Chemical Equilibrum

Chapter 15
Readings:

Be able to:

The Concept of Dynamic

Equilibrium
Section 15.2
 Reaction Dynamics
 When a reaction starts, the reactants are consumed and
products are made.
 The reactant concentrations decrease, and the product
concentrations increase.
 As reactant concentration decreases, the forward reaction rate
decreases.

 Eventually, the products can react to re-form some of the

reactants, assuming the products are not allowed to escape.
 As product concentration increases, the reverse reaction rate
increases.

 Processes that proceed in both the forward and reverse

directions are said to be reversible.

reactants products
 Dynamic Equilibrium
As the forward reaction slows and the reverse reaction
accelerates, eventually they reach the same rate.

Dynamic equilibrium is the condition wherein the

rates of the forward and reverse reactions are equal.

Once the reaction reaches equilibrium, the

concentrations of all the chemicals remain constant
because the chemicals are being consumed and
made at the same rate.
 H2(g) + I2(g) 2 HI(g)

At t = 32, more At t = 48, amount

At t = 0, only At t = 16, reactants product than of product and
reactants are and products reactant are present, reactant in the
present, only the present, so both the the forward reaction mixture haven’t
forward reaction forward reaction slows down as the changed; the
can take place. and reverse reaction reactants run out, forward and reverse
can take place. and the reverse reactions are
[H2] = 8, [I2] = 8, reaction accelerates. proceeding at the
[HI] = 0 [H2] = 6, [I2] = 6, same rate. It has
[HI] = 4 [H2] = 4, [I2] = 4, reached
[HI] = 8 equilibrium.
 H2(g) + I2(g) 2 HI(g)
As the concentration of product increases and the
concentrations of reactants decrease, the rate of the forward
reaction slows down, and the rate of the reverse reaction
speeds up.

At dynamic equilibrium, the rate of the forward reaction is equal to

the rate of the reverse reaction.

The concentrations of reactants and products no longer change.

 Types of Reaction Completion
Chemical Equilibrium: state where the concentrations
of all reactants and products remain constant with time
(Concentrations of reactants and products ARE NOT
EQUAL)
Equilibrium of a reaction can be:
Far to the left:
 The amount of reactants left when RXN reaches equilibrium is
almost equal to the initial amounts

Far to the right:

 The amount of reactants left when a RXN reaches equilibrium is
negligible compared to the initial amounts

Or somewhere between

 Equilibrium (static or dynamic)
 When a reaction reaches equilibrium the molecules still have
a large amount of activity (THEY DO NOT STOP)
 In other words the reaction continues, but…

 The forward and reverse reactions are happening at the

same rate so the concentrations of reactants and products
does not to change.
An Analogy: Population Changes

However, after a time, emigration

will occur in both directions at the
When Country A citizens feel
same rate, leading to populations in
overcrowded, some will
Country A and Country B that are
emigrate to Country B .
constant but not necessarily equal.
 EXAMPLE
 N2O4(g) 2NO2(g)

 Which of the following happens when more N2O4 is

added to a closed container of this sample?
 The forward reaction will speed up
 The reverse reaction will speed up
 Nothing will happen
 WHY?
 Forward and Reverse
 The forward reaction will speed up because of increased
decomposition of the N2O4

 The reverse reaction will also speed up because their will

be a greater production of the products.
 The reaction will continue until a new equilibrium point is
reached, WILL THE NEW EQUILIBRIUM POINT
CONTAIN FEWER OR GREATER PRODUCT
MOLECULES?
Readings:

Be able to:

The Equilibrium Constant (K)

Section 15.3
 Equilibrium Constant
 An equilibrium expression is an equation that follows the
law of mass action and results in the equilibrium constant
for a reaction
 jA + kB iC + mD

Equilibrium expression = [C]i[D]m / [A]j[B]k = K

 Where
 K = equilibrium constant (no units)
Close to zero equilibrium towards reactants
Large positive value, equilibrium towards products
 ******The concentrations used are the concentrations at the
equilibrium point******
 Sample Problem
 Write the equilibrium expression for the following reaction:
 C3H8 (g) + 5O2 3CO2 (g) + 4H2O (g)
 SAMPLE PROBLEM
 The following equilibrium concentrations were observed for the
Haber process at 127°C:

 [NH3] = 3.1 X10-2 mol/L

 [N2] = 8.5 X 10-1 mol/L

 [H2] = 3.1 X 10-3 mol/L

 1. Write the equilibrium expression for the reaction
 2. Calculate the value of K at 127°C for this reaction.
 3. Calculate the value of the equilibrium constant for the following
reaction at 127°C.

 2NH3 N2 + 3H2
 SAMPLE PROBLEM
Determine the equilibrium constant for the
system
N2O4 2NO2 @ 25°C.

 The concentrations at equilibrium are as follows:

[N2O4] = 4.24 X 10-2 M
[NO2] = 1.41 X 10-2 M
 What does K tell us?
 When the value of Keq >> 1, the reaction reaches
equilibrium where there will be many more product
molecules present than reactant molecules.
 Equilibrium position is product favored

 When the value of Keq << 1, the reaction reaches

equilibrium where there will be many more reactant
molecules present than product molecules.
 Equilibrium position is reactant favored
A Large Equilibrium Constant
A Small Equilibrium Constant
 Practice writing K expression
 Write the equilibrium expression for each of the following:
 A) 2NO2(g) + 7 H2 (g) 2NH3(g) + 4H2O (g)

 B) C6H5COOH (aq) C6H5COO- (aq) + H+ (aq)

 Equilibrium Constants and
Chemical equations
 If a chemical equation is modified, then the equilibrium
constant equation will also be modified
 Three types of changes to chemical equation
 1) Reverse the equation
 2) Multiply equation coefficents by a factor (i.e. double, triple
etc)
 3) Add two equations to obtain a third “overall” reaction

 See next slides for how to modify the equilibrium expressions

 Relationships between K and
Chemical Equations
 When the reaction is written backward, the equilibrium
constant is inverted.

For the reaction aA + bB cC + dD, For the reaction cC + dD aA + bB,

the equilibrium constant expression is the equilibrium constant expression is
as follows: as follows:
 Relationships between K and
Chemical Equations
When the coefficients of an equation are multiplied
by a factor, the equilibrium constant is raised to
that factor.

For the reaction aA + bB cC, For the reaction 2aA + 2bB 2cC,
the equilibrium constant the equilibrium constant expression
expression is as follows: is as follows:
 Relationships between K and
Chemical Equations
When you add equations to get a new equation,
the equilibrium constant of the new equation is the
product of the equilibrium constants of the old
equations.
For the reactions (1) aA bB For the reaction aA cC, the
and (2) bB cC, the equilibrium equilibrium constant expression
constant expressions are as is as follows:
follows:
 Sample Problem
 Consider the following chemical equation and equilibrium
constant at 25°C.

 2COF2 (g) CO2 (g) + CF4 (g) K = 2.2 X 106

 Calculate the equilibrium constant for the following reaction

at 25°C

 2CO2 (g) + 2 CF4(g) 4COF2 (g) K’ = ??

 Sample Problem
 Predict the equilibrium constant for the first reaction shown
below given the equilibrium constants for the second and third
reactions

 CO2(g) + 3H2 (g) CH3OH (g) + H2O (g) K1 = ???

 CO(g) + H2O (g) CO2 (g) + H2 (g) K2 = 1.0 X 105

 CO (g) + 2H2 (g) CH3OH (g) K3 = 1.4 X 107

Readings:

Be able to:

Expressing the Equilibrium

Constant in Terms of Pressure
Section 15.4
 Equilibrium Constants for
Reactions Involving Gases
The concentration of a gas in a mixture is
proportional to its partial pressure.
Therefore, the equilibrium constant can be
expressed as the ratio of the partial pressures of
the gases.
• For aA(g) + bB(g) cC(g) + dD(g), the equilibrium
constant expressions are as follows:

or
 Another example
 An example is:
 N2O4(g) 2NO2(g)

Kc Kp

 Equilibrium expression based on • Equilibrium expression

concentrations of reactants and based on partial pressures
products
(in atm)
 Kc = [NO2]2 / [N2O4] • Kp = (PNO2)2 / PN2O4

Kc and Kp will not be equal values. WHY?

Relationship between Kp and Kc is below:
Kp = Kc(0.0821T)Δn
 SAMPLE PROBLEM
 Consider the following reaction
CS2 + 4H2 CH4 + 2H2S

The equilibrium constant K is 0.28 at 900°C. What is KP at

this temperature?
 SAMPLE
 The following equilibrium pressures at a certain temperature
were observed for the reaction

 2NO2 2NO + O2

 PNO2 = 0.55 atm

 PNO = 6.5 X 10-5 atm
 PO2 = 4.5 X 10-5 atm

 Calculate the value for the equilibrium constant KP at this

temperature.
 Heterogeneous Equilibria:
Reactions Involving Solids and
Liquids
Section 15.5
 WHAT IS IT?
 Heterogeneous equilibria – is equilibria that involves
more than one phase.

 CaCO3(s) CaO(s) + CO 2(g)

 We would assume that the equilibria equation would be:

 K = [CO2][CaO] / [CaCO3]
 However the equation is actually:
 K = [CO2]
 Looking at the balanced equation, why do you think this
is the K equation?
 Heterogeneous Equilibria
The amount of C is different, but the amounts of
CO and CO2 remain the same. Therefore, the
amount of C has no effect on the position of
equilibrium.
 SAMPLE QUESTION
 Write the expression for K for the following reactions:
 P4(s) + O2(g) P4O10(s)

 NH4NO3(s) N2O(g) + 2H2O(g)

 CO2(g) + NaOH(s) NaHCO3(s)

Readings:

Be able to:

Calculating the Equilibrium

Constant
Section 15.6
 Calculating Equilibrium Constants from
Measured Equilibrium Concentrations
The most direct way of finding the equilibrium
constant is to measure the amounts of reactants
and products in a mixture at equilibrium.

The equilibrium mixture may have different

amounts of reactants and products, but the value
of the equilibrium constant will always be the
same, as long as the temperature is kept constant.
The value of the equilibrium constant is independent of
the initial amounts of reactants and products.
H2(g) + I2(g) 2HI(g) at 445 °C
 Sample problem
 Diatomic iodine [I2] decomposes at high temperature to form
I atoms according to the reaction:

 I2 (g) 2I (g) Kc = 0.011 at 1200°C

 In an equilibrium mixture, the concentration of I2 is 0.10 M.

What is the equilibrium concentration of I?
 Sample Problem
 Consider the reaction :
 N2 (g) + O2 (g) 2NO (g) Kc = 0.055 @ 1800°C

 The reaction mixture starts with [NO] =0.0100 M and no

reactants. Find the equilibrium concentrations of N2, O2 and NO
at equilibrium
 Sample Problem
 Consider the reaction:
 N2O4 2NO2 (g) Kc = 0.36 @ 100°C

 If the reaction vessel initially contains [N2O4] = 0.0250 M

and no NO2. Find the equilibrium concentrations of N2O4
and NO2.
 The Reaction Quotient:
Predicting the Direction of
Change
Section 15.7
 Reaction Quotient Q
 Determined exactly the same as the equilibrium constant,
but initial concentrations are used in place of equilibrium
conditions.
 For the reaction
 jA + kB iC + mD
 Q = [C]i[D]m / [A]j[B]k
 If Q is less than the calculated K, the reaction proceeds
forward
 If Q is greater than K, the reaction proceeds backward
 If Q = K then the reaction is at equilibrium
 Sample
 For the synthesis of ammonia at 500°C, the equilibrium
constant is 6.0 X 10-2. Predict the direction in which the
system will shift to reach equilibrium in the following:

 [NH3]0 = 2.0 X10-4 M

 [N2]0 = 1.50 X10-5 M

 [H2]0 = 3.54 X 10-1 M
Finding Equilibrium
Concentrations
Section 15.8
Steps to Solving an Equilibrium problem
 1. Write the balanced equation for the RXN.
 2. Write the equilibrium expression using the law of mass action
 3. List the initial concentrations
 4. Calculate Q, and determine the direction of the shift to
equilibrium
 5. Define the change needed to reach equilibrium, and define
the equilibrium concentrations by applying the change to the
initial concentrations.
 6. Substitute the equilibrium concentrations into the equilibrium
expression and solve for the unknown
 7. Check your calculated equilibrium concentrations by making
sure they give the correct value of K.
 More STEPS
 6. Substitute the equilibrium concentrations into the
equilibrium expression and solve for the unknown
 7. Check your calculated equilibrium concentrations by
making sure they give the correct value of K.
 SAMPLE
 Carbon Monoxide reacts with steam to produce carbon
dioxide and hydrogen. At 700 K the equilibrium constant is
5.10. Calculate the equilibrium concentrations of all species
if 1.000 mol of each component is mixed in a 1.00-L flask
 SAMPLE
 Assume that gaseous hydrogen iodide is synthesized from hydrogen
gas and iodine vapor at a temperature where the equilibrium constant
is 1.00 X 102. Suppose HI at 5.000 X 10-1 atm, H2 at 1.000 X 10-2
atm, and I2 at 5.000 X 10-3 atm are mixed in a 5.000-L flask.
Calculate the equilibrium pressures of all species.
 SAMPLE
 At 1280°C the equilibrium constant (Kc) for the reaction
 Br2(g) 2Br(g)

 Is 1.1 X 10-3. If the initial concentrations are [Br2] = 6.3 X 10-2

M and [Br] = 1.2 X 10-2 M, calculate the concentrations of
these species at equilibrium.
 Sample Problem 15.11
 The reaction between I2 and Cl2 is carried out as follows:
 I2 (g) + Cl2 (g) 2ICl (g) Kp = 81.9 @ 25°C

 The initial pressures are as follows: PI2 = 0.150 atm, PCl2 = 0.150
atm, PICl = 0.00 atm. Find the equilibrium partial pressures of all
three substances.
 Sample Problem 15.12
 Consider the reaction below:
 2H2S(g) 2 H2 (g) + S2 (g) Kc = 1.67 X 10-7 @ 800°C

 If the following information is known, determine the equilibrium

concentration for S2

 [H2S] = 0.100 M, [H2] = [S2] = 0.00 M

 Sample Problem 15.13
 Consider the reaction for the decomposition of hydrogen sulfide:
 2H2S(g) 2 H2 (g) + S2 (g) Kc = 1.67 X 10-7 @ 800°C

 If the initial concentrations are [H2S] 1.00 X 10-4 M, [H2] = 0.00 M,

and [S2] = 0.00, find the equilibrium concentration of [S2]
Readings:

Be able to:

Factors that Affect Chemical

Equilibrium
Section 15.5
 The Principal
 Le Chatelier’s Principle – if a change is imposed on a
system at equilibrium, the position of the equilibrium will
shift in a direction that tends to reduce that change.
 OR
 If a component is added to a reaction system at
equilibrium, the equilibrium position will shift in the
direction that lowers the concentration of that component.
If a component is removed, the opposite effect occurs.
 SAMPLE Concentration
For the Haber process N2 + 3H2 2NH3

Assume the following

[N2] = 0.399 M [H2] = 1.197 M [NH3] = 0.202M

What will happen if 1.00 mol/L of N2 is injected into

the system?
 The effects of a change in pressure
 Three ways to change the pressure:
 Add or remove a gaseous reactant or product
This is what we did in the last example
 Add an inert gas (one not involved in the reaction)
Has no effect on the equilibrium position
Addition of the inert gas increases the total pressure, but has no
effect on the concentrations or partial pressure of the reactants or
products
 Change the volume of the container
Changes the concentrations and partial pressures of reactants
and products
As a container reduces its volume, the system deceases its volume
by reducing the total number of gaseous molecules in the system.
 SAMPLE #1
 Predict the shift in equilibrium position that will occur for each
of the following processes when the volume is reduced.

A. P4(s) + 6Cl2(g) 4PCl3(l)

B. PCl3(g) + Cl2(g) PCl5(g)

C. PCl3(g) + 3NH3(g) P(NH2)3(g) + 3HCl(g)

 Effects of Changing Temperature
 Different from the other changes because a change in
temperature changes the value of the equilibrium
constant K.
 In order to see how the change in temperature effects the
equilibrium we will look at 2 cases, an endothermic
reaction and an exothermic reaction
 Exothermic Reactions
 N2(g) + 3H2(g) 2NH3(g) + 92kJ

 If energy is added to this system, it can be predicted

that the shift will be in the direction that consumes
energy.
 In this case, to the left
 This shift would change the concentrations of the
reactants and products and would therefore change the
value of K.
 Endothermic Reactions
 556 kJ + CaCO3(s) CaO(s) + CO2(g)

 An increase in the temperature of this system will cause a

shift to the right
 Putting more energy in, would increase the rate at which
CaCO3 decomposes causing more product to form and
therefore causing the shift to the right.
 SAMPLE
 For each of the following reactions, predict how the value
of K changes as the temperature is increased.

A. N2(g) + O2(g) 2NO(g) ΔHo = 181 kJ

B. 2SO2(g) + O2(g) 2SO3(g) ΔHo = -198kJ

 Sample Problem 15.16
 The following reaction is exothermic
 2SO2 (g) + O2 (g) 2SO3 (g)

 What is the effect of increasing the temperature of the

reaction mixture? Decreasing the temerature?
 SPECIAL NOTE
 Of the four types of changes we have discussed only
changing the TEMPERATURE will change the value of K
for any given system at equilibrium