The JouleThomson (Kelvin) coefficient

Fig.1 Joule-Thomson coefficients for various gases at atmospheric pressure. The rate of change of temperature with respect to pressure in a JouleThomson pr ocess (that is, at constant enthalpy ) is the JouleThomson (Kelvin) coefficient . This coefficient can be expressed in terms of the gas's volume , its heat capac ity at constant pressure , and its coefficient of thermal expansion as:[1][3][9 ] See the Derivation of the JouleThomson (Kelvin) coefficient below for the proof o f this relation. The value of is typically expressed in C/bar (SI units: K/Pa) a nd depends on the type of gas and on the temperature and pressure of the gas bef ore expansion. Its pressure dependence is usually only a few percent for pressur es up to 100 bar. All real gases have an inversion point at which the value of changes sign. The temperature of this point, the JouleThomson inversion temperature, depends on the pressure of the gas before expansion. In a gas expansion the pressure decreases, so the sign of is negative by defini tion. With that in mind, the following table explains when the JouleThomson effec t cools or warms a real gas: If the gas temperature is then is since is thus must be so the gas below the inversion temperature positive always negative negative cools above the inversion temperature negative always negative positive warms Helium and hydrogen are two gases whose JouleThomson inversion temperatures at a pressure of one atmosphere are very low (e.g., about 51 K (222 C) for helium). Thu s, helium and hydrogen warm up when expanded at constant enthalpy at typical roo m temperatures. On the other hand nitrogen and oxygen, the two most abundant gas es in air, have inversion temperatures of 621 K (348 C) and 764 K (491 C) respecti vely: these gases can be cooled from room temperature by the JouleThomson effect. [1] For an ideal gas, is always equal to zero: ideal gases neither warm nor cool up on being expanded at constant enthalpy. [edit]Applications In practice, the JouleThomson effect is achieved by allowing the gas to expand th rough a throttling device (usually a valve) which must be very well insulated to prevent any heat transfer to or from the gas. No external work is extracted fro m the gas during the expansion (the gas must not be expanded through a turbine, for example). The effect is applied in the Linde technique as a standard process in the petroc hemical industry, where the cooling effect is used to liquefy gases, and also in many cryogenic applications (e.g. for the production of liquid oxygen, nitrogen , and argon). Only when the JouleThomson coefficient for the given gas at the giv en temperature is greater than zero can the gas be liquefied at that temperature by the Linde cycle. In other words, a gas must be below its inversion temperatu re to be liquefied by the Linde cycle. For this reason, simple Linde cycle lique fiers cannot normally be used to liquefy helium, hydrogen, or neon. [edit]Proof that the specific enthalpy remains constant In thermodynamics so-called "specific" quantities are quantities per kilogram an d are denoted by lower-case characters. So h, u, and v are the enthalpy, interna l energy, and volume per kilogram, respectively. In a JouleThomson process the sp ecific enthalpy h remains constant.[10] To prove this, the first step is to comp ute the net work done when a mass m of the gas moves through the plug. This amou nt of gas has a volume of V1 = m v1 in the region at pressure P1 (region 1) and

a volume V2 = m v2 when in the region at pressure P2 (region 2). Then the work d one on the gas by the rest of the gas in region 1 is = m P1v1. In region 2 the a mount of work done by the gas is m P2v2. So, the total work done by the gas is The change in internal energy plus the work done by the gas is, by the first law of thermodynamics, the total amount of heat absorbed by the gas (here it is ass umed that there is no change in kinetic energy). In the JouleThomson process the gas is insulated, so no heat is absorbed. This means that where u1 and u2 denote the specific internal energies of the gas in regions 1 an d 2, respectively. Using the definition of the specific enthalpy h = u + Pv, the above equation implies that where h1 and h2 denote the specific enthalpies of the gas in regions 1 and 2, re spectively. Fig.2 Ts diagram of nitrogen. The red dome represents the two-phase region with the low-entropy side the saturated liquid and the high-entropy side the saturate d gas. The black curves give the Ts relation along isobars. The pressures are in dicated in bar. The blue curves are isenthalps (curves of constant specific enth alpy). The values are indicated in blue in kJ/kg. The specific points a, b, etc, are treated in the main text. [edit]Throttling in the Ts diagram A very convenient way to get a quantitative understanding of the throttling proc ess is by using diagrams. There are many types of diagrams (hT, hP, etc.). Commo nly used are the so-called Ts-diagrams. Fig.2 is the Ts-diagram of nitrogen as a n example.[11] In Fig.2 various points are indicated as follows: a T = 300 K, p = 200 bar, s = 5.16 kg/(kgK), h = 430 kJ/kg; b T = 270 K, p = 1 bar, s = 6.79 kg/(kgK), h = 430 kJ/kg; c T = 133 K, p = 200 bar, s = 3.75 kg/(kgK), h = 150 kJ/kg; d T = 77.2 K, p = 1 bar, s = 4.40 kg/(kgK), h = 150 kJ/kg; e T = 77.2 K, p = 1 bar, s = 2.83 kg/(kgK), h = 28 kJ/kg (saturated liquid at 1 bar); f T = 77.2 K, p = 1 bar, s = 5.41 kg/(kgK), h =230 kJ/kg (saturated gas at 1 bar ); As shown before, throttling keeps h constant. E.g. throttling from 200 bar and 3 00 K (point a in Fig.2) follows the isenthalp (line of constant specific enthalp y) of 430 kJ/kg. At 1 bar it results in point b which has a temperature of 270 K . So throttling from 200 to 1 bar gives a cooling from room temperature to below the freezing point of water. Throttling from 200 bar and an initial temperature of 133 K (point c in Fig.2) to 1 bar results in point d, which is in the two-ph ase region of nitrogen at a temperature of 72.2 K. Since the enthalpy is an exte nsive parameter the enthalpy in d (hd) is equal to the enthalpy in e (he) multip lied with the liquid fraction in d (xd) plus the enthalpy in f (hf) multiplied w ith the gas fraction in d (1-xd). So With numbers: 150 = xd 28 + (1 - xd) 230 so xd is about 0.40. This means that th e mass fraction of the liquid in the liquid-gas mixture leaving the throttling v alve is 40%.