arXiv:1012.3091v1 [physics.

class-ph] 14 Dec

Report no. pi-other-204

An exercise in thermo-dynamics
PierGianLuca Porta Mana
Perimeter Institute for Theoretical Physics, Canada <lmana@perimeterinstitute.ca> 12 December 2010 (first drafted 29 October 2010)

Abstract: An exercise in classical thermodynamics requiring an explicit treatment of the time variable is presented, solved, and further explored; a particular solution is found to be supported by experimental evidence. The exercise is discussed to argue in favour of an explicit treatment of time in classical thermodynamics as usually taught in undergraduate and graduate courses.
PACS numbers: 05.70.-a,64.10.+h,01.40.gb MSC numbers: 80-01,97M50,34-04

to Laura
‘i mean if you dont change in 2 years or even in a day, then whats the point?’ L. Pasichnyk

1 An exercise in thermo-dynamics
A vessel that can be idealized as a hollow tube of cross-section A is filled with a mass M of an ideal gas as in fig. 1. The tube is closed at one end by a piston of mass m that can move freely without friction. A constant force f acts on the piston from the outside (the force can e.g. consist in atmospheric pressure, and also in the weight of the piston itself if the tube is in a vertical position). Until time t0 the piston is at a distance L from the other base of the tube and 1
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Porta Mana

An exercise in thermo-dynamics

the gas is in equilibrium. Starting at time t0 heating is suddenly provided thereafter at a rate Φ(t). How long does it take for the piston to increase its distance by an amount λ ? How do pressure and temperature change during that same time? The gas is characterized by a massic gas constant R (i.e. R = Ri /µ with Ri the ideal-gas constant and µ the molar mass of the gas), a linear relation between internal energy and temperature with massic heat capacity c, and it is homogeneous at all times. Assume, approximately, L = 20 m, A = 10
−4

(1a)
2

m ,
−3

(1b) kg,
4

M = 2 × 10 f = 9 N,

(1c) (1e) (1f) (1g) (1h)

corresponding to a pressure f / A = 9 × 10 Pa, (1d)
2

m = 10−2 kg, R = 3 × 10 J/(kg · K), c = 7 × 10 J/(kg · K),
2

λ = 5 × 10 Φ(t) =
with

−1

m,

and

f λ ( c + R) 2cLλ m mλ 2 (8c + 6 R) ( t − t0 )3 + ( t − t0 )2 + , (1i) 243 Rτ 6 9 Rτ 3 9 Rτ 3 (1j)

τ = 1 s.

(If the value of L appears impractically large, consider that this is an idealization and the real set-up can be as in the dotted rectangle of fig. 3.)

Figure 1: Idealized experimental set-up for the exercise (for the real set-up see fig. 3)

2

Porta Mana An exercise in thermo-dynamics 2 Solution Let us denote the distance of the piston from the tube’s base at time t by h(t). h(t)[ f + mh MR (6a) from which. and the gas’ pressure. Ap(t) − f − mh where a dot indicates derivation with respect to time. and internal energy by p(t). substituting in (4) and (5). Ah(t) (4) And finally • constitutive equation for the gas’ internal energy. we also obtain an expression for the pressure: 1 ¨ (t)]. p. as specified in the problem: U (t) = McT (t). (5) (If some of these equations look unfamiliar to you. h(t)[ f + mh R 3 (6c) . T (t). U . • Energy balance for the gas: ˙ (t). temperature.1. p(t) = [ f + mh (6b) A and the internal energy: U (t) = c ¨ (t)]. take a look at § 4. U (t). The system can be easily simplified. • Constitutive law for the pressure of an ideal gas: p(t) = MRT (t) . where Q(t) is the heat received by the gas from that Φ(t) = Q some arbitrarily specified time up to time t.) The equations above constitute a system of coupled ordinary differential equations for the unknown h. Note ˙ (t). Substituting the expression for the pressure (4) in the momentum balance (2) we can express T in terms of h: T (t) = 1 ¨ (t)]. ˙ (t) = Φ(t) − p(t) Ah U (3) (2) since the volume is obviously given by Ah(t) and A is constant. The equations relevant to the problem are: • Momentum balance for the piston: ¨ (t) = 0. T .

a2 = 0. h ¨ (t0 ) = 0. and it does not seem to be solvable analytically. (11a) A 9 Aτ 3 fλ 2λ Lm fL ( t − t0 ) + ( t − t0 )3 + + T (t) = MR 9 MRτ 3 27 MRτ 3 2λ 2 m ( t − t0 )4 . . and that Φ(t) in eq. h (8) The differential equation above looks complicated. but miraculously we find that it can be solved with a3 = λ /(3τ )3 and the remaining coefficients equal to zero. and h ¨ . Seeing however that it is of third order. we can try a polynomial solution of the form h(t) = i =0 ∑ a i ( t − t0 ) i . a1 = 0. . . ¨ (t)] + cm h(t)h h(t)[ f + mh R R (7) where Φ is given. This means h ( t0 ) = L . (10) h(t) = L + λ 27τ 3 The solutions for pressure and temperature are f 2λ m + ( t − t0 ) . a6 . ˙ (t0 ) = 0. Thus the solution is ( t − t0 )3 . (1i) is a polynomial of third order in (t − t0 ). The exercise says that until t0 the initial conditions for h. Substituting the above expression for h and that for Φ (1i) in the differential equation (7) we obtain a non-linear system of equations (that I let the readers write for themselves) for the remaining coefficients a3 . 6 (9) The initial conditions (8) impose a0 = L. . This differential equation must be supplemented by appropriate ˙ .Porta Mana An exercise in thermo-dynamics From the latter two equations and the energy-balance (3) we finally obtain a differential equation of third order for h: Φ(t) = 1 + c ˙ ˙˙˙(t). h piston has been at rest at a distance L and the gas in equilibrium. 243 MRτ 6 (11b) p(t) = 4 . The system seems to be over-determined since it has ten equations for four unknowns.

2 for the numerical values (1). With the numerical values (1). The inertial force also acts on the gas. T ( t0 ) = fL = 300 K. and energy: p(t) = f . MR U (t) = cfL . An inertial force ma acts on the piston in addition to f . before the heating Φ is provided. 3 Exploring the exercise Let us examine the equilibrium conditions of the gas for t t0 . MR (13c) (13d) (13a) (13b) These solutions are shown in fig. 3 MRτ 2 p ( t 0 + 3τ ) = p ( t 0 + 3 s ) = compare with the initial values p(t0 ) = f / A = 90 000 Pa. h(t0 + t) − h(t0 ) = 0. (14a) These values are in fact valid at any time t in which the piston is ¨ (t) = 0. With those values. From eqs (6) we find the expected equilibrium values for pressure. instantaneously in uniform motion. R t t0 . but the whole system is subject to a constant acceleration a in the direction of decreasing h. T by its constant and cubic terms.5 m at t = 3 s. h even if it has a non-zero velocity. And when the piston is accelerating? If you think that the term ¨ in eqs (6) represent a deviation from equilibrium. + A 3 Aτ 2 ( L + λ )(2λ m + 3 f τ 2 ) T ( t 0 + 3τ ) = T ( t 0 + 3 s ) = = 308 K. but it is negligible if Ma/( pA) is small — just as the force of gravity on a gas is usually 5 . A T (t) = Lf . and the pressure of the gas has to compensate the sum of the two forces. (12) Also. consider a situmh ation in which the piston is at rest in relation to the tube. Φ is dominated by its quadratic term in time. i.Porta Mana An exercise in thermo-dynamics The answer to the first question of the exercise is that the piston increases its distance by λ in a time 3τ after t0 . not accelerating. temperature. f 2λ m = 90 033 Pa.e.

0 s t0 t0 t0 306 304 302 t 0.5 T K 1.0 1.0 1.5 3.5 1.5 h dm 205 204 203 202 201 t 0.0 s 1.0 2.5 2.5 3.0 s t0 Figure 2: Solution for h(t) = L + λ ues (1) 6 ( t − t0 ) 3 27τ 3 and the numerical val- .0 2.0 1.Porta Mana An exercise in thermo-dynamics Q W 15 10 5 t 0.5 3.5 2.5 3.0 1.5 p Pa 90 030 90 025 90 020 90 015 90 010 90 005 t 0.0 2.5 2.0 2.5 2.0 s 1.

Pressure and temperature f 2( t − t0 ) 4λ m sin − . (16b) A τ Aτ 2 Lf 4λ 2 m f τ 2 − 4 Lm 2( t − t0 ) 2( t − t0 ) +λ T (t) = + sin sin2 2 2 MR τ τ MRτ MRτ (16c) p(t) = 7 . From eq. In general the differential equation (7) for h given Φ would be much more difficult to solve. But numerical solutions are easily obtained when Φ. Let us now consider an oscillatory motion instead. I did not find an analytic solution for h given a generic Φ. Let us explore the behaviour of the system for other forms of the heating Φ and for other initial conditions. In the solution of the problem h is monotonically increasing. I shall comment later on the term ‘equilibrium’. Φ is then easily calculated with eq. h ¨ (t0 ) = 0.Porta Mana An exercise in thermo-dynamics neglected in exercises similar to the present one. (7) we find that such a motion would be obtained h by means of a heating Φ(t) = 2λ f (c + R)τ 2 − 4cLm 2( t − t0 ) cos − 3 τ Rτ 2c + R 4( t − t0 ) . and the physical constants of the problem are numerically given. The particular expression for Φ(t) given in the exercise was obviously chosen so that we could arrive at the solution through an educated guess. (7). motion corresponds to the initial conditions h(t0 ) = L. and I suspect there is no solution in closed form. 4λ 2 m sin τ Rτ 3 (16a) which is also having an oscillatory behaviour with amplitude around 30 W. Note that this ˙ ( t 0 ) = 2λ / τ .5 m and period πτ ≈ 3 s. From this point of ¨ does not represent a deviation from ‘instantaneous view. In the following formulae we always intend t > t0 unless stated otherwise. like h(t) = L + λ sin 2( t − t0 ) . the term mh equilibrium’. the initial conditions. τ (15) with amplitude λ = 0. We can also turn the question topsy-turvy and consider h as assigned and Φ as the unknown.

the net result is ˙ periodically vanishes. 6. the piston is at rest until t0 .5 K/s. initial equilibrium When Φ(t) = 0 it is reassuring to find numerically that if the piston is at rest and the gas in equilibrium until t0 . 3. We shall examine five cases. how the latter changes in time. with a heating of the form Φ(t) = 10 W · sin 0 W. T by its constant and sine terms. These solutions are shown in fig. τ t0 t τ + t0 .2 Second case: constant heating The heating is constant and equal to Φ(t) = 5 W. they also remain so thereafter. The temperature has an analogous behaviour.3 Third case: heating for a short time We now heat the gas in a continuous way for τ = 1 s. Φ is dominated by its cosine term. 3. The rate is not strictly constant: we observe a superimposed oscillatory motion of about 0. Now let us not cheat anymore: let us choose some reasonable heating functions Φ and initial conditions for the position h and find. as expected.1 First case: no heating.7 dm/s. t0 ∨ t τ + t0 . It is interesting to note that the period of the oscillations 8 . but maintains an oscillatory motion around a new value after the heating has vanished. While the heating is nonzero the distance h increases and then begins to decrease. so that h inthat h creases in steps. 4 for the numerical values (1). (7) gives the solution of fig.8 s period and 1 cm amplitude. Numerical integration of eq. The same behaviour can be observed in the temperature and pressure. π( t − t0 ) . This stepwise increase is reflected in the oscillatory behaviour of the pressure around a seemingly constant value. 3. with an average increase rate of 2. by numerical integration of (7). t (17) The solution is shown in fig. without becoming negative.Porta Mana An exercise in thermo-dynamics oscillate with amplitudes around 200 Pa and 7 K. 5: the distance h increases at an average rate of around 1.

We also assume an adiabatic process. by measuring the period τo approximately given by eq. (If the remaining undamped oscillatory behaviour surprises you or seems unphysical. remember that the piston is assumed to move with no friction and the gas is inviscid. as shown in fig. Φ(t) = 0. So for our fourth case let us choose 20 W. 3.Porta Mana An exercise in thermo-dynamics τo is apparently the same as in the previous case. initial acceleration What happens if at t0 the piston is at rest but has some acceleration? Now we assume that h has an initial negative acceleration of ¨ (t0 ) = −10 m/s2 (as in free fall). We almost obtain the guessed behaviour indeed. 2] as modified by Schufle [3]. with τo given by (22). One can show numerically that changing the initial acceleration only changes the amplitudes of the oscillations but not their period. Φ(t) = (18) 0 W. shown in fig. This last case can be experimentally observed with an AssmannRüchardt apparatus [1. Indeed we show in § 3. for times near t0 .8 s. 3. we may make the distance h increase and then remain stationary at a new value without residual oscillations.6 that this period is approximately given.) τo = 2π cmL ( c+ R) f 3. as shown in fig. by ≈ 0.5 Fifth case: no heating. the oscillatory behaviour we found is used to calculate the ratio of specific heats of the gas. t0 t t0 + τo . The values (1) are indeed approximately taken from 9 . In these conditions we observe an oscillatory behaviour of all quantities. which in our case is given by γ = 1 + R/c. This would be the case if the tube was placed vertically h and we suddenly dropped the piston in it at time t0 . This must be an intrinsic parameter of the system.4 Fourth case: heating for the duration of one intrinsic period The solution of the previous case suggest that if we heat the gas for a duration equal to the observed intrinsic oscillation period τo . and vanishing initial velocity h ˙ (t0 ) = 0. With that apparatus. again with the same intrinsic period. t t 0 ∨ t τo . 8. (22). 7. around 0.784 s.

784 s.e. The intrinsic period is τo = 2π cmL ≈ 0. § 3. fh (21b) R R where Q(t) is the total heat received by the gas between t0 and t. For t0 t 3τ it is found that − 4 the difference does not exceed 2 × 10 L. i. It should be remarked that for a smaller volume of gas. viz 4 mm. and our solution gives with good approximation the period of oscillation observed in his experiments. maybe. ˙ (t) + cmL h fh R R (20) Integrating between t0 and t and defining ¯ (t) := h(t) − h(t0 ) − cmL h ¨ ( t0 ) h c+R we obtain Q(t) = 1 + (21a) c ¨ ¯ (t) + cmL h ¯ (t).6 Approximations As already said. (7) can present even more interesting behaviours — to be studied. in a future memoir. 10 . the approximations (19) do not hold and eq. and if the inertial term mh variations of h(t) are small in comparison to its initial value L.e. for which we have around 10−3 L. f L the above equation can approximated by (19) Φ(t) = 1 + c ˙˙˙(t). But if the ˙˙˙(t) is small in comparison to the force f .Porta Mana An exercise in thermo-dynamics Schufle’s article. ¨ (t)] + cm h(t)h h(˙t)[ f + mh R R Φ(t) = 1 + (7)r does not seem to be amenable to a closed-form solution. 3. The last equation describes a driven harmonic motion and can be solved exactly in terms of integrals of Q. c ˙˙˙(t). ˙˙˙(t) mh h(t) − L and small. smaller L. i. the differential equation governing our problem.5. for all cases except the fifth one. ( c + R) f (22) The solutions previously obtained numerically do reasonably satisfy the conditions (19) and one can compare the numerical results with those obtained using eqs (21). or bigger piston mass m.

the same holds for h. shown in fig. 1. where Lr is the distance of the piston from the base of the real tube and Vv is the volume of the vessel connected to the latter. The part of the apparatus inside the dotted rectangle is idealized in fig. notice the piston in the left tube. The distance L of the exercise is an effective distance given by L = Lr + Vv / A. 8. can be experimentally observed. with which the solution of the fifth case. (Reprinted and adapted from Schufle [3] with the permission of the American Chemical Society) 11 . The real tube can be between one and two metres long.Porta Mana An exercise in thermo-dynamics Figure 3: Assmann-Rüchardt-Schufle apparatus.

5 3.5 2.5 3.5 1.5 3.0 2.0 2.5 2.5 T K 306 304 302 300 298 296 t 0.5 2.5 2.0 s t0 Figure 4: Solution for h(t) = L + λ sin values (1) 12 2 ( t − t0 ) τ with the numerical .5 1.0 1.Porta Mana An exercise in thermo-dynamics Q W 30 20 10 t 0.0 1.0 1.0 s t0 1.0 s t0 1.0 2.0 2.0 1.0 s t0 p Pa 90 200 90 100 90 000 89 900 t 0.5 10 20 30 h dm 204 202 200 198 t 0.5 3.

0 2.5 3.0 1.0 s t0 Figure 5: Solution for Φ(t) = 5 W. piston at rest until t0 .5 3.5 2.0 s t0 1.5 1.5 1.0 2.5 2.5 2.5 3.0 2. and the numerical values (1) 13 .0 2.5 p Pa 1.0 s t0 90 100 90 050 90 000 89 950 t 0.0 1.0 s t0 T K 307 306 305 304 303 302 301 t 0.5 2.0 1.Porta Mana An exercise in thermo-dynamics Q W 10 8 6 4 2 t 0.5 3.0 1.5 h dm 205 204 203 202 201 t 0.

0 1.0 2.0 2.5 301. 0 W elsewhere.0 1.0 302.5 h dm 1.0 1.5 1.0 s t0 Figure 6: Solution for Φ(t) = 10 W · sin τ 0 in t ∈ [t0 .5 201.0 301.0 200.5 t 0.5 t 0.0 300.0 1.5 3.0 s t0 202.5 302.5 p Pa 1.0 2.5 1. τ + t0 ].5 2.5 2. piston at rest until t0 .5 3.5 2. and the numerical values (1) 14 π( t − t ) .5 3.0 2.0 s t0 90 100 90 000 89 900 t 0.5 3.0 201.5 2.0 s t0 T K 303.Porta Mana An exercise in thermo-dynamics Q W 10 8 6 4 2 t 0.

5 h dm 205 204 203 202 201 t 0. piston at rest until t0 .5 2.0 s t0 90 400 90 200 90 000 89 800 t 0.5 3.0 2. 0 W elsewhere.5 2.5 3.0 1.5 3.5 1.5 2.0 2.5 3.0 2.5 p Pa 1.0 s t0 Figure 7: Solution for Φ(t) = 20 W in t ∈ [0.0 1.0 s t0 1.0 s t0 T K 308 306 304 302 t 0.0 2.0 1.Porta Mana An exercise in thermo-dynamics Q W 20 15 10 5 t 0.0 1. and the numerical values (1) and (22) 15 . τo ].5 2.5 1.

0 s t0 Figure 8: Solution for Φ(t) = 0 W.0 197.5 3.5 2.5 2.5 t 0.5 3.5 t 0.5 3.0 1.0 1.5 p Pa 91 000 1.0 297.0 s t0 90 500 90 000 89 500 t 0.5 1.5 296.5 1.0 199.0 0.5 2.5 T K 298. and the numerical values (1) h 16 . an initial negative acceleration of ¨ (t0 ) = −10 m/s2 .5 t 0.0 h dm 200.5 3.5 199.0 1.Porta Mana An exercise in thermo-dynamics Q W 1.0 198.5 198.5 1.0 2.0 s t0 1.0 1.5 0.0 2.0 2.0 2.0 s t0 298.5 2.

The only undergraduate textbook I found in which the thermodynamic quantities are presented with an explicit time-dependence is Sandler’s [4. ˙ . .Porta Mana An exercise in thermo-dynamics 4 Arguing for the time variable in classical thermodynamics During my undergraduate studies I have never encountered an exercise similar in spirit to the one presented here. say pressure p. (The term ‘power’ is usually reserved for the sum e. chs 3. T (t)]. T (t)]. T (t). More generally. entropy S. The latter is usually specified in terms of the independent and dependent variables of the system and their rates of change. internal energy U . Φ is the heating.g. 4. ?’. I think. or rate at which heat is received by the system. (23) U T ˙ are the rates of change of internal energy ˙ and S In these equations. So the first and second law assume the forms Φ ˙ ˙ = Φ − P. • The dependent variables. just like the position of a mass-point depends on time in mechanics. say volume V and temperature T . the latter being usually negligible in thermodynamics) 17 . depend on time: V (t). as was shown in the solution of § 2: • The independent variables describing the system. U and entropy. P = pV of working and increase of kinetic energy. e. and it is confirmed by a look at basically any thermodynamics or generalphysics textbook for physicists. and P is the working. even though that kind of question abounded in courses of mechanics and electromagnetism.g.1 Classical thermodynamics with time An explicit presence of the time variable in classical thermodynamics amounts simply to this. or rate at which work is done by the system. etc. . My experience is not untypical. also depend on time through their dependence on the independent variables: p[V (t). U [V (t). S . and therefore replaced by time derivatives. no thermodynamic exercise that posed a question like ‘in how much time. in courses of thermodynamics or statistical mechanics. 4] (written for chemical engineers). • The differentials usually appearing in the first and second laws are recognized to be differentials with respect to time.

an easier study of problems in which thermal and mechanical phenomena appear together. II]. and the already mentioned Sandler [4]. Owen [10]. the use of differentials also force him to make approximations to the behaviour of the system. in synovial fluids [12. Truesdell and Bharatha [9]. He uses differentials in deriving the necessary relations between thermodynamic quantities. its appropriate place in classical thermodynamics and thermodynamic courses. revealing that all preceding differentials were nothing else than time-derivatives in disguise. Samohýl [11. instead. Indeed it shows. derivatives).g. This consequently allows.Porta Mana An exercise in thermo-dynamics This formulation was discussed by Menger [5] and is presented in Truesdell [6. it avoids any mention of ‘inexact differentials’ and therefore does not require notions of the mathematics of differential forms. say ˙ ). Third.2 Advantages With the solution and analysis of our little exercise of § 1 I hope to have shown that time has. Its explicit presence has many advantages: First. Moreover. arriving at an expression with the differential of a force. 8. 7. 4. 13] or in pyroelecp(V. was obtained in a mathematically seamless way instead. but then he must combine these with mechanical ones. as a second advantage. owing to the presence of time in the basic thermodynamic equations. Our solution. Lecture 26. by eqs (23). why there cannot be differentials related to heating and working: because they are not the rates of change of anything. At that point he has to concede that the force is related to the double timederivative of position. which leads to ugly mathematical gymnics. T. The mathematics of differentials can barely handle 18 . ch. This kind of problems is often avoided because of the clash between the mathematics typically used in thermodynamics (differentials. Lecture 1 and Appendix1A]. it makes it possible to study more interesting thermodynamic systems for which the pressure or other quantities depend not only on volume and temperature but also on their rates of change. An example is given in Schufle’s article [3]: he must derive the equation of a harmonic oscillator in a set-up similar to that of our exercise. § 2. as it happens e. V tric materials [14]. no time) and that used in mechanics (explicit time.

would be nonsense. I should rather call such a theory thermostatics (cf.g. in Schufle’s experiment above. Eckart [15]). many mechanical problems.g. as the interesting third-order ordinary differential equation (7) shows: it leads to a rich class of mathematical problems and physical behaviours (like the driven harmonic oscillator. Cases for the explicit appearance of time in thermodynamics were already made by Eckart [15]. as we have seen e. by Bridgman [16. 24–26]. experimental evidence. which is only a special case). extensively and intensively by Menger [5].3 Common. and very forcefully. (Some people even say temperature is defined only at equilibrium.Porta Mana An exercise in thermo-dynamics such systems. II. like the harmonic oscillator or bal19 . On this generalization I recommend the very lucid and simply written work of Samohýl [11]. it is full of physical and mathematical pedagogic potentials. and practice. [6–11. pp. I do not give much weight to this view because it is simply contrary to experience. by Truesdell and his school of ‘rational thermodynamics’ (see e. According to this view all theories about non-equilibrium thermodynamics. especially ch. and mathematical arguments. providing also pedagogic material for laboratory classes. The second objection is that an explicit time dependence and the consequent appearance of differential equations is unwarranted for high-school and undergraduate students in their first years. routinely taught and used by engineers and taught in higher physics courses. physical. see e. I find both very weak: The first objection is that thermodynamics would only be concerned about equilibrium and relations between equilibria and would have nothing to say about changes and rate of changes. 17– 22]). weak objections In conversations on this topic with colleagues two main kinds of objection appear against a presentation of thermodynamics with an explicit presence of time. contradicting themselves each time they check a weather thermometer). But why should we limit ourselves to thermostatics when we do not limit ourselves to statics within mechanics? Actually the objection is that there is no proper science of the change of thermal systems — thermodynamics can only be thermostatics. But would not classical mechanics present exactly the same problem? Yet. with telling historical. 4. Fourth.g. That is preposterous.

g. Moreover. They say. Note the analogy between a ho20 . electromagnetism.Porta Mana An exercise in thermo-dynamics listic problems.. ‘quasi-static’ is misleading and counter-intuitive: in our exercise we found visible changes of more than 2 500 Pa/s and 5 K/s (see fig. linearly elastic. e. and argue that we should change them. we mean that Hooke’s law F = −k x can be applied. etc. a single pressure value.4 Inadequacy of the standard terminology of classical thermodynamics Part of the inertia against the time variable in thermodynamics comes from the terminology taught in thermodynamic courses. When we say that a spring is perfectly. Indeed. Now. When we speak of a Ohmic resistor. If a body is called ‘rigid’. ‘rigid’. a single temperature value. that a process is ‘quasi-static’ or that the thermodynamic system ‘passes through a sequence of equilibrium states’. really easier than the use of rates of change? 4. it means that its motion can be fully described by the ˙ .. counter-intuitive. instead of field quantities as in continuum thermomechanics. even those who are keen on allowing the presence of time in classical thermodynamics do so only after some verbal exorcisms. I find most of these phraseologies misleading. when in thermodynamics we say that a process is ‘quasi-static’ or that the system ‘passes through a sequence of equilibrium states’. Their inadequacy can be seen from different points of view: First: In mechanics. is the use of non-intuitive and typically poorly explained ‘inexact differentials’. without explicitly introducing the theory of differential forms. quantum theory we use particular terminologies to indicate that specific equations and laws apply to a problem. The same could surely be done with thermodynamics. But while the terms ‘elastic’. equations F = p ˙ and M = J we mean that the law ∆V = IR applies with a constant resistance R. And obviously there will be some constitutive equations — the ideal-gas law being just an example — connecting these values and maybe even their rates of change. or other similar phraseologies. we simply mean that an equation like p(t)V (t) = nRT (t) can be applied at all times. can be and are routinely approached and solved without the need to study the full theory of differential equations. 8). do we really want to call them ‘quasi-static’? Instead of ‘quasi-static’ I prefer to say that the system is homogeneous (at all times): this implies that it can be described at all times by a single density value. ‘Ohmic’ give the right ideas.

Second: The argument typically adduced for the use of the term ‘quasi-static’ is that the system can be considered static — in equilibrium — in comparison to some time scale. In mechanics and electromagnetics courses the theory of a physical phenomenon and the complex theory of measurement behind it are usually kept quite separate. Positions. If we write a kinetic energy as K = 2 is clear that v shall not be a Lorentz-relativistic velocity. we mention ‘instantaneous equilibrium’ only to mean that the ideal-gas equation can be used at all times. If we again use Hooke’s law F = −k x it is understood that the displacement x is within the range of linear elastic behaviour of the spring. accelerations. if we use p(t)V (t) = nRT (t) it is understood that the system is homogeneous and the ranges and rates of change of p(t). currents. I think that any mention of ‘equilibrium’ is misleading when thermodynamic quantities are clearly. like ‘rest’. and dynamometers. As for saying that a visibly changing system is ‘passing through a sequence of equilibrium states’. Third: It is true that the construction and use of a thermometer or a pressure gauge involves notions like response time and coupling. forces. at worst simply nonsense. away from non-linear or plastic effects for which the law is 1 mv2 with m constant it not valid. charges. Again. That is also what the experiment says. Let us keep that term. . but the same is true of velocity-gauges too. the velocity of light. visibly changing. Again. V (t). T (t) are such that the law is valid. fields are supposed to be measurable with some 21 . it sounds to me like saying that a moving object is ‘passing through a sequence of states of rest’: it is at best an unnecessary and ugly phraseology. velocity-gauges. Analogously. there is no need to mention ‘quasistatic processes’. and the gas is not in equilibrium. for situations in which quantities are not changing in time. But all we should need to say is this: the ideal-gas law is valid. Or maybe in Galileian mechanics we should call all kinematics ‘quasi-static’ because it is necessary that it be almost at rest in comparison with some velocity. But so does the construction of position-gauges. But all equations used in physics are valid in particular ranges and scales only. Some thermometers are inappropriate when the temperature changes too rapidly.Porta Mana An exercise in thermo-dynamics mogeneous body and a rigid body: rigidity and homogeneity both imply that the field quantities describing deformations in the full continuum-thermomechanical treatment can be replaced by a smaller set of mechanical or thermal quantities valid for the whole body. . If an equation is used in a physical problem it is implied that it makes sense there.

e. Springs exactly obeying Hooke’s law for arbitrary values of elastic constant and elongation are supposed to exist. is all we need to know for our problem. This liberty is rarely enjoyed in thermodynamics. or is changing in some prescribed way. the philosophicalempirical foundations of physics. that the temperature of a system is constant. Whenever anyone tries to do anything rational there. the equations for a rigid body make sense only if the forces and torques do not exceed the internal ones that keep the body together. Analogously. questions about what force and mass really are and how they are to be measured are important. in order to concentrate us upon the equations and the phenomenology these exhibit. or experimental procedures. The 22 . Thus it ought to be in thermodynamics. without further question about how that is achieved (springs? some kind of field?). without needing to mention ‘heath baths’ all the time.Porta Mana An exercise in thermo-dynamics appropriate instrument. these changes propagate from point to point and could be detected at appropriate space-time scales. he may be sure to be pestered by professionals who rise and demand he explain how to define temperature and entropy for systems not infinitesimally near to equilibrium. Persons who wish to study them are referred to works on metaphysics.. Or that there is a uniform and constant electric field. That the temperature is constant. but they are rarely mentioned in books on the mathematical theory. For example we often say that a particle is in a harmonic potential. the action of a force on a part of the body will not propagate instantly to the rest of the body: waves will propagate in its interior. according to taste. Yet we should have the right to say.g. Another example: No body is perfectly rigid. Fourth: In mechanics we enjoy the liberty to consider abstract situations leaving unmentioned how they can be realized. for the purpose of studying the mathematical structure of the theory. no body is perfectly homogeneous. no matter what branch or application he takes up. We do not usually point out all these facts when examining a rigid-body problem. Truesdell makes these points very clearly in his typical sharp and witty style: ‘In mechanics. With thermodynamics it is a different matter. and they can be detected at appropriate space-time scales. and its equations make sense only when changes happen on a smaller scale than the velocity of sound in the body. Also. We should feel the need to point out these facts neither more nor less than we do in the case of the rigid body.

isolated. reservoir. but not of what variables S is a function. regards “equilibrium” and “infinitesimally near” as primitive concepts’ [8. The same reader of the same book then reaches the chapter on thermodynamics. on pure mechanics. doubtless much more familiar than “tangent plane” and “gradient” and “tensor”. in each case. nearly in equilibrium. perfect gas. but these sciences as hitherto taught do not mesh. He is loaded with an arsenal of words like piston. ideal engine. cyclic. words the poor student of science is expected to learn to hurl for the rest of his life in a rhetoric little sharper than a housewife’s in the grocery 23 . of course he is presumed familiar with calculus as calculus has been taught for the last fifty years.Porta Mana An exercise in thermo-dynamics persecutor himself. boiler. but words that never find a place in the mathematical structure at all. and often he is told about some major problems still unsolved and is challenged to solve them himself. what the dependent and independent variables are. but that chapter presents a curious contrast with the same author’s pages. quasi-static. if we take up almost any recent book with “continuum mechanics” or “material science” in its title. T km . but even that a differential can be bigger than something which is not a differential. that δ Q is a small quantity not generally a differential. he is expected to believe not only that one differential can be bigger than another. Thus. obviously. universe— words indeed familiar in everyday life. earlier in the book. differential invariants. perhaps even Christoffel symbols and affine connections. Jacobians. pp. He is told that dS is a differential. we find a chapter on thermodynamics. which he learned to use accurately and fluently in the earlier chapters. Lecture 1. everyone studying materials has seen that both thermodynamics and mechanics must be brought to bear. ‘For ten years or more. fields of vectors and tensors.m + ρ bk = ρ x He is informed. condenser. There the reader is faced by mappings. He can understand dynamical equations in tensorial form: ¨ div T + ρ b = ρ x or ¨k . he is presented with explicit differential equations and boundary-value problems. heat bath. 78–79]. where he is faced with the “axiom” T dS ≧ δ Q. he is shown many special solutions in concrete cases and is directed to grand tomes where he can find thousands more such solutions not given in the book he is reading.

The examples or exercises require no more than calculating partial derivatives or integrals of given functions or their inverses and plugging numbers into the results. (Poggendorffs) Ann. No problems. u. no general theorems characterizing classes of solutions. Chem. Marianna. 60–61]. Phys. Zeitschr. 30 (1929). A. are solved. Acknowledgements Many thanks to Louise. d. There are no general equations to be solved. 1–36. to swing music. to R. Lecture 1. and equally unmathematical. Assmann: Ueber Erwärmung und Erkaltung von Gasen durch plötzliche Volumänderung. arXiv. 34/2 (1957). References Note: Of two years separated by a virgule. 78– 80. Schufle: Measuring the ratio of specific heats of a gas: Thermodynamic experiments involving harmonic motion. Physik. pp. Chem. Educ. MiKT X. AUCT X. perhaps otherwise explained and ordered. The mathematical structure. but no broader or clearer in concept. Miriam per i loro continui supporto e affetto. Inkscape. J. The reader must presume that thermodynamics is an exhausted as well as exhausting subject. J. Neither are any open problems stated. to Ingemar Bengtsson and Giacomo Mauro D’Ariano for discussions. The references cited lead to other books containing just the same material. is slight. the first is that of original publication or composition. and to the developers and maintainAT X. [1] C. E. 85/1 (1852). Cheese. with nothing left to be done’ [8. in turn.Porta Mana An exercise in thermo-dynamics store. in the sense that the word “problem” has in the theories of mechanics or electromagnetism or optics or heat conduction. no boundary-value or initial-value problems set. Research at ers of L E E E the Perimeter Institute is supported by the Government of Canada through Industry Canada and by the Province of Ontario through the Ministry of Research and Innovation. to Lucien Hardy and Lee Smolin for encouragement. Rüchardt: Eine einfache Methode zur Bistimmung von c p /cv . Emacs. [2] [3] 24 . 58–59.

First publ. A. pp. 1941. Truesdell III and S. C. Biochemical. Bridgman: The Nature of Thermodynamics (Cambridge. A. Antman. Phys. 1977–1984. A. 1969. Owen: A First Course in the Mathematical Foundations of Thermodynamics (New York: Springer-Verlag. I. D. 18/2 (1950). Noll: The Non-Linear Field Theories of Mechanics. With discussion. 1977. 78– 84. C. R. 78/5 (1995). (New York: Springer-Verlag. C. and W. 1965/2004). W. (Berlin: C. Bertone. Truesdell III: The Tragicomical History of Thermodynamics 1822– 1854 (New York: Springer-Verlag. C. J. L. 1980). 4th ed. 226–858.Porta Mana An exercise in thermo-dynamics [4] [5] [6] [7] [8] [9] S. (New York: John Wiley & Sons. First publ. Levick: Time-dependence of the pressure-volume relationship in the synovial cavity of the rabbit knee. 373–389. [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] 25 . Chynoweth: Dynamic Method for Measuring the Pyroelectric Effect with Special Reference to Barium Titanate. G. I. Samohýl: Thermodynamics of Irreversible Processes in Fluid Mixtures (Approached by Rational Thermodynamics) (Leipzig: BSB B. Phys. Carnot and F. A. by Stuart S. W. 27/1 (1956). Bharatha: The Concepts and Logic of Classical Thermodynamics as a Theory of Heat Engines: Rigorously Constructed upon the Foundation Laid by S. A. Truesdell III: Thermodynamics for beginners. With an appendix on invariants by Jerald LaVerne Ericksen. 859–902. In: Flügge [26] (1960). See also Thomsen [23]. A. 1987). Sandler: Chemical. Phys. 89–103. 267–269. Eckart: The thermodynamics of irreversible processes. J. (Berlin: Springer-Verlag. Appl. A. 3rd ed. 1984). 1965. Muir: Pressure-volume relationships in equine midcarpal joint. The simple fluid. 1941/1943). Menger [24]. R. A. Truesdell III: Rational Thermodynamics. and Engineering Thermodynamics. C. 139–152. J. C. Am. Appl. 1969/1984). I–VII. Rev. Hardy. first publ. K. C. P. Reech (New York: SpringerVerlag. Truesdell III and R. Phys. USA: Harvard University Press. Ed. 2nd ed. 1977/2006). D. Toupin: The Classical Field Theories. A. 335/1 (1983). I. J. Teubner Verlagsgesellschaft. Physiol. pp. Truesdell III and W. G. First publ. J. Menger: The mathematics of elementary thermodynamics. 58/3 (1940). 1977). A. A. Truesdell III: The Elements of Continuum Mechanics Springer-Verlag. In: Parkus and Sedov [25] (1968). Knight and J. 1966).

Revised ed. First publ. 476–477. L. See Menger [5]. 19/8 (1951). III/1: Principles of Classical Mechanics and Field Theory] (Berlin: Springer-Verlag. 19/8 (1951). S. Flügge. J. 1991/1998).Porta Mana An exercise in thermo-dynamics [20] [21] [22] [23] [24] [25] W. June 22–28. S. Parkus and L.: Irreversible Aspects of Continuum Mechanics and Transfer of Physical Characteristics in Moving Fluids: Symposia Vienna. J. [26] 26 . J. M. H. Thomsen: [Comment:] The mathematics of elementary thermodynamics. 1966 (Wien: Springer-Verlag. K. Am. 476. J. (New York: Springer. Šilhavý: The Mechanics and Thermodynamics of Continuous Media (Berlin: Springer-Verlag. See Menger [5] and also Menger [24].: Handbuch der Physik: Band III/1: Prinzipien der klassischen Mechanik und Feldtheorie [Encyclopedia of Physics: Vol. ed. 1988). Am. I. 1991. Phys. Thomsen [23]. Sedov. eds. 1968). Menger: [Reply:] The mathematics of elementary thermodynamics. 1997). 1960). A. Phys. Ericksen: Introduction to the Thermodynamics of Solids. Day: A Commentary on Thermodynamics (New York: SpringerVerlag.