Ingen lysbildetittel

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The History of Thermodynamics Past and Future

• Gases
• Solids
• Electrolytes
• Molecular dynamics
• Ab initio
• The future

1. Horror vacui
2. Phlogiston
3. Aether
4. Heat and work
5. Basic laws
6. Axioms
7. 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
Philosophers 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 gt 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 contd

• 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)

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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/gers
  henfeld_index.html

• Tore Haug-Warberg (2005)