Module 9001

Mass Balance

Paul Ashall, 2008

The accounting of all mass in a
chemical/pharmaceutical process is referred
to as a mass (or material) balance.

Paul Ashall, 2008

 Uses
• ‘day to day’ operation of process for
monitoring operating efficiency
• Making calculations for design and
development of a process i.e. quantities
required, sizing equipment, number of items
of equipment

Paul Ashall, 2008

 Simple example – batch mixing
process
200 kg of a 40% w/w methanol/water solution
is mixed with 100 kg of a 70% w/w
methanol/water solution in a batch mixer
unit.
What is the final quantity and composition?

Paul Ashall, 2008

 continued
Total initial mass = total final mass = 300 kg
Initial methanol mass = final methanol mass
80 + 70 = final methanol mass = 150 kg
Therefore final composition of batch is
(150/300) x 100 = 50 % by wt.

Paul Ashall, 2008

 Exercise
1000 kg of 8% by wt. sodium hydroxide
(NaOH) solution is required. 20% sodium
hydroxide solution in water and pure water
are available. How much of each is
required?

Paul Ashall, 2008

 Batch processes
Batch processes operate to a batch cycle and
are non-steady state. Materials are added to
a vessel in one operation and then process is
carried out and batch cycle repeated.
Integral balances are carried out on batch
processes where balances are carried out on
the initial and final states of the system.

Paul Ashall, 2008

 Batch cycle
• Sequence of operations/steps repeated
according to a cycle
• Batch cycle time
• Batch size

Paul Ashall, 2008

 Simple batch reaction cycle
3 steps
Add reactants etc reaction Empty reactor

Next cycle
Start cycle t=0 t, finish cycle

Paul Ashall, 2008

 Continuous processes
These processes are continuous in nature and
operate in steady state and balances are
carried out over a fixed period of time.
Materials enter and leave process
continuously.

Paul Ashall, 2008

 Law of conservation of mass
When there is no net accumulation or
depletion of mass in a system (steady state)
then:

Total mass entering system = total mass

leaving system
or total mass at start = total final mass

Paul Ashall, 2008

 General mass balance equation
Input + generation – output – consumption =
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

Paul Ashall, 2008

 Definitions
• System – arbritary part or whole of a system
• Steady state/non-steady state
• Accumulation/depletion of mass in system
• Basis for calculation of mass balance (unit
of time, batch etc)
• Component or substance

Paul Ashall, 2008

 Exercise
1000 kg of a 10 % by wt. sodium chloride
solution is concentrated to 50 % in a batch
evaporator. Calculate the product mass and
the mass of water evaporated from the
evaporator.

Paul Ashall, 2008

 Mixing of streams

F2

F1
F4

F3

Paul Ashall, 2008

 Example

Calculate E and x

evaporator feed E, composition x%

Fresh feed 1000kg, 15%

by wt sodium hydrogen carbonate

Recycle stream 300 kg, 10% satd. soln.

Paul Ashall, 2008

 Flowsheets
• Streams
• Operations/equipment sequence
• Standard symbols

Paul Ashall, 2008

 Flowsheets
• Process flow diagram
• PID

Paul Ashall, 2008

 Typical simple flowsheet
arrangement

Recycle of unreacted material

Separation &
reactor purification
product
Fresh feed
(reactants, solvents,
reagents, catalysts etc)

waste Byproducts/coproducts

Paul Ashall, 2008

 Exercise
A 1000 kg batch of a pharmaceutical powder
containing 5 % by wt water is dried in a
double cone drier. After drying 90 % of the
water has been removed. Calculate the final
batch composition and the weight of water
removed.

Paul Ashall, 2008

 Exercise – batch distillation
1000 kg of a 20% by wt mixture of acetone in
water is separated by multistage batch
distillation. The top product (distillate)
contains 95% by wt. acetone and the still
contains 2% acetone. Calculate the amount
of distillate.

Paul Ashall, 2008

 Use of molar quantities
It is often useful to calculate a mass balance
using molar quantities of materials and to
express composition as mole fractions or
mole %.
Distillation is an example, where equilibrium
data is often expressed in mole fractions.

Paul Ashall, 2008

 Molar units
• A mole is the molecular weight of a substance
expressed in grams
• To get the molecular weight of a substance you
need its molecular formula and you can then add
up the atomic weights of all the atoms in the
molecule
• To convert from moles of a substance to grams
multiply by the molecular weight
• To convert from grams to moles divide by the
molecular weight.
• Mole fraction is moles divided by total moles
• Mole % is mole fraction
Paul Ashall, 2008
multiplied by 100
 Molar units
Benzene is C6H6. The molecular weight is
(6x12) + (6x1) = 78
So 1 mole of benzene is 78 grams
1 kmol is 78 kg

Paul Ashall, 2008

 Exercise – batch distillation
1000 kmol of an equimolar mixture of
benzene and toluene is distilled in a
multistage batch distillation unit. 90 % of
the benzene is in the top product (distillate).
The top product has a benzene mole fraction
of 0.95. Calculate the quantities of top and
bottom products and the composition of the
bottom product.
Paul Ashall, 2008
 Mass balance - crystalliser
A crystalliser contains 1000 kg of a saturated solution of potassium
chloride at 80 deg cent. It is required to crystallise 100 kg KCl from
this solution. To what temperature must the solution be cooled?

Paul Ashall, 2008

T deg cent Solubility
gKCl/100 g water
80 51.1
70 48.3
60 45.5
50 42.6
40 40
30 37
20 34
10 31
Paul Ashall, 2008
0 27.6
At 80 deg cent satd soln contains (51.1/151.1)x100
% KCl i.e. 33.8% by wt
So in 1000 kg there is 338 kg KCl & 662 kg water.
Crystallising 100 kg out of soln leaves a satd soln
containing 238 kg KCl and 662kg water i.e.
238/6.62 g KCl/100g water which is 36 g
KCl/100g. So temperature required is approx 27
deg cent from table.

Paul Ashall, 2008

Mass balance filtration/centrifuge

wash water/solvent

feed suspension solid

waste water filtrate

Paul Ashall, 2008

 Filtration

5000 kg DM water

F1
Water 300 kg
Impurity 55 kg
API 448 kg
Water 2600 kg
Impurity 5 kg
API 450 kg
Water 7300 kg
Impurity 50 kg
API 2kg
Paul Ashall, 2008
Mass balance - drier

water/evaporated solvent

feed product

Paul Ashall, 2008

Mass balance – extraction/phase
split

A+B A+B

S S+B

A – feed solvent; B – solute; S – extracting solvent

Paul Ashall, 2008
Example (single stage extraction;
immiscible solvents)

feed raffinate

E1
solvent extract

Paul Ashall, 2008

F = 195 kg; xf = 0.11 kg API/kgwater
S = 596 kg chloroform
y = 1.72x, where y is kgAPI/kg chloroform in extract and x is kg API/kg
water in raffinate.

Total balance 195 + 596 = E + R

API balance 19.5 = 175.5x1 + 596y1
19.5 = 175.5x1 + 596.1.72x1
x1 = 0.0162 and y1 = 0.029
R is 175.5 kg water + 2.84 kg API
and E is 596 kg chloroform + 17.28 kg API

Note: chloroform and water are essentially immiscible

Paul Ashall, 2008

Mass balance – absorption unit
exit gas stream

feed solvent

feed gas stream

waste solvent stream

Paul Ashall, 2008

 Mass balances – multiple units
• Overall balance
• Unit balances
• Component balances

Paul Ashall, 2008

 Multiple units
W2

F1 E C F P3

R4

E – evaporator; C – crystalliser; F – filter unit

F1 – fresh feed; W2 – evaporatedPaulwater; P3 – solid product; R4 – recycle
Ashall, 2008
of saturated solution from filter unit
 Mass balance procedures
• Process description
• Flowsheet
• Label
• Assign algebraic symbols to unknowns
(compositions, concentrations, quantities)
• Select basis
• Write mass balance equations (overall, total,
component, unit)
• Solve equations for unknowns
Paul Ashall, 2008
 Exercise
A mass balance and tracking of usage of a solvent
used in an API production process is required for a
Pollution Emission Register (PER).
Discuss and outline in general terms how you would
do this.

Ref. www.epa.ie
Paul Ashall, 2008
 Definitions
• Stoichiometric quantities
• Limiting reactant
• Excess reactant
• Conversion
• Yield
• Selectivity
• Extent of reaction
Paul Ashall, 2008
 Stoichiometry
• Refers to quantities of reactants and
products in a balanced chemical reaction.
aA + bB cC + dD
i.e. a moles of A react with b moles of B to
give c moles of C and d moles of D.
a,b,c,d are stoichiometric quantities

Paul Ashall, 2008

Reactor mass balances

Paul Ashall, 2008

Example – aspirin synthesis
reaction

Paul Ashall, 2008

Limiting reactant/excess reactant
• In practice a reactant may be used in excess
of the stoichiometric quantity for various
reasons. In this case the other reactant is
limiting i.e. it will limit the yield of
product(s)

Paul Ashall, 2008

 continued
A reactant is in excess if it is present in a
quantity greater than its stoichiometric
proportion.
% excess = [(moles supplied – stoichiometric
moles)/stoichiometric moles] x 100

Paul Ashall, 2008

Example – aspirin synthesis

Paul Ashall, 2008

 Conversion
• Fractional conversion = amount reactant
consumed/amount reactant supplied
• % conversion = fractional conversion x 100

Note: conversion may apply to single pass reactor

conversion or overall process conversion
Paul Ashall, 2008
 Yield
Yield = (moles product/moles limiting
reactant supplied) x s.f. x 100

Where s.f. is the stoichiometric factor =

stoichiometric moles reactant required per
mole product

Paul Ashall, 2008

Example – aspirin synthesis

Paul Ashall, 2008

 Selectivity
Selectivity = (moles product/moles reactant
converted) x s.f. x100

OR
Selectivity = moles desired product/moles
byproduct

Paul Ashall, 2008

 Extent
Extent of reaction = (moles of component leaving
reactor – moles of component entering
reactor)/stoichiometric coefficient of component

Note: the stoichiometric coefficient of a component

in a chemical reaction is the no. of moles in the
balanced chemical equation ( -ve for reactants and
+ve for products)

Paul Ashall, 2008

 Examples
A B
i.e. stoichiometric coefficients a = 1; b = 1
100 kmol fresh feed A; 90 % single pass
conversion in reactor; unreacted A is
separated and recycled and therefore overall
process conversion is 100%
R
F P
reactor separation

Paul Ashall, 2008

Discussion - Synthesis of 3,3
dimethylindoline

Paul Ashall, 2008

Discussion - Aspirin synthesis

Paul Ashall, 2008

 References
• Elementary Principles of Chemical
Processes, R. M. Felder and R. W.
Rousseau, 3rd edition, John Wiley, 2000

Paul Ashall, 2008