CSE30337 Water and Waste Management

Lecture 5 – Reaction Kinetics and Mass

Balance for Environmental Engineering

Instructor: Ben S.-Y. Leu

Email: syleu@polyu.edu.hk

1
 Outline
 Introduction to reaction kinetics
 0, 1st, and 2nd order kinetics
 Introduction to other types of kinetics
 Adsorption
 Introduction of adsorption theories
 Adsorption isotherms
 Mass balance
 Conservation of mass
 Application in wastewater and exercises
CSE30337 Water and Waste Management 2
Introduction to Chemical Kinetics
 Thermodynamic vs. Reaction Kinetics
 Many reactions are thermodynamically
favorable but reactions may not occur in
geological time periods of a natural system
or within the hydraulic retention time of an
engineered system i.e. a treatment plant

Gibb Free Energy

 Most natural and engineered systems are H2+O2
open systems where there are inflows and
outflows of masses with their surroundings ΔG<0
 Kinetics or reaction rates are used in open H 2O
systems such as the design of water and
wastewater systems
CSE30337 Water and Waste Management 4
 Chemical Kinetics
 Chemical kinetics is concerned with the speed or velocity of
reactions
 For example, if a reaction is considered in which A, B, and C are
possible reactants, then the rate may be expressed as:
 Rate = k[A] 1st Order
 Rate = k[A]2 or k[A][B] 2nd Order
 Rate = k[A]3 or k[A]2[B] or k[A][B][C] 3rd Order
 In many calculations “mass” concentrations (shown as C, mg/L)
are used
CSE30337 Water and Waste Management 5
 Define Reaction Rate
 Kinetics is to Describe the “Rate” of Reaction
 The More Workers, The Faster The Works Get to be Done?!

CSE30337 Water and Waste Management wikimedia 6

 Define Reaction Rate

Concentration

Time

[A]final -[A]initial [A] dC

Re action Rate    
reaction time t dt
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 Zero Order Reactions
 Definition

Concentration
 Reaction rate is not related to concentration
 Expression

dC
 k C  C0  kt Time
dt

Reaction Rate
 Key Concept
 C × 2 → R = Constant
 C vs. t = Linear
Time
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 First Order Reactions
 Example

Concentration
 Decomposition of a radioactive element
 Expression

dC
  kC C  C0  e  kt Time
dt

Reaction Rate
 Key Concept
 C×2→R×2
 log C vs. t = Linear
Time
CSE30337 Water and Waste Management 9
 Second Order Reactions
 Example

Concentration
 Decomposition of a radioactive element 2nd Order
 Expression
1st Order

dC 1 1
  kC 2   kt Time
dt C C0
1/C
 Key Concept
 C×2→R×2 1/C0
 1/C vs. Linear
Time
CSE30337 Water and Waste Management chemwiki.ucdavis.edu/ 10
 0-order

1st-order

2nd-order

www.chem.purdue.edu
 Other Kinetics
Consecutive Reactions Monod Kinetics – Food vs. Growth
ABC

Growth Rate
Concentration

dCA
 k1CA
dt
dCB
 k1CA  k2CB
dt
dCC ˆsS
 k 2 CB Growth Rate  X
dt Ks  S

Substrate
Time
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Adsorption
 Adsorption
An essential physical-chemical reaction to affect the transportation of
pollutants in the soil-water environment
Hydrophobic or
hydrophilic?

extension.missouri.edu
CSE30337 Water and Waste Management Thompson, A. & Goyne, K. W. (2012) 14
 Activated Carbon

www.alarco.gr purewatergazette.net
Brita.com
 Adsorption
 Terminology
 Adsorbate – material being concentrated
 Adsorbent – adorbing solids
 What is Adsorption Isotherm?

Amount Adsorbed
Adsorbate Adsorbate

Concentration of “Free”
Adsorbent Particles
Adsorbent
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 Adsorption Isotherms

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 Langmuir Isotherm
 The isotherm assumes that a single adsorbate binds to a single site on the
adsorbent
K ads C
q=qm
1+K ads C

where q = sorbed concentration (mass adsorbate/mass

adsorbent)
qm= maximum capacity of adsorbent for adrobate
C = aqueous concentration of adsorbate (mass/voulme)
Kads =measure of affinity of adsorbate for adsorbent

CSE30337 Water and Waste Management 18

 Langmuir Isotherm

qm
q

K ads C 1 1 1 1
q=qm =  
1+K ads C q qm qm K ads C

C
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 Freundlich isotherm
Derived from Langmuir Isotherms
1/n 1
q=KC log q=logK+ logC
n

CSE30337 Water and Waste Management 20

Example 3.16 Granular activated carbon (GAC) was tested for its ability to
remove soluble organic nitrogen (SON) from treated wastewater. Different
masses of GAC were added to 1 liter of the wastewater (initial SON
concentration = 0.9 mg/L) and contacted for 2 h at 20°C and pH=7.5. Using
the data given in the table and linear regression analysis determine whether
the Langmuir or Freundlich isotherm best describes the data.
Mass GAC C, mg/L of
added SON Freundlich Langmuir
0.2 0.77 1 1 1 1 1
log q=logK+ logC =  
0.5 0.65 n q qm qm K ads C
2 0.32
5 0.19
10 0.14
20 0.09
50 0.06
Mass GAC Co, mg/L C, mg/L of q, mg SON
added of SON SON removed/g GAC
0.2 0.9 0.77 0.65
0.5 0.9 0.65 0.5
2 0.9 0.32 0.29
5 0.9 0.19 0.142
10 0.9 0.14 0.076
20 0.9 0.09 0.0405
50 0.9 0.06 0.0168

Langmuir Freundlich
1 1 1 1 1
=   log q=logK+ logC
q qm qm K ads C n
 q C 1/q 1/C Log q Log C
0.65 0.77 1.54 1.30 -0.187 -0.114
0.5 0.65 2.00 1.54 -0.301 -0.187
0.29 0.32 3.45 3.13 -0.538 -0.495
0.142 0.19 7.04 5.26 -0.848 -0.721
0.076 0.14 13.16 7.14 -1.119 -0.854
0.0405 0.09 24.69 11.11 -1.393 -1.046
0.0168 0.06 59.52 16.67 -1.775 -1.222

Langmuir Freundlich
1 1 1 1 1
=   log q=logK+ logC
q qm qm K ads C n
 70 0.0
60 f(x)-0.2
= 1.37756959486 x + 0.03279290241
R² =-0.4
0.975039636931606
50= 3.5814013708 x − 7.69501937481
f(x) -0.6
R²40
= 0.92775865800581 -0.8
-1.0

Log q
1/q 30
-1.2
20 -1.4
10 -1.6
-1.8
0 -2.0
0 2 4 6 8 10 12 14 16 18 -1.5 -1.0 -0.5 0.0
1/C Log C

Langmuir Freundlich
1 1 1 1 1
=   log q=logK+ logC
q qm qm K ads C n
 BET Isotherm
 An equation to describe adsorption behavior of a
subject onto a surface with multilayer

CSE30337 Water and Waste Management

http://www.jhu.edu 25
Mass Balance
 Basic concept
General equation:

Q1=10 L/h Q1,C1

Waste
Water Q3 = Q 1 + Q 2 Q3 = Q 1 + Q 2
Q3 = 10 + 5 water Q3C3 = Q1C1 + Q2C2
Q3 = 15 L/h Q2,C2
Q2=5 L/h
BUT C3 ≠ C1 + C2

= flowrate (Volume/time)
= concentration (Mass/volume)

CSE30337 Water and Waste Management 27

 Basic Application
In the assumption of steady state, no reaction:
= mass flow (Mass/time)
; = flowrate (Volume/time)
= concentration (Mass/volume)

Water:
Boundary condition

Qin, Cin System Qout, Cout Contaminants:

CSE30337 Water and Waste Management 28

Example 1: Steady state, no reaction
A waste stream with flow Q1 = 1 m3/s is mixed with a small river with flow Q2 = 12 m3/s. Concentration
of contaminant in waste stream is C1 = 130 mg/L. The upstream river has no initial contaminants (C2 =
0 mg/L). What is the final concentration of contaminants in the downstream river?

∑ 𝑄𝑖𝑛 𝐶𝑖𝑛=¿ ∑ 𝑄𝑜𝑢𝑡 𝐶𝑜𝑢𝑡 ¿ Known parameters:

Waste: Q1 = 1 m3/s
Upstream: Q2 = 12 m3/s
Out: Qout = ?
C1 = 130 mg/L
C2 = 0 mg/L
Cout = ?
Boundary condition Water:

Q1, C1

Q2, C2
System Qout, Cout
Contaminants:

Cout = ?
Example 2: Steady state, no reaction
In the winter, a stream flows at 10 m3/s and receives discharge from a pipe that contains road runoff. The pipe
has a flow of 5 m3/s. The stream's chloride concentration just upstream of the pipe's discharge is 12 mg/L, and
the runoff pipe's discharge has a chloride concentration of 40 mg/L. Chloride is a conservative substance.
a) Does wintertime salt usage on the road elevate the downstream chloride concentration above 20 mg/L?
b) What is the maximum daily mass of chloride (metric tons/day) that can be discharged through the road
runoff pipe without exceeding the water quality standard?
Hint: We are not asked to determine the concentration of chloride at certain time, thus we can assume that
the concentration in the effluent is constant – steady state
Water:

Q1, C1

Q2, C2
System Qout, Cout

Chloride:

(a)
Known parameters:
Stream: Q1 = 10 m3/s C1 = 12 mg/L
Runoff: Q2 = 5 m3/s C2 = 40 mg/L
Out: Qout = ? Cout = ?
Example 2: Steady state, no reaction
In the winter, a stream flows at 10 m3/s and receives discharge from a pipe that contains road runoff. The pipe
has a flow of 5 m3/s. The stream's chloride concentration just upstream of the pipe's discharge is 12 mg/L, and
the runoff pipe's discharge has a chloride concentration of 40 mg/L. Chloride is a conservative substance.
a) Does wintertime salt usage on the road elevate the downstream chloride concentration above 20 mg/L?
b) What is the maximum daily mass of chloride (metric tons/day) that can be discharged through the road
runoff pipe without exceeding the water quality standard?
Hint: We are not asked to determine the concentration of chloride at certain time, thus we can assume that
the concentration in the effluent is constant – steady state
Chloride:

Q1, C1

Q2, C2
System Qout, Cout

(b)
Known parameters:
Stream: Q1 = 10 m3/s C1 = 12 mg/L
Runoff: Q2 = 5 m3/s C2 = ?
Out: Qout = 15 m3/s Cout = 20 mg/L
Example 3: Steady state, with reaction
Leachate seeps from a landfill into a river with rate Q e = 0.01 m3/s. The river has a steady flow Qa = 10 m3/s and a cross sectional area of A = 100 m2.
The concentration of organic pollutant dioxolane downstream from the region of initial mixing between the leachate and the river flow is C m = 1.0
mg/L. The ambient concentration of dioxolane is C a = 0 mg/L.
(a) What is the mass flow of dioxolane from the landfill into the river?
(b) What is the concentration Ce of dioxolane in the leachate?
(c) As the dioxolane is carried downstream by the river, the concentration of dioxolane decreases as a result of a reaction of first-order rate kf =
0.1/day. If the drinking water standard specifies that water will have dioxolane concentration less than 0.001 mg/L, how far downstream will the
water be unsafe to drink (without additional treatment to remove dioxolane)?

Known parameters:
Upstream: Qa = 10 m3/s Ca = 0 mg/L
Leachate: Qe = 0.01 m3/s Ce = ?
Out: Qm = ? Cm = 1.0 mg/L
Cross-section area of river: A = 100 m2

Calculate:
(a)
(b)
Qa, Ca
System
(c) Distance before safe drinking = ?
Qm, Cm
Qe, Ce
Question?

33
Zero Order Reaction
dC
 k

Concentration
dt
dC = -kdt

 dC = - kdt Time
C=-kt+constant

Reaction Rate
Assume C=CO @ t=0
constant = CO
C=CO -kt
Time
Frist Order Reaction 1.0

0.8
dC C
  kC 0.6
dt Ci
1 0.4
dC = -kdt
C
0.2
1
 C dC = -  kdt lnC=-kt+constant 0.0
0 1/K
1 2/K
2 3/K
3 4/K
4 5/K
5 6/K
6
Assume C=CO @ t=0
constant = lnCO 0

lnC = lnCO -kt -1

-2

C -3
C Ln ( )
ln   kt Ci -4
CO
-5
C
 e  kt -6
CO
-7
C=CO  e -kt
1/K 2/K 3/K 4/K 5/K 6/K