≠AP Chemistry

UNIT 3 Anchor Guide Kinetics (Rates of Reactions)

Big Idea 3: Transformations:
● Why are some reactions faster than other reactions?
● How long will a marble statue last?
● How can a sports drink cure a headache?
Big Idea 4: Energy
● Why does bread rise?

Learning Objectives:
TRA-3.A Explain the relationship between the rate of a chemical reaction and experimental parameters
TRA-3.B Represent experimental data with a consistent rate law experiment
TRA-4.A Represent an elementary reaction as a rate law expression using stoichiometry TRA-4.B
Explain the relationship between the rate of an elementary reaction and the frequency, energy, and
orientation of molecular collisions
TRA-4.C Represent the activation energy and overall energy change in an elementary reaction using a
reaction energy profile
TRA-5.A Identify the components of a reaction mechanism
TRA-5.B Identify the rate law for a reaction from a mechanism in which the first step is rate limiting
TRA-5.C Identify the rate law for a reaction from a mechanism in which the first step is not rate limiting
TRA-5.D Represent the activation energy and overall energy change in a multistep reaction with a
reaction energy profile
ENE-1.A Explain the relationship between the effect of a catalyst on a reaction and changes in the
reaction mechanism

TOPIC LEARNING TARGETS I can...

activation energy
⮚ Identify four factors which affect the speed at which a reaction for
takes place. chemical
⮚ Define the term chemical kinetics. reactions.
⮚ Write and use the
⮚ Define the term reaction rate.
mathematical
⮚ Distinguish between average rate, instantaneous rate and initial equation
rate of a chemical reaction. which describes
the
⮚ Write the general rate equation for a chemical reaction and define relationship between the
each term in the rate equation. rate constant and
⮚ Define the term reaction order and explain how the order for a
temperature.
chemical reaction can be determined. ⮚ Sketch an energy profile diagram for a simple reaction and label
the important features.
⮚ Use the method of initial rates to determine the specific rate law for
a chemical reaction. ⮚ Define the terms reaction mechanism and rate
determining step.
⮚ Write and use the mathematical equation which relates the change
in concentration with ⮚ Write the rate law for a chemical reaction given the mechanism
and the rate determining step.
time (integrated rate law) for simple first order reactions. ⮚ Determine
the half-life for reactions which follow simple first order kinetics. ⮚ Suggest a possible mechanism for a chemical reaction given the
⮚ Recognize the order and determine the rate constant for a simple balanced chemical equation and the rate law. ⮚ Define the terms
reaction from a plot of ln[concentration] versus time.
reaction intermediate and catalyst. ⮚ State the two factors which
⮚ Write and use the mathematical equation which relates the change determine if a collision is effective, and how the arrhenius equation
in concentration with time (integrated rate law) for simple takes these factors into account
second order reactions.
⮚ Describe the basic structure and function of different catalysts
⮚ Determine the half-life for reactions which follow simple
second order kinetics. ⮚ Use energy distribution diagrams to show how lowering the

⮚ Recognize the order and determine the rate constant for a simple temperature lowers the reaction rate ⮚ Use energy distribution
reaction from a plot of diagrams and progress of reaction diagrams to show how a catalyst
1/ concentration versus time. increases the rate of a reaction
⮚ Define the term
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Introduction to Rates: Watch this video Rates (and how to get a date to the Prom) and summarize the key
points

RATES: KEY Goals:

(1) Understand how to determine reaction rates and develop models to create reaction mechanisms
(2) Consider the factors that control these rates

Chemical Kinetics: The area of chemistry concerned with the rates of reactions

Collision Model - Reaction rates depend on:

1. The frequency of collisions between molecules

2. Sufficient energy to stretch bonds to a critical length for bonds to be broken
3. Proper orientation of molecules for new bonds to be formed

Define the term rate of reaction:

How is the rate of a chemical change or the reaction rate usually expressed? What are the units of rate?

Consider the following video: “Elephant Toothpaste”

Which reaction is occurring at a fast rate? Slow rate? ____________________________________________
(research this reaction: can you explain WHY you are seeing what you are seeing).
If you graph a property of this reaction over time: (i)Which property are you measuring? __________________
(ii) Is it a reactant property or a product property? ________________________
(iii) Create a data table that will allow you to collect data regarding the rate of reaction
(iv) Sketch what your data would look like for both experiments (on one graph)
Data table:
Sketch of graph (include both)
(as time allows, fill in the data table)

(v) Suggest two possible reasons why the rate of reaction in the blue tube is different from the rate of reaction in the
red tub
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The reaction of hydrochloric acid with calcium carbonate can be used to illustrate the two typical curves obtained
depending on whether the concentration of reactants or products is followed:

CaCO3(s) + 2HCl(aq) --> CaCl2(aq) + H2O(l) + CO2(g)

Draw the graph of concentration of HCl(aq) per time Draw the graph of volume of CO2(g) per time

Why do the curves eventually level out?

Collision Theory

There are two conditions that must be satisfied in order for reactions to occur (A.K.A. Collision theory):

1.

2.

Reaction Profiles: Remember that this graph shows the potential energy of reactant molecules compared to
products
Draw a potential energy diagram for an exothermic reaction Draw a potential energy diagram for an
endothermic reaction

Define activation energy, Ea

Define activated complex

3
Maxwell Boltzmann Distribution Curve : Consider # molecules on y axis and Energy on x axis
Factors that can increase the frequency of collisions and the amount of energy particles help speed up the rate of
reaction.

Predict and explain, using collision theory, the qualitative effect of particle size, temperature,
concentration, and catalysts on the rate of a reaction.

A. Temperature At ____________________ temperature, the motions

of
the particles are __________________ and more chaotic than at lower
temperatures. Increasing the temperature increases both the
____________________ of collisions and the _______________ of
particles
that have enough kinetic energy to overcome activation energy barrier.

B. Concentration Cramming more particles into a fixed volume

_______________ the concentration of ______________ and consequently
the __________________ of collisions.
Increased _______________ frequency leads to higher reaction rates

C. Particle Size The total surface area of a solid or liquid reactant affects the

reaction rate. The ________________ the particle size, the __________________

is the surface area for a given mass of particles. An ___________________ in surface area

____________________ the amount of the reactants exposed for reaction, which further increase the collision

frequency and the rate of reaction

D. Catalyst A catalyst is a substance that ______________ the rate of

by
lowering the __________________________________ barrier by
providing
an alternative pathway for the reaction to happen. Now more reactant
particles have the ____________________ amount of energy to react.

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TEXT: 14.1 Factors Affecting Rates of Chemical Reactions:
 1. Phase and Surface Area of the reactants - ions collide to form precipitates fast; heterogeneous reactions
that involve solids tend to proceed faster if the surface area is increased
2. Concentration or pressure of reactants - as concentration or pressure increases, the frequency with which
the reactant molecules collide increases, leading to increased rates
3. Temperature at which the reaction occurs - Increasing temperature increases the kinetic energies of
molecules
4. Presence of a catalyst - A catalyst can stabilize a transition state, lower the activation energy and thus
increasing the rate of a reaction

14.2 Reaction Rates - the rate of reaction is the rate at which reactants are converted to products, expressed as
change in concentrations per unit time (Ms-1).

Rate of a reaction can be measured by using the properties of the reactants or products as long as they can produce
quantitative data:

1. Change in volume of gas produced over time. Mg(s)+2 HCl(aq) →MgCl2 (aq) + H2 (g) 2. Changes in
mass over time. CaCO3(s) + 2 HCl(aq) → CaCl2(aq) + CO2(g) + H2O (l) 3. Change in transmission of
light over time (colorimetry or spectrophotometry involving Beer's Law) 2 HI(g) →H2 (g) + I2 (g) colored
4. Change in concentration measured using titration over time
H2O2 (aq) + 2 H+(aq) + 2 I-(aq) →I2 (aq) + 2 H2O (l)
5. Change in concentration measured using conductivity over time
BrO3-(aq) + 5 Br-(aq) + 6 H+(aq) →3 Br2 (aq) + 3 H2O (l)
6. Change in time given different concentrations The Clock Reaction - compare rates of reactions under
different conditions

Consider the following reaction : A-->B

Average rate of disappearance of A= Average rate of appearance of B = As one molecule of A

disappears, one molecule of B appears. Sketch what this would look like over time:

Rate of disappearance of A Rate of appearance of B

(Rate of disappearance of A) = (Rate of appearance of B)

5
Consider the reaction: X → 2 Y
Sketch what this would look like over time:
Rate of disappearance of X Rate of appearance of Y
What do we mean by the term “Average Rate of Reaction”?

The negative sign in the reactant expression indicates that reactant concentration is decreasing. Rates are always expressed as
positive quantities. Rate is not constant but decreases with time because the concentration of reactants decreases.

Instantaneous rate - Rate at a particular instant in the reaction; it is determined from the slope of the curve at point of interest
Note: you will not be asked to calculate the instantaneous rate of a reaction.

Consider the reaction of butyl chloride in water:

C4H9Cl (aq) + H2O (l) → C4H9OH (aq) + HCl (aq)
Eg 1) Determine the instantaneous rate at 600 s

Instantaneous rate = Δ [C4H9Cl] over time = slope of line at that

point
At the beginning of the reaction, the slope is steep/not steep (circle one) .
This indicates a fast rate/slow rate of reaction.
The concentration of reactants is high/low. Collisions are high/low
After some time, the slope is steep/less steep. This indicates a
faster/slower rate of reaction. The concentration of reactants is high/low.
Collisions between reactants are high/low.
Reaction Rates and Stoichiometry

Eg 1) 2 HI (g) → H2 (g) + I2 (g)

_____ moles of HI disappear for ______ mole of H2 or I2 formed. The rate of disappearance of HI is _____________ the rate of
appearance of H2 or I2.
Eg 2) 2 N2O5 (g) → 4 NO2 (g) + O2 (g)
If the rate of decomposition of N2O5is 4.2 x 10-7 M/s, what is the rate of appearance of (a) NO2, and (b) O2? 6

14.3 Concentration and Rate Laws

Differential Rate Law - a mathematical expression that expresses how rate depends on reactant concentrations
raised to a power, and contains a proportionality constant called the Rate Constant k. The magnitude of k
changes with temperature.

General form of the Differential Rate Law:

Rate = k [reactant 1]m[reactant 2]n

The power m and n are called Reaction Orders. They refer to the order of the reaction with respect to a reactant.

Order with respect to reactant 1: Order with respect to reactant 2:

 Overall reaction order : sum of the powers of reactant concentrations in the rate law:

The values of powers in Rate Law expressions must be determined experimentally (cannot simply look at
coefficients in equation). Spectroscopic method can be used to measure reaction rates based on Beer's Law, where
A = εbc

Units of Rate Constants - vary depending on the overall reaction order of rate law
Rate (M/s) = k [M]exp

k = (M/s) / [M]exp or k = (Ms-1) (M-exp)

For first order: For second order:

Reaction Rate Law Overall
Unit of k
Reaction
Order

2 N2O5 → 4 NO2 + O2 Rate = k [N2O5]

CHCl2 + Cl2 → CCl4 + HCl Rate = k [CHCl3] [Cl2]½Note, this is a rare occurrence to have a
fraction

H2 + I2 → 2 HI Rate = k [H2] [I2]

7
Eg) The experimentally determined rate law for the reaction 2 NO (g) + 2 H 2 (g) → N2 (g) + 2 H2O (g) is rate = k
[NO]2[H2]. (a) What are the reaction orders in this rate law? (b) Does doubling the concentration of NO have the
same effect on rate as doubling the concentration of H2? (c) What is the unit of k?

Using Initial Rates to determine Differential Rate Laws:

Eg 1) A + B → C
Experiment No. [A] (M) [B] (M) Initial Rate (M/s)

1 0.100 0.100 4.0 x 10-5

2 0.100 0.200 4.0 x 10-5

3 0.200 0.100 16.0 x 10-5

Using these data, determine:

 a) the rate law for the reaction
b) the magnitude of the rate constant
c) the rate of the reaction when [A] = 0.050 M and [B] = 0.100 M

Eg 2) For the reaction NH4+ + NO2- → N2 + 2 H2O

Experiment No. [NH4+] initially [NO2-] initially Rate M/s

1 0.0100 M 0.200 M 5.4 x 10-7

2 0.0200 M 0.200 M 10.8 x 10-7

3 0.200 M 0.0202 M 10.8 x 10-7

4 0.200 M 0.0404 M 21.6 x 10-7

Determine the rate law and the rate constant with units.

8
14.4 Integrated Rate Law - expression of the change of concentration with time
A first-order reaction is a reaction whose rate depends on the concentration of a single reactant raised to the
first power. A → B (slow step in a multistep mechanism)
Rate = k [A] = - Δ[A] / Δt Differential Rate Law

Look at a plot of [A] vs time Now plot ln [A] vs time “natural log = ln”
Using calculus, this equation is transformed into a linear equation: y = mx + b
ln [A] = - k t +ln [A]0 Integrated Rate Law

or ln [A]t = - kt
[A]0

where y = ln [A] slope of the line -= -k intercept = ln [A]0

(1) [A] depends on time

(2) If [A0] and k are known, [A] can be calculated
(3) The plot of ln [A] vs time can be used to test if the reaction is 1st order - if it is, a straight line results

Half-life (t1/2) - time required for a reactant to reach half of its original concentrations

Half- life of First Order Reaction:

t1/2 = 0.693 / k Half life is inversely proportional to rate constant, and independent
of concentration, i.e. radioactive decays

9
Eg ) For the reaction: 2 H2O2 (aq) → 2 H2O (l) + O2 (g)

Use the following data to:

a) determine the order of the reaction

b) write the Rate Law Expression
c) calculate the rate constant with units
d) calculate [H2O2] after 1200 mins, and
e) calculate the half-life
Time (min) [H2O2] (M) Ln [H2O2] (M)

0 0.0200 -3.912

200 0.0160 -4.135

400 0.0131 -4.335

600 0.0106 -4.547

800 0.0086 -4.756

Decomposition reactions and nuclear decay reactions are all first order reactions: WHY? Collisions are not
necessary when decomposition occurs. So concentration of reactants is not a consideration when taking into
account the half life.
100 molecules X decomposes to 50 molecules in 10 min; 50 molecules decomposes to 25 molecules in 10 min….
So if you started with 1000 molecules, the half life is ____ min forming _____ molecules. Would the initial rate
be faster, slower or the same if you were comparing the decomposition of 100 molecules or 1000 molecules.
14 14 -1
Example of nuclear decay reaction: 6C → 7N + 0e

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Second-order reaction - one whose rate depends on the concentration of the reactant raised to the second
power.
Rate = k [A]2 Differential Rate Law

Look at a plot of
[A] vs time ln [A] vs time 1/[A] vs time

A plot of 1/[A] vs time will yield a straight line whose slope is the rate constant k with the following linear
equation:
1 = k t + 1 Integrated Rate Law
[A] [A]0

Half-life of Second Order Reaction

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Eg) Decomposition of nitrogen dioxide at 3000C: NO2 (g) → NO (g) + 1/2 O2 (g)
Time (sec) [NO2] (M) Ln [NO2] 1 / [NO2]

0.0 0.01000

50.0 0.00787

100.0 0.00649

200.0 0.00481

300.0 0.00380

a) Determine the order of reaction

b) Write the Rate Law Expression
c) Calculate the Rate Constant with units
d) Calculate [NO2] after 645 secs.
e) Determine the half-life

Zero-Order Rate Law (Rate is independent of the concentration of a reactant)

Half-Life of Zero-Order Reactions

 12
Summary of Kinetics for Reaction: A → Products

Order of a reaction with respect to a reactant concentration can be inferred from plots of the concentration of reactant
versus time. Experimentally it can be determined by using spectrophotometry.

14.5 Temperature and Rate

Dependence of Rate Constant on Temperature:

If the rate of reaction increases with increasing

temperature, yet the concentration of reactants stays

the same, what must change in the rate law?

k increases .

The rate of reaction approximately doubles for every 100C incase.

Collision Model: Not all collisions are successful. To get over the activation energy
barrier, molecules need sufficient ______________and proper _________________ to allow for the rearrangement of reactant
bonds to form product bonds.

The Orientation Factor

For the isomerization of methyl isonitrile, the reaction is exothermic:

Energy must be supplied to stretch the bond between the H3C

group and the N≡C group so as to allow it to rotate, so that the new
C-C bond can begin to form.

Energy Profile: gives the energy along the path that proceeds from reactants, through a transition state, to products.

Activation Energy (Ea): the minimum energy required to initiate a chemical reaction. E a = energy difference between that of the
starting molecule and the highest energy along the reaction pathway.

Activated Complex (or transition state): The particular arrangement of atoms at the top of the barrier. 13

The Maxwell-Boltzmann thermal distribution

describes
the distribution of particle energies, and how that
fraction
depends on temperature:
Only a small fraction of the collisions leads to a reaction.
At higher temperature, a larger fraction of the molecules
have greater kinetic energies than Ea, which leads to a
higher frequency of successful collisions and a faster rate of reaction.

Exercise:

Eg) Assuming that all three reactions have nearly the same frequency factors, rank the reactions from slowest to
fastest.

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14.6 Reaction Mechanisms and Rate Laws

(1) Collision Theory - Molecules must collide in order to react to form products. Only collisions having sufficient
energy and proper relative orientation of reactants lead to products.

(2) Consider the reaction proceed in a number of steps (Elementary Steps) involving one or more reactants. Very
rarely would 3 molecules collide at the same time.

(3) The mechanism of a multistep reaction consists of a series of elementary reactions (involving bond breaking
and making) that add up to the overall reaction. The balanced chemical equation of the overall reaction specifies
only the stoichiometry but not the rate.
(4) The rate is set by the slowest elementary reaction, the rate-determining step. It limits the rate and determines
the rate law.

(5) A reaction intermediate is neither a reactant nor a product; it is formed in one step and consumed in the
following step, such that it is present only while a reaction is occurring.

(6) Varying concentrations of reactants are used to determine rate law experimentally.

(7) A number of reaction mechanisms (a step-by-step process by which a reaction occurs) are postulated and
evaluated to determine which are consistent with the experimental data that are used to arrive at the rate law of an
overall reaction.

(8) A mechanism cannot be absolutely proven.

Elementary Steps:

Molecularity: number of molecules that participate as reactants in an elementary step; the order of elementary
reaction can be inferred from molecularity.

a) Unimolecular - a single molecule undergoing decomposition (first order)

b) Bimolecular - two reactant molecules collide and react (second order)

c) Termolecular - rarely do three reactant molecules collide

simultaneously and react (third order) Multistep Mechanisms (consists

of a sequence of elementary steps)

NO2 (g) + NO2 (g) → NO3 (g) + NO (g)

NO3 (g) + CO (g) → NO2 (g) + CO2 (g )

15
Eg ) The conversion of ozone into O2 proceeds by a two-step mechanism:

O3 (g) → O2 (g) + O (g)

O3 (g) + O (g) → 2 O2 (g)

(a) Describe the molecularity of each elementary reaction in this mechanism.

(b) Write the equation for the overall reaction.
(c) Identify the intermediate.
Mechanisms with a Slow Initial Step

A + A → C + X (slow)

X + B → A + D (fast)

Overall:

Rate =

Eg ) The decomposition of N2O, nitrous oxide, occurs in two-step mechanism:

N2O (g) → N2 (g) + O (g) slow

N2O (g) + O (g) → N2 (g) + O2 (g) fast

a) Write the equation for the overall reaction.

b) Write the rate law for the overall
reaction.

Mechanisms with a Fast Initial Step

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For the reaction:

2 NO (g) + Br2 (g) → 2 NOBr Rate = k[NO]2[Br2]

Does it mean it is a termolecular reaction? NO

Let us consider a possible mechanism

NO + Br2 → NOBr2 (fast) equilibrium is established

NOBr2 + NO → 2 NOBr (slow)

Since the second step is the slow step, the rate law can be written as:

But is it possible to write a rate law using an intermediate that cannot be measured?

We must be able to relate this intermediate [NOBr2] to the first step:

Generally, when a fast step precedes a slow one, the concentration of an intermediate can be solved by assuming
that equilibrium is established in the first step.

Eg) Suggest a rate law for the reaction: H2 + I2 → 2 HI

Given mechanism: I2 ↔ 2 I (fast)

H2 + 2 I → 2 HI (slow)

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14.7 Catalysis

Catalyst functions by :

(1) stabilizing a transition state and lowering the activation energy of an elementary step in a reaction
mechanism, or

(2) participating in the formation of a new reaction intermediate, thereby providing a new and faster reaction
mechanism.

Important classes include:

(1) Acid-Base Catalysis - a reactant either gains or loses a proton; this changes the rate of the reaction; it is a
homogeneous catalyst that is present in the same phase as the reacting molecules

2H2O 2 (aq) → 2H2O (l) + O2 (g) This decomposition is very slow.

But when small amounts of NaBr is added to an acidified H2O2, brown Br2is formed which then reacts with H2O2
to form O2 and regenerates Br- and H+, turning the solution back to colorless.

2 Br- + H2O2 + 2 H+ → Br2 + 2 H2O

Br2 + H2O2 → 2 Br- + 2 H+ + O2

Energy profiles for uncatalyzed and catalyzed reactions: (Note, catalyzed reactions may have a different
mechanism, such as a multistep mechanism, that leads to multiple activation energy profiles)
 (2) Surface

Catalysis
18
A heterogeneous catalyst exists in a different phase from the reactant molecules, usually as a solid in contact with
either gaseous or liquid, forming a new intermediate.

The atoms at the surface of a solid are extremely reactive in binding reactant molecules through a process called
adsorption. Upon adsorption less energy is required to break the reactant bonds, lowering the activation
energy of the reaction.

In automobile's catalytic converter, the exhaust gases of CO, unburned hydrocarbons, and nitrogen oxide (NO,
NO2) that cause air pollution come into contact with the catalytic surface composed of metals such as Pt
and transition metal oxides (CuO and Cr2O3). Adsorpton weakens the O-O bond in O2,so that oxygen
atoms are readily available to react with the exhaust gases to form CO 2, N2 and O2.

Another example is hydrogen gas reacts with ethylene gas to form ethane gas. This exothermic reaction occurs
rather easily at room temperature in the presence of a finely powdered metal, such as Ni, Pd, or Pt.

C2H4 (g) + H2 (g) → C2H6 (g) ΔΗ0 = - 137 kJ/mol

(Brown, p. 610)
(3) Enzymes in biological systems accelerate reactions by binding to the reactants in a way that lowers the
activation energy. Other enzymes react with reactant species to form a new reaction intermediate.

Enzymes are large protein molecules with molecular weights ranging from about 10,000 to about 1 million amu. As
the substrate reactant molecule enters the active site of a specific enzyme, it becomes activated from the
withdrawal or donation of electron density at a particular bond by the enzyme. The substrate fits neatly and
binds on the active site of enzyme (lock-and-key model) by intermolecular forces such as dipole-dipole
attractions, hydrogen bonds, and London dispersion forces to form a complex in a rapid reaction. After the
 reaction of the substrate is complete, the products separate from the enzyme.

19
Putting Concepts Together: Experimental data of the reaction of nitrogen monoxide and hydrogen are as follows: 2 NO (g) + 2 H 2

(g) → N2 (g) + 2 H2O (g)

Experiment Initial [NO] mol L-1 Initial [H2] mol L-1 Initial Rate of appearance
of N2mol L-1s-1

1 0.100 0.100 2.53 x 10-6

2 0.100 0.200 5.05 x 10-6

3 0.200 0.100 10.10 x 10-6

4 0.300 0.100 22.80 x 10-6

(1) Determine the order of reaction with respect to NO and with respect to H 2.
(2) Write the rate law expression for the reaction.
(3) Calculate the value for the rate constant, including its units.
(4) A suggested mechanism for the reaction is as follows:
H2 + NO ↔ X fast step
X + NO → Y + H2O slow step
Y + H2→ N2 + H2O fast step
Explain whether this mechanism agrees with the experimental rate law expression.

(5) Explain why a single step mechanism is unlikely for this reaction.
(6) Deduce the initial rate of appearance of H2O (g) compares with that of the N2 (g) in experiment 1. 20
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