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.
In formulating these facts Liebig at first retained the dualistic conception of the structure of acids; but he shortly afterwards perceived that this view lacked generality since the halogen acids, which contained no oxygen but yet formed salts exactly similar in properties to those containing oxygen, could not be so regarded.
This change only occurs when the halogen atom is in the orthoor paraposition to the - N2 - group.
It is decomposed by the halogen elements and also by sulphuretted hydrogen.
It is to be noted that only traces of the aromatic amines are produced by heating the halogen substituted benzenes with ammonia, unless the amino group be situated in the side chain, as in the case of benzylamine.
Similarly, the formation of organic halogen products may be effected by electrolytic chlorine, as, for example, in the production of chloral by the gradual introduction of alcohol into an anode cell in which the electrolyte is a strong solution of potassium chloride.
We may quote one of the principal conclusions at which they arrived: " An inspection of our maps will show that the radical of a body is represented by certain well-marked bands, some differing in position according as it is bonded with hydrogen, or a halogen, or with carbon, oxygen or nitrogen.
The amino derivatives are stable bases which readily yield substitution derivatives when acted upon by the halogen elements.
Several halogen compounds of sulphur are known, the most stable of which is sulphur fluoride, SF 6, which was first prepared by H.
Balard completed for many years Berzelius's group of " halogen " elements; the remaining member, fluorine, notwithstanding many attempts, remained unisolated until 1886, when Henri Moissan obtained it by the electrolysis of potassium fluoride dissolved in hydrofluoric acid.
We may, in fact, consider that the descriptive study of the various halogen compounds dates from about this time.
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).
Instances had already been recorded of cases where a halogen element replaced hydrogen with the production of a closely allied substance: Gay Lussac had prepared cyanogen chloride from hydrocyanic acid; Faraday, hexachlorethane from ethylene dichloride, &c. Here the electronegative halogens exercised a function similar to electro-positive hydrogen.
Considering derivatives primarily concerned with transformations of the hydroxyl group, we may regard our typical acid as a fusion of a radical R CO - (named acetyl, propionyl, butyl, &c., generally according to the name of the hydrocarbon containing the same number of carbon atoms) and a hydroxyl group. By replacing the hydroxyl group by a halogen, acid-haloids result; by the elimination of the elements of water between two molecules, acid-anhydrides, which may be oxidized to acid-peroxides; by replacing the hydroxyl group by the group. SH, thio-acids; by replacing it by the amino group, acid-amides (q.v.); by replacing it by the group - NH NH2, acid-hydrazides.
The same absorbent' quantitatively takes up any halogen and sulphur which may be present.
By actual observations it has been shown that ether, alcohol, many esters of the normal alcohols and fatty acids, benzene, and its halogen substitution products, have critical constants agreeing with this originally empirical law, due to Sydney Young and Thomas; acetic acid behaves abnormally, pointing to associated molecules at the critical point.
The abnormal specific heats of the halogen elements may be due to a loosening of the atoms, a preliminary to the dissociation into monatomic molecules which occurs at high temperatures.
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 is remarkable that the position of the halogen in the molecule has no effect on the heat of formation; for example, chlorpropylene and allylchloride, and also ethylene dichloride and ethylidene dichloride, have equal heats of formation.
Other substituent groups exercise morphotropic effects similar to those exhibited by the alkyl radicles; investigations have been made on halogen-, hydroxy-, and nitro-derivatives of benzene and substituted benzenes.
Nitroparaffins may also be obtained by the action of sodium nitrite on the a-halogen fatty acids, the a-nitro fatty acids first formed readily eliminating carbon dioxide (H.
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°.
An important nucleus-synthetic reaction is the saponification of nitriles, which may be obtained by the interaction of potassium cyanide with a halogen substitution derivative or a sulphonic acid.
The advantage of the new definition lies in the fact that the estimation of the chlorine (or rather of the total halogen expressed as chlorine) is sufficient to determine the salinity by a very simple operation.
8050 Cl where S is the salinity and Cl the amount of total halogen in a sample.
3, p. 319.) Ammonia finds a wide application in organic chemistry as a synthetic reagent; it reacts with alkyl iodides to form amines, with esters to form acid amides, with halogen fatty acids to form amino-acids; while it also combines with isocyanic esters to form alkyl ureas and with the mustard oils to form alkyl thioureas.
FLUORINE (symbol F, atomic weight iv), a chemical element of the halogen group. It is never found in the uncombined condition, but in combination with calcium as fluor-spar CaF2 it is widely distributed; it is also found in cryolite Na3A1F6, in fluor-apatite, CaF 2.3Ca 3 P 2 O 8, and in minute traces in seawater, in some mineral springs, and as a constituent of the enamel of the teeth.
Friend, The Theory of Valency (1909), p. iii.) The aqueous solution behaves on concentration similarly to the other halogen acids; E.
P. 2207); and by the action of ammonia on a-halogen ketonic compounds (W.
Chablay, Comptes rendus, 1906, 1 43, p. 123) 2CH 2 :CH CH 2 OH+2NH 3 Na = CH,:CH CH3+CH2:CH CH20Na +NaOH+2NH31 from the lower members of the series by heating them with alkyl halides in the presence of lead oxide or lime: C5H,9-I-2CH31 =2H1+ C 7 H, 4 i and by the action of the zinc alkyls upon the halogen substituted olefines.
The formation of addition compounds with the halogens, halogen hydrides, and with nitrosyl chloride, is characteristic of many, whilst others unite readily with nitrogen peroxide.
Zelinsky, Ber., 1901, 34, p. 3 2 49); and by eliminating the halogen acid from monoor di-halogen polymethylene compounds by heating them with quinoline.
Alcohols are obtained from the corresponding halogen compounds by the action of moist silver oxide, or by warming them with silver acetate and acetic acid; by the reduction of ketones with metallic sodium; by passing the vapours of monohydric phenols and hydrogen over finely divided nickel (P. Sabatier and J.
The esters of the acids may also be obtained by condensing sodio-malonic ester with a-halogen derivatives of unsaturated acids: CH H?
The Skraup reaction is a perfectly general one for primary amino-compounds; the halogen-, nitroand oxy-anilines (aminophenols) react similarly, as do also the toluidines, naphthylamines, aminoanthracene, metaand para-phenylene diamines, and orthoand 7-aminoquinoline.
The tertiary phosphines are characterized by their readiness to pass into derivatives containing pentavalent phosphorus, and consequently they form addition compounds with sulphur, carbon bisulphide, chlorine, bromine, the halogen acids and the alkyl halides with great readiness.
Halogen Compounds.-Phosphorus trifluoride, PF 3, discovered by Davy, may be obtained mixed with the pentafluoride; by direct combination of its elements; from the tribromide and arsenic trifluoride (Maclvor); from the tribromide and zinc fluoride, and from dried copper phosphide and lead fluoride (H.
It receives application in synthetic organic chemistry by virtue of its power to remove the halogen atoms from alkyl haloids, and so effect the combination of the two alkyl residues.
Compounds of antimony with all the halogen elements are known, one atom of the metal combining with three or five atoms of the halogen, except in the case of bromine, where only the tribromide is known.
They are obtained by condensing a halogen derivatives of ketones with acid-amides (M.
The dihydro-oxazoles or oxazolines are similarly formed when 13-halogen alkyl amides are condensed with alkali (S.