Chapter 1 : Thermodynamics (Gibbs Free Energy)

1.

Given the reaction of diamond converting to graphite

2C(s (diamond)→2C(s(graphite)
Determine ∆G at 298 K and determine if this reaction is spontaneous or not. What
does ∆G say about the rate of this reaction?
ΔH°f(C(s)diamond)=1.9kJ/mol
•
∆H°f(C(s)diamond)=1.9kJ/mol
•
S°(C(s)diamond=2.38J/(molK)
•
•
S°(C(s)diamond=2.38J/(molK)
S°(C(s)graphite)=5.74J/(molK)
•
Answer:
ΔG=ΔH−TΔS
∆H=(2mol C(s)(graphite)× ∆H°f C(s)graphite) )-(2mol C(s)diamond×∆H°(f
C(s)diamond) )
∆H=2(0)-2(1.9 kJ/mol)
=-3.8kJ
∆S=(2mol C(s)(graphite)× S( C(s)graphite) )-(2mol C(s)diamond× SC(s)diamond )
∆S=2(5.74 J/(mol K))- 2(2.38 J/(mol K))
=+6.72 J/mol
∆G=-3.8×10^3 J - 298.15(6.72 J/mol K)
=-5.51 kJ
This reaction is spontaneous. ∆G says nothing about the kinetics while this reaction
is thermodynamics favoured. Diamonds are kinetically stable materials.

2.
CaCl2(s)→Ca2+(aq)+2Cl−(aq)
• the ΔG°f of CaCl2 (s)= -748.1 kJ/mol,
• the ΔH of CaCl2= -795.8 kJ
• the ΔSo,
o Ca2+=-53.1 J/Kmol,
o CaCl2=104.6 J/Kmol,
o Cl-=56.5
Calculate the temperature of this reaction.
Answer:
ΔG°=ΔH−TΔS
T=ΔH−ΔG°S
T=(0-[-795.8])-(-748.1))[(2(56.5)+(-53.1)]-[104.6]
T=-34.539 K
3.
Calculate ΔGo,
CS2(l)+2O2(g)→CO2(g)+2SO2(g)
using only the following ΔG values for the reaction:
• C(s)+O2(g)→CO2(g)C(s)+O2(g)→CO2(g) with ΔGo=−394.39kJ/mol
• S(s)+O2(g)→SO2(g)S(s)+O2(g)→SO2(g) with ΔGo=−300.13kJ/mol/mol
• C(s)+2S(s)→CS2(l)C(s)+2S(s)→CS2(l) with ΔGo=67.1kJ/mol

Answer:
C(s)+O2 (g)→CO2 (g) ;∆G=-394.39 kJ/mol
2[S(s)+O2 (g)→SO2 (g)] ;∆G=2[-300.13] kJ/mol
CS2 (l)→C(s)+2S(s) ;∆G=-(67.1) kJ/mol
∆G= -394.39 kJ/mol + 2[-300.13] kJ/mol + -(67.1) kJ/mol
= -1061.75
4.
Find ΔG° at 298.15 K for reaction
2CO+O2→2CO2
ΔH°= -128.3 kJ ΔS°=- 159.5 J K-1
Answer:
ΔG°= ΔH° - TΔS°
ΔG°= (-128.3 kJ) – [298.15K x (-159.5 JK-1 x (1 J/1000kJ))]
= -80.75 kJ
5.
Assess the feasibility of the reaction below by evaluating
(ΔSorxn, ΔHorxn∆Hrxno and ΔGorxn) for this reaction at 25°C. If the reaction is
spontaneous, is it enthalpically favored, entropically favored or both?

(NH)4Cl(s)→NH3(g)+HCl(g)
Answer:

ΔSo=∑(ΔSo)(products)−∑(ΔSo)(reactants
(192.5 + 186.9) – (94.6) = 284.8 kJ/mol K
ΔHorxn=∑(ΔHo)(products)−∑(ΔHo)(reactants
(-46.11 + -92.31) – (-314.4) = 175.98 kJ/mol
The Gibbs energy can be also tabulated,
ΔGorxn=∑(ΔGo)(products)−∑(ΔGo)(reactants)
but can be calculate directly from ΔSorxn and ΔHorxn,
ΔGorxn=ΔHorxn−TΔSorxn
ΔGorxn=175.98kJ/mol–298K(284.8)=−84,737kJ/mol)
The thermal decomposition of (NH)_4Cl_{(s)} is a strongly spontaneous process that
is entropically driven, but not enthalpically driven.