CHP 294 Notes

CHP 294 LECTURE NOTES
PRINCIPLES OF MASS AND ENERGY BALANCE
CHP 294
COURSE CONTENT
- Introduction to mass and energy balance systems

- General mass balance equation for steady and unsteady flow systems
- Calculations for mass balance on single and multiple stage unit processes, including
recycle, purge and by-pass
- Mass balance with chemical reaction.
- General energy balance equation with chemical reaction
- Energy balance on flow systems and non-flow systems
- Energy balance on chemical systems
- Simultaneous energy and mass balance calculations
- Use of steam tables
- Dimensional analysis
1
MATERIAL BALANCES
They are pre-requisite to calculation of all other calculations in chemical engineering

problems.
They are based on conservation laws of matter.
The general mass balance equation with or without chemical reaction is:
{Accumulaiton
within system } { out } {generated } {consumed }
={material }− material + material − material
¿
Material balances can be carried out bassed on:
- Total mass
- Total moles
- Compound masses
- Atomic masses
- Compound moles
- Atomic species moles
- Volumes (its rarely used. Its only applied on special cases)
When there is no reaction, you neglect the generation and consumption terms.
The mass or mole balance for chemical elements do not involve the consumption and
generation terms.
Steady state problems are those which the accumulation of material equals zero.
Unsteady state problems are thos that have got material accumulating with time and they are
formulated as differential equations with respect to time.
Chemical processes may be classified as:
- Batch
- Semi-batch
- Continuous
Besides this classification, they can also be categorised as steady or unsteady systems.
Before writing material balance on a process system, you must know which of these
categories the process fall into.
Batch process: Substances are fed at once at the beginning and removed at once at the
end of the process
No mass enters or leaves at the time of charging and discharge
2
Continuous process: the inputs and outputs flow continuously throughout the duration of the
process.
Semi-batch: any process that is neither batch nor continuous e.g. slowly blending
liquids in a tank in which the first liquid is already present and there is
no material outflow.
The number of equations which are unique that can be solved in a material balance should be
equal or more than the number of variables present whose values are unknown.
The independence of an equation can be established by formulating a matrix and determining
its rank.
Solving material balance problems involving simultaneous equations
These are equations which are coupled with one another and cannot be solved individually.
They are called irreducible equations. If only two or three coupled material balances are
written for a problem, then solving by substitution can be appropriate. If they are more, then
matrix method or computer soft wares can be ideal.
A material or component that directly goes from one stream into another without changing in
any respect or having like material added to it or lost from it is called tie component/element.
Tie component enables you to write a material balance that only ties/connects two streams
(shows relationship between two streams) thus simplifying the problem.
Flow process, steady state:
EXA 1
In a physical dehydration unit shown below, calculate the mass of water removed per 100 kg
of wet sludge that enter the unit if the process is a steady state.
Solution:
Xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx
EXA 2
One thousand (1,000) kilograms of a mixture of benzene (B) and toluene (T), containing 40%
by mass of B is to be separated into two streams in a distillation column. The top output
stream of the column contains 375 kg of B and the bottom output stream contains 515 kg of
T.
(a) Perform the mass balance for B & T
(b) Determine the composition of the top and bottom streams
3
Solution
Take a basis as “1,000 kg of mixture”
In order to be able to solve for unknowns, it is necessary that the # of Eqs. must be equal to
the # of unknowns.
In this Example, since the input stream consists of only 2 components, we obtain the
following equation:
wt% of B + wt% of T = 100
Accordingly,
% T = 100 - % B
100 = 40
% T = 60%
The input stream comprises:
Benzene (B) = (1,000 kg) = 400 kg
Toluene (T) = (1,000 kg) = 600 kg
In a general form, let
Since the process is steady-state and has no reaction, the mass balance equation can be
written as follows:
Overall mass balance:
1000=P+ Q ..................................................i
Component balance:
Benzene:
4
( 0.4 × 1000 )=375+ y ...................................ii
Solving equation i and ii simultaneously, we obtain
y = 25 kg
x = 460-375 = 85 kg.
EXAMPLE 3
An experiment on the growth rate of organisms requires an environment of humid air
enriched in oxygen. Three input streams are fed into an evaporation chamber:
• liquid water, fed at the volumetric flow rate of 20 cm3/min
• air (21.0 vol% O2 & 79 vol% N2)
• pure O2, with the molar flow rate of one-fifth (1/5) of the stream of air to produce an output
stream with the desired composition
The output gas is analysed and is found to contain 1.5 mol% of water
Calculate all unknowns
(Data: Density of water is 1.0 g/cm3; and MW of water = 18.02, of O2 = 32.00, & of N2 =
28.02)
Solution
Assumption: Steady-state process

Flow chart:
Take a basis of 1 min flow of material
Molar flowrate of water:
Mass=volume × density
5
mass=20 ×1=20 g /min
mass 20
Molar flowrate= = =1.11 moles per min
RMM 18
Material balance:
Water balance:
1.11=0.015 S 4
S4 =74.07 moles per minute .................................. (i)
Nitrogen balance:
0.79 S1=x S 4 ............................................................... (ii)
Oxygen balance:
1.00 S 2 +0.21 S 1= y S 4 ................................................... (iii)
General balance:
S2=1 /5 S1 ..................................................................... (iv)
And
0.015+ x + y=1 ......................................................... (v)
Solving equation (i) and (ii)
0.79 S1=74.07 x
S1=93.76 x ................................................................ (vi)
Combining equstion (i), (iii) and (vi):
S2 +(0.21× 93.76 x)=74.07 y ............................... (vii)
Combining equation (v) and (vii):
S2 +(19.69 x )=74.07(0.985−x)
S2 +93.76 x=72.96 ............................................. (viii)
Combining equation (iv) and (vi):
S2=18.75 x ........................................................... (ix)
Combining equation (ix) and (viii):
6
18.75 x+ 93.76 x=72.96
x=0.648
And thus:
y=0.337
S1=60.76 moles/min
S2=12.15 moles/min
S3=1.11 moles/min
S4 =74.07 moles/min
SINGLE UNIT PROCESSES

1. Material Balances for Processes without Chemical Reactions
The processes involved here doesn’t involve chemical reactions.
They are called unit operations.
Examples of these processes include: mixing, evaporation, drying, humidification etc.
Mixing Process
A mixing process involves two or more streams and the resulting combined stream, for which
its concentration is to be solved
Consider the following Examples
EXAMPLE 4
Two methanol + water mixtures are contained in the separate tanks. The first mixture
contains 40 wt% methanol, and the second contains 30 wt% water. 200 g of the first mixture
is mixed with 150 g of the second one. What are the total mass and composition of the
product?
SOLUTION
Assumptions:
• Steady-state process
• NO chemical reaction between water and methanol
7
Unknowns:
• wt% of water in Stream 1
• wt% of MeOH in Stream 2
• Mass of the product (x )
• wt% of MEOH and water in the product stream (y and z )
Overall mass balance:
m1 + m2 = mproduct
mproduct = 200 g + 150 g
Thus, the mass of product (x) is 350 g
Since Streams 1 & 2 comprise only MeOH & water,
• wt% of water in Stream 1 = 100 – 40.0 = 60.0 wt%
• wt% of MeOH in Stream 2 = 100 – 30.0 = 70.0 wt%
Species balance:
We can perform a species balance for either MeOH or water.
MeOH balance:
( 0.4 × 200 ) + ( 0.7 ×150 ) =350 y
y=0.529
z=0.471
EXAMPLE 5
You are asked to make 1,000 kg of the mixed acid containing 60 wt% H2SO4, 32 wt% HNO3,
and 8 wt% water, by mixing
i) mixed acid containing 11.3% HNO3, 44.4% H2SO4, and 44.3% water,
ii) 90% HNO3 aqueous solution, and
iii) 98% H2SO4 aqueous solution
Calculate mass of Streams i, ii, and iii
SOLUTION
Assumptions:
• NO chemical reactions between water and acids and between H2SO4 and HNO3
8
Basis: 1,000 kg of the product (i.e. the resulting mixed acid solution)
Unknowns:
• Mass of Stream i (x )
• Mass of Stream ii (y)
• Mass of Stream iii (z )
Hence, we need 3 (three) equations
Overall balance:
x + y + z=1000 kg product ............................................... (i)
We still need another 2 (two) equations.
Species balance:
HNO3 balance
0.113 x+ 0.90 y=( 0.32× 1000) ............................................ (ii)
H2SO4 balance:
0.444 x +0.98 z=(1000× 0.60) ............................................ .. (iii)
Solving eqns. (i), (ii) and (iii) simultaneously yields

x = 76.4 kg
y = 346.0 kg
z = 577.6 kg
Comments:
9
In this case, there are 3 unknowns (i.e. x, y, & z) We, however, need to solve for only two,
out of three, unknowns. The last one (i.e. the 3rd unknown) is to be obtained from the
difference between 1,000 (the total amount) and the summation of the other two solved
unknowns.
In such case, we can say that the “degree of freedom (dof)” of this question is 2 (two). In
other words, we need to solve for only 2 unknowns, and the 3rd one will “automatically” be
obtained from the difference of the total value and the summation of the other TWO solved
unknowns.
Mixing Point
“The principle of a mixing point is the same as that of the mixing tank”, except that there
is/are no REAL (or ACTUAL) mixing tank/tanks
EXAMPLE 6
Stream 1, containing only substance A, is mixed with stream 2, which contains substances A
& B, at the mixing point. The flow rates of Streams 1 & 2 are 60.0 & 30.0 kg/h, respectively.
The mass fraction of A in the Stream 2 is 0.35. Determine the composition of the output
stream.
Solution
Assumptions:
• NO chemical reaction between species A and B
Basis: 1 h of operation
m1 = 60.0 kg (containing A only)
m2 = 30.0 kg (containing A & B)
Unknowns:
10
• Wt% of species B in Stream 2

• Mass of the output stream (mo)
• Wt% of species A and B in the output stream (y, and (100 − y) wt%)
Since Stream 2 contains only A & B, when mass fraction of A = 0.35 (or wt% of A = 35%),
mass percentage of B = 65% (or yB = 1.00 – 0.35 = 0.65)
Overall balance
m1 +m2 =mo
60.0 + 30.0 = mo
mo = 90.0 kg
Species B balance
Balance of A:
60+ ( 0.35 × 30 )=( 90 × y )
y=0.783 Mass fraction of A
Z = 0.217 Mass fraction of B
Drying & Concentrating Processes

Drying and concentrating processes involve two species, e.g., solutes and solvent.
Normally, a solute is to be concentrated by removing (e.g., drying) a solvent.
EXAMPLE 7
Evaporator is used to concentrate a dilute 4 wt% caustic soda (CS) solution to 25 wt%.
Calculate the amount of water to be evaporated per 100 kg of feed.
Solution

Basis: 100 kg of feed (a 4 wt% caustic soda solution)
11
Unknowns:
• Mass of the product (i.e. 25 wt% CS solution) (x)
• Mass of water evaporated (y)
Overall balance:
100= x+ y ............................................ (i)
Species balance:
Caustic soda balance:
( 100 ×0.04 )=( 0.25 x )
x=16 kg
y=84 kg water evaporated
Caustic soda is the tie component in this question.
It is a component (i.e substance or species) whose mass (or mole(s)) is (are) constant for
both inlet and outlet streams.
Physical separation process: Centrifugation
Centrifugation is a process which involves the application of the centripetal force for the
sedimentation of heterogeneous mixtures with a centrifuge, and is used in industrial and
laboratory settings. This process is used to separate two immiscible substances.
Example 8
A centrifuge is used to separate blood pellets from blood fluid. In a continuous separation of
blood fluid, 1,000 g/h of blood fluid is fed into a centrifuge, and the feed contains 2,500 ppm
of blood pellets.
12
It is required that the product must contain 80 wt% of blood pellets. Calculate the amount
of blood-pellet- free fluid has to be discharged per hour.
Solution
i.e. 1,000 g of feed
Since the fluid contains 2,500 ppm of blood pellets, the amount of blood pellets in the feed
is:
Since 1ppm = 1 mg/L or 1 mg/kg, then:
2,500 ppm = 2.5 g/kg
Blood pellets are the tie component. Hence, the feed contains the blood pellet-free fluid
Blood pellets balance:
2.5 g = 0.8P
P = 3.125 g
Therefore, the pellet free blood is 1000 – 3.125 g = 996.875 g
EXAMPLE 9
Membrane separation is a new technology for separating gases. A nano-porous membrane is
used to have a concentrated amount of oxygen in the product stream as illustrated in the
picture below.
13
If the total mole of waste stream is 75% of that of the input stream, what is the molar
composition (percentage) of the waste stream?
Solution
Assumptions:
• NO chemical reactions between N2 and O2 in the membrane
Basis: 100 g-mol of the input stream
(nInput =100 g-mol)
Thus, the input stream comprises
• O2 21 g-mol
• N2 79 g-mol
Given:
• Composition of the input stream (21% O2)
• Composition of the output stream (30% O2)
• Total mole of the Waste (= 0.75 n Input); hence, n waste =( 0.75)( 100 g-mol) = 75 g-mol
Unknowns:
• wt% of O2 in the Waste
• wt% of N2 in the Waste
Overall mole balance:
ninput = noutput + nwaste
( 100 g-mol ) = noutput + (75 g-mol)
noutput = 25 g-mol
O2 mole balance:
( 0.21 ×100 )= ( 75 x ) +( 0.3× 25)
Upon solving, we get:
x= 0.18 (18%)
Thus, the molar composition (in percentage) of the waste stream is
• O2 = 18%
• N2 = 82% (i.e. 100 – 18)
14
2. Material Balances for Processes involving Chemical Reactions

For the processes involving chemical reactions, there is an additional term in the material-
balance equation. This additional term is either for material generation or material
consumption.
Consider the chemical reactions stated below:
C H 4+ 202 yields 2C 02+ 2 H 2 O
→
N 2 +3 H 2 yields 2 NH 3
→
CO+ 2 H 2 yields 2 CH 3 OH
→
From the examples of chemical, or “stoichiometric”, reactions above, we obtain the

following information:
• What are the reactants and what are the products of each reaction
• A mole ratio/mole ratios of reactants reacting with each other
• A mole ratio/mole ratios of a resulting product per that/those of a reactant/s
Every stoichiometric equation should be balanced to be regarded as valid.
Limiting & Excess Reactants
Consider the following reaction:
2 SO 2 +O2 yields 2 SO 3
→
This is a “valid” or “balanced” chemical reaction, as number of moles of each element (i.e. S
or O on the reactant and product sides are equal to each other).
If we feed SO2 in the amount lower than 2 mol (say 1.8 mol), whereas the feeding amount of
O2 is still at 1 mol, the following situation take place: SO2 is completely consumed and O2 is
left over.
It is defined that:
- A species that is completely consumed = limiting reactant (sulphur dioxide in our
case)
- A species that is left over = excess reactant (oxygen in our case)
Fractional Excess
Let:
nfed = # of moles of a reactant actually fed into a system
nstoich = # of moles of a reactant consumed according to a stoichiometric equivalent.
Fractional excess can then be defined as:
15
n fed−nstoic h
fractional excess=
n stoich
Excess percentage = 100(fractional excess)
EXAMPLE 10:
If 10 g of N2 reacts with 10 g of H2 and NH3 is formed in the reactor,
(a) which species is the limiting reactant?
(b) which species is the excess reactant?
(c) what is the maximum number of grams of NH3 that can be produced?
(d) calculate the excess percentage of the excess reactant
Solution
The first thing we MUST do is to write a balanced stoichiometric chemical reaction, as
follows:
N 2 +3 H 2 yields 2 NH 3
→
Thus, the stoichiometric ratio for the reactants is 1:3

Moles of N2 fed = 10/28 =0.357 g-moles
Moles of H2 fed = 10/2 = 5.0 g-moles
Note that for the same # of moles of N2 (i.e.0.357 g-mol), the # of moles of H2 fed is higher
than that needed stoichiometrically (or theoretically). Some amount of H2 fed must be left
over.
It can be concluded that:
- N2 is a limiting reactant
- H2 is an excess reactant
Then fractional excess of H2 is:
Stoichiometric equivalent of H2 needed is: 1.071 g-moles
(5.0−1.071)
Excess H 2 = =3.668
1.071
since the number of moles of N2 (limiting reactant) consumed is 0.357 g-mol, the # of mol of
H2 required stoichiometrically can, thus, be calculated as follows
H 2=0.357 × 3=1.071 g−moles
but ( H2 ) actually fed n = 5.0 g-mol
Thus, the excess percentage of H2 can be obtained as follows:
% Excess = 366.8 %
16
The amount of NH3 generated (or produced) must be computed using the amount of
limiting reactant consumed.
In this Example, N2 is a limiting reactant.
Thus, the amount of NH3 generated has to be calculated based on the amount of N2 as
follows:
Limiting reagent ×2=0.357 ×2=0.714 g−moles
Mass of ammonia generated:
0.714 × RMM =0.714 ×17
Masss of ammonia is 12.138 g
EXAMPLE 11
The combustion of n-heptane is
C 7 H 16 +11 O2 yields 7 CO 2+ 8 H 2 O
→
Ten (10) kg of n-heptane is reacted with an excess amount of O2, and 14.4 kg of CO2 is
formed. Calculate the conversion percentage of n-heptane.
Solution
Since it is stated that O2 is in excess, n-heptane is, therefore, a limiting reactant.
The # of moles of 10 kg of C7H16 fed and 14.4 kg of CO2 generated can be computed as
follows
From the given chemical reaction, the stoichiometric ratio between CO2 and C7H16 can be
written as follows:
RMM of n-Heptane = 100
RMM of carbon dioxide = 44
Moles of n-heptane = 10/100 = 0.1 kg-moles
Moles of carbondioxide generated = 14.4/44 = 0.327 kg-moles
Moles of n-heptane required to produce 0.327 kg-moles of carbon dioxide = 0.327/7 = 0.0467
kg-moles
Therefore, the conversion of n-heptane is:
0.0467
f= =0.467=46.7 %
0.1
Fractional Completion
The fraction of a limiting reactant that is “partially” reacted is called “fractional
completion”
17
(note that, sometimes, “fractional completion” can be used interchangeably with “fractional
conversion”)
EXAMPLE 12
The following reactions:
C 2 H 6 yields C 2 H 4 + H 2
→
C 2 H 6 + H 2 yields 2CH 4
→
in which the second reaction is unwanted, take place in a steady-state continuous reactor. The
feed contains 85 mol% C2H6 and the balance inerts. The fractional conversion ( f ) of C2H6 is
0.50, and the yield of C2H4 is 0.47. Calculate the molar composition of the product.
Solution
Basis: 100 g-mol of feed

Hence, the feed contains
• 85 g-mol C2H6
• 15 g-mol inerts
Let
x = g-mol of C2H6 reacted in the first reaction.
y = g-mol of C2H6 reacted in the second reaction.
Thus, the # of moles of C2H6 totally reacted is x + y g-mol
It is given that
• fractional conversion ( f ) of C2H6 = 0.50
• yield of C2H4 = 0.47
Hence,
Since the mole ratios between C2H6 and C2H4 is 1:1, then the moles of C2H4 obtained equals the
moles of C2H6 used in reaction 1:
= 0.47 *85
= 39.95 g-mole of C2H6 used in reaction 1
Actual C2H6 used in reaction 1 and 2 is:
= 0.5*85
18
= 42.5 g-moles
Moles of C2H6 used in reaction 2 are:
= 42.5 -39.95
= 2.55 g-mole
Actual moles of Hydrogen generated = 39.95 g-moles
Actual moles of Hydrogen generated = 39.95 g-moles less consumed in reaction 2 (2.55)
= 37.4 g-moles
Actual amount of methane produced = 2.55*2
= 5.10 g-mole
Hence, the molar composition of the product stream can be tabulated as follows:
Atomic Balances
Since atom cannot be created nor destroyed, for any process, a number of atoms entering the
process must be equal to that leaving the process. We can employ the above “atomic
balances” principle to solve material-balance problems, as illustrated in the following
example.
EXAMPLE 13
Consider the reactor below:
19
Determine the values of n1 and n2
Solution
In the case that we do NOT know the chemical reaction in the reactor, we perform atomic
balances. This is an alternate way of solving problems involving chemical reactions,
especially when specific chemical reaction are NOT known or given.
In this Example, the given data (as shown as a diagram) are as follows:
• C2H6 is fed into the reactor in the amount of 100 g-mol
• the amount of H2 leaving the reactor is 40 g-mol
• C2H4 is another product
• C2H6 is NOT completely consumed
By utilising the principle of atomic balances, we obtain the following:
# of atoms of C (or H) entering the process = # of atoms of C (or H) leaving the process
Input
1 molecular mol of C2H6 comprises
• C = 2 atomic mol
• H = 6 atomic mol
Since the amount of C2H6 fed into the reactor is 100 molecular mol, the amounts of
• C = 2 × 100 = 200 atomic mol
• H = 6 × 100 = 600 atomic mol
Outputs
1) 1 molecular mol of H2 comprises
Since the amount of H2 leaving into the reactor is 40 molecular mol, the amount of
• H = 2 × 40 = 80 atomic mol
2) 1 molecular mol of C2H4 comprises
Since the amount of C2H4 leaving into the reactor is n1 molecular mol, the amounts of
20
• C = 2 × n1 = 2n1 atomic mol

• H = 4 × n1 = 4n1 atomic mol
3) 1 molecular mol of C2H6 comprises
Since the amount of C2H6 leaving into the reactor is n2 molecular mol, the amounts of
• C = 2 × n2 = 2n2 atomic mol
• H = 6 × n2 = 6n2 atomic mol
Performing C and H atomic balances yields
C balance:
Σ(C)input = Σ(C)output, Substituting corresponding numerical values
200 = 2n1 + 2n2
100 = n1 + n2
H balance:
Σ(H)input = Σ(H)output, Substituting corresponding numerical values
600 = 80 + 4n1 + 6n2
260 = 2n1 + 3n2
Solving simultaneously yields;
• n1 = 40 g-mol
• n2 = 60 g-mol
Thus, the total # of moles of the output stream is
= 140 g-mol
21
PRACTICE QUESTIONS
1. A thickener in a waste disposal unit of a plant is used to remove water from wet sewage
sludge, as shown in Figure 1. If the process is steady state, how many kilograms of water
leave the thickener per 100 kg of wet sludge entering the thickener?
2. A new engineer has performed a material balance for a mixing tank as summarised in
Figure 2. Check if this material balance correct, for both overall and species balances.
3. A 20 wt% sodium hydroxide (NaOH) solution is to be diluted to the concentration of 8 wt

%. Determine the amount of water needed.
4. A mixed acid is prepared from mixing 99 wt% sulphuric acid solution (A), 95% nitric acid
solution (B), and pure water (C) together. If 1,000 kg of the mixed acid, containing 50 wt%
H2SO4, 40 wt% HNO3, and 10 wt%, water is needed, calculate the amounts of A, B, and C (in
kg).
5. A 20 wt% H2SO4 solution (density = 1.139 g/cm3) is mixed with a 60 wt% H2SO4 solution
(density = 1.498 g/cm3), in order to obtain a H2SO4 solution with the concentration of 4.0
mol/L. Determine
a) the ratio between the 20 wt% H2SO4 solution and 60 wt% H2SO4 solution, in order to get
the acid solution with the desired concentration
b) the amount of the 60 wt% H2SO4 solution needed if 1,250 kg of 4.0 mol/L H2SO4 solution
is required. (MW of H2SO4 and of water are 98.08 and 18.02, respectively)
22
6. When humid air containing water vapour and air (21 vol.% O2 and 79% N2) is passed
through a condenser, water vapour in the air is condensed. A condenser can condense 95 vol
% of the water vapour entering the condenser. If the flow rate of the outgoing condensed
water is 225 L/h, calculate
a) the ratio between the humid air entering the condenser and that leaving the condenser
b) the composition (in mole fraction) of the air leaving the condenser.
7. Humid air containing 4 mol% water vapour is passed through a column filled with a
desiccant. It is found that 97 mol% of water vapour is adsorbed onto the desiccant. The
weights of the desiccant before and after the operation are 3.40 and 3.54 kg, respectively. If
the operation lasts 5 hour, determine
a) the molar flow rate (in g-mol/h) of the humid air entering the column
b) the mole fraction of water vapour adsorbed onto the desiccant, compared with the total
amount of water entering the column.
8. Ammonia (NH3) is burned with air (comprising O2 21% and N2 79% by vol.) in a reactor,
and the products are nitric oxide (NO) and water (H2O), as illustrated in the following
reaction:
4 NH 3 +5 O2 yields NO+6 H 2 O
→
a) If ammonia is fed into the reactor at the feed rate of 100 kmol/h, calculate the flow rate of
air in order to have the percentage excess of O2 of 40%
b) If NH3 and air are fed into the reactor at the flow rates of 50 and 330 kg/h, respectively.
Determine which reactant is a limiting reactant, and calculate the fractional excess of the
excess reactant
c) If the percentage conversion of this reaction is 55%, and the NO formation rate is limited
not to exceed 2 kg/h, determine the flow rates of NH3 and air when the percentage excess of
O2 is 30%
9. Highly-concentrated sugar (widely used in food industry) contains sugar 4 out of 5 parts
(by wt.). The remainder is water. The highly-concentrated sugar is to be concentrated (despite
the fact that it is already concentrated) in an evaporator, where water is heated and then
evaporated. The evaporator is able to evaporate 85 wt% of water in the highly concentrated
sugar. If it is required that 1,000 tonnes/day of highly-concentrated sugar be produced,
determine the water evaporation rate (in kg/h).
23
10. Butane (C4H10) is combusted with air. Assume that no CO is produced. Calculate the
composition of the product, when
a) C4H10 is completely consumed and the excess-air percentage is 20%
b) Conversion percentage of C4H10 is 90% and the excess-air percentage is still at 20%
11. Monochloroacetic acid (CH2ClCOOH) is produced from the reaction between acetic acid
(CH3COOH) and chlorine gas (Cl2) by having PCl3 as a catalyst. The resulting
monochloroacetic acid, however, may, in turn, react with chlorine gas (Cl2) and thus form
dichloroacetic acid (CHCl2COOH), as shown in the following reactions:
CH 3 COOH +Cl2 yields CH 2 ClCOOH + HCl
→
CH 2 ClCOOH +Cl2 yields CHCl 2 COOH + HCl

→
If monocloroacetic acid is to be produced in the amount of 5,000 kg/day, it is required that

Cl2 in the amount of 4,536 kg/day is needed and that dichloroacetic acid in the amount of 263
kg/day is to be separated from other products, using a crystalliser. If the excess reactant is
acetic acid, calculate
a) % conversion
b) % yield
c) Selectivity of monocloroacetic acid when compared with dichloroacetic acid
12. The chlorination reaction of methane (CH4) is as follows:

CH 4 +Cl 2 yields CH 3 Cl+ HCl
→
If the feed comprises CH4 40 mol%, Cl2 50%, and N2 10% and the percentage conversion of
the limiting reactant is 67%, determine the composition of the product.
13. To produce ethanol (C2H5OH) using from glucose (C6H12O6) by an anaerobic

fermentation using Saccharomyces cerevisiae yeast, the following reactions take place
C 6 H 12 O6 yields 2 C 2 H 5 OH +2 CO2
→
C 6 H 12 O6 yields 2 C 2 H 3 COOH +2 H 2 O
→
The feed, a glucose solution with the concentration of 12 wt%, is fed into a bioreactor with
the total mass of 4,000 kg. After the fermentation is ended, 120 kg of CO2 is generated, while
24
90 kg of glucose remains un-reacted. Determine the mass percentages of C2H5OH and

C2H3COOH in the product.
MATERIAL BALANCES FOR MULTIPLE UNITS
Many chemical plants are composed of many interconnected units. One can apply the general
mass balance equations to solve problems involving these units. The plant should be divided
into many sub-systems to be analysed one at a time. Also, overall material balance involving
all the units can be written. However, there shall be redundant equations arising which will
not be unique. For complex calculations, matrix method can be used to determine the
independence of the equations.
Consider the following examples:
EXAMPLE 14
Acetone vapour is considered toxic to the environment (as well as human health). As an
engineer in the chemical plant, you are asked to design an acetone recovery system having
the flow sheet illustrated below. In this Example, to make the calculation simple, all
concentrations of both gases and liquids are presented in weight percent (please note,
however, that, normally, for gas phase, the concentration is presented in “volume” and
“mole” basis)
Calculate the values of A, F, W, B, and D in kg per hour, if given G = 1,400 kg/h
Solution
25
Hence, from the basis, G = 1,400 kg and the “Feed” stream contains
• Acetone: (0.030)( 1,400) = 42 kg
• Air: (0.950) (1,400) = 1,330 kg
• Water: (0.020) (1,400) = 28 kg
The main principle of performing material balances for a system comprising multiple units is
that;
We need to carefully choose the unit/group of units that we are going to do the balances such
that the # of equations obtained from the available data/information equals that of the
unknowns.
1) Try performing the balances around the absorber unit
Overall balance
G+W = A+F
1,400 +W = A+F
There are 3 unknowns, thus, we need 3 equations. (i.e. we need another TWO equations., in
addition to the overall-balance equation)
Since the absorber column involves 3 species (i.e. acetone, air, and water), we can have up to
2 “independent” species balances
Hence,
the total # of equations = 3 (1 overall-balance equation and 2 species-balance equation)
while the # of unknowns = 3
Accordingly, the degree of freedom (DoF), which is defined as follows:
DoF = (# of unknowns) – (# of equation available)
26
for doing the material balances around the absorber column is DoF = (3) – (3) = 0
When DoF = 0, we can solve for all unknowns
Note that:
• when DoF = 0 (or when # of unknowns = # of Eq. available), all of the unknowns can be
solved
• when DoF > 0 (or when # of unknowns > # of Eq. available), we cannot solve for
Unknowns
• when DoF < 0 (or when # of unknowns < # of Eq. available), all of the unknowns can be
solved, but the technique is not called “solving”, it is rather called “optimizing” or
“performing regression analysis”
The technique of comparing the number of unknowns with that of the available equations is
called “degree of freedom analysis”
Hence, to solve for all unknowns around the absorber unit (W, A, & F ), we perform the
following species balances:
Acetone balance
Performing a species balance for acetone yields
(0.03)(1,400) = (0. 19)

221.1 kg
Air balance
Doing the same for air results in
(0.95) (1,400) = (0.995) ( )
= 1,336.7 kg
Substituting F = 221.1 kg & A = 1,336.7 kg into 1,400 +W = A+F
and solving for W gives
1,400 + W = 1,336.7 + 221.1
W = 157.8 kg
Thus, by performing the balances around the absorber unit, we obtain the values of the
following unknowns:
W = 157.8 kg
A = 1,336.7 kg
F = 221.1 kg
We still have another 2 unknowns (i.e. D and B) to solve for.
To solve for B, we try doing the following
27
2) Doing the balances around the distillation column
It is a good idea to choose to do the balances around the distillation column, since we do
NOT have any information of the stream leaving the top of the distillation column.
The distillation column involves 2 species: acetone and water
Hence, when we do not know the data of the stream leaving the top of the column, we have 3
unknowns in total, i.e.
• the value of B (or the mass flow rate of the Bottom stream)
• the mass flow rate of the top stream leaving the distillation column
• the concentration, in wt%, of either acetone or water of the top stream leaving the
distillation column
but we can set up at the maximum of 2 equations, i.e.
• 1 overall balance
• 1 species balance
The DoF is, therefore, +1, meaning that we cannot solve for the unknowns Thus, we need to
choose the NEW location to do the balances.
3) Performing the balances around the distillation column & condenser together
28
Overall balance
F = B+D
Substituting the value of F, obtained previously, gives
221.1 = B+D
There are 2 unknowns, thus, we need another equation (in order have 2 equations, in order to
solve or the unknowns – B & D
1) Acetone balance
(0.19 (221.1) = (0. 99) + (0.040)

42.01 = 0.99D + 0.04B
We have also 221.1 = B+D
Solving two equations simultaneously yields
B = 186.2 kg
D = 34.9 kg
To check the validity of all unknowns we have just solved for, we perform the overall
balance for the whole process as follows
G+W = A+B+D
Substituting corresponding numerical values, results in
1,400 + 157.8 = 1,336.7 + 186.2 + 34.9
1,557.8 = 1,557.8
This verifies that the balances performed previously is correct.
Alternatively, we can solve for the values of B & D (after we have obtained the values of W,
A, and F) by performing the balances around the whole process as follows
Overall balance
29
G+W = A+B+D
1,400 + 157.8 = 1,336.7 + B + D
B+D = 221.1
There are 2 unknowns; we, therefore, need another ONE equation
Acetone balance
(0.030) (1,400) = (0. 99) () + 4.0 ()
42 = 0.99D + 0.04B
We have also B+D = 221.1
Solving these equations simultaneously yields
B = 186.2 kg
D = 34.9 kg
which is exactly the same as done previously.

The composition, in mass fraction and in mass flow rate, of each stream, can be summarised
in the following Table
30
MATERIAL BALANCES OF PROCESSES WITH RECYCLING, BYPASSING, AND

PURGING
a. Processes with recycle stream
A recycle stream is a process stream that conducts material exiting or downstream from a unit
back to the inlet stream of the same unit.
Importance of a recycle stream:
 It necessitates the re-use of unreacted substances in the product stream
 It controls the humidity in driers by recycling humid air
 It is used in stripping more or less volatile component in distillations etc.
Balances that can be made on a process having a recycle stream.
i. About the entire process having all the units inside
ii. About the mixer of fresh feed and the recycle stream
iii. About the process
iv. About the junction point of the product and recycle separation
EXAMPLE 14
The flow chart of a steady-state process to recover crystalline potassium chromate (K2CrO4)
from the aqueous solution is shown below
Forty-five hundred kilograms per hour of 33.3% K2CrO4 solution is joined by a recycle
stream of 36.4% K2CrO4 solution, and the combined stream is fed into an evaporator. The
concentrated stream leaving the evaporator contains 49.4% K2CrO4. This stream is then fed
into a crystallizer where it is cooled, causing crystals of K2CrO4 to come out of the solution.
The resulting solution and K2CrO4 crystals are separated by a filter, dividing the product into
2 streams: the filter cake, which consists of K2CrO4 crystals and 36.4% K2CrO4 solution; and
31
the filtrate, which is the 36.4% K2CrO4 solution. The K2CrO4 crystals account for 95% of the
total mass of the filter cake. The filtrate is recycled to mix with the feed.
Calculate (a) the rate of evaporation, or the rate of water evaporated at the evaporator, and (b)
the recycle ratio [i.e. (mass flow rate of recycle)/(mass flow rate of fresh feed)]
Solution
For our convenience, let

K2CrO4 = K, Water = W
Basis 1 h of operation
To answer question (a), i.e. how many kg of water we need to evaporate, we start performing
the mass balances around the evaporator, as illustrated below:
However, if we do so, there would be 4 unknowns (m2, m3, m4, & x) to be solved for, but
we can have, at best, only 2 equations (1 overall balance equation & 1 species balance
equation)
Thus, we need to choose the new point/ location to do the balances.
32
We, then, try performing the balances for the whole process as follows:
Overall balance
m1=m3+m5+m6
The problem states that
m5 = 0.95 (m5+m6 )
Hence, by re-arranging the above equation,
m6 = 0.0526m5
m1 = 4,500 kg
Overall balance;
m1=m3+m5+m6
4,500 = m3 + m5 + 0.0526m5
4,500 = m3 + 1.0526m5
Note that, now, we have 2 unknowns to be solved.

K2CrO4 balance
(0.333) ( 4500) = ( 1) m5 + (0. 364)m6
(0.333) ( 4500) = ( 1) m5 + (0. 364)(0.0526m5)
m5 = 1,470.6 kg
Thus,
m6 = 0.0526m5 = 0.0526 (1,470.6)
m6 = 77.4 kg
Then, using equation for overall balance, we can solve for m3 as follows
4,500 = m3 + 1.0526m5
4,500 = m3 + 1.0526 (1,470.6)
33
m3 = 2,952.0 kg
Hence, the rate of water evaporation is 2,952.0 kg/h
Recycle ratio is defined as follows:
The amount material in the recycle stream per the amount of the material fed unto the system.
To obtain the value of the recycle or m7, we perform the balances around the crystalliser &
filter
Overall balance
m4 = m5 + m6 + m7
Substituting the values of m5 & m6
m4 = (1,470.6) + (77.4) + m7
= (1,548.0) + m7
K2CrO4 balance
(0.494) m4 = (1)m5 + (0.364) m6 + (0.364)m7
(0.494) m4 = (1)(1,470.6) + (0.364) (77.4) + (0.364)m7
(0.494) m4 = (1,498.8) + (0.364)m7
From overall eqn. we have
m4 = (1,548.0) + m7
Solving two equations simultaneously m4 & m7 will be
m4 = 7,194.8 kg
m7 = 5,646.8 kg
Thus, the recycle ratio is =R/F = 5646.8/4500 = 1.255
34
b. Processes involving by-pass stream
A by-pass stream in on which skips one or more stages of the process and goes directly to
another stage. They are mostly used to control the composition of the final exit stream from a
unit by mixing the bypass stream and the exit in suitable proportions.
EXAMPLE 15
In the preparation of the feedstock for a plant manufacturing gasoline, iso- and normal-
pentane are produced from process shown below. Calculate the fraction of feed that passes
through the iso-pentane tower.
In order to obtain the “fraction of feed that passes through the iso-pentane tower”, we need to
solve for the value of m1 and then compare it with that of mF (= 100 kg)
Performing the mass balances around the whole process yields
Overall balance
mF = mS + mP
100 = mS + mP
iso-pentane balance
(0.20) mF = (1) mS + (0.10) mP
(0.20)( 100) = (1) mS + (0.10) mP
Also we have
100 = mS + mP
35
Solving these equations simultaneously gives

mP = 88.9 kg
mS = 11.1 kg
The principle of separating point states that the compositions of all streams entering and
leaving the separating point are IDENTICAL. Hence, the composition of Stream 2 (&
Stream 1, too) are exactly the same as that of the Feed; i.e. the Stream 2 (& Stream 1)
contains;
• n-C5H12 80%
• i-C5H12 20%
Performing the mass balances around the mixing point yields
Overall balance
m2 +mB =mP
m2 +mB = 88.9
n-pentane balance
(0.80) m2 + (1) mB = (0.90) mP
(0.80) m2 + (1) mB = (0.90) 88.9
0.8 m2 + mB = 80.01
Also we have m2 +mB = 88.9
Solving equations simultaneously results in
m2 = 44.45 kg
mB = 44.45 kg
Performing the overall balance around the separating point gives
mF = m1 + m2
Substituting corresponding numerical values into the equation yields
100 = m1 + 44.45
36
m1 = 55.55 kg
Thus, the “fraction of feed that passes through the iso-pentane tower” is
m1/mF = 55.55/100 = 0.5555
c. Processes involving a purge stream
Purge stream is one that is bled off to remove an accumulation of inerts or unwanted material
that might accumulate in the recycle stream.
Consider the example below:
EXAMPLE 16
In conversion of hydrogen and carbon-monoxide to methanol obtained from coal, Methane
gas is present as a trace component and doesn’t participate in the reaction. A purge stream is
used to maintain the methane concentration in the exit to the separator at no more than 3.2 %.
Once-through conversion for carbon-monoxide in the reactor is 18 %. Compute the moles of
recycle, methanol per mole of feed and also determine the purge gas composition.
XXXXXXXXXXXXXXXXXXXXXXX
EXAMPLE 17
Redo the Example 14 once again, but consider the case that there is no recycle of the filtrate
to be mixed with the fresh feed. Determine
(a) the amount of K2CrO4 produced per hour and
(b) the rate that we need to evaporate water.
Solution
Without the recycle of the filtrate, we can re-draw the flow chart as shown on the next page.
We then try performing the balances around the whole process, as done previously.
37
Overall balance
m1 = m2 + m4 + m5 + m6
4,500 = m2 + m4 + m5 + m6
but, as stated in the problem statement,
m4 = 0.95 ( m4 + m5 )
Thus,
4,500 = m2 +m4 + 0.0526m4 +m6
4,500 =m2 + 1.0526m4 + m6
There are 3 unknowns ( m2 , m4 ,& m6 ), but we can have, at most, another 1 equation (i.e.
one species balance equation – either for K or W ) to add up to only 2 equations.
Hence, we need to choose the new point/ location to perform the mass balances.
Performing the balances around the evaporator gives;
Overall balance
m1 = m2 + m3
4,500 = m2 + m3
Water balance
(0.667)(4,500) = m2 + 0.506 m3
Solving these equations simultaneously yields
m3 = 3,033.4 kg
m2 = 1,466.6 kg
Thus, the rate at which water has to be evaporated is 1,466.6 kg/h (note that it is 2,952.0 kg/h
when the filtrate is recycled to be mixed with the fresh feed)
Doing the balances around the crystalliser & filter gives;
38
Overall balance
m3 = m4 +m5 +m6 , but
m4 = 0.95 (m4 + m5)
m5 = 0.0526 m4
and, from the mass balances done recently,
m3 = 3,033.4 kg
Hence, we obtain the following equation:
3,033.4 =m4 + 0.0526m4 +m6
3,033.4 = 1.0526m4 +m6
K2CrO4 balance
(0.494)m3 = (1)m4 + (0.364)m5 + (0.364)m6
(0.494)m3 = (1)m4 + (0.364)( 0.0526m4 ) + (0.364)m6
(0.494)(3,033.4) = 1,498.5 = 1.0194m4 + (0.364)m6
Also we have
3,033.4 = 1.0526m4 +m6
Solving equations simultaneously yields
m4 = 619.7 kg
m5 = 0.0526 m4 = 0.0526 (619.7)
m5 = 32.6 kg
m6 = 2.381.1 kg
The rate at which K2CrO4 is produced is 619.7 kg/h (note that it is 1,470.6 kg/h when the
filtrate is recycled)
The comparison between the “recycle” and “not recycle” cases are as follows
39
40
MATERIAL BALANCES WITH REACTIONS FOR MULTIPLE-UNIT PROCESSES

EXAMPLE 18
Propane is dehydrogenated to form propylene in a catalytic reactor:
The process is to be designed for a 95% overall conversion of propane. The reaction products
are separated into two streams: the first, which contains H2, C3H6, and 0.555% of C3H8 that
leaves the reactor, is taken off as product; the second, which contains the balance of the
unreacted propane and 5% of the propylene in the first stream, is recycled to the reactor.
Calculate (a) the composition of the product, (b) the ratio: (moles recycled)/(moles fresh
feed), and (c) the “single-pass” conversion.
Solution
Basis 100 g-mol of feed (C3H8)

Given data:
1) 95% “overall” conversion of propane (C3H8)
What is an “overall conversion”?
We have learned that
Xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx
(note that “mole(s) of remaining A” is, in fact, “mole(s) of A unreacted”)

Overall conversion A = Fractional conversion of A for the entire process.
Thus, for this Example,
XXXXXXXXXXXXXXXXXXX
41
mole(s) of remaining C3 H8 = 0.05 (mole(s) of C3H8 fed)

= 0.05 (100 g-mol)
2) n6 = 0.555% of n3
n6 = 0.00555n3
XXXXXXXXXXXXXXXXXXX
n3 = 901 g-mol
3) n10 = 5% of n7
n10 = 0.05 n7
Perform the “atomic” balances around the entire process
(as illustrated as dashed lines on previous page)
Overall C (carbon) balance
(C)fresh feed = (C)product
(C in C3H8)fresh feed = (C in C3H8)product + (C in C3H6)product
(3 × 100) = (3 × n6) + (3 × n7)
300 = 3n6 + 3n7

100 = n6 + n7
Since n6 = 5 mol
n7 = 100 – 5 = 95 mol
Overall H (hydrogen) balance
(H)fresh feed = (H)product
(H in C3H8)fresh feed = (H in C3H8)product + (H in C3H6)product
(8 × 100) = (8 × n6) + (6 × n7) + (2 × n8)
Since
n6 = 5 g-mol
n7 = 95 g-mol
then n8 = 95 g-mol
Hence, the product comprises
C3H8 5 g-mol = n6
C3H6 95 g-mol = n7
H2 95 g-mol = n8
which we can summarize in the following Table
42
The value of n10 can be obtained when we have obtained the value of n7 as follows
n10 = 0.05n7
= 0.05( 95 g-mol)
n10 = 4.75 g-mol
Doing the balances around a separator
Since NO Rxn. is taken place in a separator, the number of moles of each component is
conserved, meaning that the number of moles of each component entering the separator is
equal to that leaving the separator
C3H8 balance
n3 = n6 + n9
901 = 5 + n9
n9 = 896 g-mol
Thus, the total number of moles of the recycle stream is
n9 + n10 = 896 + 4.75 = 900.75 g-mol
Accordingly,
the recycle ratio = (moles recycled)/(moles fresh feed)
= (900.75 g-mol)/(100 g-mol)
= 9.01 ≈9
43
SINGLE-PASS CONVERSION (?)

“Single-pass conversion” is a fractional conversion of a substance obtained when it passes
through a reactor only, without having passed through any other units of the entire process
Thus, for this Example:

xxxxxxxxxxxxxxxxxxxxxx
Hence, we need the value of n1 to calculate the value of the single-pass conversion of C3H8
Doing the balances around the mixing point
Since NO Rxn takes place at the mixing point, the number of moles of each component is
conserved.
C3H8 balance : 100 + 896 = n1
n1 = 996 g-mol
Thus,
Note that the overall conversion = 95%!
xxxxxxxxxxxxxxxxxxxxxxxxxxxxx
This is why we need to recycle the product product of the reactor (or fraction of it) back to
the reactor (in order to obtain higher fractional conversion)
EXAMPLE 19
Normally, fresh orange juice consists of 10-15 wt% dissolved solids in water. In order to
reduce the cost of shipping, the juice is concentrated prior to shipping. Concentration must be
carried out in a specially-designed, short-time evaporator operated at low pressure in order to
reduce the boiling temperature, which, in turn, reduce the loss of flavour and aroma
components. Unfortunately, however, the loss of flavour and aroma is unavoidable, some
amount of fresh orange juice (called “cutback”), by-passed from the evaporator, is mixed
with the product from the evaporator to improve flavour and aroma of the product.
44
Ten thousand (10,000 kg/h) of the feed containing 12 wt% of dissolved solids is fed to the
system, and 10 wt% of the feed is to be used as a cutback. If the product from the evaporator
contains 80 wt% dissolved solids, calculate the evaporation rate and the composition of the
final product.
Thus, the feed (F1 ) is 10,000 kg
Performing the overall balance around the splitter yields

F1 = F2 + F3
10,000 = F2 + F3
It is given that F3 = (0.10)F1
Substituting F1 = 10,000 kg results in
F3 = (0.10) 10,000 = 1,000 kg
Thus, from Eqn. 10,000 = F2 + F3
10,000 = F2 + 1,000
F2 = 9,000 kg
The compositions of these 3 streams (i.e. streams 1–3) are identical and are follows
• Dissolve solids 12 wt%
• Water 88 wt%
Performing the balance around the evaporator gives

Overall balance
F2 = F4 + F5
45
9,000 = F4 + F5
Solids balance
( ysolids )2 F2 = ( ysolids )4 F4 + ( ysolids )5 F5
( 0.12 ) F2 = ( 0.00 ) F4 + ( 0.80 ) F5
0.12 F2 = 0.80 F5
0.12( 9,000) = 0.80 F5
F5 = 1,350 kg
Thus, from Eqn., 9,000 = F4 + F5
9,000 = F4 + 1,350
F4 = 7,650 kg
Thus, the evaporation rate is 7,650 kg/h
Performing the balance around mixer results in
Overall balance
F3 + F5 = F6
Substituting the numerical values of F3 & F5
1,000 + 1,350 = F6
F6 = 2,350 kg
Solids balance
( xsolids )3 F3 + ( xsolids )5 F5 = ( xsolids )6 F6
(0.12 )(1,000) + (0.80 )(1,350) = ( xsolids )6 (2,350)
( xsolids )6 = 0.511 = 51.1 %
46
PROBLEMS ON MATERIAL BALANCES FOR MULTIPLE UNITS

1. Determine the following flow chart and calculate numerical values of all unknowns
(indicated by the bold characters).
2. In order to remove salts from the sea water, the sea water has to pass through a
process called desalinisation. The desalinisation process is;
If the fresh sea water has the flow rate of 500 kg/h, determine
a) the flow rate of brine (in kg/h)
b) the daily production of desalinised water
c) the recycle ratio (i.e. the flow rate of the recycle brine/the flow rate of the fresh
feed)
3. The fruit-drying process is illustrated in the following flow chart. The fresh feed
containing 70 wt% dry fruit and 30 wt% water (moisture) is mixed with the recycle
stream, which contains 97 wt% dry fruit and 3 wt% moisture in a mixer. The product
leaving the mixer contains moisture in the amount of 15 wt%. It is then fed into a
dryer, where moisture is removed from the fruit until the moisture in the fruit is lower
than 3 wt%. The dried fruit from the dryer is divided into two parts: the first one is
47
shipped to customers, and the second one is recycled to mix with the fresh feed, as
described earlier. Calculate the recycle ratio (i.e. mass of the recycled stream/mass of
the fresh feed)
4. P is a desired product, which can be produced from the substance A, as shown below
A, in parallel, may be converted to B, which is an undesired product,
The feed consisting of A 90 mol% and inerts (I) 10 mol% is fed into the process,
shown in the following flow chart. The overall conversion of A is 80%, and %yield of
P at the reactor is 50%. Additional data regarding the process are as follows:
• The recycle stream (Stream 2) is adjusted until the Stream 3 has the composition of
84 mol% A and 16 mol% I
• The Stream 4 contains only B (the undesired product)
• The Stream 6 consists of P (the desired product) only
• The Streams 2, 7, and 8 contain only A and I, and the mole ratios of A and I in these
streams are identical
48
If the feed has the molar flow rate of 100 g-mol/s, determine the flow rate and
composition of each stream (i.e. Streams 2-8). Also calculate the recycle ratio and the
selectivity.
Hints:
• Since I is inerts, the total amount of I entering the process is equal to that leaving the
process
• The overall conversion of A can be calculated from the amount of A in the feed
(Stream 1) and that in Stream 8
• %yield of P is obtained at the reactor
WORKED OUT PROBLEMS

1. Staged distillation columns are devices used to separate volatile materials by boiling
off more volatile components (as a distillate). In order for a clean separation to take
place, these devices require that at least part of the vapour product from the top of the
column be condensed and returned back to the column. The composition of the
vapour product from the top of the column (called “overhead” is identical to those of
the distillate and the stream that returns to the column (called “reflux”)
49
Suppose that the distillation column is employed to separate a three-component (or ternary)
mixture consisting 7 mol% acetone, 61.9% acetic acid, and 31.1% acetic anhydride
The column is designed to yield the bottoms stream containing no acetone and the distillate
containing 10% acetone and 88% acetic acid If the column is operated so that 60% of the
overhead is returned as a reflux. If 700 mol/h of the distillate is to be produced, calculate the
flow rates and compositions of all streams
In this Example, we are dealing with 3 main unit operations:
• a distillation column
• a condenser
• a splitter
To obtain the answers (e.g., the flow rates and compositions of all streams in this Example),
we have to draw a material-balance system boundary for any single unit operation or for a
group of unit operations or for the whole system. The material-balance system boundary must
be chosen carefully and wisely.
The only principle for choosing the materialbalance system boundary is that the system
boundary must be chosen such that the number of unknowns for that boundary system is
equal to the number of equation that the boundary system can have.
If we draw the system boundary for the whole system, we have to determine the unknowns
for stream 1, 3, and 5.
50
Since this is a 3-component (ternary) system/mixture, specifying concentrations (in mol% or

in mole fraction) of only 2 components (or species or substances) is enough (as the mol% of
all components must be added up to 100 or mole fractions of all species must be added up to
1)
Thus, in this Example, the “mol%” of acetic anhydride in stream 3 is
100 – 10 – 88 = 2 mol%
Hence, the unknowns are
1. the flow rate of the feed

2. the flow rate of the bottoms stream
3. the concentrations of either acetic acid or acetic anhydride
So, we need 3 equations.
Can we have 3 equations, when we draw the material-balance system boundary for the whole
system?
Normally, we can have
• 1 overall-balance equation
• n −1 species-balance equations
(n = # of species)
Hence, in this Example, we can have 2 (i.e. 3 – 1) species-balance equations.
Thus, if for the whole system, we can have, in total, 1 + 2 = 3 equations. Accordingly, we
can solve for all unknowns.
This kind of “degree of freedom” analysis is necessary before we perform the numerical
calculations for any material balance problems.
Thus, the distillate (S3 ) is 700 g-mol
51
Overall balance
S1 = S3 +S5
S1 = 700 +S5
Species balance
Acetone balance
Xxxxxxxxxxxxxxxxxxxx
Thus, from overall balance

S1 = 700 +S5
1,000 = 700 +S5 =S5 = 300 g-mol
Acetic acid balance
Hence, the concentration (in mol% of acetic anhydride in stream 5 )

100 – 1 = 99%
In summary, for streams 1, 3, and 5, the flow rate and composition of each stream are as
follows;
• Stream 1: 1,000 mol/h • Acetone 7 mol%
• Acetic acid 61.9 mol%
• Acetic anhydride 31.1 mol%
• Stream 3: 700 mol/h • Acetone 10 mol%

• Acetic acid 88 mol%
• Acetic anhydride 2 mol%
• Stream 5: 300 mol/h • Acetic acid 1 mol%

• Acetic anhydride 99 mol%
How can we get the flow rates and compositions of streams 2 and 4?
It is stated that the composition of the overhead (i.e. the vapor stream coming out of the
distillation column) is equal to those of the distillate and the reflux.
Since we have obtained the composition of the distillate (stream 3) from the above
calculations, the compositions of the overhead (stream 2) and the reflux (stream 4) are known
(i.e. identical to that of stream 3)
52
To obtain the flow rates of streams 2 and 4, we perform the material balance around the
condenser + the splitter (or we draw the system boundary around the condenser + the
condenser)
Since there is NO reactions at the condenser and the splitter, we can perform the mole
balance round this point.
Overall balance
S2 = S3 +S4
S2 = 700 + S4
We have 2 unknowns, but we can have only 1 overall-balance equation, as a species
balance does NOT work for this boundary system (since the compositions of all streams are
identical). We need another equation. It is given, in the problem statement given that
60% of the overhead is returned as a reflux
which can be translated into equation form as follows
S4 = ( 0.60) S2
We have, S2 = 700 + S4
S2 = 700 + ( 0.60) S2
S2 = 1,750 g-mol
Then S4 = ( 0.60) S2
S4 = 1,050 g-mol
Thus, in summary, the flow rates of
• stream 2 = 1,750 mol/h
• stream 4 = 1,050 mol/h
53
and the compositions of streams 2 and 4

• acetone 10 mol%
• acetic acid 88 mol%
• acetic anhydride 2 mol%
which are identical to that of stream 3
2. Material Balances for Combustion Processes

A liquid fuel containing 88 wt% C and 12% H is burned with air, comprising 21 vol% O2
and 79% N2, in a combustor. The combustion product is called “flue gas”, and the flue gas
leaving the combustor is then passed through a desiccant column, to completely removed
water from the flue gas. The resulting dry flue gas is then passed through a gas analyser, to
analyse for the composition of the dry flue gas, and the analytical results are as follows: CO2
13.4% by vol., O2 3.6%, and N2 83.0%.
If the amount of fuel fed into the combustor is 100 g, calculate the amount of the dry flue gas,
in g, and determine the percentage excess of O2 (note that N2 does not react with any other
species)
Basis 100 g of feed (liquid fuel)

Thus, the feed comprises
• C 88 g
• H 12 g
54
Rxns: C + O2 CO2
H + ¼ O2 ½ H2O
Overall C (carbon) balance
xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx
C output can be calculated as follows:

From the given data, of n2 g-mol of dry flue gas, there is CO2 in the amount of 13.4% by
mol. (note that, for gas phase, %mol ≡ %vol)
The amount, in g-mol, of CO2 in the dry flue gas is then
(0.134)n2
We know that 1 molecular mol of CO2 contains 1 atomic mol of C and 2 atomic mol of O,
Thus, the amount of C in the dry flue gas is
1x(0.134)n2 = (0.134)n2 atomic mol
Hence,
C output = (0.134)n2
From the atomic balance principle
C input = C output
7.33 g-mol = (0.134)n2
Then n2 = 54.7 g-mol
Thus, the dry flue gas contains

• CO2 = (0.134) (54.7) = 7.33 g-mol
55
• O2 = (0.036) (54.7) = 1.97 g-mol

• N2 = (0.830) (54.7) = 45.4 g-mol
Since, N2 does not react,

(N2) input = (N2) output
(N2) input = (0.79)n1
(N2) output = 45.4 g-mol
Hence, (0.79)n1 = 45.4
n1 = 57.5 g-mol
Accordingly, the air entering the combustor comprises
• O2 = (0.21) (57.5) = 12.1 g-mol
• N2 = (0.79) (57.5) = 45.4 g-mol
Note: In this Example, N2 can be considered as a tie component (Do you know why?)
From the chemical Rxns.,
1 g-mol of O2 is needed to react stoichiometrically with 1 g-mol of C, and

¼ g-mol of O2 is required to react stoichiometrically with 1 mol of H.
The amount of C fed is
xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx
Thus, O2 in the amount of 1× 7.33 = 7.33 g-mol is needed

The amount of H entering the combustor is
Xxxxxxxxxxxxxxxxxxxxxxxxx
The amount of O2 needed is then (1/4)x 11.90 = 2.98 g-mol

Hence, the total amount of O2 required theoretically is
7.33 + 2.98 = 10.31 g-mol
but the amount of O2 fed into the combustor is 12.1 g-mol
56
Accordingly, the amount of UNREACTED (or excess) O2 is

12.1 – 10.31 = 1.79 g-mol
From our recent calculations, the amount of O2 in the dry flue gas is 1.97 g-mol
The discrepancy (1.97 vs 1.79 g-mol) may result from an error of the gas analyser; however,
these two numbers are close to each other (so, the error is acceptable).
Summary
Mass of the Dry Flue Gas
Since the dry flue gas comprises
• CO2 = (0.134) (54.7) = 7.33 g-mol
• O2 = (0.036) (54.7) = 1.97 g-mol
• N2 = (0.830) (54.7) = 45.4 g-mol
we can calculate the mass of each species and the total mass of the dry flue gas as illustrated
in the following Table
Excess percentage of O2
Xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx
From the calculations above, for O2,

nfed = 12.1 g-mol
nstoich = 10.31 g-mol
The percentage excess of O2 can then be calculated as follows
Xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx
= 17.4%
57
In the field of combustion, it is customary to call excess percentage of O2 (or %excess O2)
• % excess air (%XA)
• % excess oxygen
Note that %XA is identical to % excess oxygen

Normally, the amount of theoretical O2 is obtained from a valid chemical Rxn. (or valid
chemical Rxns.), and since air contains.
• 21 mol% O2
• 79 mol% N2
the amount of air and N2 can be calculated from the amount of O2 as follows
xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx
Note also that, sometimes, flue gas is called “stack gas”.

The flue or stack gas with water (H2O) is called “wet” flue or stack gas; after the water is
removed from the wet flue or stack gas, it becomes “dry” flue or stack gas
58
ENERGY BALANCES
The concept of energy conservation as expressed by an energy balance equation is central to
chemical engineering calculations. Similar to mass balance studied previously, a balance on
energy is crucial to solving many problems.
System
A “system” is an object or a collection of objects that an analysis is done on. The system has
a definite boundary, called the system boundary that is chosen and specified at the beginning
of the analysis. Once a system is defined, through the choice of a system boundary,
everything external to it is called the surroundings. All energy and material that are
transferred out of the system enter the surroundings, and vice versa. In the general case there
are very few restrictions on what a system is; a system can have a nonzero velocity, a nonzero
acceleration, and a system can even change in size with time.
An isolated system is a system that does not exchange heat, work, or material with the
surroundings.
If heat and work are exchanged across a system’s boundary, but material is not, it is a closed
system.
An open system can exchange heat, work, and material with the surroundings.
State of a System
Once a system is defined, a certain number of variables will specify its state fully.
For example, one may need to provide the temperature, pressure, composition, total amount
of material, velocity, and position in order to specify a system’s
“state.”
State Functions and State Properties
The state of a system can be changed, for example by increasing its temperature orchanging
its composition. Properties of the system whose change depends only on the initial (before)
and final states of the system, but not on the manner used to realize the change from the
initial to the final state, are referred to as state properties or state functions.
Forms of Energy: The First Law of Thermodynamics
Energy is often categorized as:
a. Kinetic Energy
b. Potential Energy
c. Internal Energy
Kinetic Energy
59
A system’s kinetic energy is associated with directed motion (e.g. translation, rotation) of the
system.
Potential Energy
Potential energy of a system is due to the position of the system in a potential field.
Internal Energy
Internal energy is the energy due to all molecular, atomic, and subatomic motions and
interactions. Usually, the complexity of these various contributions means that
no simple analytical expression is available from which internal energy can be
readily calculated.
Enthalpy
The enthalpy H of a system is defined by
H = U + PV
where P is the pressure and V is volume.
Enthalpy, therefore, can be viewed as the sum of the internal
energy of a fluid volume added to the system plus the flow work performed on the system in
order to insert the fluid.
Flow work is the work, where pressure results in the displacement of a fluid, it is given by
W = PV.
Specific Properties
The total internal energy, enthalpy, kinetic energy, and potential energy of a system are
extensive properties. An extensive property depends on the total number of molecules present
in the system and on the system’s total size.
Amount of a property per mass, is the specific property. Specific properties are intensive.
Reference States
The specific internal energy and specific enthalpy of a material are always defined relative to
a reference state. The reference state can be chosen to refer to any set of conditions,
although often it is chosen to be 0 ºC and 1 atm.
Note that, in calculations, we will only be interested in how much the internal energy or
enthalpy changed and not their absolute values.
Heat
When there is a difference in temperature between two points, heat is transferred (flows)
from high temperature to the low temperature. By convention the numerical value of heat
transferred is positive when it is transferred into the system, thereby increasing the energy
60
contained in the system. That is, if Q is the heat transferred from the surroundings to the
system, then Q > 0 means that net heat is transferred to the system so as to increase the
energy of the system. If Q < 0, then net heat is transferred from the system to the
surroundings.
Work
When a force is applied to a system and causes a displacement, then work has been done on
that system.
Rates vs Amounts
Chemical processes use process streams to transport material from one point to another.
Consider a stream with a mass flowrate m. The material in the stream carries its kinetic,
potential, and internal energy with it. Therefore, the mass transport is per force accompanied
by energy transport.
Heat transport and work can be also expressed as rates, with symbols Q and W respectively.
The General Energy Balance

“Black Box” Analysis: This method of analysis, in the context of process modeling, does not
concern itself with how individual process units work. The input and output streams are
instead analyzed by applying constraints imposed by nature, namely conservation of mass
and conservation of energy. The inner workings of the physical apparatus are not relevant.
The First Law of Thermodynamics is a statement of energy conservation.

Although energy cannot be created or destroyed, it can be converted from one form to
another (for example, internal energy stored in molecular bonds can be converted into kinetic
energy; potential energy can be converted to kinetic or to internal energy, etc.). Energy can
also be transferred from one point to another or from one body to a second body. Energy
transfer can occur by flow of heat, by transport of mass (transport of mass is otherwise
known as convection), or by performance of work. The general energy balance for a process
can be expressed in words as:
Accumulation of Energy in System =
Input of Energy into System – Output of Energy from System
Now the total energy of a system, as considered above, is composed of kinetic, potential, and
internal energies. These energies can be transferred into or out of the system by flow of mass
through process streams that bring the various forms of energy with them. In addition, they
61
can be transferred by performance of work, or by flow of heat. Expressing this energy

balance mathematically takes the form:
Consider a stationary system (i.e. the system is not experiencing an overall movement in the
frame of reference, although its boundary may be deformable). Such a system will in general
experience two types of contact work interactions with the surroundings. The first type of
work is called shaft work (symbol: Ws) and arises when a part of the boundary of the system
is displaced. Shaft work takes place at moving parts of a system’s boundary across which
there is no mass transport. The force is often exerted by some form of machinery. For
example, the surface of a rotating impeller exerts force on the fluid (the fluid being the
system) as it stirs the fluid, and hence performs shaft work on the “system.” Another example
is that of a moving wall, such as a piston. The moving piston exerts force and thus performs
shaft work on the contained fluid (the fluid again being the system).
A second classification of work is flow work. It occurs at areas of a system’s boundary
across which there is material flowing. The flow work is associated with the force and
displacement required to push the material into the system (input streams), or with the force
and displacement required to push material out of the system (output streams). A fluid cannot
flow unless it creates space for itself when it enters or exits a system. The forces that do the
necessary pushing are exerted by particles of the flowing material inside the system on the
particles of the material outside the system, and are evaluated at the stream inlets and outlets
where the transfer of material into/out of the system takes place.
The previous equation can be rewritten as:
But we know that H =U+ (PV)
62
The rate of accumulation term can be broken down into rates of accumulation of kinetic,
potential, and internal energies:
Where:
Ek, EP, and U are the total kinetic, potential, and internal energies of the system.
Integration of the above equation with respect to time, from an initial to a final time yields,
Where
mj is the amount of mass transferred into the system by stream j in the period between the
initial and final times.
Comments
If Q = 0 then the system is adiabatic. Occurs when there is a perfect thermal insulation or
when the system and surroundings are at the same temperature.
If ΔEk = 0 then there is no acceleration within the system.
If ΔEP = 0 then the system is not experiencing a displacement in the direction of the
gravitational field.
If there is no motion along the system boundary, either perpendicular or tangential, then Ws =
0.
Solving Material and Energy Balance Problems
The following steps are helpful in solving problems that combine material and energy
balance calculations.
1. Since material balances have to be obeyed even if an energy balance is to be
performed, the first thing to do is to solve the material balance part of the problem
(i.e. choose a basis, make a flowchart, identify your unknows, perform a degrees of
freedom analysis, write equations, solve).
63
2. If an energy balance calculation is required in addition, there will be an extra

unknown in the problem. This unknown may be a temperature, amount of heat added,
or some other variable that appears in the energy balance. The extra equation you’ll
use to solve for this additional variable is the energy balance. To begin, identify the
“system” and write the appropriate form of the energy balance for it (i.e. closed, open,
isolated). Also, delete any terms from the energy balance that are either zero or
negligible compared to the other terms.
3. For each species that you need H ˆ or U ˆ for, you will need to choose a reference
state. If using data from an external source (i.e. tables, graphs) the reference state will
be specified in that source. Often, it is convenient to choose one of the inlet or outlet
conditions as the reference state, as then the H ˆ or U ˆ for that stream become zero,
thus simplifying the calculations.
4. Make a list of all the terms in the energy balance that you will need to calculate or
look up in order to solve for the unknown of interest. This list may include internal
energies, enthalpies, elevations, mass flowrates (mass flowrates were presumably
already calculated in step 1), etc.
5. Calculate all the quantities identified in step 4.
6. Solve the energy balance for the remaining unknown of interest. To do so, you will
need to insert the values of all the other terms appearing in the energy balance, as
identified and calculated in steps 4 and 5.
EXAMPLE 20
A gas is contained in a cylinder fitted with a movable piston. The initial temperature of the
gas is 25 ºC. The cylinder is next placed in boiling water, and 2.00 kcal of heat is transferred
to the gas, raising its temperature to 100 ºC.
During this step, the piston is not allowed to move. What happens to the pressure of the gas?
In a second step, the piston is released and the gas does 100 J of work in moving the piston to
its new equilibrium position. The final gas temperature is 100 ºC (note that the cylinder is still
immersed in the boiling water).
Write the energy balance equation for each of the two steps. In each case, solve for the
unknown term in the equation. The gas is assumed to be ideal, and effects due to gravitational
potential energy are negligible.
64
EXAMPLE 21
The specific internal energy of helium at 300 K and 1 atm is 3800
J/mol, and the specific molar volume at the same temperature and pressure is 24.63
L/mol. Calculate the specific enthalpy of helium at this temperature and pressure, and the rate
at which enthalpy is transported by a stream of helium at 300 K and 1
atm with a molar flow rate of 250 kmol/h.
EXAMPLE 22
Five hundred kg/h of steam drives a turbine. The steam enters the turbine at 44 atm and 450
oC at a linear velocity of 60 m/s, and leaves at a point 5 m below the turbine inlet at
atmospheric pressure and a velocity of 360 m/s. The turbine delivers shaft work at a rate of
70 kW, and the heat loss from the trubine is estimated to be 104 kcal/h. Calculate the specific
enthalpy change associated with the process.
EXAMPLE 23
Saturated steam at 1 atm is discharged from a turbine at a rate of
1150 kg/h. Superheated steam at 300 ºC and 1 atm is needed as a feed to a heat exchanger; to
produce it, the turbine discharge stream is mixed with superheated steam available from a
second source at 400 ºC and 1 atm, such that the product is superheated steam at 300 ºC and 1
atm. The mixing unit operates adiabatically.
Calculate the amount of superheated steam at 300 ºC produced and the required volumetric
flow rate of the 400 ºC steam.
Mechanical Energy Balance and the Bernoulli Equation

The general energy balance derived previously can be recast into a “mechanical energy
balance.” The mechanical energy balance is most useful for processes in which changes in
the potential and kinetic energies are of primary interest, rather than changes in internal
energy or heat associated with the process. Thus the mechanical energy balance is mainly
used for purely-mechanical flow problems i.e. problems in which heat transfer, chemical
reactions, or phase changes are not present.
65
First, we assume steady state, so that all terms on the left hand side become zero. Second, we
assume that the system has only a single inlet and a single outlet.
These adjustments lead to:
Next, we divide the entire equation by m , and write specific volume (volume/mass) as Vˆ =
1/ ρ , where r is the density (mass/volume) of the flowing material.
Also assume that the flow is incompressible, so that density is constant. A constant density
means that Vˆ in = Vˆout = 1/ ρ . Also, we define ΔU ˆ = U ˆout - U ˆ in, ΔP = Pout - Pin, etc. With
these changes the equation becomes:
The term (ΔUˆ

−Q/m) in the
absence of chemical reactions, phase changes, or other sources of large amounts of heat
transfer; i.e. under typical conditions of usage for the mechanical balance equation – will
mostly represent heat generated due to the viscous friction in the fluid. In such situations, this
term is called the friction loss and we will write it as F ˆ. With this last change, the equation
assumes the usual form of the mechanical energy balance:
In many instances, the amount of energy lost to viscous dissipation in the fluid is small
compared to magnitudes of the other terms. Here, F ˆ≈ 0. Moreover, many common flows
(e.g. fluid flow through a pipe) do not have any appreciable shaft work associated with them,
so that shaft work is negligible. For such inviscid (i.e. frictionless) flows with no shaft work,
the mechanical energy balance simplifies to Bernoulli’s equation:
Bernoulli’s equation has a wide range of application, despite its simplifying assumptions.
Finally, it is often necessary to relate the volumetric flowrate V or the mass
66
flowrate m through a pipe or other conduit to the average fluid velocity u. The relation is:
m=ρV =ρAu
EXAMPLE 24
Water flows from an elevated reservoir through a conduit to a turbine at a lower level and out
of the turbine through a similar conduit. Note that the cross-sectional area of the conduits is
constant. At a point 100 m above the turbine the pressure is 207 kPa, and at a point 3 m
below the turbine the pressure is 124 kPa. What must the water flow rate be if the turbine
output is 1.00 MW?
67
EXAMPLE 25
A gas stream, containing 8 mol% CO and 92% CO2 at 500 oC, is fed to a waste heat boiler at
the rate of 1 kg-mol/h, where the hot gas flows over the outside of the tubes.
Liquid water at 25 ºC is fed to the boiler in a ratio of 0.2 g-mol of liquid water per 1 g-mol of
hot gas, and flows inside the tubes.
Heat is transferred from the hot gas through the tube walls to the liquid water, causing the hot
gas to cool, and the liquid water to heat to its boiling point and evaporate to form steam at 5
bar. The steam may be used for heating power generation in the plant or as the feed to
another process unit
The gas leaving the boiler is burned (flared) and then discharged to the atmosphere. The
boiler operates adiabatically (i.e. all the heat transferred from the hot gas goes into the liquid
water)
The flow chart of this process is as follows:
What is the temperature of the off-gas? Given:

Enthalpy of liquid water @ 25 ºC = 1,890 kJ/kg-mol
Enthalpy of steam @ 5 bar = 49,455 kJ/kg-mol
No work is takes place in this process
Energy Balances on Reactive Processes

Consider the following example:
EXAMPLE 26
The standard heat of reaction for the oxidation of methane is given below:
One hundred (100) g-mol CH4 and 300 g-mol O2/s at 25 ºC were fed into a reactor in which
CH4 is completely consumed, and the product is at 500 ºC. Calculate the rate at which heat
must be transferred to or from the reactor, assuming operation at ~1 atm.
68
First, we have to perform material balances for this process
From the given data:

• CH4 fed = 100 g-mol/s
• O2 fed = 300 g-mol/s
Thus, from the chemical reaction we obtain the fact that
100 g-mol/s CH4 ≡ 200 g-mol/s O2
Since it is given, in the problem statement, that CH4 is completely, it leads to the fact that O2
is an excess reactant, and the amount of remaining O2 is
300 – 200 = 100 g-mol/s
Also from the balanced reaction, for every 1 g-mol of CH4 consumed,
• 1 g-mol of CO2 is generated
• 2 g-mol of H2O is generated
Thus, for 100 g-mol/s of CH4 consumed,

• 100 g-mol of CO2 is generated
• 200 g-mol of H2O is generated
Accordingly, the amount of moles of each substance in the input and output streams can be
summarised, as follows:
69
To check whether or not our material-balance calculations are correct, we need to do it on

mass basis, and the calculations for the total mass of the input and output streams are as
follows;
The total mass of the “input” stream can be computed as follows:
Performing the same calculations for the “output” stream yields:
This indicates that our material-balance calculations are correct.

We can then proceed to the energy balance calculations.
We start our energy-balance calculations by setting reference states as follows
• T = 25 ºC
• H2O (g) as a combustion product
For our convenience, the enthalpy of each species (substance) for both input and output
streams is tabulated as follows:
Since Tref = 25 ºC, and = 0 is an enthalpy of O2 at 500 ºC (773 K), with reference to that at
25 ºC (298 K), or
xxxxxxxxxxxxxxxxxxxxxxx
70
EXAMPLE 27
The standard heat of reaction for the oxidation of methane is given below:
One hundred (100) g-mol CH4 and 300 g-mol O2/s at 25 oC were fed into a reactor in which
CH4 is completely consumed.
If the reactor operates adiabatically, what is the temperature of the combustion products?
Solution:
Since this Example is the same as that done just recently (Example 6.6), the material-balance
calculations are as same as the previous Example 6.6. The difference is on the ENERGY-
BALANCE calculations.
From the energy-balance equation for this system
Consider the sketch below:
100 g-mol x g-mole oxygen

methane y g-mole carbondioxide
300 g-mole
REACTOR z g-mole water
oxygen
Let the basis be 1 second
Lets us first perform the material balance and determine all the flowrates in every stream.
General material balance equation is:
0 = material in – material out + material generated – material consumed
Assumptions:
 Steady state
 Constant pressure process
From the stoichiometric equation below, the moles of the streams are:
CH 4 ( g ) +2O 2 ( g ) yields CO2 ( g ) +2 H 2 O ( g )−803 k J / g−mole

→
71
Moles consumed:
 Oxygen = 200 g-moles/s

 Methane = 100 g-moles/s
Moles generated:
 Carbon-dioxide = 100 g-moles/s

 Water = 200 g-moles/s
Excess reagent:
 Oxygen = 100 g-moles/s
Summary table of the results:
Substance Moles in Moles out (g-moles/s)

(g-moles/s)
Methane 100 0
Oxygen 300 100
Carbon-dioxide 0 100
water 0 200
From first law of thermodynamics for flow process, we know that:
But when there is no accumulation, minimal kinetic energy, absence of shaft work
and negligible changes in potential energy then:
∆ E K + ∆ EP + ∆ U ≈ 0
2
ϑj
Δ ≈0
2
72
g∆ Zj≈0
W s≈ 0
Therefore the equation reduces to:
n n
∑ mj H j− ∑ m j H j=Q
Inlet j=1 Outlet j=1
º
Q=m j H rxn =100×(−80,300)
¿ 80,300,000 J / g−mole
Let the reference state be 298.15 K
Since the reaction is occurring at constant pressure, then:
H=mC p T
Therefore:
n n
∑ m j H j− ∑ m j H j=Q
outlets j=1 inlets j=1
∑ m j H j =[ ( 100× 35.4 ) + ( 300 ×33.1 ) ] ×298.15=4,016,080

Inlet j=1
∑ m j H j =[ ( 100× 33.1 )+ (100 × 50.0 ) + ( 200× 38.5 ) ] T

Outlet j=1
Combining them we get:
16,010 T −4,016,080=80,300,000
T =5266.5 K
73
Problems on energy balances
1. Natural gas comprising CH4 87.5%, C2H6 7.0%, and C3H8 5.5% by volume is
burned with air (21 vol% O2 and 79% N2) with an excess-air percentage of 10% in an
adiabatic combustor. Determine the outlet temperature of the gaseous products.
Chemical Rxns:
CH 4 ( g ) +2O 2 ( g ) yields CO2 ( g ) +2 H 2 O ( g )−802.4 k J /kg−mole(1)

→
7
C 2 H 6 ( g ) + O ( g ) yields 2 CO2 ( g ) +3 H 2 O ( g )−1,427.9 k J / kg−mole (2)
2 2 →
C 3 H 8 ( g ) +5 O 2 ( g ) yields 3 CO2 ( g ) +4 H 2 O ( g )−2,044.0 k J / kg−mole (3)

→
Given that the heat capacities of these substances (species) are assumed to be constant
throughout the process. The reference temperature of the feed is taken to be 298 K.
CH4 = 35.4 kJ/(kg-mol-K)
C2H6 = 52.6 kJ/(kg-mol-K)
CO2 = 50.0 kJ/(kg-mol-K)
H2O (g) = 38.5 kJ/(kg-mol-K)
O2 = 33.1 kJ/(kg-mol-K)
N2 = 31.3 kJ/(kg-mol-K)
2. Natural gas comprising CH4 78.5% , C2H6 12.0 % & C3H8 9.5% by volume is burned
with air (21 vol% O2 and 79% N2) with an excess-air percentage of 18 % in an
adiabatic combustor. Determine the outlet temperature of the gaseous products if the
feed to the burner is 100 kg-mole/day of natural gas. Chemical reaction equations:
CH 4 ( g ) +2O2 ( g ) yields CO2 ( g ) +2 H 2 O ( g )−802.4 k J /kg−mole(1)

→
7
C 2 H 6 ( g ) + O ( g ) yields 2 CO2 ( g ) +3 H 2 O ( g )−1,427.9 k J / kg−mole (2)
2 2 →
C 3 H 8 ( g ) +5 O2 ( g ) yields 3 CO2 ( g ) +4 H 2 O ( g )−2,044.0 k J /kg−mole (3)

→
Given that the conversions of reaction (1), (2) & (3) are 70 %, 90 % and 100 %
respectively and the heat capacities of these substances (species) are assumed to be
constant throughout the process. The reference temperature of the feed is taken to be
298 K.
74
CH4 = 35.4 kJ/(kg-mol-K)

CO2 = 50.0 kJ/(kg-mol-K)
H2O (g) = 38.5 kJ/(kg-mol-K)
O2 = 33.1 kJ/(kg-mol-K)
N2 = 31.3 kJ/(kg-mol-K)
3. As a safety engineer, you are asked to perform a safety analysis for a power plant
boiler. The maximum design temperature for the boiler is 2,000 ºC, and the worst case
scenario is that the fuel combusts completely and no heat is transferred out of the
system; in other words, the system is operating adiabatically.
The fuel used for this boiler comprises 80 mol% methane (CH4) and 20% ethane
(C2H6), and it is preheated to the temperature of 100 ºC before entering the system.
Air (21 mol% O2 + 79% N2), which is to be burned with the fuel, is also preheated,
but to the temperature of 300 ºC, before being fed into the system. The percentage of
excess O2 (or percentage of excess air) is 10%.
Determine whether or not the boiler is going to be exploded. Note that the boiler may
be exploded when the final temperature (for the worst case scenario) of the system
exceeds 2,000 ºC.
Given that the heat capacities of these substances (species) are assumed to be constant
throughout the process:
CH4 = 35.4 J/(g-mol-K)
C2H6 = 52.6 J/(g-mol-K)
CO2 = 50.0 J/(g-mol-K)
H2O (g) = 38.5 J/(g-mol-K)
O2 = 33.1 J/(g-mol-K)
N2 = 31.3 J/(g-mol-K)
Additional data (which may or may not be used to solve this Question) Standard heat
of formation (for CH4 = –74,850 J/g-mol;
C2H6 = –84,670 J/g-mol;
CO2 = –393,500 J/g-mol;
H2O = –241,830 J/g-mol
75
76

CHP 294 Notes

Uploaded by

Copyright:

Available Formats

CHP 294 Notes

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

CHP 294 Notes

Uploaded by

Copyright:

Available Formats

CHP 294 LECTURE NOTES

PRINCIPLES OF MASS AND ENERGY BALANCE

- Introduction to mass and energy balance systems

They are pre-requisite to calculation of all other calculations in chemical engineering

They are based on conservation laws of matter.

Material balances can be carried out bassed on:

Chemical processes may be classified as:

No mass enters or leaves at the time of charging and discharge

The independence of an equation can be established by formulating a matrix and determining

Solving material balance problems involving simultaneous equations

Flow process, steady state:

Take a basis as “1,000 kg of mixture”

Overall mass balance:

( 0.4 × 1000 )=375+ y ...................................ii

Solving equation i and ii simultaneously, we obtain

Assumption: Steady-state process

Take a basis of 1 min flow of material

Molar flowrate of water:

mass=20 ×1=20 g /min

S4 =74.07 moles per minute .................................. (i)

0.79 S1=x S 4 ............................................................... (ii)

1.00 S 2 +0.21 S 1= y S 4 ................................................... (iii)

S2=1 /5 S1 ..................................................................... (iv)

0.015+ x + y=1 ......................................................... (v)

Solving equation (i) and (ii)

S1=93.76 x ................................................................ (vi)

Combining equstion (i), (iii) and (vi):

S2 +(0.21× 93.76 x)=74.07 y ............................... (vii)

Combining equation (v) and (vii):

S2 +93.76 x=72.96 ............................................. (viii)

Combining equation (iv) and (vi):

S2=18.75 x ........................................................... (ix)

Combining equation (ix) and (viii):

18.75 x+ 93.76 x=72.96

SINGLE UNIT PROCESSES

Consider the following Examples

• wt% of MeOH in Stream 2 = 100 – 30.0 = 70.0 wt%

( 0.4 × 200 ) + ( 0.7 ×150 ) =350 y

Calculate mass of Streams i, ii, and iii

x + y + z=1000 kg product ............................................... (i)

We still need another 2 (two) equations.

0.113 x+ 0.90 y=( 0.32× 1000) ............................................ (ii)

0.444 x +0.98 z=(1000× 0.60) ............................................ .. (iii)

Solving eqns. (i), (ii) and (iii) simultaneously yields

• NO chemical reaction between species A and B

• Wt% of species B in Stream 2

60+ ( 0.35 × 30 )=( 90 × y )

y=0.783 Mass fraction of A

Z = 0.217 Mass fraction of B

Drying & Concentrating Processes

Normally, a solute is to be concentrated by removing (e.g., drying) a solvent.

Assumption: Steady-state process

100= x+ y ............................................ (i)

Caustic soda balance:

( 100 ×0.04 )=( 0.25 x )

y=84 kg water evaporated

Caustic soda is the tie component in this question.

Physical separation process: Centrifugation

Since 1ppm = 1 mg/L or 1 mg/kg, then: