of an ideal gas, 77

Equilibria

simultaneous ––, 456

Equilibrium

condition for chemical ––, 298

condition, 43, 86, 324

constant in the liquid phase, 394

constant, 329

displacement laws, 345, 462

dissociation ––, 397

effect of an inert gas on a chemical ––, 347, 460

effect of pressure on a chemical ––, 346

effect of pressure on phase ––, 276, 460

effect of species in excess on a chemical ––, 348

effect of temperature and pressure on liquid vapor ––, 368

effect of temperature on a chemical ––, 345

effect of temperature on the –– constant, 343, 456

effect of volume on a chemical ––, 347

gas and condensed phase —, 141

liquid vapor ––, 364, 508

mechanical ––, 3

of a chemical system, 3

of two phases, 139-146, 276

reaction extent at ––, 458, 460, 463

reduction of iron oxides, 351-359

solid liquid ––, 276, 510

standard –– constant, 329, 539

system in a state of ––, 3

thermal ––, 3, 43

thermodynamic –– constant, 329

Equilibrium constant

in heterogeneous systems, 332

in solutions, 394

in the gas phase, 330

in the liquid phase, 394

standard ––, 329

Euler's identity, 90, 93

Eutectic

mixture, 510

temperature, 510

Evaluation of entropies, 429

Evaporation, 141

Exact differential, 9-10, 155, 157

Excess

entropy of mixing (gases), 129

entropy of mixing, 377

Gibbs energy of mixing (gases), 129

Gibbs energy of mixing, 376, 536

variable of mixing (gases), 129

variable of mixing, 376, 536

Exothermic reaction, 307

Expansion

isobaric coefficient of thermal –– of an ideal gas, 157

isobaric coefficient of thermal ––, 6, 156

isothermal –– of an ideal gas, 47

monothermal –– of an ideal gas, 47, 49-50

of a gas, 9

Explicit expression

for enthalpy, 94

for internal energy, 93

for the Gibbs energy, 95

for the Helmholtz energy, 95

Expression

explicit –– for the Gibbs energy, 95

explicit –– for the Helmholtz energy, 95

for partial molar volumes, 237, 238

general ––s of state functions for multiphase systems, 136

of the molar entropy of an ideal gas, 106

Extensive

properties of –– variables, 90

variable, 5, 93

Extent

Change of the Gibbs energy with the –– of reaction, 324, 461

change of the Gibbs energy with the –– of reaction, 326

effect of temperature on the –– of reaction, 460, 462

maximum value of the ––  of reaction, 325

of reaction and expression of enthalpy, 309

of reaction and maximum work, 316

of reaction and work, 312, 313

of reaction for independent reactions, 299

of reaction, 296, 435, 458

Extraction

liquid-liquid ––, 390

Factor

integrating ––, 157

Fermi-Dirac Statistics, 403, 405

Fermions, 405

Field

magnetic ––, 20

First law

about the ––, 21-25

of thermodynamics, 173

Fluid

continuity of the –– state, 148

Force

external ––, 14

van der Waals ––s, 116

work of an external ––, 14

Formation

standard enthalpy of ––, 303

standard Gibbs energy of ––, 303

standard Helmholtz energy of ––, 303

standard variables of ––, 302

Forward

Carnot cycle, 33

reaction, 328

Free

energy, 66, 70, See also Helmholtz energy

enthalpy, 6, 66, 71, See also Gibbs energy

Freedom

degrees of ––, 415, See also Variance

Freezing

point depression by a solute, 369, 507

spontaneous –– of water, 217

temperature of sea water, 509

––, 141

Fugacity

and the law of mass action, 329

coefficient of a pure real gas, 119, 255

coefficient, 118, 255

definition, 118

of a real gas in a mixture, 128

Function

auxiliary state ––, 65, 217

canonical partition ––, 425

homogeneous ––s, 89-90

microcanonical partition ––, 410, 416, 561, 564, 566

of mixing, 114-116

properties of homogeneous ––s, 89-90

rotational partition ––, 418

state ––, 10

thermodynamic ––s for a system of corrected boltzons, 410

thermodynamic ––s in the microcanonical ensemble, 414

translational partition ––, 416

Fundamental state variables, 4

Fusion

curve, 146

latent heat of ––, 370, 508

––, 141

Gas

constant, 11

Effect of an inert –– on vapor pressure, 144, 277

Equation of state of an ideal ––, 11

equation of state of an ideal —, 77

ideal –– mixture, 108

real ––es, 116

thermodynamics of ––es, 105-132

Gauss elimination, 338

General process, 7, 23

Generalization of Hess's law, 306

Gibbs

change of the –– energy with the extent of reaction, 435

effect of temperature on the –– energy, 310, 437, 438

excess –– energy of mixing (gases), 129

excess –– energy of mixing (solutions), 376, 536

explicit expression for the –– energy, 95

function, 6, 66

Gibbs energy

and extent of reaction, 435

and vaporization, 279

at 0 K, 431

minimum and equilibrium, 324

of a mixture of reactants, 324, 461

of formation of hydrogen ions, 398

of mixing in solutions, 368, 503

of mixing of an ideal gas mixture, 110, 251

of mixing of real gases, 129

of mixing, 112, 368, 376, 503

of reaction, 297, 300

––, 66

Gibbs-Duhem

application of the –– equation, 380, 536, 537

equation, 95

Gibbs-Helmholtz equations, 73

Global

entropy and spontaneity, 49, 189, 192, 280

entropy change during vaporization, 279

entropy, 42, 81, 82, 112, 190, 218, 219, 280, 312, 314

Graphite

equilibrium of –– and diamond, 461

Half-cell standard potential, 400

Heat

about ––, 21-22

engine, 32, 55

pump, 55, 57, 194

source, 4

system in contact with several –– sources, 42

system in contact with two –– sources, 32

transfer, 28, 190

Heat capacity

at constant pressure, 68

at constant volume, 67

molar ––, 52

of a crystal at constant volume, 425-429

of reaction, 300

statistical studies, 425

Helmholtz energy

at 0 K, 431

explicit expression for the ––, 95

of mixing, 110, 251

of reaction, 300

––, 66

Helmholtz function, 6, 66, 70

Henry's

constant, 388, 389

law, 387, 538, 539

Hess's law, 304

Heterogeneous

example of –– system, 352

system and equilibrium, 457, 460

system, 3

systems and the law of mass action, 332

Homogeneous

functions, 89-90

system, 3

Hydrogen

ion convention for aqueous solutions, 398

reduction of iron oxides by ––, 357

Ideal

enthalpy of an –– mixture of gases, 131

internal energy of an –– mixture of gases, 132

Mixture of gases, 130-132

mixture of ideal gases, 108

perfect and –– solutions, 361-374

species, 362

Ideal gas

definition, 77

equation of state of an ––, 11

law of mass action for ––es, 329

mixture of ––es, 108

partial pressure of an ––, 109

Identity

Euler's ––, 90, 93

Implications

of the first law, 23

of the second law, 38

of the third law, 431

Independent reactions

and the law of mass action, 341

number of ––, 335, 338, 456, 457

––, 334, 339, 353

Inert

effect of an –– gas on chemical equilibria, 347, 460

effect of an –– gas on vapor pressure, 144, 277

Infinitesimal process, 24

Integrating factor, 157

Intensive

properties of –– variables, 91

variable, 5, 92

Internal energy

differential expression for the ––, 45

explicit expression for the ––, 93

expression for the ––, 45

of an ideal mixture of gases, 132

of mixing, 111, 129

of reaction, 300

of van der Waals gas, 156

––, 22, 25, 69

Invariant system, 148

Inversion curve and temperature, 126, 257

Ionic strength, 397

Ions

chemical potential of –– in solutions, 396

law of mass action for ––, 398

Irreversible

(real) process, 11

adiabatic change of an ideal gas, 176

mixing, 218

mixture of ice and water, 277

process in an open system, 194, 195

process, 35, 165

vaporization, 279

Isenthalpic process, 125, 257

Isentropic process, 38, 52

Isobaric

and isothermal process, 86, 87

coefficient of thermal expansion of an ideal gas, 157

coefficient of thermal expansion, 6, 156

diagram for a perfect binary solution, 366, 505

diagram, 385

expansivity, 7

phase change, 147

process, 67, 173

Isochoric process, 66, 173, 188

Isolated system, 2

Isothermal

compressibility coefficient of an ideal gas, 157

compressibility coefficient, 6, 7, 156

compression of an ideal gas, 47

diagram, 384

expansion of an ideal gas, 47

phase change, 146

process of an ideal gas, 50

process, 188

representation of perfect solution liquid vapor equilibrium, 364

reversible process, 33, 165

Isotope

entropy of an –– mixture, 563

Joule

cycle, 63

energy unit, 22

the –– experiment, 22, 173, 189

Joule-Thomson

coefficient, 125

effect, 124, 256

Justification of the choice of the standard state pressure, 317

Kirchhoff's equation, 308-310, 438, 471

Lagrange multipliers, 136, 409, 421, 463, 562, 565, 593

Latent heat

and triple point, 276

effect of temperature on the ––, 145, 277

of fusion, 370, 508

of phase change, 141

of vaporization, 371

variation of the –– of vaporization with temperature, 279

Law

Dalton's ––, 110

displacement ––s of equilibria, 345, 462

Henry's ––, 387, 538, 539

Hess's ––, 304

of mass action for a heterogeneous system, 332, 334

of mass action for ideal gases, 329

of mass action for ions, 398

of mass action in a liquid phase, 393

of mass action in solutions, 393

of mass action, 328

Raoult's ––, 363, 364, 390

Law of thermodynamics

first ––, 21-25

second ––, 27-64

third ––, 430-432

Le Châtelier's principle, 345-350, 462

Lead storage batteries, 315

Legendre transform, 591

Lennard-Jones interaction, 117

Lever rule, 366, 367

Lewis-Randall rule, 132

Liquid

process at constant volume or pressure in a ––, 220

Loss

small ––es, 11

Magnetic field, 20

Mass action

law of ––, 328-334

Maximum

efficiency, 56

entropy, 43

of the extent of reaction, 325

usable work, 46-47

Maxwell

––'s relations, 73-75

Maxwell-Boltzmann statistics, 403

Measurement

of partial molar volumes, 100-103

Mechanical equilibrium, 3

Mechanics

statistical ––, 25, 401, 561

Metastable state, 43, 461

Microcanonical

ensemble, 408, 420

partition function, 410, 416, 566

Microstate

number of ––s, 408

Mixing

enthalpy of ––, 112, 129, 368

entropy of ––, 110, 251, 368, 503, 565

excess entropy of ––, 377

excess variable of –– (gases), 129

function of ––, 114

Gibbs energy of –– of real gases, 129

Gibbs energy of ––, 110, 251, 368, 503

Helmholtz energy of ––, 110, 251

internal energy of ––, 111, 129

irreversible –– of two ideal gases, 113

process, 27

properties of ideal solutions, 367

variable of –– for ideal gases, 110

variable of –– for real gases, 128

variable of ––, 114, 376, 536

volume of –– of real gases, 128

volume of ––, 101, 246, 368

Mixture

azeotropic ––, 383

binary ––, 503

binary, 361, 364, 366, 505, 510, 536

chemical potential of an ideal gas in a ––, 113

fugacity of a real gas in a ––, 128

ideal –– of gases, 130-132

ideal ––s of ideal gases, 108

law of mass action for a –– of gases, 328

standard state of a real gas in a ––, 128

water-acetic acid ––, 239

water-ethanol ––, 100, 237

water-glycerol ––, 238

––s of ideal gases, 108

––s of real gases, 127

Model

Debye –– for heat capacity, 427

Einstein –– for heat capacity, 425

Molality

definition, 391

scale, 391

Molar

heat capacity, 52

partial –– entropy, 377

partial –– quantities, 89-103, 237, 239

partial –– volume, 100-103

properties, 98

quantities, 96, 98

volume of a mixture, 238, 239

Molarity, 393

Mole fraction

in an ideal gas mixture, 112

intensive property, 93

of a species in a solution, 362

Molecular

interactions in real gases, 116

partition function, 410

Moment of inertia, 418

Monobaric

monothermal process, 84

Monothermal

change of a van der Waals gas, 174

irreversible process, 165, 217

monobaric process, 84

process, 31, 173

Multiple step process, 174

Multipliers

Lagrange ––, 136, 409, 421, 463, 562, 565, 593

Natural variables, 68, 592

Number

of chemical species in a system, 138, 342

of components of a system, 342

of independent  species in a system, 342

of independent reactions, 335, 338, 456, 457

of phases in a system, 138

Open system

and irreversible process, 194, 195

change, 176

––, 2, 68, 136

Osmotic pressure, 372, 509, 541

Otto cycle, 58

Oxidation of ethanol, 307

Partial

molar entropy, 377

molar quantities of pure substances, 98

molar quantities, 89, 96-103, 237, 238, 239

molar volume, 100-103, 237, 238, 239

pressure of an ideal gas, 109

Particle

energy levels for a –– in a box, 413

in a box, 412-415, 561, 564, 566

Particles

distinguishable and independent ––, 424

distinguishable ––, 403

independent and indistinguishable ––, 425

indistinguishable ––, 403

Partition

canonical –– function, 422, 561

coefficient, 390

function for a crystalline solid, 425

function for a particle in a box, 413, 566

function, 410

Perfect

and ideal solutions, 361-374

solution, 364

Phase

activity of a pure condensed ––, 332

chemical potential of a condensed ––, 331

condensed ––, 320

definition, 133

diagram, 146

law of mass action in the liquid ––, 393

number of ––s in a system, 138

rule and electrolytes, 396

rule and examples, 342

rule, 5, 138-139, 341-343

Phase change

and thermodynamic functions, 142

delays, 150

isobaric ––, 147

isothermal ––, 146

Physical meaning of

free energy, 81-84

free enthalpy, 84-86

Gibbs function, 84-86

Helmholtz function, 81-84

Point

critical ––, 148

triple ––, 35, 147

Potential

half-cell standard ––, 400

reduction ––, 400

Pressure

effect of –– on chemical equilibria, 346, 462

effect of –– on the activity coefficient, 377

intensive variable, 92

osmotic ––, 372, 509, 541

standard state ––, 106, 301

Principle

Le Châtelier's ––, 345-350, 462

Probability and entropy, 402

Probable

most –– distribution, 421

Process

adiabatic ––, 23

at constant external pressure, 16

at constant pressure, 67

at constant volume, 66

chemical ––, 295

cyclic ––, 8, 24

irreversible ––, 11, 35

isenthalpic ––, 125, 257

isobaric ––, 67, 166, 173

isochoric ––, 66, 166, 173

isothermal and isobaric ––, 86, 87

isothermal ––, 86, 166, 188

mixing ––, 27

monothermal ––, 31

multiple step ––, 174

reverse –– and work, 18

reversible adiabatic –– of an ideal gas, 51, 193

reversible ––, 11, 35

spontaneous ––, 38, 43, 113

Properties

of a state function, 10

of extensive variables, 90

of homogeneous functions, 89-90

of intensive variables, 91

Pure

chemical potential of a –– real gas, 118

real gas, 116

Quantum number

rotation ––, 418

vibration ––, 417

––s, 415

Rank of a matrix, 336, 338, 340, 353, 456, 457

Raoult's

constant, 363, 389

law, 363, 364, 390

Rare gas

standard molar entropy of ––es, 561

Reaction

endothermic ––, 307

exothermic ––, 307

extent of —, 296

forward ––, 328

independent ––s, 334-341

reverse ––, 328

spontaneous chemical ––, 323

Real

mixtures of –– gases, 127

solution, 375, 535

volume of mixing of –– gases, 128

Real gas

fugacity of a –– in a mixture, 128

partial molar  volume of a ––, 128

pure ––, 116

Reduced variables, 122

Reduction

of iron oxides, 351-359

potential, 400

Reference state for entropy, 430

Refrigerator, 55, 56

Relation

between activity coefficients in binary systems, 380, 536, 537

between Cp and CV, 78-79

between partial molar quantities, 97, 98

Reverse

Carnot cycle, 34

process and the sign of work, 18

reaction, 328

Reversible

adiabatic process of an ideal gas, 51, 193

approximation of a  –– process, 174

isothermal expansion or compression of an ideal gas, 47

process, 11, 35, 165, 174

Rotational partition function, 418

Rule

lever ––, 366, 367

Lewis-Randall ––, 132

phase –– and electrolytes, 396

phase ––, 5, 138-139

Schwarz theorem, 10, 73, 74, 80

Second law of thermodynamics

First form of the ––, 31

molecular scale, 27

––, 43

Selection of the standard state pressure, 106

SI units, 165

Sign convention for energy exchange, 13

Simultaneous

independent –– reactions, 334

reactions, 298, 456

Solid

as one crystalline form, 146

liquid equilibrium, 276

with several crystalline forms, 150

Solidification, 141

Solubility

in a binary mixture, 510

in an perfect binary mixture, 510

Solute

effect of a –– on the boiling temperature, 371, 509

freezing point depression by a ––, 369

––, 369, 386

Solution

ideal ––, 362

isothermal diagram, 364

non ideal ––, 375, 535

perfect and ideal ––s, 361-374

perfect ––, 364

real ––, 375, 535

Solvent

depression of the freezing point of a –– by a solute, 369, 507

elevation of the boiling temperature of a –– by a solute, 371, 509

––, 369, 386

Source voltage, 19

Species in excess

effect of –– on chemical equilibria, 348, 463

Spontaneous

evolution of a system, 86, 217

freezing of water, 217

process at constant Gibbs energy, 279

process, 43, 113

reaction, 298, 323

transfer of species between phases, 137

vaporization of ethanol, 279

Standard

chemical potential in liquids, 379

chemical potential using convention I, 379

chemical potential using convention II, 387

chemical potential, 106

electrochemical cell potential, 317, 439

entropy of the electron, 400

entropy, 303, 565

equilibrium constant, 329, 539

Gibbs energy of formation, 303

heat capacity at constant pressure, 303

Helmholtz energy of formation, 303

molar heat capacity at constant pressure, 303

quantity, 106

state on the molality scale, 392, 539

state pressure, 106

state, 301

thermodynamic functions of oxygen, 567

variable of combustion, 321

variable of reaction, 300, 435, 436, 437, 438

Standard state

and convention I, 536

and convention II, 539

choice of the –– for a condensed phase, 320

effect of the choice of the ––  on the thermodynamic tables, 317

effect of the choice of the –– of a real gas, 320

effect of the choice of the –– of an ideal gas, 318

of a real gas in a mixture, 128

of a real gas, 118, 320

of an ideal gas, 318

pressure, 106, 301

temperature, 301

State

corresponding ––s of real gases, 123

effect of the choice of the standard –– for an ideal gas, 318

equation of ––, 11

function, 4, 6, 10, 38

metastable ––, 43, 461

standard –– and convention I for the activity coefficient, 378, 536

standard –– and convention II for the activity coefficient, 386, 539

standard ––, 301

variable of ––, 4, 6

Statistical

mechanics of a gas mixture, 563

mechanics, 25, 401, 561

models, 403

Statistical thermodynamics

agreement of the third law with ––, 432

Statistics

Bose-Einstein ––, 403, 404

Fermi-Dirac ––, 403, 405, 565

Maxwell-Boltzmann ––, 403

Stirling

cycle, 60

engine, 62

––'s approximation, 407

Stoichiometric coefficients, 295, 456, 457, 463

Sublimation, 141

Symmetry factor, 419

System

at equilibrium, 3

binary ––, 380, 536, 537

closed adiabatic ––, 254

closed ––, 2, 66-68, 323

dilute ––, 406

divariant and trivariant ––, 342

heterogeneous –– and the law of mass action, 332

heterogeneous ––, 3

homogeneous ––, 3

in contact with one thermal reservoir, 31, 41

in contact with several thermal reservoirs, 42

in contact with two heat sources, 32, 219

interaction with environment, 2

invariant ––, 148

irreversible process in a ––, 38, 254

isolated ––, 2

open ––, 2, 68-73, 136

simple –– in statistical thermodynamics, 412

thermodynamic ––, 1

univariant ––, 139

with a gas phase and condensed phases, 320

without chemical reaction, 133-151

Temperature

critical ––, 121

Debye ––, 428

effect of –– on chemical equilibria, 345, 455, 461

effect of –– on the activity coefficient, 377

effect of –– on the equilibrium constant, 343, 456

effect of –– on the extent of reaction, 460, 462

Einstein ––, 426

in statistical thermodynamics, 411, 562

in the canonical ensemble, 423

inversion ––, 126, 257

standard state ––, 301

thermodynamic ––, 32-34

Thermal

equilibrium and entropy, 43

equilibrium, 3

expansion coefficient, 6, 7

machines, 55, 219

Thermal reservoir

definition of a ––, 4

entropy change of a ––, 48, 49, 112, 113, 314

system in contact with one ––, 31, 41

system in contact with several ––s, 42

Thermodynamic

equilibrium constant, 329

functions in the canonical ensemble, 422, 561, 566

system, 1

temperature, 32-34

Thermodynamic tables

effect of the choice of the standard state on values in the ––, 317

Third Law

implications of the ––, 431

of thermodynamics, 430

Transfer

heat ––, 28

Transform

Legendre ––, 591

Translational

partition function, 416

Triple point

and latent heat, 276

––, 147

Units

SI ––, 165

Univariant

system, 139

Usable

maximum –– work, 46

Van der Waals

adiabatic change of a –– gas, 174

coefficient, 121

complex, 118

equation of state, 120, 253

forces, 116

Internal energy of a –– gas, 156

Van't Hoff's

equation, 344

Vapor

phase composition of an ideal binary solution, 505

Vapor pressure

effect of an inert gas on ––, 144, 277

effect of temperature on ––, 145, 277

of an ideal solution, 364

temperature dependence of ––, 276

––, 141, 363

Vaporization

curve, 364, 366, 503, 505

in the presence of a gas, 277

latent heat of ––, 371

––, 141

Variable

auxiliary state ––, 4, 6

auxiliary ––, 65, 217

excess –– of mixing, 376, 536

extensive ––, 5, 65

intensive ––, 5, 65

of mixing for ideal gases, 110

of mixing for real gases, 128

of mixing, 376, 536

of reaction, 297, 300

of state, 5, 6

reduced ––s, 122

standard –– of formation, 302

standard –– of reaction, 300, 435, 436, 437, 438

Variables

characteristic ––, 592

natural ––, 68, 592

Variance

example of the use of ––, 353, 355, 356

of a system, 138

––, 342

Variation

of entropy at 0 K with volume and temperature, 431

of Gibbs function with temperature, 73

of heat capacities with pressure, 80

of heat capacities with volume, 80

of Helmholtz function with temperature, 73

Vibrational

characteristic –– temperature, 417

partition function, 416

Virial

coefficients, 119, 252

equation, 119, 252

Volume

effect of –– on chemical equilibria, 347

molar –– of a pure liquid, 363

of mixing, 101, 368

of reaction, 300

partial molar –– of a real gas, 128

partial molar –– of an ideal gas, 110

partial –– of an ideal gas, 110

work due to –– change, 47, 188, 323

Water-acetic acid mixture, 239

Water-ethanol mixture, 100, 237

Water-glycerol mixture, 238

Wave function for a particle in a box, 412

Work

and irreversible adiabatic process of an ideal gas, 191

any form of ––, 312

due to volume change, 47, 188, 323

electrical ––, 18

in an irreversible process, 217

maximum usable ––, 46-47

mechanical ––, 14

notions, 13-20

other than volume ––, 313

sign convention for ––, 13
various expressions for ––, 20