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冉 冊 冉 冊 冉 冊
are its enclosing walls before we proceed with a more real-
istic answer. S S n
dS = dT = dT 共1a兲
Energy transfer by heating a system will be used solely to T U,V n U,V T U,V
冉 冊冉 冊
increase its internal energy only if its enclosing walls are
rigid 共otherwise some of the energy transferred by heating n PV
could be used to do work on the outside兲 and the walls are = − − dT = dT. 共1b兲
T T RT T2
impermeable 共otherwise air will escape taking some of the
thermal energy with it兲. Rooms with rigid and impermeable Equation 共1b兲 follows from the mechanical equation of
walls exist, but hardly qualify as living rooms for obvious state of the ideal gas and the fundamental relation in the
reasons. entropy representation
The thermodynamic system of interest consists of the air dS = 共1/T兲dU + 共P/T兲dV + 共− /T兲dn 共2兲
in the room. The walls surrounding a room can be well char-
acterized as rigid because the thermal expansion of the walls so that
74 Am. J. Phys. 79 共1兲, January 2011 http://aapt.org/ajp © 2011 American Association of Physics Teachers 74
冉 冊
S
n U,V
=−
T
. 共3兲
兩u f − ui兩 = cV共T f − Ti兲.
Because the internal energy in an ideal gas is purely kinetic,
共7兲
冋冉 冊 冉 冊册
convection.
= 冕 Ti
Tf
dS = − PV
1 f 5
−
T f RT f 2
−
1 i 5
−
Ti RTi 2
,
Q= 冕 Tf
TdS
when the ideal gas approximation is not applicable? Like-
wise, what happens when we want to superheat steam? In
再冋 冎
Ti such situations, the simplification that constant pressure and
P 1
册 Tf
= PV ln NA 共h2/2mkB兲3/2 − c P ln共TiT f 兲 ln .
R 2 Ti
volume implies constant internal energy and volume cannot
be used. A student of thermodynamics must learn to treat
such problems in a systematic way without resorting to sim-
共6兲 plifying “tricks” as used in many books. Here, we follow the
procedure outlined in Ref. 6, Chap. 7.3. The procedure is a
Here, c P = cV + R is the specific heat at constant pressure 共c P good exercise in thermodynamic thinking and rigor.
We need the entropy change for a given temperature
= 3.48R for dry air, that is, there is a contribution of 21 R to cV change at constant pressure and volume,
冉 冊 冉 冊冉 冊
for each of three translational degrees of freedom and two
rotations, but vibrations are not excited at room tempera- S S n
dS = dT = dT. 共8兲
ture兲. T P,V n P,V T P,V
To obtain a sense for the magnitude of these changes,
consider a 4 m ⫻ 5 m ⫻ 2.5 m room with volume V We write
= 50 m3 and atmospheric pressure whose temperature is
raised from Ti = 273 K to T f = 300 K. We have to expel ther-
mal energy −Q ⬇ 10 MJ or 2.8 kW h, provided we make the
冉 冊
n
T P,V
=−
共 V/ T兲 P,n
共 V/ n兲T,P
. 共9兲
room completely air tight and thermally insulated as soon as The numerator is the thermal expansion coefficient ␣ at con-
the final temperature is reached. From the equation of state stant pressure up to a factor of V,
冉 冊
we have that n f T f = niTi so that in this heating process about
10% of the air has been expelled. The entropy change is V
V␣ = . 共10兲
⌬S ⬇ −26 kJ/ K. To put this number into perspective, we T P,n
note that the magnitude of this entropy change is about the
same as that occurs by heating and transforming four liters of For the denominator, we have the Maxwell relation
water completely into vapor at 1 atm pressure, for which
about 9 MJ is required 共⌬S and Q positive兲.
As Sommerfeld and others have discussed,4,5 although the
冉 冊
V
n T,P
=
2G
P n
=
P
冉 冊 T,n
=
V
n
. 共11兲
internal energy remains constant, the molar internal energy The last equality results from the fact that, for constant T, the
u = U / n increases by Gibbs–Duhem equation
75 Am. J. Phys., Vol. 79, No. 1, January 2011 H. J. Kreuzer and S. H. Payne 75
S
n
V
d = − dT + dP
n
共12兲 dS = ns 冋冉 冊 冉 冊册
1 V
V T P,n
−
1 S
S T P,n
dT, 共22兲
reduces to d = 共V / n兲dP. We thus obtain which is the difference between the relative volume and
entropy changes with temperature. Likewise, we obtain for
冏 冏 n
T P,V
= − n␣ . 共13兲
Eq. 共21兲,
dU = − nh 冋冉 冊 冉 冊 册
1 V
−
1 H
dT. 共23兲
We turn next to the first factor in Eq. 共8兲 and write V T P,n H T P,n
冉 冊
To see how the nonideality of the gas affects the heating
S 共 P/ n兲S,V process, we need to integrate Eqs. 共20兲 and 共23兲 for a par-
=− 共14兲
n P,V 共 P/ S兲V,n ticular gas, which can be done numerically, for example, for
water vapor using steam tables. However, a qualitative argu-
to obtain the quantities that are specified to be the natural ment can be given that suggests no great surprises. We note
variables of the internal energy, U = U共S , V , n兲. We thus ob- that switching on interactions between the gas particles will
tain a useful Maxwell relation for the numerator decrease the expansion coefficient relative to an ideal gas
冉 冊 冉 冊
because attractive forces will hinder expansion. Likewise,
P 2U the entropy will decrease because attractive forces will result
− = = 共15兲
n S,V V n V S,n in short-ranged correlations. Hence, we expect that the term
in brackets in Eq. 共22兲 will remain negative. For water vapor
=− 冉 冊 冉 冊
S T
n V S,n
+
V P
n V S,n
, 共16兲
at atmospheric pressure and 100 ° C, the change 共s / T兲 P is
−0.034R compared with the value for an ideal gas of
−0.059R. The effect of saturated water vapor
共P = 0.01 atm兲 at room temperature upon heating a room re-
where we again used Eq. 共12兲. For the denominator in Eq.
duces the entropy loss marginally because the fraction of
共14兲, we have another Maxwell relation
water vapor is only a few percent. A similar argument for the
冉 冊 P
S V,n
=−
2U
V S
=−
T
V
冉 冊 S,n
, 共17兲
change in internal energy in Eq. 共21兲 shows that it is margin-
ally negative because the expelled air takes some of the in-
ternal energy with it, due to the attractive interactions be-
tween the mloecules.10
so that
冉 冊 S
n P,V
=
S V P
−
n n V
冉 冊冉 冊 S,n
V
T S,n
=
S V P
−
n n T
冉 冊 S,n
IV. DISCUSSION
We have argued that to raise the temperature of a room
共18a兲 with permeable walls, the relevant thermodynamic process
has both volume and pressure constant. If we treat the air in
冉 冊冉 冊
the room as ideal 共which is a very good approximation兲, its
S V S T S 1 cP internal energy U = ncVT = 共cV / R兲PV remains constant, im-
= − = − . 共18b兲
n n T P,n V P,n n T␣ plying that raising the temperature is accompanied by expel-
ling air to the outside and lowering the entropy. Thus, the
Hence, we obtain for Eq. 共8兲, thermal energy that is transferred to the room is also trans-
冉 冊 S
T P,V
冉 冊
= − n␣ s −
cP
␣T
. 共19兲
ferred to the outside where it is wasted. Converse statements
apply if the room is cooled.
A skeptical reader might not be convinced and still believe
that there may be an alternate scenario. Let us analyze two
dS = − n␣ s − 冉 冊 cP
␣T
dT, 共20兲
such possibilities. Because our analysis is based on the fact
that the walls of the room are permeable 共the windows and
doors兲 so that air can escape, we now remove this assump-
where s = S / n is the molar entropy. If we express the Euler tion and investigate a hermetically sealed room.
relation for molar quantities, s = u / T + Pv / T − / T, we can For a sealed room, n is constant, and we have two options,
easily show that this general result agrees with Eq. 共1b兲 for either the volume of the room stays fixed as the temperature
an ideal gas. The quantities s, ␣, and c P are well defined is raised or the pressure remains constant. For constant vol-
ume, the pressure will rise according to
冉 冊
functions of temperature and pressure and are tabulated for
many gases of interest. P 共 V/ T兲 P,n ␣
What happens to the internal energy under conditions dP = dT = − dT = dT. 共24兲
T V,n 共 V/ P兲T,n T
when P and V are held constant? We obtain
冉 冊 冉 冊
We treat the air as an ideal gas. Increasing its temperature at
U cP constant volume from Ti = 273 K to T f = 300 K will raise the
dU = dT = − n␣ h − dT, 共21兲 pressure from Pi = 1 atm= 101.3 kPa to P f = 共T f / Ti兲Pi
T P,V ␣
= 1.1 atm.11 This increase might cause some health problems
where h = u + Pv is the molar enthalpy. For an ideal gas, not to mention that large windows might explode. No work
Eq. 共21兲 reduces to dU = 0 as required. If we use the defini- is done and the thermal energy transferred to the room is
tions of ␣ and c P, we can rewrite Eq. 共20兲 as Qi→f = U f − Ui = 共cV / R兲V共P f − Pi兲 ⬇ 0.35 kW h.
76 Am. J. Phys., Vol. 79, No. 1, January 2011 H. J. Kreuzer and S. H. Payne 76
For constant pressure, the volume will increase to V f tions of atmospheric science and astrophysics and became the
= 共T f / Ti兲Vi, again a 10% increase, causing an unacceptable cornerstones of most textbooks on these subjects. He also laid the foun-
dations of the theory of balloon flight and while considering atmospheric
bulge in the windows and walls of the room. In this case, radiation, anticipated in 1921 Bose–Einstein statistics for photons in his
work is also done to move the walls 共if that is possible兲, work on “light quanta.” See R. Emden, “Lichtquanten,” Phys. Z. 22,
namely, Wi→f = −P共V f − Vi兲 ⬇ −0.14 kW h accompanied 513–517 共1921兲 For more information on this remarkable scientist, see
by a heat transfer Qi→f = ⌬U − Wi→f = 共c P / R兲P共V f − Vi兲 具www.encyclopedia.com/doc/1G2-2830901313.html典.
2
⬇ 0.48 kW h. R. Emden, “Why do we have winter heating?,” Nature 共London兲 141,
It is the entropy that plays the dominant role in thermody- 908–909 共1938兲.
3
A. Sommerfeld, Thermodynamik und Statistik, Vorlesungen über Theore-
namics, which sets it apart from mechanics. To emphasize
tische Physik Band 5 共Diederich’sche Verlagsbuchhandlung, Mainz,
this point, we finish with another quote from the conclusions 1952兲 关translated by J. Kestin, Thermodynamics and Statistical Mechan-
of Emden’s article:2 ics, Lectures on Theoretical Physics Vol. V 共Academic, New York,
1956兲兴.
“As a student, I read with advantage a small book 4
Z. Bilkadi, “When you heat your house does the thermal energy content
by F. Wald entitled ‘The Mistress of the World and increase?,” J. Chem. Educ. 49, 493–494 共1972兲.
5
her Shadow.’ These meant energy and entropy. In J. A. Campbell, “Footnote to the house heating exemplum,” J. Chem.
the course of advancing knowledge the two seem Educ. 50, 365–366 共1973兲.
6
Herbert B. Callen, Thermodynamics and an Introduction to Thermosta-
to me to have exchanged places. In the huge manu- tistics, 2nd ed. 共Wiley, New York, 1985兲. This classic book and the fol-
factory of natural processes, the principle of en- lowing reference exemplify the approach to thermodynamics based on
tropy occupies the position of manager, for it dic- differentials.
7
tates the manner and method of the whole H. J. Kreuzer and I. Tamblyn, Thermodynamics 共World Scientific, Sin-
business, whilst the principle of energy merely gapore, 2010兲.
8
J. Kestin and J. R. Dorfman, A Course in Statistical Thermodynamics
does the book-keeping, balancing credits and 共Academic, New York, 1971兲.
debits.” 9
For R-values of insulation and building materials, see, for example,
具enwikipedia.org/wiki/R-value_insulation典.
10
We point out some flaws in Ref. 4 so that readers do not become unnec-
ACKNOWLEDGMENTS essarily confused. This article has the subtitle, “Illustrating the first law of
thermodynamics.” This subtitle is misleading because the energy in the
This work was supported by grants from the Natural Sci- room is conserved only within the model of an ideal gas. Otherwise,
ences and Engineering Council of Canada and the Office of energy is conserved in the supersystem of room plus environment. Fur-
Naval Research, Washington, DC. The authors are grateful to thermore, the process of heating the room is driven by entropy. Along
the referee who pointed out the papers by Bilkadi and Camp- with this article are some comments by Wilbur B. Bridgman, which are
misleading. We point out two major concerns: His Eq. 共9兲 is mathemati-
bell.
cally inconsistent because the left-hand side is a differential and the right-
hand side is a ratio of two differentials. The proper expression is our Eq.
a兲
Electronic mail: h.j.kreuzer@dal.ca 共21兲. Also the discussion of the crucial role of the reference state 共em-
1
The Swiss physicist Robert Emden 共1862–1940兲 was, successively, a pro- phasized in the statement at the end of his second to last paragraph
fessor of physics, meteorology, and astrophysics at the Technical Univer- “different conclusions are reached depending on the choice of reference
sity of Munich. His work Gaskugeln: Anwendungen der Mechanischen state”兲 is incorrect because thermodynamic predictions cannot depend on
Wärmetheorie auf Kosmologische und Meteorologische Probleme (Gas- the choice of a reference state, but are given by the integrals of differen-
eous Spheres, The Application of Thermodynamics to Cosmological and tials.
11
Meteorological Problems) 共Teubner, Leipzig, 1907兲 and “Thermodynam- The highest pressure ever recorded on Earth was 1.07 atm in Agata,
ics of celestial bodies,” Encyklopadie der Mathematischen Wissen- Siberia on December 31, 1968 with a temperature of −58 ° C. See
schaften 共Teubner, Leipzig, 1926兲, Vol. 6, pp. 373–532, laid the founda- 具enwikipedia.org/wiki/Atmosphere_pressure典.
77 Am. J. Phys., Vol. 79, No. 1, January 2011 H. J. Kreuzer and S. H. Payne 77