A. Much too slow. C. Basically about right. E. Much too fast

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1 Geeral Questio 1 t this poit, we have bee i this class for about a moth. It seems like this is a good time to take stock of how the class is goig. g I promise ot to look at idividual resposes, so be cadid! Is the pace of the course. Much too slow. Too slow C. asically about right D. Too fast E. Much too fast

2 Geeral Questio 2 Is the degree of rigor i the course. Much too low. Too low C. asically about right D. Too rigorous E. Much too rigorous

3 Chemical otetial Util ow, we have oly cosidered systems of fixed compositio. I order to study reactio thermodyamics, we eed to kow how the Gibbs eergy chages with the compositio of reactats ad products. This is best doe with a very importat costruct, the Chemical otetial. We geeralize G to the form G = G(T,, 1, 2,... ), where i is the umber of moles of substace i. Writig the differetial, dg G G G dg dt d d 1 T 1,, T,, T,,, 1 1 1

4 Chemical otetial... G G G dg dt d d 1 T 1,, T,, T,,, G G d T,,, T,,, 2 3 d The Chemical potetial i depeds upo, T ad the compositio of a mixture. Why Compositio?? (Compare H 2 aloe with a mixture of H 2 ad O 2. Which has more chemical potetial??) Well, we eed a few more words ad thikig about reactios. The aswer (ad thought) lies i choosig the d i.

5 Chemical otetial (2) G G G G dg dt d d d T T,, T,, T,, T,, To see the importace of ad d i, here is a example. Cosider a process i which d i moles of compoet are trasferred from state (at ) to state (at ). Thus, at costat T ad, dg d d d i i i so dg 0 if This meas that reactios proceed to the lowest chemical p potetial. Thus is completely aalogous to the potetial eergy i mechaical systems or a electrical potetial.

6 Chemical otetial (3) G G G G dg dt d d d T T,, T,, T,, T,, For a specific example, cosider the cis tras isomerizatio of dichloroethylee. Let d moles of compoet (tras) be trasferred t from state (at ) to state t (at ). Defie the extet of reactio,, H Cl i C C Cl H g g i Cl H C cos ' t total where 0 1. d is the chage i umber of moles of reactats ad products d d d d C Cl H total

7 Chemical otetial (4) G G G G dg dt d d d T T,, T,, T,, T,, Calculate the chage i the Gibbs eergy as a result of the progress of the reactio. t costat T ad, d d ad d d, so dg d d d d G ad, T G R G R reactio goes forward reactio goes backward mixture at equilibrium 0 1 compositio

8 Chemical otetial (5) Startig with a arbitrary mixture of reactats ad products, the mixture evolves util G R = 0. Nothig, however has bee said about either the rate of the process or the molecular ature of the process. Cosider a slightly more complex reactio: a g b g with ad the partial pressures of the compoets. 0 RT l 0 0 RT l 0 0 = 1 bar 0 is the chemical potetial per mole at 1 bar, the Stadard Chemical otetial We ca readily dl write GG R = b -a ad use expressios above to get b G b a RT b l RT a l G RT l R 0 0 R a 0

9 Chemical otetial (6) a g b g at equilibrium b G b a brt l art l 0 0 G RT l R R a Stadard Gibbs Eergy 0 Chage G G o RT lk R R t equilibrium, G R = 0 ad we have G o RT l K R K, the equilibrium costat for reactio (i pressure) very useful coectio betwee G ad the equilibrium costat

10 The Equilibrium Costat, K Cosider the gas-phase reactio: a + b yy + zz Similar aalysis gives the thermodyamic equilibrium costat K K y z o Y Z a b (Usual stadard state is 1 bar pressure) G = RT l K The same thig ca be doe usig cocetratios, rather tha pressures.

11 Chemical otetial a b yy zz at other pressures G = RT l K

12 Cocetratio Equilibrium Costat, K C Cosider agai the gas-phase reactio: a + b yy + zz RT c RT, where c is ow a cocetratio. V Defie the stadard equilibrium costat K C Y Z o K C a b (Usual stadard state is 1 mol dm -3 ) y G = RT l K C Note that K = K C (RT) y z a b z

13 Le Chatelier riciple Whe a chemical system at equilibrium is disturbed, it re-attais equilibrium by udergoig a et reactio that reduces the effect of the disturbace. 2 NO 2 (g) N 2 O 4 (g) I which directio does the reactio shift whe: # moles of N 2 O 4 is icreased left The total pressure is icreased (at costat volume) right

14 CocepTest #1 2 NO 2 (g) N 2 O 4 (g) (brow) (colorless) The dimerizatio of NO 2 is a exothermic process. If a sealed tube cotaiig a mixture of NO 2 ad N 2 O 4 is cooled, what is the result?. The color itesity deepes. The color itesity lightes C. There is o chage i color itesity D. It explodes

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