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ME-121 Thermodynamics - I

BS Mechanical Engineering – 2nd Semester


Credit hours – 3+0

Lecture – 3
Properties of a Pure Substance

Course Instructor: Manzar Masud


Email Id: m.masud.hscl@gmail.com
Office Address: Room # 13, POFIT Building
Department of Mechanical Engineering,
Wah Engineering College
University of Wah
Pure Substances
Substances having fixed chemical composition throughout
What sort of substances can have this characteristic
Single component Pure O2, He, H2O, CO2 etc
elements or compounds
Can a mixture of Yes as long as they have fixed
various pure substances composition throughout
be pure substances
Can a mixture of phases Yes as long as the two or
of pure substances be more phases have fixed
pure substances chemical composition
✓ 
Liquid water and ice Liquid air and gaseous air
Pure Substances
Examples A pure substance does not have to be of a single
chemical element or compound, however. A mixture of
various chemical elements or compounds also qualifies
as a pure substance as long as the mixture is
homogeneous. 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

A mixture of liquid air and gaseous air, however, is not


a pure substance since the composition of liquid air is
different from the composition of gaseous air, and thus
the mixture is no longer chemically homogeneous. This
is due to different components in air condensing at
different temperatures at a specified pressure.
Pure Substances
Substances exist in different phases
A phase
•Has a distinct molecular arrangement
• that is homogeneous throughout and
• separated from the others
• by easily identifiable boundary surfaces
Molecular Characteristics of Solids
• Intermolecular bonds are strongest in solids and weakest in gases
• Molecules/atoms in solids are arranged in a 3D pattern (lattice) that is repeated
throughout
• Molecules/atoms in solids are kept in fixed positions due to large attractive
forces
• Molecules/atoms in solids can vibrate only
Pure Substances
• The vibrational velocities depend on temperature
• At sufficiently high temperatures the vibrational velocities may overcome the
strong attractive forces
• This leads to the start of melting phenomenon
• Solids gets converted to liquids
Molecular characteristics of liquids
• Have the same order of molecular spacing as those of solids, generally increases
with temp (H2O exception)
• Except that molecules/atoms can rotate and translate freely
• In terms of Intermolecular forces; gases < liquids < solids
• At sufficiently high temperatures, intermolecular spacing increases to such an
extent that the molecules do not feel the intermolecular cohesive forces ➔
vaporization
Pure Substances
Molecular characteristics of gases
• Molecules are far apart from each other
• No molecular order or pattern
• Molecules move about randomly,
• Continuously colliding with each other and the walls of the container
• At low densities, the intermolecular forces are very small, and collisions are the
only mode of interaction between the molecules
• Molecules in the gas phase are at a considerably higher energy level than they
are in the liquid or solid phases
Energygas Energyliqids or solids
• Gas must release a large amount of its energy before it can condense or freeze
Pure Substances
Phase Change Processes of Pure Substances
Compressed Liquid and Saturated Liquid:
Consider a piston–cylinder device containing liquid water at 20oC
and 1 atm pressure (state 1, Fig. 3–5). Under these conditions,
water exists in the liquid phase, and it is called a compressed
liquid, or a subcooled liquid, meaning that it is not about to
vaporize.
Heat is now transferred to the water until its temperature rises to,
say, 40oC. As the temperature rises, the liquid water expands
slightly, and so its specific volume increases. To accommodate this
expansion, the piston moves up slightly.
As more heat is transferred, the temperature keeps rising until it
reaches 100oC (state 2, Fig. 3–6). 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. Therefore, state 2 is a saturated liquid state.
Phase Change Processes of Pure Substances
Saturated Vapor and Superheated Vapor:
Once boiling starts, the temperature stops rising until the liquid is
completely vaporized. That is, the temperature will remain constant
during the entire phase-change process if the pressure is held constant.
Midway about the vaporization line (state 3, Fig. 3–7), the cylinder
contains equal amounts of liquid and vapor. As we continue
transferring heat, the vaporization process continues until the last drop
of liquid is vaporized (state 4, Fig. 3–8).
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).
A vapor that is about to condense is called a saturated vapor.
Therefore, state 4 is a saturated vapor state. A substance at states
between 2 and 4 is referred to as a saturated liquid–vapor mixture
since the liquid and vapor phases coexist in equilibrium at these states.
Phase Change Processes of Pure Substances
Saturated Vapor and Superheated Vapor:
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 (Fig. 3–9).
At state 5, the temperature of the vapor is, let us say, 300oC; and if
we transfer some heat from the vapor, the temperature may drop
somewhat but no condensation will take place as long as the
temperature remains above 100oC (for P=1 atm). A vapor that is
not about to condense (i.e., not a saturated vapor) is called a
superheated vapor. Therefore, water at state 5 is a superheated
vapor.

The difference in saturated vapor and Superheated vapor is how


much energy they contain. Superheated vapor contains high
temperature, specific volume.
Phase Change Processes of Pure Substances
Superheated Superheated
vapours
T vapour
300oC 5
Saturated vapour Saturated Liquid-
vapour mixture
Saturated Liquid
2 3
100oC 4

70oC Saturated vapour

Saturated Liquid Subcooled Liquid /


20oC 1 Compressed liquid

v
Subcooled Liquid / T-v diagram at constant P = 1atm
Compressed liquid
Phase Change Processes of Pure Substances
Saturated Temperature and Saturated Pressure:

• At a given pressure, the temperature at which a pure substance changes phase is called
the saturation temperature Tsat.

• Likewise, at a given temperature, the pressure at which a pure substance changes phase
is called the saturation pressure Psat.

• At a pressure of 101.325 kPa, Tsat is 99.978C. Conversely, at a temperature of 99.97oC,
Psat is 101.325 kPa .
Pure Substances
Saturated Temperature and Saturated Pressure (Cont’d)

Whenever a liquid boils, it boils at a


certain temperature & pressure, these
fixed temperatures & pressures are
Saturation Temperature, Tsat

Saturation Pressure, Psat

T = 100 oC P = 1 atm
Water boils in a pan on stove
Pure Substances
Saturated Temperature and Saturated Pressure (Cont’d)
Tsat = f (Psat)
• Tsat increases with Psat.
• 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: 134oC).

A plot of Tsat versus Psat, is called a liquid–vapor saturation curve.


This curve is characteristic of all pure substances
Pure Substances
Saturated Temperature and Saturated Pressure (Cont’d)
• The atmospheric pressure, and thus the boiling temperature of water, decreases with elevation.
• Therefore, it takes longer to cook at higher altitudes than it does at sea level (unless a pressure
cooker is used). For example, the standard atmospheric pressure at an elevation of 2000 m is
79.50 kPa, which corresponds to a boiling temperature of 93.3oC as opposed to 100oC at sea
level (zero elevation).
• For each 1000 m increase in elevation, the boiling temperature drops by a little over 3oC.
Pure Substances
Large amount of energy is required to melt a solid or vaporize a liquid
Amount of energy absorbed or released during a phase-change process is
called the latent heat
Amount of energy absorbed during melting is the latent heat of fusion
= amount of energy released during freezing
Amount of energy absorbed during vaporization is the latent heat of
vaporization = energy released during condensation
Magnitudes of the latent heats depend on the temperature or pressure at
which the phase change occurs
Example: At 1 atm, the latent heat of fusion of water is 333.7 kJ/kg & the
latent heat of vaporization is 2256.5 kJ/kg.
Property Diagram and Phase Change Processes
The T-v diagram :

• The phase change process of water at 1 atm pressure was discussed in last section.

• Now, we repeat the process at different pressures to develop the T-v diagram.
Property Diagram and Phase Change Processes
The T-v diagram :
• Add weights on top of the piston until the
pressure inside the cylinder reaches 1 MPa.
• At this pressure, water has a somewhat smaller
specific volume than it does at 1 atm pressure.
• As heat is transferred to the water at this new
pressure, the process follows a path that looks
very much like the process path at 1 atm pressure
but there are some noticeable differences.
• First, water starts boiling at a much higher
temperature (179.9oC) at this pressure.
• Second, the specific volume of the saturated
liquid is larger and the specific volume of the
saturated vapor is smaller than the corresponding
values at 1 atm pressure.
• That is, the horizontal line that connects the
saturated liquid and saturated vapor states is much
shorter.
Property Diagram and Phase Change Processes
The T-v diagram :
• As the pressure is increased further, this
saturation line continues to shrink and it becomes
a point when the pressure reaches 22.06 MPa for
the case of water.
• 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.
• 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 = 373.95oC, and vcr = 0.003106
m3/kg.
• For helium, they are 0.23 MPa, 2267.85oC, and
0.01444 m3/kg.
Property Diagram and Phase Change Processes
The T-v diagram :
• 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.
• Eventually, it resembles a vapor, but we can never tell when
the change has occurred. Above the critical state, there is no
line that separates the compressed liquid region and the
superheated vapor region.
• However, it is customary to refer to the substance as
superheated vapor at temperatures above the critical
temperature and as compressed liquid at temperatures below
the critical temperature.
Property Diagram and Phase Change Processes
The T-v diagram :
• The saturated liquid states in Fig. 3–15 can be
connected by a line called the saturated liquid line,
and saturated vapor states in the same figure can be
connected by another line, called the saturated vapor
line.
• These two lines meet at the critical point, forming a
dome as shown in Figure.
• All the compressed liquid states are located in the
region to the left of the saturated liquid line, called the
compressed liquid region.
• All the superheated vapor states are located to the right
of the saturated vapor line, called the superheated
vapor region.
• In these two regions, the substance exists in a single
phase, a liquid or a vapor. All the states that involve
both phases in equilibrium are located under the dome,
called the saturated liquid–vapor mixture region, or
the wet region.
Property Diagram and Phase Change Processes
The P-v diagram :
• The general shape of the P-v diagram of a pure substance is very much like the T-v diagram.
• The T = constant lines on this diagram have a downward trend.
• Consider again a piston–cylinder device that contains liquid water at 1 MPa and 150oC.
• 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.
Property Diagram and Phase Change Processes
The P-v diagram :
• The water is allowed to exchange heat with the
surroundings so its temperature remains constant.
• As the pressure decreases, the volume of the
water increases slightly.
• When the pressure reaches the saturation-
pressure value at the specified temperature
(0.4762 MPa), the water starts to boil.
• During this vaporization process, both the
temperature and the pressure remain constant, but
the specific volume increases.
• Once the last drop of liquid is vaporized, further
reduction in pressure results in a further increase
in specific volume.
Property Diagram and Phase Change Processes
The P-v diagram :
• Notice that during the phase-change process, we
did not remove any weights. Doing so would
cause the pressure and therefore the temperature
to drop [since Tsat = f(Psat)], and the process
would no longer be isothermal.
• When the process is repeated for other
temperatures, similar paths are obtained for the
phase-change processes. Connecting the
saturated liquid and the saturated vapor states by
a curve, we obtain the P-v diagram of a pure
substance.
Property Diagram and Phase Change Processes
The P-v diagram :

Substances which contracts on freezing Substances which expands on freezing


Most substances contract during solidification i.e. Freezing process ; Others like water expand as they freeze.
Water expands upon freezing has importance in nature.
If water contracted on freezing as most other substances do, the ice formed would be heavier than liquid
water.
Property Diagram and Phase Change Processes
Triple Line: Under some conditions all three phases of a pure substance can coexist in
equilibrium. On P-v and T-v diagram , these triple phase states form a line called a triple line. The
states 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 0.01oC and
0.6117 kPa, respectively.

Sublimation :
There are two ways a substance can pass from the solid to vapor phase: either it melts first into a
liquid and subsequently evaporates, or it evaporates directly without melting first. The latter
occurs at pressures below the triple-point value, since a pure substance cannot exist in the liquid
phase at those pressures. Passing from the solid phase directly into the vapor phase is called
sublimation. For substances that have a triple-point pressure above the atmospheric pressure such
as solid CO2 (dry ice), sublimation is the only way to change from the solid to vapor phase at
atmospheric conditions.
Property Diagram and Phase Change Processes
Triple-point Temperature and
Pressures of various Pure
Substances:
Property Diagram and Phase Change Processes
The P-T diagram :
• This diagram is also called phase diagram since
all three phases are separated from each other by
the 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.
Property Diagram and Phase Change Processes
The P-v-T Surface
• Presentation as an Assignment 4 and Quiz 4 to be held on 17-4-2018
Enthalpy
1st Law of thermodynamics
Change in internal energy
of closed stationary

ΔU = Wnon-adiabatic + Q

Work done on the Amount of heat added to system


system
Constant
−W = − Fs  − W = − Fds = − PAds = − Pdv
ΔU = Q - W = Q - Pdv
1st Law in differential form dU = Q - W = Q - Pdv
Enthalpy
1st Law in differential form
dU = Q - W = Q – Pdv

0
Constant Volume
Thermodynamic Processes dU = Q – Pdv = Q

Constant Pressure
dU = Q – Pdv
Thermodynamic Processes
Repeatedly appears in various Q = dU + Pdv
thermodynamics relations
dH = dU + dPv
Defined as Enthalpy, An exact
differential. Hence, a state function h = u + pv
Property Tables
All diagrams studied are for pure substances but they
show the qualitative trends not the actual data
Actual data is presented graphical and tabular form
Graphical form is known as Mollier Diagrams
Tabular form is known as gas tables

Tabular form for water is known as steam tables

Steam Tables are of 2 types


1. Saturated Steam Tables
2. Superheated Steam Tables
1a : Saturated Liquid and Saturated Vapor States
• Properties of Saturated Liquid and
Saturated Vapor for water are listed in
Tables A-4 and A-5.
• In Table A-4, properties are listed under
temperature.
• In Table A-5, properties are listed under
pressure.
• Subscripts:
• f denoted properties of saturated liquid
• g denotes properties of saturated
vapor.
• fg denotes the difference between
saturated vapor and saturated liquid.
1a : Saturated Liquid and Saturated Vapor States
• For Example;
• vf = specific volume of saturated liquid
• vg = specific volume of saturated vapor
• vfg = difference between vg and vf (that is vfg = vg – vf)

• The quantity hfg is called the enthalpy of vaporization which represents


the amount of energy needed to vaporize a unit mass of saturated liquid
at given temperature and pressure.
1a : Saturated Liquid and Saturated Vapor States
Example 3-1
• A rigid tank contains 50 kg of saturated liquid water at 90oC.
Determine the pressure in the tank and volume of the tank.
Solution:
1a : Saturated Liquid and Saturated Vapor States
Example 3-2
• A piston cylinder device contains 0.06 m3 of saturated water vapor at
350 kPa pressure. Determine the temperature and mass of vapor inside
the cylinder?
Solution:
• Since the cylinder contains saturated vapor at 350
kPa, the temperature inside must be saturated
temperature at this pressure.
• From Table A-5 ; T = Tsat = 138.86 oC.
• Specific volume of saturated vapor at 350 kPa is
v = vg = 0.52422 m3/kg
• The mass of water vapor inside cylinder becomes:
• m = V / v = 0.114 kg
1a : Saturated Liquid and Saturated Vapor States
Example 3-3
• 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?
Solution:
1b : Saturated Liquid – vapor Mixture
• During vaporization process, a substance exists as part liquid and
part vapor, i.e. it is a mixture of saturated liquid and saturated
vapor.
• To analyze this mixture properly, proportions of the liquid and
vapor phases in the mixture is needed.
• So, we define a new property called the quality x
Mass of vapors in mixture mg
Quality = x = =
Total mass of mixture mt
𝒎𝒕𝒐𝒕𝒂𝒍 = 𝒎𝒍𝒊𝒒𝒖𝒊𝒅 + 𝒎𝒗𝒂𝒑𝒐𝒓 = 𝒎𝒇 + 𝒎𝒈
• The value of quality (x) is always between 0 and 1.
• The quality of system that consists of saturated liquid is 0 and of
saturated vapor is 1.
1b : Saturated Liquid – vapor Mixture
• The properties of the saturated liquid are the same whether it
exists alone or in mixture with saturated vapor.
• A saturated mixture can be treated as a combination of two
subsystems: the saturated liquid and the saturated vapor.
• However, the amount of mass for each phase is usually not
known.
• Therefore, it is often more convenient to imagine that the two
phases are mixed well, forming a homogeneous mixture
• Then the properties of this “mixture” will simply be the average
properties of the saturated liquid–vapor mixture under
consideration.
1b : Saturated Liquid – vapor Mixture
• The properties of the saturated liquid are the same whether it
exists alone or in mixture with saturated vapor.
• A saturated mixture can be treated as a combination of two
subsystems: the saturated liquid and the saturated vapor.
• However, the amount of mass for each phase is usually not
known.
• Therefore, it is often more convenient to imagine that the two
phases are mixed well, forming a homogeneous mixture
• Then the properties of this “mixture” will simply be the average
properties of the saturated liquid–vapor mixture under
consideration.
1b : Saturated Liquid – vapor Mixture
Mass of vapors in mixture mg
Quality = x = =
Total mass of mixture mt
Volume of vapors in mixture Vg v g
Void Fraction =  = = =
Total Volume of mixture Vt vt
Consider a tank containing a saturated liquid–vapour mixture
• The volume occupied by saturated liquid is Vf
• The volume occupied by saturated vapour is Vg
• The total volume V is the sum of the two
V = Vf + Vg mt = mf + mg
V = mv ➔ mtvavg = mf vf + mgvg➔ mtvavg = (mt - mg)vf + mgvg

mt  mg  mg
vavg =  1 −  vf + vg ➔ vavg = (1 - x)vf + xvg = vf + x vfg
mt  mt  mt
vfg = vg - vf
1b : Saturated Liquid – vapor Mixture
vavg = vf + x vfg ➔ x = (vavg–vf )/vfg

x=
( v avg − vf ) = AB
v fg AC

A state of 50 percent
lies in the middle of
this horizontal line.
1b : Saturated Liquid – vapor Mixture
➢ By changing the volume or specific volume with any other extensive or specific
intensive property one can get the corresponding two phase mixture property

vavg = vf + x vfg uavg = uf + x ufg


havg = hf + x hfg savg = sf + x sfg
➢ General Equation becomes
yavg = yf + x yfg

yf ≤ yavg ≤ yfg
1b : Saturated Liquid – vapor Mixture
Example 3-4
• A rigid tank contains 10 kg of water at 90oC. If 8 kg of the water is in the liquid form and the
rest in the vapor form, determine (a) the pressure in the tank , (b) the volume of the tank.
Solution:
1b : Saturated Liquid – vapor Mixture
Example 3-5
• A 80 L vessel contains 4 kg of refrigerant – 134a at a pressure of 160 kPa. Determine (a) the
temperature, (b) the quality, (c) the enthalpy of the refrigerant (d) volume occupied by the
vapor phase?
Solution:
1b : Saturated Liquid – vapor Mixture
Example 3-5
• A 80 L vessel contains 4 kg of refrigerant – 134a at a pressure of 160 kPa. Determine (a) the
temperature, (b) the quality, (c) the enthalpy of the refrigerant (d) volume occupied by the
vapor phase?
Solution:
2 : Superheated Vapor
• 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.
• Since the superheated region is a
single-phase region (vapor phase
only), temperature and pressure are no
longer dependent properties and they
can conveniently be used as the two
independent properties in the tables.
• The format of the superheated vapor
tables is illustrated in Figure.
2 : Superheated Vapor
• The saturation temperature is given in parentheses following the pressure value.
• 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)
2 : Superheated Vapor
Example 3-6
• Determine the internal energy of water at 200 kPa and 300 oC.
Solution:
At 200 kPa, the saturation temperature is 120.21 oC. Since T > Tsat, the
water is in the superheated vapor region.
Then the internal energy at the given temperature and pressure is
determined from the superheated vapor table to be 2808.8 kJ/kg.
2 : Superheated Vapor
Example 3-7
• Determine the temperature of water at a state of P = 0.5 Mpa and h =
2890 J/kg.
Solution:
At 0.5 MPa, the enthalpy of saturated water vapor is hg 5 2748.1 kJ/kg.
Since h > hg,, we again have superheated vapor.
Under 0.5 MPa in Table A–6 we read
3 : Compressed Liquid
• Variation of properties of compressed liquid with pressure is very mild. Increasing the pressure
100 times often causes properties to change less than 1 percent.
• In the absence of compressed liquid data, a general approximation is to treat compressed liquid
as saturated liquid at the given temperature. This is because the compressed liquid properties
depend on temperature much more strongly than they do on pressure.
𝑦 ≅ 𝑦𝑓 @ 𝑇 where y is v , u or h.
• Of these three properties, the property whose value is most sensitive to variations in the
pressure is the enthalpy h.
• Although the above approximation results in negligible error in v and u, the error in h may
reach undesirable levels.
• However, the error in h at low to moderate pressures and temperatures can be reduced
significantly by evaluating it from
ℎ ≅ ℎ𝑓 @ 𝑇 + 𝑣𝑓 @ 𝑇 (𝑃 − 𝑃𝑠𝑎𝑡 @ 𝑇 )
• Note, however, that the approximation in above equation does not yield any significant
improvement at moderate to high temperatures and pressures, and it may even backfire and
result in greater error due to overcorrection at very high temperatures and pressures.
3 : Compressed Liquid
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)
3 : Compressed Liquid
Reference State and Reference Values
Determine the missing properties and the phase descriptions in
the following table for water:
Sr, T, P, u, x Phase
No oC kPa kJ/kg quality description
1 120.21 200 1719.26 0.6 Saturated mixture
2 125 232.23 1600 0.535 Saturated mixture
3 395.2 1000 2950 NIL Superheated vapours
4 75 500 313.9 NIL Compressed Water
Tables 5 172.94 850 731.0 0.0 Saturated Liquid
A-4 vavg = vf – x vfg uavg = uf – x ufg
A-5
A-6 havg = hf – x hfg savg = sf – x sfg
A-7
Equation of State
Any equation that relates the pressure, temperature, and
specific volume of a substance
Why we need the equations of state
Property tables
1. Provide very accurate information about the properties
2. Bulky
3. Vulnerable to typographical errors
An equation relating the properties of substances that are
sufficiently general and accurate would be more desirable
This led to the evolution of Equations of State
Equation of State
Simplest relations relating P, V or T
1. Boyles Law ➔PV = constantBL OR P 1/V
2. Charles Law ➔VT-1 = constantCL OR V T
3. Avogadros Law ➔Vn-1 = constantAL OR V n
4. Combines gas Law ➔PVT-1 = constantCGL OR V T
All these laws lead to a general law
The Ideal Gas Law ➔PV  nT
PV = nRuT ➔ Pv = RuT (where v = V/n)
Where Ru = universal gas constant independent of gas
Units of Ru depends on the units of P, V, n and T
Equation of State
What happens, if for same analysis, use mass of gas instead of moles
V = total volume
V
v = = molar volume PV = n Ru T = mRT
n
P v = RuT OR Pv = RT
V
v = = specific volume The molar mass M can simply be defined as
m
the mass of one mole (also called a gram-mole,
m = M n abbreviated gmol) of a substance in grams, or
M = Molar Mass PV = n Ru T  m R T the mass of one kmol (also called a kilogram-
mole, abbreviated kgmol) in kilograms.

Universal gas constant Specific gas constant,


independent of gas gas dependent
Equation of State
The molar mass M can simply be defined as the mass of one mole (also called a
gram-mole, abbreviated gmol) of a substance in grams, or the mass of one kmol
(also called a kilogram-mole, abbreviated kgmol) in kilograms.
When we say the molar mass of nitrogen is 28, it simply means the mass of 1 kmol of
nitrogen is 28 kg, or the mass of 1 lbmol of nitrogen is 28 lbm. That is, M = 28
kg/kmol
Equation of State
Individual Gas Constant - R
Gas Imperial Units SI Units Molecular Weight
(ft lb/slug oR) (J/kg K) (g/mole)
Argon, Ar 208 39.94
Acetylene 319 26
Ammonia 488 17
Carbon Dioxide 1130 188.9 44.01
Carbon Monoxide 297 28.01
Carbonic acid 189 44
Helium 12420 2077 4.003
Hydrogen 24660 4124 2.016
Methane 3099 518.3 16.04
Nitrogen 1775 296.8 28.02
Oxygen 1554 259.8 32
Propane 189 44.09
Sulfur dioxide 130 64.07
Air 1716 286.9 28.97
Water vapor 2760 461.5 18.02
Universal Gas Constant Ru
atm.cm3/(mol.K) : 82.0575 J/(kmol.K) : 8314.472
atm.ft3/(lbmol.K) : 1.31443 (kgf/cm2).l/(mol.K) : 0.084784
atm.ft3/(lbmol.oR) : 0.73024 kPa.cm3/(mol.K) : 8314.472
atm.l/(mol.K) : 0.08206 kWh/(lbmol.oR) : 0.000582
bar.cm3/(mol.K) : 83.14472 lbf.ft/(lbmol.oR) : 1545.349
bar.l/(mol.K) : 0.083145 mmHg.ft3/(lbmol.K) : 999
Btu/(lbmol.oR) : 1.9859 mmHg.ft3/(lbmol.oR) : 555
cal/(mol.K) : 1.9859 mmHg.l/(mol.K) : 62.364
erg/(mol.K) : 83144720 Pa.m3/(mol.K) : 8.314472
hp.h/(lbmol.oR) : 0.000781 psf.ft3/(lbmol.oR) : 1545.349
inHg.ft3/(lbmol.oR) : 21.85 psi.ft3/(lbmol.oR) : 10.73
J/(mol.K) : 8.314472 Torr.cm3/(mol.K) : 62364
kJ/(kmol.K) : 8.314472
Example
Is Water Vapor an Ideal Gas
Is Water Vapor an Ideal Gas
• The error involved in treating water vapor as an ideal gas is calculated and plotted
in Figure.
• It is clear from this figure that at pressures below 10 kPa, water vapor can be
treated as an ideal gas, regardless of its temperature, with negligible error (less
than 0.1 percent).
• At higher pressures, however, the ideal gas assumption yields unacceptable
errors, particularly in the vicinity of the critical point and the saturated vapor line
(over 100 percent).
• Therefore, in air-conditioning applications, the water vapor in the air can be
treated as an ideal gas with essentially no error since the pressure of the water
vapor is very low.
• In steam power plant applications, however, the pressures involved are usually
very high; therefore, ideal-gas relations should not be used.
Real Gases – Compressibility Factor
All real gases properties can
be approximated by the ideal
gas law if the %age error  1

Compressibility factor ‘Z’


A measure of deviation from
ideal-gas behaviour

Pv Pv PV PV
Z= = = =
RT RuT mRT nRuT

For other P-v-T conditions


either use more accurate
equation or use experimental
Water Vapor as an Ideal Gas
data from tables
Real Gases – Compressibility Factor

𝑅𝑇
𝑣𝑖𝑑𝑒𝑎𝑙 =
𝑃

The farther away Z is from unity,


the more the gas deviates from
ideal gas behaviour.
Real Gases – Compressibility Factor
• We have said that gases follow the ideal-gas equation closely at low pressures and
high temperatures.
• But what exactly constitutes low pressure or high temperature? Is -100oC a low
temperature? It definitely is for most substances but not for air.
• Air (or nitrogen) can be treated as an ideal gas at this temperature and
atmospheric pressure with an error under 1 percent. This is because nitrogen is
well over its critical temperature (-147oC) and away from the saturation region.
• At this temperature and pressure, however, most substances would exist in the
solid phase.
• Therefore, the pressure or temperature of a substance is high or low relative to its
critical temperature or pressure.
Real Gases – Compressibility Factor
Gases behave differently at a given temperature and pressure. However
same behaviour when T and P are normalized w.r.t their Tcr & Pcr

The Z factor for all gases is approximately the same at the same reduced
pressure and temperature. This is called principle of corresponding states.
Real Gases

1. At PR << 1, gases behaviour as an ideal gas regardless of temperature


2. At TR = 2 ideal-gas behaviour regardless of pressure except at PR  1
3. Deviation from ideal behaviour is greatest in vicinity of critical point
PV = n Ru T = mRT
P v = RuT OR Pv = RT
0.84
0.33
Table A-4
Saturated Water –
Temperature Table
Table A-4
Saturated Water –
Temperature Table
Table A-5
Saturated Water –
Pressure Table
Table A-5
Saturated Water –
Pressure Table
Table A-6
Superheated
Water
Table A-6
Superheated
Water
Table A-6
Superheated
Water
Table A-6
Superheated
Water
Table A-7
Compressed
Liquid Water
Table A-8
Saturated Ice -
Water Vapor