633 



VALERIANIC GROUP. 



VALLEYS. 



531 



and cetacea, and in the berries of the guelder rose. It is also a product 

 of the action of caustic potash on oil of camomile ; of oxidising agents 

 on fate ; is often present in decaying cheese ; and ia formed on passing 

 amylic alcohol (fousel or fusel oil) vapour through a tube containing the 

 hydrates of soda and lime heated to 400 Fahr. In the latter process 

 valerianate of soda is produced, which, when cool, must be plunged 

 rapidly into cold water, or it would take fire spontaneously. The 

 aqueous solution acidified with sulphuric acid and distilled furnishes 

 valerianic acid. Another and more convenient method is to distil a 

 mixture of amylic alcohol, bichromate of potash, and sulphuric acid : 



C IO H II. HO + O, = 2IIO -f HO, C lt U,0., 



Amylic alcohol. 



Valerianic acid. 



Some valerianate of amyl also passes over ; the distillate should there- 

 fore be heated with caustic potash when amylic alcohol is volatilised : 

 the residual valerianate of potash may then be decomposed by sulphuric 

 acid and the mixture distilled, when pure valerianic acid will be 

 obtained. 



Valerianic acid forms two hydrates. When it is separated from the 

 aqueous solution of a valerianate by a stronger acid, it contains, 

 according to Liebig, three atoms of water, of which two may be 

 separated, by distillation, in the state of pure water, which afterwards 

 becomes milky, and at last the colourless monohydrate passes over in 

 distillation. 



This monohydrate is oleaginous, very fluid, of an acid penetrating 

 odour, like the valerian root ; its taste is acrid and sharp, with a 

 sweetish after-taste ; it produces a white spot on the tongue. It does 

 not become solid at Fahr. Ita density is 0'937, and it boils at 347 

 Fahr. The terhydrate boils at about 270. The monohydrate dis- 

 solves in 30 parts of water at about 53 : it dissolves in all pro- 

 portions in alcohol, ether, and crystallisable acetic acid; sulphuric 

 acid when heated carbonises it. It dissolves iodine and camphor. 



Valerianic aeid combines with bases to form salts, which are called 

 ralerianatet ; the potash and soda salts are very soluble, deliquescent, 

 and crystallise with difficulty. The valerianates of lime and baryta 

 are also very soluble, but they are crystallisable and unalterable in the 

 air ; the magnesian salt crystallises in efflorescent needles. The pure 

 monohydrate absorbs much ammonia, becoming, after a time, a solid 

 mass of snow-white, non-deliquescent, crystals of valerianate of 

 ammonia. Valerianate of zinc, readily prepared by double decom- 

 position and used to some extent in medicine, is a pearly white salt, 

 having a faint odour of valerianic acid and a metallic astringent taste. 



Chlum-alerixic Acid (HO.C.oCH.ClJOJ and Morovakrotic acid 

 (HO,C 1( ,(H 4 C1,)0 3 ) are formed when chlorine gas is passed into 

 valerianic acid. They are heavy colourless, inodorous liquids, and 

 form well-defined, stable monobasic salts. From the amount of 

 chlorine in them, these acids are sometimes termed trichlormalerianic 

 and tetrachloruvalerianic acid. 



,oi-alerianic Acid (HO,C 10 (H,N0 4 )0,) is a volatile, beautifully 

 crystalline body, resulting from the prolonged action of the strongest 

 boiling nitric acid on valeriauic acid. It is subUinable and forma 

 stable salts. 



Valerianic anhydride or anl,ydroia valerianic acid (C 10 H,,0,), is 

 formed when one part of oxychloride of phosphorus is gradually 

 added to six parts of dry valerianate of potash ; the product is washed 

 with dilute solution of carbonate of soda, digested in ether, the 

 etherial solution dried with chloride of calcium and evaporated, when 

 mic anhydride is left as a colourless liquid of agreeable odour; 

 sp. gr. 0-934 ; boiling point, 419 Fahr. ; vapour density, 6'23. 



VALKRIANIC GROUP. A cluster of chemical substances, each 

 supposed to contain, or be derived from, the theoretical radical raleryl 

 ' <?)- 



acid is best produced by the action of strong oxidising 

 agents on fusel oil. [VALKRIAJUC ACID.] 



raleryl-aldehyd or ralerul (C 10 H 0.,, H), hydride of raleryl, is formed 

 on oxidising fusel oil (amylic alcohol) with less powerful agents than 

 those necessary to form valerianic acid. Thus a mixture of bichro- 

 mate of potash, sulphuric acid, and fusel oil furnishes valeral. It is 

 purified by mixing with a saturated solution of bisulphite of soda, 

 recrystaUising the double salt thus formed, distilling with carbonate 

 Msh, and drying the distillate over chloride of calcium. Valeral 

 is a colourless limpid liquid of powerful penetrating odour, and burn- 

 ing taste ; soluble in alcohol, ether, and the volatile oils ; insoluble in 

 water; burns with a bright flame; boils at 230 Fahr.; vapour 

 density, 2'96 ; specific gravity, at 71 Fahr., is 0'820 ; oxidising agents 

 convert it into valerianic acid, and ammonia combines with it to form 

 crystalline rakryl-aldehyd-ammonium or vakrylide of ammonium 

 ' , ( ->j, NHJ. 



Valcraldine (C^Hj.NS.) results from the action of sulphide of 

 hydrogen on valeryl-ammoniuin suspended in water containing a small 

 quantity of free ammonia : 



3(C 10 U,0,, MI.) + 6H8 = C 31) H 31 N3,' + 6HO + 2NH.8 



It is an oily, volatile, alkaline liquid of disagreeable odour, and com- 

 bines with acids to form salta. 



Leucin, a body associated with the chemistry of animal substances, 

 appears to be a valeryl derivative, inasmuch as it may be formed by 



the action of hydrocyanic and hydrochloric acids upon valerylide of 

 ammonium. It is treated of in detail in a separate article. [LEUcm.] 



Chloride of raleryl (C 10 H 9 0,,, Cl) is formed on reacting with proto- 

 chloride of phosphorus and monohydratcd valerianic acid. It is a 

 colourless mobile, fuming, liquid ; rather heavier than water, and boils 

 at about 240 Fahr. 



Uromide of valeryl (C 10 H 9 0. 3 Br), is obtained iu the same manner as 

 the chloride, the bromide instead of the chloride of phosphorus being 

 used. It boils at about 290 Fahr. 



Valerone (C 18 H 1S 2 ), the valerylide of butyl (C 8 H 9 , C 10 H,0), is a light 

 colourless liquid of agreeable ethereal odour, produced when valeri- 

 anic acid is distilled with excess of lime. A mixture of valerate of 

 potash and acetate of soda yields, by distillation, an oil which is pro- 

 bably vala-ylide of methyl (C.,H 3 , C 10 H 9 0.,). 

 ( C 10 H 9 2 ' 



Valeramide (N < H ) is formed by boiling valeriauic ether 



( H 



(valerate of ethyl) with strong ammonia : on concentrating and cooling 

 the solution, valeramide crystallises out in brilliant plates. It is 

 neutral, fusible, volatile, and soluble in water, alcohol, or ether. Heated 

 with phosphoric anhydride it loses the elements of water and is con- 

 verted into cyanide of butyl (C 3 H 9 , NC S ) or valeronitrile (C 10 H 9 , N). 



Valeronitrile is also one of the products of the oxidation of gelatin 

 by chromic acid ; it is accompanied by another somewhat similar 

 liquid valeracetonitrile (C M H Jt N,,0,,). \~alcranilide or phenyl-mlera- 



mide (N 



is produced on digesting valerianic anhydride 



and aniline together. It crystallises in long, brilliant needles, slightly 

 soluble in water, but very soluble in alcohol ; melts at 239 Fahr., and 

 boils without decomposition at 428 Fahr. 



raierins. Combinations of valerianic acid and glycerin. Three of 

 these have been obtained, namely : 



Monovalcrin 

 Divalerin . 

 Trivalerin 



t +C,H,O, -2HO 

 1 + C H 8 O -4HO 



The proportion of the constituents, the temperature employed and 

 the state of concentration of the mixture, determines which of the 

 three shall be formed. Valerocftlorhydrin is a valeriu containing the 

 elements of hydrochloric acid. 



Valeryl-urea, or ralei-ureide has already been alluded to [UREA]. 



Oil of valerian, obtained as described under ESSENTIAL OILS, 

 generally contains about 5 per cent, of valerianic acid ; 25 per cent. 

 of a neutral volatile hydrocarbon, boiling at 160 Fahr., and termed 

 valerenc (C, H,,), identical with the borneene of Borneo camphor ; and 

 about 70 per cent, of an oxidised portion containing resin and valerol. 

 Valerol (Cj.H^O,) is a stearopten, and condenses as a crystalline solid 

 in the neck of the retort in which the oil of valerian is fractionated. 

 It is lighter than water, in which it ia insoluble ; ia readily dissolved 

 by alcohol, ether, and essential oils ; ia reainified slowly in the air, 

 more readily by nitric acid; and with sulphuric acid forms blood-red 

 tnljihmaleruUc acid. 



VALERIC ACID. [VALEHU.NIC ACID.] 



VALERIC ETHER. [ETHYL.] 



VALERINE. [VALERIANIC GROUP.] 



VALEROCHLORHYDRIN. [VALERIANIC GHOCP.] 



VALEROLE. [VALERIAMC GROOP.] 



VALERONE. [VALERIANIC GROUP.] 



VALERONITRILE. [VALERIANIC GROUP.] 



VALERUREIDE. [UREA; VALERIANIC GROUP.] 



VALERYL. [VALEHIANIC GROUP.] 



VALERYLUREA. [UREA; VALERIANIC GROUP.] 



VALLEYS. The term Valley, from the Latin Vallis or Valla, of 

 the same signification generally, may be applied, in its most compre- 

 hensive meaning, to any depression on the surface of the globe. " The 

 largeat valleys form the beds of the great oceans. Seas, bays, gulfs, 

 &c., are all valleys below, or partially below, the level of the sea." But 

 in the common acceptation of the term, valleys are those depressions 

 which are observable above the sea-level, separating or intersecting 

 mountain-ridges, and in fact breaking them up into separate mountain- 

 masses, and in which are the basins of inland seas and lakes, the beds 

 of rivers, &c. Mountains and hills, therefore, are the boundaries of 

 valleys. Occasionally a valley ia formed by a ridge of elevated land 

 entirely, or almost entirely, surrounding the basin of an inland sea or 

 of a lake. The word vale, sometimes employed synonymously, is the 

 diminutive, but is more properly applied to the depressions between 

 eminences of moderate elevation, or hills, which, together with them, 

 form what is called undulating country. Valleys parallel to the 

 mountain-ridgea or chains which they separate, or which bound them, 

 vre said to be longitudinal ; while those the direction of which is 

 transverse are so called. Both may be principal or lateral, the latter 

 designation being usually applied to the smaller transverse valleys 

 uniting the principal. But these epithets admit of innumerable 

 variations, and merge, in fact, into common descriptive language. 



The citation above, in which the term valley is applied to the 

 depressions filled by sea, is from an unquestioned authority, the Rev, 



