Beruflich Dokumente
Kultur Dokumente
Tom Holme
www.cengage.com/chemistry/brown
Chapter 12
Chemical Equilibrium
2
Chapter Objectives
• Calculate equilibrium composition from initial data and the
numerical value of the equilibrium constant.
3
Chapter Objectives
• Calculate the new equilibrium composition of a system after
an applied stress.
4
Concrete Production and Weathering
6
Concrete Production and Weathering
8
Concrete Production and Weathering
• Uses of admixtures
• Weathering of concrete
• Freeze-thaw cycles
Ca(OH)2 (s)
Ca 2 (aq) + 2OH – (aq)
2
Ca
(aq) + 2OH –
(aq) CO2 (g)
CaCO 3 (s) H 2 O(l )
12
Forward and Reverse Reactions
13
Forward and Reverse Reactions
• The equilibrium
between liquid and
vapor in a closed
container is governed
by the kinetics of
evaporation and
condensation.
14
Forward and Reverse Reactions
• At the start of a chemical reaction, the reactant concentrations
decrease over time, with a corresponding decrease in rate of the
forward reaction.
• When the rate of the forward reaction equals the rate of the reverse
reaction, the reaction has reached equilibrium.
• Reactants form products at the same rate the products reform
the reactants.
• The concentrations of reactants and products do not change
over time at equilibrium.
15
Forward and Reverse Reactions
R
Ä P
• Rate laws for the forward and reverse reaction can be written.
17
Mathematical Relationships
• At equilibrium Ratefor = Raterev.
• Therefore
kfor [R]eq krev [P]eq
• or
kfor [P]eq
krev [R]eq
18
Mathematical Relationships
kfor [P]eq
krev [R]eq
19
Equilibrium Constants
• The amounts of reactants and products are determined using
a mathematical model to describe equilibrium.
20
The Equilibrium (Mass Action) Expression
a A + b B Ä c C + d D
• A ratio of concentrations, whether or not at equilibrium, can be
defined, where Q is the reaction quotient.
[C]c [D]d
Q=
[A]a [B]b
• At equilibrium, Q = K, the equilibrium constant, and this ratio
becomes the equilibrium expression.
[C]ceq [D]deq
K=
[A]aeq [B]beq 21
Example Problem 12.1
• Write the equilibrium expression for this reaction.
22
Gas Phase Equilibria: KP vs. KC
• Equilibrium expressions can be written for gas phase
reactions using partial pressures.
• Kp is the equilibrium constant in terms of partial pressures.
a
A(g) + b B(g) Ä c C(g) + d D(g)
c d
(P ) (P )
C eq D eq
KP = a b
(P ) (P )
A eq B eq
23
Gas Phase Equilibria: KP vs. KC
(ngas )
K P K C RT
24
Homogeneous and Heterogeneous Equilibria
25
Homogeneous and Heterogeneous Equilibria
27
Numerical Importance of the Equilibrium Expression
[products]
K=
[reactants]
• For large values of K, K >> 1, products are favored.
28
Example Problem 12.3
• In Example Problem 12.2, we saw that hydroxide ions
precipitate with calcium. Magnesium ions show similar
behavior. The two pertinent equilibria are:
29
Mathematical Manipulation of Equilibrium Constants
[A]aeq [B]beq
cC + dD Ä aA + bB K' = c d
[C] [D]
eq eq
1
K'
K
30
Adjusting the Stoichiometry of the Chemical Reaction
• If changes are made to the stoichiometry (represented by factor n), the changes affect the
equilibrium expression.
• Multiply the stoichiometric coefficients in a chemical reaction by a factor n, the K for the
new chemical equation, K, equals Kn.
[C]ceq [D]deq
aA + bB Ä cC + dD K=
[A]aeq [B]beq
c d
a b c d [C] [D]
2
eq
2
eq
A+ B Ä C+ D K' = a b
2 2 2 2
[A] [B]
2
eq
2
eq
• Equation 1 was multiplied by n = 1/2.
• K = Kn or K = K1/2
31
Example Problem 12.4
• Write equilibrium expressions for:
32
Equilibrium Constants for a Series of Reactions
K 3 K1 K 2
33
Example Problem 12.5
• Given the following equilibria:
1
CO 2 (g) Ä CO(g) O 2 (g)
2
1
H 2 (g) O 2 (g) Ä H 2O(g)
2
Determine the equilibrium expression for the sum of the two
reactions.
34
Units and the Equilibrium Constant
35
Equilibrium Concentrations
• The equilibrium concentrations of reactants and products for a
chemical reaction can be predicted using the balanced
chemical equation and known equilibrium constants.
• There are three basic features for the strategy used in any
equilibrium calculation.
• Write a balanced chemical equation for the relevant
equilibrium or equilibria.
• Write the corresponding equilibrium expression or
expressions.
• Create a table of concentrations for all reacting
species.
36
Equilibrium Concentrations
• Equilibrium concentrations can be determined from initial
concentrations by realizing:
37
Example Problem 12.6
38
Equilibrium Concentrations from Initial Concentrations
39
Equilibrium Concentrations from Initial Concentrations
[HI]2 (2x)2
K= 59.3
[H 2 ][I2 ] (0.050 x)(0.050 x)
(2x)2
59.3
(0.050 x)(0.050 x)
2x
7.70
0.050 x
0.39 9.70x
x 0.040
[H 2 ] [I2 ] 0.050 x
[H 2 ] [I2 ] 0.050 0.040 0.010 M
[HI] 2x 0.080 M
41
Example Problem 12.7
• The equilibrium constant for the reaction of chlorine gas with
phosphorous trichloride to form phosphorus pentachloride is
33 at 250°C. If an experiment is initiated with concentrations
of 0.050 M PCl3 and 0.015 M Cl2, what are the equilibrium
concentrations of all three gases?
Cl
2 (g) + PCl 3 (g) Ä PCl 5 (g)
42
Mathematical Techniques for Equilibrium Calculations
43
Le Châtelier’s Principle
• Le Châtelier’s principle - When a system at equilibrium is
stressed, it responds by reestablishing equilibrium to reduce
the stress.
• Changes in concentration
• Changes in pressure
• Changes in temperature
44
Effect of a Change in Concentration
45
Effect of a Change in Concentration
[products]
Q=
[reactants]
46
Effect of a Change in Concentration
[products]
Q=
[reactants]
47
Effect of a Change in Concentration
49
Example Problem 12.8
• Predict the change in the reaction quotient, Q, when:
CH 3COOH(aq) Ä H (aq) CH 3COO (aq)
–
50
Effect of a Change in Pressure
51
Effect of a Change in Pressure
• For the equilibrium between NO2 and N2O4, the increase in pressure is
offset by reducing the moles of gas present by forming N2O4.
• Decreasing the volume to 2 L initially increases the pressure to 5.0 atm.
• Equilibrium is re-established when the pressure is reduced to 4.6
atm by reacting 2 NO2 to form N2O4.
52
Example Problem 12.9
• Predict the direction in which the reaction will go to respond to
the indicated stress.
53
Effect of a Change in Temperature on Equilibrium
54
Effect of a Change in Temperature on Equilibrium
• Temperature effect on
the equilibrium between
NO2 and N2O4, an
exothermic reaction.
• As temperature
increases, the
amount of NO2
increases, as
indicated by the
deepening color of
the NO2 gas in the
50oC water bath
(right) compared to
the ice bath (left).
55
Effect of a Change in Temperature on Equilibrium
57
Solubility Equilibria
• The insoluble solutes predicted by the solubility guidelines are also
referred to as sparingly soluble.
• Given enough fresh solvent, an insoluble salt will completely
dissolve.
59
Example Problem 12.10
• Write the solubility product constant expression for calcium
fluoride.
60
Example Problem 12.11
• What is the molar solubility of calcium phosphate, given that
Ksp = 2.0 10-33?
61
The Relationship Between KSP and Molar Solubility
x 1.1 10 7
62
Common Ion Effect
• For a sparingly soluble salt at
equilibrium, addition of a common ion
from an outside source will depress the
solubility of the salt.
• Common ions are found in both the
sparingly soluble salt and the
aqueous solution being added.
64
Reliability of Using Molar Concentrations
65
Acids and Bases
• Strong acids and strong bases completely dissociate in
solution.
66
The Role of Water in the Brønsted-Lowry Theory
68
The Role of Water in the Bronsted-Lowry Theory
69
Example Problem 12.13
• When dissolved in water, CH3COOH is called acetic acid.
Write the equilibrium for its reaction in water and identify the
conjugate acid–base pairs.
70
Weak Acids and Bases
• Weak acids react with water to produce a conjugate acid-base
system in which the acid and base in the products are
stronger than their conjugate acid and base in the reactants.
• Weak acid equilibria favor reactants.
• Only a small percentage of acid molecules ionize.
+
HA(aq)
+ H 2 O(l ) Ä H 3O (aq) + A (aq)
• The K for the dissociation of a weak acid is called the acid
ionization constant, Ka.
+
[H 3O ][A ]
Ka
[HA]
71
Weak Acids and Bases
• Acid ionization
constants for some
common acids at
25oC. Larger values
of Ka indicate stronger
acids.
72
Weak Acids and Bases
• For weak bases, an ionization equilibrium and equilibrium
expression can be written.
+
B(aq)
+ H 2 O(l ) Ä HB (aq) + OH (aq)
• The K for the reaction of a weak base with water is called the
base ionization constant, Kb.
+
[HB ][OH ]
Kb
[B]
73
Weak Acids and Bases
• The hydronium concentration for an aqueous solution can be
reported as pH.
pH log[H 3O + ]
74
Weak Acids and Bases
• The pH scale provides an
easy way to measure the
relative acidity or basicity of
aqueous solutions.
75
Example Problem 12.14
• The Ka of acetic acid is 1.8 10-5. Calculate the pH of a
0.10 M acetic acid solution.
76
Weak Acids and Bases
• The weathering of concrete by carbonation is an acid-base
reaction.
• If CO2 dissolves in water first, the resulting carbonic acid
would react with the basic calcium hydroxide.
77
Free Energy and Chemical Equilibrium
• G = 0 at equilibrium.
78
Graphical Perspective
G RT ln K
o
80
Example Problem 12.15
• Using tabulated thermodynamic data, calculate the
equilibrium constant for the following reaction at 25˚C:
1
CH 4 (g) O 2 (g) Ä CH 3OH(l )
2
81
Borates and Boric Acid
• Borax is used as a cross-linker during polymer synthesis.
83