Unit 5: Chemical Kinetics

Chapter 14

James F. Kirby
Quinnipiac University
Hamden, CT
Edited By Myriah Day
Warm Up
Consider the reaction:
X2 + 3 Y2 2 XY3.

If [X]t is 0.750 M/min, then [XY3]/t is

a. 0.750 M/min.
b. 0.225 M/min.
c. 2.25 M/min.
d. 2.25 M/min.
Agenda
1. Lecture Notes: Rate Law
2. Demonstration
3. Guided Practice: Rates of Reaction II
Determining Concentration Effect on
Rate
How do we determine what effect the
concentration of each reactant has on
the rate of the reaction?
We keep every concentration constant
except for one reactant and see what
happens to the rate.
Then, we change a different reactant.
We do this until we have seen how each
reactant has affected the rate.
 An Example of How Concentration
Affects Rate
Experiments 13 show how [NH4+] affects rate.
Experiments 46 show how [NO2] affects rate.
Result: The rate law, which shows the relationship between
rate and concentration for all reactants:
Rate = k [NH4+] [NO2]
Rate Law and Order of Reaction

The exponents tell the order of reaction with

respect to each reactant.
In our example from the last slide:
Rate = k [NH4+] [NO2]
The order with respect to each reactant is 1. (It is
first order with respect to NH4+ and NO2.)
The overall reaction is second order (1 + 1 = 2; we
just add up all of the reactants orders to get the
reactions order). This reaction is said to have an
overall reaction order of 2, or is 2nd order overall
Rate Law and Rate Constant
Rate = k [NH4+] [NO2]
The rate law equation shows how rate depends on
concentrations.
For the general reaction
aA+ b B c C + d D
The rate law generally has the form of
Rate = k [A]m [B]n
What is k? It is the rate constant. It is a temperature-
dependent quantity.
The exponents m and n are typically small whole numbers.
If we know these exponents, the orders, we can figure
out some of the steps of complex reactions.
Rate Law and Rate Constant
Once we know the rate law for a reaction and
the reaction rate for a set of reactant
concentrations, we can calculate k.
Example page 622

Once we have both the rate law and the value

of k for a reaction, we can predict the reaction
rate for any set of concentrations.
Reaction Orders: Exponents in the
Rate Law
The rate law generally has the form of
Rate = k [A]m [B]n
The exponents in the rate law equation are called
reaction orders
These numbers tell us exactly how the rate will be
affected by reactant concentrations.
In the previous example,
Rate = k [NH4+] [NO2]
The rate doubles when the concentration of NH 4+ doubles,
triples when it triples, etc. All because the rate law shows
that the exponent for [NH4+] is one.
 Learning Check:
Share with a neighbor

Write the general form for a

rate law that has reactant A
and B and has this equation:
A+BC
Reaction: A + B C + D
Rate = k[A][B]
The overall order of this
reaction is
a. first.
b. second.
c. third.
d. fourth.
 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.
Chunk Notes

and write at least one

question in the margin.
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.
Warm Up

Take a moment and discuss with a partner what you think the most important
chunk of information was last class.
Warm Up 4/1
Take out notes for me to 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 [H2] = 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 2 = k t or t =
0.693/k
Chunk Notes

and 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
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.
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
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.
If there 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

In a 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.
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
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
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.