CHAPTER 17 Chemical Equilibria 1

1
CHAPTER 17
Chemical Equilibrium
2
Chapter Goals
1. Basic Concepts
2. The Equilibrium Constant
3. Variation of K
c
with the Form of the
Balanced Equation
4. The Reaction Quotient
5. Uses of the Equilibrium Constant, K
c
6. Disturbing a System at Equilibrium:
Predictions
7. The Haber Process: A Practical
Application of Equilibrium
3
Chapter Goals
8. Disturbing a System at Equilibrium:
Calculations
9. Partial Pressures and the Equilibrium
Constant
10. Relationship between K
p
and K
c
11. Heterogeneous Equilibria
12. Relationship between AG
o
rxn
and the
Equilibrium Constant
13. Evaluation of Equilibrium Constants at
Different Temperatures
4
1. To explain how chemical equilibrium can be achieved when the
rates of two opposing processes are equal.
2. To derive an equilibrium law from a balanced chemical reaction for
a reversible reaction.
3. To explain the significance of equilibrium constant, to relate K
c
to K
p

and its use in equilibrium calculation.
4. To differentiate between homogeneous equilibria and
heterogeneous equilibria.
5. To explain the various factors that can affect chemical equilibria.
6. To explain Arrhenius, Browsted Lowry and Lewis concept of acid
and base and give examples.
7. To identify conjugate acid and base pairs in a Browsted-Lowry acid-
base pair reaction.
8. To show how the strengths of Browsted acids and bases follow
periodic trends.
9. To explain the characteristic of an amphoteric substance.
10. Define pH, pOH and water dissociation constant, K
w

11.To learn how to use pH scale to measure strength of acids and
bases and to differentiate between strong and weak acids or bases.
12. To explain what is a buffer and how buffers enable control of pH
in solutions.
LO
5
Basic Concepts
Reversible reactions do not go to completion.
Chemical reaction that can occur in either direction
Symbolically, this is represented as:

( ) ( ) ( ) ( )
g g g g
D d + C c B b + A a
6
Basic Concepts
Chemical equilibrium exists when two
opposing reactions occur simultaneously
at the same rate.
A chemical equilibrium is a reversible reaction
that the forward reaction rate is equal to the
reverse reaction rate.
Chemical equilibria are dynamic equilibria.
Molecules are continually reacting, even
though the overall composition of the reaction
mixture does not change.
7
Basic Concepts
One example of a dynamic equilibrium can
be shown using radioactive
131
I as a tracer
in a saturated PbI
2
solution.
{ }
{ }
solution. into go will iodine e radioactiv the of Some
solution. filter the then minutes, few a for Stir 2
I 2 Pb PbI
solution. PbI saturated a in PbI solid Place 1
-
(aq)
2
(aq)
O H
2(s)
2
*
2
2
+

+
8
Basic Concepts
This movie depicts a dynamic equilibrium.
9
Basic Concepts
Graphically, this is a representation of the
rates for the forward and reverse reactions
for this general reaction.
( ) ( ) ( ) ( )
g g g g
D d + C c B b + A a
10
Basic Concepts
One of the fundamental ideas of chemical
equilibrium is that equilibrium can be
established from either the forward or
reverse direction.
11
Basic Concepts
12
Basic Concepts
13
The Equilibrium Constant
For a simple one-step mechanism reversible
reaction such as:
The rates of the forward and reverse reactions
can be represented as:
| || |
| || | rate. reverse the represents which D C k Rate
rate. forward the represents which B A k Rate
r r
f f
=
=
+
+
(g) (g) (g) (g)
D C B A
14
When system is at equilibrium:
Rate
f
= Rate
r

| || | | || |
| || |
| || | B A
D C
k
k
to rearranges which
D C k B A k
: give to ip relationsh rate for the Substitute
r
f
r f
=
=
15
Because the ratio of two constants is a
constant we can define a new constant as
follows :
| || |
| || |
k
k
K and
K
C D
A B
f
r
c
c
=
=
16
Similarly, for the general reaction:
we can define a constant

| | | |
| | | |
reactions. all for valid is expression This
B A
D C
K
products
reactants
b a
d c
c
=
+
+ D d C c B b A a
(g) (g) (g) (g)
17
Kc is the equilibrium constant .
Kc is defined for a reversible reaction at a
given temperature as the product of the
equilibrium concentrations (in M) of the
products, each raised to a power equal to
its stoichiometric coefficient in the
balanced equation, divided by the product
of the equilibrium concentrations (in M) of
the reactants, each raised to a power
equal to its stoichiometric coefficient in the
balanced equation.
18
Example 17-1: Write equilibrium constant
expressions for the following reactions at
500
o
C. All reactants and products are
gases at 500
o
C.
| || |
| |
5
2 3
c
2 3 5
PCl
Cl PCl
K
Cl PCl PCl
=
+
19
You do it!
HI 2 I + H
2 2
20
| |
| || |
2 2
2
c
2 2
I H
HI
K
HI 2 I + H
=
21
You do it!
O H 6 + NO 4 O 5 + NH 4
2 2 3
22
| | | |
| | | |
5
2
4
3
6
2
4
c
2 2 3
O NH
O H NO
= K
O H 6 + NO 4 O 5 + NH 4
23
Equilibrium constants are dimensionless
because they actually involve a
thermodynamic quantity called activity.
Activities are directly related to molarity
24
Example 17-2: One liter of equilibrium mixture from the
following system at a high temperature was found to
contain 0.172 mole of phosphorus trichloride, 0.086 mole
of chlorine, and 0.028 mole of phosphorus pentachloride.
Calculate K
c
for the reaction.
Equil []s 0.028 M 0.172 M 0.086 M
You do it!

+
2 3 5
Cl PCl PCl
25
| || |
| |
( )( )
( )
53 . 0 K
028 . 0
086 . 0 172 . 0
K
PCl
Cl PCl
K
c
c
5
2 3
c
=
=
=
26
Example 17-3: The decomposition of PCl
5

was studied at another temperature. One
mole of PCl
5
was introduced into an
evacuated 1.00 liter container. The
system was allowed to reach equilibrium
at the new temperature. At equilibrium
0.60 mole of PCl
3
was present in the
container. Calculate the equilibrium
constant at this temperature.
27
( ) ( ) ( )
0 0 1.00 Initial
Cl PCl PCl
g 2 g 3 g 5
M
+
28
( ) ( ) ( )
M M M
M
0.60 + 0.60 + 0.60 - Change
0 0 1.00 Initial
Cl PCl PCl
g 2 g 3 g 5
+
29
( ) ( ) ( )
M M M
M M M
M
0.60 0.60 0.40 m Equilibriu
0.60 + 0.60 + 0.60 - Change
0 0 1.00 Initial
Cl PCl PCl
g 2 g 3 g 5
+

30
( ) ( ) ( )
( )( )
( )
T another at 90 . 0
40 . 0
60 . 0 60 . 0
K
0.60 + 0.60 + 0.60 - Change
0 0 1.00 Initial
Cl PCl PCl
'
c
g 2 g 3 g 5
= =
+
M M M
M M M
M
31
Example 17-4: At a given temperature
0.80 mole of N
2
and 0.90 mole of H
2
were
placed in an evacuated 1.00-liter
container. At equilibrium 0.20 mole of NH
3

was present. Calculate K
c
for the reaction.
You do it!
32
| |
| || |
( )
( )( )
26 . 0
60 . 0 70 . 0
20 . 0
H N
NH
K
0.20 + 0.30 - 0.10 - Change
0 0.90 0.80 Initial
NH 2 H 3 + N
3
2
3
2 2
2
3
c
3(g) 2(g) 2(g)
= = =
M M M
M M M
M M
33
Variation of K
c
with the
Form of the Balanced Equation
The value of K
c
depends upon how the balanced
equation is written.
From example 17-2 we have this reaction:
This reaction has a K
c
=[PCl
3
][Cl
2
]/[PCl
5
]=0.53
+
2 3 5
Cl PCl PCl
34
Variation of K
c
with the
Example 17-5: Calculate the equilibrium constant
for the reverse reaction by two methods, i.e, the
equilibrium constant for this reaction.
Equil. []s 0.172 M 0.086 M 0.028 M
The concentrations are from Example 17-2.
+
5 2 3
PCl Cl PCl
35
Variation of K
c
with the
| |
| || |
K
PCl
PCl Cl
c
'
5
3 2
=
36
Variation of K
c
with the
| |
| || |
( )
( )( )
K
PCl
PCl Cl
c
'
5
3 2
= = =
0 028
0172 0 086
19
.
. .
.
37
| |
| || |
( )
( )( )
K
PCl
PCl Cl
K
K
or K
K
c
'
5
3 2
c
c
' c
'
c
= = =
= = = =
0 028
0172 0 086
19
1 1 1
053
19
.
. .
.
.
.
Variation of K
c
with the
Large equilibrium constants indicate that most of
the reactants are converted to products.
Small equilibrium constants indicate that only
small amounts of products are formed.
38
The Reaction Quotient
39
40
The mass action expression or reaction quotient
has the symbol Q.
Q has the same form as Kc
The major difference between Q and Kc is that
the concentrations used in Q are not
necessarily equilibrium values.
| | | |
| | | |
b a
d c
B A
D C
Q
dD + cC bB + aA
: reaction general For this
=
41
Why do we need another equilibrium
constant that does not use equilibrium
concentrations?
Q will help us predict how the equilibrium
will respond to an applied stress.
To make this prediction we compare Q
with K
c
.
42
fractions. as K and Q of think this understand help To
extent. greater a to right the to occurs reaction The K Q
extent. greater a to left the to occurs reaction The K Q
m. equilibriu at is system The K = Q
: When
c
c
c
c
<
>
43
Example 17-6: The equilibrium constant for the
following reaction is 49 at 450
o
C. If 0.22 mole of
I
2
, 0.22 mole of H
2
, and 0.66 mole of HI were put
into an evacuated 1.00-liter container, would the
system be at equilibrium? If not, what must
occur to establish equilibrium?

| |
| || |
( )
( )( )
c
c
2
2 2
2
(g) 2(g) 2(g)
K < Q
49 K but 0 . 9 Q
0 . 9
22 . 0 22 . 0
66 . 0
I H
HI
= Q
0.66 0.22 0.22
HI 2 I H
Q. calculate can We
s. []' m equilibriu y necessaril not are
problem in the given ions concentrat The
= =
= =
+
M M M
44
Uses of the Equilibrium
Constant, K
c
Example 17-7: The equilibrium constant, K
c
, is
3.00 for the following reaction at a given
temperature. If 1.00 mole of SO
2
and 1.00 mole
of NO
2
are put into an evacuated 2.00 L
container and allowed to reach equilibrium, what
will be the concentration of each compound at
equilibrium?
+
+
(g) 3(g) 2(g) 2(g)
NO SO NO SO
45
Constant, K
c
0 0 0.500 0.500 Initial
NO SO NO SO
(g) 3(g) 2(g) 2(g)
M M
+
+
46
M x M x M x M x
M M
+ + - - Change
0 0 0.500 0.500 Initial
NO SO NO SO
(g) 3(g) 2(g) 2(g)
+
+
Constant, K
c
47
( ) ( ) M x M x M x M x
M x M x M x M x
M M
500 . 0 500 . 0 m Equilibriu
+ + - - Change
0 0 0.500 0.500 Initial
NO SO NO SO
(g) 3(g) 2(g) 2(g)

+
+
Constant, K
c
48
Constant, K
c
( ) ( )
| || |
| || |
( )( )
( )( )
equation. the sidesof both of the can take We
. square perfect a is equation This
500 . 0 500 . 0
00 . 3
NO SO
NO SO
K
500 . 0 500 . 0 m Equilibriu
+ + - - Change
0 0 0.500 0.500 Initial
NO SO NO SO
2 2
3
c
(g) 3(g) 2(g) 2(g)
x x
x x
M x M x M x M x
M x M x M x M x
M M

= = =

+
+
49
( ) ( )
| || |
| || |
( )( )
( )( )
| | | |
( ) | | | |
2 2
3
2 2
3
c
(g) 3(g) 2(g) 2(g)
NO SO 184 . 0 500 . 0
NO SO 316 . 0
73 . 2
865 . 0
; 73 . 2 0.865 ; 1.73 - 0.865
500 . 0
= 1.73
sides. both of the can take We
square. perfect a is equation This
500 . 0 500 . 0
00 . 3
NO SO
NO SO
K
500 . 0 500 . 0 m Equilibriu
+ + - - Change
0 0 0.500 0.500 Initial
NO SO NO SO
= = =
= = =
= = =

= = =

+
+
M M x
M x
x x x x
x
x
x x
x x
M x M x M x M x
M x M x M x M x
M M
Constant, K
c
50
Constant, K
c
Example 17-8: The equilibrium constant is
49 for the following reaction at 450
o
C. If
1.00 mole of HI is put into an evacuated
1.00-liter container and allowed to reach
equilibrium, what will be the equilibrium
concentration of each substance?
You do it!
(g) 2(g) 2(g)

HI 2 I + H
51
Constant, K
c
( )
| |
| || |
( )
( )( )
( )
| | | |
| | ( ) M M x
M M x
M x x x x
x
x
x x
x
M x M x M x
M x M x M x
M
78 . 0 2 00 . 1 HI
11 . 0 I H
11 . 0 ; 00 . 1 9 ; 2 00 . 1 0 . 7
2 - 1.00
= 7.0 = K
2 - 1.00
= 49 =
I H
HI
= K
2 - 1.00 m Equilibriu
2 - + + Change
1.00 0 0 Initial
HI 2 I + H
2 2
c
2
2 2
2
c
(g) 2(g) 2(g)
= =
= = =
= = =
52
Disturbing a System at
Equlibrium: Predictions
LeChateliers Principle - If a change of conditions
(stress) is applied to a system in equilibrium, the
system responds in the way that best tends to
reduce the stress in reaching a new state of
equilibrium.
We first encountered LeChateliers Principle in Chapter
14.
Some possible stresses to a system at
equilibrium are:
1. Changes in concentration of reactants or products.
2. Changes in pressure or volume (for gaseous reactions)
3. Changes in temperature.
53
For convenience we may express the amount of
a gas in terms of its partial pressure rather than
its concentration.
To derive this relationship, we must solve the
ideal gas equation.
ion. concentrat its to al proportion directly is
gas a of pressure partial the T, constant at Thus
[]RT = P
mol/L, units the has
V
n
Because
RT
V
n
P
nRT PV
|
.
|
\
|
|
.
|
\
|
=
=
54
1 Changes in Concentration of Reactants and/or Products
Also true for changes in pressure for reactions involving gases.
Look at the following system at equilibrium at 450
o
C.
( )
| |
| || |
49
I H
HI
K
HI 2 I H
2 2
2
c
g 2 2
= =
+
55
o
C.
( )
| |
| || |
side. product or right the shift to will Equilbrium
reaction. forward the favors This
. K < Q added, is H some If
49
I H
HI
K
HI 2 I H
c 2
2 2
2
c
g 2 2
= =
+
56
( )
| |
| || |
side. reactant or left, the shift to will Equilbrium
reaction. reverse the favors This
K > Q , H some remove we If
49
I H
HI
K
HI 2 I H
c 2
2 2
2
c
g 2 2
= =
+
o
C.
57
2 Changes in Volume
(and pressure for reactions involving gases)
Predict what will happen if the volume of this system at
equilibrium is changed by changing the pressure at
constant temperature:
( ) ( )
| |
| |
2
2
4 2
c
g 4 2 g 2
NO
O N
= K
O N NO 2
58
( ) ( )
| |
| |
gas. of moles fewer produces reaction forward The
reaction. forward or the formation product favors This
. K < Q pressure, the increases which decreased, is volume the If
NO
O N
= K
O N NO 2
c
2
2
4 2
c
g 4 2 g 2

59
( ) ( )
| |
| |
produced. are gas of moles More
reaction. reverse or the reactants the favors This
. K > Q pressure, the decreases which increased, is volume the If
NO
O N
= K
O N NO 2
c
2
2
4 2
c
g 4 2 g 2

60
61
3 Changing the Temperature
62
3 Changing the Reaction Temperature
Consider the following reaction at equilibrium:
( ) ( ) ( )
reaction. reactant or reverse the favors This
products. the stresses emperature reaction t the Increasing
reaction this of product a is Heat
kJ 198 + SO 2 O + SO 2
g 3 g 2 g 2

reaction? in this product or reactant a heat Is

kJ/mol 198 H SO 2 O SO 2
o
rxn 3(g) 2(g) 2(g)
= A
+
( ) ( ) ( )
reaction. forward or reactants the favors This
reactants. the stresses emperature reaction t the Decreasing
reaction. this of product a is Heat
kJ 198 + SO 2 O + SO 2
g 3 g 2 g 2

63
Introduction of a Catalyst
Catalysts decrease the activation energy of both the forward and
reverse reaction equally.
Catalysts do not affect the position of equilibrium.
The concentrations of the products and reactants will be the
same whether a catalyst is introduced or not.
Equilibrium will be established faster with a catalyst.
64
Example 17-9: Given the reaction below at
equilibrium in a closed container at 500
o
C. How
would the equilibrium be influenced by the
following?
right NH of ion concentrat the Decrease e.
right H of ion concentrat the Increase d.
right volume the decreasing by pressure the Increasing c.
right emperature reaction t the Decreasing b.
left emperature reaction t the Increasing a.
procedure reaction on Effect Factor
kJ/mol 92 H NH 2 H 3 N
3
2
o
rxn 3(g) 2(g) 2(g)
= A
+
effect no catalyst platinum a g Introducin f.
right NH of ion concentrat the Decrease e.
3
2
o
rxn 3(g) 2(g) 2(g)
= A
+
2
o
rxn 3(g) 2(g) 2(g)
= A
+
o
rxn 3(g) 2(g) 2(g)
= A
+
o
rxn 3(g) 2(g) 2(g)
= A
+
o
rxn 3(g) 2(g) 2(g)
= A
+
o
rxn 3(g) 2(g) 2(g)
= A
+
65
Example 17-10: How will an increase in pressure (caused
by decreasing the volume) affect the equilibrium in each of
the following reactions?
( ) ( ) ( )
( ) ( ) ( )
( ) ( ) ( )
right PCl Cl + PCl c.
left O H 6 + NO 4 O 5 + NH 4 b.
effect no HI 2 I + H a.
m Equilibriu on Effect Reaction
g 5 g 2 g 3
g 2 g 2(g) g 3
g g 2 g 2

( ) ( ) ( )
( ) ( ) ( )
( ) ( ) ( )
( ) ( ) ( )
right O H 2 O H 2 d.
right PCl Cl + PCl c.
left O H 6 + NO 4 O 5 + NH 4 b.
g 2 g 2 g 2
g 5 g 2 g 3
g 2 g 2(g) g 3
g g 2 g 2

( ) ( ) ( )
( ) ( ) ( )
left O H 6 + NO 4 O 5 + NH 4 b.
g 2 g 2(g) g 3
g g 2 g 2

( ) ( ) ( )
g g 2 g 2


66
Example 17-11: How will an increase in
temperature affect each of the following
reactions?
( ) ( ) ( )
left kJ 92 + HCl 2 Cl H b.
left 0 H O N NO 2 a.
g g 2 g 2
o
rxn 4(g) 2 2(g)

+
< A
( ) ( ) ( )
( ) ( ) ( )
right kJ 25 H HI 2 I + H c.
left kJ 92 + HCl 2 Cl H b.
g g 2 g 2
g g 2 g 2
o
rxn 4(g) 2 2(g)
+ = A
+
< A
o
rxn 4(g) 2 2(g)
< A
67
The Haber Process: A Practical
The Haber process is used for the
commercial production of ammonia.
This is an enormous industrial process in the
US and many other countries.
Ammonia is the starting material for fertilizer
production.
Look at Example 17-9. What conditions
did we predict would be most favorable for
the production of ammonia?
68
( ) ( ) ( )
( ) ( )
dilemma. this o solution t s Haber'
res. temperatu low at slow very are kinetics reaction e However th
e. unfavorabl is which 0 < S favorable. also 0 < H favorable. is which 0 < G
atm. 1000 to 200 = N of P and C 450 = T a at run is reaction This
gas. coal from obtained H air. liquid from obtained is N
kJ 22 . 92 H NH 2 H 3 N
2
o
g 2 g 2
o
g 3
oxides metal & Fe
g 2 g 2
A A A
= A +
69
( )
( )
( )
( )
kinetics! with the helps and yield reaction the increases This
removed. is NH because m equilibriu reaches never system reaction The
right. ly to periodical NH Remove 4
right. to N excess Use 3
right. to pressure reaction Increase 2
. decreased is yield but rate, increase to T Increase 1
dilemma. this o solution t s Haber'
3
3
2

70
This diagram illustrates the commercial
system devised for the Haber process.
71
Equilibrium: Calculations
To help with the calculations, we must determine
the direction that the equilibrium will shift by
comparing Q with K
c
.
Example 17-12: An equilibrium mixture from the
following reaction was found to contain 0.20
mol/L of A, 0.30 mol/L of B, and 0.30 mol/L of C.
What is the value of K
c
for

this reaction?
( ) ( ) ( )
+
g g g
C B A
72
( ) ( ) ( )
| || |
| |
( )( )
( )
45 . 0
20 . 0
30 . 0 30 . 0
A
C B
K
0.30 0.30 0.20 s []' Equil.
C B A
c
g g g
= = =
+
M M M
73
If the volume of the reaction vessel were
suddenly doubled while the temperature
remained constant, what would be the new
equilibrium concentrations?
1 Calculate Q, after the volume has been doubled
( ) ( ) ( )
| || |
| |
( )( )
( )
22 . 0
10 . 0
15 . 0 15 . 0
A
C B
= Q
0.15 0.15 0.10 s []' Equil.
C B A
g g g
= =
+
M M M
74
Since Q<K
c
the reaction will shift to the right to
re-establish the equilibrium.
2 Use algebra to represent the new
concentrations.
( ) ( ) ( )
M M M 0.15 0.15 0.10 s []' initial New
C + B A
g g g

75
Since Q<K
c
concentrations.
( ) ( ) ( )
M x M x M x
M M M
+ + - Change
0.15 0.15 0.10 s []' initial New
C + B A
g g g

76
Since Q<K
c
concentrations.
( ) ( ) ( )
( ) ( ) ( )M x M x M x
M x M x M x
M M M
+ 0.15 + 0.15 - 0.10 s []' Equil. New
+ + - Change
0.15 0.15 0.10 s []' initial New
C + B A
g g g

77
Since Q<K
c
concentrations.
( ) ( ) ( )
( ) ( ) ( )
| || |
| |
( )( )
( ) x
x x
M x M x M x
M x M x M x
M M M
+ +
= =
10 . 0
15 . 0 15 . 0
45 . 0
A
C B
= K
+ 0.15 + 0.15 - 0.10 s []' Equil. New
+ + - Change
0.15 0.15 0.10 s []' initial New
C + B A
c
g g g
78
0 0225 . 0 75 . 0
+ 0.30 + 0.0225 = 0.45 - 0.045
equation quadratic this Solve
2
2
= + x x
x x x
79
( ) ( )( )
( )
M x
x
x
0.03 and 78 . 0
2
81 . 0 75 . 0
1 2
0225 . 0 1 4 75 . 0 75 . 0
2a
ac 4 b b -
2
2
=

=

=

=
80
| |
| | | | ( )
disturbed. been has m equilibriu the
after ions concentrat new the are These
18 . 0 15 . 0 C B
07 . 0 ) 10 . 0 ( A
M. 0.03 is value posible only The
answer. an as 0.78 - discard can we 0.10, < < 0 Since
M M x
M M x
x
x
= + = =
= =
=
81
Example 17-13: Refer to example 17-12.
If the initial volume of the reaction vessel
were halved, while the temperature
remains constant, what will the new
equilibrium concentrations be? Recall that
the original concentrations were: [A]=0.20
M, [B]=0.30 M, and [C]=0.30 M.
You do it!
82
( ) ( ) ( )
| || |
| |
( )( )
( )
ions. concentrat m equilibriu the
determine to s expression algebraic the up Set (2)
side. reactant or left the to shifts m equilibriu the thus K Q
90 . 0
40 . 0
60 . 0 60 . 0
A
C B
= Q
halved is volume after the Q, Calculate (1)
0.60 0.60 0.40 s []' ous Instantane
C B A
c
g g g
>
= =
+
M M M
83
( ) ( ) ( )
| || |
| |
0 18 . 0 65 . 1
to reduces equation this completed, is algebra After the
) + 40 . 0 (
) - 60 . 0 )( - 60 . 0 (
45 . 0
A
C B
K
) - 60 . 0 ( ) - 60 . 0 ( ) + 40 . 0 ( Equil. New
- - + Change
0.60 0.60 0.40 s []' initial New
C + B A
2
c
g g g
= +
= = =
x x
x
x x
M x M x M x
M x M x M x
M M M
84
| |
| | | | M M x C B
M M x
x
x
x
48 . 0 ) 60 . 0 (
52 . 0 ) 40 . 0 ( A
answer. possible only the is 0.12 Thus
answer. an as 1.5 discard can we 0.60 < < 0 are limits the Because
0.12 and 1.5
2
42 . 1 65 . 1
) 1 ( 2
) 18 . 0 )( 1 ( 4 ) 65 . 1 ( 65 . 1
. expression for this equation quadratic the Solve
2
= = =
= + =
=
=

=
85
Example 17-14: A 2.00 liter vessel in which the
following system is in equilibrium contains 1.20
moles of COCl
2
, 0.60 moles of CO and 0.20 mole
of Cl
2
. Calculate the equilibrium constant.
You do it!
( ) ( ) ( )
+
g 2 g 2 g
COCl Cl CO
86
( ) ( ) ( )
| |
| || |
( )
( )( )
20
10 . 0 30 . 0
60 . 0
Cl CO
COCl
K
60 . 0 10 . 0 30 . 0 s []' Equil.
COCl Cl + CO
2
2
c
g 2 g 2 g
= = =
M M M
87
An additional 0.80 mole of Cl
2
is added to
the vessel at the same temperature.
Calculate the molar concentrations of CO,
Cl
2
, and COCl
2
when the new equilibrium
is established.
You do it!

88
( ) ( ) ( )
| |
| || |
( )
( )( ) x x
x
M x M x M x
M x M x M x
M M M
M
M M M

+
= = =
50 . 0 30 . 0
60 . 0
20
Cl CO
COCl
K
) + 60 . 0 ( ) - 50 . 0 ( ) - 30 . 0 ( Equil. New
+ - - Change
right shift K < Q 60 . 0 50 . 0 30 . 0 Initial New
40 . 0 + Add (Stress)
60 . 0 10 . 0 30 . 0 Equil. Orig.
COCl Cl + CO
2
2
c
c
g 2 g 2 g
89
| |
| |
| | M M x
M M x
M M x
x
X
x x
78 . 0 ) 60 . 0 ( COCl
32 . 0 ) 50 . 0 ( Cl
12 . 0 ) 30 . 0 ( CO
0.67 discard can we thus 0.30 < < 0 are limits
0.18 & 67 . 0
) 20 ( 2
) 4 . 2 )( 20 ( 4 ) 17 ( 17
0 4 . 2 17 20 to reduces equation
2
2
2
2
= + =
= =
= =
=

=
= +
90
Partial Pressures and the
For gas phase reactions the equilibrium
constants can be expressed in partial pressures
rather than concentrations.
For gases, the pressure is proportional to the
concentration.
We can see this by looking at the ideal gas law.
PV = nRT
P = nRT/V
n/V = M
P= MRT and M = P/RT
91
Consider this system at equilibrium at
500
0
C.
( ) ( ) ( ) ( )
| | | |
| | | |
( ) ( )
( ) ( )
2
O H
2
Cl
O
4
HCl
p
2
2
2
2
2
4
c
g 2 g g 2 g 2
2 2
2
P P
P P
K and
O H Cl
O HCl
K
O + HCl 4 O H 2 + Cl 2
= =
92
( ) ( )
( ) ( )
( ) ( )
( ) ( )
( )
( )
( )
K mol
atm L
0.0821 R use Must
(RT) K = K or (RT) K = K
reaction for this so K K
P P
P P
K
1
c p
1 -
p c
RT
1
p c
4
RT
1
5
RT
1
2
O H
2
Cl
O
4
HCl
2
RT
P
2
RT
P
RT
P
4
RT
P
c
2 2
2
O
2
H
2
Cl
2
O
HCl
=
=
= =
93
Relationship Between K
p
and K
c

From the previous slide we can see that
the relationship between K
p
and K
c
is:
( ) ( )
reactants) gaseous of moles of (# - products) gaseous of moles of (# = n
RT K K or RT K K
n
p c
n
c p
A
= =
A A
94
p
and K
c

Example 17-15: Nitrosyl bromide, NOBr, is
34% dissociated by the following reaction
at 25
o
C, in a vessel in which the total
pressure is 0.25 atmosphere. What is the
value of K
p
?
( ) ( ) ( )
g 2 g g
Br + NO 2 NOBr 2
95
p
and K
c

( ) ( ) ( )
( ) atm 0.17 atm 0.34 atm 34 . 0 - m Equilibriu
atm 0.17 + atm 0.34 + atm 0.34 - Change
0 0 atm [] Initial
Br + NO 2 NOBr 2
g 2 g g
x x x x
x x x
x
96
p
and K
c

( )
ted. undissocia 66% is it
d, dissociate 34% is NOBr Because
atm. 0.21 = thus atm, 1.17 = atm 0.25
atm 0.17 + atm 0.34 atm 34 . 0 - = atm 25 . 0
P P P P
2
Br NO NOBr Tot
x x
x x x x +
+ + =
97
p
and K
c

( )
( )( )
( )( )
( )( )
( ) ( )
( )
( ) ( )
( )
3
2
2
2
NOBr
Br
2
NO
p
Br
NO
NOBr
NOBr
10 3 . 9
14 . 0
036 . 0 071 . 0
P
P P
K
atm 036 . 0 atm 21 . 0 17 . 0 17 . 0 P
atm 071 . 0 atm 21 . 0 34 . 0 34 . 0 P
atm 14 . 0 atm 21 . 0 66 . 0 P
66 . 0 34 . 0 - P
2
2
= = =
= = =
= = =
= =
= =
x
x
x x x
98
p
and K
c
The numerical value of K
c
for this reaction
can be determined from the relationship of
K
p
and K
c
.
( ) ( )
( )( )
| |
K = K RT or K = K RT n =1
K
p c
n
c p
n
c
A A
A

= = 9 3 10 0 0821 298 38 10
3
1
4
. . .
99
p
and K
c
Example 17-16: K
c
is 49 for the following
reaction at 450
o
C. If 1.0 mole of H
2
and 1.0 mole
of I
2
are allowed to reach equilibrium in a 3.0-liter
vessel,
(a) How many moles of I
2
remain unreacted at
equilibrium?
You do it!

( ) ( ) ( )
+
g g 2 g 2
HI 2 I H
100
p
and K
c
( ) ( ) ( )
( ) ( )
| |
| || |
( )
( )
| |
mol 0.21 0.074 L 3.0 I mol ?
51 . 0 2 HI
074 . 0 ) 33 . 0 ( ] [I ] [H
256 . 0 = ; 3 . 2 = 9
- 0.33
2
0 . 7
- 0.33
2
49
I H
HI
= K
2 - 0.33 - 0.33 m Equilibriu
2 + - - Change
0 0.33 0.33 Initial
HI 2 I H
L
mol
2
2 2
2
2
2 2
2
c
g g 2 g 2
= =
= =
= = =
= = =
+
M M x
M M x
M x x
x
x
x
x
M x M x M x
M x M x M x
M M
101
p
and K
c
(b) What are the equilibrium partial
pressures of H
2
, I
2
and HI?
You do it!
102
p
and K
c
( )( )( )
( )( )( ) atm 30 K 723 0.0821 51 . 0 RT P
atm 4.4 K 723 0.0821 0.074 RT P P
K mol
atm L
L
mol
HI
K mol
atm L
L
mol
I H
2 2
= = =
= = = =
M
M
103
p
and K
c
(c) What is the total pressure in the reaction
vessel?
You do it!
104
p
and K
c
( ) atm 39 = atm 30 4 . 4 4 . 4 P P P = P
HI I H Tot
2 2
+ + = + +
105
Heterogeneous Equlibria
Heterogeneous equilibria have more than one
phase present.
For example, a gas and a solid or a liquid and a gas.

How does the equilibrium constant differ for heterogeneous
equilibria?
Pure solids and liquids have activities of unity.
Solvents in very dilute solutions have activities that are essentially
unity.
The Kc and Kp for the reaction shown above are:
2
CO p 2 c
P = K ] [CO = K
( ) ( ) ( )
C 500 at CO CaO CaCO
o
g 2 s s 3
+
106
| |
| |
undefined is K
SO
SO H
= K
p
2
3 2
c
( ) ( ) ( )
( )
You do it!
? K and K of forms the are What
solvent. the is O H
C) 25 at ( SO H O H SO
: reaction For this
p c
2
o
aq 3 2 2 aq 2
+
107
What are K
c
and K
p
for this reaction?
| || |
K = Ca F K is undefined
c
2
2
p
+
( ) ( ) ( )
C) 25 at ( F 2 Ca CaF
o - 1
aq
2
aq s 2
+
+
You do it!
108
What are K
c
and K
p
for this reaction?
| |
| |
( )
( )
K =
H
H O
K
P
P
c
2
2
p
H
H O
2
2
4
4
4
4
=
( ) ( ) ( ) ( )
C) 500 at ( H 4 O Fe O H 4 Fe 3
o
g 2 s 4 3 g 2 s
+
+
109
Relationship Between AG
o
rxn

and the Equilibrium Constant
AG
o
rxn
is the standard free energy change.
AG
o
rxn
is defined for the complete conversion of all reactants to
all products.
AG is the free energy change at nonstandard conditions
For example, concentrations other than 1 M or pressures other
than 1 atm.
AG is related to AG
o
by the following relationship.
quotient reaction = Q
re temperatu absolute = T
constant gas universal = R
Q log RT 303 . 2 G = G
or lnQ RT G = G
o
o
+ A A
+ A A
110
o
rxn

At equilibrium, AG=0 and Q=K
c
.
Then we can derive this relationship:
K log RT 2.303 - = G
or K ln RT - = G
: to rearranges which
K log RT 303 . 2 G 0
or K ln RT G 0
0
0
0
0
A
A
+ A =
+ A =
111
o
rxn

For the following generalized reaction, the
thermodynamic equilibrium constant is
defined as follows:
( ) ( )
( ) ( )
D of activity the is C of activity the is
B of activity the is A of activity the is
where = K
dD + cC bB + aA
D C
B A
b
B
a
A
d
D
c
C
a a
a a
a a
a a
112
o
rxn

The relationships among AG
o
rxn
, K, and the
spontaneity of a reaction are:
AG
o
rxn
K Spontaneity at unit concentration
< 0 > 1 Forward reaction spontaneous
= 0 = 1 System at equilibrium
> 0 < 1 Reverse reaction spontaneous
113
o
rxn
and
the Equilibrium Constant
114
o
rxn

Example 17-17: Calculate the equilibrium
constant, K
p
, for the following reaction at 25
o
C
from thermodynamic data in Appendix K.
Note: this is a gas phase reaction.
( ) ( )
g 2 g 4 2
NO 2 O N
115
o
rxn

( ) ( )
( ) ( )
( ) ( )
eous. nonspontan is reaction This
10 78 . 4 G
78 . 4 G
kJ 82 . 97 kJ 30 . 51 2 G
G G 2 G
G Calculate . 1
NO 2 O N
rxn mol
J
3 o
rxn
rxn mol
kJ
o
rxn
o
rxn
o
O N f
o
NO f
o
rxn
o
rxn
g 2 g 4 2
g 4 2 g 2
= A
= A
= A
A A = A
A
116
o
rxn

( )( )
( )
( )
J! to kJ from G e convert th not to
is mistake common A very
P
P
145 . 0 K
93 . 1
K 298 8.314 -
10 78 . 4
RT
G
K ln
K ln RT G from K Calculate 2.
o
rxn
O N
2
NO
93 . 1
p
K mol
J
mol
J
3 o
rxn
p
p
o
rxn
4 2
2
A
= = =
=
A
=
= A
e
117
o
rxn

K
p
for the reverse reaction at 25
o
C can be
calculated easily, it is the reciprocal of the
above reaction.
( )
( )
2
NO
O N
p
'
p
2
4 2
P
P
90 . 6
145 . 0
1
K
1
K = = = =
kJ/mol 78 . 4 G
O N NO 2
o
rxn
4(g) 2 2(g)
= A

118
o
rxn

Example 17-18: At 25
o
C and 1.00 atmosphere,
K
p
= 4.3 x 10
-13
for the decomposition of NO
2
.
Calculate AG
o
rxn
at 25
o
C.
You do it.
( ) ( ) ( )
+
g 2 g g 2
O NO 2 NO 2
119
o
rxn

rxn mol
kJ
rxn mol
J
4 o
rxn
mol
J
o
rxn
13 -
K mol
J
o
rxn
p
o
rxn
6 . 70 10 06 . 7 G
) 47 . 28 )( 2480 ( G
10 4.3 ln ) K 298 )( 314 . 8 ( G
K ln RT G
= = A
= A
= A
= A
120
o
rxn

The relationship for K at conditions other
than thermodynamic standard state
conditions is derived from this equation.
Q log RT 2.303 G G
or
lnQ RT G G
o
o
+ A = A
+ A = A
121
Evaluation of Equilibrium Constants
at Different Temperatures
From the value of AH
o
and K at one
temperature, T
1
, we can use the vant Hoff
equation to estimate the value of K at
another temperature, T
2
.
|
|
.
|
\
|
A
=
A
=
2 1
o
T
T
1 2
1 2
o
T
T
T
1
T
1
R
H
K
K
ln
or

T T R
) T (T H
K
K
ln
1
2
1
2
122
Example 17-19: For the reaction in
example 17-18, AH
o
= 114 kJ/mol and K
p
=
4.3 x 10
-13
at 25
o
C. Estimate K
p
at 250
o
C.
2 NO
2(g)
2 NO
(g)
+ O
2(g)

123
Evaluation of Equilibrium
Constants at Different
Temperatures

equation Hoff t van' apply the
K 523 T and K 298 T Let
2 1
= =
( )
( )( )( )
795 . 19
K
K
ln
K 298 K 523 314 . 8
298 523 ) 10 14 . 1 (
K
K
ln
equation Hoff t van' apply the
K 523 T and K 298 T Let
1
2
1
2
T
T
K mol
J
mol
J
5
T
T
2 1
=

=
= =
124
( )( )
T. higher at the favored product more is reaction The
C 25 @ 10 3 . 4 K vs C 250 @ 10 7 . 1 K
10 3 . 4 10 0 . 4 K 10 0 . 4 K
K of e known valu the substitute & K for Solve
10 0 . 4
K
K
equation. of sides both of antilog the Take
o 13 -
T
o 4
T
13 - 8
T
8
T
T T
8 80 . 19
T
T
1 2
1 2
1 2
1
2
= =
= =
= =
e
125
Synthesis Question
Mars is a reddish colored planet because it has
numerous iron oxides in its soil. Mars also has
a very thin atmosphere, although it is believed
that quite some time ago its atmosphere was
considerably thicker. The thin atmosphere
does not retain heat well, thus at night on Mars
the surface temperatures are 145 K and in the
daytime the temperature rises to 300 K. Does
Mars get redder in the daytime or at night?
126
Synthesis Question
The formation of iron oxides from iron and
oxygen is an exothermic process. Thus the
equilibrium that is established on Mars shifts to
the iron oxide (red) side when the planet is
cooler - at night. Mars gets redder at night by a
small amount.
127
Group Question
If you are having trouble getting a fire
started in the barbecue grill, a common
response is to blow on the coals until the
fire begins to burn better. However, this
has the side effect of dizziness. This is
because you have disturbed an
equilibrium in your body. What
equilibrium have you affected?
128
End of Chapter 17
This chapter is the key to the
understanding of Chapters 18, 19, & 20.
Make sure you understand this chapters
concepts!

CHAPTER 17 Chemical Equilibria 1

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1

The Equilibrium Constant

(g) 2(g) 2(g)

reaction? in this product or reactant a heat Is

m Equilibriu on Effect Reaction

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