Topic 4 The thermodynamics of mixtures

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Presentation transcript:

Topic 4 The thermodynamics of mixtures Key point: Solution

Is the properties of substances in a mixture the same as being single component? Why? Yes or No The same person, would be in the same character in different groups?

The interaction between molecules A+B A-A B-B A-B A B + B-B A-A Solution A-A ≈B-B A-A < B-B A-A > B-B Ideal solution A-B ≈ A-A≈B-B A-B ≠A-A ≠ B-B Real solution Composition of solution: m(mol.kg-1) , c(mol.L-1), w(g/kg) , x Small amount of solute B/large amount solvent A----Deluted solutions A-B/A-A

Ideal solutions (1) (2) (3) (4)

Description of properties of mixtures Components in a solution: 1,2, 3….k Induced by composition variation Z: U, H, S, A, G….

4.1 Definition of partial molar quantities Constant T and P partial molar quantity of substance i

Description of properties of solutions B: any component in the solution Gibbs-Duhem equation Binary system: A,B

Partial molar volume : Meaning, measurement and application Example: ethanol+water=alcohol Binary system:A,B V nB Measurement

4.2 Partial molar Gibbs energy: chemical potential μ ---By Gibbs and Lewis At constant temperature and pressure, ( )T,P

Thermodynamic relationship for mixed system

The new justification for composition variation of mixed system The maximum efficient (non-expansion ) work The drive force of the composition variation of mixed system The energy resource of doing work

Example 1: Phase equilibrium A:Water B:CCl4 a: I2 a/B a/A dna Happen if It can happen Get equilibrium The reverse process can happen The chemical potential of the same substance in different phases being in equilibrium are equal

Example 2: Chemical reaction A,B A,B,C νAA+νBB→νCC If dζ Initial It can happen Get equilibrium The reverse process can happen The drive force of chemical reaction

4.3 Chemical potentials of substances (1) Pure ideal gases Chemical potential at standard state

(2) Mixed ideal gases Chemical potential of pure B at T,P (3) For real gases (4) For mixed real gases

< (5) Pure liquids Gas-liquid phase equalibrium 100℃,PΘ,H2O(l) Comparing the chemical potentials: 100℃,PΘ,H2O(l) 100℃,PΘ,H2O(g) 100℃,2PΘ,H2O(l) 100℃,PΘ,H2O(g) 100℃,PΘ,H2O(l) 100℃,2PΘ,H2O(g) 100℃,2PΘ,H2O(g) 100℃,2PΘ,H2O(l) <

(6) Mixed liquids---solutions PB = ? Raoult’s law and Henry’s law

4.4 Raoult’s law and Henry’s law P A(solvent) B(solute) Gas A, (B) liquid P total Raoult’s law xA For ideal solution A solvent B solute For real solution

Chemical potential of components of ideal solutions For real solutions

Henry’s Law Relating Kx,B and A-A interaction is stronger than B-B A(solvent) B(solute) Gas A, B liquid xB kx,B A B xB很小时 xB很大时 p Relating Kx,B and A-A interaction is stronger than B-B B is easier to vaporize Kx,B > A-A interaction = B-B Kx,B =

Ideal diluted solution Solvent follow Raoult’s law Solute follow Henry’s law

Homework Excises: A: P191:7.4 7.9 P93: 5 P98: 11 Preview: Examples and explanation of Colligative properties of diluted solution Y:3.6,3.7 A: 7.4-7.8 Excises: A: P191:7.4 7.9 P93: 5 P98: 11