Reactors in series
operated somewhere in between ideal reactor modes. Reactor
One method of increasing the removal efficiency of a process is to
use a number of reactors in series. T is usually applicable for CSTRs,
though a combination of CSTRs are used, the effluent from one
reactor serves as the influent to the next reactor. There is a stepwise
decrease in the composition of reactant and the temperature as the
flow travels from one reactor to the next one.
The detention time in the ith reactor is given by:
ti = V i / Q
Where:
V = volume of reactor
Q = volumetric flow rate
REACTORS IN SERIES:
rAi = (Ai – Ai-1) / ti
Where:
rAi = rate of consumption of A in ith reactor
ti = detention time in the reactor
Ai = concentration of A in effluent from ith reactor
Ai-1 = concentration of A in effluent from (1-i)th reactor
SEMI-BATCH OR SEMI-FLOW REACTORS
Reactors used in actual treatment plants and processes may be
operation can be semi-batch or semi-flow.
Examples:
- A reactor where all the reactants are added at the same time
as a batch, but the products are discharged continuously
- A reactor where the reactants are added at different time
intervals
- A reactor where the products are removed at different time
intervals
- A batch reactor partially filled with one reactant, with
progressive addition of other reactants until the reaction is
completed.
REACTION KINETICS
A variety of chemical and biochemical reactions take place in the
environment that are of importance to environmental engineers
and scientists. These include reactions between various elements
of the air, water, and soil as well as with microorganism
Number of reactions where it depends:
1. Times
2. Temperature
3. Pressure
4. Concentration
Reaction kinetics can be defined as the study of the effects of the
temperature, pressure, and concentration of reactants and
products on the rate of a chemical reaction.
 Reaction that occur within a single phase (solid, liquid or Type of order reaction:
gaseous) are called homogenous reactions,
-Zero order reaction
Example:
-First order reaction
Nitrification in wastewater
-Second order reaction
Reactions that involve two or more phase are called
heterogeneous reaction
Zero order reaction
Example:
Proceeds at a rate that is independent of the concentration of the
Gas adsorption on activated carbon
reactants or products. Consider the following irreversible elementary
The rate of reaction, ri, is used to described the rate of formation reaction where reactant A is converted to product C:
of a product, or rate of disappearance of a reactant
A -> C
For homogeneous reaction, ri, is calculated as the moles or mass
If this reaction is zero order, the rate expression can be written as:
produced or consumed per unit volume per unit time.
rA = -k
aA + bB -> cC
(d[A]) / dt = -k[A]0 = -k[1] = -k
where:
Where:
C = product
(d[A]) / dt = rate of change of concentration of A with time
A,B = reactants
K = reaction rate constant, time
a,b,c = stoichiometric coefficient
The order of a reaction is the sum of the empirically determined
exponents, with respect to the reactants A and B, while the order is y First order reaction
with respect to its product C. The order of reaction can be a whole
number or a fraction. If the reaction is first order with respect to concentration of A, the rate
expression becomes
For a homogeneous, irreversible, elementary reaction that occurs in a
single step, the empirically determined exponents equal to the d[A]) / dt = -k[A]
stoichiometric coefficients
After integration:
[At] = [Ao] e-kt
Second order reaction
The simplest kind of second-order reaction is one whose rate is
proportional to the square of the concentration of one reactant. These
generally have the form 2A → products. A second kind of second-order
reaction has a reaction rate that is proportional to the product of the
concentrations of two reactants. Such reactions generally have the
form A + B → products. An example of the former is a dimerization
reaction, in which two smaller molecules, each called a monomer,
combine to form a larger molecule (a dimer).
The differential rate law for the simplest second-order reaction in which
2A → products is as follows:
rate=−Δ[A]2Δt=k[A]2(14.22)(14.22)rate=−Δ[A]2Δt=k[A]2
Reactors
A reactor is a tank or vessel where chemical, biological, or
biochemical reactions take place, usually in a liquid medium.
Chemical reactors
Are use in a water treatment plant in coagulation-flocculation, lime
softening, taste and odor control, disinfection, and other unit
processes that involved chemical reactions.
Reactors are used in wastewater treatment plants involve biochemical
and biological reactions
Example:
Activated sludge reactor, membrane bioreactor
Types of reactors:
1. Batch reactor
2. Plug flow reactor (PFR)
3. Continuous-flow stirred tank reactor ( CSTR )
Models developed for ideal reactors can be further modified to
represent real-life processes and flow conditions for reactors used at
treatment plants.
Batch reactor
In a batch reactor, reactants are added to the reactor and mixed for a
requisite amount of time for the reactions to occur.
At the end of the reaction time, the contents are removed from the
reactor.
One characteristic of the batch reactor is that all fluid particles have
the same residence time in the reactor
Homogeneous mixing is assumed, so that the composition of the
mixture is the same throughout the reactor
Labor costs and materials handling costs can run high, due to the time
and effort involved in filling emptying, and cleaning the reactors.
Design equation:
Rin = Rout + Racc – Rcon
Where:
Sample problem: The following data were obtained from a batch
Rin/out= rate of input/output experiment for the reaction A → P. Determine the order of the
Racc= rate of accumulation reaction.

Rcon= rate of consumption Point A B C D E F G

Time 0 10 20 30 40 60 80
(min)
Plug flow reactor A 100 74 55 30 17 9 5
(mg/L)
In a plug flow reactor, fluid particles flow through the tank and are
discharged in the same sequence as the entered. The fluid particles
move through the reactor tube as plugs moving parallel to the tube
axis. Assuming that the section of the curve between each time interval is a
straight line, the rates could be calculated from the slope of that
The plug flow reactor is suitable for gas phase reactions that take section.
place at high pressure and temperature. The average reaction rate is
usually higher in a PFR as compared with CSTR of similar volume, for So, if rA = dA/dt: 𝑑𝐴𝑑𝑡=Δ𝐴Δ𝑡=100−740−10=−2.59
the same feed composition and reaction temperature
For first interval and so on.
Plotting of ln(–rA) versus ln(A) will yield a slope that we can use for
Continuous- flow stirred tank reactors the best fit line, which is 0.935, and can be rounded-off to 1. So the
reaction is first order.
This is used mainly for liquid phase reactions at low or atmospheric
pressure.
In this reactor, the reactant flows continuously into the reactor, the
product effluent flows out continuously, and the reactor contents are
mixed on a continuous basis.
This type of reactor is also called back mix reactor or completely
mixed reactor. The basic assumption for an ideal CSTR is that the
reactor contents are completely mixed and homogeneous throughout.
 Wastewater contains a wide variety of microorganisms, some of
which are pathogens, while others play a significant role in
degradation of organic matter.
Bacteria, protozoa, and other microorganisms play an active role in
the conversion of biodegradable organic matter to simpler end
products that result in stabilization of the waste.
This is a continuous process occurring in streams and rivers as
natural purification processes. These natural purification processes
are enhanced and accelerated in engineered biological treatment
systems at wastewater treatment plants.
The three major domains of living organisms are the Bacteria, the
Archaea, and the Eukarya.
Based on cell structure, all living organisms are divided into two
types: prokaryotic and eukaryotic. The major structural difference
between prokaryotes and eukaryotes is their nuclear structure.
The major structural difference between prokaryotes and eukaryotes
is their nuclear structure. The eukaryotic nucleus is surrounded by a
nuclear membrane, contains DNA (deoxyribonucleic acid) molecules,
and undergoes division by mitosis.
On the other hand, the prokaryotic nuclear region is not surrounded
by a membrane and contains a single DNA molecule whose division is
nonmitotic.
The prokaryotes include bacteria, blue-green algae (cyanobacter),
and archaea. The archaea are separated from bacteria due to their
DNA composition and unique cellular chemistry. Examples of archaea
are the methane producers, e.g. methanococcus, methanosarcina.
The eukaryotes are much more complex and include plants and
animals, as well as protozoa, fungi, and algae.
Bacteria are unicellular prokaryotic microorganisms. They use soluble
food. Bacteria usually reproduce by binary fission, although some
species reproduce sexually or by budding. They are generally
characterized by the shape, size, and structure of their cells.
The cell wall is a rigid structure that provides shape to the cell and
protects it from osmotic pressure. The wall is usually 0.2 to 0.3 μm
thick and accounts for 10% to 50% of the dry weight of the cell. Inside
the cell wall is the cytoplasmic membrane, a critical permeability
barrier that regulates the transport of food into the cell and of waste
products out of the cell.
The interior of the cell contains the cytoplasm, the nuclear area, and
the polyribosomes. The cytoplasm is a colloidal suspension of
proteins, carbohydrates, and other complex organic compounds. The
cytoplasm contains RNA, which causes biosynthesis of proteins. The
RNA, together with proteins, forms densely packed particles called
polyribosomes, which manufacture enzymes for each specific
biochemical reaction.
A number of factors affect the growth and death of bacteria. These
include type of food or carbon source, abundance of food, nutrients,
pH, temperature, presence or absence of oxygen, and toxic
substances. Given the presence of optimal conditions, bacteria can
grow in logarithmic proportions.
The first phase is called the lag phase. This represents the time
needed by the bacteria to adjust to the new environment and start
producing enzymes necessary to degrade the substrate surrounding
them.
If the substrate is readily degradable, then the lag phase is short. If
the substrate is not readily biodegradable, then it may take time for
the bacteria to produce the necessary enzymes.
This may result in a long lag phase until the bacteria are acclimated to
the substrate and then start reproducing. If the bacteria are not able to
synthesize the necessary enzymes, the substrate may be toxic and
eventually result in death of the cells.
After the lag phase comes the logarithmic or exponential growth
phase. In this phase, the population doubles at regular intervals of
time due to abundance of substrate and optimal growth conditions.
The last phase is called the endogenous decay or death phase,
when one or more nutrients or the substrate is completely exhausted.
Cell death and lysis releases some soluble organics that are used by
surviving bacteria for a while. The death rate keeps on increasing until
all bacterial cells die off.
Heterotrophic —uses organic compounds as both their carbon and
energy source. A large number of wastewater bacteria are
heterotrophic.
Classification by oxygen requirement
1. Aerobic—requires oxygen for growth and survival.
2. Anaerobic—grows in absence of oxygen. They cannot survive in
presence of oxygen.
3. Facultative—can grow both in presence or absence of oxygen.
Classification by temperature
1. Cryophilic or psychrophilic—grows at temperatures below 20°C,
usually between 12°C and 18°C.
2. Mesophilic—grows between 25°C and 40°C, optimum at 35°C.
3. Thermophilic—grows between 50°C and 75°C, optimum at 55°C.
Growth is not limited to these temperature ranges only. Bacteria will
grow at slower rates at other temperatures and can survive over a
wide range of temperatures.
Protozoa are mostly unicellular eukaryotes that lack cell walls. They
can be free living or parasitic. Most are aerobic heterotrophs, some
are aerotolerant anaerobes, and a few are obligate anaerobes. They
reproduce by binary fission. They can range in size from a few to
several hundred μm. They are an order of magnitude larger than
bacteria.
Amoeba—They move by extending their cytoplasm in search of food.
These extensions are called pseudopods or false feet. They are
pathogenic and cause ameobic dysentery in humans.
Giardia lamblia—These are parasitic protozoa. They range in size
from 8 to 18 μm long and 5 to 15 μm wide (Hammer and Hammer,
2012).
Cryptosporidium—This forms a thick-walled oocyst in the
environment and can survive for long periods of time. The oocyst is
spherical with a diameter of 4 to 6 μm. Cryptosporidium oocysts are
present in small numbers in surface waters.
Algae are autotrophic, photosynthetic eukaryotic plants. One
exception is the blue-green algae or cyanobacter, which is prokaryotic
and produces toxins that are harmful to fish and birds, e.g. Anabena.
ALGAE
Algae are autotrophic. They use sunlight as their energy source, and
carbon dioxide or bicarbonates as their carbon source. The oxygen
that is produced during photosynthesis replenishes the dissolved
oxygen content of the water. They are often used in aerobic oxidation
ponds, since they can produce the oxygen necessary for aerobic
bacteria. Algae are important primary producers in the aquatic food
chain
Fungi
Fungi are multicellular, nonphotosynthetic, heterotrophic eukaryotes.
Most are obligate or facultative aerobes. They can reproduce sexually
or asexually by fission, budding, or spore formation.
Virus
A virus is a noncellular genetic element that uses a host cell for its
replication and also has an extracellular state. In the extracellular
state, it is called a virion. A virion is metabolically inert and does not
carry out respiratory or biosynthesis functions. Viruses are obligate
intracellular parasites.
Virus
A virus cannot reproduce or replicate on its own. It can only replicate
inside a host body. The various phases of the replication process of a
bacteriophage are given below:
1. Attachment—adsorption of the virion to a susceptible host cell.
2. Penetration—injection of the virion or its nucleic acid into the cell.
3. Replication—of the virus nucleic acid. The virus alters the cell’s
metabolism to synthesize new virus nucleic acids.
4. Synthesis—of protein subunits of the virus coat.
5. Assembly and packaging—of protein subunits and nucleic acid
into new virus particles.
6. Release—of mature new viruses from the cell by lysis as the cell
breaks open.
Natural purification processes are continually active in streams and
rivers to reduce the levels of the pollutants to acceptable or negligible
concentrations. These processes include dilution, sedimentation,
filtration, heat transfer, and chemical and biological conversions.
Dilution is a process whereby the concentration of pollutants is
reduced due to mixing of a small volume of polluted water with a large
body of water, e.g. a stream or river. This usually happens when
wastewater is discharged into a stream.
Wastewater is discharged into a stream at a flow rate Qw with a
concentration Cw of a pollutant. Prior to discharge, the stream flow
rate was Qus with a concentration Cus of the pollutant. Assuming
complete mixing at the point of discharge and no accumulation or
chemical conversion, we can calculate the downstream flow rate Qds
and concentration Cds of the mix after discharge.
From the principle of continuity,
Qw + Qus = Qds
SEDIMENTATION
Sedimentation is a process that involves the removal of suspended
solids from a water body by settling them out. The size of the solid
particles plays a major role in the efficiency of sedimentation.
MICROBIAL DEGRADATION
Wastewater discharged from municipal sources contains a large
amount of organic matter. When untreated wastewater is discharged
into streams and rivers, the organic matter is used as food by
bacteria, protozoa, and other microorganisms in the water bodies.
MEASUREMENT OF ORGANIC MATTER
A number of different methods can be used to measure the organic
content of wastewater. The commonly used techniques include
(1) biochemical oxygen demand (BOD),
(2) chemical oxygen demand (COD), and
(3) total organic carbon (TOC).
BOD is the most widely used parameter for measuring the amount of
biodegradable organic matter present in a wastewater. Standard BOD
test results are obtained after five days. This is discussed in more
detail in the following section.
COD is defined as the oxygen equivalent of organic matter that can
be oxidized by a strong chemical oxidizer in an acidic medium. COD
measures both biodegradable and nonbiodegradable organic matter.
The results can be obtained in a few hours.
The TOC test measures the total organic carbon that can be oxidized
to carbon dioxide in the presence of a catalyst. The test can be
performed rapidly and results obtained in a short period of time.
Unseeded BOD test
The BOD test is carried out in 300 ml BOD bottles according to
Standard Methods (AWWA et al., 2005). A measured volume of
wastewater is added to the bottle, together with dilution water. The
dilution water is prepared by adding phosphate buffer, magnesium
sulfate, calcium chloride, and ferric chloride.
Seeded BOD test
When wastewater does not have enough microbial population in it to
exert a measurable oxygen depletion during the BOD test, seed
microorganisms are added to the mixture.
The following equation is used to calculate the BOD of a seeded
wastewater:
𝐵𝑂𝐷𝑡=𝐷1−𝐷2−𝐵!−𝐵2𝑓𝑃
where: D1 = Initial dissolved oxygen concentration of diluted seeded
wastewater mixture, mg/L
D2 = Final dissolved oxygen concentration of diluted seeded
wastewater mixture, mg/L
B1 = Initial dissolved oxygen concentration of seed mixture from seed
BOD test, mg/L
B2 = Final dissolved oxygen concentration of seed mixture from seed
BOD test, mg/L
f = Ratio of seed volume in seeded wastewater mixture to seed
volume used in seed BOD
test=𝑚𝑙 𝑜𝑓 𝑠𝑒𝑒𝑑 𝑖𝑛 𝐷1𝑚𝑙 𝑜𝑓 𝑠𝑒𝑒𝑑 𝑖𝑛 𝐵1=0.05 𝑡𝑜 0.10
𝑃= 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑤𝑎𝑠𝑡𝑒𝑤𝑎𝑡𝑒𝑟 𝑠𝑎𝑚𝑝𝑙𝑒300 𝑚𝑙
Determination of k and L
The values of the constants k and Lo or BODult can be determined
from a series of BOD measurements.
Thomas’s graphical method
A BOD test is conducted for 7 to 10 d, and daily measurements are
taken. For each day, BOD and (time/BOD)1/3 are calculated.
Theoretical oxygen demand
The theoretical oxygen demand (ThOD) for a compound or substance
can be determined from the chemical oxidation reactions of that
compound.
 4. Steady state conditions are assumed along the stream channel,
DISSOLVED OXYGEN BALANCE resulting in the use of a single value of k2. Stream bed characteristics,
•Dissolved oxygen sag curve slopes, impoundments, etc. are not considered.

When a wastewater with a significant amount of organic matter is

discharged into a stream or river, the dissolved oxygen level
decreases and drops to a minimum value. As reaeration slowly
replenishes the dissolved oxygen, over time and with distance, the
stream DO level comes back to predischarge concentration.
Dissolved oxygen sag curve - Critical points
The lowest point on the oxygen sag curve, where the deficit is the
greatest, is called the critical deficit Dc. This point represents the
maximum impact of the waste discharge on the dissolved oxygen
content of the stream. If the BOD of the waste is too high, it may result
in a deficit that causes anaerobic conditions in the stream, i.e. DO
level goes to zero.
Sample Problems
1.A tanning industry discharges wastewater with ammonia into a
stream as illustrated. Prior to discharge, the flow rate of the stream is
30 m3/s with an ammonia concentration of 0.2 mg/L. The flow rate of
the industrial discharge is 1.3 m3/s with an ammonia concentration of
50 mg/L. Calculate the resultant flow rate and ammonia concentration
downstream from the point of discharge.
SOLUTION
Calculate resultant flow rate using equation of continuity
Qds = 30 m3/s + 1.3 m3/s Qds = 31.3 m3/s

Write a mass balance between upstream and downstream points

•Dissolved oxygen sag curve - Limitations of the oxygen sag curve
model (Mass flow rate of ammonia)in = (Mass flow rate of ammonia)out
1. The model assumes only one source of BOD discharge into the (30 m3/s × 0.2 mg/L) + (1.3 m3/s × 50 mg/L) = 31.3 m3/s × Cds
stream. If there are multiple waste discharges along the stream, they
have to be taken into account. The stream can be divided into Cds = 2.27 mg/L ans.
segments consisting of a single source of waste discharge, and the
model applied sequentially from the first to the last segment.
2. Oxygen demand due to nitrification or algal respiration is not taken
into account.
3. Contribution of algae to reaeration is not considered.