electrostatic attraction makes g more negative; the

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1 γ=0.5 is like saying the concentrations of H + and A - are less. LeChatelier says this will shift the equilibrium to the right. Electrostatic attraction makes G more negative; The reaction goes further right than expected from ideal behavior. Actual concentration is 0.2M for each ion.

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γ=0.5 is like saying the concentrations of H+ and A- are less. LeChatelier says this will shift the equilibrium to the right.

Electrostatic attraction makes ∆G more negative; The reaction goes further right than expected from ideal behavior. Actual concentration is 0.2M for each ion.

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ATP + H2O ADP + H+ + Pi

3139.997)(5.79 −=−+=−×++=

+

+

×

+∆=+∆=∆

×+=+∆=∆

++=+∆=∆

)1)(1()1()1(1)(

)1)(1()101(1)(

log3.2GlnGG

)1)(1()101(1)(]ATP][X[][P]ADP][H[

ln-31lnGG

1]ATP][X[][P]ADP][H[

ln9lnGG

7

00

'000'

7OH

i

'00'

OH

i

00

2

2

RTQQRT

RTQQRT

RTQQRT

∆G0 = +9 kJ/mol [H+]=1M but, ∆G0’ = -31 kJ/mol [H+]=10-7 M, pH7

3

77

101)1)(1(

)101][]][ −

−+

×=×

==(1)(

ATP][X[PADP][HQOH

i0'

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The famed “high energy phosphate bond” yields little more free energy than a hydrogen bond!

What is K when ∆G0’ = -31 kJ/mol ?

K = 10 ∆G0’/5.7 = 10-31/5.7= 2.7 x 105 i.e., enough but not too much.

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LeChatlier: adding heat (raising temperature) shifts equilibrium (changes K) in the direction that uses the heat (lowers temperature). Endothermic (∆H = +) use heat and lower the T therefore shift to the right (K increases) Exothermic (∆H = negative) gives off heat and raise the T; therefore shift to the left (K decreases)

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Saying the same thing with ∆G0

You will do this for the Lab experiment on the dissolving of butanol in water.

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361 Lec 19 Tue, 1oct13

∆G0’ for forming a base pair

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But, 5’ A-C is accidently = 5’ C-A and 5’ A-G is accidently = 5’ G-A

Independent of which pairs first!

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Table 4.4

Initiation Fees ∆Ginit =+8.1 kJ/mol ∆Hinit =+0.8 kJ/mol

Independent of site of initiation and direction of zipping

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5’...-A-A-...3’ 3’...-T -T-...5’

180 degree rotation 5’...-A-A-...3’

3’...-T -T-...5’

5’...-A-T-...3’ 3’...-T-A-...5’

180 degree rotation 5’...-A-T-...3’

3’...-T-A-...5’

NOT 5’...-T-A-...3’ 3’...-A-T-...5’

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Independent of site of initiation and direction of zipping Ultimately , 1 init and ALL pairing are made regardless of starting point and direction.

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p 141

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From a previous year’s homework #3

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HA --> A- + H+

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1 nM

nM