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Availability and Irreversibility

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Simple Combustion

from a particular device, given a

specific amount of fuel?

Automobile Engine

Fuel Cell

Dr. Rohit Singh Lather

provided by availability analyses

Introduction

There are many forms in which an energy can exist. But even under ideal conditions all these

forms cannot be converted completely into work. This indicates that energy has two parts :

- Available part

- Unavailable part

Available energy or Exergy: is the maximum portion of energy which could be converted into

useful work by ideal processes which reduce the system to a dead state (a state in equilibrium

with the earth and its atmosphere).

- There can be only one value for maximum work which the system alone could do while descending

to its dead state, therefore 'Available energy is a property

Unavailable energy or Anergy: is the portion of energy which could not be converted into useful

work and is rejected to the surroundings

Dr. Rohit Singh Lather

A system which has a pressure difference from that of surroundings, work can be obtained from

an expansion process, and if the system has a different temperature, heat can be transferred to

a cycle and work can be obtained. But when the temperature and pressure becomes equal to that

of the earth, transfer of energy ceases, and although the system contains internal energy, this

energy is unavailable

Summarily available energy denote, the latent capability of energy to do work, and in this sense it

can be applied to energy in the system or in the surroundings.

The theoretical maximum amount of work which can be obtained from a system at any state p1 and

T1 when operating with a reservoir at the constant pressure and temperature p0 and T0 is called

availability.

First Law of Thermodynamics (law of energy conservation) used for may analyses performed

Second Law of Thermodynamics simply through its derived property - entropy (S)

Other Second Law properties my be defined to measure the maximum amounts of work

achievable from certain systems

This section considers how the maximum amount of work available from a system, when

interacting with surroundings, can be estimated

All the energy in a system cannot be converted to work: the Second Law stated that it is

impossible to construct a heat engine that does not reject energy to the surroundings

For stability of any system it is necessary and sufficient that, in all possible variations of

the state of the system which do not alter its energy, the variation of entropy shall be

negative

This can be stated mathematically as S < 0

It can be seen that the statements of equilibrium based on energy and entropy, namely E > 0

and S < 0

System A, which is a general system of constant composition in which the work output, W, can

be either shaft or displacement work, or a combination of both

System B

System A

po

Q

ER

Qo

Thermal Reservoir To

Dr. Rohit Singh Lather

For a specified change of state these quantities, which are changes in properties, would be

independent of the process or work done. Applying the First Law of Thermodynamics to System A

gives

W = - dE + Q

If the heat engine (ER,) and System A are considered to constitute another system, System B, then,

applying the First Law of Thermodynamics to System B gives

Wnet = W + WR

Since the heat engine is internally reversible, and the entropy flow on either side is equal, then

$%&

'&

and the change in entropy of System A during this process, because it is reversible, is dS =

Wnet = - d(E ToS)

Wnet = - E + TodS

Dr. Rohit Singh Lather

$%

'

In the absence of motion and gravitational effects the energy, E, may be replaced by the intrinsic

internal energy, U, giving Wnet= -d(U - ToS)

The changes executed were considered to be reversible and Wnet was the net work obtained

from System B (i.e. System A + heat engine ER).Thus, Wnet must be the maximum quantity of

work that can be obtained from the combined system

The expression for W is called the change in the Helmholtz energy, where the Helmholtz energy

is defined as

F = U - TS

- Helmholtz energy is a property which has the units of energy, and indicates the maximum work

that can be obtained from a system

- It can be seen that this is less than the internal energy, U

- Product TS is a measure of the unavailable energy

Dr. Rohit Singh Lather

The change in Helmholtz energy is the maximum work that can be obtained from a closed system

undergoing a reversible process whilst remaining in temperature equilibrium with its surroundings

A decrease in Helmholtz energy corresponds to an increase in entropy, hence the minimum value

of the function signifies the equilibrium condition

A decrease in entropy corresponds to an increase in F; hence the criterion dF > 0 is that for

stability

-This criterion corresponds to work being done on the system

- For a constant volume system in which W = 0, dF = 0

For reversible processes, F1 = F2; for all other processes there is a decrease in Helmholtz energy

System A could change its volume by V, and while it is doing this it must perform work on the

atmosphere equivalent to po V, where po is the pressure of the atmosphere. This work detracts

from the work previously calculated and gives the maximum useful work, as Wu = Wnet - PodV

if the system is in pressure equilibrium with surroundings.

Wu = -d(E- ToS) podV

= -d(E + poV - ToS) because po= constant

Hence Wu = -d(H - ToS)

The quantity H - TS is called the Gibbs energy, Gibbs potential, or the Gibbs function, G

Hence G = H - TS

- Gibbs energy is a property which has the units of energy

- Indicates the maximum useful work that can be obtained from a system

- It can be seen that this is less than the enthalpy

Dr. Rohit Singh Lather

The change in Gibbs energy is the maximum useful work that can be obtained from a system

undergoing a reversible process whilst remaining in pressure and temperature equilibrium with its

surroundings

The equilibrium condition for the constraints of constant pressure and temperature can be

defined as:

dG)PT < 0

Spontaneous change

dG)PT= 0

Equilibrium

AG)PT > 0

Criterion of stability

Displacement Work

The work done by a system can be considered to be made up of two parts: that done against a

resisting force and that done against the environment.

The pressure inside the system, p, is resisted by a force, F, and the pressure of the environment.

Hence, for System A, which is in equilibrium with the surroundings p.A = F + po.d

System A

p

po

If the piston moves distance dx, then work done by various components p.A.dx = F.dx + po.A. dx

where P.A. dx= p dV = W = work done by the fluid in the system

poA.dx = podV = W = work done against the surroundings

Dr. Rohit Singh Lather

Hence the work done by the system is not all converted into useful work, but some of it is used to do

displacement work against the surroundings, i.e.

which can be rearranged to give

This concept will now be generalized to consider all the possible work outputs from a system that is not in

thermodynamic and mechanical equilibrium with its surroundings (i.e. not at the ambient, or dead state,

System B

conditions)

po

WS + WR = - (dU TodS)

System A

closed system is

ER

(i.e. po and To are constant) dA can be integrated to give

A = U + po V - TOS

Qo

Thermal Reservoir To

- It is a combination of properties

- A is not itself a property because it is defined in relation to the arbitrary datum values of po and

To

- It is not possible to tabulate values of A without defining both these datum levels

- The datum levels are what differentiates A from Gibbs energy G

- The maximum useful work achievable from a system changing state from 1 to 2 is given by

Wmax = A= -(A2 - Al) = Al - A2

- The specific availability, a , i.e. the availability per unit mass is

a = u + p ov - T os

- If the value of a were based on unit amount of substance (i.e. kmol) it would be referred to as

the molar availability

a = a2 - a1 = (u2 + pov2 - Tos2)- (u1 + pov1-Tos1)

= ( h2 + v2(Po-P2) - (h1+ V1(Po P1)) -To(S2 - S1)

Dr. Rohit Singh Lather

Consider a steady flow system and let it be assumed that the flowing fluid has the following

properties and characteristics; Internal energy u, specific volume v, specific enthalpy h, pressure

p, velocity c and location z

System delivers a work output W units

Inlet

P1,V1,T1

Control

Volume

Outlet

P2,V2,T2

Carnot Engine

WEngine

To(S1 S2)

Dr. Rohit Singh Lather

V12

V22

U1 + p11 +

+ gz1 Q = U2 + p22 +

+ gz2 + Ws

2

2

Neglecting the kinetic and potential energy changes

U1 + p11 Q = U2 + p22 + Ws

H1 Q = H2 + Ws

Shaft work Ws = H1 H2 Q

Heat Q rejected by the system may be made to run a reversible heat engine, the output from the

engine equals

'

Wengine = Q (1

&

'C

= Q To (S1 S2)

= H1 H2 Q + Q To (S1 S2)

Dr. Rohit Singh Lather

= H1 H2 Q + Q To (S1 S2)

= H1 To S1 (H2 ToS2)

= B1 B2

and the Keenam function

Clearly, the availability B is a state function in the strictest mathematical sense so the maximum

(or minimum) work associated with any steady state process is also independent of the path

Availability: Yields the maximum work producing potential or the minimum work requirement of a

process

- Allows evaluation and quantitative comparison of options in a sustainability context

If a certain portion of energy is available then obviously another part is unavailable

- the unavailable part is that which must be thrown away

- Diagram indicates an internally reversible process from a to b

- This can be considered to be made up of an infinite number of strips 1-m-n-4-1 where the

temperature of energy transfer is essentially constant, i.e. T1 = T4 = T

The energy transfer obeys

$%

'

$%&

'&

Where,

Q = heat transferred to system and

Qo= heat rejected from system,

As in an engine (ER) undergoing an infinitesimal Carnot cycle

- In reality Q0 is the minimum amount of heat that can be rejected

because processes 1 to 2 and 3 to 4 are both isentropic, i.e.

adiabatic and reversible

Dr. Rohit Singh Lather

= = T

L%

'

ToS

Note that the quantity of energy, Q, can be written as a definite integral because the process is an

isentropic (reversible) one

Consider the energy transfer from a high temperature reservoir at TH through a heat engine (not

necessarily reversible)

Temperature

Thermal Reservoir TH

The available energy flow

from the hot reservoir is

EH = QH -To SH

QH

TH

SH

W = QH - Qo

A

To

-Qo

I

So

Entropy

Dr. Rohit Singh Lather

Q

&

Eirrev = EH - W = QH- To .SH - W

= QH To . SH - (QH - Qo) = Qo - To .SH

= To(S0- SH)

%

In the case of a reversible engine = 0 because entropy flow is conserved, i.e. ' Q = ' &

Q

&

Hence the unavailable energy for a reversible engine is To SH while the irreversibility is zero

The available energy is depicted by the area marked A, while the energy lost due to

irreversibility is denoted I and is defined Eirrev = To(S0 - SH)

Irreversibility

The entropy of a system plus its surroundings (i.e. an isolated system) can never decrease (2nd

law).

where, = final - initial > 0 irreversible (real world)

= 0 reversible (frictionless, ideal)

In an ideal case if Q is the heat supplied from a source at T, its availability or the maximum work

it can deliver is Q(1-T0/T1) where T0 is the temperature of the surroundings.

- Invariably it will be less than this value.

- The difference is termed as irreversibility.

- Availability = Maximum possible work - Irreversibility

Wuseful = Wrev - I

Dr. Rohit Singh Lather

Irreversibility can also be construed as the amount of work to be done to restore the system to

the original state.

- Eg: If air at 10 bar is throttled to 1 bar, the irreversibility will be p.v ln (10) which is the work

required to get 10 bar back.

- Here p is 1 bar and v is the specific volume at this condition.

- Note that the system has been restored to the original state but not the surroundings

- Therefore increase in entropy will be R ln 10.

TdS u + W

- It implies that the amount of heat energy to be supplied in a real process is larger than the

thermodynamic limit

Reversible Processes do not effect the entropy of the universe

Impossible Processes decrease the entropy of the universe

S universe = 0

SUniverse = SSystem + SSurroundings

When the entropy of the universe goes so high, then some one has to come and set it right

HE SAYS HE WILL COME

Every religion confirms this

When heat Q is transferred from a finite source, the temperature does not remain constant and

decreases as the flow of heat to the engine starts

- Heat supplied at varying temperature

- The change in entropy (S2 S1) is calculated by integration as the temperature varies during

the heat transfer

Eav = Q - Eunav =Q T.dS

Consider certain quantity of heat Q is transferred from a system at constant temperature T1 to

another system at constant temperature T2 (T1 > T2)

'&

Eav2 = Q (1 )

'S

T1

'&

'&

= Q (1 ) - Q (1 )

'C

'S

%

%

= To ( )

'S 'C

This total change is called

entropy of universe or

entropy production

Temperature

T2

To

SH

f

e

c

= To (dS1 + dS2)

= To (dS)net

So

Dr. Rohit Singh Lather

Entropy

abcd is the power cycle when heat available at T1 and area under cd represents the unavailable

energy

efgd is the power cycle when the heat is available at T2 and area under dg represents the

unavailable energy

Increase in the unavailable energy due to irreversible heat transfer is then represented by the

dark area under cg and given by To ( ambient temperature) and net increase in entropy of the

interacting systems

Loss of available energy when heat transferred through finite temperature difference

Greater temperature difference, more increase in entropy

The concept of available energy provides the measure of quality of energy

Energy is degraded each time it floes through a finite temperature difference (law of energy

degradation)

The approaches derived previously work very well when it is possible to define the changes

occurring inside the system

However, it is not always possible to do this and it is useful to derive a method for evaluating the

change of availability from external parameters

If a closed system goes from state 1 to state 2 by executing a process then the changes in that

system are

S

S $%

'

S

= U 1

+ 2 1

Dr. Rohit Singh Lather

A2

S

A1= C

'&

1 '

+ 2 1

Availability transfer

accompanying

Heat Transfer

A2 A1= C 1

'&

'

Availability

transfer

accompanying

Work

Availability

destruction due to

Irreversibilities

+ 2 1

= U 1

+

= U 1

+

= 1

+

The effect of combustion 'on the availability of the system

The energy content of the universe is constant, just as its mass content is

We are always told how to conserve energy

As engineers, we know that energy is already conserved

What is not conserved is exergy, which is the useful work potential of the energy

Once the exergy is wasted, it can never be recovered

When we use energy (to heat our homes, for example), we are not destroying any energy; we are merely

converting it to a less useful form, a form of less exergy

Exergy and the Dead State

The useful work potential of a system is the amount of energy we extract as useful work

The useful work potential of a system at the specified state is called exergy

Exergy is a property and is associated with the state of the system and the environment

A system that is in equilibrium with its surroundings has zero exergy and is said to be at the dead state

The exergy of the thermal energy of thermal reservoirs is equivalent to the work output of a Carnot heat

engine operating between the reservoir and the environment

complete equilibrium with the surrounding

Pressure

1

Avalability

occur

Deas State implies that

- System is stable and uniform in composition

Avalability

Dead

State

P0

Isotherm at T0

Volume

The total useful work delivered as the system undergoes a reversible process from the given

state to the dead state (that is when a system is in thermodynamic equilibrium with the

environment), which is Work potential by definition

Work Potential = Wuseful = Wmax - P0(V0 - V1)

The work potential of internal energy (or a closed system) is either positive or zero, never

negative

The useful work potential of enthalpy can be expressed on a unit mass basis as:

here ho and so are the enthalpy and entropy of the fluid at the dead state

Reversible Work

Reversible work Wrev is defined as the maximum amount of useful work that can be produced (or

the minimum work that needs to be supplied) as a system undergoes a process between the

specified initial and final states

- This is the useful work output (or input) obtained when the process between the initial and final

states is executed in a totally reversible manner

Irreversibility

The difference between the reversible work Wrev and the useful work Wu is due to the

irreversibilities present during the process and is called the irreversibility I. It is equivalent to

the exergy destroyed and is expressed as

where Sgen is the entropy generated during the process. For a totally reversible process, the useful

and reversible work terms are identical and thus irreversibility is zero

Irreversibility can be viewed as the wasted work potential or the lost opportunity to do work. It represents

the energy that could have been converted to work but was not

Exergy destroyed represents the lost work potential and is also called the wasted work or lost work

When assessing a power cycle we define the first-law efficiency as the quotient of the net work

done by the cycle over the exterior and the heat input to the cycle

As a consequence of the 1st and the 2nd laws of thermodynamics, we get 0 < 1

Energetic efficiency does not behave this way for all energy uses and devices

Heat pumps present first law efficiencies greater than 1, because the energy input does not take

into account the heat input from the environment (the cold reservoir)

- Because the domain of is any positive real number

- the first-law efficiency does not provide a figure of merit in each energy use, but only a

quantification of the amount of energy transferred to a given desired end relative to an input

The second-law efficiency is the widely accepted and used figure of merit for energy use systems

Second-Law Efficiency

performance under reversible conditions for the same end states and is given by

th

Wu

II =

=

th, rev Wrev

other work-consuming devices

COP Wrev

II =

=

COPrev Wu

II =

Exergy recovered

Exergy destroyed

= 1

Exergy supplied

Exergy supplied

II =

dalamijh aeadfg cjnoh

With this definition, as a consequence of the second law of thermodynamics, exergy efficiency is

bonded as 0 II 1, even for refrigerators and heat pumps, and therefore expresses a figure of

the quality and closeness to perfection of a given energy use

Additionally, taking advantage of the concept of exergy, this definition can be reformulated as

II =

= p

actual exergy intake to perform the same task

Its name is due to a figure of merit based in the second law of thermodynamics, measuring for

each process the distance from the theoretical ideal processes that can be measured in terms of

exergy

It presents lower values as higher exergy is destroyed in a process

We want to measure and study the performance of energy uses throughout a country or an

economy and therefore a comparable way of measuring it becomes essential

The comparability of the energy use performance becomes clear when one states the second-law

efficiencies for several different applications

- for desired output of W, Amin = W and A = Wmax

I = Wmax - W

T

Wmax = Q1 (1 - To )

W

II = W

max

W

I = Q

1

II =

W .Wmax

I = W . Q

max

1

Q1 (1 To )

T

I = II carnot

II = I

carnot

T

If heat is involved Amin = Q1 (1 - To )

Dr. Rohit Singh Lather

The general definition of second law efficiency of a process can be obtained in terms of change in

availability during the process:

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