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Thermodynamics of heating a room

H. J. Kreuzera兲 and S. H. Payne


Department of Physics and Atmospheric Science, Dalhousie University, Halifax, Nova Scotia,
Canada B3H 3J5
共Received 5 April 2010; accepted 24 August 2010兲
A room is not heated by increasing its internal energy but by decreasing its entropy due to the fact
that during heating, the volume and pressure remain constant and air is expelled. We first present a
simple solution treating the air in the room as an ideal gas. We calculate the differential entropy
change and heat transfer and give numbers for a typical room including estimates of heat loss
through windows and walls. We also demonstrate the power of thermodynamics to derive the
entropy and internal energy changes for any gas. © 2011 American Association of Physics Teachers.
关DOI: 10.1119/1.3488987兴

I. INTRODUCTION is negligible so that the volume of the room is constant. We


will also assume that the walls are adiabatic. We will deal
In 1938, Emden1 published a short article with the title, with energy loss by conduction through walls and windows
“Why do we have winter heating?”2 He starts by giving two later. The walls of a room are approximately impermeable
answers: except for the doors and windows. Thus, overall the walls
must be treated as permeable so that air can escape and enter.
“The layman will answer: ‘To make the room Permeability implies that the air pressure inside and outside
warmer.’ The student of thermodynamics will per- the room is the same and remains constant because anything
we do to the room will hardly affect the world outside. Thus,
haps express it thus: ‘To import the lacking 共inter-
our preliminary conclusion is that during the process of rais-
nal thermal兲 energy.’ If so, then the layman’s an- ing the temperature, the pressure and volume of the room
swer is right, the scientist’s is wrong.” remain constant, and the amount of air in the room 共mole
number兲 does not. These are the conditions for which we
Emden then proved his assertion with a simple argument must formulate the solution.
based solely on regarding air as an ideal gas. Sommerfeld
included this thermodynamic problem in his textbook on
thermodynamics.3 Many years later, it was briefly discussed II. SIMPLE SOLUTION: IDEAL GAS
in two short communications.4,5 The lack of exposure and
interest in this problem is surprising, considering the impor- For the conditions applicable to human habitation, we can
tance of heating of dwellings in everyday life and how in- treat the air as an ideal gas of n moles contained in a volume
structive this example is. Over the years, we have jokingly V at pressure P so that PV = nRT. With P and V both con-
asked many physicists Emden’s question, with the result that stant, the internal energy U = ncVT = cV PV / R remains con-
embarrassingly few came up with the correct answer. We stant, where cV is the molar specific heat at constant volume.
have therefore decided to revisit this problem more formally Thus, raising the temperature of the room can only be done
and also consider situations where the ideal gas law does not by expelling air: T goes up and n = U / 共cVT兲 goes down to
hold. It is also fitting to pay tribute to Emden,1 an eminent keep U constant. Of the relevant extensive variables, the in-
scientist and thermodynamicist who first raised the issue and ternal energy U, volume V, mole number n, and entropy S
who pioneered the application of thermodynamics in atmo- = S共U , V , n兲, the only remaining thermodynamic property
spheric science and astrophysics. that can also change is the entropy. Because the entropy for
What happens when you “heat” a room to increase its an ideal gas is known 共see, for example, Refs. 6 and 7兲, we
temperature? The quick answer is you turn on a heater, thus could calculate its change directly at fixed U and fixed P.
increasing the internal energy and hence raising the tempera- However, it is a better thermodynamic practice to start from
ture. Although this answer may apply to some rooms, it is differential changes. To simplify the calculation of the
not so for rooms in which we live. We analyze this answer by change of entropy, we fix V and U rather than P
first paying careful attention to what is the system and what = UR / 共cVV兲. Thus, we need to know

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

this increase implies that at higher temperature the kinetic


The chemical potential of an ideal classical gas of molecules energy of the gas molecules is higher.
at room temperature is negative and is given by In addition to raising the temperature in a room, we also
have to raise the temperature in the walls. For a thickness of
P 3 −1 about 1 cm, the total volume of gypsum plasterboard 共com-
exp共␮/RT兲 = NA ␭ Z , 共4兲 mon in a standard North American home兲 covering the walls
RT th int 共density of about 600 kg/ m3兲 is about 1 m3, which contains
about n = 3400 mol of calcium sulfate dihydrate. The spe-
where NA is Avogadro’s number, ␭th = h / 共2␲mkBT兲1/2 is the cific heat of plasterboard is about9 1090 J kg−1 K−1. Thus,
thermal wavelength of the gas particles with average mass m, the energy transfer needed to raise the temperature of the
and Zint is the molecular partition function for the vibrational plasterboard by the same amount 共27 K兲 is QPB = ncV共T f
and rotational degrees of freedom of the air molecules 共see, − Ti兲 ⬇ 0.31 kW h, or about 1/10 of the heat transfer needed
for example, Ref. 7 or Ref. 8兲. The result is that as the tem- to raise the temperature of the air itself. In addition, we
perature is raised in the room, the entropy decreases. Thus, should keep in mind that there is energy loss by conduction
the heat transfer, dQ = TdS, is also negative, that is, we do and by convection through cracks and doors. To be specific,
transfer energy to the outside to “heat” a room. The decrease the rate of heat loss as measured by the U-factor 共the inverse
in entropy, with an increase of temperature, can only occur if of the R-value兲 is 0.5 W K−1 m−2 for a stud wall with R-20
the quantity of air in the fixed volume decreases, that is, air fiberglass insulation, 6.25 W K−1 m−2 for a single-glazed
must be expelled to the outside. window, and 2.8 W K−1 m−2 for a double-glazed window.
We can integrate Eq. 共1b兲 to obtain the entropy change and Thus, for a 2.5 m ⫻ 5 m outside wall with a 2 m2 double-
also the energy transfer needed to raise the temperature of glazed window and a temperature difference of 20 K be-
the air from Ti to T f , tween the inside of the house and the outside we must supply
about 240 W, or 6 kW h/day to compensate for the heat loss
⌬S = S f − Si through conduction, provided there are no thermal leaks by

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
,

共5兲 III. GENERAL SOLUTION

What happens at higher pressure and higher densities

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h2/2␲mkB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

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