Notes Chem Eq

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PRINCIPLES OF
CHEMICAL
EQUILIBRIUM
CONTENTS
15-1 Dynamic Equilibrium

15-2 The Equilibrium Constant
Expression
15-3 Relationships Involving
Equilibrium Constants
15-4 The Magnitude of an
Equilibrium Constant
15-5 The Reaction Quotient, Q:
Predicting the Direction
of Net Change
15-6 Altering Equilibrium
Conditions: Le Châtelier’s
Principle
15-7 Equilibrium Calculations:
Some Illustrative
Examples
➣ FOCUS ON The Nitrogen
Cycle and the Synthesis of
Nitrogen Compounds A vital natural reaction is in progress in the lightning bolt seen here:
N2(g) + O2(g) ∆ 2 NO(g). Usually this reversible reaction does not occur
to any significant extent in the forward direction, but in the high-temperature
There are many lightning bolt it does. At equilibrium at high temperatures, measurable
demonstrations that show
conversion of N2(g) and O2(g) to NO(g) occurs. In this chapter we study the
equilibrium: roll a marble in a
parabolic clear dish to show the equilibrium condition in a reversible reaction and the factors affecting it.
establishment of physical
equilibrium; pour AgNO3 into
ordinary tap water, and the
U
chloride ion in the water will ntil now, we have stressed reactions that go to completion
precipitate out leaving the water and the concepts of stoichiometry that allow us to calculate
cloudy; burn a match, and when it
goes out, equilibrium is the outcomes of such reactions. We have made occasional
established. Point out that references to situations involving both a forward and a reverse
equilibrium in chemical reactions is reaction—reversible reactions—but in this chapter, we will look at
obtained by minimizing the free
energy (see Chapter 19). them in a detailed and systematic way.
Our emphasis will be on the equilibrium condition reached when
Point out that equilibrium forward and reverse reactions proceed at the same rate. Our main
is less common than tool in dealing with equilibrium will be the equilibrium constant.
nonequilibrium. For
example, your heart and other We will begin with some key relationships involving equilibrium
biochemical processes are constants; then we will make qualitative predictions about the con-
oscillating back and forth in cycles. dition of equilibrium; and finally we will do various equilibrium
We certainly don’t want our hearts
to come to equilibrium. calculations. As we will discover throughout the remainder of the
text, the equilibrium condition plays a role in numerous natural
phenomena and affects the methods used to produce many impor-
tant industrial chemicals.
622
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15-2 The Equilibrium Constant Expression 623
Dynamic Equilibrium
15-1 DYNAMIC EQUILIBRIUM animation
Let’s begin by describing three simple physical and one chemical phenomena
that will help us to establish the core attribute of a system at equilibrium— Paiva, João C. M., Victor M. S.
two opposing processes take place at equal rates. Gil. “The Complexity of
Teaching and Learning Chemical
1. When a liquid vaporizes within a closed container, after a time, vapor Equilibrium.” J. Chem. Educ.
molecules condense to the liquid state at the same rate at which liquid 2000: 77, 1560 (December 2000).
molecules vaporize. Even though molecules continue to pass back and Silverstein, Todd P.
forth between liquid and vapor (a dynamic process), the pressure exerted “Equilibrium: A Teaching/
by the vapor remains constant with time. The vapor pressure of a liquid is a Learning Activity.” J. Chem. Educ.
2000: 77, 1410 (November 2000).
property resulting from an equilibrium condition.
2. When a solute is added to a solvent, the system may reach a point at which The two opposing
the rate of dissolution is just matched by the rate at which dissolved solute processes operate at the
microscopic level.
crystallizes—that is, the solution is saturated. Even though solute particles
continue to pass back and forth between the saturated solution and the
undissolved solute, the concentration of dissolved solute remains constant.
The solubility of a solute is a property resulting from an equilibrium condition.
3. When an aqueous solution of iodine, I 2 , is shaken with pure carbon tetra-
chloride, CCl4(l), the I 2 molecules move into the CCl4 layer. As the concen-
tration of I 2 builds up in the CCl4 , the rate of return of I 2 to the water layer
becomes significant. When I 2 molecules pass between the two liquids at
equal rates—a condition of dynamic equilibrium—the concentration of I 2
in each layer remains constant. At this point, the concentration of I 2 in the
CCl4 is about 85 times greater than in the H 2O (Fig. 15-1). The ratio of con-
centrations of a solute in two immiscible solvents is called the distribution
coefficient. The distribution coefficient, which represents the partitioning of a
solute between two immiscible solvents, is a property resulting from an equilibri-
um condition.
4. When gaseous phosphorus pentachloride is heated, it decomposes to phos-
(a) (b)
phorus trichloride and chlorine gases: PCl5(g) ¡ PCl3(g) + Cl2(g).
Consider a sample of PCl5(g) initially exerting a pressure of 1.0 atm in a ▲ FIGURE 15-1
closed container at 250 °C. The gas pressure in the container first rises Dynamic equilibrium in a
rapidly and then ever more slowly, reaching a maximum, unchanging pres- physical process
(a) A yellow-brown saturated
sure of 1.7 atm. Because two moles of gas are produced for each mole of
solution of I 2 in water
PCl5(g) that decomposes, if the reaction went to completion the final pres- (top layer) is brought into
sure would have been 2.0 atm. We conclude that the decomposition of PCl5 is contact with colorless CCl4(l)
a reversible reaction that reaches an equilibrium condition. (bottom layer). (b) I 2 mole-
The properties in the first three situations just described—vapor pressure, cules distribute themselves
between the H 2O and CCl4 .
solubility, and distribution coefficient—are examples of physical equilibria.
When equilibrium is reached,
The fourth situation is an example of chemical equilibrium. All four are de- [I 2] in the CCl4 (violet,
scribed through a general quantity known as an equilibrium constant, the sub- bottom layer) is about 85
ject of the next section. times greater than in the
water (colorless, top layer).
15-2 THE EQUILIBRIUM CONSTANT EXPRESSION

Methanol (methyl alcohol) is synthesized from a carbon monoxide–hydrogen
mixture called synthesis gas. This reaction is likely to become increasingly im-
portant as methanol and its mixtures with gasoline find greater use as motor
fuels. Methanol has a high octane rating, and its combustion produces much
less air pollution than does gasoline.
Methanol synthesis is a reversible reaction, which means that at the same
time CH 3OH(g) is being formed,
CO(g) + 2 H 2(g) ¡ CH 3OH(g) (15.1) ▲ Methanol is actively being
it decomposes in the reverse reaction considered as an alternative
fuel to gasoline.
CH 3OH(g) ¡ CO(g) + 2 H 2(g) (15.2)
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624 Chapter 15 Principles of Chemical Equilibrium
In anticipation of entropy, Are You Wondering . . .

point out that a mixing
process and a dissolution How we know that an equilibrium is dynamic—that forward and reverse
process lead to an increase in reactions continue even after equilibrium is reached?
disorder.
Suppose we have an equilibrium mixture of AgI(s) and its saturated aqueous solution.
AgI(s) ∆ AgI(satd aq)
Now let’s add to this mixture some saturated solution of AgI made from AgI
containing radioactive iodine-131 as iodide ion, as illustrated in Figure 15-2. If
both the forward and reverse processes stopped at equilibrium, radioactivity
would be confined to the solution. What we find, though, is that radioactivity
shows up in the solid in contact with the saturated solution. Over time, the ra-
dioactive “hot” spots distribute themselves throughout the solution and undis-
solved solid. The only way this can happen is if the dissolving of the solid solute
and its crystallization from the saturated solution continue indefinitely. The equi-
librium condition is dynamic.
Saturated solution only

added to beaker
(a)
(b)
▲ FIGURE 15-2
Dynamic equilibrium illustrated
(a) A saturated solution of radioactive AgI is added to a saturated solution
of AgI. (b) The radioactive iodide ions distribute themselves throughout the
solution and the solid AgI, showing that the equilibrium is dynamic.
Remind students that the Initially, only the forward reaction (15.1) occurs, but as soon as some
rates of reactions (forward CH 3OH forms, the reverse reaction (15.2) begins. With passing time, the for-
and reverse) are affected by
the concentration of reactants. ward reaction slows because of the decreasing concentrations of CO and H 2
and the reverse reaction speeds up as more CH 3OH accumulates. Eventually,
the forward and reverse reactions proceed at equal rates, and the reaction mix-
ture reaches a condition of dynamic equilibrium, which we can represent with
a double arrow ∆ .
CO(g) + 2 H 2(g) ∆ CH 3OH(g) (15.3)
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TABLE 15.1 Three Approaches to Equilibrium in the Reactiona

CO(g) 2 H2(g) ∆ CH3OH(g)
CO(g) H2(g) CH3OH(g) Point out to students that

the equilibrium state can be
Experiment 1 obtained by starting with
any combination of reactants
Initial amounts, mol 1.000 1.000 0.000 and/or products.
Equilibrium amounts, mol 0.911 0.822 0.0892
Equilibrium concentrations, mol/L 0.0911 0.0822 0.00892
Experiment 2
Initial amounts, mol 0.000 0.000 1.000

Experiment 3
Initial amounts, mol 1.000 1.000 1.000

The concentrations printed in blue are used in the calculations in Table 15.2.
a
Reaction carried out in a 10.0-L flask at 483 K.
One consequence of the equilibrium condition is that the amounts of the Silverstein, Todd P. “The Real
reactants and products remain constant with time. These equilibrium amounts, Reason Why Oil and Water
Don’t Mix.” J. Chem. Educ. 1998:
however, depend on the quantities of reactants and products present initially. 75, 116 (January 1998).
For example, Table 15.1 lists data for three hypothetical experiments. All three
experiments are conducted in a 10.0-L flask at 483 K. In the first experiment, Jordan, A. D. “Liquid-Liquid
Equilibrium: Verification of
only CO and H 2 are present initially; in the second, only CH 3OH; and in the the Lever Rule.” J. Chem. Educ.
third, CO, H 2 , and CH 3OH. The data from Table 15.1 are plotted in Figure 15-3, 2000: 77, 395 (March 2000).
and from these graphs we see that
Harrison, J. A., Buckley, P. D.
• in no case is any reacting species completely consumed; “Simulating Dynamic
• in all three cases the equilibrium amounts of reactants and products Equilibria: A Class Experiment.”
appear to have nothing in common. J. Chem. Educ. 2000: 77, 1013
(August 2000).
2.00 2.00 2.00 te

1.80 1.80 1.80
te
1.60 1.60 1.60
Moles of reactants and products
1.40 1.40 1.40

Chemical Equilibrium
activity
1.20 1.20 1.20
te
1.00 1.00 1.00
0.80 0.80 0.80
0.60 0.60 0.60
0.40 0.40 0.40
0.20 0.20 0.20

FIGURE 15-3
▲
Three approaches to equilibrium

Time Time Time in the reaction
Experiment 1 Experiment 2 Experiment 3 CO(g) 2 H2(g) ∆ CH3OH(g)
The initial and equilibrium amounts
te time for equilibrium to be reached for each of these three cases are
mol CO listed in Table 15.1. te = time for
mol H2 equilibrium to be reached.
mol CH3OH
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TABLE 15.2
[CH3OH] [CH3OH] [CH3OH]

Expt Trial 1: Trial 2: Trial 3:
[CO][H2] [CO](2 : [H2]) [CO][H2]2
0.00892 0.00892 0.00892

0.0911 * 12 * 0.08222 0.0911 * 10.082222
1 = 1.19 = 0.596 = 14.5
0.0911 * 0.0822
0.0247 0.0247 0.0247
0.0753 * 12 * 0.1512 0.0753 * 10.15122
2 = 2.17 = 1.09 = 14.4
0.0753 * 0.151
0.0620 0.0620 0.0620
0.138 * 12 * 0.1762 0.138 * 10.17622
3 = 2.55 = 1.280 = 14.5
0.138 * 0.176
Equilibrium concentration data are from Table 15.1. In Trial 1, the equilibrium concentration of CH 3OH is placed in the numerator
and the product of the equilibrium concentrations, [CO][H 2], in the denominator. In Trial 2, each concentration is multiplied by
its stoichiometric coefficient. In Trial 3, each concentration is raised to a power equal to its stoichiometric coefficient. Trial 3 has
essentially the same value for each experiment. This value is the equilibrium constant Kc .
In the three experiments, point Although it is not obvious from a cursory inspection of the data, a particu-
out that Table 15.1 is consistent lar ratio involving equilibrium concentrations of product and reactants has a
with the equilibrium
concentrations of the two reactants
constant value, independent of how the equilibrium is reached. This ratio,
and the one product in Figure 15-3. which is central to the study of chemical equilibrium, can be derived theoreti-
Put the equilibrium concentrations cally using concepts presented later in the text, but it can also be established
into the equilibrium expression
(15.4) to show that this equation
empirically, that is, by trial and error. Three reasonable attempts at formulat-
is satisfied. ing the desired ratio for reaction (15.3) are outlined in Table 15.2, and the ratio
that works is identified.
For the methanol synthesis reaction, the ratio of equilibrium concentrations
in the following equation has a constant value of 14.5 at 483 K.
[CH 3OH]
The representation of the K = ¢ ≤ = 14.5 (15.4)
equilibrium expression in [CO]([H 2])2 eq
terms of concentrations is
only valid at low concentrations, This ratio is called the equilibrium constant expression and its numerical
usually less than a few moles value is the equilibrium constant.
per liter.
Stress that “equilibrium”

THE EQUILIBRIUM CONSTANT AND ACTIVITIES
means equal forward Let’s think about expression (15.4) for a moment. We have shown that we ob-
and reverse reactions,
not equal concentrations of
tain a numerical value of 14.5 by substituting equilibrium concentrations from
reactants and products. Table 15.2 (Trial 3) into the equilibrium constant expression. But what hap-
pened to the units? The numerator in expression (15.4) has the unit mol L-1 and
the denominator, mol3 L-3. The resultant unit to accompany the numerical
value looks like it should be L2 mol -2. In later chapters we will encounter sev-
eral expressions that require the logarithm of an equilibrium constant, but we
can only take the logarithms of dimensionless numbers, not of numbers that
carry units. We took the easy way out in equation (15.4) by just “dropping” the
troublesome units. But there is a more satisfactory way to eliminate the units.
We need to replace equation (15.4) by the following expression
aCH3OH
K = ¢ ≤ = 14.5 (15.5)
aCO(aH2)2 eq
where a represents the activity of each reactant or product denoted through a

subscript formula. Activity, a thermodynamic concept introduced by G. N.
Lewis,* is the dimensionless ratio [X]>c°, where [X] represents a particular
concentration and c° corresponds to the concentration in a chosen reference
state. Our usual choice of reference state for a substance in solution is a
concentration of one mole per liter (1 mol L-1). For gases, activity can also be
expressed as the dimensionless ratio, P>P°, where P is a particular partial
*G. N. Lewis and M. Randall, Thermodynamics, McGraw Hill, New York, 1923.
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pressure and P° is the partial pressure in the reference state; and our usual Point out to students that
choice of P° is 1 bar (essentially equal to 1 atm). Pure solids and pure liquids the equilibrium constant
“14.5” calculated for the
are assigned activities of 1. methanol synthesis reaction is
Now, by returning to the methanol-synthesis example, let us establish the re- specific to a 483 K reaction
lationship between an equilibrium constant expressed in activities and the cor- temperature.
responding one expressed in concentrations. We begin by writing the activity
of each species, using the [ ] symbol for the equilibrium concentration and c 0
for the concentration in the reference state.
[CH 3OH]
aCH3OH =
c°
[CO]
aCO =
c°
[H 2]
aH2 =
c°
Then we choose the value c° = 1 mol L-1, substitute these relationships
into the equilibrium constant expression (15.5), and we have
[CH 3OH]
= 1c°2 ¢
c° 2 [CH 3OH]
K = § ¥ ≤ KEEP IN MIND
▲
= 14.5 (15.6)
[CO] [H 2] 2 [CO]([H 2])2 eq that any concentrations
¢ ≤
c° c° eq substituted into an
Notice that we have arrived at exactly the expression in equation (15.4)! In this equilibrium constant
expression, or obtained
case, however, the unwanted units have been properly cancelled rather than
from it, must be equilibrium
just conveniently dropped; that is, L2 mol -2 inside the large parentheses is concentrations.
cancelled by mol2 L-2 on the outside.
Here is another reason for basing equilibrium constants on activities: Under
conditions where gases do not obey the ideal gas law (Section 6-9) or solutions
depart from ideal behavior (Section 13-3), equilibrium constant values may
vary with total concentration or pressure. This problem is eliminated when
activities are used. As we learned in Section 13-9, activities are “effective” or
“active” concentrations. In this text we will generally assume that systems are
ideal, and that activities can be replaced by concentrations or partial pressures.
EXAMPLE 15-1
Relating Equilibrium Concentrations of Reactants and Products. These equilibrium concentrations are measured in
reaction (15.3) at 483 K: [CO] = 1.03 M and [CH 3OH] = 1.56 M. What is the equilibrium concentration of H 2?
Solution
Write the equilibrium constant expression in terms of activities aCH3OH
K = ¢ ≤ = 14.5
aCO(aH2)2 eq
Assume that the reaction conditions are such that the activities can [CH 3OH]
be replaced by their concentration values, allowing concentration K = ¢ ≤ = 14.5
units to be canceled as in expression (15.6). [CO]([H 2])2 eq
Substitute the known equilibrium concentrations into the equilibri- [CH 3OH] 1.56
um constant expression (15.6). K = 2
= = 14.5
[CO][H 2] 1.03[H 2]2
Solve for the unknown concentration, [H 2]. (An implicit calcula- 1.56
tion to restore the concentration unit is [H 2] = aH2 * c° = [H 2]2 = = 0.104
1.03 * 14.5
0.322 * 1.00 M = 0.322 M.) [H 2] = 20.104 = 0.322 M
Practice Example A: In another experiment, equal concentrations of CH 3OH and CO are found at equilibrium in
reaction (15.3). What must be the equilibrium concentration of H 2 ?
Practice Example B: At a certain temperature, K = 1.8 * 104 for the reaction N2(g) + 3 H 2(g) ∆ 2 NH 3(g).
If the equilibrium concentrations of N2 and NH 3 are 0.015 M and 2.00 M, respectively, what is the equilibrium concen-
tration of H 2 ?
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A GENERAL EXPRESSION FOR K

Remind students not to Before proceeding to other matters, let us emphasize that the equilibrium
confuse equilibrium constant expression for the methanol synthesis reaction summarized through
constant expressions
with rate equations (Chapter 14). expression (15.6) is just a specific example of a more general case. For the
The former contains stoichiometric hypothetical, generalized reaction
coefficients whereas the latter
does not. However, a similarity is aA + bB Á ∆ gG + hH Á
that both the rate constant and the
equilibrium constant vary with The equilibrium constant expression has the form
temperature.
g
(aG) (aH)h Á [G]g[H]h Á
K = = (15.7)
(aA)a(aB)b Á [A]a[B]b Á
The numerator of an equilibrium constant expression is the product of the

activities of the species on the right side of the equation (aG , aH , Á ), with each
activity raised to a power given by the stoichiometric coefficient (g, h, Á ). The
denominator is the product of the activities of the species on the left side of the
equation (aA , aB , Á ), and again, with each activity raised to a power given by
the stoichiometric coefficient (a, b, Á ). As previously noted, where equilibri-
um systems are sufficiently close to ideal in their behavior, equilibrium con-
centrations are acceptable approximations to true activities.
The numerical value of an equilibrium constant, K, depends on the particu-
lar reaction and on the temperature. We will explore the significance of these
numerical values in Section 15-4.
CONCEPT ASSESSMENT ✓
Consider a hypothetical reaction in which one molecule, A, is converted to its isomer,
B, that is, the reversible reaction A ∆ B. Start with a flask containing 54 molecules
of A, represented by open circles. Convert the appropriate number of open circles to
filled circles to represent the isomer B and portray the equilibrium condition if
K = 0.02. Repeat the process for K = 0.5 and then for K = 1.
Are You Wondering . . .

If there is a relationship between the equilibrium constant and rate
constants?
Given the requirement that the rates of the forward and reverse reactions become
equal at equilibrium, it seems that there should be a relationship. The rate laws for
the forward and reverse reactions include numerical constants (rate constants) and
concentration terms raised to powers. Moreover, if we set the rate equations equal
to one another at equilibrium, we should be able to derive an expression involving
a ratio of concentration terms (raised to powers) and a ratio of constants. A major
difficulty, however, is that the exponents of the concentration terms in the equilib-
rium constant expression must be the same as the coefficients in the balanced equa-
tion, whereas the exponents in rate laws are generally not the same as these
coefficients. The trick to discovering the relationship between rate constants and an
equilibrium constant is to work with the detailed mechanism for the reaction in the
manner outlined in Exercise 83. Still, it is generally easier to obtain K directly from
measurements on equilibrium conditions than to attempt a calculation based on
rate constants. Moreover, in Chapters 19 and 20 we will learn about much more
direct measurements and calculations leading to values of equilibrium constants.
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15-3 Relationships Involving Equilibrium Constants 629
15-3 RELATIONSHIPS INVOLVING EQUILIBRIUM

CONSTANTS
Before assessing an equilibrium situation, it may be necessary to make some
preliminary calculations or decisions to get the appropriate equilibrium con-
stant expression. This section presents some useful ideas in working with
equilibrium constants.
RELATIONSHIP OF K TO THE BALANCED CHEMICAL EQUATION

We must always make certain that the expression for K matches the corre-
sponding balanced equation. In doing so, the following hold true.
• When we reverse an equation, we invert the value of K.
• When we multiply the coefficients in a balanced equation by a common
factor (2, 3, Á ), we raise the equilibrium constant to the corresponding
power (2, 3, Á ).
• When we divide the coefficients in a balanced equation by a common fac-
tor (2, 3, Á ), we take the corresponding root of the equilibrium constant
(square root, cube root, Á ).
Suppose that in discussing the synthesis of CH 3OH from CO and H 2 , we
had written the reverse of equation (15.3)—that is,
CH 3OH(g) ∆ CO(g) + 2 H 2(g) K¿ = ?
Now, according to the generalized equilibrium constant expression (15.7), we
should write
[CO][H 2]2 1 1 1
K¿ = = = = = 0.0690
[CH 3OH] [CH 3OH] K 14.5
[CO][H 2]2
In the preceding expression, the terms printed in blue are the equilibrium con-
stant expression and K value originally written as expression (15.4). We see
that K¿ = 1>K.
Suppose that for a certain application we want an equation based on syn-
thesizing two moles of CH 3OH(g).
2 CO(g) + 4 H 2(g) ∆ 2 CH 3OH(g) K– = ?
2
Here, K– = K . That is,
[CH 3OH]2 [CH 3OH] 2
K– = 2 4
= ¢ 2
≤ = (K)2 = (14.5)2 = 2.10 * 102
[CO] [H 2] [CO][H 2]
EXAMPLE 15-2
Relating K to the Balanced Chemical Equation. The following K value is given at 298 K for the synthesis of NH 3(g)
from its elements.
N2(g) + 3 H 2(g) ∆ 2 NH 3(g) K = 3.6 * 108
What is the value of K at 298 K for the following reaction?
1 3
NH 3(g) ∆ N (g) + H 2(g) K = ?
2 2 2
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Solution
First, reverse the given equation. This puts NH 3(g) on the
left side of the equation, where we need it. 2 NH 3(g) ∆ N2(g) + 3 H 2(g)
The equilibrium constant K¿ becomes K¿ = 1>13.6 * 1082 = 2.8 * 10-9
Then, to base the equation on 1 mol NH 3(g), divide all coef- 1 3

NH 3(g) ∆ N2(g) + H 2(g)
ficients by 2. 2 2
This requires the square root of K¿. K = 32.8 * 10-9 = 5.3 * 10-5
Practice Example A: Use data from Example 15-2 to determine the value of K at 298 K for the reaction
1 2
N (g) + H 2(g) ∆ NH 3(g)
3 2 3
1
Practice Example B: For the reaction NO(g) + O2(g) ∆ NO2(g) at 184 ° C, K = 7.5 * 102. What is the value
2
of K at 184 °C for the reaction 2 NO2(g) ∆ 2 NO(g) + O2(g)?
Can you conclude whether the numerical value of K for the reaction 2 ICl(g) ∆
I 2(g) + Cl2(g) is greater or less than the numerical value of K for the reaction
1 1
ICl(g) ∆ I 2(g) + Cl2(g)? Explain.
2 2
COMBINING EQUILIBRIUM CONSTANT EXPRESSIONS

In Section 7-7, through Hess’s law, we showed how to combine a series of
equations into a single overall equation. The enthalpy change of the overall re-
action was obtained by adding together the enthalpy changes of the individ-
ual reactions. A similar procedure can be used with equilibrium constants, but
with this important difference:
When individual equations are combined (that is, added), their equilibrium constants
are multiplied to obtain the equilibrium constant for the overall reaction.
Suppose we seek the equilibrium constant for the reaction

1
N2O(g) + O (g) ∆ 2 NO(g) K = ? (15.8)
2 2
and know the K values of these two equilibria.
1
N2(g) + O (g) ∆ N2O(g) K = 2.7 * 10-18 (15.9)
2 2
N2(g) + O2(g) ∆ 2 NO(g) K = 4.7 * 10-31 (15.10)
Equation (15.8) is obtained by reversing equation (15.9) and adding it to (15.10).

This requires that we also take the reciprocal of the K value of equation (15.9).
1
(a) N2O(g) ∆ N2(g) + O (g) K(a) = 1>(2.7 * 10-18)
2 2
= 3.7 * 1017
(b) N2(g) + O2(g) ∆ 2 NO(g) K(b) = 4.7 * 10-31

1
Overall: N2O(g) + O (g) ∆ 2 NO(g) K(overall) = ?
2 2
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The overall equation is expression (15.8), and according to the general

expression (15.7),
[NO]2 [N2][O2]1>2 [NO]2
K(overall) = = * = K(a) * K(b)
[N2O][O 2]1>2 [N2O] [N2][O2]
3 3
K(a) K(b)
= 3.7 * 1017 * 4.7 * 10-31 = 1.7 * 10-13
CONCEPT ASSESSMENT ✓ Point out that the reaction

of sulfur dioxide with
oxygen gas to form sulfur
You wish to calculate K for the reaction trioxide is a reaction that takes
CH 4(g) + 2 H 2O(g) ∆ CO2(g) + 4 H 2(g) place in the atmosphere. This
results in the formation of sulfuric
and you have available a K value for the reaction acid which contributes to acid rain.
CO2(g) + H 2(g) ∆ CO(g) + H 2O(g)
What additional K value do you need, assuming that all K values are at the same
temperature?
EQUILIBRIA INVOLVING GASES: THE EQUILIBRIUM CONSTANTS,

Kc AND Kp
Mixtures of gases are as much solutions as are mixtures in a liquid solvent.
Thus, concentrations in a gaseous mixture can be expressed on a mole-per-
liter basis, and this is what we have done in writing K expressions using con-
centration units for our reference state. In order to describe gaseous reactants
and products through their partial pressures in atmospheres, which is com-
monly done, we need to switch our reference state. We will do this next.
A key step in the manufacture of sulfuric acid is the following reversible
reaction.
2 SO 2(g) + O2(g) ∆ 2 SO 3(g) (15.11)
Since all of the reaction species are in the gas phase it seems reasonable to use
a partial-pressure reference state. We begin by writing the equilibrium con-
stant expression in terms of activities
(aSO3)2
K = ¢ ≤ (15.12)
(aSO2)2aO2 eq
where the activities are
PSO2 PO2 PSO3
aSO2 = ; aO2 = ; aSO3 =
P° P° P°
The reference-state partial pressure is P° = 1 bar, which we will take to be
essentially the same as 1 atm. Substituting these relationships into equation
(15.12), we obtain
PSO3 2
¢ ≤
P° (PSO3)2
Kp = § ¥ = P° ¢ ≤ (15.13)
PSO2 2 PO
2 (PSO2)2PO2 eq
¢ ≤
P° P° eq
As expected, the equilibrium constant is dimensionless. To designate that a

partial-pressure reference state was used we add the subscript “p” to the equi-
librium constant, that is, by writing Kp .
To establish the equilibrium constant based on concentrations, we first use
the ideal gas law, PV = nRT, to relate gas concentrations and partial pressures
n PSO2 n PO2 n PSO3
[SO2] = = ; [O2] = = ; [SO3] = =
V RT V RT V RT
PETRMC15_622-662-hr 12/23/05 2:31 PM Page 632
and then express activities in terms of those concentrations, where the refer-
ence state is c° = 1 mol L-1.
PSO2 PO2 PSO3
[SO 2] RT [O2] RT [SO3] RT
aSO2 = = ; aO2 = = ; aSO3 = =
c° c° c° c° c° c°
Substituting into the equilibrium constant expression (15.12), we obtain
(PSO3)2 ([SO3]RT)2 P° [SO3]2
Kp = P° ¢ ≤ = P° ¢ ≤ = ¢ ≤ (15.14)
(PSO2)2PO2 eq ([SO2]RT)2[O2]RT eq RT [SO2]2[O2] eq
As expected the final expression is dimensionless. Because we have desig-

nated that the reference state is based on c° = 1 mol L-1, we can attach the
subscript “c” to the equilibrium constant, Kc, which is the ratio of concentra-
tions in the final parenthetical term of expression (15.14). Finally, observe that
(15.14) has a different value than (15.13). This result is not wrong. It simply
stems from a difference in the reference state in the two cases. In working with
equilibrium constant expressions, therefore, it is important to state the experi-
mental conditions and the reference state clearly. Choosing and defining a
reference state is an important concept that we will see again in our discussion
of thermodynamics in Chapter 19.
Eliminating the reference-state terms having a value of 1, the relationship
between Kp and Kc for reaction (15.11) is
Kp = Kc1RT2-1 (15.15)
If we carried out a similar derivation for the general reaction,
aA(g) + bB(g) + Á ∆ gG(g) + hH(g) + Á
the result would be
Kp = Kc1RT2¢ngas
▲
KEEP IN MIND (15.16)

that Kp = Kc only if ¢ngas = 0.
That is, Kp = Kc1RT20 = Kc where ¢ngas is the difference in the stoichiometric coefficients of gaseous prod-
because any number raised to ucts and reactants; that is, ¢ngas = 1g + h + Á2 - 1a + b + Á2. In reaction
the zero power equals one. (15.11), ¢ngas = 2 - 12 + 12 = -1, which is what we used in equation (15.15).
In summary, although we do not use units for the equilibrium constants, we
do need to use the correct dimensionless values of concentrations or pressures
for terms within equilibrium constant expressions. These are molarity for Kc
expressions and pressures in atmospheres for Kp expressions. These choices then
require that we use a value of R = 0.08206 L atm mol -1 K -1 in equation (15.16).
EXAMPLE 15-3
Illustrating the Dependence of K on the Reference State. Complete the calculation of Kp for reaction (15.11) know-
ing that Kc = 2.8 * 102 (at 1000 K).
Solution
Write the equation relating the two equilibrium constants with
different reference states. Kc = RT * Kp
Kc
Rearrange the expression to obtain the quantity desired, Kp . Kp =
RT
2.8 * 102
Substitute the given data and solve. Kp = = 3.4
0.08206 * 1000
Practice Example A: For the reaction 2 NH 3(g) ∆ N2(g) + 3 H 2(g) at 298 K, Kc = 2.8 * 10-9. What is the value
of Kp for this reaction?
Practice Example B: At 1065 °C, for the reaction 2 H 2S(g) ∆ 2 H 2(g) + S 2(g), Kp = 1.2 * 10-2. What is the
1
value of Kc for the reaction H 2(g) + S (g) ∆ H 2S(g) at 1065 °C?
2 2
PETRMC15_622-662-hr 12/23/05 2:31 PM Page 633
EQUILIBRIA INVOLVING PURE LIQUIDS AND SOLIDS

Up to this point in the chapter, all our examples have involved gaseous reac-
tions. In subsequent chapters, we will emphasize equilibria in aqueous solu-
tions. Gas-phase reactions and reactions in aqueous solution are homogeneous
reactions: They occur within a single phase. Let’s extend our coverage now
to include reactions involving one or more condensed phases—solids and
liquids—in contact with a gas or solution phase. These are called heterogeneous
reactions. One of the most important ideas about heterogeneous reactions is that
Equilibrium constant expressions do not contain concentration terms for solid or

liquid phases of a single component (that is, for pure solids and liquids).
We can think about this statement in either of two ways: (1) An equilibrium Still another way to think
▲
constant expression includes terms only for reactants and products whose con- about solids and liquids is
centrations and/or partial pressures can change during a chemical reaction. The through their densities.
concentration of the single component within a pure solid or liquid phase Density, the mass per unit
cannot change. (2) Alternatively, recall that the activities of pure liquids and volume of a substance, can be
expressed in moles per liter
solids are set equal to 1; thus the effect on the numerical value of the equilibri-
by converting the unit
um constant is the same as not including terms for pure solids and liquids at all. volume from milliliter to liter
The water–gas reaction, used to make combustible gases from coal, has re- and dividing the mass in
acting species in both gaseous and solid phases. grams by the molar mass.
C(s) + H 2O(g) ∆ CO(g) + H 2(g) The resultant molar density
(mol/L) is a concentration
Although solid carbon must be present for the reaction to occur, the equilibri- term and, at a fixed
um constant expression contains terms only for the species in the homoge- temperature, is a constant
neous gas phase: H 2O, CO, and H 2 . that would be incorporated in
aCOaH2 the Kc value.
[CO][H 2]
Kc = =
aC(s)aH2O [H 2O] Of course, the relationship
between concentration and
The activity of solid carbon is aC(s) = 1, and we have implicitly divided through pressure for gases is based here
each of the remaining concentrations by the reference-state concentration, c 0 = 1 on the ideal gas law: PV = ngasRT, or
[gas] = (ngas>V) = P>RT.
mol L-1, to obtain a dimensionless Kc .
The decomposition of calcium carbonate (limestone) is also a heterogeneous Drop two pieces of limestone, one
reaction. The equilibrium constant expression contains just a single term. large and the other small, into a
dilute solution of HCl, seal the
CaCO3(s) ∆ CaO(s) + CO2(g) Kc = [CO2] (15.17) beakers, and leave them until next
class. Some carbon dioxide will be
We can write Kp for reaction (15.17) by using equation (15.16), with ¢ngas = 1. seen bubbling off. By the next class,
the reaction will have stopped. Point
Kp = PCO2 and Kp = Kc(RT) (15.18) out that the pressure of CO2 in both
beakers is the same, but one piece of
Equation (15.18) indicates that the equilibrium pressure of CO2(g) in contact limestone is still bigger than the other.
with CaCO3(s) and CaO(s) is a constant equal to Kp . Its value is independent of That is, the concentration of CO2 does
not depend upon the amount of solid
the quantities of CaCO3 and CaO (as long as both solids are present). Figure 15-4 present. An improvement of the
offers a conceptualization of this decomposition reaction. experiment would be to attach the two
closed vessels to a U-tube manometer
to show the pressures are equal. Relate
this to Figure 15-4.
FIGURE 15-4
▲
Equilibrium in the reaction

CaCO3(s) ∆ CaO(s) CO2(g)
(a) Decomposition of CaCO 3(s) upon
heating in a closed vessel yields a few
granules of CaO(s), together with CO 2(g),
which soon exerts its equilibrium partial
pressure. (b) Introduction of additional
CaCO 3(s) and/or more CaO(s) has no
effect on the partial pressure of the
(a) (b) CO 2(g), which remains the same as in (a).
PETRMC15_622-662-hr 12/23/05 2:31 PM Page 634
One of our examples in Section 15-1 was liquid–vapor equilibrium. This is a

physical equilibrium because no chemical reactions are involved. Consider the
liquid–vapor equilibrium for water.
H 2O(l) ∆ H 2O(g)
Kc = [H 2O(g)] Kp = PH2O Kp = KcRT
So, equilibrium vapor pressures such as PH2O are just values of Kp . As we have
seen before, these values do not depend on the quantities of liquid or vapor at
equilibrium, as long as some of each is present.
EXAMPLE 15-4
Writing Equilibrium Constant Expressions for Reactions Involving Pure Solids or Liquids. At equilibrium in the
following reaction at 60 °C, the partial pressures of the gases are found to be PHI = 3.65 * 10-3 atm and
PH2S = 9.96 * 10-1 atm. What is the value of Kp for the reaction?
H 2S(g) + I 2(s) ∆ 2 HI(g) + S(s) Kp = ?
Solution
Write the equilibrium constant expression in terms of (aHI)2
activities. Note that activities for the iodine and sulfur K =
(aH2S)
are not included, since the activity of a pure solid is 1.
Substitute partial pressures for the activities into the (PHI)2

equilibrium constant expression. Kp =
(PH2S)
13.65 * 10-32
Substitute the given equilibrium data into the equilib- 2
rium constant expression. Kp = = 1.34 * 10-5
9.96 * 10-1
Practice Example A: Teeth are made principally from the mineral hydroxyapatite, Ca 5(PO4)3OH, which can
be dissolved in acidic solution such as that produced by bacteria in the mouth. The reaction that occurs is
Ca 5(PO 4)3OH(s) + 4 H +(aq) ∆ 5 Ca2+(aq) + 3 HPO4 2-(aq) + H 2O(l). Write the equilibrium constant expression
Kc for this reaction.
Practice Example B: The steam–iron process is used to generate H 2(g), mostly for use in hydrogenating oils. Iron
metal and steam [H 2O(g)] react to produce Fe3O4(s) and H 2(g). Write expressions for Kc and Kp for this reversible
reaction. How are the values of Kc and Kp related to each other? Explain.
15-4 THE MAGNITUDE OF AN EQUILIBRIUM CONSTANT

In principle, every chemical reaction has an equilibrium constant, but often
the constants are not used. Why is this so? Table 15.3 lists equilibrium con-
stants for several reactions mentioned in this chapter or previously in the text.
The first of these reactions is the synthesis of H 2O from its elements. We have
always assumed that this reaction goes to completion, that is, that the reverse
reaction is negligible and the overall reaction proceeds only in the forward di-
rection. If a reaction goes to completion, one (or more) of the reactants is used
up. A term in the denominator of the equilibrium constant expression ap-
Point out the huge range of proaches zero and makes the value of the equilibrium constant very large. A
values that equilibrium very large numerical value of K signifies that the forward reaction, as written,
constants can take.
goes to completion or very nearly so. Because the value of Kp for the water syn-
thesis reaction is 1.4 * 1083, we are entirely justified in saying that the reaction
goes to completion at 298 K.
PETRMC15_622-662-hr 12/23/05 2:31 PM Page 635
15-4 The Magnitude of an Equilibrium Constant 635
Equilibrium Constant
TABLE 15.3 Equilibrium Constants of Some Common Reactions activity
Reaction Equilibrium constant, Kp
2 H 2(g) + O2(g) ∆ 2 H 2O(l) 1.4 * 1083 at 298 K
CaCO3(s) ∆ CaO(s) + CO2(g) 1.9 * 10-23 at 298 K

1.0 at about 1200 K
2 SO2(g) + O2(g) ∆ 2 SO3(g) 3.4 at 1000 K
C(s) + H 2O(g) ∆ CO(g) + H 2(g) 1.6 * 10-21 at 298 K

10.0 at about 1100 K
If the equilibrium constant is so large, why is a mixture of hydrogen and The products formed in
oxygen gases stable at room temperature? The value of the equilibrium con- a reaction under kinetic
control are determined by
stant relates to thermodynamic stability: H 2O(l) is much more thermodynam- reaction rates. The products
ically stable than a mixture of H 2(g) and O2(g) because it lies at a lower energy formed in a reaction under
state. As noted in Chapter 14, however, the rate of a chemical reaction is thermodynamic control will depend
on the stability of the products.
strongly governed by the activation energy, Ea . Because Ea is very high for the
synthesis of H 2O(l) from H 2(g) and O2(g), the rate of reaction is inconsequen-
tial at 298 K. To get the reaction to occur at a measurable rate, we must either
raise the temperature or use a catalyst. A chemist would say that the synthesis
of H 2O(l) at 298 K is a kinetically controlled reaction (as opposed to
thermodynamically controlled).
From Table 15.3, we see that Kp for the decomposition of CaCO3(s) (lime- Equilibrium constants
stone) is very small at 298 K (only 1.9 * 10-23). To account for a very small nu- usually vary in value to a
large extent with
merical value of an equilibrium constant, the numerator must be very small temperature.
(approaching zero). A very small numerical value of K signifies that the for-
ward reaction, as written, does not occur to any significant extent. Although lime-
stone does not decompose at ordinary temperatures, the partial pressure of
CO2(g) in equilibrium with CaCO3(s) and CaO(s) increases with temperature.
It becomes 1 atm at about 1200 K. An important application of this decompo-
sition reaction is in the commercial production of quicklime (CaO).
The conversion of SO2(g) and O2(g) to SO3(g) at 1000 K has an equilibrium
constant such that we expect significant amounts of both reactants and prod-
ucts to be present at equilibrium (see Table 15.3). Both the forward and reverse
reactions are important. A similar situation exists for the reaction of C(s) and
H 2O(g) at 1100 K, but not at 298 K where the forward reaction does not occur
to any significant extent 1Kp = 1.6 * 10-212.
In light of the several cases from Table 15.3, we can conclude that
A reaction is most likely to reach a state of equilibrium in which significant quanti-

ties of both reactants and products are present if the numerical value of K is neither
very large nor very small, as a very rough approximation, in the range of about 10-10
to 1010.
Thus, we see that equilibrium calculations are not required for all reactions.
At times, we can use simple stoichiometric calculations to determine the out-
come of a reaction, and in some cases there may be no reaction at all.
Why is having a balanced equation a necessary condition for predicting the outcome
of a chemical reaction, but often not a sufficient condition?
PETRMC15_622-662-hr 12/23/05 2:32 PM Page 636
15-5 THE REACTION QUOTIENT, Q: PREDICTING THE

DIRECTION OF NET CHANGE
Let’s return briefly to the set of three experiments that we discussed in Section
15-2, involving the reaction
CO(g) + 2 H 2(g) ∆ CH 3OH(g) Kc = 14.5
Experiment 1 starts with just the reactants, CO and H 2 . An overall, or net,
change has to occur in which some CH 3OH forms. Only in this way can an
equilibrium condition be reached in which all reacting species are present. We
say that a net change occurs in the forward direction (to the right).
Experiment 2 starts with just the product, CH 3OH. Here, some of the
CH 3OH must decompose back to CO and H 2 before equilibrium can be estab-
lished. We say that a net change occurs in the reverse direction (to the left).
Experiment 3 starts with all the reacting species present: CO, H 2 , and
CH 3OH. In this system, it is not obvious in what direction a net change occurs
to establish equilibrium.
The ability to predict the direction of net change in establishing equilibrium
is important for two reasons.
• At times we do not need detailed equilibrium calculations. We may need
only a qualitative description of the changes that occur in establishing
equilibrium from a given set of initial conditions.
• In some equilibrium calculations, it is helpful to determine the direction
of net change as a first step.
For any set of initial activities in a reaction mixture, we can set up a ratio of
activities having the same form as the equilibrium constant expression. This
ratio is called the reaction quotient and is designated Q. For a hypothetical
generalized reaction, the reaction quotient, first written in terms of activities,
and then as concentrations assuming a concentration reference state, is
g g
(ainit) (ainit)h Á [G]init[H]hinit Á
Q = Qc = (15.19)
(ainit)a(ainit)b Á [A]ainit[B]binit Á
If Q = K, a reaction is at equilibrium, but our primary interest in the relation-

ship between Q and K is for a reaction mixture that is not at equilibrium. To
see what this relationship is, let’s turn again to the experiments in Table 15.1.
In Experiment 1, the initial concentrations of CO and H 2 are
1.000 mol>10.0 L = 0.100 M. Initially there is no CH 3OH. The value of Qc is
[CH 3OH]init 0
Qc = = = 0 (15.20)
[CO]init[H 2]2init (0.100)(0.100)2
We know that a net reaction occurs to the right, producing some CH 3OH.
As it does, the numerator in expression (15.20) increases, the denominator
decreases, and the value of Qc increases; eventually Qc = Kc .
If Qc 6 Kc , a net change occurs from left to right (the direction of the forward
reaction).
In Experiment 2, the initial concentration of CH 3OH is 1.000 mol>10.0 L =
0.100 M. Initially, there is no CO or H 2 . The value of Qc is
[CH 3OH]init 0.100
Qc = = = q (15.21)
[CO]init[H 2]2init 0 * 0
We know that a net reaction occurs to the left, producing some CO and H 2 . As
it does, the numerator in expression (15.21) decreases, the denominator
increases, and the value of Qc decreases; eventually Qc = Kc .
If Qc 7 Kc , a net change occurs from right to left (the direction of the reverse
reaction).
PETRMC15_622-662-hr 12/23/05 2:32 PM Page 637
15-5 The Reaction Quotient, Q: Predicting the Direction of Net Change 637
(a) (b) (c) (d) (e)

Initial condition: Pure “Left” of Equilibrium “Right” of Pure
reactants equilibrium equilibrium products
Reaction quotient, Qc 0 Kc Kc Kc
Reaction proceeds
to the right to the left
▲ FIGURE 15-5
Predicting the direction of net change in a reversible reaction
Five possibilities for the relationship of initial and equilibrium conditions are shown.
From Table 15.1 and Figure 15-3, Experiment 1 corresponds to initial condition (a);
Experiment 2 to condition (e); and Experiment 3 to (d). The situation in Example 15-5
also corresponds to condition (d).
Now let us turn to a case where direction of net change is not immediately
obvious. In Experiment 3, the initial concentrations of all three species are
1.000 mol>10.0 L = 0.100 M. The value of Qc is
[CH 3OH]init 0.100
Qc = = = 100
[CO]init[H 2]2init (0.100)(0.100)2
Because Qc 7 Kc (100 compared with 14.5), a net change occurs in the reverse
direction. Note that you can verify this conclusion from Figure 15-3. The
amounts of CO and H 2 at equilibrium are greater than they were initially, and
the amount of CH 3OH is less.
The criteria for predicting the direction of a net chemical change in a re-
versible reaction are summarized in Figure 15-5 and applied in Example 15-5.
EXAMPLE 15-5
Predicting the Direction of a Net Chemical Change in Establishing Equilibrium. To increase the yield of H 2(g) in
the water–gas reaction—the reaction of C(s) and H 2O(g) to form CO(g) and H 2(g)—a follow-up reaction called the
“water–gas shift reaction” is generally used. In this reaction, some of the CO(g) of the water gas is replaced by H 2(g).
CO(g) + H 2O(g) ∆ CO2(g) + H 2(g)
Kc = 1.00 at about 1100 K. The following amounts of substances are brought together and allowed to react at this
temperature: 1.00 mol CO, 1.00 mol H 2O, 2.00 mol CO2 , and 2.00 mol H 2 . Compared with their initial amounts, which
of the substances will be present in a greater amount and which in a lesser amount when equilibrium is established?
Solution
Our task is to determine the direction of net change by evaluating [CO2][H 2]
Qc . Write down the expression for Qc . Qc =
[CO][H 2O]
Substitute concentrations into the expression for Qc , by assuming 12.00>V212.00>V2

11.00>V211.00>V2
an arbitrary volume V (which cancels out in the calculation). Qc = = 4.00
Compare Qc to Kc. 4.00 7 1.00

Because Qc 7 Kc (that is, 4.00 7 1.00), a net change occurs to the
left. When equilibrium is established, the amounts of CO and H 2O
will be greater than the initial quantities and the amounts of CO2
and H 2 will be less.
Practice Example A: In Example 15-5, equal masses of CO, H 2O, CO2 , and H 2 are mixed at a temperature of
about 1100 K. When equilibrium is established, which substance(s) will show an increase in quantity and which will
show a decrease compared with the initial quantities?
Practice Example B: For the reaction PCl5(g) ∆ PCl3(g) + Cl2(g), Kc = 0.0454 at 261 °C. If a vessel is filled
with these gases such that the initial partial pressures are PPCl3 = 2.19 atm, PCl2 = 0.88 atm, PPCl5 = 19.7 atm, in which
direction will a net change occur?
PETRMC15_622-662-hr 12/23/05 2:32 PM Page 638
▲
KEEP IN MIND
that volume terms cancel in
a reaction quotient or A mixture of 1.00 mol each of CO(g), H 2O(g), and CO2(g) is placed in a 10.0-L flask at
equilibrium constant a temperature at which Kp = 10.0 in the reaction
expression whenever the sum
CO(g) + H 2O(g) ∆ CO2(g) + H 2(g)
of the exponents in the
numerator equals that in the When equilibrium is established, (a) the amount of H 2(g) will be 1.00 mol; (b) the
denominator. This can amounts of all reactants and products will be greater than 1.00 mol; (c) the amounts
simplify problem solving of all reactants and products will be less than 1.00 mol; (d) the amount of CO2(g) will
in some instances. be greater than 1.00 mol and the amounts of CO(g), H 2O(g), and H 2(g) will be less
than 1.00 mol; (e) the amounts of reactants and products cannot be predicted and can
only be determined by analyzing the equilibrium mixture.
15-6 ALTERING EQUILIBRIUM CONDITIONS:

LE CHÂTELIER’S PRINCIPLE
A gas at equilibrium is a At times, we want only to make qualitative statements about a reversible reac-
good example of Le tion: the direction of a net change, whether the amount of a substance will
Châtelier’s principle. Use
P = [gas]RT and imagine have increased or decreased when equilibrium is reached, and so on. Also, we
changing any one of P, [gas], or T. may not have the data needed for a quantitative calculation. In these cases, we
The ideal gas law must be satisfied, can use a statement attributed to the French chemist Henri Le Châtelier (1884).
so each time one parameter is
changed, the others must readjust. Le Châtelier’s principle is hard to state unambiguously, but its essential
meaning is stated here.
Huddle, Benjamin P.
“Conceptual Questions” on Le When an equilibrium system is subjected to a change in temperature, pressure,
Châtelier’s Principle. J. Chem. Educ.
2000: 75, 1175 (September 1998).
or concentration of a reacting species, the system responds by attaining a new equi-
librium that partially offsets the impact of the change.
Thomsen, Volker B. E. “Le
Châtelier’s Principle in the
Sciences.” J. Chem. Educ. 2000: 77,
As we will see in the examples that follow, it is generally not difficult to pre-
173 (February 2000). dict the outcome of changing one or more variables in a system at equilibrium.
EFFECT OF CHANGING THE AMOUNTS OF REACTING SPECIES

ON EQUILIBRIUM
Let’s return to reaction (15.11)
2 SO2(g) + O2(g) ∆ 2 SO3(g) Kc = 2.8 * 102 at 1000 K

2 SO2(g) O2(g) ∆ 2 SO3(g)
▲
Suppose we start with certain equilibrium amounts of SO2 , O2 , and SO3 , as

suggested by Figure 15-6(a). Now let’s create a disturbance in the equilibrium
mixture by forcing an additional 1.00 mol SO3 into the 10.0-L flask (Fig. 15-6b).
How will the amounts of the reacting species change to reestablish equilibrium?
Note that there is a time According to Le Châtelier’s principle, if the system is to partially offset an
delay between the action that increases the equilibrium concentration of one of the reacting
application of a stress and species, it must do so by favoring the reaction in which that species is con-
the establishment of equilibrium.
This is similar to Figure 15-3. sumed. In this case, this is the reverse reaction—conversion of some of the
Imagine if the applied stress is very added SO3 to SO2 and O2 . In the new equilibrium, there are greater amounts
small. In this case equilibrium is of all the substances than in the original equilibrium, but the additional
always maintained because the
change is too small to notice. Use amount of SO3 is less than the 1.00 mol that was added.
this to introduce the concept of Another way to look at the matter is to evaluate the reaction quotient im-
reversible processes. mediately after adding the SO3 .
Original equilibrium Immediately following disturbance
[SO3] [SO3]
Qc = 2
= Kc Qc = 7 Kc
[SO2] [O2] [SO2]2[O2]
PETRMC15_622-662-hr 12/23/05 2:32 PM Page 639
15-6 Altering Equilibrium Conditions: Le Châtelier’s Principle 639
Add:
1.00 mol SO3
(b) Le Châtelier’s Principle

1.46 mol SO3 movie
0.68 mol SO3
0.32 mol SO2

10.0 L 10.0 L
0.16 mol O2
0.54 mol SO2
(a) (c)
0.27 mol O2
▲ FIGURE 15-6
Changing equilibrium conditions by changing the amount of a reactant
2 SO2(g) O2(g) ∆ 2 SO3(g), Kc 2.8 : 102 at 1000 K
(a) The original equilibrium condition. (b) Disturbance caused by adding 1.00 mol
SO 3 . (c) The new equilibrium condition. The amount of SO 3 in the new equilibrium
mixture, 1.46 mol, is greater than the original 0.68 mol but it is not as great as
immediately after the addition of 1.00 mol SO 3 . The effect of adding SO 3 to an
equilibrium mixture is partially offset when equilibrium is restored.
Adding any quantity of SO3 to a constant-volume equilibrium mixture

makes Qc larger than Kc . A net change occurs in the direction that reduces
[SO3], that is, to the left, or in the reverse direction. Notice that reaction
in the reverse direction increases [SO2] and [O2], further decreasing the
value of Qc .
EXAMPLE 15-6
Applying Le Châtelier’s Principle: Effect of Adding More of a Reactant to an
Equilibrium Mixture. Predict the effect of adding more H 2(g) to a constant-volume
equilibrium mixture of N2 , H 2 , and NH 3 .
N2(g) + 3 H 2(g) ∆ 2 NH 3(g)
Solution
Increasing [H 2] stimulates the forward reaction and a shift in the equilibrium con-
dition to the right. However, only a portion of the added H 2 is consumed in this re-
action. When equilibrium is reestablished, there will be more H 2 than was present
originally, and also more NH 3 , but the amount of N2 will be smaller. Some of the
original N2 must be consumed in converting some of the added H 2 to NH 3 .
Practice Example A: Given the reaction 2 CO(g) + O2(g) ∆ 2 CO2(g), what

is the effect of adding O2(g) to a constant-volume equilibrium mixture?
Practice Example B: Calcination of limestone (decomposition by heating),

CaCO3(s) ∆ CaO(s) + CO2(g), is the commercial source of quicklime, CaO(s).
After this equilibrium has been established in a constant-temperature, constant-
volume container, what is the effect on the equilibrium amounts of materials caused
by adding some (a) CaO(s); (b) CO2(g); (c) CaCO3(s)?
PETRMC15_622-662-hr 12/23/05 2:32 PM Page 640
EFFECT OF CHANGES IN PRESSURE OR VOLUME ON EQUILIBRIUM

There are three ways to change the pressure of a constant-temperature equi-
librium mixture.
1. Add or remove a gaseous reactant or product. The effect of these actions
on the equilibrium condition is simply that due to adding or removing a
reaction component, as described previously.
2. Add an inert gas to the constant-volume reaction mixture. This has the
effect of increasing the total pressure, but the partial pressures of the react-
ing species are all unchanged. An inert gas added to a constant-volume
equilibrium mixture has no effect on the equilibrium condition.
3. Change the pressure by changing the volume of the system. Decreasing
the volume of the system increases the pressure, and increasing the system
volume decreases the pressure. Thus, the effect of this type of pressure
change is simply that of a volume change.
Let’s explore the third situation first. Consider, again, the formation of
SO3(g) from SO2(g) and O2(g).
2 SO2(g) + O2(g) ∆ 2 SO3(g) Kc = 2.8 * 102 at 1000 K
The equilibrium mixture in Figure 15-7(a) has its volume reduced to one-tenth
of its original value by increasing the external pressure. To see how the equi-
librium amounts of the gases change, let’s first rearrange the equilibrium con-
stant expression to the form
[SO 3]2 (nSO3>V)2 (nSO3)2
* V = 2.8 * 102 (15.22)
(nSO2>V)2(nO2>V)
Kc = = =
[SO 2]2[O2] (nSO2)2(nO2)
From equation (15.22), we see that if V is reduced by a factor of 10, the ratio
(nSO3)2
(nSO2)2(nO2)
0.68 mol SO3
0.32 mol SO2

0.16 mol O2
0.83 mol SO3
10.0 L 1.00 L
0.17 mol SO2
0.085 mol O2
(a) (b)
▲ FIGURE 15-7
Effect of pressure change on equilibrium in the reaction
2 SO2(g) O2(g) ∆ 2 SO3(g)
An increase in external pressure causes a decrease in the reaction volume and a
shift in equilibrium “to the right.” (See Exercise 65 for a calculation of the new
equilibrium amounts.)
PETRMC15_622-662-hr 12/23/05 2:32 PM Page 641
must increase by a factor of 10. In this way, the value of Kc is restored, as it must
be to restore equilibrium. There is only one way in which the ratio of moles of
gases will increase in value: The number of moles of SO3 must increase, and the
numbers of moles of SO2 and O2 must decrease. The equilibrium shifts in
the direction producing more SO3—to the right.
Notice that three moles of gas on the left produce two moles of gas on the
right in reaction (15.11). When compared at the same temperature and pres-
sure, two moles of SO3(g) occupy a smaller volume than does a mixture of two
moles of SO2(g) and one mole of O2(g). Given this fact and the observation
from equation (15.22) that a decrease in volume favors the production of addi-
tional SO3 , we can formulate a statement that is especially easy to apply.
NO2 ¬ N2O4
When the volume of an equilibrium mixture of gases is reduced, a net change occurs Equilibrium animation
in the direction that produces fewer moles of gas. When the volume is increased, a net
change occurs in the direction that produces more moles of gas.
Figure 15-7 suggests a way of decreasing the volume of gaseous mixture at

equilibrium—by increasing the external pressure. One way to increase the vol-
ume is to lower the external pressure. Another way is to transfer the equilibri-
KEEP IN MIND
▲
um mixture from its original container to one of larger volume. A third
method is to add an inert gas at constant pressure; the volume of the mixture that an inert gas has no effect
must increase to make room for the added gas. The effect on the equilibrium, on an equilibrium condition
however, is the same for all three methods: Equilibrium shifts in the direction if the gas is added to a system
of the reaction producing the greater number of moles of gas. maintained at constant vol-
ume, but it can have an effect
Equilibria between condensed phases are not affected much by changes in
if added at constant pressure.
external pressure because solids and liquids are not easily compressible. Also,
we cannot assess whether the forward or reverse reaction is favored by these
changes by examining only the chemical equation.
EXAMPLE 15-7
Applying Le Châtelier’s Principle: The Effect of Changing Volume. An equilibrium
mixture of N2(g), H 2(g), and NH 3(g) is transferred from a 1.50-L flask to a 5.00-L flask.
In which direction does a net change occur to restore equilibrium?
N2(g) + 3 H 2(g) ∆ 2 NH 3(g)
Solution
When the gaseous mixture is transferred to the larger flask, the partial pressure of Remind students that the
each gas and the total pressure drop. Whether we think in terms of a decrease in pressure of a particular gas
pressure or an increase in volume, we reach the same conclusion. Equilibrium shifts inside a container remains
unchanged even if an inert gas is
in such a way as to produce a larger number of moles of gas. Some of the NH 3 orig- added to the container as long as
inally present decomposes back to N2 and H 2 . A net change occurs in the direction the volume of the container is not
of the reverse reaction—to the left—in restoring equilibrium. changed. Review Dalton's Law of
Partial Pressures.
Practice Example A: The reaction N2O4(g) ∆ 2 NO2(g) is at equilibrium in
a 3.00-L cylinder. What would be the effect on the concentrations of N2O4(g) and
NO2(g) if the pressure were doubled (that is, cylinder volume decreased to 1.50 L)?
Practice Example B: How is the equilibrium amount of H 2(g) produced in the

water–gas shift reaction affected by changing the total gas pressure or the system
volume? Explain.
CO(g) + H 2O(g) ∆ CO2(g) + H 2(g)
PETRMC15_622-662-hr 12/23/05 2:32 PM Page 642
The following reaction is brought to equilibrium at 700 °C.
2 H 2S(g) + CH 4(g) ∆ CS 2(g) + 4 H 2(g)
Indicate whether each of the following statements is true, false, or not possible to
evaluate from the information given.
(a) If the equilibrium mixture is allowed to expand into an evacuated larger con-
tainer, the mole fraction of H 2 will increase.
(b) If several moles of Ar(g) are forced into the reaction container, the amounts of
H 2S and CH 4 will increase.
(c) If the equilibrium mixture is cooled to 100 °C, the mole fractions of the four
gases will likely change.
(d) If the equilibrium mixture is forced into a slightly smaller container, the partial
pressures of the four gases will all increase.
EFFECT OF TEMPERATURE ON EQUILIBRIUM

Temperature Dependence We can think of changing the temperature of an equilibrium mixture in terms
of Equilibrium animation of adding heat (raising the temperature) or removing heat (lowering the tem-
perature). According to Le Châtelier’s principle, adding heat favors the reac-
tion in which heat is absorbed (endothermic reaction). Removing heat favors
the reaction in which heat is evolved (exothermic reaction). Stated in terms of
changing temperature,
Raising the temperature of an equilibrium mixture shifts the equilibrium condition in

the direction of the endothermic reaction. Lowering the temperature causes a shift in the
direction of the exothermic reaction.
Note that an exothermic The principal effect of temperature on equilibrium is in changing the value
reaction is aided by of the equilibrium constant. In Chapter 19, we will learn how to calculate equi-
lowering the temperature
and an endothermic reaction is librium constants as a function of temperature. For now, we will limit our-
aided by raising the temperature. selves to making qualitative predictions.
You can then point out the
difference between the system and
the surroundings.
EXAMPLE 15-8
Remind students not to
confuse shifts in Applying Le Châtelier’s Principle: Effect of Temperature on Equilibrium.
equilibrium with changes Consider the reaction
in reaction rates that result from
temperature changes. Equilibria 2 SO2(g) + O2(g) ∆ 2 SO 3(g) ¢H° = -197.8 kJ
of exothermic and endothermic
reactions will shift differently Will the amount of SO3(g) formed from given amounts of SO2(g) and O2(g) be
when temperatures are increased, greater at high or low temperatures?
but the rates of exothermic and
endothermic reactions both increase Solution
with increasing temperature.
Raising the temperature favors the endothermic reaction, the reverse reaction. Low-
Stress to students that ering the temperature favors the forward (exothermic) reaction. Therefore, an equi-
changing the temperature librium mixture would have a higher concentration of SO3 at lower temperatures.
of a reaction will result in The conversion of SO2 to SO3 is favored at low temperatures.
a shift of the equilibrium and a
new equilibrium constant.
Practice Example A: The reaction N2O4(g) ∆ 2 NO2(g) has ¢H° = +57.2 kJ.
Will the amount of NO2(g) formed from N2O4(g) be greater at high or low
temperatures?
Practice Example B: The enthalpy of formation of NH 3 is ¢H f°[NH 3(g)] =

-46.11 kJ>mol NH 3 . Will the concentration of NH 3 in an equilibrium mixture with
its elements be greater at 100 or at 300 °C? Explain.
PETRMC15_622-662-hr 12/23/05 2:32 PM Page 643
▲ Sulfuric acid is produced from SO3

SO3(g) H2O(l) ∆ H2SO4(aq)
The catalyst used to speed up the conversion of SO2 to SO3 in the commercial
production of sulfuric acid is V2O5(s).
EFFECT OF A CATALYST ON EQUILIBRIUM

Adding a catalyst to a reaction mixture speeds up both the forward and re-
verse reactions. Equilibrium is achieved more rapidly, but the equilibrium
amounts are unchanged by the catalyst. Consider again reaction (15.11)
2 SO2(g) + O2(g) ∆ 2 SO3(g) Kc = 2.8 * 102 at 1000 K
For a given set of reaction conditions, the equilibrium amounts of SO2 , O2 , and
SO3 have fixed values. This is true whether the reaction is carried out by a slow
homogeneous reaction, catalyzed in the gas phase, or conducted as a heteroge-
neous reaction on the surface of a catalyst. Stated another way, the presence of a
catalyst does not change the numerical value of the equilibrium constant.
We now have two thoughts about a catalyst to reconcile: one from the pre-
ceding chapter and one from this discussion.
• A catalyst changes the mechanism of a reaction to one with a lower acti-
vation energy.
• A catalyst has no effect on the condition of equilibrium in a reversible
reaction.
Taken together, these two statements must mean that an equilibrium condi-
tion is independent of the reaction mechanism. Thus, even though equilibrium
has been described in terms of opposing reactions occurring at equal rates, we
do not have to be concerned with the kinetics of chemical reactions to work
with the equilibrium concept. This observation is still another indication that
the equilibrium constant is a thermodynamic quantity, as we shall describe
more fully in Chapter 19.
Two students are performing the same experiment in which an endothermic reaction
rapidly attains a condition of equilibrium. Student A does the reaction in a beaker
resting on the surface of the lab bench while student B holds the beaker in which the
reaction occurs. Assuming that all other environmental variables are the same, which
student should end up with more product? Explain.
PETRMC15_622-662-hr 12/23/05 2:32 PM Page 644
Good Web sites for

equilibrium calculations: 15-7 EQUILIBRIUM CALCULATIONS: SOME
http://www.chem.vt.edu/
RVGS/ACT/notes/chem-eqm.html ILLUSTRATIVE EXAMPLES
(noncommercial);
http://stokes.lance.colcostate.edu/ We are now ready to tackle the problem of describing, in quantitative terms,
tools/equil.html (noncommercial). the condition of equilibrium in a reversible reaction. Part of the approach we
use may seem unfamiliar at first—it has an algebraic look to it. But as you ad-
just to this “new look,” do not lose sight of the fact that we continue to use
some familiar and important ideas—molar masses, molarities, and stoichio-
Nitrogen Dioxide
and Dinitrogen metric factors from the balanced equation, for example.
Tetroxide movie The five numerical examples that follow apply the general equilibrium
principles described earlier in the chapter. The first four involve gases, while
the fifth deals with equilibrium in an aqueous solution. (The study of equilib-
Leenson, I. A. “Approaching
Equilibrium in the
ria in aqueous solutions is the principal topic of the next three chapters.) Each
N2O4 ¬ NO2 System: A Common example includes a brief section labeled “comments,” which is printed on a
Mistake in Textbooks.” J. Chem. yellow background. Think of the comments as the basic methodology of equi-
Educ. 2000: 77, 1652
(December 2000).
librium calculations. You may want to refer back to these comments from time
to time while you are studying later chapters.
Example 15-9 is relatively straightforward. It demonstrates how to deter-
mine the equilibrium constant of a reaction when the equilibrium concentra-
tions of the reactants and products are known.
EXAMPLE 15-9
Determining a Value of Kc from the Equilibrium Quantities of Substances. Dinitrogen tetroxide, N2O4(l), is an
important component of rocket fuels—for example, as an oxidizer of liquid hydrazine in the Titan rocket. At 25 °C,
N2O4 is a colorless gas that partially dissociates into NO2 , a red-brown gas. The color of an equilibrium mixture of
these two gases depends on their relative proportions, which in turn depends on the temperature (Fig. 15-8).
Equilibrium is established in the reaction N2O4(g) ∆ 2 NO2(g) at 25 °C. The quantities of the two gases present
in a 3.00-L vessel are 7.64 g N2O4 and 1.56 g NO2 . What is the value of Kc for this reaction?
N N
O O O O
O O
N N
O O
(a) (b)
▲ FIGURE 15-8 ▲ The Lewis structures of N2O4 and NO2(g)
The equilibrium N2O4(g) ∆ 2 NO2(g) Nitrogen dioxide is a free radical that combines
(a) At dry ice temperatures, N2O4 exists as a solid. exothermically to form dinitrogen tetroxide.
The gas in equilibrium with the solid is mostly
colorless N2O4 , with only a trace of brown NO2 .
(b) When warmed to room temperature and above, Use these examples to point
the N2O4 melts and vaporizes. The proportion of out the importance of
NO2(g) at equilibrium increases over that at low significant figures.
temperatures, and the equilibrium mixture of
N2O4(g) and NO2(g) has a red-brown color.
PETRMC15_622-662-hr 12/23/05 2:32 PM Page 645
15-7 Equilibrium Calculations: Some Illustrative Examples 645
Solution
1 mol N2O4
Convert the mass of N2O4 to moles. mol N2O4 = 7.64 g N2O4 * = 8.303 * 10-2 mol
92.01 g N2O4
8.303 * 102 mol

Convert moles of N2O4 to mol>L. [N2O4] = = 0.0277 M
3.00 L
1 mol NO 2
Convert the mass of NO2 to moles. mol NO 2 = 1.56 g NO 2 * = 3.391 * 10-2 mol
46.01 g NO 2
3.391 * 10-2
Convert moles of NO 2 to mol>L. [NO 2] = = 0.0113 M
3.00 L
Write the equilibrium constant expression, sub- [NO2]2 (0.0113)2

stitute the equilibrium concentrations, and solve Kc = = = 4.61 * 10-3
[N2O4] (0.0277)
for Kc .
Practice Example A: Equilibrium is established in a 3.00-L flask at 1405 K for the reaction
2 H 2S(g) ∆ 2 H 2(g) + S 2(g). At equilibrium, there is 0.11 mol S 2(g), 0.22 mol H 2(g), and 2.78 mol H 2S(g). What is
the value of Kc for this reaction?
Practice Example B: Equilibrium is established at 25 °C in the reaction N2O4(g) ∆ 2 NO2(g), Kc = 4.61 * 10-3.
If [NO 2] = 0.0236 M in a 2.26-L flask, how many grams of N2O4 are also present?
Comments
1. The quantities required in an equilibrium constant expression, Kc , are equilibrium concentrations in moles per
liter, not simply equilibrium amounts in moles or masses in grams. You will find it helpful to organize all the
equilibrium data and carefully label each item.
Example 15-10 is somewhat more involved than Example 15-9. We are still
interested in determining the equilibrium constant for a reaction, but we do not
have the same sort of information as in Example 15-9. We are given the initial
concentrations of all the reactants and products, but the equilibrium concentra-
tion of only one substance. This case requires a little algebra and some careful
bookkeeping. We will introduce a tabular system, sometimes called an ICE table,
for keeping track of changing concentrations of reactants and products. The table
contains the initial, change in, and equilibrium concentration of each species. It is a
helpful device that we will use throughout the next three chapters.
EXAMPLE 15-10
Determining a Value of Kp from Initial and Equilibrium Amounts of Substances: Silverstein, Todd P.
Relating Kc and Kp The equilibrium condition for SO2(g), O2(g), and SO3(g) is im- “Graphing Calculator
Strategies for Solving Chemical
portant in sulfuric acid production. When a 0.0200-mol sample of SO3 is introduced
Equilibrium Problems.” J. Chem.
into an evacuated 1.52-L vessel at 900 K, 0.0142 mol SO3 is present at equilibrium. Educ. 2000: 77, 1120.
What is the value of Kp for the dissociation of SO3(g) at 900 K? (September 2000).
2 SO3(g) ∆ 2 SO 2(g) + O2(g) Kp = ?
Solution
Let’s first determine Kc and then convert to Kp by using equation (15.16). In the ICE
table on page 646, the key term leading to the other data is the change in amount of
SO3 : In progressing from 0.0200 mol SO3 to 0.0142 mol SO3 , 0.0058 mol SO3 is disso-
ciated. The negative sign (-0.0058 mol) indicates that this amount of SO3 is consumed
in establishing equilibrium. In the row labeled “changes,” the changes in amounts of
SO2 and O2 must be related to the change in amount of SO3 . For this, we use the sto-
ichiometric coefficients from the balanced equation: 2, 2, and 1. That is, two moles of
SO2 and one mole of O2 are produced for every two moles of SO3 that dissociate.
PETRMC15_622-662-hr 12/23/05 2:32 PM Page 646
The reaction: 2 SO3(g) ∆ 2 SO2(g) O2(g)

initial amounts: 0.0200 mol 0.00 mol 0.00 mol
changes: -0.0058 mol +0.0058 mol +0.0029 mol
equil amounts: 0.0142 mol 0.0058 mol 0.0029 mol
0.0142 mol 0.0058 mol 0.0029 mol
equil concns: [SO3] = ; [SO2] = ; [O2] =
1.52 L 1.52 L 1.52 L
[SO3] = 9.34 * 10-3 M; [SO2] = 3.8 * 10-3 M; [O2] = 1.9 * 10-3 M
13.8 * 10-32 11.9 * 10-32

2
[SO2]2[O2]
Kc = = 3.1 * 10-4
19.34 * 10-32
=
[SO 3]2 2
Kp = Kc1RT2¢ngas = 3.1 * 10-4 10.0821 * 900212 + 12 - 2
= 3.1 * 10-4 10.0821 * 90021 = 2.3 * 10-2
Practice Example A: A 5.00-L evacuated flask is filled with 1.86 mol NOBr. At
equilibrium at 25 °C, there is 0.082 mol of Br2 present. Determine Kc and Kp for the
reaction 2 NOBr(g) ∆ 2 NO(g) + Br2(g).
Practice Example B: 0.100 mol SO2 and 0.100 mol O2 are introduced into an
evacuated 1.52-L flask at 900 K. When equilibrium is reached, the amount of SO3
found is 0.0916 mol. Use these data to determine Kp for the reaction
2 SO3(g) ∆ 2 SO 2(g) + O2(g).
Comments
2. The chemical equation for a reversible reaction serves both to establish the
form of the equilibrium constant expression and to provide the conversion
factors (stoichiometric factors) to relate the equilibrium quantity of one
species to equilibrium quantities of the others.
3. For equilibria involving gases, you can use either Kc or Kp . In general, if the
data given involve amounts of substances and volumes, it is easier to work
with Kc . If data are given as partial pressures, then work with Kp . Whether
working with Kc or Kp or the relationship between them, you must always
base these expressions on the given chemical equation, not on equations
you may have used in other situations.
The methods used in Examples 15-9 and 15-10 are summarized in Figure
15-9. Example 15-11 demonstrates that we can often determine several pieces
of useful information about an equilibrium system from just the equilibrium
constant and the reaction equation.
EXAMPLE 15-11
Determining Equilibrium Partial and Total Pressures from a Value of Kp . Ammonium hydrogen sulfide,
NH 4HS(s), used as a photographic developer, is unstable and dissociates at room temperature.
NH 4HS(s) ∆ NH 3(g) + H 2S(g) Kp = 0.108 at 25 °C
A sample of NH 4HS(s) is introduced into an evacuated flask at 25 °C. What is the total gas pressure at equilibrium?
Solution
Write out the equilibrium constant expression in
terms of pressures. Kp = (PNH3)(PH2S) = 0.108
PETRMC15_622-662-hr 12/23/05 2:32 PM Page 647
Are the experimental data

exclusively equilibrium data?
Yes No
Convert the data Relate changes in initial amounts,

to concentrations or concentrations, or partial pressures to
partial pressures a known equilibrium amount,
concentration, or partial pressure
Establish all the equilibrium

concentrations or partial
pressures
Substitute concentrations
into Kc or partial pressures
into Kp expressions
▲ FIGURE 15-9
Determining Kc or Kp from experimental data
Kp for this reaction is just the product of the equi-

librium partial pressures of NH 3(g) and H 2S(g),
each stated in atmospheres. (There is no term for
NH 4HS because it is a solid.) Because these gases
are produced in equimolar amounts, PNH3 = PH2S. Kp = (PNH3)(PH2S) = (PNH3)(PNH3) = (PNH3)2 = 0.108
Find PNH3 . (Note that the unit atm appears

because in the equilibrium expression the refer-
ence pressure P° was implicitly included.) PNH3 = 20.108 = 0.329 atm PH2S = PNH3 = 0.329 atm
The total pressure is Ptot = PNH3 + PH2S = 0.329 atm + 0.329 atm = 0.658 atm
Practice Example A: Sodium hydrogen carbonate (baking soda) decomposes at elevated temperatures and is one
of the sources of CO2(g) when this compound is used in baking.
2 NaHCO3(s) ∆ Na 2CO3(s) + H 2O(g) + CO2(g) Kp = 0.231 at 100 °C
What is the partial pressure of CO2(g) when this equilibrium is established starting with NaHCO3(s)?
Practice Example B: If enough additional NH 3(g) is added to the flask in Example 15-11 to raise its partial pres-
sure to 0.500 atm at equilibrium, what will be the total gas pressure when equilibrium is reestablished?
Comments
4. When using Kp expressions, look for relationships among partial pressures of the reactants. If you need to
relate the total pressure to the partial pressures of the reactants, you should be able to do this with some equa-
tions presented in Chapter 6 (for example, equations 6.15, 6.16, and 6.17).
Example 15-12 brings back the ICE format, but with a twist. This time the
known values include the equilibrium constant and an initial amount of the re-
actant, but no information is given about the equilibrium amount of the reactant
or the product. That means that we do not know how much the initial value will
change. We show this by using an “x” in that part of the table. The setup will be
quite algebraic; in fact, we must use the quadratic formula to obtain a solution.
PETRMC15_622-662-hr 12/23/05 2:32 PM Page 648
EXAMPLE 15-12
Calculating Equilibrium Concentrations from Initial Conditions. A 0.0240-mol
sample of N2O4(g) is allowed to come to equilibrium with NO2(g) in a 0.372-L flask
at 25 °C. Calculate the amount of N2O4 present at equilibrium (Fig. 15-10).
N2O4(g) ∆ 2 NO 2(g) Kc = 4.61 * 103 at 25 °C
(a) N2O4 (b)
NO2
▲ FIGURE 15-10
Equilibrium in the reaction
N2O4(g) ∆ 2 NO2(g)
at 25 °C—Example 15-12 illustrated
Each “molecule” illustrated represents 0.001 mol. (a) Initially, the bulb contains
0.024 mol N 2O 4 , represented by 24 “molecules.” (b) At equilibrium, some
“molecules” of N 2O 4 have dissociated to NO 2 . The 21 “molecules” of N 2O 4 and 6
of NO 2 correspond to 0.021 mol N 2O 4 and 0.006 mol NO 2 at equilibrium.
Most students can solve a Solution

quadratic equation, but few
of us can solve polynomials
We need to determine the amount of N2O4 that dissociates to establish equilibrium.
greater than a quadratic. Suggest to For the first time, we introduce an algebraic unknown, x. Suppose we let x = the
the students that if they get an number of moles of N2O4 that dissociate. In the following ICE table, we enter the
equation that is a cubic or higher value -x into the row labeled “changes.” The amount of NO2 produced is +2x be-
degree equation, it is likely that it cause the stoichiometric coefficient of NO2 is 2 and that of N2O4 is 1.
will simplify by using an
approximation. The reaction: N2O4(g) ∆ 2 NO2(g)
initial amounts: 0.0240 mol 0.00 mol
changes: -x mol +2x mol
equil amounts: 10.0240 - x2 mol 2x mol
equil concns: [N2O4] = 10.0240 - x mol2>0.372 L [NO 2] = 2x mol>0.372 L
2x 2
2 a b
[NO2] 0.372 4x 2
Kc = = = = 4.61 * 10-3
a b
[N2O4] 0.0240 - x 0.37210.0240 - x2
0.372
For a discussion of 4x 2 = 4.12 * 10-5 - 11.71 * 10-32x
▲
x 2 + 14.28 * 10-42x - 1.03 * 10-5 = 0

quadratic equations,
see Appendix A.
-4.28 * 10-4 ; 414.28 * 10-42 + 4 * 1.03 * 10-5

2
The symbol ; signifies
▲
that there are two possible x =

2
roots. In this problem, x must
be a positive quantity smaller -4.28 * 10-4 ; 411.83 * 10-72 + 4.12 * 10-5
than 0.0240. =
2
PETRMC15_622-662-hr 12/23/05 2:32 PM Page 649
-4.28 * 10-4 ; 44.14 * 10-5

x =
2
-4.28 * 10-4 ; 6.43 * 10-3
=
2
-4.28 * 10-4 + 6.43 * 10-3 6.00 * 10-3
= =
2 2
= 3.00 * 10-3 mol N2O4
The amount of N2O4 at equilibrium is 10.0240 - x2 = 10.0240 - 0.00302 =

0.0210 mol N2O4.
Practice Example A: If 0.150 mol H 2(g) and 0.200 mol I 2(g) are introduced into
a 15.0-L flask at 445 °C and allowed to come to equilibrium, how many moles of
HI(g) will be present?
H 2(g) + I 2(g) ∆ 2 HI(g) Kc = 50.2 at 445 °C
Practice Example B: Suppose the equilibrium mixture of Example 15-12 is Determine the direction of
transferred to a 10.0-L flask. (a) Will the equilibrium amount of N2O4 increase or net change by comparing
decrease? Explain. (b) Calculate the number of moles of N2O4 in the new equilibri- Q and K
um condition.
Comments
5. When you need to introduce an algebraic unknown, x, into an equilibrium Let x change in amount,
calculation, follow these steps. concentration, or partial
• Introduce x into the ICE setup in the row labeled “changes.” pressure of one reactant or
• Decide which change to label as x, that is, the amount of a reactant con- product to reach equilibrium
Tabulate these data in an ICE table

sumed or of a product formed. Usually, we base this on the species
that has the smallest stoichiometric coefficient in the balanced chemical
equation.
• Use stoichiometric factors to relate the other changes to x (that is, 2x,
3x, Á ). Relate changes in amounts,
concentrations, or partial
• Consider that equilibrium amounts = intial amounts + “changes.– (If
pressures of other reactants
you have assigned the correct signs to the changes, equilibrium amounts
or products to the chosen x
will also be correct.)
• After substitutions have been made into the equilibrium constant expres-
sion, the equation will often be a quadratic equation in x, which you
can solve by the quadratic formula. Occasionally you may encounter a
higher-degree equation. Appendix A-3 outlines a straightforward method
Express equilibrium
of dealing with these.
amounts, concentrations,
partial pressures
in terms of x
Our final example is similar to the previous one, but with this slight com-
plication: Initially, we don’t know whether a net change occurs to the right or
to the left to establish equilibrium. We can find out, though, by using the reac-
tion quotient, Qc , and proceeding in the manner suggested in Figure 15-11. Substitute equilibrium
Also, because the reactants and products are in solution, we can work exclu- concentrations or
sively with concentrations in formulating the Kc expression. partial pressures into Kc or Kp
expression; solve for x;
substitute the value of x
EXAMPLE 15-13 into any equation in which
x appeared to find the
Using the Reaction Quotient, Qc , in an Equilibrium Calculation. Solid silver is
desired quantities
added to a solution with these initial concentrations: [Ag +] = 0.200 M,
[Fe 2+] = 0.100 M, and [Fe 3+] = 0.300 M. The following reversible reaction occurs.
▲ FIGURE 15-11
Determining equilibrium
Ag +(aq) + Fe 2+(aq) ∆ Ag(s) + Fe 3+(aq) Kc = 2.98
concentrations and partial
pressures
What are the ion concentrations when equilibrium is established?
PETRMC15_622-662-hr 12/23/05 2:32 PM Page 650
Solution
Because all reactants and products are present initially, we need to use the reaction
quotient Qc to determine the direction in which a net change occurs.
[Fe 3+] 0.300
Qc = 2+
= = 15.0
[Ag ][Fe ]
+ (0.200)(0.100)
Because Qc (15.0) is larger than Kc (2.98), a net change must occur in the direction of
the reverse reaction, to the left. Let’s define x as the change in molarity of Fe 3+. Be-
cause the net change occurs to the left, we designate the changes for the species on
the left side of the equation as positive and those on the right side as negative. The
relevant data are tabulated as follows.
The reaction: Ag +(aq) Fe 2+(aq) ∆ Ag(s) Fe 3(aq)
Initial concns: 0.200 M 0.100 M 0.300 M
changes: +x M +x M -x M
equil concns: 10.200 + x2 M 10.100 + x2 M 10.300 - x2 M
[Fe 3+] (0.300 - x)

Kc = 2+
= = 2.98
[Ag ][Fe ]
+ (0.200 + x)(0.100 + x)
This equation, which is solved in Appendix A-3, is a quadratic equation for which
the acceptable root is x = 0.11. To obtain the equilibrium concentrations, we substi-
tute this value of x into the terms shown in the table of data.
[Ag +]equil = 0.200 + 0.11 = 0.31 M
[Fe 2+]equil = 0.100 + 0.11 = 0.21 M
[Fe 3+]equil = 0.300 - 0.11 = 0.19 M
CHECK: If we have done the calculation correctly, we should obtain a value very
close to that given for Kc when we substitute the calculated equilibrium concentra-
tions into the reaction quotient, Qc . We do.
[Fe 3+] (0.19)
Qc = 2+
= = 2.9 (Kc = 2.98)
After making an [Ag ][Fe ]
+ (0.31)(0.21)
approximation, it is always
necessary to check its
validity by substituting the Practice Example A: Excess Ag(s) is added to 1.20 M Fe 3+(aq). Given that
approximate value back into the
equation and verifying the 5% rule.
Ag +(aq) + Fe 2+(aq) ∆ Ag(s) + Fe 3+(aq) Kc = 2.98
what are the equilibrium concentrations of the species in solution?
Practice Example B: A solution is prepared with [V 3+] = [Cr 2+] = 0.0100 M
and [V 2+] = [Cr 3+] = 0.150 M. The following reaction occurs.
V 3+(aq) + Cr 2+(aq) ∆ V 2+(aq) + Cr 3+(aq) Kc = 7.2 * 102
▲
KEEP IN MIND
that if one or more of the
What are the ion concentrations when equilibrium is established?
substances appearing in Qc
(or Qp) is not present initially, [Hint: The algebra can be greatly simplified by extracting the square root of both
a net change must occur to sides of an equation at the appropriate point.]
produce some of the
substance(s). You need to
compare Qc (or Qp) with Kc Comments
(or Kp) only if all the 6. It is sometimes helpful to compare the reaction quotient Q to the equilibri-
substances appearing in um constant K to determine the direction of the net change.
these expressions are
present initially. 7. In many equilibrium calculations—often those in aqueous solutions—you
can work with molarities directly, without having to work with moles of re-
actants and solution volumes.
8. Where possible, check your calculation, for instance, by substituting
calculated equilibrium concentrations into the reaction quotient Q to see if its
numerical value is close to that of K.
PETRMC15_622-662-hr 12/23/05 2:32 PM Page 651
Integrative Example 651
Summary
15-1 Dynamic Equilibrium—Equilibrium is the condition ate value, for example, between 10 -10 and 1010, indicate
in which the forward and reverse reaction rates of re- that some of the reactants have been converted to
versible processes are equal. Chemical and physical products.
processes in equilibrium are dynamic by nature. 15-5 The Reaction Quotient, Q: Predicting the Direction
15-2 The Equilibrium Constant Expression—This condi- of Net Change—The reaction quotient, Q (equation
tion of dynamic equilibrium is described through an 15.19), has the same form as the equilibrium constant
equilibrium constant expression. The form of the equilib- expression; however, its numerical value is determined
rium constant expression is established from the balanced using the initial reaction activities. A comparison of the
chemical equation using activities to express the “effec- reaction quotient with the equilibrium constant makes it
tive” concentrations (equation 15.7). The numerical value possible to predict the direction of net change leading to
obtained from the equilibrium constant expression is re- equilibrium (Fig. 15-5). If Q 6 K, the forward reaction is
ferred to as the equilibrium constant, K. Equilibrium con- favored, meaning that when equilibrium is established the
stants are unitless. amounts of products will have increased and the amounts
of reactants will have decreased. If Q 7 K, the reverse re-
15-3 Relationships Involving Equilibrium Constants—
action is favored until equilibrium is established. If Q = K,
When the equation for a reversible reaction is written in
neither the forward nor reverse reaction is favored. The
the reverse order, the equilibrium constant expression and
initial conditions are in fact equilibrium conditions.
the value of K are both inverted from their original form.
When two or more reactions are coupled together, the 15-6 Altering Equilibrium Conditions: Le Châtelier’s
equilibrium constant for the overall reaction is the product Principle—Le Châtelier’s principle is used to make quali-
of the K values of the individual reactions. The equilibri- tative predictions of the effects of different variables on an
um constant of a reaction can have different values de- equilibrium condition. This principle describes how an
pending on the reference state used. For Kc a equilibrium condition is modified, or “shifts,” in response
concentration reference state is used, while for Kp , a pres- to the addition or removal of reactants or changes in reac-
sure reference state is used. The relationship between Kc tion volume, external pressure, or temperature. Catalysts,
and Kp is given by equation (15.16). by speeding up the forward and reverse reactions equally,
have no effect on an equilibrium condition.
15-4 The Magnitude of an Equilibrium Constant—The
magnitude of the equilibrium constant can be used to 15-7 Equilibrium Calculations: Some Illustrative
determine the outcome of a reaction. For large values of K Examples—For quantitative equilibrium calculations, a
the reaction goes to completion, with all reactants con- few basic principles and algebraic techniques are
verted to products. A very small equilibrium constant, required. A useful method employs a tabular system,
for example, a large negative power of ten, indicates that called an ICE table, for keeping track of the initial concen-
practically none of the reactants have been converted to trations of the reactants and products, changes in these
products. Finally, equilibrium constants of an intermedi- concentrations, and the equilibrium concentrations.
Integrative Example
In the manufacture of ammonia, the chief source of hydrogen gas is the following reaction for the reforming of methane
at high temperatures.
CH 4(g) + 2 H 2O(g) ∆ CO2(g) + 4 H 2(g) (15.23)
The following data are also given.
(a) CO(g) + H 2O(g) ∆ CO2(g) + H 2(g) ¢H° = -40 kJ; Kc = 1.4 at 1000 K
(b) CO(g) + 3 H 2(g) ∆ H 2O(g) + CH 4(g) ¢H° = -230 kJ; Kc = 190 at 1000 K
At 1000 K, 1.00 mol each of CH 4 and H 2O are allowed to come to equilibrium in a 10.0-L vessel. Calculate the number of
moles of H 2 present at equilibrium. Would the yield of H 2 increase if the temperature were raised above 1000 K?
Strategy
First, we should assemble the data needed to solve this problem. The amounts of substances and a reaction volume are
given, so we should be able to work with a Kc expression. However, because the Kc value for the reaction of interest is not
given, we will have to derive this value by combining the two equations for which data are given. This will yield values
of both Kc and ¢H for the reaction of interest.
To calculate the number of moles of H 2 at equilibrium we can use the ICE method, and to assess the effect of tempera-
ture on the equilibrium yield of H 2 we can apply Le Châtelier’s principle.
PETRMC15_622-662-hr 12/23/05 2:32 PM Page 652
THE NITROGEN CYCLE AND THE SYNTHESIS OF

FOCUS ON NITROGEN COMPOUNDS
environment and a variety of living organisms and back
into the environment. A simplified version of the nitrogen
cycle is depicted in Figure 15-12, which shows that elemen-
tal nitrogen from the atmosphere is fixed, becomes part of
plants, animals, and other organisms, and is then returned
to the atmosphere. The numbers in parentheses refer to the
various parts of the cycle described below.
A few leguminous plants, such as beans, peas, and al-
falfa, have bacteria residing on their roots that convert ele-
mental nitrogen from the air into compounds used to
make plant protein (1). Plants also convert nitrates in the
soil to proteins (5). Animals obtain their protein-building
nitrogen by feeding on plants and/or other animals (2).
The decay of plant and animal proteins produces ammo-
nia (3). Through a series of bacterial actions, ammonia is
converted to nitrites and nitrates (4). Denitrifying bacteria
decompose nitrites and nitrates, returning N2O and N2 to
the atmosphere, thus completing the cycle (6). Some at-
▲ Use of liquid ammonia as a fertilizer by direct injection into mospheric nitrogen is converted to nitrates during electri-
the soil.
cal storms (1a).
Reversible chemical reactions play an important role in
the nitrogen cycle. One example is the reaction of N2(g)
Nitrogen is an element essential both in living things and and O2(g) to form NO(g).
in industry. The atmosphere contains a vast pool of ele- N2(g) + O2(g) ∆ 2 NO(g)
mental nitrogen, but most organisms cannot use nitrogen
in that form. Instead, they require certain nitrogen- Kp = 4.7 * 10-31 at 298 K
containing compounds. The conversion of elemental atmo-
= 1.3 * 10-4 at 1800 K
spheric nitrogen to nitrogen compounds is called nitrogen
fixation, and in nature, this process is carried out only by The reaction does not occur to any measurable extent at
certain types of bacteria. Nitrogen fixation is part of the ni- 298 K, but at 1800 K the situation is a little different. An
trogen cycle, which is the path of nitrogen through the equilibrium mixture of N2(g) and O2(g) at 1800 K
Atmospheric
nitrogen
(6) Bacteria (1) Bacteria
(1a) Lightning
(5) Plant
Nitrates
protein
(6) Bacteria
(2)
(4) Bacteria
Animal (3) Decay
Nitrites
protein
(3) Decay
(4) Bacteria
Ammonia
▲ FIGURE 15-12
The nitrogen cycle
652
PETRMC15_622-662-hr 12/23/05 2:32 PM Page 653
of NH 3 is greatest at low temperatures. Thus, the opti-

mum conditions for the equilibrium production of NH 3 is
greatest at low temperatures. Thus, the optimum condi-
tions for the equilibrium production of NH 3 are high pres-
sures and low temperatures. However, these “optimum”
conditions do not take into account the rate of reaction.
Although the equilibrium production of NH 3 is fa-
vored at low temperatures, equilibrium is achieved so
slowly that the synthesis is not feasible at those tempera-
tures. One way to speed up the reaction is to raise the tem-
perature, even though doing so decreases the equilibrium
concentration of NH 3 . Another way is to use a catalyst.
The usual industrial operating conditions are a tempera-
ture of about 550 °C, pressures ranging from 150 to 350
atm, and a catalyst—usually iron in the presence of Al2O3 ,
MgO, CaO, and K 2O. Figure 15-13 suggests the dramatic
difference between the theoretical optimum conditions
▲ During electrical storms, N2(g) and O2(g) combine to produce and the actual operating conditions.
small quantities of NO(g) in a reversible chemical reaction. Another essential feature of the Haber–Bosch method
is to remove NH 3 as it forms. This is done by liquefying
the NH 3(g). In fact, the mixture need not be brought to
equilibrium at all, and nearly 100% conversion of N2 and
contains about 1 or 2% NO(g). NO(g) is introduced into H 2 to NH 3 is achieved.
the nitrogen cycle through this high-temperature reaction
occurring naturally in lightning flashes during thunder-
storms and artificially in high-temperature combustion
processes, as in internal combustion engines. Further reac- “Theoretical”
tions account for the formation of HNO 3(aq) in rainstorms conditions
and the introduction of nitrates into the soil.
2 NO(g) + O2(g) ¡ 2 NO2(g) 100
3 NO2(g) + H 2O(l) ¡ 2 HNO3(aq) + NO(g) 90
Ammonia at equilibrium, %
80
Ammonia is an important industrial chemical. Its syn-
thesis is achieved by the following reaction. 70
(Ratio H2/N2 3:1)
60
N2(g) + 3 H 2(g) ∆ 2 NH 3(g)
50
¢H° = -92.22 kJ Kp = 6.2 * 105 at 298 K
40
Since ammonia can be converted by soil bacteria to ni- 30
trites and nitrates that can be used by plants, one of the
principal uses of artificial NH 3 is as a fertilizer that is in- 20
jected directly into the soil. NH 3 is also used in the produc- 10 100 300 500 700 900
tion of other nitrogen compounds, such as urea, hydrazine,
ammonium sulfate, ammonium nitrate, ammonium dihy- Pressure, atm
100
drogen phosphate, and ammonium hydrogen phosphate.
C
200
e,
Several of these compounds are used as fertilizers, and

tur
others are used in the manufacture of explosives, pharma- 300

era
ceuticals, and plastics. So much nitrogen is now being

mp
400
fixed artificially that fixed nitrogen is accumulating in the
Te
environment somewhat faster than it is being returned to 500

the atmosphere. This causes environmental problems such 600
as the buildup of nitrates in groundwater.
700
Let us look at the commercial synthesis of ammonia,
called the Haber–Bosch process, from the standpoint of Commercial
chemical equilibrium and kinetics. In the synthesis reac- operating conditions
tion, two moles of gaseous product are formed for every
four moles of gaseous reactants. Carrying out the reaction ▲ FIGURE 15-13
at high pressure favors the production of NH 3 . Because Equilibrium conversion of N2(g) and H2(g) to NH3(g)
the forward reaction is exothermic, the equilibrium yield as a function of temperature and pressure
653
PETRMC15_622-662-hr 12/23/05 2:32 PM Page 654
Solution
We combine equations (a) and (b) to obtain the data needed in this problem.
(a) CO(g) + H 2O(g) ∆ CO 2(g) + H 2(g) ¢H = -40 kJ Kc = 1.4
(b) CH 4(g) + H 2O(g) ∆ CO(g) + 3 H 2(g) ¢H = 230 kJ Kc = 1>190
Overall: CH 4(g) + 2 H 2O(g) ∆ CO 2(g) + 4 H 2(g) ¢H = 190 kJ Kc = 1.4>190 = 7.4 * 10 -3
Next we set up an ICE table in which x represents the number of moles of CH 4 consumed in reaching equilibrium.
The reaction: CH4(g) 2 H2O(g) ∆ CO2(g) 4 H2(g)
initial amounts: 1.00 mol 1.00 mol 0.00 mol 0.00 mol
changes: -x mol -2x mol x mol 4x mol
equil amounts: 11.00 - x2 mol 11.00 - 2x2 mol x mol 4x mol
equil concns, M: 11.00 - x2>10.0 11.00 - 2x2>10.0 x>10.0 4x>10.0
Now we set up Kc and make substitutions into the [CO2][H 2]4

expression. Kc =
[CH 4][H 2O]2
1x>10.0214x>10.024
311.00 - x2/10.04311.00 - 2x2>10.042
=
x14x24
= = 7.4 * 10-3
10011.00 - x211.00 - 2x22
The above equation reduces to 256x 5 = 0.74311.00 - x211.00 - 2x224
and then to 256x 5 - 0.74311.00 - x211.00 - 2x224 = 0 (15.24)

The solution to this equation is x = 0.23 mol. The number
of moles of H 2 at equilibrium is 4x = 0.92 mol.
Because the reaction is endothermic 1¢H = 190 kJ2,
the forward reaction is favored at higher temperatures.
The equilibrium yield of H 2 will increase if the tempera-
ture is raised above 1000 K.
Assessment
Equation (15.24) looks impossibly difficult to solve, but it is not. It can be solved for x rather simply by the method of suc-
cessive approximations. This is done in Appendix A-3, equation (A.2). An important clue as to the possible range of val-
ues for x can be found in the ICE table. Note that the equilibrium amount of H 2O(g) is 1.00 - 2x, meaning that x 6 0.50,
or else all of the H 2O(g) would be consumed. This marks a good place to start the approximations.
Exercises
Writing Equilibrium Constant Expressions
1. Based on these descriptions, write a balanced equa- 2. Based on these descriptions, write a balanced equa-
tion and the corresponding Kc expression for each re- tion and the corresponding Kp expression for each re-
versible reaction. versible reaction.
(a) Carbonyl fluoride, COF2(g), decomposes into (a) Oxygen gas oxidizes gaseous ammonia to
gaseous carbon dioxide and gaseous carbon tetra- gaseous nitrogen and water vapor.
fluoride. (b) Hydrogen gas reduces gaseous nitrogen dioxide
(b) Copper metal displaces silver(I) ion from aqueous to gaseous ammonia and water vapor.
solution, producing silver metal and an aqueous solu- (c) Nitrogen gas reacts with the solid sodium carbon-
tion of copper(II) ion. ate and carbon to produce solid sodium cyanide and
(c) Peroxodisulfate ion, S 2O8 2-, oxidizes iron(II) ion carbon monoxide gas.
to iron(III) ion in aqueous solution and is itself re- 3. Write equilibrium constant expressions, Kc , for the
duced to sulfate ion. reactions
PETRMC15_622-662-hr 12/23/05 2:32 PM Page 655
Exercises 655
(a) 2 NO(g) + O2(g) ∆ 2 NO2(g) 10. If Kc = 5.12 * 10-3 for the equilibrium established
(b) Zn(s) + 2 Ag +(aq) ∆ Zn2+(aq) + 2 Ag(s) between liquid benzene and its vapor at 25 °C, what is
(c) Mg(OH)2(s) + CO3 2-(aq) ∆ the vapor pressure of C6H 6 at 25 °C, expressed in mil-
limeters of mercury?
MgCO3(s) + 2 OH -(aq) 11. Determine Kc for the reaction
4. Write equilibrium constant expressions, Kp , for the 1 1 1
reactions N (g) + O2(g) + Br2(g) ∆ NOBr(g)
(a) CS 2(g) + 4 H 2(g) ∆ CH 4(g) + 2 H 2S(g) 2 2 2 2
1 from the following information (at 298 K).
(b) Ag2O(s) ∆ 2 Ag(s) + O2(g) 2 NO(g) ∆ N 2(g) + O 2(g) Kc = 2.1 * 1030
2
(c) 2 NaHCO3(s) ∆ 1
NO(g) + Br (g) ∆ NOBr(g) Kc = 1.4
Na 2CO3(s) + CO2(g) + H 2O(g) 2 2
5. Write an equilibrium constant, Kc , for the formation
12. Given the equilibrium constant values
from its gaseous elements of (a) 1 mol HF(g);
1
(b) 2 mol NH 3(g); (c) 2 mol N2O(g) (d) 1 mol ClF3(l). N 2(g) + O 2(g) ∆ N 2O(g) Kc = 2.7 * 10 -18
6. Write an equilibrium constant, Kp , for the formation 2
from its gaseous elements of (a) 1 mol NOCl(g); N 2O 4(g) ∆ 2 NO 2(g) Kc = 4.6 * 10 -3
(b) 2 mol ClNO 2(g); (c) 1 mol N2H 4(g); (d) 1 mol 1
NH 4Cl(s). N (g) + O 2(g) ∆ NO 2(g) Kc = 4.1 * 10 -9
2 2
7. Determine values of Kc from the Kp values given.
(a) SO2Cl2(g) ∆ SO2(g) + Cl2(g) Determine a value of Kc for the reaction
Kp = 2.9 * 10-2 at 303 K 2 N2O(g) + 3 O2(g) ∆ 2 N2O4(g)
(b) 2 NO(g) + O2(g) ∆ 2 NO2(g) 13. Use the following data to estimate a value of Kp at 1200 K
Kp = 1.48 * 104 at 184 °C for the reaction 2 H 2(g) + O2(g) ∆ 2 H 2O(g)
(c) Sb2S 3(s) + 3 H 2(g) ∆ 2 Sb(s) + 3 H 2S(g) C(graphite) + CO2(g) ∆ 2 CO(g) Kc = 0.64
Kp = 0.429 at 713 K CO2(g) + H 2(g) ∆ CO(g) + H 2O(g) Kc = 1.4
8. Determine the values of Kp from the Kc values given. 1
(a) N2O4(g) ∆ 2 NO2(g) C(graphite) + O2(g) ∆ CO(g) Kc = 1 * 108
2
Kc = 4.61 * 10-3 at 25 °C
14. Determine Kc for the reaction N2(g) + O2(g) +
(b) 2 CH 4(g) ∆ C2H 2(g) + 3 H 2(g) Cl2(g) ∆ 2 NOCl(g), given the following data at
Kc = 0.154 at 2000 K 298 K.
(c) 2 H 2S(g) + CH 4(g) ∆ 4 H 2(g) + CS 2(g) 1
N2(g) + O2(g) ∆ NO2(g) Kp = 1.0 * 10-9
Kc = 5.27 * 10-8 at 973 K 2
9. The vapor pressure of water at 25 °C is 23.8 mmHg. 1
NOCl(g) + O2(g) ∆ NO2Cl(g) Kp = 1.1 * 102
Write Kp for the vaporization of water, with pressures 2
in atmospheres. What is the value of Kc for the vapor- 1
NO2(g) + Cl2(g) ∆ NO2Cl(g) Kp = 0.3
ization process? 2
Experimental Determination of Equilibrium Constants
15. 1.00 * 10-3 mol PCl5 is introduced into a 250.0-mL phorus compounds, coexist in equilibrium through
flask, and equilibrium is established at 284 °C: the reaction
PCl5(g) ∆ PCl3(g) + Cl2(g). The quantity of Cl2(g) PCl3(g) + Cl2(g) ∆ PCl5(g)
present at equilibrium is found to be 9.65 * 10-4 mol.
What is the value of Kc for the dissociation reaction At 250 °C, an equilibrium mixture in a 2.50-L flask
at 284 °C? contains 0.105 g PCl5 , 0.220 g PCl3 , and 2.12 g Cl2 .
16. A mixture of 1.00 g H 2 and 1.06 g H 2S in a 0.500-L flask What are the values of (a) Kc and (b) Kp for this reac-
comes to equilibrium at 1670 K: 2 H 2(g) + S 2(g) ∆ tion at 250 °C?
2 H 2S(g). The equilibrium amount of S 2(g) found is 18. A 0.682-g sample of ICl(g) is placed in a 625-mL reaction
8.00 * 10-6 mol. Determine the value of Kp at 1670 K. vessel at 682 K. When equilibrium is reached between
17. The two common chlorides of phosphorus, PCl3 and the ICl(g) and I 2(g) and Cl2(g) formed by its dissocia-
PCl5 , both important in the production of other phos- tion, 0.0383 g I 2 is present. What is Kc for this reaction?
PETRMC15_622-662-hr 12/23/05 2:32 PM Page 656
Equilibrium Relationships
19. Equilibrium is established at 1000 K, where Kc = 281 22. At 2000 K, Kc = 0.154 for the reaction 2 CH 4(g) ∆
for the reaction 2 SO 2(g) + O2(g) ∆ 2 SO 3(g). The C2H 2(g) + 3 H 2(g). If a 1.00-L equilibrium mixture at
equilibrium amount of O2(g) in a 0.185-L flask is 2000 K contains 0.10 mol each of CH 4(g) and H 2(g),
0.00247 mol. What is the ratio of [SO2] to [SO3] in this (a) what is the mole fraction of C2H 2(g) present?
equilibrium mixture? (b) Is the conversion of CH 4(g) to C2H 2(g) favored at
20. For the dissociation of I 2(g) at about 1200 °C, high or low pressures?
I 2(g) ∆ 2 I(g), Kc = 1.1 * 10-2. What volume flask (c) If the equilibrium mixture at 2000 K is transferred
should we use if we want 0.37 mol I to be present for from a 1.00-L flask to a 2.00-L flask, will the number
every 1.00 mol I 2 at equilibrium? of moles of C2H 2(g) increase, decrease, or remain
21. In the Ostwald process for oxidizing ammonia, a vari- unchanged?
ety of products is possible—N2 , N2O, NO, and NO2— 23. An equilibrium mixture at 1000 K contains
depending on the conditions. One possibility is 0.276 mol H 2 , 0.276 mol CO 2 , 0.224 mol CO, and
5 3 0.224 mol H 2O.
NH 3(g) + O2(g) ∆ NO(g) + H 2O(g)
4 2 CO2(g) + H 2(g) ∆ CO(g) + H 2O(g)
19
Kp = 2.11 * 10 at 700 K (a) Show that for this reaction, Kc is independent of
the reaction volume, V.
For the decomposition of NO2 at 700 K, (b) Determine the value of Kc and Kp .
1 24. For the reaction CO(g) + H 2O(g) ∆ CO2(g) +
NO2(g) ∆ NO(g) + O2(g) Kp = 0.524
2 H 2(g), Kp = 23.2 at 600 K. Explain which of the fol-
(a) Write a chemical equation for the oxidation of lowing situations might be found at equilibrium:
NH 3(g) to NO2(g). (a) PCO = PH2O = PCO2 = PH2 ; (b) PH2>PH2O =
(b) Determine Kp for the chemical equation you have PCO2>PCO ; (c) (PCO2)(PH2) = (PCO)(PH2O);
written. (d) PCO2>PH2O = PH2>PCO .
Direction and Extent of Chemical Change

25. Can a mixture of 2.2 mol O2 , 3.6 mol SO 2 , and 31. Starting with 0.3500 mol CO(g) and 0.05500 mol
1.8 mol SO3 be maintained indefinitely in a 7.2-L flask COCl2(g) in a 3.050-L flask at 668 K, how many moles
at a temperature at which Kc = 100 in this reaction? of Cl2(g) will be present at equilibrium?
Explain.
2 SO 2(g) + O2(g) ∆ 2 SO 3(g) CO(g) + Cl2(g) ∆ COCl2(g)
26. Is a mixture of 0.0205 mol NO2(g) and 0.750 mol Kc = 1.2 * 103 at 668 K
N2O4(g) in a 5.25-L flask at 25 °C at equilibrium? If
32. 1.00 g each of CO, H 2O, and H 2 are sealed in a 1.41-L
not, in which direction will the reaction proceed—
vessel and brought to equilibrium at 600 K. How
toward products or reactants?
many grams of CO2 will be present in the equilibrium
N2O4(g) ∆ 2 NO2(g) Kc = 4.61 * 10-3 at 25 °C mixture?
27. In the reaction 2 SO2(g) + O2(g) ∆ 2 SO3(g), 0.455 CO(g) + H 2O(g) ∆ CO2(g) + H 2(g) Kc = 23.2
mol SO2 , 0.183 mol O2 , and 0.568 mol SO3 are intro-
duced simultaneously into a 1.90-L vessel at 1000 K. 33. Equilibrium is established in a 2.50-L flask at 250 °C
(a) Is this mixture at equilibrium? for the reaction
(b) If not, in which direction will a net change occur?
28. In the reaction CO(g) + H 2O(g) ∆ CO2(g) + PCl5(g) ∆ PCl3(g) + Cl2(g) Kc = 3.8 * 10-2
H 2(g), K = 31.4 at 588 K. Equal masses of each reac- How many moles of PCl5 , PCl3 , and Cl2 are present at
tant and product are brought together in a reaction equilibrium, if
vessel at 588 K. (a) 0.550 mol each of PCl5 and PCl3 are initially intro-
(a) Can this mixture be at equilibrium? duced into the flask?
(b) If not, in which direction will a net change occur? (b) 0.610 mol PCl5 alone is introduced into the flask?
29. A mixture consisting of 0.150 mol H 2 and 0.150 mol I 2
is brought to equilibrium at 445 °C in a 3.25-L flask. 34. For the following reaction, Kc = 2.00 at 1000 °C.
What are the equilibrium amounts of H 2 , I 2 , and HI? 2 COF2(g) ∆ CO2(g) + CF4(g)
H 2(g) + I 2(g) ∆ 2 HI (g) Kc = 50.2 at 445 °C
If a 5.00-L mixture contains 0.145 mol COF2 , 0.262 mol
30. Starting with 0.280 mol SbCl3 and 0.160 mol Cl2 , how CO2 , and 0.074 mol CF4 at a temperature of 1000 °C,
many moles of SbCl5 , SbCl3 , and Cl2 are present when (a) Will the mixture be at equilibrium?
equilibrium is established at 248 °C in a 2.50-L flask? (b) If the gases are not at equilibrium, in what direc-
tion will a net change occur?
SbCl5(g) ∆ SbCl3(g) + Cl2(g)
(c) How many moles of each gas will be present at
Kc = 2.5 * 10-2 at 248 °C equilibrium?
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Exercises 657
35. In the following reaction, Kc = 4.0. 41. One sketch below represents an initial nonequilibri-
um mixture in the reversible reaction
C2H 5OH + CH 3COOH ∆ CH 3COOC2H 5 + H 2O
SO2(g) + Cl2(g) ∆ SO2Cl2(g) Kc = 4.0
A reaction is allowed to occur in a mixture of 17.2 g
C2H 5OH, 23.8 g CH 3COOH, 48.6 g CH 3COOC2H 5 , Which of the other three sketches best represents an
and 71.2 g H 2O. equilibrium mixture? Explain.
(a) In what direction will a net change occur?
(b) How many grams of each substance will be pre-
sent at equilibrium?
36. The N2O4 –NO2 equilibrium mixture in the flask on
the left in the figure is allowed to expand into the
evacuated flask on the right. What is the composition
of the gaseous mixture when equilibrium is reestab-
lished in the system consisting of the two flasks?
N2O4(g) ∆ 2 NO2(g) Kc = 4.61 * 10-3 at 25 °C
Initial mixture (a)
0.971 mol N2O4

0.0580 mol NO2 2.25 L
25 C
0.750 L
25 C
37. Formamide, used in the manufacture of pharmaceuti-

cals, dyes, and agricultural chemicals, decomposes at (b) (c)
high temperatures.
HCONH 2(g) ∆ NH 3(g) + CO(g) 42. One sketch below represents an initial nonequilibri-
um mixture in the reversible reaction
Kc = 4.84 at 400 K
2 NO(g) + Br2(g) ∆ 2 NOBr(g) Kc = 3.0
If 0.186 mol HCONH 2(g) dissociates in a 2.16-L flask at
400 K, what will be the total pressure at equilibrium? Which of the other three sketches best represents an
38. A mixture of 1.00 mol NaHCO3(s) and 1.00 mol equilibrium mixture? Explain.
Na 2CO3(s) is introduced into a 2.50-L flask in which
the partial pressure of CO2 is 2.10 atm and that of
H 2O(g) is 715 mmHg. When equilibrium is estab-
lished at 100 °C, will the partial pressures of CO2(g)
and H 2O(g) be greater or less than their initial partial
pressures? Explain.
2 NaHCO3(s) ∆ Na 2CO3(s) + CO2(g) + H 2O(g)
Kp = 0.23 at 100 °C
39. Cadmium metal is added to 0.350 L of an aqueous so-
lution in which [Cr 3+] = 1.00 M. What are the concen- Initial mixture (a)
trations of the different ionic species at equilibrium?
What is the minimum mass of cadmium metal re-
quired to establish this equilibrium?
2 Cr 3+(aq) + Cd(s) ∆ 2 Cr 2+(aq) + Cd2+(aq)
Kc = 0.288
3+
40. Lead metal is added to 0.100 M Cr (aq). What are
[Pb 2+], [Cr 2+], and [Cr 3+] when equilibrium is estab-
lished in the reaction?
Pb(s) + 2 Cr 3+(aq) ∆ Pb 2+(aq) + 2 Cr 2+(aq)
Kc = 3.2 * 10-10 (b) (c)
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Partial Pressure Equilibrium Constant, Kp
43. Refer to Example 15-4. H 2S(g) at 747.6 mmHg pres- found to be 0.0721 atm, what are the equilibrium par-
sure and a 1.85-g sample of I 2(s) are introduced into a tial pressure of O2(g) and the total gas pressure?
725-mL flask at 60 °C. What will be the total pressure 46. Concerning the reaction in Exercise 45, if KO2(s)
in the flask at equilibrium? and K 2CO3(s) are maintained in contact with air at
H 2S(g) + I 2(s) ∆ 2 HI(g) + S(s) 1.00 atm and 25 °C, in which direction will a net
change occur to establish equilibrium? Explain.
Kp = 1.34 * 105 at 60 °C [Hint: Recall equation (6.17) and the composition of
44. A sample of NH 4HS(s) is placed in a 2.58-L flask con- air (Table 6.3.)]
taining 0.100 mol NH 3(g). What will be the total gas 47. 1.00 mol each of CO and Cl2 are introduced into an
pressure when equilibrium is established at 25 °C? evacuated 1.75-L flask, and the following equilibrium
is established at 668 K.
NH 4HS(s) ∆ NH 3(g) + H 2S(g)
CO(g) + Cl2(g) ¡ COCl2(g) Kp = 22.5
Kp = 0.108 at 25 °C
For this equilibrium, calculate (a) the partial pressure
45. The following reaction is used in some self-contained
of COCl2(g); (b) the total gas pressure.
breathing devices as a source of O2(g).
48. For the reaction 2 NO2(g) ∆ 2 NO(g) + O2(g),
4 KO2(s) + 2 CO2(g) ∆ 2 K 2CO3(s) + 3 O2(g) Kc = 1.8 * 10-6 at 184 °C. What is the value of Kp for
Kp = 28.5 at 25 °C this reaction at 184 °C?
Suppose that a sample of CO2(g) is added to an evacu- 1

NO(g) + O (g) ∆ NO2(g)
ated flask containing KO2(s) and equilibrium is estab- 2 2
lished. If the equilibrium partial pressure of CO2(g) is
Le Châtelier’s Principle
49. Continuous removal of one of the products of a chem- 53. The reaction N2(g) + O2(g) ∆ 2 NO(g), ¢H° =
ical reaction has the effect of causing the reaction to go +181 kJ, occurs in high-temperature combustion
to completion. Explain this fact in terms of Le Châte- processes carried out in air. Oxides of nitrogen produ-
lier’s principle. ced from the nitrogen and oxygen in air are intimately
50. We can represent the freezing of H 2O(l) at 0 °C as H 2O involved in the production of photochemical smog.
(l, d = 1.00 g>cm3) ∆ H 2O(s, d = 0.92 g>cm3). Ex- What effect does increasing the temperature have on
plain why increasing the pressure on ice causes it to (a) the equilibrium production of NO(g); (b) the rate
melt. Is this the behavior you expect for solids in of this reaction?
general? Explain. 54. Use data from Appendix D to determine whether the
51. Explain how each of the following affects the amount forward reaction is favored by high temperatures or
of H 2 present in an equilibrium mixture in the reaction low temperatures.
3 Fe(s) + 4 H 2O(g) ∆ Fe3O4(s) + 4 H 2(g) (a) PCl3(g) + Cl2(g) ∆ PCl5(g)
¢H° = -150 kJ (b) SO2(g) + 2 H 2S(g) ∆ 2 H 2O(g) + 3 S(s)
(a) Raising the temperature of the mixture; (b) intro- (c) 2 N2(g) + 3 O2(g) + 4 HCl(g) ∆
ducing more H 2O(g); (c) doubling the volume of the 4 NOCl(g) + 2 H 2O(g)
container holding the mixture; (d) adding an appro- 55. If the volume of an equilibrium mixture of N2(g),
priate catalyst. H 2(g), and NH 3(g) is reduced by doubling the pres-
52. In the gas phase, iodine reacts with cyclopentene sure, will PN2 have increased, decreased, or remained
(C5H 8) by a free radical mechanism to produce cy- the same when equilibrium is reestablished? Explain.
clopentadiene (C5H 6) and hydrogen iodide. Explain N2(g) + 3 H 2(g) ∆ 2 NH 3(g)
how each of the following affects the amount of HI(g)
present in the equilibrium mixture in the reaction 56. For the reaction
1
I 2(g) + C5H 8(g) ∆ C5H 6(g) + 2 HI(g) A(s) ∆ B(s) + 2 C(g) + D(g) ¢H° = 0
2
¢H° = 92.5 kJ
(a) Will Kp increase, decrease, or remain constant
(a) Raising the temperature of the mixture; (b) intro- with temperature? Explain.
ducing more C5H 6(g); (c) doubling the volume of the (b) If a constant-volume mixture at equilibrium at 298
container holding the mixture; (d) adding an appro- K is heated to 400 K and equilibrium reestablished,
priate catalyst; (e) adding an inert gas such as He to a will the number of moles of D(g) increase, decrease, or
constant-volume reaction mixture. remain constant? Explain.
PETRMC15_622-662-hr 12/23/05 2:32 PM Page 659
Integrative and Advanced Exercises 659
57. What effect does increasing the volume of the system 1 1

have on the equilibrium condition in each of the fol- (a) NO(g) ∆ N2(g) + O2(g) ¢H° = -90.2 kJ
2 2
lowing reactions? 1
(a) C(s) + H 2O(g) ∆ CO(g) + H 2(g) (b) SO 3(g) ∆ SO2(g) + O2(g) ¢H° = +98.9 kJ
2
(b) Ca(OH)2(s) + CO2(g) ∆ CaCO 3(s) + H 2O(g) (c) N2H 4(g) ∆ N2(g) + 2 H 2(g) ¢H° = -95.4 kJ
(c) 4 NH 3(g) + 5 O2(g) ∆ 4 NO(g) + 6 H 2O(g)
58. For which of the following reactions would you ex- (d) COCl2(g) ∆ CO(g) + Cl2(g) ¢H° = +108.3 kJ
pect the extent of the forward reaction to increase
with increasing temperatures? Explain.
Integrative and Advanced Exercises

59. Explain why the percent of molecules that dissociate condense salicylic acid and phenol as solids; the
into atoms in reactions of the type I 2(g) ∆ 2 I(g) CO2(g) was collected over mercury and its volume
always increases with an increase in temperature. was measured at 20.0 °C and 730 mmHg. In two iden-
60. A 1.100-L flask at 25 °C and 1.00 atm pressure contains tical experiments, the volumes of CO2(g) obtained
CO2(g) in contact with 100.0 mL of a saturated aque- were 48.2 and 48.5 mL, respectively. Calculate Kp for
ous solution in which [CO2(aq)] = 3.29 * 10-2 M. this reaction.
(a) What is the value of Kc at 25 °C for the equilibri-
um CO2(g) ∆ CO2(aq)? OH OH CO2
(b) If 0.01000 mol of radioactive 14CO2 is added to the
flask, how many moles of the 14CO2 will be found in
the gas phase and in the aqueous solution when equi- COOH
librium is reestablished? 67. One of the key reactions in the gasification of coal is
[Hint: The radioactive 14CO2 distributes itself be- the methanation reaction, in which methane is pro-
tween the two phases in exactly the same manner as duced from synthesis gas—a mixture of CO and H 2 .
the nonradioactive 12CO2 .]
61. Refer to Example 15-13. Suppose that 0.100 L of the CO(g) + 3 H 2(g) ∆ CH 4(g) + H 2O(g)
equilibrium mixture is diluted to 0.250 L with water. ¢H = -230 kJ; Kc = 190 at 1000 K
What will be the new concentrations when equilibri-
um is reestablished? (a) Is the equilibrium conversion of synthesis gas to
62. In the equilibrium described in Example 15-12, the methane favored at higher or lower temperatures?
percent dissociation of N2O4 can be expressed as Higher or lower pressures?
(b) Assume you have 4.00 mol of synthesis gas with a
3.00 * 10-3 mol N2O4 3:1 mol ratio of H 2(g) to CO(g) in a 15.0-L flask. What
* 100% = 12.5%
0.0240 mol N2O4 initially will be the mole fraction of CH 4(g) at equilibrium at
What must be the total pressure of the gaseous mix- 1000 K?
ture if N2O4(g) is to be 10.0% dissociated at 298 K? 68. A sample of pure PCl5(g) is introduced into an evacu-
ated flask and allowed to dissociate.
N2O4 ∆ 2 NO2(g) Kp = 0.113 at 298 K
PCl5(g) ∆ PCl3(g) + Cl2(g)
63. Starting with SO3(g) at 1.00 atm, what will be the total
pressure when equilibrium is reached in the following If the fraction of PCl5 molecules that dissociate is de-
reaction at 700 K? noted by a, and if the total gas pressure is P, show that
a2 P
2 SO 3(g) ∆ 2 SO2(g) + O2(g) Kp = 1.6 * 10-5 Kp =
1 - a2
64. A sample of air with a mole ratio of N2 to O2 of 79 : 21
is heated to 2500 K. When equilibrium is established 69. Nitrogen dioxide obtained as a cylinder gas is always a
in a closed container with air initially at 1.00 atm, the mixture of NO2(g) and N2O4(g). A 5.00-g sample ob-
mole percent of NO is found to be 1.8%. Calculate Kp tained from such a cylinder is sealed in a 0.500-L flask at
for the reaction. 298 K. What is the mole fraction of NO2 in this mixture?
N2(g) + O2(g) ∆ 2 NO(g) N2O4(g) ∆ 2 NO2(g) Kc = 4.61 * 10-3
65. Derive, by calculation, the equilibrium amounts of 70. What is the apparent molar mass of the gaseous mix-
SO2 , O2 , and SO3 listed in (a) Figure 15-6(c); (b) ture that results when COCl2(g) is allowed to dissoci-
Figure 15-7(b). ate at 395 °C and a total pressure of 3.00 atm?
66. The decomposition of salicylic acid to phenol and car- COCl2(g) ∆ CO(g) + Cl2(g)
bon dioxide was carried out at 200.0 °C, a temperature
Kp = 4.44 * 10-2 at 395 °C
at which the reactant and products are all gaseous. A
0.300-g sample of salicylic acid was introduced into a Think of the apparent molar mass as the molar mass
50.0-mL reaction vessel, and equilibrium was estab- of a hypothetical single gas that is equivalent to the
lished. The equilibrium mixture was rapidly cooled to gaseous mixture.
PETRMC15_622-662-hr 12/23/05 2:32 PM Page 660
71. Show that in terms of mole fractions of gases and total mixture is allowed to come to equilibrium at 1000 K in
gas pressure the equilibrium constant expression for reaction (15.23). What will be the equilibrium amount,
N2(g) + 3 H 2(g) ∆ 2 NH 3(g) in moles, of each gas?
76. Concerning the reaction in Exercise 22 and the situa-
is tion described in part (c) of that exercise, will the mole
(xNH3)2 1
Kp = * fraction of C2H 2(g) increase, decrease, or remain un-
(xN2)(xH2)2 (Ptot)2 changed when equilibrium is reestablished? Explain.
77. The formation of nitrosyl chloride is given by the fol-
72. For the synthesis of ammonia at 500 K,
lowing equation: 2 NO(g) + Cl2(g) ∆ 2 NOCl(g);
N2(g) + 3 H 2(g) ∆ 2 NH 3(g), Kp = 9.06 * 10-2.
Kc = 4.6 * 104 at 298 K. In a 1.50-L flask, there are
Assume that N2 and H 2 are mixed in the mole ratio
4.125 mol of NOCl and 0.1125 mol of Cl2 present at
1:3 and that the total pressure is maintained at 1.00
equilibrium (298 K).
atm. What is the mole percent NH 3 at equilibrium?
(a) Determine the partial pressure of NO at
[Hint: Use the equation from Exercise 71.]
equilibrium.
73. A mixture of H 2S(g) and CH 4(g) in the mole ratio 2 : 1
(b) What is the total pressure of the system at
was brought to equilibrium at 700 °C and a total pres-
equilibrium?
sure of 1 atm. On analysis, the equilibrium mixture
78. At 500 K, a 10.0-L equilibrium mixture contains
was found to contain 9.54 * 10-3 mol H 2S. The CS 2
0.424 mol N2 , 1.272 mol H 2 , and 1.152 mol NH 3 . The
present at equilibrium was converted successively to
mixture is quickly chilled to a temperature at which the
H 2SO4 and then to BaSO4 ; 1.42 * 10-3 mol BaSO4
NH 3 liquefies, and the NH 3(l) is completely removed.
was obtained. Use these data to determine Kp at
The 10.0-L gaseous mixture is then returned to 500 K,
700 °C for the reaction
and equilibrium is reestablished. How many moles of
2 H 2S(g) + CH 4(g) ∆ CS 2(g) + 4 H 2(g) NH 3(g) will be present in the new equilibrium mixture?
Kp at 700 °C = ? N2(g) + 3 H 2(g) ∆ 2 NH 3 Kc = 152 at 500 K
74. A solution is prepared having these initial concentra- 79. Recall the formation of methanol from synthesis gas,
tions: [Fe 3+] = [Hg 2 2+] = 0.5000 M; [Fe 2+] = [Hg 2+] = the reversible reaction with which we began our discus-
0.03000 M. The following reaction occurs among the sion of the equilibrium constant expression (page 623).
ions at 25 °C.
CO(g) + 2 H 2(g) ∆ CH 3OH(g)
2 Fe 3+(aq) + Hg2 2+(aq) ∆ 2 Fe 2+(aq) + 2 Hg 2+(aq)
Kc = 14.5 at 483 K
Kc = 9.14 * 10-6
A particular synthesis gas consisting of 35.0 mole per-
What will be the ion concentrations at equilibrium? cent CO(g) and 65.0 mole percent H 2(g) at a total pres-
75. Refer to the Integrative Example. A gaseous mixture is sure of 100.0 atm at 483 K is allowed to come to
prepared containing 0.100 mol each of CH 4(g), equilibrium. Determine the partial pressure of
H 2O(g), CO2(g), and H 2(g) in a 5.00-L flask. Then the CH 3OH(g) in the equilibrium mixture.
Feature Problems
80. A classic experiment in equilibrium studies dating HI(g) is introduced into five identical 400-cm3 glass
from 1862 involved the reaction in solution of ethanol bulbs, and the five bulbs are maintained at 623 K.
(C2H 5OH) and acetic acid (CH 3COOH) to produce Each bulb is opened after a period of time and ana-
ethyl acetate and water. lyzed for I 2 by titration with 0.0150 M Na 2S 2O3(aq).
C2H 5OH + CH 3COOH ∆ CH 3COOC2H 5 + H 2O I 2(aq) + 2 Na 2S 2O3(aq) ¡
The reaction can be followed by analyzing the equilib- Na 2S 4O6(aq) + 2 NaI(aq)
rium mixture for its acetic acid content. Data for this experiment are provided in the table
2 CH 3COOH(aq) + Ba(OH)2(aq) ∆ below. What is the value of Kc at 623 K?
Ba(CH 3COO)2(aq) + 2 H 2O(l) Volume
In one experiment, a mixture of 1.000 mol acetic acid Time 0.0150 M Na2S2O3
and 0.5000 mol ethanol is brought to equilibrium. A Initial Bulb Required
sample containing exactly one-hundredth of the equi- Bulb Mass of Opened for Titration
librium mixture requires 28.85 mL 0.1000 M Ba(OH)2 Number HI(g), g (h) (in mL)
for its titration. Calculate the equilibrium constant,
Kc , for the ethanol–acetic acid reaction based on this 1 0.300 2 20.96
experiment. 2 0.320 4 27.90
81. The decomposition of HI(g) is represented by the 3 0.315 12 32.31
equation 4 0.406 20 41.50
2 HI(g) ∆ H 2(g) + I 2(g) 5 0.280 40 28.68
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Self-Assessment Exercises 661
82. In one of Fritz Haber’s experiments to establish the con- steps as reversible and others as going to com-
ditions required for the ammonia synthesis reaction, pletion. However, as noted in Table 15.3, every
pure NH 3(g) was passed over an iron catalyst at 901 °C reaction has an equilibrium constant even though
and 30.0 atm. The gas leaving the reactor was bubbled a reaction is generally considered to go to comple-
through 20.00 mL of a HCl(aq) solution. In this way, the tion if its equilibrium constant is very large.)
NH 3(g) present was removed by reaction with HCl. • Use the idea that when equilibrium is attained in
The remaining gas occupied a volume of 1.82 L at STP. an overall reaction, it is also attained in each step
The 20.00 mL of HCl(aq) through which the gas had of its mechanism. Moreover, we can write an equi-
been bubbled required 15.42 mL of 0.0523 M KOH for its librium constant expression for each step in the
titration. Another 20.00-mL sample of the same HCl(aq) mechanism, similar to what we did with the
through which no gas had been bubbled required steady-state assumption in describing reaction
18.72 mL of 0.0523 M KOH for its titration. Use these mechanisms.
data to obtain a value of Kp at 901 °C for the reaction • Combine the Kc expressions for the elementary
N2(g) + 3 H 2(g) ∆ 2 NH 3(g). steps into a Kc expression for the overall reaction.
83. The following is an approach to establishing a rela- The numerical value of the overall Kc can thereby
tionship between the equilibrium constant and rate be expressed as a ratio of rate constants, k.
constants mentioned in the Are You Wondering fea- Use this approach to establish the equilibrium constant
ture on page 628. expression for the overall reaction,
H 2(g) + I 2(g) ∆ 2 HI(g)
• Work with the detailed mechanism for the reaction.
The mechanism of the reaction appears to be the
• Use the principle of microscopic reversibility, the
following:
idea that every step in a reaction mechanism is re-
versible. (In the presentation of elementary reac- Fast: I 2(g) ∆ 2 I(g)
tions in Chapter 14, we treated some reaction Slow: 2 I(g) + H 2(g) ∆ 2 HI(g)
Self-Assessment Exercises
84. In your own words, define or explain the following 91. For the dissociation reaction 2 H 2S(g) ∆ 2 H 2(g) +
terms or symbols: (a) Kp ; (b) Qc ; (c) ¢ngas . S 2(g), Kp = 1.2 * 10-2 at 1065 °C. For this same
85. Briefly describe each of the following ideas or phe- reaction at 1000 K, (a) Kc is less than Kp ; (b) Kc is
nomena: (a) dynamic equilibrium; (b) direction of a greater than Kp ; (c) Kc = Kp ; (d) whether Kc is less
net chemical change; (c) Le Châtelier’s principle; than, equal to, or greater than Kp depends on the total
(d) effect of a catalyst on equilibrium. gas pressure.
86. Explain the important distinctions between each pair 92. The following data are given at 1000 K: CO(g) +
of terms: (a) reaction that goes to completion and re- H 2O(g) ∆ CO2(g) + H 2(g); ¢H° = -42 kJ;
versible reaction; (b) Kc and Kp ; (c) reaction quotient Kc = 0.66. After an initial equilibrium is established
(Q) and equilibrium constant expression (K); (d) ho- in a 1.00-L container, the equilibrium amount of H 2
mogeneous and heterogeneous reaction. can be increased by (a) adding a catalyst; (b) increas-
87. In the reversible reaction H 2(g) + I 2(g) ∆ 2 HI(g), ing the temperature; (c) transferring the mixture to a
an initial mixture contains 2 mol H 2 and 1 mol I 2 . The 10.0-L container; (d) in some way other than (a), (b),
amount of HI expected at equilibrium is (a) 1 mol; or (c).
(b) 2 mol; (c) less than 2 mol; (d) more than 2 mol but 93. Equilibrium is established in the reversible reaction
less than 4 mol. 2 A + B ∆ 2 C. The equilibrium concentrations
88. Equilibrium is established in the reaction 2 SO2(g) + are [A] = 0.55 M, [B] = 0.33 M, [C] = 0.43 M. What
O2(g) ∆ 2 SO3(g) at a temperature where Kc = 100. is the value of Kc for this reaction?
If the number of moles of SO3(g) in the equilibrium 94. The Deacon process for producing chlorine gas from
mixture is the same as the number of moles of SO2(g), hydrogen chloride is used in situations where HCl is
(a) the number of moles of O2(g) is also equal to the available as a by-product from other chemical
number of moles of SO2(g); (b) the number of moles of processes.
O2(g) is half the number of moles of SO2 ; (c) [O 2] may 4 HCl(g) + O2(g) ∆ 2 H 2O(g) + 2 Cl2(g)
have any of several values; (d) [O2] = 0.010 M.
89. The volume of the reaction vessel containing an equi- ¢H° = -114 kJ
librium mixture in the reaction SO2Cl2(g) ∆ A mixture of HCl, O2 , H 2O, and Cl2 is brought to
SO2(g) + Cl2(g) is increased. When equilibrium is equilibrium at 400 °C. What is the effect on the equi-
reestablished, (a) the amount of Cl2 will have librium amount of Cl2(g) if
increased; (b) the amount of SO2 will have decreased; (a) additional O2(g) is added to the mixture at con-
(c) the amounts of SO2 and Cl2 will have remained the stant volume;
same; (d) the amount of SO2Cl2 will have increased. (b) HCl(g) is removed from the mixture at constant
90. For the reaction 2 NO2(g) ∆ 2 NO(g) + O2(g), volume;
Kc = 1.8 * 10-6 at 184 °C. At 184 °C, the value of Kc (c) the mixture is transferred to a vessel of twice the
for the reaction NO(g) + 12 O2(g) ∆ NO2(g) is volume;
(a) 0.9 * 106; (b) 7.5 * 102; (c) 5.6 * 105; (d) a catalyst is added to the reaction mixture;
(d) 2.8 * 105. (e) the temperature is raised to 500 °C?
PETRMC15_622-662-hr 12/23/05 4:05 PM Page 662
95. An equilibrium mixture of SO2 , SO3 , and O2 gases is (b) If the number of moles of SO3 in the flask is twice
maintained in a 2.05-L flask at a temperature at which the number of moles of SO2 , how many moles of O2
Kc = 35.5 for the reaction are present?
2 SO 2(g) + O2(g) ∆ 2 SO 3(g) 96. Using the method in Appendix E, construct a concept
map of Section 15-6, illustrating the shift in equilibri-
(a) If the numbers of moles of SO2 and SO3 in the um due to the various stresses.
flask are equal, how many moles of O2 are present?
eMedia Exercises
97. After viewing the Dynamic Equilibrium animation 100. Using equal initial concentrations of reactant and
of equilibrium through a physical change (Activebook product in the Equilibrium Constant activity
15-1), describe the influence of temperature on rates (Activebook 15-4), describe how the value of the equi-
of change. librium constant is related to the concentration of the
98. After viewing the Chemical Equilibrium activity product once equilibrium has been reached.
(eBook 15-2), estimate the value of the equilibrium 101. (a) What would be the change in the results seen
constant of the reaction depicted. What information in the NO2 –N2O4 Equilibrium animation (Active-
did you use to make this estimate? book 15-6) if the pressure were decreased by a factor of
99. (a) Describe how the stoichiometry of the reaction two instead of increased? (b) Given that this forward
in the Chemical Equilibrium activity (Activebook reaction is exothermic, what would be the effect on
15-2 ) influences the values of concentrations at equi- the ratio of the NO2 and N2O4 concentrations by
librium. (b) If the initial concentrations of both reac- increasing the temperature of the system?
tants are doubled in this exercise, does this change the
value of the equilibrium constant? (c) Does this
change, if any, affect the concentration of the product
at equilibrium?

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PETRMC15_622-662-hr 12/23/05 2:31 PM Page 622

15-1 Dynamic Equilibrium

15-2 The Equilibrium Constant Expression 623

15-2 THE EQUILIBRIUM CONSTANT EXPRESSION

624 Chapter 15 Principles of Chemical Equilibrium

In anticipation of entropy, Are You Wondering . . .

Saturated solution only

15-2 The Equilibrium Constant Expression 625

TABLE 15.1 Three Approaches to Equilibrium in the Reactiona

CO(g) H2(g) CH3OH(g) Point out to students that

Initial amounts, mol 0.000 0.000 1.000

Initial amounts, mol 1.000 1.000 1.000

2.00 2.00 2.00 te

Moles of reactants and products

Moles of reactants and products

1.40 1.40 1.40

0.80 0.80 0.80

0.60 0.60 0.60

0.40 0.40 0.40

0.20 0.20 0.20

Three approaches to equilibrium

626 Chapter 15 Principles of Chemical Equilibrium

[CH3OH] [CH3OH] [CH3OH]

0.00892 0.00892 0.00892

Stress that “equilibrium”

where a represents the activity of each reactant or product denoted through a

15-2 The Equilibrium Constant Expression 627

628 Chapter 15 Principles of Chemical Equilibrium

A GENERAL EXPRESSION FOR K

The numerator of an equilibrium constant expression is the product of the

Are You Wondering . . .

15-3 Relationships Involving Equilibrium Constants 629

15-3 RELATIONSHIPS INVOLVING EQUILIBRIUM

RELATIONSHIP OF K TO THE BALANCED CHEMICAL EQUATION

630 Chapter 15 Principles of Chemical Equilibrium

The equilibrium constant K¿ becomes K¿ = 1>13.6 * 1082 = 2.8 * 10-9

Then, to base the equation on 1 mol NH 3(g), divide all coef- 1 3

COMBINING EQUILIBRIUM CONSTANT EXPRESSIONS

Suppose we seek the equilibrium constant for the reaction

Equation (15.8) is obtained by reversing equation (15.9) and adding it to (15.10).

(b) N2(g) + O2(g) ∆ 2 NO(g) K(b) = 4.7 * 10-31

15-3 Relationships Involving Equilibrium Constants 631

The overall equation is expression (15.8), and according to the general

= 3.7 * 1017 * 4.7 * 10-31 = 1.7 * 10-13

CONCEPT ASSESSMENT ✓ Point out that the reaction

EQUILIBRIA INVOLVING GASES: THE EQUILIBRIUM CONSTANTS,

As expected, the equilibrium constant is dimensionless. To designate that a

632 Chapter 15 Principles of Chemical Equilibrium

As expected the final expression is dimensionless. Because we have desig-

KEEP IN MIND (15.16)

15-3 Relationships Involving Equilibrium Constants 633

EQUILIBRIA INVOLVING PURE LIQUIDS AND SOLIDS

Equilibrium constant expressions do not contain concentration terms for solid or

Equilibrium in the reaction

634 Chapter 15 Principles of Chemical Equilibrium

One of our examples in Section 15-1 was liquid–vapor equilibrium. This is a

Substitute partial pressures for the activities into the (PHI)2

15-4 THE MAGNITUDE OF AN EQUILIBRIUM CONSTANT

15-4 The Magnitude of an Equilibrium Constant 635