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The thermodynamic systems comprise of fluids, i.e. liquids and gases and a
thermodynamic process can be defined in terms of the fluid properties within a system. The
operational parts are excluded from thermodynamic analysis through a proper choice of the
boundaries. A study of the behaviour of the working fluid (fluid properties) is, therefore
necessary for a thermodynamic analysis of energy and matter transformations. We consider
working substances at equilibrium state in form of fluid phases.
There are two points of view from which the behaviour of matter can be studied: the
microscopic and the macroscopic.
From the microscopic point of view, matter is composed of an extremely large number
of molecules, which are themselves built from atoms and are of complicated structure. For
the simplest case of gases, it may be assumed that each molecule at a given instant has a
certain position, velocity, and energy, and for each molecule these change very frequently, as
a result of collisions. The behaviour of the gas is described by summing up the behaviour of
each molecule. Such a study is made in statistical thermodynamics.
In classical thermodynamics, which is only concerned with the effects of the action of
many molecules, a macroscopic approach is adopted. Clearly speaking, a certain quantity of
matter (water in a boiler or gas in a combustion engine) is considered without the events
occurring at the molecular level being taken into account. For example, the macroscopic
quantity, pressure, is the average rate of change of momentum due to all the molecular
collisions which occur on a unit area. The effects of pressure can be felt and measured by
using, for example a pressure gauge. For thermodynamic analysis the behaviour of matter
will be described in terms of macroscopic observable properties. Engineering
thermodynamics uses the classical model. However, sometimes we will use molecular picture
(microscopic model) for a better understanding of some phenomenon.
2.1
Quantity of Matter
The thermodynamic studies normally include the quantity of matter, e.g. the quantity
of water in a boiler or the amount of gas in the cylinder of a combustion engine. The quantity
of matter is characterized by mass m and number of moles n. The amount of matter of a
system is given by the mass enclosed within its boundary.
In common language the mass of a substance is also called its weight. But they are
different conceptionally. Weight is actually the force G with which a body of mass m will be
attracted from the surface of earth at a particular place having acceleration due to gravity g:
G=mg
(2.1)
The acceleration due to gravity is not a universal constant. It depends on the place of
observation. At earths surface g = 9.81 m s -2. As the acceleration due to gravity depends on
altitude, the weight of a particular mass m will also vary with altitude.
The mass is determined through weighing by comparing with a standard mass. The
kilogram is the SI ( SI from the french System International ) unit of mass; it is equal to the
mass of the international prototype of the kilogram mass of a lump of platinum-iridium.
An alternative way to represent the amount of matter is as the number n of moles. The
mole is the amount of substance of a system which contains as many elementary entities as
there are atoms in 0.012 kilogram of Carbon-12. When the mole is used, the elementary
species must be specified. These may be atoms, molecules, ions, electrons, other particles, or
specified groups of such particles.
Examples of the use of mole:
1 mol of H2 contains about 6.022 1023 H2 molecules, or 12.044 1023 H atoms.
1 mol of Hg2Cl2 has a mass of 472.08 g.
1 mol of Hg22+ has a mass of 401.18 g.
1 mol of e- has a mass of 548.60 g.
2.2
2.2.1 Volume
The volume V is the space occupied by a substance and is measured in cubic meters
(m). The meter is the basic unit of length. Thus we write V = 1m if the system occupies 1 m
of space. One meter is defined as the length of path travelled by light in vacuum during a
time interval of 1/299792458 of a second. The second, represented by the symbol ' s ', is the
unit of time and is defined as the duration of 9192631770 periods of the radiation
corresponding to the transition between the hyperfine levels of the ground state of Caesium
-133 atom. Sometimes instead of absolute volume, the term specific volume is used. Specific
volume is the space occupied by unit mass of a substance and is measured in m/kg.
V
m
[unit is m/kg]
Similarly the volume of one mole of a substance is called molar specific volume or simply
the molar volume and is also denoted by small
V VM
n
m
[unit is m/mol]
where M [unit is g/mol] denotes the molar mass (molecular weight) of the substance, i.e. the
mass of 1 mol of substance. M = m / n.
2.2.2 Pressure
Pressure is the force exerted by a system (fluid) on a unit area. The SI unit of pressure
is defined as
pressure = force / area
= N / m
This composite unit is called ' Pascal ' and denoted by the symbol Pa
1Pa = 1N m-2
The pressure of the atmosphere is of the order of 10 5 Pa. This shows that Pascal is
rather a small unit of pressure. It is, therefore convenient to describe the pressure in terms of
kPa or MPa.
Other common unit for pressure is ' bar ', which nearly equals the pressure of one
atmosphere. The unit ' bar ' is defined as
1 bar = 105 Pa = 105 Nm-2 = 100 kPa.
The atmospheric pressure varies from region to region and is not constant throughout.
A standard atmospheric pressure is defined as
1 standard atmosphere = 1 atm = 101.325 kPa = 1.01325 bar
Figure 2.1 shows two blocks of matter which have the same mass. They exert the same force
on the surface on which they are standing, but the narrow block exerts a higher pressure
because it exerts the force on a smaller area than the fatter block.
(2.2)
Figure 2.2 shows a few pressure measuring devices (manometers). Figure (a) shows
an open u-tube manometer indicating gauge pressure, and Figure (b) shows an open u-tube
indicating vacuum, i.e. pressure below the atmospheric pressure. Figure (c) shows a closed utube indicating absolute pressure.
pu
pu
Evacuated
h
h
Hg
a)
Hg
b)
Hg
c)
h g
A
A
A
(2.3)
where F is the force of the mercury column on the gas over an area A. For mercury with a
density = 13.6*103 kg/m a 760 mm (0.760 meter) column of mercury is equivalent to
pG
2.2.3 Temperature
The temperature is a very familiar concept in everyday life as it is a measure of the
'hotness' or 'coldness' of a body or fluid. But it is quite difficult to give the concept a precise
definition. Temperature is associated with the ability to distinguish hot from cold. When two
bodies at different temperatures are brought into contact, energy (heat) flows from the higher
temperature object (hot body) to the lower temperature object (cold body). After some time
they attain a common temperature and are then said to be in thermal equilibrium. Hence, the
temperature may be defined as the property whose value is identical in the two systems which
are in thermal equilibrium.
The temperature of a fluid is one of the properties of that fluid, along with pressure
and specific volume. It is necessary to have a precise value of temperature in order to define
the state of a fluid. The basis for the temperature measurement is provided by the zeroth law
of thermodynamics: 'When a body A is in thermal equilibrium with a body B, and also
separately with a body C, then B and C will be in thermal equilibrium with each other'.
In order to obtain a quantitative measure of temperature, a reference body, say
thermometer, is used. A column of liquid inside the thermometer expands or contracts with
changes of temperature. The thermometric property is the expansibility of the liquid. When a
thermometer is brought into contact with a body at a temperature higher (greater) than itself,
then heat is transferred from that body to the glass of the thermometer and from there to the
liquid inside the thermometer raising its temperature. The heat transfer stops when a thermal
equilibrium is reached. Now the thermometer has the same temperature as that of the body
outside. The increase in temperature of the liquid results in its expansion. As the expansibility
of liquids is much higher than that of the glass, the expansion of glass may be neglected in
comparison to that of liquids. The extent of expansion of a liquid in a glass column is hence a
direct measure of the increase in the temperature of the liquid.
It is necessary to have a common temperature scale for measurement. The most
common temperature scale is the Celsius scale. This uses two arbitrary fixed points, the
freezing point and the boiling point of water under standard atmospheric conditions, to define
0 0C and 100 0C respectively. For a mercury thermometer, the difference in the length of
mercury column is divided in 100 equal parts. Each part then represents 1 0C.
This temperature scale is not satisfactory in many aspects. As each substance has a
different coefficient of thermal expansion this temperature scale will depend on the nature of
the liquid in the thermometer. Even if the thermometers made of mercury and alcohol, with
linear scales, are made to agree at two temperatures, they will not agree at some intermediate
temperature. Secondly, the division in 100 equal parts is only applicable to a linear expansion
with temperature. Strictly, the coefficient of thermal expansion is not a linear function of
temperature. Such a thermometer for temperature measurements is therefore not accurate.
Also the Celsius temperature scale shows negative values for temperatures which are below
the freezing point of water, e.g. the boiling point of liquid oxygen is -183C. This seems
physically unsound as the other properties of state, namely pressure and volume have only
positive values. It is therefore very much desirable to look for another scale for temperature.
An empirical temperature scale, which is also an absolute scale, is that of an ideal gas
thermometer which is described here in detail.
A schematic diagram of a constant volume gas thermometer is shown in Figure 2.3. A
small amount of gas is enclosed in a bulb which is connected via a capillary tube with one
limb of the mercury manometer. The other limb of the mercury manometer is open to the
atmosphere and can be moved vertically to adjust the mercury levels so that the mercury just
touches the reference mark on the capillary. The sensor is hereby the gas filled in the constant
volume bulb. The pressure in the bulb is measured through a height of the mercury column.
The thermometric property of this constant volume gas thermometer is the pressure of the
gas. It changes in a characteristic way with the temperature of the bulb and is given by the
difference in level z of the mercury column:
p = pU + z g
where pU is the atmospheric pressure and the density of mercury.
(2.4)
pu
V = const.
z =^ p
Mark
Hg tubing
Figure 2.3 : Diagram showing the working principle of an ideal gas thermometer.
= const.
If the pressure in the bulb is equal to the atmospheric pressure then z = 0. Since the
water gas
volume of the bulb is constant, a definite amount of gas (e.g. n mol) in the bulb under
thermal equilibrium conditions at a certain empirical temperature will result in a definite
value for the product (p), where V/n. For a definite temperature the value of (p) depends on
the nature of the gas. The value of can be varied by filling the bulb (of constant volume V)
air
withig different amounts n of
a gas. Figure 2.4 shows a plot of the values of (p) at a known
(pv)
temperature z = const.) against 1/ for different gases.
pv
Helium
1/v
1
0
for =const.
This relation describes an ideal gas. The instrument is called an ideal gas
thermometer. Each ideal gas thermometer, irrespective of the gas filling indicates the same
value for (pig and hence the same empirical temperature if it is in thermal equilibrium
with a system. The value of (pig can be used to define an empirical temperature ig of the
ideal gas thermometer
ig = C (pig
(2.5)
It may be pointed out that the linear relation in Equation (2.5) is chosen for the sake of
simplicity. Any other relationship between pand , e.g. quadratic could also be taken.
This definition has many advantages. The first is, that the temperature can not attain
negative values as p and have positive values only. Secondly, we need only one fixed point to
determine the constant C and hence to define the temperature scale. Thirdly, this temperature
scale does not depend on the nature of the gas (filling medium).
The scale is established by arbitrarily selecting a fixed point. The temperature of a
mixture of pure water, water vapor, and ice in thermal equilibrium is selected for this
purpose. Such a mixture exists at only one temperature (called the triple point), and the
temperature of this mixture provides an easily reproducible standard. The gas thermometer is
brought in thermal equilibrium with pure water at its triple point, the corresponding value of
(pig is determined. The value of (pig is determined by measuring the values of (p) at different
(i.e. with different fillings of a gas) and then extrapolating these to 1/ = 0. It holds then
1
Nm
( p ) igtr .,H 2O igtr ,H 2O 2271.2
C
mol
(2.6)
It is agreed that the triple point of water shall be 273.1600 K. Here K is used for
'Kelvin', which is the unit of temperature in this scale (of ideal gas thermometer). The value
of C follows
molK
C = 0.12027 Nm
(2.7)
and the unit of temperature, Kelvin:
1K
igtr , H 2 O
27316
.
(2.8)
Hence 1 Kelvin is one 273.16 th part of the empirical temperature of ideal gas thermometer at
the triple point of water.
By an international agreement in 1954 the value of 273.16 was selected to make the
unit of the new scale the same size as that of the Celsius (formally Centigrade) scale. Since
the ordinary ice point (freezing point of water) is 0.01 K lower than the triple point of water it
follows that 0C=273.15 K.
To measure the temperature of a system the gas thermometer is brought in thermal
equilibrium with the system and the value of (pig is determined. The ideal gas thermometer
temperature of the system is then
molK
Nm
ig C ( p ) ig 0.12027
( p ) ig
Nm
mol
This empirical ideal gas thermometer temperature satisfies the conditions of a
thermodynamic state property. Later on in the course of our studies of entropy an absolute
thermodynamic temperature scale will be defined. Fortunately it proves to be identical with
the ideal gas scale. It will be shown that the point which we have defined as the absolute zero
of temperature is not an arbitrary point. At present we take it for granted that the
thermodynamic scale of temperature is identical with the ideal gas thermometer temperature
scale. We write:
ig = T
(2.9)
(2.10)
where R = 1/C = 1/0.12027=8.315 Nm/(molK) and is called the molar gas constant (universal
gas constant).
In everyday life the temperature is expressed in Celcius scale. The temperature in
Celcius (C) is simply related to the thermodynamic temperature T via
t ( in C ) = T ( in K ) - T0
(2.11)
where T0 = 273.15 K represents the ordinary ice point. The Celcius temperature scale
employs a degree of the same magnitude as that of the thermodynamic temperature, but its
zero point is shifted.
A second absolute temperature scale, used with the old English system, is the Rankine
scale, defined by
T(Rankins) = 9/5 T (Kelvins)
This makes the water triple-point temperature correspond to 491.69 R. The corresponding
relative temperature scale is Fahrenheit scale. The temperature differences are identical in
degrees Fahrenheit (F) and Rankins (R), but a level of 0F corresponds to 459.67 R.
It follows, that the relationship between the Celsius and Fahrenheit scale is
F = C * (9/5)+32
(2.12)
The temperature of the ice point is about 32F and that of the steam point about 212F.
The measurement of temperature with the help of ideal gas thermometer is a tedious
process [extrapolation of many measured (p to (pig]. The temperatures are, therefore
generally measured with other types of thermometers such as thermocouple and platinum
resistance thermometers. Naturally, these have to be calibrated against absolute temperature
(measured with ideal gas thermometers). For this purpose a practical temperature scale
(International Temperature Scale-ITS) was adopted first of all in 1927 and then revised from
time to time (latest revision 1990). The ITS is defined by:
1- Assigning values to certain accurately reproducible temperatures such as boiling and melting points.
2- Specifying the type of thermometer to be used in each range of the scale.
3- Specifying the interpolation formula to be used for each thermometer between the assigned values.
This scale is a practical scale and it is based on a number of fixed and easily reproducible
points which are assigned definite numerical values of temperature, and on specified
formulae which relate temperature to the readings on certain temperature measuring
instruments. The scale was so defined that it conforms closely to the ideal gas temperature
scale. The temperature interval from the oxygen point to the gold point is divided into three
main parts, as given below in International Temperature Scale of 1968 (ITS-68).
Table 2.1: Temperatures of Fixed Points
Normal boiling point of oxygen
Triple point of water ( Standard )
Normal boiling point of water
Normal boiling point of sulphur
(Normal melting point of zinc-suggested as an
alternative to the sulphur point)
Normal melting point of antimony
Normal melting point of silver
Normal melting point of gold
Temperature C
-182.97
+ 0.01
100.00
444.60
419.50
630.50
960.80
1063.00
10
where the constants R0, A, and B are computed by measurements at ice point, steam point and
sulphur point. The temperature t is in C.
(b) From -190 to 0C:
The same platinum resistance thermometer is used, and the temperature is given by
R = R0 [1+At +Bt+ C(t-100)t]
where R0, A and B are the same as before, and C is determined from a measurement at the
oxygen point.
(c) From 660 to 1063C:
A thermocouple, one wire of which is made of platinum and the other of an alloy of 90%
platinum and 10% rhodium, is used with one junction at 0C. The temperature is given by the
formula
= a + bt + ct
where a,b and c are computed from measurements at the antimony point, silver point, and
gold point. The diameter of each wire of the thermocouple must lie between 0.35 and
0.65mm
An optical method is adopted for measuring temperatures higher than the gold point.
The intensity of radiation of any convenient wavelength is compared with the intensity of
radiation of the same wavelength emitted by a black body at the gold point. The temperature
is then determined with the help of Plancks law of radiation.
2.3
Pure Substances
The practical application of thermodynamics lies in the working of heat power plants
or refrigerating machinery etc., which operate with the help of some working fluid or system
(thermodynamic system). The processes carried out in these applications are analysed by
considering the effects produced on the systems. It is therefore, necessary to have information
on the properties of these working fluids or systems. In many cases the working fluid is a
pure substance which may change its phase (A phase is any homogeneous part of a system
that is physically distinct). The important characteristic of a pure substance is that its
chemical composition is same throughout its mass. It may exist in one or more phases. Thus,
a system consisting of a mixture of various phases of water, namely water and ice or water
and steam is a pure substance. A system consisting of oxygen as a vapor, a liquid, or a solid
or a combination of these is also a pure substance. Sometimes air, even though made up of
several gases, namely nitrogen, oxygen, carbon dioxide etc. and thus a gas mixture, is
considered and mathematically treated as a pure substance as long as there is no change of
phase. This is due to the fact that under normal conditions its composition remains constant
and that none of the constituent gases undergoes a chemical change during a thermodynamic
process. For many applications it will be treated like a pure substance. Strictly speaking, this
is not true. We should rather say that air exhibits the characteristics of a pure substance.
Pure substances are used as the working medium in many energy transformation
devices. Water is used as the working fluid in steam power plants. In heat pumps and
refrigerators the use of pure organic fluids is very common. Water vapor is used as energy
11
carrier for the heating of devices in certain matter conversion processes. It is, therefore very
much necessary to learn about the properties of pure substances.
(2.13)
where R = 8.315 Nm/(molK), is the universal gas constant and , the molar volume. So in the
1
range of low pressures the molar density ( ) increases linearly with pressure at a constant
temperature. These constant temperature curves are called isotherm ( isotherm = same
temperature ).
The isotherms appear as hyperbola in a p diagram. Figure 2.5 shows the p- diagram
for a perfect gas.
12
1.5
bar
1.0
873.15 K
0.5
573.15 K
373.15 K
T = 273.15 K
0.1
0.05
0.10
m3 /mol 0.20
v
(2.14)
where M is the molecular weight of the substance. The p- diagram is not universal but
individual (different) for every gas. This difference is not due to the fact that the function is
R
different for every gas. It is because the factor ( M ) is different for every gas and hence the
R
individuality. This factor ( M ) is called the specific gas constant.
A study of the p- diagram explains why the power plants use gases as the working
medium. The product p has the dimensions of energy, namely Nm/mol or Nm/kg. By heating
at a constant volume the temperature and the pressure (c.f. Fig. 2.5) will increase. Thus the
energy supplied in the form of heat will be stored in gas (in form of a higher pressure). This
can be converted partly into work through the relaxation of pressure (decreasing the pressure)
and may be used, e.g. to push back a piston. This forms the basis for a spark ignition internal
combustion engine (Otto engine). The increase of temperature and the consequent increase of
pressure is realized practically through combustion.
Figure 2.6 shows the schematic p- diagram of an idealized Otto cycle. Process 1-2
represents the compression of the gas without any heat transfer. Heat is then added at constant
p
3
volume
through
combustion process. This is represented in 2-3 as the increase of pressure at
constant
volume. Process 3-4 is an expansion without heat transfer. Process 4-1 is the
combustion
rejection of heat from the gas while it is disposed into the atmosphere (it is shown as
cooling). The p- behaviour of the gas therefore presents the relevant (appropriate) model for
the thermodynamic analysis of the energy transformations in an Otto process. The hatched
(marked) area in the p- diagram then represents the obtainable work from an idealized Otto
process 1-2-3-4-1. It expansion
is the difference between the work done by the system during the
expansion from 3-4 and the work done on the system during the compression from 1-2 ( this
2 be discussed in detail in chapter 5 ).
process will
cooling
4
compression
1
v
13
p=const.
(b)
5
saturated
liquid state
saturated
vapor state
V
14
m/ /
m/ m/ /
(2.15)
where m/ is the mass of the liquid and m// is the mass of the vapor at saturation. The total mass
m = m/ + m//.
Obviously the mass fraction of the liquid is (1-x). The wet vapor region at x = 0 ( m// = 0 )
then represents the state of boiling liquid ( saturated liquid state ) which lies on the saturated
liquid line. The point at x = 1 ( m/ = 0 ) represents the saturated vapor state and lies on the
saturated vapor line. The total volume of the system in wet vapor region is an extensive state
property and is made up of the liquid and vapor parts.
V = V/ + V// = m/ / + m// //
15
V m / / m // //
(1 x ) / x //
m m
m
= / + x (// - / )
(2.16)
Equation (2.16) states that the average specific volume of the two phase mixture, , is a
linear function of x, and equals the specific volume of the liquid plus the volume increase
upon vaporization (// - / ) times the mass fraction of the system vaporized. The vapor content ,
x, can be expressed explicitly by
x
/
// /
(2.17)
The temperature between the states 2 and 4, i.e. the temperature at which both liquid
and vapor coexist depends on pressure. It has higher values at higher pressures and smaller
values at smaller pressures. This temperature is called saturation temperature or boiling point
temperature and is defined as that temperature at which vaporization takes place at a given
pressure. The corresponding pressure is called the saturation (vapor) pressure. For a pure
substance there is a definite relation between the saturated temperature and saturated
pressure. This relation between temperature and pressure during evaporation and
condensation is given by the so called vapor pressure curve ( vapor pressure line ). Figure 2.8
shows the vapor pressure curve for water and some other pure substances in p-t diagram
above 0 oC.
The dependence of boiling temperature or condensation temperature on pressure, i.e.
the shape of vapor pressure curve is very important from technical point of view and forms
the basis of the steam power plants, heat pumps and refrigerators. We will have a brief look
into these. A detailed study is left for next semester.
H2O
200
bar
150
NH3
100
CO2
R12
50
100
200
300
16
Heat Q is tranferred from an external source ( furnace, where fuel is continuously burnt ) to
water in the boiler to produce steam having a pressure of 200 bar and at nearly 550 oC
(superheated steam; the boiling point of water at 200 bar is 365.81 oC). During this process
the water takes up energy which is stored in the form of high pressure and high temperature.
Hence the steam leaving the boiler has the potential (capacity) for doing work and rejecting
(giving) heat.
PSP
boiler
PT
turbine
pump
condenser
30 C according to the vapor pressure curve of water. So the vapor can reject heat Q 0 when it
is brought in contact with a cold surrounding ( condenser, where cooling water at 15 oC
circulates ). Hereby it is condensed completely. Then the liquid water is pumped back to the
boiler (pressure level 200 bar) with the help of a condensate pump by supplying energy P SP in
the form of work. Here one should note that the working of a steam power plant is possible
only because of the characteristic ( namely steep ) vapor pressure curve of water.
o
The steam power plant works only because the different pressures at the entry and exit
of the turbine correspond to technically attainable temperatures (550 C and 30 C) for the
heat supply and the heat rejection. A flat vapor pressure curve in comparison to that of water
would be unsuitable for the technical realization of the power plant cycle. Because then after
the expansion in the turbine, the vapor will attain a saturation Temperature of 30 C at a much
higher pressure. As the expansion only up to a relatively higher value for pressure would be
possible, the obtainable work will be smaller (lower work production). Also in the case of a
flat vapor pressure curve the saturation temperature corresponding to desired high pressure at
17
the entrance of the turbine would also be very high and difficult to attain. The quantitative p-t
behaviour of water is therefore technically very much important for the functioning of steam
power plants. One sees here the importance of the study of the properties of substances (e.g.,
the vapor pressure curve).
The working of a very common domestic appliance, namely the refrigerator working on the
vapor-compression refrigeration cycle, is also based on the vapor pressure curve. A simple
refrigerator consists of a compressor, a condenser, an expansion valve (or capillary), and an
evaporator, as shown in Figure 2.10.
condenser
expansion valve
compressor
evaporator
1
PV
vapor (the liquid refrigerant absorbs heat Q 0 in evaporator from the food storage
compartment) at a low pressure. It will be brought to a higher pressure by the application of
compression work Pv. Now it is also at a higher temperature (corresponding to its vapor
.
pressure curve) and has the potential to give heat Q during condensation. The fluid
(refrigerant) then leaves the compressor and enters the condenser as a vapor at some elevated
pressure (e.g., 10 bar), where it is condensed as a result of heat transfer to the surroundings
(For a condensation temperature of 40 C, surroundings in the kitchen, R12 has a pressure of
about 10 bars). The refrigerant then leaves the condenser as a higher pressure liquid. As the
liquid flows through the expansion valve (generally in the form of a long capillary tube) its
pressure is reduced from the condenser pressure to the evaporator pressure. This vapor then
enters the compressor. The refrigerator rejects in this way heat from the cool storage room (of
refrigerator) to the surroundings and keeps the temperature of storage room low. A machine
which works on similar principles may be used for heating purposes. It is then known as heat
pump. In a heat pump the heat is taken from the surroundings so as to evaporate a suitable
working substance. The vapor is compressed and gives (rejects) heat to the heating system at
18
a suitable temperature. A refrigerator and a heat pump are thus distinguished only by the
desired effect, i.e. cooling or heating.
1 atm
ice
ice
-20 C heated
(a)
1 atm
1 atm
1 atm
steam
liquid water
0 C heated
(b)
steam
liquid water
100 C heated
(c)
250 C heated
(d)
19
If the heating of ice at -20 C to steam at 250 C were done at a constant pressure of 2 bar
similar regimes of heating would have been obtained with similar saturation states.
If the initial pressure of the ice at -20 C is 0.2602 kPa, heat transfer to the ice first results in
an increase in temperature to -10 C. At this point, however, the ice would pass directly from
the solid phase to the vapor phase in the process known as sublimation. Further heat transfer
would result in superheating of the vapor.
If we start with ice with an initial pressure of 0.6113 kPa and a temperature of -20 C and
heat it slowly. Then as a result of heat transfer the temperature will increase until it reaches
0.01 C. At this point if further heat is supplied some of the ice will become vapor and some
will become liquid, because at this point it is possible to have the three phases in equilibrium
(triple point).
H
Critical point
Liquid
phase
E
Solid
phase
C
A
Vapor
phase
D
Triple point
Temperature
Figure 2.12 : Pressure-temperature diagram for a substance like water.
The curve passing through the melting points at different pressures is called the fusion
curve ( fusion line ), and the curve passing the vaporization or condensation temperatures at
different pressure is called the vaporization curve (line). The sublimation curve (line) gives
the vapor pressure of solid at different temperatures. The fusion curve, the vaporization
curve, and the sublimation curve meet at the triple point (triple phase state).
Along the fusion curve, solid and liquid phases are in equilibrium, along the
sublimation curve solid and vapor phases are in equilibrium and along the vaporization curve
the liquid and the vapor phases are in equilibrium. The intersection of these three curves at
the triple point in a p-T diagram represents the conditions under which three phases can
20
coexist in equilibrium. These conditions are represented by a point only on a pressuretemperature diagram; on other property diagrams they are represented by a line or an area.
If three phases of a pure substance exist together in a system, only one value of pressure and
only one value of temperature are possible. The state of each phase present in the system is
fixed. However, more information is required (namely, the proportions of the phases present)
to determine the state of the system (mixture of liquid + vapor) at the triple point temperature
and pressure. For example, the specific volume of the system with 1 per cent vapor content is
much less than that of the system with 10 per cent vapor content.
The triple point of water is at 0.6113 kPa and 273.16 K. The vaporization curve ends
at the critical point because there is no distinct change from the liquid phase to the vapor
phase above the critical point. The liquid and vapor are indistinguishable from each other.
There is no sudden change from the liquid state to the vapor state. The critical pressure and
the critical temperature are the highest pressure and temperature at which distinguisable
liquid and vapor phases can coexist together in equilibrium.
A look at the Figure 2.12 shows that a solid at the state A will pass directly to vapor
at state B if it is heated at constant pressure (which is less than the triple point pressure). At a
constant pressure above the triple point pressure ( from state E ) the substance first passes
from the solid to the liquid state at a definite temperature and then passes to vapor state F at a
higher temperature. The constant pressure line C-D passes through the triple point. At a
pressure above the point the change from the state G to H is not distinguishable.
Water is one of a very few substances that expand on freezing. Most substances
contract on freezing and the freezing temperature increases as the pressure increases, so that
the solid-liquid saturation curve or fusion (melting) line appears as in Figure 2.13, i.e. the
slope of the fusion line is positive. On the other hand, this slope is negative for water (see
Figure 2.12). This is also the reason that ice melts at constant temperature if the pressure
increases.
21
22
23
saturated vapor and the point r represents saturated solid at the same pressure. The points
between r and h represent solid-liquid, solid-vapor or solid-liquid-vapor mixtures. The points
between h and i represent solid-vapor, liquid-vapor or solid-liquid-vapor mixtures. The phase
transition from liquid to solid at constant pressure is accompanied by a decrease in specific
volume. It is to be pointed out again that at constant pressure the phase transition from liquid
to solid water (ice) is accompanied by an increase of specific volume.
The isotherms (lines of constant temperature) are also shown in Figure 2.14 as broken
lines. In all two phase regions the constant temperature lines coincide with constant pressure
lines.
It is to be kept in mind that the specific volume scale is greatly distorted in pdiagram. For all substances the change in specific volume between points h and i is many
times greater than between r and h and also the critical specific volume is only slightly
greater than at r or h. To emphasize this, only parts of the p-v diagrams of carbon dioxide
and water are shown in Figure 2.15 with true linear scales. Usually the volume axis is plotted
logarithmically.
Figure 2.15 : p- diagrams to true linear scale for carbon dioxide and water.
24
The temperature, pressure and specific volume at this point are called the critical temperature
(Tc), critical pressure (pc) and critical volume (c) respectively.
It will be noted that there are six distinct regions in each of the p--T surfaces.
Single Phase Region:
(a) solid:
(b) liquid:
(c) vapor:
A p--T diagram provides a better picture of the relationship among pressure, specific
volume and temeperature because here each point represents only one equilibrium state.
Various regions of a p--T diagram overlap on a p- projection. Any given point on a pdiagram can represent a solid, a solid-liquid, a liquid or a liquid-vapor mixture depending on
the temperature
25
26
27
Table 2.2 may be used to read other saturation properties at a given pressure. If data are
required for intermediate temperatures or pressures, linear interpolation is done.
Table 2.3 gives the values of the properties (volume, internal energy, enthalpy and
entropy) of superheated vapor for each tabulated pair of values of pressure and temperature,
both of which are now independent. Now the interpolation or extrapolation is to be done for
pairs of values of pressure and temperature. Table 2.4 lists the properties of subcooled water
(compressed liquid water ). Table 2.5 lists the ice-vapor saturation (sublimation) values.
Similar tables for other technically important substances are also available.
However, now with the development of computer based calculation it is more
convenient to use analytical equations, e.g. equation of state in place of these table. The
model of ideal gas (perfect/ideal gas equation) is used for the calculation of thermal
properties of gases at low densities (pressures up to a few bars). This model is based on the
universal behaviour of gases irrespective of their nature at low densities.
(p)ig = R T
or
(pV)ig = n R T
R
(pV)ig = m ( M ) T
(2.18)
(2.19)
This model is quite accurate and is used for describing the behaviour of gases at low
pressures. A real gas obeys ideal gas law at temperatures that are high relative to the critical
temperature and at pressures that are low relative to the critical pressure. The gas oxygen,
nitrogen, air or hydrogen may be treated as ideal gases at ordinary temperature and pressure.
The ideal gas equation of state p = RT is valid only under the following assumptions:
- the volume occupied by the molecules themselves is negligibly small compared to
the volume of the gas.
- there is no attraction between the molecules of the gas.
So at low pressures and high temperatures, where these conditions are fulfilled the real gases
follow ideal gas equation. But as pressure increases, the intermolecular forces of attraction
and repulsion increase, and also the volume of the molecules becomes appreciable compared
to the total gas volume. Then the real gases deviate considerably from the ideal gas equation.
To describe the behaviour of gases at higher pressures some other equation of states
may be used. A well known equation is Van der Waals Equation, which is given below:
(p
a
)( b) RT
2
(2.20)
where a and b are the constants specific to the substance. The coefficient a is introduced to
account for the existence of mutual attraction between the molecules. The coefficient b
accounts for the finite size of molecules.
Real gases conform more closely with Van der Waals equation of state than the ideal
gas equation of state, particularly at higher pressures. A widely used equation of state with
good accuracy is the Redlich-Kwong Equation:
28
RT
a
1
2
T ( b)
(2.21)
(2.22)
0.0866 RTc
pc
(2.23)
Another widely used equation for describing the properties of gases is the virial
equation of state:
or an alternative expression
p
1 B ' p C ' p D' p ....
RT
(2.24)
p
B C D
1 2 ...
RT
(2.25)
B,C, B, C etc. are called virial coefficients. B and B are called second virial coefficient, C
and C are called third virial coefficients, and so on. For a given gas, these coefficients are
p
functions of temperature only. The ratio RT is called the compressibility factor z. For an
ideal gas z = 1. The magnitude of z for a certain gas at a particular pressure and temperature
gives an indication of the extent of deviation of gas from the ideal gas behaviour. The virial
equations (2.24) and (2.25) may also be written as:
z 1 B' p C' p D' p....
(2.26)
B C D
...
2
(2.27)
or
z 1
B C D
, 2 , ...
The terms etc. arise on account of molecular interactions. If no such interactions
exist ( e.g. at very low pressures ) then B = 0, C = 0 etc. Hence z = 1, i.e. p = RT.
A similar and accurate model for liquid region does not exist. For calculation the fluid
model of ideal liquid is used:
il
= const.
According to this model (ideal liquid model) the volume (molar or specific) of a
liquid is supposed to be constant. The small dependence of volume on temperature and
29
pressure is neglected. Figure 2.18 shows the t- diagram of water. We see that the specific
volume is almost independent of temperature and pressure up to 200 C. The model of ideal
liquid will not describe the real behaviour of liquids exactly but may be used for a reasonable
and good approximation.
500
C
B
400
A
p = 200 bar
p = 100 bar
300
p = 25 bar
200
critical point
boiling liquid
saturated vapor
p = 1 bar
100
0
0
cm3 /g
v
10
(2.28)
where ps is the saturated vapor pressure at temperature T; p0, T0 and A are three substance
specific constants. According to this equation a log(p) versus 1/T plot should be linear. In
Figure 2.19 log(p) is plotted against inverse Temperature [see the logrithmic scale for p] for
some substances and we see a linear relationship. The critical temperature and triple point
temperature for the substances are also indicated. There are of course some substances which
do not show linear behaviour.
30
1000
374C
31C
112C
-147C
100
bar
10
-56C
CO2
H2
N2
1
-210C
0.1
H2O
0.01
0C
0.001
0.0001
-240C
-259C
R12
0.2
0.4
0.6
1/T
1/K
0.8
Figure 2.19 : Vapor pressure curve of some substances in log p versus 1/T diagram.
2.4
Mixtures
Raw materials are generally found in nature as mixtures. Pure substances as well
mixtures with desired properties are produced through appropriate material transformations
of substances available in nature. Mixtures of desired properties may also be produced by
mixing the pure substances in appropriate ratios. For example, the useful product ammonia is
produced by mixing hydrogen and nitrogen under suitable conditions. In many other
engineering applications we encounter thermodynamic systems, which are mixtures of pure
substances. The mixtures are sometimes referred to as solutions, particularly a solid dissolved
in liquid. A knowledge of the qualitative and quantitative behaviour of mixtures is thus
necessary for the thermodynamic analysis of the material transformation.
A mixture is defined as any collection of molecules, ions, electrons. Each of these is
called a species (or a constituent of the mixture) if it is distinguishable from the others by
virtue of its chemical structure. In reacting mixtures the amount of each constituent can not
necessarily be varied independently. In nonreacting mixtures each and every constituent can
31
be varied independently and every constituent is also a component. Components are those
constituents the amount of which can be independently varied. By varying the amount of
components the composition may be varied. The composition of a mixture is expressed in
various forms which are described below.
Mass fraction:
The ratio of the mass of a constituent a to that of the total mixture is known as the
mass fraction ( wa ) of the constituent. For instance, the mass fraction of a component a in a
mixture is:
wa
ma
mT
where mT = ma + mb + mc + ....(2.29)
If wa is multiplied by 100 we get weight per cent. The sum of all ws is equal to 1, i.e.
wi = 1.
Mole fraction:
The mole fraction xa of a component a is the amount of a expressed as a fraction of
the total amount of molecules ( i.e. moles ). It is the ratio of the number of moles of a
constituent to the total number of moles in the mixture.
xa
na
nT
Va
VT
where VT = Va + Vb + ...
(2.31)
If a is multiplied by 100 we get volume per cent. The sum of all s is equal to 1, i.e.
i
= 1.
The mass fraction and the mole fraction are related to each other as under:
wi
mi
M i ni
M i xi
mi M i n i M i x i
(2.32)
32
mi
n
Mi
xi i
ni m i
Mi
wi
Mi
w
Mi
i
(2.33)
(2.35)
where x2 is the mole fraction of say component no. 2. The dependence of on the mole
fraction of component 1 (x1) is already taken into account by considering x2 because the
relation x1 = (1 - x2 ) holds.
A similar relationship for specific volume is
33
= (t, p, w2)
(2.36)
The thermal properties of fluid mixtures in the two phase region (liquid-vapor region)
are very much important because many operations performed in chemical, petroleum, and
related industries involve the contact between phases. The analysis or design of processes
such as distillation, liquid-liquid extraction requires an understanding of principles of phase
equilibrium and an availability of equilibrium data.
For a binary system in a two phase region the number of degrees of freedom i.e. the
number of intensive phase properties is 2 (2 - 2 + 2 = 2). So if the composition and pressure
are fixed, the temperature is automatically fixed.
Now we look at the vapor-liquid equilibrium of a binary system by considering a
mixture of toluene (component 1) and cyclohexane (component 2).
120
C
110
140
kPa
Saturated
vapor
Superheated
vapor
100
80
E
D
80
C
Subcooled
liquid
Saturated
liquid
Subcooled
liquid
100
Saturated
liquid
90
120
Constant t = 90 C
60 A
Superheated
vapor
Saturated
vapor
40
70
0.0
0.5 0.65
1.0
0.0
x2
0.5 0.65
1.0
x2
Figure 2.20 : Phase diagrams for toluene (1) + cyclohexane (2) system.
Both toluene and cyclohexane exist as liquids at room temperature (vapor pressure of
toluene at 25 C = 28.47 mm Hg = 3.796 kPa ; vapor pressure of cyclohexane at 25 C=
97.77 mm Hg = 13.035 kPa). We consider a mixture of toluene and cyclohexane at 115 C at
a constant pressure of 1 atm (101.3 kPa). At this temperature both toluene and cyclohexane
exist as superheated vapors (b.p. of toluene = 110.56 C ; b.p. of cyclohexane = 80.75 C)
and form a gaseous mixture (only one phase, namely vapor phase). Applying the phase rule
we get the number of degrees of freedom F for this situation : F = C - P - 2 = 2-1+2 = 3. We
have fixed the temperature and pressure and hence there remains one more variable
(composition) which is necessary to completely describe the system. The composition can be
selected in the entire composition range ( xcyclohexane = 0.0 to 1.0 ). We select the composition of
the gas phase as xcyclohexane = 0.65 and xtoluene = 0.35. If we cool down this mixture then at a
certain temperature the vapor will start to condense as liquid and will do so over a range of
temperature. The temperature range lies between the b.p. of cyclohexane and toluene
(80.75C to 110.56C). Within this range the mixture will exist as a two phase system (one
34
vapor phase and one liquid phase) [Fig. 2.20 shows a t-x diagram]. For the two phase region
the number of degrees of freedom F = 2-2+2 = 2. So if the pressure and temperature are given
(e.g. p = 101.3 kPa, t = 90C) then there is no more variable left. The composition of the
vapor phase and of the liquid phase is fixed automatically ( points B and D ). The
compositions of liquid phase and of the vapor phase are not identical. The vapor phase is
richer in the more volatile component, namely cyclohexane (having lower boiling point and
higher vapor pressure) and the liquid phase is richer in toluene (higher b.p. and lower vapor
pressure). This fact is the basis for separation of liquid mixtures by distillation. We will learn
more about it when we study ideal systems in the forthcoming chapter.
The above mentioned mixture ( x2 = 0.65 ) of toluene and cyclohexane at 90C and at
40 kPa pressure (low pressure) will exist as a homogeneous gaseous mixture. On increasing
the pressure we will come across a two phase region (vapor-liquid region) where the
composition of the phases is different. The liquid phase will be richer in toluene and the
vapor phase will be richer in cyclohexane. So by lowering the temperature or increasing the
pressure the components of a mixture of superheated vapors may be condensed.
35
2.0
mol
1.5
1.0
0.5
100
200
300
400
500
t
Figure 2.21 : Chemical equilibrium of ammonia synthesis ( Initial composition: 1 mol N 2 + 3
mol H2 ).
(2.37)
where {xj} represents the mole fraction of all components. x i represents the mole fraction of a
component i and i, the partial molar volume of the component. The partial molar volume of a
component i, i is the molar volume of that component in the mixture. In general, it is different
from the molar volume of the pure component i. It is a complex function of temperature,
pressure and the composition.
i
= i ( T, p, {xj})
(2.38)
Relations similar to Equations (2.37) and (2.38) may be written for the corresponding
specific volumes.
The difference between the partial molar volume and the molar volume may be
understood from the following experiment:
At a given temperature and pressure (say room temperature and atmospheric pressure)
we add a small amount of water (say 1 mol) to a very large volume of pure water. The
increase in volume is found to be:
18 cm3 (= the molar volume of water, ow)
However if we add the same amount of water (i.e. 1 mol) to a large volume of pure ethanol,
the increase in volume is not 18 cm (i.e. ow ) but only 14 cm (the molar volume of water in
36
the mixture, w). Obviously, in this case the effective molar volume of water in ethanol is
smaller than the molar volume of pure water (w < ow ). The reason for the smaller increase is
that the volume a given number of water molecules (e.g. 1 mol) occupy, depends on the
molecules that surround them. In this case each water molecule is surrounded by ethanol
molecules and such a packing of molecules results in an increase of only 14 cm. The quantity
14 cm mol-1 is the partial molar volume of water in pure ethanol. In general this quantity is
denoted by w (w = 18 at xethanol = 0 and w = 14 at xethanol = 1) and is a mixture property. The
partial molar volumes of the components of a mixture vary with composition ( That is i is a
function of the composition). The partial molar volumes of water and ethanol in (water +
ethanol) mixture for the entire composition range at 25C and 1atm are shown in Figure 2.22.
58
Ethanol
Water
18.0
56
16.0
54
14.0
0.1
0.2
0.4
0.6
0.8
1.0
x (ethanol)
Figure 2.22 : The partial molar volumes of water and ethanol in water + ethanol mixture.
In future the symbol oi will be used in subscript to denote the properties of the pure
components.
= molar or specific volume of pure component i
= partial molar or partial specific volume of component i
oi
i
Simple models for the mixture set the partial molar properties or the partial specific
properties equal to the properties of pure substances, the properties which are generally
known.
For example
i
( T, p, {xj}) = oi ( T, p)
(2.39)
37
For gases the model of ideal gas mixture is used. As in the case of pure gases, it is
assumed that the molecules themselves have negligible volumes and the molecule of type i is
not influenced by the presence of molecule of type j. Each component k behaves as if it were
alone in the available space (volume) and has the pressure (its partial pressure):
RT
V
RT
RT
RT
p1ig n1
p2ig n2
p3ig n3
V ,
V ,
V ....
i.e.
pkig nk
(2.40)
RT
RT
RT
nk
n
p
V
V
V
(2.41)
(2.42)
For an ideal gas mixture, the partial pressure of a component is therefore equivalent to
the mole fraction.
Further
V ig (T , p, {n j })
V ig
i
ni RT n j RT nRT
pi
pj
p
ni RT
Voiig (T , p, ni ) ni oiig (T , p )
p
i
i
(2.43)
ig (T , p, {x j }) xi oiig (T , p )
(2.44)
One can write, therefore, for the partial molar volume of a component i in an ideal gas
mixture:
RT
iig (T , p, {x j }) oiig (T , p )
p
(2.45)
and for the partial specific volume
iig (T , p, {w j }) oiig (T , p ) (
R T
)
M p
(2.46)
The ideal gas mixture model describes the thermodynamic behavior of gas mixtures in the
same range in which the ideal (perfect) gas model describes the behavior of pure gases,
namely at low pressures up to a few bars and at a distance from the saturation vapor curve.
38
(2.47)
where pV is the partial pressure of water vapor and psV is the saturation pressure of pure water
vapor at temperature T.
vapor
dew 3
point
saturation line
liquid
39
RT
RT
mV
V
M VV
This is the pressure exerted by the vapor on the container wall if it were alone in the
volume V. Thus in an ideal gas-vapor mixture the saturated state is defined so that the partial
pressure of vapor is equal to the saturation vapor pressure of the pure vapor at the
temperature of the mixture:
pV = psV(T) = psW(T)
(2.48)
(2.49)
On further cooling more condensate is formed and the gas phase will contain less
vapor, i.e. it will be dried. The dew point temperature of a gas-vapor mixture (moist air) has a
definite value depending on the partial pressure of water vapor in the moist air. Hence the
relation between the dew point and the corresponding partial pressure of water vapor in moist
40
air is provided according to the model of ideal gas / water vapor mixture through the vapor
pressure curve of pure water.
We now look at some other definitions relevant to moist air. Specific humidity or
humidity ratio x, is defined as the mass of water vapor (or moisture) per unit mass of dry air
in a mixture of air and water vapor. If mG is the mass of dry air in mixture and mV the mass of
water vapor then
m
x V
mG
(2.50)
Specific humidity is a suitable property to describe the state of unsaturated and
saturated gas-vapor mixture. The advantage of describing the relative humidity in terms of
the mass of dry air instead of mass of the mixture is that the mass of dry air does not change
when water condenses or evaporates into the air (mass of dry air remains constant whereas
the mass of moist air changes with the amount of moisture).
Another important property of moist air is the relative humidity, The relative
humidity is defined as the ratio of the partial pressure of water vapor, pV, in a gas-vapor
mixture to the saturation pressure, psV, of pure water, at the same temperature of the mixture:
pV
p sV ( T )
The specific humidity may be related to the relative humidity and to the partial
pressure. For unsaturated gas-vapor mixture using the ideal gas law we can write:
mV pV
mG p G
and
V
R
(
)T
MV
V
R
(
)T
MG
as p = pV + pG it follows:
mV
p M
M V pV
V V
mG
pG M G M G ( p pV )
(2.52)
pV
pV
p sV ( T )
18
0.622
0.622
28.96 ( p pV )
( p pV )
( p p sV ( T ))
(2.53)
x
or
xp
(0.622 x)
(2.54)
41
MV
p sV (T )
p sV (T )
0.622
M G ( p p sV (T ))
( p p sV (T ))
(2.55)
The volume of an ideal gas-vapor mixture is given by the addition of the volume of
gas and the volume of vapor
V = VG + VV
In practice the mass of gas (air) remains constant in moist air and it is only the mass
of vapor (moisture, water vapor) which changes. It is, therefore practice to define the specific
properties of gas-vapor mixtures in terms of the mass of the gas m G. For example, the specific
volume of an unsaturated gas-vapor mixture or a just saturated gas-vapor mixtures is defined
as the volume per kg of gas:
m mV V
V
1 x
G G
G xV
mG
mG
1 x
The subscript (1+x) in
kg vapor.
1+x
RT
RT
R
R
T
x
[
x]
MG p
MV p
M G MV
p
(2.56)
For the specific volume of saturated gas-vapor mixture the volume of the condensed
phase (liquid) should also be considered. But as the specific volume of the condensate is very
small as compared to specific volume of gas, it may be neglected and the above equation
(2.56) may also be used for saturated ideal gas-vapor mixtures.
42
iil (T , p, {x j }) oil (T , p )
(2.57)
where loi (T,p) is the molar volume of pure liquid i at the temperature and pressure of the
solution (liquid mixture). We write, therefore, for the molar volume of an ideal solution
(liquid mixture)
il
(2.58)
Similar relation holds for the partial specific volume of an ideal liquid mixture.
il
(2.59)
With xi and wi we denote the mole fraction and the weight fraction of any component i in the
liquid phase. {xj} and {wj} represent the mole fractions and weight fractions of all
components.
(2.60)
These partial pressures are measurable, as are the equilibrium mole fractions x 1, x2,.... in the
liquid. Let one of the components, i, be present in relatively large amount as compared to any
of the others. Then it is found experimentally that
pi = xi ps0i
(2.61)
where ps0i is the vapor pressure of the pure component i. This is Raoults law. It states that the
partial pressure of a substance in a mixture is proportional to its mole fraction and its vapor
pressure when pure. It is a limiting law and it is followed in any solution as x i approaches
unity. Raoults law is obeyed very well over a wide range of concentrations, when the
components are similar in structure and chemical nature. An example is the mixture of nhexane and n-heptane. Similarly, a mixture of benzene and toluene (methylbenzene) obeys
the Raoults law throughout the composition range and is termed as an ideal system. The
ideal system is defined as one in which each component obey Raoults law over the entire
range of composition. According to equation (2.61) the partial pressure of species i in the
vapor phase, written on the left hand side, is equal to the product of the liquid phase mole
fraction xi of species i and its vapor pressure ps0i at equilibrium temperature T.
43
We now apply Raoults law to binary mixtures in which both components are volatile.
The partial vapor pressures of the two components of an ideal binary mixture are proportional
to the mole fractions of the components in the liquid. The total pressure of the vapor is the
sum of the two partial vapor pressures. So we have in a binary liquid solution
x1 + x2 = 1
and also
(2.62)
p2 = x2 ps02
(2.63)
(2.64)
Equation (2.64) relates the total pressure over the mixture to the mole fraction of component
2 in the liquid at constant temperature. It further shows that p is a linear function of x2. This
relationship is shown in Figure 2.24. The curve is called bubble-point curve. It is clear from
Fig. 2.24 that the bubble-point curve in an ideal system is a straight line in p-x diagram ( also
called vapor pressure diagram). The bubble-point curve connects the vapor pressures of the
pure components. The terms x2 ps02 and (1-x2 ) ps01 are also plotted in Figure 2.24 and show
the Raoults law.
The expression for the dew-point curve may be derived as follows:
x2 = p2 / p
(2.65)
[ We use "double slash" in the superscript to represent the composition (here, mole fraction)
of the vapor phase. When the liquid and the vapor phase exist together we will consistently
use "single slash" in the superscript for liquid phase and "double slash" in the superscript for
the vapor phase composition. For overall composition no superscript will be used]
44
150
Constantt = 90 C
kPa
pS02
bubble-point
curve
120
100
dew-point
curve
pS01
50
t S01
B'
100
p2is
= x2' pS02
dew-point
curve
bubble-point
curve
90
D'
80
0
0.5
1.0
70
t S02
0.5
1.0
Figure 2.24 : p-x and T-x Diagrams for an ideal binary system.
Using the values of p2 and p from equations (2.63) and (2.64) we obtain
x'2'
x '2 p s 02
x '2 p s 02
p
p s 01 x'2 ( p s 02 p s 01 )
(2.66)
or
x2'
p s 02
x 2'' p s 01
x 2'' ( p s 02 p s 01 )
(2.67)
p s 02
x 2'' p s 01 ( p s 02 p s 01 )
p s 02 x2'' ( p s 02 p s 01 )
p s 01 p s 02
x2'' ( p s 02 p s 01 )
(2.68)
Equation (2.68) expresses p as a function of x2, the mole fraction of component 2 in vapor.
This function is also plotted in Figure (2.24). It is called dew-point curve. One sees that the
dew-point curve is not a straight line but a curve.
Equation (2.68) can also be rearranged in another form.
45
x ''
x ''
1
1 2
p p s 01 p s 02
(2.69)
p s 01 (T )
p (T )
x2' s 02
p
p
(2.70)
p
p
x2''
p s 01 (T )
p s 02 (T )
(2.71)
Equations (2.70) and (2.71) can only be solved iteratively as the vapor pressure is a function
of temperature.
The bubble-point curve ( T- x2 ) is most readily constructed by solving (2.64) for the
bubble-point compositions x2 at representative values of T between the saturation
temperatures of the pure components
x 2'
p p s 01 (T )
p s 02 (T ) p s 01 (T )
(2.72)
p s 02 (T ) p s 02 (T )
[ p p s 01 (T )]
p
p
[ p s 02 (T ) p s 01 (T )]
(2.73)
The VLE (vapor-liquid equilibrium, i.e. x2 vs. x2) diagram of an ideal system at a given
temperature may be constructed most conveniently using equation (2.66). The isobaric VLE
diagram may be constructed from the corresponding T-x diagram. Figure 2.25 shows
schematic VLE diagram for an ideal system. The VLE diagrams at constant temperature and
at constant pressure do not differ much from one another. One can see from Eq. (2.66) that
for an ideal system if ps02 =ps01, i.e. if the vapor pressures of the pure components are equal,
then no material separation can be achieved as the bubble-point curve and the dew-point
curve merge into one another.
46
(2.74)
(2.75)
Equation (2.75) shows clearly that the relative volatility in a binary ideal system is the ratio
of vapor pressure of the two components, i.e. it depends only on temperature. It does not
depend on the composition of the mixture. Its temperature dependence is weak and for small
temperature ranges the relative volatility may be considered as constant.
There are only a few systems which may be considered as ideal systems. However,
the model of ideal systems helps very much to understand the behavior of real solutions.
Because now only the deviations from the ideal system behavior is to be considered. Both
liquid-phase and vapor-phase behavior may contribute to non-ideality of a system. In most of
the cases it is the non-ideal behavior of liquid phase which causes the deviations from an
ideal system. The non-ideality of the liquid phase is interpreted in terms of the deviations
from the Raoults law. A significant result of Raoults law is that the bubble-point curve of an
ideal system is a straight line. Systems for which the bubble-point and partial pressure curves
lie above the Raoults law lines, are said to exhibit positive deviations from the Raoults law.
47
Similarly, if these curves lie below the Raoults law lines, the system is said to exhibit
negative deviations from the Raoults law.
48
T0,1 a
Two-phase
region
e
c
T2
Saturated vapor
d
f
Saturated liquid
b T0,2
Subcooled liquid
x2
1.0
Figure 2.27 : Vapor-liquid phase equilibrium for substance A(1) + substance B(2) at p =
const.
We look into the T-x diagram of this system (Figure 2.27). The lower curve a-e-c-b is
called the bubble-point curve and describes the liquid composition. The upper curve a-d-f-b,
called the dew-point curve, describes the vapor composition. The curves a-e-c-b and a-d-f-b
intersect the T-axes at T0,1 and T0,2. These are the boiling points of substance A and substance
B respectively at a constant pressure of 101.3 kPa. The region on and above a-d-f-b
represents the superheated vapor. Here only vapors of component 1 (i.e.,A) and component 2
(i.e.,B) are present and the overall mole fraction x2 of B is the same as x2 (at state 5). On and
below the bubble-point curve (a-e-c-b) only liquid phase is present and the overall mole
fraction x2 of B is x2 (at state 1). Within the area enclosed by the two curves both liquid and
vapor are present and any point within this area represents quantitatively the relative amounts
of each (liquid and vapor). We note that the temperature varies from T (state 2) to T (state 4)
during the phase transition from liquid to vapor. This is in contrast to the phase transition in a
pure substance that takes place at a constant temperature (if pressure is fixed).
Mixtures within the area enclosed by a-e-c-b and a-d-f-b will consist of both liquid
and vapor parts. The equilibrium compositions of the phases are determined from the phase
49
diagram by drawing a horizontal line at constant temperature (at equilibrium state the
temperature and pressure in the two phases should be the same). The intersection of this line
with the dew-point curve yields the the value of x2 which describes the composition of the
vapor, while the intersection with bubble-point curve yields the value of x2 which describes
the composition of the liquid. Straight lines such as e-4, c-d and 2-f, which connect states in
phase equilibrium, are known as tie lines.
Tie lines are useful for deriving the overall composition in the vapor-liquid two-phase
region. Let n be the total number of moles of a mixture having a mole fraction x2 of
component 2 which separates into n moles of liquid with a mole fraction x2 and n moles of
vapor of mole fraction x2. A material balance (mole number balance) on component 2 gives
x2 n + x2n = x2 n
(2.76)
(2.77)
n '' x 2 x 2'
(2.78)
Derivation of lever principle
Dividing (2.76) by n
n'
n
x
x 2'' x 2 ''
''
n
n
(a)
n'
n
1 ''
''
n
n
(b)
n
''
Putting the value of n from (b) in (a)
n ' x 2''
n'
''
x
2
2
2
n ''
n ''
n'
( x2 x2' ) x2'' x2
n ''
We see from Figure (2.27) that (x2-x2) and (x2-x2) are the lengths of the segments 3-d and c-3
of the tie line c-d. Thus we have
n' 3 d
n '' c 3
This is known as the lever principle. It states that the ratio of the numbers of moles of
the equilibrium phases is inversely proportional to the ratio of the lengths of the
corresponding segments of the tie line.
The lever principle also holds for mass units if the analogous quantities are substituted for
mole numbers and mole fraction in the above relation.
50
m ' w2'' w2
m '' w2 w2'
(2.79)
T
T0,1
T2
T4
T6
1
R1
D1
T0,2
D2
x2
1.0
51
the more volatile component B than the original liquid. We call it distillate D1. The rest is
known as residue R1. This is the process of simple distillation.
In the process of fractional distillation, the boiling and condensation cycle is repeated
successively. When the condensate of composition x2 (at 4) is reheated, it boils at T4 (at state
5) and yields a vapor of composition x2 (at 5) which is even richer in the more volatile
component. The vapor (distillate D2) is drawn off, and the first drop condenses to a liquid of
composition x2 (at 6). The cycle can be repeated until almost pure B is obtained. The time
and labor involved in this batch type of separation is very high. Hence in practice the so
called fractionating column is used for continuous separation. The vapor passes up a vertical
fractionating column packed with glass rings or beads to give a large surface area. The
successive cycles of vaporization and condensation take place on their surfaces.