CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

Units and Dimensions

DEFINITIONS
Any physical or measurable quantity has two basic constituents, its numerical value and unit.
It is advisable to represent all such quantities in terms of both.
Dimension: It is the basic concept of measurement or it is defined as the a property which
can be measured.
length, mass, time, temperature etc.
Units: It is defines as the means of expressing the dimensions
feet or centimeter for length
pound or kilogram for mass
hour or minute for time
A quantity that has no units is referred to as a dimensionless quantity.
Some quantities which were earlier considered as dimensionless have nowadays been
associated with units.
e.g. molecular weight which is defined as mass per unit mole of substance, hence it
must have a dimension of mass/mole
Advantage of attaching units to each dimension
 it diminishes possibility of inadvertent inversion of any portion of calculation.
 it reduces the calculation in many cases to simple ratios that can easily be performed
by hand calculator.
 it may reduce the intermediate calculations thus reducing the calculation time.
 it enables to approach a problem logically rather than by remembering a formula
and plugging the number in it.
 it demonstrates the physical meaning of the numbers we use
Addition and subtraction of quantities
Two or more quantities can be added or subtracted only if their units are identical.
10 cm  5cm  15cm
5 kg  10 s is meaningless
In order to add or subtract the quantities having same dimensions, their unit must be made
identical.
1m+15 cm is meaningless expression, but after making the two units same it can
be written as:
100 cm  15cm  115 cm or 1m  0.15 m  1.15 m

Multiplication and division of quantities

Two or more quantities can be multiplied or divided without any restriction. The results
obtained by such calculations have different units.
5 cm/2s  2.5 cm/s
3 N  1.5 m  4.5 N  m
 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

10 kg / 5 m 3  2 kg / m3

CONVERSION OF UNITS, CONVERSION FACTOR

A quantity expressed in any unit can be converted into another unit by multiplying it by a
suitable number referred to as conversion factor
Conversion factor: It is defined as the ratio of the two equivalent terms of same dimensions
having the units of our interest.
e.g. to convert a length expressed in inches into centimetres, one has to multiply it by 2.54
hence the conversion factor in this case will be 2.54 in/cm

SYSTEM OF UNITS
A system of units consists of the following components
Base Units: These are defined as the units of basic dimensions such as mass, length, time,
temperature etc.
Multiple Units: These are defines as multiples or fraction of the base units
day, hour, minute, and second for time
kilogram, tonne, gram, and quintal for mass
miles, yards, foot, and inch for length
 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

Multiple units are used for convenience rather than necessity, e.g. It is convenient to write 5
days than to 4,32,000 seconds
Some common multiple units are:

symbol meaning multiply by symbol meaning multiply by

E exa 1018 d Deci 10–1
P penta 1015 c Centi 10–2
T tera 1012 m Milli 10–3
G giga 109  Micro 10–6
M mega 106 n Nano 10–9
k kilo 103 p Pico 10–12
h hecto 102 f Famto 10–15
da daca 101 a atto 10–18
Derived Units: These are defined as the units that are obtained by multiplying or dividing the
base units.
cm/s, kg/m3, kg.m/s2, lb/h etc.
some derived units are very complicated and are given special names. These units are
referred as to compound units or by defining equivalent of compound units
kg.m/s2 as N (Newton)
N/m2 as Pa (Pascal)
N.m as J (Joule)
Two most important systems of units used in chemical engineering calculations are SI system
and American Engineering system (AES) of unit.
Both systems of unit define their own base dimensions and their units.
The SI system is, however, an internationally accepted system of units for engineering
calculation because it covers all the possible dimensions as compared to American
Engineering system. The AES also has the following disadvantages
 occurrence of conversion factors like 1 ft/12 in which is not multiple of 10 as in
metric systems
 problem with units of force
The base dimensions for these systems and the units associated to these dimension are:
SI System American Engineering System
Basic Dimension
unit symbol Unit symbol
Length meter m Feet ft
Mass kilogram kg pound mass lbm
Time second s S s
Moles mole mol pound mole lb-mole
Temperature Kelvin K degree Rankin °R
Electric current Ampere A -- --
Light intensity candela cd -- --
 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

Other common systems of units used in industrial and scientific calculations are:
system length mass time force energy temp.
Absolute (dynamic) cm g s dyne erg, cal °C
system or CGS1
English absolute or FPS1 ft lb s poundal ft-poundal °F
SI2 m kg s Newton J K
Gravitational system or ft slug s pound wt. Btu or ft-lbf °F
British Engg.3
American Engineering ft lbm s or h lbf Btu or hp-h °R
System3
1. Formally common for scientific calculations
2. Internationally accepted units for industry and scientific use
3. Used by chemical and petroleum engineers in USA

FORCE AND WEIGHT

According to Newton second law of motion, force is proportional to to the product of the
mass and acceleration and hence has a unit of kg.m/s2 in SI and lbm.ft/s2 in AES. To avoid the
compound unit of it, which has been very frequently occurring in many engineering
calculations, each system of unit defines a derived unit of force which is Newton (N) in SI
and pound force (lbf) in AES defined as
Newton: 1 N force defined as the force which can accelerate a body of 1 kg by 1 m/s2.
Pound force: 1 lbf force defined as the force which can accelerate a body of 1 lbm by
acceleration equals to acceleration due to gravity at sea level and 45º latitude i.e. 32.174 ft/s2.
According to the definition of Newton and pound force, it can be written
1 N ≡ 1 kg.m/s2 and 1 lbf ≡ 32.174 lbm.ft/s2
This creates confusion between the two systems of unit as two representations are not
consistent.
To avoid this, Newton’s second law is rewritten as
F  ma or F  Cma
Thus the value of constant C in the equation in SI system is 1 N/(kg.m/s2) and that in
American Engineering system is 1/32.174 lbf/(lbm.ft/s2)
The reciprocal of C is represented by a symbol gc
The constant gc is important in the calculations that involve force or pressure. It is some times
used to denote the conversion factor from natural to derived units of force. Thus
1kg  m/s 2 32.174lb m  ft/s 2
gc  
N lbf
Thus in order to used the correct equation for force in any system of unit, the constant gc must
be included in the equation as
ma
F
gc

Weight: It is defined as the force exerted on the object by gravitational attraction.

 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

Suppose a mass m is subjected to a gravitational force W, then by definition it equals to the

product of mass and acceleration due to gravity. To use the equation in any system of units,
like force, it should be written as
g
W m
gc

DIMENSIONAL HOMOGENEITY AND CONSISTENCY

We have noticed that in order to add or subtract the different terms their dimensions and units
must be identical. This establishes the dimensional homogeneity of the equation.
Definition:
An equation is said be dimensionally homogeneous or consistent if the dimension of all the
terms in the expression subjected to either addition or subtraction are same.
An equation is said to be consistent in units if the unit of all such terms in the expression are
same.
Dimensional homogeneity and consistency in units plays an important role in determining the
units and dimension of various constants appearing in any equation.
Following rules are applied while determining the dimensional homogeneity and consistency
of the equation
1. The dimension and units of the terms on both side of equation must be same.
2. Terms subjected to addition or subtraction must have same dimension and units
3. The functions and their arguments are considered dimensionless
CONVERSION OF EMPIRICAL EQUATION EQUATIONS INTO OTHER UNITS
Mathematical equations are of two types:
Theoretical equation: An equation based on theory or law. Such equation are universally
applicable for all system of units.
v  u  at
Empirical equation: An equation based purely on experimental observation and has no
relevance with theory. The terms in such equation may have units in different system and the
equation is only used for units it is derived for.
v  3  2t
Sometimes it may be required to use an empirical equation in different units other than that it
is derived. For this purpose the equation must be converted to be used in the new units. This
is done using the following steps
1. Corresponding to each variable in the equation, define a new variable in the new
units.
2. Express the old variables in terms of the new variables by using appropriate
conversion.
3. Replace the old variables in terms of the new variable to obtain the desired results.
 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

Process and Process Variables

DEFINITIONS
Process: A process is defined as any operation or series of operations by which a particular
objective is accomplished.
Chemical Process: A process that accomplishes the objective of converting the raw material
s into the finished products is referred to as chemical process.
Input or Feed: The material that enters a process is referred to as input or feed to the
process.
Output or Product: The material that leaves a process is referred to as output or product
from the process.
A process may consists of a single step or multiple steps. Each step is carried out in different
unit.
Process Unit: A unit used to carry out the different steps of the process is referred to as
process unit.
A process or process units may consists of multiple input and output. Output from a process
units may be the input to another process units and vise-vera.
Process Stream: The input and output associated with each process unit is referred to as
process stream.
PROCESS VARIABLES
Process Variables: Variables that characterize the operation of processes and individual
process units are referred to as process variable
The process variables are of two types
Flow variables: that describes the amount and/or flow of various species in a process unit or
stream.
flow variables include mass, volume, mole or their flows and chemical compositions of
species
State variables: that describes the state of aggregation of the process unit or stream.
state variables include pressure, temperature and other characteristics that describe the state
MASS, VOLUME AND MOLE
Mass, volume and moles are used to specify the total amount or amount of an individual
species in a process unit or a process stream.
These variable are interrelated to each other by specific characteristics defined as under
Density of a substance is mass per unit volume of the substance.
  m /V
 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

The inverse of the density is specific volume defined as the volume occupied by the unit
mass of substance
v V / m
The specific gravity of a substance is the ratio of the density of the substance to the density of
a reference substance at specific condition.
S.G.   /  ref

The reference most commonly used for solids and liquids is water 4 ºC, which has the
following value:
 H O l  4 º C   1.000g / cm3  1000 kg / m3  62.43lb m / ft 3
2

The reference for the gas is taken as air at STP which has an approximate value of 1 kg/m3
The notation SG = 0.620º/4º specify that the specific gravity of the substance at 20 ºC with
reference to water at 4 ºC is 0.6
API gravity:
141.5
º API   131.5
SG
Degrees Baumé:
145
º Bé  145  for liquid lighter than water at 4 ºC
SG
140
º Bé   130 for liquid heavier than water at 4 ºC
SG
Degrees Twadell:
for liquid denser than water

º Tw  200  SG-1

molar density of a substance is number of moles per unit volume of the substance.
c  n /V
The inverse of the molar density is molar specific volume defined as the volume occupied by
the unit mole of substance

Vˆ  V / n
Mass and moles of a substance are related with the molecular weight of the substance defined
as the mass of unit mole of the substance
M  m/n
 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

FLOW RATE
Flow rate of the material is defined as the rate at which the material is transported through a
process line.
The flow rate of a process stream or a species in it may be expressed as a mass flow rate
(mass/time), as a volumetric flow rate (volume/time), or as a molar flow rate (moles/time).
Thus
mass flow rate, m  m / t
volumetric flow rate, V  V / t
molar flow rate, n  n / t
These flow rate are related to each other by the same formulas as for mass, volume, and mole
Thus
  m / V  m / V

c  n / V  n / V
M  m / n  m / n
Measurement of flow rate:
The flow rate of a process stream is measured by specific devices such as rotameter, orifice
meter, or venturi meter.
Chemical Composition
Most of the materials used in process industries are the mixture of several species. Physical
properties of such mixtures strongly depend on the mixture composition. There are several
ways to represent the composition of a mixture.
Mass and mole fraction: these are defined as the mass or mole of a species per unit mass or
mole of the mixture. Mathematically
mass fraction: i  mi /  mi  m i /  m i
i i

mole fraction: xi  ni /  ni  ni /  ni

i i

Average molecular weight: It is defined as the mass of the mixture per unit mole of the
mixture.
Average molecular weight of the mixture can be calculated from the molecular weight of
individual species and its mass or mole fraction. The following formula are used
1   
 1  2    i
M M1 M 2 i Mi

M  x1M 1  x2 M 2     xi M i
i
 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

Concentration: mass or molar concentration of a species in a mixture is defined as the mass

or mole of species per unit volume of mixture
Mathematically
mass concentration: i  mi / V  m i / V

molar concentration: ci  ni / V  ni / V

concentration of a solution is sometimes also expressed in terms of molarity defined as the

molar concentration of the solution expresses as g-moles of species per litre of solution.
Parts per Million and Parts per Billion: These units, represented as ppm and ppb
respectively, are used to express the concentrations of trace species (species present in minute
amounts) in mixture of gases and liquids.
The definition may refer to mass ratios (usually for liquids) or mole ratios (usually for gases)
and signify how many parts (gram/mole) of species are present per million or billion parts
(gram/mole) of the mixture. If yi is fraction (mass/mole) of species i, then by definition
ppm i  yi 106 ppbi  yi  109

PRESSURE
A pressure is the ratio of a force to area on which the force act. The SI unit of pressure is
N/m2, is called a Pascal (Pa)

Fluid pressure in a tank and a pipe

Hydraulic pressure of the fluid is defined as the force exerted on the base of a fluid column
divided by the area of the base.
 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

This force is thus equals the force on the top surface plus the weight of the fluid in the
column. Thus

force on base of the column = force on top surface + weight of the fluid in the column

PA  P0 A  mg / g c

mass of the fluid, m, is given by

m   hA

substituting in the above equation

PA  P0 A   hA  g / gc 

P  P0    g / gc  h

Pressure is also expressed as head of a particular fluid defines as the height of a hypothetical
column of this fluid that would exert the given pressure at its base if the pressure at the top
were zero. Thus

Ph  P / fluid  g / gc 

Atmospheric Pressure, Absolute Pressure, Gauge Pressure, and Vacuum:

Atmospheric pressure is defined as the pressure at base of an air column located at the point
of measurement.
It can be calculated by using the equation of hydrostatic pressure assuming that the pressure
at the top of the column, P0, equals zero and  and g are the average values of the density of
air and the acceleration of gravity between the top of the atmosphere and the point of
measurement.
A typical value of the atmospheric pressure at sea level, 760 mm Hg, has been designated as
a standard pressure of 1 atmosphere.
Absolute pressure is defined as the pressure at the point of measurement.
Thus the fluid pressures referred to so far are all absolute pressure
Gauge pressure is defined as the pressure relative to atmospheric pressure
Pgauge  Pabsolute  Patmospheric

Vacuum is defined as sub atmospheric pressure. It is negative of gauge pressure for absolute
pressure less than atmospheric pressure.
Fluid pressure measurement
the most common mechanical device used for pressure measurement a bourdon gauge,
which is a hollow tube closed at one end and bent into a C configuration. The open end to the
tube is exposed to the fluid whose pressure is to be measured.
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As the pressure increases, the tube tends to straighten, causing a pointer attached to the tube
to rotate. The position of the pointer on a calibrated dial gives the gauge pressure of the fluid.

A bourdon gauge
It is suitable to measure the fluid pressure from nearly perfect vacuum to about 7000 atm.
Another device to measure the fluid pressure below about 3 atm more accurately are
manometers.
A manometer is a U-shaped tube partially filled with a fluid of known density (manometer
fluid).
When the ends of the tubes are exposed to different pressures the fluid level drops in the
high-pressure arm and rises in the low-pressure arm.
The difference between the pressures can be calculated from the measured difference
between the liquid level in each arm
General Manometer Equation:

A U-tube manometer
 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

The general manometer equation can be derived from basic principle that the fluid exerts the
same force at any two points at the same height in a continuous fluid. These points are taken
as point A and point B in figure.
If the cross section area of tube is A, then at point A, the total force is the force at open end
plus the weight of fluid 1, hence
g
FA  P1 A  1 Ad1
gc

Similarly at point B, the total force is the force at open end plus the weight of fluid 2 and
manometer fluid, hence
g g
FB  P2 A   2 Ad 2   f Ah
gc gc

Equating these forces and dividing by A, the difference between pressures in two arms is
given as:
g g g
P1  P2   2 d 2  1 d1  f h
gc gc gc

This is referred to as general manometer equation and can be simplified for different types of
manometers as shown in figure below.

(a) Open end manometer:

This type of manometer is used to measure the pressure of the fluid at a point. One end of the
manometer is exposed to this point and other end is open to atmosphere. Thus P2 = Patm and
2  0. Hence
g g
P1  Patm   f h  1 d1
gc gc

here the difference of pressure gives the gauge pressure

(b) Differential manometer:
This type of manometer is used to measure the pressure difference between two points in a
process line. The fluid 1 and fluid 2 are same as the process fluid density of density . Hence
g
P1  P2    f    h
gc
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if the differential manometer is used in a process line with flow of a gas then
 f   or f    f

g
P1  P2   f h
gc

(c) Sealed end manometer:

It is same as the open end manometer except that the open end is sealed. Thus P2  0. hence
g g
P1   f h  1 d1
gc gc

If the other end of this manometer is exposed to atmosphere (P1 = Patm) the device functions
as barometer
TEMPERATURE
The temperature of a substance is measure of the average kinetic energy possessed by the
substance molecule
Since this energy cannot be measured directly, the temperature must determined indirectly by
measuring some physical property of the substance whose value depends on temperature in a
known manner.
Such properties and the temperature measuring device based on them includes
 electrical resistance of a conductor (resistance thermometer)
 voltage a the junction of two dissimilar metals (thermocouple)
 spectra of emitted radiation (pyrometer)
 volume of a fixed mass of liquid (thermometer)
Temperature Scale:
It is defined in terms of these properties, or in terms of physical phenomena, such as freezing
and boiling, that takes place at fixed temperature and pressure.
A numerical temperature scale is obtained by arbitrarily assigning numerical value to two
reproducibly measuring temperature.
Two most common temperature scales are defined using the freezing point (Tf) and boiling
point (Tb) of water at 1 atm.
Celsius (or centigrade) scale: Tf is assigned a value 0 ºC and is assigned a value Tb 100 ºC.
Fahrenheit scale: Tf is assigned a value 32 ºF and is assigned a value Tb 212 ºF.
Absolute zero: it is defined as theoretically the lowest temperature attainable in nature. In
Celsius scale its value is 273.15 ºC while in Fahrenheit scale its value is 459.67 ºF
Kelvin scale: the absolute zero has a value 0 and the size of a degree is same as Celsius
degree.
 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

Rankine scale: the absolute zero has a value 0 and the size of a degree is same as Fahrenheit
degree.
Temperature Conversion: the following conversion is applied between these temperature
scales.

T  K   T  º C   273.15

T  º R   T  º F   459.67

T  º R   1.8T  K 

T  º F   1.8T  º C   32

The temperature differences in these scales are related as:

T  K   T  º C 

T  º R   T  º F 

T  º R   1.8T  K 

T  º F   1.8T  º C 
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Stoichiometry of Chemical Reactions

DEFINITIONS
Stoichiometry is the theory of proportions in which chemical species combines with one
another
Stoichiometric equation of a chemical reaction is a statement of the relative number of
molecules or moles of reactants and products that participate in the reaction.
e.g. the stoichiometric equation
2 SO2 + O2  2 SO3
indicates that for every two molecules of SO2 that react, one molecule of O2 reacts to produce
two molecules of SO3.
The numbers that precede the formulas for each species are the stoichiometric coefficients
of reaction components
The stoichiometric coefficients are represented by the symbol  and are considered positive for the
products and negative for the reactants.

A valid stoichiometric equation must be balanced i.e. the number of atoms of each atomic
species must be same on both sides of the equation, since atoms can neither be created nor
destroyed in chemical reactions.
The stoichiometric ratio of two molecular species participating in a reaction is the ratio of
their stoichiometric coefficients in the balance reaction equation.
stoichiometric ratio can be used as a conversion factor to calculate the amount of a particular
reactant (or product) that was consumed (or produced), given a quantity of another reactant or
product that participates in the reaction
Two reactants, A and B, are said to be present in stoichiometric proportion if the ratio
(moles A present)/(moles B present) equals the stoichiometric ratio obtained from balanced
equation.
nA n A  A
 
nB n B  B

LIMITING AND EXCESS REACTANTS

If the reactants are fed to a chemical reactor in stoichiometric proportion and the reaction
proceeds to completion, all the reactants are consumed. If any of these is fed less than its
stoichiometric amount, that reactant would run out first.
The reactant that would run out if a reaction is proceeded to completion is called the limiting
reactant.
A reactant is limiting if it is present in less than its stoichiometric proportion relative to every
other reactants.
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The limiting reactant is determined as follows:

Procedure 1:
nA  or n A   A
If 
nB  or n B   B

then A is said to be limiting relative to B. The limiting reactant is determined in this way for
each pair of the reactants and the one that is limiting relative to all other reactants is identified
as limiting reactant.
Procedure 2:

the ratio nA  or n A  /  A is calculated for each reactant and the reactant with smallest such
ratio is identified as limiting reactant.
All the reactants other than the limiting reactant are called excess reactants.
Excess amount of an excess reactant A is the amount that is in excess of the stoichiometric
amount.

 nA excess   nA feed   nA stoichiometric

Fractional excess of a reactant A is the ratio of the excess amount to the stoichiometric
amount of A. Percentage excess is 100 times of fractional excess.

fractional excess of A   nA excess /  nA stoichiometric

fractional excess of A   nA excess /  nA stoichiometric 100

FRACTIONAL CONVERSION AND EXTENT OF REACTION

An incomplete reaction is the reaction in which the limiting reactant does not fully consumed
and hence the excess reactants too.
Fractional conversion of any reactant A is the ratio of its amount reacts to the amount that is
fed

f A   nA reacted /  nA feed

percent conversion is 100 times the fractional conversion

The extent of reaction is defined as the ratio of any species that is converted (or produced) in
a chemical reaction to its stoichiometric coefficient. It is represented by the symbol .
If ni,0 and ni represents the amount of a species i present before and after the chemical
reaction then extent of reaction is given by
  ni /  i

for reactants: ni  ni ,0  ni

for products: ni  ni  ni ,0

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hence, ni  ni ,0   i and ni  ni ,0   i

for multiple reactions, the above equation becomes

ni  ni ,0   i , j j and ni  ni ,0   i , j j

j j

 
where  i , j is the stoichiometric coefficient of ith species in jth reaction, and  j or  j is the
th
extent of j reaction.
MULTIPLE REACTIONS, YIELD, AND SELECTIVITY
Most chemical processes require the production of desired product in a single chemical
reaction.
Unfortunately, the reactants can usually combines in more than one way, and the product
once formed may react to yield some undesirable products which is less economic.
Either the less yield of desired product is obtained for a given quantity of raw materials or
more quantity of raw materials are required to obtain the specified yield of the desired
product.
Economy of the process requires that the desired reaction predominates over the side
reactions.
The terms yield and selectivity are used to describe the degree to which desired reaction
predominate the side reactions. These are defined as:
moles of desired product produced
Yield:
moles that would have been formed if there
were no side reactions and the reaction goes
to completion

moles of desired product formed

Selectivity:
moles of undesired product formed
It is desirable to obtain a high yield and selectivity of the desired product.
 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

Evaluation of Physical Properties

SOURCES OF PHYSICAL PROPERTIES
All chemical engineering calculations handle with various process streams that contain
various species and their mixtures. In order to carry out the calculations involving process
streams, their properties and conditions must be known.
Property is some measurable characteristics of a substance i.e. pressure, temperature, volume
or the characteristics that are deducible by these measurable characteristics such as density,
specific gravity, or internal energy etc.
The following methods are used to determine the physical properties of the process material.
Look it up: when there is need of a value for a physical property of a substance, there are
good chances that someone somewhere has measured that property and published the results.
Since the experiments are usually costly and time consuming, one can use the available
resources on physical properties.
Some of these sources are:
 D. W. Green and R. H. Perry, Eds., Perry’s Chemical Engineers’ Handbook, 8th
Edition, McGraw Hill, New York 2008
 Journal of Chemical and Engineering Data, an ACS publication issued monthly
Estimate it: in the absence of experimental data, another way to determine the physical
property is to estimate them using the available correlations. These correlations are the
empirical relationships based on the experimental measurement. A very good source of such
correlations is:
 B. E. Polling, J. M. Prausniz, and J. P. O’Connell; Properties of Gases and Liquids,
5th Edition, McGraw Hill, New York 2001
Measure it: when the properties of a substance are not found in literature and the correlations
are not available or the property is needed with higher precision then it is better to measure it
experimentally
APPLICATION OF THERMODYNAMICS
Thermodynamics plays an important role to determine the physical properties of substances.
Various theoretical and empirical correlations are available for this purpose.
Some important definitions
State of the system: Every system possesses a unique set of properties at a given instant of
time and is said to be in a particular state. State of the system is therefore defines as certain
unique set of properties that a system possesses at a given time.
Equilibrium: It is defined as a state in which there is no tendency toward spontaneous
change.
Two systems are said to be in equilibrium if they possess the same state.
 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

A matter or substance may exists in various state depending upon their internal molecular
structure. Some well-known states are gas, liquid, and solid
Phase is defines as completely homogeneous and uniform state of matter.
A matter, at any specific conditions, may exists in any of these states or phase (single phase)
or the mixture of two or more phases (multi phase).
SINGLE PHASE SYSTEMS
Density or specific volume of species in a process stream, exists as a single phase, is most
important property that is often needed in chemical engineering calculations. Different
correlations are used for density or specific volume of substances existing in different state
i.e. solid, liquid, or gas.
Liquid and solid densities:
Liquid and solid densities are usually independent of pressure and change with temperature.
Densities of various inorganic and organic liquids and solids, as pure components, are
reported in Perry’s Handbook.
Mixture density with known composition can be obtained by using the assumption of additive
volume as
1 i

 i i
Ideal Gases:
Gases are usually compressible and hence their density or specific volume depends on both
pressure and temperature. The equation of state, defines as relationship between the
properties that describes the state of a matter or substance, is used to predict the specific
volume of a gas.
Ideal gas equation of state: This is the simplest form of an equation of state. It is derived
from the kinetic theory of gases by assuming that gas molecules have a negligible volume,
exert no force on one another, and collide elastically with the wall of their container. It has
the following form:
PV  nRT PV  nRT

The equation of state may also be written as:

PVˆ  RT
A gas whose PVT behaviour is well represented by the above equation is said to behave as an
ideal gas or a prefect gas
Molar density is calculated from this equation as inverse of molar specific volume i.e.
1 P

Vˆ RT
 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

and the mass density is obtained by multiplying it by molecular weight of the species
PM

RT
Standard temperature and pressure: In order to use the ideal gas equation of state it is
necessary to have a table of value of R or remember it in different units. To avoid these
requirements a conversion from standard conditions may be used.
For an ideal gas at an arbitrary temperature T and pressure P
PV  nRT
for the same ideal gas at specified reference temperature Ts and pressure Ps (referred to as
standard temperature and pressure STP) it becomes
ˆ
s s  RTs
PV

Dividing first equation by the second yields

PV T
n
PV ˆ Ts
s s

If the standard conditions are known then V can be determined for a given value of n and vice
versa.
The standard conditions most commonly used are:
System Ts Ps Vs ns
SI 273.15 K 1 atm 0.022415 m3 1 mol
AES 491.67 ºR 1 atm 359.05 ft3 1 lb-mol
The term standard cubic meter (SCM) is often used to denote m3 (STP), and standard
cubic feet (SCF) is often used to denote ft3 (STP)
Ideal gas mixture:
Suppose a mixture of ideal gas consists of ni moles of species i are contained in a volume V at
a temperature T and total pressure P. The partial pressure pi and pure component volume vi of
species i in the mixture are defined as:
pi: the pressure that would be exerted by ni moles of i alone in same total volume V at the
same temperature T
vi: the volume that would be occupied by ni moles of i alone at the total pressure P and
temperature T of the mixture.
if the mixture and the species in it behave ideally then
PV  nRT and piV  ni RT

dividing the second equation by the first yields

pi ni
  yi  pi  yi P
P n
 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

or, the partial pressure of a species in an ideal gas mixture is the mole fraction of that species
times total pressure.
summing for all species

p
i
i P

this is called the Dalton’s law of partial pressure which states that partial pressure of the
species of an ideal gas mixture add up to total pressure.
similarly for pure component volume
PV  nRT and Pvi  ni RT

dividing the second equation by the first yields

vi ni
  yi  vi  yiV
V n
or, the pure component volume of a species in an ideal gas mixture is the mole fraction of
that species times total volume
The quantity vi/V is the volume fraction of species in the mixture, and 100 times this quantity
is the percentage by volume (%v/v) of the species.
This also shows that volume fraction of a species in an ideal gas mixture is same as its moles
fraction. Summing for all species

v
i
i V

this is called the Amagat’s law of pure component volumes which states that pure component
volume of the species of an ideal gas mixture add up to the total volume.
Non ideal gases:
Gases which do not follow the ideal behavior are called non ideal or real gases.
PVT behavior of such gases cannot be represented by ideal gas equation of state.
In general no gas is an ideal gas and it behaves ideally only at very low pressure.
Critical Temperature and Pressure:
How well or poorly the ideal gas equation of state fits PVT data for a species often depends
on the values of the system temperature and pressure relative to two physical properties of the
species.
These properties are referred to as critical pressure (Pc) and critical temperature (Tc).
Critical temperature of a species is defined as the highest temperature at which that species
can coexist in two phases (liquid and vapor)
Critical pressure of a species is defined as the pressure corresponding to its critical
temperature.
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A substance at critical temperature and pressure is said to be in critical state.

A vapor is a gaseous species below its critical temperature, and a gas is a species above its
critical temperature at a pressure low enough for the species to be more like vapor than a
liquid
Substances at temperature above its critical temperature and pressure above its critical
pressure are referred to as supercritical fluids.
The molar and the mass densities of the non-ideal gases are calculated similar to that of the
ideal gases. However the molar specific volume is calculated using the equation of states for
the non-ideal gases.
An Equation of State (EOS) is a relationship between the pressure, temperature and the
specific volume of the gas. The following equations of state are most commonly used.
 Virial Equation of State
 Cubic Equation of State
 Compressibility factor Equation of State
Virial Equation of State:

A virial equation of state expresses the quantity PVˆ / RT as a power series in the molar
density:

PVˆ B C D
 1   2  3 
RT Vˆ Vˆ Vˆ
B, C, and D are functions of temperature and are known as second, third, and fourth virial
coefficient respectively. For ideal gas, all these coefficients are zero
The accuracy of the prediction depends on the number of the terms after which the series is
truncated. Some important virial equations are:
Beattie-Bridgeman EOS:

PVˆ B B B
 1  1  22  33
RT Vˆ Vˆ Vˆ
A0 c
B1  B0   3
RT T
A0 a B0 c
B2   B0b  
RT T 3
B0bc
B3 
T3
Benedict-Webb-Rubin EOS:

PVˆ B B B B
 1  1  22  44  55
RT ˆ
V V ˆ Vˆ Vˆ
 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

A0 C
B1  B0   03
RT RT
ˆ2
a ce /V
B2  b  
RT RT 3
ˆ2
c e  /V
B4 
RT 3
a
B5 
RT
Cubic Equation of State:
A cubic equation of state is cubic in specific volume of the species. These equations have
three roots; all real or one real and two complex.
If the equation has three real roots then the largest root corresponds to the specific volume of
the species as a gas while the lowest one corresponds to the specific volume of the species as
a liquid. The middle root has no physical significance.
If the equation has only one real root, it corresponds to specific volume of the species as a gas
above its critical temperature.
Some important cubic equations of state are:
Van der Walls EOS:



a  ˆ

 P  ˆ 2  V  b  RT
V 

the constants a and b in this and all cubic equations of state are calculated from the following
two equations

 P   2 P 
 ˆ  0 and  ˆ2   0 , thus
 V Tc , Pc  V Tc , Pc

27 R 2Tc2 1 RTc
a and b
64 Pc 8 Pc

Redlich-Kwong (RK) EOS:

This equation is a modification of the previous equation

 1/2 
 P  aT  
 Vˆ  b  RT

 
Vˆ Vˆ  b  


R 2Tc2 RTc
a  0.42748 and b  0.08664
Pc Pc

Soave- Redlich-Kwong (SRK) EOS:

 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

This equation is modification of RK equation presented by Soave

 
 P  a  
 Vˆ  b  RT

 
Vˆ Vˆ  b  


R 2Tc2 RTc 2
a  0.42748 , b  0.08664 and   1  m Tr 
Pc Pc

where m  0.48508  1.55171  0.1561 2

Peng-Robinson EOS:

 a 
P  
 Vˆ  b  RT

   
Vˆ Vˆ  b  b Vˆ  b  


R 2Tc2 RTc 2
a  0.45724 , b  0.07780 and   1  m Tr 
Pc Pc

where m  0.37464  1.54226  0.26992 2

Compressibility Factor Equation of State:

Compressibility factor of a gaseous species is defined as the ratio PVˆ / RT , represent by z i.e.

z  PVˆ / RT
For ideal gases the compressibility factor equals to unity. The extent to which z differs from 1
is a measure of the extent to which the gas is behaving nonideally. The above equation is
rearranged as:

PVˆ  zRT
This equation is referred to as compressibility factor equation of state.
For a given species, the compressibility factor is a function of temperature and pressure i.e. z
= z(P,T). Perry’s chemical engineers’ handbook gives the value of z for variety of gases.
Once the value of z is known, the compressibility factor equation of state is solve for any
variable it involves.
The value of z can also be read from a chart called the compressibility chart. But use of chart
is restricted as it is not possible to prepare such chart for every possible species. To avoid it, it
is therefore required to prepare a common table or chart which can be used for all species.
Such chart is referred to as generalized compressibility chart.

Law of corresponding state:

This law states that all gases behave identically at the same reduced condition. It is defined as
the extent to a gas is away from its critical condition.
 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

Reduced temperature and reduced pressure defines the reduced condition. They are defined
as the ratio of system temperature (or pressure) to its critical temperature (or pressure). Thus
Tr  T / Tc and Pr  P / Pc

the law of corresponding state helps us to observe that a plot of z versus Tr and Pr should be
approximately same for all substances. Such a plot is referred to as generalized
compressibility chart.
The reduced ideal volume is defined as the ratio of specific volume to the ideal critical
volume.

Vˆ Vˆ PVˆ
Vˆrideal  ideal   c
Vˆc RTc / Pc RTc

The generalized compressibility charts for different pressure ranges are shown as follows:

Generalized compressibility chart at low pressures

Generalized compressibility chart at medium pressures

 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

Generalized compressibility chart at high pressures

Compressibility factor equation of state along with the generalized compressibility chart is
used to calculate the properties as described below:
1. Look up the values of Tc and Pc of the gas
2. If gas is either hydrogen or helium, determine the adjusted critical constants from the
empirical formula
Tca  Tc  8 K Pca  Pc  8 atm
These equation are known as Newton’s correction
3. Calculate the reduced values of the two known variable using the definition
T T /T r P  P/P
c r Vˆ ideal  PVˆ / RT
c r c c

4. Read the value of compressibility factor from the generalized compressibility chart
and solve for the unknown variable in compressibility factor equation of state.
Mixture of real gases:
The specific volume of mixture of real gases can be calculated using any equation of state.
To use virial or cubic equation of state, appropriate mixing rules are used to calculate the
modified parameters for the mixture. These parameters are then used in the equation of state
to obtain the required property.
Mixing rules for virial equation of states are complex and are beyond the scope at this stage.
Mixing rule for some of the cubic equations of state are discussed here.
Parameters for mixtures of real gases for different cubic equation of states are calculated as:
Van der Wall equation of state:
C
a 1/ 2   yi ai1/ 2 b   yibi
i 1 i
 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

Redlich-Kwing equation of state:

C C 0.5  C
a     yi y j  ai a j   b   yi bi
i 1  j 1  i 1

S-R-K and P-R equation of state:

C C  C
a     yi y j  ai a j  1  kij  
0.5
b   yi bi
i 1  j 1  i 1

Using the compressibility factor equation of state, the properties of mixtures of real gases are
calculated by three methods:
Dalton’s law of partial pressure:
The procedure is as follows
1. Look up the values of Tc and Pc of the gas and apply the Newton’s correction, if
required.
2. Calculate the partial pressures of all the gases assuming the ideal gas law.
3. Calculate the reduced pressure using partial pressures calculated in step 2 and reduced
values of the other known variable.
4. Read the value of compressibility factor of all the gases using generalized
compressibility chart and calculate the mean compressibility factor as
zm   yi zi
i

5. Use mean compressibility factor in compressibility factor equation of state and solve
for the unknown variable.
Amagat’s law of pure component volume:
The procedure is as follows:
1. Look up the values of Tc and Pc of the gas and apply the Newton’s correction, if
required.
2. Calculate reduced values of the two known variable.
3. Read the value of compressibility factor of all the gases using generalized
compressibility chart and calculate the mean compressibility factor as
zm   yi zi
i

4. Use mean compressibility factor in compressibility factor equation of state and solve
for the unknown variable.
Kay’s Rules:
In the previous methods, the compressibility factor is determined for all gases. If the number
of species are large, this become tedious and time consuming.
Kay’s rule provides a rather simple procedure for the mixture of non-ideal gases as given
below:
 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

1. Look up the values of Tc and Pc of the gas and apply the Newton’s correction, if
required.
2. Calculate the pseudo-critical temperature and pressure using the formulae
Tc   yiTc ,i Pc   yi Pc ,i
i i

3. Determine the reduced value of two known variables based on pseudo-critical

temperature and pressure.
4. Read the compressibility factor from the generalized compressibility chart using the
reduced values as obtained in step 3.
5. Solve the compressibility factor equation of state for unknown variables using the
compressibility factor obtained in step 4.
MULTI-PHASE SYSTEMS
Pure Component Phase Diagram:
A phase diagram of pure substance is a plot of one system variable against another that shows
the condition at which the substance exists as a solid, a liquid, and a gas. The most common
of these diagram plots pressure on the vertical axis versus temperature on the horizontal axis.
The boundaries between the single-phase regions represent the pressures and temperatures at
which two phases may coexist. The phase diagram of water is shown and described in the
figure below

Phase diagram of water

Several terms are defined with reference to phase diagram
1. If T and P corresponds to point on the vapor-liquid equilibrium curve for a substance,
P is called the vapor pressure of the substance at temperature T, and the T is called
the boiling point of the substance at pressure P.
2. The boiling point of the substance at P = 1 atm is called the normal boiling point of
that substance.
3. If (T,P) falls on the solid-liquid equilibrium curve, then T is called the melting point
or freezing point at pressure P
4. If (T,P) falls on the solid-vapor equilibrium curve, then P is called the vapor
pressure of at solid at temperature T and T is called the melting point or freezing
point at pressure P
 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

5. The point (T,P) at which solid, liquid, and vapor phases can all coexist is called the
triple point of the substance
6. The vapor-liquid equilibrium curve terminates at the critical temperature and
critical pressure (Tc and Pc). Above and to the right of the critical point, two separate
phases never coexist
7. If the substance exists in the single liquid phase at a specified temperature and
pressure, it is referred to as subcooled liquid and the temperature by which it trails the
boiling point of the substance is referred to as the degree of sub-cool.
8. If the substance exists in the single vapor phase at a specified temperature and
pressure, it is referred to as superheated vapor and the temperature by which it
exceeds the boiling point of the substance is referred to as the degree of superheat.
9. When a substance exists as a mixture of vapor and liquid phases, the fraction of liquid
phase in the two phase mixture is referred to as quality of the mixture
The vapor-liquid equilibrium curve is the most important part of the phase diagram and is to
be discussed in more details.
As discussed earlier that any point on this curve represents the co-existence of vapor and
liquid phases. The pressure at this point, the vapor pressure, varies with temperature as shown
in the diagram.
The volatility of a species is the degree to which the species tends to transfer from the liquid
(or solid) state to the vapor state. At a given temperature and pressure, a highly volatile
substance is much more likely to be found as a vapor than is a substance with low volatility,
which is more likely to be found in a condensed state (liquid or solid).
The vapor pressure of a species is measure of its volatility: the higher the vapor pressure at a
given temperature, the greater the volatility of the species at that temperature.
It is often required to obtain vapor pressure of a species at specified temperatures in most of
the engineering calculation. A good source of tabulated vapor pressure data of water at
different temperature is steam table. Such tables of other species are available are found in
literatures. In the absence of tabulated data, the vapor pressure can be measured
experimentally. But this also not always convenient and hence an alternative is to estimate
the vapor pressure using an empirical correlation for p*(T). Thermodynamics plays an
important to correlate them.
Estimation of vapor pressure:
A relationship between p*, the vapor pressure of a pure substance and T, the absolute
temperature is the Clapeyron equation

dp* Hˆ v


dT T Vˆg  Vˆl 
Unless the pressure is extremely high, the specific volume of liquid is negligible relative to
that of vapor, thus

Vˆg  Vˆl  Vˆg

 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

If the ideal gas law is assumed to apply, then

Vˆg  RT / p*

substituting it in Calpeyron equation

dp* p*Hˆ v

dT RT 2

d ln p* Hˆ v

d 1/ T  R

integrating for a small temperature range where heat of vaporization can be assumes constant
gives

Hˆ v
ln p*   B
RT
Which shows a linear relationship between ln p* and 1/T
This equation is called Clausius―Clapeyron equation and is only applicable for small
range of temperature.
For wider range of temperatures, use of reference substance plot is more suitable as described
below:
Clapeyropn equation for a reference substance at the same temperature is written as

d ln pr*


Hˆ v  r

d 1/ T  R

Dividing Clapeyron equation by the above equation

d ln p*

 
Hˆ v
d ln pr*  
Hˆ v
r

for large temperature range, the rhs of the above equation is almost constant, hence
integrating

ln p* 
 Hˆ  ln p
v *
 B
 Hˆ 
v
r
r

This is a straight line between the vapor pressure of

a pure species and that of a reference substance on
log-log scale as shown in the figure:
If the vapor pressure of the reference substance is
known then the vapor pressure of the substance can
be obtained from this plot.
 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

The reference substance is usually the water whose vapor pressure is known from steam
tables.
If the temperatures corresponding to the reference substance vapor pressures are placed
below them, the vapor pressure at any temperature can directly be read from such plot. In
fact we no long need the value of reference substance vapor pressures.
A reference substance plot with temperature scale on abscissa is shown here

Reference substance plot: temperature scale on abscissa

If vapor pressure values of reference substance are omitted from the plot, it is referred to as
Cox Chart.

Cox Chart of vapor pressures of pure species

A plot similar to the Cox chart is a plot where the temperature corresponding to the vapor
pressure of the substance is plotted against the temperature corresponding to same vapor
pressure of the reference substance. Such plot are also the straight line plot and are referred to
as Duhring plots.
 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

A relatively much simple empirical equation that correlates the vapor pressure – temperature
data extremely well is the Antoine equation
B
log10 p*  A 
T C
Gas liquid system: one condensable species
Many industrial processes involve several species out of which only one species is capable of
existing as a liquid phase at the process conditions. Separation processes that involve such
systems include:
evaporation, drying, and humidification which involve transfer of liquid into the gas phase.
condensation and dehumidification which involve transfer of the condensable species from
the gas to the liquid phase
When a liquid is contacted with a dry gas, the liquid evaporates into the gas as long as the
partial pressure of liquid vapors in the gas phase is less than the vapor pressure of the liquid
at the system temperature.
As the liquid evaporates into the gas phase, its partial pressure in the gas phase increases and
ultimately reaches to its vapor pressure at the system temperature.
The gas phase, under such condition, is said to be saturated with liquid and referred to as
saturated vapor.
The application of Gibbs phase rule (assuming the dry gas as a single species) gives:
F C 2P  2
This means that if the any two variables among the system temperature and pressure, and
composition of liquid vapors in the gas phase are known, the value of the third one can be
obtained.
The relation which exists between these variables is the condition at equilibrium, i.e.

pi  yi P  Pi sat T 

This relation is referred to as Raoult’s law for single condensable species

The vapor present in the gas in less than its saturation amount is referred to as superheated
vapor. For such vapor,

pi  yi P  Pi sat T 

If a gas containing a single superheated vapor is cooled at constant pressure, the temperature
at which the vapor becomes saturated is referred to as the dew point of the gas. Thus

pi  yi P  Pi sat Tdp 

The difference between the temperature and the dew point of the gas is called degrees of
superheat
 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

Multi component gas-liquid system

Gas-liquid processes that involve several species in each phase include:
Many chemical reactions, distillation in which each species transfers between the two phases
Absorption and stripping in which transfer of one or more species occurs between the two
phases
Vapor liquid equilibrium data
When a vapor and liquid are in equilibrium, the system variables such as temperature,
pressure, and the composition of species in the vapor and liquid phase are related by an
equilibrium relation
A set of system variables that satisfy the equilibrium relation are referred to as vapor-liquid
equilibrium (VLE) data.
Two simple form of the equilibrium relation are those which represents the Raoult’s law and
Henry’s law and are described below
Raoult’s law: when the gas phase is an ideal gas and the liquid phase is an ideal solution then
the partial pressure of a species in the gas phase is equal to the product of its mole fraction in
liquid phase and the vapor pressure of liquid at system temperature

pi  yi P  xi Pi sat T 

For the cases where the ideal conditions do not prevail, the Raoult’s law is an approximation
that is generally valid for liquid is almost pure solutions of the species.
When liquid phase is pure, the Raoult’s law reduces to the case of single condensable species
Henry’s law: this law states that the partial pressure of a species in the gas phase equals the
product of its mole fraction in liquid phase and the term which is function of temperature,
referred to as Henry’s law constant

pi  yi P  xi H i T 

Henry’s law is generally valid for dilute solution of a species provide it does not dissociates,
ionize, or react in the liquid phase.
Vapor-liquid equilibrium calculations for ideal solutions:
When a liquid is heated at the constant pressure, the temperature at which the first bubble of
vapor is formed called the bubble point temperature.
When a vapor is cooled at the constant pressure, the temperature at which the first drop of
liquid is formed called the dew point temperature.
The bubble and dew point temperatures are not same if the liquid and vapor are not pure
species.
Similarly when a liquid is allowed to expand at constant temperature the pressure at which
first bubble of vapor is formed is called bubble point pressure
 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

when a vapor is allowed to compressed at constant temperature the pressure at which first
drop of liquid is formed is called dew point pressure
The set of temperature and the compositions of the species in liquid and vapor phase at
constant pressure is referred to as T-x-y equilibrium data
The set of pressure and the compositions of the species in liquid and vapor phase at constant
temperature is referred to as P-x-y equilibrium data
Calculation of equilibrium data of a system is very complex. However, if the liquid behaves
as an ideal solution, Raoult’s law can be used to obtain the same.
Application of Gibbs phase rule gives the degrees of freedom equals to number of species. If
all the liquid or vapor phase compositions and pressure or temperature are specified then
from Raoult’s law

pi  yi P  xi Pi sat T 

Summing over all the species

 p   y P   x P T   P
i
i
i
i
i
i i
sat

In terms of vapor compositios

P
yi  xi
Pi sat
T 
Summing over all the species
P yi 1
yi
i
Pi sat
T 
  xi  1  
i i Pi sat
T 

P

The above equations are solved for temperature or pressure as the case may be. It can be
noted that these are also bubble or dew point temperature and pressure.
The vapor or liquid phase composition are then calculated as:

Pi sat  T  P
yi  xi or xi  yi
P Pi sat
T 
For binary system A-B, the degrees of freedom is 2, hence if any two variables are specified,
all other variables can be obtained to generate the VLE data for binary system.
Using Raoult’s law for the species A and B

p A  xA PAsat T  pB  xB PBsat T 

adding the two equations:

p A  pB  xA PAsat T   xB PBsat T 

or P  xA PAsat T   1  xA  PBsat T 
 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

knowing temperature and pressure, the equation can be solved for xA, once xA is known yA is
obtained from

y A  xA PAsat T  / P

If P is fixed, T-x-y data is generated for different T. The temperature range can be chosen
between the boiling point of species A and B at fixed pressure.
If T is fixed, P-x-y data is generated for different P. The pressure range can be chosen
between the vapor pressure of species A and B at fixed temperature.
Graphical representation of T-x-y and P-x-y data for binary system
T-x-y or P-x-y data can be plotted graphically by taking xA and yA on x axis and T or P on y
axis. These plots are shown as

constant temperature
constant pressure
Let the F moles of liquid with composition of A equals to zA is heated up to a temperature T at
which it exists a mixture of V moles of vapor and L moles of liquid of composition yA and xA
of species A respectively, then
F  L V z A F  xA L  y AV

simplifying
V z A  x A AB
 
L y A  z A BC

this referred to as inverse arm rule

Equilibrium between two liquid phases
When a mixture of two miscible liquids is mixed with an immiscible liquid in which only one
species is soluble then this will result in two liquid phases which are in equilibrium with each
other and the soluble species distributes in both the phases.
Miscibility and distribution coefficient
Let A and B are two liquids such that when A is added to B or vice versa, they exists in single
phase only up to some extent and after that second phase forms. if the composition one
 CHC 2010/PKC 2010: Basic Principles of Chemical Engineering

species into the other is very small, when exist in single phase, then they are called partially
immiscible
if one phase contains a negligible amount of A and other phase contains a negligible amount
of B, then they are called immiscible with each other.
If a mixture of two miscible liquids is mixed with another liquid which miscible with one
liquid and only partially miscible with the other, then this results into two liquid phases. Each
phase contains all the three species and are in equilibrium with each other.
The ratio of the composition of a species in the two phase is called its distribution coefficient.
Such mixture are referred to as ternary mixture
Phase diagram for ternary system
A mixture of three species is well represented on a triangular phase diagram, which may take
form of an equilateral triangle. It has the following characteristics:
1. The vertices represent the pure species
2. The edges represent the mixture of two species
3. The interior represents a ternary mixture.
4. The sum of the perpendicular from an interior point on the sides equals to its altitude.
A typical ternary phase diagram for the system water-acetone-methyl isobutyl ketone
(MIBK) is shown in the following figure. The water and MIBK are partially miscible while
acetone is completely miscible in water and MIBK. The curve shown in the figure is referred
to as binodal curve which separates the single and two phase region. Area above the curve
represents the single phase while that below the curve represents the two phase. The line
shown in the two phase region is called tie lines. The extreme points of the tie line which lie
on the binodal curve represents the composition of the two liquid phases that are in
equilibrium

Ternary phase diagram for water-acetone-methyl isobutyl ketone (MIBK)