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Kinetics
HANEEN AL ASHQAR
Kinetics

RATE OF REACTION. DYNAMIC

EQUILIBRIUM.
 Rate of the reaction 2. Average Reaction Rate
the change in concentration of reactants Taking the rate over long intervals
or products per unit of time.

Product concentration increases (+ive)

Reactant concentration decreases(-ive)

Δ[A]
Rate=
Δt

1. Instantaneous Reaction Rate

Simply, the rate at any time.

• To determine, calculate the slope of a

line tangent to the curve at that point in Spontaneous reaction: a reaction that will happen
time. by itself but with no information of how fast it
will happen
• The rates of change of the reactant and the product concentrations are determined
by the stoichiometry in the balanced chemical equation.

• Rate is not constant, it changes over time. Graphing the rate of a reaction will show
the average over time.
Exercise # 1:
Exercise # 2:
For the reaction N2 + 3H2 2NH3
•
Consider the following reaction:
2 NO2(g) O2(g) + 2 NO(g)
write the relative rates of change in concentration of products and reactants
Collision theory The explanation of rate of reaction
• For a reaction to proceed particles of the reactants should be collide with each other
(only two particles can collide at a time) successfully to initiate bond-breaking and bond-
making events.

• To have successful collision particles should have

1. sufficient energy (activation energy) to overcome energy barrier, the
electron/electron repulsion of the valence shell electrons of the
reactant, and to transform the translational energy into vibrational
energy in order to penetrate into each other so that the electrons can
rearrange and form new bonds.
2. orientations that allow the bonds to rearrange in the required manner.

• The Maxwell-Boltzmann distribution curve describes the distribution of particle

energies; this distribution can be used to gain a qualitative estimate of the fraction of
collisions with sufficient energy to lead to a reaction, and also how that fraction
depends on temperature.
Correct orientations producing new substance

Incorrect orientations do not produce new substance

.

You can mark the activation energy, Ea,

on a Maxwell-Boltzmann diagram.

Only the molecules to the right of the

Ea will have enough energy to react
when the collide. The rest just bounce
apart.

If we increase the temperature from T1

to T2, more molecules are energetic
enough to achieve the Ea, thus more
molecules react and the overall rate
increases.

Again, general rule of thumb, every 10oC

increase, the double the rate!
Factors that Affect Rate of Reactions
1. Nature of the reactants.
Some reactions are very fast, others are not.
Physical state:
solids react very slowly compared to liquids or aqueous phases.
• E.g. K2SO4(s) + Ba(NO3)2(s) No Reaction
However, if they are both aqueous, the reaction occurs instantaneously.
gases react faster than liquids,

Chemical Identity – what exactly is reacting?

 Ions of opposite charge react very rapidly.
 The more bonds in a molecule, the slower the reaction. (Why? More energy
is required to break the bonds in order to react.)
 Substances with large bond energies also take longer to react.
2. Concentration of reactants: The more molecules present, the more molecules that
have activation energy, the more successful collisions that can occur. The faster the
reaction can occur, then the greater the rate.

3. Temperature: the faster molecules move, the more likely they are to collide with
each other. Bonds will be broken and new bonds will form.
• An increase in temperature produces successful collisions that are able to
overcome the needed activation energy (Ea). Therefore, increased temperature
will increase the rate.

• Generally, a 10oC increase in temperature doubles the rate.

• This still depends on Ea (The activation energy) and the temperature range.
4. Surface Area of reactants: exposed areas affect speed.

• Except for substances in the gaseous or aqueous phases, reactions take place at
the boundary, or the interface between the two physical states. (In other words,
the exposed surface.)
The greater the surface area, the greater the chance of collision between
particles, thus faster reaction. E.g. coal dust is far more explosive than one piece
of coal.

• Aqueous solutions are the ultimate exposure!

5. Adding an INERT gas has NO EFFECT on the equilibrium (will be covered later in another unit)
or the rate of a reaction, since it is NOT in the reaction mechanism. (Classic trick question on
exams.)

6. Catalysis is the increase of a chemical reaction due to the participation of a

catalyst. Unlike other reactants, a catalyst is NOT consumed in the reaction, so it
can be used over and over and over again. More on catalysts later.
Rate law
1. The initial rate method
k is mostly temperature dependent and can only be
R = k [A]m [B]n found via experimentation

-The relation between the reaction rate and the concentration of the reactants
-m, n are the order of the reaction
-The order of the reaction can be determined by experiment only
-To find the exact relation between rate and concentration, we must conduct
experiments, collect data, and interpret the data.
-Begin with pure reactants, mix thoroughly, then measure the speed over the course
of the reaction. By Counting bubbles, measuring mass of precipitate, using
spectroscopy to measure color change, etc.
Zero order: the change in concentration has absolutely no effect on the rate. Rare.

• Rate = k[A]0 = k

First order: Rate is directly proportional to the change in concentration; doubling the
change in concentration, doubles the rate, very common!

Rate = k[A]1 = k[A]

• Second Order: The rate is quadrupled when the change in concentration is doubled, and times
9 when the change in concentration is tripled.

General form: rate = k[A]2 or

rate = k[A]1[B]1(overall order of 2)

• If r = k[A]m[B]n:
• Then:
• If m = 0, zero order with respect to [A]
• If m = 1, first order with respect to [A]
• If m = 2, second order with respect to [A]
• If n = 0, zero order with respect to [B]
• If n = 1, first order with respect to [B]
• If n = 2, second order with respect to [B]

• Adding together all of the orders will gives the overall order of the reaction.
Ponder the experimental data for the reaction:
A+B Product

Experiment Initial Rate Initial Initial

Number (mol/(L·hr)) Concentration [A]o Concentration [B]o
(mol/L) (mol/L)
1 0.50 x 10-2 0.50 0.20

2 0.50 x 10-2 0.75 0.20

3 0.50 x 10-2 1.00 0.20

4 1.00 x 10-2 0.50 0.40

5 1.50 x 10-2 0.50 0.60

•
•
• In the following reaction, a Co-Cl bond is replaced by a Co-OH2 bond.
[Co(NH3)5Cl]+2 + H2O [Co(NH3)5H2O]+3 + Cl-
Initial rate = k{[Co(NH3)5Cl]+2}m
Using the data below, find the order of m and calculate the value of k.

Experiment Number Initial Concentration of Initial Rate, in

[Co(NH3)5Cl]+2 in mol/L mol/(L·min)
1 1.0x10-3 1.3 x 10-7
2 2.0x10-3 2.6 x 10-7
3 3.0x10-3 3.9 x 10-7
• The reaction between bromate ions and bromide ions in acidic solution is given by the
equation:
BrO3-(aq) + 5 Br-(aq) +6 H+(aq) 3 Br2(l) + 3 H2O(l)
The table below gives the results of four experiments. Using these data, determine the
orders for all three reactants, the overall order, and the rate constant.

Trial Initial Initial Initial Measured Initial Rate

Number [BrO3-] [Br-] [H+]
1 0.10 0.10 0.10 8.0x10-4
2 0.20 0.10 0.10 1.6x10-3
3 0.20 0.20 0.10 3.2x10-3
4 0.10 0.10 0.20 3.2x10-3

• The overall order of the reaction is 1 + 1 + 2 = 4.

• k=8
 2. The integrated rate method (Concentration-Time Data)

You are in search of linear data! If you do the set of graphs in this order with
the y-axis being concentration, natural log, and reciprocal, the alphabetical
order of the y-axis leads to 0, 1, 2 orders respectively for that reactant.

|slope| = k

[A] = -kt + [A]o ln[A] = -kt + ln[A]o 1/[A] = kt + 1/[A]o

Rate constant unit mol dm-3 time-1 time-1 mol-1 dm3 s-1
The graph to the right is the radioactive
decay data collected for element ‘Q’.
Answer the following questions.

1. While you may not be able to give the order

of the reaction at first glance, you should
know what order it is NOT. Which order is
NOT the order for this reaction?

2. What is the half-life of element ‘Q’?

3. What is the molar concentration of ‘Q’ after a second

half-life has elapsed?

4. At what time has 75 % of the original sample

decayed?
For the reaction of (CH3)3CBr with OH- Time(s) [(CH3)3CBr]
0 0.100
(CH3)3CBr + OH- (CH3)3COH + Br-
30 0.074
The following data were obtained in the laboratory: 60 0.055
A. Determine the order of this reaction. Sketch your graph. 90 0.041

B. Determine the value of the rate constant with the proper units.
C. At what time is the concentration of (CH3)3CBr equal to [0.086]? Justify your answer.
D. At what time is the concentration of (CH3)3CBr equal to [0.025]? Justify your answer.
E. What is the concentration of (CH3)3CBr at 2.0 minutes? Justify your answer.

[] vs time ln[] vs time 1/[] vs time

The decomposition of N2O5 in the gas phase was studied at constant [N2O5] Time
temperature.
0.1000 0
0.0707 50
2 N2O5(g) 4 NO2(g) + O2(g)
0.0500 100
0.0250 200
The following results were collected:
0.0125 300
0.00625 400
A. Determine the rate law and calculate k.
B. Determine the concentration at 250 s. Does your calculated answer make sense? Justify your answer.
C. Determine the concentration at 600 s. Does your calculated answer make sense? Justify your answer.
D. At what time is the concentration 0.00150 M? Explain how you know your answer is correct.

[] vs time ln[] vs time 1/[] vs time

• Butadiene reacts to form its dimer by the reaction:
• 2 C4H6(g) C8H12(g)
• The following data was collected for this reaction at a given temperature:
[C4H6] Time (+/- [C4H6] Time (+/-
1s) 1s)
A) Determine the order of this reaction. Write
0.01000 0 .00313 3600
the rate law expression. Justify your answer.
.00625 1000 .00270 4400
Sketch a graph as part of your explanation.
.00476 1800 .00241 5200
B) Determine the value of the rate constant for
.00370 2800 .00208 6200
this reaction.
C) Determine the half-life for the reaction under the conditions of the experiment.

[] vs time ln[] vs time 1/[] vs time

Questions
a. A radioactive isotope of the element decays with a half life of 10 minutes
i. Calculate the value of the rate constant k for the radioactive decay include
units with your answer
ii. If 64 atoms of the radioactive isotope are originally present in a sample what
is the expected amount of time that will unlit only one atom of the isotope
remains. Show how you arrived at your answer (AP 2018)
1. A certain first order reaction has a half-life of 20.0 minutes.
A) Calculate the rate constant.
B) How much time is required for the reaction to be 75% complete?

2. The rate constant for the first order transformation of cyclopropane to propene
is 5.40 x 10-2 hr-1. Calculate the half life of this reaction. What fraction remains
after 51.2 hours? What fraction remains after 18.0 hours?
1.
•
2.
•
•
3. Mechanism of the reaction (elementary steps)
it is a series of elementary steps that must satisfy the following:

1. The sum of the elementary steps MUST agree with overall balanced equation.
2. Must agree with the experimentally determined rate law.

• A mechanism represents the sequence of bond making and bond breaking steps that
occur during the conversion of reactants to products.
• This process involves a series of smaller reactions.
• The vocabulary of mechanisms involves elementary steps and molecularity which
describes the number of molecules that participate in an atomic rearrangement.
(Another way to think of molecularity is how many molecules must collide with each
other in order to have a reaction.)
-Unimolecular: involves a collision between one reactant
-Bimolecular: involves a collision between two reactant molecules.
-Termolecular: VERY RARE: involves a collision between three reactant molecules.
 Elementary Step Molecularity Rate Expression
A Products Unimolecular Rate = k[A]
A+B Products Bimolecular Rate = k[A][B]
A+B+C products Termolecular Rate = k[A][B][C]

• Molecularity and order

• An elementary step is a reaction whose rate law can be written from its
molecularity
NOT true of the overall reaction
• Nitrogen oxide is reduced by hydrogen to give water and nitrogen.
2H2(g) + 2 NO(g) N2(g) + 2 H2O(g)

• One possible mechanism to account for this reaction is:

2 NO(g) N2O2(g)
Intermediates: molecules that are formed as a product
N2O2(g) +H2(g) N2O(g) + H2O(g) in one elementary step and are consumed in another
elementary step
N2O(g) + H2(g) N2(g) + H2O(g)
catalyst: molecules that are consumed as a reactant in
one elementary step and are formed in another
elementary step

• What is the molecularity of each of these steps? Show that the sum of these elementary
steps yields the net reaction.
• The slowest step is the rate determining step.
• The rate of the overall reaction is limited by, and is exactly equal to, the combined
rates of all elementary steps up to and including the slowest step in the mechanism.

The balanced equation for the reaction of the gases nitrogen dioxide and fluorine is
2 NO2(g) + F2 2 NO2F(g)
The experimentally determined rate law is:
rate = k[NO2][F2]
A suggested mechanism for the reaction is:
• NO2 + F2 NO2F + F slow
• F + NO2 NO2F fast
Is this an acceptable mechanism? That is, does it satisfy the two accepted
requirements?
The mechanism for the reaction of nitrogen dioxide with carbon monoxide to form
nitric oxide and carbon dioxide is thought to be:
NO2 + NO2 🡪🡪 NO3 + NO slow
NO3 + CO 🡪🡪 NO2 + CO2 fast
Write the rate law expected for this mechanism.
What is the overall balanced equation for the reaction?
Effect of temperature on the rate constant

Arrhenius equation the equation for the relationship between the rate constant and
temperature.

Look back at Equation. If Ea increases, it makes the exponent a larger negative number,
resulting in a smaller rate constant (and rate). Also, an increase in T makes the negative
exponent smaller, resulting in an increased reaction rate.

When the natural logarithm of the above Equation is taken, the result is
This equation can be utilized in two ways:
First, a graph of ln k versus 1/T can be constructed after
determining the rate constant at a variety of temperatures. This graph, is often called an Arrhenius
plot. The slope of the line is equal to −Ea/R.
Arrhenius plots are used to
1. Determine the activation energy, Ea,
2. The rate constant at any desired temperature.
The second way: is a two-point approach using only
the rate constants determined at two different temperatures. The resulting equation is

This Equation may be written using the ratio of the rates rather than the rate constants:

Two principles must be remembered:

1. The larger rate constant (or rate) will always be associated with the higher temperature.
2. The activation energy always has a positive sign.
Energy diagram

(activated complex)
(activated complex)
 Energy diagram for the mechanism (elementary steps)

• For the following mechanism:

2 NO(g) N2O2(g)
N2O2(g) +H2(g) N2O(g) + H2O(g)
N2O(g) + H2(g) N2(g) + H2O(g)

Determine the following questions

1. which step is exothermic and which is endothermic
2. The position of activated complex
3. which is the rate determining step
For the above energy diagram Determine the following
1. How many elementary steps are there?
2. which step is exothermic and which is endothermic?
3. The position of activated complex, how many are there?
4. The position of the intermediate., how many are there?
3. which is the rate determining step?
Similar to the
Maxwell-
Bozeman plots
involving
temperature,
Catalysts allow
for more
collisions to
occur.
 Catalysis
• Catalysts are substances that speed up a reaction without being consumed itself.
• Catalysts LOWER the energy pathway.
• All biological reactions that use enzymes use catalysts.
• There are two types of
catalysis reactions:
• Homogeneous
• Heterogeneous
 • Homogeneous catalysts are those that are in the same phase as the reacting
molecules.
• Heterogeneous catalysts exist in a different phase, usually a solid.
• Most often involves a gas being adsorbed on the surface of a metal.
• Adsorption = collection of one substance on the surface of another.
• Absorption = penetration of one substance into another (like water into a sponge)
• Used in many applications, catalytic converters, hydrogenation of oils into solid
fats for food

Biological Catalysis
Follows a generic formula system:
E+S E•S
E•S E+P Where
E = enzyme S =substrate
E•S = the enzyme-substrate complex
P = the products.
Example: