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t-Bu Cl
H3CH H CH3
H H3C H HH CH3 H H CH3
OH
H H H3C H Cl
H3C HH CH3 H3C HCH3 CH3 t-Bu
Cl
CH3
H3C H HCH3 H3C CH3 H3CCH3 t-Bu
H H
H3CH HH H CH3 HH H3C H
H HCH3 H CH3 OH
CH3
4 + 6 + 6 = 16 kJ/mol 11 - 4 = 7 kJ/mol 2x(11.4) - 4x(3.8) 2x(1.0) + 2x(2.1)
= 7.6 kJ/mol = 6.2 kJ/mol
∆Go = -RT lnKeq Keq = 5.7 x 10 -2
Keq = 1.4 x 10 -3 Keq = 4.46 x 10 -2 Keq = 7.92 x 10 -2
TS
E TS E
∆G
SM
∆ Go ∆G
= -120
P
SM ∆ Go
P = +20
E ∆G E TS
∆G
P SM
P
∆Go = 16 o
∆G = -2.7
SM
TS1
TS2
TS2 ∆G2 = 50
I
∆ G2
TS1 ∆ G1
I E = 200
E
∆ G1
SM
SM
∆ Go
= -80 ∆ Go
= -40
P P
3) For each energy diagram in (2), lable starting material(s) (SM), product(s) (P), intermediate(s) (I),
transition state(s) (TS‡), activation energy(s) (∆
∆G‡) and free energy (∆
∆Go).
290 K 19
Br2 Br Keq = 1.24 x 10
Br
∆Go = -RT lnKeq = -(8.315 J/K mol)(290K) ln (1.24×1019) = -106,000 J/mol = -106 kJ/mol
∆Ho = ∆Hf bonds broken – ∆Hf bonds formed = ∆Hf C=C + ∆Hf Br-Br – 2(∆Hf C-Br) – ∆Hf C-C =
611 + 193 – 2(285) – 376 = -142 kJ/mol
∆Go = -RT lnKeq = -(8.315 J/K mol)(290K) ln (3.96×1019) = -87,000 J/mol = -87 kJ/mol
∆Ho = ∆Hf C=C + ∆Hf H-Br – ∆Hf C-H – ∆Hf C-Br – ∆Hf C-C =
611 + 366 – 420 – 285 – 376 = -104 kJ/mol
∆So = - (∆Go – ∆Ho)/T = - (-87 – (-104))/290 = -0.060 kJ/K mol = -60 J/K mol
Br Br Keq = 0.13
O OH
∆Go = -RT lnKeq = -(8.315 J/K mol)(290K) ln (0.13) = 4900 J/mol = 4.9 kJ/mol
∆Ho = ∆Hf C-H + ∆Hf C-Br + ∆Hf C-C – ∆Hf O-H – ∆Hf C=C =
420 + 285 + 376 – 437 – 611 = 33 kJ/mol
∆So = - (∆Go – ∆Ho)/T = - (4.9 – 33)/290 = 0.097 kJ/K mol = 97 J/K mol