Introduction To Mechanical Engineering

INTRODUCTION TO CHEMICAL ENGINEERING
This
A fluid catalytic cracker for producing high - octane gasoline from petroleum .
of for
by the M. W. Kellogg Co. at Yorktown , Virginia ,

unit was designed and built
subsidiary the Standard Oil Co. Indiana Courtesy
the American Oil Co.
of
(
a
).
,
M. W. Kellogg Co.
Introduction to
CHEMICAL ENGINEERING
L. BRYCE ANDERSEN
caird
Associate Professor of Chemical Engineering
University of Nebraska
LEONARD A. WENZEL
Professor of Chemical Engineering
Lehigh University
McGRAW - HILL BOOK COMPANY , INC .

New York Toronto London
196 )
Engin . Library
Тр
145
• A54
INTRODUCTION TO CHEMICAL ENGINEERING
Copyright © 1961 by the McGraw - Hill Book Company , Inc. Printed in

the United States of America . All rights reserved . This book , or
parts thereof , may not be reproduced in any form without permission
of the publishers . Library of Congress Catalog Card Number 60-53472
THE MAPLE PRESS COMPANY , YORK , PA .
01607
PREFACE
To the beginner , chemical engineering appears to be a complex and

mystifying field . The general public , if it has any concept of chemical
all
engineering at usually tends with chemistry The more

to
confuse
it
,
.
sophisticated novice knows that chemical engineering distinct field
is
a
in ,
still asks questions about the work the chemical engineer
he
of
but
process industry What are the day ay activities
to
of
the chemical
a
-
.
-d
typical chemical engineer What tools does use What are the ulti he
?
?
mate products
of
his endeavor
?
answer these questions We will survey the

to
In
this book we intend .

profession engineering the processes
of
of
chemical and the chemical
industry the more important tools the engineer will
be
of
of
number
A
.
Most important among these are mass and energy

in
considered detail
.
balances which are covered thoroughly give the begin

to
Our aim
is
,
.
an
all
ning chemical engineer his chosen profession while
he
of
over view
-
learning the rigorous analytical techniques

of
of
some the field

is
also
its its on .
Upon completion this book the beginner should have
of
foundation
a
,
chemical engineering which

to
base his later work broad

in
in in
which
is
the field and which demonstrates the depth

of
of
view the field

more quantitative aspects We believe that both breadth and depth
.
desirable an introductory book

in
are
.
Chapters
of
to
and introduce the reader the broad fields chemical

2
1
process Chapters pre

in
engineering the chemical industries and

4
3
.
sent basic mathematical physical and chemical principles and methods

,
The mathematical methods presented Chap include some funda

in
3
.
an
numerical analysis and introduction computers

to
of
mental methods
.
We
subjects will grow importance

to
of
feel that both chemical

in
these
The computer general enough
to
engineers material form satis

is
a
.
any available computer

be
to
factory
It
introduction can used even

.
for
no
computer the emphasis

of
on
available the methods

is
is
where
,
for
on
analysis required computer programming rather than the details

The physical principles presented Chap are limited
to
coding
in
of
4
.
those which are necessary allow intelligent use mass and energy
to to
of
balances We have tried develop fully those areas covered rather

,
.
include material usually presented Chapters

in
later courses
to
than
5
.
vii
viii PREFACE
and 6 apply many of these principles to the calculation of mass and

energy balances in chemical processes . Differential as well as integral
balances are presented . In this way the student realizes from his first
introduction to the field that time - dependent processes are as important
as the steady -state processes . Chapters 7 , 8 , and 9 apply the techniques
developed in the previous chapters to the analysis of actual chemical
processes . The processes are selected to give a representative view of
the chemical industry .
There is material in the book for a 3 to 4 semester hour course . We
believe that the qualitative and quantitative aspects covered are of equal
importance . Chapters 1 and 2 lead to valuable classroom discussion , if
it is encouraged . Chapters 7 , 8 , and 9 provide practice in quantitative
mass and energy balances , and at the same time give a qualitative view
of the industry . Neglect of the quantitative material is unlikely ; neg
lect of the qualitative material results in an unrealistically narrow view
of chemical engineering for an introductory course . For this reason we
suggest a careful selection of topics from both areas if time does not per
mit complete coverage of the book .
This book is the result of teaching an introductory course in chemical
engineering to sophomores and juniors . Almost
all
of
the book has been
thank the students and administra
to
tested the classroom We wish

in
tion Rice University and Lehigh University for their cooperation
in
of
the development
of
this book
.
Bryce Andersen
L.
Leonard A. Wenzel
CONTENTS
Preface . vii
Symbols xi
Chapter 1. The Chemical Process Industry 1
What Is the Chemical Process Industry ? 1

Origins and Development of the Chemical Process Industry 5
The Chemical Industry Today 9
The Systematic Analysis of Chemical Processes 14
The Flow Sheet as a Representation of a Chemical Process 20
Chapter 2 . The Chemical Engineer in the Chemical Process Industry . 25
Origin of Chemical Engineering 25

What Is Chemical Engineering ? 26
What Does a Chemical Engineer Do ? 27
General Aspects of Chemical Engineering 45
Chapter 3. Useful Mathematical Methods . 48
Presentation and Correlation of Data 50

Trial -and- Error Solutions 81
Mean Values . 84
Application of Computers in Chemical Engineering 86
Dimensions and Units . 102
Chapter 4. Physical and Chemical Principles . 115
Process Variables 115

Physical States 122
Phase Equilibria 132
Reaction Rates 159
Reaction Equilibria 163
Chapter 5. The Mass Balance 174
Over - all Balances 177

Humidity 182
Chemical Reactions . 183
Bypass 189
Recycle 191
Purge 193
ix
viii PREFACE
and 6 apply many of these principles to the calculation of mass and

energy balances in chemical processes . Differential as well as integral
balances are presented . In this way the student realizes from his first
introduction to the field that time- dependent processes are as important
as the steady -state processes. , 8 , and 9 apply the techniques
Chapters 7 >
developed in the previous chapters to the analysis of actual chemical
processes . The processes are selected to give a representative view of
the chemical industry .
There is material in the book for a 3 to 4 semester hour course . We
believe that the qualitative and quantitative aspects covered are of equal
importance . Chapters 1 and 2 lead to valuable classroom discussion , if
it is encouraged . Chapters 7 , 8 , and 9 provide practice in quantitative
mass and energy balances , and at the same time give a qualitative view
of the industry . Neglect of the quantitative material is unlikely ; neg
lect of the qualitative material results in an unrealistically narrow view
of chemical engineering for an introductory course . For this reason we
suggest a careful selection of topics from both areas if time does not per
mit complete coverage of the book .
This book is the result of teaching an introductory course in chemical
engineering to sophomores and juniors . Almost
all
the book has been
of
thank the students and administra
to
tested the classroom We wish

in
for
tion Rice University and Lehigh University their cooperation
in
of
the development
of
this book
.
Bryce Andersen
L.
Leonard A. Wenzel
CONTENTS
Preface vii
Symbols xi
Chapter 1. The Chemical Process Industry 1
What Is the Chemical Process Industry ? 1

Origins and Development of the Chemical Process Industry 5
The Chemical Industry Today 9
The Systematic Analysis of Chemical Processes 14

The Flow Sheet as a Representation of a Chemical Process 20
Chapter 2. The Chemical Engineer in the Chemical Process Industry . 25
Origin of Chemical Engineering 25

What Is Chemical Engineering ? 26
What Does a Chemical Engineer Do ? 27
General Aspects of Chemical Engineering 45
Chapter 3. Useful Mathematical Methods . 48
Presentation and Correlation of Data 50

Trial -and- Error Solutions 81
Mean Values . 84
Application of Computers in Chemical Engineering 86
Dimensions and Units 102
Chapter 4. Physical and Chemical Principles . 115
Process Variables 115

Physical States 122
Reaction Rates 159
Chapter 5. The Mass Balance 174
Over -all Balances 177

Humidity 182
Chemical Reactions . 183
Bypass 189
Recycle 191
Purge 193
ix
х CONTENTS
Differential Mass Balances 195

Chapter 6. The Energy Balance 221
Forms of Energy 222

Total Energy Balance 228
Heat Effects 233
Phase Changes 242
Enthalpy - Composition Diagrams 246
Chemical Reactions 248
Industrial Reactions 257
Differential Energy Balances 263

Equivalence of Mass and Energy . 269
Chapter 7. Inorganic Chemicals 281
Sulfuric Acid Manufacture 283

Ammonium Nitrate Manufacture . 291
Chapter 8. Organic Chemicals 300
Phenol Manufacture 303

Ethyl Acetate Manufacture 307
Chapter 9. Petroleum and Petrochemicals 312
Petroleum Refining . 314

Petrochemicals . 323
Location of Chemical Plants 334
Appendixes 341
A. Conversion Factors for Units . 343

B. Densities of Various Substances 345
C. Density of Ethyl Alcohol - Water Solutions 346
D. Vapor Pressure of Various Liquids and Solids 347
E. Melting Points and Normal Boiling Points . 348
F. Henry's Law Constants for Various Gases in Water 349

G. Heat Capacities . 350
1. Empirical constants for heat capacities of gases at constant pressure . 350

2. Mean heat capacities for gases . 351
a . Low range 351
b . High range 351
3. Liquids 352
4. Aqueous H2SO4 solutions at 20 ° C 353

5. Solids . 354
H. Heat Effects of Phase Changes 355
1. Heats of vaporization 355
2. Heats of fusion 356
357
I. Heats of Formation , Solution , and Combustion
atm
1. Standard heats of formation of inorganic compounds (25 ° C , i

;
)
standard integral heats 357

25
of
solution infinite dilution

at
atm
C
1
,
°
(
).
organic compounds
of
of
Standard heats formation and combustion

2.
358
25
atm
C
1
,
°
(
Index 359
SYMBOLS
Infrequently
all
This list includes important symbols and subscripts
.
used symbols and subscripts are defined where they are introduced
in
the
text Dimensions and typical units are included
.
.
sq
L2
A A
ft
area
),
(
accumulation
component constant slope
a a
ft ;
;
O2
acceleration sec2
L
/
),
(
component constant intercept

C С b
;
;
constant total concentration molar density
cu
L3
M
moles
lb
ft
/
),
;
)
(
/
(
number components
of
component constant heat capacity molecular speed

с
;
;
;
CP heat capacity constant pressure MT Btu lbm cal mole

at
C
/g
E
/
/
),
F,
°
°
(
TP
mean heat capacity

су heat capacity MT Btu 1bm
F
constant volume
at
/g E
°
/
),
(
internal energy Btu lbm cal

F E E
mole
E
/
/
,
,
(
dimension energy
of of
dimension force
O2
gravity
of
acceleration
ft
32.2 sec2
9
L
/
/
),
(
lbm
dimensional conversion factor ML FO2 lbj

H 9c
ft
32.2 sec
/
?
),
(
-
/
enthalpy mole
M
Btu lbm cal

/g
E
/
/
,
,
(
)
ж
humidity percentage relative per cent

or
,
H. Henry's law constant mm Hg mole fraction

/g /
,
M
of of of of of of of
AHC heat combustion cal mole

E
/
,
,
(
AHp
M
heat formation cal mole

E
/g
), ), /
,
(
)
/ /M M
AH heat fusion cal mole

E
/g /g /g g
f,
/
E /
(
AHm heat mixing cal mole solute

(
AHR heat reaction cal mole

E E
,
(
)
M
ΔΗ heat solution cal mole solute

,
/
,
(
vaporization
M
ΔΗ heat cal mole

E
/g
η
/
,
(
any component
i
inlet
i
dimensional conversion factor FL

J
778 lbs Btu

ft
E
/
,
(
K. phase equilibrium constant

K.
equilibrium constant concentration units

,
Кр equilibrium constant pressure units

,
KE kinetic energy Btu lbs

ft
E
),
,
(
KE kinetic energy per unit mass

M
Btu lbm lbs lbm

ft
E
/
/
,
,
)
/
-
(
liquid
M
L
lb
of
mass lbm moles

,
,
(
)
xi
xii SYMBOLS
L
M
dimension of length
total mass ( M ) , lbm , lb moles
,
M molecular weight ( M / M ) , lbm / lb mole
M dimension of mass
т. mass ( M ) , lbm
m mass flow rate ( M 0 ) , lbm / sec/
N number ; total number of molecules
п number of moles ; number of molecules per unit volume
0 outlet
Р pressure ( F / L2 ) , lbs / sq in .,>atm , mm Hg
P number of phases
Pabs absolute pressure
Pc critical pressure
P gage- gage pressure
Po vapor pressure
р partial pressure
PE
lbs
potential energy (E ) , Btu , ft -
PE potential energy per unit mass M Btu lbs 1bm
ft
lbm
ft E
/
,
,
-
(
/
/
L3
cu
volumetric flow rate

Q Q
sec
/
/ )0,
(
system
( ( to to to
heat added Btu lbm

at at E
), E a a a
/
,
(
QP heat added system constant pressure

Qv heat added system constant volume cu
MT
T R
mole
lb
atm
R
mole
lb
gas constant Btu

R
ft
/
/
,
/
'
° ,
, )
temperature
K
R
C
T
F,
°
°
'
T. critical temperature
V V V V T
temperature
, of
dimension
cu
)L3
volume
ft
(
cu
volume per unit mass

L3
lbm liters mole

/g
ft
,
/
) ,
(
vapor
M
lb
/
of
mass Ibin moles

,
) ,
(
independent variables
L of
number
velocity sec
Ū V
ft
),
(
mean velocity
by
W system
M
work done Btu lbm

lb
1bm
ft
E
;
a
-
,
/
(
/
:W
shaft work done by system

a
variable mass fraction mole fraction

2
;
;
' Y
molar humidity
M
M
mole air
lb
lb
moles H2O
/
,
), (
humidity
Y
mole air
M
M
lb
lbm H2O
/
/
(
variable mass fraction mole fraction

y
;
;
ft of
mean value the variable

y
2 ў
height
L
),
(
compressibility factor
2
mass fraction mole fraction

2
Greek letters
α relative volatility
A increase increment
,
of
dimension time
time
©
sec
),
(
chemical potential
M
density
cu
cu
M
ft
%
lbm cm
р
g
L
/
/
),
,
(
summation
M
of
lb
mass mixture lbm moles

,
,
(
)
CHAPTER 1
THE CHEMICAL PROCESS INDUSTRY
Products of the chemical process industry are used in every
all
of
areas
day life The raising food plants and animals requires chemical
of
.
fertilizers insecticides food supplements and disinfectants Many

,
.
building materials have been chemically processed for example metals
,
,
,
concrete roofing materials paints and plastics Clothing utilizes many
,
,
.
synthetic fibers and dyes Transportation depends upon gasoline and
.
other fuels Written communication uses paper and printing ink and
;
.
electronic communication requires many chemically processed insulators
by
and conductors The nation's health maintained drugs and
is
.
all
pharmaceuticals soaps and detergents insecticides and disinfectants
,
,
-
In
products the chemical process industry addition many chemicals

of
,
.
never reach the consumer their original form but are sold within the
in
industry for further processing the production

or
of
other chemicals
in
use
for consumer use often said that the chemical industry
its
It
own
is
is
.
best customer
.
WHAT IS THE CHEMICAL PROCESS INDUSTRY

?
Any definition description the chemical process industry

or
of
bound
is
incomplete the chemical industry involve

be
Most processes
to
in
to a
.
chemical change interpreted

be
The term chemical change should

.
"
"
include not only chemical reactions but also physicochemical changes such
,
the separation and purification the components Purely

as
of
of of
mixture
a
mechanical changes are usually not considered part the chemical proc
an
they changes As example

to
ess unless are essential later chemical

,
,
.
the plastic polyethylene using ethylene produced

or of
the manufacture
,
from petroleum natural gas involves chemical process On the

a
,
other hand the molding and fabrication the resulting plastic resin into
of
,
final shapes for consumer products would not considered part

be
of
the
chemical process
.
on
Some industries which depend chemical changes are not usually

part process industry because
of
of
considered the chemical tradition

,
special processes large volume particular product such paper

as
or
of
a
,
,
1
2 INTRODUCTION TO CHEMICAL ENGINEERING
TABLE 1.1 . CHEMICAL PROCESS INDUSTRIES
Industry Typical products End uses
Inorganic Sulfuric acid Fertilizers , chemicals , petroleum

chemicals refining , paint pigments , metal
processing , explosives
Nitric acid Explosives , fertilizer
Sodium hydroxide Chemicals , rayon and film proc
essing , petroleum refining , pulp
and paper processing, lye ,
cleansers , soap , metal process
ing
Organic chemicals Acetic anhydride Rayon , resins , and plastics
Ethylene glycol Antifreeze , cellophane , dynamite ,
synthetic fibers
Formaldehyde Plastics
Methanol Formaldehyde manufacture ,
antifreeze , solvent
Petroleum and Gasoline Motor fuel
petrochemicals Kerosene Jet fuel
Oils Lubricating , heating
Ammonia Fertilizer, chemicals
Ethyl alcohol Acetaldehyde manufacture , sol
vent , other chemicals
Alkyl aryl sulfonate Detergent
Styrene Synthetic rubber , plastics
Pulp and paper Paper Books , records , newspapers , etc.
Cardboard Boxes
Fiberboard , etc. Building materials
Pigments and Zinc oxide
paint Titanium dioxide Pigments for paint , ink , plastic
Carbon black rubber , ceramics , linoleum
Lead chromate
Linseed oil Drying
oil
Basic lacquer varnish

en
Phenolic resins and

,
,
Alkyd resins amel constituents

Rubber Natural rubber (isoprene ) Automobile tires molded goods
,
Synthetic rubbers ( GR - S , and sheeting footwear elec

,
neoprene , butyl ) trical insulation

Plastics Phenol - formaldehyde
Polystyrene
Various uses all areas
of
in
Polymethylmethacrylate every
Polyvinyl chloride day life
Polyethylene
Polyesters
Synthetic fibers Rayon
Nylon
Cloth and clothing
Polyesters
Acrylics
THE CHEMICAL PROCESS INDUSTRY 3
1.1
TABLE CHEMICAL PROCESS INDUSTRIES Continued
)
.
Industry Typical products End uses
Minerals Glass and ceramics Windows containers bricks pipe
,
Cement
of
Concrete for construction
buildings highways etc.
-pby ,
its
Coal Fuel coke and roducts
,
Cleansing agents Soap
Synthetic detergents
Household and industrial clean
sodium alkyl
as
such ing
(
aryl sulfonates
)
Wetting agents
Biochemicals Pharmaceuticals and Health and medicinal applica
drugs tions
Fermentation products
:
Penicillin Medicinal use

Ethyl alcohol Solvent beverage
,
Food products Human sustenance
Metals Steel
Copper Building material machinery
,
Aluminum etc.
Zirconium
Uran um Nuclear fuel
Many complex chemical the food industry for

or
processes
in
steel
,
.
example cheese making which involves fermentation reaction are not

a
,
,
of ,
part the chemical process industry

be
to
considered On the other

.
sugars produce beverage and industrial

to
a of
hand the fermentation

,
chemical industry The huge metallurgical

as
alcohols often listed

is
industry usually distinguished from the chemical process industry

is
the special nature the processes and the vast quantities

of
of
to of
because the
products but the processing metals might also
be
be
of
considered
;
merely one segment the chemical industry

of
One possible listthe important chemical process industries given

of
is
1.1
all
Table industries which utilize chemical processing are

Not
in
all
parts the listed industries necessarily part

of
of
included nor are the

,
chemical process industry An examination the list will show the

of
.
tremendous scope the industry and will also demonstrate the problems
of
any such listing

or
of
of
involved classification consideration few

in
a
.
1.1
the products Table will show the wide scope

of
the industries listed

in
chemical processing Only few typical products are listed

of
a
.
The largest tonnage inorganic chemical sulfuric acid Little sulfuric

is
by .
industry
all
acid reaches the public nearly

of
consumed the
in
is
it
;
by
other products Large quantities are used the petro

of
manufacture
.
leum and metals industries Important organic chemicals include

.
alcohols , dyes , and intermediates used to produce other chemicals .

Many organic chemicals are produced by several industries listed in other
categories . For example , plastics and petroleum are organic materials .
Here the division is arbitrary . Ethyl alcohol, an organic chemical ,> was
primarily produced by biochemical fermentation before the Second World
War ; it is now produced primarily from petroleum or natural gas . There
fore , ethyl alcohol might be listed under organic chemicals , petrochemicals ,
or biochemicals . Ethyl alcohol production also illustrates two major
approaches to organic -chemical manufacture . In fermentation the start
ing material is a natural product ( grain , molasses , etc. ) ; whereas manu
facture from petroleum involves synthesis of the molecule from ele
mentary mineral building blocks ( ethylene and water ) .
The primary petroleum products are gasoline , other fuels , lubricants,
and petrochemicals . Since the Second World War petrochemicals have
assumed a tremendous role in the American economy . They are usually
organic chemicals made from components of petroleum or natural gas .
Paradoxically , the largest tonnage petrochemical is the inorganic chemical
ammonia , produced by reaction of hydrogen from natural gas or petro
leum with nitrogen from air . It is used as a fertilizer and as a starting
material for other products . Many plastics , such as polyethylene and
polypropylene , derive their starting materials from natural gas or petro
leum . Primary components of many synthetic detergents are produced
in the oil refinery .
The pulp and paper industry
uses many unusual processes and is often
considered separate from the chemical process industry , even though it
employs many chemical engineers . The manufacture of paint involves
combination of inorganic pigments or organic dyes for color with various
natural or synthetic organic vehicles , extenders , and drying agents . This
very old industry still relies heavily on the " art " or " practice " in its
production paints varnishes and other surface coatings although
of
;
,
many newer developments are based on better understanding

of
the
a
scientific principles
.
The division between the rubber and plastics industries not distinct
is
The various synthetic rubbers are plastics with properties similar

to
natural rubber Natural rubber made from the sap tree whereas
of
is
,
.
most synthetic rubbers are derived from petroleum Synthetic fibers are
.
usually polymeric organic compounds Rayon made from natural

.
cellulose was the first large volume synthetic textile fiber and nylon was
,
-
the first purely synthetic textile fiber Many others have been developed
.
since the Second World War

.
Important chemical process industries utilizing mineral raw materials

products
its
are glass and ceramics cement and coke and

-by
The
,
.
-pby
important coke roducts benzene and toluene compete with the same
industry
oil
materials produced in the Petroleum natural gas and
,
.
sulfur The trend cleansing agents has
of
are also minerals the field
in
.
been away from soap produced from natural fats toward synthetic deter
oil
gents many which are produced using raw materials from the
of
,
refinery
.
The biochemical process industry includes pharmaceuticals fermenta
,
tion products and food These industries either use processes involving
,
biological action such .

produce penicillin produce
or
to
fermentation as
(
)
products that are biologically active such
its
penicillin
as
medicinal
in
(
effects Pharmaceuticals are produced by controlled natural biological
).
by
synthetic organic chemistry Although much
of
processes the food
or
.
industry the chemical process industry
not generally considered part
of
is
,
those products which have been highly processed such sugar and
as
,
hydrogenated shortening may part the industry
be
be
to
of
considered
,
.
Fermentation processes produce industrial and beverage alcohols acetone
,
by
is on
biological action various sugars Most
of
and acetic acid the
.
industrial demand for these materials now met from petrochemical
sources
.
As
stated earlier the metals industry usually considered apart from

is
,
the chemical process industry although recovery and purification many
of
,
the newer metals involve much chemical processing Many chemical

of
all
engineering principles are applied the production The

of
metals
in
.
production iron and steel involves many high temperature chemical
of
by
reactions and phase equilibria Aluminum produced electro

is
.
chemical means Many new metals such

as
uranium zirconium and

,
,
.
by
titanium are produced processes involving standard chemical engineer

,
ing operations Many new metallurgical processes are being developed

.
by
by
chemical companies rather than the traditional metals companies

,
This brief survey the chemical process industry has shown that any
of
listing arbitrary and subject ambiguities More

or
to
classification
is
detailed surveys the chemical process industry may

be
of
found Refs
in
2
.
Perhaps satisfactory definition chemical process industry

of
and
is
7.
by
industry whose principal products are manufactured

an
processes
"
based upon the chemical and physical principles included

in
of
the field
chemical engineering
."
ORIGINS AND DEVELOPMENT OF THE

CHEMICAL PROCESS INDUSTRY
The chemical industry dates back prehistoric times when man first
to
attempted control and modify his environment Its development can

to
divided into two periods The prescientific period which extended

be
to
.
the eighteenth century was largely empirical with little under

of
the end
,
standing of the basic chemistry . In the scientific period of the last 150
years the chemical industry has made phenomenal progress based upon a
sound knowledge of the principles underlying chemical processes .
Prescientific Chemical Industry . The early prescientific chemical
industry developed as any other trade or craft . Since those who practiced
the craft were not of the literate or learned class , none of the few remain
ing reports of early chemical processes was written by people who were
actually engaged in the craft . From the beginning of the sixteenth
century more adequate records are available .
,
With no knowledge of chemical science and no means of chemical
analysis , the early chemical craftsman had to rely on previous art and on
superstition . Progress was slow and confusion great . For example , in
green vitriol
oil
the sixteenth century “ vitriol was made from blue
or
of
”
cupric sulfur was made by
or
as
of
now known ferrous sulfate Oil
”
(
)
.
burning sulfur The latter was initially much more expensive than the
.
-
former even though they were the same compound sulfuric acid
,
.
Probably the oldest chemical process industry fermentation although
an is
,
industry
its
earliest times was more folkcraft than Fermenta

in
it
.
the most primitive man possibly because
of
tion was known
to
of
the ease
,
discovery the oldest fermented liquor dating
to
accidental Ale the
is
,
.
Egyptians before 3000 B.C. Distillation began the first century A.D.
in
,
by
the thirteenth century distillation fermented liquors con
to
of
and
centrate alcohol was commonplace Europe
in
Recovery and use metals began before 4000 B.C. The first metals
of
found were gold and silver since they commonly occur metallic form
in
,
and are therefore easily recognized

be
The first metal extracted from

to
.
Egypt and Mesopotamia about 3500 B.C. Other

its
ore was copper

in
early metals include tin lead zinc and iron Methods smelting and
of
of
,
iron pro
of by
assaying were well developed the sixteenth century Early

.
heating the oxide ore with charcoal

to
duction involved the reduce

it
.
forced draft Roman

or
of
of
Evidence blast has been found ruins

in
a
furnaces
.
Glass cements and ceramics were known early times The earliest
in
,
cement was wet clay Egyptians used gypsum mortar and the Greeks and
;
Romans used lime mortar Little basic improvement was made until the
.
discovery portland cement the nineteenth century Ceramics began

of
in
with baked lay bricks and pottery early Many early

as
as
5000 B.C.
-c
civilizations used glazed and colored ceramics Porcelain was developed

.
the eighth ninth century China

or
in
in
Vinegar dilute acetic acid was the earliest known acid since was
it
(
)
on
fermented liquors No historical references

of
formed the oxidation

.
At
mineral acids until the fourteenth century

to
are made this time

.
nitric acid was made from saltpeter KNO3 and ferrous sulfate by heating
(
)
the mixture and condensing the distilled nitric acid . The first industrial
application of nitric acid was in the separation of gold from silver in the
sixteenth century . Industrial use of sulfuric acid developed later and
became important only in the late eighteenth century , when it was used to
produce chlorine for bleaching cloth . Hydrochloric acid was discovered

in the seventeenth century . In the early nineteenth century the Leblanc
hydro
for
process making soda Na2CO3 also produced large quantities
of
(
)
chloric acid and became the cheapest and most widely used mineral
it
,
acid the period

of
Early cleansing agents included many natural materials such
as
the
,
alkali found Truesoap was first mentioned
in
wood ashes the first
in
.
was probably made by boiling ashes with natural
oil
century
or
fat
It
.
.
The chemistry soapmaking was not understood until the early nine
of
teenth century
.
Scientific Chemical Industry Progress and growth the early
of
.
industry were slow because there was little understanding
of
chemical the
scientific principles underlying the various processes The alchemists
,
.
an
who might have contributed understanding

of to to
of
the processes were
,
preoccupied attempting convert base metals into gold and
in
in
attempting find the elixir Alchemists were superstitious and

to
life
.
mysterious and often fraudulent and deceitful

,
late eighteenth entury Europe interest

In
the scientific principles

in
,
-c
chemistry rapidly increased and great progress was made Oxygen

of
.
by
was discovered the Swedish pharmacist Carl Wilhelm Scheele
in in
by
1770–1773 and independently the English minister Joseph Priestley

At
1774–1775 the same time the great French chemist Antoine Lavoisier
.
oxygen combustion thereby refuting the popular

in
of
clarified the role

,
phlogiston theory careful work oxidation and other

in
Lavoisier's
.
sound quantitative
on
establish chemistry
to
chemical fields did much

a
basis He recognized that organic compounds contained carbon and

.
Shortly
he
hydrogen and developed methods for their determination

,
after the French Revolution the aristocratic Lavoisier was tried by the new
on
republican government obscure charges and was guillotined

at
in
1794
fifty one
the same year Joseph Priestley fled from England
In
the age
of
.
-
persecution for his religious and political

to
of
the United States because

views Between 1803 and 1808 John Dalton England developed
in
a
.
workable atomic theory which helped explain how elements combined into
on
molecules thereby making possible

to
consider chemical reactions

it
a
,
quantitative basis
.
The increased understanding improvements

to
of
chemical science led

and new developments chemical processing The principal chemical
in
industries the early nineteenth century manufactured alkalies acids

in
,
,
and metals
.
The organic -chemical industry began to develop after 1850. Although

many natural products had been purified for centuries , the lack of under
standing of organic chemistry prevented the synthesis of organic com
pounds . Cellulose was treated with nitric acid to produce nitrocellulose
explosives . Rubber was introduced in the early nineteenth century and
was first vulcanized in the 1840s . Ether and chloroform were made on a
small scale for use as anesthetics . Synthetic organic chemistry may be
considered to date from 1828 when Friederick Wöhler in Germany syn
thesized the natural organic product urea from inorganic ammonium
cyanate . The work of many great German chemists and of William
Perkin in England led to the development of the aniline dye industry , the
first large - scale synthetic organic chemical industry . Perkin established
his dye works at the age of nineteen in 1857 , but the great development
of the synthetic - dye industry was in Germany . The synthetic - drug
industry developed in Germany after 1880 . Attempts were made to
synthesize a drug which would have action similar to the natural product
quinine in reducing fever . Although early attempts to synthesize
quinine were unsuccessful , a similar -acting compound kairine was
synthesized by O. Fischer . Germany almost completely monopolized the
synthetic drug and dye industries until the First World War .
American Chemical Industry . 5 The American chemical industry
developed slowly in colonial days , and somewhat more rapidly after the
Revolution . Industry in the United States grew with development in
European industry , but America remained dependent on many European
chemical manufactures until the First World War .
Afew chemical products , such as wood tar , pot - ashes , bricks , and glass ,
were exported from the Jamestown Colony in the early 1600s . American
industry was to some extent restricted by British regulations . After the
Revolution, United States industry expanded in an attempt to become
independent of British manufactures . Sulfuric acid was first produced in
America in 1793. In 1802 a young refugee of the French revolution
Eleuthère Irénée du Pont de Nemours , who had learned to make gun
powder while a student of Lavoisier , established a powder works in
Delaware . As was the case in Europe , the American chemical industry
concentrated on processing natural products , such as sugar , textile fibers,
and coal ; on metals ; and on a few inorganic chemicals , such as alkalies ,
acids , and bleaching agents .
Most basic chemistry was of European origin until the twentieth
century . In 1905 the American Leo Baekeland developed the first
thermosetting plastic , a phenol - formaldehyde polymer called Bakelite .
This was the beginning of the world plastic industry . The impetus for a
self - sufficient American chemical industry came in the First World War ,
off
when the United States was cut from German chemicals Germany
.
was the undisputed world leader in the chemical industry . After the
First World War , the United States chemical industry expanded rapidly ,
until today it dominates the world .
THE CHEMICAL INDUSTRY TODAY
The
chemical industry in the United States today is a sprawling complex
of raw -material sources , manufacturing plants , and distribution facilities
which supplies the country and the world with thousands of chemical
products , most of which were unknown 100 years ago . As discussed at
the beginning of this chapter , no clear limit can be used to define the
chemical process industry , and within the industry it is not possible to
classify completely the various industries . This section will consider
briefly the major companies in the chemical process industry . Table 1.2
lists representative leading chemical companies , as surveyed by
120
Chemical and Engineering News. The grouping does not correspond to
1.1
that in Table primarily because many the major chemical firms

of
produce products several categories For example the Olin Mathieson

in
,
.
Chemical Corporation produces inorganic and organic chemicals cello
,
in
phane and polyethylene films paper pharmaceuticals their Squibb
,
division brass aluminum batteries and flashlights lumber firearms
in
,
,
,
(
)
their Winchester division >ammunition and explosives There are about

,
,
)
.
all
45 companies types the United States whose sales exceed one

in
of
billion dollars annually excluding financial companies
in
of
14
these are
;
(
the chemical process industry and are listed Table Many

of
the
in
1.2
.
chemical firms are the result mergers

of
of
of
smaller firms Some

aa
series ,
.
such the various Standard Oil companies the splitting

as
of
are the result

,
large corporation government antitrust action

of
as
of
result
a
To illustrate the growth diversity the chemical industry

of of
of
and
is
it
,
interest briefly history the oldest and largest

to
of
consider the one

du
companies Company
de
its E.
Pont Nemours For the first hundred

&
I.
.
:
years after founding 1802 Du Pont produced only explosives

in
of
,
:
by
In
various kinds 1902 the company was sold

of
the older members the

.
for
family
du
younger group Ponts million This agressive

to
of
12
$
a
1
new management the next nine years acquired explosive aking

64
in
-m
corporations and was process acquiring govern

69
of
the others when

in
ment antitrust action forced split Du Pont's industrial emplosives and

in
a
sporting owders business From this split came the Atlas Powder
.
-p
Company and the Hercules Powder Company which are today inde
,
pendent diversified chemical producers

.
ť
an
In
attempt diversify the new Du Pont management established

to
research laboratory investigate new products particularly

in
to
1903
,
!
This effort ultimately led the production

to
those related cellulose

to
of
.
Table 1.2 . MAJOR CHEMICAL COMPANIESŤ
Total assets , * Net sales, *

thousands of dollars thousands of dollars
Chemical : Companies engaged primarily in the manufacture of basic and intermediate

chemicals
Air Reduction Co. 222,508 200,604

Allied Chemical Corp. 759,771 719,662
American Cyanamid Co. 625,914 583,575
American Potash & Chemical Corp. 73,551 54,621
Atlas Powder Co. 53,387 70,721
Columbian Carbon Co. 88,991 76,146
Commercial Solvents Corp. 76,388 70,381
Diamond Alkali Co. 142,904 137,874
Dow Chemical Co. 856 , 945 705,442
E. I. du Pont de Nemours & Co. 2,969,578 2,114,323
W. R. Grace and Co. 521,965 469,696
Harshaw Chemical Co. 42,867 69,984
Hercules Powder Co. 212,878 283,650
Heyden Newport Chemical Corp. 56,609 55,948
Hooker Chemical Corp. 183,985 149,817
Mallinckrodt Chemical Works 38,819 34,674
Metal Hydrides , Inc. 3,487 5,921
Michigan Chemical Corp. 17,272 8,642
Monsanto Chemical Corp. 740,800 615,377
Nopco Chemical Co. 23,563 37,256
Olin Mathieson Chemical Corp. 839,170 702,032
Pennsalt Chemicals Corp. 88,162 87,534
Pittsburgh Coke & Chemical Co. 75,014 70,023
Reichold Chemicals , Inc. ,
70 737 93,616
Rohm and Haas Co. 171,636 215,909
Spencer Chemical Co. 80,267 57,584
Stauffer Chemical Co. 212,096 228,077
Stepan Chemical Co. 8,403 19,361
Thiokol Chemical Corp. 73,148 190 , 199
Union Carbide Corp. 1,632,250 1,531,344
Witco Chemical Co. 24,082 51,207
Wyandotte Chemical Corp. 104,489 93,894
Chemical Process : Companies applying chemical engineering and chemical processing

in their manufacturing operations
Catalin Corp. of America 11,350 22,261
Chemetron Corp. 118,778 130,271
Colgate - Palmolive Co. 370 , 641 581,982
Corn Products Co. 410,395 676,377
* In a recent typical year ( 1959 ) .

This table is reproduced from Ref . 2 , by permission .
1.2
TABLE MAJOR CHEMICAL COMPANIES Continued
(
.
)
Total Net
**
assets sales
,
*
of ,
of
thousands dollars thousands dollars
Corning Glass Works 168,076 204,887

Eastman Kodak Co. 915,906 914,100
Food Machinery Chemical Corp. 292,350 342,923
&
General Aniline Film Corp. 177,929 159,009

&
Glidden Co. 137,552 195 764
,,
Interchemical Corp. 64,238 122,592
Kawecki Chemical Co. 6,648 7,505
Koppers Co. 201 163 240 281
,
Libbey Owens Ford Glass Co. 249 201 306,734
,
-
-
Metal and Thermit Corp. 24,770 40,160

Minnesota Mining Mfg Co. 351,838 446,580
&
Nalco Chemical Co. 30,479 47 243
,
National Distillers Chemical Corp. 504,342 575,566
&
National Starch Chemical Corp. 28,444 52,769

&
Owens Illinois Glass Co. 491,875 552,677

-
Penick Ford Ltd. 33,417 56 940

&
,
,
Pittsburgh Plate Glass Co. 619 265 606,947

,
Procter and Gamble Co. 835,581 1,368,532

Sherwin Williams Co. 182,226 275,352
-
Sun Chemical Corp. 33,301 54,781

United Carbon Co. 71,680 62,171
Drug and Pharmaceutical chemicals and pharmaceutical

of
Producers medicinal
:
preparations
Abbott Laboratories 126,541 122,602

Allied Laboratories 28,365 30,164
American Home Products Corp. 220,183 420,843
Bristol Myers Co. 78 266 131,544
,
-
Eli Lilly and Co. 214,925 187,010

Merck and Co. 213,333 216,913
Norwich Pharmacal Co. 27,569 40,669
Parke Davis and Co. 204,273 191,527
,
Chas Pfizer and Co. 239,307 253,673

.
Schering Corp. 80,292 80,558

37,921 34,509
G.
D. Searle and Co.

Smith Kline
French Laboratories 96,284 134,891
&
,
Sterling Drug
Inc. 139,214 209,248
,
U.S. Vitamin and Pharmaceutical Co. 11,915 14,866

Upjohn Co. 158 409 156,914
,
Vick Chemical Co. 85,503 115,228

Warner Lambert Pharmaceutical Co. 115,934 190,660
In
recent typical year 1959

a
*
).
TABLE 1.2 . MAJOR CHEMICAL COMPANIES ( Continued )
Total assets , * Net sales ,

thousands of dollars thousands of dollars
Extractive and Fertilizers : Companies extracting and processing ore and minerals ,
including sulfur and phosphates as well as fertilizer producers
American Agricultural Chemical Co. 77,483 91,490

Duval Sulphur & Potash Co. 39,575 19,045
Eagle - Picher Co. 72,004 120,925
Foote Mineral Co. 18,565 20,172
Freeport Sulphur Co. 167,406 53,234
International Minerals & Chemical Corp. 131,045 112,560
International Salt Co. 47 , 446 31,149
Jefferson Lake Sulphur Co. 22,864 11,233
Lithium Corp. of America 9,514 10,841
National Lead Co. 348,412 530,551
Smith - Douglass Co. 35,861 45,926
Tennessee Corp. 75,854 76,862
Texas Gulf Sulphur Co. 124,523 63,597
U.S. Borax and Chemical Corp. 104,890 62,192
Virginia - Carolina Chemical Corp. 65,008 81,482
oil
Petroleum : Producers and refiners of and natural gas especially those with large
,
petrochemical operations
Atlantic Refining Co. 807,813 541 274
,
Cities Service Co. 1,298 235 994,879
,
Gulf Oil Corp. 3,576,318 3,170,847

Phillips Petroleum Co. 1,579,935 1,163,033
Shell Oil Co. 1,767,309 1,809 953
,
Sinclair Oil Corp. 1,494,069 232,214
,
1
Socony Mobil Oil Co. 3,347,399 3,092,911

Standard Oil Co. 2,578 296 1,564,827
of
Calif
,
.
Standard Oil Co. Ind 2,846,502 1,956,812

(
)
.
Standard Oil Co. N.J. 9,894,655 7,910 689

,
(
Standard Oil Co. Ohio 408,571 387,446

(
Sun Oil Co. 743,219 735,697

Texaco Inc. 3,347,743 2,678,029
,
707,167 423,831
of
Union Oil Co. California
Pulp and Paper pulp and paper products

of
Manufacturers
:
Champion Paper and Fibre Co. 184,408 168,750

Crown Zellerbach Corp. 585,775 527 322
,
Kimberly Clark Corp. 327,321 368,232

-
Mead Corp. 244 128 323,631

,
Rayonier Inc. 221,749 129 504

,,
St. Regis Paper Co. 454,547 474,393

In
recent typical year 1959

a
*
).
TABLE 1.2 . MAJOR CHEMICAL COMPANIES ( Continued )
Total assets , Net sales , *

thousands of dollars thousands of dollars 1
Scott Paper Co. 316,899 297,160

West Virginia Pulp and Paper Co. 256,216 233,123
Rubber : Manufacturers of rubber and rubber products

Firestone Tire and Rubber Co. 853,987 1,187,784
General Tire and Rubber Co. 339,804 676,942
B. F. Goodrich Co. 559,464 771,591
Goodyear Tire and Rubber Co. 1,002,226 1,579,258
U.S. Rubber Co. 659,425 976,766
Synthetic Fibers : Companies whose primary products are rayon and other synthetic
fibers
American Enka Corp. 99,174 109 , 176

American Viscose Corp. 276,254 239,809
Celanese Corp. of America 396,628 265 , 236
Industrial Rayon Corp. 78,276 62,068
* In a recent typical year ( 1959 ) .
celluloid pyroxylin plastic and coated fabrics . The shortage of dyes and
other German chemicals during the First World War led Du Pont to take
an interest in these fields . By the end of the war the company was
producing pyroxylin plastics , paints and other surface coatings , synthetic
dyes and other organic chemicals in addition to explosives . Since the
First World War the company has expanded rapidly by development of
many new products and acquisition of many other companies . Du Pont
first produced rayon (a French development ) in 1920 and introduced
cellophane cellulose film in 1923. After many years of research Du Pont
introduced a nylon synthetic textile fiber in 1939 , and more recently
Dacron polyester fiber and Orlon acrylic fiber . Today , in plants scattered
across the United States , Du Pont produces thousands of products in
nearly every area listed in Table 1.1 for sale to industry and to the public .
its
Today , Du Pont's total assets are more than 200 times sale price
in
explosives now small part

of
its total annual sales

of
1902 and its sale

is
a
,
Many other companies have histories development and diversifica

of
Du Pont.5 Although Table 1.2 includes

all
interesting
of
as
as
tion that
the
major corporations
the categories listed far from complete
in
is
it
,
Many important smaller companies have been omitted One major

.
companies employing chemical engineers that omitted the

is
is
group
of
design and equipment companies Companies that develop design and

,
,
.
construct chemical processes for the chemical industry include C. F.

Braun , Foster - Wheeler Corp. , M. W. Kellogg , The Lummus Co. , and the
Universal Oil Products Co. In addition many of the chemical companies
license their processes to other companies . Manufacturers of equip
ment , such as heat exchangers , distillation columns , filter presses , and
pumps , also employ many chemical engineers in design and sales .
THE SYSTEMATIC ANALYSIS OF CHEMICAL PROCESSES
Early chemical usually involved a few simple steps . Mate

processes
rials were processed in small batches . Process improvements evolved
slowly from experience gained by the operators . As the demand for
chemical products increased and the chemical industry grew , processes
had to be developed to produce large quantities at the lowest possible
cost . Improvements based on experience were no longer sufficient ; it
became necessary to build new plants for products never before produced .
Systematic analysis of chemical processes elucidated many underlying
principles which could be used in the synthesis of new processes .
Modern chemical processes are often extremely complex operations
involving hundreds of pieces of equipment . Without a systematic
approach , it would be impossible to analyze an existing process or to
design a new process . Therefore , chemical processes are broken down
into individual steps that recur in many other processes . The general
principles of these steps have been carefully studied and are frequently
well understood . If the principles are known, it is possible to design the
step to do the best possible job . The typical chemical process is analyzed
with five interdependent considerations :
1. Mass and energy balances
2. Thermodynamics and kinetics
3. Unit operations and chemical reactors
4. Instrumentation and control
5. Economics
These five subjects are closely dependent on each other , but their
principles can be studied individually .
Mass and Energy Balances . The laws of conservation of mass and
energy state that neither can be created or destroyed , but that they may
be changed in form . Thus , solid calcium carbonate can be changed into
calcium oxide and carbon dioxide by heating . A mass balance is based
on the conservation of mass : the mass of materials leaving a process must
equal the mass entering the process , if there is no accumulation of mass
within the process . The mass of the carbon dioxide and calcium oxide
must equal the mass of the original calcium carbonate . In this extremely
simple example , the mass balance is intuitively obvious . In complex

processes with dozens of chemical compounds and many process streams ,
mass balances must hold , and they are essential in accounting for the
material in process .
The law of conservation of energy requires that the energy added to a
process must equal the energy removed from the process plus any
accumulation of energy within the process . Often energy is changed in
form . Thus , in the previous example , the heat added to the calcium
its
carbonate to force decomposition converted into internal energy
of
is
the resultant carbon dioxide and calcium oxide The energy effects
of
all
an
physical and chemical changes must energy balance
be
considered
in
.
The analysis
as
of
of
nuclear reactions such the fission uranium has
,
,
be
shown that mass can converted into energy contrary the simplest
to
,
mass and energy
of
of
of
statement the law conservation There also
is
in a
.
all
mass energy conversion chemical reactions although the change

in
,
-
therefore neglected
to
mass too small measure and

is
be is
,
,
.
Mass and energy balances will considered thoroughly subsequent
in
chapters
.
Thermodynamics and Kinetics Thermodynamics deals with the

.
energy Many important

to
of
transformation from one form another

.
practical conclusions can

be
of
derived from the two fundamental laws
thermodynamics The energy balance which
of in
mentioned the
is
,
.
an
previous paragraph and developed Chap expression the

in
is
6,
.
thermodynamics The second law states that process

of
first law
in
a
.
involving heat transfer alone energy may transferred only from

be
higher temperature a
to
lower one The thermodynamic analysis

of
a
a
.
conclusions concerning the feasibility and efficiency

to
process leads
of
the
various process steps Thermodynamics also useful determining the
in
is
.
composition phases equilibrium and predicting the distribution

of
of
in
in
chemical species equilibrium

in
reaction
.
Kinetics considers the rate which chemical compounds react Data

at
reaction are necessary the design

on
of
of
rate the industrial chemical

in
reactors discussed the next section

in
thermodynamics
of
The fundamentals and kinetics covered

in
are
physical chemistry books Applications are discussed many chemical
in
.
engineering books.8,9
Unit Operations and Chemical Reactors chemical process can
be
A
.
broken down into series steps involving physical

or
chemical changes
of
a
The chemical changes are chemical reactions and are carried out
in
various
Such reactors may
be
types industrial chemical reactors

of
small
a
.
stirred pot pipe The quantitative calculation

or
of
of
of
hundreds feet
.
reactor size depends upon the rate the reaction the chemical equilib
of
rium the flow rates and other factors The chemical principles reac
of
,
.
tions are developed in physical chemistry courses . The design of reactors

is covered in books and courses on chemical engineering reaction kinetics .
A few elementary principles will be discussed in later chapters .
Often many of the steps in a chemical process involve no chemical
reaction . The handling and mixing of reactants and the separation and
purification of the products involve physical changes . Those physical
changes which are recurrent in many chemical processes are classified as
unit operations . There are a large number of unit operations ; several of
the important ones will be described briefly , so that the reader will be
familiar with what the operation accomplishes . It is necessary to under
stand the basic function of each unit operation to be able to make mass
and energy balances on the process . The principles of unit operations
are fundamental to the field of chemical engineering and are covered in
many basic courses and books..4 The principles are summarized briefly
in the following paragraphs .
the mate
all
Fluid Mechanics . In almost chemical processes some
of
,
liquid they moved through the process
be
rials are fluid
or
gas and must

,
(
by
equipment Energy supplied pump
be
or
to
move the fluid must
a
.
Quantitative evaluation energy flowing

of
other means the balance
in
.
fluids requires knowledge the fundamental thermodynamics and

all of
a
fluids Nearly the other unit operations depend upon

of
mechanics
.
Chemical engineers are sometimes referred
to
fluid mechanics
as
.
glorified plumbers theoretical plumbers Considering the maze

or
,
.”
"
"
"
piping present many chemical plants such labels are not

of
like miles
in
mechanical engineer
Of
entirely unjustified
or
course the chemical

,
.
designs the piping system the plumber installs
of
The mechanism
it
;
flowing fluid closely related

is to
momentum transfer the mechanisms

in
is
a
This analogous behavior under

in
of
heat and mass transfer useful

.
standing the three transfer processes and solving problems

in
each field
in
go .
Many chemical reactions progress more rapidly
or
Heat Transfer
.
completion the temperature other than room temperature

to
more
is
if
chemical reactions usually release

or
Furthermore absorb heat There

,
an
necessary products
in
or
to
fore often heat cool the reactants and

is
it
,
extremely important
an
industrial reaction This makes heat transfer

.
unit operation Heat transfer also involved the vaporization

in
or
is
.
process stream often possible heat one process

to
It
of
condensation
is
a
stream while cooling another piece equipment called

of
in
heat
a
a
exchanger which the fluids flow past each other separated by metal
in
a
,
wall through which heat

to
transferred from the hotter stream the

is
Recovery heat from product streams often economically

of
colder
is
.
important common example gas liquid heat exchanger

of
the
is
A
-
.
an
automobile radiator The chemical reaction automobile cylinder

is in
is
.
up
by
strongly exothermic and the heat released taken the cooling

,
water which circulates through the engine . When the cooling water
reaches the radiator , heat is transferred to the air .
Mass Transfer . In many unit operations one component of a fluid
phase is transferred to another phase because the component is more
soluble in the latter phase . The distribution of components between
phases depends upon the equilibrium of the system . Such transfer of
material between phases is called mass transfer. Mass transfer may be
used to separate products and reactants after an incomplete chemical
reaction ; it may be used to remove by- products and other impurities to
obtain highly pure products ; it may be used to purify raw materials .
The various mass - transfer operations have different names depending
its
upon the phases being processed . In distillation a liquid mixture at
boiling point contacted with saturated vapor mixture
of
the same
in is
components different proportion The components are transferred

.
between the phases until equilibrium the phases are
or
established
is
separated An important use distillation the separation

of
of
crude
in
is
.
petroleum into various components such gases gasoline lubricating

as
,
,
oil
in In
oil and fuel gas absorption component gas phase

of
dissolved
is
a
a
by ,
liquid phase contact with The opposite gas absorption

of
is
it
a
desorption stripping where component the liquid phase trans

or
of
is
a
,
the gas phase Gas absorption

to
of
ferred the manufacture
in
used
is
.
sulfuric acid where SO3 dissolved by water

in
gas stream
is
a
,
.
unit operations involve
of
number simultaneous heat and mass

A
another liquid
In
vaporized and the

or
transfer humidification water

is
,
,
.
vaporization must the liquid

be
to
of
heat transferred Dehumidification

.
vapor general the condensa

or
of
the condensation water from air

in
is
,
,
tion any vapor from permanent gas

of
of a
evaporation part vaporized and the

of
In
the solvent solution

is
a
,
evapo
In
crystallization enough
of
solution concentrated the solvent

is
7
,
.
give saturated solution from which solid crystals precipitate

to
rated
a
another liquid
In
drying evaporated from

or
water solid
is
a
,
In .
There are several solid fluid mass transfer operations solid liquid
-
-
-
by
leaching soluble component solid phase dissolved

A or
is of
aa
aa
extraction
is
,
,
liquid common example leaching the coffee pot where hot

of
a
,
.
adsorp
In
water dissolves the soluble coffee from the insoluble grounds

.
liquid adheres
of
solid
to
component
or
gas the surface

of
tion
a
a
,
In
in
of a in as
adsorbent such charcoal ion ions exchange

solution are
,
,
.
exchanged for ions the solid ion exchange resin Zeolite water softeners
-
are applications particular ion exchange resin

of
Another group unit operations depends upon the principles

of
fluid
solids and liquids
on
an
achieve separation Filtration

to
of of
mechanics
.
by
industrial scale the separation liquid from solid passing the

is
liquid through impermeable

is
to
as
medium such cloth which the

a
a
,
,
solid . Sedimentation is the settling of finely divided solid in a liquid to

increase the concentration of solids in the slurry . Elutriation separates
solid particles of different size or density , using the differences in settling
velocities in a fluid .
Many other unit operations could be listed . However , those men
tioned are the widely used ones . A great variety of equipment is used
to perform the various operations . Further information may be found
in texts and references on unit operations . 1,4,6
Instrumentation and Control. In all chemical processes it is necessary
to know such process data as flow rates , compositions , pressures , and
temperatures , so that the operator and production engineer can tell that
the process is functioning properly . In the typical chemical process
many instruments are used to measure , indicate , and record the necessary
process data .
It
is often desirable to use an automatic control , so that not only does
the instrument measure and record a variable , but it also maintains the
variable at a predetermined value . If the variable begins to change from
the proper value , the automatic control initiates corrective action to
its
return the variable to proper value For example the temperature
,
.
give the desired yield

be
of in
to
chemical reactor must often controlled
a
products the reaction endothermic the reactor might have

If
is
a
,
.
jacket supply The temperature
in
of
steam heat the materials the
to
reactor measured by temperature sensing instrument such as

is
to a
,
-
thermocouple The signal paper chart recorder

to
transmitted
is
-
.
give the operator the temperature variations with time The

of
record
a
by
temperature signal
to
also sent the controller which has been set

is
the operator maintain the desired temperature the temperature

to
If
.
the reactor begins fall below the desired value the controller opens
to
of
on
supply more heat the heating jacket

to
to
the steam valve the reactor

.
Conversely the reactor temperature too high the controller closes
is
if
,
,
The steam valve may any position between fully

be
the steam valve

in
.
open and fully closed

.
Automatic control may applied almost any process variable that

be
to
often maintained by the

be
Control
of
can measured variable

is
a
.
easily Automatic con

of
measurement another more measured variable

.
trol reduces human operators can give faster and

of
In It
the number
.
more accurate control than human operator countries with high

a
the United States rapidly

as
labor costs such automatic control

is
,
increasing
.
The coupling electronic computers makes

to
of
automatic controllers
no
possible process with human control Such plants are

to
run
it
now operation The engineer determines the best operating conditions

in
and designs the process controls and computer give the optimum
to
,
,
results . In operation , the instruments transmit process information to

the computer . The computer uses the information to determine whether
the process is operating at the best conditions . If it is not , the computer
initiates corrective action through the control system .
Although automatic process control has eliminated many low - skill
human operators , it is still necessary to have one or more highly skilled
operators present to observe that the plant is functioning properly . It
is also necessary to have a large highly trained maintenance staff to repair
the process and control system when it breaks down . The more complex
the control system , the greater the chance for breakdown . Of course ,
automated chemical plants are more expensive to build and require a
much higher degree of knowledge on the part of the design engineer and
the operating engineer .
Although the principles of chemical reactors , unit operations , and
instrumentation and control can be studied separately , in the design of
It
therefore
all
a chemical process these areas are closely
is
interrelated
.
necessary components process
to
to
of
of
consider the interaction the
an a
all
process This extremely

of
determine the over behavior often

is
a
-
difficult and complex job process dynamics must
be
of
consideration
A
.
included any complete process design

in
Economics No matter how efficiently process operates produce
to
aа a
.
final product high purity the process the product cannot

of
failure
is
if
a
,
be
profit chemical plant built thorough market

is at
sold Before
is
a
a
to .
analysis the product can

be
of
made determine how much sold and

is at
what price possible the product the price

to
of
Often sell more

if
is
it
.
lower Present and future competition from other producers must be

.
As
carefully evaluated the plant designed many economic analyses

is
,
.
determine the least expensive design which will produce the

to
are made
desired quantity product minimum price manu
at
of
of
the cost
If
a
attractive profit
an
sufficiently below the selling price give

to
facture
is
the plant will

be
built the product successful and profitable

If
is
a
.
competitor may find the market attractive and enter with perhaps
it
a
to by
an
somewhat better product produced lower price improved

at
a
process then necessary for the older producer improve his

It
is
.
be
process and product

he
will
or
of
forced out the market

,
An example the highly competitive nature the chemical industry

of
of
all
industrial ethyl alcohol Before the Second World War nearly

is
by
industrial ethyl alcohol was produced fermentation from natural

sugars Since the war production ethyl alcohol from natural gas and
of
,
.
all
petroleum has greatly increased until today about per cent

90
of
,
ethyl alcohol produced this manner Alcohol from fermentation

in
is
.
its
did not compete economically

to
and use now almost limited

is
,
medical and beverage purposes

.
The work of the chemical engineer can seldom be divorced from

economics which influences the development
, , design , construction , and
operation of any competitive chemical process .
THE FLOW SHEET AS A REPRESENTATION OF A

CHEMICAL PROCESS
The complete design specification for a medium -sized chemical process

would cover several hundred pages . It would include diagrams , tables ,
all
aspects the plant including chemical mechanical
of
and discussion of
,
,
,
electrical metallurgical and civil engineering considerations To under
,
.
engineer must have considerable training
an
stand complete design
a
,
and experience
.
flow sheets are prepared

In
many cases simplified illustrate the
to
do
process These are often for special purpose and not show all the
a
.
process common type flow sheet shows the major unit

of
of
details
A
a
operations and chemical reactors with their interconnecting piping and

an
the materials being processed The units are not

of
identification
for
scale but the drawing may resemble the equipment used
to
shown
,
the operation diagram would graphic process flow

be
Such called
a
a
.
For small process pictorial flow sheet with

of
sheet few units

a
a
,
.
drawings equipment approximately scale may Photo
be
to
of
used
.
graphs are usually unsatisfactory because the arrangement and connec
tions are seldom clear On process flow sheet the equipment arranged
is
of a
.
logically materials through the process but photo

to
show the flow
a
,
graph shows the final physical arrangement determined structural by
requirements without regard the process flow All tall distillation
to
,
columns may grouped together for structural support and large heat
be
exchangers may grouped for ease The successful

be
of
maintenance
.
engineer relate them

to
to
chemical must learn read flow sheets and to

the actual plant layout
.
sufficient data are available quantitative process flow sheet may

If
a
,
prepared showing the flow rates compositions temperatures

be
and
,
,
Such flow sheets may very compli

be
pressures throughout the process

.
simplified examples graphic quantitative

of
cated Several and flow

.
sheets are included Chaps and

in
9
7,
8,
.
Flow sheets showing instrumentation and controls are often prepared

.
graphic flow sheet distillation column showing the instrumentation

of
A
1.1
Fig
in
and controls given The figure shows more detail than

is
is
.
all
necessary for understanding process itself

an
of
the over
A
less
.
-
1.2
graphic representation distillation tower Fig

in
together
of
shown
is
a
,
.
with conventional representations other unit operations

of
and chemical
reactors These symbols are not standard because equipment varies
,
.
widely ,but they will be used along with others in the flow sheets in the
remainder of this book . The significance of the symbol can usually be
deduced by reference to the discussion of unit operations in the previous
Condenser
Cooling water
Reflux drum LLC

Reflux
FRC Distillate
PRC
product
FR
VP
RC
Feed
FRC
FRC
LLC
Steam
Reboiler
Bottoms
product
Р pressure Processstream
F – flow Signalfrom
LL – liquid level controllerto
-
VP vaporpressure
controlvalve
R recorder
C -
controller
Signalfrom
sensingelement
to instrument
Fig . 1.1 . Graphic flow sheet for a distillation column showing instrumentation and
control .
section . There are many variations on the symbols shown , especially in

chemical reactors , which have a wide variety of sizes and shapes .
Product flow sheets can be prepared for large chemical plants in which
the products of certain chemical processes are the starting materials for
others . In product flow sheets the chemical processes are shown as
simple blocks , with the starting material and product streams flowing to
and from each process block . Examples of product flow sheets will be
Piping Valve Pump Compressor
Heating or Heater or Heat Direct fired
2
cooling coil cooler exchanger heater
o do
C
Tank Chemical Agitator Filter Rotary

( storage, etc. ) reactor press filter
( various shapes )
Fig . 1.2 . Flow - sheet symbols for

various operations .
Distillation Gas absorption column

column ( similar columns for
liquid extraction , and
other mass transfer
operations )
found in Chap for a petroleum refinery and for a petrochemical plant .

. 9
Flow sheets are useful graphic representations

of chemical processes .
In this book quantitative flow sheets will frequently be used as a basis
for mass and energy balances . More information on preparation of flow
sheets may be found in Ref . 11 .
PROBLEMS
Most require reference to other sources usually available in the

of these exercises
library . references given at the end of this chapter , the following
In addition to the
sources are useful : Business Week ; Chemical Week ; R. E. Kirk and D. F. Othmer ,
“ Encyclopedia of Chemical Technology , ” Interscience Publishers , Inc. , New York ,
1947-1957 .
1.1 . For one of the following chemicals : chlorine , ammonium nitrate , calcium chlo
ride , sodium hydroxide , hydrochloric acid , titanium dioxide , methyl alcohol , acetone ,
aniline , phthalic anhydride , phenol - formaldehyde resin , polyvinyl chloride , poly
ethylene , penicillin
a . List the raw materials required .
its
b . Summarize a common process for manufacture listing unit operations and
,
chemical reactions include graphic flow sheet when possible
a
;
.
List the uses
of
the chemical
c
.
its
brief history any company listed Table 1.2 listing major
of
1.2 Write
in
a
,
.
products
.
for
1.3 Determine the total assets and net sales for the latest available year any
.
company listed Table 1.2 How do they compare with the figures listed
in
?
.
1.4 List common examples from everyday life for each the following unit oper
of
.
ations fluid mechanics heat transfer evaporation drying solid iquid extraction
,
,
:
-l
dehumidification filtration
,
1.5 Draw simplified process flow sheet from the following process description
a
:
.
by
air
Pure oxygen liquefying and distilling recover pure oxy

to
manufactured
is
it
air
gen and nitrogen The entering contacted with potassium hydroxide solution
is
.
air
gas absorption tower

of
remove carbon dioxide The carbon dioxide
is in
to
free
a
to (
)
its .
then sent through four compressors

to
increase pressure 200 atm After each .

C air
compressor there water cooled heat exchanger

to
cool the which has been

is
a
,
-
air
heated during compression

30
at
The resultant 200 atm and sent series

to
is
a
°
.
by
-30 refrigerated ammonia

to
four heat exchangers where

air of
cooled This
C
is
it
.
by
further cooled from –30 passing through heat exchangers

to
is
180
–
C
it
°
air
which use the product nitrogen and product oxygen
as
coolant fluids The cold

to is
.
air
passed through expansion valve into

an
distillation column The distilled

is
a
give distillate product per cent nitrogen and per cent oxygen and
98
of
bottoms
2
a
product per cent oxygen and per cent nitrogen

99
of
1.6 Draw simplified process flow sheet from the following process description
a
:
.
Hydrochloric acid may the following

be
manufactured from salt and sulfuric acid

in
process Sulfuric acid and salt are fed furnace where they are mixed and indi
to
of a
.
rectly heated
At
the high temperature the furnace the sulfuric acid and salt
.
off
react giving HCl gas which flows with some air from the furnace through heat
a
,
by
exchanger where cooled water The HCl gas then passed successively
is
is
it
through two gas absorption towers the top

to
of
Water fed the second tower and

is
,
-
of .
supplied the top

of
the dilute acid from the bottom the second tower the first
to
is
Strong hydrochloric acid

at
of
tower withdrawn the base the first tower and

is
.
storage tank The HCl gas enters the bottom

to
pumped
of
the first tower leaves

a
,
.
the top
of
and flows into the bottom the second tower Waste gas withdrawn
by at
is
,
the top
at
of
blower the second tower

a
.
REFERENCES
1. Badger , W. L. , and J. T. Banchero : “ Introduction to Chemical Engineering , ”

McGraw - Hill Book Company , Inc. , New York , 1955 .
2. Chemical and Engineering News , Facts and Figures of the Chemical Process Indus
try , annually , such as Sept. 5 , 1960 .
3. Eckman , D. P .: Automatic Process Control ,” John Wiley & Sons, Inc. , New
York , 1958 .
4. Foust , A. S. , L. A. Wenzel , C. W. Clump , L. Maus , and L. B. Andersen : “ Princi
ples ofUnit Operations ,” John Wiley & Sons , Inc. , New York , 1960 .
5. Haynes , Williams : “American Chemical Industry , ” D. Van Nostrand Company ,
Inc. , Princeton , N.J. , 1945–1949 .
6. Perry , J.
H. (ed .) : “ Chemical Engineers ' Handbook ,” 3d ed . , McGraw - Hill
Book Company , Inc. , New York , 1950 .
7. Shreve , R. N .: " The Chemical Process Industries ,” 2d ed . , McGraw - Hill Book
Company , Inc. , New York , 1956 .
8. Smith , J. M .: “ Chemical Engineering Kinetics ,” McGraw -Hill Book Company ,
Inc. , New York , 1956 .
9. Smith , J. M. , and H. C. Van Ness : " Introduction to Chemical Engineering
Thermodynamics ," 2d ed . , McGraw - Hill Book Company , Inc. , New York , 1959 .
>
10.
Taylor History Industrial Chemistry

F.
of
Sherwood William Heinemann
,
A
,
,
:
Ltd. London 1957

,
,
Dryden Chemical Engineering Plant Design

E.
F.
- C.
C.
11. Vilbrandt and
",
,
"
:
McGraw Hill Book Company Inc. New York 1959

ed
4th
.,
.
CHAPTER 2
THE CHEMICAL ENGINEER IN THE

CHEMICAL PROCESS INDUSTRY
Although the origins of the chemical industry may be traced back

hundreds or even thousands of years , the profession of chemical engineer
ing is little over 50 years old . The demand for the chemical engineer
began with the development of the modern chemical industry about
75 years ago and has grown rapidly with the industry .
ORIGIN OF CHEMICAL ENGINEERING1,3
As the chemical industry developed early in the nineteenth century

there was little or no intercommunication among the various parts of the
industry . Many products had been made for centuries , and the tech
niques of manufacture were based on experience . There was no recogni
tion of the elements common to several processes and no attempt to
systematize the knowledge of chemical processing .
In the latter half of the nineteenth century the great expansion in the
chemical industry led to an increased demand for leadership trained in
the fundamentals of chemical processes . This demand was first met by
industrial chemists , who were trained in chemistry and were interested
in applying their chemical knowledge to industrial processes . Industrial
chemists usually were specialists in a particular process . When college
instruction in chemical technology was initiated , it was organized around
specific industries and was generally limited to a description of the equip
ment and techniques of the particular processes . There was still little
attempt to systematize the fundamentals of chemical processing .
One of the earliest attempts to organize the principles of chemical
processing and to clarify the professional area of chemical engineering
was made in England by George E. Davis . In 1880 he tried unsuccess
fully to organize a Society of Chemical Engineers . He recognized that
the problems of the chemical industry were engineering problems requir
ing the application not only of chemistry but also of physics . In 1887 he
gave a series of lectures which were expanded and published as “ A
Handbook of Chemical Engineering " in 1901. In his lectures Davis
25
presented the concept of unit operations , although the term itself was
coined in 1915 by Arthur D. Little in the United States .
In 1888 the first course in chemical engineering in the United States
was organized at the Massachusetts Institute of Technology by Lewis M.
Norton , a professor of industrial chemistry . The course applied aspects
of chemistry and mechanical engineering to chemical processes. The
program was later expanded and modified by William H. Walker . Other
early courses in chemical engineering were given at the University of
Pennsylvania , at Tulane University , and at the University of Michigan .
In the early years of the twentieth century chemical engineering began
to gain professional acceptance . The American Chemical Society had
been founded in 1876 , and in 1908 it organized a Division of Industrial
Chemists and Chemical and authorized the publication of a
Engineers
Journal of Industrial and Engineering Chemistry , which is still a leading
publication . A week prior to the organization of the Division by the
American Chemical Society in 1908 a group of prominent chemical
engineers met in Philadelphia to found the American Institute of Chemi
cal Engineers . These two societies are today the spokesmen for the
chemical engineering profession .
As the American chemical industry expanded under the impetus of the
First World War , the demand for chemical engineers increased rapidly .
The United States achieved world industrial leadership , and chemical
engineering became almost an American institution . Although it
originated in England , it developed more rapidly in the United States ,
and was almost nonexistent in other countries of the world until after the
Second World War . In Germany , for example , there were no chemical
engineers . Germany's great chemical industry was designed and
operated by mechanical engineers and chemists . Since The Second
World War chemical engineering has developed in several countries .
WHAT IS CHEMICAL ENGINEERING ?
Chemical engineering is a synthesis of chemistry and engineering .

Although the profession grew out of industrial chemistry , today it is
based as much on physical principles as on chemical fundamentals .
There are many definitions of chemical engineering . Many of them are
either too specific or too vague . One popular definition : " A chemical
engineer carries out on a large scale reactions developed in the laboratory
by the chemist ,” is trueas far as it goes , but it does not show the broad
scope of problems encountered by the chemical engineer . The unit
operations are not obviously a part of this definition . The typical
chemist has little knowledge of any of the unit operations in theory and
practice .
THE CHEMICAL ENGINEER IN THE CHEMICAL PROCESS INDUSTRY 27
A facetious definition of chemical engineering makes a point : “ A

chemical engineer is one who talks engineering in the presence of chemists ,
chemistry in the presence of engineers , and politics in the presence of
both . " A unique characteristic of the chemical engineer is that he can
talk to and understand both chemists and other engineers . He must
understand the research findings of the chemist , and he must be able to
use engineering fundamentals to design and operate a new chemical
process based on these research findings . It is this versatility that has
made the chemical engineer indispensable in the chemical process
industry .
The
official definition of the American Institute of Chemical Engineers
is sufficiently broad to include aspects
all
the profession chemical
of
:
engineering the application the principles the physical sciences
of
of
is
,
"
together with the principles
to
of
economics and human relations fields
,
that pertain directly and process equipment
to
processes which matter
in
change state energy content composition
to
treated
or
effect
in
is
It .”
Chemical engineering unique among engineering disciplines
is
.
requires thorough understanding and mathe chemistry physics
of
a
,
do
matics whereas the other fields engineering usually
not require
of
a
,
thorough understanding chemistry For this reason chemical engineer

of
ing will probably always remain somewhat apart from both chemistry
and the other branches engineering
of
WHAT DOES CHEMICAL ENGINEER DO

A
As the chemical industry grew size and complexity

of
the work the

in
,
an
chemical engineer required ever growing background

of
education and
-
experience Today chemical engineer may work many fields

of
in
one
a
.
within the profession chemical engineering the fields require

of
of
Some
.
training beyond
an
special undergraduate curriculum The additional

.
training may graduate work the job training The

be
or
on
formal
-
major areas work within chemical engineering are given the follow
of
in
ing list
.
Research
Process development
Process design and evaluation
Plant design
Construction
Production supervision
Plant technical service
Product sales
The fields and often overlap . A chemical engineer

are interrelated
may work in a single field with a large industrial organization , or he may
work in several areas simultaneously , especially in a small company .
Transfer from field to field is very common , as company needs and the
all
engineer's interests change . In his work the chemical engineer works
closely with specialists chemistry and other fields engineering and
of
in
pure science
.
Chemical engineering research may divided into funda
be
Research
.
mental exploratory and process research Fundamental research
is
,
,
.
many areas chemical engineering Such research results
of
carried out
in
.
the development new knowledge the principles the unit opera
of
of
of
in
In
tions industrial reaction kinetics and chemical process control areas
,
.
subject experimental analyses fundamental research develop
to
to
used
is
,
new theory and experimentally For example fluid
in
to
test
it
a
,
.
currently the subject intensive theoretical
of
mechanics turbulent flow
is
,
and experimental study develop understanding an

the fundamental
to
of
physical mechanism The findings fundamental research are fre
of
.
quently immediately useful but the research program
to
initiated
is
,
increase the general knowledge rather than for specific applications The
an
chemical engineer working fundamental research must have
in
excellent background physics mathematics chemistry the
as
as
well
in
,
principles chemical engineering He often specializes and becomes an
of
expert He often has taken graduate

as
one area such mass transfer

to in
the M.S. Ph.D. chemical engineering Fundamental

in
or
work
.
in
chemical engineering
in
research carried out universities and

in
is
many industrial concerns separate and distinct from pure research

It
is
.
in
chemistry
.
Exploratory research less frequently the responsibility

of
the chemical
is
engineer More typically Here the

of
the work the chemist

it
is
,
.
.
object particular may

to
find reaction which have commercial

is
an
of oil
possibilities For example company may ask group

of
research
a
,
.
oil
study the reactions hydrocarbons found using various

in
to
chemists
catalysts The object may particular catalyst
be
to
find reaction
a
,
.
temperature and pressure which will yield product higher octane

of
a
,
number than the starting material The conversion hydrocarbons

to
of
.
In
other hydrocarbons higher octane called reforming the com

of
is is
process starting naphtha hydro

of
mercial the material mixture

is a
,
by
oil
the distillation complex mixture

of
It
carbons obtained crude

a
,
.
and many reactions occur exploratory research the chemist may

In
.
investigate several the pure compounds which are present the mix
of
in
the single component For example

to
of
ture determine the reaction

,
.
an
cyclohexane naphtha
of
It
common constituent has octane

is
a
.
for
modern gasolines
be
of
It
number 78.6 too low can reformed under

,
.
proper conditions to benzene , which has an octane number of 113.6 .

The reaction is
H H
С С
H.C CH catalyst
HC CH
900° F
11 + 3H2 ( 2.1 )
H.C CH
500
CH ,
ibs
HC
sq
2
.in
/
HС
H
The reaction equilibrium and rate give perhaps per cent conversion
90
a
cyclohexane Other catalysts
to
at
of
benzene the conditions indicated
.
and conditions give different conversions Another reforming reaction
is
.
isomerization For example normal heptane octane number may
0
,
.
,
(
)
an
isomeric heptane with higher octane number

be
to
converted
a
:
CH
3
catalyst
CH
CH3CH2CH2CH2CH2CH2CH3 CH3CCH2CH2CH3 2.2
→
,
900
)
sqF
/ °
500 lbs
in
.
CH ,
Normal heptane Isoheptane
2,2
dimethylpentane
(
)
-
octane No. 93
,
Both the reactant and product contain hydrogen

16
carbon atoms and

of 7
atoms they are therefore both isomers heptane

;
The exploratory research group would try many catalysts and various
-
on
operating conditions small laboratory scale explore wide range

to
or of
a
possibilities The research program may extend over several months

.
even years Although many

the attempts prove infeasible
of
few
a
on ,
.
results may commerically promising and these will passed

be
be
to
the
,
process research group for further study

-
Process research takes promising results from exploratory research

on
and intensively studies them determine their com

to
bench scale
a
mercial feasibility Process research determines operating conditions

.
for
commercially feasible process yields data for preliminary economic

a
a
,
evaluation and provides information for design pilot plant for further
of
a
,
development the process Starting with the results exploratory

of
of
.
research the process research group will study the process under wide
a
,
an
range operating conditions attempt

to
discover what variables

in
of
carefully controlled
be
temperature pressure concentration etc. must

,
,
,
)
(
give maximum
be
at
to
and what values these variables must maintained

a
yield the desired product For example the hydrocarbon reforming

of
in
,
.
cited above , variables to be studied would include the temperature ,

pressure , time allowed for reaction , catalyst type and size , and the flow
rate and composition of the entering stream . It may be found that the
best yields of higher -octane product are obtained at 900 ° F and
500 lbs / sq in . pressure , but that the entering hydrocarbon must be
diluted with hydrogen to prevent decomposition to carbon at this elevated
temperature . The process -research group would study not only pure
hydrocarbons , but also naphtha , the complex mixture of hydrocarbons
which would be the feed in a commercial process .
A flow sheet for the bench - scale reactor needed for process research on
reforming is shown in Fig . 2.1 . The unit is small ; the reactor may have a
Pressure
control valve
Gas
Condenser
High - pressure
gas separator
Catalytic
Hydrocarbon reactor
feed
Gas
Hydrogen Pressure -reducing
valve
feed Low - pressure
Preheaters gas separator
Liquid
product
for
2.1
Fig .
on
Bench scale catalytic reactor process research hydrocarbon reforming

-
.
.
The ultimate pilot plant and
cu
only 100 catalyst

of
of
volume cm
.
commercial installation would have continuous flow reactors therefore

-
,
;
the bench scale has continuous feed hydrocarbons and hydrogen

of
and continuous withdrawal products The

of
continuous reaction
,
hydrocarbon ydrogen feed gas The gaseous products are con

is
a
.
-h
liquid after the reactor and are separated from the remaining
to
densed
a
gas which mostly hydrogen with some light hydrocarbons

is
,
The process research group must obtain sufficient quantitative data

to
-
make possible preliminary economic process evaluation Economic

a
each step the development process

at
evaluations are made

of
in
step substantially greater than the previous

of
Because the cost each

is
step the process must look continually more promising the work
as
,
progresses Exploratory research relatively inexpensive process

is
;
.
may expensive complex equipment

be
of
research more because more

requirements and greater operating costs . The next step , process

development with a pilot plant , is very expensive , because the equipment
is closer to an actual commercial plant . A bench -scale unit for process
research may cost $ 15,000 ; a pilot plant , $ 150,000 ; and the full - size
commercial plant
, $ 3,000,000 .
Ifthe results of process research are economically promising , enough

data must be obtained to permit design of a pilot plant for process
development .
Process Development . After process research has demonstrated the
chemical feasibility of a new process and a preliminary economic process
and market evaluation has indicated a satisfactory profit , a decision must
be made concerning the extent of the process - development program .
It is seldom possible to skip process development and proceed directly
from process research to the design and construction of the full - size
plant . The large uncertainties regarding process operating conditions
and product yield almost always require the construction of a semiworks
or pilot plant . The pilot plant is a form of insurance . Although it is
expensive to build and operate , it may save much more money by elimi
nating uncertainties in the construction and operation of the commercial
plant . Any difficulties in start - up or operation of the full - size plant
results in a great monetary loss in the profit that would have been made on
the product .
In addition to supplying process information , the pilot plant may be
required to produce the new product for market research . In many
cases it is necessary to supply the prospective customer with samples of
the new product , so that he may test it and determine whether it satisfies
his needs . In this way , a market for the new product is established
before the commercial plant starts up . The pilot plant must yield a
product which is identical to the expected product of the proposed full
scale plant . Therefore , the pilot plant must duplicate the proposed
all
plant important process details

be
full - size will

It
in smaller and
.
produce less product but the units the pilot plant must function
if of in
of
the
,
same way the full size units the conventional parts

as
of
Some the
-
process need not duplicated the pilot plant For example

be
the
in
,
.
by
product must purified may general

be
be
distillation done
in
it
a
,
purpose batch distillation column usually available development

in
a
laboratory Distillation fairly well understood unit operation The

is
a
-
.
typical development laboratory has large variety general purpose

of
a
special urpose pilot plants

its
equipment addition The utiliza

in
to
.
-p
tion such equipment money and time

in
of
of
saves the construction

a
pilot plant
.
all
an
The pilot plant many respects ignorance

of
admission
in
If
of is
the fundamentals chemical engineering were well understood would

it
,
be possible to build a full - scale plant based on the results of extensive

process research . Because pilot plants are expensive and time -consum
ing , there is pressure to eliminate them whenever possible .
Process development may be divided into four steps :
1. Planning the development program

2. Designing and building the pilot plant
Operat on of the pilot plant
3.
4. Correlation , presentation , and eva uation of the data from the pilot
plant
In planning the pilot plant , the development engineer must work

closely with the process -research group and with the design engineer .
He must thoroughly understand and utilize the results of process research ,
and he must make certain that the ultimate data from the pilot unit are
what the design engineer needs to design the full - size plant . The
development engineer must plan his program to obtain the maximum
information in the least time at minimum cost . He must determine the
critical process variables . In many cases he can conclude that it is not
necessary to study certain process variables , either because he can
predict their effect from theory or because he can determine that the
existing uncertainties are unimportant so far as the final product and
economics of the process are concerned . A pilot plant must be justified
economically . An extensive development program can be undertaken
only if the process looks highly profitable . Plann ng continues during
operation of the pilot plant, because the first data may indicate a desirable
change in program .
One of the first questions in the design of a pilot plant is that of size .
A small unit costs less , but a larger unit more closely approximates full
size conditions . Problems of scale -up are often complex and a matter for
careful study . Pilot plants should be simple and flexible . Simplicity
gives ease of operation . Flexibility is essential to permit changes in
operation indicated as data are accumulated . If corrosion appears to be
a problem , it may be desirable to test materials of construction , even
though the pilot unit has a relat vely short useful life compared to the
commercial plant . Existing general - purpose equipment will be con
sidered in the design of the pilot plant .
Operation of the pilot plant will provide data for design of a commercial
plant , develop operating procedures for the full - size plant , and perhaps
train operating personnel for the commercial plant . The development
engineer will supervise the pilot - plant operation , specify operating con
ditions , and analyze the resulting data to ascertain their utility and to
determine desirable changes in operating conditions . The plant may be
actually run by skilled technicians . The engineer who will be in charge
of the operation of the commercial plant may help in the operation as part
of his training . Operating the pilot plant may show that changes in
equipment are necessary to give satisfactory results . These changes are
more easily made in the pilot plant than in the commercial plant . It is
better to make mistakes on a small scale .
Evaluation of results begins as soon as the first data are taken . The
development engineer must eva uate the data and present them in аa form
useful to the design engineer . Data which are not immediately useful
must also be carefully recorded for later possible use .
After sufficient design data have been taken , the pilot plant may con
tinue to operate to produce a product for market research and to obtain
further operating information . Even after the commercial plant is in
operation , the pilot plant may continue to operate to test suggested
improvements in the process .
The reforming process discussed earlier underwent extensive process
development . A flow sheet for the pilot plant is shown in Fig . 2.2 . The
pilot plant is much more complicated than the bench - scale unit for process
2.1
research shown in Fig . The unit uses naphtha supplied from the
.
refinery Because the composition the naphtha varies somewhat

of
is
it
,
.
necessary give the desired uniform

to
distill two distillation towers

to
in
it
feed The feed then mixed with diluent hydrogen and heated by
is
.
exchanger
in
cooling product further heated
It
heat
in
hot stream
is
a
a
The
to
molten lead heater feed then goes

the three reactors which are
a
filled with solid platinum

based catalyst Because the reforming
a
the process stream

be
to
reactions are endothermic heat must added

,
between reactors The product stream from the third reactor cooled
is
.
by
up
by
heating the feed and further cooled heating water another

in
heat exchanger the separator where the diluent hydro

to
It
then flows
.
The liquid product distillation tower for

to
gen removed sent

is
is
a
.
hydrocarbons and the final product

of
removal the most volatile

is
,
withdrawn from the bottom The

as
of
the tower stabilized reformate

.
an
hydrogen recycle gas absorption tower where hydrogen

to
sent
is
sulfide scrubbed out with monoethanolamine MEA solution The

is
sulfur compounds the feed naphtha yield hydrogen sulfide which

in
up
poisons the catalyst would continuously build the hydrogen

It
in
.
recycle ver removes the hydrogen

to
were not removed second

A
it
if
that the solution may

be
so
sulfide from the monoethanolamine solution

,
The hydrogen compressed and sent back

be
mixed with the

to
reused
is
.
The recycle hydrogen dilutes the naphtha feed

Without the
of
it
feed
.
.
naphtha decomposes giving carbon which coats the catalyst and makes
,
When the pilot plant was first built provision was made
no
inactive
to it
,
.
gas The catalyst poisoned

H
remove the was and was then

it
S
,
.
install the MEA This problem illustrates the use

to
decided scrubber
.
Light
hydrocarbons
Catalyticreactors
Storage
Storage
Reactor
Reactor
Reactor
Pump tm Em
Naphtha Leadbath Leadbath Leadbath

from heater heater heater
refinery
Light
hydrocarbon
columnDistillation
columnDistillation
gas
34
H2S gas
H2
addition
-- to
Feed product
heat exchanger Hydrogen
compressor
Heater
Stabilizer
distillation
Hydrogenrecycle column
MEA
absorbor H2S
stripper H2S
Separator
Heavy
hydrocarbons Cooler Stabilized
0
)(
reformate
Cooler product
.
.
)
(.
Fig 2.2 Reforming pilot plant Courtesy Atlantic Refining Co.

fulness of a pilot plant in determining difficulties which might arise in

the full -scale plant . Although commercial plants based on this pilot
plant have been operating for several years , the pilot plant is still used
to evaluate possible new catalysts .
Process Design and Evaluation . The process - design engineer is con
all
cerned with the design of the over - chemical process Generally
is he
,
.
not responsible for the detailed design pieces equipment this
of
of
is
;
normally the responsibility the project engineer plant design
of
in
.
Because the process esign engineer interested producing the desired
in
is
-d
as
product possible must examine many alternative
he
at
as
costlow
a
,
an
process steps economic optimum Economic evaluation
to
determine
by
the process
an
integral part process design may
be
of
It
carried out
is
.
by
an
design engineer economic nalysis group working closely with

or
-a
him
.
process design includes the following major items

A
2
:
all
Process flow sheet showing pieces equipment instrumenta of

1.
,
tion and controls and the operating pressures temperatures and flow
,
,
rates
on
on
all
Mass balances the over process and each unit the process
2.
in
-
,
all
showing yields products and purity process

of
of
streams the
in
Energy balances for

all
the process including heat xchanger

in
units
3.
requirements -e
Specification pump capacities and pressure requirements
of of
5. 4.
flow
,
,
Specification and configuration

of
size chemical reactors and

storage tanks
optimum operating conditions for the mass
of
Determination
6.
transfer operations required for the separation and purification

of
the
raw materials and products
Estimation utility requirements steam water electricity
as
of
such
7.
and fuel
an
with capital investment

of
Economic evaluation estimate and

8.
operating costs
all
The process esign engineer utilizes process research

of
the data
-d
development He works closely with the development engineer

to
and
.
determine the most economical processing units and the optimum oper
all
ating conditions Even with hand the process esign

at
information
,
.
-d
engineer must use his judgment filling gaps He never has

in
data
in
his
pre
all
must estimate many quantities using

he
he
the data needs

;
be ,
vious experience The process engineer must well rounded

as
basis
a
-g
chemical kinetics and unit operations

he
of
the fundamentals must

in
exercise his imagination and judgment design process with often

to
incomplete data His work involves numerous careful calculations

,
.
...
sometimes using available digital computers for the longer routine

calculations
.
The typical process design may divided into three progressively more
be
complete designs After exploratory and process research has shown
.
process technically promising the process esign engineer makes
be
to
a
of -d
an
quick design for magnitude estimate the process
of
order the cost
of
a
-
-
.
design necessarily superficial because only data
of
Such minimum
is
a
a
,
previous
on
The order magnitude estimate
of
available based
is
is
-
-
.
25
may within per
be
to
company experience and costs accurate
It
.
cent
.
magnitude
an
the process looks economically promising after
of
order
If
-
-
estimate process development program initiated and the process
is
a
,
,
-
design engineer uses the resulting data second design called
as to
make
,
the preliminary design This design time and data will
as
detailed
is
.
all
permit eight complete design On this

of of
It
includes items the

.
It
an
design the process may
of
based accurate estimate the cost
is
.
indicate areas which additional physical chemical and process data
in
,
final design With the preliminary
be
must taken before feasible

is
a
.
design and economic evaluation basis company management deter
as
a
mines whether the process sufficiently attractive proceed

to
Because
is
.
many attractive processes may the design and
be
under consideration
,
analysis must management judges given process on
be
If
accurate a
.
be
design that later proves inaccurate the engineer will
of
the basis
a
severely criticized for his error

.
management decides build the commercial process the process

to
If
design engineer makes his third design the final design This design
,
the most complete since the final plant will

be
constructed from
it
is
.
The process engineer uses his preliminary design basis modifying
as
a
according any new technical and economic data When the final
to
it
process design complete the plant esign group for the

to
sent
is
it
is
,
-d
detailed mechanical electrical and civil ngineering design

,
.
-e
an
Because process esign engineering requires excellent technical

-d
background many companies employ engineers with graduate training

,
the M.S. the Ph.D. The process engineer

or
an to
to
even considered
is
uphe
may called upon consult with the

be
expert
to
the area and

in
operating engineer and operation the plant

of
start
in
simplified process flow diagram commercial reforming plant

of
of is
A
shown Fig 2.3 Because simplified represents only part

in in
it
is
it
,
.
complete process design complete design would sev

be
item
A
a
1
all
eral hundred pages long and would include many flow sheets showing
flow rates temperatures pressures and compositions Figure 2.3 does
,
,
the auxiliary equipment nor does

to all
not show show the distillation

it
,
equipment remove the light hydrocarbons from the reformate The

.
H2
recycle
-
Gas liquid separator
Regenerated absorbent
Absorbent
Reactor Reactor Reactor storage
1
2
HAS
tower absorption
S
,
H
{
Reactor charge
furnace
37
WW
mW
ww Heat
exchanger
stripper H2S
Intermediate
Heater
furnace
Heat
exchanger Hydrogen product
Cooler
to
Naphtha ammonia plant
m
-
charge Gas liquid product

separator
Pump
Hydrogen
Hydrogen Crude reformed product
recycle
to
up
make compressor distillation system
Compressor
)
(
.
Co.
-
Refining
.
.
Fig 2.3 Full scale catalytic reforming plant Courtesy Atlantic
full - scale plant shown in this flow sheet closely resembles the pilot plant
shown in Fig . 2.2 . The full - scale plant uses naphtha directly from
the
plant The reforming reactions produce hydrogen Excess hydrogen
is
.
.
off
ammonia plant
an
hydrogen recycle
to
bled from the line and fed
.
Plant Design The plant design group translates results the process
of
-
.
design engineer into complete plans and specifications which will
be be
used
by
plant The plant design com
to
the constructors build the must
.
plete every detail
of
to
make firm estimate the cost
It
in
used
of
is
a
.
the plant and may serve
as
basis for contract between the chemical
it
a
,
company and the construction firm
.
The plant design group may include chemical mechanical electrical
by ,
,
-
and civil engineers The group supervised project engineer who
is
a
.
all
frequently chemical engineer with knowledge process
of
the over
is
.
He must coordinate the activities the various specialists his group
of
in
;
carefully analyzes the data supplied him by the process design
he
to
-
engineer and may make suggestions for modifying the fundamental
he
;
process which result substantial savings The process engineer and

in
.
the project engineer work closely analyzing such suggestions The
in
.
project engineer must concern himself with peripheral problems such
as
supply water and other utilities waste disposal and safety He may
of
.
the only person who has thorough understanding and responsi
be
of
a
bility for the entire design

.
Working closely with the project engineer are the designer and drafts
man The designer specialist particular phase plant
of
often
in
, is
a
.
design For example after chemical engineer has determined the num
aa
.
ber size and spacing plates distillation column mechanical

of
in
a
a
,
,
designer may specify the physical details the column the electrical
of
designer may specify the location and type instrumentation and con
of
trol and the structural designer considers the support framework and
,
for
foundations the column and auxiliary equipment The designers

.
on
make suggestions the project engineer specific points where money

to
might The designers supervise the draftsmen who make the

be
saved
.
detailed drawings each unit the process

of
of of of
the complexity modern chemical plant some design

of
Because
a
groups use small scale models the plant study the physical layout
to
-
equipment and piping Such models often bring out weaknesses

or in
of
layout which would make the plant difficult operate maintain

to
,
all
repair The project engineer ultimately responsible for

is
these
.
details
.
The project engineer works closely with the contractor who building
is
the plant Many questions arise during construction materials specified

:
.
may the time limit set further pilot lant work shows
be
in
unavailable
;
-p
that change one unit essential the contractor may suggest changes
in
is
a
;
in foundation because of unexpected soil conditions . The project engi

neer is also present at plant start - up , the completion of his months or
years of work .
The young engineer may start out as an assistant in the plant -design
group .. If he shows interest and aptitude , he becomes a designer . After
further experience , he may become a project engineer . Many draftsmen
and some designers are not college graduates , but they are highly skilled
technicians who make a career of drafting or designing .
Many of the pieces of equipment for the plant , such as pumps , heat
exchangers, and instrumentation , will be supplied by equipment vendors .
An equipment
vendor is a company that specializes in the design and
construction of a particular type of equipment . The vendor may build
a unit to the plant - design group's detailed specifications , or he may sug
gest a standard unit which the company makes . For example , the plant
design group specifies the pumping requirements , and the vendor suggests
a specific pump which will do the job . The vendor employs many
engineers in the development , design , and sale of his equipment .
Construction . The role of the chemical engineer per se in the construc
tion field is limited . A general background in engineering is helpful ,
but it need not be chemical engineering . Approximately 55 per cent of
professional chemical engineers are in construction supervision . The
construction supervisor is responsible for completing the plant in the
shortest time within the allotted budget . He must establish a construc
tion schedule which is realistic and then see to it that the schedule is
up
set
equipment delivery schedules and

he
maintained . He must must

,
expedite construction his own shops The construction supervisor

in
must carefully schedule manpower requirements keeping

in
mind the
,
various craft union regulations He must maintain good labor relations

.
avoid poor workmanship complete work stoppages

or
to
slowdowns
,
After the plant completed the construction engineer tests the equip
is
specifications
be
available for consulta

to
ment sure that meets He

is
it
tion on plant start up

.
-
All the steps the development new chemical process outlined

of
in
above are not necessarily carried out by the company that will use the
do
process few very large companies their own research development

A
,
.
design and construction Some companies carry the process through

,
design and turn construction over the several large chemical

to
of
one
design and construction firms Often the design and construction com
.
on
pany contracts complete the project relying the chemical company

to
for the necessary process development data Frequently company

a
,
.
by
may buy complete process which has been developed another com
a
by
pany the chemical design and construction

or
of
the same field one

in
all
firms These firms employ many chemical engineers fields The

in
.
.
company that developed the reforming plant described earlier contracted
its
out the plant design and construction . It has also sold design
to
oil
several other companies
.
Production Supervision The plant built but will run The
is
it
?
,
.
his
first job the production supervisor get new plant running
to
of
is
.
After days weeks intensive work the plant finally run
or
of
months
is
,
,
ning smoothly and producing the proper quantity and purity product
of
.
The plant under automatic control and few operators occasionally
is
a
,
check the instrument panel sure everything functioning properly
be
to
is
.
The production supervisor checks the daily record With the plant
.
running smoothly
what more there for the production supervisor
to
is
,
do
His job just improve operation He
to
has begun He tries
is
not
?
do
meeting design specifications
he
better
to
content with wants
.
an
always any design the
of
Because there element the unknown
in
is
,
production supervisor knows that there room for improvement He
is
.
adjusts process variables give optimum conditions improves
he
to
;
by
product quality removing contamination and reducing deterioration
:
by
reduces steam water power and materials requirements
he
careful
,
by
operation good labor relations

he
reduces labor costs efficient

;
,
methods and workable safety practices develops efficient mainte
he
;
,
procedures ensure minimum shutdown time for routine repairs

to
nance
;
up
he
procurement maintain adequate inventories

to
sets schedule
of
a
raw materials
.
After sustained and long range effort the production supervisor and
a
,
-
his staff will have the plant running perfectly They are prepared
of to
"
."
cope with any emergency equipment Their product
is
of
failure
.
excellent quality and selling well too well fact The sales depart
in
it
is
,
per cent more can the plant produce

25
25
ment states that can sell
it
per cent more than the capacity for which was designed The
it
yes Usually plant components are

of
answers often almost most the

is
overdesigned ensure their doing the job for which they are built and
to
often they can process more One unit which was designed more closely
.
an
the minimum will create attempt

to
bottleneck when made

to
is
a
increase production The production supervisor and his staff must find
.
by
equipment Care
of
and eliminate the bottleneck often the addition

,
ful analysis can increase plant capacity substantially and bring greater
profits The production supervisor can see his profits directly
in
more
.
efficient operation and additional production

.
the pilot plant

on
The process evelopment group continues work

to to
-d
important modification
an
and may develop produce better product

a
more cheaply The production supervisor works closely with process

.
development and design modifying the plant Process development

in
.
up
may come with totally new process that economically justifies shut
a
ting down the existing process after several years of operation . A com
peting new product may capture the market and force shutting down
the old plant .After years of intensive effort , the production supervisor
must be ready to abandon the old plant and move on to a new one .
his
Because the problems of the production supervisor and
of
staff
production engineers cover very wide range they need broad back
a
,
ground engineering rather than specialized training This broad
in
.
background gained experience by
The graduating chemical engineer
is
.
an
may start assistant production engineer

As as
of
small area the
to in
a
up
gains experience production engineer
he
he
process will move
,
,
.
assistant supervisor supervisor and perhaps ultimately plant manager
to
,
.
The reforming plant developed the earlier discussion has been
operating for several years Fig 2.4 Several additional in
It
shown
in
is
.
.
the plant pic
on
plants have been built the same design The product
of
.
used the higher octane automotive fuels needed today Some
in
tured
is
.
reforming plants recover and purify the benzene toluene and xylenes
,
produced and sell them starting materials for organic petrochemicals
as
.
Plant Technical Service The plant technical service group assists
.
up -
the operating engineer and operation prob
of
the solution his start

in
This group plant problem develops

as
lems serves the whole When

a
a
.
one area they move analyze the problem and suggest solution
to
in
in
a
,
operator Their work

to
the identical the more technical and less

is
.
production engineer The boundary responsi

of
routine duties
of
a
bility between the technical service group and the production supervisor
-
varies greatly among companies Some companies consider technical

.
no
all
part production
be
to
of
service and have over technical service

a
The production engineer solves his own problems

as
group described
,
the .
At
previous section the other extreme the production supervisor

in
,
.
all
technician with long experience who turns his technical problems

is
a
He
plant group handle rou

to
of to
over the technical service continues

-
.
In
tine problems range division

of
between these extremes

is
a
.
technical problems between production engineers and technical service

-
some cases the technical service group may only make

In
engineers
-
.
In
suggestions the final decision the production supervisor's others

is
;
the technical service supervisor may initiate changes especially where the
,
-
operator not an engineer

of is
the previous section may

to be
Much the technical work described

in
engineer He may
be
the technical service

to
delegated called
in
-
process difficulty
to
or
analyze breakdown determine and eliminate

a
,
for
increased production modernize the process

to
to
bottlenecks increase
,
product purity
.
The technical service group extremely important start p

of
in
is
a
-
-u
new process Often unusual and complex problems are encountered

.
.
1
4
8 6
Fig . 2.4 . Catalyticreforming plant : ( 1) furnace ; (2 ) building housing three reactors ;

for
purification reformed product H2S absorption tower

of
(3 ) distillation column
;
4
;
(
)
H2S stripper hydrogen compressor house control house heat exchangers

5
8
;
.
)
(
)
(
)
(
)
Courtesy Atlantic Refining Co.

)
(
Rarely does a large chemical process start without a hitch . The tech
nical -serviceengineer works closely with process development , process
design , and plant design in starting up a plant . Minor design and con
struction errors must be corrected . The process may operate but pro
duce a product of inadequate quantity and purity . Start- up may require
weeks or even months before the plant is functioning properly . The
engineers involved in start - up need a wealth of theoretical and practical
knowledge to overcome the difficulties encountered .
Product Sales . The ultimate economic justification of a chemical
process is the sale of
its
products For the present purposes product
,
.
sales may divided into four closely related areas
be
to
of
interest chemical
engineers market research product development technical sales and
,
,
:
customer technical service the chemical engineer chooses product

If
.
he
as as
sales his field will work closely with business specialists such
in
,
fields marketing and sales

economics
,
Market the first step new product sales begins long before
in
research
,
,
the new process operation answers the fundamental question
in
It
is
as ,
.
Will sell The market research group begins its analysis
as
it
soon
“
?
”
by
promising result reported the exploratory research group

is is
a
.
proposed product completely new market research contacts potential
,
users determine their needs and thereby establish whether

to
market
a
on
exists management decides continue the project
to
of
the basis
If
.
this preliminary market survey the pilot plant may produce sufficient
,
product supply samples potential customers that they may test

to
to
so
the product for their applications the proposed product one already
If
is
.
on the market market research determines how much more the mate
of
,
rial could produced New uses for the existing product are
be
sold
if
explored Market research continually surveys the chemical market

to
.
supply management with facts

on
general trends new products

It
in
may suggest areas possible economic return the exploratory research

to
of
group
.
Product development finds uses for new products and new uses for estab
lished products applied research and may require the
of
It
form
is
a
.
solution complex chemical and engineering problems

of
It
considered
is
.
part product sales because more concerned with the sale

of
the
of
is
it
a
product than
its
with manufacture The product evelopment

is
it
-d
by
group assists market research suggesting and developing new uses for
by
product assists the technical salesman developing modified

it
a
a
;
product for the particular assists the customer

of
use customer
it
a
service group by suggesting processing methods which the customer might

use with the product developing uses for products
of
Some the work

in
.
long range and exploratory Other product evelopment problems

is
-d
need immediate answers the problem major one the product

If
is
a
,
.
the
development engineer consults with his research department and
For example
to
customer work out solution customer may require
a
,
.
a very high purity product for his application The usual product may
.
-
be
not sufficiently pure The product development engineer will work
.
purifying
or
of
out means either before after sold the customer
to
it
in it
is
.
might suggest
he
On the other hand change the customer's process
a
,
eliminate the need for the high purity thereby saving the customer
to
,
money and selling the less pure product
.
Technical sales and customer technical service are inseparably related
.
The same engineer may act both capacities The technical salesman
in
.
on
He
its
sells his product proved technical superiority
it of
the basis
If .
must show the customer that will satisfy the requirement the
.
customer tries the product the technical salesman must retain the market
,
by
of
helping his customer solve any problems that arise the use
in
the
product This assistance customer technical service Some com
is
.
.
panies have special groups that assist the salesmen this area others
in
;
expect their salesmen handle the customer's technical problems
to
.
on
The technical salesman may call the product evelopment group
to
-d
is in
answer customers questions The product development group this
is
-
.
'
sense involved customer technical service Often product

in
sold
is to a
.
company willing supply

of
because
to
the service the customer
is
a
.
An excellent example the develop
of
in
customer technical service
the synthetic fiber industry after the Second World War The
of
ment
-
.
potential market for synthetic fibers was obviously the textile industry
.
But the textile industry was very old industry relying
on
natural fibers
a
cotton and wool and using dyeing spinning and weaving proc
as
such
,
,
all
esses developed over many years experience Not the processes

of
worked with synthetic fibers The textile companies were naturally

.
spend large amounts

for
money develop processes
to
reluctant
to
of
dyeing spinning and weaving synthetic fibers when natural fiber mate
,
rials were satisfying public demand As result the major chemical

a
to ,
.
companies producing synthetic fibers were forced develop dyeing and

weaving processes before they could sell their fibers the textile con
to
cerns They then allowed the textile companies use these new proc
to to
.
they would buy the fiber Dyeing proved difficult problem

be
aa
esses
if
with some synthetic great product develop

of
fibers deal research and

A
.
ment was required overcome this problem The tremendous growth

in to
synthetic fibers clothing shows how well this customer technical

of
service has paid off

.
Most product sales involves contact with customers

of
the work
in
For this reason the engineer interested working this area must have
in
in
,
personality work with people Although pleas

to
the interest and

a
is .
an
antly impressive personality the salesman's tech

in
asset sales
it
is
,
nical knowledge of his product that keeps the customer satisfied so that
he continues to buy .
GENERAL ASPECTS OF CHEMICAL ENGINEERING
Communications. The successful chemical engineer must be able to

express his technical ideas in oral and written communication . Tech
nical brilliance is of limited use if the engineer cannot transmit his ideas
to others . Often the major contact the young engineer has with the
administrative officer who decides on his promotion is through written
reports . All the engineer's reports should be written clearly and con
cisely with the reader in mind . Writing and speaking are important in
all
chemical engineering from research
to
of
fields sales
.
by
company showed that the young engi

oil
recent surveyt large

A
written and oral communication His supervisors

in
neer weakest
is
.
were satisfied with his technical ability > but were highly critical
of
his
,
written reports The survey reported that the young engineer spends
.
third written and oral communication The remainder

in in
of
one his time

-
.
spent
of
of
his time collection and correlation data one fourth
is
),
(
-
calculations one third and other activities The young engineers who
-
),
(
were the subject the survey also indicated their own dissatisfaction
of
with their writing and speaking Many them wished they had taken
of
.
report writing and public speaking when college

in
in
courses
.
all
Human Relations Almost the engineer's activities require close

.
engineers
be
work with other scientists and technicians He must able

,
work effectively group sell his ideas effectively

be
He must
to
able
in
to
and tactfully Many failures the chemical engineering profession are

in
.
be
attributed
to to
to
of
not due technical weakness but can failure the

,
engineer work effectively group Effective group activity depends

to in
a
.
on
primarily the sensitivity and respect for the rights The

of
others
.
it no
engineer must realize that may

to
matter how lucid his idea him

is
it
,
right
to
be
may
be
not clear others and not

,
The increasing complexity the chemical industry makes group

of
activity more essential than ever before The research and development
.
engineer frequently discusses his technical problems with his colleagues

an
get their suggestions may supervise group

he
of
technicians
in
to
a
;
experimental program and regularly discusses his work with his super
he
;
all
At cognizant the rights and needs

he
be
of
of
visor levels must

.
As
others mentioned earlier the development and design engineers

,
.
work closely together and with their respective groups The production
.
engineer must work with other engineers and with unionized labor force
aa
service engineer works closely with the operators

of
The technical
a
-
process carefully explaining suggested process changes The sales engi

,
.
neer must be particularly sensitive to his customers ' needs . The cus
tomer is not always right , but it will do no good to tell him point blank
that he is wrong .
Professional Activities . All engineers should be active in their pro
fessional societies . The chemical engineer has a choice of two major
societies . The American Institute of Chemical Engineers holds several
all
national meetings each year at which new developments in fields
of
engineering Local sections AICHE which
of
chemical are discussed
,
.
hold monthly meetings exist many parts the country The Insti
of
in
,
.
tute publishes several periodicals
as
the next section
in
discussed
.
The American Chemical Society serves the needs
of
chemists and
chemical engineers the largest the professional societies
of
of
It
one is
,
.
with over 90,000 members holds several national meetings each year
It
,
.
where the meetings the Division Industrial and Engineering Chem

of
of
istry are particular interest the chemical engineer The ACS pub
to
of
.
lishes many technical journals Many other more specialized professional
.
various fields within chemical engineering

of
societies meet the needs
.
Technical Reading The chemical engineer should keep up
to
date
.
by
by
his field not only attending professional meetings but also
in
,
reading technical journals general publications
of
There are number
a
.
and many specialized publications chemical engineering Two weekly

in
.
news magazines are Chemical Week and Chemical and Engineering News
.
the chemical industry
on
They both report current developments

in
.
all
Chemical and Engineering News sent ACS members The semi

to
is
monthly magazine Chemical Engineering particular interest pro .
to
of
is
duction and plant technical service engineers Chemical Engineering

-
all
Progress the monthly publication AIChE received by members
of
is
.
general feature magazine most chemical engineers
to
of
interest
It
is
a
.
-
Industrial and Engineering Chemistry similar monthly general feature

is
a
-
in by
magazine published the ACS chemical engineering

of
Results
.
research are reported the AICHE Journal the Insti

of
Transactions
in
,
Engineers Britain Engineering

of
tution Chemical and Chemical

in
),
(
Science Many more specialized publications exist For example there

,
.
.
the petroleum industry

on
periodicals
at
10
are least
.
PROBLEMS
2.1 Interview chemical engineer local industrial concern Perhaps your

in
a
a
.
professor will make available recent AICLE Directory from which can find
a
up
local chemical engineers perhaps will make

he
of
list local chem

or
of
the names
a
,
ical engineers who will cooperate this interview Obtain the following information
in
:
.
What his position

is is
a
?
.
responsibility and authority

of
What his area

b
?
.
What are his daily duties

?
c
.
d. To whom does he report and how ?

e. What has been his career ? ( His college ; his interest at graduation time , his
succession of positions , his interests now .)
Report this in oral or written form as desired by your professor , but do not divulge
the name , company , or complete position of the engineer you interview .
2.2 . Look up in the library , and report on , the career of an outstanding chemical
engineer .Such careers may be found in Who's Who in Engineering . Subjects for
such a reportmay be taken from lists of officers of AICHE , and from officers of
major chemical companies as listed in their yearly reports .
REFERENCES
1. Garner , F. H .: The Chemical Engineer , in H. W. Cremer and Trefor Davies (eds .) ,

“Chemical Engineering Practice ,” Academic Press , Inc. , New York , 1956 .
2. Harper , I. (ed .) : “ Chemical Engineering in Practice ,” Reinhold Publishing
J.
Corporation , New York , 1954 .
3. Lewis , W. K. , et al .: Chemical Engineering's Early Roots , Chem . Eng. Progr .,
54 :50–67 ( 1958 ) .
4. Packie , J.
W. , and C. W. Smith : A Petroleum Industry Look at the Chemical Engi
neer's Curriculum , J. Eng. Educ . , 49 :691 ( 1959 ) .
CHAPTER 3
USEFUL MATHEMATICAL METHODS
Mathematics may be applied to the solution of many problems in

chemical engineering . The type of mathematics required depends upon
the system under analysis . Many physical systems may be described
by rigorous mathematical expressions ; others may be described by
approximate expressions ; and still others are best described by graphical
or tabular presentation .
Analysis of a Problem . The analysis of a new problem in chemical
engineering may be divided into four steps .
1. Consideration of the physical situation

2. Mathematical description of the physical situation
3. Solution of mathematical relationships to give a final expression
to describe the physical situation
4. Verification of the mathematical expression with experimental data
all
In the first step , the physical situation are considered

of
details
If
.
chemical reaction involved the mechanism analyzed
If
unit
is
is
a
a
,
.
operation included the physical basis for the operation established
is
is
be .
In
many cases the physical mechanisms involved are too complex
to
fully understood
all
In
such cases the engineer finds out that known

is
.
and then develops physical model which simplification

of
the actual
is
a
a
,
physical situation but which may describe the behavior the system
of
,
with sufficient accuracy

.
be
many simple physical situations the physical model can

In
described
by rigorous algebraic differential equation For example mass
or
a
,
.
balances are often simple algebraic expressions On the other hand many
,
.
by
physical situations complex that they cannot

be
so
are described
a
rigorous equation Frequently the physical mechanism

the process
of
In the be is
.
In
not understood other cases even though the mechanism can

,
.
described the mathematical expression cannot

be
written Even
if
,
equation can cannot always solved rigorously

be
be
written
it
,
simplified
be
many cases the physical model must

so
that the resultant

,
mathematical equation solvable Unfortunately this simplification

is
,
.
the
no
accurately
go
may expression longer describes

so
far that the

actual physical situation
.
48
USEFUL MATHEMATICAL METHODS 49
Setting up the mathematical equation requires a thorough understand

ing of the physical basis of the process . Without this understanding ,
the resulting expression may not describe the situation . Therefore , it is
necessary to check the theoretical expression using actual data from the
process . If the data agree with the expression , one can infer that the
expression is adequate to describe the physical situation , but only within
the range of data used . One may also infer that the physical description
was adequate . This latter inference is not necessarily correct . More
data in a different range of perhaps temperature , pressure , or concentra
tion may not agree at
all
with the expression The physical model may
.
have been adequate only for limited range
of
conditions
a
.
The
chemical engineer cannot abandon his attempt
to
understand
a
by
process simply because neat rigorous mathe
be
cannot described
it
,
matical expression He must still predict the behavior the process and
of
.
design
on
equipment basedthis prediction the process complex
If
is
,
.
In
he must use approximate elementary physics
to
methods describe
it
.
and chemistry courses rigorous expressions based upon simple physical
,
models are derived Occasionally these are applied
to
few actual
a
.
physical situations which are chosen because they the theory Unfor
fit
,
do
tunately many systems with which the chemical engineer deals not
,
fit simple
theory For example the perfect as law fits certain real
,
.
-g
gases moderate temperatures and pressures but many real gases can
at
;
be
not described by this ideal model especially extreme temperatures

at
>
,
and pressures
.
In
recent years the trend toward more theoretical basis for chemical
a
engineering has accelerated Many observers believe that future prog

.
by
largely determined theoretical developments Ideally

be
ress will
,
.
the chemical engineer will use rigorous mathematical derivations from

Practically
an
accurate physical model wherever possible will carry

an he
,
.
far possible and then apply empirical

as
as
the theoretical treatment

on
approach based theory and experience complete the analysis

or
to
on
design workable process The increased emphasis theory requires

of
a
higher mathematical level than previously used chemical engineering

in
a
Although this trend will continue many systems with which chemical
,
engineers work are complex doubtful that empiricism will ever

so
is
it
,
completely eliminated
be
Application Engineering Problems

to
of
Mathematics Chemical
.
Proper application made only

be
to
real process can

of
mathematics
a
after the physical mechanism the process clearly understood For

of
is
this reason applied mathematics best studied while learning about the
,
is
physical mechanism the process The reader expected

to
of
have
is
.
algebra and elementary calculus He will learn

to
taken courses
in
apply the mathematical principles

of
these and other mathematics courses

in his courses in chemical engineering . Several useful mathematical

methods are not sufficiently developed in basic mathematics courses .
The remainder of this chapter will be devoted to a discussion of selected
topics in applied mathematics which the reader will find useful in this
book and in his other chemical engineering courses . Graphical methods
of correlation of data , addition , subtraction , integration , and differentia
tion will Numerical methods may also be used to fit equa
be discussed .
tions to data and to interpolate , integrate , and differentiate experimental
data . Such methods are useful in calculations on digital computers ,
where graphical methods cannot be used . A simple numerical method
of fitting an equation to data is discussed in a following section . The
application of more advanced mathematics in chemical engineering is
discussed in Ref . 5 .
PRESENTATION AND CORRELATION OF DATA
Experimental data in chemical engineering may be presented using a

table , a graph , or an equation . Tabular presentation permits retention
all
the significant figures the original numerical data Therefore

of
of
it
,
.
the most numerically accurate way reporting precise data How
of
is
.
ever tables may long and unwieldy interpolate
be
to
It
often difficult
is
,
between data points within tables and random errors from the actual
,
smooth function are not easily recognized

.
be
In no
Graphical tabular presentation theoretical
or
of
data must used

empirical equations can developed if
be
or
fit
to
the data some cases

.
very complicated empirical expressions might possible but the work

be
make tabular graphical

or
or
involved their evaluation use would
in
simply reporting experi

of
of
methods more desirable table data
A
is
a
.
mental results ice might

be
For example heat capacities tabulated

be of
.
various temperatures Data may also presented graphically

at
.
Although graphs are inherently less accurate than numerical tabulations
,
they are useful for visualizing the variation data and for interpolation
in
and extrapolation
is .
Interpolation quantity lying

of
of
the determination
the value
a
between existing experimental values Thus heat capacity

of
the values
if
,
.
interpolation will give

at
at
are known 100 and 200 value

F
150
a
F,
°
°
.
Extrapolation quantity lying beyond

to
of
used determine the value

is
at
the existing experimental data Thus the heat capacity known

if
is
,
.
extrapolation would yield

50
or
to at
100 and 200 value the

If
250
F,
F
°
°
.
function tabular data are difficult interpolate

to
not linear and

is
extrapolate Graphs empirical equations are more easily used

or
.
Graphical presentation data shows more clearly the general trend

of
data and permits easy interpolation

of
smooth curve drawn

If
is
a
.
through the data points , an estimate of the experimental error can be

made . It is easy to identify points which are not in agreement with the
smooth curve which is the best estimate of the actual function . Graphs
are limited in their numerical precision . Of course , if the data are not
originally very accurate , no precision will be lost by plotting them . In
cases where data are presented graphically , it is often convenient to use
the graphs for calculations based on the data .
Empirical equations are frequently used in chemical engineering . An
empirical equation is based upon experimental data . In some cases the
form of the equation will be determined by theory from a physical model ,
and the numerical value of the coefficients and exponents in the equation
will be determined from experimental data . In other cases the equation
may have no basis in theory . It is determined by fitting an equation
to the data and is justified by the time - honored engineering argument :
" It works !" A typical example of an empirical expression is that for
heat capacity for a gas . *
Cp = a + b + cT2 (3.1 )
cal
cal
where cp = heat capacity ,

or
mole mole
K
/g
/g
C
°
= absolute temperature °
K
= =
T
,
°
empirical constants determined from experimental data

c
b,
a,
Equation theory but represent

no
to
3.1 has basis has been found
in
it
,
(
heat capacities over wide temperature range The constants and

a
a,
b,
.
are evaluated for each gas from large quantity experimental data
of
a
c
.
For example for water vapor between 300 and 1500 Eq
K
3.1
is
>
,
,
°
)
.
3.2
+
10-3T 0.0459
x
X
CP 7.136 2.640 10-6T2

(
simple empirical equations will

be
of
of
few methods evaluation

A
described later the chapter very simple physical model predicts

in
A
.
that heat capacities are constant with temperature More sophisticated

.
physical models predict variation with temperature Experimental

a
Eq
an
evidence shows variation and 3.1 empirical equation not

is
a
)
.
Another empirical equa

on
theory used
is to
based describe the variation

.
tion for heat capacity

bT
+
3.3
=
СР
a
)
(
3.1
This equation apply because simpler than Eq

as to
easier but
is
is
it
;
,
)
.
closely high accuracy

fit
will not the data the data are not

If
of
it
,
.
.Eq
3.3 may adequate

be
(
by
Experimental data are frequently represented mathematical equa

a
by
The equation may graphical

or
be
to
tion fitted the data numerical

.
heat capacity are referred Chap

do
of
who not recall the definition

to
Readers
6
.
.
methods , as discussed in the following sections . The resulting empirical

equation may be used to calculate accurate values of one variable from
values of the other , provided that the original data were precise and that
the equation was carefully fitted to the data . Graphical curve fitting
all
suffers from the inherent inaccuracy of graphical methods Numerical
.
methods may used for greater accuracy Curve fitting using numeri
be
.
cal methods may involve tedious repetitive calculations which are best
,
carried out on digital computer
a
.
Equations describing data are much more convenient digital
to
in
use
computer calculations than are graphical tabular data For this
or
.
great importance
to
of
reason numerical methods are the modern chemical
engineer
.
The following sections will consider graphical and numerical methods

fitting equations and performing common mathematical manipula
of
of
integration
as
tions such and differentiation

,
.
Graphical Methods
Graphical presentation used not only for interpolation be
of
data can
an
and extrapolation but also for development empirical equation
of
to
The data may
be
describe the variation
in
almost any
of
the data
.
type encountered chemical engineering They may physical
be
in
.
as
property data such the variation capacity viscosity
or
heat with
in
,
They may pres

as
temperature process data such
be
the variation
in
,
in .
drop pipe with flow rate

of
sure the fluid

a
be .
Curve Fitting Fitting curves very difficult job Only

to
data can
a
.
.
graphical Further
be
simple cases will this section

in
few considered
a
.
information may The data are first plotted
be
found Refs and

in
5.
1
.
on
on
rectangular coordinates they appear fall straight line

a to
If
a
,
.
they give curve various techniques

be
simple equation can written

If
,
.
involve plotting the

all
may applied
to be
The methods covered here

.
data yield straight line Graph papers useful for developing equa
a
tions use rectangular semilogarithmic and log og coordinates

,
.
-l
Rectangular Coordinates Two variables must have simple linear

a
.
on
relationship give straight rectangular coordinates

to
line The
a
equation straight
of
the line
is
3.4
+
ax
=
(
b
Y
)
on
on
where plotted the vertical axis and the horizontal axis Such
is
y
.
3.1
Fig
the
plotted rectangular coordinates The slope

on
of
line
in
is
a
.
by
line determined taking the derivative Eq 3.4

of
is
,
(
)
.
dy
3.5
Slope =
a
(
)
dx
The intercept of the line is found at x = 0 from Eq . ( 3.4 )
Intercept = at x = 0
b = y (3.6 )
If it is believed that the data may be represented by an equation of the
form of Eq . they are plotted on rectangular coordinates , and a
(3.4 ) ,
straight line is drawn through the data . The slope and intercept are
determined from the graph and are substituted in Eq . ( 3.4 ) to give the
final equation .
+b
→
1
у
y=ax n -
m
Slope = n = a
* Intercept =b
Fig . 3.1 . A straight line on rectangular coordinates .
The two constants may be evaluated analytically or graphically from

of possible experimental inaccuracies
only two data points , but because
more points are desirable .
Example 3.1 . From the following experimental data determine an empirical equa
tion for the specific heat capacity of liquid ethylene glycol at constant pressure .
T, ° C /
CP , cal g ° C
-40 0.508
0 0.555
40 0.600
80 0.645
120 0.690
160 0.738
200 0.780
Solution . The data are plotted on rectangular coordinates . Either centigrade or

The
3.2
Kelvin temperatures may be used , as shown in the plot of the data , Fig .
.
very straight through slope may

be
to
data fall close the line drawn them The

.
By measurement
m As
any point
on
at
the line shown the slope

m
measured
is
/n
,
,
.
0.113 cal
C /g
C
°
= slope
a
n 100
°
0.00113 cal
/g
)C
2
°
(
The intercept at T = 0 ° C is found :
b = Cp (at T 0 °C) /
0.555 cal g ° C
Therefore , the empirical equation is
CP = 0.555 + 0.00113T
where cp is in calories per gram degree centigrade and T is in degrees centigrade .
for
The equation TºK has the same slope but different intercept Interpolation
is
a
,
.
easily accomplished with Fig 3.2 but extrapolation should
be
done with caution over
,
.
only limited temperature range
a
.
0.800
°8/
C
,,
cal
Cp
0.700
m
Specific heat capacity
0.600
n
for
Intercept
C
T
°
)
(
0.500
-40 40 80 120 160 200
0
C
°
T,
233 273 313 353 393 433 473

T.
K
°
Fig Example 3.1

to
3.2 Solution
.
Semilogarithmic Exponential functions may plotted

be
Coordinates
.
on
straight lines semilogarithmic graph paper Semilog coordinates

as
Fig
3.4
have one linear axis and one logarithm axis

as
shown
in
,
The logarithmic scale the major multiplication scales

on
to
identical
is
The scale may

be
slide rule Fig 3.3 by plotting

as
constructed shown
in
.
,
.
the log The

to
or as
of
of
10
the base number function the number

a
.
on
logarithmsare found from table slide rule The log10

N
the is
a
On the right hand scale

on
plotted the left hand scale plotted

is
-
-
.
by
number corresponding the logarithm

to
as
shown the construction

,
ine for N = 5. On the logarithmic scale the distance between numbers

different by a factor of 10 is constant . That is , the distance from 0.1 to
1.0 is the same as the distance from 1.0 to 10 . For this reason semilog
graph paper is useful for plotting data where one variable varies over a
wide range , perhaps several factors of 10. The range of a factor of 10 is
called an order of magnitude or a cycle . Figure 3.4 is a two - cycle semilog
graph .
1.2
4 5 6 POON
1.0 O
0.8
1
-
0.6 +
-2 -3
0.4
0.2
Logarithmic scale
N 0
Ooncon
miooo
10810
-0.2 0.6
0.5
0.4
-0.4
0.3
-
-0.6
0.2
1
-0.8
-1.0 0.1
0.09
0.08
0.07
-1.2 0.06
0.05
-1.4 0.04
14
15
11
12
13
10 16
3
7
0
N9
5
1
Number
,
Fig logarithmic scale

of
3.3 Construction
a
.
.
An exponential equation may have the form

3.7
=
b'eau
y
natural logarithms and and are

of
where the base 2.71828

is
as b
e
'
e
I
constants Because logarithmic graph paper uses the base

10
does
,
.
be
most engineering practice Eq 3.7 may

as
rewritten
=
1
)
(
.
610ar 3.7a
=
y
where Eq
of
The common logarithm each side

is
of
constant
a
b
7
.
.
3.7a taken
is
(
ax
log log 3.8

+
y
=
)
(
b
10.0
OOO
9.0
8.0
7.0
6.0
5.0
4.0
3.0
6
log
+
2.0
y=ax
log
у
Slope
=
a
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
Intercept
=
b
0.2
0.1
10 20 30 40 50 60
X
Fig
on
3.4 straight line semilogarithmic coordinates

A
.
.
of an
This equation straight line log plotted

as
of
of
instead
is
is
y
if
a
appropriate for the plot

as
function Semilog graph paper shown

is
x
,
.
by
Fig 3.4 differentiating Eq

3.8
The slope
of
in
the line obtained

is
)
.
log
y
3.9
d
=
(
Slope
)
)
(
dx
Fig 3.4 the slope

on
logarithms
of
Because the scale not shown

is
is
,
.
by
on
evaluated picking any two points the straight line The integral
.
form of Eq . ( 3.9 ) is
a =
log y2 – log yı
( 3.9a )
X2 X1
The intercept is obtained by setting x = 0 in Eq . ( 3.7a ) or ( 3.8 ) . It

follows that the intercept b = y at x = 0 .
Example 3.2 . Cane sugar (sucrose ) may be hydrolyzed in aqueous solution accord
ing to the reaction
C12H2201 + H2O + 2C6H1206
The rate of hydrolysis of sucrose is believed to be directly proportional to the con

centration of sucrose in the aqueous solution . * Determine the proportionality con
stant in the equation relating the rate to the concentration , using the following data " :
Time , min 0 30 60 90 130 180
Concentration of sucrose , c , g moles / liter | 10.023 9.022 8.077 7.253 6.297 5.347
Solution . The rate of hydrolysis is dc / de . Therefore the required expression is
dc
do
ko
The minus is included because the concentration of sucrose decreases with time (i.e. ,
dc/ de has a negative numerical value ) . Integration between the limits of c = co at
0 O and c =: cat o O gives
dc
- со с
Se
с
=ke
So
do
- In ko
Со
or C = Coe -k co
This expression is of the exponential form of Eq . (3.7 ) , and the data should give a
straight line on semilog coordinates . The data are plotted in Fig . 3.5 . To determine
the
k, equation put logarithmic form

in
is
log
log log
Co
+
=
e
k
c
(
-
t
)
The slope log the slope obtained from Fig 3.5

of
of
the line The value

is
is
e
k
(
-
).
log 6.5 log 9.02

––
Slope -0.00158 min

-1
120 30
-0.00158 -0.00158
Therefore ke 0.00364 min
-1
log -0.434
–
e
co
The intercept
at
10.023
=
is
=
O
c
e
The rate equation becomes
10.023e 0.003640
-
=
c
Chap
as
as
This known first order reaction discussed

in
is
4
a
,
*
.
.
15.0
14.0
13.0
12.0
11.0
10.04
9.0
moles
liter
8.0
8
7.0
6.0
5.0
4.0
30 60 90 120 150 180
min
t,
Fig Solution Example 3.2

to
3.5
.
.
on
log
Log logarithmic scales both the horizontal

of
Coordinates Use
.
-
and vertical axes gives log og graph Log log coordinates are useful
a
-
.
-l
plotting equations the frequently occurring form

of
in
bxa 3.10
=
y
logarithms this equation there results )

of
of
are taken both sides

If
log log log

+
3.11
=
y
b
x
a
)
log
plotted equivalently plotted

a or
log
of
on as
function
y
If
a of if
is
y
,
is
x,
log log coordinates straight line slope and

of
as
function
a
x
,
a
by
intercept Fig 3.6 This figure cycle

as
will result
in
shown
is
2
1
,
b
.
on
log log graph The slope measured linear scale and 1.21 The
is
is
.
-
If
by
= Eq 3.11
be
i.e. log
on to
intercept
=
found
at
.y
.
=
is
=
b
x
x
0
1
)
,
(
.
)
(
the data are not the range including any point the line may
in
=
x
1,
used together with Eq slope

to
evaluate
be
3.10 and the

a
b
.
)
.
(
water through
of
The pressure loss due

to
Example 3.3 flow circular

in
friction
a
.
velocity the following

be
in
length
of
pipe the water

to
known function
of
known
is
form
ΔΡ kur
-
,
50
40
30
.
25
20
15
у
10
9
8
m = 8.5 units
7
6
5
n = 7 units
Slope, a = 8,5
= 1.21
=
3
2.5
-Intercept
=
,
b
2.5
2
10
1.0 1.5 2.0 2.5

3
7
8
9
Fig
on
3.6 straight line log og coordinates

A
.
.
-l
sq
the pressure loss Ibs

in
where AP
–
,
,
average velocity
ft
of
the water sec

= =
,
r v
empirical constants
k,
through smooth pipe

70
of
inside
in
at
of
Evaluate and for flow water

F
1
a
ft k
°
a
.
r
.
diameter 100 long using the following experimental data

.
Determine the pressure drop

20
at
sec and
ft
sec
ft
2
b
/
.
12 15
9
sec
3
1
5
ft
7
v,
-AP 4.5 8.2 21.0 32.5

sq
lbs 0.26 1.75 12.5

in
,
Solution The logarithm the pressure loss equation

of
taken
is
a
.
,
-
.
log -AP log log

+
:)
=
q
k
v
(
on
The equation will give straight line slope and intercept log log coordinates
of
k
a
cycles will needed on the horizontal

be
An
of
examination the data shows that

v
2
(
)
-AP
by
The data are plotted cycle

on
cycles
on
scale and the vertical scale

3
2
3
.
3.7
coordinates Fig From the figure the slope and intercept are obtained
in
,
.
m 8.8
slope = 1.76
=
n 5.0
intercept = AP at
=
=
-
k
1
v
:
0.26
Therefore , the final empirical equation is
- AP , = 0.26v1.76
All
are
empirical equations limited the conditions under which the data were taken
to
. .
This equation useful only for water flowing through smooth pipe
70
at
of
in
is
1
°
inside diameter More general empirical correlations for pressure drop are available
;
.
but they are more complicated
?
.
100
80
60
40
30
20
.
10
8
,/
in
6
sq m 8.8 units
=
lb
Pp
2
-A 5.0 units
=
n
1.0
0.8
.
0.6
0.4
0.3
0.2
0.1
/ 10
20 30 40 60 80 100
1
3
4
5
6
v, 8
sec
ft

to
3.7
.
Values may read from Fig 3.7 calculated from the equation above
be
or
b
,
.
At
sq
ft
AP 0.88 lbs
in
sec
--
= =
2
v v
/ /
,
/
:
At
20
sq
by 51
in
ΔΡ lbs
ft
sec
,
/
,
on
The pressure drop the correct interpolation the graph

at
sec obtained
ft
is
2
lbs
20 by
1.0
sq
substantially different from the value linear interpola

of
obtained
in
ft a
/
The graphical extrapolation

to
probably
of
tion the tabulated data

is
sec
=
v
/
.
accurate because not far from the last data point

is
it
Only few simple cases curve fitting have been covered

in
of
this
a
The major problem determining the form equation

of
section the
is
.
which the data will not always practical attempt plot
fit
to
to
It
is
..
straight line Other methods are covered the section on
in in
as
data
a
.
numerical methods Further information available Refs and
is
6
.
.
Graphical Addition and Subtraction Graphical evaluation
of
mass
.
balances often involves graphical addition and subtraction The most
.
elementary examples are considered here More complex cases encoun
.
Ref
in
mass transfer are discussed
in
tered
2
.
.
ol.o
0.1 0.9
0.2
0.8
b 0.3 0.7 ,
Xc
component
mass
fraction
0.6
fraction
component
,
0.5
mass
c
190
Xb 0.4
0.7
0.3
0.8
0.2
0.9
0.1
o
1.0'0
1.01
0.9
0.3
0.1
0.2
0.1 0.8
mass fraction component
ta
a
,
for
3.8
Fig Equilateral triangular coordinates three omponent mixtures

.
.
-c
two mixtures containing the same three components different

in
If
proportions are mixed together mixture having different composition

a
a
,
Graphical addition may determine the final composi

be
to
results used
.
.Fig
3.8
Equilateral triangular graph paper

to
often used
is
tion
)
(
.
record the composition three component mixtures The three com

of
ponents may designated and their respective mass fractions

be
and
b,
c,
a,
Mass fraction convenient way expressing

in of
Xb
Xa
and
Xc
one
of is
are
,
all
composition The mass fractions components present mixture

a
.
must total 1,
xa + x2 + xo 1 ( 3.12
The mass fraction of component a ( x ) is plotted on the horizontal side
of the triangular , the mass fraction of b on the left side , and the mass
fraction of c on the right side . The scales run from 0 ( none of the
component ) to 1.0 ( pure component , none of the other two ). Any point
in the triangle represents the composition of a mixture . For example ,
point P gives the composition of a mixture , xo
xa = 0.55 , Xo = 0.10 , xe = 0.35 .
1.0
0.8
0.6
Ic
-
0.4
- - - P
0.2
0.2 0.4 0.6 0.8 1.0
Fig . 3.9 . Right triangular coordinates .
Equilateral triangular coordinates require special graph paper and are

sometimes inconvenient to use . Right - triangular coordinates ( Fig . 3.9 )
are easily constructed from ordinary rectangular coordinates and are
perhaps easier to use . If X , is plotted on the horizontal scale and xe
is plotted on the vertical scale , any point on the diagram represents the
composition of a ternary mixture . Although xh is not explicitly plotted ,
it is implicitly represented , because by Eq . ( 3.12 ) Xo = 1 ха
Xa Xc . A – –
perpendicular from the right angle to the hypotenuse may be used as the
Xó scale , but there is no need to plot it , because the composition can be
uniquely determined by plotting xa and xc . The region outside the right
triangle on rectangular coordinates does not represent physically real
solutions , because at least one composition would have a negative value .
The point P on Fig . 3.9 represents the same composition as P on Fig . 3.8 .
From Fig . 3.9 , Xa = 0.55 , Xc 0.35 , and xy = 1 Xa Xc 0.10 . –
If two mixtures of masses M , and M2 are added , a mixture of mass M3

will result . The mixing is shown schematically in Fig . 3.10 . The
compositions of mixtures 1 and 2 can be located on a right - triangular
diagram ( Fig . 3-11 ) . It will be demonstrated that the composition of
mixture 3 lies on a straight line between the compositions of mixtures 1
and 2 , as shown .
The total mass of mixture 3 must equal the sum of the masses of mix
M
Xal
x61
Xcl
M3
2.3
263
Xc3
M2
Xa2
162
Xc2
Fig . 3.10 . Mixing of two mixtures .
uc
201
My
M3 B
Хcз
M2 a
402
202 Xa3 ха,

Xa
Fig . 3.11 . Graphical addition .

1.0
0.8
mass fraction HNO3 M
0.6
, 0.4
Ms
+
n
Xc
Mm
0.2
0.6 0.8
0.2 0.4
Mó11.0
Xa
Mw mass fraction H2SO4

,

to
3.12
.
per cent H2O per cent HNO3

68
32
cent H2SO4 nitric acid per cent H2O and
2
),
),
),
(
water
.
each material required give 10,000

to
of
of
Calculate the mass mixed acid

lb
.
added together give the mixed acid Sym
be
to
Solution Three materials must

.
bolically .
,
Mn Mw
+
+
M
8,
m
M
where per cent H2SO

98
of of of of
total mass sulfuric acid

,
68 (
Mn total mass nitric acid per cent HNO3

.
Mw total mass water

total mass mixed acid 10,000
lb
Mm
(
Let component H2SO4

= =
C b a
H20
-
= HNO3
Fig
on
To begin the calculation the four compositions are plotted 3.12

,
:
.
Mg Xas 0.98 Xcs

=
0
=
xem,
:
Mn Xan 0.68
0, 0,
:
Mw Xaw Xcw
=
0
=
:
Mm Xam 0.45 Xcm 0.30

=
,
:
Only two quantities added graphically

M
be
be
will
at
to
so
one time added Mn

,8
can
;
To add Mn straight line drawn between them

M
and their sum added Mw

to
to
is
a
,
,
.
on
of as
shown Somewhere this line lies the mixture Because the total masses
to M
+
8
8
n
.
.
not possible locate the composition

of
these mixtures are not known the

it
is
,
Ms
must give Mm
to
of
sum However known that the addition Mw Ms

it
+
+
is
n
n
,
.
(
).
That
is
,
Ms M.
+
Mm
1
+
(
)
n
n
Therefore , the compositions of Mw , Mm , and the mixture Ms+n must
lie
on
straight
a
The compositions Mv and Mm are known straight line
so
of
line drawn between
is
a
;
.
the
these points
be
8 and Mn must
. of
The intersection the line with that between
M
+ ,
.
Ms
composition the mixture Ms The quantities Mv and
be
+
of
8
1
can determined
8
+
n
n
from Eq with new subscripts Using
or
or
from the line segments 3.16 3.17
)
of .
.
Eq describe the addition Eq gives
to
3.16
1
(
(
)
.
.
Moth am Law
I
Mw 4,8 Xam
+
X
n
From the graph X9,8 0.50
+
n
,
M
0.45
––
0
8th 9.0
Then
Mw
,
0.50 0.45
11
M
9.0Mw
+
8
By Eq
1
),
(
.
Mw = 10,000
lb
Ms +
+
n
lb
Therefore Mw 1,000 lb 9,000
Moth
,
-
by
The masses M. and Mn are now determined Eq 3.16
),
(
.
M. Xan
X
+
a
8,
n
Mn Xas Xa
0 +
8,
n
3
)
(
0.50
–
1.04
0.98 0.50
–
M. S
In
addition Mn M8 9,000
8
+
,
1
-
1.04Mn Mn
+
Therefore 9,000
,
Mn
lb
lb
4,400 Ms 4,600
per cent sulfuric acid 4,400 per cent nitric acid and
98
68
4,600
of
of
Therefore
lb
lb
of ,
,
additional water are required the specified acid
to
1,000 make 10,000

of
lb
lb
the
The inverse lever arm rule also applies directly the line segments through
to
-
points For example instead Eq the following relationship can

be
of
used
3
,
),
(
:
.
Ms length
of of
line
j
M. length line
k
24.5 units
1.04
=
23.5 units
This checks the result Eq

of
).3
(
.
Graphical subtraction based on the same principles

as
addition
is
Equation 3.13 may

be
written
as
(
M1 M3 M2
=
3.13a
(
)
M
M2 subtracted from the remainder has composition

If
which
is
M
,
of a
3
on
lies the straight line through the compositions mixtures and

2
3
.
on
in lie
The composition will the line extended beyond

of of
the remainder
M
1
the composition Fig All the inverse

as
shown mixture 3.11

3,
lever arm equations derived for addition also hold for subtraction
-
.
Graphical Integration . Graphical integration is useful when no

analytical expression of the function exists . To evaluate the integral
I X2
may
dx
11
Sa
3.20
)
necessary the integral
to
know how varies with constant
If
is
is
y
is it
,
.
=
x2
x1
–
I
3.21
y
(
)
expressed an analytical for example
be
as
of
can function
If
y
x,
,
y 4.3x2 3.22
)
the integral should evaluated analytically
be
:
X
** 2
dx
21 4.3x2 de
=
{
S
I
4.3
–
x23 X13 3.23

(
)
3
the limits
x¡
of
of
Substitution numerical values and would enable
let x2
quantitative evaluation the integral For example
of
and
x1
ft
=
2
,
.
Then
ft
:=
X
6
2
=
4.3
28
63
I
)
(
3
299 cu
ft
3.24
)
(
An
integral can also evaluated by determining the area under the

be
For example Eq 3.22 plotted

in
function
as
of
of
is
curve
y
2 x
a
)
.
Fig 3.13a The limits are shown The area under

X1
ft
ft
X2
6
.
.
.
,
the
curve and between the limits equal the integral The area
to
is
.
by
by
counting squares and then multiplying

be
may evaluated the

Each square has
of of
20 15
value each square There are squares

a
.
= .
=
sq
cu
20
Therefore
=
ft
ft
ft
value side
1.0 side
(y
x
,
(
)
(
.
cu
=
which checks the analytical method within

20
15
ft
300
X
=
.Eq the =
I
accuracy the graphical integration Graphical integration

of
of
.
merely Normally
, to
3.23 shown here demonstrate the method

is
(
Eq
x be
analytic integration preferable but the cannot

in
3.20
y
if
is
as (
)
.
analytically the values may plotted

be
expressed function
of
of
,
and graphical integration

carried out
a
Actual counting tedious and many less laborious methods

squares
of
is
by
are
The method rectangles approximates the area

is of
of
used series
a
.
rectangles take equal

to
It
vertical convenient but not essential

,
,
.
increments along the horizontal scale The upper end each rectangle
of
.
so
placed that the area included below the curve but excluded from the
is
160
140
120
100
,y
ft
sq 80
??
4.3
y =
60
40
20
X1 X2
0
1
0
, 3
6
ft
x
Fig 3.13a Graphical integration area under curve

,
.
the
rectangle just equal

to
the area above the curve included

to in
is
rectangle Figure 3.136 shows the general method applied the

.
previous example The ordinates are chosen for increments

in
y
l,
.
and the integral

is
=
n
i
X
2
may
Διές
dx
So
3.25
Σ
y
21
(
9
:
=
1
i
all
the equal
If
increments are
x
=
n
i
X2
dx Ax
non
da
Yi
3.26
se
y
)
(
=Σ
X
1
1
i
160
140
94
120 Equal
100
33
,y
ft
sq 80
Equal
60
I
2
Equal
40
21
Equal
20
0
Axi Ax2 Дх3 Ax4
0 1 2 3 4 5 6
x , ft
Fig . 3.136 . Graphical integration , method of rectangles .
For the case at hand , Ax 1 ft , and y values are obtained from Fig . 3.13b
X2
T1
y dx (1 ft ) ( 27 + 53 + 89 + 130 sq ft )
So
= 299 cu ft
The method of trapezoids replaces the smooth curve by a series of

straight - line segments between data points . The area of each trapezoid is
evaluated , and the results are summed for the total area . With reference
to Fig . 3.13c , the area of the first trapezoid is
Y. Axı + ( y2 – yı ) Ax1 =
y2 + yi
2
AX1
160
35
140
120
100
,y
ft
s5
q 80
60
‫ال‬
40
20
Yi
0
AXI Дх2 Axg
DXA
0 1 2 3 4 5 6.
x , ft
Fig . 3.13c . Graphical integration , method of trapezoids .
+
The total integral is
12
Yi
+
Yi
+
1
dx Axi
STO
3.27
y
)
(
2
X1
-
all
If
increments are equal

x
in
yi
+
Yi
+
Ax
1
Lyde yunus
' o
2
-
yı
)
+
Yn
+
y2
Yn
AX
+
3.28
)
-
(
1
2
=
Ax
Fig
39
y2
17
For the previous example

yı
with
=
ft
3.13c
=
,
,
,
1
)
(
.
Y3 = 69 , 44 = 109 , ys = 155
I2 17 + 155
y dx (1 ft ) + 39 + 69 + 109
11 2
303 sq ft
In this approxi
case , the area is somewhat high because each straight - line
mation includes slightly more area than the curve .
Both the method of rectangles and the method of trapezoids may be
applied to a series of data points without plotting the data . Equations
(3.25 ) and ( 3.27 ) are examples of the general subject of numerical methods ,
discussed in аa later section . They may be applied to graphs or to numeri
cal data .
2,000
/ft
min
1,500
,
cu
flow rate
,
1,000
Q 500
N.
P.M. 12 M. A.M. A.M. 12 P.M. P.M. 12 M. A.M.

4
8
8
8
Time day
of
Fig Example 3.5

to
3.14 Solution
.
Example 3.6 product from chemical process measured and

of
The flow rate

is
a
.
continuously during the operation The chart recording the data shown
hr is
recorded
.
Fig 3.14 product made during the period

24
of
Determine the total volume

in
-
.
from midnight midnight

to
develop analytical expression for flow rate

be
an
to
as
would difficult
It
Solution
.
graphical integration will

be
The total flow

so
of
function time used

F
is
a
a
12M
F
de
Q
-
12M
cubic feet per minute and the time minutes The

in
the flow rate

in
where
is
is
Q
.
of
of
horizontal the chart

scale time and the vertical scale rate flow Therefore
is
is
,
,
.
the total flow simply the area under the flow rate curve between the midnights
is
.
-
Fig 3.14 There are approximately 30.5 rectangles and

cu on
These limits are shown

,
.
60
hr
of
value min min Therefore

aa
hr
ft
each has 250

X
X
4
/
,
).
/
(
60
hr
hr
cu cu
min min
F
30.5 250
ft ft
hr 4
/
/
)
)
(
(
)
(
24
in
1,830,000
-
Graphical Differentiation . Graphical differentiation may be used to

determine the slope of a curve relating two variables . If the analytical
relationship is known , the differentiation may be performed analytically
for a precise answer . If the function is not known , the data may be
the the
plotted and the slope may be determined by drawing a tangent to
point the proper slope
at
of
of
curve a However determination
,
.
tangent often uncertain especially the experimental data are inaccu
if
is
a the
Graphical differentiation
to
of
rate used obtain accurate values
is
.
slope tabulated data'are available the data are plotted Ay Ax

If
as
as
/
,
.
function This will be step curve The best smooth curve

of
is
x
.
by
/dy
dx
drawn through the step curve give
to
the relation
dy Δy
limit 3.29
(
dx
)
0,4x
Ax
Cp
Example 3.6 The heat capacity aH BT
as
of
material defined where
H
=
is
,
/
a
)
(
.
the enthalpy From the following approximate

or
of
heat content the material

is
for
experimental data determine the variation heat capacity with temperature
in
,
ethylene glycol constant pressure

at
TABLE E3.6 DATA FOR EXAMPLE 3.6

.
AH heat added cal AT AH AT cal

C
>
/g
C
/g
°
,
11.3 0- 20 0.565
11.8 20- 40 0.590
12.2 40- 60 0.610
12.7 60– 80 0.635
13.1 80–100 0.655
13.6 100-120 0.680
14.0 120-140 0.700
14.5 140-160 0.725
15.0 160-180 0.750
15.4 180-200 0.770
The quantity AH AT temperature and

of
Solution calculated for each interval

is
/
.
then plotted temperature Fig 3.15

as
so
function smooth curve drawn

of
A
as is
is
a
).
split each step approximately

a on
This smooth
to
as
half the average shown

in
straight line
In
ah aT this case the curve The line checks that

of
curve
is
.p
is
.
(
)
3.1
cp
Example may
be
of
Values read from the line

.
Numerical Methods
Graphical
methods are not always convenient
to
use for example

,
equation
In
digital computers polynomial

of
with this case sufficient

a
.
terms may experimental data points and the resultant

be
to
of
fitted set
a
equation may represent the experimental

be
to
used data general

A
.
polynomial equation is
Y = a + bx + cx2 + dx3 + ex4 + ( 3.30 )
where x and y are variables and a , b , c , d , and e are constants . The

minimum number of data points needed to given polynomial expres
fit
a
sion equal expression For example
to
of
the number constants the
in
is
,
.
0.800
aH
ат
0.750
AH
/
°
C AT
g 0.700
cal
AHAT
0.650
0.600
0.550
40 80 120 160 200
C
T,
°

to
3.15
.
be
two data points are known only two constants and can evaluated
if
b
,
that straight line described

so
is
a
buc 3.31
=
y
)
an
More data may show that straight line inadequate description

of
is
a
system points only straight line larger

If
the but two can describe

be a
a
,
points polynomial with more terms may fitted

of
number known
is
a
,
as
the data shown Examples 3.7 and 6.3

in
to
The resulting polynomial may mathematical manipulations

, be
in
used
,
integration differentiation However great care

be as
such and addition

,
,
.
differentiating
because the polynomial may
fit
taken the data

in
must
,
may
be
experimental
to
too well That the error sufficient scatter the

is
,
.
an
points give polynomial

of
data and which follows the random error

a
otherwise smooth function . Differentiationwould yield the slope of the

polynomial curve at a point , rather than the slope of the actual smooth
function .
If a polynomial of the wrong form or with too few terms is applied to a
the points chosen
of
set of data , it will
fit
to
determine the constants the
Example
all
fit
equation may not
at
as
of
but the rest the data shown
in
it
,
,
3.7 The polynomial may also give erroneous values for the function
.
between the data points
.
Another useful polynomial form
is
+ x2 + +
e
+
+
3.32
=
y
)
x4
The choice between Eqs 3.30 and 3.32 depends upon the general
(
(
.
)
Equation 3.30 usually useful when the
/ be
to
of
trend the data fitted
is
(
)
.
dy
dx
increases and Eq gives

of
absolute value
dy as
increases 3.32
dx x
a
(
)
.
between points when approaches zero
fit
byas
better increases
x
/
.
The change slope with may often examining
be
of
determined
Of x
of a
rough plot course either form may
be
to
of
the data fitted set
a
,
.
data points but the resulting equation may give erroneous values
,
as
between points Example 3.8

be
will shown
in
,
.
Although
an
Method Lagrange principle equation may
of
in
be
.
for
set
each data point and the resulting equations solved
written of
simultaneously the procedure becomes very tedious polynomials in
of
,
In
more than three terms such cases any several numerical methods
of
.
Only the Lagrangian method will

.33
be
may
be
used mentioned here
.
data points polynomial terms may be
)yi
written
of
there are
If
Xi
n
n
a
,
,
(
:
=
n
i
Xn
Xi Xi
–
+
Xi (x
X1 x
Xi x
( (x
x
1
1
- Xi-1
)
Xn )
( (
)
(
=
Yi 3.33
y
)
xi
–
Vi
–
Xi
+
X
1
31
;
)
)
(
function corresponding
to
is at
of
of
where the value

x7, Xi
the
is
y
;y
is
y
a
x;
data point point and

at
of
the value the first data the

is
y
x
,
:)
;
x
;
(
the last data point The indicated summation

at
of
value carried
= is
x
any data point

At
all
xi
out through data points from and

to
x
n
,
1
Eq 3.33 reduces equation

be
to
so
can seen that the fits each

y
it
=
y
;
(
)
.
data point also gives smooth function between

It
useful because
it
is
a
.
data points For this reason called the Lagrangian interpolation

it
is
A .
formula simple example will show how Eq 3.33 used

is
(
)
.
Example 3.7 Fit polynomial equation the following data

to
a
:
.
4
0
18 43
Yi
4
Solution . Inspection shows that \dy / dx ! increases as x increases ; so Eq . (3.30 ) with

four terms will be used . With Lagrange's equation :
y = 3
- 1) (x – 3 (x 4)
+4 ( 2x – 0) (x –- 3 ) (x 4)
(0 –
-
1) (0 – 3 ) (0 4) (1 0) (1 3) (1 4)
+ 18
(x 0 ) (x
-
1) (2
- 4)
+43
(x – 0 ) (x 1 ) (x – 3)
(3 - 0 ) (3 – 1) (3 4) (4 – 0 ) (4 – 1) (4 –
-
3)
Solving gives
y 3 + 2x 2x2 + x3
A value of y at x = 2 may be obtained using this equation to interpolate :
y = 3 + 2 (2 ) – 2 (2 ) 2 + 23 = 7
Example 3.8 . From the following experimental data for superheated n-butane at
160 ° F,> calculate the following by numerical methods :
a . An equation relating the pressure to the specific volume
V2
b. The work required to compress the gas from 20 to 100 lbs sq in .; / W P dĎ
= Soap
c. The rate of change of pressure with volume at 30 lbs / sq in .; ( 8P / 87 ) .
Point 1 2 3 4 5 6 7 8 9 10
P , lbs / sq in . 14.7 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 100.0
, cu ft / lbm 7.627 5.564 3.659 2.704 2.131 1.748 1.474 1.268 1.107 0.9780
There are 10 data points , so that it would be possible to polynomial

fit
Solution . a
10
terms very tedious and probably more

be
of
However this calculation would

.
complex than the accuracy The choice the number terms of

of
of
the data warrants

.
compromise between the time required for calculation and the desired accuracy
of
is
. a
Both Eqs
be
and 3.32 will fitted the data show the difference

fit
to
to
3.30
,
(
)
.
made among the data points

be
to
between them choice must desirable
It
A
is
.
choose points spread over the entire range choosing

be
data but care must taken

in
of
this case three and five chosen points will

be
In
fit
points ensure the best

to
used
.
be is a .
Inspection the plotted data Fig 3.16 shows that the slope increases from
of
a
)
.
.
/dy
large negative value smaller negative value

dx
as
Therefore
to
increases
✓
a
,
.
However Eq 3.30 will also

be
approaching zero and Eq 3.32 should used

,
)
(
.
(
.
.
demonstrate the difference

to
used
.
Using Eq 3.30 with points gives

10
1,
3,
(
)
.
cV2
+ + + +
b✓
P
+ + + +
= = =
a a a
14.7 7.627b 7.627

3c 2c c
?
(
) ) )
30.0 3.659b 3.659

(
100.0 0.978b 0.978

a
may solved simultaneously Lagrange's equation may

is be
be
or
These equations used

,
The resulting equation

P
137.514 41.631 3.347

✓
V
2
-
The signs and the resulting curve Fig 3.16 curve oscil
of
the terms alternate

A
,
,
(
)
.
for
It
the fitted points very poor

fit
of
lates between the remainder the data

is
a
.
.
.Eq
use
/dy
approaching zero
dx
undesirable
fit
to
the case where

of
Thus 3.30
is
is
,
.
(
)
100 10
A P = 137.514-41.631 V + 3.347 v2
9 ( through points 1, 3 , 10 )
114.021 15.887
80
B P = 0.025 + V v2
8
. CP
( through points 1, 3 , 10 )
=213.528-167.741 V
A +56.7078 V2-8.60967 V3
/,
1
in
= 60 6 +0.464299 V4
sq ( through points 1, 2 , 4 , 7 , 10 )
5
1b
P 40
+
-
3
20 B
1
1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0

V , cu ft /1b
Fig . 3.16 . Fitting a polynomial to experimental data .
Using Eq . (3.32 ) with points 1, 3 , and 10 gives

b с
Р = a + +
V Ő2
Lagrange's equation will be used to develop the polynomial .
Point 1 3 10
Yi = Р 14.7 30.0 100.0
Xi = 1 /V | 0.1311 0.2733 1.0225
P 14.7
(x – 0.2733 ) (x – 1.0225 )
(0.1311 - 0.2733 ) (0.1311 1.0225 )
+ 30
(x – 0.1311 ) (x – 1.0225 )
(0.2733 – 0.1311 ) (0.2733 1.0225 )
+
(x - 0.1311 ) (x – 0.2733 )
100
( 1.0225 – 0.1311 ) ( 1.0225 – 0.2733 )
Solving and substituting x = 1 / V gives
114.021 15.887
Р 0.025 + +
✓ V2
the data points very well Fig

all
This equation fits curve certainly

It
B
3.16
is
,
)
(
.
.
preferable the previous expression

to
10
used with the five points

to
Equation 3.30 may show the

fit
and
of
be
>
1
2
7,
is ,
,
4,
(
this form with five points The resultant equation

.
V3
V2
0.46430
P
213.528 8.60967
=
–
+
56.7078
V
163.741
V
4
This equation , which is very laborious to derive , oscillates badly between the fitted
points ( Fig . 3.16 , curve C ) . This solution has demonstrated the importance of the
initial choice of equation form .
b. The equation derived using Eq . (3.32 ) is the only adequate one ; so it will be used
to evaluate the work . Actually , the other two equations would give approximately
correct answers in this case . At Pi - 20 , V , 5.564 , and at P2 100 , V2 = 0.978 .
Then
V2 114.021 15.087
W =
SM (
0.025 +
V
+
ū2 ) ar
- 186.5 lb , cu ft / sq in . Ibm
c. The term ( aP / aV ) T is the slope of the curve at any point . Obviously the slopes
of the curves based upon Eq . (3.30 ) are seriously in error at many points . Therefore ,
only the equation of the form of Eq . (3.32 ) will give a correct answer , since curve B
fits the data well . Differentiation gives
ap
*(
( ** ), - dÝ
114.021 15.887
d
0.025
+
V 0.99
T
114.021 31.774
+
V2
Ý
sq
30
At
lbs
.in
Therefore
V
3.659
=
/
,
.
ӘР
-7.852
=
(
9)T
in By
comparison gives gives -3.578 both
of
curve 17.138 and curve which are
–
A
C
,
error
.
Method Least Squares

polynomial Fitting
experi
of
to
of
set
a
a
.
as
mental data described the previous sections often not the best
in
is
an
develop equation representing the data for the following

to
method
,
reasons large number data points are available necessary

of
If
to
of is
it
a
.
select the least possible number the proposed

to
evaluate the constants

polynomial The other data points are not considered The resulting
.
polynomial will points exactly may

fit
the selected but oscillate

it
,
violently between the points and not actually represent the true smooth
experi
of all
Generally experimental data are subject

at
to
function
,
.
mental errors measurement the data are subject

to
If
random errors
.
the experimental values will differ from the actual values dan
so
is
it
;
polynomial exactly
fit
to
to
gerous data that are not exact

a
least squares overcomes the objections discussed above

of
The method
.
an
all
may equation
be
fit
to
to
as
as
used well possible the available

It
experimental data The resulting equation may not any point

fit
.
exactly will give representation the true smooth func

of
but better
it
a
,
tion
on
The method the principle least squares

of
based which states

is
.
set ,
most probable value obtainable from measure

or
of
that the best

a
“
equal precision that value for which the sum the squares
of
of
of
ments
is
the errors minimum This principle derived from considera

is
is
a
a
?
"
.
tion of statistics and probability . It will be used in this section to
fit
a
set
polynomial experimental data Generally
be to
of
three terms
of
a
,
a .
any number may compromise
of
terms used and three terms
is
,
three term polynomial
fit
of
of
between closeness and ease solution
is
-
.
sufficiently accurate for many cases where the data are subject experi
to
mental error
.
The general polynomial expression
is
cx
bx
+
+
3.34
y
=
a
)
which may each data point from
be
written for
to
n
1
:
Yi
+
cxı
=
bx1
?
=
cx
+
+ 3.35
Yi
bxi
=
2;
a
)
+
+
=
Yn bxn cxna
a
by
true value mayrepresented the right side these equations

be
The
of
,
by
and the measured value given the left side The error for each
vi
is
measurement then
is
Yi
+
+
bxi cxi
-
=
Vi
all
By the principle least squares the polynomial will best
fit
the data
of
the squares
of
when the sum

of
the errors
=
n
i
tun
••
+
+
2
ví
vz
3.36
?vi
?
?
)
(
=
1
i
minimum Substituting Eq into gives

is
3.35 3.36
a
)
.
=
n
i
bxi
£
yi
+
F
cx
3.37
+
;?
a
c
a,
b,
(
?
)
)
-
(
)
=
1
i
states that the sum the squares function

of
where the
of
is
F
a
c
a,
b,
(
The numerical value Eq will

of
quantities
be
and 3.37
a
(
)
c
a,
b,
.
.
minimum when the derivatives the expression are zero

of
ƏF af aF
3.38
0
0
:
ab
(
да ac
Substitution Eq these expressions gives

of
of
3.37 into the first

(
)
.
=2 =
n
[ i
bx
cx
+
–
;?
:)
?2
a
a
ƏF
]
;
(
-
1
i
3.39
0
=
да да
from which follows

na + bExi + c # x ; 2 == Σy : ( 3.40 )
Similarly ,
i =n
-
;) ]
af o [ i =£1 ( a + bx : + cx ;? Y
0
ab ab
and axi
αΣυ + ; + ΟΣ , 2 . + cΣ ,;33 = Συ ; 4:; (3.41 )
[{
ian
;
bxi
Σ (a +
cx
+
;?
[
]
?
ƏF
)
o
Finally
=
1
i
,
ac ac
so that
αΣ
2y
ΕΣ
+
+
cΣ
=
Συ 3.42
2
4
,
,
)
Equations may solved for the required constants
be
to
3.40 3.42
(
)
by
and substituting
the appropriate functions for the data points
c
a,
b,
least squares may applied equations

be
xi
yi
The method
to
of
of
(
,
)
.
various forms Example 3.9

as
shown
in
,
Example 3.9 Develop vapor pressure with tem

of an
expression
of
for the variation
.
perature using the method least squares with the following experimental data for
,
ethyl alcohol
:
10 30 70
C
50 90
T
°
Pv
mm Hg 1,180
25
80 215 545
,
an
In
Chap vapor pressure equation

fit
to
of
Solution data are found the form

4,
-
.
log
4.39
C
PV
,
+
T
)
=
C
.
Comparing Eq 4.39 with Eq 3.34 shows that

(
)
.
T 1
C2
C1
log Pvi Xi =
Yi
=
0
=
=
cC
TI
b
,
,
:
Calculated numerical values are shown

of
Substitution the numerical

in
Table E3.9
.
TABLE E3.9 NUMERICAL CALCULATIONS FOR EXAMPLE 3.9

.
10
10
10
12
Po Ti Yi Xiyi yi 10
T
Xi2 xi3 Xi4

X
+
+
X
6
X
X
8
:l
283 25 0.00353357 1.39794 12.4861 44.1205 155.903 0.0049397 17.4548

303 80 0.00330033 1.90309 10.8922 35.9478 118.640 0.0062803 20.7288
323 215 0.00309598 2.33244 9.58509 29.6752 91.8738 0.0072212 22.3566
343 545 0.00291545 2.73640 8.49985 24.7809 72.2472 0.0079778 23.2590
363 1160 0.00275482 3.07188 7.58903 20.9064 57.5933 0.0084625 23.3126
Sum 0.0156002 11.44175 49.0523 155.4308 496.257 0.0348815 107.112
23
values into Eqs . (3.40 ) and (3.41 ) give

5a + 0.01560026 11.44175 ( 3.40a)
0.0156002a + 49.0523 x 10-66 = 0.0348815 (3.41a )
so that a = 9.0140 , b = -2155.63 .
2155.63
Therefore , log P ,0 = 9.0140
T
(1)
This equation and the original data are plotted in Fig .
fit
the equation
of
3.17 . The
1,200
1,000
800
P
600
log
2155.63
,
9.0140-
=
PP
400
200
0
280 290 300 310 320 330 340 350 360 370
,
K
T
°
Fig Curve fitting using the method least squares

of
3.17
.
.
be
good term with the constant

fit
obtained
to
better could
cс
the data
is
if
A
is
a
.
included
:
с
b
log Po
+
=
a
+
T
T2
data from Table E3.9 into Eqs gives

to
of
Substitution 3.40 3.42

(
)
.
+
+
5a 0.0156002b 49.0525 10-60 11.44175

=
10
0.0348815
x
+ +
+ +
0.0156002a 49.0525 10-66 155.4308

X X
=
c
-'
10-9 496.257 10-12c 107.112 10-6

X
49.0525 10-6a 155.4308

X
Solving gives -2160.61 1217. Then

b
9.0176
=
a
c
,
,
2160.61 1217
log Po
+
9.0176
2
(
)
T2
T
As shown in the following table , this equation is not sufficiently better than the two
constant form to warrant the additional calculations required .
P », experimental 25 80 215 545 1180
,
Pv , calculated from ( 1) 24.94 79.38 218.9 536.3 1190.1
P », calculated from (2 ) 25.01 79.44 218.8 535.6 1188.0
A desk calculator was used to evaluate the numbers in this problem , because a slide
rule did not give sufficient significant figures . Use of a slide rule will lead to a highly
inaccurate final equation .
TRIAL -AND - ERROR SOLUTIONS
Chemical engineers must often solve equations which have no simple

analytical solution . For example , consider the equation
ex² X = 14.2 ( 3.43 )
The most convenient way to solve this equation is to assume values of x

until the left side of the equation equals the right . The equation should
be inspected carefully to determine the general effect of a variation in x .
Perhaps one term is substantially smaller than the others , and it may be
neglected for aa first estimate of x . In Eq . (3.43 ) , x is probably small com
pared to ez?
As a first approximation for x , ez ? = 14.2 and x = 1.63 but
ex² X = 14.2 16.3 = 12.6 + 14.2
Inspection of Eq . ( 3.43 ) shows that a

a somewhat larger value of x should
be used . For the second trial , let x = 1.70 . Then
1.7
1.7 17.8 1.7

+
e( 16.1 14.2
)
an
Therefore the second trial assumed which too large The two
is
x
,
Fig 3.18 Although the function extremely non

on
points are plotted

is
.
linear straight line drawn between the first and second approxima
is
a
,
The third approximation

at
of
tions taken the intersection this line

is
.
ez
and the line Checking the third approximation

ex
=
-
14.2
x
(
:
–
)
.
= 1.665 gives
x2
=
1.665) 1.665 15.9 1.665 14.2

2
e
(
within slide rule accuracy

In
The third trial many engineering calcu

is
to -
lations not necessary plot the trials for new estimate The
is
it
experienced engineer can often make mental estimates and interpolations

be .
An alternative iterative procedure may the equation

be
to
used
if
17.0
2nd approximation
16.0
15.0
ex2 - x =14.2 ( desired value )

ex ?
3rd approximation
14.0
13.0
-1st approximation
12.0
1.60 1.65 1.70
Fig . 3.18 . Graphical estimation in a trial - and -error procedure .
solved can be properly rearranged to give a value of x which on successive

evaluations approaches the correct value . The method is not useful if
successive yalues of x diverge from the correct value . For example , Eq .
( 3.43 ) may be rearranged :
x = exa 14.2
A = 2 is substituted as a first approximation

value of x = on the right - hand
side and x on the left is solved for
X = ex² - 14.2 = 40.4
If ( x = 40.4 ) is substituted on the right and the x on the left is again

evaluated ,it will be a much larger number . Thus , x is rapidly diverging
from the right answer ; so this method is not suitable with the equation
If an x lower than the correct answer is chosen here ,
the
as written .
will get progressively and rapidly smaller thereby
of
iterative values
x
diverging from the correct answer

.
As
Equation 3.43 may rearranged give converging solution

be
to
.
(
is )
general rule necessary solve for the which appears the term
to
in
it
x
a
changes Eq undergoes greater varia

to
In
most sensitive
in
3.43
er
x
so ,
.
)
(
.
in
tion than the other terms when varied the this term
is
is
solved
x
x
;
for
2
ex ? = x + 14.2
X = Vin (x + 14.2 )
Then assume x = 2 on the right , and solve for x on the left
X
x =
= In (2 + 14.2 )
1.67
let
For the
on
first iteration 1.67 the right Then
=
x
.
= Vin
X
1.67 14.2
+
(
)
= 1.662
The approximate has converged the correct value after only
to
of
value
x
one iteration second iteration would not change signifi
of
the value
A
x
.
cantly give convergent

of
value less than the correct one will also

A
a
.
solution Sometimes not possible rearrange the equation give

to
to
is
it
.
converging solution and necessary the trial and error

to
to
resort
it
is
a
-
method outlined first this section
in
Many
engineering problems require the solution set
of
of
simultaneous
a
equations
no
The solution algebraic equations presents
of
of
sets new
.
problems This sort solution was first presented high school algebra
of
in
.
.
the equations are differential equations the principles are unchanged
If
,
but the solution may
be
too difficult for direct solution trial and error

A
-
.
procedure will often give the required solution but the principle that the
,
number independent
equations must equal the number
to of
of
unknowns
unique give forgotten
be
in
order solution should not

a
.
set
very common form quation

of
simultaneous which one

in
A
one
is
-e
or
of
table data
A
of
equations analytical
is a or
more the are not form

in
graph may form functional relation between the system variables that
a
Of
part
be
the equation set graph could

of
or
course the table

a
be is ,
.
an
equation but this usually difficult and time consuming

to
reduced
,
Instead trial and error procedure can used which values from the
in
a
,
graph table are used with the analytical equations the solu
or
to
at
arrive
Again equa
, no
possible unless the number

of
tion for the set solution

is
,
.
tions analytical graphical tabular equals the number

or
of
unknowns
,
,
,
The trial and error procedure offers nothing magical merely

It
is
a
-
.
an
solving equation equations

or
up of
of
brute force method set

a
-
Example 3.10 the solution Example 4.11

to
Set
In .
Example 4.11 the temperature two omponent benzene

at
Solution which
a
(
.
-c
At
vapor first begins required this temperature the vapor

to
toluene condense
is
)
composition unchanged and the mole fractions the components the liquid phase
of
in
is
,
up
to
add 1.0
:
хь
1.0
+
х,
1
(
)
The relation between gas and liquid compositions is obtained through Raoult's law
and the specification that the total pressure is 1 atm ; from this
Pьхь
Yo = 0.4 = (2)
760
Pecade
yь = 0.6
760
There are now three equations ( 1) , (2 ) , and (3 ) in the four unknown variables Xb , Ii ,
for
Pub ,, Pvt .These equations are obviously insufficient unique solution Two more
.
relationships are available the vapor ressure curves Appendix
D.
of
of
the form
in
-p
In
functional notation
,
vb =
fi
Pob
T T
4
= =
(
)
( (
) )
Put
f2
5
(
)
Xb
Now five relationships are available the five variables Pob Poi and but two
Xt
in
,
,
as ,
T,
these are not expressed analytically
of
of
The method solution follows
is
:
.
reasonable temperature estimated

3. 2. 1.
A
is
.
Appendix this temperature
at
read obtain Pob and Pvt to

D
is
.
vb and Pvt are inserted into Eqs obtain
to
The values obtained for Pub and
It
2
3
(
)
(
)
.
and
Xt
Xh .
are put into Eq and the equality greater
+
and tested
If
xt
4.
is
X6 is
X
x
is ),
(
.
.
new higher temperature chosen and the procedure repeated
+
than
If
It
is
a
1,
.
the new temperature should lower than the one chosen originally
be
less than
1,
.
Example 4.11 gives the complete numerical solution
.
MEAN VALUES
Frequently necessary quantity
of as
of
to
determine mean value

it
is
a
a
change The definition

y of
varies because some other variable

in
it
.
of
the mean value

is
X
2
dx
yy
*
S
3.44
)
(
2
SenaT
dx
21
where
y
X2
xi
of
mean value between and

y
.
an
analytical expression for the equation may integrated

be be
there
If
is
,y
analytically Graphical determination mean values may

no
of
used
if
.
analytical method applicable

is
Example 3.11 the heat capacity ethylene glycol

of
of
Determine the mean value

.
50
between and and 100

C
for C
1
0
2
0
,
°
°
(
)
(
)
.
An
Solution analytical expression the heat capacity was developed Exam

in
.
ple 3.1
Cp
0.00113T
+
0.555
=
Therefore , the mean value is
T2
** (0.555 + 0.00113T ) AT
CP =
T2
dT
0.555 ( T ,2 – T ) + 0.00113 ( T , 2 –- 1,2 ) / 2

T ,2 – Ti
( T2 + T. )
= 0.555 + 0.00113
2
For part a,
+ 0.00113 (50 + 0)
Op = 0.555
2
= 0.583 cal / g ° C
For part b,
0.00113 ( 100 + 0)
Cp = 0.555 +
2
= 0.612 cal /g °C
Example 3.12 . Determine the mean value of the flow rate from the data given in
Example 3.7 , for the period from midnight to midnight .
2,000
/ft,
1,500
min
1,000
cu
Q
=
At
ē
,
500
@
@
1
2
8 0
N.
P.M. 12 M. A.M. A.M. 12 P.M. P.M. 12 M. A.M.

8
4
4
hours
e
,
Fig 3.19 Solution Example 3.12

to
.
.Fig
the mean may accomplished graphically

be
of
Solution Determination 3.19

(
)
.
from the data Fig 3.14

of
The average flow rate

is
.
02Som
do
Q
01
=
ē
do
01
02
or
So
02
)01
-
–
Q
de
(
Q
*
The right hand side the equation

of
the area under the curve which was evaluated

is
,
-
in Example 3.7 . Therefore ,
F 1,830,000 cu ft
Q
02 01
1,270 cu ft min /
(24 hr ) (60 min / hr )
Alternatively , may be represented by a horizontal line which has the same area
under it from 0 , to 02 as does the curve . The line is adjusted visually to It
is
often
fit
.
adjust the line equal
to
so
easier that the space below the line and above the curve
is
to
Fig The correct
as
the space below the curve and above the line shown
in
3.19
.
be
value shown to
cu
1,270 min
is
7
=
ft
/
.
APPLICATION OF COMPUTERS IN CHEMICAL ENGINEERING
Computers are revolutionizing chemical engineering Long tedious cal
.
,up
culations are greatly speeded thereby releasing engineers for other
now possible take into account more varia
to
It
more creative work

is
.
more rigorous solution complex problems Com

to
at
of
bles and arrive
a
.
puters permit more adequate analysis and correlation experimental
of
Designs chemical processes may optimized i.e. computers
to be
of
data
,
.
perform the complex calculations necessary find the best possible com
bination design variables Computers are used run actual
to
of
of
dozens
.
experiments For example chemical process whole chemical plant

of or
a
a
,
.
may computer and the effect changing process varia

be
simulated
in
a
bles may Computers may

be
studied without ever building the plant

.
reliability oper
be
processes assuring greater

to
used control chemical
of
,
ation the largest uses computers the business aspects

of
of
of
One
in
is
.
industry such payroll inventory and sales records materials and proc
as
,
ess scheduling and market research

,
is be
Computers may carried
be
used wherever basic calculation must

a
many times with various combinations

of
It
out variables seldom

.
practical computer for single solution problem because

to
of
of
use
a
,
up
problem for machine calculation

to
the substantial time needed set the

.
reality they are quite

In
Computers have been called mechanical brains

.
stupid because they can carry out only few simple operations Their
a
,
advantage speed ingenuity required the engineer

of
of
one Great
is
is
.
up
who must set problem for machine computation He must thor

a
oughly understand the physical situation accu

in he
so
that can describe

it
rately computer description simple

to
the Accurate the terms

as a
.
computer understands requires complex applied mathematics such

numerical methods Thus computers have released the engineer from
,
.
the drudgery the same time chal

at
of
tedious calculations and have

,
,
on
lenged his ingenuity developing methods the computer

of
calculation
in
To meet this challenge the modern chemical engineer needs higher level
a
,
understanding the fundamental physical mecha

of
of
of
mathematics and
of
nisms chemical processes

.
From this short description it is apparent that , although computers

may be considered as " super slide rules , ” they are really much more ver
satile than this . Their ability to explore a much wider range of possible
approaches to a problem and their ability to simulate a system are more
important and of wider usefulness than is their ability to perform more
rapidly the same computations now being done by hand .
Types of Computers . Both digital and analog computers are in use
today . The cave man used digital computing when he counted on his
fingers - and also , for more complex problems , on his toes . Most com
mon computing devices use the digital principle ; they make calculations
by counting discrete units . In the case of the cave man , the discrete
unit was obvious , and hence man developed a decimal system of counting .
In a small adding machine the discrete unit may be a gear tooth or a
shaft rotation in the mechanical linkage . In large electronic digital com
puters , the discrete unit may be an electrical charge on a vacuum tube , a
transistor , or a magnetic film . The digital computer counts discrete units
and manipulates them to add , subtract , multiply , and divide . Very high
accuracy is obtainable .
The analog computer represents a number with some other physical
measurement . For example , the slide rule is an analog computer . It
represents numbers ( or more precisely , their logarithms) by a physical
measurement of length on the rule . As the slide is moved , lengths and
hence logarithms are added and numbers are multiplied . The slide rule
is a mechanical analog ; i.e. , it is a mechanical device for representing
numbers . Another common mechanical analog computer is the planim
eter , which is an integrating device for finding areas included within irreg
ular curves . Analog computers often use electrical properties such as
voltage for analogy to the numerical values .
Analog computers represent numbers by continuously measuring a
physical variable , such as length , as opposed to digital computers which
count discrete units . Continuous measurement enables an analog com
puter to represent continuous functions and give a continuous solution as
the independentvariable is changed . This is an advantage over the digi
an tal
computer which must complete the calculation with one value

of
,
on
independent variable before can start another On the other

it
.
by
hand the accuracy analog computers the precision

of
limited the
of
is
,
required physical measurements

.
on
For example slide rule accuracy depends the precision with which
,
Cheap warped rules are inaccurate and even the

or
the rule made

is is
,
.
four place accuracy Generally analog

or
to
best rule limited three-

,
-
..
computers are less accurate than digital computers but they have the
,
advantage continuous reading Both types computers are very

of
of
.
expensive large sizes Since analogs read continuously earh step

in
in
,
.
the calculation must be done on a separate unit . In a digital computer

the discrete calculation steps permit reuse of computer units in the same
calculation . For this reason digital computers are more versatile at
present , and they dominate current applications . Analogs are used as
research tools , especially for process simulation , but digital computers
handle the bulk of the numerical calculations .
Digital - computer Operation . It is not necessary to know how a digital
computer works to be able to use it , but it is helpful to have a general
idea of the function of the various components . All digital computers
have the functional units shown in Fig . 3.20 , although the design of each
unit may differ widely among various computers . The input enables the
operator to feed data and instructions into the computer . The informa
tion is usually fed through the control unit into the memory where it is
stored for later use . The input mechanism may involve automatic read
ing of prepunched cards , punched tape , or magnetic tape . Information
can be manually supplied with an electric typewriter . The control gov
erns the passage of information among the various other computer units .
It interpretsand carries out instructions which may be stored in memory ,
supplied through the input , or supplied manually by the operator through
the external control panel ( usually a collection of control buttons ) .
all
The memory stores data and instructions supplied The mem
to
to it
.
ory should large and fast
be
Present computers hold up 30,000 sepa

.
rate numbers or instructions
.
Memories are magnetic
or
cores
Arithmetic
unit drums or electrostatic devices
.
Slower auxiliary memories may
magnetic tape
of
consist
.
The arithmetic section actually

Input Control Output
does the calculation adds sub
It
,
.
In
tracts multiplies and divides
,
addition performs certain logic

it
,
Memory and test functions For example

,
.
can test whether number

is
it
Fig 3.20 Functional components positive negative and choose one

or
of
a
.
digital computer
two alternative instructions on
of
.
This section
of
the basis the test

.
also contains registers which information may temporarily stored

be
in
during calculation
.
The output records the answers the problem and other requested
to
information typed pages punched cards

as
some convenient form such

in
and punched magnetic tape

or
The interrelation between these units shown schematically Fig

in
is
.
all
The control unit dictates the action computer

of
3.20 the other units

.
.
The input unit supplies information to memory only . The arithmetic

unit receives information from memory and returns other information to
memory . The output unit receives information from memory only
its
.
small transistorized computer Fig 3.21 This computer
A
shown
in
is
.
has magnetic core memory Input and output may through the
be
-
.
paper tape reader and punch directly from the typewriter The tape
or
-
.
reader feeds information 150 characters per second while output
in
at
,
speeds are characters per second Arithmetic logical and transfer
10
to
15
,
,
.
operations occur about 5,000 such steps per second
at
rates of
.
C
Fig 3.21 The IBM 1620 digital computer the right contains the con
on
The unit
I
.
.
trol panel with associated indicating lights the arithmetic unit the magnetic core
,
,
for
and the typewriter output and manual input

on
memory The unit shown the

,
left contains paper tape reader and space for paper tape punch This tape unit
a
.
by
be
provides higher speed access the computer than could the typewriter
to
obtained
.
Courtesy International Business Machines Corporation

(
.)
Using Computer Using digital computer solve problem requires

to
a
a
.
First the problem must

be
steps
to
reduced numerical
of
succession
a
The computer can handle only simple arithmetic steps and yes
or
form
.
that integrals differentials trigonometric functions loga

no
so
decisions
,
;
is ,
these simple operations This

be
to
rithms etc. must reduced done

,
.
,
by
this chapter plus others such

as
the methods discussed earlier the

in
infinite series instead trigometric functions and the replacing

of
of
of
use
,
differentials by finite differences

.
be
Next the problem must programmed This means that each suc
,
cessive step
In
planned
be
complete program
of
the calculation must

a
,
.
numbers from the memory

to
as
steps such
of
the transfer the arithmetic

unit and the print out
be
information must
of
included These are called

-
.
for
nonproductive steps and usually account the opera

of
over half
“
,
tions in the program . Each step represents an operation and contains a

single piece of information , called a " word .”
The word contains a statement of the operation to be performed , such
as add , transfer , multiply , etc. , and a number signifying the " address "
of the data on which this operation is to be performed . The address
refers to a location within the memory and is directly analogous to the
address of a house . It gives no indication of what will be found at the
indicated address ; it only tells the computer where to go for the required
data . This finished program gives a complete logical picture of the
sequence of operations required by the computer .
A computer program may be presented in simplified and abbreviated
form in a flow chart or block diagram . Here the steps are presented as
blocks connected with flow lines . Information is given within the block
concerning the operation , or series of operations , to be performed . The
detail with which successive steps are shown depends upon the require
ments of the programmer . He may wish to present each computer
step , or only indicate the succession of major equation solutions , address
changes , and logical decisions . Several block diagrams of varying detail
are presented below , especially in Examples 3.13 and 3.14 .
The program must next be coded . This requires that the program be
rewritten in a language understandable to the computer and that every
detail of necessary instruction be included . Coding requires complete
information on the particular computer to be used . Thus , it can be
for
learned only in conjunction with the manuals the given computer and
Coding often
on
learned with practice the computer itself

be
can best
is
.
by computer Some com

of
done staff technicians who work with the

a
puters can arranged

be
so
that the machine codes itself

.
program This can be done

be
The coded must now checked for errors

.
by
by
operating the program step step and checking answers each step
at
unnecessary checking
be
Often this and short cut methods can used

is
.
no
However the program may give may

or
not checked answers

is
it
it
if
,
give wrong answers Checking like coding job for someone familiar
is
a
,
,
.
with the details the particular computer usually

of
use and hence

in
it
is
,
computer program necessary

to
to
of
left the staff revision the

If
is
.
obtain correct solutions the originator will probably have

to
make these
,
corrections
.
Finally the program must This involves the operation

be
of
run the
,
input data from which results are

all
corrected program using

of
the sets
required production usually routine operation and
be
Such can
it
is
,
.
by
carried out computer operator who need not have the mathematical
a
by
understanding required the person who programs

or
codes
.
Programming for Digital computer Solution The engineer faced with

-
tedious calculation can usually obtain computer solution even though

a
a
he is not familiar in detail with the available computer . In most organi

zations where a computer is available , he will not have to code the pro
gram . Perhaps he may find that help is available on writing his program .
In any case , the programming procedures are similar enough so that once
a standard procedure and set of instructions are learned they need only be
modified slightly to make them applicable to any given machine .
Table 3.1 lists instructions available on most digital computers . This
is a very much abbreviated list and does not contain detailed input and
output instructions, decimal - location instructions , nor
all
the transfer
,
arithmetic and logical instructions that are usually available However
,
,
.
will suffice for the simple programming that will
be
considered here
it
.
The instruction along with typical address given the left hand
in
is
a
,
-
No significance should
be
The address
to
column attached the address
.
.
any one the memory locat ons can the program dictates
be
as
of
of
used
,,
.
The explanation for each instruction presented the right hand col
in
is
-
umn These explanations should complete enough
be
to
of
allow use the
.
instruction programming
in
.
all
digital computers use now standard programs called subrou

in
On
,
tines are available These will allow data input and output and will com
.
pute logarithms antilogs trigonometric functions exponential functions

,
,
The programmer need only list the subroutine code
to
etc. have the
computer perform these steps
.
As
simple programming example the calculation

of
the molar volume

a
perfect gas 400 psia can The required calculation

be
at
aa
used
is of
100
F,
°
RT
cu
V
sia
+
mole
lb
R
ft
10.73 100 460

/
°
(
)
(
)
-p
n 400 psia
Р
V
cu
mole
lb
ft
15.02
/
n
as an
an
the computer
be
automatic desk calculator with

to
used were
If
operator the instructions might

be
follows
,
Set the keyboard decimal oint indicator and the carriage decimal
1.
-p
point indicator between the second and third column from the right
.
Enter 100 on the keyboard

2.
Punch the add button

3.
Enter 460 on the keyboard

5. 4.
Punch the add button

.
on
on
Enter the sum found the carriage the keyboard

8. 7. 6.
on ,
Enter 1073 the auxiliary keyboard

.
Move the carriage decimal point indicator point between the

to
a
-
fourth and fifth column from the right

.
Punch the multiply button

9.
.
TABLE 3.1 . DIGITAL - COMPUTER INSTRUCTIONS
Instruction and address Explanation
Bring 1000 * Clear the arithmetic unit to zero , and then bring the con
tents of memory location 1000 to the arithmetic unit .
The contents of memory location 1000 are unaltered .
Add 1001 Add the contents of memory location 1001 to the contents
of the arithmetic unit , keeping the algebraic sum in the
arithmetic unit . The contents of memory location 1001
are unaltered .
Subtract 1002 Subtract the contents of memory location 1002 from the
contents of the arithmetic unit , keeping the algebraic
difference in the arithmetic unit . The contents of mem
ory location 1002 are unaltered .
Multiply 1003 Multiply the contents of memory location 1003 by the con
tents of the arithmetic unit . If the product exceeds the
storage capacity of the arithmetic unit , the most signifi
cant digits are retained . The contents of memory loca
tion 1003 are unaltered .
Divide 1004 Divide the contents of the arithmetic unit by the contents
of memory location 1004 , and keep the algebraic quotient
in the arithmetic unit . The contents of memory location
1004 are unchanged .
Hold 1005 Store the contents of the arithmetic unit in memory location
1005. The contents of the arithmetic unit are unaltered ,
but anything previously in memory location 1005 is
destroyed .
Clear 1006 Store the contents of the arithmetic unit in memory location
1006. The arithmetic unit is cleared to zero , and any
previous contents of memory location 1006 are destroyed .
Store address 1007 Store the address portion of the arithmetic unit into the
address portion of memory location 1007. The contents
of the arithmetic unit and the remainder of the contents of
memory location 1007 are unaltered .
Transfer 1008 The control transfers to memory location 1008 and carries
out the instruction found there . The program proceeds
sequentially from there until a new transfer instruction
is given .
Test 1009 The sign of the arithmetic unit is tested . If it is negative ,
control is transferred to memory location 1009. If it
is zero or positive , the next sequential instruction is
followed .
con
Stop 0000 Stop computing . When used with an address this is a

the
ditional stop which allows computing

to
continue
if
proper control button pressed

is
.
*
an
Any memory address may place

be
as
example
of
the one shown here

in
used
,
except for the stop order

.
obsery
on
on
10. Enter the product found the carriage the keyboard
,
ing the proper decimal point
.
11. Punch the enter dividend button
.
on
12. Enter 400 the keyboard
.
13. Punch the divide button
.
lb on
14.
Read the answer the carriage and record
it
.
Answer 15.02 mole cu
ft
/
(
)
:
.
Writing out this entire procedure may seem tedious and unnecessary
for
simple computation necessary the operator
be
It
such would
if
a
.
were completely untrained otherwise the mere statement Determine
,
;
,
“
might The digital
be
of
to +
the value 10.73 100 460 400 sufficient )
”
/
(
.
computer very similar desk calculator with completely ignorant
is
a
but very accurate operator The same problem programmed for com
,
.
puter solution would appear follows

as
,
Bring 3000
. 1.
Add 3001
6. 5. 4. 3. 2
Multiply 3002
Divide 3003
Clear 3004
Stop 0000
This program could used only after the necessary information was
be
In mem
in
this case the number 100 must be stored
in
stored memory
.
ory location and 400 The

in
in
in
460 3000
3001 10.73 3002 3003.
;
program itself also stored the computer perhaps memory locations

in
in
is
After storing the program the operator manually trans

to
3005 3010.
,
memory location 3005 and starts the computer The com

to
fers control
.
puter brings 100 found memory location 3000 into the arithmetic unit
at
;
,
address 3001 multiplies the

be
to
since 460 would found

in
adds 460
it
;
by
10.73 which address 3002 divides this product by 400

finds
in
it
sum
;
transfers this answer into memory location 3004

in
obtained address 3003

;
leaving the arithmetic unit clear and stops The print out
of
the answer
;
-
.
can
using might memory

be
in
be
done subroutine code which stored

a
for
locations 3011 and 3012. Figure 3.22 gives flow diagram this
a
calculation
.
This program involves very simple computation

and one which cer
a
tainly does not tax the engineer with his slide rule
he
however were
If
,
,
.
an
compute the molar volume 400 psia and

to
be at
at
ideal gas
of
asked
computer use might more attractive
to
10
intervals from 100 1000

,
F
F
°
This would require program like the following

a
The input routine would have stored 100 memory location

in
10
in
in
in
in
in
3000 460 3001 10.73 3002 400 3003 3004 1010

;
;
;
;
in
3005 and 3006

;
.
The remainder of the program is given below :
Location Instruction Address Comments
3010 Bring 3000 100 is brought into arithmetic unit .

3011 Add 3001 560 is now in arithmetic unit .
3012 Multiply 3002 6008 in arithmetic unit .
3013 Divide 3003 15.02 in arithmetic unit .
3014 Clear 1000 First answer is now stored in address 1000 .
3015 Bring 3014 These steps add 1 to the instruction in 3014 .
3016 Add 3006 Thus , address 3014 is altered to read “clear
3017 Store address 3014 1001 ” after the first use .
3018 Bring 3000 These steps add 10 to the number stored in
3019 Add 3004 3000. Thus , address 3000 contains 110 after
3020 Hold 3000 the first use .
3021 Subtract 3005 1010 is subtracted from the temperature .
all
When the result is zero , necessary temper
atures have been used
.
3022 Test 3010 This makes the test When arithmetic unit
is
.
negative control transfers
to
to
3010 repeat
.
Otherwise the program continues
to
3023
.
3023 Stop 0000
This program involves loop That one point the compu

at
in
is
a
"
.”
tation the answer compared with value brought from memory

is
If
a
.
equal larger than the memory value computation
or
to
the answer
is
Store data and ,

Bring Add
Start
in
program
460
=
100
A
=
T
memory
by
by
Multiply Store
in
Divide
10.73 400 memory
=
=
R
Print out
and Stop
P,
T,
answer
Fig 3.22 Flow diagram for molar volume calculation

.
.
continues sequentially the answer smaller than the memory value

If
is
,
..
the program loops back beginning repeats The repeat

to
the and done

is
.
with different numbers however this case each loop repeats the cal
In
,
the molar volume using new temperature higher than

of
10
culation
F
a
,
the temperature previously used Computation stops when the tempera

.
ture reaches 1010 ° F . Another feature of this program is that an arith

metic operation has been performed on an instruction . Specifically , the
“ clear 1000 ” instruction in location 3014 has the number 1 added to it
on each loop through the program so that it becomes successively “ clear

1000 , " " clear 1001 , " " clear 1002 , " etc.
Of course , the program itself is modified as computing progresses . As
a result , a repeat computation would store the answers starting in 1100
rather than in 1000. This is often undesirable , and a method of avoiding
this sort of progression will be given below .
A flow chart for this program is shown in Fig . 3.23 . The simplifi
cation , when compared with the program listed above , is evident ; but
the most important advantage of the flow chart is in the visual pre
sentation of the successive steps and their relation to each other . The
Store data
Start
Bring T Add Multiply by
and program
( 100 ) A = 460 R = 10.73
in memory
Clear to Add 1 to
Divide by Add 10
storage
P = 400 ( 1,000 ) to T
address
Answer negative
D
Subtract
Print
1010 from Test Stop
out
new T
Answer
zero or
positive
Fig . 3.23 . Flow diagram for repetitive molar volume calculations .
address modification which permits storing answers in memory locations

between 1000 and 1100 is shown by the arrow returning to the block
by
for
using the address to be modified . The test completion shown

is
the diamond haped block and the alternate possible arrows one for zero
,
-s
positive answer one for negative answer The loop occurs with the
or
a
,
negative answer control being returned the early part the program
to
of
;
program developed problem variables modi

A of
The above has one the

fied by constant addition each step more common slightly more
at
a
,
.
be
that occurring when

to
complex case
of
whole set values used

is
is
a
,
The the need

in
problem values set

or
to of
for one more the variables

.
no
have relation each other For example the calculation which was
,
.
performed above will be repeated using 100 independent values of tem

perature . The set has no simple internal relation that holds from value
to value . Temperatures of 100 , 175 , 212 , 325 , 440 , 441 , 445 , 495 ° F , ...
could be the first few values of such a set . The program required might
be as follows :
The input routine would have stored 460 in memory location

3001 ; 10.73 in 3002 ; 400 in 3003 ; 3107 ( one more than the highest
address for temperature storage ) in 3005 ; and 1 in 3006. The
100 temperature values would be stored in memory locations
3007 to 3106 .
The remainder of the program is given below :
Location Instruction Address Comments
3107 Bring 3126

3108 Store address 3115
These are initializing steps that put the correct
are
initial addresses in those locations that
3109 Bring 3125
changed during looping
Store address
.
3110 3111
3111 Bring
)
(
3112 Add 3001

do
3113 Multiply 3002 These steps the required arithmetic and

store the answers obtained
.
3114 Divide 3003
3115 Clear
(
3116 Bring 3115
by
These steps modify the address
in
3115
3117 Add 3006
adding each time through
1
Store address 3115

.
3118
3119 Bring 3111
by
These steps modify the address
in
3111
3120 Add 3006
adding each time through
1
3121 Store address 3111

.
3122 Subtract 3005

3123 Test 3111
3124 Stop 0000
3125 3007
3126 1000
this program the steps filled into memory locations 3111 and 3115
In
by
are initially incomplete They are completed the first four initializ
"
.
ing
steps These steps put the proper addresses into these locations
”
by
regardless how they have been altered the program looping

of
in
a
In
previous use program program where data are brought

of
the this
,
.
loop initialize would result

to
memory
at
from new locations each failure

,
the
being brought memory

in
at
extraneous values from each use

in
of
program after the first one

.
The flow chart given Fig 3.24

in
is
.
These programs have been developed in a language as close as possible

to that of a gebra and arithmetic . Recently a shorthand language , called
algorithms , has been used . This language is independent of machine
type , and on many machines a program in this language may be fed into
the computer which prepares a final program in computer language .
Using algorithms , the flow chart of Fig . 3.24 would be as follows :
Algorithm Explanation
Dim T 100 100 memory locations are reserved for values of tem
1 perature . To call for one of these values the symbol
T must be used and an index number showing which
of the T values is required .
Index i The index number is designated by the symbol i.
0 :1 The initial value of i = 0 .
Read R Put R 10.73 in memory .
Read P Put P 400 in memory .
Read j Put j 100 in memory . This is the number of T
values .
S1 read Ti Put Ti in memory . This is the ith value
of T (originally , the 1st value , with i designated as 0 ) .
i +1 = i Add i to i to get next i .
When i less j trn si j
Compares new i to . If i < , control transfers to j
statement Si . Otherwise the next sequential oper
ation is used .
0 :2 The index is reset to zero . At this point input oper
all
ations are complete and numerical calculation can
be
done starting again with the first value
T.
of
,
Using the ith value

S2
of
Mvol the molar volume calculated

+
460
X
Ti
R
is
T
P
,
(
)
/
:
using arithmetic steps indicated

.
Ti
Print The ith value printed

of
T
is
Print Mvol
S2
The molar volume calculated statement printed

in
is
Iterate by adding
to
to
Iter get new new

j
82
. If
less
is
it
1
a
i
i
i.
S2
is to
than control transfers statement Otherwise

j ,
the next sequential step used

.
Stop Stop calculating

.
Except for the dimensioning and indexing step this program like
is
,
that developed before The dimensioning step sets aside enough com
.
all
sequentially
to
puter space
of of
take values
T.
These are then read

in
The index values show which 100 spaces being filled

or
these which
is
,
an
being called for essentially

It
these 100 values address

of
is
is
T
an
After the read loop there calculating loop Both loops use
in
is
a
,
-
.
on
loop this
In
the index value the read

in
iteration shown two

in
is
-
i.
compressed one step the calculating loop Looping

to
while
in
steps
it
is
,
.
by
designating statements looping instruction

to
made easier which

is
a
Si
S2
as
refers etc.
,
,
Programming through the use of algorithms has several advantages ,

but these advantages are only fully realized if the computer has a pro
gram available for translating the algorithms into language the computer
understands . Most computers now have such a program . With algo
rithms the programmer can call for a succession of arithmetic steps with
a single statement , he can similarly call for a complete logical operation
with a single statement , and he no longer has to keep track of the location
Store data Calculate

Start Bring
and program Initialize (460+T')10.73
T
in memory 100
Store
Modify storage Modify T
address by +1 address by +1
no , T- address less than 1+ final storage address
Test
T Print
address Stop
out
(yes,
T - address
equals 1+
final storage
address
and
Fig
for
3.24 Flow chart repetitive molar volume calculation with initializing

.
.
looping
.
In
the memory
in
of
of
information most cases the location the decimal

.
by
Finally efforts
in are
point automatically taken care the computer

of
is
,
.
being made standardize the algorithms program written

to
so
that
a
on
algorithms can almost any computer and will

be
be
run understanda
,
ble
by
the
anyone familiar with computer programming regardless

of
,
he
computer on which most skilled

is
for
3.9
Example 3.13 Example five data points vapor pressure

In
of
variation
the of
.
ethyl alcohol with temperature are given

to
These are used obtain constants

in
.
equation
log
C
, =
+
C
=
T
P
:
by
the least squares method Develop flow sheet for carrying out this calculation
a
-
on digital computer
a
.
Solution . This solution will be more easily understood by reference to Example 3.9 .
Pertinent equations are given there . The flow chart for this computation is as follows :
Store Pu, T data;

numbers 1, 5, and 273 ; to
Start Initialize
and program in 1
memory
Store Hold
1
Bring Add
HT +273 =T, °K
Bring Divide
and store
to
T ,° C 273 1 by T , ° K 2
temporarily Уток =x;
no, fewer than n data to

Modify Test points calculated 1
Multiply Store number
2. addresses of
by x; of t, 1 , x2? loops
yes, n or more data to
points calculated 3
all
xil
At this point memory

of
values and have been calculated and stored
in
Xi
T,
,
.
long flow lines simplify the chart
to
of
Transfer numbers have been used instead
.
by
The test performed here most easily done bringing the number from some
is
0
storage address adding storing the sum back the same address while holding
in
it
,
1,
the arithmetic unit subtracting and testing

in
n
,
Calculate
Bring Hold and Multiply to
Pv
log using
3
=
y
Pu
by
;
yi
store
4
xi
subroutine
a
No fewer than
n
,
data points calculated

3
Modify Test
Hold and number
addresses
4
store xiyi of loops

;;
Pu
;,
of
or
more data
Y
X
Yes
X
;
)
Y;
n
,
95
points calculated
all
this point
79
and Xiyi Table E3.9 page

of
the values have been

At
in
?,
Yi
Xi
xi
T,
,
,
calculated and stored memory The next step add each the columns
in
to
of
is
.
.
Finished
0-25
Modify Test
Add Store
of
Clear address no
.
X
loops
6
of
x
Not finished
Calculate
7 to
xyz
;,
y
?.
£
6
*i
using program
5
6
(
)
Now that the sums have been calculated , Eqs . (3.40 ) and (3.41 ) can be solved .
Algebraically , the solution would be as follows :
The two least - squares equations are
αη + ΟΣΑ ;
αΣυ ; + Σα 2
; Σy :
Στ : !:
( 3.406)
(3.416)
These are rearranged and solved for a and b.
ΟΣ ; Σy:
α + n n
2
ΌΣα ; 2 Στ : 9:
α +
Σας Σr,
Subtracting equations gives
Σα Σy : Στiy
και
2;
:
Στ
n Στι
ΣΙ
n
)
-
.
(
;
Σy Σα Σα
/η
2 4
;
/ /
, ;
:
so that
:
b
ΣΥ Σα
Σ
η
;
;
/
Σy ΌΣα
;
and = :
α
n
for
the computer program carry out this sequence

to
steps given
of
The flow chart
is
by
byAs
below the algebraic solution the coefficient first obtained dividing

in
is
b
,
.
through
of
the coefficients
a
.
Bring Divide Store Bring Divide Store to

Η
7
by
by
8
Συ
Σα
Σα Σ
n
,
n
»
η
η
;
/.
/
to
Bring Divide Store Bring Divide Store
8
by
by
Σα
Σα
Σα Σx
Σκ
Σα
,
,
Σκην
,
;
;
/
./
:
Store
Bring Subtract Bring Subtract to
Σα
Σα
9
10
?
;
../
Σχ
Σα
Σα
Σκ
Σα
Σα
n
,
,
,
Σα
:
/
/
/
;
by
Divide Hold
Subtract Divide
)
Multiply to
Σα
and store
? 2
Σα
10
,
11
by
by
Σα
Σ
n
6
»;
n Σα
;
Clear
Subtract Store Print out
and store
-
11
- α and
Stop
α
b
a
α
Example 3.13 illustrates computer program involving address modi

a
repetitive No trial and error

or
fication and calculation iterative solu

-
-
.
tion is required . In Example 3.14 a program is developed for a simple

trial - and - error calculation .
Example 3.14 . Using the relation
T+
CP
log P, = a +
T'2
where vapor pressure mm Hg
T P
,
,
temperature K
,
°
constants
=
c
b,
a,
of
for values of
T.
The coefficients and are known
P,V
calculate set
a
c
a,
b,
.
Solution Since and are not readily separable trial and error solution
P,V
is
a
,
-
.
To
on
computer the programmer must decide what error

do
this
in
indicated
a
P,
.
that the computer can stop when has approximated

be
so
can tolerated close
all P
it
,
Let required within 0.1 per cent
us
enough
of
assume that itself for values
is
P,
.
The flow chart then might given Fig E3.14

be
T.
as
in
of
.
6
Calculate
all
Store
a,
1, T b,
, c,
to
at
of
values the T; b
Start
log
Initialize
=
P.
numbers and
1
2
1,000 memory and store

in
log
Calculate
=
",
P
Find antilog
2 to
Store and Calculate
=
cP
.';
P
at
1
using subroutine
cP
hold
**
T3
:P
+
T
?
and store
neg
5 to
.
Calculate
Find Store and Subtract
P Pi
antilog Test
2
P
."
-
X1,000
1
hold
P
pos
or
PL
3 to
'
.
"
zero
PI
Calculate
Store and to
2 +
3
";
P
Pi
:
hold
4
=
P
no modified address less

T
6 to
,
than final storage address

T
Modify address
Store
Pi of
of
and
T
Test
5
by
P
storage
!
adding Print values

1
Stop
yes
PP
of
and
T;
Fig E3.14 Calculation flow chart for Example 3.14

.
.
This flow chart presumes that the initial relation is converging in Py . This is prob
ably correct , but depends on the values of a , b, and c , and on the range of T to be
employed .
With the methods discussed in this section the reader should be able to
develop preliminary computer programs and flow charts for simple engi
neering problems . Of course , these programs must be extensively refined
before they can be used on any commercial computer . Most computers
will have a much more extensive list of available instructions , so that
some of the steps done here rather clumsily can be accomplished much
more readily . No attempt has been made here to deal with the problems
of scaling ( decimal - point location and the retention of significant figures ),
of coding into the language understood by the computer , of optimizing a
program so that it requires a minimum of memory capacity and computer
time , or of checking the program and operating the computer . The engi
neer can depend upon the computer staff for help with most of these
steps . However , unless he appreciates at least the rudiments of program
ming , he may not realize either the difficulties or advantages of computers .
DIMENSIONS AND UNITS
A dimension is a description of а
a physical extent . A unit is a defined
measure of the physical extent . Several systems of dimensions and units
the
are in use . In scientific work the absolute system of dimensions and
metric system units are commonly used However several other sys
of
,
.
tems are used engineering work The English engineering system

in
is
.
by
usually used chemical engineers but frequently the absolute metric

,
system used for basic physical data Therefore the engineer must
be
is
,
.
translate his calculations from one system

to
to
able another
.
The fundamental dimensions the absolute system are

of
Dimensions
..
length and temperature All other possible dimen

M
T.
mass time
o
L,
in
expressed Force used

be
is
of
sions can terms these four some

in
systems expressed system

be
using
of
It
dimensions can the absolute

in
.
Newton's law
ma 3.45
=
f
/
F
where force
,
f
m = mass M
,
= acceleration
=
L
2
a
be ,
Equation may
of
to
3.45 used define the dimensions force

:
(
ML
F
3.46
(
m2
This expression defines force mass length and time Energy

of
terms
in
may also expressed mass length and time The kinetic

be
of
terms
in
E
.
energy of mass m is
KE =
12 mv2 ( 3.47 )
L // O
where v = velocity ,, L O .. Equation ( 3.47 ) defines the dimensions of
energy in the absolute system :
ML ?
E ( 3.48 )
The property usually called heat is aa form of energy with the dimensions
of Eq . ( 3.48 ) .
,
The dimensions of other commonly encountered variables
are listed in Table 3.2 .
The gravitational system of dimensions defines force F , length L , time
and temperature T and derives an expression for mass . Obviously , from
Eq . (3.46 ) , M = FO / L .
In energy balances , chemical engineers often implicitly use the system
mass M , energy E , length L , time o , and temperature T. This system is
redundant , because E can be expressed in terms of M , L , and o . How
ever , it is convenient to use and is listed in Table 3.2 as the MELOT
TABLE 3.2 . SYSTEMS OF DIMENSIONS
Gravi
Absolute MELOT MFLOT
tational
system system system
system
Mass m M FO2 / L M M
Length 2 L L L L
Time 0
Temperature T T T T T
Force f ML / O2 F ML / O2 or E /LF
Energy E or H MLP / 02 FL E ML2 / 02 or FL
Area A L2 L2 L2 L2
Volume V L3 L3 L3 L3
Density p M / L3 FO2 / L4 | M / L3 M /L 3
Pressure P M / LO2 F / L2 M / LO2 or E / L3 F / L2
Velocity v L /O L/ L / L/
Acceleration a L /02 L / O2 L / O2 L /@ T
Heat capacity CP L2 /0²T /
L2 OPT E / MT L ’ / 0²T
Thermal conductivity k ML / Q3T F / OT E / OLT ML / 03T or F / OT
Viscosity u M / LO F /OL ? M / LO M / LO or FO / L2
Mass diffusivity D , L2 / 0 L' / L2 /0 L’ /0
MLP / 02 ML / O2
Conversion factor Jgc 9c
E F
system . Another redundant system frequently used by chemical engi

neers is the MFLOT system , listed in Table 3.2 . This arises in the defini
tion of both the pound force and pound mass in the English engineering
the
system of units . Obviously , the MFLOT system is a combination of
a
absolute and gravitational systems
.
Consistency Equations must dimensionally
be
Dimensional con
.
Each additive term must have the same dimensions
as
sistent the other
. Consider for example the energy balance per unit mass
of
terms flow
a
,
,
.
ing fluid which will developed Chap
be
in
6
.
:
Av2
PV
Az
W
ΔΕ
+
+
–
3.49
=
Q
Δ
)
(
(
2
where AE difference internal energy between reference points
of in
=
,
dimensions energy mass
/
V P
pressure force area
/
,
= specific volume volume mass
/
,
= velocity length time
-
V
/
,
gravitational
acceleration length time
= = = =
g
/
?
,
= height
reference point length
of
z
the system energy mass ,

to
heat added
, Q
/
shaft work done by the system energy mass
W
/
/
,
In
the absolute system the dimensions length
M
of
the terms are mass
,
L,
energy ML force ML
L®
time volume and area The
?,
?,
L
?.
,
?
/
Eq
of
dimensions the terms

in
3.49 are therefore

,
,
(
)
.
MLP ML O2L3 L2 MLP ML

L
2
?
/
/
/
+
M L2 M M M
(
Canceling dimensions gives

L2 L2 L2
+ L2 L2 L2
+
+
3.50
02
2
)
©
02
(
2
2
and the equation dimensionally consistent On the other hand the

is
if
,
.
used for force and for energy the dimensions Eq

of
dimension 3.49
is
F
)
.
are
2
E
L3
L
E
F
+
+
+
M LPM M M 3.51
(
)
(
)
This equation dimensionally

inconsistent The first second and third
be is
,
.
terms cannot added their present form This problem arises because
in
the redundant MFELOT system To achieve

of
dimensions was used

.
dimensional consistency necessary use dimensional constants relat

to
it
is
,
ing the redundant dimensions The two con

to
the fundamental ones

.
usually
ge
stants defined are and

J ,
ML
gc
3.52
)
(
2F
FL
J
3.53
(
)
E
Equation ( 3.52 ) defines ge as the ratio of force dimension in the absolute

system to the force dimension in the gravitational system . Equation
( 3.53 ) defines J
as the ratio of energy dimensions in the gravitational
system to the energy dimension in MELOT system . is referred to as
energy equivalent of heat ," where FL is mechanical
J
the " mechanical
energy and E is heat . The factor ge should not be confused with the
acceleration of gravity gg. Although they may have equal numerical val
ues , they always have different dimensions . The numerical values of go
and J depend upon the units used , as discussed later .
Equation ( 3.51 ) may be converted to a dimensionally consistent form
by insertion of gc and J.
Equations ( 3.52 ) and ( 3.53 ) may be written
=
ML
Fgc ( 3.52a )
2
and ЕЈ FL ( 3.53a )
Combining Eqs . ( 3.52a ) and ( 3.53a ) gives
ML2
EJC 2 ( 3.54 )
The right -hand side of Eq . ( 3.52a ) is the correct dimensions of force in

the absolute system ; therefore , Fge should be used in Eq . ( 3.51 ) instead
of F. Similarly , Eq . ( 3.54 ) shows that energy should be EJg . instead of
E. With these corrections Eq . ( 3.51 ) becomes
EJSC Fgeс L3
2 L EJSC EJg .
L
M +
L2 M + (51) ori +
M M ( 3.55 )
This equation can be shown to be dimensionally consistent by combining

Eqs . ( 3.52a ) and ( 3.54 ) with it . For this system of dimensions Eq . ( 3.49 )
becomes
AEJg. + A ( PV ) g . +
Δυ2
2
+ g Az
g = QJg
Q . -- W
W Jg . (3.56 )
Whenever a redundant dimensional system such as MFELOT is used ,

dimensional conversion factors must be included . From a scientific point
of view , it would be preferable to avoid conversion factors by avoidance
of redundant dimensions . However , engineering practice often uses M ,
F , and E at the same time , making and ge necessary . J
Application of dimensional consistency to Newton's law ( Eq . ( 3.45 ) ] is
informative . In the MFLOT system the dimensions are
ML
F
2 ( 3.57 )
which is dimensionally inconsistent . The correct form is

ML
Fg . (3.58
and Eq . ( 3.45 ) becomes

fg . = ma ( 3.59
This equation is the only correct form of Newton's law if dimensions of

force F and mass M are both used . If
only the absolute system is used ,
Eq . ( 3.45 ) is correct as written . This point will be further clarified in
the discussion on units .
Units . Units are arbitrarily defined measures of
a dimension . For
example the metric unit for the mass dimension is the gram ; the metric
,
unit for the force dimension is the dyne ; and the metric unit for the energy
dimension is the joule . The units for several dimensional systems
are
given Table 3.3 which deserves careful study The metric and English
in
.
systems widely The English engineering system
of is of
units are both used .

units the English system units applied
to
of
of
the redundant MFLOT

system dimensions
.
the metric system the dyne and joule are defined

In
so
that the dimen
,
are both unity the English system
In
ge
sional conversion factors and

J
,
.
poundal unity
ge
so
the and slug are defined that the for each How
is
.
ever the pound force lbs and pound mass lbm are more frequently
,
not unity Many special units have been defined

ge
for
used and
is
,
specific applications For example the calorie and the Btu are energy
,
.
units used heat measurements Many subdivisions and multiples

in
of
.
units are used for example kilometers meters centimeters millimeters

>
,
,
,
etc.
The terms mass and weight are often confused Weight has dimen
.
the force exerted by gravity For exam

on
of
sions force
It
is
mass
a
.
by
the
ple one pound weight may

be
as
lbs defined the force exerted

1
,
on )
(
gravity one pound mass By Eq 3.59

of
acceleration
9
(
)
(
.
)
.
fgc = ma 3.59
)
(
32.2 sec
a
ft
g
т =
1
lbm
gc
32.2
ft
lbm
lb
sec2
,
-
//
mg sec
lb ft
lbm 32.2
1
)
, /
(
)
(
Therefore
f
=
,
gc
32.2
ft
lbm sec
/
-
?
=
lbs
1
Although have the same numerical value they have different

gc
and
g
dimensions and units constant varies with altitude and lati

is
.g
g
a
;
.
its
variation influence most engineering calcula

to
is
tude but too small

,
FOR VARIOUS DIMENSIONAL SYSTEMS
.
TABLE 3.3 TYPICAL UNITS
Absolute Dimensions Gravitational Dimensions MFELOT System

Physical extent
and symbol Dimen Dimen Dimen
Metric unit English unit Metric unit English unit Metric unit English unitt
sion sion sion
m
/ L
*)
Mass
ft
1
M
/
or
g
M
(
)
gram pound lbm FO2 dyne sec2 cm lbs sec2 Ibm slug
-1
(
/)
slug
1
L
ft
)
( )f(t
ft
Length centimeter cm foot cm cm
o
Time
()
second sec sec sec sec sec sec
°
F
°
C
°
C
°
F
T
Temperature degreescenti- degrees Fahr
grade enheit
F
F
ſ
g
*
/
Force
(or
ML M2 sec2 lbm sec2 dyne Ibg
cm
dyne lbs poundal
)g( ( ( )
1
1(
) )
dyne poundal
1
=
) ft-
joule Btuf 778 lbs
E
(F° /ft /ft
-ft
- -
/ /
sq
-
FL
I
)°C 1( /
sq
Energy
g
ML2 02 sec2 lbm sec2 dyne cm lbs = FL 0.239 cal
cm
1
-
dyne cm
A
Area L2
ft
sq cm sq L2 89 cm sq L2 sq cm sq
V
ft ft
ft ft
Volume
107
L3 cu cm cu L3 cu cm cu L3 cu cm cu
M
ft
4
|
/
4
cu
L4
ft
ft
g
L3
cu
Density cm lbm cu FO2 dyne sec2 cm lbj sec2 cm lbm
MM
in
sq
in
sq
Pressure
gg
L3 L2
cu sq
.
sq
LO2cm seca lbm sec2 dyne cm lbs dyne lbs

cm
oP v
L2 M
Velocity cm sec sec cm sec sec cm sec fps
a
Acceleration ft
ft
02 sec2 sec2 O2 sec2 sec2 O2 cm sec2 sec
C
°
C
°
L2
cmsq
°
cmsq
L2
g
C
cp
F
ft ft sq
sq
2T
Heat capacity 02T sec sec2 sec2 sec2 MT joule Btu lbm
cm
cm
k
°C
FF
/F/L L /F
2°
F
°C
°ft
Thermal conductivity ML O3Tgcm sec3 lbm sec3 OT dyne sec Ibs sec OLT joule sec Btu sec
° cm
u
L2
°C sq/
ft
/ // g
/ // -
sq
Viscosity LO sec lbm sec FO dyne sec cm Ibs sec LO cm sec Ibm sec
cm
/ / /L /L // / /
/ // //
M L2
/ f/t/ / /ft /-ft /ft /ft
/ // / /
-/// // - /
M L2
/ / / /g /
ft / / / / / / /
Do
sq
/. F°/ F° ft/ /
sq
sq
sq
Mass diffusivity
-/ft/ / ft / - ft
sec sec L2 sec sec cm2 sec ft2 sec
cm
cm
ft
g
lg 32.2 lbm
cm
gc
Conversion factor
=
ML F2gc gc
dyne sec2 lbs sec2
1
- - - ft
- -
--
dyne cm 778 lbs

J
=
J
Conversion factor
/ /F /L /L /E /E / 0/ / E/
FL
joule Btu
In
.
be
be
this book pounds mass will abbreviated lbm pounds force will abbreviated lbs
,
of
.
English engineering system with the addition thermal energy units
of
* †|
(
of
in
is
(
.)
The calorie cal and the British thermal unit Btu are special units energy used connection with thermal energy heat One calorie the quantity
to
to
g
1
; ) .°C1
is
of
of
1
1
of
.°F
heat required raise the temperature water One Btu the heat necessary raise lbm water
ft
J , )( -
-ft
slug lbm
1
=
1
=
gc
-
lbj sec2 poundal sec2
tions . The specific weight is defined as the weight per unit volume . It
has dimensions of force per volume .
Because chemical engineers frequently process masses of material , they
use the absolute unit of pound mass , analogous to the chemists ' gram
mass . However , other branches of engineering more frequently are con
cerned with forces and use the pound weight or force . Strictly speaking ,
the weight of an object varies with location ( as g varies ) , but the mass is
a constant .
The poundal is sometimes taken as the unit of force in the English
absolute system . It is the force that gives one pound mass an accelera
tion of 1 ft / sec ?. By Eq . ( 3.59 )
ma ( 1 lbm ) ( 1 ft / sec )
Ic =
f 1 poundal
lb m ft sec ?
= 1
poundal
The poundal is defined so that ge equals 1. Although this is convenient ,

the poundal is seldom used .
The slug is defined as a unit of mass in the English gravitational system
so that ge = 1. It is the quantity of mass accelerated to 1 ft sec ? by /
one pound force . Therefore ,
( 1 slug ) ( 1 ft / sec slug- ft / sec
gc 1
1 lbs lbs
The slug is equal to 32.2 lb mass .
Conversion of Units . The engineer spends considerable time convert
ing from one system of units to another . A systemic approach to con
version can save time and eliminate errors . After an engineer has com
pleted his numerical calculation must check units to be sure they are
, he
consistent . Conversion is most easily accomplished by the

of units
multiplication of the number to be converted by appropriate unit ratios .
For example , suppose an energy of 100 Btu must be converted to units
of foot - pounds force . From Table 3.3 or Appendix A , it is found that
1 =
Btu = 778 ft -lb ,
Rearranging gives the unit ratio
778 ft- lbs 1

1 Btu
The 100 Btu may be multiplied by the unit ratio ( i.e. , by 1) without
its
changing value Therefore

,
.
lbs
-ft
778
Btu
=
100 77,800 lbs

ft
Btu
-
1
The units Btu are canceled just like numbers

.
Example 3.16 . The liter - atmosphere is an energy unit . Convert 25 liter -atm
to Btu .
Solution . The atmosphere is a special pressure unit which does not explicitly use
the units of pressure . It is equal to the standard atmospheric pressure , which is the
pressure exerted by a column of mercury 760 mm high at 0 °C . The pressure could
be calculated if the density of mercury were known . Alternatively , Appendix A
states that
1 atm = 14.7 lbs / sq in .
1 ft 12 in . 30.4 cm
1 liter 1,000 cu cm
1 Btu =· 778 ft- lbs
Then
1,000 cu cm 1 ft * 14.7 lbs / sq in . ( 12 in . ) ? 1 Btu

25 liter - atm
1 liter 30.4 cm:) ' 1 atm ( it )" 778 ft - lbs
12 ft
( 25) ( 1,000 ) ( 14.7 ) ( 12) : ( liter -atm ) (cm ) (ft ) (lb ) ( in ) ( Btu )
(30.4 ) *(778 ) ( liter ) ( cm (atm ) ( in ( ft ( ft- 16 )
All the units except Btu cancel , and 25 liter -atm 2.52 Btu .
PROBLEMS
3.1 . Develop an empirical equation to express the variation in heat capacity of

isobutyl alcohol with temperature , using the following data :
T , °C 0 10 20 30 40 50 60 70 80 90 100
/
CP, cal g °C 0.505 0.537 0.570 0.607 0.642 0.675 0.705 0.737 0.770 0.808 0.840
log
3.2
on
Plot the following equations rectangular semilog and log

of
each
,
-
.
coordinates
:
a. Y
+
24.1 3.2x
b. Y 4.5e0.32
3x4
. C.
y Y
2x2
5
d
3.3
Find data for any phenomenon you believe and develop

be
to
linear function
a
,
.
equation for
an
it
.
by
decay can the following equation

be
3.4 Radioactive expressed

:
.
dN
-AN
do
nuclei present
N
where
of
at
number time
0
decay constant
λ
Evaluate the decay constant for iodine 131 from the following data
:
hr
Time 50 100 150 200 250 300 350

0
,
1.00 0.84 0.69 0.58 0.49 0.40 0.34 0.280

N
N
0
/
3.5
The viscosity liquid follow the following relationship over

to
of
believed
is
a
.
short temperature ranges

:
CeA
=
T
M
/
where u = viscosity , centipoise

T absolute temperature , ° K
A, C empirical constants
Determine A and C from the following data for carbon tetrachloride :
T , °C 20 30 40 50 60 70 80
M, centipoise 0.969 0.843 0.739 0.651 0.585 0.524 0.468
3.6 . Determine empirical equations for the following data . Fill in the missing
value by extrapolation or interpolation .
a. X 0 5 10 15 20 25 30 35
Y 0.20 0.30 0.45 0.67 1.0 1.50 2.25 ?
b. x 10 20 40 60 120 240 480 640 960
Y 40 27.5 18.5 14.7 9.9 6.7 4.6 ? 3.1

c. 0 20 40 60 80 100
Y 180 135 90 45 0 ?
3.7 . The viscosity u of a gas is approximately proportional to the absolute tem

perature raised to some power ( TP ) . Determine the exponent on T and the propor
tionality constant from the following data for carbon dioxide at 1 atm pressure . Use
both graphical and numerical methods and compare results .
T, ° K 288 293 303 313 372 455 575
M, centipoise 0.01457 0.01480 0.0153 0.0157 0.01861 0.02221 0.0268
T, K
° 763 958 1123 1325
M, centipoise 0.0330 0.0380 0.0436 0.0479
3.8 . The heat - transfer coefficient h is related to the velocity of flow v by the equa
tion h auß . Determine the constants a and ß from the following data :
v, ft / sec 1 3 5 7 9 12
h, Btu / hr sq ft °F 150 370 565 750 920 1160
3.9 . Calculate compositions and masses for the following additions and subtrac
tions graphically on a right - triangular diagram . Plot salt on the horizontal axis and
water on the vertical axis .
a . Two mixtures are mixed together . 100 lb : 25 per cent salt , 45 per cent water ,
30 per cent sand ; and 250 lb : 10 per cent salt , 70 per cent water , 10 per cent send .
b. 200 lb salt , 100 lb sand , 400 lb water are mixed together .
c. 200 lb of solution is drained from the following mixture : 700 lb containing 20
per cent salt , 40 per cent water , 40 per cent sand .
d . 100 lb of water is evaporated from 500 lb of mixture containing 30 per cent
water , 40 per cent salt , 30 per cent sand .
3.10 . A mixed acid is to be prepared from spent acid , 99 per cent sulfuric acid ,
95 per cent nitric acid , and water if necessary . Determine graphically :
a. The masses of sulfuric acid , nitric acid , and water necessary to convert 1,000 lb
,
of spent acid (40 per cent H2SO4 , 20 per cent HNO3 , 40 per cent H2O ) to a mixed
acid of 50 per cent H2SO4 , 40 per cent HNO3 , 10 per cent H2O .
b. The mass of water which must be evaporated from 1,000 lb of the spent acid to
produce a mixed acid of 66 per cent H2SO4 , 33 per cent HNO3 , and 1 per cent H , O .
3.11 . Using Eqs . (3.13 ) and (3.14 ) derive
M = Xa3 Xa2
M Xal - X a2
Show how this expression may be used in graphical addition and subtraction .
3.12 . Using the data of Prob . 3.1 , calculate
80 ° C
ΔΗ Cp dT
( a) analytically , with the empirical equation , (b) graphically .

3.13 . Calculate the approximate total daily production and the average hourly
production rate from the following data :
Time 12 M 3 A.M. 6 A.M. 9 A.M. 12 N 4 P.M. 8 P.M. 12 M
Production rate , lb / hr 2,000 2,000 5,000 9,000 12,000 12,000 8,000 2,000
3.14. In filtration , the volume of filtrate collected is related to the time of collection
by an equation of the form
0 = CV2
where @ = time , min
V = filtrate volume , cu ft
C = empirical constant
Using graphical differentiation determine the constant C. ( Hint : de / dV 2CV .)
0, min 0 2 4 5 7 9 12 15 20
V, cu ft 0 1.80 2.54 2.84 3.37 3.80 4.40 4.90 5.70
3.16. Using Eq . (3.2 ) calculate the mean heat capacity of water vapor between
100 and 300 °C: (a ) analytically , (b) graphically .
Fit
for
an
equation the following approximate data the following

to
of
3.16. each
cases
:
three term equation solving the equations simultaneously for the required
A
a
,
-
.
constants
.
three term equation using Lagrange's equation

A A
b
,
-
.
five term equation using Lagrange's equation

c
,
-
.
Plot the resulting equations calculating several points between those fitted
,
.
/dy
for each equation Which equation

60
10
40
dx
the best
at
Calculate and
is
=
x
representation
of
all the data

?
5.0 10.0 20.0 30.0 40.0 50.0 60.0 70.0

X
9.0 17.0 28.5 36.0 43.0 46.5 53.0 56.5

y
Using the method least squares three term polynomial

fit
to
of
3.17 the data

a
,
-
.
given Prob 3.16

in
.
3.18 . Using the method of least squares , polynomial
fit
to
the data given
in
a
Prob 3.1
by
3.19 Develop three term polynomial for the following data Lagrange's
a
-
(
)
:
.
by
method the method least squares
of
6
,
(
)
.
0.0 2.0 4.0 6.0 8.0 10.0
X
0.0 1.0 3.5 6.0 9.0 13.0
y
/dy
Find 4.0 for each polynomial
dx
at
=
x
c
(
)
an
Fit polynomial the following data using appropriate method
to
3.20
a
:
.
0.5 1.0 2.0 3.0 4.0 5.0 6.0
130 70 40 30 25 22 20
y
3.21 Solve the following equations for
x
x2 .
:
x4
13
+
+
era
a
.
3x3 2x2 1.3x 20

b
.
1
2
2
x
3
x
)
(
)
(
)
(
=
2
c
.
+
1
2
x
(
)
x2
12
=
d
.
for
Write computer flow charts and programs given
of
obtain the values
yy
to
3.22
.
the following equations

In
of
of
values and are constants

in
each each case
d
x
a,
b,
c,
.
of
known value
.
bx
dx3
+
+
cx2
= =
y
a
1 a
.
bx
x2
+
y
b
)c
(
/
.
X d
sin
C.
=
y
23
! 29
...
Note sin
-
-
=
2
z
:
No
-
)
9
-
+
+
(
*7!
ši3!
ă5!
cear
=
d
Y
dx
.
+
b
(
22
23
= Note
+
+ ! 2
1+
ez
Note
+
+
=
.
:
:)
(
:
!3
1
!
x2
x3
+
+
e
Y
b
a
c
(
)
(
)
(
)
.
computer program solve the following set equations for

to
of
3.23 Write and

.y
a
x
.
.
10y 235
+
x
ху 160
by
-by
Solve this problem also hand computation following step step the com
b
-
.
puter program written above

of .
money fixed compound interest

at
of
3.24 The future worth sum invested

P
S
a
.
rate for years given by the relation

is
n
i
+
S
1
"
(
i)
for
Develop program and flow chart the computation 10,000

of
of
the future worth

$
a
per cent interest for times ranging from years

20
at
invested
to
6
for
3.25 Using the relation Prob 3.24 develop computer flow chart calculating
of
a
,
.
for
at
per cent
10
20,000 invested
of
of
the future worth interest rates and

$
3,
4,
5,
6,
periods ranging from years

20
to
5
.
3.26 . Develop a computer flow chart to obtain values of
dx
so" et 2 X
where x takes integer values from 10 to 30 .

3.27 . Develop a computer flow chart to solve Prob . 3.5 .
3.28 . The virial equation of state gives the following relation between pressure ,
for
volume , and temperature gas
f2
V (T
fi
PV RT
T
)
(
)
+
+
V2
Write computer program given

to
f2
calculate for and when and
fi
V
T
a
T
(
)
(
)
are known
.
3.29 Draw the computer flow chart for the program obtained Prob 3.28
in
.
.
3.30 Using the virial equation given Prob 3.28 draw computer flow chart
in
to
a
.
.
100 150 200 250 300 350 and 400 psia tempera
50
calculate
at
for pressures
of
V
,
tures
of
100 200 300 400 and 500

F
,
°
as by .
3.31 Write the program required the calculation outlined Prob
in
3.30
.
.
3.32 differential equation such
A
.
dy
?by
+
=
a
dx
be
can approximated with difference equation

a
Δy
?by
+
=
a
AX
Yi
Yi
+ +
or
1 1
by
+
=
:2
a
Xi Xi
-
The excellence approximation increases For the above

of
→
of
Yi
as
Yi
course
+
,
Yn 1
,
.
of for
equation develop computer flow chart

determining
. of
from known values
n, a
, ,
X1
Xn
equal increments
Y1
an xn
of
and where the number between and

xı
is
n
in x
,
a,
b,
all
3.33 Determine the dimensions for the quantities listed Table 3.2 for
.
FEOT system
of
dimensions
.
an
all
the quantities ELOT

of
3.34 Determine the dimensions Table 3.2 for

in
.
system
of
dimensions
.
3.35 Check the following equations for dimensional consistency See Table 3.3
(
.
for definition symbols

of
)
.
-AP
D2
where
D
diameter
ft
32lvu
. a
/
,
,
.
KA AT heat transfer rate Btu

g hr
where
b
9
,
/l,
, /
Na
hr
ca
where transfer rate and concen

D
,V
Aca mass moles

c
=
N
A
.
/
/l,
,
cu
tration moles cm
g
/
,
Eq
so
of
of
3.36 Write the dimensions 3.49 that each term has the dimensions
(
)
.
FL
M
M
E
)6
a
/
,
(
)
Write Eq 3.47 the MELOT system inserting necessary dimensional con

in
3.37
,
(
)
.
version factors
.
3.38 The following equation dimensionally inconsistent the units specified

in
is
.
Insert appropriate dimensional conversion factors

.
2ρ
ΔΡ
–
U
D )
(
V
CA2
D2
1
(
-
/
)
*
where w = flow rate , lbm / sec

A 2 = area , sq ft
p density , lbm / cu ft
-ΔΡ pressure loss , lb ; / sq ft
D2 , Di diameters , ft
C =
= dimensionless constant
3.39 . Convert the following quantities to the units indicated , using basic conversion
.
factors :
a . Density of 1 g / cu cm to lb / cu ft
b. Pressure of 1 atm to dynes / sq cm
c. 1 hp -hr to joules
d . Heat capacity of 1 joule / g ° C to Btu / lb ° F
e. Viscosityof 1 poise to lbs - sec / sq ft
f . Mass of 1 slug to grams
g . Force of 1 poundal to dynes
h . Thermal conductivity of 1 Btu / hr sq ft (° F / ft ) to cal / sec sq cm (° C / cm )
3.40 . Several dimensionless ratios are used in chemical engineering . For each of
the ratios listed below , determine that it is dimensionless , and suggest appropriate
units .
a . Dup / u, where D = diameter
b. Cpu k /
c. u /pDv>, where D, is the mass diffusivity
REFERENCES
66
1. Davis , Dale S .: Empirical Equations and Nomography ,” McGraw - Hill Book
2. Foust , A. S. , et al .: “ Principles of Unit Operations , ” John Wiley & Sons, Inc. ,
New York , 1960 .
3. Hildebrand , F. B .: “ Introduction to Numerical Analysis , ” McGraw - Hill Book
4. Laidler , K. J6
.: “ Chemical Kinetics ,” McGraw - Hill Book Company , Inc. , New
York , 1950 .
5. Mickley , H. S. , T. K. Sherwood , and C. E. Reed : “ Applied Mathematics in
Chemical Engineering ,” 2d ed . , McGraw - Hill Book Company , Inc. , New York ,
1957 .
6. Perry , J. H. (ed .) : “ Chemical Business Handbook ,” McGraw - Hill Book Company ,

Inc. , New York , 1954 .
7. Scarborough , James B .: “ Numerical Mathematical Analysis ,” Johns Hopkins
Press , Baltimore , 1955 .
CHAPTER 4
PHYSICAL AND CHEMICAL PRINCIPLES
The chemical engineer applies principles of physical chemistry to solve

many problems in chemical processing . Physical chemistry is concerned
with physical equilibrium between phases , with reaction equilibrium
between chemical compounds , and with the rate of chemical reactions .
These subjects , together with process variables , will be considered in this
chapter. Physical chemistry is also concerned with the energy or heat
effects of physical and chemical changes. Chapter 6 will deal with these
heat effects .
There is no clear division between the fields of physics and physical
chemistry or between physical chemistry and chemical engineering . The
distinction perhaps is that the engineer is more interested in applying
the principles elucidated by the physicist or the chemist . In any case ,
the engineer must have a thorough understanding of the principles before
he can apply them .
PROCESS VARIABLES
To determine how well a process is functioning the chemical engineer

must measure process variables , such as temperature , pressure , com
position , density , and flow rates . In such measurement and recording of
process variables automatic equipment is frequently employed .
Temperature . Temperature is an extremely important process vari
able . Chemical - reaction equilibria and reaction rates depend upon tem
perature ; the physical characteristics of a substance are dependent on
temperature ; the unit operation of heat transfer involves transfer of
energy as heat between two regions of different temperature .
From a physical point of view , temperature is a measure of the average
kinetic energy of the molecules of the substance . Energy is the ability
to do work , that is , to overcome a resisting force through a distance .
Kinetic energy is that energy associated with the motion of a body
through space . In contrast , potential energy is energy resulting from
the position or configuration of a body . A raised weight , a stretched rub
ber
all
band the explosive charge rifle cartridge possess potential

—
in
a
,
115
the rubber band released , or
the
energy . When the weight is dropped ,
off
explosive set the potential energy released other energy forms
in
is
,
,
kinetic energy and heat
as
such
a the
any substance can have kinetic energy result
as
of
of
Molecules
a
the molecules through space They also have energy
of
movement
as
.
the vibration
of
the atoms within the molecules and
of
as
sult result
a
,
the atoms within the molecules
Of of
of
of
the rotation the molecules and
.
course any substance contains molecules with wide range
of
kinetic
a
proportional
the
energies The temperature being bulk property
to
is
a
,
,
.
these various molecular kinetic energies

of
mean
.
an
the
body energy increase results either
in
of to
When heat added
is
,
kinetic energy potential energy
of
or
form the molecules
of
the form
in
associated with the molecule spacing energy being
to
molecule Heat
is
-
-
a also
by
temperature driving force Energy may

of
transferred means
a
.
work but the driving force would
be
of
be
transferred the form
in
,
pressure gradient electrical potential height above
or
as
directed one such

,
,
datum plane The interrelated phenomena energy heat work and
of
a
,
,
,
.
temperature will discussed more fully Chap They are intro

be
in
6.
.
gas
an
develop understanding temperature and

to
duced here
of
of
behavior
.
The temperature body cannot measured directly Tempera

be
of
a
.
actually property
on
ture measuring devices depend some other which

-
varies with temperature For example the gas thermometer depends

,
.
upon the increase volume the gas with increase temperature

in
in
, of
the at
constant pressure Similarly the mercury thermometer utilizes
.
the liquid the temperature rises The resistance

in as
of
increase volume
in
change conductor with

of
thermometer utilizes the electrical resistance

a
temperature Temperature measurement with the thermocouple
is
.
based upon the temperature dependence the electrical potential existing

of
the boundary between two dissimilar metals The use the high
at
of
.
temperature optical pyrometer depends upon the increase intensity

in
of
the temperature
as
visible radiation increased above 500

is
C
°
.
Definition unit and scale for measuring the dimension tempera

of
of
aa
aa
arbitrary
on
centigrade
of
ture The scale based the definition

is
is
C
0
°
.
the freezing point pure water and 100 the boiling point
at
at
of
of
water
C
,
°
atmospheric pressure the unit

at
both the standard Therefore

of
,
1
.
degree centigrade equal 1oo the temperature difference

to
C
is
1
°
(
freezing point boiling point the expansion

of
between the and water

If
.
carefully measured various pressures the data may

at
real gas
of
be
is
a
extrapolated zero pressure perfect gas From these

to
to
simulate
a
data found that for every rise temperature the extrapolated

in
it
is
C
1
,
°
by
the
This suggests
at
gas volume increases the fraction 273.16

C
0
1
/
°
.
absolute temperature scale where the zero point

an
of
definition taken
is
PHYSICAL AND CHEMICAL PRINCIPLES 117
at the limit of contraction of the ideal gas . The absolute centigrade

scale is called the Kelvin scale and is defined as
T (°K ) = T (°C ) + 273.16 ( 4.1 )
The temperature in degrees Kelvin is equal to the temperature in degrees

centigrade plus 273.16
engineering calculations 273.16 is usually
. In
off
It
The temperature
to
of
rounded called absolute zero
K
273.
is
0
°
.
be
noted that the unit the Kelvin scale the centi
as
of
should the same
is
grade scale The zero points
of
the scales are different but the
C
,
1
,
°
.
of
size the degree the same

is
was originally based
on
The Fahrenheit the freezing point
of
scale
an
on
an
ammonium chloride solution erroneous value for the and
F
0
°
(
)
temperature the human body now defined based upon
96
of
It
F
is
°
(
) .
the freezing point and the boiling point
32
of
of
water water 212
F
F
°
°
(
(
) .
an
As
absolute temperature scale may
be
before defined The Rankine
,
.
scale defined by
is
+
R
459.69 4.2
T
T
F
°
°
)
(
)
off
may engineering
be
The
to
The constant rounded work

in
460
.
equal
to
Rankine degree the Fahrenheit degree

in
size
is
.
There are 180 Fahrenheit degrees and 100 centigrade degrees between
freezing boiling points
of
the and water Therefore

,
.
ΔΤ 180
F
°
(
AT 100
C
(°
)
or AT 1.8 AT 4.3
C
F
°
°
(
)
This equation useful for temperature differences Substituting the
is
temperature the lower reference point into Eq 4.3 gives

at
of
value
(
)
.
= 1.8
32
–
T
–
F
C
0
°
(
((
°
)
or 1.8T
+
32 4.4
C
F
°
This equation useful converting temperatures between the two

in
is
scales
.
on
There one temperature which identical the Fahrenheit and centi

is
is
by
immediately setting
be
This can
in
grade scales found

=
F
C
T
T
°
°
.
.Eq
4.4 Then
(
).
= 1.8T
+
T
32
F
F
°
-40
-
T
F
°
that -40 -40

C
so
F
°
particularly convenient temperature con

as
of
This can serve means

a
The procedure would the temperature whether

40
to be
to
or to
version add
,
.
by
centigrade multiply 1.8 depending

or
Fahrenheit divide
is
it
the scale with smaller sized degrees

to
upon whether the conversion

is
-
at the limit of contraction of the ideal gas . The absolute centigrade

scale is called the Kelvin scale and is defined as
T (°K ) = T (°C ) + 273.16 ( 4.1 )
The temperature in degrees Kelvin is equal to the temperature in degrees

centigrade plus 273.16
engineering calculations 273.16 is usually
. In
off
It
The temperature
to
of
rounded called absolute zero
K
273.
is
0
°
.
be
noted that the unit the Kelvin scale the centi
as
of
should the same
is
grade scale The zero points
of
the scales are different but the
C
,
1
,
°
.
of
size the degree the same

is
was originally based
on
The Fahrenheit the freezing point
of
scale
an
on
an
ammonium chloride solution erroneous value for the and
F
0
°
(
)
temperature the human body now defined based upon
96
of
It
F
is
°
(
) .
the freezing point and the boiling point
32
of
of
water water 212
F
F
°
°
(
(
) .
an
As
absolute temperature scale may
be
before defined The Rankine
,
.
scale defined by
is
+
R
459.69 4.2
T
T
F
°
°
)
(
)
off
may engineering
be
The
to
The constant rounded work

in
460
.
equal
to
Rankine degree the Fahrenheit degree

in
size
is
.
There are 180 Fahrenheit degrees and 100 centigrade degrees between
freezing boiling points
of
the and water Therefore

,
.
ΔΤ 180
F
°
(
AT 100
C
(°
)
or AT 1.8 AT 4.3
C
F
°
°
(
)
This equation useful for temperature differences Substituting the
is
temperature the lower reference point into Eq 4.3 gives

at
of
value
(
)
.
= 1.8
32
–
T
–
F
C
0
°
(
((
°
)
or 1.8T
+
32 4.4
C
F
°
This equation useful converting temperatures between the two

in
is
scales
.
on
There one temperature which identical the Fahrenheit and centi

is
is
by
immediately setting
be
This can
in
grade scales found

=
F
C
T
T
°
°
.
.Eq
4.4 Then
(
).
= 1.8T
+
T
32
F
F
°
-40
-
T
F
°
that -40 -40

C
so
F
°
particularly convenient temperature con

as
of
This can serve means

a
The procedure would the temperature whether

40
to be
to
or to
version add
,
.
by
centigrade multiply 1.8 depending

or
Fahrenheit divide
is
it
the scale with smaller sized degrees

to
upon whether the conversion

is
-
Pressure The pressure at a boundary of a material is the average

.
force on a unit area of boundary resulting from the repeated collisions of

molecules with the boundary . The molecules of gas in a closed container
collide with the wall of the container , exerting a force . As the tempera
ture is increased at constant volume , the molecules will move faster , and a
greater force will be exerted on the wall by the molecules . Therefore ,
the pressure increases . At constant temperature , if the volume of the
container is decreased , the molecules are closer together and collide more
frequently with themselves and with the wall . The increased frequency
of collision with the wall exerts a greater force and gives a greater pressure .
Pressure may be measured by balancing various forces against it .
In a manometer , the weight of аa column of liquid is balanced against the
pressure . In the usual dial pressure gage , sometimes called a Bourdon
gage , the pressure deforms an elastic metal tube to a degree proportional
to the pressure .
Mechanical pressure gages and some manometers measure the dif
ference between the actual pressure and atmospheric pressure . This
difference is called the gage pressure. The actual or absolute pressure is
usually required in calculations . The absolute pressure is given by
Pabs Pgage + Patm ( 4.6 )
The standard atmospheric pressure is defined as the pressure exerted by a

column of mercury 760 mm in height at 0 ° C . This pressure is equal to
/
14.70 lbf sq in . and is defined as 1 atm .
Density . The densities of gases , liquids , and solids vary with tem
perature and pressure , as will be discussed later in this chapter . As
shown in Table 3.3 , density has dimensions of M / L3 and units of grams
per cubic centimeter or pounds mass per cubic foot . The maximum
density of water is at 3.98 ° C where
p =
= 0.999973 /
g cu cm = 1.000000 /
g ml
=
= 62.3 lbm cu ft
The specific weight is for engineering purposes numerically equal to the
density ; but it has dimensions of F / L , as discussed in the previous
chapter .
The specific gravity is usually defined as the ratio of the mass of a
material to the mass of an equal volume of water at 4 ° C or other specified
temperature . The temperatures of both the material and the water
must be specified , because the density varies with temperature . For
example , the specific gravity of a material at 20 ° C referred to water at
4° C is
P20°C
SG 20°/ 4° ( 4.7 )
PH20,4°C
The density of water at 4 ° C is 1.0 g cu / cm , and

P20°C
SG 20°/ 4° ( 4.7a )
1 g /cu cm
The specific gravity is numerically equal to the density expressed in

grams per cubic centimeter , but it is dimensionless . The specific gravity
of a gas is occasionally used . It is defined as the ratio of the gas density
to the density of air at a specified temperature and pressure .
Composition . The composition of a gas , liquid , or solid mixture may
be expressed in many ways . Several of the important ones are discussed
here .
Mass fraction , as the term implies , is the ratio of the mass of any one
component to the total mass of the mixture . Mass per cent is obtained
by multiplying by 100.
all
The sum of the mass fractions for components
of
the mixture must total that

is
1
;
,
i
Xi = =
1
4.8
(
)
where the mass fraction for any component Weight fraction
Xi
is
is
.
numerically equal Both terms are dimensionless
to
mass fraction
..
.
Mole fraction one component
in of
the ratio
of
the number
of
moles
is
to
of
of
the total number moles the mixture One mole material has
a
.
numerically equal the molecular weight gram mole

to
mass which
A
is
.
has the mass grams pound mole has the mass pounds
in
in
Therefore
a
,
,
.
mole
lb
The sum
of
453.6 moles the mole fractions must total

g
1
1
;
.
that
is
,
Ś2-1
Xi = 4.8a
Σ
)
the
where the mole fraction for any component The mole has
xi
is
dimension mass and the mole fraction dimensionless

of
is
,
Volume fraction frequently used for gases and occasionally for liquid
is
solutions the volume one component would occupy

It
to of
the ratio
is
.
by
under the existing pressure the total volume occupied the gas For
.
numerically equal
to
as
ideal gases the mole fraction discussed later

it
is
,
in
this chapter
.
mass per volume Typical units

of
Concentration has the dimensions

c
are the
cu
liter moles liter

cu
and moles Because

lb
in ft
ft
are
/g
lbm
/
//
/
,
total mass fixed volume varies with temperature concentrations

a
temperature dependent
.
Traditionally certain units have been given

of
these concentration
,
the
special terms Thus concentration expressed normality refers

to
in
a
.
gram equivalents solute per liter The molarity

of
of
solution
of
number
.
the
gram moles solute per liter

to
of
of
refers the number solution and

of
of ,
molality gram moles solute per 1,000

of
of
the number solvent

is
.
These units have been most frequently applied by the laboratory chemist .
Thus they are often seen in tables of chemical data or in the results of
chemical analyses .
Example 4.1 . A liquid contains 60 mass per cent ethyl alcohol and 40 mass per
cent water at 30 °C and 1 atm . Calculate :
a . The mole fraction .
b. The concentration in grams ethyl alcohol per liter of solution .
c. The concentration in pound moles ethyl alcohol per cubic foot of solution .
=
Solution . The molecular weight of ethyl alcohol is Me 46.1 ; of water , 18.0 .
The density of a 40 per cent ethyl alcohol , 60 per cent water solution at 30 ° C is
found to be 0.938 g / cu cm , from Appendix C. This is an experimental value ; it
cannot be calculated .
a. It is convenient to select a basis for calculation . In this case a mass of M =
100 lbm will be satisfactory .
Mass fraction ethanol , te = 0.40
Mass fraction water , Xw = 0.60
Mass ethanol , M. = Mxe ( 100 ) (0.40 ) 40 lbm
Mass water , My MXw ( 100 ) (0.60 ) = 60 lbm
Moles ethanol Me / M . 40 / 46.1 = 0.869 lb moles
Moles water Mw / M. 60 / 18.0 3.33 lb moles
Total moles 0.869 + 3.33 4.20
Mole fraction ethanol , ae = 0.869 / 4.20 0.207
Mole fraction water , Xw = 3.33 / 4.20 = 0.793
b. BASIS : 1 liter solution .
liter =
cu
Mass solution
in
cu
0.938 cm 1,000 cm 938

g
/g
1
:
(
)
(
Mass ethanol Mxe 938 0.40 375 g

)g
:
(
)
Ce
liter
of
Therefore concentration ethanol 375

g
=
/
,
solution
ft
C.
BASIS cu
1
.
:
/gIbm
( 62.3
cu /
Mass solution
)ft
in
cu
cu
cu
/
ft
cu
cm 58.4 lbm
=
ft
0.938
g
1
)
(
62
)
(
/
(
0.40 58.4 lbm

(
)
(
Moles ethyl alcohol 0.506

=
cu
in
ft
1
46.1 lbm mole

lb
/
cu
moles
lb
ce
Therefore
ft
0.506
/
,
Flow Rate Many process instruments

to
are used measure flow rate

.
Many measure some other property the flowing

of
of
the instruments
be
Instruments have been

to
system which can related the flow rate

.
developed for measuring point velocities volumetric flow rates and mass
,
Each these would have different applications The

of
flow rates
.
principles elementary fluid

in
or of
various flowmeters are discussed

mechanics unit operations books
.
may expressed feet per second miles per hour

in be
The flow velocity

in
v
The velocity pipe varies from zero maxi

to
at
the wall
of
etc. flow
is a
a
pipe The average velocity desig

at
of
of
mum the center the flow

.
nated by
7
.
may expressed cubic feet per second

be
The volumetric flow rate

in
Q
,
gallons per minute , etc. In a pipe or closed flow duct of cross - sectional
flow area A ,
Q Αύ ( 4.9 )
Equation is a basic relationship between the flow velocity and the

( 4.9 )
volumetric flow rate .
The mass flow rate m is expressed in pounds mass per hour , grams per
second , etc. It is related to the volumetric flow rate by
m = pQ (4.10 )
PHYSICAL STATES
Matter may exist in one of three states of aggregation : gas , liquid , or

solid . The molecules of a crystalline solid are held in a fixed array by
strong intermolecular attractive forces . The molecules vibrate around
fixed positions , but usually do not migrate within the solid . As energy is
added to the molecules ( by heating , for example ) they vibrate more
rapidly , until at the melting point the vibrations overcome the inter
molecular forces and the fixed molecular array of the solid breaks down
into the disordered arrangement of a liquid . The liquid still possesses
significant intermolecular forces which hold the molecules close together ,
so that there are frequent collisions between molecules . Individual
liquid molecules migrate slowly through the bulk of the liquid . As the
liquid is heated , the molecular energy increases , until at the boiling point
it overcomes intermolecular forces . The resulting gas molecules migrate
freely through the volume occupied by the gas , frequently colliding with
other molecules . Intermolecular forces still exist , but they are much
smaller than in liquids . The gas molecules are more energetic than
liquid molecules , and the liquid molecules are more energetic than those
in the solid . It follows that the temperature of a gas is higher than that
for a liquid of the same composition and pressure , and the liquid tempera
ture is greater than that of the solid . A substantial quantity of energy
must be added at the melting and boiling points to change the physical
state .
Gases . The volumetric behavior of gases has been studied since the
Reformation . In the seventeenth century Robert Boyle stated that the
its
volume of a gas is inversely proportional to absolute pressure That

is
,
.
V2 = Р. at constant
T
Vi P.
was not until the early nineteenth century that Jacques

It
Charles and
Gay Lussac stated that the volume gas directly propor
L.
of
also
J.
is
a
-
tional to its temperature . Thus :
V2 T
at constant P
Vi Ti
The laws of Boyle and of Charles may be rewritten as
V2
Vi = $1(T)P.
) (
P2
Pi and
V2
V: =
02 ( P ) T2
)Ti
where 01 ( T ) is a function of temperature only and $ 2( P ) is aa function of

It
T2
pressure only .
fix
01
is clear that these two relations and
T
=
1
T
/
(
)
P1 P2. Combining the laws Boyle and Charles gives
of
of
02
=
P
/
(
)
V2 PiT2
1
V P2 Ti
or
P.V2 = PV constant
T.
=
T
apply Including this

to
gas
of
of
These relations course fixed mass
a
,
.
gram moles pound moles
or
as
of
the relation above number

in
mass
a
:
P.V1
constant The constant usually
T2
PzV2
X
called the
=
is
=
n
T
/
.
1
R.
gas constant and given the symbol Using this constant the
”
"
ideal gaslaw results

-
PV nRT
=
=
( 4.11
where total pressure )

P
F
L
/
,
total volume
L3
=
n V
= number M
of
of
moles gas
,
= gas
MT MT
LP
or
constant
E
T R
= =
/
,
L
(F
/
)
(
)
/
absolute temperature
T
,
the gas constant depends upon the units chosen

of
The numerical value

for the other terms For example pressure pounds force per square
in
if
is
.
pound degrees Rankine

in
inch volume cubic feet moles and

in
in
T
n
,
=
cu
R
sq
mole
lb
R
in
lbs
ft
10.73
/
'
)
/
)
(
(
for other units are given Appendix

of
A.
Values
in
R
More recently the perfect gas law has been derived from simplified
a
of ,
kinetic theory This theory visualizes gas phase being made

as
gases
a
.
up
very large number molecules acting independently

of
These
of
a
molecules move straight line paths altering direction only upon colli
in
,
-
with the walls The collisions

or
of
sion with each other the container

.
the colliding molecules

of
are elastic that the momentum conserved

is
is
;
The model requires that there nor repulsive force

be
neither attractive
between molecules and that the volume of the molecules themselves be

essentially zero .
Consider a unit area of the wall enclosing this model gas . This wall is
bombarded by molecules moving at an average speed c , but in random
the
directions . The molecular velocity may be expressed in terms of
so
vector velocities and the and directions that
in
w
,y
z
u,
v,
x,
y2
u2
+
c2
+
=
w2 4.12
)
no
Since the gas phase has bulk velocity the vector velocities totaled
,
( all The mean
of
algebraically for the particles must equal zero the
.
velocities squared will not equal zero but must
be
uz
the same for any
,
)
given direction averages for large number
of
Therefore terms
in
of
a
.
particles
and
02
+
v2
c2
u2 u2
=
=
w2 W2 13.02 4.13
)
In
do
the small time interval molecules with the velocity component
,
perpendicular the wall will strike the wall they are located within
Un
to
if
the distance uido from the wall This
.
gas uide
of
describes volume
in
which
a
,
molecules will have the required veloc
ni
U
ity component
In
the gas phase there
.
-ll molecules per unit volume

ne
are also
velocity component etc. These
U2
vith
,
also strike the wall during
de
they
if
Molecule
are originally within the volume uzdo
,
u
etc.
Unde
Since the collisions are perfectly elastic
site ,
the particles will leave the collision
they had
of
-Wall unit area

with the
of as
samemomentum
,
before collision but the sign the veloc

,
Fig 4.2 Gas molecule colliding ity component

be
will reversed This

is
.
with container wall

Fig 4.2
.
The change
in
shown
in
momen
.
the particles striking

all
tum then 2mu for each impact For unit

of is
a
,
area wall
,
Change momentum
in
1
2m
2mEnu = niui
+
nguza
=
n1u1
•
?
Unit time
:) )
(
4.14
(
appears because only those particles having component

12
The factor
velocities directed toward the wall will strike Reducing this
to
func
it
a
.
tion
of
the mean velocity component

,
пju пи
++
+
.
2
?
,
u2
ni
+
n2
+
пju
+
+
пzu uant 4.15

2
,
2
)
(
The change in momentum per unit time is

Momentum change 1
2mu’nt = mnru ? ( 4.16 )
Unit time 2
or in terms of molecule speed ,
Momentum change 1 Ñ
Unit time mnrc ?
= т ‫م‬2
( 4.16a )
3 3 ✓
Ñ is Avogadro's number ( the number of molecules per gram mole ) ;

V is the volume per gram mole ; and nt is the total number of molecules
per unit volume . From mechanics the force equals the rate of change
of momentum . Since a unit area has been considered ,
F 1 Ñ
= P m
A 3 V
or PÕ 12 m Ñ c = 23 x 12 mÑcz ( 4.17 )
all
The term 12 m Ñ CZ is the kinetic energy of the molecules present and
is
,
proportional the temperature
to
therefore
,
PV kinetic energy at
23
4.18
=
)
This the perfect gas law again designated
as
the constant
If
aa
is
is
R
-
,
.
the universal gas constant

,
RT = KE
23 23
KE
lg
or for
R
mole 4.19
(
)
T
be
this way the gas constant

of
found the ratio the total

to
In
R
is
,
,
all
to
energy associated with

of
the translational motion the molecules

on
the
Of
temperature
of
course this derivation based model the

is
a
.
real physical situation which very much simplified More realistic

is
different quantitative results but the qualitative

to
models would lead

,
result would not be changed

.
by
Example 4.2 Calculate the volume occupied

of
200 lbm methane CH4

a
(
)
)
.
at
225 and atm conditions are changed

F
to
and atm what volume

If
5
°
100
F
.
,
°
(
)
does the gas occupy

?
Solution
atm
T n P
a
5
.
lb
16
mole 12.5 moles

=
200 lbm lbm

lb
=
/(
)
/
+
460 225 685

R
°
From Appendix
cu
atm
lb
Therefore
R
A
0.7302 mole
.R
=
ft
/
-,
,
-
nRT
cu
atm mole
lb
lb
12.5 moles 0.7302 685

R
R
ft
/
°
V
'
(
)
(
)
(
atm
Р
5
cu
1,250
ft
b. At the conditions of part a (conditions 1)
PiVi n (RT1
At the new conditions (2 )
P2V2 n2RT2
Therefore ,
Pivi ni Ti
P.V. n2 T2
In this case , ni = n2
Pi = 5 atm P2 = 1 atm
Ti 685 ° R T2 = 460 + 100 = 560 ° R
Vi 1,250 cu ft
PT'2,
V: =
P , Vi
5 atm 560 ° R
1,250 cu ft
1 atm 685 ° R
= 5,110 cu ft
The ideal - gas law specifies that the gram -molar volumes( or pound
all
gases are equal equal temperatures and pressures

at at
molar volumes ) of
.
Thus stating the volume gas fixed temperature and pressure
of
a
,
specification For this purpose

to
amounts the mass has been con

of
it
.
pick arbitrary values temperature and pressure and desig

to
of
venient
The most common standard condi
as
nate these standard conditions

.
Hg and 14.7 psia

32
At these
or
tions are and 760 mm

F
C
0
°
°
(
)
.
conditions the perfect gas law gives the volume
as
of
mole
lb
1
-
RT
V
10.73 492
✓
359 cu
=
)
(
ft
=
п 14.7
P
Similarly the volume Obviously the statement

of of
mole 22.4 liters

g
is
1
,
lb ,
.
cu
nitrogen equivalent
to
359 standard the statement

1
ft
“
is
,
“
nitrogen nitrogen Even

or
of
of
28
mole 359 standard

lb
cu
if
,
ft
”
.”
nitrogen cooled and compressed for example

59
to
of
and 100 psia

–
F
is
,
°
there still mole present

is
lb
1
use
These conditions are not the only standard conditions

in
“
14.7 psia
60
Engineering practice often uses

as
standard conditions
,
F,
°
cu
resulting mole The American cylinder gas industry

in
lb
ft
379
/
Hg standard conditions resulting pound mole

68
30
as
cu in
in
uses
a
F,
°
con
In
occupying 386 standard conditions this book standard

at
ft
ditions will always refer 14.7 psia but this

32
to
not universal
is
F
,
;
°
practice
.
at
Real Gases Real gases deviate from the ideal gas law extreme
-
.
pressures and temperatures The derivation the ideal gas law assumes
of
-
.
no
intermolecular forces and negligible volume molecules compared

of
to
an
the space between them Van der Waals developed equation

to
take
.
into account these factors :
(
a
– RT
P V2
+ ) (V b) ( 4.20 )
n²a
nRT
P +
(V –
or
=
4.21
m2 )
+ V2
)
v nb ) =
where the molar volume and and are empirical constants deter
is
b
for each gas
?2
mined The term accounts for the attractive forces
Õ
a
/
.
of
between molecules and corrects for the volume b the molecules
,
.
for few gases are given
of
of
and Table 4.1 number
in
A
Values
a
a
b
.
more accurate empirical equations state have been developed since the
of
Van der Waals equation.5
TABLE 4.1 VAN DER WAALS CONSTANTS
*
.
'
Gas liters atm mole liters mole
g
g
2
b,
/
a,
/
(
)
(
)
(
Ammonia 4.170 ) 0.03707

Benzene 18.00 0.1154
Carbon dioxide 3.592 0.04267
Diphenyl 52.79 0.2480
Helium 0.03412 0.02370
Nitrogen 1.390 0.03913
Oxygen 1.360 0.03183
Water 5.464 0.03049
by
Reproduced from Ref permission

2,
*
by
Example 4.3 Calculate the volume occupied water vapor

at
of
mole 900
g
C
1
°
.
by
and 100 atm the perfect gas law using Van der Waals equation
6
a
,
-
(
)
(
)
:
.
'
Solution
= 0.08206
K
liter atm mole

=
g
R
°
/
K
1173
P T
100 atm
5.464 liters atm mole

=
)2
n b a
)
/g ?(
)
/(
0.03049 liters mole

mole
g
1
nRT mole 0.08206 liter atm mole 1173

g
/g
K
1
)
°
°
)
(
V
)
(
a
P.
.
100 atm
0.963 liter
=
by
Van der Waals equation solved for trial and error

6.
V
is
'
a
RT
)
vV
+.
M
–
=
P
(
b
)
)(
1173
-++
100
) )
5.464 0.03049 0.08206

–
= =
v
)
(
)
(
96.3
Let V 1.0
( 100 + 5.464 ) ( 1 – 0.0305 ) 102 € 96.3
Let V 0.9
( 100 + 6) (0.9 – 0.0305 ) = 92 + 96.3
Let V 0.94
( 106.2 ) (0.91 ) = 96.6 . 96.3

Therefore V = 0.94 liter .
Another equation of state for real gases includes a compressibility

factor 2 ,
PV nzRT ( 4.22 )
The compressibility factor may be determined from measurements on the

gas itself. Itmay also be obtained from generalized correlations appli
5
all
cable to gases with moderate accuracy These correlations recognize
.
the similarity between the volumetric behavior
at
different gases
of
the
same relative distance from their liquefaction points
in .
Gas Mixtures When several components exist gas phase mole
,
.
each component are distributed evenly throughout the entire

of
cules
by
its
phase Each component contributes molecules with
of
collisions
,
.
the containing wall part the total system pressure

of
Also any
a
,
,
as of .
by
it all
given molecule the presence the com
of
affected molecules
is
ponents present the same way

so
that seldom moves would

in
of it
if
it
,
existed within phase the same temperature and

at
like molecules
a
pressure This interaction effect between components real gas phase in

a
.
quite complex and this book cannot consider constructively There

is
it
,
.
fore the discussion that follows applies
of
ideal gases mixtures

to
,
.
The partial pressure component the pressure which
as
of
defined
is
a
the component alone occupied the volume formerly

be
would exerted
if
by
occupied the mixture Therefore Eq 4.11 describes the total

if
,
is (
)
.
a .
mixture the partial pressure component

of
,
paV nRT 4.23

=
n
)
(
partial pressure
pa
where component
of
= =
component
in of
mixture
na in
na
moles
is a
by
The mole fraction Dividing Eq

ya
the gas 4.23 4.11

/n
(
.
)
.
gives
na
Р Pa
=
Ya
4.24
(
)
п
the partial pressure composition term related

to
Therefore the mole

is
,
fraction
.
Dalton's law states that for gaseous the partial

of
mixture the sum

a
pressures equals the total pressure

.
4.25
P
pi
=
{
)
The pure - component volume is the volume a component would occupy

at the temperature and total pressure of the system . The pure -com
ponent volume V ,a is defined by
PV . =
= nRT ( 4.26 )
Dividing Eq . ( 4.26 ) by ( 4.11 ) gives
Vo na
= Ya (4.27 )
V п
Therefore the volume fraction Va / V is equal to the mole fraction Ya .
The concentration Ca may be obtained by rearranging Eq . ( 4.23 ),
na = Pa
Ca =
V RT (4.28 )
Combining Eqs . ( 4.24 ) and ( 4.28 ) gives
Pya
са ( 4.29 )
RT
The concentration is directly proportional to the total pressure and
inversely proportional to the temperature . The total concentration C
is equal to the sum of the individual concentrations Ci ,
1
С
ÉcCi ( 4.30 )
The total concentration is also the molar density , that is , the total moles
per unit volume , as shown by combining Eq . (4.30 ) with ( 4.29 ) .
Ci
C = {
Pyi
C= RT
P
С (4.31 )
RT
n
Therefore , С ( 4.32 )
V
Gas- phase compositions can be expressed and calculated using either

the
partial pressure the pure component volume quite common

or
It
is
-
express gas phase compositions per this case Eq

so as
volume cent
In
to
.
.
-
always presumed
apply that the volume per cent composi
to
is
4.27
(
is )
equal per composition On the other hand

to
the mole cent

is
it
tion
.
the partial ressure basis

on
carry out calculations

to
more normal
.
-p
Although the results are the same partial ressure considerations are
,
-p
physical situation than are volume per cent

to
much closer the actual

considerations . Partial pressures are useful when calculating con

densation temperatures or deviations from ideal - gas behavior .
Example 4.4 . For 100 cu ft / min of a gaseous mixture of 10 per cent CH4 , 30 per
cent C2H6 , 60 per cent H , (by volume ) at 70 ° F and 20 lbs / sq in . gage , calculate :
a . The mole fraction of each component .
b. The concentration of each component ( pound moles per cubic foot ) .
c. The partial pressure of each component .
d . The molar density of the mixture .
e. The mass flow rate of the mixture .
f. The average molecular weight of the gas .
Solution
a . The mole fraction is equal to the volume fraction ; therefore ,
YH , = 0.6 Усн . = 0.1 YC2H6 0.3
b. By Eq . (4.29 ) , with T = 460 + 70 = 530 ° R and Pabs 20 + 14.7 = 34.7

lbs / sq in . ,
CH2
Рун .
RT
/
(34.7 lbs sq in .) (0.6 )
[ 10.73 (lbs /sq in . ) (cu ft ) / lb mole ° R ](530 ° R )
=
0.00366 lb moles cu ft/
Similarly , CCH4
= 0.00051 lb
mole cu / ft
CC2H6 0.00183 lb mole / cu ft
c. By Eq . (4.24 )
PH2 - Pyh , (34.7 lbs /sq in .) (0.60 )
20.8 lbs /sq in .
Similarly , PcH4 = 3.5 lbs / sq in .
=
PC2H6 10.4 lbs sq in . /
d. By Eq . (4.31 )
Р 34.7 lbs / sq in .
C =
=
RT [ 10.73 (lbs / sq in .) (cu ft) / lb mole ° R ](530 ° R )
0.00610 lb mole / cu ft
e. BASIS : 1 lb mole of gas
NH2 0.6 пси , 0.1 C2H6 = 0.3
MA2 = nu , H , M (0.6 lb mole ) (2 lbm lb mole ) / = 1.2 lbm

Similarly , Mcha (0.1 ) ( 17 ) 1.7 lbm
Mc, (0.3 ) (30 ) 9.0 lbm
Total mass ΣΜι = 11.9 lbm
Volume occupied by 1 lb mole at standard conditions 359 cu ft
Volume occupied by 1 lb mole at 70 °F and 34.7 lbs / sq in . ,

PAT2 14.7 530
V2 Vi 359
P2T1 34.7 492
= 164 cu ft
Therefore ,
11.9 lbm
р
164 cu ft
0.0725 lbm cu / ft
and
m == P Q = (0.0725 lbm cu ft ) ( 100 cu/ ft /min ) /
- 7.25 lbm min
=
f. From e, 1 lb mole of gas mixture has a mass of 11.9 lbm .. Therefore , Mar
/
11.9 lbm lb mole .
Liquids . As the temperature of a gas is lowered , intermolecular attrac

tive forces become more effective until the gas condenses into a liquid at a
fixed temperature . This temperature , the boiling point , has a unique
value for a given pure material at a constant pressure . The boiling point
varies with total pressure . In mixtures , condensation occurs over a
range of temperature , as discussed later in this chapter .
Liquid mixtures may consist of two or more liquids ( such as ethyl
alcohol and water ) , gases dissolved in a liquid ( such as ammonia in water ),
or solids dissolved in a liquid

( such as salt in water ) . When two com
ponents are mixed , the properties of the mixture cannot always be pre
dicted . The volume of the mixture may be less than the original volume
of the two components , and the density cannot be predicted . Therefore ,
it is necessary to have experimental data on density of liquid mixtures
available . Data for ethyl alcohol and water solutions are given in
Appendix C.
Example 4.5 . One U.S. gallon of ethyl alcohol is mixed with one U.S. gallon of
water at 68 °F . Determine :
a . The composition of the resulting solution as mass fraction .
b. The composition as mole fraction .
c. The volume of the resulting solution .
d. The composition as volume per cent .
Solution
a . From Appendix C,
Pure ethyl alcohol at 68 °F , e = 0.789 g / ml
Pure water at 68 °F , e = 0.998 g / ml
1 gal 3.785 liters
Mass of 1 gal ethyl alcohol
( 1 gal ) (3.785 liters / gal ) ( 1,000 ml / liter ) (0.789 /

g ml )
2,990 g
Similarly , mass of 1 gal of water = 3,780 g

Total mass =- 2,990 + 3,780 6,770 g
2,990
Therefore , Xalcohol = = 0.441
6,770
3,780
= 0.559
XH20
6,770
b. Mole fraction
2,990 g = 65 g moles
Moles ethyl alcohol in 1 gal
/
46.1 g g mole
3,780 g
Moles water in 1 gal 21 g moles
/
18.0 g g mole
Total moles 65 + 21 86 g moles
65
Therefore , Xalcohol 86 = 0.756
XH20 = 2186 0.244
c. From Appendix C , the density of a solution of 44.1 per cent ethyl alcohol , 55.9 per
cent water (by weight ) at 68 °F , is
р = 0.9271 /
g ml
Total mass of solution - 6,770 g
6,770 g
Volume
(0.9271 /
g / ml ) ( 1,000 ml liter ) (3.785 liter / gal )
= 1.932 gal
Therefore , on mixing 1 gal of ethyl alcohol with 1 gal of water , there is a volume
reduction of 3.4 per cent .
d . Because of the decrease in volume on mixing , there is no rigorous definition of
volume per cent . However , the alcohol industry defines the proof scale by a volume
per cent which is the ratio of the volume of alcohol required to make up a mixture to
the volume of the mixture . In this case , the volume per cent alcohol would be
1 gal
100 = 51.7 %
1.932 gal
This solution is 103.4 proof , since the proof scale is simply twice the volume per cent
calculated in this way .
The composition of solutions of gases or solids in liquids may be

expressed in mass or mole fraction or as concentration in mass per unit
volume of solution . The temperature must be specified with a concen
tration because density is temperature and composition dependent .
Solids . A solid results when sufficient energy is removed from a liquid
so that the intermolecular forces restrain the molecules into vibration at
fixed points in a crystal lattice . Solid solutions are common , for example ,
in metals . In other cases a solid may be a more or less intimately mixed
heterogeneous aggregation of elements and compounds , as in an ore .
Compositions of solids are expressed as mass or mole fraction or per cent .
The transition from liquid to solid is called the freezing or melting point .
It is a unique temperature for a pure substance , and it is only slightly
sensitive to pressure . For example , at a pressure of 325 atm the melting
Appendix
ice
point of Various melting points are tabulated

in
–
2.5
is
C
..
°
E.
PHASE EQUILIBRIA
The chemical engineer frequently concerned with the distribution

of
is
components between two phases The unit operations

of
mass transfer
.
are based upon differences composition between two phases equilib

in
in
two phases different composition are brought into contact

of
If
rium
,
.
the various components will transfer between the phases until the rate
each component equal
of
of
transfer both directions When this

in
is
composi
no
dynamic equilibrium occurs there will change

be
further
in
,
the two phases

of
tion
.
The phases involved may be gas , liquid , or solid . The chemical engi
neer must be able to determine or predict the compositions of phases in
equilibrium . In a few cases theoretical relationships predict phase
equilibria ; in others empirical equations are used ; in many cases the
experimental data are reported directly by tables or graphs .
Willard Gibbs applied the concepts of physics and mathematics to a
study of phase equilibria . He was able to show that there is a quantita
tive relation between the composition of a component in one phase and
that of the same component in any second phase provided that the two
phases are in equilibrium . His development resulted in the statement :
Mi = ui ' = Mi ( 4.33 )
where mi , ma' , Min are the chemical potentials of component i in the phases
designated by the primes . Qualitatively , the chemical potential is a
measure of the “ escaping tendency ” of the compound , or the likelihood
of molecules of the compound to leave the phase in question . The
chemical potential is a function of phase composition , temperature , and
pressure . For solutions of ideal gases it is proportional to the partial
pressure . This relation assumes that equilibrium exists between phases
( ), ( " ), and ( "' ' ) . An important condition of equilibrium is that the
all
be
all
temperatures and pressures of phases must equal Thus
,
.
potentials are balanced including and
u
,
T,
P,
an
With these relations between chemical potentials important restric

by
on
phase equilibria can obtained merely matching the number

be
tion
equations system Suppose that there
of
in to
of
the number variables

in
a
phases equilibrium with components existing throughout these

P
are
C
,
phases Then the existing independent relations are

.
ТР equations
P
-
T
T
T
'
pl
1
PI PP equations
.
P
1
-
11
equations
Mi
.
M2 MI
M1
1
?
P
-
M21
M2
equations
-
.
M2²
1
uc
Mc
uc
equations
==
uc
-
P
=
1
all
Adding these independent equations gives
Number equations
of
4.34
–
P
2
1
)
(
(
)
)
(
The independent variables would pressure temperature

be
and
–
C
1
,
composition variables for each phase There are not independent

C
.
composition variables for each phase because
x1 + x2 + x3 + x'c 1.0 4.8a
)
Adding
all
the independent variables gives
Number variables =
of
+
4.35
–
P
C
2
(
(
)
)
equations relating
be
of
balance can now made between the number
A
As
independent variables any set
of
the variables and the number
in
of
.
simultaneous equations complete specification requires that the number
equations equal the number When this happens every
of
of
variables
.
The experimenter may not
all of
intensive variable the system fixed
is
he
be
sure that there are
of
of
know the values these variables but can
,
unique values the variables are greater number than the equations
in
If
.
relating them the system not completely specified the vari
of
Some
is
.
by
given
be
the experimenter before the system can
of be
ables must values
completely specified the number equations exceeds the number of
If
.
independent variables too many specifications have been made These
.
excess specifications are either redundant actually conflicting In
or
of .
they
be
either case should removed before further examination the

system Thus general
in
,
.
be
equations
to
fixed
+
of
Number Variables
=
V
(
)
(
Number independent variables

of
4.36
(
(
)
Substituting Eqs 4.34 and 4.35 into 4.36 gives
.
(
=
+
+
P
–
-
4.37
V
P
=
CC
C
1
1
(
)
(
)
Upon simplifying this becomes the phase rule
:
+
4.38
V
P
=
C
where phases present

of of of
number
P
= = =
= components present
number
V C
intensive variables which may independently

be
=
number
or
specified sometimes called the degrees

of
freedom the
,
variance
the quantity
on
one whose value does not depend

An intensive variable
is
the phase present For example pressure temperature density and

of
,
.
composition are intensive variables On the other hand total volume

is
,
.
the quantity present and

on
an
dependent therefore extensive variable

is
,
,
Similarly even though the compositions individual phases are inten

of
,
all
system composition
an
sive variables the over extensive variable

is
,
-
its
the phase compositions depends upon the extent

to
of
since relation
each phase
.
A component is aa discrete chemical substance , the composition of which

is unrelated to that of other substances present . For example , in a salt
solution the chemical species present are NaCl , H , 0 , Na + , Cl- , H + , OH- .
Despite this there are only two components since the ion concentrations
are limited by the fact that they are formed from the compounds and that
the solution must be electrically neutral. The number of components
may be defined as the number of chemical species minus the number of
chemical equations relating them .
The factor of 2 appears in the phase rule because the temperatures and
all
the pressures of phases present equilibrium must equal
be
In
at
the
..
following discussion the phase rule will applied few simple cases
be
to
a
,
.
This section will first consider phase equilibria pure components and
of
then mixtures
of
Pure Components
system contains only one component and the phase rule
If
=
C
a
1
;
,
.Eq
=
three phases are simultaneously
to
reduces
If
3.
P
4.38
V
=
[
)
]
equilibrium becomes zero This means that the system completely

in
is
..
Such equilibrium can occur only one temperature and pres

at
an
fixed
.
sure Since composition cannot vary the phase relations can repre
be
.
,
On on
sented two dimensional diagram with pressure and temperature
as
a
axes
this diagram three hase equilibrium would appear
as
.
a
-p
point two phases are equilibrium becomes one In this case

in
If
V
.
the system not completely fixed unless either temperature pressure

or
is
set
Once one set the other arbitrarily fixed For example the
is
is
is
,
.
equilibrium between water and steam can occur over range tempera
of
a
ture and pressure the pressure specified 760 mm Hg

at
However
is
C if
,
,
.
its the
temperature must for equilibrium between pure water and

be
100
°
vapor the pressure specified 400 mm Hg the required tem

as
If
is
,
.
pressure temperature diagram two hase

83
perature On the
is
C
°
-
.
-p
as
equilibrium would appear line

a
Gas Liquid Equilibria The pressure vapor equilibrium with

of
in
a
a
-
liquid given temperature called the vapor pressure

at
at
pure that
is
a
At
temperature the gas liquid interface molecules are continually

,
-
.
breaking away from the liquid and entering the gas This breaking away
.
occurs when liquid molecule has acquired enough energy

to
overcome
a
the intermolecular attractive forces which hold the liquid Gas

in
it
molecules constantly collide with the liquid the interface lose energy
at
the liquid by intermolecular forces the number

If
to
and are then bound

.
molecules leaving the liquid greater than the number gas molecules
of
is
of
condensing into the liquid there net vaporization

of
the number
If
is
,
a .
gas molecules entering the liquid greater there net condensation

is
is
molecules leaving the liquid equal

to
of
the number the number

is
If
joining the liquid from the gas , there is no net change in either the liquid
or gas , and equilibrium exists .
The condensation mechanism can be most easily understood in relation
to the forces between molecules , or the intermolecular energy . Such an
energy diagram is shown in Fig . 4.3 . This diagram shows the potential
energy existing because of intermolecular spacing as a function of this
spacing . At high separations the molecules attract each other . The
energy of attraction , represented as a negative potential energy , is a
maximum at a separation rm , but decreases as the separation increases
beyond this point . As the molecules move closer together , the attraction
force is replaced by a repulsion . At separation rõ the attractive and
→ Repulsion
Potential energy
Attraction O
+
ro
m
Intermolecular distance
Fig 4.3 Intermolecular energy diagram

.
repulsive forces balance giving net potential energy

At
of
zero
a
,
separations less than strong repulsive force exists between the mole
r,
a
The shape this energy curve has been approximated analyti

of
cules
.
cally and the resulting expression has been used predict the behavior
to
,
real gases and liquids with some success

of
gas phase normally exist such large separations that

at
Molecules
in
or a
no
there little intermolecular potential energy Only during

is
a
.
collision are the attractive and repulsive forces large and these are over
,
by
do
the kinetic energy prevent

of
balanced the molecules These forces

..
by
such collisions from being perfectly elastic required the simplified

as
,
As
kinetic theory model the temperature lowered the kinetic energy

is
,
-
Ultimately the kinetic energy will low enough

be
so
reduced that
is
colliding molecules are unable separate but vibrate around the radius
to
,
ro . Such a pair may be split by further collisions , or it may trap addi

tional molecules until a liquid droplet results .
Molecules of various compounds have different properties which affect
their tendency to vaporize and condense . The size , speed , and inter
molecular attractive forces associated with a given type of molecule
influence the phase equilibrium . Small high - speed nonpolar molecules
such as hydrogen or methane tend to break loose from the liquid easily
and retain sufficient energy as a gas molecule on collision with the liquid
interface to avoid condensation . Such small molecules have very high
vapor pressures and low normal boiling points , because they have a strong
tendency to remain in the gaseous state . On the other hand , large slow
moving molecules tend to have lower vapor pressures and higher boiling
its
points . Water has a relatively high boiling point in spite of low molec
a
weight strong
a of
ular because intermolecular attractive forces
.
on
Vapor pressure complex function dependent many variables
is
,
predict the
to
of of
It
some them mentioned above therefore difficult

is
.
value vapor pressure from theory Vapor pressure data are usually
-
.
graphically tabularly Vapor pressure increases rapidly

or
presented
.
by
an
with temperature expressed approximately empirical
be
It
can
.
equation the form

of
log
Ci
++
C2 4.39
P,
)
(
T
vapor pressure temperature

at
=
where
T
P, C2
empirical constants evaluated for each gas

C1
= =
,
T
on
The vapor pressure plotted rectangular coordinates

is in in
of
water
is
accordance with Eq
on
Fig 4.4 and semilog coordinates

in
4.39
(
)
.
.
on
Fig 4.5 that plotted the logarithmic vertical axis and

T
is
is
P,V
/
1
,
;
.
Vapor pressure data for other

on
plotted the linear horizontal axis

-
.
do
on
liquids are plotted Appendix straight

D.
The data not fall

in
Fig 4.5 one straight line may drawn for low temperatures and
be
in
line
;
.
another for high temperatures This shows that experimental vapor

.
extrapolated over only short range

be
pressure data should For

a
.
In
Appendix the
D
convenience the nonlinear

scale also shown
is
T
,
linear omitted and only the

scale scale shown
is
is
T
T
/
1
vapor pressure curves end some higher temperature

All
Above
at
.
-
it At
this temperature only gas phase can exist this point the kinetic
a
by
great that
be
so
energy
of
the molecules has become cannot overcome

the intermolecular attractive force This true no matter how close
is
.
together the molecules are forced The temperature above which only
a
.
tem
regardless the pressure called the critical

of
gas phase can exist

is
,
,
are the
perature Tc . The vapor pressure at the critical temperature is
the gas and liquid phases
Pc
pressure All properties
of
critical
.
the critical point and the two phases are indistinguishable
at
identical
.
9,000
8,000
7,000
6,000
5,000
Hg
mm
Pus
4,000
3,000
2,000
1,000
1
100 200
C
°
T,
Fig Vapor pressure

of
4.4 water
.
The existence the critical point emphasizes the similarity between

of
liquid and gas phases any temperature and pressure can

at
gas
be
A
.
compressed heated and cooled until reaches any point the liquid
in
it
,
phase region this path can arranged

be
so
no
Moreover that there

is
,
.
abrupt phase change any point The properties change continuously

at
from the gas hase properties the liquid phase

to
of
It
those inter
is
.
-p
esting that no critical point has been found for phase boundaries involving
the solid phase . This leads some persons to consider that there are only
solid and fluid states .
50,000
40,000
30,000
20,000
Critical
10,000
8,000
6,000
4,000
3,000
)
2,000 Liquid
liquid melting point
1,000
(
,P -
gas
0
Hg 300
-
mm
quid
Solid
888
Solid Gas
10
triple point
(
)
3 4
-
gas
2
Solid
1
0.0040 0.0030 0.0020

-1 -1
T,
K
1
°
T, 50 /
1
25 1
1
1
-25 100 150 200 250300

0
C
°
Fig equilibria
on
pressure phase
of
of
4.5 Effect water

.
ressure data may determine the equilibrium tem

be
Vapor
to
used
-p
pressure deter
or
point
to
perature i.e. the boiling the specified

is
if if
,
,
)
(
equilibrium pressure the temperature specified The

is
mine the
.
normal boiling point the equilibrium temperature atmospheric pres

at
is
sure 760 mm Hg
(
)
.
Example 4.6 . Determine the boiling point of pure water and of pure propane at
pressures of (a ) 200 mm Hg , (b) 760 mm Hg , (c) 10,000 mm Hg , (d ) 50,000 mm Hg .
Solution . The data of Appendix D are used . Because of graphical inaccuracies ,
the values will be accurate only within 1° C at low temperatures and 5 ° C at high
temperatures .
a . The temperature at which propane has a vapor pressure of 200 mm Hg is T =
- 69 ° C . For water , T 66 ° C .
b. These values are the normal boiling points . At 760 mm Hg : propane , To =
- 43 °C ; water , To 100 ° C.
c. At 10,000 mm Hg : propane , T = 38 ° C ; water , T 192 ° C .
= 97 ° ,
d . 50,000 mm Hg is above the critical point of propane ( T. C PC 32,000
mm Hg ,
) . Therefore because there can be no equilibrium , there is no boiling point .
For water , T 280 ° C ( + 5 ° C ) .
Gas - Solid Equilibria . A solid may vaporize directly into a gas without
melting . All solids have vapor pressures . Water freezes at 0 ° C , and
the vapor pressure of ice is shown below that temperature on Fig . 4.5 .
In Appendix D , the vapor - pressure curves for other solids are shown .
Vaporization of solids is called sublimation . Sublimation pressures
for
solids are equivalent vapor pressures for liquids
to
.
Liquid Solid Equilibria Equilibrium may exist between pure liquid
a
-
.
its
the melting freezing point The melting point

or
at
and solid form
.
By the phase rule
at
usually measured atmospheric pressure

is
C
=
,
1,
.
the pressure
as
and Therefore before specified

=
P
is
V
=
1.
if
,
,
2,
,
the melting temperature uniquely determined Melting points vary
is
in .
only slightly with pressure Fig 4.5 Because

as
shown for water
the Hg no of
,
.
.
the scale the melting point curve appears

be
vertical line with

to
a
,
variation temperature with pressure Actually

of
at
100,000 mm
,
.
the melting point about –1 For engineering purposes

of
water
is
C
°
.
melting point with pressure may neglected Melting

be
variation
in
points various materials are given Appendix pure substance

E.
or of
in
A
As
single temperature
at
at
melts freezes heat removed the freez

is
a
ing point solid will precipitate from the liquid until completely
is
it
,
solidified The further removal heat will lower the temperature

of
.
Other Equilibria Pure components exhibit certain other phase

.
no By
equilibria solid liquid and gas may mutual equilibrium

be
, in
A
,
,
.
.
=
the phase rule

PP
and therefore and there are

=
V
=
C
,
3
;
0,
independent variables The temperature and pressure are unique For

.
water this point occurs and 4.579 mm Hg see Fig

at
0.0075 4.5
C
(
°
).
The point three hase equilibrium called the triple point

of
is
.
-p
The liquid and solid phases may have more than one form The
.
its
solid may change crystal structure unique temperature and two

at at
a
solid phases may exist equilibrium this temperature This trans

in
great importance metallurgy

is of
formation
in
is
.
an
Figure 4.6 extended phase diagram for the water system There
.
are several solid phases , one liquid phase , and one gas phase . The phase
boundaries intersect at triple points which are unique for the three phases
in equilibrium . Seven of these triple points are shown on the diagram ,
for
though only three are specifically named . The triple point gas
24,000
Ice VII
22,000
ice
ice
VI
-Liquid VII
-
-
triple point
20,000
18,000
16,000
Ice VI
,
14,000
Pressure atm
12,000
10,000
8,000 Liquid
ice
ice
VI
-Liquid triple point

V
-
6,000
V.
Ice
4,000
Ice Ice III

II
2,000
ice
Gas iquid Critical

I
-
-l
Triple point point

Ice
I
Gas
0
-100 100 200 300 400 500 600 700

Temperature
F
°
Fig 4.6 Phase diagram for water

.
.
ice
Fig 4.5
on
liquid shown coincident with the zero pressure axis

of in
is
-
At
Fig 4.6 region which the gas phase exists

as
most the other

in
is
,
.
points the phase boundaries are conditions equilibrium between two

of
In
phases the areas between phase boundaries only the single phase
.
noted can exist equilibrium However nonequilibrium conditions can

at
,
.
be extremely long lived , particularly with solid phases . Note that four
phase equilibria do not exist , as predicted by the phase rule .
If water vapor at a very low pressure and about 0 ° F is compressed ,
it initially forms snow of ice I crystalline form . As the pressure increases
ice
further , this would melt into liquid Further pressure would force
.
the liquid
to
freeze into ice III
crystal form and this crystal form would
,
and ultimately VII VI
The path
of
evolve into that ice indicated
is
>
,
.
by
by
Fig
on
the
4.6 line The solid phases are distinguishable their
F
0
°
.
.
different crystalline forms which have different densities specific heats
ice ,
,
In
and other physical properties the water system the only
is
I
,
.
solid form which less dense than the equilibrium liquid
is
.
Phase Equilibria Mixtures
in
Phase equilibrium mixtures becomes extremely complex
as
the num
in
ber components increases This section will consider few represent

of
a
.
ative simple cases for the most part limited three components
or
to
two
,
.
For two component systems the phase rule gives
4.
There
=
V
P
-
fore four phase equilibria can exist but only fixed temperature pres
at
,
,
-
sure and composition each phase With three phase equilibria

of
V
=
1
,
-
.
.
Thus specification the composition any one phase
or
of
of
is
needed
If T,
P,
by
fix
the system the phase relations are represented

to
three
a
.
dimensional diagram having and composition one component

by of
P
as
>
T,
,
axes three phase equilibria would represented

be
lines These lines

,
points four phase equilibria For two phase .

at
of
would terminate
-
.
-
equilibria there are two degrees Specification temperature

of
freedom
of
and the composition one phase would allow determination the pres
of
of
sure and the composition the other phase

of
For three component systems the phase rule gives

+
P
V
=
5.
It
-
possible have five phases equilibria

be
With two phase

to
would
in
-
.
equilibria there are three independent variables

so
that the composition

,
one component one phase must specified

be
as
as
the temperature
of
well
in
no
fix
and pressure The system may longer

to
the system
be
order
in
in .
by
completely represented diagram three dimensional space

a
Gas Liquid Equilibria The various components liquid gas mix

of
a
-
-
.
vaporize
to
as
ture have different tendencies discussed earlier The

,
.
on
the
the phases will dependent the tendency

be
of
concentration
of
an
components vaporize For example extremely vola

to
of
mixture
a
,
.
oxygen with relatively non volatile material like

a as
tile material such

a
water would have much higher concentration oxygen

of
the vapor
of in
than the liquid Equilibrium between gas and liquid more than
in
a
.
one component may analyzed several ways

be
For few ideal sys

in
a
.
tems theoretical and semiempirical equations may

be
used For many

,
systems data are reported graphically

.
for
Law . A theoretical relationship
Raoult's vapor liquid equilibria
-
for mixtures components Raoult's law
of
of
useful similar structure
is
.
This law states that the partial pressure any component vapor
of
in
is
a
the vapor pressure the pure component times the mole fraction
to
equal
of
that component the equilibrium liquid For component
in
of
a,
ра = Pvaxa 4.40
)
(
for
Equation
all
This expression may writtenbe the components
.
be
4.40 may also written

)
(
Pva
Ya
Xa 4.41
)
= mole fraction
ya
of
component vapor
=
where
in
a
vapor pressure pure ppendix
of
Pva
=
D
a
)
(A
ca = mole fraction component liquid

of
in
a
total system pressure

Р
Eqs possible deter
to
of
Combination 4.24 4.25 and 4.41 makes
it
,
(
(
)
(
)
.
mine the composition given the necessary data
as
each phase
of
shown
in
,
,
the following example By the
ya
Xa
and are intensive variables

P,
T,
,
.
.
phase rule any two are set the system uniquely determined
is
if
,
,
.
Example 4.7 liquid phase contains mole per cent benzene and mole per
30
70
A
at .
temperature
40
of
cent toluene
C
a
°
.
Calculate the composition the vapor phase equilibrium with the liquid
of
in
. a
.
.
Calculate the total pressure
b
Solution Benzene and toluene have similar structures Therefore Raoult's law
,
.
.
At
the vapor pressure 180 mm Hg that

40
be
may
of
of
used benzene toluene

C
is
,
°
.
mm Hg By Eq 4.40
60
),
(
.
Pt ре рь рь
Benzene Pьхь
:
180 0.30 54 mm Hg
(
)
(
Toluene Prixi
:
mm Hg
42
pi 60
P. =
0.7
= (
)
(
pt )
96 mm Hg
+
b
.
54
0.564
a
Yb
=
.
96
42
0.436
=
Yt
96
Example 4.8 ethane propane and temperature

at
of
mixture butane exists

A
a
,
-
.
-10 total pressure 3,000 mm Hg Determine the compositions

of
of
and the
of
a
°
vapor and liquid phases

.
propane
at to an
of
Solution Ethane and butane are three consecutive members

n
,
-
.
organic hydrocarbon series Therefore their structures are sufficiently similar

,
.
permit Vapor pressure data are obtained Appendix

of
Raoult's law
in
use
D
-
.
-10
.C
°
Ethane Pve 14,000 mm Hg

:
Propane Pop = 2,700 mm Hg

:
Butane Hg
rb
500 mm
P
:
Equation (4.40 ) may be written for each component :
Pe = 14,000xe (1)
Pp 2,700 Xp (2)
рь = 500х
, (3)
From Eq . ( 4.8a )
xe + x₂ + xo
= 1
(4)
From Eq . (4.25 )
pe + Pp + po = P = 3,000 mm Hg (5)
There are now five equations and six unknowns . The equations cannot be solved ,
because there is no unique answer to the problem as stated . There are three com
ponents , and therefore three independent variables should be specified , but only two
were specified ( T , P ) . Therefore , a third must be specified before the problem is
i.e.
meaningful . Let the compositions of propane and butane be equal in the liquid ,
,
20
Xp
6
(
)
There are now six equations and solution possible Equations and
is
3
a
,
),
),
(
(
)
.
are added and combined with Eq
5
(
)
.
pe
po
Pp
14,000x 2,700xp
+
+
500x0
or
14,000xe 2,700xp 3,000 mm Hg
+
500.20
7
(
)
Combining Eqs and gives
4
6
(
)
(
)
.
de
+
2x1
1
-
or de 2X1
–
(8
1
)
:
Xp
Substituting for de and Eq gives

in
7
(
)
.
14,000 2,700X0 3,000

+
+
2.0 500x6
=
1
(
Solving for gives

xo
X = 0.444
-
Therefore Xp = xь = 0.444
,
Xe 2x6 0.112
=
1
For the vapor phase

pe 14,000 0.112 1,570 mm Hg
(
)
(
Pp ,700 0.444 1,200 mm Hg

)
(
)
(2
= 222 mm Hg
рь
500 0.444
(
)
(
= 2,992 mm Hg
P
within slide rule accuracy 3,000 mm Hg For mole fractions

of
P
is
.
Pe
Pp
yь
0.525 Yp 0.401 0.074

=
Ye
=
Р
Р
Ey 1.000
=
Henry's Law Relatively few mixtures follow Raoult's law Henry's

.
.
on
law may used for presenting data certain systems

be
Pa HaXa 4.42
)
(
He
of
the Henry's law constant relating the partial pressure

pa
where
is
a
H.
component the liquid composition The constant

to
the gas
Xa
in
a
.
is experimentally . The value of H a, depends upon the units

determined
of Henry's law is frequently used to express the solubility of
Pa and Xa .
“ permanent ” gases such as nitrogen and oxygen in a liquid such as water .
Values for H , are found in Appendix F for a few gases .
In
very dilute solutions , Henry's law may hold for the solute gas , and
Raoult's law must then hold for the solvent liquid . For example , in
air
equilibrium between and liquid water the solubility oxygen and
of
,
by
nitrogen given Henry's law
so
water Because gases are
in
these
is
.
slightly soluble Raoult's law may
be
to
water used determine the
in
quantity vapor the air

in
of
water
.
Example 4.9 Calculate the compositions the gas and liquid phases for mixture
of
a
.
of
air and liquid water and 760 mm Hg

68
at
F
°
.
oxygen and nitrogen extremely
be be
the water will
of
Solution The concentrations
in
.
low because they are only slightly soluble These concentrations can calculated
,
from Henry's law

ро H0,202
,
PNZ HN CN
,
,
From Appendix
F,
Но 3.04 107 mm Hg mole fraction

X X
,
HN2 6.10 107 mm Hg mole fraction

/
by
Dry air contains approximately per cent oxygen and per cent nitrogen vol
21
79
ume Therefore neglecting the water vapor concentration

.
760 mm Hg 160 mm Hg
a
ро 0.21
,
)
(
=
PN 0.79 760 mm Hg 600 mm Hg
=
,
)
(
With these values

PO2 160 mm Hg
X02
Но 3.04 107 mm Hg mole fraction
X
/
?
10-6 mole fraction

x
5.25
=
=
5.25 ppm parts per million
)
(
PN2 600
=
XN2
HNA 6.10 107
X
10-6 mole fraction

x
9.85
=
9.85 ppm
the gas phase may

be
The concentration water vapor calculated from Raoult's

of
in
the liquid almost pure water molecular simi

so
of
law because that the criterion

is
,
larity satisfied By Raoult's law

is
ph
P
0
420XH20
»
,
But
x
X1,0 9.85 10-6 1.0

=
10-6
–
5.25
X
1.0
–
=
air
the partial pressure water vapor equal the vapor pressure

to
of
Therefore the
in
is
at ,
17.5 mm Hg
20
Pv
From Appendix
of
water 4,0 Therefore

D
.C
°
,
,
PH20 17.5 mm Hg
=
17.5 mm Hg
or YH20 0.023 mole fraction
760 mm Hg
Now , the mole fractions of oxygen and nitrogen must be calculated
YN2 + YO2 + 4H20 1.0

Therefore , YN2 + Yoz 0.977
YN2 0.79
Also
Yo2 0.21
Solving these equations gives
YN2 0.772
=: 0.205
Y02
These values could be used instead of 0.79 and 0.21 in the first part of the solution ,
but the correction is negligible .
In a mixture of completely immiscible liquids in equilibrium with
the
its
vapor phase each component exerts own full vapor pressure
at
the
,
temperature The total pressure the vapor

of
of
the mixture the sum
is
.
pressures
.
Volatility The volatility component the gas phase

of
of
the ratio
is
a
-
.
the liquid hase mole fraction

to
mole fraction
.
-p
Ya
Ka 4.43
)
Xa
Experimental data are frequently presented and correlated
in
terms
of
volatilities Volatilities are often called vapor liquid equilibrium ratios
,
-
.
simply The relative volatility two components

of or
of
K
values the ratio
is
-
their volatilities The relative volatility component

of
to
aby
is
a
b
.
K
K
YaXb
dab
Xayo
=
=
yo
Because and
Ya
–
=
Xa
1
,
(ya
xa
1
aab 4.44
(
)
–
Yabxa
1
(
For binary mixtures following Raoult's law Qab Pva Pvb and for binary
=
;
//
,
Qab
following Henry's =
mixtures law H2
Ha The relative volatility
=
).b
H
,
constant with composition for substances following Raoult's and

is
Henry's laws For many other mixtures the relative volatility varies
.
For example the relative volatility ethanol water systems varies

of
,
greatly This system deviates widely from Raoult's law An equilib

.
Fig
4.7
diagram system given

at
rium for the ethanol water atm

in
is
1
-
is .
For comparison constant relative volatility

of
of
curve 4.0 also

a
,
on
shown Further information nonideal solutions which follow neither

,
.
Henry's may
be
Raoult's law nor law found Refs and

in
5
,
,
3,
.
Condensation and Vaporization gas phase equilibrium

in
with
. A
a
.
liquid phase Any reduction temperature

be
to
said
in
saturated
is
or
pressure will cause part the vapor

In
to
many
of
increase condense
in
.
all
vapor phase may
be
all
the components condensable and
of
cases
,
a
on
cooling the vapor An example
to
may
of
condense some extent
do is
.
the benzene toluene system atmospheric pressure Vapor mixtures
at
-
.
one temperature pure vapor does The temperature
at
as
not condense
.
byas
vapor begins the temperature
to
which condense lowered
at
is
at is
a
point calculating the temperature
It
called the dew determined
is
.
which given vapor mixture saturated
is
a
.
1.0
vapor
in
0.8
mole fraction more volatile component
ab
4.0
=
a
Ethanol water
-
at
atm
1
0.6
0.4
,
Ya
0.2
0.2 0.4 0.6 0.8 1.0

Xa
mole fraction more volatile component liquid

in
,
Fig 4.7 Vapor liquid equilibrium diagram

.
-
.
The bubble point liquid mixture the temperature

at
as
of
defined
is
a
begins vaporize the temperature The bubble

as
increased
to
which
is
it
point also the temperature which the last vapor condenses and the
at
is
dew point also the temperature which the last liquid vaporizes
at
is
Example 4.10 Determine the dew point vapor containing

40
mole per cent

of
a
.
mole per cent toluene the composition

of
60
the first
at
benzene and atm What

is
1
liquid formed the dew point

at
Above the dew point Raoult's law has meaning because the gas
no
Solution
,
.
At
be
equilibrium liquid the dew point the vapor

to
in
considered
no
phase has
is
of .
by
equilibrium with the first drop liquid formed Then Raoult's law
,
.
Pub X
yь
= 0.4
760
304
or хь
Pub
Pri 0.6
=
Yi
=
760
456
or =
X
Pot
At the correct temperature

хь + х. = 1.0
304 456
or + 1.0 (1)
Pub Pot
The vapor pressures are not simple analytical functions of temperature ; therefore
Eq . ( 1) is solved by trial and error , using the data of Appendix D. A temperature is
are
.Eq
assumed ; vapor pressures determined from Appendix and substituted into
D
the left side equals 1.0
to
see
if
1
(
)
; .
.Hg
let
For first trial 100 then Pub 1,330 mm Hg Pve 560 mm
C
T
°
a
,
,
Checking
,
304 456
?
1.0
+
1,330 560
1.043 1.0
+
0.228 0.815
+
Therefore the correct temperature slightly higher Let 105 Pob 1,500
C
=
=
is
,
°
,
.
mm Hg put 610 mm Hg Then
,
304 456
?
+
1.0
1,500 610
+
0.202 0.750 0.952 1.0

=
too high Interpolation gives the correct temperature +
at
Therefore 105 about
C
is
,
of .
102 The composition the first liquid condensate determined from vapor
C
is
°
.
1,400 mm Hg Pvt = 580 mm Hg

at
pressures 102 Pvb

=
C
,
°
:
304
хь 0.215
=
1,400
456
0.785
=
X1
=
580
Example 4.11 Calculate the bubble point Example 4.10

of
the mixture
in
.
The liquid mole per cent benzene .

40
60
at
Solution atm and contains mole

is
,
.
per cent toluene

.
Pьхь
рь
ob
0.4P
:
рі
Puikt
0.6P
vt
-
760 mm Hg
рь
vt рі
+
760 mm Hg
vb
0.4P 0.6P
+
760
=
At
This requires trial and error solution using Appendix

80
D.
Pob
=
=
T
C
a
,
°
-
mm Hg Pot 300 mm Hg
,
0.4 760 0.6 300 484

=
(
(
)
(
Try Hg
80
85
Therefore too low where Pub 880 mm Pot 350

=
C
C
is
,
,
,
°
°
.
mm Hg
762 760
=
+
0.4 880 0.6 350

(
)
(
)
(
)
(
The liquid starts vaporize

85
Therefore the temperature

85
at
to
and
C
is
.C
is
°
°
,
completely vaporized
at
102
.C
°
the gas phase is nearly insoluble in the liquid , as in the air -water
If
system , application of Raoult's law to the liquid shows that the saturation
pressure is equal to the vapor pressure , and the dew point is equal to the
temperature at which the partial pressure equals the vapor pressure of
the pure liquid component
In Example 4.9 the air is saturated with
.
water vapor at 68 ° F ( Psat Hg ) at 760 mm Hg total pressure .
17.5 mm
If the temperature ,
is lowered water vapor will condense out . Therefore ,
68 ° F is the dew point for water vapor in air at the given concentration .
Humidity and Saturation . The air - water system is of great importance
in many industrial and everyday situations . Air conditioning is based
on the cooling and water - vapor reduction of humid air . Weather reports
regularly mention “ humidity .” This section will discuss various aspects
air
water system but the principles developed apply the equilib
to
of the
,
-
any volatile liquid and noncondensable gas

of
rium
.
The humidity water vapor
of
of
measure the concentration
of in
is
a
humid air expressed vapor per

as
unit mass
It
of
mass water
is
Y
,
.
'
dry air The molar humidity expressed water per mole as
of
moles
is
.
Y
is air
air
the mole fraction water vapor
ya
dry the humid and

in
If
of
is
,
.
dry air air then the molar

of
the mole fraction the humid

Ya
in
1
-
humidity ,
is
Mya Ya molan
Y
4.45
)
(
)ya
–
Ya
-
1
M
(1
molar humidity moles H20 per mole dry air

lb
lb
where
M Y
=
,
of
total moles humid air moles

lb
=
the molar humidity may partial

be
of
defined terms
in
Because
=
y
,
P
/
pressures
Pa pa
=
Y
4.46
)
(
Р
рь
Pa
where pa partial pressure water vapor

of of
partial pressure
po
air
=
The composition often expressed relative

to
humid air saturated

of
is
air
There are two common measures relative humidity and percentage

:
.
When these measures are applied systems other than air

to
humidity
.
water they are referred

to
as
relative saturation and percentage saturation

,
Relative saturation the actual partial pressure

of
the ratio
at of
is
the
liquid component the vapor pressure the liquid
to
the gas
of
the
in
temperature The relative saturation usually expressed

as
existing
is
a
.
percentage
,
Pa
Cr 100 4.47
)
(
va
where H
= relative saturation , per cent
5C,
pa = partial pressure of liquid a in vapor
=
Pa
P va = vapor pressure of liquid a at existing temperature
Equation ( 4.47 ) defines the relative humidity when component a is
water and is air . The relative humidity is included in weather reports .
b
Percentage humidity is the ratio of the actual molar humidity to
the
saturated molar humidity expressed percentage
as
a
,
,
Ср 100 Y. 4.48
Ya
sat
)
,
by
The molar humidity Eq
at
saturation 4.46
is
(
)
.
Ya Pva
sat
4.49
,
)
Pva
-
Therefore combining Eqs 4.46 4.48 and 4.49 gives
,
,
(
)
(
)
.
Pa
P Pva
(
)pa)
Ср 100
=
4.50
)
va
P
P
(
by
Percentage saturation for systems other than air water also defined
is
Eqs 4.48 and 4.50 Percentage humidity -
as
not the same
is
relative
(
(
as )
.
humidity expressed per cent The former engineering
in
more useful
of is
.
calculation The difference lies the ratio inert gas partial pressures
in
-
.
given parentheses Eq 4.50 At saturation this ratio

in
in
is
and
1,
(
).
.
Hp = Jlr 100
.
of
Example 4.12 and 750 mm Hg has relative humidity
85
Air 75
at
per cent
F
a
°
.
.
Calculate
pa
:
partial pressure water vapor Hraloo

of
The the air

in
. a
pa
.
Pr
molar humidity
The
C. b
.
Pb
humidity
The pounds H20 per pound dry air
in
percentage humidity
The
d
.
30.7 mm Hg Appendix
85
The vapor pressure

at
Solution
of
water
D
is
F
°
.
)
(
From Eq 4.47
a
.
)
.
pa
75 100
30.7 mm Hg
23.0 mm Hg
Pa
=
By Eq 4.46
b
)
.
23.0 mm Hg
lb
mole H2O
Y
0.0316
=
750 mm Hg mole dry air

lb
23.0
(
mole dry air 29.0 lbm

lb
Basis
C.
1
:
18
From mole H20 0.57 lbm

lb
0.0316 0.0316
b,
;
(
)
(
)
lb
0.57 H2O
Y
0.0197
'
29.0 dry air

lb
As PHYSICAL AND CHEMICAL PRINCIPLES 151
shown here 1829 for the air water system
Y
'Y
=
,
.
By Eq 4.49
d
.
)
. Ya,
30.7
sat
0.0427
750
–
30.7
Therefore
,
0.0316
FCp 100 = per cent
74
0.0427
Example Hydrogen partial pressure
40
20
at
4.13
of
of
and atm has ethane
–
F
a
.
°
atm
2
Calculate the percentage saturation

a
.
.
the pressure increased when will ethane start
to
at
constant
If
condense
is
b
,
.
temperature
?
Hydrogen will
40
be
at
Solution gas these conditions because well
is
F
a
°
.
above its critical temperature

.
From Appendix for ethane Pva 5,700 mm Hg 7.5 atm By Eq

D
4.50
a
),
(
,
.
.
( 20
7.5
–
Hp = 100
2
18.5 per cent

(
)
(
) )
20
7.5
–
2
(
its
Ethane will start partial pressure

, to
equal the vapor pres

6.
when
to
condense
is
-40 That
at
when
is
sure
F
°
.
ра Pva 7.5 atm

pa
Ya
the total pressure must higher than constant
20
be
be
For
is
7.5 atm atm
to
.
up
the lower pressure

to
at
as
the pressure increases saturation

;
atm
2
Ya 0.1
20 atm
At
the higher pressure

,
P
7.5
Ya 0.1
and = 75 atm
P
air
and water vapor may

gas phase such
be
as
of
The concentration
a
by
an
measured using together with ordinary

wet bulb thermometer
a
dry bulb thermometer may

be
The wet bulb thermometer

a to
identical
-
-
.
the dry bulb unit except that the thermometer bulb covered with
is
,
-
porous cloth sleeve saturated with the liquid whose vapor concentration
The liquid evaporates into the large volume
be
gas
of of
measured
to
is
surrounding the thermometer bulb The heat vaporization the

of
.
by
liquid supplied the remaining liquid whose temperature decreases

is
is .
the liquid temperature decreases below the gas temperature

As
heat
,
the liquid Ultimately equilibrium tem

to an
to
transferred from the gas

.
the liquid
on
of
the
of
perature reached when the rate transfer heat

is
supply the heat vaporize the liquid the existing

to
to
at
bulb sufficient
is
The liquid temperature will then This temperature

be
rate constant
.
.
.
always temperature
as
temperature gas
It
the wet bulb less than the

is
is
.
-
by dry except gas

at
saturation the saturated

If
the bulb
is
measured
,
.
with the vapor of the liquid , no liquid can evaporate

from the wet bulb
and the wet -bulb temperature equals the dry - bulb temperature . The
wet- and dry -bulb temperatures uniquely determine the concentration
of the vapor in the gas .
0.20
0.18
0.16 _130 °
0.14
air
E 0.12
dry
mole
/
lb 1200
moles H2O
0.10
,Y
Ib 0.08
110
0.06
°
0.04 % 2000
%% %% %
80Ve
I %
X50
=100
90
50 40
30
70
20
%
10
0.02
900
Twb
5
700
600 800
0
50 70 90 110 130 150 170 190

F
T,
°
Fig 4.8 Molar humidity chart for the air water system =
atm
P
=
1
-
.
The humidity chart convenient way for reporting the variation

in
is
a
for any other system vapor and

or
of
water concentration air

in
gas
a
.
air
humidity chart for given Fig where the

in
and water 4.8 molar

is
A
,
.
humidity
air
temperature The curve showing

as
plotted
of
function
is
.
saturated with water vapor is labeled " 100 % ." The other curves
labeled with percentages are lines of constant percentage humidity . The
diagonal lines running from the saturation curve down to the right are
lines of constant wet-bulb temperature .
The constant wet- bulb temperature lines for the air -water system are
also adiabatic humidification lines . An adiabatic system is one to and
air
from which no heat is transferred . For example , if unsaturated
of is
contacted with liquid water some water will vaporize and the heat
by
vaporization will supplied constant tem
be
the air
at
the water
is
if
,
air
perature The will cool constant wet bulb temperature until

at
is
it
a
to -
.
saturated The water may initially cool the wet bulb temperature
..
,
-
but will then remain temperature
at
this For the air water system

it
,
.
-
the wet bulb temperature approximately equal the adiabatic satura
to
is
-
tion temperature The adiabatic saturation curve the path air
of
is
.
conditions during the adiabatic process described
.
For systems other than air water the adiabatic saturation lines are not
,
-
constant wet bulb temperature Two families

to
of
identical the lines

-
.
humidity diagram for such systems
on
diagonal lines would appear

of
a
“
.
Example 4.14 psychrometer determines that the dry bulb temperature
of
Use
a
-
.
and the wet bulb temperature

95
75
at
for air atm Determine the

is
F
is
a
1
°
(
)
-
:
.
molar humidity the percentage saturation

b
,
(
)
by
Figure 4.8 represented the inter
of
Solution used The condition the air

is
is
.
At
vertical dry bulb line with the diagonal wet bulb line
95
75
of
section the
F
F
°
°
-
.
this point
,
mole H20 mole air

lb
lb
a
0.022
.
per cent
39
жp
b
.
Example 4.15 Air initially percentage humidity

20
adiabatic
at
and
%
120
is
F
°
.
ally humidified
.
the lowest temperature which could

be
What reached this process What

in
is
is
a
?
.
the humidity this temperature

at
the final dry bulb temperature the final humidity

90
what
If
is
is
b
?
F,
°
-
.
Fig 4.8 gives

At
percentage humidity reference

.F 20
to
Solution and
%
120
F
a
.
,
°
.
wet bulb temperature also the adiabatic saturation temperature

83
of
This
is is
a
,
°
-
by
The humidity following the

83
83
and the answer determined wet bulb

F
F
is
= -
.
line diagonally upward 0.04

to
the left until reaches the saturation curve where

Y
it
mole H2O mole dry air

F /lb
lb
followed only dry bulb temperature

at 83
90
to
of
The wet bulb line the

is
b
F;
°
°
-
-
.
0.037 5p
humidity = per cent
this point
75
Y
is
LiquidLiquid Equilibria When two pure liquids are brought into

-
each liquid will dissolve into the other

If
to
contact some extent

,
the two liquids are similar the liquids may completely

be
of
the molecules
,
Such miscible liquids form one homogeneous phase

in
soluble each other

.
two liquids have greatly different molecular structures they may have
If
very low mutual solubility and may

be
considered immiscible Between

a
.
these two extremes are liquids that are partially miscible . An example of
a completely miscible liquid pair is water and acetic acid . On the other
hand water and isopropyl ether are only slightly soluble in each other .
,
Temperature affects solubility markedly . Some liquids are more soluble
at higher temperatures ; others are less soluble .
A third component dissolved in two relatively immiscible liquids may
affect their mutual solubility . If the third component is a solid , it may
have a higher solubility in one liquid compared to the other . It may
therefore be possible to extract the component from one liquid phase by
contact with the other liquid in which the solute is more soluble . An
equilibrium concentration of solute will be established in the two liquids
in contact . This is the basis for liquid - liquid extraction . For example ,
the purification of uranium is accomplished by the liquid extraction of
uranyl nitrate ( UO2 ( NO3 ) 2) , which is soluble in both aqueous and organic
phases .
If the third component is a liquid in significant concentration , it will
alter the solubility of the original liquids . It may cause the two immis
cible phases to become completely miscible , thereby making liquid
extraction impossible . It may cause complete miscibility only in certain
concentration ranges . For example , in the three - component system
water - acetic acid - isopropyl ether , some mixtures form two phases , and
others only one .
Compositions of three - component mixtures are easily represented on a
triangular diagram . The solubility and equilibrium data for the system
water - acetic acid - isopropyl ether are given in Fig . 4.9 . The curve shown
on the triangular diagram divides the region of completely miscible ( one
phase ) mixtures on the right from the region of partially miscible (twc
phase ) mixtures on the left . This curve is called the phase envelope . The
horizontal axis represents mixtures of acetic acid and water . These two
components are completely soluble in each other , and the horizontal axis
lies in the one - phase region . Similarly , the diagonal represents mixtures
of isopropyl ether and acetic acid , and it lies entirely in the one -phase
region . On the other hand , water and isopropyl ether ( vertical axis ) are
only slightly soluble . The phase envelope intersects the vertical axis
at two places , showing that isopropyl ether and water are soluble in each
other to a concentration of about 1 per cent . All other mixtures of these
two components will form two phases.
all
All mixtures whose over - composition lies the two hase region
in
-p
will exist two phases equilibrium with each other The composition
in as
in
.
by
phases equilibrium given the equilibrium curve shown below

of
is
by
the triangular diagram The phases represented the lower part

as of
the
.
phase envelope have high water concentration and are referred

to
the
a
" water layer . " The phases on the upper part of the phase envelope
have a high concentration of isopropyl ether and are called the “ ether
layer .” By the addition rule developed in Chap . 3 , the compositions of
the two liquids in equilibrium and the composition of the mixture of the
1.0
0.8
mass fraction isopropyl ether
0.6
,,
0.4
Two
phases
Yo
Xc 0.2 One
phase
0.2 0.4 0.6 0.8 1.0

Xa
Ya
mass fraction acetic acid

,
,
0.6
Equilibrium curve for

the two phase region
ether layer
0.4
in
,
0.2
Ya
0.2 0.4 0.6 0.8 1.0

Xa
mass fraction acetic acid water layer

in
,
4.9
The liquid system water acetic acid isopropyl ether

20
FIG
at
C
-
°
.
.
on
of lie
straight line called the

tie
two must line Furthermore the com

,
a
,
.
the two equilibrium phases must

on
lie
positions the phase envelope

.
Example 4.16 per cent water per cent acetic

45
20
mixture contains acid

A
.
,
by
per cent isopropyl ether weight

35
).
Determine the composition the two phases which exist

of
this mixture
in
. a
.
each phase
of
of
Determine the mass mixture

in
100 lbm
b
.
Solution . a . The composition of the mixture is plotted in Fig . E4.16 . The composi
tie
on
lie
tions of the two phases must line through the mixture composition and also
a
on
the phase envelope Any straight line drawn through the mixture composition
is
.
intersects the phase envelope two points This line labeled
at
and extended until
is
it
.
trial now necessary check these two compositions using the equilibrium
to
It
1
is
.
,
curve The acetic acid composition the water layer read from the triangular
of
is
.
1.0
Ether phase composition
0.8
mass fraction isopropyl ether
0.6
Trial
||
Correct
1
tie line
,,
0.4
Mixture
yc
0.2
Xc
Water phase composition

-
O
0.2 0.4 0.6 0.8 1.0

Xa
Ya

,
,
0.6
ether layer
0.4
in
,
0.2
Ya
0.2 0.4 0.6 0.8 1.0

in .
Xa
mass fraction acetic acid water layer

,
Fig E4.16 Solution Example 4.16

to
.
diagram
Ya as
From the equilibrium curve below the diagram

= Xa
an
0.285 ether
=
,
.
phase 0.285 but the

of
equilibrium with water phase

Xa
be
will
ya of
in
0.14
a
actual ether phase composition Therefore

to
0.05
of
trial have
in
is
seen
,
1
.
for
the line drawn trial does not connect two equilibrium phases new line
A
is
1
.
By
drawn through the mixture point and checked trial and error the correct
it
is
,
,
.
as
tie line found shown Then from the correct tie line
is
Water layer 0.255 0.035 Xo = 0.71

= =
Xa Xc
=
:
Ether layer 0.030

Yo
0.115 0.855
=
Ya ус
:
tie
The inverse lever -arm rule may be applied to the correct line determine
to
6.
each phase
of
the mass
:
Mass water layer 0.855 0.35
––
1.605
=
Mass ether layer 0.35 0.035
Mass ether layer mass water layer 100 lbm
=
+
Therefore
,
100
Mass ether layer 38.4 lbm
+
1.605
1
Mass water layer 61.6 lbm
=
Liquid Equilibria Equilibrium solid and liquid mixtures
of
Solid
-
may types pure may equilibrium

be
be
phase
of
one several solid
in
A
.
In
with
of
saturated solution the solid solvent
in
another case the
a
,
the liquid
In
solid phase may the same components
be
as
of
mixture
a
.
liquid
on
may
be
still another case the
of
adsorbed the surface the solid
,
,
where the solid completely insoluble
is
the exist
at
saturated solution one which can dissolve no more solid
A
is
ing temperature the temperature evaporated

lowered solvent or
If
is
is
,
.
the solution becomes supersaturated and solid may precipitate out The
.
equilibrium The unit operation crystalli
be
solid and solution will
of
in
.
on
the precipitation
of
It
zation based solids from solution often
is
is
.
by
possible purer more uniform product crystallization

to
get
It
is
a
.
also possible separate two solutes by crystallization
to
solubility curve shows the variation with temperature the concen

of
A
Figure 4.10 gives the

of
tration material the saturated solution

in
a
solubility curves for sodium chloride and potassium chlorate The

.
solubility potassium chlorate varies greatly with temperature there

of
by ;
possible crystallize solid potassium chlorate

be
lower
to
fore would
it
,
On
ing the temperature

of
saturated solution the other hand the

a
,
.
solubility sodium chloride varies only slightly with temperature

so
of
necessary evaporate solvent crystallize the solid

be
to
to
that would
it
Many inorganic salts form hydrates

on
crystallization For example

,
.
magnesium sulfate forms hydrates with

of
12
and molecules water

1
,
6,
7,
The phase diagram for magnesium sulfate given Fig 4.11 The
in
is
point labeled the composition solution which remains liquid

to
of
the
is
e
lowest temperature
In
It
called the eutectic this case the eutectic

is
,
.
composition 16.5 per cent MgSO4

at
of
has and this solution freezes

a
Each region the diagram show the phases present

in
to
25
labeled
is
F
°
.
.
80 An
Example 4.17 aqueous solution containing per cent MgSO

35
cooled first
is
,
.
and finally For each temperature determine the

30
to
then
to
to
130
.F
F,
F,
°
compositions the solid and solution present

of
.
At
Figure 4.11 per cent MgSO4 the solid

35
Solution used 130 and

F
is
at is
,
°
.
by
MgSO4.6H20 The solution composition obtained drawing horizontal

is
a
.
60
50
H2O
40
g
Naci
/,
100
g 30
Solubility
KCIO
20
10
20 40 60 80 100
C
T,
°
Fig 4.10 Solid solubilities

.
220
200
Solution
180
1
MgSO
H
,
,
0
160 solid
Solution
140 +++
MgSO4-6H20
,T
Solution
F
°
120 solid
Solution
+
F100
MgSO4.7H20
solid
80
*
60 MgSO4.7H20
, 1
Solution MgSO solid

+
MgSO 12H
Ice
Ice 12
H2O solid solid

40
solution
+
20 Eutectic MgSO4-12H2O
+
Ice eutectic
+
MgSO4
+
MgSO4.12 H20
0.10 0.20 0.30 0.40 0.50
Composition mass fraction MgSO4
,
Fig 4.11 Solubility diagram for magnesium sulfate

.
.
130°F . The intersection of the horizontal with the line separating the solution region
from the two - phase region gives the solution composition . It is 34 per cent MgSO4 ..
At 80 ° F , the solid is MgSO4.7H20 and the solution contains 27.2 per cent MgSO4 .
At 30 ° F , the solid is MgSO4.12H20 and the solution contains 18.7 per cent MgSO4 .
REACTION RATES
The fact that a specific chemical reaction occurs does not ensure that
the chemical engineer can use the reaction on an industrial scale . He
must also know the rate at which the reaction takes place . Many reac
tions , such as those between ionic inorganic compounds , are very fast
and proceed to completion in a short time . Many organic reactions are
slower , and the engineer must allow for sufficient time for the reaction
to take place when he designs an industrial chemical reactor . It is
therefore necessary to study the kinetics of a chemical reaction in order
to design the reactor properly .
Often reverse and competing reactions occur . The products of a reac
tion may decompose or recombine to give the reactants . In this case
the reverse reaction destroys the desired product , and ultimately an
equilibrium between the forward and reverse reactions is established .
This equilibrium limits the possible yield of the desired product . It will
be discussed in the next section . Reactions other than the desired one
often occur when the reactants are brought together . The engineer must
of he
he all
competing that knows the conditions under

so
study such reactions

,
which can obtain the maximum yield the desired product He .

up
catalyst that
so
frequently uses
to
speed the desired reaction

it
a
dominates other competing reactions

.
measured experimentally The theory

be
of
of
The rate reaction can
a
chemical reactions not sufficiently developed permit

to
accurate pre
is
reaction rates although theory helpful understanding the

of
diction
in
is
,
mechanism by which reaction takes place

a
is an
reaction mechanisms specify the existence

of
of
Present theories
intermediate compound between reactant and product states This
.
B an
called activated complex The simple reaction between compounds

.
and then follows the path

A
AB
=
4.51
D
+
A
C
=
B
)
(
[
where reactant molecules

A
B
= = =
,
AB activated complex
[
product molecules
D
C
,
go
to
The double arrows are used show that the reactions can either
in
by
direction The activated complex formed collisions between react

is
.
ant molecules provided that these collisions occur high enough energy
at
,
levels . The number of collisions must be proportional to the concentra

tion of reacting molecules , but the fraction of these collisions that results
in complex formation depends upon the energy level required and the
temperature of the system . The kinetic theory pictures molecules with
a wide range of energies , so that there will be some few with the necessary
high energy . The proportion of these high - energy molecules will increase
as the temperature increases . The activated complex is not particularly
stable and may decompose into the products or into the reactants .
Again , the proportion of activated - complex molecules that decomposes
into products depends on the relative energy requirements of two paths .
However , theory postulates that the activated complex decomposes into
reactants , and is formed from reactants , much more readily than it
the
decomposes into products . Thus the reaction rate is controlled by
decomposition activated complex The activated complex
of
of
rate
-
.
by
proportional
to
of
concentration the concentration the reactants
is
equilibrium restrictions
of
the sort that are discussed below Therefore
,
.
still proportional
to
of
of
the rate reaction the number collisions
to is
the fraction the reactant molecules having the

or
of of
between reactants
an
necessary high energy The concept activated complex however
is
,
,
.
explaining measured reaction rates

as
of
convenient consistent method

in a
.
For example solid catalyzed reactions the activated complex includes
,
on -
an
adsorption site the catalyst surface which allows the required

,
energy level reduced thus increasing the reaction rate

be
to
.
The simplest reaction unimolecular reaction which one molecular
in
is
a
species decomposes rearranges The reactant single molecular

or
is
a
.
species
A
,
→
E
A
( 4.52
where the sole product )

or
E
is
+
+
E
A
4.53
)
(
where and are the two products The best known unimolecular
E
-
.
reaction radioactive decay nuclear reaction For example uranium

is
a
,
,
.
by
decays neptunium
to
239 239 the reaction

B
Np239
+
U239 4.54
)
(
typical unimolecular
an
ß-
the
where electron chemical reaction

is
is
.
decomposition
of
N205
:
42
02
N206 N204
+
4.55
)
(
In
the simple case unimolecular reactions are also first order first
A
,
proportional
of
order reaction which the rate reaction

in
to
one
is
is
the
concentration of a single reacting species . That is ,

dca
do
kica (4.56 )
where ca = concentration of reacting species A

ke proportionality constant between rate and concentration
0 time
-dca / de = rate of disappearance of reactant A
Examples of first - order reactions are given in Example 3.2 and Prob . 3.4 .
First -order reactions are not necessarily unimolecular ; reactions involving
two or more molecules may be first order . For example , the hydrolysis
of sucrose in aqueous solution is first order , as shown in Example 3.2 ,
even though two molecules take part in the reaction .. In this case , the
dur
its
water is in great excess , and concentration essentially constant
is
so
ing the reaction
of
that does not influence the rate reaction
it
,
.
Bimolecular reactions occur when two molecules collide and react
.
That
is
,
2A +
+ +
E E
F F
4.57
)
+
+
or
B
A
4.58
)
For example NO decomposes according the equation
to
,2
,
2N02 2NO
+
02 4.59
)
Therefore two molecules NO must collide before the reaction can take
of
,
place An example bimolecular reaction with two reacting species

of
a
.
hydrolysis ethyl acetate with sodium hydroxide

of
the
is
:
+
CH3COOC NaOH CH3COONa OH

+
+
H
4.60
C
,
,
,
,
)
(
Bimolecular reactions may also pro

be
second order where the rate

is
,
portional the product the two reacting species

to
of
of
the concentrations
.
For Eq 4.58
(
)
.
dca
KCACB 4.61
(
do
where
CA
of of
reaction mixture
in in
concentration
B A
CB = concentration reaction mixture

ko
second order reaction rate constant

-
-
'
For Eq 4.57
(
)
.
dca
=
k''CA 4.62
=
de
an
which also expression for second order reaction

is
Trimolecular reactions are those where three molecules must collide

Most trimolecular reactions actually consist
of
and react two successive

.
bimolecular reactions . In general , a trimolecular reaction may be rep

resented by
A + B + C + E +F ( 4.63 )
An example is
2NO + 02 → 2N02 ( 4.64 )
the reverse of Eq . ( 4.59 ) . The reaction of Eq . ( 4.64 ) is also third order .

In general, a third - order reaction rate is given by
dca
k'"' CACBCC (4.65 )
d
where =
k " third -order reaction -rate constant
For Eq . ( 4.64 ) , this becomes
dono =
cor
k " ( cno ) ? ( 4.66
)
dt
)
method for evaluating first order reaction rate constants was shown
A
-
-
Example 3.2 Similar methods may used for second- and third be
in
order reactions
.
The order not necessarily the same the molecularity
as
of
reaction
is
a
.
the examples cited above the two are the same On the other hand
In
,
,
Example 3.2 gives first order bimolecular reaction for reasons discussed
a
,
-
The order determined experimentally the molec

of
earlier reaction
is
a
;
.
ularity theoretical concept determined by examining one possible

is
a
In
reaction mechanism many cases the reaction mechanism very
of is
.
complex and not fully understood

be
There may number inter

a
.
do
all
mediate steps which not appear the over equation For example
in
,,
-
the reaction
3KI 2KBr
→
KIZ
+
C2H4Br2 C2H4 4.67

(
has been shown experimentally

be
to
second order
.
Zero order reactions are known where

,
-
dca
=
kc
4.68
:
dt
(
Obviously zero molecular reaction impossible Fractional order

is
a
,
-
.
reactions are frequently encountered For example the experimentally

,
.
determined exponent may give 1.6 order reaction

a
,
-
dca
1.6
CA
ke
4.69
)
dt
(
on
ele
chemical reaction kinetics may

be
Further discussion found

in
1,3
mentary physical chemistry books

.
PHYSICAL AND CHEMICAL PRINCIPLES . 163
Example 4.18 . What yield of hydrolyzed sucrose after

would be the percentage
4 hr in a solution which initially contains sucrose per liter of solution ?
80 g moles
3.2
Solution . This reaction was shown to be first order in Example The rate
.
constant 0.00364 min Then
is
-1.
k
.
dca
-0.00364CA
d
[
At
time CA0 moles liter
g
9
/
0 0,
At time = 240
CA
=
min
?
,
,
Integration gives
240 min
Sot
CA2 dCA
min
dt
0.00364
-
62
***
(
CA
- 1
)
In CA2 0.00364 min 240 min
0
-1
)
-
–(
)
(
9
CA
Therefore 3.73 g moles liter

=
/
,
3.73
–
9 = 58.5
=
Sucrose hydrolyzed
%
9
REACTION EQUILIBRIA
an
Most reactions have opposing reverse reaction The rates
of
the
.
an
forward and reverse reactions will determine equilibrium distribution

the reactants and products
of
In
the reversible second order reaction

.
-
=
+
+
E
B
A
4.58
)
of
the rate the forward reaction

is
dca
=
R''CACB 4.61
dt
where the reaction constant for the forward reaction For the
is
k
.'
reverse reaction
dce
=
k''CECF 4.70
dt
where the reaction constant for the reverse reaction At equilib

ke
is
'
production just equal consumption

to
of
of
of
rium the rate the rate

A
is
A. ,
by
The rate consumption given Eq 4.61 The rate

of
of
of
is
)
.
production found from Eq equal the negative

be
to
to
of
4.58 the
is
)
.
consumption for every mole

E.
That
of of
of
rate consumed one

E
of
is
,
mole produced From Eq

is
A
4.70
.
)
(
dca dce
K'CECF 4.71
ast
)
(
dt
dt
).
(
At equilibrium the rates production and consumption are equal

of
:
Card
.-
4.72
dt
)
dt
).
( .*
)
-
=
Combining Eqs . ( 4.61 ) , ( 4.71 ) , and ( 4.72 ) gives
k " CACB Kreece
k! СЕСЕ
or ( 4.73 )
CACB
k"
The ratio of the rate constants is defined as the equilibrium constant Kc ,
k ' CECF
Ko CACB
( 4.74 )
' k'o
The equilibrium defined by Eq may
be
It
constant 4.74 measured
is
(
.
).
experimentally directly An irreversible reaction
or
from rate constants

,
.
Once the reactants are mixed they
no
one that has reverse reaction

is
,
.
completely products given enough time Radioactive

to
are converted ,
.
Many
an
decay
so
irreversible reaction reverse reactions are slow
is
be .
that the forward reaction may considered approximately irreversible
.
complex
an
The formation from reactant molecules occurs

of
activated
equilibrium Here the reaction might
be
at
as
discussed earlier
,
AB 4.75
+
A
=
B
)
]
For this reaction the equilibrium constant

is
AB
C
Ko =
[
4.76
)
CACB
proportional activated complex

to
of
the rate the concentration

If
is
dca
AB
4.77
=
k'C
dt
)
[
by
activated complex can sub

be
Then the concentration

of
removed
stituting Eq 4.76 into Eq 4.77
(
:
)
.
dca
K.K
-
k''CACB 4.61
=
CACB
(
)
d
Equation the standard rate equation for second order reaction

4.61
aа
is
)
(
and was previously written directly from the reaction equation Thus
,
.
an
postulating the existence activated complex does not alter the rate
if of
equation that obtained the activated complex equilibrium with

in
is
is
the reactants
.
For gaseous
reactions the concentration terms the equilibrium
in
constant equation are conveniently replaced with partial pressures This

.
may be done since

na pa
Ca =
V RT ( 4.28 )
For the reaction given by Eq . ( 4.58 ) the equilibrium constant then

becomes
K. ( pe / RT ) ( PF / RT ) PEPF
KP ( 4.78 )
( PART ) ( PB . / RT ) PAPB
where Kp is the equilibrium constant expressed in partial pressure units .

Equation (4.58 ) had an equal number of reactant and product mole
cules . Generally , the number of molecules reacting will differ from the
number of product molecules formed . For this general case ,
aA + B =E + fF ( 4.79 )
where a , b , e, f are the stoichiometric quantities of A , B , E , and F com

pounds entering in the reaction , in moles . For this reaction the equilib
rium constant is
cacho
Kc (4.80 )
A
CaCOB
If partial pressures are desired ,
( pe / RT ) * (PF / RT ')
K.
( pa / RT ) " ( PB / RT )
ppe e +f - a- 6
PAP ((RT) f - -
e+ a 6
( 4.81 )
or K. KP 4.82
( RT )
***
Often equilibrium constants are expressed

of
of
terms mole fractions

in
reactants and products This especially common for gaseous reac

is
.
For the reaction 4.79 Eq 4.81 may

be
tions altered
>,
(
.
)
.
:
+
a
e
peper
-
f
(( RT
K.
***
RT
-
PAPE
)
((
Pye Py's
+
-6
e
f
-a
=
R1
Pya Py RT
)
),
yeye
-6
-a
e
f
1
+
Pe -2-6 4.83
RT
(
Yay's
****
+
6
e
a
a
e
-
-
-
-
K. Ky RT
or
4.84
RT ****
(
)
(,
(
=
41
K
)
1
+
the equilibrium constant

K
of
where terms mole fractions

in
is
,
expressions for the equilibrium used only

be
These constant can the

if
gas phase is ideal . Other expressions are available for use with nonideal
gases .. All these expressions relate compositions at equilibrium . In
are
order to find these compositions when initial reactant compositions
given the mass balances must solved simultaneously with the equilib
be
,
rium relations computation are treated
of
of
Details this kind
in
Chap
.
5
.
Example 4.19 Develop expression for the equilibrium
an
. constant for the reversi
ble reaction
2NO = 2NO
+
02
,
Solution For the third order forward reaction
-
.
deno
20
CNO
=
k
-(
?
(
) )
(
)
."(
dt
-
).
(
For the second order reverse reaction
-
deno denoz
es
--
,)2
ladt
dt zkowo
)
).
(
-
. (
st
At
equilibrium
deno
e
deno
dt
dt
)
-
(1
(
Therefore
,
602
eno
cno
)?,
k
=
),
'( "
k
?
"(
)
(
CNO
Co ?
K.
!"
,
k
)
(
and
CNO
(
'()
kic
Example 4.20 The equilibrium constant for the reaction

.
2NO2 N204
Determine the quantity NO2 present

77
at
of
6.56 atm mole

in
lb
of
is
mix
.F
-1
a
°
of
at
ture NO2 and N204 atm total pressure

1
Solution The equilibrium constant

is
.
CN204
K.
(1)
CNO
2
(
given reciprocal atmospheres atm

By is
Because the value

of
it
the constant
in
is
,
(
-1)
.Eq
necessary partial ressure units which are commonly used

to
to
convert
1
,
(
)
.
-p
Eq 4.28
),
(
.
pa
=
Ca
RT
PN204 RT PN RT
,
0,
Then K.
/
PN02 RT PNO2
2
2
/
)
)
(
The equilibrium constant pressure units

in
is
Ke PN204
)
KP 6.56 atm
(2
-1
RT
)
22
noz
)
(p
Now , the total pressure is 1 atm :
PNO , + PN , 04 = 1 atm (3 )
Solving Eqs . (2) and (3 ) gives
PNOZ = 0.322 atm
Therefore , there is 0.322 lb mole of N0 , in the mixture .
In this chapter various aspects of physical chemistry which have

important applications in chemical engineering have been discussed .
Further information on these and other topics may be found in Refs .
1 , 3 , and 5 .
PROBLEMS
4.1
Make the following temperature conversions using appropriate formulas

,
:
.
Kelvin
to C to to
279 degrees
R ° F C
a
°
.
425 degrees Kelvin

C. b
°
.
.
to
200 degrees Rankine

–
725 degrees Kelvin

. d
°
.
.
to
2250 degrees Fahrenheit

C
€
centigrade
to
200 degrees
–
F
°
f.
proposed temperature scale based upon benzene
be
° to
to
establish called
It
4.2
is
,
.
the
the melting point

of
benzene scale On this new scale benzene and
B
)B
is
0
T,
°
(
100 the boiling point

B
is
°
be on .
What temperature this scale would correspond

to
absolute zero
?
. a
.
Data on benzene melting point

on
What would 200 the centigrade scale

B
° b
:
5.5
boiling point 80.1

C
. C,
°
.
4.3
computer program TºB see Prob 4.2 for

to
Develop
to
convert from
T
C
°
a
.
of
definition
B
°
) .
. 4.4
Develop computer program

to
to
convert from
R
T
T
C
a
°
.
.
4.5
Express standard conditions degrees Rankine and feet

of
of
units water
in
,
(
)
degrees Kelvin and dynes per square centimeter

(6
)
90 .
4.6 Calculate the specific gravity compared

32
at
to
.F at
of
benzene water
F
.F
°
°
.
Calculate the specific gravity compared

32
32
at
to
of
water
to at
benzene
F
°
°
4.7
The specific gravity compared

20
at
at
of
carbon tetrachloride water

in C
C
4
°
°
.
Calculate the density pounds per cubic foot

of
1.595 carbon tetrachloride

is
.
by
. 4.8
Calculate the volume occupied

25
of
helium and atm

lb
at
moles 500
F
/ at 2
at °
.
.
4.9
Hydrogen flows compressor

70
cu
to
5,000
at of
rate min and 750

ft
F
a
sq a
°
.Hg
compressed Assuming the perfect gas

80
10,000 lbs
to
in
It
mm
is
F
°
.
law calculate
. 3,
The volumetric flow rate out the compressor

of
. a
The mass flow rate

b
cu
at
of
4.10 What the volumetric flow rate standard conditions min

of
300
ft
° is
/
.
at
methane 250 and 730 mm Hg

C
He
10
NHz and
at
gaseous mixture contains and

N
4.11 lbm lbm lbm 160

A
F
1
5
,
°
. .
atm Calculate
2
The composition volume per cent

as
a
.
The partial pressure each component

of
b
.
.
c. The pure - component volume of each component .

d . The mass density of the mixture .
e. The molar density of the mixture .
f. The average molecular weight of the mixture .
by
air
4.12 . Knowing that per cent oxygen and per cent nitrogen
21
79
volume
is
),
(
its
calculate average molecular weight
by
per cent ethane C2H6 and per cent hydrogen
85
15
4.13 gas contains
A
(
.
sq
15
75
at
and lbs Calculate
in
volume
F
/
°
:
.
)
The partial pressure each component
of
. a
.
.
The molar density
b
.
each component
of
The mass fraction
c
.
.
nitrogen present
cu
at
using
of
Calculate the mass 200 atm and
in
ft
4.14
a
F,
°
(
)
.
the perfect as law using Van der Waals equation

b
,
(
)
lb .
'
-g
Determine the pressure required diphenyl
to
of
contain mole
in
4.15 volume
a
.
using Van der Waals equation

50
of a 70
cu
at
of
ft
F,
°
.
'
the
for
Write
4.16 simplified computer program and calculation flow chart
° a
.
diphenyl psia inter
70
10
at
determination the molar volume of
at
and pressures
F
500 psia using Van der Waals equation
10
to
vals from
.
'
supplied
at 40
cu
to
1,000
it of
of
flow min ammonia and atm
. at
ft
4.17 com
A
is
1
a
/
°
.
pressor where sq
70
200 lbs
to
compressed Calculate the volumetric

in
F
is
°
/
der
compressed using the perfect gas law using Van
of
flow rate ammonia
b
a
,
,
-
(
)
(
)
Waals equation
'
lbm
Develop computer program determine the specific volume
cu
to
4.18
ft
° a
/
(
)
.
and 150 psia using van der Waals equation Solve the problem
byof
at
benzene 200
F
.
'
by
hand following your program step tep

,
.
-s
properties real gases are often fitted the equation to

of
4.19 The
P
V
T
-
-
:
.
с
pro
PV
v1
4.
1-
*B.
(1
vm
RT
)]
--
(11
(
1
1
-
™
=
-
+
v
)
(
A.
B.
where and are constants Write calculational flow chart

to
com
R
V A
a
,
,
b,
c,
pute for given values

of
and when the constants are known

P
in T
4.20 For the equation given the preceding problem write calculational flow
a
.
compute for given values

to
chart and when the constants are known

of
V
Two gallons ethyl alcohol gal

20
20
at
at
of
of
4.21 mixed with water

C
is
C
1
°
°
.
Calculate
:
The composition
as
of
the mixture mass fraction

a
.
pound moles per cubic foot

of
The concentration ethanol the solution

in
in
b
)
.
° .
ethyl alcohol and water has specific gravity

20
at of
of
solution
at
4.22 0.9411
A
C
a
.
compared
to
water Determine
.C
4
as as as °
The composition mass fraction

a
.
The composition mole fraction

b
.
The composition conventional volume per cent

c
.
Estimate the vapor pressure furfuryl alcohol

at
at
and
of
100 200 from

C
4.23
C
°
°
.
170
of ;Hg
the following data vapor pressure normal boiling point

68
10
at
mm
C
°C
,
,
°
.
:
4.24 Knowing only that the normal boiling point entane 36.1 estimate
C
is
n
,
°
.
-p
the vapor pressure Hint Use Appendix recalling that butane pentane,
50
D
at
–
.C
,
°
and hexane have similar structures

.
for
Develop analytical expression the vapor pressure methyl iodide from

an
of
4.25
.
the following data :
Temperature , ° C Vapor pressure , mm Hg

-55 5
- 45.8 10
-35.6 20
- 24.2 40
– 16.9 60
-7.0 100
8.0 200
25.3 400
42.4 760
4.26 . Develop a calculation flow chart for computer solution of Prob . 4.25 .
4.27 . Estimate the boiling point at 300 mm Hg of pyridine from the following vapor
2.5
pressure data : vapor pressure at mm Hg normal boiling point 115.4

of C
.C
5
,
,
°
°
4.28 Determine the boiling point 100 mm Hg 760 mm Hg
at
ammonia
6
,
.
,
(
)
(
)
50,000 mm Hg
c
(
)
liquid phase solution contains mole per cent mole per

75
25
4.29 octane and
A
n
at -
-
- .
cent total pressure

of of
decane atm
n
Determine the composition the equilibrium vapor

6. a
.
.
Determine the equilibrium temperature
.
per cent ethane per cent propane and per cent

10
30
60
4.30 gas phase contains
at A
,
.
butane 60
.F
°
Determine the total pressure equilibrium

at
. a
.
Determine the composition the equilibrium liquid

of
b
mole per cent methyl alcohol

60
40
mole per cent toluene

of
4.31 mixture
A
is
,
.
At
atmospheric pressure what temperature does the mixture start

to
heated boil
at
?
.
the composition the first vapors evolved

of
What
is
For the mixture specified Prob 4.30 calculate the dew point and the bubble
in
4.32
.
point Develop simplified computer program

to
calculate these values

a
.
refinery stream containing mole per cent ethane mole per cent pro
is 10
30
4.33
A
,
.
mole per cent butane constant pressure 150 psia

60
at
pane
of
and cooled
a
,
Develop calculation flow chart that would allow computer

to
calculate the fraction

a
liquefied and the composition liquid and vapor streams five evenly spaced tem
at
of
As
peratures between the bubble point and dew point first step calculate the dew
a
,
.
point and bubble point

.
vapor liquid equilibrium mixture

60
at
of
4.34 benzene and toluene exists

A
C
°
-
.
and 300 mm Hg
.
Calculate the compositions the liquid and vapor

of
a
.
Determine the relative volatility

to
of
benzene toluene
b
.
Develop computer program curves for ideal binary

to
4.36 calculate the

y
a
to x
-
.
mixtures having relative volatilities ranging from 1.0

of
increments
in
4.0 0.2
.
0.1
Ax
The program should determine points

of
intervals Calculate the curve for

at
.
-by
Q = 2.0 following your program step step

,
in .
Hydrogen gas and liquid water are equilibrium Cal

20
at
4.36 and atm

C
2
°
.
hydrogen the liquid and the partial pressure

of
of
culate the mole fraction water

in
in
the gas
.
if At
equimolar mixture and octane begin

10 an
what pressure will

to
of
4.37 hexane
.
condense the temperature

C
is
°
?
4.38 . Calculate the bubble point and dew point of the following mixture at a pres
sure of 1 atm : 15 per cent ethane , 45 per cent propane , 10 per cent butane , 30 per cent
hexane .
4.39 . A liquid containing 30 mole per cent toluene and 70 mole per cent benzene is
to be vaporized at 1 atm pressure .
and
a . Determine the composition of the first vapor formed as the liquid is heated ,
the last liquid aporize
of
to
also that
.
Over what temperature range does vaporization take place
b
?
.
At
four component gas stream
be
to
4.40 cooled and condensed limited
A
is
a
-
.
.
range temperature and atm pressure the volatilities for the components may
at
of
1
represented
be
as
follows
: Original mole
%
Component
K
=
T
R
°
(
)
20 0.01 .001T
+
D С B A
30 0.4
+ +
10-6T2
x
3
40 1.0 .005T +0.1
X
10-6T2
22
10 0.5
+
10-6T2
X
Develop calculational flow diagram
to
determine the dew and bubble points
a
a
.
this mixture Note the program must choose and calculate the
of
values
by T
It
K
a
(
-
:
.
.
must then test whether this the correct one determining whether the total
T
is
Ey
or
mole fraction Ex 1.0 1.0 whichever necessary
If
not new must is
T
to ,
,
.
Write the program the right direction and adjust
stop when
be
to
as in
selected
T
,
.
'
Ex -1 when Ey
or
0.0001 required
+
0.0001
+
1
)
.
by
not
Do
Solve the problem hand for one trial following your flow chart
b
.
.
attempt
to
achieve 0.0001 accuracy

.
pound moles per cubic foot oxygen
of
What the concentration
90 in
in
4.41 water
is
)
.
air
equilibrium with
at
which
in
F
is
?
°
and
air
water vapor
10
at
of
Determine the mole fraction saturated

in
4.42 atm
.F .
200
°
An immiscible liquid mixture

25
at
of
4.43 benzene and water exists C

°
.
.
Determine the total pressure

a
.
Determine the composition the equilibrium vapor

at an of
b
.
4.44 Water and hexane form immiscible liquid mixture Calculate the com
.
position the equilibrium vapor total pressure

of
of
atm
a
80 1
.Hg
air
The partial pressure water vapor

20
at
of
and atm
in
4.45 mm
is
1
F
°
.
Calculate
:
The relative humidity

a
.
The percentage humidity

b
.
The molar humidity

. c
.
The humidity pounds H2O per pound dry air

in
d
hydrogen and acetone vapor

80
at
of
mixture relative saturation

of
4.46 has
A
a
°
.
per cent
75
at
atm Calculate
1
:
.
The partial pressure

of
acetone
. a
.
The percentage saturation

b
60
Air contains 0.02 mole fraction

at
4.47 atm total pressure and hexane.

F
n
1
-
.
Calculate
:
The relative saturation

a
.
The percentage saturation

b
.
.
-dry
air
The wet bulb temperature

75
be
to
of
4.48 was found when the bulb

F
°
-
.
temperature was
92
at
atm
F
1
°
.
a . Determine the percentage humidity .

b . Determine the mass of water vapor per pound of air .
4.49 . Air at 95 °F and 75 % percentage humidity is cooled to 60 °F .
a . What is the molar humidity of the resulting air ?
If the air
its
95
what will percentage humidity
to
be
b. reheated
is
°
F,
?
39 for
4.50 The following values are available the vapor pressure liquid carbon
of
.
Stull Ind Eng Chem

D.
tetrachloride A.
517 1947
.,
[
)]
:
:
.
.
Pv mm Hg
T
C
°
,
10 19.6
-
20 -8.2
40 +4.3
60 +12.3
100 23.0
200 38.3
400 57.8
760 76.7
Develop the equation

fit
to
to
calculational flow sheet these data
a
:
.
B
T A
In
Pa
+
C
T2
using the method least squares

of
computer program
to
From the constants obtained above write determine the
b
a
,
.
air
humidity diagram for the carbon tetrachloride system

on
at
saturation curve
1
a
-
70
atm total pressure and temperatures between and

of C
0
°
.
Extend the above program permit calculation

to
of
lines constant relative

c
.
on
10
the same diagram

at
these programs assume that

In
saturation
of %
increments
(
.
done through available subroutines

be
ex
the calculation
In
and can The
In
x
subroutine occupies the memory between 3000 and 3200 and the
ex
subroutine
x
,
To
occupies memory locations 3201 these subroutines put the

to
of
3500. use one

the arithmetic unit and transfer unconditionally
to
of
number the location the

in
x
F in by
The subroutine will replace the required function

of
of
start the subroutine

x
x
.
in
the main program

to
the arithmetic unit and return the next instruction

. .)
Air saturated with water vapor

70
at
to
atm and heated

is
4.51 150
F
1
°
.
What the percentage humidity

at is is
a
?
.
the molar humidity

What
b
10 ?
.
Air percentage humidity

at
atm and humidified constant

is %
4.52 100
is
1
a
F,
,
°
.
wet bulb temperature until the air saturated

. -
What the saturation temperature

is
a
F, ?
air
what are the final molar and percentage

90
to
the then reheated

If
is
b
°
.
humidities
?
atm has temperature and relative humidity per cent

90
50
Air
at
of
of
aа
4.53
F
1
of a
°
.
What the dew point the air

is
Determine the molar humidity which has dew point

85
65
at
of
of
4.54 air
F
F
.F a
°
°
.
per cent humidity

50
70
4.55 Air Plot the moisture

at
to
120 and cooled

is
F
°
°
.
air temperature Show the dew point

as
A of
of
content the air function

a
an .
of .
all
two hase liquid mixture composition per cent

20
10
at
4.56 has over

C
°
-
.
20 -p
per cent isopropyl ether and per cent water Determine the com
70
acetic acid
of ,
position the liquid phases

of
each
.
the following liquid mixtures exists

as
two phases
of
4.57 Which Determine the

?
.
compositions of the two phases :
Acetic acid , % Water , % Isopropyl ether , %
a 20 20 60
b 60 30 10
с 30 10.5 59.5
d 40 30 30
4.58 . To what temperature must a mixture of 30 per cent MgSO4 , 70 per cent H ,0
(by weight ) be heated to ensure that the MgSO4 is completely dissolved ?
4.59 . A 40 per cent (by weight ) solution of MgSO4 in water is cooled from 220°F
the
to 20 ° F . List the phases present during cooling and the temperature at which
all
Assume that equilibrium exists
at
phases change times
.
in .
Determine the composition the phases present
20
per cent
of
of
4.60 mixture
a
.
by
MgSO4 per cent H20 weight

80
20
for at
F
,
°
(
.
the decomposition
of
Determine the rate constant tetra
in
4.61 N2O5 carbon
.
chloride solution from the following data

:
Time sec Concentration N2O5 moles liter
g
,
/
2.33
0
184 2.08
319 1.91
526 1.67
867 1.36
1,198 1.11
1,877 0.72
2,315 0.55
3,144 0.34
Calculate the concentration

at
of
N2O5 4,000 sec

to .
4.62 Develop simplified computer program solve Prob 4.61

a
.
.
for
the hydrolysis ethyl acetate

of
Determine the rate constant

in
4.63 sodium
a
.
.
hydroxide solution using the following data

25
at
C
°
of
Concentration
of
Concentration
Time sec ethyl acetate NaOH
,
,
,
moles liter moles liter

g
g
/
0.00486 0.00980
0
178 0.00398 0.00892

273 0.00370 0.00864
531 0.00297 0.00792
866 0.00230 0.00724
1,510 0.00151 0.00645
1,918 0.00109 0.00603
2,401 0.00080 0.00574
Calculate the concentration ethyl acetate

of
at
3,000 sec
b
.
.
4.64 . The gas - phase reaction
H2 + 12 = 2HI
is reversible .
a . Write expressions for the rate of the forward reaction , for the rate of the reverse
reaction , and for the equilibrium constant .
b. For 698.2 ° K at equilibrium , Ch , 0.4789 g mole /liter , Ci , 0.4789 g mole /
liter , Chi =- 3.531 g moles / liter . Calculate the equilibrium constant .
c. At 698.2 ° K what will be the equilibrium concentration of HI when CH, 1.83
and ci , 3.13 g moles / liter .
4.65 . Ammonia is formed through the reversible gaseous reaction
12 N2 + 32 H2 = NH3
At 500 ° F the equilibrium constant for this reaction is 434 ( g mole / liter ) -1 .
a . Write expressions for this equilibrium constant in terms of concentration of
reactant and product molecules , and in terms of partial pressures .
b. What effect would an increase in total pressure have on the equilibrium per cent
conversion of N ,2 and H , to NH ;?
c. Calculate the value of the equilibrium constant in partial pressure units .
d. What would be the equilibrium partial pressures of H , and of NH , in a reactor
operated at 500 ° F and 100 atm in which the partial pressure of N2 is 10 atm ?
4.66 . The reaction
CO2 + C = 2CO
is carried out by passing carbon dioxide through a bed of coke at 2000 ° F and 100 atm
total pressure . At this temperature the equilibrium constant is 630 atm . Calculate
the
equilibrium partial pressures the gas phase

of
of
CO2 and CO Since exists

in
C
(
.
its
pure solid concentration does not enter into the equilibrium constant
as
here
a
expression
.)
additional problems are needed

computer programming Probs 4.9 4.15
in
If
,
by.
4.63 4.66 may writing

of- be
4.17 4.29 4.30 4.34 4.39 4.45 solved

4.47 4.56
is a
,
or ,
computer program many these problems

In
calculational flow chart

it
.
up
by
the program flow chart and then solve the problem

or
to
instructive set hand

-by
following the program step

or
flow chart step

-
REFERENCES
R.
Alberty Physical Chemistry John Wiley

F.
A.
Daniels and Sons Inc.

1.
&
”,
,
,
:
New York 1955

,
D. .
Hodgman Chemistry and Physics

ed
C.
of
Handbook Chemical Rubber

2.
”,
,
“
(
)
:
.
Publishing Co. Cleveland Ohio 1959

,
Physical Chemistry Prentice Hall Inc. Englewood

2d
ed
Moore W.
3.
",
J.:
,
.,
,
"
Cliffs N.J. 1955

,
( .
Perry Chemical Engineers

3d
ed
ed
H.
Handbook McGraw Hill

J.
4.
,
,
.,
-
)
:
.
'
Book Company Inc. New York 1950

,
.
M.
Chemical Engineering
H.
C.
Smith and Van Ness Introduction

to
5.
J.
,
"
:
Thermodynamics McGraw Hill Book Company

2d
ed
Inc. New York 1959

, ”
.,
,
-
.
CHAPTER 5
THE MASS BALANCE
all
A
mass balance is an accounting for the material process The
in
a
.
single process may intuitively
be
mass balance for unit obvious but
a
,
complete mass balances for large process are often very complex
a
.
systemic approach desirable calculating mass balance
in
A
Several
is
.
steps may be listed
:
Draw simple schematic flow diagram the process showing
all
of
1.
chemical reactions and physical changes

.
all
List available relevant data including flow rates temperatures

2.
,
,
,
pressures compositions and other physical data which may
be
necessary
,
.
on
helpful list process directly
to
the flow sheet labeling

It
often data
is
,
the appropriate streams
.
Study the flow diagram and process data develop the necessary
to
3.
relationships between known and unknown quantities the mass balance

in
be the .
For complex mass balances the necessary relationships may
be
in
,
mathematical equations simpler cases the balances may

In
of
form
,
.
solved without using formal equations

be
more obvious and can

,
the
resulting relationships and list the resulting data
on
Solve the
4.
flow sheet
.
no
Step the most difficult and important There are convenient

is
3
.
no
equations which always work there are general rules which can
be
;
blindly applied first necessary understand the process thor

to
It
is
.
oughly and develop plan The necessary data for solu

to
of
solution
a
.
be
too little data are available

or
tion must obtained Often too much

.
The engineer must eliminate extraneous data and obtain more data where
necessary
.
always necessary The

of
to
choose basis calculations basis

It
is
is
as a
quantity
10
usually
lb
of
reactant
of
matter such moles 100 lbm

of
a
,
,
liquid 100
cu
entering gas etc. The choice proper basis often

of
of
ft
a
,
simplifies the solution the problem The proper basis not always
of
is
.
its
obvious choice requires careful study

of
the data available Choice

a
;
less
perhaps
of
another basis still allows correct solution but

a
conveniently
.
The mass balance based upon the law

of
of
conservation mass which

is
174
THE MASS BALANCE 175
states that mass can be neither created nor destroyed . In a closed

system no material enters or leaves . Therefore , the mass in a closed
system must be constant . The
mass may change form , but the M
total quantity remains unchanged .
In а flow system , the mass of
streams entering the system must
equal the mass leaving , plus any Mą
accumulation of mass within the Accumulation =MA →
-M5
system . A system is shown
flow M3
in Fig . 5.1 . The streams of masses
M1 , M2 , and M3 are entering the
system ; streams of masses M4 and
MA
M5 are leaving ; and mass MA is
accumulating Fig .
5.1 . Mass balance in a flow system .
within the system .
If the “ accumulation has a neg
"
ative value , there is a depletion within the system . A mass balance

states :
Mass input = mass output + mass accumulation ( 5.1 )
For the system of Fig . 5.1 , this expression is
M1 + M2 + Mg3 = M4 + Mg5 + MA (5.2)
The symbol M may be a mass or a mass flow rate , and MA А is either the
accumulated mass or the rate of accumulation . M should be in pounds

mass . If there are no chemical reactions involved >, M may be in pound
moles . Frequently where gases are involved , M in pound moles is more
convenient . However , if there is a chemical reaction with a change in
number of moles , Eq . (5.2 ) does not hold in pound mole units .
Steady state exists when the accumulation is zero . Then
Input =
= output
and M1 + M, + M2 M4 + M5 ( 5.3 )
The number of streams shown in Fig . 5.1 is arbitrary . In general , with i

inlet streams and o outlet streams , Eq . ( 5.1 ) becomes
Σ
Ż MM,; = ΣM
M. +
+ MA ( 5.4 )
Example 5.1 . A 50,000 - gal gasoline storage tank is filled from four sources . Dur
thethe ing
one day's operation the sources supply 10,000 17,000 and 23,000 gal
to
6,000
,
During the same period 65,000 gal gasoline At

of
tank withdrawn for use

is
.
beginning the day the tank was half full How much gasoline
of
the tank
in
at
is
.
the day
of
the end
?
10,000 gal
6,000 gal
25,000 gal 65,000 gal
17,000 gal + V
23,000 gal
Fig . E5.1 . Flow sheet for gasoline storage tank .
Solution . The tank is shown schematically in Fig . E5.1 . A basis of one day is
chosen , It will
all
be assumed that the same temperature
at
streams are that the
so
,
By
density constant Then the mass directly proportional
to
the volume
is
is
.
.
Eq 5.4 with constant density
p
a
(
)
.
,
VŠ
ΣΜ
++
Σ
Μ
Μ
M
É
-
.
.
;
.
i
V. PVA
+
p
Š
0
or
Σν v Σv
v,Vi
=
Ý
+
.
V
.
-- =
+
where Vi individual volume
in
=
V.
individual volume out
VA total volume accumulated
Then from the data given
,
10,000 6,000 23,000 gal 65,000 gal VA
+
17,000
+
Therefore VA -9,000 gal

=
,
The tank initially contained 25,000 gal -9,000 gal

an
With
of
accumulation the
,
.
final volume
in
the tank
is
25,000 -9,000 16,000 gal

+
=
(
Equation 5.4 the total material balance that considers the

is
is
it
;
,
in of of (
)
total mass each stream frequently necessary

of to
consider the
If It
is Xi is
.
components the streams the mass fraction particular

is
a
.
component the stream Mi

xa
the mass fraction Mo and the

in
xo
,
mass fraction MA component balance

in
is
a
,
5.5
Ź
w
Μαι M.X.
+
A
4X4
-
(
)
M
=
Σ
an
Most material balances require the this equation equivalent

is of
or
use
M
calculation pound moles

in
If
mole fraction there

is
If
is
x
a
,
a
.
chemical reaction involved the process Eq 5.5 holds for either mass
in
)
.
atomic fraction but not necessarily for mole fraction

or
fraction
,
Often component goes through the chemical process unchanged

If
a
sufficient data are given about this component

be
can
in
used
it
com
a
,
ponent balance determine for example the total masses the entering
to
of
,
leaving component
to
as
and streams Such sometimes referred the

is
a
.
key component Key components may compounds

be
as
such
.”
"
(
H2SO4 ), unchanged groups in compounds ( such as SO3 in H2SO4 formation
its
from SO3 ) , or elements ( such as S ) . The key component must retain
identity as
passes through the process Obviously except for nuclear
it
,
.
sulfur may always key component
be
reactions elements such
as
as
used
a
,
,
because they not change identity even though they may undergo
do
a
Thus H2SO4 may
be
chemical reaction key component only
as
used
a
.
may any
be
when
at
does not react but used time
it
S
,
.
component that enters the system only one stream and leaves
in
in
A
only one stream usually the most convenient choice for use key
as
is
a
oil
component For example from soybeans the
of
the extraction in
,
,
.
it oil
inert pulp enters along with the the raw beans The entering sol
is in
.
oil
vent may also contain

as
often recovered and reused but
In it
some
,
no
contains inert pulp

Thus the pulp enters only with the beans
.
.
the exit streams the extract light product from the top
of
the column
,
)
no
oil
contains solvent and but pulp The underflow sludge heavy

,
(
.
product from the bottom
oil
the column contains pulp
of
and solvent
.
,
)
Thus the pulp enters only one stream the raw bean feed and leaves
in
:
only one stream the underflow sludge unchanged the proc
It
in
of in
is
).
(
an
ess Thus forms ideal key component The choice key com
it
..
other systems will the examples

be
ponents
of
this
in
illustrated
in
chapter
.
OVER ALL BALANCES

-
equip
on
frequently possible unit

to
of
It
determine mass balance

is
to a
on
an
process without sufficient data describe the

or
ment entire
on
process detail Sufficient data the streams entering and leaving the
in
be .
on
process must available but data streams within the process are
,
not needed
.
Fig 1.1 separates

a an
Example 5.2 distillation column similar that shown

in
to
A
of -- .
ethyl alcohol water feed into high urity alcohol and waste water The feed has
.
-p
composition mole per cent ethyl alcohol mole per

20
85
The distillate contains

.
cent ethyl alcohol and the bottoms have per cent alcohol concentration
3
a
,
feed calculate the quantity

45
For
of hr
of
of
distillate and bottoms

lb
moles
6. a
,
.
What percentage the alcohol the feed recovered the distillate

in
in
is
Solution The flow sheet Fig E5.2 shows only the external streams Nothing
a
.
)
.
known about the internal operation For example the flow rates
of
of
the column
is
,
.
to
the reflux streams from the condenser and reboiler back the column are not known
.
no
chemical reactions involved the mass balance may

be
Because there are written

,
pound moles per hour and

M
be
be
of
terms Let
the molar flow rate
in
moles
in
A x
.
the
Steady state that Ma

so
mole fraction ethanol

in
each stream assumed

is
is
,
.
zero Application the total material balance Eq 5.4 gives

of
.
)]
.
Mi = M2 M3
+
hr
or M2 M3
lb
45 moles
/
The component balance for the alcohol is , by Eq . (5.5 ) ,
MX1 = M 2x2 + M 3X3

or (45 ) (0.20 ) 0.85M2 + 0.03M 3
With two equations and two unknowns , a solution for M2 and M3 is possible :
M3 = 45 – M2
(45 ) (0.20 ) = 0.85M2 + 0.03 (45 M2 )
M2 9.3 lb moles / hr
M3 35.7 lb moles / hr
M212 ( 9.3 ) (0.85 )
b. Percentage recovery 88 per cent
MiX 1 (45 ) (0.20 )
In this problem ethyl alcohol was chosen as the key component because , since it was
Distillate , M , Ib moles / hr
*2= 0.85
Feed, M = 45 lb moles /hr .
Xq= 0.20
6
-Bottoms , Mg Ib moles / hr
X3 = 0.03
Fig . E5.2 . Distillation column .

its
not involved in a chemical reaction , it retained identity A balance could also

.
have been written with water the key component

as
PHASE EQUILIBRIA
Mass transfer operations frequently require mass balance involving

a
be
phase equilibrium few fundamental cases will considered here

A
.
a
mass transfer operations

of
more detailed discussion mass balances

in
A
found unit operations

in
is
texts
.
Raoult's law was used Chap calculate the composition vapor

to
of
in
4
.
be
to
liquid phases equilibrium The calculation can extended

in
and
.
determine the quantity each phase present mixture Because

in
of
phase equilibria
no
there are chemical reactions involved the mass

in
particularly convenient
, on
balance may This

be
taken molar basis

is
a
vapor liquid equilibria because Raoult's law and Henry's law involve
in
mole fractions total mass balance for vapor liquid equilibrium

is
A
.
-
+
5.6
2
V
=
L
where liquid
L
moles
lb lb
of of
mass
= = =
vapor
Σ V
mass moles
,
of
total mass mixture moles

lb
,
A mass balance for component a gives
Lxa + Vya = Sza (5.7 )
where xa = mole fraction a in liquid

Ya mole fraction a in vapor
2a mole fraction a in mixture
for
A similar balance equation may be written the components
of
each
.
With sufficient data and equations possible solve for the unknown
to
is
it
,
quantities
.
Example 5.3 An equilibrium mixture containing mole per cent benzene and
75
.
mole per cent toluene total pressure 900 mm Hg must sepa

25
be
at
of
200 and
F
a
°
rated into vapor phase and liquid phase

a
.
Calculate the compositions and quantities the two phases for 100
of
of
moles
lb
a
.
the initial mixture

.
Calculate the composition and quantities the phases the temperature of

6.
if
is
to
lowered 100
F
°
.
V
lb
moles vapor
Yc Yo
moles mixture
lb
26 {
0.75
==
0.25
2,
moles liquid
Ib
хь L
Xt
Fig E5.3 Schematic representation equilibrium mixture

an
of
.
Solution Fig E5.3 The compositions the vapor

a
of
The flow sheet shown

in
is
.
.
and liquid are determined

At
Chap Appendix
as
shown
in
1,150
D
200 Pvb
F
=
4
°
(
)
.
.
mm Hg Pvt 460 mm Hg By Eq 4.41

,
)
.
1,150 460
хь
Yc
Yo Xt
900 900
yo
X6
and
=
+
+
yt
Because
Xt
1
1
1,150 460
Xb
x6
–
1
1
t
900 900
and Xb = 0.636 Xt = 0.364

yь 0.814 0.186
Yt
of
obvious moles mixture The total mass balance

lb
The basis here 100

is
is
:
100
+
V
L
By
Eq 5.7 the benzene component balance

is
(
)
.
0.636L 0.814V 0.75 100

(
)
The toluene component balance is
0.364L + 0.186 V 0.25 ( 100 )
Only two of these three equations are independent . ( The last two add up to equal
the first .) Any two of them may be used to solve for the two unknowns . With the
first and second equations ,
V = 100 -L
and 0.636L + 0.814 ( 100 – L) 0.75 ( 100 )
L = 35.9 lb moles
V = 64.1 lb moles
6. At 100 °F , Pob 155 mm Hg , Pvt = 52 mm Hg . As before ,

155 52
Yo хь Yt х:
900 900
155 52
хь + (1 Xb) 1
900 900
Solving gives x6 = 8.2 . This result is obviously impossible . An examination of the

vapor pressures shows that they are both less than the total pressure . Therefore ,
only a liquid phase exists at 100 °F . The value of xy has no meaning because Raoult's
law applies only to a two - phase equilibrium .
Mass balances for liquid - liquid equilibria may be determined graphi

cally . Graphical mass balances are discussed at length in Chap . 3 .
Example 3.4 is a graphical mass balance . The same technique may be
applied to a problem in liquid - liquid extraction , as shown below .
Example 5.4 . Acetic acid is to be extracted from aqueous solution using isopropyl
ether . 125 lbm of a 40 per cent acetic acid , 60 per cent water solution is mixed with
75 lbm of pure isopropyl ether . The mixture is allowed to come to equilibrium , and
the resulting two phases are separated .
a . Determine the composition and mass of each phase .
b. What percentage of the acetic acid was removed from the aqueous phase ?
Mi = 125 1b -M3
x = 0.40 xo
Xg = 0.60 Mixer *b
separator хс
M2 =75 16
Xc = 1.0 MA
ха
Xb
Xc
Fig . E5.4a . Mixer - separator .
Solution . a . The flow sheet is shown in Fig . E5.4a . First, M ,1 and M2 are mixed
graphically , as shown in Fig . E5.46 . The process is
Mi + M2 = Σ = M3 + M4
The point representing the composition E is located by the inverse lever - arm rule
1.005 M2
-M3
0.8
0.6
Tie
xc , Yc line
0.4
Σ
0.2
Ma
M
o
0.2 0.4 0.6 0.8 1.0
Xa, Ya
0.6
0.4
ya
0.2
0.2 0.4 0.6 0.8 1.0

Xo
Fig . E5.46 . Solution to Example 5.4 .
/
2 = 75 ( 125 + 75 ) 0.375 of the distance from M , to M2 . Then the mixture
splits into two equilibrium phases, whose compositions are determined by trial and
Fig E5.46
tie
on
error, as shown in Example 4.16 . The correct line shown By

it is
.
to
application a rm rule the tie line found that

of
the inverse lever

is
,
-
Xc
lb lb
0.165 0.790
= =
M3 89.5 Xa
M4 110.5 Xa = 0.315 Xc 0.040
M
of
Mass acetic acid M3

in
b
34a
.
89.5 0.165
(
)
lb (
14.8
M.
of
Mass acetic acid Mixa

in
125 0.4
(
lb )
(
50
14.8
=
Acetic acid removed from M1

50
%
29.6
HUMIDITY
Mass balances involving humidity are made for drying , humidifica

tion , air conditioning , and water cooling .
5.5
Example dry inorganic paint pigment
an
tunnel drier 1,000
to
used
is
.
.
pigment containing per cent water 0.5 per cent water
10
be
hr
to
of
dried
lb
to
is
/
.
air
The pigment 760 mm Hg 140
to
at
passed countercurrent which enters and
F
is
,
°
,Hg
per cent humidity and leaves per cent humidity
10
95
70
at
750 mm and
F,
°
.
of
What flow rate air must be maintained
?
#lhr
.
70 air
hr
air
% hr
F, Ib
MA
° Ib
M
,
/
10 /
90
humidity 140 humidity

%
°
F,
750 mm Hg 760 mm Hg
1,000 My
hr
hr
% % lb
lb
M
/
/
1090
Pigment Pigment 99.5
%%
Water Water 0.5
Fig E5.5 Tunnel drier

.
air
Fig E5.5
go
Solution The flow sheet shown The pigment and through
in
is
.
air
unchanged The process transfers water from the pigment
to
the Two methods

.
.
will be illustrated
.
METHOD wet pigment The key component the dry pig

hr
Basis 1,000 lbm

1
is
it .
/
:
ment since does not change quantity

in
,
Dry pigment
hr
in
1,000 900 lbm

=
0.90
=
/
(
)
(
hr )
Dry pigment out 900 lbm

/
900 lbm
hr
Solids out M3 904.5 lbm

/
,
0.995
H2O leaving
hr
M3
in
0.005 904.5 4.5 lbm

=
V
/
(
)
(
V
H2O entering Mi 100 lbm hr
in
0.10 1,000
/
(
)
(
4.5 = 95.5
to
H2O transferred air

hr
100
–
lb
/
up
by
The H2O picked mole dry air

of
mole air now calculated basis

lb
lb
is
1
1
(
)
:
From Fig 4.8 mole dry air

Y2
mole H2O
lb lb
lb lb
0.025
/ /
,
.
YA 0.042 mole H2O mole dry air

mole dry air
18
to
Water added
lb
0.042 0.025
1
0.31 lbm H2O

95.5
dry air required = dry
air
hr
Therefore
lb
310 moles
,
0.31
/
of
Moles
hr
wet air
) in
lb
+
318 moles
+ =
310 0.025
1
/
) )
-
( (
)
(
hr
29
18
M2 9,130 lbm
=
310 310 0.025

/
(
)
(
)
(
)
(
At
Gas rates are usually expressed volumetrically

32
standard conditions 760

F,
°
(
.
mm Hg ) 1 lb mole occupies 359 cu ft . Therefore ,
V2 (318 lb moles ) (359 cu ft lb mole ) /

114,000 cu ft at standard conditions /hr
At 140 °F and 760 mm Hg
460 + 140
V2 114,000
460 + 32
139,000 cu ft / hr
On the other hand ,
M4 (310 ) (29 ) + (310 ) (0.042 ) ( 18) 9,220 lbm /hr

V E 132,500 cu ft / hr
(310 ) ( 1 + 0.042 ) (359 ) (555492 ) (760450 )
METHOD 2. This problem may also be solved using analytical expressions :
YA (0.025 ) ( 1829 ) 0.0155 lbm H2O / Ibm dry air
and the mass fraction
X2 = 0.0155 /
( 1 + 0.0155 ) - 0.0153
Similarly , Y == (0.042 ) ( 1829 ) 0.0260 lbm H20 /1bm dry air
and /
24 = 0.026 ( 1 + 0.026 ) 0.0254
Total mass balance :

Mi + M2 M3 + M4
or 1,000 + M2 M 3: + M4
Water balance :
MX1 + M 2x2 M 3X3 + M 4X4
( 1,000 ) (0.10 )+ 0.0153M2 = 0.005M3 + 0.0254M4
Pigment balance :
( 1,000 ) (0.90 ) 0.995M 3
There are three equations and three unknowns ( M2 , M3 , M4 ) . Solving gives
( 1,000 ) (0.90 )
M3 0.995
/
904.5 lbm hr
M2 9,200 lbm / hr
M4 · 9,300 lbm hr /
These values check those obtained by the first method within slide -rule accuracy .
The second method is more formal ; the first perhaps is more easily followed step by
step . In many problems , the first method is preferable . In others , the second
method is shorter and clearer .
CHEMICAL REACTIONS
A balanced equation for a chemical reaction gives a quantitative rela

tionship between the reactants and the products . In the simplest case ,
usually covered in freshman chemistry , exactly enough of both pure
reactants are available , and they react completely to give the desired
product . In an industrial process , the reactants usually are not pure ;
one reactant may be in excess ; and the desired reaction may not go to
completion because of rate or equilibrium considerations . There may be

other competing reactions which reduce the yield of desired product .
All these and other factors must be considered in writing a mass balance
on an industrial process .
The terms used to describe a reaction that does not involve stoichio
metric ratios of reactants must be carefully defined in order to avoid con
fusion . If the reactants are not present in formula ratio , one is said to be
limiting ; the others are said to be in excess . Consider the reaction
SO2 + 1202 = SO3
as occurring between lb mole of SO , and 3 lb moles of oxygen . Here

1
SO , is the limiting reactant, with O2 present in excess . There are 222

lb moles of excess O2 because
, only 22 lb mole is required for the reaction .
Thus , there is 500 per cent excess oxygen present . The per cent excess
must be defined in relation to the amount of the reactant necessary to
react completely with the limiting reactant . Thus , if only part of the
SO2 actually reacts , this does not alter the fact that the oxygen is in excess
by 500 per cent . However , there are often several possible products .
For instance ,
S + 02 = SO2
S + 32 02 = SO :
can occur simultaneously . In this case , if there were 3 moles of oxygen

present per mole of sulfur , the oxygen would be in excess . The extent
of this excess could not be definitely fixed . It is customary to choose one
product and specify the excess reactant in terms of this product . For this
case , there is 200 per cent excess oxygen for reaction to SO2 , or there is
100 per cent excess oxygen for reaction to SO3 .
Frequently , one reactant enters in several feed streams . For instance ,
blast -furnace gas typically contains 10 per cent C02 , 27.5 per cent CO ,
,
0.5 per cent 02 , 2.7 per cent H2 , 59 per cent N2 , and 0.3 per cent CH .
( compositions by volume ). If this gas were to be burned in air , the oxy
gen required would be that necessary to convert CO , H2 , and CH4
entirely to CO2 and H20 . The 0.5 per cent 0 , in the gas itself would
have to be subtracted from this total requirement to get the theoreti
cally required 02. From this the theoretically required air could be cal
culated and any per cent excess air determined .
The conversion is defined as the per cent of the limiting reactant which
is consumed in any way . It does not matter that there may be several
competing reactions or that much of the reactant may be converted to a
by - product .
The percentage yield is defined as the ratio of the actual mass of desired
product to the mass which would have been obtained if the desired reac
-
....
tion had gone to completion . Incomplete reactions and side reactions

reduce the yield . Often chemical equilibrium makes it impossible to
reach 100 per cent yield in one pass through a reactor .
Example 5.6 . Sulfuric acid is produced as a by - product in the manufacture of zinc
from sulfide The ore (70 per cent ZnS , 30 per cent inert impurities ) is burned in
ores .
a furnace . The resulting SO , is oxidized to SO3 and absorbed by water to give sulfuric
acid . The acid is 98 per cent H2SO4 , 2 per cent water . 99 per cent of the sulfur in
the ore is recovered as acid .
a . Calculate the quantity of sulfuric acid produced in a zinc plant processing 200
tons of ore per day .
b . How much water is required ?
M tons
waste gas
,
M tons H20
air
Soz +
Absorber
Air
Oxidizer
Furnace .99
200 tons ore
M
% =
70 ZnS Ma tons
SO
air
+
,
Zno product acid

luo + 98
% H2SO4
.9
impurities
t
142.29
X. 7
.
Fig E5.6 Sulfuric acid plant

99X9
.
Not enough data are given complete flow sheet sche

to
Solution draw but

of a
a
,
.
matic diagram Fig E5.6 useful for purposes calculation

is
(
)
of .
BASIS 200 tons ore

:
Molecular weights
:
ZnS 97.5 H20 18.0 SO2 64.1 32.1 H2SO4 98.1

S
Reactions
:
Furnace
12 32
02
+→→
ZnS ZnO
+ +
SO2
:
Oxidizer SO2 02 SO3

:
Absorber
+
SO3 H2O H2SO4

:
The sulfur may the key element this problem because appears
be
as
taken
in
it
a
,
.
the initial reactant and

in
the product
in
ton Zns 32.1 tons

S
0.70
Mass
of
200 tons ore

in
ore
S
ton ore
:)
(
46.1 tons
=
98.1 tons H2SO4

produced
of
Mass H2SO4 46.1 tons 0.99 32.1 tons

S
(
)
(
139 tons
=
139
142 tons
98
M.
of
Mass
%
acid
,
0.98
b. By the absorber equation , 1 lb mole H2O is needed for each pound mole of H2SO4
produced . Additional water dilutes the acid to 98 per cent .
18.0 tons H2O
9,80
acid
0.02
98 .
Mass H2O , 139 tons H2SO4 + ( 0.02 142 tons acid
((98.1
(
ton
)
M2 = tons H2SO4
.)
= 28.3 tons
-by
The step step procedure used this problem
of
the solution more convenient
in
is
-
than the formal total and component mass balance equations used other problems
in
-
.
However possible use the balance equations here desired
to
if
is
it
,
.
The combustion
of
fuel involves several chemical reactions Common
.
oil
industrial fuels include coal fuel natural gas and various manufac
,
All these fuels contain carbon hydrocarbons
or
as
tured gases major
a
.
though compounds containing oxygen and sulfur may
be
constituent
,
present Noncombustible inerts are often present Complete combus

.
.
give CO2 and H20 not usually possible even with
an
to
tion
is
excess
,
supply that the combustion products will usually contain
CO
so
of
air
,
.
O2
usually obtained only when the air supply
or
much less than
H
is
is
,
that theoretically required

.
Example 5.7 Natural gas 78.8 per cent CH4 14.0 per cent C2H6 0.4 per cent
40 ,
,
(
.
74 by
C02 6.8 per cent volume burned with per cent excess air The hydro
N
to is
,
.
per cent per cent Calculate the com
26
to
carbons are converted CO2 and CO
.
position the gas leaving
of
air
Mą moles
lb
0,79
21
N2
%
excess
40
%
Burner
100 moles natural gas moles exit gas
lb
M2
lb
M
=
;
78.8
% % % %
CHA CO2
14.0 C2H6 CO
0.4 CO HO
,
6.8
O2
N2
N
Fig E5.7 Gas burner

.
Solution METHOD natural gas because

of
convenient basis
A lb
100 moles
1
is
.
,
.
.Fig
the molar analysis the natural gas flow diagram given

of
in
available
is
is
E5.7
.
lb
BASIS 100 moles natural gas

:
1
1
NATURAL GAS
lb
CH4 78.8 moles

:
C2H8 14.0
:
CO2 0.4
t4
:
N2 6.8
zt
Hut
32
Ho
Co
í
2
C
care
2
AIR SUPPLIED
Total carbon in hydrocarbons 78.8 + 2 X 14.0 = 106.8 lb moles

( The 2 appears because thereare 2 atoms of C per mole of C2H6 .)
O2 required for complete combustion ( C + O2 → CO2 ) 106.8
Total hydrogen in hydrocarbons 2 X 78.8 + 3 X 14 199.6 lb moles

O , required for complete combustion ( H , +12 02 = H2O ) = 199.6 / 2 = 99.8 lb
moles
Total O2 required = 106.8 + 99.8 = 206.6 lb moles
O2 supplied (40 per cent excess over that required for complete combustion to
CO2 and H2O ) = ( 1.40 ) (206.6 ) 289 lb moles
0.79
N2
air
79
21
02
N2 with 0 , in 1,085 moles
lb
% 289
%
=
,
0.21
(
)
moles
+
lb
M2 1,085 289 1,374
ACTUAL COMBUSTION
74 per cent
to
CO2
of
C
+
0
0.74 106.8 CO2

(C
)
(
)
(
)
+
79C 7902 79CO2

or
CO
to
26 per cent
of
C
→ 12
02
CO
+
0.26 106.8
(C
)
(
)
(
or 27.80 27.8CO
+
13.902
All
to
H2O
H
,
199.6H2O
+
199.6H2 99.802
EXIT GASES
Mole volume per cent
or
79.4
lb
CO2 0.4 79.0 79.4 moles 5.3

+
1494.9
CO 27.8 1.9
H20 199.6 13.3
289 79 13.9 99.8 96.3 6.4
–
O2
-
1,091.8 73.1
+
N2 6.8 1085
Total moles 1,494.9 100.0
lb
moles
An
up
METHOD
set
alternate procedure that may prove convenient

to
2
the
.
is
The advantage here that components

of
balances tabular form

in
results mass
is
.
are less likely forgotten the analysis more formal approach

be
to
used The
in
is
.
logical method presenting results and

of
table forms framework which controls

a
a
of
the sequence calculations

.
All components are

for be
The same basis natural gas will

lb
of
100 moles used

(
Table E5.7 where separate columns are given feed streams conversion
in
in
listed
,
the burner and products

,
the table by the negative

on
All the methane and ethane are burned This shown

is
.
Change burner column The water formed from this

of in
quantities the
in
entered
”
as “
of
calculated water for each mole CH4 and moles water

of
combustion moles
is
3
for each mole of C2H6 . The results are entered into the table beside the water entry .
The CO2 formed is next determined . This CO , contains 74 per cent of the number of
in is the
C atoms in the hydrocarbons . The results are entered into the table opposite
CO listing The CO formed similarly calculated and listed The oxygen used
is
,
,
.
then equal the CO2 formed plus half the This also shown
to
and CO formed
is
H
0
,
.
the table The solution now requires only the calculation
be
This must
of
. M2 done
.
TABLE E5.7 SOLUTION TO EXAMPLE 5.7 METHOD
2
(
)
.
Com
Feed Change burner Product
in
ponent
199.6
79.0
02 0.21M2
++
0.21M2 192.7
27,8
+
6
-
(
)
2
N2 6.8 0.79M2 6.8 0.79M2
+
+
CHA 78.8 -78.8
14.0 14.0
-
C2H6
0.4 0.4
14
CO2 +0.74 78.8 79.0
+
79.4
X
+ + +
=
2
(
)
14
H2O 78.8 199.6
X
+
X
2
) 3
(
)
CO +0.26 78.8
14
27.8
X
2
(
+
2n
74
hydrocarbons
of
%
++
02
22
)
(
C.H3n nCO2 H
+
0
+
+
1
(n
–
+
2
+ nn
)
1
n
,
(
2n
1
nCO
26
H2O
+
hydrocarbons
of
+
02
+
CnH2n
%
+
1
n
2
)
(
2
exactly
as
Method The calculation made there and the results are collected
in
1.
is
useful way showing what needed
be
Note that the table
of
there
to
has been done
aa
.
completed
be
and what had been done
as
The calculations must still shown
in
.
Method
.1
air
Example Pure propane give the following

an
to
of
5.8 burned with excess

is
.
stack gas
:
Volume per cent

CO2 5.0
CO 3.5
H2O 11.4
02 7.0
N2 73.1
air
Calculate the percentage and the percentage completion

of
of
excess the combustion

to
of
carbon CO2
.
Because the composition given

be
will
as
stack gas
of
Solution used basis.

it
is
a
,
.
moles stack gas

is lb
BASIS 100
:
Fig E5.8 moles air

lb
flow sheet shown

in
moles propane
M
M1
A
lb
=
.
,
.
balance
C
3M1
lb +
5.0 3.5
=
Mi 2.8 moles
balance
N
,
0.79M2 73.1
=
lb
M2 92.6 moles
air
M2 lb moles
Burner
Ib
M1 moles propane M3 100 moles
lb
CzHg stack gas
%
100
(
lb lb lb lb Ib
CO2 5.0 moles
CO 3.5 moles
H2O 11.4 moles
N2 02
7.0 moles
73.1 moles
Fig E5.8 Gas burner

.
.
M2
be
somewhat longer
an
can also evaluated from balance but the calculation

O
,
2
)
3.5 11.4
92.97
+
+
0.21M2 5.0 7.0

+
orin
=
2
2
lb
M2 92.6 moles
=
02
required 2.8 C3Hg 3C02 4H20

+
502
(
)
:
lb
Mass 02 2.8 14.0 moles
X
5
0.21 92.6 14.0

(
)
(
Excess oxygen
%
3812
14.0
+ 5
59
Percentage
to
CO2
%
burned
C
3.5
5
BYPASS
some cases part process stream may bypassed around

be
In
unit
of
a
in a
the process rejoin the main stream after the unit Fig
to
as
shown
of
.
5.2
Without the bypass the desired product would not

be
obtained
,
.
Bypass
Gross Process Gross

feed Feed unit Product product
Fig 5.2 Bypass stream

.
Example 5.9 per cent humidity

95
90
be
Air
at
to
atm and conditioned

by°F
is
1
,
60 .
air
per cent humidity cooling part and mixing

75
50
° to
of
and the with

to
ft it
F
F
°
uncooled air
cu
The resulting mixture will

75
be
For 1,000
to
reheated min
.F
.
/
air
per cent humidity calculate entering

air
75
60
of
and the volume

at
) of
a
,
,
°
(
)
:
air
the percentage entering bypassed

of
that
in is
b
(
The flow sheet Fig E5.9

to
Solution shown convenient express the

It
is
of is
air .
air
on
dry basis that the pound moles dry the entering wet
in
of
mass
M
is
is
',
a
;
air
,
dry
air
Ma Ib moles bypass basis
)
-B
others
?
Cooler
Heater
condenser
Mg
1b
Mi
molesi Me moles
Ib
moles
lb
entering air air final air

dry basis 50 saturated dry basis
)
°
)
(
(
90 95
atm 75
F
1
% °
% °
F,
60
humidity humidity
H20
Fig E5.9 Air conditioning unit

.
.
cu
75
60
1,000 per cent
of
min final air

ft
BASIS
/
F,
°
).
(
:
cu
1,000
R
ft
535
492
R
/
°
SC °
)
moles wet air
lb
)
lb (
(
M3 2.56
a
.
at
cu
359 mole
ft
/
From Fig 4.8 per cent humidity

75
60
at
,
F,
°
.
mole dry air

lb
0.018 moles H2O

lb
Y;
M3 mole dry air
lb
1.0
+ (
)
moles wet air
lb
M's 2.56
(
wet air
lb
+
0.018 moles
lb :Y
1
)
(
2.52 moles air

all
An over mass balance around the entire system dotted loop shows that for air
A
(
)
-
M1
air
M
moles
lb
2.52
=
=
;
From Fig per cent humidity

95
90
at
4.8
,
°
F,
,
.
H2O mole dry air

lb
lb
0.053 moles
=
Y
Therefore
,
Mi
+
2.52 1.053
M
M
= =
=
(1
Y
)
)
(
moles
lb
2.66
)(sc
555
)
383
at
359
Vi
ft
O
cu
moles
lb
2.66 359
=
492
)
(
(
)
(
hinta
)
Ub'mols
cu
1,077 min
ft
/
.177 To determine the fraction bypass material balance taken around dotted
of
F, is
a
b
,
.
50
per cent humidity

At 90
to
loop
95
becomes saturated
at
B.
and
it
air cooled
If
is
F
Y4 °
°
the saturated humidity The bypass

50
and water condenses out 0.012

.
F,
,
°
.
per cent mass balance for dry air

95
90
at
Y2
so
and that
A
0.053
is
Y
°
around loop gives

B
, M
+ +
M
M
,
or M.
M
2.52
water balance
A
is
MY2
M
+
MAYA
4
=
;
Y3,
or 0.053M 0.012M4 =
+
2.52 0.018
,
)
(
Solving
,
0.36 MA 2.12
M
',
0.36
M
',
Percentage entering air bypassed

%
of
14.3
M1 2.52
RECYCLE
Many organic reactions do not give a 100 per cent yield of the desired
product . A catalyst which specifically speeds up the desired reaction is
frequently used . Even then , the yield may be limited by equilibrium
considerations . In cases where the yield is low , the unreacted starting
Recycle
Feed Gross Process Gross Net

feed unit product product
Fig . 5.3 . Recycle .
materials are separated from the product and sent back to the reactor as
recycle stream , as shown in Fig . 5.3 . A recycle is also used in several of
the unit operations for various purposes , generally to gain a more desirable
product .
Example 5.10 . Methanol is produced by the reaction of carbon monoxide with

hydrogen :
CO + 2H2 + CH3OH
Only 15 per cent of the CO entering the reactor is converted to methanol , so that a
recycle of the unconverted gases is necessary . As shown in Fig . E5.10 , the methanol
product is condensed and separated from the unreacted gases , which are recycled .
M2 lb moles /hr recycle gas ( 66.67 % H2, 33.33 % CO )

100 ° F , 300 atm
Compressor
Reactor
300 atm Condenser
M, Ib moles /hr M3 300 ° F M4 lb moles /hr
feed gas reactor product
66.67 % H2 CO , H2
19
33.33 % CO CH2OH
100 ° F, 300 atm
Separator
C H₂O
M Ib moles / hr
methanol
product
Fig . E5.10 . Methanol synthesis .
The methanol product contains small amounts of impurities introduced by side reac
tions , such as CO + 3H2 CH4 + H20 , but these will be neglected in this calcula
tion . Calculate : (a ) the volume of feed gas , and (b) the volume of recycle gas
/gal
required to produce 1,000

70
hr
at
of
methanol with reactor conversion

F
a
°
per cent
15
efficiency
of
ft Cart co
(il
)
0
(
all
Solution . a . The flow sheet is shown above . An over - mass balance will give
the feed gas rate
.
product methanol assume 100 per cent purity
hr
Basis 1,000 gal
(
:
).
Density Appendix
cu
70
at
ft
of
methanol 49.3 lbm
=
B
F
p ft /
°
)
1,000
6,600
Mass
cu lbm
1
hr gal
15.-
1bm
19.3
7.4
methanol product
) )
ft
hr
hr
gal cu
(
of
=
)(
)
(
/
6,600 lbm
/
Ms
hr
lb
206 moles
/
32
mole
lb
lbm
/
all
only one stream entering and one leaving

an
In
over balance there M3
M
is
;
,
(
(
)
a -
therefore carbon balance gives

,
0.333M Ms 206
lb =
Mi S
hr
618 moles
/
atm 560
R
1
°
=
Vi
hr
cu
at
mole SC
lb
lb
ft
618 moles 359
=
/
300 atm 492
(
)
(
R
°
cu
hr
840 feed gas rate

=
ft
/
)
The quantity recycle obtained by writing partial mass balance around the
of
is
b
a
.
separator and then around the reactor

.
as
BASIS Same
a
:
all
CH3OH balance stream My goes out
as
so
methanol M5 that the
in
SEPARATOR
,
:
methanol from the reactor M1 hr

in
lb
206 moles
=
/
(
.
The recycle
15
per cent CH3OH

of
the CO the reactor converted

to
to
REACTOR
is
:
.
and feed have the same composition There
to
so
that the CO the reactor 0.333M
is
3
,
.
per cent
15
fore the CO converted CH3OH

to
of
the reactor the total CO
in
is
,
:
0.15 0.333M3 206
=
(
)
(
and = 4,120
hr
M3
lb
moles
/
Because Mi M2 =
+
M3
the recycle M2 4,120
–
618
·
hr
3,502
lb
moles
/
-
atm 560 R R
1
°
and SC
hr
at
cu
V2 ,502 mole
lb
ft
lb
moles 359
/
300 atm 492

)
)
(
/
(3
°
hr
cu
4,780
ft
/
The recycle nearly six times the feed

is
The volumes calculated here are based upon the perfect as law which error
in
is
,
-g
at 300 atm more correct approach would use Eq generalized

be
to
4.22 and
A
a
.
)
.
compressibility chart see Ref

6
(
.
).
Example 6.11 The SO3 absorption tower sulfuric acid plant see Example 5.6
in
aa
)
.
by
weight liquid absorbent because SO

as
uses sulfuric acid 99.0 per cent H2SO4

a
;
,
(
Fig E5.11 the 99.0 per cent

As
particularly soluble 99.0 per cent acid shown

in
in
is
,
.
up
absorbs SO3 leaving 99.5 per cent acid

as
acid fed into the tower where Make

is
it
-
.
water dilutes this acid back 99.0 per cent product and the
as
to
Part withdrawn
is
,
.
recycled
to
rest the absorber

is
What the flow rate make p water

of
is
a
?
.
-u
per cent acid recycled into the tower plant producing

99
How much
in
is
b
a
.
100 tons day per cent product acid

99
of
/
on
all
Solution BASIS 100 tons product acid An over material balance loop
a
.
(
.
:
will give the quantity water assuming negligible H2O gas streams The key
in
as of
A
,
)
component H20 both water and the H2SO4 molecule

in
is
.
removed in the products , it must accumulate until purged . In some

processes , the nonreactive material may be removed in a product stream ;
in other systems , it accumulates and must be purged .
Example 5.12 . In the methanol synthesis described in Example 5.10 small quanti
ties of nonreactive gaseous impurities ( N2 , hydrocarbons ) are present in the feed .
They do not dissolve to any appreciable extent in the liquid methanol product ; so
the
they must be removed by a purge in the recycle line . If they are not removed ,
impurities and the pressure will increase
to
of
the detriment
of
concentration the
to at 0.1
H2
desired reaction The feed gas contains 66.6 per cent 33.3 per cent CO and
,
.
/gal
per cent nonreactive impurities The plant produces 1,000
hr
of
methanol
be
the purge rate
70
15
the reactor What must
in
with per cent conversion
a
F,
°
by
maintain the impurity concentration the recycle below per cent volume
in
?
(
)
Mo
moles purge
66Ib
H2
%% %
33 CO
impurities
1
66
Recycle gas H2,33 imp
%
CO
1
,
(
)
.
100 300 atm
°
F,
Compressor
Reactor
300 atm Condenser
Ib
moles
M
300
,
F
°
feed gas
66.6
° % % %
H2
33.3 CO
0.1 impurities
100 300 atm Separator
F,
206 mg
X
=
M1 133
+
1333 406
mf lomb Mg moles
Ib
+
mi methanol
Mi =
a
m6 64206
x
product
m
mi tool
=
Fig E5.12 Methanol synthesis with purge

ar isol
.
.
1
Solution product methanol The flow sheet shown Fig

in
1,000 gal
hr
is
BASIS
.
.
/
.
:
At
steady state the quantity impurities system

be
of
E5.12 the must

in
constant
.
the .
all
balance will give the quantity impurities which leave

an
of
Therefore over
in
,
purge From Example 5.10 M5

lb
206 moles
=
.
Over all balance for 206

C
=
-
m
6
:
1333x10 ???
::
0.333M1 M5 0.33M6
+
=
mor
for
all
impurities Because none the nonreactive impurities leave

of
Over balance
in
-
:
all
the methanol product impurities entering My leave

in
in
M
6
,
0.001M 0.01M6
Solving these equations gives = 687 and

M6
hr
M
hr
lb
moles 68.7 moles

lb
,
/
,
equal per cent

10
The purge
Vo
hr
of
the feed When there

cu
to
ft
93.5
is
=
.
.
the
purge more feed required produce 1,000 gal product because

of
to
of
is
is
a
the purge setting the purge rate economic considerations

In
of
loss reactants
in
,
.
would be necessary to balance the cost of reactants lost against the cost of larger
equipment .
DIFFERENTIAL MASS BALANCES
All the mass balances considered so far have been at steady state ; that
is , there was no variation of flow rates or compositions with time . In
unsteady - state processes , where conditions vary with time , it is often
necessary to write the mass balance as a differential equation . The
resulting equation is integrated , and the constants of integration are
evaluated from boundary conditions , such as data at time zero .
For simple unsteady -state processes , the mass balance may be devel
oped by considering the change in each mass term in a differential time
interval de .. Generally ,
Input output + accumulation (5.1 )
If mi is the mass flow rate into the system , me is the mass flow rate out ,
da
and MAА is the mass present in the
system , the total mass balance is Vapor flow
BB BB dV Ib moles / hr
mi do = m2 do + dMÀ ( 5.8 ) y mole fraction
more volatile
component
where dM АA is the change in the sys
tem mass in the time do . A compo
nent balance gives
Condenser
m 1X1 do = m 2x2 do + d ( M 4x A )
(5.9 )
where x1 , x2 , and xa are the mass Condensate

fractions for any one component . Vaporizer
Differential Distillation . One sim
L TbmolesTiquids Storage
ple exampleof an unsteady -state x mole fraction . tank
process is differential distillation . more volatile

Ecomponent
EV Ib moles
A two - component liquid is slowly
vaporized in a closed container ( Fig .
5.4 ) . The resulting vapor is con- Fig . 5.4 . Differential distillation .
densed and stored in another tank .
Because of the difference in relative volatilities , the vapor will have a
composition different from the liquid . The liquid will become depleted
in more volatile component as time passes .
Let L =
= total moles of liquid present at any time
V= moles of vapor distilled
x = mole fraction of more volatile component in the liquid
y = mole fraction of more volatile component in the vapor
There is no input after the initial filling of the stili pot ; so by Eq .
Vaporization after 10 hr is 20 lb moles . Therefore , Li 50 , L2 - 50 – 20 = 30 .

By Eq . (5.14 ) :
1 X2
-6.a
30
X 2
In =
50 2.52 1 [ ln ( @ ) -- 2.52 In
(1 0.4
)]
Solving gives remaining the stillpot
x2
the mole fraction benzene
in
= 0.285
.
Chemical Reactors The typical industrial chemical reactor con
is
a
.
tinuous flow process The reactants continuously enter one point and
at
,
-
the product mixture continuously withdrawn another point The
at
is
.
time the reactants spend the reactor and therefore the time permitted
is in
,
by
for
to
of
the reaction occur determined the size the reactor and the
,
The time
of
of
flow rate the reactants reaction and the reaction rate
.
determine the degree completion the reaction and the yield

of
of
of
desired
Of
product course the equilibrium represents limiting yield
a
,
.
.
hr
hr
m
lb
lb
,
ma
/
mass mass /
4,
2
*
fraction fraction
=
r
,
k
x
Fig 5.5 Stirred tank reactor

-
.
stirred tank reactor consists tank equipped with propeller

of
A
as a
-
keep the concentration uniform

to
which stirs the contents shown

in
,
5.5
differential
A
Fig The tank equipped with inlet and outlet lines

be is
.
mass balance may written for the following conditions

.
M
Original tank content lbm mass fraction reacting solute

0
,
X,
,
:
Input
m2 mı
hr
reacting solute
xi
lbm mass fraction

/ /
,
:
Output mass fraction reacting solute

hr
x2
lbm
,
:
Reaction rate the rate per pound

hr
of
lbm where
=
kzxn lbm
is
r
r
,
total phase present depends upon the order In the

of
the reaction
n
.
.
time interval do
Input mix1 do
=
Output
+
m2x2 do do
r
Accumulation Mx
=
d
(
)
The output consists of two terms , the first expressing physical flow out of
the tank and the second representing removal by chemical reaction . The
differential mass balance for the reacting species is
m 1X1 do = m 2x
2X ,2 de + d ( Mx ) + r M de (5.15 )
With thorough mixing the output composition is the same as that in the
tank , i.e. , X 2 = x . Then
m 1X1 do = max do + M dx + x dM + kqMx " do
At any time M = Mo + ( mi
0,
M - m2 ) 0 and dM = ( mi - m2
my ) do . Sub
stituting these expressions gives
m 1X1 do = m 2x do + [ M ,0 + ( mı –- m2 ) 0) dx + x (mı
mi – m2 ) do
de
+ kz [ M . + ((mi – m2 ) ]0. x "
which upon rearranging becomes

dx
+
M.
mix miX 1
) -k * (5.16 )
d + ( mi m2 ) 0 M. + (mi my
In reactor , the initial mass ( M. ) , flow rates ( m1 , M2 ) , and rate

a typical
constants (kz ,n ) would be specified . The equation could then be inte
grated . Suppose , for example , that there is no reaction ( k = 0 ) and that
the flow rate into the tank equals that out ( mı = m2 ) . The problem then
is simply one of unsteady - state mixing . Equation ( 5.16 ) becomes
dx mi m 1X1
+ X = ( 5.17 )
do Mo M.
Integration gives
X1 Xo
= mi
In 0 ( 5.18 )
X1 M.
0 =
=
with the limits x = xo at = 0 and x = x at 0 = 0. Another simple
solution occurs with a first -order reaction (n 1) , where also mi = m2 .
Then ,
In
m 1X1
-
Xo ( mı + kzM . ) = mi + k M. 0 ( 5.19 )
miX 1 -
x mı + k M.)
( Mo
Example 5.14 . A tank initially contains 1,000 lbm of an aqueous solution of 10 per
cent salt . How many pounds of water must be fed to the tank to reduce the salt
content to 1 1 per cent ? The contents of the tank are thoroughly mixed , and the mass
in the tank is maintained at 1,000 lbm by draining . The feed and drain are con
tinuous streams at constant rate .
Solution . M. 1,000 lb , Xo = 0.10 , mi ? , X1 0. By Eq . (5.18 ) ,
0 - 0.10 m10
In
0 – 0.01 1,000
m }
1 2
-18 ft
Reactants Reactor Product

L3 in. diam
10 cu ft /min NO
10 % NO NO2
78 % N2 N₂
12% O2 02
Fig . E5.15 . Pipeline reactor .
The cross - sectional area of reactor is
1-1 (
А
4
0.0491
i )'
2
sq ft
The velocity of flow is
Qay 10 cu ft / min
204 ft / min
A 0.0491 sq ft
The time of reaction is
reactor length 18 ft 60 sec

0 = 5.3 sec
V 204 ft /min 1min
It is now necessary to integrate the rate equation
dpΝΟ
23.2pkopo ,
do
To integrate , the variable po , must be expressed in terms of the variable pno . By

the reaction , every mole of NO reacting requires 14 mole of O2 , so that approximately *
2,1
12 ( pno.1 pro ) ( po por

)
where PNO and PO 2,1are the entering partial pressures

1,
Therefore pno
12
12
P02,1
+
Po PNo.1
=
,
= 0.10 atm po2,1 0.12 atm

PNO
1,
and
12
+
PO2 0.07 PNO

-
dpΝΟ
Then 23.2pno pno
12
+
0.07
?
(
do
Separating variables and placing limits

,
PNO -dpno 5.3 sec

2,
do
26
23.2
2
12
PNO
+
PÃO 0.07 PNO

,
Integration gives
12 12
1
1
1
0.07 PNo.2 0.1

+ +
(p
In 23.20
(
)
=
].
0.07 PNO PNO 0.07 0.07 PNo.1 pNo.2

2
2
1
,
)
(
)
.
Substituting known values gives

pixora
12 PNo.2 0.10
1
1
1
0.07
In
5.3
X
23.2
)
(
)
(
0.07 -0.10 -260

+
0.05 pNo.2
]]
PNO 0.07 0.07

(
2
[
2
Neglecting the change

of
total number
in
moles
*
.
This equation must be solved by trial and error .

TRIAL 1 : Assume that the term including the logarithm is negligible :
1 1
0.10
0.07 [. PNO , 2
23.2 X 5.3
]
PNO ,2 = 0.055 atm
negligible
to
Check see the term

if
is
–
0.07
1
0.055 0.10
2
/
In
)
(
)
39.9
=
0.07 0.12 0.055
2
(
)
(
)
the equation
of
TRIAL Subtract 39.9 from the left side
2
:
39.9
23.5
5.3
0.07 0.10
-
X
=
LPNO ]
.
Then pno 0.0475
.
: 2,
TRIAL
3
0.07 0.0475 0.10

1
/2
In
(
)
(
)
51
=
0.07 0.12 0.0475
)
2
)
(
)
1 (
0.10
+
51 23.2 5.3
X
=
0.07
[
PNO
]
2,
0.046
=
Then PNO
.
2
,
SO
gives Pn0,2 convergent value
of
Trial 0.046 The trials have shown PNo.2
=
4
;
is .
sufficiently accurate value PN0,2 0.046 atm

a
Then
12
ро 0.093 atm
+
0.07 0.046
,
0.10 0.046 0.054 atm

=
PNO PNO PNO

–2
,
1,
0.046 0.093 0.054 0.807 atm

–
PN
=
1
-
,
Composition
:
Volume per cent

NO 4.6
NO 5.4
,
9.3
N2 80.7
REACTION EQUILIBRIA
by
the equilibrium
an
The yield
of
reaction industrial
often limited
is
products Example To
as
of
concentration reactants and shown

in
5.16
,
higher yield than that equilibrium necessary

at
obtain
to
remove
it
is
a
the products from the reaction mixture many cases consecu

In
or of
some
.
tive simultaneous The equilibrium

of
reactions occur each reaction

.
may influence products and

of
the ultimate concentration the various

Example 5.17
as
reactants shown
in
,
by
Example 6.16 Ethyl alcohol produced from ethylene vapor hase hydration
is
.
-p
ethylene using catalyst The steam ethylene ratio 0.6 mole

of
mole C2H4
H
0
is
a
/
,
.
this temperature the equi

At
sq
The reactor operates

= at
and 1,000 lbs

in
570
F
/
°
.
for
librium constant Kp
=
atm the reaction H2O C2H5OH

+
0.0023 C2H4
-1
.
JS
Calculate the maximum yield of ethyl alcohol at equilibrium for a single pass through
the reactor .
Solution . BASIS : 1 lb mole C2H , feed .
Fig E5.16 is a schematic flow sheet .
Reactor
1 lb mole C2H4 na Ib mole C2H5OH
0.6 lb mole H20 ne lb mole C2H4
nw Ib mole H20
Fig . E5.16 . Catalytic reactor .
Let na = pound moles ethyl alcohol at equilibrium

пе = pound moles ethylene at equilibrium
nw = pound moles water at equilibrium
pa partial pressure of alcohol at equilibrium
Pe partial pressure of ethylene at equilibrium
Pw = partial pressure of water at equilibrium
Р = total pressure 1,000 / 14.7 68 atm
pa
KP 0.0023 atm - 1
Pepw
= na / En , so that pa
but pa / P = η Ρ / Ση . Then
nqP / En
0.0023 atm - 1
(neP / En ) (nvP / En )
η Ση
0.0023P
nenw
(0.0023 atm - 1) (68 atm )
0.156
At equilibrium the moles C2H , reacted will equal the moles C , H , OH produced :
na = 1 ne
or ne 1 na
For every mole of C2H5OH formed , 1 mole of H2O is consumed , and

-
nw = 0.6 na
Ση = na + ne + nw
= na + ( 1 – na ) + (0.6 – na )
1.6 na
These values are substituted into the equilibrium expression :

na En
0.156
nenu
(na ) ( 1.6 – na )
= 0.156
(1 na ) (0.6 na )
Solving gives na = 0.052 lb moles
no 0.948
nw = 0.548
Ση = 1.548
0.052
Percentage yield of C2H5OH
1
5.2 %
4.2
A similar industrial reactor ( which does not reach equilibrium ) gives a per cent
yield Obviously recycle unreacted ethylene necessary
of
is
a
,
.
.
Example 5.17 the reforming cyclohexane two simultaneous reactions may
In
of
,
.
occur
3
:
СH
H2
H2C С
?
CH2 HC CH
+
3H2
HC
!!
KP 106atm3
=
H2C CH at 950
CH
F
°
C
H
H2
Cyclohexane C6H12 Benzene C6H6
(
)
H2 CH3
С
CH
HC CH2
,
KP 12
=
CH H2C CH
h
at 950
F
°
H2C -CH2
H2
Cyclohexane C6H12 Methylcyclopentane MCP
(
)
per mole cyclohexane prevent
to
to
of
The feed the reactor contains

H
moles
4
thermal decomposition the cyclohexane Total pressure

41
of
atm Calculate the

is
.
as .
composition the equilibrium mixture

of
leaves the reactor

it
Solution moles H2
lb
mole C6H12
lb
BASIS
4
1
.
.
:
For the first reaction

:
PuPC6H6 106 atm

=
PC6H12
For the second reaction
:
PMCP
12
PC6H12
nap
with =
41
P
pa
Substituting atm
,
En
nu3
En
En
P3 nceHP
,
/
[
(
)
][
]
/
106 atm3
nC6H12P En
/
nů3
nC6H6 106 106

or
14.7
=
P3
41
2n
nC6H12
3
3
)
(
)
(
Similarly for the second reaction

:
En En
nmcpP
/
12
=
nC6H12P
/
All
be
terms will permit solution

in
to
expressed terms
of
ncqH12
n
NMCP
=
121C6H12
By the two simultaneous reactions

,
=
пMcP
1
nC6812 nC6H12
Combining equations gives
1 .
nC6H12 12nC6H12 NC6H6
1 -- nC6H6
nC6H12
13
Three moles of H , are formed per mole of benzene formed . There were 4 moles H , to
start with , so that
пн . =4 + 3ncello
Ση = nmcp + nColla + na , ' + ngoHo
In terms of C6H6 this becomes
12 1 nC6H6
Ση = (1 ncoH6) + +4 + 3ncoHo + ncoHo
13 13
= 5 + 3nceH6
These equivalents may be substituted into the original equilibrium relationship ,
3
ni ,nC6H6 14.7
nC6H12( En ) 3
(4 + 3nc.H. ) ' (nC6H6)
14.7
[( 1 nC6H6) / 13 ](5 + 3nC6H6) 3
Trial - and -error solution gives
Volume per cent

nC6H6 = 0.640 lb mole 9.25
Then
1 – 0.640
0.028 lb mole 0.40
nC6H12 13
12 ( 1 – 0.640 ) = 0.332 lb mole 4.80

NMCP =
13
nh2 4 + 3 (0.640 ) = 5.920 lb moles 85.55
Ση = 5 + 3 (0.640 ) 6.920 lb moles
At this pressure , 64 per cent of the cyclohexane is converted to benzene .
PROBLEMS
and
5.1
mixture containing mole per cent butane mole per cent pentane
20
35
A
,
,
.
by
mole per cent hexane separated

be
45
fractional distillation into

to
distillate
is
product with composition mole per cent butane mole per cent pentane and
95
4
a
mole per cent hexane and a bottoms product The distillate product must contain
1
a
,
the
per cent the butane charged Determine the composition

90
of
the feed
in
of
.
bottoms product
.
by
5.2
air
Pure oxygen produced liquefying and distilling low temperatures

at
is
it
.
separate the nitrogen and oxygen The two distillation columns used are shown
to
.
All
schematically Fig P5.2 compositions are mole per cent

in
the
air
Calculate the percentage the oxygen that

of
the feed
in
in
recovered
is
a
.
product oxygen stream

.
product oxygen
hr
of
of
Calculate the flow rate stream for 100

lb
moles
A
b
/
.
.
Nitrogen product
99 % N2,1 % O2
ol ma
1
Stream B
99 % N2 , Oxygen product
1% O2 0.5 % N2
99.5 % O2
Mi
1995
nitialni
N
21.995
niitma
21 air
Liquefied feed
lo
N2
O2
79
%
%
,
Stream
O2
60
N2,40
%
lao
Fig P5.2 Air distillation
21
.
5.3 Two distillation columns are arranged Fig P5.3 produce nearly
to
as
shown
in
.
All .
pure benzene toluene and xylenes from feed mixture compositions are mole
a
,
per cent
.
its
Determine the percentage recovery each feed component own product
of
in
a
.
stream
.
A.
Determine the composition

of
the intermediate stream

b
.
Benzene product Toluene product

1 99
toluene
% %%
96
%%
benzene
toluene benzene
1 3
xylenes
2
1
Feed
%%%
40 benzene
35 toluene
25 xylenes
Xylenes product
toluene
%%
9.5
A
90.5 xylenes
Fig P5.3 Benzene toluene ylene distillation

-
.
.
-x
liquid extraction system consisting mixer separator units

of
of
5.4 number
A
a is
a
-
.
separate acetic acid and water using isopropyl ether

to
as
being used
of
mixture
a
solvent The flow conditions are shown Fig P5.4 Calculate the complete com
in
.
position and quantity extract product assuming that equilibrium phase

an
of
is
it
,
.
Extract product Solvent

16 % acetic acid 99 % isopropyl ether
isopropyl ether 1% acetic acid
water
Feed, 1,500 lb/ hr

40 % acetic acid
1 2
A 3 4
Raffinate product
3 % acetic acid
60 % water 2 % isopropyl ether
95 % water
Fig . P5.4 . Countercurrent liquid - liquid extraction .
In
oil
5.5 . A crude repetitive process extracts from soy beans this process the
.
fresh solvent which
of
crushed beans are stirred with successive batches then
is
After solvent removal the pulp retains per cent
20
removed and stored
oil
of
the
oil it
.
held before solvent addition plus entrained quantity an
of
solvent and dissolved
The original beans
oil
weighing four times the pulp plus unextracted
as
as
much
.
oil
per cent solvent weighs the original beans

20
as
as
of
contain and each batch much
,
.
to to
Develop computer program and calculational flow sheet determine the fraction
a
oil
of
unrecovered after three successive extractions and determine the concen
,
in A of
tration oil the collected solvent

in
liquid absorbent hydrogen stream
As
to
5.6 used remove H2S from

is
a
.
.
Fig P5.6 two columns are used
In
shown the first column absorber the liquid

,
),
(
.
the
the second column stripper
In
contacts the gas and absorbs most

of
the H2S
),
(
.
solution heated and the H2S removed The absorbent then reused
is
is
is
.
.
H2S gas leaving the stripper
of of
Calculate the flow rate

a
.
of .
Calculate the flow rate absorbent entering the top the stripper
b
.
.
Purified gas Pure H2S Hg
770 mm Hg
90
70
F
,
760 mm
°
F
°
,
H2
100
%
negligible
H
S
,
(
Absorber
Stripper
Feed gas
cu
1,000 min -Regenerated absorbent

ft
/
90
780 mm Hg 100 min pure liquid

lb
F
°
% ,
/
99
H2,1 absorbent negligible H2S

%
H2S
(
Fig P5.6 H2S absorption system

.
.
the
the
the
5.7
4.8
Example vapor phase

all
of
What fraction mixture

in
in
over
if
is
-
.
2p
composition
26
0.195
ze
of
the mixture 0.39 0.415

?
is
,
,
5.8
Determine the quantity each phase present

of
moles the mixture

lb
in
of
in
100
.
all
Prob 4.29 the over composition Zoctane 0.82

if
is
.
,
-
.
liquid 0.72
26
of of
Calculate the fraction the mixture Prob 4.34 which

.
in
to =-
5.9
if
is
a
,
.
a .
5.10 For the gas mixture Prob 4.30 write calculational flow chart give
.
.
the temperature at which 80 per cent , 60 per cent , 40 per cent , and 20 per cent of the
feed stream will be liquid at 1 atm total pressure . The program should also give the
composition of the two equilibrium phases at each of these points .
6.11 . A liquid mixture of 50 lbm benzene and 50 lbm toluene is heated in a closed
container to a temperature of 210 °F at a total pressure of 1 atm . The vapor formed
is withdrawn and compressed to 1.2 atm at 210 °F , so that part of it condenses . What
percentage of the benzene in the initial liquid is present in the compressed vapor ?
5.12 . Butane is to be removed from an ethane stream by compressing and cooling
the gas . The initial gas contains 20 per cent butane and 80 per cent ethane at 70 ° F
and 1 atm . The gas is first compressed to 10 atm at 100 °F . The mixture is then
cooled to 32 ° F at 10 atm .
a . Calculate the percentage of butane condensed on compression .
b. Calculate the percentage of butane condensed after cooling .
C. Calculate the percentage of ethane condensed after cooling .
5.13 . Hydrogen gas contains 1 per cent ethane at 50 atm pressure .
a . To what temperature must the gas be cooled to give a gas composition of 0.1
per cent ethane ?
b. How much ethane is condensed per pound mole of original gas mixture ?
5.14 . Acetic acid is to be extracted from a 35 per cent ( by weight ) aqueous solution ,
using pure isopropyl ether . How much isopropyl ether must be used to ensure a 90
per cent removal of the acetic acid from the aqueous phase ?
6.16 . 100 lbm of a solution containing 20 per cent acetic acid , 80 per cent water is
mixed with 50 lbm of a solution of 97 per cent isopropyl ether , 3 per cent acetic acid .
What percentage of the acetic acid originally in the aqueous phase is extracted into the
final ether phase ?
5.16 . Determine the quantity of each phase per 250 lbm of the mixture in Prob . 4.56 .
5.17 . Determine the quantity of each phase present for 100 lbm of the mixture in
Prob . 4.60 .
/
6.18 . 100 lbmт hr of a 30 per cent MgSO4 solution in water at 120 °F is cooled to 40 °F .
2 lbm / hr of MgSO4.7H20 seed crystals is added to the solution to initiate crystalliza
tion . The resulting crystals are filtered off the remaining solution .
a . What is the net hourly production of crystals ?
b. What percentage of the original dissolved MgSO , is recovered as crystals ?
5.19 . It is desired to produce a maximum quantity of MgSO4 :61,0 crystals from a
15 per cent solution of MgSO4 in water . How might this be done ? For your process ,
calculate the mass of crystals produced from 1,000 lbm of original solution .
5.20 . A brine solution contains 20 per cent sodium chloride , 80 per cent water . It
is desired to recover 95 per cent of the salt as crystals from the brine by evaporating
the solution . What percentage of the water in the original solution must be evapo
rated to ensure the desired recovery of NaCl ?
6.21 . An aqueous solution of KClO3 at 100 ° C contains 33 per cent KCIO3 . Specify
a process which will recover 80 per cent of the KCIO3 as crystals .
5.22 . Nitrogen is used to vaporize the solvent benzene in a drier . The incoming
nitrogen at 120 °F and 1 atm is to have a benzene concentration of 5 per cent (by
volume ) . The nitrogen leaving the drier at 100 °F and 1 atm has aa benzene dew point
of 90 °F . The drier must remove 100 lbm /hr of benzene from the material being dried .
The exit nitrogen is cooled to condense out the benzene , heated back to 120 °F , and
returned as the nitrogen entering the drier .
a . What is the volumetric flow rate of gas entering the drier ?
b. To what temperature must the exit gas be cooled to condense out the benzene ,
so that the nitrogen may be recirculated ?
c. How much benzene is condensed out on cooling of the exit gases ?
5.23 . Raw ammonia synthesis gas may analyze 60 mole % H2 , 20 mole % N2 , 16

mole % CO2 and 4 mole % CO , CH4 , and A. The CO2 must be removed from this
the
stream before it enters the ammonia converters . This may be done by absorbing
by
250 psig and
80
at
CO2 into water The absorbed gases are removed reducing
.F
°
atmospheric after which the water recycled
to
the pressure the countercurrent
to
is
,
absorption tower The water stream leaving the absorption tower equilibrium
in
is
.
with the raw synthesis gas and the water stream leaving the pressure reduction cham
,
ber equilibrium with the off gases that are released
in
is
.
the composition the water leaving the absorption tower
of of
What
is is is
a
?
.
What the composition the water leaving the desorption chamber

b
?
.
the atmosphere
to
the gases vented
of
What the concentration
. c
?
.
For raw synthesis gas stream
is cu
4,000 standard min what recycle rate
of
ft
is
d
/
required for the water absorbent Assume all the CO2 absorbed
, ?
.
What fraction the atmosphere
of
to
the inlet vented
H
is
e
?
.
methane saturated with water vapor

cu
at
1,000
of
min atm and 120

ft
5.24
is
F
1
/
°
.
that part the water vapor

50
to
so
of
cooled condensed The methane then
is
is
F,
°
.
to
at
reheated 75 atm
F
1
°
What the volumetric flow rate the exit methane of

is
a
?
.
How much water condensed

is
b
?
.
by
per cent humidity
95
5.26 Warm summer air 105 conditioned passing
is
F,
°
(
)
.
the air through
up
cold water spray The air cooled the water spray
to in
as
picks
is
a
it
-
moisture The air leaves saturated and reheated 70
F
is
°
.
.
air
F At
what temperature must the leave the water spray
air
the conditioned
if
a
.
per cent humidity

70
50
at
to
have
is
a
°
evaporated the spray chamber

or
How much water condensed

in
6.
is
?
heat sensitive organic material dried using nitrogen vacuum drier
in
5.26
A
is
a
,
-
.
.
pressure with
200 mm Hg The nitrogen enters
80
at
at
The drier operates
of
a
F,
°
.
dew point dew point

35
75
65
at
of
at of
with How much water

It
leaves
F
.F
is a
a
F,
°
°
.
the entering gas flow rate 200 mm Hg and
80
cu
removed min
ft
100
if
is
F
/
?
°
(
)
per
spray dried from slurry containing
40
be
Chromic oxide cent Cr20

to
5.27
is
a
-
to :
.
by
weight product containing per cent H20 production rate equivalent

hr to
A
2
of a
air
2,000 lbm anhydrous Cr203 desired The drying medium which enters
is
is
/
relative humidity per cent

air
20
at
atm pressure with

of
the drier 100 The

1
a
F,
,
to °
then heated steam heater before entering the drying chamber

in
260 The
F
is
a
°
slurry being sprayed preheated

to
107
.F
is
the minimum entering air rate

cu
What
in
min
/ft
is
a
?
.
the
are
? 1.5
air
At
times this minimum rate what the temperature and dew point
of
b
.
exiting air
on
military equipment performance the test room

In
5.28 environmental studies

be .
by
kept with wet bulb temperature planned

75
do
to
at
to
of
It
130 this
F
is
is
F
a
°
°
-
.
air
air
compressing room cooling the compressed separating out the con

to
130
,
F,
°
the
cir
water and reducing pressure isothermally one atmosphere before

to
densed
,
culating the air through the test room

.
compressed
at be
To what pressure must the air

a
?
.
air
per cent relative humidity how many

70
the compressor
to
inlet 110
If
is
,
F,
b
°
.
air
pounds per 1,000

of
of
water are condensed cubic feet inlet

?
air
5.29 Air with mole dry originally

of
moisture content mole H2O

lb
lb
0.02
is
of a
/
.
temperature and total pressure This air cooled

of
atm
at
at
120 constant
is
F
1
a
a
to .
and then compressed isothermally 100 psia What

of
pressure
80
the ratio
to
is
F
.
°
initial volume
to
final
?
percentage humidity
at 10
5.30 Air originally cooled adiabatically

%
at
and
is
110
F
°
.
by
contacting the wet bulb temperature the gas

of
with water which

it
is
.
a. What is the lowest temperature to which the air may be cooled ?

6. How much water is vaporized per pound of dry air in reaching the temperature
determined in part a ?
is gel
gel
5.31 . Air is dried by contacting it with a silica adsorbent The silica can
to .
.gel
gel
adsorb 0.05 lbm H2O per pound How much required reduce the humidity
air
percentage humidity
72
90
10
cu
at
to
100,000
of
of
%
from
-c ft
%
F
?
°
air
onditioning unit refrigerates air originally dry bulb and
95
90
at
An
F
5.32
F
°
°
.
wet bulb
at to
condense out water vapor give the desired
to
The air then reheated
is
.
percentage humidity
70
50
room air and %
F
°
.
To what temperature must the air
be
cooled
a
?
.
How much water vapor
cu
removed from 100,000
of
air
ft
is
b
?
.
by
air
air
conditioner operates cooling part and passing this
is of
5.33 An the inlet
.
part through
all
constant tempera
an
at
adsorber bed which the water removed
in
ture The dried air
an
to
get
of
then mixed with the rest the inlet air outlet air
is
.
per cent relative humidity

70
50
of
stream
F,
°
air
computer program
be
to
to
of
Write determine the fraction the cooled and
a
a
.
dried and the dry air outlet temperature for any inlet condition Assume that inlet
.
air temperature and humidity are known
.
Computers are available that could give con

to be
to
to
direct connected this unit
b
-
.
Be
tinuous automatic control prepared discuss class the connections between in

,
instrument and computer that would necessary

be
do
to
this
.
an
unconventional sulfur mining operation the crude

In
dissolved CS
in
5.34
is
S
,
.
while the inerts are insoluble and collect on the tank bottom The CS with its dis
,
.
solved then evaporated the crystallizing out the evaporator

in
is
S
S
;
.
wt
Vapor from the dissolving tank contains flows through

20
CS air
in
It
a
,
sec linear velocity and 110

12
10
compressed 10
at
diam duct After

in
to it
ft
is
F
/
°
-
it .
.
its
temperature drops
50
a to
atm goes cooler condenser where The cooled

.F
- a
°
-
gas leaves diam duct

in
in
How much liquid CS2

hr
How much gaseous CS lost from the condenser

is in
lbm
is
?
,
the velocity
hr
recovered from the condenser What the outlet duct

in
in
is
lbm
/
?
?
An adiabatic humidification chamber brings atmospheric pressure
at
5.35 air
in
.
,
by
dew point spraying water into the

95
This air
of
180 with humidified

F
is
a
F,
°
°
.
per cent relative humidity

70
at
chamber 108 until reaches

.F
it
°
What the outlet air temperature

is
a
?
.
evaporated per 1,000

4 cu
of
How much water inlet air

ft
is
b
?
.
wt
atm total pressure contains

30
at
is of
at %
6.36 mixture air and benzene C6H6

A
)
.
benzene This gas and then expanded atmospheric pressure

to
cooled 100
to
F
°
.
constant temperature
.
How much benzene condensed and separated after cooling but before expansion
is
a
?
.
the dew point temperature atm gas

of
What the final 100

is
1
b
?
F,
°
.
for
hydrochloric acid H2SO4 and NaCl

In
the salt process

of
5.37 the manufacture

,
.
off
are heated together furnace The resultant HCl gas driven the reaction
in
it is
a
by
mixture cooled purified and passed

an
to
to
absorber where absorbed water

is
,
,
hy
produce weight HCl solution To produce per

32
32
per cent
of
water ton
in
1
(
lb )
of .
cent hydrochloric acid 1,050 100 per cent sulfuric acid are
of
salt and 945 lbm

,
,
all
charged completion and the HCl formed goes

to
is to
the furnace The reaction goes

,
.
HCl
of
the absorption tower where most small amount

to
is
A
of
absorbed
it
,
the waste gases leaving the absorption tower The solid products the reac
in
of
lost
.
tion are withdrawn from the furnace and sold

as
salt cake
.
its
percentage excess
of
Which the reactants What

in
excess
is
is
. a
?
.
What percentage the HCl produced the waste gas

of
the furnace lost

in
in
is
b
Determine the mass and composition salt cake produced per ton
of
of
acid
c
.
.
5.38 . In acetylene manufacture from CaC , the main raw material is limestone con
taining 95 per cent CaCO3 , 5 per cent inerts . This is “ burned ” in a kiln (CaCO3 →
CaO + CO2 ), and then the solid products are reacted in an electric arc with dry pow
dered coke ( 100 per cent C ) to give CaC . (CaO + 3C → CaC2 + CO ) . The kiln reac
tion goes to completion , but the carbide - forming reaction goes only 95 per cent to
completion when 10 per cent excess CaO is fed to the furnace .
The CaC2 - containing solid product from this furnace is then reacted with water
( CaC2 + H2O → CaO + C2H2 ) to give acetylene . This reaction goes to completion
when a 1 : 1.2 mole ratio of reactants is used .
/
a . For a 50 ton day production of pure C , H , how much limestone must be mined ?
b. What is the volume of CO formed (cu ft min ) at 735 mm Hg total pressure and/
70 ° F ?
c. The C , H , is evolved saturated with water vapor at 100 °F and 735 mm Hg total
its
pressure . What is concentration mole per cent
in
to ?
25
of
The C2H dried and then absorbed concentration
in
%
acetone mole
is
d
a
,
.
.
the vapor pressure For acetylene the critical point
70
of
What this solution
at
° is
F
?
20 °
61.6 atm and the vapor pressure
10
at
36.5 atm
–
C
C
is
is
,
°
.
The gas from sulfur burner sulfuric acid plant has the following compo
in
5.39
a
a
: .
sition
Per cent
by
volume
(
SO2 6.50 )
SO3 2.78
02 10.65
N2 80.07
What was the percentage completion
to
of
of
the oxidation sulfur SOz

a
?
.
What was the percentage excess oxygen supplied over that required for complete
b
.
combustion
?
all
passed through
so
the SO2
of
that
to
The gas series converters oxidized is
is
a
c
.
Calculate composition the gas leaving the converters

of
SO3
.
and 740 mm Hg
by at
The gas leaves the converters 150 Calculate the volume

F
d
°
.
gas leaving the converters per ton pure sulfur burned

of
of
5.40 Aluminum sulfate made reacting crushed bauxite ore with 77.7 per cent
is
.
55
sulfuric acid The bauxite ore contains per cent Al2O3 the remainder impurities
,
.
.
produce
to
bauxite and 1,140 lbm

of
of
sulfuric acid are used ton

of
670 lbm crude

1
aluminum sulfate which contains 84.3 per cent Al2 SO4 3.9H20
,
Determine the percentage

of
the reactant
in
excess
a
.
to .
What percentage
of
each reactant was converted

3
Al2 SO4 3.9H

0
b
?
,
(
)
.
by
5.41 Nitrobenzene produced nitrating benzene using mixed acid The

is
a
,
.
reaction
is
19 63
mixed acid
H2O
+
HNO3 C6H5NO2
+
C6H6
14
Benzene
§
12. Nitrobenzene
lbm
per cent complete

97
to
1,000
of
of
The conversion benzene nitrobenzene

is
per cent HNO3

39
benzene and 2,070 lbm mixed acid are used The mixed acid
of
is
,
.
53
per cent H2SO4 and per cent

H
0
8
,
,
.
How much excess HNO3 used

is
a
?
.
How much pure nitrobenzene produced

is
b
?
.
by
hy
reacting chlorobenzene with sodium

be
5.42 Phenol can manufactured

.
droxide
:
C6H5C1 NaOH C6H5OH NaCl

+
Chlorobenzene Phenol
To produce 1,000 lbm of phenol , 1,200 lbm of NaOH and 1,320 lbm of chlorobenzene
are used .
a. Calculate the percentage excess of the excess reactant .
b. Calculate the percentage yield of phenol .
5.43. Chlorobenzene is manufactured by reacting dry chlorine with liquid benzene ,
using a ferric chloride catalyst . Both mono- and dichlorobenzene are formed by two
reactions :
C6H6 + Cl2 → C6H3Cl + HCI
C6H3Cl + Cl2 C6H4Cl2 + HCI
per
per cent
15
the mono
of
of
90 cent the benzene forms monochlorobenzene and
,
supplied
to
per
20
chlorobenzene reacts further form dichlorobenzene Chlorine
is
.
that required for complete monochlorination The HCl and excess
of
in
cent excess
.
leave the reactor The liquid product contains unreacted benzene and
Cl
as
gases
,
mono- and dichlorobenzene For 100 lbm benzene reacting calculate of
,
.
The mass and composition the liquid product

of of
a
.
.
The mass and composition the gas leaving the reactor
b
.
.
by
5.44 Formaldehyde the catalytic oxidation methanol using
of
manufactured
is
.
an
of
excess air
:
CH3OH CHO
12
02
→
+
H2O
+
Methanol Formaldehyde
secondary oxidation occurs conditions are not properly controlled

if
A
:
CHO +12 02 HCOOH
-
Formaldehyde Formic acid
The product gases test run have the following composition

in
a
Per cent
by
volume
(
CH3OH 8.6 p
}
CHO 3.1
HCOOH 0.6
H2O 3.7
F
02 16.0
N2 68.0
Determine
The percentage conversion formaldehyde 3Y
to
of
methanol
a
.
The percentage the secondary reaction 6/1

of of
methanol lost
in
C. b
.
.
83 to
The molar ratio feed air feed methanol

.
by
per cent CH4 and per cent C2H6

17
5.46 natural gas contains volume

A
.
.
air
an
The gas dry and yields the following combustion gas

of
burned with excess

is
Before analysis the combustion gas was dried

,
(
)
.
Per cent
by
volume
(
CO2 6.76
CO 2.77
+2.7
02
N2
5.63
84.84
32
5,63
I't
2
Calculate
15.16
The percentage excess air supplied
a
.
requel
.
Iz
The percentage completion

of
of
oxidation carbon
2.77+
b
.
.
=
c. The mass of water vapor per 1,000 cu ft of wet combustion gas at 800 °F and
1 atm .
A coal with the following analysis is burned with a 30 per cent excess of
air
5.46 .
:
Per cent
by
weight
)
Carbon 70
Available hydrogen
va 5
Moisture
7
Nitrogen
15 2 1
Sulfur
Ash
of
The ash does not burn Part the carbon also does not burn discarded with
It
is
.
.
per cent
15
In
Assuming
of
the ash this case the carbon the coal does not burn
in
,
.
.
that the remaining carbon forms CO2 the available hydrogen forms H20 the moisture
,
,
vaporizes the nitrogen forms N2 and the sulfur forms SO2
,
,
.
on
Calculate the composition the gas formed the coal
of of
of
combustion
. a
.
.
Calculate the composition the unburned residue
b
the
The first step sulfuric acid manufacture from pyrites consists burning
of
in
5.47
.
pyrites air
In
this combustion the reactions

in
Jooz
Son
.
Ain't
7-8
or
52
+
FeS2 02 FeO + 2802

→
1
(
)
82
02
4802 N2
+
2FeS2
+
112 Fe2O3
2
(
)
both take place
.
O2
From one such burner the flue gases analyze 10.2 mole SO2 7.8 mole %
%
and
,
on
dry basis and 780 mm Hg total pressure

%
at
82.0 mole
N
600
C
a
,
.
In
do
what ratio reactions and take place

a
to 1
?
.
(
)
(
)
F all
How much excess air fed the burner the pyrites fed burned
if
is
is
b
?
.
air
and 735 mm Hg total pressure

of to
at
The fed the burner saturated 100

is
c
°
.
.
How many moles water vapor are the flue gas per mole dry flue gas
of
in
?
flue gas are generated per ton pyrites fed
to
How many
of
the burner
cu
of
ft
if
d
.
wt
the pyrites contains inerts with the FeS2 analyzes

42
so
that
it
S
?
5.48 fuel oil analyzes

A
.
Per cent
by
weight
(
Carbon 84
Hydrogen
13
combustible
(
Sulfur 1.0
Oxygen 1.0
Water 1.0
The combustion products analyze

:
Per cent
Ni Dailis
by
19
xial
volume
14
vo
(
oslo
2
CO2
Airina
9
.
CO 1.6
179
1
84
H2O 10.8
(
0.05 19.67
2
SO2
O2 3.7 t.138
?
N2 74.0
.
19.8
etwa coi
13
h
C
8
?
9.5
=
19.67
THE MASS BALANCE Et
)
1015x13.8-136-1.374%
213
57
for
air
a . Calculate the percentage of excess supplied over that required complete
combustion
of
the fuel oil
.
What
to
of
the mass ratio air fuel oil
is
?
b
.
Air
be
Air
to
so .) at
5.49 dehumidified for industrial use with
is silica gel adsorber
a
.
.
per cent humidity per cent humidity
75
95
25
F; 75
be
and
to
to to
reduced
at
F
F
is
at (
°
°
gel
air
passed through per cent humidity
75
The silica reduces the
it
°
part bypassed around the adsorber and mixed with the air leaving
of
the feed air is

give the required final air
to
of
the adsorber What fraction the feed air
is
.
bypassed
?
In
Example 5.10 what would the required recycle ratio moles recycle
be
5.50
,
/
.
the reactor conversion efficiency drops per cent
10
to
moles fresh feed
if
in ?
,
by
contacting absorp
be
an
5.51 Air can dried with concentrated sulfuric acid
in it
.
tion tower The arrangement shown Fig P5.51 used
is
.
.
.
ma
acid
%
93
air
Dry
acid
%
99
99
go
Max .925420
=
x
addition
98
g8
acid
%
92.5
removal
MI
m2
° Air
cu
mit lolt
500 min
ft
18x.99
)
,
70 atm
F.
1
98
acid
%
92.5
saturated with H20
M3
1.07
1923
+
4
6292 Fig P5.51 Air drying with

3
H2SO4
)M
8
x
98
+
.
%
=
119.7
0247
,
per cent sulfuric acid the top flows down through the
93
to
of
the tower
It
fed
is
.
air
tower removing water vapor from the This additional water dilutes the acid
,
,
.
92.5 per cent H2SO4 this weaker acid were recirculated directly
at
which leaves
If
,
.
to
would continue H2SO4 concentration and increase total mass

in
in
decrease
it
).
air
efficiently remove water vapor from

at as
to of so
Dilute acid does not the concentration

;
must be maintained per cent

93
Therefore small amount 92.5 per cent acid

a
,
is .
per cent acid return the strength per cent

99
93
to
removed and added

is
.
99 on
Using the data the flow sheet calculate

,
The mass per cent acid added per hour

of
a
.
The recycle rate per cent acid entering the tower

93
of
b
.
by
5.52 The fissionable isotope separated from U238 gaseous

of
uranium U235
is
of ,
,
.
units consisting stages three tage unit

of
thousands shown
in
in
diffusion
A
is
.
-s
Fig P.5.52 Half the gas entering stage diffuses through porous metallic barrier
a
a
.
.
gas
recycled the previous stage

to
of
of
The other half the the feed Calculate the

is
for
as
as
the feed appearing rich product and lean product

) of
fraction the unit

a
(
)
shown for unit with five stages

a
b
,
(
.
gas
by
air
5.63 producer plant operates alternately passing and steam through

A
.
by
air
flow period the coal burns

In
coal the the reactions

of
bed
a
02 CO2
+
C
1
(
)
+12 02 CO
→
C
2
(
)
Recycle 2–1
Feed 11 3
U235 - rich
product
Recycle 3-2
-
U235 lean
product
Fig . P5.52 . Three - stage gaseous diffusion system .
and heats . In the steam flow period the coal reacts as follows
C + H2O + CO + H2 (3)
C + 2H2O + CO2 + 2H2 (4)
the
and cools . The gases from the air flow period are vented to atmosphere , while
gases from the steam flow period are collected gas holder
20 in
a
.
wt
wt
80
of
%
Consider that the coal consists ash and that the total volume
C
,
,
air
standard conditions fed during the flow period equals the total volume air
at at
of
of
steam standard conditions fed during the steam flow period
.
Of
per cent During the air flow period

90
the coal fed consumed the reactions

in
as is
,
.
During the steam flow
as as
reaction converts twice much does reaction

C
1
2
(
)
(
).
02
period reaction All the
as
converts four times much does reaction
C
3
4
(
)
(
).
the air fed reacts but only
85
per cent
of
the steam fed reacts

in
.
producer gas collected H2O gage pressure and
80
at
of
Determine the volume

in
F
6
°
.
per ton coal fed and the volumetric analysis this gas
In of
of
,
the synthesis N2 stream contacted with

is
of
a
NH3 mole ratio
H
5.54
3
1
a
,
:
.
promoted iron oxide catalyst 15,000 psi and 1000 The usually obtained
at
H
of .F
is
,
°
by
of by
byoil
partial oxidation
to
of
fuel followed conversion CO and steam CO and
..
H
,
by
air
O2
The usually obtained removal from this same partial oxidation

N
is
,
.
of As
result the feed gas contains argon from the air and CH4 from reduction
of
traces
a
H2
N2
typical feed analysis

as
as
CO well
and 73.2 mole
H
%
24.4 mole
A
is
,
,
.
argon
%
2.1 mole
CH4 and 0.3 mole
%
N2
,
The reaction system Fig P5.54 Sixty five per cent

of
the N2 mix
H
shown
to in
is is
,
:
-
.
per cent the NH formed liquefies

70
entering the converter

of
reacted NH3 and

,
,
gas
the purge gas contains

20
the cooler per cent CH what the total purge

in
If
is
,
.
all
analysis and what percentage yield liquid NH3

of
the over
is
?
,
Recycle
compressor
Cooler
165 condenser
12.3
roovon Purge
ECatalyst
H2 1312 Liquid
afilih NH3
il
Feed
clie Converter
Fig P5.54 Reactor for ammonia synthesis

11
.
5.56. Ethylene is catalytically hydrated to ethyl alcohol , but the reaction does not
go to completion in a single pass through the reactor . Therefore , much of the eth
ylene must be recycled , as shown in Fig . P5.55 . After the reactor , the water and
alcohol are condensed out , and the unreacted ethylene is recycled . The molar ratio
of water to ethylene entering the reactor must be 0.6 . The conversion of ethylene per
pass is 4.2 per cent .
a. Calculate the recycle ratio (moles ethylene recycle per mole fresh feed ) required
all
to give an over - 100 per cent
of
conversion
.
Calculate the composition
of of
the fresh feed
b
.
.
Calculate the composition the alcohol water product Hut H2o
Ca
c
-
.
Ca
malas
Barsi GOH
H
Pure ethylene recycle
4
Toox.042 m22
!VA
.6
o
cannat
of
-66
H2O
m2
412 M4
mac
=
Reactor Condenser
ч
(
Feed
loor
H20
114
;
Go
ethylene
Cart M2
+
- =
.. M
1042 m3
m'4
60
=
Ethyl alcohol
=
+
H2O
6
.Fig
15.8
P5.55 Ethylene hydration mut lca
.
=
3
4,2
Calculate mys
5.56
95
Air
to
leaving
drier frequently recirculated minimize costs
.
is
.
a
.
Fig P5.56 Calculate also the mass rate

as
of
the fraction air recirculated shown

in
fresh air supplied

of
mo .ji 5300
%
of
Basis Recycle air

?
13
m
.
'
Moist air
dry
air
5,000
1
hr
basis
lb lb
/
1b (
)
air
dry Fresh air

dry 1
0.048 H20
/
1b
air
0.012
lb
H2O
/
Drier
xiou
Entering wet polymer Leaving dry polymer
n'exis
+
hr
100
lb lb
16
0.25
lb
H20
/
dry
/
1b
1.30 H20 polymer dry polymer

Too
/
20
í
Fig P5.56 Countercurrent drier

.
the water thylene feed Prob 5.55 contains 0.05 mole per cent nonreac
in
If
5.67
.
.
-e
the recycle which must purged

be
to
tive gases calculate the fraction keep the inerts

of
,
entering the reactor below per cent Other conditions are the same
of
concentration
1
a
.
as
those stated
in
Prob 5.55
.
5.58 Calculate the purge rate Example the impurities the feed gas
in
in
5.12
if
.
to
increase 0.2 per cent

.
For the conditions Example 5.13 plot the composition

of
of
5.59 the accumulated

,
.
up
condensed vapor What percentage recovery

12 25
hr hr
as
of
of
function time the

to
a
condensed vapor What percentage

as
of
benzene attained after the benzene

is
of ?
originally charged can

80
be
recovered solution mole per cent benzene

in
a
?
5.60 . An open tank initially contains an equimolar mixture of n-hexane and
the
air
n -octane . The tank is open to the and the liquid slowly evaporates
If
,
.
liquid and air are determine the composition the remaining liquid after
70
at
of
F,
°
mole per cent the original liquid has evaporated Assume that the moving
air
25
of
.
carries away the vapor formed
.
5.61 Work Prob 5.60 starting with equimolar mixture ethyl alcohol and
an
of
,
.
.
evaporation continues what would the composition
be
the last drop
of
water
If
,
.
remaining
?
mass per cent solution
20
tank contains 1,000 gal
of
of
5.62 sodium chloride
A
a
.
.
10
at
at
gal min and solution
of
Water added rate withdrawn the same volu
is
is
a
/
,
salt remaining after Assume thorough
30
of
metric rate Determine the mass min
.
.
mixing the tank
A in
porous solid being dried
an
rate approximately
at
oven
in
dries
It
6.63
is
a
.
.
its
proportional half the solvent evaporates

it to
moisture content the first hour
in
If
,
.
how long will per cent per cent
90
99
to
of
take remove the moisture
6
a
?
of ,
(
)
(
)
large meeting room has meeting the
cu
volume 20,000 Before
ft
6.64
A
a
.
.
CO2 concentration air 0.04 per cent One half hour after the meeting room
in
is
is
-
.
ventilated by 10,000
occupied the CO2 concentration 0.12 per cent The room
is
is
,
in be
What will
cu
fresh air 0.04 per cent CO2 the CO2 concentration after
of
min
hr ft
/
).
to
What must be the ventilation rate fresh air order maintain the con of
6
0.08 per cent CO2

at
centration
in
the room
?
5.2 years How long would

60
pound
its of
5.65 Cobalt has half life take for
it
a
a
of *
-
.
per cent
60
25
to
25 of
cobalt lose cobalt How much cobalt would remain after

?
years
?
of Is 235
5.66 The United States stockpiling the nuclear eapon fuel uranium
is
.
.
-w
Uranium 235 decays radioactively and has half life 7.13 108 years of
X
a
.
there any serious danger the stockpile decaying away For every 1,000
be of
lb
?
up
by
U235 stockpiled what must the annual production
to
make for losses decay
is ?
,
treat thyroid disorders

to
5.67 Radioactive iodine 131 used The isotope

is
.
nuclear reactor and shipped the hospital

131to
8.06 days
of
made half life
in
It
has
a
-
.
.
an
on
hospital receives shipment

of
solution which arrival contains micro

A
1
of a
gram 10-6 gram 1131. They use the solution

at
0.1 microgram
of
the rate week

/
(
.
For how many weeks will the original shipment last
?
shampoo solution which had been sold without perfume

be
to
5.68 changed
A
is
.
per cent perfume 20,000 gal holding tank originally

an
to
of
include addition
A
1
per
filled with unperfumed shampoo fed continuously with shampoo containing

is
cent perfume starting 9:00 A.M. while product from the tank
at
withdrawn continu
is
,
ously the filling machines Feed and product rates are each gal min
20
to
The
/
so .
tank may well agitated that the concentration

be
be
to
assumed uniform through

is
Develop computer program calculate the composition shampoo being

to
of
out
a
.
the filling machines hourly periods extending until the perfume concen
to
at
sent
tration reaches 0.98 per cent
.
air
storage vessel contains liquid atmospheric pressure

50
at
of
5.69 liters Heat

A
.
per
flow through the vessel walls rapid enough liquid vaporizes

so
O2 of
that one liter

is
Under these conditions the relative volatility may

be
to
as
of
hour taken
N
con
,
.
the
computer program give the concentration

at
to
liquid
of
stant Write
in
2.07
O
a
,
.
The density liquid air

cu
as
of
of
function time
ft
54.6 lbm
is
a
/
.
5.70 first order reversible reaction

A
-
.
=
B
A
half
for
the time required

as
of
The half life radioactive element defined one

is
a
*
to -
-
by
decay away
of
the mass first order reaction

a
.
gives a rate equation of the form
- dca
kica – k2CB
do
where k2 is the rate constant for the reverse reaction . Develop a calculational flow
chart for the computation of ca as a function of time where ki , k , and the initial values
of ca and CB are known .
5.71 . A tank with a 5,000 lbm capacity initially contains 2,000 lbm of water . A
50 per cent ( by weight ) solution of ethyl alcohol and water is added at the rate of
500 lbm / hr , and the mixed solution is withdrawn from the tank at 250 lbm / hr . What
is the composition of liquid in the tank just as it becomes full ? Assume thorough
mixing in the tank .
5.72 . A chemical compound A reacts simultaneously by two first - order reactions to
give products B and C :
A+ B kz 0.2 sec -1
A → C kz 0.4 sec 1 -
What is the composition of aa sample of initially pure A one minute after the reaction
begins ?
5.73 . A water tank 20 ft high and 10 ft in diameter is drained by an orifice at the
bottom on one side . The rate of flow out of the orifice is proportional to the square
root of the height of water above the orifice :
V = 0.61A V2g Ah
where V = flow rate , cu ft / sec

A cross -sectional area of orifice , sq ft
g = acceleration of gravity , 32.2 ft / sec2
Δh height of liquid above orifice , ft
The orifice is 4 in . in diameter , and the tank is initially full .
hr of its
a . How long will it take to drain the tank to half of capacity

?
the top
40
be
min what will
cu
at
is 60 at
of
water added the tank rate

If
ft
is
b
/
.
the depth Explain

20 10
of
water the tank after min min

in in
5
?
5.74 tank diameter and high drained by two orifices One orifice
ft
ft
A
6
.
.
of
diameter and from the bottom the tank The other diameter
in
ft in
in
in
ft
is
is
3
2
.
How long does take the liquid level drop

to
of
and from the bottom the tank

ft it
2
10 .
20
15
15
10
to
to
to
from
ft
ft
ft
ft
ft
6
5
a
?
,
,
(
)
(
)
(
)
See Prob 5.73 for the orifice flow relationship

.
6.75 stirred tank reactor used for hydrolyzing sucrose See Example 4.18
A
is
-
.
(
.
for rate data For each the following cases calculate the composition
of
of
the
)
.
,
hr
effluent stream after the process starts

4
Initial solution Input

in
tank
Output
,
Condition Sucrose Sucrose

Volume Flow rate liters min
/
,
liters concentration concentration

,
,
liters min
/
moles liter moles liter

g
g
/
/
OO OO
50 12
a
5
too
50 10 12 10
OO8
с b
50 10 10
ooo8
OO 8
50 10 12
5
8
d
for
5.76 . Develop
a differential mass balance each component the following
in
by
Initially
to
situation and react second order reaction form
C.
stirred
B
A
a
,
-
charged with fed continuously
B.
, of
of
tank reactor solution solution
to
A
at is
is
a
hr
the reactor constant rate After the mixed reactants and product are with
1
is .
at
drawn the same rate added
.
Calculate the composition the gas leaving the reactor Example 5.15 when
, is of
in
5.77
.
the composition the entering gas
as
of
follows
N2
per cent per cent
of 73 78 78
a.
17
, 02
per cent NO
10 17 5
.
per cent NO per cent per cent N2
, 02
17 5
b
,
.
.
per cent per cent N2
02
per cent NO
c
,
.
.
Compare the results percentage NO oxidized
as
.
Calculate the composition the gas leaving the reactor Example 5.15
of
in
5.78
if
.
the total pressure atm Other process variables are constant

is
2
in .
of .
ethylene has been studied the laboratory
to
The conversion ethane
at
6.79
K .
910
°
.
+
C2H6 C2H4 H2
approximately
32
be
to
has been found order reaction

It
-
dcc2H6
32
CC2H6)
k
do
(
where 1.13 liter mole Calculate the composition initially pure ethane
of
%
sec
g
k
2
!
/
total pressure atm assuming that the reverse reaction

at
of
of
after sec reaction

5
2
a
negligible
is
sq
Calculate the equilibrium yield ethyl alcohol lbs
at
pressure 1,500
of
of
5.80
in
a
.
/
.
Example 5.16 Other data remain the same

in
.
.
at
5.81 Calculate the equilibrium yield ethyl alcohol Example 5.16
of
in
steam
a
.
ethylene ratio
of
as
Other conditions are the same those stated the example

in
2.0
.
.
Determine the equilibrium composition initially pure ethyl alcohol when
of
5.82
.
to
sq
at
heated pressure 500 lbs

of
570
of in
is
it
F
°
6.83 Solve Example 5.17 total pressure

10
at
atm 100 atm Compare

6
a
,
(
)
(
)
.
the results with the example

.
5.84 The equilibrium constant for the reaction

.
Kp
=
2N02 N204
given by
is
2993
log Kp 9.226
-
-
T
where Kp = equilibrium constant atm

-1
,
T
K
of of ,
°
Calculate the composition nitrogen dioxide gas

at
100 and atm

F
N21
6. a
°
.
80 .
Calculate the composition

at
gas 100 and atm where moles

=
F
1
a
;
°
NO2 20 moles
+
2N204
to .
at
5.85 Sulfur burned SO and SO3 The gases leave the furnace
At
727
.C
is
..
°
.
this temperature the equilibrium constant for the reaction

,
12
02
=
SO
+
SO3
,
P803
KP
is
po
%
Pso
,)
(
:
and Kp 1.85 atm - 22. Pure sulfur is burned with air 30 per cent in excess over that
required for complete oxidation to SO3 . Calculate the composition of the gases
leaving the furnace at 727 °C and 1 atm , assuming equilibrium .
5.86 . The equilibrium constant for the reaction
NO + 12 02 = NO2
is
T °F Kp , atm - 42
86 5 X 106
900 2.5
Calculate the composition of a gas which initially contains 1 lb mole NO and 1 lb mole
O2 at 7 atm pressure : (a ) at 86 °F , (b) at 900 °F .
This reaction is important at high and low temperatures in the manufacture of
nitric acid .
5.87 . The Wisconsin process for the manufacture of nitric acid proposed as a first
air
step reacting the nitrogen and oxygen of the high temperatures For the
at
.
reaction
= 2NO
+
N2 02
Кр 10-4 at 2500
X
K
6
equilibrium NO this temperature and

at
of
Determine the concentration atm
,
air
N2
starting with per cent

79
21
1 02
per cent
,
(
).
In
fed con
to
of
of
6.88 the manufacture ammonia mole ratio and N2 H
is
3
a
,
.
tinuously catalyst chamber high temperature and pressure For the reaction
to
at
a
.
=
12
32
NH3
+
N2 H2
the
equilibrium constant Kp has the following values

:
TºKP KP atm
1
-
,
400 6.30
500 0.32
600 0.040
700 0.0063
800 0.0025
computer program for calculating the data needed plot equilibrium

to
Write
a
of a
.
NH temperature for total pressures

to
as
of
of
and function
H
of N
conversion
a
,
100 atm and 1,000 atm

.
by
Using your program hand the equilibrium conversion

as
model calculate
a
,
b
.
at
500 and 500 atm

C
°
5.89 For the reaction

.
2H2O
+
CO2 2H2
C
the
equilibrium constant partial pressures

of
in
terms
is
log Kp
K
5.88 0.52 104

X
=
T
/
°
to
of
to
Write calculational flow chart determine the fraction converted CO2

C
at a
a
.
The feed may

be
any given temperature this the only reaction taking place

if
is
.
50
all
50
as
temperatures
%
at
mole
C %
taken mole H20

C
,
following your flow chart

at
of
Calculate the fraction converted 1000

b
,
°
.
.
5.90 . The reaction in Prob . 5.87 is accompanied by the reaction
NO + 12 02 = NO2
where Kp ( at 2500 °K ) = 0.0045 atm - 43. Considering these two reactions , outline
air
how you would calculate the equilibrium composition of
at
the con
Is
2500
K
°
.
NO appreciable this temperature
at
of
centration
?
,
the following reaction the equilibrium constant Kp 1.60
In
+ at
5.91 986
is
:
°
.
CO2 = H2O CO
+
H2
Calculate the equilibrium composition resulting from initial composition
70
an
of
mole
per cent CO2 mole per cent
30
at
atm
1
,
,
5.9
additional problems are needed computer programming Probs
If
in
5.7 5.8
,
.
5.11 5.13 5.22 5.26 5.31 5.39 5.41 5.44 5.47 5.49 5.51 5.52 5.54 5.57 5.59 5.60
,
be ,
by ,
5.63 5.66 5.67 5.72 5.73 5.75 5.77 5.79 5.81 5.84 5.86 5.90 may solved
,
In
many
or
writing computer programs
of
both
or
calculational flow charts these
.
up
the
problems the program
or
to
instructive set flow chart and then solve

is
byit
,
,
by
problem hand following the program flow chart step or
step
.
REFERENCES
L.
W. Clump
C.
B.
A.
A.
L.
L.
Foust Wenzel Maus and Andersen Principles

1.
S.
,
“
:
Unit Operations John Wiley Sons Inc. New York 1960
of
&
J. ,
”
.
M.
Dudley and Troeltzsch Ind Eng Chem
48
F.
L.
Kastens
J.
2.
2230–2240
,
.,
:
:
.
.
1948
(
).
Harper Chemical Engineering

, G.
ed
Mills Process Research

in
J.
3.
in
I.
.:
,
),
“
(
.
Practice Reinhold Publishing Corporation New York 1954

C. ”
50 ,
.
M.
Couter Chem Eng Progr

T. R.
Nelson and 526-531 1954

R. L.
5. 4.
..,
(
:
:
.
2d ).
Pigford Absorption and Mc
K.
ed
L.
Sherwood and Extraction ”,

,
.,
:
Graw Hill Book Company Inc. New York 1952

C. ,
,
-
.
M.
H.
to
Smith and Van Ness Introduction Chemical Engineering

6.
J.
,
"
:
Thermodynamics McGraw Hill Company Inc.

2d
ed
New York 1959

”,
.,
,
-
.
CHAPTER 6
THE ENERGY BALANCE
The complete description of a physical system requires specification of

its
those other physical properties discussed earlier

as
as
energy well
.
the ability
do
Energy may generally defined the object
be
to
as
of
work
,
resisting force through Certainly the
to
that overcome distance

is
a
,
.
properties
of
of
hot stove burner are different from those the same
a
an
Similarly
on
burner when cold automobile moving highway
it
is
a
.
has properties different from the same automobile standing still The
.
the energy these objects
of
differences here are the two different

in
in
by
In
these cases the energy the temperature
of
states evidenced the
is
.
burner and the motion system can also possess

of
the automobile
A
.
the earth's gravity field

its
as
energy position
of
of
result the relative
in
of a
,
its
its
position the chemical bonding
as
of
of
molecules atoms and
a
,
,
variety
of
of
result other causes

a
its
From the early recognition energy
of
men have studied effects

,
to its
its
upon objects object object and

to
transfer from transformation

,
This field study called thermodynamics

of
from one form another

is
.
.
study was the realization that energy
of
of
One the first results this

is
a
byan
unique property the system That the energy object depends

of
of
is
,
.
its
only upon present state The energy possessed the automobile

.
mentioned above does not depend upon the route previously traveled
;
nor does the energy the burner depend upon the number
of
of
times has
it
by
previously been heated Thus energy determined the measurable

is
.
variables that define the state such temperature pressure velocity

is as
,
,
mass and height For this reason called state function

it
a
,
.
.
Another early result this study was the conclusion that energy
of
is
may readily
be
from
or
to
It
conserved transferred from form form

,
.
body destroyed The energy

or
to
body
byof
but never created the

it
is
,
entire universe thus constant This conclusion expressed the

is
is
a
thermodynamics
of
of
of
first law sometimes called the law conservation

,
energy The law results from large accumulation

of
observations not
a
,
.
any general theory More recently the studies Einstein and

of
from
.
appli
in on
its
energy and mass and spectacular

of
others the interrelation

,
cation the atomic nergy field have pointed out that energy not
is
,
-e
221
conserved . However , in normal chemical and physical processes the loss

or gain in mass is undetectable , and the independent conservation of
mass and of energy can be assumed with confidence .
the
is all
The energy balance makes use of the first law to account for
energy chemical process any other process The process
or
in
con
aa
in
.
an
sidered separate from the rest imaginary boundary
of
the universe
is
;
an
placed around the portion process energy balance
of
the for which
as is
process boundary usually
be
The
to
written within the referred
to
is
.
the system Everything outside the boundary called the surroundings
is
.
.
The system and the surroundings together constitute the universe
.
the energy the system and the energy
of
of
of
Therefore the sum the sur
,
roundings constant
is
a
After the system defined the energy balance considers the energy
is
entering the system across the boundary the energy leaving the system
,
across the boundary and the accumulation energy within the system
of
;
,
so
that
6.1
Energy energy out energy accumulation
+
in
=
)
(
This expression has the the mass balance Eq
As
as
same form 5.1
(
.
).
steady state the accumulation
is at
before zero Before the energy

is
,
more explicit terms will necessary be .
to
balance written
of in
consider
it
,
the various forms energy

.
FORMS OF ENERGY
an
All energy must energy balance In

be
many
of
forms included
in
energy changes
in
processes certain forms remain constant and them
be ,
may recognized and

be
neglected However these forms must under

,
.
stood before their magnitude and constancy can

be
determined Some
.
energy are easily recognized everyday life the energy

of
forms
off in
of
a
:
by
moving automobile the energy given burning flame the energy

of a
,
pan energy are less easily recog

In of
of
content hot water Other forms

a
all
the energy balance expressed quantitatively

be
nized forms must

,
.
be
so
the same dimensions and units that the terms can added
in
is .
The typical chemical process involves flowing fluid which being

a
the
changed physically chemically The forms energy considered

or
of
in
.
following discussion are those which must flowing fluid

be
considered
is of in
a
system based upon one pound mass

be
Each term will fluid

.
Kinetic Energy KE The energy moving object

of
kinetic energy
a
(
).
.
by
baseball thrown the pitcher possesses definite kinetic energy

A
as
it
a
pound flowing fluid possesses

of
travels toward the catcher definite

A
.
travels through the flow duct

as
kinetic energy Kinetic energy

it
.
its
an
equal object times the square velocity divided

of
to
of
the mass
is
THE ENERGY BALANCE 223
by 2:
mv2
KE ( 6.2 )
2
= kinetic energy , ML2 / 02 , lbm
ft²
where KE sec2
/
M
mass
m
lbm
= =
,
,
V = velocity sec
ft
C
,
/
L
v
O
,
/
Customarily the terms the energy balance are expressed force
in
in
,
go
dimensions and units Therefore the dimensional conversion factor
,
.
inserted Eq 6.2
in
is
)
.
mv2
KE 6.3
)
2gc
where KE kinetic energy LF

= =
lb
ft
,
,
,
-
ge
dimensional conversion factor

,
ML FO² 32.2 lbm lbs sec2
ft
/
/
,
For one pound mass the specific kinetic energy

is
,
v2
KE 6.4
29
)
.
where KE
specific kinetic energy LF
M
lbs 1bm
ft
/
/
,
-
As
discussed Chap and numerically equivalent

is in
are
of lb
lbm
1 ,
1
1
3,
.
.
That the weight For this Eq
of
lbm reason the units
is
lb
,
1
,
,
.
.
are sometimes written simply feet and KE
as
6.4 sometimes referred

is
,
as )
(
Although this accepted practice the

to
the kinetic energy head

is
,
-
canceling pounds force with pounds mass not strictly correct

of
is
.
by
by
Potential Energy PE The energy possessed

of
mass virtue
a
(
).
its
position the earth's gravitational field called potential energy

in
A
is
boulder lying the top cliff possesses potential energy with reference
of at
.. of
a
pushed off the cliff its poten

to
the bottom the cliff the boulder

If
is
tial energy transformed into kinetic energy Similarly

as
falls
is
it
by its a
,
.
flowing system possesses potential energy because

of
of
mass fluid
in
an a
height above arbitrary reference level Potential energy defined

is
.
PE
=
mzg 6.5
(
where PE potential energy ML2 02 lbm

ft
sec2
,
т
,
/
/
M
mass lbm
2 m
=
= height above reference level

ft
,
L,
gravity
of
acceleration O2
ft
=
sec2
g
,
L
,
/
/
In
force units the potential energy

is
,
mzg
PE 6.6
(
)
gc
,
where PE
potential energy , LF , ft -lb
For one pound mass ,
29
PE (6.7 )
9c
where PE specific potential energy , ft -lb , / lbm

As discussed in Chap . 3 , g and ge are numerically equal for engineering
calculations , although they have different dimensions . PE is often
referred to as the potential - energy head .
Internal Energy ( E ) . The component molecules of a substance are
constantly moving within the substance . This motion imparts internal
energy to the material . The molecules may rotate , vibrate , or migrate
within the substance . As discussed in Chap . 4 , the addition of heat to a ,
molecular activity and hence
its
its
material increases internal energy
.
its
The temperature internal energy Inter
of
of
material measure
is
a
.
nal energy designated by the symbol although sometimes used
U
E
is
is
.
The dimensions internal energy are the same the other energy units
as
of
,
ML Typical units are foot pounds force
LF Btu
or
in or
The British
?
-
/
.
an
thermal unit Btu energy unit commonly used engineering work

is
It (
)
with heat defined below

is
.
its
Heat When energy transferred between system and sur
is
Q
a
(
) .
as
roundings Thus heat

or
as
transferred either work heat

it
is
is
,
,
.
energy This type energy transfer occurs whenever
of
transit hot
in
a
.
body brought into contact with cold body Energy flows
as
is
heat
a
from the hot body the cold body until the temperature difference
to
is
destroyed that until thermal equilibrium established For this
is
is
;
reason heat may energy being transferred over

be
as
considered tem
a
,
perature gradient No system can contain heat

Heat addition
to
a
.
.
system increases the system energy usually the internal energy Con
,
versely heat removal from system decreases the system energy

It
is
a
,
use the symbol designate the energy transferred

to to
to
conventional
Q
the
assign positive value for heat transfer into

as
heat and
it
a
,
system
.
usually expressed units either Btu Although

or
of
calories
in
is
Q
units are most precisely defined electrical energy they

of
terms
of in
these
,
conveniently defined the heat capacity

is be
of
can terms water

in
A
.
the quantity energy required raise the temper

to
of as
of
Btu defined
63
64
to
of
ature water from calorie defined

A
as
lbm
g is
F
the
1
°
.
quantity energy required raise the temperature

of
of
water from
to
of
1
In In
the energy balance usually defined per pound

to
14.5 15.5
is
C
Q
,
°
°
.
fluid flowing other applications may refer

to
of
rate
of
it
heat
a
.
transfer
.
Work Work is also energy in transit .

(W
W).
Work is done whenever
a force acts through a distance :

X=1
W = So 0 of
osda (6.8 )
where W =
work , LF , ft -lbs
f == force , F, lb ,
dx = distance , L , ft
1 = total distance , L , ft
If the force is constant , with distance ,
W = fl (6.9 )
Chemical engineers are frequently concerned with the compression or

expansion of a gas . For example , in a cylinder of cross -sectional area A
with a piston , the force exerted on the gas is equal to the pressure (i.e. ,
force per unit area ) times the area of the piston A. The distance the
piston travels is equal to the volume of the cylinder V divided by the
area A. Therefore , by Eq . ( 6.8 )
2 V
- " PA d A
W d
Pav
6.10
P
)
Vi
SC
sq
where total pressure gas

is on L3 of
lbs
VP
=
ft
ft /F
>
L
/
,
’ ,
= volume gas
cu
of
,
by
Work done the system the surroundings positive

as
defined
is
From this discussion evident that work energy

to
in
contrast
it
,
by
does depend upon the path followed the system The integration
.
Eq 6.10 requires knowledge

of
at
of
each value
of
the value
P
of
)
.
V2
Fig 6.1 where the work

Vi
between and This illustrated

in
is
is
1
along paths process starting

at
evaluated several alternate for and

to a
1
In
ending each case the work equal the area 1-3-4-2 but since
at
2.
is
,
Of
case the work

A to
curve 1-2 differs from case also different the three

is
paths shown that gives least work and that the

of
of
the case
C
case
,
,
Other paths could devised yielding work quantities ranging

be
most
.
infinity for the same initial and final states Regardless

to
at of
from zero
.
path energy constant and the energy

at
the chosen the state

is
2
,
state constant
is
1
.Eq
the integral 6.10 also requires that single

of
of
The evaluation
a
(
each point along the process path and that these points
at
pressure exist
be
This condition limits the processes that can

to
be
continuous treated
.
approximate differentially separated equilib

of
those which succession

a
rium states . Processes involving shock waves , explosions , etc. , cannot

be treated by conventional thermodynamics .
Energy as work may be added to a system in several forms . A com
pressor or pump adds energy to the fluid by doing work . Work must be
done to push the fluid into and out of the system , as defined by the
В.
P A
1
Padv
3 V 4
Fig . 6.1 . Dependence of work on process path .
imaginary boundary . Energy as work can also be lost from the system
by conversion to heat through frictional mechanisms . The total work
done by the system can be split into two terms :
W W' + W,
where W work done by the system

W ' = work appearing in the surroundings
Wi work lost due to frictional effects
Of course the ideal process would operate without frictional effects , and
there would be no lost work .. All the work done by the system would
but
appear in the surroundings . In practice these losses always occur ,

they can often theory
be
eliminated The lost work cannot represent

in
energy appear thermal energy the system and

as
in
loss but must

in
in
a
surroundings For instance fluid piping operation the lost work

of in
the
a
,
.
by
by
drop pressure compensated

its
the fluid rise

in
in
shown
is
is a
a
temperature The work appearing the surroundings obtained

in
'
.
forcing system
as
of
work done the fluid into and out the and

as
in
work
by
by
done mechanical device operated the fluid the system

in
a
Wi
W
6.11
W
W2
= =
)
+
8,
(
+
1
'
or W2 6.11a
W
W
+
+
1
)
8,
Wo8 is the work accomplished through a compressor , pump , or turbine .

Itis often called shaft work . W 8 By definition ,
, is a positive number
when the system transfers energy to the surroundings , through a turbine ,

the system and W
for
example pump compressor adds energy
or
to
A
is ,
.
negative value this case In flow system the basis usually
in
has
a
a
.
flowing fluid the compression work required
to
as
of
taken lbm
is
1
1
.
the fluid into the system Fig
of
as
In
shown
in
force lbm 6.2 this case
1
,
.
.
do
on
the surroundings work the system negative value
so
must have
a
;
.
the specific volume The constant
of
of
The volume lbm fluid
V1
1.
is
1
System
boundary
Flow area A1 Surroundings System

VA
,
-:
E
P.
Flow
direction
Flow duct
V
at
of
of
volume fluid entrance

lb
=
temperature and pressure
Fig the fluid enters the system

as
6.2 Work done

.
.
is on
force exerted the fluid P1A1 and A1 the distance through

is
is
/1
--
,
Al
enters the system

as
which the fluid forced the cross sectional

is
it
-
.
of
area the flow duct Thus

,
.
= P1A1
=
W
-(
A1 6.12
)
*
)
Wi
-P
=
=
on
The minus sign indicates that the force acts from the sur
–
A ,
V
A
1
/
the system
on
roundings similar analysis

at
the system the exit

to
.
do
shows that the system must the surroundings

to
force the
on
work
so
fluid out that

,
V.
W
P
=
6.13
2,
)
(
The symbol
W
customarily defined per unit mass system this equation

as
of
in
is
,
*
Similarly and are usually defined per unit mass system

of
E
Q
,
,
Combining Eqs . ( 6.10 ) through (6.13 ) gives
W = W ,8 + W1 + W2 + W
V2
Si P dƯ 8
– P.V. + P , V +
1 2 ,
SP
= W. + W
W.,
W 8 = - ( P, V, - P.V ) + PdV W
SA(PV)
V
+ Si Pdỹ
P – W
V,
J ( -P Mỹ – 7 4P + P Mỹ ) – W.
Sonia
=
-
W
d
P2
or Wi
P
W
6.14
W
SP
)
–
-
V
by
This expression useful determining the work done the fluid
in
in
is
a
or
pump compressor turbine There are often times when the engineer
,
.
,
compare the performance his equipment
to
the theoretical of
to
wishes
maximum shaft work There are other times when the lost work
is
.
In
small compared the other energy
or
to
work terms both these cases
.
W
dropped from Eq
to
6.14 obtain
is
1
)
.
P2
W.
P
6.14a
d
)
SP
V
-
Other Forms Energy energy such
as
of
of
Other forms electrical

,
in .
energy may the energy balance They would appear

be
included
be in
,
.
W.
Because these seldom appear chemical processes they will not

in
considered here
.
TOTAL ENERGY BALANCE
The various forms energy are added algebraically give the total
in to
of
6.3
energy balance conventional flow system shown Fig

A
is
The
.
system the fluid the flow duct between reference points

in
and
of is
the 2
.
Choice reference points arbitrary but once chosen they define

is
be
energy effects between the two points must

all
system and considered

,
the .
Applying Eq 6.1 the system Fig steady state gives

at
to
6.3
in
(
.
.
total energy balance

:
Energy energy out

in
= =
Ei
PE
KE1 KEZ PE
+
+
E
6.15
Q
2,
)
'
'
The primes designate heat and work quantities removed from appear
or
,
no
ing =
the surroundings there are frictional effects
= in
If
so
=
that
W
,
,
.
,
0,
by
W.
= Expanding applying Eq
W
and gives
=
6.11
Q
)
'
'
'
1
Wi
PE
Ej
W.
W.
KE KEZ PE2
+
+
–
1
2
1
6.16
Q
E,
.
:
)
'
Heat exchanger
Adiabatic
chemical
reactor
Turbine
W
2
W2
A2 U2
P2
KE2
W -A1 72 PE2
Vi E2
P
Vi
KE ,
PE ,
E,
Arbitrary reference height
Fig . 6.3 . Energy balance in a flow system .
Substitution of more specific terms gives , per pound of fluid ,
Piſt
2
vi ? 219 V22 229
El + 1 + + Q =
= E , + P2V ,2 + + + W. ( 6.17 )
2gc Gc 29 . gc
Rearranging as a difference equation gives

Azg
ΔΕ + Δ ( PV ) +
A ( v2)
29 .
+
9c
Q – W ( 6.18 )
Equations ( 6.17 ) and ( 6.18 ) are typical expressions for the total energy
balance in a flow system . In specific cases, various terms may be zero

or negligible , and the equation simplifies .
The group E + PV has been defined as the enthalpy , H. The enthalpy
is a convenient and widely used function . Like E , H is a state function .
its
all
This is apparent since definition are properties

of
the terms state

in
With this definition Eq 6.18 becomes

,
)
.
Azg
+
v2
ΔΗ
+
A
W. 6.19
(
)
–
Q
)
(
go
2gc
many chemical processing applications changes velocity and

In
in
in
that the kinetic energy and potential energy terms

so
height are small

,
are
negligible Then
.
ΔΗ W. 6.19a
-
Q
)
(
'
.Fig
10 6.1
is to 6.3
Example enthalpy the system
of
of
Calculate the increase water
in
sq in
,
.
hp
85
where
. sq
A1
pump adds
22
zı
ft
>
ft
=
0.1 A2
ft
ft
0.5
A
=
1
,
,
-
.
the system and heat exchanger removes 10,000 Btu
hr
of
The flow rate water
70 a
/
,
100 gal min
PH
cu
at
62.3 lbm
to ft
.F
/
0
°
the
by
The velocity equal
of
Solution flow the volumetric flow rate divided
is
.
cross sectional area
-
:
KE
:
sq 60
100 gal min min sec
1
/
/
(
cu )
(
)
Vi =
7.48 gal 0.1
ft
ft
/
(
)
(
)
2.23 sec
ft
=
/
gal min
sq 60
100 min sec
(1
/
(
/
cu )
)
V2
7.48 gal 0.5
ft
ft
/
(
)
(
)
0.45 sec
ft
/
–
ft
ft
= V22 0.45 sec 2.23 sec
–
vi
AKE
)2
lbj
?
/
=
=
(
ft (
-0.074
ft
lbj lbm
-
2gc
/
32.2 lbm seca
2
(
)
(
)
/
Ws hp lbs sec
ft
550
1
:
/ /
-
cu
100 gal min
ft
62.3 lbm
Mass flow rate
/ /
(
)
(
)
60
cu
7.48 gal sec min
ft
(
)
(
)
13.9 lbm sec
=
- /
lbs sec
ft
550 / /
Ws –39.6
ft
Therefore lbs lbm
,
/
13.9 lbm sec
Q
':
Btu
hr
10,000 Btu
lb
778 ft
/ /;
=
/
-
(
)
(
)
=
Q
'
hr
13.9 lbm sec 3,600 sec
/
(
)
(
)
–154 lbs lbm
=
ft
/
-
APE
:
Azg
APE
85 9c
10
- ft
32.2 sec2
–
ft
ft
/
(
ft )(
32.2 lbm lbj sec2

-
/
75
lbs lbm
ft
-
Applying Eq 6.19 gives

(
)
.
Azg
Δ
2
ΔΗ
)
(
W.
+
+
–
Q
gc
2gc
AH -0.074
75
ft
+
lbs lbm lbs lbm lbs 1bm

ft
+
ft
154 39.6
–
/
/
(
Therefore AH lbs lbm

-
ft
189.3
,
Nonflow Systems The energy balance may also applied

be
to
non
.
the
flow systems where the system remains enclosure throughout

an
in
,
operations
, be
to
of
entire series considered Chemical reactants being

.
during gas being cylinder and

an
stirred tank reaction heated

in
in
a
oven containing sample for drying typical examples

In
are these
a
.
no
to no
cases there change kinetic energy and

v1
v2
in
change
is
in
(
potential energy Equation 6.15 then reduces

21
22
=
.
(
)
).
ΔΕ
W
–
6.20
Q
)
(
'
which relates the internal energy change the system

to
of
the quantities
appearing surroundings Usually
of
heat and work the more

in
it
is
.
the system only For

to
convenient consider effects

in
frictionless
a
.
process
ΔΕ Q W ( 6.20a )
for
be
Equation ( 6.20a ) is generally valid ;
frictional effects can always
the walls bounding the nonflow process
, to
considered occur outside
.
separated from
W
W
be
or
W
W
The terms and 2 cannot because there
'
entering leaving fluid
no
or
is
.
Equations 6.19a and 6.20a both equate change state function
in
a
of )
(
(
)
to
of
value the sum heat and work terms Since the left side these
Of
right
be
equations state function the side must also the two
is
a
.
the right Eqs 6.19a and 6.20a the work term whether
on
of
terms
(
(
.
path function
as
W
shown above Therefore the other term

or
W
is
,
a
)
.
the right these equations path function
be
or
of
on
must also
Q
a
,
',
.
path
W
be
of
Moreover must function such form that and
-
it
Q
a
,
are both independent path This path dependence must

W
be
It of
–
8
Q
on
when evaluating
be
will
Q.
treated the section heat
in
considered
effects
.
Example 6.2 Helium compressed cylinder equipped with piston and

in
is
a
.
cooling jacket
an
cu
at
compressed
of
The helium initial volume from
atm
ft
is
1
a .
The cooling jacket removes heat

70
70
cu
to
at
of
of
and final volume
0.1
ft
F
.F
°
compression from the helium Calculate the heat removed the internal energy
if
.
remains constant AE
=
0
(
.)
Solution This nonflow process By Eq 6.20

is
a
.
)
.
ΔΕ = W a
Q Q
Therefore W
,
.Eq
By
gas the cylinder

of
for the total mass

in
6.10
,
(
SiV2
=
Pav
W
=
By
the perfect gas law PV nRT

-
= nRT1
Р
V2 dV
AV
W nRT
V
2 ,1
In
nRT
Vi
,
Because =
PV
n
RT
P.Vilni
W
=
Pi = atm
1
Vi
ft
V2
ft
cu 0.1 cu
=
1
0.1
W
log
atm
2.3
cu
11
W
1.0
ft ft
= = =
)
(
C
1
6
(
)
(
-2.3 atm cu
-2.3 atm
cu
cu
2.72 Btu atm

ft
ft
Q
/
(
)
(
-6.25 Btu
Therefore 6.25 Btu removed from the helium
,
is
.
Constant -volume Process . If the volume of a system remains con

stant during a process , the work done is zero :
V2
pdV
Sri
0
W =
Therefore Eq 6.20 becomes
,
)
(
.
AE Qv
=
6.21
)
This expression states that the increase internal energy any con
in
in
stant volume process equal the heat added during the process
to
For
is
-
the
restricted type process the path function has been equated
of
to
Q
a
,
This allows numerical evaluation
of
difference value state function
in
a
a
.
by
taking the difference between the initial and final values

be
to
done
of
by
rather than integrating the heat added along process path

E
a
,
.
Many
are
Constant pressure Process steps chemical process
in
a
-
In
to
order the process
at
carried out constant pressure control
it
is
,
.
necessary accurately possible

as
effects
in
the heat
to
as
know constant
a
pressure process At constant pressure
.
V2
AV
PAV
W
=
=
/
*P
and Eq 6.20 becomes

(
)
.
AE = QP PAV
-
=
or AE PAV
+
QP
=
6.22
)
By the definition enthalpy
of
PV
+
H
E
=
and ΔΗ ΔΕ
+
PV 6.23
Δ
)
(
)
At constant pressure Eq 6.23 gives
,
)
.
ΔΗ AE PAV
+
6.24
)
(
Combining Eqs 6.22 and 6.24 gives

(
)
.
AH QP 6.25
)
(
The increase enthalpy system

is
constant pressure process

of
in
in
to a
equal
to
the heat added the system

Because constant pressure
.
processes are chemical processes the enthalpy function

so
in
common
is
,
original definition was due partly

Its
to
very important the relation

.
the
ship stated Eq The next several sections will consider

in
6.25
)
(
.
.
enthalpy increase various constant pressure physical and chemical

in
of -
The enthalpy increase course equal

to
processes the heat added

is
,
,
.
during the constant ressure process Here again the path function
this Q
,
.
by-p
has been replaced difference state function values Again

in
,
a
.
can be done only because the path is specified . The calculational

advantages are obvious .
HEAT EFFECTS
Changes of enthalpy and resultant consumption or liberation of heat

accompany the heating , vaporization , condensation , fusion , freezing , and
mixing of materials . All these heat effects must be considered quantita
tively in an energy balance . This section surveys available data and
methods of presentation . No attempt is made to discuss the measure
ment and correlation of these variables (see Refs . 4, 5 , and 8) .
Heat Capacity
its
As heat is added to a material , temperature rises The heat capacity
.
quantitative temperature
the exact degree
of
of
statement increase
in
is
for a
specified addition capacity may generally
be
The heat
of
heat
a
c
.
an
as
the increase heat added with temperature

in
increase
in
defined
:
=
C
6.26
ST
)
SQ
very small amount

to
is of
The term used indicate that heat
is
is
a
path
be
involved The exact differential dQ cannot used since Q
a
,
.
Equation 6.26 can

M
and integrated
be
to
function written for mass
(
)
.
give
SMcdT 6.27
=
Q
)
but the integral cannot evaluated without specifying the path
be
Since
.
M
nor dT
path ependent the path ependent
be
neither must
is
c
,
-d
-d
the integral give any value between

be
Paths can
to
selected
in
term
c
.
zero and infinity but only two heat capacities are common use These
in
,
.
,cp
the heat capacity for constant volume process and CP the heat
cv
are
a
,
capacity for constant pressure process

a
For constant volume process combination Eqs 6.21 and 6.26

of
a
)
(
(
-
gives
Cy
aQ - aE
=
6.28
(
aT
(
)
),
85
(
).
-
at cy
Thus fundamentally the heat capacity equal

at
constant volume
is
,
the differential change internal energy with temperature

in
to
constant
Eq 6.26 has been replaced
of
volume Here the inexact differential

.
)
.
possible only because the

by
the exact differential aQ aT V. This

is
.y
/
(
path has been fixed making exact differential along that path
an
The
Q
,
partial derivative notation specifies that only one the several possible
of
vary
In
independent this case temperature may

to
variables allowed
is
.
vary , but volume is held constant . The relation between E, V , and T

would form a surface on a three -dimensional diagram having E ,> V , and
T coordinates . If this surface were cut by a plane having V = constant ,
the slope of the line of intersection would be cy .
Rearrangement and integration of Eq . ( 6.28 ) gives
T'2
DEV
ΔΙ
dT
Сү
cvy
6.29
57
)
=
*
This expression evaluate the change internal energy
( to
in
used
in
is
a
Ev
constant volume process The heat capacity frequently
Cy
is
a
).
-
temperature
of
function
The heat capacity . pressure by
at constant obtained combining
is
Eqs 6.25 and 6.26
(
)
.
aH
CP 6.30
aT
)7,
07
),
)
Р
(
-
P
(
the
Cp
the heat capacity constant pressure equal
at
Therefore
to
is
,
differential change enthalpy with temperature

of
.
The change enthalpy with temperature constant ressure
in
in
process
-p
obtained by integrating Eq 6.30
is
)
.
T2
6
dT
AHp
cp
6.31
)
=
*
Cp
The heat capacity varies with temperature for real substances
.
In
Heat Capacity Chap the simplified kinetic theory

of
Gases was
4
.
develop the relation

to
used
KE RT
32
4.19
)
(
the the
applying for ideal gases the kinetic energy
be of
the molecules
as
If
is
.
energy existing
to
only form this relation can used obtain

of
specific heat
KE KE ΔΕ
T2
T1
32
–
–
R
22
11
)
(
upon differentiation
or
:
,
әЕ
.- 2 3
(
at
R =
CV 6.32
)
(
)
6
V
Equation give close approximation

to
to
found
6.32 measured
is
a
)
(
cy
argon and helium

as
for the inert monatomic gases such

of
values
.cy .
gases with more complicated molecules give higher values

of
However
,
This because these molecules have rotational vibrational and elec

is
energy translational energy

as
as
gas phase
of
tronic forms well When

a
.
the are
heated the translational rotational and vibrational energies

is
Usually the electronic nergy levels are not affected

Of
increased
.
.
-e
heat added to the gas , only part is used to increase the translational
energy level and therefore the temperature . The rest is accepted by the
molecules and results in increased levels of translational and rotational
energy but is not directly measurable as a temperature increase .
In the development of Eq .( 4.19 ) the square of the components of the
mean molecular velocity in the x , y , and z directions was shown in each
case to be one - third of the mean velocity squared . Thus the kinetic
energy may be considered as the sum of the kinetic - energy components
in the directions of the coordinate axes . That is ,
=
( KE ) . + ( KE ) y, + ( KE ) , = KE = 72
12 RT + Y2 RT + 12 RT (6.33 )
In a similar way , the rotational and vibrational energies can be separated

into components along their major coordinate axes . By the equipartition
of energy theorem , each of these component energies could contribute
12 RT to the total energy .
Consider a molecule containing two atoms . This molecule can have
velocity components in each of the three coordinate axes , so that the
translational energy can contribute 3 ( 12 RT ) to the total energy . It can
rotate around the axis containing the molecular centers and also around
an axis perpendicular to this one , so that the rotational energy can con
tribute 2012 RT ) to the total . Finally , it can vibrate along the axis
containing the atomic centers . Since this vibration contributes potential
as well as kinetic energy to the molecule , it can contribute 2012 RT ) to
the total energy . For this molecule then ,
ΔΕ -
(3 X 12 + 2 X 12 + 2 X 12 ) RAT
a E 7
and
1 ) V. –
( at 2 R
=
=
CV (6.34 )
Experimentally , it is found that many such diatomic gases have

specific heats increasing gradually with temperature , but giving values
close to 52 R over extended temperature ranges . The value of 52 R may
indicate that the vibrational -energy level is not increased as the temper
ature rises . The gradually increasing heat capacity may be explained
all
all
by postulating that possible modes

of
movement are not active

of in
the molecules but that the temperature increases more and more
as
the
,
molecules are excited into more the possible modes energy

of
of
complete explanation the experimental heat capacities can given

be
of
A
only the quantum theory which recognizes that only discrete

of
terms
in
,
for
energy levels are possible the possible energy forms

of
each These
.
stepwise increases energy single molecule are masked measure

of
in
in
a
molecules by the fact that these increases

on
large numbers
of
ments
gradually increasing proportions the total molecules present
of
in
occur
the temperature increases Reference discusses this more fully
as
3
.
.
For a nonlinear molecule of n atoms there would still be only three

а diatomic
possible components of translational motion , but in contrast to a
molecule , there would be three components of rotational motion and
( 3n – 6 ) modes of vibrational motion . Again each mode of vibrational
motion contributes both a kinetic- and potential -energy component .
The total energy of such a molecule would then be
E =
3 ( 12 RT') + 3 ( 42 RT ) + 2 ( 3n - 6) ( 2 RT ) = ( on – 6 ) ( Y2
72 RT )
so that
aE
).
= Сү
( 3n 3) R ( 6.35 )
aT V
all
Of course , this specific heat would be obtained only when possible
of
modes molecular motion are excited
.
Ideal Gases The ideal gas model does not recognize attractive and
-
.
repulsive forces between molecules Therefore for such gas the internal
a
,
.
energy and enthalpy must independent pressure Equations 6.28

all be
of
)
.
and 6.30 then hold for not just for those
at
processes constant ,
(
constant pressure Differentiating the defining relation
for
or
at
volume
.
ng
enthalpy and apply the perfect gas law gives

-
RIT
dE
PV dE
+
dH PT
+
6.36
=
)
(
From Eqs 6.28 and 6.30 but without the restrictions imposed there
,
,
(
)
.
= dT
Cy
de
= =
6.37
)
(
dH Cp dT 6.38
)
Combining Eqs gives
to
6.36 6.38
(
)
.
Cy
+
R
=
Cp ( 6.39
)
an
This expression valid for ideal gas irrespective

of
molecular com
is
plexity requires only that internal energy and enthalpy are inde
It
.
pendent pressure and that PV = RT

of
..
The heat capacity real gases generally varies with

of
Real Gases
.
accurately predicted from theory

be
temperature and cannot Because

.
many processes constant pressure most experimental

at
of
interest occur
,
.Cp
data are reported Heat apacity data are conveniently reported

as
-c
by
an
empirical equation the polynomial form

of
bT
K +
+
Ср cT2
=
6.40
a
)
Cp
heat capacity cal

CP
where mole
=
'
,
temperature
K
T
=
,
'°
= empirical constant
K
cal mole
a
/g /g /g
'
,
empirical constant
K
cal mole
b
;32
°
,
= empirical constant
K
cal mole
cC
=
°
(
)
The constants a , b , and c are determined from experimental data , as

mentioned in Chap . 3. Frequently , it is desirable to have cp in English
units , Btu per pound mole degree Rankine , and T in degrees Rankine .
The constants a , b , and c must be individually converted to the new
units . Although Cp may be converted from units of cal / g mole 'K to
Btu / lb mole ° R with a conversion factor of 1.0 , this is not true of the
constants and c in Eq . ( 6.40 ) . The heat capacity may be expressed

b
for
pounds grams molar units

or pound moles gram
or
or
of
of
mass
a
The heat capacity
or
to
as
of
moles lbm often referred the
g
is
1
1
.
specific heat The term specific heat
of
also used for the ratio the heat
is
.
capacity
to
at
of
of
15
substance that water These two definitions
C
a
°
.
specific heat give the same numerical value but the latter definition
of
,
yields dimensionless quantity
a
mean heat capacity temperature range may defined using
be
over
.Eq A
3.44
(
)
.
T2
// T2
dT
dT
ēp
Ср
52c 6.41
Cp
)
=
Combining Eqs 6.40 and 6.41 and integrating gives

(
)
.
T2 T2
//
577
Ź at
bT
b
cT
)
dt
Ĉp
+
+
=
°
(
)
b
T.2
T2
)Tw
T10
++
T12
a
–
))
+
(
ş
T;
(
=
T2
T.
-
b
==
6.42
(
T12
T1
12
T.
?,?
)
+
+
T
T
3
2
a
)
:
(
repetitive mean heat capacities are

of
For routine calculations tables

,
They can from Eq and are given

be
calculated
in
useful 6.42
,
(
)
.
.
G.
Appendix
Mean heat capacities are always evaluated between some reference
Appendix
on
temperature and the desired temperature based

G
is
.
heating cooling between and the desired temperature

25
77
or
If C
T,
°
°
(
)
on
heating cooling
or
given the horizontal scale carried out between

is
.
two temperatures using mean

25
of
neither which the calculation

is
C
,
,
°
heat capacities must

be
done two steps

in
:
-1
25
25
7p
7p
T1
AHT 6.43
ČP
-
–
=
25–7 25–7
,
(,
,
,
)
(
T
,
,
(
T
Note that the two mean heat capacities Eq have different

in
6.43
(
)
.
values
.
Values for the constants Eq 6.40 are given for various real gases
of
)
.
expressed by
in an
all
Appendix heat apacity data can

be
G.
Not
in
-c
equation the form Eq 6.40 Usually the equation applies only

of
of
(
.
).
limited temperature range

a
.
Р
AH = fcd (2
P ΔΗ , AH2
Sep
dT
Ho=
PO
1
T2
Ti
T
Fig
on
pressure heat capacity
of
6.4 Effect
.
on
Heat Capacity pressure
on
The effect
of
of
Effect Pressure heat
.
capacity can using Fig enthalpy change
be
examined Here the
of
6.4
a
.
.
gas being heated from constant high pressure
to
at
calculated
, is
T
2
a
T
,
using two alternate paths Since enthalpy state function
is
a
.
H2 Hi =
H
+
H
H4 H3 H4
–
-
:3
,
(
)
)
-
T2 T2
dT
AH
AH
or Cp
+54
CP
dT
6.44
,cp
Δ
+
,
)
S
,
,
and AH are
Cp
the heat capacity the base pressure and AH

at
where
is
,
,
both enthalpy changes occurring constant temperature Expanding

at
.
these terms
əН
ΔΗ dP
=
=
6.45
,
ӘР
)
S (
T1
) )
aH
AH2 dP 6.45a
OF
ӘР (
)
(
T2
For an
Po
cp
where base pressure usually atm for which known

aH aa
is
is
>
1
,
.
no
attrac
as
ideal gas zero discussed earlier since there are

is
P
(
)
/
,
In
tive and repulsive forces between molecules this case

.
T2 T2
Cp dT
dT
SOCI
sa
cp
and Cp = CPO 6.46

(
quite small
at
For real gas not zero However moder

it
is
is
rT
,
H
a
P
(
)
/
usually negligible
be
ate pressures and temperatures and may

as
taken
,
pressures below about Methods are available for calculating

10
at
atm
.
aP
aH from PVT data and correlations are available for estimating

at /
,
(
)
Cp
elevated pressures
?
.
Gas Mixtures The heat capacity gases may

of
of
mixture
be
a
.
evaluated from the pure component heat capacities taking into consider
-
ation the gas composition

.
CPΣ 6.47
2
XiCpi
(
)
where Cpx = heat capacity of mixture of i components

Cpi = heat capacity of one component , cal g mole / 'K
Xi = mole fraction of component
Equation ( 6.47 ) applies only to ideal solutions of gases . Ideal solutions
show no volume change or heat effect on mixing . This definition of the
heat capacity of a mixture is adequate at moderate pressures in most
cases . At high pressures and in other cases experimental data are
needed to determine the heat capacity of a mixture .
Example 6.3 . Calculate the heat required to raise the temperature of 1 g mole of
ethylene from 100 ° C to 700 ° C at 1 atm using the following experimental data .
TºK CP, cal / g mole 'K

298 10.41
500 15.16
700 18.76
1000 22.57
Solution . Several alternate methods will be illustrated .

METHOD 1. A graphical integration of Eq . (6.31 ) is accomplished by plotting the
experimental cp as a function of T ( Fig . E6.3 ) . The limits of integration are Ti =
373°K , T2 973 ° K . The area is
973
ΔΗ
373
Cp dT /
11,000 cal g mole
METHOD 2. An empirical equation may be developed using the data . The equa
tion may be used for this and other calculations . There is no simple convenient
graphical method for fitting an equation to the four data points . However a numerical
method or an analytical method using Eq . (6.40 ) and any three data points may be
used to obtain an approximate equation . The points at 298 , 500 , and 1000 ° K will
be used , because they cover the required temperature range .
At 298 ° K : 10.41 = a + 298b + (298 )2c

At 500 ° K : 15.16 a + 500b + (500 ) ?c
At 1000 ° K : 22.57 = a + 1000b + ( 1000 ) 2c
Solving these equations gives
/
a = 1.35 cal g mole ' K
b /
: 0.034 cal g mole (° K ) 2
C = -1.28 X 10-5 cal g mole (° K ) 3/
By Eqs . (6.31 ) and (6.40 )
S.
T2
AH = AT
1 * (a + b+ + cT ") at
b
3: с
T33
+
T32
)7,9
–
++
= a(T. T ») +
)
(
–
–
(
T;
")
0.034 10-5
X
1.28
373
+
1.35 973 9732

–
3732 9733 3733

-
–
(
(
)
)
:
3
2
10,800 cal mole

g
/
The empirical equation developed here does not agree with that found Appendix
G.
in
on
The equation the Appendix more data and more accurate

in
based
is
is
.
20
15
ºk
/,
mole
g
cal
10
Cp
973
Cp
dT
Spor
373
5
200 400 600 800 1,000

K
°
T,
Fig E6.3 Solution Example 6.3

to
.
will
no
be
METHOD the mean heat capacity offers advantage here but

of
Use
it
3
,
.
By Eq
of
demonstrated 6.42 and the data method

2
(
:
.
10-5
x
0.034 1.28
Cp
X
3732
+
1.35 9732 973 373

=
973 373
)
(
(
)
2
18.0 cal
K
mole
/g
Therefore
,
AH CP ΔΤ
-=
373
-
–
18.0 973
)
(
)
(
10,800 cal mole

g
/
centigrade could used with the mean heat capacities this problem
be
Temperature
in
in
.
Example 6.4 . A volume of 100 cu ft of gas at 1 atm and 800 ° F is cooled to 100 ° F .
The gas is 60 per cent hydrogen and 40 per cent ammonia by volume . Calculate the
heat removed .
Solution . METHOD 1. By Eq . (6.47 ) with data from Appendix G ,
CP = CHCP.H , + 2NH4CP,NH
= 0.6 (6.947 0.200 X 10-3T + 0.481 X 10-6T2 )
+ 0.406.086 + 8.812 X 10-3T – 1.506 X 10-6T2 )
CPI = 6.695 + 3.41 X 10-37 °K 0.315 x 10-6T °K2
The data are in degrees Kelvin , so that the equation may be converted :
TºR
TºK
1.8
TºR ° \ 2
+ 3.41 X 10-3 x
CPE = 6.695
1.8
· 0.315 10-6
( 1.8 )
= 6.695 + 1.89 X 10-3T °R – 0.0973 X 10-6 ( TºR ) 2
The cpe may be either in metric or English units , because /

1 cal g mole ° K 1 Btu /lb
mole °R . Then
560°
9.89
ΔΗ 10-3T 10-6T2 dT
X
0.0973
-
= S1200R (6.695 +
-
1.89 10-3
X
5602
+
6.695 560 1260 12602

(
)
)
(
0.0973 10-8
X
1260
-
5603
(
)
3
-5820 Btu mole

lb
/
In
cu
at
gas
of
and atm
ft
100 800
1
F
°
cu cu
100 492 1260

ft ft
lb
°
=
(
)
(
0.109 mole
/
n
at
SC
lb
359 mole
/
Therefore
,
Heat removed
lb
mole Btu mole

lb
0.109
= =
5820
(
)
(
)
/
634 Btu
METHOD Using mean heat capacities The mean heat capacities given
In in
2.
Appendix are good only when final temperature

25
either the initial

or
Ti G
C
is
T2 °
this case 800 426 and 100 37.7 Therefore necessary

)C
F
is
it
C
F
°
in °
,
(
).
by
make the calculation Eq

to
two steps 6.43

..
(
)
:
426
AH AH 426 AH 37.7to 25
25
.7
to
to
to
37.7
=
426
25
First AH From Appendix

to
G
,
, CP
7.00 cal moleºK XH 0.6

/g /g
=
H
, :
,
,
,
10.05 cal moleºK 0.4

25 =
CP NH CNH
AH 426
25
0.6 7.00 0.4 10.05 426

to
–
[
(
)
(
)
(
)]
(
-3290 cal mole mixture

/g
=
Similarly
25
AH37,7
to
,
KK
TP.H2 6.90 cal mole

/g /g
TP.NA 8.55 cal mole

'
,
ΔΗ37.7 25
25
to
0.6 6.90 0.4 8.55 37.7

–
[
(
96 )
(
)
(
)]
(
cal mole mixture

–
/g
Therefore , AH 426to 37.7 = -3290 - ( -96 )

-
-3194 cal/g mole
= - 5750 Btu / lb mole
This checks the answer of method 1 within graphical and slide -rule accuracy .
Liquids and Solids . Heat capacities of liquids and solids are also
determined experimentally . Data are sometimes reported in the form
of Eq . ( 6.40 ) , frequently as the specific heat . The variation of the heat
capacities of liquids and solids with temperature is less than for gases .
Selected heat capacities for liquids and solids may be found in Appendix G.
More complete data are available in Ref . 4. The variation with pressure
for
of heat capacities for liquids and solids is negligibly small , and
.cy
no
Cp
engineering purposes distinction made between and
is
,
solid are available Kopp's rule may applied

no
be
data for
If
to
a
,
very rough estimate the heat capacity Kopp's rule states
of
obtain
all a
cal .
6.2
molecules have heat capacities for each
of
that atom
C
/g
°
except for the following atoms 20
at
of
constituent atom the molecule

C
,
,
°
which have the values shown 4.0 3.8
Si
H
1.8 2.3 2.7
0
C
B
5.0
= of >
;
;
,
F,
:
5.4 Thus Kopp's rule predicts that the heat capacity solid urea
P,
,
.
NH CONH
20
27.4 cal
of +
at
+
+
X
1.8 2.3 4.0 6.2
X
to C
g
is
2
,
/
°
(
an
mole compared experimental value 19.2 cal mole
/g
C
C
°
,
.
°
Kopp's rule useful only for temperatures near since heat capacit
20
is
C
,
°
solids vary with temperature

of
simple accurate procedure for estimating the heat capacities

no
There
is
for
liquid and solid solutions Experimental data

of
, for in be
each solution must
.
available Heat capacities for several aqueous solutions are given

.
other data are available Eq 6.47 may

no
Appendix
be
G.
If
used
,
)
.
For heterogeneous liquid and solid mixtures

an
approximate value
.
Eq 6.47 holds
(
.
Phase Changes
Energy must change liquid and
In be
to
to
to
added
solid change
a
liquid gas many solid crystalline substances show heat

to
addition
on a
,
.
transition from one crystal structure

to
effects another
.
on
Vaporization and Condensation The enthalpy increase vaporiza

.
usually called the latent heat vaporization may

be
designated
of
It
tion
is
.
by
the symbol AH The heat vaporization varies with temperature

of
,.
H.
and pressure Selected values are given Appendix More complete

in
.
Ref prediction are discussed

of
data are found and methods

in
in
4,
be .
vaporize exactly the same

to
Ref Heat must added substance

5.
;
.
quantity
be
to
of
heat must removed condense the same substance

.
on
Fusion and Solidification The enthalpy increase

or
fusion melting
.
by
usually called the latent heat fusion and designated AHf The
of
is
.
heat of fusion is measured at the melting point . Both the melting point
and the heat of fusion are insensitive to changes in pressure . Selected
values for heats of fusion are given in Appendix H. For further informa
tion see Refs . 1 and 2 .
Sublimation . Solids vaporize without melting at temperatures below
the
be all
triple point where three phases may coexist The latent heat
of
,
.
sub
may
be
to
of
of
sublimation AH considered the sum the heat fusion
vaporization given temperature rigorously
at
of
and the heat This
is
a
.
true only the triple point but good approximation even some
at
at
is
a
,
what lower temperatures

.
Example 6.5 heating
20
to
of
Calculate the heat added water from
in
100
–
g
it
.
to
130 at atm pressure

C
1
°
Necessary data from

be
Solution The process must broken into several steps

.
.
the Appendix are given for each step
.
Heating ice from -20

to
C
1.
0
°
°
Op
For ice 0.485 cal -20 to

=
/g
C
)C
,
0
°
°
(
AT
TP
AH solid 0.485 -20

0
)]
-
)
(
=
9.7 cal 175 cal mole

/g
=
/g
at
Fusion
of
2.
ice
C
0
°
AH 1436 cal mole

g
=
,
Heating liquid water from

to
of
3.
100
C
0
) to
СР 18.03 cal
K
mole 100
/g
C
0
°
°
(
= CP ΔΤ
ΔΗι 18.03 100
–
0
(
)
(
=
1803 cal mole
/g
Vaporization
at
of
water atm
4.
100
C
1
,
°
AH 9717 cal mole

,
=
/g
Heating
of
steam from 100 atm

to
5.
130
C
1
°
)
K
°
AH
dt
, g
eta
10
10-07
x
x
+
S3790 7.256 2.298 0.283

= =
*
K
°
-
(
246.6 cal mole

/g
AH total AH golid AH AH AH
+
AH
+
+
,
,
+
175 1436 1803 9717 247

13,377 cal mole
/g
to
Heat added 100 1028 13,377

g
)
(
74,320 cal 100

g
/
Mixing The isothermal mixing

or
of
of
Heat more substances two

.
usually involves the absorption Such heat effects may

or
of
release heat
.
negligibly small the mixing two similar organic liquids

or
as
of
be
in
,
very large the mixing

as
of of
sulfuric acid and water

in
,
by
enthalpy given
of
The solution solute solvent

in
is
B
A
a
ngH
na
6.48
+
NAHA NBHB AH
=
m
В
8
)
,
where H. , HA ,, HB = enthalpy of solution , of A , and of B per mole of
all
each , respectively , the same temperature
at
respectively
of
of
of
пA пв moles solution and
B
A
= =
,
п
,
,
.,
mixing based upon moles
of
of
AHm heat solute
,
mixing may upon any quantity
be
as
The heat based such the total
of
,
customary give data per mole
to
as of
moles solution However
of
it
is
,
.
Eq
of
solute the last term indicates 6.48
,
.
.
The heat absorbed when
in
Heat solid dissolved
of
is
Solution
a
a
.
liquid
in of
solution are determined
of
called the heat solution Heats
is
.
experimentally Typical curves are shown Fig 6.5 The integral
.
.
-18,000
CuSO4
H2SO4
ZnCl21
mole solute
NaOH NaOH
/,
-10,000
g
(
NH₃ NH37
ΝΗΝΟ HNO3
,
cal
solution
,
504
Na
of CH3COOH
0
-NaCl
heat
NaCl
2
Phenol
NaNO3
Hm KCI
A -KC1
NaNO
+10,000
10 20 30 40 8
0
Moles H20 mole solute

/
Fig Integral heats

of
6.5 solution
.
.
.
preparing solution
as
in
the heat absorbed

of
of
heat solution defined

is
given concentration from pure solid and pure solvent The heat effect
of a
.
an
already dilute solution very small

to
of
solvent
an is
the addition
.
Therefore the integral heats approach asymptotic

to
of
solution tend
,
infinite dilution Often only the

in at
is of
value which the heat solution

is
,
given Appendix Most solids release

as
infinite dilution
on at
value
I.
,
dissolving therefore by convention most heats

of
heat solution are

,
,
;
negative
.
liquids similar structure may have negligible heat

of
of
Solutions
of
a
that case Eq 6.48 becomes

In
mixing
or
solution
(
)
.
6.48a
+
H
xAHA XBHB
=
)
8
,
Example 6.6 . Calculate the heat released when 100 lbm of H2SO4 is mixed with
100
by
all
70
at
H20 and atm the heat absorbed the solution what
If
lbm of
is
,
F
1
°
.
the final temperature
is
?
Solution
3
10 10
18 98
lb lb lb
NH2804 1.02 moles
% %
NH20 5.55 moles
nH20 5.55 H20
mole
5.45
1.02 moleH2SO4
lb
NH2804
From Fig 6.5
,
.
ΔΗ -13,800 cal mole H2SO4
/g
η
English units
In
-13,800 cal mole
lb
g 454 mole mole
/
(
)
(
)
/
ΔΗm
252 cal Btu
/
lb (
)
24,900 Btu H2SO4
-
mole
/
Therefore
,
Heat released 24,900 Btu mole mole

lb
lb
-
ΔΗm 1.02
-
)
(
(
)
-
25,400 Btu
by
Temperature the heat absorbed the solution

If
is
,
:
AH solution AHM
+
AH solution -25,400 Btu 200 lbm acid

= =
/
Tp
AH solution AT
100 lbm
Acid strength = 50
%
200 lbm
From Appendix 0.595 Btu lbm

G
F
=
p
/
,
°
(
25,400 Btu
AT
F
=
214
°
0.595 200 lbm acid

(
+ )
(
Ts = 214 284
F
70
F
°
°
The normal boiling point

no
will boil
so
of
the solution 254 that heat

if
is
is
at it
F,
°
removed and this final temperature not actually attained atmospheric pressure
is
,
of .
Example 6.7 Calculate the final temperature the acid resulting when 200 lbm
of
.
no
50
70
70
at
at
per cent sulfuric acid

of
diluted with 100 lbm water with heat

F
is
F,
°
loss
.
The acid may

be
unmixed calculations and then remixed with the

in
Solution
“
,
.
Fig E6.7
as
shown
in
water
,
-AHm
+
AH
m
all
ΔΗover
2,
1
,
From Example 6.6

,
,
24,900 mole H2SO4

lb
ΔΗm Btu
–
1
,
/
,
Final acid
si
m
For AH
.2
‫دام‬
:
NH2804 1.02
20
11.1
18
nu 20
%
NH2O 11.1
10.9
=
nH2804 1.02
=
s
From Fig 6.5

,
.
ΔΗ 15,700 cal mole

-
/ /g
η
2
,
-28,300 Btu
lb
mole
‫یرب‬
100 lb
H,SO4
200 lb acid 70 °F 300 lb acid
( 50 % H2O, 33.3 % H2SO4
50 % H2502) - Hm , 1 66.7 % H2O
70 °F f ΔΗη , 2:
100 lb
H2O
70 °F
200 lb
AHM
m=0 HO
70 °F
100 lb
Н, 0
70 °F
Fig . E6.7 . Acid mixing .
Therefore ,
Hover 24,900 -28,300
% lb +
all
)
(
)
-
-3,400 Btu mole H2SO4
-
/
Acid strength = 10 300
10
33
%
=
Tp
From Appendix 0.74 Btu

G
lbm
F
=
,
°
/
70
1098 3,470 Btu 0.74 Btu
–
lbm
-
F
300 lbm
F
T
°
°
)
)
(
(
)
(
T)
(
)
(
and 86 /
F
°
Enthalpy Composition Diagrams

-
The variation enthalpy with composition two component system

of
in
a
-
on
conveniently
expressed diagram where composition
be
can plotted
is
a
1on
on
All
the horizontal axis and enthalpy plotted the vertical axis
is
.
the heat effects which have been discussed are included the enthalpy
in
composition diagram
.
An enthalpy composition diagram for sulfuric acid water mixtures

are is
-
-
on
shown Fig 6.6 The enthalpy values plotted the vertical axis
in
given relative for water

at
to
for 100 per cent

to
H
32 and
F
O
O
°
60 These bases are selected arbitrarily since enthalpy

at
H2SO4
is
a
°F
.
relative quantity particularly

32
The use for H20

at
of
H
-=
is
F
0
°
.
of the
all
convenient because the basis used almost tabulations

in
of
is
it
thermodynamic properties diagram shows loci This

.4
of
water
constant temperature along with solid- and vapor hase boundaries
.
,
-p
The solid phase boundaries are the two dotted curves shown
at
the bottom
-
the per
the diagram high concentrations For example

40
at
at
of
82
and
F
,
°
.
lbm
cent H2SO4 the enthalpy would

be
of
120 Btu solution and

–
,
/
the temperature were reduced solid

be
solution would saturated

If
,
.
crystals would begin

to
form
.
the
The diagram incomplete and hence does not indicate whether

is
,
,
solid crystals would pure H2SO4 hydrate

be
or
It
of
H2SO4 also does

a
not permit the quantitative calculation the mass fraction crystals

of
of
present at any enthalpy . The vapor - phase boundary is the curve at the
top of the diagram at which the lines for constant temperatures of 220 to
400 ° F show sharp breaks . For example , at 41 per cent H2SO4 , 240 ° F , the
/
its
solution has an enthalpy of 26 Btu lbm of solution and is at boiling
point more heat added the solution enthalpy increases through the
If
is
,
.
200
300
220
240
400
160 °F
120
400
80
Vapor
solution
/,
40
lbm
,H
Btu
300
O
Enthalpy
40
-
-80
-
120
Liquid
-160
20 40 60 80 100
Mass per cent H2SO4
Fig 6.6 Enthalpy omposition diagram for sulfuric acid and water
.
.
-c
enough heat were added

to
increase the
to of
evolution water vapor

If
.
enthalpy 200 Btu lbm the total system would represented by

be
a
/
,
point the top the diagram and composition per cent H2SO4
41
at
of
of
a
The temperature would Physically the system would

be
about 265
,
F
°
.
water vapor and boiling solution per cent H2SO4

53
of
of
consist about
a
.
by
tie
This found drawing line through the point representing the

is
a
tie
total system parallel to the lines for 240 and 300 and noting
its
F
°
intersection with the saturation locus The amount liquid present can
of
..
be obtained from material balance
+
0.53x
X
0.41
x
0
1
)
(
0.775 liquid lbm total material
=
lbm
/
by
tie
The the top the diagram continue
of
lines which are cut
to
the
enthalpy and composition nearly pure water vapor
at
atm pressure
of
1
and the temperatures shown
be
These values can found from steam
.
tables
4
.
on
Because both energy enthalpy and mass balances hold mixing
,
(
)
the enthalpy composition diagram may used for graphical calculations
be
-
no
systems where heat removed The enthalpy balance

in
is
is
.
ngHB
+
NmHg nAHA
=
6.49
)
upno
process where That
on
for heat removed the heat released
is
is
a
,
the resulting solution .
to
solution goes heat
.
Example 6.8 Repeat Example 6.7 using Fig 6.6
.
6.6
on
Solution per cent acid designated Fig
50
70
at
as
is of
The 200
lb
A
F
is
lb .
.
By the inverse lever arm rule the mixture
70
at
to B.
as
The 100 H20 shown

F
,
°
is -
be
Elies 100/300 The temperature
B.
the distance from then read
to
about
of
which checks Example 6.7 within the accuracy the graphical readings
84
of
F,
°
.
Chemical Reactions
Heat effects occur all chemical reactions chemical reaction
in
A
.
involves the rearrangement

of
of
the electrons the constituent atoms
to
destroy existing chemical bonds and The destruction
to
create new ones

.
chemical bond requires energy and the formation

of
is of
bond releases
a
a a
,
energy An exothermic reaction one which there net release

as in
of
is
.
energy This energy must

be
removed heat constant temperature

if
a
be .
be an
In
to
maintained endothermic reaction there net energy

is
is
a
.
requirement which must supplied

as
heat the reaction temperature

if
to
be maintained
is
specified temperature
be
Industrial reactions often must

at
carried out
a
give the desired rate and yield

to
the reaction Chemical engineers

in
the
must therefore design equipment

to
or
to
remove add heat maintain

desired reaction temperature design process
In
be to
order involving
a
.
chemical reaction the engineer must

to
able determine the heat

a
Although would probably possible

be
to
of
effect the reaction deter

it
.
experimentally
of
mine the heat the reaction much more convenient

it
is
,
and rapid
at to
Because chemical reactions may

be
use available data

.
any temperature any pressure obviously impossible

or
carried out
all is
at it
,
all
possible reactions possible conditions

to
of
tabulate the heats

.
For this reason , a systematic approach to heats of reaction has been

developed . A number of arbitrary definitions and specifications make
it possible to calculate the heat of reaction from a minimum of tabulated
data .
Standard Heat of Reaction . The heat effect of a given reaction
depends upon the temperature and pressure of the reactants and products .
all
To systematize the calculations , a standard state is defined for reactants
and products The standard state
as
of
defined the natural state the
is
.
component At
25
at
and atm conditions most real gases

these
C
1
°
.
approximate ideal behavior sometimes necessary
to
It
state whether
is
.
given component liquid For example the natural
or
gas solid
is
a
,
a
.
liquid
25
at
of
water and atm However sometimes
it
state
is
at is
C
,
°
.
specify the standard state gaseous water
25
to
as
desirable and
C
°
atm even though cannot actually exist For this reason
it
is is
it
1
,
.
list the state each reactant and product where there
to
of
desirable
any doubt The heat reaction where the reactants and products
of
.
at
of
are their standard states called the standard heat reaction and
is
of a is
by
designated specified when

be
AHR The exact reaction should
..
its
given For example the standard heat

of
numerical value heat

is
,
.
nitric oxide and oxygen give nitrogen dioxide

to
13,559
of
reaction
–
is
as cal
mole but gram mole The value for product

of
of
what mole
is
g
/g
1
?
,
given by
NO 4202 AHR 13,559 cal
-
+
NO2
-
-
→
but for the reaction based on oxygen

of
mole
g
1
+
2NO 2NO 27,118 cal

+
02 AHR
--
,
The negative numerical value for the heat reaction indicates that the
of
reaction exothermic
is
Unfortunately tabulation only the standard heats reaction for

of
of
a
,
possible reactions would too long

be
be
all
of to
usable Therefore
is
it
,
.
calculate the standard heat reaction from more limited

to
necessary
a
special reactions The two commonly tabulated reactions

of
number
.
of
of
are heats formation and heats combustion

.
In
Heat chemical compound

of
Formation formation reaction

is
a
a
,
.
its
produced from The standard heat

of
constituent elements formation

.
AH
the enthalpy increase the formation reaction which occurs

in
g is
(
product The reactants and products are

of
when mole formed

of C is
1
The standard heat

of
of
the standard state

at
25 and atm formation

1
°
sulfuric acid the heat the following reaction

of
is
-193,910 cal
→
AH
+
H2 H2SO4
,
202
=
S
g
F
1
s
(
(
(
)
(
)
actually
be
as
Most formation reactions cannot carried out written

,
The elements simply do not react in the manner indicated . Several

intermediate steps may be necessary . The heats of formation must be
calculated from the heats of other reactions which are evaluated experi
mentally . Heats of formation for many compounds have been deter
mined from experimental data and are tabulated in various books.4.6.7
A selected list is given in Appendix I.
The standard heat of any reaction may be calculated if sufficient
heat of formation data are available . The formation reactions and their
enthalpies can be added and subtracted like mathematical equations to
give the desired reaction . From the definition of heat of formation , it
follows that all elements in their standard states have zero standard heat
of formation .
AH
soz ( g) and H2018 ) H2SO4 ( l )
AME
-ΔHP ( H , 0 ) H2500
)
SO3 +302
-AH
8
S
(
)
SO3
s
8
(
)
(
)
(
and and
O2
H2
H2
02
(g
+
g
{
8
8
)
(
)
(
)
(
)
FIG
of
of
of
6.7 Calculation standard heat reaction from heat formation data

-
-
.
.
The calculation
of
of
of
standard heats reaction from heat formation

by
an
possible because the heat effect can replaced

be
data enthalpy
is
by
Eq 6.25 The enthalpy difference can then

as
difference shown
(
)
.
..
its
an
evaluated using artificial reaction path since

be
value depends
,
on
solely
of
end conditions Consider the formation sulfuric acid from

.
an
SO and water The actual reaction path and artificial path involving
,
Fig 6.7 The actual reaction path

of
heats formation are shown

in
by is
.
shown by the solid arrow For this path given

of
the heat reaction

It is
.
by
AHR The artificial path shown the dotted arrows involves

is
.
the decomposition
to
their elements and the recombina

of
the reactants
form the final product The heat
for
to
of
tion these elements effect

.
this path
is
802
)1,0
AHP
-
AH AHP
+
1,802
(
the
Since both paths start the same point and end

at
at
the same point

,
enthalpy differences must equal

be
AHR AHP 502 AHP AHP

+
4,0 1,80
(
)
(
)
)
This result may be generalized to the statement that the standard -state
heat of reaction equals the heats of formation of the products minus the
heats of formation of the reactants .
Example 6.9 . Calculate the standard heat of reaction for
H2SO4 (l ) + 2NaOH (aq ) → Na2SO4 ( aq ) + 2H2O (l )
Solution . The symbol ( aq ) implies that the NaOH and Na2SO4 are in dilute solu
tion (strictly speaking , infinitely dilute solution ) . Therefore , the heats of solution
must be included . Heats of formation and solution are obtained from Appendix I.
To obtain the appropriate equation , the heats of formation of H2SO4 ( l) and NaOH ( aq )
must be subtracted from the heats of formation of Na2SO4 (aq ) and 2H20 . To accom
plish this , the formation reactions of H2SO4 (l ) and NaOH (aq ) are reversed and the
sign is changed on the heat of formation , which is now a “ heat of decomposition . ”
The solution step may be written like a reaction , as shown . The & indicates HO
infinite dilution .
H2SO4 (1) H2 (g ) + S (s) + 202 (g ) -AH , 193,910

2NaOH (s) → 2Na (s ) + O2 ( g ) + H2 (g ) - 2ΔΗΣ 2 ( 101,990 )
2NaOH (aq ) + 2NaOH (s ) + H2O -24H ; 2 ( 10,246 )
2Na (s) + S (s) + 202 ( g) ΔΗ -330,900
-
Na2SO4 (s )
Na2SO4 (s) + c H , O → Na2SO4 ( aq ) AH ; 560
2H2 ( g ) + O2 ( g ) 2H2O (1) 2ΔΗΣ = 2 ( –68,317 )
H2SO4 (l ) + 2NaOH ( aq ) → Na2SO4 ( aq ) + 2H2O (l ) AHR —48,802 cal
six
equations give the desired reaction

to
as
The written are added Note that

,
.
for
twice the formation and solution equations NaOH and twice the formation equa
give the desired reaction adding the reactions
In
to
water were necessary

of
tion
,
.
quantities that appear opposite sides

on
of
two reactions cancel

.
give the heat

to
as
of
of
The heats the reactions written are added the desired

reaction
:
ΔΗ 193,910 101,990 10,246 330,990 560 8,317

+
2
2
)
(
(6
48,802 cal
-
be
to
48,802
of
The reaction exothermic cal heat must removed maintain the

° is
.
25
products
at
C
.
In
Example artificial reaction path involved heats

of
6.9 the solution

vaporization must also
be as
as
of
is of
well heats formation

heats Often
,
.
included particularly when water vapor

or
of
one the reactants

,
products The necessity for including these steps becomes obvious when
.
mind that any artificial path must More

at be
fixed continuous
in
is
it
the exact initial state and end

at
over must start the exact final state

it
,
met whenever the partial reaction equations

be
These restrictions will

-
up
the total reaction equation

to
add
-
do
Heat not
of
Combustion Because most formation reactions

.
actually
be
of
occur standard heats formation must calculated from

,
experimental data for other reactions common reaction combus

A
is
.
tion i.e. the rapid oxidation compound Most organic compounds

of
a
,
few inorganic compounds can

be
The heat
of
and burned combustion

a
.
can be measured experimentally in a calorimeter . For example , with a

bomb calorimeter the reaction takes place in a heavy steel vessel which is
immersed in a large liquid bath . After equilibrium is attained , the tem
perature change of the bath is carefully measured , and an analysis is
made of materials in the bomb . The heat of combustion is determined
from the temperature change and heat capacity of the bath , including
1,8
the bomb itself and the bath container .
typical combustion reaction
of
the combustion aniline
A
is
:
02
N2
→
72
12
+
+
C6H 6CO2 H2O
N
314
g
,
(
I)
(
)
(
)
= (l
AHC
ΔΗ -812,000
-
cal mole aniline
g
/
The standard combustion products are CO2 HCl
)aq
H2O N2
g
,
,
(
)
l()
(
)
(
arbitrary because
25
The choice
at
of
and SO2 and atm N2
is
C
g
,
1
°
(
)
(
)
.
nitrogen may oxidize
of
Standard heats combustion are tabulated
in
.
Appendix
I.
combustion may
be
to
of
of
Heats used calculate heats formation and
reaction by the addition appropriate
of
heats
of
and subtraction equa
tions used directly
be
Also heats
to
of
combustion can calculate heats

.
often necessary use an artificial reaction path

of to
of
It
reaction using
is
.
This should
of
no
both heats formation and heats combustion .
cause
added difficulty the principles equations are kept
of
the addition of
if
in
mind
.
Example liquid
of
6.10 Calculate the standard heat formation of methanol

.
CH3OH from combustion data

.
)
(
Solution The desired reaction

is
.
O2
AH
12
CH2OH
;
=
+
2H2
)g
)g
C
?
s
(
)
(
)
by
2H
This reaction may adding the combustion reactions for
be
obtained and and

C
,
O2
subtracting the combustion reaction obviously cannot

12
CH3OH
of
The
)g
(
.
undergo combustion The additions and subtraction mentioned above will introduce
.
O2
12
the desired
).g
(
ΔΗ 94,052
)g ) +
CO2
C
-
+ + 0
(1 )g
O2 )9
(,
s
(
( ( )
2H2 2H2O 2ΔΗ 21–68,317

g
)g
)
(
-ΔΗ
32
02
→
CO2 2H2O CH3OH 173,650

+
)g
(1
)
(
)
cal
O2
CH3OH AH
12
57,036
+
;
-
+
2H2
)g
C
)g
(1
s
)
(
)
From the heats

of
as
combustion written
,
AH –94,052 -68,317 173,650

+
+
2
(
= -57,036 cal
for
Example 6.11 the hydration ethyl

of
Calculate the standard heat reaction

of
.
give ethyl alcohol

to
ene
.
The desired reaction may

be
Solution written
.
ΔΗ
→
OH
+
H2O
H
?
C
)g
C
(1
,
,
,
)
.
(l
The desired heat of reaction is obtained by adding the heats of combustion of the
reactants and subtracting the heat of combustion of the product . However the heat
of combustion of water is zero , because it is already fully oxidized .
C2H4 (g ) + 302 → 2CO2 ( g ) + 2H2O (l ) ΔΗ -337,234

2C02 ( g ) + 3H20 (1) → C2H5OH ( ) + 302 ( g ) -AH 326,700
C , H . (9) + H2O (l ) → C , H , OH (1) AHR - 10,534 cal
The original statement of the problem did not specify the states of the reactants and
products ; so the standard states were chosen . However , the reaction actually occurs
in the gas phase
C2H4 (g ) + H2O ( g ) → C2H , OH ( g ) AHR ,26°C = ?
To determine the heat of this reaction , the latent heats of vaporization at 25 ° C must
be included , as shown below .
C2H4 (g ) + H2O ( l C2H5OH ( ) ΔΗ -

- 10,534
H2O ( g ) H20 (1) -AH , 10,519

C2H5OH ( ) → C2H5OH (g ) ΔΗ - 10,120
C2H4 (g ) + H2O ( g) → C2H5OH (9) ΔH R, 25°c -10,135 cal
Effect of Temperature on Heat of Reaction . Industrial chemical reac

tions are seldom carried out at 25 ° C . The reactants may be at one
temperature and the products at another temperature . Therefore , it is
necessary to convert standard heats of reaction ( at 25 ° C ) to other
temperatures . The heat of reaction at any temperature T may be
calculated by setting up an imaginary process in which the reactants
are cooled from T to 298 ° K , the reaction takes place at 298 ° K , and the
products are heated from 298 ° K back to T ,> as shown in Fig . 6.8 . The
enthalpy change in going from an initial state to a final state is the same
Reactants Desired reaction Products
TºK TºK AHRT TºK
Cooling 298
T
CH2
reactants AH , Cp.dT Cp dT
FIL
react
298prod
=
C
products
|
Standard
Reactants 298 Products
reaction
K
,
298 298
K
ΔΗ
°
Fig
on
temperature
of
of
6.8 Effect the heat reaction

.
.
regardless of the path taken . Therefore ,
ΔH R.T ΔΗ , + ΔHR + ΔΗ 2 ( 6.50 )
This equation may be used to calculate the heat of reaction at any

temperature , provided that heat - capacity data are available . A slight
simplification may be made :
298
T
Salon
react
AHRT = dT
AH
dT
206
SA
;
+
+
Cp , 298 CP.prod
or
SCT
AH
dT
CP
AHRT R react 6.51
,
+
;
(
298
)
–
CP.prod
(
The combined heat capacity defined by
of
reactants
is
CP react NiCP reactant
,
i
any reactant similar definition
A
where
ni
of
the number
of
moles
is
.
for the products gives
CP prod niCP product

Σ
,
,
i
Example 6.12 the gas hase reaction
of
Calculate the heat

.
-p
→
H2O C2H5OH
+
C2H4
)g
)g
)g
(
(
at
300
°
.
-10,135
25
at
be
of
The heat
to
Solution reaction
K
298 was found AHR

C
°
.
°
(
cal Example 6.11 Heat apacity data are found Appendix

in
in
G
.
-c
Cp
10-3T
+ + +
28.601
X X
C2H4 2.830 8.726 10-6T2

X
=
H2O CP 10-3T 10-67

x
+
7.256 2.298 0.283

°2
Cp
C2H5OH 6.990 39.741 10-3T 11.926 10-6T2

X
X
-
=
Fig
25
be
The process shown will carried out between 300 and The react
in
6.8
.C
°
.
of
of
ants are mole C2H4 and mole H20 therefore

g
g
1
298 K
°
dt
CP
ΔΗ
SH
dT
+
CP.C2H4 720
,,
573
(
=
° K
:
°
298
K
2.830
7.256
28.60
+
6730 10-31
K
+
-
%
2.298
*
°
(
)
10-6T2 dT
+
0.283
+
8.726
-
]
)
(
30.90 10-3
X
+
10.086 298 573 2982

–
5732
(
(
)
)
2
8.443 10-6
5733
–
2983
)
(
3
6015 cal
-
The sole product C2H5OH

is
573
ΔH
=
2
S293 CP.c.al
on
di
,
573
2009
dt
-T
10
10
PT
+
6.990 39.741 11.926

–
X
X
$
= =
^
-
(
6025 cal
Therefore , AHR ,300°C -6015 + ( -10,135 ) + 6025

= -10,125 cal
The change in the heat of reaction here was very small . It is often more significant .
Equation (6.51 ) may be used to give the same results . Mean heat capacities may be
used instead of the polynomial expressions .
In many cases the reactants and products are at different tempera

tures . The heat of reaction may be calculated by a method similar to
Products
Desired
reaction T2 OK
AHR.
Reactants Heating
products
TºK
.Tz
AH2
dT
ΔΙ
ср
fcporod
=
298
298
Cooling
ΔΗ dT
CP
,
reactants
,
=
react
Reactants Standard reaction Products

298 298
K
K
°
AHA 298
K
°
,
Fig reaction with reactants and products different temperatures

at
of
6.9 Heat
.
.
.Fig
6.9
the
Equation 6.50 holds

as
one discussed above outlined

in
,
)
as .
for this process and AH AH shown Fig 6.10

in
and are defined

1
.
.
,
Example 6.13 the following reaction

of
Calculate the heat

:
.
12
,200 O2 H2O 9,700

+
200
(g
H
C
0
,
,
°
°
)
)
-
(9
This the combustion reaction for hydrogen

or
Solution the formation reaction

is
.
for
57,798 cal mole

At
gaseous atm from Appendix

25
water
–
AHR
C
.
/
1
,
I,
°
.
Using polynomial expressions for

:cp
METHOD
1.
298
K
°
:cp.u
AH
at
54730k Yscp.o.
6.947 +
- :
° K
=
298 K 3.102
6.78
-0.200 10-3T
+
+
(
02
**
473
K
6.148
2
+
:)
°
(
(
0.923
0.481
+
223
DT
eta
2
10
]
(
)
-
-1840 cal
=
973
K
°
dT
AH
,2
=
298
12000K CP.1,0
°
973
K °
ek K
Soos
dT
dt
298 10-57 10-6T

x
x
+
7.256 2.298 0.283

°
5970 cal
Therefore
AHR AH , + AHR + AH ,
– 1840 –- 57,798 + 5970
- - 53,668 cal
METHOD 2. Using mean Cp data from Appendix G.2 :
ΔΗ , ( CP, Hz + 12 Tp.02) (25 200 ° C )

(6.95 + 7.17 /2 ) (25 – 200 °C )
- 1840 cal
TP.H , and Tp.0 , were read from Appendix G.2 at 200 ° C.
ΔΗ 2 CP.4,0 (700 – 25 )
(8.83 ) (700 – 25 )
5960 cal
Tp.4,0 was found on Appendix G.2 at 700 ° C. Adding gives
AHR - 1840 57,798 + 5960

- 53,680 cal .
Using mean heat capacities introduces the error of reading graphical data .
Adiabatic Reactions. Some industrial reactors are adiabatic . No

heat is added or removed from the reactants and products . For example ,
the heat released in an exothermic reaction would heat up the products,
because it is not removed from the reactor by a cooling medium . Equa
tion ( 6.50 ) may be used to describe the process .
ΔH R = AH + AHR + AH ,
For an adiabatic reaction , AH r = 0, so that
AH2 =
– ΔΗ , AHR ( 6.52 )
Effect of Pressure on the Heat of Reaction . The effect of pressure on

a heat of reaction may be analyzed in a manner similar to that for temper
ature effects . Figure 6.10 outlines the procedure . The enthalpy of
reaction at pressure P is
P
["COM
(4
AH
ΔH R,P = ΔΗ , +
+ ΔΗ R + AH2
+ ΔΗ2
L. ), - ( :)) ]ar
ӘН ,prod ,
aH react
AHR + ap dP (6.58 )
ӘР T
ah
of the
)aP
To evaluate effect quantitatively necessary

to
know
it
is
,
/
(
r.
an
The enthalpy ideal gas independent pressure and

of
is
=
0
H
.T
P
(
moderate pressures deviate only slightly from the ideal and

is at
Real gases
,
aP
ah negligible The enthalpy change liquids and solids with

of
,
/
(
.
)
pressure negligibly small Therefore for engineering calculations

at
is
,
.
Reactants ΔΗR.P Products
Patm P atm
/*(
ӘН.react P ән ,
ΔΗ, =
prod
Sie ap dP AH2 =
=
ap dP
Reactants Standard reaction Products

0
1 atm ΔΗ'R 1 atm
Fig . 6.10 . Effect of pressure on the heat of reaction .
moderate pressures ,
ΔH R ,P AHR (6.54 )
At high pressures , the variation in enthalpy must be taken into account ,

and ( aH / aP ) t must be calculated or determined experimentally .
The practicing engineer often meets reactions involving both high
pressures and high temperatures . In these cases corrections must be
made both for the effect of temperature and for the effect of pressure
on the heat of reaction . The procedure would be exactly as described
above , and Eq . ( 6.53 ) would apply except that AH Rt would be used
rather than AHR .
INDUSTRIAL REACTIONS
The calculation of the energy balance in an industrial chemical process

may be complicated by several factors . There may be an excess of
reactants ; the reactants may be impure ; the reaction may not go to
completion because of an equilibrium or a slow rate ; several reactions
may occur simultaneously . All these factors affect the energy balance
and must be taken into account . In writing an energy balance , it is
often convenient to evaluate the absolute enthalpy H of a stream . This
may be done by choosing an arbitrary state where H =: 0. It is con
venient to choose the standard state of 25 ° C and 1 atm with the enthalpy
of pure elements equal to zero . The following example will illustrate
an energy balance around a simple chemical process .
Example 6.14 . In the following reforming process , determine the rate of heat addi
tion to the reactors , the rate of heat removal from the cooler -condenser , and the work
added at the pump and compressor . The fresh feed may be considered to be pure
cyclohexane . * The molar ratio of hydrogen to cyclohexane entering the preheater is
areare
10 : 1. The yields of benzene and methylcyclopentane in the three -reactor system
approximately the equilibrium values The following data
at
these conditions
.
available
.
Pabs Composition Other data
,
Stream
F
,
°
T
sq
lbs mole and remarks
%
in
.
/
Fresh feed 77 14.7 Flow rate
%
100 C6H12
,
5,000 gal
hr
/
Preheater feed
% %
100 610 9.1 C6H12
90.9 H2
Reactor feed 950 610
Reactor effluent 900 590
Cooler condenser effluent 77 590 All cyclohexane
-
,
methylcyclo
pentane and
,
benzene are
liquid
Separator gas 77 590 Essentially pure
H
,
Separator liquid 77 590 Benzene ,

cyclo
hexane methyl
,
cyclopentane
Fig E6.14a
in
The process outlined

is
-Ws
i,
H2
H2
recycle
Recycle
Hą
product
compressor
Reactors
-W
950 Cooler
F
in lb °
Preheater condenser
600
/
Fresh sq
.
Feed
feed -Q3
pump
109
Separator
Benzene product
with methylcyclopentane
(
'
and cyclohexane
)
Fig E6.14a Reforming process

.
de
as
Actually the feed reforming plant complex mixture

an
industrial
in
is
a
,
*
scribed Chap
in
.2
.
Solution . The energy balance will be only approximate , because data at 600 lbs /
sq in . for the heat capacities and heats of reaction are not available . However , the
error in using data for atmospheric pressure at 600 lbs / sq in . will be small , and the
results will be approximately correct .
MASS BALANCE . It is necessary to make a mass balance to determine the compo
sitions of reactor effluent and cooler - condenser effluent . First , the flow rates of hydro
gen and cyclohexane are calculated .
Cyclohexane : density S 0.78 g / ml , molecular weight 84
( 5,000 gal / hr ) (0.78 X 62.4 lbm / cu ft )
Flow rate of cyclohexane to the reactor 7.48 gal / cu ft
32,500 lb m// hr
Flow rate of hydrogen to the reactor

( 32,500 /
lbm hr ) ( 10 lb moles H2 / lb mole C6H12 ) (2 lbm / lb mole H2 )
84 lbm / lb mole C6H12
= 7,740 lbm hr /
In Example 5.17 , it was shown that at equilibrium both benzene and methylcyclo
pentane are produced and some cyclohexane remains . Using the procedure of Exam
a basis of 1 lb mole cyclohexane and 10 lb moles H2 gives the equilibrium
ple 5.17 with a
composition :
3
nu ,nC6H6 14.7
ncaH ( En )
пMcP 1 nC6H6
and = 12 nC6H12
nC H12 13
пMCP
12 ( 1 – nC6H6)
mHg = 10 + 3nC6H6
13
En = nmCP + nC6H12 + NH2 + nC6H6
= 11 + 3nC6H6
These equations are substituted into the original expression :

( 10 + 3nC6H6) 3nC6H6
14.7
[( 1 – /
nC6H6) 13 ]( 11 + 3nC6H6) 3
Solving gives nC6H16 0.53 nC6H12 0.036
nMCP = 0.434 nH2 11.59
Now the flow rate of reactor effluent is calculated :
Cyclohexane flow
(0.036 mole C6H12 out ) ( 32,500 lbm hr ) / 1,175 lbm hr /
1.0 mole C6H12 in
Benzene flow
(0.53 mole C6H6 out ) (78 lbm lb mole / C6H6 ) ( 32,500 lbm /hr )
1.0
12
84
mole C6H
in
lb
( lbm mole C6H12

/
)
(
)
hr
16,000 lbm
/
Similarly
,
Hydrogen flow = 8,970 lbm

hr
hr
Methylcyclopentane flow 14,100 lbm

=
/
/
Total flow
hr
1,175 16,000 14,100 8,970 40,245 lbm

+
+
+
This checks the total flow rate into the reactor the cooler condenser everything
In
-
.
but the hydrogen condensed

is
hr
Flow rate liquid product 14,100 31,275 lbm

of
1,175 16,000
+
+
recycle hydrogen
hr
Flow rate
of
7,740 lbm
/
hr
Flow rate product hydrogen 1,230 lbm

of
8,970 7,740
/
–
Energy balances can now

be
on
made the desired units

.
Solution . The energy balance will be only approximate , because data at 600 lbs /
sq in . for the heat capacities and heats of reaction are not available . However , the
error in using data for atmospheric pressure at 600 lbs / sq in . will be small , and the
results will be approximately correct .
MASS BALANCE . It is necessary to make a mass balance to determine the compo
sitions of reactor effluent and cooler - condenser effluent . First , the flow rates of hydro
gen and cyclohexane are calculated .
Cyclohexane : density S 0.78 g / ml , molecular weight 84
( 5,000 gal / hr ) (0.78 X 62.4 lbm / cu ft )
Flow rate of cyclohexane to the reactor 7.48 gal / cu ft
32,500 lb m// hr
Flow rate of hydrogen to the reactor

( 32,500 /
lbm hr ) ( 10 lb moles H2 / lb mole C6H12 ) (2 lbm / lb mole H2 )
84 lbm / lb mole C6H12
= 7,740 lbm hr /
In Example 5.17 , it was shown that at equilibrium both benzene and methylcyclo
pentane are produced and some cyclohexane remains . Using the procedure of Exam
a basis of 1 lb mole cyclohexane and 10 lb moles H2 gives the equilibrium
ple 5.17 with a
composition :
3
nu ,nC6H6 14.7
ncaH ( En )
пMcP 1 nC6H6
and = 12 nC6H12
nC H12 13
пMCP
12 ( 1 – nC6H6)
mHg = 10 + 3nC6H6
13
En = nmCP + nC6H12 + NH2 + nC6H6
= 11 + 3nC6H6
These equations are substituted into the original expression :

( 10 + 3nC6H6) 3nC6H6
14.7
[( 1 – /
nC6H6) 13 ]( 11 + 3nC6H6) 3
Solving gives nC6H16 0.53 nC6H12 0.036
nMCP = 0.434 nH2 11.59
Now the flow rate of reactor effluent is calculated :
Cyclohexane flow
(0.036 mole C6H12 out ) ( 32,500 lbm hr ) / 1,175 lbm hr /
1.0 mole C6H12 in
Benzene flow
(0.53 mole C6H6 out ) (78 lbm lb mole / C6H6 ) ( 32,500 lbm /hr )
1.0
12
84
mole C6H
in
lb
( lbm mole C6H12

/
)
(
)
hr
16,000 lbm
/
Similarly
,
Hydrogen flow = 8,970 lbm

hr
hr
Methylcyclopentane flow 14,100 lbm

=
/
/
Total flow
hr
1,175 16,000 14,100 8,970 40,245 lbm

+
+
+
This checks the total flow rate into the reactor the cooler condenser everything
In
-
.
but the hydrogen condensed

is
hr
Flow rate liquid product 14,100 31,275 lbm

of
1,175 16,000
+
+
recycle hydrogen
hr
Flow rate
of
7,740 lbm
/
hr
Flow rate product hydrogen 1,230 lbm

of
8,970 7,740
/
–
Energy balances can now

be
on
made the desired units

.
Nonreacting gas
950 ° F
7,740 lb H2
1,175 lb C6H12
ΔΗ , Nonreacting gas
900 °F
Reacting gas
7,740 lb H2
950 °F
1,175 lb CoH 12
31,325 lb C6H12
ΔΗ ,
Products
900 °F
16,000 lb CHE
ΔΗ ,
1,230 lb H2
14,100 lb MCP
ΔΗ ,
Reacting gas Products

77 ° F ( 25 °C ) 77 ° F ( 25 ° C )
31,325 lb CH12 AHR.COM
16,000 lb CoHo
1,230 lb H2
AH R,MCP 14,100 lb MCP
Fig . E6.146 . Reaction scheme for the reforming process heat balance .
Fig . E6.146 .The calculation may be carried out in two ways . First , AH , AH , +
298
AHR , that the unreacted materials are simply cooled from 950
so
AH2
+
to
900
,
F
°
tal
AH2 Then AHt ΔΗ take the reacting

to
The second method

+
ΔΗΛ
F, .4
is
(
).
and unreacting gas from 950 carry out the reaction and then heat the prod
77
° to
be ,
to
ucts and unreacted gas 900 The latter method will used
F
.
AHH
+
AH2 AHC6H12
° ,
537
TºR TºR
SHu
ΔΗ
1K dT
X
6.947
+
–
0.200
X
10-3 0.481 10-6

Savoer
.
6.947 1.8
= =
1.8
;
]
(
)'
–6130 cal mole

/g
454 7740
-6130 cal Btu
hr
mole 252
x
-4.27 107
g
/
(
Similarly for cyclohexane

,
40,190 cal mole

—
AHC6H12
g
/
454 32,500
-40,190 cal -2.81
hr
mole 107 Btu

=
X
/g
/
(
252 84
Then
AH –4.27 -2.81 Btu
hr
x
107
X
X
=
7.08
–
107 10²
,
/
(
For heating the products plus the unreacted gases

:
ΔΗ AHH
+
AHMCP
+
AHC6H12 AHC6H6
3
Each term
is
evaluated
:
ału
1360° R
AHH dT
CP
:
5720 cal mole

=
H
,
/g
(
,
,
537
R
°
hr
5720 cal mole 454/252 ,970 lbm

g
AHA
(
)
(
/
)
(8
,
lb
lbm mole H2
2
/ hr
107 Btu
X
4.62
/
-
By a similar procedure for benzene , cyclohexane , and methylcyclopentane ,
AHC6H6 = 1.0 X 10 Btu / hr

AHCHE 0.097 X 107 Btu hr /
AHMCP = 1.70 X 107 Btu / hr
Therefore ,
ΔΗ3 = 4.62 X 107 + 1.0 X 107 + 0.097 X 107 + 1.70 X 107
- 7.42 X 107 Btu / hr
The enthalpy increase for the whole process is equal to the heat added to the reactor Q2.
Q2 AH tot
ΔΗ2 + ΔH R.CAHA + ΔHMCP + ΔΗ3
-7.08 X 107 + 2.40 X 107 + 0.119 X 107 + 7.42 X 107
= 2.86 x 107 Btu /hr
ENERGY BALANCE Cooler Condenser Benzene methylcyclopentane and cyclo
,
-
:
.
hexane are condensed the cooler condenser and hydrogen cooled For purposes
in
is
,
-
.
calculation each component will considered separately
be
of
.
the dew point and partially condensed
to
is as
Benzene The gas cooled the tem
is
is
:
perature drops below the dew point until final temperature
77
of
reached
F
a
be is .
However for purposes
to
assume that the gas
of
calculation more convenient

is
it
to ,
vaporization may
77
77
of
cooled and then condensed The latent heat
at
F
F
°
°
.
H.
obtained from Appendix

537
R
°
gas
Cooling -27,110 cal

H6
ΔΗ mole
=
CP.C
d
g
&
/
1360
:
R
°
Condensing ΔΗ -8090 cal Appendix

–
mole
H
/g
.
:
Therefore AH C6H6 -27,110 -8090 -35,200 cal mole

-
+
/g
,
)
(
454 16,000
35,200
-
252 78
Btu
hr
1.30 107
–
X
=
Cyclohexane
to
The calculation similar that for benzene

is
:
.
gas
Cooling 38,500 cal mole

/g
H
-
:
Condensing -AH –7895 cal mole

/g
:
454 1175
AHC6H12 -38,500 7895
)
252 84
(
-0.12 Btu
hr
107
X
=
Methylcyclopentane
:
gas
= =
Cooling AH 56,580 cal mole

-
g
g /
:
Condensing ΔΗ
–
7580 cal mole

–
.
:
454 14,100
AHMCP -56,580 7560
–
84
)
(
252
-1.94 Btu
hr
X
107
/
Hydrogen
:
Cooling = -4.62 Btu

hr
ΔΗ
as
calculated earlier
X
107
H
Η
/
,
:
Finally
,
AH total AHMCP AHH

+
+
X X+
Q
AHC6H6 AHC6H12
,
:
-1.30 107
X
4.62
X
1.94 107
X
107 0.12 107

-7.98 Btu
hr
107
/
-Q3 107 Btu

hr
The heat removed from the cooler condenser 7.98

X
-
is
/
-
.
Btu
-Ws, 1 = 135,000
hr
/
H2
Hą
recycle
Recycle
Hą product
lbm
compressor 7,740
hr
/
hr
1.230 lbm
/
-Q
hr
7.98 107 Btu
X
2=
/
-Ws
,
7,400 Btu Reactors

hr
/
950 Cooler
F
in lb °
Preheater
condenser
/
600
sq
.
Fresh feed Feed
Qi
32,500 pump
3.88 X10
Ibhr
?
=
Qz
m
hr
Btu
/
Separator
2.86 x10
?
hr
Btu
/
Benzene methylcyclopentane
-
product with cyclohexane
)
31,275.1bm
hr
/
Fig E6.14c Quantitative flow sheet for reforming process
.
.
ENERGY BALANCE Hydrogen Recycle Compressor
to
of
interest calculate the
It
is
.
:
energy added the hydrogen compression has been shown for flow process
in
It
to
a
.
that the isothermal shaft work for an ideal gas

is
P2
dP RT P2
In
V
W5,1
Pi
SA
The hydrogen temperature compression The energy added may increase

89
on
F
is
.
the
temperature but the gas cooled between compressor stages and the compression
is
,
the inlet and outlet temperatures

be
be
W to
at
may the average

of
assumed isothermal
.
3,1
-
= 2.3 log
61
90
1.987 Btu mole

lb
549
R
R
/
°
(
)
(
)
(
)
35
Btu mole
lb
/
=
hr
Btu 53.1 hp
35
77402 135,000
/
(
)
(
Cyclohexane Feed Pump that liquid cyclo

be
will
It
ENERGY BALANCE assumed

:
incompressible
so
hexane that constant

is
is
Ő
,
.
1
1
V
cu
ft
62.3
X
0.021 lbm
=
0.78
р
-W
5,2
VAP
sq
in./sq
sq
lbs
cu
in
ft
ft
0.021 lbm 600 14.7 144

/
(
)
(
)
(
)
/
177 lbs lbm

ft
-
Btu
1
hr
lbs 1bm 32,500 lbm

ft
177
/
/
-
(
)
(
778 lbs
ft
-
= 7400 Btu 2.91 hp

hr
=
=
/
.Fig
for
E6.14c shows the resulting quantitative flow sheet the reforming process
.
DIFFERENTIAL ENERGY BALANCES
energy balances may describe systems

be
written
to
Differential
in
energy input output varies with time The energy

or
of
which the rate

.
6.1
based upon Eq
all
energy terms related

to
balance written include

is
),
(
.
the system To illustrate the general method differential energy

to
a
,
.
balance will be written around the stirred -tank reactor shown in Fig . 6.11 .
An energy balance may be written in a similar manner for any physical
system .
The stirred -tank reactor operates at constant pressure , so that the
various energy terms may be expressed as enthalpies . The process
streams entering and leaving have masses of mı and me and enthalpies
of H and H2 , respectively . The reaction will proceed at a rater and
will absorb AHR units of heat per mole of product . The heat of reaction
for
AH R is an output term for an endothermic reaction and an input
an
R
Stirred tank reactors often have heating
or
exothermic reaction cooling
-
.
Fig input
for
coils As shown heat term representing
in
6.11
is
q
,
,
-
.
.
H2 m2
lb hr
1b hr
lb
lb
H m
/
, ,
/
Btu Btu
/
/
Ib
moles
r
hr
lb
MIb Btu
A
HR
lb
mole
Btu
Btu
/lb
hr
-
-9 Btu hr
,
,
9
/
Fig 6.11 Stirred tank reactor
-
.
example steam eating coil The heat loss accounts for heat lost
92
—
a
,
.
-h
through the walls

to
the reactor the atmosphere The differential

of
energy balance
do
written for time interval

is
Input output
+
accumulation 6.1
(
)
rM AHR MH
de
de
de
de
do
91
42
+
miH m2H
-
=
6.55
+
d
,
MH
MAHR
d
-92
q1
)
qı
miH
+
m2H 6.56
=
m
)
(
do
= rate heat input Btu

qı
where
of
hr
q1
=
hr /
mi mass input rate lbm

= =
/
,
enthalpy input stream Btu

of
=
lbm
H
/
,
-92 heat output Btu

hr
of
rate
= = = = = =
/
,
m2 output
hr
mass rate lbm

т
/
,
H2 enthalpy output stream Btu

H
of
lbm
,
/
,
moles product
hr
lb
of
lb
rate reaction
p
/
,
M any time lbm

lb at
total mass
in
reactor
,
=
AHR reaction Btu
of
heat mole
/
,
H
=
enthalpy Btu lbm

of
mass
/
,
hr
time
=
0
,
The accumulation term in Eq . ( 6.55 ) , d ( MH ) , is simply the differential

increase in total enthalpy of the mass in the reactor over the time interval
do . If the mass M in the reactor is a constant , the accumulation becomes
MdH . The rate of heat input qı is proportional to the temperature
gradient ( T ; –
T ) and to the area for heat transfer A1 :
91 = U , A1 ( T; – T) ( 6.57 )
where Btu / hr sq ft ° F
U1 = heat - transfer coefficient ,
A heat - transfer area , sq ft
T = temperature of fluid in reactor , ° F
Ti = temperature of heating or cooling fluid , ° F
The heat -transfer coefficient U may be determined from experimental
data or from empirical correlations . It depends on the reactor fluid ,
on the heating or cooling fluid , on the agitation in the reactor , and on the
material and thickness of the reactor wall . The magnitude and meaning
of each of these effects is considered in the unit operation of heat transfer .
The heat - loss term may be expressed by
-92 = U , A2T - T. ) ( 6.58 )
where U, = heat -transfer coefficient

A2heat - transfer area
T
= reactor fluid temperature
T , = temperature of surroundings
The enthalpy terms H and H , may be related to the temperature
by Hi . ( Ti1
= čp 1 – T ) ( 6.59 )
and H2 = 7p , ( T, - Tr ) ( 6.60 )
where Ti
= temperature of input stream
T2 temperature of output stream ( often equal to tank fluid
temperature T )
T , = arbitrary reference temperature for evaluating enthalpies
Similarly , the accumulation term in Eq . ( 6.55 ) may be written in terms
of temperature ,
d ( MH ) = d [ MẼP ( T - T6 ) ] (6.61 )
where the initial temperature T , is chosen as a reference . The general

differential energy balance [ Eq. ( 6.55 ) ] may be applied to many physical
systems. For example , if there is no reaction the term for the heat of
reaction drops out , and there remains an expression for the unsteady
state heating or cooling of a fluid . If mi
mı = 0 and m2 = 0 , the system
becomes a batch reactor or heater . There is no need to remember Eq .
for
( 6.55 ) or ( 6.56 ) . The required expression may be developed each

necessary remember only the form the indi
of
to
It
new situation
is
.
vidual terms . The following examples will illustrate the utility of the
differential energy balance .
Example 6.16 . A vertical cylindrical tank is full of a solution of Co60 which is too
radioactive to discard . The radioactive decay of Co60 releases energy which heats
up the solution . The warm solution loses heat through the walls of the tank to the
surroundings . The solution in the tank is stirred to give a uniform temperature , and
it releases heat at the rate of 100 Btu / hr cu ft . The following data are available
Tank : 10 ft high by 6 ft in diameter resting on the ground

Surroundings temperature T2 70 °F
Initial solution temperature To 70 °F
Heat capacity of solution cp = 1.1 Btu / lbm ° F
Density of solutions 65 lbm / cu ft
Average heat-transfer coefficient to the surroundings at the tank sides and top .
U2 =
1.2 Btu / hr sq ft °F
a . What will be the temperature of the solution in the tank 1 day after it is filled ?
b. What is the maximum temperature the solution will attain ?
Solution . a . The heat input by radioactive decay is 100 Btu / hr cu ft ; the output
by heat loss is –
92 U2A2 ( T T2 ) ; and the rate of accumulation caused by the heat
ing up of the solution is Mcp (dT /do) . By Eq . (6.1 )
dT
V X 100 Btu / hr cu ft = U2A2 ( T T2 ) + Mcp
do
762
V 10 = 283 cu ft
4
62
A2 ( 10 ) (76 ) + 218 sq ft
4
M = 283 X 65 18,400 lb
Then
(283 cu ft ) ( 100 Btu /hr cu ft ) ( 1.2 Btu / hr sq ft °F ) (218 sq ft ) ( T – 70 °F )

d
+ ( 18,400 lbm ) ( 1.1 Btu / lbm °F ) de
dT
28,300 Btu / hr 262 ( T 70 ) Btu / hr + 20,200 do Btu / hr
Separating variables and integrating from 0 = 0, T Toto 6 0, T = T gives
0 77 In
178 – T.
178 – T
Solving with 24 hr and To = 70 °F gives T 101 °F .
b. At the maximum temperature , dT /do = 0 , and the rate of accumulation is zero.
Then
Input =
= output
28,300 Btu / hr 262 ( T – 70 ) Btu / hr
T 178 ° F
Example 6.16 . Sulfuric acid is to be neutralized with an aqueous sodium hydroxide

solution in a stirred tank where the heat of reaction is removed by a cooling co l.
lb.me/
200 lbm of an aqueous 25 per cent sulfuric acid solution at 80 ° F is charged to the tank.
The 10 per cent sodium hydroxide solution at 70 °F is then added at the rate of 20
min until neutralization is complete . The heat-transfer coefficient for the cooling
/ hr sq ft °F , and the cooling area is 2.0 sq ft . The average cooling -water
coils is 95 Btu
of all
temperature is 60 ° F . Assuming that the heat capacity of
at
solutions constant
is
1.0 Btu lbm the temperature
of
determine the variation the solution with time
/
F,
°
.
This semibatch operation since the acid charged
is as
Solution batch and
is
is
a
a
,
is .
no
added continuously with mass output The reaction very fast
so
the base
,
.
that the sodium hydroxide reacts
as
as
fast added and does not accumulate
is
it
.
MASS BALANCE Input 3 output accumulation
+
:
Total mass
+
mi do dM
=
0
:
dM
mi
=
de
M
M
at
Integrating with
=
0
0,
0,
M Mo mio
+
=
NaOH 1X1do
m
TM accumulation
+
do
0
:
0
(
)
mi
20
60
0.10 = 120 hr
1
?
so
that =
(
)
(
)
(
)
-1
M M
r
This expression states simply that the rate equal
to
of
of
reaction the rate addition is
NaOH for this very fast reaction
of
First
to
necessary
of
ENERGY BALANCE calculate the heat reaction From
is
it
:
.
Appendix I.2 and Fig 6.5 for per cent H2SO4
25
H2O
in
,
,
.
nh20
AHF 193,910 16,500 210,400 cal mole for 16.3
=
-
/g
2804
n
AHF -68,317 cal mole for H2O

g
)1
(
/
AH 330,900 500 -331,400 cal mole for dilute Na2SO4

=
–
/g
)aq
)aq
)aq
Na2SO4
→
2NaOH
+ +
H2SO Na280 2H2O

(1
1
(
)
.
AHR -331,400 –68,317 21-112,300 -210,400

–
–
2
(
-33,000 cal mole Na2SO4

/g
this problem are dilute

so
of
of
The solutions that use this heat reaction value for

in
be ,
-
-
of
infinitely dilute Na2SO4 solutions will approximately correct The heat reaction
.
per pound NaOH

of
is
-33,000 454
ΔΗ 743 Btu NaOH
-
lbm
/
40 252
X
2
The energy balance

is
Input output accumulation

- +
do
T1
rMAH
T.
A1
micp Mcp
do
do
T.
-
–-
–
+
–
U
T
T
'R
),
d
(
) ]
-
term may split

be
The accumulation
,
McdT
cp
Mcp
T.
dM
+
-
-
=
T
T
d
((
[
)]
But dM
do
mi
so
=
T.
To
MCp Mcp dT
de
micp
+
T
–
T
d
)]
[
)
To
possible Then with substitution and rearrangement the

to
choose
It
is
,
T,
energy balance becomes
dT
T.
M.
cp
A1
T.
micp
+
MIXI AHR
+
m10
–
T
–
0
U
=
T,
,
(
do
Available numerical values are :
mi = 1,200 lbm / hr X1 = 0.10

Ср 1.0 Btu / lbm °F ΔΗ S -
743 Btu /lbm
U 95 Btu / hr sq ft °F Мо 200 lbm
A1 2.0 sq ft X0 = 0.25 ( H2SO4 )
T. 60 °F T. 80 °F
Substitution of these values into the energy balance gives
de d .
200 + 12000 187,500 1390T
Integrating between the limits T To 80 °F at a = 0 and T at any value of 0
200 + 12000 187,500 – 1390 (80 )

200 - 187,500 1390T
Rearranging gives
55.0
T 135.0 -
(1)
1 + 60
Initially
all
This expression holds until the sulfuric acid has been neutralized
,
.
200 0.25
(
)
(
)
Moles H2SO4 0.51
98
Moles NaOH needed 1.02
=
0.51
2
(
)
) 40
= 1.02
Time required 20.4 min
(
( )
(
)
Of
=
,
20
0.1
(
0.34 hr
=
no
the acid will cool because reaction supplies energy

hr
is of
After 0.34 heat The

,
.
mi
longer needed
no
be
NaOH stream will turned off because The energy

it
0
)
(
.
balance then becomes
Input = output accumulation
+
do dt
A1
T2
T.
Mcp
U
+
–
=
O
but M
+
Mo mios 608 lbm

+
200 1200 0.34

(
Substituting numerical values into the energy balance gives
dT
–
0.312do
60
T
-
gives
Oc
Integrating any value

at
at
of
between and
T
T
=
T,
Ts 60
In 0.03120c
=
2
(
)
T
60
.Eq
Ts
where temperature when neutralization complete calculated from

is
(1
)
(
at
hr
os
0.34 116.9
)F
T's
,
°
0c
05
time since neutralization complete

is
)
(
Figure E6.16 shows the variation temperature with time Curve

of
shows that
b a
.
the temperature increases with time until the acid neutralized Curve shows that
is
.
off
the solution cools after neutralization approaching the coolant temperature

,
asymptotically
.
120
110
( a)
100
90
T, OF (6)
80
70
60
0.1 0.2 0.3 0 4 8 12
O, hr oc, hr
Fig . E6.16 . Solution to Example 6.16 .
EQUIVALENCE OF MASS AND ENERGY
On an atomic and subatomic scale , it is difficult to distinguish between

mass and energy . The interaction of atomic particles such as protons ,
neutrons and electrons may result in a conversion of mass to energy ,
,
and the reverse . In a nuclear reaction the nucleus of the atom under
goes rearrangement as it interacts with atomic particles , releasing a large
quantity of energy and perceptibly losing mass . Mass is also converted
into energy in a chemical reaction , which involves the rearrangement of
electrons outside the nucleus . However , the mass change is too small
to be detectable . An exothermic chemical reaction may be thought of
as one in which mass is converted into energy . In an endothermic
reaction , energy is converted into mass . However , the effects are too
to disrupt the mass balance in
all
chemical processes Even

in
small
.
compared
to
nuclear reactions the mass change relatively small the

is
,
total nuclear mass

.
The Einstein equation relates mass energy

to
ΔΕ Amc2 6.62
=
-
)
(
ΔΕ
sq
where energy
=
increase ergs cm
of in in
sec2
/
,
)
-
Am decrease
-
mass
g
,
= velocity light
cm
X
sec
=
1010
3
c
/
Example 6.17 . 1 lbm of U235 releases 3.6 X 1010 Btu of energy when it undergoes
off
on
nuclear fission . One type of coal gives 12,000 Btu lbm burning Calculate
.
energy
be to
the mass converted
to in
each case
.
will convert Eq 6.62 English units
to
Solution useful
It
)
.
.
Btu
sq
or
1.055 1010 ergs cm sec2
/
,
454
g
lbm
1
Uranium
:
ΔΕ
sq
Btu Btu
X
3.6 1010 1.055 1010 cm sec2
/
(
)
(
)
-
Δm 1bm
?2
(
)
1010 cm sec
lb
X
454
/g
c
?
/
(
)
(
)
0.00093 lbm
=
0.1
per cent even with this
of
Therefore the loss the uranium less than
of in
mass
is
,
,
tremendous release energy
.
Coal
:
12,000 Btu 1.055 1010
X
-Am
(
)
(
X
=
3.1 10-10 lbm
=
1010 454
X
(3
)2
(
)
This very small undetectable
in
loss mass
is
PROBLEMS
enthalpy and internal energy for benzene
70
at
6.1 Calculate the increase
in
in
F
°
.
between points and the system shown Fig P6.1 Calculate W.

in
in
1
2 Reactor
/ 60
Benzene gal min

,
sq
21 AqP1
14.7
sq lb
in
= = =
lbe
.
sq
22 Az Pz
in
0.2 400
= = =
ft
ft /
.
sq
0.3
ft
0
25
ft
1,000 Btu min

=
Q
Heater
10m
Ws
-50
-lb
=
ft
Fig P6.1 Flow system

.
.
sq
6.2
sq
the outlet pressure

80
pump
13
The inlet pressure lbs

70 to
in
lbs
in
.;
is
is
° a
.
.
/gal
the
through pump
20
at
of
The flow rate water min The inlet and outlet

is
F
.
W.
W
pipes are the same size and elevation Calculate and assuming that water
is
,
.
incompressible
.
con
compressor operates that isothermal reversible compression occurs

so
6.3
A
.
tinuously gas being compressed obeys the equation

of
the state
If
.
PŨ
T
RT
b
(
)
++
==
+
(
)
a
ÝT
V2
100
develop determine the work required

to
to
calculational flow chart compress

a
standard cubic feet per minute of this gas from P , and Ti to P 2

, and Tı . Assume that
the functions a ( T ) and b ( T ) are known at Tı .
6.4 . Helium is heated in a constant volume of 1 cu ft from 70 ° F and 1 atm to 500 °F .
Calculate Qv , AE , and AH , assuming ideal - gas behavior .
6.5 . Helium is heated at a constant pressure of 1 atm from an original volume of
1 cu ft at 70 °F to 500 ° F.
Calculate QP , AE , and AH , assuming that helium behaves
like an ideal gas .
Liquid
its
from 180 °F to 80 ° F by transferring heat cooling
to
6.6 . benzene is cooled
heat exchanger The cooling water changes temperature from
60
to
water
in
in
F
a
°
of .
For flow rate calculate the cooling water flow
hr
12,500 lbm
of
120 benzene
.F
,
°
-
rate
.
of for
6.7
Develop computer program calculating the final temperature resulting

a
.
from the addition fixed quantity The gas has heat capacity
of
to
heat gas
a
a
.
by
temperature the equation

to
which related
is
Cp
bT
+
+
cT2
=
a
initial gas temperature moles gas heated and quantity

of
of
of
Values heat
a,
b,
c,
,
added are given
as
of
data for each five cases

.
computer program calculate the mean heat capacity

to
as
6.8 Write function
a
a
.
H2
N2
temperature for gas mixture

of
mole mole
3
1
a
6.9 The heat capacity methylcyclopentane vapor has the following values
of
:
.
TºK
K
CP
cal mole
/g
'
,
298 26.24
500 44.94
700 58.68
1000 72.44
.Eq
Develop empirical equation represent these data

an
of
be of
the form
to
6.40
(
.
Heat capacity data for gases may equation
an
of
6.10 correlated with the form

.
с
be
CP
T2
+
=
a
Using the data this equation for methyl

of
Prob evaluate and

in
6.9
a
c
,
a,
b,
.
cyclopentane
.
Determine the average heat capacity between 450 and 600

K
b
°
.
The heat capacity acetaldehyde

of
6.11
is
.
10-3T 10-6 T2
+
CP 3.364 35.722 12.236

x
X
cp
calories per gram mole degree centigrade

K
with
in
and
in
T
°
Calculate the mean heat capacity between 350 and 600

K
a
°
.
.
cp cp
Convert the equation Btu per pound mole degree Rankine

to to
and
in in
in in
C R
b
'
.
Convert the equation and calories per gram mole degree centi
T
c
°
.
grade
.
for
6.12 Develop empirical equation the specific heat

an
of
solid water from the

.
following data
:
CP
C
cal
C
/g
°
°
,
0.0361
- --
250
200 0.156
150 0.246
-100 0.332
-40 0.435
0.492
0
6.13 . Develop an expression for the specific heat of liquid SO2 from the following
data :
T °C CP , cal / g ° C
- 20 0.313
0 0.318
20 0.327
100 0.418
6.14 . Calculate the heat added to 10 lbm of ethane gas in heating it from 77 °F to
300 ° F : (a ) using the empirical equation , (b) using the mean heat capacity .
6.15 . Determine the heat added to 1 lb mole of ammonia vapor in heating it from
800 °F to 1800 °F : (a ) using the empirical equation , (b) using the mean heat capacity .
gas
6.16 . Calculate the heat required to increase the temperature of 1,000 cu ft of
to
at atm and 100 per cent ethane
35
40
1000 The gas contains per cent
F
F
1
°
°
,
per cent
25
propane and butane

n
.
-
,
necessary benzene vapor
hr
to
of
cool and condense 100 lbm
It
at
6.17 atm
is
1
/
.
to
be
at
from 200 45 Calculate the rate which heat must removed Btu per
.F
F
°
(
hour
).
Calculate the heat required heat and vaporize
75
to
ammonia originally
of
6.18 lbm
.
-40
at
and atm The final temperature
70
at
F
atm
1
°
is
F
.
1
°
.
by
vaporization given accurately
of
6.19 The latent heat

is
.
AH dPv dT
-
-
=
y
V
T
,
(
)
(
)
/
where dPv slope dt the vapor pressure curve

of
at
= =
T
/
saturated gas and liquid respectively

of
Vi
molar volumes
V
0 ,,
.
Develop AHy
to
by at
of
Vi
calculational flow chart determine the value where
is
a
negligibly small compared the vapor pressure curve given

Ve
to
is
,
T a
Py
In
+
=
and given by
is
V,
RT
+
V,g
=
c
Assume that and are given

T,
a,
b,
hot summer day theater air conditioner takes outside air

in
at
6.20 On 100
F,
°
a
a
.
wet bulb temperature

of
the water from

. 95
cools this air and condenses much

It
F
°
humidity
70
50
at
The air then reheated and enters the theater

is
it
air F,
°
.
To
air
what temperature must the

be
cooled the conditioner

in
. a
of ?
.
condensed from this stream per 200,000

air
cu
How much water inlet

in ft
is
b
?
air
For the same quantity inlet air how much heat removed the condi
of
is
c
.
tioner
?
For the same quantity

to
inlet air how much heat returned the gas stream

of
is
d
.
the reheat step

in
the
6.21 Ice sublimes when the sun supplies the necessary heat even though
,
.
be
to
temperature well below freezing Estimate the heat that must added sublime
at is
.
of
lbm ice
C
1
0
°
.
dissolving 100 lbm NaOH

of
Determine the heat evolved

° in
in
of
6.22 200 lbm water

.
To what temperature would the solution

77
the temperature
at
constant
F
if
is
= .
CP
heat no heat removed 0.79 Btu lbm

if
solution
.F
of is
/
°
,
an
potassium chloride and 1,000 lbm

of
water are mixed

in
6.23 100 lbm insulated

.
tank . If the temperature of the two constituents was 70 °F , what is the final tempera
ture ? TP.solution 0.88 Btu / lbm ° F .
6.24 . Calculate the final temperature when adding 2,000 lbm of water to 1,000 lbm
of solution containing 70 per cent H2SO4, 30 per cent H2O by weight . Initial tempera
tures are 80 °F . There are no heat losses .
6.26 . An aqueous solution of NaOH is to be concentrated from 10 per cent to
off
60 per cent NaOH by weight , by boiling water
be
Estimate the heat which must
.
added per pound NaOH
of
solution
in
.
Calculate the enthalpy change when 100 lbm per cent H2SO4 per cent
30
at 70
of
6.26
,
at .
per cent H2SO4 per cent H20

70
90
10
H20
of
mixed with 200 lbm
in
160
is
F
F
,
°
°
an insulated tank What the final temperature
is
?
.
by
chemical process spent acid weight temperature
20
In
at
of
93 %
6.27 H2SO
a
at a
,
.
by weight
of
70
at be
of
200 must mixed with fresh acid The
%
H2SO4
F
.F
°
°
product done continuously
50
be
to
H2SO4 concentration and 150 this
If
is
is
.F
°
being concentrated how much cooling must done per
20
be
with tons
hr
of
acid
3
,
the cooling circuit failed what would the maximum temperature attained
be
hour
If
?
by the product acid

?
computer program
be
of to
Write
6.28 determine the heat which must removed
a
.
added when mixing two solutions H2SO isothermally
25
or
at
Include this
in
.C
,
°
program the development empirical equation the data given Fig 6.5 fit
to
an
in
of
.
using empirical equation for the data
an
of
of
6.29 Solve Prob 6.28 but instead
,
.
Fig 6.5 store values regular intervals

at
to
of
of
of
AH the mole ratio water
m
H2SO4
,
.
memory and interpolate linearly between these values the required

to
at
get aHm
in
concentrations
.
6.30 Determine the enthalpy the mixture resulting when 100 lbm per cent
95
of
at of
.
per cent sulfuric acid

50
20
at
of
sulfuric acid 120 mixed with lbm 120 with

is
F
F,
°
°
no heat loss the physical state
of
What the final mixture

is
.
the following
25
at
of
of
6.31 Calculate the heat reaction and atm for each

C
1
°
.
reactions
:
→→
2NaCl 2HCl
+ +
H2SO4 Na2SO4
)g
. a
)g s
s
( (
)
(1 (
) l)
(
)
(
.
2NH3 H2SO4 NH4 2SO4

b
(
+ ) s)
+ + ) aq
)aq
Na2CO3 2HNO3 2NaNO3 H2O CO2

+
+
+ +
)g
c
)aq s
(
(
)
(
.
(l
aq
( Zn
→→ +
CuSO4 ZnSO4 Cu
d
g s
(1 ) s
)g ) (
( (
) ) )
(
g (
)
.
4NH3 4NO 6H2O

+ +
502
)g
( (g
e
(
.
Ca
)aq
CaC2 H2O C2H2 OH

2
s
(
)
(
f.
the following materials

of
of
of
6.32 Calculate the standard heat formation each

.
combustion data
of
from heat
-
-
Acetone
H
Methane CH4
C
O
)g
1
,
,
a
(
)
,
. .g f.
.
Ethanol C2H5OH Urea CH4N20

s
)g (1
b
,
,
(
)
)
.
Acetylene C2H2 Carbon tetrachloride

)]aq 1
h
,
c
(
)
)g (
.
HCl
to
Cl
Styrene C8H3 burns

“
. d
"
,
(
, (
.
Formaldehyde CH2O Carbon disulfide CS2

9
e
(
)
(1
,
i.
the following
25
at
of
of
6.33 Calculate the heat reaction and atm for each

C
1
°
.
reactions
:
HCHO
+
O2
H2O
12
)g
CH2OH
)g
+
)g
)g
(
a
(
(
(
.
HCHO
→
HCOOH
12
02
+
)g
)g
b
)g
.
(
(
Formaldehyde Formic acid

c. C , H16 ( g ) → C , H , (g ) + 4H2 ( g)
Heptane Toluene
d. C6H6 (l ) + HNO : (l ) → C6H ; NO : (l ) + H2O (1)
Benzene Nitrobenzene
e. 4C6H5NO2 ( ) + 9Fe (s) + 4H2O (l ) + 4C6H ; NH , ( ) + 3Fe3O4 (s)
Nitrobenzene Aniline
f. C2H4 ( g ) + Cl2 (g ) C2H4Cl2 (1)
Ethylene Ethylene dichloride
g . CO (g ) + 2H2 (g ) CH ,OHg)
Methyl alcohol
h. C2H2 ( g ) + H2O ( g ) + CH3CHO ( g)
Acetylene Acetaldehyde
i. C2H , OH (I ) + CH3COOH ( ) + CH3COOC2H5 (1) + H2O (1)
Ethyl Acetic acid Ethyl acetate
alcohol
6.34 . Calculate the heat of the following reaction at 600 ° C and 1 atm :
C , H16 (g ) → C , H2
C (g ) + 4H2 (g )
Heptane Toluene
6.35 . Calculate the heat of reaction at 900 °C for
C (s ) + H2O ( g ) → CO ( g ) + H2 (g )
6.36 . In 1951 some 840,000 tons of carbon black were produced in this country .
Three - quarters of this was compounded with rubber , thus boosting tire life by a
factor of ten . About half of the carbon black is made from fuel
oil
by the furnace
by
process the other half from natural gas the older channel process
,
.
oil
assumed composition CnH2n

In
in
burned
of
the furnace process fuel about

is
60
In the burner
is air
%
theoretically required for complete combustion
of
half the
.
the remainder going

to
byto
The gases
of
the fed converted free CO and CO2

C
C
,
and are quenched spraying water originally

at
to
leave the furnace 2600 550

F
F
°
is °
(
by
at
100 into the gas stream The carbon black then removed electrostatic
F
°
)
% are
, off
precipitation and wet scrubbing and the

to
gases sent the stack These

29 ,
the N2
H2
off ases analyze 7.7 vol CO2 6.5 vol CO and the remainder
%
vol
%
,
,
-g
air
from the used assumed bone dry and H20 partly from combustion and
,
(
remainder from quench The collected carbon black pelletized before sale
is
.
for .
the requirement quench

of
the carbon black formed collected what

If
100
is
is
,
gallons per ton black produced

of
water
in
6.37 Urea very valuable commercial fertilizer made

in
It
is
enormous
is
a
.
.
by
tonnages 400 atm pressure

at
of
the reaction 200 NH3 and CO2 The reactions

C
,
°
are
:
=
+
CO2 2NH3 NH4CO2NH2 AHR 67,000 Btu mole

lb
-
Ammonium carbamate
NH CONH2
-
NHẠCONH4 +18,000 Btu

lb
H2O ΔΗ mole
+
)g
,
/
(
Urea
25
of
of
of
Determine the heat combustion ammonium carbamate and urea

at
to
C
°
give standardized combustion products

.
6.38. Consider the absorption tower in which NO is oxidized to NO , and converted

to the acid in the production of HNO3 . In this column the reactions
3N02 + H2O = 2HNO3 + NO

2N0 + 02 = 2N02
occur successively and continuously to convert 90 % of the NO fed to HNO3 . Gas
air
from the catalytic NH3 converter and additional
of
enter the bottom the column
.
on
O2
The converter gas NO 17.2
%
H2O and 68.9
% mole basis
O2 %
4.7 9.2 N2
is
a
,
to ,
.
air
Water enters
O2
The extra added supplies equal the the converter gas
in
.
wt
the top
65
at
as
of
the column absorbs the NO2 and leaves HNO3 the bottom
%
,
.
Waste gases leaving the top the column may
be
of considered water free The
.
its
cooled along length operates psia with temperatures close
at
column
It
100
to is
ambient that sensible heat effects may
be
enough neglected
Determine the
% .
cooling required Btu column making day
55
65
hr
of
for tons nitric acid
of a
/
/
,
.
C an ammonia air mix containing
10
In
%
6.39 the manufacture nitric acid mole
-
.
NH platinum catalyst and 100 psia The following reactions

to
at
fed 800
is
a
,
.
occur
:
→+
4NH3 4NO 6H2O

+ +
+ +
502
1
(
)
4NH3 302 2N2 6H2O
2
(
)
At
what temperature the gases leave the catalyst chamber
90
do
the NH3
? of
( %
if
a
.
form NO while the remainder combines according

to
reaction
to
reacts
2
)
by
vaporizing liquid ammonia stored 100 psia
at
The NH3 obtained How
is
b
.
.
for
vaporization gas heating per
of
much heat and feed mole NH3 delivered
is
needed
at
the reactor Ambient air

to
is
80
of .F
?
6.40 One process for manufacture CS reacts natural gas with vapor over S
a
,
.
silica gel catalyst according the reaction

to
:
4S
=
CH4 2H2S
+
CS2
enter the catalyst chamber

at
design the gaseous feeds are
to
proposed process
In
° a
700 but the reaction occurs adiabatically thereafter Pilot runs indicate that with
C
,
N2 .
natural gas containing reacting with

,
of 60
40
%
mole CH4 mole the conversion

%
S
,
natural gas are fed per mole

80
The process flow sheet

of
%
when two moles

S.
is
is
shown Fig P6.40

The feed preheater and vaporizer most economically set
in
is
S
.
Will the product gases supply

up
heating medium
use product gases
as
be so as
to
shown
,
the heat necessary what temperature will they leave the unit not how
If
at
If
,
?
much extra heat must supplied

?
For H2S Btu

lb
Ср
R
9.50 mole
=
'
,
for CS2 Ср 7.59

,
gas
for
TP
and 8.71
TP
liquid 7.03
S,
synthetic detergents the final formation

In
of
of
6.41 the manufacture the active

.
ingredient requires neutralization the alkyl aryl sulfonate according

to
of
the reaction
C12H25 C12H25
NaOH
+
H2O
SOH SOzNa
reaction per mole neutralizing H2SO4 with

as
of
The heat the same that found

in
is
recycle system
as
NaOH The sulfonate and caustic solutions react shown

in
in
a
.
Products ,
minimum
temperature
= 200 ° C
150 °C
Sio
Natural gas
P = 1 atm
Molten
sultur
200 °C
Extra heat
if needed
Fig . P6.40 . Carbon disulfide manufacture .
Fig . P6.41 . The addition of caustic solution is controlled to give a neutral solution
not
at point 1, and the rate of recycle is controlled so that the temperature at 1 does
exceed 120
F
°
.
Calculate the recycle rate pounds fluid flowing past point per pound
of
in
arylof
2
sulfonate feed and the product composition The specific heat both alkyl
of
,
sulfonate and sodium alkyl aryl sulfonate may both

be
as
taken 0.25 cal
/g
.C
°
To vacuum
water vapor
(
2
90
at
F
°
)
Product
70
Sulfonate mix
F
,
°
1
% %%
60 wt sulfonate
80 35 wt water
wt
H2SO4
5
70
Caustic
F
,
°
10
wt
%
NaOH
(
Fig P6.41 Detergent manufacture

,
.
Calculate the final temperature the following adiabatic reaction

in
6.42
:
.
,950 4H
H
H16
)F
g
C
,
(9
T
,
,
°
')
(
)
(9
hydrogen heptane
10
to
of
of
with molar ratio the feed

in
1
a
:
.
6.43 . Calculate the final temperature in Prob . 6.42 if the ratio of hydrogen to hep
tane in the feed is 5 : 1.
6.44 . Methane is burned with 50 per cent excess air . The reactants enter the
burner at 77 ° F . Calculate the maximum temperature the products may attain .
6.45 . A natural gas containing 83 per cent methane , 17 per cent ethane is burned
in a boiler firebox with 30 per cent excess air . The gas and air enter at 77 ° F and
1 atm ; the combustion products leave at 1500 °F . Calculate the heat supplied to the
boiler per 1,000 cu ft of entering natural gas , assuming complete combustion .
6.46 . The equilibrium constant for the reaction of hydrogen with oxygen depends
upon temperature . For
H , + 12 02 HO
12,900
log Kp. 2.86
TºK
Calculate the final composition and temperature when 1 lb mole H , and 12 lb mole 02
are reacted at 1 atm . The initial temperature is 1000 °K .
6.47 . The conversion of ethylene to ethyl alcohol is sketched in Example 5.16 and
in Prob . 5.55 . In the industrial reaction the fresh ethylene feed contains 3 mole %
C2H6 , and the combined ethylene feed stream to the reactor contains 15 % C.H ..
Conversion is 4.2 % of the feed C2H , per pass through the reactor when 0.6 mole of
H20 / mole of total C2H4 is fed .
a . Calculate the concentration of gas vented from the recycle stream , and the
recycle ratio (moles ethylene recycled / mole fresh feed ) .
b. If the combined feed enters the reactor at 570 °F , 1000 psia , at what temperature
does it leave ?
c. Example 5.16 calculated the equilibrium concentration at 570 ° F and 1,000 psia .
Calculate the equilibrium concentration at the conditions that would exist at the
reactor exit if equilibrium were reached in the reactor . Consider the inert C2He as a
diluent which reduces the partial pressure of each reactant and product . At 600 ° F
Кр 0.0018 atm - 1 and at 650 ° F KP 0.0011 atm - 1 (see Ref . 4 , Chap . 5 ) .
for
6.48 . Develop a computational flow chart determining the equilibrium tempera

ture and conversion for the gaseous reaction
=
+
B
A
which atmospheric pressure

at
carried out The feed gas containing only

is
and
B
A
,
.
any proportions enters the reactor temperature above

25
25 Tı
at
Assume that
in
C
1
C a
,
),
°
.
7p
The equilibrium constant

Ti
AHR and for and between and are known

B
A
,
, ,
°
TP2
,Kp
for
all
and the mean heat capacities components between Tequil and

25
C
,
°
by
linear interpolation the computer memory

be
may determined table stored

in
in
a
6.49 Formaldehyde important raw material

an
of
the manufacture several

in
,
.
by
plastics usually made The following reactions occur

of
oxidation methanol
is
,
:
.
=
=
12
AHR
02
CH20 H2O -36,800 cal

+
CH3OH mole
g
)1
(
/
CH3OH = CH2O ΔΗ
AHR 28,800 cal mole
+
H2
=
2
(
)
/
air
vaporized mixed with silver gauze catalyst where the

to
Methanol and fed

is
a
,
occurs adiabatically the catalyst

60 at
The feed and contains

to
reaction 170
F
° of is
of °
.
air per pound

cu
of
of
26.7 std methanol Conversion the methanol

ft
is
.
with the gases leaving the reaction zone only reactions

at
If
realized 1100
F
1
,
(
)
.
the analysis the gases leaving the converter For methanol

of
and occur what

is
2
?
(
)
lbm
use cp
for
cp
=
0.45 Btu formaldehyde 0.55 Btu lbm

=
.F
F
/
,
°
°
/
6.50 . Develop a computational flow chart for determining the heat of reaction at
any elevated temperature for the reaction :
aA + bB ECC + dD
The following data are available :

a . Values of a , b , c , d and the temperature , T ° C .
b. The heats of formation at 25 ° C for A , B , C , and D.
c. The feed concentration . The feed contains only A and B , but not necessarily
in stoichiometric proportions .
d . The equilibrium constant , K , which is large enough to insure that the limiting
reactant is almost entirely consumed .
e. Values of Tp for A , B , C , and D between 25 °C and T °C .
is calcined in a furnace to produce lime .
6.51 . Limestone 1,000 lbm hr of / lime
stone (95 per cent CaCO3 , 5 per cent H20 ) is charged to the furnace at 77 ° F .The
product gases leave the furnace at 600 ° F , and the calcined lime leaves at 1500 °F .
Calculate the heat added to the furnace to calcine the lime , neglecting unknown heat
losses through the furnace walls . TP.Cao = 12.2 Btu / lb mole ° F between 77 and
1500 °F .
6.52 . The synthetic fuel water gas is produced by reacting steam with incandescent
coke at 1900 °F :
C (amorphous ) + H2O ( g ) → CO ( g ) + H2 (g )
( Coke ) ( Water gas )
and C (amorphous ) + 2H2O ( g ) + CO2 ( g ) + H2 ( g )
The second reaction is less desirable and is suppressed by operating at high tempera
tures . The reaction is endothermic , so that the bed must be reheated by passing
air
through supplied and the prod
to
at
burn some coke for heat Steam 300

is
it
F,
°
.
The coke bed weighs supplied

20
at
uct gas leaves tons and steam
. at
1900
51 is
F
,
°
.
per cent CO2 per cent CO per cent
theHz
47
hr
1,000 lbm The exit gas contains

2
/
,
.
all
cooling degrees Fahrenheit per minute
of
of
Calculate the rate the bed

in
if
(
)
steam reacts
.
stopped Example 6.15 the heat transfer coeffi

of
the stirrer the tank

in
If
6.53
is
-
.
sq
Ui
cient drops Calculate the temperature

hr
hr
0.5 Btu after the

to
ft
=
.F
1
/
stirrer stops assussuming that the initial tank temperature was the steady state value
,
the new steady state temperature without the stirrer Assume that
be
What will
?
-
natural convection gives sufficient mixing without the stirrer maintain the liquid
to
at
uniform temperature
a
initially filled with water

A
6.54 An agitated 500 al tank steam coil

70
at
is
F
°
an .
.
-g
sq
using condensing
at
of
with area heats the water steam 250 The heat

ft
F
5
°
.
sq
transfer coefficient for heating 200 Btu

hr
The tank loses heat

to
ft
the
is
F
/
°
of .
its
sq
surroundings through
90
an
walls which have The heat transfer

ft
area
,
-
.
for
sq
and the surroundings temperature

hr
coefficient heat loss Btu

ft
is
is
2
F,
°
How long will the boiling point

89
to
to
at
take heat the water atm Neglect

.F
it
?
°
the heat capacity

of
the tank walls

.
6.55 An insulated stirred 100 gal tank initially full

70
at
of
water Water
F
is
°
-
.
gpm and water

An
70
of 10
at
at
at
of
added rate withdrawn the same rate

F
is
at is
a
,
°
electric heater supplies

10
to
kw heat the water constant rate

a
the temperature the water leaving the tank after

hr
heating
of
of
What
is
?
hra.
heating
of
5
heating what will

be
hr
of
the heater turned off after the exit water tem

If
is
1
b
,
.
hr
perature min later later

1
5
?
?
6.56 . A stirred 300 - gal tank is initially half full of benzene at 60 ° F . Benzene at
70 ° F is added at a rate of 20 gpm , and benzene is withdrawn at a rate of 10 gpm .
The benzene is heated by steam condensing at 212 ° F with a heat-transfer coefficient
of 150 Btu / hr sq ft ° F and a heat -transfer area of 5 sq ft . Will the benzene boil
( at 1 atm ) before the tank is filled ? If yes , what volume of benzene is in the tank
when it starts to boil ? If no , what is the temperature of the benzene when the tank
is just filled ?
6.57 . An aqueous nuclear waste is stored in a spherical tank 6 ft in diameter .
Radioactive decay releases heat at the rate of 50 Btu /min per cubic foot of solution .
a . What must be the heat -transfer coefficient to ensure that the solution will not
exceed 200 ° F 6 hr after the tank is filled ?
b . What must be the heat-transfer coefficient to ensure that the solution tempera
ture will never exceed 200 ° F ?
6.58 . An open tank containing 1,000 lbm of water initially at 70 ° F and 1 atm is to be
heated with steam condensing at 300 ° F in a coil with 5 sq ft of heat - transfer area .
The heat -transfer coefficient is 1.10 Btu / hr sq ft ° F . How long will it take to vapor
ize 300 lbm of water after the steam is turned on ?
6.59 . Liquids A and B react in an endothermic second -order reaction to give
compound C : A + B → C. It is proposed to charge a stirred -tank reactor with a
The
all
mass of B , and then slowly feed A at a constant rate until the reacted
B
is
.
temperature Develop
be
To
to
at
the reactor maintained constant differen
in
is
a
.
by
tial energy balance supplied
be
to
to
determine the heat steam coil the reactor
in
a
.
all
Integrate the differential equation Carefully define symbols you use and state
.
the assumptions made

.
6.60 An air conditioner takes air from the room cools and returns the room
to
it
,
of it,
.
by .
is air
hr air
the temperature
10
on
When the conditioner turned the the room

in
is
by
20
The air conditioner removes 12,000 Btu from the air but
ft
100
F
8
,
°
.
heat transferred into the room through the window glass from the outdoors which
is
sq
50
at
and the average heat transfer

sq of
The area the windows

ft
is
100
is .F
is
,
°
to -
0.5 Btu How long will
hr
coefficient take the air conditioner reduce

ft
it
.F
? /
air
Neglect water vapor and neglect the heat capacity

70
to
the room air the

in
F
°
the qualitative effect considering these

be
of
furniture wall etc.

of
What would
,
neglected factors
?
Substance undergoes first order reaction aqueous solution where

in
6.61
A
-
.
-25,000
50 70
ké
at
0.7e1.2
of
sec The heat the exothermic reaction constant

T
is
-1
(
cal mole aqueous solution containing 1.2 per cubic foot

° a an
cu
- lb
of
/g
mole
ft
A
.
charged The heat transfer coefficient for

ft to
of
solution stirred batch reactor

is
.
sq
75
Btu the reacting solution and the

hr
the coil Plot the temperature

of
is
.F
/
Assume that the aqueous solution has the

of as
of
of
concentration function time

A
physical properties water

.
Example 6.16 plot the temperature profile when per cent

10
In
6.62 the
a
,
(
)
.
sodium hydroxide solution flows per cent solution flows

40
20
at
at
min
in
lb
in
b
a
/
,
(
)
lb
10 min
/
.
Plot the cooling curve for Example 6.16 when the per cent sodium hydrox
10
6.63
.
to
ide solution continues flow after neutralization

.
Example 6.16 the heat transfer coefficient

on
the stirrer not turned

If
in
6.64
is
-
.
With other conditions unchanged what

sq
only
15
Btu the maximum

hr
ft
is
.F
is
,
/
temperature attained
?
In
Example 6.16 the heat was used even though the

25
at
reaction
of
6.65
C
,
°
.
solution temperature varied this justified

Is
?
.
its
6.66 . The fission of uranium is induced by
in
as
reaction with neutron shown
,
the typical nuclear reaction
139
La
57
42
→
+
92U 235 oni
+
Mo95 2on1
The relative masses the components are
of
92
U235 235.124
I
on 1.00897
139
La
42 57
138.955
Mo95 94.945
by
Calculate the energy released
of
of
the fission uranium the reaction shown
in
lbm
.
additional problems are needed computer programming
6.6 6.9 Probs
If
in
6.4
,
.
6.10 6.12 6.16 6.18 6.23 6.25 6.26 6.30 6.53
6.39 6.40 6.41 6.42 6.45 6.46 6.47
,
,
6.54 6.55 6.56 6.57 6.58 6.59 6.61 may
be
of
solved the form calculational flow
in
a
,
up
computer program many these problems
In
or
to
of
chart instructive set
is
it
a
,
.
by
the program flow chart and then solve the problem hand following the program
or
flow chart step y step

or
.
-b
REFERENCES
“6
R.
Bichowsky Thermochemistry
D.
F.
F.
of
and Rossini Chemical Substances
1.
”,
,
Reinhold Publishing Corporation New York 1936

,
Comings
W
High Pressure Technology McGraw Hill Book Company Inc.

E.
2.
.:
“
,
”
,
-
New York 1956

,
“ .
Physical Chemistry
2d
D.
ed
of
Glasstone Textbook Van Nostrand

3.
.>
",
.:
S
,
Company Inc. Princeton N.J. 1946

,
,
,
.
H.
Perry Chemical Engineers Handbook

3d
ed
ed
McGraw Hill Book

J.
4.
,
,
.,
(
-
:
.
'
Company Inc. New York 1950

,
,
,
”, >
Gases and Liquids McGraw
of
R.
The Properties
K.
T.
C.
Reid and Sherwood

5.
“
:
Hill Book Company Inc. New York 1958

.: .: ,
.
F. R.
, D.
Rossini Natl Bur Standards

U.S. Circ 500 1952
et et
7. 6.
al al
,
),
(
(
.
).
Physical and Thermodynamic Properties

D.
of
Rossini Values
Selected
,
Hydrocarbons and Related Compounds American Petroleum Institute

of
, ”
Research Project Carnegie Institute Technology 1953

44
of
,
Weissberger Physical Methods Organic Chemistry Pub

of
Interscience
8.
”,
.:
,
"
lishers Inc. New York 1949

,
.
CHAPTER 7
INORGANIC CHEMICALS
Inorganic chemical processes have existed for thousands of years .

Many early processes involved simple treatment of natural materials .
For example , limestone was heated by a fire to produce lime for mortar ;
clay was fired to produce water - resistant pottery . Slowly more complex
processes evolved . These may have consisted of several steps involving
the reaction of several natural raw materials . With the development
of the scientific chemical industry , many more inorganic chemicals were
produced . Today , a great number of inorganic chemicals are produced
7.1
and used . Table the major inorganic chemicals

of
It
lists few
a
.
omits many areas such paint pigments cement gypsum and metals
as
,
,
which also involve processing inorganic materials More complete
of
may for the entire chemical process

be
tabulations found Ref

in
2
.
industry
.
Inorganic processes are often more easily developed than are organic
Often inorganic reactions proceed rapidly and
go
processes nearly
to
.
-pby
completion with few any side reactions give roducts The

to
if
,
problem thermal decomposition unimportant many inorganic

of
in
is
compared heat sensitive organic compounds

to
materials
,
the inorganic processes operating today have developed over

of
Some
In
many years others are recent development

of
some cases newer

a
;
,
.
more economical process has displaced the older process for making the
same chemical For example the contact process has almost displaced
.
the chamber process

of
the manufacture sulfuric acid

in
its
questions arise considering manu

in
of
number chemical and

A
facturing processes
.
From what raw materials can the product

be
made and where

1.
are the raw materials available

?
What alternative manufacturing processes may

be
used
4. 3. 2.
What are the markets for the product

?
Considering the raw materials processes and markets the pro

is
,
duction the material economically justifiable This economic analysis

of
may also consider data plant Location may

on
the best location for

a
compromise between raw material site and markets Transporta

be
a
tion power and labor costs are important factors

,
281
Table 7.1 . MAJOR INORGANIC CHEMICALS *

Annual production ,
tonst
Aluminum chloride :
Anhydrous 29,000
Liquid or crystal 17,000
Ammonia , synthetic anhydrous 3,831,000
Ammonium nitrate 2,521,000
Ammonium sulfate , synthetic 1,094,000
Calcium carbide 903,000
Calcium phosphate , dibasic 233,000
Carbon dioxide :
Liquid and gas 363,000
Solid ( dry ice ) 471,000
Chlorine ( gas ) 3,600,000
Hydrochloric acid 828,000
Hydrofluoric acid 84,000
Hydrogen ( million cu ft ) 43,000
Nitric acid 2,698,000
Oxygen , high purity ( million cu ft ) 38,000
Phosphoric acid 1,727,000
Phosphorus 335,000
Potassium hydroxide :
Liquid 77,000
Solid 16,000
Sodium (metal) 110,000
Sodium bicarbonate (est .) 80,000
Sodium bichromate and chromate 97,000
Sodium carbonate :
Ammonia - soda process 3,887,000
Natural 627,000
Sodium chlorate 67,000
Sodium hydroxide :
Liquid 4,055,000
Solid 458,000
Sodium phosphates ( total , est .) 883,000
Sodium silicate ( soluble , anhydrous ) 483,000
Sodium sulfate :
Refined 238,000
Salt cake 664,000
Glauber's salt 107,000
Sulfuric acid ( 100 % H2SO4 ) :
Chamber process 1,736,000
Contact process 14 , 115,000
* Data in this table are reprinted from Ref . 2 , with permission .

† For a typical year ( 1958 ) ; in short tons unless otherwise noted .
INORGANIC CHEMICALS 283
To illustrate the consideration of some of these questions , sulfuric acid

and ammonium nitrate manufacture will be described in detail .
SULFURIC ACID MANUFACTURE
Sulfuric acid is the largest tonnage inorganic chemical produced .

Although very little of it reaches the consumer in the form of acid , large
quantities are involved in the production of many consumer items .
Raw Materials . The three raw materials needed to manufacture sulfu
ric acid are air , water , and sulfur . The first two are readily available ,
the last may be obtained in a number of forms ( Table 7.2 ) . Most of the
TABLE 7.2 . SOURCES OF SULFUR *
Long tonst
Element sulfur :
Frasch process 4,643,000
Recovered 640,000
Ores 2,000
Imported 591,000
Other sulfur sources :
Iron pyrites 567,000
By - product , such as zinc gases , H2S , etc. 452,000
Decomposition 310,000
all
Total , sources 7,760,000

*
Data this table are reprinted from Ref with permission

in
2,
.
long ton 2,240 lbm

=
1
†
sulfur listed significant quantity

to
used make sulfuric acid but

is
is
a
,
used rubber carbon disulfide and other chemical manufacture About

in
,
,
.
80
per cent The Frasch

of
sulfuric acid made from elemental sulfur

of is
process accounts for most the elemental sulfur The process devel
,
.
by
oped around 1900 Herman Frasch forces superheated water into

,
underground sulfur deposits The molten sulfur brought

to
the
is
.
surface by pressurized hot air The resulting sulfur very high purity
of
is
.
99.9 per cent and therefore particularly suitable for production

to
99.5
is
(
by
pure sulfuric acid American production

of
of
elemental sulfur the

.
Frasch process concentrated near the Texas and Louisiana Gulf Coast
is
Recovered sulfur produced from the hydrogen sulfide and other

is
Of
sulfur compounds natural gas and petroleum course

in
sour
"
,
.
sulfuric acid may produced using SO2 from the complete oxidation
be
of
HZS without producing intermediate elemental sulfur

.
iron pyrites FeS2 produce sulfuric acid requires purification

to
of
Use
(
on
the burner gases produced roasting the mineral because small

of
impurities can deactivate the catalyst

of
amounts
.
In
economically justifiable use sulfur bearing

to
some cases
is
it
-
the
by - products of other manufacturing processes . For example , in
roasting produced and can
be
zinc sulfide ores SO used for sulfuric
of
is
,
,
acid after purification Hydrogen sulfide many crude oils must
be
in
..
produce satisfactory motor oils and fuels
be
to
It
removed can oxidized
.
give so for sulfuric acid manufacture the refinery
to
as
shown
in
,
,
diagrammed Fig
in
9.2
for
Process There are two major processes producing sulfuric acid
,
.
the chamber process and the contact process The older chamber process
.
employs nitric acid and nitrogen oxides
to
in to
oxidize the SO2 SO3 The
.
SO
contact process catalytically oxidizes SO2 essentially
to
and used
is
,
all
Nearly
all
new plants built today per cent
90
sulfuric acid
of
is
.
of by
produced the contact process because the older chamber process pro
,
an
duces acid uneconomically low concentration
.
Only the contact process will Figure 7.1 shows
be
discussed here
a
.
by
sulfuric acid process based upon plant designed and operated the
a
5
Monsanto Chemical Company pure sulfur although the con
It
uses
.
,
tact process may The plant
be
used with SO2 gas from various sources
.
per cent acid and oleum H2SO4 with dissolved S03
98
produces both
(
).
The three chemical reactions the contact process are
in
02
Combustion
→
+
SO 7.1
+ S
,
:
)
Conversion SO2 420 SO 7.2
→
,
:
)
(
:
Absorption +
+
SO3 H2O H2SO4 7.3
)
(
:
Pure sulfur brought from the storage pile the sulfur elting tank
to
is
by
-m
by
small scoop trucks
at
It
melted and maintained 135 steam C

is
°
.
coils At 135 the viscosity about centipoises and the sulfur

C
is
is
8
,
°
.
by
pumped Air for combustion supplied large cen

to
the burner
is
a
.
by
trifugal blower contacting

to 98
The air
first dried with per cent
is
it
.
an
absorption tower
be
sulfuric acid The air must dried prevent

in
..
avoid acid mist forming

to
corrosion and the waste gas from the last

of in
Drying the air permits use ordinary steel eliminating

of
absorber
,
.
the need for lead equipment

.
The sulfur burner cylindrical steel vessel lined with insulating

is
a
brick and firebrick The molten sulfur flows the top and down
at
in
.
also supplied the top

At
The air
at
over firebrick checkerwork

is
a
.
up
oil
at
of
temporary the base the sulfur

or
gas burner installed

is
start
to a
-
up
the checker brick the ignition temperature

to
of
burner heat sulfur

.
Another type sprays molten sulfur into horizontal combustion

aa
of
burner
chamber
.
The gas leaving the burner

at
about 850 and contains per cent

is
9
°
Part passed through

to
the gas
of
waste heat boiler

its
SO2 reduce
is
-
.
temperature the desired converter inlet temperature Bypass

to
part
of
.
the gas around the boiler gives more accurate temperature control
of
.
20
air
Dry
%
98
acid product
%
98
21 acid
-
Water cooled
22 Acid return acid coolers
Air
Drying
3
tower
Steam 11 12
15
Heat
6
Steam
exchanger
Boiler 16
1
Boiler
Sulfur 13
8
17
4
10
285
Air cooled 14
%
Gas Oleum 98 acid

Sulfur Gas heat
tower tower
burner filter converter exchanger
Sulfur
.melter
Feed water heater
-
Water cooled acid coolers

3
Boiler
%
98
Oleum acid 118

feed
storage
- up
water storage tank Make

tank
water
19 Oleum
product
7.1
.
.
.
(.
.)
to
Fig Sulfuric acid plant Numbers identifying flow streams refer Table 7.3 Courtesy Industrial and Engineering Chemistry
The steam produced in the waste -heat boiler is used for heating in the
plant . Such recovery and use of heat which would otherwise be wasted
is commonly employed in industry to reduce process costs .
The hot gas is filtered to remove any dust or ash and flows to the first
stage of the converter , where the SO , is catalytically oxidized to SO3 .
The catalyst which speeds up the reaction is vanadium pentoxide depos
ited on inert pellets . There are four layers of pellets supported by iron
grids .
At room temperature the rate of oxidation of SO2 to SO3 is low , but the
equilibrium conversion is essentially 100 per cent .. The rate of oxidation
increases with temperature , but the equilibrium shifts away from SO :
as the temperature rises . Therefore , it is necessary to choose a compro
mise temperature where the rate of reaction is sufficiently fast to give
nearly the equilibrium conditions and where the equilibrium gives a
reasonable conversion to SO3 .
The equilibrium constant , as shown by Eq . (7.2 ) ,
Psos
KP 22 (7.4 )
Pso2Po2
is given as a function of temperature by !
5186.5
log Kp =
T + 0.611 ( log T) – 6.7497 ( 7.5 )
where T is in degrees Kelvin . The gas enters the first stage of the con
verter at 410 ° C ( see Fig . 7.2 ) .. The rapid exothermic reaction increases
the gas temperature to 600 ° C . At this temperature the equilibrium
conversion is only 70 per cent , which is not adequate for an economic
process . For this reason , the gas is sent to a second waste -heat boiler
where it is cooled to 430 ° C . The equilibrium conversion at this tempera
ture is over 97.5 per cent , but the rate of oxidation is lower , and three
catalyst stages are required to allow sufficient time for reaction .
The gas leaving the converters at 445 ° C must be cooled before it can
be absorbed to give sulfuric acid . This cooling is accomplished in a heat
exchanger in which the feed water to the boilers is heated to 220 ° C .
Such an arrangement conserves heat . The gas is further cooled by
atmospheric air .
The gas flows to the first absorption tower in which the absorbent
is 20 per cent oleum ( i.e. , in 100 lb of the oleum , there are 20 lb of SO3
and 80 lb of H2SO4 )). The oleum absorbs SO ,3 and is increased in strength ,
but it is diluted back to 20 per cent oleum by addition of 98 per cent acid
at the bottom of the oleum tower . The temperature of the oleum enter
ing the tower determines the vapor pressure of SOz over the oleum , and
hence fixes the amount of SO3 which is absorbed in the oleum tower .
100
To
Gas leaving converter
90
-Last three stages

of converter
80
70 -T To
,
SOZ
Gas cooling in second

waste heat boiler
to
60
So
of
Percentage conversion
50
40
30
1st stage
of
converter
20
10
Gas entering
T5
200 400 600 800 1,000 1,200 1,400

Temperature
C
,
°
on
Fig 7.2 shown schematically equilibrium conversion

an
to
Conversion SO
of
SO2
,,
3
.
diagram
.
The higher the entering oleum temperature the higher the SO3 vapor
is
,
pressure the absorption The temperature

of
of
and the lower S03 the

is
..
is ,
increased by the heat absorption the enter

of
of
of
oleum SO3 the heat

),
ing
per cent acid

98
gases and the heat mixing with the The oleum

of
.
,
water cooled heat exchanger before sending the oleum

to
in
aa
cooled
it
is
product storage tank

.
The gas leaving the oleum tower contains significant S03

so
is
it
;
by
per
98
second absorption tower where the SO3 absorbed

to
passed
is
a
TABLE 7.3 . SULFURIC ACID PROCESS DATA *

Basis : 250 tons ( 100 % H2SO4 ) as 20 % oleum
1. Sulfur to burner
Mass of sulfur : 83.8 tons / day
Temperature : 135 °C
2. Air to drying tower
Flow rate : 14,500 cu ft / min (at standard conditions )
Temperature : 50 ° C
Pressure : 45 in . H2O
3. Air to sulfur burner
Moisture content : 1 mg / cu ft ( at standard conditions )
4. Gas leaving sulfur burner
Composition : 9.0 % SO , ( volume )
5. Gas entering converter
6. Gas leaving first stage of converter and entering waste-heat boiler
Conversion : about 70 % of the SO , has been converted to SO , at this point
7. Gas leaving waste - heat boiler and entering second stage of converter
8. Gas leaving converter
Conversion : 97.5 % of original SO2 from the burner has been converted to SO ;
9. Gas leaving economizer
10. Gas entering oleum tower
11. Oleum entering oleum tower
Temperature variable ; for example , 75 ° C
Flow rate : 400 gal / min
Composition : 20 % oleum
12. Gas leaving oleum tower and entering 98 % acid tower
SO
All
the
O2
of N2
Composition : unreacted from the converter plus and from

,
,
air
SO3 depends the temperature

on
of
Concentration the oleum The

.
oleum temperature may substantially less than the exit gas temperature
be
in .
SO3
the
Generally equilibrium the partial pressure

so
of
not achieved
is
;
,
greater than the vapor pressure SO3 over the entering oleum
of
the exit gas

is
Nevertheless the temperature the entering oleum determines the partial

of
,
that the temperature must carefully regu

be
so
pressure the exit gas

of
in
SO3
,
SO
the vapor pressure over oleum may

be
on
of
lated Data found

in
Ref
6
,
.
.
.
TABLE 7.3 . SULFURIC ACID PROCESS DATA * ( Continued )

13. Stream of 98 % acid to dilute oleum back to 20 % after it has absorbed SO3 . Flow
rate depends upon the oleum strength , which in turn depends upon the SO3
absorbed and the temperature of the entering oleum .
14. Oleum leaving oleum tower
Temperature depends upon SO3 absorbed , etc.
Composition : 20 % oleum
15. Waste gas
Composition : 0.262 % ( volume ) SO2 , 90.97 % N2 , 8.77 % 02
16. 98 % acid to the 98 % tower ; flow rate depends upon the quantity of SO 3 ; to be
absorbed
17. Acid from the 98 % tower . Since the acid has absorbed SO3 , it will be stronger ,
for example , 99.0 % , and at a higher temperature .
18. Make - up water . Water must be added to react with SO3 . Some is supplied
from the air in the drying tower , the rest is added as make -up water to the 98 %
acid storage .
19. Oleum product is withdrawn from the oleum storage tank
20. 98 % acid product may be withdrawn when desired , if there is a need for it . The
plant described normally makes only 20 % oleum .
21. Feed acid to the drying tower
Flow rate : 500 gal / min
Composition : 98 % H2SO ,
22. Exit acid from drying tower
The temperature will be higher and the concentration lower than that of the acid
entering , because of the water vapor absorbed .
* The data in this table are drawn largely from Ref . 5 , with permission . To per
mit more complete mass balances , some of the data have been adjusted and augmented
with additional realistic values .
cent acid . The SO3 absorbed increases the acid strength slightly , and
make - up water is added to the 98 per cent acid storage tank to maintain
the concentration . Some of the 98 per cent acid is supplied to the tops
of the drying tower and the absorption tower . The acid is slightly
diluted in the drying tower by the water vapor removed from the air .
The diluted acid is returned to the 98 per cent acid storage tank . The
waste gas from the 98 per cent acid tower contains only a trace of SO3 and
less than 0.3 per cent SO , by volume .
More detailed process data from a plant producing 250 tons / day of
H2SO4 as 20 per cent oleum are given in Table 7.3 . These data may be
used for mass and energy balances .
Markets . Sulfuric acid is widely used in producing other chemicals
and consumer products . The largest use is in the manufacture of phos
phate fertilizers . Other uses are given in Table 7.4 . Because of the
low unit cost † of sulfuric acid , transportation costs must be kept to a
† 100 per cent sulfuric acid sells for about $24 per ton in tank -car lots , excluding
transportation costs .
all
minimum . Therefore , plants are located over the country near the
cheaper ship the sulfur raw material long distances
to
It
markets
is
is .
than the finished acid Much sulfur shipped by water transporta
it
is
.
tion whenever possible may shipped molten sulfur
be
or
as
in
It
the
.
solid form
.
Many users sulfuric acid produce their own acid because
of
is
it
,
cheaper than buying from someone else Substantial quantities
of
acid
7.1
Fig 7.3 Sulfuric acid plant This plant Fig
to
almost identical that shown

in
is
.
.
The major units pictured from right
to
left are the horizontal sulfur burner the vertical

,
converter the short hot gas filter the air rying tower the absorption tower and
a
,
,
-
-d
water storage tank The plant differs from that shown Fig 7.1 by having hori
in
aa
.
-
in by
zontal spray sulfur burner and only one absorption tower The plant was built
.
their phosphate fertilizer plant

at
the Monsanto Chemical Co. for Swift and Co.

Agricola Fla ourtesy Monsanto Chemical Co.
,
)
.
(C
recovered and used other applications For example most

in
are
of
,
.
for
required TNT production

In be
the acid can recovered more dilute

in
a
the
state and used for other applications petroleum refineries

.
hydrocarbon acid sludge may produce SO2 for conversion

be
to
burned
-
to new acid
.
The sulfuric acid process based upon few simple chemical reactions
is
air
and requires only one raw material other than and water However
,
.
the design and construction commercial plant require careful con

of
a
many engineering problems This discussion has covered

of
sideration
.
TABLE 7.4 . USES OF SULFURIC ACID *

Approximate
per cent of total
production
Phosphate fertilizers 26
Inorganic pigments 8
Ammonium sulfate (fertilizer )

Synthetic 5
Coke oven 3
Aluminum sulfate 3
Other chemicals ( explosives , etc. ) 7
Cervecer
Iron and steel pickling 5
Petroleum products 4
Rayon 3
Nonferrous metal processing A
Other uses 32
100
* Reprinted from Ref. 2 , with permission .
only the important points commercial sulfuric acid plant

of
few
A
a
,
.
similar Fig 7.3

to
the one described this section shown

is
in
in
,
.
AMMONIUM NITRATE MANUFACTURE
The Stengel process for the manufacture based
of
ammonium nitrate
is
upon the simple reaction ammonia and aqueous nitric acid with sub
of
sequent drying crystallization and grinding the product con To

of
,
produce more uniform product several recycle

to
serve materials and

a
employed Ammonium nitrate used primarily

as
streams
a
are
is
.
an
fertilizer and also explosive The plant described below operated

as
is
.
by
Solvents Corporation Sterlington

at
the Commercial Louisiana

4
,
Raw Materials Liquid anhydrous ammonia and aqueous nitric acid

.
are the two raw materials Ammonia supplied from plant miles
is
5
.
by
away through pipeline The ammonia produced the reaction

in
is
4
a
-
.
.
hydrogen from the reforming natural gas and high purity nitrogen
of
of
recovered from air The ammonia arrives the nitrate plant liquid
at
as
a
.
at
10
about
F
°
.
Nitric acid manufactured by the catalytic oxidation

of
ammonia
is
plant located adjacent the nitrate plant The acid 59.5 per cent
to
in
a
(
.
gal
HNO3 stored stainless steel storage tanks

two 71,000
in
is
-
)
Process flow sheet for the Stengel process shown Fig 7.4 and
in
A
is
,
.
detailed process data for mass and energy balances are presented
in
Table 7.5 The basic reaction simple

is
.
:
+
NH3 HNO3 NH4NO3

+
7.6
(
)
by
The ammonia vaporized and heated

to
255 steam before

is
is
it
F
°
Ammonia heaters
Ammonia
M
M
Waste
Condensate
gas
Vapor
3
8
Acid
heaters Reactor Air
Water
Nitric acid Air Final
2
heater condenser
6
Charge tank
Water
Liquid Partial
vapor condenser
separator Weir
box Oversize
recycle
292
7
Fines 10
dissolving Coating
tank
Cooling belt agent
Breaker
Grinders 11
12
Screens Finished
Coating NH4NO3
to
drum bagging
and shipping
5
NH4NO3 Fines recycle

7.5
to
(.
7.4
.
and Engineering
.
Fig Ammonium nitrate plant Numbers identifying flow streams refer Table Courtesy Industrial
.).
Chemistry
fed to the reactor Aqueous nitric acid is fed to an acid charge tank ,
.
where it is mixed with two recycle streams containing ammonium nitrate ,

which will be discussed later . The acid -nitrate solution is heated to
300 ° F before it is fed to the reactor The first acid heater is stainless
.
steel , but the second is tantalum to avoid corrosion by the higher - temper
ature acid .
The reactor is 16 in . inside diameter and 10 ft tall . It operates at
50 lbs / sq in . gage between 400 and 460 ° F , so that the ammonium nitrate
TABLE 7.5 AMMONIUM NITRATE PROCESS DATA *
1. Gaseous ammonia to reactor

Temperature : 225 ° F
Pressure : 50 lbs / sq in . gage
Flow rate : 3,865 lbm / hr
2. Nitric acid feed to charge tank
Composition : 59.5 % HNO3
3. Acid feed to reactor
Temperature : 300 °F
Pressure : 50 lbs / sq in . gage
Flow rate : 28,587 lbm // hr
Composition : HNO3 , NH4NO3 (from recycles ) , H2O
4. Condensate recycle to acid charge tank
Flow rate : 841 lbm / hr
Composition : 80 % NH4NO3 , 20 % H2O (by weight )
5. Fines recycle to acid charge tank
Flow rate : 3,558 lbm / hr NH4NO3
6. Vapor - liquid mixture of NH4NO3 and H2O
7. Molten ammonium nitrate
8. Vapor phase from separator
Flow rates : 673 lbm / hr NH4NO3 , 9,978 lbm / hr H20 , plus an unknown quantity
of air
9. Air for drying molten nitrate
Pressure : 18 in . Hg
10.
Recycle
of
oversize flakes
hr
Flow rate 3,327 lbm

/
:
11.
Coating agent
Diatomaceous earth
12. Finished ammonium nitrate
Temperature 125
F
% °
:
Composition
97
NH4NO3 diatomaceous earth

%
3
,
:
this table are drawn largely from Ref with permission

In
The data few

in
a
4,
*
to .
cases the data have been augmented and adjusted permit more complete mass
balances
.
is formed as liquid droplets and the water in the acid is vaporized . The
reaction is fast and goes essentially to completion . A slight excess of
ammonia is used .
The reaction product mixture flows tangentially into the centrifugal
liquid -vapor separator . The liquid nitrate droplets are thrown to
the
by
the separator centrifugal force and flow down
to
of
walls the base
to air
separator Hot bubbled through the molten nitrate
of
the
to
is
.
reduce the water content 0.2 per cent
.
air
The hot water vapor from the acid excess ammonia and some
,
,
vaporized nitrate leave the top the separator and pass through
at
of
all
an air heater into partial condenser where the nitrate and ammonia
a
,
and some water are condensed out To conserve the nitrate the con
,
.
recycled charge The vapor from the partial
to
densate the acid tank

is
.
the final condenser where the water vapor con
to
condenser passes
is
atmosphere
to
to
so
densed that does not escape the create nuisance

it
.
Molten nitrate product flows from the bottom the separator into
of
a
on
split into four streams Each stream flows
to
weir box where
is
it
a
.
stainless steel cooling belt where the nitrate forms layer
ft
wide and
2
-
long and move

36
thick The belts are
at
20
the rate
/ in
of
ft
332
to
.
up
At the end
of
min the belt the nitrate sheet broken

to ft
100 and
is
.
sent grinder by conveyor belts

a
The hammermill grinder reduces the size the large flakes

of
The
.
by
ground material conveyor belts

to
sent the screens where the

is
, flakes
are separated into three size ranges The nitrate flakes the proper
in
.
size range are fed the coating drum where per cent diatomaceous
to
prevent sticking and caking

to
of
earth added the nitrate The over

is
nitrate are recycled grinder and returned

to
in to
of
size flakes the screens

a
.
be
The undersize flakes fines which would undesirable the product

),
(
dusting are recycled fines dissolving tank

to
of
because Here they

a
,
with circulating nitric acid and fed the acid charge tank
to
are dissolved
.
The product nitrate bagged 100-1b bags which are loaded

in
is
into
box cars for shipment

by an
Because ammonium nitrate classified

as
is
.
its
explosive manufacture transportation and use are regulated

,
Federal law and appropriate safety precautions must

be
followed
,
Markets Until the end the Second World War ammonium nitrate
of
.
was used primarily explosives Its high nitrogen

as
of
constituent
a
per cent and low cost have made popular fertilizer

34
content about
it
a
*
)
(
since the war per cent ammonium nitrate production now

90
About
of
.
Total annual production

2,650,000 tons
As
fertilizer
to
goes
is
a
.
.
nitrogen fertilizer ammonium nitrate must compete with anhydrous

,
ammonia ammonia solutions ammonium sulfate sodium nitrate and

,
,
urea handle than anhydrous ammonia but the latter

to
It
easier
is
.
per ton
65
About bags freight extra

in
$
*
.
has a higher nitrogen content ( 82 per cent ) and a

a wider use as a fertilizer. *
The use of urea , manufactured from ammonia and carbon dioxide , is
increasing . Its solid form and higher nitrogen content ( 45 per cent ,
fertilizer grade ) make it competitive with ammonium nitrate , in spite
of its higher cost .
PROBLEMS
Problems 7.1 to 7.14 are based upon the data of Fig . 7.1 , Table 7.3 , and the accom
panying text .
7.1 . Calculate the complete composition of the gas leaving the sulfur burner .
7.2 . By writing a heat balance determine the heat loss by radiation from the sulfur
burner . ( For sulfur , Cp 0.20 Btu / lbm °F below 135 ° C .)
7.3 . Estimatethe quantity of steam produced in the two waste-heat boilers .
7.4 . Determine the composition and volumetric flow rate of the gas leaving the
first stage of the converter , assuming 70 per cent conversion .
7.5 . The actual conversion of SO2 to SO3 is essentially the equilibrium value at the
existing temperature . Check the stated percentage conversions after the first stage
and after the last stage of the converter with the equilibrium values . air
7.6 . Calculate the heat removed from the gas by the cooled heat exchanger
-
.
20
Calculate the mass per cent oleum product

of
7.7
.
.
air
entering the drying tower has percentage humidity per cent
20
of
the
, If
7.8
a
° .
50
calculate
at
acid leaving the drying tower

22
of
The concentration stream

. a
(
.
).
make up water stream

18
The flow rate

of
b
.)
7.9 Calculate
:
.
SO
The partial pressure the gas leaving the oleum tower

of
in
a
98 ,
.
13
The flow rate

to
per cent acid

of of
diluent the oleum tower stream

b
(
.
).
16
98
an
The flow rate

to
acid stream the per cent acid tower with exit

c
)
.
composition
17
99.0 per cent H2SO

of
stream
(
.
).
7.10 Using the conditions necessary

as
as
of
Prob 7.8 well other data calculate

if
98 ,
,
.
the composition and flow rate acid entering the per cent acid storage tank
of
.
15
Calculate the flow rate

of
7.11 waste gas stream

.
).
Using the conditions necessary other data esti

as
as
of
7.12 Prob 7.8 well

if
,
.
mate the temperature the acid leaving the per cent acid tower assuming
98
no
of
unaccounted heat losses

.
SO
the partial pressure the gas leaving the oleum tower con
of
How
in
7.13
is
,
.
trolled Why controlled

is
it
?
proposed change the operation the system

to
as
so
as
of
described
It
to
7.14
is
.
produce both
98
20
per cent acid and per cent oleum The sulfur and air feed rates
to .
SO3 will ultimately yield per

98
will remain the same but half the sulfur converted

,
cent acid and half will give

20
to
per cent oleum

of
The flow rate oleum the oleum

,
unchanged and the stated conditions Prob 7.8 prevail Determine

of
tower
is
:
,
oleum product and per cent acid product

98
of
The flow rates

. a
.
The flow rate make p water

of of of
b
.
-u
13
The flow rate diluent acid stream

c
98 (
.
).
16
to
The flow rate acid the per cent acid tower stream
d
(
.
).
rade anhydrous ammonia sells for about per ton

86
Fertilizer tank car lots

in
$
*
.
-g
grade per cent nitrogen 103 per ton

45
Fertilizer carload lots delivered

in
$
),
†
.
1
the
Problems 7.15 to 7.22 are based upon the data of Fig . 7.4 , Table 7.5 , and
accompanying text
.
Calculate the daily production
of
7.16 finished ammonium nitrate for the raw
.
material feed rates given
.
Calculate the composition the acid stream entering the reactor
of
7.16
.
it .
the
7.17 What percentage excess ammonia supplied and where does leave
is
,
.
process
?
7.18 List the terms required for energy balance around the reactor
an
What
.
.
be
evaluate the energy balance quantitatively
to
data must obtained
?
Calculate the heat released the reaction which occurs
in
7.19 the reactor assum
in
.
,
ing that average temperature
an
at
takes place
of
of
The heat fusion
of of
430
is it
F
° °
. .
cal
NH NO3 the melting point The heat capacity
° to at
of
1300 mole 169.6
/g
C
cal
liquid NH4NO3 The heat capacity per cent
60
be
of
estimated 0.4
/g
C
is
°
.
nitric acid about 0.64 cal /g
C
is
.
7.20 Estimate the heat lost through the reactor walls and otherwise unaccounted
.
for See Probs 7.18 7.19 Assume that the heat capacity
of
the acid mixture
,
(
.
entering the reactor per cent nitric acid Make any other
60
as
the same that for
is
.
necessary assumptions assumptions
on
reasonable basis but state these your
in
a
solution
)
.
air
Assuming that supplied the liquid vapor separator

to
of
7.21 the bottom
cu is
-
.
min and that the air supplied the preheater

at
to
of
rate 300 standard
at
ft
is
F, a
75
°
Calculate the composition mass per cent the vapor leaving the separator
of
. a
)
.
.
the
Estimate the temperature the vapor leaving the air heater
as
of
flows
to
it
b
partial condenser
.
Determine the composition the vapor leaving the partial condenser

of
c
.
.
the screening operation determine the percentage
In
of
7.22 ammonium nitrate
.
which was oversize and the percentage undersize

.
7.1
report any chemical listed The report should include

on
Write Table
in
7.23
of a
.
and
discussion raw materials alternate manufacturing processes and markets
a
economic considerations Include flow diagrams when possible

.
Fig P7.24 and the following description

on
to
Problems 7.24 7.32 are based

.
.
They are interdependent only selected problems are assigned necessary
be
to
so
that
if
,
previous problems should supplied

to in be
of
results
.
The schematic flow sheet shown Fig P7.24 small high pressure
of
that
is
,
.
for
oxygen plant such make oxygen hospital welding

be
or
as
would used aviation

,
, are
breathing use produces 1,100 std oxygen standard conditions

hr
cu
% of
ft
It
(
.
by
air
atm pressure and recovering

68
19
02
at
as
of
taken the inlet 99.5 mole

%
F
1
°
)
air
N2
product psia and then passed

45
In
to
0.5 mole this process compressed

%
is
,
,
10 .
wt
NaOH solution packed column

In
to
countercurrent this column

in
a
CO2 reacts with the NaOH

to
of
form Na2CO3 The remainder the air CO2 free)

(
-
.
1,200 psia being cooled after each stage compression

to
compressed
of
It
then
is
is
,
.
gel
air
passed through silica drier where the water removed from the From here
is
a
the dry CO2 free air cooled till partly liquefied This cooling done
in
aa
heat
is
is
is
it
,
,
-
exchanger where the feed gas flows countercurrent the two products from the plant
to
the .
air
These products are warmed from liquid temperature room temperature

to
as
At
feed gas any point along the length the exchanger the temperature
of
cooled
is
gas
.
the feed gas will always greater than the temperature either product
in be
of
of
The feed gas then distilled double column from which the product gases return
is
the heat exchanger actually two distillation columns

to
The double column

is
.
placed top The pressure drop between the two columns

on
adjusted
of
each other
is
.
Air feed
T =100 °F
Twb =70 ° F
P = 1 atm H2O H204 H2O
1st stage 2nd , 3rd, and 4th stages

of of compression with coolers
drier
drier
compressor and moisture separators
10 %
after each stage
| NaOH O2 O2
Si Si
Heat
Air feed Oxygen product
:
02 N2
% % % %
78.09 mole
20.95 mole Nitrogen product
A
0.93 mole
CO 0.03 mole
)
,
Heat exchanger
Hydrocarbons trace
-
M
pressure
psia
Rare gases trace

column
-
Low
(
www
N2
www
% 20
99
)
100 psia
pressure
column
High
(
Hydrocarbon
absorber
%
35
02
Fig P7.24 Oxygen plant

.
that the boiling liquid cold enough

to to
so
the low pressure column condense the

in
is
-
vapors the high pressure column This arrangement necessary economically

in
is
-
obtain complete separation low temperatures

O at
air
feed and the hydro

all
7.24 Assuming the and CO2 are removed from the

H
,
,
.
carbons are trapped within the system determine the concentration

of
the outlet
,
air
nitrogen product required

hr
How much
in
( lb
feed moles
is
/
?
air ,
.
the humidity The air leaving the scrub

of
7.25 What the inlet

6
is
is (a
)
?
)
.
What would be its dew

its
humidity
80
to at
column water saturated What

.F
is
?
°
-
point were expanded atmospheric pressure

2d
3d
The and 4th stages

it
if
c
?
,
(
)
compression have the same ratio Each stage followed

to
inlet pressures
of
outlet
is
byof
a .
which the air temperature drops water trap that collects

80
in to
cooler and
in
F
a
these traps
hr
of
the condensate How much water collected

in
each lbm
is
/
?
,
.
air
an
In the first stage of compression the may
be
as
7.26 . considered ideal gas
its
properties const
fit
to
and the relation V1.3
.
What the outlet gas temperature from this stage
In is
to ?
the scrub tower the air flows counter NaOH solution initially
at
7.27
of a
.
by
wt continuously recycled
10
NaOH which All

%
the CO2 removed the
is
is
.
reactions
:
2NaOH
+→
Na2CO3 H2O
+ +
+
CO2
1
(
)
NaOH CO2 NaHCO3
2
(
)
Air leaving the tower
80
at
water saturated
is
F
°
-
.
changed once every hours and enough
24
The NaOH solution charged
if of
is
is
no it
a
,
.
ultimately
90
be
the NaOH could
so
of
%
that converted Na2CO3 NaHCO
to
;
were formed How much NaOH solution charged
is
?
.
wt
wt
spent caustic solution contains carbonates analyzing
60
40
%
Na2CO3
If
air %
b
,
.
NaHCO3 what the entire spent solution concentration Remember that

is
?
,
enters this column directly from the first compressor stage
.
by
pouring
at 10
50
The NaOH solution made NaOH solution
at
%
%
7.28
is
a
(
)
.
80 into water 80 What the solution temperature immediately after the

F
is
°
°
.
NaOH solution enters the top

sq 10
of
mixing process the scrub column
of ft %
The
b
?
(
)
hr
The air stream enters the bot

of
at
1,000 lbm bed cross section

of
rate
a
at /
ft ).
(
)
(
sq
air
hr
1,500 lbm
of
of
tom the column rate bed cross section
If
the
° a
(
)
/
).
80
80
and the NaOH solution enters
at
at
at
leaves the column what temperature
F,
F,
°
does the solution leave the column
?
per
as air
7.29 The purified hydrocarbons

of
stream still contains moles C2H6
5
)
.
gases passes through the heat exchanger These hydrocarbons

of
million moles
( it
.
35
02
stream into the low pressure column where they

%
are carried the crude

in
-
)
the
O2
the liquid oxygen They are not present the and N2 streams from
in
collect
in
.
To
O2
low ressure column liquid removed pumped
of
remove them small stream is

a
,
.
-p
is air
through charcoal and pumped back into the feed
an
as
of
adsorbent bed stream

,
hydrocarbons 90
of
%
%
shown this stream contains mole which
If
removed
1
,
.
hr
the adsorber what its flow rate

in
moles
lb
is
?
(
,
/
)
–---
air
500 joules
80 At
and 1,200 psia enthalpy

do of an
80
of
has mole relative

/g
7.30
F
°
.
Btu lbm feed air enters the distillation column from

to
at
air and atm

If
F
5
1
/
°
the
O2
N2
the surroundings what temperature product streams leave

at
the and
,
exchanger the same temperature and that there

to at
Assume these streams leave

?
,
no
mixing for mixing

of
heat and form air

N
O
is
.
of . air
water saturated but containing

80
no
7.31 The enters the silica gel drier

all at
F,
,
°
.
an
entrained water the remaining water adsorp

It
The silica gel removes has

to .
.gel
12 0.1
tion capacity designed

be
so
of
of
silica The drier

H
lbm lbm that

0
is
/
,
. The
for
can operate before switching the flow into freshly reactivated drier
on hr
it
sec
gas velocity based flow through the empty drier shell must not exceed
ft
1
the silica gel weighs lbm bulk cubic foot what are the required diameter and
50
If
,
/
height
of
the drier bed

?
by
passing part the nitrogen product through

be
to
of
7.32 The drier reactivated

is
.
thealso
after this nitrogen has been electrically heated Nitrogen flow must
to
350
it
.F
°
velocity the empty drier shell

be
on
As
of
maintained below
ft
sec based
1
a
nitrogen flows through the drier the silica gel finally

so
heated and dried that

it
is
,
the
at 98
temperature
of an of
of
%
the adsorbed moisture and attains

If
loses 250
.F
at ? N
a
:
°
how long does

to
average temperature take reactivate the drier

of
150
it
leaves
as F
,
°
desorption may equal vaporization

be
to
of
The heat taken the latent heat

the same temperature Silica gel has heat capacity 0.2 Btu lbm
of
F
a
/
°
.
.
REFERENCES
1. Bodenstein , M. , and W. Pohl : Z. Elektrochem . , 11 :373 ( 1905 ) .

2. Chem . Eng . News, 37 (36 ) , Sept. 7 , 1959 .
3. Faith , W. L. , D. B. Keyes , and R. L. Clark : “ Industrial Chemicals , ” John Wiley
& Sons , Inc. , New York , 1957 .
4. Hester , A. S. , J. J. Dorsey , and V. T. Kaufman : Ind . Eng . Chem . , 45 :622 ( 1954 ) .
5. Kastens , M. L., and J. C. Hutchison : Ind . Eng . Chem ., 40 : 1340 ( 1948 ) .
6. Perry , J. H. (ed .) : “ Chemical Engineers ' Handbook ,” 3d ed . , McGraw - Hill Book
CHAPTER 8
ORGANIC CHEMICALS
The chemical industry produces a wide variety of synthetic organic

chemicals . Major categories include dyes , pigments , flavor and perfume
materials , medicinals , plasticizers , plastics and synthetic resins , synthetic
fibers , synthetic rubbers , rubber - processing chemicals , surface - active
agents ( detergents ), pesticides and other agricultural chemicals , and
intermediates .
Intermediates , which are chemicals used in the manufacture of other

organic chemicals , have the largest annual production of any of the
categories listed . A few of the more important intermediates are acetic
anhydride , aniline , formaldehyde , phenol , phthalic anhydride , and sty
rene . Organic chemicals have a wide variety of end uses , and in some
cases they can be produced by several alternate processes . For example ,
phenol is a very large volume intermediate . There are five alternate
processes for producing it , as shown in the product flow diagram , Fig .
the 8.1
.
Originally the only source phenol was from coal tar produced
of
in
,
of
of
destructive distillation the manufacture coke for blast

in
coal
furnaces The phenol present the coal tar was simply separated
in
and
.
purified After the First World War the sulfonation chlorination and
,
,
,
.
regenerative processes were introduced These processes used benzene

.
Until the Second World War most benzene was

as
raw material
a
.
-by
product
to
produced the destructive distillation

of
coal
of
give
as
a
so by
Since the war production catalytic reforming

of
coke benzene
of
,
.
petroleum fractions has been rapidly increasing that today the greater
,
portion produced from petroleum The cumene

of
benzene process
is
for phenol more recent development

which produces acetone
an
as
co is
- a
important product The production

synthetic phenol has com
of
.
pletely overshadowed the natural coal tar phenol which now less than
is
,
-
per cent the total production the phenol production

of
of
Details
5
.
be
processes may Refs and

in
found
5
2
.
.
an
several applications and

of as
Phenol such
in
used intermediate
is
is
Fig
8.1
the production large variety

as
of
chemicals shown
in
in
a
Over half the phenol produce phenolic resins for plastics

to
used
is
and
an
the
surface coatings About per cent serves

as
intermediate
in
5
.
300
Major Manufactoring Products using phenol Ultimate products
raw materials process as an intermediate and end uses
of
Refining
oil
lubricating
Benzene Phenolic resins
Benzene
as
Sulfuric acid such phenol Thermosetting
Sodium sulfite sulfonic formaldehyde
,
acid plastics surface
Sodium hydroxide coatings
-
process 2,4 Dichloro
phenoxyacetic
D
→
- weedkiller
acid 2,4
Benzene COOH
CIV
OCH
Acetylsalicylicacid
CI
Chlorine Chlorobenzene COOH
Aspirin
3
Sodium hydroxide process OCOCH
Salicylicacid
COOH Medicinals
OH
Methyl salicylate
oil
of
Benzene Synthetic
Pentachloro ÇOOCH3
Air OH wintergreen
PHENOL phenol o
Regenerative
CI
Water
,
process OH Wood preservative

OH fungicide
CICI
CI
Hydrochloric acid
CI
301
Picric acid
OH
Benzene
Propylene
Cumene
NO271NO
NOZ , Explosive dye
as
oxidation
,
,,
Epoxyresin such Adhesives

Air process OH
,
A
Bisphenol surface coatings
Acetone plastics
CH3 CHCH
ICH
-
,
.
HO -OH condice
сн
-food
CHE
Coal tar Coal tar Phenolphthalein

distillation Naphthalene HO OH Indicator
Cresol
,,
medicinal
C
0
=
Benzene laxative
Other products
Various dyes
as
such
→
Dyes
paperyellow
of
.
.
,
,
.
Fig 8.1 Raw materials manufacturing processes and end uses phenol
TABLE 8.1 . SELECTED ORGANIC CHEMICALS *
Production , tons
Acetanilide 1,390
Acetic acid (synthetic ) 273,077
Acetic anhydride 478,221
Acetone 305,384
Acetylsalicylic acid ( aspirin ) 10,410
Amyl acetates (90 % ) 4,547
Aniline 50,702
Barbituric acid derivatives 425
Butyl alcohol (primary , normal ) 105,279
Carbon disulfide 234,197
Carbon tetrachloride 156 , 438
Chlorobenzene ( mono ) 193,999
Cresols (total ) 20,828
Cresylic acid ( refined ) ,,
28 885
Dibutyl phthalate 6,451
Dichlorodiphenyltrichloroethane ( DDT ) 72,664
Dyes , Naphthol AS 305
Direct black EW 2,354
Chrome blue black R 505
Ethyl acetate (85 % ) 42,876
Ethyl alcohol ( thousands of proof gallons ) :
Synthetic 418 , 742
Fermentation and other natural sources 75,634
Ethylene glycol 564,852
Formaldehyde (37 % ) 679 2, 222
Methanol , synthetic 711,052
Naphthalene (refined ) 30,934
Penicillin and salts ( billion units 8) 391,574
Phenol 253 , 183
Phthalic anhydride 150,652
Pigment blue 24 1,091
Pyridine (refined ) 691
Streptomycin 90
Styrene 611,867
Sulfa drugs 1,863
Tetramethylthiuram sulfides 2,073
Tricresyl phosphate 13,232
Vitamins :
Ascorbic acid (vitamin C ) and derivatives 2,086
Ergosterol (vitamin D ) (billion units ) 16,906
Niacin and niacinamide 1,478
Pyridoxine (vitamin B6 ) 24
Thiamine derivatives ( vitamin B1 ) 75
* This table is reproduced from Ref . 1, with permission .

† In short tons unless otherwise noted .
| One billion units of penicillin is 600 g . The unit is defined by the biological activ
ity of the sodium salt of penicillin G.
ORGANIC CHEMICALS 303
manufacture of 2 , 4 - D weed killer , which is widely used . About 3 per

cent is used in the liquid extraction of lubricating oils , where phenol acts
as a solvent to remove undesirable constituents of the oils . Other end
product uses include fungicides , weed killers , explosives , dyes , and
medicinals . Only a few of the more important end products are shown in
Fig . 8.1 .
Product flow diagrams similar to Fig . 8.1 may be drawn for organic
and inorganic chemicals to show the starting materials , manufacturing
processes , and end uses . Table 8.1 lists representative organic chemicals ,
and Table 8.2 gives the major plastics and resin materials .
TABLE 8.2 . PLASTICS AND RESINS *
Production , tons
Alkyd resins 251,295
Cellulose plastics 70,680
Coumarone -indene and petroleum polymer resins 133,970
Epoxy resins 20,634
Phenolics and other tar -acid resins 243,931
Polyester resins 58,623
Polyethylene resins 432,364
Rosin esters 13,707
Silicone resins 1,599
Styrene resins 381,529
Urea and melamine resins 174,607
Vinyl and vinyl copolymer resins 434,708
Miscellaneous (acrylic , polyamide , etc. ) 96,159
* This table is reproduced from Ref . 1, with permission .
Because many synthetic organic chemicals are produced from raw

materials obtained from petroleum or natural gas , they may also be
classed as petrochemicals . For example , phenol is produced primarily
from benzene , much of which is produced from petroleum . Therefore ,

phenol may be considered a a petrochemical . The manufacture of phenol
from cumene is described in the following section .
PHENOL MANUFACTURE
Of the five processes used to manufacture phenol , the newest process ,

cumene oxidation , will be discussed here . The description of the process
is simplified , but the process data given are representative of actual
conditions , which may vary depending on the particular process . A
typical cumene - phenol plant produces 30 million lbm / year of phenol . AA
flow sheet is given in Fig . 8.2 , and additional process data may be found
in Table 8.3 .
Acetone
1
Cumene feed Cumene recycle
product
Hydrogen
Hydrogenator Water
3
Filter
Air
for
(
02
)
7
recovery cumene
purification phenol
recovery acetone
– Solid
- - phenol
Oxidizer Crystallizer
N₂
,
product
O₂
extractor acid Residual
304
tower Distillation
distillation Vacuum
Phase separator
distillation Vacuum
Water
+
up
-
Make dilute acid
sulfuric acid
9
6
8
Cleavage
reactor Crude acetophenone
Crude byproduct
Recycle
acid product
Separator
TABLE 8.3 . CUMENE -PHENOL PROCESS DATA *

(All compositions in mass per cent )
1. Ratio of fresh pure cumene to recycle is approximately 1 : 4 .

2. Recycle cumene
Composition : 98 % cumene , 2 % a - methylstyrene
3. Hydrogenator effluent
-
50 parts per million a -methylstyrene
1
4. Washed organic phase
Composition : 9.1 % acetone , 15.2 % phenol , 0.8 % acetophenone , 1.5 % a -methyl
styrene , 73.4 % cumene
5. Acetoneproduct : essentially pure acetone
6. Bottom product from cumene recovery column
Composition : 94 % phenol , 6 % acetophenone
7. Phenol product : essentially pure solid phenol
8. Acetophenone by - product :
Composition : 15 % phenol , 85 % acetophenone
9. Dilute sulfuric acid ( 10 % )
Molecular weights
Phenol 94.1 ,
a - Methylstyrene 118.2
Cumene 120.2 Acetone 58.1
Cumene hydroperoxide 152.3 Acetophenone 120.1
*
The process described in this table and accompanying text is based on Ref . 2 ,
supplemented with additional realistic values .
Raw Materials . Cumene is manufactured by the reaction of benzene

and propylene , as described in Chap . 9 . Both the benzene and propylene
are
derived from petroleum Air used for oxidation and dilute

is
,
.
supplied the cleavage reactor

to
sulfuric acid
is
recycle
of
Process Fresh cumene feed and unreacted cumene are

a
.
quantity
fed
methylstyrene from the

to
of
reactor where the small

a
reacted with hydrogen

at
to
to
recycle 210 and atm convert

is
it
F
1
°
cumene
.
CH CH
,
nickel
catalyst
-CH = CH2 -CH
+
H2 8.1
(
CH
a Methylstyrene Cumene
a
-
The ratio impure recycle cumene

to
of
fresh cumene about

is
4
1
:
.
The nickel catalyst finely divided and suspended the reaction

in
is
is
mixture by mechanical agitation The cumene product decanted from

is
.
the
catalyst
to
to
reactor filtered remove and sent the next stirred reactor

,
for oxidation
.
air
pure cumene gives low yields but the yield may

be
of
The oxidation
,
increased by emulsifying the cumene in a buffered aqueous sodium

carbonate solution ( pH of 8.5 to 10.5 ) . In this emulsified mixture of
aqueous and organic phases , the conversion of cumene to cumene hydro
peroxide varies from 25 to 40 per cent , depending upon such factors as
the ratio of aqueous to organic phases . The reactor operates at 265 ° F ,
and the reaction is
CH3 CH ;
CH + 02 → -COOH (8.2 )
CH , CH ,
Cumene Cumene hydroperoxide
Oxygen is supplied by bubbling air through the emulsion . The oxidation

reaction is autocatalytic . That is , as cumene hydroperoxide is formed ,
it increases the rate of reaction . Phenol and a - methylstyrene inhibit
the oxidation ; so they must be removed from the feed to the oxidizer ,
The organic phase is separated from the reaction mixture and passed
to a final reactor where the cumene hydroperoxide is split in an acid
medium to give phenol and acetone :
CH , CH
H2SO4
catalyst
-COOH -OH + C = 0 ( 8.3 )
CH CH
Cumene hydroperoxide Phenol Acetone
Dilute sulfuric acid is supplied to the cleavage reactor . After cleavage ,

the acid is separated from the organic phase and recycled , with the addi
tion of fresh acid . The cumene hydroperoxide is completely decomposed
to give primarily an equal number of moles of phenol and acetone . Ace
tone , a valuable organic intermediate and solvent , is a product equal in
importance to the phenol . The sale of the acetone co - product makes the
entire process economically feasible . Small quantities of a -methylsty
*
rene and acetophenone * are also produced as by - products .
The remainder of the process is the separation and purification of
products and remaining reactants . The organic phase is first extracted
* CH3
Acetophenone :
= 0
with water to remove residual sulfuric acid . The washed organic phase
contains acetone , phenol , a -methylstyrene , acetophenone , and cumene .
This mixture is sent to a series of three distillation columns where the
various products are separated . In the first column , which operates at
atmospheric pressure , acetone is separated as an overhead product .
The stream from the bottom of the first column is sent to the second
column , which operates under a vacuum to keep the distillation tempera
ture low . the cumene and a - methylstyrene
Here are the overhead
products . This stream is recycled to the hydrogenator . The stream
must be free of phenol because it inhibits the oxidation reaction . The
bottom product from the second column contains essentially phenol and
acetophenone , which are separated in the third column . The third
column operates under a vacuum , with phenol as the overhead product
and an acetophenone - phenol mixture as the bottoms product . When it
is economically justified , the acetophenone may be recovered and sold .
It is used as a perfume constituent , a solvent , and an intermediate .
Markets. The uses for phenol have been discussed earlier . Phenol
from cumene must compete with phenol produced by the other processes
8.1
shown in Fig . The sale product acetone equally impor

co
of
the
is
-
.
determining the economics process

in
as
tant the Acetone used
of
is
as a
.
wide variety
an
as
of
solvent and intermediate for chemicals such

a
,
acetic anhydride bisphenol methyl isobutyl ketone and methyl
A
,
,
by
methacrylate Acetone produced the cumene phenol process must

-
.
compete with acetone produced by other processes Large quantities

.
by
are produced from isopropyl alcohol and small quantity produced
is
,
recently developed process for hydrogen

of
fermentation molasses
A
.
peroxide manufacture produces more acetone than peroxide using iso

,3
propyl alcohol starting material High purity synthetic phenol

as
a
-
.
cents per pound the plant cents per

20
17
sells for about

or
at
drums
in
pound tank car lots

in
This discussion phenol show the wide variety

to
of
of
intended raw
is
processes typical large organic

of
materials and end uses volume

a
,
chemical Although phenol relatively old and established organic

is
a
.
chemical new processes and uses are still being developed

,
ETHYL ACETATE MANUFACTURE4

by
Ethyl acetate produced simple reaction between ethyl alcohol

is
Typical
its
organic processes production

of
and acetic acid concerned

is
,
.
largely with the separation the product from unreacted reactants and
of
an
an
impurities The reaction between organic acid and alcohol

is
.
ethyl alcohol and acetic acid

In
of
called esterification the esterification

,
of .
.
catalyst The
as
small amount concentrated sulfuric acid used

is
a
a
.
reaction is reversible and gives a 67 per cent yield at equilibrium , starting
an
all
with equal moles of reactants . To obtain higher over - yields excess
,
of
alcohol and the water formed the reaction
in
is
used removed
is
.
The process flow sheet given Fig 8.3 and process data are found
in
is
in
,
.
Table 8.4
.
Raw Materials The three starting materials are common industrial
.
chemicals Ethyl alcohol produced from ethylene obtained from
is
.
Water
12
7
Crude
product Mixer
Separation column
5
Product column
Sulfuric Organic 11
acid phase
Esterification column
10 Aqueous
3
Ethyl phase
alcohol Preliminary
Mixer product Settler
1
and
2
preheater
Acetic
acid
13
Ethyl
acetate
product
Alcohol
recycle
Water sulfuric
-
acid waste
Fig 8.3 Ethyl acetate manufacturing process

.
per
as
petroleum The alcohol produced and sold

or
natural gas
95
is
a
..
cent aqueous solution The manufacturing process for ethyl alcohol

is
.
Chap Acetic acid may any concentration

be
described used
in
in
9.
in
.
aqueous solution produced by variety processes The largest

of
It
is
a
.
.
of
of
volume method manufacture the reaction methane and carbon

is
i
by
also produced acetaldehyde

of
monoxide Acetic acid the oxidation

is
.
by
ethyl alcohol the latter The ethyl acetate process

or
fermentation
,
described here uses 100 per cent acetic acid although other acid concen
,
trations may small quantity per cent sulfuric acid

98
be
of
used
A
is
.
as
used catalyst
a
.
TABLE 8.4 . ETHYL ACETATE PROCESS DATA *

( All compositions in mass per cent )
Plant production : 425 lbm / hr ethyl acetate product
1. Ethyl
alcohol feed
Composition : 95 % ethanol , 5 % H2O
2. Acetic acid feed : 100 % acetic acid
3. Sulfuric acid catalyst
Composition : 98 % H2SO4 , 2 % H2O ,
Flow rate : 13 lbm / hr
4. Preliminary product
Of the original acetic acid 65 % has been converted to ethyl acetate at this point .
5. Crude product
Composition : 66.2 % ethanol , 24.2 % ethyl acetate , 9.7 % H2O
6. Water -acid waste
Composition : 97.10 % H20 , 0.94 % H2SO4 , 1.45 % ethyl acetate , 0.51 % ethanol
7. Overhead from separation column
Composition : 85.2 % ethyl acetate , 9.5 % ethanol , 5.3 % water
8. Alcohol recycle
Composition : 48.6 % ethanol , 47.7 % H20 , 3.7 % ethyl acetate
9. Water feed
Composition : pure H2O
10. Organic phase to separation column
Composition : 88 % H20 , 8 % ethyl acetate , 4 % ethanol
11. Organic phase to product column
Composition : 94 % ethyl acetate , 4 % H20 , 2 % ethanol
12. Overhead from product column
6.7
2.9
Composition : 90.4 % ethyl acetate ,

%
H20 ethanol
%
,
13. Ethyl acetate product

Composition 99.0 ethyl acetate 0.75
%
ethanol 0.25
H
0
,
,
:
hr
Flow rate 425 lbm

/
:
Data this table are reproduced from Ref with permission The data have
in
4,
*
been slightly adjusted and augmented permit more complete mass balances
to
Process The basic reaction

is
.
catalyst
CH3CH2OH CH3COOH CH3COOCH CH3
+
H2O 8.4
→
Ethyl alcohol Acetic acid Ethyl acetate
Approximately stoichiometric quantities

of
ethanol and acetic acid

the mixer preheater along with the sulfuric acid catalyst
to
are fed
,
-
The reaction fast and reaches the near equilibrium conversion per
65
of
is
The resulting mixture distillation

to
of
cent the acetic acid fed

is
a
.
To force the equilibrium toward complete conversion

of
column the
.
an
ethanol rich recycle stream supplied

to
acetic acid the column

is
,
,
-
off
and the ethyl acetate and excess ethyl alcohol are distilled
as
crude
product From the bottom
of
the column water and sulfuric acid are

,
.
withdrawn
.
The crude product the second distillation column The

to
sent
is
.
overhead from this column is a ternary azeotrope * of ethyl acetate , ethyl

a substantial quantity of ethyl alcohol and water
alcohol , and water ; but a
is removed of the column .. This stream is recycled
from the bottom
to the esterification column to provide an excess of ethyl alcohol so that
all
the acetic acid consumed Because the three omponent azeotrope
is
-c
top the column contains only per cent ethyl acetate
85
of
from the
it
,
by
purified
be
must further means other than distillation The one phase
-
.
azeotrope a mixer where mixed with water and with stream
to
sent
is
it
is
a
a
from the product column This mixture separates into two phases The
.
aqueous phase the separation column
to
to
returned recover small
is
quantities alcohol and acetate present The organic phase

of
sent
to
99 is
a
.
final distillation column where the product withdrawn per cent
of as
is
,
acetate from the bottom the column The overhead

of the product
.
the ternary azeotrope and binary
of
column consists
of
mixture
a
a
azeotrope ethyl alcohol and water This overhead stream recycled
of
is
recover ethyl acetate and ethyl alcohol .
to
.
This process demonstrates well how recycle streams may
be
used
to
by
conserve valuable raw materials and products Often only such con
.
process economically
be
servation can made feasible

a
.
Energy requirements for organic processes must carefully evaluated
be
.
Energy balances may any process
be
as
determined for such the two
,
described this chapter sufficient data are available The techniques
in
if
,
determining the energy balances are those discussed Chap .
in
6.
of
In
.
practice heat capacities heats
or
of
heats formation combustion
of
,
,
,
vaporization thermodynamic properties
of
and other materials involved

,
process must
be
on an
of or
known estimated measured before energy

in
a
energy balances
be
balance can made The calculation organic

.
processes the problems Chap

of
in
included
is
9
.
.
PROBLEMS
8.1
8.1
Fig
for
Prepare product flow diagram similar

to
raw material rocess

a
-
of .
.
-p
any the major organic chemicals listed Table 8.1

in
theend
8.1
all
8.2 For any the major chemicals listed possible

of
Table determine
in
,
.
an
uses
all
as
the chemical intermediate determine the end use

If
of
used
is
.
ultimate products Where possible indicate what property

of
the chemical makes

it
,
.
particularly suitable for each application

.
Fig 8.2 Table 8.3 and the accom

on
to
of
Problems 8.3 8.11 are based the data

,
,
.
panying text
.
plant producing 3,750 lbmт solid phenol product calculate the flow
hr
8.3 For
of
,
/
a
.
the following streams cumene recycle acetone prod

of
rates cumene feed

6
a
c
(
)
,
,
:
(
)
(
)
-pby
uct acetophenone roduct stream

d
,
(
)
An azeotrope particular composition which the equilibrium

in
of
mixture
is
a
a
*
by
be
vapor and liquid have the same composition Such mixture cannot separated
a
.
simple distillation
.
8.4 . How much hydrogen is required to convert the a- methylstyrene in a plant

producing 3,750 lbm / hr of solid phenol product ?
8.5 . How much oxygen is required in the oxidizer in a plant producing 3,750 lbm / hr
of phenol ?
8.6 . How are the a - methylstyrene and acetophenone by - products formed ?
8.7 . Some plants recover a- methylstyrene from the cumene recycle for sale as a by
product . In a plant producing 3,750 lbm / hr of phenol product , how much a -methyl
styrene is produced and recovered ? How does this recovery change the process ?
8.8 . What percentage of the cumene entering the reactor is converted to phenol in
one pass ?
all
percentage conversion phenol
to
of
8.9 . What is the over - the entire
in
cumene
process
?
all
percentage yield
of
8.10 What the over acetone
is
?
-
.
recycle cumene Check the approximate

to
of
8.11 Calculate the ratio fresh feed
(
.
.
value given
to
of
Table 8.3
in
1
)
.
Fig
on
Table 8.4 and the accom

to
of
Problems 8.12 8.19 are based the data 8.3
,
.
panying text
.
the ethyl alcohol and acetic acid feeds

of
8.12
Calculate the flow rates
.
.
at
8.13
How much water added the mixer stream
of is
9
?
(
)
.
8.14 What percentage the acetic acid charged ethyl acetate
to
converted
in
is
.
the ethyl acetate product

?
the composition the preliminary product

of of
8.15 What
is
?
.
8.16 Determine the flow rates the four streams entering and leaving the sepa
.
ration column
.
all
composition the mixture flowing from the mixer
to
of
8.17 Calculate the over

-
.
the settler
.
organic phase and aqueous phase from the settler

of
8.18 Determine the flow rates

.
of .
8.19 The ethyl acetate process
80
be
an
to
to
modified use per cent solution

is
.
The crude product from the top

as
of
acetic acid water the esterification

in
feed
a
have the same composition and the total production Calcu

to
as
column before
is
is
,
.
all
late the flow rates and compositions streams that change when per cent acid
80
of
substituted for 100 per cent acid

is
REFERENCES
Eng Sept.
37
36
News
2. 1.
Chem 106ff 1959

,
7,
(
)
(
:
.
).
R.
Keyes and John Wiley

D.
Faith W. Clark
B.
L.
L.
Industrial Chemicals
&
”,
,
“
:
Sons Inc. New York 1957

C. ): ,
,
,
.
36
11
Petrol Refiner 273 November

4. 3.
1957
,
,
D. (
(
.
).
K.
Chemical Engineering Data Book

T.
Ross and Freshwater Leonard

”,
,
“
:
Hill Books London 1958

,
,
.
W
P.
Sherwood Petrol Proc 1348 1953

5.
8
.:
.,
,
).
:
.
CHAPTER 9
oil PETROLEUM AND PETROCHEMICALS
Crude has been known since ancient times the many places where
in
petroleum
to
has seeped
of
the surface Where such natural sources
it
.
fuel for lighting ancient Sicily and Babylon
as
as
existed was used
in
it
a
,
.
by
early French
oil
In
the United States seepages
of of
were noticed
,
missionaries The greatest source petroleum was along Oil Creek
in
.
oil
western Pennsylvania Early settlers this region used recovered
as in
.
In
from small surface springs exclusively medicine about 1847
,
.
Samuel Kier Pittsburgh began bottle petroleum recovered from salt
to
of
remedy for rheumatism gout neuralgia and blind

to
as
wells and sell

it
,
ness About 1850 Kier developed distillation
to
of
crude method
.
a
,
by
improve the fuel characteristics the petroleum eliminating the smoke
of
oil
and odor He called the new product carbon Demand soon
.”
"
.
the supply increase the supply were

to
exceeded Various methods

.
unsuccessful until 1859 when Edwin Drake drilled successful discovery

a
Titusville Pennsylvania This well showed that petroleum could

at
well
,
commercial quantities and launched the modern petro

be
recovered
in
leum industry
.
Refining petroleum was initially confined distillation the crude

of to
of
of
Products initially
oil
into several fractions interest were kerosene

.
The more volatile frac

oil
for lighting lubricating and paraffin wax

,
tions including gasoline were too dangerous for use illuminants and
as
?,
were frequently discarded 1900 kerosene was the most important

In
>
,
.
petroleum product
.
With the advent the turn the century gasoline

at
of
of
the automobile
,
for internal combustion engines rapidly became the major product

.
-
Only limited quantity rather low rade gasoline could obtained by

be
so of
a
-g
oil
distillation necessary develop processes

of
to
crude was convert

it
be to
;
as
oil
other components
to
materials that could used

of
the crude
oil
gasoline the complexity refinery

to
Much
of
of
the modern due the

is
.
numerous processes for making higher rade gasoline More recently

,
.
-g
the growing interest the production chemicals and plastics from

of
in
components petroleum many new processes for the

to
of
certain has led

recovery components from the refinery streams Natural gas
of
these
.
raw materials for chemical manufacture Chemicals

of
also source
is
312
PETROLEUM AND PETROCHEMICALS 313
made from any component of petroleum or natural gas are called petro
chemicals . Fuels and lubricating oils are generally excluded from this
definition , even though they may contain substantial quantities of com
oil
ponents produced from the chemical processing of crude - fractions
.
by
For example benzene produced reforming the petroleum refinery
in
is
,
.
Often increase the octane num
to
as
not recovered such but used
is
is
as of it
ber gasoline fuel pure form and
In
other cases recovered
in
of is
it
*
as
used raw material for production chemicals such phenol
a
.
When used gasoline benzene not petrochemical recovered
in
If
is
be a
,
a .
and used chemical synthesis may petrochemical
as
considered
in
it
,
.
Any such classification arbitrary
is
. oxygen
an
Petroleum usually occurs near shore marine sediments
in
in
-
oil
deficient environment Most produced the United States comes
in
.
from Texas Louisiana and Oklahoma Since ancient seas covered much
,
Wyo
oil
of
inland locations such
as
the Americancontinent found
in
is
,
ming and Illinois generally believed that petroleum originated

It
the
in
is
.
decomposition organic matter debris from living plants and animals

of
.
Conversion processes which took place over millions years may include
of
,
,
thermal decomposition fatty oils radiation induced reactions from
of
radioactive rocks bacterial action and reactions catalyzed by minerals

,
be .
oil
The youngest crude produced the United States
to
estimated
in
is
oil
million years old formed and became sufficiently

10
As the
to
13
fluid gradually seeped into the geological formations from

it to
flow
it
,
which recovered today

is
Crude petroleum complex mixture several hundred compounds

of
is
a
No complete analysis has been made Petroleum composition varies .

.
substantially with crude oils are primarily hydro

its
all
location but
,
carbon compounds including paraffins

or
as
such butane octane

,
,
(
cycloparaffins cyclohexane
as
as
such and aromatics such benzene

,
(
(
).
Oxygen organic acids may reach per cent some crude oils Sulfur
as
in
3
compounds are present many crude oils For example Wyoming

in
,
.
crudes may have per cent sulfur Nitrogen compounds

as
as
much
5
,
.
metals etc. are sometimes found low concentrations No unsaturated

in
,
hydrocarbons ethylene propylene

or
as
such found natural

in
are
(
petroleum
.
Natural usually largely methane with varying smaller quantities

gas
is
other gaseous paraffin hydrocarbons hydrogen sulfide nitrogen

of
,
,
carbon dioxide helium and water vapor Methane content may range
,
.
of
of
Octane number measure the antiknock characteristics fuel for an

is
a
a
*
by
internal combustion engine Knocking caused irregular combustion the

in
a is
-
by
of its
engine cylinder given fuel comparing

of
The octane number determined

is
in .
performance standard experimental engine with the performance

of
mixtures
a
heptane octane number and isooctane octane number 100

0
n
(
-
).
from 50 to 99 per cent . Natural gas occurs under pressure in under

ground cavities , and it is frequently associated with petroleum .
Because petroleum has a complex composition , the chemical reactions
involved in processing are not always clear cut . It is frequently neces
sary to work with average properties both in raw materials and final
products . The same complex composition provides a wealth of starting
compounds for the manufacture of petrochemicals .
PETROLEUM REFINING
oil
Modern petroleum refining is planned to yield products from crude
oil
which are most attractive economically Simple distillation crude
of
,
.
which the first step refining produces insufficient high octane
in
is
, -
gasoline meet today's increased requirements many
to
Therefore
.
convert other fractions from the initial
to
processes have been devised
distillation into high octane components for gasoline Figure 9.1 shows
-
.
Gas
%
4
%
;
Gas
1
23
%
Gasoline
low quality
(
Gasoline and
related products
45
%
Kerosene and
jet fuels
14
%
Heating oils
and diesel fuel
16
%
Kerosene and
gjet fuels %
9
Heating oils
31
oil
Gas
|
and diesel fuels

28
%
oil
Lubricating
%
3
oil
Lubricating
%
5
Heavy residual
oil
Fuel and
12
%
for fuel
%
residuals
9
(
Initial components from Ultimate products

oil
crude distillation after refining
Fig 9.1 Typical initial components and ultimate products from crude petroleum
.
.
typical products from crude - distillation and ultimate products after
oil
further processing The quantity and quality gasoline are substan
of
.
tially Heating
oil
increased since demand the product most
in
is
it
,
,
.
diesel fuels and lubricating oils products The quan are also important
,
.
tity gas increases because decomposition larger molecules
of
of
of
of in
several the refining processes
of
When desired small quantities
,
.
various components may recovered for petrochemical use The out
be
.
put refinery can varied according
be
to
of
consumer demands and other

a
oil
economic factors The type supplied will influence ultimate
of
crude
.
plant products For example plant processing high sulfur crude

a
a
,
-
.
-pby
may produce sulfur roduct
as
or
sulfuric acid
.
Typical Petroleum Refinery processes and prod To illustrate the
A
an .
actual medium sized refinery will
be
ucts petroleum refineries
of
-
described The refinery located near the Delaware River and receives
is
.
It
by
oil
its crude tanker from Texas Venezuela and the Middle East
,
.
processes over 150,000 barrels petroleum each day The refinery has
of
oil
developed large paraffin wax market and therefore buys crude
a
a
,
-
with high wax content Much significant sulfur

of
the crude also has

a
.
content that sulfur removal and recovery facilities are necessary

so
,
.
Figure 9.2 shows the major process units and the major products Each
.
process unit complete chemical process itself Raw material and
in
is
tie a
product lines the process units together The products shown are
.
the major ones There are many others For example wide variety
of
a
,
.
waxes are produced

.
The refinery shown includes the catalytic reforming process discussed

in
earlier chapters Most the reformer product goes gasoline

to
, of
.
blending
In
other refineries benzene toluene and the xylenes are

,
,
.
recovered before the product stream gasoline blending

to
sent
is
High octane streams the gasoline blending plant flow from several
to
-
9.2
Fig Catalytic cracking reforming polymeriza

as
sources shown
in
,
,
.
tion and alkylation were

all
developed produce higher octane fuel

to
a
,
obtained from simple crude distillation More recently

be
than could
,
.
the products have proved more valu

be
to
these processes
of
of
several
as
starting petrochemical than for use

as
able materials manufacture

in
fuel
.
The detergent plant utilizes propylene tetramer and sulfuric

benzene
,
,
all
acid which are the produced

refinery plus sodium hydroxide The
in
,
,
final product sodium dodecylbenzene sulfonate widely used house

in
is
,
hold and industrial detergents The required sulfuric acid produced

is
.
H2S removed from various refinery streams such

as
from the reformer

,
feed
.
Hydrogen from the reformer combined with nitrogen from the air
is
as
produce ammonia for use synthesis and fertilizer Benzene

in
to
a
,
,
.
,
Methane ethane Fuel
(
)
Propane Liquified petroleum gas LPG fuel
(
- C6
Cy
Catalytic Light isomer
Light Propane Detergent
Light gases manu Detergent
) )(
gas Propylene polymerization Propylene tetramer C12
recovery facture C12H25 -503Na
,
Butane butylene Butane
Alkylation
Isooctane
,
Benzene Hyso NaOH
Gasoline Sulfur Catalytic Hydrogen
Ammonia
(
removal Ammonia
)
reforming Gasoline high octane
(
)
low quality manu
Nitrogen facture NH3
to
-
Solvent HS H2SO4plant
naphtha Solvent naphtha
Gases
,
Crude
jet
Kerosene Kerosene fuel
oil
,
Gas oil Catalytic Cracked gasoline Gasoline blending Gasolines
distillation Crude
additives
316
cracking
Lubricating
oil
Domestic heating
oil
stock
Thermal
Residuum
oil
cracking Industrial fuel

viscosity
reduction
,
Treating
blending Lubricating
oil
Lube
Phenol additives oils
Propane Deasphalted Treated MEK solvent
solvent
oil
oil
deasphalting dewaxing Wax
extraction Acid Paraffin
treating wax
Asphalt
.
.
. (
Fig 9.2 Petroleum

)
refinery Courtesy Atlantic Refining Co.

detergent , and ammonia are considered petrochemicals . The sulfuric

acid also has a petroleum origin .
Petroleum Processes . A number of petroleum processes will be
described briefly . Because the feed and product streams are frequently
complex mixtures of numerous compounds , the exact composition is not
always known , and rigorous material and energy balances are not often
possible .. However , approximate balances using average properties may
be employed . The chemical reactions written for the processes described
are often typical reactions which are frequently accompanied by several
others of a similar type .
Crude distillation is carried out in a series of large distillation columns .
One column separates the most volatile components from the bulk of the
oil
oil . A second column further separates the into several fractions
,
and third column operating under vacuum separates the least volatile
a
heavy components obtained from the bottom the second column into
of
(
several fractions Auxiliary equipment includes heat exchangers fur
,
.
naces for heating the feed and steam strippers for purifying the product
,
streams All the streams leaving the crude distillation unit are complex
.
by
mixtures The mixtures are usually characterized their boiling range
.
.
The most volatile components vaporize the lowest temperature and
at
,
the heaviest components vaporize the highest temperature given
at
at
a
To
pressure prevent thermal decomposition the heaviest components

,
..
lower their boiling temperatures

to
are distilled under vacuum

a
Catalytic cracking major process for converting heavy fraction .

is
a
,
As
oil
gas into high octane gasoline the name implies the process
,
,
-
splits large molecules into smaller ones Typical reactions would

be
.
catalyst
CH2CH =CH2
+
C12H26 C9H20 9.1

(
900
F
°
Dodecane Propylene Nonane

catalyst
=
CH2CH
+
H20 CH2 C6H14 9.2

C,
900
F
°
Nonane Propylene Hexane

CH
,
catalyst
CH3 CH2CH CHCH
+
-CHCH2CH3 CH 9.3
=
900
F
°
sobutyltoluene Butylene Toluene

m
-I
Because the feed complex mixture many reactions occur The major
is
a
products catalytic cracking high gasoline

93
from are octane octane

-
propylene butane and butyl

oil
as
unleaded heating and gases such

>
),
,
(
which are used various other refinery processes see Fig 9.2
in
ene
)
).
oil
A typical modern catalytic cracker converts gas per cent
58
into
oil
gasoline per cent fuel
24
and the remainder gases
.
large catalytic cracker the frontispiece
of
shown this book
A
is in
A
is
.
simplified flow diagram given Fig 9.3 Units
of
this
in
of
the unit
.
.
oil
type may process 2,500 100,000 barrels per day gas feed depend
of
to
,
in on
ing the unit Often the catalytic
of
the size cracker the tallest
is
.
the refinery Some reach the height story building
25
unit
of
a
-
.
.
Flue gas stack
to
Gas
recovery
Cyclones system
to
separate solid
catalyst from gas
Gasoline
Reflux
Regenerator
Distillation
column
-Air Light cycle
oil
Cracked product
Spent Cyclone
to
11,1
catalyst separate solids
-Regenerated
Reactor
catalyst
Slurry D
Recycle
oil
Gas
feed
i
Steam
Air
W.
Fig 9.3 Catalytic cracking process Courtesy M. Kellogg Co.

(
)
.
The catalytic cracker consists three major units catalyst

of
reactor
aa
a
,
:
regenerator and product eparation distillation column The reactor

a
,
.
-s
Al
located under the regenerator The catalyst mixture

03
of
is
and
,
.
SiO2 very finely divided and flows easily like fluid

it
is
a
,
the
oil
The recycle stream and fed

mixed with
to
gas feed
of
base
is
reactor where contacts the hot fluid catalyst coming from the regenera
it
,
up
tor The gas reacts through the agitated catalyst

as
passes The
it
.
gas then flows into cyclone separator where much entrained catalyst
a
the
removed from the gas The product gas flows from the reactor
to
is
.
product distillation column , where the gas , gasoline , fuel
to oil
and recycle
,
streams are separated slurry stream also returned the reactor
is
A
.
.
, on
As the reaction proceeds carbon deposited the catalyst the
in
is
,
The carbon reduces the catalyst activity
be
reactor
so
that must
it
.
burned off the regenerator The catalyst
of
the center the reactor
in
in
in up .
blown by
an
into the regenerator where the carbon
is
air stream
is
,
off
burned the regenerator

The air added
to
aid combustion flows
in
.
out through cyclone separators The separators
to
several the stack
.
remove entrained catalyst from the combustion gases The burning
of
.
up
the carbon heats the catalyst which then flows back down
in to
the
,
by
off
reactor The heat supplied burning the carbon used the
is
..
reactor the cracking reactions are endothermic

because Many other
,
.
types reactor regenerator and catalyst are used The system illus
of
,
,
.
by
trated was developed the M. W. Kellogg Company
.
Thermal cracking usually used split molecules the heavy com
to
of
is
ponents may used for producing
be
the residuum reduced crude
It
in
).
(
gasoline and а heavy residue may produce catalytic cracker feed

or
it
a
a
;
oil
and Fig 9.2 The process involves heating the

to as
fuel shown
in
a
lbs
sq
reduced crude about 950 under pressures above 200 The
in
/
°
F
.
6. by
molecules are split and the new species are separated distillation
,
.
In
Catalytic reforming was discussed Chaps and reforming
in
2,
5,
,
.
the carbon atom chains the petroleum molecules are rearranged usu
in
-
as ,
ally into branched chain cylic patterns The sulfur removed
or
H2S
-
from the reforming feed and other refinery streams may

be
as
recovered
elemental sulfur Sulfur must frequently
or
to
converted sulfuric acid

.
to be
removed from refinery streams prevent poisoning catalysts and

to
of
improve the properties products One large Texas refinery pro

of
duces 300,000 day high purity sulfur

of
lb
/
of -
Light gas recovery consists distillation columns where the

of
series
a
-
various dissolved gases present petroleum are separated These gases

in
are primarily hydrocarbons with one Methane

to
four carbon atoms

.
may
be
CH4 burned with the

as
burned fuel Ethane C2H6

is
be a
(
)
.
may separated and cracked give ethylene C2H4

or
to
methane
it
a
,
),
(
starting material for many petrochemicals No olefins appear crude

in
.
petroleum however the heating the crude distillation column causes

in
;
some thermal cracking that propylene and butylene are produced

so
,
.
In
catalytic cracking olefin gases including ethylene propylene and

,
butylene are produced and recovered The propane C3H8 -propylene

(
)
.
C2H6 fraction separated the light gas recovery unit and sent
to
in
is
(
-
)
catalytic polymerization The butane C4H10 -butylene C4H fraction

,
(
)
.
separated and sent the alkylation plant Fig

to
as
shown
in
9.2
is
.
for
the starting point butyl and

as
other refineries this fraction used

is
GR synthetic rubbers
S
-
.
Catalytic polymerization involves the combination of two or more
for
olefinic hydrocarbons to give a larger molecule . For example ,
propylene
,
catalyst
2CH C6H12 9.4
)
Propylene Propylene dimer
catalyst
and 4C3H6 C12H24 9.5
)
(
Propylene Propylene tetramer
Propylene dimer and trimer are used gasoline blending Propylene
in
-
dodecylbenzene C6H5
of
tetramer used the manufacture
in
is
C12H25
),
(
detergent intermediate Many isomers the products will
be
of
formed
in a
catalytic polymerization The dodecylbenzene used detergent
in
.
polymerization proceeds
of
manufacture mixture several isomers
If
is
a
.
beyond the tetramer ultimately low rade polypropylene resin would
a
,
-g
result This material which normally manufactured
in
different
is
a
,
.
process rapidly growing resin for plastics The unreactive propane

is
a
,
be
removed for use fuel liquefied petroleum gas LPG may
as
or
is
it
a
;
(
)
give ethylene and propylene
to
cracked
.
Alkylation an
an
usually the combination isoparaffin with
of
olefin
is
produce larger molecule volatility and higher octane
for
to
of
lower
a
gasoline the refinery shown Fig isobutane and butylene react

In
in
9.2
,
.
give isooctane
to
CH3 CH
;
catalyst
=
CH3CH CH2CH CHCH CH3CCH CHCH

+
9.6
,
;
)
heat :
CH CH CH
,
Isobutane Butylene Isooctane

n
-
2,2,4 trimethylpentane
(
)
-
give different isomers octane may occur

is to
of
Various other reactions

.
4,8
The reaction mechanism complex

.
An alkylation particular interest the reaction between propylene

of
is
give cumene isopropyl benzene

to
and benzene
(
)
:
CH
9.7
-CH
→
CHCH2
+
CH
=
)
(
o
1
CH3
Benzene Propylene Cumene
The process for the manufacture cumene was developed the Second
in
of
be
World War when cumene was found

for
to
valuable constituent
a
aviation gasoline where high power was required More recently

.?
cumene has become a valuable starting material in the manufacture of

phenol and acetone , as described in Chap . 8. Cumene manufacture is an
olefin - aromatic alkylation , as opposed to the more typical olefin - iso
paraffin alkylation described earlier .
The cumene process ( Fig . 9.4 ) consists of a reactor using a solid phos
phoric acid catalyst and three distillation columns to separate the product
and reactants . Data for a typical process are given in Table 9.1 .
Benzene recycle
Propane Cumene
Reactor feed product
product
9
Propane recovery column
Cumene purification column

Benzene recovery column
Heater
Reactor
Coolant
5
3
Propane and
propylene
w 10
Heat Heavy
Feed tank
1
exchanger bottoms
2
Benzene
Fig 9.4 Cumene manufacturing process Courtesy Chemical Engineering Progress

(
)
.
The feed benzene must

be
sulfur free prevent catalyst poisoning

to
-
The propylene supplied mixed with propane comes from the light
as
is
it
gas recovery unit the refinery The feed benzene recycle benzene and
in
,
in .
propane propylene are mixed preheated

to
feed tank and fed the

,
a
,
-
be
The reaction that heat must

so
reactor exothermic removed from

is
,
.
maintain the temperature The reactor pressure

to
the reactor
at
250
C
°
.
sq
400
.in
is
lb
,
/
of by
The vapor reaction mixture the heat exchanger used

to
cooled
to is
preheat the feed and passed series three distillation columns

a
.
In
the first column propane and unreacted propylene

of
small amount
a
,
In
propane cracking
or
to
to
are removed and sent either fuel gas the

.
removed and recycled An excess

of
second column excess benzene

is
,
used initially
In
as
much propylene possible

to
as
benzene convert the

is
.
*
TABLE 9.1 . CUMENE PROCESS Data *
( All compositions in mass per cent )
1. Propane - propylene feed

Composition : 48 % propane , 52 % propylene
Flow rate : 3,720 lb / hr
2. Benzene feed
Composition : pure benzene
3. Recycle benzene
Composition : 95.3 % benzene , 4.7 % propane
4. Reactor feed ( gas )
Pressure : 400 lbs / sq in .
Composition : molar ratio of benzene to propylene is 3 : 1
5. Reactor effluent ( gas )
Pressure : 400 lbs / sq in .
Conversion of 94.5 % of propylene to cumene . The remainder is converted to
all
heavier molecules , assumed to be diisopropylbenzene
.
Propane product
6.
Composition propane with negligible traces benzene and propylene

of
:
Benzene column feed

7.
Composition cumene benzene propane and heavy impurities iisopropyl

,
,
:
(d
benzene
)
Cumene column feed

9. 8.
Cumene product
Composition 99.4 diisopropylbenzene
%
cumene 0.5 benzene 0.1

::
,
,
10. Heavy bottoms

6.6
Composition heavy benzene derivatives from side reac

%
%
cumene 93.4
,
:
tions assume diisopropylbenzene

(
Physical Data for Cumene

ml
Density
25
at
0.859
/g
C
°
:
38.3 66.1 107.3 129.2 143.5 152.4 163.3 180.7

T
C
°
Vapor
pressures
mm Hg 10 40 200 400 600 760 1,000 1,500
P,
vaporization
at 25
AH
at
at
10,789 cal 8,970 cal

of of
Heat mole mole

,:
152.4
cal g
/g
25 C
( C
° ;
,
Heat combustion AHc 1,257,310 mole cumene gas

H
CO2
0
/g
)]g
C
,
),
(
I(
:
Heat capacity 126.8 226.8 326.8

T
C
25
°
38.3 48.0 57.9 66.2

CP
cal mole
g
°
,
on
The process described this table Ref and reprinted with

in
based
is
is
7,
*
permission
.
final column , cumene is recovered ( 99.4 per cent pure ) , and heavy mate
rials formed by side reactions go out the bottom of the column .
After the Second World War many cumene plants were shut down for
lack of demand . With the development of the cumene - phenol process ,
many of these plants have been reopened .
by
The lubricating -
oil
improve
to
stock treated several processes
is
various characteristics the oil propane deasphalting propane
of
In
is
,
.
oil
used extract the lubricating from the heavy residual asphalt The
to
.
.
propane Asphalt must
be
recovered and recirculated removed from
is
.
lubricating
oil
to
because tends oxidize easily Phenol extraction
it
.
removes polycyclic aromatics from the lubricating
oil
Such compounds
.
undergo large viscosity changes with temperature and are therefore
unsatisfactory motor oils MEK extraction necessary because
in
is
.
petroleum waxes
oil
lubricating crystallize out low temperatures
at
in
.
Methyl MEK
oil
ethyl ketone processing causes the
to
added the
in
an (
wax crystallize easily filterable form when the solution chilled

to
in
is
.
The wax filtered off treated and sold for various uses such
as
wax
is
coating for paper milk cartons The MEK solvent recovered for
is
.
The lubricating
oil
reuse further treated and blended Often ad

is
.
.
ditives are included the oil
in
The processes described briefly here are representative the very
of
large number processes petroleum refining
of
References and
in
used
5
.
give more complete summaries petroleum processes

of
PETROCHEMICALS
Petrochemical production the most rapidly growing segment

of
the
is
chemical industry today Since the Second World War petrochemicals

,
.
have grown per cent the total tonnage chemicals produced

28
to
of
of
over
today Development new processes and products expected
be to
of
is
.
In all
that by 1970 over per cent chemical tonnage will

50
so
of
continue
,
produced from petroleum and natural gas dollar value petrochem

in ,
.
per production
60
nearly the United

of
icals are cent the total chemical

11
States
.
Although the petrochemical industry large compared with chemical

is
manufacturing small when the entire petroleum industry consid

is
is
it
,
all
per cent petroleum and natural gas produced

of
ered Less than

is
2
.
used petrochemicals
in
Raw Materials By definition petrochemical produced from raw

is
or a
,
.
materials derived from petroleum natural gas Often several refinery

.
streams are potential sources raw materials leading given finished

to
of
may
be
product refinery useful for several

In
other cases stream

a
,
.
purposes and economic considerations determine for which purpose the

,
stream will be used . For example , the product stream from catalytic
reforming contains benzene , toluene , and xylenes , which may be either
left in the stream to increase octane number or removed as starting
materials for petrochemicals . An economic analysis must be made to
determine the desirability of recovering the aromatics . Such analyses
are often complex , because they must consider the effect of a change in
with regard to gasoline pro
one stream on the whole refinery , especially
duction . Removing the high -octane aromatics from the reformer prod
uct requires addition of other high -octane components in gasoline
blending
To illustrate the diversity of sources and end products , the most
important petrochemical raw material , ethylene , will be considered in
detail . Years ago ethylene was produced as a by - product along with
so oil
other light olefins in the cracking of heavier give gasoline
to
fractions
.
Ethylene was too volatile for motor fuels
as
was used gaseous
it
a
;
the
relatively To increase the value ethylene
of
of
fuel low value the
,
.
light gas stream was processed ethyl alcohol

to
to
recover and convert
it
,
by
which was sold competition with ethyl alcohol produced fermenta
in
for
As
sugars the lower riced synthetic ethanol

of
tion the demand

.
-p
as
grew more ethylene was required than was available cracking
>
a
,
-pby
roduct ethylene Today be

to
of
Other sources had found
it
is
.
.
by
also produced the thermal dehydrogenation

of
ethane
heat :
=
CH.CH
+
CH2 CH2 H2 9.8

3
3
)
Ethane Ethylene
and by the thermal decomposition propane

of
heat
CH.CH CH CH2 9.9
+
CH CH4
3,
)
(
Propane Ethylene Methane
These processes gave higher purity ethylene large quantities which

in
,
a
possible make ethyl alcohol with new processes and

to
to
made develop
it
direct uses for ethylene

.
Figure 9.5 shows important sources and uses ethylene

It
of
used
is
.
produce wide variety organic chemicals many which are them

to
of
of
a
In
selves starting materials for other organic chemicals recent year

a
,
.
per cent the ethylene produced this country was separated from
10
of
in
gas
per cent was produced from the ethane

40
refinery gases natural

in
,
refinery gases and per cent came from propane cracking.3

50
30 or
About
,
per cent ethylene make ethylene oxide per cent

24
per for
to
used
of
is
ethyl alcohol per cent for polyethylene per cent for styrene
20
10
,
8
,
cent for ethyl chloride and the remainder for other chemical syntheses
,
Ethylene has been the most important building block for organic petro
of
Raw material Methods Intermediate End products
sources preparation chemical products and uses
Plasticfilmandsheet
Polyethylene
,,
electricalinsulation
,)
(-
CH2CH2 molding containers
Refinery gas
from Ethylene separation Styrene ,
thermal and and Polystyrene
=
-CH CH2 otherplastics
Q
catalytic purification
cracking Antifreeze
Ethylene
glycol Cellophane
Dynamite
H₂
-
CH₂
OH OH Terephthalatefibers
and plastics
Syntheticrubber
Ethane Acrylonitrile
→ Plastics
=
Light gas dehydrogenation CH2 CHCN
ETHYLENE Ethylene fibers
Synthetic
fraction oxide
from HH H2C- CH2 Gasabsorbent
petroleum
,,
=
Mono- di- Detergents
distillation Propane
325
C1Н.
and tri
Cн
cracking Textiletreating
ethanolamine Waxes
Detergents
EthylchlorideC2H.CI Tetraethyllead
,
-
Anti knockfluid
)
Halogenated EthylenedichlorideC2H4Cl2 vinylchlorideplastics

ethylenes
( (
)()
Ethane PerchlorethyleneC2C14 Cleaningfluid

fraction Ethane
from Fluoroethylenes Refrigerants
dehydrogenation Aerosolpropellents
natural gas
Acetaldehyde Acetic acid solvents
Ethyl alcohol
Aceticanhydriderayon
CH3CHO
CH2CH2OH
)
(
)
intermediate Butanol coatingssolvent

Pentaerithritol
resins
) )( ,,)
plasticsdryingoils
( ((, ,
Solvents
otherchemicals
.
.
.
Fig 9.5 Ethylene sources and uses

chemicals Other important raw materials include benzene , toluene ,

.
propylene butylene , acetylene , and methane .
,
Products . As indicated in Fig . 9.5 , petrochemicals are used in many

areas in everyday life . They have such diverse applications as fertilizer
( ammonia ) , explosives ( toluene for TNT ) , and synthetic rubber (buta
diene , styrene , etc. ) . Petrochemicals may be aliphatic, aromatic , or
inorganic . The largest tonnage petrochemical is ammonia , an inorganic
chemical utilizing hydrogen from various petroleum sources . It may be
considered a petrochemical , even though only about 18 per cent of
its
mass the hydrogen from petroleum source
is
The principal petro
a
(
.
chemicals are listed below
.
Acetaldehyde Ethylene glycol
Acetic acid Ethylene oxide
Acetic anhydride Formaldehyde
Acetone Glycerol
Acetylene Hydrazine
Acrylonitrile Hydrogen peroxide
Ammonia Isoprene
Amyl alcohols Isopropyl alcohol
Aniline Maleic anhydride
Butadiene Methanol
Butyl alcohols Methyl ethyl ketone
Carbon black Perchlorethylene
Carbon disulfide Phenol
Carbon tetrachloride Phthalic anhydride
Chlorethanes and ethylenes Polyethylene
Chloromethanes Polypropylene
Dodecylbenzene Propyl alcohol
Ethanolamines Styrene
Ethyl alcohol Sulfur
Ethyl chloride Vinyl chloride
Ethylene dichloride
Most the production

of
of
chemicals are intermediates

in
these other
all
complete list chemicals derived from petroleum

of
chemicals
be or
A
.
extremely long Further information may

be
natural gas would

.
found
in
Refs
11
and
3
.
Diversified Petrochemical Plant large petrochemical plant

A
is
.
oil 9.6
Fig
on
shown The plant located the Houston Ship Channel

in
is
.
it its
an
adjacent refinery from which

It
gets raw materials

an to
it
is
.
also near electrolytic brine plant from which receives chlorine and
by
by
sodium hydroxide pipeline Petrochemical products are shipped

.
rail barge and tankers Ocean oing tankers supply the East and West
,
,
-g
Coasts , while barges supply inland points as distant as Chicago and

Pittsburgh .
A product flow sheet is given in Fig . 9.7 . The plant primarily produces
a wide range of solvents for many applications . In addition , it makes
ethyl chloride
for
, which is sold tetraethyl lead manufacture and epoxy
,
resins which are rapidly growing surface coating and plastic materials
,
.
The formula given for the epoxy resin Fig 9.7 only one
of
wide
in
is
a
.
F
Fig large petrochemical plant The ethyl alcohol plant described the text
in
9.6
A
.
.
on
the right edge the picture just behind the long low building
of
located Three
is
furnaces and three reactors operating parallel are visible together with the com
in
,
pressor house distillation columns and product storage tanks Courtesy Shell
,
(
.
Chemical Co.
)
variety epoxy formulations The plant also produces sulfuric acid

of
from hydrogen sulfide recovered the various processes and from the
in
neighboring refinery Many important special products and by prod

-
.
on
ucts not shown the flow sheet are also produced For example
of a
,
,
.
-pby
large quantity isopropyl ether roduct

of
the manufacture
in
is
a
isopropyl Dichloropropane and dichloro

as
alcohol sold solvent

is
it
a
;
.
by
propene are roducts the allyl chloride manufacture They are

of
.
-p
soil fumigant for killing certain soil borne insects and

as
marketed
a
parasites
.
This huge petrochemical plant employs 1,800 workers and produces

Sulfuric USES
Hydrogen
sulfide acid
Table7.4
see
H2S H2SO4
Ethylalcohol ,
Solvent intermediate
CH3CH2OH
Propane Ethylene
( (see Figure9.5
Tetraethyllead
=
CH3CH2CH3 Cracking CH2 CH2 antiknockfluid
Ethylchloride ethylcelluloseplastics
Hexyleneglycol
CH3CH2C1
) ) , ,
,
Brakefluid solvent
CH3
plasticizer
CH
,
,
CCH2CHCH
он он Methylisobutyl
Diacetonealcohol carbinol
,
CH
Methylisobutyl CH3 Coatings
ketone
;
solvent
Cracking
CH3CCH2CCH
Acetone CH3CHCH2CHCH3
0
OH
CH
OH
CH3CCH3 CH3CHCH2CCH3
!
Isopropy
Ő
alcohol Coatingssolvent
Solvent brakefluid
CH3CHCH3
OH Solvent intermediate
Propylene Allylalcohol
,, ,
,
Solvent drugscosmetics
328
=
-
=
OH
CH2CH CH2 CH2 CHCH2 Intermediate
Allylchloride
Intermediate
=
CH2 CHCH2
ċi
Dichlorhydrin Glycerol
,
Resins tobacco
;,
CH2CHCH2 CH2CHCH2 explosivesetc.
ĆI
ĆI
ÓH
Epichlorhydrin OH OH OH
CH2 CHCH2 Intermediate
1СІ
-o
as
Acetone Epoxyresin such

CH3CCH3 CH3
,
Cumene Bisphenol Plastics coatings

Benzene CH2CHCH20 -OCH2CHCH2
CH3 CH3
CH3
с
-с-
-
но
CH он
Phenol termediate
3
CH
CH3
(
)
-OH see Figure8.1
0
Sec butylalcohol Methylethylketone
Butylene
CH
,
CH3CH2CHCH CH2CCH3 Coatingssolvent
=
|
CH2CH2CH CH2
Ő0
OH
Solvent
.
.
a
)
, (.
Fig 9.7 Product flow sheet for petrochemical plant Courtesy Shell Chemical Co.
over a million pounds of products daily . It is only one of several plants

of the Shell Chemical Company . Other plants of the company produce
many of the same products , plus ammonia , mesityl oxide , hydrogen
peroxide , and many other chemicals .
Ethyl Alcohol Manufacture . A representative petrochemical process
is the direct hydration
of ethylene to yield ethyl alcohol . Two major
processes are used to make synthetic ethanol from ethylene . The older
all
process , which accounts for 73 per cent of ethyl alcohol production
,
ethylene with sulfuric acid and subsequent
of
involves the reaction
a
hydrolysis with water The newer process described here involves the
.
direct catalytic hydration ethylene The first plant was built

of
in
1948
,
.
produced by this process
all
per cent ethyl alcohol

15
The
of
and now
is
.
remaining alcohol produced by fermentation grain molasses and
of
is
,
other natural products
.
Process The basic reaction direct hydration simple

in
is
.
:
H3PO4
catalyst
CH CH2 CH3CH2OH
+
H2O 9.10
=
)
Ethylene Ethyl alcohol
sq
at
The reaction the vapor phase

carried out and 1,000
in
of in
570
F
is
lb
/
°
.
As
was shown Example the equilibrium conversion

in
5.16
,
ethylene ethylene must recycled

be
to
alcohol low Therefore

is
,
.
.
-pby
quantities roducts
to
of
Several side reactions occur form small
:
H3PO4
2CH3CH2OH CH3CH2OCH2CH3
+
H2O 9.11
→
)
Ethyl alcohol Diethyl ether
The acetylene impurity the feed reacts

in
H3PO4
CH = CH CH3CHO
+
H2O 9.12
→
Acetylene Acetaldehyde
To
remove the acetaldehyde the product stream hydrogenated

is
,
:
+
CH3CHO CH3CH2OH
+
H2 9.13
(
Acetaldehyde Ethyl alcohol
flow sheet for the process given Fig 9.8 and detailed data are found
in
A
is
Table 9.2 recycle ethylene

in
Fresh and are mixed with water and

.
an
heated exchanger where the reactor product cooled The react

in
is
gas fired furnace and passed

is to
to
ants are then heated the

in
570
F
a
°
The reactor packed with pellets the catalyst which

of
reactor
is
,
.
equi
on
an
phosphoric acid deposited

of
inert solid carrier Because

.
only per ethylene

to
of
librium considerations 4.2 cent the converted

is
,
alcohol The reactor product cooled and some alcohol and water
is
.
,
16
Diethyl ether
other volatiles
Alcohol
recycle
18
6
Feed Hz
Purge
13
19
Product
ethyl
Water alcohol
%
94
(
)
15
Reactor
10
Absorber
le 21
columnPurification
componentsLight
columnseparation
column
Ethyl
concentration
330
recycleHe
alcohol
%
94
(
)
Hydrogenator
Alcohol
Heating Gas liquid 11 Steam 20
5
furnace
3
separator
17
9
14
Heat
Waste
columnRecovery
exchanger
lu
water
2
Water
4
8
1
Compressed Final waste
-
ethylene Gas liquid

separator V22
3
Ethylene recycle
.
.
.
Fig 9.8 Ethyl alcohol manufacturing process

TABLE 9.2 . ETHYL ALCOHOL PROCESS Data *
( All compositions are in mass per cent )

1. Fresh ethylene feed
Composition : 97.2 % ethylene , 0.5 % methane , 2.0 % ethane , 0.3 % acetylene
2. Water feed
Composition : 100 % H2O
Flow rate : 60 gal / min (measured at 68 °F )
3. Ethylene recycle
Composition : 85 % ethylene , 3.0 % methane , 12.0 % ethane
4. Feed mixture to heat exchanger
Pressure : 1,000 lb ; / sq in . gage
5. Feed mixture to preheat furnace
Pressure : 1,000 lbs / sq in . gage
6. Feed mixture to reactor
7. Reactor product
Composition : 4.5 % of the ethylene entering the reactor is converted to ethyl
alcohol . 0.05 % of the ethylene is converted to diethyl ether . All the
acetylene is oxidized to acetaldehyde . Methane and ethane do not react .
8. Reactor product after cooling
9. Liquid separator product
9.1
all
Composition : ethyl alcohol 90.5 water plus the ethyl ether and
%
%
,
acetaldehyde formed
10. Gas separator product
Composition ethylene 10.3
26
%
methane 72.6 ethane 10.6 water

,
,
:
ethyl alcohol
%
3.8
11. Liquid absorber effluent
all
Composition contains the ethyl alcohol and water which entered the
:
ethyl alcohol
15
85
%
absorber water
,
.
the concentration column including alcohol recycle

to
12. Feed
(
)
all
Composition ethyl alcohol water plus ethyl ether and acetalde

13
87
%
%
,
,
:
hyde
13. Concentrated alcohol
Composition ethyl alcohol plus acetaldehyde ethyl ether water
85
%
,
:
14. Waste water

Composition essentially pure water
:
light components column

to
15. Feed
Composition except acetaldehyde has been completely
13
as
same stream
,
:
ethyl alcohol
to
converted
16. Ethyl ether product
Composition ethyl ether ethyl alcohol
83
10
%
water
7
,
,
:
TABLE 9.2 . ETHYL ALCOHOL PROCESS DATA * ( Continued )
17. Feed to purification column

Composition : 86 % ethyl alcohol , 14 % water
18. Alcohol recycle
Composition : 94 % ethyl alcohol , 6 % water , with traces of undesirable com
ponents
19. Product ethyl alcohol
20. Waste to recovery
21. Recovered ethyl alcohol
22. Final waste
* The process described in this table is based on Ref . 8 , with permission . The data
have been augmented to permit more complete mass balances .
condense . The gas - liquid mixture is sent to a separator where the gas
( mostly ethylene ) is removed from the liquid alcohol solution . The gas
is further cooled to condense out alcohol , and the remaining gas is sent
to an absorber where the remainder of the alcohol vapor is absorbed by
water . The resulting alcohol solution is combined with the solution
from the separator and is sent to the purification section of the plant .
The ethylene gas from the absorber is recycled . However , a small purge
is the
is necessary to remove methane and ethane >
, which were present in
feed ethylene The purge the ethylene plant where
to
returned
is
it
.
purified and reused

.
The crude alcohol solution

to
sent the alcohol concentration column

by is
,
where water removed open steam distillation The overhead
is
product rich ethanol and contains some acetaldehyde formed

in
is
in
it
a
,
side reaction The stream therefore hydrogenated using nickel

is
a
,
.
catalyst convert the acetaldehyde ethyl alcohol The reaction

to
to
mixture separated and the hydrogen recycled The alcohol solution

is
is
separated from diethyl ether and other volatile impurities the next
in
is
distillation column The quantity ether impurity Finally

to of
small
is
,
.
.
by
per weight the purifi

94
the alcohol solution concentrated cent

in
is
cation column Concentrated alcohol which contains small amount

the of
a
.
impurities removed from the top

to
of
the column and returned

is
The bottom prod

to
alcohol concentration column recover the alcohol

.
uct from the purification column which

of
dilute solution alcohol

aa
is
is
,
recovery The product ethyl alcohol

as
shown
to
sent column
is
a
per cent by weight ethanol The remainder No

94
water greater
is
.
.
of by
an
concentration practical simple distillation because azeotrope

is
is
,
by
95.6 per cent ethanol weight Addi

at
formed concentration
a
).
tional 94 per cent alcohol is produced by the recovery column . This

plant is pictured in Fig . 9.9 .
Markets . Major uses of ethyl alcohol are given in Fig . 9.5 . Over
half the production is used to make acetaldehyde , and over one - quarter
Fig .9.9 . A section of an ethyl alcohol plant . In the foreground are three reactors
operating in parallel , with accompanying heat exchangers and absorption columns .
Behind the reactors is the low roof of the compressor building , where ethylene is
compressed . In the background are three distillation columns for concentrating and
recovering the alcohol . ( Courtesy Shell Chemical Co. )
is used as a solvent . To prevent diversion to beverage purposes and

bypassing of the heavy tax on beverage alcohol , the Federal government
closely supervises ethyl alcohol production , even though synthetic
ethanol is not normally used for beverages . Industrial alcohol must be
denatured to prevent diversion to beverage use . Many special denatur
ants are used . Ethyl alcohol of 190 proof ( 95 volume per cent , 92.4 mass
per cent ) is sold for about 55 cents per gallon in tank -car lots , and for
as high as 80 cents per gallon in small drum lots . By contrast , 190 proof
tax - paid alcohol sells for over $ 20 per gallon . About 90 per cent of the
total ethyl alcohol production uses ethylene as a raw material , because
synthetic ethanol is generally cheaper than fermentation alcohol . Only
when molasses is low priced can this source compete . However , the
molasses price picture is unstable , since it depends upon the sugar - cane
crop . Beverage alcohols are made from grain , which accounts for only
1.5 per cent of the total production .
LOCATION OF CHEMICAL PLANTS
Many factors must be considered in determining the best location

for a new chemical plant . Among the most important factors are raw
material supply , labor supply , transportation , and markets . The major
factors to be considered in choosing a new plant site are listed below.10
1. Raw materials : availability from existing suppliers ; alternative sup

pliers ; alternative materials
2. Labor : cost ; availability by types ; quality ; labor relations
3. Physical features : foundation requirements ; drainage ; area size ; flood
danger
4. Transportation ( for raw materials and products ) : pipelines ; water ;
rail
5. Markets : nearness ; freedom from tracing raw -material supply routes
in shipping products
6. Utilities : electric power , quality , dependability ; fuels , cost , availabil
ity , and dependability
7. Water : quantity ; quality ; dependability
8. Waste disposal : stream pollution , air pollution
9. Living conditions : housing , availability , cost ; nearness to population
centers
10. General economic environment : taxes ; state and local laws ; industrial
conditions
11. Climate : temperature ; climate upheavals
12.
general facilities and utilities

of
Construction excessive cost labor

;
:
cost and availability material costs

;
Vulnerability nearness important wartime facilities

13.
to
concentration
::
vital industry
of
Raw material supply frequently the deciding factor location

to in
of
is
-
Frequently
an
new plant new plant built adjacent existing

is
a
a
.
because products the older process are needed

as
installation
of
raw
same company that is building the new one . Long - term agreements on
purchase of products are very common in the chemical industry , because
it is the most economical solution to raw -material problems in many
cases . Examples of interdependence of chemical plants are very com
mon . Synthetic ethanol plants are built near petroleum refineries or
natural - gas pipelines for a source of ethylene . On the other hand , sul
furic acid plants are often built near the markets , because it is cheaper to
ship sulfur than it is to ship an equivalent quantity of sulfuric acid .
Other sulfuric acid plants are located near special sources of supply , such
as ore -roasting plants and petroleum refineries .
A particularly interesting example of the location and interdependence
of chemical plants is the huge chemical complex along the Texas Gulf
Coast near Houston . This area will be considered briefly to illustrate
the application of the factors listed above . The area also demonstrates
how complex chemical interdependence may become .
Immediately available raw materials include petroleum , natural gas ,
sulfur , and salt . All these are extremely important starting materials
for chemical manufacture . The Gulf Coast area has the only significant
deposits of elemental sulfur in the United States , as discussed in Chap . 7 .
Additional sulfur is obtained from petroleum and natural gas .
The labor supply is good , with many experienced oil - refinery workers .
Labor relations are average and are influenced by the huge industry oil
.
Physical features include large areas for plant sites but with poor drain
,
age and foundation conditions

.
Transportation includes adequate rail facilities excellent barge service

,
along the coast and up the Mississippi and other rivers excellent ocean
,
going shipping and numerous raw material and product pipelines The
,
Houston area long distance from the major markets the north
of
is
a
eastern United States This serious disadvantage partially compen

is
.
sated by the good transportation the East Coast

to
Electric power readily available reasonably priced and dependable

is
the primary fuel for power stations

an
Natural gas There abun

is
is
.
no
oil
and natural gas but the severe limitations

of
of
dance coal One

,
the Texas Gulf Coast limited supply fresh and cooling water
it of
of
is
a
Fresh water may contaminated by salt and

be
may necessary
be
to
use
,
brackish water for cooling Industrial plants must compete with agri
.
culture for the available fresh water Waste disposal difficult because
is
.
air
no
low stream flows With natural gas there pollution problem

of
is
,
-
.
with coal
as
from the fuel source there

is
,
Housing for workers Although plant

at
available moderate cost

is
far from population centers roads are good

be
to
sites tend Taxes are

,
moderate state laws and industrial conditions are conducive

of to
the
;
development chemical industry The climate

of
mild most the

is
a
.
,
Houston
Texas Texas KEY
Butadiene
or
Katy Chemical Salt Storage
Gas Field Shell Oil
O
Plant Dome
U.
S.
Petroleum
Industrial Gas Field
BP
Chemicals Refinery
NaOH
Brine
Shell
Chemical Acetone
H2
C₂H4 Bakers Hill C2H2 Acetylene Hydrogen

MIBC Salt and C2H4 Ethylene HCI Hydrogenchloride
Celanese
Lubrizol Storage Dome MIBC Methylisobutyl
C2H6 Ethane
Cl2
Diamond CzHg Propane carbinol
C2H4 Ethyl
C2H4
Alkali
Corp. CAH6 Butadiene NaOH Sodiumhydroxide
Rohm
H2
NaOH
BP
CAHg Butylene Refinerybyproducts

and
Acetone
O O
C2H4 HCI HCI Haas CAH10Butane
Phillips Cl2 Chlorine Brine
C2H2 Humble
C3H8andC2H6
Chemical
Oil
10
C2H4 Brine CAH
10
CAH Goodrich
336
Sinclair Socony Firestone
O
Phillips Hull Mobil

,
C2H4 Storage Beaumont Texas C2H4

CHg C2H6
H²O
Goodyear Dome U.S.
Petro Tex O
Rubber Allied
CzHg Chemical
Monsanto Jefferson
Clemens Chemical
,
C2H4 Spindletop Orange

Storage Salt Dome Texas
Amoco
C₂H4
Dome
Texaco
C4H8 CAH
Texas City Neches Butane
Dupont
Line
Bryan Union Carbide C2H4
CAHg
Salt Dome C2H4
Gulf C2H4
Oil Spencer
Brine C2H4
Dow
Fannet
,
Freeport Koppers
Texas Storage Dome
.
Fig
.
.(
9.10
.)
Chemical pipelines on the Texas Gulf Coast Courtesy Fortune

year , with long hot humid summers . Hurricanes and tropical storms
with possibilities of flooding must be considered . For building the plant ,
skilled labor and materials may have to be brought in from long distances
at high cost . There are no significant wartime facilities , and industry
is generally spread over a large area .
Consideration of these 13 points for plant location has shown that
excellent raw -material supplies and transportation offset problems in
markets , water supply , and waste disposal . That this conclusion is valid
is made evident by the tremendous growth of chemical industry in this
area since the Second World War .
The industry of the Houston area graphically illustrates the inter
dependence of chemical industry . Products of one plant are sent to
another by truck , rail ,, barge , and pipeline . The chemical pipeline net
work is extensive , as shown in Fig . 9.10 . This diagram does not show
the large quantities of products shipped by other means of transportation ;
hence few final products are indicated . The diagram also does not show
the extremely complex network of petroleum and natural - gas pipelines
in this area . However , the interrelation among the various plants is
shown . Although Fig . 9.10 is not geographically to scale , it represents
an area about 120 miles long and up to 60 miles wide .
The Houston area includes the Shell Chemical Company plant which
was described earlier in this chapter . It can be seen from Fig . 9.10
that Shell Chemical obtains hydrocarbon raw materials from the neigh
boring Shell Oil refinery and chlorine and sodium hydroxide solution
from the Diamond Alkali plant . From the Shell plant, pipelines feed
acetone to the nearby Rohm and Haas plant , where it is used to manu
facture methylmethacrylate , the starting material for Plexiglas plastic .
Shell sends ethylene to Diamond Alkali , where it is chlorinated and sold
2
for solvent and cleaning fluid . Methyl isobutyl carbinol is piped to the
Lubrizol plant , where motor -
oil
additives are made

.
Many more chemical plants than those shown Fig 9.9 are located
in
along the Texas Gulf Coast This complex chemical industry pro
of
.
duces tremendous variety chemicals based on petroleum

of
natural gas
a
sulfur and salt list the major products would include synthetic
of
A
,
rubber polyethylene plastic alcohols and other solvents chlorinated

,
hydrocarbons sulfuric acid sodium hydroxide and ammonia Consider

,
ation plant location has shown why the Houston

of
the factors involved

in
America's fastest growing chemical centers

of
area one
is
PROBLEMS
a 9.1
For the following petroleum refining processes prepare report includ

of of
one
a
,
-
.
ing the raw materials and final products and description the major
of
discussion
a
process flow sheet for a typical process : crude distillation , light ,

steps , with a process
gas recovery , catalytic polymerization , fluid catalytic reforming , catalytic cracking ,
alkylation , isomerization , polymerization , furfural refining , phenol extraction , pro
pane deasphalting , visbreaking (viscosity reduction ) , MEK solvent dewaxing , hydro
sulfurization , sweetening .
Problems 9.2 to 9.10 are based upon the cumene manufacturing process described in
this chapter .
9.2 . Calculate the production rate of the final cumene product .
9.3 . What percentage of the benzene fed to the reactor is converted to cumene in
one pass ?
9.4 . What are the compositions of the reactor feed and effluent , assuming that the
all
heavy by - products are diisopropylbenzene
?
9.6 Calculate the composition
of
the benzene column feed
of -
.
.
9.6 Calculate the composition and flow rate the cumene column feed
-
.
.
9.7 What percentage the cumene produced lost the heavy bottoms from
in
of
is
.
the cumene column

?
all
propylene
to
9.8 What the over conversion of
finished cumene stream
is
9
?
(
)
-
.
9.9 By energy balance around the reactor determine approximately the quan
an
,
of .
tity removed by the coolant

be
heat which must Btu per hour
in
(
).
Estimate the temperature and phase compositions the reactor product
of
9.10
.
leaving the heat exchanger

.
on
the petrochemicals listed page 326 prepare report including

of
9.11 For one
a
,
.
raw materials manufacturing processes and final end products and uses
,
.
Prepare Fig 9.5 for benzene
to
9.12 flow sheet similar Include sources inter

a
,
.
.
mediate products and end uses
,
9.13 Repeat Prob 9.12 for acetylene

.
9.14 Write the chemical reactions involved making the chemicals shown
in
in
.
Fig 9.7
.
.
data for the ethyl alcohol process given

on
to
Problems 9.15 9.28 are based
in
this
chapter
.
Calculate the compositions the gas entering and the gas leaving the reactor
of
9.15
.
.
Estimate the phase distributions and compositions the product mixture
of
9.16
.
leaving the reactor product cooler

.
at
9.17 How much water added the absorber

is
?
.
purge What percentage the ethylene

of
of
9.18 What the flow rate

in
the fresh
is
?
is .
lost the purge

in
feed
?
Determine the complete composition

to
of
9.19 the feed the alcohol concentration

.
column
.
the alcohol recycle from the purification column

of
What the flow rate

to
9.20
is
.
the concentration column

?
How much feed hydrogen must supplied the hydrogenator

be
to
9.21
?
.
Determine the complete composition the light components

to
of
9.22 the feed

.
column
.
Determine the production rate per cent ethyl alcohol from both product
94
of
9.23
.
19
21
sources streams and

(
).
all
percentage conversion feed ethylene

to
product
of
9.24 Calculate the over

-
.
ethyl alcohol
.
the diethyl ether product stream

of
9.25 What the flow rate

a is
?
.
or
Make heat balance around the reactor any heat lost unaccounted
Is
9.26
.
for
?
9.27 . Make a heat balance around the feed - product heat exchanger . What is the
rate of heat transfer between the two streams (in Btu per hour ) ?
9.28 . At what rate (in Btu per hour ) is heat supplied to the reactor feed by the
furnace ?
REFERENCES
1. Cornell , P. W. ), and V. N. Hurt : Raw Materials for the Petrochemical Industry ,

in K. A. Kobe and J. J. McKetta (eds .) , “ Advances in Petroleum Chemistry and
Refining , ” vol . 2 , Interscience Publishers , Inc. , New York , 1959 .
2. Giddens , P. H .: “ Early Days of Oil,” Princeton University Press , Princeton ,
N.J. , 1948 .
3. Goldstein , R. F .: " The Petroleum Chemicals Industry ,” John Wiley & Sons , Inc. ,
New York , 1958 .
4. Hengstebeck , R. J .: “ Petroleum Processing : Principles and Applications ,”
McGraw - Hill Book Company , Inc. , New York , 1959 .
5. Hoffman , H. L. (ed .) : Process Handbook , Petrol . Refiner , 37 (9 ) : 209ff . ( Septem
ber , 1958 ) .
6. Kirk , R. E. , and D. F. Othmer : “ Encyclopedia of Chemical Technology , ” Inter
science Publishers , Inc. , New York , 1947–1957 .
7. McAllister , S. H. , J. Anderson , E. F. Bullard : Chem . Eng. Progr .*, 43 : 189 ( 1947 ) .
8. Nelson , C. R. , and M. L. Courter : Chem . Eng . Progr ., 50 :526 ( 1954 ) .
9. Payne , R. E .: Petrol . Refiner , 37 (9 ) : 316ff . ( September , 1958 ) .
10. Perry , J. H. (ed .) : " Chemical Business Handbook , ” McGraw - Hill Book Com
pany , Inc. , New York , 1954 .
11. Ponder , T. C. (ed .) : Petrochemical Handbook , Petrol . Refiner , 38 ( 11 ) : 183ff.
( November , 1959 ) .
APPENDIXES
REFERENCES
The data in the appendixes are reproduced here by permission from the following
references .
1. Kelley , K. K .: U.S. Bureau of Mines , Bulletin 476 , 1949 .

2. Perry , J. H. (ed ) : “ Chemical Engineers ' Handbook ,” 3rd ed . , McGraw - Hill Book
3. Rossini , F. D. , et al .: “ Selected Values of Physical and Thermodynamic Properties
of Hydrocarbons and Related Compounds , ” American Petroleum Institute
Research Project 44 , Carnegie Institute of Technology , Pittsburgh , 1953 .
Rossini , F. D. , et al .: “ Selected Values of Chemical Thermodynamic Properties , "
National Bureau of Standards , Circular 500 , 1952 .
4. Smith , J. M. , and H. C. Van Ness : " Introduction to Chemical Engineering
Thermodynamics , ” 2d ed . > , McGraw - Hill Book Company , Inc. , New York , 1959 .
5. Spencer , H. M. , et al .: J. Am . Chem . Soc . , 56 :2311 ( 1934 ) ; 64 :2511 ( 1942 ) ; 67 : 1859
( 1945 ) .
Spencer , H. M. , et al .: Ind . Eng . Chem . , 40 :2152 ( 1948 ) .
341
APPENDIX A. CONVERSION FACTORS FOR UNITS
Mass , Length , Time (M , L, O)

1 cubic foot 28.316 liters
28,317 cubic centimeters
= 7.481 gallons ( U.S. )
1 foot = 30.480 centimeters
1 gallon = 3.7853 liters
= 231 cubic inches
1 inch 2.540 centimeters
1 mile ( U.S. ) = 1.60935 kilometers
1 pound mass (avoirdupois ) = 453.5924 grams
- 7,000 grains
1 slug 32.174 pounds mass
1 square foot 929.034 square centimeters
1 ton (short ) 2,000 pounds mass
1 ton (long ) 2,200 pounds mass
1 ton (metric ) · 1,000 kilograms
2,204.62 pounds mass
Temperature (T )
Temperature in Kelvin , TºK T °C + 273.18
Temperature in Rankine , ° T ° F + 459.69
Temperature in Fahrenheit , T ° F % T ° C + 32 = % ( T ° C + 40 ) – 40
Temperature in centigrade , T ° C 59 ( T °F 32 ) = 59 ( T °F + 40 ) – 40
AT ° F 1.84T ° C
ML /02 )
Till
Force ( F
(
Tu
1 dyne 1 g -cm / sec2
1 poundal : 1 lbm - ft / sec
=
TC "
1 pound -force 32.174 poundals
9rende
4.448 X 105 dynes
Density ( M / L3 )
1 gram / cubic centimeter
Pressure ( F / L2 )
/
62.43 lbm cu ft
Ti & =
1 atmosphere 760 mm Hg at 0 ° C (density , 13.5951 g cu cm ) /

29.921 in . Hg at 32 ° F
/
14.696 lbs sq in . ( psi )
33.899 ft water at 39.1 ° F
= 1.01325 X 106 dynes / sq cm
Energy ( E == FL ML2 / 02 )
1 British thermal unit = 251.98 g -cal
=
777.97 ft -lbs
= 10.409 liter - atm
1054.8 joules
= 0.555 pound - centigrade unit *
= 0.2930 watt -hr
343
APPENDIX A. CONVERSION FACTORS FOR UNITS ( Continued )
Diffusivity (L2 /0 )
/
1 (centimeter ) ? second = 3.87 (ft ) 2 hr /
Viscosity /
( M LO )
1 centipoise = 0.01 poise
0.01 g cm sec /
= 0.000672 lbm / ft- sec
/
= 2.42 lbm ft - hr
Thermal conductivity ( E / OL ? ( T / L )]
1 Btu / (hr ) (sq ft ) (°F / ft ) 0.24808 cal / (sec ) (sq cm ) (° C / cm )
1
Heat capacity (E / MT )
1 Btu / lbm °F 1 cal / g ° C = 1 Pcu / lbm ° C *
Gas constant
1.987 Btu / lb mole 'R = 1.987 cal g mole/ 'K
= 1.987 Pcu / lb mole 'K
= 82.057 atm - cu cm / g mole °K
0.7302 atm - cu ft / lb mole 'R
10.73 (lbs / sq in .) - cu ft / lb mole 'R
* 1 pound - centigrade unit ( Pcu ) is the quantity of heat required to increase the
temperature of 1 lbm of water 1° C .
APPENDIXES 345
APPENDIX B. DENSITIES OF VARIOUS SUBSTANCES2
Substance T °C Density , g / ml
Water 0 0.9999
4 1.0000
10 0.9997
20 0.9982
30 0.9956
40 0.9922
50 0.9881
60 0.9832
70 0.9778
80 0.9718
90 0.9653
100 0.9584
100 % 50 % 25 % (wt )
Methyl alcohol
(aqueous solution ) 0 0.8102 0.9287 0.9666
10 0.8009 0.9221 0.9632
15 0.7958 0.9158 0.9611
20 0.7917 0.9158 0.9592
100 % 50 % 25 % (wt )
Sulfuric acid
(aqueous solution ) 0 1.852 1.411 1.191
20 1.831 1.395 1.178
40 1.811 1.380 1.165
60 1.792 1.364 1.152
80 1.349 1.139
100 1.335 1.125
50 % 20 %
Sodium hydroxide
( aqueous solution ) 0 1.540 1.230
20 1.525 1.219
40 1.511 1.208
60 1.497 1.196
80 1.483 1.183
100 1.469 1.170
24 % 12 %
Sodium chloride
( aqueous solution ) 0 1.190 1.092
25 1.178 1.084
40 1.170 1.077
60 1.158 1.067
80 1.146 1.055
100 1.133 1.042
Benzene 10 0.8895
20 0.8790
30 0.8685
40 0.8577
50 0.8469
APPENDIX C. DENSITY OF ETHYL ALCOHOL - WATER SOLUTIONS ?
0.98
15 %
0.96
25 %
0.94
0.92
0.90
/g,P
50 %
ml
0.88
0.86
0.84
75 %
0.82
0.80
100 %
0.78
10 15 20 25 30 35 40
T, ° C
1
APPENDIXES 347
APPENDIX D. VAPOR PRESSURE OF VARIOUS LIQUIDS AND SOLIDS ?
100,000
waters
80,000
Benzene
alcohol
60,000 NH3
əuanion
hexaneEthyl
40,000 SO2
30,000
20,000
-
n
10,000
8,000
pentane
6,000
4,000
3,000 n -
Ethane
2,000
1,000
800
600
8H
400
ind ww
300 Propane
C
200
SHN
100
60 80
40
butane
SO2
n-
30
20
6
6 8 10
pentane
-
000
U
Naphthalene
n
alcohol
Toluene
decane
hexane
Acetone
n-
-
Benzene
Mercury
Water
Oct
Ethyl
NW
-n
1
100
125
150
175
200
250
300
350
10
20
30
° 40
50
60
80
-70 -60 -50 -40 -30 -20 -10

0
C
T,
APPENDIX E. MELTING POINTS AND NORMAL BOILING POINTS2
Substance Melting point , ° C Normal boiling point, ° C
Acetic acid 16.7 118.1

Acetone -94.6 56.5
Aluminum 660 2056
Ammonia –77.7 -33.4
Argon - 189.2 - 185.7
Benzene 5.5 80.1
n- Butane - 135 -0.6
Carbon dioxide 56.6 ( 5.2 atm ) -78.5 subl
Carbon tetrachloride - 22.6 –76.8
Chlorine - 101.6 - 34.6
Ethane -172 - 88.6
Ethyl alcohol -112 78.4
Helium - 272.2 - 268.9
n - Heptane -90.6 98.4
n-Hexane -94 64
Hydrogen - 259.1 -252.7
Hydrogen chloride -111 -85
Mercury -38.87 356.9
Methane -182.6 - 161.4
Methyl alcohol -97.8 64.7
Naphthalene 80.2 217.9
Nitric acid -42 86
Nitrogen -209.9 -195.8
Nitrogen dioxide ( NO2 ) -9.3 21.3
Oxygen -218.4 -183
n-Octane -56.5 125.7
n-Pentane -129.7 36.3
Propane -187.1 -42.2
Toluene -95 110.8
0- Xylene -25 144
m - Xylene -47.4 139.3
p - Xylene 13.2 138.5
APPENDIXES 349
APPENDIX F. HENRY's Law CONSTANTS FOR VARIOUS GASES IN WATER ?
N2
Air
1x105
9 CO ZH2
8
7 GHz
CH 4, and 02
N2 6 -C₂H6
Air NO
co
3
сні
NO
C2H6
mole fraction
C2H4
1X104
5 6 7 89
/, un
atm
4
Ha co
3
OL
N
,
2
C₂H₂ H2S
1x103
5 6
3
2x102
!
20 40 60 80 100 120
C
T,
°
APPENDIX G. HEAT CAPACITIES
for
1. Empirical heat capacities constant pressure Ideal gas
of
constants gases
at
-
.
to
state
K
298 1500 K.5
P
=
0
°
°
(
).
Cp
bT cT2
+
+
=
a
cp
or
where in and cal mole Btu mole
in
lb
K
R
/g
is
is
T
/
°
'
10
cal cal
X
103 cal
%
K g
/g
/g
c
b
Substance Formula
,
a,
,
' /
mole mole
)K
mole
K
2
"
(
°
(
)
Acetylene C2H2 7.331 12.622 -3.889
Ammonia NH 6.086 8.812 -1.506
,
Benzene C6H6 -0.409 77.621 26.429
-
Butane C4H10 3.844 73.350 22.655
n
-
-
Carbon dioxide CO2 6.214 10.396 -3.545
Carbon monoxide CO 6.420 1.665 -0.196
Chlorine Cl2 7.576 2.424 -0.965
Cyclohexane C6H12 -7.701 125.675 -41.584
Ethane C2H6 2.247 38. 201 11.049
-
Ethyl alcohol C2H5OH 6.990 39.741 -11.926
Ethylene C2H4 2.830 28.601 -8.726
Heptane C7H16 7.094 123.447 -38.719
n
- -
Hexane C6H14 6.011 106.746 -33.363

n
Hydrogen H2 6.947 -0.200 0.481

Hydrogen chloride HCI 6.732 0.433 0.370
Hydrogen sulfide H2S 6.662 5.134 -0.854
Methane CHA 3.381 18.044 -4.300
Methyl alcohol CH3OH 4.394 24.274 -6.855
Methylcyclopentane C6HẠCH -3.261 112.590 36.243
,
Nitric oxide NO 7.020 -0.370 2.546

Nitrogen N2 6.524 1.250 -0.001
Oxygen 02 6.148 3.102 -0.923
Pentane C5H12 4.895 90.113 -28.039
n
-
Propane 2.410 17.533

H
57.195
C
,
,
-
.
Sulfur dioxide SO2 7.116 9.512 3.511

Sulfur trioxide SO3 6.077 23.537 -0.687
Toluene 0.576 93.493 31.227
H
C
-
-
Water H2O 7.256 2.298 0.283

APPENDIXES 351
APPENDIX G. HEAT CAPACITIES ( Continued )

2. Mean heat capacities for gases4 : (a ) low range (25 °C to T ° C ) , (b) high range
(25 ° C to T ° C ) .
8.50
Cl2
F
° 8.25 H20 02
mole
/
1b
Btu
8.00
Air or CO
7.75
or N2
C
°
(a)
7.50
/,
mole
g HCl
7.25
19
cal
H₂
Cp
7.00
6.75
200 400 600 800 1,000 1,200 1,400 1,600 1,800 2,000
C
T,
°
32 392 752 1,132 1,472 1,832 2,192 2,552 2,912 3,272 3,632
F
T,
°
18.0
C2H4
)
SO3
17.0
16.0
F
° 15.0
mole
/
CH4
lb
14.0
Btu
or
° 13.0
C
À cal./8 mole
6
(
)
,
12.0 SO2
CO2
Cp 11.0
ca
NH3
10.0
H2O
9.0
Cl2
8.0
200 400 600 800 1,000 1,200 1,400
0
C
T,
°
32 392 752 1,132 1,472 1,832 2,192 2,552

F
°
T,
APPENDIX G. HEAT CAPACITIES (Continued )
3. Liquids.
Specific
No. Liquid Range° heat
C
29 0-80
%
Aceticacid100
32 Acetone 20- 50
52 Ammonia 70 50
INN
--
--
37 Amylalcohol 50 25
Temperature 26 Amylacetate 0-100 0.2
30 Aniline 0-130
C
F
°
23 Benzene 10- 80 2A
200 Benzylalcohol 20 30
27
--- -
-
10 Benzylchloride 30- 30 ЗА
49 25 40- 20
%%
Brine CaCl2
, ,
51 Brine25 NaCl 40 20 4A
-
350 44 Butylalcohol 0-100
Carbondisulfide -100- 25 0.3
own
Carbontetrachloride 10 60
-
0-100 50
Chlorobenzene
6
Chloroform 0-50
.
150 21 Decane 80 25 6A
- --
- --
300 30 60
6A Dichloroethane
7A
10
Dichloromethane 40 50
9
15 Diphenyl 80-120 80
N
22 Diphenylmethane 30-100 0.4
16 12
Diphenyloxide 0-200 11
-250 16 Dowtherm 0-200 13A
A
Ethylacetate 50 25 14 13
24
-
-- -
42 11 alcohol 30 80 16. 18 20
% %%
100
46 95 20 80
11
17
24
100 50 50 20 80 22.
-
25 benzene 0-100 23
200 0.5
7 Mūrns
bromide 5-25 25
chloride 30 40 .26
Covena
-
--
‫ليييييييييييييييييييييييييييلب‬
36 ether -100 25 29 30
11 iodide 0-100 27 31
34
39
Ethylene glycol -40-200 33

150 28 32 35
37 38 36
41 39 0.6
50
45
8
42
100 48
43
460 47
49
- No. Liquid Range 0.7
C
°
50
2A
1211
Freon
CCI3F 20- 70
-
-
-40-15
( ( ( (
CCI2F2
6
o
) ) )
-20-70
2221
4A CHCI2F
7A CHCIF2 -20 60
- -
70
ЗА 113( CCI2F- CC1F2-20

)
-
38 Glycerol -40-20
o
28 Heptane 0-60
2050 0.8
80
35 Hexane 510
-
-
30
48 Hydrochloric 20-100
%
acid
,
41 Isoamyl alcohol 10-100

43 Isobutylalcohol 0-100
-50 47 Isopropyl alcohol 20 50
-
-
-50 31 Isopropyl ether -80-20

|
40 Methylalcohol -40-20
13A Methylchloride -80-20
14 Naphthalene 90-200 0.9
12
100 Nitrobenzene 0-100

-
.
34 Nonane -50-25
33 Octane -50-25
Perchlorethylene 30-140
--
3
45 Propylalcohol 20-100
20 Pyridine -50-25
-100
98
Sulfuricacid 10-45 530

%
52
9
Sulfurdioxide 20-100 1.0

-
-
23 Toluene 0-60
53 Water 10-200
19 Xylene ortho 0-100
18 meta 0-100
17 para 0-100
APPENDIXES 353
APPENDIX G. HEAT CAPACITIES ( Continued )

4. Aqueous H2SO4 solutions at 20 °C2
1.00
0.90
0.80
& 0.70
0.60
0.50
0.40
0.30
O 10 20 30 40 50 60 70 80 90 100
Sulfuric acid concentration , wt. % H2SO4
APPENDIX G. HEAT CAPACITIES (Continued )
1,2
5. Solids .
с
Cp
bT
+
+
=
a
T2
cp
or
where and cal mole Btu mole
in
in
K
R
lb
/g
T
is
is
°
'
/
Solid Formula Range
X
103 10-5
X
a
K
b
°
,
Calcium carbonate CaCO3 24.98 5.24 6.20 298-1200
-
Calcium oxide Cao 11.67 1.08 -1.56 298-1800
Carbon graphite 4.10 1.02 -2.10 298–2300
С
(
Sodium chloride NaCl 10.98 3.90 298-1073

Sulfur rhombic 3.58 6.24 298–369
S
(
Substance cal Temperature

CP
C
C
g
,
°
°
,
/
Benzene 0.227 100
-
0.299 --50
375
0
0
Ethanol 0.232 -190
0.282
-----
160
0.376 130
Water 0.036 250
0.156 200
0.246 150
0.332 100
–
0.435 -50
0.492
0
APPENDIXES 355
APPENDIX H. HEAT EFFECTS OF PHASE CHANGES

1. Heats of vaporization .”
To- T Latent heat

°C cal / g
1000 10
900
800
700
600
500 20
400
- 30
300
40
200
3
50
60
8
11 10
‫ידיויויויויויךיייוייייייייייייי‬
12 70
Range Tch 14 13
No. 156 80
8
Tc
Compound
°C
1627289
T,
-
18 Aceticacid 100-225 321 21 90

100
23
22 Acetone 120-210235 22 100

90 29 Ammonia 50-200 133 24
25
13 Benzene
@
10-400 289
)
80 16 Butane 90-200 153

21 Carbondioxide 10-100 31
70 Carbondisulfide 140-275 273 26
3 87 24
Carbontetrachloride 30-250 283

60 Chloroform 140-275263 27 28
Dichloromethane 150-250 216
50 Diphenyl 175-400 527
25 Ethane 25-150 32 29 200
26
Ethylalcohol 20-1401 243

28 11 140-300 243
40 17Ethylchloride 100-250 187
2 13
Ethyl ether 10-400 194 30

)
211211
Freon CCI3F 70-250 198

300
( ( ( ( (
30 CCl2F2) 40-200 111

CHCIF 70-250 178
11
)
))
22 CHCI 50-170 96
F
113 CCI2F CCIFZ 90-2501 214

-
10 Heptane 20-300 267 400

11 Hexane 50-225 235
20 15 Isobutane 80-200 134
ANNA
27 Methanol 40-250 240 500

20
Methylchloride 70-250 143

)
19 Nitrousoxide 25-150 36
Octane 600
9
30-300 296
12 Pentane 20-200 197
)
23 Propane 40-200 96 700

24
Propylalcohol 20-200 264

14 Sulfurdioxide 800
90-160 157
]
30 Water 100-500 374 900

10
1000
APPENDIX H. HEAT EFFECTS OF PHASE CHANGES ( Continued )

2. Heats of fusion .?2
Substance Melting point , ° C AH ;, cal / g
Acetylene -81.5 23.0

Ammonia –77.7 79.6
Benzene 5.53 30.1
n - Butane - 138.33 19.2
Carbon dioxide -57.5 43.2
Carbon monoxide - 205.0 7.15
Chlorine - 101.0 21.6
Ethane - 183.23 22.7
Ethyl alcohol -114.4 25.8
Ethylene - 169.15 28.5
n - Heptane -90.60 33.5
n-Hexane -95.32 36.1
Hydrogen - 259.2 14.0
Hydrogen chloride -114.2 13.4
Hydrogen sulfide -85.5 16.7
Methane - 182.48 14.0
Methanol -97.8 23.7
Nitric acid -163.6 18.3
Nitrogen - 210.0 6.15
Oxygen -218.9 3.32
n-Pentane - 129.72 27.9
Propane -187.65 19.1
Sulfur (rhombic ) 115.0 9.37
Sulfur dioxide -75.5 27.7
Toluene -95.0 17.17
Water 0.0 79.7
APPENDIXES 357
APPENDIX I. HEATS OF FORMATION , SOLUTION , AND COMBUSTION
1. Standard heats of formation of inorganic compounds (25 ° C , 1 atm ) ; standard

integral heats of solution at infinite dilution (25 ° C , ! atm ) .3
AH F°, ΔΗ , °,
Compound Formula State
cal / g mole cal / g mole
Ammonia NH, g -11,040 -8,280

1 -16,060 -3,260
Ammonium nitrate NH.NO , 8 -87,270 6,160
Ammonium sulfate ( NH4 ) 2SO4 8 -281,860 1,480
Calcium carbide CaCl , S -15,000
Calcium carbonate CaCO , $ -288,450
Calcium chloride CaCl2 8 - 190,000
- -19,820
Calcium hydroxide Ca ( OH ) 2 S -235,800 -3,880
Calcium oxide CaO 8 - 151,900 -19,460
Carbon (graphite ) С S 0
Amorphous , in coke С 8 2,600
Carbon dioxide CO2 9 –94,051.8 -4,640
Carbon disulfide CS2 g 27,550
1 21,000
Carbon monoxide CO g -26,416
Carbon tetrachloride ССІ , g —25,500
1 -33,340
Copper sulfate CuSO4 8 -184,000 -17,510
Hydrochloric acid НСІ g -22,063 - 17,960
Hydrogen sulfide H2S g -4,815 -4,580
Iron oxide Fe304 -267,000
Iron sulfate FeSO4 8 - 220,500 -15,500
Nitric acid HNO , 1 -41,404 – 7,968
Potassium chloride КСІ 8 -104,175 4,115
Potassium hydroxide KOH 8 -101,780 -13 , 220
Potassium nitrate KNO : -117,760 8,350
Potassium sulfate K2SO4 8 -342,660 5,680
Sodium carbonate Na , Co , -270,300 -5,600
Na, C0 , 101,0 8 –975,600 16,500
Sodium chloride NaCl 8 -98,232
- 930
Sodium hydroxide NaOH -101,990 -10,246

Sodium nitrate NaNO , -101,540 -5,111
Sodium sulfate Na2804 8 -330,900 – 560
Na2SO 4 10H , O 1,033,480 18,850
Sulfur dioxide SO2 g -70,960 9,900
Sulfur trioxide SO : g -94,450 -54,130
Sulfuric acid H SO 1 - 193,910 - 22,990
Water H20 g -57,798
1 –68,317
Zinc sulfate ZnSO4 S -233,880 -19,450
APPENDIX I. HEATS OF FORMATION , SOLUTION , AND COMBUSTION ( Continued )
2. Standard heats of formation and combustion of organic compounds (25 ° C , 1 atm ) .3

Combustion products : H20 (1) , CO2 ( g ) , N2 ( g ) , HCl (aq ) , SO2 ( g ) .
ΔΗΕ , AHcº ,
Compound Formula State
cal /g mole cal / g mole
Acetaldehyde CH3CHO g -39,760 - 284,980
Acetic acid CH3COOH 1 -116,400 – 208,340
Acetone CH3COCH , 1 -59,320 -427,790
Acetylene C2H2 g 54,194 -310,620
Aniline C6H5NH , 1 -812,000
Benzene C6H6 g 19,820 – 789,080
1 11,720 – 780,980
n -Butane C , H10 g -30,150 -687,640
Carbon disulfide CS2 g 27,550 - 263,520
Carbon monoxide CO g – 26,416 -67,636
Carbon tetrachloride CCIA g -25,500 - 92,010
1 -33,400 -84,170
Cumene CH , CH (CH3)2 g 940 -1,257,310
1 -9,848 -1 , 246,520
Cyclohexane C6H12 g -29,430 -944,790
1 -37,340 -936,880
Ethane C2H6 g -20,236 -372,820
Ethyl acetate CH , COOC2H5 1 -538,760
Ethyl alcohol C2H5OH g -56 , 240 -336,816
1 -66,356 -326,700
Ethyl ether C2H5OC2H5 1 -65,200 -652,590
Ethylene C2H4 g 12,496 -337 , 230
Ethylene dichloride CH , CICH , CI 1 - 296,770
Ethylene glycol CH , OHCH , OH 1 -108,580 -284,480
Formaldehyde HCHO g -27,700 - 134 , 670
Formic acid HCOOH 1 -97,800 -75,700
-
n - Heptane C , H16 g -53,630
i - 46,600 -1,511,270
n - Hexane C.H4 g -39,960 -1,002,570
Isopropyl alcohol CH3CHOHCH 1 –74,320 -481,110
Methane CH4 g -17,889 -212,800
Methyl alcohol CH3OH g -48 , 100 - 182,590
1 -57,036 - 173,650
Methylcyclopentane CHỊCH 3 g -25,500 -948 , 720
i -33,070 -941 , 140
Naphthalene C10H , S -1,231,600
Nitrobenzene C6H5NO2 1 –739,000
n - Pentane C5H12 g -35,000 -845,160
Phenol CH он
, 1 –731,460
Propane C3H6 g -24,820 -530 ,600
Styrene CH , CHCH , g 35,220 -1,060,900
Toluene CH.CH g 11,950 :-943,580
1 2,870 -934,500
Urea NH , CONH , S –79,634 - 151,050
0- Xylene C6H ( CH3 ) 2 1 -5,841 -1,088,160
INDEX
Absolute dimension system , 102 Checking of computer program , 90

Absorption , 17 Chemical engineering , definition , 7 , 26
Adiabatic reactions , heat effects in , 256 general aspects , 45
Addition , graphical , 61 history , 25 , 26
Adsorption , 17 origin , 25
Algorithms, 97 work in , 27
Alkylation , 315 , 320 construction , 39
American Chemical Society , 26 , 46 plant design , 38
American Institute of Chemical Engi process design , 35
neers, 26 , 46 process development , 31
Ammonia from petroleum gas , 315 production supervision , 40
Ammonium nitrate , manufacture , 291 research , 28
markets , 294 sales , 43
process , 291 technical service , 41
see
raw materials , 291 Chemical industry ( Chemical process

Analog computer industry
87
,
Analysis problem Chemical plants interdependence 335

48
of
,
,
Azeotrope 310 337

,
location factors 334

,
Chemical process analysis

14
,
,
all
20
Balance over 177 flow sheet

,
,
-
See also Energy balance Mass bal- Chemical process industry American
;
,
(
ance 8-14
)
Basis calculational 174 companies 10-13

,
,
29
Bench scale research definition

1
,
,
-
Blending gasoline 315 history

9
5,
,
Boiler waste heat 285 prescientific

6
,
,
,
-
Boiling point normal 139 products

,
3
, ,
7 2,
of
various substances data 348 scientific

),
(
Boyle's law 122

in
Chemical reactions heat effects 248

,
,
, ,
Btu
in
224 mass balances 183

,
Bubble point 147 See also Reaction

,
15 )
Bypass mass balances with 189 Chemical reactors 197

,
,
,
25
Chemists industrial
of ,
Coding digital computer program

90
,
Calorie 224 Combustion 186

,
Calorimeter 252
of
heat 251
,
Catalytic cracking 317 data 358

,
Catalytic polymerization
45
320 Communications
,
Catalytic reforming 319 Companies chemical list 9–13

,
),
,
Charles law 122 Complex activated 159

,
,
,
'
359
Component , 135 Development , process , 31
Composition , expressions for, 120 Dew point , 147
Compressibility factor , 128 Differential distillation , 195
Computer program , address modification , Differentiation , graphical , 72
95 Digital computers , 87
checking , 90 components , 88
coding , 90 operation , 88
flow chart , 90 programming , 89 , 90
initializing , 96 programming instructions ( table ) , 92
looping , 94 Dimensions , 102
using algorithms , 97 consistency , 104
Computers , application in chemical engi systems , 103
neering , 86 table , 107
types , 87 Distillation , 17
Concentration , 120 differential , 195
of gas mixtures , 129 Drake , Edwin , 312
Condensation , 146 Du Pont Company , history , 9–13
Conservation , of energy , 221
of mass, 174
Construction of chemical plant , 38 Economic evaluation , 35
Control , automatic , 18 , 19 Economics , 19
Convergence in iterative solutions , 83 Einstein , Albert , 221 , 269
Conversion , in chemical reaction , 184 Elutriation , 18
of units , 108 Empirical equations , 57
factors for (table ) , 343 by Lagrange method , 74
Correlation of data , 50 by least squares, 77
graphical methods , 52 Endothermic reactions , 248
numerical methods , 72 Energy , 221
Cracking , catalytic , 315 , 317 dimensions , 102
flow sheet , 318 equivalence to mass , 269
thermal , 319 forms , 222
Crude distillation , 317 intermolecular , 136
Crude petroleum , fractions , 314 internal , 224
Crystallization , 17 , 157 kinetic , 103 , 222
Cumene , physical data , 322 law of conservation , 15
process for , 321 potential , 223
process data , 322 Energy balance , 14 , 15 , 222
Curve fitting , 52 differential , 263
Cycle on logarithmic coordinates , 55 in nonflow systems, 230
total, 228
English engineering system of units , 102
Dalton's law 128 Enthalpy , 229
,
Data presentation Enthalpy - composition diagrams , 248

50
,
Density 119 Equilibria , gas - liquid , 135

,
see
ethyl alcohol water solutions data phase ( Phase equilibria

-
)
),
(
346 reaction 163 201

,
,
Equilibrium constant 164

of
various substances data 345

),
,
(
Design final process Equilibrium ratios vapor liquid 146

36
,
of ,
-
,
magnitude
36
preliminary process Estimate order

36
,
,
-
-
,
Designer Ethyl
38
acetate manufacture 307–310

,
,
Detergent plant 315 raw materials for 308

,
,
INDEX 361
Ethyl alcohol , direct hydration process , Heat , 224

329-331 of combustion , 251
manufacture , 329 data , 358
markets , 333 dimensions , 103
price , 334 of formation , 249
process data , 331 data , 357
proof scale , 132 of fusion , 242
Ethylene sources and uses , 325 data , 356
Eutectic , 157 of mixing , 243
Evaluation , process design and , 35 of reaction , 249
Evaporation , 17 effect on , of pressure , 256
Excess reactant , 184 of temperature , 253
Exothermic reaction , 248 of solution , 244
Extraction , 17 specific , 237
methyl ethyl ketone , 323 standard , 249
phenol , 323 data , 357
Extrapolation , 50 of vaporization , 242
data , 355
(See also Latent heat )
Fahrenheit temperature scale , 117 Heat balance (see Energy balance )
Filtration , 17 Heat capacity , at constant pressure , 234
Flow chart of computer program , 90 at constant temperature , 233
Flow rate , 121 at constant volume , 233
Flow sheet , graphic , 20 effect on , of pressure , 238
product , 21 of temperature , 236
quantitative , 20 gas mixtures , 238
symbols for , 22 gases , 234
Fluid mechanics , 16 data , 350
Force , 102 ideal , 236
Formation , heat of , 249 real, 236
data , 357 liquids and solids , 242
Frasch process , 283 mean , 237
Friction , 226 of various substances (data ) , 351
solids , 242
data , 354
Gas , natural , 313 sulfuric acid solutions , 353
Gas absorption , 17 various liquids (data ) , 352
Gas constant , R , 123 various substances , 350
values for , 344 Heat effects , 233–257
Gases, 122 in chemical reactions , 248
Gibbs , Willard , 133 on mixing , 243
Graphical methods , addition and sub- in phase changes , 242
traction , 61 data , 355 , 356
curve fitting , 52 Heat exchangers , 16
differentiation , 72 Heat transfer , 16
integration , 67 Henry's law , 144
Gravitational dimension system , 103 constants (data ) , 349
Houston , Texas , 335
Human relations , 45
Head , kinetic - energy , 223 Humidification , 17
potential- energy , 224 adiabatic , 153
Humidity , 149 Mass 106
,
mass balances in , 182 equivalence energy 269
to
,
air
Humidity chart ,
14
water system 152
15
Mass balance
,
,
-
with bypass 189
,
chemical reactions 183
in
,
Ideal as law 123 component 176
,
-g
,
25
Industrial chemists
,
differential 195
,
Industrial reactions heat effects
in
257 humidity 182
in
,
Industry see Chemical process industry
all
over
(
177
,
-
Inorganic chemicals list 282
, with purge 193
,
processes for 281
,
reaction 201
in
,
Instructions for digital computer pro
with recycle 191
,
gramming
92
,
in
steps 174
,
18
Instrumentation
total
,
175
,
Integration graphical
67
,
,
Mass fraction 120
,
rectangles
67
of
method
,
,
17
Mass transfer
,
trapezoids
69
of
Material balance see Mass balance
)
Intermediates organic 300
of , 84
,
Mean values
,
Interpolation
17 74 50
MEK extraction 323

,
Lagrangian
Melting point
,
various substances
Ion exchange
,
data 348
),
Isooctane 320
(
Memory digital computer
88
,
,
Iterative procedures
81
Metric unit system 102

,
,
Mixtures of gases 128
,
of
equilibrium
46
Journals technical phase 142
,
,
Model physical 48
,
Molality 120
,
K
values 146 Molar humidity 149

,
Kelvin temperature 117 Molarity 120

,
Key component 176 Mole fraction 120

,
Kier Samuel 312

,
,
Kinetic theory 123-125

,
15
Kinetics Natural gas 313

,
Kopp's rule 242 Newton's law 102

,
Normality 120
,
72
Lagrange method Numerical methods

74
,
,
Latent heat 242

,
of of
sublimation 243
,
Octane number 313

,
vaporization 242
,
for various liquids data Oil crude 313

,
,
355
),
(
Leaching Oleum 286

17
,
,
Olin Mathieson Chemical Corporation

Least squares principle
77
of
,
products
Light gas recovery 319
9
,
,
36
-
Order magnitude estimate

of
Liquid state
,
-
-
131
,
Log og coordinates Organic chemicals production list 302

curve fitting
on
,
58
,
,
Oxygen high ressure process 297

-l
LPG
,
,
320
-p
,
oil
Lubricating treatment 323

,
Percentage humidity 149

,
Magazines
46
technical Petrochemicals 323–334

,
,
Market research list

43
326
,
,
INDEX 363
Petrochemicals , raw materials for , 323 Professional activities , 46

typical plant , 326 Programming , computer , 89
Petroleum , crude , constituents , 313 Project engineer , 38
early United States history , 312 Proof scale , 132
origin , 313 Propane deasphalting , 323
processes 317 Propylene polymers , 320
refining , 314-323 Pure components , phase equilibria , 135
typical refinery , 315 Purge , mass balances with , 193
Phase changes , heat effects in , 242
Phase envelope , 154
Rankine temperature , 117
Phase equilibria , 132
Raoult’s law , 143
mass balances in , 178
in mixtures , 142 Rate of reaction , 159
gas - liquid , 142 Reactant , limiting , 184
liquid - liquid , 153 Reaction , heat of , 249
effect of temperature on , 253
solid - liquid , 157
in pure components , 135 standard , 249
molecularity , 160
gas - liquid , 135
gas - solid , 140 order , 160
liquid - solid , 140 reversible , 163
Phase rule , 134 Reaction equilibria , 163

Phenol , manufacture mass balances in , 201
from cumene , 303–
307 Reaction rates , 159
Real gases , 126
markets , 307
Recovery , light - gas , 319
raw materials and uses , 301
Rectangular coordinates , curve fitting
sources , 300
with , 52
Phenol extraction , 323
Physical states , 122 Recycle , mass balances with , 191
Refinery , petroleum , typical , 315
Pilot plant , 31
Pipelines , chemical , on Texas Gulf Refining , petroleum , 314-323
Reforming , 312
Coast , 336
catalytic , 319
Plant design , 38
Plant location factors , 334 definition , 28 , 29
pilot plant , 33 , 34
Plant technical service , 41
plant flow sheet , 37
Plastics and resins (list ) , 303
Polymerization , 315 Relative humidity , 149
catalytic , 320 Relative saturation , 149
Potential, chemical , 133 Relative volatility , 146
Research , exploratory , 28
Poundal, 108
Pressure , 119 market , 43
process , 29
critical , 138
partial , 128
vapor , 137 Sales , of product , 43
Pressure gage , 119 technical , 44
Process design , 35 Saturated phase , 146
Process development , 31 Saturated solution , 157
Process industry (see Chemical process Saturation , relative , 149
industry )
Sedimentation , 18
Product development , 43 Semilogarithmic coordinates , construc
Product sales , 43 tion , 54
Production supervision , 40 curve fitting with , 55
Shell Chemical Company , Houston Temperature , Fahrenheit , 117

plant , 327 , 337 Kelvin , 117
Slug, 108 Rankine , 117
SO2 , conversion to SO3), 286 wet-bulb , 157
Solid state , 132 Thermal cracking , 319
Solubility of solids in liquids , 157 Thermodynamics , 15 , 221
NaCl , KCIO3 , MgSO4 , 158 first law , 221
Solution , heat of , 244 Tie line , 155
data , 357 Trial -and -error solutions , 81
saturated , 157 Triangular graph paper , 61
Specific gravity , 119 Triple point , 140
Specific heat , 237
(See also Heat capacity )
Standard conditions , 126 Unit , definition , 102
State function , 221 Unit operations , 15–19
States , physical , 122 Units , 106
Steady state, 175 conversion , 108
Stengel process , 291 English system , 106
Stirred -tank reactor , energy balance , 264 metric system , 106
Stripping , 17 Universe , definition , 222
Sublimation , 140 Unsteady state , 195
Subtraction , graphical , 61
Sulfur sources , 283
Sulfuric acid , heat capacity of solutions van der Waals ' equation , 127
(data ) , 353 Vapor pressure , 135
manufacture , 283 various liquids and solids ( data ) , 347
markets , 289 Vaporization , 146
process , 284 Variable , intensive , 134
raw materials , 283 Velocity , flow , 121
uses ( table ) , 291 Volatility , 146
-
Sulfuric acid water system , enthalpy Volume , pure component , 129
data , 247 Volume fraction , 120
Surroundings , definition , 222
System , closed , 175
definition , 222 Waste - heat boiler , 285
flow , 175 Water , phase equilibria , 139
Weight , 106
Wet -bulb temperature , 151
Technical sales , 44 Work , 225
Technical service , customer , 44 in constant - pressure process , 232
plant , 41 in constant - volume process , 232
Temperature , 115 lost , 226
adiabatic saturation , 153 shaft , 227
centigrade , 116
conversion , 118
critical , 137 Yield in chemical reaction , 184
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INTRODUCTION TO CHEMICAL ENGINEERING

by the M. W. Kellogg Co. at Yorktown , Virginia ,

McGRAW - HILL BOOK COMPANY , INC .

INTRODUCTION TO CHEMICAL ENGINEERING

Copyright © 1961 by the McGraw - Hill Book Company , Inc. Printed in

THE MAPLE PRESS COMPANY , YORK , PA .

To the beginner , chemical engineering appears to be a complex and

engineering at usually tends with chemistry The more

answer these questions We will survey the

this book we intend .

Most important among these are mass and energy

balances which are covered thoroughly give the begin

ning chemical engineer his chosen profession while

learning the rigorous analytical techniques

some the field

chemical engineering which

base his later work broad

the field and which demonstrates the depth

view the field

desirable an introductory book

and introduce the reader the broad fields chemical

process Chapters pre

engineering the chemical industries and

sent basic mathematical physical and chemical principles and methods

The mathematical methods presented Chap include some funda

numerical analysis and introduction computers

subjects will grow importance

feel that both chemical

engineers material form satis

any available computer

introduction can used even

computer the emphasis

available the methods

analysis required computer programming rather than the details

balances We have tried develop fully those areas covered rather

include material usually presented Chapters

and 6 apply many of these principles to the calculation of mass and

tested the classroom We wish

tion Rice University and Lehigh University for their cooperation

Chapter 1. The Chemical Process Industry 1

What Is the Chemical Process Industry ? 1

The Systematic Analysis of Chemical Processes 14

The Flow Sheet as a Representation of a Chemical Process 20

Chapter 2 . The Chemical Engineer in the Chemical Process Industry . 25

Origin of Chemical Engineering 25

Chapter 3. Useful Mathematical Methods . 48

Presentation and Correlation of Data 50

Chapter 4. Physical and Chemical Principles . 115

Process Variables 115

Chapter 5. The Mass Balance 174

Over - all Balances 177

and 6 apply many of these principles to the calculation of mass and

tested the classroom We wish

Chapter 1. The Chemical Process Industry 1

What Is the Chemical Process Industry ? 1

The Systematic Analysis of Chemical Processes 14

Chapter 2. The Chemical Engineer in the Chemical Process Industry . 25

Origin of Chemical Engineering 25