Chemical
Kinetics
By :- Divyam verma
Ankur kumar
Deepak kumar
Factors that Affect Reaction Rates
The area of chemistry that is concerned
with the speeds, or rates, of reactions is
called chemical kinetics.
Reaction rates depend on the frequency
of the collisions between the particles.
The four factors that affect the rate of
reaction are the physical states of the
reactants, concentration of reactants,
temperature, and presence of a catalyst.
Physical States
Reactions occur the fastest when the
molecules are colliding quickly.
When the reactants are the same state of
matter, reactions tend to occur faster.
When a solid has a larger surface area
(crushed), a reaction proceeds faster.
Concentration
Most chemical reactions proceeds faster
if the concentration of one or more of the
reactants is increased.
The increase in reaction rate is due to an
increase in collisions of particles.
Temperature
The rate of a chemical reaction increases
as temperature increases.
As temperature increases, the particles
collide more frequently and with greater
energy.
Catalyst
Catalysts speed up a reaction be
changing the mechanism that leads to
the products.
Catalysts are not considered reactants or
products and are listed about the yield
sign.
Reaction Rates
Therate of a reaction can be expressed as either
the disappearance of the reactant or the
appearance of the product.
AB
Appearance of B = D[B]
Dt
Disappearance of A = -D[A]
Dt
Reaction Rates with Time
Itis typical for rates to decrease as a
reaction proceeds because the
concentration of reactants decreases.
Instantaneous Rate
Graphs showing us the change in concentration
with time allow us to calculate the instantaneous
rate, the rate at a particular moment.
The instantaneous rate is the slope of a line drawn
at a point on the graph. (tangent)
Stoichiometry
When determining the reaction rates for a chemical
reaction, the coefficients must be used.
aA + bB cC + dD
Reaction = - 1 D[A] = -1 D[B] = 1 D[C] = 1 D[D]
Rate a Dt b Dt c Dt d Dt
The Rate Law: The Effect of
Concentration on Rate
The rate law shows how the rate of a
reaction depends on the concentration
of the reactants.
The rate law of a reaction can only be
determined experimentally, not by the
coefficients of a reaction.
Rate Law
The rate law is written as follows:
aA + bB cC + dD
Rate = k[A]m[B]n
k = rate constant which changes with
temperature
m and n = typically small whole numbers
Determining Rate Law
Using the chart, we can see that the rate
law would be
Rate = k[NH4+][NO2-]
Since the rates change with a direct
proportion to the concentrations of both
reactants.
Reaction Orders
The exponents m and n in a rate law are
called the reaction orders.
The overall reaction order is the sum of
the reaction orders.
Rate = k[NH4+][NO2-]
NH4+ = 1st order
NO2- = 1st order
Overall reaction order = 2nd order
Units for Rate Constants
Theunits for the rate constant depend on
the overall reaction order of the rate law.
The Change of Concentration with
Time
A first order reaction is one whose rate
depends on the concentration of a single
reactant to the first power.
Differential Rate Law Rate = k[A]
Integrated Rate Law ln[A]t = -kt + ln[A]0
You
can use this equation to solve for
concentration or time.
Reaction Rate Graphs
For a 1st order reaction, a graph of ln[A]t
vs. time will give a straight line.
ln[A]t = -kt + ln[A]0
y = mx + b
Second Order Rates
A second order reaction is one whose
rate depends on the reactant
concentration to the 2nd power or 2
reactants to the 1st power.
Differential Rate Law Rate = k[A]2
Integrated Rate Law 1/[A]t = kt + 1/[A]0
y = mx + b
Half-Life
The half-life of a reaction, t1/2, is the time
required for the concentration of a
reactant to reach one-half of its initial
value, [A]t1/2 = ½ [A]0.
A fast reaction will have a short half-life.
Half-life for a 1st order reaction.
t1/2 = 0.693/k
Half-Life
Using the equation from the previous slide,
you can see that the half-life of a first
order reaction does not depend on initial
concentration.
In a 1st order reaction, the concentration
of the reactant decreases by ½ in each of
a series of regularly spaced time intervals,
t1/2.
Half-life for 2nd Order
The half-life of a 2nd order reaction does
depend on initial concentration.
t1/2 = 1/k[A]0
The lower the initial concentration, the
larger the half-life.
Temperature and Rate
The rates of most chemical reactions
increase as the temperature increases.
The rate constant for a reaction increases
as temperature increases.
Collision Model
The collision model is based on the idea
that particles must collide in order to
react.
The greater the number of collision, the
greater the reaction rate.
As the concentration of reactants
decreases, the number of collisions
decreases.
Collision Model
Asthe temperature increases, the number
of collisions increases. The energy of the
collisions also increases.
Activation Energy
Toreact, colliding molecules must have a
total kinetic energy equal to or greater
than a minimum value called the
activation energy, Ea.
Activation Energy
The activation energy is energy difference
between the energy of the reactants and
the highest point on the energy pathway.
The highest point on the energy pathway
is called the activated complex or
transition state.
Transition State
The transition state is very unstable.
Arrhenius Equation
Arrhenius discovered that most reaction
rate data obeyed 3 factors:
1. fraction of molecules possessing Ea.
2. number of collisions per second.
3. fraction of collisions with proper
orientation.
Reaction Mechanisms
A balanced equation for a chemical
reaction indicates the substances present
at the start of the reaction and those
produced as the reaction proceeds.
The process by which a reaction occurs is
called the reaction mechanism.
Elementary Reactions
Reactions that occur in a single step are
called elementary reactions.
The number of molecules that participate
are reactants in an elementary reactions
defines the molecularity.
Molecularity
Unimolecular = a single molecule is
rearranged.
Bimolecular = 2 molecules collide.
Termolecular = 3 molecules collide.
Elementary reactions that involve 3 or
more molecules colliding are rarely
encountered.
Intermediate
An
intermediate is a substance formed
and then consumed during the reaction
mechanism.
Rate Laws
Every reaction is made up of a series of
one or more elementary steps, and the
rate laws and relative speeds of these
steps will dictate the overall rate law.
If a reaction is an elementary reaction,
then its rate law is based directly on its
molecularity.
A products
Rate = k[A]
Catalysis
A catalyst is a substance that changes
the speed of a chemical reaction without
undergoing a permanent chemical
change itself in the process.
A catalyst that is present in the same
phase as the reacting molecules is called
a homogenous catalyst.
Catalyst
Neither a catalyst nor an intermediate is
listed in the overall reaction.
The catalyst is there at the start of the
reaction, whereas the intermediate is
formed during the course of the reaction.
A catalyst lowers the overall activation
energy for the chemical reaction.
Catalyst
A heterogeneous catalyst
exists in a different phase
from the reactant molecules,
usually as a solid in contact
with either gaseous reactants
or with reactants in a liquid
solution.
The initial step in
heterogeneous catalysis is
usually adsorption of
reactants.