He held that every fermentation consisted of molecular motion which is transmitted from a substance in a state of chemical motion - that is, of decomposition - to other substances, the elements of which are loosely held together.
In 1894 and 1895, Fischer, in a remarkable series of papers on the influence of molecular structure upon the action of the enzyme, showed that various species of yeast behave very differently towards solutions of sugars.
Let us now imagine what degree of transparency of air is admitted by its molecular constituents, viz.
In 1831, from a study of the specific heats of compounds, he formulated "Neumann's law," which expressed in modern language runs: "The molecular heat of a compound is equal to the sum of the atomic heats of its constituents."
In such experiments the molecular energy of a gas is converted into work only in virtue of the molecules being separated into classes in which their velocities are different, and these classes then allowed to act upon one another through the intervention of a suitable heat-engine.
The molecular weight determinations of W.
The extent of the area affected and of the variation in the turgor depends upon many circumstances, but we have no doubt that in the process of modifying its own permeability by some molecular change we have the counterpart of muscular contractibility.
The alkyl derivatives may be obtained by heating phenol with one molecular proportion of a caustic alkali and of an alkyl iodide.
Hantzsch (Ber., 1901, 34, p. 3337) has shown that in the action of alcohols on diazonium salts an increase in the molecular weight of the alcohol and an accumulation of negative groups in the aromatic nucleus lead to a diminution in the yield of the ether produced and to the production of a secondary reaction, resulting in the formation of a certain amount of an aromatic hydrocarbon.
This oxide exists in two forms. The aform is readily fusible and melts at 14.8° C. It corresponds to the simple molecular complex S03.
It corresponds to the molecular complex (S03)2.
With Sydney Young and others he investigated the critical state and properties of liquids and the relationship between their vapour pressures and temperature, and with John Shields he applied measurements of the surface tension of liquids to the determination of their molecular complexity.
Chemistry and physics, however, meet on common ground in a well-defined branch of science, named physical chemistry, which is primarily concerned with the correlation of physical properties and chemical composition, and, more generally, with the elucidation of natural phenomena on the molecular theory.
In place of the relative molecular weights, attention was concentrated on relative atomic or equivalent weights.
Gerhardt found that reactions could be best followed if one assumed the molecular weight of an element or compound to be that weight which occupied the same volume as two unit weights of hydrogen, and this assumption led him to double the equivalents accepted by Gmelin, making H= 1, 0 =16, and C = 12, thereby agreeing with Berzelius, and also to halve the values given by Berzelius to many metals.
From a study of the free elements Cannizzaro showed that an element may have more than one molecular weight; for example, the molecular weight of sulphur varied with the temperature.
Thus, the symbols 14 2 and P4 indicate that the molecules of hydrogen and phosphorus respectively contain 2 and 4 atoms. Since, according to the molecular theory, in all cases of chemical change the action is between molecules, such symbols as these ought always to be employed.
The molecular formula of a compound, however, is always a simple multiple of the empirical formula, if not identical with it; thus, the empirical formula of acetic acid is CH 2 O, and its molecular formula is C2H402, or twiceTCH 2 O.
they appear to differ in character; but if they are correctly represented by molecular equations, or equations which express the relative number of molecules which enter into reaction and which result from the reaction, it will be obvious that the character of the reaction is substantially the same in both cases, and that both are instances of the occurrence of what is ordinarily termed double decomposition H2 + C12 = 2HC1 Hydrogen.
This view was modified by Liebig, who regarded ether as ethyl oxide, and alcohol as the hydrate of ethyl oxide; here, however, he was in error, for he attributed to alcohol a molecular weight double its true value.
He also postulated, with Regnault, the existence of " molecular or mechanical types " containing substances which, although having the same number of equivalents, are essentially different in characters.
the molecular weights were the same as in use to-day.) This connecting link, C2, was regarded as essential, while the methyl, ethyl, &c. was but a sort of appendage; but Kolbe could not clearly conceive the manner of copulation.
isomerism, or the existence of two or more chemically different substances having identical molecular weights, is adequately shown; and, most important of all, once the structure is determined, the synthesis of the compound is but a matter of time.
These bands are due to molecular oscillations; Hartley suggests the carbon atoms to be rotating and forming alternately single and double linkages, the formation of three double links giving three bands, and of three single links another three; Baly and Collie, on the other hand, suggest the making and breaking of links between adjacent atoms, pointing out that there are seven combinations of one, two and three pairs of carbon atoms in the benzene molecule.
The first set provides evidence as to the molecular weight of a substance: these are termed " colligative properties."
In any attempts to gain an insight into the relations between the physical properties and chemical composition of substances, the fact must never be ignored that a comparison can only be made when the particular property under consideration is determined under strictly comparable conditions, in other words, when the molecular states of the substances experimented upon are identical.
When this is done, such densities are measures of the molecular weights of the substances in question.
Deviation from this rule indicates molecular dissociation or association.
It is found that isomers have nearly the same critical volume, and that equal differences in molecular content occasion equal differences in critical volume.
Kopp, begun in 1842, on the molecular volumes, the volume occupied by one gramme molecular weight of a substance, of liquids measured at their boiling-point under atmospheric pressure, brought to light a series of additive relations which, in the case of carbon compounds, render it possible to predict, in some measure, the cornposition of the substance.
In practice it is generally more convenient to determine the density, the molecular volume being then obtained by dividing the molecular weight of the substance by the density.
These values hold fairly well when compared with the experimental values determined from other compounds, and also with the molecular volumes of the elements themselves.
Recent researches have shown that the law originally proposed by Kopp - " That the specific volume of a liquid compound (molecular volume) at its boiling-point is equal to the sum of the specific volumes of its constituents (atomic volumes), and that every element has a definite atomic value in its compounds " - is by no means exact, for isomers have different specific volumes, and the volume for an increment of CH 2 in different homologous series is by no means constant; for example, the difference among the esters of the fatty acids is about 57, whereas for the aliphatic aldehydes it is 49.
We may therefore conclude that the molecular volume depends more upon the internal structure of the molecule than its empirical content.
The molecular volume is additive in certain cases, in particular of analogous compounds of simple constitution.
Schroeder the silver salts of the fatty acids exhibit additive relations; an increase in the molecule of CH2 causes an increase in the molecular volume of about 15'3.
From the ratio Cp/C„ conclusions may be drawn as to the molecular condition of the gas.
456) has given the formula Cp=6.5--aT, where a is a constant depending on the complexity of the molecule, as an expression for the molecular heat at constant pressure at any temperature T (reckoned on the absolute scale).
We now proceed to discuss molecular heats of compounds, that is, the product of the molecular weight into the specific heat.
Regnault confirmed Neumann's observations, and showed that the molecular heat depended on the number of atoms present, equiatomic compounds having the same molecular heat.
Kopp systematized the earlier observations, and, having made many others, he was able to show that the molecular heat was an additive property, i.e.
Similarly, by taking the difference of the molecular heats of compounds differing by one constituent, the molecular (or atomic) heat of this constituent is directly obtained.
It may he shown theoretically that the absolute boiling-point is proportional to the molecular volume, and, since this property is additive, the boiling-point should also be additive.
These relations have been more thoroughly tested in the case of organic compounds, and the results obtained agree in some measure with the deductions from molecular volumes.
Mag., 18 93 [5), 35, p. 45 8) has shown that, while an increase in molecular weight is generally associated with a rise in the boiling-point, yet the symmetry of the resulting molecule may exert such a lowering effect that the final result is a diminution in the boiling-point.
The series H 2 S = - 61°, CH 3 SH = 21 °, (C 11 3) 2 S=41 ° is an example; in the first case, the molecular weight is increased and the symmetry diminished, the increase of boiling-point being 82°; in the second case the molecular weight is again increased but the molecule assumes a more symmetrical configuration, hence the comparatively slight increase of 20°.
He introduced the idea of comparing the refractivity of equimolecular quantities of different substances by multiplying the function (n-1)/d by the molecular weight (M) of the substance, and investigated the relations of chemical grouping to refractivity.
Although establishing certain general relations between atomic and molecular refractions, the results were somewhat vitiated by the inadequacy of the empirical function which he employed, since it was by no means a constant which depended only on the actual composition of the substance and was independent of its physical condition.
compounds having the same composition, have equal molecular refractions, and that equal differences in composition are associated with equal differences in refractive power.
This is shown in the following table (the values are for Ha) Additive relations undoubtedly exist, but many discrepancies occur which may be assigned, as in the case of molecular volumes, to differences in constitution.
Atomic refractions may be obtained either directly, by investigating the various elements, or indirectly, by considering differences in the molecular refractions of related compounds.
By subtracting the value for CH 2, which may be derived from two substances belonging to the same homologous series, from the molecular refraction of methane, CH 4, the value of hydrogen is obtained; subtracting this from CH 2, the value of carbon is determined.
Hydroxylic oxygen is obtained by subtracting the molecular refractions of acetic acid and acetaldehyde.
A table of the atomic refractions and dispersions of the principal elements is here given: Dispersion and Composition.-In the preceding section we have seen that substances possess a definite molecular (or atomic) refraction for light of particular wave-length; the difference between the refractions for any two rays is known as the molecular (or atomic) dispersion.
Since molecular refractions are independent of temperature and of the state of aggregation, it follows that molecular dispersions must be also independent of these conditions; and hence quantitative measurements should give an indication as to the chemical composition of substances.
We may here notice an empirical rule formulated by Nietzski in 1879: - the simplest colouring substances are in the greenish-yellow and yellow, and with increasing molecular weight the colour passes into orange, red, violet, blue and green.
It may be generally inferred that an increase in molecular weight is accompanied by a change in colour in the direction of the violet.
Hydrocarbons of similar structure have been prepared by Thiele, for example, the orange-yellow tetraphenyl-para-xylylene, which is obtained by boiling the bromide C6H4[CBr(C6H5)2]2 with benzene and molecular silver.
(3) If a colourless compound gives a coloured one on solution or by salt-formation, the production of colour may be explained as a particular form of ionization (Baeyer), or by a molecular rearrangement (Hantzsch).
Mendeleeff endeavoured to obtain a connexion between surface energy and constitution; more successful were the investigations of Schiff, who found that the " molecular surface tension," which he defined as the surface tension divided by the weight.
molecular weight, is constant for isomers, and that two atoms of hydrogen were equal to one of carbon, three to one of oxygen, and seven to one of chlorine; but these ratios were by no means constant, and afforded practically no criteria as to the molecular weight of any substance.
2 7, p. 45 2), assuming that two liquids may be compared when the ratios of the volumes of the liquids to the volumes of the saturated vapours are the same, deduced that yV 3 (where y is the surface tension, and V the molecular volume of the liquid) causes all liquids to have the same temperature coefficients.
Soc. 63, p. 1089; 65, p. 167), whose results have thrown considerable light on the subject of the molecular complexity of liquids.
Obviously equimolecular surfaces are given by (Mv) 3, where M is the molecular weight of the substance, for equimolecular volumes are Mv, and corresponding surfaces the two-thirds power of this.
Now the value of K, -y being measured in dynes and M being the molecular weight of the substance as a gas, is in general 2.121; this value is never exceeded, but in many cases it is less.
In order to permit a comparison of crystal forms, from which we hope to gain an insight into the prevailing molecular conditions, it is necessary that some unit of crystal dimensions must be chosen.
To reduce these figures to a common standard, so that the volumes shall contain equal numbers of molecules, the notion of molecular volumes is introduced, the arbitrary values of the crystallographic axes (a, b, c) being replaced by the topic parameters' (x, ?i, w), which are such that, combined with the axial angles, they enclose volumes which contain equal numbers of molecules.
Kryst., 1894), in his researches on the tetragonal potassium and ammonium dihydrogen phosphates and arsenates, found that the replacement of potassium by ammonium was attended by an increase of about six units in the molecular volume, and of phosphorus by arsenic by about 4.6 units.
Chloraloxime, CC1 3 CH: NOH, is obtained when one molecular proportion of chloral hydrate is warmed with four molecular proportions of hydroxylamine hydrochloride and a little water.
It crystallizes in prisms which melt at 39° C. A chloral hydroxylamine, CC1 3 [[Choh Nhoh]], melting at 98° C. is obtained by allowing a mixture of one molecular proportion of chloral hydrate with two molecular proportions of hydroxylamine hydrochloride and one of sodium carbonate to stand for some time in a desiccator.
18.14%, S=0.96%, O = 22.66%, which points to the formula C720H1134N218S50241, corresponding to the molecular weight 16,954.
A high molecular weight characterizes these substances, but so far no definite value has been determined by either physical or chemical means; A.
For instance, to take the two solutions to which we have already referred, we have of ions between molecules at the instants of molecular collision only; during the rest of the life of the ions they were regarded as linked to each other to form electrically neutral molecules.
In 1887 Svante Arrhenius, professor of physics at Stockholm, put forward a new theory which supposed that the freedom of the opposite ions from each other was not a mere momentary freedom at the instants of molecular collision, but a more or less permanent freedom, the ions moving independently of each other through the liquid.
Molecular Depressions of the Freezing Point.
The evidence in favour of dissociation in the case of solutions does not apply to fused salts, and it is possible that, in their case, a series of molecular interchanges, somewhat like Grotthus's chain, may represent the mechanism of conduction.
If µ be the molecular conductivity, and its value at infinite dilution, the fractional number of molecules dissociated is k /µop, which we may write as a.
a V(I - a) This constant k gives a numerical value for the chemical affinity, and the equation should represent the effect of dilution on the molecular conductivity of binary electrolytes.
The equation then becomes a 2 /V = k, or a = A / Vk, so that the molecular conductivity is proportional to the square root of the dilution.
According to the molecular theory, diffusion is due to the motion of the molecules of the dissolved substance through the liquid.
Under certain conditions, as when latex is allowed to stand or is centrifugalized, a cream is obtained consisting of the liquid globules, which may be washed free from proteid without change, but, either by mechanical agitation or by the addition of acid or other chemical agent, the liquid gradually solidifies to a mass of solid caoutchouc. The phenomenon therefore resembles the change known to the chemist as polymerization, by which through molecular aggregation a liquid may pass into a solid without change in its empirical composition.
The properties of caoutchouc clearly show, however, that its actual molecular structure is considerably more complex than is represented by the empirical formula, and that it is to be regarded as the polymer of a terpene or similar hydrocarbon and composed of a cluster of at least ten or twenty molecules of the formula C5H8.
The exact chemical nature of caoutchouc is, however, not determined, and recent researches point to the view that its molecular structure may even be somewhat different from that of the terpenes.
Molecular Theory of Magnetism.
One of the fragments may again be broken, and again two bipolar magnets will be produced; and the operation may be repeated, at least in imagination, till we arrive at molecular magnitudes and can go no farther.
This experiment proves that the condition of magnetization is not confined to those parts where polar phenomena are exhibited, but exists throughout the whole body of the magnet; it also suggests the idea of molecular magnetism, upon which the accepted theory of magnetization is based.
The process of magnetization consists in turning round the molecules by the application of magnetic force, so that their north poles may all point more or less approximately in the direction of the force; thus the body as a whole becomes a magnet which is merely the resultant of an immense number of molecular magnets.
These observations have an important bearing upon the molecular theory of magnetism, which will be referred to later.
Weber's theory of molecular magnetism.
The width of the gap may be diminished until it is no greater than the distance between two neighbouring molecules, when it will cease to be distinguishable, but, assuming the molecular theory of magnetism to be true, the above statement will still hold good for the intermolecular gap. The same pressure P will be exerted across any imaginary section of a magnetized rod, the stress being sustained by the intermolecular springs, whatever their physical nature may be, to which the elasticity of the metal is due.
This explanation was not accepted by Wiedemann,' who thought that the effect was accounted for by molecular friction.
Until the mysteries of molecular constitution have been more fully explored, perhaps D may be most properly regarded as the fundamental phenomenon from which the others follow.
Among other researches relating to atomic and molecular magnetism are those of 0.
Molecular Theory Of Magnetism According to W.
Soc., 1890, 48, 342) has demonstrated that it is quite unnecessary to assume either the directive force of Weber, the permanent set of Maxwell, or any kind of frictional resistance, the forces by which the molecular magnets are constrained being simply those due to their own mutual attractions and repulsions.
With small magnetizing forces the hysteresis was indeed somewhat larger than that obtained in an alternating field, probably on account of the molecular changes being forced to take place in one direction only; but at an induction of about 16,00o units in soft iron and 15,000 in hard steel the hysteresis reached a maximum and afterwards rapidly diminished.
In one case the hysteresis loss per cubic centimetre per cycle was 16,100 ergs for B =1 5,900, and only 1200 ergs for B = 20,200, the highest induction obtained in the experiment; possibly it would have vanished before B had reached 21,000.2 These experiments prove that actual friction must be almost entirely absent, and, as Baily remarks, the agreement of the results with the previously suggested deduction affords a strong verification of Ewing's form of the molecular theory.
The fact being established that magnetism is essentially a molecular phenomenon, the next step is to inquire what is the constitution of a magnetic molecule, and why it is that some molecules are ferromagnetic, others paramagnetic, and others again diamagnetic. The best known of the explanations that have been proposed depend upon the magnetic action of an electric current.
Since that date it has more than once been suggested that the molecular currents producing magnetism might be due to the revolution of one or more of the charged atoms or " ions " constituting the molecule.
Diamagnetism, in short, is an atomic phenomenon; paramagnetism and ferromagnetism are molecular phenomena.
Weber's molecular theory, which has already been referred to, appeared in 1852.5 An event of the first importance was the discovery made in 1819 by H.
Ampere's experimental and theoretical investigation of the mutual action of electric currents, and of the equivalence of a closed circuit to a polar magnet, the latter suggesting his celebrated hypothesis that molecular currents were the cause of magnetism.
2 His well-known modification 3 of Weber's molecular theory, published in 1890, presented for the first time a simple and sufficient explanation of hysteresis and many other complexities of magnetic quality.
In the German Patent 1 57573 (1904) it is shown that by the action of at least two molecular proportions of an alkyl formate on two molecular proportions of a magnesium alkyl or aryl haloid, a complex addition compound is formed, which readily decomposes into a basic magnesium salt and an aldehyde, C H MgBr-f-H000R-ROï¿½CHï¿½C H.
Molecular physics also attracted his notice, and he announced in 1824 his purpose of treating the subject in a separate work.
But the increase of size which constitutes growth is the result of a process of molecular intussusception, and therefore differs altogether from the process of growth by accretion, which may be observed in crystals and is effected purely by the external addition of new matter - so that, in the well-known aphorism of Linnaeus, the word "grow" as applied to stones signifies a totally different process from what is called "growth" in plants and animals.
This, however, is not exactly accurate, if it be thereby implied that all living things have a visible organization, as there are numerous forms of living matter of which it cannot properly be said that they possess either a definite structure or permanently specialized organs: though, doubtless, the simplest particle of living matter must possess a highly complex molecular structure, which is far beyond the reach of vision.
A mass of living protoplasm is simply a molecular machine of great complexity, the total results of the working of which, or its vital phenomena, depend - on the one hand, Life con- of this water is absolutely incompatible with either moister by a ctual or potential life.
No method has yet been devised by which the molecular weight can be ascertained.'
conceptions will be opened out, not in bacteriology only, but also in biological chemistry and in molecular physics.
Now, what is remarkable in these and many other reactions is not only that effects apparently very opposite may result from minute differences of molecular construction, but also that, whatever the construction, agents, not wholly indifferent to the body or part, tend to anchor themselves to organic molecules in some way akin to them.
Putting (12) a vortex line is defined to be such that the tangent is in the direction of w, the resultant of, n, called the components of molecular rotation.
Projected perpendicularly against a plane boundary, the motion is determined by an equal opposite vortex ring, the optical image; the vortex ring spreads out and moves more slowly as it approaches the wall; at the same time the molecular rotation, inversely as the cross-section of the vortex, is seen to increase.
The plane projection of molecular structures which differ stereochemically is discussed under Stereoisomerism; in this place it suffices to say that, since the terminal groups of the hexaldose molecule are different and four asymmetric carbon atoms are present, sixteen hexaldoses are possible; and for the hexahydric alcohols which they yield on reduction, and the tetrahydric dicarboxylic acids which they give on oxidation, only ten forms are possible.
In regard to methods and apparatus, mention should be made of his improvements in the technique of organic analysis, his plan for determining the natural alkaloids and for ascertaining the molecular weights of organic bases b y means of their chloroplatinates, his process for determining the quantity of urea in a solution - the first step towards the introduction of precise chemical methods into practical medicine - and his invention of the simple form of condenser known in every laboratory.
The present article, as explained under Electrochemistry, treats only of those processes in which electricity is applied to the production of chemical reactions or molecular changes at furnace temperatures.
the production of graphite from coke or gas-carbon) the heat is applied solely to the production of molecular or physical changes.
Titanium trichloride, TiC131 forms involatile, dark violet scales, and is obtained by passing the vapour of the tetrachloride mixed with hydrogen through a red-hot tube, or by heating the tetrachloride with molecular silver to 200°.
The tertiary amines possess the power of combining with one molecular proportion of an alkyl iodide to form quaternary ammonium salts.
The composition of the distillate is determinate (by Avogadro's law) if the molecular weights and vapour pressure of the components at the temperature of distillation be known.
If M 1, M2, and P 1, P 2 be the molecular weights and vapour pressures of the components A and B, then the ratio of A to B in the distillate is M 1 P 1 /M 2 P 2.
P 1 greater than P2, if the molecular weight of A be much less than that of B, then it is obvious that the ratio M 1 P 1 /M 2 P 2 need not be very great, and hence the less volatile liquid B would come over in fair amount.
These con-, ditions pertain in cases where distillation with steam is successfully practised, the relatively high volatility of water being counterbalanced by the relatively high molecular weight of the other component; for example, in the case of nitrobenzene and water the ratio is I to 5.
He wrote a lucid account of the phenomena of phosphorescence, and adduced a molecular magnetic theory which anticipated some of the chief features of the hypothesis of to-day.
The isomerism which occurs as soon as the molecule contains a few carbon atoms renders any classification based on empirical molecular formulae somewhat ineffective; on the other hand, a scheme based on molecular structure would involve more detail than it is here possible to give.
When a quantity of heat, H, is supplied to a body, part is expended in raising the temperature of the body, or in expanding the volume against molecular forces, and is represented by an increase in the total quantity of energy contained in the body, which is generally called its Intrinsic Energy, and will be denoted by the symbol E.
The energy is less than that of an ideal gas by the term npc. If we imagine that the defect of volume c is due to the formation of molecular aggregates consisting of two or more single molecules, and if the kinetic energy of translation of any one of these aggregates is equal to that of one of the single molecules, it is clear that some energy must be lost in co-aggregating, but that the proportion lost will be different for different types of molecules and also for different types of co-aggregation.
If the molecules and molecular aggregates were more complicated, and the number of degrees of freedom of the aggregates were limited to 6, or were the same as for single molecules, we should have n-= so/R.
M, Molecular weight.
The problem of the stresses in rarefied gaseous media arising from inequalities of temperature, which is thereby opened out, involves some of the most delicate considerations in molecular physics.
In later memoirs Reynolds followed up this subject by proceeding to establish definitions of the velocity and the momentum and the energy at an element of volume of the molecular medium, with the precision necessary in order that the dynamical equations of the medium in bulk, based in the usual manner on these quantities alone, without directly considering thermal stresses, shall be strictly valid - a discussion in which the relation of ordinary molar mechanics to the more complete molecular theory is involved.
Hull, with the result that there is a certain pressure at which the molecular effect of the gas.
The density gives very important information as to the molecular weight, since by the law of Avogadro it is seen that the relative density is the ratio of the molecular weights of the experimental and standard gases.
This subject owes its importance in modern chemistry to the fact that the vapour density, when hydrogen is taken as the standard, gives perfectly definite information as to the molecular condition of the compound, since twice the vapour density equals the molecular weight of the compound.
Biltz, Practical Methods for determining Molecular Weights (1899).
For the detailed chemical significance of these terms, see Chemistry; and for the atomic theory of the chemist (as distinguished from the atomic or molecular theory of the physicist) see Atom; reference may also be made to the article Matter.
The leading historical stages in the evolution of the modern conception of the molecular structure of matter are treated in the following passage from James Clerk Maxwell's article Atom in the 9th edition of the Ency.
" The opposite school maintained then, as they have always done, 1 It wiII be noted that Clerk Maxwell's " atom " and " atomic theory " have the significance which we now attach to " molecule " and " molecular theory."
In this way the science of hydrostatics may be built upon an experimental basis, without any consideration of the constitution of a fluid as to whether it is molecular or continuous.
THE Molecular Structure Of Matter An enormous mass of experimental evidence now shows quite conclusively that matter cannot be regarded as having a continuous structure, but that it is ultimately composed of discrete parts.
In point of fact it is found that the properties which are most easily explained are those connected with the gaseous state; the explanation of these properties in terms of the molecular structure of matter is the aim of the " Kinetic Theory of Gases."
The results of this theory have placed the molecular conception of matter in an indisputable position, but even without this theory there is such an accumulation of electrical and optical evidence in favour of the molecular conception of matter that the tenability of this conception could not be regarded as open to question.
Apart from speculation, the first definite evidence for the molecular structure of matter occurs when it is found that certain physical phenomena change their whole nature as soon as we deal with matter of which the linear dimensions are less than a certain amount.
The agreement of the values obtained for the same quantity by different methods provides valuable confirmation of the truth of the molecular theory and of the validity of the methods of the kinetic theory of gases.
Roughly speaking, it is found that there are three main types of molecular motion corresponding to the three states of matter - solid, liquid and gaseous.
As a preliminary to examining further into the nature of molecular motion and the differences of character of this motion, let us try to picture the state of things which would exist in a mass of solid matter in which all the molecules are imagined to be at rest relatively to one another.
Thus the molecular theory of matter, as we have now pictured it, leads us to identify heat-energy in a body with the energy of motion of the molecules of the body relatively to one another.
The point of view which has now been gained enables us to interpret most of the thermal properties of solids in terms of molecular theory.
This is the conception which the molecular theory compels us to form of the gaseous state.
In terms of the molecular theory this indicates that the total energy of the gas is the sum of the separate energies of its different molecules: the potential energy arising from intermolecular forces between pairs of molecules may be treated as negligible when the matter is in the gaseous state.
The kinetic theory of gases attempts to give a mathematical account, in terms of the molecular structure of matter, of all the non-chemical and non-electrical properties of gases.
The determination of the series of configurations developing out of given initial conditions is not, however, the problem of the kinetic theory: the object of this theory is to explain the general properties of all gases in terms only of their molecular structure.
If in formula Molecular (?3) we put p=I 013X10 6, (v +v'+ ..
If p is the density corresponding to pressure p, we find that,}, formula (Ii) assumes the form P = 3PC2, where C is a velocity such that the gas would have its actual translational energy if each molecule moved with the same velocity C. By substituting experimentally determined pairs of values of p and p we can calculate C for different gases, and so obtain a knowledge of the magnitudes of the molecular velocities.
von Nageli's investigations on molecular structure and the growth of the cell membrane we recognize the origin of modern methods of the study of cellstructure included under cytology.
Soc., 1889, 55, p. 163) determined the vapour density of hydrofluoric acid at different temperatures, and showed that there is no approach to a definite value below about 88° C. where it reaches the value 10.29 corresponding to the molecular formula HF; at temperatures below 88° C. the value increases rapidly, showing that the molecule is more complex in its structure.
But in the transition from molecular theory to the electrodynamics of extended media, all magnetism has to be replaced by a distribution of current; the latter being now specified by volume as well as by flow so that (u,v,w) ST is the current in the element of volume 6T.
Lorentz, on the general lines suggested by the electron-theory of molecular constitution.
This fact, coupled with the determination of the vapour density of the gas, establishes the molecular formula CO.
This was based on the assumption that the medium in which the light is propagated is discontinuous and molecular in character, the molecules being subject to a mutual attraction.
Silver cyanide, AgNC, is formed as a white precipitate by adding potassium cyanide to silver nitrate solution; or better, by adding silver nitrate to potassium silver cyanide, KAg(NC) 2, this double cyanide being obtained by the addition of one molecular proportion of potassium cyanide to one molecular proportion of silver nitrate, the white precipitate so formed being then dissolved by adding a second equivalent of potassium cyanide.
In many of these salts one finds that the elements of water are frequently found in combination with the metal, and further, that the ammonia molecule may be replaced by such other molecular groups as - N02, &c. Of the types studied the following may be mentioned: the diammine chromium thiocyanates, M[Cr(NH3)2 (SCN)4], the chloraquotetrammine chromic salts, R 1 2 [Cr(NH 3) 4 H 2 0 C1], the aquopentammine or roseo-chromium salts,R 1 3 [Cr(NH 3) 6.
They may also be obtained by the molecular rearrangement of the diazoamines, when these are warmed with the parent base and its hydrochloride.
Spectrum analysis thus passed quickly out of the stage in which its main purpose was " analysis " and became our most delicate and powerful method of investigating molecular properties; the old name being no longer appropriate, we now speak of the science of " Spectroscopy."
When the molecule is losing energy the intensity of each kind of radiation depends principally on the rapidity with which it can be renewed by molecular impacts.
Radiation is a molecular process, and we can speak of the radiation of a molecule but not of its temperature.
highest temperatures at our command it is small compared with the energy of translatory motion, but as the temperature increases, it must ultimately gain the upper hand, and if there is anywhere such a temperature as that of several million degrees, the greater part of the total energy of a body will be outside the atom and molecular motion ultimately becomes negligible compared with it.
The homogeneity of vibration may also be diminished by molecular impacts, but the number of shocks in a given time depends on pressure and we may therefore expect to diminish the width of a line by diminishing the pressure.
It is not, however, obvious that the sudden change of direction in the translatory motion, which is commonly called a molecular shock, necessarily also affects the phase of vibration.
Such spectra seem to be characteristic of complex molecular structure, as they appear when compounds are raised to incandescence without decomposition, or when we examine the absorption spectra of vapours such as iodine and bromine and other cases where we know that the molecule consists of more than one atom.
If the medium which contains the vibration is divided into a sphere equal to k times the molecular vibration outside of which the effects of these molecules may be averaged up, so that its Roy.
The subject wants further investigation, especially with a view to deciding the connexion between the molecular rush and the discharge.
While some of the phenomena seem to indicate that the projection of metallic vapours into the centre of the spark is a process of molecular diffusion independent of the mechanism of the discharge, the different velocities obtained with bismuth, and the probability that the vibrating systems are not electrically neutral, seem to indicate that the projected metallic particles are electrified and play some part in the discharge.
When we now speak of the identification of spectra we like to include, wherever possible, the identification of the particular compound which is luminous and even - though we have only begun to make any progress in that direction - the differentiation between the molecular or electronic states which yield the different spectra of the same element.
To explain this great variability of spectroscopic effects we may either adopt the view that molecular aggregates of semi-stable nature may be found in vacuum tubes, or that a molecule may gain or lose one or more additional electrons and thus form new vibrating systems. It seemed that an important guide to clear our notions in this direction could be obtained through the discovery of J.
It will be remembered that Fechner regarded every composite body as the appearance of a spirit; so that when, for example, molecular motion of air is said to cause a sensation of sound in me, it is really a spirit appearing as air which causes the sensation in my spirit.
He ingeniously suggested that the external agent is one feeling regarded objectively, and the internal effect another feeling regarded subjectively; " and therefore," to quote his own words, " to say that it is a molecular movement which produces a sensation of sound, is equivalent to saying that a sensation of sight produces a sensation of hearing."
That orthoboric acid is a tribasic acid is shown by the formation of ethyl orthoborate on esterification, the vapour density of which corresponds to the molecular formula B(0C2H5)3; the molecular formula of the acid must consequently be B(OH) 3 or H 3 B0 3.
The original memoirs themselves on radiant heat and on magnetism were collected and issued as two large volumes under the following titles: Diamagnetism and Magne-crystallic Action (1870); Contributions to Molecular Physics in the Domain of Radiant Heat (1872).
The process of cooling is thus represented by a path which runs vertically downwards till it cuts the 0 Molecular Percentage of Na t S04 Siluer Copper FIG.
On the fundamental hypotheses of the molecular theory, Value we must regard a solution as composed of a number osmotic of separate particles of solute, scattered through- p out the solvent.
A quantity of gas measured by its molecular weight in grammes when confined in a volume of one litre exerts a pressure of 22.2 atmospheres, and thus the osmotic pressure of a dilute solution divided by its concentration in gramme-molecules per litre has a corresponding value.
In the vapour pressure equation p - p' = Pa/p, we have the vapour density equal to M/v 1, where M is the molecular weight of the solvent.
Each molecular complex, formed by solution and solvent, is treated as a single molecule.
The solution of sodium aluminate, containing aluminium oxide and sodium oxide in the molecular proportion of 6 to 1, is next agitated for thirty-six hours with a small quantity of hydrated alumina previously obtained, which causes the liquor to decompose, and some 70% of the aluminium hydroxide to be thrown down.
But carbon affects the properties of iron not only by giving rise to varying proportions of cementite, but also both by itself shifting from one molecular state to another, and by enabling us to hold the iron itself in its unmagnetic allotropic forms, 0and 7-iron, as will be explained below.
In the cold this transformation cannot take place, because of molecular rigidity or some A C VII' B Solid ' Legend' ustenite diagram = Comentite-Austenite diagram show) for comparison ...
Primary a Austenite 'Molten Metal ' usually to between 200° and 300° C., so as to relax the molecular rigidity and thereby to allow the arrested transformation to go on a little farther, shifting a little of the 0-iron over into the a state.
that to which the hardened steel is thus reheated, the more is the molecular rigidity relaxed, the farther on does the transformation go, and the softer does the steel become; so that, if the reheating reaches a dullred heat, the transformation from austenite into ferrite and cementite completes itself slowly, and when now cooled the steel is as soft and ductile as if it had never been hardened.
The molecular freedom which this high temperature gives enables the cementite to change gradually into a mixture of graphite and austenite with the result that, after the castings have been cooled and their austenite has in cooling past Aci changed into pearlite and ferrite, the mixture of cementite and pearlite of which they originally consisted has now given place to one of fine or " temper " graphite and ferrite, with more or less pearlite according to the completeness of the transfer of the carbon to the state of graphite.
In carrying out this process the castings are packed in a mass of iron oxide, which at this temperature gradually removes the fine or " temper " graphite by oxidizing that in the outer crust to carbonic oxide, whereon the carbon farther in begins diffusing outwards by " molecular migration," to be itself oxidized on reaching the crust.
Jochem (Ber., 1901, 34, p. 3337), who arrived at the conclusion that the normal decomposition of diazonium salts by alcohols results in the formation of phenolic ethers, but that an increase in the molecular weight of the alcohol, or the accumulation of negative groups in the aromatic nucleus, diminishes the yield of the ether and increases the amount of the hydrocarbon formed.
On mixing dilute solutions of the diazonium hydroxide and the alkali together, it is found that the molecular conductivity of the mixture is much less than the sum of the two electrical conductivities of the solutions separately, from which it follows that a portion of the ions present have changed to the non-ionized condition.
Cryoscopic determinations of its molecular weight show that it is H 2 0 2.
The one group included those isomers where the identity in composition was accompanied by identity in molecular weight, i.e.
the vapour densities of the isomers were the same, as in butylene and isobutylene, to take the most simple case; here the molecular conception admits that the isolated groups in which the atoms are united, i.e.
iroXb, many) was chosen for compounds like butylene, C 4 H 8, and ethylene, C 2 H 4, corresponding to the same composition in weight but differing in molecular formula, and having different densities in gas or vapour, a litre of butylene and isobutylene weighing, for instance, under ordinary temperature and pressure, about 2.5 gr., ethylene only one-half as much, since density is proportional to molecular weight.
Polymerism required no particular explanation, since this was given by the difference in molecular magnitude.
The cases of mutual transformation are generally characterized by the fact that in the compound of higher molecular weight no new links of carbon with carbon are introduced, the trioxymethylene being O CH2-0 CH 2 whereas honey-sugar correg probably C C H 2 -0% sponds to CH 2 0H [[Choh Choh Choh Choh Cho]], each point representing a linking of the carbon atom to the next.
The conception of metamerism, or isomerism in restricted sense, has been of the highest value for the development of our notions concerning molecular structure, i.e.
By Wilhelm Ostwald especially, attempts have been made to substitute the notion of atoms and molecular structure by less hypothetical conceptions; these ideas may some day receive thorough confirmation, and when this occurs science will receive a striking impetus.
The third most valuable indication which molecular structure gives about these isomers is how to prepare them, for instance, that normal hexane, represented by CH 3 CH 2 CH 2 CH 2 CH 2 CH3, may be obtained by action of sodium on propyl iodide, CH 3 CH 2 CH 2 I, the atoms of iodine being removed from two molecules of propyl iodide, with the resulting fusion.
In this equation a relates to molecular attraction; and it is not improbable that in isomeric molecules, containing in sum the same amount of the same atoms, those mutual attractions are approximately the same, whereas the chief difference lies in the value of b, that is, the volume occupied by the molecule itself.
Now taking the isomers H 3 C CC1 3 (M„ = 108) and C1H 2 C CHC1 2 (M„ = we see the negative chlorine atoms heaped up in the left hand formula, but distributed in the second; the former therefore may be presumed to occupy a larger space, the molecular volume, that is, the volume in cubic centimetres occupied by the molecular weight in grams, actually being 108 in the former, and 103 in the latter case (compare Chemistry: Physical).
Conduction, however, is generally understood to include diffusion of heat in fluids due to the agitation of the ultimate molecules, which is really molecular convection.
Its vapour density has been determined by Nilson and Pettersson, and corresponds to the molecular formula BeC12.
According to Rabuteau the toxic properties of the higher alcohols increase with their molecular weight and boiling point.
Perceiving a molecular isonomy between them and the inorganic compounds of the metals from which they may be formed, he saw their true molecular type in the oxygen, sulphur or chlorine compounds of those metals, from which he held them to be derived by the substitution of an organic group for the oxygen, sulphur, &c. In this way they enabled him to overthrow the theory of conjugate compounds, and they further led him in 1852 to publish the conception that the atoms of each elementary substance have a definite saturation capacity, so that they can only combine with a certain limited number of the atoms of other elements.
The Well Known Experiments Of Regnault And Wiedemann On The Specific Heat Of Gases At Constant Pressure Agree In Showing That The Molecular Specific Heat, Or The Thermal Capacity Of The Molecular Weight In Grammes, Is Approximately Independent Of The Temperature And Pressure In Case Of The More Stable Diatomic Gases, Such As 112,02, N2, Co, &C., And Has Nearly The Same Value For Each Gas.
Since Much Smaller Values Are Found For More Complex Molecules, We May Suppose That, In These Cases, The Energy Of Rotation Of A Polyatomic Molecule May Be Greater Than Its Energy Of Translation, Or Else That Heat Is Expended In Splitting Up Molecular Aggregates, And Increasing Energy Of Vibration.
Atomic And Molecular Heats.
For A Diatomic Gas, The Molecular Heat Would Be Nearly Five Calories, Or The Atomic Heat Of A Gas In The Diatomic State Would Be 2.5.
No Doubt There Must Be Approximate Relations Between The Atomic And Molecular Heats Of Similar Elements And Compounds, But Considering The Great Variations Of Specific Heat With Temperature And Physical State, In Alloys, Mixtures Or Solutions, And In Allotropic Or Other Modifications, It Would Be Idle To Expect That The Specific Heat Of A Compound Could Be Accurately Deduced By Any Simple Additive Process From That Of Its Constituents.
For example, from the evidence of molar changes due to the obvious parts of bodies, science first comes to believe in molecular changes due to imperceptible particles, and then tries to conceive the ideas of particles, molecules, atoms, electrons.
(The human soul is still an exception.) Form is bound up with the molecular structure and change of structure of a body, one of whose qualities or activities it expresses in wider relations.
(8) where is the molecular weight of the vapour, and R the gasconstant which is nearly 2 calories per degree for a gramme-molecule of gas.
The most important apparent exceptions to Raoult's law in dilute solutions are the cases, (I) in which the molecules of the dissolved substance in solution are associated to form compound molecules, or dissociated to form other combinations with the solvent, in such a way that the actual number of molecules n in the solution differs from that calculated from the molecular weight corresponding to the accepted formula of the dissolved substance; (2) the case in which the molecules of the vapour of the solvent are associated in pairs or otherwise so that the molecular weight m of the vapour is not that corresponding to its accepted formula.
p. 631) showed how to calculate the effective number of molecules n" = (1 +ek/ko)n,from the molecular conductivity k of the solution and its value ko at infinite dilution, for an electrolyte giving rise to e +I ions.
The theory of the ionization of salts in solution has raised much discussion amongst chemists, but the general fact is certain that electricity only moves through liquids in association with matter, and simultaneously involves chemical dissociation of molecular groups.
The next step is to deduce this surface-tension from a hypothesis as to the molecular constitution of the liquid and of the bodies that surround it.
The scientific importance of this step is to be measured by the degree of insight which it affords or promises into the molecular constitution of real bodies by the suggestion of experiments by which we may discriminate between rival molecular theories.
But for those who wish to study the molecular constitution of bodies it is necessary to study the effect of forces which are sensible only at insensible distances; and Laplace has furnished us with an example of the method of this study which has never been surpassed.
The only difference is in the manner in which this quantity H depends on the law of the molecular forces and the law of density near the surface of the fluid, and as these laws are unknown to us we cannot obtain any test to discriminate between the two theories.
The experimental evidence which Dupre obtained bearing on the molecular structure of liquids must be very valuable, even if our present opinions on this subject should turn out to be erroneous.
[The continued coexistence of various thicknesses, as evidenced by the colours in the same film, affords an instantaneous proof of this conclusion.] The phenomena of very thin liquid films deserve the most careful study, for it is in this way that we are most likely to obtain evidence by which we may test the theories of the molecular structure of liquids.
If, however, it were negative, the displacement of the liquids which tends to enlarge the surface of contact would be aided by the molecular forces, so that the liquids, if not kept separate by gravity, would at length become thoroughly mixed.
In such a film it is possible that no part of the liquid may be so far from the surface as to have the potential and density corresponding to what we have called the interior of a liquid mass, and measurements of the tension of the film when drawn out to different degrees of thinness may possibly lead to an estimate of range of the molecular forces, or at least of the depth within a liquid mass, at which its properties become sensibly uniform.
We shall therefore endeavour to apply to this subject the methods used in Thermodynamics, and where these fail us we shall have recourse to the hypotheses of molecular physics.
Integrating with respect to f from f =z to f=a, where a is a line very great compared with the extreme range of the molecular force, but very small compared with either of the radii of curvature, we obtain for the work (1,G (z) - 111(a))dw, and since (a) is an insensible quantity we may omit it.
Hence the tension is the same for all films thicker than e, the range of the molecular forces.
In fact, the quantity 41rp 2 K, which we may call with van der Waals the molecular pressure, is so great for most liquids (5000 atmospheres for water), that in the parts near the surface, where the molecular pressure varies rapidly, we may expect considerable variation of density, even when we take into account the smallness of the compressibility of liquids.
Suppose that the transition from o to s is made in two equal steps, the thickness of the intermediate layer of density la being large compared to the range of the molecular forces, but small in comparison with the radius of curvature.
All such phenomena, however, are likewise due to the disturbance of the molecular constitution of living cells.
Still another view, advocated by Bordet, is that the union of toxin and antitoxin is rather of physical than of strictly chemical nature, and represents an interaction of colloidal substances, a sort of molecular deposition by which the smaller toxin molecule becomes entangled in the larger molecule of antitoxin.
In 1844, by experiments on the tenacity of soap-bubbles, he showed that the molecular cohesion of water is equal (if not superior) to that of ice, and hence, generally, that solids and their liquids have practically the same amount of cohesion (Proc. Am.
Molecular silver is a grey powder obtained by leaving metallic zinc in contact with silver chloride which has been precipitated in the cold and washed till nearly free from acid.
Hydrobromic acid is one of the "strong" acids, being ionized to a very large extent even in concentrated solution, as shown by the molecular conductivity increasing by only a small amount over a wide range offdilution.
For the molecular theory of absorption, see SPECTROSCOPY.
It exists in two forms, one having the formula P 4 5 10, and the other a lower molecular weight.
The term "perfect gas" is applied to an imaginary substance in which there is no frictional retardation of molecular motion; or, in other words, the time during which any molecule is influenced by other molecules is infinitesimally small compared with the time during which it traverses its mean free path.
It also dissolves in alcohol and ether; boiling point determinations of the molecular weight in these solutions point to the formula FeCl3.
Her other works are the Connexion of the Physical Sciences (1834), Physical Geography (1848), and Molecular and Microscopic Science (1869).
Divers obtains it by mixing cold saturated solutions containing one molecular proportion of sodium nitrate, and two molecular proportions of acid sodium sulphite, and then adding a saturated solution of potassium chloride to the mixture.
It has been maintained, on the one hand, that any theory which presupposes a direct correspondence between the molecular movements of the brain, and the states of consciousness which accompany them must make the freedom of the will impossible.
No direct causal relationship between a molecular movement and a state of consciousness has ever been established.
And many scientific thinkers, while professing allegiance to a theory which insists upon the independence of each parallel series, in reality tacitly assume the superior importance if not the controlling force of the physical over the psychical terms. But a mere insistence upon the complete independence of the physical series coupled with the belief that its changes are wholly explicable as modes of motion, that the study of molecular physics is competent to explain all the phenomena of life and organic movements, is sufficient to eliminate the possibility of spontaneity and free origination from the universe.
The physical properties of the alcohols exhibit a gradation with the increase of molecular weight.
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