AVAILABILITY AND IRREVERSIBILITY

The second law of thermodynamics puts limit on the conversion of a certain amount of heat
into work. Complete conversion of heat into work is not possible. A portion of the heat
supplied to any engine must be rejected. This implies that no heat engine can have an
efficiency equal to 100%. On the contrary, the electrical energy can be completely converted
into mechanical work without any loss (neglecting friction and turbulence effects). The
different sources of energy may therefore be divided into two
i. High grade energy: this is the energy that can be completely transformed into shaft
work without any loss and hence fully utilizable. Examples include mechanical and
electrical work; water, wind and tidal power; kinetic energy of jets; animal and
manual power.
ii. Low grade energy: this is the energy which only a certain portion can be converted
into mechanical or shaft work. Examples are heat or thermal energy; heat from
nuclear fusion or fission; heat from combustion of fuels such as coal, wood, oil etc.
Available and Unavailable Energy
The portion of thermal energy input in cyclic engine which gets converted into mechanical
work is referred to as available energy. The portion of thermal energy which is not utilizable
and rejected to the sink (surrounding) is called unavailable energy.
The term exergy and anergy are synonymous with available and unavailable energy
respectively. Therefore,
Energy = exergy + anergy
The lower the temperature at which heat is rejected, the lesser would be the amount of heat
rejected and the more would be the work output for a given amount of heat supplied. Lower
temperature corresponds to the temperature of the atmosphere or a large mass of water
(ocean). The available work for a system becomes maximum when its state is brought in
equilibrium to the state of the surroundings. This maximum work is known as availability
which may be defined as the maximum work available when a system comes to equilibrium
with its environment by means of work and heat transfer, Availability is therefore composite
property depending on the state of both the system and surroundings.
When the system comes to complete equilibrium with its environment, all intensive and
specific properties will be common, and no energy difference will exist to promote further
work. Such a state of system is called dead state. The concept of dead state of a system
implies that:
i. The system is stable and uniform in composition
ii. Its pressure and temperature are equal to that of the surroundings
iii. The system has a zero velocity and minimum potential energy
The dead state is designated by affixing the subscript ‘0’ to the properties.
Any change in the state of the system from the dead state is a measure of the available work
that can be obtained from it. The farther a system is from its dead state (either above or
below), the higher will be the available energy. Available work of system decreases as a
system approaches the dead state.
 Pressure

When the system is reduced in state to temperature To of the environment, its capacity to do
work by utilizing the temperature difference ceases and its available energy become zero.
Similar situation of zero available energy prevails when the pressure and potential heads of
the system are reduced to the level of the surrounding. The following two cases arise when
considering available and unavailable portion of heat energy.
Case 1: Heat withdrawn at constant temperature
 The figure above represents a reversible heat engine that operates between a constant
temperature reservoir at temperature T and a sink at temperature To. Corresponding to the
heat supplied by the reservoir Q is the available work Wmax which is given by

( )

( )

( )

Where
is the availability on the T-S diagram which is represented by 1-2-3-4. The area 3-4-5-
6 represents the unavailable portion of heat supplied to the engine. In fact, unavailable energy
is the energy rejected from the engine, and hence represents the portion of heat supplied that
cannot be converted into work. The unavailable energy equals the product of the lowest
temperature of heat rejection and the change of entropy of the system during the process o
heat supply (unavailable energy = ).
Case 2: Heat withdrawn at varying temperature
For a finite reservoir, the temperature changes as heat is withdrawn from it and as such, the
supply of heat to the engine is at varying temperature. The analysis is then made by breaking
the process into a series of infinitesimal Carnot cycles each supplying of heat at
temperature T (different for each cycle) and rejecting heat at constant temperature
Maximum amount of work (available energy) then equals

∫( )

∫ ∫

∫ ∫

It is seen that the expressions for both the available and unavailable parts are identical in both
cases
Example
1. Calculate the availability and unavailability of a system that absorbs 15000 kJ of heat
from a heat source at 500 K temperature while the environment is at 290 K temperature.
2. 0.2 kg of air initially at 575 K temperature receives 300 kJ of heat reversibly at constant
pressure. Determine the available and unavailable energies of the heat added. Take cp for
air = 1.005 kJ/kg and temperature of surroundings 300 K.
3. A lump of 800 kg of steel at 1250 K is to be cooled to 500 K. If it is desired to use the
steel as source of energy, calculate the available and unavailable energies. Take specific
heat of steel as 0.5 kJ/kg K and ambient temperature 300 K

Availability of a non-flow or closed system

For piston-cylinder arrangement (closed system) in which the fluid properties at p1,V1, T1
expands reversibly to the environmental state with parameters p0,V0, T0 as shown. The
following energy (work and heat) interactions take place:

- The fluid expands and the expansion work Wexp is obtained. From the principle of
conservation
, therefore,
( )
The heat interaction is negative since heat is leaving the system. Therefore

( )
- The heat rejected by the piston cylinder assembly may be made to run a reversible
heat engine. The output from the reversible heat engine equals
- ( ) ( )

The sum total of the expansion work Wexp and the engine work Weng gives the maximum
work obtainable from the arrangement
[( ) ] [ ( )]
( ) ( )
The piston moving outwards has to expend work in pushing the atmosphere against its own
pressure. The work which may be called the surrounding work, is simply dissipated nd as
such not useful. It is given by
( )
The energy available for work transfer less the work absorbed in moving the environment is
called the useful work or net work. Therefore the maximum available useful or net work is
given by

( ) ( ) ( )
( ) ( )

Where ( ) is known as the non-flow availability function. It is a

composite property of the system and surroundings as it consists of three extensive properties
of the system (U, V and S) and two intensive properties (( ).
When the system undergoes a change from state 1to state 2 without reaching the dead state,
then
( ) ( ) ( )
It is worth noting that availability is a function of the properties of the surroundings as well as
the end states of the closed system.
The changes in entropy for the closed system are calculated from the property relation

Integrating between the initial and final states, we obtain

∫ ∫ ∫

∫ ∫ since

Therefore,

Example
One kg of air is contained in a piston cylinder assembly at 10 bar pressure and 500K
temperature. The piston moves outwards and the air expands at 2 bar pressure and 350K
temperature. Make calculations for the following:
i. Availability in the initial and final states
ii. The maximum useful work
Assume that the system is insulated and the environmental conditions are at 1 bar 290K.
Further information for air are R = 0,287 kJ/kgK, cv = 0.718 kJ/kg K, and cp = 1.005 kJ/kg K
Availability of a steady flow system
Consider a steady flow system and assume that the flowing fluid has the following
characteristics:
Internal energy U, specific volume v, specific enthalpy h, pressure p, velocity C and location
z.

The properties of the fluid would change when flowing through the system. Let the subscript
1 indicate the parameters of the system at the inlet and 2 designate the parameters at the
outlet. Further let Q units of heat be rejected and Ws unit of work. The steady flow energy
equation may be written as

Eliminating potential energy and kinetic energy

Therefore, shaft work ( )

The heat rejected by the system may be used to run a reversible heat engine which is given by

( ) ( )

Maximum available useful work or net work is given by

( ) ( )
( ) ( )
The quantity ( ) is called the steady state availability function. It is a composite
function of the system and the surrounding involving extensive properties H and S of the
system and intensive property of the surrounding. Alternative names for the term are the
Darrieus function and the Keenam function.
When the system changes from state 1 to some intermediate state 2, the change in steady flow
availability function is given by
( ) ( )
The changes in entropy for steady flow can be calculated from the property relation

Integrating between the initial and final states, we obtain

∫ ∫ ∫

∫ ∫ since

Therefore,

Example
A single stage air turbine is to operate with an inlet pressure and temperature of 6 bar and 800
K. the outlet pressure and temperature are 1.0 bar and 500 K. During expansion, the turbine
losses 25 kJ/kg to the surroundings which are at 1 bar and 300 K. For a unit mass flow rate,
determine the decreased availability, the maximum work and reversibility. For air, take cp =
1.005 kJ/kg K and R = 0,287 kJ/kgK
Effectiveness and Irreversibility
The concept of availability leads to the following parameters which are helpful in the
assessment of a process or cycle
i. Effectiveness: this represents the fraction of maximum useful work (Wu)max actually
utilized and it is expressed as a ratio of useful work Wu to the maximum useful work
(Wu)max. During cooling or expansion process (i.e. work producing), the work
produced is at the expense of loss of availability of the system, and the work produced
increases the availability of the environment which is the objective.
( )

All of the work performed by a system is not available for delivery; a certain portion
of it has to be spent in pushing out the atmosphere. The work done on the atmosphere
equals p0dv where p0 is the atmospheric pressure and dV is the change in volume

Also, the maximum useful work is given by

 ( ) in a steady flow
For a reversible process,
( ) Implying that effectiveness is unity
For heating or compression process

ii. Irreversibility: this denotes the loss of work due to the fact that all real processes are
irreversible, and is defined as the difference between maximum work output from the
system and the expansion work. That is
[( ) ( )] [ ( )]
( )

Change in entropy of environment due to addition of heat Q at constant atmospheric

temperature
( ) ( )

Note that the sign convention for heat interaction is negative for the system but
positive for the surroundings
[( ) ( ) ]
( )
( )

Similarly, for steady flow process.

[( ) ( )] [( ) ]
( ) #
( ) ( )
(( ) ( ) )
( ) ( )

From above, the same expression for irreversibility apply to both to flow and non-
flow processes, and it prescribes that irreversibility is equal the product of
temperature of surroundings and entropy production. The quantity ( ) also
represents an increase in unavailable energy (anergy) and can be stated that
irreversibility mounts to increase in anergy.
In terms of rate of loss of energy, we can write irreversibility I as
( )

This is referred to as the Gouy-stodola equation. There would be minimum exergy

loss with minimum rate of entropy generation in a thermodynamically efficient
process.
Example
One kg of air is heated from 25°C to 50 °C by mixing it with certain quantity of air t
120°C. Assuming the mixing process to be adiabatic and neglecting changes in kinetic
and potential energies, evaluate the mass of heating air and effectiveness of heating
process. Take cp = 1.005 kJ/kg K and ambient temperature to be 20°C.