Lecture no.

11

MATERIAL BALANCES
Conservation laws occupy a special place in science and engineering.
Common statements of these laws take the form of "mass (energy) is neither created
nor destroyed," "the mass (energy) of the universe is constant," "the mass (energy) of
any isolated system is constant," or equivalent statements. To refute a conservation
law, it would be sufficient to find just one example of a violation.
Why study material balances as a separate topic? You will find that material
balance calculations are almost invariably a prerequisite to all other calculations in the
solution of both simple and complex chemical engineering problems. Furthermore,
skills that you develop in analyzing material balances are easily transferred to other
types of balances and other types of problems.

In this chapter we discuss the principle of the conservation of matter and how
it can be applied to engineering calculations, making use of the background
information discussed in Chap. 1. Figure 2.0 shows the relations between the topics
discussed in this chapter and the general objective of making material and energy
balances. In approaching the solution of material balance problems, we first consider
how to analyze them in order to clarify the method and the procedure of solution. The
aim will be to help you acquire a generalized approach to problem solving so that you
may avoid looking upon each new problem, unit operation, or process as entirely new
and unrelated to anything you have seen before. As you scrutinize the examples used
to illustrate the principles involved in each section, explore the method of analysis,
but avoid memorizing each example by rote, because, after all, they are only samples
of the myriad of problems that exist or could be devised on the subject of material
balances. Most of the principles we consider are of about the same degree of
complexity as the law of compensation devised by some unknown, self-made
philosopher who said: "Things are generally made even somewhere or some place.
Rain always is followed by a dry spell, and dry weather follows rain. I have found it
an invariable rule that when a man has one short leg, the other is always longer!"

2.1 THE MATERIAL BALANCE

To make a material balance (or an energy balance as discussed in Chap. 4) for

a process, you need to specify what the system is and outline its boundaries.
According to the dictionary, a process is one or a series of actions or operations or
treatments that result in an end [prodnct]. Chemical engineering focuses on operations
that cause physical and chemical change in materials such as:
Chemical manufacture
Fluid transport
Handling of bulk solids
Size reduction and enlargement
Heat generation and transport
Distillation
Gas absorption
Bioreactions
 .

and so on. Thhe exampless we use inn this book k often refeer to abstraactions of these
t
proccesses, becaause we doo not have the space here h to desccribe the deetails of anny of
themm. By systtem we meean any arrbitrary porrtion or whhole of a pprocess set out
speccifically forr analysis. Figure
F 2.1 shows
s a sysstem in whhich flow annd reaction take
placce; note parrticularly thhat the systeem boundary y is formallly circumsccribed aboutt the
proccess itself too call attenttion to the importance
i of carefullyy delineatinng the systemm in
eachh problem you work. An open (or flow) system is one in whhich materiaal is
trannsferred acrooss the systtem boundaary, that is, enters the system, leaaves the sysstem,
or both.
b A closed (or batchh) system iss one in whiich there is no n such trannsfer during g the
timee interval off interest. Obviously,
O iff you charg
ge a reactor with reactannts and takee out
the products, annd the reacttor is designnated as thee system, maaterial is traansferred accross
the system bouundary. But you might ignore the transfer, annd focus atteention solely on
the process of reaction
r thaat takes placce only afterr charging is completedd and beforee the
prodducts are wiithdrawn. SuchS a proceess would occur withinn a closed syystem.

A syystem bounndary may be b fixed witth respect too the processs equipmennt as in Fig. 2.1,
or the
t boundarry may be an imaginaary surface that grows or shrinkss as the pro ocess
goes on. Thinkk of a tube of
o toothpastee that is squ
ueezed. A fixed boundaary might bee the
tubee itself, in which
w case mass
m crossees the bounddary as youu squeeze thhe tube. Or, you
can imagine a flexible booundary suurrounding the t toothpaaste itself thhat followss the
extrruded toothppaste, in whhich case noo mass crossses the bounndary.

A material
m balaance is nothhing more thhan an acco
ounting for material
m flow
ws and chan nges
in innventory off material for
f a systemm. Examine Fig. 2.2. Equation
E (2.1) describees in
worrds the prinnciple of thhe material balance ap pplicable too processes both with and
withhout chemiccal reaction:
As a generic teerm, materiaal balance caan refer to a balance onn a system ffor the
1. Total
T mass
2. Total
T moles
3. Mass
M of a chhemical com mpound
4. Mass
M of an atomic
a species
5. Moles
M of a chemical
c com
mpound
6. Moles
M of an atomic speccies
7. Volume
V (posssibly)

Witth respect to a total mass

m balancee, in this book
b the geeneration annd consump ption
termms are zero whether a chemical
c reaaction occurrs in the sysstem or not (we neglecct the
trannsfer betweeen mass andd energy in ordinary
o ch
hemical proccessing); heence

accumulatiion = input – output (2.22

Witth respect to'abalance

t oillfie totaal moleg,-iffacnem:ic'aJJ-reaction-ddoes-occur,'yyou-
mosst likely willl have to taake into acccount the geeneration or consumptioon terms. In n the
abseence of chemical reactiion, the genneration and d consumptiion terms doo not apply y to a
singgle chemicaal compoundd such as water
w or acettone; with a chemical rreaction preesent
in thhe system, the
t terms doo apply.
From thhe viewpoinnt of both a mass balance or a mole m balancce for elemments
themmselves, succh as C, H, or 0, the geeneration an nd consumpttion terms aare not invo olved
in a material balance.
b Fiinally, Eq. (2.1) shoulld not be applied
a to a balance on o a
voluume of matterial unlesss ideal mixiing occurs (see( Sec. 3..1) and the densities off the
streams are thhe same. In this chhapter, info ormation about
a the ggeneration and
consumption teerms for a chemical
c com mpound wiiJI be given a priori or can be infeerred
fromm the stoichhiometric equations
e innvolved in the
t problem m. Texts treeating chem mical
reacction engineeering descrribe how too calculate from
f basic principles
p ggains and lo
osses
of chemical
c commpounds.
In Eq. (2.1)
( the acccumulation term refers to a changee in mass orr moles (plu us or
minnus) within the system m with resppect to timee, whereas the transfeers through h the
systtem boundaaries refer too inputs to anda outputss of the systtem. If Eq. (2. I) is wrritten
in symbols
s so that the vaariables aree functions of time, thhe equationn so formullated
wouuld be a diffferential eqquation. As an examplee, the differrential equaation for thee O2
matterial balancce for the syystem illustrrated in Fig. 2.1 might be written aas
wheere , withhin system denotes
d thee moles of oxygen witthin the sysstem
bouundary, andd denotes the raate at whicch oxygen enters, leaaves or reacts,
resppectively, as
a indicatedd by the suubscript. Eaach term inn the differrential equaation
reprresents a raate with the units of, saay, moles per
p unit tim me. Problems formulateed as
diffferential equuations witth respect to t time aree called unnsteady-statee (or transiient)
probblems and area discusseed in Chapp. 6. In co ontrast, in steady-state
s e problemss the
valuues of the variables in thet system do not chan nge with tim
me, hence thhe accumulaation
term
m in Eq. (2.11) is zero byy definitionn.
In this Chapter forr conveniennce in treatmment we use an integraal balance form
f
of Eq.
E (2.1). What
W we doo is to takee as a basiss a time peeriod such as one hou ur or
minnute, and inntegrate Eq.. (2.la) withh respect to o time. Thee derivativee (the left hand
h
sidee) in the diffferential equuation becoomes

wheere LIn is thhe differencce in the n022 within thee system at tz less that at t.. A term
m on
the right hand side
s of the differential
d equation beecomes, as for
f examplee the first teerm,

wheere no2 in represents

r thhe entire neet quantity of oxygen introduced
i into the sysstem
betwween t, and tz- If the fllow rate of O2 into thee system shoown in Fig.. 2.1 is consstant
at thhe rate of 12200 moles/hhr, by choossing a basis of one hour

Mosst, but not all,

a of the problems
p discussed in this
t chapterr are steadyy-state probllems
treaated as integgral balancces for fixed time periiods. If no accumulatiion occurs in a
probblem, and the geneeration andd consump ption termss can be omitted from f
consideration, the
t materiall balances reduce
r to thee very simpple relation

We should alsoo note in passing that balances using u Eq. (22.1) can be made on manym
otheer quantitiess in additionn to mass annd moles. Balances
B onn dollars aree common (y your
bankk statementt, for exampple) as are balances on n the numbber of entitiies, as in traffic
counnIs, populaation balannces, and social
s services. We nown look aat some sim mple
exammples of thee applicatioon of Eq. (2.. I)
EXAMPLE 2.1 Total Mass Balance
A thickener in a waste disposal unit of a plant removes water from wet sewage sludge
as shown in Fig. E2.1. How many kilograms of water leave the thickener per 100 kg
of wet sludge that enter the thickener? The process is in the steady state.

Solution

The system is the thickener (an open system). No accumulation, generation, or

consumption occur. Use Eq. (2.3). The total mass balance is

Consequently, the water amounts to 30 kg.

EXAMPLE 2.2 Mass Balances for a Fluidized Bed

Hydrogenation of coal to give hydrocarbon gases is one method of obtaining gaseous-
fuels with sufficient energy content for the future. Figure E2.2 shows how a free-fall
fluidized-bed reactor can be set up to give a product gas of high methane content.
Suppose, first, that the gasification unit is operated without steam at room
temperature (25'C) to check the gas flow rate monitoring instruments.

(a) If 1200 kg of coal per hour (assume that the coal is 80% C, 10% H, and 10% inert
material) is dropped through the top of the reactor without the air flowing, how many
kg of coal leave the reactor per hour?
(b) If, in addition to the coal supplied, 15,000 kg of air per hour is blown into the
reactor, at 25°C, how many kg of air per hour leave the reactor?
(c) Finally, suppose that the reactor operates at the temperatures shown in Fig. E2.2,
and that 2000 kg of steam (H20 vapor) per hour are blown into the reactor along with
15,000 kg/hr of air and the 1200 kg of coal. How many kg of gases exit the reactor per
hour assuming complete combustion of the coal?

Solution
Basis: I hr
The system is the fluidized bed.
(a) If coal is dropped into the vessel without airflow or reaction, as would be the case
at 25°C, 1200 kg of coal must remain in the reactor representing the accumulation:
Accumulation = Input - Output
1200 = 1200 - 0
Hence 0 kg of coal leave the reactor per hour.
(b) Because the accumulation is zero for air in the reactor, and no reaction occurs
Output = Input - Accumulation
15,000 = 15,000 - 0
The output is 15,000 kg/hr.
(c) All the material except the inert portion of the coal leaves as a gas. Consequently,
we can add up the total mass of material entering the unit, subtract the inert material,
and obtain the mass of combustion gases by difference

(a) If coal is dropped into the vessel without airflow or reaction, as would be the case
at
25°C, 1200 kg of coal must remain in the reactor representing the accumulation:
Accumulation = Input - Output
1200 = 1200 - 0
Hence 0 kg of coal leave the reactor per hour.
(b) Because the accumulation is zero for air in the reactor, and no reaction occurs
Output = Input - Accumulation
15,000 = 15,000 - 0
The output is 15,000 kg/hr.
(c) All the material except the inert portion of the coal leaves as a gas. Consequently,
we can add up the total mass of material entering the unit, subtract the inert material,
and obtain the mass of combustion gases by difference: