Index 1377
Raman, Chandrasekhara Venkata, 985
Raman shift, 986
Raman spectrophotometer, 985, 985f
Raman spectroscopy, 949, 985–991,
985f, 997
process of, 985–987
rotational, 987
vibrational, 987–991, 989–990f
Random walk, Fick’s second law of diffusion
and, 451–452
Randomness, disordervs., 137–138
Raoult, Francois Marie, 238
Raoult’s law, 237–240, 299
deviation from, 248–249, 249f
dilute solutions and, 256–257
ideal solution and, 238–239
nearly ideal solution and, 240, 240f
osmotic pressure and, 297
vapor pressure lowering and, 296
Rate constant
apparent, 504
of chemical reactions, 487
reverse, 508
temperature dependence of, 487, 533–539
Rate law(s), 487
of autocatalysis, 586–587
of chemical reactions, 485, 521, 523–562
first-order, 489–490
nth-order, 493
second-order, 491
zero-order, 494
with definite orders, 487, 1106
determination of, 485, 521
integration of, 499–502
of photochemistry, 559
reaction mechanisms and, 540–553
deduction of, 549–553
determination of, 540–541
Lindemann mechanism, 545–547
more than two step mechanisms,
547–549, 1245–1246
rate-limiting step approximation,
541–543
steady-state approximation, 543–545
temperature dependence, 553
for reaction order determination,
494–495, 495f
Rate of adsorption, in heterogenously
catalyzed reactions, 572
Rate of change of Gibbs energy per mole of
reaction, 305
Rate of collisions, in collision theory,
535–536, 535f
Rate of desorption, in heterogenously
catalyzed reactions, 572
Rate of flow, Poiseuille’s equation for,
453–455
Rate of reaction, 486.See alsoChemical
reaction rates
Rate of shear
in liquids, 471
viscous flow, 445
Newton’s law of, 453
Rate-limiting step approximation, for rate law
approximation, 523
with reaction mechanisms, 541–543
Rayleigh, Baron.SeeStrutt, John William
Rayleigh–Jeans theory, of blackbody
radiation, 641–642, 642f
Reactant
concentration
chemical reactions dependence on, 485
in reaction mechanism, 511–512, 511f
forward reactions with more than one,
499–505
method of initial rates, 502–504
method of isolation, 504–505
rate law integration, 499–502
forward reactions with one, 488–497
first-order, 489–491
nth-order, 493–494
reaction order determination, 494–497,
495f, 497f
second-order, 491–493
zero-order, 494
Reaction coordinate
in activation overpotential, 602–603, 603f
in potential energy surfaces, 1107–1108,
1108f
Reaction cross section, in collision theory, 525
Reaction diameter
in bimolecular processes, 529
for hydrogen and hydroxide ions, 531
Reaction kinetics, of polymer formation, 565,
589–594, 592f, 594f
Reaction mechanisms
autocatalysis, 585–587
catalysis, 566–580
enzyme, 575–580, 576f, 578–579f
heterogenous, 566–572
homogenous, 573–575
chain reactions, 556–561branching-chain, 560–561
hydrogen reaction with halogens,
559–560
photochemical, 558
for chemical reactions, 510–512, 511f,
521, 561
concentration in, 511–512, 511f
equations for, 510–511
competing of, 583–585, 583f
elementary processes in gases and, 523–527
collision theory of bimolecular processes,
523–526
collision theory of termolecular
gas-phase reactions, 527
collision theory of unimolecular
processes, 527
general statement for, 527
elementary processes in liquids and,
527–532
bimolecular, 528–532
termolecular and unimolecular, 532
experimental molecular study of, 608–614
detection of reactive intermediates,
609–610
molecular beam reactions, 610–611f,
610–614, 613f
nonequilibrium electrochemistry, 595–608
electrochemical cells with finite currents,
596–599
overpotential, 600–608
rates of electrode processes, 599–600
polymerization kinetics, 589–594,
592f, 594f
principle of detailed balance, 583–585, 583f
rate laws and, 540–553
deduction of, 549–553
determination of, 540–541
Lindemann mechanism, 545–547
more than two step mechanisms,
547–549, 1245–1246
rate-limiting step approximation,
541–543
steady-state approximation, 543–545
temperature dependence, 553
summary of, 561–562, 615
Reactive intermediate
in chemical reaction, 510, 524
detection of, 609–610, 615
in steady-state approximations, 543–544
Reciprocal identity, 1236
Recursion relation, 1195–1196