Mit. It. ltAIL'1'ON ON XX.-On some New Compounds of Phosphorous dcid. By ROBEHTRAILTON,F.C.S. STUDENT IN THE LABORATORY OF UNIVEXSITP COLLEGE. According to Wurtz's vicw of the constitution of the phospliites they are all bibasic. The crystallisecl hydrate of phosphorous acid contains three atoms ol water two of which are basic and may bc replaced by two atoms of a metallic oxide; but the third he says is inseparably bound up with the acid and is essential to its existence as an acid. Phosphorous acid may indeed be regarded as phos- phoric acid in which one atom of oxygen is replaced by hydrogen. According to this view the formula of the crystallised hydrate will be 2H0,PHO, and the general formula of a phosphite 2M0 PHO,. The experiments forming the subject of the present papcr 'cvcrc made with the view of proving that the hydrogen which Wurtz con- siders essential to the existence of a phosphite may be replaced by ethyl amyl &c A quantity of ethylate of soda was prepared by acting upon per- fectly absolute alcohol with sodium and evaporating to dryness at a temperature of about 120' C.A retort was used of about thrcc times the capacity required for the bulk of ethylate of soda produced. The retort containing the dry ethylate of soda was connected with an apparatus for upward distillation and a funnel which admits of being closely corked was secured in the tubulure. On the opposite page is a sketch of the apparatus used; but of course any other arrauge- ment which will cause the condensed vapour to return into the retort will answer the purpose.For every three atoms of sodium used one atom of terchloride of phosphorus was weighed out and mixed with five times its bulk of pure ether. This mixture was introduced into the retort by the funnel a fcw drops at a time the retort during the wholc of the process beins heated up to the boiling point of ether by a water-bath. The intro- duction of the mixture of ether and terchloride of phosphorus occupies a considerable time and must be conducted with caution as the action on each successive introduction is somewhat violent. After all the terchloride of phosphorus had been introduced the hcat was con-tinued until the vapour evolved no longer reddcned blue litmus paper. The ether was then distilled ogby the water-bath the retort trans- f(wed to an oil-bath and tlic oil gradually hcatcd up to 200' C.at S(fME NEW COMPOUNDS OP PHOSPHOROUS ACID. The end of the tnbc dips into nicwury. which point it was steadily maintained until the whole of thc ~ICW product was eliminated. When the operation is carefully conducted very nearly the theo- retical quantity requircd by the formula is obtained. The reaction is easily explained by the following cquation :-3 (NaO C,H,O) +PCl,= 3 C,R,O PO i-3 Na C1. The crude product is distilled in a current of hydrogen as it is found to oxidise if distilled in air and that portion which comes over at 188' C. is collected and redistilled. Towards the end of each redistillation when only a very minute quantity of the substancc is left in the retort a frothing occurs the thermometer falls phos-phuretted hydrogen is given off and if the retort be opened at this juncture the gas inflames spontaneously with a violent explosion.I may here mention a remarkable fact regarding the boiling point of this body. In air it is comtant at 191O C. ; in hydrogen at 188' C. 218 MR. R. RATLTON ON Phosphite of ethyl is a neutral somewhat oily substance possessing a peculiarly offensive odour. It is soluble in water alcohol and ether and burns with a bluish-white flame; its sp. gr. is 1.075 at 60' F. The carbon and hydrogen were estimated by the ordinary method ; the phosphorous acid as follows :-Weighed quantities of the liquid were introduced into stoppered bottles and concentrated nitric acid added.The bottles were left loosely stoppered in a tolerably warm situation for several days ; they were then gently heated until nitrous fumes were no longer evolved. The contents of each bottle were then transferred into separate beakers and the phosphoric acid precipitated as phospliate of magnesia and ammonia which was ignited. The analysis furnished the following results :-0-2405 grm. yielded 0.3786 grm. of carbonic acid I I , 0.11320 , water. 0.5115 , , 0.8047 , carbonic acid ,> >> , 0,4155 , water. 0.4513 , , 0,3020 , 2MgO PO,. 0*4110 , , 0.27140 , >? The percentages are- Cdculuted. Found. /---Q-12C . 72 43.11 42.91 42.89 15H . 15 8.98 8.87 9.03 30 .24 14*37 15.16 14.66 YO,. -56 33.54 33.06 33.42 L___-167 100-00 3 OO*OO 100.00 The vapour-density was ascertained by two experiments ~011-clucted according to the method described by me in the Society's Journal for October 1853 ; and it will be seen that they agree with the calculated density 1 =5*800 Experimental densities { 2 = 5.877 Calculated = 4 volumes 5.763 Tribasic Phosphite of AmyL-This body was prepared from arnylate of soda in a precisely similar manner to that described for the preparation of tlie cthyl-conipound and the analysis was con- ductctl by thc mile process. SOME NEW COMPOUNDS OF PHOSPHOROUS ACID. 219 The production of this body may be explained by the following equation :-3 (NaO CloHllO) +PC1,=3 C,,H,,O PO + 3 Na C1.Its analysis furnished the following results :-0.2477 grm. gave 0.5571 grm. of carbonic acid , 0.2521 , water. ?J ,? 0.31'72 , , 0.7123 , carbonic acid , , 0.3300 , water. 2MgO PO, ,? I.2763 , , 04855 , 14200 , ,) 0.5405 , > The percentages will be as follows :-Calculated. Found. /-.61.3430C. . 180 61.43 61-24 33H . 33 11.26 11.31 11-55 30 . 24 8.20 8-56 8.40 PO . 56- 19.11 1.8.79 18.81 293 100.00 100~00 1 oo*oo Phosphite of amyl is an oily neutral body possessing a still more ofknsive odour than the ethylcompound and is more easily decom- posed by heat. It boils in hydrogen at 236' C. is insoluble in water but soluble in alcohol and in ether. Phosphite of ethyl appears to form two classes of salts accordins to the amount of metallic base presented to it.Thus by acting upon it by one and two atoms of hydrate of baryta respectively in a manner which will be described further on we obtain first a salt in which one atom of ethyl is replaced by one atom of barium,-a reaction which the following equation will explain :-3 C,H,O PO + BaO HO = BaO 2C4H,0 PO + C41-1602. The formation of the second salt may be thus explained :-3 C4H,0 PO + 2 (BaO 130) = 2 BaO C,H,O PO + 2C,H60,. I may here remark that I could not succeed in replacing the third atom of ethyl by barium. BaO 2C,H,O PO,.-This salt is formed when to one atom of baryta dissolved in hot water one atom of phosphite of ethyl is added and the whole gently heated for a few minutes. Alcohol is given off the liquid becomcs neutral and if carefully evaporated in a water- bath deposits the salt as a confused crystalline mass.This salt is extremely soluble in water soluble in dilute alcohol but ouly slightly MR. It. RAILTON ON so in absolute alcohol. The baryta salt was recrystallised the crystals dried between folds of blotting-paper and then under an exhausted receiver over sulphuric acid until it ceased to lose weight. It W~H then transferred to an oil-bath and heated up to 108' C. which teniperature does not decompose it. It is very deliquescent and consequently the analysis shows a somewhat greater increase of hydrogen and deficiency of carbon than might be otherwise expected. 0.8320 grm. yielded 0.6910 grm. of carbonic acid , 0.3710 , water.Y> fJ 1,6195 , , 1.3505 , carbonic acid 9 1) It 0.7455 , water. 1.1065 , , 0*6285 ,) BaO so, , 0*6070 , 2Mg0 PO,. 1) 1.Y 1.1301 , , 0.6380 , BaO SO, YY J9 , 0.6190 , 2Mg0,PO,. Ik'roxn which results the following percentages were deduced :-Calculatect. Found. -SC . . 48-00 23.22 22.65 22.74 1011 . . 10.00 4.84 4.95 5-11 20 . . 16-00 7-74 7.98 8-00 BaO . 76.66 37.09 37.32 37.09 PO . 56.00 27.11 27-10 27.06 206.64 100~00 100~00 100*00 The combustion in the first experiment was made with oxide of copper; in the second with chromate of lead. The baryta and phoaphoroas acid were estimated from the same salt. The salt was dissolved in water and the baryta precipitated with pure sulphuric acid. The filtrate froin the sulphate of baryta was then carefully evaporated to a small bulk and the phosphorous acid oxidised by means of concentrated nitric acid then Precipitated as the phosphate of magnesia and ammonia which was well washed dried and ignited.The potash salt was obtained from the baryta salt by double de- composition with sulphate of potash. It crystallises with difficulty in thin plates radiating from the centre; is soluble in alcohol but not in ether and is deliquescent. The soda salt was obtained in a pirriilar manner and has similar properties. I did not succeed in crystallising it. The nickel zinc iron and magnesia salts were also fornied by cloublc dcconilmitioii with thcir sulphatcs Noiic of them crystallise . SONE NEW COMPOUNDS OF PHOSPHOROUS ACID.221 they are extremely soluble in water but appear to be insoluble iu alcohol. In attempting the formation of the copper salt the copper was reduced even on evaporating ii2 vucuo. 2 BaO C,H,O BO,.-When two atoms of baryta are dissolved in hot water and one atom of phosphite of ethyl added to it and the whole gently heated alcohol is given off and this salt is procluced. It does not crystallise nor do any of the salts prepared from it by double decomposition with the various sulphates. It was dried at 108' C. and gave the following results :-0.7025 grm. yielded 0.2495 grm. of carbonic acid > 9 , 0.1805 , water. 1.82CO , , 1*7%10 , BaO SO, I >> , 0.8372 , 2MgO,PO,. 1.1600 , , 1.0950 , BaO SO, , J7 ,) 05335 , 2MgO PO,.The percentages are ns follows :-Calculated. Founcl. 4c . * . 24.00 9\75 9.69 5 H . . . 5.00 2-03 2.06 0 . . . 8.00 3-35 3.40 2BaO . . 153.28 62.23 62.13 PO . . 56.00 22.74 22.72 -246.28 100.00 100~00 When imre than two atoms of baryta are mixed with one atom of phosphite of ethyl the excess of baryta is gradually deposited on evaporation as carbonate or if the evaporation takes place in uacuo as hydrate. This salt may be evaporated in a water-bath without decomposing but on boiling it is readily deconipoged into alcohol which is given off and diphosphite of baryta which is deposited in shining scales. Analysis of the deposited salt :-1.5510 grm. yielded 1.5905 grm. of BaQ SO, >3 >7 , 0.7720 , 2 MgO.PO,.0.9605 f , 0.9850 , BaO SO, >? 2) , 0.4780 , zni4g0 PO,. From these analyses the formula of this salt will be 2 1x0 2 BaO YO,; or on Wurtz's view NO 2BaO,PHQ,; as will be seen by coriiparing the percentages. Mlt. R. RAILTON ON NITROGLYCERTNE AND Cakmltited. Pound. 2 €10 . . 18-00 7.92 -\ I 99 8.04 2BaO . . 153.28 67-44 67-42 67.38 PO . . 56-00 - 2 4-64 24-59 24-58 -.__ s__- 227.28 1 oo*oo 100.00 100~00 The aiialysis of this salt was conducted in a similar manner to the others except that it was dissolved in dilute hydrochloric acid.