Chapter 12 Environmental Chemical

Reactions and Transformations

There are more than 70,000 synthetic chemicals that are

in daily use.

solvents
components of detergents
dyes and varnishes
additives in plastics and textiles
chemicals used for construction
antifouling agents
herbicides
insecticides
fungicides

The US EPA in the 1990 Clean Air Amendments

estimates that there are ~2000 excess deaths in the US
each year due to exposures to hazardous chemicals

1
Chapter 12 Environmental Chemical Reactions and
Transformations

Photochemical
Biological-Microbial
Dark reactions

1.kinetics

order of a reaction

Arrhnenius temperature -rate const

rate limiting steps

steady-state approximation

Hammett relationships and rate constants

Langmiurian rate constants

kinetic simulations

2.mechanisms

hydrolysis

organics in the environment

2
Kinetics: the rate law of a reaction must be verified by
experimentation

1st order reactions

A ---> B

-d [A] /dt = krate [A]

- d [A]/[A] = kratedt

,t t
ln[ A ] A
A, t 0 k t

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

typically to get a 1st order fit, 70% of A needs to react if

the rate constant is independent of concentration

-CH - Cl
2 + H2O---> -CH - OH + H
2
+
+ Cl-
benzyl chloride benzyl alcohol

3
Figure 12.1 page 470 Fig. 12.2

4
 t1/2 = time it takes for [A] to decrease by a
factor of 2

ln [A]/[A]o=-k t1/2 ; ln2 /k =t1/2

life times are define slightly differently

ln e = -k
1/k =

1/k = time scale for the reaction

Pseudo first order rate constants

A. The reaction of benzyl chloride to produce benzyl

alcohol water reacts with benzyl chloride

CH2 -Cl + H2O CH2-OH + H+ + Cl-

5
d[benz-Cl]/dt= -k [benz-Cl] [H2O]
k here is a second order rate const. in L mol-1sec-1

If we assume that the reaction is run in dilute

solutions as we could say that the [H2O] is constant

kpseudo = k[H2O]

d[benz-Cl]/dt= -kpseudo [benz-Cl]

B. Consider the reaction of methyl mercaptan in

water to produce dimethyl disulfide

2CH3 SH + O2 ----> H3 C-S-S-CH3

d[CH3 SH]/dt = k [CH3 SH]2 [O2]1/2

if we assume that O2 is constant

d[CH3 SH]/dt = kpseudo [CH3 SH]2

6
 For the special case of [A] reacting with [A]

A + A products

Since A is reacting with A

d[ A ] d[ A ]
dt
k [ A ]2 and [ A ]2
kdt

1 At
Ao
k t
[ A]

1 1
k t
[ A] t [ A] o

for this type of simple second order reaction, plot of 1/[A]t

vs. t gives a straight line with a slope of...??? and an
intercept of....?

the half-life is when [A]t = [A]o

1
k t1 / 2
[A]o

7
 More on second order reactions

if A + B----> products
and x is the amount of A and B reacted

the differential equation that describes a second

order rate law for the change in x with respect to time

dx/dt = - k[A] [B]

or
dx/dt = - k [Ao-x] [Bo-x]
1 x dx dx t

[ A o ] [Bo ] 0
(
[ A o ] x [Bo ] x
)k dt
0

this has an exact solution

1 [B ]( [ A o ] x )
ln o kt
[ A o ][B o ] [ A o ]( [B o ] x )

so if we measure the amount reacted, x, over time and

plot the left side of the equation vs time, the rate
constant, k can be measured

Rate Constants and Temperature

1850 - Wilhelmy related rate constant to temperature

8
1862 - Bertholet proposed k = A eDT

1889 - Arrhenius showed that the rate constant

increases exponentially with 1/temp.

lnK c U
1884 - vant Hoff Equation
T p RT 2

where
Kc= concentration equilibrium constant
U = standard internal energy change
and
Kc = k1/k-1

so

d ln k1 d ln k 1 U

dT dT RT 2

d ln k1 d ln k 1 U

dT dT RT 2

vant Hoff proposed two energy factors, so that

U = E1 - E-1
9
 It follows that: ln k1 = - E1/RT +const

or k1 = A e-E /RT (Arrhenius Equation)

1

There are other equations relating temp and rate

constants

1898 vant Hoff rate equation usually give very good

empirical fits
2
k AT m e (B DT )/ T

The Arrhenius equation is most widely used because it

provides insight into how reactions proceed

k1 = A e-Ea/RT ln k1 = ln A - Ea/RT

(see Table 12.2 page 349- old book) effect of temp on

rate constants (new book does not have this table)

krate (Ti/T2) = eEa (1/T2-1/T1)/R

krate relative to 25oC x 100 (%)

Ea 10oC 20oC 30oC Avg

10
kJ/mol increase
in krate
40 42 76 130 1.8
50 34 71 139 2.0
60 28 43 149 2.3

Theory of Arrhenius

11
 Consider the reaction of B +C ---> D + E

dB/dt = -k [B] [C]

to react B and C have to collide, and the rate should

depend

1. on the frequency of encounters of B and C which is

proportional to the conc. of B and C and how fast B
and C move (diffuse) toward each other.

2. the orientation of B and C

3. the fraction of the collisions that will have sufficient

energy to break the bonds of B and C.

The fraction of reaction species with an energy greater

than the activation energy is given by the Botlzmann
distribution of energies
e-Ea/RT

hence in rate = A e-Ea/RT[B] [C]

the coef A must include frequency and orientation

factors
Activated Complex or transition state theory
12
the reaction of B + C ---> on its way to products goes
though an activated intermediate called [BC]

B + C ---> [BC]--> [D] + [E]

it is assumed that there is an equilibrium between
the reactants and the activated complex [B-C]

and that [B-C] decomposes to products with a
rate constant of
kT/h

where k = Boltzmann const

1.38 x10-23 J K-1
h= Plancks const,
1.63 x10-34 J/sec

k T/h assumes that the rate constant is directly

proportional to the vibrating frequency of the transition
state and the energy associated with this is
proportional to kT
E kT h

= kT/h
[BC] --> [D] + [E]

13
 rate = kT/h [BC]

since we said

B+C -->
<-- [B-C]

[BC]
K
[B][C]

substituting for [BC]* in: rate = kT/h [BC]

rate = kT/h K [B] [C]

The equilibrium const. is related to the free energy of

activation by

K= e-G/RT
and G = H-TS

14
 kT
rate eS /R e H /RT [B][[C]
h

kT
k eS /R e H /RT
h

for a bimolecular reaction H = Ea - RT

kT
k eS /R e1 e Ea /RT
h

this looks like k= A e-Ea / RT

the entropy term in A --> orientation probability

and temp in A may be related to the frequency of

encounters; # collisions ~ (RT)1/2

15
Composite Reactions
Simultaneous Reactions

A--> Y

A---> Z

Competition reactions

A + B --> Y

A + C --> Z

Opposing Reactions

A+ B Z

Consecutive reactions

A--> X--> Y-->Z

Feedback
A--> X--> Y---> Z

16
Consecutive Reactions

k1 k2
A ---> X---> Z

-d[A]/dt = k1 [A] [A] = [A]o e-k1t

+d[X]/dt = k1[A]

d[X]/dt = +k1[A] - k2[X]

d[X]/dt = +k1[A]oe-k1t +- k2[X]

solution

[X] =[A]ok1/(k2-k1) (e-k t- e-k t)

1 2

[Z] =[A]o/(k2-k1) [k1(1-e-k t) -k1(1- e-k t)

1 2

These types of expressions are cumbersome

17
 (Steady- state approximation)

The rate of change of the concentration of an

intermediate, to a good approximation, can be
set equal to zero whenever the intermediate is
formed slowly and disappears rapidly -D.L.
Chapman and L.K. Underhill, 1913

Use of the Steady-State Assumption

(Consecutive Reactions with an Opposing Reaction as

the 1st step)

Consider the reaction of OH radicals in the

atmosphere with SO2 to form sulfuric acid
particles.
k1
OH + SO2 HOSO2
k-1

k3
HOSO2 + M ---> HOSO2 + M

for the rate of formation of HOSO2, we would write

d [HOSO2]/dt = +k1[OH][SO2]
18
for the loss we have
-k-1[HOSO2]
and
-k3[HOSO2]

so the total rate expression is

d [HOSO2]/dt = +k1[OH][SO2]
-k-1 [HOSO2] -k3[HOSO2]

at steady state d[HOSO2]/dt = zero

0=+k1[OH][SO2] -k-1[HOSO2] -k3[HOSO2]

k [OH][SO 2 ]
[HOSO2 ] 1
k 1 k 3

for the formation of product HOSO2

HOSO2 + M ---> HOSO2 + M

19
 d[HOSO2]/dt = +k3[HOSO2]

Substituting [HOSO2]

[HOSO 2 ] k1k 3[ OH][ SO 2 ]

dt k 1 k 3

20
In the atmosphere the formation of ozone can be
represented as

h
NO2 -------> NO + O. k1= 0.4xTSR

M
O. + O2 ----> O3 k2 = fast,fast

O3 + NO -----> NO2 k3

a. derive a steady state relationship for O3 as a function

of NO2, NO, k1 and k3; assume that dNO2/dt is at ss..
b. calculate the equilibrium ozone for the following
conditions

time 7:00 9:00 12:00 15:00

NO (ppm) 0.1 0.05 0.03 0.005

NO2 (ppm) 0.03 0.14 0.15 0.10
Temp (oC) 25 27 35 34
TSR(cal cm-2min-1) 0.05 0.2 0.5 0.3

plot your results for NO, NO2, and O3 and if this was a
real atmosphere explain.

21
Rate determining steps

k1 k3
A + B X Z
k-1

[HOSO 2 ] k1k 3[ OH][ SO 2 ]

dt k 1 k 3

[ Z] k1k 3[ A][B]

dt k 1 k 3

if k3 >> k1

[ Z]
k1[ A] [B]
dt

22
 The Hammett Equation and rates constants

In 1940 Hammett recognized for substituted benzoic

acids the effects of substituent groups on the
dissociation of the acid group
COOH
COO-

+H+

R
R

Go= GoH + Goi

Effect on the free energy change from dissociation could

be represented as the sum of the free energy change by
the unsubstituted benzoic acid and the contributions from
the various R groups.

we know that

Go = -2.303 RT log Ka
and
GoH = -2.303 RT log KaH
Goi = -2.303 RTi

23
-2.303 RT log Ka=-2.303 RT log KaH +-2.303 RTi

log (Ka / KaH )= i

when considering other compound classes, like phenyl

acetic acids the values developed for benzoic acid can
be used
log (Ka / KaH) = i

Figure 8.7 page 174

24
if an aromatic reaction is going through a transition
state

B + C ---> [BC]--> [D] + [E]

we said that the rate

rate = (kT/h) K [B] [C]

the rate constant is (kT/h) K

log krate= log (kT/h)+ log K

since -2.303 RT log K= Go

Using the Hammett argument that

Go= GoH + Goi

show that
log(krate) = log krateH + m,p

or log(krate/krateH) = m,p

25
Figure 12.2 page 354 (old book) new book
does not have this figure

Different rates are obtained in different solvents, so

reaction rates are not directly applicable to water if in
another solvent

26
The Taft Relationship

Attempts to extend Hammett type LFERs to aliphatic

compounds.

G= Gref + Gi,electronic+Gi,steric
k
log * * E s
k ref

= polar effects Es= steric effects

and are fitting parameters to a reference system

Taft chose the hydrolysis of carboxylic acid ester system

because he could use different R groups with different
steric and inductive effects

By varying R1 but keeping R2, solvent and temp.

constant, Taft proposed that the steric effects of R1
as compared to a methyl group and can be derived

27
directly from the rate constant kA for the acid-
catalyzed hydrolysis reaction.

Es = log (ka/ kA, ref)

This implies that the acid-catalyzed reaction

compared to the base catalyzed reaction does not
have inductive effects (when we look at this we will
see why in about two lectures).

To determine inductive effects (*)the reaction is run

under a basic catalyzed regime and when both
inductive and steric effects are operative.

* = log (kB/kB,ref) log (ka/ kA, ref )

In the literature, you will sometimes see

* = * /2.48 ,to put it on the same scale as the
Hammett values.
The direction and tends of * values, is similar to
Hammett values; ie withdrawing groups (Fl, Cl,
NO2) are positive and donating slightly positive or
negative (C2H5)

28
page 356 Table 12.4

29