Developing and Using Stio Tables Notes

Stoichiometric Table Batch System
Stoichiometry set up of equations with A as basis
aA + bB cC + dD
specie initial
change
i = Nio/NAo
= (d/a) + (c/a) (b/a) - 1
remaining
NAo
NBo = NAo B
-(b/a)NAo X
NB = NAo[B (b/a)X]
NCo = NAo C
+(c/a)NAo X
NC = NAo[C +(c/a)X]
NDo = NAo D
+(d/a)NAo X
ND = NAo[D +(d/a)X]
NI = NAo I
NI = NAo I
NTo = NAo i
NT = NTo +NAoX
-NAo X
NA = NAo(1 X)
Stoichiometric Tables
Express table in terms of concentrations
Concentration (batch):
Ni
Ci =
V
Constant Volume Batch
V = V0
NA NA 0 (1 X )
=
= C A 0 (1 X )
CA =
V
V0
CB =
CC =
ND NA 0
c
c
+
X
=
C
+
X
C
A0
C
V
V0
a
a
ND NA 0
d
d
b
NB NA 0
b
=
=
+
=
+
C
X
C
X
=
X
=
C
D
D
A0
D
A0 B
a
V
V0
a
V
V0
a
a
Elementary rate law substitution:
aA + bB cC + dD
a b C cCCDd
rA = k A C A CB
KC
NA NA 0 (1 X )
CA =
=
= C A 0 (1 X )
V
V0
CB =
CC =
ND NA 0
c
c
+
X
=
C
+
X
C
A0
C
V
V0
a
a
ND NA 0
d
d
NB NA 0
b
b
=
=
+
X
=
C
+
X
C
=
X
=
C
D
D
A0
D
A0 B
V
V0
a
a
V
V0
a
a
Stoichiometric Table Flow System

Stoichiometry set up of equations with A as basis
aA + bB cC + dD
specie initial
i = Fio/Fao= Cioo/Cao o= yio/yao

= (d/a) + (c/a) (b/a) - 1
change
remaining
FAo
FBo = FAo B
-(b/a)FAo X
FB = FAo[B (b/a)X]
FCo = FAo C
+(c/a)FAo X
FC = FAo[C +(c/a)X]
FDo = FAo D
+(d/a)FAo X
FD = FAo[D +(d/a)X]
FI = FAo I
-FAo X
FTo = FAo i
i
FA = FAo(1 X)
FI = FAo I
FT = FTo +FAoX
concentration (liquid flow):
Fi
Ci =
constant volumetric flowrate
= 0
FA FA 0 (1 X )
CA = =
= C A 0 (1 X )
0
FB FA 0
b
b
CB = =
B X = C A 0 B X
a
a
0
concentration for variable
volumetric gas flow:
Fi
Ci =
From compressibility factor EOS

FT T P0
= 0
FT 0 T0 P
T P
= 0 (1 + y A 0 X ) 0
T0 P
FA 0 T P0
= 0 1 +
X
FT 0 T0 P
T P0
= 0 (1 + X )
T0 P
Fi
Ci =

T P0
= 0 (1 + X )
T0 P
FA 0 1 X T0 P
C A =

0 1 + X T P0
FA
CA =
1 X T0 P
CA = CA0

1 + X T P0
Fi
Ci =

T P0
= 0 (1 + X )
T0 P
B [b a]X T0 P
CB = C A 0

+
1
X
T P0
FA
CA =
1 X T0 P
CA = CA0

1 + X T P0
Example
The following elementary gas-phase reaction takes place in a constantpressure isothermal vessel (1 atm, 25C):
h
CH4 (g) + 2Cl2 (g)
CH2Cl2 (g ,l) + 2HCl(g)
k = 0.2 dm6/(smol2) at 25C (estimated)

CH2Cl2: Pvap = 400 mm Hg (53 kPa) at 25C.
Set up a stoichiometric table, assuming the feed

is in stoichiometric proportions and comprised
only of reactants. Use chlorine as the basis for
calculation.
Example
h
CH4 (g) + 2Cl2 (g)
Component
Symbol
Initial
Change
Out
Cl2
-X
1-X
CH4
0.5
-0.5X
0.5(1-X)
CH2Cl2
+0.5X
0.5X
HCl
+X
Total
1.5
1.5
Example
h
CH4 (g) + 2Cl2 (g)

Calculate .
= y Ao
=0
d c b
= + 1
a a a
= 2 +12 1
=0
Example
h
CH4 (g) + 2Cl2 (g)

Evaluate rA in terms of conversion of chlorine,

the specific reaction rate, and the initial chlorine
concentration.
Example
h
CH4 (g) + 2Cl2 (g)

0.2 dm6/(smol2) 3rd Order (assume elementary)
rA = kC2A CB
Need stoichiometry for CA & CB
Example
h
CH4 (g) + 2Cl2 (g)

System is gas phase until Pc = 400 mm Hg. Need to find
conversion at which CH2Cl2 condenses
n1P1 = n2P2
(1.5)(760) = (0.5 X')(400)
X' = 1.58
C A = C Ao (1 X A )
1
CB = C Ao (1 X A )
2
Therefore, CH2Cl2 does not condense in this system
Example
h
CH4 (g) + 2Cl2 (g)

Substitute stoichiometry into rate law
rA = kC2A CB
= k[C Ao (1 X A )]2 [(C Ao 2)(1 X A )]

k 3
= C Ao (1 X A )3
2
Example
h
CH4 (g) + 2Cl2 (g)

What is the concentration of chlorine at X = 60% ?

C Ao = y Ao
P
RT
1
1 atm
=
1.5 (0.082L atm mol K )(298.2K )
= 0.027mol dm3
C A = C Ao (1 X A )
C A = 0.027mol dm3 (1 0.6 )

= 0.011 = mol dm3
Example
h
CH4 (g) + 2Cl2 (g)

What is the rate of reaction at X = 60%?

k
rA = C3Ao (1 X A )3
2
0.2 dm6 s mol2
3 3
=
0.027mol dm (1 0.6 )3
2
= 1.26 10 7 mol dm3 s
Example
h
CH4 (g) + 2Cl2 (g)

What is the activation energy if the frequency

factor is 2 x 1012 dm6/smol2 ?
k = Ae E RT
Arrhenius Equation
0.2 dm6 s mol2 = 2 1012 dm6 s mol2 e E (8.314 J molK )(298.2K )

E = 74212 J mol
Example
h
CH4 (g) + 2Cl2 (g)

What is the specific reaction rate at 100C ?
k100
1
E 1
= exp
= 410
k 25
R 373.2 298.2
k100 = k 25 410 = 81.95 dm6 s mol2
Arrhenius
Equation
Example (with phase change)

The gas-phase reaction between chlorine and methane to
form carbon tetrachloride and hydrochloric acid is to be
carried out at 75C and at 950 kPa in a continuous-flow
reactor.
4Cl2 + CH4 CCl4 + 4HCl
The vapor pressure of carbon tetrachloride at 75C is 95 kPa.

Volumetric flow rate is 0.4 dm3/s
Set up a stoichiometric table for this reaction with phase change. Calculate
the conversion of methane at which condensation begins.
Plot the concentrations and molar flow rates of each species as well as the
total molar flow rate as a function of conversion for a stoichiometric feed.

T = 75C = 348 K
P = 950 kPa = 9.39 atm
PV ,CCl4 = 95 kPa = 0.94 atm
PV 95
y CCl4 ,e = =
= 0.1
P 950

Stoichiometry set up of equations with CH4 as basis

change
remaining
(PD<PV) before
condensation
remaining
(PD=PV) after
condensation
specie
initial
A - CH4
FAo
-FAo X
FA = FAo(1 X)
FAo(1 X)
B - Cl2
4 FAo
-4FAo X
FB = 4FAo[1 X]
4FAo[1 X]
C - HCl4
+4FAo X
FC = 4FAoX
4FAoX
D(g) - CCl4 (g)
+FAo X
FD = FAoX
0.1 FT
FT = 5FAo
FT = FAo(5-X)
FTo = 5FAo
(0.9)

When condensation begins,
FT = F'T
5 Xc
5FAo = FAo
0.9
X c = 0.5
Therefore, condensation begins at 50% conversion

Before Condensation
Total concentration is constant
= y Ao
=0
=0
Po
gmol
T
=
P
=
0
C T = C To =
= 0.329
RTo
L
1
0.329
gmol
C Ao = C To =
= 0.0658
5
5
L
gmol
L
gmol
0.4 = 0.02631
FAo = C Ao o = 0.0658
s
L
s
Fi
Fi
Fi
=
Ci = =
o (1 + X ) o

Expressing stoichiometric table column remaining (PD<PV) before
condensation in terms of
Fi
Ci =
o
specie
Fi
Ci
A - CH4
FAo(1 X)
CAo(1 X)
B - Cl2
4FAo[1 X]
4CAo(1 X)
C - HCl4
4FAoX
4CAoX
D(g) - CCl4 (g)
FAoX
CAoX
total
5FAo
5CAoX

After Condensation
FT '
= o
FTo
FAo (5 X )
= o
5FAo (0.9 )
5X
= o
4.5
Fi Fi 5 X
Ci = =
o 4.5

Expressing stoichiometric table column remaining (PD=PV) after
condensation in terms of
Fi 5 X
Ci =
o 4.5
Fi
Ci
A - CH4
FAo(1 X)
CAo(1 X) (4.5)/(5-X)
B - Cl2
4FAo[1 X]
4CAo(1 X)(4.5)/(5-X)
C - HCl4
4FAoX
4CAoX(4.5)/(5-X)
D(g) - CCl4 (g)
0.1 FT
CAo(5-X)(4.5)/(5-X) = 0.5CAo
total
FAo(5-X)/0.9
CAo(5-X)(4.5)/(5-X) = 0.5CAo
specie

Developing and Using Stio Tables Notes

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Developing and Using Stio Tables Notes

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Stoichiometric Table Batch System

Stoichiometry set up of equations with A as basis

Constant Volume Batch

Stoichiometric Table Flow System

i = Fio/Fao= Cioo/Cao o= yio/yao

constant volumetric flowrate

From compressibility factor EOS

From compressibility factor EOS

From compressibility factor EOS

k = 0.2 dm6/(smol2) at 25C (estimated)

Set up a stoichiometric table, assuming the feed

k = 0.2 dm6/(smol2) at 25C (estimated)

k = 0.2 dm6/(smol2) at 25C (estimated)

Evaluate rA in terms of conversion of chlorine,

k = 0.2 dm6/(smol2) at 25C (estimated)

0.2 dm6/(smol2) 3rd Order (assume elementary)

Need stoichiometry for CA & CB

k = 0.2 dm6/(smol2) at 25C (estimated)

Therefore, CH2Cl2 does not condense in this system

k = 0.2 dm6/(smol2) at 25C (estimated)

= k[C Ao (1 X A )]2 [(C Ao 2)(1 X A )]

k = 0.2 dm6/(smol2) at 25C (estimated)

What is the concentration of chlorine at X = 60% ?

C A = 0.027mol dm3 (1 0.6 )

k = 0.2 dm6/(smol2) at 25C (estimated)

What is the rate of reaction at X = 60%?

k = 0.2 dm6/(smol2) at 25C (estimated)

What is the activation energy if the frequency

0.2 dm6 s mol2 = 2 1012 dm6 s mol2 e E (8.314 J molK )(298.2K )

k = 0.2 dm6/(smol2) at 25C (estimated)

What is the specific reaction rate at 100C ?

Example (with phase change)

4Cl2 + CH4 CCl4 + 4HCl

The vapor pressure of carbon tetrachloride at 75C is 95 kPa.

Example (with phase change)

Example (with phase change)

4Cl2 + CH4 CCl4 + 4HCl

D(g) - CCl4 (g)

Example (with phase change)

Example (with phase change)

Example (with phase change)

D(g) - CCl4 (g)

Example (with phase change)

Example (with phase change)

D(g) - CCl4 (g)

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