Unit 5: Chemical Kinetics

Day 4: Rate Law Continued

James F. Kirby
Quinnipiac University
Hamden, CT
Edited By Myriah Day
Warm Up
Reaction: A + B C + D
Rate = k[A][B]
The overall order of this reaction is

a. first.
b. second.
c. third.
d. fourth.
Agenda
1. Learning Check
2. Lecture Notes: Rate Law
1st, 2nd, 0 Order
3. Answer Guided Inquiry Questions
4. Next Class: Begin Lab Set Up
Reaction Orders: Exponents in the Rate Law
But what if the exponent for either reactant concentration was
not one?
If the order for any reactant is 2, then doubling the
concentration of that reactant will do what to the rate?
What if you triple the concentration, what will happen to the
rate?
Although the exponents in the rate law equation are
sometimes the same as the coefficients in the balanced
equation, this is not always the case. For any reaction, the
rate law must be determined experimentally.
Context
In 2000, over 20 million kilograms of the pesticide 1,3-
dichloropropene (1,3-D) were applied to crops in the U.S.
[Before its use?] Scientists investigated the rate of
decomposition of 1,3-D in acidic, basic, and neutral
solutions as well as in soil. For each case they generated
plots of the amount of intact 1,3-D persisting versus time
and found that the reaction could be characterized as
pseudo first order. Knowing the order allowed them to
determine the half life of intact 1,3-D. In acidic
solutions, the half life was 8 days. In basic solutions, it
was four days. Experimentally determined data like this
is vital to the ability of society to use chemicals more
wisely to improve not only the quality of life for
humans, but to preserve the health of our ecosystems.
LEARNING CHECK
The following data were measured for the reaction of
nitric oxide with hydrogen:
2 NO(g) + 2 H2(g) N2(g) + 2 H2O(g)
Experiment [NO] [H2] Initial Rate
(M/s)
1 0.10 0.10 1.23 x 10-3
2 0.10 0.20 2.46 x 10-3
3 0.20 0.10 4.92 x 10-3

a. Determine the rate law for this reaction

b. Calculate the rate constant
c. Calculate the rate when [NO] = 0.050 M and [H 2] =
0.150 M
First Order Reactions
Some rates depend only on one
reactant to the first power.
These are first order reactions.
The rate law becomes:
Rate = k [A]
 First Order Reactions
rate = k [A]
rate = [A] / t
So: k [A] = [A] / t
Rearrange to: [A] / [A] = k t
Integrate: ln ([A] / [A]o) = k t
Rearrange: ln [A] = k t + ln [A]o
Note: this follows the equation of a
line: y = m x + b
So, a plot of ln [A] vs. t is linear.
An Example: Conversion of Methyl
Isonitrile to Acetonitrile
The equation for the reaction:
CH3NC CH3CN
It is first order.
Rate = k [CH3NC]
 Finding the Rate Constant, k
Besides using the rate law, we can find
the rate constant from the plot of
ln [A] vs. t.
Remember the integrated rate law:
ln [A] = k t + ln [A]o
The plot will give a line. Its slope will
equal k.
 Half-life
Definition: The amount of time it takes
for one-half of a reactant to be used up
in a chemical reaction.
First Order Reaction:
ln [A] = k t + ln [A]o
ln ([A]o/2) = k t + ln [A]o
ln ([A]o/2) + ln [A]o = k t
ln ([A]o / [A]o/2) = k t
ln 1/2 = - k t
t = 0.693/k
Chunk Notes
Write at least one question
in the margin.
Table Talk
Share one thing you learned
Share one thing you are not
sure about or confused about
The value of the rate constant
(k) for a first-order reaction is
0.010 sec1. What is the half-
life of this reaction?
a. 10 seconds
b. 69 seconds
c. 100 seconds
d. 690 seconds
Second Order Reactions
Some rates depend only on a
reactant to the second power.
These are second order reactions.
The rate law becomes:
Rate = k [A]2
Solving the Second Order
Reaction for A Products
rate = k [A]2
rate = [A] / t
So, k [A]2 = [A] / t
Rearranging: [A] / [A]2 = k t
Using calculus: 1/[A] = 1/[A]o + k t
Notice:The linear relationships for first
order and second order reactions differ!
 An Example of a Second Order
Reaction: Decomposition of NO2

A plot following NO2

decomposition shows
that it must be second
order because it is linear
for 1/[NO2], not linear
for ln [NO2].
Equation:
NO2 NO + O2
Half-Life and Second Order
Reactions
Using
the integrated rate law, we can see
how half-life is derived:
1/[A] = 1/[A]o + k t
1/([A]o/2) = 1/[A]o + k t
2/[A]o 1/[A]o = k t
t = 1 / (k [A]o)
So,
half-life is a concentration dependent
quantity for second order reactions!
 Zero Order Reactions
Occasionally, rate is
independent of the
concentration of the
reactant:
Rate = k
These are zero order
reactions.
These reactions are linear
in concentration.
Select the incorrect statement.
a. The exponents in a rate law are taken
from the coefficients in the balanced
reaction.
b. For a first-order reaction, the plot of
ln[A] versus time is linear.
c. For a zero-order reaction, the plot
of [A] versus time is a parabola.
d. The slope of 1/[A] versus time is the
half-life of a first-order reaction.
If tripling the concentration of
reactant A multiplies the rate
by a factor of nine, the reaction
is _______ order in A.
a. zeroth
b. first
c. second
d. third
Factors That Affect Reaction Rate
1. Temperature
2. Frequency of collisions
3. Orientation of molecules
4. Energy needed for the reaction to take
place (activation energy)
 Temperature and Rate
Generally, as
temperature increases,
rate increases.
The rate constant is
temperature dependent:
it increases as
temperature increases.
Rate constant doubles
(approximately) with
every 10 C rise.
 Frequency of Collisions
The collision model is based on the kinetic
molecular theory.
Molecules must collide to react.
Ifthere are more collisions, more reactions
can occur.
So, if there are more molecules, the reaction
rate is faster.
Also,if the temperature is higher, molecules
move faster, causing more collisions and a
higher rate of reaction.
The Collision Model
Ina chemical reaction, bonds are broken
and new bonds are formed.
Molecules can only react if they collide
with each other.
Orientation of Molecules
Molecules can often collide without forming
products.
Aligning
molecules properly can lead to
chemical reactions.
Bonds must be broken and made and atoms
need to be in proper positions.
Energy Needed for a Reaction to
Take Place (Activation Energy)
Theminimum energy needed for a reaction to
take place is called activation energy.
An energy barrier must be overcome for a reaction
to take place, much like the ball must be hit to
overcome the barrier in the figure below.
Warm Up
Below are graphs of how the concentration of a reactant, A, changed
over time during a reaction. Based on the graphs, what order reaction is
this?
Todays Plan
Kinetics of Crystal Violet Fading
Read: New Lab Handout
Answers to Pre-Lab Together
Introductory Activity (in lab)
Guided Inquiry Design Discussion/Help
Kinetics of Crystal Violet
Fading
Concentration
Pre-Lab Volume of Volume of
(mol/L)
1. 2.5 x10-5 CV distilled water
(mL)

2.5 x10-5 = 25 uM 10.0 mL 0.0 mL

2.5 x10-6 = 2.5 uM
5.0 x10-6 = 5.0 uM
7.5 x10-6 = 7.5.0 uM
10.0 x10-6 = 10.0 uM
12.5 x10-6 = 12.5 uM 5.0 mL 5.0 mL
Kinetics of Crystal Violet
Fading
Guided Inquiry Design and Procedure
Part A
CV+ + OH- CVOH

What percent of OH- ions will remain at the end

of a reaction if the initial concentrations of
each reactant were equal (1:1 ratio)?
WARM UP 4/12
Please take out a computer from the computer cart.
Open the file I sent you and your team over email
Kinetics of Crystal Violet
Fading
Review:

CV+ + OH- CVOH

purple colorless

Rate = k[CV+]m [OH-]n

Kinetics of Crystal Violet
Fading
Rate Law:
Rate = k [CV+]m
where k = k [OH-]n

The constant k is a new pseudo rate

constant. The new pseudo rate law is valid
when the concentration of OH- ions is much
greater than the concentration of CV+ ions.
Under these conditions, the [OH-] term in the
original rate law will not change much over the
course of the reaction and may be treated as a
constant in the rate equation.
Kinetics of Crystal Violet
Fading
 Kinetics of Crystal Violet
Fading

BIG IDEA:
The more color,
the more
concentrated,
the more
absorbance.
Absorbance =
Concentration
Part B: Procedure Outline
1. NaOH conc. needs to be changed, not CV+, so that the
effect on k can be calculated and the order of reaction
with respect to OH- determined
Part B: Procedure Outline
1. NaOH conc. needs to be changed, not CV+, so that the
effect on k can be calculated and the order of reaction
with respect to OH- determined
2. Colorimeter must be zeroed with a blank, equal volumes
0.01 M NaOH and water
Part B: Procedure Outline
1. NaOH conc. needs to be changed, not CV+, so that the
effect on k can be calculated and the order of reaction
with respect to OH- determined
2. Colorimeter must be zeroed with a blank, equal volumes
0.01 M NaOH and water
3. To make 10 mL of 0.01 M NaOH, measure 5.0 mL of 0.02 M
NaOH in a serological pipet and
Part B: Procedure Outline
1. NaOH conc. needs to be changed, not CV+, so that the
effect on k can be calculated and the order of reaction
with respect to OH- determined
2. Colorimeter must be zeroed with a blank, equal volumes
0.01 M NaOH and water
3. To make 10 mL of 0.01 M NaOH, measure 5.0 mL of 0.02 M
NaOH in a serological pipet and
4. Clean the pipet with small portions of crystal violet
solution. Measure 10 mL of 25 uM crystal violet solution
Part B: Procedure Outline
1. NaOH conc. needs to be changed, not CV+, so that the effect
on k can be calculated and the order of reaction with
respect to OH- determined
2. Colorimeter must be zeroed with a blank, equal volumes 0.01
M NaOH and water
3. To make 10 mL of 0.01 M NaOH, measure 5.0 mL of 0.02 M
NaOH in a serological pipet and
4. Clean the pipet with small portions of crystal violet solution.
Measure 10 mL of 25 uM crystal violet solution
5. After the absorbance vs. time data are recorded, the
absorbance values need to be converted into concentration,
then separate data columns for ln[CV+] and 1/[CV+] need to
be created and analyzed to determine k for the new
concentration of NaOH, 0.01 M.
 Transition State (Activated
Complex)
Reactants gain energy as the reaction proceeds until the particles reach the
maximum energy state.
The organization of the atoms at this highest energy state is called the
transition state (or activated complex).
The energy needed to form this state is called the activation energy.
 Reaction Progress
Plots are made to show the energy
possessed by the particles as the reaction
proceeds.
At the highest energy state, the transition
state is formed.
Reactions can be endothermic or
exothermic after this.
 Distribution of the Energy of
Molecules
Gases have an average temperature, but each individual molecule has its own
energy.
At higher energies, more molecules possess the energy needed for the reaction
to occur.
The Relationship Between Activation
Energy & Temperature
Arrheniusnoted relationship between activation
energy and temperature: k = AeEa/RT
Activationenergy can be determined graphically
by reorganizing the equation: ln k = Ea/RT + ln A
Law vs. Theory
Kinetics gives what happens. We call the description the rate law.
Why do we observe that rate law? We explain with a theory called a
mechanism.
A mechanism is a series of stepwise reactions that show how
reactants become products.
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.
Molecularity

The molecularity of an elementary reaction

tells how many molecules are involved in that
step of the mechanism.
Termolecular?
Termolecular steps require three molecules to simultaneously collide
with the proper orientation and the proper energy.
These are rare, if they indeed do occur.
These must be slower than unimolecular or bimolecular steps.
Nearly all mechanisms use only unimolecular or bimolecular
reactions.
What Limits the Rate?
Theoverall reaction cannot occur faster than
the slowest reaction in the mechanism.
We call that the rate-determining step.
 What is Required of a Plausible
Mechanism?
The rate law must be able to be devised from the rate-determining step.
The stoichiometry must be obtained when all steps are added up.
Each step must balance, like any equation.
All intermediates are made and used up.
Any catalyst is used and regenerated.
 A Mechanism With a Slow Initial Step

Overall equation: NO2 + CO NO + CO2

Step 1: NO2 + NO2 NO + NO3 (slow)

Step 2: NO3 + CO NO2 + CO2 (fast)

 A Mechanism With a Slow Initial Step

Overall equation: NO2 + CO NO + CO2

Step 1: NO2 + NO2 NO + NO3 (slow)

Step 2: NO3 + CO NO2 + CO2 (fast)

NO2 + NO2 + NO3 + CO NO + NO3 + NO2 + CO2

 The sum of the two steps = overall
equation
Overall equation: NO2 + CO NO + CO2

Step 1: NO2 + NO2 NO + NO3 (slow)

Step 2: NO3 + CO NO2 + CO2 (fast)

NO2 + NO2 + NO3 + CO NO + NO3 + NO2 + CO2

 Notice the intermediate?

Overall equation: NO2 + CO NO + CO2

Step 1: NO2 + NO2 NO + NO3 (slow)

Step 2: NO3 + CO NO2 + CO2 (fast)

NO2 + NO2 + NO3 + CO NO + NO3 + NO2 + CO2

 Rate law: Rate = k [NO2]2

Overall equation: NO2 + CO NO + CO2

Step 1: NO2 + NO2 NO + NO3 (slow)

Step 2: NO3 + CO NO2 + CO2 (fast)

NO2 + NO2 + NO3 + CO NO + NO3 + NO2 + CO2

Rate law: Rate = k [NO2]2

Step 1: NO2 + NO2 NO + NO3 (slow)

Since the slow step determines the

rate

Rate = k [NO2]1 [NO2]1

Rate = k [NO2]2
A Mechanism With a Slow Initial Step
(completed)
Rate law: Rate = k [NO2]2
Since the first step is the slowest step, it
gives the rate law.
Ifthe first step is the rate-determining step,
the coefficients on the reactants side are the
same as the order in the rate law!
Ifyou add up all of the individual steps (2 of
them), you get the stoichiometry.
Eachstep balances, this is a plausible
mechanism.
Catalysts
Catalysts increase the rate of a reaction by
decreasing the activation energy of the
reaction.
Catalystschange the mechanism by which
the process occurs.
Types of Catalysts

1) Homogeneous catalysts
2) Heterogeneous catalysts
3) Enzymes
Homogeneous Catalysts
The reactants and catalyst are in the same phase.
Many times, reactants and catalyst are dissolved in the same solvent, as
seen below.
 Heterogeneous Catalysts
The catalyst 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.
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.
Lock-and-Key Model
In the enzymesubstrate model, the substrate fits into the active site
of an enzyme, much like a key fits into a lock.
They are specific.