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
and B, we observe that E
 When reactant
and F are the end products
molecules collide with
the right orientation and A+ B → C + D slow
energy level to form new
bonds 2C → E fast
 Many “observable” A+ D → C + F fast
reactions are really just
combinations of
elementary reactions
2A + B → E + F

David Reckhow CEE 680 #5 2

 S&M: Fig. 2.11
Pg. 72

Cont.

 Elementary
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 [ DCM ] − d [OH ] d [CM ] d [Cl ]
Rate = k[ DCM ][OH ] = = = =
dt dt dt dt
 First order in each reactant, second order overall

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

→ products
aA + bB  k

where,
rate = kC Aa C Bb
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 order
“n” in reactant “c” dc = − kc n
dt
 When n=0, we have a
simple zero-order 90

Concentration
80
reaction 70
60
c = co − kt
50
40
30 Slope
20

dc 10 k = 10mg / l / min
= −k 0
0 20 Time40
(min) 60 80
dt
David Reckhow CEE 680 #5 9
Reaction Kinetics (cont.)
 When n=1, we dc
have a simple = − kc1
dt
first-order 90
reaction 80
70
− kt
 This results in
c = co e
Concentration

60
an “exponential 50
decay” 40
30
20
10 k = 0.032 min −1
0
0 20 40 60 80
Time (min)
David Reckhow CEE 680 #5 10
Reaction Kinetics (cont.)
dc
 This equation can
= − kc1
dt
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
Reaction Kinetics (cont.) dt
= − kc 2

 When n=2, we have a simple second-order

reaction 90
 This results in 80
1
an especially 70
c = co
Concentration

wide range in
rates
60
50 1 + kco t
40
 More typical to 30 k = 0.0015 L / mg / min
have 2nd order 20
in each of two 10
different 0
reactants 0 20 40 60 80

David Reckhow CEE 680 #5

Time (min) 12
Reaction Kinetics (cont.)
dc
 Again, the equation can be linearized = − kc 2
to estimate “k” from data dt
Time (min)
0 20 40 60 80
0.12
1 1
= + kt 0.1
1/Concentration

c co 0.08
0.06
Slope
0.04
k = 0.0015 L / mg / min
0.02
David Reckhow CEE 680 #5 0 13
Comparison of Reaction Orders
 Curvature as order changes: 2nd>1st>zero

90
80 Zero Order
70
Concentration

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

David Reckhow CEE 680 #5

Time (min) 14
 dc
= −kc1 c2
1 1

Reaction Kinetics (cont.) dt

 For most reactions, n=1 for each of two different
reactants, thus a second-order overall reaction
c2  Many of these will have
one reactant in great
excess
 These become “pseudo-
k = 3.9 x10 −5 Lmg −1 min −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
= − kc11c12
Reaction Kinetics (cont.) dt

− k obs t
c1 = c1o e  Since C2 changes little
90 from its initial 820 mg/L,
80 −5 it is more interesting to
kobs ≈ kc2 = 3.9 x10 (820)
70 focus on C1
Concentration

60 ≈ 0.032 min −1  C1 exhibits simple 1st

50
40 order decay, called
30 pseudo-1st order
20  The pseudo-1st order
10 rate constant is just the
0 “observed rate” or kobs
0 20 40 60 80
Time (min)
David Reckhow CEE 680 #5 16
Variable Kinetic Order
 Any reaction order, except n=1

dc
= −kc n
dt
+ (n − 1)kt
1 1
n −1
= n −1
c c
o

1
c = co
[1 + (n − 1)kc t ] ( n −1
o
1
n −1)

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 − kt 1
t 12 =
2 k
 For a first order reaction:

ln(2)
− kt
− kt 1 t 12 =
c = co e 0.5co = co e 2
k
0.693
=
David Reckhow CEE 680 #5
k 18
Reactions in Series
A → B → C → D
k1 k2 k3

k1=k2=k3=0.1 day-1

Fig. 2.9
Pg. 68

David Reckhow CEE 680 #5 19

Reversible reaction kinetics
For a general reversible reaction: kf
aA + bB ↔ pP + qQ
kb
And the rate law must consider both forward and reverse reactions:
r A = k f CaA CbB - k b CpP CqQ
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 1 st order reactions
 Kinetic law
dB Fig. 2.10
= k1[ A] − k 2 [ B]
dt Pg. 69
 Eventually the
reaction slows and,
 Reactant
concentrations
approach the
equilibrium values
dB
= 0 = k1[ A] − k 2 [ B ]
dt
[ B] k1
= ≡ K eq
[ A] k 2
David Reckhow CEE 680 #5 21
 Temperature Effects
Temperature Dependence
• Chemist's Approach: Arrhenius Equation
Activation energy Pre-exponential Factor
d (ln k ) Ea
= kTa = Ae − Ea / RTa
dTa RTa2
R = universal gas constant
E a ( Ta − 293)/ RTa 293
k Ta = k 293o K e = 1.987 cal/oK/mole
Ta = absolute temp (oK)

• Engineer's Approach:

kT = kTo θ T −To
Or more generally where
k T = k 20o Cθ T − 20o C
To is any “baseline”
temperature
Typical values:
David Reckhow θ=1.02 to 1.15 22
Determination of Ea and A
− Ea / RTa
kTa = Ae
 Use Arrhenius equation
 Take natural log of both  Ea  1 
sides ln kTa = ln A −   
 R  Ta 
 Evaluate slope
and intercept

David Reckhow CEE 680 #5 23

 ∆
GΠ

Catalysis ∆
G
 A Catalyst enhances rates reactants

by providing alternative
pathways with lower activation products

energies Reaction coordinate

 It is not “consumed” in the reaction
 Homogeneous
 Acid/base catalysis
 Trace metal catalysis
 Heterogeneous
 Reactions on particle surfaces
 Reactions mediated by microorganisms (enzymes)
 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 as  The rates are:
follows: rf = k f { A}{B} rb = kb {C}{D}
 And at equilibrium the two
A+B=C+D
are equal, rf=rb
 Since all reactions are k f { A}{B} = kb {C}{D}
reversible, we have two
 We then define an
possibilities
equilibrium constant (Keq)
A + B → C + D
kf
kf {C}{D}
A + B ←
kb
C+D K eq ≡ =
kb { A}{B}

David Reckhow CEE 680 #5 26

 Kinetic model with moles
 In terms of molar concentrations, the rates are:

rf = k f [A]γ A [B ]γ B rb = kb [C ]γ C [D ]γ D

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

k f [A]γ A [B ]γ B = kb [C ]γ C [D ]γ D

 And solving for the equilibrium constant (Keq)

K eq ≡
kf
=
[C ]γ C [D ]γ D [C ][D ]  γ C γ D 
=  
kb [A]γ A [B]γ B [A][B]  γ Aγ B 
David Reckhow CEE 680 #5 27
  To next lecture

David Reckhow CEE 680 #5 28