Material Balances

{Input} + {Genn} - {Consumption} – {Output} = {Accumulation}

Sungging Pintowantoro
Department of Materials and Metallurgical Engineering,
Faculty of Industrial Technology (FTI),
Sepuluh Nopember Institute of Technology Surabaya (ITS),
Kampus ITS, Keputih Sukolilo, Surabaya 60111,
Telp/Fax : 031-5997026

Department of Materials and Metallurgical Engineering, FTI-ITS (1)

 Material Balances
For all except nuclear processes, atoms can neither be created nor destroyed.
This principle is a simple statement of the law of conservation of mass, and is the
fundamental principle for making material balances. In the design stage of a
process, an exact material balance can be made because certain assumptions are
made about the extent of reactions, the loss of minor elements (which are often
ignored in a preliminary design), and the accuracy of measurements on feed
rates.

General mass balance equation

{Input} + {Genn} - {Consumption} – {Output} = {Accumulation}
Notes: 1. generation and consumption terms refer only to generation of
products and consumption of reactants as a result of chemical reaction. If
there is no chemical reaction then these terms are zero.
2. Apply to a system
3. Apply to total mass and component mass

Department of Materials and Metallurgical Engineering, FTI-ITS (2)

 Material Balances
Schematic diagram of a system showing material and energy transfers,
and material accumulation. Each lettered arrow indicates a stream.

Department of Materials and Metallurgical Engineering, FTI-ITS (3)

 Material Balances
Examples of some of the more complex stream materials found in materials
processes are:

• A bulk raw material such as an ore. This is usually a very heterogeneous

material, and likely consists of several minerals; it may be wet, and has air
amongst the particles. It often enters the system through an open conveyor.
• A sludge or dust from some other process or from another part of the
existing process. This is likely to be a stream of variable composition, and
be enhanced in elements that enter the some other part of the process in
very dilute form.
• A dusty offgas containing hazardous or restricted materials. The
composition and flowrate of such a stream may require particular attention
if the amounts of certain substances are controlled by regulation.
• A gas containing combustible substances, which if not carefully confined,
could attain explosive compositions.
• A waste material of no economic value that may be disposed of by
stockpiling, so long as the level of toxic contaminants is below certain limits.

Department of Materials and Metallurgical Engineering, FTI-ITS (4)

 Material Balances
Process Classifications
Processes can be classified as batchy semi-batch, continuous, steady-state or
transient. Before working on the material balance, you should classify the process
according to these definitions.
• Batch processes. Raw materials are added to a vessel at the beginning of the
process, and kept there until the desired final state is reached. An example is the
metallothermic Chapter 4 Fundamentals of Material Balances in Non-Reacting
Systems reduction of uranium fluoride by calcium. Another example is the
production of intermetallic compounds by direct-reaction synthesis.
Semi-batch processes. Some reactants are put into a vessel, and then other
substances are added steadily until the desired final state is reached. This is a very
common type of process in the extraction industry. One example is the passage of
a drying gas over a batch of wet sludge. Semi-batch processes are used in the
production of many metals, and the sintering of ceramic parts.
Continuous process. The in- and outstream material flows continuously
throughout the duration of the process. Continuous processes are common in the
chemical industry, such as in the refining of petroleum and the production of
industrial chemicals. Examples from the materials industries are the production of
Portland cement in a rotary kiln, the
electroplating of zinc on steel, and the production of glass.

Department of Materials and Metallurgical Engineering, FTI-ITS (5)

 Material Balances
Flowsheets
A written description of a process can contain all of the essential information needed
for making a material balance. However, a textual description is not a good way to
present information that contains a lot of numerical data and technical information. A
better way is to present the same information diagrammatically, showing points of
entry and removal, the relative position of equipment, and the path of material from
one piece of equipment to another. Such a diagram is called a flowsheet, and
consists of boxes or other symbols to represent process devices, and lines with
arrows to represent streams.

Typical indicative flowsheet for the production of gold from ore.

Department of Materials and Metallurgical Engineering, FTI-ITS (6)

 Material Balances
Flowsheet for fluid bed roasting of zinc concentrate using shapes to describe the
various devices. Dashed lines indicate the flow of gas, and solid lines the flow of
solids. Calcine is the oxide product of roasting. A waste-heat boiler (designated W-
H) recovers heat from the gas to generate steam. The ESP is an electrostatic
precipitator for final dust removal.

Department of Materials and Metallurgical Engineering, FTI-ITS (7)

 Material Balances
Simplified flowsheet for
the AISI-DOE process
for direct smelting of
iron ore. Post-
combustion refers to
oxidation of CO and H2
in the upper half of the
smelting vessel. Heat
transfer efficiency refers
to the fraction of post-
combustion heat that is
transferred to the
molten bath. 80 % of
the water vapor from
the top of the shaft
furnace condenses in
the scrubber.

Department of Materials and Metallurgical Engineering, FTI-ITS (8)

Material Balances
SYSTEMS
 Systems
 OPEN or CLOSED
 Any arbitrary portion of or a whole process that you
want to consider for analysis
 Reactor, the cell, mitochondria, human body, section of a
pipe
 Closed System
 Material neither enters nor leaves the system
 Changes can take place inside the system
 Open System
 Material can enter through the boundaries

Department of Materials and Metallurgical Engineering, FTI-ITS (9)

 Material Balances
STEADY-STATE
 Steady-State
 Nothing is changing with time
 @ steady-state accumulation = 0

500 kg 100 kg/min

100 kg/min
H2O H2O H2O

Rate of addition = Rate of removal

 Unsteady-State (transient system)

 {Input} ≠ {Output}

CHBI 201 10
Department of Materials and Metallurgical Engineering, FTI-ITS (10)
 Material Balances
PROCESSES
 Batch Process
 Feed is fed at the beginning of the process

 Continuous Process
 The input and outputs flow continuously throughout the
duration of proces

 Semibatch Process
 Any process neither batch nor continuous

CHBI 201 11
Department of Materials and Metallurgical Engineering, FTI-ITS (11)
 Material Balances
Balances on Continuous Steady-state Processes
 Input + Generation = Output + Consumption
 If the balance is on a nonreactive species, the generation and
consumption will be 0.
 Thus, Input = Output
 Example
Input of 1000 kg/h of benzene+toluene containing 50% B by mass is separated
by distillation column into two fractions.
B: the mass flow rate of top stream=450 kg/h
T: the mass flow rate of bottom stream=475 kg/h
m1 kg Toluene/h
450 kg Benzene/h
1000 kg /h
Benzene + Toluene Distillation
%50 Benzene by
mass 475 kg Toluene/h
CHBI 201 M2 kg Benzene/h 12
Department of Materials and Metallurgical Engineering, FTI-ITS (12)
Material Balances
Balances on Continuous Steady-state Processes
 Solution of the example Input = Output
 Benzene balance

1000 kg/h · 0.5 = 450 kg/h + m2

m2 = 50 kg/h Benzene

 Toluene balance

1000 kg/h · 0.5 = 475 kg/h + m1

m1 = 25 kg/h Toluene

Department of Materials and Metallurgical Engineering, FTI-ITS (13)

 Material Balances
BALANCES ON BATCH PROCESSES
 Initial Input + Generation = Final Output + Consumption
 Objective: generate as many independent equations as the
number of unknowns in the problem

D F=B+D
F.xF = D.xD + B.xB
F
F.yF = D.yD + B.xB
(W+A)
x: mole fraction of W
B y: mole fraction of A

CHBI 201 14
Department of Materials and Metallurgical Engineering, FTI-ITS (14)
 Material Balances
EXAMPLE (Batch Process)

 Centrifuges are used to seperate particles in the range of 0.1 to 100 µm

in diameter from a liquid using centrifugal force. Yeast cells are
recovered from a broth ( a mix with cells) using tubular centrifuge.
Determine the amount of the cell-free discharge per hour if 1000 L/hr is
fed to the centrifuge, the feed contains 500 mg cells/L, and the product
stream contains 50 wt% cells. Assume that the feed has a density of 1
g/cm3.

Feed (broth) 1000 L/hr Concantrated cells P(g/hr)

Centrifuge
500 mg cells/L feed 50 % by weight cells

( d= 1 g/cm3)
Cell-free discahrge D(g/hr)

Department of Materials and Metallurgical Engineering, FTI-ITS (15)

 Material Balances
EXAMPLE (Batch Process)
 Centrifuges are used to seperate particles in the range of 0.1 to 100 µm in diameter from
a liquid using centrifugal force. Yeast cells are recovered from a broth ( a mix with cells)
using tubular centrifuge. Determine the amount of the cell-free discharge per hour if
1000 L/hr is fed to the centrifuge, the feed contains 500 mg cells/L, and the product
stream contains 50 wt% cells. Assume that the feed has a density of 1 g/cm3.

Feed (broth) 1000 L/hr Concantrated cells P(g/hr)

Centrifuge
500 mg cells/L feed 50 % by weight cells

(d= 1 g/cm3)
Cell-free discharge D(g/hr)
 Cell balance

500 mg cells 1g 0.5 g cells

1000 L feed . .  . P[g/hr]
1 L feed 1000 mg 1gP
P  1000 g/hr
 Fluid balance
Input: (10 – 500) g/h fluid
L 1g 10 cm 3 1dm
3
6 g
6
1000 ( )  10
Output 1: 1000g/h . 0.5 = 500 g/h fluid h cm 3
1dm L h
Output 2: D(g/h) = (106 – 500)g/h – 500 g/h = (106 -103)g/h fluid
CHBI 201 16
Department of Materials and Metallurgical Engineering, FTI-ITS (16)
 FLOW CHARTS
 Boxes and other symbols are used to represent process
units.
 Write the values and units of all known streams
 Assign algebraic symbols to unknown stream variables

100 mol C3H8

Combustion 50 mol C3H8
Condenser
Chamber 750 mol O2
1000 mol O2 3760 mol N2
3760 mol N2 150 mol CO2

200 mol H2O

CHBI 201 17
EXAMPLE (Flow charts)
 Humidification and Oxygenation Process in the Body: An exp. on the growth rate of certain organisms requires an environemnt of
humid air enriched in oxygen. Three input streams are fed into an evaporator to produce an output stream with the desired composition. A:
liquid water, fed at a rate of 20 cm3/min, B: Air, C: Pure oxygen (with a molar flow rate one-fifth of the molar flow rate of stream B)

.
0.2 n1 mol O2/min
.n3 mol/min
0.015 mol H2O/mol
C y mol O2/mol
(0.985 – y ) mol N2/mol
.n1 mol air/min B A

0.21 mol O2/mol 20 cm3 H2O /min

0.79 mol N2/mol
.n2 mol H2O/min
CHBI 201 18
 EXAMPLE
n2 = 20 cm3 H2O/min . 1 g H2O/cm3 . 1 mol/18.02 g
n2 = 1.11 mol H2O/min
 H2O Balance
n2 mol H2O/min = n3 mol/min . 0.015 mol H2O/mol
n3 = 74.1 mol/min
 Total Mole Balance
0.2 n1 + n1 + n2 = n3
n1 = 60.8 mol/min
 N2 Balance
n1 mol/min . 0.79 mol N2/mol = n3 mol/min . (0.985-y) mol N2/mol
y = 0.337 mol O2/mol

CHBI 201 19
 FLOWCHART SCALING

n1
n3
A
n2

Scale factor: 100 100 n1

100 n3
A
100 n2

CHBI 201 20
DEGREE OF FREEDOM ANALYSIS (df)
 ndf = nunknowns – nindep.eqn’s

 If ndf = 0
 Problem can be solved (determined)
 If ndf > 0
 Unknowns > knowns (underspecified)
 If ndf < 0
 overspecified (no solution)

 Material balances,
 Energy balances,
 Process specificaitons,
 Physical props&laws,
 Physical constraints
CHBI 201 21
 EXAMPLE 1
 Example ρH20 is given
Humid air Condenser Dry air
(n4) O2 In the
(n0) O2 condenser,
(n5) N2
(n1) N2 (n6) H2O 95% of H2O
(n2) H2O
in the inlet
air is
(n3) H2O condensed.
225 L/h
7 unknowns (n0 -> n6) 7 equations needed
 3 independent material balance
 n3 = ρ.V
 n0/n1 = 21/79
 n3 = 0.95 n2

 One more equation is needed

 Volume is not conserved!
 Use consistent units (mole, kg)
 Do not make mole balances in reactive processes.

CHBI 201 22
EXAMPLE
 A continuous mixer mixes NaOH with H2O to produce
an aqueous solution of NaOH. Determine the
composition and flow rate of the product, if the flow
rate of NaOH is 1000 kg/hr and the ratio of the flow
rate of H2O to the product solution is 0.9.

Nsp = number of species System boundary

Ns = number of streams
Nu = total number of variables
H2O NaOH
M

Product
CHBI 201 23
EXAMPLE 2 - continue
Streams FEED WATER PRODUCT

Species
NaOH FNaOH WNaOH PNaOH Nu = 3(2+1) = 9
H2O FH2O WH2O PH2O
Total F W P Last row in the tabl

Specifications: ratio of two streams

the % conversion in a reaction
the value of each concentration, flow
rate, T, P, ρ, V, etc.
a variable is not present in a stream,
hence ,it is 0
CHBI 201 24
EXAMPLE
 A cylinder containing CH4, C2H6, and N2 has to be prepared containing
a CH4 to C2H6 mole ratio of 1.5 to 1. Avaliable to prepare the mixture
are
1) a cylinder containing a mixture of 80% N2 and 20% CH4
2) a cylinder containing a mixture of 90% N2 and 10% C2H6
3) a cylinder containing a mixture of pure N2
What is the number of degrees of freedom?

CHBI 201 25
 EXAMPLE 3 - continue

F4
F1
CH4 xCH4
CH4 0.2 F3
N2 xN2
N2 0.8 N2 1
C2H6 xC2H6

F2
C2H6 0.1
N2 0.9

Unknowns: 3 xi and 4 Fi

CHBI 201 26
 EXAMPLE 3 - continue

Equations:
 Material balance (CH4, C2H6, N2)
 One specified ratio xCH4/xC2H6 = 1.5
 One summation of mole fractions x 1 for F
 5 independent equations i 4

Ndf = 7 – 5 = 2

If you pick a basis as F4=1, one other value has to

be specified in order to solve the problem.

CHBI 201 27
 Balances on Multiple-unit Processes
40 kg/hr 30 kg/hr

0.9 kg A/kg 0.6 kg A/kg

0.1 kg B/kg 0.4 kg B/kg

Q1 Q2
1 3
x1 x2 Q3
100 kg/hr 2
x3
0.5 kg A/kg
0.5 kg B/kg 30 kg/hr 4

0.3 kg A/kg
0.7 kg B/kg
CHBI 201 28
Balances on Multiple-unit Processes
Q : mass flow rate
xA : mass fraction of A  You should treat any
1-xA : mass fraction of B junction as a process unit!
Number of unknowns = 6
Number of equations = 2+2+2 = 6
 Therefore, solution exists

100 = 40 + Q1 Q1 = 60 kg/hr
100.(0.5) = 40.(0.9) + 60.(x1) x1 = 0.233
1
30 + Q1 = Q2 Q2 = 90 kg/hr
x2 = 0.256 2

30 + Q3 = Q2 Q3 = 60 kg/hr x3 = 0.083

3
CHBI 201 29
CHBI 201 30
 RECYCLE & BYPASS STREAM
 It is rare that a chemical reaction A  B proceeds to
completion in a reactor. Its efficiency is never 100. Some A
in the product !
 To find a way to send the “A” back to feed you need a
seperation and recycle equipment, this would decrease the
cost of purchasing more A.
 If a fraction of the feed to a process unit is diverted
around the unit and combined with the output stream, this
process is called bypass.

Feed Product Feed Process

rxn Sep. Unit

Recycle Bypass stream

CHBI 201 31
 EXAMPLE (pg 110)

 Feed: Fresh air with 4 mole% H2O(v) is “cooled” and “dehumidified” to a

water content of 1.7 mole% H2O.
Fresh air is combined with a recycle stream of dehumidified air.
The blended stream entering unit contains 2.3 mole% H2O. In the air
conditioner some of the water is removed as liquid.
Take 100 mole of dehumidified air delivered to the room, calculate
moles of feed, water condensed, dehumidified air recycled.

CHBI 201 32
 EXAMPLE - continue

n5 (mol) 0.983 DA, 0.017 W

n1 (mol)
AIR n4 (mol) 100 mol
0.04 W CONDITIONER 0.017 W 0.983 DA
0.96 DA
0.983 DA 0.017 W(v)

n3 mole W(ℓ)
n2 (mol)
0.977 DA
CHBI 201 0.023 W(v) 33
 EXAMPLE - continue
 Overall system: 2 variables (n1, n3)
2 balance equations (two species)
Degree of freedom = 0
 (n1, n3) are determined!!!

 Mixing point: 2 variables (n2, n5)

2 balance equations (two species)
Degree of freedom = 0
 Cooler: 2 variables (n2, n4)
2 balance equations (two species)
Degree of freedom = 0
 Splitting point: 2 variables (n4, n5) Donot use SP in the solution
1 balance equation
Degree of freedom = 1

CHBI 201 34
 EXAMPLE - continue
Overall DA balance:
0.96 n1 = 0.983 (100)  n1 = 102.4 mol fresh feed
Overall mole balance:
n1 = n3 + 100  n3 = 2.4 mol H2O condensed
Mole balance on Mixing point:
n1 + n5 = n2
Water blance on Mixing point:
0.04n1 + 0.017n5 = 0.023n2

n2 = 392.5 mol
n5 = 290 mol recycled

CHBI 201 35
CHEMICAL REACTION STOICHIOMETRY
 If there is a chemical reaction in a process
 More complications

 The stoichiometric ratios of the chemical reactions

 Constraints

 The stoichiometric equation 2SO2 + O2  2SO3

2 molecules of SO2 reacts with 1 molecule of O2 and yields 2
molecules of SO3

 2, 1 and 2 are stoichiometric coefficients of a reaction

CHBI 201 36
 LIMITING & EXCESS REACTANTS

 If the reactants are not in stoichiometric proportion

 one of them will be excess, the other will be limiting

[ (n ) - (n ) ]
Fractional excess of A  A feed A stoich
(n )
A stoich.

moles reacted
Fractional conversion of A 
moles fed

n -n
Extend of reaction ()  i i0
ν
i

CHBI 201 37
 EXAMPLE (pg 120)

 C3H6 + NH3 + 3/2 O2  C3H3N + 3 H2O

Feed: 10 mol % of C3H6, 12 mole % NH3 and 78 mole % air
A fractional converison of limiting reactant = 30%
Taking 100 mol of feed as a basis, determine which reactant
is limiting, and molar amounts of all product gas constituents
for a 30% conversion of the limiting reactant.

100 mol nC3H6

0.1 mol C3H6/mol nNH3

REACTOR nO2
0.12 mol NH3/mol
0.78 mol air/mol nN2

0.21 mol O2/mol air nC3H3N

0.79 mol N2/mol air nH2O

CHBI 201 38
 EXAMPLE – continue
Feed: nC3H6= 10 mole nNH3=12 mole nO2= 78.(0.21) =16.4 mole
nNH3/nC3H6= 12/10 = 1.2  NH3 is excess (stoich. 1)
nO2/nC3H6= 16.4/10 = 1.64  O2 is excess (stoich. 1.5)
(nNH3)stoich.= 10 mole (nO2)stoich.= 15 mole

(% excess)NH3 = (12-10) /10 x 100 = 20% excess NH3

Moles reacted
Moles fed
(% excess)O2 = (16.4-15) /15 x 100 = 9.3% excess O2

(nC3H6)out=0.7 x (nC3H6)0= 7 mole C3H6 (since the fractional conversion of C3H6 is 30%)

Extent of reaction = ζ = 3 mole (since ni = ni0 + i ξ => 7= 10 - 1. ξ)

nNH3 = 12- ζ =9 mole nO2=16.4 – 1.5.(ζ)= 11.9
nC3H3N= ζ = 3 mole nH2O=3.(ζ) = 9 mole
nN2= (nN2)0=61.6 mole

CHBI 201 39
 CHEMICAL EQUILIBRIUM
 If you are given a set of reactive species and reaction
conditions;
a) What will be the final (equilibrium) composition of
the reaction mixture?
b) How long will the system take to reach a specified
state short of equilibrium?
 Chemical equilibrium thermodynamics & Chemical Kinetics

 A reaction can be
 Reversible
 Irreversible

CHBI 201 40
 EXAMPLE
CO (g) + H2O (g) CO2 (g) + H2 (g)
Given @ T=1105 K, K=1
nCO= 1 mol, nH2O= 2mol, initially no CO2 and H2
Calculate the equilibrium composition and the
fractional converison of the limiting reactant.

Equilibrium constant;
yCO2 y H 2
K(T) =
yCO y H 2O

CHBI 201 41
 EXAMPLE – continue
nCO = 1-ζe , nH2O = 2-ζe , nCO2 = ζe , nH2 = ζe

yCO = (1-ζe)/3 yH2O = (2-ζe)/3

yCO2 = ζe /3 yH2 = ζe /3

K(T) = (ζe)2 / (1-ζe) (2-ζe) = 1

ζe = 0.667 mole
yCO = 0.111 yH2O = 0.444
yCO2 = 0.222 yH2 = 0.222
Limiting reactant is CO. nCO = 1-0.667 = 0.333
Fractional conversion = (1-0.333) / 1 mol feed = 0.667

CHBI 201 42
 Material Balances

Department of Materials and Metallurgical Engineering, FTI-ITS (43)