I have already shown that there are two methods of dividing the particles of bodies, the mechanical and chemical. The former only separates a solid mass into a great number of smaller masses; and for these purposes various species of forces are employed, according to circumstances, such as the strength of man or of animals, the weight of water applied through the means of hydraulic engines, the expansive power of steam, the force of the wind, &c. By all these mechanical powers, we can never reduce substances into powder beyond a certain degree of fineness; and the smallest particle produced in this way, though it seems very minute to our organs, is still in fact a mountain, when compared with the ultimate elementary particles of the pulverized substance.
The chemical agents, on the contrary, divide bodies into their primitive particles. If, for instance, a neutral salt be acted upon by these, it is divided, as far as is possible, without ceasing to be a neutral salt. In this Chapter, I mean to give examples of this kind of division of bodies, to which I shall add some account of the relative operations.
In chemical language, the terms of solution and dissolution have long been confounded, and have very improperly been indiscriminately employed for expressing both the division of the particles of a salt in a fluid, such as water, and the division of a metal in an acid. A few reflections upon the effects of these two operations will suffice to show that they ought not to be confounded together. In the solution of salts, the saline particles are only separated from each other, whilst neither the salt nor the water are at all decomposed; we are able to recover both the one and the other in the same quantity as before the operation. The same thing takes place in the solution of resins in alkohol. During metallic dissolutions, on the contrary, a decomposition, either of the acid, or of the water which dilutes it, always takes place; the metal combines with oxygen, and is changed into an oxyd, and a gasseous substance is disengaged; so that in reality none of the substances employed remain, after the operation, in the same state they were in before. This article is entirely confined to the consideration of solution.
To understand properly what takes place during the solution of salts, it is necessary to know, that, in most of these operations, two distinct effects are complicated together, viz. solution by water, and solution by caloric; and, as the explanation of most of the phenomena of solution depends upon the distinction of these two circumstances, I shall enlarge a little upon their nature.
Nitrat of potash, usually called nitre or saltpetre, contains very little water of cristallization, perhaps even none at all; yet this salt liquifies in a degree of heat very little superior to that of boiling water. This liquifaction cannot therefore be produced by means of the water of cristallization, but in consequence of the salt being very fusible in its nature, and from its passing from the solid to the liquid state of aggregation, when but a little raised above the temperature of boiling water. All salts are in this manner susceptible of being liquified by caloric, but in higher or lower degrees of temperature. Some of these, as the acetites of potash and soda, liquify with a very moderate heat, whilst others, as sulphat of potash, lime, &c. require the strongest fires we are capable of producing. This liquifaction of salts by caloric produces exactly the same phenomena with the melting of ice; it is accomplished in each salt by a determinate degree of heat, which remains invariably the same during the whole time of the liquifaction. Caloric is employed, and becomes fixed during the melting of the salt, and is, on the contrary, disengaged when the salt coagulates. These are general phenomena which universally occur during the passage of every species of substance from the solid to the fluid state of aggregation, and from fluid to solid.
These phenomena arising from solution by caloric are always less or more conjoined with those which take place during solutions in water. We cannot pour water upon a salt, on purpose to dissolve it, without employing a compound solvent, both water and caloric; hence we may distinguish several different cases of solution, according to the nature and mode of existence of each salt. If, for instance, a salt be difficultly soluble in water, and readily so by caloric, it evidently follows, that this salt will be difficultly soluble in cold water, and considerably in hot water; such is nitrat of potash, and more especially oxygenated muriat of potash. If another salt be little soluble both in water and caloric, the difference of its solubility in cold and warm water will be very inconsiderable; sulphat of lime is of this kind. From these considerations, it follows, that there is a necessary relation between the following circumstances; the solubility of a salt in cold water, its solubility in boiling water, and the degree of temperature at which the same salt liquifies by caloric, unassisted by water; and that the difference of solubility in hot and cold water is so much greater in proportion to its ready solution in caloric, or in proportion to its susceptibility of liquifying in a low degree of temperature.
The above is a general view of solution; but, for want of particular facts, and sufficiently exact experiments, it is still nothing more than an approximation towards a particular theory. The means of compleating this part of chemical science is extremely simple; we have only to ascertain how much of each salt is dissolved by a certain quantity of water at different degrees of temperature; and as, by the experiments published by Mr de la Place and me, the quantity of caloric contained in a pound of water at each degree of the thermometer is accurately known, it will be very easy to determine, by simple experiments, the proportion of water and caloric required for solution by each salt, what quantity of caloric is absorbed by each at the moment of liquifaction, and how much is disengaged at the moment of cristallization. Hence the reason why salts are more rapidly soluble in hot than in cold water is perfectly evident. In all solutions of salts caloric is employed; when that is furnished intermediately from the surrounding bodies, it can only arrive slowly to the salt; whereas this is greatly accelerated when the requisite caloric exists ready combined with the water of solution.
In general, the specific gravity of water is augmented by holding salts in solution; but there are some exceptions to the rule. Some time hence, the quantities of radical, of oxygen, and of base, which constitute each neutral salt, the quantity of water and caloric necessary for solution, the increased specific gravity communicated to water, and the figure of the elementary particles of the cristals, will all be accurately known. From these all the circumstances and phenomena of cristallization will be explained, and by these means this part of chemistry will be compleated. Mr Seguin has formed the plan of a thorough investigation of this kind, which he is extremely capable of executing.
The solution of salts in water requires no particular apparatus; small glass phials of different sizes, Pl. II. Fig. 16. and 17. pans of earthern ware, A, Fig. 1. and 2. long-necked matrasses, Fig. 14. and pans or basons of copper or of silver, Fig. 13. and 15. answer very well for these operations.
This is an operation used in chemistry and manufactures for separating substances which are soluble in water from such as are insoluble. The large vat or tub, Pl. II. Fig. 12. having a hole D near its bottom, containing a wooden spiget and fosset or metallic stop-cock DE, is generally used for this purpose. A thin stratum of straw is placed at the bottom of the tub; over this, the substance to be lixiviated is laid and covered by a cloth, then hot or cold water, according to the degree of solubility of the saline matter, is poured on. When the water is supposed to have dissolved all the saline parts, it is let off by the stop-cock; and, as some of the water charged with salt necessarily adheres to the straw and insoluble matters, several fresh quantities of water are poured on. The straw serves to secure a proper passage for the water, and may be compared to the straws or glass rods used in filtrating, to keep the paper from touching the sides of the funnel. The cloth which is laid over the matters under lixiviation prevents the water from making a hollow in these substances where it is poured on, through which it might escape without acting upon the whole mass.
This operation is less or more imitated in chemical experiments; but as in these, especially with analytical views, greater exactness is required, particular precautions must be employed, so as not to leave any saline or soluble part in the residuum. More water must be employed than in ordinary lixiviations, and the substances ought to be previously stirred up in the water before the clear liquor is drawn off, otherwise the whole mass might not be equally lixiviated, and some parts might even escape altogether from the action of the water. We must likewise employ fresh portions of water in considerable quantity, until it comes off entirely free from salt, which we may ascertain by means of the hydrometer formerly described.
In experiments with small quantities, this operation is conveniently performed in jugs or matrasses of glass, and by filtrating the liquor through paper in a glass funnel. When the substance is in larger quantity, it may be lixiviated in a kettle of boiling water, and filtrated through paper supported by cloth in the wooden frame, Pl. II. Fig. 3. and 4.; and in operations in the large way, the tub already mentioned must be used.
This operation is used for separating two substances from each other, of which one at least must be fluid, and whose degrees of volatility are considerably different. By this means we obtain a salt, which has been dissolved in water, in its concrete form; the water, by heating, becomes combined with caloric, which renders it volatile, while the particles of the salt being brought nearer to each other, and within the sphere of their mutual attraction, unite into the solid state.
As it was long thought that the air had great influence upon the quantity of fluid evaporated, it will be proper to point out the errors which this opinion has produced. There certainly is a constant slow evaporation from fluids exposed to the free air; and, though this species of evaporation may be considered in some degree as a solution in air, yet caloric has considerable influence in producing it, as is evident from the refrigeration which always accompanies this process; hence we may consider this gradual evaporation as a compound solution made partly in air, and partly in caloric. But the evaporation which takes place from a fluid kept continually boiling, is quite different in its nature, and in it the evaporation produced by the action of the air is exceedingly inconsiderable in comparison with that which is occasioned by caloric. This latter species may be termed vaporization rather than evaporation. This process is not accelerated in proportion to the extent of evaporating surface, but in proportion to the quantities of caloric which combine with the fluid. Too free a current of cold air is often hurtful to this process, as it tends to carry off caloric from the water, and consequently retards its conversion into vapour. Hence there is no inconvenience produced by covering, in a certain degree, the vessels in which liquids are evaporated by continual boiling, provided the covering body be of such a nature as does not strongly draw off the caloric, or, to use an expression of Dr Franklin's, provided it be a bad conductor of heat. In this case, the vapours escape through such opening as is left, and at least as much is evaporated, frequently more than when free access is allowed to the external air.
As during evaporation the fluid carried off by caloric is entirely lost, being sacrificed for the sake of the fixed substances with which it was combined, this process is only employed where the fluid is of small value, as water, for instance. But, when the fluid is of more consequence, we have recourse to distillation, in which process we preserve both the fixed substance and the volatile fluid. The vessels employed for evaporation are basons or pans of copper, silver, or lead, Pl. II. Fig. 13. and 15. or capsules of glass, porcellain, or stone ware, Pl. II. A, Fig. 1. and 2. Pl. III. Fig. 3 and 4. The best utensils for this purpose are made of the bottoms of glass retorts and matrasses, as their equal thinness renders them more fit than any other kind of glass vessel for bearing a brisk fire and sudden alterations of heat and cold without breaking.
As the method of cutting these glass vessels is no where described in books, I shall here give a description of it, that they may be made by chemists for themselves out of spoiled retorts, matrasses, and recipients, at a much cheaper rate than any which can be procured from glass manufacturers. The instrument, Pl. III. Fig. 5. consisting of an iron ring AC, fixed to the rod AB, having a wooden handle D, is employed as follows: Make the ring red hot in the fire, and put it upon the matrass G, Fig. 6. which is to be cut; when the glass is sufficiently heated, throw on a little cold water, and it will generally break exactly at the circular line heated by the ring.
Small flasks or phials of thin glass are exceeding good vessels for evaporating small quantities of fluid; they are very cheap, and stand the fire remarkably. One or more of these may be placed upon a second grate above the furnace, Pl. III. Fig. 2. where they will only experience a gentle heat. By this means a great number of experiments may be carried on at one time. A glass retort, placed in a sand bath, and covered with a dome of baked earth, Pl. III. Fig. 1. answers pretty well for evaporations; but in this way it is always considerably slower, and is even liable to accidents; as the sand heats unequally, and the glass cannot dilate in the same unequal manner, the retort is very liable to break. Sometimes the sand serves exactly the office of the iron ring formerly mentioned; for, if a single drop of vapour, condensed into liquid, happens to fall upon the heated part of the vessel, it breaks circularly at that place. When a very intense fire is necessary, earthen crucibles may be used; but we generally use the word evaporation to express what is produced by the temperature of boiling water, or not much higher.
In this process the integrant parts of a solid body, separated from each other by the intervention of a fluid, are made to exert the mutual attraction of aggregation, so as to coalesce and reproduce a solid mass. When the particles of a body are only separated by caloric, and the substance is thereby retained in the liquid state, all that is necessary for making it cristallize, is to remove a part of the caloric which is lodged between its particles, or, in other words, to cool it. If this refrigeration be slow, and the body be at the same time left at rest, its particles assume a regular arrangement, and cristallization, properly so called, takes place; but, if the refrigeration is made rapidly, or if the liquor be agitated at the moment of its passage to the concrete state, the cristallization is irregular and confused.
The same phenomena occur with watery solutions, or rather in those made partly in water, and partly by caloric. So long as there remains a sufficiency of water and caloric to keep the particles of the body asunder beyond the sphere of their mutual attraction, the salt remains in the fluid state; but, whenever either caloric or water is not present in sufficient quantity, and the attraction of the particles for each other becomes superior to the power which keeps them asunder, the salt recovers its concrete form, and the cristals produced are the more regular in proportion as the evaporation has been slower and more tranquilly performed.
All the phenomena we formerly mentioned as taking place during the solution of salts, occur in a contrary sense during their cristallization. Caloric is disengaged at the instant of their assuming the solid state, which furnishes an additional proof of salt being held in solution by the compound action of water and caloric. Hence, to cause salts to cristallize which readily liquify by means of caloric, it is not sufficient to carry off the water which held them in solution, but the caloric united to them must likewise be removed. Nitrat of potash, oxygenated muriat of potash, alum, sulphat of soda, &c. are examples of this circumstance, as, to make these salts cristallize, refrigeration must be added to evaporation. Such salts, on the contrary, as require little caloric for being kept in solution, and which, from that circumstance, are nearly equally soluble in cold and warm water, are cristallizable by simply carrying off the water which holds them in solution, and even recover their solid state in boiling water; such are sulphat of lime, muriat of potash and of soda, and several others.
The art of refining saltpetre depends upon these properties of salts, and upon their different degrees of solubility in hot and cold water. This salt, as produced in the manufactories by the first operation, is composed of many different salts; some are deliquescent, and not susceptible of being cristallized, such as the nitrat and muriat of lime; others are almost equally soluble in hot and cold water, as the muriats of potash and of soda; and, lastly, the saltpetre, or nitrat of potash, is greatly more soluble in hot than it is in cold water. The operation is begun, by pouring upon this mixture of salts as much water as will hold even the least soluble, the muriats of soda and of potash, in solution; so long as it is hot, this quantity readily dissolves all the saltpetre, but, upon cooling, the greater part of this salt cristallizes, leaving about a sixth part remaining dissolved, and mixed with the nitrat of lime and the two muriats. The nitre obtained by this process is still somewhat impregnated with other salts, because it has been cristallized from water in which these abound: It is completely purified from these by a second solution in a small quantity of boiling water, and second cristallization. The water remaining after these cristallizations of nitre is still loaded with a mixture of saltpetre, and other salts; by farther evaporation, crude saltpetre, or rough-petre, as the workmen call it, is procured from it, and this is purified by two fresh solutions and cristallizations.
The deliquescent earthy salts which do not contain the nitric acid are rejected in this manufacture; but those which consist of that acid neutralized by an earthy base are dissolved in water, the earth is precipitated by means of potash, and allowed to subside; the clear liquor is then decanted, evaporated, and allowed to cristallize. The above management for refining saltpetre may serve as a general rule for separating salts from each other which happen to be mixed together. The nature of each must be considered, the proportion in which each dissolves in given quantities of water, and the different solubility of each in hot and cold water. If to these we add the property which some salts possess, of being soluble in alkohol, or in a mixture of alkohol and water, we have many resources for separating salts from each other by means of cristallization, though it must be allowed that it is extremely difficult to render this separation perfectly complete.
The vessels used for cristallization are pans of earthen ware, A, Pl. II. Fig. 1. and 2. and large flat dishes, Pl. III. Fig. 7. When a saline solution is to be exposed to a slow evaporation in the heat of the atmosphere, with free access of air, vessels of some depth, Pl. III. Fig. 3. must be employed, that there may be a considerable body of liquid; by this means the cristals produced are of considerable size, and remarkably regular in their figure.
Every species of salt cristallizes in a peculiar form, and even each salt varies in the form of its cristals according to circumstances, which take place during cristallization. We must not from thence conclude that the saline particles of each species are indeterminate in their figures: The primative particles of all bodies, especially of salts, are perfectly constant in their specific forms; but the cristals which form in our experiments are composed of congeries of minute particles, which, though perfectly equal in size and shape, may assume very dissimilar arrangements, and consequently produce a vast variety of regular forms, which have not the smallest apparent resemblance to each other, nor to the original cristal. This subject has been very ably treated by the Abbé Haüy, in several memoirs presented to the Academy, and in his work upon the structure of cristals: It is only necessary to extend generally to the class of salts the principles he has particularly applied to some cristalized stones.
As distillation has two distinct objects to accomplish, it is divisible into simple and compound; and, in this section, I mean to confine myself entirely to the former. When two bodies, of which one is more volatile than the other, or has more affinity to caloric, are submitted to distillation, our intention is to separate them from each other: The more volatile substance assumes the form of gas, and is afterwards condensed by refrigeration in proper vessels. In this case distillation, like evaporation, becomes a species of mechanical operation, which separates two substances from each other without decomposing or altering the nature of either. In evaporation, our only object is to preserve the fixed body, without paying any regard to the volatile matter; whereas, in distillation, our principal attention is generally paid to the volatile substance, unless when we intend to preserve both the one and the other. Hence, simple distillation is nothing more than evaporation produced in close vessels.
The most simple distilling vessel is a species of bottle or matrass, A, Pl. III. Fig. 8. which has been bent from its original form BC to BD, and which is then called a retort; when used, it is placed either in a reverberatory furnace, Pl. XIII. Fig. 2. or in a sand bath under a dome of baked earth, Pl. III. Fig. 1. To receive and condense the products, we adapt a recipient, E, Pl. III. Fig. 9. which is luted to the retort. Sometimes, more especially in pharmaceutical operations, the glass or stone ware cucurbit, A, with its capital B, Pl. III. Fig. 12, or the glass alembic and capital, Fig. 13. of one piece, is employed. This latter is managed by means of a tubulated opening T, fitted with a ground stopper of cristal; the capital, both of the cucurbit and alembic, has a furrow or trench, r r, intended for conveying the condensed liquor into the beak RS, by which it runs out. As, in almost all distillations, expansive vapours are produced, which might burst the vessels employed, we are under the necessity of having a small hole, T, Fig. 9. in the balloon or recipient, through which these may find vent; hence, in this way of distilling, all the products which are permanently aëriform are entirely lost, and even such as difficultly lose that state have not sufficient space to condense in the balloon: This apparatus is not, therefore, proper for experiments of investigation, and can only be admitted in the ordinary operations of the laboratory or in pharmacy. In the article appropriated for compound distillation, I shall explain the various methods which have been contrived for preserving the whole products from bodies in this process.
As glass or earthen vessels are very brittle, and do not readily bear sudden alterations of heat and cold, every well regulated laboratory ought to have one or more alembics of metal for distilling water, spiritous liquors, essential oils, &c. This apparatus consists of a cucurbit and capital of tinned copper or brass, Pl. III. Fig. 15. and 16. which, when judged proper, may be placed in the water bath, D, Fig. 17. In distillations, especially of spiritous liquors, the capital must be furnished with a refrigetory, SS, Fig. 16. kept continually filled with cold water; when the water becomes heated, it is let off by the stop-cock, R, and renewed with a fresh supply of cold water. As the fluid distilled is converted into gas by means of caloric furnished by the fire of the furnace, it is evident that it could not condense, and, consequently, that no distillation, properly speaking, could take place, unless it is made to deposit in the capital all the caloric it received in the cucurbit; with this view, the sides of the capital must always be preserved at a lower temperature than is necessary for keeping the distilling substance in the state of gas, and the water in the refrigetory is intended for this purpose. Water is converted into gas by the temperature of 80° (212°), alkohol by 67° (182.75°), ether by 32° (104°); hence these substances cannot be distilled, or, rather, they will fly off in the state of gas, unless the temperature of the refrigetory be kept under these respective degrees.
In the distillation of spiritous, and other expansive liquors, the above described refrigetory is not sufficient for condensing all the vapours which arise; in this case, therefore, instead of receiving the distilled liquor immediately from the beak, TU, of the capital into a recipient, a worm is interposed between them. This instrument is represented Pl. III. Fig. 18. contained in a worm tub of tinned copper, it consists of a metallic tube bent into a considerable number of spiral revolutions. The vessel which contains the worm is kept full of cold water, which is renewed as it grows warm. This contrivance is employed in all distilleries of spirits, without the intervention of a capital and refrigetory, properly so called. The one represented in the plate is furnished with two worms, one of them being particularly appropriated to distillations of odoriferous substances.
In some simple distillations it is necessary to interpose an adopter between the retort and receiver, as shown Pl. III. Fig, 11. This may serve two different purposes, either to separate two products of different degrees of volatility, or to remove the receiver to a greater distance from the furnace, that it may be less heated. But these, and several other more complicated instruments of ancient contrivance, are far from producing the accuracy requisite in modern chemistry, as will be readily perceived when I come to treat of compound distillation.
This term is applied to the distillation of substances which condense in a concrete or solid form, such as the sublimation of sulphur, and of muriat of ammoniac, or sal ammoniac. These operations may be conveniently performed in the ordinary distilling vessels already described, though, in the sublimation of sulphur, a species of vessels, named Alludels, have been usually employed. These are vessels of stone or porcelain ware, which adjust to each other over a cucurbit containing the sulphur to be sublimed. One of the best subliming vessels, for substances which are not very volatile, is a flask, or phial of glass, sunk about two thirds into a sand bath; but in this way we are apt to lose a part of the products. When these are wished to be entirely preserved, we must have recourse to the pneumato-chemical distilling apparatus, to be described in the following chapter.
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