Integrated Rate Laws and Half Life

Order Integrated Rate Law Half Life The half life for this
reaction gets shorter over time
0 [A}t = -kt + [A]0 t 1/2 = [A]0/2k
1 -ln[A]t = -kt + ln[A]0 t = 0.693/k The half life for
this reaction is constant over time (does not change)
2 1/[A} t = kt + 1/[A}0 t1/2 = 1/k[A]0 The half life
for this reaction gets smaller over time

Effect of Temperature on Reaction Rate

Changing the temperature changes the rate constant of the rate law
Relationship given by k = Ae-EaRT
o T= temperature in kelvins
o R = gas constant
o Ea= activation energy (extra energy needed to start the reaction

Activation Energy Barrier Illustration

Activation energy is the PE barrier needed to be cocverome in order for a

reaction to occur
o High point of the diagram is the transition state
 Barrier separating the two minima energies
The species present at the transition state is the called the activated
complex
The energy gap btwn the reactants and activated complex is the activation-
energy complex

Thermal Energy Distribution

Temperature is defined as a measure of the average kinetic energy of

molecules in a sample
At any temperature there is a wide distribution of kinetic energies
o If a sample is heated, there is a larger region above the curve that is
above the minimum energy needed to react
As the temperature increases, the curve flattens and broadens

Catalysts

Catalysts are substances that affect the rate of a reaction without being
consumed
o Ie. acid catalyzed esterification
Methanol
Carboxylic Acid
Add sulfuric acid to catalyze the reaction
 Catalysts work by providing an alternative mechanism for the reaction
with a lower activation energy
Catalysts can be consumed in an early mechanism step and then made in a
later step
As written does this reaction mechanism have an intermediate and/or catalysts?
H2O2 + I - H2O + IO-
H2O2 + IO- H2O + O2 + I-
a. only an intermediate
The intermediate is indicating that it is both in the products and
reactants
b. only a catalyst
c. an intermediate and a catalyst
d. neither an intermediate nor a catalyst

Factors Affecting Reaction Rate: Catalysts

Catalysts are substances that affect the speed of a reaction without being
consumed
o Are used to speed up a reaction
o They give the reactant molecules a different path to follow through a
lower activation energy
Homogeneous catalysts: are present in the same phase
o React with one of the reactant molecules to form a more stable
activated complex
Heterogeneous catalysts: are present in different phases
o Require the proper orientation for the reaction to occur when the
collision takes place
Catalysts Types
 Homogenous catalysts are in the same phase as the reactant particles
o Ie. chlorine in the destruction of ozone; esterification rxn
Heterogeneous catalysts are in a different phase than the reactant particles
o Ie. solid catalytic convert in a car exhaust system

Illustration of Catalyst Types

Which statement is FALSE?

a. catalyst increases the rate of a reaction
b. a catalyst changes the reaction mechanism
c. a catalyst lowers the activation energy of the reaction
d. catalysts are not consumed in the reaction
e. all of the statements are true

Biological Catalysts: Enzymes

Enzyme + Substrate EnzymeSubstrate Fast

EnzymeSubstrate Enzyme + Product

Activation Energy Profiles

Catalysis

Zero Activation Energy

Given the initial rate data, determine the rate law and rate constant for
the following reaction:
NH4 + (aq) + NO2- (aq) N2 (g) + H2O (l)

Experiment Initial [NH4+] Initial [NO2-] (M) Rate (M/s)

(M)
1 0.100 0.0050 1.35 x 10-7
2 0.100 0.010 2.65 x 10 -7
3 0.200 0.010 5.34 x 10-7

[NO2-]1 Rate Order is First Order

[NH4 -1] Rate Order is First Order