Chapter 15: Chemical Equilibrium

Chem 102
Dr. Eloranta
Equilibrium

State in which competing processes are balanced so

that no observable change takes place as time passes.

Lift

Gravity

Sometimes called “dynamic equilibrium”

2
Physical Equilibrium

• Balance of competing physical

processes:
• Evaporation vs. condensation
• Freezing vs. melting

• At equilibrium: rate of
evaporation equals rate of
condensation
• Net result: No observable
change (individual molecules
move in a balanced way)

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Chemical Equilibrium
• Balance of two or more chemical reactions

• At equilibrium: rate of
decomposition equals rate of
dimerization
• [N2O4] and [NO2] do not change
over time
• Individual molecules react but in a
balanced way
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Dynamic equilibrium

rate of forward reaction = rate of reverse reaction

• Reactions are still occurring, but the rates are equal

• An individual molecule could react (or not)
• No net change in concentrations of reactants or
products over time
• concentrations of reactants and products are not
necessarily equal to each other!
• all chemical reactions are theoretically reversible, but
sometimes this can be ignored because reverse rate
is very small
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Dynamic Equilibrium
Side note:
IUPAC prefers: ⇌
May use: ⇄
• At equilibrium: Do not use ⟷, ⇔, ⥋
• forward rate = reverse rate
note: kf does not necessarily equal kr

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7
 The Equilibrium Constant, K

• Concentrations of the reactants and products are not

necessarily equal at equilibrium
• Quantify relative concentrations (at equilibrium) with the
equilibrium constant (K)

Products
Law of mass action:
Reactants

Note: K and k are different quantities!

8
Relationship between K and k

For an elementary step at equilibrium (because we

know the reaction order from the coefficients):

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Equilibrium constant - notes

• Do not include pure liquids or solids in K expression

(later: their activity is equal to one)
• Solutions: Use molarity (M) units
• Gases: Use pressure in atmospheres (atm)
• K has no units, regardless of the form of the equation
(you can learn more about this in Chem 321/351)
• K is temperature dependent
• More later:
Kc for solutions (concentration - M)
Kp for gases (partial pressure - atm)

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Significance of K

• What does the magnitude of K tell us about the reaction

at equilibrium?

• At equilibrium, would you expect a higher concentration

of reactants or products?

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Significance of K

• What does the magnitude of K tell us about the reaction

at equilibrium?

• At equilibrium, would you expect a higher concentration

of reactants or products?

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K math rules

If you reverse the reaction (as written), invert K

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K math rules

If you multiply an equation by a factor, raise the equilibrium

constant to the same factor

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K math rules

If you add two equations to get an overall reaction,

multiply the equilibrium constants to get the overall
equilibrium constant

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Kc and Kp

• Kc refers to K with units of molarity

• Kp refers to K using the partial pressure of the gases in
units of atmospheres

• The two are related to one another via the ideal gas law:

• Here: R = 0.08206 L atm / mol K

• Δn = difference in total moles of gas (gas moles in
products - gas moles in reactants)
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Heterogeneous equilibria

• Heterogeneous: More than one state present

(solid, liquid, gas)
• Remember: do not include pure solids or liquids in K

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Heterogeneous equilibrium example

• Write K expression for:

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Concentration changes during a reaction to reach
equilibrium

Given the following balanced reaction: A(g) ⇌ 2 B(g)

Initial Equilibrium

Change 0.75M A
1M A
-0.25 M A 0.50M B
+0.50 M B
(Stoichiometry)

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 The Reaction Quotient, Q

• Given a set of conditions, can we predict which way the

reaction will proceed?
• Q is defined the same way as K, except Q is the actual
ratio of products to reactants under given conditions, not
necessarily at equilibrium

K is always evaluated using equilibrium concentrations!

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Q example

• Say you start a reaction with only the reactants present

•Q=

• Say you start a reaction with only the products present

•Q=

• Say you had equal concentrations of reactants and products

•Q=

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Reaction quotient, Q

We can compare Q and K to determine

• Is the reaction at equilibrium?
• If not at equilibrium, which direction would the reaction
need to proceed to reach equilibrium?
Relationship Condition Direction

Q=K At equilibrium At equilibrium (no change)

Too little
Q<K product / too Toward products (to the right)
much reactant

Too much
Q>K product / too Toward reactants (to the left)
little reactant

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Reaction quotient, Q

Given the following concentrations, which way would the

reaction proceed to try to reach equilibrium?

A⇌B
Eq. concentrations!

[A] (M) [B] (M) Q Reaction direction?

3.0 1.0
1.0 1.0
5.0 1.0
3.0 1.5

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ICE Charts or ICE Tables (aka BRA Charts)
Set up a table to describe what will happen in the reaction
• Units are always M or atm
• Use Q to determine which way the reaction will proceed

A⇌B
A ⇌ B

Initial Initial [A] (M) Initial [B] (M)

Quantity changed in Quantity changed in

Change the reaction (M) the reaction (M)

Equilibrium [A] Equilibrium [B]

Equilibrium
(M) (M)
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ICE Charts

Given an initial set of conditions, and a value for K, can

we determine the equilibrium concentrations?
Plug in and solve
A⇌B

A ⇌ B

Initial 1.0 (M) 0.0 (M)

Change -x +x At equilibrium:
[A] = 0.17 M = 1 - 0.83
Equilibrium 1.0 - x x [B] = 0.83 M

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ICE Charts

A⇌B

A ⇌ B

Initial 1.0 (M) 1.0 (M)

Change -x +x At equilibrium:
Equilibrium 1.0 - x 1.0 + x [A] = 0.33 M
[B] = 1.67 M

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Stoichiometry matters

Cl2(g) ⇌ 2 Cl(g), K = 0.2 (not really, used for simplicity)

Cl2(g) ⇌ 2 Cl(g)

1.0 0.0
Initial
(M) (M)
Change -x +2x

Equilibrium 1.0 - x 2x

Quadratic equation!!!
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Quadratic Equation

Cannot have a negative concentration, so x = 0.2 M

[Cl2] = 1.0 - x = 0.8 M [Cl] = 2x = 0.4 M

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Multiple reactants/products
H2CO3(aq) ⇌ H (aq) + HCO (aq) K = 4.3x10
+
3
- -7

H2CO3(aq) ⇌ H+(aq) HCO3-(aq)

Initial 0.1 M 0M 0M

Change -x +x +x

Equilibrium 0.1 - x x x

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A shortcut for quadratic equations

If x < 5% of the term with it, you can ignore it in the

denominator to simplify the equation

Assume x is small compared to 0.1

Much easier to solve:

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Must test our assumption to see if it was valid

In our case, we assumed x < 5% (0.1)

Is this true?

In this case, we made a good assumption (0.21% < 5%)

Notice that we got the same answer (within rounding).

Note: x is not zero, just small.

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Method of successive approximations
-
HF(aq) ⇌ H (aq) + F (aq)
+
K = 7.2x10-4

HF(aq) ⇌ H+(aq) F-(aq)

Initial 0.01 M 0M 0M

Change -x +x +x

Equilibrium 0.01 - x x x

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Method of Successive Approximations

• Clearly, our assumption

was bad, > 5 %!
• Cannot use this answer
• Must solve exactly with
quadratic equation

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Method of Successive Approximations

• Quadratic equation slows down calculations

• Often it is also possible to obtain the solution by iteration:
Take your answer from assuming x was small
First approximation

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Method of successive approximations

Plug back into your equation and solve for x again:

2nd 3rd
approximation approximation

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Method of successive approximations

Plug back into your equation and solve for x again:

4th
approximation

5th
approximation

Usually within 3-5 iterations, x will be

obtained with sufficient accuracy
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Method of successive approximations

HF(aq) ⇌ H+(aq) + F-(aq) K = 7.2x10-4

HF(aq) ⇌ H+(aq) F-(aq)

Initial 0.01 M 0M 0M

Change -x +x +x

Equilibrium 0.01 - x x x

At equilibrium: [H+] = 0.002 M (after rounding to

[HF] = 0.008 M [F-] = 0.002 M correct sig. figs.)

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Le Chatelier’s Principle

How does a system at equilibrium

respond to disturbances?
Henry Louis Le Châtelier
1850 - 1936

When a chemical system at equilibrium is

disturbed, the system shifts in a direction
that minimizes the disturbance.

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 Example - Changing concentration

N2O4 (g) ⇌ 2 NO2 (g) N2O4 will react to

reach equilibrium
At equilibrium Add extra N2O4 again

N2O4 N2O4 N2O4

NO2 N2O4 NO2 NO2
NO2 NO 2
NO2
NO2

Adding a higher concentration of reactant will cause the

equilibrium to shift right to attempt to reach equilibrium
again (Q = K)
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40
 Example - Changing concentration

N2O4 (g) ⇌ 2 NO2 (g) NO2 will react to

reach equilibrium
At equilibrium Add extra NO2 again

N2O4 N2O4 N2O4

NO2 NO2 N2O4
NO2 NO 2 NO2
NO2 NO2
NO2

• Adding a higher concentration of product will cause the

equilibrium to shift left to attempt to reach equilibrium
again (Q = K)
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42
Effect of concentration change on equilibrium

• Increasing concentration of one or more reactant (Q < K)

Reaction will shift right (toward products)
• Increasing concentration of one or more products (Q > K)
Reaction will shift left (toward reactants)

• Decreasing concentration of one or more reactants (Q > K)

Reaction will shift left (toward reactants)
• Decreasing concentration of one or more products (Q < K)
Reaction will shift right (toward products)

• K is constant, concentrations are changing such that Q → K

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Volume/Pressure changes in equilibrium

H2O (l) ⇌ H2O (g)

Higher P:
Equilibrium shifts left
(away from gas)

Lower P:
Equilibrium shifts right
(toward gas)

“Gas would like to

occupy more space
than liquid”

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 Volume/Pressure changes in equilibrium

N2(g) + 3 H2(g) ⇌ 2 NH3(g)

Higher P:
Equilibrium shifts
toward fewer moles of gas

Lower P:
Equilibrium shifts
toward more moles of gas

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Effect of volume (or pressure) change on
equilibrium
• Decreasing volume (increasing pressure) causes
equilibrium to shift to fewer moles of gas particles
• Increasing volume (decreasing pressure) causes
equilibrium to shift to more moles of gas particles

• If equal number of moles of gas on both sides of the

reaction, change in volume or pressure has no effect
• Adding an inert gas to a mixture (at fixed volume) has no
effect

• K is constant as long as T is constant

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Le Chatelier’s Principle and Temperature

• Think of heat as a “reactant” or “product”

• Exothermic reaction: A + B ⇌ C + D + heat

• Endothermic reaction: A + B + heat ⇌ C + D

• Adding or removing heat will change the equilibrium

removing heat = lower T
adding heat = higher T
• K is changing in this case

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Endothermic reaction

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Le Chatelier’s Principle and Temperature

• Increasing temperature: Exothermic reaction shifts toward

reactants
• Increasing temperature: Endothermic reaction shifts toward
products

• Decreasing temperature: Exothermic reaction shifts toward

products
• Decreasing temperature: Endothermic reaction shifts toward
reactants

• Adding heat favors endothermic reaction

• Removing heat favors exothermic reaction

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General tips for this section

• Understand definitions
Dynamic equilibrium, how rates relate, equilibrium
constant, Kc vs. Kp, reversibility, etc.
• Understand Q vs. K
Which way will the reaction proceed?
• Understand ICE charts
Be able to solve any ice chart:
• may need quadratic equation or successive approx.
• Understand the 5 % validity test
• Le Chatelier’s principle

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Additional example #1

What is Kc for the reaction

2 CH4(g) ⇌ C2H2(g) + 3 H2(g)
if we start with only CH4, the initial [CH4] is 0.300 M and
the equilibrium [C2H2] = 0.045 M?

Note, we have a mixture of some initial and some

equilibrium concentrations

The best way to answer this problem is using an ICE

table.
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Additional example #1
1. First set up the ICE table and add the values in the problem
2 CH4(g) ⇌ C2H2(g) + 3 H2(g)

[CH4] [C2H2] [H2]

Initial 0.300 M 0.000 M 0.000 M
Change
Equilibrium 0.045 M

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 Additional example #1
2. For a substance whose initial and equilibrium concentrations are
known, complete ‘change’
2 CH4(g) ⇌ C2H2(g) + 3 H2(g)

[CH4] [C2H2] [H2]

Initial 0.300 M 0.000 M 0.000 M
Change +0.045 M
Equilibrium 0.045 M

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Additional example #1
3. Use reaction stoichiometry to complete the rest
of the ‘change’ row
2 CH4(g) ⇌ C2H2(g) + 3 H2(g) Signs are
important!

[CH4] [C2H2] [H2]

Initial 0.300 0.000 0.000
Change -0.090 x2 +0.045 x3 +0.135
Equilibrium 0.045

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 Additional example #1
4. Sum each column to find the equilibrium
concentrations of all substances
2 CH4(g) ⇌ C2H2(g) + 3 H2(g)

[CH4] [C2H2] [H2]

Initial 0.300 0.000 0.000
+ +
Change -0.090 +0.045 +0.135
Equilibrium =0.210 0.045 = 0.135

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Additional example #1
5. Finally, use the equilibrium concentrations to
calculate Kc
2 CH4(g) ⇌ C2H2(g) + 3 H2(g)

3
[C2 H2 ][H2 ]
Kc  2
We calculated
[CH4 ] Kc even without
Kc is small, 3 all equilibrium
equilibrium
0.045 0.135 concentrations
 2 in the problem
lies on the 0.210
left 3
2.51x10

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Additional example #2
When given Kc and all but one of the equilibrium
concentrations, what is the equilibrium [CO2] in the
reaction: 2 COF2(g) ⇌ CO2(g) + CF4(g)
if Kc = 2.00 at 1000 °C, the equilibrium [COF2] = 0.255 M
and equilibrium [CF4] = 0.118 M?

We know
[CO 2 ][CF4 ]
all terms Kc  2
except
[CO2] [COF2 ]

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Additional example #2
To solve, simply rearrange the Kc equation

[CO 2 ][CF4 ]
Kc  2
[COF2 ] 2
Kc [COF2 ]
[CO 2 ] 
[CF4 ]
To check, insert 2
values into 2.00 (0.255 M)

expression 0.118 M
Kc = 1.99 ≈ 2.00
1.10 M


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Additional example #3

What is the equilibrium concentration of

H2 for the reaction:
2 H2S(g) ⇌ 2 H2(g) + S2(g)
if Kc = 1.67x10-7 at 800 °C and the
reaction initially contains only 0.0125 mol
H2S in a 0.500 L flask?

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Additional example #3

• The initial [H2S] is 0.0125 mol/0.500 L = 0.025 M

• Notice Kc = 1.67x10-7 is very small compared with
the initial [H2S]
• We expect the [H2S] to change only very slightly
from its initial conditions and we can ignore this
change in calculations - this simplifies the algebra
• Next, set up an ICE table

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Additional example #3

2 H2S(g) ⇌ 2 H2(g) + S2(g)

[H2S] [H2] [S2] [H2S]

decreases
Initial 0.025 0.000 0.000 and [H2] and
[S2] increase
Change -2x +2x +x as the system
Equilibrium 0.025-2x +2x +x approaches
equilibrium

Next, solve for ‘x’

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Additional example #3

[H2 ]2 [S2 ]
Kc 
[H2 S]2
(2x)2 x
1.67x10 7 
(0.0250  2x)2
4x 3 A cubic

(0.0250  2x)2 equation that is
difficult to solve!

If x is small, we can ignore


it in the denominator of this
equation

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 Additional example #3

4x 3 4x 3
1.67x10 7  
(0.0250)2 6.25x10 4
7 4
1.67x10 6.25x10
x3 
4 No need to solve
x 2.97x10 4 a cubic equation!
?

 • The equilibrium [H 2] = 2·x = 5.94x10 -4 M

• If this value is < 5% of the initial concentration, the assumption

error is small and the method is acceptable (in this case 2.4%)

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 Additional example #4

Consider heterogeneous equilibrium:

When the system is compressed from 10.0 L to 0.1 L at

constant temperature of 650 K, how many grams of
MgCO3(s) is formed? Assume that CO2 can be treated as an
ideal gas and sufficient amounts of both solids are present.

1. Before compression: V1 = 10.0 L, P1 = 0.026 atm

(from Kp = PCO2), and T = 650 K. Ideal gas law:

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Additional example #4

2. After compression: V2 = 0.100 L, P2 = 0.026 atm

(from Kp = PCO2), and T = 650 K. Ideal gas law:

3. The number of moles of CO2 consumed:

Based on the stoichiometry, this also gives the number of

moles of MgCO3(s) formed (4.826x10-3 mol). The mass is:

(molar mass of MgCO3 is 84.3130 g/mol)

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