TOPIC 11:

KINETICS AND EQUILIBRIUM

Part 1 – Kinetics
Part 2 – General Equilibrium
 AIM#1 : How does Kinetics affect the
rate of chemical reactions?

 Kinetics: the branch of chemistry that deals with the

rates (how fast the reaction is) of chemical reactions
 Collision Theory:
1. In order for a reaction to occur, reactants must
collide with each other

2. An effective collision is when reactants come

together with the correct amount of energy and in
the correct position to form a product
 As the amount of effective collisions increases,
the faster products are formed
 How can we increase the reactions rate (increase
the # of effective collisions??
 FACTORS THAT AFFECT THE RATE OF
CHEMICAL REACTIONS

1. Nature of Reactants
2. Concentration
3. Surface Area
4. Pressure
5. Temperature
6. Adding a Catalyst
1. NATURE OF REACTANTS:

Reactions involve the breaking of old bonds and the

formation of new bonds. In general:

1. Covalent bonds are slower to react than ionic bonds

2. Breaking more bonds requires more energy than

making bonds during collisions
2. CONCENTRATION:

Increase concentration increase rate of reaction

(More particles available for collisions)

(especially if volume is decreased)

3. SURFACE AREA:

the more surface area that is exposed the more

chances there are for collisions (effective

collisions) and will increase rate of reaction

4. PRESSURE:
No effect on solids and liquids, only gases

Increasing pressure, decreases the volume, increasing

the rate of effective collisions – increases the rate of
reaction
5. TEMPERATURE:

Increasing temperature increases kinetic energy of

molecules, leading to an increase in the amount of

effective collisions – increasing the rate of reaction

6. CATALYST

Addition of a catalyst increases the rate of the reaction by

providing a different and easier pathway for the reaction

 AIM #2: HOW CAN WE CLASSIFY
ENERGY IN CHEMICAL REACTIONS?

 Enthalpy (H) – flow of energy (heat exchange)

at constant pressure when two systems are in
contact
 Measure only the change in enthalpy ΔH (the
difference between the potential energies of
the products and reactants)
 Δ H = + reaction is endothermic and
heat energy is added into the system

 Δ H = - reaction is exothermic and heat

energy is lost from the system
1. Look at the reactions (where is E term?)

CH4 + 2O2 CO2 + 2H2O + 890.4kJ

N2 + O2 + 66.4kJ 2NO2

2. Look at the H = heat of the reaction (Table I)

3. Potential Energy Diagrams

H = PE products – PE reactants
 Practice using Table I

 A negative value means that the reaction is exothermic

 If we were to rewrite the equation with the heat of the reaction
shown it would look like this

 It is added to the right side of the equation because it is exothermic

reaction in which heat is released as a product
 Exothermic can be also called spontaneous
 A positive value means that the reaction is endothermic
 If we were to rewrite the equation with the heat of the reaction shown
it would look like this

 It is added to the left side of the equation because it is endothermic

reaction in which heat is absorbed as a reactant
ENTROPY ΔS: disorder or randomness of
the matter and energy of a system (more
disordered/dispersal is favored)

Nature favors CHAOS (high entropy low

energy)
Thermodynamically favored processes or
reactions are those that involve a
decrease in internal energy of the
components and increase in entropy
These are spontaneous or
thermodynamically favored
 AIM: What is entropy?

Ex)Predict which has the largest increase in

entropy:

CO2(s)  CO2(g)
H2(g) + Cl2(g)  2HCl(g)
KNO3(s)  KNO3(l)
C(diamond)  C(graphite)
2 Conditions for a reaction to be considered spontaneous
1. Tendency toward lower energy (PE) exothermic
ΔH = (-) Table I
* products have lower energy and more stable
 2. Tendency toward randomness ΔS = (+)
Entropy  measure of randomness or disorder
Physical changed and entropy :

Solid Liquid Gas

Intermediate
Low Entropy High Entropy
Entropy
Table I (stability) greater exothermic reaction the more stable the products are ( lower PE)
 Spontaneous reactions: DOESN’T REQUIRE EFFORT
(proceed on their own without intervention)
Ex) ice melting, nuclear reactions- natural transmutation
Chemical changes and Entropy:

- Free elements (ex. O2, Na, Fe) high entropy

- Compounds (ex. H2O, NH3) lower entropy

- ***NATURE FAVORS REACTIONS THAT HAVE

LOW ENERGY AND HIGH ENTROPY***

ΔH  (negative, exothermic)
ΔS  (positive, high entropy)
 AIM # 3: HOW CAN WE INTERPRET
POTENTIAL ENERGY DIAGRAMS?

Show how the potential energy of reactant particles changes to

chemical potential energy stored in bonds

PE diagrams keep track of PE changes during a chemical

reaction in stages
For Example: A + B AB

The forward reaction is read from left to right

Compare the potential energy of the reactants to the potential
energy of the products in the forward reaction (PE diagram #1)

PE REACTANTS: 25 Joules PE PRODUCTS: 75Joules

*Energy must have been absorbed during the reactions

PE diagrams with this pattern represent endothermic reactions
 AIM: HOW CAN WE INTERPRET
POTENTIAL ENERGY DIAGRAMS?

FORWARD REACTION!!
 AIM: HOW CAN WE INTERPRET
POTENTIAL ENERGY DIAGRAMS?
Lets Label the Diagram
A. PE of Reactants

B. PE of Products

C. H (heat of reaction) = H = PE products – PE reactants

If H is positive [PE products  PE reactants] – endothermic
If H is negative [PE products  PE reactants] – exothermic
Table I – shows different chemical reactions and H for each one
 AIM: HOW CAN WE INTERPRET
POTENTIAL ENERGY DIAGRAMS?

Label the Diagram

D. PE of Activated Complex – intermediate molecule that forms when
reactants have an effective collision. It is unstable and temporary

E. Activation Energy of forward reaction – amount of energy needed to

start the reaction in the forward direction

F. Activation Energy (with catalyst) – amount of energy needed to start

the reaction if a catalyst is added

* Catalysts – speed the reaction rate by lowering the activation energy

needed to start a reactions (gives an alternate pathway)
For Example: A + B AB

Compare the potential energy of the reactants to the potential

energy of the products in the reverse reaction (PE diagram #2)

PE REACTANTS: 75 Joules PE PRODUCTS: 25Joules

*Energy must have been released during the reactions

PE diagrams with this pattern represent exothermic reactions
Which diagram is endothermic?
Exothermic?
 EQUILIBRIUM
AIM # 4: What is equilibrium?
 Equilibrium: when the forward and reverse reactions occur
at the same rate – it is a state of balance

 Physical Equilibrium: the changes that take place in

chemical reactions during physical processes such as
changes of state or dissolving.
- Phase Equilibrium: Equilibrium between phases
1. Solid and liquid phase – during melting the rate of dissolving
is equal to the rate of crystallization in a closed container
(system) (H20 (s) H2O (l))
 EQUILIBRIUM

2. Liquid and Gas phase – during this phase the rate of

evaporation is equal to the rate of condensation in a closed
container (H20 (l) H2O (g))
 Solution Equilibrium:
1. Solid/Liquid Solution – saturated solutions are examples of
solid/liquid solution equilibrium in a closed system (C12H6O11 (s)
/ C12H22O11 (aq)

2. Gas/Liquid Solution – in a closed system or container, there is

equilibrium between the gaseous and dissolved state of the gas

Chemical Equilibrium
as time progress in a reaction, the concentration of the
reactants can decrease causing the overall reaction to slow. As
this occurs the concentration of the products can increase
causing the reaction to reverse (indicated by a double arrow)
 AIM # 5: What are external factors that
affect a reaction at equilibrium?

Le Chateliers Principle
 If a stress is applied to a system at equilibrium the
equilibrium will shift to release the effects of the stress

Stressors:
1. Temperature
2. Concentration
3. Pressure
 TEMPERATURE
If you increase temperature, ALL reactions will speed up. The
endothermic reaction will speed up the most (away from
where the heat is)

Increase in temperature favors the endothermic reaction

Decrease in temperature will favor the exothermic reaction

* *The side you shift towards will increase and the side you shift
away from will decrease**
4Nh3 + 5O2  4NO + 6H2O + heat
 CONCENTRATION

 If you increase the concentration of a substance the

reaction will shift away from the substance

 4Nh3 + 5O2  4NO + 6H2O + heat

 Le Chateliers Principle

Increase conc. of Favors FORWARD reaction SHIFTS RIGHT

reactants Speeds up the forward direction

Decrease conc. of Favors REVERSE reaction SHIFTS LEFT

reactants Speeds up the REVERSE direction

Increase conc. of products Favors REVERSE reactions SHIFTS LEFT

Speeds up the REVERSE direction

Decrease conc. of the Favors FORWARD reaction SHIFTS RIGHT

products Speeds up the FORWARD direction
 CONCENTRATION

 ADD AWAY (increase)

 TAKE TOWARDS (decrease)

 Pen/pencil will go up on which ever side you shift

towards
 PRESSURE

Need to know how many gas molecules are on the reactant side
and on the product side

Equal # of gas molecules – pressure will have no effect!!

Increase pressure – shift from more gas molecules  towards less

gas molecules

Decrease pressure – shift from less  toward more

 PRESSURE

Ex)

4NH (g) + 5O2(g) 4NO(g) + 6H2O(g)

4 + 5 = 9 gas molecules 4+6 = 10 gas molecules

Increase pressure: shift to the left (more to less) 9 10

Decrease pressure: shift to the right (less to more) 9 10
What are the conditions at equilibrium?

 At equilibrium the rate of the forward

reaction is equal to the rate of the reverse
reaction
 Concentrations are constant not equal
 Adding a catalyst would speed up the
forward and reverse reactions to the same
extent