1.

Reaction kinetics

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 Why do we need to know
reaction kinetics?

 How long does a contaminant persist in

the environment?
 Design using reaction kinetics

2
 You need to know
1. Elementary reaction vs. non-elementary
reaction
2. Determine order of reaction based on
experimental data
3. Relationship between concentration of
reactants and reaction rate
4. Reaction in series, parallel and reversible

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 Reaction (Chapter 9)
 Elementary and non-elementary (Clark book
9.6)
 Zero order reaction (Clark book 9.5)
 First order reaction (Clark book 9.2)
 Second order reaction (Clark book 9.3)
 Pseudo-first order reaction (Clark book 9.4)
 Reversible reaction (Clark book 9.8)
 Effect of temperature on reaction rate (Clark
book 9.10)
 Group 1 presents paper on 8/31/2016
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 Elementary Reactions
aA + bB ® pP
reactants products
𝑑𝐶𝐴 𝑥 𝑦
𝑟𝐴 = = −𝑘𝐴 𝐶𝐴 𝐶𝐵
𝑑𝑡
rA=reaction rate kA=reaction rate constant
If x=a, and y=b Stoichiometry suggests kinetics
𝑑𝐶𝐴
𝑟𝐴 = = −𝑘𝐴 𝐶𝐴𝑎 𝐶𝐵𝑏
𝑑𝑡
Order=a+b
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Which of the following is NOT correct for this
elementary reaction aA+bB→pP
dC A
A) rA    ka C A CB ;
a b

dt
dCB
B) rB    kb C A a C B b ;
dt
dCP
C ) rP    k p C A a CB b
dt
1 1 1
D)  rA  rB   rP
a b p
k a kb k p
E)  
a b p
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For an elementary reaction aA+bB→pP:
dC A
rA = = -kaC AaC Bb ;
dt
dC B
rB = = -kbC AaC Bb ;
dt
dC P
rP = = +k pC AaC Bb
dt
1 1 1
rA = rB = - rP
a b p
k a kb k p
= =
a b p 7
Zero order reaction kinetics A→B

Zero order reaction rate does not depend on

the reactant concentration
dC A
rA = = -k;
dt
dC B
rB = = +k;
dt

When we plot C A vs. time,what is the intercept?

and what is the slope?

Is zero-order reaction elementary?

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 Examples of first order elementary
reactions of environmental interest
• Dissociation of hydrogen sulfide in solution (H2S
produced by bacteria)
H2S → H++HS-
• Dissociation of bicarbonate into CO2 and OH-
HCO3- → CO2+OH-
• Hydrolysis of alum for coagulation/flocculation
Al(H2O)63+ → Al(H2O)5OH+ + H+

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First order elementary reaction A→B
dC A dC B
rA = = -kC A ; rB = = +kC A
dt dt

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For a first order elementary reaction A→B,
what is the conversion at time t?

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0 order reaction: 1st order reaction:
dC A dC A
rA = = -kC A ; rA = = -kC A ;
dt dt
dC B dC B
rB = = +kC A rB = = +kC A
dt dt

Unit of k for first order reaction?

Unit of k for zero order reaction?
If we plot lnC A vs. time for first order reaction,
what is the intercept and slope?

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First order reaction kinetics

8.00 y = -0.100x + 4.500

4.00 2
R = 0.999
ln[A]

0.00
-4.00
-8.00
0 40 80 120
time (min)

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 Second Order Elementary Reaction

• H+ + HS- → H2S
• CO2 + OH- → HCO3-
• NO + O3→NO2+O2
• The forward reaction is second order
• The reverse reaction may be not

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Which of the following is NOT correct for this
second order elementary reaction
A + B →P
dC A
A) rA = = -kC AC B
dt
dC B
B) rB = = -kC AC B
dt
C) rP = -kC AC B
D) To find an expression for reaction rate,
dC A
solve equation rA = = -kC AC B with
dt
t = 0 C A = C A0and C B = C B0
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Solution for second order reaction kinetics

When CA0=CB0 Unit of k?

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 Solution for second order reaction kinetics

When CA0≠CB0

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 You are usually given the design goal:
e.g. reduce concentration of certain
contaminant by 80%
C B0
1-
CA C A0
=
C A0
1-
C B0
C A0
{exp éë - ( C A0 ) }
- C B0 kt ùû

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 Second-order kinetics
C B0
1-
CA C A0
=
C A0
1-
C B0
C A0
{exp éë - ( C A0 ) }
- C B0 kt ùû [B0]/[A0]= 0.1 - 100
CA/CA0
0.1

0.5

10-100 First-order
B0>>A0
0.9
1.1

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 Pseudo-first order reaction kinetics
if CA0<<CB0

C B0
1-
CA C A0
=
C A0
1-
C B0
C A0
{
exp éë - ( C A0 - CB0 ) kt ùû }

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Derive a concentration rate equation for
a pseudo-first order reaction

A. C A  C A,0 exp(ktCB 0 )
B. ln C A  ln C A0  CB 0 kt
C.None of the above

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 Pseudo-first order reaction
CA
 exp(CB 0 kt )
C A0
C A  C A,0 exp(ktCB 0 )
ln C A  ln C A0  CB 0 kt
Plot ln C A as a function of time to find
intercept ln C A0 and slope CB 0 k

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 Summary
(do at home, useful for review and exams)
Reaction Rate expression
order
Zero

First

Second

Pseudo-first

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 Consider the following elementary reaction:
B+2D→3T Which of the following is NOT
correct

A) rB  k B CB CD 2 ;
B) rD  k D CB CD 2 ;
C) rT  kT CB CD 2 ;
D) 1 mol of B reacts with 2 mol of D to form 3 mol of T
E) The rate of B dissappearance is half of the rate of D dissapperance
and 1/3 rate of T formation
1 1 1 1
rB  rD   rT or k B  k D  kT
2 3 2 3

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For the complex elementary reaction with
stoichiometric A +3B →2R + S
and with second-order rate expression
–rA=k1CACB

1) Are the reaction rates related as follows:

rA=rB=rR?

2) If their rates are not so related, then how are they

related? Remember to account for the signs, + or –
(Do at home)

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Consider the following complex elementary reaction
with stoichiometry A + B →2R + S and with second
order rate expression –rA=kA/BCACB

How are the rate rA, rB and rR related?

Do at home

A. rA = rB = rR
B. 2rA = 2rB = -rR

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Consider the following elementary reaction with
stoichiometry A + B →2R and with second order
rate expression –rA=kA/BCACB
Write the rate expression for R. (Do at home)

A. rR=kRCACB
B. rR=-kRCACB
C. Not enough information

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 What can we do next?
Given a set of experimental data, we can
determine the order of the reaction:
• Plot CA vs t in different form of CA;
• Examine the correlation coefficient of each
order;
• Determine the order with the smallest error.

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A reaction has the stoichiometric
equation A + B →2R. What is the order
of reaction?

A. First order
B. Second order
C. Cannot determine with this given
information

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On doubling the concentration of
reactant A, the rate of reaction triples.
Find the reaction rate order?

A. n=1
B. n=2
C. n=1.585
D. None of the above

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 Reversible Reaction
𝐶𝐵,𝑒𝑞 𝑘2
¾¾
A¬ ¾ ®B
¾
k1
= = 𝐾𝑒𝑞
k 2 𝐶𝐴,𝑒𝑞 𝑘1
dimensionless concentration
1.0

0.8 CB/CA0
0.6 Equilibrium
concentrations
0.4

0.2 CA/CA0
t
1 2 3 4 5 6

Do at home: Expression of CA(t)

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 Reactions in Series
k1 k2
first order elementary reaction A ® B® C
dC A
first reaction for A rA = = -k1C A
dt
dC B
first reaction for B formation rB = = +k1C A
dt
dC B
second reaction for B dissapearing rB = = -k2C B
dt
dC B
both reactions for B rB = = +k1C A - k2C B
dt
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 Reactions in Series
dimensionless concentration
CC/CA0
1.0

0.8
k1 k2
0.6
A → B →C
0.4

0.2 CB/CA0
CA/CA0
t
5 10 15 20 25 30 Which is for k2/k1=0.1
dimensionless concentration
CC/CA0
and which is for k2/k1=10?
1.0

0.8
CA/CA0
0.6

0.4

0.2
CB/CA0
t 33
5 10 15 20
 Parallel Reactions
A R
AS
dC A
first reation  k1C A ;
dt
dC A
second reation   k2C A ;
dt
dC A
   k1  k2  C A ; C A  C A0 exp    k1  k2  t 
dt

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 Arrhenius’s law

𝐸𝑎
−𝑅𝑇
𝑘 = 𝐴𝑒
Ea
ln k  ln A 
RT
k : reaction rate;
A  Arrhenius frequency factor
E a : Activation energy

Rate of reactions depends on temperature

(if exothermic, rate increases with T) 35
 Arrhenius’s law
Inactivation kinetics of bacteriophage MS2
3
UVB MS2
2 y = -1397x + 6.7
Ln(kobs) (hr )
-1
R² = 0.999
UVB
1 y = -1335x + 5.6
R² = 0.990
0 UVA
y = -2396x + 8.0
R² = 0.994
-1 y = -3672x + 10.6
R² = 0.993

-2 UVA
0.0032 0.0034
1/Temperature (1/K)
UVB (0 mg/L TOC)
UVA (20 mg/L TOC)
UVB- (20 mg/L TOC)
UVA (0 mg/L TOC) 36