REACTION KINETICS
A variety of chemical and biochemical reactions take place in the
environment that are of importance to environmental engineers
MODULE 3 and scientists. These include reactions between various elements of
the air, water, and soil, as well as with microorganisms.
Reaction Kinetics and Chemical Reactors A number of these reactions are dependent on:
ILOs: a) Time
1. Recall Reaction Kinetics b) Temperature
2. Discuss principles about Chemical c) Pressure
Reactors d) Concentration
3. Derive necessary equations for the types of
reactors
For example: biodegradation of organic matter, bacterial growth
4. Solve complex problems about kinetics and
and decay, and chemical disinfection.
reactors
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A→C
Where:
α = order of the reaction (e.g. 0, 1, 2, etc.)
k = reaction rate constant
A→C Integrating the equation from initial values to values after time t
[𝐴𝑡 ] 𝑡
If this reaction is zero order, the rate expression can be written as: 𝑑 𝐴 = −𝑘 𝑑𝑡
[𝐴0 ] 0
rA = –k
[𝐴𝑡 ] – [𝐴𝑜 ] = – 𝑘𝑡
𝑑[𝐴] 0 Where:
= −𝑘 𝐴 = −𝑘 1 = −𝑘
𝑑𝑡 [Ao] = initial concentration of reactant A at time zero, mg/L
[At ] = concentration of A after time t, mg/L
𝐴𝑜 1 1
log 𝑒 = 𝑘𝑡 − = 𝑘𝑡
𝐴𝑡 [𝐴𝑡 ] 𝐴0
𝐴𝑡 = 𝐴0 𝑒 −𝑘𝑡
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REACTORS REACTORS
A reactor is a tank or vessel where chemical, biological, or There are three (3) types of ideal reactors:
biochemical reactions take place, usually in a liquid medium. (1) batch reactor,
(2) plug flow reactor (PFR), and
Reactions can also take place in solid or gaseous medium or in a (3) continuous-flow stirred tank reactor (CSTR).
combination.
The hydraulics and conversion efficiencies of these reactors can be
Chemical reactors are used in a water treatment plant in determined using mathematical models.
coagulation–flocculation, lime softening, taste and odor control,
disinfection, and other unit processes that involve chemical Models developed for ideal reactors can be further modified to
reactions. represent real-life processes and flow conditions for reactors used
at treatment plants.
Reactors used in wastewater treatment plants involve mostly
biochemical and biological reactions, e.g. activated sludge reactor,
membrane bioreactor.
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.
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The PFR makes more efficient use of reactor volume, which makes
it suitable for processes that require large volumes. With
sufficiently high recycle rates, the behavior of the PFR becomes
similar to that of a CSTR.
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Design equation
REACTORS IN SERIES
𝑅𝑖𝑛 = 𝑅𝑜𝑢𝑡 + 𝑅𝑎𝑐𝑐 − 𝑅𝑐𝑜𝑛
One method of increasing the removal efficiency of a process is to
use a number of reactors in series. This is usually applicable for
At steady state conditions, rate of accumulation = 0. So the design
equation can be written as: CSTRs, though a combination of CSTR and PFR can also be used.
When a series or cascade of CSTRs are used, the effluent from one
𝐴𝑡 − [𝐴0 ] reactor serves as the influent to the next reactor.
𝑟𝐴 =
𝑡
There is a stepwise decrease in the composition of reactant and
where all the terms have the same meanings as defined in the temperature as the flow travels from one reactor to the next one.
previous sections. Assuming that the conditions in any individual reactor in the series
are not influenced by downstream conditions, and conditions of the
When the order of the reaction is known, an expression for rA can inlet stream and those prevailing in the reactor are the only
be substituted into the left side of the above equation to obtain the variables that influence reactor performance (Hill, 1977), the
design expression. following design equation can be written for steady state
conditions:
Where:
rAi = rate of consumption of A in ith reactor
ti = detention time in ith reactor
[A]i = concentration of A in effluent from ith reactor
[A](i–1) = concentration of A in effluent from (i–1)th reactor
= concentration of A in influent to ith reactor
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SAMPLE PROBLEMS
SAMPLE PROBLEMS
Solution-01:
Assuming that the section of the curve between each time interval
Problem-01: The following data were obtained from a batch is a straight line, the rates could be calculated from the slope of that
experiment for the reaction A → P. Determine the order of the section.
reaction.
So, if rA = dA/dt:
𝑑𝐴 ∆𝐴 100 − 74
Point A B C D E F G = = = −2.59
𝑑𝑡 ∆𝑡 0 − 10
Time(min) 0 10 20 40 60 80 100
For first interval and so on.
A (mg/L) 100 74 55 30 17 9 5
Plotting of ln(–rA) versus ln(A) will yield a slope that we can use for
the best fit line, which is 0.935, and can be rounded-off to 1. So the
reaction is first order.
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Solution-02:
For a first order reaction, rA = –k[A] Substitute the expression for
rA in equation:
𝑑[𝐴]
= −𝑘 𝐴
𝑑𝑡
Solution-03: The given reaction is first order with k = 0.38/s, 𝑡 = 7.88 𝑠𝑒𝑐𝑠.
[Ao] = 0.25 mol/L. With 95% conversion, [At] = (1 – 0.95) [Ao] =
0.05 × 0.25 = 0.0125 mol/L. We can now solve for the Volume of PFR,
Solution-04:
Thus, we can say that:
For the first order reaction, we’ll use the formula: 1 45 𝑳
𝐴𝑜 𝑘= − 1 = 𝟎. 𝟎𝟎𝟏𝟒
𝑘𝑡 = −1 5 36 36 𝒎𝒈 ∙ 𝒎𝒊𝒏
𝐴𝑡
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Sample Problems
Problem-06: In Problem-05, if another CSTR was used as the
second reactor instead of the PFR, what would be the effluent
concentration of A? Calculate the conversion efficiency. Determine
the concentration of reactant A in the first and second reactors.
Solution-06:
Using the equation for CSTR for the first order reaction in reactor
#2:
𝑚𝑔 0.05
𝐴1 = 36 ; 𝑘𝐶𝑆𝑇𝑅 = ; 𝑡 = 5𝑚𝑖𝑛
𝐿 𝑚𝑖𝑛
𝐴1 36 𝒎𝒈
𝑘𝑡 = − 1; 0.05 5 = − 1; 𝑨𝟐 = 𝟐𝟖. 𝟖𝟎
𝐴2 𝐴2 𝑳
45 − 28.80
𝑂𝑣𝑒𝑟𝑎𝑙𝑙 𝑐𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 = × 100% = 𝟑𝟔%
45