CHAPTER 2 PROPERTIES OF PURE SUBSTANCES

2.1 Pure Substance - A substance that has a fixed chemical

composition throughout (ex: water, nitrogen, helium, and CO2 )

- 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

2.2 Vapour-Liquid-Solid Phase Equilibrium

- There are 3 principal phases for a working fluid i.e solid, liquid and gas

- Let us carry out an experiment

- Consider as a system 1 kg of water contained in the piston-cylinder 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,

additional heat transfer results in a change of phase, as indicated in Figure 2.1(b)

- 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

- This relationship is in the form of a curve known as the vapor-pressure curve

Pressure
Vapor pressure curve

Temperature

FIGURE 2.1 Constant-pressure change from liquid to vapor phase for a substance

FIGURE 2.2 Temperature-Volume diagram for water

- 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

pressure for the given temperature

- 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%

- Quality is an intensive property and is given the symbol x

X =

mvapour mvapour + mliquid

- 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

saturated-liquid

and

saturated-vapour

states have the same pressure and the same temperature, but are definitely not the same state

- In a saturation state, pressure and temperature are not independent properties

- 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

- Gases are highly superheated vapours

We can also sketch the pressure versus temperature diagram for a substance such as water. This diagram is shown in Figure 2.3

Liquid phase Pressure Vapour phase

Solid Phase

Triple point

Temperature

Figure 2.3 Pressure-Temperature Diagram

- 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

2.3 Independent substance -

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

saturated-liquid

and

saturated-vapour

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

- The state of air, which is a mixture of gases of definite composition, is determined by

specifying two properties as long as it remains in the gaseous phase

- In this regard, air can be considered as a pure substance

2.4 Property Tables - Some thermodynamics properties can be

measured easily, but others cannot and are calculated by using the relations between them and measurable properties

- The

results

of

these

measurements

and

calculations are presented in tables in a convenient format

- The steam tables will be used to demonstrate the use of thermodynamic property tables

- Property tables of other substances are used in the same manner

- For

each

substance,

the

thermodynamic

properties are listed in more than one table

- 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

- Examples of macroscopic forms of energy are kinetic and potential energies

- 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 a combination of the properties U + PV.

- 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 A-4(Temperature table) and A-5(Pressure table)

Both tables give the same information

The subscript f is used to denote properties of a saturated liquid

The subscript g is used to denote the properties of saturated vapour

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
-

Saturated Liquid-Vapour Mixture

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

mg = mass of vapour mf = mass of liquid m = total mass = mf + mg

Consider a container that contains a saturated liquid-vapour 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

v = (1 x)vf + xvg vfg = vg - vf v = vf + xvfg

similarly,

h = hf + xhfg u = uf + xufg s = sf + xsfg

- Quality has significance for saturated mixtures only

- It has no meaning in the compressed liquid or superheated regions

- Its value is between 0 and 1

- The quality of a system that consists of saturated liquid is 0 or 0 percent

- The quality of a system that consists of saturated vapour is 1 or 100 percent

- 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

- Superheated region is a single-phase region

- Temperature and pressure can be used as two independent properties to determine a state - Table A-6 in the textbook lists superheated properties for water the

2.4.4

Compressed Liquid

- Compressed

liquid

tables

are

not

commonly available

- Table A-7 is the only compressed liquid table in the textbook

- Compressed liquid properties depend on temperature much more strongly than they do on pressure

- In the absence of compressed liquid data, a general approximation is to treat

compressed liquid as saturated liquid at the given temperature - Thus, y = yf@T where y is v, u, or h

2.4.5

Reference state and reference value

- The values of u, h and s cannot be measured directly

- They are calculated from measurable properties using the relations between properties

- These relations give the changes

in

properties, not the values of properties at specified states

- We need to choose a reference state and assign a value of zero for a

property/properties at that state

- 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 P-v-T Surface

- The

state

of is

simple by

compressible any two

substance

fixed

independent, intensive properties

- Once the two appropriate properties are fixed, all the other properties become dependent properties

- Any

equation

with

two

independent

variables in the form z = z(x,y) represents a surface in space

- Thus,

we

can

represent

the

P-v-T

behaviour of a substance as a surface in space

- T

and

may

be

viewed

as

the

independent variables (the base) and P as the dependent variable (the height)

- All the points on the surface represent equilibrium states

- Single-phase regions appear as curved surfaces

- Two-phase

regions

are

surfaces

perpendicular to the P-T plane

- All the 2-D diagrams are the projections of this 3-D surface onto the appropriate planes

- A P-v diagram is a projection of the P-v-T surface on the P-v plane

Figure 2.4 P-v-T surfaces

2.6 Equation of State - Property tables provide very accurate

information about properties

- 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 best-known equations of state for substances in the gas phase is the ideal-gas equation of state

- This equation predicts the P-v-T 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 P-v-T behaviour of gases at low density is closely given by the ideal-gas 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

Dividing equation by the molecular weight, M, we obtain: Pv = RT M M

v = V/N v/M = V/NM

NM = jisim = m

v/M = V/m = v
R = Ru/M R is the gas constant and is different for each gas

Equation 2.1 then becomes Pv = RT (2.2)

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 ?

To answer both questions, lets introduce the compressibility factor, Z Z = Pv RT or Pv = ZRT

- For an ideal gas, Z = 1

- The farther away Z is from unity, the more the gas deviates from ideal-gas behaviour

- The pressure or temperature of a substance is high or low relative to its critical temperature or pressure

- Gases

behave

differently

at

given

temperature and pressure

- 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

temperature. This is known as the principle of corresponding states

- The experimentally determined Z values are then plotted against PR and TR for several gases

- By curve-fitting 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 ideal-gas behaviour is greatest in the vicinity of the critical point. In this region it is preferable to use the property tables

2.7 Other Equations of State

- The ideal-gas equation of state is vey simple, but its range of applicability is limited

- It is desirable to have equations of state that is accurate over a larger region

- Such equations are naturally more complicated

- Examples of such equations are:

Equation Van der Waals Beattie-Bridgeman Benedict-Webb-Rubin Virial Equation Formula ( P + a v 2 (v b ) = RT

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 constant-volume 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 A-17). This is the easiest and most accurate By using the Cv and Cp relations as a function of temperature and performing the integrations (Table A-2c). 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.

The u and h of ideal gases are expressed as

2

u = u2 u1 = Cv (T)dT Cv,av(T2 T1)

1

h = h2 h1 = Cp (T)dT Cp,av(T2 T1)

1

Cv,av and Cp,av are evaluated from Table A-2b 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 A-3) The u and h of incompressible substances are given by

u = C (T )dT C av (T2 T1 )
1

h = u + vP