Boiling Points and Boiling Point Numbers of Some Substituted Perfluoroalkanes.

1965 ◽  
Vol 10 (4) ◽  
pp. 379-382 ◽  
Author(s):  
H. H. Anderson
Keyword(s):  

Part I. — Pressures below 760 mm . In a previous communication (‘Proc.’, A, vol. 82, 1909, p. 396) the approximate boiling points of a number of metals were determined at atmospheric pressure. Apart from the question of finding the exact relation between the boiling point and pressure, it is an important criterion of any method for fixing the temperatures of ebullition to demonstrate that the experimental values obtained are dependent on the pressure. It is specially desirable when dealing with substances boiling at temperatures above 2000° to have some evidence that the points indicated are true boiling points. Previous work on the vaporisation of metals at different pressures has been confined to experiments in a very high vacuum except for metals like bismuth, cadmium, and zinc, which boil at relatively low temperatures under atmospheric pressure. The observations were limited to very low pressures on account of the difficulty of obtaining any material capable of withstanding a vacuum at temperatures over 1400° and the consequent necessity for keeping the boiling point below this limit by using very low pressures. Moreover in the case of the majority of the metals, e. g. , copper, tin, ebullition under reduced pressure has never been observed. The difficulties indicated above were avoided by using a similar type of apparatus to that previously described, and arranging the whole furnace inside a vacuum enclosure, thus permitting of the use of graphite crucibles to contain the metal.


1880 ◽  
Vol 30 (200-205) ◽  
pp. 323-329 ◽  

In a paper read before the Chemical Society, in May, 1879, I gave an account of a method of determining what is termed by Kopp the “specific volumes” of liquids; that was shown to be the volume of liquid at its boiling-point, at ordinary atmospheric pressure, obtainable from 22,326 volumes of its gas, supposed to exist at 0°. Being desirous of extending these researches, with the view of ascertaining such relations at higher temperatures, since April, 1879, I have made numerous experiments, the results of, and deductions from which I hope to publish before long. The temperatures observed vary from the boiling-points of the liquids examined, to about 50° above their critical points; and in course of these experiments I have noticed some curious facts, which may not be unworthy of the attention of the Society. It is well known that at temperatures above that which produces what is termed by Dr. Andrews the “critical point” of a liquid, the substance is supposed to exist in a peculiar condition, and Dr Andrews purposely abstained from speculating on the nature of the matter, whether it be liquid or gaseous, or in an intermediate condition, to which no name has been given. As my observations bear directly on this point, it may be advisable first to describe the experiments I have made, and then to draw the deductions which appear to follow from them.


It appeared that further experiments on the viscosity of air were desirable in order to discriminate between the results of F. A. Williams* and those of most previous observers, and to test his conclusion respecting the validity of Sutherland’s law of the variation of viscosity with temperature. It happened that this could be done easily and expeditiously in the laboratories of the Imperial College. Mr. R. S. Edwards, the author of the following paper, was in the midst of preparations for determining the viscosity of neon at a number of temperatures ranging from atmospheric temperature to the normal boiling point of sulphur, and at my suggestion diverted his attention to the behaviour of air at the same temperatures. It is true that this range (about 430 centi­grade degrees) is not so extensive as the thousand degrees covered by Williams’ experiments, but it includes all that region in which, according to Williams, the value of Sutherland’s constant displays the large increase upon which I have cast doubt. Edwards’ method of temperature control and estimation involves heating by the saturated vapour of selected substances of well-established boiling points, and would appear to be more reliable than the electrical heating, and particularly the temperature measurement by a single thermocouple, as employed by Williams. In the present experiments also, considerable variations of the pressure conditions have been made, with consistent results, thus proving the validity of the transpiration formula assumed. No such internal evidence of accuracy was provided in Williams’ experiments.


1860 ◽  
Vol 150 ◽  
pp. 257-276 ◽  

The researches which I beg, in the following pages, to submit to the Royal Society, embody the results obtained in the further development of an observation which I made a considerable number of years ago, and which, since that time, I had to defend against the objections of others, both by experimental inquiries of my own, and by the collection and discussion of facts elicited in the investigations of other observers. As far back as 1841* I pointed out that in analogous compounds the same difference of composition frequently involves the same difference in boiling-points. The assertion of the existence of this law-like relation between the chemical composition of substances and one of their most important physical properties, when first enunciated, met rather with the opposition than with the assent of chemists. In Germany especially it was contested by Schröder in his memoir “On the Molecular Volume of Chemical Compounds.” These objections led me to collect additional evidence in favour of my views, and to show more particularly that in very extensive series of compounds (alcohols C n H n+2 O 2 ; acids C n H n O 4 ; compound ethers C n H n O 4 , &c.) an elementary difference x C 2 H 2 is attended by a difference of x X 19°C. in the boiling-points, and how this fact is intimately connected with other regularities exhibited by the boiling-points of organic compounds. Almost at the same period Schröder § convinced himself that the relation I had pointed out obtains in most cases. He collected himself a considerable number of illustrations of the regularities I had traced, and showed that the relation in question is rendered more especially conspicuous if the compounds be expressed by formulæ representing equal vapour-volumes of the several substances. Some of the views, however, which were peculiar to Schröder have not gained the approbation of chemists. This physicist was inclined to consider the boiling-point of a substance as the most essential criterion of its proximate constituents, as the most trustworthy indicator of its molecular consti­tution. His views were chiefly based upon the assumption that the elementary difference C 2 H 2 , when occurring in alcohols C n H n+2 O 2 , involved a difference of boiling-points other than that occasioned by the same elementary difference obtaining in acids C n H n O 4 and that the isomeric compound ethers differed from one another in their boiling-points. An extensive series of boiling-point determinations* which I made of these isomeric ethers, proved that the latter assumption is not founded on facts. The exertions made by Schröder, Gerhardt, Löwig and others, in the hope of recognizing the influence of the constituent elements on the boiling-point of a compound, have also essentially remained without result.


On the average the critical point of a substance is 1·5 times its absolute boiling-point. Therefore the critical point of carbon should be about 5800° Ab. But the absolute critical temperature divided by the critical pressure is for all the elements so far examined never less than 2·5; this being about the value Sir James Dewar finds for hydrogen. So that, accepting this, we get the maximum critical pressure as follows, viz., 2320 atmospheres:— 5800° Ab./CrP = 2·5, or CrP = 5800° Ab./2·5, or 2320 atmospheres. Carbon and arsenic are the only two elements that have melting-point above the boiling-point; and among compounds carbonic acid and fluoride of silicium are the only other bodies with similar properties. Now the melting-point of arsenic is about 1·2 times its absolute boiling-point. With carbonic acid and fluoride of silicium the melting-points are about 1·1 times their boiling-points. Applying these ratios to carbon we find that its melting-point would be about 4400°.


2021 ◽  
Author(s):  
Simon Mukwembi ◽  
Farai Nyabadza

Abstract A general perception among researchers is that boiling points, which is a key property in the optimization of lubricant performance, are difficult to predict successfully using a single-parameter model [5, 6]. In this contribution, we propose a new graph parameter which we call, for lack of better terminology , the conduction of a graph. We exploit the conduction of a graph to develop a single-parameter model for predicting the boiling point of any given alkane. The accuracy of our model compares favourably to the accuracy of experimental data in literature. Our results have significant implications on the estimation of boiling points of chemical compounds in the absence of experimental data.


Author(s):  
Dennis Sherwood ◽  
Paul Dalby

An analysis of the colligative properties of the elevation of the boiling point and depression of the freezing point. A unique feature of this chapter is the analysis of the depression of the freezing point, which is subtly – but importantly – different from, and much more logical than, the analysis presented in many other texts.


Introduction . —In the course of some work, communicated to the Royal Societ by one of us, in which determinations of the boiling points of some saturated solutions were made by Buchanan’s method (the so-called Landsberger-Sakurai method), it was pointed out that these boiling points probably varied according to the height of liquid operated upon. During the course of that research a few experiments, which, however, are not recorded in the paper, were made on the boiling point of water; and it was found that this boiling point was approximately that due to a head of water equal to half the total height of liquid. The paper cited mentioned the hope that direct osmotic pressure measurements might be obtained; this hope has not been fulfilled, but as an exact connection between the vapour-pressure and the osmotic pressure of a solution has since been worked out, a knowledge of the boiling points will enable the osmotic pressure to be calculated.


1974 ◽  
Vol 52 (16) ◽  
pp. 1521-1531 ◽  
Author(s):  
J. Ancsin

Boiling points, freezing points, and vapor pressures (from 56 K to the normal boiling point) for pure and various doped N2 samples have been measured. The normal boiling points for N2 and N2 doped with 100 v.p.p.m. of O2, Ar, Kr, and CO impurities were found to be 77.3439 K, 77.3458 K, 77.3452 K, 77.3454 K, and 77.3444 K respectively. The triple points of the same samples are 63.14635 K, 63.1445 K, 63.14575 K, 63.1487 K, and 63.14675 K respectively. The values obtained for the heats of sublimation, vaporization, and fusion at the triple point of pure N2 were 6773.8, 6049.6, and 724.3 J/mole respectively and the above impurities changed these quantities by the amounts given in Tables 5 and 6.


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