I. Considerations on the abrupt change at boiling or conden­ sing in reference to the continuity of the fluid state of matter

Abstract

When we find a substance capable of existing in two fluid states different in density and other properties while the temperature and pressure are the same in both, and when we find also that an introduction or abstraction of heat without change of temperature or of pressure will effect the change from the one state to the other, and also find that the change either way is perfectly reversible , we speak of the one state as being an ordinary gaseous, and the other as being an ordinary, liquid state of the same matter; and the ordinary transition from the one to the other we would designate by the terms boiling or condensing, or occasionally by other terms nearly equivalent, such as evaporation, gasification, liquefaction from the gaseous state, &c. Cases of gasification from liquids or of condensation from gases, when any chemical alteration accompanies the abrupt change of density, are not among the subjects proposed to be brought under consi­deration in the present paper. In such cases I presume there would be no perfect reversibility in the process; and if so, this would of itself be a criterion sufficing to separate them from the proper cases of boiling or condensing at present intended to be considered. If, now, the fluid sub­stance in the rarer of the two states (that is, in what is commonly called the gaseous state) be still further rarefied, by increase of temperature or diminution of pressure, or be changed considerably in other ways by alterations of temperature and pressure jointly, without its receiving any abrupt collapse in volume, it will still, in ordinary language and ordinary mode of thought, be regarded as being in a gaseous state. Remarks of quite a corresponding kind may be made in describing various conditions of the fluid (as to temperature, pressure, and volume), which would in ordinary language be regarded as belonging to the liquid state. Dr. Andrews (Phil. Trans. 1869, p. 575) has shown that the ordinary gaseous and ordinary liquid states are only widely separated forms of the same condition of matter, and may be made to pass into one another by a course of continuous physical changes presenting nowhere any interruption or breach of continuity. If we denote geometrically all possible points of pressure and temperature jointly, by points spread continuously in a plane Surface, each point in the plane being referred to two axes of rectangular coordinates, so that one of its ordinates shall represent the temperature and the other the pressure denoted by that point, and if we mark all the successive boiling- or condensing-points of temperature and pressure as a continuous line on this plane, this line, which may be called the boiling­ line , will be a separating boundary between the regions of the plane cor­responding to the ordinary liquid state and those corresponding to the ordinary gaseous state. But, by consideration of Dr. Andrews’s experimental results, we may see that this separating boundary comes to an end at a point of pressure and temperature which, in conformity with his lan­guage, may be called the critical point of pressure and temperature jointly; and we may see that, from any ordinary liquid state to any ordinary gaseous state, the transition may be effected gradually by an infinite variety of courses passing round outside the extreme end of the boiling-line.