CHE 101:Chemistry

Chemical Kinetics
lecture no.8

Dr Harpreet Kaur Lovely School of Engineering & School of Technology Chemical Kinetics

Kinetics
Studies the rate at which a chemical process occurs. Besides information about the speed at which reactions occur, kinetics also sheds light on the reaction mechanism (exactly how the reaction occurs).
Chemical Kinetics

Outline: Kinetics
Reaction Rates
Rate Laws Integrated Rate Laws Half-life Arrhenius Equation Mechanisms
How we measure rates.
How the rate depends on amounts of reactants. How to calc amount left or time to reach a given amount.

How long it takes to react 50% of reactants.

How rate constant changes with T. Link between rate and molecular Chemical scale processes.
Kinetics

Factors That Affect Reaction Rates

Concentration of Reactants
As the concentration of reactants increases, so does the likelihood that reactant molecules will collide. At higher temperatures, reactant molecules have more kinetic energy, move faster, and collide more often and with greater energy.

Temperature

Catalysts
Speed rxn by changing mechanism.
Chemical Kinetics

Reaction Rates
Rxn Movie

Rates of reactions can be determined by monitoring the change in concentration of either reactants or products as a function of Chemical time. [A] vs t Kinetics

The factors mentioned will affect the composition of the reaction mixture at any given time.

Therefore
The change in composition of the reaction mixture with time is the rate of reaction, denoted by R, r or .

R is the same whether monitoring reactants or products

Generally,

aA + bB

cC + dD
Chemical Kinetics

Rate laws, rate constants, reaction order

R = ([A][B]) And, R [A]m [B]n

With the use of a proportionality constant k, which is the rate constant (independent of conc. but dependent on temp.), R = -d[A]/dt = k [A]m [B]n
Such an equation is called the rate law
Chemical Kinetics

The exponents m and n are the order of the reaction with respect to reactant A and the order of the reaction with respect to reactant B respectively. The order of the reaction = m + n
If m = n =1, then the reaction is first-order in A and first-order in B, but second-order overall, therefore: R = k [A][B] Hence, 3 1
k R mol dm s dm3 mol 1 s 1 [ A][ B ] ( mol dm 3 ) 2
Units for rate constant

If first-order overall????
R mol dm s 1 k s 1 [ A] mol dm3
3

for 2nd order reaction

Units for rate constant for 1st order reaction

Chemical Kinetics

Lecture no.9-10

Chemical Kinetics

Experiment [S2O8 ]

Determine the rate law and calculate the rate constant for the following reaction from the following data: S2O82- (aq) + 3I- (aq) 2SO42- (aq) + I3- (aq) rate = k [S2O82-]x[I-]y Initial 2[I ] Rate (M/s) 2.2 x 2.2 x 10-4 10-4 1 0.08 0.034

2
3

0.08
0.16

0.017
0.017

1.1 x 10-4

y=1 x=1 rate = k [S2O82-][I-]

Double [I-], rate doubles (experiment 1 & 2)

Double [S2O82-], rate doubles (experiment 2 & 3)

2.2 x 10-4 M/s rate k= = = 0.08/Ms 2-][I-] [S2O8 (0.08 M)(0.034 M)
Chemical Kinetics

13.2

First-Order Reactions
[A] product rate = rate = k [A] t rate k = [A] = M/s = 1/s or s-1 M [A] is the concentration of A at any time t [A] = k [A] [A]0 is the concentration of A at time t=0 t ln[A] = ln[A]0 - kt [A] = [A]0exp(-kt)

Chemical Kinetics

Zero-Order Reactions
A product [A] rate = t rate = k [A]0 = k
[A] =k t
[A] is the concentration of A at any time t [A]0 is the concentration of A at time t=0

k = rate = M/s [A]0 [A] = [A]0 - kt

t = t when [A] = [A]0/2

[A]0 t = 2k

Chemical Kinetics

Second-Order Reactions
A product

[A] rate = t

rate = k [A]2 [A] = k [A]2 t

k = rate = M/s = 1/Ms M2 [A]2 1 1 = + kt [A] [A]0

[A] is the concentration of A at any time t [A]0 is the concentration of A at time t=0

t = t when [A] = [A]0/2

t = 1 k[A]0
Chemical Kinetics

Reaction Orders For the reaction: A B, the rate law is: rate = k [A]m
Order (m) Zero (0) 1st (1) [A] by a factor of: 2, 4, 15, , etc. 2 Effect on rate None 2X

3
2 3

3X
4X 9X X
Chemical Kinetics

2nd (2)

First-Order Processes

If a reaction is first-order, a plot of ln [A]t vs. t will yield a straight line with a slope of -k. So, use graphs to determine rxn order.
Chemical Kinetics

First-Order Processes
Consider the process in which methyl isonitrile is converted to acetonitrile.

CH3NC

CH3CN

How do we know this is a first order rxn?

Chemical Kinetics

First-Order Processes
CH3NC
This data was collected for this reaction at 198.9C.

CH3CN

Does rate=k[CH3NC] for all time intervals?

Chemical Kinetics

First-Order Processes

When ln P is plotted as a function of time, a straight line results.

The process is first-order. k is the negative slope: 5.1 10-5 s-1.
Chemical Kinetics

Second-Order Processes
Similarly, integrating the rate law for a process that is second-order in reactant A:

Rearrange, integrate:

also in the form

y = mx + b
Chemical Kinetics

Second-Order Processes
So if a process is second-order in A, a plot of 1/[A] vs. t will yield a straight line with a slope of k.
First order: If a reaction is first-order, a plot of ln [A]t vs. t will yield a straight line with a slope of -k. Chemical
Kinetics

Half-Life
Half-life is defined as the time required for one-half of a reactant to react. Because [A] at t1/2 is one-half of the original [A], [A]t = 0.5 [A]0.
Chemical Kinetics

Half-Life
For a first-order process, set [A]t=0.5 [A]0 in integrated rate equation:

NOTE: For a first-order process, the half-life does not depend on [A]0.

Chemical Kinetics

Half-Life- 2nd order

For a second-order process, set [A]t=0.5 [A]0 in 2nd order equation.

Chemical Kinetics

Lecture no. 11

Chemical Kinetics

Activation Energy
In other words, 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.

Chemical Kinetics

Temperature and Rate

Generally, as temperature increases, so does the reaction rate. This is because k is temperature dependent.
Chemical Kinetics

Maxwell-Boltzman Distribution

At higher temperatures, more molecules will have adequate energy to react. This increases the reaction rate.
Chemical Kinetics

The Collision Model

In a chemical reaction, bonds are broken and new bonds are formed. Molecules can only react if they collide with each other.
Chemical Kinetics

The Collision Model

Furthermore, molecules must collide with the correct orientation and with enough energy to cause bond breakage and formation.

Chemical Kinetics

Reaction Coordinate Diagrams

It is helpful to visualize energy changes throughout a process on a reaction coordinate diagram like this one for the rearrangement of methyl isonitrile.
Chemical Kinetics

Reaction Coordinate Diagrams

It shows the energy of the reactants and products (and, therefore, E). The high point on the diagram is the transition state.

The species present at the transition state is called the activated complex. The energy gap between the reactants and the activated complex is the activation energy barrier.

Chemical Kinetics

Arrhenius Equation
Svante Arrhenius developed a mathematical relationship between k and Ea:

where A is the frequency factor, a number that represents the likelihood that collisions would occur with the proper orientation for Chemical reaction. Kinetics

Arrhenius Equation
Taking the natural logarithm of both sides, the equation becomes 1 RT
y = mx + b When k is determined experimentally at several temperatures, Ea can be calculated from the slope of a plot of ln k vs. 1/T.

Chemical Kinetics

Outline: Kinetics
First order
Rate Laws
Integrate d Rate Laws

Second order

Second order

complicated

Half-life

complicated

k(T)
Chemical Kinetics

Lecture no.12

Chemical Kinetics

Reaction Mechanisms
The sequence of events that describes the actual process by which reactants become products is called the reaction mechanism.

Chemical Kinetics

Reaction Mechanisms
Reactions may occur all at once or through several discrete steps. Each of these processes is known as an elementary reaction or elementary process.
Chemical Kinetics

Reaction Mechanisms

The molecularity of a process tells how many molecules are involved in the process. The rate law for an elementary step is written directly from that step.
Chemical Kinetics

Multistep Mechanisms
In a multistep process, one of the steps will be slower than all others. The overall reaction cannot occur faster than this slowest, rate-determining step.

Chemical Kinetics

Slow Initial Step

NO2 (g) + CO (g) NO (g) + CO2 (g)
The rate law for this reaction is found experimentally to be Rate = k [NO2]2 CO is necessary for this reaction to occur, but the rate of the reaction does not depend on its concentration. This suggests the reaction occurs in two steps.
Chemical Kinetics

Slow Initial Step

A proposed mechanism for this reaction is Step 1: NO2 + NO2 NO3 + NO (slow) Step 2: NO3 + CO NO2 + CO2 (fast)

The NO3 intermediate is consumed in the second step.

As CO is not involved in the slow, rate-determining step, it does not appear in the rate law.

Chemical Kinetics

Fast Initial Step

The rate law for this reaction is found (experimentally) to be

Because termolecular (= trimolecular) processes are rare, this rate law suggests a two-step mechanism.

Chemical Kinetics

Fast Initial Step

A proposed mechanism is

Step 1 is an equilibriumit includes the forward and reverse reactions.

Chemical Kinetics

Fast Initial Step

The rate of the overall reaction depends upon the rate of the slow step. The rate law for that step would be

But how can we find [NOBr2]?

Chemical Kinetics

Fast Initial Step

NOBr2 can react two ways:
With NO to form NOBr By decomposition to reform NO and Br2

The reactants and products of the first step are in equilibrium with each other. Therefore, Chemical Ratef = Rater Kinetics

Fast Initial Step

Because Ratef = Rater , k1 [NO] [Br2] = k1 [NOBr2] Solving for [NOBr2] gives us k1 [NO] [Br2] = [NOBr2] k1

Chemical Kinetics

Fast Initial Step

Substituting this expression for [NOBr2] in the rate law for the rate-determining step gives

Chemical Kinetics