ACEE 219

E i
Environmental
t l Chemistry
Ch i t

Week
W k2
March 9, 2010
Innovation Hall 127
ACEE 219 Spring 2010 HDP 1
 Lecture of the Last Week

1. Chemistry gives a foundation for understanding

environmental engineering
g gp processes.
2. Water molecule is a dipole and forms hydrogen
bonds with electronegative
g atoms,, which g
gives
water anomalous fluid.
3. Human activities affect water compositions
p in rain,,
river, groundwater, and sea.
4. Mass, molar, and normal concentrations.

ACEE 219 Spring 2010 HDP 2

 CHAPTER 2.

CHEMICAL KINETICS

ACEE 219 Spring 2010 HDP 3

 What is Kinetics?
• Chemical
Ch i l kinetics
ki ti is i th
the study
t d off rates
t off chemical
h i l processes.
• Chemical kinetics deals with the experimental determination of reaction
rates from which rate laws and rate constants are derived.

SLOW!!

FAST!!

http://a espncdn com/photo/2008/0523/rpm i indy500 580 jpg

http://a.espncdn.com/photo/2008/0523/rpm_i_indy500_580.jpg

ACEE 219 Spring 2010 HDP 4

Collisions of Reacting Species
Reactant particles must collide for a reaction to occur, but only a
certain fraction of the total collisions have the energy to connect
effectively and cause the reactants to transform into products. This is
because only yapportion of the molecules have enough g energygy and
the right orientation (or "angle") at the moment of impact to break
any existing bonds and form new ones. (Wikipedia)

http://upload wikimedia org/wikipedia/commons/4/41/Molecular collisions jpg

http://upload.wikimedia.org/wikipedia/commons/4/41/Molecular-collisions.jpg

ACEE 219 Spring 2010 HDP 5

Expressing the Reaction Rates
reactants products

A + 2B → C + 2D

d[A] 1 d[B] d[C] 1 d[D]

• Reaction Rate = = =- =-
dt 2 dt dt 2 dt
= -k[A]a[B]b[C]c[D]d
where,
[A], [B], [C], [D] : molar concentrations for A, B, C, and D, respectively
a,, b,, c,, d: constants
k: reaction rate constant

• Reaction Order = a+b+c+d

ACEE 219 Spring 2010 HDP 6

 Example 2
2--1
NH3 + HOCl → NH2Cl + H2O
d[HOCl]
• Reaction Rate = = −k[HOCl][NH3 ]
dt
k 5 1 x10
k=5.1 106 liter/mole/sec
lit / l /
(a) What is the overall reaction order? 2

(b) What % decrease in reaction rate occurs if the concentration of

each reactant is reduced by 50%?
initial reaction rate = k[HOCl][NH
[ ][ 3]
new reaction rate = k0.5[HOCl]0.5[NH3] = 0.25 initial reaction rate

(c) Determine k when unit is changed to mg/L.

d[HOCl]
= −k[HOCl][NH3 ] k’=k/(17x103) = 300 liter/mg/sec
dt
(52 46 × 10 (HOCl)
d 52.46 3
) ( )(
= −k 52.46 × 10 3 (HOCl) 17 × 10 3 (NH3 ) )
dt
ACEE 219 Spring 2010 HDP Snoeyink & Jenkins Example 2-2 7
 Zero Order Reaction
A → products
d[A]
• Reaction Rate = = -k[A]n = -k[A]0 = -k
dt
d[A] = −kdt

[A] t
∫
[A]0
d[A] = −k ∫ dt
0

[A] = [A]0 - kt

ACEE 219 Spring 2010 HDP 8

 Zero Order Reaction,
Reaction Cont’d
Cont d
A → products
d t

[[A]] = [[A]]0 - kt
Intercept = [A]0

[A]

Slope = -k

ACEE 219 Spring 2010 HDP 9

 1st Order Reaction
A → products
d[A]
• Reaction Rate = = -k[A]n = -k[A]1 = -k[A]
dt
d[A]
= −kdt
[A]
[A] d[A] t
∫[A]0 [A] = −k ∫0 dt

ln[A] = ln[A]0 - kt

ACEE 219 Spring 2010 HDP 10

 1st Order Reaction,
Reaction Cont
Cont’d
d
A → products
d t
ln[A] = ln[A]0 - kt
Intercept = ln[A]0

ln[A]

Slope = -k

ACEE 219 Spring 2010 HDP 11

 2nd Order Reaction
A → products
d[A]
• Reaction Rate = = -k[A]2 = -k[A]2 = -k[A]2
dt
d[A]
2
= −kdt
[A]
[A] d[A] t
∫[A]0 [A]2 = −k ∫0 dt

1 1
= + kt
[[A]] [ ]0
[A]

ACEE 219 Spring 2010 HDP 12

 2nd Order Reaction,
Reaction Cont
Cont’d
d
A → products
d t

1 1
= + kt
[A] [A]0

1
[A]
Slope = k

1
Intercept =
[A]0

ACEE 219 Spring 2010 HDP 13

 Half Life
• Half life ((t1/2)): time for 50% of the initial concentration to react

Zero Order First Order Second Order

[ A] = [ A]0 − kt 1 1
l [ A] = ln[
ln[ l [ A]0 − kt = + kt
k
[ A] [ A]0
0.5[ A]0 = [ A]0 − kt1/ 2 ln(0.5[ A]0 ) = ln([ A]0 ) − kt1/ 2
1 1
kt1/ 2 = 0.5[ A]0 kt1/ 2 = ln
l 2 = + kt1/ 2
0.5[ A]0 [ A]0
0.5 0.693
t1/ 2 = [ A]0 t1/ 2 = 1
k k kt1/ 2 =
[ A]0
1
t1/ 2 =
k[ A]0
ACEE 219 Spring 2010 HDP 14
 Example 2
2--2
Determine the rate constant and order of this reaction,,
2H2O2 → 2H2O + O2

Time, min [H2O2] ln[H2O2] 1/[H2O2]

0 0.0320 -3.44 31.25
10 0.0230 -3.77 43.48
20 0.0180 -4.02 55.56
30 0 0130
0.0130 -4.34
4 34 76 92
76.92
40 0.0099 -4.62 101.01
50 0.0071 -4.95 140.85

Snoeyink & Jenkins Example 2-2

ACEE 219 Spring 2010 HDP 15

 Example 2
2--2
2, Cont’d
Cont d
0.0350 -3.00 160.00

0.0300 140.00
0 order -3.50 1st order 2nd order
120.00
0.0250
-4.00
100.00

1/[H2O2] (M-1)
0.0200

ln [H2O2]
H2O2 (M)

-4.50 80.00
0.0150 Sl
Slope = -kk 60.00
0.0100
-5.00 = -0.029 min-1
40.00
-5.50
= -4.8x10-4 sec-1
0.0050 y = -0
0.029x
029x - 3.448
3 448 20 00
20.00

0.0000
R² = 0.998 0.00
-6.00
0 20 40 60 0 20 40 60 0 20 40 60
time (min) Time (min) Time (min)

1 1
[A] = [A]0 - kt ln[A] = ln[A]0 - kt = + kt
[A] [A]0

ACEE 219 Spring 2010 HDP 16

 Effect of Temperature
• Arrhenius equation:
the dependence of the rate constant k of chemical
reactions on the temperat
temperature
re T
( −E a /RT)
k = Ae
Ea
lnk = lnA −
RT
Where,
A: pre-exponential
pre exponential factor (unit depends on reaction nature)
Ea: activation energy (cal/mole, J/mole)
R: ideal gas constant (1.987 cal/mole.oK, 8.314 J/mole.oK)
T: absolute temperature (oK)

ACEE 219 Spring 2010 HDP 17

 Activation Energy
Activated complex

• Activation Energy: the energy

Ea that must be overcome in order
Reactants
for a chemical reaction to occur.
ergy
Ene

∆H
Products

Reaction Path

Ea: activation
ti ti energy for
f the
th forward
f d reaction
ti (cal/mole)
( l/ l )
∆H: enthalpy change for the forward reaction (cal/mole)

ACEE 219 Spring 2010 HDP 18

 Maxwell--Bolzmann Theory
Maxwell
The relation of the variation of the number of molecules
with an energy equal to or greater than a given energy
level to the absolute temperature

−E
( )
N = N0De RT
with statted energyy

N: # of molecules with energy equal to

# of molecules

or greater than E
N0: total # of molecules
D: constant
E: stipulated energy level (cal/mole)
R: gas constant (cal/mole.oK)
T: absolute temperature (oK)
E Energy

Only molecules with an energy level equal to or greater than E are capable of forming
the high energy-level transition complex

ACEE 219 Spring 2010 HDP 19

 Example 2
2--3
Determine the activation energy (Ea) for this reaction and
the value of the pre-exponential factor (A) assuming the
reactants concentrations were constant.

H2O2 + 2KI + 2H+ ↔ 2H2O + 2I2(aq) + 2K+

p , oC
Temperature, Rate Constant,, k
44.5 1.66 x 10-3
35.0 1.02 x 10-3
25 7
25.7 6 63 x 10-4
6.63
15.1 2.98 x 10-4
4.5 1.17 x 10-4
Unit of rate constant: liter/mole/sec
Snoeyink & Jenkins Example 2-3
ACEE 219 Spring 2010 HDP 20
 Example 2
2--3
3, Cont’d
Cont d
-6.0
60
⎛ Ea ⎞ 1
lnk 1/T -6.5
lnk = lnA − ⎜ ⎟ ⋅
-6.401
6 401 0 003148
0.003148 70
-7.0 ⎝R⎠ T
-6.888 0.003245 -7.5
slope

lnk
-7.319 0.003346
-88.00
-8.118 0.003469
y = -5819.6x + 12.007
-8.5
-9.053 0.003601 R² = 0.9901
-9.0 y-axis
y axis intercept
-9.5
0.00310 0.00320 0.00330 0.00340 0.00350 0.00360 0.00370

Y-axis intercept=lnA 1/T

12.007=lnA, A=1.64x105liter/mole/sec
Slope=-E
Slope Ea/R
Ea=-R x Slope=-1.99x(-5819.6)=11581cal/mole=11.6kcal/mole
ACEE 219 Spring 2010 HDP 21
 Estimating k2 @ T2
• If the value of activation energy (Ea) and the rate constant @ T1 (k1)
are known, we can determine the rate constant @ T2 (k2) as follow:
Ea
lnk 1 = lnA −
RT1
Ea
lnk 2 = lnA −
RT2
Ea Ea
lnk 2 − lnk 1 = − +
RT2 RT1
k2 Ea ⎛ 1 1 ⎞
ln = − ⎜⎜ − ⎟⎟
k1 R ⎝ T2 T1 ⎠
⎡ Ea ⎛ 1 1 ⎞⎤
k 2 = k 1exp ⎢− ⎜⎜ − ⎟⎟⎥
⎣ R ⎝ T2 T1 ⎠⎦

ACEE 219 Spring 2010 HDP 22

 Catalysis
• Catalyst: A substance that increase the rate of reaction
• Mechanism: modifying reaction pathway or nature of activated
complex → lower activation energy

Activated complex

Ea,11: activation energy without catalyst

Reactants Ea,2 : activation energy with catalyst

Enerrgy

∆H
Products

Reaction Path

ACEE 219 Spring 2010 HDP 23

 Biological Reaction
• Enzyme (biological catalyst) mediated reaction

A →B+C

B C

http://i183.photobucket.com/albums/x319/coachstevetoth/Enzymecomplex2400x300.jpg

ACEE 219 Spring 2010 HDP 24

Biological Reaction,
Reaction Cont
Cont’d
d
saccharase
C12H22O11 + H2O → C6H12O6 + C6H12O6
Sucrose glucose fructose

35

30

25
In itial vvelo city
(m g /liteer/m in )

20
Vmax [S]
15 V=
10 K m + [S]
5

0
0 0.05 0.1 0.15 0.2 0.25 0.3
Sucrose conc. (mole/liter)

ACEE 219 Spring 2010 HDP 25

 Biological Reaction,
Reaction Cont
Cont’d
d
⎯⎯→
kk1
1

S+E ES ⎯⎯→
k3
P+E
←⎯⎯
k2

If the ES formation P is negligible (this is only hold for the initial stage),
the reaction rate is
dP
= k3 [ ES ]
dt
Also, @ steady-state:
Al t d t t
rate of ES formation = rate of ES removal

k1[ E ][ S ] + k 4 [ E ][ P ] = k 2 [ ES
S ] + k3[ ES
S]
[ ES ] [ ES ]
k1[ S ] + k 4 [ P ] = k 2 + k3
[E] [E]
ACEE 219 Spring 2010 HDP 26
 Biological Reaction,
Reaction Cont
Cont’d
d
[E] ( k 2 + k3 )
=
[ ES ] k1[ S ] + k 4 [ P]

k 4 [ ES ] << k1[ S ] [ E ]t [ S ]
[ ES ] =
[ E ]t = [ E ] + [ ES ] [(k 2 + k3 ) / k1 ] + [ S ]

dP k3 [ E ]t [ S ] Vmax [ S ]
= k3 [ ES ] = =
dt [(k 2 + k3 ) / k1 ] + [ S ] K m + [ S ]
where,
Vmax: maximum rate of reaction
Km: Michaelis-Menten
Michaelis Menten constant

ACEE 219 Spring 2010 HDP 27

 Microbial Growth
M
Monod
d Equation
E ti
Growth rate μ max [ S ]
μ=
K S + [S
[S ]

μ, growth rate, (dX/dt)/X

μmax, maximum growth rate
X: microbial mass
Conc of substrate
Conc. S: substrate concentration
Ks: half saturation constant

• The equation for microbial growth is similar to

the Michaelis and Menten Equation
• Microorganisms are “bags full of enzymes”

ACEE 219 Spring 2010 HDP 28

 Lecture for the Next Week

1. Chemical equilibrium

2. Gibbs free energy

3. Temperature dependence on chemical equilibrium

4. Chemical activity

ACEE 219 Spring 2010 HDP 29