双语物理化学之统计热力学的应用.pptVIP

Chapter 20;Chapter 20 / Oct15, 2010;Introduction;Chapter 20 ;Thermodynamic functions;Chapter 20 ;(c) The enthalpy, H ;(d) The Gibbs energy ;20.2 The molecular partition function;20.2 The molecular partition function;20.2 The molecular partition function;(a) The translational contribution;分子平动配分函数 ;其中;同理 ;例2 求算25℃及105Pa时，1mol NO气体分子的;(b) The rotational contribution;(b) The rotational contribution;Example 20.2 Evaluating the rotational partition function explicitly-I;Example 20.2 Evaluating the rotational partition function explicitly-II;Where A, B, and C are the rotational constants of the molecule. ;A useful way of expressing the T above which the rotational approximation is valid is to introduce the rotational temperature, . Then ‘ high T’ means ;Note !! : you will have to read the justification on how to prove the above eqns after class.;The same care must be exercised for other types of symmetrical molecules, and for nonlinear molecule we write ;In NH3 , there are three indistinguishable orientations around its C3 axis. For CH4, any of three 120 0 rotations about any of its four C-H bonds leaves the molecule in an indistinguishable state, so the symmetry number is . ;The rotational contribution;rotations;E: the identity, consist of doing nothing. The corresponding symmetry element is the entire body. Because every molecule is indistinguishable from itself if nothing is done to it.;A more formal way of arriving at the value of symmetry number is to note that is the order (the number of elements) of the rotational subgroup of the molecule. The rotational subgroup of H2O is {E, C2}, so . The rotational subgroup of NH3 is {E, 2C3}, so . The recipe makes it easy to find the symmetry numbers for more complicated molecules. The rotational subgroup of CH4 is obtained from the T character table as {E, 8C3, 3C2}, so .