1. Chapter 17 Spontaneity, entropy and free energy

2. Spontaneous l A reaction that will occur without outside intervention. l We need both thermodynamics and kinetics to describe a reaction completely. l Thermodynamics compares initial and final states. l Kinetics describes pathway between.

3. Thermodynamics l 1st Law- the energy of the universe is constant. l Keeps track of thermodynamics doesn’t correctly predict spontaneity. l Entropy (S) is disorder or randomness l 2nd Law the entropy of the universe increases.

4. Entropy l Defined in terms of probability. l Substances take the arrangement that is most random. l Calculate the number of arrangements for a system.

5. l 2 possible arrangements l 50 % chance of finding the left empty

6. l 4 possible arrangements l 25% chance of finding the left empty l 50 % chance of them being evenly dispersed

7. l 4 possible arrangements l 8% chance of finding the left empty l 50 % chance of them being evenly dispersed

8. Gases l Gases completely fill their chamber because it is more random than to leave half empty. l S solid <S liquid <<S gas l there are many more ways for the molecules to be arranged as a liquid than a solid. l Gases have a huge number of possible arrangements.

9. Entropy l Solutions form because there are many more possible arrangements of dissolved pieces than if they stay separate. l 2nd Law of thermodynamics  S univ =  S sys +  S surr If  S univ is positive the process is spontaneous. If  S univ is negative the process is spontaneous in the opposite direction.

10. For exothermic processes  S surr is positive. For endothermic processes  S surr is negative. Consider this process H 2 O(l)  H 2 O(g)  S sys is positive  S surr is negative  S univ depends on temperature.

11. Temperature and Spontaneity l Entropy changes in the surroundings are determined by the heat flow. l An exothermic process is favored because by giving up heat the entropy of the surroundings increases. The size of  S surr depends on temperature  S surr = -  H/T

12.  S sys  S surr  S univ Spontaneous? --- +++ +-? +-? Yes No, Reverse At Low temp. At High temp.

13. Gibb's Free Energy  G=  H-T  S at constant temperature l Divide by -T -  G/T = -  H/T-  S -  G/T =  S surr +  S -  G/T =  S univ If  G is negative at constant T and P, the process is spontaneous.

14. Let’s Check For the reaction H 2 O(s)  H 2 O(l)  Sº = 22.1 J/K mol  Hº =6030 J/mol Calculate  G at 10ºC and -10ºC Look at the equation  G=  H-T  S Spontaneity can be predicted from the sign of  H and  S.

15.  G=  H-T  S HH SS Spontaneous? +- At all Temperatures ++ At high temperatures, “entropy driven” -- At low temperatures, “enthalpy driven” +- Not at any temperature, Reverse is spontaneous

16. Third Law of Thermo l The entropy of a pure crystal at 0 K is 0. l This gives us a starting point. l All others must be>0. l Standard Entropies Sº ( at 298 K and 1 atm) of substances are listed. Products - reactants to find  Sº l More complex the molecule, the higher Sº.

17. Free Energy in Reactions  Gº = standard free energy change. l Free energy change that will occur if reactants in their standard state turn to products in their standard state. l Can’t be measured directly, can be calculated from other measurements.  Gº=  Hº-T  Sº l Use Hess’s Law with known reactions.

18. Free Energy in Reactions There are tables of  Gº f. l Products-reactants again. l The standard free energy of formation for any element in its standard state is 0. l Remember- Spontaneity tells us nothing about rate.

19. Free energy and Pressure  G =  Gº +RTln(Q) where Q is the reaction quotients (P of the products /P of the reactants all raised to their coefficients). CO(g) + 2H 2 (g)  CH 3 OH(l) l Would the reaction be spontaneous at 25ºC with the H 2 pressure of 5.0 atm and the CO pressure of 3.0 atm?  Gº f CH 3 OH(l) = -166 kJ  Gº f CO(g) = -137 kJ  Gº f H 2 (g) = 0 kJ

20. How far?  G tells us spontaneity at current conditions. When will it stop? l It will go to the lowest possible free energy which may be an equilibrium. At equilibrium  G = 0, Q = K  Gº = -RTlnK

21.  Gº K =0=1 1 >0<1

22. Temperature dependence of K  Gº= -RTlnK =  Hº - T  Sº ln(K) =  Hº/R(1/T)+  Sº/R

23. Free energy And Work l Free energy is that energy free to do work. l The maximum amount of work possible at a given temperature and pressure. l Never really achieved because some of the free energy is changed to heat during a change, so it can’t be used to do work.