B51EQ1 - APPLIED THERMODYNAMICS

ENTROPY AND AVAILABILITY

The Available Energy of system is the energy which can be converted to work when the
system is brought into equilibrium with the surroundings. The First Law of
Thermodynamics tells us that Energy is conserved, the Second Law of
Thermodynamics tells us that, if a process is not reversible, then the Available Energy
of the Universe must decrease. We can use the loss of Available Energy as a measure of
how irreversible a process is.
First we will look at an example
Let us consider a system comprising 5kg of water which cools from 100OC to 80oC,
transferring heat to the environment at 20oC.
Calculate:
(a) The change in entropy of the system
(b) The change in entropy of the Universe
(c) The lost opportunity to do work
(d) The change in the parameter (U-ToS) for the system
(e) The value of ToSuniverse
(a) There is negligible change in volume of the system, therefore we can say:
T
353
Ssystem mc ln 2 5x4..19x ln

373
T1
1155
. kJ / K

(b) For the surroundings, all heat is received at To, Therefore:

Q
T
Q U system mc T2 T1

S surr

419kJ
419
1.430
293
S system

S surr
S universe S surr

1.430 1.155 0.275kJ / K

(c) To evaluate the lost opportunity to do work we must consider the work which
would be done if we were to transfer heat to the environment reversibly. We therefore
imagine a reversible heat engine linking the system to the environment.

T h e S y s te m
3 7 3 -3 5 3 K
Q in

out

Q out
S U R R O U N D IN G S
293K
The work produced by the imaginary engine, R, is the work for which, by allowing the
system to cool, we have missed the opportunity to produce.
Consider an infinitesimal heat transfer to R
dW out dQin dQout

dWout
T
rev 1 o
dQin
Tsys
dQin mc dTsys

(Note : - ve dTsys leads to + ve dQin )

Combining the above:

T
dWout 1 o

Tsys

mc dTsys

T
Wout 1 o

Tsys
1

mc dTsys

T
mc T2 T1 To ln 2
T1

353

mc 353 373 293 ln

373

81kJ

(c) The change in U T0S for the system is given by:

U T0 S U 2 U1 T0 S2 S1
419 293 1155
.

81kJ

(d) The value of ToSuniverse may be calculated directly

T0Suniverse 293 x 0.275

81kJ

Examination of the calculations involved shows that the formulae used in calculating
the answers in (c), (d), and (e) above are all identical so it is unsurprising that all yield
the same answer. Let us now examine whether we can use this result in a more general
fashion.

Non-Flow Availability
The above example involved a closed system at constant volume (and, by implication,
pressure). Let us now consider a system which can change in pressure and volume.
The system is initially at condition 1 and we shall consider the work which it could do
if it reversibly moved into equilibrium with the surroundings at To and po.
V
The System

Qin

Wout,e
Qout

SURROUNDINGS
To,Po
The First Law applied to a closed system tells us, for our system including the
reversible engine R,:
Wout U 0 U 1 Q
However, Wout comprises the work output from the reversible engine and the expansion
work done by the system. A portion, W*out, of the expansion work is used to displace
the surroundings as the system expands from V1 to V0 and is therefore of no use to us:
'
Wout
p 0 Vo V1
Therefore, the useful work, Wout, is given by:
'
Wout
U o U 1 Q p 0 V0 V1
In order to determine the value of Q, the heat interaction with the system (again, our
system includes the hypothetical reversible engine, therefore Q is numerically
equivalent to the heat rejected by the engine, Qout but is negative.) we can invoke the
Second Law to state that the entropy of the Universe must increase. Since all heat is
transferred to the surroundings at T0, we can say:
S system

Q
0 (remember heat transferred from the system is - ve)
T0

Q T0 S system

(NOTE because of the sign convention this implies that, for a system initially warmer
than the surroundings, Q is negative and the magnitude of the heat interaction will be
GREATER than or equal to the MINIMUM set by T0 Ssystem)
'
Wout
U 0 U 1 T0 S 0 S 1 p 0 V0 V1

U 1 p 0V1 T0 S 1 U 0 p 0V0 T0 S 0

Which may be written:

Where:

Wmax A1 A0

A U p0V T0S

The parameter A is known as the Non-Flow Availability Function, It is not a property

of the system since it depends not only on the fluid properties, but also on the
conditions of the surroundings. The maximum useful work which a system could
perform in moving from state 1 to state 2 is given by:
Wout Re v A1 A2

(If A2>A1 then work is done on the system, the reversible work is the minimum work
which must be done)
If the work output during a process 1-2 is less than A1-A2 then there is a loss of
Available Energy equal to (A1-A2)-Wout
Steady Flow Availability
Let us consider a steady flow of fluid which is brought from an initial state 1 to
equilibrium with the surroundings (state 0). We can apply the steady flow energy
equation:

12 mC12 mgz1 H 0 mgz0 Q Wout

Neglecting KE and PE:

Wout H1 H 0 Q

0
R

S U R R O U N D IN G S

We will consider the fluid expanding through a reversible adiabatic turbine to po and
then being cooled to T0 by heat exchange through a series of reversible heat engines.
it can be shown that:

Wout H 1 H 01 T0 S 0 S1

Wout ,max H 1 T0 S1 H 0 T0 S 0
B1 B0
B H T0S is the Steady Flow Availability Function
Loss of Available Energy due to Irreversibility
Consider a steady flow process:
If the process is reversible:
B1 B2 Wout ,rev

H1 H 2 T0 S1 S 2

(Note : S1 S 2 S sys )

Wout ,rev H1 H 2 T0 S sys

Applying the steady flow energy equation (neglecting P.E. and K.E.)

H1 H 2 Qrev

And for the surroundings:

S surr

Wout ,rev

Qrev
T0

H1 H 2 T0 (S surr ) Wout ,rev

Equating expressions for Wout,rev leads to:

H1 H2 T0 Ssys

H1 H2 T0 Ssurr

Ssys Ssurr
Ssys Ssurr Suniverse 0

This is what we expect for a reversible process.

Now let us consider an irreversible process:
H1 H 2 Qirrev Wout ,irrev
S surr

H1 H 2 S surr

Qirrev
T0

Wout ,irrev

Remembering that, for the ideal or reversible process:

Wout , rev H1 H 2 T0 S sys

We can say that the loss in available work during an irreversible process is given by:
Wout , rev Wout , irrev H1 H 2 T0 S sys H1 H 2 T0 S surr
T0 S sys S surr
T0 Suniv

This is a general case:

The loss in available work due to irreversibility

is given by T0Suniv

Exergy
The term exergy is frequently used to describe the useful work which could be
extracted if the system was brought to thermal and mechanical equilibrium with the
surroundings:
Non- flow exergy in state 1, n1 U1 p0V1 T0S1 U0 p0V0 T0S0
A1 A0
Steady- flow exergy in state 1, f 1 H1 T0S1 H0 T0S0
B1 B0

The term anergy has been used, but not commonly, to describe that portion of the
energy of a system which cannot be converted into work, for the steady-flow case.
anergy = enthalpy - exergy
Examples:
Non-Flow
(i) 1 kg of steam at 10 bar, 300oC is contained in the cylinder of a reciprocating engine.
It is expanded irreversibly until the pressure in the cylinder is 1 bar. During the
expansion the steam does a total of 200kJ of work on the surroundings and rejects
150kJ of heat to the surroundings. The surroundings are at 1bar, 15oC.
Calculate the loss of available energy in the process.
(ii) Calculate the non-flow exergy of an ice block, mass 1kg, in an environment at
(a) 25oC
(b) 0+oC
in both cases the block and surroundings are at 1 bar.

Steady-flow
(iii)In the compressor of a gas turbine 50kg/s of air is compressed with a pressure ratio
15:1, isentropic efficiency 90%, from atmospheric conditions of 10oC, 1 bar. Kinetic
energy changes may be neglected. Calculate the rate of gain of available energy of the
air during the compression and the overall loss of available power.
(iv) Calculate the steady flow specific exergy of:
(a) Saturated Water at 100oC
(b) Saturated Steam at 100oC
(c) Saturated R12 liquid at -30oC
(d) Saturated R12 vapour at -30oC
The surroundings are at -30oC, and at approximately 1 bar (i.e. at the saturation
pressure of the fluid)