Concise Physical Chemistry

405 Pages·2013·2.41 MB·English

by  Rogers, Donald W.

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CONCISE PHYSICAL
CHEMISTRY
DONALDW.ROGERS
DepartmentofChemistryandBiochemistry
TheBrooklynCenter
LongIslandUniversity
Brooklyn,NY
AJOHNWILEY&SONS,INC.,PUBLICATION
P1:OTA/XYZ P2:ABC
fm JWBS043-Rogers October8,2010 21:3 PrinterName:YettoCome
P1:OTA/XYZ P2:ABC
fm JWBS043-Rogers October8,2010 21:3 PrinterName:YettoCome
CONCISE PHYSICAL CHEMISTRY
P1:OTA/XYZ P2:ABC
fm JWBS043-Rogers October8,2010 21:3 PrinterName:YettoCome
P1:OTA/XYZ P2:ABC
fm JWBS043-Rogers October8,2010 21:3 PrinterName:YettoCome
CONCISE PHYSICAL
CHEMISTRY
DONALDW.ROGERS
DepartmentofChemistryandBiochemistry
TheBrooklynCenter
LongIslandUniversity
Brooklyn,NY
AJOHNWILEY&SONS,INC.,PUBLICATION
P1:OTA/XYZ P2:ABC
fm JWBS043-Rogers October8,2010 21:3 PrinterName:YettoCome
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Concisephysicalchemistry/byDonaldW.Rogers.
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Summary:“Thisbookisaphysicalchemistrytextbookthatpresentstheessentialsofphysical
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Comprisedof21chapters,thebookaddressesidealgaslaws,realgases,thethermodynamicsofsimple
systems,thermochemistry,entropyandthesecondlaw,theGibbsfreeenergy,equilibrium,statistical
approachestothermodynamics,thephaserule,chemicalkinetics,liquidsandsolids,solutionchemistry,
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ISBN978-0-470-52264-6(pbk.)
1.Chemistry,Physicalandtheoretical–Textbooks. I.Title.
QD453.3.R632010
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2010018380
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CONTENTS
Foreword xxi
Preface xxiii
1 IdealGasLaws 1
1.1 EmpiricalGasLaws, 1
1.1.1 TheCombinedGasLaw, 2
1.1.2 Units, 2
1.2 TheMole, 3
1.3 EquationsofState, 4
1.4 Dalton’sLaw, 5
PartialPressures, 5
1.5 TheMoleFraction, 6
1.6 ExtensiveandIntensiveVariables, 6
1.7 Graham’sLawofEffusion, 6
MolecularWeightDetermination, 6
1.8 TheMaxwell–BoltzmannDistribution, 7
Figure1.1TheProbabilityDensityforVelocitiesofIdeal
GasParticlesatT (cid:2)=0., 8
Boltzmann’sConstant, 8
Figure1.2AMaxwell–BoltzmannDistributionOver
DiscontinuousEnergyLevels., 8
1.9 ADigressionon“Space”, 9
Figure1.3TheGaussianProbabilityDensityDistribution
in3-Space., 10
TheGaussianDistributionin2-and3-and4-Space, 10
v
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vi CONTENTS
1.10 TheSum-Over-StatesorPartitionFunction, 10
Figure1.4TheProbabilityDensityofMolecularVelocities
inaSphericalVelocitySpace., 12
ProblemsandExercises, 12
Exercise1.1, 12
Exercise1.2, 13
Problems1.1–1.13, 15–16
ComputerExercise1.14, 16
Problems1.15–1.18, 16–17
2 RealGases:EmpiricalEquations 18
2.1 ThevanderWaalsEquation, 18
2.2 TheVirialEquation:AParametricCurveFit, 19
2.3 TheCompressibilityFactor, 20
Figure2.1AQuadraticLeast-SquaresFittoan
ExperimentalDataSetfortheCompressibilityFactorof
Nitrogenat300KandLowPressures(Sigmaplot11.0(cid:1)C)., 21
File2.1PartialOutputFromaQuadraticLeast-Squares
CurveFittotheCompressibilityFactorofNitrogenat
300K(SigmaPlot11.0(cid:1)C)., 22
Figure2.2TheSecondVirialCoefficientofThreeGasesas
aFunctionofTemperature., 22
2.3.1 CorrespondingStates, 23
Figure2.3The Z = f(p)CurveforTwoDifferentGasesor
fortheSameGasatTwoDifferentTemperatures., 23
2.4 TheCriticalTemperature, 24
Figure2.4ThreeIsothermsofavanderWaalsGas., 24
Figure2.5ConversionofaLiquidtoItsVaporWithout
Boiling(1–4)., 25
2.4.1 SubcriticalFluids, 25
2.4.2 TheCriticalDensity, 26
Figure2.6Densityρ CurvesforLiquidandGaseous
Oxygen., 26
2.5 ReducedVariables, 27
2.6 TheLawofCorrespondingStates,AnotherView, 27
Figure2.7CompressibilityFactorsCalculatedfromthe
vanderWaalsConstants., 28
2.7 DeterminingtheMolarMassofaNonidealGas, 28
ProblemsandExercises, 28
Exercise2.1, 28
Figure2.8Boyle’sLawPlotforanIdealGas(lowercurve)
andforNitrogen(uppercurve)., 29
Exercise2.2, 30
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CONTENTS vii
Table2.1ObservedRealGasBehaviorfrom10to100bar
Expressedas(p,pV )., 30
m
Figure2.9ExperimentalValuesof pV =z(p)vs. pfora
m
RealGas., 30
Table2.2ObservedRealGasBehaviorExpressed
as(p,pV )., 31
m
Figure2.10QuadraticRealGasBehavior., 32
Problems2.1–2.15, 32–34
Figure2.11CubicRealGasBehavior., 34
3 TheThermodynamicsofSimpleSystems 35
3.1 ConservationLawsandExactDifferentials, 35
3.1.1 TheReciprocityRelationship, 36
3.2 ThermodynamicCycles, 37
Figure3.1DifferentPathTransformationsfromAtoB., 38
3.2.1 Hey,Let’sMakeaPerpetualMotionMachine!, 38
3.3 LineIntegralsinGeneral, 39
Figure3.2DifferentSegmentsofaCurvedRod., 39
3.3.1 MathematicalInterlude:TheLengthofanArc, 40
Figure3.3PythagoreanApproximationtotheShort
ArcofaCurve., 40
3.3.2 BacktoLineIntegrals, 41
3.4 ThermodynamicStatesandSystems, 41
3.5 StateFunctions, 41
3.6 ReversibleProcessesandPathIndependence, 42
Figure3.4TheEnergyChangeforReversibleExpansionof
anIdealGas., 43
3.7 HeatCapacity, 44
3.8 EnergyandEnthalpy, 44
3.9 TheJouleandJoule–ThomsonExperiments, 46
Figure3.5InversionTemperatureT asaFunctionof
i
Pressure., 47
3.10 TheHeatCapacityofanIdealGas, 48
Table3.1HeatCapacitiesandγ forSelectedGases., 48
Figure3.6.TypicalHeatCapacityasaFunctionof
TemperatureforaSimpleOrganicMolecule., 50
3.11 AdiabaticWork, 50
Figure3.7TwoExpansionsofanIdealGas., 51
ProblemsandExample, 52
Example3.1, 52
Problems3.1–3.12, 52–55
Figure3.8C =DiagonalAlongx =1to y =1., 53
Figure3.9C=Quarter-CircularArc., 53