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Topic 3 - Reaction Kinetics and Reaction Theory

This document summarizes key concepts in reaction kinetics and reactor theory. It discusses reaction rates, orders of reaction, types of reaction rates including zero, first, and second order reactions. It also covers concepts like steady state, types of reactors including batch, completely mixed flow, and plug flow reactors. Retention time and how to analyze different reactors is described through examples.

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Yousef Zam
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© © All Rights Reserved
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45 views

Topic 3 - Reaction Kinetics and Reaction Theory

This document summarizes key concepts in reaction kinetics and reactor theory. It discusses reaction rates, orders of reaction, types of reaction rates including zero, first, and second order reactions. It also covers concepts like steady state, types of reactors including batch, completely mixed flow, and plug flow reactors. Retention time and how to analyze different reactors is described through examples.

Uploaded by

Yousef Zam
Copyright
© © All Rights Reserved
Available Formats
Download as PPTX, PDF, TXT or read online on Scribd
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Topic 3 – Reaction Kinetics and Reactor

Theory

Chapter 2
Spring 2012
Kazi Parvez Fattah
Reaction Rate

 A mathematical expression describing the rate at which the


mass or volume of some material A is changing with time t
is:

 Reaction rate can be a function of (one or a combination of


the following)
 Temperature

 Pressure

 Reacting components or products

 pH

 Other environmental factors

4/5/2019 2
Reaction Order

 The reaction rate is given as


r = ±kCn
Where, k = reaction rate constant (in s-1 or d-1)
C = concentration of the substance
n = exponent of reaction order
 The ± sign in the equation indicates that the

substance or chemical species is either consumed


(decreasing) or being formed (increasing)

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Types of Reaction Rates

Zero order (n=0)


Inorganic sleeve fouling for UV
𝑑𝐶
reactors
= ±𝑘; 𝐶𝑡 = 𝐶0 ± 𝑘𝑡
𝑑𝑡
Reaction not a factor of the
chemical/substance

First order (n=1) 𝑑𝐶


BOD decay = ±𝑘𝐶; 𝐶𝑡 = 𝐶0 𝑒 ±𝑘𝑡
Radioactive decay 𝑑𝑡

Second order (n=2) 𝑑𝐶 2


1 1
Ozone generation
= ±𝑘𝐶 ; = ± 𝑘𝑡
𝑑𝑡 𝐶𝑡 𝐶0
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Zero Order Reaction - Example

 Typical Figure  Example


 Nitrogen gas strips oxygen
from water before an
aeration test is performed.
Initial oxygen concentration
was 9.5 mg/L and a zero
order reaction rate coefficient
was 0.075/s. How long until
the oxygen concentration
reaches below 0.5 mg/L?

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First Order Reaction - Example

 Typical Figure  Example


 A wastewater has an
initial BOD of 220
mg/L. BOD is decayed
with a first order rate
constant of 0.011/hr.
 How long will it take to
reduce BOD to 30 mg/L?
 What will the BOD be
after 5 days?

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Second Order Reaction - Example

 Typical Figure  Example


 Ozone generation has
second order kinetics. If
the ozone concentration
in a container is 0.0015
g/m3 before a generator
is turned on and 0.002
g/m3 after 1 minute,
what is the ozone
concentration after 3
minutes?
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Steady State

 When a system has operated in such a way that the


following is true:
Rate of input = Rate of output
 Therefore, the rate of accumulation is zero
(i.e. dM/dt = 0)
 Steady state does not imply equilibrium

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Reactor
 Reactions are often required as part
of an engineered system
 Reactors are tanks in which
physical, chemical and biochemical
reactions occur
 Key aspects of reactors
 Flow characteristics

 Mixing conditions

 Control volumes

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Determination of Flow Characteristics

 A tracer used in a reactor


to understand the flow
dynamics and mixing
behavior
 Conservative, that is,
does not react
 Non-conservative, that is,
it reacts
 For monitoring practice
conservative tracer is
used
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Types of Reactor

 Batch Reactor

 Completely Mixed Flow Reactor (CMFR)

 Plug Flow Reactor (PFR)

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Batch Reactor

 They are of the fill-and- Material added


draw type to the reactor

 Materials added are mixed


for sufficient time to react
and then drained.
Mixing and
 Composition within the reacting
tank changes with time as
reaction proceeds
 A batch reaction is Reactor is
unsteady drained

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Completely Mixed Flow Reactor (CMFR)

 Also known as
continuous-flow stirred
tank reactor (CSTR)
 Contents in the tank are
ideally uniform
throughout
 Composition of the
effluent is the same as
the composition in the dM d(in) d(out)
tank = − − kCV
dt dt dt
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Plug Flow Reactor (PFR)

 Fluid particles pass


through the tank in
sequence
 Assumed that no
mixing occurs in the
lateral direction
(direction of flow)

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Batch Reactor

 Rate   Rate  Rate  Rate   Rate 


 Accumulated   in   out    produced   consumed 
         

No inflow and no outflow in a typical batch reactor


 Rate   Rate   Rate 
 Accumulated    produced   consumed 
     
dC
V  rV
dt
Typical reaction rate equations can be used to compute
• Retention time
• Effluent concentration
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Detention (or Retention) Time

 It is the time that a fluid particle remains in the


reactor
 It is also known as hydraulic detention time (for
liquid systems), retention time or detention time
 The detention time in real tanks is generally less
than the theoretical detention time
 The time is calculated by the following equation
Volume(V )

Flow rate(Q )

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Retention Time for Decay Reactions

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Example
First order
 An industry wants to use a long
reaction
drainage ditch that can be C
assumed to act as a plug flow ln   kt
C0
reactor in removing odor from
their waste. The odor reduction 0.1C0
ln   kt
behaves as a first-order reaction, C0
with the rate constant k = 0.35 ln( 0.1)  (0.35)t
days-1. The flow rate is 1600
L/day. How long must the ditch t  6.57 days
be if the velocity of the flow is length of the ditch
0.5 m/sec and 90% odor
m sec
reduction is desired?  0.5  6.57 days  86400
sec day
 2.84 105 m
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Reactor Analysis

 The selection of the reactor depend on the desired


behavior or model representation
 Important to understand the behavior of the reactor
system’s response to sudden increase or decrease
when a certain material is added to the reactor
 What is the response (effluent concentration) to a
step or pulse (or spike) change in the influent
concentration

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Tracer Studies - Step or Pulse Increase

Step
Step decrease
increase

Pulse or spike
increase

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Tracer Studies – Batch Reactor

Reactor response to a
step or pulse increase
in concentration of a
conservative
substance

Reactor response for (a) decay of a non-conservative substance


4/5/2019 and (b) formation reaction – 1st order reaction. 21
Tracer Studies – Batch Reactor contd.

 Inexpensive and easy to build


 Used in cases where the flow rate is less than
150 m3/d
 Easy to operate
 e.g. to check the wastewater for regulatory
compliance before discharge

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Tracer Studies – Completely Mixed Flow
Reactors (CMFR)
General equation for a 𝑡 𝑡
𝐶𝑡 = 𝐶0 exp − + 𝐶1 1 − exp −
nonreactive contaminant 𝜃 𝜃

For flushing of a nonreactive 𝑡


𝐶𝑡 = 𝐶0 exp −
contaminant 𝜃

For flushing of a reactive 𝑡


𝐶𝑜𝑢𝑡 = 𝐶0 exp − + 𝑘 𝑡
contaminant 𝜃

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Tracer Studies – Completely Mixed Flow
Reactors (CMFR) contd.

 Used for chemical mixing


 Flow rate is usually greater than 150 m3/d
 e.g. a) application of equalization tank to adjust pH
b) chemical precipitation to remove metals
 Ponds, lakes, streams and air mixing can be
modeled as a CMFR

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Reactive Conservative
substance substance Step
response response increase

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Tracer Studies – Plug Flow Reactors (PFR)

25
Example Problem

 1) CMFR - Adapted from book example 2.9


 2) PFR
 A continuous PFR is to be designed to treat an influent
stream containing 250 mg/L of methanol at a flow rate of
300 L/min. a second order removal reaction is occurring.
The rate constant (k) was determined in the laboratory to
be 0.0090 L/mg.h.
 Determine (a) the detention time in hours and (b) the
volume of the reactor needed, in m3, to achieve 90%
removal of the methanol.

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Review of Material Balance, Reaction
Kinetics and Reactors

 Material balance
 Mass balance
 Examples and problems
 Mass balance with transformation
 Reaction rates
 Zero, First and Second order
 Examples and problems
 Different types of reactors
 Batch, CMFR, Plug
 Examples and problems
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