Chemical

Equilibrium
Chapters 14 & 16
Chemical Kinetics
 Chemical kinetics is a branch of chemistry
which deals strictly with the speed of
chemical reactions
 otherwise known as the rate of reaction
 The Collision Theory
Reactions occur when atoms or molecules
collide in an effective collision.
An effective collision is one which results in a
chemical reaction.
In order to have an effective collision the
particles must collide with:
 A proper alignment.
 Enough force to affect electrons and bonds.
Potential Energy Diagrams: Graphing
a Reacion
Activation Energy
 Activation energy is the energy required to
initiate a chemical reaction
 An activated complex is a molecule in an
intermediate state between the reactant and the
product
Endothermic Reaction
Exothermic Reaction
Intermediates
 Molecules that are created in the first stage
of a chemical reaction that is in the middle
between the initial reactant and the final
product
 The intermediate is completely consumed in a
reaction
 The intermediate is the species that is canceled
out when applying Hess’s Law
Reaction Mechanism
 A reaction mechanism is the way in which a
chemical reaction takes place and is
expressed in a series of chemical equations
Rate-Limiting Step
 The limiting reactant controls the amount of
product that is formed

 The Rate-Limiting Step is the slowest step

of a multi-step reaction that determines the
overall speed or rate
•Which car is the fastest?

•Why is the red car slower

than the yellow car?
What factors affect rate?
 To determine which factors affect rate, it
is important to determine what happens
during a chemical reaction first of all
 The particles of each of the reactants are
colliding with one another and transferring
energy
 The speed of the reaction depends on the
number of collisions and how effective those
collisions are
And those factors are …
 Nature of the Reactants
 Concentration of the Reactants
 Temperature
 Surface Area
 Catalysts
Nature of Reactants
 Bond Types
 Remember those IM forces!
 Metallic, Hydrogen, Ionic, Polar Covalent and
Non-polar Covalent
 The stronger the bond, the slower the reaction
 HOWEVER, remember that an Ionic
compound in an aqueous solution is broken
down into it’s cations and it’s anions which
react quickly
Concentration of Reactants
 As the concentration of the reactants
increases, the frequency of collisions
increases as does the rate
 In a gas system, the greater the
concentration, the greater the pressure;
therefore, increase in pressure leads to
an increase in reaction rate
Temperature
 As the average kinetic energy increases,
that would be the temperature, the number
of collisions increases and therefore the
rate of reaction increases
Surface Area
 The greater the surface area, the greater
the probability of surface collisions;
therefore, the reaction rate increases
Catalyst
 The presence of a catalyst lowers the
activation energy required to initiate a
reaction by providing an alternative
pathway. This alternative pathway allows
for a faster reaction rate
Energy of Reaction: Potential Energy
Diagram

Reactants

Products

{
potential energy

A R Activation
Energy

Addition of a catalyst

0
0 time
Reversible Reactions &
Dynamic Equilibrium
Define these terms.
 Reactant
 Product
 Dynamic Equilibrium
 Reversible Reaction
 Completion Reaction
Reversible Reaction
 A chemical reaction that proceeds in both
directions at the same time.
 As the product decomposes back into reactants
as it is being produced
 Ex. Ca2+(aq) + SO42-(aq) CaSO4(s)
Equilibrium
When two opposing changes occur at the
same rate
Physical:
evaporation  condensation
Chemical:
H2 + I2  2HI
HC2H3O2 + H2O  H3O+ + C2H3O2-
Chemical Equilibrium
 The point in a chemical reaction when
dynamic equilibrium has been achieved
and the concentration of the reactants and
products remains constant
Dynamic Equilibrium
 The rate of the forward reaction equals the
rate of the reverse reaction; AND,
 the concentration of the products and
reactants remain the same.
Rates can be graphed
 Reaction rates are graphed by plotting the
concentration in moles per liter by the time
in seconds
Comparison of Rates
 Let’s look at the reversible reaction of
Hydrogen and Iodine to form Hydrogen
iodide
H2 + I2 2HI
Forward Reaction Rate
 The rate of the forward reaction decreases
over time, because the concentration of the
reactants decreases

H2 + I2 2HI
Reaction Rate

Time
Reverse Reaction Rate
• The rate of the reverse reaction increases
over time, because the concentration of the
products increases
Reaction Rate

2HI  H2 + I2

Time
Rate Comparison
 The rates of opposing reactions equalize
at equilibrium
H2(g) + I2(g) ↔ 2HI(g)
H2 + I2 2HI
Reaction Rate

2HI  H2 + I2 equilibrium

Time
 What evidence might lead you to believe
that a chemical reaction was NOT at
equilibrium?
The Equilibrium Constant
 The equilibrium constant (Keq) is a number
that represents the concentrations of
reactants and products of a reversible
reaction at a given temperature
Keq = [products]
[reactants]
What does it mean?
 If the equilibrium constant is a high number,
the reaction favors the products; the
concentration of the products is greater
than that of the reactants
Calculating Keq
1. Write and balance the reaction equation
including states of matter.
2. Set up the equation:
[product 1]coefficient 1 ÷ [reactant 1]coefficient 1
*the concentration of any solid or pure liquid
is left out because the concentration
remains constant
Decomposition of water to form
Hydrogen gas and Oxygen gas.
1. 2H2O(l)  2H2(g) + O2(g)
2. Keq= [O2] x [H2]2
Solubility Constant
 The solubility product constant (Ksp) is a
number that represents the concentrations
of a solid and its aqueous ions at a given
temperature
Keq = [ion] [ion]
What it means
 If the solubility product constant is high, the
ions are favored over the solid. The higher
the Ksp, the greater the extent of dissolution.
 When would Ksp not apply?
Le Châtelier’s Principle
 How will a system at equilibrium respond to
additional stress?
 “When a system at equilibrium is subjected to a
stress, the system shifts in order to relieve the
effects of the stress and restore the equilibrium
conditions as closely as possible.”
What do you do when your foot
falls asleep?
 Adjust your legs so that the circulation will
be restored to your feet.
What do you do when your
stomache growls from hunger?
 Feed it!
What do you do when your checking
account is at a zero balance?
 Have your mom deposit more money, of
course!

 All of these are examples of how a system

at equilibrium responds to a stress in order
to regain the state of equilibrium
Huh?
 Chemical reactions respond to similar
stresses to the system

 Note: when a system returns to a state of

equilibrium, there is a new equilibrium point
because the original conditions have been
changed.
Effects of Le Châtelier’s
 Stresses due to change in concentration,
temperature and pressure are subject to Le
Châtelier’s Principle
Chemical Shift
 A chemical shift is when either the forward
or reverse reaction is favored by the
introduction of a stress.

Equilibrium
So . . .
 A forward shift is to the right of the reaction
in response to a stress

 A reverse shift is to the left of the reaction

in response to a stress
 For Example
Let’s look at the Haber Process
Haber Process
 The Haber Process is a process that is
used to produce ammonia
N2(g) + 3H2(g) 2NH3(g)

 Notice that it is a reversible reaction.

Haber Equilibrium
 At equilibrium, the rate of ammonia
production equals the rate at which
ammonia is decomposed into its elements.

 The concentrations (molarity) of ammonia,

nitrogen and hydrogen are constant.
Effect of Concentration
 If the [N2] is increased, in other words, we
add more reactant,

 Then, the reaction will shift to the right,

forward shift, in order to remove any
additional nitrogen
Forward Shift
 As a result, the [NH3] increases and the [H2]
decreases

N2 (g
)+
3H
2 (g)
2NH
3 (g)
Reverse Shift
 Suppose instead of nitrogen, the [NH3] is
increased.
 As a result of the [NH3] increasing, the [N2]
and the [H2] increases

( g)
) 2NH 3
3H 2( g
( g) +
N2
Completion
 A chemical reaction in which one of the
products is continuously removed will never
achieve equilibrium.

 This reaction is said to go to completion

Completion Reactions
 A chemical reaction that continues to
completion
 All (or nearly all) of the reactants are used up
in the chemical reaction.
 Products do not re-form any of the reactants.
 Also known as an irreversible reaction.
Common Ion Effect
 In a saturated solution of an ionic
compound, the ions are in equilibrium with
it’s solid form

AgCl(s) Ag+(aq) + Cl-(aq)

 If you add additional Cl- from a different

ionic parent, more AgCl will be produced
Reduction of Solubility
 The common ion effect reduces the
solubility of slightly soluble compounds
Effect of Volume Change
 What happens when you reduce the
volume of a system?
 The pressure increases, and the particles are
closer together

 The stress can be relieved by producing a

smaller number of particles
Example
 Let’s look again at the Haber process
N2(g) + 3H2(g) 2NH3(g)
 There are 4 moles of reactants and 2
moles of product

 Reducing the volume would shift the

reaction to the right where there are
fewer particles
Another Example
 Let’s look at the reaction of Hydrogen and
Chlorine to form Hydrochloric Acid
H2(g) + Cl2(g) 2HCl(g)

 There are 2 moles of reactant AND product

so an increase or a decrease in volume
would not cause the reaction to shift
Pressure Changes
 Pressure changes have almost no effect on
equilibrium reactions in solution

 Pressure effects the equilibrium of gaseous

species
Inert Gas
 The pressure of an equilibrium system can
be changed by adding an inert gas

 An inert gas does not react with any of the

reactants or products and so therefore does
not affect the equilibrium of the system
Changing the Temperature
 We can raise the temperature of a system
by adding energy in the form of heat
 Adding heat to a system is endothermic
 Removing heat from a system is exothermic
Lower the Temperature
 Because an exothermic reaction releases
heat, it will favor a decrease in the
temperature
 Lower the temperature in a system and the
reaction will shift to the exothermic side in order
to replace some of the lost heat
Raise the Temperature
 Because an endothermic reaction absorbs
heat, it will favor an increase in the
temperature
 Raise the temperature in a system and the
reaction will shift to the endothermic side in order
to absorb the excess
Again with the Haber Process
 Let’s add the change in enthalpy as part of
our reaction and see what happens

N2(g) + 3H2(g) 2NH3(g) + 91.8kJ

 What happens when we lower the
temperature?
Lower the Temperature in the
Haber Process
 When we lower the temperature, the
reaction shifts toward the exothermic side

N2(g) + 3H2(g) 2NH3(g) + 91.8kJ

 The [NH3] is increased and the [N2] and [H2]
is decreased
Effects of a Catalyst
 At equilibrium, a catalyst increases the
forward and reverse reactions equally

 However, if a system is NOT at equilibrium,

a catalyst will shorten the time needed to
achieve equilibrium
Summary of Effects
Direction of Stress Result of Shift
 [ ] decreases  Some substance replaced
 [ ] increases  Some substance removed
 Volume increases (pressure  Fewer product produced
dec)
 Volume decreases (pressure  More product produced
inc)
 Temperature increases  Endothermic reaction
favored
 Temperature decreases  Exothermic reaction favored
 Catalyst is added  No shift occurs
Problems, Yahoo!
 Consider the following reaction
904 kJ + 6H2O(g) + 4NO(g) 4NH3(g) + 5O2(g)

 What is the effect of . . .

 decreasing the temperature
 a shift to the left
 decreasing the volume
 shift right
Problems, continued
 904 kJ + 6H2O(g) + 4NO(g) 4NH3(g) + 5O2(g)

 What is the effect of . . .

 increasing [NO]
 shift right
 decreasing [H2O]
 shift left
The Equilibrium Constant (Keq)
 The Equilibrium Constant, known by Keq or
K, tells us how much reactant used or
product produced
What does that tell you?
 The larger the value for the equilibrium
constant the more the reaction goes to
completion. Irreversible reactions can
be thought to have an infinite
equilibrium constant so there are no
reactants left.
That means . . .
 The value for K is large when products
dominate the mixture.
 The value for K is small when the reactants
dominate the mixture.
Homogenous System
 For a homogenous system at equilibrium,
you divide the [product] by the [reactant]
A(g) B(g)

Keq = [B] / [A]

Let’s Try Calculations
 For a simple homogenous system, if the
concentration of the reactant is 0.2M and
the product is 0.02M, what is Keq?

Keq = [B] / [A]

Keq = 0.02M / 0.2M
Keq = 0.1
Let’s get more complicated!
 What if our system has more parts than a
single reactant and product
xA(g) + yB(g) zC(g) + qD(g)
then
Keq = [C]z[D]q / [A]x[B]y
Solve it!
 Write a Keq equation for the following
reaction and evaluate Keq if [NH3]=0.2M;
[N2]=0.04M, and [H2]=0.01M.
N2(g) + 3H2(g) 2NH3(g)
Keq = [NH3]2 / [N2][H2]3
Keq = (0.2M)2/(0.04M)(0.01M)3
Keq = 1 x 106
ignore the units!!!
Solubility Product Constant (Ksp)
 The Solubility Product Constant (Ksp) is a
special type of equilibrium that measures
the concentration of ionic compounds in
water
Ionic Compounds Dissociate in
Water
 An ionic compound dissolves in water
AB(s) A+(aq) + B-(aq)
Keq = [A+][B-] / [AB]
so . . .
Keq . [AB] = [A+][B-] = Ksp
Let’s write some Ksp
 Write the Ksp expression for BaSO4
BaSO4 Ba2+ + SO42-
Ksp BaSO4 = [Ba2+] . [SO42-]

 Now, try to write the Ksp for PbI2

PbI2 Pb2+ + 2I-
Ksp = [Pb2+] . [ I-]2
Problems with Keq
 Problem: In an experiment, hydrogen gas
and iodine gas were placed in a container
which was sealed and allowed to come to
equilibrium with Hydrogen iodide gas. At the
start of the experiment, [H2]=0.001M and
[I2]=0.002; and at the end, the
[HI]=0.00186M.
 a. calculate [ ] for H2 and I2 in M
 b. calculate Keq
Step 1:
 Write out the equation for the reaction
H2(g) + I2(g) 2HI(g)
Step 2:
 Start solving the problem by first
constructing a table for the information

Substance [H2] [I2] [HI]

(M) (M) (M)
Initial [ ] 0.001 0.002 0.00
[]
Equil. [ ] 0.00186
Step 3:
 Use the coefficients as simple whole
number ratios in order to calculate the
proportions of products to reactants
 It takes 1 mole of H2 and 1 mole of I2 to produce
2 moles of HI
 Therefore, if there were 2 moles of HI produced,
it required 1 mole of H2 and 1 mole of I2
Step 3: continued
 Calculate the proportions and add the
information into the table

Substance [H2] [I2] [HI]

(M) (M) (M)
Initial [ ] 0.001 0.002 0.00
[] -0.00093 -0.00093 +0.00186
Equil. [ ] 0.00186
Step 4:
 If you can calculate the change in
concentration, you can calculate the
equilibrium concentration by taking the
initial concentration and adding or
subtracting the change
Step 4: continued
 Calculate the equilibrium concentration and
add the information to the table

Substance [H2] [I2] [HI]

(M) (M) (M)
Initial [ ] 0.001 0.002 0.00
[] -0.00093 -0.00093 +0.00186
Equil. [ ] 7.00 x 10-5 1.07 x 10-3 0.00186