ADDIS ABABA SCIENCE AND TECHNOLOGY UNIVERSITY

COLLEGE OF ELECTRICAL ENGINEERING

MECHANICAL ENGINEERING DEPARTMENT
Engineering Thermodynamics
(EMEg3101)
CHAPTER- TWO
P R O P E R T I E S O F P U R E S U B S TA N C E S

Lecture
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lecture notes prepared by by
BonsaBonsa
R. R.
 Learning objectives
 By the end of this chapter you will be able to:
 Define pure substance and phase of a pure substance.
 Explain phase change process using property diagrams.
 Use steam table to get property values at different regions of phase change process.
 Differentiate ideal gases from real gases.
 Used ideal gas equation of state to determine unknown properties.
 Explain the advantages and disadvantages of ideal gas equation of state and other
equations of states.

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 What is pure substance?
 A substance that has a fixed chemical composition throughout is called a pure
substance. Example: Water, nitrogen, helium, and carbon dioxide.
 Chemical elements and compounds are pure substances.
 A mixture of various chemical elements or compounds also qualifies as a pure substance as long as
the mixture is homogeneous. Example: Air
 A mixture of two or more phases of a pure substance is still a pure substance as long as the
chemical composition of all phases is the same.

A mixture of liquid and gaseous water is a pure

substance, but a mixture of liquid and gaseous air
is not.
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Phases of a pure substance
 A phase is identified as having a distinct molecular arrangement that is homogeneous
throughout and separated from the others by easily identifiable boundary surfaces.
 The two phases of H2O in iced water represent a good example of this.
 There are three principal phases; solid, liquid, and gas.
 A substance may have several phases within a principal phase, each with a different
molecular structure.
 For example, Carbon, may exist as graphite or diamond in the solid phase.
 Helium has two liquid phases.
 Iron has three solid phases.
 Ice may exist at seven different phases at high pressures.

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Phase of a pure substance

Solids Liquids Gases

• Strong intermolecular bonds • weakest intermolecular forces

• Molecules closely packed and • groups of molecules move • No molecular order exist.
arranged in a lattice. about each other. • Collusion is the only mode of
• Molecules oscillate about • Intermolecular forces are interaction.
equilibrium position. weaker than solids but • Are relatively at higher energy
• Oscillation velocity increase with stronger than gases. level.
temperature.

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Phase change process
 There are many practical situations where two phases of a pure substance coexist in
equilibrium.
 Water exists as a mixture of liquid and vapor in the boiler and the condenser of a steam power
plant.
 The refrigerant turns from liquid to vapor in the freezer of a refrigerator.
 As a familiar substance, water is used to demonstrate the basic principles involved.
 Remember, however, that all pure substances exhibit the same general behavior.

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Compressed liquid / Subcooled liquid Phase change process
 Water exist in liquid form and when a
1
slight amount of heat is added, the water
wont vaporise.
 As the temperature rises, the liquid water
expands slightly, and so its specific volume
increases.
 As more heat is transferred, the
temperature keeps rising until it reaches
100°C
At 1 atm and 20°C, water exists in the
liquid phase (compressed liquid)
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Saturated Liquid Phase change process
2
 At this point water is still a liquid, but
any heat addition will cause some of the
liquid to vaporize.
 That is, a phase-change process from
liquid to vapor is about to take place.
 A liquid that is about to vaporize is
called a saturated liquid.

At 1 atm pressure and 100°C, water exists as a

liquid that is ready to vaporize (saturated liquid).

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Saturated Liquid-Vapor mixture Phase change process
3
 Once boiling starts, the temperature
stops rising until the liquid is
completely vaporized.
 During a boiling process, the only
change we will observe is a large
increase in the volume and a steady
decline in the liquid level as a result of
more liquid turning to vapor.
As more heat is transferred, part of the
saturated liquid vaporizes (saturated liquid–
vapor mixture)
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Saturated Vapor Phase change process
4  At this point all the liquid is converted
in to vapor at atmospheric pressure and
100°C.
 If a slight heat is lost then the vapor will
start condensing.
 A vapor that is about to condense is
called a saturated vapor.

At 1 atm pressure, the temperature remains

constant at 100°C until the last drop of liquid is
vaporized (saturated vapor)
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Superheated Vapor Phase change process
5
 Once the phase-change process is
completed, we are back to a single
phase region again (this time vapor),
and further transfer of heat results in an
increase in both the temperature and
the specific volume.
 A vapor that is not about to condense
(i.e., not a saturated vapor) is called a
As more heat is transferred, the temperature of superheated vapor.
the vapor starts to rise (superheated vapor)

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 Fig.T-v diagram of a constant pressure heating process of water
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 latent heat
 It is the amount of energy absorbed or released during a phase-change process.
 latent heat of fusion: energy absorbed during melting / energy released during
freezing.
 latent heat of vaporization: energy absorbed during vaporization /energy released
during condensation.
 The magnitudes of the latent heats depend on the temperature or pressure at which the phase
change occurs.

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 Saturation temperature and saturation pressure
 The temperature at which water starts boiling depends on the pressure; therefore, if the
pressure is fixed, so is the boiling temperature.
 At a given pressure, the temperature at which a pure substance changes phase is called the
saturation temperature Tsat.
 at a given temperature, the pressure at which a pure substance changes phase is called the
saturation pressure Psat.
 At Pressure 101.325 Kpa, Tsat is 100oC.
 If the pressure inside the cylinder were raised to 500 kPa by adding weights on top of the
piston, water would start boiling at 151.88oC

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Saturation temperature and saturation pressure
 Tsat increases with Psat. Thus, a substance at higher
pressures boils at higher temperatures.

The liquid–vapor saturation curve of a pure substance

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 Consequences of Tsat and Psat Dependence
 vacuum cooling

• Based on reducing the pressure of the sealed

cooling chamber to the saturation pressure at the
desired low temperature and evaporating some
water from the products to be cooled.
• Its expensive and fast cooling which is more
desirable for products with larger surface area to
mass ratio like lettuce and spinach.

Vacuum freezing

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Property diagrams for phase-change processes
 The variations of properties during phase-change processes are best studied and
understood with the help of property diagrams.
The T-v Diagram
• Adding weight on top of the piston rises the
pressure which is accompanied by :
• State 1: smaller specific volume
• State 2: elevated saturation temperature
and increased specific volume

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 The T-v Diagram
 State 3: shorter line connecting the saturated states.
 State 4: lesser specific volume.
 State 5: lesser specific volume for the same temperature value.
 As we keep increasing the pressure the line connecting the saturated liquid and saturated
vapor shorten and become a point; which is called critical point.
 At critical point the saturated liquid and saturated vapor are identical.
 At critical point we have critical properties; such as critical pressure, critical temperature,
critical specific volume etc…
 Pcr =5 22.06 MPa, Tcr =5 373.958oC, and vcr =5 0.003106 m3/kg

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 The T-v Diagram
 At supercritical pressures (P > Pcr), there is no distinct
phase-change (boiling) process.
 there is no line that separates the compressed liquid region
and the superheated vapor region.
 Its considered as superheated vapor at temperatures above
critical temperature and compressed liquid at
temperatures lower than critical temperature.
 A saturation dome is formed connecting all the saturated
liquid and saturated vapor points .

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The T-v Diagram

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 The P-v Diagram
 Its much like that of T-v diagram except the constant
temperature line has a downward trend.
 Consider a compressed liquid at 1 MPa and 150℃.
 As mass is removed gradually the pressure reduced.
 To keep the temperature constant, the water exchange heat with
the environment.
 When the pressure reaches 0.4762MPa, the water starts
vaporizing. At this point we stop removing weight.
 During vaporization both pressure and temperature are
constant.

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The P-v Diagram

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 The P-v Diagram
 It can be extended to include the solid phase.
 under some conditions all three phases of a pure substance coexist in equilibrium.
 On P-v or T-v diagrams, these triple-phase states form a line called the triple line.
 The states on the triple line of a substance have the same pressure and temperature but
different specific volumes.
 The triple line appears as a point on the P-T diagrams and, therefore, is often called the triple
point.
 For water, the triple-point temperature and pressure are 0.01°C and 0.6117 kPa,
respectively.

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 The P-v Diagram

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 The P-v Diagram
 At triple point all the three phases coexist in equilibrium.
 No substance can exist in the liquid phase in stable equilibrium at
 𝑃 < 𝑃𝑡𝑝 for all substances and
 𝑇 < 𝑇𝑡𝑝 for substance that contract during freeing.
 substances at high pressures can exist in the liquid phase at temperatures below
the triple-point temperature.
 water cannot exist in liquid form in equilibrium at atmospheric pressure at temperatures
below 0°C, but it can exist as a liquid at −20°C at 200 MPa pressure.
 Passing from the solid phase directly into the vapor phase is called sublimation.
 occurs at pressures below the triple point value, since a pure substance cannot exist in the
liquid phase at those pressures.

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The P-T Diagram
 This diagram is often called the phase diagram since all three phases are separated from each
other by three lines.
 The sublimation line separates the solid and vapor regions.
 The vaporization line separates the liquid and vapor regions and
 The melting (or fusion) line separates the solid and liquid regions.
 These three lines meet at the triple point, where all three phases coexist in equilibrium.
 The vaporization line ends at the critical point because no distinction can be made between liquid
and vapor phases above the critical point.
 Substances that expand and contract on freezing differ only in the melting line on the P-T diagram.

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 The P-v-T Surface
 we can represent the P-v-T behavior of a substance as a surface in space.
 Here T and v 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. All states along the path of a
quasi-equilibrium process lie on the P-v-T surface since such a process must pass through
equilibrium states.
 All the two-dimensional diagrams we have discussed so far are merely projections of this
three-dimensional surface onto the appropriate planes

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 P-v-T surface of a substance that P-v-T surface of a substance that
contracts on freezing. expands on freezing (like water).

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Property tables
 the relationships among thermodynamic properties are too complex to be expressed by
simple equations.
 Some properties can be measured and others can be calculated and found by some relations.
 The results of these measurements and calculations are presented in tables in a convenient
format.
 the steam tables are used to demonstrate the use of thermodynamic property tables.
 Before we get into the discussion of property tables, we define a new property called
enthalpy.

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 Enthalpy
 It’s a combination property, most often in analysis of
certain types of process (in power generation and
refrigeration) we encounter with internal energy (u) and
Pv.
 Grouping them simplifies the equation and the
summation of the two is called enthalpy (h).

ℎ = 𝑢 + 𝑃𝑣 (kJ/kg)

H = 𝑈 + 𝑃𝑉 (kJ)

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Saturated Liquid and Saturated Vapor States
 The subscript f is used to denote properties of a
saturated liquid and the subscript g to denote the
properties of saturated vapor.
 The subscript commonly used is fg, which
denotes the difference between the saturated
vapor and saturated liquid values of the same
property.
 𝑣𝑓 = specific volume of saturated liquid
 𝑣𝑔 = specific volume of saturated vapor
 𝑣𝑓𝑔 = 𝑣𝑔 − 𝑣𝑓
 ℎ𝑓𝑔 represent the enthalpy of vaporization /
latent heat of vaporization. (zero at the
critical point)

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 Saturated Liquid and Saturated Vapor States
 Examples
1. A rigid tank contains 50 kg of saturated liquid water at 90°C. Determine the
pressure in the tank and the volume of the tank.
2. A mass of 200 g of saturated liquid water is completely vaporized at a constant
pressure of 100 kPa. Determine (a) the volume change and (b) the amount of
energy transferred to the water.

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 Saturated Liquid–Vapor Mixture
 we need to know the proportions of the liquid and vapor phases in the mixture.
 This is done by defining a new property called the quality x as the ratio of the mass
of vapor to the total mass of the mixture:
𝑚𝑣𝑎𝑝𝑜𝑟
 𝑥= where; 𝑚𝑡𝑜𝑡𝑎𝑙 = 𝑚𝑣𝑎𝑝𝑜𝑟 + 𝑚𝑙𝑖𝑞𝑢𝑖𝑑
𝑚𝑡𝑜𝑡𝑎𝑙
 Quality has significance for saturated mixtures only.
 Its value is between 0 (saturated liquid) and 1 (saturated vapor).
 A saturated mixture can be treated as a combination of two subsystems.

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 Saturated Liquid–Vapor Mixture
 Consider a tank that contains a saturated liquid–vapor mixture. The volume
occupied by saturated liquid is Vf , and the volume occupied by saturated vapor is
Vg. The total volume V is the sum of the two:

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 Saturated Liquid–Vapor Mixture
 For others also

More generally
Where y can be; u , h, or v

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 Saturated Liquid–Vapor Mixture
 Example:
1. A rigid tank contains 10 kg of water at 90°C. If 8 kg of the water is in the liquid form and the
rest is in the vapor form, determine (a) the pressure in the tank and (b) the volume of the tank.
2. A 0.08 m3 vessel contains 4 kg of water at a pressure of 150 kPa. Determine (a) the
temperature, (b) the quality, (c) the enthalpy of the water, and (d) the volume occupied by the
vapor phase.

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 Superheated Vapor
 We have superheated region to the right side of saturated vapor line and also above critical
temperature.
 Since we have single phase temperature and pressure are independent.
 Compered to saturated vapor, this region is characterised by:
 Lower pressures (P < Psat at a given T )
 Higher temperatures (T > Tsat at a given P)
 Higher specific volumes (v > vg at a given P or T)
 Higher internal energies (u > ug at a given P or T )
 Higher enthalpies (h > hg at a given P or T)

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 Superheated Vapor
 Example :
1. Determine the temperature of water at a state of P = 0.5 MPa and h = 2890
kJ/kg.

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 Compressed Liquid
 Compressed liquid tables are not as commonly available.
 They are very much like the format of the superheated vapor tables.
 Variation of properties of compressed liquid with pressure is very mild.
 In the absence of compressed liquid data, a general approximation is to treat compressed liquid
as saturated liquid at the given temperature.
 𝑦 ≅ 𝑦𝑓@𝑇 where y is v, h, u
 Form the three; v, u and h, enthalpy (h) is sensitive to pressure

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 Compressed Liquid
 Instead of taking hf for low to moderate pressures and temperatures,
 ℎ ≅ ℎ𝑓@𝑇 + 𝑣@𝑇 𝑃 − 𝑃𝑠𝑎𝑡@𝑇
 In general, a compressed liquid is characterized by;
 Higher pressures (P > Psat at a given T )
 Lower temperatures (T < Tsat at a given P)
 Lower specific volumes (v < vf at a given P or T)
 Lower internal energies (u < uf at a given P or T )
 Lower enthalpies (h < hf at a given P or T )

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 Compressed Liquid
 Example:
1. Determine the internal energy of compressed liquid water at 80°C and 5 MPa,
using (a) data from the compressed liquid table and (b) saturated liquid data.
What is the error involved in the second case?

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 Example
Determine the missing properties and the phase descriptions in the following table for water:

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 The ideal gas equation of state
 Property tables give accurate information about properties of a system but they are bulky
and prone to typographic error.
 It is desirable to have some relation among properties which is general and accurate.
 Any equation that relates the pressure, temperature, and specific volume of a substance is
called an equation of state.
 The simplest and best-known equation of state for substances in the gas phase is the ideal-
gas equation of state.
 This equation predicts the P-v-T behavior of a gas quite accurately within some properly
selected region.

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 The ideal gas equation of state
 The ideal gas equation of state is given by;
𝑃𝑣 = 𝑅𝑇
 Where : P is the absolute pressure in (KPa)
o v is the specific volume in (m3/kg)
o T is absolute temperature in (K)
o R is a gas constant in (kJ/kg.K)
 R is different for different gases and its obtained by:
𝑅𝑢
𝑅=
𝑀
Where Ru is the universal gas constant and M is the molar mass

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 The ideal gas equation of state
 molar mass M can simply be defined as the mass of one mole.
 For example; when we say the molar mass of nitrogen is 28, it simply means the mass of 1 kmol of
nitrogen is 28 kg; or 1gmol of nitrogen is 28 g.
 The mass of a system is equal to the product of its molar mass M and the mole number N;
 𝑚 = 𝑁𝑀 (Kg)
 The ideal-gas equation of state can be written in several different forms:
 𝑃𝑉 = 𝑚𝑅𝑇
 𝑃𝑉 = 𝑁𝑅𝑢 𝑇
 𝑃 𝑣ҧ = 𝑅𝑢 𝑇

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 The ideal gas equation of state
 For a fixed mass writing the ideal gas equation twice at two states :
𝑃1 𝑉1 𝑃2 𝑉2
 =
𝑇1 𝑇2
 An ideal gas is an imaginary substance that obeys the ideal gas relation.
 Real gases behave as ideal gas at lower density, i.e at lower pressure and higher temperature.
 Dense gases such as water vapor in steam power plants and refrigerant vapor in refrigerators,
however, should not be treated as ideal gases, instead property tables are used.

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 At lower pressures below 10 kPa water vapour
can be treated as an ideal gas regardless of
temperature with negligible error.

Is Water Vapor an Ideal Gas?

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 The ideal gas equation of state
 Example:
1. The gage pressure of an automobile tire is measured to be 210 kPa before a trip
and 220 kPa after the trip at a location where the atmospheric pressure is 95 kPa.
Assuming the volume of the tire remains constant and the air temperature before
the trip is 25°C, determine air temperature in the tire after the trip.

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 Compressibility factor Z
 Gases deviate from ideal-gas behavior significantly at states near the saturation
region and the critical point.
 This deviation from ideal-gas behavior at a given temperature and pressure can
accurately be accounted for by the introduction of a correction factor called the
compressibility factor Z.
𝑃𝑣
𝑍= ------------------------ 𝑃𝑣 = 𝑍𝑅𝑇
𝑅𝑇
 It can be also expressed as
𝑣𝑎𝑐𝑡𝑢𝑎𝑙 𝑅𝑇
𝑍= ; where is ; 𝑣𝑖𝑑𝑒𝑎𝑙 =
𝑣𝑖𝑑𝑒𝑎𝑙 𝑃

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 Compressibility factor Z
 Gases behave very much the same at temperatures and pressures normalized with
respect to their critical temperatures and pressures called reduced temperature and
reduced pressure respectively.
𝑇
 Reduced temperature : 𝑇𝑅 =
𝑇𝑐𝑟
𝑃
 Reduced pressure: 𝑃𝑅 =
𝑃𝑐𝑟
 The Z factor for all gases is approximately the same at the same reduced pressure
and temperature. This is called the principle of corresponding states.

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 Compressibility factor Z
 The following observations can be made from the generalized compressibility
chart.
 At very low pressures (PR << 1), gases behave as ideal gases regardless of temperature.
 At high temperatures (TR > 2), ideal-gas behavior can be assumed with good accuracy
regardless of pressure (except when PR >> 1)
 The deviation of a gas from ideal-gas behavior is greatest in the vicinity of the critical
point.

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 Compressibility factor Z
 When T and v or P and v are given instead of T and P the generalized compressibility chart
can still be used to determine the third property (pseudo-reduced specific volume vR)
𝑣𝑎𝑐𝑡𝑢𝑎𝑙
 𝑣𝑅 = 𝑅𝑇𝑐𝑟
ൗ𝑃𝑐𝑟

 Lines of constant vR are also added to the compressibility charts, and this enables one to
determine T or P.

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  Example:
1. Determine the specific volume of refrigerant-134a at 1 MPa and 50°C, using (a)
the ideal-gas equation of state and (b) the generalized compressibility chart.
Compare the values obtained to the actual value of 0.021796 m3/kg and
determine the error involved in each case.

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 Other Equations of State
 Ideal gas equation of state is simple but with limited rage of application.
 It is desirable to have equations of state that represent the P-v-T behavior of
substances accurately over a larger region with no limitations.
 Such equations are naturally more complicated; several has been proposed.

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 van der Waals Equation of State
 Van der Waals equation improves the ideal gas equation by considering the effects
of intermolecular attraction forces and volume occupied by the molecules
themselves.
𝑎
 𝑃+ 𝑣 − 𝑏 = 𝑅𝑇
𝑣2
 The two constants a and b are determined at critical point of the substance, where the
𝑎
intermolecular force is accounted by the term 2 and that of volume occupied by
𝑣
molecules by 𝑏
 As the pressure increases, the volume occupied by the molecules becomes an
increasingly significant part of the total volume

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 van der Waals Equation of State
 The two constants are determined from the critical isotherm line; which is
horizontal at critical point, so

 Performing the differentiation and eliminating 𝑣𝑐𝑟

 Its desirable to express the constants a and b over wide range instead of
single point.

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 Beattie-Bridgeman Equation of State
 equation of state based on five experimentally determined constants. It is
expressed as

 Where

 The Beattie-Bridgeman equation is known to be reasonably accurate for densities up to

about 0.8ρcr.
 The constants appearing in this equation are given in Table 3–4 for various substances.

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 Beattie-Bridgeman Equation of State

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 Benedict-Webb-Rubin Equation of State
 Extended version of Beattie-Bridgeman, have 8 constants.

 The values of the constants appearing in this equation are given in Table 3–4.
 This equation can handle substances at densities up to about 2.5ρcr.

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 Virial Equation of State
 The equation of state of a substance can also be expressed in a series form

 coefficients a(T), b(T), c(T), and so on, that are functions of temperature alone are
called virial coefficients.
 These coefficients can be determined experimentally or theoretically from statistical
mechanics.
 As pressure approaches zero, all the viral coefficients vanish and we remain with the
ideal gas equation.

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  van der Waals: 2 constants. Accurate over a limited range.
 Beattie-Bridgeman: 5 constants. Accurate for ρ ≤ 0.8ρcr
 Benedict-Webb-Rubin: 8 constants. Accurate for ρ ≤ 2.5ρcr
 Strobridge: 16 constants. More suitable for computer calculations.
 Virial: may vary. Accuracy depends on the number of terms used.

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  Example:
1. Predict the pressure of nitrogen gas at T = 175 K and v = 0.00375 m3 /kg on the basis
of (a) the ideal-gas equation of state, (b) the van der Waals equation of state, (c) the
Beattie-Bridgeman equation of state, and (d) the Benedict-Webb-Rubin equation of
state. Compare the values obtained to the experimentally determined value of 10,000
kPa.

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 End of chapter

70 lecture notes prepared by Bonsa R. 10/27/2024