Gas

The symbol used to represent temperature in equations is T with SI units of kelvins.

The speed of a gas particle is proportional to its absolute temperature. The volume of the balloon in the video shrinks when the trapped gas particles slow down with the addition of extremely cold nitrogen. The temperature of any physical system is related to the motions of the particles (molecules and atoms) which make up the [gas] system. In statistical mechanics, temperature is the measure of the average kinetic energy stored in a particle. The methods of storing this energy are dictated by the degrees of freedom of the particle itself ( energy modes). Kinetic energy added ( endothermic process) to gas particles by way of collisions produces linear, rotational, and vibrational motion. In contrast, a molecule in a solid can only increase its vibrational modes with the addition of heat as the lattice crystal structure prevents both linear and rotational motions. These heated gas molecules have a greater speed range which constantly varies due to constant collisions with other particles. The speed range can be described by the Maxwell-Boltzmann distribution. Use of this distribution implies ideal gases near thermodynamic equilibrium for the system of particles being considered.

Specific volume

The symbol used to represent specific volume in equations is "v" with SI units of cubic meters per kilogram.

The symbol used to represent volume in equations is "V" with SI units of cubic meters.

When performing a thermodynamic analysis, it is typical to speak of intensive and extensive properties. Properties which depend on the amount of gas (either by mass or volume) are called extensive properties, while properties that do not depend on the amount of gas are called intensive properties. Specific volume is an example of an intensive property because it is the ratio of volume occupied by a unit of mass of a gas that is identical throughout a system at equilibrium. 1000 atoms a gas occupy the same space as any other 1000 atoms for any given temperature and pressure. This concept is easier to visualize for solids such as iron which are incompressible compared to gases. Since a gas fills any container in which it is placed, volume is an extensive property.

Density

The symbol used to represent density in equations is ρ (rho) with SI units of kilograms per cubic meter. This term is the reciprocal of specific volume.

Since gas molecules can move freely within a container, their mass is normally characterized by density. Density is the amount of mass per unit volume of a substance, or the inverse of specific volume. For gases, the density can vary over a wide range because the particles are free to move closer together when constrained by pressure or volume. This variation of density is referred to as compressibility. Like pressure and temperature, density is a state variable of a gas and the change in density during any process is governed by the laws of thermodynamics. For a static gas, the density is the same throughout the entire container. Density is therefore a scalar quantity. It can be shown by kinetic theory that the density is inversely proportional to the size of the container in which a fixed mass of gas is confined. In this case of a fixed mass, the density decreases as the volume increases.

Microscopic

If one could observe a gas under a powerful microscope, one would see a collection of particles (molecules, atoms, ions, electrons, etc.) without any definite shape or volume that are in more or less random motion. These neutral gas particles only change direction when they collide with another particle or with the sides of the container. In an ideal gas, these collisions are perfectly elastic. This particle or microscopic view of a gas is described by the Kinetic-molecular theory. The assumptions behind this theory can be found in the postulates section of Kinetic Theory.

Kinetic theory

Kinetic theory provides insight into the macroscopic properties of gases by considering their molecular composition and motion. Starting with the definitions of momentum and kinetic energy, one can use the conservation of momentum and geometric relationships of a cube to relate macroscopic system properties of temperature and pressure to the microscopic property of kinetic energy per molecule. The theory provides averaged values for these two properties.

The theory also explains how the gas system responds to change. For example, as a gas is heated from absolute zero, when it is (in theory) perfectly still, its internal energy (temperature) is increased. As a gas is heated, the particles speed up and its temperature rises. This results in greater numbers of collisions with the container per unit time due to the higher particle speeds associated with elevated temperatures. The pressure increases in proportion to the number of collisions per unit time.

Brownian motion

Brownian motion is the mathematical model used to describe the random movement of particles suspended in a fluid. The gas particle animation, using pink and green particles, illustrates how this behaviour results in the spreading out of gases (entropy). These events are also described by particle theory.

Since it is at the limit of (or beyond) current technology to observe individual gas particles (atoms or molecules), only theoretical calculations give suggestions about how they move, but their motion is different from Brownian motion because Brownian motion involves a smooth drag due to the frictional force of many gas molecules, punctuated by violent collisions of an individual (or several) gas molecule(s) with the particle. The particle (generally consisting of millions or billions of atoms) thus moves in a jagged course, yet not so jagged as would be expected if an individual gas molecule were examined.

Intermolecular forces

As discussed earlier, momentary attractions (or repulsions) between particles have an effect on gas dynamics. In physical chemistry, the name given to these intermolecular forces is van der Waals force. These forces play a key role in determining physical properties of a gas such as viscosity and flow rate (see physical characteristics section). Ignoring these forces in certain conditions (see Kinetic-molecular theory) allows a real gas to be treated like an ideal gas. This assumption allows the use of ideal gas laws which greatly simplifies calculations.

Proper use of these gas relationships requires the Kinetic-molecular theory (KMT). When gas particles possess a magnetic charge or Intermolecular force they gradually influence one another as the spacing between them is reduced (the hydrogen bond model illustrates one example). In the absence of any charge, at some point when the spacing between gas particles is greatly reduced they can no longer avoid collisions between themselves at normal gas temperatures. Another case for increased collisions among gas particles would include a fixed volume of gas, which upon heating would contain very fast particles. This means that these ideal equations provide reasonable results except for extremely high pressure (compressible) or high temperature (ionized) conditions. Notice that all of these excepted conditions allow energy transfer to take place within the gas system. The absence of these internal transfers is what is referred to as ideal conditions in which the energy exchange occurs only at the boundaries of the system. Real gases experience some of these collisions and intermolecular forces. When these collisions are statistically negligible (incompressible), results from these ideal equations are still meaningful. If the gas particles are compressed into close proximity they behave more like a liquid (see fluid dynamics).

Simplified models

An equation of state (for gases) is a mathematical model used to roughly describe or predict the state properties of a gas. At present, there is no single equation of state that accurately predicts the properties of all gases under all conditions. Therefore, a number of much more accurate equations of state have been developed for gases in specific temperature and pressure ranges. The "gas models" that are most widely discussed are "perfect gas", "ideal gas" and "real gas". Each of these models has its own set of assumptions to facilitate the analysis of a given thermodynamic system. Each successive model expands the temperature range of coverage to which it applies.

Ideal and perfect gas models

The equation of state for an ideal or perfect gas is the ideal gas law and reads

where P is the pressure, V is the volume, n is amount of gas (in mol units), R is the universal gas constant, 8.314 J/(mol K), and T is the temperature. Written this way, it is sometimes called the "chemist's version", since it emphasizes the number of molecules n. It can also be written as

where is the specific gas constant for a particular gas, in units J/(kg K), and ρ = m/V is density. This notation is the "gas dynamicist's" version, which is more practical in modeling of gas flows involving acceleration without chemical reactions.

The ideal gas law does not make an assumption about the specific heat of a gas. In the most general case, the specific heat is a function of both temperature and pressure. If the pressure-dependence is neglected (and possibly the temperature-dependence as well) in a particular application, sometimes the gas is said to be a perfect gas, although the exact assumptions may vary depending on the author and/or field of science.

For an ideal gas, the ideal gas law applies without restrictions on the specific heat. An ideal gas is a simplified "real gas" with the assumption that the compressibility factor Z is set to 1 meaning that this pneumatic ratio remains constant. A compressibility factor of one also requires the four state variables to follow the ideal gas law.

This approximation is more suitable for applications in engineering although simpler models can be used to produce a "ball-park" range as to where the real solution should lie. An example where the "ideal gas approximation" would be suitable would be inside a combustion chamber of a jet engine. It may also be useful to keep the elementary reactions and chemical dissociations for calculating emissions.

Real gas

Each one of the assumptions listed below adds to the complexity of the problem's solution. As the density of a gas increases with pressure rises, the intermolecular forces play a more substantial role in gas behaviour which results in the ideal gas law no longer providing "reasonable" results. At the upper end of the engine temperature ranges (e.g. combustor sections – 1300 K), the complex fuel particles absorb internal energy by means of rotations and vibrations that cause their specific heats to vary from those of diatomic molecules and noble gases. At more than double that temperature, electronic excitation and dissociation of the gas particles begins to occur causing the pressure to adjust to a greater number of particles (transition from gas to plasma). Finally, all of the thermodynamic processes were presumed to describe uniform gases whose velocities varied according to a fixed distribution. Using a non-equilibrium situation implies the flow field must be characterized in some manner to enable a solution. One of the first attempts to expand the boundaries of the ideal gas law was to include coverage for different thermodynamic processes by adjusting the equation to read pVⁿ = constant and then varying the n through different values such as the specific heat ratio, γ.

Real gas effects include those adjustments made to account for a greater range of gas behaviour:

• Compressibility effects (Z allowed to vary from 1.0)
• Variable heat capacity (specific heats vary with temperature)
• Van der Waals forces (related to compressibility, can substitute other equations of state)
• Non-equilibrium thermodynamic effects
• Issues with molecular dissociation and elementary reactions with variable composition.

For most applications, such a detailed analysis is excessive. Examples where "Real Gas effects" would have a significant impact would be on the Space Shuttle re-entry where extremely high temperatures and pressures are present or the gases produced during geological events as in the image of the 1990 eruption of Mount Redoubt.

Historical synthesis

Boyle's law

Boyle's Law was perhaps the first expression of an equation of state. In 1662 Robert Boyle 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. The image of Boyle's Equipment shows some of the exotic tools used by Boyle during his study of gases.

Through these experiments, Boyle noted that the pressure exerted by a gas held at a constant temperature varies inversely with the volume of the gas. For example, if the volume is halved, the pressure is doubled; and if the volume is doubled, the pressure is halved. Given the inverse relationship between pressure and volume, the product of pressure (P) and volume (V) is a constant (k) for a given mass of confined gas as long as the temperature is constant. Stated as a formula, thus is:

Because the before and after volumes and pressures of the fixed amount of gas, where the before and after temperatures are the same both equal the constant k, they can be related by the equation:

Charles's Law

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. He noted that, for an ideal gas at constant pressure, the volume is directly proportional to its temperature:

Gay-Lussac's Law

In 1802, Joseph Louis Gay-Lussac published results of similar, though more extensive experiments. Gay-Lussac credited Charle's earlier work by naming the law in his honour. Gay-Lussac himself is credited with the law describing pressure, which he found in 1809. It states that the pressure exerted on a container's sides by an ideal gas is proportional to its temperature.

Avogadro's law

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, which is referred to as the molar volume.

Avogadro's law states that the volume occupied by an ideal gas is proportional to the number of moles (or molecules) present in the container. This gives rise to the molar volume of a gas, which at STP is 22.4 dm³ (or litres). The relation is given by

where n is equal to the number of moles of gas (the number of molecules divided by Avogadro's Number).

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:

Pressure_total = Pressure₁ + Pressure₂ + ... + Pressure_n

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:

• 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

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 (v_sρ) 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 Reynolds number provides the link between modeling results (design) and the full-scale actual conditions. It can also be used to characterize the flow.

Viscosity

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

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.