 It can exist in more than one phase but its chemical composition is the same in all the phases. A good example is water
Steam Liquid water
 A chemical analysis will show that in a mixture of liquid water and steam, the hydrogen and oxygen atoms are in the ratio of 2 : 1 regardless of which sample (steam or liquid water) is analyzed
 Sometimes a mixture of gases, such as air, is considered a pure substance as long as there is no change of phase
 A mixture of liquid air and gaseous air is not a pure substance, since the composition of the liquid phase is different from that of the vapour phase
 There are 3 principal phases for a working fluid i.e solid, liquid and gas
 Consider as a system 1 kg of water contained in the pistoncylinder arrangement shown in Figure 2.1(a).
 Suppose the piston and weight maintain a pressure of 0.1 MPa (1 bar) in the cylinder, and that the initial temperature is 20oC
 As heat is transferred to the water, the temperature increases appreciably, the specific volume increases slightly, and the pressure remains constant
 When
the
temperature
reaches
99.6oC,
 Some of the liquid becomes vapour, and during this process both the temperature and pressure remain constant, but the specific volume increases considerably
 When the last drop of liquid has vapourized, further transfer of heat results in an increase in both temperature and specific volume of the vapour as shown in Figure 2.1 (c)
 The term saturation temperature designates the temperature at which vaporization takes place at a given pressure
 This pressure is called the saturation pressure for the given temperature
 Thus for water at 99.6oC, the saturation pressure is 0.1 MPa, and for water at 0.1 MPa, the saturation temperature is 99.6oC
 For a pure substance, there is a definite relation between saturation pressure and
saturation temperature
Pressure
Vapor pressure curve
Temperature
FIGURE 2.1 Constantpressure change from liquid to vapor phase for a substance
 If a substance exists as liquid at the saturation temperature and pressure, it is called saturated liquid.
 If the temperature of the liquid is lower than the saturation temperature for the existing pressure, it is called either a subcooled liquid or a compressed liquid
 A
subcooled
liquid
implying
that
the
temperature is lower than the saturation temperature for the given pressure
 A compressed liquid  implying that the pressure is greater than the saturation
 When a substance exists as part liquid and part vapor at the saturation temperature, its
quality, x is defined as the ratio of the mass of vapour to the total mass
 Thus in Figure 2.1(b), if the mass of vapour = 0.2 kg and the mass of the liquid = 0.8 kg, the quality = 0.2/1.0 atau 20%
X =
 X = 0 : saturated liquid
 X = 1 : saturated vapour
 Quality has meaning only when the substance is in a saturated state i.e. at saturation pressure and temperature
 If a substance exists as vapour at the saturation temperature, it is called saturated vapour (quality is 100 percent or x =1)
 The
saturatedliquid
and
saturatedvapour
states have the same pressure and the same temperature, but are definitely not the same state
 Two independent properties such as pressure and specific volume or pressure and quality are required to specify a saturation state of a pure substance
 When the vapour is at a temperature greater than the saturation temperature, it is said to exist as superheated vapour
 The pressure and temperature of superheated vapour are independent properties, since the temperature may increase while the pressure remains constant
We can also sketch the pressure versus temperature diagram for a substance such as water. This diagram is shown in Figure 2.3
Solid Phase
Triple point
Temperature
 This diagram shows how the solid, liquid & vapour phases may exist together in
equilibrium
 Along the sublimation line, the solid & vapour phases are in equilibrium
 Along the fusion line, the solid & liquid phases are in equilibrium
 Along the vaporization line, the liquid & vapor phases are in equilibrium
 The only point at which all three phases may exist in equilibrium is the triple point
 The vaporization line ends at the critical point because there is no distinct change from the liquid phase to the vapour phase above the critical point. The coordinates of this point are
known as the critical temperature Tc, critical pressure Pc & critical specific volume vc
 Although we have made these comments with specific reference to water, all pure substance exhibit the same general behaviour
(qualitatively)
 Quantitatively, the triple point temperature and critical temperature vary greatly from one substance to another
properties
of
pure
The state of a simple compressible pure substance is defined by two independent properties
 If
the
pressure
and
temperature
of
superheated steam are specified, the state of the steam is determined. This also applies to a compressed liquid
 However, in a saturation state, pressure and temperature are not independent properties
 The
saturatedliquid
and
saturatedvapour
states have the same pressure and the same temperature, but are definitely not the same state
 Two independent properties such as pressure and specific volume or pressure and quality are required to specify a saturation state of a pure substance
measured easily, but others cannot and are calculated by using the relations between them and measurable properties
 The
results
of
these
measurements
and
 The steam tables will be used to demonstrate the use of thermodynamic property tables
 For
each
substance,
the
thermodynamic
 A separate table is prepared for each region : superheated vapour, compressed liquid and saturated(mixture) regions
 Total energy of a system can be catogorized in two groups: macroscopic and microscopic
 The macroscopic forms of energy are those a system possesses as a whole with respect to some reference frame
 The microscopic forms of energy are those related to the molecular structure of a system and the degree of the molecular activity
 The sum of all the microscopic forms of energy is called the internal energy of a system and is denoted by U
 Enthalpy is also a property and is given the symbol H : H = U + PV Or per unit mass, h = u + Pv (kJ/kg) (kJ)
 Enthalpy is often encountered in the analysis of power plants and refrigeration systems
2.4.1
Saturated States
The
properties
of
saturated
liquid
and
saturated vapour for water are listed in the textbook as Tables A4(Temperature table) and A5(Pressure table)
Subscript fg denotes the difference between the saturated vapour and saturated liquid values of the same property
For example : vf = specific volume of saturated liquid vg = specific volume of saturated vapour vfg = difference between vg and vf
vfg = vg vf The quantity hfg is called the enthalpy of vaporization ( or latent heat of vaporization )
hfg represents the amount of energy needed to vaporize a unit mass of saturated liquid at a given temperature or pressure
hfg decreases as the temperature or pressure increases, and becomes zero at the critical point
2.4.2

During a vaporization process, a substance exists as part liquid and part vapour ( mixture )
To analyze this mixture, we need to know the proportions of the liquid and vapour phases in the mixture
This is done by defining a new property called the quality, x as the ratio of the mass of vapour to the total mass of the mixture
x = mg mf + m g
1 x = mf m f + mg
where
Consider a container that contains a saturated liquidvapour mixture with mass m and a quality , x
Volume of this mass is equal to the volume of the saturated liquid and the saturated vapour V = Vliquid + Vvapour or mv = mliquidvf + mvapourvg Dividing the above equation by the total mass and introducing the quality, x, we have: mliquid = mf mvapour = mg m = mf + mg mv = mliquidvf + mvapourvg m m m
 In saturated mixtures, quality can serve as one of the two independent intensive properties needed to describe a state
2.4.3
Superheated vapour
 A substance exists as superheated vapour in the region to the right of the saturated vapour line and at temperatures above the critical point temperature
 Temperature and pressure can be used as two independent properties to determine a state  Table A6 in the textbook lists superheated properties for water the
2.4.4
Compressed Liquid
 Compressed
liquid
tables
are
not
commonly available
 Compressed liquid properties depend on temperature much more strongly than they do on pressure
compressed liquid as saturated liquid at the given temperature  Thus, y = yf@T where y is v, u, or h
2.4.5
 They are calculated from measurable properties using the relations between properties
in
 For water, the state of saturated liquid at 0.01oC is taken as the reference state, and the internal energy and entropy are assigned zero values at that state
2.5
 The
state
of is
simple by
substance
fixed
 Once the two appropriate properties are fixed, all the other properties become dependent properties
 Any
equation
with
two
independent
 Thus,
we
can
represent
the
PvT
 T
and
may
be
viewed
as
the
independent variables (the base) and P as the dependent variable (the height)
 Twophase
regions
are
surfaces
 All the 2D diagrams are the projections of this 3D surface onto the appropriate planes
 A more practical approach would be to have some simple relations/equations among the properties that are sufficiently accurate
 Any equations that relates the pressure, temperature, and specific volume is called an equation of state
 Property relations that involves other properties of a substance at equilibrium states are also known as equations of state
 There are several equations of state, some simple and others very complex
 The simplest and bestknown equations of state for substances in the gas phase is the idealgas equation of state
 This equation predicts the PvT behaviour of a gas accurately within some selected region
 The vapour phase of a substance is called a gas when it is above the critical temperature
 Vapour usually implies a gas that is not far away from a state of condensation
 From experimental observations it has been established that the PvT behaviour of gases at low density is closely given by the idealgas equation of state :Pv = RuT (2.1)
where v = V/N and N is the mole number Ru is the universal gas constant Ru = 8.3144 kJ/kmol K
v/M = V/m = v
R = Ru/M R is the gas constant and is different for each gas
This equation can also be written in terms of the total volume PV = mRT And for a fixed mass, the properties of an ideal gas at two different states are related by : P1V1 = P2V2 T1 T2
At very low density all gases and vapours approach ideal gas behaviour
At higher densities, the behaviour may deviate substantially from the ideal gas equation of state
Two questions arises : 1) over what range of density will the ideal gas equation of state hold with accuracy ? 2) how much does an actual gas at a given pressure and temperature deviate from ideal gas behaviour ?
 The farther away Z is from unity, the more the gas deviates from idealgas behaviour
 The pressure or temperature of a substance is high or low relative to its critical temperature or pressure
 Gases
behave
differently
at
given
 Gases
behave
very
much
the
same
at
temperatures and pressures normalized with respect to their critical temperatures and pressures
 The normalization is done as : Reduced pressure, PR = P/Pcr Reduced temperature, TR = T/Tcr Reduced specific volume, vR = vactual RTcr/Pcr
 The Z factor for all gases is approximately the same at the same reduced pressure and
 The experimentally determined Z values are then plotted against PR and TR for several gases
 By curvefitting all the data, we obtain the generalized compressibility chart that can be used for all gases (Fig. A 15 in the textbook)
 The following observations can be made from the generalized compressibility chart:
o At very low pressures (PR < < 1), the gases behave as an ideal gas regardless of temperature o At high temperatures ( TR > 2 ), ideal gas behaviour can be assumed with good accuracy regardless of pressure (except when PR > > 1) o The deviation of a gas from idealgas behaviour is greatest in the vicinity of the critical point. In this region it is preferable to use the property tables
 The idealgas equation of state is vey simple, but its range of applicability is limited
P=
Ru T c A 1 3 (v + B ) 2 2 v vT v
2.8 SPECIFIC HEATS It takes different amounts of energy to raise the temperature of identical masses of different substances by one degree We need about 4.5 kJ of energy to raise the temperature of 1 kg of iron to from 20 to 30oC It takes about 41.8 kJ of energy to raise the temperature of 1 kg liquid water from 20 to 30oC It is desirable to have a property that will enable us to compare the energy storage capabilities of various substances This property is the specific heat The specific heat is defined as the energy required to raise the temperature of a unit mass of a substance by one degree In thermodynamics, we are interested in two kinds of specific heats: o Specific heat at constant volume, Cv o Specific heat at constant pressure, Cp
Cv is defined as :
u Cv = T v
Cp is defined as
h Cp = T p
These equations are property relations and are independent of the type of processes They are valid for any substance undergoing any process Like any other property, the specific heats depend on the state of a substance The only relevance Cv has to a constantvolume process is that Cv happens to be the energy transferred to a system during a constantvolume process per unit degree rise in temperature This is how the values of Cv are determined This is also how the name specific heat at constant volume originated
The same explanation applies to Cp Cv is related to the changes in internal energy. It is a measure of the variation of internal energy of a substance with temperature Cp is related to the changes in enthalpy. It is a measure of the variation of enthalpy of a substance with temperature A common unit for specific heats is kJ/kg.oC or kJ/kg.K
2.9 INTERNAL ENERGY, ENTHALPY, AND SPECIFIC HEATS OF IDEAL GASES The behaviour of an ideal gas is given by the relationship : Pv = RT It has been demonstrated mathematically and experimentally that for an ideal gas, the internal energy is a function of temperature only, i.e : u = u(T) Using the definition of enthalpy and the equation of state of an ideal gas h =u + Pv Pv = RT h = u + RT Since R is constant and u = u(T), it follows that the enthalpy of an ideal gas is a also a function of temperature only: h = h(T) Since u and h depend only on temperature for an ideal gas, the specific heats Cv and Cp also depend on temperature only Thus, the partial derivatives in the definition for Cv and Cp can be replaced by ordinary derivatives
The differential changes in the internal energy and enthalpy of an ideal gas is given by: du = Cv (T) dT dh = Cp (T) dT The change in internal energy or enthalpy for an ideal gas during a process from state 1 to state 2 is obtained by integrating the above equations There are 3 ways to determine the internal energy and enthalpy changes of ideal gases 1. By using the tabulated u and h data ( Table A17). This is the easiest and most accurate By using the Cv and Cp relations as a function of temperature and performing the integrations (Table A2c). This is inconvenient for hand calculations but desirable for computerized calculations By using average specific heats (Table A2b). This is very simple and convenient when property tables are not available. They are reasonably accurate if the temperature interval is not very large
2.
3.
Cv,av and Cp,av are evaluated from Table A2b at the average temperature (T1 + T2)/2
A special relationship between Cv and Cp for ideal gases can be obtained by differentiating the relation h = u + RT, which yields dh = du + RdT Replacing dh by CpdT and du by CvdT and dividing the results by dT, we obtain Cp = Cv + R This is an important relationship since it enables us to determine Cv from a knowledge of Cp and the gas constant R The specific heat ratio k is defined as k = Cp/Cv For incompressible substances (liquids and solids), both the are identical and denoted by C: Cv = Cp = C (refer Table A3) The u and h of incompressible substances are given by
u = C (T )dT C av (T2 T1 )
1
h = u + vP