Chapter I: On Water and Its Compounds (5)

In the existing state of our knowledge concerning solution, such
solutions may be looked on as a transition between emulsion and
ordinary solutions, but no fundamental judgment can be formed
about them until a study has been made of their relations to
ordinary solutions (the solutions of even soluble colloids freeze
immediately on cooling below 0°, and, according to Guthrie, do
not form cryohydrates), and to supersaturated solutions, with
which they have certain points in common.

Solutions of salts on refrigeration below 0° deposit ice or crystals (which then frequently contain water of crystallisation) of the salt dissolved, and on reaching a certain degree of concentration they solidify in their entire mass. These solidified masses are termed _cryohydrates_. My researches on solutions of common salt (1868) showed that its solution solidifies when it reaches a composition NaCl + 10H_{2}O (180 parts of water per 58·5 parts of salt), which takes place at about -23°. The solidified solution melts at the same temperature, and both the portion melted and the remainder preserve the above composition. Guthrie (1874-1876) obtained the cryohydrates of many salts, and he showed that certain of them are formed like the above at comparatively low temperatures, whilst others (for instance, corrosive sublimate, alums, potassium chlorate, and various colloids) are formed on a slight cooling, to -2° or even before.[58] In the case of common salt, the cryohydrate with 10 molecules of water, and in the case of sodium nitrate, the cryohydrate[59] with 7 molecules of water (_i.e._ 126 parts of water per 85 of salt) should be accepted as established substances, capable of passing from a solid to a liquid state and conversely; and therefore it may be thought that in cryohydrates we have solutions which are not only undecomposable by cold, but also have a definite composition which would present a fresh case of definite equilibrium between the solvent and the substance dissolved.

[58] Offer (1880) concludes, from his researches on cryohydrates, that
they are simple mixtures of ice and salts, having a constant
melting point, just as there are alloys having a constant point
of fusion, and solutions of liquids with a constant boiling point
(_see_ note 60). This does not, however, explain in what form
a salt is contained, for instance, in the cryohydrate NaCl +
10H_{2}O. At temperatures above -10° common salt separates out in
anhydrous crystals, and at temperatures near -10°, in combination
with water of crystallisation, NaCl + 2H_{2}O, and, therefore,
it is very improbable that at still lower temperatures it would
separate without water. If the possibility of the solidified
cryohydrate containing NaCl + 2H_{2}O and ice be admitted, then
it is not clear why one of these substances does not melt before
the other. If alcohol does not extract water from the solid mass,
leaving the salt behind, this does not prove the presence of ice,
because alcohol also takes up water from the crystals of many
hydrated substances (for instance, from NaCl + 2H_{2}O) at about
their melting-points. Besides which, a simple observation on the
cryohydrate, NaCl + 10H_{2}O, shows that with the most careful
cooling it does not on the addition of ice deposit ice, which
would occur if ice were formed on solidification intermixed with
the salt.

I may add with regard to cryohydrates that many of the solutions
of acids solidify completely on prolonged cooling (for example,
H_{2}SO_{4},H_{2}O), and then form perfectly definite compounds.
For the solutions of sulphuric acid (_see_ Chapter XX.)
Pickering obtained, for instance, a hydrate, H_{2}SO_{4},4H_{2}O
at -25°. Hydrochloric, nitric, and other acids also give similar
crystalline hydrates, melting at low temperatures and presenting
many similarities with the cryohydrates.

[59] _See_ note 24.

The formation of definite but unstable compounds in the process of solution becomes evident from the phenomena of a marked decrease of vapour tension, or from the rise of the temperature of ebullition which occurs in the solution of certain volatile liquids and gases in water. As an example, we will take hydriodic acid, HI, a gas which liquefies, giving a liquid which boils at -20°. A solution of it containing 57 p.c. of hydriodic acid is distinguished by the fact that if it be heated the hydriodic acid volatilises together with the water in the same proportions as they occur in the solution, therefore such a solution may be distilled unchanged. The solution boils at a higher temperature than water, at 127°. A portion of the physical properties of the gas and water have in this case already disappeared--a new substance is formed, which has its definite boiling point. To put it more correctly, this is not the temperature of ebullition, but the temperature at which the compound formed decomposes, forming the vapours of the products of dissociation, which, on cooling, re-combine. Should a less amount of hydriodic acid be dissolved in water than the above, then, on heating such a solution, water only at first distils over, until the solution attains the above-mentioned composition; it will then distil over unaltered. If more hydriodic acid be passed into such a solution a fresh quantity of the gas will dissolve, but it passes off with great ease, like air from water. It must not, however, be thought that those forces which determine the formation of ordinary gaseous solutions play no part whatever in the formation of a solution having a definite boiling point; that they do react is shown from the fact that such constant gaseous solutions vary in their composition under different pressures.[60] It is not, therefore, at every, but only at the ordinary, atmospheric pressure that a constant boiling solution of hydriodic acid will contain 57 p.c. of the gas. At another pressure the proportion of water and hydriodic acid will be different. It varies, however, judging from observations made by Roscoe, very little for considerable variations of pressure. This variation in composition directly indicates that pressure exerts an influence on the formation of unstable chemical compounds which are easily dissociated (with formation of a gas), just as it influences the solution of gases, only the latter is influenced to a more considerable degree than the former.[61] Hydrochloric, nitric, and other acids form _solutions having definite boiling points_, like that of hydriodic acid. They show further the common property, if containing but a small proportion of water, that they _fume in air_. Strong solutions of nitric, hydrochloric, hydriodic, and other gases are even termed 'fuming acids.' The fuming liquids contain a definite compound whose temperature of ebullition (decomposition) is higher than 100°, and contain also an excess of the volatile substance dissolved, which exhibits a capacity to combine with water and form a hydrate, whose vapour tension is less than that of aqueous vapour. On evaporating in air, this dissolved substance meets the atmospheric moisture and forms a visible vapour (fumes) with it, which consists of the above-mentioned compound. The attraction or affinity which binds, for instance, hydriodic acid with water is evinced not only in the evolution of heat and the diminution of vapour tension (rise of boiling point), but also in many purely chemical relations. Thus hydriodic acid is produced from iodine and hydrogen sulphide in the presence of water, but unless water is present this reaction does not take place.[62]

[60] For this reason (the want of entire constancy of the composition
of constant boiling solutions with a change of pressure), the
existence of definite hydrates formed by volatile substances--for
instance, by hydrochloric acid and water--is frequently denied.
It is generally argued as follows: If there did exist a constancy
of composition, then it would be unaltered by a change of
pressure. But the distillation of constant boiling hydrates
is undoubtedly accompanied (judging by the vapour densities
determined by Bineau), like the distillation of sal ammoniac,
sulphuric acid, &c., by a complete decomposition of the original
compound--that is, these substances do not exist in a state
of vapour, but their products of decomposition (hydrochloric
acid and water) are gases at the temperature of volatilisation,
which dissolve in the volatilised and condensed liquids; but
the solubility of gases in liquids depends on the pressure,
and, therefore, the composition of constant boiling solutions
may, and even ought to, vary with a change of pressure, and,
further, the smaller the pressure and the lower the temperature
of volatilisation, the more likely is a true compound to be
obtained. According to the researches of Roscoe and Dittmar
(1859), the constant boiling solution of hydrochloric acid
proved to contain 18 p.c. of hydrochloric acid at a pressure of
3 atmospheres, 20 p.c. at 1 atmosphere, and 23 p.c. at 1/10 of
an atmosphere. On passing air through the solution until its
composition became constant (_i.e._ forcing the excess of aqueous
vapour or of hydrochloric acid to pass away with the air),
then acid was obtained containing about 20 p.c. at 100°, about
23 p.c. at 50°, and about 25 p.c. at 0°. From this it is seen
that by decreasing the pressure and lowering the temperature of
evaporation one arrives at the same limit, where the composition
should be taken as HCl + 6H_{2}O, which requires 25·26 p.c. of
hydrochloric acid. Fuming hydrochloric acid contains more than
this.

In the case already considered, as in the case of formic acid
in the researches of D. P. Konovaloff (note 47), the constant
boiling solution corresponds with a minimum tension--that
is, with a boiling point higher than that of either of the
component elements. But there is another case of constant boiling
solutions similar to the case of the solution of propyl alcohol,
C_{3}H_{8}O, when a solution, undecomposed by distillation, boils
at a lower point than that of the more volatile liquid. However,
in this case also, if there be solution, the possibility of the
formation of a definite compound in the form C_{3}H_{8}O + H_{2}O
cannot be denied, and the tension of the solution is not equal to
the sum of tensions of the components. There are possible cases
of constant boiling mixtures even when there is no solution nor
any loss of tension, and consequently no chemical action, since
the amount of liquids that are volatilised is determined by
the product of the vapour densities into their vapour tensions
(Wanklyn), in consequence of which liquids whose boiling point
is above 100°--for instance, turpentine and ethereal oils in
general--when distilled with aqueous vapour, pass over at a
temperature below 100°. Consequently, it is not in the constancy
of composition and boiling point (temperature of decomposition)
that evidence of a distinct chemical action is to be found in
the above-described solutions of acids, but in the great loss
of tension, which completely resembles the loss of tension
observed, for instance, in the perfectly-definite combinations of
substances with water of crystallisation (see later, note 65).
Sulphuric acid, H_{2}SO_{4}, as we shall learn later, is also
decomposed by distillation, like HCl + 6H_{2}O, and exhibits,
moreover, all the signs of a definite chemical compound. The
study of the variation of the specific gravities of solutions as
dependent on their composition (see note 19) shows that phenomena
of a similar kind, although of different dimensions, take place
in the formation of both H_{2}SO_{4} from H_{2}O and SO_{3}, and
of HCl + 6H_{2}O (or of aqueous solutions analogous to it) from
HCl and H_{2}O.

[61] The essence of the matter may he thus represented. A gaseous or
easily volatile substance _A_ forms with a certain quantity of
water, _n_H_{2}O, a definite complex compound _An_H_{2}O, which
is stable up to a temperature t° higher than 100°. At this
temperature it is decomposed into two substances, _A_ + H_{2}O.
Both boil below _t_° at the ordinary pressure, and therefore at
_t_° they distil over and re-combine in the receiver. But if a
part of the substance _An_H_{2}O is decomposed or volatilised,
a portion of the undecomposed liquid still remains in the
vessel, which can partially dissolve one of the products of
decomposition, and that in quantity varying with the pressure and
temperature, and therefore the solution at a constant boiling
point will have a slightly different composition at different
pressures.

[62] For solutions of hydrochloric acid in water there are still greater
differences in reactions. For instance, strong solutions
decompose antimony sulphide (forming hydrogen sulphide, H_{2}S),
and precipitate common salt from its solutions, whilst weak
solutions do not act thus.

Many compunds containing water of crystallisation are solid substances (when melted they are already solutions--_i.e._ liquids); furthermore, they are capable of being formed from solutions, like ice or aqueous vapour. They may be called _crystallo-hydrates_. Inasmuch as the direct presence of ice or aqueous vapour cannot be admitted in solutions (for these are liquids), although the presence of water may be, so also there is no basis for acknowledging the presence in solutions of crystallo-hydrates, although they are obtained from solutions as such.[63] It is evident that such substances present one of the many forms of equilibrium between water and a substance dissolved in it. This form, however, reminds one, in all respects, of solutions--that is, aqueous compounds which are more or less easily decomposed, with separation of water and the formation of a less aqueous or an anhydrous compound. In fact, there are not a few crystals containing water which lose a part of their water at the ordinary temperature. Of such a kind, for instance, are the crystals of soda, or sodium carbonate, which, when separated from an aqueous solution at the ordinary temperature, are quite transparent; but when left exposed to air, lose a portion of their water, becoming opaque, and, in the process, lose their crystalline appearance, although preserving their original form. This process of the separation of water at the ordinary temperature is termed the _efflorescence_ of crystals. Efflorescence takes place more rapidly under the receiver of an air pump, and especially at a gentle heat. This breaking up of a crystal is dissociation at the ordinary temperature. Solutions are decomposed in exactly the same manner.[64] The tension of the aqueous vapour which is given off from crystallo-hydrates is naturally, as with solutions, less than the vapour tension of water itself[65] at the same temperature, and therefore many anhydrous salts which are capable of combining with water absorb aqueous vapour from moist air; that is, they act like a cold body on which water is deposited from steam. It is on this that the desiccation of gases is based, and it must further be remarked in this respect that certain substances--for instance, potassium carbonate (K_{2}CO_{3}) and calcium chloride (CaCl_{2})--not only absorb the water necessary for the formation of a solid crystalline compound, but also give solutions, or _deliquesce_, as it is termed, in moist air. Many crystals do not effloresce in the least at the ordinary temperature; for example, copper sulphate, which may be preserved for an indefinite length of time without efflorescing, but when placed under the receiver of an air pump, if efflorescence be once started, it goes on at the ordinary temperature. The temperature at which the complete separation of water from crystals takes place varies considerably, not only for different substances, but also for different portions of the contained water. Very often the temperature at which dissociation begins is very much higher than the boiling point of water. So, for example, copper sulphate, which contains 36 p.c. of water, gives up 28·8 p.c. at 100°, and the remaining quantity, namely 7·2 p.c., only at 240°. Alum, out of the 45·5 p.c. of water which it contains, gives up 18·9 p.c. at 100°, 17·7 p.c. at 120°, 7·7 p.c. at 180°, and 1 p.c. at 280°; it only loses the last quantity (1 p.c.) at its temperature of decomposition. These examples clearly show that the annexation of water of crystallisation is accompanied by a rather profound, although, in comparison with instances which we shall consider later, still inconsiderable, change of its properties. In certain cases the water of crystallisation is only given off when the solid form of the substance is destroyed: when the crystals melt on heating. The crystals are then said _to melt in their water of crystallisation_. Further, after the separation of the water, a solid substance remains behind, so that by further heating it acquires a solid form. This is seen most clearly in crystals of sugar of lead or lead acetate, which melt in their water of crystallisation at a temperature of 56·25°, and in so doing begin to lose water. On reaching a temperature of 100° the sugar of lead solidifies, having lost all its water; and then at a temperature of 280°, the anhydrous and solidified salt again melts.[65 bis]

[63] Supersaturated solutions give an excellent proof in this respect.
Thus a solution of copper sulphate generally crystallises in
penta-hydrated crystals, CuSO_{4} + 5H_{2}O, and its saturated
solution gives such crystals if it be brought into contact with
the minutest possible crystal of the same kind. But, according
to the observations of Lecoq de Boisbaudran, if a crystal of
ferrous sulphate (an isomorphous salt, _see_ note 55), FeSO_{4}
+ 7H_{2}O, be placed in a saturated solution of copper sulphate,
then crystals of hepta-hydrated salt, CuSO_{4} + 7H_{2}O,
are obtained. It is evident that neither the penta-nor the
hepta-hydrated salt is contained as such in the solution. The
solution presents its own particular liquid form of equilibrium.

[64] Efflorescence, like every evaporation, proceeds from the surface.
In the interior of crystals which have effloresced there is
usually found a non-effloresced mass, so that the majority of
effloresced crystals of washing soda show, in their fracture, a
transparent nucleus coated by an effloresced, opaque, powdery
mass. It is a remarkable circumstance in this respect that
efflorescence proceeds in a completely regular and uniform
manner, so that the angles and planes of similar crystallographic
character effloresce simultaneously, and in this respect the
crystalline form determines those parts of crystals where
efflorescence starts, and the order in which it continues. In
solutions evaporation also proceeds from the surface, and the
first crystals which appear on its reaching the required degree
of saturation are also formed at the surface. After falling to
the bottom the crystals naturally continue to grow (_see_ Chapter
X.).

[65] According to Lesc[oe]ur (1883), at 100° a concentrated solution of
barium hydroxide, BaH_{2}O_{2}, on first depositing crystals
(with + H_{2}O) has a tension of about 630 mm. (instead of
760 mm., the tension of water), which decreases (because the
solution evaporates) to 45 mm., when all the water is expelled
from the crystals, BaH_{2}O_{2} + H_{2}O, which are formed, but
they also lose water (dissociate, effloresce at 100°), leaving
the hydroxide, BaH_{2}O_{2}, which is perfectly undecomposable
at 100°--that is, does not part with water. At 73° (the tension
of water is then 265 mm.) a solution, containing 33H_{2}O,
on crystallising has a tension of 230 mm.; the crystals,
BaH_{2}O_{2} + 8H_{2}O, which separate out, have a tension of
160 mm.; on losing water they give BaH_{2}O_{2} + H_{2}O. This
substance does not decompose at 73°, and therefore its tension =
0. In those crystallohydrates which effloresce at the ordinary
temperature, the tension of dissociation nearly approximates
to that of the aqueous vapour, as Lesc[oe]ur (1891) showed. To
this category of compounds belong B_{2}O_{3}(3 + _x_)H_{2}O,
C_{2}O_{4}H_{2}(2 + _x_)H_{2}O, BaO(9 + _x_)H_{2}O, and SrO(9
+ _x_)H_{2}O. And a still greater tension is possessed by
Na_{2}SO_{4}10H_{2}O, Na_{2}CO_{3}10H_{2}O, and MgSO_{4}(7 +
_x_)H_{2}O. Müller-Erzbach (1884) determines the tension (with
reference to liquid water) by placing tubes of the same length
with water and the substances experimented with in a desiccator,
the rate of loss of water giving the relative tension. Thus,
at the ordinary temperature, crystals of sodium phosphate,
Na_{2}HPO_{4} + 12H_{2}O, present a tension of 0·7 compared
with water, until they lose 5H_{2}O, then 0·4 until they lose
5H_{2}O more, and on losing the last equivalent of water the
tension falls to 0·04 compared with water. It is clear that
the different molecules of water are held by an unequal force.
Out of the five molecules of water in copper sulphate the two
first are comparatively easily separated even at the ordinary
temperature (but only after several days in a desiccator,
according to Latchinoff); the next two are more difficultly
separated, and the last equivalent is retained even at 100°. This
is another indication of the capacity of CuSO_{4} to form three
hydrates, CuSO_{4}5H_{2}O, CuSO_{4}3H_{2}O, and CuSO_{4}H_{2}O.
The researches of Andreae on the tension of dissociation of
hydrated sulphate of copper showed (1891) the existence of three
provinces, characterised at a given temperature by a constant
tension: (1) between 3-5, (2) between 1-3, and lastly (3) between
0-1 molecule of water, which again confirms the existence of
three hydrates of the above composition for this salt.

[65 bis] Sodium acetate (C_{2}H_{3}O_{2}Na,3H_{2}O) melts at 58°, but
re-solidifies only on contact with a crystal, otherwise it
may remain liquid even at 0°, and may be used for obtaining a
constant temperature. According to Jeannel, the latent heat
of fusion is about 28 calories, and according to Pickering
the heat of solution 35 calories. When melted this salt boils
at 123°--that is, the tension of the vapour given off at that
temperature equals the atmospheric pressure.

It is most important to recognise in respect to the water of crystallisation that its ratio to the quantity of the substance with which it is combined is always a constant quantity. However often we may prepare copper sulphate, we shall always find 36·14 p.c. of water in its crystals, and these crystals always lose four-fifths of their water at 100°, and one-fifth of the whole amount of the water contained remains in the crystals at 100°, and is only expelled from them at a temperature of about 240°. What has been said about crystals of copper sulphate refers also to crystals of every other substance, which contain water of crystallisation. It is impossible in any of these cases to increase either the relative proportion of the salt or of the water, without changing the homogeneity of the substance. If once a portion of the water be lost--for instance, if once efflorescence takes place--a mixture is obtained, and not a homogeneous substance, namely a mixture of a substance deprived of water with a substance which has not yet lost water--_i.e._ decomposition has already commenced. This constant ratio is an example of the fact that in chemical compounds the quantity of the component parts is quite definite; that is, it is an example of the so-called _definite chemical compounds_. They may be distinguished from solutions, and from all other so-called indefinite chemical compounds, in that at least one, and sometimes both, of the component parts may be added in a large quantity to an indefinite chemical compound, without destroying its homogeneity, as in solutions, whilst it is impossible to add any one of the component parts to a definite chemical compound without destroying the homogeneity of the entire mass. Definite chemical compounds only decompose at a certain rise in temperature; on a lowering in temperature they do not, at least with very few exceptions, yield their components like solutions which form ice or compounds with water of crystallisation. This leads to the assumption that solutions contain water as water,[66] although it may sometimes be in a very small quantity. Therefore solutions which are capable of solidifying completely (for instance, crystallo-hydrates capable of melting) such as the compound of 84-1/2 parts of sulphuric acid, H_{2}SO_{4}, with 15-1/2 parts of water, H_{2}O, or H_{2}SO_{4},H_{2}O (or H_{4}SO_{5}), appear as true definite chemical compounds. If, then, we imagine such a definite compound in a liquid state, and admit that it partially decomposes in this state, separating water--not as ice or vapour (for then the system would be heterogeneous, including substances in different physical states), but in a liquid form, when the system will be homogeneous--we shall form an idea of a solution as an unstable, dissociating fluid state of equilibrium between water and the substance dissolved. Moreover, it should be remarked that, judging by experiment, many substances give with water not one but _diverse_ compounds,[67] which is seen in the capacity of one substance to form with water many various _crystallo-hydrates_, or compounds with water of crystallisation, showing diverse and independent properties. From these considerations, _solutions[68] may be regarded as fluid, unstable, definite chemical compounds in a state of dissociation_.[69]

[66] Such a phenomenon frequently presents itself in purely chemical
action. For instance, let a liquid substance _A_ give, with
another liquid substance _B_, under the conditions of an
experiment, a mere minute quantity of a solid or gaseous
substance _C_. This small quantity will separate out (pass
away from the sphere of action, as Berthollet expressed it),
and the remaining masses of _A_ and _B_ will again give _C_;
consequently, under these conditions action will go on to the
end. Such, it seems to me, is the action in solutions when they
yield ice or vapour indicating the presence of water.

[67] Certain substances are capable of forming together only one
compound, others several, and these of the most varied degrees
of stability. The compounds of water are instances of this
kind. In solutions the existence of several different definite
compounds must be acknowledged, but many of these have not
yet been obtained in a free state, and it may be that they
cannot be obtained in any other but a liquid form--that is,
dissolved; just as there are many undoubted definite compounds
which only exist in one physical state. Among the hydrates such
instances occur. The compound CO_{2} + 8H_{2}O (_see_ note
31), according to Wroblewski, only occurs in a solid form.
Hydrates like H_{2}S + 12H_{2}O (De Forcrand and Villard), HBr
+ H_{2}O (Roozeboom), can only be accepted on the basis of a
decrease of tension, but present themselves as very transient
substances, incapable of existing in a stable free state.
Even sulphuric acid, H_{2}SO_{4}, itself, which undoubtedly
is a definite compound, fumes in a liquid form, giving off
the anhydride, SO_{3}--that is, it exhibits a very unstable
equilibrium. The crystallo-hydrates of chlorine, Cl_{2} +
8H_{2}O, of hydrogen sulphide, H_{2}S + 12H_{2}O (it is formed
at 0°, and is completely decomposed at +1°, as then 1 vol. of
water only dissolves 4 vols. of hydrogen sulphide, while at 0·1°
it dissolves about 100 vols.), and of many other gases, are
instances of hydrates which are very unstable.

[68] Of such a kind are also other indefinite chemical compounds; for
example, metallic alloys. These are solid substances or
solidified solutions of metals. They also contain definite
compounds, and may contain an excess of one of the metals.
According to the experiments of Laurie (1888), the alloys of zinc
with copper in respect to the electro-motive force in galvanic
batteries behave just like zinc if the proportion of copper in
the alloy does not exceed a certain percentage--that is, until
a definite compound is attained--for in that case particles of
free zinc are present; but if a copper surface be taken, and it
be covered by only one-thousandth part of its area of zinc, then
only the zinc will act in a galvanic battery.

[69] According to the above supposition, the condition of solutions
in the sense of the kinetic hypothesis of matter (that is, on
the supposition of an internal motion of molecules and atoms)
may be represented in the following form:--In a homogeneous
liquid--for instance, water--the molecules occur in a certain
state of, although mobile, still stable, equilibrium. When a
substance _A_ dissolves in water, its molecules form with several
molecules of water, systems _An_H_{2}O, which are so unstable
that when surrounded by molecules of water they decompose and
re-form, so that _A_ passes from one mass of molecules of water
to another, and the molecules of water which were at this
moment in harmonious motion with _A_ in the form of the system
_An_H_{2}O, in the next instant may have already succeeded in
getting free. The addition of water or of molecules of _A_
may either only alter the number of free molecules, which in
their turn enter into systems _An_H_{2}O, or they may introduce
conditions for the possibility of building up new systems
_Am_H_{2}O, where _m_ is either greater or less than _n_. If
in the solution the relation of the molecules be the same as
in the system _Am_H_{2}O, then the addition of fresh molecules
of water or of _A_ would be followed by the formation of new
molecules _An_H_{2}O. The relative quantity, stability, and
composition of these systems or definite compounds will vary in
one or another solution. I adopted this view of solutions (1887,
Pickering subsequently put forward a similar view) after a most
intimate study of the variation of their specific gravities, to
which my book, cited in note 19, is devoted. Definite compounds,
_An__{1}H_{2}O and _Am__{1}H_{2}O, existing in a free--for
instance, solid--form, may in certain cases be held in solutions
in a dissociated state (although but partially); they are similar
in their structure to those definite substances which are formed
in solutions, but it is not necessary to assume that such
systems as Na_{2}SO_{4} + 10H_{2}O, or Na_{2}SO_{4} + 7H_{2}O,
or Na_{2}SO_{4}, are contained in solutions. The comparatively
more stable systems _An__{1}H_{2}O which exist in a free state
and change their physical state must present, although within
certain limits of temperature, an entirely harmonious kind of
motion of _A_ with _n__{1}H_{2}O; the property also and state of
systems _An_H_{2}O and _Am_H_{2}O, occurring in solutions, is
that they are in a liquid form, although partially dissociated.
Substances _A__{1}, which give solutions, are distinguished by
the fact that they can form such unstable systems _An_H_{2}O,
but besides them they can give other much more stable systems
_An__{1}H_{2}O. Thus ethylene, C_{2}H_{4}, in dissolving in
water, probably forms a system C_{2}H_{4}_n_H_{2}O, which easily
splits up into C_{2}H_{4} and H_{2}O, but it also gives the
system of alcohol, C_{2}H_{4},H_{2}O or C_{2}H_{6}O, which is
comparatively stable. Thus oxygen can dissolve in water, and it
can combine with it, forming peroxide of hydrogen. Turpentine,
C_{10}H_{16}, does not dissolve in water, but it combines with it
as a comparatively stable hydrate. In other words, the chemical
structure of hydrates, or of the definite compounds which are
contained in solutions, is distinguished not only by its original
peculiarities but also by a diversity of stability. A similar
structure to hydrates must be acknowledged in crystallo-hydrates.
On melting they give actual (real) solutions. As substances which
give crystallo-hydrates, like salts, are capable of forming a
number of diverse hydrates, and as the greater the number of
molecules of water (_n_) they (_An_H_{2}O) contain, the lower
is the temperature of their formation, and as the more easily
they decompose the more water they hold, therefore, in the first
place, the isolation of hydrates holding much water existing in
aqueous solutions may be soonest looked for at low temperatures
(although, perhaps, in certain cases they cannot exist in the
solid state); and, secondly, the stability also of such higher
hydrates will be at a minimum under the ordinary circumstances
of the occurrence of liquid water. Hence a further more detailed
investigation of cryohydrates may help to the elucidation of
the nature of solutions. But it may be foreseen that certain
cryohydrates will, like metallic alloys, present solidified
mixtures of ice with the salts themselves and their more stable
hydrates, and others will be definite compounds.

In regarding solutions from this point of view they come under the head of those definite compounds with which chemistry is mainly concerned.[70]

[70] The above representation of solutions, &c., considering them as
a particular state of definite compounds, excludes the
independent existence of indefinite compounds; by this means that
unity of chemical conception is obtained which cannot be arrived
at by admitting the physico-mechanical conception of indefinite
compounds. The gradual transition from typical solutions (as
of gases in water, and of weak saline solutions) to sulphuric
acid, and from it and its definite, but yet unstable and liquid,
compounds, to clearly defined compounds, such as salts and their
crystallo-hydrates, is so imperceptible, that in denying that
solutions pertain to the number of definite but dissociating
compounds, we risk denying the definiteness of the atomic
composition of such substances as sulphuric acid or of molten
crystallo-hydrates. I repeat, however, that for the present the
theory of solutions cannot be considered as firmly established.
The above opinion about them is nothing more than a hypothesis
which endeavours to satisfy those comparatively limited data
which we have for the present about solutions, and of those
cases of their transition into definite compounds. By submitting
solutions to the Daltonic conception of atomism, I hope that we
may not only attain to a general harmonious chemical doctrine,
but also that new motives for investigation and research will
appear in the problem of solutions, which must either confirm the
proposed theory or replace it by another fuller and truer one;
and I for my part cannot consider this to be the case with any of
the other present doctrines of solutions (note 49).

We saw above that copper sulphate loses four-fifths of its water at 100° and the remainder at 240°. This means that there are two definite compounds of water with the anhydrous salt. Washing soda or carbonate of sodium, Na_{2}CO_{3} separates out as crystals, Na_{2}CO_{3},10H_{2}O, containing 62·9 p.c. of water by weight, from its solutions at the ordinary temperature. When a solution of the same salt deposits crystals at a low temperature, about -20°, then these crystals contain 71·8 parts of water per 28·2 parts of anhydrous salt. Further, the crystals are obtained together with ice, and are left behind when it melts. If ordinary soda, with 62·9 p.c. of water, be cautiously melted in its own water of crystallisation, there remains a salt, in a solid state, containing only 14·5 p.c. of water, and a liquid is obtained which contains the solution of a salt which separates out crystals at 34°, which contain 46 p.c. of water and do not effloresce in air. Lastly, if a supersaturated solution of soda be prepared, then at temperatures below 8° it deposits crystals containing 54·3 p.c. of water. Thus as many as five compounds of anhydrous soda with water are known; and they are dissimilar in their properties and crystalline form, and even in their solubility. It is to be observed that the greatest amount of water in the crystals corresponds with a temperature of -20°, and the smallest to the highest temperature. There is apparently no relation between the above quantities of water and the salts, but this is only because in each case the amount of water and anhydrous salt was given in percentages; but if it be calculated for one and the same quantity of anhydrous salt, or of water, a great regularity will be observed in the amounts of the component parts in all these compounds. It appears that for 106 parts of anhydrous salt in the crystals separated out at -20° there are 270 parts of water; in the crystals obtained at 15° there are 180 parts of water; in the crystals obtained from a supersaturated solution 126 parts, in the crystals which separate out at 34°, 90 parts, and the crystals with the smallest amount of water, 18 parts. On comparing these quantities of water it may easily be seen that they are in simple proportion to each other, for they are all divisible by 18, and are in the ratio 15 : 10 : 7 : 5 : 1. Naturally, direct experiment, however carefully it be conducted, is hampered with errors, but taking these unavoidable experimental errors into consideration, it will be seen that for a given quantity of an anhydrous substance there occur, in several of its compounds with water, quantities of water which are in very simple multiple proportion. This is observed in, and is common to, all definite chemical compounds. This rule is called _the law of multiple proportions_. It was discovered by Dalton, and will be evolved in further detail subsequently in this work. For the present we will only state that the law of definite composition enables the composition of substances to be expressed by formulæ, and the law of multiple proportions permits the application of whole numbers as coefficients of the symbols of the elements in these formulæ. Thus the formula Na_{2}CO_{3},10H_{2}O shows directly that in this crystallo-hydrate there are 180 parts of water to 106 parts by weight of the anhydrous salt, because the formula of soda, Na_{2}CO_{3}, directly answers to a weight of 106, and the formula of water to 18 parts, by weight, which are here taken 10 times.

In the above examples of the combinations of water, we saw the gradually increasing intensity of the bond between water and a substance with which it forms a homogeneous compound. There is a series of such compounds with water, in which the water is held with very great force, and is only given up at a very high temperature, and sometimes cannot be separated by any degree of heat without the entire decomposition of the substance. In these compounds there is generally no outward sign whatever of their containing water. A perfectly new substance is formed from an anhydrous substance and water, in which sometimes the properties of neither one nor the other substance are observable. In the majority of cases, a considerable amount of heat is evolved in the formation of such compounds with water. Sometimes the heat evolved is so intense that a red heat is produced and light is emitted. It is hardly to be wondered at, after this, that stable compounds are formed by such a combination. Their decomposition requires great heat; a large amount of work is necessary to separate them into their component parts. All such compounds are definite, and, generally, completely and clearly definite. The number of such definite compounds with water or _hydrates_, in the narrow sense of the word, is generally inconsiderable for each anhydrous substance; in the greater number of cases, there is formed only one such combination of a substance with water, one hydrate, having so great a stability. The water contained in these compounds is often called _water of constitution_--_i.e._ water which enters into the structure or composition of the given substance. By this it is desired to express, that in other cases the molecules of water are, as it were, separate from the molecules of that substance with which it is combined. It is supposed that in the formation of hydrates this water, even in the smallest particles, forms one complete whole with the anhydrous substance. Many examples of the formation of such hydrates might be cited. The most familiar example in practice is the hydrate of lime, or so-called 'slaked' lime. Lime is prepared by burning limestone, by which the carbonic anhydride is expelled from it, and there remains a white stony mass, which is dense, compact, and rather tenacious. Lime is usually sold in this form, and bears the name of 'quick' or 'unslaked' lime. If water be poured over such lime, a great rise in temperature is remarked either directly, or after a certain time. The whole mass becomes hot, part of the water is evaporated, the stony mass in absorbing water crumbles into powder, and if the water be taken in sufficient quantity and the lime be pure and well burnt, not a particle of the original stony mass is left--it all crumbles into powder. If the water be in excess, then naturally a portion of it remains and forms a solution. This process is called 'slaking' lime. Slaked lime is used in practice in intermixture with sand as mortar. Slaked lime is a definite hydrate of lime. If it is dried at 100° it retains 24·3 p.c. of water. This water can only be expelled at a temperature above 400°, and then quicklime is re-obtained. The heat evolved in the combination of lime with water is so intense that it can set fire to wood, sulphur, gunpowder, &c. Even on mixing lime with ice the temperature rises to 100°. If lime be moistened with a small quantity of water in the dark, a luminous effect is observed. But, nevertheless, water may still be separated from this hydrate.[71] If phosphorus be burnt in dry air, a white substance called 'phosphoric anhydride' is obtained. It combines with water with such energy, that the experiment must be conducted with great caution. A red heat is produced in the formation of the compound, and it is impossible to separate the water from the resultant hydrate at any temperature. The hydrate formed by phosphoric anhydride is a substance which is totally undecomposable into its original component parts by the action of heat. Almost as energetic a combination occurs when sulphuric anhydride, SO_{3}, combines with water, forming its hydrate, sulphuric acid, H_{2}SO_{4}. In both cases definite compounds are produced, but the latter substance, as a liquid, and capable of decomposition by heat, forms an evident link with solutions. If 80 parts of sulphuric anhydride retain 18 parts of water, this water cannot be separated from the anhydride, even at a temperature of 300°. It is only by the addition of phosphoric anhydride, or by a series of chemical transformations, that this water can be separated from its compound with sulphuric anhydride. Oil of vitriol, or sulphuric acid, is such a compound. If a larger proportion of water be taken, it will combine with the H_{2}SO_{4}; for instance, if 36 parts of water per 80 parts of sulphuric anhydride be taken, a compound is formed which crystallises in the cold, and melts at +8°, whilst oil of vitriol does not solidify even at -30°. If still more water be taken, the oil of vitriol will dissolve in the remaining quantity of water. An evolution of heat takes place, not only on the addition of the water of constitution, but in a less degree on further additions of water.[72] And therefore there is no distinct boundary, but only a gradual transition, between those chemical phenomena which are expressed in the formation of solutions and those which take place in the formation of the most stable hydrates.[73]

[71] In combining with water one part by weight of lime evolves 245
units of heat. A high temperature is obtained, because the
specific heat of the resulting product is small. Sodium oxide,
Na_{2}O, in reacting on water, H_{2}O, and forming caustic soda
(sodium hydroxide), NaHO, evolves 552 units of heat for each part
by weight of sodium oxide.

[72] The diagram given in note 28 shows the evolution of heat on the
mixture of sulphuric acid, or monohydrate (H_{2}SO_{4}, _i.e._
SO_{3} + H_{2}O), with different quantities of water per 100
vols. of the resultant solution. Every 98 grams of sulphuric
acid (H_{2}SO_{4}) evolve, on the addition of 18 grams of water,
6,379 units of heat; with twice or three times the quantity of
water 9,418 and 11,137 units of heat, and with an infinitely
large quantity of water 17,860 units of heat, according to the
determinations of Thomsen. He also showed that when H_{2}SO_{4}
is formed from SO_{3} (= 80) and H_{2}O (= 18), 21,308 units
of heat are evolved per 98 parts by weight of the resultant
sulphuric acid.

[73] Thus, for different hydrates the stability with which they hold
water is very dissimilar. Certain hydrates hold water very
loosely, and in combining with it evolve little heat. From
other hydrates the water cannot be separated by any degree of
heat, even if they are formed from anhydrides (_i.e._ anhydrous
substances) and water with little evolution of heat; for
instance, acetic anhydride in combining with water evolves an
inconsiderable amount of heat, but the water cannot then be
expelled from it. If the hydrate (acetic acid) formed by this
combination be strongly heated it either volatilises without
change, or decomposes into new substances, but it does not again
yield the original substances--_i.e._, the anhydride and water,
at least in a liquid form. Here is an instance which gives the
reason for calling the water entering into the composition of the
hydrate, water of constitution. Such, for example, is the water
entering into the so-called caustic soda or sodium hydroxide
(_see_ note 71). But there are hydrates which easily part with
their water; yet this water cannot be considered as water of
crystallisation, not only because sometimes such hydrates have no
crystalline form, but also because, in perfectly analogous cases,
very stable hydrates are formed, which are capable of particular
kinds of chemical reactions, as we shall subsequently learn.
Such, for example, is the unstable hydrated oxide of copper,
which is not formed from water and oxide of copper, but which is
obtained just like far more stable hydrates, for example, the
hydrated oxide of barium BaH_{2}O_{2} equal to BaO + H_{2}O, by
the double decomposition of the solution of salts with alkalies.
In a word, there is no distinct boundary either between the water
of hydrates and of crystallisation, or between solution and
hydration.

It must be observed that in separating from an aqueous solution,
many substances, without having a crystalline form, hold water in
the same unstable state as in crystals; only this water cannot
be termed 'water of crystallisation' if the substance which
separates out has no crystalline form. The hydrates of alumina
and silica are examples of such unstable hydrates. If these
substances are separated from an aqueous solution by a chemical
process, then they always contain water. The formation of a new
chemical compound containing water is here particularly evident,
for alumina and silica in an anhydrous state have chemical
properties differing from those they show when combined with
water, and do not combine directly with it. The entire series of
colloids on separating from water form similar compounds with
it, which have the aspect of solid gelatinous substances. Water
is held in a considerable quantity in solidified glue or boiled
albumin. It cannot be expelled from them by pressure; hence,
in this case there has ensued some kind of combination of the
substance with water. This water, however, is easily separated on
drying; but not the whole of it, a portion being retained, and
this portion is considered to belong to the hydrate, although
in this case it is very difficult, if not impossible, to obtain
definite compounds. The absence of any distinct boundary lines
between solutions, crystallo-hydrates, and ordinary hydrates
above referred to, is very clearly seen in such examples.

We have thus considered many aspects and degrees of combination of various substances with water, or instances of the compounds of water, when it and other substances form new homogeneous substances, which in this case will evidently be complex--_i.e._ made up of different substances--and although they are homogeneous, yet it must be admitted that in them there exist those component parts which entered into their composition, inasmuch as these parts may be re-obtained from them. It must not be imagined that water really exists in hydrate of lime, any more than that ice or steam exists in water. When we say that water occurs in the composition of a certain hydrate, we only wish to point out that there are chemical transformations in which it is possible to obtain that hydrate by means of water, and other transformations in which this water may be separated out from the hydrate. This is all simply expressed by the words, that water enters into the composition of this hydrate. If a hydrate be formed by feeble bonds, and be decomposed even at the ordinary temperature, and be a liquid, then the water appears as one of the products of dissociation, and this gives an idea of what solutions are, and forms the fundamental distinction between them and other hydrates in which the water is combined with greater stability.