CHAPTER 1

MASS BALANCES
FACULTI OF APPLIED SCIENCES

1
 CONTENT
 Introduction to mass transfer.
 General Mass Balance Equations.
 Mass Balance Calculations-Non-Reactive
Process.
 Mass Balance on Multiple Unit Process.
 Mass Balances Calculations-Reactive
Process

2
 Introduction to mass transfer
 Mass transfer is a transfer of a material from one
homogenous phase to another. With or without
phase change.
 Mass transfer may occur in a gas mixture, a liquid
solution or solid.
 Mass transfer occurs whenever there is a
gradient in the concentration of a species.
 The basic mechanisms are the same whether the
phase is a gas, liquid, or solid.

3
 GENERAL MASS BALANCE EQUATIONS

 Mass balance is a systematic method of keeping

track with amount of materials that flows into or out
of process.
 A balance on a conserved amount (total mass, mass
of particular species, energy, momentum) in a
system (single process, collection of units, or entire
process) may be written as follows:

Input + Generation – Outputs – Consumption = Accumulation

4
General mass balance equation:

Input + Generation – Outputs – Consumption = Accumulation

 Input - Amount al all mass that cross the system boundary into
a system
 Outputs - Amounts of all mass that cross the system boundary
out of a system
 Generation - Amount of all mass that are generated within a
system boundary by chemical reactions
 Consumption - Amount of all mass that are consumed within a
system boundary by chemical reactions
 Accumulation
• Net change in amount of mass within a system boundary.
• +ve change means there is an increase in materials within a
system.
• -ve change means there is decrease in materials within a
system
5
 Generation within the
Inputs system by reactions Outputs
Consumption within the
system by reactions

System boundary

6
 CONSTRUCTING AND LABELING AN
ARROW AND BLOCK DIAGRAM (FLOW CHART)

 An arrow and block diagram (flow chart) consists of a

combination of one or more rectangular blocks and arrow.
 A rectangular block symbolizes a process unit or series of
process units.
 Inward pointing arrow represents an input process stream unit.
 Outward pointing arrow represents an output process stream
unit.

Input process stream PROCESS Output process stream

UNIT

Inward Outward
pointing arrow pointing arrow
Block
7
  You must label the block and arrow diagram
with proper symbol.
 Rates or amount of process streams are
normally written on the arrows.
 Compositions or process stream are written
below the arrows.
 Unknown rates or amount and unknown
compositions must be labeled by certain
symbols.
 The choice of symbols for unknown
compositions must be picked such that it
minimizes the number of unknowns and it
does not conflicts with other symbols.
8
 STEP BY STEPS GUIDE

 Once you know exactly what the question wants,

begin drawing the flow sheet according to the
process information described in the question.
 2 ways of labeling flowchart:
• Compositions of process streams are labeled in
terms of mass or mole fractions of each species
present in the streams.
• Compositions of process streams are labeled in
terms of mass flow rate, molar flow rate or
amount of each species present in the streams.

9
 Known mass flow Unknown flow
rates of process rates of process
450 kg/h water streams
streams

1000 kg/hr wet P kg/hr product

sugar sugar
0.5 water
DRYING x water
0.5 dry sugar (1-x) dry sugar
1 1

Known composition in
Unknown composition in
terms of mass fractions
terms of mass fractions
of species
of species

10
 Known mass flow
rates of process
streams
450 kg/h water

Wet sugar Product sugar

DRYING
500 kg/h water W kg/h water
500 kg/h dry sugar V kg/h dry sugar

Known composition in
Unknown composition in
terms of mass flow rates
terms of mass flow rates
of species
of species

11
  Do not forget to label the flow sheet and assign
proper symbols to the unknown.
 If the number of species with unknown mass or mole
fractions in n, then you should assign symbols to
n-1 species only.

 Eg 1:
• If a stream has a total of 6 species, which all are
unknown, then you should assign 5 symbols (6-1)
to 5 species only (x,y,z,w,v).
• The mass or mole fraction of the sixth species is
simply:
1-x-y-z-w-v

Since the total mass or mole fraction of the stream

is 1.
12
 Eg 2:
• Ifthe for example, a stream has 3 species and
one species mass fraction is known, say 0.2.

• Then the number of unknown species is only 2.

• So, only 1 symbol (2-1) to 1 species (x) should
be assigned.

• The mass fraction of the last species is simply:

1- 0.2 - x or 0.8 - x

13
 TEST YOURSELF

DILUTION PROCESS

A stream containing (by mass) 30%

methanol in water is to be diluted with a
second stream containing 5% methanol
to form a product containing 20%
methanol. Draw a completely labeled
flow sheet for this process.

14
 All composition are in mass percent, so the streams must use
mass NOT mole.

A kg/h 30% P kg/h 20%

methanol solution methanol solution
0.30 methanol Dilution 0.20 methanol
0.70 water 0.80 water
1
process 1

B kg/h 5%
methanol solution
0.05 methanol
0.95 water
1

15
 TEST YOURSELF 2

MIXING PROCESS

10 kgmol/h acid solution containing (by moles)

10% H2SO4, 4% HCI, 5% HNO3 is to be
concentrated by adding 6.3 kg/h of pure liquid
HNO3.
a) Draw a completely labeled flow sheet for
this process.
b) Determine the molar composition of the
product concentrated solution.

16
 10 kgmol/h product
acid solution
0.10 H2SO4
0.04 HCI
0.05 HNO3
0.81 water P kgmol/h product
1 Mixing acid solution
Process x H2SO4
y HCI
z HNO3
1-x-y-z water
6.3 kg x kgmol = 0.1 kgmol/h HNO 1
3
h 63kg

1 HNO3

17
 BASIS OF CALCULATION

 After the flow sheet is properly drawn and

unknowns are completely labeled, you must
choose a basis of calculation in solving the
material balance problem.
 A basis of calculation is an amount (mass or mole)
or a flow rate (mass or molar) of one stream or
stream component in a process.
 Main purpose of assigning a basis is:
• To facilitate your mass balance calculation.
• Without a basis, it is almost impossible to solve
material balance problems.

18
  A known basis of calculation is a basis based on
a process stream which amount or rate is known or
already given in the problem statement.
 When all stream amounts or flow rates are
unknown, you must assume 1, if possible that
stream with a known composition.

 Eg:
• If mass fractions are known, choose a total mass
or mass flow rate as a basis.
• If mole fractions are known, choose a total mole
or molar flow rate as a basis.

 This basis is called an assumed basis of

calculation.
19
 INDEPENDENT EQUATION

 After the basis has been established, you must do an

analysis by checking how many independent equations that
could be written and how many unknowns are present.
 An independent equation is an equation that exists on its
own without depending on the presence of any other
equations.
 Two main sources of independent equations, which are:
a) Independent equations form material balances:
 Total number of independent equations from material
balances is always equal to total number of species
that are present within the process.

b) Independent equations process specifications:

 Process specifications are direct assignment of
values to the stream variables or the imposition
20
of relationships between stream variables.
  Once the total number of independent equations
(from material balances and process specifications)
and number of unknown have been analyzed and
identified, you would probably be left either one of
the following condition, and you must proceed as
explained below according to which condition you
face:

a) Total number of independent equations = total

number of unknowns.

 The problem has a unique solution.

 So, you can go ahead and solve the
simultaneous equations.

21
 b) Total number of independent equations < total
number of unknowns
 The problem has been underspecified.
 Thus, it can’t be solved unless extra
information are known.
 Do not solve this type of problem.

c) Total number of independent equations > total

number of unknowns
 The problem has been overspecified and it
has no unique solution.
 Instead it has many solutions.
 Do not solve this type of problem.

22
 EXAMPLE 1 – DILUTION PROCESS

A stream containing (by mass) 30% methanol

in water is to be diluted with a second stream
containing 5% methanol to form a product
containing 20% methanol.

a) Draw a completely labeled flow sheet for

this process.
b) Indicate the basis.
c) Analyze the unknowns and independent
equations.

23
 A kg/h 30% P kg/h 20%
methanol solution methanol solution
0.30 methanol Dilution 0.20 methanol
0.70 water 0.80 water
1
process 1

B kg/h 5%
methanol solution
0.05 methanol
0.95 water
1

24
  Since all streams is unknowns, you must pick an
assumed basis.
 Any stream can be used, but it is much easier if you
pick the stream with known composition.

Assumed basis = 100 kg/h 30% methanol solution (A)

Analysis:
 Number of unknowns = 2 (P & B)
 Number of independent equations = 2 (2 material
balances, that is methanol and water)
 Thus unknowns have unique solutions and can be
solved.

25
 EXAMPLE 2 – MIXING PROCESS

10 kgmol/h acid solution containing (by moles)

10% H2SO4, 4% HCI, 5% HNO3 is to be
concentrated by adding 6.3 kg of pure liquid
HNO3.

a) Draw a completely labeled flow sheet for

this process.
b) Indicate the basis.
c) Analyze the unknowns and independent
equations.
26
 10 kgmol/h product
acid solution
0.10 H2SO4
0.04 HCI
0.05 HNO3
0.81 water P kgmol/h product
1 Mixing acid solution
Process x H2SO4
y HCI
z HNO3
1-x-y-z water
0.1 kgmol/h HNO3 1

27
  Since two streams are known, you just pick any
stream as a basis.

Known basis = 10 kgmol/h acid solution

or
= 0.1 kgmol/h HNO3

Analysis:
 Number of unknowns = 4 (P,x,y,z)
 Number of independent equations = 4 (4 material
balances, that is H2SO4, HCI, HNO3 and water)
 Thus unknowns have unique solution and can be
solved.

28
 EXAMPLE 3 – DISTILLATION PROCESS

1000 kg/h of a mixture containing equal parts by

mass of Benzene and Toluene are distilled. The flow
rate of the overhead product stream is 488 kg/h and
the bottom stream contains 7.11 % benzene (by
mass).

a) Draw a completely labeled flow sheet for this

process.
b) Indicate the basis.
c) Analyze the unknowns and independent
equations.

29
 488 kg/h overhead

x toluene
1-x benzene
1
1000 kg/h mixture
DISTILLATION
0.5 toluene
0.5 benzene
1

B kb/h bottom
0.9289 toluene
0.0711 benzene
1

30
  Since two streams are known, you just pick any
stream as a basis.

Known basis = 1000 kg/h mixture

Analysis:
 Number of unknowns = 2 (B,x)
 Number of independent equations = 2 (2 material
balances, that is benzene and toluene)
 Thus unknowns have unique solution and can be
solved.

31
 EXERCISE

Sludge is wet solid which remains after processing

municipal sewage by Indah Water Konsortium
(IWK). The sludge containing 60% water and 40%
solid by mass is passed through a drier, and the
resulting product contains 25% water.

a) Draw a completely labeled flow sheet for this

process.
b) Indicate the basis.
c) Analyze the unknowns and independent
equations.

32
 solution

33
 DEGREE OF FREEDOM ANALYSIS

 Degree of freedom (DOF) analysis is to determine

whether we have enough information to solve a
given problem.
 To perform DOF analysis, we must:
a) Draw and completely labeled a flowchart.
b) Count the unknown on the chart.
c) Count the independent equation.
d) Subtract the second number from the first.
 The result is the number of Degree of Freedom (DOF)
of the process.
nDOF = nunknowns – nidependent equations

34
 There are 3 possibilities of DOF analysis:
a) If nDOF = 0
 The problem can be solved.
b) If nDOF > 0
 There are more unknown than independent
equations relating them, and at least nDOF
additional values must be specified before all of
the remaining variable value can be determined.
 The problem is likely to be waste of time to
be calculated solved.
c) If nDOF < 0
 There are more independent equations than
unknown.
 Either the flowchart is incompletely labeled.
 The problem is likely to be waste of time to be
calculated solved.
35
 MATERIAL BALANCE CALCULATION

 General material balance equation:

Input + Generation – Outputs – Consumption = Accumulation

 Rules used to simplify the material balance equation:

a) If the balanced substance is a nonreactive process,
set the generation = 0 and consumption = 0.
b) If the balanced equation is total mass, set
generation = 0 and consumption = 0.
c) If the system is at steady state, set the
accumulation = 0.

36
 Two types of balances may be written:
a) Differential balances
 Balance that happen in a system at an instant of time.
 Each term of the balance equation is a rate and has unit of the
balanced quantity unit divided by a time unit (kg/hr,
people/hr…)
 This type of balance normally applied to a continuous
process.
Inputs flow rates = Output flow rates

b) Integral balances
 Balances that describe what happens between two instant of
time.
 Each term of balance equation is an amount (people, g O2…)
 This type of balance normally applied to a batch process, with
the two instants of time being the moment after the input takes
place and the moment before the product withdrawn.
Amount of inputs = Amount outputs
37
 EXAMPLE

250 kg solution containing 20% salt is

to be evaporated to yield a solution 50%
salt. Calculate the amount of water
evaporated and amount of the final
solution.

38
 W kg water

250 kg diluted salt

solution P kg final solution
EVAPORATION
0.20 salt 0.50 salt
0.80 water 0.50 water
1 1

39
  Known basis = 250 kg solution
 Number of unknowns = 2 (W,P)
 Number of independent equations = 2 (salt and water)
 Thus unknowns have unique solution and can be solved.

Total mass balance :

mass diluted salt solution = mass water removed (W) + Mass final solution (P)
250 kg = W + P
W = 250kg - P

Salt mass balance:

mass salt in diluted salt solution= mass salt in water removed + mass salt in final solution

0.2(250 kg ) = 0W + 0.5P
P = 50kg /0.5
P= 100 kg

W = 250 kg- P
W = 250kg -100kg
40 = 150 kg
 BALANCES ON
MULTIPLE UNIT PROCESS

 It is a very rare that raw materials undergo only a single

process.
 Often these materials have to go through a series of processes
before final products are obtained.
 This series of processes is called a multiple unit process.
 Eg: a flowchart with simple multiple unit process.

Raw materials Product

in Process 1 Process 2 Process 3 out
in in in
unit 1 unit 2 unit 3

41
 Flowchart of a two unit process

Feed 2

B C
D E
UNIT UNIT Product 4

Feed 1
1 2

Product 1 Product 2 Product 3

Where:
A =Overall boundary
B = Unit 1 boundary
C = Unit 2 boundary
D = Mixing point boundary
E = Mixing point boundary
42
 Below is a labeled flowchart for a steady state of two unit process.
Determine the values of all unknowns.

475 g/s
200 g/s x A
1C y B
(1-x-y) C

800 g/s UNIT M g/s N g/s UNIT

0.2 A 1 z A m A 2
0.8 B (1-z) B n B
(1-m-n) C

P g/s

100 g/s 0.012 A

0.588 B
1A
0.400 C
43
 MATERIAL BALANCE FOR OVERALL BOUNDARY

200 g/s
1C 475 g/s
x A
y B
800 g/s (1-x-y) C
0.2 A OVERALL
0.8 B
BOUNDARY

P g/s
0.012 A
100 g/s 0.588 B
0.400 C
1A

44
 Total material balance:
800 + 200 = 100 + 475 + P
575 + P = 1000
P = 425 g/s

A balance:
0.2(800) = 1(100) + x(475) + 0.012(425)
100 + 475x + 5.1 = 160
475x + 105.1 = 160
x = 0.116

B balance:
0.8(800) = y(475) + 0.588(425)
475y + 249.9 = 640
y = 0.821

45
 MATERIAL BALANCE AT UNIT 1

800 g/s UNIT M g/s

0.2 A 1 z A
0.8 B (1-z) B

100 g/s
1A

Total material balance:

800 = 100 + M
M = 700 g/s

A balance:
0.2(800) = z(700) + 1(100)
700z + 100 = 160
z = 0.086

46
 MATERIAL BALANCE AT MIXING POINT

200 g/s
1C

700 g/s Mixing N g/s

0.086 A
point m A
0.914 B n B
(1-m-n) C

Total material balance:

700 + 200 = N
N = 900 g/s

A balance:
0.086(700) = m(900)
m = 0.067

B balance:
0.914(700) = n(900)
47 n = 0.711
 EXERCISE

Below is a labeled flowchart for a steady state of two unit process.

Determine the values of all unknowns.

40 kg/h
0.9 A 30 kg/h
0.1 B
0.6 A
0.4 B

100 kg/h UNIT P kg/h N kg/h UNIT M kg/h

0.5 A 1 x A y A 2 z A
0.5 B (1-x) B (1-y) B (1-z) B

30 kg/h
0.3 A
0.7 B
48
 RECYCLE AND BYPASS

RECYCLE STREAM

 Part of an output process stream that has been

split and returned to mix with an input process
stream.
 Reason for using recycle in chemical process:
a) To recover and reuse unconsumed reactants
that comes out in the output streams.
b) To recover and reuse catalyst.
c) To dilute a process stream.
d) To control a process variable.
e) To circulate a working fluid.

49
 Mixing point Splitting point

Fresh Final
feed Feed PROCESS Output product
UNIT

Recycle stream

Mixing point Splitting point

Fresh Final
feed Feed PROCESS PROCESS product
UNIT 1 UNIT 2

Recycle stream

50
51
 BYPASS STREAM

 In a chemical process a stream that skips one or

more stages and joins another stream of a stage
further down the process is called a Bypass
Stream
 Part of a feed to a process unit that has been
diverted around the unit and then combined with
an output stream.
 Why are there Bypass Streams in a chemical plant?
– To dilute a process stream especially when a stream needs to be filtrated
and the concentration of the slurry (suspended solids) is too high (the filter
will clog up)

– To control a process variable. If a reaction releases a large amount of

heat it makes the reactor hard and expensive to control thus the
concentration of the fed stream can the lowered by diluting the stream with a
bypass stream that acts as capacitance for the heat transfer. Thus lowering
52 the temperature of the stream.
 Some of the important applications of bypass stream
are as follow:

 1. Pumping of liquid from a storage tank by a more

efficient pump of high horsepower to a small
process unit at desired lower flow rate.

 2. Separation of mixtures by a more efficient

distillation column, so that a bypass stream is used
to control the composition of the product at the
desired value.

53
 Splitting point Mixing point

Fresh Final
feed Feed PROCESS Output product
UNIT

Bypass stream

Splitting point Mixing point

Fresh Final
feed Feed PROCESS PROCESS product
UNIT 1 UNIT 2

Bypass stream
54
55
  Recycle and bypass calculations are approached in
exactly the same manner, which are:
a) The flowchart is drawn and labeled.
b) Overall balances, balances around the process
unit or the stream of mixing point and splitting
point are used to determine unknown variables.
c) Perform an DOF analysis before going further
with calculation.

56
 You can write material balances for several different
systems, namely:
a) About the entire process.
 These balances contain information of fresh feed,
product and final product only.
 These balances contain no information about the
recycle stream.
b) About the mixing point.
 These balances contain information of fresh feed and
recycle/ bypass stream.
c) About the splitting point.
 These balances contain information about the
recycle/bypass stream
d) About the basic process itself.
 These balances contain information of feed and output
only.
 These balance do not contain any information of
recycle stream.
57
 EXAMPLE

In a country where its fresh water source is limited,

desalinization is widely employed to treat salt water to
be produced to potable (drinkable) water. Given is flow
chart of a reverse osmosis process sea water
desalinization. Calculate:

a) The flow rate of brine waste (C), brine recycle (B)

and the potable water (D).
b) The flow rate of stream G and E.
c) Ratio of brine cycle (B) compared to brine leaving
the cell (E).

58
 Below is flow chart of a reverse osmosis process sea water
desalinization.

Brine recycle, B kg/h

3000 kg/h
sea water G kg/h REVERSE E kg/h Brine waste, C kg/h
4.5 wt % salt 5.0 wt % salt OSMOSIS 5.3 wt % salt

Potable water D kg/h

0.048 wt % salt

59
 SOLUTION:

Brine recycle, B kg/h

3000 kg/h
sea water G kg/h REVERSE E kg/h Brine waste, C kg/h
0.045 salt 0.05 salt OSMOSIS 0.053 salt

Potable water D kg/h

4.8 x 10-4 salt

60
 MATERIAL BALANCE AT OVERALL BOUNDARY

3000 kg/h OVERALL C kg/h

0.045 salt BOUNDARY 0.053 salt

D kg/h
4.8 x 10-4 salt

Total material balance:

3000 = C + D
D = 3000 - C (1)

Salt mass balance:

0.045(3000) = 0.053(C) + 4.8 x 10-4(D)

0.053C + 4.8 x 10-4D = 135 (2)
61
 Substitute (1) into (2):

0.053C+ 4.8 x 10-4(3000 – C) = 135

0.053C + 1.44 - 4.8 x 10-4C = 135
1.44 + 0.0525C = 135
0.0525C = 133.56
C = 2544 kg/h
From (1):

D = 3000 - C
= 3000 – 2544
= 456 kg/h

62
 MATERIAL BALANCE AT MIXING POINT

B kg/h
0.053 salt

3000 kg/h MIXING G kg/h

0.045 salt POINT 0.05 salt

Total material balance:

3000 + B = G (1)

Salt material balance:

0.045(3000) + 0.053(B) = 0.05(G)
135 + 0.053B = 0.05G (2)

63
 Substitute (1) into (2):

135 + 0.053B = 0.05(3000 + B)

135 + 0.053B = 150 + 0.05B
0.003B = 15
B = 5000 kg/h

From (1):

3000 + B = G
G = 3000 + 5000
= 8000 kg/h

64
 MATERIAL BALANCE AT SPLITTING POINT

5000 kg/h

E kg/h SPLITTING 2544 kg/h

POINT 0.053 salt

Total material balance:

E = 5000 + 2544
= 7544 kg/h

65
 Ratio of brine cycle (B) compared to brine leaving
the cell (E).

B = 5000
E 7544
= 0.66

66
 EXERCISE

To save energy, stack gas from a furnace is used to dry rice as

shown in the following flow diagram. What is a mount of recycle
gas per 100 Ib of P if 5.20 wt% of water in the gas stream entering
the dryer.

R Ib recycle gas W Ib wet gas

S Ib stack gas 9.31 wt% water
Q Ib
4.73 wt% water gas feed
95.27 wt% dry gas
5.20 wt% water

DRYER
F Ib rice feed P Ib dried rice
25 wt% water 5 wt% water
75 wt% rice 95 wt% rice

67
 SOLUTION

Given basis = 100 Ib dried rice (P)

R Ib recycle gas W Ib wet gas

S Ib stack gas 0.0931 water
Q Ib 0.9069 dry gas
0.0473 water gas feed
0.9527 dry gas
0.052 water

DRYER
F Ib rice feed P Ib dried rice
0.25 water 0.05 water
0.75 rice 0.95 rice

68
 MATERIAL BALANCE AT OVERALL BOUNDARY

W Ib wet gas
0.0931 water
0.9069 dry gas
S Ib stack gas
0.0473 water OVERALL 100 Ib dried rice
0.9527 dry gas BOUNDARY 0.05 water
0.95 rice

F Ib rice feed
0.25 water
0.75 rice

69
 Total material balance:
S + F = W + 100 (1)

Rice balance:
0.75(F) = 0.95(100)
0.75F = 95
F = 126.67 Ib (2)

Dry gas balance:

0.9527(S) = 0.9069(W)
0.9527S = 0.9069W
S = 0.9519W (3)

70
 Substitute (2) and (3) into (1):

0.9519W + 126.67 = W + 100

-0.0481W = -26.67
W = 554.47 Ib

S = 0.9519W
= 0.9519(554.47)
= 527.8 Ib

71
 MATERIAL BALANCE AT MIXING POINT

R Ib
0.0931 water
0.9069 dry gas

527.8 Ib MIXING Q Ib
0.0473 water POINT 0.052 water
0.9527 dry gas 0.948 dry gas

72
 Total material balance:
527.8 + R = Q (1)

Water balance:
0.0473(527.8) + 0.0931(R) = 0.052(Q)
24.964 + 0.0931R = 0.052Q
480.077 + 1.79R = Q (2)

(1) – (2):
47.723 - 0.79R = 0
0.79R = 47.723
R = 60.41 Ib
From (1):
527.8 + 60.41 = Q
Q = 588.2 Ib

73
 TEST YOURSELF

A distillation column separates 10,000 kg/hr of a

mixture containing equal mass of benzene and toluene.
The product D recovered from the condenser at the top
of the column contains 95% benzene, and the bottom
W from the column contains 96% toluene. The vapor V
entering the condenser from the top of the column is
8000 kg/hr. A portion of the product from the
condenser is returned to the column as reflux R, and
the rest is withdrawn as the final product D. Assume
that V, R, and D are identical in composition since V is
condensed completely. Find the ratio of the amount
refluxed R to the product withdrawn D.

74
75
 At the end of chapter, student should be able to:
a) Perform a DOF analysis for given problems.
b) Solve problem for single unit process by selecting
right material balance equation.
c) Solve problem for multiple unit process by
selecting the right material balance equation and
right boundaries.
d) Explain, draw the flow chart of recycle and bypass
process.
e) Solve problem for recycle and bypass process by
selecting the right material balance equation and
right boundaries.

76
MATERIAL BALANCES WITH
CHEMICAL REACTION
CHEMICAL REACTION
STOICHIOMETRY
 STOICHIOMETRY

 Stoichiometry is the theory of the proportion in

which chemical species combine with one other.
 The word stoichiometry derives from two Greek
words, which stoicheion (meaning element) and
metron (meaning measure).
 Stoichiometry provides a quantitative means of
relating the amount of products produced by
chemical reactions to the amount of reactants.
 STOICHIOMETRIC EQUATION

 Stoichiometry equation of a chemical reaction is a statement of

relative number of molecules or moles of reactants and
products that participate in the reaction.
 Eg:
2SO2 + O2 2SO3
 From equation, indicates that for every two molecules of SO2
and one molecule of O2 react to produce two molecules of SO3.
 The numbers that precede the formulas for each species are
the stoichiometric coefficients of the reaction components.
 A valid equation must be balanced, that is, the number of
atoms of each atomic species must be the same on both sides
of the equation.
 STOICHIOMETRIC RATIO

 The ratio at which reactant and product are related by

its balanced chemical equation is called stoichiometric
ratio.
 This ratio can be used as conversion factor to calculate
the amount of a particular reactant or product that was
consumed or produced, given a quantity of another
reactant of product that participated in the reaction.
 For the equation:
2SO2 + O2 2SO3
 You can write the stoichiometric ratios:
2 mol SO3 generated , 2 Ibmol SO2 generated ,
1 mol O2 consumed 1 Ibmol O2 consumed
so on…
 EXAMPLE

Limestone is a type of rock that contains carbonate.

Upon heating, limestone releases CO2 gas leaving
behind solid lime. A limestone analysis yields:
CaCO3 80%
MgCO3 19%
Insoluble/ inert 1%

a) How many kg of lime that can be made per metric

ton on limestone?
b) How many pounds of limestone are needed to
make 0.5 metric ton of oxides?
c) How many liters of CO2 that can be produced at
STP per pound of limestone?
 SOLUTION

 Read the problem carefully.

 The carbonates are decomposed to oxides.
 You should recognized that lime is oxides of Ca
and Mg, will also include other inert compounds
present in the limestone that remain after the
CO2 has been driven off.
The reactions are:

CaCO3 CaO + CO2

MgCO3 MgO + CO2

Basis: 1 metric ton limestone

Mass of lime = total mass of oxides + mass of inert
a) How many kg of lime that can be metric per metric ton on limestone?

Basis: 1 metric ton limestone

From stoichiometric ratio:
Mol CaO = 1metric ton mol CaO
Mol CaCO3 1metric ton mol CaCO3

Mol CaO = 1metric ton mol CaO x mol CaCO3

1 metric ton mol CaCO3
= 1metric ton mol CaO x 0.8 metric ton x 1 metric ton mol CaCO3
1 metric ton mol CaCO3 100 metric ton CaCO3
= 8 x 10-3 metric ton mol CaO

Mass CaO = mol x MW

= 8 x 10-3 metric ton mol CaO x 56 metric ton CaO
metric ton mol CaO
= 0.448 metric ton
From stoichiometric ratio:
Mol MgO = 1 metric ton mol MgO
Mol MgCO3 1 metric ton mol MgCO3

Mol MgO = 1 metric ton mol MgO x mol MgCO3

1 metric ton mol MgCO3
= 1metric ton mol MgO x 0.19 metric ton x 1 metric ton mol MgCO3
1 metric ton mol MgCO3 84 metric ton MgCO3
= 2.26 x 10-3 metric ton mol MgO

Mass MgO = mol x MW

= 2.26 x 10-3 metric ton mol MgO x 40 metric ton MgO
metric ton mol MgO
= 0.0904 metric ton
Mass of inert = 0.01 metric ton
Mass of CaO = 0.448 metric ton
Mass of MgO = 0.0904 metric ton

So,
Mass of lime = total mass of oxides + mass of in
= 0.01 + 0.048 + 0.0904
= 0.5484 metric ton lime

Kg of lime per metric ton limestones:

= 0.5484 metric ton lime x 1 kg
1 metric ton limestone 0.001 metric ton lime
= 548.4 kg lime per metric ton limestone
b) How many pounds of limestone are needed to make 0.5 metric
ton of oxides?
c) How many liters of CO2 that can be produced at STP per
pound of limestone?

Basis = 1 Ibm limestone

From stoichiometric ratio:

Mol CO2 = 1
Mol CaO 1
Mol CO2 = mol CaO
= 8 x 10-3 Ibmol

Mol CO2 = 1
Mol MgO 1
Mol CO2 = mol MgO
= 2.26 x 10-3 Ibmol

So, moles CO2 = 8 x 10-3 Ibmol + 2.26 x 10-3 Ibmol

= 0.0103 Ibmol x 453.593 gmol
1 Ibmol
= 4.67 gmol
Standard Temperature Pressure, STP

Standard condition for gases:

System T P V n

SI 273 K 1 atm 0.022415 m3 1 mol

CGS 273 K 1 atm 22.415 L 1 mol

AE 492ºR 1 atm 359.05 ft3 1 Ib mol

Molarity of CO2 = number of moles CO2
(mol/dm3) volume of CO2
Volume of CO2 at STP = number of moles CO2
molarity of CO2
= 4.67 gmol x 22.4 dm3
1 gmol
= 104.608 dm3

Liter of CO2 per Ib of limestone:

= 104.608 dm3 CO2
1 Ib limestone
= 104.608 dm3 x 1L
1 Ib limestone 1dm3
= 104.608 L per Ib of limestone
 EXERCISE

A commercial HCI contains 92% HCI and 8% water. If the

limestone with the following mass composition is
treated with the commercial acid, calculate:

CaCO3 60%
MgCO3 38%
Insoluble/ inert 2%

a) How many kg CO2 produced at STP per ton

limestone treated?
b) How many kg of commercial acid required ton of
limestone treated?
How many kg CO2 produced at STP per ton limestone
treated?

Basis = 1 ton limestone

Mass of CaCO3 = 0.60 ton

Mass of MgSO3 = 0.38 ton

The reaction:
CaCO3 + 2HCI CaCI2 + H2O + CO2
MgCO3 + 2HCI MgCI2 + H2O + CO2
From stoichiometric ratio:
Mol CO2 = 1 ton mol CO2
Mol CaCO3 1 ton mol CaCO3

Mol CO2 = 1 ton mol CO2 x mol CaCO3

1 ton mol CaCO3
= 1 ton mol CO2 x 0.6 ton CO2 x 1 ton mol CaCO3
1 ton mol CaCO3 100 ton CaCO3
= 6 x 10-3 ton mol CO2

Mass CO2 = mol x MW

= 6 x 10-3 ton mol CO2 x 44 ton CO2
1 ton mol CO2
= 0.264 ton CO2
From stoichiometric ratio:
Mol CO2 = 1 ton mol CO2
Mol MgCO3 1 ton mol MgCO3

Mol CO2 = 1 ton mol CO2 x mol MgCO3

1 ton mol MgCO3
= 1 ton mol CO2 x 0.38 ton x 1 ton mol MgCO3
1 ton mol MgCO3 84 metric ton MgCO3
= 4.52 x 10-3 mol CO2

Mass CO2 = mol x MW

= 4.52 x 10-3 ton mol CO2 x 44 ton CO2
ton mol CO2
= 0.199 ton CO2
Mass CO2 = 0.264 ton + 0.199 ton
= 0.463 ton CO2

So,
kg of CO2 produced at STP per ton limestone:
= 0.463 ton CO2 x 0.453593 kg
1 ton limestone 5 x 10-4 ton CO2
= 420.03 kg CO2 per ton limestone
b) How many kg of commercial acid required ton of
limestone treated?

Basis = 1 ton limestone

From stoichiometric factor:

Mol HCI = 2 ton mol HCI
Mol CO2 1 ton mol CO2
Mol HCI = 2 ton mol HCI x mol CO2
1 ton mol CO2
= 2 ton mol HCI x (6 x 10-3 ton mol CO2)
1 ton mol CO2
= 0.012 ton mol HCI

Mass HCI = 0.012 ton mol HCI x 36.5 ton HCI

ton mol HCI
= 0.438 ton HCI
From stoichiometric factor:

Mol HCI = 2 ton mol HCI

Mol CO2 1 ton mol CO2
Mol HCI = 2 ton mol HCI x mol CO2
1 ton mol CO2
= 2 ton mol HCI x (4.52 x 10-3 ton mol CO2)
1 ton mol CO2
= 9.04 x 10-3 ton mol HCI

Mass HCI = 9.04x 10-3 ton mol HCI x 36.5 ton HCI
1 ton mol HCI
= 0.33 ton HCI
Total mass CO2 = 0.33 ton + 0.438 ton
= 0.768 ton HCI
So,
kg of HCI per ton limestone:
= 0.768 ton HCI x 0.453593 kg HCI
1 ton limestone 5 x10-4 ton HCI
= 696.72 kg HCI
1 ton limestone

kg of commercial acid per limestone:

= 696.72 kg HCI x 1 kg commercial acid
1 ton limestone 0.92 kg HCI
= 757.3 kg commercial acid per ton limestone
 LIMITING AND EXCESS REACTANT

 Limiting reactant is the species in a

chemical reaction that would theoretically
run out first (would be completely
consumed) if the reaction were to proceed
to completion according to chemical
equation.
 The other reactant is called excess
reactant.
 HOW TO DETERMINE
LIMITING AND EXCESS REACTANT?

 Limiting reactant can be determined by calculate the

maximum extent of reaction, §max for each reactant based
on the complete reaction of the reactant.
 The reactant with the smallest maximum extent of reaction
is the limiting reactant.
 The other reactant will be the excess reactant.

§max = ni - nio
vi
Where:
§max = extent of the system
ni = moles of species in the system after the reaction occurs
nio = moles of species in the system when reaction starts
vi = Coefficient of species
 EXAMPLE

C7H16 + 11O2 7CO2 + 8H2O

If the feed contains 1 gmol C7H16 and 12.2 gmol 11O2,
determine the limiting reactant and excess reactant.

SOLUTION:

§max C7H16 = 1.0 gmol = 1.0 gmol

1
§max O2 = 12.2 gmol = 1.11 gmol
11

Thus the limiting reactant is C7H16 and excess

reactant is O2.
 PERCENT CONVERSION

 Conversion is the fraction of the feed/reactant that

is converted to products.
 Conversion is related to the degree of completion
of a reaction namely the percentage or fraction of
the limiting reactant.

% conversion = moles of reactant reacted x 100

moles of reactant feed
 PERCENT EXCESS REACTANT

 An excess reactant is a reactant that is present in

amount more than its stoichiometric amount.
 Percent excess reactant can be calculated as:

moles of - moles of
reactant fed theoretical reactant
% excess reactant =
moles of theoretical reactant

where;
Theoretical reactant = number of moles of reactant
required to react with the
limiting reactant
EXAMPLE

Ethane gas, C2H6 burns in oxygen to produce

CO2 and water. 50 g of C2H6 is burned in
0.24 Ibm O2 and at the end of the reaction, 40 g
of water is formed. Determine:
a) The limiting reactant and the excess
reactant.
b) The percent excess reactant.
c) The percent conversion.
SOLUTION

The balanced equation is:

C2H6 + 7/2O2 2CO2 + 3H2O

Mole C2H6 = 50 g
30 g/gmol
= 1.67 gmol

Mole O2 = 0.24 Ib
32 Ib/Ibmol
= 7.5 x 10-3 Ibmol
= 7.5 x 10-3 Ibmol x 453.593 gmol
1 Ibmol
= 3.40 gmol
 C2H6 + 7/2O2 2CO2 + 3H2O

§max C2H6 = 1.67 gmol

1
= 1.67 gmol

§max O2 = 3.40 gmol

3.5
= 0.97 gmol

Thus,
The limiting reactant is O2
The excess reactant is C2H6
b) The percent excess reactant

Limiting reactant = O2, Excess reactant = C2H6

Moles of C2H6 required to react completely with LR, O2:

From stoichiometric ratio:
Mole C2H6 = 1
Mole O2 3.5
mole C2H6 = 1 x mol O2
3.5
= 1 x 3.40 gmol
3.5
= 0.971 gmol

Percent excess reactant = 1.67 - 0.971 x 100

0.971
= 71.99 %
c) The percent conversion O2.

Moles of O2 actually reacted:

From stoichiometric ratio:
mole O2 = 3.5
mole H2O 3
mole O2 = 3.5 x mole H2O
3
= 3.5 x 40 g
3 18 g/gmol
= 2.59 gmol

Percent conversion = 2.59 gmol x 100

3.40 gmol
= 76.18 %
EXERCISE

Ethane gas, C2H6 burns in oxygen to produce

CO2 and water. If 65 g of C2H6 is burned in
122 g O2, determine:
a) The limiting reactant and the excess
reactant.
b) The percent excess reactant.
c) How much grams of C2H6 burned per liter
of CO2 produced at STP.
SOLUTION:

The balanced equation is:

C2H6 + 7/2O2 2CO2 + 3H2O

Mole C2H6 = 65 g
30 g/gmol
= 2.17 gmol

Mole O2 = 122 g
32 g/gmol
= 3.81 gmol
a) The limiting reactant and the excess reactant.
The balanced equation is:
C2H6 + 7/2O2 2CO2 + 3H2O

§max C2H6 = 2.17 gmol

1
= 2.17 gmol

§max O2 = 3.81 gmol

3.5
= 1.09 gmol
Thus,
The limiting reactant is O2
The excess reactant is C2H6
b) The percent excess reactant

Limiting reactant = O2, Excess reactant = C2H6

Moles of C2H6 required to react completely with LR, O2:

From stoichiometric ratio:
Mole C2H6 = 1
Mole O2 3.5
mole C2H6 = 1 x mol O2
3.5
= 1 x 3.81 gmol
3.5
= 1.09 gmol

Percent excess reactant = 2.17 - 1.09

x 100
1.09
= 96.33 %
b) The percent excess reactant

Limiting reactant C2H6=, Excess reactant = O2

Moles of O2 required to react completely with LR, C2H6 :

From stoichiometric ratio:
Mole O2 = 3.5
Mole C2H6 1
mole O2 = 3.5 x mol C2H6
1
= 3.5 x 2.17 gmol
1
= 7.6 gmol

Percent excess reactant = 1.67 - 0.971

0.971
= 71.99 %
c) How much grams of C2H6 burned per liter of CO2
produced at STP.

Basis = 1 liter CO2

Mole C2H6 = 1
Mole CO2 2
Mole C2H6 = 1 x mole CO2
2

Molarity CO2 = number of mole CO2

volume CO2
Mole CO2 = molarity x volume
= mol x volume
dm3
= 1 gmol x 1 liter
22.4 L
= 0.047 gmol
So,
Mole C2H6 = 1 x mole CO2
2
= 1 x 0.047 gmol
2
= 0.024 gmol

So,
Mass C2H6 = mole C2H6 x MW
= 0.024 gmol x 30 g
gmol
= 0.72 g C2H6 per liter CO2
BALANCES ON REACTIVE
PROCESSES
General material balance:

Input + Generation – Output – Consumption = Accumulation

Material balance for reactive process and at steady

state:
 Accumulation = 0, generation ≠ 0, consumption ≠ 0
since product are generated by reaction while
reactants are consumed.

Input + Generation – Output – Consumption = 0

or
Input + Generation – Consumption = Output
or
Input + Generation = Output + Consumption
 A number of different balances could be written on
reactive process, including:
a) Total mass balances
b) Molecular species balances
♦ Must contain generation and/or consumption
terms.
a) Atomic species balances ( C, H, O, etc).

 Each approach leads to same results, but any one of

them may be more convenient for a given
calculation, especially using total mass balances
and atomic species balances.
 Material balances equation for molecular species
balances is:
Input + Generation = Output + Consumption

 Material balances equation for molecular species

balances is:
Input = Output

Since atomic species can neither be generated nor

consumed in chemical reaction.
EXAMPLE

100 kmol/min of C2H6 is fed to the reactor. The

molar flow rate of H2 in the product stream is
40 kmol/min. The chemical reaction for
dehydrogenation of ethane.
C2H6 C2H4 + H2
Find the value of x and y.

REACTOR
100 kmol/min C2H6 40 kmol/min H2
x kmol/minC2H6
y kmol/min C2H4
 THE END

122