(Benjamin, 1.6) : Print Version
(Benjamin, 1.6) : Print Version
(Benjamin, 1.6) : 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 ADC
elementary reactions F
2ABE
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
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
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
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
Reaction Kinetics dt
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
cn1 n
c 1kt
n1 o
1
c
1 t
o 1
n n1
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
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
equation Ea 1
ln ln A
Take natural log of a
a
both sides kT R T
Evaluate
slope and
intercept
Catalysis
A Catalyst enhances G reactants
rates by providing
alternative products
Acid/base catalysis
Heterogeneous
Reactions mediated by microorganisms
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
k f A A B B kb C C
Dequilibrium
And solving for the D constant
(Keq)
C C D D C D C
k
K eq D
kb A A B B AB A
f
B
David Reckhow
CEE 680 #5
27
To next lectur
e