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Chapter 1

This document discusses thermodynamics concepts including Gibbs free energy. It contains 5 examples calculating thermodynamic properties: 1. It calculates the Gibbs free energy for the reaction of diamond converting to graphite at 298K, finding it is spontaneous but does not provide information about reaction kinetics. 2. It calculates the temperature at which the dissolution of CaCl2(s) into its ions becomes non-spontaneous. 3. It calculates the standard Gibbs free energy for the reaction of CS2(l) with oxygen using standard Gibbs free energy values for other reactions. 4. It calculates the standard Gibbs free energy at 298K for the reaction of two carbon monoxide molecules with oxygen producing two

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Yu Ae Li
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© © All Rights Reserved
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Download as PDF, TXT or read online on Scribd
312 views

Chapter 1

This document discusses thermodynamics concepts including Gibbs free energy. It contains 5 examples calculating thermodynamic properties: 1. It calculates the Gibbs free energy for the reaction of diamond converting to graphite at 298K, finding it is spontaneous but does not provide information about reaction kinetics. 2. It calculates the temperature at which the dissolution of CaCl2(s) into its ions becomes non-spontaneous. 3. It calculates the standard Gibbs free energy for the reaction of CS2(l) with oxygen using standard Gibbs free energy values for other reactions. 4. It calculates the standard Gibbs free energy at 298K for the reaction of two carbon monoxide molecules with oxygen producing two

Uploaded by

Yu Ae Li
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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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.

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