The inversion temperature in thermodynamics and cryogenics is the critical temperature below which a non-ideal gas (all gases in reality) that is expanding at constant enthalpy will experience a temperature decrease, and above which will experience a temperature increase. This temperature change is known as the Joule–Thomson effect, and is exploited in the liquefaction of gases. Inversion temperature depends on the nature of the gas.
For a van der Waals gas we can calculate the enthalpy using statistical mechanics as
where is the number of molecules, is volume, is temperature (in the Kelvin scale), is the Boltzmann constant, and and are constants depending on intermolecular forces and molecular volume, respectively.
From this equation, if enthalpy is kept constant and there is an increase of volume, temperature must change depending on the sign of . Therefore, our inversion temperature is given where the sign flips at zero, or
where is the critical temperature of the substance. So for , an expansion at constant enthalpy increases temperature as the work done by the repulsive interactions of the gas is dominant, and so the change in kinetic energy is positive. But for , expansion causes temperature to decrease because the work of attractive intermolecular forces dominates, giving a negative change in average molecular speed, and therefore kinetic energy. [1]
Enthalpy is the sum of a thermodynamic system's internal energy and the product of its pressure and volume. It is a state function in thermodynamics used in many measurements in chemical, biological, and physical systems at a constant external pressure, which is conveniently provided by the large ambient atmosphere. The pressure–volume term expresses the work that was done against constant external pressure to establish the system's physical dimensions from to some final volume , i.e. to make room for it by displacing its surroundings. The pressure-volume term is very small for solids and liquids at common conditions, and fairly small for gases. Therefore, enthalpy is a stand-in for energy in chemical systems; bond, lattice, solvation, and other chemical "energies" are actually enthalpy differences. As a state function, enthalpy depends only on the final configuration of internal energy, pressure, and volume, not on the path taken to achieve it.
In thermodynamics, the specific heat capacity of a substance is the amount of heat that must be added to one unit of mass of the substance in order to cause an increase of one unit in temperature. It is also referred to as massic heat capacity or as the specific heat. More formally it is the heat capacity of a sample of the substance divided by the mass of the sample. The SI unit of specific heat capacity is joule per kelvin per kilogram, J⋅kg−1⋅K−1. For example, the heat required to raise the temperature of 1 kg of water by 1 K is 4184 joules, so the specific heat capacity of water is 4184 J⋅kg−1⋅K−1.
In thermodynamics, the enthalpy of vaporization, also known as the (latent) heat of vaporization or heat of evaporation, is the amount of energy (enthalpy) that must be added to a liquid substance to transform a quantity of that substance into a gas. The enthalpy of vaporization is a function of the pressure and temperature at which the transformation takes place.
Thermodynamic temperature is a quantity defined in thermodynamics as distinct from kinetic theory or statistical mechanics.
The Boltzmann constant is the proportionality factor that relates the average relative thermal energy of particles in a gas with the thermodynamic temperature of the gas. It occurs in the definitions of the kelvin (K) and the gas constant, in Planck's law of black-body radiation and Boltzmann's entropy formula, and is used in calculating thermal noise in resistors. The Boltzmann constant has dimensions of energy divided by temperature, the same as entropy and heat capacity. It is named after the Austrian scientist Ludwig Boltzmann.
The ideal gas law, also called the general gas equation, is the equation of state of a hypothetical ideal gas. It is a good approximation of the behavior of many gases under many conditions, although it has several limitations. It was first stated by Benoît Paul Émile Clapeyron in 1834 as a combination of the empirical Boyle's law, Charles's law, Avogadro's law, and Gay-Lussac's law. The ideal gas law is often written in an empirical form:
The kinetic theory of gases is a simple classical model of the thermodynamic behavior of gases. It treats a gas as composed of numerous particles, too small to see with a microscope, which are constantly in random motion. Their collisions with each other and with the walls of their container are used to explain physical properties of the gas—for example, the relationship between its temperature, pressure, and volume. The particles are now known to be the atoms or molecules of the gas.
An ideal gas is a theoretical gas composed of many randomly moving point particles that are not subject to interparticle interactions. The ideal gas concept is useful because it obeys the ideal gas law, a simplified equation of state, and is amenable to analysis under statistical mechanics. The requirement of zero interaction can often be relaxed if, for example, the interaction is perfectly elastic or regarded as point-like collisions.
In thermodynamics, the Joule–Thomson effect describes the temperature change of a real gas or liquid when it is expanding; typically caused by the pressure loss from flow through a valve or porous plug while keeping it insulated so that no heat is exchanged with the environment. This procedure is called a throttling process or Joule–Thomson process. The effect is purely an effect due to deviation from ideality, as any ideal gas has no JT effect.
Heat capacity or thermal capacity is a physical property of matter, defined as the amount of heat to be supplied to an object to produce a unit change in its temperature. The SI unit of heat capacity is joule per kelvin (J/K).
In thermodynamics, the Gibbs free energy is a thermodynamic potential that can be used to calculate the maximum amount of work, other than pressure-volume work, that may be performed by a thermodynamically closed system at constant temperature and pressure. It also provides a necessary condition for processes such as chemical reactions that may occur under these conditions. The Gibbs free energy is expressed asWhere:
The internal energy of a thermodynamic system is the energy of the system as a state function, measured as the quantity of energy necessary to bring the system from its standard internal state to its present internal state of interest, accounting for the gains and losses of energy due to changes in its internal state, including such quantities as magnetization. It excludes the kinetic energy of motion of the system as a whole and the potential energy of position of the system as a whole, with respect to its surroundings and external force fields. It includes the thermal energy, i.e., the constituent particles' kinetic energies of motion relative to the motion of the system as a whole. The internal energy of an isolated system cannot change, as expressed in the law of conservation of energy, a foundation of the first law of thermodynamics. The notion has been introduced to describe the systems characterized by temperature variations, temperature being added to the set of state parameters, the position variables known in mechanics, in a similar way to potential energy of the conservative fields of force, gravitational and electrostatic. Internal energy changes equal the algebraic sum of the heat transferred and the work done. In systems without temperature changes, potential energy changes equal the work done by/on the system.
An isothermal process is a type of thermodynamic process in which the temperature T of a system remains constant: ΔT = 0. This typically occurs when a system is in contact with an outside thermal reservoir, and a change in the system occurs slowly enough to allow the system to be continuously adjusted to the temperature of the reservoir through heat exchange (see quasi-equilibrium). In contrast, an adiabatic process is where a system exchanges no heat with its surroundings (Q = 0).
The Clausius–Clapeyron relation, in chemical thermodynamics, specifies the temperature dependence of pressure, most importantly vapor pressure, at a discontinuous phase transition between two phases of matter of a single constituent. It is named after Rudolf Clausius and Benoît Paul Émile Clapeyron. However, this relation was in fact originally derived by Sadi Carnot in his Reflections on the Motive Power of Fire, which was published in 1824 but largely ignored until it was rediscovered by Clausius, Clapeyron, and Lord Kelvin decades later. Kelvin said of Carnot's argument that "nothing in the whole range of Natural Philosophy is more remarkable than the establishment of general laws by such a process of reasoning."
The Joule expansion is an irreversible process in thermodynamics in which a volume of gas is kept in one side of a thermally isolated container, with the other side of the container being evacuated. The partition between the two parts of the container is then opened, and the gas fills the whole container.
The Van 't Hoff equation relates the change in the equilibrium constant, Keq, of a chemical reaction to the change in temperature, T, given the standard enthalpy change, ΔrH⊖, for the process. The subscript means "reaction" and the superscript means "standard". It was proposed by Dutch chemist Jacobus Henricus van 't Hoff in 1884 in his book Études de Dynamique chimique.
In thermodynamics, heat is energy in transfer between a thermodynamic system and its surroundings by modes other than thermodynamic work and transfer of matter. Such modes are microscopic, mainly thermal conduction, radiation, and friction, as distinct from the macroscopic modes, thermodynamic work and transfer of matter. For a closed system, the heat involved in a process is the difference in internal energy between the final and initial states of a system, and subtracting the work done in the process. For a closed system, this is the formulation of the first law of thermodynamics.
In thermodynamics, the volume of a system is an important extensive parameter for describing its thermodynamic state. The specific volume, an intensive property, is the system's volume per unit mass. Volume is a function of state and is interdependent with other thermodynamic properties such as pressure and temperature. For example, volume is related to the pressure and temperature of an ideal gas by the ideal gas law. The physical region covered by a system may or may not coincide with a control volume used to analyze the system.
In thermodynamics, the enthalpy of fusion of a substance, also known as (latent) heat of fusion, is the change in its enthalpy resulting from providing energy, typically heat, to a specific quantity of the substance to change its state from a solid to a liquid, at constant pressure.
Entropy production is the amount of entropy which is produced during heat process to evaluate the efficiency of the process.