Technology compounds over time.
The astringent principle is a peculiar kind of tannic acid, called by chemists quercitannic, which, yielding more stable compounds with gelatine than other forms, gives oak bark its high value to the tanner.
By using urea, guanidine, thiourea and related compounds instead of amidines, one obtains the uracils.
For the preparation of yttrium compounds the best raw material is gadolinite, which, according to Kiinig, consists of 22.61% of silica, 34.64.
Pure terbium compounds were obtained by G.
His first original paper (1799) was on the compounds of arsenic and antimony with oxygen and sulphur, and of his other separate investigations one of the most important was that on the compound ethers, begun in 1807.
Molybdenum combines with the halogen elements in varying proportions, forming with chlorine a di-, tri-, tetraand penta-chloride, and similar compounds with bromine and iodine.
Those Fungi which are saprophytic can only live when supplied with organic compounds of some complexity, which they derive from decomposing animal or vegetable matter.
Habitats rich in mineral salts, especially calcium carbonate, poor in acidic humous compounds, and characterized by ash woods, beech woods, and calcareous pasture.
Civilization, like technology, also compounds over time, as do its benefits.
The symbols of compounds become very concise, as the number of atoms of one kind in a molecule can be expressed by a sub-index.
A study of the whole vegetable kingdom, however, negatives the theory that the compounds absorbed are in the strict sense to be called food.
In addition, certain inorganic salts, particularly certain compounds of potassium, are apparently necessary, but they seem to take no part in the chemical changes which take place.
It is frequently used as a reducing agent: in acid solutions it reduces ferric to ferrous salts, arsenates to arsenites, permanganates to manganous salts, &c., whilst in alkaline solution it converts many organic nitro compounds into the corresponding amino derivatives.
Compounds were represented by copulating simpler symbols, e.g.
The mono-amino derivatives or eurhodines are obtained when the arylmonamines are condensed with orthoamino zo compounds; by condensing quinone dichlorimide or para-nitrosodimethyl aniline with monamines containing a free para position, or by oxidizing ortho-hydroxydiaminodiphenylamines (R.
He was the first to discover uranium, zirconium and titanium, and to characterize them as distinct elements, though he did not obtain any of them in the pure metallic state; and he elucidated the composition of numerous substances till then imperfectly known, including compounds of the then newly recognized elements: tellurium, strontium, cerium and chromium.
Now, as the materials which plants absorb are carbon dioxide from the air, and various inorganic compounds from the soil, together with water, it is clear that if this view is correct, vegetable protoplasm must be fed in a very different way from animal, and on very different materials.
When the young sporophyte first begins its independent lifewhen, that is, it exists in the form of the embryo in the seedits living substance has no power of utilizing the simple inorganic compounds spoken of.
As the action of the chlorophyll apparatus is directly dependent upon light, and the immediate result of its activity is the building up of complex compounds, it has become usual to speak of the processes it sets up under the name of photosynthesis.
Similar observations have been made in the case of various compounds of nitrogen, though these have not been so complex as the proteids.
The law of multiple proportions asserts that if two elements form more than' one compound, then the weights of the one element Law of which are found combined with unit weight of the other multiple in the different compounds, must be in the ratio of two propor or more whole numbers.
345), that only compounds containing two carbon atoms yielded fulminates, points to (Hcno) 2; on the other hand, Wohler (loc. cit.
If chemical compounds can be proved by experiment to obey these laws, then the atomic theory acquires a high degree of probability; if they are contradicted by experiment then the atomic theory must be abandoned, or very much modified.
A large number of cobalt compounds are known, of which the empirical composition represents them as salts of cobalt to which one or more molecules of ammonia have been added.
Fermentation now includes all changes in organic compounds brought about by ferments elaborated in the living animal or vegetable cell.
PYRIMIDINES, METADIAZINES or Miazines, in organic chemistry, a series of heterocyclic compounds containing a ring complex, composed of four carbon atoms and two nitrogen atoms, the nitrogen atoms being in the meta-position.
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."
At one of your compounds.
This is one of D's compounds.
the formation of nitrites and nitrates from ammonia and its compounds in the soil, was formerly held to be a purely chemical process, until Schloesing and Mintz suggested in 1877 that it was biological.
They are solid crystalline compounds.
On the other hand, they show faintly acid properties since the hydrogen: of the amido group can be replaced by metals to give such compounds as mercury acetamide (CH 3 CONH) 2 Hg.
Cell Membrane.The membrane which surrounds the protoplasts in the majority of plants is typically composed of cellulose, together with a number of other substances which are known as pectic compounds.
In the Fungi it is usually composed of a modified form of cellulose known as fungus cellulose, which, according to Mangin, consists of callose in combination either with cellulose or pectic compounds.
They are compounds which greatly resemble the mixed ethers of the aliphatic series.
Columbus is near the Ohio coal and iron-fields, and has an extensive trade in coal, but its largest industrial interests are in manufactures, among which the more important are foundry and machine-shop products (1905 value, $6,259,579); boots and shoes (1905 value, $5,425,087, being more than one-sixtieth of the total product value of the boot and shoe industry in the United States, and being an increase from $359,000 in 1890); patent medicines and compounds (1905 value, $3,214,096); carriages and wagons (1905 value, $2,197,960); malt liquors (1905 value, $2,133,955); iron and steel; regalia and society emblems; steam-railway cars, construction and repairing; and oleo-margarine.
So also other compounds of api-.
Germanium compounds on fusion with alkaline carbonates and sulphur form salts known as thiogermanates.
Alkyl compounds of germanium such as germanium tetra-ethyl, Ge(C2H5)4, a liquid boiling at C., have been obtained.
Gaseous compounds, e.g.
Several halogen compounds of sulphur are known, the most stable of which is sulphur fluoride, SF 6, which was first prepared by H.
Walden (ibid.) has shown that certain salts dissolve in liquid sulphur dioxide forming additive compounds, two of which have been prepared in the case of potassium iodide: a yellow crystalline solid of composition, KI 14 S0 2, and a red solid of composition, KI 4S0 2.
It reacts most energetically with many organic compounds, removing the elements of water in many cases and leaving a carbonized mass.
It combines directly with many elements and compounds and frequently acts as energetic oxidizing agent.
Several compounds of a type introduced by W.
- For thermochemical calculations it is of great importance to know the heat of formation of compounds from their elements, even when the combination cannot be brought about directly.
Since heats of formation afford such convenient data for calculation on the above method, they have been ascertained for as many compounds as possible.
Amongst endothermic compounds may be noted hydriodic acid, HI, acetylene, C 2 H 2, nitrous oxide, N 2 O, nitric oxide, NO, azoimide, N 3 H, nitrogen trichloride, NC1 3.
Neither of the above rules can be applied to carbon compounds containing nitrogen.
Perhaps the most remarkable discovery of modern chemistry is the existence of compounds, which, whilst possessing an identical composition, are absolutely different bodies, judged of by their properties.
Of the nitrogenous compounds in food, on the other hand, only a small proportion of the whole consumed is finally stored up in the increase of the animal - in other words, a very large amount of nitrogen passes through the body beyond that which is finally retained in the increase, and so remains for manure.
Commercially, barytes is used in the preparation of barium compounds, as a body for certain kinds of paper and cloth, and as a white pigment ("permanent white").
In the presence of a dehydrating agent (such as acetic anhydride), it combines with aldehydes to form compounds of the type R CH: C(COOH) 2, or their decomposition products (formed by loss of C02) R CH: CH COOH.
It is found that transparent oils under the influence of light absorb oxygen, becoming deeper in colour and opalescent, while strong acidity and a penetrating odour are developed, these changes being due to the formation of various acid and phenylated compounds, which are also occasionally found in fresh oils.
SOAP, a chemical compound or mixture of chemical compounds resulting from the interaction of fatty oils and fats with alkalis.
In a scientific definition the compounds of fatty acids with basic metallic oxides, lime, magnesia, lead oxide, &c., should also be included under soap; but, as these compounds are insoluble in water, while the very essence of a soap in its industrial relations is solubility, it is better to speak of the insoluble compounds as " plasters, " limiting the name " soap " as the compounds of fatty acids with soda and potash.
Resin soaps are compounds of soda or potash with the complex acids (chiefly abietic) of which coniferous resins consist.
Similar systems of symbols, but elaborated to include compounds, appear in Greek MSS.
9), violent and ecstatic exercises, ceremonial acts of bowing and kissing, the preparing of sacred mystic cakes, appear among the offences denounced by the Israelite prophets, and show that the cult of Baal (and Astarte) included the characteristic features of heathen worship which recur in various parts of the Semitic world, although attached to other names.5 By an easy transition the local gods of the streams and springs which fertilized the increase of the fields became identified with 2 Compounds with geographical terms (towns, mountains), e.g.
The peroxide, Ru04, is formed when a solution of potassium ruthenate is decomposed by chlorine, or by oxidizing ruthenium compounds with potassium chlorate and hydrochloric acid, or with potassium permanganate and sulphuric acid.
On the nitroso, nitroso-ammonium and nitroso-diammonium compounds see C. E.
Marine Gasteropods are occasionally termed "sea-snails," and the compounds "pond-snails," "river-snails," "water-snails" are in common use.
tempus opportunum), which occurs as part of many compounds.
The fundamental chemical classification of matter, on the other hand, recognizes two groups of substances, namely, elements, which are substances not admitting of analysis into other substances, and compounds, which do admit of analysis into simpler substances and also of synthesis from simpler substances.
This section includes a brief history of the subject, and proceeds to treat of the principles underlying the structure and interrelations of organic compounds.
The analysis of organic compounds is also noticed.
At the same time he clarified the conception of elements and compounds, rejecting the older notions, the four elements of the " vulgar Peripateticks " and the three principles of the " vulgar Stagyrists," and defining an element as a substance incapable of decomposition, and a compound as composed of two or more elements.
To him is also due a rigorous examination of the nature of elements and compounds; he held the same views that were laid down by Boyle, and with the same prophetic foresight predicted that some of the elements which he himself accepted might be eventually found to be compounds.
The beginning of the i 9th century was attended by far-reaching discoveries in the nature of the composition of compounds.
that fixed proportions of elements and compounds combine only under exceptional conditions, the general rule being that the composition of a compound may vary continuously between certain limits.2
This may be due in some measure to the small number of gaseous and easily volatile substances then known, to the attention which the study of the organic compounds received, and especially to the energetic investigations of J.
Compounds were denoted by joining the symbols of the components, and by varying the manner of joining compounds of the same elements were distinguished The symbol V was used to denote a liquid, and a vertical line to denote a gas.
If two compounds combined, the + signs of the free compounds were discarded, and the number of atoms denoted by an Arabic index placed after the elements, and from these modified symbols the symbol of the new compound was derived in the same manner as simple compounds were built up from their elements.
with the adoption of simple rules as a first attempt at representing a compound, he availed himself of other data in order to gain further information as to the structure of compounds.
While successfully investigating the solid elements and their compounds gravimetrically, Berzelius was guilty of several inconsistencies in his views on gases.
The gradual accumulation of data referring to organic compounds brought in its train a revival of the discussion of atoms and molecules.
And from the study of compounds he showed that each element occurred in a definite weight or in some multiple of this weight.
This generalization was of great value inasmuch as it permitted the deduction of the atomic weight of a non-gasifiable element from a study of the densities of its gasifiable compounds.
From a detailed study of organic compounds Gerhardt had promulgated a " theory of types " which represented a fusion of the older radical and type theories.
This theory brought together, as it were, the most varied compounds, and stimulated inquiry into many fields.
ously studied by Sir Edward Frankland, who from the investigation, not of simple inorganic compounds, but of the organo-metallic derivatives, determined the kernel of the theory of valency.
He regarded the chemical properties of a substance as due to (1) the chemical atoms composing it, and (2) the structure, and he asserted that while different compounds might have the same components (isomerism), yet only one compound could have a particular structure.
Such isomerism, named stereoisomerism (q.v.),hasbeen assiduously developed during recentyears; it prevails among many different classes of organic compounds and many examples have been found in inorganic chemistry.
Hydrogen and oxygen are, therefore, of very opposite natures, and this is well illustrated by the circumstance that oxygen combines, with very few exceptions, with all the remaining elements, whilst compounds of only a limited number with hydrogen have been obtained.
For example, compounds of oxygen are oxides, of chlorine, chlorides, and so on.
The affixes -ous and sub- refer to the compounds containing more of the positive element, -ic and per- to those containing less.
Compounds in which all the units of affinity of the contained elements are engaged are said to be saturated, whilst those in which the affinities of the contained elements are not all engaged by other elements are said to be unsaturated.
According to this view, it is necessary to assume that, in all unsaturated compounds, two, or some even number of affinities are disengaged; and also that all elements which combine with an even number of monad atoms cannot combine with an odd number, and vice versa, - in other words, that the number of units of affinity active in the case of any given element must be always either an even or an odd number, and that it cannot be at one time an even and at another an odd number.
Again, when tungsten hexachloride is converted into vapour it is decomposed into chlorine and a pentachloride, having a normal vapour density, but as in the majority of its compounds tungsten acts as a hexad, we apparently must regard its pentachloride as a compound in which an odd number of free affinities are disengaged.
It is often convenient to regard compounds as formed upon certain types; alcohol, for example, may be said to be a compound formed upon the water type, that is to say, a compound formed from water by displacing one of the atoms of hydrogen by the group of elements C 2 H 5, thus - H C2H5 O H O H Water Alcohol.
- Chemical change or chemical action may be said to take place whenever changes occur which involve an alteration in the composition of molecules, and may be the result of the action of agents such as heat, electricity or light, or of two or more elements or compounds upon each other.
Changes of the first and second kind, according to our views of the constitution of molecules, are probably of very rare occurrence; in fact, chemical action appears almost always to involve the occurrence of both these kinds of change, for, as already pointed out, we must assume that the molecules of hydrogen, oxygen and several other elements are diatomic, or that they consist of two atoms. Indeed, it appears probable that with few exceptions the elements are all compounds of similar atoms united together by one or more units of affinity, according to their valencies.
These compounds also afford examples of the fact that, generally speaking, those compounds are most readily formed, and are most stable, in the formation of which the most heat is developed.
In this, as in most other cases in which substances act upon one another under such circumstances that the resulting compounds are free to react, the extent to which the different kinds of action which may occur take place is dependent upon the mass of the substances present in the mixture.
Inorganic Chemistry Inorganic chemistry is concerned with the descriptive study o f the elements and their compounds, except those of carbon.
Reference should be made to the separate articles on the different elements and the more important compounds for their preparation, properties and uses.
Among the Arabian and later alchemists we find attempts made to collate compounds by specific properties, and it is to these writers that we are mainly indebted for such terms as "alkali," " sal," &c. The mineral acids, hydrochloric, nitric and sulphuric acids, and also aqua regia (a mixture of hydrochloric and nitric acids) were discovered, and the vitriols, alum, saltpetre, sal-ammoniac, ammonium carbonate, silver nitrate (lunar caustic) became better known.
The compounds of mercury attracted considerable attention, mainly on account of their medicinal properties; mercuric oxide and corrosive sublimate were known to pseudo-Geber, and the nitrate and basic sulphate to " Basil Valentine."
The action of these acids on many metals was also studied; Glauber obtained zinc, stannic, arsenious and cuprous chlorides by dissolving the metals in hydrochloric acid, compounds hitherto obtained by heating the metals with corrosive sublimate, and consequently supposed to contain mercury.
The scientific study of salts dates from this period, especial interest being taken in those compounds which possessed a medicinal or technical value.
Antimonial, bismuth and arsenical compounds were assiduously studied, a direct consequence of their high medicinal importance; mercurial and silver compounds were investigated for the same reason.
Returning to the history of the discovery of the elements and their more important inorganic compounds, we come in 1789 to M.
The great number and striking character of the compounds of this group of metals have formed the subject of many investigations, and already there is a most voluminous literature.
Cleve, the first to make a really thorough study of these elements and their compounds.
Of especial note are the curious compounds formed by the union of carbon monoxide with platinous chloride, discovered by Paul Schiitzenberger and subsequently investigated by F.
Foerster and by Pullinger; the phosphoplatinic compounds formed primarily from platinum and phosphorus pentachloride; and also the " ammino " compounds, formed by the union of ammonia with the chloride, &c., of these metals, which have been studied by many chemists, especially S.
The beginning of the 19th century witnessed the discovery of certain powerful methods for the analysis of compounds and the isolation of elements.
In the same year Berzelius discovered selenium in a deposit from sulphuric acid chambers, his masterly investigation including a study of the hydride, oxides and other compounds.
Thenard discovered hydrogen dioxide, one of the most interesting inorganic compounds known, which has since been carefully investigated by H.
Matthiessen in 1855, who obtained the metal by electrolysis and thoroughly examined it and its compounds.
We may, in fact, consider that the descriptive study of the various halogen compounds dates from about this time.
del Rio; subsequent elaborate researches by Sir Henry Roscoe showed many inaccuracies in the conclusions of earlier workers (for instance, the substance considered to be the pure element was in reality an oxide) and provided science with an admirable account of this element and its compounds.
These elements occur in the minerals columbite and tantalite, and their compounds became known in the early part of the 19th century by the labours of C. Hatchett, A.
Nilson, and subsequently (1904) by Hall, rendered notable additions to our knowledge of these elements and their compounds.
Of other phosphorus compounds we may here notice Gengembre's discovery of phosphuretted hydrogen (phosphine) in 1783, the analogy of which to ammonia was first pointed out by Davy and supported at a later date by H.
Of the halogen compounds of phosphorus, the trichloride was discovered by Gay Lussac and Thenard, while the pentachloride was obtained by Davy.
The oxychloride, bromides, and other compounds were subsequently discovered; here we need only notice Moissan's preparation of the trifluoride and Thorpe's discovery of the pentafluoride, a compound of especial note, for it volatilizes unchanged, giving a vapour of normal density and so demonstrating the stability of a pentavalent phosphorus compound (the pentachloride and pentabromide dissociate into a molecule of the halogen element and phosphorus trichoride).
The term allotropy has also been applied to inorganic compounds, identical in composition, but assuming different crystallographic forms. Mercuric oxide, sulphide and iodide; arsenic trioxide; titanium dioxide and silicon dioxide may be cited as examples.
In the separation of the constituents of the complex mixture of oxides obtained from the " rare earth " minerals, the methods generally forced upon chemists are those of fractional precipitation or crystallization; the striking resemblances of the compounds of these elements rarely admitting of a complete separation by simple precipitation and filtration.
Of recent years the introduction of various organic compounds as precipitants or reagents has reduced the labour of the process; and advantage has also been taken of the fairly complex double salts which these metals form with compounds.
The purity of the compounds thus obtained is checked by spectroscopic observations.
After having been somewhat neglected for the greater attractions and wider field presented by organic chemistry, the study of the elements and their inorganic compounds is now' rapidly coming into favour; new investigators are continually entering the lists; the beaten paths are being retraversed and new ramifications pursued.
Organic Chemistry While inorganic chemistry was primarily developed through the study of minerals - a connexion still shown by the French appellation chimie minerale - organic chemistry owes its origin to the investigation of substances occurring in the vegetable and animal organisms. The quest of the alchemists for the philosopher's stone, and the almost general adherence of the iatrochemists to the study of the medicinal characters and preparation of metallic compounds, stultified in some measure the investigation of vegetable and animal products.
It is true that by the distillation of many herbs, resins and similar substances, several organic compounds had been prepared, and in a few cases employed as medicines; but the prevailing classification of substances by physical and; superficial properties led to the correlation of organic and inorganic compounds, without any attention being paid to their chemical composition.
Taking as a basis the nature of the source of compounds, he framed three classes: " mineral," comprising the metals, minerals, earths and stones; " vegetable," comprising plants, resins, gums, juices, &c.; and " animal," comprising animals, their different parts and excreta.
Theoretical speculations were revived by Lavoisier, who, having explained the nature of combustion and determined methods for analysing compounds, concluded that vegetable substances ordinarily contained carbon, hydrogen and oxygen, while animal substances generally contained, in addition to these elements, nitrogen, and sometimes phosphorus and sulphur.
Lavoisier, to whom chemistry was primarily the chemistry of oxygen compounds, having developed the radical theory initiated by Guyton de Morveau, formulated the hypothesis that vegetable and animal substances were oxides of radicals composed of carbon and hydrogen; moreover, since simple radicals (the elements) can form more than one oxide, he attributed the same character to his hydrocarbon radicals: he considered, for instance, sugar to be a neutral oxide and oxalic acid a higher oxide of a certain radical, for, when oxidized by nitric acid, sugar yields oxalic acid.
At the same time, however, he adhered to the classification of Lemery; and it was only when identical compounds were obtained from both vegetable and animal sources that this subdivision was discarded, and the classes were assimilated in the division organic chemistry.
At this time there existed a belief, held at a later date by Berzelius, Gmelin and many others, that the formation of organic compounds was conditioned by a so-called vital force; and the difficulty of artificially realizing this action explained the supposed impossibility of synthesizing organic compounds.
In addition to the vitalistic doctrine of the origin of organic compounds, views based on purely chemical considerations were advanced.
Berzelius, in 1813 and 1814, by improved methods of analysis, established that the Daltonian laws of combination held in both the inorganic and organic kingdoms; and he adopted the view of Lavoisier that organic compounds were oxides of compound radicals, and therefore necessarily contained at least three elements - carbon, hydrogen and oxygen.
2 Compound radicals came to be regarded as the immediate constituents of organic compounds; and, at first, a determination of their empirical composition was supposed to be sufficient to characterize them.
However, in 1833, Berzelius reverted to his earlier opinion that oxygenated radicals were incompatible with his electrochemical theory; he regarded benzoyl as an oxide of the radical C 14 H 1Q, which he named " picramyl " (from 7rucp6s, bitter, and &uvyalk, almond), the peroxide being anhydrous benzoic acid; and he dismissed the views of Gay Lussac and Dumas that ethylene was the radical of ether, alcohol and ethyl chloride, setting up in their place the idea that ether was a suboxide of ethyl, (C2H5)20, which was analogous to K 2 0, while alcohol was an oxide of a radical C 2 H 6; thus annihilating any relation between these two compounds.
Bunsen, the discoverer of the cacodyl compounds.
According to this theory a " chemical type " embraced compounds containing the same number of equivalents combined in a like manner and exhibiting similar properties; thus acetic and trichloracetic acids, aldehyde and chloral, marsh gas and chloroform are pairs of compounds referable to the same type.
According to Gerhardt, the process of substitution consisted of the union of two residues to fo- m a unitary whole; these residues, previously termed " compound radicals," are atomic complexes which remain over from the interaction of two compounds.
Similarly he represented the reactions investigated by Liebig and Wehler on benzoyl compounds as double decompositions.
Williamson showed how alcohol and ether were to be regarded as derived from water by substituting one or both hydrogen atoms by the ethyl group; he derived acids and the acid anhydrides from the same type; and from a comparison of many inorganic and the simple organic compounds he concluded that this notion of a " water-type " clarified, in no small measure, the conception of the structure of compounds.
Taking as types hydrogen, hydrochloric acid, water and ammonia, he postulated that all organic compounds were referable to these four forms: the hydrogen type included hydrocarbons, aldehydes and ketones; the hydrochloric acid type, the chlorides, bromides and iodides; the water type, the alcohols, ethers, monobasic acids, acid anhydrides, and the analogous sulphur compounds; and the ammonia type, the amines, acid-amides, and the analogous phosphorus and arsenic compounds.
He rejected the Berzelian tenet as to the unalterability of radicals, and admitted that they exercised a considerable influence upon the compounds with which they were copulated.
From similar investigations of valerianic acid he was led to conclude that fatty acids were oxygen compounds of the radicals hydrogen, methyl, ethyl, &c., combined with the double carbon equivalent C2.
The brilliant researches of Frankland on the organo-metallic compounds, and his consequent doctrine of saturation capacity or valency of elements and radicals, relieved Kolbe's views of all obscurity.
The doctrine of copulae was discarded, and in 1859 emphasis was given to the view that all organic compounds were derivatives of inorganic by simple substitution processes.
He was thus enabled to predict compounds which were then unknown.
the secondary and tertiary alcohols; and with inestimable perspicacity he proved intimate relations between compounds previously held to be quite distinct.
The " structure theory " (or the mode of linking of the atoms) of carbon compounds, founded by Butlerow, Kekule and Couper and, at a later date, marvellously enhanced by the doctrine of stereo-isomerism, due to J.
Classification of Organic Compounds.
into two groups: (r) those exhibiting properties closely analogous to the aliphatic series - the polymethylenes, and (2) a series exhibiting properties differing in many respects from the aliphatic and polymethylene compounds, and characterized by a peculiar stability which is to be associated with the disposition of certain carbon valencies not saturated by hydrogen - the " aromatic series."
There also exists an extensive class of compounds termed the " heterocyclic series " - these compounds are derived from ring systems containing atoms other than carbon; this class is more generally allied to the aromatic series than to the aliphatic.
We now proceed to discuss the types of aliphatic compounds; then, the characteristic groupings having been established, an epitome of their derivatives will be given.
Accepting the doctrine of the tetravalency of carbon (its divalency in such compounds as carbon monoxide, various isocyanides, fulminic acid, &c., and its possible trivalency in M.
Three such compounds are possible according to the number of valencies acting directly between the carbon atoms. Thus, if they are connected by one valency, and the remaining valencies saturated by hydrogen, we obtain the compound H 3 C CH 3, ethane.
These last two compounds are termed unsaturated, whereas ethane is saturated.
It will be noticed that compounds containing two double linkages will have the same general formula as the acetylene series; such compounds are known as the " diolefines."
Hydrocarbons containing any number of double or triple linkages, as well as both double and triple linkages, are possible, and a considerable number of such compounds have been prepared.
CH(CH3) CH2 CH31 from isobutane we may also derive two compounds, one identical with (2), and a new one (3) CH 3 (CH 3)C(CH 3)CH 3.
Deferring the detailed discussion of cyclic or ringed hydrocarbons, a correlation of the various types or classes of compounds which may be derived from hydrocarbon nuclei will now be given.
and >- CH, the first characterizing the polymethylene and reduced heterocyclic compounds, the second true aromatic compounds.
OH, >CH OH, and ?C OH; these compounds are known as alcohols (q.v.), and are termed primary, secondary, and tertiary respectively.
Polymethylenes can give only secondary and tertiary alcohols, benzene only tertiary; these latter compounds are known as phenols.
Compounds containing the group - CH: O are known as aldehydes (q.v.), while the group >C: O (sometimes termed the carbonyl or keto group) characterizes the ketones (q.v.).
Sulphur analogues of these oxygen compounds are known.
We may also notice that thio-ethers combine with alkyl iodides to form sulphide or sulphonium compounds, R3; SI.
These compounds may be regarded as oxides in just the same way as the alcohols are regarded as hydroxides.
Organic acids also condense with alcohols to form similar compounds: the fats, waxes, and essential oils are naturally occurring substances of this class.
An important class of compounds, termed amines (q.v.), results from the condensation of alcohols with ammonia, water being eliminated between the alcoholic hydroxyl group and a hydrogen atom of the ammonia.
From the primary amines are derived the diazo compounds and azo compounds; closely related are the hydrazines (q.v.).
compounds containing an oxy in addition to an aldehydic or ketonic group) undergo both condensation and oxidation when treated with phenylhydrazine, forming compounds known as osozones; these are of great importance in characterizing the sugars (q.v.).
The carboxyl group constitutes another convenient startingpoint for the orientation of many types of organic compounds.
This group may be considered as resulting from the fusion of a carbonyl (:CO) and a hydroxyl (HO-) group; and we may expect to meet with compounds bearing structural resemblances to the derivatives of alcohols and aldehydes (or ketones).
The structural relations of these compounds are here shown: R C0.
It is necessary clearly to distinguish such compounds as the amino- (or amido-) acids and acid-amides; in the first case the amino group is substituted in the hydrocarbon residue, in the second it is substituted in the carboxyl group.
By transformations of the carbonyl group, and at the same time of the hydroxyl group, many interesting types of nitrogen compounds may be correlated.
Here we meet with a great diversity of types: oxygen, nitrogen, sulphur and other elements may, in addition to carbon, combine together in a great number of arrangements to form cyclic nuclei, which exhibit characters closely resembling open-chain compounds in so far as they yield substitution derivatives, and behave as compound radicals.
In classifying closed chain compounds, the first step consists in dividing them into: (1) carbocyclic, in which the ring is composed solely of carbon atoms - these are also known as homocyclic or isocyclic on account of the identity of the members of the ring - and (2) heterocyclic, in which different elements go to make up the ring.
A similar behaviour has since been noticed in other trimethylene derivatives, but the fact that bromine, which usually acts so much more readily than hydrobromic acid on unsaturated compounds,, should be so inert when hydrobromic acid acts readily is one still.
B aeyer has suggested that his hypothesis may also be applied to explain the instability of acetylene and its derivatives, and the still greater instability of the polyacetylene compounds.
From these nuclei an immense number of derivatives may be obtained, for the hydrogen atoms may be substituted by any of the radicals discussed in the preceding section on the classification of organic compounds.
This and other facts connected with the stability of benzenoid compounds are clearly shown when we consider mixed aliphatic-aromatic hydrocarbons, i.e.
compounds derived by substituting aliphatic radicals in the benzene nucleus; such a compound is methylbenzene or toluene, C 6 H 5 CH 3.
In general, the aliphatic residues in such mixed compounds retain the characters of their class, while the aromatic residues retain the properties of benzene.
Further differences become apparent when various typical compounds are compared.
The introduction of hydroxyl groups into the benzene nucleus gives rise to compounds generically named phenols, which, although resembling the aliphatic alcohols in their origin, differ from these substances in their increased chemical activity and acid nature.
The amines also exhibit striking differences: in the aliphatic series these compounds may be directly formed from the alkyl haloids and ammonia, but in the benzene series this reaction is quite impossible unless the haloid atom be weakened by the presence of other substituents, e.g.
Mixed aromatic-aliphatic amines, both secondary and tertiary, are also more strongly basic than the pure aromatic amines, and less basic than the true aliphatic compounds; e.g.
1.2 or 1.6, named ortho- (o), 1.3 or 1.5, named meta- (m), and 1.4, named para- compounds (p).
In the case of tetra-substituted compounds, thirty isomers are possible when all the groups are different.
Orientation of Substituent Groups.-The determination of the relative positions of the substituents in a benzene derivative constitutes an important factor in the general investigation of such compounds.
Confining our attention, for the present, to di-substitution products we see that there are three distinct series of compounds to be considered.
Intermolecular transformations-migrations of substituent groups from one carbon atom to anotherare of fairly common occurrence among oxy compounds at elevated temperatures.
It is necessary, therefore, to avoid reactions involving such intermolecular migrations when determining the orientation of aromatic compounds.
Such a series of typical compounds are the benzene dicarboxylic acids (phthalic acids), C 6 H 4 (000H) 2.
Starting with the three isomeric compounds, he found that one gave two tribrombenzenes, another gave three, while the third gave only one.
The orientation of higher substitution derivatives is determined by considering the diand tri-substitution compounds into which they can be transformed.
Experience has shown that such mono-derivatives as nitro compounds, sulphonic acids, carboxylic acids, aldehydes, and ketones yield as a general rule chiefly the meta-compounds, and this is independent of the nature of the second group introduced; on the other hand, benzene haloids, amino-, homologous-, and hydroxy-benzenes yield principally a mixture of the orthoand para-compounds.
By further substitution of orthoand para-diderivatives, in general the same tri-derivative [1.2.4] is formed (Ann., 1878, 192, p. 219); meta - compounds yield [1.3.41 and [1.2.
x u x?X x x HZ which exist between aliphatic and benzenoid compounds make the transformations of one class into the other especially interesting.
In the first place we may notice a tendency of several aliphatic compounds, e.g.
methane, tetrachlormethane, &c., to yield aromatic compounds when subjected to a high temperature, the so-called pyrogenetic reactions (from Greek 7rup, fire, and - yon, fco, I produce); the predominance of benzenoid, and related compounds-naphthalene, anthracene, phenanthrene, &c.-in coal-tar is probably to be associated with similar pyrocondensations.
Long-continued treatment with halogens may, in some cases, result in the formation of aromatic compounds; thus perchlorbenzene, C 6 C1 6, frequently appears as a product of exhaustive chlorination, while hexyl iodide, C 6 H 13 I, yields perchlorand perbrom-benzene quite readily.
Certain a-diketones condense to form benzenoid quinones, two molecules of the diketone taking part in the reaction; thus diacetyl, CH 3 CO CO CH 3, yields p-xyloquinone, C 6 H 2 (CH 3) 2 0 2 (Ber., 1888, 21, p. 1411), and acetylpropionyl, CH 3 CO CO C 2 H 5, yields duroquinone, or tetramethylquinone, C 6 (CH 3) 4 0 2, Oxymethylene compounds, characterized by the grouping > C:CH(OH), also give benzene derivatives by hydrolytic condensation between three molecules; thus oxymethylene acetone, or formyl acetone, CH 3 CO.
Hitherto we have generally restricted ourselves to syntheses which result in the production of a true benzene ring; but there are many reactions by which reduced benzene rings are synthesized, and from the compounds so obtained true benzenoid compounds may be prepared.
If we accept Kekule's formula for the benzene nucleus, then we may expect the double linkages to be opened up partially, either by oxidation or reduction, with the formation of di-, tetra-, or hexa-hydro derivatives, or entirely, with the production of open chain compounds.
Certain compounds withstand ring decomposition much more strongly than others; for instance,.
benzene and its homologues, carboxylic acids, and nitro compounds are much more stable towards oxidizing agents than.
Strong oxidation breaks the benzene complex into such compounds, as carbon dioxide, oxalic acid, formic acid, &c.; such decompositions are of little interest.
Zincke; and his researches have led to the discovery of many chlorinated oxidation products which admit of decomposition into cyclic compounds containing fewer carbon atoms than characterize the benzene ring, and in turn yielding openchain or aliphatic compounds.
These compounds are both decomposed by water, the former giving dichloraceto-trichlorcrotonic acid (4), which on boiling with water gives dichlormethylvinyl-a-diketone (5).
Hantzsch (Ber., 1889, 22, p. 1238) succeeded in ob R taining derivatives of o-diketo-R-hexene, which yield R-pentene and aliphatic compounds on decomposition.
2 and 1.6 compounds were identical, then we should expect the two well-known crotonic acids, CH 3 CH: CH COOH and CH 2: CH CH 2 000H, to be identical.
He assumed that if we have one atom 1 It is now established that ortho compounds do exist in isomeric forms, instances being provided by chlor-, brom-, and amino-toluene, chlorphenol, and chloraniline; but arguments, e.g.
Baeyer pointed out that although benzene derivatives were obtainable from hexamethylene compounds, yet it by no means follows that only hexamethylene compounds need result when benzene compounds are reduced.
The stronger argument against the ethylenoid linkages demanded by Kekule's formula is provided by the remarkable stability towards oxidizing and reducing agents which characterizes all benzenoid compounds.
From the fact that reduction products containing either one or two double linkages behave exactly as unsaturated aliphatic compounds, being readily reduced or oxidized, and combining with the halogen elements and haloid acids, it seems probable that in benzenoid compounds the fourth valencies are symmetrically distributed in such a manner as to induce a peculiar stability in the molecule.
It is difficult to determine which configuration most accurately explains the observed facts; Kekule's formula undoubtedly explains the synthetical production of benzenoid compounds most satisfactorily, and W.
cluded that in compounds the benzene nucleus appears to be capable of existence in two tautomeric forms, in the sense that each particular derivative possesses a definite constitution.
From a study of the reduction of compounds containing two ethylenic bonds united by a single bond, termed a "conjugated system," E.
Reduction to hexamethylene compounds necessitates the disruption of three of the edges of the octahedron, the diagonal linkings remaining intact, or, in the plane projection, three peripheral linkages, the hexamethylene ring assuming the form (III); In 1888 J.
Soc. Trans., 1902, p. 961) shows the proximity of the ortho-positions, but fails to explain the identity of 1.2 and 1.6 compounds.
Restricting ourselves to compounds resulting from the fusion of benzene rings, we have first to consider naphthalene, C10H8, which consists of two benzene rings having a pair of carbon atoms in common.
Here we shall only discuss the structure of these compounds in the light of the modern benzene theories; reference should be made to the articles Naphthalene, Anthracene and Phenanthrene for syntheses, decompositions, &c.
The compounds so obtained, alicyclic-,-tetrahydronaphthylamine and alicyclic-atetrahydronaphthol, closely resemble f3-aminodiethylbenzene, C 6 H 4 (C 2 H C 2 H 4 NH 2, and 3-oxydiethylbenzene,C 6 H 4 (C 2 H 5) C2H40H.
If a-naphthylamine and a-naphthol be reduced, the hydrogen atoms attach themselves to the non-substituted half of the molecule, and the compounds so obtained resemble aminodiethylbenzene, C 6 H 3 NH 2 (C 2 H 5) 21 and oxydiethylbenzene, C 6 H 3.
During recent years an immense number of ringed or cyclic compounds have been discovered, which exhibit individual characters more closely resembling benzene, naphthalene, &c. than purely aliphatic substances, inasmuch as in general they contain double linkages, yet withstand oxidation, and behave as nuclei, forming derivatives in much the same way as benzene.
By reduction, the double linkages become saturated, and compounds result which stand in much about the same relation to the original nucleus as hexamethylene does to benzene.
In general, therefore, it may be considered that the double linkages are not of exactly the same nature as the double linkage present in ethylene and ethylenoid compounds, but that they are analogous to the potential valencies of benzene.
It is remarkable that sulphur can replace two methine or CH groups with the production of compounds greatly resembling the original one.
Similarly a CH group may be replaced by a nitrogen atom with the production of compounds of similar stability; thus benzene gives pyridine, naphthalene gives quinoline and isoquinoline; anthracene gives acridine and a and 3 anthrapyridines.
As a useful preliminary it is convenient to divide heterocyclic ring systems into two leading groups: (I) systems resulting from simple internal dehydration (or similar condensations) of saturated aliphatic compounds - such compounds are: the internal anhydrides or cyclic ethers of the glycols and thioglycols (ethylene oxide, &c.); the cyclic alkyleneimides resulting from the splitting off of ammonia between the amino groups of diaminoparaffins (pyrrolidine, piperazine, &c.); the cyclic esters of oxycarboxylic acids (lactones, lactides); the internal anhydrides of aminocarboxylic acids (lactams, betaines); cyclic derivatives of dicarboxylic acids (anhydrides, imides, alkylen-esters, alkylenamides, &c.).
These compounds retain their aliphatic nature, and are best classified with open-chain compounds, into which, in general, they are readily converted.
Systems which are generally unsaturated compounds, often of considerable stability, and behave as nuclei; these compounds constitute a well-individualized class exhibiting closer affinities to benzenoid substances than to the open-chain series.
The transition between the two classes as differentiated above may be illustrated by the following cyclic compounds, each of which contains a ring composed of four carbon atoms and one oxygen atom: CH CH/ CH CH/ CH CO I CH CO' CH =CH c Tetramethylene But yrolactone.
The three primary members are furfurane, thiophene and pyrrol, each of which contains four methine or CH groups, and an oxygen, sulphur and imido (NH) member respectively; a series of compounds containing selenium is also known.
The formulae of these substances are: By substituting one or more CH groups in these compounds by nitrogen atoms, ring-systems, collectively known as azoles, result.
As before, only true ring nuclei, and not internal anhydrides of aliphatic compounds, will be mentioned.
From the pyrone ring the following series of compounds are derived (for brevity, the hydrogen atoms are not printed): Penthiophene gives, by a similar introduction of nitrogen atoms, penthiazoline, corresponding to meta-oxazine, and para-thiazine, CH 2 CH 2o CH CO „ .„0 C ?
Benzo-ortho-diazines exist in two structural forms, cinnolin and phthalazine; benzo-meta-diazines are known as quinazolines; benzo-para-diazines are termed quinoxalines; the dibenzo-compounds are named phenazines, this last group including many valuable dyestuffs - indulines, safranines, &c. In addition to the types of compounds enumerated above we may also notice purin, tropine and the terpenes.
Analytical Chemistry This branch of chemistry has for its province the determination of the constituents of a chemical compound or of a mixture of compounds.
He realized that the composition by weight of chemical compounds was of the greatest moment if chemistry were to advance.
He applied himself more particularly to the oxygen compounds, and determined with a fair degree of accuracy the ratio of carbon to oxygen in carbon dioxide, but his values for the ratio of hydrogen to oxygen in water, and of phosphorus to oxygen in phosphoric acid, are only approximate; he introduced no new methods either for the estimation or separation of the metals.
The limits of space prevent any systematic account of the separation of the rare metals, the alkaloids, and other classes of organic compounds, but sources where these matters may be found are given in the list of references.
A sublimate may be formed of: sulphur - reddish-brown drops, cooling to a yellow to brown solid, from sulphides or mixtures; iodine - violet vapour, black sublimate, from iodides, iodic acid, or mixtures; mercury and its compounds - metallic mercury forms minute globules, mercuric sulphide is black and becomes red on rubbing, mercuric chloride fuses before subliming, mercurous chloride does not fuse, mercuric iodide gives a yellow sublimate; arsenic and its compounds - metallic arsenic gives a grey mirror, arsenious oxide forms white shining crystals, arsenic sulphides give reddish-yellow sublimates which turn yellow on cooling; antimony oxide fuses and gives a yellow acicular sublimate; lead chloride forms a white sublimate after long and intense heating.
Some of these insoluble compounds can be detected by their colour and particular reactions.
It is unnecessary here to dwell on the precautions which can only be conveniently acquired by experience; a sound appreciation of analytical methods is only possible after the reactions and characters of individual substances have been studied, and we therefore refer the reader to the articles on the particular elements and compounds for more information on this subject.
In the second group, we may notice the application of litmus, methyl orange or phenolphthalein in alkalimetry, when the acid or alkaline character of the solution commands the colour which it exhibits; starch paste, which forms a blue compound with free iodine in iodometry; potassium chromate, which forms red silver chromate after all the hydrochloric acid is precipitated in solutions of chlorides; and in the estimation of ferric compounds by potassium bichromate, the indicator, potassium ferricyanide, is placed in drops on a porcelain plate, and the end of the reaction is shown by the absence of a blue coloration when a drop of the test solution is brought into contact with it.
The elements which play important parts in organic compounds are carbon, hydrogen, nitrogen, chlorine, bromine, iodine, sulphur, phosphorus and oxygen.
Messinger, and we may hope that with subsequent improvements it may be adapted to all classes of organic compounds.
The first class includes those substances which require no preliminary treatment, and comprises the amides and ammonium compounds, pyridines, quinolines, alkaloids, albumens and related bodies; the second class requires preliminary treatment and comprises, with few exceptions, the nitro-, nitroso-, azo-, diazoand amidoazo-compounds, hydrazines, derivatives of nitric and nitrous acids, and probably cyanogen compounds.
With iodine compounds, iodic acid is likely to be formed, and hence the solution must be reduced with sulphurous acid before precipitation with silver nitrate.
The oxidation with nitric acid in sealed tubes at a temperature of 150° to 200° for aliphatic compounds, and 250° to 260° for aromatic compounds, is in common use, for both the sulphur and phosphorus can be estimated, the former being oxidized to sulphuric acid and the latter to phosphoric acid.
Identity in composition, but difference in constitution, is generally known as " isomerism " (q.v.), and compounds satisfying this relation differ in many of their physical properties.
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.
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.
The molecular volume is additive in certain cases, in particular of analogous compounds of simple constitution.
Specific Heat and Composition.-The nature and experimental determination of specific heats are discussed in the article Calorimetry; here will be discussed the relations existing between the heat capacities of elements and compounds.
We now proceed to discuss molecular heats of compounds, that is, the product of the molecular weight into the specific heat.
Neumann, who, in 1831, deduced from observations on many carbonates (calcium, magnesium, ferrous, zinc, barium and lead) that stoichiometric quantities (equimolecular weights) of compounds possess the same heat capacity.
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.
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.
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.
In the aromatic compounds there is no regularity between the increments due to the introduction of methyl groups into the benzene nucleus or side chains; the normal value of 20 0 -21° is exhibited, however, by pyridine and its derivatives.
As a general rule, compounds formed tive with a great evolution of heat have high boiling-points, and vice versa.
A similar depression is presented by methyl alcohol (67°) and methyl ether (-23 °) Among the aromatic di-substitution derivatives the ortho compounds have the highest boiling-point, and the meta boil at a higher, or about the same temperature as the para compounds.
Of the tri-derivatives the symmetrical compounds boil at the lowest temperature, the asymmetric next, and the vicinal at the highest.
An ethylenic or double carbon union in the aliphatic hydrocarbons has, apparently, the same effect on the boiling-point as two hydrogen atoms, since the compounds C 0 H 2 „ +2 and CoH2n boil at about the same temperature.
An acetylenic or triple linkage is associated with a rise in the boiling-point; for example, propargyl compounds boil about 19.5° higher than the corresponding propyl compound.
In the article Thermo Chemistry a general account of heats of formation of chemical compounds is given, and it is there shown that this constant measures the stability of the compound.
The same difference attends the introduction of the methyl group into many classes of compounds, for example, the paraffins, olefines, acetylenes, aromatic hydrocarbons, alcohols, aldehydes, ketones and esters, while a slightly lower value (157.1) is found in the case of the halogen compounds, nitriles, amines, acids, ethers, sulphides and nitro compounds.
It therefore appears that the difference between the heats of combustion of two adjacent members of a series of homologous compounds is practically a constant, and that this constant has two average values, viz.
Thomsen deduces the actual values of X, Y, Z to be 14.71, 13.27 and zero; the last value he considers to be in agreement with the labile equilibrium of acetylenic compounds.
compounds having the same composition, have equal molecular refractions, and that equal differences in composition are associated with equal differences in refractive power.
Atomic refractions may be obtained either directly, by investigating the various elements, or indirectly, by considering differences in the molecular refractions of related compounds.
Colour and Constitution.-In this article a summary of the theories which have been promoted in order to connect the colour of organic compounds with their constitution will be given, and the reader is referred to the article Colour for the physical explanation of this property, and to Vision for the physiological and psychological bearings.
The azo-group is particularly active, both the aliphatic and aromatic compounds being coloured.
The simplest aliphatic compounds, such as diazo-methane, diazoethane, and azo-formic acid, are yellow; the diamide of the latter acid is orange-red.
Of the aromatic compounds azo-benzene is bright orange-red, and a-azonaphthalene forms red needles or small steel-blue prisms. The azogroup, however, has little or no colouring effect when present in a ring system, such as in cinnolene, phthalazine and tolazone.
Examination of the absorption spectra of coloured compounds shows that certain groupings displace the absorption bands in one direction, and other groupings in the other.
The quinonoid structure of many coloured compounds has been proved experimentally, as, for example, by Hewitt for the benzene-azo-phenols, and Hantzsch for triaminotriphenyl methane and acridine derivatives; but, at the same time, many substances cannot be so explained.
Soc., 1906, 89, p. 1787) have disputed the correctness of this explanation, and the latter has prepared melliteins and pyromelliteins, which are highly-coloured compounds produced from mellitic and pyromellitic acids, and which cannot be formulated as quinones.
Meyer, which are formed when nitrous acid acts on primary aliphatic nitro compounds.
Meyer formulated these compounds as nitroximes or nitro-isnitroso derivatives, viz.
He suggests that the term " quinone " theory be abandoned, and replaced by the Umlagerungs theory, since this term implies some intermolecular rearrangement, and does not connote simply benzenoid compounds as does " quinonoid."
Normal values of K were given by nitrogen peroxide, N204, sulphur chloride, S 2 C1 21 silicon tetrachloride, SiC1 4, phosphorus chloride, PC1 3, phosphoryl chloride, POC1 31 nickel carbonyl, Ni(CO) 4, carbon disulphide, benzene, pyridine, ether, methyl propyl ketone; association characterized many hydroxylic compounds: for ethyl alcohol the factor of association was 2.74-2.43, for n-propyl alcohol 2.86-2.72, acetic acid 3.62 -2.77, acetone 1 .
It is remarkable that a great many polymorphous substances assume more symmetrical forms at higher temperatures, and a possible explanation of the increase in density of such compounds as silver iodide, &c., may be sought for in the theory that the formation of a more symmetrical configuration would involve a drawing together of the molecules, and consequently an increase in density.
Many instances have been recorded where substitution has effected a deformation in one particular direction, the crystals of homologous compounds often exhibiting the same angles between faces situated in certain zones.
The equivalent volumes and topic parameters are tabulated: From these figures it is obvious that the first three compounds form a morphotropic series; the equivalent volumes exhibit a regular progression; the values of x and t,t, corresponding to the a axes, are regularly increased, while the value of w, corresponding to the c axis, remains practically unchanged.
It is thus seen that the ordinary plane representation of the structure of compounds possesses a higher significance than could have been suggested prior to crystallographical researches.
For the historical development of the proximate analysis of organic compounds see M.
Pyrrol is readily converted into pyridine derivatives by acting with bromoform, chloroform, or methylene iodide on its potassium salt, t3-brom-and O-chlorpyridine being obtained with the first two compounds, and pyridine itself with the last.
He also found that diaceto succinic ester reacts with compounds of the type NH 2 R(R = H, CH 3, OH, NHC 6 H 5, &c.) to form pyrrol derivatives CH3 CO CH CO 2 R, C(CH3) :C C02R A NH 2 R -?- - RN(CH 3 CO CH CO 2 R C(CH3) :C C02R By using compounds of the type NH 2 R and acetophenone acetoacetic ester C 6 H 5 CO CH 2.
Edmond Becquerel was associated with his father in much of his work, but he himself paid special attention to the study of light, investigating the photochemical effects and spectroscopic characters of solar radiation and the electric light, and the phenomena of phosphorescence, particularly as displayed by the sulphides and by compounds of uranium.
OXIMES, in organic chemistry, compounds containing the grouping > C: N OH, derived from aldehydes and ketones by condensing them with hydroxylamine.
They may also be prepared by the reduction of primary nitro compounds with stannous chloride and concentrated hydrochloric acid; by the reduction of unsaturated nitro compounds with minium amalgam or zinc dust in the presence of dilute acetic acid' Bouveault, Comptes rendus, 1902, 134, p. 1145):R2C:[[Chno 2 -R 2 C: Ch Nhoh - R 2 Ch Ch: Noh]], and by the action of alkyl iodides on the sodium salt of nitro-hydroxylamine (A.
It is invariably present in soils, where compounds are formed by nitrifying bacteria.
The chief importance of nitrogenous compounds depends upon their assimilation by living plants, which, in their development, absorb these compounds from the soil, wherein they are formed mainly by the action of nitrifying bacteria.
Since these compounds are essential to plant life, it becomes necessary to replace the amount abstracted from the soil, and hence a demand for nitrogenous manures was created.
The acid finds considerable use in organic chemistry, being employed to discriminate between the different types of alcohols and of amines, and also in the production of diazo, azo and diazo-amino compounds.
The liquid boils at -5° C. and the solid melts at -65° C. It forms double compounds with many metallic chlorides, and finds considerable application as a means of separating various members of the terpene group of compounds.
Mineral nitrogenous compounds (nitrates, nitrites and ammonia) are much more rare.
If this is admitted the poverty of tropical sea-water in mineral nitrogen compounds is explained by the higher temperature, which accelerates the activity of denitrifying bacteria.
It would seem that, on the whole, nitrogen compounds in the ocean (whether existing in the organic or inorganic forms) remain constant in amount.
The putrefaction of the latter sets free sulphuretted hydrogen, which then acts on the iron compounds, precipitating ferrous sulphide.
This list is not exhaustive; other products are given in Gustav Mann, Chemistry of the Proteids (1906), to which reference should be made for a complete account of this class of compounds.
Other varieties or classes of these compounds are: plant caseins, phyto-vitellines, legumins and conglutins.
Haemoglobin is composed of a basic albumin and an acid substance haematin; it combines readily with oxygen, carbon dioxide and carbon monoxide to form loose compounds.
THIAZOLES, in organic chemistry, a series of heterocyclic compounds containing the grouping shown below; the replaceable hydrogen atoms in which are designated a, (3 and µ.
In the vegetable kingdom glucose occurs, always in admixture with fructose, in many fruits, especially grapes, cherries, bananas, &c.; and in combination, generally with phenols and aldehydes belonging to the aromatic series, it forms an extensive class of compounds termed glucosides.
Lowry and Armstrong represent these compounds by the following spatial formulae which postulate a y-oxidic structure, and 5 asymmetric carbon atoms, i.e.
Caoutchouc, like other "unsaturated" molecules, forms compounds with chlorine, bromine, iodine and sulphur.
From 1827 to 1833 he was occupied mainly with chemical researches, which resulted in the discovery of the first of the platino-ammonium compounds ("Magnus's green salt" is Pt11 2j 2NH 3), of sulphovinic, ethionic and isethionic acids and their salts, and, in conjunction with C. F.
In regard to the ancients' knowledge of lead compounds, we may state that the substance described by Dioscorides as, uoXv,3Saiva was undoubtedly litharge, that Pliny uses the word minium in its present sense of red lead, ana that white lead was well known to Geber in the 8th century.
Since all soluble lead compounds are strong cumulative poisons, danger is involved in using lead cisterns or pipes in the distribution of pure waters.
Compounds of Lead.
At the same time, however, it forms a number of compounds in which it is most decidedly tetravalent; and thus it shows relations to carbon, silicon, germanium and tin.
The Kassner process for the manufacture of oxygen depends upon the formation of calcium plumbate, Ca2Pb04, by heating a mixture of lime and litharge in a current of air, decomposing this substance into calcium carbonate and lead dioxide by heating in a current of carbon dioxide, and then decomposing these compounds with the evolution of carbon dioxide and oxygen by raising the temperature.
These salts are like those of tin; and the resemblance to this metal is clearly enhanced by the study of the alkyl compounds.
Here compounds of divalent lead have not yet been obtained; by acting with zinc ethide on lead chloride, lead tetraethide, Pb(C 2 IH Q) 4, is obtained, with the separation of metallic lead.
It is decomposed by heat into oxide, nitrogen peroxide and oxygen; and is used for the manufacture of fusees and other deflagrating compounds, and also for preparing mordants in the dyeing and calico-printing industries.
Beyond the small fertile valley in which it stands is the barren desert, on which rain rarely falls and which has no economic value apart from its minerals (especially saline compounds).
Magnetic Properties of Alloys and Compounds of Iron.
Practically the metals iron, nickel and cobalt, and some of their alloys and compounds constitute a class by themselves and are called ferromagnetic substances.
In the case of the ferromagnetic metals and some of their alloys and compounds, the permeability has generally a much higher value.
Alloys And Compounds Of Iron In 1885 Hopkinson (Phil.
Many of their compounds are very strongly magnetic, erbium, for example, in Er203 being four times as strong as iron in the familiar magnetite or lodestone, Fe203.
The susceptibilities of some hundreds of inorganic compounds.
Various compounds of the word are used, e.g.
ALDEHYDES, a class of chemical compounds of the general formula Rï¿½CHO (R=an alkyl or an aryl group).
They form many addition compounds, combining with ammonia to form aldehyde ammonias of the type R.
These are colourless crystalline compounds, which are most readily prepared by passing ammonia gas into an ethereal solution of the aldehyde.
With sodium bisulphite they form the so-called bisulphite compounds Rï¿½CH(OH)ï¿½SO Na, which are readily resolved into their components by distillation with dilute acids, and are frequently used for the preparation of the pure aldehyde.
These aldols generally lose the elements of water readily and pass into unsaturated compounds; aldol itself on distillation at ordinary atmospheric pressure gives crotonaldehyde, CH 3 ï¿½ CH: CH.
Unsaturated aldehydes are also known, corresponding to the olefine alcohols; they show the characteristic properties of the saturated aldehydes and can form additive compounds in virtue of their unsaturated nature.
Columbium compounds are usually prepared by fusing columbite with an excess of acid potassium sulphate, boiling out the fused mass with much water, and removing tin and tungsten from the residue by digestion with ammonium sulphide, any iron present being simultaneously converted into ferrous sulphide.
Nature has provided several species of animals, birds and reptiles, to feed upon these insects, and various poisonous and suffocating compounds are used to destroy them, but with no great degree of success.
NITRO COMPOUNDS, in organic chemistry, compounds containing the monovalent radical -NO 2 directly combined with carbon.
The nitro compounds of the lower members of the paraffin series cannot be prepared by the direct action of nitric acid on the hydrocarbons themselves, but, in the case of some of the higher members of the series direct nitration is possible (M.
The nitro compounds are colourless, somewhat pleasant smelling liquids, which distil without decomposition and possess boiling points much higher than those of the isomeric nitrous esters.
Hantzsch (Ber., 18 99, 3 2, pp. 577 et seq.) are probably derived from the isomeric iso-nitro compounds R: NO(OH), and thus the nitro derivatives are to be looked upon as pseudo-acids.
The hydrogen in the primary and secondary nitro compounds which is attached to the same carbon atom as the nitro group is readily replaced by bromine in alkaline solution.
The primary compounds form nitrolic acids of the type R C (: NOH) NO, the secondary yield pseudo-nitrols of the type RR': C(NO)(NO 2), whilst the tertiary nitro compounds are not acted upon by nitrous acid.
Tetranitromethane, C(N02)4, obtained by adding nitroform to a hot mixture of nitric and sulphuric acids, is a crystalline solid which melts at 13° C. Chlorpicrin, CC1 3 NO 2, is a liquid of suffocating odour obtained by the action of nitric acid and chloride of lime on many organic compounds.
Aromatic Nitro Compounds.-The aromatic nitro compounds are generally obtained by the direct action of nitric acid.
Nitro compounds have also been prepared by the action of cuprous oxide on diazonium salts (T.
The mono-nitro compounds are stable and distil without decomposition; they have a pale yellow colour and possess an agreeable odour.
Most of the polynitro compounds are not volatile, but undergo deco Imposition on heating.
Several different products may be obtained by the reduction of the aromatic nitro compounds, the substances formed in any particular case depending on the conditions of experiment.
In acid solution, amines are obtained, in alkaline solution, azoxy, azo and hydrazo compounds, and in neutral solution hydroxylamino compounds.
The electrolytic reduction of the aromatic nitro compounds gives rise to substituted hydroxylamines which are immediately transformed into aminophenols or amines.
They discriminate between the red or erythro-salts, which are well crystallized, very explosive and unstable compounds, and which regenerate the colourless nitrolic acid on the addition of dilute mineral acids, and the leuco-salts, which are colourless salts obtained by warming the erythro-salts or by exposing them to direct sunlight.
The following structural formulae are assigned to these compounds: R CAN OH R.CCN(OK) > O R C N02K NO 2 N(:O) NO nitrolic acid; erythro-salt; leuco-salt.
They are unstable compounds which readily split into the red salt and the free acid on standing.
Nitrosohydrocarbons have been prepared in the aliphatic series by the oxidation of the corresponding hydroxylamino compounds.
Numerous nitroso compounds are met with in the aromatic series.
It abolished the conception of life s an entity above and beyond the common properties of matter, and led to the conviction that the marvellous and exceptional qualities of that which we call " living " matter are nothing more nor less than an exceptionally complicated development of those chemical and physical properties which we recognize in a gradually ascending scale of evolution in the carbon compounds, containing nitrogen as well as oxygen, sulphur and hydrogen as constituent atoms of their enormous molecules.
We do not yet know whether such absolute blending is possible or not, or whether all apparent blending is only a more or less minutely subdivided " mosaic " of non-combinable characters of the parents, in fact whether the combinations due to heredity in reproduction are ever analogous to chemical compounds or are always comparable to particulate mixtures.
TRIAZINES, in organic chemistry, a series of cyclic compounds, containing a ring system composed of three carbon and three nitrogen atoms. Three series are possible, the positions of Marine Trias Of The Alpine And Indian Types.
Busch, Ber., 1899, 32, p. 2960): N C(SH):N C 6 H 5 /N C:NC6H5 C. 2 S 7Hs " H s d-H N NH C,H 7 C7 "N N C,H7 C. Harries (Ber., 1895, 28, p. 1223) has also shown that as-phenylhydrazino-acetic esters, when heated with formamide and substituted formamides under pressure, yield dihydrotriazines: CO 2 R CO-NR'-CH H2 N(C6H5)NH2 +R'NH CHO --> CH 2 N(C 6 H 5) IV The phen-a-triazines are yellow-coloured crystalline compounds of a somewhat basic character.
artificial pitchblende, which serves as a starting-point for the preparation of uranium compounds.
If forms two series of salts, one, the uranous compounds, are derived from the oxide U02, the other, the uranyl compounds, contain the divalent group U02.
Ammonium uranate heated to redness yields pure U308, which serves as a raw material for uranium compounds.
The new form takes on the characters of that from which it arose; exhibits the same power of propagating itself by means of an offshoot; and, sooner or later, like its predecessor, ceases to live, and is resolved into more highly oxidated compounds of its elements.
And it remains to be seen, how far the death of any form of living matter, at a given temperature, depends on the destruction of its fundamental substance at that heat, and how far death is brought about by the coagulation of merely accessory compounds.
Compounds of Tin.
Tin compounds when heated on charcoal with sodium carbonate or potassium cyanide in the reducing blowpipe flame yield the metal and a scanty ring of white Sn02.
Crum was probably the first to recognize that some hydrogen atoms of the cellulose had been replaced by an oxide of nitrogen, and this view was supported more or less by other workers, especially Hadow, who appears to have distinctly recognized that at least three compounds were present, the most violently explosive of which constituted the main bulk of the product commonly obtained and known as guncotton.
The products of the action of nitric acid on cellulose are not nitro compounds in the sense that picric acid is, but are nitrates or nitric esters.
It is excreted when many aromatic compounds, such as benzoic acid and toluene, are taken internally.
It forms crystalline compounds with bromine and with many metallic salts.
TRIAZOLES (pyrro-a and (3'-diazoles), in organic chemistry, a series of heterocyclic compounds containing the ring complex (annexed formula).
These compounds may be considered as 5-triazolones, a series of isomeric 3-triazolones resulting from the condensation of phenylsemicarbazide with aromatic aldehydes in the presence of an oxidant.
Busch (Ber., 1905, 38, pp. 856, 4049) has isolated a series of bridged ring compounds which he describes as endo-iminodihydrotriazoles, the triphenyl derivative (annexed formula) being prepared by condensing triphenylaminoguanidine with formic acid.
Leber experimented with several chemical compounds to find what reaction they had on these cells; by using fine glass tubes sealed at the outer end and containing a chemical substance, and by introducing the open end into the blood vessels he found that the leucocytes were attracted - positive chemiotaxis - by the various compounds of mercury, copper, turpentin, and other substances.
Aniline and similar bases are oxidized and partially nitrated by nitroglycerin, with the production of non-explosive compounds.
Fraser proved that by substitution of molecules in certain compounds a stimulant could be converted into a sedative action; thus by the addition of the methyl group CH 2 to the molecule of strychnine, thebaine or brucine, the tetanizing action of these drugs is converted into a paralysing action.
In the former he was one of the leading workers, in collaboration from 1879 to 1887 with Emile Edmond Sarasin (1843-1890), at the formation of minerals by artificial means, particularly in the wet way with the aid of heat and pressure, and he succeeded in reproducing a large number of the natural compounds.
1839), for many years a professor at the Massachusetts Institute of Technology, Boston, he obtained various organometallic compounds of silicon.
It was based on an accidental observation of the action of metallic aluminium on amyl chloride, and consists in bringing together a hydrocarbon and an organic chloride in presence of aluminium chloride, when the residues of the two compounds unite to form a more complex body.
Kolbe had an important share in the great development of chemical theory that occurred about the middle of the 19th century, especially in regard to the constitution of organic compounds, which he viewed as derivatives of inorganic ones, formed from the latter - in some cases directly - by simple processes of substitution.
Kolbe was a very successful teacher, a ready and vigorous writer, and a brilliant experimentalist whose work revealed the nature of many compounds the composition of which had not previously been understood.
Acridine and its homologues are very stable compounds of feebly basic character.
It is convenient to treat these glasses as " normal " glasses, but they are in reality mixtures of silicates, and cannot rightly be regarded as definite chemical compounds or represented by definite chemical formulae.
The organic derivatives of silicon resemble the corresponding carbon compounds except in so far that the silicon atom is not capable of combining with itself to form a complex chain in the same manner as the carbon atom, the limit at present being a chain of three silicon atoms. Many of the earlier-known silicon alkyl compounds were isolated by Friedel and Crafts and by Ladenburg, the method adopted consisting in the interaction of the zinc alkyl compounds with silicon halides or esters of silicic acids.
The atomic weight of silicon has been determined usually by analysis of the halide compounds or by conversion of the halides into silica.
The compounds formed in the first case, which may be either definite chemical compounds or solid solutions, are discussed under Alloys; in this place only combinations with non-metals are discussed, it being premised that the free metal takes part in the reaction.
Hydrogen, as was shown by Graham, is capable of uniting with or being occluded by certain metals, notably with palladium (q.v.), into metal-like compounds.
Benzene is of exceptional importance commercially on account of the many compounds derivable from it, which are exceedingly valuable in the arts.
Chemically it is one of the most interesting substances known, since it is the parent of the enormous number of compounds styled the " aromatic " or " benzenoid " compounds.
The constitution of the benzene ring, the isomerism of its derivatives, and their syntheses from aliphatic or openchain compounds, are treated in the article Chemistry.
A summary of its chemical transformations may be given here, and reference should be made to the articles on the separate compounds for further details.
He held the doctrine that the chemical elements are compounds of equal and similar atoms, and might therefore possibly be all derived from one generic atom.
Formerly the name was given to compounds having a sweet taste, e.g.
- The cyanhydrins on hydrolysis give monocarboxylic acids, which yield lactones; these compounds when reduced by sodium amalgam in sulphuric acid solution yield a sugar containing one more carbon atom.
When such compounds are converted into corresponding dibasic acids, CO 2 H.[CH(OH)) 3.00 2 H, the number of asymmetric carbon atoms becomes reduced from three to two, as the central carbon atom is then no longer associated with four, but with only three different radicles.
The a-halogen compounds are obtained by heating styrolene chloride (or bromide) with lime or alcoholic potash; they are liquids which have a penetrating odour, and yield acetophenone when heated with water to 180°.
The diortho and dipara dinitro compounds result from the action of alcoholic potash on orthoand para-nitrobenzyl chlorides.
1% present these fertilizers are not usually called for except perhaps in soils containing a high percentage of iron compounds.
025 or 03%, respond freely to applications of phosphates; probably in such cases even the weak acid is capable of dissolving out phosphates from the humus or other compounds which yield little or none to the roots of grasses and clovers.
The compounds of ammonia thus formed from the complex substances by many varied kinds of micro-organisms are ultimately oxidized into nitrates.
In the first stage the ammonium compounds are oxidized to nitrites by the agency of very minute motile bacteria belonging to the genus Nitrosomonas.
An important group of soil organisms are now known which have the power of using the free nitrogen of the atmosphere for the formation of the complex nitrogenous compounds of which their bodies are largely composed.
For the carrying on of their functions they all need to be supplied with carbohydrates or other carbon compounds which they obtain ordinarily from humus and plant residues in the soil, or possibly in some instances from carbohydrates manufactured by minute green algae with which they live in close union.
Later the nitrogen-content of the nodule decreases, most of the organisms, which are largely composed of proteid material, becoming digested and transformed into soluble nitrogenous compounds which are conducted to the developing roots and seeds.
Gas-lime is a product obtained from gasworks where quicklime is used to purify the gas from sulphur compounds and other objectionable materials.
As some of these sulphur compounds have a poisonous effect on plants, gas-lime cannot be applied to land directly without great risk or rendering it incapable of growing crops of any sort - even weeds - for some time.
i nto compounds which when ploughed into the land become humus.
The carbon compounds of the latter are of no direct nutritive value to the succeeding crop, but the decaying vegetable tissues very greatly assist in retaining moisture in light sandy soils, and in clay soils also have a beneficial effect in rendering them more open and allowing of better drainage of superfluous water and good circulation of fresh air within them.
Pharmacology And Therapeutics Of Zinc Compounds Zinc chloride is a powerful caustic, and is prepared with plaster of Paris in the form of sticks for destroying warts, &c. Its use for this purpose at the present day is, however, very rare, the knife or galvanocautery being preferred in most cases.
His contributions to inorganic chemistry were numerous, including investigations on the compounds of antimony, aluminium, silicon, &c., on the separation of nickel and cobalt, and on the analysis of mineral waters, but they are outweighed in importance by his work on organic substances.
In 1832 he published, jointly with Willer, one of the most famous papers in the history of chemistry, that on the oil of bitter almonds (benzaldehyde), wherein it was shown that the radicle benzoyl might be regarded as forming an unchanging constituent of a long series of compounds obtained from oil of bitter almonds, throughout which it behaved like an element.
These on the one hand resulted in the enunciation of his ethyl theory, by the light of which he looked upon those substances as compounds of the radicle ethyl (C 2 H 5), in opposition to the view of J.
Dumas, who regarded them as hydrates of olefiant gas (ethylene); on the other they yielded chloroform, chloral and aldehyde, as well as other compounds of less general interest, and also the method of forming mirrors by depositing silver from a slightly ammoniacal solution by acet aldehyde.
Rejecting the old notion that plants derive their nourishment from humus, he taught that they get carbon and nitrogen from the carbon dioxide and ammonia present in the atmosphere, these compounds being returned by them to the atmosphere by the processes of putrefaction and fermentation - which latter he regarded as essentially chemical in nature - while their potash, soda, lime, sulphur, phosphorus, &c., come from the soil.
(-anthrol and anthranol give the corresponding amino compounds (anthramines) when heated with ammonia.
It forms addition compounds similar to those formed by stannic chloride, and combines with ammonia to form TiCl 4.8NH 3 and TiC1 4.6NH 3, both of which with liquid ammonia give titanamide, Ti(NH2)4.
The structural relations of these compounds may be shown thus: NH 3; NH2R; Ammonia; primary amine; NHR 2; NR3; NR41.
- These compounds possess properties very similar to those of ammonia, the lowest members of the series being combustible gases readily soluble in water.
With benzene sulphochloride in the presence of alkali, the primary amines yield compounds of the type C 6 H 5 S0 2 NHR, soluble in alkalies, whilst the secondary amines yield compounds of the type C 6 H 5 S0 2 NR 2, insoluble in alkalies (0.
They may also be obtained by the reduction of nitroso compounds and of hydrazo compounds and of hydrazones (J.
The ortho-compounds condense to azimido benzenes, the metacompounds yield azo-dyestuffs, and the para-compounds yield bis-diazo compounds of the type XN2ï¿½C6H4ï¿½N2X.
With substances prone to discolorization, as, for example, certain amino compounds, the operation may be conducted in an atmosphere of carbon dioxide, or the water may be saturated with sulphuretted hydrogen.
At one time it was thought that these mixtures of constant boiling-point (an extended list is given in Young's Fractional Distillation) were definite compounds.
Prior to 1830, little was known of the process other than that organic compounds generally yielded tarry and solid matters, but the discoveries of Liebig and Dumas (of acetone from acetates), of Mitscherlich (of benzene from benzoates) and of Persoz (of methane from acetates and lime) brought the operation into common laboratory practice.
and places which they explain as compounds of Yahu or Yah.'
Another question to which he gave much attention was the connexion of the boiling-point of compounds, organic ones in particular, with their composition.
Both these compounds afford delicate, unobtrusive and effective grounds for inlaying with gold, silver and other metals, as well as for sculpture, whether incised or in relief.
The chlorine reacts with the caustic soda, forming sodium hypochlorite, and this in turn, with an excess of chlorine and at higher temperatures, becomes for the most part converted into chlorate, whilst any simultaneous electrolysis of a hydroxide or water and a chloride (so that hydroxyl and chlorine are simultaneously liberated at the anode) also produces oxygen-chlorine compounds direct.
At the same time, the diffusion of these compounds into contact with the cathode leads to a partial reduction to chloride, by the removal of combined oxygen by the instrumentality of the hydrogen there evolved.
Rotating zinc cathodes were used, with scrapers to prevent the accumulation of a layer of insoluble magnesium compounds, which would otherwise increase the electrical resistance beyond reasonable limits.
This and other reasons led to his rejection of the dualistic hypothesis and the adoption, on the ground of probability, and much more from convenience, of the tenet that " acids are particular compounds of hydrogen, in which the latter can be replaced by metals "; while, on the constitution of salts, he held that " neutral salts are those compounds of the same class in which the hydrogen is replaced by its equivalent in metal.