Announcements

Chapter 16
Chem 11 Exam 1 Kinetics: Rates and Mechanisms of
December 18
Schmitt Hall 114 (Non-majors) C-109 (Majors)
Chemical Reactions
6PM - 7:30PM
Chapter 12, 13 & 16 16.1 Factors that influence reaction rates
Format (40MC + 2 long questions) 16.2 Expressing the reaction rate,
average, instantaneous and initial rates

Problem Set: Kinetics Chapter 16 16.3 The rate law and its components
3,4,5,11,14,16,18,20,21,22,26,28,29,31,33,36,3 16.4 Integrated rate laws: Concentration changes over
8,41,50,59,67,72,74,76,78,79,80,82,87 time
16.5 Reaction mechanisms: Steps in the overall reaction
16.6 Catalysis: Speeding up a chemical reaction

Different theories tell us different things. Kinetics Concept Map

Thermodynamic theory: gives information on the

energetics of a reaction and whether a chemical
reaction can occur, but no information on how fast
a reaction can occur.

Kinetics gives information on how fast or slow a

chemical reaction is, but it can not tell us the
energetics or the extent a reaction will occur.

Equilibrium theory tells us the extent a chemical

reaction occurs but not on how fast it will occur.

Kinetics focus is “the rate”at which concentrations

of reactants or products change with time.

Rate = k [A]m [B]n

Time: 0
Five factors affect the rate of a chemical reaction. State or Phase of reacting molecules
1. Nature of Reactants--bonds break and form during a A hot steel nail glows in
reaction. Element and compounds have “inherent
tendencies to react”.
O2 but the same mass of
steel wool bursts into
2. Concentration - molecules must collide to react; the flames.
more molecules there are---the faster the reaction.

3. State or Phase of reacting molecules must mix to

collide, gas, liquids and solids have different surface The greater the surface
area to volume ratios varying reactivity.
area per unit volume
4. Temperature - molecules must collide with a minimum means more metal atoms
energy in order to react. Higher temperatures mean can react with O2 and
higher KE during a collision. increases the reaction
rate.
5. Presence of a catalyst: catalyst increase reaction
rates without being consumed in the reaction itself.

A reaction rate is expressed as the change in the A balanced chemical equation relates the rates of
concentration (molarity) of a reactant or a product disappearance of reactants to the rate of appearance
a change in time. By convention, rate is always a of products.
positive number with units of Molarity/sec.
C3H8 (g) + 5O2 (g) ===> 3CO2 (g) + 4H2O(g)
A B For every 1 mol C3H8 (M) per unit time requires 5 mol O2 per unit time
For every 1 mol C3H8 (M) per unit time produces 3 mol CO2 per unit time
[A]t - [A]t=0 reactant For every 1 mol C3H8 (M) per unit time produces 4 mol H2O per unit time
rate = - ![A] = - >0 disappearance
!t t - t0 ![O2] ![C3H8] ![CO2] this is confusing
rate = - = -5 = 5/3 so we avoid it!
[A] is a reactant. It decreases with time, place a negative sign in !t !t !t
front.
We use a “unified rate” such that the stoichiometry is considered
and a single positive value rate of reaction can be written.
![B] [B]t - [B]t=0 product
rate = = >0 formation
!t t - t0 ![C3H8] 1 ![O2] 1 ![CO2] 1 ![H2O]
rate = - =- = =
!t 5 !t 3 !t 4 !t
[B] is a product. It increases with time, there is no negative sign.

To avoid the ambiguity in a reaction rate, we use a Suppose you are given the following generalized
“scaled or unified rate” such that one number reaction.
describes the rate of change of all reactants and aA + bB cC + dD
all products.
What is the rate of the chemical reaction written or
C3H8 (g) + 5O2 (g) ===> 3CO2 (g) + 4H2O(g) expressed as a function of change in [A], [B], [C] and
[D]?

![C3H8] 1 ![O2] 1 ![CO2] 1 ![H2O]

rate = - =- = =
!t 5 !t 3 !t 4 !t

stoichiometric coefficients!
notice the negative sign for the reactants!

Rate > 0 (it’s a positive number)!

Suppose you are given the following generalized Suppose you are monitoring the reaction below. It is
reaction. found that the rate of appearance of NO2 is measured
aA + bB cC + dD and found to be 2 Molar sec-1. What is the rate of
disappearance, ![N2O5] and the rate of formation of O2 ?
What is the rate of reaction written as a function of !t
change in [A], [B], [C] and [D]?
2 N2O5(g) ! 4 NO2(g) + O2(g)

1 ![A] 1 ![B] 1 ![C] 1 ![D]

rate = - =- = =
a !t b !t c !t d !t

Suppose the rate of appearance of NO2 is measured and Hydrogen gas is used for fuel aboard the space
found to be 2 Molar sec-1. What is the rate of shuttle and may be used by automobile engines in
disappearance, ![N2O5] and the rate of formation of O2 ? the near future.
!t 2H2(g) + O2(g) 2H2O(g)

![NO2]
2 N2O5(g) ! 4 NO2(g) + O2(g) = 2 M s-1 (a) Express the reaction rate in terms of changes in [H2],
!t
[O2], and [H2O] with time.
∆[N2 O5 ] 2M NO2 2M N2 O5 1M N2 O5
Method 1 - = × = (b) If [O2] decreases at 0.23 mol O2/L/s, at what rate is
∆t sec 4M NO2 sec [H2O] increasing?

![NO2] - 1 "[N2O5] = 1 ![O2]

Method 2 - 1 =
1 !t
4 !t 2 "t
2M NO2 "[N2O5] ![O2]
- 1 = -1 = 1
4 sec 2 "t 1 !t

Hydrogen gas is used for fuel aboard the space We need to understand average, instantaneous
shuttle and may be used by automobile engines in and initial rates of a chemical reaction.
the near future.
2H2(g) + O2(g) 2H2O(g)
Suppose we have drive to Alabang starting from White Plains
(a) Express the reaction rate in terms of changes in [H2], t=0 15 min 20 min 50 min
[O2], and [H2O] with time.
(b) If [O2] decreases at 0.23 mol O2/L/s, at what rate is 0 km 25 km 30 km 60 km
[H2O] increasing? Edsa White Sucat Alabang Canlubang
Plains
1 ![H2] ![O2] 1 ![H2O] The “rate” expresses how a quantity changes with respect to some
(a) rate = - =- =+
specified time interval. Our rate (speed) varies with traffic!
2 !t !t 2 !t

P ositionAlabang − P ositionEdsa
![O2] 1 ![H2O] Avg Rate of SpeedAlabang =
(b) - = 0.23 mol/L.s =+ T imeAlabang − T imeEdsa
!t 2 !t
![H2O] ∆d 30 km 1.5 km
= 0.46 mol/L.s Avg Rate of SpeedAlabang = = =
!t ∆t 20 min min
 We can measure the distance from a point on In chemical reactions we can observe the rate of
Edsa by looking at the odometer of the car and disappearance of a reactant, or the appearance of a
noting the distance & time from the starting point. product: Consider a transformation: A ==> B

!Distance !D Di - D0
rate of speed = = =
!time !t Ti - T0 0s 10 s 20 s 30 s 40 s 50 s 60 s
Time Distance Rate of Speed
Place Traveled (km)
(min) (km/min)

Ateneo 0 0 0 Note there 40 30 22

A 15 12 8 6
are different 0 B 10 18 25 28 32 34
Sucat 20 25 1.25 km/min rates or
speeds ∆[A] Change in Concentration A [A]t − [At=0 ]
rate = − =− =−
Alabang 40 30 0.75 km/min
depending ∆t Change in time t − t0
on traffic
and where ∆[B] Change in Concentration B [B]t − [Bt=0 ]
Canalubang 60 60 1.0 km/min we are. rate = + = =
∆t Change in time t − t0

We can choose any two data points to determine an An Example: Reduction of Bromine to Bromide
average rate during the chemical reaction A ==> B?
0s 30 s 60 s
Br2(aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)
10 s 20 s 40 s 50 s
40 30 22 15 12 8 6
0 10 18 25 28 32 34

What is the average rate of disappearance of A after 40 secs? Br2(aq) 2Br-

time
t=0 t = ti
We can easily monitor the change in [Br2] with an lab instrument.
∆[A] [At ] − [At=0 ] Beer’s Law
rate = =
∆t t − t0 Absorbance = "bC Br2(aq)

393 nm
(12M − 40M)
=− = 11M/s
(40 s − 0 s)

393 nm light
Detector

Suppose we monitor the color change and we plot average rate of ![Br2] [Br2]final – [Br2]initial
the reaction data: =- =-
disappearance !t tfinal - tinitial
Br2(aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)
Avg
Lab Data Time (s) [Br2] (mM) ![Br2]
Rate
Time (s) [Br2] (mM) 0.0 12.0 mM 2.00 0.04
12.0 Just like driving
50.0 10.0 mM in a car and
[Br2] (milliMolar)

0.0 12.0 mM 1.54 0.031

9.5 100.0 8.46 mM sometimes
50.0 10.0 mM 1.36 0.027 going fast, then
100.0 8.46 mM 150.0 7.10 mM slow, then fast
7.0 1.14 0.023
200.0 5.96 mM again---the
150.0 7.10 mM 0.019
0.96 average rate of a
200.0 5.96 mM 4.5 250.0 5.00 mM chemical
0.80 0.016
250.0 5.00 mM 300.0 4.20 mM reaction also
2.0 0.65 0.013 varies over time!
300.0 4.20 mM 0 50 100150200250300350400 350.0 3.55 mM
0.59 0.01
350.0 3.55 mM Time (seconds) 400.0 2.96 mM
400.0 2.96 mM
The average rate of disappearance of Br2 is the slope of The instantaneous rate of disappearance of Br2 is
the line between any two points on the curve. We can the slope of the line tangent at any point along the
pick any two points and get an average rate. curve.
Instantaneous Rate of Change
Slope of the tangent line at a point
12.0 rate = - [Br2]final – [Br2]initial 12.0
tfinal - tinitial
[Br2]t+!t – [Br2]t

[Br2] (milliMolar)
[Br2] (milliMolar)

=-
9.5 [3]final – [12]initial 9.5 !t
rate = - ![Br2]
400 - 0 7.0 !t
7.0

4.5
![Br2] 4.5
!t
2.0 2.0
0 50 100 150 200 250 300 350 400 0 50 100 150 200 250 300 350 400

Time (seconds) Time (seconds)

There are an infinite number of instantaneous rate Because chemical reactions are reversible as we
along the curve but not all are relevant in chemistry! move away from t = 0, chemists are interested in
the “initial” instantaneous rate.

kforward
O2 (g) + 2NO (g) 2NO2 (g)
kreverse

Use method of initial rates (i.e.

slope of measure rates close to t=0 sec)
tangent
and we avoid kreverse and
slope of convolution of kinetic data!
tangent
slope of kforward
tangent O2 (g) + 2NO (g) 2NO2 (g)

What was that instantaneous thing again? One goal of a kinetic experiment is to measure
data to determine an equation that “summarizes”
Initial Rate Tangent line at t -> 0 the “rate” at which a particular reaction occurs.
0.900
![O2]
=-
[0.689] – [0.882]
= 3.21 X 10-3 M/s Consider: a A + b B " c C + d D
!t 60s - 0s Initial Rate
0.675
Rate = k [A]m [B]n
[O2] (Molar)

rate of a reaction exponents

0.450 rate constant Reactant concentrations
• k is the temperature dependent “rate constant”.
0.225
• m and n are experimentally determined, and indicate how
sensitive the chemical reaction is to changes in [A] and [B].
0 • We call the sum of m + n the “order of the reaction”.
0 60 120 180 240 300 360 420 480 540 600
Time (seconds) • Rate Units are always (M/sec) so units of k change!
 The Method of Initial Rates Is Used To Reaction rates always has units of M/sec. The units
Determine the reaction “rate” by choosing a of the rate constant, k, in the rate law therefore
time very close to t = 0 where we can rid the depend on the exponents in the rate law.
kreverse from the rate. Consider a simple reaction:

kforward A C rate (M/sec) = k [A]m

O2 (g) + 2NO (g) 2NO2 (g)
kreverse
1. If m = 0 then [A]0 = 1 rate is a constant = k must
have units of M/sec
kforward
O2 (g) + 2NO (g) 2NO2 (g) 2. If m = 1 [A]1 = [A] means rate depends linearly on
concentration of A, k must have units of s-1
Our math is simplified greatly
in this regime. 3. If m = 2 [A]2 the rate quadruples when A is doubled
and k must have units of 1/M-1 s-1

Connecting Dots: Rate law vernacular and usage. For each of the following reactions, determine the
reaction order with respect to each reactant and
Suppose we do a kinetic study of the reaction of H2 and ICl
the overall reaction order from the given rate law.
H2 + ICl =>I2 + 2HCl
Note that the rate laws were determined experimentally not from
The rate law containing unknown variables can be written the equations given
immediately with unknowns k, m and n.
Rate = k [H2]m [ICl]n (a) 2NO(g) + O2(g) 2NO2(g); rate = k[NO]2[O2]
Obtaining (or be provided with) experimental data
allows us to calculate the unknowns k, m and n. (b) CH3CHO(g) CH4(g) + CO(g); rate = k[CH3CHO]3/2
Rate = k [H2 ]2 [ICl]1 = k [H2] [ICl]
Chemists then say “the reaction is 2nd order with respect (c) H2O2(aq) + 3I-(aq) + 2H+(aq) I3-(aq) + 2H2O(l);
rate = k[H2O2][I-]
to H2 and 1st order with respect to ICl”. The overall
reaction order m + n = 3 (3rd order) .

For each of the following reactions, determine the Connecting the Kinetic Dots
reaction order with respect to each reactant and Suppose we are asked to determine the rate law, k the rate
the overall reaction order from the given rate law. constant, and the order of the reaction. How do we do it?

(a) 2NO(g) + O2(g) 2NO2(g); rate = k[NO]2[O2]

O2 (g) + 2NO (g) 2NO2 (g)
1. Write a balanced chemical equation ✓
(a) The reaction is 2nd order in NO, 1st order in O2, and 3rd order
2. Write the generic rate law expression with all unknowns (you
overall.
don’t need any data to do this just a balanced equation)
(b) CH3CHO(g) CH4(g) + CO(g); rate = k[CH3CHO]3/2 ✓
(b) The reaction is 3/2-order in CH3CHO and 3/2-order overall.
rate = k [O2]m [NO]n
3. To solve the equation with need experimental data either from a
(c) H2O2(aq) + 3I-(aq) + 2H+(aq) I3-(aq) + 2H2O(l); lab measurement or in Chem 11 from data provided. There are many
rate = k[H2O2][I-] unknowns (k, m and n) but we devise ways to simplify. ✓
(c) The reaction is 1st order in H2O2, 1st order in I- and zero 4. Analyze the data using mathematics that we must get comfortable
order in H+, and 2nd order overall. with. Not hard once you get use to it.
Given the experimental data on the production of Use data ratios to eliminate unknowns in the rate law
initial reactant
nitrogen dioxide from oxygen and nitrogen concentrations (mol/L) initial rate
experiment
monoxide: determine the rate law, the total order O2 NO (mol/L.s)
of the reaction and the rate constant k,. 1 1.10 x 10-2 1.30 x 10-2 3.21 x 10-3
2 2.20 x 10-2 1.30 x 10-2 6.40 x 10-3

O2 (g) + 2NO (g) 2NO2 (g) � �m

O]✘
m m
Rate2 k [O2 ] 2 [N O]n Rate2 [N✘
k✁ [O2 ] 2 ✘ n
[O2 ]2
= = = =
O]✘
[N✘ [O2 ]1
m m
Rate1 k [O2 ] 1 [N O]n Rate1 k✁ [O2 ] 1 ✘ n
initial reactant
Measured Rate
concentrations (mol/L) � �m
Rate2 6.40 × 10−3 M s−1 2.20 × 10−2 mol/L
Experiment [O2] [NO] rate (mol/L.s) = =
Rate1 3.21 × 10−3 M s−1 1.10 × 10−2 mol/L
1 1.10 x 10-2 1.30 x 10-2 3.21 x 10-3
Rate2
2 2.20 x 10-2 1.30 x 10-2 6.40 x 10-3
Rate1
= 1.99 = (2.00)m m=1
3 1.10 x 10-2 2.60 x 10-2 12.8 x 10-3
rate = k [O2]1 [NO]n

Use the same approach to solve for n We can summarize our answer:
initial reactant concentrations (mol/L) initial rate
experiment O2 NO (mol/L.s) O2 (g) + 2NO (g) 2NO2 (g)
1 1.10 x 10-2 1.30 x 10-2 3.21 x 10-3
2 2.20 x 10-2 1.30 x 10-2 6.40 x 10-3 Rate Law: rate = k [O2]1 [NO]2
3 1.10 x 10-2 2.60 x 10-2 12.8 x 10-3
Total Order: (1 + 2) third order overall.
m
✟ � m �n
Rate3 k [O2 ] 3 [N O]n Rate3 [O✟
k✁ [N O] 3 ✟ 2]
n
[N O]3
= = = = Rate constant k (from any of the data set)
Rate1 m
k [O2 ] 1 [N O]n Rate1 m
[O✟
k✁ [N O] 1 ✟ ✟ [N O]1
2]
n

� � m
Rate3 12.8 × 10−3 M s−1 2.60 × 10−2 mol/L rate 3.21 × 10−3 M/sec
= = k= =
Rate1 3.21 × 10 M s
−3 −1 1.30 × 10 mol/L
−2
[O2 ] [N O]2 1.10 × 10−2 M × (1.30 × 10−2 M )
2

Rate3
= 4 = (2.00)n n=2
Rate1 k = 1.73 × 103 M −2 sec−1
rate = k [O2]1 [NO]2

In many instances we can determine the Many gaseous reactions occur in a car engine and
order of the reaction by inspection of the exhaust system. One such reaction is as follows:
data.

Use the following data to determine the individual and

overall reaction orders.
aA + bB " cC + dD Rate = k [A]x [B]y

experiment initial rate (M/s) initial [NO2] (M) initial [CO] (M)

2 [B]2
k[A]m n
Rate2 1 0.005 0.10 0.10
Ratio of Rates = 2 0.08 0.40 0.10
1 [B]1
k[A]m
Rate1 n
3 0.0050 0.10 0.20
 rate = k [NO2]m[CO]n Determine the rate law and calculate the rate
constant for the following reaction from the following
First, choose any two experiments in which [CO] remains
data:
constant and [NO2] varies.

rate 2 k [NO2]m2[CO]n2 [NO2] 2 m

rate 1 = k [NO2]m1 [CO]n1
=
[NO2] 1
S2O82- (aq) + 3I- (aq) 2SO42- (aq) + I3- (aq)
0.080 0.40 m
The reaction is
0.0050 = 0.10 ; 16 = 4m and m = 2 2nd order in NO2.

[S2O82-] Initial Rate

rate 3 k [NO2]m3[CO]n3 [CO] 3 n Experiment [I-]
= (M/s)
rate 1 = k [NO2]m1 [CO]n1 [CO] 1
n
1 0.08 0.034 2.2 x 10-4
0.0050 0.20 The reaction is
; 1= 2n and n = 0
0.0050 = 0.10 zero order in CO.
2 0.08 0.017 1.1 x 10-4

3 0.16 0.017 2.2 x 10-4

Rate Law: rate = k [NO2]2[CO]0 = k [NO2]2
The reaction is second order overall.

Determine the rate law and calculate the rate A Summary So Far and A Transition......
constant for the following reaction from the following
data: S2O82- (aq) + 3I- (aq) 2SO42- (aq) + I3- (aq) 1. Rate of Disappearance = - 1 ![A] = - 1
![B]
a !t b !t
Initial
Experiment [S2O8 2-] [I-] Rate (M/ 2. Rate Law: Rate = k [A]m [B]n Order of A Reaction = m + n
s)
1 0.08 0.034 2.2 x 10-4
3. Rate Constant: k: temperature and reaction dependent and
2 0.08 0.017 1.1 x 10-4
determined from experimental data
3 0.16 0.017 2.2 x 10-4

Rate = k[S2 O2−

8 ] [I ]
m − n
4. We use the method of initial rates (and ratios of data) to
determine rate law, order of reaction and rate constant.
By inspecting Ex. 1&2: Rate doubles when doubles ==> n = 1 [I-]
Inspect Ex. 2&3: Rate doubles when [S2O82-] doubles ==> m = 1
The rate law is nice--as it ties the rate of reaction
Rate = k[S2 O2−
8 ] [I ]
1 − 1
to reactant concentration, but it would be better to
rate 2.2 x 10-4 M/s have a function that can tell us the concentration
k= = = 0.08/M•s of [A] at anytime time, t.
[S2O8 ][I ]
2- -
(0.08 M)(0.034 M)

Time-dependent forms or “integrated rate laws” Integrated rate laws are functions derived by solving the
can be derived from the rate law. differential form of the rate law using integral calculus.
The new functions link reactant concentration with time.
Suppose we have: A C
Differential Form Integrated rate laws
Oth Oth
∆[A] d[A] ∆[A] d[A] [A]t = −k t + [A]t=0
rate = − =− = k[A]0 rate = − =− = k[A]0
∆t dt ∆t dt
Calculus New functions
with time as an
1st 1st
∆[A] d[A] independent ∆[A] d[A]
rate = − =− = k[A] rate = − =− = k[A] ln[A]t = −k t + ln[A]t=0
∆t dt
variable ∆t dt

2nd
2nd ∆[A] d[A] 1 1
∆[A] d[A] rate = − =− = k[A]2 = kt +
rate = − =− = k[A]2 ∆t dt [A]t [A]0
∆t dt
For each differential form we can separate the Summary of Kinetic Reaction Equations
variables and integrate each giving 3 new functions.
A!C 0th Order 1st Order 2nd Order
∆[A] d[A]
rate = − =− = k[A] rate law rate = k rate = k[A] rate = k[A]2
∆t dt
integrated rate law in
[A]t = -k t + [A]0 ln[A]t = -k t + ln[A]0 1/[A]t = k t + 1/[A]0
straight-line form
d[A]
∫ = -k ∫ dt
[A] straight line plot [A]t vs t ln[A]t vs t 1/[A]t vs t

slope, y-intercept -k, [A]0 -k, ln[A]0 k, 1/[A]0

ln[A]t = −k t + ln[A]t=0
t1/2 half-life [A]0/2k 0.693/k 1/k[A]0

This equation links [A]t with any time t during the units for k mol/L.s 1/s 1/M sec
reaction. k an [A]0 must be known.

Oth Order Reaction: Deriving the Integral Form 1st Order Reaction: Deriving the Integral Form

∆[A] d[A]
− =− =k ∆[A] d[A]
∆t dt − =− = k[A] Plotting ln[A]t vs
∆t dt
d[A] = −k dt d[A] Time gives a line
Plotting [A]t vs = −k dt with -k = slope!
� � [A]
At t
Time gives a line
dA = −k dt with -k = slope!
� At � t
d[A]
At=0 0 = −k dt
At=0 [A] t=0
[A]t − [A]t=0 = −k t
ln[A]t
ln[A]t − ln[A]t=0 = −k t
[A]t = −k t + [A]t=0
[A]t
ln[A]t = −k t + ln[A]t=0
Time
y = mx+ b y = mx+ b
Time

2nd Order Reaction: Deriving the Integral Form Summary of Kinetic Reaction Equations
∆[A] d[A] Oth 1st 2nd
=− = k[A]2
−
∆t dt
Plotting 1/[A]t vs
A!C order order order
d[A] Time gives a line
= −k dt rate law rate = k rate = k[A] rate = k[A]2
[A]2 with +k = slope!
� At � t
d[A] units for k mol/L.s 1/s 1/M sec
= −k dt
At=0 [A]
2
t=0 integrated rate law in
[A]t = -k t + [A]0 ln[A]t = -k t + ln[A]0 1/[A]t = k t + 1/[A]0
straight-line form
1 1 1/[A]t
− + = −kt
[A]t [A]0 straight line plot [A]t vs t ln[A]t vs t 1/[A]t vs t

1 1 slope, y-intercept -k, [A]0 -k, ln[A]0 k, 1/[A]0

= kt +
[A]t [A]0 Time

y = mx+ b
Suppose the following data was given for the Suppose the following data was given for the
decomposition of N2O5. Determine the order of the decomposition of N2O5. Determine the order of the
reaction and the rate constant. reaction and the rate constant.

2N2O5 ==> 2N2 + 5O2 2N2O5 ==> 2N2 + 5O2 Rate = k [N2O5]m

First, we transform the original data in Excel as shown

below in the table.
Oth 1st 2nd

Then we plot the

Excel data
The linear ln plot shows
The graph that gives a that the reaction is 1st
straight order
line shows us the order
of the reaction. Rate = k [N2O5]m
Oth Order Plot 1st Order Plot 2nd Order Plot
1st Order Plot
Plot shows that the order m = 1
Rate = k [N2O5]

Now pick any two points from

the 1st order data and
determine k.
-k = slope of the line = -k = slope of the line =
-4.68 - -4.104/(20 s - 0 s)
= 0.0288 sec-1 -4.68 - -4.104/(20 s - 0 s)
= -0.0288 sec-1

The half-life, t1/2 is the time for the initial Half-lives, t1/2, can be obtained for all the integrated
concentration [A]t=0 to reduce to 1/2 [A]t=0. rate laws by substituting 1/2[A]o for [A]t in each
t=0 integrated equation.
2N2O5 ==> 2N2 + 5O2 [A]t - [A]0 = -kt
The half-life, t1/2
0th Order 1/2[A]0 - [A]0 = -kt
depends on the 0.6 t1/2 1/2[A]0 = kt
order of the
reaction. 0.5 t1/2 = [A]0/2k
2t1/2
0.4 ln[A]t - ln[A]0 = -kt
3t1/2
[N2O5]

0.3 1st Order ln(1/2[A]0) - ln[A]0 = -kt

ln(1/2) = -kt
0.2 t1/2 = 0.693/k
0.1
1/[A]t - 1/[A]0 = kt
0.0 2nd Order 1/1/2[A]0 - 1/[A]0 = kt
0 24 48 72
t1/2 =1/k[A]0
Time (min)
Transforming the integrated rate laws into We can use the logarithmic form or the
exponential form is useful for time-dependent exponential form of the integrated rate law.
questions. ln[A]t = −k t + ln[A]0
[A] vs time ln [A] vs time
ln[A]t − ln[A]0 = −k t Moving ln[A]0 to the left side
[A]t = [A]t=0 exp(-kt) ln[A]t = −k t + ln[A]t=0
ln[A]t
= −k t ln A - ln B = ln (A/B)
ln[A]0
� �
ln[A]t
[A]

Slope = -k exp = exp(−k t) Take the exp of each side

ln[A]0
ln [A]
Exponential Form of
[A]t = A0 exp(−k t) Integrated Rate Equation

[A]t Fractional Form useful for

= exp(−k t)
Time Time [A]0 problems

Radioactive decay is a well known first order Radioactive decay is a well known first order kinetic
kinetic process. Suppose the half-life of process. Suppose the half-life of radioactive I-132
radioactive I-132 is 2.295h. What percentage is 2.295h. What percentage remains after 24
remains after 24 hours? hours?

For a 1st order reaction ==> t1/2 = 0.693/k

Rearranging: k = 0.693/2.295 hr = 0.302 h-1
Use 1st order integrated law: ln[A]t = -k t + ln[A]0

ln[A]t - ln[A]0 = -k t = ln [A]t/ln[A]0 = ln([A]t/A0) - kt

exp (ln ([A]t/[A]0) = exp(-kt)
[A]t/[A]0 = exp(-k t) = exp(-0.302 24) = 0.000711

%Aremaining = .000711 X 100 = 0.0711

Imagine that the rate law for the reaction of A ! B Imagine that the rate law for the reaction of A ! B
is zero order in reactant A and that the rate is zero order in reactant A and that the rate
constant, k, is known to be 0.02 M/s. If the constant, k, is known to be 0.02 M/s. If the
reaction begins with 1.50 M A, what is [A] 15 reaction begins with 1.50 M A, what is [A] 15
seconds after the reaction starts? seconds after the reaction starts?

The problem states it is 0th Order so we must use the 0th

Order Integrated Rate Law to determine [A] after 15 seconds
elapses.

[A]t = - k t + [A]0
= - (0.02M/sec) (15 sec) + 1.50M

[A]t = 1.3M
The rate law for the reaction of A!2B is zero The rate law for the reaction of A!2B is zero
order in A and has a rate constant of 0.12 M/s. order in A and has a rate constant of 0.12 M/s.
If the reaction starts with 1.50 M A, after what If the reaction starts with 1.50 M A, after what
time will the concentration of A be 0.90M? time will the concentration of A be 0.90M?

In this case the problem gives us: [A]0 = 1.50M

[A]t = 0.90M
k = 0.12 M/sec

It zero order so: [A]t = - k t + [A]0

Rearrange t = -([A]t - [A]0)/k
t = (1.50M - 0.90M)/0.12M/sec
t = 5 sec

The reaction 2A B is first order in A with a rate The reaction 2A B is first order in A with a rate
constant of 2.8 x 10-2 s-1 at 800C. How long will it constant of 2.8 x 10-2 s-1 at 800C. How long will it
take for A to decrease from 0.88 M to 0.14 M ? take for A to decrease from 0.88 M to 0.14 M ?

Given: 1st order process and time = t

[A]0 = 0.88 M [A]t = 0.14 M k = 0.028 sec-1

ln[A]t - ln[A]0 = - k t

k t = ln[A]0 – ln[A]t

[A]0 0.88 M
ln ln
ln[A]0 – ln[A] [A] 0.14 M
t= = = = 66 s
k k 2.8 x 10-2 s-1

Summary of Kinetic Reaction Equations The first order rate constant is 1.87 x 10-3 min-1 at 37˚C
for a reaction of cisplatin (a cancer drug) with water.
Suppose that the concentration of cisplatin in the blood
A!C zero
order
first
order
second
order stream in a cancer patient is 4.73 x 10-4 mol/L. What
will be the concentration of cisplatin 24 hours later?
rate law rate = k rate = k[A] rate = k[A]2

integrated rate law in [A]t = -k t + [A]0 ln[A]t = -k t + ln[A]0 1/[A]t = k t + 1/[A]0

straight-line form

straight line plot [A]t vs t ln[A]t vs t 1/[A]t vs t

slope, y-intercept -k, [A]0 -k, ln[A]0 k, 1/[A]0

t1/2 half-life [A]0/2k 0.693/k 1/k[A]0

units for k mol/L.s 1/s L/mol.s

 The first order rate constant is 1.87 x 10-3 min-1 at 37˚C for a At 10000C, cyclobutane (C4H8) decomposes in a
reaction of cisplatin (a cancer drug) with water. Suppose
that the concentration of cisplatin in the blood stream in a
first-order reaction to two molecules of ethylene
cancer patient after injection is 4.73 x 10-4 mol/L. What will (C2H4) with a known rate constant, k, of 87s-1, .
be the concentration of cisplatin 24 hours later?
(a) If the initial C4H8 concentration is 2.00M,
Given: [A]0 = 4.73 X 10-4 M and k = 1.87 x 10-3 min-1, t = 24hr
what is the concentration after 0.010 s?
ln[A]t = −k t + ln[A]0
ln[A]t − ln[A]0 = −k t (b) What fraction of C4H8 has decomposed
ln[A]t in this time?
= −k t
ln[A]0
� � PLAN:
ln[A]t
exp = exp(−k t) We need to find the [C4H8] at time, t. We have to use
ln[A]0
the integrated rate law for a 1st order reaction. Once
[A]t = A0 exp(−k t) that value is found, divide the amount decomposed by
[A]t = (4.73 x 10-4) exp(-1.87 x 10-3 min-1 x 24 hr x 60 min/hr) the initial concentration.
= 3.20 X 10-5M

At 10000C, cyclobutane (C4H8) decomposes in a At 10000C, cyclobutane (C4H8) decomposes in a

first-order reaction, with the very high rate constant 2nd-order reaction, with the very high rate constant
of 87s-1, to two molecules of ethylene (C2H4). of 87 L/mol s, to two molecules of ethylene (C2H4).
(a) If the initial C4H8 concentration is 2.00M, what is the
concentration after 0.010 s? (a) If the initial C4H8 concentration is 2.00M, what
is the concentration after 0.010 s?
(a) ln[A]t = −k t + ln[A]0
2nd order rate equation: 1/[A]t = k t + 1/[A]0
ln[A]t
= −k t = ln [C4H8]t = -kt Given: [A]0 = 2.00 M, k = 87, t = 0.010 sec
ln[A]0 [C4H8]0 Rearranging: [A]t = 1/(kt + 1/[A]0)
[C4H8]t Rearranging: [A]t = 1/[(87 s-1 (0.01 s)) + 1/2M] = 0.7299M
= ln = -(87s-1)(0.010s)
2.00
[C4H8] = (2 M) X exp(-87s-1)(0.010s) = 0.837 M (b) What fraction of C4H8 has decomposed in this time?
Fraction decomposed = ([A]0 - [A]t) /[A]0
(b) What fraction of C4H8 has decomposed in this time?
Fraction decomposed = (2M - 0.7299) /2M = 0.635 ~ 0.64
[C4H8]0 - [C4H8]t 2.00M - 0.837M
(b) = = 0.58
[C4H8]0 2.00M

The rate constant for the second order reaction The rate constant for the second order reaction
2A!B is 5.3"10-5 M-1s-1. What is the original 2A!B is 5.3"10-5 M-1s-1. What is the original
amount present if, after 2 hours, there is amount present if, after 2 hours, there is
0.35M available? 0.35M available?

A0 = 0.40 M
The rate constant for a second order reaction B
The rate constant for a second order reaction is
==> C is 4.5"10-4 M-1s-1. What is the half-life
4.5"10-4 M-1s-1. What is the half-life if we start
of this reaction if the reactions begins with a
with a reactant concentration of 5.0 M?
reactant concentration of 5.0 M?
We have to
know that the
half-life for
second order is:

t1/2 =440 s
=7.4 min

The Chernobyl nuclear reactor accident occurred in 1986.

The reactor exploded some 2.4 MCi of radioactive 137Cs
into the atmosphere (1000Ci received over a period of
several minutes is deadly). Assuming first-order kinetics
and knowing that the half-life of 137Cs is 30.1 years, what
year will the amount of 137Cs released from Chernobyl
finally decrease to 100 Ci? A Ci is a unit of radioactivity
called the Curie.

Cyclopropane is the smallest cyclic hydrocarbon. Cyclopropane is the smallest cyclic hydrocarbon.
Because its 60o bond angles allow poor orbital overlap, Because its 60o bond angles allow poor orbital
its bonds are weak. As a result, it is thermally unstable overlap, its bonds are weak. As a result, it is
and rearranges to propene at 1000 oC via the following thermally unstable and rearranges to propene at
first-order reaction: 1000 oC via the following first-order reaction:
CH2
! CH2
H2 C CH2 (g) CH3-CH=CH2 !
H2 C CH2 (g) CH3-CH=CH2
Suppose the rate constant k = 9.2 s-1. Suppose the rate constant k = 9.2 s-1.

(a) How long will it take for for 1/2 of cyclopropane to (a) How long will it take for for 1/2 of cyclopropane to
rearrange to propene (ie. what is the half-life--t1/2) ? rearrange to propene (ie. what is the half-life--t1/2) ?

(b) How long does it take for [cyclopropane] to reach one- t1/2 = 0.693 / 9.2 s-1 = 0.075 s
quarter of its initial value? (b) How long does it take for [cyclopropane] to reach one-
quarter of its initial value?
It takes 1 half-life to get to 1/2 [A]0 another to get to 1/4 of
[A]t=0 2 t1/2 = 2 (0.075 s) = 0.15 s
Experiments show that reaction rate If we plot k vs T data we observe that k increases
increases when temperature increases. exponentially as T increases.
R-COOR’ + H2O R-COOH + R’OH
ester acid alcohol

Note both Rate = k [RCOOR’]m [H2O]n

reactant
concentrations Rate
Temperature Constant
are
Increased Increased

k (L/mol sec)
held constant
Exponential
increase of k with T Temperature alters
the rate constant, k
of a chemical
reaction!

NICE EQUATION BUT NOT SO USEFUL AS IS Temperature (Kelvin)

Physicist Svante Arrhenius showed that the rate Plotting ln k vs 1/T, we get a straight line with a
constant, k ,varies with temperature according to: slope Ea/R. It’s called an Arrehenius Plot.
−Ea 1
ln k = + ln A
R T Arrehenius Plot
k = A e−Ea /RT = A exp(−Ea /RT) y = -m x + b
Slope = -Ea/R
Temp k
• k: reaction rate constant (°C) (M-1 s-1)
• Ea = Activation energy (specific for any given reaction) ln k
283 3.52E-07
• A = Frequency factor (related to geometry and # of
collisions for any given reaction) 356 3.02E+05

• T = temperature in Kelvin 393 2.19E-04

• R = gas constant (R = 8.314 J/mol . K) 427 1.16E-03

508 3.95E-02 1/T (K-1)

Because the rate of a chemical reaction depends The Arrehenius equation links the macroscopic
on the temperature, different temperatures give rate constant, k, to the fraction of molecular
different rate constants (k). collisions with proper spatial orientation and Ea
Consider the first order reaction and pretend someone finds of collision theory at a molecular level.
that the experimental rate law is first order:
k = A e−Ea /RT Arrehenius equation

A " C rate = k(T) [A]1

Activation Gas
Energy Constant

Temperature (K)
What is the molecular origin of the temperature
dependence? k = pZe−Ea /RT
Fraction of
collisions Constant Fraction of collisions
with proper related with sufficient
orientations to collision energy
frequency for reaction
If we plug the Arrehenius factor into our “rate law We can transform the Arrhenius equation to
expression” we can see the temperature useful graphical form by taking the natural
dependence that we could not see before. logarithm (ln) of each side.

aA + bB " cC + dD rate = k [A]m [B]n

k = A e−Ea /RT = A exp(−Ea /RT)

substituting for k
ln k = ln (A exp(−Ea /RT)) Take ln of both sides
rate = A exp (-Ea/RT) [A]m [B]n Rate law showing ln k = ln A + ln(exp(−Ea /RT)) Expanding
temperature
rate = pZ exp (-Ea/RT) [A]m [B]n dependence −Ea 1
ln k = + ln A This equation has the form
R T
y = mx + b
Normally, we are interested in rates and rate laws at y = -m x + b
some single temperature T

We can also transform the Arrhenius equation The decomposition reaction of hydrogen iodide,
into something more useful using ratios of two
different rate constants at two different temps. 2HI(g) H2(g) + I2(g)
has a rate constant of 9.51 x 10-9 L/mol.s at 500. K and
k2 A e−Ea /RT2 one of 1.10 x 10-5 L/mol.s at 600. K. Find the activation
= =e −Ea /RT2 − −Ea /RT1
k1 A e−Ea /RT1 energy, Ea.
= e−Ea /RT2 + Ea /RT1
� �
k2 Ea 1 1
= exp −
k1 R T1 T2
� � � �
k2 Ea 1 1
ln = −
k1 R T1 T2

IT SAYS: If we have data for k2 at T2 we can

determine k1 and some other temperature T1

The decomposition reaction of hydrogen iodide, There are unanswered questions using the equations
of kinetics which are largely macroscopic.
2HI(g) H2(g) + I2(g)
1) Why does the reaction rate depend on
has a rate constant of 9.51 x 10-9 L/mol.s at 500. K and
temperature but yet there is no T in the rate law
one of 1.10 x 10-5 L/mol.s at 600. K. Find the activation
energy, Ea. equation?
� � � � 2) Why are [A] and [B] multiplied in the rate law equations?
k2 Ea 1 1
ln =− −
k1 R T2 T1
3) What is happening at the molecular level?
� �−1
k2 1 1
Ea = −R ln − 4) Why does the reaction rate depend on
k1 T2 T1
� �� �−1 concentration of reactants to varying degrees?
1.10 × 10−5 L/mol s 1 1
Ea = −(8.314 J/mol K) ln −
9.51 × 10−9 L/mol s 600 K 500 K Two models help chemists understand what is
happening at a molecular level: 1) collision theory
Ea = 1.76 x 105 J/mol = 176 kJ/mol
and 2) transition state theory.
The framework of the kinetic models.
Collision Theory provides the “microscopic basis” of
the rate law, and explains the following:
1. Collision Theory--is like Kinetic Molecular theory
of gases. Chemical reactions occur only when reactant
molecules collide. Those molecules with a certain
minimum activation energy (Ea), temperature and correct • Why Concentrations Are Multiplied in the Rate Law
spatial orientation will transform into products.
• How Temperature affects a Reaction Rate by linking k, the
rate constant to temperature, molecule collision frequency,
molecule spatial orientation and fraction of molecules that
2. Transition State Theory--graphical model used to have sufficient energy to react (the Activation Energy, Ea)
describe the thermodynamics of a reaction while
postulating what reactants and products look like in • Spatial Orientation of Reactants
transforming reactants to products. We get “reaction – Molecules must be oriented in a certain way called “effective
mechanisms” that useful in organic chemistry. collisions” in 3-D space in order for a collision to lead to a
chemical reaction.

The reactants are multiplied in the rate law Reactants must be collide with the proper spatial
because a product must collide to transform to a orientation in order to transform from reactant to
product. Multiplying gives # collisions. product.
Why
A + B C rate = k [A][B] Multiplication?

A B 4 collisions
We multiply because the
2x2=4 rate depends on the
A B
number of collisions
(which is found by Collision 1 Collision 2
multiplication)
A
B 6 collisions

A 3x2=6
A B
B
9 collisions
A
A B 3x3=9
Add another
molecule of A A B Collision 3 Collision 4

Activation energy, Ea, is the minimum kinetic energy The Arrehenius equation links the macroscopic
needed for a reaction to occur. Higher T results in rate constant to fraction of molecular collisions
greater fraction of molecules with critical energy > Ea with proper spatial orientation and Ea of collision
theory.
fraction = e-Ea/RT
called the
no reaction Ea Boltzman k = A e−Ea /RT
Fraction of Collisions, f

Increasing T
serves to factor
produce a larger Activation Gas
Energy Constant
fraction of
molecules > Ea Temperature (K)
T1 k = pZe−Ea /RT
only this fraction
T2 > T 1 can react Fraction of
collisions Constant Fraction of collisions
with proper related with sufficient
orientations to collision energy
Kinetic Energy frequency for reaction
The reaction rate constant, k, increases when Because all chemical reactions are reversible, there
either the activation energy (Ea) decreases or the is an activation energy, Ea for both the forward
temperature increases. reaction and the reverse reaction directions.
kforward
k = A e−Ea /RT = A exp(−Ea /RT) A + B C + D
kreverse Ea is a property of the height of
The Effect of Ea and T on the Reactants Products the hill (i.e. the chem reaction)
Fraction of Collisions With
Sufficient Energy to Transform
The rate constant is Ea
altered by changing Forward
the fraction of Eb-a
energetic A + B Reverse
molecules.
!H

C+D

Same information as preceding slide but shown in a Key Points of Collision Theory
more “chemistry-like” way. Formal. 1. increased T increased average speed and KE of
particles increased collision frequency increased
fraction of reacting molecule increase reaction rate

kforward
A + B C + D 2. Significance of Activation Energy, Ea : only molecular collisions
kreverse with energy ! Ea can yield products.
Reactants Products

3. Reactants must collide with the “correct” spatial orientation

Ea to react and give products.
Is this reaction
exothermic or
endothermic? 4. Either decreasing Ea and/or increasing T enhances the
fraction of productive collisions, f increases and through the
Arrenhius equation k and the reaction rate increases.

Transition State Theory explains the energetics and Reaction energy diagrams are used to depict the
postulate what substances look like as they are energetics and events that occur as reactants are
transforming from reactants to products. transformed to products.

--A reaction energy A Reaction Energy Diagram

diagram depicts the Transition State
transition state, A....B....C
Potential Energy (kJ)

activation energy, and (Transition State)

thermodynamics.
Eforward
--The theory postulates Ea
Energy

“intermediate Ereverse
A + BC
structures” called a N2 O(g) + NO(g)
(Reactants)
transition state or ∆H AB + C Reactants ∆H =
activated complex and
(Products) -139kJ Products
energy barriers
(activation energy) as Reation Progress N2 (g) + NO2 (g)
a reaction occurs.
Reaction Progress
Reaction energy diagrams include the energetics Example: Consider the proposed transition state for
for enthalpies and levels of activation energy. the reaction:
CH3Br + OH ===> CH3OH + Br
- -

NO(g) + O3 (g) −−→ NO2 (g) + O2 (g) tetrahedral Transition tetrahedral

geometry State geometry

∆H > 0 ∆H < 0 ∆H < 0

2 NOCl(g) −−→ 2 NO(g) + Cl2 (g)

Example: Consider the proposed transition state for CH3Br + OH- ===> CH3OH + Br-
the reaction:
CH3Br + OH- ===> CH3OH + Br-
tetrahedral tetrahedral
geometry geometry

The postulated transition

state is NOT
TETRAHEDRAL but
rather trigonal
bipyramidal; note the
elongated forming C---Br
and the breaking C---O
bonds.

The activation energy, Ea can be viewed as the Transition state theory says that every step in a
energy required to stretch and deform bonds forming reaction goes through a transition state from which it
a an activated complex or transition state. continue in either the forward or reverse directions.

Ea E

∆
∆H
A key reaction in the upper atmosphere is O3(g) + O(g) 2O2(g)
The Ea(fwd) is 19 kJ, and !Hrxn for the reaction is -392 kJ.
O3(g) + O(g) 2O2(g)
Draw a reaction energy diagram for this reaction, a
transition state, and calculate Ea(rev).
The Ea(fwd) is 19 kJ, and !Hrxn for the reaction is -392 kJ.
transition state
Draw a reaction energy diagram for this reaction, a Not to scale!
transition state, and calculate Ea(rev).

Ea(rev) = (392 + 19) kJ

= 411 kJ

!Hrxn = Hf - Hi = -392kJ

Each elementary step is characterized by its

Reaction Mechanisms--Why and What For molecularity, which is the number of molecules
A balanced chemical equation tells us what reactants react reacting in the elementary step....this also is the
and what products are made. It does not tell us how the order of the reaction for that elementary step.
transformation occurs on a molecular level.
experimentally
2 A + B −−→ E + F Rate = k[A][B] derived
A reaction mechanism is a series of postulated chemical
equations or events called “elementary steps” which are
posited “molecular events” for reactant molecules.
Elementary step 1: A + B −−→ C intermediates
Elementary step 2: C + A −−→ D Elementary step: NO2 + NO2 NO3 + NO bimolecular
Elementary step 3: D −−→ E + F Elementary step: NO3 + CO NO2 + CO2 bimolecular
Overall reaction: 2 A + B −−→ E + F Overall reaction: 2NO2 + CO NO + CO2
An intermediate is formed in an early elementary step and
consumed in a later elementary step.

Correlating A Reaction Mechanism with the Rate Law The experimental rate law for the reaction between NO2
(1) the sum of the elementary steps must give the and CO to produce NO and CO2 is rate = k[NO2]2. The
overall balanced equation for the reaction. reaction is believed to occur via two steps:
(2) The rate law for each elementary step is given by
the equation stoichiometry and must be reasonable. Step 1: NO2 + NO2 NO + NO3
(3) The rate limiting step (slowest step) determines This rate law is Step 2: NO3 + CO NO2 + CO2
the rate law of the overall reaction! See below determined by
experiment. What is the equation for the overall reaction?

NO2 (g) + CO (g) NO (g) + CO2 (g) Rate = k[NO2]2

What is the intermediate?

Here is the postulated mechanism intermediate This matches the

experimental. What is the molecularity and order of each step?
Elementary step: NO2 + NO2 NO3 + NO Rate = k[NO2]2
Elementary step: NO3 + CO NO2 + CO2 Rate = k2[NO3][CO] What can you say about the relative rates of steps 1 and 2?
Overall reaction: NO2 + CO NO + CO2 Rate = k[NO2]2
 The experimental rate law for the reaction between NO2 Each elementary step has its own rate law and
and CO to produce NO and CO2 is rate = k[NO2]2. The rate constant k and....it’s own activation energy,
reaction is believed to occur via two steps: Ea. We can show these in a reaction energy
diagram.
Step 1: NO2 + NO2 NO + NO3
2NO2 + F2 => 2NO2F
Step 2: NO3 + CO NO2 + CO2
Exp. Rate = k[NO2][F2]
What is the equation for the overall reaction?

NO2+ CO NO + CO2 rate = k[NO2]2

Steps:
What is the intermediate? NO3
NO2 + F2 => NO2F + F
What is the molecularity and order of each step? bi-2 and bi-2 NO2 + F => NO2F
What can you say about the relative rates of steps 1 and 2?
rate = k[NO2]2 is the rate law for step 1 and rate2 = k[NO3][CO] 2NO2 + F2 ==> 2NO2F
therefore step 1 must be rate limiting (it matches the
experiment)

The following elementary steps are proposed as the The following elementary steps are proposed as the
mechanism of an overall reaction: mechanism of an overall reaction:
(1) NO2Cl(g) NO2(g) + Cl (g) (1) NO2Cl(g) NO2(g) + Cl (g)
(2) NO2Cl(g) + Cl (g) NO2(g) + Cl2(g) (2) NO2Cl(g) + Cl (g) NO2(g) + Cl2(g)

(a) Write the overall balanced equation. (a) Write the overall balanced equation.
(b) Determine the molecularity of each step. (b) Determine the molecularity of each step.
(c) Is there an intermediate? (c) Is there an intermediate?
(d) What is the rate law for each step? (d) What is the rate law for each step?
(e) If the experimental rate law is found to be 1st order which (e) If the experimental rate law is found to be 1st order which
reaction is rate-limiting? reaction is rate-limiting?
SOLUTION: (b) Step(1) is unimolecular.
(a) (1) NO2Cl(g) NO2(g) + Cl (g) Step(2) is bimolecular.
(2) NO Cl(g) + Cl (g) NO2(g) + Cl2(g) (c) rate1 = k1 [NO2Cl]
2
rate2 = k2 [NO2Cl][Cl]
2NO2Cl(g) 2NO2(g) + Cl2(g)

Summary A catalyst is any substance that increases the rate

of a chemical reaction without itself being
• The overall chemical reaction is a sequence of consumed in the reaction.
elementary steps called the reaction mechanism.

--increases reaction
• The rate law of each elementary step can be determined rate in both directions
from stoichiometry and determines the molecularity. by increasing k via
lowering the activation
• Therefore, the experimentally observed rate law for an Uncatalyzed
energy, Ea of the Pathway Catalyzed
overall reaction must depend on the reaction reaction. Pathway
mechanism.
--The reaction thermodynamics (enthalpy,
• The slowest elementary step in a multistep reaction is entropy) are unaffected!
called the rate-determining step---it determined by the
--No change in the yield of the reaction!
rate of the rate-determining step.
• The overall reaction cannot occur faster than the speed of --The catalyzed reaction proceeds via a different reaction
mechanism than the uncatalyzed reaction.
the rate-determining step.
A catalyst increases k by lowering the activation
energy, Ea, relative to an uncatalyzed reaction.

Both
reactions
have the same
enthalpy, !H

Catalyst does Ea Uncatalyzed

not alter the No
Potential Energy

yield of the Catalyst

reaction Ea
relative to Uncatalyzed
Ea
uncatalyzed Catalyzed Catalyzed
pathway.

The reaction Reactants

!Hreaction
pathway
(mechanism)
is different in Products
a catalyzed
reaction
Reaction Progress