Physical Chemistry PDF
Preview Physical Chemistry
HEMISTRY 3rd edition Laidler/Meiser ) 00 <> 2 He Helium 4.002602 S 0) *§ rro3--> 18 Ar Argon 39.948 36Kr Krypton 8830 in CT 0N0D ^C r^ 71 Lu Lutetium 174.967 103Lr Lawrenc-ium (262) i> r"I~?< ON ' O--Nr 127.2CI Chlorine 35.4527 33.50Br Bromine 79.904 oc in 5 1< o 710.1Yb Ytterbium 173.04 102 No Nobelium (259) 5 ~> 00 o o| rT 12.64S Sulfur 32.066 32.45Se Selenium 78.96 iSn rE- or- 3!j £1£e o 6191Tm Thulium 168.93421 11021Md Mendele-vium (258) 2 m< t"»iZ *u6£iJ i8rs-C —ri — &oSo-gu snPa£ ^^t*/) £OE J—ONN Kor-it=/j .<1B>c5^ oo « 1 o0omo^0 618.1Er Erbium 167.26 110.02Fm Fermium (257) ON o c o " 1.1 - 5K J* Sc O S-2 g O c = o[o— jaa. "3S o .r Ho Holmium 164.93032 1.2Es Einstein-ium (2521 NO 00 67 99 2sc mN pa Cc§Q °£—° m—*-< 1—<3E§ o<nfo£o*oNn —-^«" O.Ba2 mOsCNo O0-N0—B -3.Ea2 00 2 E3 oeson nNoO ^ Q>N7) N—O 918.2Cf Califor-nium (251) J E ° 2 ^ o 8»S3 QO <ni 3 3 r^; 1.1Tb Terbium 158.92534 1.2Bk Berkelium (247) 00 65 97 -£9 Os w3 ^cO d*^> r- <" 030 0"^ <9 6? SO0kNNO^bO -—^= DM3 cirj 614.1Gd Gadolin-ium 157.25 916.2Cm Curium (247) o — _ ^t 2 E3 2 E3 0p0 £ Ec & fN 7" 00 nToT So- S oo cu i0r>i o3 a— S3 61.30Eu Europium 151.965 91.52Am Americium (243) Electronegativity - - ° - E 3 B On•>—< CrN~).(JoU oO""oN> Si NX "5 o> „o2ng"^ |s*>3- Sri 61.21Sm Samarium 150.36 91.42Pu Plutonium (244) number; weight •KgS3 J 00 sNoO [«^ 3—"ta9 I|E33 'c3- N—OOc« 6.£EE d ooo "('"« .IES2 >S/3N 61.11Pm Prome-thium (145) 91.32NpNeptunium (237) CQ 2 E O E li AtomicSymbolName Atomic 1 > IS g1 ON 3- acsj .|2 sd Nd Neodym-ium 144.24 1.2 Uranium 238.0289 60 92 2.2H Hydrogen 1.00794 NOC-Q *"^^f"^.2-EEE uo3-(i <NS Sotg -r - S od ^o=«onSlo,iEs"p 51.91Pr Praseo-dymium140.90765 91.11Pa Protac-tinium (123 s" 1Es °—„ 5 2 c1cC P2H f12£3 2 Q IQE S 518.1Ce Cerium 140.115 9l0.lTh Thorium 232.0381 C/3 •ec4-* CQ R-l P^ ^«I r"-* N g CCii -5a^s £3E Os <2 -t s oi<U |a1) s 2 E £ <y o s: CQ O .Tm32 Voo^Nn ON > 1>E bXX5' o oo * ^1 - -*§J * HXe<)du hPSj. Nt§ ts»O- a4ai C—«>=E3Q, rpa«0->-;0'i "fill OO-Ua OJ2E! g"o»o• - £3 r-- ^nq~O~ « C3EQ — X) OES w^ -ooo 4O•P5 -< 3* ic o o 3E ° q*s- o£2 oofonnoS 2 Ml£ «S 5 Si«§ 1Scr--. odnn>Wt» 'U£3I O—orSn tr — ^ m ir, NO <u cu P0U3J Table of Atomic Weights (Relative Atomic Masses) Atomic Atomic Atomic Atomic Name Symbol Number Weight Name Symbol Number Weight Actinium* Ac 89 (227.028) Mercury Hg 80 200.59(2) Aluminum Al 13 26.981539(5) Molybdenum Mo 42 95.94(1) Americium* Am 95 (243) Neodymium Nd 60 144.24(3) Antimony (Stibium) Sb 51 121.757(3) Neon Ne 10 20.1797(6) Argon Ar 18 39.948(1) Neptunium* Np 93 (237.048) Arsenic As 33 74.92159(2) Nickel Ni 28 58.6934(2) Astatine* At 85 (210) Niobium Nb 41 92.90638(2) Barium Ba 56 137.327(7) Nitrogen N 7 14.00674(7) Berkelium* Bk 97 (247) Nobelium* No 102 (259) Beryllium Be 4 9.012182(3) Osmium Os 76 190.23(3) Bismuth Bi 83 208.98037(3) Oxygen O 8 15.9994(3) Bohrium* Bh 107 (262) Palladium Pd 46 106.42(1) Boron B 5 10.811(5) Phosphorus P 15 30.973762(4) Bromine Br 35 79.904(1) Platinum Pt 78 195.08(3) Cadmium Cd 48 112.411(8) Plutonium* Pu 94 (244) Cesium Cs 55 132.90543(5) Polonium* Po 84 (209) Calcium Ca 20 40.078(4) Potassium(Kalium) K 19 39.0983(1) Californium* Cf 98 (251) Praseodymium Pr 59 140.90765(3) Carbon C 6 12.011(1) Promethium* Pm 61 (145) Cerium Ce 58 140.115(4) Protactinium* Pa 91 231.03588(2) Chlorine CI 17 35.4527(9) Radium* Ra 88 (226.025) Chromium Cr 24 51.9961(6) Radon* Rn 86 (222) Cobalt Co 27 58.93320(1) Rhenium Re 75 186.207(1) Copper Cu 29 63.546(3) Rhodium Rh 45 102.90550(3) Curium* Cm 96 (247) Rubidium Rb 37 85.4678(3) Dubnium* Db 105 (262) Ruthenium Ru 44 101.07(2) Dysprosium Dy 66 162.50(3) Rutherfordium* Rf 104 (261) Einsteinium* Es 99 (254) Samarium Sm 62 150.36(3) Erbium Er 68 167.26(3) Scandium Sc 21 44.955910(9) Europium Eu 63 151.965(9) Seaborgium* Sg 106 (263) Fermium* Fm 100 (257) Selenium Se 34 78.96(3) Fluorine F 9 18.9984032(9) Silicon Si 14 28.0855(3) Francium* Fr 87 (223) Silver Ag 47 107.8682(2) Gadolinium Gd 64 157.25(3) Sodium (Natrium) Na 11 22.989768(6) Gallium Ga 31 69.723(1) Strontium Sr 38 87.62(1) Germanium Ge 32 72.61(2) Sulfur S 16 32.066(6) Gold Au 79 196.96654(3) Tantalum Ta 73 180.9479(1) Hafnium Hf 72 178.49(2) Technetium* Tc 43 (98) Hassium* Hs 108 (265) Tellurium Te 52 127.60(3) Helium He 2 4.002602(2) Terbium Tb 65 158.92534(3) Holmium Ho 67 164.93032(3) Thallium Tl 81 204.3833(2) HIynddiruomgen HIn 491 1141..801087(934)(7) TThhuolriiuumm* TThm 9609 213628..09338412(11()3) Iodine I 53 126.90447(3) Tin Sn 50 118.710(7) Iridium Ir 77 192.22(3) Titanium TWi 22 47.88(3) Iron Fe 26 55.847(3) Tungsten (Wolfram) 74 183.84(1) Krypton Kr 36 83.80(1) Ununbium* Uub 112 (277) Lanthanum La 57 138.9055(2) Ununnilium* Uun 110 (269) Lawrencium* Lr 103 (262) Unununium* Uuu 111 (272) Lead Pb 82 207.2(1) Uranium* U 92 238.0289(1) Lithium Li 3 6.941(2) Vanadium V 23 50.9415(1) Lutetium Lu 71 174.967(1) Xenon Xe 54 131.29(2) Magnesium Mg 12 24.3050(6) Ytterbium Yb 70 173.04(3) Manganese Mn 25 54.93805(1) Yttrium Y 39 88.90585(2) Meitnerium* Mt 109 (266) Zinc Zn 30 65.39(2) Mendelevium* Md 101 (258) Zirconium Zr 40 91.224(2) *Theelementsmarkedwithanasteriskhavenostableisotopes. RecommendedbytheIUPACCommissiononAtomicWeightsandAtomicAbundances;furtherdetailsaretobefoundin"Atomicweightsoftheelements 1991,"PureandAppliedChemistry,64, 1519-1534(1992).Thevaluesarereliableto±thefiguregiveninparentheses,applicabletothelastdigit.Numbersfor atomicweightsinparenthesesareestimates. Physical Chemistry Physical THIRD EDITION Chemistry KEITH LAIDLER J. University of Ottawa, Emeritus JOHN MEISER H. Ball State University HOUGHTON MIFFLIN COMPANY BOSTON NEW YORK Editor-in-Chief: Kathi Prancan SeniorSponsoringEditor: RichardStratton EditorialAssistant: SarahGessner PackagingServices Supervisor: Charline Lake SeniorManufacturingCoordinator: PriscillaJ.Abreu Marketing Manager: PenelopeHoblyn Coverdesign: WalterKopec Coverimage: TeresaLarsen usingGRAMPS byT. J. O'Donnell on aTitan 3000 Workstation, MolecularGraphicsLabofArthurOlsenatTheScripps Research Institute, LaJolla, California The figureon thefrontcoverisbasedon acomputer-generatedpotential-energydiagram forwater.The vertical axis is forpotentialenergy;thetwohorizontal axesrelateto interatomicdistances.Theplaneofthehorizontal axes indicatestheenergyofthe separated atoms 2H + O.Thegreenishplanecorrespondstothe zero-pointlevel ofthemolecule. PhotoCredits RobertBoyle,page 11: CourtesyofEdgarFahs Smith Collection, Universityof PennsylvaniaLibrary RudolfJulius Emmanuel Clausius, page97: Courtesy ofEdgarFahs SmithCollection, University ofPennsylvaniaLibrary JacobusHenricus van'tHoff, page 155: CourtesyofEdgarFahsSmithCollection, UniversityofPennsylvaniaLibrary Michael Faraday, page 269: CourtesyofEdgarFahs SmithCollection,Universityof PennsylvaniaLibrary SvanteAugustArrhenius, page 274: CourtesyofEdgarFahs SmithCollection, Universityof PennsylvaniaLibrary Henry Eyring, page 395: CourtesyofManuscripts Division,J.WillardMarriottLibrary, UniversityofUtah GilbertNewtonLewis, page 552: CourtesyofMITMuseum GerhardHerzberg, page604: UPI/Corbis-Bettmann Ludwig Boltzmann, page716: CourtesyofOthmerLibrary oftheChemical Heritage Foundation DorothyCrowfootHodgkin,page 941: UPI/Corbis-Bettmann Copyright© 1999by Houghton MifflinCompany.All rightsreserved. 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Library ofCongressCatalogCardNumber: 98-72056 ISBN: 0-395-91848-0 123456789-QK-0201 009998 7 5 Contents Preface xiii 1.13 Equations of State 36 ThevanderWaalsEquationofState 36 TheLawof The Nature ofPhysical Chemistry and CorrespondingStates 39 OtherEquationsofState 41 1 the Kinetic Theory ofGases 1 1.14 The Virial Equation 41 Appendix: Some Definite Integrals Often Used in 1.1 The Nature of Physical Chemistry 3 Physical Chemistry 44 1.2 Some Concepts from Classical KeyEquations 44 Problems 45 SuggestedReading 49 Mechanics 4 Work 4 KineticandPotentialEnergy 5 2 The First Law of 1.3 Systems, States, and Equilibrium 6 Thermodynamics 51 1.4 Thermal Equilibrium 8 TheConceptofTemperatureandItsMeasurement 8 2.1 Origins of the First Law 52 1.5 Pressure and Boyle's Law 9 2.2 States and State Functions 53 Biography: RobertBoyle 11 2.3 Equilibrium States and Reversibility 54 1.6 Gay-Lussac's (Charles's) Law 12 2.4 Energy, Heat, and Work 55 1.7 The Ideal Gas Thermometer 14 TheNatureofWork 57 ProcessesatConstant 1.8 The Equation of State for an Ideal Gas 1 Volume 61 ProcessesatConstantPressure: Enthalpy 61 HeatCapacity 62 TheGasConstantandtheMoleConcept 15 1.9 The Kinetic-MolecularTheory of Ideal 2.5 Thermochemistry 64 Gases ExtentofReaction 64 StandardStates 65 1 MeasurementofEnthalpyChanges 67 Calorimetry 69 ThePressureofaGasDerivedfromKineticTheory 19 RelationshipbetweenAt/andA// 69 Temperature KineticEnergyandTemperature 20 Dalton'sLaw DependenceofEnthalpiesofReaction 70 Enthalpiesof ofPartialPressures 22 Graham'sLawofEffusion 22 Formation 73 BondEnthalpies 75 MolecularCollisions 23 2.6 Ideal Gas Relationships 77 1.10 The Barometric Distribution Law 27 ReversibleCompressionatConstantPressure 77 1.11 The Maxwell Distribution of Molecular ReversiblePressureChangeatConstantVolume 79 Speeds and Translational Energies 29 ReversibleIsothermalCompression 80 Reversible TheDistributionofSpeeds 29 TheDistributionof AdiabaticCompression 82 TranslationalEnergy 32 2.7 Ideal Gases 84 1.12 Real Gases 33 TheJoule-ThomsonExperiment 84 VanderWaals Gases 87 CondensationofGases:TheCriticalPoint 33 Usesof SupercriticalFluids 35 KeyEquations 89 Problems 89 SuggestedReading 94 93 VI Contents 3 The Second and Third Laws 4.2 Equilibrium in Nonideal Gaseous Systems 64 ofThermodynamics 95 1 4.3 Chemical Equilibrium in Solution 164 Biography: RudolfJulius Emmanuel Clausius 97 4.4 Heterogeneous Equilibrium 166 3.1 The Carnot Cycle 98 4.5 Tests for Chemical Equilibrium 167 EfficiencyofaReversibleCarnotEngine 102 Carnot's 4.6 Shifts of Equilibrium at Constant Theorem 102 TheThermodynamicScaleof Temperature 168 Temperature 104 TheGeneralizedCycle:TheConcept ofEntropy 105 4.7 Coupling of Reactions 170 3.2 Irreversible Processes 106 4.8 Temperature Dependence of Equilibrium Constants 173 3.3 Molecular Interpretation of Entropy 109 3.4 The Calculation of Entropy Changes 111 4.9 Pressure Dependence of Equilibrium Constants 77 1 ChangesofStateofAggregation 112 IdealGases 11 EntropyofMixing 114 SolidsandLiquids 116 KeyEquations 178 Problems 179 SuggestedReading 184 3.5 The Third Law ofThermodynamics 11 Cryogenics:TheApproachtoAbsoluteZero 120 AbsoluteEntropies 122 5 3.6 Conditions for Equilibrium 123 Phases and Solutions 185 ConstantTemperatureandPressure:TheGibbsEnergy 124 ConstantTemperatureandVolume:TheHelmholtz Energy 125 5.1 Phase Recognition 186 3.7 The Gibbs Energy 126 PhaseDistinctionsintheWaterSystem 186 Phase EquilibriainaOne-ComponentSystem:Water 187 MolecularInterpretation 126 GibbsEnergiesof Formation 128 GibbsEnergyandReversibleWork 129 5.2 Vaporization and Vapor Pressure 190 3.8 Some Thermodynamic Relationships 130 ThermodynamicsofVaporPressure:TheClapeyron Equation 190 TheClausius-ClapeyronEquation 193 MaxwellRelations 130 ThermodynamicEquationsof EnthalpyandEntropyofVaporization:Trouton'sRule 195 State 132 SomeApplicationsofThermodynamic VariationofVaporPressurewithExternalPressure 197 Relationships 133 FugacityandActivity 135 5.3 Classification ofTransitions in Single- 3.9 The Gibbs-Helmholtz Equation 138 Component Systems 198 3.10 Thermodynamic Limitations to Energy 5.4 Ideal Solutions: Raoult's and Henry's Conversion 139 Laws 200 FirstLawEfficiencies 139 SecondLawEfficiencies 140 RefrigerationandLiquefaction 141 HeatPumps 143 5.5 Partial Molar Quantities 203 ChemicalConversion 144 RelationofPartialMolarQuantitiestoNormal KeyEquations 146 Problems 147 SuggestedReading 152 ThermodynamicProperties 205 5.6 The Chemical Potential 207 4 5.7 Thermodynamics of Solutions 209 Chemical Equilibrium 153 Raoult'sLawRevisited 209 Ideal Solutions 212 NonidealSolutions:ActivityandActivityCoefficients 214 Biography: Jacobus Henricus van't Hoff 155 5.8 The Colligative Properties 216 4.1 Chemical Equilibrium Involving Ideal FreezingPointDepression 216 IdealSolubilityand Gases 156 theFreezingPointDepression 219 BoilingPoint EquilibriumConstantinConcentrationUnits 159 Units Elevation 220 OsmoticPressure 221 oftheEquilibriumConstant 160 KeyEquations 224 Problems 224 SuggestedReading 228
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