Basic Principles and Calculations

in Chemical Engineering
Y. Mortazavi
mortazav@ut.ac.ir
Catalyst and Reaction Eng. Lab.
Tel.: ext. 2242

University of Tehran
Fall 1399
Introduction
– In industrial reactions you will rarely find exact stoichiometric
amounts of materials used.

– To make a desired reaction take place or to use up a costly

reactant, excess reactants are almost always used.

• This excess material comes out together with, or perhaps

separately from, the product—and sometimes can be used
again.

• Even if stoichiometric quantities of reactants are used, but if

the reaction is not complete or there are side reactions, the
products will be accompanied by unused reactants as well
as side products.

2
Introduction
– In these circumstances some new definitions
must be understood:

a. Limiting reactant is the reactant that is present in

the smallest stoichiometric amount.

3
Introduction
• Excess reactant is a reactant in excess of the
limiting reactant.

• The percent excess of a reactant is based on the

amount of any excess reactant above the
amount required to react with the limiting
reactant according to the chemical equation, or
moles in excess
% excess =  (100)
moles required to react with limiting reactant

moles in excess = the total available moles of a reactant 

the moles required to react with the limiting reactant. 4
Introduction
• A common term, excess air, is used in
combustion reactions;

It means the amount of air available to react

that is in excess of the air theoretically
required to completely burn the combustible
material.

5
Introduction

• The required amount of a reactant is

established by the limiting reactant and is
for all other reactants the corresponding
stoichiometric amount.

• Even if only part of the limiting reactant

actually reacts, the required and excess
quantities are based on the entire amount
of the limiting reactant.

6
Introduction
• Air requirements for combustion vary with
the need to ensure full utilization of the
fuel's heating value but not generate
excessive air pollutants.

– Fuel oil, for instance, requires 5 -20% excess

air depending on burner design.

– Excess air is considered as a measure of

heater performance.

7
Introduction
• Three other terms that are used in
connection with chemical reactions have
less clear-cut definitions: conversion,
selectivity, and yield.

• Conversion: fraction of the feed or

some material in the feed that is
converted into products.

8
Introduction
• What the basis in the feed is for the
calculations and into what products the
basis is being converted must be clearly
specified or endless confusion results.

– Conversion is related to the degree of

completion of a reaction, which is usually the
percentage or fraction of the limiting reactant
converted into products.

9
Introduction
• Selectivity: ratio of the moles or mass of a
particular (usually the desired) product produced
to the moles or mass of another (usually
undesired) product
produced in a set of reactions.

• Yield, for a single reactant and product, is the

weight or moles of final product divided by the
weight or moles of initial reactant (P lb of product A
per R lb of reactant B).

10
Introduction
• If more than one product and more than one
reactant are involved,
– the reactant upon which the yield is to be based
must be clearly stated.

• Suppose there is a reaction sequence as follows:

A B C

with B the desired product and C the undesired

one. 11
Introduction
• Yield of B is:
mass (moles) of B produced / mass (moles) of A consumed,

• Selectivity of B is
mass (moles) of B produced / mass (moles) of C produced.

• The terms "yield" and "selectivity" are terms that measure

the degree to which a desired reaction proceeds relative to
competing undesired reactions.

• As a designer of equipment you want to maximize

production of the desired product and minimize production
of the unwanted products.

– Do you want high or low selectivity? Yield?

12
Introduction
– EXAMPLE 28 Limiting Reactant and Incomplete
Reaction

– Antimony (Sb) is obtained by heating pulverized

stibnite with scrap iron and drawing off the molten
antimony from the bottom of the reaction vessel:
Sb 2S3 + 3Fe  2Sb + 3FeS

– Suppose 0.600 kg of stibnite and 0.250 kg of iron

turnings are heated together to give 0.200 kg of Sb
metal.
13
Introduction
– Calculate:
a. The limiting reactant,
b. The percentage of excess reactant,
c. The degree of completion (fraction),
d. The percent conversion,
e. The yield.

14
Introduction
– Solution

– The molecular weights needed to solve the

problem and the gram moles forming the
basis are: Sb 2S3 + 3Fe  2Sb + 3FeS

component kg mol . wt . g mol

Sb 2S3 0.600 339.7 1.77
Fe 0.250 55.8 4.48
Sb 0.200 121.8 1.64
FeS 87.9 15
Introduction

a. Limiting reactant: we examine the chemical

reaction equation and note that if 1.77 g mol
of Sb2S3 reacts, it requires 3(1.77) = 5.31 g
mol of Fe, whereas if 4.48 g mol of Fe
reacts, it requires (4.48/3) = 1.49 g mol of
Sb2S3 to be available.

• Thus Fe is present in the smallest stoichiometric

amount and is the limiting reactant; Sb2S3 is the
excess reactant.

16
Introduction
b. The percentage of excess reactant is
1.77 - 1.49
% excess =  100 = 18.8% excess Sb 2S3
1.49

c. Although Fe is the limiting reactant, not all the

limiting reactant reacts. We can compute from the
1.64 g mol of Sb how much Fe actually does react:

1.64 g mol Sb 3 g mol Fe

 2.46 g mol Fe
2 g mol Sb

17
Introduction
• If by the fractional degree of completion is meant
the fraction conversion of Fe to FeS, then
2.46
fractional degree of completion =  0.55
4.48

d. The percent conversion can be arbitrarily based on

the Sb2S3 if our interest is mainly in the stibnite:

1.64 g mol Sb 1 g mol Sb 2S3

= 0.82 g mol Sb 2S3
2 g mol Sb
0.82
% conversion of Sb 2S3 to Sb =  100=46.3%
18
1.77
Introduction
e. The yield will be stated as kilograms of Sb
formed per kilogram of Sb2S3 that was fed to
the reaction:
0.200 kg Sb 1 kg Sb
yield = 
0.600 kg Sb 2S3 3 kg Sb 2S3

19
Introduction
– EXAMPLE 29 Limiting Reactant and Incomplete Reactions

– Aluminum sulfate can be made by reacting crushed bauxite

ore with sulfuric acid, according to the following equation:

A12O3 + 3H 2SO 4  A12 (SO 4 )3 + 3H 2O

– The bauxite ore contains 55.4% by weight of aluminum oxide,

the remainder being impurities. The sulfuric acid solution
contains 77.7% H2SO4, the rest being water.

– To produce crude aluminum sulfate containing 1798 lb of pure

aluminum sulfate, 1080 lb of bauxite ore and 2510 lb of sulfuric
acid solution are used.

20
Introduction

a. Identify the excess reactant.

b. What percentage of the excess reactant was consumed ?

c. What was the degree of completion of the reaction ?

21
Introduction
– Solution

– The pound moles of substances forming the basis of the

problem can be computed as follows:

1798 lb Al 2 (SO 4 ) 3 1 lb molAl 2 (SO 4 ) 3

 5.26 lb mol Al 2 (SO 4 ) 3
342.1 lb Al 2 (SO 4 ) 3
1080 lb bauxite 0.554 lb Al 2O 3 1 lb mol Al 2O 3
 5.87 lb mol Al 2O 3
1 lb bauxite 101.9 lb Al 2O 3
2510 lb acid 0.777 lb H 2SO 4 1 lb mol H 2SO 4
 19.88 mol H 2SO 4
1 lb acid 98.1 lb H 2SO 4

22
Introduction
a. Assume that Al2O3 is the limiting reactant. Then 5.87 × 3 = 17.61
lb mol of H2SO4 would be required, which is present. Hence
H2SO4 is the excess reactant.

b. The Al2(SO4)3 formed indicates that

5.26 lb mol Al 2 (SO 4 ) 3 3 lb mol H 2SO 4

 15.78 lb mol H 2SO 4 was consumed
1 lb mol Al 2 (SO 4 ) 3
15.78
 100  79.4%
19.88

c. The fractional degree of completion was

5.26
 0.90
5.87
23
Introduction
– EXAMPLE 30 The Meaning of Selectivity and Yield
– Two well-known reactions take place in the dehydrogenation of
ethane:
C2H 6  C2H 4 + H 2 (a)
C 2 H 6 + H 2  2CH 4 (b)

– Given the following product distribution (in the gas-phase reaction of

C2H6 in the presence of H2)
component percent
C2H 6 35
C 2H 4 30
H2 28
CH 4 7
Total 100

– what is (a) the selectivity of C2H4 relative to CH4 and (b) the yield of
24
C2H4 in kilogram moles of C2H4 per kilogram mole of C2H6?
Introduction
– Solution
Basis: 100 kg mol of products
– The selectivity (as defined) is
30 kg mol C 2 H 4 mol C 2 H 4
 4.29
7 kg mol
7 kg CHCH mol CH 4
4 4

– The moles of C2H6 entering into the reaction can be determined

from the C2H4 and the CH4 formed.
30 kg mol C 2 H 4 1 kg mol C 2 H 6
 30 kg mol C 2 H 6
1 kg mol C 2 H 4
7 kg mol CH 4 1 kg mol C 2 H 6
 3.5 kg mol C 2 H 6
2 kg mol CH 4
33.5 kg mol C 2 H 6
30 kg mol C 2 H 4 kg mol C 2 H 4
 0.90 25
33.5 kg mol C 2 H 6 kg mol C 2 H 6
Material balance
– Conservation laws have a special place in science
and engineering.

– Common statements of these laws take one of the

following forms;
• “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.

26
Material balance

– Processes involving nuclear transformations

extend our law to include the conservation of
both energy and matter.

• The word process will be taken to mean a series

of physical operations on or physical or
chemical changes in some specified material.

27
Material balance
– Why study mass balances as a separate
topic?

• Mass balance calculations are almost a

prerequisite to all other calculations in the solution
of both simple and complex chemical engineering
problems.

• Skills that are developed in analyzing mass

balances are easily transferred to other types of
balances and other types of problems.

28
Material balance

Hierarchy of topics to be studied

in this chapter

29
Material balance

– The aim of this part of course will be to help you

acquire a generalized approach to problem solving

• You may avoid looking upon each new problem, unit

operation, or process as entirely new and unrelated to
anything you have seen before.

– In working the problems you will encounter, it is

necessary to employ some engineering judgment.

30
Material balance
– You think of mathematics as an exact
science.

• Suppose that it takes 1 man 10 days to build a

brick wall; then

– 10 men can finish it in 1 day.

– 240 men can finish the wall in 1 hr,

– 14,400 can do the job in 1 min,

– and with 864,000 men the wall will be up before a single

brick is in place!
31
– Is this approach practical?!!
Material balance
– To take into account the flow of material in and out of a system,
the generalized law of the conservation of mass is expressed as
a material balance.

 mass   mass   mass   mass   mass 

 accumlation   input   output  generation   consumption 
         
 within    through    through    within    within 
 the   system   system   the   the 
         
 system   boundaries   boundaries   system   system 
General mass balance equation

• The generation and consumption terms refer to

gain or loss by chemical reaction.

32
Material balance
– The accumulation may be positive or
negative.

• It should be noted that in reading the words

in the above equation refers to a time
interval of any desired length, including a
year, hour, or second, or a differential time.

33
Material balance

– The equation reduces to the following equation for cases in

which

• there is no generation or usage of material within the system,

accumulation = input - output

– and reduces further to when there is, in addition,

• no accumulation within the system,

input = output
34
Material balance

– If there is no flow in and out of the system, the general mass

balance equation reduces to the basic concept of the
conservation of one species of matter within a closed (isolated)
system:

accumulation = generation - consumption

35
Material balance
– Inherent in the formulation of each of the balances
above is the concept of a system for which the
balance is made.

– By system it is meant;

• any arbitrary portion or

• whole of a process as designated for analysis.

36
Material balance

Flow (open) system

with combustion.

– Note that the system boundary is formally circumscribed about the

process itself to call attention to the importance of carefully depicting the
system in each problem you work.

– An open (or flow or continuous) system is one in which material is

transferred across the system boundary, that is, enters the system,
leaves the system, or both.

– A closed (or batch) system is one in which there is no such transfer

during the time interval of interest.
37
Material balance
– If you charge a reactor with reactants and
take out the products, and the reactor is
designated as the system, material is
transferred across the system boundary.

• You might ignore the transfer, and focus attention

solely on the process of reaction that takes place
only after charging is completed and before the
products are withdrawn.

– Such a process would occur within a closed system.

38
Material balance

39
Material balance
– In all the problems considered in this part of the
lecture the mass accumulation term will be
zero; i.e., steady-state problems will be
considered.

– For a steady-state process we can say, "What

goes in must comes out."

• Material balances can be made for a wide

variety of materials, at many scales of size
for the system and in various degrees of
complication.

40
Distribution and annual rates
of transfer of nitrogen in the
biosphere (in millions of
metric tons).
Material balance
– The figure displays the distribution of nitrogen in the
biosphere as well as the annual transfer rates, both in
millions of metric tons.

• The two quantities known with high confidence are the

amount of nitrogen in the atmosphere and the rate of
industrial fixation.

• Because of the extensive use of industrially fixed nitrogen,

the amount of nitrogen available to land plants may
significantly exceed the nitrogen returned to the atmosphere
by denitrifying bacteria in the soil.

42
Material balance
– In the process industries, material balances
assist in the planning for process design, in
the economic evaluation of proposed and
existing processes, in process control, and
in process optimization.

– Material balances are also used in the hourly

and daily operating decisions of plant
managers.

43
Material balance

– If there are one or more points in a process

where it is impossible or uneconomical to
collect data, then

» if sufficient other data are available, by

making a material balance on the process it
is possible to get the information you need
about the quantities and compositions at
the inaccessible location.

44
Material balance

– In most plants a mass of data is accumulated on the

quantities and compositions of
» raw materials,
» intermediates,
» wastes,
» products, and
» by-products
– that is used by the production and accounting
departments and that can be integrated into a revealing
picture of company operations.

45
Material (and energy)
balances in the
manufacture of
phenol presented
in the form of a
ledger sheet.
Material balance
– EXAMPLE 1 Water Balance for a River Basin
– Water balances on river basins for a season or for a year can be used
to check predicted groundwater infiltration, evaporation, or precipitation
in the basin. Prepare a water balance, in symbols, for a large river
basin, including the physical processes indicated in the following figure
(all symbols are for 1 year and S — storage or inventory).

47
Material balance
– Solution
– There is no reaction in the system., thus

accumulation = input - output

– Each term in this equation may be

represented by symbols defined in the figure.
Let the subscript t2 designate the end of the
year and t1 designate the beginning of the
year.
48
Material balance
– If the system is chosen to be the atmosphere plus the
river plus the ground, then the accumulation is:

S At2    
 S At1  S Rt2  S Rt1  SGt2  SGt1 
– The inputs are A1 + R1 + G1 and the outputs are A2 +
R2 + G2.
S At2    
 S At1  S Rt2  S Rt1  S Gt2  S Gt1 
  A1  A2    R1  R2    G1  G2 

– If the system is chosen to be just the river (including

the reservoir),
S Rt2 
 S Rt1   R1  P    R2  E  W 
accumulation input output 49