双语物理化学之统计热力学的应用解决方案.ppt

Justification 20.4 - continued Now we can write As we know, which gives Justification 20.4 - continued In terms of the stoichiometric numbers, we would write We shall illustrate the application of eqn 54 to an equilibrium in which a diatomic molecule X2 dissociates into its atoms: (b) A dissociation equilibrium According to eqn 54 ( with a = 1, b = 0, c = 2, and d = 0): with Where D0 (X-X) is the dissociation energy of the X-X bond. The standard molar partition function of the atoms X are (b) A dissociation equilibrium - continued gX is the degeneracy of the electronic ground state of X. The diatomic molecule X2 also has rotational and vibrational degrees of freedom, so its standard molar partition function is The standard molar partition function of the atoms X are Where gX2 is the degeneracy of the electronic ground state of X2. Then the K is (b) A dissociation equilibrium - continued Therefore the K is All the quantities in this expression can be calculated from spectroscopic data. The are defined in Table 20.3 and depend on the masses of the species and the temperature; the expression for rotational and vibrational partition functions are also available in Table 20.3 and depend on the rotational constant and vibrational wavenumber of the molecule. Oct 29, 2010 Example 20.7 Evaluating an equilibrium constant Method: The partition function required are specified in eqn 59. The are evaluated by using the expressions in Table 20.3. For a homonuclear diatomic molecule, . In the evaluation of kT/p0 use p0 = 105 Pa and 1 Pa m3 = 1 J. K and partition function Evaluate the K for the dissociation of Na2 (g) ? 2 Na (g) at 1000 K from the following data: B = 0.1547cm-1. The Na atoms have doublet ground terms. Oct 29, 2010 Table 20.3 Contributions to the molecular partition function (partial ) Example 20.7 Evaluating an equilibrium constant - continued K and partition function Answer: The partition func