Thermodynamics

Chapter 4:
properties of pure substances

Main concepts:
Pure Substances
Phase change processes of pure substance at
constant pressure on T-Q Diagram
T-V Diagram for a pure substance
P-V Diagram for a pure substance
P-T Diagram for a pure substance
p-V-T- surface
T-S and h-s diagrams,
Mollier Charts,
Phase Transformations
Dryness Fraction
Clausius Clapeyron Equation
Steam Calorimeters

Phase and Pure Substance

Pure Substance: A substance that is uniform and invariable in chemical composition.

May each of these be considered a pure substance?

Helium gas
in a tank?

Air
Ice

Yes

Oil

Water

Honey

A contents of a
glass containing
water and ice?

Yes

Atmospheric
air?
Yesmaybe

A jar of honey,
water, oil, and
ice topped
with air?
No

Phase and Pure Substance

Phase: Matter which is homogeneous throughout in both its chemical

composition and physical structure.
Bottle Contents : Air (N2, O2, ect.)
Homogeneous chemical composition?
Homogeneous physical structure?
Bottle : Glass
Homogeneous chemical composition?
Homogeneous physical structure?
Cap : Aluminum?
Homogeneous chemical composition?
Homogeneous physical structure?

PHASE CHANGE PROCESSES OF PURE SUBSTANCE AT

CONSTANT PRESSURE

Formation of steam

Fig. T-Q. Diagram for Phase change from Ice into steam.

Fig. T-V. Diagram for Phase change from Ice into steam.

Fig. p-V diagram for water (solid-liquid-vapor region)

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The points on the

sublimation curve
represent the
coexistence of solid
and vapor.
The points on the
vaporization curve
represent the
coexistence of liquid
and vapor.
The points on the
fusion curve
represent the
coexistence of liquid
and solid.
p-T diagram for a substance such as water.

P-v-T relation

3D p-v-T surface model:

A representation of how
p, v, and T take on specific
values depending upon their
intensive properties and
phase changes.

The different surfaces of

the model represent
different phases of a pure
substance (like H20) which
depend only on the
pressure, temperature,
and specific volume of the
state.

11

P-v-T relation

12

Phase Diagram from the 3D p-v-T surface model:

If you pull off the Pressure-Temperature projection you create a plot
given as the Phase Diagram.

Critical Point

Pressure

mp
Te

at
er

ur

Triple point

P-v-T relation

13

Pressure

p-V Diagram from the 3D p-v-T surface model:

The Pressure-Specific Volume projection
of the surface model is a useful tool
for showing processes involving
ice-water-water vapor system.

Sp
e

ci f

ic
Vo
l.

P-v-T relation

14

Projections of p-v-T surface:

Triple Point--the state at which solid, liquid, and gas coexist
Critical Point-- the point where saturated liquid and saturated vapor lines meet.

Isotherms--Lines of constant temperature

Isotherms

Phase diagram

p-V Diagram

P-v-T relation

15

T-v diagram from the 3D p-v-T surface model:

If you pull off the Temperature-Specific Volume projection you create
a plot that can be useful for showing
e
ur
lines of constant pressure.
at
r
pe
m
Te

isobar: line of constant pressure

Spe
c if
ic

Vol
um
e

16

T-S Diagram for a pure substance

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MOLLIER DIAGRAM

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Linear Interpolation:

yunknown y1 xknown x1

y2 y1
x2 x1

yunknown

y2 y1
y1
( xknown x1 )
x2 x1

y2
yunknown
y1

*
x1

xknown

x2

Evaluating P, v, T

You try it: What is the specific volume of a water at 40 bar and 140 oC?
Linear Interpolation will be needed.
Given the following:
@ 140C & 25 bar, v1 = 1.0784 m3/kg
@ 140C & 50 bar, v2 = 1.0768 m3/kg
Find the spec. vol at p = 40 bar.

v v1

v2 v1
( p p1 )
p2 p1

v 1.0784

(1.0768 1.0784)
(40 25) 1.0774
(50 25)

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MEASUREMENT OF DRYNESS FRACTION
There are four methods of determining the dryness fraction of steam experimentally.

They are as follows:

(A) Bucket or barrel calorimeter
(B) Separating calorimeter
(C) Throttling calorimeter
(D) Combined separating and throttling calorimeter.
(A) Bucket or barrel calorimeter
Before steam sampling: Note down the following observations
Mass of empty copper vessel = m1(say)
Mass of cold water of vessel = m2(say)
Temperature of cold water and copper vessel = t1(say)
Specific heat of copper vessel = Cp,copper(say)
Specific heat of water = Cp,water(say)

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After steam sampling: Note down the following observations
Mass of warm water in vessel = m3 (say)
Temperature of warm water and copper vessel after mixing of steam sample in cold water= t 2 (say)
Calculations to find dryness fraction, x:
Mass of wet steam sample condensed in cold water = m3 m2 = m (say)
Mass of dry steam in wet steam sample = x m
If there is no heat lost then according to conservation of energy,
Heat lost by mass of wet steam sample = Heat gain by copper vessel and cold water
-----(1)
Where,
Heat lost by mass of wet steam sample = Latent heat lost by mass of dry steam in wet steam sample + Sensible heat
lost mass of wet steam sample
=
------------------ (2)
Heat gain by copper vessel and cold water = Sensible heat gain by mass of copper vessel + Sensible heat gain by
mass of cold water
-------------(3)
By using equations (2) and (3) in equation (1), we have

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(B) Separating calorimeter:
Principle: The principle of determining the dryness fraction from separating calorimeter is to
separate out the moisture content from the wet steam.

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Procedure:
Before steam sampling: Note down the following observations
Level of water in the inner chamber = L1(say)
Mass of water in the steam condensing chamber = m1(say)

Before steam sampling: Note down the following observations

Level of water in the inner chamber = L2 (say)
Mass of water in the steam condensing chamber = m2 (say)

Calculations of dryness fraction, x:

Mass of water separated from the wet steam sample and collected at the bottom portion of the
inner chamber

= m , kg (say)
Mass of dry steam condensed in steam condensing chamber = (m2 - m1) = M , kg(say)
Dryness fraction of wet steam from main steam pipe,

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(C) Throttling calorimeter:
Principle: The principle of the throttling calorimeter is to throttle the wet steam so that it
becomes superheated.

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During steam sampling: Note down the following observations:
Pressure of the wet steam before throttling = p1 bar
Pressure of the superheated steam after throttling = p2 bar
Temperature of the superheated steam after throttling = tsup,2 C

Calculations of dryness fraction of wet steam, x1:

Enthalpy of wet steam at point 1 corresponding to pressure p1 is given by ,

h1= hf1 + x1. hfg1

Enthalpy of a superheated throttled steam corresponding to pressure p2 and temperature tsup,2 is
calculated by

sup2

= hg2 + Cp(tsup2 - tg2), kJ/kg.

where Cp is sp. heat of superheated steam = 2.607 kJ/kg K

Since during throttling process, the enthalpy remains constant, hence

h1 = hsup2
hf,1 + x1. hfg,1 = hg,2 + Cp(tsup,2 - tg,2)

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(D) Combined separating and throttling calorimeter:
Principle: In this calorimeter
()The moisture from wet steam sample is first removed in separating calorimeter, so that dryness
fraction of wet steam sample is increased above 0.95 before steam sample is entering into
throttling calorimeter. During this process pressure and temperature remains constant.
()The sample coming out from separating calorimeter is then passed through throttling
calorimeter where it expands to superheated steam.

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During steam sampling: Note down the following observations:
Pressure before throttling = p1 (say) bar
Pressure after throttling = p2 (say) bar
Temperature of a throttled superheated steam = tsup,C (say), oC
After steam sampling: Note down the following observations:
Mass of condensate collected in the container provided at the bottom of throttling calorimeter
(i.e. mass of steam coming from separating calorimeter into throttling calorimeter through
throttling valve) = M (say),kg
Mass of water collected in the inner chamber of the separating calorimeter (i.e. mass of water
separated in the separating calorimeter = m (say),kg

Representation of two processes of separating-throttling calorimeter on T-s and h-s diagrams

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Calculations of dryness fraction of wet steam, x:
Partial dryness fraction of wet steam coming from main steam pipe, measured by separating
calorimeter alone,

Dryness fraction of steam entering into throttling calorimeter from separating calorimeter
through throttling valve, measured by throttling calorimeter alone,

Where,
hf,B is enthalpy of saturated water at p1 (from steam tables), kJ/kg.
hfg,B is Latent heat of vapouization at p1 (from steam tables),kJ/kg
hsup,C is enthalpy of a throttled superheated steam corresponding to pressure p 2 and temperature tsup,C
(from superheated steam table),kJ/kg .
The total dryness fraction of wet steam collected from main steam pipe measure by Combined
Separating and Throttling Calorimeter

x = x1.x2