First law of thermodynamics

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The first law of thermodynamics is a version of the law of conservation of energy,
adapted for thermodynamic processes, distinguishing two kinds of transfer of energy,
as heat and as thermodynamic work, and relating them to a function of a body's state,
called Internal energy.
The law of conservation of energy states that the total energy of an isolated system is
constant; energy can be transformed from one form to another, but can be neither
created nor destroyed.
For a thermodynamic process without transfer of matter, the first law is often
formulated[1][nb 1]

,
where ΔU denotes the change in the internal energy of a closed system, Q denotes
the quantity of energy supplied to the system as heat, and W denotes the amount of
thermodynamic work done by the system on its surroundings. An equivalent
statement is that perpetual motion machines of the first kind are impossible.
For processes that include transfer of matter, a further statement is needed: 'With
due account of the respective reference states of the systems, when two systems,
which may be of different chemical compositions, initially separated only by an
impermeable wall, and otherwise isolated, are combined into a new system by the
thermodynamic operation of removal of the wall, then

,
where U0 denotes the internal energy of the combined system,
and U1 and U2 denote the internal energies of the respective separated systems.'

Contents

 1History
o 1.1Original statements: the "thermodynamic approach"
o 1.2Conceptual revision: the "mechanical approach"
 2Conceptually revised statement, according to the mechanical approach
 3Description
o 3.1Cyclic processes
o 3.2Sign conventions
 4Various statements of the law for closed systems
 5Evidence for the first law of thermodynamics for closed systems
o 5.1Adiabatic processes
o 5.2Adynamic processes
o 5.3General case for reversible processes
o 5.4General case for irreversible processes
o 5.5Overview of the weight of evidence for the law
 6State functional formulation for infinitesimal processes
 7Spatially inhomogeneous systems
 8First law of thermodynamics for open systems
o 8.1Internal energy for an open system
o 8.2Process of transfer of matter between an open system and its surroundings
o 8.3Open system with multiple contacts
 8.3.1Combination of first and second laws
o 8.4Non-equilibrium transfers
 9See also
 10Remarks
 11References
o 11.1Cited sources
 12Further reading
 13External links

History
The first law of thermodynamics was developed empirically over about half a
century. A main aspect of the struggle was to deal with the previously
proposed caloric theory of heat.
In 1840, Germain Hess stated a conservation law for the so-called 'heat of
reaction' for chemical reactions.[2] His law was later recognized as a
consequence of the first law of thermodynamics, but Hess's statement was not
explicitly concerned with the relation between energy exchanges by heat and
work.
In 1842, Julius Robert von Mayer made a statement that has been rendered
by Truesdell (1980) in the words "in a process at constant pressure, the heat
used to produce expansion is universally interconvertible with work", but this is
not a general statement of the first law.[3][4]
The first full statements of the law came in 1850 from Rudolf Clausius[5][6] and
from William Rankine. Some scholars consider Rankine's statement less distinct
than that of Clausius.[5]
Original statements: the "thermodynamic approach"
The original 19th-century statements of the first law of thermodynamics
appeared in a conceptual framework in which transfer of energy as heat was
taken as a primitive notion, not defined or constructed by the theoretical
development of the framework, but rather presupposed as prior to it and already
accepted. The primitive notion of heat was taken as empirically established,
especially through calorimetry regarded as a subject in its own right, prior to
thermodynamics. Jointly primitive with this notion of heat were the notions of
empirical temperature and thermal equilibrium. This framework also took as
primitive the notion of transfer of energy as work. This framework did not
presume a concept of energy in general, but regarded it as derived or
synthesized from the prior notions of heat and work. By one author, this
framework has been called the "thermodynamic" approach.[6]
The first explicit statement of the first law of thermodynamics, by Rudolf
Clausius in 1850, referred to cyclic thermodynamic processes.
In all cases in which work is produced by the agency of heat, a quantity of heat is
consumed which is proportional to the work done; and conversely, by the
expenditure of an equal quantity of work an equal quantity of heat is produced. [7]
Clausius also stated the law in another form, referring to the existence of a
function of state of the system, the internal energy, and expressed it in terms
of a differential equation for the increments of a thermodynamic
process.[8] This equation may be described as follows:
In a thermodynamic process involving a closed system, the increment in the
internal energy is equal to the difference between the heat accumulated by the
system and the work done by it.
Because of its definition in terms of increments, the value of the internal
energy of a system is not uniquely defined. It is defined only up to an
arbitrary additive constant of integration, which can be adjusted to give
arbitrary reference zero levels. This non-uniqueness is in keeping with
the abstract mathematical nature of the internal energy. The internal
energy is customarily stated relative to a conventionally chosen standard
reference state of the system.
The concept of internal energy is considered by Bailyn to be of
"enormous interest". Its quantity cannot be immediately measured, but
can only be inferred, by differencing actual immediate measurements.
Bailyn likens it to the energy states of an atom, that were revealed by
Bohr's energy relation hν = En'' − En'. In each case, an unmeasurable
quantity (the internal energy, the atomic energy level) is revealed by
considering the difference of measured quantities (increments of internal
energy, quantities of emitted or absorbed radiative energy).[9]
Conceptual revision: the "mechanical approach"
In 1907, George H. Bryan wrote about systems between which there is
no transfer of matter (closed systems): "Definition. When energy flows
from one system or part of a system to another otherwise than by the
performance of mechanical work, the energy so transferred is
called heat."[10] This definition may be regarded as expressing a
conceptual revision, as follows. This was systematically expounded in
1909 by Constantin Carathéodory, whose attention had been drawn to it
by Max Born. Largely through Born's[11] influence, this revised conceptual
approach to the definition of heat came to be preferred by many
twentieth-century writers. It might be called the "mechanical approach". [12]
Energy can also be transferred from one thermodynamic system to
another in association with transfer of matter. Born points out that in
general such energy transfer is not resolvable uniquely into work and
heat moieties. In general, when there is transfer of energy associated
with matter transfer, work and heat transfers can be distinguished only
when they pass through walls physically separate from those for matter
transfer.
 The "mechanical" approach postulates the law of conservation of energy.
It also postulates that energy can be transferred from one thermodynamic
system to another adiabatically as work, and that energy can be held as
the internal energy of a thermodynamic system. It also postulates that
energy can be transferred from one thermodynamic system to another by
a path that is non-adiabatic, and is unaccompanied by matter transfer.
Initially, it "cleverly" (according to Bailyn) refrains from labelling as 'heat'
such non-adiabatic, unaccompanied transfer of energy. It rests on the
primitive notion of walls, especially adiabatic walls and non-adiabatic
walls, defined as follows. Temporarily, only for purpose of this definition,
one can prohibit transfer of energy as work across a wall of interest. Then
walls of interest fall into two classes, (a) those such that arbitrary systems
separated by them remain independently in their own previously
established respective states of internal thermodynamic equilibrium; they
are defined as adiabatic; and (b) those without such independence; they
are defined as non-adiabatic.[13]
This approach derives the notions of transfer of energy as heat, and of
temperature, as theoretical developments, not taking them as primitives.
It regards calorimetry as a derived theory. It has an early origin in the
nineteenth century, for example in the work of Helmholtz,[14] but also in the
work of many others.[6]

Conceptually revised statement, according to the

mechanical approach
The revised statement of the first law postulates that a change in the
internal energy of a system due to any arbitrary process, that takes the
system from a given initial thermodynamic state to a given final
equilibrium thermodynamic state, can be determined through the physical
existence, for those given states, of a reference process that occurs
purely through stages of adiabatic work.
The revised statement is then
For a closed system, in any arbitrary process of interest that takes it from an
initial to a final state of internal thermodynamic equilibrium, the change of internal
energy is the same as that for a reference adiabatic work process that links those
two states. This is so regardless of the path of the process of interest, and
regardless of whether it is an adiabatic or a non-adiabatic process. The reference
adiabatic work process may be chosen arbitrarily from amongst the class of all
such processes.
This statement is much less close to the empirical basis than are the
original statements,[15] but is often regarded as conceptually
parsimonious in that it rests only on the concepts of adiabatic work
and of non-adiabatic processes, not on the concepts of transfer of
energy as heat and of empirical temperature that are presupposed by
the original statements. Largely through the influence of Max Born, it
is often regarded as theoretically preferable because of this
conceptual parsimony. Born particularly observes that the revised
approach avoids thinking in terms of what he calls the "imported
engineering" concept of heat engines.[11]
Basing his thinking on the mechanical approach, Born in 1921, and
again in 1949, proposed to revise the definition of heat. [11][16] In
particular, he referred to the work of Constantin Carathéodory, who
had in 1909 stated the first law without defining quantity of
heat.[17] Born's definition was specifically for transfers of energy
without transfer of matter, and it has been widely followed in
textbooks (examples:[18][19][20]). Born observes that a transfer of matter
between two systems is accompanied by a transfer of internal energy
that cannot be resolved into heat and work components. There can
be pathways to other systems, spatially separate from that of the
matter transfer, that allow heat and work transfer independent of and
simultaneous with the matter transfer. Energy is conserved in such
transfers.

Description
Cyclic processes
The first law of thermodynamics for a closed system was expressed
in two ways by Clausius. One way referred to cyclic processes and
the inputs and outputs of the system, but did not refer to increments in
the internal state of the system. The other way referred to an
incremental change in the internal state of the system, and did not
expect the process to be cyclic.
A cyclic process is one that can be repeated indefinitely often,
returning the system to its initial state. Of particular interest for single
cycle of a cyclic process are the net work done, and the net heat
taken in (or 'consumed', in Clausius' statement), by the system.
In a cyclic process in which the system does net work on its
surroundings, it is observed to be physically necessary not only that
heat be taken into the system, but also, importantly, that some heat
leave the system. The difference is the heat converted by the cycle
into work. In each repetition of a cyclic process, the net work done by
the system, measured in mechanical units, is proportional to the heat
consumed, measured in calorimetric units.
The constant of proportionality is universal and independent of the
system and in 1845 and 1847 was measured by James Joule, who
described it as the mechanical equivalent of heat.
Sign conventions
 In a non-cyclic process, the change in the internal energy of a system
is equal to net energy added as heat to the system minus the
net work done by the system, both being measured in mechanical
units. Taking ΔU as a change in internal energy, one writes

where Q denotes the net quantity of heat supplied to the system

by its surroundings and W denotes the net work done by the
system. This sign convention is implicit in Clausius' statement of
the law given above. It originated with the study of heat
engines that produce useful work by consumption of heat.
Often nowadays, however, writers use the IUPAC convention by
which the first law is formulated with work done on the system by
its surroundings having a positive sign. With this now often used
sign convention for work, the first law for a closed system may be
written:

[21]

This convention follows physicists such as Max Planck,[22] and

considers all net energy transfers to the system as positive
and all net energy transfers from the system as negative,
irrespective of any use for the system as an engine or other
device.
When a system expands in a fictive quasistatic process, the
work done by the system on the environment is the
product, P dV, of pressure, P, and volume change, dV,
whereas the work done on the system is -P dV. Using either
sign convention for work, the change in internal energy of the
system is:

where δQ denotes the infinitesimal amount of heat supplied

to the system from its surroundings and δ denotes
an inexact differential.
Work and heat are expressions of actual physical
processes of supply or removal of energy, while the
internal energy U is a mathematical abstraction that keeps
account of the exchanges of energy that befall the system.
Thus the term heat for Q means "that amount of energy
added or removed by conduction of heat or by thermal
radiation", rather than referring to a form of energy within
the system. Likewise, the term work energy for W means
"that amount of energy gained or lost as the result of
 work". Internal energy is a property of the system whereas
work done and heat supplied are not. A significant result of
this distinction is that a given internal energy
change ΔU can be achieved by, in principle, many
combinations of heat and work.

Various statements of the law for

closed systems
The law is of great importance and generality and is
consequently thought of from several points of view. Most
careful textbook statements of the law express it for closed
systems. It is stated in several ways, sometimes even by
the same author.[6][23]
For the thermodynamics of closed systems, the distinction
between transfers of energy as work and as heat is central
and is within the scope of the present article. For the
thermodynamics of open systems, such a distinction is
beyond the scope of the present article, but some limited
comments are made on it in the section below
headed 'First law of thermodynamics for open systems'.
There are two main ways of stating a law of
thermodynamics, physically or mathematically. They
should be logically coherent and consistent with one
another.[24]
An example of a physical statement is that
of Planck (1897/1903):
It is in no way possible, either by mechanical, thermal, chemical, or other
devices, to obtain perpetual motion, i.e. it is impossible to construct an engine
which will work in a cycle and produce continuous work, or kinetic energy, from
nothing.[25]
This physical statement is restricted neither to closed
systems nor to systems with states that are strictly
defined only for thermodynamic equilibrium; it has
meaning also for open systems and for systems with
states that are not in thermodynamic equilibrium.
An example of a mathematical statement is that of
Crawford (1963):
For a given system we let ΔE kin = large-scale mechanical energy, ΔE pot = large-
scale potential energy, and ΔE tot = total energy. The first two quantities are
specifiable in terms of appropriate mechanical variables, and by definition
For any finite process, whether reversible or irreversible,

The first law in a form that involves the principle of conservation of energy more
generally is

Here Q and W are heat and work added, with no restrictions as to whether the
process is reversible, quasistatic, or irreversible.[Warner, Am. J. Phys., 29, 124
(1961)][26]
This statement by Crawford,
for W, uses the sign
convention of IUPAC, not that
of Clausius. Though it does
not explicitly say so, this
statement refers to closed
systems, and to internal
energy U defined for bodies in
states of thermodynamic
equilibrium, which possess
well-defined temperatures.
The history of statements of
the law for closed systems
has two main periods, before
and after the work
of Bryan (1907),[27] of Carathé
odory (1909),[17] and the
approval of Carathéodory's
work given
by Born (1921).[16] The earlier
traditional versions of the law
for closed systems are
nowadays often considered to
be out of date.
Carathéodory's celebrated
presentation of equilibrium
thermodynamics[17] refers to
closed systems, which are
allowed to contain several
phases connected by internal
walls of various kinds of
impermeability and
permeability (explicitly
including walls that are
permeable only to heat).
Carathéodory's 1909 version
of the first law of
thermodynamics was stated
in an axiom which refrained
from defining or mentioning
temperature or quantity of
heat transferred. That axiom
stated that the internal energy
of a phase in equilibrium is a
function of state, that the sum
of the internal energies of the
phases is the total internal
energy of the system, and
that the value of the total
internal energy of the system
is changed by the amount of
work done adiabatically on it,
considering work as a form of
energy. That article
considered this statement to
be an expression of the law of
conservation of energy for
such systems. This version is
nowadays widely accepted as
authoritative, but is stated in
slightly varied ways by
different authors.
Such statements of the first
law for closed systems assert
the existence of internal
energy as a function of state
defined in terms of adiabatic
work. Thus heat is not defined
calorimetrically or as due to
temperature difference. It is
defined as a residual
difference between change of
internal energy and work
done on the system, when
that work does not account for
the whole of the change of
internal energy and the
system is not adiabatically
isolated.[18][19][20]
The 1909 Carathéodory
statement of the law in
axiomatic form does not
mention heat or temperature,
but the equilibrium states to
which it refers are explicitly
defined by variable sets that
necessarily include "non-
deformation variables", such
as pressures, which, within
reasonable restrictions, can
be rightly interpreted as
empirical temperatures,[28] and
the walls connecting the
phases of the system are
explicitly defined as possibly
impermeable to heat or
permeable only to heat.
According to Münster (1970),
"A somewhat unsatisfactory
aspect of Carathéodory's
theory is that a consequence
of the Second Law must be
considered at this point [in the
statement of the first law], i.e.
that it is not always possible
to reach any state 2 from any
other state 1 by means of an
adiabatic process." Münster
instances that no adiabatic
process can reduce the
internal energy of a system at
constant
volume.[18] Carathéodory's
paper asserts that its
statement of the first law
corresponds exactly to Joule's
experimental arrangement,
regarded as an instance of
adiabatic work. It does not
point out that Joule's
experimental arrangement
performed essentially
irreversible work, through
friction of paddles in a liquid,
or passage of electric current
through a resistance inside
the system, driven by motion
of a coil and inductive
heating, or by an external
current source, which can
access the system only by the
passage of electrons, and so
is not strictly adiabatic,
because electrons are a form
of matter, which cannot
penetrate adiabatic walls. The
paper goes on to base its
main argument on the
possibility of quasi-static
adiabatic work, which is
essentially reversible. The
paper asserts that it will avoid
reference to Carnot cycles,
and then proceeds to base its
argument on cycles of forward
and backward quasi-static
adiabatic stages, with
isothermal stages of zero
magnitude.
Sometimes the concept of
internal energy is not made
explicit in the statement.[29][30][31]
Sometimes the existence of
the internal energy is made
explicit but work is not
explicitly mentioned in the
statement of the first postulate
of thermodynamics. Heat
supplied is then defined as
the residual change in internal
energy after work has been
taken into account, in a non-
adiabatic process.[32]
A respected modern author
states the first law of
thermodynamics as "Heat is a
form of energy", which
explicitly mentions neither
internal energy nor adiabatic
work. Heat is defined as
energy transferred by thermal
contact with a reservoir, which
has a temperature, and is
generally so large that
addition and removal of heat
do not alter its
temperature.[33] A current
student text on chemistry
defines heat thus: "heat is the
exchange of thermal energy
between a system and its
surroundings caused by a
temperature difference." The
author then explains how heat
is defined or measured by
calorimetry, in terms of heat
capacity, specific heat
capacity, molar heat capacity,
and temperature.[34]
A respected text disregards
the Carathéodory's exclusion
of mention of heat from the
statement of the first law for
closed systems, and admits
heat calorimetrically defined
along with work and internal
energy.[35] Another respected
text defines heat exchange as
determined by temperature
difference, but also mentions
that the Born (1921) version is
"completely
rigorous".[36] These versions
follow the traditional approach
that is now considered out of
date, exemplified by that of
Planck (1897/1903).[37]

Evidence for the

first law of
thermodynamics
for closed systems
The first law of
thermodynamics for closed
systems was originally
induced from empirically
observed evidence, including
calorimetric evidence. It is
nowadays, however, taken to
provide the definition of heat
via the law of conservation of
energy and the definition of
work in terms of changes in
the external parameters of a
system. The original
discovery of the law was
gradual over a period of
perhaps half a century or
more, and some early studies
were in terms of cyclic
processes.[5]
The following is an account in
terms of changes of state of a
closed system through
compound processes that are
not necessarily cyclic. This
account first considers
processes for which the first
law is easily verified because
of their simplicity,
namely adiabatic
processes (in which there is
no transfer as heat)
and adynamic processes (in
which there is no transfer as
work).
Adiabatic processes
Main article: Adiabatic
process
In an adiabatic process, there
is transfer of energy as work
but not as heat. For all
adiabatic process that takes a
system from a given initial
state to a given final state,
irrespective of how the work is
done, the respective eventual
total quantities of energy
transferred as work are one
and the same, determined
just by the given initial and
final states. The work done on
the system is defined and
measured by changes in
mechanical or quasi-
mechanical variables external
to the system. Physically,
adiabatic transfer of energy
as work requires the
existence of adiabatic
enclosures.
For instance, in Joule's
experiment, the initial system
is a tank of water with a
paddle wheel inside. If we
isolate the tank thermally, and
move the paddle wheel with a
pulley and a weight, we can
relate the increase in
temperature with the distance
descended by the mass.
Next, the system is returned
to its initial state, isolated
again, and the same amount
of work is done on the tank
using different devices (an
electric motor, a chemical
battery, a spring,...). In every
case, the amount of work can
be measured independently.
The return to the initial state is
not conducted by doing
adiabatic work on the system.
The evidence shows that the
final state of the water (in
particular, its temperature and
volume) is the same in every
case. It is irrelevant if the
work is electrical, mechanical,
chemical,... or if done
suddenly or slowly, as long as
it is performed in an adiabatic
way, that is to say, without
heat transfer into or out of the
system.
Evidence of this kind shows
that to increase the
temperature of the water in
the tank, the qualitative kind
of adiabatically performed
work does not matter. No
qualitative kind of adiabatic
work has ever been observed
to decrease the temperature
of the water in the tank.
A change from one state to
another, for example an
increase of both temperature
and volume, may be
conducted in several stages,
for example by externally
supplied electrical work on a
resistor in the body, and
adiabatic expansion allowing
the body to do work on the
surroundings. It needs to be
shown that the time order of
the stages, and their relative
magnitudes, does not affect
the amount of adiabatic work
that needs to be done for the
change of state. According to
one respected scholar:
"Unfortunately, it does not
seem that experiments of this
kind have ever been carried
out carefully. ... We must
therefore admit that the
statement which we have
enunciated here, and which is
equivalent to the first law of
thermodynamics, is not well
founded on direct
experimental
evidence."[15] Another
expression of this view is
"... no systematic precise
experiments to verify this
generalization directly have
ever been attempted."[38]
This kind of evidence, of
independence of sequence of
stages, combined with the
above-mentioned evidence, of
independence of qualitative
kind of work, would show the
existence of an important
state variable that
corresponds with adiabatic
work, but not that such a state
variable represented a
conserved quantity. For the
latter, another step of
evidence is needed, which
may be related to the concept
of reversibility, as mentioned
below.
That important state variable
was first recognized and

denoted by Clausius in
1850, but he did not then
name it, and he defined it in
terms not only of work but
also of heat transfer in the
same process. It was also
independently recognized in
1850 by Rankine, who also

denoted it ; and in 1851

by Kelvin who then called it
"mechanical energy", and
later "intrinsic energy". In
1865, after some hestitation,
Clausius began calling his

state function "energy".

In 1882 it was named as
the internal energy by
Helmholtz.[39] If only adiabatic
processes were of interest,
and heat could be ignored,
the concept of internal energy
would hardly arise or be
needed. The relevant physics
would be largely covered by
the concept of potential
energy, as was intended in
the 1847 paper of Helmholtz
on the principle of
conservation of energy,
though that did not deal with
forces that cannot be
described by a potential, and
thus did not fully justify the
principle. Moreover, that
paper was critical of the early
work of Joule that had by then
been performed.[40] A great
merit of the internal energy
concept is that it frees
thermodynamics from a
restriction to cyclic processes,
and allows a treatment in
terms of thermodynamic
states.
In an adiabatic process,
adiabatic work takes the
system either from a

reference state with

internal energy to an

arbitrary one with

internal energy , or from

the state to the

state :

Except under the special,

and strictly speaking,
fictional, condition of
reversibility, only one of
the

processes or
is empirically feasible by a
simple application of
externally supplied work.
The reason for this is
given as the second law of
thermodynamics and is
not considered in the
present article.
The fact of such
irreversibility may be dealt
with in two main ways,
according to different
points of view:

 Since the work of

Bryan (1907), the most
accepted way to deal
with it nowadays,
followed by
Carathéodory,[17][20][41] is
to rely on the
previously established
concept of quasi-static
processes,[42][43][44] as
follows. Actual
physical processes of
transfer of energy as
work are always at
least to some degree
irreversible. The
irreversibility is often
due to mechanisms
known as dissipative,
that transform bulk
kinetic energy into
internal energy.
Examples are friction
and viscosity. If the
process is performed
more slowly, the
frictional or viscous
dissipation is less. In
the limit of infinitely
slow performance, the
dissipation tends to
zero and then the
limiting process,
though fictional rather
than actual, is
notionally reversible,
and is called quasi-
static. Throughout the
course of the fictional
limiting quasi-static
process, the internal
intensive variables of
the system are equal
to the external
intensive variables,
those that describe the
reactive forces exerted
by the
surroundings.[45] This
can be taken to justify
the formula

 Another way to
deal with it is to
allow that
experiments with
processes of heat
transfer to or from
the system may be
used to justify the
formula (1) above.
Moreover, it deals
to some extent
with the problem of
lack of direct
experimental
evidence that the
time order of
stages of a
process does not
matter in the
determination of
internal energy.
This way does not
provide theoretical
purity in terms of
adiabatic work
processes, but is
empirically
feasible, and is in
accord with
experiments
 actually done, such
as the Joule
experiments
mentioned just
above, and with
older traditions.
The formula (1) above
allows that to go by
processes of quasi-
static adiabatic work

from the state to

the state we can

take a path that goes
through the reference

state , since the

quasi-static adiabatic
work is independent of
the path

This kind of
empirical evidence,
coupled with
theory of this kind,
largely justifies the
following
statement:
For all adiabatic processes between two specified states of a closed system of
any nature, the net work done is the same regardless the details of the process,

and determines a state function called internal energy, .

Adynamic
processes
See
also: Thermody
namic
processes
A
complementary
observable
aspect of the
first law is
about heat
transfer.
Adynamic
transfer of
energy as heat
can be
measured
empirically by
changes in the
surroundings of
the system of
interest by
calorimetry.
This again
requires the
existence of
adiabatic
enclosure of
the entire
process,
system and
surroundings,
though the
separating wall
between the
surroundings
and the system
is thermally
conductive or
radiatively
permeable, not
adiabatic. A
calorimeter can
rely on
measurement
of sensible
heat, which
requires the
existence of
thermometers
and
measurement
of temperature
change in
bodies of
known sensible
heat capacity
under specified
conditions; or it
can rely on the
measurement
of latent heat,
through measu
rement of
masses of
material that
change phase,
at
temperatures
fixed by the
occurrence of
phase changes
under specified
conditions in
bodies of
known latent
heat of phase
change. The
calorimeter can
be calibrated
by adiabatically
doing
externally
determined
work on it. The
most accurate
method is by
passing an
electric current
from outside
through a
resistance
inside the
calorimeter.
The calibration
allows
comparison of
calorimetric
measurement
of quantity of
heat
transferred with
quantity of
energy
transferred as
work.
According to
one textbook,
"The most
common
device for

measuring
is an adiabatic
bomb
calorimeter."[46]
According to
another
textbook,
"Calorimetry is
widely used in
present day
laboratories."[47]
According to
one opinion,
"Most
thermodynamic
data come from
calorimetry..."[48]
According to
another
opinion, "The
most common
method of
measuring
"heat" is with a
calorimeter."[49]
When the
system evolves
with transfer of
energy as heat,
without energy
being
transferred as
work, in an
adynamic
process,[50] the
heat
transferred to
the system is
equal to the
increase in its
internal energy:

General
case for
reversibl
e
processe
s
Heat
transfer is
practically
reversible
when it is
driven by
practically
negligibly
small
temperature
gradients.
Work
transfer is
practically
reversible
when it
occurs so
slowly that
there are no
frictional
effects
within the
system;
frictional
effects
outside the
system
should also
be zero if
the process
is to be
globally
reversible.
For a
particular
reversible
process in
general, the
work done
reversibly
on the
system,

, and
the heat
transferred
reversibly to
the
system,

are not
required to
occur
respectively
adiabaticall
y or
adynamicall
y, but they
must
belong to
the same
particular
process
defined by
its particular
reversible

path, ,
through the
space of
thermodyna
mic states.
Then the
work and
heat
transfers
can occur
and be
calculated
simultaneou
sly.
Putting the
two
complemen
tary aspects
together,
the first law
for a
particular
reversible
process can
be written

This
combine
d
stateme
nt is the
expressi
on the
first law
of
thermod
ynamics
for
reversibl
e
process
es for
closed
systems
.
In
particula
r, if no
work is
done on
a
thermall
y
isolated
 closed
system
we have

.
This
is
one
aspe
ct of
the
law
of
cons
erva
tion
of
ener
gy
and
can
be
state
d:
The internal energy of an isolated system remains constant.
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