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Free Energy *

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Abstract
By the end of this section, you will be able to:
• Dene Gibbs free energy, and describe its relation to spontaneity
• Calculate free energy change for a process using free energies of formation for its reactants and
products
• Calculate free energy change for a process using enthalpies of formation and the entropies for its
reactants and products
• Explain how temperature aects the spontaneity of some processes
• Relate standard free energy changes to equilibrium constants
One of the challenges of using the second law of thermodynamics to determine if a process is spontaneous
is that we must determine the entropy change for the system and the entropy change for the surroundings.
An alternative approach involving a new thermodynamic property dened in terms of system properties only
was introduced in the late nineteenth century by American mathematician Josiah Willard Gibbs. This new
property is called the Gibbs free energy change (G) (or simply the free energy ), and it is dened in
terms of a system's enthalpy and entropy as the following:

G = H − TS (1)

Free energy is a state function, and at constant temperature and pressure, the standard free energy
change (∆G ◦ ) may be expressed as the following:
∆G = ∆H − T ∆S (2)

(For simplicity's sake, the subscript sys will be omitted henceforth.)

We can understand the relationship between this system property and the spontaneity of a process by
recalling the previously derived second law expression:

qsurr
∆Suniv = ∆S + (3)
T
The rst law requires that q surr = −qsys , and at constant pressure q sys = ∆H, and so this expression may
be rewritten as the following:

∆H
∆Suniv = ∆S − (4)
T
* Version 1.14: Feb 15, 2018 4:27 pm -0600
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∆H is the enthalpy change of the system. Multiplying both sides of this equation by −T, and rearranging
yields the following:

−T ∆Suniv = ∆H − T ∆S (5)

Comparing this equation to the previous one for free energy change shows the following relation:

∆G = −T ∆Suniv (6)

The free energy change is therefore a reliable indicator of the spontaneity of a process, being directly related
to the previously identied spontaneity indicator, ∆S univ . Table 1 summarizes the relation between the
spontaneity of a process and the arithmetic signs of these indicators.

Relation between Process Spontaneity and Signs of Thermodynamic Properties

∆S univ > 0 ∆G < 0 spontaneous

∆S univ < 0 ∆G > 0 nonspontaneous

∆S univ = 0 ∆G = 0 reversible (at equilibrium)

Table 1

1 Calculating Free Energy Change

Free energy is a state function, so its value depends only on the conditions of the initial and nal states
of the system. A convenient and common approach to the calculation of free energy changes for physical
and chemical reactions is by use of widely available compilations of standard state thermodynamic data.
One method involves the use of standard enthalpies and entropies to compute standard free energy changes
according to the following relation as demonstrated in Example 1.

∆G ◦ = ∆H ◦ − T ∆S ◦ (7)

Example 1
Evaluation of ∆ G ◦
from ∆H ◦ and ∆ S ◦

Use standard enthalpy and entropy data from Appendix G to calculate the standard free energy
change for the vaporization of water at room temperature (298 K). What does the computed value
for ∆G ◦ say about the spontaneity of this process?
Solution
The process of interest is the following:

H2 O (l) −→ H2 O (g) (8)

The standard change in free energy may be calculated using the following equation:

◦
∆G298 = ∆H ◦ − T ∆S ◦ (9)

From Appendix G, here is the data:

Substance (kJ/mol) S298 (J/K·mol)

◦ ◦
∆Hf
H2 O(l ) −286.83 70.0

H2 O(g ) −241.82 188.8

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Table 2

Combining at 298 K:

◦ ◦ ◦
∆H ◦ = ∆H298 = ∆Hf (H2 O (g)) − ∆Hf (H2 O (l))
(10)
= [−241.82 kJ − (−286.83)] kJ/mol = 44.01 kJ/mol

◦ ◦ ◦
∆S ◦ = ∆S298 = S298 (H2 O (g)) − S298 (H2 O (l))
(11)
= 188.8 J/mol·K − 70.0 J/K = 118.8 J/mol·K

∆G ◦ = ∆H ◦ − T ∆S ◦ (12)

Converting everything into kJ and combining at 298 K:

◦
∆G298 = ∆H ◦ − T ∆S ◦
(13)

1 kJ
× 118.8 J/mol·K) × 1000
= 44.01 kJ/mol − (298 K
J
44.01 kJ/mol − 35.4 kJ/mol = 9.6 kJ/mol (14)
◦
◦
At 298 K (25 C) ∆G298 > 0, and so boiling is nonspontaneous (not spontaneous).
Check Your Learning
Use standard enthalpy and entropy data from Appendix G to calculate the standard free energy
change for the reaction shown here (298 K). What does the computed value for ∆G ◦ say about the
spontaneity of this process?

C2 H6 (g) −→ H2 (g) + C2 H4 (g) (15)

◦
◦
note: ∆G298 = 102.0 kJ/mol; the reaction is nonspontaneous (not spontaneous) at 25 C.

The standard free energy change for a reaction may also be calculated from standard free energy of
formation
◦

∆Gf , values of the reactants and products involved in the reaction. The standard free energy
of formation is the free energy change that accompanies the formation of one mole of a substance from its
◦
elements in their standard states. Similar to the standard enthalpy of formation, ∆Gf is by denition zero
◦
for elemental substances under standard state conditions. The approach used to calculate ∆G for a reaction
◦
from ∆Gf values is the same as that demonstrated previously for enthalpy and entropy changes. For the
reaction

mA + nB −→ xC + y D, (16)

the standard free energy change at room temperature may be calculated as

◦ ◦ ◦
∆G298 = ∆G ◦ =
P P
ν∆G298 (products) − ν∆G298 (reactants) (17)

◦ ◦ ◦ ◦
x∆Gf (C) + y∆Gf (D) m∆Gf (A) + n∆Gf (B) .
   
= −

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Example 2
Calculation of ∆G298
◦

Consider the decomposition of yellow mercury(II) oxide.

1
HgO (s, yellow) −→ Hg (l) + O2 (g) (18)
2
◦
Calculate the standard free energy change at room temperature, ∆G298 , using (a) standard free
energies of formation and (b) standard enthalpies of formation and standard entropies. Do the
results indicate the reaction to be spontaneous or nonspontaneous under standard conditions?
Solution
The required data are available in Appendix G and are shown here.

Compound (kJ/mol) (kJ/mol) S298 (J/K·mol)

◦ ◦ ◦
∆Gf ∆Hf
HgO (s, yellow) −58.43 −90.46 71.13

Hg(l ) 0 0 75.9

2
O (g ) 0 0 205.2

Table 3
(a) Using free energies of formation:

◦ X ◦ X ◦
∆G298 = νGSf (products) − ν∆Gf (reactants) (19)

 
◦ 1 ◦ ◦
= 1∆Gf Hg (l) + ∆Gf O2 (g) − 1∆Gf HgO (s, yellow) (20)
2
 
1
= 1 mol(0 kJ/mol) + mol(0 kJ/mol) − 1 mol(−58.43 kJ/mol) = 58.43 kJ/mol (21)
2
(b) Using enthalpies and entropies of formation:

◦ X ◦ X ◦
∆H298 = ν∆Hf (products) − ν∆Hf (reactants) (22)

 
◦ 1 ◦ ◦
= 1∆Hf Hg (l) + ∆Hf O2 (g) − 1∆Hf HgO (s, yellow) (23)
2
 
1
= 1 mol (0 kJ/mol) + mol (0 kJ/mol) − 1 mol (−90.46 kJ/mol) = 90.46 kJ/mol (24)
2
◦ X ◦ X ◦
∆S298 = ν∆S298 (products) − ν∆S298 (reactants) (25)

 
◦ 1 ◦ ◦
= 1∆S298 Hg (l) + ∆S298 O2 (g) − 1∆S298 HgO (s, yellow) (26)
2
 
1
= 1 mol (75.9 J/mol K) + mol (205.2 J/mol K) − 1 mol (71.13 J/mol K) = 107.4 J/mol K (27)
2
1 kJ
∆G ◦ = ∆H ◦ − T ∆S ◦ = 90.46 kJ − 298.15 K × 107.4 J/K·mol × (28)
1000 J

∆G ◦ = (90.46 − 32.01) kJ/mol = 58.45 kJ/mol (29)

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◦
Both ways to calculate the standard free energy change at 25 C give the same numerical value (to
three signicant gures), and both predict that the process is nonspontaneous (not spontaneous)
at room temperature.
Check Your Learning
Calculate ∆G ◦ using (a) free energies of formation and (b) enthalpies of formation and entropies
◦
(Appendix G). Do the results indicate the reaction to be spontaneous or nonspontaneous at 25 C?

C2 H4 (g) −→ H2 (g) + C2 H2 (g) (30)

note: (a) 140.8 kJ/mol, nonspontaneous

(b) 141.5 kJ/mol, nonspontaneous

2 Temperature Dependence of Spontaneity

As was previously demonstrated in this chapter's section on entropy, the spontaneity of a process may
depend upon the temperature of the system. Phase transitions, for example, will proceed spontaneously in
one direction or the other depending upon the temperature of the substance in question. Likewise, some
chemical reactions can also exhibit temperature dependent spontaneities. To illustrate this concept, the
equation relating free energy change to the enthalpy and entropy changes for the process is considered:

∆G = ∆H − T ∆S (31)

The spontaneity of a process, as reected in the arithmetic sign of its free energy change, is then determined
by the signs of the enthalpy and entropy changes and, in some cases, the absolute temperature. Since T is
the absolute (kelvin) temperature, it can only have positive values. Four possibilities therefore exist with
regard to the signs of the enthalpy and entropy changes:

1. Both ∆ H and ∆S are positive. This condition describes an endothermic process that involves an
increase in system entropy. In this case, ∆G will be negative if the magnitude of the T ∆S term is
greater than ∆H. If the T ∆S term is less than ∆H, the free energy change will be positive. Such a
process is spontaneous at high temperatures and nonspontaneous at low temperatures.
2. Both ∆ H and ∆ S are negative. This condition describes an exothermic process that involves a
decrease in system entropy. In this case, ∆G will be negative if the magnitude of the T ∆S term is less
than ∆H. If the T ∆S term's magnitude is greater than ∆H, the free energy change will be positive.
Such a process is spontaneous at low temperatures and nonspontaneous at high temperatures.
3. ∆ H is positive and ∆S is negative. This condition describes an endothermic process that involves
a decrease in system entropy. In this case, ∆G will be positive regardless of the temperature. Such a
process is nonspontaneous at all temperatures.
4. ∆ H is negative and ∆S is positive. This condition describes an exothermic process that involves
an increase in system entropy. In this case, ∆G will be negative regardless of the temperature. Such
a process is spontaneous at all temperatures.

These four scenarios are summarized in Figure 31.

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Figure 31: There are four possibilities regarding the signs of enthalpy and entropy changes.

Example 3
Predicting the Temperature Dependence of Spontaneity
The incomplete combustion of carbon is described by the following equation:

2C (s) + O2 (g) −→ 2CO (g) (32)

How does the spontaneity of this process depend upon temperature?

Solution
Combustion processes are exothermic (∆H < 0). This particular reaction involves an increase in
entropy due to the accompanying increase in the amount of gaseous species (net gain of one mole
of gas, ∆S > 0). The reaction is therefore spontaneous (∆G < 0) at all temperatures.
Check Your Learning
Popular chemical hand warmers generate heat by the air-oxidation of iron:

4Fe (s) + 3O2 (g) −→ 2Fe2 O3 (s) (33)

How does the spontaneity of this process depend upon temperature?

note: ∆H and ∆S are negative; the reaction is spontaneous at low temperatures.

When considering the conclusions drawn regarding the temperature dependence of spontaneity, it is im-
portant to keep in mind what the terms high and low mean. Since these terms are adjectives, the
temperatures in question are deemed high or low relative to some reference temperature. A process that is
nonspontaneous at one temperature but spontaneous at another will necessarily undergo a change in spon-
taneity (as reected by its ∆G) as temperature varies. This is clearly illustrated by a graphical presentation
of the free energy change equation, in which ∆G is plotted on the y axis versus T on the x axis:

∆G = ∆H − T ∆S (34)

y = b + mx (35)

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Such a plot is shown in Figure 37. A process whose enthalpy and entropy changes are of the same arithmetic
sign will exhibit a temperature-dependent spontaneity as depicted by the two yellow lines in the plot. Each
line crosses from one spontaneity domain (positive or negative ∆G ) to the other at a temperature that is
characteristic of the process in question. This temperature is represented by the x -intercept of the line, that
is, the value of T for which ∆G is zero:

∆G = 0 = ∆H − T ∆S (36)

∆H
T = (37)
∆S
And so, saying a process is spontaneous at high or low temperatures means the temperature is above or
below, respectively, that temperature at which ∆G for the process is zero. As noted earlier, the condition
of ∆G = 0 describes a system at equilibrium.

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Figure 37: These plots show the variation in ∆G with temperature for the four possible combinations
of arithmetic sign for ∆H and ∆S.

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Example 4
Equilibrium Temperature for a Phase Transition
As dened in the chapter on liquids and solids, the boiling point of a liquid is the temperature at
which its liquid and gaseous phases are in equilibrium (that is, when vaporization and condensation
occur at equal rates). Use the information in Appendix G to estimate the boiling point of water.
Solution
The process of interest is the following phase change:

H2 O (l) −→ H2 O (g) (38)

When this process is at equilibrium, ∆G = 0, so the following is true:

∆H ◦
0 = ∆H ◦ − T ∆S ◦ or T = (39)
∆S ◦
Using the standard thermodynamic data from Appendix G,

◦ ◦
∆H ◦ = ∆Hf (H2 O (g)) − ∆Hf (H2 O (l))
(40)
= −241.82 kJ/mol − (−286.83 kJ/mol) = 44.01 kJ/mol

◦ ◦
∆S ◦ = ∆S298 (H2 O (g)) − ∆S298 (H2 O (l))
(41)
= 188.8 J/K·mol − 70.0 J/K·mol = 118.8 J/K·mol

∆H ◦ 44.01 × 103 J/mol ◦

T = ◦ = = 370.5 K = 97.3 C (42)
∆S 118.8 J/K·mol
◦
The accepted value for water's normal boiling point is 373.2 K (100.0 C), and so this calculation
is in reasonable agreement. Note that the values for enthalpy and entropy changes data used were
derived from standard data at 298 K (Appendix G). If desired, you could obtain more accurate
results by using enthalpy and entropy changes determined at (or at least closer to) the actual boiling
point.
Check Your Learning
Use the information in Appendix G to estimate the boiling point of CS . 2
note: 313 K (accepted value 319 K)

3 Free Energy and Equilibrium

The free energy change for a process may be viewed as a measure of its driving force. A negative value for
∆G represents a nite driving force for the process in the forward direction, while a positive value represents
a driving force for the process in the reverse direction. When ∆G is zero, the forward and reverse driving
forces are equal, and so the process occurs in both directions at the same rate (the system is at equilibrium).
In the chapter on equilibrium the reaction quotient, Q, was introduced as a convenient measure of the
status of an equilibrium system. Recall that Q is the numerical value of the mass action expression for the
system, and that you may use its value to identify the direction in which a reaction will proceed in order
to achieve equilibrium. When Q is lesser than the equilibrium constant, K, the reaction will proceed in the
forward direction until equilibrium is reached and Q = K. Conversely, if Q > K, the process will proceed in

the reverse direction until equilibrium is achieved.

The free energy change for a process taking place with reactants and products present under nonstandard
conditions, ∆ G, is related to the standard free energy change, ∆G ◦ , according to this equation:

∆G = ∆G ◦ + RT ln Q (43)

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R is the gas constant (8.314 J/K mol), T is the kelvin or absolute temperature, and Q is the reaction

quotient. We may use this equation to predict the spontaneity for a process under any given set of conditions
as illustrated in Example 5.

Example 5
Calculating ∆G under Nonstandard Conditions
What is the free energy change for the process shown here under the specied conditions?
T = 25
◦
C, PN2 = 0.870 atm,P H2 = 0.250 atm, and PNH3 = 12.9 atm
2NH3 (g) −→ 3H2 (g) + N2 (g) ∆G ◦ = 33.0 kJ/mol (44)

Solution
The equation relating free energy change to standard free energy change and reaction quotient
may be used directly:

!
0.2503 × 0.870


◦ kJ J J
∆G = ∆G +RT ln Q = 33.0 + 8.314 × 298 K × ln = 9680 or 9.68 kJ/mol
mol mol K 12.92 mol

(45)
Since the computed value for ∆G is positive, the reaction is nonspontaneous under these conditions.
Check Your Learning
◦
Calculate the free energy change for this same reaction at 875 C in a 5.00 L mixture containing
0.100 mol of each gas. Is the reaction spontaneous under these conditions?

note: ∆G = −47 kJ; yes

For a system at equilibrium, Q = K and ∆G = 0, and the previous equation may be written as

0 = ∆G ◦ + RT ln K (at equilibrium) (46)

∆G ◦
∆G ◦ = −RT ln K or K = e− RT (47)

This form of the equation provides a useful link between these two essential thermodynamic properties,
and it can be used to derive equilibrium constants from standard free energy changes and vice versa. The
relations between standard free energy changes and equilibrium constants are summarized in Table 4.

Relations between Standard Free Energy Changes and Equilibrium Constants

K ∆G ◦ Comments
> 1 < 0 Products are more abundant at equilibrium.

< 1 > 0 Reactants are more abundant at equilibrium.

= 1 = 0 Reactants and products are equally abundant at equilibrium.

Table 4

Example 6
Calculating an Equilibrium Constant using Standard Free Energy Change
+ −
Given that the standard free energies of formation of Ag (aq ), Cl (aq ), and AgCl(s ) are 77.1
kJ/mol, −131.2 kJ/mol, and −109.8 kJ/mol, respectively, calculate the solubility product, K sp , for
AgCl.

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Solution
The reaction of interest is the following:

AgCl (s)
Ag
+ (aq) + Cl− (aq) Ksp =

Ag
+  Cl−  (48)

The standard free energy change for this reaction is rst computed using standard free energies of
formation for its reactants and products:

◦
∆G ◦ =∆G298 = ∆Gf
◦ + (aq)
+ ∆G ◦ − ◦
f (aq) − ∆Gf (AgCl (s))

  
Ag Cl (49)

=[77.1 kJ/mol − 131.2 kJ/mol] − [−109.8 kJ/mol] = 55.7 kJ/mol

The equilibrium constant for the reaction may then be derived from its standard free energy change:

◦
 
− ∆G ◦ × 103 J/mol
− ∆G − 8.31455.7


K sp =e RT = exp RT
= exp J/mol·K × 298.15 K
= exp (−22.470) = (50)

−22.470 −10
e = 1.74 × 10
This result is in reasonable agreement with the value provided in Appendix J.
Check Your Learning
Use the thermodynamic data provided in Appendix G to calculate the equilibrium constant for
◦
the dissociation of dinitrogen tetroxide at 25 C.

2NO2 (g)
N2 O4 (g) (51)

note: K = 6.9

To further illustrate the relation between these two essential thermodynamic concepts, consider the obser-
vation that reactions spontaneously proceed in a direction that ultimately establishes equilibrium. As may
be shown by plotting the free energy change versus the extent of the reaction (for example, as reected in
the value of Q ), equilibrium is established when the system's free energy is minimized (Figure 51). If a
system consists of reactants and products in nonequilibrium amounts (Q 6= K ), the reaction will proceed

spontaneously in the direction necessary to establish equilibrium.

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Figure 51: These plots show the free energy versus reaction progress for systems whose standard
free energy changes are (a) negative, (b) positive, and (c) zero. Nonequilibrium systems will proceed
spontaneously in whatever direction is necessary to minimize free energy and establish equilibrium.

4 Key Concepts and Summary

Gibbs free energy (G ) is a state function dened with regard to system quantities only and may be used to
predict the spontaneity of a process. A negative value for ∆G indicates a spontaneous process; a positive
∆G indicates a nonspontaneous process; and a ∆G of zero indicates that the system is at equilibrium. A

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number of approaches to the computation of free energy changes are possible.

5 Key Equations
ˆ ∆G = ∆H − T ∆S
ˆ ∆G = ∆G ◦ + RT ln Q

ˆ ∆G ◦ = −RT ln K

6 Chemistry End of Chapter Exercises

Exercise 1 ◦
What is the dierence between ∆ G, ∆ G ◦ , and ∆G298 for a chemical change?

Exercise 2 ◦ ◦
(Solution on p. 19.)
A reaction has ∆H298 = 100 kJ/mol and ∆S298 = 250 J/mol·K. Is the reaction spontaneous at
room temperature? If not, under what temperature conditions will it become spontaneous?

Exercise 3
Explain what happens as a reaction starts with ∆G < 0 (negative) and reaches the point where
∆G = 0.

Exercise 4 (Solution on p. 19.)

Use the standard free energy of formation data in Appendix G to determine the free energy change
◦
for each of the following reactions, which are run under standard state conditions and 25 C.
Identify each as either spontaneous or nonspontaneous at these conditions.
(a) MnO2 (s) −→ Mn (s) + O2 (g)
(b) H2 (g) + Br2 (l) −→ 2HBr (g)
(c) Cu (s) + S (g) −→ CuS (s)
(d) 2LiOH (s) + CO2 (g) −→ Li2 CO3 (s) + H2 O (g)
(e) CH4 (g) + O2 (g) −→ C (s, graphite) + 2H2 O (g)
(f ) CS2 (g) + 3Cl2 (g) −→ CCl4 (g) + S2 Cl2 (g)

Exercise 5
Use the standard free energy data in Appendix G to determine the free energy change for each of
◦
the following reactions, which are run under standard state conditions and 25 C. Identify each as
either spontaneous or nonspontaneous at these conditions.
(a) C (s, graphite) + O2 (g) −→ CO2 (g)
(b) O2 (g) + N2 (g) −→ 2NO (g)
(c) 2Cu (s) + S (g) −→ Cu2 S (s)
(d) CaO (s) + H2 O (l) −→ Ca(OH)2 (s)
(e) Fe2 O3 (s) + 3CO (g) −→ 2Fe (s) + 3CO2 (g)
(f ) CaSO4 ·2H2 O (s) −→ CaSO4 (s) + 2H2 O (g)

Exercise 6 (Solution on p. 19.)

Given:
◦
P4(s) + 5O2 (g) −→ P4 O10 (s) ∆G298 = −2697.0 kJ/mol
◦
2H2 (g) + O2 (g) −→ 2H2 O (g) ∆G298 = −457.18 kJ/mol
◦
6H2 O (g) + P4 O10 (s) −→ 4H3 PO4 (l) ∆G298 = −428.66 kJ/mol
◦
(a) Determine the standard free energy of formation, ∆Gf , for phosphoric acid.
(b) How does your calculated result compare to the value in Appendix G? Explain.

Exercise 7
3 2
Is the formation of ozone (O (g )) from oxygen (O (g )) spontaneous at room temperature under
standard state conditions?

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Exercise 8 (Solution on p. 19.)

Consider the decomposition of red mercury(II) oxide under standard state conditions.
2HgO (s, red) −→ 2Hg (l) + O2 (g)
(a) Is the decomposition spontaneous under standard state conditions?
(b) Above what temperature does the reaction become spontaneous?

Exercise 9
Among other things, an ideal fuel for the control thrusters of a space vehicle should decompose in a
spontaneous exothermic reaction when exposed to the appropriate catalyst. Evaluate the following
substances under standard state conditions as suitable candidates for fuels.
(a) Ammonia: 2NH3 (g) −→ N2 (g) + 3H2 (g)
(b) Diborane: B2 H6 (g) −→ 2B (g) + 3H2 (g)
(c) Hydrazine: N2 H4 (g) −→ N2 (g) + 2H2 (g)
1
(d) Hydrogen peroxide: H2 O2 (l) −→ H2 O (g) + (g)
2 O2
Exercise 10 (Solution on p. 19.)
Calculate ∆G ◦ for each of the following reactions from the equilibrium constant at the temperature
given.
(a) N2 (g) + O2 (g) −→ 2NO (g) ◦
T = 2000 C Kp = 4.1 × 10−4
◦
(b) H2 (g) + I2 (g) −→ 2HI (g) T = 400 C Kp = 50.0
◦
(c) CO2 (g) + H2 (g) −→ CO (g) + H2 O (g) T = 980 C Kp = 1.67
◦
(d) CaCO3 (s) −→ CaO (s) + CO2 (g) T = 900 C Kp = 1.04
+ −
(e) HF (aq) + H2 O (l) −→ H3 O (aq) + F (aq)
◦
T = 25 C Kp = 7.2 ×
10−4
(f ) AgBr (s) −→ Ag
+ (aq) + Br− (aq) T = 25 ◦
C Kp = 3.3 × 10−13
Exercise 11
Calculate ∆G ◦ for each of the following reactions from the equilibrium constant at the temperature
given.
(a) Cl2 (g) + Br2 (g) −→ 2BrCl (g) ◦
T = 25 C Kp = 4.7 × 10−2
◦
(b) 2SO2 (g) + O2 (g)
2SO3 (g) T = 500 C Kp = 48.2
◦
(c) H2 O (l)
H2 O (g) T = 60 C Kp = 0.196 atm
◦
(d) CoO (s) + CO (g)
Co (s) + CO2 (g) T = 550 C Kp = 4.90 × 102
+
(e) CH3 NH2 (aq)+H2 O (l) −→ CH3 NH3 (aq)+OH (aq)
−
T = 25 C
◦
Kp =
−4
4.4 × 10
(f ) PbI2 (s) −→ Pb
2+
(aq) + 2I− (aq) ◦
T = 25 C Kp = 8.7 × 10−9
Exercise 12 (Solution on p. 19.)
◦
Calculate the equilibrium constant at 25 C for each of the following reactions from the value of
∆G ◦ given.
(a) O2 (g) + 2F2 (g) −→ 2OF2 (g) ∆G ◦ = −9.2 kJ
(b) I2 (s) + Br2 (l) −→ 2IBr (g) ∆G ◦ = 7.3 kJ
(c) 2LiOH (s) + CO2 (g) −→ Li2 CO3 (s) + H2 O (g) ∆G ◦ = −79 kJ
◦
(d) N2 O3 (g) −→ NO (g) + NO2 (g) ∆G = −1.6 kJ
(e) SnCl4 (l) −→ SnCl4 (l) ∆G ◦ = 8.0 kJ
Exercise 13
◦
Calculate the equilibrium constant at 25 C for each of the following reactions from the value of
∆G ◦ given.
(a) I2(s) + Cl2 (g) −→ 2ICl (g) ∆G ◦ = −10.88 kJ
(b) H2 (g) + I2 (s) −→ 2HI (g) ∆G ◦ = 3.4 kJ
(c) CS2 (g) + 3Cl2 (g) −→ CCl4 (g) + S2 Cl2 (g) ∆G ◦ = −39 kJ
(d) 2SO2 (g) + O2 (g) −→ 2SO3 (g) ∆G ◦ = −141.82 kJ
(e) CS2 (g) −→ CS2 (l) ∆G ◦ = −1.88 kJ

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Exercise 14 (Solution on p. 19.)

Calculate the equilibrium constant at the temperature given.
(a) O2 (g) + 2F2 (g) −→ 2F2 O (g) (T = 100 ◦ C)
(b) I2 (s) + Br2 (l) −→ 2IBr (g) (T = 0.0 ◦ C)
◦
(c) 2LiOH (s) + CO2 (g) −→ Li2 CO3 (s) + H2 O (g) (T = 575 C)
(d) N2 O3 (g) −→ NO (g) + NO2 (g) (T = −10.0 ◦ C)
(e) SnCl4 (l) −→ SnCl4 (g) (T = 200 ◦ C)
Exercise 15
Calculate the equilibrium constant at the temperature given.
(a) I2(s) + Cl2 (g) −→ 2ICl (g) (T = 100 ◦ C)
(b) H2 (g) + I2 (s) −→ 2HI (g) (T = 0.0 ◦ C)
◦
(c) CS2 (g) + 3Cl2 (g) −→ CCl4 (g) + S2 Cl2 (g) (T = 125 C)
(d) 2SO2 (g) + O2 (g) −→ 2SO3 (g) (T = 675 ◦ C)
(e) CS2 (g) −→ CS2 (l) (T = 90 ◦ C)
Exercise 16 (Solution on p. 19.)
Consider the following reaction at 298 K:
N2 O4 (g)
2NO2 (g) KP = 0.142
What is the standard free energy change at this temperature? Describe what happens to the
initial system, where the reactants and products are in standard states, as it approaches equilibrium.

Exercise 17
2 2
Determine the normal boiling point (in kelvin) of dichloroethane, CH Cl . Find the actual boiling
point using the Internet or some other source, and calculate the percent error in the temperature.
Explain the dierences, if any, between the two values.

Exercise 18 (Solution on p. 19.)

Under what conditions is N2 O3 (g) −→ NO (g) + NO2 (g) spontaneous?

Exercise 19
w
At room temperature, the equilibrium constant (K ) for the self-ionization of water is 1.00 ×
10
− 14 . Using this information, calculate the standard free energy change for the aqueous reaction
of hydrogen ion with hydroxide ion to produce water. (Hint: The reaction is the reverse of the
self-ionization reaction.)

Exercise 20 (Solution on p. 19.)

Hydrogen sulde is a pollutant found in natural gas. Following its removal, it is converted to
3
sulfur by the reaction 2H2 S (g) + SO2 (g)

8 S8 (s, rhombic) + 2H2 O (l) . What is the equilibrium

constant for this reaction? Is the reaction endothermic or exothermic?

Exercise 21
3 2
Consider the decomposition of CaCO (s ) into CaO(s ) and CO (g ). What is the equilibrium partial
pressure of CO 2 at room temperature?

Exercise 22 (Solution on p. 19.)

3
In the laboratory, hydrogen chloride (HCl(g )) and ammonia (NH (g )) often escape from bottles of

4
their solutions and react to form the ammonium chloride (NH Cl(s )), the white glaze often seen on
glassware. Assuming that the number of moles of each gas that escapes into the room is the same,
what is the maximum partial pressure of HCl and NH 3 in the laboratory at room temperature?
(Hint: The partial pressures will be equal and are at their maximum value when at equilibrium.)

Exercise 23
Benzene can be prepared from acetylene. 3C2 H2 (g)
C6 H6 (g) . Determine the equilibrium
◦ ◦
constant at 25 C and at 850 C. Is the reaction spontaneous at either of these temperatures?
Why is all acetylene not found as benzene?

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Exercise 24 (Solution on p. 19.)

Carbon dioxide decomposes into CO and O 2 at elevated temperatures. What is the equilibrium
partial pressure of oxygen in a sample at 1000
◦
C for which the initial pressure of CO 2 was 1.15
atm?

Exercise 25
Carbon tetrachloride, an important industrial solvent, is prepared by the chlorination of methane
at 850 K.
CH4 (g) + 4Cl2 (g) −→ CCl4 (g) + 4HCl (g)
What is the equilibrium constant for the reaction at 850 K? Would the reaction vessel need to
be heated or cooled to keep the temperature of the reaction constant?

Exercise 26 (Solution on p. 19.)

3 2
Acetic acid, CH CO H, can form a dimer, (CH CO H) , in the gas phase. 3 2 2
2CH3 CO2 H (g) −→ (CH3 CO2 H)2 (g)
The dimer is held together by two hydrogen bonds with a total strength of 66.5 kJ per mole of
dimer.

At 25
◦
C, the equilibrium constant for the dimerization is 1.3 × 3
10 (pressure in atm). What is
◦
∆S for the reaction?

Exercise 27
3
Nitric acid, HNO , can be prepared by the following sequence of reactions:
4NH3 (g) + 5O2 (g) −→ 4NO (g) + 6H2 O (g)
2NO (g) + O2 (g) −→ 2NO2 (g)
3NO2 (g) + H2 O (l) −→ 2HNO3 (l) + NO (g)

3
How much heat is evolved when 1 mol of NH (g ) is converted to HNO (l )? Assume standard 3
◦
states at 25 C.

Exercise 28 (Solution on p. 19.)

Determine ∆G º for the following reactions.
◦
(a) Antimony pentachloride decomposes at 448 C. The reaction is:
SbCl5 (g) −→ SbCl3 (g) + Cl2 (g)
An equilibrium mixture in a 5.00 L ask at 448
◦
5
C contains 3.85 g of SbCl , 9.14 g of SbCl , 3
and 2.84 g of Cl . 2
(b) Chlorine molecules dissociate according to this reaction:
Cl2 (g) −→ 2Cl (g)
1.00% of Cl 2 molecules dissociate at 975 K and a pressure of 1.00 atm.

Exercise 29
Given that the ∆Gf 2+ (aq) and Cl− (aq) is −24.3 kJ/mole and −131.2 kJ/mole respectively,
◦
for Pb
determine the solubility product, K sp , for PbCl2 (s ).

Exercise 30 (Solution on p. 19.)

◦
Determine the standard free energy change, ∆Gf , for the formation of S
2− (aq) given that the
∆Gf for Ag+ (aq) and Ag2 S(s ) are 77.1 kJ/mole and −39.5 kJ/mole respectively, and the solubility
◦

−51
product for Ag2 S(s ) is 8 × 10 .

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Exercise 31
Determine the standard enthalpy change, entropy change, and free energy change for the conversion
of diamond to graphite. Discuss the spontaneity of the conversion with respect to the enthalpy and
entropy changes. Explain why diamond spontaneously changing into graphite is not observed.

Exercise 32 (Solution on p. 19.)

The evaporation of one mole of water at 298 K has a standard free energy change of 8.58 kJ.
◦
H2 O (l)
H2 O (g) ∆G298 = 8.58 kJ
(a) Is the evaporation of water under standard thermodynamic conditions spontaneous?

P
(b) Determine the equilibrium constant, K , for this physical process.
(c) By calculating ∆G, determine if the evaporation of water at 298 K is spontaneous when the
partial pressure of water, PH2 O , is 0.011 atm.
(d) If the evaporation of water were always nonspontaneous at room temperature, wet laundry
would never dry when placed outside. In order for laundry to dry, what must be the value of PH2 O
in the air?

Exercise 33
In glycolysis, the reaction of glucose (Glu) to form glucose-6-phosphate (G6P) requires ATP to be
present as described by the following equation:
◦
Glu + ATP −→ G6P + ADP ∆G298 = −17 kJ
In this process, ATP becomes ADP summarized by the following equation:
◦
ATP −→ ADP ∆G298 = −30 kJ
Determine the standard free energy change for the following reaction, and explain why ATP is
necessary to drive this process:
◦
Glu −→ G6P ∆G298 =?
Exercise 34 (Solution on p. 20.)
One of the important reactions in the biochemical pathway glycolysis is the reaction of glucose-6-
phosphate (G6P) to form fructose-6-phosphate (F6P):
◦
G6P
F6P ∆G298 = 1.7 kJ
(a) Is the reaction spontaneous or nonspontaneous under standard thermodynamic conditions?
(b) Standard thermodynamic conditions imply the concentrations of G6P and F6P to be 1
M, however, in a typical cell, they are not even close to these values. Calculate ∆G when the
concentrations of G6P and F6P are 120 µM and 28 µM respectively, and discuss the spontaneity
◦
of the forward reaction under these conditions. Assume the temperature is 37 C.

Exercise 35
Without doing a numerical calculation, determine which of the following will reduce the free energy
change for the reaction, that is, make it less positive or more negative, when the temperature is
increased. Explain.
(a) N2 (g) + 3H2 (g) −→ 2NH3 (g)
(b) HCl (g) + NH3 (g) −→ NH4 Cl (s)
(c) (NH4 )2 Cr2 O7 (s) −→ Cr2 O3 (s) + 4H2 O (g) + N2 (g)
(d) 2Fe (s) + 3O2 (g) −→ Fe2 O3 (s)

Exercise 36 (Solution on p. 20.)

When ammonium chloride is added to water and stirred, it dissolves spontaneously and the resulting
solution feels cold. Without doing any calculations, deduce the signs of ∆G, ∆H, and ∆S for this
process, and justify your choices.

Exercise 37
An important source of copper is from the copper ore, chalcocite, a form of copper(I) sulde. When

2
heated, the Cu S decomposes to form copper and sulfur described by the following equation:
Cu2 S (s) −→ Cu (s)+ S (s)
◦
(a) Determine ∆G298 for the decomposition of Cu S(s ). 2

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(b) The reaction of sulfur with oxygen yields sulfur dioxide as the only product. Write an
◦
equation that describes this reaction, and determine ∆G298 for the process.

2
(c) The production of copper from chalcocite is performed by roasting the Cu S in air to produce
the Cu. By combining the equations from Parts (a) and (b), write the equation that describes the
roasting of the chalcocite, and explain why coupling these reactions together makes for a more
ecient process for the production of the copper.

Exercise 38 (Solution on p. 20.)

What happens to ∆G (becomes more negative or more positive) for the following chemical reactions
when the partial pressure of oxygen is increased?
(a) S (s) + O2 (g) −→ SO2 (g)
(b) 2SO2 (g) + O2 (g) −→ 2SO3 (g)
(c) HgO (s) −→ Hg (l) + O2 (g)

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Solutions to Exercises in this Module

Solution to Exercise (p. 13)
The reaction is nonspontaneous at room temperature.
Above 400 K, ∆G will become negative, and the reaction will become spontaneous.
Solution to Exercise (p. 13)
(a) 465.1 kJ nonspontaneous; (b) −106.86 kJ spontaneous; (c) −53.6 kJ spontaneous; (d) −83.4 kJ sponta-
neous; (e) −406.7 −30.0 kJ spontaneous
kJ spontaneous; (f )
Solution to Exercise (p. 13)
(a) The standard free energy of formation is 1124.3 kJ/mol. (b) The calculation agrees with the value
in Appendix G because free energy is a state function (just like the enthalpy and entropy), so its change
depends only on the initial and nal states, not the path between them.
Solution to Exercise (p. 14)
◦
(a) The reaction is nonspontaneous; (b) Above 566 C the process is spontaneous.
Solution to Exercise (p. 14)
2
(a) 1.5 × 10 kJ; (b) −21.9 kJ; (c) −5.34 kJ; (d) −0.383 kJ; (e) 18 kJ; (f ) 71 kJ
Solution to Exercise (p. 14)
13
(a) K = 41; (b) K = 0.053; (c) K = 6.9 × 10 ; (d) K = 1.9; (e) K = 0.04
Solution to Exercise (p. 14)
In each of the following, the value of ∆G is not given at the temperature of the reaction. Therefore, we
must calculate ∆G from the values ∆H ◦ and ∆S and then calculate ∆G from the relation ∆G = ∆H ◦ −
T ∆S ◦ .
(a) K = 1.29;
(b) K = 2.51 × 10−3 ;
(c) K = 4.83 × 103 ;
(d) K = 0.219;
(e) K = 16.1
Solution to Exercise (p. 15) ◦
The standard free energy change is ∆G298 = −RT ln K = 4.84 kJ/mol. When reactants and products are
in their standard states (1 bar or 1 atm), Q = 1. As the reaction proceeds toward equilibrium, the reaction
shifts left (the amount of products drops while the amount of reactants increases): Q < 1, and ∆G298
becomes less positive as it approaches zero. At equilibrium, Q = K, and ∆G = 0.
Solution to Exercise (p. 15)
The reaction will be spontaneous at temperatures greater than 287 K.
Solution to Exercise (p. 15)
K = 5.35 × 10
15
The process is exothermic.
Solution to Exercise (p. 15)
−8
1.0 × 10 atm. This is the maximum pressure of the gases under the stated conditions.
Solution to Exercise (p. 16)
x = 1.29 × 10−5 atm = PO 2
Solution to Exercise (p. 16)
−0.16 kJ
Solution to Exercise (p. 16)
(a) 22.1 kJ;
(b) 61.6 kJ/mol
Solution to Exercise (p. 16)
90 kJ/mol
Solution to Exercise (p. 17)
(a) Under standard thermodynamic conditions, the evaporation is nonspontaneous; (b) K p = 0.031; (c) The
evaporation of water is spontaneous; (d) PH 2 O must always be less than K p or less than 0.031 atm. 0.031

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◦
atm represents air saturated with water vapor at 25 C, or 100% humidity.
Solution to Exercise (p. 17) ◦ ◦
= 1.7 × 103 + 8.314 × 310 × 28


(a) Nonspontaneous as ∆G298 > 0; (b) ∆G = ∆G +RT ln Q,∆G ln
120 =
−2.1 kJ. The forward reaction to produce F6P is spontaneous under these conditions.
Solution to Exercise (p. 17)
∆G is negative as the process is spontaneous. ∆H is positive as with the solution becoming cold, the
dissolving must be endothermic. ∆S must be positive as this drives the process, and it is expected for the
dissolution of any soluble ionic compound.
Solution to Exercise (p. 18)
(a) Increasing the oxygen partial pressure will yield a decrease in Q and ∆G thus becomes more negative.
(b) Increasing the oxygen partial pressure will yield a decrease in Q and ∆G thus becomes more negative.
(c) Increasing the oxygen partial pressure will yield an increase in Q and ∆G thus becomes more positive.

Glossary
Denition 51: Gibbs free energy change (G)
thermodynamic property dened in terms of system enthalpy and entropy; all spontaneous processes
involve a decrease in G

Denition 51: standard free energy change (∆G ◦ )

change in free energy for a process occurring under standard conditions (1 bar pressure for gases,
1 M concentration for solutions)

Denition 51: standard free energy of formation

◦

∆Gf
change in free energy accompanying the formation of one mole of substance from its elements in
their standard states

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