Chapter 17

CHAPTER 17
Chemical Equilibrium
1
Chapter Goals
 Basic Concepts
 The Equilibrium Constant
 Variation of Kc with the Form of the
Balanced Equation
 The Reaction Quotient
 Uses of the Equilibrium Constant, Kc
 Disturbing a System at Equilibrium:
Predictions
 The Haber Process: A Practical
2
Chapter Goals
 Disturbing a System at Equilibrium:
Calculations
 Partial Pressures and the Equilibrium
Constant
 Relationship between Kp and Kc
 Heterogeneous Equilibria
 Relationship between ∆Gorxn and the
Equilibrium Constant
 Evaluation of Equilibrium Constants at
Different Temperatures 3
Basic Concepts
 Reversible reactions do not go to completion.
 They can occur in either direction

Symbolically, this is represented as:
→cC +dD
a A ( g ) + b B( g ) ← ( g) ( g)
4
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.
5
Basic Concepts
 One example of a dynamic equilibrium can
be shown using radioactive 131I as a tracer
in a saturated PbI2 solution.
{1} Place solid PbI*2 in a saturated PbI 2 solution.
H

2O
→ 2+
PbI 2(s) ← Pb (aq) + 2 I -(aq)
{ 2} Stir for a few minutes, then filter the solution.
Some of the radioactive iodine will go into solution.
6
Basic Concepts
 This movie depicts a dynamic equilibrium.
7
Basic Concepts
 Graphically, this is a representation of the
rates for the forward and reverse reactions
for this general reaction.
→c C + d D
a A ( g ) + b B( g ) ← (g) (g)
8
Basic Concepts
 One of the fundamental ideas of chemical
equilibrium is that equilibrium can be
established from either the forward or
reverse direction.
9
Basic Concepts
10
Basic Concepts
11
The Equilibrium Constant
 For a simple one-step mechanism reversible
reaction such as:
A (g) →
+ B(g) ← C (g) + D (g)
 The rates of the forward and reverse reactions
can be represented as:
Rate f = k f [A ][B] which represents the forward rate.
Rate r = k r [C][D ] which represents the reverse rate.
12
 When system is at equilibrium:
Ratef = Rater
Substitute for the rate relationship to give :
k f [ A ][ B] = k r [ C][ D]
which rearranges to
k f [ C][ D]
=
k r [ A ][ B]
13
 Because the ratio of two constants is a
constant we can define a new constant as
follows :
kf
= Kc and
kr
Kc =
[ C][ D]
[ A ][ B]
14
 Similarly, for the general reaction:
a A (g) →
+ b B(g) ← c C (g) + d D (g)
we can define a constant
Kc =
[ C] [ D ]
c d
← products
[ A ] [ B]
a b ← reactants
This expression is valid for all reactions.
15
 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. 16
 Example 17-1: Write equilibrium constant
expressions for the following reactions at
500oC. All reactants and products are
gases at 500oC.
→
PCl 5 ← PCl 3 + Cl 2
Kc =
[ PCl 3 ][ Cl 2 ]
[ PCl5 ] 17
→
H 2 + I 2 ← 2 HI
You do it!
18
→
H 2 + I 2 ← 2 HI
Kc =
[ HI]
2
[ H 2 ][ I 2 ]
19
→
4 NH 3 + 5 O 2 ← 4 NO + 6 H 2 O
You do it!
20
→
4 NH 3 + 5 O 2 ← 4 NO + 6 H 2 O
Kc =
[ NO] [ H 2 O]
4 6
[ NH 3 ] [ O 2 ]
4 5
21
 Equilibrium
constants are dimensionless
because they actually involve a
thermodynamic quantity called activity.
 Activities are directly related to molarity
22
 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 Kc for the reaction.
→
 Equil []’s 0.028 M 0.172 M 0.086 M
You do it!
23
Kc =
[ PCl 3 ][ Cl 2 ]
[ PCl5 ]
Kc =
( 0.172 )( 0.086 )
( 0.028)
K c = 0.53
24
 Example 17-3: The decomposition of PCl5
was studied at another temperature. One
mole of PCl5 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 PCl3 was present in the
container. Calculate the equilibrium
constant at this temperature.
25
PCl 5( g ) →
← PCl 3( g ) + Cl 2( g )
Initial 1.00 M 0 0
26
PCl 5( g ) →
← PCl 3( g ) + Cl 2( g )
Initial 1.00 M 0 0
Change - 0.60 M + 0.60 M + 0.60 M
27
PCl 5( g ) →
← PCl 3( g ) + Cl 2( g )
Initial 1.00 M 0 0
Change - 0.60 M + 0.60 M + 0.60 M
Equilibrium 0.40 M 0.60 M 0.60 M
28
PCl 5( g ) →
← PCl 3( g ) + Cl 2( g )
Initial 1.00 M 0 0
Change - 0.60 M + 0.60 M + 0.60 M
K '
=
( 0.60 )( 0.60 )
= 0.90 at another T
c
( 0.40) 29
 Example 17-4: At a given temperature
0.80 mole of N2 and 0.90 mole of H2 were
placed in an evacuated 1.00-liter
container. At equilibrium 0.20 mole of NH3
was present. Calculate Kc for the reaction.
You do it!
30
N 2(g) →
+ 3 H 2(g) ← 2 NH 3(g)
Initial 0.80 M 0.90 M 0
Change - 0.10 M - 0.30 M + 0.20 M
Kc =
[ NH 3 ]
2
=
( 0.20 )
2
= 0.26
[ N 2 ][ H 2 ] ( 0.70)( 0.60)
3 3
31
Variation of Kc with the
Form of the Balanced Equation
 The value of Kc depends upon how the balanced
equation is written.
 From example 17-2 we have this reaction:
→
 This reaction has a Kc=[PCl3][Cl2]/[PCl5]=0.53
32
 Example 17-5: Calculate the equilibrium constant
for the reverse reaction by two methods, i.e, the
equilibrium constant for this reaction.
→
PCl 3 + Cl 2 ← PCl 5
Equil. []’s 0.172 M 0.086 M 0.028 M
The concentrations are from Example 17-2.
33
'
Kc =
[ PCl5 ]
[ PCl3 ][ Cl2 ]
34
'
Kc =
[ PCl5 ]
=
( 0.028)
= 19
.
[ PCl3 ][ Cl2 ] ( 0172
. )( 0.086)
35
'
Kc =
[ PCl5 ]
=
( 0.028)
= 1.9
[ PCl3 ][ Cl2 ] ( 0.172)( 0.086)
Kc = 1 or K '
= 1 = 1 = 1.9
Kc ' c Kc 0.53
 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.
36
The Reaction Quotient
37
38
 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.
For this general reaction :
→
aA + bB← cC + dD
Q=
[ C] [ D ]
c d
[ A ] [ B]
a b
39
 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 Kc.
40
When :
Q = Kc The system is at equilibrium.
Q > K c The reaction occurs to the left to a greater extent.
Q < K c The reaction occurs to the right to a greater extent.
To help understand this think of Q and K c as fractions.
41
 Example 17-6: The
The concentrat ionsequilibrium
given in theconstant
problemfor the
following reaction is 49 at 450oC. If 0.22 mole of
I2, 0.22are not necessaril
mole of H2, andy 0.66equilibriu
molemof[]'HI
s. were put
We can
into an evacuated calculate
1.00-liter Q.
container, would the
system be H at equilibrium?
+ I → 2 IfHInot, what must
←
2(g) 2(g) (g)
occur to establish equilibrium?
0.22 M 0.22 M 0.66 M
Q=
[ HI]
2
=
( 0.66)
2
= 9.0
[ H 2 ][ I 2 ] ( 0.22)( 0.22)
Q = 9.0 but K c = 49
Q < Kc 42
Uses of the Equilibrium
Constant, Kc
 Example 17-7: The equilibrium constant, Kc, is
3.00 for the following reaction at a given
temperature. If 1.00 mole of SO2 and 1.00 mole
of NO2 are put into an evacuated 2.00 L
container and allowed to reach equilibrium, what
will be the concentration of each compound at
equilibrium?
SO 2(g) + NO 2(g) →
← SO 3(g) + NO (g)
43
Constant, Kc
SO 2(g) + NO 2(g) →
← SO 3(g) + NO (g)
Initial 0.500 M 0.500 M 0 0
44
Constant, Kc
SO 2(g) + NO 2(g) →
← SO 3(g) + NO (g)
Initial 0.500 M 0.500 M 0 0
Change - xM - xM +xM +xM
45
Constant, Kc
SO 2(g) + NO 2(g) →
← SO 3(g) + NO (g)
Initial 0.500 M 0.500 M 0 0
Equilibrium ( 0.500 − x ) M ( 0.500 − x ) M xM xM
46
Constant, Kc
SO 2(g) + NO 2(g) →
← SO 3(g) + NO (g)
Initial 0.500 M 0.500 M 0 0
Kc =
[ SO 3 ][ NO]
= 3.00 =
( x )( x )
[SO 2 ][ NO 2 ] ( 0.500 − x )( 0.500 − x )
This equation is a perfect square.
We can take the of both sidesof the equation.
47
Constant, Kc
SO 2(g) + NO 2(g) →
← SO 3(g) + NO (g)
Initial 0.500 M 0.500 M 0 0
Kc =
[SO 3 ][ NO] = 3.00 = ( x )( x )
[SO 2 ][ NO 2 ] ( 0.500 − x )( 0.500 − x )
This equation is a perfect square.
We can take the of both sides.
x
1.73 =
0.500 − x
0.865 - 1.73 x = x; 0.865 = 2.73 x; x = 0.865
2.73
x = 0.316M = [SO 3 ] = [ NO]
( 0.500 − x ) M = 0.184M = [SO 2 ] = [ NO 2 ] 48
Constant, Kc
 Example 17-8: The equilibrium constant is
49 for the following reaction at 450oC. 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?
→
H 2(g) + I 2(g) ← 2 HI (g)
You do it! 49
Constant, Kc
→ 2 HI
H 2(g) + I 2(g) ← (g)
Initial 0 0 1.00M
Change + x M + xM - 2x M
Equilibrium xM xM (1.00 - 2 x ) M
Kc =
[ HI]
2
= 49 =
(1.00 - 2 x )
2
[ H 2 ][ I 2 ] ( x )( x )
K = 7.0 =
( 1.00 - 2 x )
c
x
7.0 x = 1.00 − 2 x; 9 x = 1.00; x = 0.11 M
[ H 2 ] = [ I 2 ] = xM = 0.11 M
[ HI] = (1.00 − 2 x ) M = 0.78 M 50
Disturbing a System at
Equlibrium: Predictions
 LeChatelier’s 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 LeChatelier’s 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. 51
 For convenience we PVmay express the amount of
= nRT
a gas in terms of its partial pressure rather than
its concentration. P =  RT
 n
  V  we must solve the
To derive this relationship,
n
ideal gas equation.
Because  has the units mol/L,
V
P = []RT
Thus at constant T, the partial pressure of a gas
is directly proportional to its concentration.
52
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 450oC.
→ 2 HI
H 2 + I2 ← ( g)
Kc =
[ HI]
2
= 49
[ H 2 ][ I 2 ]
53
→ 2 HI
H 2 + I2 ← ( g)
Kc =
[ HI]
2
= 49
[ H 2 ][ I 2 ]
If some H 2 is added, Q < K c .
This favors the forward reaction.
Equilbrium will shift to the right or product side.54
→ 2 HI
H 2 + I2 ← (g)
Kc =
[ HI]
2
= 49
[ H 2 ][ I 2 ]
If we remove some H 2 , Q > K c
This favors the reverse reaction.
Equilbrium will shift to the left, or reactant side.
55
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 NO 2( g ) ← N 2 O 4( g )
Kc =
[ N 2O 4 ]
[ NO 2 ] 2
56
→N O
2 NO 2 ( g ) ← 2 4( g )
Kc =
[ N 2O 4 ]
[ NO 2 ] 2
If the volume is decreased, which increases the pressure, Q < K c .
This favors product formation or the forward reaction.
The forward reaction produces fewer moles of gas.
57
→N O
2 NO 2( g ) ← 2 4( g )
Kc =
[ N 2O 4 ]
[ NO 2 ] 2
If the volume is increased, which decreases the pressure, Q > K c .

This favors the reactants or the reverse reaction.
More moles of gas are produced.
58
59
3 Changing the Temperature
60
3 Changing the Reaction Temperature
 Consider the following reaction at equilibrium:
2 SO + + →
←
O →→
← 2 SO∆ =198
−198
) +198 kJ kJ/mol
o
2 SO
2 SO O
2(g) 2 ( g2 () g+ O 2 ( 2g()g←
)2(g) 2 SO
) 23(g) H
SO 3(3g()grxn
+ kJ
Heat
Is heat
Heat isaaproduct
product
aisreactant ofofthis
thisreaction
or product reaction.
in this reaction?
Decreasingthe
Increasing thereaction
reactiontemperature
temperaturestresses
stressesthe
theproducts.
reactants.
This
Thisfavors
favorsthethe reverse oror
reactants reactant
forward reaction.
reaction.
61
 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.
62
 Example 17-9: Given the reaction below at
equilibrium in a closed container at 500oC. How
would the equilibrium be influenced by the
following?
N 2(g) + 3 H 2(g) ← → 2 NH ∆Hooooo = −92 kJ/mol
→ 22 NH
→
← ∆ rxn==
=−−−92
3(g) ∆H rxn = −92 kJ/mol
N 2(g)
2(g) + 3
3 H
H 2(g)
2(g)
2(g) ← 3(g)∆
NH3(g)
3(g)
3(g) ∆HH
Hrxn
rxn
rxn 92 kJ/mol
92kJ/mol
kJ/mol
Factor Effect on reaction procedure
Factor Effect
Effect
Effect on
Effecton reaction
onreaction
on procedure
reactionprocedure
reaction procedure
procedure
a. Increasing the reaction temperature ← left
a. Increasing
Increasing the the reaction
reaction ttemperature
temperature
emperature ←←←left
left
left
b. Decreasing the reaction temperature → right
b. Decreasing the reaction
reaction ttemperature
emperature →→right
right
c. Increasing the pressure by decreasing the volume → right
c. Increasing the pressure by decreasing the volume → right
d. Increase the concentration of H 2 → right
d. Increase the concentration of H 2 → right
e. Decrease the concentration of NH 3 → right
e. Decrease the concentration of NH 3 → right
f. Introducing a platinum catalyst no effect 63
 Example 17-10: How will an increase in pressure (caused
by decreasing the volume) affect the equilibrium in each of
the following reactions?
Reaction
Reaction
Reaction Effect
Effect
Effect
Effect onon
on
on
Effect Equilibriu
Equilibriu
Equilibriu
Equilibriu
on mm
m
Equilibriumm
→
→
→222HI
H222(((ggg))) +++III222((g(gg) ) )←
a. H ←
← HI
HI
( g((gg)( g)) ) nono
noeffect
noeffect
effect
effect
b. →
← →
→444NO ←←
b. 44 NH
NH333( (g(gg) ))+++555OO 2(g) ←
O2(g)
2(g) ← ( g()g( +
NO
NO 6 H 2H
g) )++66H
OO
2 2( gO
)( g()g ) left
←left
left
→→
c. PCl3( g ) + Cl2( g ) ←
c. PCl
3( g )
+ Cl
2( g ) ←PCl PCl5( g )
5( g )
→→ right
right
→2H O
d. 2 H 2( g ) + O 2( g ) ← → right
2 ( g)
64
 Example 17-11: How will an increase in
temperature affect each of the following
reactions?
Reaction
Reaction Effect
Effect onon
Effect Equilibriu
Equilibriu
on m mm
Equilibriu
→
→
→
← ∆ rxn < < ←←
o oo
a. 2 NO2(g) ←
a. 2 NO 2(g)
2(g)←NN OO4(g) ∆∆H
N2 O
22
HH
4(g)
4(g)
0<00
rxn
rxn
leftleft
← left
→
→ 22 HCl
b. H 2( g ) + Cl 22((gg)) ←
← HCl( (gg) ) ++92
92kJ
kJ ←
←left
left
c. H 2( g ) + I 2( g ) → 2 HI ( g ) ∆H = +25 kJ → right
65
The Haber Process: A Practical
Application of Equilibrium
 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?
66
N 2 ( g ) + 3 H 2( g ) ←  → 2 NH 3( g ) ∆H o = −92.22 kJ
Fe & metal oxides
N 2( g ) is obtained from liquid air. H 2( g ) obtained from coal gas.

This reaction is run at a T = 450 o C and P of N 2 = 200 to 1000 atm.
∆G < 0 which is favorable. ∆H < 0 also favorable. ∆S < 0 which is unfavorable.
However the reaction kinetics are very slow at low temperatures.
Haber' s solution to this dilemma.
67
Haber' s solution to this dilemma.
(1) Increase T to increase rate, but yield is decreased.
( 2) Increase reaction pressure to ⇒ right.
( 3) Use excess N 2 to ⇒ right.
( 4) Remove NH 3 periodically to ⇒ right.
The reaction system never reaches equilibrium because NH 3 is removed.
This increases the reaction yield and helps with the kinetics!
68
 This diagramillustrates the commercial
system devised for the Haber process.
69
Equilibrium: Calculations
 To help with the calculations, we must determine
the direction that the equilibrium will shift by
comparing Q with Kc.
 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 Kc for this reaction?
A( g) →
← B( g ) + C ( g )
70
A( g) →
← B( g ) + C ( g )
Equil. []' s 0.20 M 0.30 M 0.30 M
Kc =
[ B][ C] ( 0.30 )( 0.30 )
= = 0.45
[ A] ( 0.20)
71
 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
A( g) →
← B( g ) + C ( g )
Equil. []' s 0.10 M 0.15 M 0.15 M
Q=
[ B][ C] ( 0.15)( 0.15)
= = 0.22
[ A] ( 0.10) 72
 Since Q<Kc the reaction will shift to the right to
re-establish the equilibrium.
2 Use algebra to represent the new
concentrations.
A( g) →
← B( g ) + C ( g )
New initial []' s 0.10 M 0.15 M 0.15 M
73
concentrations.
A( g) →
← B( g ) + C ( g )
New initial []' s 0.10 M 0.15 M 0.15 M
Change -x M +xM +xM
74
concentrations.
A →
← B + C
( g) ( g) ( g)
New initial []' s 0.10 M 0.15M 0.15M
Change - xM + xM + xM
New Equil. []' s ( 0.10 - x ) M ( 0.15 + x ) M ( 0.15 + x ) M
75
concentrations. →
A( g) ← B( g ) + C ( g )
New initial []' s 0.10 M 0.15M 0.15M
Change - xM + xM + xM
New Equil. []' s ( 0.10 - x ) M ( 0.15 + x ) M ( 0.15 + x ) M
Kc =
[ B][ C]
= 0.45 =
( 0.15 + x )( 0.15 + x )
[ A] ( 0.10 − x ) 76
Solve this quadratic equation

2
0.045 - 0.45 x = 0.0225 + 0.30 x + x
x + 0.75 x − 0.0225 = 0
2
77
- b ± b − 4ac
2
x=
2a
− 0.75 ± ( 0.75) − 4(1)( − 0.0225)
2
x=
2(1)
− 0.75 ± 0.81
x= = −0.78 and 0.03 M
2
78
Since 0 < x < 0.10, we can discard - 0.78 as an answer.

The only posible value is x = 0.03 M.
[ A] = (0.10 − x) M = 0.07 M
[ B] = [ C] = ( 0.15 + x ) M = 0.18 M
These are the new concentrations after
the equilibrium has been disturbed.
79
 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!
80
A( g) →
← B( g ) + C ( g )
Instantaneous []' s 0.40 M 0.60 M 0.60 M
(1) Calculate Q, after the volume is halved
Q=
[ B][ C] ( 0.60 )( 0.60 )
= = 0.90
[ A] ( 0.40)
Q > K c thus the equilibrium shifts to the left or reactant side.
(2) Set up the algebraic expressions to determine
the equilibrium concentrations.
81
→
A( g) ← B( g ) + C( g )
New initial []' s 0.40 M 0.60M 0.60M
Change +xM -xM -xM
New Equil. (0.40 + x) M (0.60 - x) M (0.60 - x) M
Kc =
[ B][ C]
= 0.45 =
(0.60 - x)(0.60 - x)
[ A] (0.40 + x)
After the algebra is completed, this equation reduces to
x 2 − 1.65 x + 0.18 = 0
82
Solve the quadratic equation for this expression.
1.65 ± (−1.65) 2 − 4(1)(0.18)
x=
2(1)
1.65 ± 1.42
x= = 1.5 and 0.12
2
Because the limits are 0 < x < 0.60 we can discard 1.5 as an answer.
Thus 0.12 is the only possible answer.
[ A] = (0.40 + x) M = 0.52 M
[ B] = [ C ] = (0.60 − x) M = 0.48 M
83
 Example 17-14: A 2.00 liter vessel in which the
following system is in equilibrium contains 1.20
moles of COCl2, 0.60 moles of CO and 0.20 mole
of Cl2. Calculate the equilibrium constant.
→ COCl
CO ( g ) + Cl 2( g ) ← 2( g )
You do it!
84
→ COCl
CO ( g ) + Cl 2( g ) ← 2( g )
Equil. []' s 0.30 M 0.10 M 0.60 M
Kc =
[ COCl 2 ]
=
( 0.60 )
= 20
[ CO][ Cl 2 ] ( 0.30)( 0.10)
85
 An additional 0.80 mole of Cl2
is added to
the vessel at the same temperature.
Calculate the molar concentrations of CO,
Cl2, and COCl2 when the new equilibrium
is established.
You do it!
86
→
CO ( g ) + Cl 2 ( g ) ← COCl 2 ( g )
Orig. Equil. 0.30 M 0.10 M 0.60 M
(Stress) Add + 0.40 M
New Initial 0.30 M 0.50M 0.60 M Q < K c ∴ shift right
Change -xM -xM +xM
New Equil. (0.30 - x) M (0.50 - x) M (0.60 + x) M
Kc =
[ COCl 2 ]
= 20 =
( 0.60 + x )
[ CO][ Cl 2 ] ( 0.30 − x )( 0.50 − x )
87
equation reduces to 20 x − 17 x + 2.4 = 0
2
17 ± (−17) − 4(20)(2.4)
2
X= = 0.67 & 0.18
2(20)
limits are 0 < x < 0.30 thus we can discard 0.67
[ CO] = (0.30 − x) M = 0.12M
[ Cl 2 ] = (0.50 − x) M = 0.32M
[ COCl 2 ] = (0.60 + x) M = 0.78M
88
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
89
 Consider this system at equilibrium at
5000C.
→ 4 HCl + O
2 Cl 2( g ) + 2 H 2 O ( g ) ← ( g) 2( g )
[ HCl] [ O 2 ]
4
( PHCl ) ( PO )
4
Kc = and K p =
( PCl ) ( PH O )
2
[ Cl 2 ] [ H 2O]
2 2
2
2
2
2
90
Kc =
( )( )
PHCl 4 PO2
RT
= RT
( P ) ( )
×
( PHCl ) 4
O2
1 5
RT
( ) ( ) (P ) (P ) ( )
PCl2
RT
2 P
H 2O
RT
2
Cl 2
2
H 2O
2 1 4
RT
K c = K p ( RT
1
) so for this reaction
-1 1
K c = K p (RT) or K p = K c (RT)
L atm
Must use R = 0.0821
mol K 91
Relationship Between Kp and Kc
 From the previous slide we can see that
the relationship between Kp and Kc is:
K p = K c ( RT ) or K c = K p ( RT )
∆n − ∆n
∆n = (# of moles of gaseous products) - (# of moles of gaseous reactants)
92
 Example 17-15: Nitrosyl bromide, NOBr, is
34% dissociated by the following reaction
at 25oC, in a vessel in which the total
pressure is 0.25 atmosphere. What is the
value of Kp?
2 NOBr( g ) →
← 2 NO ( g ) + Br2( g )
93
2 NOBr( g ) →
← 2 NO ( g ) + Br2( g )
Initial [] x atm 0 0
Change - 0.34 x atm + 0.34 x atm + 0.17 x atm
Equilibrium ( x - 0.34 x ) atm 0.34 xatm 0.17 x atm
94
PTot = PNOBr + PNO + PBr2

0.25 atm = ( x - 0.34 x ) atm + 0.34 x atm + 0.17 x atm
0.25 atm = 1.17 x atm, thus x = 0.21 atm.
Because NOBr is 34% dissociated,
it is 66% undissociated.
95
PNOBr = ( x - 0.34 x ) = 0.66 x

PNOBr = ( 0.66 )( 0.21 atm ) = 0.14 atm
PNO = 0.34 x = ( 0.34 )( 0.21 atm ) = 0.071 atm
PBr2 = 0.17 x = ( 0.17 )( 0.21 atm ) = 0.036 atm
( PNO ) ( PBr
2
) = ( 0.071) ( 0.036) = 9.3 ×10
2
−3
Kp = 2
( PNOBr ) 2
( 0.14) 2
96
 The numerical value of Kcfor this reaction
can be determined from the relationship of
Kp and Kc.
K p = Kc ( RT) or Kc = K p ( RT)
∆n − ∆n
∆n = 1
Kc = 9.3 × 10 −3
[ ( 0.0821)( 298) ] −1
= 38
. × 10 −4
97
 Example 17-16: Kc is 49 for the following reaction
at 450oC. If 1.0 mole of H2 and 1.0 mole of I2 are
allowed to reach equilibrium in a 3.0-liter vessel,
H 2( g ) →
+ I 2( g ) ← 2 HI ( g )
(a) How many moles of I2 remain unreacted at
equilibrium?
You do it!
98
H 2( g ) + → 2 HI
I 2( g ) ← (g)
Initial 0.33M 0.33M 0
Change -xM -xM + 2x M
Equilibrium ( 0.33 - x ) M ( 0.33 - x ) M 2x M
Kc =
[ HI]
2
= 49 =
( 2x)
2
∴ 7. 0 =
2x
[ H 2 ][ I 2 ] ( 0.33 - x ) 2
0.33 - x
9 x = 2.3; x = 0.256 M
[H 2 ] = [I 2 ] = (0.33 − x) M = 0.074 M
[ HI] = 2 x M = 0.51M
? mol I 2 = 3.0 L × 0.074 mol L = 0.21 mol 99
(b) What are the equilibrium partial
pressures of H2, I2 and HI?
You do it!
100
PH 2 = PI 2 = MRT = ( 0.074 mol L ) ( 0.0821 mol )

K ( 723 K ) = 4.4 atm
L atm
PHI = MRT = ( 0.51 mol L ) ( 0.0821 mol )

K ( 723 K ) = 30 atm
L atm
101
(c) What is the total pressure in the reaction
vessel?
You do it!
102
PTot = PH 2 + PI2 + PHI = ( 4.4 + 4.4 + 30) atm = 39 atm
103
Heterogeneous Equlibria
 Heterogeneous equilibria have more than one
phase present.
 For example, a gas and a solid or a liquid and a gas.
CaCO 3( s ) →
← CaO ( s ) + CO 2( g ) at 500 C o
 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:
K c = [CO 2 ] K p = PCO 2
104
For this reaction :
SO 2 ( aq ) →
+ H 2 O ( ) ← H 2SO 3( aq ) o
(at 25 C)
H 2 O ( ) is the solvent.
What are the forms of K c and K p ?
You do it!
Kc =
[ H 2SO 3 ]
K p is undefined
[SO 2 ]
105
 What are Kc and Kp for this reaction?
CaF2( s ) → 2+
← Ca ( aq ) + 2 F( aq )
1- o
(at 25 C)
You do it!
[
Kc = Ca 2+
][ F ]
− 2
K p is undefined
106
 What are Kc and Kp for this reaction?
→ Fe O + 4 H
3 Fe( s ) + 4 H 2 O ( g ) ← ( at 500 o
C)
3 4( s ) 2( g )
( P )
4
Kc =
[ H2 ] 4
Kp =
H2
[ H 2 O] (P )
4 4
H 2O
107
Relationship Between ∆Gorxn
and the Equilibrium Constant
 ∆Gorxn is the standard free energy change.
 ∆Gorxn is defined for the complete conversion of all reactants to
all products.
 ∆G is the free energy change at nonstandard conditions
• For example, concentrations other than 1 M or pressures other
than 1 atm.
 ∆G is related to ∆Go byo the following relationship.
∆G = ∆G + RT lnQ or
∆G = ∆G o + 2.303 RT log Q
R = universal gas constant
T = absolute temperature
Q = reaction quotient 108
 At equilibrium, ∆G=0 and Q=Kc.
 Then we can derive this relationship:
0 = ∆G + RT ln K or
0
0 = ∆G + 2.303 RT log K
0
which rearranges to :
∆G = - RT ln K or
0
∆G = - 2.303 RT log K
0
109
 For the following generalized reaction, the
thermodynamic equilibrium constant is
defined as follows:
→
aA + bB ← cC + dD
K=
( aC ) ( a D )
c d
where
( aA ) ( aB )
a b
aA is the activity of A aB is the activity of B

aC is the activity of C aD is the activity of D
110
 The relationships among ∆Gorxn, K, and the
spontaneity of a reaction are:
∆Gorxn K Spontaneity at unit concentration
<0 >1 Forward reaction spontaneous
=0 =1 System at equilibrium
>0 <1 Reverse reaction spontaneous
111
Relationship Between ∆Gorxn and
the Equilibrium Constant
112
 Example 17-17: Calculate the equilibrium
constant, Kp, for the following reaction at 25oC
from thermodynamic data in Appendix K.
N 2O 4( g ) →
← 2 NO 2( g )
 Note: this is a gas phase reaction.
113
N 2O 4( g ) →
← 2 NO 2( g )
1. Calculate ∆G o
rxn
∆G o
rxn = 2∆G o
f NO 2 ( g ) − ∆G o
f N 2O 4 ( g )
∆G o
rxn = 2( 51.30 kJ ) − ( 97.82 kJ )
∆G o
rxn = 4.78 kJ mol rxn
∆G o
rxn = 4.78 ×10 3 J
mol rxn
This reaction is nonspontaneous. 114

2. Calculate K from ∆G orxn = − RT ln K p
∆G o
4.78 × 10 mol 3 J
ln K p = =
rxn
= −1.93
− RT - ( 8.314 J mol K )( 298 K )
Kp = e −1.93
= 0.145 =
( P ) NO 2
2
(P ) N 2O 4
A very common mistake is

to not convert the ∆G o
rxn from kJ to J!
115
 Kpfor the reverse reaction at 25oC can be
calculated easily, it is the reciprocal of the
above reaction.
→
2 NO 2(g) ← N 2 O 4(g)
∆G orxn = −4.78 kJ/mol
K =
1
'
=
1
= 6.90 =
( PN 2O4 )
p
K p 0.145 ( PNO2 ) 2
116
 Example 17-18: At 25oC and 1.00 atmosphere,
Kp = 4.3 x 10-13 for the decomposition of NO2.
Calculate ∆Gorxn at 25oC.
2 NO 2( g ) →
← 2 NO ( g ) + O 2( g )
You do it.
117
∆G o
rxn = − RT ln K p
∆G o
rxn = −(8.314 J
mol K )(298 K ) ln 4.3 ×10 -13
∆G o
rxn = −(2480 J mol)(−28.47)
∆G o
rxn = 7.06 ×10 4 J
mol rxn = 70. 6 kJ
mol rxn
118
 The relationship for K at conditions other
than thermodynamic standard state
conditions is derived from this equation.
∆G = ∆G o + RT lnQ
or
∆G = ∆G + 2.303 RT log Q
o
119
Evaluation of Equilibrium Constants
at Different Temperatures
 From the value of ∆Ho and K at one
temperature, T1, we can use the van’t Hoff
equation to estimate the value of K at
another temperature, T2.
K T2 ∆H o (T2 − T1 )
ln =
K T1 R T2 T1
or
K T2 ∆H o 1 1
ln =  − 
K T1 R  T1 T2  120
 Example 17-19: For the reaction in
example 17-18, ∆Ho = 114 kJ/mol and Kp =
4.3 x 10-13 at 25oC. Estimate Kp at 250oC.
2 NO2(g) ↔ 2 NO(g) + O2(g)
121
Evaluation of Equilibrium
Constants at Different
Temperatures
T1 T=
LetLet 1 =298
298K andTT
K and ==
2 2 523523
K K
apply
apply thethevan'
van'tt Hoff
Hoffequation
equation
K T2 (1.14 ×10 mol)( 523 − 298)
5 J
ln =
K T1 ( 8.314 J mol K )( 523 K )( 298 K )
K T2
ln = 19.795
K T1
122
Take the antilog of both sides of equation.
K T2
= e19.80 = 4.0 ×108
K T1
Solve for K T2 & substitute the known value of K T1
( )(
K T2 = 4.0 ×10 K T1 = 4.0 ×10 4.3 ×10
8 8 -13
)
K T2 = 1.7 ×10 −4 @ 250o C vs K T1 = 4.3 ×10 -13 @ 25o C
The reaction is more product favored at the higher T.
123
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?
124
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.
125
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?
126
End of Chapter 17
 This chapter is the key to the
understanding of Chapters 18, 19, & 20.
 Make sure you understand this chapter’s
concepts!
127

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This expression is valid for all reactions.

If the volume is increased, which decreases the pressure, Q > K c .

 Catalysts do not affect the position of equilibrium.

N 2( g ) is obtained from liquid air. H 2( g ) obtained from coal gas.

Solve this quadratic equation

Since 0 < x < 0.10, we can discard - 0.78 as an answer.

Equil. []' s 0.30 M 0.10 M 0.60 M

∆n = (# of moles of gaseous products) - (# of moles of gaseous reactants)

PTot = PNOBr + PNO + PBr2

PNOBr = ( x - 0.34 x ) = 0.66 x

PH 2 = PI 2 = MRT = ( 0.074 mol L ) ( 0.0821 mol )

PHI = MRT = ( 0.51 mol L ) ( 0.0821 mol )

PTot = PH 2 + PI2 + PHI = ( 4.4 + 4.4 + 30) atm = 39 atm

 How does the equilibrium constant differ for heterogeneous

aA is the activity of A aB is the activity of B

>0 <1 Reverse reaction spontaneous

This reaction is nonspontaneous. 114

A very common mistake is

 If you are having trouble getting a fire

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