202-NYB - KINETICS

Figure 16.2 The wide range of reaction rates.

Figure 16.1 Reaction rate: the central focus of chemical kinetics
Factors That Influence Reaction Rate

Under a specific set of conditions, every reaction has its own

characteristic rate, which depends upon the chemical nature of
the reactants.

Four factors can be controlled during the reaction:

2. Concentration - molecules must collide to react;
3. Physical state - molecules must mix to collide;
4. Temperature - molecules must collide with enough energy to react;
5. The use of a catalyst.
Figure 16.3 The effect of surface area on reaction rate.
Figure 16.4 Collision energy and reaction rate.
 Expressing the Reaction Rate

reaction rate - changes in the concentrations of reactants or

products per unit time

reactant concentrations decrease while product concentrations

increase
for A B

change in concentration of A conc A2-conc A1

rate of reaction = - =-
change in time t2-t1

∆ (conc A)
-
∆t
 Table 16.1 Concentration of O3 at Various Time in its
Reaction with C2H4 at 303K

C2H4(g) + O 3(g) C 2H4 O(g) + O2(g)

Time (s) Concentration of O3 (mol/L)

0.0 3.20x10-5
∆ (conc A)
- 10.0 2.42x10-5
∆t
20.0 1.95x10-5
30.0 1.63x10-5
40.0 1.40x10-5
50.0 1.23x10-5
60.0 1.10x10-5
Figure 16.5
The concentrations of O3 vs. time during its reaction with C2H4
C2H4(g) + O 3(g) C 2H4 O(g) + O2(g)

rate =

∆ [C2H4]
- =
∆t

∆ [O3]
-
∆t
 Figure 16.6 Plots of [C2H4] and [O2] vs. time.

Tools of the 
Laboratory
In general, for the reaction

aA + bB cC + dD

1 ∆[A] 1 ∆[B] 1 ∆[C] 1 ∆[D]

rate = - = - = + = +
a ∆t b ∆t c ∆t 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.
Sample Problem 16.1 Expressing Rate in Terms of Changes in
Concentration with Time

PROBLEM: Because it has a nonpolluting product (water vapor), hydrogen

gas is used for fuel aboard the space shuttle and may be used
by Earth-bound 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?
PLAN: Choose [O2] as a point of reference since its coefficient is 1. For every
molecule of O2 which disappears, 2 molecules of H2 disappear and 2
molecules of H2O appear, so [O2] is disappearing at half the rate of
change of H2 and H2O.
SOLUTION: ∆[H2] ∆[O2] ∆[H2O]
1 1
(a) rate = - 2 =- =+
∆t ∆t 2 ∆t
∆[O2] ∆[H2O] ∆[H2O]
(b) - = - 0.23mol/L*s = + 1 ; = 0.46mol/L*s
∆t 2 ∆t ∆t
Sample Problem 16.2 Determining Reaction Order from Rate Laws

PROBLEM: For each of the following reactions, determine the reaction order
with respect to each reactant and the overall order from the
given rate law.
(a) 2NO(g) + O2(g) 2NO2(g); rate = k[NO]2[O2]
(b) CH3CHO(g) CH4(g) + CO(g); rate = k[CH3CHO]3/2
(c) H2O2(aq) + 3I-(aq) + 2H+(aq) I3-(aq) + 2H2O(l); rate = k[H2O2][I-]

PLAN: 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 3/2 order in CH3CHO and 3/2 order overall.

(c) The reaction is 1st order in H2O2, 1st order in I- and zero order in H+,
while being 2nd order overall.
Table 16.2 Initial Rates for a Series of Experiments in the
Reaction Between O2 and NO

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

Initial Reactant
Initial Rate
Concentrations (mol/L)
Experiment (mol/L*s)
O2 NO

1 1.10x10-2 1.30x10-2 3.21x10-3

2 2.20x10-2 1.30x10-2 6.40x10-3

3 1.10x10-2 2.60x10-2 12.8x10-3

4 3.30x10-2 1.30x10-2 9.60x10-3

5 1.10x10-2 3.90x10-2 28.8x10-3

 Determining Reaction Orders
Using initial rates -

Run a series of experiments, each of which starts with a different set

of reactant concentrations, and from each obtain an initial rate.
See Table 16.2 for data on the reaction

O2(g) + 2NO(g) 2NO2(g) rate = k [O2]m[NO]n

Compare 2 experiments in which the concentration of one reactant

varies and the concentration of the other reactant(s) remains constant.

rate2 k [O2]2m[NO]2n [O2]2m m

[O2]2
= = =
rate1 k [O2]1 [NO]
m n [O2]1m [O2]1
1

6.40x10-3mol/L*s 2.20x10-2mol/L m
= ; 2 = 2m m=1
3.21x10-3mol/L*s 1.10x10-2mol/L

Do a similar calculation for the other reactant(s).

Sample Problem 16.3 Determining Reaction Order from Initial Rate Data

PROBLEM: Many gaseous reactions occur in a car engine and exhaust

system. One of these is

NO2(g) + CO(g) NO(g) + CO2(g) rate = k[NO2]m[CO]n

Use the following data to determine the individual and overall reaction orders.

Experiment Initial Rate(mol/L*s) Initial [NO2] (mol/L) Initial [CO]

(mol/L)
1 0.0050 0.10 0.10
2 0.080 0.40 0.10
3 0.0050 0.10 0.20

PLAN: Solve for each reactant using the general rate law using the
method described previously.

SOLUTION: rate = k [NO2]m[CO]n

First, choose two experiments in which [CO] remains

constant and the [NO2] varies.
Sample Problem 16.3 Determining Reaction Order from Initial Rate Data

continued

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

= = The reaction is
rate 1 k [NO2] 1 [CO]
m n
[NO2] 1
1 2nd order in NO2.
0.080 0.40 m
= ; 16 = 4m and m = 2
0.0050 0.10

rate 3 k [NO2]m3[CO]n3 [CO] 3 n

The reaction is
= =
rate 1 k [NO2]m1 [CO]n1 [CO] 1 zero order in CO.

0.0050 0.20 n
= ; 1 = 2n and n = 0
0.0050 0.10

rate = k [NO2]2[CO]0 = k [NO2]2

 Integrated Rate Laws

∆[A]
rate = - = k [A] first order rate equation
∆t
[A]0
ln = - kt ln [A]0 = -kt + ln [A]t
[A]t
∆[A]
rate = - = k [A]2 second order rate equation
∆t
1 1 1 1
- = kt = kt +
[A]t [A]0 [A]t [A]0

∆[A]
rate = - = k [A]0 zero order rate equation
∆t
[A]t - [A]0 = - kt
Table 16.3 Units of the Rate Constant k for Several Overall
Reaction Orders

Overall Reaction Order Units of k (t in seconds)

0 mol/L*s (or mol L-1 s-1)

1 1/s (or s-1)

2 L/mol*s (or L mol -1 s-1)

3 L2 / mol2 *s (or L2 mol-2 s-1)

Sample Problem 16.4 Determining Reaction Concentration at a Given Time

PROBLEM: At 10000C, cyclobutane (C4H8) decomposes in a first-order

reaction, with the very high rate constant of 87s-1, to two
molecules of ethylene (C2H4).
(a) If the initial C4H8 concentration is 2.00M, what is the
concentration after 0.010 s?
(b) What fraction of C4H8 has decomposed in this time?

PLAN: Find the [C4H8] at time, t, using the integrated rate law for a 1st order
reaction. Once that value is found, divide the amount decomposed by
the initial concentration.
SOLUTION: [C4H8]0 2.00
ln = kt ; ln = (87s-1)(0.010s)
(a) [C4H8]t [C4H8]

[C4H8] = 0.83mol/L

(b) [C4H8]0 - [C4H8]t 2.00M - 0.87M

= = 0.58
[C4H8]0 2.00M
Figure 16.7 Integrated rate laws and reaction order

1/[A]t = kt + 1/[A]0

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

ln[A]t = -kt + ln[A]0
Figure 16.8 Graphical determination of the reaction order for the
decomposition of N2O5.
Figure 16.9 A plot of [N2O5] vs. time for three half-lives.

for a first-order process

ln 2 0.693
t1/2 = =
k k
 Sample Problem 16.5 Determining the Half-Life of a First-Order Reaction

PROBLEM: Cyclopropane is the smallest cyclic hydrocarbon. Because its

600 bond angles allow poor orbital overlap, its bonds are weak.
As a result, it is thermally unstable and rearranges to propene at
10000C via the following first-order reaction:
CH2
∆
H C CH (g) H3C CH CH2 (g)
2 2
The rate constant is 9.2s-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 = , to find the half-life.
k
One-quarter of the initial value means two half-lives have passed.
SOLUTION:

(a) t1/2 = 0.693/9.2s-1 = 0.075s (b) 2 t1/2 = 2(0.075s) = 0.150s

 Table 16.4 An Overview of Zero-Order, First-Order, and
Simple Second-Order Reactions

Zero Order First Order Second Order

Rate law rate = k rate = k [A] rate = k [A]2

Units for k mol/L*s 1/s L/mol*s

Integrated rate law in [A]t = ln[A]t = 1/[A]t =

straight-line form k t + [A]0 -k t + ln[A]0 k t + 1/[A]0

Plot for straight line [A]t vs. t ln[A]t vs. t 1/[A]t = t

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

Half-life [A]0/2k ln 2/k 1/k [A]0

Figure 16.10 Dependence of the rate constant on temperature
The Effect of Temperature on Reaction Rate

The Arrhenius Equation

Ea where k is the kinetic rate constant at T

k = Ae− RT Ea is the activation energy

R is the energy gas constant

T is the Kelvin temperature

ln k = ln A - Ea/RT
A is the collision frequency factor

k2 Ea 1 1
ln = - -
k1 RT T2 T1
Figure 16.11 Graphical determination of the activation energy

ln k = -Ea/R (1/T) + ln A
Sample Problem 16.6 Determining the Energy of Activation

PROBLEM: The decomposition of hydrogen iodide,

2HI(g) H2(g) + I2(g)

has rate constants of 9.51x10-9L/mol*s at 500. K and 1.10x10-5

L/mol*s at 600. K. Find Ea.

PLAN: Use the modification of the Arrhenius equation to find Ea.

SOLUTION: -1
k2 Ea 1 1 k2 1 1
ln = - - Ea = - R ln -
k1 R T2 T1 k1 T2 T1

1.10x10-5L/mol*s 1 1
Ea = - (8.314J/mol*K) ln -
9..51x10-9L/mol*s 600K 500K

Ea = 1.76x105 J/mol = 176 kJ/mol

Figure 16.12
Information sequence to determine the kinetic parameters of a reaction.

Series of plots
of concentra-
tion vs. time Initial
rates Reaction Rate constant
Determine slope  orders (k) and actual
of tangent at t0 for  Compare initial  rate law
each plot rates when [A]  Substitute initial rates, 
changes and [B] is  orders, and concentrations  Find k  at 
held constant and  into general rate law:      varied T
vice versa rate = k [A] [B]
m n

Activation
Rate constant energy, Ea
Integrated and reaction Find k  at 
rate law order
Plots of varied T
(half-life,
concentration t1/2) Rearrange to 
vs. time linear form and 
Use direct, ln or  graph
inverse plot to 
find order
Figure 16.13

The dependence of possible collisions on the product

of reactant concentrations.

A B
4 collisions
A B

A
B
Add another 6 collisions
molecule of A A
B
A
A B

Add another A B
molecule of B
A B
Table 16.5 The Effect of Ea and T on the Fraction (f) of Collisions
with Sufficient Energy to Allow Reaction

Ea (kJ/mol) f (at T = 298 K)

50 1.70x10-9

75 7.03x10-14

100 2.90x10-18

T f (at Ea = 50 kJ/mol)

250C(298K) 1.70x10-9

350C(308K) 3.29x10-9

450C(318K) 6.12x10-9
Figure 16.14
The effect of temperature on the distribution of collision energies
Figure 16.15 Energy-level diagram for a reaction

ACTIVATED STATE

Ea (forward)
Collision Energy

Collision Energy
Ea (reverse)

REACTANTS

PRODUCTS

The forward reaction is exothermic because the

reactants have more energy than the products.
Figure 16.16 An energy-level diagram of the fraction of collisions
exceeding Ea.
Figure 16.17

The importance of molecular orientation to an effective collision.

NO + NO3 2 NO2

A is the frequency factor

Z is the collision frequency
A = pZ where
p is the orientation probability factor
 REACTION MECHANISMS

Table 16.6 Rate Laws for General Elementary Steps

Elementary Step Molecularity Rate Law

A product Unimolecular Rate = k [A]

2A product Bimolecular Rate = k [A]2

A+B product Bimolecular Rate = k [A][B]

2A + B product Termolecular Rate = k [A]2[B]

Figure 16.22

Reaction energy diagram of a catalyzed and an uncatalyzed process.