History of Thermodynamics ========================= The history of thermodynamics is a complicated, convoluted mess. Things didn't happen in a linear fashion. There were lots of false starts and steps backwards. It was only relatively recently -- in the last 100 years -- that we've really been able to bring this subject together into a cohesive whole. Even now, some concepts in thermodynamics are begging for simplification or further investigation. This field plays an important role in cryophysics (the study of the super-cold) and solid state physics (the study of how matter actually behaves). But the concepts of thermodynamics are found in every field of physics, and plays an important role. .. toctree:: before_classical_greeks.rst classical_greeks.rst thermometers_and_barometers.rst ideal_gas_law.rst phlogiston_caloric.rst steam_engines_calorimeters.rst atomic_kinetic_theory.rst cryophysics.rst Timeline --------- - 3000 BC: Egyptians viewed heat as related to mythologies. Heat and temperature are viewed as purely speculative religious subjects. Whatever is in scripture or taught by priests is the law and there is no questioning of it. - c. 624-546 BC: Thales "All is water" - c. 570-495 BC: Pythagoras "All is number" - c. 500 BC: Parmenides argued against zero, vacuum; for monism. Parmenides marks the beginning of people questioning what they were told about nature and the gods, and the first time that ideas are constrained by reality. Nothing changes. Any change we see is an illusion. "Whatever is is and what is not cannot be". - 535-475 BC: Heraclitus AKA "The Weeping Philosopher" taught that change was the essential part of the unvierse. "flux and fire" -- "Panta rhei" = "everything flows". "Logos" dictates what is going to happen -- logos being word, reason, etc... Things change form. - Empedocles "On Nature": Volume of a gas proportional to temperature? - c. 470-499 BC: Socrates - c. 428-348 BC: Plato, dualism AKA platonic reality. Theory of Forms. Academy of Athens. - 384-322 BC: Aristotole, the Father of Western Philosophy and thus modern science. - Five Elements (four + Aether) - Observation and reasoning, no experiment. - ??? BC: Empedocles four elements, atomic theory, vacuum - ??? BC: Atomism by Leucippus, Democritus, Epicureans - 280?-220? BC: Philo of Byzantium: Thermoscope - Aristotle. Classify and name all the things based on their properties. Proposes "hot" and "cold" as properties of the four elements, but not substances of themselves. Argues against atomism but in favor of a vacuum. - 10 - 70 AD: Hero of Alexander argued for a vacuum. Thermoscope? First steam engine. Knew volume of gas related to temperature. - 400 AD - 1500 AD: Middle Ages. During this time, philosophers are consumed with questions regarding the nature of God and the universe, the essence of reality and truth. The ability to argue becomes critical to identify and coutner heresy. Greek philosophy and Jewish and Christian religion freely mingles together with various results. - 1300s AD: Empiricism, the idea that you must be able to repeat experiments, began to replace Aristotlean ideas about observation and reasoning alone. - 1500s AD: The Reformation. People begin to question Rome and Papal authority. They intend to read and understand for themselves, and many do not consider rulings of the pope to be the ultimate arbiter of truth. People begin experimenting with ideas such as freedom of expression and thought, and the Roman Catholic Church is not able to stop it anymore. - 1500s - 1800s AD: The Early Modern Period. Europe begins to leave its bubble and branch out. The Catholic Church loses its grip on thinking and science. People begin to embrace strange new ideas. - 1300s - 1600s AD: The Renaissance, a rediscovery of the ancients, a rebirth in human thought. Humanism, the idea that man was meant to enjoy and understand life, and not just endure misery, is born. - 1550s AD: Cornelius Drebbel, Robert Fudd, Galileo Galilei, Santorio Santorio and the thermoscope. - 1596-1650 AD: Rene Descartes. In addition to unifying geometry and algebra, he lays the groundwork for modern science by declaring, "I think, therefore I am." That is, the only thing he knows to exist is his own thoughts, or his capacity to thought. All the senses can be fooled, but he believes that God will always provide a way to obtain truth, even in the face of demonic influences that deceive the senses. Descartes rejected the idea that things were predestined to be the way they are, instead asserting that God created the universe to act on its own. - 1600s - 1900 AD: The Scientific Revolution! People begin to rely on carefuly measurements to compare theories with reality. If they find reality to not comport with ideas about reality, they reject those ideas and replace them with new ones. People begin to be free to share crazy ideas without worry of religious persecution. - 1600s AD: Phlogiston, later understood to be oxidation. - 1611-1613 AD: The first thermometers with a scale drawn on them, but either Francesco Sagredo or Santorio Santorio. - 1617 AD: The first clear diagram of a thermoscope is published by Giuseppe Biancani. - 1618-1648 AD: Thirty Years' War devastates Europe. - 1620 AD: Francis Bacon proposes heat is a a form of motion, not a substance, in "Novum Organum." - 1624 AD: The word "Thermometer" appears in a work by J. Leurechon. He describes one with 8 degrees. - 1629 AD: Joseph Solomon Delmedigo publishes the first description and illustration of a sealed liquid-in-glass thermometer with a scale. He doesn't take credit for it but doesn't name the inventor. - 1638 AD: Robert Fludd publishes a picture of a thermoscope with a scale -- the first thermometer. This was a vertical tube closed by a bulb of air at the top with the lower end opening into a vessel of water, what we would call an air thermometer, and measured air pressure and temperature. - 1642-1651 AD: The English Civil War. - 1643 AD: Galileo Galilei encouraged former pupil Evangelista Torricelli to investigate the limitations of the pumps in mines only being able to pump water 30 feet in the air. Torricelli proposes "Horror Vacui" is not a thing and that it is the pressure of the air outside that pushes the water up. Filled a tube with mercury and created a vacuum! Mercury rises only according to the pressure of the air. VACUUM CREATED. PRESSURE UNDERSTOOD. - 1654 AD: Ferdinando Il de'Medici creates the first sealed liquid-in-glass thermometer. - 1656 AD: Robert Boyle and Robert Hooke build an air pump. Notice PV = k. - 1660s AD: Richard Towneley and Henry Power note that pressure and volume are related, inversely proportional to one another. - 1662 AD: Boyle's Law (AKA Boyle-Maroitte Law or Mariotte's Law): PV = k when T and N held constant. Boyle imagined air to be made of particles at rest with invisible springs between them. Boyle disagreed that air was one of the four classical elements. Boyle probably wanted to understand air as an essential element of life. Used a J-shaped tube to compress air with mercury. Noted that pressure and volume were inversely proportional. - 1665 AD: Christiann Huygens suggests using the melting and boiling points of water to make standard thermometers. - 1679 AD: Edme Mariotte discovered Boyle's Law independently. Also noted that temperature changes the volume of air. - 1679 AD: Denis Papin builds a bone digester, which uses high pressure steam to dissolve bones. Adding a release valve to keep it from exploding, Papin conceived of the idea of a piston and cylinder. - 1687 AD: Isaac Newton's Philosophiae Naturalis Principia Mathematica showed that particles at rest with repulsive forces inversely proportional to their distance (classic spring in physics) behave according to Boyle's Law. - 1689 AD: John Locke's "An Essay Concerning Human Understanding" argues that only direct experience can unlock true knowledge. In other words, don't trust what others have told you, see for yourself. This is a hallmark in empiricism. - 1694 AD: Carlo Renaldini proposes using the melting and boiling point of water as the universal scale for thermometers. - 1697 AD: Thomas Savery builds the first steam engine using Papin's designs. - 1700 AD: Guillaume Amontons and Francis Hauksbee describe that volume and temperature of air is proportional. - 1701 AD: Isaac Newton proposes using the melting point of ice and body temperature as the scale for thermometers, with 12 degrees between them. - 1712 AD: Newcomen Engine invented. - 1714 AD: Daniel Gabriel Fahrenheit invents the first reliable thermometer using mercury rather than alcohol and water. - 1724 AD: Fahrenheit proposes the Fahrenheit temperature scale. 0 degrees is the temperature of a mixture of ice, water and ammonium chloride or sea salt. 96 degrees was human body temperature. Rumor is that he chose 0 to be the coldest day in Danzig in the winter of 1708-09, and then saw it matched the temperature of the ice-brine mixture. - 1738 AD: Daniel Bernoulli publishes "Hydrodynamics", deriving an equation for calculating the pressure of a gas considering the collision of atoms with the walls of the container. Proves pressure, according to this model, is 2/3 the average KE of the gas in a unit volume. This thinking is lost due to the popularity of Caloric Theory. - 1742 AD: Anders Celsius proposes the reverse Celsius scale: 0 is boiling point of water at 1 atm, 100 is melting point of water. - 1743 AD: Jean-Pierre Christin, independent of Celsius, develops a scale where 0 is the melting point of water and 100 the boiling point. - 1744 AD: Carl Linnaeus reverses Celsius' scale. - 1750s - 1850s AD: Age of Revolutions. The Western world is in political turmoil as kings begin to be replaced by republics. - 1750s AD: Joseph Black and Caloric Theory - 1756-1763 AD: Seven Years' War fought on five continents involving every European great power. - 1761 AD: Joseph Black introduces the concept of latent heat. - 1763 AD: Watt Engine in development. - 1772 AD: Johan Wilcke calculates the latent heat of ice. - 1776 AD: A committe lead by Henry Cavendish fixed 32 F = 0 C and 212 F = 100 C. - 1776 AD: US War of Independence. Benjamin Thompson (later Count Rumford of the Holy Roman Empire) flees after a mob attacks his house for raising loyalists to fight the rebels. Thompson measures the force of gunpowder while advising General Gage and Lord George Germain. - 1780 AD: Antoine Lavoisier used the heat from a guinea pig's respiration to melt snow, showing that respiration was a form of combustion. The amount of snow melted could determine how much heat was made, and thus the first calorimeter was born. - 1780s AD: Jacques Charles discovers V = Tk for air. (Charles' Law) - 1781 AD: Benjamin Thompson publishes his findings on the force of gunpowder and is recognized as a scientist in London. - 1781 AD: Johan Wilcke creates the concept of and coins the term "specific heat", related to "specific gravity". - 1782-1783 AD: Antoine Lavoisier and Pierre-Simon Laplace use the world's first ice calorimeter to determine the heat from various chemical processes. Thermochemistry is born. - 1780s-1840s AD: The Industrial Revolution begins in England and Great Britain as steam engines are used to pump water out of mines. - 1789 AD: French Revolution begins. - 1798 AD: Benjamin Thompson (Count Rumford of the HRE) challenges Caloric Theory by observing boring cannons produced heat due to friction. Suggests heat is a form of motion as a results of his experiments. No attempt to reconcile the theory, however. - 1801 AD: John Dalton demonstrates in a series of four essays that all gases and vapors (well above their boiling point) that he studied expanded by the same amount between two fixed points of temperature. (Dalton's Law) Notes that the law doesn't work for things near their boiling point. - 1802 AD: Joseph Louis Gay-Lussac confirmed Dalton's presentation citing Jacques Charles' work. Confirms limitations near the boiling point. - 1803 - 1815 AD: Napoleonic Wars - 1808 AD: Joseph Louis Gay-Lussac notes that the pressure and temperature is proportional for a fixed amount of gas at a fixed volume. P = kT He also publicly releases the Law of Combining Volume, noting that 2 volumens of hydrogen gas + 1 volume of oxygen gas reacts to make 2 volumes of water. - 1808 AD: John Dalton's work convinces most chemists of atomic theory. Physicists, aside from a few (Boltzmann, Maxwell, Gibbs), reject it. - 1811 AD: Amedeo Avogadro hypothesizes that two gasses at the same T, P, V have the same number of particles. This is widely discredited, partially due to the relative obscurity of Avogadro, but also because experimental results contradict this conclusion. - 1814 AD: Andre-Marie Ampere publishes a similar law as to Avogadro's independently. Ampere is more famous than Avogadro, and so gets a lot of the credit for it until Avogadro is recognized 50 years later. - 1820 AD: John Herapath independently formulates a kinetic theory, but mistakenly associates momentum, not KE, with temperature. Paper fails peer review, and was neglected. - 1824 AD: Sadi Carnot publishes Reflection on the Motive Power of Fire, a discourse on heat, power, and engine efficiency. Thermodynamics is now a modern science, with people interested in it to build better, more efficent engines. - 1827 AD: Robert Brown, a botanist, describes Brownian Motion, discovered while looking through a microscope at pollen immersed in water. - 1834 AD: Emile Clapeyron combines Boyle's Law, Charles Law, Gay-Lussac's Laws and Avogadros' Laws into the Ideal Gas Law. - Steam Engine? Focus turned to how much heat you can get out of different types of coal. - Joseph Black investigated the latent heat of water via ice calorimeter. - Lavoisier did first experiments trying to quantify the amount of heat in chemical reactions using a calorimeter. - 1843 AD: John James Waterston provided a largely accurate account of kinetic theory independently, but fails peer review. - 1843+ AD: James Prescott Joule does more serious research on quantifying thermodynamics and the mechanical equivalent of heat. - 1845 AD: James Prescott Joule's famous experiment where a falling weight spins a paddle in a barrel of water. 4.41 J/cal. - 1848 AD: William Thomson (Lord Kelvin) describes Absolute Zero as the point at which Dalton's Law predicts zero volume. The Kelvin scale is proposed, with absolute zero set to 0 K = -273.15 C. - 1850 AD: William Thomson still trying to explain Joule's observations with caloric theory. - 1850 AD: Rudolf Clausius coins the term "entropy". - 1852 AD: William Thomson defines Absolute Zero in terms of the second law of thermodynamics. - 1854 AD: William Thomson coins the term "thermodynamics" in "On the Dynamical Theory of Heat" - 1857 AD: Rudolf Clausius publishes "On the nature of the motion called heat", stating clearly that heat is the average kinetic energy of molecules. Kinetic theory is now accepted. - 1859 AD: James Clerk Maxwell derives the Maxwell Momentum Distribution based on Clausius' kinetic theory. - 1859 AD: William John Macquorn Rankine proposes the Rankine scale, with 0 set at absolute zero and the degrees the same as for the Fahrenheit scale. 0 R = -459.67 F. - 1860 AD: Stanislao Cannizzaro announces that the discrepencies seen with Avogadro's Law were due to molecular dissociation at high temperatures. Avogadro's Law can be used to not only determine molecular masses, but atomic masses as well! Avogadro's Law is accepted. - 1860 AD: Maxwell derives Maxwell-Boltzmann distributions by theorizing about molecular collisions in the Kinetic theory of gases. - 1865 AD: Johann Josef Loschmidt estimates the size of a molecule. - 1866 AD: Thomas Clifford Allbutt invents a clinical thermometer that can give a body temperature reading in five minutes rather than 20. - 1870 AD: Ludwig Boltzmann describes that the Absolute Zero of the Second Law is the same as the Absolute Zero of Dalton's Law. - 1871 AD: James Clerk Maxwell and Rudolf Clausius collaborate to formulate statistical mechanics. - 1872 AD: Boltzmann derives the same formulas that Maxwell derived in 1860. - 1875 AD: Ludwig Boltzmann connects entropy and molecular motion. :math:`S = k \log W`. - 1876 AD: William Gibbs publises "On the Equilibrium of Heterogeneous Subtances", formulating the Gibbs free energy equation. Introduces the concept of Enthalpy H. (Heike Kamerlingh Onnes coined the term.) - 1877 AD: Liquid Air! - 1877 AD: Boltzmann - 1900 AD: Caloric Theory is largely obsolete. - 1905 AD: Albert Einstein weighs in on atomic theory with his theory of Brownian motion. - 1906 AD: Boltzmann commits suicide on vacation with his family. His mental state was deteriorating. His life's work, trying to convince the physics community of the reality of atomic theory, lays unfinished and rejected. - 1909 AD: Perrin's study of colloidal suspensions, combining Einstein's theoretical work, convinces the physics world that atomic theory is correct. Boltzmann is vindicated posthumously. Perrin receives the Nobel Prize in 1926 for his work on atomic theory. - 1910 AD: Millikan's Oil Drop experiment determines the charge of an electron. - 1910 AD: Jean Baptiste Perrin is able to quantify Avogadro's Constant using Millikan's results. - 1999 AD: Francesco Pompei introduced the first temporal artery thermometer, that can produce an accurate reading in 2 seconds.