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INDEX

Absolute temperature , (see Temperature, absolute) Accessibility -, 82, 83 Activity -, determination of 269, 270, 271, 278, 279, 327, 328, 329, 330, 331, 332, 333, 336, 337 -, of dissolved components 274, 277, 280, 281, 287, 327, 334, 335, 336, 352, 355, 393 -, of electrolytes 386, 387, 388, 389, 391, 394, 395, 396, 397 -, of gases 267, 268, 301 -, of pure materials 300, 301 -, product 403 -, relative 293 -, variation with temperature or pressure 272, 273, 323 Activity coefficient -, (see under activity) Adiabatic conditions or

processes -, 86 Adiabatic demagnetization -, 517, 518 Adsorbate -, 458 Adsorbent -, 458

Adsorption isotherm -, 464 Adsorption processes -, 458, 459, 464, 465 Affinity -, 198, 200, 264, 265 Algebraic equivalents -, 70
Anode -, 408

Arrhenlus theory -, 384, 385 Barometric -, 455 formula

591

592
Body --, 2

,NDEX

-,

96

-, first theorem 96
-, second

theorem 9 6

Boiling point elevation -, 235, 236 Boundaries


--, 2

Cas imlr-Ons age r reciprocity conditions -, 549 Cathode

-, adiabatic 3 -, diathermic -, impermeable -, permeable 2 2 Centigrade -, 14 scale 2, 8 2


-, 408

Celsius scale -, 14

-, semipermeable Boyle' s law -, 13

Characteristic temperature -, 379 Charles' 18 Law

Bragg-Wlll lares approximation -, 373, 374 Brunauer, Emmett, isotherm -, 464, 474 Calorie 139 Teller

-,

Chemical affinity -, 542 Chemical cells -, (see Galvanic cells) Chemical potential -, 166, 168, 193 -, canonical form 222, 223, 267 -, of electrolytes 386

-,

Calorimetry -, 140, 141 Canonical form -, 222, 223, 274, 278, 282 Carath@odory' s theorem -, 71, 78, 82 Carnot efflclencles

-, at equilibrium 193, 194, 195

INDEX

593
Coefficient stress -, 48 of thermal

-, generalized 543
-,

of high polymers 355 for ideal gas 220, 221

-,

-, for ideal solutions 225, 226, 227


-,

Common tangent constructlon -, 361, 362, 363 Components -, (See Independent components ) Composition of solutions -, temperature dependence 231 Concentration cells double 438

for nonldeal gases 267, 268

-. of nonldeal solutions 277, 285, 288, 290, 291, 293, 336


-,

for radiation 488 reference 226, 277, 279

-,

-,

-, standard 221, 226, 227, 277


-,

Chemical reaction -, general formulation 237, 579


-,

with liquid junctions 437, 438

-, ordinary 436, 437


-,

unit advancement 238

with transference 439

Clauslus -, inequallty 94 -, statement of Second Law 97 Clausius-Clapeyron equation -, 208, 209 Coefficient of elastic compliance -, 130 Coefficient of elastic stiffness -, 130 Coefficient of thermal strain 48

Concentrations - of electrolytes 387,

Configuration space -, (see Phase space) 5 Conjugate variables -, 198, 545, 548 Conservation Equation 538 Conservation of mass 539 Conventions relating to operation of Galvanic

-,

-,

-,

594

INDEX

cells -, 419, 420, 421 Coordinates -, thermodynamic (see also Variables of state) 4 Critical conditions -, 211, 212 Critical magnetic field in superconductivity -, 521, 522, 523 Curie's law -, 504, 517, 518, 519 Current flux -, 568 Daniell cell -, 408, 409, 410, 411 Debye-HOcke i theory -, 390, 391, 392, 393 Debye theory of specific heats -, 147 Degrees of freedom -, (see also Variables state) -, 4 Degrees of freedom, -, 191 Dependence -, functional -, parametric

Detailed balance -, (see Principle of detailed balance) Differential -, 171 quantities

Differentials -, exact 26, 72 -, inexact 26, 72 Displacement vector 29 equation

-,

Duhem-Margules -, 228

Efficiency of heat engines -, 95, 96 Elastic compliance -, (see Coefficient elastic compliance) Elastic stiffness -, (see Coefficient elastic stlffness)

of

of

of

Electrical Conductivity -, 569 Electrochemical cells -, (see Galvanic cells) Electrochemical potential -, 407 Electrodes, types of -, 425, 426, 427 Electroklnetlc effects

number of

27 27

Degree of order -, 379

INDEX

~9~

-, 561,

562, 563 equations

-, s o u r c e of, in galvanic cells 414 Energy -, 53, 54, 55, 89, 115, 168, 540

Electroklnetic -, First 565 -, Second 565 Electrolytes, -, 400, 401

weak

4~8of adsorbed , 4 8 1 , 482

phase

Electro-osmosls -, 564, 566 Electro-osmotlc - , 566 flux

-, and calorimetry -, conservation 539, 540

140

of 55,

Emf - applications

-, in electromagnetic fields 486, 487, 495, 498, 516 444, 445, 446, -, flux vector 540, 542 of 408, 409, -, of a gas 113 of 433 541,

4; 7

-, description 411, 415

-, determination -, expressions 415, 431

-,

radiation 487

for 411, 414,

-, in shock front 528 Enthalpy -, 106, 115, 168 4~9of adsorbed phase , 460, 467, 468, 470 -, and calorimetry - determination emf measurements
|

- , of half ractions 418, 419, 420, 421, 422, 423


-, relation to activities -, relation to Gibbs free energy change 418 -, standard 418 -, standard emfs, of 422
-

418

141

from 442 of 149,

short table

-, determination 150

standard oxidation emf's

422

-, in electromagnetic fields 507, 508, 512

~96
-, integral, in adsorption 467, 468, 470 -, numerical evaluation 149, 150 -, of mixing 347, 378 -, partial molal 171 Entropy -, change in irreversible processes 88, i00, i01, 127, 128, 262, 263 -, determination from emf measurements 442 -, differential, 469, 470, 471 in adsorption -, of mixing 225, 347

INDEX

- numerical evaluation 146, 147, 148 -, parable 90

-, properties of 86, 87, 88, 93, 94, 95, 99, I00, i01, 102 -, radiant 487 -, rate of generation locally 198, 200, 263, 264, 265

-, in electromagnetic 497, 502, 511, 513 -, empirical 83, iii -, excess i00, i01

fields

in reactions 263, 264, 265


I

5~3of superconductors

-, flux vector 198, 542, 543, 571 -, of a gas 113, 218 - integral, in adsorption 466, 467, 468 -, local rate of generation 544, 546 -, at low temperatures 157, 158, 159 -, measurement of 442 -, metrical 85, iii, 112 156,

Equation of continuity for -, 537 Equation of state -, Berthelot 131, 274 -, caloric 118, 512 -, general definition Ii -, for a perfect or ideal gas 113 -, for shock front 533 -, thermodynamic 172 118,

INDEX

597 -, van der Waals 210, 214 Equilibrium -, chemical 237, 238, 239, 240 -, in electrolytes 396, 397, 398, 400, 401, 402, 403, 404 -, in heterogeneous systems 255 -, phase 190, 193 -, in solutions 248, 249, 250, 251, 252, 253 -, thermodynamic 3, Ii -, in two phases 260, 261 -, vapor-liquid 208, 209, 235, 236 Equilibrium constants -, calculations 316, 317 -, changes with temperature and pressure 243, 244, 256, 324, 325, 326 -, of electrolytes 396, 397, 400, 401, 402, 403, 404 -, for gases 240 -, for heterogeneous systems 255, 256, 257, 258, 297, 298 -, relation to standard emf 440 -, for solutions 240, 249, 250, 251, 252, 253, 254, 295, 296, 297, 300, 302, 303, 324, Exact differentials -, (see Differentials, exact) External fields, effects of -, gravitational 450 4~8radlatlon 484, 485, 326 Ettlngshausen coefficient -, 575 Ettlngshausen effect 575

-,

Euler's theorem of homogeneous functions -, 23, 24 Eutectlc -, 368 Eutectlc temperature -, 368

-, surface 458, 464, 465, 466 Faraday -, 410 Fick's law of diffusion -, 547 First Law -, (see Laws of Thermodynamics ) -, as a parable 67, 68

~98

INDEX

Flux
-, 198, 200

272
-, temperature and pressure dependence of

-, electro-osmotlc 564, 565


-,

562, 563,

273, 274, 275


Fugacity coefficient -, (see under Fugacity) Functions of state -, 5, 24, 26, 69, 115

generalized 544

-, volume 562 Forces -, conservative

38 -, in adsorption 459 50 -, conjugate (See Conjugate varlables) -, differential 469, 470, 476, 477 -, in electromagnetic fields 507, 508, 511, 512, 515 -, external 102, 108 -, in gravitational fields 455, 456 -, integral 469, 470, 476, 477 -, in irreversible processes 534 -, for mixing processes 346, 347, 348, 349 -, for radiant fields 487, 488 -, relation to equilibrium constants 240, 241, 242, 243, 244,

-, electromagnetic

-, generalized 35, 544 -, radiation 485 -, surface 45, 46 -, thermodynamlc 32, 35

Force Density -, electromagnetic 50

(Lorentz)

Fourier's law of heat conduction -, 199, 546

Fourth law -, (see Laws of Thermodynamics ) Freezing point lowering -, 232, 233, 234, 235, 341, 342, 343, 344, 345 Fugaclty -, 267 -, determination of 270, 271,

INDEX

599

248, 250, 253, 255, 256, 257, 295, 296, 297, 298, 299, 303,
324, 325, 326 Galvanic cells -. general description 410, 411, 412, 413, 414, 416, 417, 421 -, types of operating cells 435, 436, 437, 438, 439, 440 Galvano-thermomagnetic effects -, 572, 573, 574, 575, 576, 577, 578 Gauge invariance 285 consequences of 286, 288, 289, 290

251, 252, 253, 257, 298, 299, 326


-, in electromagnetic f i e l d s 488, 500, 501 - , of mixing 225, 346, 347, 355, 356, 359, 360, 361, 378
-, for operation of galvanic cells 413, 424, 441 -, in relation to equilibrium constants 240, 241, 242, 243, 248, 250, 253, 255, 257, 295, 297, 298, 299 -, standard change 241, 242 Gibbs phase rule -, 194 Gravitational Field Effects -, 450, 451, 452 Gravochemlcal potential -, 452, 453 Hall coefficient -, 574 Hall effect -, 574, 575

-,
-

Gauss theorem -, 32, 33 Gibbs adsorption equation -, 464, 466, 468 Gibbs equation -, 123 G ibbs-Duhem relation -, 162, 166, 175 Gibbs-Helmholtz - , 122 equation

Gibbs free energy -, 105, 115, 166, 168 -, change in ionization 384 -, change in a reaction 237, 238, 239, 241, 243, 248, 250,

Heat -, 53, 54, 55, 139


-, of adsorption 465, 468, 475, 476, 477, 479,

600 480
-, of dilution 314, 321 - flow or flux 53, 54, 55, 140, 141, 197 -, of formation 312, 313, 320 -, of mixing 347 -, of reaction 141, 142, 321 -, of solution, 314 differential Hess ' law -, 312 -, in electromagnetic fields 488, 495, 497, 498, 513 Henry's law -, 261, 276, 330, 354

INDEX

353,

Holonomic f u n c t t o n s 69, 70, 72, 73, 74, 75, 76, 77

-,

of solution,

integral 314

Homogeneous functions -, of degree one 23 Hooke' s law -, 63 Hugoniot' s equation -, 529 Hydraulic permeability -, 565

-, standard,

of formation 313

Heat capacity -, 118, 120, 172 -, of absorbed phase 481, 482 -, changes 121 fields

-, in electromagnetic 500, 516, 517 -, at low temperature -, of noble metals 148 -, of 0 2 150 -, of superconductors Heat engine -, 95 Helmholtz free energy -, 104, 115, 168

Hydraulic permlttivity -, 557 Hydraulic resistance - , 566 Hydrolysis -, 403

147, 155

523

Ideal gas, properties -, 216, 217, 220 Ideal solutions, properties of - , 223 Immiscibility

of

INDEX

~01
-,

variation with temperature

375 Independent components, number of -, 190, 191 Inequalities, thermodynamic -, 185, 186, 187, 188 Inexact differentials (see Differentials, inexact)

-, (See Processes, irreversible)

Isenthalps -, 136, 138, 139 Isotherm -, (see Adsorption isotherm) Joule -, 139 Joule-Thomson coefficient -, 123, 124, 134, 135 Joule-Thomson experiment -, 123, 124 Kelvin temperature scale -, (see Temperature, absolute or Kelvin) Kelvln's formulation of Second Law -, 97 Kirchhoff' s equation -, 122
Lambda a n o m a l y - , 380 Lambda p o i n t - , 380

--,

Integrable functions -, (see Holonomlc functions) Integrals with variable limits -, 505, 506, 507 Integrating denominator -, (see Integrating factor) Integrating factor -, 70 Interfaclal Tension -, 46 Interference coefficients -, 548 Inversion temperature -, 124, 135 Ionic strength -, 389 Ionization of electrolytes -, 385, 386, 387, 388, 400, 401, 402, 403

Langmuir adsorption isotherm -, 471, 473 Lavoisier and Laplace' s Law -, 312

Irreversible Processes

602

INDEX

Law of electroneutrallty -, 386

Macroscopic coefficients -, (see Phenomenological coefficients) Macroscoplc equations -, (see Phenomenologlcal equations) Magnetlte-zlnc ferrite 310solld solutions 309,
, 311

Law of mass action -, 581, 586 Laws of Thermodynamics -, First 52, 53, 54, 55, 56, 541 -, Fourth 589, 590 -, Second 68, 83, 542, 543 -, Third 156 -, Zeroth 9 Le Chatelier's Principle, extens ion of -, 551, 522 Legendre transformations -, 115, 183, 184 Lever rule -, 359, 361, 362 Line integral -, 36, 37 Liquld junc t ions -, 427, 428, 429, 430 Liquid junction potentials -, 427, 428, 429, 430 Liquldus -, 365 Mach number ~ -, 532

Margules equation -, 349 Maxwell relations -, 116 -, for adsorption phenomena 462, 463 -, for electromagnetic phenomena 502, 509, 510 Membrane conductivity -, 565 Microscopic reversibility - , ( s e e Principle of microscopic reversibility) Miscibility gap -, 365 Mixing functions -, 347 Molallty -, of electrolytes 387, 388 -, of pure material 284

INDEX

603
-, relation to mole fraction 249, 284 Molarity -, of electrolytes,
-,
-, 171

Path
--, 5

387, 388 -, cyclic 91, 92, 93, 94

of pure material 2 8 4
Perttectic -, 370 phase diagram

-, relation to mole fraction 249, 284 Nernst coefficient transverse 576, 578

Peritectic temperature
-, 370

-,

Nernst distribution law -, 261 Nernst effect transverse 576, 578

Pfafflan forms -, 30, 38, 69, 70

pH
-, determination of 446, 447 Phase -, 190 Phase diagrams -, 206, 207, 210, 364, 365, 366, 367, 368, 369, 370, 371
P h a s e rule -, (see Gibbs rule ) Phase
--, 5

-,

Nernst equation - , 418 Nernst heat theorem -, 159 Nonacces s ib i I i ty -, 71 Ohm's law -, 547, 569 Onsager Reciprocity Conditions -, 549, 552, 554 Order parameter 379

phase

space

-,

Otto engine -, 99 Partial molal quantities -, (see also under Properties, partial molal)

Phase s tabil I ty and separation -, 349, 350, 351, 352, 353, 358, 360, 361
Phase transitions -, 210

604

INDEX

Phenomenologlcal coefficients -, 199, 200, 548 Phenomenologlcal equations 200, 201, 548 585

-.

adiabatic 5, 52, 53, 54, 106, i07, 120, 121, 155

-,

-, cyclic 91, 92, 93, 94 -, fictitious 7 6, 534,

-, for reactions Point,


--, 5

representative

-, irreversible 535, 536, 537

Porous plug experiment -, 123, 124 Potential -, 38 function

-, isentroplc 86, 105, 106, 120, 121


-,

isobaric 105, 106 104, 106 103

-, isochorlc Poyntlng' s relation -, 214 Pressure -, electro-osmotic -, generalized 508, 514


-,

-, Isoenergetlc -, isothermal 105 -, macroscopic -, quaslstatic

103, 104,

564

thermodynamic

5 5 5, 6 I01

radiation 489, 490, 491, 492, 499

-, reversible -, spontaneous

Prigoglne' s theorem -, 550, 551 Principle of detailed balance -, 585 Principle of local state -, 534 Principle of microscopic reversibility -, 585 Process -, (see also System)

-, steady state 6, 7 -, virtual 109 Proper coefficients -, 548 Properties -, thermodynamic

Raoult' s law - 223, 224, 225, 228, 229, 260

INDEX

~0~
-,

departures from 275, 353

-, 564 Second law -, (see Laws of Thermodynamics ) Seebeck coefficient -, 570, 576, 577
Shock phenomena -, 524

Radiation effects -, 484, 485 -, pressure 484, 485, 486 Reaction rates or velocities -, 538, 539, 580, 581, 582, 583, 584, 585, 586, 587 Reactions, coupled and uncoupled -, 579, 582, 584, 585, 587, 588 Reciprocal theorem -, 21 Reciprocity theorem 22

-, equation of state for 533 -, shock front 525 -, shock strength 530 -, temperature in shock front 530 -, velocity of shock front 526, 531, 532 Solidus -, 365 Solubility product constant -, 401 Solution c u r v e s 31, 71

-,

Reference state -, 267, 277, 279 Reservoir


--, 4

Resistivity -, electrical 565, 574, 575 Reynolds transport equation -, 536 Righi-Leduc coefficient -, 577 Righi-Leduc effect -, 577 Rutger' s equation -, 523 Saxdn' s law

-,

Sommerfeld theory of specific heat -, 147 Sorer effect -, 558, 559, 560 Specific heat ratio -, determination from

606
sound velocity 532 527, 530, 531,
-,

'NDEX

564

Spreading pressure, dimensional - , 459

two

Streaming potential -, 564


Stress

-, 41 Stability criteria -, 184, 185, 186, 187, 188, 189 Standard chemical potential -, (see Chemical potential, standard) Standard conditions or states -, 142, 267, 276, 277, 417 Standard free energy changes in reactions -, 241, 242, 299 State, equation of -, (see Equation of state) State space 5 -, (see Phase space) Steady state conditions -, 550, 551, 552 S te fan-Bo I tzmann Law -, 487 Stokes -, 33
'

Subsystem --, 2

Superconductors -, 521, 522 Surfaces -, 458, 459 -, mathematical 29

Surroundings 2, 56, 57, 58, 59, 60, 61, 62

System
--, 2

-,

adiabatic

-, closed 2 -, continuous
-,

2
2

heterogeneous 2

theorem

-, homogeneous -, isentroplc

105,

106

Stiffness -, 130 Strain -, 41

coefficients -, isobaric -, isochorlc 105, 106 104, 106 103

-, isoenergetic S treaming current

INDEX

607
The rmodynamlc func t ions -, (see Functions of state) Thermoelectric effects 567, 568, 569, 570, 571. 572, 573

-, isolated 3, 102 -, isothermal -, open 2 Tangent construction -, (see Common tangent construction) Temperature (function) 103, 104

Thermoelectric power -, (see Seebeck coefficient) Thermomechanlcal effects -, 554, 555, 556, 557, 558 Thermometers -, gas 13, 14 -, types of 13, 16 Third law -, (see Laws of Thermodynamics )

-, absolute or Kelvin 15, 86, 156 -, calibration 16, 17 -, characteristic -, empirical -, ultimate 379

Ii, 12, ii0, iii 589, 590

Thermal conductivity -, 199, 546, 557, 570, 576, 577 Thermal strain -, 129, 130 Thermal stress -, 129, 130 Thermochemical -, 312 Thermochemistry -, 311 Thermodynamic forces -, (see Forces, thermodynamic) laws

Tie-llne -, 365 Transference numbers -, 429 Triple point -, 15 van der Waals equation of state -, (see Equation of state, van der Waals) van' t Hoff' s equation -, 243, 324, 325 Variables

~08
-, extenslve 5
-,

INDEX

-, general 36, 56, 57, 58, 59, 60, 61, 62 -, gravitational 41, 42

intensive 5 of 18, 19, -, in shock front 527, 528


-, of 64 stretching 62, 63,

-, transformations 20, 21 Variables of state


--, 4

Vector theorems -, 33 Vlrlal coefficient -, 133 Virtual changes or processes -, 102 Volume -, changes in electromagnetic field 503 -, change in mixing 347 -, flux (see Flux, volume) -, molar 162 -, partial molal 161, 163, 164, 165, 166 Walls -, (see Boundarles) Work -, adiabatic 51, 106, 107 -, of compression 38, 39, 40, 62, 63, 64 45 electromagnetic 42, 43, 44, , 493, 494

-, surface expansion 41, 45, 46 Young' s modulus - , 48, 129 Zero th i aw -, (see Laws of Thermodynamics )