 A reaction may be thermodynamically

favored but not kinetically favored.

 Kinetics studies the rates of a chemical
process.
 The study of kinetics gives insights into the
reaction mechanism (i.e., how a reaction
occurs).
 Defined as a measure of how fast a reaction
takes place.
 The rate of a reaction is often expressed as a
change in amount or concentration of a
substance (reactant or product) per unit time.
 Chemical kinetics is the study of rates of
reactions and factors that affect them.
Rates of reactions can be determined
by monitoring the change in
concentration of either reactants or
products as a function of time.
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 Homogeneous catalyst:
In homogeneous catalysis, reaction mixture and
catalyst both are present in the same phase. Both
catalyst and reactants show high homogeneity
which results in high interaction between them
that leads to high reactivity and selectivity of the
reaction under mild reaction conditions.
 Homogeneous catalyst:
Some examples of homogeneous catalysts are
Brønsted and Lewis acids, transition metals,
organometallic complexes, organocatalyst. Some
notable chemical processes that occur through
homogeneous catalysis are carbonylation,
oxidation, hydrocyanation, metathesis, and
hydrogenation.
 Homogeneous catalyst:
 Heterogeneous catalyst:
In heterogeneous catalysis, catalysts exist in a
different phase than the reaction mixture. Some of
the exemplary processes that use heterogeneous
catalysts are Haber-Bosch process for the
synthesis of ammonia, Fischer–Tropsch process to
produce a variety of hydrocarbons.
 Heterogeneous catalyst:
Heterogeneous catalysts dominate major industrial
processes because of the easy separation of product and
recovery of catalyst. Heterogeneous catalysts may be
used as fine particles, powders, granules. These
catalysts may be deposited on the solid support
(supported catalysts), or used in bulk form (unsupported
catalysts).
 Heterogeneous catalyst:
 Heterogenized homogeneous Catalysts:
Heterogeneous catalysts in contrast to their
homogeneous counterparts are much more difficult to
develop practically. One reason is their complexity,
which precludes their analysis at a molecular level and
development through structure–reactivity relationships.
In addition, traditional heterogeneous catalysts (metal
oxides or supported metals) exhibit less selectivity and
reactivity. In order to surmount these issues, the
homogeneous catalyst is grafted onto the solid supports
to prepare their heterogenic analogs.
 Heterogenized homogeneous Catalysts:
Presently, the solid-supported homogeneous catalysts are
widely recognized and well exploited in academic and
industrial research. The aim of this approach is to overlap the
positive features of both homogeneous (selectivity and
reactivity) and heterogeneous catalyst (reproducibility) and
this can be achieved through the immobilization of catalysts
such as metal complexes, organometallic compounds on the
solid surface either through physisorption or chemisorption.
Covalent grafting of catalytic active species on solid surfaces
is found to be the most favoured approach for designing
heterogenized homogeneous catalyst.
 Biocatalysts:
Natural proteins (enzymes) or nucleic acids (RNA or
ribozymes and DNAs) used to catalyze specific chemical
reactions outside the living cells is called biocatalysis.
Enzymes are obtained from animal tissues, plants and
microbes (yeast, bacteria or fungi). High selectivity, high
efficiency, eco-friendliness and mild reaction conditions
are the driving forces for their large scale utilization and
making biocatalysts an alternative to conventional
industrial catalysts.
 Biocatalysts:
Significant progress in the field of protein engineering and molecular
evolution has revolutionized the world of biocatalysis for the industrial
scale syntheses of fine chemicals, active ingredients (APIs) biofuels (e.g.
lipase for the production of biodiesel from vegetable oil), dairy industry
(e.g. protease, lipase for lactose removal, renin for cheese preparation),
baking industry (e.g. amylase for bread softness and volume, glucose
oxidase for dough strengthening), detergent manufacturing (e.g.
proteinase, lipase, amylase used to remove stains of proteins, fats,
starch, respectively) leather industry (e.g. protease for unhairing and
bating), paper industry, textile industry (e.g. amylase for removing
starch from woven fabrics). Immobilization of enzymes on solid
supports turns enzymes into heterogeneous solid catalyst which
enhances the activity, stability and increase the lifetime of catalyst that
can be reused for many cycles.
for a reaction to proceed,
 contact is necessary between reactants
 contact must lead to breaking of bonds (need
sufficient energy)
 the reactants must have proper orientation
 If a reaction occurs, during the collision, the
particles that separate are different from
those that collide.
 When the particles collide, the molecules
slow down. Thus, the total kinetic energy
(K.E.) they possess decreases. Because
energy cannot disappear, this means that the
total potential energy (P.E.) of the particles
must increase.
 There is a minimum amount of energy
required for reaction: the activation energy,
Ea.
 Just as a ball cannot get over a hill if it does
not roll up the hill with enough energy, a
reaction cannot occur unless the molecules
possess sufficient energy to get over the
activation energy barrier.
Figure 1. A potential energy diagram for a reaction. (Image source: http://
schools.birdville.k12.tx.us/cms/lib2/tx01000797/centricity/domain/912/chemlesso
ns/Lessons/
Energy/image001.jpg)
A catalyst provides a path for the reaction with a lower activation energy.
When a catalyst is present, more molecules possess the minimum amount of
energy needed for effective collisions.!
 Initial Rates
 Rates measured at the beginning of the
reaction, which is dependent on the initial
concentrations of reactants.
 Instantaneous Rates
 Rates measured at any point during the
reaction.
 Average Rates
 An overall rate measured over a period or
time interval.
 C4H9Cl(aq) + H2O(l) → C4H9OH(aq) + HCl(aq)
• Note that the
average rate decreases
as the reaction
proceeds.
• This is because as the
reaction goes forward,
there are fewer
collisions between
reactant molecules.
 C4H9Cl(aq) + H2O(l) → C4H9OH(aq) + HCl(aq)
• A plot of concentration
versus time for this
reaction yields a curve
like this.
• The slope of a line
tangent to the curve at
any point is the
instantaneous rate at
that time.
 rate = change in conc. / change in time
 aA + bB → cC + dD
1∆[𝐴] 1∆ 𝐵 1∆[𝐶] 1∆[𝐷]
𝑅𝑎𝑡𝑒 = 𝑅 = − 𝑎∙∆𝑡 = - 𝑏∙∆𝑡 = =
𝑐∙∆𝑡 𝑑∙∆𝑡

The rate can be related to the concentration

of the reactants or products. Reactants will
have a negative sign. Don’t forget to use
the stoichiometric coefficients.
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 Rate = R = k [A]x [B]y
 k is the rate constant for this reaction.
 x = order of the reaction with respect to the
concentration of reactant A
 y = order of the reaction with respect to the
concentration of reactant B
 x+y = overall reaction order or (total) order of
the reaction.
 Table 1: Summary Table for Orders of Reaction
Order of Reaction Change in Concentration of Change in Rate of Reaction
Reactant

1. Zero Order (x=0) Concentration is Doubled No change

Rate = k[A]0
Concentration is Tripled No Change
2. First Order (x=1) Concentration is Doubled Doubled
Rate = k[A]1
Concentration is Tripled Tripled
3. Second Order (x=2) Concentration is Doubled Quadrupled
Rate = k[A]2
Concentration is Tripled Increase ninefold
Consider the hypothetical reaction: A + B → C. The table below
shows the result of the three different experiments conducted
using this reaction at varying concentration of reactants.
 How long does it take an iron nail exposed to the rain
to rust?
 Compare the rusting of iron to how fast milk curdles
when an acid like vinegar or calamansi juice is
added to it.
 Which has a more rapid reaction, the burning of liquid
gasoline in air, or gasoline in a car engine that
is first vaporized, then mixed with air?
 Do you think you could light a log with a single
matchstick?
 How about twigs or smaller pieces of wood?
 Baking powder or sodium bicarbonate
(NaHCO3), is used in baking to make cakes rise
because the carbon dioxide gas produced when
baking powder reacts with water in the cake
batter. Compare the volume of a cake prepared
with the right amount of baking powder, with
that of just about half the amount needed.
 Why do we keep food in the refrigerator?
 How do particles move at high temperatures
compared at low temperatures?