Chapter 17 Entropy Free Energy and Equilibrium
Chapter 17 Entropy Free Energy and Equilibrium
Chapter 17 Entropy Free Energy and Equilibrium
and Equilibrium
Chapter 17
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spontaneous
nonspontaneous
spontaneous
nonspontaneous
H2O (s)
NH4NO3 (s)
disorder
S = Sf - Si
If the change from initial to final results in an increase in randomness
Sf > Si
S > 0
For any substance, the solid state is more ordered than the
liquid state and the liquid state is more ordered than gas
state.
Ssolid < Sliquid << Sgas
H2O (s)
H2O (l)
S > 0
Entropy
W = number of microstates
S = k ln W
S = Sf - Si
S = k ln
Wf
Wi
Example: Br2(l)
S > 0
Br2(g)
Example: I2(s)
I2(g)
S > 0
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Entropy
State functions are properties that are determined by the state
of the system, regardless of how that condition was achieved.
Examples:
energy, enthalpy, pressure, volume, temperature, entropy
Review
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Example 17.1
Predict whether the entropy change is greater or less than
zero for each of the following processes:
(a) freezing ethanol
(b) evaporating a beaker of liquid bromine at room
temperature
(c) dissolving glucose in water
(d) cooling nitrogen gas from 80C to 20C
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Example 17.1
Strategy
To determine the entropy change in each case, we examine
whether the number of microstates of the system increases or
decreases. The sign of S will be positive if there is an increase
in the number of microstates and negative if the number of
microstates decreases.
Solution
(a) Upon freezing, the ethanol molecules are held rigid in
position. This phase transition reduces the number of
microstates and therefore the entropy decreases; that is,
S < 0.
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Example 17.1
(b) Evaporating bromine increases the number of microstates
because the Br2 molecules can occupy many more positions
in nearly empty space. Therefore, S > 0.
(c) Glucose is a nonelectrolyte. The solution process leads to a
greater dispersal of matter due to the mixing of glucose and
water molecules so we expect S > 0.
(d) The cooling process decreases various molecular motions.
This leads to a decrease in microstates and so S < 0.
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Spontaneous process:
Equilibrium process:
cC + dD
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Example 17.2
From the standard entropy values in Appendix 3, calculate the
standard entropy changes for the following reactions at 25C.
(a) CaCO3(s)
CaO(s) + CO2(g)
2NH3(g)
2HCl(g)
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Example 17.2
Strategy
To calculate the standard entropy of a reaction, we look up the
standard entropies of reactants and products in Appendix 3 and
apply Equation (17.7). As in the calculation of enthalpy of
reaction [see Equation (6.18)], the stoichiometric coefficients
have no units, so Srxn is expressed in units of J/Kmol.
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Example 17.2
Solution
(a)
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Example 17.2
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Example 17.2
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Example 17.3
Predict whether the entropy change of the system in each of
the following reactions is positive or negative.
(a) 2H2(g) + O2(g)
(b) NH4Cl(s)
(c) H2(g) + Br2(g)
2H2O(l)
NH3(g) + HCl(g)
2HBr(g)
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Example 17.3
Strategy
We are asked to predict, not calculate, the sign of entropy
change in the reactions. The factors that lead to an increase in
entropy are: (1) a transition from a condensed phase to the
vapor phase and (2) a reaction that produces more product
molecules than reactant molecules in the same phase. It is also
important to compare the relative complexity of the product and
reactant molecules. In general, the more complex the molecular
structure, the greater the entropy of the compound.
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Example 17.3
Solution
(a) Two reactant molecules combine to form one product
molecule. Even though H2O is a more complex molecule
than either H2 and O2, the fact that there is a net decrease
of one molecule and gases are converted to liquid ensures
that the number of microstates will be diminished and hence
S is negative.
(b) A solid is converted to two gaseous products. Therefore,
S is positive.
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Example 17.3
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Exothermic Process
Ssurr > 0
Endothermic Process
Ssurr < 0
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S = k ln W
W=1
S=0
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Equilibrium process:
Gibbs free
energy (G)
G < 0
G > 0
G = 0
The standard free-energy of reaction ( G0rxn) is the freeenergy change for a reaction when it occurs under standardstate conditions.
aA + bB
cC + dD
0
Grxn
= [ cG0f (C) + dG0f (D) ] - [ aG0f (A) + bG0f (B) ]
0
Grxn
= nG0f (products) - mG0f (reactants)
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Example 17.4
CO2(g) + 2H2O(l)
2Mg(s) + O2(g)
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Example 17.4
Strategy
To calculate the standard free-energy change of a reaction, we
look up the standard free energies of formation of reactants and
products in Appendix 3 and apply Equation (17.12). Note that all
the stoichiometric coefficients have no units so Grxn is
expressed in units of kJ/mol, and Gf for O2 is zero because it
is the stable allotropic element at 1 atm and 25C.
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Example 17.4
Solution
(a)According to Equation (17.12), we write
Grxn = [Gf (CO2) + 2Gf (H2O)] - [Gf (CH4) + 2Gf (O2)]
We insert the appropriate values from Appendix 3:
Grxn =[(-394.4 kJ/mol) + (2)(-237.2 kJ/mol)] [(-50.8 kJ/mol) + (2) (0 kJ/mol)]
= -818.0 kJ/mol
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Example 17.4
(b) The equation is
Grxn = [2Gf (Mg) + Gf (O2)] - [2Gf (MgO)]
From data in Appendix 3 we write
Grxn = [(2)(0 kJ/mol) + (0 kJ/mol)] - [(2)(-569.6 kJ/mol)]
= 1139 kJ/mol
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Efficiency =
Th - Tc
X 100%
Th
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G = H - TS
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H0 = 177.8 kJ/mol
S0 = 160.5 J/Kmol
G0 = H0 TS0
At 25 oC, G0 = 130.0 kJ/mol
G0 = 0 at 835 oC
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G0 = 0 = H0 TS0
H2O (l)
H2O (g)
S =
H
40.79 kJ/mol
=
T
373 K
= 1.09 x 10-1 kJ/Kmol
= 109 J/Kmol
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Example 17.5
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Example 17.5
Strategy
At the melting point, liquid and solid benzene are at equilibrium,
so G = 0. From Equation (17.10) we have G = 0 =
H - T S or S = H/T. To calculate the entropy change for
the solid benzene liquid benzene transition, we write
Sfus = Hfus/Tf. Here Hfus is positive for an endothermic
process, so Sfus is also positive, as expected for a solid to
liquid transition. The same procedure applies to the liquid
benzene vapor benzene transition. What temperature unit
should be used?
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Example 17.5
Solution
The entropy change for melting 1 mole of benzene at 5.5C is
Sfus
H fus
=
Tf
(10.9 kJ/mol)(1000 J/1 kJ)
=
(5.5 + 273)K
= 39.1 J / K mol
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Example 17.5
Similarly, the entropy change for boiling 1 mole of benzene at
80.1C is
S vap =
H vap
Tb
Q=K
0 = G0 + RT lnK
G0 = RT lnK
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G0 < 0
G0 > 0
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G0 = RT lnK
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Example 17.6
2H2(g) + O2(g)
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Example 17.6
Strategy
According to Equation (17.14), the equilibrium constant for the
reaction is related to the standard free-energy change; that is,
G = -RT ln K. Therefore, we first need to calculate G by
following the procedure in Example 17.4. Then we can
calculate KP. What temperature unit should be used?
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Example 17.6
Solution According to Equation (17.12),
Grxn = [2Gf(H2) + Gf(O2)] - [2Gf(H2O)]
= [(2)(0 kJ/mol) + (0 kJ/mol)] - [(2)(-237.2 kJ/mol)]
= 474.4 kJ/mol
Using Equation (17.14)
o
Grxn
= -RTlnK p
1000 J
474.4 kJ/mol
= -(8.314J/K mol)(298 K)lnK p
1 kJ
lnK p = -191.5
K p e 191.5 = 7 10-84
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Example 17.6
Comment
This extremely small equilibrium constant is consistent with the
fact that water does not spontaneously decompose into
hydrogen and oxygen gases at 25C. Thus, a large positive
G favors reactants over products at equilibrium.
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Example 17.7
Ag+(aq) + Cl-(aq)
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Example 17.7
Strategy
According to Equation (17.14), the equilibrium constant for the
reaction is related to standard free-energy change; that is,
G = -RT ln K. Because this is a heterogeneous equilibrium,
the solubility product (Ksp) is the equilibrium constant. We
calculate the standard free-energy change from the Ksp value of
AgCl. What temperature unit should be used?
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Example 17.7
Solution The solubility equilibrium for AgCl is
AgCl(s)
Ag+(aq) + Cl-(aq)
Ksp = [Ag+][Cl-] = 1.6 x 10-10
Using Equation (17.14) we obtain
G = -(8.314 J/Kmol) (298 K) ln (1.6 x 10-10)
= 5.6 x 104 J/mol
= 56 kJ/mol
Check The large, positive G indicates that AgCl is slightly
soluble and that the equilibrium lies mostly to the left.
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Example 17.8
The equilibrium constant (KP) for the reaction
N2O4(g)
2NO2(g)
2 4
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Example 17.8
Strategy
From the information given we see that neither the reactant nor
the product is at its standard state of 1 atm. To determine the
direction of the net reaction, we need to calculate the freeenergy change under nonstandard-state conditions (G) using
Equation (17.13) and the given G value. Note that the partial
pressures are expressed as dimensionless quantities in the
reaction quotient QP because they are divided by the
standard-state value of 1 atm (see Table 17.2).
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Example 17.8
Solution Equation (17.13) can be written as
G = G o + RTlnQp
= G o + RTln
2
PNO
2
PN 2O4
(0.122) 2
= 5.40 10 J/mol + (8.314J/K mol)(298 K) ln
0.453
= 5.40 103 J/mol - 8.46 103 J/mol
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Example 17.8
Check
Note that although G > 0, the reaction can be made to favor
product formation initially by having a small concentration
(pressure) of the product compared to that of the reactant.
Confirm the prediction by showing that QP < KP.
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High Entropy
Low Entropy
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Coupled Reactions
Example:
Alanine + Glycine
G0 = +29 kJ
Alanylglycine
K<1
ADP + H3PO4 + Alanylglycine
K>1
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