Module II: application of mass balance in reactor

design, Fundamentals of process kinetics

Dr. Shihabudheen. M. Maliyekkal, PhD

Associate Professor, School of Mechanical and Building Sciences, VIT
Chennai, Campus, Chennai, India
https://scholar.google.com/citations?user=QYutTIcAAAAJ
http://www.researchgate.net/profile/Shihabudheen_Maliyekkal
 Material balance
mass balances are based on the
fundamental law of conservation of
mass
Doing a material balance is similar in
principle to accounting.

Accumulation Mass out

Mass in Reaction: Decay
and generation

Control
volume
 Material Balance
Fate of mass inside control volume
(CV)
May leave the CV unchanged
May accumulate with in the CV
May be converted to some other
substance
May produce more substance inside
the CV
Accumulation = {(Mass in - Mass
out) + reaction}

Accumulation rate = {(rate of mass -

rate of mass out) + reaction} Reaction = rate of generation-
rate of consumption
 Types of Balance
Differential Balance
It is a balance taken at a specific instant in time. It is generally
applied to a continuous process. If the process is at steady
state, a differential balance applied at any time gives the same
result. Each term in a differential balance represents a process
stream and the mass flow rate of the materials in that
stream.
Integral balance
It is a balance taken at two specific instants in time. It
describes what has happened over the time period between the
two points. An integral balance is generally applied to the
beginning and the end of a batch process. It accounts for what
happens to the batch of chemicals. Each term in an integral
balance represents a process stream and the mass of the
material(s) in that stream.
 Material Balance
Steady-state process.
Process that does not change with time. Every time
we take a snapshot, all the variables have the same
values as in the first snapshot.

Unsteady-state (Transient) process

Process that changes with time. Every time we take a
snapshot, many of the variables have different values
than in the first snapshot.
 Material Balance Cond..
Steady state conservative system
Input rate = output rate

Stream 1
Cs, Qs
Mixed
Accumulation
stream
Reaction: Decay and
Cm Qm
Waste generation
Cw Qw

Cs Qs + CwQw = CmQm
 Batch system with Neoconservative pollutant

No flow into or out of the system

Accumulation rate = Reaction rate

C = C o kt
V dC/dt = -VKo
C =C 0 e kt
V dC/dt = -VK1C
C0
V dC/dt = -VK2C2 C=
1 + C 0 kt

Ko rate coefficient (mg/L s) zero order

K1 rate coefficient (1/s) first order
 Zero Order Reaction

Conc. of reactant, C
rC = k 0
dC
= k 0 Slope = -ko
dt
Ct t
dC Time, t

C0
dt
= k 0
o

Ct = Co k 0 t
First Order Reaction
dC
= k1 C
dt
Ct

lnCt
dC
= k1C Slope = -k1

C0
dt
Time, t
k1t
C t =C 0 e
ln C t =ln C 0 k1t Linear form
 Second order reaction
Slope = k2
dC

1/Ct
= k 2 C 2

dt
Ct t
dA
= 2k C 2 Time, t

C0
dt o

C0
Ct =
1 + C0 k 2t
1 1
= kt Linear form
Ct Co
Conc., mg/L Batch system with neoconservative pollutant

Time, h
Batch system first order kinetics
Batch system zero order kinetics
Decay

Batch system second order kinetics

 Steady-state system with nonconservative pollutants

Accumulation = 0.0
0=Input output rate +reaction rate

Problem: 1
Consider a 10 x 106 m3 lake fed by polluted stream having flow rate of
5.0 m3/s and pollutant concentration equal to 10 mg/L . There is
also a sewage outfall that discharges 0.5 m3/s of wastewater having
a pollutant concentration of 100 mg/L. The stream and sewage
wastes have a decay rate coefficient of 0.20/day. Assuming the
pollutant is completely mixed in the lake and assuming no
evaporation or other water loss or gains, find the steady-state
pollutant concentration in the lake ( Ans = 3.5 mg/L)
 Problem 2

Every year, a group of birds move along 4.75 km stretch of

stream connecting a lake to the ocean to catch the
fingerling salmon as they migrate downstream connecting a
lake to the ocean. The birds are efficient in catching fish
and will consume 10,000 fingerlings per kilometer of stream
each hour regardless of the number of salmon in the stream
(number of salmon available are not limited). The streams
average cross-sectional area is 20 m2, and the salmon move
downstream with the streams flow rate of 700 m3/min. If
there are 7 fingerlings per m3 in the water entering the
stream, what is the concentration of salmon that reach the
ocean when birds are feeding?
Ans: ~ 6 fish/m3
Hint: Zero order reaction
 Problem 3
A smoking room with volume 500 m3 has 50 smokers in it, each
smoking 2 cigarettes per 60 min. An individual cigarette emits,
among other things, about 1.4 mg of formaldehyde (HCHO). HCHO
converts to carbon dioxide with a reaction rate coefficient, K=0.4/h.
Fresh air enters the smoking room at the rate of 1,000 m3/h, and
polluted air leaves at the same rate. The analysis of inlet air showed
that the concentration of HCHO outside the smoking room is =0.0.
Assuming complete mixing, estimate the concentration of
formaldehyde in the outlet air.
Ans: 0.117 mg/m3
Hint : steady state condition ---- accumulation = 0
Reaction term = Generation Decay ( first order reaction)
 Non-steady state system

Flow in Flow out

CV
Q, Ci Volume = V
Conc. = C Q, C

Accumulation rate = {(rate of mass in - rate of mass out) +

reaction}
V dC/dt= {(QCi - QC VKdC+ KgV)

V = box volume (m3)

C= conc. of the pollutant inside the box and the effluent (g/m3)
Ci = inlet conc. of the pollutnat ( g/m3)
Q = the flow rate (m3/s)
Kd = decay rate coefficient (I /h)
Kg= generation rate coefficient (g.m/h)
At steady state condition,

,
dc
=0
dt
QC i + k g V
C =
Q + k dV
C = Conc. at time t
Conc. before reaching steady state condition

dc Q QC i + K g V
= + k d .
C
3
dt V Q + K dV
Equation 3 can be rewritten as
Q
+ k d .(C C )............ 4
dc
=
dt V
Substitute (C C ) = y...............5
dy dC
= ...............6
dt dt
dy Q
= + k d y...............7
dt V
y
Q
t

y dy / y =
V
+ k d dt ...............8
0
o

Q
+ k d
y = y0 e V
...............9
Q
+ k d t
C C = (C 0 C )e V
...............10
Q
+k d t
C( t) = C +( C 0 C ) e V
.......... .....11
Problem 4
The smoking room in the Problem 3 had volume of 500 m3 with fresh air entering at
the rate of 1, 000 m3/h. Suppose when the bar open at 5. pm., the air is clean. If
HCHO, with decay rate = 0.4/h, is emitted from cigarette smoke at the constant rate of
140 mg/h starting at 5 P.M., what would be the concentration at (a)6 P M, and (b) 8
PM?

Problem 5
Consider the 10 x 106 m3 lake analyzed in example problem 1which, under the
considerations given, was found to have a steady state pollution concentration 3.5
mg/L. The pollution is nonconservative with reaction rate constant kd =0.2/day.
Suppose the condition of the lake is deemed unacceptable. To solve the problem, it is
decided to completely divert the sewage outfall from the lake, eliminating it as source
of pollution. The incoming stream still has flow Qs = 5.0 m3/s and concentration Cs =
5.0 m3/s. Assuming complete-mix conditions, find the concentration of pollutant in the
lake one week after the diversion, and find the new final steady state concentration?
Wastewater Treatment
Basics
 Reactions
Reaction Kinetics
Reactions are dependent on various factors
Temperature
Pressure
Time
Concentration
Examples: biodegradation of organic matter, chemical
oxidation of pollutants, chemical disinfection
Reaction kinetics: Study of the effect of above mentioned
parameters on the rate of a reaction
Homogenous reaction reaction that occur with in a
single phase
Heterogeneous reaction reactions that involve two or
more phases
 Rate of a reaction: this describe the rate of formation of a
product or rate of disappearance of a reactant

Reactants product

aR1 + bR2 cP

Stoichiometric coefficient
Rate of reaction:
rA = k [ R1 ] [ R2 ]
x y
= k[ P] z

K = reaction rate constant

x, y, z empirically determined from
experiment
[R1], [R2], [P] - molar concentration of R1, R2,
and P Zero order
Reaction rate

First order

Second order
time
 Order of reaction = sum of the empirically determined
constant
x+y with respect to R1 and R2
z- with respect to P
For a homogenous, irreversible, elementary reaction
that occur in a single step, the empirically determined
exponent are equal to the stoichiometric coefficient

rA = k [ R1 ] a [ R2 ]b = k [ P ] c
 How to find the order of a reaction

AB
rA = k [ A] x

ln( rA ) = ln(k ) + x ln[ A]

Concentration of the reactant,

ra, = Slope of the tangent

[A]

Time, t
 Log(-rA)

Slope = x

X= order of the
log(k) reaction
k= reaction rate
Log [A] constant
 The following data were obtained from a batch
experiment for the reaction A P. determine the
order of the reaction

Time ( min) A ( mg/L)

0 100
10 74
20 55
40 30
60 17
80 9
100 5
 Zero Order Reaction

Conc. of reactant, A
rA = k 0
dA
= k 0 Slope = -ko
dt
At t
dA Time, t

A0
dt
= k 0
o

At = Ao k 0 t
First Order Reaction
dA
= k1 A
dt
At

lnAt
t
dA
= k1 A Slope = -k1

A0
dt o
Time, t
k1t
At = A0 e
ln At =ln A0 k1t

Linear form
 Second order reaction
Slope = k2
dA

1/At
= k 2 A 2

dt
At t
dA
= k 2 A 2 Time, t

A0
dt o

A0
At =
1 + A0 k 2 t
1 1
= kt Linear form
At Ao
 Reactors
Batch Reactors

Concentration
of reactant

Time

Accumulation = input mass- output mass + Rate

of consumption
 For a batch reactor, input mass = output mass =0.0
(Here the reaction starts just after the reactor is filled
and the reaction ends just before the contents are
emptied)

Rate of consumption=Accumulation

rA = V (dC / dt )
Vk1C = V (dC / dt ) First order
reaction
Vk 2 C 2
= V (dC / dt ) Second order

= V (dC / dt )
reaction
Vk o C 0
Zero order reaction
Vk o = V (dC / dt )
 Consider a first order reaction taking place in a batch
reactor. Develop an expression for the detention time
in the reactor.
 Continuous flow stirred tank reactor (CSTR) or
completely mixed reactor

Influent, Effluent
Co C

Effluent reactant conc.

V, C

Time, t
 Assumptions:
Reactor content are completely mixed and homogenous
throughout
When a reactant [Co] enters the reactor, it is subjected to
instantaneous and complete mixing. This leads to the immediate
reduction to the final effluent concentration
Reactor is running under steady state condition

% particles

Residence time
 A tracer molecule in the influent has equal probability
of being located anywhere in the reactor after a small
time interval
All fluid elements in the reactor have equal probability
of leaving the reactor with effluent in the next time
increment
 Governing equations

Accumulation rate= input mass rate- output

mass rate + Rate of consumption
Steady state condition
0.0 = input mass- output mass + Rate of
consumption
dC
V = QC o QC t + rCV
dt
0 = QC o QC t + ArAV
0 = QC o QC t + kCV first order
0 = QC o QC t + kV Zero order
0 = QC o QC t + kC 2V . Second order
V (dC / dt ) = QC o Qe C t Vk1C t first order
0 = QC o Qe C t Vk1C t
Ct 1
=
C o 1 + k1 [V / Q]
Ct Q
V = 1
Co k1
Ct 1
=
C o 1 + k1 [t ]
Co 1
t = 1 .....................t = HRT
Ct k1
................................................................................................
V (dC / dt ) = QC o Qe C t Vk 2 C t2 .............Second order
0 = QC o Qe Ct Vk 2 C t2 .
Co Ct Q
V =
2 k
C t 2
Ct 1
=
C o 1 + k 2 tC t
1 Co Ct
t =
k 2 C t2
1 Co
t= 2 1......................t = HRT
k 2 Ct C
t
 A chemical reaction takes place in CSTR, where A is
converted to Product P. The initial concentration of A
is 45 mg/L. After 5 min, concentration of A is
measured as 36 mg/L.

Calculate the rate coefficient assuming that the

reaction is first order
Calculate the rate coefficient assuming that the
reaction is second order
 Problem for practice
(deadline 4-10-13)
Problem: Determine the order and reaction rate of
the reaction for the following data obtained from
a batch experiment. (Use excel or origin)

Conc. 235 135 100 55 30 20

mg/L
Time, min 0 7 15 25 35 40
 Fit the given adsorption data using the following expressions
and find out the best fit. Also, estimate the value of the of the
parameters qe, k. (Use excel or origin). The amount of
adsorbent used is 1 g/L. Initial concentration of fluoride= 5
mg/L

Pseudo first order

qt = q e 1 e ( k1t
)
model
qe2 k 2t
Pseudo second order qt =
model 1 + qe k 2t
qe amount of fluoride removed from aqueous solution at equilibrium (mg g-1)
qt amount of fluoride adsorbed on the adsorbent surface at any time t (mg g-1)
k1 pseudo-first-order rate constant of adsorption (min-1)
k2 pseudo-second-order rate constant of adsorption (g mg-1 min-1)
t reaction time (min)

Note:q = (Co-Ce)/adsorbent dose

Initial conc. of time,
fluoride, Co min Ce Qexp
5 0 5 0
5 2.5 1.6 6.8
5 7 0.63 8.74
5 12 0.4 9.2
5 17 0.34 9.32
5 22 0.31 9.38
5 30 0.209 9.582
5 45 0.192 9.616
5 60 0.19 9.62
5 90 0.18 9.64
5 120 0.16 9.68
5 180 0.15 9.7
 Derive an expression for the detention time in a batch
reactor. Assume the reaction follows first order.
Derive an expression for the detention time in a batch
reactor. Assume the reaction follows zero order.
Derive an expression for the detention time in a batch
reactor. Assume the reaction follows second order.
 A CSTR is used to treat 10 MLD of wastewater. The reactor is
designed to bring a influent BOD concentration of 250 mg/L
to an effluent BOD concentration of 20 mg/L through
chemical oxidation. The value of reaction rate constant is
estimated to be 0.6/day.
Determine the volume of the reactor
Determine the hydraulic retention time

Find the HRT and volume of the reactor for a reaction rate
constant of 0.05 L/mg d
 A batch reactor of volume 80000 L is used to treat
wastewater from a milk processing industry (BOD=1000
mg/L). The reactor is designed to achieve a removal
efficiency of 90%. Calculate the maximum volumetric
loading that the reactor can handle .
Due to some complaints form the local people, the
pollution control board has asked the industry to increase
the efficiency of treatment to 99%. What modification
your would suggest to achieve the new treatment
efficiency.
.
 Reactor in series
Influent,
Influent, C1 Effluent
Co C2

C1 1 C2 1
= =
C o 1 + k1 [V / 2Q] C1 1 + k1 [V / 2Q]
 C1
C2 =
1 + k1 [V / 2Q]
C1
C2 =
1 + k1 [V / 2Q]
1 C0
C2 =
1 + k1 [V / 2Q] 1 + k1 [V / 2Q]
C0
C2 = 2
(1 + k1 [V / 2Q])
 A CSTR reactor is designed to treat wastewater (Q =
1500 m3/d) from a milk processing industry. The reactor
is designed to remove 90% of the influent BOD. Assume
the reaction rate 0.23/day.