Thermodynamics with friction. I.

The Clausius inequality revisited

João P. S. Bizarro

Citation: Journal of Applied Physics 108, 054907 (2010); doi: 10.1063/1.3477189

View online: http://dx.doi.org/10.1063/1.3477189
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 JOURNAL OF APPLIED PHYSICS 108, 054907 共2010兲

Thermodynamics with friction. I. The Clausius inequality revisited

João P. S. Bizarroa兲
Associação Euratom–IST, Instituto de Plasmas e Fusão Nuclear – Laboratório Associado, Instituto Superior
Técnico, 1049-001 Lisboa, Portugal
共Received 21 June 2010; accepted 15 July 2010; published online 13 September 2010兲
The different forms of the Clausius inequality are generalized to explicitly include frictional work,
which can be partly dissipated as heat in the surroundings and thus contribute to increase its entropy
so, in a cyclic process, the net entropy leaving the surroundings with the heat directly exchanged
with the system is no longer constrained by the second law to be nonpositive. Likewise, the lower
bound for the system’s entropy change in an arbitrary transformation is not now determined solely
by the heat transferred from the surroundings but can be smaller by a term given by frictional
dissipation in the latter. A wide range of applications is discussed, from thermal engines to
mesoscopic devices, including the efficiency of dithermal engines and the problem of information
erasure. Moreover, it is verified that the macroscopic approach utilized to extend standard
macroscopic equilibrium theory in such a manner as to incorporate friction can be cast as well in the
continuous, fieldlike formulation of nonequilibrium thermodynamics. © 2010 American Institute of
Physics. 关doi:10.1063/1.3477189兴

I. INTRODUCTION AND PRELIMINARIES
The Clausius inequality is the pillar upon which modern
thermodynamic analysis has been built, having led, together
with Clausius’ introduction of the entropy function, to the
formal, mathematical statement of the second law.1,2 It reads
Not only the Clausius inequality remains a player in
modern physics, chemistry, and engineering, as when esti-
mating the heat generated by information erasure,4,5 or ana-
lyzing thermal performance in linear irreversible
thermodynamics,6 but is still an object of active research,
attracting the interest of physicists, chemists, and engineers,

冖 –dQ
T
ⱕ 0, 共1兲
for instance, when it comes to its apparent violation in the
quantum regime,7 its proof as an emergent phenomenon in a
low-entropy environment,8 its rectification to obtain expres-
for a cyclic transformation of a given closed system during sions for entropy production,9 also when searching for a me-
which the infinitesimal amount of heat –dQ is delivered to it chanical representation of entropy,10 or its restatement in the
when its absolute temperature is T, or presence of heat transfer via radiative fluxes,11 the purpose of
–dQ this article being precisely to revisit and generalize it when
dS ⱖ , 共2兲 frictional work is explicitly accounted for. The importance of
T
the subject addressed stems not only from the quintessential
if written in terms of the system’s entropy change dS for an role the Clausius inequality has never ceased to play in ther-
infinitesimal process. A slightly different, somewhat less modynamics, a branch of science whose birth was driven by
stringent form is the need to find the physics underlying the technology of the
time, which still today is the mantra of applied physics, but
Q
兺i Tii ⱕ 0, 共3兲 also from the fundamental, timeless interest in combining
together the second law and friction, the former, arguably the
for a cyclic process in which the system receives the quan- ultimate driving principle in the natural world, the latter,
tities of heat Qi from a series of reservoirs with temperatures most likely nature’s primary source of dissipation.
Ti. Splitting dS into an internal entropy production term dSint Friction has often made its appearance in thermodynam-
and the entropy –dQ / T flowing into a closed system through ics, almost always from the point of view of applied physics
its boundary,3 and engineering, which is that of finite-time thermodynamics
where most of the analyses have been carried out,12–16 and
–dQ only sporadically has frictional work been treated from a
dS = dSint + , 共4兲
T more basic perspective.17 In a recent paper,18 a new approach
has been proposed to include friction explicitly in the frame-
Eq. 共2兲 can still be put in the form
work of classical thermodynamics, its starting and most dis-
dSint ⱖ 0. 共5兲 tinctive point being to acknowledge that, in such a case, the
work –dW delivered to a system is not equal to the work –dW 0
a兲
Electronic mail: bizarro@ipfn.ist.utl.pt. performed by its surroundings, or environment, but that

0021-8979/2010/108共5兲/054907/9/$30.00 108, 054907-1 © 2010 American Institute of Physics

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 054907-2 João P. S. Bizarro J. Appl. Phys. 108, 054907 共2010兲

–dW = –dW + –dW 共6兲 with examples of relevance for applied physics, such as heat
0 fric
engines, mesoscopic devices, and heat transport, the findings
instead, with –dWfric the work done against friction forces. being summarized and conclusions being drawn in Sec. III.
Due to the first law, or energy conservation, one also has
–dQ = –dQ − –dW , 共7兲 II. ANALYSIS, RESULTS, AND DISCUSSION
0 fric
A. Macroscopic framework
where –dQ0 and –dQ are the net heat fluxes flowing out of the
surroundings and into the system, respectively, Eqs. 共6兲 and To restate the Clausius inequality when friction is dealt
共7兲 clearly stating that frictional work is dissipated as heat, with explicitly, one has only to incorporate Eqs. 共6兲–共9兲
an interpretation as old as Joule’s famous paddle-wheel above in first and second law analysis and carry out the stan-
experiment.18 Since, in general, –dWfric will be dissipated dard program of macroscopic thermodynamics. Using Clau-
sius’ own formulation, that the energy of the universe is a
partly in the system and partly in the environment, –dQ0 and
constant and that its entropy tends to a maximum,2 the first
–dQ will have each a term coming from frictional work in
and second laws formally read
addition to the heat –dQexch directly exchanged between them,
dUuniv = 0 共10兲
so
and
–dQ = –dQ –
exch + ␣ dWfric 共8兲
dSuniv ⱖ 0, 共11兲
and
the universe representing here an isolated system formed by
–dQ = –dQ –
0 exch − 共1 − ␣兲dWfric , 共9兲 the actual, smaller system under study and the surroundings,
or reservoirs, with which it interacts. If a system undergoes a
␣ designating the fraction of –dWfric that ends up going to the cyclic process during which it receives the work W and the
system.19 heat Q, these must obey
Of course, the question may be raised if making the
Q + W = 0, 共12兲
contribution of friction explicit in thermodynamics, as done
below for the Clausius inequality, is a mere rewriting of because, returning the system to its initial state, its internal
well-known, old physics, or if it is indeed a true generaliza- energy has not changed, the same being true for its entropy,
tion. The answer lies somewhere in between since, no, there whence
will be no introduction of new fundamental physics, as the
⌬S = 0. 共13兲
analysis will not go beyond the much respected and vener-
ated first and second laws, and, yes, there will be novel Moreover, if the amounts of heat transferred directly to the
physical results and implications presented, ranging from the system by a series of reservoirs during the transformation are
efficiency analysis of thermal engines to the energetics of designated by Qexch,i and those of frictional work dissipated
Landauer’s bound and memory erasure,4,5 including as well in them by 共1 − ␣i兲Wfric,i, then the heat effectively lost by
friction at the interface between two systems due to the slid- each of them is, by Eq. 共9兲,
ing of one with relation to the other.20 Also, as opposed to
Q0,i = Qexch,i − 共1 − ␣i兲Wfric,i . 共14兲
so-called internal friction due, for instance, to viscous flow,3
the present paper will focus on, say, frictional dissipation at Recalling that the entropy change for the ith reservoir is
the system’s boundary, the paradigm being sliding friction
Q0,i
which is, furthermore, particularly suited to illustrate the dis- ⌬Si = − , 共15兲
tinction between quasistatic and reversible processes.17,18 In Ti
addition, and notwithstanding that the scientific program and Eqs. 共11兲 and 共13兲–共15兲 imply
output in this article will be carried out and stated mostly
Qexch,i 共1 − ␣i兲Wfric,i
within the classical framework of macroscopic thermody-
namics, consistency will be shown with the consecrated local
兺i Ti
ⱕ兺
i Ti
, 共16兲

theory of nonequilibrium thermodynamics, formulated in

terms of continuous, fieldlike state variables.3,20 Although, which generalizes Eq. 共3兲 to the case where frictional work
for the sake of pedagogy, classical mechanical analogies and must be accounted for and which, considering Eq. 共14兲, can
examples will be used, friction is to be here understood in its be written alternatively as
broadest sense meaning, as detailed above, that frictional Q0,i
work is present whenever the work output from the sur- 兺i Ti
ⱕ 0, 共17兲
roundings is not identical to the work input to the system
under study. So, after this Sec. I, with its introductory and very much resembling, but by no means being the same as
preliminary considerations, the Clausius inequality with fric- Eq. 共3兲. When compared with Eq. 共3兲, Eq. 共16兲 has a very
tion will be comprehensively studied in Sec. II using not simple physical interpretation: since the heat resulting from
only the standard macroscopic formulation but the nonequi- frictional dissipation effectively contributes to increase the
librium approach as well, always discussing the results de- entropy of the reservoirs, the net entropy coming into the
rived, with its implications and applications, and illustrating latter due to heat exchange with the system, or −兺iQexch,i / Ti,
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 054907-3 João P. S. Bizarro J. Appl. Phys. 108, 054907 共2010兲

no longer needs to be strictly non-negative to comply with designating the efficiencies for dithermal engines with and
the second law. As stated by Eq. 共17兲, it is the total entropy without friction as
flowing to the ensemble of reservoirs, from both friction and
兩W0兩
system, which is −兺iQ0,i / Ti, that has to be positive or vanish. ␩fric = 共22兲
Comparing Eq. 共17兲 with Eq. 共3兲, it may be tempting to state Q0,h
that the well-know forms of the Clausius inequality recalled and
in Sec. I can be trivially generalized to include friction by
merely replacing –dQ or Qi, whatever suitable, by –dQ0 or Q0,i, 兩W兩
␩= , 共23兲
respectively, and then using Eq. 共9兲 or Eq. 共14兲.21 Although Qh
this rule of thumb may apply in some circumstances, it will
be shown below to be not always true, so it must be used respectively, Eqs. 共21兲–共23兲 yield
carefully to avoid pitfalls. 兩W兩 − Wfric
Besides its intrinsic, fundamental interest, Eq. 共16兲 is ␩fric = ␩ , 共24兲
兩W兩 − ␩Wfric,h
also of practical utility, for instance, as a starting point to
reformulate the analysis of thermal engines to incorporate so, since ␩ is no greater than unity and Wfric,h no greater than
friction from the very first stage. Schematically, combining Wfric,
Eq. 共12兲 with the first law, Eq. 共10兲, written for the system
plus reservoirs, one gets for the effective work output ␩fric ⱕ ␩ , 共25兲
an obvious, expected result, yet one whose formal, universal,
− W0 = 兺 Q0,i , 共18兲 hence model-independent derivation has been made possible
i
by the formalism here developed. Although the analysis con-
which, as follows from Eq. 共6兲 and should be stressed, is not ducted here above on engine efficiency seems more directly
equal to the work −W performed by the system. Then, put- concerned with macroscopic thermal systems, such as those
ting together Eqs. 共14兲, 共16兲, and 共18兲, the expression found in applied thermodynamics, it is no less important for

冉 冊
T0
− W0 ⱕ 兺 1 − 关Qexch,i − 共1 − ␣i兲Wfric,i兴
i Ti
follows for the maximum work that can be extracted from
the device, where the reservoir with T0 has been taken as
playing the role of surroundings.22 Note that Eq. 共19兲 has
been written for a work-producing engine or power plant
whereas, for a refrigeration machine or plant, it must be mul-
tiplied by minus one to yield the minimum amount of work
one needs to have it functioning.
As a particular, illustrative example, take a dithermal
engine operating between a hot and a cold reservoir with
temperatures Th and Tc, respectively, in which case Eqs. 共14兲
chemical systems or mesoscopic devices as, for instance,
共19兲 when studying the interface between two materials at differ-
ent temperatures or the behavior of biological
macromolecules.9
Going from the realm of thermal engines and reservoirs
to that of thermodynamic processes, it becomes more conve-
nient to have the Clausius inequality written in terms of the
system’s temperature, as in Eqs. 共1兲 or 共2兲, the respective
derivation being usually done with recourse to a cyclic trans-
formation in which a reversible engine is inserted between
the system and the environment.1 This is better understood
by noting that, when a system interacts with its surroundings
giving off the heat −d – Q , the amount −d – Q⬘ rejected to
exch
the latter lies within the interval
exch

and 共19兲 yield

兩W0兩 Tc
ⱕ1− ,
Q0,h Th
thus recovering Carnot’s classical result imposing a limit on
the engine’s efficiency.1,2 However, an important difference
should be remarked: the efficiency 兩W0兩 / Q0,h is now defined
in terms of the work effectively delivered to the environment
and of the net heat lost by the hot reservoir, instead of being
written as 兩W兩 / Qexch,h using the work and heat flowing out
and into the system, respectively. To better appreciate the
distinction, note that
T0 –
− ⬘ ⱕ − –dQexch ,
dQexch ⱕ − –dQexch 共26兲
共20兲 T
the lower value corresponding to use −d –Q
exch to drive a re-
versible engine operating between the system and the
reservoir,1 and the higher to a direct, nonmediated transfer of
heat between the two. Therefore, the contribution to the en-
tropy increase in the universe in such a cyclic transforma-
tion, which comes only from the environment because of Eq.
共13兲, follows from combining Eq. 共9兲 with a form similar to
Eq. 共15兲, provided the heat –dQexch in Eq. 共9兲 is replaced by
–dQ⬘ given in Eq. 共26兲, whence

冖冋 册
exch
兩W0兩 兩W兩 − Wfric
= , 共21兲 –dQ –W
共1 − ␣兲d
Q0,h Qexch,h − Wfric,h −
exch
−
fric
ⱕ ⌬Suniv ⱕ
T T0

冖冋 册
as follows from Eqs. 共6兲 and 共7兲 and where Wfric represents
the work lost due to friction in the entire cycle, while Wfric,h –dQ –W
共1 − ␣兲d
exch fric
is that part dissipated during the interaction with the reser- − − . 共27兲
T0 T0
voir at Th, Eq. 共21兲 already paving the way for an analysis of
the impact of friction on an engine’s efficiency. For instance, Since Eq. 共11兲 must apply to both ends of Eq. 共27兲, then
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 054907-4 João P. S. Bizarro J. Appl. Phys. 108, 054907 共2010兲

冖 –dQ
T
exch
ⱕ 冖 T0
–W
共1 − ␣兲d fric
共28兲 dSuniv ⱖ 冉 1 1 –
−
T T0
冊
dQexch 共35兲

and and yields as a natural lower bound for dSuniv the contribu-
tion arising from the irreversible heat exchange between the

冖 –dQ
T0
exch
ⱕ 冖 T0
–W
共1 − ␣兲d fric
, 共29兲
Eq. 共28兲 hereabove extending the Clausius inequality in Eq.
共1兲 to include friction, whereas Eq. 共29兲 is the continuous,
cyclic integral form of Eq. 共16兲 and can also be derived from
it by going to a continuum of reservoirs.1 It is worth remark-
ing that Eq. 共28兲 is a stronger inequality than Eqs. 共16兲 or
共29兲, as the latter can be derived directly from the former
because Eq. 共26兲 implies
–dQ –dQ
exch exch
ⱖ ,
T T0
which is equivalent to Clausius’ statement of the second law
that heat cannot pass spontaneously from a colder to a
warmer body.1,2 Recalling a previous comment, made in con-
nection with Eq. 共17兲, it must be noted that the strongest
form of the Clausius inequality Eq. 共28兲 does not follow
from Eq. 共1兲 by simply replacing –dQ by –dQ0 and so will not
some of its forms derived below with respect to their coun-
terparts in Sec. I.
Following the standard approach,1,2 the closed path in
Eq. 共28兲 can be split into a reversible process, in which
–dW evidently vanishes and the ratio on the left-hand side
fric
of Eq. 共28兲 gives the system’s entropy change dS, and an
irreversible one, the outcome of such an exercise being, al-
ready in infinitesimal form,
system and the surroundings when they are not in thermal
equilibrium with each other. Even if the sources of mechani-
cal irreversibility, namely, friction and deviations from qua-
sistatic conditions,18 are left out of Eq. 共35兲, such an expres-
sion can be of use as an estimate by default for entropy
production when the dissipative work is not known.9,23
It is now useful to illustrate Eq. 共31兲 with the paradig-
matic example of a gas slowly, or quasistatically, compressed
by, or expanding against, a piston with sliding friction,17,18
taking
–dW = ⫿ P dV, 共36兲
fric fric
共30兲
with Pfric a friction force considered constant and divided by
the piston cross-sectional area, V the gas volume, and the
upper and lower signs corresponding to compression and ex-
pansion, respectively, so –dWfric is always positive. For an
isothermal process with n moles of an ideal gas, in which
case T and T0 are identical whereas –dQ and –dW are sym-
metrical, one has
–dQ = nRT0dV 共37兲
V
with R the ideal gas constant, so, inserting Eqs. 共8兲, 共36兲, and
共37兲 in Eq. 共31兲, one gets
nRdV PfricdV
dS ⱖ ⫾ , 共38兲
V T0

–dQ –W which, upon integration, gives

共1 − ␣兲d
冉 冊
exch fric
dS ⱖ − . 共31兲 ⌬V Pfric兩⌬V兩
T T0 ⌬S ⱖ nR ln 1 + − . 共39兲
V T0
This reads as a nontrivial extension of Eq. 共2兲, obviously
leading to Eq. 共11兲 for an isolated system, when there is no If the transformation is adiabatic, so –dQexch vanishes,18 Eqs.
–dQ
exch and ␣ reduces to unity, meaning that frictional dissi- 共31兲 and 共36兲 yield
pation takes place entirely in the system. Putting together
共1 − ␣兲PfricdV
Eqs. 共4兲, 共8兲, and 共31兲, the Clausius inequality becomes dS ⱖ ⫾ , 共40兲
T0
␣ –dWfric 共1 − ␣兲d–Wfric whence
dSint ⱖ − − 共32兲
T T0
共1 − ␣兲Pfric兩⌬V兩
or ⌬S ⱖ − , 共41兲
T0
dSint + dSfric ⱖ 0, 共33兲 constituting a straightforward exercise to check the bounds
after identifying in Eqs. 共39兲 and 共41兲 are consistent with the well-known
expression for ⌬S of an ideal gas as well as with previous
␣ –dWfric 共1 − ␣兲d–Wfric results.18
dSfric = + 共34兲 It is probably worth to stress that the fundamental as-
T T0
sumptions and validity of the results derived within the
with the total entropy increase resulting from frictional present macroscopic framework are precisely those of equi-
dissipation,18 Eq. 共33兲 reading as a beautifully simple and librium thermodynamics: state functions such as tempera-
intuitive refinement of Eq. 共5兲, hence of the second law. ture, internal energy, and entropy are well-defined quantities
Another way of writing Eq. 共31兲 comes from adding to it throughout the system for any of its equilibrium states,
the environment’s entropy change, as given by the infinitesi- whereas heat and work exchanges take place while the sys-
mal versions of Eqs. 共14兲 and 共15兲, which leads to tem evolves from one such state to another. In particular, the
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 054907-5 João P. S. Bizarro
different forms of the Clausius inequality presented here,
which are taken and written between two equilibrium states
and evidently presuppose a time scale no shorter than the
system’s characteristic relaxation time, are not limited by any
considerations or peculiarities regarding the velocity or path
dependence of the frictional process. The examples based on
Eq. 共36兲 above have been chosen essentially because of sim-
plicity and assuming a constant, velocity-independent fric-
tion force, are typical of sliding friction between dry sur-
faces, besides providing one of the few instances where the
thermodynamics of irreversible quasistatic transformations
can be studied.17 An alternative, more practical example
arises from frictional dissipation in well-lubricated nonideal
heat engines, where the friction force is usually supposed to
be linear in the macroscopic velocity Ẋ, hence the quadratic
law
Ẇfric = ␮Ẋ2 ,
for the frictional power loss, with ␮ some friction
coefficient.12–14,16 For a purely sinusoidal motion of a piston
in a standard four-stroke engine, Eq. 共42兲 can be integrated to
give
冖 –W =
共1 − ␣兲d fric
2␲2共1 − ␣兲␮共⌬X兲2
␶
, 共43兲
with 共1 − ␣兲␮ the mean of the overlined quantity in one
cycle, the latter having period ␶ and encompassing two
crankshaft revolutions, and ⌬X the full excursion of the pis-
ton motion.13 So, Eqs. 共31兲 and 共43兲 combine to yield
⌬S ⱖ 冖 –dQ
T
exch
−
2␲2共1 − ␣兲␮共⌬X兲2
␶T0
, 共44兲
the first term in Eq. 共44兲 depending on the details of the heat
transfer during the thermodynamic cycle.
A further inequality, derived from Eqs. 共30兲 and 共31兲, or
directly from Eq. 共29兲, is
–dQ –W
共1 − ␣兲d
exch fric
dS ⱖ − ,
T0 T0
or, because of Eq. 共9兲,
–dQ
dS ⱖ
0
, 共46兲
T0
whose usefulness can be illustrated, entering the world of
device physics, by considering Landauer’s bound for the
minimum heat generated by the erasure of one bit of infor-
mation in a binary memory.4,5 Basically, restoring N memo-
ries to a definite state, without leaving any trace of their
previous values and no matter which of the two possible
states they were initially in, must be accompanied by a re-
duction in the system’s entropy
⌬S = − NkB ln 2,
where kB is Boltzmann’s constant. If the memories are im-
mersed in an environment with temperature T0, inserting Eq.
共47兲 in Eq. 共46兲 then gives
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J. Appl. Phys. 108, 054907 共2010兲
兩Q0兩 ⱖ NkBT0 ln 2 共48兲
as a lower bound for the net amount of heat absorbed by the
surroundings as a result of the erasure operation, which is not
a minimum for the dissipative work due to friction, the latter
being bounded instead according to
Wfric ⱖ Qexch + NkBT0 ln 2, 共49兲
as follows from Eq. 共45兲 if one assumes ␣ is nil, so frictional
work is totally dissipated in the environment. A measure of
success for the macroscopic formulation here utilized to ac-
count for friction is that, without recourse to a microscopic
model of the memory device, it immediately clarifies one of
the issues at stake when discussing the validity of Landauer’s
bound: what is indeed meant by “heat generation required by
information erasure” or what quantity is indeed bounded by
kBT0 ln 2?4 The answer is naturally conveyed by Eqs. 共9兲,
共42兲 共48兲, and 共49兲, leading to the correct interpretation that the
memory device not only generates but also absorbs heat from
the surroundings, in the amounts given by Wfric and Qexch,
respectively, being the difference between these two quanti-
ties that actually enters 共48兲.4
B. Nonequilibrium formulation
In many engineering problems and physics applications
one has to resort to a description in terms of continuous
media, in which case thermodynamics must be incorporated
in the appropriate system of transport equations, this being
carried out with recourse to a nonequilbrium formulation.3,20
In nonequilibrium thermodynamics the state parameters are
treated as field variables, that is, as continuous functions of
space and time, so the basic equations of the theory should
be set from the start in local form. Moreover, the so-called
entropy balance equation plays a central role, expressing “the
fact that the entropy of a volume element changes with time
for two reasons: first because entropy flows into the volume
element, second because there is an entropy source due to
irreversible phenomena inside the volume element.”3 So,
“for open systems, 关…兴 which may exchange heat as well as
共45兲 matter with their surroundings,” introducing the mass density
␳, the entropy per unit mass s, the entropy flow per unit area
and unit time Js, and the entropy production per unit volume
and unit time ␴, the so-called entropy source strength,3 one
may write
冕
S= ␳sdV 共50兲
for a system’s entropy and
dS
dt
= 冕 ⳵ 共␳s兲
⳵t
dV 共51兲
for its time rate of change or, in the form of a balance equa-
tion,
共47兲
冕 ⳵ 共␳s兲
⳵t
dV = − 冕 共Js + ␳sv兲 · ndA + 冕 ␴dV. 共52兲
Here dV is the volume element and n the unit normal to the
surface at the element of area dA pointing outward, v is
 054907-6 João P. S. Bizarro J. Appl. Phys. 108, 054907 共2010兲

velocity, ␳sv being thus the convected entropy flow, whereas
the surface integral in Eq. 共52兲 is the rate at which “entropy
关is兴 supplied to the system by its surroundings” and the vol-
ume integral
component Jq,exch due to direct heat flow from the surround-
ings, plus a term Jq,fric resulting from friction, namely,
Jq = Jq,exch + Jq,fric , 共63兲

冕
such that, with Eqs. 共62兲 and 共63兲, Eq. 共61兲 becomes

冉 冊
dSint
= ␴dV, 共53兲 ds Jq,exch + Jq,fric − 兺k␮kJk
dt ␳ =−ⵜ· + ␴. 共64兲
3 dt T
the rate at which “entropy 关is兴 produced inside the system.”
Reformatting Eq. 共52兲 with the help of Gauss’ theorem Because frictional dissipation is considered in this paper to
leads to take place at the boundary between the system and surround-

冕冋 册 ings, such as sliding friction,17,18 the following relation ap-

⳵ 共␳s兲
+ ⵜ · 共Js + ␳sv兲 − ␴ dV = 0, 共54兲 plies:
⳵t
共Jq0,fric − Jq,fric兲 · n = ␬fric , 共65兲
and rewriting Eq. 共5兲 as
where Jq0,fric is the flow of frictional heat to the environment
dSint and the source ␬fric the rate at which heat arising from fric-
ⱖ0 共55兲
dt tion is produced per unit area at the boundary.24 To facilitate
the confrontation with the equilbrium, macroscopic formula-
gives
tion, for instance, with Eqs. 共7兲–共9兲, note that

冕 ␴dV ⱖ 0, 共56兲
Q̇exch = − 冕 Jq,exch · ndA, 共66兲

whence
⳵ 共␳s兲
⳵t
= − ⵜ · 共Js + ␳sv兲 + ␴ , 共57兲
Ẇfric = 冕 ␬fricdA, 共67兲

with
␴ ⱖ 0, 共58兲
␣Ẇfric = − 冕 Jq,fric · ndA, 共68兲

since Eqs. 共54兲 and 共56兲 must hold for an arbitrary volume, and
Eq. 共57兲 being equivalent, accounting for mass conservation
⳵␳
= − ⵜ · 共␳v兲 共59兲
共1 − ␣兲Ẇfric = 冕 Jq0,fric · ndA. 共69兲

⳵t Evidently,
and considering that − Jq,fric · n ⱖ 0 共70兲
ds ⳵ s and
= + v · ⵜs, 共60兲
dt ⳵ t
Jq0,fric · n ⱖ 0, 共71兲
to
whereby

冕 冕
ds
␳ = − ⵜ · Js + ␴ , 共61兲 dSfric Jq,fric · n Jq0,fric · n
dt =− dA + dA 共72兲
dt T T0
which reads as the local entropy balance equation written in
a general, synthetic form.3 The subsequent step in the analy- verifies
sis consists in expanding the right-hand side of Eq. 共61兲, dSfric
giving for ␴ a sum of products of a flow or rate quantity ⱖ 0, 共73兲
dt
times its conjugate thermodynamical force, basically the gra-
dient or difference of an intensive state variable, whose de- as expected, Eq. 共72兲 coinciding, via Eqs. 共68兲 and 共69兲, with
tails are of no relevance for the present study, and yielding Eq. 共34兲 when T and T0 are uniform within the system and
for Js the expression surroundings, respectively.
Going now backward, introducing Eqs. 共62兲 and 共63兲 in
J q − 兺 k␮ kJ k
Js = , 共62兲 Eq. 共54兲, and using again Gauss’ theorem to perform the
T integration over the volume of a closed system, in which
with Jq and Jk representing the heat and matter flows, respec- case both 兰Jk · ndA and 兰␳sv · ndA vanish, one obtains
tively, and ␮k the chemical potential of component k.3
If friction is to be explicitly introduced in a continuous
nonequilibrium formulation of thermodynamics, Jq must
冕 ⳵ 共␳s兲
⳵t
dV = − 冕 共Jq,exch + Jq,fric兲 · n
T
dA +
dSint
dt
共74兲

than be split, following the lines suggested by Eq. 共8兲, into a and, if use is still made of Eqs. 共51兲, 共53兲, and 共72兲,
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 054907-7 João P. S. Bizarro J. Appl. Phys. 108, 054907 共2010兲

dS
dt
=− 冕 Jq,exch · n
T
dA − 冕 Jq0,fric · n
T0
dA +
dSfric dSint
dt
+
dt
.
contributions to Jq in Eq. 共63兲 and hence single out Jq,fric,
with the thermodynamic driving, most notably the tempera-
ture gradient, governing the heat flow Jq as a whole and
共75兲 being unable to discriminate between its two components.
Combining next Eq. 共33兲, restated as When giving Jq0,fric and Jq,fric at the system’s boundary,
it must be noted that they are not independent, because of
dSfric dSint energy conservation as expressed by Eq. 共65兲. For demon-
+ ⱖ 0, 共76兲
dt dt strative purposes, and assuming there is no heat flow within
the boundary and, as in previous work,18 that the latter has a
with Eq. 共75兲 implies vanishing heat capacity, so all the heat produced by friction
dS
dt
ⱖ− 冕 Jq,exch · n
T
dA − 冕 Jq0,fric · n
T0
dA, 共77兲
is transferred locally to the system or the surroundings, Eqs.
共65兲 and 共67兲 become
兩Jq0,fric兩 + 兩Jq,fric兩 = ␬fric , 共79兲
“which is equivalent with the 关…兴 Clausius 关…兴 关inequality
Eq. 共32兲兴 as it should,”3 more precisely and accounting for to be complemented by a local version of Eq. 共68兲, namely,
Eqs. 共66兲 and 共69兲, Eq. 共77兲 reduces to Eq. 共32兲 if the system
and surroundings are in equilibrium each, with uniform tem- 兩Jq,fric兩 = ␣␬fric . 共80兲
peratures throughout their volumes, confirming once more So, from a formal point of view, what remains to be done is
the correctness of the approach adopted to deal with friction to compute
in thermodynamics and constituting yet another extension of
a previous result.25 dẆfric
It is always possible to ask if Eq. 共76兲 is simply a rewrit- ␬fric = , 共81兲
dA
ing of the well-established result Eq. 共5兲,3 or if it is indeed an
extension of the latter, given that dSint could, eventually, in- a detailed prescription of which, however, lies outside the
corporate all causes of entropy increase pertaining to the sys- scope of the present work and will most likely turn to some
tem, whether they occur within it or at its surface. The fore- sort of empirical law.27–30
going analysis points clearly toward the second option It must be said that frictional forces on surfaces have
because, not only dSfric contains a term coming from the already appeared within the context of nonequilibrium ther-
surroundings, as made apparent in Eqs. 共34兲 and 共72兲, but the modynamics, namely, when the latter has been applied to the
sources of entropy production accounted for in dSint and interface between two immiscible fluids, treating it as a sin-
dSfric are structurally different. In fact, comparing Eq. 共53兲 gular layer.20 Basically, the standard linear phenomenologi-
with Eq. 共72兲, dSint is determined by the volume-distributed cal laws between thermodynamical forces and fluxes have
sources of entropy, which are intimately linked to the gradi- been collapsed onto a surface, so the frictional contribution
ents or thermodynamic forces,3 whereas dSfric arises from a to the pressure tensor appears as a viscous-type term propor-
surface contribution, which is governed by heat flows. This tional to the relative sliding velocity v at the interface. This
is also apparent in the generalization of Eq. 共58兲 and local leads to an entropy production rate per surface area due to
translation of Eq. 共76兲 friction that reads31

␴+ⵜ· 冉 T0
−
T
冊
Jq0,fric Jq,fric
ⱖ 0, 共78兲 ␴surf =
␤兩v兩2
Tsurf
, 共82兲

obtained by combining Eqs. 共53兲, 共72兲, and 共76兲 and making with ␤ a friction coefficient and Tsurf a so-called surface tem-
use once more of Gauss’ theorem. Note that, while frictional perature which, in the present case, that theory predicts to be
dissipation at the system’s boundary, which constitutes the essentially given by20
focus of the present article and is well examplified by sliding
friction between dry solid surfaces,17,18 is incorporated in T + T0
Tsurf = . 共83兲
dSfric, so-called internal friction due to viscous flow is usu- 2
ally included in dSint.3,26 Alternatively, following the prescription here proposed in
If the explicit inclusion of friction in a nonequilibrium Eqs. 共79兲–共81兲, the frictional heat currents at the surface are
formulation of thermodynamics is to be of use for concrete given by the frictional dissipated power per surface area,
applications, some words must be said on the form of the
frictional heat currents Jq0,fric and Jq,fric which, being gener- ␬fric = ␤兩v兩2 , 共84兲
ated within a very thin contact layer between the system and
surroundings, should be regarded essentially as boundary for a friction force proportional to v, whence, combining
conditions to be prescribed on the system’s surface. One Eqs. 共79兲, 共80兲, and 共84兲 with a local version of Eq. 共72兲,
might think of specifying Jq,fric inside the system as well, for
instance, via some constitutive relation similar to the linear
phenomenological laws linking irreversible flows to thermo-
␴surf = 冋 ␣ 1−␣
T
+
T0
册
␤兩v兩2 , 共85兲

dynamic forces,3 but that would not be feasible since it which can still be put in a form similar to Eq. 共82兲 by defin-
would be virtually impossible to separate therein the two ing
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 054907-8 João P. S. Bizarro
1 ␣ 1−␣
= + . 共86兲
Tsurf T T0
Comparing Eq. 共83兲 with Eq. 共86兲, both are averages of the
temperatures of the system and surroundings, the first a
simple arithmetic mean and the second an inverse average
weighted by the fractions of frictional heat lost to the system
and reservoir.32 Within the domain of validity of the theory
leading to Eq. 共83兲, which demands that “the deviations from
equilibrium are not “too large”,”20 one can actually combine
the two definitions for Tsurf to estimate ␣ as
T tional dissipation entering then as an additional contribution
␣= , 共87兲
T + T0
which is obviously meaningless when T / T0 becomes very
large or very small, in which case ␣ approaches unity or
zero, respectively, an indication that T and T0 are signifi-
cantly different, so one is clearly far from equilibrium and
Eq. 共83兲 no longer holds.33
III. SUMMARY AND CONCLUSIONS
The second law as stated by the Clausius inequality has
been refined to make clear the impact of frictional work, the
material presented in this article remaining within the strict
boundaries defined by the classical formulation of the first
and second laws:1,2 no new dawn in macroscopic thermody-
namics is announced nor is there any intent to lay down new
foundations for it. The purpose has been simply to incorpo-
rate frictional work explicitly in the framework and machin-
ery of standard thermodynamic analysis, thus providing not
only a general, unified approach to friction, in contrast to the
usual model-dependent treatment found in finite-time
thermodynamics,12–16 but also bringing basic thermodynam-
ics closer to actual engines, processes, and devices, in which
friction forces are omnipresent actors. This is a first step to
encompass friction from scratch in the classical formulation
of thermodynamics, a program covering a broad spectrum of
interests in physics, chemistry, and engineering, particularly
when involving entropy production in situations where dis-
sipation due to friction must be included, either because it is
already known to be important or has still to be evaluated. In
the first case one finds thermal science and the optimization
of engine, refrigerator, or power plant performance via
entropy-generation minimization,12–16 whereas in the second
one may cite the behavior of biological and macromolecular
systems or of mesoscopic devices,9 or still the self-
organization of magnetic fusion plasmas due to entropy
maximization.34
A distinct feature when considering friction on its own in
thermodynamics is that the energy fluxes into a system and
from its surroundings, be it in the form of work or heat, are
no longer reciprocal, the difference between them yielding
the amount of frictionally dissipated heat.18 As a conse-
quence, and one to be stressed, the new, generalized forms of
the Clausius inequality derived in Sec. II cannot be reduced
to the consecrated ones, given in Sec. I, when friction is
effectively present, so the former are more than a simple
rewriting of the latter.35 Several implications related to fric-
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J. Appl. Phys. 108, 054907 共2010兲
tion in thermodynamics have been discussed, for instance,
the expected result that frictional work always contributes to
reduce the efficiency of dithermal engines has been formally
demonstrated in an universal manner, while a better under-
standing has emerged regarding the energetics of Landauer’s
bound for the heat generated by information erasure.4,5
Moreover, the macroscopic framework set up to address fric-
tion, which is based on classical thermodynamic analysis,18
has been translated into the standard, continuous formalism
of nonequilibrium thermodynamics, written in terms of local
differential equations for fieldlike variables,3,20 with fric-
to the heat flow whose source is located on the boundary
between the system and surroundings.
The basic, fundamental conclusion that comes out from
the different generalized forms of the Clausius inequality de-
rived in this work is that the constraints imposed by the
second law on a system’s entropy change are lessened be-
cause of entropy production due to friction, which allows the
lower bound for that change to become smaller than usually
stated. Although, truly speaking, this result does not classify
as a full surprise it has, nonetheless, been presented here in a
systematic, comprehensive, and detailed manner, via a series
of expressions that are well suited for quantitative analysis
and cover a wide range of applications. Finally, a call of
attention on how important it would be to have frictional
dissipation included in a quantum formulation of thermody-
namics, where the most challenging questions about the va-
lidity of the Clausius inequality, and thus also of the second
law, have been raised, namely, in situations where entangle-
ment plays a crucial role,7,8 as well as in the most recent
expansion of thermodynamics, the so-called constructal law
and the phenomenon of design and evolution in nonequilib-
rium flow systems.36
ACKNOWLEDGMENTS
This work was carried out under the auspices of the Con-
tract of Association between the European Atomic Energy
Community and the Instituto Superior Técnico 共IST兲 and of
the Fundação para a Ciência e a Tecnologia 共FCT, Lisboa兲.
The content of this paper is the sole responsibility of the
author and does not necessarily represent the views of the
European Commission, of FCT, of IST, or of their services.
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Remark that the introduction in Ref. 18 of a parameter ␣ to split frictional
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A similar trend can be found in Ref. 18 by comparing Eqs. 共7兲–共9兲 with
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from the former by replacing –dQ and –dW by –dQ0 and –dW0, respectively.
22
If Eq. 共19兲 pertains to some kind of power or refrigeration plant, T0 is
usually the temperature of the atmospheric reservoir as in Ref. 15.
23
The terms missing on the right-hand side 共rhs兲 of Eq. 共35兲, and which
would turn it into an equality, can be easily identified in Eq. 共22兲 of Ref.
18.
24
As in Ref. 18, it has been assumed that the boundary has a vanishing heat
capacity, otherwise ␬fric in Eq. 共65兲 would have to be reduced by subtract-
ing a term like cbounddTbound / dt, with cbound the boundary’s heat capacity
per unit area and Tbound its temperature.
25
Indeed, the Clausius inequality in the form Eq. 共77兲 generalizes Eq.
共III.22兲 of Ref. 3 to situations where there is frictional dissipation.
26
Recall that in Ref. 17, an earlier work on friction and thermodynamics, a
distinction was already made between viscous and sliding friction with
regard to the difference between quasistatic and reversible processes.
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130.209.6.50 On: Mon, 22 Dec 2014 19:47:37
J. Appl. Phys. 108, 054907 共2010兲
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Indeed, Eq. 共82兲 can be obtained from Ref. 20 by taking the second term
on the rhs of Eq. 共5.3兲 therein, which is the one identified with friction,
plugging it into the third term on the rhs of Eq. 共4.13兲, while noting the
sentence just after Eq. 共4.18兲, putting the relative velocity v+ − v− as simply
v, and replacing ␴s and Ts by ␴surf and Tsurf, respectively.
32
The strict arithmetic mean for Tsurf in Eq. 共83兲 may arguably be interpreted
as a mathematical artifact born from using in Ref. 20 a Heaviside step
function to describe the surface as a singular layer, whereas the weighted
average in Eq. 共85兲 looks more physically minded, with the parameter ␣
eventually retrievable by calorimetry.
33
However, Eq. 共86兲 is still meaningful as a definition for a surface tempera-
ture since, when ␣ becomes one, it makes Tsurf equal to T as if the bound-
ary surface had become part of the system which, according to Eq. 共85兲, is
precisely what happens from the point of view of the second law, the same
reasoning applying, mutatis mutandis, when ␣ vanishes.
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A simple rewriting would have been, for instance, to take Eq. 共8兲 and plug
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共31兲!
36
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