Heads of Lectures on a Course of Experimental Philosophy: Particularly Including Chemistry Part 12

This calx turns blue by exposure to light; and an hundred grains of it heated with charcoal will yield sixty grains of a peculiar metal, in small particles, which, when broken, look like steel. It is soluble in the vitriolic or marine acids, and reduced to a yellow calx by nitrous acid or aqua regia.

_Of Molybdena._

Molybdena is a substance which much resembles plumbago; but its texture is scaly, and not easily pulverized, on account of a degree of flexibility which its laminae possess. With extreme heat, and mixed with charcoal, it yields small particles of a metal that is grey, brittle, and extremely infusible; and uniting with several of the metals, it forms with them brittle or friable compounds. By heat it is converted into a white calx.

_Of Solid Combustible Substances._

There yet remains a cla.s.s of solid substances, of the _combustible_ kind, but most of them have been already considered under the form of the fluids, from which they are originally formed, as _bitumen_, _pit-coal_, and _amber_; or under the princ.i.p.al ingredients of which they are composed, as _sulphur_ and _plumbago_.

There only remains to be mentioned the _diamond_, which is of a nature quite different from that of the other precious stones, the princ.i.p.al ingredient in which is siliceous earth, which renders them not liable to be much affected by heat. On the contrary, the diamond is a combustible substance; for in a degree of heat somewhat greater than that which will melt silver, it burns with a slight flame, diminishes common air, and leaves a soot behind. Also, if diamond powder be triturated with vitriolic acid, it turns it black, which is another proof of its containing phlogiston.

The diamond is valued on account of its extreme hardness, the exquisite polish it is capable of, and its extraordinary refractive power; for light falling on its interior surface with an angle of incidence greater than 24 will be wholly reflected, whereas in gla.s.s it requires an angle of 41 degrees.

LECTURE XXIX.

_Of the Doctrine of Phlogiston and the Composition of Water._

It was supposed to be a great discovery of Mr. Stahl, that all inflammable substances, as well as metals, contain a principle, or substance, to which he gave the name of phlogiston, and that the addition or deprivation of this substance makes some of the most remarkable changes in bodies, especially that the union of a metallic calx and this substance makes a metal; and that combustion consists in the separation of phlogiston from the substances that contain it. That it is the same principle, or substance, that enters into all inflammable substances, and metals, is evident, from its being disengaged from any of them, and entering into the composition of any of the others. Thus the phlogiston of charcoal or inflammable air becomes the phlogiston of any of the metals, when the calx is heated in contact with either of them.

On the contrary, Mr. Lavoisier and most of the French chemists, are of opinion, that there is no such principle, or substance, as phlogiston; that metals and other inflammable bodies are simple substances, which have an affinity to pure air; and that combustion consists not in the separation of any thing from the inflammable substance, but in the union of pure air with it.

They moreover say, that water is not, as has been commonly supposed, a simple substance, but that it consists of two elements, viz. pure air, or _oxygene_, and another, to which they give the name of _hydrogene_, which, with the principle of _heat_, called by them _calorique_, is inflammable air.

The princ.i.p.al fact adduced by them to prove that metals do not lose any thing when they become calces, but only gain something, is, that mercury becomes a calx, called _precipitate per se_, by imbibing pure air, and that it becomes running mercury again by parting with it.

This is acknowledged: but it is almost the only case of any calx being revived without the help of some known phlogistic substance; and in this particular case it is not absurd to suppose, that the mercury, in becoming precipitate per se, may retain all its phlogiston, as well as imbibe pure air, and therefore be revived by simply parting with that air. In many other cases the same metal, in different states, contains more or less phlogiston, as cast iron, malleable iron, and steel. Also there is a calx of mercury made by the acid of vitriol, which cannot be revived without the help of inflammable air, or some other substance supposed to contain phlogiston: and that the inflammable air is really imbibed in these processes, is evident, from its wholly disappearing, and nothing being left in the vessel in which the process is made beside the metal that is revived by it. If precipitate per se be revived in inflammable air, the air will be imbibed, so that running mercury may contain more or less phlogiston.

The antiphlogistians also say, that the diminution of atmospherical air by the burning of phosphorus is a proof of their theory; the pure air being imbibed by that substance, and nothing emitted from it. But there is the same proof of phosphorus containing phlogiston, that there is of dry flesh containing it; since the produce of the solution of it in nitrous acid, and its effect upon the acid, are the same, viz. the production of phlogisticated air, and the phlogistication of the acid.

Their proof that water is decomposed, is, that in sending steam over hot iron, inflammable air (which they suppose to be one const.i.tuent part of it) is procured; while the other part, viz. the oxygene, unites with the iron, and adds to its weight. But it is replied, that the inflammable air may be well supposed to be the phlogiston of the iron, united to part of the water, as its base, while the remainder of the water is imbibed by the calx; and that it is mere water, and not pure air, or oxygene, that is retained in the iron, is evident, from nothing but pure water being recovered when this calx of iron is revived in inflammable air, in which case the inflammable air wholly disappears, taking the place of the water, by which it had been expelled.

In answer to this it is said, that the pure air expelled from the calx uniting with the inflammable air in the vessel, recomposes the water found after this process. But in every other case in which any substance containing pure air is heated in inflammable air, though the inflammable air be in part imbibed, some _fixed air_ is produced, and this fixed air is composed of the pure air in the substance and part of the inflammable air in the vessel. Thus, if _minium_, which contains pure air, and _ma.s.sicot_, which contains none, be heated in inflammable air, in both the cases lead will be revived by the absorption of inflammable air; but in the former case only, and not in the latter, will fixed air be produced. The calx of iron, therefore, having the same effect with ma.s.sicot, when treated in the same manner, appears to contain no more pure air than ma.s.sicot does.

Besides this explanation of the facts on which the new theory is founded, which shews it to be unnecessary, the old hypothesis being sufficient for the purpose, some facts are alledged, as inconsistent with the new doctrine.

If the calx of iron made by water, and charcoal made by the greatest degree of heat, be mixed together, a great quant.i.ty of inflammable air will be produced; though, according to the new theory, neither of these substances contained any water, which they maintain to be the only origin of it. But this fact is easily explained upon the doctrine of phlogiston; the water in this calx uniting with the phlogiston of the charcoal, and then forming inflammable air; and it is the same kind of inflammable air that is made from charcoal and water.

Also the union of inflammable and pure air, when they are fired together by means of the electric spark, produces not pure water, as, according to the new theory, it ought to do, but _nitrous acid_.

To this it has been objected, that the acid thus produced came from the decomposition of phlogisticated air, a small portion of which was at first contained in the mixture of the two kinds of air. But when every particle of phlogisticated air is excluded, the strongest acid is procured.

They find, indeed, that by the slow burning of inflammable air in pure air, they get pure water. But then it appears, that whenever this is the case, there is a production of phlogisticated air, which contains the necessary element of nitrous acid; and this is always the case when there is a little surplus of the inflammable air that is fired along with the pure air, as the acid is always procured when there is a redundancy of pure air.

That much water should be procured by the decomposition of these kinds of air, is easily accounted for, by supposing that water, or steam, is the basis of these, as well as of all other kinds of air.

Since air something better than that of the atmosphere is constantly produced from water by converting it into vapour, and also by removing the pressure of the atmosphere, and these processes do not appear to have any limits; it seems probable, that _water_ united to the principle of _heat_; const.i.tutes atmospherical air; and if so, it must consist of the elements of both dephlogisticated and phlogisticated air; which is a supposition very different from that of the French chemists.

LECTURE x.x.x.

_Of Heat._

Heat is an affection of bodies well known by the sensation that it excites. It is produced by friction or compression, as by the striking of flint against steel, and the hammering of iron, by the reflection or refraction of light, and by the combustion of inflammable substances.

It has been long disputed, whether the cause of heat be properly a _substance_, or some particular affection of the particles that compose the substance that is heated. But be it a substance, or a principle of any other kind, it is capable of being transferred from one body to another, and the communication of it is attended with the following circ.u.mstances. All substances are expanded by heat, but some in a greater degree than others; as metals more than earthy substances, and charcoal more than wood. Also some receive and transmit heat through their substance more readily than others; metals more so than earths, and of the metals, copper more readily than iron. Instruments contrived to ascertain the expansion of substances by heat, are called _pyrometers_, and are of various constructions.

As a standard to measure the degrees of heat, mercury is in general preferable to any other substance, on account of its readily receiving, and communicating, heat through its whole ma.s.s. _Thermometers_, therefore, or instruments to measure the degrees of heat, are generally constructed of it, though, as it is subject to become solid in a great degree of cold, ardent spirit, which will not freeze at all, is more proper in that particular case.

The graduation of thermometers is arbitrary. In that of Fahrenheit, which is chiefly used in England, the freezing point of water is 32, and the boiling point 212. In that of Reaumur, which is chiefly used abroad, the freezing point of water is 0, and the boiling point 80. To measure the degrees of heat above ignition, Mr. Wedgwood has happily contrived to use pieces of clay, which contract in the fire; and he has also been able to find the coincidence of the degrees in mercurial thermometers with those of his own.

To measure the degrees of heat and cold during a person's absence, Lord George Cavendish contrived an instrument, in which a small bason received the mercury, that was raised higher than the place for which it was regulated by heat or cold, without a power of returning. But Mr. Six has lately hit upon a better method, viz. introducing into the tube of his thermometer a small piece of iron, which is raised by the ascent of the mercury, and prevented from descending by a small spring; but which may be brought back to its former place by a magnet acting through the gla.s.s.

Heat, like light, is propagated in right lines; and what is more remarkable, cold observes the same laws. For if the substance emitting heat without light, as iron below ignition, be placed in the focus of a burning mirror, a thermometer in the focus of a similar mirror, placed parallel to it, though at a considerable distance, will be heated by it, and if a piece of ice be placed there, the mercury will fall.

Heat a.s.sists the solvent power of almost all menstrua; so that many substances will unite in a certain degree of heat, which will form no union at all without it, as dephlogisticated and inflammable air.

If substances be of the same kind, they will receive heat from one another, in proportion to their ma.s.ses. Thus, if a quant.i.ty of water heated to 40 be mixed with another equal quant.i.ty of water heated to 20, the whole ma.s.s will be heated to 30. But if the substances be of different kinds, they will receive heat from each other in different proportions, according to their _capacity_ (as it is called) of receiving heat. Thus, if a pint of mercury of the temperature of 136 be mixed with a pint of water of the temperature of 50, the temperature of the two after mixture will not be a medium between those two numbers, viz. 93, but 76; consequently the mercury was cooled 60, while the water was heated only 26; so that 26 degrees of heat in water correspond to 60 in mercury. But mercury is about 13 times specifically heavier than water, so that an equal weight of mercury would contain only one thirtieth part of this heat; and dividing 26 by 13, the quotient is 2.

If _weight_, therefore, be considered, the heat discovered by water should be reckoned as 2 instead of 60; and consequently when water receives 2 degrees of heat, an equal weight of mercury will receive 60; and dividing both the numbers by 2, if the heat of water be 1, that of the mercury will be 30. Or since they receive equal degrees of heat, whether they discover it or not (and the less they discover, the more they retain in a latent state) a pound of mercury contains no more than one thirtieth part of the heat actually existing in a pound of water of the same temperature. Water, therefore, is said to have a greater capacity for receiving and retaining heat, without discovering it, than mercury, in the proportion of 30 to 1, if weight be considered, or of 60 to 26, that is of 30 to 13; if _bulk_ be the standard, though, according to some, it is as 3 to 2.

The capacity of receiving heat in the substance is greatest in a state of vapour, and least in that of a solid; so that when ice is converted into water, heat is absorbed, and more still when it is converted into vapour; and on the contrary, when vapour is converted into water, it gives out the heat which it had imbibed, and when it becomes ice it gives out still more.

If equal quant.i.ties of ice and water be exposed to heat at the temperature of 32, the ice will only become water, without receiving any additional sensible heat; but an equal quant.i.ty of water in the same situation would be raised to 178, so that 146 degrees of heat will be imbibed, and remain in latent in the water, in consequence of its pa.s.sing from a state of ice: and heat communicated by a given weight of vapour will raise an equal weight of a nonevaporable substance, of the same capacity with water, 943 degrees; so that much more heat is latent in steam, than in the water from which it was formed.

This doctrine of latent heat explains a great variety of phaenomena in nature; as that of cooling bodies by evaporation, the vapour of water, or any other fluid substance, absorbing and carrying off the heat they had before.

Water, perfectly at rest, will fall considerably below the freezing point, and yet continue fluid: but on the slightest agitation, the congelation of the whole, or part of it, takes place instantly, and if the whole be not solid, it will instantly rise to 32, the freezing point. From whatever cause, some motion seems necessary to the commencement of congelation, at least in a moderate temperature; but whenever any part of the water becomes solid, it gives out some of the heat it had before, and that heat which was before latent becoming sensible, and being diffused through the whole ma.s.s, raises its temperature.

On the same principle, when water heated higher than the boiling point in a digester is suddenly permitted to escape in the form of steam, the remainder is instantly reduced to the common boiling point, the heat above that point being carried off in a latent state by the steam.

Had it not been for this wise provision in nature, the whole of any quant.i.ty of water would, in all cases of freezing, have become solid at once; and also the whole of any quant.i.ty that was heated to the point of boiling, would have been converted into steam at once; circ.u.mstances which would have been extremely inconvenient, and often fatal.

This doctrine also explains the effect of freezing mixtures, as that of salt and snow. These solid substances, on being mixed, become fluid, and that fluid absorbing much heat, deprives all the neighbouring bodies of part of what they had. But if the temperature at which the mixture is made be as low as that to which this mixture would have brought it, it has no effect, and in a lower temperature this new fluid would become solid; for that mixture has only a certain determinate capacity for heat, and if the neighbouring bodies have less heat, they will take from it.

It has been observed, that the comparative heat of bodies containing phlogiston is increased by calcination or combustion; so that the calx of iron has a greater capacity for heat, and therefore contains more latent heat, than the metal.

In general it is not found, that the same substances have their capacity for receiving heat increased by an increase of temperature; but this is said to be the case with a mixture of ardent spirit and water, and also that of spirit of vitriol and water.

Since all substances contain a greater or less quant.i.ty of heat, and in consequence of being deprived of it become colder and colder, it is a question of some curiosity to determine the extent to which this can go, or at what degree in the scale of a thermometer any substance would be absolutely cold, or deprived of all heat; and an attempt has been made to solve this problem in the following manner. Comparing the capacity of water with that of ice, by means of a third substance, viz. mercury, it has been found, that if that of ice be 9, that of water is 10; so that water in becoming ice gives out one tenth part of its whole quant.i.ty of heat. But it has been shown, that ice in becoming water absorbs 146 degrees of heat. This, therefore, being one tenth part of the whole heat of water, it must have contained 1460 degrees; so that taking 32 degrees, which is the freezing point, from that number, the point of absolute cold will be 1426 below 0 of Fahrenheit's scale.

By a computation, made by means of the heat of inflammable and dephlogisticated air, at the temperature of 50, Dr. Crawford finds, that it contains nearly 1550 degrees of heat; so that the point of absolute cold will be 1500 below 0. But more experiments are wanted to solve this curious problem to entire satisfaction.