Boyle

Mary Boyle,47 like Field, another petitioner for admission to the Chemical Society, was also a stalwart of the Chemistry Department at RHC. She was bom in 1874 and entered the Royal College of Science in 1898. Boyle took the full three-year course for chemistry before transferring to RHC in 1901, where she gained her B.Sc. after one year of study. She remained at RHC, firstly as a Demonstrator, then Assistant Lecturer in 1906, rising to Staff Lecturer. 

In 1910, only four years after being appointed as Lecturer, Boyle received her D.Sc., the subject of her research being the iodosulphonic acids of benzene. One of her obituaries noted  

This extensive research, the work of many years, was published in four large instalments from 1910 to 1919 [all under her name alone]. Five of the six theoretically possible diio-dosulphonic acids, three of the six theoretically possible triio-dosulphonic acids, and one tetraiodosulphonic acid, were first prepared by her, and incidentally she prepared a large number of new nitro- and amino-sulphonic acids. The orientation of these substances was worked out, their important derivatives were accurately characterised, and the electrolytic behaviour of the more important members was investigated. 

Our knowledge of this group of substances still rests mainly on Dr. Boyle s work. After 1920, the expansion of the teaching 

Boyle retired in 1933, moving to Leeds to be near her family, particularly her many nephews and nieces and their children, and she became active in community service. She died in November 1944. 

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Figure 1 shows second virial coefficients for four pure fluids as a function of temperature. Second virial coefficients for typical fluids are negative and increasingly so as the temperature falls only at the Boyle point, when the temperature is about 2.5 times the critical, does the second virial coefficient become positive. At a given temperature below the Boyle point, the magnitude of the second virial coefficient increases with... 

Boyle s law At constant temperature the volume of a given mass of gas is inversely proportional to the pressure. Although exact at low pressures, the law is not accurately obeyed at high pressures because of the finite size of molecules and the existence of intermolecular forces. See van der Waals equation. 

The properties of hydrocarbon gases are relatively simple since the parameters of pressure, volume and temperature (PVT) can be related by a single equation. The basis for this equation is an adaptation of a combination of the classical laws of Boyle, Charles and Avogadro. 

Knowledge of internal molecular motions became a serious quest with Boyle and Newton, at the very dawn of modem natural science. Flowever, real progress only became possible with the advent of quantum theory in the 20th century. The study of internal molecular motion for most of the century was concerned primarily with molecules near their equilibrium configuration on the PES. This gave an enonnous amount of inunensely valuable infonuation, especially on the stmctural properties of molecules. 

For convenience, one of the systems will be taken as an ideal gas whose equation of state follows Boyle s law,... 

One assumes the existence of a fluid that obeys Boyle s law (equation (A2.1.4) ) and that, on adiabatic expansion into a vacuum, shows no change in temperature, i.e. for which/yF=/(0) and = 0. (All... 

Figure A2.1.7 shows schematically the variation o B = B with temperature. It starts strongly negative (tiieoretically at minus infinity for zero temperature, but of course iimneasiirable) and decreases in magnitude until it changes sign at the Boyle temperature (B = 0, where the gas is more nearly ideal to higher pressures). The slope dB/dT remains...

It is widely believed that gases are virtually ideal at a pressure of one atmosphere. This is more nearly tnie at relatively high temperatures, but at the nonnal boiling point (roughly 20% of the Boyle temperature), typical gases have values of pV/nRT that are 5 to 15% lower than tlie ideal value of unity. 

The temperature at which 2(7) is zero is the Boyle temperature Jg. The excess Hehuholtz free energy follows from the tlrenuodynamic relation... 

The first seven virial coefficients of hard spheres are positive and no Boyle temperature exists for hard spheres. 

Theta conditions in dilute polymer solutions are similar to tire state of van der Waals gases near tire Boyle temperature. At this temperature, excluded-volume effects and van der Waals attraction compensate each other, so tliat tire second virial coefficient of tire expansion of tire pressure as a function of tire concentration vanishes. On dealing witli solutions, tire quantity of interest becomes tire osmotic pressure IT ratlier tlian tire pressure. Its virial expansion may be written as... 

Boyle s law states that the volume of a given quantity of a gas varies inversely as the pressure, the temperature remaining constant. That is. 

Combining the laws of Boyle and Charles into one expression gives... 

The behavior of all gases that obey the laws of Boyle and Charles, and Avogadro s hypothesis, can be expressed by the ideal gas equation ... 

In Chap. 1 we referred to these as 0 conditions, and we shall examine the significance of this term presently. Note that 0 conditions for a polymer solution are analogous to the Boyle temperature of a gas Each behaves ideally under its respective conditions. 

It is interesting to note that for a van der Waals gas, the second virial coefficient equals b - a/RT, and this equals zero at the Boyle temperature. This shows that the excluded volume (the van der Waals b term) and the intermolecular attractions (the a term) cancel out at the Boyle temperature. This kind of compensation is also typical of 0 conditions. 

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