Reaction 1

1
-:
-:
.1
.2
1
CHAP . 1 MOLE BALANCES
The rate of the reaction , -rA
The rate of the reaction tell us how fast a number of moles of one
chemical species are being consumed to form another chemical
species .
The term chemical species refers to any chemical component or

element with a given identity.
The identity of a chemical species is determine by
1.kind 2. Number 3.configuration of that species "

atoms " .
Any change ( 1.2.3 ) identity change
Ar : - chemical species ( change in A identity per unit time per unit

volume )
* The symbol rj
-rj : - ( mole j consumed / reacted / disappeared ) / time * volume
rj : - ( mole j produce /appeared ) / time * volume )

Various type of industrial reactors :-
1. continuous reactor
2. batch reactor
3. semi batch reactor
1 continuous flow reactor
a. CSTR :- continuous stirred tank reactor
b. PFR :- plug flow reactor
c. packed fed reactor
TYSIR SARHAN HAYTHAM ALZOUBI

2
2.batch reactor
t0=0 t 1 = final time
NA0 :- initial mole of A

CA0 = CA =

Batch reactor balance
In out +generation = accumulation
In =out = 0
Generation = accumulation

=

t= assume v = v0 = constant

Time necessary to reduce the number of moles of A from NA0 to NA.

X= =

NA :- MOLES OF A UNREACTED
-rA= K CA CB
+=n
th order with respect to A
order with respect to B
n order overall
K : constant rate of chemical reaction =

((volume / mole ) n-1)/time

3
EX1
What the time needed so that the final moles of A become

10% of its initial value in 10 L batch reactor
Where rA = 0.1 min-1 CA

t=

t= . CA = NA / V

t=-10 * NA=0.1 NA0

t = 23 min
.
X= = = X = 0.9

PROBLEM 1/15 /d
The reaction A
calculate the time necessary to consume 99.9%

of species A in a 1000 dm3 constant volume batch reactor with
CAo = 0.5 mol/dm3

(a) -rA = k with k = 0.05
.
( )
t= =

=
. .
.
t= -20 * ( 0.001 CA CA )

.
t= -20 *-0.999 *0.5 = 9.99 h

(b) -rA = kcA k = 0.0001 s-1

c) -rA = kcA2 =
.

4
CSTR( molar flow rate)
In out +generation=accumulation
Assumption
a. good mixing ( ci = cf )
b. steady state
* for liquid phase v=v0
*for gas phase vv0 ( (
FA0-FA+rA*v=0
CSTR volume necessary to reduce the molar flow

rate from FA0 to FA.

V= FA = CA * V


5
Problem 1/15
The reaction A
is to be carried out isothermally in a
continuous-flow reactor. Calculate
the CSTR reactor volume necessary to
consume 99% of A
(CA= 0.01CA,) when the entering molar flow
rate is 5 mol/h, assuming the reaction
rate -rA is:
(a) -rA = k with k = 0.05 mol/L.h
(b) -rA = kCA with k = 0.0001 s-1
(c) -rA = kCA with k = 3 dm3/mol.h
*The entering volumetric flow rate is 10 dm3/h
For a constant volumetric flow rate v=v 0
a:-

V= FA = CA * V FA0 = CA0 * V

3
CA0 = = 0.5 mol / dm

V=

V= . (. )
.
.
V= 99 L or 99 dm3

6
Plug Flow Reactor
( Tubler , PFR , plug )

CA decreasing as L increasing
X increasing as L increasing
X = 1 CA0 = 0 when reversible and complete reaction
X PFR > X CSTR
X or CA change axially or longitudinally( )
( no change in r direction )
In tubluar reactor when CA decrease V increase and X
increase
Assumption
Steady state
X or CA change in L direction
X or CA doesn't change in r direction

V =

what is the volume of tubler reactor so that FA= 0.1

V = -10 * -0.9 * 10 = 90
FA0
L
given
FA0= 10 mol / min v0= 0.1L/S
a) rA=k when k is 0.1 b) -rA=k CA k = 0.1/s

2
V = = =

N=0

1. K= 0.1 mol / L.S

V = V = V=


7
C ) -rA=k CA 2 k = 0.1 L / mole . s

( * ) V = (v2/k ) FA = 0.1 * 10 = 1

MOL / S

) (
= rA = = -k CA

V = ( v0/k) ln


8
Example
1. A certain reaction has a rate given by -r, = 0.005C2, mol/cm3 .

min If the concentration is to be expressed in mol/liter and time in
hours, what would be the value and units of the rate constant?
2. consider a liquid phase A
The first order (-rA = kcA) reaction is carried out in a tubular

reactor in which the
Volumetric flow rate , v is constant
a) Determine the reactor volume necessary to reduce the exiting

concentration to
10% of the entering concentration when the volumetric flow rate is
10 dm3/min
and the specific reaction rate k is 0.23 min -1
b) Calculate the volume of a CSTR for the conditions in a.

Which volume is larger ANS ( 391.3 L )
c) Calculate the time to reduce the number of moles of A to 1% of

its initial value
in a constant-volume batch reactor for the reaction and data in a.
ANS ( 20 MIN )
3) A 10 miute experimental run shows that 75% of liquid reactant is

converted to product by 0.5 order rate . what would be the fraction
converted in a half- hour run ?

9
Reactor Mole Balances Summary

10

11

12
CH2:- CONVERSION AND FREACTOR SIZING
Chapter 2
Conversion and reactor sizing
batch reactor
-rA = f ( X )
NA = NA0 - NA0 X
NA :- MOLE OF A IN REACTOR AT t
NA0 :- MOLE OF A INITIALLY FED AT t=0
NA0 X :- MOLE OF A THAT HAVE BEEN CONSUMED BY

CHEMICAL REACTION ( RACTED )
NA0 = NA0 ( 1-X )
dNA = - NA0 dX

t=

Ex :- In a liquid phase A of calculate time taken to achieve 90 %

conversion in a 200 dm3 (constant volume )batch reactor with
CA0=1M after mixing at temperature 77
Given :- K = 0.1 min-1 ( * first order )

t= = -k -1 ln ( 1- X ) = -10 min ln 0.1 = 23 min
( )
t in this case depend on k,x
K = 0.1 MOL / MIN . L ( zero order )

.
t = = = . =
.
how would your answer change if rA= k cA2

13
Ideal gas law
CA0 = ( yA0 * P0 ) / ( R*T0)

yA0= = =

Example 2 1
A gas of pure A at 830 kpa enters a reactor with a volumetric flow rate of
2 dm3 / s at 500 k , calculate
1. entering concentration of A .
CA0 = ( yA0 * P0 ) / ( R*T0)

CA0 = . . = . mol/dm3

.
2. entering molar flow rate
FA0 = CA0 * V0
FA0 = ( 0.2 mol / dm3 ) * 2 dm3 / s = 0.4 mol / s
Note
( equimolar flow of A & inert ) yA0 = 0.5
3. calculate time ( in hour ) taken to consume 50% of A in 2 dm3
(constant volume ) batch reactor with CA0=0.20 mol / L
Given :- -rA= k CA02 ( 1-X )2 when k = 0.001 L / MOL. S

14
CSTR REACTOR

V=

Example ( the second order liquid phase reaction A )
Calculate the volume ( in m3 ) to achieve 80 % conversion in a CSTR reactor ,

A enters the reactor at a molar flow rate 0.4 mol / s and volumetric flow rate 1
L/ S
Given k = 0.003 L/MOL . S
V = ( v02*X)/ ( k*FA0)(1-X)2
V = ( 1 (L2 / S2) * 0.8 ) / ( 0.003 (L/MOL.S) * 0.4 (MOL/S) * 0.22)
V= 16.6 m3
How would your answer change if

1. The reaction is zero order
2. The reaction is first order

15
PFR REACTOR

= / =

The first order reaction A B
i s c a r r i e d o u t i n a t u b u l a r r e a c t o r i n w h i c h v o l u me t r i c f l ow
rate is constant v
d e t e r mi n e the reactor volume necessary to achieve 90 % conversion ,
w h e n t h e volumetric flow rate is 10 liters/min. and specific reaction
rate k is 0.23/ min

V =

ANS V = 100 L
Example
The irreversible liquid phase second order reaction 2A
Is carried out in CSTR reactor , the entering concentration of A , CA0 is 2 molar and the exit
concentration
Of a is 0.1 molar . the entering and exiting volumetric flow rate v0 is constant at 3 dm3/s
Given k = 0.03
1. what is the UNIT of k ?
2. what is the molar flow rate of A ?
3. the conversion ( X ) = .
4. what is the volume of the reactor ? ANS ( V=47.5 L )

16
Example
A +
A 200 dm3 constant volume batch reactor is prussurized to 20 atm with amixture
of 75% A and 25% inert
The gas phase reaction is carried out isothermally at 227 .
a) Assuming that the ideal gas law is valid ( ( how many mol of A are in
the reactor initially ? what is the initiall concentration of A ?
NT0 = /
.
NT0 = ( 20 atm * 200 dm3 ) / ( 0.082 * 500 K ) = 97.6 mol
.
NA0 = NT0 * yA0 = 97.6 mol * 0.75 = 73.2 mol
CA0 = NA0 / V0 = 73.2 mol / 200 dm3 = 0.366 mol / dm3
b) is the reaction is first order when k = 0.1 min-1 calculate the time to consume
99% of A

t= = = 46 .1 min
()
c) if the reaction is second order ( k = 0.7 dm3 / mol . min ) calculate the time to
consume 80 % of A

t= t = = 15.6 min
( )()
d) calculate the pressure in the reactor at the time in the part c if the temperature
227 ( )
NT=NA+NB+NC+NI
NT=0.25 NT0 +0.2 NT0 +0.8 NA0 +0.8 NA0 = ( 0.25*97.6 mol ) + ( 1.8 * 73.2 mol ) =
156.1 mol
. .
P = ( NT R T / V ) = ( 156.1 mol * * 500 K ) / 200 L )
.
P = 25.6 atm

17
Reactor sizing
PFR X
CSTR

18
Example 2-2
The reation described by the data in table 2-2
Is to be carried out in a CSTR reactor . species A enters the reactor at amolar

flow rate of 0.4 mol / s
a) calculate the volume necessary yo achieve 80 % conversion in a CSTR

V= V = 8 m3 * 0.8 = 6.4 m3

b) shade the area that would give the CSTR volume necessary to achieve 80
% conversion

X,

) CSTR (

19
PFR ) f(X ) f( CA ) f( NA

5 POINT

X1=0.2 X2=0.4 X3=0.6
X1=0.1 X2=0.2 X3=0.3
5 POINT 5

4 POINT 4
PFR 1/-rA

=V = } ) { f ( X0 ) + 4f ( X1 ) + 2f ( X2 ) +4f ( X3 ) + f ( X4

) f( x0 1/-rA X0

=


20

Example 2-3
The reaction described by the data in tables below is to be carried out in a PFR . the entering molar flow
rate of A is 0.4 mol/s
a) use the most accurate of the integration formula to determine the PFR reactor
volume necessary to achieve 80 % conversion .

V= = { f ( X0 ) + 4f ( X1 ) + 2f ( X2 ) +4f ( X3 ) + f ( X4 ) }

X0=0 X1=0.2 X2=0.4 X3=0.6 X4=0.8 = = ( 0.8 0 ) / 4 = 0.2

.
V= { 0.89 + 4(1.33) +2(2.05) + 4(3.54) + 8 } = 2.165 m3

b) shade the area that would give the PFR the volume necessary to achieve 80 %
conversion .

21

22
Reactor in series
In series the conversion is increase but in parallel arrangement conversion

is the same .
Given rA as a function of conversion one can also design any sequence of

reactors :
Volume of CSTR in series
V n = ( FA0/-rAn ) * ( X n Xn-1 ) -rA exist at Xn
Volume of PFR in series

=


23

24
Example 2-5
For the two CSTERs in sreies . 40% conversion is achieved in the first
reactor . what is the volume of each of the two reactors necessary to
achieve 80 % overall conversion of the entering species A
For reactor 1 when X=0.4
V1= ( FA0 / -rA1 )X1 * X1 = 2.05 m3 * 0.4 = 0.82 m3
For reactor 2 when X2 = 0.8 then
V 2 = ( FA0/-rA2 ) * ( X 2 X1)
V2 = ( 8 m3 ) * ( 0.8 -0.4 ) = 3.2 m3
Vt = V1+V2 = 0.82+3.2=4.02 m3
The volume necessary to achieve 80 % conversion in one CSTR
V = 8*0.8 = 6.4 m3
The sum of the two CSTR reactor volumes in series is less than the volume
of one CSTR to achieve the same conversion

25
Example 2-7
n C4H10
The isomerization of butane was carried out adiabatically in the liquid phase
and the data in table below were obtained
Calculate the volume of each of the reactor for an entering molar flow rate of
n-bentane of 50 Kmol / h
1:- ( CSTR reactor at X=0.2 )
V1 = ( FA0 / -rA ) * X1 = 0.94 m3 * 0.2 = 0.188 m3
2:- ( PFR reactor when X1 = 0.2 and X2 = 0.6 )

.
V2 = .

3 POINT
. ( .. )
V2 = . = ( /) ( FA0 ) { f ( X0) + 4 f ( X1 ) + f ( X2 ) } =

V2 = ( 0.2 / 3 )( 50 kmol / h ){ 0.01887 +4*0.017 + 0.02632 )( kmol.m3/h) = 0.38m3
V3 ( CSTR ) = 2m3 * ( 0.65-0.6 ) = 0.1 m3

26
Space time
is obtained by dividing the reactor volume by the volumetric flow rete

entering the reactor
= ( V/v0 )
space time is the time necessary to process one volume of reactor fluid at
the entrance conditions. This is the time it takes for the amount of fluid
that takes up the entire volume of the reactor to either completely enter
or completely exit the reactor.

27
Example
1 calculate the reactor volume V1 and V2 for the plug flow sequence shown
below when the intermediate conversion is 40 % and the final conversion is
80 %

28
2 A first order liquid phase and irreversible reaction
A +
Is carried out in a batch reactor over the period of an 60 minute a conversion

of 90 % is achieved . the stirred tank reactor that is currently used in batch
mode is under consideration for conversion to a CSTR in order to increase
the tons of B and C that can be produced per year what is the space time
required to achieve 90 % conversion in a CSTR .
-rA= k CA
For batch reactor t = ( 1/k ) ln ( 1 / ( 1-X ) )
60 min = ( 1/ k ) ln ( 1/ ( 1-0.90 ) ) k = 2.3 hr-1
For CSTR reactor V= ( FA0 * X ) / -rA CA = CA0 ( 1-X ) CA0 = FA0/V0
= X / ( ( k * ( 1-X ) ) = 3.9 hr

29
3 A CSTR is fed with a solution of reactant A of concentration 10 k mole/m3
At a volumetric flow rate is 0.02 m3/s .
The product mixture from the 1st CSTR is fed into a 2nd CSTR of twice the
volume of the first CSTR . the two CSTRs in series are required to achieve an
overall conversion of 80 % .
The reaction ( A ) is first order in A with a reaction rate constant
Is 0.2 s-1 .
what is the volume of the 1st CSTR ??
V1 = ( v0 * X1 ) / ( k ( 1-X1 ) )
) X1 , V 1 )
CA1 CA0
CA2 CA1
X2 = ( CA0 CA2 ) / CA0 = 0.80 when CA0 = 10 k mol / m3 CA2 = 2 k mol/m3

( )
V2 =

FA0 = 10* 0.02 = 0.2 K mol /s
V2 = 2V1
( )
=2*
( )
X1 = 0.459
..
V1 = = = 0.0848 m3
( ) .( . )
P ( 2-4/7/8/9) PROBLEMS

30
CH3 :- RATE LAWS AND STOICHIOMETRY
A homogeneous reaction is one that involves one phase but a heterogeneous

involves more than one phase .
A irreversible reaction is one that process only on one direction and continuous
in that direction until the reaction exhausted ( ) .
A reversible direction can proceed in each direction
Depending on the concentration of reaction and product relative the

corresponding equilibrium on the concentration .
In irreversible reaction no chemical completely .
The molecularity of reaction is the number of atoms / ions and molecules
aA +b B cC+dD A is limiting reactant
) limiting reactant (

limiting reactant
) a ,b ( stoichiometry coefficient
C+o2 co2
2 mol of c and 1 mol of o2 fed to the reactor
Determine the limiting reactant
O2 is the limiting reactant

A + ( b/a ) B ( c/a ) C + ( d/a ) D if A is the limiting reactant
( -rA / a ) = ( -rB / b ) = ( rC / c ) = ( rD / d ) ( )

31
Example
2NO+O22NO2
If NO2 is formed at a rate 4 mole / m3.s
Find the rate of disappearance of NO
( -rNO / 2 ) = ( rNO2 / 2 )
rNO2 = -4 mol / m3.s
Power rate law
aA +b B cC+dD
-rA = f ( CA , T , P , type of catalyst )
-rA = k cA cB
+ = n ( overall order )
as T increase k increase
, :- from experimental
k = f( T ) = A /
E :- activation energy A :- preexponential factor/ frequency factor
If ( a = ) and ( b = ) called elementary reaction
Example
0.5 A + B 2D + C
What is the rate of D information
=a = 0.5 =b = 1
( -rA/0.5 ) = ( rD/2 ) rD= -4 rA
rD = 4 kA CA0.5 CB

32
Reversible reaction
aA + bB cC+ dD
at equilibrium the rate of reaction is identically zero for all species
rA = -rA = 0
the concentration at equilibrium are related by the thermodynamic relationship

for the equilibrium KC
KC =( CCec * CDed ) / ( CAe * CBeb ) e :- equilibrium
The unit of KC are ( mol / dm3 ) d+c-a-b
Example 2B D + H2
what is the net rate of disappearance of B
For reversible reaction
a. forward reaction
2B D + H2
-rB ( forward ) = kB * CB2
b. backward reaction
D + H2 2B
rB ( backward ) = k -B * CD * CH2
the net rate of formation
rB = rB forward + rB backward
rB = - kB * CB2 + k -B * CD * CH2
-rB = - kB * CB2 + k -B * CD * CH2
At equilibrium ( rA = rA = 0 ) and elementary reaction
KC = ( kB / k-B )e this is called thermodynamically consistent

33
Example
AB+C
Given rAf = k CA -rAb = k-1 CB2 CC
Is the reaction thermodynamically ???
At equilibrium rA = 0
rA = -k CA + k-1 CB2 Cc
0 = -k CA + k-1 CB2 CC ( k / k-1 ) = ( CB2 * Cc ) / CA
KC = ( CB CC ) / CA KC ( k / k-1 )
This reaction isn't thermodynamically consistent
The reaction rate constant
k = f( T ) = A /
Extrapolation
Ln k = ln A - ( E / RT ) unit of A is the same unit of k
Y ln k X T-1
E = -slope * R

34
Example 3-1-1
A B C
1 K ( s-1 ) Ln k T-1 K-1
2 0.00043 -7.75 0.0032
3 0.00103 -6.88 0.00314
4 0.0018 -6.32 0.0031
5 0.00355 -5.64 0.00305
6 0.00717 -4.94 0.00300
SLOPE
-1
-2
ln k = -14017T-1 + 37.12
-3
-4
-5
-6
-7
-8
-9
-14017 SLOPE
E= -slope * R = -14017 K * 8.314 j/mol . K = 116.5 kj/mol
intercept
37.12
Ln A = intercept = 37.12
A = 1.32 * 1016 s-1
k =1.32 * 1016 s-1 exp { -14017 K/T}

35
A -rA = 0.1 CA
A -rA = 0.1 CA
rA
Determine the frequency factor from the following data if activation energy equal
1000 j / mol
k ( min -1 ) 0.01 ??
T(c) 50 100
k1= A / k2= A /
( k1 / k2 ) = exp { ( -E/R ) * ( T1-1 T1-1 }
0.1 min-1 / k2 = exp { ( -1000 / 8.314 ) * (323-1373-1) } =0.013644 min-1

36
Stoichiometry table for a batch reactor at v constant
aA + bB cC + dD if A is a limiting reactant
Species Initial mol Change mol Remaining mol

A NA0 -NA0 X NA=NA0-NA0X
B NB0 -(b/a) NA0 X NB= NB0 -(b/a) NA0 X
C NC0 (c/a) NA0 X NC= NC0+(c/a) NA0 X
D ND0 (d/a) NA0 X ND=ND0+ (d/a) NA0 X
I ( INERT ) NI0 ----- -----
Total NT0 ----- NT=NT0 = ((d/a)+
(c/a) -(b/a)-1)* NA0 X
General equation

CJ = CA0 ( X) :- Stoichiometry coefficient (b/a) ( d/a)(c/a)(a/a)

+ : product - : reactant

FJ = FA0 ( X)

V=V0
Example :- In a liquid phase elementary reaction A+B
calculate time taken to achieve 60 % conversion in a 200 dm3 (constant volume )

batch reactor with NA0=20 mol , NB0=20 mol and NC0 = 50 mol
Given :- k = 0.1 L/mol.min n=2
-rA=k CA CB
CA= CA0 ( 1-X ) CB=CA0 ( 1-X ) CA0 = 0.1 mol / L
-rA = k CA02 ( 1-X )2

.
t= = 100 min * (( 1/ ( 1-X )) -1) = 150 min
()( )
what is the final mol of C ? NC = 20 mol ((50/20) +3*0.6 ) = 86 mol
is the reaction thermodynamically consistent ( show your work )
what is the unit of KC

37
V is constant
1 ) in liquid phase ( compressible )
2 ) in gas phase if
a) given ( constant volume )
b) = 0 = ( c/a ) + ( d/a ) ( b/a ) 1
In a gas phase
P V = NRT if ( T P V ) is constant
N will change due to the chemical reactant
If V variable V=V0 ( 1+ X ) ( T/T0) (P/P0)
V :- volume of the reaction mixture at any time
V0 :- initial volume of the reaction mixture
:- yA0 * yA0 = NA0 / NT
T=T0 isothermal p=p0 isobaric

CJ = ( CA0/ 1+ ) ( ( X ) at isothermal and isobaric


38
Problem 3/13
NO2CL + 2NH3 NO2NH2+NH4CL
The liquid phase reaction is first order in both ONCB ( NO2CL ) and ammonia
with k = 0.0017 m3/kmol.min at 188 with E = 11273 cal / mol . the initial
entering concentration of ONCB and ammonia are 1.8 kmol /m3
and 6.6 kmol / m3 , respectively
a . write the rate law for the rate of disappearance of ONCB in terms of
concentration
ONCB is a limiting reactant
A + 2B C+D
Assume A and B both first order
-rA = k CA CB

CA = CA0 ( 1* X ) CB= CA0 ( 2X)

.
CA =1.8 * ( 1-X ) CB= 1.8 ( 2X)
.
-rA= k * 3.24 kmol2/m6 ( 1-X )( 3.67 2X )
f . what is the rate of the reaction when X = 0.9 at T = 25
k = k0 exp ( ( E/R ) ( T0-1 T-1 ))

k = 0.0017 m3/kmol . min exp ( (11273 cal / mol ) / ( 1.987 cal /mol .K ) ( 461-1 -298-1) k-1
k = 2.027 * 10-6 m3/kmol.min
-rA= 2.027 * 10-6 m3/kmol.min * 1.82 kmol2/m6 * ( 1-0.9 ) * ( 3.67-2*0.9 )
-rA = 1.228 *10-6 kmol/m3.min
g . what would be the concentration CSTR reactor volume at 25 to achieve

90% conversion for fed rate of 2 dm3 / min

V = = = ( 0.9 * 1.8 kmol/m3*0.002 m3/ min ) / ( 1.228*10-6 kmol /m3.min)

V= 2638.436 m3

39
Stoichiometric table for a flow system
Species Fed rate Change Effluent/exist

A FA0 -FA0X FA= FA0 ( X )

B FB0 -(b/a)FA0X FB= FA0 (

(b/a) X )

C FC0 (c/a)FA0X FC= FA0 (

+ (c/a) X )

D FD0 +(d/a)FA0X FC= FA0 (

+ (d/a) X )

I FI0 ------ FI= FA0 ( )
FT = FT0 + ( (d/a)+ (c/a)-(b/a)-1) *FA0*X
= (d/a)+ (c/a)-(b/a)-1
FT = FT0 + FA0X
= ( change in total number of moles ) / mole of A reacted
The gas phase reaction
0.5 N2 +1.5 H2 NH3
Is to be carried out isothermally . the molar fed is 50% H2 and 50% N2 , at a

pressure 16.4 atm and 227
a) what are CA0 , , ? calculate the concentration of ammonia and hydrogen

when the conversion of H2 is 60 %
H2 is the limiting reactant
b) if the reaction is elementary with kN2 = 40 dm3 /mol . s
write the rate of reaction as a function of conversion for a flow system and a
constant volume batch system

40
KC conversion at equilibrium
Example 3-6
The reversible gas phase decomposition of nitrogen tetroxide ,N2O4 to dioxide

NO2
N2O4 2NO2 is to be carried out at constant temperature . the feed consists of

pure N2O4 at 340 K and 202.6 kpa ( 2 atm ) . the concentration equilibrium
constant at 340 K is 0.1 mol / dm3
a) calculate the equilibrium conversion of N2O4 in a constant volume batch

reactor
A 2B
KC = ( CBe2/CAe )
CA = CA0 ( 1-Xe ) CB= 2CA0 Xe
CA0 = ( yA0 * p ) / ( RT )
yA0 = 1
CA = 2 atm / ( 0.0821 atm . dm3 / mol . k ) * 340K = 0.07174 mol/dm3
KC = (4CA02 Xe2) / ( CA0 (1-Xe)) = (4CA0 Xe2)/ (1-Xe) = 0.1 mol / dm3
0.1 mol / dm3 = ( 4*0.07174 mol/dm3 * Xe2 ) / ( 1- Xe)
0.28696 X2+0.1 X -0.1=0
Xe = 0.44
b) calculate the equilibrium conversion of N2O4 in a flow reactor
v is not constant
calculate ,
= 2-1 = 1 = yA0 * = 1*1 = 1
v = v0 ( 1+ Xe )

41
CA = (CA0(1-X))/(1+X) CB = (2CA0X)/(1+X)
KC = 4X2/(1-X)2 ( 0.28696+0.1 )X2 -1 =0
Xe=0.51
c) assuming the reaction is elementary , express the rate of the reaction solely
as a function of conversion for a flow system and for a batch system
for a batch system ( assume v is constant )
rA = rAf + rAb = -k CA + k-1 CB2
-rA = k ( CA ( CB2/KC )) = k ( CA0 ( 1-X ) ( 4CA02X2)/KC )
For a flow system
Assume the volume is not constant
-rA = k (CA0 ( 1-X/1+X) ( 4CA02X2/( 1+X)2 .KC))
d) determine the CSTR volume necessary to achieve 80% of equilibrium

conversion for a fed rate 3 mol/min and kA = 0.5min-1
X=0.8 Xe = 0.8 * 0.51 = 0.4
From b c at flow system rA = 0.00070 mol / dm3 . min
V= ( FA0 * X ) / -rA = (3 mol/min) * ( 0.4 ) / (0.00070 mol / dm3 . min)=1.71 m3
: + expansion
- Shrinking
- 0 constant

42

43
Ch4 :- isothermal reactor design
Example 4-2 page 163
It is desired to produce 200 million pounds per year of EG ( ethylene glycol ) .
The reactor is to be operated isothermally . A 1 lb mol/ft3 solution of ethylene

oxide ( EO ) in water is fed to the reactor ( show in figure below ) together with
equal volumetric solution of water containing 0.9 wt % of catalyst H2SO4 . the
specific reaction rate constant is 0.311 min-1 , determine
1. if 80 % conversion is to be achieved , determine the necessary CSTR volume
2. if two 800-gal reactor were arranged in parallel , what is the corresponding

conversion .
3. if two 800-gal reactor were arranged is series , what is the corresponding

conversion .
C2H4O + H2O C2H6O2
V = ( FA0.X )/(-rA)
-rA = k CA
CA =CA0 ( 1-X )
FA0 v0 CA0
FC = FA0.X
FC = 6.137 lbm-mol/min
200*106 1 year 1 days 1hour lb-mol

lbm
year 365 days 24 hour 60 min 62 lbm
FA0 = 7.67 lbm-mol/min

44

( ) DILUTION
CA1 = 1lb-mol /Ft3
V1= ( FA0)/CA1 = ( 7.67/1) = 7.67 Ft3
MW
CH2O = 62.4/18 = 3.4667 lb-mol/Ft3
V0 = VA +VB = 2 * 7.67 Ft3/min = 15 .34 Ft3/min
Dilution
CA1 * VA1 = CA0*V0
CA0 = 0.5 lb-mol/Ft3
) CA = 0.5 ( 1-0.8
-rA = 0.311 min-1 * 0.1 lb-mol/Ft3 = 0.031 lb-mol /Ft3.min
V CSTR = 197.34 Ft3

45
CSTR in parallel and series
V = (FA0 FA) / -rA
V = ( CA0.V0 - CA.V0 ) / rA
V0
= CA0 ( 1-X )
= ( CA0.V0 - CA.V0 ) / rA
At first order
X = ( k ) / ( 1+ )
Damkohler number = Da = k at first order
Da = ( -rA .v ) / FA0 = kCA0 v / v CA0 = k
The Damkohler number for a second order
Da = ( -rA .v ) / FA0 = kCA02 v / v CA0 = k CA0
If the reactor in series CAn = CA0 / ( 1+ Da )n

46
X Da
Da X
-rA =( k CA0 ) / ( 1+ k)n
The rate of disappearance of A in the n reactor
CSTR in parallel
V = ( FA0 .X ) / -rA
The conversion achieved in any one of the reactor in parallel is identical
X1 = X2 = Xn
For a second order liquid phase reaction

V = FA0.X / -rA = FA0.X/k CA02
CA = CA0(1-X)
FA0=CA0.v0
V = ( CA0.v0.X )/kCA02( 1-X ) 2
= X / kCA0( 1-X )2
X = k CA0 ( X2-2X+1)
Da = k CA0
Da X2 -2Da X X + Da =0

+(+)
X=


47
2 / In parallel
X = ( k ) / ( 1+ )
I Ft3=7.48 gal
V = v0 /2
800 gal 1 Ft3*2 1

7.48 gal 15.34 Ft3 / min
= 13.94 min
X=
13.94 min * 0.311 min-1

1+ ( 13.94 min * 0.311 min-1 )
X=0.812

48
3/ in series
X1 = ( k ) / ( 1+ )
= V1/v01
800 gal 1 Ft3 1

7.48 gal 15.34 Ft3/min
= 6.97 min
Da = k = 6.97 min * 0.311 min-1 = 2.168
X1 = ( 2.168) / 3.168 = 0.684
ch2
V = FA0 ( ( X2-X1)/-rA )
-rA2 = kCA2
CA2 = CA0 ( 1-X2)
V/v0 = ( X2-X1) / ( k ( 1-X2 ))
X2 = ( Da + X1 ) / (1+Da ) = 0.90

49
Tubular reactor

V = FA0 second order -rA = k CA2

Liquid phase reaction CA= CA0 ( 1-X )
V = FA0/kCA02 ( X/1-X )
FA0 = CA0 .v0
Da = k CA0
X = Da / ( 1+Da )
Tubular reactor ( v is variable )

V = FA0 second order -rA = k CA2

CA = FA / v = FA / ( v0 ( 1+X) )
CA = CA0 ( 1-X )
CA = CA0 ( 1-X ) / ( 1+ X )

50
Example 4/3
Determine the plug flow reactor volume necessary to produce 300 million pound
of ethylene a year from cracking a feed stream of pure ethane . the reaction is
irreversible and follows an elementary rate law . we want achieve 80 %
conversion of ethane . operating the reactor isothermally at 1100 K at pressure of
6 atm
Given k = 0.072 s-1 at 1000 K
C2H6 C2H4 + H2
A B+ C
FB = 300 * 106 lb / year
300 * 106 lb 1 Year 1 days 1h 1 lb-mol

Year 365 days 24 h 3600 s 28 lb
FB = 0.340 lb-mol / s
FB = FA0 .X
FA0 =0.34/0.8 = 0.424 lb-mol / s

51

V = FA0 -rA = k CA

CA = CA0 ( ( 1-X ) / ( 1+ )
= 1+1-1=1
yA0 = 1 = * yA0 = 1
1 Rankin = 1.8 Kelvin
Temperature = 1980 R
R = 0.73 Ft3.atm/lb-mol. R
CA0 = yA0. P / RT0
Pressure = 6 atm
CA0 = 4.15 * 10-3
E = 82000 cal
R = 1.987 cal / mol.K
T1 = 1000 K T2 = 1100 K

k ( T2 ) = k ( T1 ) exp ( ( T1-1 - T2-1 ) )

k = 3.07 s-1
V = 80.5 Ft3

52

53
CH 5 : - COLLECTION AND ANALYSIS OF RATE DATA
Kinetics of chemical reaction
Chemical kinetics, also known as reaction kinetics, is the study of rates of

chemical processes.
Chemical kinetics includes investigations of how different experimental

conditions can influence the speed of a chemical reaction and yield
information about the reaction's mechanism and transition states, as well as
the construction of mathematical models that can describe the characteristics
of a chemical reaction
The rate of reaction is the change in the amount of reactants or products

over a time interval .The rate of reaction in chemistry, is usually expressed in
moles/second (mol/s) or molarities/second(mol/Ls)
The speed of a chemical reaction is affected by factors such as the

temperature, concentration ,volume, surface area, and orientation.
When the temperature is greater, there is a greater fraction of particles that

have more energy than the activation energy, enabling them to collide and
react. These particles also have more kinetic energy.
At the end of this chapter we can determine the reaction order and specific
reaction rate from experimental date
Analysis of data to find rate law
1) differential method of analysis

2) integral method of analysis

54
Differential method
A product
-rA = ( -dCA /dt ) = k CA slope = ( CA / t )
extrapolation
Ln ( -rA ) = Ln k + Ln CA
Slope = intercept = Ln k
Example
The liquid phase reaction A B
-rA ( mol / L.s ) 0.002 0.008

CA ( M) 0.1 0.2
What is the general form of power rate lat for this reaction at constant
temperature ?
-rA1 = k CA1 -rA2 = k CA2
( 0.002 / 0.008 ) = ( 0.1/0.2) = 2
-rA = k CA2
What is the value of power rate constant
0.002( mol / L.s ) = k * ( 0.1 )2 ( mol/L)2
k= 0.2 L / mol .s

55
INTEGRAL METHOD
To determine the reaction order ( liquid phase batch reactor )
Need to guess reaction order

Integrate the differential form of equation used to model the reactor used
If the right reaction order is assume the plot of concentration time data
should be linear .

56
C :- intercept = CA0
m :- slope = -k

57
Example
A+BC+D
Time 0 50 100 150 200 250 300

(min)
CA 0.0500 0.0380 0.00306 0.00256 0.00222 0.00195 0.00174
3
(mol/dm )
it was reported that the reaction is second order w.r.t.A.
GIVEN CB0= 0.5 mol/dm3
1.using the data confirm the reaction is second order
2.what is the value and unit of k ?
3.what is the value of CA0

58
1.
Time 0 50 100 150 200 250 300

(min)
CA 0.0500 0.0380 0.00306 0.00256 0.00222 0.00195 0.00174
3
(mol/dm )
CA-1 20 26.32 326.8 390.63 450.45 512.82 574.71
2. k=slope = 0.1248 dm3/mol.min
3.intercept = CA0-1 = 20.118 CA0 = 0.0497 mol/dm3

59
The plot in terms of conversion
At zero order
X = ( k/CA0) *t
Slope = ( k/CA0)
at first order
ln ( 1-(1-X) ) = k t
slope = k
at second order
( X / (X-1 )) = CA0 k t
Slope = CA0 k
Half time
Is defined as the time it takes for the concentration of reactant to fall to half of its
initial value
A PRODUCT -rA = kCA
Slope = 1- 1

half time

60
Example
The half period of a first order reaction is 50 min , in what time will it go to
90% completion .
CA = 0.5 CA0 X = ( CA0 CA ) /CA0 X= 0.5
Time of batch reactor at first order t = ( -1/k ) * ln ( 1-X )
X= 0.5 t = 50 min t1/t2 = ln(1-X1)/ln(1-X2)
t 90%=166 min
Example
A first order reaction is 75 % completed in 72 min how will time will it take
for
1) 50 % completion 2) 87.5 % completion
Problem 5/10
The gas phase decomposition A B + 2C is carried out in a constant volume

batch reactor . Runs 1 through 5 were carried out at 100 . while run 6 was
carried out at 110
A ) from the data in the table below , determine the reaction order and specific
reaction rate constant
run CA0 Half life

1 0.025 4.1
2 0.0133 7.7
3 0.01 9.8
4 0.05 1.96
5 0.075 1.3
6 0.025 2

61
Run Ln CA0 LN ( t1/2 )

1 -3.6888795 1.410987
2 -4.3199912 2.0412203
3 -4.6051702 2.282382
4 -2.9957323 0.67294447
5 -2.5902672 0.26236426
6 -3.6888795 0.693147
2.5
1.5
1
y = -1.0129x - 2.3529
0.5
0
-5 -4 -3 -2 -1 0
ln CA0
Slope = 1- = -1.012 = 1+1.012 2
Intercept = ln ( ( 2 -1-1) /( k ( -1) ) = -2.352
k= 10.516 L/gmol.min at T = 100
B ) what is the activation energy for this reaction
at T = 110 CA0 = 0.025 from the table
0.693147 = ln ( 1/ k(2-1)) + ( 1-2 ) ln 0.025
k= 20 L/gmol.min

62
k1= A e ( -E/RT1) k2= A e ( -E/RT2)
T1 = 373 K T2=383 K R = 8.314 J/mol.K
k1/k2 = e ( -E/RT1) + e (E/RT2)
E=76.53 kJ/mol
A second order liquid reaction is 20% complete in 10 min . calculate
1.the specific rate constant .
2.the time taken for the reaction go to half life.
Given CA0 = 1 mol / L

63

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1

CHAP . 1 MOLE BALANCES

The rate of the reaction , -rA

The term chemical species refers to any chemical component or

The identity of a chemical species is determine by

1.kind 2. Number 3.configuration of that species "

Any change ( 1.2.3 ) identity change

Ar : - chemical species ( change in A identity per unit time per unit

-rj : - ( mole j consumed / reacted / disappeared ) / time * volume

rj : - ( mole j produce /appeared ) / time * volume )

3. semi batch reactor

1 continuous flow reactor

a. CSTR :- continuous stirred tank reactor

b. PFR :- plug flow reactor

c. packed fed reactor

TYSIR SARHAN HAYTHAM ALZOUBI

CHAP . 1 MOLE BALANCES

t0=0 t 1 = final time

NA0 :- initial mole of A

Batch reactor balance

In out +generation = accumulation

Time necessary to reduce the number of moles of A from NA0 to NA.

th order with respect to A

order with respect to B

K : constant rate of chemical reaction =

TYSIR SARHAN HAYTHAM ALZOUBI

CHAP . 1 MOLE BALANCES

What the time needed so that the final moles of A become

Where rA = 0.1 min-1 CA

calculate the time necessary to consume 99.9%

(b) -rA = kcA k = 0.0001 s-1

TYSIR SARHAN HAYTHAM ALZOUBI

CHAP . 1 MOLE BALANCES

CSTR( molar flow rate)

CSTR volume necessary to reduce the molar flow

TYSIR SARHAN HAYTHAM ALZOUBI

CHAP . 1 MOLE BALANCES

TYSIR SARHAN HAYTHAM ALZOUBI

CHAP . 1 MOLE BALANCES

Plug Flow Reactor

( Tubler , PFR , plug )

what is the volume of tubler reactor so that FA= 0.1

FA0= 10 mol / min v0= 0.1L/S

a) rA=k when k is 0.1 b) -rA=k CA k = 0.1/s

TYSIR SARHAN HAYTHAM ALZOUBI

CHAP . 1 MOLE BALANCES

C ) -rA=k CA 2 k = 0.1 L / mole . s

TYSIR SARHAN HAYTHAM ALZOUBI

CHAP . 1 MOLE BALANCES

1. A certain reaction has a rate given by -r, = 0.005C2, mol/cm3 .

2. consider a liquid phase A

The first order (-rA = kcA) reaction is carried out in a tubular

a) Determine the reactor volume necessary to reduce the exiting

b) Calculate the volume of a CSTR for the conditions in a.

c) Calculate the time to reduce the number of moles of A to 1% of

3) A 10 miute experimental run shows that 75% of liquid reactant is

TYSIR SARHAN HAYTHAM ALZOUBI

CHAP . 1 MOLE BALANCES

Reactor Mole Balances Summary

TYSIR SARHAN HAYTHAM ALZOUBI

CHAP . 1 MOLE BALANCES

TYSIR SARHAN HAYTHAM ALZOUBI

CHAP . 1 MOLE BALANCES

TYSIR SARHAN HAYTHAM ALZOUBI