LECTURE FOUR

STOICHIOMETRIC TABLE

3. (A) Batch Systems :-

Example:-

the stoichiometric reaction for the formation of soap from aqueous coastic soda

and glyceral streat, set up a stoichiometric table expressing the concentration

of each species in terms of its initial concentration and the conversion.

Consider the reaction to occur in a batch system? The reaction is:-

3 NaOH (aq )+ ( C17 H 35 COO )3 C3 H 5 → 3 C17 H 35 COO Na+C 3 H 5 ( OH )3

Solution:-
3 A + B →3 C+ D

Since this is a liquid phase reaction, the density is to be considered constant,

therefor V=Vo
N A N A 0 ( 1−x )
C A= = =C A 0 (1−x )
V V0

CB0 C C
θ B= ; θC = C 0 ; θ D = D 0
CA 0 C A0 C A0

Speices Initiall Change Change Remaining concentratio

y n
NaOH A NAO - NAO x - NAO x NAO(1-x) CAO(1-x)
(C17H35COO)3C3H5 B NBO -(b/a) NAO x -(1/3)NAO x NAO(ϴB-x/3) CAO(ϴB-x/3)
C17H35COONa C NCO NAO x )c/a(+ NAO x NAO(ϴC +x) CAO(ϴC +x)
C3H5(OH)3 D NDO NAO x )d/a(+ NAO x )1/3( NAO(ϴD+x/3) CAO(ϴD+x/3)
Water I NIO NIO CIO
NTO NTO CTO

3. (B) Flow Systems :-

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 This system is applied for the tubular reactor(PFR) and the backmix

reactor(CSTR).

mol F A ( mol /s ) molar flow rate

CA ( )
m 3
= 3
v ( m /s )
=
volumetric flowrate

F A 0−F A 0 x F A 0 (1−x )
C A= = 3. B .1
v v
b
F B 0− F x
FB a A0
C B= = 3. B .2
v v
c
FC 0+ F x
F a A0
C C= C = 3. B .3
v v
D
F D 0+ F x
FD a A0
CD= = 3. B .4
v v

Multiply Eqns. 3.B2,3,4 by(FAO/FAO) to obtain:-

b c d
( a ) a ( ) a( )
F B=F A 0 θB − x ( 3. B .5 ) ; FC =F A 0 θC + x ( 3. B .6 ) ; F D =F A 0 θ D + x ( 3. B .7 )

Where :-
F B 0 C B 0 v o C B 0 YC B 0
θ B= = = =
F A 0 C A 0 v o C A 0 YC A 0

So as for other quantities of ϴC; ϴD ;ϴI

For liquids, the volume change with reaction is negligible when no changes are taking
place. Consequently, we can take v=vo then :-

FA 0
C A= ( 1−x )=C A 0 ( 1−x ) ( 3. B .8 )
vo

b
( )
C B=C A 0 θB − x ( 3. B .9 )
a

c
( )
C C =C A 0 θC + x (3. B .10 )
a

d
( )
C D =C A 0 θ D + x ( 3. B .11 )
a

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3. (C) Volume change with reaction :-

Most gaseous reactions undergo volume changes, for example, the synthesis of
ammonia:-

CA,CB, and CC can be determined by expressing the volume (V) for a batch system or
volumetric flow rate (v) for a flow system as afuction of conversion:-
V 1=f 1 ( x ) ; v=f 2 ( x )

To derive the relations, starting from equation of state:-

P V =ZN T RT ( C1 )

Where :-

P is total pressure (KPa), 1 atm=101 KPa

Z compressibilty factor

V is volume dm3

atm. dm 3 KPa . dm3

R is gas constant 0.082 =8.314
gmol . K gmol . K

At time=0 (initial condition):-

Po V o=Z o N ¿ R T o ( C 2)

Divide Eqn.C1 on C2

PV Z N T RT
=
PoV o Z0 N¿ R T o

V =V o ( PP )( NN )( TT )( ZZ )(C )
o T

¿ o 0
3

N T =N ¿ + δ N Ao x ( C 4 )

δ =( c )−(a+ b)

Divide both side of Eqn.(C4) on NTO:-

NT δ N Ao x
=1+ =1+δ y A 0 x ( C 5 )
N¿ N¿
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Define ε=change in total number of moles when reaction is completed
ε = y A0 δ (C 6)

substitute C6 into C5:-

NT
=1+ε x ( C7 )
N¿

Substitute C7 into C3:-

Po
V =V o ( )( TT )( ZZ ) ( 1+ ε x ) (C )
P o 0
8

The compressibilty factor will not change significantly; Z=Zo

V =V o ( PP )( TT )( 1+ ε x ) (C )
o

o
9

Eqn. C9 represent the volume of gas for batch reaction.

v=v o ( PP )( TT ) ( 1+ε x ) (C
o

o
10 )

Eqn. C10 represent the volumetric flow rate of gas for batch reaction.
Fj
C j= (C )
v 11

Where j any component in the reaction mixture.

F jo ( θ j + v j x )
C j=
v

F jo ( θ j + v j x )
C j=
vo ( PP )( TT ) ( 1+ε x )
o

( θ j +v j x ) P To
C j=C jo ( ( 1+ε x ) )( )( )
Po T
( C 12)

Eqn. C12 represent the gas phase concentration as a function of conversion.

For the reaction in a flow system (volume change):-

aA +bB → cC+ dD

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 b c d
v A =1 ; v B= , v C = ,¿ v D =
a a a

N Ao N Bo N Co N Do
θA= , θB = ,θ C = ,∧θ D = ,
N Ao N Ao N Ao N Ao

( 1−x ) P T o
C A=C Ao
( )( )
( 1+ε x ) Po T
( C 13)

( θ B−v B x ) P T o
C B=C Ao
1+ ε x
( ( )( )
) P T
o
( C 14 )

θC −v C x P T o
C C =C Ao
( )( )
( 1+ ε x ) P o T
( C 15 )

( θD −v D x ) P T o
C D =C Ao
1+ ε x
( ( )( )
) P To
( C 16 )

Ex:-

A mixture of 28% SO2 and 72 % air is charged to a floe reactor in which SO2 is
oxidized
2 S O2 +O2 →2 S O3

a) Set up a stoichiometric table evaluating the symbols(i.e., ϴi,Ci)

b) Prepare a stoichiometric table evaluating numerically when the total pressure is
1485 KPa and the temperature is 227 oC?
Sol:-

a) Taking SO2 as a basis of calculations:-

2 A + B→ 2 C

Species Symbol Initially Change Change Remaining

SO2 A FAO -FAOx -FAOx FA=FAO(1-x)
O2 B FBO=ϴB FAO -(b/a) FAOx -FAOx/2 FB=FAO(1-x)
SO2 C 0 +(c/a) FAOx +FAOx FC=FAOx
N2 I FIO=ϴI FAO - FI=FIO= ϴI FAO
FTO FT=FTO- FAOx/2

b) Initially 72% of the total number of moles is air, containing 21% O2 and 79% N2
F o SO =F Ao=0.28 F ¿ ; F oO 2=0.72∗0.21 F ¿ =F Bo
2

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 F Bo 0.72∗0.21 F ¿
θ B= = =0.54
F Ao 0.28 F¿
F 0.72∗0.79 F ¿
θ I( N )= Io = =2.03
2
F Ao 0.28 F ¿

F A F Ao (1−x ) Po
C A=
v
=
v
; v=v o ( 1+ ε x )( )( TT )
P o

For isothermal operation(T=To) so (T/To)=1

For isberic operation (∆P=0) so (Po/P)=1
CTo= total concentration of component
Po 1485 KPa
C ¿= = =0.1 mol /¿ /dm3 ¿
RTo KPa . lit
8.314 ∗500 K
mol . k
1
(
ε = y Ao δ=0.28 1− −1 =−0.14
2 )
( 1−x )
C A=0.1 mol /¿/dm3 ¿
1−0.14 x
1
θ B− x
2 ( 0.54−0.5 x )
C B=C Ao =0.1 mol /¿/dm3 ¿
( 1+ ε x ) 1−0.14 x

C Ao x 0.1 x
C C= = mol/¿ /dm3 ¿
(1+ ε x ) 1−0.14 x
C θ 0.1 (2.03 )
C I = Ao I = mol /¿/dm3 ¿
( 1+ε x ) 1−0.14 x

Species X=0 X=0.5 X=0.75

SO2 CA=0.1 CA=0.054 CA=0.028
O2 CB=0.054 CB=0.031 CB=0.018
SO2 CC=0.0 CC=0.054 CC=0.084
N2 CI=0.203 CI=0.218 CI=0.227
CT=0.357 CT=0.357 CT=0.357

Tubular Reactor:-
Gas phase reactions are carried out primarly in tubular reactors. By assuming that there
are no radial gradients in either temperature, velocity, or concentration, we model the
flow in the reactor as Plug Flow.
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−dF A
=−r A ( 2.14 )
dV

For a flow system, FA has previously been given in terms of the entering molar flow
rate FAo and the conversion x
F A=F Ao−F Ao x (2.10 )

Combine these equations:-

dx
F Ao =−r A ( 2.15 )
dV

We now separate the variables and integrate with limit V=0 when x=0 to obtain the
PFR volume necessary to a chieve a specifide conversion x:-
x
dx
V =F Ao∫ ( 2.16 )
0 −r A

Where :-

V is the volume of PFR , m3

FAo is rate of feed of A in moles per time

X is conversion of A, percentage or fraction.

rA is rate of reaction , kmol/m3.s

i) If the mass flow rate of A is (ṁ) in kg/s given , to calculate FAo we need only
to divide the value of (ṁ) by the M.wt of A.
ii) If the production rate is given, to calculate FAo:-
ṁ product
M . wt product
F Ao=
x

dx
V =v o C Ao∫
−r A

V dx
τ= =C ∫ (2.17)
vo Ao −r A

Space time (τ ):-

Time needed to treat(i.e., process) one reactor volume of feed measured at specifide
conditions:-
dx
τ =C Ao ∫
−r A
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Mean residence time (t́ ):-

Time of flowing material in the reactor :-

V C Ao V
t́= = (2.18 )
vo F Ao

For constant density system ( all liquids and constant density gases):-
V
τ =t́= (2.19)
v

Space velocity (1/τ ):-

Number of reactor volumes of feed measured at specifide conditions which can be

treated in unit time(1/time).

Example:-

A space time of 2 minute mean that evry 2 minutes one reactor volume of feed at
specifide conditions is being treated by the reactor.

A space velocity of 5 hr-1 means that five reactor volumes of feed at specifide
conditions are being fed into the reactor per hr.

Example:- PFR second order reaction

1- PFR design equation

dx
V =F Ao ∫
−r A
2- Substitutiing the rate law for special case of a second order reaction gives:-
dx
V =F Ao∫
K C2A

3- For constant temperature and constant pressure gas phase reactions, the
concentration is expressed as a function of conversion:-
1−x
C A=C Ao
1+εx
4- Then substituted into the design equation:-
x 2
( 1+ εx )
V =F Ao∫ 2 2
dx
0 K C Ao ( 1−x )

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5- The entering (initial) concentration Cao can be taken outside the integral sign
since it is not a function of conversion and also the specific reaction rate constant
may be considured constant since the reaction is carried out isothermally:-
x 2
F Ao ( 1+εx )
V= 2 ∫ 2
dx
K C Ao 0 ( 1−x )
6- From the integral equations in Appendix A-2, Fogler, we find that:-
vo ( 1+εx )2 x
V=
K C Ao [
2 ε (1+ ε ) ln ( 1−x )+ ε 2 x+
1−x ]
(4.20)

7- If we divide both sides of Eqn. 4.20 by the cross sectional area of the reactor, Ac,
we obtain the following equation relating reactor length to conversion:-

vo (1+ εx )2 x
L=¿
K C Ao A C [
2 ε ( 1+ε ) ln ( 1−x ) + ε 2 x +
1−x ](4.2 1)

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