Kinetics &

Stoichiometry
Steve Chapra

Civil and Environmental Engineering

Tufts University

19 June 2012

KINETICS &
STOICHIOMETRY
! Kinetics
! Zero & First-order reactions
! Temperature effects

! Stoichiometry

MASS-BALANCE FOR
WELL-MIXED LAKE
Qc

W
dc
V
dt

kVc

vAc
dc
V
dt
accumulation

= W-

Qc -

kVc -

vAc

= load - outflow - reaction - settling

1 teaspoon of sugar in a
covered bathtub
Sugar 20 ppm
20

csugar
0

t, days
0

10

15

20

SIMPLE KINETICS
Reversible reaction (equilibrium chemistry)

c C + dD
aA + bB
Irreversible reaction (non-equilibrium chemistry)

aA + bB c C + d D
Decomposition of organic matter (glucose) in water

C6 H12 O6 + 6O2
SUGAR + OXYGEN

6CO2 + 6H2 O
CARBON
+ WATER
DIOXIDE

RATE EXPERIMENT
c0

c1

c2

c3

t=0

t=1

t=2

t=3

time
concentration

0
c1

1
c2

2
c3

3
c4

rate
t

REACTION MODEL
c
c
Mass balance:

end products

dc
n
=
-
k c
dt
reaction rate

reaction order

REACTION ORDER
Zero-order reaction (n = 0)

dc
=
-
k
dt
where k = zero-order reaction rate [(mg/L)/d]

First-order reaction (n = 1)

dc
=-kc
dt
where

= first-order reaction rate [/d = per day]

ZERO-ORDER REACTION
dc
=
-
k
dt

c
c0

where c = c0 at t = 0,

c = c0 - kt
0

FIRST-ORDER REACTIONS
-kt
c = c0e
c
c0

0.5c0
0.25c0
0.125c0
t

FIRST-ORDER REACTION
ln c
ln c0

dc
= - kc
dt
where c = c0 at t = 0

c = c0 e

-k

- kt

ln c = - kt + ln c0

c0 = e

ln c0

THE MEANING OF A
FIRST-ORDER RATE COEFFICIENT
If its magnitude is less than 0.5, k can be
interpreted as the fraction of the pollutant that
is lost per unit time.
0.25/d

25%/d

0.1/yr

10%/yr

2.4/d

240%/d ???

change units so < 0.5

2.4

d
= 0.1/hr
d 24 hr

10%/hr

Where does the 0.5 come from?

MACLAURIN SERIES APPROXIMATION
OF EXPONENTIAL FUNCTION

e -x
e-x

x3
=1- x +
+
2! 3!
1- x
First-order Approximation
x2

Approximation
breaks down

e- x

1- x
0
0

0.5

1.5

TEMPERATURE EFFECTS
c

T = 10oC
T = 20oC
T = 30oC

TEMPERATURE EFFECTS
-E

Arrhenius equation:
-E

k(Ta2)
k(Ta1)

relatively
constant

Ae

RTa2
a
-E

Ae

RTa
=
k (Ta ) Ae

E(Ta2 Ta1)

=e

RTa1
a

RTa2Ta1

=e

E
RTa2Ta1

E
(Ta2 Ta1)
RTa2Ta1

TEMPERATURE EFFECTS
T2 T1
k(T2)
=
k(T1)
Reference temperature
Chemical engineering: 25oC
Environmental engineering: 20oC*
*Because average river T in north temperate
zone in summer 20oC

k(T) = k(20)

T 20

Q10: Used widely by biologists

! How much the rate changes per 10 oC rise in
temperature

Q10

k1
=
k2

10/(T2 - T1)

k(20)
Q10 =
k(10)
k(20) = k(10) Q10
Q10 = 10

= Q 0.1

Typical water-quality processes

Q10

1.024
1.047
1.066
1.07
1.08

1.27
1.58
1.89
2
2.16

k(T)
k(20)

Reaction
Oxygen gas transfer
BOD decomposition
Phytoplankton growth
Biological rule of thumb
Sediment oxygen demand
= 1.1

= 1.08
= 1.07

3
2

biotic

= 1.047
gas
= 1.024 transfer
=1

1
0
0

10

20

T(oC)

30

STOICHIOMETRY

Crude representation of decomposition of

organic matter:

C6 H12 O6 + 6O2 6CO2 + 6H2 O

More complete representation of decomposition of
organic matter:

C106H263O110N16P +106O2 +14H+

106CO2 + 16NH4+ + HPO42- + 106H2O
But that's not the end of it!

NH4+ + 2O2 2H+ + H2O + NO3-

WHAT QUESTIONS CAN WE ANSWER?

For example:
If 1 mgC/L of organic matter is decomposed,
how much ammonia is released expressed as
mgN/L?
C106H263O110N16P +107O2 +14H+ 106CO2 + 16NH4+ + HPO42- + 106H2O

Atomic weights:
mgC
1 L 1

16 gC/moleC

14 gN/moleN

mgN
gC 16 molesNH4 14 gN/molesNH4
= 0.176

L
m3
106 molesC 12 gC/molesC

Question: How much oxygen is consumed?