CHAPTER

ChEng2205

2 Thermodynamics
Lecture Notes:3
Tesfa Nega
Faculty of Chemical and
Engineering, Bahir Dar Institute Properties of
of Technology, Bahir Dar,
Ethiopia Pure Substances

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Objective of the chapter

 The objectives of this chapter are to introduce property relations relevant

to engineering thermodynamics and provide several examples illustrating
the use of the closed system energy balance together with the property
relations.

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Learning outcomes
 When you complete your study of this chapter, you will be able to...
 understanding of key concepts . . . including phase and pure substance, state principle for simple compressible
systems, saturation temperature and saturation pressure, two-phase liquid-vapor mixture, quality, enthalpy, and
specific heats.
 apply the closed system energy balance with property data.
 sketch T–y, p–y, and phase diagrams, and locate states on these diagrams.
 retrieve property data from Tables A-1 through A-23.
 apply the ideal gas model for thermodynamic analysis, including determining when use of the model is
warranted.

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What is Pure Substances?

 A substance that has a fixed chemical composition throughout is called a
pure substance.
 A pure substance does not have to be of a single chemical element or
Nitrogen and gaseous air are pure
compound. A mixture of two or more phases of a pure substance is still a substances.
pure substance as long as the chemical composition of all phases is the
same..
 Air, for example, is a mixture of several gases, but it is often considered
to be a pure substance because it has a uniform chemical composition.
 However, a mixture of oil and water is not a pure substance. Since oil is
A mixture of liquid and gaseous
not soluble in water, it will collect on top of the water, forming two water is a pure substance, but a
chemically dissimilar regions. mixture of liquid and gaseous air
is not.

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Phases of A Pure Substance

 Phase refers to a quantity of matter that is homogeneous throughout in both chemical

composition physical structure and separated from the others by easily identifiable boundary
surfaces.. Homogeneity in physical structure means that the matter is all solid , or all liquid, or
all vapor (or equivalently all gas).
 The substances exist in different phases, e.g. at room temperature and pressure, copper is solid
mercury, is a liquid and nitrogen is a gas.
 Under different conditions, each may appear in a different phase.
 Even though 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.

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Phases of A Pure Substance

 Carbon, for example, 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.
 When studying phases or phase changes in thermodynamics, one does not need to be concerned
with the molecular structure and behavior of different phases.
 However, it is very helpful to have some understanding of the molecular phenomena involved in
each phase.
 Solid: Intermolecular bonds are strongest in solids, this is why molecules in solids are closely
packed together.

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Phases of A Pure Substance

Because of the small distances between molecules in a solid, the attractive forces of

molecules on each other are large and keep the molecules at fixed positions.

In a solid, the attractive and repulsive forces between the molecules tend to

maintain them at relatively constant distances from each other

Solid

Liquid: intermediate intermolecular bonds

The molecular spacing in the liquid phase is not much different from that of

the solid phase, except the molecules are no longer at fixed positions relative to

each other and they can rotate and translate freely.

Liquid
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Phases of A Pure Substance

Gas: weak intermolecular bond

they are separated by relatively large distances

Molecules in the gas phase are at a considerably higher energy level

than they are in the liquid or solid phases.

Therefore, the gas must release a large amount of its energy before it
Gas
can condense or freeze.

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Phase-change Processes of Pure Substances

 There are many practical situations where two phases of a pure substances coexist in equilibrium. E.g. water exists as
a mixture of liquid and vapor in the boiler and etc.

 Consider a piston–cylinder device containing liquid water at 20°C and 1 atm pressure (state 1, Fig. a)

 Under these conditions, water exists in the liquid phase,  At this point water still a liquid, but any heat addition will cause some of

and it is called a compressed liquid, or a sub cooled liquid. the liquid to vaporize.

 As the temperature rises, the liquid water expands slightly,  That is, a phase change process from liquid to vapor is about to take place.
 A liquid about to vaporize is called saturated liquid.
and so its specific volume increases.

At 1 atm and 20°C, water exists in the liquid

phase (compressed liquid). At 1 atm pressure and 100°C, water exists as a liquid
that is ready to vaporize (saturated liquid).
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Phase-change Processes of Pure Substances

 Once boiling starts, the temperature stops rising until the
liquid is completely vaporized (it is a constant phase -  At this point, the entire cylinder is filled with vapor that

change process at p constant). is on the borderline of the liquid phase.

 During this process the only thing is change in volume.  Any heat loss from this vapor will cause some of the

 At this stage liquid and vapor phase coexist in vapor to condense (phase change from vapor to liquid).

equilibrium and it is called saturated liquid-vapor  The vapor that is about to condense is called a saturated

mixture. vapor.

As more heat is transferred, part of the saturated liquid vaporizes At 1 atm pressure, the temperature remains constant at 100°C
(saturated liquid– vapor mixture) until the last drop of liquid is vaporized (saturated vapor).

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Phase-change Processes of Pure Substances

 At this stage the phase-change process is completed, we back to a single-

phase region (vapor).
 Further transfer of heat will result 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
superheated vapor.

As more heat is transferred, the temperature of the vapor starts

to rise (superheated vapor).

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Phase-change Processes of Pure Substances

 If the entire process between state 1 and 5 described in the figure is reversed by cooling the water while

maintaining the pressure at the same value, the water will go back to state 1, retracing the same path, and

in so doing, the amount of heat released will exactly match the amount of heat added during the heating

process.

T-v diagram for the heating

s
process of water at constant
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Saturation Temperature and Saturation Pressure

 Water boils at 100°C at 1 atm pressure.” The only reason water started boiling at

100°C was because we held the pressure constant at 1 atm (101.325 kPa)

 If the pressure inside the cylinder were raised to 500 kPa by adding weights on top

of the piston, water would start boiling at 151.8°C.

 That is, the temperature at which water starts boiling depends on the pressure;

therefore, if the pressure is fixed, so is the boiling temperature.

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Saturation Temperature and Saturation Pressure

 Saturation is defined as a condition in which a mixture of vapor and liquid can
exist together at a given temperature and pressure.

 Saturation pressure is the pressure at which the liquid and vapor phases are in
equilibrium at a given temperature

 At a given pressure, the temperature at which a pure substance changes

phase is called the saturation temperature Tsat.

 For a pure substance there is a definite relationship between saturation pressure and saturation
temperature. The higher the pressure, the higher the saturation temperature

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Saturation
During a phase-change process, pressure and temperature are obviously dependent properties, there is
a definite relation between them, that is, Psat = f(Tsat).
The graphical representation of this relationship between temperature and pressure at saturated
conditions is called the vapor pressure curve

 Tsat increases with Psat. Thus, a substance at higher pressures boils at

higher temperatures. In the kitchen, higher boiling temperatures mean
shorter cooking times and energy savings.
 A beef stew, for example, may take 1 to 2 h to cook in a regular pan that
operates at 1 atm pressure, but only 20 min in a pressure cooker operating at
3 atm absolute pressure (corresponding boiling temperature: 134°C).

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Saturated and Sub-cooled Liquids

 If a substance exists as a liquid at the saturation

temperature and pressure, it is called a 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

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Saturated and Superheated Vapors

 If a substance exists entirely as vapor at saturation
temperature, it is called saturated vapor.

 When the vapor is at a temperature greater than the saturation

temperature, it is said to exist as superheated vapor.

 The pressure and temperature of superheated vapor are independent

properties, since the temperature may increase while the pressure
remains constant

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Latent Heat
 Latent heat: The amount of energy absorbed or released during a phase-change process.

 Latent heat of fusion: The amount of energy absorbed during melting. It is

equivalent to the amount of energy released during freezing.

 Latent heat of vaporization: The amount of energy absorbed during vaporization

and it is equivalent to the energy released during condensation.
 At 1 atm pressure, the latent heat of fusion of water is 333.7 kJ/kg and the latent
heat of vaporization is 2256.5 kJ/kg.

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Property Diagrams For Phase- Change Process

 The variations of properties
during phase-change processes As the pressure is increased further, this
are best studied and saturation line continues to shrink, as
understood with the help of shown in Fig, and it becomes a point
property diagrams such as the when the pressure reaches 22.06 MPa
T-v, P-v, and P-T diagrams for for the case of water
pure substances.

This point is called the critical point,

and it is defined as the point at which
the saturated liquid and saturated
vapor states are identical.

T-v diagram of constant-pressure phase-change processes of a pure

substance at various pressures (numerical values are for water).
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Property Diagrams For Phase- Change Process

 The temperature, pressure, and specific volume of a substance at the critical point are called, respectively, the
critical temperature Tcr, critical pressure Pcr, and critical specific volume vcr. The critical-point properties of
water are Pcr = 22.06 MPa, Tcr = 373.95°C, and vcr = 0.003106 m3/kg.

At pressures above the critical pressure, there is not a distinct phase-change

process . Instead, the specific volume of the substance continually increases, and at
all times there is only one phase present.

Above the critical state, there is no line that separates the compressed liquid
region and the superheated vapor region.

However, substance as superheated vapor at temperatures above the critical

temperature and as compressed liquid at temperatures below the critical
At supercritical pressures (P > Pcr), there is temperature
no distinct phase-change (boiling) process.

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Property Diagram:The T-V Diagram

• Saturated liquid line: The saturated liquid states connected by a line

• Saturated vapor line:The saturated vapor states connected by a line

• These two lines meet at the critical point, forming a dome

• Compressed liquid region: All the compressed liquid states are located
in the region to the left of the saturated liquid line

• Superheated vapor region: All the superheated vapor states are located to the
right of the saturated vapor line

• Saturated liquid–vapor mixture region (wet region):All the states that involve
both phases in equilibrium are located under the dome

T-v diagram of a pure substance.

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Property Diagram:The P-v Diagram

The general shape of the P-v diagram of a pure substance is very much like the
T-v diagram, but the T = constant lines on this diagram have a downward trend

Water at this state exists as a compressed liquid.

Now the weights on top of the piston are removed
one by one so that the pressure inside the cylinder
decreases gradually.

The pressure in a piston–cylinder device can be

P-v diagram of a pure substance. reduced by reducing the weight of the piston.
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Property Diagram: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.

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Important Definition
o Critical point - the temperature and pressure above which there is
no distinction between the liquid and vapor phases.

o Triple point - the temperature and pressure at which all three

phases can exist in equilibrium.

o Sublimation - change of phase from solid to vapor.

o Vaporization - change of phase from liquid to vapor.

o Condensation - change of phase from vapor to liquid.

o Fusion or melting - change of phase from solid to liquid.

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Property Table

 For most substances, the relationships among thermodynamic properties are too complex

to be expressed by simple equations.

 Therefore, properties are frequently presented in the form of tables.

 Some thermodynamic 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.

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Property Table

 If you have 2 properties, you can find the others using the thermodynamic property tables.

 E.g. If you have pressure and temperature for steam, you can find it’s specific volume, enthalpy,

internal energy, and entropy.

 There are separate property tables for saturated mixtures, subcooled liquids, superheated vapors, and

ideal gases.

 Thermodynamic property tables can be found in the back of your textbook or various places online.

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Property Table

 For example if the pressure and specific volume are specified, three questions are asked; to
determine whether or not a substance is a saturated mixture for the given pressure.

 If the answer to the first question is yes, the state is in the compressed liquid region,
Is v  vf
and the compressed liquid table is used to find the properties. (or using saturation
temperature table)

 If the answer to the second question is yes, the state is in the saturation region, and
Is v f  v  vg
either the saturation temperature table or the saturation pressure table is used.

 If the answer to the third question is yes, the state is in the superheated region and Is vg  v
the superheated table is used.
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Property Table
Temperature Table

 Use the temperature table for when you

are given the temperature of a saturated
mixture
 Use the temperature and the quality to
determine the other properties

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Property Table
Pressure Table

 Use the pressure table for when you are

given the pressure of a saturated mixture
 Like the temperature table, use the
pressure and the quality to determine the
other properties

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Property Table
Superheated Gas Tables

 Used for temperatures higher than the

saturation temperature at a given pressure.
 Any two properties allow you to find all
other properties at that state

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Property Table
Subcooled Liquid Tables

 Used for temperatures lower than the

saturation temperature at a given pressure
 Any two properties allow you to find all other
properties at that state.

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Property Table: Interpolation

 Interpolation allows you to find values that are in between what the table provides

 The interpolation factor is consistent throughout the table for each individual state and is
v  vl
given by: a
vh  vl
 where v is the actual (given) property value, vl is the lower value on the chart, and vh is the

higher value on the chart.

 Other properties are found by:

v  vl  a (vh  vl )
u  ul  a (uh  ul )
h  hl  a ( h h  h l )
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Property Table

Examples: Saturated liquid and saturated vapor states of water on T-v and P-v diagrams.

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Enthalpy—A Combination Property

 A person looking at the tables will notice two new properties: enthalpy h and

entropy s.

 The combination u + Pv is frequently encountered in the analysis of control

volumes.

The product pressure  volume has energy units.

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Saturated Liquid–Vapor Mixture

The relative amounts of liquid and vapor phases in a saturated mixture are
specified by the quality x.

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Quality

 When a substance exists as part liquid and part vapor at saturation conditions, its quality (x) is defined
as the ratio of the mass of the vapor to the total mass of both vapor and liquid.

 The quality is zero for the saturated liquid and one for the saturated vapor (0 ≤ x ≤ 1)

 Quality has significance for saturated mixtures only.

 It has no meaning in the compressed liquid or superheated vapor regions

 For example, if the mass of vapor is 0.2 g and the mass of the liquid is 0.8 g, then the quality is
0.2 or 20%.

masssaturated vapor mg
x  
masstotal m f  mg
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Quality

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:

Quality is related to the

horizontal distances on P-v
and T-v diagrams.
The v value of a saturated liquid–
vapor mixture lies between the vf and vg
values at the specified T or P

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Superheated Vapor
In the region to the right of the saturated
Compared to saturated vapor, superheated
vapor line and at temperatures above the
critical point temperature, a substance vapor is characterized by
exists as superheated vapor.
In this region, temperature and pressure
are independent properties.

At a specified P,
superheated vapor
exists at a higher h
than the saturated
vapor

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Compressed Liquid
The compressed liquid properties
depend on temperature much more Compressed liquid is characterized by
strongly than they do on pressure.
y  v, u, or h
A more accurate relation for h

At a given P and T, a
A compressed liquid pure substance will exist
may be approximated as a compressed
as a saturated liquid at liquid if
the given temperature.
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Reference State and Reference Values

 The values of u, h, and s cannot be measured directly, and they are calculated from measurable
properties using the relations between properties.
 However, those relations give the changes in properties, not the values of properties at specified
states.
 Therefore, we need to choose a convenient reference state and assign a value of zero for a convenient
property or properties at that state.
 The referance state for water is 0.01°C and for R-134a is -40°C in tables.
 Some properties may have negative values as a result of the reference state chosen.
 Sometimes different tables list different values for some properties at the same state as a result of
using a different reference state.
 However, In thermodynamics we are concerned with the changes in properties, and the reference
state chosen is of no consequence in calculations.

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Reference State and Reference Values

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Example 2.1
Determine the saturated pressure, specific volume, internal energy
and enthalpy for saturated water vapor at 45 oC and 50oC.

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Example 2.2
Determine the saturated pressure, specific volume, internal energy
and enthalpy for saturated water vapor at 47 ⁰ C .

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Solution:
 Extract data from steam table

T Psat v u h
45 9.5953 15.251 2436.1 2582.4
47 Psat v u h
50 12.352 12.026 2442.7 2591.3

 Interpolation for Psat

Psat  9.5953 47  45

12.352  9.5953 50  45 Interpolation Scheme for Psat
Psat @ 47  10.698 kPa

 Do the same principal to

others!!!!
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Reading assignment
 The Ideal-gas Equation of State
 Compressibility Factor—a Measure of Deviation
From Ideal-gas Behavior
 Other Equations of State

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THANK YOU..

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