1. CHAPTER 16: SPONTANEITY, ENTROPY, & FREE ENERGY Dr. Aimée Tomlinson Chem 1212

2. What you should know about thermochemistry Review from Chapter 8

3. Enthalpy

4. Hess’s Law

5. Hess’s Law Example

6. Spontaneous Processes & Entropy Section 16.1-16.2

7. Oh to be spontaneous

8. Entropy Defn: system disorder, randomness, motion

9. Entropy & Probability Skip it – YIPPEE!!! Section 16.3

10. Effect of Temperature on Entropy Section 16.4

11. Effect of T on S Entropy changes as a consequence of heat flow Heat flow at lower T has a greater impact

12. System, Surroundings and heat  The sign is dependent on the direction of heat flow  The magnitude is dependent on T

13. Mathematically

14. Two Directions of Heat Flow

15. Entropy Changes in Chemical Reactions Sections 16.5

16. Laws of Thermodynamics

17. Standard Molar Entropy Defn: Entropy of a substance at P = 1 bar & T = 298.15K For homework you will be asked to look up values in the appendix

18. Example Entropy of Reaction C 3 H 8(g) + 5O 2(g)  3CO 2(g) + 4H 2 O (g) Compound S ⁰ (J/mol K) C 3 H 8(g) 269.9 O 2(g) 205.0 CO 2(g) 213.6 H 2 O (g) 188.7

19. Entropy & the Second Law of Thermodynamics Section 16.6

20. The Second Law of Thermo  If we increase the number of gas moles from reactants to products we increase  S univ  Recall the previous example: C 3 H 8(g) + 5O 2(g)  3CO 2(g) + 4H 2 O (g) – we increase from 6 to 7 gas moles so as expected our  S univ > 0

21. Free Energy Section 16.7

22. Gibb’s Free Energy – meet  G There are two driving forces for any chemical reaction:  Formation of low energy products from high energy reactants,  H rxn  Formation of high entropy products from low entropy reactants,  S rxn

23. How Gibb’s Works

24. Gibb’s Example I The standard enthalpy and entropy changes for the combustion of methane are -801 kJ and -5 J/K, respectively Is the reaction spontaneous under standard conditions?

25. Free Energy & Chemical Reactions Section 16.8 & 16.9

27. Gibb’s Example II Is the reaction below exothermic or endothermic? Is the reaction spontaneous at all temperatures? Determine the Gibb’s free energy from the given data as well as using the mathematical equation Compound ΔH⁰f (kJ/mol) S o (J/mol*K) ΔG⁰f (kJ/mol) N 2(g) 0.0191.50.0 H 2(g) 0.0130.60.0 NH 3(g) -46.1192.3-16.5

28. Section 16.10 Free Energy & Pressure

29. Relationship between Gibb’s & P

30. Gibb’s Example III Determine the Gibb’s free energy for the reaction below. NO (g) O 3(g) NO 2(g) O 2(g) ΔG ⁰ (kJ/mol) 87163520 P (atm)1x10 -6 2x10 -6 1x10 -7 1x10 -3

31. Sections 16.11 Free Energy & Equilibrium

32. Relationship between Gibb’s & K At equilibrium ΔG = 0

33. Relationship between Gibb’s & K

34. Plotting to get Enthalpy & Entropy