CHEM211 Problem Set

Reaction Energetics

1) For the molecules below:

a) Draw the most stable and least stable conformations.
b) Calculate the difference in energy between the conformations.
c) Calculate the equilibrium constant (Keq) for conversion between the conformations at room
temperature (70 oF, 21 oC, 294 K).
OH

(H3C)2HC CH3 H3CH2C CH(CH3)2

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

2) Sketch an energy diagram to match each of the following descriptions:

a) Fast reaction; ∆Go = -120 kJ/mol.
b) Slow reaction; ∆Go = 20 kJ/mol.
c) Very slow reaction; Keq = 1.36×10 –3.
d) Fast reaction; Keq = 3.0.
e) A two step reaction; first step is fast; second step is slow; ∆Go = -80 kJ/mol.
f) ∆G1‡ = 200 kJ/mol; ∆G2‡ = 50 kJ/mol; ∆Go = -40 kJ/mol.

TS
E TS E
∆G
SM
∆ Go ∆G
= -120
P
SM ∆ Go
P = +20

reaction coordinate reaction coordinate

 TS

E ∆G E TS

∆G
P SM
P
∆Go = 16 o
∆G = -2.7
SM

reaction coordinate reaction coordinate

TS1
TS2
TS2 ∆G2 = 50
I

∆ G2
TS1 ∆ G1
I E = 200
E
∆ G1
SM
SM
∆ Go
= -80 ∆ Go
= -40
P P

reaction coordinate reaction coordinate

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).

4) For the reactions below, calculate ∆Go, ∆Ho and ∆So.

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 = ∆Ho – T∆So

∆So = - (∆Go – ∆Ho)/T = - (-106 – (-142))/290 = -0.124 kJ/K mol = -124 J/K mol
 HBr Keq = 3.96 x 10 15
Br

∆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