INDEX A boldface page number refers to a definition. A page number followed by b is for a biographical sketch, one followed by n is for a footnote, and one followed by p is for a problem. Absolute zero, unattainability of, 161 Acid dissociation constant, 409 Activity, 269, 408 of an electrolyte solute, 292 of a gas, 185, 272 of an ion, 288 of a mixture constituent, 272 of a pure liquid or solid, 272 relative, 269 of a solute, 272 of a solvent, 272 of a symmetrical electrolyte, 290 Activity coefficient, 257, 258 approach to unity, 260 of a gas, 185 from the Gibbs Duhem equation, 264 265 of an ion, 287 from the Debye Hückel theory, 294 mean ionic from the Debye Hückel theory, 296 of an electrolyte solute, 292 from the Nernst equation, 463 from the osmotic coefficient, 299 from solubility measurement, 391 of a symmetrical electrolyte, 289 from the osmotic coefficient, 265 267 of a solute in dilute solution, 260 from gas fugacity, 261 264 of a solvent, 370n from gas fugacity, 261 264 stoichiometric, 293 Activity quotient, 350 Additivity rule, 229, 233, 237, 242, 289, 291, 293, 303, 307, 328, 346 Adiabat, 77 Adiabatic boundary, 28 calorimeter, 168 170, 333 demagnetization, 158, 160 flame temperature, 341 process, 51, 57, 95, 128 Advancement, 314 Affinity of reaction, 342n Amount, 21,37 Amount of substance, 21, 37, 470 Ampere, 470 Anisotropic phase, 30, 74 Antoine equation, 220p Athermal process, 304 Avogadro constant, 21, 471 Azeotrope, 405, 435 minimum-boiling, 435 vapor-pressure curve, 436 Azeotropic behavior, 433 Azeotropy, 435 Bar, 39 Barometric formula, 197, 276 Barotropic effect, 33 Base units, 19, 470 Binary mixture, 223 in equilibrium with a pure phase, 374 Binary solution, 224 Bivariant system, 199, 419 Body, 28 520
INDEX 521 Boiling point, 203 curve, 204, 433 elevation in a solution, 375, 380 Bomb calorimeter, 320, 333, 335 340 Bomb calorimetry, 361p Boundary, 27 adiabatic, 28 diathermal, 28 Boyle temperature, 35 Brewer, Leo, 271 Bridgman, Percy, 179, 495 Bubble-point curve, 433 Cailletet and Matthias, law of, 205 Caloric theory, 62 Calorie, 86n Calorimeter, 168 adiabatic, 168 170, 333 bomb, 320, 333, 335 340 Bunsen ice, 341 combustion, 333 constant-pressure, 170, 213 constant-volume, 169 continuous-flow, 173 flame, 341 heat-flow, 341 isoperibol, 171, 333, 334, 341 isothermal-jacket, 171 173, 333, 334, 341 phase-change, 340 reaction, 333 335 Calorimetry bomb, 335, 361p drop, 190p to evaluate an equilibrium constant, 354 to measure heat capacities, 168 to measure transition enthalpies, 213 reaction, 322, 333 341, 410 Candela, 470 Carathéodory s principle of adiabatic inaccessibility, 118 Carnot cycle, 105, 105 108 engine, 105, 105 108 heat pump, 108 Carnot, Sadi, 106b Cell diagram, 450 electrochemical, 449 galvanic, 449 reaction, 451 with transference, 451 without liquid junction, 451 without transference, 451 Cell potential, 89, 453 equilibrium, 89 Celsius scale, 41 Center of mass, 500 Center-of-mass frame, 54, 58, 499 502 Centigrade scale, 41 Centrifugal force, 503 Centrifuge, 274 cell, 276 279 Charge electric, 452 number, 294 Chemical amount, 21n Chemical equation, 312 Chemical potential, 136, 142 of an electrolyte solute, 292 of electrons, 456 as a function of T and p, 214 of a liquid or solid, 185 of a pure substance, 181 of a solvent from the freezing point, 370 372 from the osmotic coefficient, 369 from osmotic pressure, 372 374 of a species in a mixture, 235 standard, 257, 269 of a gas, 182 of a gas constituent, 240 of an ion, 287 of a pure substance, 182 of a symmetrical electrolyte, 289 total, 196 Chemical process, 302 subscript for, 477 Chemical work, 136 Circuit electrical, 86 88 heater, 168, 169, 171, 172 ignition, 336, 338 Clapeyron equation, 216 Clapeyron, Émile, 217b Clausius inequality, 118 statement of the second law, 103 Clausius, Rudolf, 102, 103, 109b, 127, 131 Clausius Clapeyron equation, 218, 369 CODATA, 504 Coefficient of thermal expansion, 163 Coexistence curve, 200, 213 liquid gas, 33
INDEX 522 Colligative property, 375 to estimate solute molar mass, 376 Common ion effect, 391, 444 Component, 421 Components, number of, 47, 228n Composition variable, 222, 225 relations at infinite dilution, 225 Compressibility factor, 35 Compression, 51 Compression factor, 35 Concentration, 29, 223 standard, 253 Condensation curve, 433 Conditions of validity, 23n Congruent melting, 429 Conjugate pair, 137 phases in a binary system, 430 in a ternary system, 443 variables, 59, 137 Consolute point, 430 Constants, physical, values of, 471 Contact force, 493 potential, 455, 456 Continuity of states, 33 Convergence temperature, 172 Conversion factor, 23 Coriolis force, 276n, 503 Coulomb s law, 489 Critical curve, 439 opalescence, 205 point of partially-miscible liquids, 430 of a pure substance, 33, 205 pressure, 205 temperature, 205 Cryogenics, 156 161 Cryoscopic constant, 378 Cubic expansion coefficient, 163, 210, 218 of an ideal gas, 188p negative values of, 163n Curie s law of magnetization, 160 Current, electric, 86, 87, 168, 169, 449, 470 Cyclic process, 52 Dalton s law, 239 Debye crystal theory, 152 Debye, Peter, 158, 294, 295b, 297, 298 Debye Hückel equation for a mean ionic activity coefficient, 296, 297, 464 for a single-ion activity coefficient, 294 limiting law, 296, 330, 332, 390 theory, 294 299 Deformation, 30 elastic, 36 plastic, 36 work, 69 74 Degree of dissociation, 410 Degrees of freedom, 199, 419 Deliquescence, 439 Density, 29 measurement of, 38 Dependent variable, 46 Derivative, 479 formulas, 479 Dew-point curve, 433 Dialysis, equilibrium, 395 Diathermal boundary, 28 Dieterici equation, 26p Differential, 24, 481 exact, 52, 481 inexact, 52 total, 134, 481 of the internal energy, 135 137 Dilution process, 324 Dimensional analysis, 24 25 Disorder, 129 Dissipation of energy, 65, 66, 80, 83, 90 92, 94, 95, 113, 123, 129, 170 Dissipative work, 83, 89, 91, 94, 135 Dissociation pressure of a hydrate, 437 Distribution coefficient, 394 Donnan membrane equilibrium, 396, 396 399 potential, 396 Duhem Margules equation, 404 Ebullioscopic constant, 380 Efficiency of a Carnot engine, 111 113 of a heat engine, 110 Efflorescence, 438 Einstein energy relation, 54, 182n Elastic deformation, 36 Electric charge, 452 current, 86, 87, 168, 169, 449, 470 potential, 45, 286, 297, 298, 452
INDEX 523 inner, 286, 452 potential difference, 87, 88, 396, 453 power, 173 resistance, 44, 88, 169 Electrical circuit, 86 88 conductor of a galvanic cell, 449 force, 489 heating, 88 89, 168, 169, 173 neutrality, 235, 422 resistor, 60, 88, 90 work, 61, 86 91, 95, 168 170, 173, 213, 338, 455 Electrochemical cell, 449 potential, 287n Electrode, 450 hydrogen, 450 standard, 465 potential, standard, 465 reaction, 451 Electrolyte solution, 285 300 symmetrical, 288 290 Electromotive force, 453n Electron chemical potential, 456 conductor of a galvanic cell, 449 number, 451 Emf, 453n Endothermic reaction, 318 Energy, 53, 488 495 dissipation of, 65, 66, 80, 83, 90 92, 94, 95, 113, 123, 129, 170 Gibbs, 137 Helmholtz, 137 internal, 53, 53 54 kinetic, 488 potential, 490 of the system, 52 54 thermal, 62, 495 Energy equivalent, 169, 170, 172, 173, 333, 334, 337, 338 Enthalpy, 137 change at constant pressure, 176 of combustion, standard molar, 335, 340 of dilution integral, 326 molar differential, 326 molar integral, 327 of formation of a solute, molar, 327 of formation, standard molar, 319 of an ion, 322 of a solute, 320 of mixing to form an ideal mixture, 304 molar reaction, 314 molar, effect of temperature on, 323 324 partial molar, 248 in an ideal gas mixture, 241 relative, of a solute, 329 relative, of the solvent, 328 of a solute in an ideal-dilute solution, 256 reaction standard molar, 319, 320, 368, 369, 410 standard molar of a cell reaction, 461 relative apparent, of a solute, 330 of solution at infinite dilution, 325 integral, 325 molar differential, 324, 325, 385 molar integral, 325, 328, 357 of vaporization molar, 211 standard molar, 213 Entropy, 102, 119, 129 change at constant pressure, 176 at constant volume, 175 an extensive property, 122 as a measure of disorder, 129 of mixing to form an ideal mixture, 304, 306 negative value, 304 molar, 151 156 from calorimetry, 152 of a nonequilibrium state, 122 partial molar, 248 of a solute in an ideal-dilute solution, 256 reaction standard molar, 410, 412p standard molar of a cell reaction, 462 residual, 155 156 scale conventional, 154 practical, 154 standard molar, 155, 410 of a gas, 186, 241 third-law, 151 zero of, 149 151 Equation
INDEX 524 chemical, 312 reaction, 312 stoichiometric, 313 Equation of state, 46, 47 of a fluid, 33 of a gas at low pressure, 35, 244, 281p, 362p of an ideal gas, 33 thermodynamic, 166 virial, 34 Equilibrium dialysis, 395 gas gas, 440 liquid gas, 399 408 liquid liquid, 391 394 mechanical, 48 phase transition, 69, 344 position, effect of T and p on, 356 358 reaction, 48, 343, 408 410 solid liquid, 383 391 thermal, 48 transfer, 48 Equilibrium cell potential, 89, 453 Equilibrium conditions for a gas mixture in a gravitational field, 274 276 in a gravitational field, 195 in a multiphase multicomponent system, 235 237 in a multiphase one-component system, 193 194 for reaction, 343 349 for a solution in a centrifuge cell, 276 279 Equilibrium constant mixed, 409 on a pressure basis, 352 thermodynamic, 351 of a cell reaction, 461 temperature dependence, 368 Equilibrium state, 48, 48 50 Euler reciprocity relation, 482 Eutectic composition, 427 halt, 428 point, 426, 429 temperature, 427, 428 Eutonic composition, 444 point, 443 Exact differential, 52, 481 Excess function, 146 quantity, 305 work, 91 Exergonic process, 302n Exothermic reaction, 318 Expansion, 51 free, 79 reversible, of an ideal gas, 126 work, 71, 71 79, 95 reversible, 77 Expansivity coefficient, 163 Extensive property, 28 Extent of reaction, 314 External field, 28, 49, 58, 195 Faraday constant, 286, 452, 471 Field external, 28, 49, 58, 195 gravitational, 28, 36, 49, 54, 195, 274 magnetic, 160 First law of thermodynamics, 56, 135 Fluid, 31,32 33 supercritical, 32, 33, 205, 210, 211 Flux density, magnetic, 158 Force, 486 495 apparent, 276n, 496 centrifugal, 503 contact, 493 Coriolis, 276n, 503 effective, 496 electrical, 489 fictitious, 276n, 496, 498 frictional, 69 gravitational, 37, 197, 489, 503 Formation reaction, 319 Frame center-of-mass, 54, 58, 499 502 lab, 53, 58, 59, 79, 274, 276, 487, 490 493, 495, 496, 499, 500 local, 53, 57, 58, 69, 79, 276, 278, 495, 497, 498 nonrotating, 499 502 rotating, 276, 496, 502 503 reference, 28, 53 earth-fixed, 503 inertial, 53, 486, 487, 490 Free expansion, 79, 128 Freezing point, 203 curve, 383 for a binary solid liquid system, 426 of an ideal binary mixture, 384 for solid compound formation, 388
INDEX 525 depression in a solution, 375 378 to evaluate solvent chemical potential, 370 372 of an ideal binary mixture, 383 384 Friction internal, 91 94 sliding, 495 Frictional force, 69 Fugacity effect of liquid composition on, 400 404 effect of liquid pressure on, 399 of a gas, 183 of a gas mixture constituent, 242 Fugacity coefficient of a gas, 184 of a gas mixture constituent, 243, 245 Fundamental equation, Gibbs, 235 Fundamental equations, Gibbs, 142, 286 Galvani potential, 286, 452 Galvanic cell, 89, 449 in an equilibrium state, 49 Gas, 32 ideal, 74 mixture, 239, 241 perfect, 74n solubility, 405 407 thermometry, 42 44 Gas constant, 471 Gas gas immiscibility, 440 Giauque, William, 158, 159b Gibbs equations, 139, 141 fundamental equation, 235 fundamental equations, 142, 286 phase rule for a multicomponent system, 418 425 for a pure substance, 199 Gibbs energy, 137 of formation, standard molar, 354 of an ion, 354 of mixing, 303 to form an ideal mixture, 304 molar, 303 molar, 141, 181 molar reaction, 342 of a cell reaction, 457 461 reaction, standard molar, 350, 410 total differential of, for a mixture, 235 Gibbs, Josiah Willard, 142 Gibbs, Willard, 138b Gibbs Duhem equation, 230, 232, 233, 254, 264 265, 267, 300, 306, 388, 401 Gibbs Helmholtz equation, 367 Gravitational field, 28, 36, 49, 54, 195, 274 force, 37, 197, 489, 503 work, 79 81, 95 Gravitochemical potential, 196 Green Book, see IUPAC Green Book Hückel, Erich, 294, 297, 298 Heat, 56, 89, 494 flow in an isolated system, 127 128 reservoir, 50, 61, 103, 104, 107, 113, 115, 117, 118, 120, 121, 124, 125, 128, 130 technical meaning of, 61 transfer, 67 69 Heat capacity, 62, 142 143 at constant pressure, 62, 143 molar, 143 partial molar, 248 at constant volume, 62, 142 of an ideal gas, 75 molar, 143 at constant volume and constant pressure, relation between, 167 measurement of, by calorimetry, 168 molar reaction, 322 Heat engine, 103, 105 Heater circuit, 168, 169, 171, 172 Heating at constant volume or pressure, 174 176 curve, of a calorimeter, 169, 171, 173 electrical, 88 89, 168, 169, 173 reversible, 126 Helium, 202n Helmholtz energy, 137 Henry s law, 249 not obeyed by electrolyte solute, 285 Henry s law constant, 249 effect of pressure on, 407 effect of temperature on, 407 evaluation of, 252 Henry s law constants, relations between different, 252 Henry, William, 250b Hess s law, 319, 320, 335 Hess, Germain, 321b Homogeneous phase, 30 Hydrogen electrode, 450
INDEX 526 standard, 465 Ice point, 41 Ice, high pressure forms, 203 Ideal gas, 74 equation, 23, 33, 74 internal pressure, 166 mixture, 239, 241 in a gravitational field, 274 276 and Raoult s law, 247 Ideal mixture, 248, 258 mixing process, 303 and Raoult s law, 247 Ideal solubility of a gas, 406 of a solid, 386 Ideal-dilute solution, 252 partial molar quantities in, 255 256 solvent behavior in, 254 255, 401 Ideal-gas temperature, 40, 115 Ignition circuit, 336, 338 Impossible process, 66 Independent variables, 46, 192 of an equilibrium state, 119 number of, 198, 420 Indicator diagram, 77 Inertial reference frame, 53, 487, 490 Inexact differential, 52 Inner electric potential, 452 Integral, 480 formulas, 480 line, 72, 480 Integral enthalpy of dilution, 326 Integral enthalpy of solution, 325 Integrand, 480 Integrating factor, 122 Intensive property, 29 Interface surface, 30 Internal friction, 91 94 pressure, 165, 165 166, 168 of an ideal gas, 166 resistance, 455 Internal energy, 53,53 54 of an ideal gas, 74 of mixing to form an ideal mixture, 304 partial molar, 248 International System of Units, see SI International temperature scale, 41 Invariant system, 199, 419 Ionic conductor of a galvanic cell, 449 Ionic strength, 294, 296, 298 effect on reaction equilibrium, 409 Irreversible process, 66, 101, 123 125, 127 129 Isobaric process, 51 Isochoric process, 51 Isolated system, 28,48 spontaneous changes in, 127 Isoperibol calorimeter, 171, 333, 334, 341 Isopiestic process, 51 solution, 268 vapor pressure technique, 268 Isopleth, 427 Isoteniscope, 203 Isotherm, 77, 209 Isothermal bomb process, 335, 337 338, 340 compressibility, 163, 210, 218 of an ideal gas, 188p of a liquid or solid, 180 magnetization, 160 pressure changes, 180 181 of a condensed phase, 180 of an ideal gas, 180 process, 51 Isotropic phase, 30 IUPAC, 19 IUPAC Green Book, 19, 137, 181, 211, 259n, 324, 351, 453n, 470 Joule coefficient, 188p experiment, 188p paddle wheel, 84 86, 103 Joule, James Prescott, 58, 62, 84, 85b, 86, 99p, 188p Joule Kelvin coefficient, 157 experiment, 156 Joule Thomson coefficient, 157, 179 experiment, 156 Kelvin (unit), 40, 470 Kelvin, Baron of Largs, 102, 104, 113, 114b Kelvin Planck statement of the second law, 104, 118 Kilogram, 470 Kinetic energy, 488 Kirchhoff equation, 323, 338 Konowaloff s rule, 405
INDEX 527 Lab frame, 53, 58, 59, 79, 274, 276, 487, 490 493, 495, 496, 499, 500 Laplace equation, 198, 280p Law of Cailletet and Matthias, 205 of rectilinear diameters, 205 scientific, 56 Le Châtelier s principle, 357, 358 Legendre transform, 137, 141, 160, 484, 484 485 Lever rule, 208, 426 for a binary phase diagram, 427 general form, 208 for one substance in two phases, 206 for partially-miscible liquids, 431 for a ternary system, 442 Lewis and Randall rule, 281p Lewis, Gilbert Newton, 105, 149, 270b, 294 Line integral, 72, 480 Liquid, 32 Liquid junction, 449, 451, 457 potential, 451, 457 Liquidus curve, 429 for a binary system, 426 for a binary liquid gas system, 432 435 for a binary solid liquid system, 426 at high pressure, 439 Liter, 37 Local frame, 53, 57, 58, 69, 79, 276, 278, 495, 497, 498 nonrotating, 499 502 rotating, 496 Magnetic enthalpy, 160 field, 160 flux density, 158 Magnetization, isothermal, 160 Mass, 470 meaurement of, 36 37 Mass fraction, 223 Maxwell relations, 140 Maxwell, James Clerk, 40 McMillan Mayer theory, 261n Mean ionic activity coefficient, see Activity coefficient, mean ionic Mean molar volume, 230 Melting point, 203 normal, 42 Membrane equilibrium Donnan, 396, 396 399 osmotic, 395 Membrane, semipermeable, 49, 372 Metastable state, 50 Meter, 470 Method of intercepts, 230, 231 Metre, 470 Microstate, 130 Milliter, 37 Minimal work principle, 91 Miscibility gap in a binary system, 312, 430 in a ternary system, 443 Mixing process, 302 Mixture binary, 223 of fixed composition, 225 gas, in a gravitational field, 274 276 ideal, 258 and chemical potential, 248 and Raoult s law, 247 simple, 308 Molal boiling-point elevation constant, 380 Molal freezing-point depression constant, 378 Molality, 223 standard, 253 Molar differential reaction quantity, 316 excess quantity, 305 integral reaction quantity, 316 mass, 37 from a colligative property, 376 from sedimentation equilibrium, 279 quantity, 29, 175 reaction quantity, 316 standard, 318 Mole, 21,37,470 Mole fraction, 222 standard, 254 Mole ratio, 224 Molecular mass, relative, 37 Molecular weight, 37 Natural variables, 137, 140, 141 Nernst distribution law, 394 equation, 462 heat theorem, 149 Nernst, Walther, 149n, 150b Neutrality, electrical, 235, 422 Newton s law of cooling, 171 Newton s law of universal gravitation, 489 Newton s second law of motion, 70, 197, 487
INDEX 528 Newton s third law of action and reaction, 488, 489, 498 Nonexpansion work, 135, 145 Normal boiling point, 204 melting point, 42, 204 Optical pyrometer, 45 Osmosis, 373 Osmotic coefficient, 265, 381 evaluation, 269 of a mean ionic activity coefficient, 299 Osmotic membrane equilibrium, 395 Osmotic pressure, 49, 373, 375, 381, 395 to evaluate solvent chemical potential, 372 374 van t Hoff s equation for, 381 Paddle wheel, 60 Joule, 84 86, 103 Partial specific quantity, 234 specific volume, 234 Partial derivative, 479 expressions at constant T, p, and V, 176 179 Partial molar enthalpy, 248 in an ideal gas mixture, 241 relative, of a solute, 329 relative, of the solvent, 328 of a solute in an ideal-dilute solution, 256 entropy, 248 in an ideal gas mixture, 241 of a solute in an ideal-dilute solution, 256 Gibbs energy, 142 heat capacity at constant pressure, 248 internal energy, 248 quantity, 225 of a gas mixture constituent, 244 in general, 233 general relations, 237 238 in an ideal mixture, 248 in an ideal-dilute solution, 255 256 volume, 226 228, 248 in an ideal gas mixture, 241 interpretation, 227 negative value of, 227 Partial pressure, 239 in an ideal gas mixture, 239 Partition coefficient, 394 Pascal (unit), 39 Path, 50 Path function, 52, 61 Peritectic point, 429 Perpetual motion of the second kind, 103n Phase, 30 anisotropic, 30, 74 boundary, 200 coexistence, 31 homogeneous, 30 isotropic, 30 rule, see Gibbs phase rule separation of a liquid mixture, 310 312, 391, 430 transition, 31 equilibrium, 32, 69, 151, 344 Phase diagram for a binary liquid gas system, 432 for a binary liquid liquid system, 430 for a binary solid gas system, 436 for a binary solid liquid system, 426 for a binary system, 425 at high pressure, 439 of a pure substance, 199 for a ternary system, 441 Physical constants, values of, 471 Physical quantities, symbols for, 472 475 Physical state, 30 symbols for, 476 Pitzer, Kenneth, 271 Plait point, 443 Planck, Max, 102, 104, 116b Plasma, 32 Plastic deformation, 36 Plimsoll mark, 181 Potential chemical, 136 electric, 452 energy, 490 function, 489 standard cell, 461, 462 evaluation of, 464 thermodynamic, 134 Potentiometer to measure equilibrium cell potential, 454 Poynting factor, 399 Prefixes, 21 Pressure changes, isothermal, 180 181 of a condensed phase, 180
INDEX 529 of an ideal gas, 180 dissociation, of a hydrate, 437 internal, 165, 165 166, 168 in a liquid droplet, 197 measurement of, 38 40 negative, 166n partial, 239 standard, 39, 181, 274, 359p, 467p sublimation, 203 vapor, see Vapor pressure Pressure factor, 271, 272 274 of an electrolyte solute, 292 of an ion, 288 of a symmetrical electrolyte, 290 Pressure volume diagram, 77 Process, 50 adiabatic, 51, 57, 95, 128 chemical, 302 subscript for, 477 compression, 51 cyclic, 52 dilution, 324 expansion, 51 impossible, 66, 101, 102 104 irreversible, 66, 101, 123 125, 127 129 isenthalpic, 157 isobaric, 51 isochoric, 51 isopiestic, 51 isothermal, 51 mechanical, 129 mixing, 302 purely mechanical, 66 quasistatic, 64 reverse of a, 64 reversible, 62, 62 66, 94 95, 101, 102, 129 solution, 324 spontaneous, 62, 64 66, 101, 129, 342 throttling, 156 Product, 313 Proper quotient, 350 Property extensive, 28 intensive, 29 molar, 175 Quantity molar, 29 specific, 29 Quantity calculus, 22 Quartz crystal thermometer, 45 Quasicrystalline lattice model, 308 Quasistatic process, 64 Randall, Merle, 105, 149, 294 Raoult s law deviations from, 402 404, 433 for fugacity, 246, 247 in a binary liquid mixture, 402 in an ideal-dilute solution, 255 for partial pressure, 246, 246 in a binary system, 432 Raoult, François, 245 Raoult, François-Marie, 379b Reactant, 313 Reaction between pure phases, 344 cell, 451 endothermic, 318 equation, 312 equilibrium, 408 410 exothermic, 318 in a gas phase, 352 353 in an ideal gas mixture, 346 349 in a mixture, 344 346 quotient, 350, 462 in solution, 353 Reaction quantity molar, 316 molar differential, 316 molar integral, 316 Reciprocity relation, 140, 147p, 482 Rectilinear diameters, law of, 205 Redlich Kister series, 310 Redlich Kwong equation, 26p, 34 Reduction to standard states, 335 Reference frame, 28, 53 earth-fixed, 503 inertial, 486 Reference state, 257 of an element, 319 of an ion, 287 of a mixture constituent, 259 of a solute, 252 253, 259 of a solvent, 259 Regular solution, 309 Relative activity, 269 Relative apparent molar enthalpy of a solute, 330 Relative molecular mass, 37 Relative partial molar enthalpy of a solute, 329 of the solvent, 328
INDEX 530 Residual entropy, 155 156 Resistance electric, 44, 88, 169 internal, 455 Resistor, electrical, 60, 88, 90 Retrograde condensation, 440 vaporization, 440 Reverse of a process, 64 Reversible adiabatic expansion of an ideal gas, 75 adiabatic surface, 119 expansion and compression, 71 expansion of an ideal gas, 126 expansion work, 77 heating, 126 isothermal expansion of an ideal gas, 75 phase transition, 69 process, 62, 62 66, 94 95, 101, 102, 129 work, 94 Rotating local frame, 276, 502 503 Rubber, thermodynamics of, 148p Rumford, Count, 62, 63b Salt bridge, 457 Salting-out effect on gas solubility, 405, 414p Saturated solution, 385 Saturation temperature, 203 vapor pressure, 203 Second, 470 Second law of thermodynamics Clausius statement, 103 equivalence of Clausius and Kelvin Planck statements, 108 110 Kelvin Planck statement, 104, 118, 121 mathematical statement, 102, 125 derivation, 115 123 Sedimentation equilibrium, 279 Shaft work, 81,81 86 Shear stress, 30 SI, 19 base units, 20, 470 derived units, 20 prefixes, 21 Simple mixture, 308 Solid, 30, 36 viscoelastic, 31 Solid compound, 386, 428, 436 of mixture components, 386 389 Solidus curve for a binary system, 426 Solubility curve, 383 for a binary solid liquid system, 426 of a gas, 405 407 ideal, 406 of a liquid, relation to Henry s law constant, 393 of a solid, 385 of a solid electrolyte, 389 391 of a solid nonelectrolyte, 385 386 Solubility product, 390, 461 temperature dependence, 391 Solute, 223 reference state, 252 253, 259 Solution, 223 binary, 224 in a centrifuge cell, 276 279 ideal-dilute, 252 multisolute electrolyte, 292 process, 324 regular, 309 saturated, 385 solid, 245, 428 Solvent, 223 activity coefficient of, 370n behavior in an ideal-dilute solution, 254 255, 401 Species, 222, 419 Specific quantity, 29 volume, 29 Spontaneous process, 62, 64 66, 101, 129, 342 Standard boiling point, 204 cell potential, 461, 462 evaluation, 464 chemical potential, see Chemical potential, standard composition, 253 concentration, 253 electrode potential, 465 hydrogen electrode, 465 melting point, 204 molality, 253 mole fraction, 254 pressure, 39, 181, 274, 359p, 467p Standard molar properties, values of, 504 506 quantity, 185 evaluation of, 410 411
INDEX 531 of a gas, 185 187 reaction quantity, 318 Standard state of a gas, 181 of a gas mixture constituent, 239 of an ion, 287 of a mixture component, 269 of a pure liquid or solid, 181 of a pure substance, 181 State of aggregation, 30, 476 equilibrium, 48,48 50 metastable, 50 physical, 30, 476 standard, see Standard state steady, 50 of a system, 45,45 50 State function, 45, 45 47 change of, 51 Statistical mechanics, 34, 130, 131 Boyle temperature, 35 Debye crystal theory, 152 Debye Hückel theory, 297 ideal mixture, 261 McMillan Mayer theory, 261n mixture theory, 308 molar entropy of a gas, 154 molar heat capacity of a metal, 152 second virial coefficient, 244 virial equations, 34 Steady state, 50 Steam engine, 107 Steam point, 41, 205 Stirring work, 83,83 84 Stoichiometric activity coefficient, 293 addition compound, see Solid compound coefficient, 315 equation, 313 number, 315, 320, 350 Sublimation point, 203 pressure, 203 temperature, 203 Subscripts for chemical processes, 477 Substance, 222 Subsystem, 28 Supercritical fluid, 32, 33, 205, 210, 211 Superscripts, 478 Supersystem, 28, 115, 117, 120, 121, 124, 125 Surface tension, 144 Surface work, 143 144 Surroundings, 27 Symbols for physical quantities, 472 475 System, 27 closed, 28 isolated, 28,48 open, 28, 227, 228, 235 state of, 45,45 50 System point, 200 Systéme International d Unités, see SI Temperature Boyle, 35 convergence, 172 critical, 205 equilibrium systems for fixed values, 42 ideal-gas, 40, 115, 166 international scale, 41 measurement of, 40 45 scales, 40 41 thermodynamic, 40, 113, 113 115, 166, 470 upper consolute, 430 upper critical solution, 430 Thermal analysis, 428 conductance, 171 energy, 62, 495 reservoir, 50 Thermocouple, 45, 456n Thermodynamic equation of state, 166 equilibrium constant, 351 potential, 134 temperature, 40, 113, 113 115, 166, 470 Thermometer Beckmann, 44 constant-volume gas, 42 liquid-in-glass, 40, 44 optical pyrometer, 45 quartz crystal, 45 resistance, 44 thermocouple, 45 Thermometry, gas, 42 44 Thermopile, 45, 341, 456n Third-law entropy, 151 Third law of thermodynamics, 120, 149 Thompson, Benjamin, 62, 63b Thomson, William, 104, 114b Throttling process, 156
INDEX 532 Tie line, 200 on a binary phase diagram, 426 on a ternary phase diagram, 442 Torque, 82 Total differential, 134, 481 of the Gibbs energy of a mixture, 235 of the Gibbs energy of a pure substance, 181 of the internal energy, 135 137 of the volume, 228 Triple line, 95n, 200 point, 200 cell, 42 of H 2 O, 40 Ultracentrifuge, 276 279 Units, 22 Non-SI, 20 SI, 20 SI derived, 20 Univariant system, 199, 419 Upper consolute temperature, 430 Upper critical solution temperature, 430 van t Hoff, Jacobus, 382b van t Hoff equation, 369 van t Hoff s equation for osmotic pressure, 381 Vapor, 33 Vapor pressure, 203 curve, 204 of a liquid droplet, 400 lowering in a solution, 375, 380 381 saturation, 203 Vaporization, 369 molar enthalpy of, 211 molar heat of, 211 Vaporus curve for a binary system, 426 for a binary liquid gas system, 432, 434, 435 at high pressure, 439 Variables conjugate, 137 dependent, 46 independent, 46 natural, 137, 140, 141 number of independent, 47 Variance, 199, 419 Virial coefficient, 34 equation for a gas mixture, 243 for a pure gas, 34 Virtual displacement, 194 Viscoelastic solid, 31 Volume mean molar, 230 meaurement of, 37 of mixing to form an ideal mixture, 304 molar, 30, 38 partial molar, 248 in an ideal gas mixture, 241 specific, 29 total differential in an open system, 228 Washburn corrections, 339, 340, 363p Work, 56, 57 59, 487 495 chemical, 136 coefficient, 59 coordinate, 59, 119 deformation, 69 74 dissipative, 83, 89, 91, 94, 135 of electric polarization, 95 electrical, 61, 86 91, 95, 168 170, 173, 213, 338, 455 excess, 91 expansion, 71,71 79,95 gravitational, 79 81, 95 of magnetization, 95, 158 mechanical, 95 nonexpansion, 135, 145 reversible, 94 reversible expansion, 77 shaft, 81, 81 86, 95 stirring, 83,83 84 stretching, 95 surface, 95, 143 144 Working substance, 105, 113 Zeotropic behavior, 436 Zeroth law of thermodynamics, 40