PHYSICAL
`
`FIFTH EDITION
`
`P. W. Atkins
`
`University Lecturer and Fellow
`
`of Lincoln College, Oxford
`
`CHEMISTRY
`
`
`
`
`.-I
`
`W. H. FREEMAN AND COMPANY
`N
`Y
`W ORK
`
`Merck 2007
`Merck 2007
`Argentum v. Merck
`Argentum V. Merck
`IPR2018-00423
`IPR2018-00423
`
`

`

`The cover as illustrated by Ian Walpole, is based on Peter Atkins’ represmtation
`of the amplitude ofthe antibonding orbitalformed from the overlap of two H13
`orbitals.
`
`Library of Congress Cataloging—in-Publication Data
`
`Atkins, P. W. (Peter William), 194-0—
`Physical Chemistry/Peter Atkins. — 5th ed.
`p.
`cm.
`includes index.
`ISBN 0—7167'2402—2
`
`1. Chemistry, Physical and theoretical. 1. Title
`QD4531.2.A88 1994b
`541 .3— chO
`
`Copyright © 1978, 1982, 1986, 1990, 1994- by Peter Atkins
`
`No part of this book may be reproduced by any mechanical, photographic,
`or electronic process, or in the form of a phonographic recording, nor may
`it be stored in a retrieval system, transmitted, or otherwise copied for public
`or private use, without written permission of Oxford University Press.
`
`Printed in the United States of America
`
`1234567890KP99876543
`
`This edition has been authorized by the Oxford University Press For sale in
`the USA and Canada only and not for export therefrom.
`
`

`

`Lagrange multipliers A35
`Laguerrc polynomial 426
`Lamb formula 630
`lamp-dip spectroscopy 552
`lamellar micelle 973
`laminar flow 822
`Langevin function 758
`Langmuir isotherm 9B7
`LangmuirBlodgett film 969
`Langmuir—Hinshelwood mechanism
`993
`Uplace equation 963
`Laporte selection rule 596
`[armor frequency 625
`laser 600
`applications in chemistry 611(T)
`argomion 607
`carbon dioxide 608
`cavity 602
`characteristics 602, 6] HT)
`chemical 608
`dye 609
`diode 606
`excirrier 609
`exciplex 609
`ferntochemistry 945
`four—level 601
`gas 607
`helium-neon 607
`hydrogen fluoride 608
`isotope separation 613
`krypton-ion 608
`mode 602
`neodymium 606
`nitrogen 608
`photochemistry 610
`power and energy 603
`pulsed 603
`radiation, characteristics 602,
`61 l (T)
`ruby 606
`semiconductor 609
`solid-state 606
`spectroscopy 510
`summary of applications 6110’)
`summary of characteristics 61 KT)
`laser-induced fluorescence 951
`lartice
`Bravsis 723
`crystal 722
`enthalpy 85, C16ET)
`planes
`identification 723
`separation 725
`space 722
`Laue, M. von 726
`law 1
`Beer—Lambert 545
`Boyle’s 27
`Bragg’s 726
`Charles‘s 28
`Curie 776
`Dalton’s 3i
`Debye—Hi’ickel 321
`Dulong and Petit 363
`Fick's first 822, 848
`Ficlt‘s second 851
`First 60
`
`gas 27
`Gay Lussac’s 28
`Graham's 819
`Henry’s 218
`Hess’s 84
`Hooke’s A38
`
`independent migration of ions 83?
`Kirchhofi‘s 89
`Kohlrausch‘s 837
`limiting 27
`Newron‘s A12
`Newton’s cooling l54
`Ohm’s 1015
`Ostwald dilution B39
`Raoult’s 217
`rate 17, 866
`Rayleighijeans 361
`scientific l
`Senond 120
`Starkifiinstcin 906
`Stefan—Boltzmann 361
`Third 140
`Wein’s 360
`Zeroth 25
`LCAO 475
`symmetry criteria 531
`Le Chatelier’s principle 283
`lead—acid battery 328, 1025
`leading solution 843
`lead/lead sulfate electrode 328
`LED 610
`LEED 981
`step density 983
`Legendre function, associated A26
`length
`bond 462
`kinetic chain 911
`Lennard-Jones potential 773,
`C26(T)
`
`level 448
`lever rule 248
`Lewis, G. N. 462
`LFER 947
`lifetime broadening 553
`ligand field splitting 595
`light
`colour and energy C24(T)
`polarized 762
`scattering 800
`speed 5
`light-emitting diode 610
`limit cycle 919
`limiting
`current density 10l9
`enthalpy of solution 78, (.37le
`ionic conductance C29(T)
`law 27, 322
`Debyeifliickel 321
`molar conductivity 837
`transport number 842
`Linde refrigerator 107
`LindemanneHinshelwood
`mechanism 891
`
`linear
`combination of atomic orbitals 475
`combinations, symmetry-adapted
`531
`Free energy relation 947
`
`Index
`
`E9
`
`momentum All
`operator 379
`wavelength 368
`rotor
`defined 556
`energy levels 559
`superposition 380
`linear-sweep voltammetry 1020
`linewidth
`and temperature 552
`magnetic resonance 646
`natural 553
`liquid
`crystal 832
`phase diagram 834
`junction potential 329
`mixtures 22]
`structure 830
`surface 962
`viscosity 833
`liquid rrvapour phase boundary I97
`liquid—solid phase diagrams 254
`limit cycle 919
`lithium atom 439
`little orthogonality theorem 528
`London
`formula 770
`interaction 770
`long period 44-1
`long-range order 830
`longitudinal
`mode 602
`relaxation 646
`Lorentzian line 649
`Lotka-Volterra mechanism 918
`low-energy electron difl‘raction 981
`lower critical temperature 252
`Luggin capillary 1016
`LUMO 497
`lunar rock 613
`Lyman series 422
`lyophilic 971
`lyophohic 97]
`lyotropic mesomorph 973
`lysozyme, Raman spectrum 584
`
`M shell 43!
`macromolecule
`dilfusion coefficients C270")
`osmometry 228
`magic-angle spinning 653
`magnesium sulphate, partial molar
`volume 21 1
`
`magnetic
`currents 632
`field 5, 625
`flux density 776
`induction 625, 776
`interaction, spin-orbit coupling
`448
`moment 624, 777, C25(T)
`induced 778
`moment of electron 456
`ordering 745, 778
`properties 775
`quantum number 417
`resonance, nuclear 624
`
`scattering 745
`susceptibility 632, 776, C26(T)
`magnetically equivalent nuclei 639
`magnetizability 776
`magnetization 776
`vector 643
`magnetogyric ratio 456
`nuclear 624
`magneton
`Bohr 456
`nuclear 624
`manometer 24
`
`many-electron atom 42!
`scrcuture 438
`Markil‘louwink equation 798
`MAS 653
`mass-average molar mass 705
`material—balance equation 938
`matrix representation 521
`matter 417
`maximum multiplicity
`see Hund's rule 442, 639
`maximum
`non-expansion work
`Gibbs energy 153
`turnover number 891
`velocity, enzymolysis 39]
`work 150
`thermodynamic criterion 66
`Maxwell
`construction 46
`distribution of speeds 15, 37
`experimental verification 38
`relations 163, 163m
`Maxwellifloltzmann distribution Al
`Mayer f-function 709
`McConnell equation 65?
`McMillan—Mayer theory 787
`111.6811
`
`activity cocfiicient 320, C200")
`bond enthalpy 80, C80")
`cube molar mass 785
`distance of diifusion 855
`energy 703
`equipartition I5, 703
`free path 40
`and random walk A39
`radius of orbital 433
`speed 34
`square
`molar mass 785
`speed 34
`value A1
`mechanical
`definition of heat 62
`equilibrium 22
`mechanism, reaction 17
`melting
`incongruent 256
`temperature 185, C4(T)
`pressure dependence, water
`186, 197
`variation with pressure 192
`Ice fuction
`membrane potential 334
`meniscus formation 966
`mercury atom
`as photosensitizer 909
`
`

`

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`This material may be protected by Copyright law (Title 17 us, Code]
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`
`Vapour,
`pressure p
`
`
`
`Liquid
`or solid
`
`
`
`6.3 The vapour pressure of a liquid or
`solid is the pressure exerted by the
`vapour in equilibrium with the condensed
`phase.
`
`
`
`(a)
`
`(1))
`
`(cl
`
`6.4 la] A liquid in equilibrium with its
`vapour. [bl When a liquid is heated in a
`sealed container, the density of the
`vapour phase increases and that of the
`liquid decreases slightly. {The decrease in
`quantity of liquid is a result of
`vaporization] (cl There comes a stage at
`which the two densities are equal and the
`interface between the fluids disappears.
`This occurs at the critical temperature.
`The container needs to be strong: the
`critical temperature of water is 374°C and
`the vapour pressure is then 218 atm,
`
`6.1 Phase boundaries
`
`185
`
`6.1 Phase boundaries
`
`Consider a sample of a pure substance in a closed vessel of constant
`volume. The pressure of a vapour in equilibrium with its condensed
`phase at a specified temperature is called the vapour pressure of the
`substance at that temperature (Fig. 6.3). Hence, as anticipated above,
`the phase boundaries between the liquid and the vapour and between the
`solid and the vapour show how the vapour pressures of the two
`condensed phases vary with temperature. The vapour pressure of a
`substance increases with temperature because, at higher temperatures,
`the molecules can escape more readily from the attractive interactions
`that bind them to their neighbours in the condensed phase.
`
`Critical paints and boiling points
`The behaviour of a liquid heated in an open vessel differs from that of a
`liquid in a sealed vessel. In an open vessel, the liquid vaporizes from its
`surface as it is heated. At the temperature at which its vapour pressure
`would be equal to the external pressure, vaporization can occur through-
`out the bulk of the liquid and the vapour can expand freely into the
`surroundings. The condition of free vaporization throughout the liquid is
`called boiling. The temperature at which the vapour pressure of a liquid
`is equal to the external pressure is called the boiling temperature at that
`pressure. Note that a liquid does not suddenly start to form a vapour at
`its boiling temperature,
`for even at
`lower temperatures there is an
`equilibrium between the liquid and its vapour: at the boiling point the
`vapour pressure is great enough to drive back the atmosphere and
`vaporization can occur freely. For the special case of an external pressure
`of 1 arm, the boiling temperature is called the normal boiling point Tb.
`With the replacement of latm by lbar as standard pressure, there is
`some advantage in modifying the definition so that
`the transition
`temperature refers to that pressure;
`the term standard boiling point
`is
`then used. Because lbar is
`slightly less than 1 atm (1.00 bar =
`0.987 arm), the standard boiling point of a liquid is slightly lower than its
`normal boiling point. The normal boiling point of water is 100.0°C5 its
`standard boiling point is 99.6°C.
`\When a liquid is heated in a sealed vessel, boiling does not occur.
`Instead, the temperature, vapour pressure, and the density of the vapour
`rise continuously (Fig. 6.4). At the same time, the density of the liquid
`decreases as a result of its expansion. There comes a stage at which the
`density of the vapour is equal to that of the remaining liquid and the
`surface between the two phases disappears. The temperature at which
`the surface disappears is the critical temperature TC (which we first
`encountered in Section 1.4). The corresponding vapour pressure is the
`critical pressure pt. Ar and above this temperature a single uniform
`phase fills the container and an interface no longer exists. That is, above
`the critical temperature the liquid phase of the substance does not exist.
`
`Melting points and triple points
`The temperature at which, under a specified pressure, liquid and solid
`coexist
`in equilibrium is called the melting temperature. Because a
`
`