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Eso201A: Thermodynamics 2020-21 Ist Semester IIT Kanpur Instructor: P.A.Apte

The document discusses thermodynamic properties and property diagrams of pure substances including water. It describes phase changes and equilibrium conditions at different pressures and temperatures. Tables of properties for various states such as saturated liquid and vapor, compressed liquid and superheated vapor are also presented with examples of using the tables to determine changes in properties during phase change processes.

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Jitesh Hemji
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94 views

Eso201A: Thermodynamics 2020-21 Ist Semester IIT Kanpur Instructor: P.A.Apte

The document discusses thermodynamic properties and property diagrams of pure substances including water. It describes phase changes and equilibrium conditions at different pressures and temperatures. Tables of properties for various states such as saturated liquid and vapor, compressed liquid and superheated vapor are also presented with examples of using the tables to determine changes in properties during phase change processes.

Uploaded by

Jitesh Hemji
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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ESO201A : THERMODYNAMICS

2020-21 Ist semester


IIT Kanpur

Instructor : P.A.Apte
Lecture 5
Copyright: The instructor of this course (ESO201A) owns the copyright of all the
course materials. The lecture material was distributed only to the students
attending the course ESO201A of IIT Kanpur, and should not be distributed in
print or through electronic media without the consent of the instructor. Students
can make their own copies of the course materials for their use.
T-v plots resulting from constant pressure expansion of water at various pressures

NOTE : “critical” point occurs at Pcr = 22.06 MPa, Tcr = 373.95 0C, vcr = 0.03106 m3/kg

As critical point is approached, the saturated liquid and saturated vapor phases ‘merge’.
Constant pressure expansion :

Note that above critical pressure (P > Pcr), no phase change is observed
in constant pressure expansion

The state of the substance above critical pressure and critical


temperature is called as “gas” since it does not condense upon cooling
or compression
Property diagrams of a pure substance :

Note that Tsat = f(P).

As P increases, Tsat also


increases.

T-v plot of a pure substance


The green curve is known as “saturation curve”. It can be divided into two
parts : one corresponding to saturated liquid and the other corresponding
to saturated vapor. On the left hand side of the curve, below the critical
point we have a region where liquid is the stable phase and is called as
compressed liquid region. On the right hand side below the critical point,
we have superheated vapor region. Here the vapor phase is the stable
phase. Inside the curve we have two-phase region where both saturated
liquid and saturated vapor coexist.
Constant temperature expansion of a pure
substance :

The constant temperature


expansion can be brought
about by removing weights
on the piston successively
while providing heat so as P-v plot of a pure substance
to maintain constant At P = Psat, expansion occurs at constant temperature and pressure.
temperature
Note also, that Psat = f(T). As T increases, Psat also increases.
Phase changes involving solid phase:
There are two types of phase changes involving solid phase :
sublimation and melting

Melting involves solid to liquid transition at constant temperature


and constant pressure.

Sublimation involves direct conversion of solid phase into vapor


phase at constant temperature and constant pressure.

These changes can be brought about by constant pressure


heating starting from the solid phase.

There are two phase regions (solid—vapor and solid—liquid)


associated with sublimation and melting, just like in case of
vaporization (liquid—vapor).
Constant temperature expansion of a pure substance :
The P-v diagram resulting from constant temperature expansion of a pure substance
involving all three phases is shown below:

This plot is for substances in


which solid phase has a lower
specific volume than the
liquid phase at coexistence.
Constant temperature expansion of a pure substance :
liquid (at solid (at melting
freezing point) point)

This plot is for substances (for


example, water) in which solid
phase has a higher specific
volume than the liquid phase
at coexistence.
Triple point of a pure substance :
Note that in the last two slides, triple line is seen which
corresponds to the overall specific volume (v) of a
system in which all three phases coexist.

Such a system exists at the temperature and pressure


corresponding to a unique point known as “Triple point”

For water, triple point temperature and pressure are


0.01 0C and 0.6117 kPa, respectively.

At a specific volume corresponding to the triple line (see


last two slides), we have the condition :
v = x g v g + x f v f + xs vs
mg mf ms
xg = , xf = , xs =
mt mt mt
mg = mass of vapor phase, mf = mass of liquid phase, ms = mass of solid phase,
and mt = (mg + mf + ms ) is the total mass
P-T diagram of a pure substance that exists in 3 phases:

• Unlike the P-v or T-v diagrams, there is no two phase region in P-T diagram.

• The green curves are also known as coexistence curves or saturation curves.

• Sublimation (solid-vapor transition) occurs below triple point temperature. For


example, camphor undergoes sublimation at ambient conditions. This is because the
triple point of camphor is at (180.1 °C; 51.44 kPa)
Property Tables : For water, these tables are as listed below (Table numbers
refer to Appendix 1 of the textbook).

Saturated water – Temperature table (Table A-4)


Saturated water – Pressure table (Table A-5)
Superheated water (Table A-6)
Compressed liquid water (Table A-7)

Table A-4 is partially reproduced below. Note that subscript “f” and “g” refer to
saturated liquid and saturated vapor at the given temperature. “u” is internal
energy per unit mass and “s” is a property known as entropy (which we will
explain later in the course) per unit mass. Psat is the saturation pressure at the
given temperature.
Reference states for the property tables:
The absolute values of properties like internal energy cannot be
measured. However as demonstrated by Joule’s experiments,
change in internal energy can be measured. Hence a convenient
reference state is chosen at which properties such as internal energy
and entropy are taken as zero.

For water, the reference state is liquid water at the triple point. The
first row of the Tables A-4 (previous slide) corresponds to the triple
point. In the first row (triple point) of Table A-4 , uf = 0, sf = 0.

Saturated water—Pressure table (A-5) is reproduced below partially.


Property tables:

Note that in Tables A-4 and A-5, the symbol “fg” refers to the
difference between properties of saturated liquid (f) and saturated
vapor (g).

For example, hfg = hg – hf . This quantity (hfg) is known as


enthalpy of vaporization (or latent heat of vaporization).

The values of vfg , ufg , hfg , and sfg decreases with increasing
temperature or increasing pressure and becomes zero at the
critical point. This is because the saturated liquid and saturated
vapor states approach each other as we approach critical point
upon incresing pressure or increasing temperature (see previous
slides).
Example : A mass of 1 kg of saturated liquid water is completely vaporized to
saturated vapor at constant pressure of 100 kPa. Determine (a) volume change
(b) the heat transferred to water assuming slow expansion

Solution : Since it’s a constant pressure process involving saturated liquid and
saturated vapor, we will use Table A-5. The relevant portion of Table A-5 is
reproduced below.

Volume change is : ΔV = m(vg – vf)


= (1)(1.6941-0.001043)
= 1.693 m3
Heat transferred (assuming slow expansion) is :
Qin = m(hg – hf ) [Since it’s a constant pressure process]
= (1)(2257.5)
= 2257.5 kJ
Mixture of saturated liquid and saturated vapor:
In certain processes, we deal with a mixture in which saturated liquid and
saturated vapor are present. The specific volume of such a mixture
corresponds to the area inside the saturation curve shown below.

The specific volume of this mixture is obtained as follows : v = (1-x) vf + x vg

where x = mg/mt is the mass fraction of the vapor phase and mt = (mf + mg ) is
the total mass. The quantity ‘x’ is often referred to as the dryness fraction or
the quality. Similarly we can calculate other specific properties of the mixture.
Superheated water table:

Superheated water table (A-6) is reproduced below partially. Note that in this
table (A-6), the temperature in the parenthesis corresponds to the saturation
temperature at given pressure. For example, at P = 0.01 Mpa, Tsat = 45.81 0C.
The properties of saturated vapor at P = 0.01 MPa are listed in the top row
starting with the letters “Sat.”
Properties of compressed liquid:
As per the state postulate, the state of compressed liquid is
completely determined by specifying temperature (T) and
pressure (P). For a compressed liquid, P > Psat where Psat is the
saturation pressure at T. The properties of compressed liquid
(Table A-7) are listed only for a limited set of conditions. Since
liquid properties are not strongly affected by pressure, the
following approximation can be made to estimate compressed
liquid properties in case these are not explicitely available in
tables:
u(T,P) ≈ uf@T , v(T,P) ≈ v f@T , s(T,P) ≈ s f@T

Please note that uf@T = u(T,Psat)


vf@T = v(T,Psat)
sf@T = s(T,Psat)
Properties of compressed liquid:
The specific enthalpy of a compressed liquid is estimated as :
P
 ∂h 
h(T,P) -h(T,Psat ) = ∫   dP
Psat 
∂P T
P
 ∂(u + Pv) 
= ∫  dP
Psat 
∂P T
≈ v f@Psat (P -Psat )
In the above derivation, pressure dependence of u and v at
constant T has been neglected. Also, the remaining integral
term has been simplified using the approximation
v(T, P) ≈ v(T,Psat) = vf@T (independent of P).

Since h(T,Psat) = hf@T , the above equation can be re-arranged


as:
h(T,P) ≈ hf@T + v f@T (P -Psat )
Example: Determine the enthalpy of compressed liquid water at 80 0C and
5 MPa using (a) compressed liquid data and (b) saturated liquid data. What is
the error involved in the second case.
Solution : Relevant part of the compressed liquid table (A-7) is reproduced
below. (a) Using Table A-7, the internal energy is h = 338.96 kJ/kg

(b) Using saturated liquid data (Table A-4) see below, and expression on last slide
h ≈ hf@80C + vf@80C(P-Psat) = 335.02 + (0.001029)(5000-47.416) = 340.11 kJ/kg.
The percentage of error involved is = (340.11-338.96)(100)/(338.96) = 0.34 %
This error is small and hence the approximation used in (b) is good.

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