Sadi Carnots contribution to the second law of thermodynamics

Don S. Lemons and Margaret K. Penner Citation: Am. J. Phys. 76, 21 (2008); doi: 10.1119/1.2794346 View online: http://dx.doi.org/10.1119/1.2794346 View Table of Contents: http://ajp.aapt.org/resource/1/AJPIAS/v76/i1 Published by the American Association of Physics Teachers

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Sadi Carnots contribution to the second law of thermodynamics

Don S. Lemons and Margaret K. Penner
Bethel College, North Newton, Kansas 67117

Received 6 June 2006; accepted 13 September 2007 We identify an operative principle in Sadi Carnots only publication that is closely related to a distinct version of the second law of thermodynamics. Although Carnot did not propose the second law of thermodynamics, he assumed its equivalent in proving Carnots theorem. We show that, in the absence of the rst law, Carnots assumption is equivalent to Clausius version of the second law. Both Carnots assumption and Clausius version, in the absence of the rst law, are more restrictive than Kelvins statement of the second law. 2008 American Association of Physics Teachers. DOI: 10.1119/1.2794346 I. INTRODUCTION Many textbooks and popular histories of thermodynamics acknowledge Sadi Carnot for inventing the concept of a reversible cycle, in particular, the Carnot cycle, and for proving Carnots theoremno heat engine operating between two heat reservoirs can be more efcient than a reversible heat engine.1 But rarely do textbooks directly associate Carnot with the discovery of the second law of thermodynamics and they never attribute to him a denite statement of the second law. Instead, textbooks refer to Thomson Lord Kelvin and to Clausius for the rst statements of the second law.2 Yet primary and scholarly secondary sources suggest that Carnot did contribute directly to the development of the second law. Barnett characterizes Carnot as founding without formally proposing the second law of thermodynamics.3 Kestin credits Carnot with the rst verbal formulation of the second law.4 Clausius and Thomson were powerfully motivated by Carnots theorem; they regarded Carnots theorem as true but ultimately were not able to accept all the elements of Carnots proof. Their rst task upon formulating their versions of the second law was to prove Carnots theorem.5,6 Current thermodynamics texts also use the second law of thermodynamics to prove Carnots theorem.7 Yet Carnot was able to prove his theorem without formally advancing the second law. How did Carnot prove his theorem? In what sense did Carnot provide a foundation for the second law? Our approach is to discuss the rst 12 pages of Carnots only publication, Reections on the motive power of heat and the machines tted to develop that power,8 and to imagine the intellectual context in which Carnot and other scientists and engineers worked in 1824. We nd that Carnot used a principle that is very closely related but not identical to a statement of the second law of thermodynamics. Carnots operative principle and other assumptions, which were quite natural in 1824, allowed Carnot to complete his proof. Expressing Carnots operative principle in a language that neither assumes nor denies energy conservation produces what we call Carnots version of the second law or, for convenience, Carnots second law. Although Carnot never advanced this version of the second law, we show that he assumed its logical equivalent. This paper may tax the imaginations of its readers because we ask them to suspend their belief in the rst law of thermodynamics. We realize that such a suspension is extremely difcult. But Carnots Reections appeared in 1824 before Joules experiments began to compel acceptance of the law
21 Am. J. Phys. 76 1, January 2008 http://aapt.org/ajp

of conservation of energy in the late 1840s. In 1824 Carnot subscribed, as did many other scientists and engineers, to the concept of calorican ingenerate, indestructible, and probably massless uid that in owing from one body to another usually cooled the rst and heated the second.9 We do not ask readers to accept the concept of caloric uncritically, but we do ask them to enter into the intellectual world of Carnots Reectionsa world in which energy was not a well-developed concept.10 Historical accuracy is one reason to carefully consider Carnots contribution to the second law, but this reason might not be high priority for physics students and teachers. Axiomatic presentations of thermodynamics consciously adopt an ahistorical approach.11 Physics students and teachers have another reason for considering the historical evolution of thermodynamics: Its history encourages us to confront a larger context of ideas. This larger context constitutes a space of possible ideas that constrains the way we can think about thermodynamics.12 Carnot, the calorist, realized certain ideas out of this space; Clausius and Thomson, as energists, realized others. This possibility space allows us to formulate versions of the second law free from either the conservation of caloric or the conservation of energy, that is, free of the rst law of thermodynamics. If the logical content of any statement consists of all that can be deduced from it, studying deductions from the second law, apart from the rst, may help us better understand the second laws meaning. Some may wonder whether it is possible to conceptualize the content of the second law without, at least implicitly, assuming the rst law or an alternative to the rst law such as the law of conservation of caloric. That we and others13 do so provides an empirically based answer to this question. Nonetheless, the question is a good one. It is not possible to consider consequences of the second law apart from the zeroth law of thermodynamics, because the latter makes the concept of empirical temperature meaningful and statements of the second law refer to higher and lower empirical temperatures. Statements of the second law also exploit the concepts of work and heat. Work can always be reduced to a purely mechanical concept, and heat can be given a precise operational denition in terms of purely calorimetric concepts.14 But there is no necessary linkage between the rst and second laws of thermodynamics. Our paper is organized as follows: Section II identies Carnots operative principle and the version of the second law that is closely related to it. Section III points out that not all formulations of the second law are logically equivalent.
2008 American Association of Physics Teachers 21

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In particular, we show that what we call Carnots second law is more restrictive than Thomsons second law and is logically equivalent to Clausiuss second law. Section IV briey summarizes our conclusions. II. CARNOTS PRINCIPLE AND SECOND LAW Carnots rst proof of Carnots theoremno heat engine operating between two heat reservoirs can be more efcient than a reversible heat engineis in the Thurston translation of Carnots Reections Ref. 8, pp. 1112. Because the theorem usually requires some form of the second law for its proof, we look into the rst 12 pages of Ref. 8 for its operational equivalent. After an interesting cosmological and geopolitical introduction Carnot gives his main theme on p. 6 in the 19th paragraph.8 Carnot remarks that The production of motion in steam-engines is always accompanied by a circumstance on which we should x our attention. This circumstance is the re-establishing of equilibrium in the caloric; that is, its passage from a body in which the temperature is more or less elevated, to another in which it is lower.15 So taken was Carnot with this idea, that in a heat engine the caloric passes from a body in which the temperature is more or less elevated, to another in which it is lower, he repeated it six times in the six subsequent paragraphs.16 We understand his phrase the re-establishing of equilibrium in the caloric to mean the passage of caloric from a body in which the temperature is more or less elevated, to another in which it is lower. Evidently Carnot regarded the mere passage of caloric from a hotter body to a colder one sufcient to produce work in a heat engine. The sentences in which these repetitions occur are We easily recognize in the operations that we have just described the re-establishment of equilibrium in the caloric, its passage from a more or less heated body to a colder one. The production of motive power is then due in steam-engines not to an actual consumption of caloric, but to its transportation from a warm body to a cold body, According to this principle, the production of heat alone is not sufcient to give birth to the impelling power: it is necessary that there should also be cold; without it, the heat would be useless. Wherever there exists a difference of temperature, wherever it has been possible for the equilibrium of the caloric to be re-established, it is possible to have also the production of impelling power. We have shown that in steam-engines the motive-power is due to a re-establishment of equilibrium in the caloric; this takes place not only for steam engines, but also for every heat-engine, that is, for every machine of which caloric is the motor. These changes are not caused by uniform temperature, but rather by alternations of heat and cold. Figure 1a illustrates Carnots simplest heat engineone that produces work by transferring caloric from a hotter heat reservoir to a cooler one. A rectangle represents a heat reservoir, that is, an object with indenitely large heat capacity; a circle stands for a heat engine that has experienced a cycle; and an arrow indicates the direction of non-vanishing heat or work transfer. Because our purpose is to isolate a principle equivalent to the second law of thermodynamics, that is, Carnots principle, from conservation of caloric and conservation of energy, we generalize Carnots simplest heat engine by transforming it as shown in the movement from Fig. 1a to Fig. 1b. In Fig. 1b no assumption is made about the relative sizes of the quantities QH, QC, and Wonly that
22 Am. J. Phys., Vol. 76, No. 1, January 2008

Fig. 1. a Carnots simplest heat engine with caloric conserved. b Carnots simplest heat engine assuming neither that caloric is conserved, QH = QC = Q, nor that energy is conserved, QH = QC + W. By supposition, Q 0, QH 0, QC 0, and W 0.

they are all positive. If caloric is conserved, QH = QC = Q; if energy is conserved, QH = QC + W; without either we know only that QH 0, QC 0, and W 0. If, according to Carnots principle, the simplest cyclic heat engine is one that must extract heat from one reservoir and reject heat to another cooler reservoir, cyclic heat engines that produce work while exchanging heat with fewer than two reservoirs are too simple to be possible. Such heat engines, forbidden by Carnots principle, are illustrated in Fig. 2. Carnot would have found the explicit prohibition of heat engine cycles that violate conservation of caloric, such as those in Figs. 2a and 2b, unnecessary. According to this view, Carnots real original contribution lies in forbidding heat engine cycles that do not exchange heat yet produce work see Fig. 2c.17 Carnot exploited this prohibition of this kind of perpetual motion machine to prove Carnots theorem. His proof is indirect because it assumes the contrary of Carnots theorem and absurdly concludes that this would be not only perpetual motion, but an unlimited creation of motive power without consumption either of caloric or of any other agent whatsoever.18 Carnots indirect proof also involves another absurditya violation of energy conservation. The rst law of thermodynamics would make redundant the prohibitions in Figs. 2b and 2c, and so reduce Carnots principle to the prohibition in Fig. 2a, which is equivalent to Thomsons statement of the second law of thermodynamics. Carnots proof of his theorem makes two assumptions: conservation of caloric, which in effect prohibits the cycles in Figs. 2a and 2b, and the absurdity of a cycle that produces work out of nothing, that is, the cycle in Fig. 2c. But whatever Carnots motivation, these assumptions are logically equivalent to holding both conservation of caloric and conservation of energy in abeyance, and adopting all three

Fig. 2. Cyclic heat engines that are too simple to be possible. Each one violates Carnots principle. Don S. Lemons and Margaret K. Penner 22

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Fig. 3. a Cyclic heat transfer forbidden by Clausiuss statement of the second law. b Cyclic heat engine forbidden by Thomsons statement of the second law.

Fig. 5. a A heat engine that violates Carnots second law and an allowed refrigerator. b The combined heat transfer resulting from the adjustment W = W. The combined heat transfer violates Clausiuss second law.

prohibitions of the cycles in Fig. 2, as a new lawthe second law of thermodynamics. Recasting the prohibitions of the cycles in Fig. 2 into a verbal statement produces what we call Carnots statement of the second law of thermodynamics: A heat engine whose only nal result is to produce work and exchange heat with fewer than two heat reservoirs is impossible.19 Although Carnot never advanced this version of the second law of thermodynamics, he adopted its logical equivalent in his proof of his theorem. III. THE CLAUSIUS AND THOMSON STATEMENTS OF THE SECOND LAW Soon after James Joule established the equivalence of work and heat, Clausius5 in 1850 and Thomson Lord Kelvin6 in 1851 proposed distinct versions of the second law of thermodynamics.20 Figure 3a illustrates Clausiuss second law: A process whose only nal result is to extract heat from a reservoir and reject heat to a hotter reservoir is impossible. Clausiuss second law, stripped of rst law content, forbids cyclic heat transfers of the kind diagrammed in Fig. 3a for QH 0 and QC 0, and not only for rst law compliant, that is, QH = QC, heat transfers. Figure 3b illustrates Thomsons second law: A process whose only nal result is to extract heat from a single reservoir and produce work is impossible. Thomsons second law, stripped of rst law content, forbids cyclic heat engines of the kind in Fig. 3b for any Q 0 and W 0 and not only for rst law compliant, that is, Q = W, cyclic heat engines. Planck corrected Thomsons original 1851 statement of the second law by insisting that the word only be included.21

Apart from the rst law, Thomsons second law prohibits fewer types of cycles than Carnots second law and, for this reason, is less restrictive than Carnots second law. In addition, the Clausius and Carnot statements of the second law are logically equivalent, but some effort is required to show this.22 To prove that Carnots second law and Clausiuss second law are logically equivalent we rst show that Clausiuss second law implies Carnots and then show that Carnots second law implies Clausiuss. Together these demonstrations establish the logical equivalence of the Carnot and Clausius statements. We prove that Carnots second law implies Clausiuss second law by showing that a denial of Clausiuss second law leads to a denial of Carnots second law. If Clausiuss second law can be denied, heat QC 0 can be extracted from one reservoir at temperature TC and heat QH 0 rejected to a hotter reservoir at temperature TH TC as shown in cycle 1 of Fig. 4a. Combine this supposed heat transfer with an allowed heat engine23 of the type shown in Fig. 1b and illustrated by cycle 2 in Fig. 4a, which extracts heat QH from the hotter reservoir at temperature TH, produces work W, and rejects heat QC to the colder reservoir at temperature TC. Adjust QC = QC to produce the combined engine 1 + 2 illustrated in Fig. 4b. Given two engines we can always make one and only one such adjustment by allowing each engine to complete an appropriate number of cycles.24 The combined heat engine 1 + 2 exchanges heat with at most one reservoir whatever the sign or value of QH QH and produces work. For this reason, it contradicts Carnots second law. To show that Clausiuss second law implies Carnots second law we again prove the contrapositive, that is, violating

Fig. 4. a A heat transfer that violates Clausiuss second law and an allowed heat engine. b The combined engine resulting from the adjustment QC = QC . The combined engine violates Carnots second law whatever the sign or value of QH Q H. 23 Am. J. Phys., Vol. 76, No. 1, January 2008

Fig. 6. a A heat engine that violates Carnots second law and an allowed refrigerator. b The combined heat transfer resulting from the adjustment W = W. The combined heat transfer violates Clausiuss second law. Don S. Lemons and Margaret K. Penner 23

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Fig. 7. a A heat engine that violates Carnots second law and an allowed refrigerator. b The combined heat transfer resulting from the adjustment W = W. The combined heat transfer violates Clausiuss second law.

Carnots second law leads to a violation of Clausiuss second law. There are three ways to violate Carnots second law. We will chose one and show the reader how to complete the proof when choosing the other two.25 Suppose, contrary to Carnots second law, an engine can produce work W by extracting heat Q from a single reservoir at temperature TC as shown in Figs. 2a and 5a. Combine this supposed heat engine with an allowed refrigerator24 that consumes work W, extracts heat QC from the colder reservoir at temperature TC, and rejects heat QH to a hotter reservoir at temperature TH TC. Adjust W = W so that the combined engine merely extracts heat Q + QC 0 from the reservoir at temperature TC and rejects heat QH 0 to the hotter reservoir at temperature TH as illustrated in Fig. 5b. This combined cycle 1 + 2 directly violates Clausiuss statement of the second law for any values Q 0, QH 0, and QC 0. To complete the proof we must show that violating Carnots second law in the two remaining ways, that is, assuming the forbidden cycles found in Figs. 2b and 2c, also leads to violations of Clausiuss statement of the second law. These inferences follow closely the pattern shown in Fig. 5. Figures 6 and 7 illustrate the logic sufcient to complete the proof. IV. CONCLUSION We have identied in Carnots essay8 a principle that, with conservation of caloric, played the role of the second law of thermodynamics. This principle states that the simplest possible cyclic heat engine is one that produces work by extracting heat from one heat reservoir and rejecting heat to a cooler heat reservoir. In terms of more contemporary language and separated from the content of the rst law of thermodynamics or any alternative to it, this principle constitutes the following statement of the second law of thermodynamics: A heat engine whose only nal result is to produce work and exchange heat with fewer than two heat reservoirs is impossible. Although Carnot never advanced this version of the second law of thermodynamics, he assumed its logical equivalent. We have also shown that what we call Carnots statement of the second law is, apart from the rst law, logically equivalent to Clausiuss version of the second law and both of these are more restrictive than Thomsons. ACKNOWLEDGMENTS The authors acknowledge the helpful comments of Galen Gisler, Dwight Neuenschwander, Ralph Baierlein, and a referee.
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See, for example, C. J. Adkins, Thermodynamics McGraw-Hill, London, 1978, pp. 5961. 2 E. Fermi, Thermodynamics Dover, New York, 1936, pp. 3031, and Ref. 1, p. 56. 3 M. K. Barnett, Sadi Carnot and the second law of thermodynamics, Osiris 13, 333357 1958. 4 Joseph Kestin, The Second Law of Thermodynamics Dowden, Hutchinson and Ross, Stroudsburg, PA, 1967, p. 12. 5 Rudolph Clausius, On the motive power of heat, and on the laws which can be deduced from it for the theory of heat, found in Reections on the Motive Power of Fire, edited by E. Mendoza and translated by W. F. Magie Dover, New York, 1960, pp. 107152. 6 W. Thomson, On the dynamical theory of heat, with numerical results deduced from Mr. Joules equivalent of a thermal unit, and M. Regnaults observations on steam, excerpted in Ref. 4, pp. 110111. 7 See Ref. 4. 8 Sadi Carnot, Reections on the Motive Power of Fire, edited by E. Mendoza and translated by R. H. Thurston Dover, New York, 1960, pp. 159. 9 The view that Carnot employed the caloric theory of heat in the Reections has been adopted by most expositors and contested by a few. For an extended discussion and further references see T. S. Kuhn, La Mers version of Carnots cycle, Am. J. Phys. 23, 387389 1955; T. S. Kuhn, Carnots version of Carnots cycle, Am. J. Phys. 23, 9195 1955; V. K. La Mer, Some current misinterpretations of N. L. Sadi Carnots memoir and cycle II, Am. J. Phys. 23, 95102 1955; and V. K. La Mer, Some current misinterpretations of N. L. Sadi Carnots memoir and cycle, Am. J. Phys. 22, 2027 1954. 10 Carnots posthumously published notes reveal that Carnot came to believe, within a few years following the publication of the Reections, that energy rather than caloric was conserved. See Ref. 8, pp. 6069. 11 Caratheodorys axiomatization of thermodynamics is one example of an ahistorical presentation of thermodynamics; Callens postulational approach is another. For the former see C. J. Adkins, Thermodynamics McGraw-Hill, London, 1978, pp. 93104; for the latter see H. B. Callen, Thermodynamics Wiley, New York, 1962. 12 The concept of a space of possible ideas that shapes our thinking about a subject is borrowed from Ian Hacking, The Emergence of Probability Cambridge U. P., Cambridge, 1975, p. 9. 13 See H. Schamp, Independence of the rst and second laws of thermodynamics, Am. J. Phys. 30, 825829 1962. 14 Qualitatively heat can be dened as that which changes the state of a thermodynamic system without work interactions or mass transfer. 15 Reference 8, p. 6. 16 Reference 8, pp. 79. 17 A statement prohibiting the cycle in Fig. 2c is what Kestin meant as the rst verbal formulation of the second law. See Ref. 4. 18 Reference 8, p. 12. 19 J. T. Vanderslice, H. W. Schamp, and E. A. Mason adopt this version of the second law in their text Thermodynamics Prentice Hall, Englewood Cliffs, NJ, 1966, p. 29, and loosely, but we believe misleadingly, characterize it as similar to the statement given by William Thomson in 18511852. 20 That Thomson proposed his statement of the second law independently of Clausiuss statement of the second law has been disputed by Levi Tansjo in Comment on the discovery of the second law, Am. J. Phys. 56, 179182 1988. Whether or not Thomsons discovery was independent of Clausiuss discovery, the Thomson statement of the second law is verbally and logically distinct from the Clausius statement. 21 M. Planck, Treatise on Thermodynamics Dover, New York, 1945, pp. 82 ff. 22 Seventy years ago the Nobel Laureate Percy Bridgman observed, There have been nearly as many formulations of the second law as there have been discussions of it.and not all these formulations can be exactly equivalent, but it is possible to distinguish stronger and weaker forms. See Percy Bridgman, The Nature of Thermodynamics Harvard U. P., Cambridge, MA, 1941, p. 116. Bridgman adds, in the ellipsis of this quotation, the seemingly adventitious remark, I question whether such an examination would be of great physical interest. We disagree. 23 Thermodynamics texts always assume that some cyclic processes are possible in the course of proving that others are impossible. See, for instance, Ref. 2, Fermi, pp. 31, 3435, and Ref. 1, Adkins, pp. 5657. We do the same in assuming that a heat engine and a refrigerator are possible
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Don S. Lemons and Margaret K. Penner

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with some combination of values QH 0, QC 0, and W 0. There is some unknown relation for example, energy or caloric conservation or some other relation among QH, QC, and W that, given any two quantities, determines the third. This unknown relation precludes us from making more than one adjustment. In general n 1 adjustments of heat or

work can be made among quantities describing n engines. See Ref. 2, Fermi, p. 37. 25 These deductions are assigned as Problem 3 of Chap. 5 in Ref. 19, and E. A. Mason, Thermodynamics Prentice Hall, Englewood Cliffs, NJ, 1966, p. 47.

Overbecks Cross Pendulum. This piece of apparatus, at Case Western Reserve University, is listed in the 1900 catalogue of Max Kohl of Chemnitz, Germany as Overbecks cross pendulum. I can see two uses for this apparatus, which has an axle with masses that can be set out various distances from it. If the masses are adjusted so that the center of mass is not at the axis, the system will oscillate as a physical pendulum. The location of the center of mass is calculated and the moment of inertia found either by calculation or by experiment, and the resulting calculated period compared with experiment. Or, the masses can all be set out the same distance from the axle, and the calculated moment of inertia compared with that found by winding a string around the axle and observing the motion of a falling mass fastened to the other end of the string. Photograph and Notes by Thomas B. Greenslade, Jr., Kenyon College

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