83

Lecture 1: Brief Review of Thermodynamics 1

84

85

86

87

88

89

90

91

92

93



94

95

96

97
98
Exergy, availability and irreversibility

This topic relates to the maximum useful work that you can do with a system in a given state, if
the system moves to the state of the environment (called the dead state).

Profs. Lee and Bergthorson cover this material in a different way, so I wont go over it all again.
Go over this material if you dont remember how exergy is defined.

Calculation of exergy for complex engineering systems are done in industrial systems to
optimize the efficiency of the system. We wont develop the concept of exergy further in Thermo
2.
99
Thermo 1 review (or not), contd: Properties of Pure Substances

Background reading: Cengel & Boles (and Moran & Shapiro), Chap. 3

A puresubstancehas a fixed chemical composition. Which of the following are pure substances?











Phases of a pure substance:







Solid Liquid Gas
100
Compressed Liquid and Saturated Liquid




















A saturated liquid is just about to vaporize.
Also called a subcooled liquid, a liquid
in this state in not about to vaporize
water
101
Saturated Vapour, Saturated Vapour and Superheated Vapour
and Sat. Liquid mixture
















A vapour in equilibrium with a liquid is called a saturated vapour/liquid mixture. A saturated vapour is just about to
condense. A superheated vapour is heated above the normal saturation temperature (temperature at which
vapour and liquid are in equilibrium) and hence is not about to condense.
102
Saturation Temperature and Pressure

The saturation temperature is the temperature at which a pure substance changes phase. For water, at 1 atm, this
temperature is the same as the normal boiling point.




Temperature-Volume (T-v) diagram for the heating
process of water at a constant pressure of 1 atm
103
Latent Heat

The energy absorbed or released during a phase change is called the latent heat, e.g., latent heat of fusion (for
freezing) or latent heat of vaporization (for vaporization). A phase change from a solid to gas is called
sublimation.

During a vaporization process, the liquid
and vapour are in equilibrium (at the
saturation p and T) and pressure and
temperature remain fixed. The relation
between p and T during this phase change
is called the liquid-vapour saturation
curve:


104
Property Diagrams: T-v diagram




Constant pressure lines on a T-v diagram
At supercritical pressures
(p > p
cr
), there is no distinct
phase-change (boiling)
process
105
T-v diagram, continued:



Note the shape of the constant pressure lines
106
p-v diagram:




Note the shape of the constant temperature lines
107
p-v diagram, including the freezing/melting curve (for water which expands upon freezing):






Note the triple linewhere the liquid, vapour and solid are all in equilibrium
108
p-T diagram(often called the phase diagram):





109

The p-v-T surface

Since the state of a simple compressible substance is fixed by 2 independent properties, p = p(v, T), for example,
defines a surface:



This substance contracts on freezing This substance expands on freezing (like water)
110

111
Property Tables

The properties of water (and some other substances) are tabulated. The properties of saturated vapour and liquid
are given in saturation tables (Tables A-4 and A-5 in Cengel & Boles) whereas the properties of superheated
vapour are given in Table A-6 and compressed liquid in Table A-7.




















112
For saturated liquid-vapour mixtures, the ratio of the mass of vapour to the total mass of the mixture is called the
quality, x:
x =m
vapour
/m
total

In the 2-phase region, all properties can be written as a weighted sum of the saturated liquid and vapour values, e.g.,

V = V
liq
+V
vap
=m
liq
v
f
+m
vap
v
g
and now divide by m
total
: V/m =v
avg
=(1 x) v
f
+x v
g


v
avg
=xv
g
+(1 x)v
f
=v
f
+x(v
g
v
f
) =v
f
+xv
fg


so x =(v
avg
v
f
)/v
fg


113

The energy functions can also be written as a sum in the saturation region, i.e.,


h =h
f
+x(h
g
h
f
) =h
f
+xh
fg
,


where h
fg
is referred to as the enthalpy of vaporization.


Reference State and Reference Values

The values of the energy functions (u, h, etc.) cannot be measured directly, only the changes in these properties. So
we need to choose a reference stateand assign a value of zero at that state. For water, the state of saturated liquid
at 0.01C is taken as the reference state.

Note that some tables choose a different reference point for u = 0 and h = 0 and so mixing property values from
different tables should be avoided.

114

Approximations for liquids:

Specific volume and internal energy are not very sensitive to p, so the following approximations are reasonable for
engineering calculations:


So if compressed liquid tables are not available, the specific volume and
internal energy in the subcooled region can be estimated to a good
approximation by using saturation values for a saturated liquid at the
same temperature.




v T,p ~ v
f
T ; u T,p ~ u
f
T
andsinceh u+pv, h T,p ~ u
f
T +pv
f
T
115

Incompressible Assumption:

To simplify evaluations involving liquids and solids, it is often assumed that the specific volume (or density) is
constant and the specific internal energy is assumed to vary only with temperature. A substance idealized in this way
is called incompressible, i.e., in summary for an incompressible substance

(1) =1/v =constant and

(2) u =u(T) only


In this case

Enthalpy varies with p and T:

So since v is constant for an incompressible substance,



c
v
=
du
dT

h T, p =uT +pv

c
p
=
ch
cT
p
=
du
dT
=c
v
116
Hence

And if c is taken as a constant, then for an incompressible substance













c
v
=c
p
=c

Au=cAT
Ah=cAT +vAp
117

Example 1:
Water vapor at 3.0 MPa and 300C (state 1) is cooled at constant volume to 200C (state 2), then compressed
isothermally to 2.5 MPa (state 3).

(a) Find states 1, 2 and 3 on a p-v diagram.
(b) Find v
1
, v
2
, v
3
, and x
2
.



118
119

120
Example 2:
Water is contained in a piston-cylinder assembly at (p, T) = (10 bar, 400C).

Process 1-2: water cooled at constant pressure to saturation conditions.
Process 2-3: cool at constant volume to 150C.

(a) Sketch processes on p-v, p-T and T-v diagrams.
(b) Find work and heat transfer, per unit mass.


















121

Is Water Vapour an Ideal Gas?

Yes, but only for certain regions
(relatively low pressures and away from
the 2-phase region).

To the right is shown the % error in the
specific volume comparing the steam
tables with the ideal gas assumption:




122
Compressibility Factor, Z

The dimensionless ration pv/RT is called the compressibility factor,
Z and it gives a measure of the divergence from ideal gas
behaviour.

When the compressibility factor is plotted versus reduced pressure
for a given reduced temperature, where

p
R
= p/p
c
and T
R
= T/T
c

also define a pseudo-reduced volume
c
c
R
p
T
R
v
v =
'


the results for most gases coincide (for 30 different gases, the deviation from the average is at most on the order of
5% and for most ranges is much less). This is referred to as the principle of corresponding states .

The chart produced is referred to as a generalized compressibility chart.



123
Generalized Compressibility Chart


124

Ideal Gas Tables

For small changes of temperature, we can assume that c
v
and c
p
are
constant, and find Ah = c
p
AT. However, in general, c
v
and c
p
are a
function of T - polynomial functions for c
p
(T) are given in Table A-2 of
the text (Cengel & Boles), and an integral must be performed. For
example, if we take h = 0 at T
ref
= 0 K, then



For air, Table A-17 in the text gives values of h and u,
calculated using the above integral. Ideal gas tables should
be used to obtain more accurate values for Ah and Au for
problems involving large changes in temperature (e.g.,
problems involving combusting gases).


hT = c T dT
0
T
1

Supplementary Reading: Heat and Work

Excerpt from Thermodynamics by Herbert Callen

It will be noted that we use the terms heat and heat flux interchangeably. Heat, like work, is only
a form of energy transfer. Once energy is transferred to a system, either as heat or as work, it is
indistinguishable from energy which might have been transferred differently. Thus, although oQ and
oW add together to give dU, there are no quantities Q nor W which have any separate meanings. The
infinitessimal quantity oW is not a differential of some hypothetical function W, and to avoid this
implication we use the symbol o. This is true also of the quantity oQ. Mathematically, infinitesimals
such as oW and oQ are called imperfect differentials.
The concepts of heat, work, and energy may possibly be clarified in terms of a simple analogy.
A certain gentleman owns a little pond, fed by one stream and drained by another. The pond also
receives water from an occasional rainfall and loses it by evaporation, which we shall consider as
negative rain. In the analogy we wish to pursue the pond is our system, the water within it is the
internal energy, water transferred by the streams is work, and water transferred as rain is heat.
The first thing to be noted is that no examination of the pond at any time can indicate how much
of the water within it came by way of the stream and how much came by way of rain. The term rain
refers only to a method of water transfer.
Let us suppose that the owner of the pond wishes to measure the amount of water in the pond.
He can purchase flow meters to be inserted in the streams, and with these flow meters he can measure
the amount of stream water entering and leaving the pond. But he cannot purchase a rain meter.
However, he can throw a tarpaulin over the pond, enclosing the pond in a wall impermeable to rain (an
adiabatic wall). The pond owner consequently puts a vertical pole into the pond, covers the pond with
his tarpaulin, and inserts his flow meters into the streams. By damming one stream and then the other,
he varies the level in the pond at will, and by consulting his flow meters he is able to calibrate the pond
level, as read on his vertical stick, with total water content (U). Thus, by carrying out processes on the
system enclosed by an adiabatic wall, he is able to measure the total water content of any state of his
pond.
Our obliging pond owner now removes his tarpaulin to permit rain as well as stream water to
enter and leave the pond. He is then asked to ascertain the amount of rain entering his pond during a
particular day. He proceeds simply: he reads the difference in water content from his vertical stick, and
from this he deducts the total flux of stream water, as registered by his flow meters. The difference is a
quantitative measure of the rain. The strict analogy of each of these procedures with the thermodynamic
counterparts is evident.
Since work and heat refer to particular modes of energy transfer, each is measure in energy units.