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Chemistry: A Molecular Approach, 2nd Ed.

Nivaldo Tro

Chapter 13 Chemical Kinetics


Roy Kennedy Massachusetts Bay Community College Wellesley Hills, MA
Copyright 2011 Pearson Education, Inc.

Chemical Kinetics
Chemical kinetics is the study of the factors
that affect the rates of chemical reactions
Such as temperature

The speed of a chemical reaction is called its


reaction rate

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Defining Reaction Rate


The rate of a chemical reaction is generally
measured in terms of how much the concentration of a reactant decreases in a given period of time
or product concentration increases

For reactants, a negative sign is placed in front of


the definition

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Reaction Rate Changes Over Time

As time goes on, the rate of a reaction


generally slows down
because the concentration of the reactants decreases

At some time the reaction stops, either


because the reactants run out or because the system has reached equilibrium

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Reaction Rate and Stoichiometry


In most reactions, the coefficients of the balanced
equation are not all the same H2 (g) + I2 (g) 2 HI(g) For these reactions, the change in the number of molecules of one substance is a multiple of the change in the number of molecules of another
for the above reaction, for every 1 mole of H2 used, 1 mole of I2 will also be used and 2 moles of HI made therefore the rate of change will be different

To be consistent, the change in the concentration of


each substance is multiplied by 1/coefficient

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Example 13.1: For the reaction given, the [I] changes from 1.000 M to 0.868 M in the first 10 s. Calculate the average rate in the first 10 s and the D[H+]. H2O2 (aq) + 3 I(aq) + 2 H+(aq) I3(aq) + 2 H2O(l)
solve the rate equation for the rate (in terms of the change in concentration of the given quantity)
solve the rate equation (in terms of the change in the concentration for the quantity to find) for the unknown value
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Practice If 2.4 x 102 g of NOBr (MM 109.91 g) decomposes in a 2.0 x 102 mL flask in 5.0 minutes, find the average rate of Br2 production in M/s 2 NOBr(g) 2 NO(g) + Br2(l)

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Factors Affecting Reaction Rate: Nature of the Reactants


Nature of the reactants means what kind of reactant
molecules and what physical condition they are in
small molecules tend to react faster than large molecules gases tend to react faster than liquids, which react faster than solids powdered solids are more reactive than blocks more surface area for contact with other reactants certain types of chemicals are more reactive than others e.g. potassium metal is more reactive than sodium

ions react faster than molecules


no bonds need to be broken
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Factors Affecting Reaction Rate: Temperature Increasing temperature increases reaction rate
chemists rule of thumbfor each 10 C rise in temperature, the speed of the reaction doubles
for many reactions

There is a mathematical relationship between the


absolute temperature and the speed of a reaction discovered by Svante Arrhenius, which will be examined later

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Factors Affecting Reaction Rate: Catalysts


Catalysts are substances that affect the speed

of a reaction without being consumed Most catalysts are used to speed up a reaction; these are called positive catalysts
catalysts used to slow a reaction are called negative catalysts.

Homogeneous = present in same phase Heterogeneous = present in different phase How catalysts work will be examined later
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Factors Affecting Reaction Rate: Reactant Concentration Generally, the larger the concentration of
reactant molecules, the faster the reaction
increases the frequency of reactant molecule contact concentration of gases depends on the partial pressure of the gas
higher pressure = higher concentration

Concentrations of solutions depend on the


solute-to-solution ratio (molarity)

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The Rate Law


The rate law of a reaction is the mathematical
relationship between the rate of the reaction and the concentrations of the reactants
and homogeneous catalysts as well

The rate law must be determined experimentally!! The rate of a reaction is directly proportional to the
concentration of each reactant raised to a power

For the reaction aA + bB products the rate


law would have the form given below
n and m are called the orders for each reactant k is called the rate constant

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Reaction Order
The exponent on each reactant in the rate law
is called the order with respect to that reactant The sum of the exponents on the reactants is called the order of the reaction The rate law for the reaction
2 NO(g) + O2(g) 2 NO2(g) is Rate = k[NO]2[O2] The reaction is

second order with respect to [NO],


first order with respect to [O2], and third order overall
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Sample Rate Laws

The bottom reaction is autocatalytic because a product affects the rate. Hg2+ is a negative catalyst; increasing its concentration slows the reaction.

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Example: The rate equation for the reaction of NO with ozone is Rate = k[NO][O3]. If the rate is 6.60 x 105 M/sec when [NO] = 1.00 x 106 M and [O3] = 3.00 x 106 M, calculate the rate constant Given: Find: Conceptual Plan: Relationships: Solve:
[NO] = 1.00 x 106 M, [O3] = 3.00 x 106 M, Rate = 6.60 x 106 M/s k, M1s1

Rate, [NO], [O3] Rate = k[NO][O3]

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Practice The rate law for the decomposition of acetaldehyde is Rate = k[acetaldehyde]2. What is the rate of the reaction when the [acetaldehyde] = 1.75 x 103 M and the rate constant is 6.73 x 106 M1s1?

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Finding the Rate Law: the Initial Rate Method


The rate law must be determined experimentally The rate law shows how the rate of a reaction
depends on the concentration of the reactants Changing the initial concentration of a reactant will therefore affect the initial rate of the reaction
if for the reaction A Products
then doubling the initial concentration of A doubles the the quadruples does not change the initial initial reaction rate reaction rate
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Rate = k[A]n
If a reaction is Zero Order, the rate of the reaction
is always the same
doubling [A] will have no effect on the reaction rate

If a reaction is First Order, the rate is directly


proportional to the reactant concentration
doubling [A] will double the rate of the reaction

If a reaction is Second Order, the rate is directly


proportional to the square of the reactant concentration
doubling [A] will quadruple the rate of the reaction
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Determining the Rate Law When there Are Multiple Reactants

Changing each reactant will effect the


overall rate of the reaction By changing the initial concentration of one reactant at a time, the effect of each reactants concentration on the rate can be determined In examining results, we compare differences in rate for reactions that only differ in the concentration of one reactant
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Example 13.2: Determine the rate law and rate constant for the reaction NO2(g) + CO(g) NO(g) + CO2(g) given the data below

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Practice Determine the rate law and rate constant for the reaction NH4+ + NO2 N2 + 2 H2O given the data below

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Half-Life
The half-life, t1/2, of a
reaction is the length of time it takes for the concentration of the reactant to fall to its initial value The half-life of the reaction depends on the order of the reaction
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Rate = k[A]0 = k

Zero Order Reactions

constant rate reactions

[A] = kt + [A]initial Graph of [A] vs. time is straight line with


slope = k and yintercept = [A]initial t = [Ainitial]/2k When Rate = M/sec, k = M/sec

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First Order Reactions


Rate = k[A]1 = k[A] ln[A] = kt + ln[A]initial Graph ln[A] vs. time gives straight line with
slope = k and yintercept = ln[A]initial
used to determine the rate constant

t = 0.693/k The half-life of a first order reaction is


constant When Rate = M/sec, k = s1
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The Half-Life of a First-Order Reaction Is Constant

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Second Order Reactions


Rate = k[A]2 1/[A] = kt + 1/[A]initial Graph 1/[A] vs. time gives straight line with
slope = k and yintercept = 1/[A]initial
used to determine the rate constant

t = 1/(k[A0]) When Rate = M/sec, k = M1s1

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Example 13.4: The reaction SO2Cl2(g) SO2(g) + Cl2(g) is first order with a rate constant of 2.90 x 104 s1 at a given set of conditions. Find the [SO2Cl2] at 865 s when [SO2Cl2]initial = 0.0225 M Given: [SO2Cl2]init = 0.0225 M, t = 865, k = 2.90 x 10-4 s1 Find: [SO2Cl2]
Conceptual Plan: Relationships:

[SO2Cl2]init, t, k

[SO2Cl2]

Solution:

Check: the new concentration is less than the original, as expected


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Practice The reaction Q 2 R is second order in Q. If the initial [Q] = 0.010 M and after 5.0 x 102 seconds the [Q] = 0.0010 M, find the rate constant

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Graphical Determination of the Rate Law for A Product


Plots of [A] vs. time, ln[A] vs. time, and 1/[A] vs.
time allow determination of whether a reaction is zero, first, or second order Whichever plot gives a straight line determines the order with respect to [A]
if linear is [A] vs. time, Rate = k[A]0 if linear is ln[A] vs. time, Rate = k[A]1 if linear is 1/[A] vs. time, Rate = k[A]2
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Relationship Between Order and Half-Life


For a zero order reaction, the lower the initial
concentration of the reactants, the shorter the half-life
t1/2 = [A]init/2k

For a first order reaction, the half-life is


independent of the concentration

For a second order reaction, the half-life is

t1/2 = ln(2)/k

inversely proportional to the initial concentration increasing the initial concentration shortens the half-life
t1/2 = 1/(k[A]init)
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Example 13.6: Molecular iodine dissociates at 625 K with a firstorder rate constant of 0.271 s1. What is the half-life of this reaction? Given: k = 0.271 s1

Find: t1/2
Conceptual Plan: Relationships:

t1/2

Solution:

Check: the new concentration is less than the original, as expected


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Practice The reaction Q 2 R is second order in Q. If the initial [Q] = 0.010 M and the rate constant is 1.8 M1s1 find the length of time for [Q] = [Q]init

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The Effect of Temperature on Rate Changing the temperature changes the rate

constant of the rate law Svante Arrhenius investigated this relationship and showed that:

where T is the temperature in kelvins R is the gas constant in energy units, 8.314 J/(molK)

A is called the frequency factor, the rate the reactant energy approaches the activation energy
Ea is the activation energy, the extra energy needed to start the molecules reacting
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Activation Energy and the Activated Complex


There is an energy barrier to almost all
reactions The activation energy is the amount of energy needed to convert reactants into the activated complex
aka transition state

The activated complex is a chemical species


with partially broken and partially formed bonds
always very high in energy because of its partial bonds
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The Arrhenius Equation: The Exponential Factor


The exponential factor in the Arrhenius equation is a
number between 0 and 1 Tt represents the fraction of reactant molecules with sufficient energy so they can make it over the energy barrier
the higher the energy barrier (larger activation energy), the fewer molecules that have sufficient energy to overcome it

That extra energy comes from converting the kinetic


energy of motion to potential energy in the molecule when the molecules collide
increasing the temperature increases the average kinetic energy of the molecules therefore, increasing the temperature will increase the number of molecules with sufficient energy to overcome the energy barrier therefore increasing the temperature will increase the reaction rate
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Arrhenius Plots
The Arrhenius Equation can be algebraically
solved to give the following form:

this equation is in the form y = mx + b where y = ln(k) and x = (1/T) a graph of ln(k) vs. (1/T) is a straight line

(8.314 J/molK)(slope of the line) = Ea, (in Joules)


eyintercept = A (unit is the same as k)
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Example 13.7: Determine the activation energy and frequency factor for the reaction O3(g) O2(g) + O(g) given the following data:

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Example 13.7: Determine the activation energy and frequency factor for the reaction O3(g) O2(g) + O(g) given the following data:

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Arrhenius Equation: Two-Point Form


If you only have two (T,k) data points, the
following forms of the Arrhenius Equation can be used:

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Example 13.8: The reaction NO2(g) + CO(g) CO2(g) + NO(g) has a rate constant of 2.57 M1s1 at 701 K and 567 M1s1 at 895 K. Find the activation energy in kJ/mol
Given: T1 = 701 K, k1 = 2.57 M1s1, T2 = 895 K, k2 = 567 M1s1 Find: Ea, kJ/mol
Conceptual Plan: Relationships:

T1, k1, T2, k2

Ea

Solution:

Check: most activation energies are tens to hundreds of kJ/mol so the answer is reasonable
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Collision Theory of Kinetics


For most reactions, for a reaction to take place,
the reacting molecules must collide with each other
on average about 109 collisions per second

Once molecules collide they may react together


or they may not, depending on two factors 1. whether the collision has enough energy to "break the bonds holding reactant molecules together"; and 2. whether the reacting molecules collide in the proper orientation for new bonds to form
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Effective Collisions Orientation Effect

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Effective Collisions
Collisions in which these two conditions are
met (and therefore lead to reaction) are called effective collisions The higher the frequency of effective collisions, the faster the reaction rate When two molecules have an effective collision, a temporary, high energy (unstable) chemical species is formed the activated complex

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Reaction Mechanisms
The probability of more than 3 molecules colliding
at the same instant with the proper orientation and sufficient energy to overcome the energy barrier is negligible Most reactions occur in a series of small reactions involving 1, 2, or at most 3 molecules Describing the series of reactions that occurs to produce the overall observed reaction is called a reaction mechanism Knowing the rate law of the reaction helps us understand the sequence of reactions in the mechanism

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An Example of a Reaction Mechanism


Overall reaction:
H2(g) + 2 ICl(g) 2 HCl(g) + I2(g) Mechanism:

The reactions in this mechanism are


elementary steps, meaning that they cannot be broken down into simpler steps and that the molecules actually interact directly in this manner without any other steps
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1. H2(g) + ICl(g) HCl(g) + HI(g) 2. HI(g) + ICl(g) HCl(g) + I2(g)

Elements of a Mechanism Intermediates

H2(g) + 2 ICl(g) 2 HCl(g) + I2(g) 1) H2(g) + ICl(g) HCl(g) + HI(g) 2) HI(g) + ICl(g) HCl(g) + I2(g)

Notice that the HI is a product in Step 1, but then a reactant in Step 2 Because HI is made but then consumed, HI does not show up in the overall reaction Materials that are products in an early mechanism step, but then a reactant in a later step, are called intermediates
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Molecularity
The number of reactant particles in an
elementary step is called its molecularity A unimolecular step involves one particle A bimolecular step involves two particles
though they may be the same kind of particle

A termolecular step involves three particles


though these are exceedingly rare in elementary steps

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Rate Laws for Elementary Steps


Each step in the mechanism is like its own
little reaction with its own activation energy and own rate law The rate law for an overall reaction must be determined experimentally But the rate law of an elementary step can be deduced from the equation of the step 1) H2(g) + ICl(g) HCl(g) + HI(g) Rate = k1[H2][ICl]
Rate = k2[HI][ICl]

H2(g) + 2 ICl(g) 2 HCl(g) + I2(g)

2) HI(g) + ICl(g) HCl(g) + I2(g)


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Rate Laws of Elementary Steps

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Rate Determining Step


In most mechanisms, one step occurs slower than the
other steps The result is that product production cannot occur any faster than the slowest step the step determines the rate of the overall reaction We call the slowest step in the mechanism the rate determining step
the slowest step has the largest activation energy

The rate law of the rate determining


step determines the rate law of the overall reaction

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Another Reaction Mechanism


NO2(g) + CO(g) NO(g) + CO2(g) 1. NO2(g) + NO2(g) NO3(g) + NO(g) 2. NO3(g) + CO(g) NO2(g) + CO2(g) The first step is slower than the second step because its activation energy is larger. The first step in this mechanism is the rate determining step. The rate law of the first step is the same as the rate law of the overall reaction.
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Rateobs = k[NO2]2 Rate = k1[NO2]2 Slow Rate = k2[NO3][CO] Fast

Validating a Mechanism To validate (not prove) a mechanism, two


conditions must be met: 1. The elementary steps must sum to the overall reaction 2. The rate law predicted by the mechanism must be consistent with the experimentally observed rate law

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Mechanisms with a Fast Initial Step When a mechanism contains a fast initial step,

the rate limiting step may contain intermediates When a previous step is rapid and reaches equilibrium, the forward and reverse reaction rates are equal so the concentrations of reactants and products of the step are related
and the product is an intermediate

Substituting into the rate law of the RDS will


produce a rate law in terms of just reactants
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An Example
1. 2 NO(g) N2O2(g) 2. H2(g) + N2O2(g) H2O(g) + N2O(g) 3. H2(g) + N2O(g) H2O(g) + N2(g)
k1 k1

Fast Slow Rate = k2[H2][N2O2] Fast

2 H2(g) + 2 NO(g) 2 H2O(g) + N2(g) Rateobs = k [H2][NO]2

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Practice Mechanism
Determine the overall reaction, the rate determining step, the rate law, and identify all intermediates of the following mechanism 1. 2. A + B2 AB + B A + B AB Slow Fast

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Catalysts
Catalysts are substances that affect the rate of a

reaction without being consumed Catalysts work by providing an alternative mechanism for the reaction
with a lower activation energy

Catalysts are consumed in an early mechanism


step, then made in a later step
mechanism without catalyst O3(g) + O(g) 2 O2(g) V. Slow mechanism with catalyst Cl(g) + O3(g) O2(g) + ClO(g) ClO(g) + O(g) O2(g) + Cl(g)
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Fast Slow

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Practice Mechanism
Determine the overall reaction, the rate determining step, the rate law, and identify all catalysts and intermediates of the following mechanism 1. HQ2R2 + R Q2R2 + HR Fast 2. Q2R2 Q2R + R Slow

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Catalysts
Homogeneous catalysts are in the same
phase as the reactant particles

Heterogeneous catalysts are in a different


phase than the reactant particles
solid catalytic converter in a cars exhaust system

Cl(g) in the destruction of O3(g)

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