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Thermodynamics
Entropy, Free Energy and the Direction
of Chemical Reactions
20-1
Thermodynamics
Entropy, Free Energy, and the Direction of Chemical
Reactions
20-2
The Larger Question
A B
20-3
Limitations of the First Law of Thermodynamics
DE = q + w
DEsystem = -DEsurroundings
20-4
A spontaneous endothermic chemical reaction
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water
DHorxn = + 62.3 kJ
20-6
The number of ways to arrange a deck of playing cards
Figure 20.2
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20-7
Spontaneous expansion of a gas
This process occurs
stopcock spontaneously
closed without a change in
the total internal
energy of the
system!
This is an entropy-
1 atm evacuated driven process!
stopcock
opened
20-10
Random motion in a crystal
(increased arrangements, greater S)
Ssystem = 0 at 0 K
Figure 20.4
20-11 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
The Third Law leads to absolute values for the entropies of substances!
units: J/mol/K at 25 oC
20-12
Predicting relative So values of a system
1. Temperature changes
So increases as temperature rises.
2. Physical states and phase changes
So increases as a more ordered phase changes to a less
ordered phase.
3. Dissolution of a solid or liquid
So of a dissolved solid or liquid is usually greater than So of the
pure solute. However, the extent depends on the nature of the
solute and solvent.
4. Dissolution of a gas
A gas becomes more ordered when it dissolves in a liquid or solid.
5. Atomic size or molecular complexity
In similar substances, increases in mass relate directly to entropy.
In allotropic substances, increases in complexity (e.g., bond
flexibility) relate directly to entropy.
20-13
The increase in entropy from solid to liquid to gas
Figure 20.5
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The entropy change accompanying the dissolution of a salt
pure solid
MIX
pure liquid
solution
Figure 20.6
20-15 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
The small increase in entropy when ethanol dissolves in water
Figure 20.7
20-16 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
The large decrease in entropy when a gas dissolves in a liquid
O2 gas
O2 dissolved
Figure 20.8
20-17 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Entropy and vibrational motion
NO
N2O4
NO2
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 oxygen gas (O2) or 2 mol of ozone gas (O3)
(d) 1 mol of KBr(s) or 1 mol of KBr(aq)
(e) seawater in mid-winter at 2 oC or in mid-summer at 23 oC
(f) 1 mol of CF4(g) or 1 mol of CCl4(g)
PLAN: In general less ordered systems have higher entropy than ordered
systems and entropy increases with increasing temperature.
SOLUTION:
(a) 1 mol of SO3(g) - more atoms (d) 1 mol of KBr(aq) - solution > solid
(b) 1 mol of CO2(g) - gas > solid (e) 23 oC - higher temperature
(c) 3 mol of O2(g) - larger # mols (f) CCl4 - larger mass
20-19
Standard Entropies of Reaction, DSorxn
20-20
Sample Problem 20.2 Calculating the standard entropy of reaction, DSorxn
DSorxn = [(3 mol)(So CO2) + (4 mol)(So H2O)] - [(1 mol)(So C3H8) + (5 mol)(So O2)]
20-21
We can’t forget entropy changes in the surroundings!
20-22
Combining these ideas......
DSsurr = -qsys/T
DSsurr = -DHsys/T
20-23
Sample Problem 20.3 Determining reaction spontaneity
SOLUTION: DHorxn = [(2 mol)(DHof NH3)] - [(1 mol)(DHof N2) + (3 mol)(DHof H2)]
DHorxn = -91.8 kJ
DSosurr = -DHosys/T = -(-91.8 x 103J/298 K) = +308 J/K (>+197 J/K)
DSouniv = DSosurr + DSosys = 308 J/K + (-197 J/K) = +111 J/K
20-26
Components of DSouniv for spontaneous reactions
exothermic
endothermic
exothermic
20-28
Deriving the Gibbs free energy equation
DSsurr = -DHsys/T
DGsys = -TDSuniv
20-29
Some Key Concepts
20-30
Standard Free Energy Changes
A reference state; similar to DHo and So
20-31
Sample Problem 20.4 Calculating DGo from enthalpy and entropy values
20-32
Sample Problem 20.4 (continued)
DG0rxn = -133 kJ
20-33
Another way to calculate DGorxn
DGof = the free energy change that occurs when 1 mol of compound
is made from its elements, with all components in their standard states.
Thus,
20-34
Sample Problem 20.5 Calculating DGorxn from DGof values
PROBLEM: Use DGof values to calculate DGorxn for the following reaction:
D
4KClO3(s) 3KClO4(s) + KCl(s)
DGorxn = -134 kJ
20-35
DG and Work
An example of a
gas doing work
20-36
More Key Concepts
20-37
Effect of Temperature on Reaction Spontaneity
20-38
Table 20.1 Reaction Spontaneity and the Signs of
DHo, DSo and DGo
- + - - 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
20-39
Sample Problem 20.6 Determining the effect of temperature on DGo
At 298 K, DGo = -141.6 kJ, DHo = -198.4 kJ, and DSo = -187.9 J/K.
(a) Use these data to decide if this reaction is spontaneous at 25 oC, and
predict how DGo will change with increasing T.
(b) Assuming DHo and DSo are constant with increasing T, is the reaction
spontaneous at 900. oC?
20-40
Sample Problem 20.6 (continued)
20-41
Determining the Temperature at which a
Reaction Becomes Spontaneous
DHo = TDSo
T = DHo/DSo
20-42
The effect of temperature on reaction spontaneity
Cu2O(s) + C(s)
2Cu(s) + CO(g)
DHo = +58.1 kJ
DSo = +165 J/K
DHo: relatively
insensitive to T
DSo: increases
with increasing T
Figure 20.11
20-43
The cycling of metabolic free energy through ATP
Figure B20.4
20-44
The coupling of a nonspontaneous reaction to
the hydrolysis of ATP
Figure B20.5
20-46
End of Assigned Material
20-47
Free energy, equilibrium and reaction direction
DG = RT ln Q/K = RT ln Q - RT ln K
If Q/K < 1, then ln Q/K < 0; the reaction proceeds to the right (DG < 0)
If Q/K > 1, then ln Q/K > 0; the reaction proceeds to the left (DG > 0)
DGo = - RT ln K
20-48
Table 20.2 The relationship between DGo and K at 25 oC
FORWARD REACTION
50 2 x 10-9
REVERSE REACTION
10 2 x 10-2
1 7 x 10-1
Forward and reverse reactions
0 1 proceed to the same extent
-1 1.5
-10 5 x 101
-50 6 x 108
Forward reaction goes to
-100 3 x 1017
completion; essentially no reverse
-200 1 x 1035 reaction
20-49
Sample Problem 20.7 Calculating DG at non-standard conditions
20-50
Sample Problem 20.7 (continued)
DGo = -RTln K so
(-141.6 kJ/mol)(103 J/kJ)
At 298 K, the exponent is -DGo/RT =- = 57.2
(8.314 J/mol.K)(298 K)
= e57.2 = 7 x 1024
= e1.50 = 4.5
20-51
Sample Problem 20.7 (continued)
pSO32 (0.100)2
(b) The value of Q = = = 4.00
(pSO2)2(pO2) (0.500)2(0.0100)
Since Q is < K at both temperatures the reaction will shift right; for 298 K
there will be a dramatic shift while at 973 K the shift will be slight.
20-52
The relation between free energy and the extent of reaction
Figure 20.12
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