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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


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CHAP . 1 MOLE BALANCES

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

TYSIR SARHAN HAYTHAM ALZOUBI


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CHAP . 1 MOLE BALANCES

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 =
.

TYSIR SARHAN HAYTHAM ALZOUBI


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CHAP . 1 MOLE BALANCES

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

TYSIR SARHAN HAYTHAM ALZOUBI


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CHAP . 1 MOLE BALANCES

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

TYSIR SARHAN HAYTHAM ALZOUBI


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CHAP . 1 MOLE BALANCES

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=

TYSIR SARHAN HAYTHAM ALZOUBI


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CHAP . 1 MOLE BALANCES

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

TYSIR SARHAN HAYTHAM ALZOUBI


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CHAP . 1 MOLE BALANCES

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 ?

TYSIR SARHAN HAYTHAM ALZOUBI


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CHAP . 1 MOLE BALANCES

Reactor Mole Balances Summary

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CHAP . 1 MOLE BALANCES

TYSIR SARHAN HAYTHAM ALZOUBI


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CHAP . 1 MOLE BALANCES

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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

TYSIR SARHAN HAYTHAM ALZOUBI


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CH2:- CONVERSION AND FREACTOR SIZING

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

TYSIR SARHAN HAYTHAM ALZOUBI


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CH2:- CONVERSION AND FREACTOR SIZING

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

TYSIR SARHAN HAYTHAM ALZOUBI


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CH2:- CONVERSION AND FREACTOR SIZING

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 )

TYSIR SARHAN HAYTHAM ALZOUBI


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CH2:- CONVERSION AND FREACTOR SIZING

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

TYSIR SARHAN HAYTHAM ALZOUBI


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CH2:- CONVERSION AND FREACTOR SIZING

Reactor sizing

PFR X

CSTR

TYSIR SARHAN HAYTHAM ALZOUBI


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CH2:- CONVERSION AND FREACTOR SIZING

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 (

TYSIR SARHAN HAYTHAM ALZOUBI


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CH2:- CONVERSION AND FREACTOR SIZING

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

=

TYSIR SARHAN HAYTHAM ALZOUBI


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CH2:- CONVERSION AND FREACTOR SIZING


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 .

TYSIR SARHAN HAYTHAM ALZOUBI


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CH2:- CONVERSION AND FREACTOR SIZING

TYSIR SARHAN HAYTHAM ALZOUBI


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CH2:- CONVERSION AND FREACTOR SIZING

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



=

TYSIR SARHAN HAYTHAM ALZOUBI


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CH2:- CONVERSION AND FREACTOR SIZING

TYSIR SARHAN HAYTHAM ALZOUBI


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CH2:- CONVERSION AND FREACTOR SIZING

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

TYSIR SARHAN HAYTHAM ALZOUBI


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CH2:- CONVERSION AND FREACTOR SIZING

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

TYSIR SARHAN HAYTHAM ALZOUBI


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CH2:- CONVERSION AND FREACTOR SIZING

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.

TYSIR SARHAN HAYTHAM ALZOUBI


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CH2:- CONVERSION AND FREACTOR SIZING

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 %

TYSIR SARHAN HAYTHAM ALZOUBI


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CH2:- CONVERSION AND FREACTOR SIZING

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

TYSIR SARHAN HAYTHAM ALZOUBI


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CH2:- CONVERSION AND FREACTOR SIZING

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

TYSIR SARHAN HAYTHAM ALZOUBI


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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 ) ( )

TYSIR SARHAN HAYTHAM ALZOUBI


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CH3 :- RATE LAWS AND STOICHIOMETRY

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

TYSIR SARHAN HAYTHAM ALZOUBI


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CH3 :- RATE LAWS AND STOICHIOMETRY

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

TYSIR SARHAN HAYTHAM ALZOUBI


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CH3 :- RATE LAWS AND STOICHIOMETRY

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

TYSIR SARHAN HAYTHAM ALZOUBI


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CH3 :- RATE LAWS AND STOICHIOMETRY

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}

TYSIR SARHAN HAYTHAM ALZOUBI


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CH3 :- RATE LAWS AND STOICHIOMETRY

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

TYSIR SARHAN HAYTHAM ALZOUBI


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CH3 :- RATE LAWS AND STOICHIOMETRY

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

TYSIR SARHAN HAYTHAM ALZOUBI


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CH3 :- RATE LAWS AND STOICHIOMETRY

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

TYSIR SARHAN HAYTHAM ALZOUBI


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CH3 :- RATE LAWS AND STOICHIOMETRY

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

TYSIR SARHAN HAYTHAM ALZOUBI


39

CH3 :- RATE LAWS AND STOICHIOMETRY

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

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CH3 :- RATE LAWS AND STOICHIOMETRY

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 )

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41

CH3 :- RATE LAWS AND STOICHIOMETRY

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

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42

CH3 :- RATE LAWS AND STOICHIOMETRY

TYSIR SARHAN HAYTHAM ALZOUBI


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

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Ch4 :- isothermal reactor design


( ) 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

TYSIR SARHAN HAYTHAM ALZOUBI


45

Ch4 :- isothermal reactor design

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

TYSIR SARHAN HAYTHAM ALZOUBI


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Ch4 :- isothermal reactor design

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=

TYSIR SARHAN HAYTHAM ALZOUBI


47

Ch4 :- isothermal reactor design

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

TYSIR SARHAN HAYTHAM ALZOUBI


48

Ch4 :- isothermal reactor design

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

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49

Ch4 :- isothermal reactor design

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 )

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Ch4 :- isothermal reactor design

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

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51

Ch4 :- isothermal reactor design


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

TYSIR SARHAN HAYTHAM ALZOUBI


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Ch4 :- isothermal reactor design

TYSIR SARHAN HAYTHAM ALZOUBI


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

TYSIR SARHAN HAYTHAM ALZOUBI


54

CH 5 : - COLLECTION AND ANALYSIS OF RATE DATA

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

TYSIR SARHAN HAYTHAM ALZOUBI


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CH 5 : - COLLECTION AND ANALYSIS OF RATE DATA

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 .

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CH 5 : - COLLECTION AND ANALYSIS OF RATE DATA

C :- intercept = CA0

m :- slope = -k

TYSIR SARHAN HAYTHAM ALZOUBI


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CH 5 : - COLLECTION AND ANALYSIS OF RATE DATA

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

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CH 5 : - COLLECTION AND ANALYSIS OF RATE DATA

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

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CH 5 : - COLLECTION AND ANALYSIS OF RATE DATA

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

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CH 5 : - COLLECTION AND ANALYSIS OF RATE DATA

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

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CH 5 : - COLLECTION AND ANALYSIS OF RATE DATA

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

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CH 5 : - COLLECTION AND ANALYSIS OF RATE DATA

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

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CH 5 : - COLLECTION AND ANALYSIS OF RATE DATA

TYSIR SARHAN HAYTHAM ALZOUBI