Module 2

Water and wastewater quality enhancement

Concept and application of mass balance in reactor design,
Fundamentals of process kinetics
 Water Quality Parameters
• Surface and subsurface water quality
Size classification of solids in water
 Dissolved ( <1 nm)
 Colloidal (>1 nm and < 1000 nm)
 Suspended (> 1μm and < 100 μm)
 Nano ( 1- 100 nm)

• Water quality parameters

• Physical
• Chemical Sources , impacts and measurements
• Biological
• Physical- those parameters that responds to the senses of sight,
touch, taste, or smell
Suspended solids
Turbidity
Color
Taste
Odor
Temperature

– Sources
Inorganic
Organic
erosive action of water flowing over the surface.
• Suspended solids – gravimetric test
– Filterable residue
– Non filterable residue

• Turbidity
• Measure of the extent to which light is either absorbed or scattered by SS
in water
• Qualitative, not quantitative
• Nature of the solids and the secondary products they produce are more
important
• Sources
Erosion of colloidal material ( clay, silt, metal oxides from soil)
Food particles, vegetable fibers
Soaps and detergents, etc.
• Color
Apparent color – color partly due to SS
True color- color after removing SS
Sources: iron and manganese oxides, organic debris, Industrial
WW, mining, refining, etc.
• Impacts
– Exert chlorine demand, Aesthetically displeasing
– Unsuitable for laundering, dyeing, paper making, etc.
• Measurement:
– comparison with standardized coloured materials
– TCU (True Color Unit)- 1 TCU = unit equivalent to the color
produced by 1 mg/L of platinum in the form of chlorplatinate ions
• Taste and odor
– Aesthetically displeasing

• Temperature
– A cooler water- wider diversity of biological species
– Higher order species, such as fish, are affected by
temp.
• Higher solubility of chemicals
– change in factors with water quality
– temperature stratification in lakes
Major pollutants in Wastewater
 Material balance
 Mass balances are based on the fundamental
“law of conservation of mass”

Accumulation Mass out

Mass in Reaction: Decay
and generation

Control
volume
 Material Balance
A mass balance is only meaningful in terms of
a specific region of space, which has
boundaries across which the terms and are
determined. This region is called the control
volume.

Theoretically, any volume of any shape and

location can be used. Realistically, however,
certain control volumes are more useful than
others. The most important attribute of a
control volume is that it have boundaries over
which you can calculate mass input (min )and
mass output (mout)
Reaction = rate of generation-
Accumulation = {(Mass in - Mass out) + reaction} rate of consumption

Accumulation rate = {(rate of mass in - rate of mass out) + reaction}

Material Balance

 Steady-state process.
 Process that does not change with time.

 Unsteady-state (Transient) process

 Process that changes with time.
 Mass balance in self purification
• From beginning of 20th century, effluent disposal practices were based
on the premise that “ the solution to pollution is dilution”.
• Dilution was considered as the most economical means of
wastewater disposal and a good engineering practice.
• The dilution capacity of a river can be calculated using the principle
of mass balance.
• i.e., CRQR + CWQW = CMQM
• CM = (CRQR + CWQW)/QM
• where, C represents the concentration of the pollutant;
• Q represents the volumetric flow rate
• R, W, M designate river, waste stream and mixed stream /river
Oxygen Sag Curve
 Problem 1
• An effluent from a wastewater treatment plant is discharged in to a stream. The characteristics
of the effluent and the stream are as follows:
• Effluent Stream
• Flow = 8640 m3/d Flow = 1.2 m3/s
• BOD = 4550 ppm BOD = 2.1 mg/L
• NH4+ = 47 mg/L NH4+ = 3 mg/L
• Cl - = 150 mg/L Cl - = 5 ppm
• Temperature = 45°C Temperature = 15°C
• TSS = 1200 mg/L TSS = 20 mg/L

(a) Determine the stream characteristics after mixing with the effluent using a neatly draw
sketch.
(b) Comment on the dilution effect on the changed characteristics of the stream.
(c) Justify the significance of dilution as a self-purification methods
 Chemical Kinetics
Thermodynamics – does a reaction take place?
Kinetics – how fast does a reaction proceed?

Reaction rate is the change in the concentration of a reactant or a product with

time
A B
D[A] D[A] = change in concentration of A over
rate = -
Dt time period Dt
D[B] D[B] = change in concentration of B over
rate =
Dt time period Dt
Because [A] decreases with time, D[A] is negative.
 A B

time

D[A]
rate = -
Dt

D[B]
rate =
Dt
 Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)

slope of
tangent
slope of
tangent
slope of
tangent

D[Br2] [Br2]final – [Br2]initial

average rate = - =-
Dt tfinal - tinitial
instantaneous rate = rate for specific instance in time
 Factors that Affect Reaction Rate

1. Temperature
Collision Theory: When two chemicals react, their molecules have to
collide with each other with sufficient energy for the reaction to take
place.
Kinetic Theory: Increasing temperature means the molecules move
faster.
2. Concentrations of reactants
More reactants mean more collisions if enough energy is present
3. Catalysts
Speed up reactions by lowering activation energy
4. Surface area of a solid reactant
Bread and Butter theory: more area for reactants to be in contact
5. Pressure of gaseous reactants or products
Increased number of collisions
 Zero-Order Reactions

D[A]
rate = - rate = k [A]0 = k
Dt
[A] is the concentration of A at any time t
[A] - [A]0 = -kt [A]0 is the concentration of A at time t=0

Half life for zero order

t½ = t when [A] = [A]0/2
[A]0
t½ =
2k
 First-Order Reactions

D[A]
rate = - rate = k [A] [A] = [A]0e-kt
Dt

[A] is the concentration of A at any time t

ln[A] - ln[A]0 = - kt
[A]0 is the concentration of A at time t=0

13.3
Decomposition of N2O5
 Second-Order Reactions

D[A]
rate = - rate = k [A]2 [A] is the concentration of A at any time t
Dt [A]0 is the concentration of A at time t=0

1 1 Half life for second order

- = kt
[A] [A]0 t½ = t when [A] = [A]0/2
1
t½ =
k[A]0
 Problem
• The following data were obtained for an irreversible elementary reaction. Plot
the data and determine the order of the reaction (Zero, First or Second) and
the rate constant k.
Time, (min) Reactant A (Concentration, mmol/L)
0 2.80
1 2.43
2 2.12
5 1.39
10 0.69
20 0.17
• Note: Use a graph sheet to plot and fit a curve.
The reaction 2A B is first order in A with a rate constant of 2.8 x
10-2 s-1 at 800C. How long will it take for A to decrease from 0.88 M to
0.14 M ?
[A] = [A]0e-kt
[A]0 = 0.88 M
ln[A] - ln[A]0 = - kt [A] = 0.14 M
ln[A]0 - ln[A] = kt
[A]0 0.88 M
ln ln
ln[A]0 – ln[A] [A] 0.14 M
t= = = = 66 s
k k 2.8 x 10-2 s-1
 First-Order Reactions

The half-life, t½, is the time required for the concentration of a

reactant to decrease to half of its initial concentration.
t½ = t when [A] = [A]0/2

[A]0
ln
[A]0/2 Ln 2 0.693
t½ = = =
k k k

What is the half-life of N2O5 if it decomposes with a rate constant of 5.7 x 10 -4 s-1?

t½ = Ln 2 = 0.693
= 1200 s = 20 minutes
k -4
5.7 x 10 s -1
Summary of the Kinetics of Zero-Order, First-Order
and Second-Order Reactions

Concentration-Time
Order Rate Law Equation Half-Life
[A]0
0 rate = k [A] - [A]0 = - kt t½ =
2k
Ln 2
1 rate = k [A] ln[A] - ln[A]0 = - kt t½ =
k
1 1 1
2 rate = k [A]2 - = kt t½ =
[A] [A]0 k[A]0
Problem
• 𝟐𝑵𝟐 (𝒈) + 𝟐𝑯𝟐 (𝒈) → 𝑵𝟐 (𝒈) + 𝟐𝑯𝟐 𝑶 ( 𝒈) (at 1280 °C)

Experiment trial No [NO] M [H2] M Rate (M/s)

1. 0.0050 0.0020 1.25*10-5

2. 0.0100 0.0020 5.00 *10-5

3. 0.0050 0.0040 1.00 *10-4

a) Determine the rate law

b) What is the overall order of reaction
c) Find the rate constant K
 A+ B C+D
Exothermic Reaction Endothermic Reaction

The activation energy (Ea) is the minimum amount of energy required to initiate
a chemical reaction.
Temperature Dependence of the Rate Constant

k = A • exp( -Ea/RT )
(Arrhenius equation)
Ea is the activation energy (J/mol)
R is the gas constant (8.314 J/K•mol)
T is the absolute temperature
A is the frequency factor

-Ea 1
Ln k = - + lnA
R T
 Reaction Mechanisms

The overall progress of a chemical reaction can be represented at the molecular

level by a series of simple elementary steps or elementary reactions.

The sequence of elementary steps that leads to product formation is the

reaction mechanism.

2NO (g) + O2 (g) 2NO2 (g)

N2O2 is detected during the reaction!

Elementary step: NO + NO N 2 O2
+ Elementary step: N2O2 + O2 2NO2
Overall reaction: 2NO + O2 2NO2
 Reaction Intermediates

Intermediates are species that appear in a reaction mechanism but not in the
overall balanced equation.

An intermediate is always formed in an early elementary step and consumed

in a later elementary step.

Elementary step: NO + NO N 2 O2
+ Elementary step: N2O2 + O2 2NO2
Overall reaction: 2NO + O2 2NO2
 Rate Laws and Rate Determining Steps
Writing plausible reaction mechanisms:
• The sum of the elementary steps must give the overall balanced equation for the
reaction.
• The rate-determining step should predict the same rate law that is determined
experimentally.

The rate-determining step is the slowest

step in the sequence of steps leading to
product formation.
A catalyst is a substance that increases the rate of a
chemical reaction without itself being consumed.
Ea k

uncatalyzed catalyzed

ratecatalyzed > rateuncatalyzed

Enzyme Catalysis
 Kinetics and Reactor Design

Chemical kinetics is defined as Confines where chemical Obtain sizing

rate of chemical reactions, that is, reactions take place. parameters such as
with the quantitative description OR area, length, volume
of how fast chemical reactions A device in which change in …etc
occur, and factors affecting these composition of matter occurs
rates. by chemical reactions
 Chemical Reaction:

Classification of
Chemical Reactions

Phase Reversibility Molecularity

1. Homogeneous reactions 1. Unimolecular reactions:

1. Reversible reactions A B
2. Heterogeneous reactions 2. Irreversible reactions 2. Bimolecular reactions:
2A  B A B C
3. Termolecular reaction
2A  B  C
 Batch Reactor:
Definition:
Batch Reactors are defined as reactors in which no flow of mass across the reactor
boundaries, once the reactants have been charged.
Schematic Representation of Batch Reactors:
Stirrer
Liquid Surface
Tank V
 Batch Reactor:

Characteristics of Batch Reactor:

1. Each batch is a closed system.

2. The total mass of each batch is fixed.
3. The volume or density of each batch may vary as reaction proceeds.
4. The energy of each batch may vary as reaction proceeds; heat exchanger may be provided
to control temperature.
5. The reaction (residence) time for elements of the reacting fluid is the same.
6. The operation of the reactor is inherently unsteady-state; batch composition changes with
respect to time.
7. At any time, the batch is uniform in composition, temperature because of the efficient
and vigorous stirring
Continuous Stirred Tank Reactor (CSTR):
Definition:
Continuous Stirred Tank Reactors (CSTR) are defined to be flow reactors characterized by
intense mixing so that the properties anywhere inside the reactor are exactly the same as that
of the exist stream.
Schematic Representation of CSTR: Stirrer

Liquid Surface
Input Rate V

Output Rate
Continuous Stirred Tank Reactor (CSTR):
Characteristics of Continuous Stirred Tank Reactor (CSTR):

1. The flow through the vessel(s), both input and out streams, is continuous but not
necessary at a constant rate.
2. The system mass inside each vessel is not necessary fixed.
3. The volume or density of each batch may vary as reaction proceeds.
4. The energy of each batch may vary as reaction proceeds; heat exchanger may be provided
to control temperature.
5. The reaction (residence) time for elements of the reacting fluid is the same.
6. The operation of the reactor may be steady state or unsteady-state.
7. The fluid properties are uniform in composition, temperature anywhere in the vessel
because of the efficient and vigorous stirring
Plug Flow Reactors(PFR):

Definition:
Plug Flow Reactors (PFR) are defined to be flow reactors characterized by the absence of
mixing in the direction of flow and absence of variation normal to the direction of flow.

Schematic Representation of PFR:

Plug Flow Reactors(PFR):
Characteristics of Plug Flow Reactors(PFR):
1. The flow through the vessel(s), both input and out streams, is continuous
but not necessary at a constant rate.
2. The system mass inside each vessel is not necessary fixed.
3. The density of the flowing system may vary in the direction of flow.
4. There is no axial mixing of fluid inside the reactor, composition changes
along the flow direction.
5. There is complete radial mixing of fluid inside the reactor; uniform fluid
properties along the direction normal to flow direction.
6. The energy may vary as reaction proceeds; heat exchanger may be provided
to control temperature.
7. The reaction (residence) time for elements of the reacting fluid is the same.
8. The operation of the reactor may be steady state or unsteady-state.
Packed Bed Reactor
 Characteristics of PBR

1. Used primarily in heterogeneous has phase reactions with a

catalyst
2. High conversion per unit mass of catalyst
3. Low operating cost
4. Continuous operation
5. Undesired thermal gradients may exist
6. Poor temperature control
7. Channeling may occur
8. Unit may be difficult to service and clean
Fluidised Bed reactor
Characteristics of a Fluidised bed reactor

• Heterogeneous has phase reactions with a catalyst

• Good mixing
• Good uniformity of temperature
• Catalyst can be continuously regenerated with the use of an
auxiliary loop
• Bed-fluid mechanics not well known
• Severe agitation can result in catalyst destruction and dust
formation
• Uncertain scale-up