CHEMICAL KINETICS – the area of chemistry concerned with the speed or rate at which chemical reaction occurs

COLLISION THEORY – explains how a chemical reaction take place. According to this theory two conditions must be satisfied for
a chemical reaction to occur:
1) particles of reactants must collide with one another
2) colliding particles must have sufficient energy

Energy of Activation (Ea)  activation energy; the minimum amount of energy needed for a reaction to occur

ENERGY DIAGRAMS

THE RATE OF CHEMICAL REACTION

REACTION RATE /Rate of Reaction  is the change in the concentration of a reactant or a product per unit time
∆𝐶
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = − ∆𝑡 for reactants (negative sign is indicated because the concentration decreases with time)

∆𝐶
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = ∆𝑡
for products (no need to indicate negative if concentration of products is increasing)

Change in Concentration (ΔC) of the products is always a positive quantity.

Consider the reaction of hydrogen with fluorine:

𝑯𝟐 (𝑔) + 𝑭𝟐 (𝑔) → 𝟐 𝑯𝑭 (𝑔)
Each mol per liter of H2 produces 2 mol per liter of HF. It means that the rate at which HF appears is twice as fast as H2
disappears. The rate of disappearance of H2 can be expressed as
∆[𝐻2 ]
𝑟𝑎𝑡𝑒 = −
∆𝑡
where Δ[H2] = change in concentration of H2
Δt = change in time

The change in the concentration of H2 can be expressed as

∆[𝐻2 ] = [𝐻2 ]𝑓𝑖𝑛𝑎𝑙 − [𝐻2 ]𝑖𝑛𝑖𝑡𝑖𝑎𝑙
where [H2]final = final concentration of H2
[H2]initial = initial concentration of H2

Note the Δ[H2] is negative since [H2]final is less than [H2]initial. The rate of reaction is always positive. The presence of the negative
sign in the above rate expression makes the value of the rate of the disappearance of H2 positive.

The rate of reaction for the given example in terms of each component can be expressed as
∆[𝐻2 ] ∆[𝐹2 ] 1 ∆[𝐻𝐹]
𝑟𝑎𝑡𝑒 = − = − =
∆𝑡 ∆𝑡 2 ∆𝑡
where:
∆𝐻𝐹
= 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑎𝑝𝑝𝑒𝑎𝑟𝑎𝑛𝑐𝑒 𝑜𝑓 𝐻𝐹
∆𝑡
For the reaction
𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷
the rate of the reaction in terms of each component can be expressed as
1 ∆[𝐴] 1 ∆[𝐵] 1 ∆[𝐶] 1 ∆[𝐷]
𝑟𝑎𝑡𝑒 = − = − = =
𝑎 ∆𝑡 𝑏 ∆𝑡 𝑐 ∆𝑡 𝑑 ∆𝑡

The RATE LAW

RATE LAW – is an equation that expresses the rate of a reaction as a function of the concentration of reactants
“the rate of reaction is directly proportional to the concentration of the reactants raised to certain power”
𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷+ . ..
the rate of the reaction is
𝑟𝑎𝑡𝑒 = 𝑘[𝐴]𝑥 [𝐵]𝑦 . . …
where k = proportionaly constant
x and y = powers of [A] and [B], respectively

The proportionality constant (k) is known as the rate constant and is specific for the reaction shown at a particular temperature.
The rate constant changes with temperature, and its units depend on the sum of the concentration term exponents in the rate law.
The exponents (x and y) must be experimentally determined and do not necessarily correspond to the coefficients in the balanced
chemical equation.

Reaction Order – the sum of the powers to which the concentration of the reactants are raised in the rate law
For the following reaction between nitrogen dioxide and carbon monoxide:
NO2(g) + CO(g) → NO(g) + CO2(g)

The rate law is experimentally determined to be: rate = k[NO2]2

Therefore, we would say that the overall reaction order for this reaction is second-order (the sum of all exponents in the rate law is
2), but zero-order for [CO] and second-order for [NO2].
The reaction order is most often a whole number such as 0, 1, or 2; however, there are instances where the reaction order may be
a fraction or even a negative value.

𝑟𝑎𝑡𝑒 = 𝑘[𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡]𝑥
𝑈𝑛𝑖𝑡𝑠 𝑜𝑓 𝑟𝑎𝑡𝑒 = (𝑢𝑛𝑖𝑡𝑠 𝑜𝑓 𝑟𝑎𝑡𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡)(𝑢𝑛𝑖𝑡𝑠 𝑜𝑓 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛)𝑥
𝑢𝑛𝑖𝑡𝑠 𝑜𝑓 𝑟𝑎𝑡𝑒
𝑈𝑛𝑖𝑡𝑠 𝑜𝑓 𝑟𝑎𝑡𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 =
(𝑢𝑛𝑖𝑡𝑠 𝑜𝑓 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛)𝑥
𝑀/𝑠
=
𝑀𝑥
Therefore, the units of the rate constant should be:
Different Values of Reaction Order
 Zero: A zero order indicates that the concentration of that species does not affect the rate of a reaction
 Negative integer: A negative order indicates that the concentration of that species INVERSELY affects the rate of a
reaction
 Positive integer: A positive order indicates that the concentration of that species DIRECTLY affects the rate of a reaction
 Non-Integer: Non-integer orders, both positive and negative, represent more intricate relationships between
concentrations and rate in more complex reactions.

Chemical reactions can be classified into the following types based on the dependence of the rate on the concentration.
1) Zero Order Reactions
 The rate of reaction is independent of the concentration of the reactants in these reactions.
 A change in the concentration of the reactants has no effect on the speed of the reaction
 Examples of these types of reactions include the enzyme-catalyzed oxidation of CH3CH2OH (ethanol) to CH3CHO
(acetaldehyde)
2) First-Order Reactions
 The rates of these reactions depend on the concentration of only one reactant, i.e. the order of reaction is 1.
 In these reactions, there may be multiple reactants present, but only one reactant will be of first-order concentration
while the rest of the reactants would be of zero-order concentration.
 Example of a first-order reaction: 2H2O2 → 2H2O + O2
3) Pseudo-First Order Reactions
 In a pseudo-first order reaction, the concentration of one reactant remains constant and is therefore included in the rate
constant in the rate expression.
 The concentration of the reactant may be constant because it is present in excess when compared to the concentration
of other reactants, or because it is a catalyst.
 Example of a pseudo-first order reaction: CH3COOCH3 + H2O → CH3COOH + CH3OH (this reaction follows pseudo-
first order kinetics because water is present in excess).
4) Second-Order Reaction
 When the order of a reaction is 2, the reaction is said to be a second-order reaction.
 The rate of these reactions can be obtained either from the concentration of one reactant squared or from the
concentration of two separate reactants.
 The rate equation can correspond to r = k[A]2 or r = k[A][B]
 Example of a second-order reaction: NO2 + CO → NO + CO2

FACTORS AFFECTING RATE OF REACTION

1) surface area of the reactants
- the rate of reaction increases as the surface area increases
2) concentration of the reactants
- increase in concentration of reactants results in increase of rate of reaction
3) temperature
- temperature is directly proportional to kinetic energy
- increase in temperature results in increase in kinetic energy of the reacting particles
4) presence of catalyst
Catalyst – is a substance that speeds up a chemical reaction without being consumed in the reaction
CHEMICAL EQUILIBRIUM – is the state in which the forward and backward reactions of a reversible chemical reaction are
occurring at equal rate

The concentration of the reactants and the products remain constant at equilibrium as long as the temperature does not
change.
Characteristics of chemical equilibrium:
1) the rates of the opposing reaction are equal
2) concentration remain constant at equilibrium even though the opposing reactions are continuing
3) attainment of equilibrium does not occur immediately, it often requires time

Equilibrium Constant – is equal to the product of the concentrations of the products each raised to the power of its coefficient in
the balanced chemical equation, divided by the product of reactant concentrations
- is a measure of the extent to which a reaction proceeds to completion
-
𝑎𝐴 + 𝑏𝐵 → 𝑝𝑃 + 𝑞𝑄

[𝑃]𝑝 [𝑄]𝑞
𝐾𝑒𝑞 =
[𝐴]𝑎 [𝐵]𝑏
Keq = equilibrium constant

The value of equilibrium constant determines the equilibrium position.

Equilibrium Position – qualitative description of the extent of chemical reaction

A large equilibrium constant indicates that the equilibrium mixture contains more products than reactants.
A small value means that the equilibrium lies toward the reactant side

REACTION QUOTIENT (Q) – used to measure the extent of chemical reaction; used to determine how far from equilibrium the
chemical reaction is

When the reaction quotient is equal to the equilibrium constant, (Q=Keq), the system is at equilibrium.
When Q>Keq, the reaction will proceed toward the formation of more reactants to achieve equilibrium.
When Q<Keq, the reaction will move toward equilibrium forming more products.

LE CHATELIER’S Principle – states that if a system in equilibrium is disturbed, the equilibrium will shift to minimize the effect of the
disturbing influence
 Effect of Changes in Concentration on Reaction equilibrium
 Effect of Changing Pressure and Volume
 Effect of Changing Temperature
 Effect of Catalyst

THERMOCHEMISTRY – the study of the heat formed or required by the chemical reaction
Energy – the ability to do work or transfer heat
Types of Energy:
 potential E
 kinetic E

Heat – energy that can be transferred from one object to another, causing a change in temperature of each

Units of Energy:
 Joule (J)  1 J = 1kg.m2s-2
 Calorie
Energy Units Equivalent (J)
Calories (cal) 4.184
Electron volt (eV) 9.6485 x 104
Liter – atmosphere (L-atm) 1.01325vx 102
Erg 1.0 x 10-7
System and Surroundings
System –part of universe (open/close/isolated)
Surroundings – everything else in the universe around the system
FIST LAW OF THERMODYNAMICS – the law of conservation of energy

Internal Energy – the sum of all possible energy in the system

Change in Energy (ΔE) – the change in the total energy of the system as it transforms from one state to another
∆𝐸 = 𝐸𝑓𝑖𝑛𝑎𝑙 − 𝐸𝑖𝑛𝑖𝑡𝑖𝑎𝑙
Positive ΔE – the system absorbed energy from the surroundings
Negative ΔE – the system released or given up energy to the surroundings

∆𝐸 = 𝑞 + 𝑤
ΔE = total change in the internal energy
q = heat change between system and surroundings
w = work exchanged between system and energy

ENTHALPY(ΔH) – the heat transferred between the system and the surroundings under constant pressure; the heat content of a
system
∆𝐻 = 𝐻𝑓𝑖𝑛𝑎𝑙 − 𝐻𝑖𝑛𝑖𝑡𝑖𝑎𝑙

Enthalpy of a reaction (ΔHrxn) - the enthalpy change that accompanies a reaction

∆𝐻𝑟𝑥𝑛 = Ʃ𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − Ʃ𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

HESS’S LAW – states that if a reaction occurs in two or more steps, the enthalpy for the reaction is the sum of the enthalpies of the
individual steps

HEAT CAPACITY – is the amount of heat needed to raise the temperature of an object by 1 degree Celcius or 1K

Molar Heat Capacity – refers to the heat capacity of one mole of substance

Specific Heat – is the heat capacity of one gram of substance