MATERIAL BALANCES

CONSERVATION OF MASS
Mass is neither created nor destroyed
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3 5
Reactor
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1
Distillation 4
2
12 13

6 Heat 8
Seperator
Exchanger

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7

{Input} = {Output} +{Accumulation}+ {Consumption}- {Gen}

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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

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 STEADY-STATE
❑ Steady-State
✔ Nothing is changing with time
✔ @ steady-state accumulation = 0

100 kg/min H2O 500 kg 100 kg/min H2O

H2O

Rate of addition = Rate of removal

❑ Unsteady-State (transient system)

✔ {Input} ≠ {Output}

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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

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

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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)

Centrifug
500 mg cells/L feed e 50 % by weight cells

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

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 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)

Centrifug
500 mg cells/L feed e 50 % by weight cells

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

❑ Fluid balance
Input: (106 – 500) g/h fluid
Output 1: 1000g/h . 0.5 = 500 g/h fluid
Output 2: D(g/h) = (106 – 500)g/h – 500 g/h = (106 -103)g/h fluid
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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
Distillation
Benzene + Toluene
%50 Benzene by mass
475 kg Toluene/h
M2 kg Benzene/h 9
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
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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

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 EXAMPLE 1
❑ Example ρH20 is given
Humid air Condenser Dry air
(n4) O2 In the
(n0) O2
(n5) N2 condenser,
(n1) N2 95% of H2O in
(n6) H2O
(n2) H2O the inlet air is
condensed.
(n3) H2O
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. 12
 EXAMPLE 2

❑ 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
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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 table

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

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EXAMPLE 3
❑ 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?

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EXAMPLE 3 - continue

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

F2
C2H6 0.1
N2 0.9

Unknowns: 3 xi and 4 Fi

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 EXAMPLE 3 - continue

Equations:
✔ Material balance (CH4, C2H6, N2)
✔ One specified ratio xCH4/xC2H6 = 1.5
✔ One summation of mole fractions
✔ 5 independent equations

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.

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 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

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 Balances on Multiple-unit Processes
Q : mass flow rate
xA : mass fraction of A
✔ You should treat any junction as
1-xA : mass fraction of B
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 2
x2 = 0.256

30 + Q3 = Q2 Q3 = 60 kg/hr x3 =
0.083 3
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 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

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Recycle Stream
Recycle stream is a term denoting a process stream that returns material from downstream
of a process unit back to the process unit.

There are several reasons one might employ a recycle stream:

increase conversion of a reactant to product

recovery of catalyst
dilution of a process stream (either to improve flow of the stream or control the rate of a reaction)
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re-use of a "working fluid" (like a lubricant or refrigerant)
Bypass Stream
Bypass stream is a stream that skips one or more stages of the process and goes
directly to another downstream stage.

This practice is far less common than recycle, but may be used if your ultimate
goal is a material with properties "in-between" the untreated reactant and the
process outlet product.
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Purge Stream
Purge stream is a stream bled off to remove an accumulation of
inerts or unwanted material that might otherwise build up in the
recycle stream.

This is common with multi-phase systems where only 1 phase is either removed or
recycled (i.e., if one recycles catalyst pellets, but adds "make-up" fresh catalyst a
purge will be needed to discard some "spent" catalyst).
Solving Recycle and Bypass Problems

The methods for solving recycle and bypass problems are basically the same. In the
steady state, there is no buildup or depletion of material within the system or recycle
stream of a properly designed and operated process.

When solving, you can write balances (total material or component) around:

the entire process structure

the mixing point
the splitter
the processing unit (inside the recycle/bypass)

Only three of these will be independent (the fourth is a linear combination).

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If you pick the right balances, you may be able to organize the problem for sequential
 You are asked to find three things:
(i)the recycle flow (labeled R on the drawing),
(ii)the production rate (labeled C on the drawing), and
iii)the recycle ratio, which will be calculated as R/10000 if we don't change the basis.

Let's call the fresh feed F.

Two are given as %KNO3, one as %H2O, and one as lb KNO3 per lb H2O.

We'd usually prefer all the numbers to be in percent.

Shifting the water percentage to nitrate is easy, just subtract from 100.

The other stream (R) requires a calculation.

Do we really need to calculate the mass fraction nitrate in R?

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 And we have all the compositions in terms of mass fractions.
We're given F, xF, W, xW = 0, xM, xC, and xR.
Unknowns are W, M, C, and R.
The problem asks for R, C, and R/F. Which balances can we write? Which should we write?

We can write:
The system balances will only involve two unknowns (W and C), one of which is a desired answer.
•On
Moreover,
the entiresince there
system -- is no nitrate
a total in stream
material, W, there
a nitrate, and/orisaawater
zero term.
balance
•On the evaporator -- a total material, a nitrate, and/or a water balance
•On the crystallizer-- a total material, a nitrate, and/or a water balance
•On the mixing point-- a total material, a nitrate, and/or a water balance

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Unknowns in the evaporator balance are R, M, and (R+F); in the crystallizer R and M, and in the mixing point balance R and (R+F).
Note that having found C, I've reduced the number of unknowns in the crystallizer balance relative to the others, so we'll start there.
There are still two unknowns, but this can be resolved by solving both the total and nitrate balances.

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 EXAMPLE2

❑ 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.

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 EXAMPLE2 - continue

n5 (mol) 0.983 DA, 0.017 W

n1 (mol)
n4 (mol) 100 mol
AIR
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
0.023 W(v) 30
 EXAMPLE 2 - 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
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EXAMPLE 2 - 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

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Energy Balance Procedure

Typically, solving energy balance problems is only marginally more involved than mass balances alone.
In addition to whatever else we might be solving in the mass balance, we will now be asked to calculate the amount of
heat or work going to/from the system or possibly determine something about the state of one of the streams (by
finding an unknown enthalpy or energy).

The procedure to solve mass/energy balances...

Perform all material balances (doing degrees of freedom and all the rest of that procedure)...it's possible that you will
have to count the energy balance as an additional equation in your degrees of freedom analysis (of course, you must
then also count any unknowns that arise in the energy equation in this analysis)

Write down the appropriate energy balance equation (closed or open)

Choose a reference state for all the species in the process (T, P, phase)

Simplify the energy balance equation (see previous lectures for hints here)

Obtain values for all the specific energies (U) or enthalpies (H) and
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calculate the changes in these values (remember that you are adding all the ins (initials) for each species and all the
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

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LIMITING & EXCESS REACTANTS

❑ If the reactants are not in stoichiometric proportion

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

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O2 is consumed.

Hint...
The reaction is

2 C2H6 + 7 O2 = 4 CO2 + 6 H2O

4 mol CO2 35.0 mol O2 ---------- = 20.0 mol CO2 7 mol O2 Discussion...
A balanced equation for the reaction is a basic requirement for identify the limiting reagent even if amounts of reactants
are known.

Example 2

Two moles of Mg and five moles of O2 are placed in a reaction vessel, and then the Mg is ignited according to the
reaction Mg + O2 = MgO.
Balance this equation and identify the limiting reagent in this experiment.
Hint...
The balanced reaction is, 2 Mg + O2 = 2 MgO

Thus, two moles of Mg require only ONE mole of O2.

Four moles of oxygen will remain unreacted. Oxygen is the excess reagent, and Mg is the limiting reagent.

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Discussion...
Solution:

1) Balance the equation:

Al2S3 + 6H2O ---> 2Al(OH)3 + 3H2S

2) Determine moles, then limiting reagent:

Al2S3 ⇒ 316.0 g / 150.159 g/mol = 2.104436 mol

H2O ⇒ 493.0 g / 18.015 g/mol = 27.366 mol
Al2S3 ⇒ 2.104436 / 1 = 2.104436
H2O ⇒ 27.366 / 6 = 4.561
Al2S3 is the limiting reagent.

3) Determine grams of water that react:

The molar ratio to use is 1:6

1 is to 6 as 2.104436 mol is to x
x = 12.626616 mol of water used
12.626616 mol times 18.105 g/mol = 227.4685 g

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4) Determine excess:
EXAMPLE 5

❑ 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

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 EXAMPLE 5 – 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

Moles reacted
(% excess)NH3 = (12-10) /10 x 100 = 20% excess NH3
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 + ni 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

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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

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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;

K(T) =

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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

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 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

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 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 cm 3/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

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 EXAMPLE(Flow chart)

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

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 FLOWCHART SCALING

n1
n3
A
n2

Scale factor: 100 100 n1

100 n3
A
100 n2

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Thank you

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