Real Gases.doc

Real Gases §1. Molecular interactions Real gases show deviations from the perfect gas law because their molecules interact with one another. Repulsive forces are short-range interactions, significant only when molecules are almost in contact. Attractive intermolecular forces have a relative long range; they are important when the molecules are fairly close together and assist compression of the gas. The variation of the potential energy of two molecules on their separation. 【Atkins’ Physical Chemistry (9e), p.30, Fig1.13.】 At moderate pressures, when the average separation of the molecules is only a few molecular diameters, the attractive forces dominate the repulsive forces. In this case, the real gas can be expected to be more compressible than a perfect gas. §2. The compression factor The compression factor, Z, of a gas is the ratio of its measured molar volume, Vm = V/n, to the molar volume of a perfect gas, Vmo, at the same pressure and temperature: The variation of the compression factor, Z, with pressure for several gases at 0 oC. 【Atkins’ Physical Chemistry (9e), p.31, Fig1.14.】 *如果溫度、體積固定，從左往右壓力越來越大，表示容器內氣體數量越來越多，分子間的距離越來越小，相當於前一個圖形從右往左。 ，b、Rcompression factor。如果在某一個溫度與壓力，氣體的莫耳體積 Vm = 10b，compression factor。 §3. Virial equation of state and Notice that the terms in parentheses in the above equation is just the compression factor, Z. The coefficients B, C, …, which depend on the temperature, are the second, third, … virial coefficients. The values of the virial coefficients of a gas are determined from measurements of its compression factor. Second virial coefficients, B (cm3/mol) 　 100 K 273 K 373 K 600 K Air -167.3 -13.5 3.4 19.0 Ar -187.0 -21.7 -4.2 11.9 CH4 -53.6 -21.2 8.1 CO2 -142.0 -72.2 -12.4 H2 -2.0 13.7 15.6 He 11.4 12.0 11.3 10.4 Kr -62.9 -28.7 1.7 N2 -160.0 -10.5 6.2 21.7 Ne -6.0 10.4 12.3 13.8 O2 -197.5 -22.0 -3.7 12.9 Xe 　 -153.7 -81.7 -19.6 【Data: AIP, JL For Ar at 273 K, C = 1200