General Chemistry

Principles and Modern Applications

Petrucci Harwood Herring
8th Edition

Chapter 20: Spontaneous Change:

Entropy and Free Energy
Philip Dutton
University of Windsor, Canada
N9B 3P4
Prentice-Hall 2002

Contents
20-1
20-2
20-3
20-4
20-5
20-6
20-7
20-8

Spontaneity: The Meaning of Spontaneous Change

The Concept of Entropy
Evaluating Entropy and Entropy Changes
Criteria for Spontaneous Change:
The Second Law of Thermodynamics
Standard Fee Energy Change, G
Free Energy Change and Equilibrium
G and Keq as Functions of Temperature
Coupled Reactions
Focus On Coupled Reactions in Biological Systems

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20-1 Spontaneity: The Meaning of

Spontaneous Change

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Spontaneous Process
A process that occurs in a system left to itself.
Once started, no external actions is necessary to make
the process continue.

A non-spontaneous process will not occur without

external action continuously applied.
4 Fe(s) + 3 O2(g) 2 Fe2O3(s)
H2O(s) H2O(l)

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Spontaneous Process
Potential energy decreases.
For chemical systems the internal energy U is
equivalent to potential energy.
Berthelot and Thomsen 1870s
Spontaneous change occurs in the direction in which
the enthalpy of a system decreases.
Mainly true but there are exceptions.

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20-2 The Concept of Entropy

Entropy, S.

U = H = 0

The greater the number

of configurations of the
microscopic particles
among the energy
levels in a particular
system, the greater the
entropy of the system.
S > 0 spontaneous

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The Boltzmann Equation for Entropy

S = k lnW
States, S.
The microscopic energy levels
available in a system.

Microstates, W.
The particular way in which particles are distributed
amongst the states. Number of microstates = W.

The Boltzmann constant, k.

Effectively the gas constant per molecule = R/NA.
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Boltzmann Distribution

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Entropy Change

S =

qrev
T

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20-3 Evaluating Entropy and

Entropy Changes
Phase transitions.
Exchange of heat can be carried out reversibly.
S =
H2O(s, 1 atm) H2O(l, 1 atm)

H
Ttr
Hfus = 6.02 kJ at 273.15 K

Hfus
6.02 kJ mol-1
Sfus =
=
= 2.2010-2 kJ mol-1 K-1
Ttr
273.15 K
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Troutons Rule

S =

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Hvap
Tbp

87 kJ mol-1 K-1

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Raoults Law

PA = APA

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Absolute Entropies
Third law of thermodynamics.
The entropy of a pure perfect crystal at 0 K is zero.

Standard molar entropy.

Tabulated in Appendix D.

S = [ pS(products) - rS(reactants)]

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Entropy as a Function of Temperature

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Vibrational Energy and Entropy

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20-4 Criteria for Spontaneous Change:

The Second Law of Thermodynamics.
Stotal = Suniverse = Ssystem + Ssurroundings
The Second Law of Thermodynamics:
Suniverse = Ssystem + Ssurroundings > 0
All spontaneous processes produce an
increase in the entropy of the universe.
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Free Energy and Free Energy Change

Hypothetical process:
only pressure-volume work, at constant T and P.
qsurroundings = -qp = -Hsys

Make the enthalpy change reversible.

large surroundings, infinitesimal change in temperature.

Under these conditions we can calculate entropy.

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Free Energy and Free Energy Change

For the universe:
TSuniv. = TSsys Hsys = -(Hsys TSsys)
-TSuniv. = Hsys TSsys
For the system:

G = H - TS
G = H - TS
Gsys = - TSuniverse

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Criteria for Spontaneous Change

Gsys < 0 (negative), the process is spontaneous.

Gsys = 0 (zero), the process is at equilibrium.
Gsys > 0 (positive), the process is non-spontaneous.

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Table 20.1 Criteria for Spontaneous

Change

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20-5 Standard Free Energy Change, G

The standard free energy of formation, Gf.
The free energy change for a reaction in which a
substance in its standard state is formed from its
elements in reference forms in their standard states.

The standard free energy of reaction, G.

G = [ p Gf(products) - r Gf(reactants)]

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20-6 Free Energy Change and Equilibrium

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Free Energy Change and Equilibrium

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Relationship of G to G for
Nonstandard Conditions
2 N2(g) + 3 H2(g) 2 NH3(g)
G = H - TS

G = H - TS

For ideal gases H = H

G = H - TS

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Relationship Between S and S

Vf
qrev = -w = RT ln
Vi
qrev
Vf
= R ln
S =
T
Vi
Pf
Pi
Vf
= R ln
= -R ln
S = Sf Si = R ln
Pi
Pf
Vi
P
P
= S - R ln P
= S - R ln
S = S - R ln
1
P
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2 N2(g) + 3 H2(g) 2 NH3(g)

SN2 =

SH2 =

SN2 Rln PN2

SH2 Rln PH2

SNH3 =
SNH3 Rln PNH3

Srxn = 2(SNH3 Rln PNH3) 2(SN2 Rln PN2) 3(SH2 Rln PH2)
3

PN22PH2

Srxn = 2 SNH3 2SN2 3SH2+ Rln

2
PNH
3
3

Srxn = Srxn + Rln

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PN22PH2
2
PNH
3

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G Under Non-standard Conditions

3

G = H - TS

Srxn = Srxn + Rln

PN22PH2
2
PNH
3

G = H - TSrxn TR ln

G = G + RT ln

PN22PH2
2
PNH
3

2
NH3

PN22PH2

G = G + RT ln Q

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G and the Equilibrium Constant Keq

G = G + RT ln Q
If the reaction is at equilibrium then:
G = G + RT ln Keq= 0
G = -RT ln Keq

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Criteria for Spontaneous Change

Every chemical reaction consists of both a
forward and a reverse reaction.
The direction of spontaneous change is the direction
in which the free energy decreases.

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Significance of the Magnitude of G

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The Thermodynamic Equilibrium

Constant: Activities
For ideal gases at 1.0 bar:
P
P
= S - R ln
S = S - R ln
1
P
PV=nRT or P=(n/V)RT, pressure is an effective concentration
Therefore, in solution:

c
= S - R ln a
S = S - R ln
c

The effective concentration in the standard

state for an ideal solution is c = 1 M.
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Activities
For pure solids and liquids:
a = 1
For ideal gases:
a = P
(in bars, 1 bar = 0.987 atm)
For ideal solutes in aqueous solution:
a = c
(in mol L-1)

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The Thermodynamic Equilibrium

Constant, Keq
A dimensionless equilibrium constant expressed
in terms of activities.
Often Keq = Kc
Must be used to determine G.
agah
G = G + RT ln
aaab

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20-7 G and Keq as Functions

of Temperature
G = H -TS

G = -RT ln Keq

-G
-H
TS
ln Keq =
=
+
RT
RT
RT
-H
S
ln Keq =
+
RT
R
ln

Keq2
Keq1

1
-H
S -H
S -H 1
=
+
+
=
RT2
R
RT1
R
R T2 T1

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Temperature Dependence of Keq

-H
S
ln Keq =
+
RT
R
-H
slope =
R
-H = R slope
= -8.3145 J mol-1 K-1 2.2104 K
= -1.8102 kJ mol-1
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20-8 Coupled Reactions

In order to drive a non-spontaneous reactions we
changed the conditions (i.e. temperature or
electrolysis)
Another method is to couple two reactions.
One with a positive G and one with a negative G.
Overall spontaneous process.

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Smelting Copper Ore

Cu2O(s)
2 Cu(s) + O2(g)G673K = +125 kJ

Non-spontaneous reaction:

Cu2O(s) 2 Cu(s) + O2(g) +125 kJ

Spontaneous reaction: C(s) + O2(g) CO(g)

-175 kJ

Cu2O(s) + C(s) 2 Cu(s) + CO(g)

-50 kJ

Spontaneous reaction!

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Focus On Coupled Reactions in

Biological Systems
ADP3- + HPO42- + H+ ATP4- + H2O
G = -9.2 kJ mol-1
aATPaH2O
G = G + RT ln
aADPaPiaH3O+
But [H3O+] = 10-7 M not 1.0 M.
G = -9.2 kJ mol-1 + 41.6 kJ mol-1
The biological standard state:
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Focus On Coupled Reactions in

Biological Systems

Glucose 2 lactate + 2 H+
2 ADP3- + 2 HPO42- + 2 H+ 2 ATP4- + 2 H2O

-218 kJ
+64 kJ

2 ADP3- + 2 HPO42- + glucose 2 ATP4- + 2 H2O + 2 lactate

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-153 kJ

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Chapter 20 Questions
Develop problem solving skills and base your strategy not
on solutions to specific problems but on understanding.

Choose a variety of problems from the text as examples.

Practice good techniques and get coaching from people who

have been here before.

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