Saturday, April 24, 2010

Historical synthesis

Boyle's Law


Boyle's equipment.
Boyle's Law was perhaps the first expression of an equation of state. In 1662 Robert Boyle, an Irishman, performed a series of experiments employing a J-shaped glass tube, which was sealed on one end. Mercury was added to the tube, trapping a fixed quantity of air in the short, sealed end of the tube. Then the volume of gas was carefully measured as additional mercury was added to the tube. The pressure of the gas could be determined by the difference between the mercury level in the short end of the tube and that in the long, open end. Through these experiments, Boyle noted that the gas volume varied inversely with the pressure.[18] The image of Boyle's Equipment shows some of the exotic tools used by Boyle during his study of gases.
  • Boyle's Law - describes a gas in which the number of particles and Temperature are constant.
  • PV = constant in this situation constant = nRT from the ideal gas law.

Law of volumes

In 1787, the French physicist and balloon pioneer, Jacques Charles, found that oxygen, nitrogen, hydrogen, carbon dioxide, and air expand to the same extent over the same 80 kelvin interval.

In 1802, Joseph Louis Gay-Lussac published results of similar, though more extensive experiments, indicating a linear relationship between volume and temperature. Gay-Lussac credited Charle's earlier work by naming the law in his honor. In the absence of this linkage, Dalton could have been in contention for this honor for his previously published work on partial pressures.

  • Law of Volumes - Both Charles and Gay-Lussac played a role in developing this relationship.[19]
  • V/T = constant - notice that constant = nR/P from the ideal gas law.

Avogadro's Law


Dalton's notation.

In 1811, Amedeo Avogadro verified that equal volumes of pure gases contain the same number of particles. His theory was not generally accepted until 1858 when another Italian chemist Stanislao Cannizzaro was able to explain non-ideal exceptions. For his work with gases a century prior, the number that bears his name Avogadro's constant represents the number of atoms found in 12 grams of elemental carbon-12 (6.022×1023 mol−1). This specific number of gas particles, at standard temperature and pressure (ideal gas law) occupies 22.40 liters and is referred to as the molar volume.

  • Avogadro's Law - describes a gas in a container in which the pressure and temperature are constant. The simplified form for the ideal gas law follows:
  • V/n = constant – notice that constant = RT/P from the ideal gas law.

Dalton's Law

In 1801, John Dalton published the Law of Partial Pressures from his work with ideal gas law relationship: The pressure of a mixture of gases is equal to the sum of the pressures of all of the constituent gases alone. Mathematically, this can be represented for n species as:

Pressuretotal = Pressure1 + Pressure2 + ... + Pressuren

The image of Dalton's journal depicts symbology he used as shorthand to record the path he followed. Among his key journal observations upon mixing unreactive "elastic fluids" (gases) were the following.[20]:

  • Unlike liquids, heavier gases did not drift to the bottom upon mixing.
  • Gas particle identity played no role in determining final pressure (they behaved as if their size was negligible).

Special topics

Compressibility


Compressibility factors for air.

Thermodynamicists use this factor (Z) to alter the ideal gas equation to account for compressibility effects of real gases. This factor represents the ratio of actual to ideal specific volumes. It is sometimes referred to as a "fudge-factor" or correction to expand the useful range of the ideal gas law for design purposes. Usually this Z value is very close to unity. The compressibility factor image illustrates how Z varies over a range of very cold temperatures.

Reynolds Number

In fluid mechanics, the Reynolds number is the ratio of inertial forces (vsρ) to viscous forces (μ/L). It is one of the most important dimensionless numbers in fluid dynamics and is used, usually along with other dimensionless numbers, to provide a criterion for determining dynamic similitude. As such the Reynold's number provides the link between modeling results (design) and the full scale actual conditions. It can also be used to characterize the flow.

Viscosity


Satellite view of weather pattern in vicinity of Robinson Crusoe Islands on 15 September 1999, shows a unique turbulent cloud pattern called a "von Kármán vortex street."

Viscosity, a physical property, is a measure of how well adjacent molecules stick to one another. A solid can withstand a shearing force due to the strength of these sticky intermolecular forces. A fluid will continuously deform when subjected to a similar load. While a gas has a lower value of viscosity than a liquid, it is still an observable property. If gases had no viscosity, then they would not stick to the surface of a wing and form a boundary layer. A study of the delta wing in the Schlieren image reveals that the gas particles stick to one another (see Boundary layer section).

Turbulence


Delta wing in wind tunnel. The shadows form as the indices of refraction change within the gas as it compresses on the leading edge of this wing.

In fluid dynamics, turbulence or turbulent flow is a flow regime characterized by chaotic, stochastic property changes. This includes low momentum diffusion, high momentum convection, and rapid variation of pressure and velocity in space and time. The Satellite view of weather around Robinson Crusoe Islands illustrates just one example.

Boundary layer

Particles will, in effect, "stick" to the surface of an object moving through it. This layer of particles is called the boundary layer. At the surface of the object, it is essentially static due to the friction of the surface. The object, with its boundary layer is effectively the new shape of the object that the rest of the molecules "see" as the object approaches. This boundary layer can separate from the surface, essentially creating a new surface and completely changing the flow path. The classical example of this is a stalling airfoil. The delta wing image clearly shows the boundary layer thickening as the gas flows from right to left along the leading edge.

Maximum entropy principle

As the total number of degrees of freedom approaches infinity, the system will be found in the macrostate that corresponds to the highest multiplicity. In order to illustrate this principle, observe the skin temperature of a frozen metal bar. Using a thermal image of the skin temperature, note the temperature distribution on the surface. This initial observation of temperature represents a "microstate." At some future time, a second observation of the skin temperature produces a second microstate. By continuing this observation process, it is possible to produce a series of microstates that illustrate the thermal history of the bar's surface. Characterization of this historical series of microstates is possible by choosing the macrostate that successfully classifies them all into a single grouping.

Thermodynamic equilibrium

When energy transfer ceases from a system, this condition is referred to as thermodynamic equilibrium. Usually this condition implies the system and surroundings are at the same temperature so that heat no longer transfers between them. It also implies that external forces are balanced (volume does not change), and all chemical reactions within the system are complete. The timeline varies for these events depending on the system in question. A container of ice allowed to melt at room temperature takes hours, while in semiconductors the heat transfer that occurs in the device transition from an on to off state could be on the order of a few nanoseconds.

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