MASS BALANCE

REACTOR THEORY
Dr-Ing Marisa Handajani, ST, MT

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Uses
 Essential tp solution of a greater number of
environmental engineering and science problems, such as:
 Pollutant movement
 Monitoring operating efficiency in ‘day to day’ operation of
process (process control)
 Calculations for design and development of a process i.e.
quantities required, sizing equipment, number of items of
equipment
Law of conservation of mass

“Mass can neither be produced

nor destroyed”

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Mass Balance

(Mass at time t + Δ t ) =
(mass at time t ) +
(mass that entered from t to t + Δ t ) –
(mass that exited from t to t + Δ t ) +
(net mass of chemical produced from
other compounds by reaction between t
and t + Δ t )
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 Mass Flux Balance
 Rate at which mass enters or leaves a system
 Mass which enters or leaves a system in a certain time
range Δ t
 Dividing the mass balance equation by Δ t
 F = mass flux unit (mass/time)

𝒎𝒂𝒔𝒔 𝒂𝒄𝒄𝒖𝒎𝒖𝒍𝒂𝒕𝒊𝒐𝒏 𝒓𝒂𝒕𝒆 = 𝒎𝒂𝒔𝒔 𝒇𝒍𝒖𝒙 𝒊𝒏 +

𝒎𝒂𝒔𝒔 𝒇𝒍𝒖𝒙 𝒐𝒖𝒕 +
𝒏𝒆𝒕 𝒓𝒂𝒕𝒆 𝒐𝒇 𝒄𝒉𝒆𝒎𝒊𝒄𝒂𝒍 𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒊𝒐𝒏

𝑑𝑁
= 𝐹𝑖𝑛 − 𝐹𝑜𝑢𝑡 + 𝐹𝑟𝑥𝑛
𝑑𝑡

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 A mass balance is only meaningful in terms of a specific
region of space, which has boundaries across which the
term of min and mout are determined

 Control Volume has boundaries over which min and mout

can be calculated

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Mass Balance on Reactive System
 In - out + gen - cons = accumulation
FA0 FA
Rate of flow in Rate of flow out
System

GA
Rate of
generation/
consumption

 A mass balance for the system is

 NA is the mass of “A” inside the system.

dN A
FA0  FA  G A 
dt
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 The reaction term can be written in more familiar terms,
GA = rA V
 V is volume of the system.
 Note that the units for this relation are consistent:

mass mass
  volume
time volume  time
 If GA (and hence rA) varies with position in the system
volume, we can take this into account by evaluating this
term at several locations. Then DGA1 = rA1 DV1,

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Chemical Reaction (generation) Rate Forms
Possibilities
1. Conservative Compounds
 No chemical formation or loss within the control volume
 Not affected by chemical or biological reaction
𝒅𝑪ൗ
𝒅𝒕𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏 𝒐𝒏𝒍𝒚 = 𝑮𝑨 = 𝟎
1. Zero Decay
 Rate of loss of the compound is constant
𝒅𝑪ൗ = −𝒌 𝐚𝐧𝐝 𝑮𝑨 = −𝑽𝒌
𝒅𝒕𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏 𝒐𝒏𝒍𝒚
2. First order Decay
 Rate of loss of the compound is directly proportional to its
concentration
𝒅𝑪Τ = −𝒌𝑪 𝒂𝒏𝒅 𝑮𝑨 = −𝑽𝒌C
𝒅𝒕𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏 𝒐𝒏𝒍𝒚
4. Production
 Rate depends on the concentration of other compounds in the reactor
𝒅𝑪ൗ
9 𝒅𝒕𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏 𝒐𝒏𝒍𝒚 > 𝟎
 Summing the reactions over the entire volume yields:

k k
G A   DG Ai   rAi DVi
i 1 i 1

 As k   (that is, as we decrease the size of these cubes

and increase their number)

 DV  0 which gives
V
GA   rA dV
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Generalized Design Equation for Reactors

 In - out + gen - cons = accumulation

V
dN A
FA0  FA   rA dV 
dt

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 Mass Accumulation rate (dN/dt)
 Assume that the volume control is completely mixed
𝑑𝑁 𝑑 𝑉. 𝐶
=
𝑑𝑡 𝑑𝑡
So the concentration and hence the mass within the control volume
remains constant

𝑑𝑁
 In steady state =0
𝑑𝑡
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Process Classification

 Chemical processes can be classified as batch,

continuous or semi-batch and as either transient
or steady state

 Batch process is one in which the feed is charged into the

system at the beginning of the process, and the products
are removed all at once some time later

 Continuous process is when the inputs and outputs flow

continuously across the boundaries throughout the
duration of the process.

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Types of Reactors
 Batch
 No flow of material in or out of reactor
 Changes with time
 Fed- Batch
 Either an inflow or an outflow of material but not both
 Changes with time
 Continuous
 Flow in and out of reactor
 Continuous Stirred Tank Reactor (CSTR)
 Plug Flow Reactor (PFR)
 Steady State Operation

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Batch Reactor
 Generalized Design Equation for
Reactors V
dN A
FA 0  FA   rA dV 
dt
 No flow into or out of the reactor,
then, FA = FA0 = 0
dN A V
  rA dV
dt
 Good mixing, constant volume
dN A d N A V  dC A
 rAV or   rA
dt dt dt
Batch reactors are often used in the early stage of
development due to their ease of operation and
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analysis
 If the reaction is describe by first order kinetics
𝑑𝐶
= 𝑘𝐶
𝑑𝑡

 The reaction time for realizing a desired reactant concentration can

be determined by integrated between the limit C0 (initial) and Cd
(desired)
1 𝐶0
𝑡 = 𝑙𝑛
𝑘 𝐶𝑑

 Batch reactors are often used in the early stage of development due
to their ease of operation and analysis
 Very limited use in field-scale biological wastewater treatment
process, although it should considered for some operation in small
plants and for sludge digestion

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Fed Batch Reactor

 Reactor Design Equation

V dN A
FA0  FA   rA dV 
dt
 No outflow FA = 0
 Good Mixing rA dV term
out of the integral

dN A d C A V 
FA0  rA V  
dt dt
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 Convert the mass (NA) to concentration. Applying integration
by parts yields

dC A dV
 Since FA0  rAV  V  CA
dt dt
dV
 Then  FA0
dt
dC A
 Rearranging FA0  rAV  V  C A FA0
dt
dC A FA0 C A FA0
  rA 
dt V V
 Or dC A FA0
 1  C A   rA
dt V
 Used when there is substrate inhibition and for bioreactors with cells.
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Continuous Stirred Tank Reactor

Q C A0

Q, C A
V, C A

 Assume rate of flow in = rate of flow out

 FA = Q C A and FA0 = Q C A0
 Q = volumetric flow rate (volume/time)
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CSTR - continued
 General Reactor Design Equation
V dN A
FA0  FA   rA dV 
dt
 Assume Steady State dN A  0
dt
V
 Well Mixed  rA dV  VrA
FA0  FA
 So FA0  FA  VrA  0 or V
 rA
 If the reaction rate is assumed a first order reaction 𝑟𝐴 = 𝑘𝐶𝑒 ,
the above eq. is rearranged into the form
𝐶𝑒 1
=
𝐶0 1 + 𝑘 𝑉/𝑄

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 The nominal hydraulic retention time in CSTR is defined
as
𝑉
𝑡𝐶𝑆𝑇𝑅 =
𝑄

𝐶𝑒 1
=
𝐶0 1 + 𝑘𝑡𝐶𝑆𝑇𝑅
 The reaction time required to achieve a desired reactant
concentration :
1 𝐶0
𝑡𝐶𝑆𝑇𝑅 = −1
𝑘 𝐶𝑒

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CSTR in Series
𝐶1 1
=
Q, C0 𝐶0 1 + 𝑘𝑡𝐶𝑆𝑇𝑅
V,C1
𝐶2 1
=
𝐶1 1 + 𝑘𝑡𝐶𝑆𝑇𝑅
V,C2

Q, C2
2
𝐶2 𝐶1 𝐶2 1
= =
𝐶0 𝐶0 𝐶1 1 + 𝑘𝑡𝐶𝑆𝑇𝑅

𝑛 𝑛
𝐶𝑛 1 𝑛 𝐶0
= 𝑛𝑡𝐶𝑆𝑇𝑅 = −1
𝐶0 1 + 𝑘𝑡𝐶𝑆𝑇𝑅 𝑘 𝐶𝑒

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Plug Flow Reactor (PFR)

 Tubular Reactor
 Pipe through which fluid flows and reacts.
 Poor mixing
 Difficult to control temperature variations.
 An advantage is the simplicity of construction.

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 PFR Design Equation
Design Equation V dN A
 FA0  FA   rA dV 
dt
 Examine a small volume element (DV) with length Dy
and the same radius as the entire pipe.
Flow of
Flow of
A out of
A into
Element
Element
 If the element is small, then spatial variations in rA
are negligible, and
Assumption of “good
V mixing” applies only to
 rA dV  rA DV the small volume
element
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 If volume element is very small, then assume steady state with no changes in
the concentration of A.
dN A
0
dt
 Simplify design equation to: FA  y   FA  y  Dy   rADV  0

 rA is a function of position y, down the length of the pipe and reactant

concentration
 The volume of an element is the product of the length and cross-sectional
area,
DV = A Dy
 Design Equation becomes:

 FA  y  Dy   FA  y 
   ArA
 Dy 
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 take the limit where the size of a volume element becomes infinitesimally
small dFA
 ArA
lim
Dy  0 dy

dFA
 or because Dy A = V,  rA
dV
𝑑𝐹𝐴 𝑄.𝑑𝐶 𝑄.𝑑𝐶 𝑄.𝑑𝐶 𝑑𝐶
= = = =
𝑑𝑉 𝐴.𝑑𝑦 𝐴.𝑣.𝑑𝑡 𝑄.𝑑𝑡 𝑑𝑡
 In case of first order reaction
𝑑𝐶
= −𝑘𝐶
𝑑𝑡
𝐶𝑡
= 𝑒𝑥𝑝 −𝑘𝑡
𝐶0
 The time required to obtain a desired reactant concentration in the effluent
1 𝐶0
𝑡𝑃𝐹 = 𝑙𝑛
𝑘 𝐶𝑒
 This is the Design Equation for a PFR

 Bioapplications - Sometimes hollow fiber reactor analysis is simplified to a

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Operating Characteristic of Different
Reactor Systems

Reactor Type Variation of Variation of

Composition with time Composition with
position in reactor
CMB Yes No
CSTR No No
PF Yes Yes

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Homework
Compare the total volume requirement for the following
reactor systems:
a. CMB reactor
b. Single CST reactor
c. Two CST reactor connected in series
d. PF reactor
It is desired that the reactant concentration be reduced
from 100 mg/L to 20 mg/L for the flow 50m3 day-1. Assume
the first order reaction kinetics are followed and the rate
constant has a value of 0.216 day-1.

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