CHEMICAL PROCESS CALCULATIONS

LECTURE 2.FUNDAMENTALS OF
MATERIAL BALANCES - MATERIAL
BALANCE FOR NONREACTIVE
PROCESSES
Recall: Processes

■ A process refers to any operation or series of operations by which a

particular objective is accomplished.

Input/Feed Output/Product
Process unit
Recall: Classification of processes
according to mode of operation
■ Batch process: The feed is charged into a vessel at the beginning of
the process and are removed some time later. No mass crosses the
system boundary between the time the feed is charged and the time the
product is removed.
■ Continuous process: The input and output flows continuously
throughout the entire process duration.
■ Semi-batch process: Any process that is neither batch nor continuous.
Steady state vs. unsteady state operation

■ Steady-state: occurs when the values of all process variables

(temperature, pressure, flow rates) do not change with time, except
possibly for minor fluctuations about constant mean values.
■ Transient/unsteady-state: process variables change with time.
 General Balance Equation

■ A balance on a conserved quantity (mass, energy, momentum) in

system is generally written according to general balance equation.

Entering through Leaving through Produced within Consumed within Build-up within the system
the system the system the system the system
boundaries boundaries
Types of Balances

■ Differential balances: indicate what is happening in a system at an

instant; each term in the balance is a rate and has units of the
balanced quantity per unit time; usually applied to continuous
processes.

■ Integral balances: describe what happens between two instant of

time; each term in the balances is an amount of the balanced quantity;
usually applied to batch processes.
Material balances
■ General balance equation:

■ To simplify material/mass balance equations:

(1) If total mass is being balanced, generation and consumption terms
are zero.
(2) If the balanced substance is a nonreactive species, generation and
consumption terms are zero.
(3) If the system is at steady state, accumulation term is zero.
Material balances

■ For a continuous steady-state process:

■ For a continuous steady-state process with no reactions:

■ Consider the following process:
The catalytic dehydrogenation of propane is carried out in a continuous
packed-bed reactor. One thousand kilograms per hour of pure propane is
preheated to a temperature of 670oC before it passes into the reactor. The
reactor effluent gas, which includes propane, propylene, methane, and
hydrogen, is cooled from 800oC to 110oC and fed to an adsorption tower,
where the propane and propylene are dissolved in oil. The oil then goes to a
stripping tower in which it is heated, releasing the dissolved gases; these
gases are recompressed and sent to a distillation column in which propane
and propylene are separated. The propane stream is recycled back to join the
feed to the reactor preheater. The product stream from the distillation column
contains 98% propylene and recycle stream is 97% propane. The stripped oil
is recycled to the absorption tower.

Question: How would you illustrate this process?

Process Flowchart
■ A process flowchart is a representation of processes using boxes or
other symbols to represent process units (reactors, mixers, separation
units, etc.) and lines with arrows to represent inputs and outputs.
Drawing Process Flowcharts

(1) Identify the process units and streams described in the process.
(2) Write the values and units of all known stream variables at the
location of the streams on the chart.
(3) Assign algebraic symbols to unknown stream variables and write
these variable names and their associated units on the chart
Example 1

An ethanol/water mixture stream flowing at 1000 kg/h enters a

distillation column. The composition of ethanol in the feed is 20% by
weight. A vapor product that is 90% by weight ethanol is drawn from
the top of the column and a liquid product that is 5% by weight ethanol
is drawn from the bottom of the column. Draw the process flowchart
of the described process.
 D kg/h
90 wt% EtOH
10 wt% H2O

1000 kg/h
20 wt% EtOH
80 wt% H2O
DISTILLATIO
N COLUMN

B kg/h
5 wt% EtOH
95 wt% H2O
Example 2

A process is designed to concentrate an aqueous solution containing

15% NaOH and 0.5% NaCl. A feed of this mixture is charged to an
evaporator at a rate of 6000 kg/h. The concentrated solution is mixed
with an aqueous NaOH solution entering at a rate of 2000 kg/h in a
mixer. The mixer effluent is analyzed to contain 40% NaOH and
0.85% NaCl. Draw the process flowchart of the described process.
 W kg/h S kg/h
100% H2O xS,NaOH
xS,H2O

EVAPORATO
MIXER
R
6000 kg/h C kg/h 2000 kg/h
15% NaOH xC,NaOH 40% NaOH
0.5% NaCl xC,NaCl 0.85% NaCl
84.5% H2O 59.15% H2O
xC,H2O
Choosing a Basis of Calculation
■ A basis of calculation is an amount (mass or moles) or flow rate
(mass or molar) of one stream or stream component in a process.
■ Choosing a basis for calculation is an initial step in balancing a
process; all unknown variables are determined consistent to the
basis.
■ If a stream amount or flow rate is given in a problem, it is usually
most convenient to use this as the basis of calculation. If no amounts
or flow rates are known, assume one, preferably that of a stream
with known composition.
Example 1
An ethanol/water mixture stream flowing at 1000 kg/h enters a
distillation column. The composition of ethanol in the feed is 20% by
weight. A vapor product that is 90% by weight ethanol is drawn from
the top of the column and a liquid product that is 5% by weight ethanol
is drawn from the bottom of the column. What is an appropriate basis
for the balancing of this process?
Example 1
An ethanol/water mixture stream flowing at 1000 kg/h enters a
distillation column. The composition of ethanol in the feed is 20% by
weight. A vapor product that is 90% by weight ethanol is drawn from
the top of the column and a liquid product that is 5% by weight ethanol
is drawn from the bottom of the column. What is an appropriate basis
for the balancing of this process?

Answer: 1 h operation (1000 kg/h of feed)

Example 2

A gaseous mixture of a saturated hydrocarbon and nitrogen gas is

burned with 30% excess air. The combustion gases were analyzed and
its composition on a dry-basis (excluding water) were reported as
follows: 8.95% CO2, 0.99% CO, 1.99% H2, 6.46% O2 and 81.61% N2.
What is an appropriate basis for balancing this process?
Example 2

A gaseous mixture of a saturated hydrocarbon and nitrogen gas is

burned with 30% excess air. The combustion gases were analyzed and
its composition on a dry-basis (excluding water) were reported as
follows: 8.95% CO2, 0.99% CO, 1.99% H2, 6.46% O2 and 81.61% N2.
What is an appropriate basis for balancing this process?

Answer: 100 moles of dry combustion gases

Overall mass balance and component
mass balance
B
xB,1
■ An overall material/mass balance
xB,2
accounts for the masses of all
components in a process unit or xB,3
system.
Process unit
Assuming continuous steady-state A C
operation with no reaction: xA,1 xC,1
xA,2 xC,2
xA,3 xC,3
Overall mass balance and component
mass balance
B
xB,1
■ A component material/mass balance
xB,2
accounts for the mass of a single
component entering a process unit or xB,3
system
Process unit
Assuming continuous steady-state A C
operation with no reaction: xA,1 xC,1
Component mass balance of component 1 xA,2 xC,2
xA,3 xC,3
Example 1
An ethanol/water mixture stream flowing at 1000 kg/h enters a
distillation column. The composition of ethanol in the feed is 20% by
weight. A vapor product that is 90% by weight ethanol is drawn from
the top of the column and a liquid product that is 5% by weight ethanol
is drawn from the bottom of the column. What is an appropriate basis
for the balancing of this process?
 D kg/h
90 wt% EtOH
10 wt% H2O

1000 kg/h Basis: 1 h (1000 kg/h feed)

20 wt% EtOH
80 wt% H2O Overall mass balance:
DISTILLATIO
N COLUMN
Ethanol mass balance:

B kg/h
5 wt% EtOH
95 wt% H2O
Degree of Freedom Analysis

■ A degree of freedom analysis determines whether the number of

unknowns and equations for a given process is enough for its complete
specification.
■ The number of degrees of freedom ND for a given process is given by:

where NU: number of unknowns

NE: number of independent equations
Degree of Freedom Analysis
Case ND Classification for Solution

NU = NE 0 Exactly specified; a solution exists

NU > NE > 0 >0 Underspecified; more independent equation

required
NU < NE < 0 <0 Overspecified; in general, no solution exists
unless some constraints are eliminated or
some additional unknowns are included in
the problem
Degree of freedom analysis

■ What equations can be written?

(1) Material balances
(2) Process specifications
(3) Physical properties and laws
(4) Physical constraints
(5) Stoichiometric relations
(6) Energy balance
Example

■ 1000 kg of mixed acid of composition 40% H2SO4, 45% HNO3 and

15% H2O is to be produced by strengthening waste acid of 30%
H2SO4, 36% HNO3 and 34% H2O by weight. Concentrated sulfuric
acid of strength 95% and concentrated nitric acid containing 80%
acid are available for this purpose. Do a degree of freedom analysis
for this process. Is the process exactly specified?
■ Basis: 1000 kg of mixed acid
Sulfuric acid, S kg Nitric acid, N kg
95% H2SO4 80% HNO3
5% H2O 20% H2O

MIXER
Waste acid, W kg Mixed acid, M = 1000 kg
30% H2SO4 40% H2SO4
36% HNO3 45% HNO3
34% H2O 15% H2O
 Sulfuric acid, S kg Nitric acid, N kg
95% H2SO4 80% HNO3
5% H2O 20% H2O

MIXER
Waste acid, W kg Mixed acid, M = 1000 kg
30% H2SO4 40% H2SO4
36% HNO3 45% HNO3
34% H2O 15% H2O
Unknowns: S, N, W
Equations: 1 overall mass balance
2 component mass balance
ND = 3 – 3 = 0. Hence, the process is EXACTLY SPECIFIED.
General Procedure for Single-Unit Process
Material Balance
(1) State the assumptions for the problem.
(2) Choose a basis of calculation an amount or flow of one of the process
streams.
(3) Draw the process flowchart. Show all known variable values and
unknown stream variables on the flowchart.
(4) Do a degree of freedom analysis.
(5) If the degree of freedom is zero, write all independent equations
necessary to completely specify the process.
(6) Solve the equations. Calculate all required quantities.
Key/Tie Component
B
xB,1
■ A key/tie component is a component
xB,2
entering a process unit on one stream and
leaves on only one stream.
■ In the following example, component 3 is
the tie component. Process unit
Component mass balance for component 3 A C
xA,1 xC,1
xA,2 xC,2
xA,3 xC,3
Drying
■ Involves removal of water or other liquids in a solid material
■ Involves blowing hot dry air over the wet solid, evaporating water,
and leaving a dry product and producing humid air

Moisture, W
100% H2O

Wet material, F Dry material, P

xF,solid DRYER xP,solid
xF,H2O xP,H2O
Example
■ A batch dryer can handle 5000 kg feed per hour. 5000 kg of a
material containing 30% moisture is to be dried. How much
moisture evaporates per hour if the dried material contains 5%
moisture?
Assume: steady-state operation
Basis: 1 hr operation (5000 kg of feed)
Water evaporated, W kg

Feed 5000 kg Dry material, P kg

DRYER
30% moisture 5% moisture
70% dry solid 95% dry solid
 Water evaporated, W kg

Feed 5000 kg Dry material, P kg

DRYER
30% moisture 5% moisture
70% dry solid 95% dry solid

■ Unknown: P, W
■ Equations
Overall mass balance:
Dry solid balance:
 Evaporator
Vapor (V)
■ Used to concentrate a solution
containing a non-volatile solute and a Feed (F)
xF
volatile solvent
■ Involves vaporization of a portion of EVAPORATOR
the solvent to produce a concentrated Steam (S)
solution or thick liquor.
Overall mass balance: Condensate(C)

Solute balance:
Thick Liquor (L)

xL
 Example
Vapor (V)

Feed F 500 gpm

■ A 1oBx sugar solution at 60oF was fed to 60oF
an evaporator at a rate of 500 gpm. The 1oBx
concentrate leaving the evaporator flows EVAPORATOR
at a rate of 200 gpm. A sugar content of Steam (S)
12oBx was analyzed from the concentrate.
What is the mass of water (lbm) that is
Condensate(C)
evaporated in a one-hour operation?
Assumption: steady-state operation
Basis: 1 min (500 gallons of feed) Thick Liquor (L)
200 gpm
12o Bx
 ■ Recall oBx definition
Vapor (V)

■ Convert the sugar content in oBx to SG(60oF) and

Feed F 500 gpm find the masses of the feed stream and the thick
60oF liquor.
1oBx
Feed stream: SG(60oF, 1oBx) = 0.9975
EVAPORATOR
Steam (S)

Condensate(C)

Thick liquor: SG(60oF, 12oBx) = 0.9709

Thick Liquor L 200 gpm

12o Bx
 ■ Overall material balance:
Vapor (V)

Feed F 500 gpm

60oF
1oBx This is for a on a basis of 1 minute operation. For a
EVAPORATOR one-hour operation of the evaporator:
Steam (S)

Condensate(C)

Thick Liquor (L)

12o Bx
 Distillation (D)
Distillation xD

■ Separation of mixtures based on the

differences in volatilities
■ Feed mixture of two or more component is Feed (F)
xF DISTILLATI
separated into two or more products, ONCOLUMN
including and more often limited to, an
overhead distillate and a bottoms product
Overall mass balance:

Component mass balance (volatile): Bottoms (B)

xB
Example

■ An ethanol/water mixture stream flowing at 1000 kg/h enters a distillation

column. The composition of ethanol in the feed is 20% by weight. A vapor
product that is 90% by weight ethanol is drawn from the top of the column
and a liquid product that is 5% by weight ethanol is drawn from the bottom of
the column. What is the percent recovery of ethanol in the distillate?
Assume: steady-state operation
Basis: 1 hr. of operation (1000 kg of feed)
 D kg/h
Overall mass balance:
90 wt% EtOH
10 wt% H2O
Ethanol mass balance:

1000 kg/h
20 wt% EtOH DISTILLATI
80 wt% H2O ON
COLUMN

B kg/h
5 wt% EtOH
95 wt% H2O
Crystallization

■ Involves formation of solid particles with a homogenous solid phase (i.e.

liquid solution) by either cooling or removing some of the solvent
■ Two-phase mixture of mother liquor (ML) and crystals (C) occupying the
crystallizer and withdrawn as product called magma
■ Adhering mother liquor is removed either by filtration or centrifugation
and the balance is removed by washing with fresh solvent. Crystal with
most of the mother liquor removed is called the wet crop.
Crystallization
Solvent (S)

Feed (F) CRYSTALLIZE Magma Wet crop

CENTRIFUGE
R (WC)
OR FILTER

Final Mother
Liquor (ML’)
Example

■ One thousand kilograms of a 64% NaNO3 solution in water is at a

temperature of 100oC. This is sent to a crystallizer where it is cooled
to 30oC. At this temperature, the solubility of NaNO3 is 96 g of
NaNO3 per 100 g of water. Calculate the amount of crystals that
precipitate if 5% of the original water evaporates during cooling.

Basis: 1000 kg of feed

 Water evaporated in crystallizer:
Water evaporated S
5% of water in feed

1000 kg Mother liquor M Overall mass balance:

64% NaNO3 96 g NaNO3/100 g H2O
CRYSTALLIZER
NaNO3 balance:

Crystals C

Solving:

.
Material Balances on Multiple Unit
Processes
■ Material balances in a multi-unit system is similar for a single-unit
system
■ An overall mass balance and component mass balance are set around
the whole system. Then, balances around individual units are
performed. Likewise, balances around joints where mixing of
streams occur and points of splitting of streams are set up.
 Example: Multiple-effect Evaporator
■ A triple-effect evaporator concentrates 100 kg/h of a 10% NaOH
solution to 50% according to the following flowchart . Assuming
equal amounts of evaporation in each effect, calculate the flow rates
and concentration of the solution leaving each effect.
Steam S E1 kg/h E2 kg/h E3 kg/h

Effect 1 Effect 2 Effect 3

Feed F 100 kg/h P1 kg/h P2 kg/h P3 kg/h
10% NaOH xP.1 xP.2 xP.3

C1 C2 C3
Example: Crystallization Unit
■ Sodium chloride crystals are to be produced from 1000 kg of a solution
containing 10% NaCl, 1% KOH, and 89% H2O. The solution is first sent to an
evaporator where 790 kg of the water from the solution is removed. The hot
concentrated solution is cooled to 20oC and NaCl crystals precipitate. Each kg
of crystals carries with it 0.1 kg of adhering mother liquor. The wet crop is
then treated into a dryer where 95% of the water is removed. Calculate:
a) The composition of the concentrated solution from the evaporator
b) The composition of the final crystal product
c) The percent recovery of NaCl from the original solution
Data: At 20oC, the solutibility of NaCl in H2O is 36 g NaCl/100 g H2O. KOH is
non-volatile and soluble in H2O.
 Process Flowchart D kg H2O
95% of water in W
790 kg H2O

Wet crop W kg
0.1 kg mother
liquor/kg crystals Final crystal
product P kg
EVAPORAT CRYSTALLIZ
DRYER
OR ER
1000 kg
10% NaCl
1% KOH
89% H2O
Saturated solution S
36 g NaCl/100 g H2O
 Recycle stream

■ Recycle stream refer to a process stream wherein part of the material

from the downstream of a process unit is returned and mixed with the
fresh feed entering the process unit.
■ Purpose of using a recycle stream
(1) Recovery and re-use of unconsumed reactants
(2) Recovery of catalysts
(3) Dilution of a process stream
(4) Control of a process variable
(5) Circulation of a working fluid
 1 E

Process unit
A B C
D
3 4
Recycle stream with separator
■ A product separator unit may separate the products of a process
unit. Some of the products from the separator unit is recycled and
mixed with the fresh feed while the other products are withdrawn
from the process.

PRODUCT
REACTOR SEPARATIO
NUNIT
Problem

■ 4500 kg/h of a solution that is 33.3% K2CrO4 by mass is joined by a recycle

stream containing 36.4% K2CrO4 and the combined stream is fed into an
evaporator. The concentrated stream leaving the evaporator contains 49.4%
K2CrO4; this stream is fed into a crystallizer in which it is cooled (causing
crystals of K2CrO4) to come out of the solution) and then filtered. The filter
cake consists of K2CrO4 crystals and a solution that contains 36.4% K2CrO4 by
mass; the crystals account for 95% of the total mass of the filter cake. The
solution that passes through the filter, also 36.4% K2CrO4, is the recycle stream.
Calculate the rate of evaporation, the rate of production of crystalline K2CrO4,
the feed rates of the evaporator and the crystallizer must be designed to handle
and the recycle ratio (mass of recycle/mass of fresh feed)
 Process Flowchart

Gross feed G kg/h W kg/h Filter cake

100% H2O S kg/h K2CrO4 crystal
L kg/h 36.4% K2CrO4
C kg/h solution
Fresh feed F (filter cake is 95% crystal
49.4% K2CrO4
4500 kg/h CRYSTALLIZE by mass)
EVAPORATOR R AND FILTER
33.3% K2CrO4

R kg/h
36.4% K2CrO4
■ Assumption: steady-state operation
■ Basis: 1 hr. of operation (4500 kg/h) of fresh feed
■ Specification: Filter cake is 95% crystal by mass

Overall mass balance (around the system)

K2CrO4 balance (around the system)

Solving the system of equations:

Overall mass balance (around crystallizer):

Water balance (around crystallizer):

Solving the system of equation

Thus, the recycle ratio is given by:

Mass balance around the recycle-fresh feed mixing point

Bypass stream

■ Bypass stream refers to a process stream which is initially part

of the fresh feed that is mixed with the gross product of a
process unit
■ Purpose of using a bypass stream
(1) Attain precise control of process variables (concentration,
temperature, etc.)
(2) Dilution of a process stream
 1 E

Process unit
A B C
D
3 4
 Example Bypass stream B
kg/h
100% H2O
■ It is desired to produce 7% NaNO3 solution
continuously according to a process
described in the following flowchart. The Net product
water line (NaNO3-free) is split in two. 500 P kg/h
kg/hr of water is sent to a tank where pure Fresh feed F 7% NaNO3
NaNO3 crystals are added. The mixture is kg/h Saturator
stirred well to form a saturated solution of 100% H2O Gross product
NaNO3 (49 g NaNO3/100 g solution). The Process G kg/h
feed 47.9% NaNO2
other line bypasses the tank and is mixed
500 kg/h
with the saturated solution. What is the 100% H2O
flowrate of the bypass stream and the final
product? NaNO3
N kg/h
 Bypass stream B
kg/h
100% H2O

Net product
P kg/h
Fresh feed F 7% NaNO3
kg/h Saturator
100% H2O Gross product
Process G kg/h
feed 47.9% NaNO2
500 kg/h
100% H2O
Purge stream

■ A purge or bleed stream is a process stream used in recycling

operations where a fraction of the recycle stream is removed to
avoid accumulation of inerts or unwanted material that might
buildup in the recycle stream
 1 E G

2
F

Process unit
A B C
D
3 4
 Make-up water M
Example 30 ppm CaCO3 Evaporation
1200 kg/h

A cooling tower cools water by contacting it with

air intimately. Some water evaporates. It gets the
latent heat required from the bulk of the liquid
water. This provides the cooling effect. This
evaporated water is replenished by addition of
make-up water. The water used normally contains Cooling
Process
tower
CaCO3. To avoid scale formation in the process
pipes, the CaCO3 should be kept below 130 ppm.
This is done by providing a purge stream.
In a certain cooling tower, the make-up water
contains 30 ppm CaCO3. The evaporation is 1200
kg/h. What should be the minimum flow of the
Purge P
purge stream to avoid deposition of CaCO3? 130 ppm CaCO3
Assume no entrainment of water in the air occurs.
Basis: 1 hr. of operation (1200 kg of evaporated Make-up water M
water) 30 ppm CaCO3 Evaporation
1200 kg/h

Overall mass balance:

CaCO3 balance:
Cooling
Process
tower

Purge P
130 ppm CaCO3