INDUSTRIAL STOICHIOMETRY II

3rd Semester,
B.Sc. Chemical Engineering
Session 2011
Delivered by:

Mr. Usman Ali

Department of Chemical Engineering
University of Engineering & Technology, Lahore

Units and Dimensions

Base Units
Multiple Prefixes
Derived Units

Reference for Practice

Loebel Arnold B. Chemical Problem-Solving by

Dimensional Analysis 2nd Ed. Houghton Miffin
Company. Boston Publisher.

Strategy for Analyzing/Solving

Problems
Read the problem carefully.
Draw a sketch/figure of the process.
Label flow streams with symbols.
Put all the known information/values of different
parameters(temperature, pressure, composition, chemical
reactions etc.) on the figure/respective streams.
Select a basis.
Make a list of unknown values/parameters or mention them
on the respective streams.
Write down the independent equations.
Solve the equations.
Check the answer (if possible).

Example
A limestone analysis is
CaCO3 = 92.89%
MgCO3 = 5.41%
Insoluble = 1.70%
Calculate;
1.
2.

lbs of CaO can be made from 5 ton of limestone

lbs of CO2 can be recovered per lb of limestone
CaCO3

CaO + CO2

MgCO3

MgO + CO2

Draw a sketch/figure of the

process

Heating

Label the flow streams

P1
R

Heating
P2

Put all the known data

P1
R

Heating
P2

Select a Basis:

100 lbs of limestone

P1

Heating
P2

Specify the unknown/s

lbs of CaO from 5 ton of limestone
lbs of CO2 per lb of limestone

P1
R

Heating
P2

Part 1

1 ton = 2240 lbs

1 lbmol CaCO3 = 100 lbs of CaCO3

100 lbs of CaCO3 = 56 lbs of CaO
92.89 lbs = (56/100) x 92.89 = 52 lbs of CaO
92.89 lbs of CaCO3 = 52 lbs of CaO
(2240x5x.9289)lbs ..= (52/92.89)x(.9289x2240x5) = 5824 lbs of CaO

Part 2

100 lbs of CaCO3 = 44 lbs of CO2

92.89 lbs = (44/100) x 92.89 = 41 lbs of CO2
84 lbs of MgCO3 = 44 lbs of CO2
5.41 lbs of MgCO3 = (44/84)x5.41 = 2.8 lbs of CO2
Total CO2 produced per 100 lbs of limestone = 41+2.8=43.8lb
Total CO2 produced per 1 lb of limestone = 43.8/100 = 0.44lbs

Process
Input
Output
Process Unit
Output

Input

Process Unit

Process Classification
Batch

Continuous

Semi-Batch

Activity
A balloon is filled with air at steady rate of 2 g/min.
A bottle of milk is taken from refrigerator and left on the
kitchen table.
Water is boiled in an open flask.
Carbon monoxide and steam are fed into a tubular reactor
at a steady rate and react to form carbon dioxide and
hydrogen. Products and unused reactants are withdrawn at
the other end. The reactor contains air when the process is
started up. The temperature of the reactor is constant and
the composition and the flow rate of the entering reactant
stream are also independent of the time. Classify the
process (a) initially and (b) after a long period of time has
elapsed.

Activity
Each year 50,000 people move into a city,
75,000 people move out, 22,000 are born and
19000 die. Write a balance on the population
of the city.

Material Balances on Continuous

Steady State Processes
One thousand kilograms per hour of a mixture of
benzene (B) and toluene (T) that contains 50% benzene
by mass are separated by distillation into two fractions.
The mass flow rate of benzene in the top stream is
450kg B/h and that of toluene in the bottom stream is
475kg T/h. The operation is at steady state. Write
balances on benzene and toluene to calculate the
unknown component flow rates in the output
streams.(F&R)

Material Balances on Continuous

Steady State Processes

Batch Process
Two methanol-water mixtures are contained in
separate flasks. The first mixture contains 40
wt% methanol, and the second contains 70 wt%
methanol. If 200g of first mixture are combined
with the 150g of the second, what are the mass
and composition of the product? (F&R)

Activity
To prepare a solution of 50% sulphuric acid , a
dilute waste acid containing 28% H2SO4 is
fortified with a purchased acid containing 96%
H2SO4. How many kilograms of the purchased
acid must be bought for each 100kg of dilute
acid.(Himmelblau)

Activity
Sludge is wet solids that result from the
processing in municipal sewage systems. The
sludge has to be dried before it can be
composted or otherwise handled. If a sludge
containing 70% water and 30% solids is passed
through a drier, and the resulting product
contains 25% water, how much water is
evaporated per ton of sludge sent to dryer.
(Himmelblau)

Activity
The catalytic dehydrogenation of propane is carried out in a
continuous packed-bed reactor. One thousand kilograms per
hour of pure propane is preheated to a temperature of 670oC
before it passes into the reactor. The reactor effluent gas, which
includes propane, propylene, methane and hydrogen, is cooled
from 800oC to 110oC and fed to an absorption tower, where the
propane and propylene are dissolved in oil. The oil then goes to
a stripping tower in which it is heated, releasing the dissolved
gases; these gases are recompressed and sent to a distillation
tower in which the propane and propylene are separated. The
propane stream is recycled back to join the feed to the reactor
preheater. The product stream from the distillation column
contains 98% propylene and recycle stream is 97% propane. The
stripped oil is recycled to the absorption tower.(F&R)

Problem Bookkeeping
Counting the number of unknown variables on
the flowsheet/chart, and then counting the
number of independent equations relating
them.
Material Balance
An Energy Balance
Process Specification
Physical Properties and Laws
Physical Constraints

Degree of Freedom
Degree of freedom = total number of stream variables
- total number of independent
balance equations
-total number of specified
independent stream variables
- total number of subsidiary relations

Activity
Examine figure E3.4a, which presents a simple
flow sheet for a single unit. Only the value of D
is known. What is the minimum number of
other measurements that must be made to
determine all other stream and composition
values? (Himmelblau)

Activity
A feedstock available at the rate of 1000mol/h and consisting of
20% propane
30% isobutane

20% isopentane
30% n-pentane
Is to be separated into two fractions by distillation. The distillate
is to contain all of the propane fed to the unit and 80% of the
isopentane fed to unit and is to consist of 40% isobutane. The
bottom stream is to contain all the n-pentane fed to the unit.
(Rekalitis)

Activity
In a new pigment plant that is to produce 4000lb/h dry TiO2
product, an intermediate stream consisting of TiO2 precipitate
suspended in an aqueous salt solution, is to be purified of salt so
that the final product contains, on water free basis, at most 100
parts per million of salt. The slat removal is to be accomplished
by washing the precipitate with water. If any pigment stream
contains 40% TiO2, 20% salt and the rest water ( all mass %) and
if the washed pigment is, upon settling, projected to consist of
about 50% TiO2 solids. What will be the composition of the
waste water stream be? (Rekalitis)

Activity
A labelled flowchart of continuous steady state
two unit distillation process is shown below.
Each stream contains two components, A and B,
in different proportions. Three streams whose
flow rates and compositions are not known are
labelled 1,2 and 3. calculate the unknown flow
rates and compositions of streams 1,2 and 3.
(F&R)

Activity
A mixture containing 50% acetone and 50%
water by weight is to be separated into its
components. The separation process consists of
extraction of the acetone from the water into
solvent that dissolves acetone but is nearly
immiscible with water, followed by distillation to
separate the acetone from the solvent. The
description that follows introduces some of the
terms commonly used in reference to liquid
extraction processes.

The acetone(solute)-water(feed solvent) mixture is first contacted with the

MIBK(wash solvent) in a mixer that provides good contact between two liquid
phases. Most of the acetone in the feed transfers from the aqueous(water)
phase to the organic (MIBK) phase in this step. The mixture passes into the
settling tank, where the phases separate and are separately withdrawn. The
phase rich in the feed solvent(water) is refereed to as the raffinate, and the
phase rich in the wash solvent(MIBK) is the extract.
The raffinate passes to second extraction stage, where it is contacted with the
second stream of the pure MIBK, leading to the transfer of more acetone. The
extracts from the two mixer-settler stages are combined and fed to the
distillation column. The vapour product(overhead) from the column is rich in
the acetone and is the product of the process. The bottoms stream is rich in
the MIBK, and in real process it is further treated and recycled back to the
extractors.

In a pilot plant study, for every 100kg of acetone-water fed to the

first extractor, 100kg of the MIBK are fed to the first extractor
and 75kg are fed to the second extractor. The extract from the
first extractor is found to contain 27.5% acetone. The second
stage raffinate has a mass of 43.1kg and consists of 5.3%
acetone, 1.6% MIBK, and 93.1% water, and the second stage
extract contains 9% acetone, 88% MIBK, and 3 % water. The
overhead from the distillation column contains 2% MIBK, 1%
water and the balance acetone.
For an assumed basis of 100kg acetone-water feed, calculate the
masses and the compositions (component percentages by mass)
of the stage 1 raffinate and the extract, the stage 2 extract, the
combined extract, and the distillation overhead and the bottoms
products. (F&R)

Activity
The flowchart of a steady state process to recover
crystalline potassium chromate(K2CrO4) from an
aqueous solution of this salt is shown.
Forty five hundred kilograms per hour of a solution that
is 1/3K2CrO4 by mass is joined by a recycle stream
containing 36.36% K2CrO4, and the combined stream is
fed to the evaporator. The concentrated stream that
leaves the evaporator in which it is cooled(causing
crystals of K2CrO4 to come out of solution) and then
filtered.

The filter cake consists of K2CrO4 crystals and a solution

that contains 36.36% K2CrO4 by mass; the crystals
account for 95% of the total mass of the filter cake. The
solution that passes through the filter, also 36.36%
K2CrO4, is recycle stream.
Calculate the weight of water removed in the
evaporator, the rate of production of crystalline K2CrO4 ,
the ratio (kg recycle)/(kg fresh feed), and the feed rates
that the evaporator and the crystallizer must be
designed to handled. (F&R)

Activity
Suppose that the filtrate was discarded instead
of being recycled. Calculate the production rate
of crystals. What are benefits and costs of
recycling?

Activity
Seawater containing 3.50 wt % salt passes
through a series of 10 evaporators. Roughly
equal quantities of water are vaporized in each
of the 10 units and then condensed and
combined to obtain a product stream of fresh
water. The brine leaving each evaporator but the
tenth is fed to the next evaporator. The brine
leaving the tenth evaporator contains 5.00 wt%
salt.

a) Draw a flowchart of the process showing the first, fourth,

and the tenth evaporators. Label all the streams entering
and leaving these three evaporators.
b) Write in the order the set of the equations you would solve
to determine the fractional yield of fresh water from the
process(kg H2O recovered/kg H2O in process feed) and the
weight per cent of salt I n the solution leaving the fourth
evaporator. Each equation you write should contain no more
than one previously undetermined variable. In each
equation, circle the variable for which you would solve. Do
not do the calculations.

c) Solve the equations derived in part (b) fort the two specified
quantities.

Activity
An
equimolar
liquid
mixture of benzene and
toluene is separated into
two product streams by
distillation. A process
flowchart
and
a
somewhat oversimplified
description
of
what
happens in the process
follow:

Inside the column a liquid stream flows downward and a vapor stream
rises. At each point in the column some of the liquid vaporizes and
some of the vapor condenses. The vapor leaving the top of the
column, which contains 97 mole % benzene, is completely condensed
and split into two equal fractions: one is taken as the overhead
product stream, and the other(the reflux) is recycled to the top of the
column. The overhead product stream contains 89.2% of the benzene
fed to the column. The liquid leaving the bottom of the column is fed
to a partial reboiler in which 45% of it is vaporized. The vapour
generated in the reboiler(the boilup) is recycled to become the rising
vapor stream in the column, and the residual reboiler liquid is taken off
as the bottom product stream. The composition of the streams leaving
the reboiler are governed by the relation, where yB and the xB are the
mole faction of the benzene in the liquid and the vapor stream.

(a) Take a basis of 100 mol fed to the column. Draw and
completely label a flowchart, and for each of four
systems(overall, column, condenser, reboiler), do the
degree-of-freedom analysis and identify a system with
which the process analysis might appropriately begin.
(b) Write in order the equations you would solve to determine
all unknown variables on the flowchart, circling the variables
for which you would solve in each equation.
(c) Calculate the molar amounts of the overhead and the
bottom products, the mole fraction of the benzene in the
bottom product , and the percentage recovery of the
toluene in the bottom product(100xmoles of toluene in
bottoms/moles toluene in feed)

Activity
In an absorption tower, a gas is contacted with a liquid under conditions such
that one or more species in the gas dissolve in the liquid. A stripping tower
also involves a gas contacting a liquid, but under conditions such that one or
more components of the feed liquid come out of the solution and exit in the
gas leaving the tower.

A process consisting of an absorber and a striper is used to separate the

components of a gas containing 30 mole % CO2 and the balance CH4. A
stream of this gas is fed to the bottom of the absorber. A liquid containing 0.5
mole % dissolved CO2 and the balance methanol is recycled from the bottom
of the stripper and fed to the top of the absorber. The product gas leaving the
top of the absorber contains 1mole % of CO2 and the essentially all of the
CH4 fed to the unit. The CO2-rich liquid solvent the bottom of the absorber is
fed to the top of the stripper and a stream of nitrogen gas is fed to the
bottom.

Ninety precept of the CO2 in the liquid feed to the stripper come out of the
solution in the column, and the nitrogen/CO2 stream leaving the column
passes out to the atmosphere through stack. The liquid stream leaving the
stripping tower is 0.5% CO2 solution recycled to the absorber. The absorber
operate at temperature Ta and pressure Pa and the stripper operates at Ts
and Ps. Methanol may be assumed to be non-volatile- that is none enters the
vapor phase in either column-and the nitrogen may be assumed insoluble in
the methanol.
(a)In your own words, explain the overall objective of the two unit process
and the functions of the absorber and the stripper in the process.
(b) The streams fed to the top of the each tower have something in common,
as do the streams fed to the bottoms of each tower. What are these
commonalities and what is the probable reason for them.

(c)Taking a basis of 100mol/h of the gas fed to the absorber, draw and label a
flowchart of the process. For the stripper outlet gas, label the component
molar flow rates rather than the total flow rate and the mole fractions. Do
the degree of freedom analysis and write in order the equations you would
solve to determine all unknown stream variables except nitrogen flow rate
entering and leaving the stripper.
(d) Calculate the fractional CO2 removal in the absorber(moles absorbed/
mole in feed) and the molar flow rate and the composition of the liquid feed
to the stripper.
(e) Calculate the molar flow rate of the gas to the absorber required to
produce the absorber product gas flow rate of 1000kg/h.
(f) Would you guess that Ts would be higher or lower than Ta. Explain? What
about the relationship of Ps to Pa?
(g) What properties of the methanol would you guess make it the solvent of
the choice for this process?

Material Balance Involving

Chemical Reactions

Activity
Consider the reaction,
C4H8 + 6O2 --------> 4CO2 + 4H2O
1. Is the stoichiometric equation balanced?
2. What is the stoichiometric co-efficient of CO2?
3. What is the stoichiometric ratio of H2O to O2?
4. How many lb-moles of O2 react to form 400 lbmoles of CO2?
5. One hundred g-moles/min of C4H8 are fed into a
reactor, and 50% reacts. At what rate is water
formed?

Activity
Acrylonitrile is produce in the reaction of propylene, ammonia,
and oxygen;
C3H6 + NH3 + 1.5 O2-----> C3H3N + 3H2O
The feed contains 10 mol % propylene, 12% ammonia, and 78%
air. A fractional conversion of 30% limiting reactant is achieved.
Taking 100 mol of feed as a basis, determine which reactant is
limiting, the percentage by which each of the other reactants is
in excess, and the molar amounts of all product gas constituents
for a 30% conversion of the limiting reactant.

Activity

Activity

Activity
Methane is burned with oxygen to yield carbon
dioxide and water. The feed contains 20 mole %
CH4, 60 % O2, 20% CO2, and the 90%
conversion of the limiting reactant is achieved.
Calculate the molar composition of the product
stream using
(1) Balances on molecular species
(2) Atomic balances
(3) The extent of reaction.

Activity

Activity
Methanol may be produced by the reaction of carbon dioxide
and hydrogen.
CO2 + 3H2 --------> CH3OH + H20
The fresh feed to the process contains hydrogen and carbon
dioxide in a stoiciometric proportion , and 0.5% inert(I). The
reactor effluent passes to a condenser, which removes
essentially all of the methanol and the water formed, and none
of the reactant or inerts. The latter substances are recycled to
the reactor. To avoid build-up of the inerts in the system, a purge
stream is withdrawn from the recycle. The feed to the reactor
contains 2% inerts, and the single-pass conversion is 60%.
Calculate the molar flow rates of the fresh feed, the total feed to
the reactor, and the purge stream for a methanol production
rate of 1000mol/h.