Beruflich Dokumente
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Chemistry
The Molecular Nature of
Matter and Change
Fifth Edition
Martin S. Silberberg
17-1 Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Chapter 17
17-2
Equilibrium: The Extent of Chemical Reactions
17-3
Kinetics applies to the speed of a reaction, the concentration of
product that appears (or of reactant that disappears) per unit time.
17-4
Figure 17.1
Reaching equilibrium on the macroscopic and molecular levels of
the reaction: N O (g) 2NO (g).
2 4 2
17-5
If rateforward = ratereverse then
kforward[reactants]m = kreverse[products]n
kforward [products]n
= = K the equilibrium constant
kreverse [reactants]m
17-6
Figure 17.2 The range of equilibrium constants.
small K
large K
intermediate K
17-7
Q - The Reaction Quotient
At any time, t, the system can be sampled to determine the amounts of
reactants and products present. A ratio of products to reactants,
calculated in the same manner as K tells us whether the system has come
to equilibrium (Q = K) or whether the reaction has to proceed further from
reactants to products (Q < K) or in the reverse direction from products to
reactants (Q > K).
17-8
Table 17.1 Initial and Equilibrium Concentration Ratios for
17-9
Figure 17.3 The change in Q during the N2O4-NO2 reaction.
17-10
Sample Problem 17.1 Writing the Reaction Quotient from the Balanced
Equation
PROBLEM: Write the reaction quotient, Qc, for each of the following reactions:
(a) The decomposition of dinitrogen pentoxide, N2O5(g) NO2(g) + O2(g)
(b) The combustion of propane gas, C3H8(g) + O2(g) CO2(g) + H2O(g)
SOLUTION:
[NO2]4[O2]
(a) 2 N2O5(g) 4NO2(g) + O2(g) Qc =
[N2O5]2
[CO2]3[H2O]4
(b) C3H8(g) + 5 O2(g) 3 CO2(g) + 4H2O(g) Qc =
[C3H8][O2]5
17-11
Sample Problem 17.2 Writing the Reaction Quotient and Finding K for an
Overall Reaction
PROBLEM: Understanding reactions involving N2 and O2, the most abundant
gases in air, is essential for solving problems dealing with
atmospheric pollution. Here is a reaction sequence between N2 and
O2 to form nitrogen dioxide, a toxic pollutant that contributes to
photochemical smog.
(1) N2(g) + O2(g) 2NO(g) Kc1 = 4.3x10-25
(a) Show that the Qc for the overall reaction sequence is the same as the
product of the Qcs of the individual reactions.
(b) Calculate the Kc for the overall reaction.
PLAN: Write the sum of the overall reactions; write the Qc. Write the Qcs for
the individual reactions and then multiply the expressions.
We are given the Kcs for the individual reactions, so we multiply those
values.
17-12
Sample Problem 17.2 Writing the Reaction Quotient for an Overall Reaction
17-13
Calculating Variations on Q and K
[C]c[D]d
aA + bB cC + dD Qc =
[A]a[B]b
cC + dD aA + bB Q’ = 1/Qc
n aA + bB cC + dD Qc’ = (Qc)n
17-14
Sample Problem 17.3 Finding the Equilibrium Constant for an Equation
Multiplied by a Common Factor
(a) The reference equation is multiplied by 1/3, so Kc(ref) will be to the 1/3 power.
Kc = [Kc(ref)]1/3 = (2.4x10-3)1/3 = 0.13
(b) The reference equation is reversed and halved, so Kc(ref) is to the -1/2 power.
17-15
Figure 17.4 The reaction quotient for a heterogeneous system.
solids do not
change their
concentrations
17-16
Expressing Equilibria with Pressure Terms
Kc and Kp
n P n
PV = nRT P= RT = =M
V RT V
2
PNO [NO2]2
QP 2
2
Qc =
PNO PO2 [NO]2 [O2]
Kp = Kc (RT)n(gas)
17-17
17-18
Sample Problem 17.4 Converting Between Kc and Kp
PROBLEM: A chemical engineer injects limestone (CaCO3) into the hot flue
gas of a coal-burning power plant for form lime (CaO), which
scrubs SO2 from the gas and forms gypsum. Find Kc for the
following reaction, if CO2 pressure is in atmospheres.
17-19
Figure 17.5 Reaction direction and the relative sizes of Q and K.
Reaction Reaction
Progress Progress
17-20
Sample Problem 17.5 Using Molecular Scenes to Determine Reaction
Direction
PROBLEM: The reaction of A(g) B(g) at 175oC is composed of [A] =
2.8x10-4 M and [B] = 1.2x10-4 M. Which direction does the reaction
shift in each of these molecular scenes (A is red; B is blue)?
PLAN: Calculate Kc from the actual reaction data. Use number of spheres from
depiction to calculate Qc and compare to Kc to determine direction.
SOLUTION: [B] 1.2x10-4 [B]
Kc = = = 0.43 Qc =
[A] 2.8x10-4 [A]
1. Qc > Kc; left 2. Qc = Kc; no change 3. Qc > Kc; left 4. Qc < Kc; right
17-21
Sample Problem 17.6 Comparing Q and K to Determine Reaction Direction
17-22
Sample Problem 17.7 Calculating Kc from Concentration Data
PLAN: First find the molar concentration of the starting material and then find
the amount of each component, reactants and products, at equilibrium.
SOLUTION: [HI] = 0.200 mol
= 0.100 M
2.00 L
17-23
Sample Problem 17.7 Calculating Kc from Concentration Data
initial 0.100 0 0
change -2x +x +x
equilibrium 0.100 - 2x x x
17-24
Sample Problem 17.8 Determining Equilibrium Concentrations from Kc
PROBLEM: Fuel engineers use the extent of the change from CO and H2O to
CO2 and H2 to regulate the proportions of synthetic fuel mixtures. If
0.250 mol of CO and 0.250 mol of H2O are placed in a 125-mL flask
at 900 K, what is the composition of the equilibrium mixture? At this
temperature, Kc is 1.56 for the equation
CO(g) + H2O(g) CO2(g) + H2(g)
17-26
Sample Problem 17.9 Determining Equilibrium Concentrations from Initial
Concentrations and Kc
x
1.56 = = +/-1.25
2.00-x
17-27
Sample Problem 17.10 Calculating Equilibrium Concentrations with a
Simplifying Assumption
PLAN: After finding the concentration of starting material, write the expressions
for the equilibrium concentrations. When solving for the remaining
amount of reactant, see if you can make an assumption about the initial
and final concentrations which could simplify the calculating by ignoring
the solution to a quadratic equation.
17-28
Sample Problem 17.10 Calculating Equilibrium Concentrations with a
Simplifying Assumption
(x)(x)
[CO][Cl2] (a) Kc = 8.3x10-4 =
Kc = (0.500 - x)
[COCl2]
assume x is << 0.500 so that we can drop x in the denominator
(x)(x) 4.15x10-4 = x2 x ≈ 2 x 10-2
8.3x10 = -4
(x)(x)
(b) Kc = 8.3x10 =-4
(0.010 - x)
Dropping the -x will give a value for x = 2.9x10-3 M. (0.010 - x) ≈ 0.0071 M
17-29
Sample Problem 17.11 Predicting Reaction Direction and Calculating
Equilibrium Concentrations
In one experiment, 1.00 mol of CH4, 1.00 mol of CS2, 2.00 mol of H2S, and 2.00 mol
of H2 are mixed in a 250-mL vessel at 960oC. At this temperature, Kc = 0.036.
(a) In which direction will the reaction proceed to reach equilibrium?
(b) If [CH4] = 5.56 M at equilibrium, what are the equilibrium concentrations of the
other substances?
PLAN: Find the initial molar concentrations of all components and use these to
calculate a Qc. Compare Qc to Kc, determine in which direction the
reaction will progress, and draw up expressions for equilibrium
concentrations.
SOLUTION: [CH4]initial = 1.00 mol/0.25 L = 4.0 M [CS2]initial = 1.00 mol/0.25 L = 4.0 M
17-30
Sample Problem 17.11 Predicting Reaction Direction and Calculating
Equilibrium Concentrations
17-32
Le Chatelier’s Principle
17-33
Figure 17.7 The effect of a change in concentration.
17-34
Table 17.3 The Effect of Added Cl2 on the PCl3-Cl2-PCl5 System
Disturbance +0.075
Change -x -x +x
17-35
Figure 17.8 The effect of added Cl2 on the PCl3-Cl2-PCl5 system.
17-36
Sample Problem 17.12 Predicting the Effect of a Change in Concentration
on the Equilibrium Position
PROBLEM: To improve air quality and obtain a useful product, chemists often
remove sulfur from coal and natural gas by treating the fuel
contaminant hydrogen sulfide with O2:
2H2S(g) + O2(g) 2S(s) + 2H2O(g)
What happens to
(a) [H2O] if O2 is added? (b) [H2S] if O2 is added?
(c) [O2] if H2S is removed? (d) [H2S] if sulfur is added?
SOLUTION: Q = [H2O]2
[H2S]2[O2]
Q= [H2O]2
[H2S]2[O2]
17-38
Figure 17.9 The effect of pressure (volume) on a system at
equilibrium.
+
lower P
(higher V)
more moles
of gas
higher P
(lower V)
fewer moles
of gas
17-39
Sample Problem 17.13 Predicting the Effect of a Change in Volume
(Pressure) on the Equilibrium Position
PROBLEM: How would you change the volume of each of the following
reactions to increase the yield of the products.
(a) CaCO3(s) CaO(s) + CO2(g)
SOLUTION: (a) CO2 is the only gas present. To increase its yield, we
should increase the volume (decrease the pressure).
(b) There are more moles of gaseous reactants than products, so we should
decrease the volume (increase the pressure) to shift the reaction to the right.
(c) There are an equal number of moles of gases on both sides of the
reaction, therefore a change in volume will have no effect.
17-40
The Effect of a Change in Temperature on an Equilibrium
17-41
Sample Problem 17.14 Predicting the Effect of a Change in Temperature
on the Equilibrium Position
PROBLEM: How does an increase in temperature affect the concentration of
the underlined substance and K for the following reactions?
(a) CaO(s) + H2O(l) Ca(OH)2(aq) Ho = -82 kJ
17-42
The van’t Hoff Equation
The Effect of T on K
R = universal gas constant
K2 Horxn 1 1
ln = - - = 8.314 J/mol*K
K1 R T2 T1 K1 is the equilibrium constant at T1
Temperature Dependence
K2 Ea
1 1 P2 Hvap 1 1
ln = - - ln = - -
K1 R T2 T1 P1 R T2 T1
K2 Horxn 1 1
ln = - -
K1 R T2 T1
17-43
17-44
Sample Problem 17.15 Determining Equilibrium Parameters from
Molecular Species
PROBLEM: For the reaction X(g) + Y2(g) XY(g) + Y(g) H > 0
the following molecular scenes depict different reaction mixtures.
(X = green, Y = purple)
17-45
Sample Problem 17.15 Determining Equilibrium Parameters from
Molecular Scenes
Q = 15 Q = 2.0 Q = 0.33
17-46
Figure B17.1 The biosynthesis of isoleucine from threonine.
Figure B17.2
The effect of inhibitor binding on the shape of an active site.
17-47
Figure B17.3 Liquid ammonia used as fertilizer.
17-48
Table B17.1 Effect of Temperature on Kc for Ammonia Synthesis
T (K) Kc
17-49
Figure B17.4 Percent yield of ammonia vs. temperature (oC) at
five different operating pressures.
17-50
Figure B17.5
17-51