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17-1
17-2
Figure 17.1
17-4
2NO2(g)
2
eq
2
kfwd
[NO
]
2 eq
=
then
krev
[N2O4]eq
17-5
Figure 17.2
small K
The reaction mixture
contains mostly
reactants.
large K
The reaction mixture
contains mostly
products.
17-7
intermediate K
Figure 17.3
17-9
Table 17.1
Initial
Expt
[N2O4]
[NO2]
Equilibrium
Q, [NO2]2
[N2O4]eq
[NO2]eq
[N2O4]
K, [NO2] 2eq
[N2O4]eq
0.1000
0.0000
0.0000
0.0357
0.193
10.4
0.0000
0.1000
0.000924
0.0982
10.4
0.0500
0.0500
0.0500
0.00204
0.146
10.4
0.0750
0.0250
0.0833
0.00275
0.170
10.5
17-10
PROBLEM: Write the reaction quotient, Qc, for each of the following
reactions:
(a) The decomposition of dinitrogen pentaoxide,
(b) The combustion of propane,
PLAN: We balance the equations and then construct the reaction
quotient.
SOLUTION:
(a)
(b)
17-11
Qc =
[NO2]4[O2]
[N2O5]2
Qc =
[CO2]3[H2O]4
[C3H8][O2]5
Forms of K and Q
For an overall reaction that is the sum of two more
individual reactions:
Qoverall = Q1 x Q2 x Q3 x .. and
Koverall = K1 x K2 x K3 x
The form of Q and K depend on the direction in which the
balanced equation is written:
Qc(rev) =
17-12
1
Qc(fwd)
Kc(rev) =
1
Kc(fwd)
Forms of K and Q
If the coefficients of a balanced equation are multiplied by
a common factor,
c
d
[C]
[D]
Q' = Qn = [A]a[B]b
17-13
and K' = Kn
(a) Show that the overall Qc for this reaction sequence is the same as
the product of the Qc's of the individual reactions.
(b) Given that both reactions occur at the same temperature, find Kc
for the overall reaction.
PLAN: We first write the overall reaction by adding the individual
reactions and then write the overall Qc. Then we write the Qc for
each step. We add the steps and multiply their Qc's, canceling
common terms. We can then calculate the overall Kc.
17-14
Qc(overall) =
[NO2]2
[N2][O2]2
[NO]2
Qc1 =
[N2][O2]
[NO2]2
Qc2 =
[NO2]2
[NO]2[O2]
[NO2]2
[NO]
=
Qc1 x Qc2 =
x
[N2][O2]
[N2] [O2] 2
[NO]2[O2]
2
(b)
17-15
= 2.8x10-15
(b)
17-16
17-17
= 20
Figure 17.4
17-19
Table 17.2
17-20
Qp =
P NO2
P 2NO x PO
Qc =
[NO2]2
[NO]2 [O2]
Kp = Kc (RT)n(gas)
If the amount (mol) of gas does not change in the reaction,
ngas = 0 and Kp = Kc.
17-21
17-22
17-23
Figure 17.5
Q>K
Q<K
17-24
Q=K
17-25
17-26
(0.55)2
(0.12)
= 2.5
17-27
17-28
Initial
Change
Equilibrium
CO2(g) +
2CO(g)
C(graphite)
2CO(g)
0.458
-x
+2x
0.458 -x
2x
17-29
17-30
2
PCO
2(eq)
PCO(eq)
2
= 0.598
0.159
= 2.25
17-31
Calculating [HI]:
0.200 mol
2.00 L
= 0.100 M
2HI(g)
H2(g) +
I2(g)
Initial
0.100
- 2x
+x
+x
0.100 - x
Change
Equilibrium
17-32
[H2] [I2]
[HI]
(0.011)(0.011)
(0.078)
= 0.020 = Kc
PLAN: First we write the balanced equation and the expression for Qc.
We calculate the equilibrium concentrations from the given
numbers of moles and the flask volume. We then use the value
of Kc to solve for [H2O].
SOLUTION:
CH4(g) + H2O(g)
CO(g) + 3H2(g)
0.041 mol
0.26 mol
[CH4]eq =
= 0.13 M
[CO]eq =
= 0.81 M
0.32 L
0.32 L
0.091 mol
[H2]eq =
= 0.28 M
0.32 L
17-33
[H2O] =
17-34
[CO][H2]3
[CH4][H2O]
[CO][H2]3
[CH4] Kc
(0.81)(0.28)3
(0.13)(0.26)
= 0.53 M
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.
PLAN: We have to find the concentrations of all species at equilibrium
and then substitute into a Kc expression. First we write a
balanced equation, calculate initial concentrations and set up a
reaction table.
SOLUTION:
CO(g) + H2O(g)
CO2(g) + H2(g)
0.250 mol
Calculating initial concentrations,[CO] = [H2O] =
0.125 L
17-35
= 2.00 M
CO(g) + H2O(g)
2.00
2.00
-x
-x
+x
+x
2.00 - x
2.00 - x
Change
Equilibrium
Qc = K c =
=
(x)(x)
[CO2][H2]
=
[CO][H2O]
(2.00 - x) (2.00 - x)
x
2.00-x
= 1.25
17-36
CO2(g) + H2(g)
x = 1.11 M
(x)2
=
(2.00 - x)2
2.00 - x = 0.89 M
17-37
COCl2 (g)
Initial
0.500
Change
Equilibrium
Kc =
17-38
[CO][Cl2]
[COCl2]
-x
0.500 - x
x2
=
= 8.3x10-4
0.500 - x
CO(g) + Cl2(g)
0
+x
+x
x2 (8.3x10-4)(0.500)
so x 2.0x10-2
17-39
17-40
17-41
17-42
17-43
= 4.00 M
[CS2][H2]4
[CH4][H2S]
(4.0)(8.0)4
(4.0)(8.0)
= 64
Since Qc > Kc, the reaction will proceed to the left. The reactant
concentrations will decrease and the product concentrations will
increase.
17-44
CH4(g) + 2H2S(g)
CS2(g) + 4H2(g)
Initial
4.00
8.00
4.00
8.00
Change
+x
+2x
-x
-4x
Equilibrium
4.00 + x
8.00 + 2x
4.00 -x
8.00 - 4x
17-45
Figure 17.6
17-46
Figure 17.6
continued
SOLVING FOR x AND EQUILIBRIUM
QUANTITIES
17-47
Le Chteliers Principle
When a chemical system at equilibrium is disturbed, it
reattains equilibrium by undergoing a net reaction that
reduces the effect of the disturbance.
A system is disturbed when a change in conditions forces
it temporarily out of equilibrium.
The system responds to a disturbance by a shift in the
equilibrium position.
A shift to the left is a net reaction from product to reactant.
A shift to the right is a net reaction from reactant to product.
17-48
17-49
Figure 17.7
17-50
PCl3(g) +
0.200
Disturbance
New initial
Change
New equilibrium
17-51
0.125
PCl3(g)
0.600
+0.075
0.200
0.200
0.600
-x
-x
+x
0.200 - x
0.200 - x
0.600 + x
(0.637)*
Cl2(g)
Figure 17.8
PCl3(g) + Cl2(g)
PCl5(g)
17-52
17-53
2
Qc = [H2O]
[H2S]2[O2]
17-54
Figure 17.9
17-56
SF6(g)
2ICl(g)
17-57
17-58
17-59
Temperature and K
The only factor that affects the value of K for a given
equilibrium system is temperature.
For a reaction with Hrxn > 0, an increase in temperature
will cause K to increase.
For a reaction with Hrxn < 0, an increase in temperature
will cause K to decrease.
The vant Hoff equation shows this relationship:
ln
17-60
K2
K1
o
H
rxn
= R
1
T2
1
T1
R = 8.314 J/molK
K1 is the equilibrium constant at T1
17-61
CaO(s) + CO2(g)
S(s) + O2(g)
17-62
17-63
17-64
Molecular
PROBLEM: For the reaction
X(g) + Scenes
Y2(g)
XY(g) + Y(g) H > 0
the following molecular scenes depict different reaction
mixtures. (X = green, Y = purple):
17-65
5x3
= 15
1x1
For scene 3: Qc =
17-66
[XY][Y]
[X][Y2]
For scene 2: Qc =
3x1
=
3x3
4x2
=2
2x2
Q = 15
Q = 2.0
Q = 0.33
17-67
17-68
2NH3(g)
Hrxn = -91.8 kJ
T (K)
Kc
200.
7.17x1015
300.
2.69x108
400.
3.94x104
500.
1.72x102
600.
4.53x100
700.
2.96x10-1
800.
3.96x10-2
17-69
17-70
At very high P and low T (top left), the yield is high, but the
rate is low. Industrial conditions (circle) are between 200 and
300 atm at about 400C.
17-71
Chemical Connections
Figure B17.1 The biosynthesis of isoleucine from threonine.
17-72
Chemical Connections
Figure B17.2
17-73