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The History of Thermodynamics: Past and Future
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Gases
Horror
vacui seminar 8NTNU,
ThermoTech
2. December 2005
Solids
Phlogiston
Tore 9
Haug-Warberg
10 Electrolytes
Aether
11 Molecular dynamics
Heat and work
12 Ab initio
Basic laws
13 The future
Axioms
Kinetic gas theory
The History of Thermodynamics
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Horror vacui
Nature 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.
The History of Thermodynamics
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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 atmospheric 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).
The History of Thermodynamics
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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.
The History of Thermodynamics
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Steam engines
The 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).
The History of Thermodynamics
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Phlogiston
A 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.
The History of Thermodynamics
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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.
The History of Thermodynamics
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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”?
The History of Thermodynamics
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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).
The History of Thermodynamics
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The 2nd law of thermodynamics
The entropy of the universe tends to a maximum (Clausius)
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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”.
The History of Thermodynamics
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The 1st law of thermodynamics
The energy of the universe is constant (Clausius)
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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”.
The History of Thermodynamics
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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).
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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”.
The History of Thermodynamics
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The 3rd law of thermodynamics
The entropy tends to zero in the limit of zero temperature.
Requires that Cp approaches zero faster than T itself.
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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.
The History of Thermodynamics
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The rise and fall
In 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).
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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”.
The History of Thermodynamics
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Axiomatic thermodynamics
The 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.
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Laszlo Tisza (1966): Rational thermodynamics.
Herbert B. Callen (1985):
A1 S a = S (U a ,V a , N 1a , K , N na )
A2 S eq = min S tot
A3 S tot = S a + S b + L + S w
A4 ¶ U/ ¶ S ® 0
Þ
S ® 0
C3 S (l U , l V , l N 1, K , l N n ) = l S (U ,V , N 1, K , N n )
The History of Thermodynamics
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Gas laws
Thermodynamics is a general framework without predictive
power. For this purpose physical models are needed. The
most important example is ideal gas (pV = NRT):
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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
The History of Thermodynamics
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Kinetic theory
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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.
The History of Thermodynamics
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Real gases
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Johannes Diderik van der Waal (1873): The first nontrivial 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).
The History of Thermodynamics
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Theoretical models
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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.
The History of Thermodynamics
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Molecular dynamics
Newtonian mechanics in electric force fields
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N. A. Metropolis et al (1953):
Equation of state calculations by fast
computing machines.
A. Rahman (1964): The first
molecular dynamics simulation
on the Lennard-Jones fluid.
Stephen Wolfram (1984): Cellular
automata (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).
The History of Thermodynamics
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Ab initio
OK, 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.
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Max Planck Institute
ETH
MIT
NTNU
Etc.
D. Alfe et al (2000): Recent developments in ab
initio thermodynamics.
The History of Thermodynamics
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The future
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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
The History of Thermodynamics