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EE - 14 Sept-Class Notes

The document discusses first order reactions and steady state systems for non-conservative pollutants in continuously stirred tank reactors (CSTRs). It provides examples of how to use mass balance equations to model and calculate pollutant concentrations in CSTR systems. For a first order decay reaction in a batch reactor, the concentration decays exponentially over time. A CSTR can achieve steady state where the input and output reaction rates are equal, allowing the use of mass balances to determine pollutant concentrations.

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59 views5 pages

EE - 14 Sept-Class Notes

The document discusses first order reactions and steady state systems for non-conservative pollutants in continuously stirred tank reactors (CSTRs). It provides examples of how to use mass balance equations to model and calculate pollutant concentrations in CSTR systems. For a first order decay reaction in a batch reactor, the concentration decays exponentially over time. A CSTR can achieve steady state where the input and output reaction rates are equal, allowing the use of mass balances to determine pollutant concentrations.

Uploaded by

PraphulJain
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© © All Rights Reserved
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MATERIAL AND ENERGY BALANCE ……

First Order reaction


For most of the non-conservative pollutants the decay is a first order reaction. In such cases, the rate of
the reaction r(C ) is dependent on the amount of pollutant present.

r(c) = k*C (generation) or r(C ) = - k*C (for decay)

dC/dt = -k*C

where k is the reaction rate constant. Here k has a unit of per time (t-1).
Example: Radioactive decay of radon gas follows the first order reaction. The mass that decays in a given
time is directly proportional to the mass that is present at that time.
This equation can be integrated by separation of variables and then integrated between time t = 0 to t =
−kt
t to give the relationship as: C=C 0 e

In a first-order reaction, the concentration of a substance decays exponentially. The first order decay
and growth for a batch reactor is shown in Figure 6.

250

200
Concentration

150
Decay Growth
100

50

Time

Figure 6. Growth and decay for a first order reaction in a batch reactor.
Steady state system with non-conservative pollutants (CSTR reactors)

When a system has operated in such a way that the rate of input and the rate of output are
constant and equal, then, of course, the mass rate of accumulation is zero.

The mass balance equation will be:


Input rate – output rate + reaction rate = 0 (1)

In solving mass balance problems, it is convenient to make an assumption that steady-state


conditions have been achieved.

It is to be noted that steady state does not imply equilibrium. For example, water running into
and out of a pond at the same rate is not at equilibrium, otherwise it would not be flowing.
However, if there is no accumulation in the pond, then the system is at steady state. For steady
state:

Output rate = Input rate + reaction rate

The batch reactor can’t describe a steady state system for non-conservative substance because
now there is input and output. Such system can be described by a continuously stirred tank
reactor (CSTR) or a perfectly mixed flow reactor or complete mix box model.

Examples of a CSTR system are:


a) water in a pond with inlet and outlet; b) air in a well-ventilated room
In a CSTR the concentration C in the tank is uniform everywhere.
The reaction rate can be either + ve (for generation) or – ve (for decay). The reaction rate can
be approximated by a zero-, first-, or second- order reactions.

If the tank volume = V; and Concentration of pollutant = C, then Reaction rate


Reaction type Reaction rate
Zero order Vk (-Vk)
First order VkC (-VkC)
2nd order VkC2 (-VkC2)

For a CSTR with 2nd order reaction rate for a non-conservative pollutant
Output rate = Input rate – kVC2 (for decay)
Example: A bar with volume 500 m 3 has 50 smokers in it, each smoking 2 cigarettes
per hour. An individual cigarette emits about 1.4 mg of formaldehyde (HCHO).
Formaldehyde converts to carbon dioxide with a reaction rate coefficient k = 0.40/hr.
Fresh air enters the bar at the rate of 1,000 m 3/hr, and stale air leaves at the same rate.
Assuming complete mixing, estimate the steady-state concentration of formaldehyde in
the air. At 250C and 1 atm of pressure, how does the result compare with the threshold
for eye irritation of 0.05 ppmv? (Taken from Masters and Ela)

Solution: The bar acts as a CSTR reactor, and the complete mixing inside means the
concentration of formaldehyde C in the bar is the same as the concentration in the air leaving
the bar.

The formaldehyde concentration in fresh air is considered 0.


The input rate in equation 1 is also 0.
The mass balance equation then becomes: Output rate = reaction rate
Both a generation term (the cigarette smoking) and a decay term (the conversion of
formaldehyde to carbon oxide) are contributing to the reaction rate. If we call the generation
rate, G, we can write

G = 50 smoker x 2 cigs/hr x 1.4 mg/cig = 140 mg/hr

=> Q*C = G – kCV

140 mg/hr
G
C= = m3 0.40 = 0.117 mg/ m3
Q+ kV 1,000
hr
+ ( )
hr
X 500m 3

We have to convert mg/m3 to ppmv. The molecular weight of formaldehyde is 30, so

C( mg/m 3)× 24.465 o .117 ×24.465


[HCHO] = = =0.095 ppmv
mol wt 30

This is nearly double the 0.05 ppmv threshold for eye irritation.

Thus there will be eye irritation to many people inside the bar.
Example 2. A well-mixed sewage lagoon (a shallow pond) is receiving 430 m 3/d of untreated
sewage. The lagoon has a surface area of 10 ha (hectares) and a depth of 1.0 m. The pollutant
concentration in the raw sewage discharging into the lagoon is 180 mg/L. The organic matter in
the sewage degrades biologically (decays) in the lagoon according to first-order kinetics. The
reaction rate constant (decay coefficient) is 0.70 d-1 . Assuming no other water losses or gains
(evaporation, seepage, or rainfall) and that the lagoon is completely mixed, find the steady-state
concentration of the pollutant in the lagoon effluent. (Source: Davis Book)

Solution:

The mass balance equation may be written as:

Accumulation = input rate - output rate - decay rate

Assuming steady-state conditions, that is, accumulation 0, the Input rate = output rate + decay rate

This may be written in terms of the notation in the figure as:

Solving for Ceff, we have:

Q = 430 m3/d x 1000 L/m3 = 430000 L/d


The input mass rate (Cin Q in) = (180 mg/L) (430 m3 /d) (1,000 L/m3) = 77,400,000
mg/d

Lagoon volume = (10 ha) (104 m2 /ha) (1 m) = 100,000 m3

Decay coefficient = 0.70 d-1 ,

The decay rate is = kCV = (0.70 d-1 )(100,000 m3 )(1,000 L/m3 )(C lagoon) =
(70,000,000 L/d)(C lagoon)

Now we use the assumption that the lagoon is completely mixed. Therefore, C eff
= C lagoon.

Thus, kCV = (70,000,000 L/d)(C eff)

C eff x Q eff = 77,400,000 mg/d – (70,000,000 L/d x C eff)

C eff x 430000 L/d = 77,400,000 mg/d – (70,000,000 L/d x C eff)

C eff x 70,430,000 L/d= 77,400,000 mg/d

C eff = (77,400,000 mg/d )/ (70,430,000 L/d) = 1.10 mg/L

Ceff = 1.10 mg/L

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