厦大课件物化chapter

1、1Chapter 11Reaction Equilibrium in Nonideal SystemsPhysical ChemistryNonideal Systems2The Equilibrium ConstantFor the ideal-gas reaction(4.36)the equilibrium condition(11.2)*(11.1)(11.3)Physical ChemistryNonideal Systems3The Equilibrium Constant(11.4)*(11.3)(11.5)*(11.6)*Standard equilibrium constan

2、tActivity equilibrium constantEquilibrium constantPhysical ChemistryNonideal Systems4Reaction Equilibrium in nonelectrolyte solutions(11.6)*(11.7)(11.8)(11.9)Physical ChemistryNonideal Systems5Reaction Equilibrium in nonelectrolyte solutions(11.6)*Physical ChemistryNonideal Systems6Reaction Equilibr

3、ium in electrolyte solutionsMany ionic reactions in solution are acid-base reactions.(11.10)Brnsted definition of acid/baseAcid: a proton donorBase: a proton acceptorwater: amphoteric, either a proton donor or a proton acceptor(11.6)*(11.11)The standard state of the solvent H2O is pure H2O.Physical

4、ChemistryNonideal Systems7Reaction Equilibrium in electrolyte solutionsIn aqueous solutionsFor the H2O ionizationOmission of the solvents activity.For dilute aqueous solutions(11.12)*dilute aqueous solutionPhysical ChemistryNonideal Systems8Reaction Equilibrium in electrolyte solutionsFor the ioniza

5、tion of the weak acid HX in aqueous solution(11.13)(11.14)In dilute solution(11.15)dilute solutionThe pair of ions H3O+/X-Physical ChemistryNonideal Systems9Reaction Equilibrium in electrolyte solutionsFor an aqueous solution of the weak acid HX with stoichiometric molality m, the degree of dissocia

6、tion (11.15)dilute solutionPhysical ChemistryNonideal SystemsKa has a dimension of m10Reaction Equilibrium involving pure solids or pure liquidsMany reactions involve one or more pure solids or liquids.(11.13)equilibrium condition(11.2)*(11.20)pure solid or liquidat const. TPhysical ChemistryNonidea

7、l Systems11Reaction Equilibrium involving pure solids or pure liquidsat const. T(11.20)pure solid or liquidpure solid or liquid, const. T(11.22)(11.21)pure solid or liquid, const. Tpure solid or liquid(11.23)Since solids and liquids are rather pressibleVm,i is independent of PPhysical ChemistryNonid

8、eal Systems12Reaction Equilibrium involving pure solids or pure liquidsConsider the equilibrium(11.13)If P is not very high(11.24)(11.25)Must include solids!Physical ChemistryNonideal Systems13Reaction Equilibrium involving pure solids or pure liquidsConsider the equilibrium between a solid salt(11.

9、13)(11.26)Solubility product (SP) equilibrium constant(10.43)(11.27)*Valid for any salt (only slightly soluble in water)!Physical ChemistryNonideal Systems14Using the limiting law to analyze an equilibriumAnswer.Physical ChemistryNonideal SystemsThe solubility of silver chloride in water at 25oC is

10、1.27410-5 mol/kg. Calculate (a) the standard reaction Gibbs energy for and (b) the solubility of silver chloride in 0.020 mol/kg K2SO4(aq).(a) The equilibrium constant for the dissolution of AgCl isThe ionic strength of the solution is (1:1 electrolyte)15Using the limiting law to analyze an equilibr

11、iumAnswer.Physical ChemistryNonideal Systems(a) The equilibrium constant for the dissolution of AgCl isThe ionic strength of the solution is (1:1 electrolyte)(10.69)16Using the limiting law to analyze an equilibriumAnswer.Physical ChemistryNonideal Systems(b) The ionic strength of the solution is (1

12、:2 electrolyte)(10.69)The solubility of potassium sulfate in water is 1.710-5 mol/kg.17HomeworkNonideal SolutionsPhysical ChemistryP337, Section 11.111.1P337, Section 11.311.5*, 11.6, 11.9, 11.14P338-339, Section 11.411.27, 11.30, 11.31, 11.3218Reaction Equilibrium in nonideal gas mixturesThe activi

13、ty ai of component i of a nonideal gas mixture is(11.28)(11.29)(11.30)Physical ChemistryNonideal Systems(10.96)(10.99)*19The Equilibrium Constant(T dependence)(11.31)(11.32)*Physical ChemistryNonideal Systems20The Equilibrium Constant (P dependence)(11.31)(11.33)Physical ChemistryNonideal Systems(9.

14、31)21Summary of Standard StatesPhysical ChemistryNonideal SystemsSubstance Standard stateGas (pure or in gas mixture)Pure ideal gas at 1 bar and TPure liquid or pure solidPure substance at 1 bar and TSolution component, IPure i at T and P of solutionSolvent APure A at T and P of solutionNonelectrolyte solute: IIFictitious statexi=1=II,iElectrolyte solute: m-scaleFictitious state =1= m,i /moTable 11.122Gibbs Energy Change for a Reaction(11.34)(11.37)Physical Che