CHEMICAL

EQUILIBRIU
M
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 Reation
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
)+3
H2 (g
)
2 NH
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

H ( g )
) 2N 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