CRE-Stoichiometric Tables

Summary-Problems
Chemical Reaction Engineering (CRE) is the
field that studies the rates and mechanisms of
chemical reactions and the design of the
reactors in which they take place.
 Lecture 4
Block 1
Mole Balances
Size CSTRs and PFRs given rA=f(X)
Block 2
Rate Laws
Reaction Orders
Arrhenius Equation
Block 3
Stoichiometry
Stoichiometric Table
Definitions of Concentration
Calculate the Equilibrium Conversion, Xe

2
Review Lecture 3
Algorithm
How to find r A fX

Step 1: Rate Law rA g Ci

Step 2: Stoichiometry Ci h X

Step 3: Combine to get rA f X

3
 Stoichiometric Tables
Stoichiometric Tables are like account statements
of the reactors.
Very useful bookkeeping tool for writing rate laws
in terms of conversion.
Can be used for batch or flow reactors
Can be written in terms of N, C, or F
Table includes the following columns:
1. Particular species, reactant or product
2. Number of moles initially present
3. Change in number of moles due to the reaction
4. Number of moles remaining

4
 on
gas phase concentration
Concentration, by definition is moles of species per unit volu
ni
Ci
V

The idea here is to find out if and how

concentration may vary with pressure and
temperature.
Equation of State for a Real Gas

PV z n R T z=1 for ideal gas

n P Concentration of a species in

V z RT gas phase is a function of
both pressure and
temperature.
 Effect of pressure and temperature on
liquid phase concentration
Let us say that we have ni moles of a chemical species
in a total liquid volume of V. Accordingly, the
concentration nof species i is:
Ci i

Our interest is in determining how the volume of

liquid changes with temperature and/or pressure.

The liquid density does not change significantly

with temperature and pressure, therefore, the
volume of a fixed mass of liquid does not change
significantlyConcentration
Conclusion: either. of a species in liquid-phase
can be considered to vary negligibly with changes in
pressure and temperature.
Stoichiometric Table for
Batch Reactors
Batch System - Stoichiometry Table

Species Symbol Initial Change Remaining

A A NA0 -NA0X NA=NA0(1-X)
B B NB0=NA0B -b/aNA0X NB=NA0(B-
b/aX)
C C NC0=NA0C +c/aNA0X NC=NA0(C+c/aX
)
D D ND0=NA0D +d/aNA0 ND=NA0(D+d/aX
Inert I NI0=NA0I X
---------- )
NI=N A0 I

NT0 NT=NT0+NA0X
Ni0 Ci 0 0 Ci 0 yi 0 d c b
Where: i 1
N A0 C A0 0 C A0 y A0 and a a a
8
= change in total number of mol per mol A reacted
 Some Useful Definitions
b c d
Reaction: A B C D
a a a
1. Net mole change for the reaction
For above reaction, let us define a term , which represents net
change in total number of moles per mole of A reacted

d c b
1
a a a

2. Relationship between and initial mole fraction of A

Change in total number of moles when complete conversion of A is attained

Total number of moles of all species fed to the reactor

N AO NT NT 0 X N A0
y A0 1 X
N TO N TO NT 0
Calculating Concentration for Batch Reactors

From stoichiometric table, we have Ni = f(X). The concentration of

individual species (reactants and products) can be calculated if
we know the volume occupied by the reacting mixture.
Ni
Concentration in Batch Reactors : Ci
V
The calculation method for volume will depend on the
reaction condition as well as on the reactor type.

Reaction Condition
(i) Gas-phase reaction
(ii) Liquid-phase reaction

Reactor types
A. Constant volume reactors
B. Variable volume reactors
Calculating Concentration for Batch Reactors (Continued)

A. Constant volume reactors

Case I: Liquid Phase-Reaction e.g. polymerization reaction

Case II: Gas Phase-Reaction with =0

e.g. water gas shift reaction: CO + H2O CO2 + H2
methane oxidation : CH4 + 2O2 CO2 + 2H2O

Case III: Gas Phase-Reaction with 0

e.g. ammonia synthesis: N2 + 3H2 2 NH3 [ <0]
propane oxidation: C3H8 + 5O2 3CO2 + 4H2O [ >0]

B. Variable volume reactors:

Case IV: Gas Phase-Reaction in Variable Volume Reactor
e.g. combustion engine
 Calculating Concentration for Batch Reactors
Constant Volume Batch Reactors Cases I & II
(Continued)
Recall, our goal is to calculate volume for the different N
Ci i
batch reactor operations. We can get the number of moles V
of any species (Ni) as a function of conversion from
stoichiometry table.
Case I: Constant Volume Reactor + Liquid Phase-
Reaction
For liquid phase reaction, the volume of interest for
calculation of concentration is the volume that liquid
occupies, which is usually the initial volume of liquid (V 0).

V = V0 volume of liquid in the reactor, could be < reactor

volume]

Case II: Constant Volume Reactor Gas Phase-Reaction

with=0
Calculating Concentration for Batch Reactors
Constant Volume Batch Reactors Case III

Case III: Constant Volume Reactor Gas Phase-Reaction

with 0

V = V0 = VR [gas occupies the total volume of the

reactor]
The pressure in such systems varies with conversion.
Variation of pressure has been used to monitor the
progress of a reaction. Pressure (P) at any conversion
X can be expressed according to the following
relationship:
T P0
Gas Phase Flow/batch 0 1 X
T0 P
System:
T
P Po (1 X )
To
Calculating Concentration for Batch Reactors
Variable Volume Batch Reactor Case IV

Case IV: Variable Volume Reactor with Gas Phase-

Reaction (0) V V0

The pressure in such systems may be constant or vary

with conversion. At any given conversion, X, the
reactor volume may be related to initial reactor
volume (V0) and other operating parameters (P0, T0, P,
and T)
N T Po T Z NT Po T
V Vo ( ) ( ) V Vo ( )
N TO P To Z o For ideal gas N TO P To
P T Z Po T
Vo (1 X )( o ) ( ) Vo (1 X )( )
P To Z o P To
Flow Reactors
 Flow System Stoichiometric Table

Species Symbol Reactor Feed Change Reactor Effluent

A A FA0 -FA0X FA=FA0(1-X)
B B FB0=FA0B -b/aFA0X FB=FA0(B-b/aX)
C C FC0=FA0C +c/aFA0X FC=FA0(C+c/aX)
D D FD0=FA0D +d/aFA0X FD=FA0(D+d/aX)
Inert I FI0=FA0I ---------- FI=FA0I
FT0 FT=FT0+FA0X

Fi 0 Ci 0 0 Ci 0 y d c b
Where: i i0 and 1
FA0 C A0 0 C A0 y A0 a a a

FA
Concentration Flow System C A
16
Calculating Concentration for Flow Reactors

Fi
Concentration in Flow ReactorsC:i
v
From stoichiometric table, we have Fi = f(X)
What value of v should we use to calculate
concentration?
Liquid phase reactions: v = vO
For isothermal and isobaric reactors
Gas phase reactions
Po T with no change in number of moles
v vo (1 X )( ) (i.e. =0)
P To
v = vo
Exercise 1.1 SO 2 12 O 2 SO 3
A mixture of 28% SO2 and 72% air is charged to a
flow reactor in which SO2 is oxidized. The total
pressure is 1485 kPa (14.7 atm) and the
temperature is constant at 227 C. If the rate law
for this reaction were first order in SO2 (i.e., A,
limiting reactant) and in O2 (i.e., B) with k=200
dm3/mol.s
Please write an expression of rate of reaction as
a function of conversion
Exercise 1.2: A mixture of 28% SO2 and 72% air is charged to a flow reactor in
which SO2 is oxidized: First, set up a stoichiometric table using only the
symbols (i.e., i, Fi) and then prepare a second stoichiometric table evaluating
numerically as many symbols as possible for the case when the total pressure
is 1485 kPa (14.7 atm) and the temperature is constant at 227 C.1
Taking SO2 as the basis of SO 2 2 O 2 SO 3
calculation:

FA0 (0.28) FT 0
FB 0 (0.72)(0.21) FT 0
FI 0 (0.72)(0.79) FT 0

FB 0 (0.72)(0.21) FI 0 (0.72)(0.79)
B 0.54 I 2.03
FA0 0.28 FA0 0.28
 SO 2 12 O 2 SO 3
y A0 (0.28)(1 1 12 ) 0.14

P0 T
v v0 1 X
FA FA0 (1 X ) T0
P FA0 (1 X ) 1 X
CA CA C A0
v v v0 (1 X ) 1 X
P 1 X
C A0 y A0CT 0 y A0 0 C A C A0
RT0

1 X
1485kPa
0.28 1 X
8 .314 kPa dm 3
/( mol K ) 500  K 0.1 mol / dm
3

0.1mol / dm3
1 0.14 X

 FT FT 0 y A0XFT 0
1 X 1 X CT
C A C A0 0.1 mol / dm
3
v v0 (1 X )
1 X 1 0.14 X
FT 0 (1 X )
B 12 X 0.54 0.5 X 3
C B C A0 0.1 mol / dm v0 (1 X )
1 X 1 0.14 X
P0
C X
CC A 0
0. 1 X
mol / dm 3
CT 0
1 X 1 0.14 X RT0
C (0.1)(2.03) 1485kPa
C I A0 I mol / dm 3
1 X 1 0.14 X [8.314kPa dm 3 / mol K ](500K )
0.357 mol / dm 3

Change concentration!
If the rate law for this reaction were first order in SO2
(i.e., A) and in O2 (i.e., B) with k=200 dm3/mol.s:

rA kC AC B
1 X 0.54 0.5 X
C A 0.1 mol / dm C B 0.1
3
 mol / dm 3

1 0.14 X 1 0.14 X
2(1 X )(0.54 0.5 X )
rA
(1 0.14 X ) 2