Chemistry 143

Chapter 14
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 th
an one phase
14.5 When K is large, the position of equilibrium lies toward the prod
ucts
14.6 Le Chateliers principle tells us how a chemical equilibrium res
ponds when disturbed.
14.7 Equilibrium concentrations can be used to predict equilibrium co
nstants, and vice versa
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
Equilibrium - What Does it Mean?

As quickly as product is being made, some is also
consumed to form reactants
The process is continually occurring, but the
amounts present stop changing
For the reaction N2O4 2NO2
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
become equal
Mass Action Expression

Called the reaction quotient (Q) at any time, and the
equilibrium law, K only when the reaction is known
to be at equilibrium
Stoichiometric coefficients are the exponent for each
substance
If Q K, system is not at equilibrium
aA + bB cC + dD
c
d
[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)
2CO(g) + O2(g) 2 CO2(g)
N2 + 3H2(g) 2NH3(g)
Q
Q
[N 2 O 4 ]
[NO 2 ]2
[CO 2 ]2
[CO]2 [O 2 ]
[NH3 ]2
[N 2 ][H 2 ]3
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(NH3 ) 4 2+ ]
2+
[Cu ][NH 3 ]
B.
[Cu(NH3 ) 4 2+ ]
C.
[Cu 2+ ][NH 3 ]4
2+
[Cu ][NH 3 ]
2+
[Cu(NH3 ) 4 ]
Q
Q
Q
D. None of these
The Equilibrium Constant, K

For a chemical equilibrium to exist in a reaction
mixture, the reaction quotient, Q, must be euqatl
to the equilibrium constant, K
Symbolized Kc when concentrations for all
substances in M are substituted into the mass
action expression
Changes with temperature
Is a numeric value, specific to the reaction and the
specified states
Equilibrium Constants and Their Reactions

When we multiply an equation by a constant, the
value of the equilibrium constant for the new
equation is raised to the exponent of the multiplier
n* Rxn Kn
When we reverse an equation, the value of K for
the new equation is its inverse (1/K)
When we add reactions, we multiply their K
values for the net 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
11
The Equilibrium Constant, Kp

Based on reactions in which the substances are
gaseous
Assumes gas quantities are expressed in
atmospheres in the mass action expression
Compare Kc to KP
Kc
NH3
N2 H2
KP
2
PNH
3
PN 2 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
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 K c (RT )
Kp
(RT )
Kc
11.7 = Kc
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.
B.
C.
D.
E.
0.99
2.0
24
2400
None of these
15
Heterogeneous Equilibria
Involve more than one state of matter

Solutions are expressed in M
Gases are expressed in M
Governed by Kc
Solids and liquids are replaced with 1 in the mass action expression
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 PO 4 ]
Q
[H3 PO 4 ]
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 ]
18
Your Turn
Given the reaction:
3Ca2+(aq) + 2PO43-(aq) Ca3(PO4)2(s)
what is mass action expression for the reverse
reaction?
[Ca 2+ ]3 [PO43 ]2
A.
[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 ]
19
The Significance of K Values

If K is large, the reaction is efficient (makes
product effectively)
If K is small, the reaction is inefficient (makes
little product)
If 10-3 < K < 103, the reaction has much of both
product and reactant present
At equilibrium, the Q = K
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?
Since K is small, this is a reactant favored reaction,
although significant amounts of both reactant and
product are present
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
22
Equilibrium Positions
Equilibrium positions are a combination of
concentrations that allow Q = K
There are an infinite number of possible
equilibrium positions
14.6 Le Chateliers principle tells us how a chemical equilibrium responds when

disturbed.
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)

disturbed.
24
Factors Affecting Quantities Present at

Equilibrium
Concentration affects the value of Q, and helps
predict the reaction progress
Pressure and volume of gases both affect the value
of Q and predict the reaction progress
P n/V, hence increasing gas pressure increases
molarity
M = n/V, hence increasing volume decreases the
molarity of a gas

disturbed.
25
Temperature Affects the Value of K

Endothermic reactions increase K with increasing
temperature
Exothermic reactions decrease K with increasing
temperature
Shift effects may be predicted using heat as a
variable in the mass action expression

disturbed.
26
An Approach to Using Le Chteliers Principle

Write the mass action expression for the reaction
Examine the relationship between the affected
concentration and Q (direct or indirect)
Compare Q to K
If the change causes Q > K, reaction shifts left
If the change causes Q < K, reaction shifts right
If the change has no effect on Q - no shift expected

disturbed.
27
Learning Check
Cu(H2O)62+(aq) + 4NH3(aq) [Cu(NH3)42+](aq) + 6H2O(l)
What is expected if:
Initially, Q = K
[NH3] is inverse to Q
NH3(aq) is added
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+ NH 3
Initially, Q = K
[Cu2+] is inverse to Q
increasing [Cu2+] decreases Q
Q < K shifts right

disturbed.
28
Learning Check
In the reaction: N2(g) + 3H2(g) 2NH3(g) What will
happen if pressure is increased?
2
NH3
Q
3
N2 H2
Increasing pressure affects all gases
There are more moles of gas on reactant side, hence

effect is larger
Increasing pressure of product decreases Q
Q < K shifts right

disturbed.
29
Learning Check: More Shift Predictions

In the reaction:
H3PO4(aq) + 3OH-(aq) 3H2O(l) + PO43-(aq)
What will happen if PO43- is removed?
Q is proportional to the [PO43-]
Decreasing [PO43-] decreases Q
Q < K shifts right
Q
PO4
OH
H3 PO 4

disturbed.
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
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.
disturbed.
32
Learning Check
[PO 43- ] heat

[OH - ]3 [H 3 PO 4 ]
The reaction
H3PO4(aq) + 3OH-(aq) 3H2O(l) + PO43-(aq) is
exothermic. What will happen if the system is cooled?
Since the reaction is exothermic, heat is a product
Heat is directly proportional to Q
Decreasing the temperature appears to decrease Q
Q < K (actually because K increased) shifts to the right

disturbed.
33
Catalysts and Equilibrium

The catalyst lowers
the Ea for both the
forward and reverse
reaction.
The change in Ea
affects the kr and kf
equally
Catalysts have no
effect on equilibrium

disturbed.
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)
It is noted that heating a pink sample cause it to turn

violet.
Is the reaction:
A. Endothermic
B. Exothermic
C. Cannot tell from the given information
disturbed.
35
Determining Kc From Equilibrium

Concentrations
When all concentrations at equilibrium are known, use
the mass action expression to find Kc
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?
2
0.21
H3O HC 2 O 4
Kc
Kc = 5.58 10-2
Q
0.79
H 2 C2 O 4
14.7 Equilibrium concentrations can be used to predict equilibrium constants, and vice
versa
36
Determining Equilibrium Concentrations from Kc

When all concentrations but one are known, use the
mass action expression to relate the concentrations to
Kc
Learning Check
In the reaction N2(g) + O2(g) 2NO(g), Kc = 4.8 10-31 If
the concentrations of N2 and NO are both 2 M, what is the
concentration of O2 at equilibrium?
NO
Kc
N 2 O2
2
2
2
4.8 1031
2 O 2
[O2] = 4.2 1030 M
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
versa
38
Determining Equilibrium Concentrations from

Kc When Initial Concentrations are Given
Write the mass action expression
Using concentrations present, compare Q vs K to
predict shift direction
Set up ICE (Initial, Change, Equilibrium) table
Allow reaction to proceed as expected, using x to
represent the quantity
Substitute equilibrium terms from table into mass action
expression and solve
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?
I (M) 2.0
C (M) -x
E (M) 2.0 - x
5.0
Q
2.0 2.0
2
6.25
Q K shifts right
2 .0
-x
2.0 - x
5.0 2x
10, 000
2
2.0-x
2D
5.0
Q
B A
+ 2x
5.0 + 2x
2
x = 1.91
[A] = [B] = 0.09 M
[D] = 8.82 M
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
versa
41
Simplifications: Dropping the x Term in

Binomials
In a mass action expression we sometimes get very
complicated mathematical problems
If the equilibrium constant is small, the change to
reach equilibrium (x term) is also small
In binomial terms, compare the constant to the value
of K: if the constant is > 400K, then the x term may
be dropped
Use a proof to show that the dropped x term was
sufficiently small
dropped x term ?
0.05
(2-x) x = K
constant of binomial
versa
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 10
16
0.2
x = 1.4 10-17
[B] = 1.4 10-17 M
proof: is 1.4 10-17/0.2 < 0.05?
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.
B.
C.
D.
0.3 M
0.002 M
0.04 M
0.5 M
versa
44

Chemistry 143

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Chemistry 143

Uploaded by

Copyright:

Available Formats

Chapter 14

Chemical Equilibrium: General

Equilibrium - What Does it Mean?

Mass Action Expression

2CO(g) + O2(g) 2 CO2(g)

The Equilibrium Constant, K

Equilibrium Constants and Their Reactions

The Equilibrium Constant, Kp

Involve more than one state of matter

The Significance of K Values

14.6 Le Chateliers principle tells us how a chemical equilibrium responds when

14.6 Le Chateliers principle tells us how a chemical equilibrium responds when

Factors Affecting Quantities Present at

14.6 Le Chateliers principle tells us how a chemical equilibrium responds when

Temperature Affects the Value of K

14.6 Le Chateliers principle tells us how a chemical equilibrium responds when

An Approach to Using Le Chteliers Principle

14.6 Le Chateliers principle tells us how a chemical equilibrium responds when

increasing [NH3] decreases Q

14.6 Le Chateliers principle tells us how a chemical equilibrium responds when

Increasing pressure affects all gases

There are more moles of gas on reactant side, hence

Increasing pressure of product decreases Q

Q < K shifts right

Learning Check: More Shift Predictions

14.6 Le Chateliers principle tells us how a chemical equilibrium responds when

[PO 43- ] heat

Since the reaction is exothermic, heat is a product

Heat is directly proportional to Q

Decreasing the temperature appears to decrease Q

Q < K (actually because K increased) shifts to the right

Catalysts and Equilibrium

14.6 Le Chateliers principle tells us how a chemical equilibrium responds when

It is noted that heating a pink sample cause it to turn

Determining Kc From Equilibrium

Determining Equilibrium Concentrations from Kc

[O2] = 4.2 1030 M

Determining Equilibrium Concentrations from

Simplifications: Dropping the x Term in

You might also like