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Exergy

From Wikipedia, the free encyclopedia


"Available energy" redirects here. For the meaning of the term in particle collisions, see Available
energy (particle collision).
In thermodynamics, the exergy of a system is the maximum useful work possible during
a process that brings the system into equilibrium with a heat reservoir.
[1]
When
thesurroundings are the reservoir, exergy is the potential of a system to cause a change as it
achieves equilibrium with its environment. Exergy is the energy that is available to be used. After
the system and surroundings reach equilibrium, the exergy is zero. Determining exergy was also
the first goal of thermodynamics. The term "exergy" was coined in 1956 by Zoran Rant (1904
1972) by using the Greek ex and ergon meaning "from work"
[1][3]
, but the concept was developed
by J. Willard Gibbs in 1873.
[4]

Energy is never destroyed during a process; it changes from one form to another (see First Law
of Thermodynamics). In contrast, exergy accounts for the irreversibility of a process due to
increase in entropy (see Second Law of Thermodynamics). Exergy is always destroyed when a
process involves a temperature change. This destruction is proportional to the entropy increase
of the system together with its surroundings. The destroyed exergy has been
called anergy.
[2]
For an isothermal process, exergy and energy are interchangeable terms, and
there is no anergy.
Exergy analysis is performed in the field of industrial ecology to use energy more efficiently.
Engineers use exergy analysis to optimize applications with physical restrictions, such as
choosing the best use of roof space for solar energy technologies.
[3]
Ecologists and design
engineers often choose a reference state for the reservoir that may be different from the actual
surroundings of the system.
[4]

Exergy is a combination property
[5]
of a system and its environment because it depends on the
state of both the system and environment. The exergy of a system in equilibrium with the
environment is zero. Exergy is neither a thermodynamic property of matter nor a thermodynamic
potential of a system. Exergy and energy both have units of joules. TheInternal Energy of a
system is always measured from a fixed reference state and is therefore always a state function.
Some authors define the exergy of the system to be changed when the environment changes, in
which case it is not a state function. Other writers prefer
[citation needed]
a slightly alternate definition
of the available energy or exergy of a system where the environment is firmly defined, as an
unchangeable absolute reference state, and in this alternate definition exergy becomes a
property of the state of the system alone.
However, from a theoretical point of view, exergy may be defined without reference to any
environment. If the intensive properties of different finitely extended elements of a system differ,
there is always the possibility to extract mechanical work from the system.
[6][7]
Also, it is possible
to formulate the exergetic content of a single body in thermodynamical disequilibrium (with
intensive properties varying with location, such as having a temperature gradient).
[8]

The term exergy is also used, by analogy with its physical definition, in information theory related
to reversible computing. Exergy is also synonymous with: availability, available energy, exergic
energy, essergy (considered archaic), utilizable energy, available useful work, maximum (or
minimum) work, maximum (or minimum) work content, reversible work, and ideal work.
The exergy destruction of a cycle is the sum of the exergy destruction of the processes that
compose that cycle. The exergy destruction of a cycle can also be determined without tracing the
individual processed by considering the entire cycle as a single process and using one of the
exergy destruction equations. ---Information found in thermodynamics by Yunus A. Cengel
Contents
[hide]
1 Mathematical description
o 1.1 An application of the second law of thermodynamics
o 1.2 A historical and cultural tangent
o 1.3 A potential for every thermodynamic situation
o 1.4 Chemical exergy
1.4.1 Important equations
1.4.2 Total exergy
2 Applications
o 2.1 Engineering applications
o 2.2 Applications in natural resource utilization
o 2.3 Applications in sustainability
o 2.4 Assigning one thermodynamically obtained value to an economic good
o 2.5 Implications in the development of complex physical systems
o 2.6 Philosophical and cosmological implications
3 Quality of energy types
o 3.1 Exergy of heat available at a temperature
4 History
o 4.1 Carnot
o 4.2 Gibbs
5 See also
6 Notes
7 References
8 Further reading
9 External links
Mathematical description[edit]
An application of the second law of thermodynamics[edit]
See also: Second law of thermodynamics
Exergy uses system boundaries in a way that is unfamiliar to many. We imagine the presence of
a Carnot engine between the system and its reference environment even though this engine
does not exist in the real world. Its only purpose is to measure the results of a "what-if" scenario
to represent the most efficient work interaction possible between the system and its
surroundings.
If a real-world reference environment is chosen that behaves like an unlimited reservoir that
remains unaltered by the system, then Carnot's speculation about the consequences of a system
heading towards equilibrium with time is addressed by two equivalent mathematical statements.
Let B, the exergy or available work, decrease with time, and S
total
, the entropy of the system and
its reference environment enclosed together in a larger isolated system, increase with time:

For macroscopic systems (above the thermodynamic limit), these statements are both
expressions of the second law of thermodynamics if the following expression is used for
exergy:

where the extensive quantities for the system are: U = Internal energy, V = Volume,
and N
i
= Moles of component i
The intensive quantities for the surroundings are: P
R
= Pressure, T
R
= temperature,
i,
R
= Chemical potential of component i
Individual terms also often have names attached to them: is called "available PV
work", is called "entropic loss" or "heat loss" and the final term is called "available
chemical energy."
Other thermodynamic potentials may be used to replace internal energy so long as
proper care is taken in recognizing which natural variables correspond to which potential.
For the recommended nomenclature of these potentials, see (Alberty, 2001)
[2]
. Equation
(2) is useful for processes where system volume, entropy, and number of moles of
various components change because internal energy is also a function of these variables
and no others.
An alternative definition of internal energy does not separate available chemical potential
from U. This expression is useful (when substituted into equation (1)) for processes
where system volume and entropy change, but no chemical reaction occurs:

In this case a given set of chemicals at a given entropy and volume will have a
single numerical value for this thermodynamic potential. A multi-state system may
complicate or simplify the problem because the Gibbs phase rule predicts that
intensive quantities will no longer be completely independent from each other.
A historical and cultural tangent[edit]
In 1848, William Thomson, 1st Baron Kelvin asked (and immediately answered) the
question:
Is there any principle on which an absolute thermometric scale can be founded? It
appears to me that Carnots theory of the motive power of heat enables us to give an
affirmative answer.
[3]

With the benefit of the hindsight contained in equation (3), we are able to
understand the historical impact of Kelvin's idea on physics. Kelvin suggested
that the best temperature scale would describe a constant ability for a unit of
temperature in the surroundings to alter the available work from Carnot's engine.
From equation (3):

Rudolf Clausius recognized the presence of a proportionality constant in
Kelvin's analysis and gave it the name entropy in 1865 from the Greek for
"transformation" because it describes the quantity of energy lost during
transformation from heat to work. The available work from a Carnot engine
is at its maximum when the surroundings are at a temperature of absolute
zero.
Physicists then, as now, often look at a property with the word "available" or
"utilizable" in its name with a certain unease. The idea of what is available
raises the question of "available to what?" and raises a concern about
whether such a property is anthropocentric. Laws derived using such a
property may not describe the universe but instead describe what people
wish to see.
The field of statistical mechanics (beginning with the work of Ludwig
Boltzmann in developing the Boltzmann equation) relieved many physicists
of this concern. From this discipline, we now know that macroscopic
properties may all be determined from properties on a microscopic scale
where entropy is more "real" than temperature itself (see thermodynamic
temperature). Microscopic kinetic fluctuations among particles cause
entropic loss, and this energy is unavailable for work because these
fluctuations occur randomly in all directions. The anthropocentric act is
taken, in the eyes of some physicists and engineers today, when someone
draws a hypothetical boundary, in fact he says: "This is my system. What
occurs beyond it is surroundings." In this context, exergy is sometimes
described as an anthropocentric property, both by those who use it and
those who don't. Entropy is viewed as a more fundamental property of
matter.
In the field of ecology, the interactions among systems (mostly ecosystems)
and their manipulation of exergy resources is of primary concern. With this
perspective, the answer of "available to what?" is simply: "available to the
system", because ecosystems appear to exist in the real world. With the
viewpoint of systems ecology, a property of matter like absolute entropy is
seen as anthropocentric because it is defined relative to an unobtainable
hypothetical reference system in isolation at absolute zero temperature.
With this emphasis on systems rather than matter, exergy is viewed as a
more fundamental property of a system, and it is entropy that may be
viewed as a co-property of a system with an idealized reference system.
A potential for every thermodynamic situation[edit]
In addition to and , the other thermodynamic potentials are
frequently used to determine exergy. For a given set of chemicals at a given
entropy and pressure, enthalpy His used in the expression:

For a given set of chemicals at a given temperature and
volume, Helmholtz free energy A is used in the expression:

For a given set of chemicals at a given temperature and
pressure, Gibbs free energy G is used in the expression:

The potentials A and G are utilized for a constant temperature
process. In these cases, all energy is free to perform useful
work because there is no entropic loss. A chemical reaction that
generates electricity with no associated change in temperature
will also experience no entropic loss. (See fuel cell.) This is true
of every isothermal process. Examples are gravitational
potential energy, kinetic energy (on a macroscopic scale), solar
energy, electrical energy, and many others.
If friction, absorption, electrical resistance or a similar energy
conversion takes place that releases heat, the impact of that
heat on thermodynamic potentials must be considered, and it is
this impact that decreases the available energy.
Chemical exergy[edit]
Similar to thermomechanical exergy, chemical exergy depends
on the temperature and pressure of a system as well as on the
composition. The key difference in evaluating chemical exergy
versus thermomechanical exergy is that thermomechanical
exergy does not take into account the difference in a system
and environment's chemical composition. If the temperature,
pressure or composition of a system differs from the
environment's state, then the overall system will have exergy.
[9]

The definition of chemical exergy resembles the standard
definition of thermomechanical exergy, but with a few
differences. Chemical exergy is defined as the maximum work
that can be obtained when the considered system is brought
into reaction with reference substances present in the
environment.
[10]
Defining the exergy reference environment is
one of the most vital parts of analyzing chemical exergy. In
general, the environment is defined as the composition of air at
25C and 1 atm of pressure. At these properties air consists of
N
2
=75.67%, O
2
=20.35%, H
2
O(g)=3.12%, CO
2
=0.03% and other
gases=0.83%.
[9]
These molar fractions will become of use when
applying Equation 1 below.
C
a
H
b
O
c
is the substance that is entering a system that one
wants to find the maximum theoretical work of. By using the
following equations, one can calculate the chemical exergy of
the substance in a given system. Below, equation 1 uses the
Gibbs function of the applicable element or compound to
calculate the chemical exergy. Equation 2 is similar but uses
standard molar chemical exergy, which scientists have
determined based on several criteria, including the ambient
temperature and pressure that a system is being analyzed and
the concentration of the most common components.
[11]
These
values can be found in thermodynamic books or in online
tables.
[12]

Important equations[edit]

Where:
Gibbs function of the specific substance in the system
at . ( refers to the substance that is entering the
system)
The Universal gas constant (8.314462 J/molK)
[13]

Temperature that the system is being evaluated at in
absolute temperature
The molar fraction of the given substance in the
environment i.e. air

Where:
The standard molar chemical exergy taken from a table
for the specific conditions that the system is being evaluated
Equation 2 is more commonly used due to the simplicity of only
having to look up the standard chemical exergy for given
substances. Using a standard table works well for most cases,
even if the environment conditions vary slightly, the difference is
most likely negligible.
Total exergy[edit]
After finding the chemical exergy in a given system, one can
find the total exergy by adding it to the thermomechanical
exergy. Depending on the situation, the amount of chemical
exergy added can be very small. If the system being evaluated
involves combustion, the amount of chemical exergy is very
large and necessary to find the total exergy of the system.
Applications[edit]
Applying equation (1) to a subsystem yields:

This expression applies equally well for theoretical ideals in
a wide variety of applications: electrolysis (decrease
in G), galvanic cells and fuel cells (increase
in G), explosives(increase in A), heating and
refrigeration (exchange of H), motors (decrease in U)
and generators (increase in U).
Utilization of the exergy concept often requires careful
consideration of the choice of reference environment
because, as Carnot knew, unlimited reservoirs do not exist
in the real world. A system may be maintained at a constant
temperature to simulate an unlimited reservoir in the lab or
in a factory, but those systems cannot then be isolated from
a larger surrounding environment. However, with a proper
choice of system boundaries, a reasonable constant
reservoir can be imagined. A process sometimes must be
compared to "the most realistic impossibility," and this
invariably involves a certain amount of guesswork.
Engineering applications[edit]
Application of exergy to unit operations in chemical
plants was partially responsible for the huge growth of
the chemical industry during the 20th century. During this
time it was usually called availability or available work.
As a simple example of exergy, air at atmospheric
conditions of temperature, pressure, and
composition contains energy but no exergy when it is
chosen as the thermodynamic reference state known
as ambient. Individual processes on Earth like combustion
in a power plant often eventually result in products that are
incorporated into a large atmosphere, so defining this
reference state for exergy is useful even though the
atmosphere itself is not at equilibrium and is full of long and
short term variations.
If standard ambient conditions are used for calculations
during plant operation when the actual weather is very cold
or hot, then certain parts of a chemical plant might seem to
have an exergy efficiency of greater than 100% and appear
on paper to be a perpetual motion machine! Using actual
conditions will give actual values, but standard ambient
conditions are useful for initial design calculations.
One goal of energy and exergy methods in engineering is to
compute what comes into and out of several possible
designs before a factory is built. Energy input and output
will always balance according to the First Law of
Thermodynamics or the energy conservation principle.
Exergy output will not balance the exergy input for real
processes since a part of the exergy input is always
destroyed according to the Second Law of
Thermodynamics for real processes. After the input and
output are completed, the engineer will often want to select
the most efficient process. An energy efficiency or first law
efficiency will determine the most efficient process based
on wasting as little energy as possible relative to energy
inputs. An exergy efficiency or second-law efficiency will
determine the most efficient process based on wasting and
destroying as little available work as possible from a given
input of available work.
Design engineers have recognized that a higher exergy
efficiency involves superior design and often leads to a
higher return on investment. For example, in the case of
allocating roof space for solar energy collection between
thermal systems and photovoltaic technology, photovoltaic
thermal hybrid solar collector technology provide the
highest exergy efficiency and optimized solution.
[14]

Applications in natural resource
utilization[edit]
In recent decades, utilization of exergy has spread outside
of physics and engineering to the fields of industrial
ecology, ecological economics, systems ecology,
and energetics. Defining where one field ends and the next
begins is a matter of semantics, but applications of exergy
can be placed into rigid categories.
Researchers in ecological economics and environmental
accounting perform exergy-cost analyses in order to
evaluate the impact of human activity on the current natural
environment. As with ambient air, this often requires the
unrealistic substitution of properties from a natural
environment in place of the reference state environment of
Carnot. For example, ecologists and others have developed
reference conditions for the ocean and for the Earth's crust.
Exergy values for human activity using this information can
be useful for comparing policy alternatives based on the
efficiency of utilizing natural resources to perform work.
Typical questions that may be answered are:
Does the human production of one unit of an economic good by method A utilize more of
a resource's exergy than by method B?
Does the human production of economic good A utilize more of a resource's exergy than
the production of good B?
Does the human production of economic good A utilize a resource's exergy more
efficiently than the production of good B?
There has been some progress in
standardizing and applying these methods.
Measuring exergy requires the evaluation of a
systems reference state environment.
[15]
With
respect to the applications of exergy on natural
resource utilization, the process of quantifying
a system requires the assignment of value
(both utilized and potential) to resources that
are not always easily dissected into typical
cost-benefit terms. However, to fully realize the
potential of a system to do work, it is becoming
increasingly imperative to understand exergetic
potential of natural resources,
[16]
and how
human interference alters this potential.
Referencing the inherent qualities of a system
in place of a reference state environment
[15]
is
the most direct way that ecologists determine
the exergy of a natural resource. Specifically, it
is easiest to examine
the thermodynamic properties of a system, and
the reference substances
[17]
that are
acceptable within the reference
environment.
[17]
This determination allows for
the assumption of qualities in a natural state:
deviation from these levels may indicate a
change in the environment caused by outside
sources. There are three kinds of reference
substances that are acceptable, due to their
proliferation on the planet: gases within
the atmosphere, solids within the Earths crust,
and molecules or ionsin seawater.
[15]
By
understanding these basic models, its possible
to determine the exergy of multiple earth
systems interacting, like the effects of solar
radiation on plant life.
[18]
These basic categories
are utilized as the main components of a
reference environment when examining how
exergy can be defined through natural
resources.
Other qualities within a reference state
environment include temperature, pressure,
and any number of combinations of substances
within a defined area.
[15]
Again, the exergy of a
system is determined by the potential of that
system to do work, so it is necessary to
determine the baseline qualities of a system
before it is possible to understand the potential
of that system. The thermodynamic value of a
resource can be found by multiplying the
exergy of the resource by the cost of obtaining
the resource and processing it.
[15]

Today, it is becoming increasingly popular to
analyze the environmental impacts of natural
resource utilization, especially for energy
usage.
[19]
To understand the ramifications of
these practices, exergy is utilized as a tool for
determining the impact potential
of emissions, fuels, and other sources of
energy.
[19]
Combustion of fossil fuels, for
example, is examined with respect to
assessing the environmental impacts of
burning coal, oil, and natural gas. The current
methods for analyzing the emissions from
these three products can be compared to the
process of determining the exergy of the
systems affected; specifically, it is useful to
examine these with regard to the reference
state environment of gases within
the atmosphere.
[16]
In this way, it is easier to
determine how human action is affecting the
natural environment.
Applications in sustainability[edit]
In systems ecology, researchers sometimes
consider the exergy of the current formation of
natural resources from a small number of
exergy inputs (usually solar radiation, tidal
forces, and geothermal heat). This application
not only requires assumptions about reference
states, but it also requires assumptions about
the real environments of the past that might
have been close to those reference states. Can
we decide which is the most "realistic
impossibility" over such a long period of time
when we are only speculating about the
reality?
For instance, comparing oil exergy to coal
exergy using a common reference state would
require geothermal exergy inputs to describe
the transition from biological material to fossil
fuels during millions of years in the Earth's
crust, and solar radiation exergy inputs to
describe the material's history before then
when it was part of the biosphere. This would
need to be carried out mathematically
backwards through time, to a presumed era
when the oil and coal could be assumed to be
receiving the same exergy inputs from these
sources. A speculation about a past
environment is different from assigning a
reference state with respect to known
environments today. Reasonable guesses
about real ancient environments may be made,
but they are untestable guesses, and so some
regard this application as pseudoscience or
pseudo-engineering.
The field describes this accumulated exergy in
a natural resource over time as embodied
energy with units of the "embodied joule" or
"emjoule".
The important application of this research is to
address sustainability issues in a quantitative
fashion through a sustainability measurement:
Does the human production of an economic good deplete the exergy of Earth's natural
resources more quickly than those resources are able to receive exergy?
If so, how does this compare to the depletion caused by producing the same good (or a
different one) using a different set of natural resources?
Assigning one
thermodynamically obtained
value to an economic
good[edit]
A technique proposed by systems
ecologists is to consolidate the three
exergy inputs described in the last
section into the single exergy input of
solar radiation, and to express the total
input of exergy into an economic good
as a solar embodied joule or sej.
(See emergy) Exergy inputs from
solar ^ , tidal, and geothermal forces
all at one time had their origins at the
beginning of the solar system under
conditions which could be chosen as
an initial reference state, and other
speculative reference states could in
theory be traced back to that time.
With this tool we would be able to
answer:
What fraction of the total human depletion of the Earth's exergy is caused by the
production of a particular economic good?
What fraction of the total human and non-human depletion of the Earth's exergy is
caused by the production of a particular economic good?
No additional thermodynamic
laws are required for this idea,
and the principles
of energetics may confuse
many issues for those outside
the field. The combination of
untestable hypotheses,
unfamiliar jargon that
contradicts accepted jargon,
intense advocacy among its
supporters, and some degree
of isolation from other
disciplines have contributed to
this protoscience being
regarded by many as
a pseudoscience. However, its
basic tenets are only a further
utilization of the exergy
concept.
Implications in the
development of
complex physical
systems[edit]
A common hypothesis in
systems ecology is that the
design engineer's observation
that a greater capital
investment is needed to create
a process with increased
exergy efficiency is actually
the economic result of a
fundamental law of nature. By
this view, exergy is the
analogue of economic
currency in the natural world.
The analogy to capital
investment is the accumulation
of exergy into a system over
long periods of time resulting
in embodied energy. The
analogy of capital investment
resulting in a factory with high
exergy efficiency is an
increase in natural
organizational structures with
high exergy efficiency.
(See maximum power).
Researchers in these fields
describe biological evolution in
terms of increases in organism
complexity due to the
requirement for increased
exergy efficiency because of
competition for limited sources
of exergy.
Some biologists have a similar
hypothesis. A biological
system (or a chemical plant)
with a number of intermediate
compartments and
intermediate reactions is more
efficient because the process
is divided up into many small
substeps, and this is closer to
the reversible ideal of an
infinite number
of infinitesimal substeps. Of
course, an excessively large
number of intermediate
compartments comes at a
capital cost that may be too
high.
Testing this idea in living
organisms or ecosystems is
impossible for all practical
purposes because of the large
time scales and small exergy
inputs involved for changes to
take place. However, if this
idea is correct, it would not be
a new fundamental law of
nature. It would simply be
living systems and
ecosystems maximizing their
exergy efficiency by utilizing
laws of thermodynamics
developed in the 19th century.
Philosophical and
cosmological
implications[edit]
Some proponents of utilizing
exergy concepts describe
them as
a biocentric or ecocentric alter
native for terms like quality
and value. The "deep ecology"
movement
viewseconomic usage of these
terms as
an anthropocentric philosophy
which should be discarded. A
possible universal
thermodynamic concept of
value or utility appeals to
those with an interest
in monism.
For some, the end result of
this line of thinking about
tracking exergy into the deep
past is a restatement of
the cosmological
argument that the universe
was once at equilibriumand an
input of exergy from
some First Cause created a
universe full of available work.
Current science is unable to
describe the first
10
43
seconds of the universe
(See Timeline of the Big
Bang). An external reference
state is not able to be defined
for such an event, and
(regardless of its merits), such
an argument may be better
expressed in terms ofentropy.
Quality of energy
types[edit]
The ratio of exergy to energy
in a substance can be
considered a measure
of energy quality. Forms of
energy such as macroscopic
kinetic energy, electrical
energy, and chemicalGibbs
free energy are 100%
recoverable as work, and
therefore have an exergy
equal to their energy.
However, forms of energy
such as radiation and thermal
energy can not be converted
completely to work, and have
exergy content less than their
energy content. The exact
proportion of exergy in a
substance depends on the
amount of entropy relative to
the surrounding environment
as determined by the Second
Law of Thermodynamics.
Exergy is useful when
measuring the efficiency of an
energy conversion process.
The exergetic, or 2nd Law,
efficiency is a ratio of the
exergy output divided by the
exergy input. This formulation
takes into account the quality
of the energy, often offering a
more accurate and useful
analysis than efficiency
estimates only using the First
Law of Thermodynamics.
Work can be extracted also
from bodies colder than the
surroundings. When the flow
of energy is coming into the
body, work is performed by
this energy obtained from the
large reservoir, the
surrounding. A quantitative
treatment of the notion of
energy quality rests on the
definition of energy. According
to the standard
definition, Energy is a
measure of the ability to do
work. Work can involve the
movement of a mass by a
force that results from a
transformation of energy. If
there is an energy
transformation, the second
principle of energy flow
transformations says that this
process must involve the
dissipation of some energy as
heat. Measuring the amount of
heat released is one way of
quantifying the energy, or
ability to do work and apply a
force over a distance.
However, it appears that the
ability to do work is relative to
the energy transforming
mechanism that applies a
force. This is to say that
some forms of energy perform
no work with respects to some
mechanisms, but perform work
with respects to others. For
example, water does not have
a propensity to combust in an
internal combustion engine,
whereas gasoline does.
Relative to the internal
combustion engine, water has
little ability to do work that
provides a motive force. If
energy is defined as the
ability to do work then a
consequence of this simple
example is that water has no
energy according to this
definition. Nevertheless, water,
raised to a height, does have
the ability to do work like
driving a turbine, and so does
have energy.
This example means to
demonstrate that the ability to
do work can be considered
relative to the mechanism that
transforms energy, and
through such a conversion
applies a force. From this
observation we might wish to
use the word quality, and the
term energy quality to
characterise the energetic
differences between
substances and their
propensities to perform work
given a specific mechanism.
That is the abilities of different
energy forms to flow and be
transformed in certain
mechanisms. With this lexicon,
we can say that energy quality
is mechanism-relative, and the
energy efficiency of a
mechanism is energy quality-
relative an internal
combustion engine running on
water has nearly 0% efficiency
since it has the propensity to
transform little or no water-
energy into thermal-energy. In
order to clarify things here we
might think of this as the
water-efficiency. The
mechanism of interest is also
our system of reference, such
that the choice of energy
quality specifies a certain
system of reference. Thus with
respects to the internal
combustion system of
reference, it has a low water-
efficiency.
Exergy of heat available
at a temperature[edit]
Maximal possible conversion
of heat to work, or exergy
content of heat, depends on
the temperature at which heat
is available and the
temperature level at which the
reject heat can be disposed,
that is the temperature of the
surrounding. The upper limit
for conversion is known
as Carnot efficiency and was
discovered by Nicolas Lonard
Sadi Carnot in 1824. See
also Carnot heat engine.
Carnot efficiency is

where T
H
is the higher
temperature and T
C
is the
lower temperature, both
as absolute temperature.
From Equation 1 it is clear
that in order to maximize
efficiency one should
maximize T
H
and
minimize T
C
.
For calculation of exergy
of heat available at a
temperature there are two
cases: the body releasing
heat is higher than the
surrounding, or, the
temperature of the body is
lower than the
surrounding.
Exergy exchanged is then:

where T
source
is the
temperature of the
heat source, and T
o
is
the temperature of the
surrounding.
History[edit]
Carnot[edit]
In 1824, Sadi
Carnot studied the
improvements
developed for steam
engines by James
Watt and others.
Carnot utilized a
purely theoretical
perspective for these
engines and
developed new ideas.
He wrote:
The question
has often been
raised whether
the motive
power of heat
is unbounded,
whether the
possible
improvements
in steam
engines have
an assignable
limita limit
by which the
nature of
things will not
allow to be
passed by any
means
whatever In
order to
consider in the
most general
way the
principle of the
production of
motion by
heat, it must
be considered
independently
of any
mechanism or
any particular
agent. It is
necessary to
establish
principles
applicable not
only to steam-
engines but to
all imaginable
heat-
engines The
production of
motion in
steam-engines
is always
accompanied
by a
circumstance
on which we
should fix our
attention. This
circumstance
is the re-
establishing of
equilibrium
Imagine two
bodies A and
B, kept each
at a constant
temperature,
that of A being
higher than
that of B.
These two
bodies, to
which we can
give or from
which we can
remove the
heat without
causing their
temperatures
to vary,
exercise the
functions of
two unlimited
reservoirs...
[4]

Carnot next described
what is now called
the Carnot engine,
and proved by
a thought
experiment that any
heat engine
performing better than
this engine would be
a perpetual
motion machine. Even
in the 1820s, there
was a long history of
science forbidding
such devices.
According to Carnot,
"Such a creation is
entirely contrary to
ideas now accepted,
to the laws of
mechanics and of
sound physics. It is
inadmissible."
[4]

This description of an
upper bound to the
work that may be
done by an engine
was the earliest
modern formulation of
the second law of
thermodynamics.
Because it involves no
mathematics, it still
often serves as the
entry point for a
modern understanding
of both the second law
and entropy. Carnot's
focus on heat
engines, equilibrium,
and heat reservoirs is
also the best entry
point for
understanding the
closely related
concept of exergy.
Carnot believed in the
incorrect caloric
theory of heat that
was popular during his
time, but his thought
experiment
nevertheless
described a
fundamental limit of
nature. As kinetic
theory replaced caloric
theory through the
early and mid-19th
century (see timeline),
several scientists
added mathematical
precision to the first
and second laws of
thermodynamics and
developed the concept
of entropy. Carnot's
focus on processes at
the human scale
(above
the thermodynamic
limit) led to the most
universally applicable
concepts in physics.
Entropy and the
second-law are
applied today in fields
ranging from quantum
mechanics to physical
cosmology.
Gibbs[edit]
In the 1870s, Josiah
Willard Gibbs unified a
large quantity of 19th
century thermochemis
try into one compact
theory. Gibbs's theory
incorporated the new
concept of a chemical
potential to cause
change when distant
from a chemical
equilibrium into the
older work begun by
Carnot in describing
thermal
and mechanical
equilibrium and their
potentials for change.
Gibbs's unifying
theory resulted in
the thermodynamic
potential state
functions describing
differences
from thermodynamic
equilibrium.
In 1873, Gibbs derived
the mathematics of
"available energy of
the body and medium"
into the form it has
today.
[3]
(See the
equations below). The
physics describing
exergy has changed
little since that time.

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