CHG 2317

Introduction to Chemical
Process Analysis
Chapter 4: Material Balances

Contents
 Process classification
 Fundamentals of mass balance calculations
 Balances on multi-unit processes
 Systems with recycling and purging
 Balances on reactive systems

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 Process classification
 Feed and Discharge Modes
 Batch processes (batch): nothing in, nothing out
 Semibatch processes (fed-batch): something in, nothing
out
 Continuous processes: both in and out
 Changes with time?
 Steady-state processes:
 System parameters do not change with time
 Unsteady-state (transient) processes:
 At least one system parameter changes with time

Fundamentals of mass balance

calculations
General Balance Equation (total mass, species mass, energy,
momentum):

What  What is  What  What is  What 

 + -  -  = 
enters generated leaves consumed accumulates
 Applies to total mass, species mass, energy, momentum
 For total mass, set ?=0 and ?=0;
 Non-reactive, set ?=0 and ?=0;
 Continuous process, set ?=0

Forms for batch, semi-batch (fed-batch), continuous, steady-state

processes, non-reactive, reactive, nuclear,…

Two types of approaches: integral and differential

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 Fundamentals of mass balance
calculations
General Procedure for Mass Balance Calculations
1. Draw a flowchart and identify all known and unknown variables
2. Choose a convenient basis of calculation
3. For a multiple unit process, identify the subsystems for which
balances might be written
4. Unit conversion (if not initially consistent)
5. Determine DOF (if DOF=0, <0, >0…then)
6. Analysis for the overall system and each possible subsystem
7. Formulate and simplify the appropriate balance equations
8. Solve the equations
9. Calculate the quantities in question
10. Scale if the base case is different from what is in the problem
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Material balance calculations,

degrees of freedom
From mathematics, we know that sets of equations
can be solved only if the number of independent
equations equals the total number of unknowns,
then a set of unique solutions can be obtained.
 DOF = # of unknowns - # of equations
 If DOF > 0, try to find more equations or try to
examine another part of the whole system
 If DOF < 0, verify if all the equations are
independent
 Until DOF = 0 and solve
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 Material balance calculations,
degrees of freedom analysis
1. For selected sub-system(s), list ALL the governing
equations
 Mass balances (“i” independent equations for “i”
species);
 Process specifications (i.e., A = 0.4B, conversion of
?, % excess of ?…);
 Physical properties or laws;
 Reaction stoichiometry (# of equations = # of
independent reactions)
2. If # of unknowns = # of equations, can be solved first;
otherwise look at other sub-systems.

Example, DOF of multiple unit system

Complete system: DOF = 0; 2 unknowns (m3 & x3), two

balances (A & B);
Unit #1: DOF=0; 2 unknowns (m1 & x1), 2 balances (A &
B);
Unit #2: DOF=2; 4 unknowns, 2 balances. 8

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 Recycle, bypass, mixing point, splitting
point, and purge

Fresh feed Feed to Unit 1

Output

Recycle

Stoichiometry of reactions

 Reactions react in proportion:

N2 + 3H2 2NH3

If a unit of N2 reacts with b units of H2 and

produces c units of NH3, one situation must
be, a=1; b=3, and c=2.
No matter what, a, b, and c, always exist as
a/1 = b/3 = c/2.
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 Some chemical reaction
terminology
 Limiting and excess reactants
 Fractional (also %) conversion: reacted/fed
 Extent of reaction: the quantity of a reference
reactant that is reacted;
 Yield: moles formed/moles that would form if there were no
side reactions
 Selectivity: desired product/undesired product(s)
 Equilibrium constant: product of the mole fractions
of all products/product of the mole fractions of all reactants
(yNH3/yH2*yN2)
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Extent of Reaction (ξ)

 In reaction: C2H2 + 2H2  C2H6

if ξ moles of C2H2 reacted, then 2ξ moles of H2 would have been
consumed, and ξ moles of C2H6 would be formed. The number of
moles of the species would be:
n C2H2 = (n C2H2 )0 – ξ,
n H2 = (n H2 )0 – 2ξ, and
n C2H6 = (n C2H6 )0 + ξ,

In reaction: 3H2 + N2  2NH3

if ξ moles of N2 reacted, then 3ξ moles of H2 would have been
consumed, and 2ξ moles of NH3 would be formed.

 Now let νi be the stoichiometric coefficient of species i in a chemical

reaction, making it negative for reactants and positive for products; ξ is
the extent of reaction or the quantity of a reference reactant that is
reacted, then
ni = ni0 + νiξ
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 Equilibrium Constant of
Chemical Reactions
 CO (g) + H2O (g) CO2 (g) + H2 (g)

y y
CO2 H2
K (T ) 
y y
CO H 2O

 Equilibrium constant (K) may be expressed by KP

(if pressures are used for the denominators and
numerators) or KC (if concentrations are used).

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Balances on Reactive Processes

 3 different methods:
 Molecular balances (used for single reactions)
Input + generation = output + consumption,
(for each substance)

 Atomic balances (no generation term, used

for multiple reactions)
Input = output (for each atomic element)
 Extent of reaction method

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 Independent equations,
species and reactions
 Independent equations:
Example: Given two equations x+y=0 and 2x+y=5. If there is not a non-
zero number (λ) such that [(x+y)+ λ(2x+y-5)] = 0, then the two
equations are independent. Judge 5xy+4y=12 and 2y=6-2.5xy
Definition: equations f(x)=0 and g(x)=0 are independent if f(x)+λg(x)≠ 0
except for the case that λ=0 or there are limited roots of the equations.

Occurrence in mass balance: If two species are in the same ratio

whenever they appear in a process and this ratio is incorporated in the
flowchart labeling
Example: 2C2H4  C4H8
# of independent atomic balances =
# of independent species =

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Independent reactions
 Independent equations:
Chemical reactions are independent if the stoichiometric equation
of any one of them cannot be obtained by adding or subtracting
multiples of the stoichiometric equations of the others.
Example:
[1]: A 2B
[2]: B C
[3]: A 2C

How many independent ones? (note [1]+2*[2][3])

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 DOF analysis in reactive systems

 Molecular balances

DOF = # of unknowns
+ # of independent reactions
– # of molecular species balances (reactive
and non-reactive)
– # of other equations relating the unknowns

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DOF analysis in reactive systems

 Atomic balances

DOF = # of unknowns
– # of independent atomic balances
– # of molecular balances on independent
non-reactive species
– # of other equations relating the unknowns

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 DOF analysis in reactive systems

 Extent of reaction method:

DOF = # of unknowns
+ # of independent reactions (one extent of
reaction each)
– # of independent reactive species (one
equation for each species in terms of
extents of reaction)
– # of independent non-reactive species (one
balance equation each)
– # of other equations relating the unknowns
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Independent species

• Example: independent species,

n 1 mol O 2 /s n 3 (mol O 2 /s)

3.76n 1 mol N2 /s 3.76n 3 (mol N2 /s)
Humidification n 4 (mol H2O(V) /s)

n2 mol H 2O ( L) / S n 5 (mol H2O(L) /s)

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 Independent Atomic Balances

• Example: Independent atomic balances

200 mol/s 2C2H4  C4H8 n 1 (mol C 2H4 /s)

0.60 mol C 2H4 /mol n 2 (mol C 4H8 /s)
Reactor
0.40 mol N2 /mol n 3 (mol N2 /s)

mol 0.60 mol C2H4 2 mol C mol C 2H4 2 mol C mol C4H8 4 mol C
C: 200 = n 1 + n 2
s mol mol C 2H4 s mol C 2H4 s mol C 4H8
mol 0.60 mol C2H4 4 mol H mol C2H4 4 mol H mol C 4H8 8 mol H
H: 200 = n 1 + n 2
s mol mol C2H4 s mol C2H4 s mol C4H8
C: 240 = 2n 1 + 4n 2  H: 480 = 4n 1 + 8n 2
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Combustion
Terminology in combustion
 Combustion: rapid reaction of fuel + oxygen 
CO2 +…
 Complete combustion ( CO2)
 Partial combustion ( CO)
 Composition on a wet basis: water accounted
for
 Composition on a dry basis: water not counted
 Stack gas or flue gas
 Theoretical and excess air

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 Balances on reactive processes
 Example: Calculate the missing data from the
following flowchart:
n 1 (mol C 2H6 /s)
100 mol C2H6 /s n 2 (mol C2H4 /s)
Reactor
30 (mol H2 /s)
10 (mol CH4 /s)
C2H6  C2H4 + H2
C2H6 + H2  2CH4

 Solution: Three methods are available

 Balance on the atomic elements
 Balance on the number of moles reacted (extent of reaction)
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Solution: 1. Balance on the atomic

elements
 mol H  
H balance:   nIn = n Out
 s 
6 mol H 6 mol H 4 mol H
100 mol C 2H6 = n 1 mol C2H6 + n 2 mol C 2H4
mol C2H6 mol C 2H6 mol C2H4
2 mol H 4 mol H
+ 30 mol H2 + 10 mol CH4
mol H2 mol CH4
6 n 1 + 4 n 2 = 500
2 mol C 2 mol C 2 mol H
100 mol C 2H6 = n 1 mol C 2H6 + n 2 mol C2H4
mol C2H6 mol C2H6 mol C 2H4
0 mol C 1 mol C
+ 30 mol H2 + 10 mol CH4
mol H2 mol CH4
2 n 1 + 2 n 2 = 190
n 1 = 60 mol/s ; n 2 = 35 mol/s
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 Solution 2: Balance on the
number of moles reacted
C2H6  C2H4 + H2
C2H6 + H2  2CH4
For this case (basis of calculation) :
ξ 1 = moles C2H6 /s that reacted in the 1st reaction
ξ 2 = moles C2H6 /s that reacted in the 2nd reaction
 
n C2H6 = n C0 2H6 -  1 -  2 n CH4 = 0 + 2 2 = 10   2 = 5 mol/s
n C2H4 = n 0C2H4 +  1 n H2 = 0 +  1 -  2 = 30   1 = 35 mol/s

n H2 = n H0 2 +  1 -  2 n C2H4 = ξ 1 = n 2 = 35 mol/s
n CH4 = n 0CH4 + 2 2 n C2H6 = 100 - ξ 1 - ξ 2 = n 1 = 60 mol/s
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