Updated: 30 January 2019 Print version

Lecture #5
Kinetics and Thermodynamics: Fundamentals
of Kinetics and Analysis of Kinetic
Data
(Stumm & Morgan, Chapt.2 )
(pp.16-20; 69-81)
(Benjamin, 1.6)
David Reckhow CEE 680 #5 1
 Elementary Reactions
Starting out with some A
When reactant and B, we observe that E
and F are the end
molecules collide with
products
the right orientation A  B  C  slow
and energy level to form
new bonds D
fast
Many “observable” 2C  E
reactions are really fast
just combinations of ADC
elementary reactions F
2ABE
F
David Reckhow CEE 680 #5 2
 S&M: Fig. 2.11
Pg. 72

Cont.

 Elementar
y reactions
A single step in a
reaction
sequence
Involves 1 or 2
reactants and 1 or
2 products
Can be described by classical
chemical kinetics
David Reckhow CEE 680 #5 3
Kinetics
Examples
Fe+2 oxidation by O2
 almost instantaneous at high
pH
 quite slow at low pH
 high D.O. may help

Oxidation of organic material

Formation of solid phases
 Aluminum hydroxide
 Quartz sand

David Reckhow CEE 680 #5 4

 Kinetics
Base Hydrolysis of dichloromethane
(DCM)
 Forms chloromethanol (CM) and chloride

 Classic second order reaction (molecularity of

2)
 d[OH  d[CM ] d[Cl 
Rate  k[DCM ][OH  ]    
 ]
]
 First order in each reactant, second order dt
d[ DCM ]
dt
overall dt
dt
David Reckhow CEE 680 #5 5
Reaction Kinetics
Irreversible reaction
 is one in which the reactant(s) proceed to product(s), but
there is no significant backward reaction,
 In generalized for, irreversible reactions can be
represented as:

aA + bB  Products

i.e., the products do not recombine or change to form reactants in any

appreciable amount. An example of an irreversible reaction is hydrogen
and oxygen combining to form water in a combustion reaction. We do
not observe water spontaneously separating into hydrogen and oxygen.

David Reckhow CEE 680 #5 6

 Reaction Kinetics:
Reversibility
A reversible reaction
is one in which the reactant(s) proceed to product(s),

but the product(s) react at an appreciable rate to
reform reactant(s).
aA + bB  pP + qQ
Most reactions must be considered reversible

An example of a reversible biological reaction is the formation of adenosine

triphosphate (ATP) and adenosine diphosphate (ADP). All living organisms
use ATP (or a similar compound) to store energy. As the ATP is used it is
converted to ADP, the organism then uses food to reconvert the ADP to
ATP.
David Reckhow CEE 680 #5 7
Kinetic principles
Law of Mass Action
 For elementary
reactions

aA  bB   k

products a b
where,
rate  kC C
A B
CA = concentration of reactant species A, [moles/liter]
CB = concentration of reactant species B, [moles/liter]
a = stoichiometric coefficient of species A

b = stoichiometric coefficient of species B

k = rate constant, [units are dependent on a and b]
David Reckhow CEE 680 #5 8
Reaction

Kinetics (cont.)
Reactions of dc
order “n” in  kc n
reactant “c” dt
When n=0, we have a
simple zero- 90

Concentration
80
order reaction 70
60
c  co 
50
40
kt
30
20
Slope
dc 10 k  10mg / l /
 k min
0 20 60 80
dt 0 Time4(0mi
n)
David Reckhow CEE 680 #5 9
Reaction Kinetics (cont.)
When n=1, dc
 kc1
we have a
dt
simple first- 90
order 80
70
reaction
c  co e  kt
Concentration

60
This results in 50
an “exponential 40
decay” 30
20
10 k  0.032
0
min 1
0 20 40 60 80
Time
David Reckhow CEE 680 #5 (min) 10
Reaction Kinetics (cont.)
dc
 kc1
This equation dt
can be linearized 100

Concentration (log scale)

good for
assessment of “k” ln c  ln co  kt
from data
Slope
k  0.032 min 1
10
0 20 40 60 80
Time
(min)
David Reckhow CEE 680 #5 11
 dc
 kc 2
Reaction Kinetics dt
(cont.)
 When n=2, we have a simple second-order
reaction 90
This results 80
1
in an 70
c  co
Concentration

60
especially
wide range in 50 1 kco
rates
40
30
t
k  0.0015L / mg /
More typical 20 min
to have 2nd 10
order in each 0
of two 0 20 40 60 80
different Time
David Reckhow CEE 680 #5 12
Reaction Kinetics (cont.) dc
Again, the equation can be  kc 2
dt
linearized to estimate “k” from data
Time (min)
0 60 80
0.1
1 1
  2 20

ckt co 0.1 40
1/Concentration

0.0
8
Slope
0.0
6
k  0.0015L / mg /
min
David Reckhow 0.0 13
Comparison of Reaction Orders
Curvature as order changes:
2nd>1st>zero
90
80 Zero Order
70
First Order
Concentration

60
50 Second Order
40
30
20
10
0
0 20 40 60 80

David Reckhow CEE 680 #5

Time 14
 1 1
dc kc1 c 2
 
Reaction Kinetics dt
For most reactions, n=1 for each of two
(cont.)
different reactants, thus a second-order overall
reaction c2  Many of these will have
one reactant in great
excess
 These become “pseudo-
k  3.9x10 Lmg min
5 1 1
1st order in the limiting
reactant, as the reactant
in excess really doesn’t
c1 change in concentration

David Reckhow CEE 680 #5 15

 dc  kc1c1
1 2

Reaction Kinetics dt

(cont.)c1  c 1oe k t obs

Since C2 changes little
90 from its initial 820
80
70 k obs  kc2  3.9 x10 5 (820) itmg/L,
is more interesting to
focus on C1
Concentration

60 1
 0.032 C1 exhibits simple 1st
50
min order decay,
40
30 called pseudo-1st
20 order
10 The pseudo-1st order
0 rate constant is just
0 20 40 60 80 the “observed rate” or
kobs
Time
David Reckhow (min)
CEE 680 #5 16
Variable Kinetic
Order
dc
 kc n
Any reaction order, except n=1
dt
1 1
cn1    n
c 1kt
n1 o

1
c
1 t
o 1
n n1
c 1o

David Reckhow CEE 680 #5 17
Half-lives
Time required for initial concentration to drop
to half, i.e.., c=0.5co
For a zero order
reaction: 0.5co
c  co  kt 0.5co  co  t 12 
2 k
kt
For a first order
1
reaction: 1

1 1

c kt 0.5co  2 2
k
co e co e 0.693

David Reckhow CEE 680 #5 8
Reactions in Series
A k  B k  C k  D
1 2 3

k1=k2=k3=0.1 day-1

Fig. 2.9
Pg. 68

David Reckhow CEE 680 #5 19

Reversible reaction kinetics
kf
For a general reversible reaction:
aA + bB  pP +
qQ k b
And the rate law must consider both forward and reverse
reactions:
r A = k f aA bB - k b pP qQ
C C C C
where,
kf = forward rate constant, [units depend on a and b]
kb = backward rate constant, [units depend on a and b]
CP = concentration of product species P, [moles/liter]
CQ = concentration of product species Q, [moles/liter]
p = stoichiometric coefficient of species P
q = stoichiometric coefficient of species Q

David Reckhow CEE 680 #5 20

Reversible
Kinetic
1 st order
21

reactions
law dB
Fig. 2.10
dt
 k 1[ A]  k2
[B] Pg. 69
Eventually
the
reaction slows
and,
Reactant
concentrations
approach the
dB
equilibrium
 0  k 1[ A]  k2
dt
values
[B]
[B] k1  K eq

[ A] k 2
David Reckhow CEE 680 #5
 Temperature
Temperature
Effects
 Dependence
Chemist's Approach: Arrhenius
d (ln k) E
Equation Activation Pre-exponential
 energy
R
2 kT  Ae RT  EFactor
a / a

a a a

dTa T R = universal gas constant

k T  k 293 o
K
= 1.987 cal/oK/mole
e Ea (Ta 293)/ RTa Ta = absolute temp o
a ( K)
293
 Engineer's Approach:
 T 20 Or more generally where
k T  kT T
k T  k 20 C o
To is any “baseline”
To
C
temperature
Typical o
David Reckhow 22
values:
Determination of Ea and A
kT  Ae  E a /
Use Arrhenius a RTa

equation  Ea 1 

ln  ln A 
Take natural log of a
 a 
both sides kT  R  T
 Evaluate
slope and
intercept

David Reckhow CEE 680 #5 23

 
G

Catalysis 
A Catalyst enhances G reactants

rates by providing
alternative products

pathways with lower Reaction coordinate

activation energies
 It is not “consumed” in the
reaction
 Homogeneous

Acid/base catalysis


 Trace metal catalysis

 Heterogeneous
 Reactions mediated by microorganisms

(enzymes)on particle surfaces

 Reactions
 Engineered surface catalysis

 Catalytic converters, activated carbon

David Reckhow CEE 680 #5 24

Analysis of Rate Data
Integral Method
Least squares regression of linearized form
Differential Method
estimate instantaneous rate at known time
and reactant concentration
Initial rate Method
more rigorous, but slow
Method of Excess
only when 2 or more reactants are involved

David Reckhow CEE 680 #5 25

 Kinetic model for equilibrium
Consider a reaction The rates
as follows: are: rb  kb {C}
rf  k  {D}
f {A}{B}
And at equilibrium the
A+B=C+D
two are equal, rf=rb
Since all reactions are k f {A}{B}  kb {C}{D}
reversible, we have
We then define an
two possibilities
equilibrium constant (Keq)
A  B   kf

K eq  k  {C}
A B
C D  C 
bk
kb {D}
f
{A}
D
{B}
David Reckhow CEE 680 #5 26
 Kinetic model with moles
In terms of molar concentrations, the rates
are:
rb  kb C  C
 k f A A B  B
rf
D D

And at equilibrium the two are equal, rf=rb

k f A A B  B  kb C  C
Dequilibrium
And solving for the D constant
(Keq)
 C C D D  C D C
k 
K eq  D

kb A  A B B AB  A
f
B 
 
David Reckhow
 CEE 680 #5
 27
 To next lectur
e

David Reckhow CEE 680 #5 28