Environmental Engineering Unit Operations

MU- Department of -Env.Eng.- Enve 301 Course Notes- Dr.
Bilge Alpaslan Kocamemi
ENVE 301
Environmental Engineering Unit Operations
CHAPTER: 2
Reaction kinetics
Material balances
Assist. Prof. Bilge Alpaslan Kocamemi

Marmara University
Department of Environmental Engineering
Istanbul, Turkey
1
MU- Department of -Env.Eng.- Enve 301 Course Notes- Dr. Bilge Alpaslan Kocamemi
Stoichiometry Reaction Kinetics

Material Balances
Stoichiometry:
aA + bB + cC +
A, B, C
P, Q, R
a, b, c, p, q, r
pP + qQ + rR +
Reactant species
Product species
Stoichiometric coefficients
Reactant stoichiometric coeff. = ( - ) sign

for irreversible reactions
Product stoichiometric coeff. = ( + ) sign
aA + bB + cC +
Pp + qQ + rR +
Signs of both reactants and products ( + )
for reversible reactions

2
Classes of Reactions That Occur In Nature

Homogenous Reactions
Heterogenous Reactions
Reactions that occur within a single phase

(i.e., liquid, solid or gas)
Reactions that occur at surfaces between

phases.
Reactants are distributed continuously(but

not necessarily uniformly) throughout the
fluid.
Examples:
Reactions on the surface of ion exchange resin
Reactions that require the presence of a solid
phase catalyst
1a. Single irreversible reaction:

A
B A+A
B
aA + bB
1b. Multiple irreversible reaction:
B
A
(Parallel reaction) A
B
C
C
(consecutive or series reaction)
1c. Reversible reaction:
A B
A+B C+D
Rate and Order of Reaction

Rate of reaction
The rate at which reactant disappears or a

product is formed in any given stoichiometric
reaction.
For homogeneous rxn
Rate of reaction (r )
For heterogeneous rxn
Reactants
Products
mol
r=
Lt
mol
r=
mt
2
have negative (-) rates of rxn.

have positive (+) rates of rxn.
4
@ constant temperature,
the rate of rxn. (disappearance of a reactant or formation of a product) is
some function of the concentration of the reactants
aA + bB
cC + dD
order of the rxn. respect to individual reactants A and B
(0, 1, 2 may be fractional)
Overall rate of rxn = r=
k [A] [B]
(mol/Lt)
molar concentrations of
reactants (mol/ L)
reaction rate
constant
Overall order of rxn = +

Order of rxn with respect to reactant A =
Order of rxn with respect to reactant B =
Unit of k (reaction rate constant)

For 0 order rxn.
r = k[A]
For 1st order rxn.

r = k [A]
For 2nd order rxn.

r = k [A]
k=
mol
Lt
r=k
mol
1
k = Lt =
mol
t
L
mol
L
Lt
k=
=
(mol / L ) mol .t
2
Example :
r = k [A] [B]
Order of overall rxn. = 2 + 1 = 3
Order of rxn. with respect to reactant A = 2
Order of rxn. with respect to reactant B = 1
Stoichiometric Relationships Between Rates of

Reactions
ra = rb = rc = rd
aA + bB
cC + dD
a b c d
Example :
3A
2B + C
If the overall rate of rxn is 1st order wrt to A , then r = k [A]
ra = rb = rc
r = 3 2 1
ra = rxn. rate wrt to A = -3 k [A]
rb = rxn. rate wrt to B = 2 k [A]
rc = rxn. rate wrt to C = k [A]
The one limits the overall rxn rate
slowest one
Types of Reactions and Reaction Rates
irreversible rxns
reversible rxns
saturation rxns
autocatalytic rxns
9
Irreversible Reactions
a)Single Irreversible Rxns:
A
P
A+A
aA + bB
P
P
ra
rb
r=
=
= rp
a b
Example:
aA
pP
r = k [A]
ra = -a k [A]
rp = p k [A]
(Rxn. rate
1st order)
10
b)Multiple Irreversible Rxns:

b-1) Parallel rxns:
k1
r
1
bB
aA
r
r
r = a = c
2 a c
k2 cC
Overall rate of rxn:
r
r
a = b
a b
r1 + r2
ra
= 2
a
r r
= b+ c
b c
Rate of rxn with respect to A = ra = -ar1 ar2

Rate of rxn with respect to B = rb = b r1
Rate of rxn with respect to C = rc = cr2
11
k1
bB
k2
cC
aA
If both of the rates of rxn
1st order
r1= k1[A]
r2= k2[A]
rA= -ak1[A] - ak2[A]
rB= bk1[A]
rC= ck2[A]
12
b-2) Consequtive rxns
k1
k2
aA bB cC
k1
aA bB
k2
bB cC
ra rb
r =
=
1 a b
r
r = rb = c
2 b c

r1= k1[A]
r2= k2[B]
ra = - a r 1
rb = b r 1 b r 2
rc = c r2
1st order
ra= -ak1[A]
rb= bk1[A] - bk2[B]
rc= ck2[B]
13
Reversible Reactions
aA
k1
bB
k2
aA
bB
k1
k2
bB
aA
r
r
r = a = b
1 a b
r
r
r = b= a
2 b a
ra = ar1 + ar2
rb = br1 + br2
Note:
for reversible rxns signs of stoichiometric coefficients
(both reactants & products) are always positive (+)
r1= k1[A]
r2= k2[B]
1st order
ra= ak1[A] + ak2[B]

rb= bk1[A]+ bk2[B]
14
Saturation Type Reactions

Saturation type reactions have a maximum rate that is a point at which
the rate becomes independent of concentration A.
For the reaction aA
bB
k [A]
r=
K + [A]
r = rate of rxn, mol /Lt
[A] = conc. of reactant, mol / L
k = rxn rate constant, mol/ Lt
K = half saturation constant, mol/ L
Fig.1.Graphical representation of Saturation Type Reaction

Ref: Tchobanoglous and Scroeder, 1985, Addison-Wesley Publishing Company
15
Saturation Type Reactions (continue)

k[A]
r=
K + [A]
When K << [A]
r = k [A] k (zero order)

K + [A]
Negligible
Ref: Tchobanoglous and Scroeder, 1985, Addison-Wesley Publishing Company
When K >> [A]
r = k [A] k [A] (first order)

K + [A]
K
Negligible
16
Saturation Type Reactions (continue)

For the reaction A + B
[A] [B]
k [A] [B]
= k
r=
K + [A] K + [B]
K + [A]
1
2
17
Autocatalytic Reactions
Autocatalytic reaction rates are functions of the product concentration.
Example: Bacterial growth

(rate of increase in bacterial number is proportional to the number present)
Autocatalytic rxns can be
1st order
2nd order
Saturation Type
Partially Autocatalytic (function of
reactant & product)
18
1st order Autocatalytic Rxn.

aA
bB
ra rb
=
r = k [B] =
a
b
ra = a k [B]
rb = b k [B]
2nd order Autocatalytic Rxn.

aA
Bb
ra rb
=
r = k [B] [A] =
a
b
ra = a k [A][B]
rb = b k [A] [B]
19
Effects of Temperature On
Reaction Rate Coefficients
The temperature dependence of the rate constant is given by
Vant Hoff- Arhenius relationship
k2
( T2 _ T1 )
=
k1
20
Analysis of Experimental Data

Methods to determine the order of a reaction from experimental data
1-) Method of Integration

Most commonly used
2-) Differential Method
3-) Time Reaction Method
4-) Isolation Method
21
I.Method of Integration
Integrated forms of the various rate expressions (Oth order, 1st order etc)
Plotting the experimental data functionally based on the integrated form
of the rate expression
If straight line plot is obtained
It is assumed that the order of the rxn

corresponds to the rxn. plotted
Determine the reaction rate constant from the plotting

22
a) Irreversible Zero-Order Reaction

rA =
d[ A ]
= k [ A ]0 = k
dt
rA =
d[ A ]
= k
dt
c a(t )
ca 0
( ) d[ A ] = k.dt
To determine reaction rate constant (k)
Ca(t)
Ca( t) = Ca(0) kt
Plot Ca(t) versus t

23
b) Irreversible First Order Reaction

rA =
C a (t)
C a (0)
d[A]
= k[A]
dt
t
d[A]
= k dt
[A]
0
LnC a(t) LnC a(0) = kt

C
Ln a(t) = kt
C a( 0 )
C =C e
kt
a(t)
a(0)

C
Plot Ln a(t) versus t
Ca(0)
24
Half Life
Time required for the amount of substance to decrease to half its initial value
Ca
( t1 / 2
=
)
Ca
(0 )
For 1st order rxn :
Ca
Ca
(t)
(t1 /2 )
Ca
2
(0 )
C a(0 ) . e
=
Ca
1 2=e
kt
.
(0 ) e
a (0 ) . e
k .t1 /2
k .t1 /2
k . t1 / 2
1
Ln = Ln. ek.t1 /2
2
1
Ln = k.t 1 / 2
2
t1 / 2 =
Ln2 0 .693
=
k
k
25
c) Irreversible Second Order Reaction

rA =
C a
A+A
d[A]
= k[A]2
dt
(t)
C a (0)
t
= k dt
2
[A]
0
d[A]
1
1
= kt +
C a ( t)
C a (0 )

1
Plot
versus t
C a (t )
1/Ca(t)
1 Ca (t)
|Ca (0) = kt
[A]
26
d) Irreversible Parallel Reaction (1st order)

k1
bB
k2
cC
r1 = k 1 [A] =
ra
r
= b
a
b
r2 = k 2 [A] =
ra
r
= c
a c
aA
a, b, c = 1
d [A]
ra =
= k 1 [A] k 2 [A]
dt
rb =
d[B]
= k 1 .[A]
dt
rc=
d[C]
dt
= k 2 [A]
27
d) Irreversible Parallel Reaction (1st order-continue)

d[A]
= k 1 [A] k 2 [A]
dt
k1
bB
ra =
k2
cC
d[A]
= (k 1 + k 2 ).[A]
dt
aA
t
Ca (t)
d[A]
= (k + k ). dt
1
2
[A]
Ca (0)
0
(LnC
LnC
(t)
Ca
Ln
Ca
(t)
LnC
a(0 ) )
LnC a ( 0 ) =
( t)
= (k 1 + k 2 ). t
(k 1 + k 2 ). t
= (k 1 + k 2 ). T
(0 )
C a( t) =
C a(0 ) . e
(k 1 + k 2 ). . t
28
k1
bB
rb
d[B]
=
rc
d[C]
dt
k .[A]
= 1
dt
k 2 .[A]
aA
k2
cC
Cb
d [B]
Cb
(t)
rb
d[B]
k
=
= 1
rc
d[C]
k2
k2
(0)
Cc
[C]
Cc
(t)
= k1
(0)
k 2 .[C b ( t ) C b ( 0 ) ] = k1 .[Cc ( t ) Cc ( 0 ) ]
k1 =
k 2 [C b ( t ) C b ( 0 ) ]
[ Cc
(t )
Cc
(0)
29
II.Differantial Method
Assumption: The rate of rxn is proportional to the nth power of concentration.
d[A]
rA =
= k[A] n
dt
For 2 different concentrations at 2 different times;

t = t1 ,
A = A1
t = t2 ,
A = A2
d [ A1 ]
= k [ A1 ] n
dt
d [ A2 ]
= k [ A2 ] n
dt
30
If logarithm of each of the above equation is taken and the k values are
equated:
d[A 1 ]
= k[A 1 ] n
dt
d[A 1 ]
log
= logk + nlog[A 1 ]
dt
n=
d[A 2 ]
d[A 2 ]
n
log
= logk + nlog[A 2 ]
= k[A 2 ]
dt
dt
log( d[A 1 ] dt ) log( d[A 2 ] dt )

log[A 1 ] log[A 2 ]
31
Example:
Determine the order of the reaction and the reaction rate constant for the
following data derived from on experiment carried out in a batch reactor.
Solve the problem
a)Using Integration Method
b)Using Differential Method
Time
(min)
0
1
2
3
4
5
6
7
8
9
10
[A]
mol/L
100
50
37
28.6
23.3
19.6
16.9
15.2
13.3
12.2
11.1
32
A)Integration Method
For
1st
order rxn ; C a(t) = C a
(0)
e t
C a(t)
Ln
= kt
C a(0)
For 1st Order Reaction

Time
(min.)
0
1
2
3
4
5
6
7
8
9
10
[A]
mol/L
100
50
37
28.6
23.3
19.6
16.9
15.2
13.3
12.2
11.1
Time -Ln [Ca(t)/Ca(0)]

0
1
2
3
4
5
6
7
8
9
10
0
0.69
0.99
1.25
1.46
1.63
1.78
1.88
2.02
2.10
2.20
Time (t)
33
For 2nd order rxn;
C A ( t)
= kt +
1
C A (0)
For 2nd Order Reaction

[A]
mol/L
100
50
37
28.6
23.3
19.6
16.9
15.2
13.3
12.2
11.1
Time
0
1
2
3
4
5
6
7
8
9
10
1
C a (t )
0.01
0.02
0.03
0.03
0.04
0.05
0.06
0.07
0.08
0.08
0.09
0,10
0,08
1/Ca(t)
Time
(min.)
0
1
2
3
4
5
6
7
8
9
10
0,06
0,02
y = 0,0079x + 0,0112
R = 0,9994
y = 0,0079 x + 0,0112
0,00
R 2 = 0,9994
0,04
10
15
Time (min)
Slope(k) 0,0079 L/mol.t
34
B) Differential Method
log (- d[A 1 ]/ dt ) - log (- d[A 2 ]/ dt )
n=
log [A 1 ] - log [A 2 ]
[A t +1 ] - [A t 1 ]
dt
Choose any data;

Time
[A] ,mol/L
37
16.9
d[A]/dt
28 .6 - 50
= -10.7
3-1
15 .2 - 19.6
= -2.20
7-5
log( -(-10.7)) - log(-(-2.2 0)) 1 .029 - 0.34

n=
=
=2
log [37 ] - log[16.9]
0 .34
35
To find k;
@ t=2min
d[A ]
= -10.7
dt
[A]=16.9 mol/L
d[ A ]
= -kC 2
[dt ]
-10.7=-k.372
k=0.0078
[A]=37 mol/L
@ t=6min
rA =
d[A]
= -2.20
dt
d[A]
rA =
= -kC 2
[dt]
-2.20=-k.16.92
k=0.0078
36
Materials Balance
Materials Balance
(mass balance )
quantitative description of all materials

that enter, leave and accumulate
in a system with defined boundaries.
based on the law of conservation of

mass (mass is neither created nor
destroyed)
is developed on a chosen control

volume.
37
Rate of
Rate of flow
accumulation
of mass into
of mass within = the system
the system
boundary
boundary
Accumulation =
Inflow
Rate of flow
of mass out
of the system
boundary
Outflow
Rate of mass
generation
+
within
the system
Generation
38
Accumulation = Inflow - Outflow + Generation

Generation term. can be + or -
[Most of the materials of interest disappear and therefore generation term is - in most cases.]
Symbolic Representation:
Accumulation =
dC
dt
Inflow
Outflow
( QC O
) - QC
+ Generation
= volume of the reactor, m3

dc
= rate of change of reactant concentration within the reactor (g / m3 sec)
dt
Q = flow into and out of the reactor ( m3 /sec)

Co=concentration of reactant in the influent (g/ m3 )
C=concentration of reactant in the reactor and effluent (g/ m3 )
r = rate of generation (g/ m3 sec)
39
Operational states that must be considered in the application of materials

balances:
Steady state:
There is no accumulation in the system.
All rates and concentration do not vary with time.
CA
t
=0
Example: Pump discharging constant value of water within time.
Unsteady (transient) State:

Rate of accumulation is changing with time
C A
0
t
Example: Filling a reservoir pumping, of the contents of a tank.
40

Environmental Engineering Unit Operations

Încărcat de

Informații document

Descriere originală:

Drepturi de autor

Formate disponibile

Partajați acest document

Partajați sau inserați document

Opțiuni de partajare

Vi se pare util acest document?

Este necorespunzător acest conținut?

Drepturi de autor:

Formate disponibile

Environmental Engineering Unit Operations

Încărcat de

Drepturi de autor:

Formate disponibile

MU- Department of -Env.Eng.- Enve 301 Course Notes- Dr.

Bilge Alpaslan Kocamemi

Assist. Prof. Bilge Alpaslan Kocamemi

Stoichiometry Reaction Kinetics

Reactant stoichiometric coeff. = ( - ) sign

Signs of both reactants and products ( + )

for reversible reactions

Classes of Reactions That Occur In Nature

Reactions that occur within a single phase

Reactions that occur at surfaces between

Reactants are distributed continuously(but

1a. Single irreversible reaction:

Rate and Order of Reaction

The rate at which reactant disappears or a

have negative (-) rates of rxn.

Overall rate of rxn = r=

Overall order of rxn = +

Unit of k (reaction rate constant)

For 1st order rxn.

For 2nd order rxn.

Stoichiometric Relationships Between Rates of

Types of Reactions and Reaction Rates

b)Multiple Irreversible Rxns:

Overall rate of rxn:

Rate of rxn with respect to A = ra = -ar1 ar2

If both of the rates of rxn

b-2) Consequtive rxns

If both of the rates of rxn

ra= ak1[A] + ak2[B]

Saturation Type Reactions

Fig.1.Graphical representation of Saturation Type Reaction

Saturation Type Reactions (continue)

When K << [A]

r = k [A] k (zero order)

Ref: Tchobanoglous and Scroeder, 1985, Addison-Wesley Publishing Company

When K >> [A]

r = k [A] k [A] (first order)

Saturation Type Reactions (continue)

Example: Bacterial growth

Autocatalytic rxns can be

1st order Autocatalytic Rxn.

2nd order Autocatalytic Rxn.

Analysis of Experimental Data

1-) Method of Integration

If straight line plot is obtained

It is assumed that the order of the rxn

Determine the reaction rate constant from the plotting

a) Irreversible Zero-Order Reaction

To determine reaction rate constant (k)

Plot Ca(t) versus t

b) Irreversible First Order Reaction

LnC a(t) LnC a(0) = kt

To determine reaction rate constant (k)

For 1st order rxn :

c) Irreversible Second Order Reaction

To determine reaction rate constant (k)

d) Irreversible Parallel Reaction (1st order)

d) Irreversible Parallel Reaction (1st order-continue)

For 2 different concentrations at 2 different times;

log( d[A 1 ] dt ) log( d[A 2 ] dt )

order rxn ; C a(t) = C a

For 1st Order Reaction

Time -Ln [Ca(t)/Ca(0)]