[物理化学英语课件]统计热力学Elementary_statistical_thermodynamics.ppt

Chapter8Elementarystatisticalthermodynamics

8.1IntroductionStatisticalthermodynamics,orstatisticalmechanics,isthestudyofthemicroscopicbehaviorsofthermodynamicsystemsusingstatisticalmethodsandprobabilitytheory.TheessentialprobleminstatisticalthermodynamicsistodeterminethedistributionofagivenamountofenergyEoverNparticlesinasystem.Themacroscopicproperties,suchasthermodynamicenergy,heatcapacity,etc.,canbecalculatedintermsofpartitionfunctions.Statisticalthermodynamicsisabridgeofconnectingbetweenmacroscopicandmicroscopicpropertiesofasystem.Definitionofstatisticalthermodynamics

TherearetwokindsofsystemsInteractingsystem(相倚子系统)Non-interactingsystem(独立子系统，forinstance,idealgas)Onlythelatterwillbeintroducedinthischapter.

TwokindsofparticlesIdenticalparticles,orindistinguishableparticles(suchasgaseousmolecules),isalsocallednon-localizedparticles.Distinguishableparticles(Suchastheatomsincrystal),isalsocalledlocalizedparticles.

8.2Energylevelanditsdegeneracy012345Energylevelsaresaidtobedegenerate,ifthesameenergylevelisobtainedbymorethanonequantummechanicalstate.Theyarethencalleddegenerateenergylevels.Thenumberofquantumstatesatthesameenergyleveliscalledthedegreeofdegeneracy.

Amolecularenergystateisthesumofanelectronic(e),nuclear(n),vibrational(v),rotational(r)andtranslational(t)component,suchthat:

ThedegreeoffreedomofmovementTranslation:x,y,zF=3

RotationForlinearmolecules,F=2Fornon-linearmolecules,F=3

VibrationApolyatomicmoleculecontainingnatomshas3ndegreesoffreedomtotally.Threeofthesedegreesoffreedomcanbeassignedtotranslationalmotionofthecenterofmass,twoorthreetorotationalmotion.3n-5foralinearmolecule;3n-6foranonlinearmolecule

CO2has3×3-5=4degreesoffreedomof