Chapter Two: Properties of Pure Substances

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Chapter Two

Properties of Pure Substances


Engineering Thermodynamics I
What is Pure Substances?
 A substance that has a fixed
chemical composition
throughout is called a pure
substance.
Pure substance may exist in
different phases, but the chemical
compositions is the same.
 water made up of two atoms
of hydrogen and one atom
oxygen. It will have the same
composition when in ice,
liquid and vapor forms.

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Phases of A Pure Substance

 The substances exist in different phases, e.g. at


room temperature and pressure, copper is solid
and mercury is a liquid.

 It can exist in different phases under various


condition.

 There are 3 Principal phases


• solid
• Liquid
• gas
Each with different molecular structures. 3
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.
 Solid: strong intermolecular bond
 Liquid: intermediate intermolecular bonds
 Gas: weak intermolecular bond

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Solid Liquid Gas
• Consider the piston-cylinder device containing liquid
water at 20oC and 1atm.

 Under these conditions, water exists in


the liquid phase, and it is called a
compressed liquid, or a sub cooled
liquid.
 As the temperature rises, the liquid
water expands slightly, and so its
specific volume increases.
• At this point water 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 about to vaporize is
called saturated liquid.
• Once boiling starts, the temperature
stops rising until the liquid is
completely vaporized (it is a phase
change process at p-constant).
• During this process the only thing
that is changing is the volume.
• At this stage liquid and vapor phase
coexist in equilibrium and it is called
saturated liquid-vapor mixture.
• At this point, the entire cylinder is
filled with vapor that is on the
borderline of the liquid phase.
• Any heat loss from this vapor will
cause some of the vapor to condense
(phase change from vapor to liquid).
• The vapor that is about to condense
is called a saturated vapor.
• At this stage the phase-change process
is completed, we get another 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.
This constant
pressure heating
process can be
illustrated as:

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Property Diagram

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Saturation

 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
 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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The graphical representation of this relationship between temperature
and pressure at saturated conditions is called the vapor pressure curve

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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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P-V-T diagram

substance that contracts on freezing. substance that expands on freezing.


T

Top view
v

P
P
view
v
P P
T vi
ew

v T
The T-V diagram

• Experimental result tells us, as the pressure is increased


further, the saturation line of the process will continue to get
shorter and it will become a point.

• This point is called the critical point of the substance and it


may be defined as the point at which the saturated liquid
saturated vapor states are identical.

• At pressures above the critical pressure, there is not a distinct


phase-change process.

• We can never tell when the change has occurred.


The T-V diagram
The P-V diagram
The P-T diagram
Thermodynamic Property Table
 Thermodynamic properties of substance are usually given in tabular form to
facilitate calculation.

 Among them saturated, superheated steam and compressed liquid are the
most frequently used properties.

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Saturated liquid-vapor mixture
 During a vaporization process, a substance exists as part
liquid and part vapor. 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)

 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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Moisture Content

 The moisture content of a


substance is the opposite of its
quality. Moisture is defined as the
ratio of the mass of the liquid to
the total mass of both liquid and
vapor
mg mg
 Recall the definition of quality x x 
m m f  mg
 Then
mf m  mg
  1 x
m m

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Quality

Mixture of liquid and vapor


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 Take specific volume as an example. The specific volume of the
saturated mixture becomes

v  (1  x )v f  xv g
 The form that is most often used

v  v f  x (v g  v f )

u  u f  xu fg
h  h f  xh fg
s  s f  xs fg
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Saturated Liquid and Saturated Vapor States
• The properties of saturated liquid and saturated vapor for water
are listed in Thermodynamics tables.
Superheated steam table
• In the region to the right of the saturated vapor line and at
temperatures above the critical point temperature, a substance
exists as superheated vapor.
• Compared to saturated vapor, superheated vapor is
characterized 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)
Compressed liquid table
• Compressed liquid tables are not as commonly available.
• In the absence of compressed liquid data, a general
approximation is to treat compressed liquid as saturated liquid
at the given temperature.

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)
How to Choose the Right Table
• Given the temperature or pressure and one other property from
the group v, u, h, and s, the following procedure is used.
• For example if the pressure and specific volume are specified,
three questions are asked: For the given pressure,

 If the answer to the first question is yes, the state is in the


compressed liquid region.
 If the answer to the second question is yes, the state is in the
saturation region.
 If the answer to the third question is yes, the state is in the
superheated region
Example 2.1
Determine the saturated pressure, specific volume, internal energy
and enthalpy for saturated water vapor at 45oC and 50oC.

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

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Example 2.2
Determine the saturated pressure, specific volume, internal energy
and enthalpy for saturated water vapor at 47⁰ C .

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Example 2.2
Determine the saturated pressure, specific volume, internal energy
and enthalpy for saturated water vapor at 47⁰ 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 for other values

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Exercises

1. Fill in the blank using R-134a

2. Determine the saturated temperature, saturated pressure and


enthalpy for water at specific volume of saturated vapor at
10.02 m3/kg .

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Example 2.3 Is v  v f ? No
Determine the enthalpy of 1.5 Is v f  v  v g ? Yes
kg of water contained in a Is v g  v ? No
volume of 1.2 m3 at 200 kPa.
 Find the quality
v  v f  x (v g  v f )
Solution:
v  vf
 Specific volume for water x
vg  v f
Volume 12. m3 m3 0.8  0.001061
v   0.8 
mass 15
. kg kg 0.8858  0.001061
 From steam table:  0.903 (What does this mean?)
 The enthalpy
v f  0.001061 m3
kg
h  h f  x h fg
vg  0.8858 m3
kg  504.7  (0.903)(2201.6)
kJ
 2492.7
kg 39
Example 2.4
Determine the internal energy of refrigerant-134a at a temperature
of 0C and a quality of 60%.

Solution:
 From table :  The internal energy of R 134a
at given condition:
kJ
u f  51.63 u  u f  x (u g  u f )
kg
kJ  51.63  (0.6)(230.16  51.63)
u g  230.16
kg kJ
 158.75
kg

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Example 2.5

Consider the closed, rigid container of


water as shown. The pressure is 700 mg, Vg
kPa, the mass of the saturated liquid is
Sat. Vapor
1.78 kg, and the mass of the saturated
vapor is 0.22 kg. Heat is added to the
water until the pressure increases to 8 mf, Vf
MPa. Find the final temperature, Sat. Liquid

enthalpy, and internal energy of the


water

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Solution:
 Theoretically: State 2:

v2  v1  Information :
P2  8 MPa v2  0.031 mkg
3

 The quality before pressure


increased (state 1).  From table A-5:
mg 1 m3
x1  v f,2  0.001384
m f 1  mg 1 kg vg 2  v2
m3
0.22 kg v g,2  0.02352
  0.11 kg
(1.78  0.22) kg
 Since that it is in superheated
 Specific volume at state 1 region, use table A-6:
v1  v f 1  x1 (vg1  v f 1 ) T2  361.8o C
 0.001108  (0.11)(0.2728  0.001108) h2  3024 kJ
kg
m3 u2  2776 kJ
 0.031 kg
kg
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Exercises
1. Four kg of water is placed in an enclosed volume of 1m3.
Heat is added until the temperature is 150°C. Find ( a )
the pressure, ( b )the mass of vapor, and ( c ) the volume
of the vapor.

2. A piston-cylinder device contains 0.1 m3 of liquid water and


0.9 m3 of water vapor in equilibrium at 800 kPa. Heat is
transferred at constant pressure until the temperature reaches
350°C.
(a) what is the initial temperature of the water,
(b) determine the total mass of the water,
(c) calculate the final volume, and
(d) show the process on a P-v diagram with respect to
saturation lines.

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Exercises
3. For a specific volume of 0.2 m3/kg, find the quality of steam
if the absolute pressure is (a) 40 kPa and ( b ) 630 kPa. What
is the temperature of each case?

4. Water is contained in a rigid vessel of 5 m3 at a quality of


0.8 and a pressure of 2 MPa. If the a pressure is reduced to
400 kPa by cooling the vessel, find the final mass of vapor
mg and mass of liquid mf.

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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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Equation of State

The relationship among the state variables, temperature,


pressure, and specific volume is called the equation of state.

There are several equations of state, some simple and others


very complex.

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.
• Based on our experience in chemistry and physics we recall that the
combination of Boyle’s and Charles’ laws for gases at low pressure
result in the equation of state for the ideal gas as

T 
P  R   Pv  RT PV  mRT  nMRT
v
• The constant of proportionality R is called the gas constant.
• The gas constant R is different for each gas and is determined from

Ru
R  (kJ / kg.K )
M

• Where Ru is the universal gas constant and M is the molar mass

(also called molecular weight) of the gas. The constant Ru is the


same for all substances, and its value is 8.314KJ/Kmol K

m  nM
• The ideal-gas equation of state can be written in several different
forms

V  mv  PV  mRT
mR  ( MN ) R  NRu  PV  NRuT
V  Nv  Pv  RuT
• the properties of an ideal gas at two different states are related to each
other by
PV PV
1 1
 2 2
T1 T2

• Air, nitrogen, oxygen, hydrogen, helium, argon etc can be treated as


ideal gases.
 The amount of energy needed to raise the
temperature of a unit of mass of a substance by one
degree is called the specific heat at constant volume
Cv for a constant-volume process and the specific
heat at constant pressure Cp for a constant pressure
process. They are defined as

 u   h 
C v    and C P   
 T  v  T  P
 Using the definition of enthalpy (h = u + Pv) and writing the
differential of enthalpy, the relationship between the specific
heats for ideal gases is
h  u  Pv
dh  du  RdT
CP dt  CV dt  RdT
CP  CV  R

 The specific heat ratio, k is defined as

CP
k
Cv
 For ideal gases u, h, Cv, and Cp are functions of temperature alone.
The Δu and Δh of ideal gases can be expressed as

u  u 2  u1  C v (T2  T1 )

h  h2  h1  C P (T2  T1 )
Compressibility factor (measure of deviation from ideal gas)

• The ideal-gas equation is very simple and thus very convenient


to use.
• 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 defined as

• For real gases Z can be greater than or less than unity.

PV  ZRT
P T
PR  TR 
Pcr Tcr
Example
1. Determine the mass of the air in a room whose
dimensions are 4 m X 5 m X 6 m at 100 kPa and 25°C.

(R=0.287 kJ/kg. K)
2.A piston–cylinder device initially contains 0.2 kg of
steam at 200 kPa and 300°C. Now, the steam is cooled
at constant pressure until it is at 150°C. Determine the
volume change of the cylinder during this process
using the ideal gas equation and compare the result to
the actual value.
Solution:
3. An ideal gas is contained in given
a closed assembly with an
state 1
initial pressure and temperature
of 220 kPa and 700C P1  220 kPa
respectively. If the volume of T1  70  273K  343 K
the system is increased 1.5 state 2
times and the temperature drops
to 150C, determine the final T2  15  273  288 K
pressure of the gas. V2  1.5V1
 From ideal-gas law:
PV PV
1 1
 2 2
T1 T2
V1  288 
P2   
1.5V1  343 
220  10 3

 123.15 kPa
59
4. An automobile tire with a
volume of 0.6 m3 is inflated to a
gage pressure of 200 kPa.
Calculate the mass of air in the
tire if the temperature is 20°C.
Solution:  From ideal-gas law:
given
PV
state 1 m
RT
P  200  100 kPa

300  103 N
m3  0.6m 
2

T  20  273K  293 K
287 kgNm.K  293K 
 2.14 kg

60
Problems
1. The pressure in an automobile tire depends on the temperature of the air
in the tire. When the air temperature is 25°C, the pressure gage reads 210
kPa. If the volume of the tire is 0.025 m3, determine the pressure rise in
the tire when the air temperature in the tire rises to 50°C. Also, determine
the amount of air that must be bled off to restore pressure to its original
value at this temperature. Assume the atmospheric pressure is 100 kPa.
[ 26 kPa, 0.007
kg]

2. A 1-m3 tank containing air at 25°C and 500 kPa is connected through a
valve to another tank containing 5 kg of air at 35°C and 200 kPa. Now
the valve is opened, and the entire system is allowed to reach thermal
equilibrium with the surroundings, which are at 20°C. Determine the
volume of the second tank and the final equilibrium pressure of air.
[ 2.21 m3, 284.1 kPa]

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3. A 1 m3 rigid tank has propane at 100 kPa, 300 K and connected by a
valve to another tank of 0.5 m3 with propane at 250 kPa, 400 K. The
valve is opened and the two tanks come to a uniform state at 325 K.
What is the final pressure?
[ 139.9
kPa]

4. A cylindrical gas tank 1 m long, inside diameter of 20 cm, is


evacuated and then filled with carbon dioxide gas at 25°C. To what
pressure should it be charged if there should be 1.2 kg of carbon
dioxide?
[ 2152
kPa]

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