REACTION RATES

HAPPY BEKA CHIMBENDE

 Learning Objectives:

Explain examples of chemical reactions.

❑ Expressing the Reaction Rate.
❑ Factors that affect rates of reaction.
❑ State the equilibrium law and Lechateliers
principle.
❑ Expressing equilibrium constants
❑ Explain chemical reactions of biological
compounds and interpretation of results
 CHEMICAL REACTIONS
▪ Divided into 2 categories
1. Chemical kinetics – deals with chemical
reactions(system) from the initiation stage to the
point where the system seems to undergo no further
chemical change.
2. Chemical Equilibria –study of a chemical system
after all apparent chemical changes have stopped
▪ A chemical reaction will occur when there is:
i. Effective collisions between compounds
( reactants)
ii. Chemical bond breaking between reactants
iii. Creation of new bonds into new products
 CHEMICAL KINETICS
▪ Deals with the following aspects of a chemical
reaction:
i. Rate (speed) of chemical reactions.
ii. Energy Changes involved in the reactions.
iii. Molecular structural characteristics of chemical
system
iv. Reaction mechanism of chemical species.
 RATES OF CHEMICAL REACTIONS
▪ Rate at which products are formed or rate at
which reactants are used up in a chemical
reaction.
▪ Vary immensely from reaction to the other:
i. Instantaneous rates –reactants used up very
fast to form products, e.g., explosions,
neutralisation or many other ionic reactions.
ii. Gradual/ Slow rates –take a considerable
time to form products, e.g., fermentation,
decomposition, corrosion etc.
EXPRESSING THE REACTION RATE
▪ Measured in moles of reactants disappearing or moles
of product appearing per unit time.
▪ For a reaction of compounds A and B to produce C
written as: 𝐀 + 𝐁 → 𝐂, the rate of reaction will given
by:
∆𝑨 ∆𝑩 ∆[𝑪]
𝑹𝒂𝒕𝒆 = − =− =+
∆𝒕 ∆𝒕 ∆𝒕
where ∆ 𝑨 = 𝑨𝟐 − 𝑨𝟏 𝒂𝒏𝒅 ∆𝒕 = 𝒕𝟐 − 𝒕𝟏

▪ And 𝐴2 is the molar concentration at some time 𝑡2 and

𝐴1 is the molar concentration at an earlier time 𝑡1
▪ The –ve sign indicates a decrease in molar
concentrations of reactants and +ve sign is increase of
molar concentration of products
 EXPRESSING THE REACTION RATE
General reactions that undergo self decomposition:
A → B, we measure the concentration of A at t1 and at t2:

change in concentration of A conc A2 - conc A1 D[A]

Rate = =- =-
change in time t2 - t1 Dt

Square brackets indicate a concentration in moles per liter.

The negative sign is used because the concentration of A is

decreasing.
Example: Concentration of O3 at Various Times in its
Reaction with C2H4 at 303 K

Concentration of O3
Time (s) (mol/L)

0.0 3.20x10-5 D [C2H4]

rate = -
10.0 2.42x10-5 Dt
20.0 1.95x10-5 D [O3]
=-
30.0 1.63x10-5 Dt
40.0 1.40x10-5
50.0 1.23x10-5
60.0 1.10x10-5
PLOTS OF [REACTANT] AND [PRODUCT] VS. TIME.
C2H4 + O3 → C2H4O + O2

[O2] increases just as fast as

[C2H4] decreases.

D[C2H4] D[O3]
Rate = - =-
Dt Dt

D[C2H4O] D[O2]
= =
Dt Dt
PLOTS OF [REACTANT] AND [PRODUCT] VS. TIME.
H2 + I2 → 2HI
[HI] increases twice as
fast as [H2] decreases.

D[H2] D[I2] 1 D[HI]

Rate = - =- =
Dt Dt 2 Dt

D[IH] D[H2] D[I2]

Rate = = -2 = -2
Dt Dt Dt

The expression for the rate of a reaction

and its numerical value depend on which
substance serves as the reference.
In general, for the reaction

aA + bB → cC + dD

where a, b, c, and d are the coefficients for the balanced

equation, the rate is expressed as:

1 D[A] 1 D[B] = 1 D[C] = 1 D[D]

rate = - =-
a Dt b Dt c Dt d Dt
 EXAMPLE
• 6. In the reaction H2O2(aq) → H2O(l) + ½ O2(g),
the initial concentration of H2O2 is 0.2546 M,
and the initial rate of reaction is 9.32×10–4 M s–
1. What will be [H O ] at t = 35 s?
2 2
Solution
• Use the definition of rate (change in
concentration over change in time), recognizing
that the initial rate for the loss of hydrogen
peroxide is negative and at t = 0 s, [H2O2] =
0.2546 M
Solution Continue
 FACTORS THAT AFFECT RATES OF REACTION
1. CONCENTRATION
▪ The higher the concentration of reactants, the
greater the reaction rate.
▪ High concentration increases the rate of reaction
due to the increased number of molecules.
▪ Probability of collision increases as the
concentration of reactants increases.
▪ For low concentrated reactions, the rate of
reaction will be decreased due to fewer number
of molecules ( reactants) in the solution.
 FACTORS THAT AFFECT RATES OF REACTION
2. TEMPERATURE
▪ Increase in temperature of the reactive system
increases the rate of reaction.
▪ The increased temperature increases the number of
collisions of the molecules by increasing the
average kinetic energy of the molecules.
3. CATALYSTS
▪ Speeds up the rate at which the reaction proceeds
by reducing the activation energy for the reaction.
▪ Changes the nature of the transition complex or
introduce new steps that are faster than uncatalysed
reaction without altering the final product.
 CHEMICAL EQUILIBRIUM
▪ In many chemical reactions, when all the reactants
are converted to products , it signifies that the
reaction has gone to completion (irreversible).
▪ However, there are many cases in which, as products
are formed, they react with each other to form back
their reactants.
▪ Such reactions are reversible.
▪ A reversible reaction is characterised by
simultaneous occurrence of two opposed chemical
reactions:
i. Forward reaction, and
ii. Reverse reaction.
 CHEMICAL EQUILIBRIUM
▪ While irreversible reactions reach completion,
reversible reactions proceed in both directions
▪ In reversible reactions, when the rate of forward
reaction equals the rate of reverse reaction, it
means the system is at chemical equilibrium.
▪ At a chemical equilibrium, concentrations of
reactants and products remain constant but not
necessarily equal.
▪ Therefore, the number of reacting molecules do
not change at that point.
 EQUILIBRIUM POINT
▪ An increase in rate of a forward reaction
produces more products which in turn may
also increase the rate of a backward reaction
hence restoring another equilibrium state
▪ Therefore an equilibrium point can favor the
products(lie to the right) or the reactants(lie to
the left)
▪ When an equilibrium is reached , any change
in the system effectively shifts the equilibrium
position
 EQUILIBRIUM POINT CONT’D
▪ At equilibrium, an equilibrium constant,
𝑲𝒆𝒒 can be obtained by taking the ratio of the
products concentration to the concentration of
the reactants
▪ For example:𝑁2 (𝑔) + 𝑂2 (𝑔) ↔ 2𝑁𝑂(𝑔)
[𝑵𝑶]𝟐
∴ 𝑲𝒆𝒒. =
[𝑵𝟐 ][𝑶𝟐 ]
▪ The molar concentrations are raised to a power
equal to the stoichiometric of the
stoichiometrically balanced equation.
 CHARACTERISTICS OF A SYSTEM IN CHEMICAL
EQUILIBRIUM
▪ Rates of the forward and reverse reactions are
equal;
▪ the system does not undergo any observable
change;
▪ The system is a closed system.
FACTORS AFFECTING THE EQUILIBRIUM
• Different factors affect the position of the
equilibrium position i.e. can shift either to the
left or to the right
• The factors include concentration, pressure but
not catalyst
• These factors only affect the position of the
equilibrium position and not the value (or
magnitude) of the equilibrium constant itself
• Only temperature can affect the value of an
equilibrium position
 EQUILIBRIUM CONSTANT
• Equilibrium constant can be expressed in terms of
concentrations (𝐾𝑐 ) for liquid solutions or pressure (𝐾𝑝 )
for gaseous state. Suppose you have an equilibrium
established between four substances A, B, C and D.

• Then the equilibrium constant can be expressed as the

equilibrium law below where c can be p i.e.
concentrations be pressure
EQUILIBRIUM CONSTANT cont..d
▪ Pure liquids and solids do not appear in the
equilibrium constant expression for which they take
part.
▪ Reason: the concentration, moles per litre, of pure
solid or liquid cannot be varied, and hence cannot
affect the equilibrium state.
▪ For example: 𝑪 𝒔 + 𝑶𝟐 (𝒈) ↔ 𝑪𝑶𝟐 (𝒈), has
[𝑪𝑶𝟐 ]
𝑲𝒆𝒒. =
[𝑶𝟐 ]
▪ What is the 𝐾𝑒𝑞. of the reaction below

𝑩𝒂𝟐+ 𝒂𝒒 + 𝑺𝑶𝟒𝟐− 𝒂𝒒 ↔ 𝑩𝒂𝑺𝑶𝟒 𝒔 ?

IMPORTANT NOTES ABOUT THE EQUILIBRIUM LAW
▪ The equilibrium law applies only to systems at
equilibrium.
▪ Kc or Kp is constant only so long as the
temperature remains constant. If the temperature
changes, the value of Kc or Kp will change
▪ The numerical value of Kc or Kp is unaffected by
changes in in concentrations of either reactants or
products
▪ Kc or Kp indicates the extent(how far) of a
chemical reaction but nothing about the rate(how
fast) of the reaction. The larger the Kc/p value the
near to completion the reaction
 THE EQUILIBRIUM LAW AND LE
CHATELIER’S PRINCIPLE
▪ Frenchman Henri Louis Le Chatelier was one
of the first chemists to investigate the effects
of different factors (such as temperature,
concentration and pressure) on equilibrium
▪ Then he made the following generalization
which still works today
▪ “if a system in equilibrium is subjected to a
change, processes will occur which tend to
counteract the change imposed”
 CHANGING CONCENTRATION
▪ The position of equilibrium is changed if you
change the concentration of something present
in the mixture.
▪ According to Le Chatelier's Principle, the
position of equilibrium moves in such a way as
to tend to undo the change that you have made.
▪ If you decrease the concentration of C(in
equation below), for example, the position of
equilibrium will move to the right to increase
the concentration again.
▪ If you decrease the concentration of C, the top
of the Kc expression gets smaller. That would
change the value of Kc. For that not to happen,
the concentrations of C and D will have to
increase again, and those of A and B must
decrease until a new balance is reached
 CHANGING PRESSURE
▪ This only applies to systems involving at least
one gas.
▪ That means that if you increase the pressure,
the position of equilibrium will move in such a
way as to decrease the pressure again - if that
is possible.
▪ It can do this by favouring the reaction which
produces the fewer molecules. If there is the
same number of molecules on each side of the
equation, then a change of pressure makes no
difference to the position of equilibrium.
TEMPERATURE AND EQUILIBRIUM
POSITION
▪ The position of equilibrium also changes if
you change the temperature.
▪ If you increase the temperature, the position of
equilibrium will move in such a way as to
reduce the temperature again. It will do that by
favouring the reaction which absorbs heat.
▪ Note that when the forward reaction is
exothermic then the reverse reaction would be
endothermic
TEMPERATURE vs. Kc VALUE
▪ With any equilibrium where the forward
reaction is exothermic, increasing the
temperature decreases the value of the
equilibrium constant.
▪ Where the forward reaction is
endothermic, increasing the temperature
increases the value of the equilibrium
constant.
 ADDING A CATALYST
▪ Equilibrium constants aren't changed if you add
(or change) a catalyst.
▪ The position of equilibrium is not changed if you
add (or change) a catalyst.
▪ A catalyst speeds up both the forward and back
reactions by exactly the same amount. Dynamic
equilibrium is established when the rates of the
forward and back reactions become equal. If a
catalyst speeds up both reactions to the same
extent, then they will remain equal without any
need for a shift in position of equilibrium.
 IMPORTANCE OF KINETICS AND
EQUILIBRIA
• Many people (managers, economists
,engineers etc.) will be involved in decisions
about the methods and materials in any
industrial processes
• But the major problems confronting a chemist
are to convert reactants into products as
1. quickly as possible
2. completely as possible
 NOTE THAT
▪ Rate of reaction is concerned with how fast
while an equilibrium is concerned with the
extent of the reaction
▪ The greater the rate value, the faster the
reaction
▪ The greater the equilibrium constant value, the
nearer the reaction to completion(i.e. the
reaction is almost complete)
▪ Would you interpret the reaction extent when
Kc ˂ 1, Kc ˃ 1 or Kc = 1 ?
 IMPORTANCE CONT’D
• The first problem is a kinetic one. It involves
obtaining a maximum rate of reaction and rate
of product formation
• The second problem is one of equilibrium. It
involves the choice of those conditions which
favour an optimum proportion of the product
in the equilibrium mixture
 SAMPLE PROBLEM:
Conder the reaction: 𝟐𝑯𝑰 𝒈 ↔ 𝑯𝟐 𝒈 + 𝑰𝟐 𝒈 .
Calculate the stoichiometric amount of moles left at
equilibrium for HI when its initial amount was 2
moles. The equilibrium constant for the reaction is
10.
PLAN: Write the 𝑲𝒆𝒒 expression for the reaction.
At equilibrium some of the HI will have
been converted to products, and therefore
𝑰𝟐 𝑎𝑛𝑑 𝑯𝟐 will have appeared. An expression
to account for the changes in concentration
leading to equilibrium must be shown.
 SAMPLE SOLUTION:

a. 1st write the equilibrium constant :

[𝐇𝟐 ][𝐈𝟐 ]
𝐊𝐜 =
[HI]2
b. Account for changes that have occurred at
equilibrium:
Species HI 𝐈𝟐 𝐇𝟐
Start 2.0 0.0 0.0
Change -2x +x +x
Final 2.0 – 2x x x
 SAMPLE SOLUTION : cont..d
c. Substitute the final concentrations into the 𝑲𝒄 :
𝒙 [𝒙]
𝑲𝒄 = 𝟐
= 𝟏𝟎
[𝟐. 𝟎 − 𝟐𝒙]
Take square root of both sides and then solve for x,
[𝒙]
= 𝟑. 𝟏𝟔
[𝟐. 𝟎 − 𝟐𝒙]

𝒙 = 𝟎. 𝟖𝟔
Therefore, at equilibrium:
𝑯𝑰 = 𝟐. 𝟎 − 𝟐 𝟎. 𝟖𝟔 = 𝟎. 𝟐𝟖𝑴
𝑰𝟐 = 𝑯𝟐 = 𝒙 = 𝟎. 𝟖𝟔𝑴
 PRACTICE QUESTION
1. 2CO2(g) 2CO(g) + O2(g), ∆H=+135kcal.
What would happen to the equilibrium position and
the value of equilibrium constant if
a) pressure is decreased.
b) temperature is increased.
2. In the reaction 3𝑂2 (𝑔) → 2𝑂3 (𝑔)(𝑜𝑧𝑜𝑛𝑒), the
rate of appearance of ozone was 1.50mol./ min.
What is the rate of disappearance of oxygen?
 PRACTICE QUESTION
3. The equilibrium constant for the reaction
𝑁𝐻4 𝐶𝑙 𝑠 ↔ 𝑁𝐻3 𝑔 + 𝐻𝐶𝑙 𝑔 𝑎𝑡 250 𝐶 is
𝐾𝑐 = 1.38 × 10−5 . Calculate the concentrations of
the components of the equilibrium mixture.
4. 1 mole of nitrogen and 3 moles of hydrogen were
mixed at 593K and 2.0 × 107 𝑃𝑎. At equilibrium the
mixture contained 1.5 moles of ammonia.
i. Write the equilibrium expression for 𝐾𝑐 .
ii. Find the mole fraction of each component and
thus their molar concentration.