the history of thermodynamics: past and future

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The History of Thermodynamics

The History of Thermodynamics: Past and Future

8 Gases9 Solids10 Electrolytes11 Molecular dynamics12 Ab initio13 The future

1. Horror vacui2. Phlogiston3. Aether4. Heat and work5. Basic laws6. Axioms7. Kinetic gas theory

ThermoTech seminar NTNU, 2. December 2005Tore Haug-Warberg

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Horror vacuiNature abhors a vacuum

• Aristoteles (around 350 BC): Horror vacui became the prevailing axiom for 1800 years.

• Evangelista Torricelli (1644): Invented the barometer and thereby recognized vacuum.

• Otto von Guericke (1654): Convincing demonstrations of Magdeburg hemispheres.

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Vacuum (force)Condensing water can be used to create a partial vacuum upon which the atmosphere can do mechanical work.

• Denis Papin (1690): Demonstrated the principle of atmo-spheric work (boiler, cylinder and condenser the same thing).

• Thomas Newcomen (1712): The first practical atmospheric steam engine (with separate cylinder and boiler).

• James Watt (1769): The improved atmospheric steam engine (with separate cylinder, boiler and condenser).

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Pressure (force)Boiling water can be used to create a pressure which is suitable for mechanical work.

• Heron of Alexandria (ca. 50): Invented the aeolipile. Ignored for 1800 years.

• Richard Trevithick (1808): “Catch me who can”.

• Charles A. Parsons (1884): Reaction turbine.

• Gustaf de Laval (1888): Action turbine.

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Steam enginesThe development of the nearly perfect atmospheric steam engine required no thermodynamics.

• Newcomen and Watt atmospheric engines.

• Trevithick and other high-pressure, saturated steam, engines.

• Steam engines and steam turbines running on superheated steam.

• Carnot efficiency (at saturated steam temperature).

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PhlogistonA substance without color, odor, taste, or weight that is given off in burning. In modern terms: antioxygen. It initiated an attempt to rationalize chemistry, and eventually caused the death of alchemy and the search of Philosopher’s stone.

• Johann J. Becher (1699): Phlogiston theory.

• Jospeh Priestley (1774): Kept two mice and a candle alive in dephlogisticated air (oxygen).

• Antoine Lavoisier (1782): Demonstrated the principle of mass conservation => the swane song of phlogiston.

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Aether A substance of a more subtle kind than visible bodies, supposed to exist in those parts of space which are apparently empty.

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Aether cont’d

• Aristoteles (around 350 BC): Earth, air, fire, and water. The fifth element (the quintessence), was the aether.

• Albert A. Michelson & Edward Morley (1887): Attempted to measure the aether wind, but achieved the contrary.

• Lord Kelvin (1896): ... “I know no more of electric and magnetic force, or of the relation between ether, electricity, and ponderable matter than I knew fifty years ago”.

• Albert Einstein (1920): ... ”space is endowed with physical qualities; in this sense, therefore, there exists an ether”...

• Paul Dirac (1951): “Is there an aether”?

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Caloric (French) An invisible fluid which transfer heat from one body to another without being created or destroyed.

• Antoine Lavoisier (1783): Introduced the caloric to remedy the flaws of phlogiston theory.

• Sadi Carnot (1824): Reflections on the motive power of fire (steam engine analysis).

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The 2nd law of thermodynamicsThe entropy of the universe tends to a maximum (Clausius)

• Sadi Carnot (1824): “Reflections on the motive power of fire”.

• Clapeyron (1833): The first version of the second law based on a study of steam engines.

• Rudolf J. E. Clausius (1854): Proposes the function dQ/T as a way to compare heat flows.

• Rudolf J. E. Clausius (1865): “The entropy of the universe tends to a maximum”.

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The 1st law of thermodynamics The energy of the universe is constant (Clausius)

• Benjamin Thompson alias Count Rumford, (1798): “An experimental inquiry concerning the cource of the heat which is excited by friction”.

• Julius Robert von Mayer (1842): “On the forces of the inanimate nature”.

• James Prescott Joule (1843): Measurements on the mechanical equivalent of heat.

• Hermann Helmholtz (1847): ”On the Conservation of Energy”.

• Rudolf J. E. Clausius (1865): “The energy of the universe is constant”.

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The 0th law of thermodyn.If two systems A and B are in (thermal) equilibrium, and B and C are also in equilibrium, then A and C are in equilibrium (Maxwell).

• Santorre Santorio (1575): Used an early thermoscope (differential thermometer).

• Gabriel Daniel Fahrenheit (1714): The first mercury thermometer.

• Anders Celsius (1742): Observations on two persistent degrees on a thermometer.

• Lord Kelvin (1848): A scale of absolute temperature based on the theory of Carnot.

• James Clerk Maxwell (1872): “Two systems A and B in thermal equilibrium with a third system C, are in thermal equilibrium with one another”.

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The 3rd law of thermodynamicsThe entropy tends to zero in the limit of zero temperature. Requires that Cp approaches zero faster than T itself.

• Walther Nernst (1906): In the limit of absolute zero temperature, both the entropy change and the heat capacity go to zero.

• Albert Einstein (1907): Quantum mechanic model for the specific heat of solids deriving the law of Dulong and Petit.

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The rise and fallIn no other discipline have the same equations been published so many times by different authors in different notations and therefore claimed as his own by each (Truesdell).

• Rudolf J. E. Clausius (1865): i) “The entropy of the universe tends to a maximum”. ii) “The energy of the universe is constant”.

• Josiah Willard Gibbs (1876): On the equilibrium of heterogenous substances.

• Constantine Caratheodory (1908): Investigations about the foundation of thermodynamics.

• The next 60 years nothing important happens!

• Clifford A. Truesdell (1983): “The tragicomical history of thermodynamics”.

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Axiomatic thermodynamicsThe 4 laws of thermodynamics tell only something about the interaction of the system and the environment, but nothing about the mathematical properties of the system itself.

• Laszlo Tisza (1966): Rational thermodynamics.• Herbert B. Callen (1985):

()()()111A1 ,,,,A2 minA3 A4 U/0 0 C3 ,,,,,,,,neqtottotnnSSUVNNSSSSSSSSSUVNNSUVNNaaaaaabwlllll===+++¶¶®?®=KLKK

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Gas lawsThermodynamics is a general framework without predictive power. For this purpose physical models are needed. The most important example is ideal gas (pV = NRT):

• Robert Boyle (1661): PV = C

• Jackues-Alexandre Charles (1787): V/T = C

• John Dalton (1801): p/N = C

• Gay-Lussac (1802): p/T = C

• Amedeo Avogadro (1811): V/N = C

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Kinetic theory

• Daniel Bernoulli (1733): Gave birth to kinetic gas theory. Forgotten until 1859.

• John Herapath (1816): Awaked kinetic theory. Ignored.

• John James Waterston (1843): Awaked kinetics theory. Ignored.

• James Clerk Maxwell (1859): Rigorously established kinetic theory.

• Ludwig Boltzmann (1871): Ergodic theorem.

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Real gases

• Johannes Diderik van der Waal (1873): The first non-trivial equation of state (cubic).

• Joseph Edward Mayer and Maria Goeppert-Mayer (1936): Virial equation of state.

• Otto Redlich and J. N. S. Kwong (1949): First realistic two-phase equation of state (cubic).

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Theoretical models

• Albert Einstein (1907): Vibrating crystals.

• O. Sackur and H. Tetrode (1912): Monoatomic gases.

• Peter Debye and Erich Huckel (1923): Dilute electrolytes.

• Albert Einstein (1925): Boson gases (superfluids).

• Enrico Fermi (1925): Fermion gases (electrons).

• Lars Onsager (1942): The 2-dimensional Ising model.

• Benjamin Widom (1965): Surface tension theory using van der Waals theory.

• Kenneth Wilson (1971): Renormalization group theory applied to fluids at the critical point.

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Molecular dynamicsNewtonian mechanics in electric force fields

• N. A. Metropolis et al (1953): Equation of state calculations by fastcomputing machines.

• A. Rahman (1964): The first molecular dynamics simulationon the Lennard-Jones fluid.

• Stephen Wolfram (1984): Cellularautomata (fluid dynamics).

• It is a sad fact that this research area has developed into a political issue due to the high cost of supercomputing (figure to the right).

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Ab initioOK, the Schrødinger equation is maybe the answer to “Life, Universe and Everything”, but the calculated physical properties depend entirely on the boundary conditions. This is there the real challenge is.

• Max Planck Institute

• ETH

• MIT

• NTNU

• Etc.

• D. Alfe et al (2000): Recent developments in ab initio thermodynamics.

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The future• Lord Kelvin (1894): Radio has no future.

• A. A. Michelson (1894): The future of science will consist of adding a few decimal places to the results already obtained.

• Thomas Watson viz. chairman of IBM (1943): The world market is maybe five computers.

• John von Neumann (1955): ... a few decades hence, (nuclear) energy may be free -- just like the unmetered air ...

• Tore Haug-Warberg (2005): The computer was born in the lab. It has now entered our homes. It will next be designed and made according to our own specifications. Then, finally, we can do serious computations! See e.g. Neil Gershenfeld at http://www.edge.org/3rd_culture/gershenfeld03/gershenfeld_index.html

• Tore Haug-Warberg (2005):

the history of thermodynamics: past and future

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