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In a recent article (1) Michael Laing claims that if two liquids are made up of molecules that have exactly the same intermolecular cohesive attractions, molecules of both liquids should have the same escape velocities, regardless of mass. His argument is that the process of molecules breaking loose from attractive forces holding them in the liquid is not unlike that of a satellite breaking free of the earth’s gravitational field. While it is true that all satellites have the same escape velocity, independent of mass, it is not true for molecules evaporating from a liquid. For a satellite to escape the earth’s gravitational field, it must have a kinetic energy at least as large in magnitude as its gravitational potential energy at the earth’s surface. The minimum kinetic energy necessary for escape is  Here m is the mass of a satellite, ve its escape velocity, G the universal gravitational constant, M the mass of the earth, and RE the radius of the earth. It follows that the minimum velocity for escape, ve, is given by  and is independent of the mass of the satellite. The potential energy of a molecule leaving a liquid is a function of only its distance from its starting position at or near the surface of the liquid; it is not a function of mass. If we represent this potential energy by the expression U(r), where r is the distance the molecule is from its initial position in the liquid, the minimum kinetic energy a molecule must possess to escape the liquid will be  where U(0) is the initial potential energy of the escaping molecule. For such a molecule, the escape velocity, ve, is given by  This result means that the escape velocity of a molecule does depend on its mass, contrary to what Laing asserts. At the end of his paper, Laing concludes that molecular mass somehow plays a role in determining boiling points. He suggests that since plots of boiling points versus molecular mass for several groups of halogenated methanes are linear, there must be a causal relationship between the two quantities. However, plots of the number of electrons versus molecular weight for each of the groups of substituted methanes he is considering are also quite linear, so there is an equally good correlation between boiling points and the number of electrons in a molecule. Given the nature of intermolecular forces, it seems far more likely to me that it is the number of electrons in a molecule, rather than its mass, that figures in determining boiling points. Literature Cited - Laing, M. J. Chem. Educ. 2001, 78, 1544–1550.
See the author's reply.
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