化学平衡、熵、gibbs函数.ppt

B. Partial Pressure Change from Volume Change T constant, V?V/x (compressing), pi ? x pi Σ?B (g) 0, x Σ? B(g) 1, J K? Equilibrium shifts to reactants ii) Σ?B (g) 0, x Σ? B(g) 1, J K? Equilibrium shifts to products Σ? B(g) = 0, x Σ?B(g) = 1, J = K? Equilibrium does not shift Compression of a reaction mixture at equilibrium tends to drive the reaction in the direction that reduces the number of gas phase molecules 3) 温度对化学平衡的影响 ln ( k2 / k1 ) = ( Ea /R ) ( 1/ T1 – 1 / T2 ) = Ea (T2 –T1 ) / RT1T2 ? r H m? 0 ( exothermic ): T2 T1 , K2 K1 [ Raising the temperature of an exothermic reaction favors the formation of reactants ] ? r H m? 0 ( endothermic ): T2 T1 , K2 K1 [ Raising the temperature of an endothermic reaction favors the formation of products ] 4 ) Le Chateliers principle A change in any of factors that determine the equilibrium conditions of a system will cause the system to change in such a manner as to reduce or counteract the effect of the change. N2(g) + 3H2 (g) ? 2 NH3(g) ? r H m? = -99.22kJ? mol-1 T: 733K-823K, p: 32MPa 四. Spontaneous Change and Entropy(自发变化、熵) 1. Spontaneous change : a change that occurs without outside intervention. Non-spontaneous change : a change that occurs only if it is driven by external force . Notes: a) A tendency to change. b) Need not fast c) A definite direction. d) The reverse process is not spontaneous Enthalpy and Spontaneous Change （焓和自发变化） Endothermic Process:吸热过程 Exothermic process:放热过程 Disorder, Number of Microstate and Entropy 混乱度，微观状态数和熵 i. Disorder: Numbers of microstate( thermodynamic probability): 微观状态数（热力学几率） 2. Mathematic probabilities: 1 / 2, 1 / 2. Total probabilities: P = 1 / 2+ 1/2 = 1 ii. Numbers of Microstate and Entropy: Numbers of microstate( thermodynamic probability):