Chemical Kinetics Reaction Rate Formula

• Rate is a change in concentration over a time period: Δ[ ]/Δt.

• study the rate (or speed) at which a chemical process occurs.
• also sheds light on the reaction mechanism, a molecular-level view of the Appearance of product = ∆ [product]
path from reactants to products.
∆ time

Factors that Affect Reaction Rates Disappearance of reactant = - ∆ [reactant]

1) Physical state of the reactants ∆ time

 The more readily the reactants collide, the more rapidly they react.
 Homogeneous reactions are often faster. Plotting Rate Data
 Heterogeneous reactions that involve solids are faster if the
surface area is increased; i.e., a fine powder reacts faster than a
pellet or tablet.

2) Reactant concentrations
 Increasing reactant concentration generally increases reaction
rate.
 Since there are more molecules, more collisions occur.

3) Reaction temperature
 Reaction rate generally increases with increased temperature. Differential Rate Laws
 Kinetic energy of molecules is related to temperature.
• Dependence of reaction rate on the concentration of reactants is called the
 At higher temperatures, molecules move more quickly, increasing rate law, which is unique for each reaction
numbers of collisions and the energy the molecules possess • For a general reaction, a A + b B + c C →products
during the collisions. • the rate law has the general form
• reaction rate = k [A]X [B]Y [C]Z
4) Presence of a catalyst the rate constant
The Rate Law
 Catalysts affect rate without being in the overall balanced
equation. expresses the relationship of the rate of a reaction to the rate constant and the
 Catalysts affect the kinds of collisions, changing the mechanism concentrations of the reactants raised to some powers.
(individual reactions that are part of the pathway from reactants to
products).  always determined experimentally
 Catalysts are critical in many biological reactions.  always defined in terms of reactant (not product) concentrations
 order of a reactant is not related to the stoichiometric coefficient of the
reactant in the balanced chemical equation.
First Order Reactions/ differential rate law Factors That Affect Reaction Rate

 depend only on one reactant to the first power  Temperature

• rate law becomes:  Frequency of collisions
Rate = k [A]  Orientation of molecules
 Energy needed for the reaction to take place (activation energy)
Integrated rate law:
Temperature and Rate
ln [A] = − k t + ln [A]o
 rate constant is temperature dependent
Second Order Reactions
 Rate constant doubles (approximately) with every 10 ºC rise.
• depend only on a reactant to the second power.

• The rate law becomes: Frequency of Collisions

• Rate = k [A]2  collision model (Molecules can only react if they collide with each
other.) is based on the kinetic molecular theory.
 Molecules must collide to react.
 If there are more collisions, more reactions can occur.
Zero Order Reactions/linear in concentration.

• rate is independent of the concentration of the reactant: Orientation of Molecules

• Rate = k
 atoms need to be in proper positions.

Integrated Rate Law Energy Needed for a Reaction to Take Place (Activation Energy)

[A]t = -kt + [A]0  minimum energy needed for a reaction to take place
 An energy barrier must be overcome for a reaction to take place
Half-life

Transition State (Activated Complex)

 organization of the atoms at this highest energy state

 energy needed to form this state is called the activation energy
The Relationship Between Activation Energy & Temperature Plausible Mechanism

• activation energy and temperature: k = Ae−Ea/RT  rate law must be able to be devised from the rate-determining step.
 The stoichiometry must be obtained when all steps are added up.
• Activation energy can be determined graphically by reorganizing the Mechanism With a Slow Initial Step
equation: ln k = −Ea/RT + ln A
 Overall equation: NO2 + CO → NO + CO2
• k = rate constant  Rate law: Rate = k [NO2]2
• Ea = activation energy

• A = frequency factor Mechanism With a Fast Initial Step

• R = 8.314 J/mol-K  Equation for the reaction:

2 NO + Br2 ⇌ 2 NOBr
• T = Absolute Temperature (K)  The rate law for this reaction is found to be
Rate = k [NO]2 [Br2]
Mechanism is a series of stepwise reactions that show how reactants become Rate Law
products.
 overall reaction depends upon the rate of the slow step.
Reaction Mechanisms  The rate law for that step would be
Rate = k2[NOBr2] [NO]
 Some reactions occur in a single event or step
Catalysts
 These processes are known as an elementary reactions
 molecularity of a reaction is the number of molecules reacting in an  increase the rate of a reaction by decreasing the activation energy of the
elementary step. reaction.
 Catalysts change the mechanism by which the process occurs.
 Unimolecular reaction – elementary step with 1 molecule
Types of Catalysts
 Bimolecular reaction – elementary step with 2 molecules
1) Homogeneous catalysts
 Termolecular reaction – elementary step with 3 molecules
 The reactants and catalyst are in the same phase.
Termolecular
 Many times, reactants and catalyst are dissolved in the same
 steps require three molecules to simultaneously collide with the proper solvent, as seen below.
orientation and the proper energy.
2) Heterogeneous catalysts

 is in a different phase than the reactants.

 Often, gases are passed over a solid catalyst.
 The adsorption of the reactants is often the rate-determining step
3) Enzymes

 Enzymes are biological catalysts.

 They have a region where the reactants attach. That region
is called the active site. The reactants are referred to as
substrates.