PHYSICAL
`CHEMISTRY
`
`IPR2018-00423
`
`
`FIFTH EDITION
`
`P. W. Atkins
`University Lecturer and Fellow
`of Lincoln College, Oxford
`
`isa
`W. H. FREEMAN AND COMPANY
`New YORK
`
`Merck 2007
`Merck 2007
`Argentum v. Merck
`Argentum v. Merck
`IPR2018-00423
`
`

`

`The cover as illustrated by lan Worpole, is based on Peter Atkins’ representation
`of the amplitude ofthe antibonding orbitalformed from the overlap of two H1s
`orbitals.
`
`Library of Congress Cataloging-in-Publication Data
`
`Atkins, P. W. (Peter William), 1940-
`Physical Chemistry/Peter Atkins. — 5th ed.
`p.
`cm.
`Includes index.
`ISBN O-7167-2402-2
`1. Chemistry, Physical and theoretical. I. Title
`QD4531.2.A88 1994b
`541.3-de20
`
`Copyright © 1978, 1982, 1986, 1990, 1994 by Peter Atkins
`
`Nopart 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
`
`12.345 6 7.89 0- KP 9 9-8 7655 4.3
`
`This edition has been authorized by the Oxford University Pressfor sale in
`the USA and Canada only and notfor export therefrom.
`
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`

`

`Lagrange multipliers A35
`Laguerre polynomial 426
`Lamb formula 630
`Lamp-dip spectroscopy 552
`lamellar micelle 973
`laminar flow 822
`Langevin function 758
`Langmuir isotherm 987
`Langmuir-Blodgett film 969
`Langmuir-Hinshelwood mechanism
`998
`Laplace equation 963
`Laporteselection rule 596
`Larmorfrequency 625
`laser 600
`applications in chemistry 611(T)
`argon-ion 607
`carbon dioxide 608
`cavity 602
`characteristics 602, 611(T)
`chemical 608
`dye 609
`diode 606
`excimer 609
`exciplex 609
`femtochemistry 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,
`611(T)
`ruby 606
`semiconductor 609
`solid-state 606
`spectroscopy 510
`summary of applications 611(T)
`summary of characteristics 611(T)
`laser-induced fluorescence 951
`
`Bravais 723
`crystal 722
`enthalpy 85, C16(T)
`planes
`identification 723
`separation 725
`space 722
`Laue, Mi. von 726
`
`Beer-Lambert 545
`Boyle’s 27
`Bragg’s 726
`Charles’s 28
`Curie 776
`Dalton’s 31
`Debye-Hiickel 321
`Dulong and Petit 363
`Fick’s first 822, 848
`Fick’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 837
`Kirchhoff’s 89
`Kohlrausch’s 837
`limiting 27
`Newton’s Al2
`Newton’s cooling 154
`Ohm’s 1015
`Ostwald dilution 839
`Raoult’s 217
`rate 17, 866
`Rayleigh—Jeans 361
`scientific 1
`Second 120
`Stark-Einstein 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
`ligandfield splitting 595
`light
`colour and energy C24(T)
`polarized 762
`scattering 800
`speed 5
`light-emitting diode 610
`limit cycle 919
`limiting
`current density 1019
`enthalpy of solution 78, C7(T)
`ionic conductance C29(T)
`law 27, 322
`Debye-Hiickel 321
`molar conductivity 837
`transport number 842
`Linderefrigerator 107
`Lindemann-Hinshelwood
`mechanism 891
`
`linear
`combination of atomic orbitals 475
`combinations, symmetry-adapted
`531
`free energy relation 947
`
`Index
`
`E9
`
`momentum Al1
`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 221
`structure 830
`surface 962
`viscosity 833
`liquid-vapour phase boundary 197
`liquid—solid phase diagrams 254
`limit cycle 919
`lithium atom 439
`little orthogonality theorem 528
`London
`formula 770
`interaction 770
`long period 444
`long-range order 830
`longitudinal
`mode 602
`relaxation 646
`Lorentzian line 649
`Lotka-Volterra mechanism 918
`low-energy electron diffraction 981
`lowercritical temperature 252
`Luggin capillary 1016
`LUMO 497
`lunar rock 618
`Lymanseries 422
`lyophilic 971
`lyophobic 971
`lyotropic mesomorph 973
`lysozyme, Raman spectrum 584
`
`M shell 431
`macromolecule
`diffusion coefficients C27(T)
`osmometry 228
`magic-angle spinning 653
`magnesium sulphate, partial molar
`volume 211
`
`magnetic
`currents 632
`field 5, 625
`flux density 776
`induction 625, 776
`interaction, spin-orbit coupling
`448
`moment 624, 777, C25(T)
`induced 778
`momentofelectron 456
`ordering 745, 778
`properties 775
`quantum number417
`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 421
`strcuture 438
`Mark-Houwink equation 798
`MAS 653
`mass-average molar mass 785
`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 number891
`velocity, enzymolysis 891
`work 150
`thermodynamiccriterion 66
`Maxwell
`construction 46
`distribution of speeds 15, 37
`experimental verification 38
`relations 163, 163(T)
`Maxwell—-Boltzmanndistribution Al
`Mayer f-function 709
`McConnell equation 657
`McMillan—-Mayer theory 787
`mean
`
`activity coefficient 320, C20(T)
`bond enthalpy 80, C8(T)
`cube molar mass 785
`distance of diffusion 855
`energy 703
`equipartition 15, 703
`free path 40
`and random walk A39
`radius of orbital 433
`speed 34
`square
`molar mass 785
`speed 34
`value Al
`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
`see fuction
`membranepotential 334
`meniscus formation 966
`mercury atom
`as photosensitizer 909
`
`

`

`
`This material may beprotected by Copyrightlaw (Title 17 U.S. Code)
`
`
`
`
`
`
`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)
`
`(b)
`
`(c)
`
`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.
`
`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
`
`Critical points 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 temperatureat 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 atm, the boiling temperature is called the normalboiling point 7,.
`With the replacement of 1 atm by 1 bar 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 1 bar is
`slightly less than latm (1.00 bar=
`0.987 atm), the standard boiling pointof a liquid is slightly lower than its
`normal boiling point. The normal boiling point of water is 100.0°C; 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
`6.4 (a) A liquid in equilibrium with its
`density of the vapour is equal to that of the remaining liquid and the
`vapour. (b) Whenaliquid is heated in a
`surface between the two phases disappears. The temperature at which
`sealed container, the density of the
`the surface disappears is the critical temperature T. (which wefirst
`vapour phase increases and that of the
`encountered in Section 1.4). The corresponding vapour pressure is the
`liquid decreasesslightly. (The decrease in
`critical pressure p.. At and above this temperature a single uniform
`quantity of liquid is a result of
`phasefills the container and an interface no longer exists. That is, above
`vaporization.) (c) There comes a stage at
`which the two densities are equal and the
`the critical temperature the liquid phase of the substance does not exist.
`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.
`
`