Lesson 1: Chemical Kinetics

Chemical Kinetics is the study of the rate of chemical reactions,

including the mechanism by which a reaction occurs and the different
factors that affect it

Rate of reaction can be defined as the change in the concentration of

a reactant or product per change in time. The molar concentration of a
reactant or product is presented in square bracket [ ]

Example:
Consider the balanced equation for the decomposition of the colorless
gas dinitrogen pentoxide (N2O6) into the brown dioxide gas and oxygen Catalyst speed up the rate of a chemical reaction by
gas. providing an alternative route for the reaction to occur with
lower activation energy. Reaction involving catalysts may be
classified as heterogeneous or homogeneous.

The rate of this reaction may be expressed in terms of the change in Types of Catalyst
concentration of
Heterogeneous Catalyst - uses a catalyst that is of a different
phase from that of the reactants and products.

Homogeneous Catalyst - the catalyst is of the same phase as

that of the reactants and products

The Order of the reaction

The order of the reaction indicates the magnitude by
which rate change in concentration.
Various Factors Influence the Rate of Reaction
1. Reactivity 0. Zero-order reaction has a constant rate that is equal to its
2. Concentration rate constant regardless of changes in the concentration of
3. Surface Area the reactant.
4. Temperature
5. Catalyst 1. First-order reaction, the rate doubles when the
concentration of a reactant is doubled
Reactivity
The impulse for which a chemical substance undergoes a chemical 2. Second-order reaction, increasing the reactant
reaction, either by itself or with other materials. Rate of a reaction concentration to twice as much quadruples the original
depends on the nature of bonding in the reactants. Usually the ionic reaction rate.
compounds react faster than covalent compounds.
Example : zinc is more reactive than copper, so it reacts with silver nitrate faster than
Rate Laws for Different Reaction Orders Based on the Reaction
copper does.
A ----> products
Concentration
Increasing the concentration of one or more reactants will often Reaction Order Rate Law
increase the rate of reaction. This occurs because a higher Zero
concentration of a reactant will lead to more collisions of that reactant
in a specific time period. First
Example: The brighter flame in the jar containing a greater amount of oxygen indicates
an increase in reaction rate. The higher oxygen concentration accounts for the faster Second
reaction.

Surface Area
The rate of a reaction increases with increase in the surface area of Molecular Collisions
solid reactants, it they used. The more molecules present, the more collisions will happen
- Molecules must collide first before they can react.
Example: The greater surface area of the steel wool means that more collision can - In order to effectively initiate a reaction, collisions
occur between the metal and oxygen.
must be sufficiently energetic (KE) to bring about this
bond disruption
Temperature
- As the temperature rises, molecules move faster and
An increase in temperature typically increases the rate of reaction.
collide more vigorously, greatly increasing the
An increase in temperature will raise the average kinetic energy of the
likelihood of bond cleavages and rearrangements.
reactant molecules. Therefore, a greater proportion of molecules will
- Most reactions involving neutral molecules cannot
have the minimum energy necessary for an effective collision.
take place at all until they have acquired the
Example: food stored in refrigerator . Increasing the temperature of a reaction
activation energy needed to stretch, bend or
increases the frequency of collisions and therefore the rate of the reaction. Increasing otherwise distort one or more bonds.
the temperature also raises the kinetic energy of the particles.
Low Concentration; few collisions : High Concentration; more collision
Catalyst
A catalyst is a substance that accelerates a reaction by participating Lesson 2 : Laws of Thermodynamics
in it without being consumed. Catalysts provide an alternative
reaction pathway to obtain products. They are critical to many 1st Law - Energy of the Universe is constant
biochemical reactions. “Energy can be converted from one form to another but
cannot be created nor destroyed”
Aside from colliding with one another, the reactant particles must 2nd Law - Entropy of universe increases
also have sufficient energy during collision. They must be able to “The entropy of the universe increases in a spontaneous
surpass an energy barrier, called the activation energy of the process and remains unchanged in an equilibrium process.”
transition state (Ea), to successfully form the products. At the 3rd Law - At absolute zero, the entropy of a perfect crystal is 0
transition state, the reactants form an activated (or transition) “ The entropy of a perfect crystalline substance is zero at
complex that eventually forms the product. the absolute zero of temperature” (T = 0K= -273.15 C)

How does a catalyst affect the reaction rate? Spontaneous Process is a physical or chemical change that
A catalyst increases the rate of reaction by decreasing the activation occurs by itself. These processes occur without requiring an
energy. Decreased activation energy means less energy required to outside force and continue until equilibrium is reached.
start the reaction. Opposite of such is a Non-Spontaneous Process.

The graph below shoes the energy of the reaction both with and Thomsen-Berthelot Principle - most of all exothermic
without a catalyst present. The x-axis is the reaction coordinate or chemical processes are spontaneous
progression of the reaction from the reactant (left side) to product
(right side). This y-axis is the energy. Randomness influences spontaneity.
Entropy, S - is a thermodynamic quantity that is a measure of how
spread out or dispersed the energy of a system is among different
possible ways that system can contain energy.
Lesson 3 : Gibbs Free Energy and Spontaneity
It is a quantity that is generally used to describe the course
of a process,that is, whether it is a spontaneous process and has a Gibbs free energy also determines the spontaneity of a reaction.
probability of occurring in a defined direction, or a non spontaneous
process and will not proceed in the define direction but in the reverse G=H −TS
direction. Gibbes-Helmoholtz equation expressed as ,
Most processes are accompanied by entropy change. The following are
processes that lead to an increase in entropy of the system. ∆ G=∆ H −T ∆ S
Process Order Disorder All the quantities in the equation pertain to the system, the
temperature T is the temperature of the system.
melting solid liquid
- G has units of energy; both H and Ts are in energy units
vaporization liquid vapor - H, S and G are all state functions.
dissolving solute solution
heating System at T1 System at T2 (T2>T1) The value of ∆ G determines the spontaneity of a chemical
reaction at constant pressure and temperature
The spreading out of more concentrated molecules and the spreading
out of more concentrated energy are changes from more order to more A reaction is spontaneous if ∆G negative, non-spontaneous if
random. The changes that occur are the ones that lead to an increase
randomness of the universe. Entropy is sometimes referred as the
∆G is positive. This follows that for a reaction to be
spontaneous, either these two conditions must be met:
measure of randomness and disorder.

Entropy Change Examples ∆ H must be negative, while is ∆ S positive.

1. Molecules of gas at high pressure always spread to lower pressure If is ∆ H positive, ∆ S must be large or T must be high enough
regions
2. Gas in balloon spreads out into room and deflated but never see so that will be negative ∆ G .
balloon spontaneously fill itself with air
3. Heat always goes from high temperature into cooler regions If the entropy of the universe increases then the ∆ G of the
4. Hot coffee in a room gets cooler and the heat spreads out into the system will decrease. The direction of spontaneous change is
room, but never sees a cold cup of coffee spontaneously warm up negative ∆ G for system. The ∆ G tells us if a change can
Factors that Influence Entropy occur for a chemical reaction.
1. Temperature - a change in temperature can result in change in
entropy. The third law of thermodynamics states that “ a perfectly If ∆ S univ is (+) for universe then ∆ G for system is (-). The for
ordered pure crystalline solid at zero Kelvin will have zero entropy”. the system is a convenient way to predict a change.
2. Number of Particles - chemical reactions that produce a higher
number of product particles than reactant particles are usually
spontaneous
∆ S univ ∆G ∆ S univ Reaction
+ - increase Spontaneous, will go
product particles > reactant particles = spontaneous
0 0 stay the same No change at equilibrium
- + decrease Not spontaneous, will not
go, the reverse will.

Under standard conditions of 1 atm at 25 ℃ , the standard

free energy change ( ∆G ° ) of a chemical reaction can be
obtained from the standard enthalpy change (∆ H ° )and
standard entropy change( ∆ H ° ). The Gibbs-Helmholtz
equation then becomes:

∆ G °=∆ H ° −T ∆ S °
The standard free energy change of reaction can also be
calculated from the standard free energy of formation ∆ G °f of
the reactants and products
3. Phase Change - a steady increase in entropy as the temperature is
raised for a particular phase, then an abrupt increase once the
temperature for phase change is reached, ∆ G °=∑ ∆ G° f ( products)− ∑ ∆ G ° f ( reactants)
Dissolutions of silver chloride (AgCl)
Standard Molar Entropy
The standard molar entropy (S° ) of a substance is the entropy of one
mole of a substance at the standard conditions ( 1 atm and 25 ℃ , in
Kelvin = 298.15 K (S° > 0)
Substance
The standard entropy of reaction (∆ S °) ∆ G ° f (kJ/
mol)
∆ S °=∑ S ° ( products) − ∑ S ° (reactants)

Substance
S°¿
Determine the spontaneity of the dissociation of ammonium nitrate
(NH4NO3), the compound used in cold packs. Interpret the values from
the calculations.

Substance
∆ H ° f (kJ/
mol)
S°¿