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2 3 PRACTICAL OPERATING DEVICES THAT HARNESS TRANSFERS OF ENERGY AS HEAT
thermodynamics.[12] This was the way of the historical working body, the hot reservoir, the cold reservoir, and
pioneers of thermodynamics.[13][14] the work reservoir. A cyclic process leaves the working
body in an unchanged state, and is envisaged as being
repeated indenitely often. Work transfers between the
2 Transfers of energy as heat be- working body and the work reservoir are envisaged as
reversible, and thus only one work reservoir is needed.
tween two bodies But two thermal reservoirs are needed, because transfer
of energy as heat is irreversible. A single cycle sees en-
Referring to conduction, Partington writes: If a hot body ergy taken by the working body from the hot reservoir
is brought in conducting contact with a cold body, the and sent to the two other reservoirs, the work reservoir
temperature of the hot body falls and that of the cold body and the cold reservoir. The hot reservoir always and only
rises, and it is said that a quantity of heat has passed from supplies energy and the cold reservoir always and only
the hot body to the cold body.[15] receives energy. The second law of thermodynamics re-
quires that no cycle can occur in which no energy is re-
Referring to radiation, Maxwell writes: In Radiation,
ceived by the cold reservoir. Heat engines achieve higher
the hotter body loses heat, and the colder body receives
eciency when the dierence between initial and nal
heat by means of a process occurring in some intervening
[16] temperature is greater.
medium which does not itself thereby become hot.
Maxwell writes that convection as such is not a purely
thermal phenomenon.[17] In thermodynamics, convec- 3.2 Heat pump or refrigerator
tion in general is regarded as transport of internal energy.
If, however, the convection is enclosed and circulatory, Another commonly considered model is the heat pump
then it may be regarded as an intermediary that trans- or refrigerator. Again there are four bodies: the work-
fers energy as heat between source and destination bod- ing body, the hot reservoir, the cold reservoir, and the
ies, because it transfers only energy and not matter from work reservoir. A single cycle starts with the working
the source to the destination body.[9] body colder than the cold reservoir, and then energy is
taken in as heat by the working body from the cold reser-
voir. Then the work reservoir does work on the working
3 Practical operating devices that body, adding more to its internal energy, making it hot-
ter than the hot reservoir. The hot working body passes
harness transfers of energy as heat to the hot reservoir, but still remains hotter than the
heat cold reservoir. Then, by allowing it to expand without
doing work on another body and without passing heat to
another body, the working body is made colder than the
In accordance with the rst law for closed systems, energy cold reservoir. It can now accept heat transfer from the
transferred solely as heat leaves one body and enters an- cold reservoir to start another cycle.
other, changing the internal energies of each. Transfer,
between bodies, of energy as work is a complementary The device has transported energy from a colder to a
way of changing internal energies. Though it is not log- hotter reservoir, but this is not regarded as being by an
ically rigorous from the viewpoint of strict physical con- inanimate agency; rather, it is regarded as by the har-
cepts, a common form of words that expresses this is to nessing of work . This is because work is supplied from
say that heat and work are interconvertible. the work reservoir, not just by a simple thermodynamic
process, but by a cycle of thermodynamic operations and
Cyclically operating engines, that use only heat and work processes, which may be regarded as directed by an ani-
transfers, have two thermal reservoirs, a hot and a cold mate or harnessing agency. Accordingly, the cycle is still
one. They may be classied by the range of operating in accord with the second law of thermodynamics. The
temperatures of the working body, relative to those reser- eciency of a heat pump is best when the temperature
voirs. In a heat engine, the working body is at all times dierence between the hot and cold reservoirs is least.
colder than the hot reservoir and hotter than the cold
reservoir. In a sense, it uses heat transfer to produce work. Functionally, such engines are used in two ways, distin-
In a heat pump, the working body, at stages of the cycle, guishing a target reservoir and a resource or surrounding
goes both hotter than the hot reservoir, and colder than reservoir. A heat pump transfers heat, to the hot reservoir
the cold reservoir. In a sense, it uses work to produce as the target, from the resource or surrounding reservoir.
heat transfer. A refrigerator transfers heat, from the cold reservoir as
the target, to the resource or surrounding reservoir. The
target reservoir may be regarded as leaking: when the
3.1 Heat engine target leaks hotness to the surroundings, heat pumping
is used; when the target leaks coldness to the surround-
In classical thermodynamics, a commonly considered ings, refrigeration is used. The engines harness work to
model is the heat engine. It consists of four bodies: the overcome the leaks.
3
4 Macroscopic view of quantity of which drives electric current and iontophoresis; such ef-
fects usually interact with diusive ux of internal energy
energy transferred as heat driven by temperature gradient, and such interactions are
known as cross-eects.[23]
According to Planck, there are three main conceptual ap- If cross-eects that result in diusive transfer of inter-
proaches to heat.[18] One is the microscopic or kinetic nal energy were also labeled as heat transfers, they would
theory approach. The other two are macroscopic ap- sometimes violate the rule that pure heat transfer occurs
proaches. One is the approach through the law of conser- only down a temperature gradient, never up one. They
vation of energy taken as prior to thermodynamics, with would also contradict the principle that all heat transfer is
a mechanical analysis of processes, for example in the of one and the same kind, a principle founded on the idea
work of Helmholtz. This mechanical view is taken in this of heat conduction between closed systems. One might
article as currently customary for thermodynamic theory. to try to think narrowly of heat ux driven purely by tem-
The other macroscopic approach is the thermodynamic perature gradient as a conceptual component of diusive
one, which admits heat as a primitive concept, which con- internal energy ux, in the thermodynamic view, the con-
tributes, by scientic induction[19] to knowledge of the cept resting specically on careful calculations based on
law of conservation of energy. This view is widely taken detailed knowledge of the processes and being indirectly
as the practical one, quantity of heat being measured by assessed. In these circumstances, if perchance it hap-
calorimetry. pens that no transfer of matter is actualized, and there
Bailyn also distinguishes the two macroscopic approaches are no cross-eects, then the thermodynamic concept and
as the mechanical and the thermodynamic.[20] The ther- the mechanical concept coincide, as if one were dealing
modynamic view was taken by the founders of thermo- with closed systems. But when there is transfer of mat-
dynamics in the nineteenth century. It regards quantity ter, the exact laws by which temperature gradient drives
of energy transferred as heat as a primitive concept co- diusive ux of internal energy, rather than being exactly
herent with a primitive concept of temperature, mea- knowable, mostly need to be assumed, and in many cases
sured primarily by calorimetry. A calorimeter is a body are practically unveriable. Consequently, when there is
in the surroundings of the system, with its own temper- transfer of matter, the calculation of the pure 'heat ux'
ature and internal energy; when it is connected to the component of the diusive ux of internal energy rests
system by a path for heat transfer, changes in it mea- on practically unveriable assumptions.[24][quotations 1][25]
sure heat transfer. The mechanical view was pioneered This is a reason to think of heat as a specialized concept
by Helmholtz and developed and used in the twentieth that relates primarily and precisely to closed systems, and
century, largely through the inuence of Max Born.[21] It applicable only in a very restricted way to open systems.
regards quantity of heat transferred as heat as a derived In many writings in this context, the term heat ux is
concept, dened for closed systems as quantity of heat used when what is meant is therefore more accurately
transferred by mechanisms other than work transfer, the called diusive ux of internal energy; such usage of the
latter being regarded as primitive for thermodynamics, term heat ux is a residue of older and now obsolete
dened by macroscopic mechanics. According to Born, language usage that allowed that a body may have a heat
the transfer of internal energy between open systems that content.[26]
accompanies transfer of matter cannot be reduced to
mechanics.[22] It follows that there is no well-founded
denition of quantities of energy transferred as heat or
as work associated with transfer of matter. 5 Microscopic view of heat
Nevertheless, for the thermodynamical description of
non-equilibrium processes, it is desired to consider the In the kinetic theory, heat is explained in terms of the mi-
eect of a temperature gradient established by the sur- croscopic motions and interactions of constituent parti-
roundings across the system of interest when there is no cles, such as electrons, atoms, and molecules.[27] The im-
physical barrier or wall between system and surroundings, mediate meaning of the kinetic energy of the constituent
that is to say, when they are open with respect to one an- particles is not as heat. It is as a component of internal
other. The impossibility of a mechanical denition in energy. In microscopic terms, heat is a transfer quantity,
terms of work for this circumstance does not alter the and is described by a transport theory, not as steadily lo-
physical fact that a temperature gradient causes a diu- calized kinetic energy of particles. Heat transfer arises
sive ux of internal energy, a process that, in the thermo- from temperature gradients or dierences, through the
dynamic view, might be proposed as a candidate concept diuse exchange of microscopic kinetic and potential
for transfer of energy as heat. particle energy, by particle collisions and other interac-
In this circumstance, it may be expected that there may tions. An early [28][29]
and vague expression of this was made by
also be active other drivers of diusive ux of inter- Francis Bacon. Precise and detailed versions of it
nal energy, such as gradient of chemical potential which were developed in the nineteenth century.[30]
drives transfer of matter, and gradient of electric potential In statistical mechanics, for a closed system (no transfer
4 8 INTERNAL ENERGY AND ENTHALPY
of matter), heat is the energy transfer associated with a 8 Internal energy and enthalpy
disordered, microscopic action on the system, associated
with jumps in occupation numbers of the energy levels For a closed system (a system from which no matter can
of the system, without change in the values of the energy enter or exit), one version of the rst law of thermody-
levels themselves.[31] It is possible for macroscopic ther- namics states that the change in internal energy U of
modynamic work to alter the occupation numbers with- the system is equal to the amount of heat Q supplied to
out change in the values of the system energy levels them- the system minus the amount of work W done by sys-
selves, but what distinguishes transfer as heat is that the tem on its surroundings. The foregoing sign convention
transfer is entirely due to disordered, microscopic action, for work is used in the present article, but an alternate
including radiative transfer. A mathematical denition sign convention, followed by IUPAC, for work, is to con-
can be formulated for small increments of quasi-static sider the work performed on the system by its surround-
adiabatic work in terms of the statistical distribution of ings as positive. This is the convention adopted by many
an ensemble of microstates. modern textbooks of physical chemistry, such as those
by Peter Atkins and Ira Levine, but many textbooks on
physics dene work as work done by the system.
supplied to a system in which no irreversible processes 8.1 Heat added to a body at constant pres-
take place and which has a well-dened temperature T, sure
the increment of heat Q and the temperature T form the
exact dierential If a quantity Q of heat is added to a body while it does
expansion work W on its surroundings, one has
Q
dS = ,
T
H = U + (P V ) .
and that S, the entropy of the working body, is a function
of state. Likewise, with a well-dened pressure, P, behind If this is constrained to happen at constant pressure with
the moving boundary, the work dierential, W, and the P = 0, the expansion work W done by the body is given
pressure, P, combine to form the exact dierential by W = P V; recalling the rst law of thermodynamics,
one has
W
dV = ,
P U = Q W = Q P V and (P V ) = P V .
with V the volume of the system, which is a state variable.
Consequently, by substitution one has
In general, for homogeneous systems,
H = Q P V + P V
dU = T dS P dV.
Associated with this dierential equation is that the in- =Q pressure. constant at
ternal energy may be considered to be a function U (S,V)
of its natural variables S and V. The internal energy rep-
In this scenario, the increase in enthalpy is equal to
resentation of the fundamental thermodynamic relation is
the quantity of heat added to the system. Since
written
many processes do take place at constant pressure, or
approximately at atmospheric pressure, the enthalpy
U = U (S, V ). [39][40] is therefore sometimes given the misleading name of
'heat content'.[43] It is sometimes also called the heat
If V is constant function.[44]
In terms of the natural variables S and P of the state func-
T dS = dU (V constant) tion H, this process of change of state from state 1 to state
2 can be expressed as
and if P is constant
S2 ( ) P2 ( )
H H
H = dS + dP
T dS = dH (P constant) S1 S P P1 P S
S = S + S .
Soverall = S + S S = S .
T dS = Q + T dSuncompensated > Q.
T dS Q (second law) .
where by denition
12 Relation between heat and tem- wood in his pyrometer. The temperature reached in a
process was estimated by the shrinkage of a sample of
perature clay. The higher the temperature, the more the shrinkage.
This was the only available more or less reliable method
Before the discovery of the laws of thermodynamics, of measurement of temperatures above 1000 C. But such
quantity of energy transferred as heat was measured by shrinkage is irreversible. The clay does not expand again
changes in the states of the participating bodies. on cooling. That is why it could be used for the measure-
ment. But only once. It is not a thermometric material in
Some general rules, with important exceptions, that will
the usual sense of the word.
be indicated noted in following paragraphs of this section,
can be stated as follows. Nevertheless, the thermodynamic denition of absolute
temperature does make essential use of the concept of
Most bodies, over most temperature ranges, expand on
heat, with proper circumspection.
being heated. Mostly, heating a body at a constant vol-
ume increases the pressure it exerts on its constraining
walls, and increases its temperature. Also mostly, heat-
ing a body at a constant pressure increases its volume, and
increases its temperature.
13 Relation between hotness and
Beyond this, most substances have three ordinarily recog-
temperature
nized states of matter, solid, liquid, and gas, and a fourth
less obviously recognized one, plasma. Many have fur- According to Denbigh, the property of hotness is a con-
ther, more nely dierentiated, states of matter, such as cern of thermodynamics that should be dened without
for example, glass, and liquid crystal. In many cases, at reference to the concept of heat. Consideration of hot-
xed temperature and pressure, a substance can exist in ness leads to the concept of empirical temperature.[55]
several distinct states of matter in what might be viewed All physical systems are capable of heating or cooling
as the same 'body'. For example, ice may oat in a glass others.[56] This does not require that they have ther-
of water. Then the ice and the water are said to con- modynamic temperatures. With reference to hotness,
stitute two phases within the 'body'. Denite rules are the comparative terms hotter and colder are dened by
known, telling how distinct phases may coexist in a 'body'. the rule that heat ows from the hotter body to the
Mostly, at a xed pressure, there is a denite temperature colder.[57][58][59]
at which heating causes a solid to melt or evaporate, and If a physical system is inhomogeneous or very rapidly or
a denite temperature at which heating causes a liquid to irregularly changing, for example by turbulence, it may
evaporate. In such cases, cooling has the reverse eects. be impossible to characterize it by a temperature, but still
All of these, the commonest cases, t with a rule that heat- there can be transfer of energy as heat between it and
ing can be measured by changes of state of a body. Such another system. If a system has a physical state that is
cases supply what are called thermometric bodies, that regular enough, and persists long enough to allow it to
allow the denition of empirical temperatures. Before reach thermal equilibrium with a specied thermometer,
1848, all temperatures were dened in this way. There then it has a temperature according to that thermome-
was thus a tight link, apparently logically determined, be- ter. An empirical thermometer registers degree of hot-
tween heat and temperature, though they were recognized ness for such a system. Such a temperature is called
as conceptually thoroughly distinct, especially by Joseph empirical.[60][61][62] For example, Truesdell writes about
Black in the later eighteenth century. classical thermodynamics: At each time, the body is as-
There are important exceptions. They break the obvi- signed a real number called the temperature. This number
is a measure of how hot the body is.[63]
ously apparent link between heat and temperature. They
Physical systems that are too turbulent to have tempera-
make it clear that empirical denitions of temperature are
tures may still dier in hotness. A physical system that
contingent on the peculiar properties of particular ther-
mometric substances, and are thus precluded from the passes heat to another physical system is said to be the
title 'absolute'. For example, water contracts on beinghotter of the two. More is required for the system to have
heated near 277 K. It cannot be used as a thermomet- a thermodynamic temperature. Its behavior must be so
ric substance near that temperature. Also, over a certain
regular that its empirical temperature is the same for all
temperature range, ice contracts on heating. Moreover, suitably calibrated and scaled thermometers, and then its
many substances can exist in metastable states, such ashotness is said to lie on the one-dimensional hotness man-
with negative pressure, that survive only transiently and
ifold. This is part of the reason why heat is dened fol-
in very special conditions. Such facts, sometimes called
lowing Carathodory and Born, solely as occurring other
'anomalous, are some of the reasons for the thermody- than by work or transfer of matter; temperature is advis-
namic denition of absolute temperature. edly and deliberately not mentioned in this now widely
In the early days of measurement of high temperatures, accepted denition.
another factor was important, and used by Josiah Wedg- This is also the reason why the zeroth law of thermo-
9
15 Heat, temperature, and thermal Carathodory way regards calorimetry only as a sec-
ondary or indirect way of measuring quantity of energy
equilibrium regarded as jointly transferred as heat. As recounted in more detail just
primitive notions above, the Carathodory way regards quantity of energy
transferred as heat in a process as primarily or directly
Before the rigorous mathematical denition of heat based dened as a residual quantity. It is calculated from the
on Carathodorys 1909 paper, recounted just above, dierence of the internal energies of the initial and nal
historically, heat, temperature, and thermal equilibrium states of the system, and from the actual work done by
were presented in thermodynamics textbooks as jointly the system during the process. That internal energy dif-
primitive notions.[70] Carathodory introduced his 1909 ference is supposed to have been measured in advance
paper thus: The proposition that the discipline of ther- through processes of purely adiabatic transfer of energy
modynamics can be justied without recourse to any hy- as work, processes that take the system between the ini-
pothesis that cannot be veried experimentally must be tial and nal states. By the Carathodory way it is pre-
regarded as one of the most noteworthy results of the re- supposed as known from experiment that there actually
search in thermodynamics that was accomplished during physically exist enough such adiabatic processes, so that
the last century. Referring to the point of view adopted there need be no recourse to calorimetry for measurement
by most authors who were active in the last fty years, of quantity of energy transferred as heat. This presuppo-
Carathodory wrote: There exists a physical quantity sition is essential but is explicitly labeled neither as a law
called heat that is not identical with the mechanical quan- of thermodynamics nor as an axiom of the Carathodory
tities (mass, force, pressure, etc.) and whose variations way. In fact, the actual physical existence of such adi-
can be determined by calorimetric measurements. James abatic processes is indeed mostly supposition, and those
Serrin introduces an account of the theory of thermo- supposed processes have in most cases not been actually
dynamics thus: In the following section, we shall use veried empirically to exist.[76]
the classical notions of heat, work, and hotness as primi-
tive elements, ... That heat is an appropriate and natural
primitive for thermodynamics was already accepted by 16 Heat transfer in engineering
Carnot. Its continued validity as a primitive element of
thermodynamical structure is due to the fact that it syn-
thesizes an essential physical concept, as well as to its suc-
cessful use in recent work to unify dierent constitutive
theories.[71][72] This traditional kind of presentation of
the basis of thermodynamics includes ideas that may be
summarized by the statement that heat transfer is purely
due to spatial non-uniformity of temperature, and is by
conduction and radiation, from hotter to colder bodies.
It is sometimes proposed that this traditional kind of pre-
sentation necessarily rests on circular reasoning"; against
this proposal, there stands the rigorously logical mathe-
matical development of the theory presented by Truesdell
and Bharatha (1977).[73]
This alternative approach to the denition of quantity of
energy transferred as heat diers in logical structure from A red-hot iron rod from which heat transfer to the surrounding
that of Carathodory, recounted just above. environment will be primarily through radiation.
This alternative approach admits calorimetry as a primary
or direct way to measure quantity of energy transferred The discipline of heat transfer, typically considered an
as heat. It relies on temperature as one of its primitive aspect of mechanical engineering and chemical engineer-
concepts, and used in calorimetry.[74] It is presupposed ing, deals with specic applied methods by which thermal
that enough processes exist physically to allow measure- energy in a system is generated, or converted, or trans-
ment of dierences in internal energies. Such processes ferred to another system. Although the denition of heat
are not restricted to adiabatic transfers of energy as work. implicitly means the transfer of energy, the term heat
They include calorimetry, which is the commonest prac- transfer encompasses this traditional usage in many en-
tical way of nding internal energy dierences.[75] The gineering disciplines and laymen language.
needed temperature can be either empirical or absolute Heat transfer includes the mechanisms of heat conduc-
thermodynamic. tion, thermal radiation, and mass transfer.
In contrast, the Carathodory way recounted just above In engineering, the term convective heat transfer is used
does not use calorimetry or temperature in its primary to describe the combined eects of conduction and uid
denition of quantity of energy transferred as heat. The ow. From the thermodynamic point of view, heat ows
11
into a uid by diusion to increase its energy, the uid [6] Bailyn, M. (1994), p. 82.
then transfers (advects) this increased internal energy (not
[7] Guggenheim, E.A. (1949/1967), p. 8
heat) from one location to another, and this is then fol-
lowed by a second thermal interaction which transfers [8] Planck. M. (1914)
heat to a second body or system, again by diusion. This
entire process is often regarded as an additional mecha- [9] Chandrasekhar, S. (1961).
nism of heat transfer, although technically, heat transfer [10] Maxwell, J.C. (1871), Chapter III.
and thus heating and cooling occurs only on either end of
such a conductive ow, but not as a result of ow. Thus, [11] Maxwell, J.C. (1871), p. 7.
conduction can be said to transfer heat only as a net re- [12] Planck, M. (1903).
sult of the process, but may not do so at every time within
the complicated convective process. [13] Partington, J.R. (1949).
Although distinct physical laws may describe the behav- [14] Truesdell, C. (1980), page 15.
ior of each of these methods, real systems often exhibit a
[15] Partington, J.R. (1949), p. 118.
complicated combination which are often described by a
variety of mathematical methods. [16] Maxwell, J.C. (1871), p. 10.
[5] Reif, F. (1965), pp. 67, 73. [43] Adkins, C.J. (1968/1983), p. 46.
12 18 REFERENCES
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[64] Lieb, E.H., Yngvason, J. (2003), page 190.
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14 19 EXTERNAL LINKS
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