Open main menu
This page needs to be proofread.

P. J. Schestakov (J. Russ. Phys. Chem. Soc.; 1905, 37, 'p. 1 1=) obtained hydrazine by oxidizing urea with sodir11'h-Yp01{11101'lf° in the presence of benzaldehyde, which, by combihingwxth the hydrazine, protected it from oxidation. F. 'Raschig (Germain Patent x98307, 1908) obtained good yields by oxidizing ammonia with sodium hypochlorite in solutions made-viscous with glue. Free hydrazine is a colourless liquid which boils at 113- 5° and solidifies about o° C. to colourless crystals; it isheavler than water, in which it dissolves with; rise of temperature. It is rapidly oxidized on exposure, is a strong reducing agent, and reacts vigorously with the halogens. Under certain conditions it may be oxidized to azoimide (A. Browne and F. F. Shetterly, J. Amer. C.S., 1908, p. 53). By fractional distillation of its aqueous solution by azine hydrate N2H4~H20 (or perhaps H2N4NI'LOH), a'strong base, is obtained, which precipitates the metals from solutions 'of copper and silver salts at ordinary temperatures; It dissociates completely in a vacuum at r43°, and when heated under atmospheric pressure to 183° it decomposes into ammonia and nitrogen (A. Scott, J. Chem. Soc., x9o4, 85, p. 913). The sulphate NéH4-HQSO4, crystallizes in tables which are slightly soluble” in c'old water and readily soluble in hot water; it is decomposed by heating above 2 5o° C. with explosive evolution of gas and liberation of sulphur. By the addition of barium chloride to the sulphate, a solution of the hydrochloride is obtained, from which the crystallized salt may be obtained on evaporation.

Many organic 'derivfztivc-s Offhydrazine are kriOWIl, theumrmst important being phenylhydrazine; which was discovered bi Emil Fischer in 1877. It can be best prepared by V. Meyer and ' e¢co's method (Ber., 1883, 16, p. 2976), °5WhiCh' consists in reducing phenyldiazoniurn chloride in concentratedghydrochloric acid, s0luti0n, W1th stannous chloride also dissolved ixpconcentrated hydrochloric acid. Phenylhydrazine is liberated from the hydrochloride so obtained by adding sodium hydroxide, the solution being then extracted with ether, the ether distilled off, and the residual oil purified by distillation under reduced pressure. Anothei' method due to E, , iBamberger. The diazonium chloride, by” the addition of an alkaline sulphite, is converted into a diazosulphonate, which is then reduced by zinc dust and acetic acid to phenylhydrazine potassium' sulphlte. This salt is then hydrolysed by heating it with hydrochloric acid('6H5NgCl + KZSO3 = + C5H5N2'SO3K, /

L'5H5N2'SO3K + = C5H5'NH'NH'SO3K, " 'l

C, H;NH»NH-SOBK-+-HCl+ H2O=C¢H»-NH~NH»1l-ICl-+ KHSO4. Phenylhydrazine is a colourless oily liquid which"'t'i1irris Brown on exposure. It boils at 241° C., and mclts at I7-5° C. It'is 'slightly soluble in water, and is .strongly basic, forming welhiiefined salts with acids. For the detection of substances containing the, carbonyl group (such for example as aldehyde's and ketones) phenylliydrazme rs a very important reagent, since it combines with them with elimination of water and the formation of well-defined kydrqzones (see ALDEHYDES, Kmoxns and SUGARS). It is a strong reducing agent; it precipitates cuprous oxide when heated 'With Fe, hling'S solution, nitrogen and benzene beipg formed at the sa-me time-f C6H5-NH-Nl-I2'+ 2Cu() = CugO+N, +H2O+ CGH4 By energetic reduction of phenylhydrazine (e.g. by use of zinc dust and-hydrochloric acid), ammonia and aniline are produced—C@H5N'H-NH; +~.2H = C@H, NH, + Nl-lg. It is also a most important synthetic reagent. It combines with acetb-acetic ester to forrn phénylmetlry, lpyrazoloneQ from which antipyrine (q.v.) may be obtained. 'Indolés'(qHv.) are formed by heating certain hydra zones with anhydrous zinc c loride; while semicarbazides, pxrrols (q.v.) and many otherxypes of organic compounds may be synt ésized by the use of suitable phenylhydrazine derivatives.

HYDRAZONE, in chemistry, a compound formed by the condensation of a hydrazine with a carbonyl group (see Aldehydes; Ketones).

HYDROCARBON, in chemistry, a compound of carbon and hydrogen. Many occur in nature in the free state: for example, natural gas, petroleum and paraffin are entirely composed of such bodies; other natural sources are india-rubber, turpentine and certain essential oils. They are also revealed by the spectroscope in stars, comets and the sun. Of artificial productions the most fruitful and important is provided by the destructive or dry distillation of many organic substances; familiar examples are the distillation of coal, which yields ordinary lighting gas, composed of gaseous hydrocarbons, and also coal tar, which, on subsequent fractional distillations, yields many liquid and solid hydrocarbons, all of high industrial value. For details reference should be made to the articles wherein the above subjects are treated. From the chemical point of view the hydrocarbons are of fundamental importance, and, on account of their great number, and still greater number of derivatives, they are studied as a separate branch of the science, namely, organic chemistry.

See Chemistry for an account of their classification, &c.

HYDROCELE (Gr. ὕδωρ, water, and κήλη, tumour), the medical term for any collection of fluid other than pus or blood in the neighbourhood of the testis or cord. The fluid is usually serous. Hydrocele may be congenital or arise in the middle-aged without apparent cause, but it is usually associated with chronic orchitis or with tertiary syphilitic enlargements. The hydrocele appears as a rounded, fluctuating translucent swelling in the scrotum, and when greatly distended causes a dragging pain. Palliative treatment consists in tapping aseptically and removing the fluid, the patient afterwards wearing a suspender. The condition frequently recurs and necessitates radical treatment. Various substances may be injected; or the hydrocele is incised, the tunica partly removed and the cavity drained.

HYDROCEPHALUS (Gr. ὕδωρ, water, and κέφαλὴ, head), a term applied to disease of the brain which is attended with excessive effusion of fluid into its cavities. It exists in two forms—acute and chronic hydrocephalus. Acute hydrocephalus is another name for tuberculous meningitis (see Meningitis).

Chronic hydrocephalus, or "water on the brain," consists in an effusion of fluid into the lateral ventricles of the brain. It is not preceded by tuberculous deposit or acute inflammation, but depends upon congenital malformations or upon chronic inflammatory changes affecting the membranes. When the disease is congenital, its presence in the foetus is apt to be a source of difficulty in parturition. It is however more commonly developed in the first six months of life; but it occasionally arises in older children, or even in adults. The chief symptom is the gradual increase in size of the upper part of the head out of all proportion to the face or rest of the body. Occurring at an age when as yet the bones of the skull have not become welded together, the enlargement may go on to an enormous extent, the spaces between the bones becoming more and more expanded. In a well-marked case the deformity is very striking; the upper part of the forehead projects abnormally, and the orbital plates of the bone being inclined forwards give a downward tilt to the eyes, which have also peculiar rolling movements. The face is small, and this, with the enlarged head, gives a remarkable aged expression to the child. The body is ill-nourished, the bones are thin, the hair is scanty and fine and the teeth carious or absent.

The average circumference of the adult head is 22 in., and in the normal child it is of course much less. In chronic hydrocephalus the head of an infant three months old has measured 29 in. and in the case of the man Cardinal, who died in Guy's Hospital, the head measured 33 in. In such cases the head cannot be supported by the neck, and the patient has to keep mostly in the recumbent posture. The expansibility of the skull prevents destructive pressure on the brain, yet this organ is materially affected by the presence of the fluid. The cerebral ventricles are distended, and the convolutions are flattened. Occasionally the fluid escapes into the cavity of the cranium, which it fills, pressing down the brain to the base of the skull. As a consequence, the functions of the brain are interfered with, and the mental condition is impaired. The child is dull, listless and irritable, and sometimes imbecile. The special senses become affected as the disease advances; sight is often lost, as is also hearing. Hydrocephalic children generally sink in a few years; nevertheless there have been instances of persons with this disease living to old age. There are, of course, grades of the affection, and children may present many of the symptoms of it in a slight degree, and yet recover, the head ceasing to expand,

and becoming in due course firmly ossified.