CH 6 - Equilibrium-1

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Chapter 6: Chemical Equilibrium

6.1
6.2
6.3
6.4
6.5
6.6
67
6.7
6.8
6.9
The Equilibrium Condition

The Equilibrium
q
Constant
Equilibrium Expressions Involving Pressures
The Concept of Activity
Heterogeneous Equilibria
Applications of the Equilibrium Constant
Sol
Solving
ing Eq
Equilibrium
ilib i m P
Problems
oblems
Le Chtelier's Principle
Equilibria Involving Real Gasses
Stoichiometry vs. Equilibrium

Previous stoichiometric calculations have assumed
complete reactions
Limiting
g reagent
g
is used up
p
Maximum amount of product is formed
2NO2
N 2 O4
reddish-brown
colorless
Most reactions, however, do not

reach completion.
They reach chemical equilibrium
NO2
Mix of
NO2
and
N 2 O4
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Chemical Equilibrium
Chemical reactions are not a one-way street
2 NO2 (g)
N2O4 (g)
Every reaction has a forward and a reverse!

Stoichiometry calculations assume just a forward
reaction.
Equilibrium calculations look at the forward and
reverse reactions.
Reaching Equilibrium on the

Macroscopic and Molecular Levels
DECOMPOSITION
N2O4 (g)
Colorless
2 NO2 (g)
Brown
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2 NO2 (g)
N2O4 (g)
Two reactions are happening:

pp
g
Dimerization of nitrogen dioxide
Decomposition of dinitrogen tetroxide
Chemical equilibrium is the state at which the
concentrations of all reactants and products remain
th same.
the
At chemical equilibrium the rate of formation and the
rate of decomposition are equal.
N2O4(g) 2 NO2(g)
Over time, the reaction
looks like this:
The
Th amountt off N2O4
decreases
The amount of NO2
increases
Eventually the
concentrations of
each species stop
changing.
Equilibrium, however,
is a dynamic
process.
EQUILIBRIUM
TIME
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Characteristics of Chemical
Equilibrium States
Reaching equilibrium requires that reactions

occur.
Chemical reactions occur via collisions of reacting
molecules. The energy released during collisions breaks
bonds in reactant molecules, allowing the atoms to
rearrange to form a product.
Once equilibrium is reached, there is no

macroscopic evidence of further change.
Reached through dynamic balance of

forward and reverse reaction rates.
Equilibrium is reached when the forward and reverse
reactions are balanced, so there is no net change in the
concentrations of reactants or products.
Where this balancing point occurs can be different for each
reaction:
(leaves few reactants)
2H2 (g)+ O2 (g) 2H2O (g)
Equilibrium lies far to the right
2CaO (s) 2Ca (s)+ O2 (g)
(~no solid Ca forms)
Equilibrium lies far to the left
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SO, how do we know if the equilibrium is
to
to the right?
to the left?
in the middle?
Where will equilibrium be?
WE DO EXPERIMENTS!!
And Later Thermodynamics!!
Initial and Equilibrium Concentrations for the

N2O4-NO2 System at 100C
Initial
[N2O4]
[NO2]
Equilibrium
[N2O4]
[NO2]
Ratio
[NO2]2 [N2O4]
0.1000
0.0000
0.0491
0.1018
0.211
0.0000
0.1000
0.0185
0.0627
0.212
0.0500
0.0500
0.0332
0.0837
0.211
0.0750
0.0250
0.0411
0.0930
0.210
=K
Experiments carried out at a certain temperature, but with

different initial concentrations, yield the same value for the
EQUILIBRIUM CONSTANT, K.
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The Equilibrium Constant
This is a constant at a
given temperature
the equilibrium
constant
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The Equilibrium Constant:

N2 + 3 H2 2 NH3
The Equilibrium Constant:

N2 + 3 H2 2 NH3
Varying the starting concentrations gives different

equilibrium concentrations, but K is the same in each case
(6.02 x 10-2)
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Equilibrium Constant - UNITS

We actually express K in terms of activity of reactants and
products:
Activity of
product E
This definition of the equilibrium

q
constant replaces
p
the
definition provided by Zumdahl in Section 6.2.
This definition means K is unitless, as it should be! (Zumdahl
only uses units in Ch. 6 and calls them apparent units.)
Activities
To relate concentration (or pressure) of a reactant or
product to its activity, we divide by a reference
For concentration, the reference is 1 M
aHCl(aq) = [HCl]/1M
For pressure, the reference is 1 atm
aHe(g) = PHe/1 atm
Pure
P
solids
lid and
d pure liquids
li id have
h
an activity
ti it off 1
aHg(l) = 1
aFe(s) = 1
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The Equilibrium Constant (contd.)

Example from Zumdahl (done with activities)
At equilibrium [NH3] = 3.1 x 10-2 M, [N2] = 8.5 x 10-1 M, and

[H2] = 3.1 x 10-3 M. What is the equilibrium constant?
We write Kc to indicate that we are using concentrations.
The Equilibrium Constant (contd.)
Notice that dividing by a reference state makes K unitless.
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Reaching Equilibrium from Different

Starting Points
CO (g) + 2 H2 (g) CH3OH (g)
K = [CH3OH]
[CO][H2]2
Different initial
concentrations
Differentt final
Diff
fi l
concentrations
SAME ratio of
products / reactants

A reaction can have many equilibrium constants
you need to specify the temperature of the reaction
At that temperature, the equilibrium constant is
constant, regardless of initial concentrations.
The set of equilibrium concentrations (based on your
initial concentration) is called the equilibrium
position.
Since there are an infinite number of initial
concentrations, there are also an infinite number
of equilibrium positions for each constant!
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2H2 (g)+ O2 (g) 2H2O (g)
(leaves few reactants)
Equilibrium lies far to the right

What can K tell us about this reaction?
Equilibrium concentration of reactants is low
Equilibrium concentration of products is high
Since
i
K is
i the
h ratio
i off products
d
over reactants
K must be large

2CaO (s) 2Ca (s)+ O2 (g)
(~no solid Ca forms)
Equilibrium lies far to the left

What can K tell us about this reaction?
Equilibrium concentration of reactants is high
Equilibrium concentration of products is low
low
Since K is the ratio of products over reactants
K must be small
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Equilibrium:
Constant vs. Position
Equilibrium Constant:
ratio
ti off products
d t to
t reactants
t t
depends only on TEMPERATURE
versus
Chemical equilibrium (the equilibrium position)
a dynamic situation
can be affected by temperature, pressure, and/or
initial concentration of reactants and products.
Solving Equilibrium Problems

At this point, you should be able to do these things
involving the equilibrium constant:
Write an equilibrium expression
Use the magnitude of K to predict if the
equilibrium lies to the left or right (favors products
or reactants)
Given equilibrium concentrations, calculate K
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Sample Problems
Problem: Write the equilibrium constant expression for
the following reactions:
a. N2 (g) + O2 (g) 2NO (g)
b. 2CO (g) + O2 (g) 2CO2 (g)
c. N2O4 (g) 2NO2 (g)
Sample Problems
Problem: Predict where the equilibrium lies for these
reactions
a. N2 (g) + O2 (g) 2NO (g); K = 1 x 10-30
b. 2CO (g) + O2 (g) 2CO2 (g); K = 2.2 x 1022
c. N2O4 (g) 2NO2 (g); K = 0.211
Plan: Remember that large
g K favors p
products, small K
favors reactants.
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Sample Problems
Problem: Predict where the equilibrium lies for these
reactions
a N2 (g) + O2 (g) 2NO (g); K = 1 x 10-30
a.
K is very small, the reaction favors reactants
b. 2CO (g) + O2 (g) 2CO2 (g); K = 2.2 x 1022
K is very large, the reaction favors products
c. N2O4 (g) 2NO2 (g); K = 0.211
K is intermediate (somewhat close to one), the
reaction has significant amounts of reactants and
products at equilibrium
Sample Problems
Problem: At 360C, the reaction
COCl2 (g) CO (g) + Cl2 (g)
has equilibrium concentrations of:
[COCl2] = 0.480 M, [CO] = 2.0 x 10-2 M, [Cl2] = 2.0 x 10-2 M
What is the value of K at 360C for this reaction?
Plan: Write the equilibrium constant expression for the
reaction and then substitute in the equilibrium concentrations
to solve for K.
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Sample Problems
Problem: At 360C, the reaction
has equilibrium concentrations of:
[COCl2] = 0.480 M, [CO] = 2.0 x 10-2 M, [Cl2] = 2.0 x 10-2 M
What is the value of K at 360C for this reaction?
K = [CO][Cl2] = [2.0 x 10-2][2.0 x 10-2]
[COCl2]
[0.480]
K = 8.3 x 10-4
Determining Equilibrium Concentrations from K

Methane can be made by reacting carbon disulfide with
hydrogen gas:
CS2 (g) + 4 H2 (g) CH4 (g) + 2 H2S (g)
K for this reaction is 27.8
27 8 at 900oC.
C At equilibrium the
reaction mixture in a 5.0 L flask is: 0.250 mol CS2, 1.10
mol of H2, and 0.45 mol of H2S. How many moles of
methane are formed?
Plan:
Calculate the
equilibrium
concentrations
Use moles and V
Concentration of
methane
Use K and equilibrium
expression
Convert
molarity to
moles
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Determining Equilibrium Concentrations from K

[CS2] =
0.250 mol
= 0.05 M
5.0 L
[[H2S]] =
0.450 mol
= 0.09 M
50L
5.0
K=
[CH4] =
1.10 mol
= 0.22 M
5.0 L
[H2] =
[CH4] = ?
[CH4][H2S]2
= 27.8
[CS2][H2]4
K[CS2][H2]4
(27.8)(0.05)(0.22)4
=
[H2S]2
(0 09)2
(0.09)
= 0.40 M
moles CH4 = 0.40 M x 5.0 L = 2.0 moles
Using and Rearranging K

The equilibrium expression for a reaction written in reverse is
the reciprocal of that for the original expression:
[CO2][SO2]2
[CS2][O2]3
CS2(g) + 3 O2(g) CO2(g) + 2 SO2(g)
K=
CO2(g) + 2 SO2(g) CS2(g) + 3 O2(g)
K =
[CS2][O2]3
1
=
2
[CO2][SO2]
K
If the original reaction is multiplied by a factor n, the new

equilibrium constant is the original raised to the power n.
2 CS2(g) + 6 O2(g) 2 CO2(g) + 4 SO2(g)
K =
[CO2] 2[SO2]4
= K2
[CS2] 2[O2]6
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Example
The following equilibrium concentrations were observed for the
reaction between CO and H2 to form CH4 and H2O at 927oC.
CO (g) + 3 H2 (g) CH4 (g) + H2O (g)
[CO] = 0.613 mol/L
[H2] = 1.839 mol/L
[CH4] = 0.387 mol/L

[H2O] = 0.387 mol/L
a) Calculate the value of K at 927oC for this reaction.

b) Calculate the value of the equilibrium constant at 927oC for:
H2O (g) + CH4 (g) CO (g) + 3 H2 (g)
c) Calculate the value of the equilibrium constant at 927oC for:
1/3 CO (g) + H2 (g) 1/3 CH4 (g) + 1/3 H2O (g)
Example
a) Calculate the value of K at 927oC for this reaction.
K=
[CH4] [H2O]
=
[CO] [H2]3
(0.387) (0.387)
(0.613) (1.839)3
= 0.0393
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Example contd.
b) Calculate the value of the equilibrium constant at 927oC for:
H2O (g) + CH4 (g) CO (g) + 3 H2 (g)
K =
K
]3
[CO][H2
=
[H2O][CH4]
(0.613) (1.839)3
(0.387) (0.387)
= 25.45
25 45
Shortcut if K is known: K is just the reciprocal of K from part a:

1
K = 1 =
= 25.45
K
0.0393
c) Calculate the value of the equilibrium constant at 927oC for:
1/3 CO (g) + H2 (g) 1/3 CH4 (g) + 1/3 H2O (g)
K =
[H2O]1/3 [CH4]1/3
=
[CO]1/3 [H2]
(0.387)1/3 (0.387)1/3
(0.613)1/3 (1.839)
Shortcut if K is known: K =(K)1/3 = (0.0393)1/3 = 0.3399
Summary
Some Characteristics of the Equilibrium Expression
The equilibrium expression for a reaction written in reverse is
the reciprocal of that for the original reaction.
Knew = 1/Koriginal
When the balanced equation for a reaction is multiplied by a
factor n, the equilibrium expression for the new reaction is
the original expression raised to the nth power.
Knew = (Koriginal)n
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Types of Equilibrium Constants

Dissociation constant (acids, bases, salts; Ch. 7 & 8)
Solubility product (precipitation reactions; Ch. 8)
Stability constant (complexation reactions; Ch. 8)
Standard potentials (redox reactions; Ch. 11)
Equilibrium arises through dynamic balance

between forward and reverse reactions
k1
Forward:
2NO2 (g) NO3 (g) + NO (g)
Reverse:
NO3 (g) + NO (g) 2NO2 (g)
k -1
Forward rate = k1[NO2][NO2] = k1[NO2]2

Reverse rate = k-1[NO3][NO]
k1 and k-1 reflect probabilities that one collision leads to
reaction
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Kinetic Approach to Equilibrium

k1 NO2 k1 NONO3
2
k1 NONO3
K
2
k1
NO2
The RATE of forward reaction decreases as the reaction

progresses since the initial concentration of reactants
decreases over time.
Extent of the Reaction

A value of K >> 1 means that at equilibrium the system will
consist mainly of products
A value of K << 1 means that the system consists mainly of
reactants the chemical reaction does not occur to much
extent
K and the time required to reach equilibrium are NOT
directly related
Rates of chemical reactions are temperature dependent
and so are the equilibrium positions and constants
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The Reaction Quotient, Q

OR
How do we know the reaction is at
equilibrium?
q
Consider the reaction:
aA(g) + bB(g) cC(g) +dD(g)

The reaction quotient, Q is defined as:
[C]tc [D]td
Q=
[A]ta [B]tb
Q has same form as K, but the concentrations are the actual

concentrations at any time (t) rather than the concentrations
after equilibrium is reached.
Equilibrium Constant, K
vs.
Reaction Quotient, Q
The equilibrium constant describes equilibrium
concentrations
The reaction quotient uses initial concentrations to
determine in which direction a reaction will proceed.
if Q<K, the system will produce products
(forward reaction; shifts to the right)
g
if Q=K, the system is in equilibrium
(no change in concentrations of products or reactants)
if Q>K , the system will consume products
(reverse reaction; shifts to the left)
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Reaction Direction and the

Relative Sizes of Q and K
Excess products
initially
Excess reactants
initially
N2O4 (g) 2NO2 (g)
Q = [NO2]2
[N2O4]
TIME
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Ways of Expressing Q and K values

Form of Chemical Equation
Forward reaction: A
Reversed reaction: B
Form of Q
[B]
[A]
Q = 1 = [A]
Qfwd [B]
Qfwd =
Reaction as sum of two steps:

(1) A
(2) C
Q1 =
Q2 =
Value of K
Kfwd =
[B]eq
[A]eq
1
K=
Kfwd
[C]
[A]
[B]
Qoverall = Q1 x Q2
Koverall = K1 x K2
[C]
Reaction with pure solid or liquid component:

A(s)
B
Q = [B]
K = [B]
Predicting Reaction Direction using Q

Consider the following reaction:
CH4 (g) + 2 H2S (g) CS2 (g) + 4 H2 (g)
1.00 mol CH4, 1.00 mol CS2, 2.00 mol H2S and 2.00 mol H2
are mixed in a 250 mL vessel at 960oC. If K = 0.036 at this
temperature, calculate Q and figure out in which direction
will the reaction proceed in order to reach equilibrium?
Plan:
Calculate actual
concentrations
Calculate Q
Compare to K
Use moles and

vessel volume
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CH4(g) + 2 H2S(g) CS2(g) + 4 H2(g)

[CH4]0= 1.00 mol/0.250 L = 4.00 M
[H2S]0 = 2.00 mol/0.250 L = 8.00 M
K = 0.036
[CS2]0 = 1
1.00
00 mol/0
mol/0.250
250 L = 4.00
4 00 M
[H2]0 = 2.00 mol/0.250 L = 8.00 M
Calculate the value of Q:
Q=
[CS2]o[H2]o4
[CH4]o[H2S]o
=
2
(4.00 M)(8.00 M)4

(4 00 M)(8.00
(4.00
M)(8 00 M)2
= 64
Comparing Q and K: Q > K, so the reaction goes to the left.

[reactants] increase and [products] decrease
N2 (g) + 3 H2 (g) 2 NH3 (g)
For the synthesis of ammonia at 500oC, the equilibrium constant is

6.0 x 10-2. Predict the direction in which the system will
shift to reach equilibrium in each of the following cases.
[N2]0= 1.0 x 10-5 M
[H2]0=2.0 x 10-3 M
a) [NH3]0 = 1.0 x 10-3 M
b) [NH3]0 = 2.00
2 00 x 10-4 M
[N2]0= 1
1.50
50 x 10-5 M [H2]0= 3
3.54
54 x 10-1 M
c) [NH3]0 = 1.0 x 10-4 M
[N2]0= 5.0 M
[H2]0= 1.0 x 10-2 M
Solution:
a) First we calculate Q:
[NH3]o2
(1.0 x 10-3 )2
Q=
=
[N2]o[H2]o3
(1.0 x 10-5 )(2.0 x 10-3 )3
= 1.3
1 3 x 107
Since K = 6.0 x 10-2 L2/mol2, Q is much greater than K. For the
system to attain equilibrium, [products] must decrease and
[reactants] must increase.
N2 (g) + 3 H2 (g)
2 NH3 (g)
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Example contd.
K = 6.0 x 10-2 L2/mol2
b) We calculate the value of Q:

Q=
[NH3]o2
[N2]o[H2]o3
6 01 x 10-2
= 6.01
(2.00 x 10-4 )2
(1.50 x 10-5 ) (3.54 x 10-1 )3)
In this case Q = K, so the system is at equilibrium..

N2 (g) + 3 H2 (g) =
c) The value of Q is:

Q=
[NH3]o2
[N2]o[H2]o3
= 2.0 x 10-3
2 NH3 (g)
(1.0 x 10-4 )2
(5.0 ) (1.0 x 10-2 )3
N2 (g) + 3 H2 (g)
2 NH3 (g)
Here Q is less than K, so the system will shift to the right, attaining
equilibrium by increasing [product] and decreasing [reactants]:
More ammonia!

Given the reaction:
H2 (g) + F2 (g) HF (g)
And initial concentrations:
[H2]0 = 1.00 M
[F2]0 = 2.00 M
What will the equilibrium concentrations be for
reactants and products?
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First: Make sure the reaction is balanced!
H2 (g) + F2 (g) 2 HF (g)

Second: Construct the equilibrium expression:
HF
1M
2
K C 1.15
1 15 10
H 2 F2
1 M 1 M
2

Third: Using the stoichiometry of the reaction, derive
expressions for concentrations at equilibrium.
You can think through this process by considering the
initial, change in, and equilibrium concentrations. Easy
to do using an ICE table:
H2 (g) + F2 (g) 2 HF (g)

Conc. (M)
H2 (g)
F2 (g)
2 HF (g)
Initial
1.00
2.00
Change
-x
-x
+2x
Equilibrium
1.00 - x
2.00 - x
2x
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What is this x of which you speak?

-x
x
PCl5(g)
PCl3(g)
x
+
Cl2(g)
Initially only PCl5 present.

As reaction proceeds, for each PCl5 that decomposes,
one PCl3 and one Cl2 is formed (stoichiometry).
x represents the change in composition between the
initial conditions and equilibrium.

Third: Using the stoichiometry of the reaction, derive
expressions for concentrations at equilibrium.
You can think through this process by considering the
initial, change in, and equilibrium concentrations. Easy
to do using an ICE table:
H2 (g) + F2 (g) 2 HF (g)

Conc. (M)
H2 (g)
F2 (g)
2 HF (g)
Initial
1.00
2.00
Change
-x
-x
+2x
Equilibrium
1.00 - x
2.00 - x
2x
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Fourth: Substitute equilibrium concentrations into the
equilibrium expression and solve.
HF
1M
2
K C 1.15 10
H 2 F2
1 M 1 M
2
Species
Equilib. Conc. (M)
H2
1.00 - x
F2
2.00 - x
HF
2x
By solve we mean solve

for x which can use to
determine equilib.
concentrations!

Continuing with the example:
2
2x M
2
2x
1M
2
1.15 10
1.00 x M 2.00 x M 1.00 x 2.00 x
1M
1M
1.15 10 2 1.00 x 2.00 x 2 x
1.1110 x 3.45 10 x 2.30 10 0

2
We need to solve this last equation for x.
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The last expression is a quadratic equation of the form:
ax2
bx
=0
1.1110 x 3.45 10 x 2.30 10 0

2
The solution to this equation can be determined using

the quadratic formula:
b b 2 4ac
x
2a

Applying the quadratic formula to our example:
1.1110 x 3.45 10 x 2.30 10 0

2
2
b b 2 4ac 3.45 10
x
2a
3.45 10 4 1.1110 2.30 10

2 1.11 10
2 2
x 2.14, 0.968
Which root is correct? The answer is the correct root is

the one that makes physical sense. Recall that since
[H2]eq = 1.00 x. Only x = 0.968 makes physical sense.
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Last: Using expression for x, determine the equilibrium
concentrations.
x 0.968
Species
Equilib. Conc. (M)
H2
1.00 - x
3.2 x 10-2 M
F2
2.00 - x
1.03 M
HF
2x
1.94 M
Which species are present to the greatest extent at

equilibrium? What does that tell us about the extent to
which the reaction proceeds towards products?

Zumdahls Steps:
Write the balanced equation for the reaction.

Write the equilibrium expression.
List the initial concentrations.
Define the change in concentrations using the stoichiometry of
the reaction.
Using the initial concentrations and change, write down the
expressions for equilibrium concentrations.
Substitute equilibrium concentrations into the expression for K,
K
and solve.
Using the physically-reasonable solution, determine the
equilibrium concentrations.
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Calculating Equilibrium Partial Pressures

Using Quadratic Equation
The reaction between nitrogen and oxygen to form nitrogen
monoxide proceeds according to the following reaction:
N2 (g) + O2 (g) 2 NO(g)
K = 4.1x10-4 at 2000K
Initially 0.500 moles of N2 and 0.860 moles of O2 are put into a

2.00 L vessel. Calculate the concentrations of all the species at
equilibrium.
IInitial
iti l concentration
t ti off N2 = 0.500
0 500 mol/2.00
l/2 00 L = 0.250
0 250 M
Initial concentration of O2 = 0.860 mol/2.00 L = 0.430 M
Initial concentration of NO = 0
Q = 0, therefore the reaction proceeds to the right
Construct the reaction table.

N2 (g) + O2 (g) 2NO(g)

Conc. (M)
N2 (g)
O2 (g)
2NO (g)
Initial
0.250
0.430
Change
-x
-x
+2x
Equilibrium
0.250 - x
0.430 - x
2x
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Substituting the equilibrium concentrations from the I.C.E. table into
the equilibrium expression:
K=
[NO]2
[N2][O2]
(2x)2
= 4.10 x 10-4
(0.250-x)(0.430-x)
This expression simplifies to:

(4.00)x2 + (2.79 x 10-4)x (4.41 x 10-5) = 0
We obtain two possible solutions:
x = -3.35 x 10-3 and x = 3.28 x 10-3

Since only the positive root leads to all positive concentrations, we
ignore the negative root.
Calculating equilibrium concentrations:
[NO] = 2x = 6.56x10-3 M
[N2] = 0.250 M x = 0.247 M
[O2] = 0.430 M x = 0.427 M
Ch k
Check:
K=
[NO]2
[N2][O2]
(6.56x10-3)2
(0.247)(0.427)
= 4.10x10-4
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Solving equilibrium problems with

simplifying assumptions
Phosgene decomposes into CO and Cl2 when heated according
to the equation.
K = 8.3x10-4 at 360oC
Calculate the concentration of all species
p
at equilibrium
q
if
5.00 moles of phosgene are placed into a 10.0 L flask.
[COCl2] =
5.00 mol
10.0 L
= 0.500 M

K = 8.3x10
8 3x10-4 at 360
360C
C
Conc. (M)
COCl2 (g)
CO (g)
Cl2 (g)
Initial
0.500
Change
-x
+x
+x
Equilibrium
0.500 - x
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K=
[CO][Cl2]
[COCl2]
x2
0.500 - x
= 8.3 x 10-4
For K to be so small, (0.500 x) >>x2, so 0.500-x 0.500

x2
0.500 - x
x2
= 8.3 x 10-4
0.500
x = 2.037 x 10-2 2.04 x 10-2

Check to see if this assumption works 0.500 2.04 x 10-2 = 0.4796
Approximation gives error of ~4% (0.500/0.4796 = 95.92%).
This ASSUMPTION can ONLY be made for SMALL VALUES of K!!
Use the 5% rule if the error is less than 5%, the assumption is valid.
(if x < 5% of [ ]o, then [ ] < 5%...assumption is valid)
Calculating K from Concentration Data

Problem: Hydrogen iodide decomposes at moderate temperatures by the
reaction:
2 HI (g) H2 (g) + I2 (g)
When 4.00 mol HI were placed in a 5.00 L vessel at 458oC, the equilibrium
mixture was found to contain 0.442 mol I2. What is the value of Kc ?
Plan: First we calculate the molar concentrations of HI and I2, and then
substitute them into the equilibrium expression to find the value of Kc.
Solution:
Starting conc. of HI = 4.00 mol = 0.800 M
5.00 L
E ilib i
Equilibrium
conc. off I2 =
Conc. (M)
Starting
Change
Equilibrium
2HI (g)
0.800
- 2x
0.800 - 2x
0.442 mol = 0.0884

0 0884 M
5.00 L
H2 (g)
I2 (g)
0
+x
x
0
+x
x = 0.0884
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Calculating K from Concentration Data

[I2] = x = [H2] = 0.0884 M
[HI] = (0.800 (2 * 0.0884)) M = 0.623 M
Kc =
[H2] [I2]
[HI]2
(0.0884)(0.0884)
(0.623)2
= 0.0201
The equilibrium
q
constant for the decomposition
p
of hydrogen
y
g iodide at
o
458 C is only 0.0201, meaning that the decomposition does not
proceed very far under these temperature conditions.
Equilibrium
We talked about Q, the equilibrium quotient, as a
snapshot of where the reaction is at any time, t.
[C]tc [D]td
Q=
[A]ta [B]tb
[C]eqc [D]eqd
K=
[A]eqa [B]eqb
Three p
possibilities: Q > K, Q = K, Q < K
Today well explore what happens if we push a
reaction out of equilibrium by adding or removing
reactants or products.
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Equilibrium Position
Factors that control the position of chemical equilibria
are:
Concentration
Pressure
Temperature
NOTE: catalysts influence rate
rate, not position of equilibrium
The Effect of a Change in Concentration

Given an equilibrium equation such as :
CH4 (g) + NH3 (g)

Add NH3
HCN (g) + 3 H2 (g)

Forces equilibrium to
produce more product.
What happens to Q when we add NH3?
[HCN]t [H2]t3
Q=
[CH4]t [NH3]t
[NH3] increases
Q then decreases
Q < K, so more
products must form to
return to equilibrium
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The Effect of a Change in

Concentration
CH4 (g) + NH3 (g)
Remove NH3
HCN (g) + 3 H2 (g)
Forces the reaction equilibrium to go back

to the left and produce more of the reactants.
What happens to Q when we remove NH3?

[NH
[ 3] decreases
Q then increases
Q > K, so more
reactants must form to
return to equilibrium
[HCN]t [H2]t3
Q=
[CH4]t [NH3]t
CH4 (g) + NH3 (g)
HCN (g) + 3 H2 (g)
Forces equilibrium to go
toward the reactants.
CH4 (g) + NH3 (g)

Forces equilibrium to make more
product and replace the lost HCN.
Add H2
HCN (g) + 3 H2 (g)

Remove HCN
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Le Chteliers Principle
If a change in conditions (a stress) is imposed on a system
at equilibrium, the equilibrium position will shift in a direction
that tends to reduce that change in conditions.
A + B
C + D + Energy
For example, in the reaction above:

Add A or B reaction will make more product
Remove
e o eAo
or B reaction
eac o will form
o more
o e reactants
eacta ts
Add C or D reaction will form more reactants
Remove C or D reaction will shift to form more products
If the reaction is heated you will get more reactants
If the reaction is cooled you will get more products

Concentration
If a gaseous reactant
t t or product
d t is
i added
dd d to
t a
system at equilibrium, the system will shift in a
direction to reduce the concentration of the
added component.
If a gaseous reactant or product is removed from a
system at equilibrium,
lb
the
h system willll shift
h f in a
direction to increase the concentration of the
removed component.
38
12/27/2015

Consider the following reaction:
2 H2S (g) + O2 (g) 2 S ((s)) + 2 H2O (g)

What happens to:
(a) [H2O] if O2 is added?
The reaction proceeds to the right so [H2O] increases.
(b) [H2S] if O2 is added?
Some H2S reacts with the added O2 to move the reaction to
the right, so [H2S] decreases.

2 H2S (g) + O2 (g) 2 S (s) + 2 H2O (g)
(c) [O2] if H2S is removed?
The reaction proceeds to the left to re-form H2S, more O2
is formed as well, [O2] increases.
(d) [H2S] if S(s) is added?
S is a solid, so its activity does not change. Thus, [H2S] is
unchanged.
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Pressure (Volume)
Pressure changes mainly involve gases (liquids and solids
are nearly incompressible). For gases, pressure changes can
occur in three ways:
Change the concentration of a gaseous component
Add an inert gas (one that does not take part in the
reaction)
Change the volume of the reaction vessel
The Effect of a Change in Pressure

(Volume)
When you change the volume of a system at
equilibrium, the equilibrium position shifts to reduce the
effect of the change.
If the volume decreases (increased partial
pressure), the total number of gas molecules
decreases (reaction shifts to side with fewer moles
of gas).
If the volume increases (decreased partial
p
pressure), the total number of gas molecules
increases (reaction shifts to side with more moles of
gas).
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12/27/2015
Pressure Change
2 NO2 (g) N2O4 (g)
Brown
Colorless
We can summarize
pressure changes as
follows:
Increase pressure
equilibrium shifts
toward side with fewer
moles of gas
Reduce pressure
equilibrium shifts
toward side with more
moles of gas
Equilibrium is reestablished, shifts to

fewer moles of gas
At equilibrium
Pressure is increased
rapidly (concentration of
both gases increases)
Cant we change P in other ways?

We can add or remove a gaseous reactant or product!
but this is just the same as changing the concentration of
a species.
We can add a gas that is not involved in the reaction!
adding a chemically inert gas to the reaction mixture will
change the TOTAL pressure, but will have no effect on the
chemistry and, therefore, no effect on the equilibrium.
So the only P change that has any effect on equilibrium
position is a change in external P, which you get by
changing the volume of the reaction system.
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The Effect of a Change in Pressure (Volume)

How would you change the total pressure or volume in the
following reactions to increase the yield of the products:
((a)) CaCO3((s)) CaO(s)
( ) + CO2 (g)
The only gas is the product CO2. To move the reaction to the right,
increase the volume.
(b) S(s) + 3 F2 (g) SF6 (g)
With 3 moles of gas on the left and only one on the right, we
increase the pressure (decrease volume) to form more SF6.
(c) Cl2(g) + I2(g) 2 ICl (g)
The number of moles of gas is the same on both sides of the
equation, so a change in pressure or volume will have no
effect on the equilibrium.
The Effect of a Change in Temperature

Only temperature changes will alter the equilibrium constant, and that
is why we always specify the temperature when giving the value of K.
The best way to look at temperature effects is to realize that
temperature is a component of the equation, the same as a reactant or
product.
O2 (g) + 2 H2 (g)
Energy + 2 H2O (g)
2 H2O (g) + Energy
= Exothermic
2 H2 (g) + O2 (g) = Endothermic
A temperature increase favors the endothermic direction and a

temperature decrease favors the exothermic direction.
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Changes in Temperature (contd.)

Why would a reaction be exothermic (release heat)?
Chemical bonds of the products are more stable than
those of the reactants.
During solvation (Ch. 4), the potential energy of the ions
dissolved in solution is less than in the solid form.
Why would a reaction be endothermic (absorb heat)?
Ch
Chemical
i l bonds
b d off products
d t are less
l
stable
t bl th
than those
th
of the reactants.

Heat + N2O4 (g) 2 NO2 (g)
C
Colorless
l l
N2O4 gas
decomposes to form
reddish-brown NO2.
This reaction involves
the breaking of a
chemical bond.
The breaking of the chemical bond required energy (in the
form of heat) to be added to the system.
Therefore, this reaction is endothermic (with heat on the
reactant side).
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Heat + N2O4 (g) 2 NO2 (g)
What if we increase the
p
at which the
temperature
reaction occurs.
Increase in T means an
increase in energy available to
break the chemical bond.
Equilibrium shifts to products!
We can summarize temperature effects as follows:

For an endothermic reaction, an increase in T shifts equilibrium
towards products
For an exothermic reaction, an increase in T shifts equilibrium
towards reactants
Exothermic vs. Endothermic Reactions

Exothermic
Endothermic
Role of energy
gy in the
reaction:
Released as a
product
Absorbed as a
reactant
Effect of increasing
temperature:
Equilibrium shifts
toward the
reactants
Decreases
Equilibrium shifts
toward the
products
Increases
Change in K because
of increased T:
Change in concentration at constant T changes the

equilibrium position, but not the value of K (ratio of
products to reactants).
44
12/27/2015
Example
How does an increase in temperature affect the equilibrium
concentration of the substance in bold and K for the following
reactions:
(a) CaO(s) + H2O (l) Ca(OH)2 (aq) + energy
(b) CaCO3 (s) + energy + CaO(s) + CO2 (g)
(c) SO2 (g) + energy S(s) + O2(g)
Example
How does an increase in temperature affect the equilibrium
concentration of the substance in bold and K for the following
reactions:
(a) CaO(s) + H2O (l) Ca(OH)2 (aq) + energy
Increasing T shifts the system to the left, where it absorbs energy.
[Ca(OH)2] and K decrease.
(b) CaCO3 (s) + energy + CaO(s) + CO2 (g)
Increasing T shifts the system to the right, where it absorbs
energy. [CO2] and
d K iincrease.
(c) SO2 (g) + energy S(s) + O2(g)
Increasing T shifts the system to the right, where it absorbs
energy. [SO2] will decrease and K increases.
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Effect of Various Stresses on an

Equilibrium System
Stress
Net Direction of Reaction
Effect on Value of
K
Concentration:
Increase [reactant]
Decrease [reactant]
Toward formation of products None

Toward formation of reactants None
Pressure (constant T):

Decrease P (raise V)
Increase P (lower V)
Toward larger amount of gas None

Toward smaller amount of gas None
Temperature:
Increase T
Catalyst added:
None
Toward products if energy is a K increases with

reactant (endothermic)
increasing T
Toward reactants if energy is a K decreases with
product (exothermic)
increasing T
Rates of forward and reverse
reactions increase equally
None
46

CH 6 - Equilibrium-1

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12/27/2015

Chapter 6: Chemical Equilibrium

The Equilibrium Condition

Stoichiometry vs. Equilibrium

Most reactions, however, do not

Every reaction has a forward and a reverse!

Reaching Equilibrium on the

Two reactions are happening:

Reaching equilibrium requires that reactions

Once equilibrium is reached, there is no

Reached through dynamic balance of

(~no solid Ca forms)

Equilibrium lies far to the left

Initial and Equilibrium Concentrations for the

Experiments carried out at a certain temperature, but with

The Equilibrium Constant

The Equilibrium Constant

The Equilibrium Constant:

The Equilibrium Constant:

Varying the starting concentrations gives different

Equilibrium Constant - UNITS

This definition of the equilibrium

The Equilibrium Constant (contd.)

At equilibrium [NH3] = 3.1 x 10-2 M, [N2] = 8.5 x 10-1 M, and

We write Kc to indicate that we are using concentrations.

The Equilibrium Constant (contd.)

Notice that dividing by a reference state makes K unitless.

Reaching Equilibrium from Different

The Equilibrium Constant

The Equilibrium Constant

(leaves few reactants)

Equilibrium lies far to the right

The Equilibrium Constant

(~no solid Ca forms)

Equilibrium lies far to the left

Solving Equilibrium Problems

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

c. N2O4 (g) 2NO2 (g)

Determining Equilibrium Concentrations from K

Determining Equilibrium Concentrations from K

moles CH4 = 0.40 M x 5.0 L = 2.0 moles

Using and Rearranging K

CS2(g) + 3 O2(g) CO2(g) + 2 SO2(g)

CO2(g) + 2 SO2(g) CS2(g) + 3 O2(g)

If the original reaction is multiplied by a factor n, the new

[CH4] = 0.387 mol/L

a) Calculate the value of K at 927oC for this reaction.

Shortcut if K is known: K is just the reciprocal of K from part a:

Shortcut if K is known: K =(K)1/3 = (0.0393)1/3 = 0.3399

Types of Equilibrium Constants

Equilibrium arises through dynamic balance

2NO2 (g) NO3 (g) + NO (g)

NO3 (g) + NO (g) 2NO2 (g)

Forward rate = k1[NO2][NO2] = k1[NO2]2

Kinetic Approach to Equilibrium

The RATE of forward reaction decreases as the reaction

Extent of the Reaction

The Reaction Quotient, Q

aA(g) + bB(g) cC(g) +dD(g)

Q has same form as K, but the concentrations are the actual

Reaction Direction and the

N2O4 (g) 2NO2 (g)

Ways of Expressing Q and K values