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Reaction Orders
Arrhenius Equation
Stoichiometric Table
Definitions of Concentration
Calculate the Equilibrium Conversion, Xe
1
We shall set up Stoichiometry Tables using species A as our basis
of calculation in the following reaction. We will use the
stochiometric tables to express the concentration as a function
of conversion. We will combine Ci = f(X) with the appropriate
rate law to obtain -rA = f(X).
b c d
A + B→ C + D
a a a
A is the limiting Reactant.
2
NA = NA 0 − NA 0 X
For every mole of A that react, b/a moles of B react. Therefore
moles of B remaining:
b NB 0 b
N B = N B 0 − N A 0 = N A 0 − X
a NA 0 a
Let ΘB = NB0/NA0
Then:
b
N B = N A 0 B − X
a
c c
NC = NC 0 + N A 0 X = N A 0 C + X
3 a a
Species Symbol Initial Change Remaining
A A NA0 -NA0X NA=NA0(1-X)
B B NB0=NA0ΘB (-b/a)NA0X NB=NA0(ΘB-b/aX)
C C NC0=NA0ΘC (+c/a)NA0X NC=NA0(ΘC+c/aX)
4
δ = change in total number of mol per mol A reacted
Note: If the reaction occurs in the liquid phase
or
if a gas phase reaction occurs in a rigid (e.g. steel) batch reactor
Then V = V0
N A N A 0 (1 − X )
CA = = = CA 0 (1 − X )
V V0
NB NA 0 b b
CB = = B − X = C A 0 B − X
V V0 a a
etc.
5
Suppose − rA = k AC AC B
Batch: V = V0
b
− rA = k AC A0
2
(1 − X ) B − X
a
Equimolar feed: B = 1
b
Stoichiometric feed: B =
a
6
if −rA = k A CA2 CB then
b
−rA = CA 0 3
(1 − X ) B − X ConstantVolume Batch
2
a
and we have −r = f (X )
A
1
− rA
7
X
Calculating the equilibrium conversion
for gas phase reaction,Xe
Consider the following elementary reaction with KC=20 dm3/mol
and CA0=0.2 mol/dm3.
Xe’ for both a batch reactor and a flow reactor.
2A B
2 CB
− rA = k A C A −
KC
8
Calculate Xe
C A0 = 0.2 mol dm 3
K C = 20 dm3 mol
Step 1: dX −rAV
=
dt NA 0
Step 2: rate law, − rA = k A C 2A − k BC B
2 CB
− rA = k A C A −
K C
kA
KC =
9 kB
Calculate Xe
Symbol Initial Change Remaining
A NA0 -NA0X NA0(1-X)
B 0 ½ NA0X NA0 X/2
@ equilibrium: -rA=0 C Be
0=C −2
Ae
KC
CBe N Ae
Ke = 2 CAe = = CA 0 (1 − X e )
CAe V
Xe
CBe = CA 0
10 2
Calculating the equilibrium conversion
for gas phase reaction
Solution:
At equilibrium 2 C Be
− rA = 0 = k A C Ae −
K C
C Be
KC = 2
C Ae
Stoichiometry A → B/ 2
Constant volume V = V0
Batch
Species Initial Change Remaining
A NA0 -NA0X NA=NA0(1-X)
B 0 +NA0X/2 NB=NA0X/2
11 NT0=NA0 NT=NA0-NA0X/2
Xe
CA0
2 Xe
Ke = =
C A 0 (1 − X e ) 2C A 0 (1 − X e )
2 2
= 2(20)(0.2) = 8
Xe
2K e C A 0 =
(1 − X e )2
X eb = 0.703
12
Writing -rA Solely as a Function of X.
13
Rate Law: -rA=kC3AC2B
Stoichiometry:
Species A
Liquid phase, v = vo (no volume change)
Species B
Where: i = Fi 0 = Ci 0 0 = Ci 0 = yi 0
FA 0 C A 0 0 CA0 yA0
and d c b
= + − −1
a a a
Concentration – Flow System C A = FA
17
Species Symbol Reactor Feed Change Reactor Effluent
A A FA0 -FA0X FA=FA0(1-X)
B B FB0=FA0ΘB -b/aFA0X FB=FA0(ΘB-b/aX)
C C FC0=FA0ΘC +c/aFA0X FC=FA0(ΘC+c/aX)
D D FD0=FA0ΘD +d/aFA0X FD=FA0(ΘD+d/aX)
Inert I FI0=FA0ΘI ---------- FI=FA0ΘI
FT0 FT=FT0+δFA0X
Fi 0 C C y d c b
Where: i = = i0 0 = i0 = i0 and = + − −1
FA 0 C A 0 0 C A 0 y A 0 a a a
FA
Concentration – Flow System C A =
18
FA
Concentration Flow System: C A =
Liquid Phase Flow System: = 0
FA0 (1 − X )
= C A0 (1 − X ) Flow Liquid Phase
FA
CA = =
0
N B N A0 b b
CB = =
B − X = C A0 B − X
V V0 a a
etc.
19
If the rate of reaction were − rA = kC AC B
b
then we would have − rA = C A0
2
(1 − X ) B − X
a
This gives us − rA = f ( X )
FA0
− rA
20
X
Combining the compressibility factor equation of
state with Z = Z0
Stoichiometry: P
CT =
ZRT
P0
CT 0 =
Z 0 R0T0
FT = CT
FT 0 = CT 00
We obtain:
FT P0 T
= 0
FT 0 P T0
21
FA P T0 FT 0 FA P T0
C A = FA = =
FT P0 T 0 FT P0 T
0
F0
CT 0 = FT 0 0
FB P T0
C B = CT 0
FT P0 T
22
23
The total molar flow rate is: F = F + F X
T T0 A0
Substituting FT gives: = 0 FT 0 + FA0X
T P0
FT 0 T0 P
FA0 T P0
= 0 1 + X
FT 0 T0 P
= 0 (1 + y A0X )
T P0
T0 P
= 0 (1 + X )
T P0
24 T0 P
FA
Concentration Flow System: C A =
= 0 (1 + X )
T P0
Gas Phase Flow System:
T0 P
FA FA0 (1 − X ) C (1 − X ) T0 P
CA = = = A0
0 (1 + X )
T P0 (1 + X ) T P0
T0 P
b b
FA0 B − X C A0 B − X
CB =
FB
= a
= a T0 P
(1 + X ) T P0 (1 + X ) T P0
0
25 T0 P
If –rA = kCACB
b
(1 − X ) B − a X P T 2
− rA = k AC A0
2 0
(1 + X ) (1 + X ) P0 T
This gives us
FA0/-rA
26 X
Xef
Consider the following elementary reaction with KC=20 dm3/mol
and CA0=0.2 mol/dm3.
Calculate Equilibrium Conversion or both a batch reactor (Xeb)
and a flow reactor (Xef).
2A B
2 CB
− rA = k A C A −
27 KC
2A B
X eb = 0.703
X ef = ?
Solution:
2 CB
Rate law: − rA = k A C A −
K C
1
A→ B
2
28
Species Fed Change Remaining
A FA0 -FA0X FA=FA0(1-X)
B 0 +FA0X/2 FB=FA0X/2
FT0=FA0 FT=FA0-FA0X/2
29
A FA0 -FA0X FA=FA0(1-X)
B 0 FA0X/2 FB=FA0X/2
V = V0 (1+ X )
FA 0 (1 − X ) CA 0 (1 − X )
CA = =
V0 (1+ X ) (1+ X )
FA0 X 2 C A0 ( X )
CB = =
30
V0 (1 + X ) 2(1 + X )
C (1 − X ) 2 C A0 X
− rA = k A A0
−
(1 + X ) 2(1 + X )K C
Pure A → yA0=1, CA0=yA0P0/RT0, CA0=P0/RT0
1
= y A0 = (1) − 1 = −
1
2 2
@ eq: -rA=0
X e (1 + X e )
2 K C C A0 =
31 (1 − X e )2
dm3 mol
2 K C C A0 = 2 20 0.2 3 = 8
mol dm
1 1
= y A 0 = 1 −1 = −
2 2
X e − 0.5X e 2
8=
(1 − 2X e + X e
2
)
8.5X e 2 −17X e + 8 = 0
36