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GENERAL
CHEMISTRY
Chapter 20:
Thermodynamics:
Entropy, Free
Energy, and the
Direction of
Chemical
Reactions
20-2
Thermodynamics: Entropy, Free Energy, and the
Direction of Chemical Reactions
20-3
Spontaneous Change
20-4
The First Law of Thermodynamics Does
Not Predict Spontaneous Change
Energy is conserved. It is neither created nor destroyed,
but is transferred in the form of heat and/or work.
DE = q + w
20-5
DH Does Not Predict Spontaneous Change
A spontaneous change may be exothermic or endothermic.
Spontaneous exothermic processes include:
• freezing and condensation at low temperatures,
• combustion reactions,
• oxidation of iron and other metals.
Spontaneous endothermic processes include:
• melting and vaporization at higher temperatures,
• dissolving of most soluble salts.
20-6
Figure 20.1 A spontaneous endothermic chemical reaction.
Ba(OH)2 ·8H2O(s) + 2NH4NO3(s) → Ba2+(aq) + 2NO3-(aq) + 2NH3(aq) + 10H2O(l)
DH°rxn = +62.3 kJ
water
This reaction occurs spontaneously when the solids are mixed. The
reaction mixture absorbs heat from the surroundings so quickly that
the beaker freezes to a wet block.
20-7
Freedom of Particle Motion
20-8
Microstates and Dispersal of Energy
• Just as the electronic energy levels within an atom are
quantized, a system of particles also has different
allowed energy states.
• Each quantized energy state for a system of particles is
called a microstate.
– At any instant, the total energy of the system is dispersed
throughout one microstate.
• At a given set of conditions, each microstate has the
same total energy as any other.
– Each microstate is therefore equally likely.
• The larger the number of possible microstates, the larger
the number of ways in which a system can disperse its
energy.
20-9
Entropy
20-10
Figure 20.2 Spontaneous expansion of a gas.
20-11
Figure 20.3 The entropy increase due to the expansion of a gas.
20-12
Figure 20.4 Expansion of a gas and the increase in number of
microstates.
20-13
DS for a Reversible Process
DS = qrev
T
20-14
Figure 20.5 Simulating a reversible process.
20-15
The Second Law of Thermodynamics
20-16
Comparing Energy and Entropy
The total energy of the universe remains constant.
DEsys + DEsurr =DEuniv = 0
DH is often used to approximateDE.
For enthalpy there is no zero point; we can only measure
changes in enthalpy.
20-17
The Third Law of Thermodynamics
Ssys = 0 at 0 K
20-18
Standard Molar Entropies
20-19
Factors Affecting Entropy
20-20
Figure 20.6A Visualizing the effect of temperature on entropy.
20-21
Figure 20.6B Visualizing the effect of temperature on entropy.
20-22
Figure 20.6C Visualizing the effect of temperature on entropy.
20-23
Figure 20.7 The increase in entropy during phase changes
from solid to liquid to gas.
20-24
Figure 20.8 The entropy change accompanying the dissolution
of a salt.
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
pure solid
MIX
pure liquid
solution
The entropy of a salt solution is usually greater than that of the solid
and of water, but it is affected by the organization of the water molecules
around each ion.
20-25
Figure 20.9 The small increase in entropy when ethanol
dissolves in water.
Ethanol (A) and water (B) each have many H bonds between their own
molecules. In solution (C) they form H bonds to each other, so their
freedom of motion does not change significantly.
20-26
Figure 20.10 The entropy of a gas dissolved in a liquid.
20-27
Entropy and Atomic Size
HF HCl HBr HI
Molar mass (g/mol) 20.01 36.46 80.91 127.9
S°(s) 173.7 186.8 198.6 206.3
20-28
Entropy and Structure
For allotropes, S° is higher in the form that allows the
atoms more freedom of motion.
S° of graphite is 5.69 J/mol·K, whereas S° of diamond is 2.44 J/mol·K.
20-29
Figure 20.11 Entropy, vibrational motion, and molecular
complexity.
20-30
Sample Problem 20.1 Predicting Relative Entropy Values
PROBLEM: Choose the member with the higher entropy in each of the
following pairs, and justify your choice [assume constant
temperature, except in part (e)]:
(a) 1 mol of SO2(g) or 1 mol of SO3(g)
(b) 1 mol of CO2(s) or 1 mol of CO2(g)
(c) 3 mol of O2(g) or 2 mol of O3(g)
(d) 1 mol of KBr(s) or 1 mol of KBr(aq)
(e) seawater at 2°C or at 23°C
(f) 1 mol of CF4(g) or 1 mol of CCl4(g)
20-31
Sample Problem 20.1
SOLUTION:
(a) 1 mol of SO3(g). For equal numbers of moles of substances with
the same types of atoms in the same physical state, the more
atoms in the molecule the higher the entropy.
(c) 3 mol of O2(g). The two samples contain the same number of
oxygen atoms but different numbers of molecules. Although each
O3 molecule is more complex than each O2 molecule, the greater
number of molecules dominates because there are many more
microstates possible for 3 mol of particles than for 2.
20-32
Sample Problem 20.1
(d) 1 mol of KBr(aq). The two samples have the same number of
ions, but their motion is more limited and their energy less
dispersed in the solid than in the solution. An ionic substance in
solution usually has a higher entropy than the solid.
20-33
Entropy Changes in the System
The standard entropy of reaction, DS°rxn, is the entropy
change that occurs when all reactants and products are in
their standard states.
20-34
Predicting the Sign of DS°rxn
We can often predict the sign of DS°rxn for processes that
involve a change in the number of moles of gas.
20-35
Sample Problem 20.2 Calculating the Standard Entropy of
Reaction, DS°rxn
PROBLEM: Predict the sign of DS°rxn and calculate its value for the
combustion of 1 mol of propane at 25°C.
C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(l)
PLAN: From the change in the number of moles of gas (6 mol yields
3 mol), the entropy should decrease (DS°rxn < 0). To find
DS°rxn, we apply Equation 20.4, using the S° values from
Appendix B.
SOLUTION:
ΔS°rxn = [(3 mol CO2)(S° of CO2) + (4 mol H2O)(S° of H2O)]
- [(1 mol C3H8)(S° of C3H8) + (5 mol O2)(S° of O2)
= [(3mol)(213.7J/K·mol) + (4 mol)(69.9J/K·mol)]
– [(1mol)(269.9 J/K·mol) + (5 mol)(205.0 J/K·mol) = -374 J/K
20-36
Entropy Changes in the Surroundings
A decrease in the entropy of the system is outweighed
by an increase in the entropy of the surroundings.
The surroundings function as a heat source or heat sink.
In an exothermic process, the surroundings absorbs the
heat released by the system, and Ssurr increases.
qsys < 0; qsurr > 0 and DSsurr > 0
20-37
Temperature at which Heat is Transferred
Since entropy depends on temperature, DS°surr is also
affected by the temperature at which heat is transferred.
For any reaction, qsys = -qsurr. The heat transferred is
specific for the reaction and is the same regardless of the
temperature of the surroundings.
The impact on the surroundings is larger when the
surroundings are at lower temperature, because there is
a greater relative change in Ssurr.
20-38
Sample Problem 20.3 Determining Reaction Spontaneity
SOLUTION:
DH°rxn = [(2 mol)(DH°f of NH3)] - [(1 mol)(DH°f of N2) + (3 mol)(DH°f of H2)]
= [(2 mol)(-45.9 kJ/mol)] - [(1 mol)(0 kJ/mol) + (3 mol)(0 kJ/mol)]
= 91.8 kJ
20-39
Sample Problem 20.3
-91.8 kJ x 1000 J
DHsys 1 kJ
DSsurr = - =- = 308 J/K
T 298 K
20-40
Figure 20.12 A whole-body calorimeter.
20-41
DS and the Equilibrium State
20-42
Figure 20.13AB Components of DS°univ for spontaneous reactions.
exothermic exothermic
20-43
Figure 20.13C Components of DS°univ for spontaneous reactions.
endothermic
20-44
Gibbs Free Energy
The Gibbs free energy (G) combines the enthalpy and
entropy of a system; G = H – TS.
20-45
Calculating DG°
20-46
Sample Problem 20.4 Calculating DG°rxn from Enthalpy and
Entropy Values
PROBLEM: Potassium chlorate, a common oxidizing agent in
fireworks and matchheads, undergoes a solid-state
disproportionation reaction when heated.
+5 Δ +7 -1
4KClO3(s) 3KClO4(s) + KCl(s)
PLAN: To solve for DG°, we need values from Appendix B. We use
DHf° to calculate DH°rxn, use S° values to calculate DS°rxn and
then apply the Gibbs equation.
SOLUTION:
DH°rxn = SmDHf°(products) - SnDHf°(reactants)
= [(3 mol KClO4)(DHf° of KClO4) + (1 mol KCl)(DHf° of KCl)]
‒ [(4 mol KClO3)(DHf° of KClO3)]
= [(3 mol)(-432.8 kJ/mol) + (1 mol)(-436.7 kJ/mol)
– [(4 mol)(-397.7 kJ/mol)] = 144 kJ
20-47
Sample Problem 20.4
1000 J
DG°sys = DH°sys - T DS°sys = 144 kJ – (298 K)(-36.8 J/K)
1 kJ
= -133 kJ
20-48
Sample Problem 20.5 Calculating DG°rxn from DG°f Values
PLAN: We apply Equation 20.8 and use the values from Appendix
B to calculate DG°rxn.
SOLUTION:
DG°rxn = SmDG°products - SnDG°reactants
= [(3 mol KClO4)(DGf° of KClO4) + (1 mol KCl)(DGf° of KCl)]
‒ [(4 mol KClO3)(DGf° of KClO3)]
= [(3 mol)(-303.2 kJ/mol) + (1 mol)(-409.2 kJ/mol)]
‒ [(4 mol)(-296.3 kJ/mol)]
= -134 kJ
20-49
DG° and Useful Work
20-50
Figure 20.14 An expanding gas lifting a weight.
20-51
Effect of Temperature on Reaction Spontaneity
DGsys = DHsys - T DSsys
Reaction is spontaneous at
all temperatures
If DH < 0 and DS > 0
DG < 0 for all T
Reaction is nonspontaneous
at all temperatures
If DH > 0 and DS < 0
DG > 0 for all T
20-52
Effect of Temperature on Reaction Spontaneity
20-53
Table 20.1 Reaction Spontaneity and the Signs of DH, DS, and DG
DH DS -TDS DG Description
– + – – Spontaneous at all T
+ – + + Nonspontaneous at all T
+ + – + or – Spontaneous at higher T;
nonspontaneous at lower T
– – + + or – Spontaneous at lower T;
nonspontaneous at higher T
20-54
Sample Problem 20.6 Using Molecular Scenes to Determine the
Signs of DH, DS, and DG
PROBLEM: The following scenes represent a familiar phase change
for water (blue spheres).
(a) What are the signs of DH and DS for this process? Explain.
(b) Is the process spontaneous at all T, no T, low T, or high T? Explain.
PLAN: (a) From the scenes, we determine any change in the amount
of gas, which indicates the sign of DS, and any change in
the freedom of motion of the particles, which indicates
whether heat is absorbed or released.
(b) To determine reaction spontaneity we need to consider the
sign of DG at different temperatures.
20-55
Sample Problem 20.6
SOLUTION:
20-56
Sample Problem 20.7 Determining the Effect of Temperature on ΔG
20-57
Sample Problem 20.7
SOLUTION:
(a) DG < 0 at 209 K (= 25°C), so the reaction is spontaneous.
With DS < 0, the term -TDS > 0 and this term will become more
positive at higher T.
DG will become less negative, and the reaction less spontaneous,
with increasing T.
(b) DG = DH - TDS
Convert T to K: 900. + 273.15 = 1173 K
Convert S to kJ/K: -187.9 J/K = 0.1879 kJ/K
DG = -198.4 kJ – [1173 K)(-0.187.9 kJ/K) = 22.0 kJ
20-58
Figure 20.15 The effect of temperature on reaction spontaneity.
The sign of DG
switches at
T = DH
ΔS
20-59
Sample Problem 20.8 Finding the Temperature at Which a
Reaction Becomes Spontaneous
PROBLEM: At 25°C (298 K), the reduction of copper(I) oxide is
nonspontaneous DG = 8.9 kJ). Calculate the temperature
at which the reaction becomes spontaneous.
SOLUTION:
DH 58.1 kJ
T= = = 352 K
DS 0.165 kJ/K
At any temperature above 352 K (= 79°C), the reaction becomes
spontaneous.
20-60
Chemical Connections
Figure B20.1 The coupling of a nonspontaneous reaction to
the hydrolysis of ATP.
20-61
Chemical Connections
Figure B20.2 The cycling of metabolic free energy.
20-62
Chemical Connections
Figure B20.3 ATP is a high-energy molecule.
20-63
DG, Equilibrium, and Reaction Direction
A reaction is at equilibrium if
Q = K; Q = 1 so ln Q = 0 and DG = 0
K K
20-64
DG, Q, and K
Q
DG = RT ln = RT lnQ – RT lnK
K
20-65
ΔG and the Equlibrium Constant
20-66
Table 20.2 The Relationship Between DG° and K at 298 K
FORWARD REACTION
REVERSE REACTION
10 2x10-2
1 7x10-1
0
-1
1
1.5
{ Forward and reverse reactions proceed
to same extent
-10 5x101
-50 6x108
3x1017
-100
-200 1x1035
{ Forward reaction goes to completion;
essentially no reverse reaction
20-67
Sample Problem 20.9 Using Molecular Scenes to Find DG for a
Reaction at Nonstandard Conditions
PROBLEM: These molecular scenes represent three mixtures in which
A2 (black) and B2 (green) are forming AB. Each molecule
represents 0.10 atm. The equation is
A2(g) + B2(g) 2AB(g) DGo = -3.4 kJ/mol
20-68
Sample Problem 20.9
PLAN:
(a) Mixture 1 is at equilibrium, so we first write the expression for Q
and then find the partial pressure of each substance from the
number of molecules and calculate K.
(b) To find DG, we apply equation 20.13. We can calculate the value
of T using K from part (a), and substitute the partial pressure of
each substance to get Q.
(c) Since 1.0 atm is the standard state for gases, DG = DG°.
SOLUTION:
PAB2
(a) A2(g) + B2(g) 2AB(g) Q=
PA2 x PB2
(0.40)2
K= = 4.0
(0.20)(0.20)
20-69
Sample Problem 20.9
20-70
Sample Problem 20.9
Mixture 3:
(0.60)2
Q= = 36
(0.10)(0.10)
DG = DG° + RT lnQ
= -3400 J/mol + (8.314 J/mol·K)(295 K)(ln 36)
= -3400 J + 8800 J = +5.4x10-3 J
Mixture 2 has the most negative DG, and mixture 3 has the
most positive DG.
20-71
Sample Problem 20.10 Calculating DG at Nonstandard Conditions
(b) Two containers are filled with 0.500 atm of SO2, 0.0100 atm of
O2, and 0.100 atm of SO3; one is kept at 25°C and the other at
700.°C. In which direction, if any, will the reaction proceed to
reach equilibrium at each temperature?
20-72
Sample Problem 20.10
PLAN:
(a) We know DG°, T, and R, so we can calculate the values of K at
each temperature.
(b) To determine if a net reaction will occur, we find Q from the given
partial pressures and compare Q to K from part (a). of each
substance to get Q.
(c) These are not standard-state pressures, so we find DG at each
temperature using the equation DG = DG° + RT lnQ.
SOLUTION:
(a) DG° = -RT lnK so K = e -(DG°/RT)
-141.6x103 J/mol
At 298 K, -(DG°)/RT = = 57.2
8.314 J/mol·K x 298 K
K at 298 K = e57.2 = 7x1024
20-73
Sample Problem 20.10
-12.12x103 J/mol
At 973 K, -(DG°)/RT = = 1.50
8.314 J/mol·K x 973 K
K at 973 K = e1.50 = 4.5
20-74
Sample Problem 20.10
(c)
DG298 = DG° + RT ln Q
= -141.6 kJ/mol + (8.314x10-3 kJ/mol·K x 298 K x ln 4.00)
= -138.2 kJ/mol
DG973 = DG° + RT ln Q
= -12.12 kJ/mol + (8.314x10-3 kJ/mol·K x 973 K x ln 4.00)
= -0.9 kJ/mol
20-75
Figure 20.16 Free energy and the extent of reaction.
20-76