BMEE203L- Engineering Thermodynamics

Module 2 : Properties of Pure

Substances
Dr. Feroskhan M
Associate Professor
SMEC
Module 2 – Properties of Pure Substances

Topic Date
Phases of a pure substance, phase change process
22/08/2022
of pure substances

property diagrams for phase change processes, 24/08/2022

vapour property tables
26/08/2022
Problems
Ideal gas equation of state, real gases - Van der
29/08/2022
Waals equation of state

compressibility factor, Benedict -Webb Rubin 02/09/2022

equation.
Problems
03/09/2022

MEE1003 - Engineering Thermodynamics

 Pure Substance
• 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 compound
• A mixture of various chemical elements or
compounds is a pure substance as long as the
mixture is homogeneous, e.g. Air
• A mixture of oil and water is not a pure substance
as oil is not soluble in water
3
 Pure Substance…
• 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, e.g. Mixture of ice and water
• A mixture of liquid air and gaseous air is not
pure substance as the compositions are
different

4
 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, e.g. iced
water
• Substances are present in three phases-Solid,
Liquid and Gas (vapour)

5
 Phases of a Pure Substance…
• The molecules in a solid are arranged in 3-D
pattern
• Due to the small distances between the
molecules in a solid, the attractive forces of
molecules on each other are large and keep the
molecules in fixed positions
• The molecular spacing in the liquid phase is
similar to that in solids except that the molecules
are no longer at fixed positions relative to each
other and can rotate and translate freely
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 Phases of a Pure Substance…
• In the gas phase, the molecules are far apart
from each other and molecular order is
nonexistent
• Gas molecules move about random,
continually colliding with each other and the
walls of the container
• Molecules in the gas phase are at a
considerably higher energy level than they are
in the liquid and solid phases

7
 Phase Change Processes
• Phase change processes take place in practical
situations
• Water exists as liquid and vapour in a boiler
and a condenser
• The refrigerant turns from liquid to vapour in
a refrigerator
• Here, water is used to explain the process but
the principles are equally applicable to other
pure substances
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Phase Change Processes in a Pure
Substance

State 1: Compressed Liquid

State 2: Saturated Liquid
State 3: Saturated liquid +
Vapour
State 4: Saturated Vapour
State 5: Superheated Vapour9
 Definitions
• Compressed or Sub-Cooled liquid means that it is
not about to vapourize
• Saturated Liquid is a liquid that is about to
vapourize
• Saturated Vapour is a vapour that is about to
condense
• Saturated Liquid-Vapour Mixture is a condition
where liquid and vapour coexist in equilibrium
• Superheated Vapour is a vapour that is not about
to condense

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Definitions…

11
 Definitions…
• Saturation Temperature (Tsat) is the
temperature (at a given pressure) at which a
pure substance changes phase
• Saturation Pressure (Psat) is the pressure (at a
given temperature) at which a pure substance
changes phase
• Latent Heat of Vaporization is the amount of
energy absorbed during evaporation

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Liquid-Vapour Saturation Curve
Tsat=f(Psat)

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T-V Diagram

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 Critical Point
• Critical Point is defined as the point at which
the saturated liquid and saturated vapour
states are identical
• For water, Pcr=22.06 Mpa
• Tcr=373.95 0C

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T-V Diagram…

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 Liquid-Vapour Mixture

Mass of Vapour mvapour mvapour

Quality  Dryness Fraction, x   
Total Mass mtotal mliquid  mvapour

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Properties of Liquid-Vapour Mixture

v  1  x v f  xv g
u  1  x u f  xu g F (for fluid)
h  1  x h f  xhg
=Liquid
G (for gas)
s  1  x s f  xs g =Vapour

y  1  x  y f  xy g

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Characteristics of Superheated vapour
• Compared to saturated vapour, superheated
vapour is characterized by
Lower Pressures P  Psat at a given T 
Higher Temperatures T  Tsat at a given P 
Higher Specific Volumes v  v g at a given P or T 
Higher internal energies u  u g at a given P or T 
Higher Enthalpies h  h g at a given P or T 

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 Characteristics of Compressed Liquid
• 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  v f at a given P or T 
Lower internal energies u  u f at a given P or T 
Lower Enthalpies h  h f at a given P or T 
• However, the properties of compressed liquid are
not much different from the corresponding
saturation liquid values
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 Problem Table 1
T, 0C P, kPa V, m3/kg Phase Description
50 4.16
200 Saturated Vapour
250 400
110 600

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 Problem Table 2
T, 0C P, kPa h, kJ/kg x Phase
Description
200 0.7
140 1800
950 0.0
80 500
800 3162.2

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 Problem 1
A rigid tank with a volume of 2.5 m3 contains 15
kg of saturated liquid-vapour of water at 75 0C.
Now the water is slowly heated. Determine the
temperature at which the liquid in the tank is
completely vaporized. Also, show the process on
a T-v diagram with respect to saturation lines.

Ans: 187 0C

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 Problem 2
Superheated water vapour at 1.4 MPa and 250
0C is allowed to cool at constant volume until

the temperature drops to 120 0C. At the final

state, determine (a) the pressure, (b) the quality,
and (c) the enthalpy. Also, show the process on
a T-v diagram with respect to saturation lines.

Ans: (a) 198.7 kPa, (b) 0.1825, (c) 905.7 kJ/kg

24
 Problem 3
A sample of steam from a boiler drum at 3 MPa
is put through a throttling calorimeter in which
the pressure and temperature are found to be
0.1 MPa and 120 0C respectively. Find the quality
of the sample taken from the boiler.

Ans: 0.951

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 Problem 4
Steam enters a turbine operating at steady state
with a mass flow rate of 4600 kg/h. The turbine
develops a power output of 1000 kW. At the inlet,
the pressure is 60 bar, the temperature is 400 C,
and the velocity is 10 m/s. At the exit, the pressure
is 0.1 bar, the quality is 0.9 (90%), and the velocity
is 50 m/s. Calculate the rate of heat transfer
between the turbine and surroundings, in kW.

Ans: 61.3 kW
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 Ideal Gas
• The equation Pv=RT is known as the Ideal Gas
Equation or the Ideal Gas Equation of State
• A gas which obeys this equation is called an
Ideal Gas
• P is absolute pressure, T is absolute
temperature and v is specific volume
Ru kJ
R
M kg - K
Ru  Universal Gas Constant
M  Molar Mass or Molecular Weight
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Universal Gas Constant
 kJ
8.31447 kmol - K

8.31447 J
 mol - K
Ru   3
8.31447 kPa - m
 kmol - K
 3
0.0831447 bar - m
 kmol - K

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 Molar Mass and Mole
• Molar Mass is the mass of one mole of a
substance in grams, or the mass of one kmol
in kilograms
• Number of Moles (n) is the ratio of the mass
(m) to the molecular weight (M)

m
n
M

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 Other Forms of the Ideal Gas Equation
PV  mRT
PV  nRuT For a gas undergoing a process1  2,
PV  RuT the Ideal Gas Equation can be used to write
Where P1V1 P2 V2

P  Absolute Pressure, Pa T1 T2

V  Volume, m 3
m  Mass, kg
n  Moles
R  Specific Gas Constant, kJ/kg  K
Ru  Universal Gas Constant, kJ/kmol  K
T  Absolute Temperatur e, K
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Applicability of The Ideal Gas Equation
• The Ideal Gas Equation closely approximates the
P-V-T behaviour of Real gases at low densities
• At low pressures and high temperatures, the
density of a gas decreases, and the gas behaves
as an ideal gas
• Many familiar gases like air, nitrogen, oxygen,
hydrogen, helium, argon, neon, krypton, carbon
dioxide are ideal gases
• Dense gases like water vapour, refrigerants must
not be treated as ideal gases
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 Other Equations of State
• The ideal gas equation is simple but range of
applicability is limited
• To cover a wider range, few other equations
are suggested
• Van der Waals equation (one of the earliest)
• Beattie-Bridgeman equation (one of the best
known and reasonably accurate)
• Benedict-Webb-Rubin equation (one of the
most recent and very accurate)
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Van der Waals Equation

 a
 P  2 v  b   RT
 v 
27 R 2Tcr2 RTcr
a and b 
64 Pcr 8Pcr

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 Beattie-Bridgeman Equation
RuT  c 
P  2 1  3 v  B   2
A
v  vT  v
 a  b
A  A0 1   and B  B0 1  
 v  v

The constants A0, a,B0,b and c can be obtained from

tables.
The Equation is reasonably accurate for densities up
to about 0.8 cr
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 Benedict-Webb-Rubin Equation

RuT  C0  1 bRuT  a a c     / v 2
P   B0 RuT  A0  2  2   6  3 2 1  2 e
v  T v v 3
v vT  v 

The constants A0, a, B0, b, C0, c, α, and  can be

obtained from tables.
The Equation is reasonably accurate for densities up
to about 2.5 cr

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 Compressibility Factor (Z)
• The deviation from ideal gas behaviour at a
given temperature and pressure can
accurately be accounted by the
Compressibility Factor
Pv
Z or Pv  ZRT
RT

36
 Compressibility Factor (Z)…
• The value of Z can be found from charts using
the values of Reduced Pressure (Pr) and
Reduced Temperature (Tr)
P T
PR  and TR 
Pcr Tcr
• The value of Z is approximately the same at
the same reduced pressure and temperature.
• This is called the Principle of Corresponding
States
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Generalized Compressibility Chart

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 Some Observations
• At very low pressures (PR<<1), gases behave as
an ideal gas regardless of temperature
• At high temperatures (TR>2), ideal gas
behaviour can be assumed with good accuracy
regardless of pressure (except when PR>>1)
• The deviation of a gas from ideal gas is
greatest in the vicinity of the critical point

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Some Observations…

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 Problem 1
Determine the specific volume of superheated
water vapour at 10 MPa and 400 0C, using (a)
the ideal-gas equation, (b) Van der Waals
equation, (c) the generalized compressibility
chart and (d) the steam tables.

Ans: (a) 0.03106 m3/kg, (b) ,(c) 0.02609 m3/kg

and (d) 0.02644 m3/kg

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 Problem 2
Determine the specific volume of nitrogen gas at 10
MPa and 150 K based on (a) the ideal-gas equation
and (b) the generalized compressibility chart.
Compare these results with the experimental value
of 0.002388 m3/kg, and determine the error
involved in each case. For Nitrogen, Pcr=3.39 MPa,
Tcr=126.2 K.

Ans: (a) 0.004482 m3/kg, 86.4%, (b) 0.002404

m3/kg, 0.7%
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 Van der Waals equation of state
• (p + a/v2) (v – b) = RT on mass basis
• (p + a/ṽ2) (ṽ – b) = RuT on mole basis
• a/v2 accounts for intermolecular forces
• b represents volume occupied by molecules per unit mass
• a, b are functions of pcrit, Tcrit, R
27 R 2Tcr2 RTcr
• Alternative form: a ; b
64 pcr 8 pcr
• p = RT/(v – b) – a/v 2

Gas a (N.m4/(kmol2) b (m3/kmol)

H2 25105 0.0262
O2 139250 0.0314
CO2 362850 0.0423
Air 135522 0.0362
Steam 551130 0.0300

MEE1003 - Engineering Thermodynamics

Thank You