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Engineering Thermodynamics (UES003)

Lecture
on
Pure substances and steam tables
Dr. Hiralal Bhowmick
Thapar University

Introduction to pure substance


Homogeneous:
A substance that has uniform thermodynamic properties throughout is
said to be homogeneous.

Phase:
A phase is defined as having a distinct molecular arrangement that is
homogenous throughout and separated from others (if any) by easily
identifiable boundary surfaces.

Pure Substance:
A pure substance is one whose chemical composition does not change
during thermodynamic processes.
A pure substance has a homogeneous and invariable chemical composition
and may exist in more than one phase or physical state.
Mixtures are not pure substances. (eg: Humid air)
Water and refrigerants are examples of pure substances.

Water :

Introduction to pure substance


It exists in three states namely, solid ice, liquid water and
water vapour and undergoes transformation from one state to
another.
In our discussion we will take water as the representative pure
substance

Water has peculiar properties compared to other


liquids.
Solid phase is less dense than the liquid phase (ice floats on
water).
Water expands on cooling (a fully closed vessel filled with water will
burst if it is cooled below the freezing point).

The largest density of water near atmospheric pressure is at


4c.

Evaluation of thermodynamic properties


In order to perform thermodynamic calculations, one has to know
various thermodynamic properties of the system.
In a majority of cases, a minimum of two properties are required
to define the state of a system.
The best choice is an extensive property and an intensive property, such as
P or T and some other properties.

Measureable properties:
P, v, T
Non-Measurable Properties:
Internal energy, enthalpy and entropy.

Evaluation of thermodynamic properties


Quantification of Non-Measurable Properties:
The properties which cannot be measured directly such as
internal energy, enthalpy and entropy of a system, are
evaluated
w.r.t. change in the energy of the system,
in terms of the measurable properties such as pressure, temperature,
volume, specific heat etc.

Hence one can determine u, h, s, but not the absolute


values of these properties.
Therefore it is necessary to choose a reference state to which
these properties are arbitrarily assigned some numerical values.
For water, the triple point (T = 0.01o C and P = 0.6113 kPa) is
selected as the reference state, where the internal energy and
entropy of saturated liquid are assigned a zero value.

Evaluation of thermodynamic properties


In general thermodynamic properties can be evaluated from:
Thermodynamic equations of state
Thermodynamic tables & charts
Direct experimental results, and
The formulae of statistical thermodynamics

Already discussed

Equations of state and thermodynamic relations


Equation of state:
An equation of state (EOS) is a fundamental equation, which expresses
the relationship between pressure, specific volume and temperature.
experiments on the variables of state (such as T, P, V, and n) showed that only two of
these variables of state need to be known to know the state of a sample of matter.

Ideal gas and Real gases


Compressibility factors & van der Waals equation

Thermodynamic relations for ideal gases

Already discussed

Equations of state and thermodynamic relations


Other Thermodynamic relations
There are some more general thermodynamic relations, which are useful
for determination of several thermodynamic properties from measured
data on a few properties.
The following relationships are generally used for the evaluation of entropy
change.
Will be discussed later

Tds Equations:.

These are obtained by applying first and second laws of thermodynamics

Thermodynamic charts

T-v diagram
P-v diagram
P-T diagram
P-v-T diagrams
Temperature-entropy (T-s) charts
pressure-enthalpy (P-h) charts

Thermodynamic property charts are very useful in evaluating


properties of substances and also for representing the
thermodynamic processes and cycles.

Let us start with different states of water by a T-v plot, which will
be followed by development of various charts for pure substance.

States of Water and Basic Nomenclatures


Lets consider the results of heating liquid water from 20 C, 1 atm
while keeping the pressure constant.
The following events will occur and shown in T-v plot

States of Water and Basic Nomenclatures

vg

In the saturation region the T


and P are dependent
properties; if one is known,
then the other is automatically
known

States of Water and Basic Nomenclatures

vf

vg

States of Water and Basic Nomenclatures

vf

States of Water and Basic Nomenclatures


 Saturation properties:
A state where a phase change begins or ends is
called a saturation state.
The temperature at the saturated state is called
saturation temperature.
If a liquid (pure substance) is heated at constant
pressure, the temperature at which it boils is
called saturation temperature.
for water at 0.1 Mpa, the saturation temperature is
99.6 C

Characteristics
This temperature will remain constant during
heating until all the liquid boils off.
The saturation temperature of a pure
substance is a function of pressure only.
At atmospheric pressure, the saturation
temperature is called normal boiling point .

States of Water and Basic Nomenclatures


 Saturation properties :
At a specified temperature, the pressure at
which the phase change takes place is called
saturation pressure.
If a substance exists as liquid at the saturation
temperature and pressure it is called saturated
liquid.
If a substance exists as vapor at the saturation
temperature, it is called a saturated vapor.

 If the temperature is of the liquid is lower


than saturation temperature at the
existing pressure it is called sub-cooled
liquid or compressed liquid.
 When the vapor is at a temperature
greater than the saturation temperature,
it is said to exist as superheated vapor.

States of Water and Basic Nomenclatures


when a solid is heated at constant pressure,
it melts at a definite temperature called
melting point.
Similarly cooling of a liquid causes freezing
at the freezing point .
The melting point and freezing point are
same at same pressure for a pure substance.

If the vapor of a pure substance is cooled at


constant pressure, the
temperature at
which the condensation starts, is called dew
point temperature.
For a pure substance, dew point and boiling
point are same at a given pressure.

For all pure substances there is


a
temperature at which all the three phases
exist in equilibrium.
This is called triple point .

States of Water and Basic Nomenclatures


 Saturated liquidvapor mixture:
The zone between the saturated liquid
and the saturated vapour region is called
the two phase region or saturated
mixture region where both liquid and
vapor are in equilibrium.

States of Water and Basic Nomenclatures


 Saturated liquidvapor mixture:
When a substance exists as part liquid and part vapor at the
saturation temperature, its quality (X) is defined as the ratio of the
mass of vapor to the total mass.

States of Water and Basic Nomenclatures


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.

Temperature-volume diagram
The locus of all the saturated states gives
the saturated liquid curve AC and the
locus of all the saturated vapor states gives
the saturated vapor curve BC.
The point C represents the critical point.
A liquid below the critical point when
heated first becomes a mixture of liquid
and
vapour and then becomes
saturated vapour and finally a
superheated vapour.
There is a clear-cut meniscus between
liquid and vapour, until all the liquid
evaporates

Critical Point
It is the highest temperature below which the liquid and vapour phases
can coexist.
At critical point there is no distinction between liquid state and vapour
state; these two merge together.
At the critical point
vg = vf
hfg ,ufg and vfg are zero.
The temperature, pressure and specific volume at critical point are
denoted by Tc, Pc and vc, respectively.
At supercritical pressures, the substance is simply termed fluid rather
than liquid or vapor.

For water:
Triple point: 0.1oC, 0.006112 bar
Critical point: 221.2 bar, 647.3K
and 0.00317 m3/kg

For Dry Ice (CO2) :


Triple point: 5.18 bar, -56.6oC
Critical point: 73.8 bar, 31oC

Pressure-volume diagram
If we plot P versus v for a large
number of isotherms, we obtain a
pressure-volume diagram
The pressure-volume (P-V) diagram
for a pure substance is shown in
Figure.
The curves AC and BC represent the
saturated liquid curve and saturated
vapor curve, respectively,
Point E represents 100% saturated liquid
Point F represents 100% saturated
vapor
Point C is critical point.

Pressure-volume diagram
The area under the curve ACB
represents the two-phase region.
Any point M in this region is a
mixture of saturated liquid (shown
as f) and saturated vapor (g).

The isotherm T2 and T3 appear


on three segments DE, EF, FG
DE: almost vertical because the
change in the volume of liquid is
very small for large change in
pressure.
FG: less steep because the vapor
phase is highly compressible
EF: volume change takes place for
phase change at constant P and T

Extending P-v diagram of pure substance to include the solid phase

P-T plots of pure substance

A P-T diagram is the most common way to show the phases of a substance.
The line that separates the solid and vapor phases is called the sublimation line.
The line that separates the solid and liquid phases is called the fusion/melting line.
The line that separates the liquid and vapor phases is called the vaporization line.
The point where the three lines meet is called the triple point.
At the triple point the system becomes invariant
The point where the vaporization line ends is called the critical point.
At temperatures and pressures greater than those at the critical point, no substance
can exist as a liquid no matter how great pressure is exerted upon it.

P-v-T plots of pure substance

Enthalpy-Entropy (h-s) or Mollier diagram


The h-s diagram was introduced by
Richard Mollier and was named after
him.
Basis of h-s diagram
Tds = dh vdp
h
=T
s p

It plots the following on enthalpy


versus entropy coordinates
constant pressure lines,
constant temperature lines and
constant volume lines.
In the two-phase region, the constant
pressure and constant temperature
lines coincide.

Thermodynamic tables (Steam Tables)


Thermodynamic properties of various pure substances are
available in the form of tables.
Steam tables are used extensively in power plants and
industrial processes.
Thermodynamic charts though has its inherent advantages,
still the values obtained from them may be not as precision
as that of steam tables.
The steam tables provide the data of useful thermodynamic
properties like T, P, v, u, h and s for saturated liquid,
saturated vapor and superheated vapor.

During phase transition, the pressure and temperature are not


independent of each other.
If the temperature is specified, the pressure at which both phases
coexist in equilibrium is equal to the saturation pressure.

Thermodynamic tables (Steam Tables)


Hence, it is possible to choose either temperature or
pressure as the independent variable, to specify the state
of two-phase system.

Depending on whether the temperature or


pressure is used as the independent variable, the
tables are called temperature or pressure tables.
In the saturated steam tables, the properties of
saturated liquid that is in equilibrium with
saturated vapor are presented.
The two phases- liquid and vapor can coexist in a
state of equilibrium only up to the critical point.
Therefore the listing of the thermodynamic
properties of steam in the saturated steam tables
ends at the critical point (374.15o C and 212.2 bar).

Use of thermodynamic charts and tables


Properties at Saturation:
The properties of refrigerants and water for saturated states are available in the
form of Tables. Data tables will list properties at the two ends of saturation.
The properties along the saturated liquid line are indicated by subscript f for
example vf, uf , hf and sf indicate specific volume, internal energy, enthalpy and
entropy of saturated liquid respectively.
The corresponding saturated vapour states are indicated by subscript g for
example vg, ug, hg and sg respectively.

Properties at superheated condition


If the steam exists in only one phase (superheated steam), it is necessary to specify
two independent variables, pressure and temperature, for the complete
specification of the state. In the superheated steam tables, the properties- v, u, h,
and s- are tabulated from the saturation temperature to some temperature for a
given pressure.

Use of thermodynamic charts and tables


Properties at two phase region
All properties with subscript fg are the difference between saturated
vapour and satura ted liquid states. For example, hfg = hg - hf, the latent
heat of vaporization.
The specific volume, internal energy, enthalpy and entropy of the mixture
in two-phase region may be found in terms of quality, x of the mixture.
The quality of the mixture denotes the mass (kg) of the vapour per unit
mass (kg) of the mixture. That is there is x kg of vapour and (1-x) kg of
liquid in one kg of the mixture.

Use of thermodynamic charts and tables


Reference states to calculate the thermodynamic property

Illustration of using proper steam table


Given the temperature or pressure and one other property from the group
v, u, h, and s, the following procedure is used, to evaluate the other
thermodynamic properties from the steam table.
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, and the compressed liquid tables are used to find the
properties of the state.
If the answer to the second question is yes, the state is in the saturation
region, and either the saturation temperature table or the saturation
pressure table is used to find the properties.
Then the quality is calculated and is used to calculate the other properties, u, h, and s .

If the answer to the third question is yes, the state is in the superheated
region and the superheated tables are used to find the other properties.

Illustration of using proper steam table


Some tables may not always give the internal energy.
When it is not listed, the internal energy is calculated from the
definition of the enthalpy as

Other types of thermodynamic charts:


T-s diagrams for a pure substance

Other types of thermodynamic charts:


T-s diagrams for a pure substance

Other types of thermodynamic charts:


p-h diagrams for a pure substance

Example: T-s and p-h diagrams for a pure substance


Two figures show typical T-s diagram and p-h diagrams, respectively for
a pure substance.
The T-s diagram shows two constant pressure lines for pressures P1 and
P2 where P1 > P2.
The constant pressure line 1-2-3-4 is for pressure P1.
The portion 1-2 is in the sub-cooled region,
2-3 is in wet region, that is mixture of liquid and vapour, and
3-4 is in superheated region.

Let us take the example of liquid at state a

Example: T-s and p-h diagrams for a pure substance

Measurement of steam quality


 The state of pure substance is fixed by two independent
properties
 Measurement of p & T are easier
 So whenever these two are independent the state is defined by
these two, for example in subcooled liquid region or superheated
vapor region

 But in saturation or two-phase region p & T are not


independent
 So to fix the state besides, p or T and one more properties
from v, u, h, s, x, etc are required to fix the state.
 Now measurement of specific volume of a mixture is
relatively difficult.
 one suitable alternative is to measure quality of steam (which
can not be measured simply by measuring p and T in two
phase region).

Measurement of steam quality: Throttling Calorimeter


 Throttling calorimeter is a device which is used to determine the
quality (x) or dryness fraction of steam or enthalpy of the
mixture.
 Throttling is a constant enthalpy process
 Enthalpy of fluid remains constant when it is throttled from high
pressure to low pressure.

 In the measurement of quality,


 the object is always to bring the state of the substance from two-phase
region to the single phase superheated region, where both p and T
becomes independent.

Measurement of steam quality


 Working principle:
 It is based on Joule-Thomson expansion principle
 A small amount of wet steam flowing through a steam main is throttled
to a low pressure, such that the exit steam is superheated.

Measurement of steam quality


 Working principle:
 Since throttling is an isenthalpic process, the enthalpy of the wet steam
is equal to the enthalpy of superheated steam leaving the throttling
calorimeter.
 Thus measuring p and T in superheated vapour region and determining
the corresponding enthalpy, we can find out the quality in the original
region by applying the principle of constant enthalpy

he h f

he = hi = h f + xh fg
x=

h fg

Thank You
Further Readings: Books by
Cengel & Boles
PK Nag
YVC Rao