First law of thermodynamics

The first law of thermodynamics is a formulation of the law of conservation of energy in the context of thermodynamic processes. The law distinguishes two principal forms of energy transfer, heat and thermodynamic work, that modify a thermodynamic system containing a constant amount of matter. The law also defines the internal energy of a system, an extensive property for taking account of the balance of heat and work in the system. Energy cannot be created or destroyed, but it can be transformed from one form to another. In an isolated system the sum of all forms of energy is constant.

An equivalent statement is that perpetual motion machines of the first kind are impossible; work done by a system on its surroundings requires that the system's internal energy be consumed, so that the amount of internal energy lost by that work must be resupplied as heat by an external energy source or as work by an external machine acting on the system to sustain the work of the system continuously.

The ideal isolated system, of which the entire universe is an example, is often only used as a model. Many systems in practical applications require the consideration of internal chemical or nuclear reactions, as well as transfers of matter into or out of the system. For such considerations, thermodynamics also defines the concept of open systems, closed systems, and other types.

Description

Cyclic processes

The first law of thermodynamics for a closed system was expressed in two ways by Clausius. One way referred to cyclic processes and the inputs and outputs of the system, but did not refer to increments in the internal state of the system. The other way referred to an incremental change in the internal state of the system, and did not expect the process to be cyclic.

A cyclic process is one that can be repeated indefinitely often, returning the system to its initial state. Of particular interest for single cycle of a cyclic process are the net work done, and the net heat taken in (or 'consumed', in Clausius' statement), by the system.

In a cyclic process in which the system does net work on its surroundings, it is observed to be physically necessary not only that heat be taken into the system, but also, importantly, that some heat leave the system. The difference is the heat converted by the cycle into work. In each repetition of a cyclic process, the net work done by the system, measured in mechanical units, is proportional to the heat consumed, measured in calorimetric units.

The constant of proportionality is universal and independent of the system and in 1845 and 1847 was measured by James Joule, who described it as the mechanical equivalent of heat.

Since the work of Bryan (1907), the most accepted way to deal with it nowadays, followed by Carathéodory,^[30]^[49] is to rely on the previously established concept of quasi-static processes,^[50]^[51]^[52] as follows. Actual physical processes of transfer of energy as work are always at least to some degree irreversible. The irreversibility is often due to mechanisms known as dissipative, that transform bulk kinetic energy into internal energy. Examples are friction and viscosity. If the process is performed more slowly, the frictional or viscous dissipation is less. In the limit of infinitely slow performance, the dissipation tends to zero and then the limiting process, though fictional rather than actual, is notionally reversible, and is called quasi-static. Throughout the course of the fictional limiting quasi-static process, the internal intensive variables of the system are equal to the external intensive variables, those that describe the reactive forces exerted by the surroundings.^[53] This can be taken to justify the formula
$W_{A\to O}^{\text{adiabatic, quasi-static}}=-W_{O\to A}^{\text{adiabatic, quasi-static}}\,.$ (1)

[27]

Another way to deal with it is to allow that experiments with processes of heat transfer to or from the system may be used to justify the formula () above. Moreover, it deals to some extent with the problem of lack of direct experimental evidence that the time order of stages of a process does not matter in the determination of internal energy. This way does not provide theoretical purity in terms of adiabatic work processes, but is empirically feasible, and is in accord with experiments actually done, such as the Joule experiments mentioned just above, and with older traditions.

1 Laws of thermodynamics

Perpetual motion

– includes microscopic definitions of internal energy, heat and work

Microstate (statistical mechanics)

Entropy production

Relativistic heat conduction

Adkins, C. J. (1968/1983). Equilibrium Thermodynamics, (first edition 1968), third edition 1983, Cambridge University Press, 0-521-25445-0.

ISBN

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Bailyn, M. (1994). A Survey of Thermodynamics, American Institute of Physics Press, New York, 0-88318-797-3.

ISBN

(1949). Natural Philosophy of Cause and Chance, Oxford University Press, London.

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(1907). Thermodynamics. An Introductory Treatise dealing mainly with First Principles and their Direct Applications, B. G. Teubner, Leipzig.

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(1997). Statistical Dynamics; Matter out of Equilibrium, Imperial College Press, London, ISBN 978-1-86094-045-3.

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Buchdahl, H. A. (1966), The Concepts of Classical Thermodynamics, Cambridge University Press, London.

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(1909). "Untersuchungen über die Grundlagen der Thermodynamik". Mathematische Annalen. 67 (3): 355–386. doi:10.1007/BF01450409. S2CID 118230148. A translation may be found here. Also a mostly reliable translation is to be found at Kestin, J. (1976). The Second Law of Thermodynamics, Dowden, Hutchinson & Ross, Stroudsburg PA.

Carathéodory, C.

(1850), "Ueber die bewegende Kraft der Wärme und die Gesetze, welche sich daraus für die Wärmelehre selbst ableiten lassen", Annalen der Physik, 79 (4): 368–397, 500–524, Bibcode:1850AnP...155..500C, doi:10.1002/andp.18501550403, hdl:2027/uc1.$b242250. See English Translation: On the Moving Force of Heat, and the Laws regarding the Nature of Heat itself which are deducible therefrom. Phil. Mag. (1851), series 4, 2, 1–21, 102–119. Also available on Google Books.

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de Groot, S. R., Mazur, P. (1962). Non-equilibrium Thermodynamics, North-Holland, Amsterdam. Reprinted (1984), Dover Publications Inc., New York, 0486647412.

ISBN

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Denbigh, K. (1954/1981). The Principles of Chemical Equilibrium. With Applications in Chemistry and Chemical Engineering, fourth edition, Cambridge University Press, Cambridge UK, 0-521-23682-7.

ISBN

Eckart, C. (1940). The thermodynamics of irreversible processes. $I.$ The simple fluid, Phys. Rev. 58: 267–269.

Fitts, D. D. (1962). Nonequilibrium Thermodynamics. Phenomenological Theory of Irreversible Processes in Fluid Systems, McGraw-Hill, New York.

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Gyarmati, I. (1967/1970). Non-equilibrium Thermodynamics. Field Theory and Variational Principles, translated from the 1967 Hungarian by E. Gyarmati and W. F. Heinz, Springer-Verlag, New York.

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Haase, R. (1971). Survey of Fundamental Laws, chapter 1 of Thermodynamics, pages 1–97 of volume 1, ed. W. Jost, of Physical Chemistry. An Advanced Treatise, ed. H. Eyring, D. Henderson, W. Jost, Academic Press, New York, lcn 73–117081.

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Bibcode

Kestin, J. (1966). A Course in Thermodynamics, Blaisdell Publishing Company, Waltham MA.

Oppenheim, I. (1961). Chemical Thermodynamics, McGraw-Hill Book Company, New York.

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ISBN

Lebon, G., Jou, D., Casas-Vázquez, J. (2008). Understanding Non-equilibrium Thermodynamics, Springer, Berlin, 978-3-540-74251-7.

ISBN

Mandl, F. (1988) [1971]. Statistical Physics (2nd ed.). Chichester·New York·Brisbane·Toronto·Singapore: . ISBN 978-0471915331.

John Wiley & Sons

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ISBN

(1949). An Advanced Treatise on Physical Chemistry, volume 1, Fundamental Principles. The Properties of Gases, Longmans, Green and Co., London.

Partington, J.R.

(1957/1966). Elements of Classical Thermodynamics for Advanced Students of Physics, original publication 1957, reprint 1966, Cambridge University Press, Cambridge UK.

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(1897/1903). Treatise on Thermodynamics, translated by A. Ogg, Longmans, Green & Co., London.

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Pokrovskii, Vladimir (2020). Thermodynamics of Complex Systems: Principles and applications. IOP Publishing, Bristol, UK. :2020tcsp.book.....P.

Bibcode

(1947). Étude Thermodynamique des Phénomènes irréversibles, Dunod, Paris, and Desoers, Liège.

Prigogine, I.

(1955/1967). Introduction to Thermodynamics of Irreversible Processes, third edition, Interscience Publishers, New York.

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Tschoegl, N. W. (2000). Fundamentals of Equilibrium and Steady-State Thermodynamics, Elsevier, Amsterdam, 0-444-50426-5.

ISBN

Goldstein, Martin; Inge F. (1993). . Harvard University Press. ISBN 0-674-75325-9. OCLC 32826343. Chpts. 2 and 3 contain a nontechnical treatment of the first law.

The Refrigerator and the Universe

Çengel Y. A.; Boles M. (2007). Thermodynamics: an engineering approach. McGraw-Hill Higher Education. 978-0-07-125771-8. Chapter 2.

ISBN

Atkins P. (2007). Four Laws that drive the Universe. OUP Oxford. 978-0-19-923236-9.

ISBN

(PDF file) by Jerzy Borysowicz for Project PHYSNET.

MISN-0-158, The First Law of Thermodynamics

in the MIT Course Unified Thermodynamics and Propulsion from Prof. Z. S. Spakovszky