8StatisticalThermodynamics概论.ppt

8-5 Statistical thermodynamics 1. Internal energy(内能) 1)the thermal energy of translational motion of a gas: 2)the average rotational motion of a linear molecule: a nonlinear molecule: 3)The vibrational motion: 2. Entropy(熵) the statistical thermodynamic definition of entropy S is: W is the statistical weighting for a particular distribution of populations in each molecular energy level therefore: 1) Translational contribution to the entropy terms 2) Rotational contribution to the entropy terms A linear molecule: A nonlinear molecule: 3) Vibrational contribution to the entropy terms 4) Electronic contribution to the entropy terms 3. Pressure To express the pressure in terms of the partition function: Partition function 4. Enthalpy(焓) The enthalpy is related to the internal energy: 5. Heat capacity The heat capacity at constant volume is: 6. The ground-state energy The energy of gas would have if every molecule were in its lowest energy level. It is also the internal energy or the enthalpy would have at 0K(E0=H0) 基态: 是指原子的能量最低状态.处于基态的原子最为稳定.不受外界作用时,原子可无限长时间处于基态 ,因此原子基态能级的宽度为零.通常在没有外加激发条件下,由于热运动,并非全部原子都处于基态.热平衡时,原子在各能态上的分布遵从玻耳兹曼分布律.在常温下,绝大多数原子处于基态.在外加激发条件下,原子吸收能量跃迁到较高的原子激发态 The thermal enthalpy at some temperature of interest T: 8. Statistical Thermodynamics A chemically reacting flow 1)Thermodynamic 2)Chemical kinetic 3)Transport quantities This chapter gives an overview of the fundamental physical basis for the thermodynamic(Enthalpy, Entropy and heat capacity) properties of chemical species. Method: Statistical thermodynamics Derived from well-known relationships, such as Newton’s second law, the ideal gas law, and so on.. 8-1 Kinetic theory of gas(气体分子运动论) The assumptions for the kinetic theory of gas: 1)a gas is composed of small, structureless particles in randomly directed translational motion; 2)Molecules interact with one another namely instantaneous collisions; 3)Collis