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Chemical Equilibrium: General Concepts: Brady and Senese, 5th Edition
Chemical Equilibrium: General Concepts: Brady and Senese, 5th Edition
Index
14.1 Dynamic equilibrium is achieved when the rates of forward and
reverse processes become equal
14.2 A law relating equilibrium concentrations can be derived from
the balanced chemical equation for a reaction
14.3 Equilibrium laws for gaseous reactions can be written in terms of
either concentrations or pressures
14.4 Heterogeneous equilibria involve reaction mixtures with more
than one phase
14.5 When K is large, the position of equilibrium lies toward the
products
14.6 Le Chateliers principle tells us how a chemical equilibrium
responds when disturbed.
14.7 Equilibrium concentrations can be used to predict equilibrium
constants, and vice versa
2
Dynamic Equilibrium
Many reactions are reversible: this is to say that when
the reaction appears to be complete, amounts of both
reactant and product exist.
We show reversible reactions using a double arrow
or
The forward reaction is read left to right, while the
reverse reaction is read right to left.
HC2H3O2(aq) + H2O(l) H3O+(aq) + C2H3O2-(aq)
14.1 Dynamic equilibrium is achieved when the rates of forward and reverse processes
become equal
14.1 Dynamic equilibrium is achieved when the rates of forward and reverse processes
become equal
In a Closed System
The overall quantities are fixed
Whether we started with all reactant or all product,
we will always have the same composition at
equilibrium under the same conditions
14.1 Dynamic equilibrium is achieved when the rates of forward and reverse processes
become equal
[C] [D]
[A]a [B]b
14.2 A law relating equilibrium concentrations can be derived from the balanced
chemical equation for a reaction
Learning Check
Write the mass action expressions for the following:
2NO2(g) N2O4(g)
N2 + 3H2(g) 2NH3(g)
Q
Q
[N 2 O 4 ]
[NO 2 ]2
[CO2 ]2
[CO]2 [O2 ]
[NH3 ]2
[N 2 ][H 2 ]3
14.2 A law relating equilibrium concentrations can be derived from the balanced
chemical equation for a reaction
Your Turn
Which of the following is the correct mass action
expression for the reaction:
Cu2+(aq) + 4NH3(aq) [Cu(NH3)42+](aq)
A.
[Cu(NH 3 ) 4 2+ ]
2+
[Cu ][NH 3 ]
B.
[Cu(NH 3 ) 4 2+ ]
C.
[Cu 2+ ][NH 3 ]4
2+
[Cu ][NH 3 ]
2+
[Cu(NH 3 ) 4 ]
Q
Q
Q
D. None of these
14.2 A law relating equilibrium concentrations can be derived from the balanced
chemical equation for a reaction
14.2 A law relating equilibrium concentrations can be derived from the balanced
chemical equation for a reaction
14.2 A law relating equilibrium concentrations can be derived from the balanced
chemical equation for a reaction
10
Learning Check
For the reaction N2(g) + 3H2(g) 2NH3(g), Kc = 500
for a particular temperature. What would be Kc for
the following:
0.002
2NH3(g) N2(g) + 3H2(g)
N2(g) + 3/2H2(g) NH3(g)
20
14.2 A law relating equilibrium concentrations can be derived from the balanced
chemical equation for a reaction
11
Kc
NH3
N2 H2
KP
2
PNH
3
PN2 PH22
14.3 Equilibrium laws for gaseous reactions can be written in terms of either
concentrations or pressures
12
Kp vs Kc
If PV = nRT, then P/RT = n/V
Substituting P/RT for molar concentration into the mass
action expression, Kc, results in a pressure-based formula
ng = [moles of gas in product] [moles of gas in the
reactant]
R = 0.0821 L atm mol-1 K-1
KP = Kc(RT)n
14.3 Equilibrium laws for gaseous reactions can be written in terms of either
concentrations or pressures
13
Learning Check
Consider the reaction of 2NO2(g) N2O4(g)
If the Kp for the reaction is known to be 0.480 at 25 C,
what is the value of Kc at the same temperature?
K p Kc (RT )n
Kp
(RT )
Kc
11.7 = Kc
14.3 Equilibrium laws for gaseous reactions can be written in terms of either
concentrations or pressures
14
Your Turn
Consider the reaction A(g) + 2B(g) 4C(g) If the Kc
for the reaction is 0.99 at 25 C, what would be the Kp?
A. 0.99
B. 2.0
C. 24
D. 2400
E. None of these
14.3 Equilibrium laws for gaseous reactions can be written in terms of either
concentrations or pressures
15
Heterogeneous Equilibria
14.4 Heterogeneous equilibria involve reaction mixtures with more than one phase
16
Learning Check
Write the mass action expression for the following:
Ag+(aq) + Cl-(aq) AgCl(s)
1
Q
[Ag + ][Cl ]
H3PO4(aq) + H2O(l) H3O+(aq) + H2PO4-(aq)
[H3O][H 2 PO4 ]
Q
[H3PO4 ]
14.4 Heterogeneous equilibria involve reaction mixtures with more than one phase
17
Your Turn!
Given the reaction:
3Ca2+(aq) + 2PO43-(aq) Ca3(PO4)2(s)
what is the mass action expression?
[Ca 2+ ]3 [PO43 ]2
A.
Q
[Ca 3 (PO 4 ) 2 ]
[Ca 2+ ]3 [PO 43 ]2
B.
Q
1
[Ca 3 (PO 4 ) 2 ]
C.
Q
2+ 3
3 2
[Ca ] [PO4 ]
1
D.
Q
2+ 3
3 2
[Ca ] [PO 4 ]
14.4 Heterogeneous equilibria involve reaction mixtures with more than one phase
18
Your Turn
Given the reaction:
3Ca2+(aq) + 2PO43-(aq) Ca3(PO4)2(s)
what is mass action expression for the reverse
reaction?
2+ 3
3 2
A.
[Ca ] [PO4 ]
Q
[Ca 3 (PO 4 ) 2 ]
[Ca 2+ ]3 [PO 43 ]2
B.
Q
1
[Ca 3 (PO 4 ) 2 ]
C.
Q
2+ 3
3 2
[Ca ] [PO4 ]
1
D.
Q
2+ 3
3 2
[Ca ] [PO 4 ]
14.4 Heterogeneous equilibria involve reaction mixtures with more than one phase
19
14.5 When K is large, the position of equilibrium lies toward the products
20
Learning Check
Consider the reaction of 2NO2(g) N2O4(g) if the
Kp for the reaction is known to be 0.480 at 25 C,
does the reaction favor product or reactant at this
temperature?
14.5 When K is large, the position of equilibrium lies toward the products
21
Your Turn!
The following are equilibrium constants for the
reaction of acids in water, Ka. Which is the most
efficient reaction?
A. Ka = 2.2 10-3
B. Ka = 1.8 10-5
C. Ka = 4.0 10-10
D. Ka = 6.3 10-3
14.5 When K is large, the position of equilibrium lies toward the products
22
Equilibrium Positions
Equilibrium positions are a combination of
concentrations that allow Q = K
There are an infinite number of possible
equilibrium positions
23
Equilibrium Shifts
Le Chteliers principle - a system at equilibrium
(Q = K) when upset by a disturbance that causes
(Q K) will shift to offset the stress
A shift to the right is when the forward reaction is
dominant (Q < K)
A shift to the left is when the reverse direction is
dominant (Q > K)
24
25
26
27
Learning Check
Cu(H2O)62+(aq) + 4NH3(aq) [Cu(NH3)42+](aq) + 6H2O(l)
What is expected if:
Initially, Q = K
NH3(aq) is added
[NH3] is inverse to Q
increasing [NH3] decreases Q
Q < K shifts right
Cu2+ is added which forms
Cu(H2O)62+
Cu NH 2+
3 4
Q
Cu(H 2 O)6 2+ NH3 4
Initially, Q = K
[Cu2+] is inverse to Q
increasing [Cu2+] decreases Q
Q < K shifts right
28
Learning Check
In the reaction: N2(g) + 3H2(g) 2NH3(g) What will
happen if pressure is increased?
2
NH 3
Q
3
N 2 H 2
29
PO4
OH
H PO
3 4
30
Your Turn
Consider the reaction Ag+(aq) + Cl-(aq) AgCl(s)
which of following will shift the reaction to the
right?
A. Add HCl(aq)
B. Add AgNO3
C. Remove AgCl
D. Two of these will shift the reaction to the right
E. None of these will shift the reaction to the
right
14.6 Le Chateliers principle tells us how a chemical equilibrium responds when
disturbed.
31
Temperature Effects
The product efficiency of the reaction depends on
the temperature, and whether the reaction is
endothermic or exothermic
Write mass action expression with heat term as if
it were a concentration and predict shifts as before
Figure 14.6 The effect of temperature on the
equilibrium Cu(H2O)42++ 4Cl
CuCl42 + 4H2O.
In the center, an equilibrium mixture of the two
complexes. When the solution is cooled in ice (left),
the equilibrium shifts toward the blue Cu(H2O)42+.
When heated in boiling water (right), the equilibrium
shifts toward CuCl42-. This behavior indicates that the
reaction is endothermic in the forward direction.
14.6 Le Chateliers principle tells us how a chemical equilibrium responds when
disturbed.
32
Learning Check
[PO43- ] heat
[OH- ]3 [H3 PO4 ]
The reaction
H3PO4(aq) + 3OH-(aq) 3H2O(l) + PO43-(aq)
is exothermic. What will happen if the system is
cooled?
33
34
Your Turn
The equilibrium between aqueous cobalt ion and the
chlorine ion is shown:
[Co(H2O)6]2+(pink, aq) + 4Cl-(aq) [Co(Cl)4]2-(blue,aq) + 6H2O(l)
35
Learning Check:
In the reaction
H2C2O4(g) + H2O(l) H3O+(aq) + HC2O4-(aq),
1 mol H2C2O4 is placed into a liter of water. If the
equilibrium concentrations of H3O+(aq) and HC2O4-(aq)
are both 0.21 M, what is value of Kc?
H3O HC2 O 4
Q
H 2 C2 O 4
0.21
Kc
0.79
Kc = 5.58 10-2
14.7 Equilibrium concentrations can be used to predict equilibrium constants, and vice
versa
36
Kc
N2 O2
2
4.8 1031
2O2
14.7 Equilibrium concentrations can be used to predict equilibrium constants, and vice
versa
37
Your Turn!
For the reaction : 2A(aq) + B(aq) 3C(aq), the
equilibrium concentrations are: A = 2.0 M, B = 1.0
M and C = 3.0 M. What is the expected value of Kc
at this temperature?
A. 14
B. 0.15
C. 1.5
D. 6.75
14.7 Equilibrium concentrations can be used to predict equilibrium constants, and vice
versa
38
14.7 Equilibrium concentrations can be used to predict equilibrium constants, and vice
versa
39
Learning Check
For the reaction A + B 2D, K = 10,000, what are the
equilibrium concentrations if we start with 2.0 M A, 2.0 M B,
and 5.0 M D?
A
+
B
2D
2
D
I (M) 2.0
2 .0
5.0
Q
B A
C (M) -x
-x
+ 2x
E (M) 2.0 - x
2.0 - x
5.0 + 2x
5.0
5.0 2x
Q
6.25 10, 000
2.0
2.0
2
Q K shifts right
2.0-x
x = 1.91
14.7 Equilibrium concentrations can be used to predict equilibrium constants, and vice
versa
40
Your Turn
For the reaction shown, Kc = 5.88 10-32
Ag2S(s) + 2H+(aq) 2Ag+(aq) + H2S(aq)
If we start with 2 M AgNO3, and 0.1 M H2S, 2 M
HNO3 , and 25 g of Ag2S in which direction will it
proceed?
A. left because Q < K
B. right because Q < K
C. left because Q > K
D. right because Q > K
14.7 Equilibrium concentrations can be used to predict equilibrium constants, and vice
versa
41
42
Learning Check
For the reaction 2A(g) B(g) given that the Kp = 3.5 10-16
at 25 C, and we place 0.2 atm A into the container, what will
be the pressure of B at equilibrium?
p N 2 O 4
Kp
2
2A
B
p NO
I
C
E
0.2
-2x
0.2 - 2x
0.2
0.2
Q K shifts right
0 atm
+x
x
3.5 1016
0.2 2
x = 1.4 10-17
[B] = 1.4 10-17 M
proof: is 1.4 10-17/0.2 < 0.05?
14.7 Equilibrium concentrations can be used to predict equilibrium constants, and vice
versa
43
Your Turn!
In the reaction shown, K = 1.8 10-5
HC2H3O2(aq) + H2O(l) H3O+(aq) + C2H3O2-(aq)
If we start with 0.3 M HC2H3O2, what will be the
equilibrium concentration of C2H3O2-?
A. 0.3 M
B. 0.002 M
C. 0.04 M
D. 0.5 M
14.7 Equilibrium concentrations can be used to predict equilibrium constants, and vice
versa
44