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Chapter 1
Chemical Kinetics
Copyright 2011 Pearson Education, Inc.
Kinetics: Rates and Mechanisms of Chemical Reactions

1.1 Expressing Reaction Rate: Differential rate law Graphical representation of reaction rate 1.2 The Rate Law : Order of reaction, Initial rate method Integrated rate law, rate constant, half -life 1.3 Collision Theory: Activation energy, effective collisions 1.4 Factors affecting reaction rate: Concentration, temperature, catalyst, nature of reactants 1.5 Transition State Theory: Activated complex 1.6 Arrhenius Equation: Determination of rate constant and activation energy 1.7 Reaction Mechanism: Intermediates, molecularity, rate determining step
Chemical Kinetics
The speed of a chemical reaction is called its
reaction rate. The rate of a reaction is a measure of how fast the reaction makes products, or how fast the reactants are consumed. Chemical kinetics is the study of the factors that affect the rates of chemical reactions:
Such as temperature, reactant concentrations
Tro: Chemistry: A Molecular Approach, 2/e
Factors that Affect Reaction Rates

Kinetics is the study of how fast chemical reactions occur. There are 4 important factors which affect the kinetics or rates of reactions:
reactant concentration, temperature, action of catalysts, and surface area.
Aim: to understand chemical reactions behaviour at molecular level.

4 Copyright 2011 Pearson Education, Inc.
Defining Reaction Rates

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:
Reaction Rates
For a reaction A p B change in number of moles of B Average rate ! change in time (moles of B ! (t
at t = 0 [A] = 8 [B] = 8 [C] = 0 at t = 16 [A] = 4 [B] = 4 [C] = 4 (?A ? ? 1 A 1 (?CA A ?CA2A A2CA? A Rate Rate ! !! t t 2 t 21 t1 (t(t 44 ! ! .0.25 08 Rate 0 25 Rate ! 116 6 00
Tro: Chemistry: A Molecular Approach, 2/e 7
at t = 0 [X] = 8 [Y] = 8 [Z] = 0 at t = 16 [X] = 7 [Y] = 7 [Z] = 1
((ZXA ?Z?X2?ZAXA ??A !! A2 A ? 1 1 Rate ! Rate ! t t 2 2t1 t1 t ((t 0 17 8 !!000625 Rate ! ..0625 Rate ! 6 11600
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.
Average Rate
The average rate is the change in measured
concentrations in any particular time period linear approximation of a curve
Change of Rate with Time Most useful units for rates are to look at molarity.
Since volume is constant, molarity and moles are directly proportional.
Tro: Chemistry: A Molecular Approach, 2/e 9 Copyright 2011 Pearson Education, Inc.
Reaction Rate and Stoichiometry

In most reactions, the coefficients of the balanced
equation are not all the same. H2 (g) + I2 (g) p 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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H2
I2
HI
Stoichiometry tells us that rate is The average for every 1 mole/L of H2 used, the the change in 2 moles/L of concentration in a HI are made. given time period Assuming a 1 L container, at 10 s, we used 0.181 moles of In the first 10 of H2. Therefore the amount s, the ([H2] is 0.181 HI made is 2(0.181 moles) =M, 0.362 moles.so the rate is At 60 s, we used 0.699 moles of H2. Therefore the amount of HI made is 2(0.699 moles) = 1.398 moles.
average rate in a given time period = slope of the line connecting the [H2] points; and +slope of the line for [HI]
the average rate for the first 80 s is 0.0108 M/s
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Instantaneous Rate
The instantaneous rate is the change in
concentration at any one particular time. Determined by taking the slope of a line tangent to the
concentartion vs time curve at any particular point.
The initial rate is the reaction rate at the

beginning of a reaction. slope of a line tangent to the curve at time t = 0 No product formed yet, reversed rate = 0
H2 (g) + I2 (g) p 2 HI (g)

Using [H2], the instantaneous rate at 50 s is
Using [HI], the instantaneous rate at 50 s is
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Problem 1.1: For the reaction given, the [I] changes from1.000 M to 0.868 M
in the first 10 s. Calculate the average rate in the first 10 s, and ([H+]/(t.
H2O2 (aq) + 3 I(aq) + 2 H+(aq) p 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
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) p 2 NO(g) + Br2(l)
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Practice If 2.4 x 102 g of NOBr decomposes in a 2.0 x 102 mL flask in 5.0 minutes, find the average rate of Br2 production 2 NOBr(g) p 2 NO(g) + Br2(l)
Given: 240.0 gBr2, 3.0200.0 mL,5.0 min. 5.45 M NOBr, 0.2000sL, 5.0 min. x 102 Find: ([Br2]/(t, M/s
Conceptual Plan:
( mole Br2 ( min
(M
} (s
Rate
Relationships: 2 mol NOBr:1 mol Br2, 1 mol = 109.91g, 1 mL=0.001 L Solve:
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Practice: Consider the reaction: 8A(g) + 5B(g) p 8C(g) + 6D(g) If [C] is increasing at the rate of 4.0 mol L1s1, at what rate is [B] changing? A. -0.40 mol L1s1 B. -2.5 mol L1s1 C. -4.0 mol L1s1 D. -6.4 mol L1s1 E. None of these choices is correct, since its rate of change must be positive.
Tro: Chemistry: A Molecular Approach
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In general, the differential rate law for the reaction aA + bB cC + dD
rate =
1 a
([A] (t
= -
1 b
([B] (t
= +
1 c
([C] (t
= +
1 d
([D] (t
The numerical value of the rate depends upon the substance that serves as the reference. The rest is relative to the balanced chemical equation.
Expressing Rate in Terms of Changes in Concentration with Time

PROBLEM 1.2:
Because it has a nonpolluting product (water vapor), hydrogen gas is used for fuel aboard the space shuttle and may be used by earthbound engines in the near future.
2H2(g) + O2(g)
2H2O(g)
(a) Express the rate in terms of changes in [H2], [O2], and [H2O] with time. (b) When [O2] is decreasing at 0.23 mol/L*s, at what rate is [H2O] increasing? SOLUTION: (a) (b) ([O2] (t ([H2O] (t
rate =
1 2
([H2] (t =+ 1 2
=-
([O2] (t ([H2O] (t
=+
1 2
([H2O] (t
= - 0.23 mol/L*s
= 0.46 mol/L*s
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 p 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 overall order of the reaction. The rate law for the reaction given:
2 NO(g) + O2(g) p 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.
Concentration and Rate

Using Initial Rates to Determines Rate Laws A reaction is zero order in a reactant if the change in concentration of that reactant produces no effect. A reaction is first order if doubling the concentration causes the rate to double. A reaction is nth order if doubling the concentration causes an 2n increase in rate. Note that the rate constant does not depend on concentration.
Determining Reaction Order from Rate Laws

PROBLEM 1.3:
For each of the following reactions, determine the reaction order with respect to each reactant and the overall order from the given rate law.
2NO2(g) rate = k[NO]2[O2] I3-(aq) + 2H2O(l) rate = k[H2O2][I-]
(a) 2NO(g) + O2(g)

PLAN:
(b) H2O2(aq) + 3I-(aq) + 2H+(aq)
Look at the rate law and not the coefficients of the chemical reaction.
SOLUTION: (a) The reaction is 2nd order in NO, 1st order in O2, and 3rd order overall. (b) The reaction is 1st order in H2O2, 1st order in I- and zero order in H+, while being 2nd order overall.
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 k
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, M1ys1
Rate, [NO], [O3] Rate = k[NO][O3]
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Practice: The rate law for the decomposition of acetaldehyde, CH3CHO, is Rate = k[CH3CHO]2. What is the rate of the reaction when the [CH3CHO] = 1.75 x 103 M and the rate constant is 6.73 x 106 M1s1?
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Practice What is the rate of the reaction when the [CH3CHO] = 1.75 x 103 M and the rate constant is 6.73 x 106 M1s1?
Given: [CH3CHO] = 1.75 x 103 M, k= 6.73 x 106 M1s1 Find: Rate, M/s Conceptual k, [acetaldehyde] Rate Plan: Relationships: Rate = k[acetaldehyde]2 Solve:
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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 doubles of A quadruples the does notthe initial reaction rate change the initial reaction rate. Thus, n = 0 (Zero Order)
Rate = k[A]n
Rate = k
Proposed rate law: 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
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) p NO(g) + CO2(g) given the data below
Comparing Expt #1 and Expt #2, the [NO2] changes but the [CO] does not
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n = 2, m = 0
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Example 13.2: Determine the rate law and rate constant for the reaction NO2(g) + CO(g) p NO(g) + CO2(g) given the data below Substitute the concentrations and rate for any experiment into the rate law and solve for k Initial Initial Rate Expt. Initial (M/s) Number [NO2], (M) [CO], (M) 1. 0.10 0.10 0.0021 2. 3. 4.
for expt 1 0.0021
M s
0.20 0.20 0.40
0.10 0.20 0.10
0.0082 0.0083 0.033
Rate ! k[NO2 ]2 ! k 0.10 M
0.0021 Ms k! ! 0.21 M1 y s1 0.01 M2

Practice Determine the rate law and rate constant for the reaction NH4+ + NO2 pN2 + 2 H2O given the data below
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Practice Determine the rate law and rate constant for the reaction NH4+ + NO2 pN2 + 2 H2O given the data below Rate = k[NH4+]n[NO2]m
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Integrated Rate Laws

For the reaction A p Products,
the rate law depends on the concentration of A. Applying calculus to integrate the rate law gives another equation showing the relationship between the concentration of A and the time of the reaction this is called the Integrated Rate Law
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First Order Reaction

Rate = k[A]1 = k[A]
(differential rate law)
ln[A] = (k) t + ln[A]initial (integrated rate law)

y = m. x + b 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. ([ A] Rate ! ! k[A] The half-life of a first order reaction (t ln?A A ln?A A is constant. t initial ! kt ln?A A ! kt ln?A A When Rate = M/sec, k = s1 t initial
ln[A]initial
ln[A]
time
HalfHalf-Life Half-Life
The half-life, t1/2, of a reaction is the 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. ln 1 2 k
t1 !
2
! 0.693
k
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The Half-Life of a First-Order Reaction Is Constant
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Rate Data for: C4H9Cl + H2O p C4H9OH + HCl
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C4H9Cl + H2O p C4H9OH + 2 HCl
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slope = 2.01 x 103 k= 2.01 x 103 s-1
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Zero Order Reaction

Rate = k[A]0 = k
(differential rate law) [A] = kt + [A]initial (integrated rate law) Graph of [A] vs. time is straight line with slope = k and yintercept = [A]initial t = [Ainitial]/2k = [A0]/2k When Rate = M/sec, k = M/sec
[A]initial
[A]
time
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Second Order Reaction

Rate = k[A]2
(differential rate law) 1/[A] = kt + 1/[A]initial (integrated rate law) 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 = M1ys1 For a second order reaction, half-life depends on the initial concentration. The lower the initial concentration the higher is the half-life. Copyright 2011 Pearson Education, Inc. Tro: Chemistry: A Molecular Approach, 2/e 49
1/[A]
1/[A]initial
time
Determining the Half-Life of a First-Order Reaction

PROBLEM 1.3: Cyclopropane is the smallest cyclic hydrocarbon. It is
thermally unstable and rearranges to propene at 1000oC via the following first-order reaction:
CH2 H2C CH2 (g) ( H3C CH CH2 (g)
The rate constant is 9.2 s-1, (a) What is the half-life of the reaction? (b) How long does it take for the concentration of cyclopropane to reach one-quarter of the initial value? 0.693 PLAN: Use the half-life equation, t1/2 = k One-quarter of the initial value means two half-lives have passed.
SOLUTION:
(a) t1/2 = 0.693/9.2 s-1 = 0.075 s
(b)
2 t1/2 = 2(0.075 s) = 0.150 s
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Table 1 Units of the Rate Constant k
Overall Reaction Order 0
Units of k (t in seconds) mol/L*s (or mol L-1 s-1)
1/s (or s-1)
L/mol*s (or L mol -1 s-1)
L2 / mol2 *s (or L2 mol-2 s-1)
Example 13.4: The reaction SO2Cl2(g) p 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

Practice The reaction Q p 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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Practice The reaction Q p 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 Given: [Q]init = 0.010 M, t = 5.0 x 102 s, [Q]t = 0.0010 M Find: k
[Q]init, t, [Q]t
Solution:
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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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Practice Complete the Table and Determine the Rate Equation for the Reaction A p 2 Product
What will the rate be when the [A] = 0.010 M?

Practice Complete the Table and Determine the Rate Equation for the Reaction A p 2 Product
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Conclusion for the determination of the rate equation for the reaction A p 2 Product Because the graph 1/[A] vs. time is linear, the reaction is second order, Rate ! k[A]2 k ! slope of the line ! 0.10 M1y s 1
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Relationship Between Order and HalfHalf-Life

For a zero order reaction, the half-life is directly
proportional to the initial concentration. The lower the initial concentration of the reactants, the shorter the half-life of the concentration. (t1/2 = constant) t1/2 = ln(2)/k For a second order reaction, the half-life is inversely proportional to the initial concentration increasing the initial concentration shortens the half-life
t1/2 = 1/(k[A]init)
For a first order reaction, the half-life is independent
t1/2 = [A]init/2k
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
t1/2
Solution:
Check: the new concentration is less than the original, as expected

Practice The reaction Q p 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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Practice : The reaction Q p 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 Given: [Q]init = 0.010 M, k = 1.8 M1ys1 Find: t1/2, s
[Q]init, k
t1/2
Solution:
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Collision Theory
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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The greater the number of collisions the faster the rate. The more molecules present, the greater the probability of collision and the faster the rate. The higher the temperature, the more energy available to the molecules (collision) and the faster the rate. (Eg. food spoils when not refrigerated.) Complication: not all collisions lead to products. In fact, only a small fraction of collisions lead to product.
Activation Energy
Molecules must possess a certain minimum kinetic
energy called the activation energy for a reaction to occur.
molecules. Reaction with low activation energy is easier to take place, and is faster.
energy needed to break the bonds of the reacting
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Effective Collisions
Kinetic Energy Factor
For a collision to be effective, the reacting molecules must have sufficient kinetic energy to overcome the energy barrier.
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Orientation Factor
The proper orientation results when the atoms
are aligned in such a way that the old bonds can break and the new bonds can form. The more complex the reactant molecules, the less frequently they will collide with the proper orientation. In order for reaction to occur the reactant molecules must collide in the correct orientation and with enough energy to form products.
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Consider: Cl + NOCl p NO + Cl2 There are two possible ways that Cl atoms and NOCl molecules can collide; one is effective and one is not.
Orientation Effect
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Collision Frequency
The collision frequency is the number of collisions
that happen per unit time. The more collisions per second there are, the more collisions can be effective and lead to product formation.
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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. Any factor that can increase the frequency of effective collisions would increase the rate of a reaction.
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Factors Affecting Reaction Rate

Under specific conditions, every reaction has its own characteristic rate, which may be controlled by four factors:
1. 2. 3. 4.
Concentrations of reactants Chemical nature of reactants Temperature The use of a catalyst
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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 effective collisions between reactant molecules concentration of gases depends on the partial pressure of the gas
Concentrations of solutions depend on the soluteto-solution ratio (molarity)
higher pressure = higher concentration
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Factors Affecting Rate Temperature
Increasing the temperature raises the average kinetic

energy of the reactant molecules.
Increasing the temperature increases the number of

molecules with sufficient kinetic energy to overcome the activation energy, leads to increase in frequency of effective collisions. Hence, increasing the rate of reaction.
The distribution of kinetic energy is shown by the Boltzmann

distribution curves.
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Increased number of
molecules (T1>T2)
Sufficient kinetic
energy to overcome the activation energy (T1>T2) Faster rate
Higher kinetic energy required

Tro: Chemistry: A Molecular Approach, 2/e 81
to overcome the activation energy (T2 >T1) Slower rate
Factors Affecting Rate Catalyst
Catalysts are substances that affect the rate of a
reaction without being consumed. Catalysts generally speed up a reaction. They give the reactant molecules a different path to follow with a lower activation energy.
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Catalysts
Homogeneous catalysts are in the same phase

as the reactant particles
Cl(g) in the destruction of O3(g)
Heterogeneous catalysts are in a different

phase than the reactant particles
solid catalytic converter in a cars exhaust system
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Types of Catalysts
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Homogeneous Catalysis
Generally, catalysts operate by lowering the activation energy for a reaction. Chlorine atoms are catalysts for the destruction of ozone. A single CFC molecules can destroy 100,000 ozone molecules. The catalyst and reacting molecules are in one phase.
Hydrogen peroxide decomposes very slowly: 2H2O2(aq) p 2H2O(l) + O2(g) But, in the presence of the bromide ion, the decomposition occurs rapidly. A catalyst may add intermediates to the reaction. When a catalyst adds an intermediate, the activation energies for both steps must be lower than the activation energy for the uncatalyzed reaction. Example: In the presence of Br-, Br2(aq) is generated as an intermediate in the decomposition of H2O2.
Heterogeneous Catalysis
The catalyst is in a different phase of the reactants and products. Typical example: solid catalyst, gaseous reactants and products (catalytic converters in cars). Most industrial catalysts are heterogeneous. First step is adsorption (the binding of reactant molecules to the catalyst surface). Adsorbed species (atoms or ions) are very reactive. Molecules are adsorbed onto active sites on the catalyst surface.
Consider the hydrogenation of ethylene: C2H4(g) + H2(g) p C2H6(g), (H = -136 kJ/mol. (Ethylene) (Ethane) In the presence of a metal catalyst (Ni, Pt or Pd) the reaction occurs quickly at room temperature. Ethylene and hydrogen molecules are adsorbed onto active sites on the metal surface. The H-H bond breaks and the H atoms migrate about the metal surface. When an H atom collides with an ethylene molecule on the surface, the C-C T bond breaks and a C-H W bond forms. When C2H6 forms it desorbs from the surface. When ethylene and hydrogen are adsorbed onto a surface, less energy is required to break the bonds and the activation energy for the reaction is lowered.
Enzymes Catalysis
Enzymes are biological catalysts. Most enzymes are protein molecules with large molecular masses (10,000 to 106 amu). Substrates undergo reaction at the active site of an enzyme. A substrate locks into an enzyme and a fast reaction occurs. The products then move away from the enzyme. Only substrates that fit into the enzyme lock can be involved in the reaction. If a molecule binds tightly to an enzyme so that another substrate cannot displace it, then the active site is blocked and the catalyst is inhibited (enzyme inhibitors). The number of events (turnover number) catalyzed is large for enzymes (103 - 107 per second).
Enzymes
Factors Affecting Reaction Rate: Nature of the Reactants
Nature of the reactants means what kind of reactant

molecules and what physical conditions 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
Transition State Theory

There is an energy barrier to almost all reactions. There exists an intermediate stage when reactant
molecules change into products. The activated complex or transition state is a chemical species with partially broken and partially formed bonds an intermediate formed between reactant and product molecules has highest energy and extremely unstable
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Figure 2
Reaction energy diagrams and possible transition states.
Energy Profile of a Catalyzed Reaction
polar stratospheric clouds contain ice crystals that catalyze reactions that release Cl from atmospheric chemicals
Drawing Reaction Energy Diagrams and Transition States

PROBLEM 1.5: A key reaction in the upper atmosphere is
O3(g) + O(g)
2O2(g)
The activation energy, Ea(fwd) is 19 kJ, and the enthalpy of reaction, (Hrxn for the reaction is -392 kJ. Draw a reaction energy diagram for this reaction, postulate a transition state, and calculate Ea(rev).
PLAN:
Exothermic reaction. The reactants are at a higher energy level than the products and the transition state is slightly higher than the reactants.
Potential Energy
SOLUTION:
Ea= 19 kJ O3+O transition state Ea(rev)= (392 + 19) kJ = 411kJ 2O2

Reaction progress breaking bond
(Hrxn = -392 kJ
O O
forming bond
Example: Rearrangement of Transition State

Consider the rearrangement of methyl isonitrile to form acetonitrile:
H3C N C H3C N C H3C C N
In H3C-N|C, the C-N|C bond bends until the C-N bond breaks and the N|C portion is perpendicular to the H3C portion. This structure is called the activated complex or transition state. The energy required for the above twist and break is the activation energy, Ea. Once the C-N bond is broken, the N|C portion can continue to rotate forming a C-C|N bond.
The change in energy for the reaction is the difference in energy between CH3NC and CH3CN. (() The activation energy is the difference in energy between reactants, CH3NC and transition state. (Ea) The rate depends on Ea, not ()the lower Ea, the faster the reaction. * If a forward reaction is exothermic (CH3NC p CH3CN), then the reverse reaction is endothermic (CH3CN p CH3NC).
Connection between Activation Energy with Temperature and Rate

How methyl isonitrile molecule gain enough energy to overcome the activation energy barrier? It does so through collision with other molecules. From kinetic molecular theory, we know that as temperature increases, the total kinetic energy increases. We can show the fraction of molecules, f, (with energy equal to or greater than Ea) is
f !e
Ea
RT
- where R is the gas constant (8.314 J/molK).

Arrhenius Equation
Changing the temperature changes the rate constant,
k, of the rate law The Arrhenius Equation shows the relationship between absolute temperature, T, and rate constant, k :
where T is the temperature in kelvins R is the gas constant in energy units, 8.314 J/(molK) A is called the Arrhenius constant (which includes the frequency factor and the orientation factor). Ea is the activation energy, the minimum energy needed for the molecules to react.
The Arrhenius Equation: The Exponential Factor
The exponential factor in the Arrhenius equation is a

number between 0 and 1
The larger the activation energy, Ea, the fewer molecules Increase in temperature, T, will gives a larger k value
that have sufficient energy to overcome the energy barrier, the smaller the rate constant k.
therefore increasing the temperature will increase the reaction rate
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Arrhenius Plots
The Arrhenius Equation: The integrated form
this equation is in the linear form y = mx + b where y = ln(k) and x = (1/T) A graph of ln(k) vs. (1/T) is a straight line
Slope of Ea/R, or (R)(slope of the line) = Ea (in Joules) R = 8.314 J/(molK) eyintercept = A (unit is the same as k)
Example 13.7: Determine the activation energy and frequency factor for the reaction O3(g) p 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) p O2(g) + O(g) given the following data:
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Example 13.7: Determine the Ea and the Arrhenius constant, A, for the reaction O3(g) p O2(g) + O(g) given the following data:
slope, m = 1.12 x 104 K yintercept, b = 26.8
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Arrhenius Equation: Two-point Form Two If we do not have a lot of data, then we recognize: Ea Ea ln k1 ! ln A and ln k 2 ! ln A RT1 RT2
Ea Ea ln k 2 ln k1 ! RT ln A RT ln A 2 1 k 2 Ea 1 1 ln ! k1 R T1 T2
Or if you only have two (T,k) data points:
Example 13.8: The reaction NO2(g) + CO(g) p 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
T1, k1, T2, k2
Ea
Solution:
Check: most activation energies are tens to hundreds of kJ/mol so the answer is reasonable
Practice: It is often said that the rate of a reaction doubles for every 10 C rise in temperature. Calculate the activation energy for such a reaction.
Hint: make T1 = 300 K, T2 = 310 K and k2 = 2k1
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Practice Find the activation energy in kJ/mol for increasing the temperature 10 C doubling the rate
Given: T1 = 300 K, T1 = 310 K, k2 = 2 k1 Find: Ea, kJ/mol
T1, k1, T2, k2
Ea
Solution:
Check: most activation energies are tens to hundreds of kJ/mol so the answer is reasonable
Reaction Mechanism
We generally describe chemical reactions with an
equation listing all the reactant molecules and product molecules. But 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.
An Example of a Reaction Mechanism
Overall reaction: H2(g) + 2 ICl(g) p 2 HCl(g) + I2(g) Mechanism: Step 1: H2(g) + ICl(g) p HCl(g) + HI(g) Step 2: HI(g) + ICl(g) p HCl(g) + I2(g) The reactions (1) and (2) in this mechanism are called the 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.
* Elementary step: any process that occurs in a single step.
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Multistep Mechanisms
Some reaction proceed through more than one step: NO2(g) + NO2(g) p NO3(g) + NO(g) NO3(g) + CO(g) p NO2(g) + CO2(g) Notice that if we add the above steps (using Hess Law), we get the overall reaction: NO2(g) + CO(g) p NO(g) + CO2(g)
Intermediates
Overall: H2(g) + 2 ICl(g) p 2 HCl(g) + I2(g) Step (1): H2(g) + ICl(g) p HCl(g) + HI(g) Step (2): HI(g) + ICl(g) p 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.
the overall equation.
Adding equations (1) and (2), removing HI, will give

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 directly from the equation of the step. The rate law of an elementary step is determined by its molecularity: Unimolecular processes are first order, Bimolecular processes are second order, and Termolecular processes are third order.
H2(g) + 2 ICl(g) p 2 HCl(g) + I2(g) 1) H2(g) + ICl(g) p HCl(g) + HI(g) Rate = k1[H2][ICl] 2) HI(g) + ICl(g) p HCl(g) + I2(g) Rate = k2[HI][ICl]
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 formation 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) p NO(g) + CO2(g) 1. NO2(g) + NO2(g) p NO3(g) + NO(g) 2. NO3(g) + CO(g) p 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.
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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Example 1: Mechanisms with a Fast Initial Step

2NO(g) + Br2(g) p 2NOBr(g) The experimentally-determined (observed) rate law is: Rate = k[NO]2[Br2] Consider the following mechanism:
Step 1: NO(g) + Br2(g) Step 2: NOBr2(g) + NO(g) k1 k-1 k2 NOBr2(g) (fast)
2NOBr(g) (slow)
The rate law is (based on Step 2): Rate = k2[NOBr2][NO] The rate law should not depend on the concentration of an intermediate (NOBr2 is intermediates (unstable).
NOBr2 is the intermediate (unstable), so we express the concentration of NOBr2 in terms of NO and Br2 assuming there is an equilibrium in step 1 we have: k1 [ NOBr2 ] ! [ NO][Br2 ] k1 By definition of equilibrium:
k1[ NO][Br2 ] ! k1[ NOBr2 ]

Therefore, the overall rate law becomes:
k1 k1 2 Rate ! k2 [ NO][Br2 ][ NO] ! k2 [ NO] [Br2 ] k1 k1
Note the final rate law is consistent with the experimentally-observed rate law, Rate = k[NO]2[Br2]
Example 2: Mechanisms with a Fast Initial Step

1. 2 NO(g) N2O2(g)
k1 k1
Fast Slow Rate =k2[H2][N2O2] Fast
2. H2(g) + N2O2(g) p H2O(g) + N2O(g) 3. H2(g) + N2O(g) p H2O(g) + N2(g)
2 H2(g) + 2 NO(g) p 2 H2O(g) + N2(g)
Rateobs = k [H2][NO]2
final rate law is consistent with the observed rate law

Example 13.9: Show that the proposed mechanism for the reaction 2 O3(g) p 3 O2(g) matches the observed rate law: Rateobs = k[O3]2[O2]1 1. O3(g) O2(g) + O(g)
k1 k1
Fast Rate = k2[O3][O]
2. O3(g) + O(g) p 2 O2(g) Slow
final rate law is consistent with the observed rate law

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 p AB + B A + B p AB Slow Fast
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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 p AB + B A + B p AB Slow Fast
reaction 2 A + B2 p 2 AB B is an intermediate The first step is the rate determining step Rate = k[A][B2], same as RDS
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PENGUMUMAN
1) Sila lengkapkan Entrance Survey di portal i-Learn sebelum 14/12/2011 (Rabu) 2) Taklimat pengambilan dan kemasukan ke Kyushu University, Japan pada 14/12/2011 1.00-2.00 petang (Rabu) di DKF 7
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Chapter 1

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Kinetics: Rates and Mechanisms of Chemical Reactions

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Factors that Affect Reaction Rates

Aim: to understand chemical reactions behaviour at molecular level.

Defining Reaction Rates

For reactants, a negative sign is placed in front of

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at t = 0 [X] = 8 [Y] = 8 [Z] = 0 at t = 16 [X] = 7 [Y] = 7 [Z] = 1

Reaction Rate Changes Over Time

At some time the reaction stops, either

Tro: Chemistry: A Molecular Approach, 2/e

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Reaction Rate and Stoichiometry

To be consistent, the change in the concentration of

Tro: Chemistry: A Molecular Approach, 2/e

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the average rate for the first 80 s is 0.0108 M/s

the average rate for the first 40 s is 0.0150 M/s

the average rate for the first 10 s is 0.0181 M/s

Tro: Chemistry: A Molecular Approach, 2/e

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The initial rate is the reaction rate at the

H2 (g) + I2 (g) p 2 HI (g)

Using [HI], the instantaneous rate at 50 s is

Tro: Chemistry: A Molecular Approach, 2/e

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H2O2 (aq) + 3 I(aq) + 2 H+(aq) p I3(aq) + 2 H2O(l)

Tro: Chemistry: A Molecular Approach, 2/e

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Relationships: 2 mol NOBr:1 mol Br2, 1 mol = 109.91g, 1 mL=0.001 L Solve:

Tro: Chemistry: A Molecular Approach, 2/e

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Tro: Chemistry: A Molecular Approach

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In general, the differential rate law for the reaction aA + bB cC + dD

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Expressing Rate in Terms of Changes in Concentration with Time

The Rate Law

For the reaction aA + bB p products the rate

Tro: Chemistry: A Molecular Approach, 2/e

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Concentration and Rate

Determining Reaction Order from Rate Laws

(a) 2NO(g) + O2(g)

(b) H2O2(aq) + 3I-(aq) + 2H+(aq)

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Given: Find: Conceptual Plan: Relationships: Solve:

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

Tro: Chemistry: A Molecular Approach, 2/e

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Tro: Chemistry: A Molecular Approach, 2/e

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Tro: Chemistry: A Molecular Approach, 2/e

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Finding the Rate Law: The Initial Rate Method

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Proposed rate law: Rate = k[A]n

H2O2 (aq) + 3 I(aq) + 2 H+(aq) p I3(aq) + 2 H2O(l)

0.0021 Ms k! ! 0.21 M1 y s1 0.01 M2