摘要:

MASON AND WHEELER THE PROPAGATION OF FLAME ETC. 1227 CXXXII1.-The Propagation of Flame in Mixtures of Methane and Air. Part II. Vertical Pro-pagation. Part 1'1. Propagation in Currents of the Mixtures. By WALTER MASON a.nd RICHARD VERNON WHEELER. PART II.-VERTI CAL PROPAGATION. THE olb'je.ctt off the1 eixpelrimeInts. herein described on the velrt.lc.al propagation od flame in mixtures of melthane a,nd air was to! obtain informamtion as to the1 magnitude od t,he ejffe.ct8 olf conve,ctioa curre'nts on the s p e d of t'he flme. Exc,eptl pelrhaqs during the '' unif o m movement," * the trans-f elrelncel of heat by coavection ourrente clelarly plays aln important part in the transmission of fla,mel a.nd is accountlabla for many of ite phenomenat. Folr example the1 well-known fact tha't the limits of inflammabilit'y of gaseous mixtures vary with the posittio,n of the1 paint of ignition a.acoIrding as t.hei flame has to pass upwards or downwards fhrough the1 mixture morel combastiblef gas b,eiing requireid tol f olm a lowe:r-limitl mixtlurei undelr the1 la.t'telr colnditdons, is elxplicab,le on the assumptioln thatl during the do'wnwasd pro.pagatlion of flame colnvelctioa curre'nts do1 not ma,te,ria,lly a,ffeIc& the tra(nsfe1rence of he1a.t tlo unburnt la,yersl 0.f the mixtlure. A like explanat,ioa can be given f o r tlhel fa.& tha,t when mixtures of methane and air aontaining lees than 7.5 and momre than 12.5 pelr cent'. of methane are ignitod a t the cent'rel olf a clolse'd spherical vessel flame reach= the1 bolttom of the v e s d later than itl reaches the1 t'op by a,n interval of time1 which varies with thei meltdhanet-matent of the mixture (T.1918 113 S45). I n general it would seem probable1 thatl flame sho,uld travel vertioally in a given mixture molre rapidly wheln i t is ignited from b l o w t'han whe'n it ,is ignite'd from a,b,ove if only by virtue of the ourrent produced by the1 heiateld gases. Undelr the spelciad c:ondi-tions olf ignitlioln a t the1 centre of a closeld vessel howelver any differenw there may be1 bet$welen the spele8ds o:f upwa,rd and down-wa.rd propagation of flame! is inappreciable with mixtares in which * The " uniform movement " is the term generally applied to the initial slow propagation of flame a t 8 uniform speed that occurs when an inflammable mixture is ignited at the open end of a horizontal tube closed at the other end.Under such conditions the propagation of flame is assumed by Le Chatelier to be '' normal " and to be effected mainly by the conduction of heat from the burning to the unburnt grtses 1228 msoN AND WHEELER THE PROPAGATION OF the s p d of flame is comparativelly rapid (mixtures coataining betwwn 7.5 and 12.5 pen cent. of methane). As belaring on this point mrtaia observations by Schloesing a,nd dO Mondesir on the combustion of mixtmrea of carbon monoxide and air should be noted. Having remarked that one ra,relly olbsetmes the ‘‘ no’rmal ” propaga,ti,oi.oln of flame b,eIca,use of t,ha development of moivemelnts in the gaseloas mixtures duel to the combustion itself they suggest tha,t one of the prinaipal causes of moIvment o r agitation of the burning mixture is the diffelrencm in density between the helabed a8nd the aoild gases “ Un m6lange gazeux a h m 6 pa,r la partie inf6rieturq b’dle toujoars plus vite que lolrsqu’il est allurn6 par 1s partie sup6rieare.Lea gaz ahaads s’618vent en effet a travers leis gax froids aveo une vitlease qui vient s’ajouter B la vitesse normale de propagahion. Mais l’a.oc616ratdon ainsi produita w t toujours tres faib3ei; ella n’elst sensibsle qu’avetc lea d l a n g e s gamux t&s lent6 et renferm6s dans dec; ttubw de grand diamBtm” ( A m . des Mimm, 1883 [viii] 4 298). As regards the (‘ unifolrm movement” (thak is to say “ normal” propagatiom of flame) we drew the colndusion (T. 1917 111, 1053) that if Le Cha,tetlietr’s definition olf it as “la mode de propaga-tion pa8r oolnduatibilit4” be acoepted it is a strictly limited phew-manan obtainable mly in t u b a within a certain range of diametm, hrge etnoagh tlo prewelnt appreciable cololling by the walls but narrow enolugh to suppress the influence of convection ourrents so that the diameter of tthe tube in which the flames travel sholuld be spelcrified wheln speeds purporting t,a be those of the1 ‘(uniform movement ” ojr ‘( nolrmad ” propaga’tion olf flame a8re reoolrded.Alterna,tiveily the initial slow movementl olf flame a.t a unifolrm spmd sh.ould be regasded simply as a past,iculas phase in t,he propaga,tioln of flame thamtl omurs when ignit’ioln is etffeded (in a quies,cmt mixture) a.t the open elnd of a straight horizontal tube (of any diameter) dosed a t the olther end and notl as reeulting from a pa,rtdcular m,olde of hela$ tra,nsfeIreaxe.* As.a result olf the present investigation i t is shown tha.t the1 lahter is the prelferablei if not the only co.rrectl way oif regarding the uniform movemeat; for tbe idea tha,t this “noirmal ” prolpagation of flame is soletly by con-duct<ion of heah frolm layelr to layer of the mixt;uret is untena>ble. Furtheir it is shown tha,t there is a uniform r6gime in the propaga-tion of flame from the open to1 the closed end of a straight tube * The influence of convection currents is noticeable with the fastest flames in mixtures of methane and air in tubes 10 cm. in diameter the visible effect being a turbulence of the flame-front; whilst in tubes of smaller diameter (5 to 9 cm.) although there is no turbulent appearance the shape of the flame-front shows that there is a definite movement of the hotter gases t;owards the upper part of the tube (T.1914 105 2609) FLAME t& MIXTURES OF ME~HANE AND AIR. P A B ~ II. 122 when the tube is vertiml a'nd the1 direction of travel of the flm0 is either upwards or downwards. I. lgniti,om ait the Open End of a VmticaJ Tuba Closed at the oltlter End.-Under them ooinditions t'he first phase in the propa-gation of flame in a horizotntlal tuba is tlhe uniform move8ment. If this uniform moveunat of flame in a holrizontd tube represents welntially t\he t,ransfelrence of heat by conduction from layer to layer od thei mixtarel simi1a.r conditions off ignitioin witb al vertioal tubs should produce a similar uniform movelment when the open end of the tube is above so that t'he flame! tra,vells downwards; for convectioa currmtls oannoit tlhetn b'e helld to platy a greater part in the transfe,rence of hetat toi t,he unbu,rnt mixture than wheln the flame is tlra,vedling horiz,ont'ally.Moreover tlhet initlal speieds oif the flames in like1 mixhures dul-ing theiir downwa,rd propagahioln in a vertical tube and during the uniform molveimetnt in a horizontal t,ube should be a,pproxima,tdy the same at all eve1nt.e in narrow tubes in which the aation of convelatiotn ourrent8 during horizonta.1 propagatioa may be1 assumed to be at a minimum. During upward prolpagation on the contrary the initial speelds of the flmm should be faster than during the '' normal " uniform movetment in a horizontlad tube aad i t would seem unlikelly that any phase in tqhe propagation s f flame corresponding with the uniform movement would be of long duration.A glass t ' u h 5 am. in diamet'elr and 5 m. long was employeld for ttha fir& series of experiments with screen-wires " folr recording tlhe speeds of flames stlretcheld a80roIss a,t intelrvals of 50 cm. Ignition was at a 5 nun. spark-gap 4 an. from the open end 04 the tube, and the first surelea-wire was str&ched a.t a distance of 20 crn. from the point of ignition. The moluth of the tuba wm provided with a flange ground t a relceive an end-pi- which was helld in position by metal clips whilstl t,he tubs wa,s being filleld witb the mixt\ure.Before ignitJag the mixture this end-piece wa)s slid gently ts onel side in such a maanelr as t a avoid caasing dist,urb,-anm of the gaaea within the t4ube. The methold of reicolrding the t,imes of fusion of the sclreen-wires and t>he general mode of pro+ mdure far similar expesiments are described in T. 1914 105 2609. As mt,iaipated t'ha speleds ab whioh the fla'mee traveilled down-wards were with all the1 mixtures employed unifoirm over a con-sidetrable dist'anae from t1he pointl of ignitioln. A viblra8tolry mow-ment bega,n in genera,l solmewhat ea(r1ier than during holrizontal propaga,tioin in a tube of the same1 diameter but witb no mixture was the distanw traveilled by t'hel flame1 a't a unifotrm speed lelss tha,n 100 om.and with t'hose containing thei lowelr pelrcentages o t metthanel it somettimes exceeded 200 0121. z z" 1230 MASON AND WHEELER THE PROPAGATION OB As regards t'he magnitudes off the speeids however our expelotea-tion (based o1n the assumptbm thab the propagation of flame during the uniform movemelnt in a horizointal tubs of small diatmetler is mainly by colnduot,ion ob heat) was falsified. I n Fig. 1 the results otbt'aineld for dolwnward propagation of fla'mel acre recorded as a speed-pelrcelntage ourvei for ootmpwisoln witlh the curve for the uniform movement in a holrizont8al tube of the same diameter. Fxa. 1. Bolth mvw are 04 the same type but the speeds of the flames during the initial &age of downward propagation are over the whollei range of inflaznmab'ls mixtluree but- t'wwol-thirds the speeds during the unif olrm movement.Prelsumab~ly t>hpn the1 t-raasfelrenm of helat by convect-ion pla#ys a aonsidelra,blel pa,r2 in aiding the propamgation of flaime during the (ho'rizontlal) unifolrm movemelnt wein in fairly nasrow tubes. This being so i t seemeld probable that contmry to our first assumption, the speled of propaga,tdon of flame upwa'rds would be not muuh i FLAME IN MIXTURES OF METHANE AND AIR. PART 11. 1231 a.ny faster ttha*n during horizoiita'l pro!paga,tion unless furt*heIr belnelfit from convection currents is obtained during the fo'rmer condi tions. Measure,ments of the speeds during t'he upward propagatlon od fla8me were notl easily made b.y the! met,hod od screlein-wires except at or nelar the limits of inflammabilitly.Over moat of the1 range of inflammable1 mixt,ures t,hhs flames somelt,imes began ta vibrate violentdy within 50 or 60 cm. of t,he open end of the tube. From t3he moment of ignition hoiwevetr the flames even those that tsave1le:d fastest seetmed to mo've a,t unifolrm or but slightly accelesating speeds. Attempts welrel theselfore madel to1 measure, t,he,se speelds the first screen-wire being placed 10 cm. from the point of ignition and the succeeding wires at distances of 25 m. from eaclh other. The1 speed of t'he flame between the first and selcrond serelea-wires was sometimes enhanced by the impettus given by the source8 of ignitiolii a distance of travel1 otf 10 cm. beling baseJy su.fficientl to allow t'his impeltus t.o die amway and a vibratory movemeat often began a t or before.the third screeln-wire. Howelver t,het measuremelnts were consistent enolugh to show t.ha,t otver tlhe cmnparafivelly short period during which the speed olf the flame travelling upwards could be reigarded as oonstant that1 speeid for a,ny mixtnrel of met,hanel and air was not grelater than du.ring t,he uniform molvvemetnt in a horizontal tube; it was someltimm less'. The reaults are inserted in Fig. 1 as approximate po,iiit,s markeld by oirclee. With the rnixtsres near the limits of inflammability, such 8,s those ccmt'aining 5.45 5-55 a.nd 13.4 pesr celnt'. of rmtha.net, the flame6 travelled over a distanwl of 200-300 cm. a.t uniform spwds which could be deltermineld a,ccura,teIly and were distinctly slower t'han thoisel of the1 unif olrm mo'vvemelnt in corresponding mixtures in a horizontal tabel.To confirm the'w reaults two1 selriea of de;telrmina,tions of speeds of flamee in a numbelr of mixturels of melthanel a.nd air were1 made by photographing on a rapidly revolving film the illuminatioln of a quartz window in a brass tubel 5 an. in diameter along which the fla;mea t'ravelleld (1) ho,rizolntally and (2) ve'rtioally upwa,rds (see t,his vol. p. 37). As t'hus melasureid the speeds ovelr the1 who3e range od mixturw welrel from 3 to 5 am. per second less whetn the flames trawlled upwasds than when t,heiy tsave1lle:d horizont,ally . Probably this slight diffelreaoe in the! speelds a,rises frofm t.he differ-ence there is in the shajpe od t,hel flame-front,; wheln travelling horizontally the flame-front has an ellipttical cross-section (see T., 1914 105 2609 Fig.2) whelrela8s when tra.vedling upwards it is cllroular so tha<t iii a t,ube8 04 give'n diamelter t'hhs circumfere,nce of The remsultls were ra,thelr irregula'r. z z" 1832 MASON AND WHEELER THE PROPAGATlON OF t-he flams-front relahive tlo its arela is greatetr with an upward-than with a hosizontally-moving flame and the uoo'ling elffeat of the walls olf the tube is correepondingly grea,teir. Sinm with flames tlrawlling horizontally thel lelngt'h of the1 major axis of the elliptioal flamefront is a t its maximum with mixtlurels nelar tlhel limit's 09 inflammability the maximum diffelreinoe in speed betwen upward-and horizontallly-moving flames in a tubel od given diameter should be found with such mixtures.This is so. Di agramm atio r e p eaeii t.a t i oins of Fra. 2. 2 Distance along the tube measured from the point of ignition. Cm. the comphtel progrem of the flames travellling in a 10 per wlnt. mixture of methane and air from elnd to elnd (240 an.) of the brass tubel with a quartz windoiw are1 giveln in Fig. 2. These diagrams have been reduced in size from tracings taken from the actual photographs which measured 60 x 40 am. and welre olbtained in the manner derscribed in Part I of this research. For the purpose of cornpaxison the flames should be regarded as travelling from right t-o left of the diagram and the photographia film as moving vextically upwards ; aatu-ally the flame was moving vectieally upwards far A , vertically dolwnwards for B, and horizontally forC.The last-named is a traoing of the pholtoigraph repro-duced as Fig. 1 Plate I oln p. 66 olf this volume,. - The rate of revolution olf the film was not the same f o r eaoh selt of photographs, so that direct comparison olf the spwlds of the fla;ntes oannot be made from the diagrams whioh however &ow clearly that the general behaviour of a fiame travelling from tlhe open to the dosed end of ik tube is not dependent on the position of the tube. WB hafve alrelady commented on the irregularity of some of the resulk obtained wheln attempting to1 mewwe the initial speeds of the flames by the smeen-wire method during upward propagation C D [To face 3 ~ ~ 6 1233 Trans FLAME m MIXTURES OF METHANE AND AIR.PART II. 1933 The reason foir the irregularity under such conditions od experiment hluame apparelnt when t.he molvemelnt of the flamee w a photo-graphed. For it was foand that with mixturm containing beltween 9.0 and 11.0 per cent. of melthane the flames were very sansitive t o the efiect olf resonannoel of the tuba and could acquire either of two speleids (but not speelds intelrmeldiata beltweem the two). If rwolnancsel was set up in the usuarl way by the movement of the flame along the tube the speeld of the flame was normal but if by some action on the part of the1 eixperimelntelr the tube was caused t a rmonate at o r very shortly after the momentl of ignition, the melan speed of the flcwnei was 20 cm.per selcolnd slower than normal. It has already been olbselrved and is in fact apparent from the photographs and diagrams thatl the1 incidence of rewnmce retards the general folrward movement od the flame until suoh time rn a wtgain delgres of turbulence is imparted to the mixture. This reltarding effect is well illustrated by the photographs reproduced in the Plate which show the progress of the flame in a 9.7 per mnt. mixture od methane and air in tlhe b r w tube over the distance 25-55 an. from the point of ignition ( A ) when the tube was remnating and ( B ) when it was not. The photographs were taken within a felw minute8 off each othelr on the same film, which was revolving at the1 same speed in each instance. Further infolrma,tiola as to the diffelream in ahara,ak between the two flamm was obtlaineld from photographs sholwing the shape of the flame-front (see Plate).A quartz tlube 5 m. in dimelm, was fixeid v e r t i d l y and mvelreld with black paper except for a slit 2.5 mm. broad a t right a8ngles tlol the axis of the tuba and 25 am. from t<he open end (the lolwer elnd) a t which ignition was &mteii. Flames travelling up the tlube in a mixture containing 8.3 per cent. of methane were photographed as they passed the slit oln a film which also travelled upwards. As each portioa of the flame-frojnt appeared a t the slit it was thus pholtographed on a fresh portion of the film and its shape was relcordeld. The arrange m a t of the quaztz lens used to1 focus the slit on the photograiphia film was suoh that an image onequarter the size of the object was obtained; the speed olf the film was therefore regulated to be as nearly 8,s possible onequarter that of the flames so as tol preeerve their relative propotiims.It will be seen that in C when the t u b wa9 raonating the undulahions olf the flame-froint are well defined aind it is unsymmetrical; in D when the tube was not resonating the flame-front is quite symmebrioal. The important point t o have established is that a phase in the propagat?ion of flame during whioh the speed is uniform is obtained when the flame trs~vels from the open to the c1-d end of a tub 1234 MASON AND WREELER THE PROPAGATION or whetheir the direction of t'ravel is horizoatlal velrt'ioally upwa,rds or vert<ioally downwards and that t,his unifolrrn speed for any given mixture is sloweat during downwasd propagation This means thab it is not permissiblei t o regard the '' uniform movement " (that is tfol say the phase of uniform speed of flame during horizontal propagation) as repremnt'ing " la viteese normals d s propagation de la fla,mme pas cofnductibilit6." I f propagation od flame solefly by conductioa of hea.t olbtains at a,ll our enrperimenh show that it is mast likely to olcmr when the1 flame travells downwards the effect of oonveatioln currelntls being assumed t,heIn t'o be negligible.When travelling dmvnwa,rds in a' glass tube 5 am. in diameter, the flame-front during the period olf uniform speed of prodpagation of flame is with all mixturw olf rmthane and air a steiady olr but gentdy undula.ting disk.There is no suspicion olf turbulence suah as mahm i& appeia,ranoe with the more rapid fla'mes wheln they travel holrizontally in such it tube. Itl seemeld possible therefore, that if convectioa currents doc nolt ma,terially assist the flame in i h propagation downwa,rds a considerable increase in t-ha diameter of t'he t,ub.e do'wn whiclh &he flamea tram1 could be made withoutl tlhelir speeds beling augmented. On trial however u&ng a met'al tube 23 an. in diameter a,nd 7 m. long i t was found thaft with mixtura aontaining mare than 7 and less than 12 per cent. of met'hane the speleds of tqhe flamea welre considerably grelater than in a glass tubme 5 am. in diamekelr a5 the curve in dotted line i n Fig. 1 shows.Wit$ the mixtures containing bet,ween 9 and 11 per cent'. of mstha.ne the1 ratio between the speed of the flame a.nd the diameter o'f the t,ube wa,s nelarly tlhe game a's when the flamels t'ravell horimntaJly (see Fig. 3 T. 1917 11.1 1052). HO~W-ever it may be during the downwasd propagation of flame in mixture6 oontaining lem than 7 olr moire than 1 2 per mnt. of methane it is obvious thelrelf o,re tha.t somet'hing othelr than con-duction of he1a.t is responsible1 f olr tlhel delvdopmelnt of tlhe molrei rapidly moving flamels in the1 tube olf lasger diametelr. The enhanced speeds ON€ t8hhel flamels as they travel downwards in the larger tubel are1 no1 dolubt. duel to turbulelnce of the flamekfront eingendemd by convelation or eddy currelnts. We can t'hhen fully elndorse Schloesing a,nd de MondBsir's st.ate melnt that the1 no1rma.l propaga,tion 0.f flame is ra8rely oibserveld wheln the word " normal" is tlakeln to imply "by wnduct,ion of h a t ." It is highly a.bnorma,l t,ha.tl such a model off helat t,rans-ference should alone1 be operativet during t'hhet prolpaga.tdo;ll of flame. In so far t.here,forel as t,he te,rm '' unifolrm movement" of flame has bwn helld to be1 the1 no,rmad propaga;t,ian of flame by conduction of heat it ought tol be discasded. The1 t,elrm is howewr a usefu FLAME IN MIXTURES OF METHANE AND AIR. PART II. 1235 one and fittingly describes a phase in the propagation of flame ( obtainalble under a variet,y olf conditions which should be specified) t,he identifioatioln and measurement of which is of considerable FIU.3. 0 0.6 1.0 1.5 2.0 C Time. Seconds. 5 value. As a name withouh implying a moldel olf heatl transfelrence during the phenomena itl deearibee there is no1 reason why it should not be retained a8nd it may be conveaielnt to do so. 11. Ignition at Ona End o f a Vertical Tubs Opem at bofth Ends. -Under thew coinditlims the tube in which the' flame travel 1236 MUOPT AND WHEELER THE PROPAGATION OF besom- a ('chimney,'' and t'here is added tot the speed oC a flame travelling up the tube the speed of the draught produced by the chimney. I n addition t'h mechaaical effeat of this draught in promolting tnrbulemm of the! mixtlure proba,b3y aagmeats tshs speed olf the flame. Flame doles not pass downwards if the mixture is ignited a t the t o p of the tube but aolnttinues to1 burn a t the1 mouth until the whole of the mixture has been drawn up.FIQ. 4. Methane per cent. I n Fig 3 are shown timedist<ancei curves for the prolpagatim of flame upwards in several mixture8 oif me\thane and air in a velrtiaal glass tube 5 m. in diaslelteir and 5 m. loag open a t both ends. Them curve8 should ba compared with those obtained wheln the tube was horizontal (Fig. I this voll. p. 42). The clharahr of bokh sets orf ourves is similar and indioatles a gradual and regular amdelratioa of speled as the flme travels from elnd to end of the tuba. This acaderation mmrs with the lowar-limit mixture (5. FLAME IN MIXTURES OE' METHANE AND AIR. PART 111. 1237 per mnt. of methane) when the flame travels upwards a result which displays dearly tlhe chimney e$e& of the tube for t3he speed of the flame in the lowelr-limit mixture is quite uniform when i t travels horizontally.The spwds of the flames a t all stage3 of their propagattion are wnsidmably faster during upward than during horizontal propa-gation for the reasons already given. Fig. 4 records the mean speeds over measureld distaaoes f o r the whole range of inflammable mixtwm ( A ) for the distance 50-100 an. measured from the fir& smmn-wire whiah was 10 an. from the point olf ignition and ( B ) for the distanaer 200-300 cm. A mrve (C) shoiwing the mean s p e d over the distanaa 50-100 cm. during holrizolntal propagatioi in the same tube is given for croimparison. Curve B presents a characteristio novel to thew invatigations on the propagation of flame in mixtures of methane and air, inasmuah as the maximum speed of flame is foiund not L ~ B is usual, with mixtures containing between 9.5 and 10.5 per cent.of methwe but with thoee containing about 12 pelr cent. This result which is of course due t o the chimney &eat of the tube, is probably q u i b adventitioas ; with. the particular diameter and length of tube employed the chimney effect assumed a maxirnum with mixtures colntaining about 12 per mt. of methane perhaps by reason of the ompoeition of the products of combustion of those zllixturm. 111. ZgnitioYn at the Closed E d of a Vertical Tube Open at the olther Ertd.-When the mixture is ignited a t the aloaed end of a tube olpen at the other end the positlion of the tube does not affeot the resulk.The rwulh obtained when the tube is holrizontal have been d e m i b d in Part I. PART III.-THE PROPAGATION OF FLAME IN CURRENTS OF MIXTURES OF METHANE. AND AIR. The object) olf these experiments was (i) ta determine whether the f a a t that the g a m were moving as a ourrent would simply add to the speed of the flame the s p e d of that o u r r a t or whether an effaat of turbulence would be introduced and (ii) tol s w if a maller quantity of methane than that which f m s the lower-limit mixture (5.4 per cent. for horizmtal or upward propagation of flame) in al sttill atmoaphere woluld be oapable of aonveying flame from one place ta another if the mixture itedf were moving. (i) The experiments with a vertiaal tuber open at1 bath ends, deaaribed in Part I1 of this rewarah had shown that the speed o 1238 MASON AND WHEELER THE PROPAGATION OF the current induced in such a tube acting as a chimney was added to the speed of a flame travelling upwards in it- and it was assumed thah turbulence caussd by the current further increased the speed of thet flame though no proof of this oould be given sinm the velocity of tthe current was indeterminate.A tube 2.5 om. in diameter and 220 can. long was fixed hori-zontally and conneloteid by rubber tubing ta it large metal gas-holder al short brass tube with a disk of metal gaum at either end being intelrposed to pre,vent flame travelling baok into the holder. Strelams of a mixture of methane and air could be caused to pass at differentl speelds along the tube both ends of whiah were open, by varying the counter-weight8 on the bell of the holder and open-ing tlhe wide-bore meitlal tap thereloa to ita full extent The mixtures+ were ignited electrioally at a point 26 am.from the colnnexion la the brass t u b and the speeds of the flames were measured by means of smeen-wirea the firstr soreen-wire being 50 am. from tlhe point of ignition. A mixture oontaining 6-35 per cent<. of methane was uwd as being one in which the speteld of flame in a still atmosphere under the conditions of the1 expelrimeats would not be excessive in corn-parison with thatt of the currents that could be p r o d u d . The rwults giving the mean sp*lds of the flames over 100 cm. were as follow : . Speed of current.Speed of flame. Difference. Cm. per second. Cm. per second. Cm. per second. Nil 287 287 23 682 559 43 952 909 75 1527 3462 Itl is thus apparent tlhat the major effeut of the ourrent is that of turbulence. The fact that suah a cmparatively gentle mover ment o0f the mixture as is represented by a speed of 23 m. per s e d sholuld nearly double the speed of tlhe flame is very striking and emphasim the important part that oonvwtioln ourrents must play in the transmission of flame. (ii) When a homogelne,ous mixture of methane and air aantaining b&ween 4 and 5 per cent. of methane is caused to1 travel1 slowly Q V ~ T a small flame such its that of a. candle flares of flame off burning methane are produced which follow the direc-tion of the current# and may eixtend for a oolnsiderable distance-a distance greater than the length of the “cap” p r o d u d by a similar mixture around such a flame in a still atmosphere.These flares of burning methane may eveln bwome detaahed from the sourcw of heah around which they form and float away for a short, distance in the stream of mixture) (T. 1914 105 2594) FLAME IN MIXTURES OF METHANE AND AIR. PART 1x1. 1239 We had also obtlained evidence that if a sufficient degree of turbulence is prolduced in a closed vessel by means of a rapidly revodving fan in a mixture od methane and air colntaining not less than 5.0 per cent. of methane flame will travel throughout the mixture following the current induced by the fan (T. 1914 105, 2595). Since the elffelct of causing SL mixture af methane and air ta travel along a tube at a fairly slow speed is tol impart turbulence ta the mixtum and sinm tghe degree of turbulence thus imparted is sufiioient greatly to increase the speed of propagation of flame in (that is t o say the1 rats of combustion of) the mixture it semned probable that tlhe loiwer limit of inflammability which is partly dependent on t<he rate of combustiion of the gas might be 10% with a slow stream of methane and air than with a quiescent mixture, just as the lolwelr limit is less for upward propagation of flame (5.4 per cent.) wheln the1 combustioln is aided by conveotion current8 than for downward (6.0 per cent.).A horizontlal glass t l u h 5 cm. in diameter and 320 cm. long was used for the elxperimelnts which were conducted in a similar manner to thow already described.The point of ignition was 17 am. from the brass t’ube ooanelotYing the1 glass tubel to1 the gas-holdelr and the first smwn-wire was 35 cm. from the point! of ignition. The elxperimenta were as fallow : (a) CH, 5.15 per cent.-Speled of current 65 om. pelr second. A flame aboutl 2.5 am. long tlravelled the whole1 length of the t u b moupying the upper half af it. The speed of the flame inmemeld gradually over the last 200 am. from 75 ta 85 m. per s e n d . ( 6 ) CH, 5.10 per cemt.-Spmd of current 65 am. per second. Observations as in previous experiment the speed of the flame being about 70 om. per seioond throughout. (c) CH, 5-05 per cent.-Spd of current 65 m. per second. A more powerful secondary disoharge had to be used to ignite this mixture.The flame produced was only 1.2 m. long but it travelled the whole length of the tqube at1 a speed of 65 om. per second-that is to say at the speed of the mrrent of mixture. (d) CH, 5.02 per cent.-The intense flaming ” discharge obtained when a Wehnelt ekmtrolytid interrupter is used in the primary cimuit of an induction coil had ~ Q I be used to ignite this mixture. Whein ignited a small flame tlravelled throughout the lengt-h od the tubel a t the sped od the current of mixture namely, 65 50 and 35 cm. per second in successive trials. With a faster s p d of curreat (about 80 cm. per second) or a slower s p d (abut 30 am. per seoond) the flame1 travelled from 200 t o 250 cm, and then did orutr 1940 MUON AND WHEELER THE PROPAGATION OF FLAME1 ETC.(e) CH, 5.00 per cemt.-With no speed of aurrent would flame travel mare than about 50 caa. from tlhe point of ignition. This was so whether the Wehnellt disaharge used to ignite the mixture WM maintained or passed mo~melntlarily, Experimenb (d) and (e) were repeated many times with the same remits a qixture containing 5-02 oc 5.03 per celnt. of methane dolea not enable flame to brave1 in it when it is a6 rest,, but when it i5 moving i~19 a crumelntl along a hbe flame travels in it at tlhe spwd of the current. A mixture containing 5.00 per cent. od methane oould not be a a w d to propagate flame under the wnditions of the exp&nente. Mixtures containing 4.95 4-90 cx 4.85 per m t . of methane gave flaresl of flame extending a few am. only along the tube. The scale on which these expmimelnlis were conduded is perhaps wasdy suffioient tor warrant the conclusiozl that flame would be aarried indeifinitely in a homogeneous mixture contlaining 5-02 pelr wnk. of methane along the roadway of a mine folr example so l a g as a aurrelnt of from 35 to 65 am. per waond was maintained. The general charadm 09 the expelriments howelver pointed to a sharp distindion between a mixture1 (5.00 per cent. methane) obviously inaapable 04 maintaining a flame apart from tihe source of heat which oiriginateld it and one (5.02 pelr clelnt. methane) in which flame was maintaineld afteir the1 ignitling souroe had been withdrawn. The flame would travel alolng tihe rood of the roadway. The waaluding parts of $,his research will dsal gelnerally with the e$eate of turbulelnoel oln the propagation olf flame in mixtura of methane and air aa prolducrd by tlhe passage of the mixtures as mrrenb almg a tube or gdlery and as induced loloally by the presence of ratridions in the gallery. Horn OFP~UB EXPERIMENTAL STATION, ESKMTALS CUMBERLAND. [Received August Qlst 1930.

ISSN:0368-1645    

DOI:10.1039/CT9201701227

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

THE OXIDISING PROPERTIES OF SULPHUR DIOXIDE. 1241 CXXXIV.-The Oxidising hoperties of Sulphur Dioxide. Part 11. Iron Phosphates. By WILLIAM WARDLAW SIDNEY RAYMOND CARTER and FRANCIS HERBERT CLEWS. THE obj& vf the experiments deearibed in the present mznmmi-clat3ion was ta determine whether the olxidising a&im of sulphur dioxide exhibited in oolnaetratd hydroohloio acid solution (Wardlaw and Clews this vol. p. 1093) was ~est~richd tol b h b add or was operaltive in ofther acid solutions. Phwphoria acid wa8 wl&d on m u a t of its noln-volatility and its mmexpdj suitlability for quantitatrive measurmentsi. EXPERIMENTAL. BxfieiGrnemt with F e v o w Pholsphta S h t w m . Solutions of f errolus phospha#b were prepared by dissolving im in phmphoria aleid (Erlenmeyer Ancnaalem 1878 194 182) and tai.ela8ting with sulphur dioxide.Essentdallly theref orel the rn0thd of procedure was practioally identical with that pemibudly employed for the investigatim of fenma uhbridei redwnb (loc. cit.). As illustrative off the met*hold used th0 following d e t d s off the1 first experiment may be given. One grah of pure iroin was dissolved in 50 U.U. of phbsphorio a,aid (I3 1-75 89 pelr centl. H,PO,) aointained in al dolsed flak a ahream of aarbon dioxide being Colntinudly passed tkotlgh the apparatus. A mloiurlessl solutibn of ferrous phosphate wm thus o;btla,ined. The evolution of hydrogen having oea+sd sulphur dioxide wm passed through the soluticm at 115O. After about ten minutes a faint milkiness was seen in the nmk of the 3mk, and in the oorursei od t l h e partides od sulphur appeared.The solution remained collolurless tjhroughout. After the sulphur dioxide had passed for four hours the gasl wit8 removed from the sollubim by the passage oif a a r h n dioxide. The femme md total iron wem detbrmined by titratioin with ptasS;um di&rmn.at.e solution. The first experiment showed that 8-1 per aeatt. of f t d a phosphah had been foirmed under the uonditims mentioned. Ih v i m of the extreme susoeptibility oif felrrous phmphatp tiol a h * sphetia d d a t i o a (Erlenmeyer Zoc. cit.) khe oxidation by d p h u r dioxide was not unexpeatad 1242 WARDLAW CARTER AND CLEWS THE OXIDISING Tempera8turel 115'. Experiments with Ferm'c Pholsphate Sollutiolns. To dehmine whether sulphur dioxide had any reducing adion on ferria phwphate 3 grams od ferria phosphata were dissolved in 50 0.0.of glaoiad phospholrio add and sulphur dioxide wa8 passed through the solutioln maintained a t 115O f o r three hours. On andysing the solution no ferrous iron muld be debated. Further elxperiments o n similar lines gave no1 evidence of reduction of the feirriu phmphate. This result s e a s to a,grea with the well-known stability of ferria phmphate in the reducing blowpipe flame. A boralx belad containing ferria iron is radily reduced whereas a, f m i o mioroawmio bead is r e d u d with diffiuulty. Temperature 150O. Experiments witit Fewow- f ewic Phosplhcat ei Sdutwws. The objwt of thew experiments was to determine whether the prolonged aution olf sulphur dioxide on ferrous phosphate would reault i n cotmplete oxidatlion to the ferria stratel.The mixtures were made by dissolving iroln in phosphoric acid excluding air during the process a,nd adding a solution of ferria phosphate in concentrated phmphoria said. Ferric iron. Per cent. I m G r T 2 a l . 0.0 8.1 12-5 15.7 21.9 24.7 25.0 28.0 39.7 -55.7 66-9 100.0 100.0 Sulphur deposit. Heavy. Moderate. Moderate. Moderate. Very light. Just noticeable. None. Ferric iron. Per cent. Ini&r%& 43.2 46.7 57.1 60.5 63.4 65.2 72.0 74.2 79.1 79.9 100.0 100.0 Sulphur deposit. Moderate. Moderate. Light. Light. Just noticeable. None. The prmnae olf the great exms of phosphoria auid teinded make tihe titration somewhat diffiault but the clharaohr of the sulphur depmit served as a goad indication of the progre&s of oxidation espeaia,lly in those case5 where1 i t wcrurred only to a slight extent.Cornpanson of the reeiults obtaJned a8t the t'wa temperaturea suggeats that felrrougi phosphate wonld be completely oxidiseld t PROPERTIES OF SULPHUR DIOXIDE. PART 11. 1243 the ferrio state but tha,t at the temperatures used in thew ex@-m0nb the velmity of reaotion is belcoming slow wit'h increasing proportion of ferria salt. Hence during the four holurs very little oxidation is deteloteld with the higher propoctions of ferrio iron. Limit of Oxidation. of Ferrous Phosphate. Expmirnentg to determine the limit of olxidation were oarried out in a spmial apparatus primarily designed for obtaining the velcrcrity of reactlion.The relactioln vewell colnsisbd of a wide-neaked flask of about 600 0.0. capacity fitted with a rubber stopper, through which pas& the bearing for a stirrelr a syphoa sampling-t u b made of uapillary tube of fairly wide bolre an inlet tube for the sulphur dioxide and al wa,ter-uololed exit tube. The syphon sampling-tube wits connected with a water-ooolled 10 0.0. buratb, whioh in turn was colnnelotleid with a suatioln pump. The stirrer was fitted with it mercury seal and clmd a t the end so that sulphur dioxide w d d be maintaineld at a slight pressure in the1 flask without leakage. A simple device was used to colntrol the pressure of sulphur dioxide in the flask. The gas issuing from a sulphur dioxide syphon was divideid by a T-piecel one arm being oonnmhd with the reactlion flask a8nd the oather connected witlh a gauge-tube containing cmmntrated sulphuria acid.By allowing the sulphur dioxide t o bubble velry dolw1y through the sulphurio atid the prwure in the reaotioln flask was maintained a t a value greater than atmospheriu the ex- pressure being proportional ta the height of the mlphurio acid column. Method of Procedure.-To 250 0.c. of phosphorio acid contained in the flask wibs addeld a definitei welight of pure iron. A ourrent of oarboa dioxide wae. then passed through the apparatus and on warming the iron dissolved. When solution was complete( the temperature of the theirmostat was adjustad tlo 150° and the stream of oarboln dioxide replaced by one of sulphur dioxide.By closing the exit tube the pressure of sulphur dioxide was adjusted. Samples of solution were periodically drawn off into the burette, allowed to awl t o the ordinary temperature the volume adjusted, and run into a flask filled with carboln dioxide. The solution was then diluted with 30 per cent. phosphofria acid and the sulphur dioxide driv0a off. The volume was made up to 100 C.O. aad titrated with N / ZO-potassium psrmanganata The titre was assumed ta be proportional to the conmntrahition of ferrous iron in the reaotion flask at the moment od sampling. Froan experiments conduotd in this way a coastlant ferric content was found to be e&ablisheld at the end of from two to three1 days and the1 following were the results obtained 1244 WA~DLAW CARTER AND CLEWS THE OXIDISfNG (a) A t a aolnae4tiratioln of 7-35 grams of iron per 250 0.0.olf plhosphoria add the aixture aotntained 36 per oecnt. of flerria irofi. ( 6 ) At a corllaentratioln od 3-65 grams per 250 u.o. the mixture mntaJnd 45 per oentl. of ferric iron. These results differ distinctly from those obtained from the synthetio mixtureis of felrrous and ferric phosphahes. This differ-ence d g h t conceivably be due to the sulphur formed in the sdu-tions ccmtlaining initia(1ly ody ferrous phosphate whiuh is absmt in the case od the synt(he1tia mixt,ures. Expelriments with synthetic mixturm of felrrolua and ferria phmphatles ta whiuh had been added finely divided or co3loidad sulphur showed that this had no observ-able deut on the degree od olxidatJoln by sulphur dioxide.In addition sulphur wm found to ha,ve no appreciable reducing power on ferria phospha’h in concentrated phosphoilic acid solution. Maquenne (BUZZ. Bolc. chim. 1890 [iii] 3 401) has shown that aqueous solutions af phosphorous acid ar0 oxidised by sdphm dioxide cmpleitely to phosphoric a,oid (compare also W Ohler, A d e m 1841 89 252 and Caxazzi Gaazetto 1886 16 169). The posaibility of the reaction 2E3P03+ S02=2H,P04 + S beJng reversible was not overlooked but experiments did not mnfim this oolnjeoture. Velocity nindl Order of Reactim.-Expdments made with the appamtius described above with a+ v i m tol dekmina the rate and order olf reactlioln gave no vary definite results prob’ably awing tlo the disturbing aotim of sulphur.L k i t i m g Comcmtratmom of Pholsphov-ic A&.-This has been determined b t w e m narrow limits for ferrous phoephate at looo. The p r d u r e followed was similar to that used in the uase of hydrolahloriu acid solutions (Wardlaw and Clews this vol. p. 1097). One graa of iron was dissolved in 50 a.a. of phmphmia mid of different mncentratioins kh0 values folr which were obtained by measuring the spwific gravity oif the phosphoric aoid and aahu-laling the colllaentrations from the tablea (Hager ‘‘ fiommelntar ziir Phasmaqija Germanisai ” ; Gmdin-Kraut’e “ Handbuah,” Val. I, Pt. 3). A gravhetric estimation was made on the solution in expt. 6 maording t a Finkmar’s melthold (Ber. 1878 11 1640) axld it was shown tlol colntain 400.7 grams of phosphoris acid per litrel, whilst 32.83 p w cent.phoaphoriu acid (elxpt. 6) contains 397.2 grams per litre. Assuming the iroln t a be in cambination as Fel(H,PO,) (Erlenmeyer Zolc. cit.) the frm aoid in 1 litre of the ferroas phosphate solution was 400.7 - 68.6 =332*1 grams. The raults are shown in table 111 PROPERTIES OF SULPHUR DIOXIDE. TABLE In. ConcentratJon of i r o n 1 gram per 50 0.0. Temperature looo. Durahicm of experiment8s foiur hours. Concentration of HsP04 per cent. .............................. 76.27 45-93 Observations ..................... sulphur. sulphur. Concentration of HSPO4 per cent. .............................. 34.38 32.83 Observations ..................... Minute Very Experiment 1. 2. Oxidation per cent. ............ 2.1 1.3 Experiment 6.6. - I Oxidation per cent. ............ amounts. minute deposit. PART 11, 3. 40.87 1.0 sulphur. 7. 31-80 N O deposit. -1246 4. 37-17 sulphur. 8. 20.02 N O deposit. --Ib is aonaluded thelrefow that oxida4tion of felrrcnxs phosphate by sulphur dioxide is just pelrceptible in a solution cmtaining 332.1 grams olf ( ‘ f r e ~ ” phwpholria acid per litre at 100’. Discussim of R esuEts. The reaoticms of sulphur dioxide with iron phmphah in the preaehae of concentrated phosphorio acid differ in several ways from tlhme with iron ohlolrides in concentrated hydrochloric acid sdutioa. I n the first plaoel there! is no1 elvidelnm tqhatl sulphur dioxide1 clan act as a reducing agelnt in the presence oC concentrated phosphoric acid folr ferria pholsphate unlike feInic ohloridel in the preseam olf the comwponding concentrated acid is not affected by the a,&ioln of sulphur diolxidei.The relaation betlwelen sulphur dioxide and iron phosphatlee in concentrated phosphoric aoid solu-tion is theiredore sollelly one olf oxidation and may be e x p r d by the equation 4Fel(HzP0,) + 4H,PO + SO = 4Fe(H2P04) + 2H,O + S. The question now arise6 as to whether the1 reachion is a revelrsible onei like1 the mrraponding felrroas chloride relaction or whether it proceeds to m p l e t i o a . The faat thab mixed ferrous-ferric phosphate sollutions gave evidence of olxidatim with relatively large perrcrentlagea olf ferric salt rather swms to indioate that the readion would ultimately proceied to completion.This idea also seems to be supported by the non-raduclibility of ferria phosphate by sulphur. Against this conception however must be plaaed the limited yield od ferrio salt from an initially pure ferrous phosphate solution and the favourable influam of the oonaentrakd phos-pholrio said on the axidaltion. Both these fa& wmld be deduce 1246 WARDLAW CARTER AND CLEWS THE OXIDISINC; from the la4w of mass action if a,pplield t o the above equation, tlaking it as relpresentjing a re8vewible reaction Undoubtedly the complimting fea,ture in tlhel raotion is t'he f ormattion of the st,able aomplelx compoand whic;h fe,rricl pholsphafe is known to form with phoepholric; a.cid. This woald accolunt for the greater yield of felrric sa,lt( from a pure1 felrroius phospha,tel solution than from a pure ferrous chloride solution owing to1 tlhe fact that the ferricl; sa,lt formeld would be removed from the1 reaction in the form of the stab,le complelx oompwnd and henoel favour the degree of oxida-tion.This forma.tion of the1 c,omplelx sa.lt may also a,cclount fomr the non-reducibility olf t'hel felrrio phosphate in concentrated phosphoria acid sollutlioln bly tlhe action of sulphur. It is quite conaeiva4b3e t8ha,t sulphur ma'y reiduclel felrric phospha,te when not in t'he form od the clolmplex compolund. Such ccmdit'ions a,re probably prelselnt wheln sulphur diolxide is passed into1 a pure ferrous phos-p h a b wlutXion. 'Thet sulphur libelraked is in a very a,ctivs state and may rea'ch with t'he ferric; phosphah genera'teld before itl is t.aken up in the folrm of the1 complex.A considera,tioln of t h w fa.ottolrs indinel the1 authofrs to the idela that the reladion of sulphur dioxide1 wit.h ferrous phosphate is a reversibmle one simi1a.r to that of sulphur diolxide with felrrous chloride in the prmence of their corresponding oonaelntlra,tletd acids but tha.t itl is modified in the case od the1 fesrous phmpha,te by the forma,tbon of the cl~nplex stable1 oo,mpound which felrric; phosphatei forms with phmphorio acid, The faclts that sulphur diolxide redurn most reladily in a veiry dilute a,cid medium and tchalt it oaidises most readily in a strong acid meidium ma4y be correlated i f oxidation a,nd relduotion a,re explained an an ionic b'asis oxidahion being retpreseated by the surrender of poaitive chasgesl and reduotioa by the trmsferenw of nelga,tive uharges.Sulphur dioxide in a,queo,us solut'ioln is genetrally regarded as a modeirately weak aaid ionising principally inta H* HSO,' and SO," ions. Itl is in this condit'ion that it reaots as a reducing agent. Thus: 2Fe'"+ SO," + H20=2Fe" +SO,"+ 2H'. I n strongly a,&d solution containing a large number of hydrions, t,he mnaelnt'ra;tioln of SO," ions will be r e d u d and on the1 above assumption its powelr of reduoing should be diminished. This is in amolrdance with expeirimental results. Nolw let it be assumed that sulphur dioixide is oapable of ionising tlo an ext#remeily minute e x t a t als a b,a,se yielding a correspond-ingly minutxet amount of sulphur ions.Itl has been shown that the sulpholxidet3 the orgvio analogue6 of sulphur dioxide hav PROPERTIES OF SULPHUR DIOXIDE. PART 11. 1247 basia propelrtiee ( F r m and Raiziss Amnalen 1910 374 90; F r o m ;bid. 1913 396 75). This tlendelncy will be all the g r a t e r tfhe larrger the number of hydrions present in solution. Thus : SO ,? OS(OH) G? SO" + 2(OH)', SO" &? S"" + 2(OH)'. In view of the large number od hydrions present in the solution, tlhe oonmntratioln of hydrolxyl ions would be reduced to a very low value and the reaction towa]rds the rightl fa,voured. Oxidation is now represented : H2O HZ* S"" + 4Fe" -+ 4Fe'" + S. I f oxidation takea place due to the ion SO", 2SO" + 4Fe" + 4Fa"' + 250, 250 + H20 + H2S,0,, which represents an intmmdiate stage in t'he reduction of sulphur dioxide to1 sulphur. Thiosulphuria acid would break u p into sulphur dioxide and sulphur. Itt may be observed thaf the latter hypotheeis is in many respects a restatement olf t#hel thionyl chloride hypot-hesis (Wardlaw and Clelws this vol. p. 1103) applield ioniclally and more generally. The oxidising prolpertiee of arsenio acid uranyl ohloride per-manganic acid and chromio acids have been explained by Stieglitz (" Qualitative Chemical Analysis," Voll. I p. 282 et s e q . ) on a similar assumption. There appears to be room for investigation of these mactions fmm the point of view o'f delelcrtlriric;al potentials when some of the assumptiolnns matdo in the1 absove coald be teateld and it is hoped that efxprimelnts nolw in progrea may throw some further light-on this hypothesis. CHEMISTRY DEPARTMENT, THE UNIVERSITY BIRMINGHAM. [Received Auqwt 27th 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701241

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

1248 PICKARD HUNTER LEWCOCK AND DB PENNINQTON: CXSXV.-The Alcohols of the Hydroaromatic and Terpene Series. Part ILL.* isoPuEegol. By ROBERT HOWSON PICKARD HAROLD HUNTER WILLIAM LEWCOCK and HANNAH SMITH DE PENNINGTON. TIEMANN and Schmidt (Bey. 1896 29 914) olbtiained the a81cohol isopulegal (11). by the hydrolysis of the condensation product of amtia anhydride aad aitrmellaldelhyde (I). The produot was so named ta distinguish it from the1 yet unknown i m e r i a secondary alcohol whiah would correspond with the keltlolne pulegone (111). Samplesl of oitmnelladdehyde often vary considerably i n deurtroratatory power and prolbably uontain the oolmpoiund, as well as tlhat of formula I (see inter diq Prins, Weekblad 1917 14 692). CM~:CH*CHz.CH,*CfHM~*CH,*CHO, c'p tiaal Chem.Our preparations of ilsopulegol from the same sample of aldehyde ([u]' + 11'6O) by the method desmibeld by Tielmaan and Schmidt, or by the mdifioattions of the same proposed by Semmler (Bm., 1909 42 2014) and by Wegsaheider and %path (Mcmatsh. 1910, 30 825) gavel isopulegol of rotaltory power [a]= k2O. In no case, however did these produds yield after olxida8tioln with chromio add any ketone forming a bisnitroeol-derivative sa oharaateristio of pulegone and similar aP-unsaturated ketolnes (compare Baeyer and Helinrich Ber. 1895 28 654). During the condensation and due to the formaftion of tlhe cyclohelxanei ring two additional aarbon atoms b m e asymmetrical so that four stmx&m.nerro pairs of dextrol- and laevwroltatolry uompounds of the formula asoribeld above to isopulagoll a.re theloretlica1ly poasible.The1 nomenolature f o r such isomerides proposed by Asohan and used in Part I1 for the melnthols is inaolnvenient heirel as it would muemitate the use of the prefix isoh twice olveir so the isopulegolls may be h e w simply deaoribed as isoipulepl a- P- and y-isolpulegoils as it is not yeltl pwible to1 determine the oonfigurations oif the respechive ismelrides. A detailed invwtigatioln of the mixtures of kpulegols obt+ained * Part I. T. 1907 91 1973. Part II. T. 1912 101 109 ALCOEOLS OF THE HYDROAROMATIC AND 'l!ERPENE SERIES. 1269 from t'he oondensat'ion of dextrorotatory oitronellaldahyde has now shown thatl two (and probably not morel) of the four possible* isomeridm are folrmetd and as the yield of the isopulegyl acwtatee rarely amounts to 50 per memt.it is probable that the aldehyde taking past in the condensation is t'he pure dexkorotatcq cam-pound of formula I. The hydrogen phthalia mters of the mixture of alcmhods obtained from the oolndelnsation prduot can be aepparated by the fractional arystallisation of t,he magnesium t and f- 15" 3.10 +5 2 0 2 % g -5 'Y & -10 - 15 - 20 i -loo li' h w - -20 ; s I ^^ 2 3 4 5 6 7 8 9 1 0 1 1 1 2 1 3 1 4 Number of carbon atoms in growing acyl chain. strychnine s d k . In this manner starting from dcitronell-aldehyde the esters of Fisopulegol and d-a-isopulegol have been isolated and it has been found that the two alcohols when reduced, yield rwpeotiveJy Z-menthol and d-neoLmentho1 both of whiah, when olxidised give I-menthone (Part 11).The analogy of theee aaseg to that of d-borne01 and Z-isobomeol which as sholwn in Part I bokb colrrespolnd with &camphor is very sltriking whilst Tschugaev (Ber. 1912 45 1293) has shown that tanamtone when * That is assuming no racemisation takes place during the condensation. 7 B&h magnesium salb are dextroroWory in ethfl-dcoholic sdution 1250 PIUKARD HUNTER LEWGOCK AND DE PENNINGTON : reduced forms bwol tanacetyl alcohols of diff elrent configuration and opposite in rstaltory power. It would appear that in general, the redudion of an optically active cyolia ketone to the corre-sponding semndary alcohol yields a mixture1 of the two possible cis- and trams-isomelrides of opposite rotatojry powers.In this connexion further analogiee may be mentioned as Asohan has described (Annulem 1901 316 196) the conversioln of d-camphorio -8 -w . U ) $ -10 ” 8 -12 -& t j F4 -14 -s1 & & 8 -16 --18 % -20 --22 I I ‘ . I I . . , 2 3 4 6 6 7 8 9 1 0 1 1 1 2 1 3 1 4 Number of carbon atoms in growing acyl chain. acid (the cis-isomeride) into E-isosamphoria acid (the trans-isomwide) and Folrster (T. 1898 73 386) the formation of d0xtro-rotatory hrnylamine and laevorotatsry meobolrnylamine from d-cramphor. The values obtained for tlhe optical rotatory polwer for ~ 4 3 5 8 ta 6438 of Z-isopulegol in the homogeneous stdate( a t 20° correspond with a olne-ter- Drude equation almost to within the experimental error but at higher temperaturw they da not.The rotator ALCOHOLS OF THE HYDROAROMATIC AND TERPENE SERIES. 1251 powers of its esters with the normal fatty acids offelr a strong contrast to those of the estelra of Z-meatlhol. Thus in the homo-logous series their molemlar rotatory powers telnd to a ooiistlant value only ah higher tempsraturee (see table I) and do not in the homogeneous state at any temperature from loo to 160° agree with a one-term Drude elquation beling visibly anomalous in dis-persive power a t tlhe ordinary temperature (me( for example], Fig. 3). Further when plotteld against mollecular weight the specifio rotatlory powers unlike1 those oif thei menthyl esters show - 0' - 6 - 10 %> n I5 -16 ! -20 p -26 Q -35 24 ' -30 s - 40 - 45 - 50 Fra.3. - - 1 ,.-I h- . - A - - - L - . - . - - - - ~ 0 20 40 60 80 100 120 140 160 180 Temperaturs. maltima (molre prolminelnt at the lower teimperatures see Fig. 2) for the valeIrato and undecoatel thah is wheln the growing ohain may be assumed to return on itself. I n elthyl-alooholia solutqion there are in addition indications of irregularities in such a ourve at t'he pro1pionat-a and olotoat.e.* The spelcial pmitions of the valerate and undelcojate on this ourve are well illustrateid in Fig. 1 which also1 shows the same pheno-menon in the curve drawn to connect moleculas weight and the temperatures (extrapollated where neoessary frolm observations * Compare in this connexion somewhat similar phenomena in the rotations of the esters of d-l-naphthyl-n-hexylcarbinol (Pickard and Kenyon T.1914, 105 2644) 1262 PICKARD HUNTER LEWCOCK AND b E PENNINGTON : given on p. 1256) atl which the esters have a dispersion ratio equal to unity for A 6438 and 4358. The rot$atolry powers are1 given in the1 tables but furthelr dimussion OX these and similar results dlbtaineld by olnel olf us and Ketnyon (T. 1914 105 830 et seq.) or olf tihe criticism by Frankland and Garnec (T. 1919 115 639) of the tentative hypothesis adolpted tlol elxplain them is post8poaeld until furthes evidence is availablel. The1 variation of the specific rolta8tlolry polwers of the1 esters with temperature from loo to! 180° is nearly linear (illustrated in Fig. 3 for the butyrate) and should be considered along with similar raults obtained by Kenyon (T., 1914 105 2226) in view of the suggestions of Patterson (T.1913, 103 156). TABLE I. Molecular Rotaltolry Polwers o$ 1-isolPuZegoll and i t s Esters in the Bomoyemeoug State. I-isoPulego1.. ............. Acetate .................. Propionate ............... n-Butyrate ............ n-Valerate ............... n-Hexoate ............... n . Hept oat e n-Octoate ............... n-Nonoate ............... n-Decoate ............... n-Undecoate ............ n-Dodecoate ............ Mpistate ............... ............ [M]$k--28.1' 18.8 17.2 12.4 14.9 13.1 12.9 12-9 12.8 12.8 13.9 12-9 13-9 [M]%P -29.9' 33.0 30.1 26.6 29.0 27.9 27.1 27.4 27.1 27.8 27.8 27.9 28.4 [M]%a-- 66.3' 30.7 25.6 14.1 20.5 14.7 14.6 14.7 14.5 16.9 17.8 16.6 16.3 [MI%.- 72.2' 61-9 61.0 62.4 57.4 54.1 53.2 53-4 53.3 63.5 53-0 63.5 64.7 E X P E R I M E N T A L. Isohtiom of l-isoPdegoJ. The mixture (b. p. 82-90"/10 m.) od alcmholls (obtained by the hydrolysis of the condenaatioln product u1f &tronellaldeIhyde, [a]= +11*6O and aoetio anhydride) is hsateld in an oil-bahh at l l O o for twelve hours with an equimolemlar amount of phthalic anhydride. The pradud is dissollved in al very dilute cold aquelous solutlion oE sodium ca,rbonatle which is then carefully axtraated with ether to remolve neutral compounds. Any dissolved ether is removed by a ourrent of air and thein the solution precipitated with the aalmlated amount of a solution od magneiurn chloride.The resulting pasty mass is straineld olff and crystalbed eight times from alcohol aontaining some water which is diminished as the separation nears completion. By working up the mother liquors (a) by coincentratlion od the alooholiu soilutions and ( b ) by reuover o l the1 hydrogen phthalic esters froin the1 more soluble fractions and re-working these as before a yield of just over 40 per cent. of the magnesium salt1 of I-isopulegyl hydrogen phthalate is obtained. Hagnesiunz. I-isopaclegyl phthalate crystallises from aqueous alcohol in lustrous flakes with GH20 (Found Mg=3.3; H20 = 14-3. C,,H,,0,Mg,6€120 requires Mg = 3.3 ; H,Q = 14.6 per centd.) which melt at 111' and are1 scluble in chlorcform o r acetone. It has [a]6438 + 7 * 8 O + 18-2O [aIjjF + ? 3 * 2 O [a]50sc -1 30-3O, a i d [a]4358 +57-4' in alcohol ( c = 5 ) a t 20'.It is decomposed by cold hydrochloric acid which preicipitates 1-isopulegyl hyldroge?, phthalate. This ester crystallises from glacial acetic acid in stogt prisms which mellt a t 106'. It has -19*39O -25.77'; [a]',893 - 23*55O - 31.91'; [a]54cl - 28*59' - 39.10°; [a]508G - 33*44', -37.55'; and [a]1358 -53.32O and - 7 5 ~ 5 8 ~ in alcohd and benzene respectiveily (c = 5) a t the tempelrctturei of the laboratory. The strychnine salt crystallisea from absolute alcohol in long, prismatic needles which melt atl 205O. The1 holmolgenelity of the eider was inferred from the constancy of its lzvorotation in alcohol and chloroform (i) aft,er an attempted fractional crystallisation from acetio acid and (ii) after conversion into1 the1 strychnine salt, which was repeatedly recrystallised and its recovery.I-isopulegol is obtained by the hydrolysis of the hydrogen phthalatei with an excess of sodium hydroxide dissolved in et?hyl alcolhol. It boils at 88'jlO mm. and its rotatory power is unaltered by partial estelrification with either phthalia o r ac&ic anhydridel the unestell-ified isopulegol and thati obtaiiield from the hydrolysis of the esters having identical rotations. When suspendeid in water containing 10 p e r cent. of gum arabic in the presence of colloidal palladium it is reduced rapidly by hydrolgen to1 a crystalline solid (m. p. 42' and [a]g"-49.4') identJca1 with I-menthol. d-ccisoPuZegoZ.-The more soluble1 oomponent obt aiiied in the selparation a,s describeld above1 od the1 magnesium saltl of I-isopulegyl hydrogeln phtlhalatei remains after the removal of the alcohol as a pasty mass which is strongly dextrorot4atosy in ebthyl-alcoholic, sollution.The mixture1 of hydrogen phthalates is recovelred from the magne(sium salts has a. specific rotatory power abofut +Oo and by oareiful fraotdonad crystallisation from aceltia acid can be further sepa,rateld the most- soluble fraotioln having [a] about + 8 O in 5 pelr cent,. ethyl-a,lcoholia solution. This dextrorotatory ester was dissoilvsd in the caloulatsd axnounti of a dilute solution of sodium carbonate and fractionally precipitated by small amounts olf mag-nesium chlotride solution. Aftelr repeating the process tern timea, VOL.CXVII. 3 1254 PICKARD HUNTER LEWCOCK AND DE PENNINGTON : the mostt soluble magnesium salt yieldetl a liydrogeii phtllalatej whioh had [a] -t-3O.lo in ethyl alcohol (c=5) and solidified in flat prisms melting at 117'. When hydrollyssd it yielded a dextro-rotatofry uisopulegol (still oontaining appareatly about 10 pelr cent. of liisolpulegol) which had DC5* 0.9172 [u3E5"" +29.3O, [a]::;' + 34.5O and [ u ] ~ ~ ~ + 54.9'. When reduced by hydrogen in the presence) of colloidal palladium it gave an impure d-neomenthol with [a]& + 10*92O, which yielldeld a hydrogen suocinatei melting a t 68' aftelr two) erystallisations from light petroleum whelreias the1 I-meomenthol demribed in Partl I1 (Zoc. cht.) had -21.32' and gave a hydrogeln suaoinate melting a t 67-68O.The amount of material available did not pelrmit of a furthelr relpetition of the exceedingly tedious procelss of separatioa. The1 zsopulegones obtained from I-isopulegol and the impure d-a-isopulegol by oxidation with chromic acid atl 50' gave identical laworotatory olximels (m. p. 121' and volatile1 in steam) and semicarbazones (m. p. 171'). Esters of l-imPulegol and Normal ,4liphatic A c i d s . The esters were prepared by the1 action of the1 requisite acid chlorides on a. solution olf isopulegofl in pyridine except in the case of the acetatel propimate valesate and heptoate where the acid anhydrides were emplopd. All are1 fragrant limpid liquids a t the ordinary temperature. Samples off isolpulegol recoveired frolm the esterifica;t.ion proaess and also from the esters after theisel had undergone polarimeltria elxamination were unaltelred in rotar tory poiweir.Two samples od isopulegyl valerate welre also pre-pareid by fractional eatmifioatiom of the alcohol and were identical in roltatory power. In table I1 are1 given some of their physical properties in table I11 the relsults of the delterminations of their density (D $), and negative rotatory power (aloomm.) thO secoad setj of figures for tIhe compounds being the1 relsulting calculated values at the tleimperature nacmetd 04 the specific rotatory polwer and in table IV the data of deitelrminatdons of rotatory power in elthyl a1oohoP. The densities were determined in a pyknometer holding abolut 1.5 G.C. except in the case1 of isopulegol its acstatel and propionate, when ma hollding 4 U.C.was useid. The1 rotations were measured in tubes of 50 mm. lelngtlh round which cooled water or heated minelral oil was cirmlated by means of a pump but are here given as for 100 mm 2-isoPulego1 ............... Acetate .................. Propionate ............... n-Butyrate ............... n-Valerate ............... 1%-Hexoate ............... n-Heptoate ............... n-Octoate ............... n-Nonoate ............... n-Decoat,e ............... n -Undec oate ............ n-Dodecoate ............ Rlyris tate ............... Boiling point "C. /mm. 94"/14 103'/14 91'/4 116'15 119'14 153"/13 134'13 159'15 161°/6 158'12 164"/2 188'13 189'12 TABLE 11. I-isoPutego1 and i t s Esters.D:"v. 0.9110 (at 20") 0.9350 0.9300 0.9245 0.91 85 0.9150 0-9113 0.9065 0.9053 0.9020 0.8969 0.8969 0.8933 (at 20") 180 1240 1.4723 (at 20') 1.4565 1.4558 1.4563 1.4578 1.4581 1.4588 1.4584 1.4601 1.4603 1.4614 1.4621 1.4618 (at 20") Molecular n2-d + observed. 103.10 112.10 * The structure of the isopulegyl ring causes an increment of about 0.25 above members of homologous series containing five and eleven atoms in the growing chain t These values when plotted against molecular weight lie approximately on a refraction according to the Loreiitz and Lorenz formula. It has often been obscrved the calculated values by small amounts just greater than the experimental error. the ninth member of the series 1256 PIC1E;ARD.HUNTER. LEWCOCK. AND DE PENNINGTON : Temp .......... D ............ Temp .......... Temp .......... Temp .......... Temp .......... Temp .......... Temp .......... [ aIt643s ......... [a]&a ......... [a]50s 6 ......... [alkoo ......... [a$358 ......... aG4ss ......... a6461 ......... a608, ............ a4800 ......... a4s68 ............ Temp .......... Di ............ Temp .......... aG4s8 ............ Temp .......... Temp .......... Temp .......... ad800 ......... Temp .......... a4358 ............ Temp .......... [ a jLs ......... [a jL1 ......... [a$m6 ......... [a&~O ......... [a]",,, ......... 0.5461 ............ a 5 0 8 6 ......... 18.4" 0.9123 15.5" 16-60 15.5" 23.60 15.5" 27.64 15.5" 31.46 15.5" 39-20 TABLE 111 .l.isoP.uZeyo1 . 36.5" 70.5" 98.5" 131" QaS963 0.8661 0. 8415 0.8134 57.5" 105" 147" 16.61 16-66 16.72 56.5" 93.5" 141.5" 23.74 23.70 23.82 57" 101.5" 148" 27.76 27.86 28.22 56.5" 105.5" 150" 31.78 32.36 32.80 56.5" 103.5" 147" 39-86 40.52 41.38 172" 0.7764 163" 16-74 168" 23-98 165" 38.38 166.5" 32-98 20" 40' 60" 80' 100" 120" 140" 160" 15-23 18.61 18.98 19.39 19-83 20.26 20-73 21.22 25-90 26.46 27.05 27.65 28.28 28.95 29.66 30.38 30.31 31.01 31-74 32.47 33.25 34.08 34.95 35.83 34.51 35.43 36-37 37.35 38.37 39.45 40.57 41.74 43.07 44.30 45.55 46.86 48.22 49.67 51.16 52.71 1-isoPu1egy.Z A ce ta t e . 16.1" 0-9364 5.5" 7.54 0.5' 8-78 5.5" 10.16 5.5" 10.74 0" 9.48 20" 9.58 12.22 13.61 14.57 16.65 41.4" 0.9149 21" 41" 9.10 10.62 5.5" 21" 9.40 11.56 21" 41 ' 12.92 15-90 21O 41" 13.80 17.34 5.5" 21' 10.98 14.82 40 " 60" 11-61 13.65 15-32 18.34 17.18 20.74 18-71 22.83 21.24 26.35 84.1" 0.8794 66.5" 12-84 41" 14.18 65" 19.40 65.5" 21.48 41 " 19.70 SO" 15.s2 21.23 24.16 26-95 31.56 131.9" 0.8359 82 " 14.14 64.5" 84" 17.06 19.12 81.5' 21.54 84.5" 24.48 64.5" 83" 24.70 28.5 ALCOHOLS OF THE HYDROAROMATIC AND TERPENE SERIES .1257 TABLE I11 . (continued) . 1 -isolPu legy l Propbmt e . Temp .......... 12.2" 16.3" 44.6" 56.4" 82.6" 89.6" 131.3" J-$ ............ 0.9346 0.9315 0.9084 0.8987 0.8771 0.8721 0.8337 Temp ..........Temp .......... a6461 ......... Temp .......... a6086 ......... Temp .......... Temp .......... Temp .......... [a]& s ......... [a15461 .......... [algosfi ......... [aj&O ......... [a1&8 ......... ......... ......... ap368 ......... Temp .......... 3" 21.8" 46" 67 " 5.74 7.78 9.82 11.44 2" 21-8" 45" 67" 6.80 9-64 13.08 15.58 2.5" 21.8" 46" 67 " 7.02 10-68 14.46 17.62 2" 21.8" 45.5" 67" 7-20 11.14 15.80 19.38 2" 21.8" 45" 67.5' 6.66 11.86 17-66 22.76 20" 40" 60" 80" 8.19 10.17 12-22 14.33 10.13 13.49 16.58 19.63 11.06 14-80 18-51 22.21 11.63 16.12 20.36 24.68 1 2 . 3 5 17.98 23.54 29.04 84.6" 13.02 85" 17.88 84.5" 20.28 8 4 ~ 5 ~ 22.60 85" 26.64 1-isolPmlegyl n.Butyrate .20" 43.5" 54" 72" 113" 131" 147" D 1 ........... 0.9230 0.9046 0.8965 0.8822 0.8451 0.8293 0.8137 Temp .......... asdS8 ......... Temp .......... a5461 ......... Temp .......... a6088 ......... Temp .......... Temp .......... Temp .......... a4800 ......... a4368 ......... [.a];433s ......... [a54661 ......... [ a ] &fi ......... ......... [a).& ......... 3" 3-20 3" 3.10 3" 2.90 3" 2.78 3" 1.00 20" 5-53 6.46 7.02 6.93 6.28 15" 34" 52" 71" 82" 108" 134" 4.50 6.46 8.08 9-70 10.76 12.76 14.68 15" 34" 55" 71.5" 86" 112" 132" 5.02 5-20 11-20 13.26 14.88 18.08 19.96 15" 34" 55" 75" 84" 109" 140" 5.60 8.82 12-28 15.36 16.66 20.50 24.00 15" 34" 54" 75" 86" 108" 133" 5.34 9.42 13.40 16.62 15.28 22-96 25.90 15" 34" 55" 72" 86" 110" 132" 4-32 9.52 14.98 18.84 22.04 27.12 31.28 40" 60" 80" 100" 120" 140" 160" 7.78 9.87 ll*S7 14.12 16.31 18.21 20.12 9.99 13.32 16-24 19.39 22.40 26.54 28.60 10.98 14.69 18-35 22.41 26.00 29.34 32.77 11-77 16.13 19.88 24-65 28.77 32-96 37.20 12.34 18.10 23.41 29.09 34.59 39.86 45.24 163" 16.30 1610 23.00 164" 26.80 165" 30-54 161" 36.5 1258 PICKARD.HUNTER. LEWCOCK. AND DE PENNINGTON : TABLE I11 . (corztzkvwed) . I-isoPu1e:gyl n- Vderate . Temp .......... 22" 30" 56-5" 68.5" 75" 87" 127' D ............ 0.9259 0.9095 0.8882 0.8787 0.8735 0.8630 0.8264 Temp .......... Temp .......... Temp .......... aSoB6 ......... Temp .......... 44800 ......... Temp .......... a4958 .........Temp .......... ......... 0 5 4 6 1 ......... [4$*3* ......... [Q]&l ......... [ a]:gOo ......... [a]& ......... [a]&% ......... Temp .......... Temp .......... a6438 ......... Temp .......... Temp .......... a5081 ......... Temp .......... Temp .......... 44358 ......... Temp .......... D ............ ......... O.4800 ......... cQ]:438 ......... [Qlt5Lc 1 ......... W 0 . 3 6 ......... W S * O ......... r ai;:j5s ......... 2" 14.5" 3.74 5-24 2" 15" 4.10 6.24 2" 15" 4.26 6.78 1.5" 15" 4.12 6.92 0-5" 15" 3-02 6.66 20" 6.28 7.57 8-25 8-57 8.63 16" 6-36 16" 6.32 16" 6.88 16" 7.02 16" 6.78 40 " 8.39 10.87 11.99 12-87 14.16 41" 7.64 41" 9.98 41" 10.90 41" 11-66 41" 12-92 51.5" 8.54 51" 11.14 51.5" 12-54 51" 13-72 51.5" 15.38 60" 10.32 13.78 16.47 17.12 19.36 l-isopulegyl n- H exoat e .14.6' 32.8" 42' 0.9187 0.9040 0.8972 6" 14.5" 40.5" 68" 3- 32 4-14 6.76 8.84 6.5" 16" 41-50 68" 3.62 4.54 8.38 11.44 6" 14.5" 41.5" 68" 3.44 4.72 9.10 12.92 6.6" 15" 41" 68" 3- 12 4.84 9.62 14.18 6.5O 15" 42" 68" 1-94 4.16 10.52 16-28 20" 40 " 60" 5-19 7.45 9.33 6.19 9-54 13.3 1 6.30 10.46; I .I .5B 5-95 9-04 11-93 5 84 11.46 16-66 61" 870 9-20 11.06 60.5" 87' 12-20 15.16 61" 87' 13-80 17.20 60" 87" 15.28 19.20 60" 87.50 80° 12.19 16.51 18-79 20.95 24.11 17.14 22.32 56.2' 0-8870 83.5" 9.84 84.5" 13.42 83.5" 15-02 84' 16-54 80.5" 18.70 80' 11.06 14.86 16.77 18.41 21.4 ALCOHOLS O F THE RYDROARORIATIC AND TERPENE SERIES .1269 Temp .......... Di ............ Temp .......... Temp .......... Temp .......... Temp .......... a 4 800 ......... Temp .......... Temp .......... 46438 ......... c15.461 ......... 0 5 0 8 6 ......... 4 1 3 5 8 ......... CO1-$'39 ......... [ a]:lf. ......... [also86 ......... [ a ji8o0 ......... [ a]l.75* ......... Temp .......... Dt ............ Temp .......... a e43 8 ......... Temp .......... Temp .......... Temp .......... Temp .......... Temp .......... [a]L3* ......... a ] L ......... ra-&M ......... ra]:sJo ......... rC&m ......... a 5 4 6 1 ......... a 5 0 8 6 ......... 44800 .........44368 ......... 18" 0.91 11 5.5" 3.08 6.5" 3.20 5.5" 2.92 6.5" 2.70 7" 1-82 20" 4.84 5.48 5.76 5.83 5.50 19" 39.5" 0.8946 21.5" 4.48 21.5' 5-10 2 1-5" 5.42 2 1.5" 5.56 21.5" 5.28 60 " 0.8802 33.5" 5.54 33.5" 6.66 34" 7.56 34" 8.00 33.5" 8-16 40" 6.71 8.45 9.44 10.07 10.74 96" 0.8522 44" 6.22 44" 8.04 40 " 8.56 44" 9.64 44" 10.44 60" 8.43 11-27 12.57 13.82 15-41 I - i d d e g y l n-Octmt e . 23" 38" 0.9056 0.9028 0.8923 G6-5" 7-90 66' 10-56 65.5" 11.72 66" 13.12 65-50 14.54 83" 9-05 87" 12.78 840 14.06 85" 15.84 87" 18.74 80" 10.17 13-88 15.68 17.53 20.00 52.5" 0.8826 3" 17.3" 42" 45" 62" 76.5" 82" 2.40 3.90 6-06 6.24 7.32 8.28 8.56 3.5" 1'7.3" 37" 42" 63" 68.5" 86.5" 2.64 4.36 6.74 7.30 9.54 10.12 11.90 3" 2.44 3" 2.00 3.5" 0.74 20" 4.60 5.23 5.68 5.N 5.9; 15" 41.5" 67.5" 4.50 8.10 11-30 17.3" 41.5" 61" 67" 4-78 8-86 11-76 12-56 17.3" 37" 43.5" 60" 4.08 8.36 9.70 13.08 40 " 60" 6.58 8.28 7-92 10.52 8.84 1l.SS 9.68 13.23 10.10 14.83 85-50 13.32 84" 14-90 71.5" 15-06 80" 9.78 13.09 24.8'1 16.69 19.0 1260 X'XCKAED.HUNTER. LEWCOCK. AND DE PENNINGTON Temp .......... Di ............ Temp .......... Temp .......... Temp .......... Temp .......... Temp .......... Temp .......... [a]& ......... [a j",,, ......... [a];o86 ......... [a)& ......... [aj&j .........a64s8 ......... a 5 4 6 1 ......... as086 ......... a4800 ......... a4868 ......... Temp .......... D ............ Temp .......... aGPs8 ......... Temp .......... 4" 2.58 4.5" 3.44 4" 2-43 4" 2.30 4.5" l - 1 G 20" 4.36 4-98 5.38 5-51 4.94 17" TABLE 111 . (comtiimed) I-isolPulegyl n.No.noate . 19.3" 0.9042 23-5" 4-26 23.5" 4.94 23" 5.34 23.5" 5.52 23.5" 5 1 4 40 " 6-20 7-G4 8.43 9.22 9.47 36" 0.8925 49.5" 6.18 47" 7.58 46' 9.68 57.4" 0.87G8 64.5" 6.94 63" 9.34 49" 8.64 48" 9-34 63" 12-72 60" 7-72 10.24 11-39 12.64 13-94 I-isdulegyl n.Decoate . 45.5" 65" 0.9028 0.8821 0.8684 81.5" 8.00 82.5" 10.98 81.5" 12.22 81.5" 13.54 82" 18.94 SO" 9.20 12.57 14.06 15.62 15.12 84" 0.8546 10 140 440 60" 77" 98" 119" 141.5" 170" 5.50 3.32 5.46 6.44 7.62 8.50 10.16 11.22 12.50 3" 1.4" 42" 59" 77" 94-5" 118" 141.5" 168" ~ 5 4 6 1 .........2.30 3.70 Temp .......... 1" 14" asoS6 ......... 1.90 3.80 Temp .......... 1" 14" ~ 4 8 0 0 ......... 1.96 3.90 Temp .......... 3" 14" ......... 0.58 3.38 Temp .......... 20" [ a]&1 ......... 4.93 [U$os ......... 5.20 [a]:y), ......... 5-35 [a & ......... 5.15 ......... 4-15 6.90 8.32 42" 59" 7.46 9.64 41" 58" 7.88 10.38 43" 68" 8.94 11.48 40" 5.78 7.52 S.19 8.71 !f.(iO 10.10 11.34 13.28 15.00 16.S6 78" 95" 120" 140.5" 170" 11-56 13-30 15-56 17-40 19-98 79" 95" 121° 140.5" 170" 12.98 14.74 17.72 19.74 22.S6 77" 94.5' 117.5" 141" 166.5" 14.48 16.86 20.22 23.46 26.23 GO" 500 7-41 9.02 9.75 11.92 11.10 13.69 12-23 15.20 13.54 17.3 ALCOHOLS OF THE HYDROAROMATIC AND TERPENE SERIES .1261 Temp .......... D ............ Temp .......... Temp .......... Temp .......... Temp .......... Temp .......... Temp .......... [ a ] L ......... [U$4til ......... [a]S"sc ......... [a]t4yfio ......... [a]& ......... aa438 ......... a 5 4 6 1 ......... (150 8 6 ......... a4800 ......... a4358 ......... Te.np. ......... D ............ Tern p .......... Temp .......... Temp .......... Temp .......... Temp .......... Te n p .......... [ujL; ......... [a j k ......... [ a ] L j ......... [altisco .........[a]:;:35 ......... a 6 4 7 8 ......... a 5 4 6 1 ......... a 5 0 8 5 ......... e.1 800 ......... a4358 ......... TABLE I11 . (conlinued) . l-is.o9ulegyl n-Undecoate . 17" 0-8972 3.5" 2-58 2" 2.46 4" 2.70 4.5" 2-56 2.5" 1.48 20" 4.31 4.98 5-29 5-54 5.54 55" 0-8715 15.5" 3.42 15.5" 3-96 15" 4.00 15.5" 4.22 15.5" 37.5" 4.18 7.90 40" 5.94 7.35 8.21 8-94 9-41 88.5" 0.8475 38.5" 56" 5.16 6.12 38.5" 56" 6-28 7.96 38.5" 55.5" 7.10 9.06 39" 55.5" 7.78 9-74 53" 68.5" 10-34 12-42 60" 7.31 9.48 10.83 11.82 13.18 1-is0 Pulegyl n-Bodecoat e . 14" 20" 43" 58.5" 0.8996 0.8959 0.8794 0.8684 4" 17.5" 39" 56" 2.44 3.30 4-64 5.78 4.5" 17" 40" 57" 2-40 3.663 5.90 7-48 4" 18" 38" 55" 2.36 4-10 6.46 8.34 4" 1 S" 38" 55" 2-10 4.16 7.00 9-12 4.5' 17.5" 38" 53" 69.8" 1-44 3-52 7-26 9.58 13-08 40 " 60 " 20" 3.84 5-35 6-89 4-42 6-69 8.88 4.83 7-60 10.14 4.98 5-23 11-18 4-65 5-57 12-27 n 131' 0.81 38 88" 7.74 88.5' 10.38 90" 11-86 91' 13.46 87" 15.02 80" 8.65 11.48 13-02 14-52 16.44 80" 0.8540 51" 7.14 80" 0.40 81" 10.70 81" 11.82 82' 13.90 80" 8-32 11.01 12.47 13-75 15.93 3 A 1262 PICKARD. HUNTER. LEWCOCK. AND DE PENNINGTON : Temp .......... D\ ............ Temp .......... ag4as ......... Temp .......... a 58 61 ......... Temp .......... 4 b 0 8 6 ......... Temp .......... a4 800 ......... Temp .......... a 4 3 5 8 ......... Temp .......... [a$438 ......... [&61 ......... [u$@gt3 ......... [ 4 3 5 3 ......... [a]:800 ......... 5" 2-44 5" 2.40 5" 2.52 5" 2.42 4.5" 1.66 20 " 3.81 4.23 4.68 4.84 4.48 12-4" 0.8985 22" 3.54 22" 3.96 22" 4.44 22" 4.58 22" 4.26 40 " 5.30 6.30 7.05 7-62 8-07 34.8" 0.8832 43" 4.84 43" 5.86 43" 6.54 43" 7-08 4 3 O 7-58 54.8" 0.8693 65.5" 6-00 65" 7.63 65.5" 8.54 65.5" 9.26 66" 10.56 60 O 6.63 8.32 9.38 10-28 11-44 84-5" 6-82 83.5" 9.10 54" 10.36 83.5" 11.44 84" 13.36 80" 7-82 10.33 11.69 13.00 15-02 Some of the materials weld in this work were purchased from 8 grant made by the1 Govelrnmentl Commitltee of the Royal Society ; the relm:iiptl of a personal gmnt from the1 Depa. rtment od Scientifio and Industrial Researoh to one of the authors is acknowledged. whilst the authors' thanks are aka due to Messrs . Schimmel. od Leipzig. for a. prel-war gift4 of crudel isopulegyl aoeltatet ALCOHOLS OF THE HYDROAROMATIC AND 'J'ERPENE SERIES. 1263 3 4

ISSN:0368-1645    

DOI:10.1039/CT9201701248

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

1264 SAUNDERS SOME NEW CXXXV1.--Some New A xop yrazolones and Allied Compounds. By KENNETH HERBERT SAUNDERS. IN seeking t o asmirt'ain the eiffecit procduced on the co3our of com-polunds of the a,zo-typel belonging to the1 benzene naphthalene and anthraquinone grolups b'y inmelasing moleculas weight by a corn-pa,risoln. od the abslolrption spectra' o,f the various members it was folmd that sca,rcmly any of the required substa,nms beyond t'he belnzeiaeazol- a'nd na~ht;halane;a~o-selrias have be'en prepared. Alth,oagh a,zobenzelneI arnd the a,zonaghthalelneis are. very well knolwn a-azoa,nthra,quino~ne ha's ,olnly beten disaomreld in recelnt yelam (Gattelrma,nn a8nd Eberti Ber. 1916 49 2117) whilstl the a.zoa,nthra,aenes a,rei unknolwn. For the1 purposel oif such a' oom-pa,rison the azopyrazollones being more strongly coloure4d and much f a8ster to1 light tha,n t'he c,orreaponding membelrs of the! azobenzene series woluld seeelem t,ol be more suitahlel and haw therefocel been se;leateld for the investigation.A clolmpleta series of co8mpolunds ha,s been preparead in whic8h the ant'hra.quinolne1 nucleus is intro-duwd e1ithe:r into the 1-position of the1 pyrazolone ring or as tthe first colmponent of a,n amzopyramzolonel compolund or in b0t.h positions tcogether. The 1 -a,nt8hraquinonylpyraxo~lones cannot be ob,t8ainemd by the simple prolaess of he:a,ting ethyl amceltioa~ceta8te with the relquired h y d r axi nei bemuse' rea#ction inva'r i ably s t,op s with t,he f osm a,ti on olf the hydra.zone. The further action olf condensing agents is nelceesary before tlhe fl-anthra#quinonylhydrazons of ethyl amto-acetlats can be convelrteld into a.pyrazolom. Although bo,iling sulphuria a,&d will elffect tlhia change' in one stsagel t,he yield of the pyrazolone is sma(l1 a large proportion od tihe original hydra(zine1 b,eing rege,nelra;t;ed. A far more satisfa<otory method is to! b,oil the hydralzolne with acetic anhydride( wherebsy l-P-a,ntfhra.quinonyl-5-a~~tyl-3-me~thylpyra~zolone~ is produoeld (Mohlaa and Re'iner Ber., 1912 45 2244> and tlhsn hydrollyse with hydrochlorio acid. 1 -P-Anthra~u,~Onyl-3-methy~-5-1ryrarzolo~e is olbtaineld in tlhis way 8.5 an olrangei powder showing all the! propertiels of the cla.ss except tha,t the a,ntlhra8quinona n u o h s causes i t to1 be highly insoluble and rather slow to enter int'o relaction.It aouplee with diazonium salts in a,aeltic a,cid solution to1 give t-ypical a,ryla.zopyra.zodones od great stability which do not sho'w delfinite melting pain& but slowly begin to deloo8mpose abomve 250° olr thereatbout'. The so3e prolduct of the1 compbtel conde.nsa,ticm of the a-a.nthra AZOPYRAZOLONES AND ALLIED COMPOUNDS. 1265 quinonylhydrazone of ethyl aaeltoamt-ate is pyrazoleanthrorie and the required pyrazolone cannot be obtained (Reiner Diss., Dresden 1912; Mohlau and Viertd Ber. 1912 45 3238). Difficulty i n obtaining the a-isomeride is also1 expelrienceld in the preparation of the l-na4phthyl-5-pyrazolones (Knolrr Ber. 1884, 17 550) for whilst l-j3-naphthyl-5-pyrazolonel is easily prolduoeld, t!he produd olbtained from the fusion of a-naphthylhydrazine with ethyl acetoacetate contains scarmly any pyrazoloine whilst in solvent8 the colndelnsation does not take place1 at all.As noted above the colour of P-anthraquinonylpyrazolone is orange althoagh all the ohher pyrazolonels olf this type1 hitherto described are1 colsur-less. The colour vibration may be selti up by tlhe carbonyl group off the pyrazolone reacting with that of the anthraquinone nucleus, owing t o their being so a,rranged in space that they are in the closssb proximity. Thatl the1 colour is concerned with these1 two1 groups is shown by the fact that amtylation od the pyrazolone changes the collour t a lemon-yellojw. It seems possible thereforel, that the codour of the produde and also the diffiaulty oif intro-ducing the a-anthraquinonyl group may be referred to1 the con-tiguous position od the carbonyl groups in the anthraquinonel and pyrazoilone nuclei.Evidenoei f o r this view vmuld be1 the pix-pa,ra;trion od the 1-a-naphthyl- and l-a-anthraquinonyl-3-pyrazolone, but thew compounds do1 nolt yet seem tot have! beleii described, For the preparation of the arylazo-derivatives of the abovb anthraquinolnylpyradonei the alternative process due to1 Bulolw and Helcking (Ber. 1911 44 437) has also beein investigated. The first two 5teps are easily accomplished P-anthraquinone-diazonium sulphatel for example readily combining with ethyl acetolamtate whilst the1 azol-compound so formed o n boiling with hydroxylamine passe@ inta the isooxazolone.When however the isooxazolone is treateld with hydraziiies although a yield approach-ing theoretioal is olbtaineld from hydrazina itself the yield steadily falls as phenyl naphthyl and anthraquinonyl nuclei are introl-dumd so that the1 methold is useless for produ-cing the higher members of the series. Sodium dihydroxytastratel dscomposss below a temperature a t which P-anthraquinonylhydrazine will mad excepting with extreme shvnelss so thatl it1 was found impossible to olbtain new members of the tartcazins group by this method all products of readion. from a large variety of solvents beling for ther most part a mixtlure of the decompoaitioln proiducts of the dihydroxytartrate . The antlhraquinoinelazopyrazolones whether unsubstituted in the 1 -position olr substituted by phenyl naphthyl o r anthraquinonyl rwidues are1 aharauterised by having at best only a sparing sdu 1266 SAUNDERS SOME NEW bilitly in most osga.nio solvents.They can be ary&allisd fairly well from pyridinei or nitrollsenzeiiel. They also ham t~he property oQ many anthraquinonelaz&compolunds of dissolving in warm alkali hydrolxide to1 form a deep purple solutio'n a<nd in the case of 4-B-ant hra;qu,imomneaz 0- 3 m e t h y I- 5 -pyratz o h o.rz.e w hi oh is very reladil y soluble1 in this reagentl a rnolnosoldim saltl can be mystallised by saJting the wa,m. sollutioin. Thelir melting points a<ret very high so, t8halt o 4 t a decompoaitioln 14eltls in bef o'rel fusion t,akels place'. The prolpelrty which firstl atlt'racted a.t,tentlion t o the group is tha't 4-~-anthraquino~ne~azo~-l-phenyl-3-met~hyl-5-pyra~zolone can exist in t'wo differelntly cololured moldificat'ions (1) yedlolw unst,ablel, and (2) red stable (Mohlau and Relinea Rer.1912 45 2240). These ant'holrs prepared b,otlh forms and forund tha't the same absorptioln speotrum is give'n by both a8nd tfhat on hela.t.ing the ydhw foran. chafnge.s into the1 md withoat melltling. The sa4me behaviour is sholwn by 4-~-amthra~purin~om~ca~zo~-l-~-naphthyl-m.ethyl-5-pyrazo~lo.ne esce'pting that1 tlhe yelllolw form is still less stlabmle a,nd oinly appeers direlotlly a.f telr colmbination ha,s ttakeln place', rapidly cha-nging tlol the md fo'rm. oln wa'rming. On th0 olthelr ha,nd 4-~-antlhra~quino~nea~z~-3-methyl-5-pyra~zollo~ne~ and 4-P-mt hra-quin8mleaz ocl -P-ailz,tIzrai~ui/n,~ln.~yl- 3-methyl-5 -pyraz crloin,e exist in the solid stlattel only in yelloiw forms and by no means ca,n be induced ta crystallise olthelrwiss.It1 would a,ppear t8hhereifoirel thah a phenyl a,nd molrel partimla8rly a napht,hyl nucleus substibutling the 1 -pit,io'n olf tlhe; pymzollolne ring causes the ordinary yedlolw form t'ol be unstable( with the1 result that slightl re8arrangsmenb takes p1a.m on crystlallisa,tioa a rno're st'able reld f olrm being produced. The eolour olf tlhe s,olutiolns od the amnthraquinonea,zopyra8zololnea is deep yellow almolst indistinguishablet to1 t'he eye from those! of the( benzeneazopyrazollonea the am-colmpoiunds derived f rm l-~-ant~hraquino~nyl-3-me~t~hyl-5-pyra~zo~lo~ne noIt.withst.anding t,he red cololur of this compound shotwing practically the1 same colour as those in which the a,nthraquinone nucleas is absentl f r o m the 1-position of the pyrazollonel ring.This agrees well1 with Hewitt's bheolry (T. 1907 91 1251) since the t'wot aarb'olnyl groups in the ant.hraquinotne1 nudelus cut shojrtl the chain oif double a7nd single bolnds isollating the benzelnel ring beyo,nd sol tha8t~ it1 c,a.nnolt add its e)ffe,ct acrid thus ths nelt rea,ult+ on the1 cotloar of an anthraquinone group in a,n a,zol-c:olrnpoand of this type is pradioaslly t,hat' of a single be,nz.ene ring. I3 x P E R I M E N T A L. &A I t tki*uIT'iiiiO~i,!ilh~lrJ1.azi?i e.-For the purpose oif this reeeaarch, a considerable quantity of tlhis hydrazinel was required. Th AZOPYRAZOLONES AND ALLIED COMPOUNDS.1267 synt.he&s has been described in detail by Mohlau Viertel and Reiner in a comprelhensive paper (Ber. 1912 45 2233) and also by Mohlau (&id. p. 2244). The1 latter paper delals wit.h the pre-pasa.tJon f rolm P-ohloroanthraquinone by heating with hydrazine hydra,& but as the yielldsi ase olnly about 20 pelr celnt?. the process is useless on t,hel la'rge sca'le. The1 fotrmelr paper is a,n account otf the1 process oatdineld in D.R.-P. 163447 consi&ing in the reduction of P-anthraquinonediatzonium su1phat.e in aqueous so1utio.n with potassium hydrolgeln sulphitei f o'llowed by hydrollysis od the hydraaineldisulpholnic a#cid wit,h hydrochlolric a,oid. Owing ts t'lie fact that all the1 intelrmeidiatel compounds ha,vel to be isolated in t'hei sollid stla.te! the proow is lengthy a,nd cumbelrsomel on accolunt~ of the ra4t,helr large volume of water nelcessary f o'r the1 spasingly solu b,lei P-a<nthr a8quinonediarzoaium su1pha;te.T he1 relduct ioln o:f t he1 diazonium chloride with &annous chlolridel has the'ref o'rel been trield. If p-aminoa,nthraquinolnel is boiled wit'h excess of coaclent'rated h y d ronhlolr ic a clid un ti1 comple,tedy convelr ted t'ol the hy d r olclhl o'ri d e, it aa,n b,a dia.zoltise!d a.6 the1 ordinasy tempesakure as recrlily a.s i n concent8rated sulphuric acid. ColmpletJon is shown when a. drop oif t,he liquid diluted witlh water gives yellow diazomnium sulphate, soilublei oln shaking inst The1 a,&don of stannoas chlolride on such a solution is compleix and leatds to poor yie,lds of P-antlhraquinolnylhydra,zinel.Even whe8n strongly cooled wit'h ice and salt' nit'rolgen is emollved during the reacltioin and tlhel tot'al nit,roigen coatsnt olf the final prolduct nelver rises above 7.5 per cent. This seems to be duel to1 at t'wo-folld causel. First the ant:hraquinone-aarbolnyl grotups are more easily reduced tlha.n the diarzo8-group a,nd secolndly st'erio hindrance causa the getnelra'l sluggishness of the1 a-hydrogen in the1 hydra'zine, reduoing agelntls noit being able t'o a4dd this hydrolgeln thus musing fissioin of the dia,zonium chloride t'ol t'akei pla,oe instread. Itl was further found that the a.dditi0.n of one1 molecule1 o'f st,annic chloride ca,useid the reactioa t,o pro,ceed more smoothly a gre,en int,elr-meldiatel produet beling folrmetd but on isollating t,hhs free1 base! it gave no1 b'ettea results oln analysis.The hydra.zons prepreid from this hydraxine was purified oaly with difficulty a,iid finally t'he b,ulk off the hydra,zinei was preparetd by t,ha use of po,t,assium salts, whiclh give bettelr yiellds aad morel uniform results t,han those 0.f sodium a c:onst.antl yielld of 70 per cents. being obtained. d of a,minolant,hra,quinonel in reld flakels 1268 SAUNDERS SOME NEW P-Anthraquinonylhydrazinet was co,ndeaaed with ethyl aceto-ace.tafe in amyl alcohol sollution and the hydrazonei recrysta,llise.d from a h h o l . Ten grams of this boileld with 100 C.C. olf acet'io anhydride gave 7.5 grams olf t'he a,wltylpyra.zolonel which was dis-sollved in a mixture1 oif 200 e.a.olf glaoia.1 a,c,etic a.cid and 75 c . ~ . od hydrochloric a,cid and hydrolysed by two hoiurs' boiling lamt~telrly with t'he addition of animal chasaoa\l. The1 mixturet was coole'd, filt8elred and polureld into1 elxmss of wafelr when 1 -P-an,th1"a,qzcino.nyI-3 -met h yl-5-pyraz o1on.e selpa8r afeld as a yellolwish-r eld gella,tinous mass whioh was wa,sheId ma,ny times wit'h colld watelr and clried at, looo. The yielld wa6s 6.5 grams. . The pyrazolloae is so3uble in glacial a.cet,ic acid to1 an orange solution which deposits minuts red crjmtals otn coolling mom re.a,dily sol in pyridine but only sparingly sol in alcohol1 and momst, &her organic so'lvents ; insoluble in wa,te.r dilute acids or allia,lis, but giving a reld solution in concentra4t'eld sulphuric acid and a polrt-wine ooloaretd vat in a,lkaline hyposulphite.It wa8s recryst.alliseld from pyridine giving an olrangel powder, but a,ltholugh many co,mbustions were1 ca,rried out neithe'r satis-f aot,ory nor concolrda,nt reslulta welre olbtaineld. This woald seen t a be due to the impossibility olf effelct.ing colmpleltel combustion t3he nit,roge.n continuing t.01 bet evolveid f o r long pelriolds elven a't al bright red heat. The same trolublel ocourreld t'ol a leis de,gres with the azol-deriva,tives heIa$t.ing having t.01 be1 contdnued f oc an unusua.1 time1 before nit,rogeln oeawd to1 be evollveid. The folllowing reamctlioiis cha,ra,ct,e8ristic of the1 pyra'zolones welrej sholwn. I n acetda a,cid so<lut<ion t,hei coniponnd reta.dily rela8cta' with nitrous acid to give a spasingly sollublel palel yelllolw isornitroso.cmmpound. Bromine wa,te,r a,dde!d tot thel same1 solutdoln is atl onm det601101rised and a yedlow preIcipitlate of the dibromopyrazolonel is folrmeld. Sol far a delfinit'el memb,er of the a'ntipyrinel group ha's notl bmean obt'aineld. 4-Beltz en eazoil -P-a,mt hrapuinomy l- 3 -met lzyl-5-pyramz o b n e, To a solution od the1 pyrazolonej in glacial acetic acid the! requi-site quantity of benzeaeldiazcnium chloride was addeld. I n the! prese'nm of sodium aceitate combination a,tl once took plaml a AZOPYRAZOLONES AND ALLIED COMPOUNDS. 1269 yelllow gedatdnous mass se'pasating. After stirring f o r an hour at, Oo itl was ponreld int,o wa.ter collectsd wa,sheld and dried.It crystallisels from pyridine, in which it is ve,ry rea'dily soluble in minutq yelbw neeiclles. It is soluble1 in nit'rotbenzene and to a s,ma,llelr elxtmt in g1ac:ia.l a.celtda acid ; in concelntrated sulphuric a.cid i t gives a deep olrangs sollutioln (Found N=13.58. C,H,,Q,N requires N = 13.71 pelr cent'.). 4 - a - Nn ph t halcn e m 0-1 - p -an t h rap. uin o n1yl-3-m e t h y I - 5 -pyraz olome and 4-P-Napht halenenzo- I-P-ant hra p i n onyl-3-met hyl-5-pyramzolone, N:CMe I >CH.N:N*Cl,H7. C,,H +-I,* N-CO Thetse were prelpa,red in eIxactly t,he same way a.s t,he belnzenela.zoc compoand. The former was obtaineld in minuto velrmilion needlea 0.a crystallisat,ion frolm pyridine in which it is very sparingly so'luble (a.bout 0.75 gram in 100 c.c.).It gives a purple1 sollution in concelnt ra8ted sulp huria acid whetreas the P-naphthalelneazol-componnd is de!ep osangei in t'his solvent the1 usual test which ServeiS tot distinguish the1 two1 isomelridee no! rnatkm what the I-substltuent olf t'hei pyra,zololneI ring is (Foand N = 12.06. C28H,,03N4 requires N=12*22 pe,r cent.). The second compund beling almost insoluble1 in pyridine was cryata,lliseld from nit,robeiizelne giving a dull red po1wde:r. Bot,h are1 insoduble. in most olrgania solvents (Found N = 12.10. C,,H,,O,N relquirea N = 12.22 per cent.). 4 -p- A n. t hraqzcirzon eazo-1 -p-an t hraqi~inOnyl-3-me t hyl-5 -pyrazolome, >CH.N:N-C!,,H,O2. :CMe c1 H70,. K-co P-Aminoanthraquinonel (I * 1 grains) after convewion to the hydrochloride was diazotised in 30 C.C.of glacial acetic acid with 30 per cent. excess of amyl nitpite (Kaufler Zeitsch. Farben-lnd., 1903 2 469). This was combined with 1.5 grams of the pyrazolonei in acetio acid soilution giving a theoireitioal yield od the crude1 azol-compound. When orystalliseld f rom nitrobenzene it f o m s finel microscopic yellow needles ; variation of the conditions faileld to1 produce1 any other form. Itl is insoluble in a11 solvents except nitrobenzene and to1 a less extent in pyridine (Found: N = 10.26. C,H,,O,N requires N= 10.39 per aent.) 1.270 SAUNDERS SOME NEW 4-P - A ?L t hTaq 1 ~imoneaz 0- 3-nze t h y 1 - 5-p'y ra z d o n e r= CMe>CB N :N C',*H7* . NH-CO P-Amino8a,nthraquinoiiel (2.5 grams) was dissolved in 19 C.C. of sulphuria acid (D 1-84) wibh me,chanica.l st'irring.The1 bsaker was susroundeid witlh EL wa8ter-ja,cket8 and 4.5 grams of dry crushed ice we're added to t,hei solutiolii. I n five1 minute,s a volluminous, white pa,st,el oif P-aminola.nthra(quinone1 sulphat,el was folrmeld. A so1u.tion olf 1 gram olf soldium nitsitel wa,s t'hea added frolm a t.ap funnel wit,h a velry fine nolzzle sol tha't a8n holur elapsed before all ha'd beeln run in whilstl tlhel ttempelratturel ,elf the1 acid and t.he surrounding barnth wa's allolweld to1 rise to 30° under t'he helast( of dilution. As t'he diazolt<isation proceeldeld the! P-amino,ant.hraquin-one sulpha,te diasodveld md on c:o'mpleltion at cle.a#r bmwn sollution resulted a drop of which a8dded t,a waltelr7 ga,ve a yedlolw precipitate, dissoilving to1 a velry palel yelllow sollutioln 0111 shaking.Sufficient ice to d i h t e t+hel wa.rm solutioln emofugh t'ol st,ast8 the! erystfa.llisa,tion of tha fl~-antehra8quino~nedia.zolnium sulphate was a8ddeld and the whole1 set aside to1 ciool. In ha#lf an hour the1 dia'zonium salti cryst8a.llised in shining yellow plates the content's of the1 belake'r set'ting solid. The nmss wa,s sciraped outq 0;11 t'ol crushetd ice] collected and wa.shed oncei w i t,h icei- w a,te>r. The fl- a4n th r aquinolnediazonium sul p h a t,el was olbtained in this way as a yedlo~w st'a'ble crystallinel powder in a yield of 87 per ceati. olf tlhe tllielo~ret6aa81. It' was dissolved by stirring into 400 a a . olf wa,t.er a-l; 200 and decompoeed wit.h a so3utioln olf 5 grams olf soldium a,e8ttatei.Tein grams of 3-metrhyl-5 -pyra,zollone~ ha'ving bewi dissoilved in 350 O.C. of wa,tec the dia,zo-solution was addeld with st,irring and immejdia;tfelly tfhel azoI-compolund selpasa;t8ed in ye~llo~w flakes. It was colllelcteld washeld twice wit'h bolt water and drieid at looo ; t,he yield was t'he'oretioal . This colmpolund wars folund t.01 he cha.ra.oteriseb b,y extreme1 in-solubilit<y in a,ll o>rganio sollvents. Itl was crystallised from pyridine, in which it dissollveld t o the1 e,xtent o1f lem tlha4n 1 pelr clent. the crystals f o,r,ming microiscolpio nesdles. It wa,s aJsol spa,ringly soluble in nitro)belnzeael or a,myl adcoholl ; in c,o,ncentra#ted sulphuric acid the sotlutioln was oirangel (Folund N = 17.12. CI2Hl2O3N4 requims N = 16-90 pelr centl.).Whein warmeld with diluta soldium hydrolxide sollutlion it dis-so,lved rela.dily giving a deleip purple soJutioa. On sadtdng the hot, solu tiotn shining pu rplish-bl a,ck cry st'ads welrei delp osi teid and o ii acidifying a sollutiotn oIf these' the original azolpyrazollone was pre-cipit>a,t.ed as a yelllo8w jellly. By t.it,rat.ion of a solution with 0*117-AZOPYRAZOLONES AND ALLIED COMPOUNDS. 1271 hydrochloric acid using the above colour change1 as indicator it was found that the1 salt coatained one atolm of sodium. 4-p- A nthraquinomeaz 01- 1 -j3-?zaph t h y l-3-m e t h y l- 5-pp-a~ 01 one -SJ:CMe C,,H7 *N-GO >CH* N N*C ,H,O,. Four gra,ms of 1 -~-naphthyl-3-met~hyl-5-pyra~zolo8ne~ dissollveid in glacial a ceitdc aci d we're.con1 bineld w it'h thei anthr aquinoineidia,zolnium slulpha.tei prepased from 4.6 grams olf P-aminolaathra,quinone diazoltiseld a,s a,b,oIvel. The am-compolund obt'aineld a8 a' flocculeint, ora,nge mass on dilut'ion witlh. wa,t.elr was collelcteid washeid twice1 with colld waher and once with holt, and dried a.t looo'. It gave brick-reld needlee whein cryst alliseid frolm nitrobelnzeliiel in which it is f a.irly solubslei a t the1 boiling polint,. Cryst'allisatioa of t<hei cool solutJoln dilutgd wit'h a,lcoiholl ckndit;lons undelr which 4-P-antlhra-quinoneazo-1-phenyl-3-me~tJhyl-5-pyra.zo~1oae~ gives a hrga propoIrtdo,n od the yellow form fa,ileld tot givei any oltheir vatrie;ty. It is adso soluble in pyridinel or glacial aceitJc acid whilstl in a(1coholic soldium hydroxide it gives t,heI typical purplei sodutlioln ; in concentrakd sulphuria a.cid its sollut,ion is deep red (Foand N=12.46.C,,H,,O,N requirels N = 12.25 peir cent,.). Attempts welre ma,de to prepa,rel thei isolmeric 4-P-anthraquinolne-azo~l-a-napht~hyl-3-metlhyl-5-pyra~z~o~lone~ bfut the remits webre unsa,t.isf a,ct,ory a'nd a pure1 substmael was noit obtained. E thy I &Ant h.1.a,qu~~o~ea,zol~cetoacetat e , C,,H,0,*N:N*CHAc*CO2Et. The /3-anthraquinolneidiazolnium sulpha,te resulting from the dia.zoltisatioin of 10 grams of &a,minolanthraquinonel was dissoilveld in a litre of water to which were added 20 grams of sodium acetate. Tot this a d u t i o n of 5.1 grams od &hyl amltolamta8te dissollved in 39 C.O. of fl-soldium hydrolxidel was added and the1 whole stirreid unt,il the odolur olf the1 eist,elr hard dis,appela,reid.The1 yeillotw a,zol-compound being quitel insotluble in wat.telr sepra,tsd a.tl olncm a,nd wa,s c!oillelot,eld wa,shed and drield. The1 yieild was t'heolretiaal calm-la,t,ing from the a,ntihra,quinoneldia,zonium sulphate used. Thel orude substlancmei ha,d a gre,eln t.iiige butl aftes boiling with a.nima.1 cha,rcolal and recrystmatllising f rolm glacial a,celtia acid it ga,vel a, yeillow powder mellting a.t. 21 6-218O. Itl is surprisingly sollublel f o r an a,nthra,quinonei delrivative; dissollving in adaolho~l ohlolroform, benzenei t,odu elnet ni trolbetnzelnel or pyridine. Alka.li hydroxide t.urns itr purplei butl it is sparingly soluh.lei a,nd a,cids prelcipitatre! i t as a yellolw jelly (Found N = 7-84.C,,H,,O,N requires N = 7.69 pe.r cent.) 1272 SOME NEW AZOPYRAZOLONES AND ALLIED COMPOUNDS. 4-&A mt hraquiao.neaz0~3 -met h y li~o~oxrazolone, Eight grams od elthyl P-anthraquinoneazoaceltolacetate were dis-solveld in a mixture1 of 175 c . ~ . of glacial acetic acid and 25 c . ~ . of an aqueioius dutyion of 3 grams of soldium acetatel. To the warm solutian 1 -5 g r m e od hydroxylaminel hydrolohloride dissolveld in 10 a.a. od wa,ter were1 added and the1 whola was boiled for two hours when a drop no longer shoiweld a relducing action on Fehling’s solution. The cololur was then orange. Animal. charcoal was added and the whole boiled f o r a furtheir ten minutes filtered hot, though asbestos and slowly cololed.A mass of orange needle-shaped crystals was depositsd and these were1 collleoted and dried ; the yield was 6 grams. The substance! melteid and decomposed at 188-191’. It was soluble in acetio acid alaohol ahlolro~form, bnmnel o r toluene inaoiluble in water or dilute mineral acids and sparingly soluble to1 a purple1 solution in alkali hydroxide1 (Found: N = 12.01. C,,H,,O,N requires N = 12.68 per cent .). On trelating an acetic acid solution of the1 icooxazoloiiel with hydrazine so voluminous a preoipitate of 4-P-anthraquinoneazo-3-me~t~hyl-5-pyrazolone was obtained that the whollel selt sollid. This substlance was idelntified by the propertiea given above. With phenylhydrazinel al small crop olf 4-P-anthraquinonelazoi-l-phenyl-3-meltlhyl-5-pyrazolone~ was olbtaineld and identifieid by its melting point. With the1 napht?hylhydrazines the produds were t o o impure and tairry tot identify with crertainty. When 1 gram was boiled with 0.9 gram of P-anthraquinonylhydrazinel a precipitate of 0.8 gram of a reid substance was obtained. By its insollubility in all soilvent& except nitrolbenzenei and its giving a relddish-purple solution in alkaline hypoisulphitel i t was concluded that it was 4-P-ant hraq~inone~azol- 1 -&ant hraquinonyl- 3-met hyl-5 -pyrazol-one but the yield being so poor and the product sol impure( this methoid of prelparation was abandoned as beling tool wasteful of the1 valuable P-anthraquinonylhydrazine. The author wishes to elxprelss his thanks t o thel Salters’ Institute olf Industrial Chemistry f o r a Fellowship which enahled the work to he colnducted tot Sir William Pope for his inspiration and intlerest and to Dr. M. 0. Forster for his guidance1 throughoiut the1 course of the work. THE UNIVERSITY CHEMICAL LABORATORY, CAMBRIDGE. [Received Srptentbc? 1 Sth 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701264

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

JAMES JONES AND LEWIS ACTION OF AMINES ETC. 1273 CXXXVI1.- The Action oJ’ Arniizes on Trinitrophenyl-methylnitroamine. By THOMAS CAMPBELL JAMES JAMES IVOR MORGAN JONES and ROBERT ILLTYD LEWIS. IT is a well-known propelrty of polynitro-aromatic aompoands that they form additive derivatives with various types of aromatic substanm such as hydrocarbons phenols amines etc. The most recent work on thesel derivatives has beten carried o a t by Sud-boroagh and his collaborators who1 have examined in detlail the €olrmat,ion and propertiea of a large series of the a,dditive com-pounds formed by s-trinitrobenzene. I n a review of the compounds prepared by them Sudborough and Beard (T. 1910 97 773) were leid to1 suggest a possible formula for the compound of trinitro-belnzenel with aniline relpreseating it as polsseesing a hemi-quinonoid The prewnt investigation was undertaken with a view to ascertain whether tlrinitropheiiylmethylnitro~arnine (tetryl) forms additive compounds of a similar type t o s-trinitrobenzene.It was olbselrveld that solutions of this subsLance in a variety of solvents belame deeply coloureld on tlhei addition of any amine primary, seaondary or tertiary except in such cases where the amine con-tlains strongly negative1 radicles and in a large number of cases it has been possible t o isolate from these solutions definite) crystalline aompounds which are without) exception compoands oh tebryl and the base united in equimolecular proportions. Owing to the fact that the additive1 compounds are1 largely dissociated in solution the separation of the pure! prolduct is difficult in oases whetre the constituents are less readily soluble than the additive product.The1 geaeral conclusions drawn by Sudborough and Beard (Zoc. c i t . ) regarding stability and depth of colour have been confirmed, altlhough the stability of this series of compounds is on the whole, less than $hat of the corresponding compounds of the trinitro-benzene series. Thus additive compounds of tetryl with phenols and tertiary amines have noti been isolated in a pure statq although evidence oif their formation is affordeid by the production of a red coloar wheln solutions of the components are mixeid and also i 1274 JAMES JONES AND LEWIS THE ACTION OF solrrie cases by ail iiivestjgation of tbs indting points of niixfures od the components.Hydrccarbon: and nitrophenols do not yield additive prolducts. The chied polintl od diffeIrelnm between t'hs additive compounds under consideration and those of the1 trinitroibenzelnei series is that, in many cases like the additjive compounds of picryl chloride with bases described by Sudbolrough and Piaton (T. 1906 89 583), they readily undergo a change to1 a condensed compound ; thus the' clompou nd o f t r i nit r oip heln y lme t h y lni t r o am inel and anilinel on storing in a sealed tube o r on slow crystallisation from a hotl solvent, yiedds 2 4 6-trinitrojdiphenylamine condensation appar-elntly ocaurring accolrding tot the equation C6H2(N02)3-NMel-N0,,N13,Ph = C,H,( NO,),*NHPh + NHMel-NO,. We have nolt succeeded in isolating the1 methylnitrofamine despite varioas attempts and itl is probably decomposed during the con-densatlion.The proiducts are idetntical with those formed by the action od picryl ohloridel on the aminel and in al numbw of cases exist in two olr mocel modifioations differing in crystalline1 form and mlour (compare Sudborolugh and Picton Zoc. c i t . ; Busch and Pungs J . p. Chem. 1909 [ii] 79 546; Hantzsch Bey. 1910 43 1678). It is of interest to1 nolte howelver thatl the1 first produotl is generally of a md aoIloIur whilst yelllaw or ocange mojdifications are obtained by the use of picryl ohloridel this beling duel to thei presence of hydrogen chloride which is instrumental in converting red forms into yedlow. Molle8ml ad - weight detelrmi na t i ons of the1 additive comp ounds indicate that noitwithst anding the delvellopmentl of deep1 collolur in the solutio'ns dissolaiation into tlhel compoaelnts is almost cmp1et.e in dilute solution.E x P E R I M E N T A L. The method olf work consisted in gefnelral in allowing a cold sattnrafleld solution of t,et,ryl in alcohol a,cet.one or be'nzene and t,realkld wit'h ra,thelr motre than o'ne molecular pro\portio:n of the aminel in the sa,rneI solvent1 or in ethe,r t o l remaJn untdl arystallisa-tioin took place. In many oa,ses oryst'als olf the a.dditive compojund were depoisited wit>h elasel ; in oitlhetrs condensation t,ook pla,m and t,he picry1 delrivative wa5 ob,taineld a,s first product. When the mixed sollutio8ns were helateid for some time o'n a water-bath or wheln the cryst,allisstioin was prolonged by leaving the solvent to evaporate slowly on a hot' plate t,hei coind,ensa8tioln cvrmpolund was usually deposited.Ammorn&z.-The addition of an a,lcolholic solution of ammonia (one and two equivalents reapectively were used in differea A'RIINES ON TRINITROPHENYI,MET€IYIA~ITROAM~NE. 1275 elxperimeiits) t o a sat8iiratetl alcoholic sulutioii of tcltryl yielcletl a deep red solutioii olf an additive conipcmnd which i t was not possi6lel to isolate. The deep colour gradually disappeared on warming and from tlhe reisulting yellolw solution picramide (m. p. ISSO) in a yield corresponding with 53 per cent. of the1 theioretical, crystallised out. The1 filtrate on evapolration prolvided a further yield of crystals which pyoved t o bet axnmolnium picrate.When dry ammonia was passed into a sollution of tetryl in benzelne little aotion took place but 011 the1 addition of a small amountl of amtone a deep red sollution was produced from whiclh a fluorescentl green oil separated. This solidified on keeping to1 a deep green mass which when freshly prepared had a strong odolur of ammonia. It is soluble in wateir or alcohol giving orange-coloured solutlions but i t has not been olbtaineld in good crystallinel form and the melting point is indefinite the substance delcom-posing explosively on heating abolvve 100'. After elxcess of ammolnia is relmoved the substance oontains C =34*19 H = 3.61, and N=24.97 per cent. correapoading with the formula Methylamioae.-When treateld witah an alcoholio sollution of m&hylaminel tetryl givee a deep red-codoared solutlion which after slight warming deposits reddish-brolwn neeldles (m.p. 112O) con-sisting of 2 4 6-t4rinitromethylanilinel (Romburgh Rec. trav. chim. 1883 2 105). On remystallising from alcohol containing a small proportion oif acid purei yellow needles melting a t 114.8O are obtlained (Found N= 23.45. Calc. N =23*09 per cent.). Benzylamime.-This yields 2 4 6-tTz'nitrophenylb emzykamke, oonsisting of ohocolate-cdoured needles (m. p. 143*3O) which when crystallised from alcolhol containing a little acid becomes golden-yellow and melt8 at 144-8O (Found N=17*70 C13H100,N, requires N = 17-61 pelr cent.). 9 niZine.-Thel additive compound of tetryl with aniline was readily olbtlained from belnzenei solution and folrms orangel-red plates melting at 64O (Found N = 21.35.CI3Hl2O8NG relquires N = 22.11 per centl.). The1 substanael declomposes oln keeping in the1 air by treatmeat with acids and by treatment with. many solvents regenerahing teltryl (0.5425 treateld with acid gavel 0.4064 tetryl = 74.91. Calo. t&ryl= 75-48 per oent.). On keeping in a selaleld tuba folr several weelks the substarnoe became moist and the product on crystlallisartion proved to be 2 4 6-trinitrodiphenylamine~ This substance is also obtained by slow mystallisation od the original mixture from warm benzene, acetme o r alcohol solutions. Itl forms orange crystals melting a t C,OHl20*N6 1276 JAMES JONES AND LEWIS TIIE ACTJON OF 1 7 8 O corresponding with the descripthi of Bamberger and Muller (Ber.1900 33 188). ol-ToJaidhe .-An additive1 compo urLd with tetryl is readily obtained by adding a slight excess of the base to a hot solution ol tetryl in 'benzene solution and allowing t o crystallise. It consists of brick-red crystals melting a t 63O (Found N =21.18; tetryl= 72.7. C,,Hl,08N requires N = 21.32 ; tetryl= 72.8 per cent .). The substance decomposes on exposure t o the atmospherel and also on reorystallisation yiellding tettryl. It doe@ not however, yield a condeinsation product; and 2 4 6-trinitrolphenyl-o-tolyl-atmine( is not formeid even when thel mixture) of components is boiled for forty-eight hours in a reiflux apparatus using various solvents. m-Toluidine.-The additive compound in this casel has not.bee111 obtained in a pure form as it is rapidly changed even a t the ordinary teimpraturel to a coindenseid derivativel. The productl obtained from a mixture1 otf the components in benzene solution clonsists od deep reld needles melting at about SOo which on treatr ment with acid regenerate hltryl. On warming this product with benzene o r with a' mixturel of chloroform and light petroIeum and allolwing to crystallise bright scarlet needles are1 deposited which melt a t 118.5O (Found N = 17.37. C,,H,,,O,N requires N = 17.73 per cent.). This substance wheln first prepared oould be recrystallised from alcohol1 without changel but ofn the additJon of a drop of acid to a saturated solutioa in alcohol orangepyellow prismatJc crystqals separa,ted.These1 melt at 129O and correspond with 2 :4 6-tri-nitrolphenyl-m-tolylamine as describeid by Busch and Pungs ( J . pr. Chern. 1909 [ii] 79 550). Theee autholrs state) that the sub-stance occurs in two forms an orange1 modification (m. p. 129.5") and a pure yellow form (m. p. 130'). The forms obtained by us are1 readily soluble in alkali hydroxide yielding deep red solutions, which on acidifying yield a pure yellow form melting at 1 3 9 O . We have been unablel so far t o reconvert the stable yellow form into the labile scarlet form melting a t 1 1 8 . 5 O . pToZuidime.-In the case of this amine an additive compound with t rini trop hen ylme thylnit ro amins is reladil y obtained by cry st al-lising a mixture1 olf the componeats from benzene or alcohol.It consists of deep red needles melting at 54" which are1 readily decaniposed by acids regenerating tetryl (Found N = 20.82 ; tetryl= 72.1. C14H1408N6 requires N = 21.32 ; tetryl = 72.8 per mnt.). The1 coadensation compound 2 4 6-trinitrophenyl-p-tolylaniine, was obtained in the manner described above and was isolateld i AWNES ON TRlNI!l!ROPHENYLMETHYLNI!L’ROAMINE. 1277 the two forms described by Busoh and Pungs (Zoc. cit. p. 548) a8 orange-yellow needles (m. p. 163-164O) and b l d - r e d prisms (m. p. 165O). m-XyZidine.-This base yields with tetryl a very unstable additive compound which undergoes condensation very readily to form 2 4 6-trinitrophenyl-m-xyZyhine, this crystallises in orange-yellow needles melting at 157O (Found : N*= 17.11.C,,H,,O,N re-quirea N= 16-86 per oent.). o-Anisidine.-We were unable to isolate an additive compound in this case although the colour of the solution indioated that suoh a compound is formed. From a warm solution in aleohol red crystals of 3/ 4/ 6/-trinitrc~2-methoxydiphenylamine separated, melting a t 143O (Busch and Pungs Zoc. c i t . p. 552 give 1 4 2 O ) . p-Anisidine.-In this case again no additive compound was isolated for 2/ 41 6’-trinitrc4-4-methoxydiphenylamine wits obtained even when cold solutions of the components were mixed. This consists of orange-red needles melting a t 172-5O (Found: N=16*75. Calc. N=16-77 per cent.). Busch and Pungs (loc. cit. p. 552) describe this compound as melting at 138O. We have repeated their preparation of the aub-stance from picryl chloride and p-anisidine and find that the product melts a t 172*5O as given above.p-A?~zinopher~oZ.-The additive compound in this case has not been obtained pure and readily passes into the condensed deriv-ative 2/ 4/ 6/-trinitro-4-hydroxydiphenylamine which consists of brick-red needles melting a t 174O (Turpin T. 1891 59 718). a-Naphthylaminc-The additive compownd of this base is readily obtained by crystallising a mixture of the components in equivalent amounts from benzene. It consists of well-defined black prisms melting at 94O. Tho compound is of considerably greater stability than the additive compounds previously described, but is partly decomposed by crystallisation from many solvents, and completely by warming with acids (Found N = 19.73 ; tetryl= 66.46.C,7H,,0,N6 requires N = 19.53 ; tetryl= 66-73 per aent.). N o condensation product is formed even after prolonged boiling of the additive compound or of a mixture of the components in a variety of solvents. P-Naphthy1amine.-The additive coml?ou?td is similar to the above and is obtained in black prisms melting at 90° (Found: N = 19.72. C,,H,,08N requires N = 19.53 per cent.). The mnipoiind is fairly stable and does not yield a condensed derivative. C,H,( NO,),*NH* C,H,M% 1278 JAMES JONES AND LEWIS THE ACTION OF m-Phe.12y~e~e~~~?n~ne .-Thel additive compo.tcnd od this base is madily obtaineld by crystallisation from benzene solution and colnsists of silky brolwn netedles melting at 84O whidh are moderateily stable[ but are partly decomposed by recrystallisation and completeily by warming with acids (Found N=24*94.C,,H,,O,N relquirea N = 24.81 per cent(.). The1 condetnsa,tion compound 2 4 6-triiiitro-nz-aminodiphenyl-amine is olbtainetd by slow crystallisation from hot acetone and folrms al deep red crystlalline powder mellting a t 207O (compare Jaubert Ber. 1898 31 1182). MethyZarlziZ&tze .-This base yields an additive cornpm~rlznd with trinitlrophenylmelthylnitroamine which consists of deep reld plates meltling a t 86O (Found N = 21.86. C,,H,,O,N require6 N = 21.32 per cent.). The condensation compound has not been obtained by our general methold. Dimelthylanilinei elthylanilinel and diethylanilinel all yietld deeply collolureld sollutions when mixed with solutions of tetryl but pure1 additive compoands have1 nolt yetl been olbtained in these cams.Moreolver condensatioln to1 picryl derivatives does notl occur elven aftler prolonged boiling in alcohol or acetonel solutions. Similarly nz-nitroaniline m d p n i troaiiilinel yietld slightly coloured solutions with tetryl but t>he separation of pure additive compounds has not been achieived. An investigation of the freezing-point curvels of mixturm of these bases with tetryl indicates that unsta,bls modecular compounds can exist. Halogen-substituted axnines give oaly feeble1 colorations with solutions of tettryl and form no additlive1 compounds ; condelnsation is also1 not possible. Su,mmary and Cowclusion~. Trinitrophenylmelthylnitroamine ( teltryl) reladily f olrms q u i -molecular additive1 compounds with the siinplelr arninm which in many cams readily condemse t o form pimylamines.The presence of alkyl substituelnts in the ortho-position in the1 amins does not affect the forniation of the1 additive compound but inhibits the colndeinsatioa The1 presence of the meltholxy-group in tho olrtho. position does not howevelr prevent the condeasation (oompare o-talixidinel and o-anisidinel). On the1 other hand sitbstitution in the meta-position renders the molecular compoiind unstable and it readily pashes iiito tfie corresponding picrylaminel. Thet naphthylaminels and the! secondary amines yield stablet additiv AMINES ON TRI~ITROPHENYLMETHYLNITROBMINE. 1279 CoinpoIunds which do notl pass intot condensatlion derivatives (colmpam Sudborough and Picbn Zolc.c i t . p. 589). According to Werner the components of molecular compounds Percentage of tetryl. Freezing-point curves of tstryl-m-nitroaniline (I) and totryl-p-nitroaniline mixtures (11). of this type are to be repraenteid as united by the residual or auxiliary valencies of the1 nitro- and amino-groups (I) 1280 MAXTED THE INFLUENCE OF HYDROGEN SULPHIDE ON It may be pointed ofut howelver that a representation in accord-ancel with Sudbolrough and Beard’s suggestion (p. 1273) brings the nitroaminel group into close proximity with the amino-group. If the amine be represented as possessing a hemi -quinonoid structure, the1 intense coilour of the1 molecular compounds and the1 comparative stability of the derivativels of secondary amines may also1 be explaineld. Thus the molecular compound with methylaniline might be representeld as (11). The influence of substituents in the1 phenyl grolup of the) amine on the ease with which condensation can take1 place1 is not4 obvious in a formula of this type whereas in tIhe case olf the Werner formula such substituents may be represented as modifying tho amount of residual valency whereby the aminel is attached to1 the ni troLgroup . We desire1 to thank Mr. Talfryn James f o r assistance in the1 preiparatioa oE some1 of the substances described. THE EDWARD DAVIES CHEMICAL LABORATORIES, ABERYSTWPTH. [Rcccived September 13th 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701273

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

1280 MAXTED THE INFLUENCE OF HYDROGEN SULPHIDE ON CXXXVII1.- The I n j h e n c e of Hydrogen Sulphide o n the Occli~~ion of Hydq-ogen by Palladium. Part 11. By EDWARD BRADFORD MAXTED. IN a previofus papelr (T. 1919 115 1050) it has been shown that whilst colmparatively small quantities of occluded hydrogen sulphide are sufficient totally t o inhibit the1 subsequent occlusion of hydrogen by palladium this occluded hydrogen sulphidel on being heated to1 looo in a vacuum evolves an equal volumel of hydrogen and passes into a sulphur complelx which is f a r less poisonous than hydrogein sulphids itself. The inhibitive effect of sulphur in the l a t h r form could be prediclted hy assuming the folrmation of a, oolmplelx Pd,S which is incapable of occlusion and ascribing to the re6dual palladium its normal occlusivei poiwer for hydrogen.In the preivious paper the1 minimum volumei of hydrogen sulphidei as such required f o r the1 complete1 inhibition of the1 occlusive poiwer s f palladium f o r hydrogen was not1 determined, it being noltled holwever that the volume of gas absorbed by palladium on exposure' for a short time to hydropn sulphide-this amounting in an experiment to1 13.5 C.C. per gram of metal T€I% OCCLTJSION OF RYDROGICN BY PALLADIUM. PART I J . 1281 was sufficient to1 prevent the ordinary occlusion of hydrogen on subsequently admitting the1 gas. . The1 subjeict has now been investigated further with the object of following quantitatively the inhibitive effect' of successive incre-melnt,s in the! hydrogsn sulphide content of a given welighti of palladium this hydrogen sulphide being present in the form in which itl is olriginally occluded and being added t o the palladium in small known quantities which for the majority of the1 measure-inelnts were less than the volume1 required for saturation.The poisoning curve1 for undecomposeid occluded hydrogen sulphide was FIG. 1. found t o be) linear in form. Evidence was also1 obtained of the gradual and spontaneoas dissociatioln of the1 occluded hydrogen sulphide men a t %he ordinary temperature( with the formation od hydrogen and of the Pd,S coinplex. This reaction is aocompanieid by a colrresponding change in the ocdusive power. E X P E R I M E N TAL. The apparatus elmployeld is shown diagrammatically in Fig. 1. It consists of a small absorptioln tube -4 containing a known weight oif palladium which was weighed out as chloride and redumd in situ as before.I n order t o intlroduce into the system hydroge 1282 MAXTED THE INFLUENCE OF HYDROGEN SULPHIDE ON or hydrogen sulphidei as requireid two gas burettes U a i d C' wcrc provided. These! had a capacit?y of 25 C.C. and 5 C.C. reapectively, the larger burethe being employed for hydrogen. The1 systelni zoluld be exhausteld by means olf a Sprengel pump IT or where more convenient by lowering and raising the mercury in B the three-way cock being turned as required. All parts of the apparatus weIra joined by fusion and all stopcocks weirel mercury-sealeld. I n view of tha inhibitive effect of mercury on the1 occlusive polwer of palladium obseirved by Paal and Hartmann (Be?-.1918, 51 711) a short plug of gold leaf 11 was inserted as a precau-tion against the1 possible! penetration 04 traoes of melrcury vapour into the absorption tube. The hydrogen useld for reducing the palladium chloride in A and for filling B was obtained frolm a cylindelr of the electrolytlic gas and was freed from traces of oxygeln by passagel through a " half-watt" lamp K follolwed by a soda-lime tube G and phosphoricl oxide tube F . The hydrogen sulphide was prelpared by the1 action of helat on magnesium hydroc sulphidel and was dried by passage elver calcium chloride. In order to relduce the volume! of the1 absorbing system t o as small a value as possible capillary connexiolns were1 employed throughoutl. The volume olf this system was redetesmiiied for each a,bsorptisn tubel the1 value being relquired in order tlo obtain the tlrue olaclusive powelr of the preparation froim the vollume of hydrogen absorbed from B .Each measurement was begun by sealing on a fresh absorption tubs containing a known weightl of palhdium ahloride. This was retduced t o metal by means of hydrogen a t looo the1 current of gas passing out of the system by way of the open end of A which was subsequently sealed off. The vodumel of hydrogeln which was capable of beling evolved a t 100' or occluded a t the ordinary temperature having been determinefd as before A was exhausted a t looo and after cololing to the ordinary texnpelrature E wa5 clmeld and a known small volume1 of hydrogen sulphidel allofwed to pass from C into the! absorption tube!.This gas was found to be quickly and practically colmpletely absorbeld by the palladium and, on subselquentlly admitting hydrogeln from B occlusion of this gas tofok place ta an extent delpendent? on the1 degree 04 poisoning which had been induced by the preliminary treatment with hydrogen sulphide. The reeults of the various measurements are summarised in table I in which the elxperimelnts are arranged in order of inareasing hydrogen sulphide content. The vollumes of gas are in every aase reducetd to Oo and 760 mm. the experiments being, however carried outl a t 20' No. of expt. 1 2 3 4 5 6 7 8 9 Weight of palladium. Gram. 0.1033 0.2380 0.0976 0.1714 0*2000 0.2795 0.1890 0.1422 0.0993 Original oc c h i ve power.7.25 16.45 6.86 C.C. H2. 12.1 14.1 19.0 13.1 9.9 6-25 Equivalent occlusive power in C.C. H per gram Pd. 70.0 69.2 70.1 70.5 70.5 68-0 69.3 69.6 68.0 TABLE I. C.C. H,S. absorbed. 0.23 0.65 0.38 0.78 1.35 2.00 1-61 1.68 1.75 C.C. H,S per gram Yd. 2.2 2.74 3.9 4.56 6.75 7.16 8.52 11.8 17.6 Subsequent primary occlucion. C 1284 MAXTED 1 THE INFLUENCE OF HYDROGEN SULPIITDli OW It will be s e a that the1 occlusive power of palladium for hydrogen is diminished progressively by the presence of increasing concentra-tions of hydrogen sulphidel. Provided that the ratio of hydrogen sulphide to palladium is less than a certain critical quantity a volume of hydrogen varying with the concentration of the inhibit<ant is occluded at once in a normal manner as is the case with unpoisoned palladium.This primary prolcess of practically inst,antaneous absorption is followed by a secondary process during which a further quantity od hydrogen is gradually and slowly ocduded. Evidence will be adduced later in the preaelnt< paper that secondary absorption is due tol dissooiation of the1 occluded hydrogen sulphide. On passing through a critical va,lue of aboutl 8.5 C.O. of hydrogen SO 70 60 60 4 0 30 20 10 0 2 4 - 6 C.C. of H,S pcr gram of Pd. sulphide per gram of palladium primary absorption celases and seloondary olcdusion only is observed ; further on plotting occlusive power against hydrolgen sulphide content itl is seen that the influence of this inhibitant both on primary occlusion and on total oloclusion is linear in nature.This result which is analogous t o that obtained for decomposed hydrogen sulphidel is illustrated in Curvels I and I1 in Fig. 2. In oases whelre the concentra4tlion of hydrogen sulphide is con-siderably in excess of that necessary totally to inhibit primary occlusioln the firstl stages of secondary absorption may take place sufficiently slolwly to mask the process unless the) system is kept under olbselrvation folr a oonsiderabls time after admimion of hydrogen. The prolcress of wcolndary absorption after beginnin THE OCCLUSION OE” HYDROGEN BY PALLADIUM. PART 11. 1285 slowly gradually increases in velocity and finally the velocity diminishes to zero as the limit of total occlusion is approached.With concentrations of hydrogen sulphidej below the1 clritical rattio, secondary absorption may om the okher hand take place a t a velocitly sufficieliit to reInder necessary a very careful following of the moveineint of the( mercury in the hydrogen burette in order to map accurately the progress oi the) first stages of the prolcess and to differentiate i t from primary absorption. Measurements in which readings of the1 volume occluded were takea in such cases, every few seconds during the first stagea of secondary occlusion, FIG. 3. 0 10 SO 30 40 50 60 70 80 90 100 Time in minutes. have however shown that the general form of this absorption curve although more rapid.is similar t o that4 observed with higher concentrations of hydrogen sulphide in which secondary occlusion is slower and more easily followed. The form of the various absorption curves is well shown in Fig. 3 in which the progress of absorption of certain of the) measurements is plotteld against the ti me. In order to obtain information reapelcting the nature of the process involveld during secondary occlusion careful analyses were iriade of the gas remaining in the absorptio$n pipette after secondary absorption had taken place for the purpose of ascertaining whether VOL. OXVII. 3 1286 MAXTED THE INFLUENCE OF HYDROGEN SULPHIDE ON or not hydrogen sulphide is evolved during the! change, simultaneously with the slow absolrption of hydrogen.I n no case was hydroagen sulphide in appreciable quantity oibselrved and eixhaustion of the] gas follolwed by thhe introduotion of fresh hydrogen a150 faileld to) cause! the' frecsh increase in occlusive power whioh wonld be expected if selcolndary olcclusion were! duel either to the! gradual displacement of hydroigein sulphide by hydrogen or to the relduction of a sulphide complex with elvolution of the sulphur as hydrogen sulphide. The! process appears on the1 other hand to be due tot it change FIQ. 4. Time in minutes. in the condition of the occluded hydrogen sulphide itself in that the change in ocollusive power is found to take1 place1 spontaneously on standing. In order to investigate this point' three nieasurements were carried out with three specinlens of palladium which were in each case allotwed to! absorb about 11.8 C.C.olf hydrogen sulphidel per gram of palladium the1 subsequent8 admission of hydrolgen f o r the determinatioii o l the ocalusive power being delaye'd for six minutes, four hours and twenty-three hours respectively. The absorption ourves olbt'ainecl are reproduced in Fig. 4 from which it will be seen that whilst' the1 final voli~n~e of hydroigen occluded by pre-parations containing an approsiinately q u a 1 volume otf hydrolgen sulphide is the sariiel in each caw. the form of thel absorption curv THE OCCLUSTON OF HYDROG~N BY PALLAD~UM. PART IT. 1287 has been influeiiced by the time which has been allowed t o ellapse beltween treatment with hydrogen sulphidei and subsequelnt measure-ment of the1 occlusivs power f o r hydrogen almost complet0 suppression of the slow process of secondary occlusion having bem induced by alloiwing the system to stand.The1 nature of the change1 undergone by occluded hydrogen sulphidel during the1 comparativeily slow passage of th0 system a t 20° from a state of lower t o one of highelr occlusive power would seem to be! similar to) thatl obtained instantaneously at looo in whioh the hydrogen of the1 hydrogen sulphide has belea shown to be wolved as such the1 sulphur being retained by the palladium as a Pd,S ooimplelx. This view is suppolrteld by considering the dissociation relaction H,S -C 2H+S in connexion with the1 volume od hydrogen occluded during primary and secondary absorption. During this dissociation a volume of hydrogein equal whilst in the! moleoular condition to that of the hydrogen sulphidei wcluded is setl free and must be added to the volume of hydrogen subsequently absorbed in order to delrive the true ocolusive power of the preparation.The total volume of hydrogen thus contained in the palladium shoald if the relaction postulated is the correct onel fall on the1 known poisoining curve, caloulateld oln the1 basis of the1 presence of Pd,S complex in amount equal to the1 sulphur coiitained in the hydrogeln sulphide omluded. The dose agreelmeliit beltween the observed olcclusive powers and the values calculateid from the Pd,S curve is shown in tablet 11 the reeults being also plotted graphically in curve 3 of Fig. 2. TABLE 11. No. of expt.1 2 3 4 5 6 7 8 9 C.C. H,S per gram palladium. 2.2 2.74 3.9 4.56 6.75 7.16 8.52 11.8 17-6 Hydrogen occluded. C.C. 64.0 62.5 59.5 59.8 53.7 51-9 47.8 43.0 27-7 Total hydrogen. C.C. 66.2 65.2 634. 64-4 60-5 59.1 56.3 54.8 45.3 Total hydrogen calculated from Pd,S curve. 66.0 65.4 63.8 62- 9 60.0 59.5 57.7 53-3 45.6 For the purpose of the calculatioa required fotr the above table, the occlusive power for hydrogen of 1 gram of unpoisoaed palladium under the1 giveln conditions has been taken as 69 o.c., this value being in agreement both with the) measurements 3 B 1288 R~DIIAL AND HAWKINS CATALYSIS 1" THE: colntained in the present papelr and with t h m previously publisheid .The palladium in addition to fundioning as an occluding medium would thus appear to induce the catlalytia disslmiation of the ooduding hydrogen sulphide. This gradual dismcliation affords Blsol EL ready explanation of the non-elxistence of a definite1 solu-bility of hydrogen sulphide in palladium. It has previously been sho1w-n that after preliminary saturatioa a slow but continuous absolrption of hydrogen sulphide takes place occlusion of as much as 42 0.0. per gram being obselrved by allowing palladium to remain folr three wmks in excess of hydrogetn sulphide. It will be seeln tlhaii the gradual disappearance od occluded hydrogen suIphide as such due t o the passage of the sulphur into1 the Pd,S form should aausa the system to cease to be satarated for hydrogeln sulphide. Fresh hydrogen sulphide is thus olacluded and the process continues until the olocluding palladium has been eliminated as Pd,S complelx. It would be expeoted that the catalytic activity of the palla,dim, necessary for causing dissolciation woluld also decrease progressivelly as poisoning proceeds so that the velocity s f this dissooiatioln and consequently of the absorption of fresh hydrogen sulphide should rapidly diminish with inmaasa in the sulphur colntent of the palladium. This deoreaw in the velocity of the dissociation of hydrogen sulphide with increasing sulphur content is demonstrated in it striking mannelr by the curvea of Fig. 3. It should be emphasiseld that the coimplex Pd,S cannotl without furtshelr investigation be assumed to be a true sulphide of palladium the charaoter of this mmplex having yet to be detelrmineld . CHARLES STREET, WALSALL STAFFS. [Receiued September 30th 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701280

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

1288 R~DIIAL AND HAWKINS CATALYSIS 1" THE: CXXX1X.-Catalysis in the Hydyolysis of Esters by Infra-red Radiation. By ERIC KEIGHTLEY RIDEAL and JAMES ARTHUR HAWKINS. ACCORDING tlol the quantum ra8diamtion hypothesis of chemical and physicad actions as deweloped by Trautz Lewis and Perrin (com-pare Ann. Physique 1919 [ix] 11 5) molecules only become reactive after absosptnioln ojf al definite! amount of energy the oritical energy inoremelntl although it appelars probable that fa HYDROLYSIS OF ESTERS BY INB'RA-RED RADIATION 1289 different readdons the degree olf activa'tion necessa,ry may diff sr, yet tnhw va,rious &ages of a,ctlivaltion corresponding with various ariticad elnergy incremelnts a,re rehtetd t'o olne atnother in a simple manner. This e.nelrgy acquired by t'hei moIle.de is poltentlia81 and is assumed to be supplield by radiahioa; thus all re'a8ctjions in the brolad sense of the1 te,rm are1 phot,ochemica,l o'r pholtophysical.The chaicad and physical eIffec8ts proiduced by a-particles. and edectlroins may be includeld sinc,el the chasact.e,ristics olf photsohmioal relac-tiona may be quaatit,a,tiveIly interpreted with tlhe grea.test f acilitiy on a aolrpwaular tlheory of ra,diatdoa. Up ta the praent timel with tthe exceptlion of the photaahemical reamatlions taking pla,ce in the actlinio part of the spect'rum there hae bean no direr& prmf of bhe vadidity of t~he extensioln od this hypolthesisl into the &her pasts of tlhe spectrum especially the infracred tlhe arguments in favour od such a,n hypothesis being indireut based an expelrimeintla81 datla such as the tempera'ture-mlefficient of uhetmioa,l aad physicall retaotiolns the he8a.ts of form-a,tion of chemical compounds or the lamteat' heat of evapration of t'he element@.The tempwature-ooe~fficie;nt oaf methyl acetate has beeln studied in detail by Lamble and Lewis (T. 1914 105 2330) who1 found tthamt the critiaal energy increme~nt was ab3oat 17,000 ca'lories per gram-moleoule whiah on t,he quaatturn thelolry would be provided by light of frequency of v=1'6 x lo1* or wave-length h=1*9 p in the infrwxd portioln of the spectrum. I n a constant temperatlure enclolsure such as a t,helrmosmtla,tl the density of the activahing ra,diatio<n u, is cmstant and t'he m a t convenient method of causing a.n altelratfion in a, and the4re:fore of the remtion-veloloity is by a,ltelra4tlioin of the telmpelra,tarel.u, mn holwever be alt elreld bmy elither decre'a.sing or increasing the absor bab,la r a,di ati on density wit.hou t a.lter ing the meIan temper a,-turei. Thus plants which a.re photosensitive tlo the a,ctinia part of the spestrum practioally cease growing in t,he dark alt,holugh main-tained aii the same tempera8ture aad otlher t,ypioal phot,ochemical a,nd photwatadytdu rea8ct~ioiis behave in like manner. I n the case, of infra-red ra8dia8tion however itl is difficultl to shield a,ny pa,rtl olf the reciding system from radiaibon of any pa.rticulas absorbable! frequenay since the system itsellf ca>n emitl t*his ra,dia,tio>n either as a reault of intramolleculas vibra(tion or even intermo~lwula,r oollisions (s,ee Nernst " Die Theoretischen und Exp.Grundlagen des neuen Warmesatzes," Halle 1918 p. 63). Alteration of the medium in which t.hs rela8cting molecules a.rel disperse<d doea how-ever prduoe an a.lt8e.ra.tion in the! reactlion velocity but as pointed out above it is atl preisent unmrt,ain whethelr this is t.he relsult of 3B" 1290 RIDEAL AND HAWKINS1 CATALYSIS IN THE an altsrattlio~n in u, t'he activating radia,tbon density or due t,o an alteration in v equivalent to an alteration in the activating ra(diatio1n ,f relquencies and ths mechaaism of the re,action or to both f ad'ors. It is holwever quite. possible t'ol inorebasel the1 density of the activating radiation v by illumination with radiation of the colrrect wa-vet-length A = 1.9 p.In the1 course of t.ime this radiation will be1 absorbeld and thei elnelrgy will be1 equally distributed over t,he whollel spectrum reeulting in a,n etlelva4tioln of tempeIrat.ure but 'if t,he relaotion is t,ruly photochemical and seIlelotivdy absorbs ra,dia,tion of this f rsque,noy a marked accmletratioa in the re.a&ion-vellocity shoiuld result withoat a.n appreciable1 rise in ttemperaturel. To1 teat this point a selries of pre3imina.ry elxperimente was con-dudmd oln the1 ratel of hydro'lysis of methyl a,mtate dissolved in dilutei hydrochlorio a.cid and etxposeld tlo inf racreld ra'diation ; the1 velocity-coelfficietnts obtained in this way wetre compareid with t4he norma,l va1ues o;bmt'aineld from idelntJcal solutions madained in the dark.EX P E R I M EN T A L. As a soiUrce 04 inf ra,-reid ra4diahioln pretlimina,ry e,xpelrimenla indioa'tsld tha,tt a'n a,ro lamp was unsuitlablel sincw although the cmrboln .speotsum lines could be maintaineid ah fairly unif olrm intensity the inf ra,-reld polrtion olf the spedcum (pmduced by the hot vapours) fludua,teld in intmsit,y. A uniform a,lthough rda-tbvely feeble infra-red belam was obtained from a sma,ll bundle of the oxide filaments mmmoinly emplolyeld in the Nernst glow-lamp. A number olf experiments wetre likewise oo.nduchd with a niohrome spiral raised to 600O; t'hha mlahively large quantity of noa-ra.diant heat prowed holwever to be1 a serious disadva.ntage. The1 sun was fo,und ta be the1 rnoetl convenielntl solurcet of suitab'le radiafiotn.I n all casea tlhei spelctirum wa's obt,ained by dispersion throlugh a simple1 opt'ioal syst'em of leinsea aslid quastz prism a d t prism not being a~vailalble. No1 a,ttemptl was made select any narrolw spectiral beam but thatl part of the spect.rum was employed come'ncing wit'h the portioln od the red just beyond the visible and stretching to an indefinite elxt.entl into the infra-red. To e81iminaate as far as polssible t,he material a,bsoirption od the1 ra,dia-tJon and thus minimise the dissipation of t,hel eiielrgy as heat,, the1 methyl acetate was illuminateld directly wit$ the radiation wit,hsut tihe int8emrvelntion of any glass. The solution undergoing hychlysis was. cont,aine;d in a 100 C.O. betake,r covereld on the out-side with tinfolil a similar beaker containing the1 cont'rd mlutio'n HYDROLYSIS OF ESTERS BY INFRA-RED RADIATION.1291 Both belakers were) maint,ained atl uniform tempe~ra,ture by immeasicm in a tmhermost.amtl or in broke'n icel a.nd water. The tempera.tnrel otf elach solution wa's cmtdnually o'bserveid and samples f o'r aaa,lysis wit.hdra,wn a t simultane.ous intervals for t,it,ratJoii wit,h 0'054A7-ba,ryt~a. I n all respe~cts elxce,ptl for illumina.tioa both soluticms wemret maint,ained undelr i den t i cagl condi t'ions and tse alted in the same ma.nner. I n the foillotwing t.ab,les a,rel givelii the) datmaL of a' number of elxpelriments aad the velocitly-c~elfficielnt~ t,he,red rom. Ill~rninant~ Nernst Filame,nts. Acid 0.1987N-HC1. I; calculated as a unimolecular coastant.(1.) Time. + Min-Hrs. utes. 1 55 2 9 2 39 3 4 4 15 5 25 U 12 46 12 58 1 14 1 31 1 46 2 14 3 10 4 45 oc (111.) Time. + Min-Hrs. utes. 9 35 9 49 10 7 10 49 11 49 1 0 a Control. - Tempera- Titre. ture. C.C. 21.75" 7-36 - 7.50 21-75 8.22 - 8.34 21.75 8.80 - 9.48 - 15.19 20.9" 22.3 23.4 23.7 24.9 24.5 18-35 18-35 -7.30 7.34 7-37 7.45 8.01 8.16 8.51 9.84 (?) 11.40 Illuminated. - Tempera- Titre. k x lo4. ture. c.C. 7cx 104. 21.75" 7.36 - -12.71 - 7.76 36.79 23-16 21.80 8.54 36.81 22.46 - 8-64 25-77 14.10 21.80 8.83 14.39 15.07 - 9-50 15.24 - - 15.19 -- 21.1" 7.20 (?) 26.00 7-39 22.3 7.45 31-67 6.00 23.7 7.65 41-35 9.26 23.85 8.00 42.09 25.22 24.7 8.38 41.69 (Time 2 hrs.4 mins.) 26.54 24.2 8.57 -24.27 18-2 9-10 40.15 41.94 17.9 9.55 41-94 - 11.40 - -Titre. C.C. +-\ Illum-Control. inated. 6-09 6.09 6.26 6.25 6.50 6.57 7.08 7.38 7-31 7.67 8-46 8.79 12-21 12.21 Temper at ure . & Illum-Control. inated. 21-70" 21.70" 21.70 21.70 21.30 21.30 21.20 21.25 20.75 20.75 20.75 20-80 20.75 20.75 7c x 104. -7 Illum-Control. inated. - Dark. 19.66 19.66 20-04 26.22 22.99 30.83 16-42 18.21 23.39 27.78 - 1292 RIDEAL AND HAWKINS CATALYSIS IN THE Illuminant : Time. - Min-Hrs. utes. 1 28 1 39 1 51 2 3 2 13 2 29 2 51 3 52 00 Sunlight. Illuminant: Time. - Min-Hrs. utes. Temper at ure . & Con- Illum-trol. inated. 1.0" 1-0" 0.5 0.5 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1-0 1.0 4.0 4.0 - -1 50 2 3 2 12 9 23 2 53 3 14 6 9 Time.+-Min-Rrs. utes. 1 50 2 3 2 12 2 23 2 53 3 14 6 9 00 Titre. C.C. - Con- Illum-trol. inated. 7-20 7-20 7-22 7-23 7.23 7.25 7.26 7.30 7.28 7-31 7-30 7.35 7.34 7.38 7.48 7.54 11.06 11.06 k x lo4. - Con- Illum-trol. inated. Remarks. 4.99 8.47 -4.46 5-82 -4-39 6-85 -4.34 6.28 Sun clouded. 4-23 6.26 -4-34 5.75 Sun clouded. 4.39 5-47 -- - I - - -Sunlight' and Niahrolma Coil. Temperature. , Control. 4.0" 2.0 1.5 1.5 1.5 1-5 1-5 -Sun. 4.0" 4.0 2.5 2.5 2.5 2-5 2.6 --I Nichrome. 14.0" 11.0 11.5 11.0 11.0 11.0 11.0 -Titre. C.C. c Control. Sun.Nichrome. 7-10 7.10 7.10 7.13 7-15 7.17 7-18 7.28 7.35 7.23 7.28 7.37 7-25 7.30 7.62 7-25 7.30 7.67 7-70 7-81 8.49 13.29 13.29 13-29 k x lo4. Nichrome calculated A > Control. Sun. Nichrome. 3-84 4.89 12-21 18-97 4.93 12.29 18.49 3.80 7-41 13.48 2.37 5.34 13.82 4.05 3.34 9.61 - 4.85 10.12 - -on temperature basis. 9.02 12-23 11-90 9-19 5.73 5.27 -It is elvidelnt thati the illuminateld methyl -tab is hydrolysed much more rapidly than that maintaineld at the1 same temperature in the dark. That the1 variability in the1 velocity-copefficient of the illuminated reactants is chiefly due( ts an altelratlion in the intensity of the infraxed radiation was evident from the obvious alteratlion i n the intensity olf tlhe sunlight by the1 passage od crloluds.To1 control this factor elxpelriments were conductled in which the rate of liberation of iodine by catalytia atmosphelriu olxidatioln from acidifield potassium ioldidei was simultanelously measured. This reaation is a typical pholtochemical one. It is ewidelnt from the follolwing figures thatl the same1 fador namely the1 radiation intensity affects both reactions an alteration in the velocity-coefficient of one! relaction coinciding approximately with a similar alteration in thei &her Illuminant Sun. Time. Hrj-ins. 1 38 1 53 2 9 2 23 2 40 3 1 3 22 3 41 00 1 12 1 26 1 46 2 2 2 17 2 31 2 46 m Titre. C.C. - Control. Illuminated. 5.90 5.90 5.93 5.93 5.96 6-03 6-00 6.08 6.03 6.10 6.06 6.16 6-11 6-20 6.13 6-23 9.73 10.90 5-88 5.90 5.93 5.95 6.02 6.02 6.05 11.60 5.82 5.85 6.05 6.08 6.11 6.10 6.17 11.14 Temperature.& Control. Illuminated, 9.0 3.0 0.5 0-5 0-5 2.0 1.0 1.0 -9.0 3.5 0.5 0.5 0-5 2.0 1.0 0.5 -6.0 9.0 1.0 3.0 1.0 1.0 1.0 0.5 1.0 1.0 1.0 1.0 1.0 1.0 -& Control. 3.32 3-33 3.66 3.66 3.36 -3.47 3.21 -2.78 2.69 2.48 3.68 3.05 2.94 1294 RIDEAL AND HAWKINS CATALYSIS IN THE Illurninant' Sun. Tempesature Oo. Time. Control. Illuminated. Milligram of A - iodine liberated Hrs. Mins. Titre. C.C. k x 10'. Titre. C.C. k x lo4. per minute. 2 35 5.75 1.87 5.75 -2 51 5.77 2.06 5-85 9.92 0.0043 3 8 5.81 3-70 5.86 4.11 0.0025 3 33 5-88 4-36 5-90 * 4.39 0.0025 3 51 5.95 - 5-97 5.99 0.0030 CC 11.85 - 11-85 - --It seemed possible] that t,he radiation falling omn the1 surface of the methyl amaelt,attei solution would proldum a looal rise of tempera-tlure aad t,hat~ the1 he.a,t would be carrie'd by conduction to the walls of the vessel beforel t*hel who3e.boldy o!f tihe so,lution ac.quired it highelr telmpelratnrel; thus locad rapid hydro'lysis might be1 pro-duced. This possibilitly was in relalitly relmote8 since the1 solut,ioa was f requelntlly agitated and no1 difference) in telmpesa8turei was olbserved. Nelverthelees it' was thought derjirablel to test this point, eIxperimentlarlly. A small vetssell conhining oil which could be ma.intaineld ah any det3ire.d t'elmperaturel by me'ans od an e'lectrio rwist,anm hnmelrsed in it was lowered just undelr the1 surface omf t'he rneit8hyl amlt'atel d u t i o n and sufficient elnergy was supplield to the oil t'ol maintsain the methyl acelt,a,tel a,bout.0 . 5 O higher than tshe coatroll elxpariment. The velocity-mefficielnts olbtaineld in t'his way agreed veiry closely with thoee calculated from the1 cont.ro1 eixpelriments after corretcltio8n for a rise1 in tetmpesattnrel of 0.6O as is elvide'nceld from the] following values : k x lo4 observed ............... 2.13 3.98 3-73 3.92 3-96 k x lo4 calculated ............... 2.13 3.99 3.73 3.86 3.96 From these elxpe.riment,s i t would seem tha,t t'he hydrolysis of me.thyl acetlat.e is in reality a.c*ellera.ted by irradiation in t,hel infra-reld portJoln of the speotrum an intelresting example of infra-reld photochemicad actioln ; furthesmore tha.t this speldral region is the1 region o'f adivity a,nhicipa.ted by t'he app1ica;tdon of t,hei activat,ion and quantum themies t'o chemical change.It is hopeld to continuel and extmd t8he8w e,xpelrirnelnts in the, near future in order if possible to e'lucida.te tlhe melchanism o f the cahalytic activity olf the acid e,mployed. There1 amre] two t,ena,ble theoriw to1 explain this cata,lyticl activit'y either bry an inorelasel in the a&va.t.ing radiation de,nsity or by an aclte8ration in the meoha.nism of the re:action. Although the1 above expesiment,al dab limit,e'd to1 olnel acid con-ceatsatioln a,rel tool limited to draw any definite condusio~n it would appear probable t.ha,t the1 second hypothesis, na.medy an alteIrahio HYDROLYSIS OF ESTERS BY INFRA-RED RADIATION.1295 in t4he meloha,nism of the relarotion t,hat is the intelrmediab compound thelory of catla,lysts is the correct one. It will be noted t.ha.t during the first period of illurninahion there is a very remarkable inmelase in the1 velocity-ooelfficient and that sub,sequently the1 ratel od refa,ction diminishes t'o a fairly aonstant valuel which is howelver still greaker than tha,t~ of the unillwnina,td sample. This phenomenon is not readily intelligible on the assumption of the action od t,he acid as afiecting a simple inoreass in the ra,diat,ioln delnsity sinw a f urthelr inorease in t,he ra.diatbm density should increase the1 reaction vellotoit~y pro1 ra.ta.On the inter-meldia3te-compolund theory hotwelver t,hs observed result is to be antioipa,bd. Briefly if the twa reactions be1 reprewnted by tnha follocwing purely hypothetical ecptionns : (i) CH,*CO,Me + H20 (ii) CH,*CO,Me + HCl + H20 MeOH + CH,*CO,H CH,*CO,Me,HCI,H1O CH,*CO,Me,HCl,H,O IT MeOH + CH,*C02H + HCI. t'he rate olf decompositioln in sach case beling unimolecular in exoeas of wa4telr t,hen the1 first reta,ctlion-velocity is gove'rned by the rate of a.otiva,tdon od the1 methyl aoatat'e to! re,aotl with t'he a,ctive wa,ter, a,nd t,he swond by two relatct8ioiis namely the1 ratel ojf activa8tioa of the1 melthyl acetatel to react with active1 hydrochlo'ria acid and by the rate of adiva,tion of the complelx t o bre,ah down into the pro-ducts of the reaction.The rate of any sequent reaction is always governed by the slowat od the1 inklrme.diatet relacotions ; thus i f we assume the slowest one in hhis case1 t.o be the decomposition of the1 mrnples theln illumina,tion with a' pa,rticula.r frequenay of light will acce;leIra.tel the decompo'sition of the compla so tha,t the re:action-velocity will t'heln be1 govermd by the next sloweat rwa tIon which we have assumed to ba t'hel co!mbination of the methyl amtlate and hydra,ted hydrochloric a'oid. This relaation however, t a k a p1a.m) morel rapidly tlhan the1 combinatioa of methyl acetate and waf,er. On this hypothesis of selries reactions t<he prima4ry acceleration on illumination is to be aikributed to the rapid decom-pwition of the ampletx which is premnt in redactively large quaati-ties since it bre.aks down but slowly; the primary acmlelrates then fadls off until the! normal rate of the1 next slowest rsaotion sets in. Summary. Preliminary experiments have1 indicated that! the hydrolysis of methyl amtatel is ca,taJytically awe;lerated by infra-red radiation. 3 B* 1296 HINKEL THE ACTION OF CHLORINE ON The speotral region of photoachivity is in agrtxmeint with that ca,lcrulalhd o n the aativation and quantum tbwria of chemical &lion. The experimental data obtained asa most readily interpreted on the1 intermediate-mmpounds hypothesis in the caw of thel hydrolysis of esters by dilute acids. It is propoaed to1 extend thew experirneat's in order ta obtain further information as to the number and nature of these intmediatel colmpaunds and t o examine the spectral region o f their a4ctivation in more detail. UNTVE~SITY OF ILLINOIS U.S.A. AND TRINITY HALL CAMBRIDGE. [Received July 15th 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701288

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

1296 HINKEL THE ACTION OF CHLORINE ON CXL.-The Action of Chlorine on 3 5-Dichloro-1 1 -d imethy l- A 4- cy clohexad ien e. By LEONARD ERIC HINKE'L. IN the study oif the conversion olf hydraaromatic derivative6 into compoands olf the aromatJa wries the action of bromine on 3 5-dichlorol-l l-dimeithyl-A2:4-~yclo~hexadiene was fully investi-gatled (Croasley T. 1904 85 264). It was shown that the reac-tlio8n was largelly influeaoed by oolnditlion of eurpelrimelnt~ 2 molecules of bromine giving rise tlcr a visoid liquid whioh on distillatioa gave 3 5 -dichlor(~-4-bro~moto~-xyleae and a qstialline solid C8H,Cl,Br,, preswn eld t a be di C;hl o'rotri bmm odime thy lcy clo hexeael, On tlhe othelr hand 1 molecule of bromine1 gavel as principal pro-d u d 3 5-dichlaro-6-bromo-o-xyle1ne1.Explanations of the produc-tion of the various suhtancw are suggested in the original paper, but as sevelral poinh remaineld to be cleared up the work wab repeateld using chlorine instead of bromine[ in the hope thatt more light would be thrown on the meohanism od this type of relaation. When 3 5-diohloro-1 l-dimehhyl-h2:4-~ycZohexadiene is treated witb ohlorinel the1 proiduclt consistts of a visoous syrup whioh yields a small quantitly oif a crystalline solid C,H,Cl,. The1 syrupy filtrate1 from the crystals yields 0111 distillation the two1 isomeric t richloro - ocx ylenes and also t&achloro+o-xylene. The1 oompon nd C8H,Cl is evidently a pendachlorrodimethytcycloihexem correspond-ing with and formed in a manner similar t o the diclhloroltribromo-dimethylcyclohexene demribed by Crossley (toc.cit .) and in like manner accounts for tlhe formation of 3 4 5-trichlorcr-o-xylene i 3 5-DICHLORO- 1 I-DIMETHYL-A2:4-CYCLOHEXADIENE. 1297 the filtrate from the orystals since the pentachlorecompound docompow on heatling into1 3 4 5-trichlorol-o-xylene. The farm-ation of pentlac;hlorodimethylcycZohexelne doee not however a m u n t for the production of elithelr 3 5 6-t75ichlo~ro~ol-zyJene or htr* chlorol-oi-xylene. The action of chlorine1 on dichlorodimethylcyclo-hexadiene must be more delep-seated since 100 grams of the latter yield only 28 grams of pentachlolroclimethylcycZohexene 18-20 grams of 3 5 6-trichlorol-o-xylene~ and 10-12 grams of a mixture of 3 4 5-triohloro+o~xylene and teltrachlom-ocxylelne.Moreover, when 1 molecule of chlorine acts on dichloroldimelthylcyclo-hexadienel the resulting liquid always contains a clonsidelrable quantity of the unchanged original compound together with 3 5-di- and 3 5 6-tri-chlorolxylenes; tlhe yield od 3 5 6-trichlo1rol-obxylene is small being oaly 16-18 grams frofm 100 grams of dichlolradimethylcycZohexatlielne. The product of the action of one malleoular proportion of chlorine on dichlorodimethylcyclo-helxadielne is probably tetrachlorodimethylcychhexelne~ (I) ; this substance is unstable$ and very reladily evohesl hydroigen chloride even at, low temperatures. probably forming a trichlorodimethyl-cycloihexadiene (11) whioh then slowly loses another molecule of hydrogen chloride yielding 3 5-dichloro-ol-xylene (111).A com-pound of folrmula I1 would combine witlh 1 modecule od chlorine in a mannelr similar to dichlorodimethylcyclohelxadiene yielding #' (111.) CMe<CCl=CCl>CH 'CMe - CC1 (VII.) 3 B** 1298 HINKEL THE ACTION OF CHLORINE ON a.n unstable substa*nm (IV) from which by 1- of 1 moileoule of hydrogen chloride 3 5 6-tsiohloro-o-xylelne (V) would result. The1 formation of teltsa7chlorol-o-xylelne oa,n be explaineld by sup-po'sing tlhah wit'h exmss of chlorina t'he tlwo compolunds I1 and IV are sucoessively f olrmeid and t8hajt more chlorine1 co,mb,ines with IV, yielding a.n unst,able substt.a,nco ha,ving tIha formula VI which immeldiatelly losea hydroigeln clhlolride giving rise1 t'o tet<ra,chlorol-oi xylelne (VII). The only point tlol be decidejd is the1 positlion off t,hel ohlorins ahoms in tIhe two1 pmsiblel t.riolilo~rol-o-xyleaes.3 4 5-Trichlorwo~xylene was t,helref ore synthelsis,ed from ol-$-xylidetnel whioh was chlolrina,ted, a.nd the a,niinol-group t'heln displaced by ohlorine. The 3 4 5-tri-chlora-obxylenel obt'aineld in t,his way melteld a8t 96O and its melt+ ing point rejmained unchanged when mixed with the substlance obmtained by heafing peint8a80hlorodim.ethylcyclolhexelnel. Co!nse+ quently the; olthsr tlrichloroio-xylene must have the chlorine atoms in t,hs 3 5 6-position. Bohh tlhel t,riohloro-exylelnes yield oln f urt'her chlorination the same1 t'eitlra,ohloro-oi-xyleae melting ' a't 223-224O which was identical with the compound obtained by t'he actioln of nitAcl a,cid on pent8a.chlorodimethylcycZohexenel and also with.the subst8ancel, melting a t 223-224O isohted in the1 distIilla,te olbhadned from t,he fil hate from pen t,a clhlotr odim ethyl cy clohexem . 3 4 5-Trichlo~ro-o-xylene1 oln brominatdon reladily yields 3 4 5-tr~cItZ~ol-6-broinzo~-o~xyLe.ne~ but on brominating 3 5 6-trichlorol-0-xylelllei in a simihr manner an unsxpecteid rea.ction takes place, giving rise t o 3 5-dichloro-4 6-dib,romo-oi-xyleae1 and not 3 5 6-taichlo~ro-4 -br omoi-o-xylene~. Bohh the1 tlricichlorctexylenes rewmble the diohlorobromo!-o-xylelnes in thelir behaviour towards nitric a,cid. Thus 3 4 5-tlri-ohlorow-xylelnel gives wit'h fuming nitriria acid 3 4 5-trichtlo~o-6-nitroLo-xyZe:me whe,rea.s 3 5 6-trichlolr~o-xyle~ne unde'r similas tre8a8tanelnt gives 3 5-dichloroi-4 6-dinitro-o-xylene.E X P E R I N E N TAL. Actiom of Excess of Chlovm'ne om 3 5-Dichloro-1 I-dimethyl-A2 4-cyclohexadiene. Selvem ty grams of freshly p r epareld di chlm oldimet h y 1 cy c lo+ hexadisnel were1 dissolvsd in 70 grams of dry chloroform and a rapid stream of chlorine was passeld in the1 whole1 being cooled in ice(. Hydrogen chloride1 was immeldiately elvolved and subae-queatly in tocrrents. After saturation with ohlolrinel the chloro-form was evaporated on the watelr-bath and the viscid yello liquid was plamd in a vacuum over sodium hydroxide whein i t gradually deposited oolourless crystals. These were collected (18.5 grams) (filtrate==) and after being rapidly washed with light petroleum purified by crystdlisation from alcohol (Found : C1= 62-62.C,H,Cl re,quires C1= 62.83 per cent.). 2 3 3 4 5-Pentachlwo~-l l-d2'rnethyl-h~-cyclohexene, is readily soluble in the) cold in ether chloroform acetone beinzene, o r methyl and ethyl alcohols and in light petroleum on warming. It crystallises in stout prismatic neeldles melting atl 103.5'. A c tion 01 f Hen t on Pen to c h lor.odim e t h y lcy cloh ex en e . The substance was heated atl 120-130° in a sulphuria acid bath, when it mellted to a colourlese liquid and copious evolution of hydrogen chloride occurreld. The liquid was thea removed from the acid-bath and heated more strongly until no1 further evolution of hydrogen chloride occurred and the liquid began t a boil. The rmidue solidified on coding and was crystallised from alcohol (Found Cl=61.16.3 4 5-Trichloro-o-xylelne is very readily soluble in ether chlors-f o m benzene light petjroleum or hot alcohol crystallising from the latter in masses of felt-like needles which o n pressing form a waxy mass melting atl 96O. It distils unchanged a t 261° is volatile in steam and is ewidelntly identical with the1 aompound describeid by Claus and Kautz (Ber. 1885 18 1369) who give m. p. 93O and b. p. 265O. On chlorination and brominatioa in the1 preseacs of iron it gives respeotivedy 3 4 5 6-te1t~rachloro~-o-xylene melting atl 223-224O (p. 1300) and 3 4 5-trichloro-6-bromo-o-xylene melting at 226O (p. 1300). Fuming nitric acid converts i t into 3 4 5-tri-chloro-6-nitro-o-xylene melting a t 149O (p.1301). Calc. C1=50-83 per cent.). Actiom of Nitric Acid om Pentachlorodimethylcycbhexeme. Five grams of the cyclohexenei derivative were heated with 40 O.C. of fuming nitric acid over a watelr-bath. A vigorous action elnsud and after heating for ten minutes the1 contelnts of the flask were pauretd into cold water. The pasty solid was dlected, washed witb water and after three crystallisations f r m elthyl aceitate the neeidles melltsd a t 223-224° ; the melting point was not altered on mixing with 3 4 5 6-te1trachlorol-ol-xylenq (p. 1300) (Found C1=58.4. Calc. C1=58.19 per cent.) 1300 HINKEL THE ACTION OF CHLORINE ON Examination of Filtrate A (p. 1299). The liquid was helated in a distilling flask tot 140° and gradually raised tlo 180'; a copious evolution of hydrogen ohloride occurred.The liquid was maintaineld a t 180-2QQo folr one hour and then gently distilleld three main fractions beling obtaineld boiling a t 225-245O 245-260° and 260-27Q0. The first two1 fractions, whiah partly sollidified oa keeping were subjeded to carelful and relpeiated fractional distillation and the main fractioa b. p. 230-240° solidified colmpletely o n c ing to a collourless orystal-line! mass which after being crystalliwd several time6 from alcmholl melteld sharply a t 47.5O and colnsisted of 3 5 6-trichloro-o-xylene (p. 1302) (Found C1= 50.99. C,H,Cl requires C1= 50.83 per mnt.). The residue of higher boiling point was addeld t o the1 third fradlion (b. p. 260-270°) and on submitting the mixture to repelated fradiolnal distillation two1 main fraotions b.p. 255-265O and 275-280° welrel olbtainetd. These were1 subjelcteld tot repelated fractiolnal orystallisatioa from aloohol and then from ethyl acetate, in which the fraction od higher boiling point is less readily soluble, and al partdal separation was effected yielding two1 substances one crystallising f r m alcohol in feilt,-likei neledles rnellting a t 96O and atl tlhe same telmperatme wheln mixed with 3 4 5-trichloro-o-xylene (p. 1299) the other crystallising from ethyl acetate in long, transparentl needles melting a t 223-224O and a t the same telmperature when mixed with 3 4 5 6-tetrachloro-o~xylene (below). Actionl of ChloTine om 3 4 5-Trvichlo~o~ocxyZe~~e Foil.maltiom! of 3 4 5 6-Tetrachloro~-o~-xylene (VII).Two grams of the substance were dissollved in 10 O.C. of dry uhlosoform and chlorine1 was rapidly passed into the solution in the prelsenaei oif a small quantity of iroln filings. On warming sub-stitution readily took placel. The chlorofolm was evaporated and the residue mystallised from ethyl aceitlatle. The substance1 is very readily solluble in elthelr alnd readily sol in chlorolform hot aloohol, or &hyl aueltate crystqallising from the1 lahtelr in long blender, glistening needles medting a t 223-224O (Claus and Kaxitz b c . c i t . give 215O). d c t b n of Bromin8e om 3 4 5-Tr'ichZovol-ol-xyleme Forlmaltiom o'f 3 4 5-Trichlo~o~6-brom~o~-o-zylene. The substance wa's dissolveld in at sma(l1 quantJty of ohlosoform, On wa4rming and broknine added in t>he prselnclel of iron filings substitution taok place and the sparingly soluble brmclderivative wpmated.The ohlorofom was evapwated and the residue dis-solved in benzene the solution being washed with water dried, mnoentrated and allowed ta crystallise (Found C1= 36.67 ; Br = 28.06. C,H,Cl,Br requires C1= 36.92 ; Br = 27.73 per oent.). The compound is readily soluble in ether or benzene sparingly so in chloroform or alcohol and crystallisee from ethyl acetab in slender glistening needles melting at 226O. A c t i m of Nitric Acid om 3 4 5-Trichlol.ol-cr-xylema F s r m t i m of 3 4 5-Trichloro-6-nitro-cr-xylene. Four grams of the substance were gradually added to 40 C.C. of fuming nitria acid and warmed un the water-bath for twenty minutes when the solid gradually dissolved.The mixture wag poured i n b water and the separated solid cryshllised from doohol in which i t is sparingly soluble (Found N=5*436. C,H,O~Cl requires N=5*5 per cent.). The compound is readily solubls in ether aaetone benzene, chloroform or light petroleum and moderately 80 in hot almhol or ho6 glacial amtic auid; i t orystallises from alcohol in stout, transparent crystals possessing a slight yellow tinge and melting at 149O. Synthesis of ,3 4 5-Trkhlsra-o-xylene. e4-Xylidine was acetylated and chlorinated as deercrihd by Crossley (loc. cit.). Three grams of the resulting 3 5-diahloro-a-Cxylidine were suspended in 15 C.C. of conwntrated hydrouhlorio aoid in which it is not soluble in the cold a solution of 1.5 grams of freshly prepared ouprous chloride in 15 0.0.of concentrated hydrochlorio aoid was added and a solution of 1.1 grams of sodium nitrite in the least amcrunt of wabr dropped into the mixture, which was heated on a water-bath to 60-70°. After one hour, the whole was distilled in a current of s h a m when solid pas& over which melted at 82O. After recrystdlising twice frm alcohol the crystals melted sharply at 96O and the mdting point wa4 not ohanged when the substance was mixed with the triahloro-o-xylene described on p. 1299. A c t b of One Molecular Propodion of Chlorine om 3 5-DichtOlro-1 1 -&met hyl-Az 4-cryclohexadiem. Dichlorodimet-hylcyclolhexadiene (1 mol.) was dissolved in twice ita weight of dry chloroform and the solution aoioled in a freezing mixture of ice and salt.Chlorine was paseed into tho niixture 1302 RINKEL THE ACTION OF CHLORINE ETC. and thel hydrogen chloride which was immediately evolved, absorbed in a soddime tube. The passage of ohlorine was stopped when the inoreasel in total weight of the apparatus was equivalent to one molecular proportion of ohlorins. On evaporating the chloroform a pale yelllow liquid remaineld which showed no signs of crysttallisation elven after remaining for a long time in a vacuum over sodium hydroxide. The liquid was heated to 150-180° for me hour when much hydrogen chloride was evolveid. The liquid was theln distilled and a clear yellow liquid boiling between 215O and 241° passed over. The liquid was submitted to careful and repeated fractional distillation and three fractions boiling at 217-220° 222-226° and 228-233O welrel collected.b . p. 217-220°.-This liquid when left in the air, rapidly darkened and resinifield and whein hydrolysed with 30 per cent. sulphuric acid yielded dimethyldihydroresorcin sholwing that it colntainsd 3 5-dichloro-l 1 -dimethylcyclohexadiene. Fraction b . p . 222-226°.-This liquid could not be separated into al portion boiling cmnstlantly a t 226O (3 5-dichlolra-o-xyletne). When treated with bromine1 in the premnm of iroln filings it gave 3 5-dichloro-4 6-dibromwo+xylene which after arystallisation from ethyl acetate melted a t 233O (compare Croesley Zoc. cit., p. 284) and an nitration gave 3 5-dichloro.4 6-dinitro-o-xylens melting a t 173-174" and identical with the compound obtained by the action of nitric acid on 3 5 6-trichloro-o-xylene (p.1303). B'ralctiom b. p . 228-233°.-The~ liqbid almost entirely solidified on cooling. The crystals werel callelated and the\ filt-rate was dis-solved in warm alcohol and the sollutdoln cooled in icei wheln a further yield of crystals was otbtained which after crystdlising several times from alcohol meilted a t 47.5O. This melting point was not altered when the substance was mixed with 3 5 6-trichlolro~ o-xylene (p. 1300). 3 5 6-T?.ic~.losol-o-lcylene is readily solublet in the cold in &her, benzene ohlorof ormy light petroleum or ethyl acetIate orystallises from methyl or ethyl alcohol in short ooloarless crystlals and oan ba distilled unahanged. It is readily acted on by chlorine in the presence od iron filings; the sotlid product crystallises from ethyl amt?tate in long glistening needles meilting a t 223-2240 and is identical with 3 4 5 6-tetrachloro-o-xylene (p.1300). Fraction A c t i m of Bromine om 3 1 5 6-Trichloro-cr-zyZene. Two grams of the subst8ancxtl were1 dissolveid in 10 C.C. of dry chloroform and exmm of br-inel was added in tlhet presence' of iron filings. On warming substitmuttion takes plaw readily. Th BARKER AND PORTER THE EFFECT OF ASYMMETRY. 1303 solid productt crystallised from eithyl acetate in long silky needles melting at 233O and this melting point was not changed when the substance was mixed with 3 5-dichloro-4 6-dibrolmo-o~xy1elne (Found C1,=21*65; Br==47*63. Cab. C1=21*32; Br=48-05 per cent.).Actiom of Nitric Acid o n 3 5 6-Trichloro-o-xyler~e. Five grams of the substance1 were( slowly addeld to1 30 0.0. of fuming nitric acid and warmeld on the water-bath when the sollid dissolved after which a rather vigorous action took place. The1 helating was continued for twelnty-five minuteis the mixture poured into oold water and the1 separated semi-solid after being washed with warm water cryst(a1lised from alcohol. Considelrable difficulty was experienced in purifying this material by me1ans of alcohol, and it was therefore twice1 recrystallised from light peltroleum (b. p. 40-60°) and finally from alcoholl. The flat plates obtained in this way melteld a t 174O and were identdfield as 3:5-dichloro-4 6-dinitro-o-xylene (Crossley loc. c i t . p. 284) (Found N= 10.51. Calc. N=10-56 per cent.). The author wishes t'o express his indebtedness to1 Colonel A. W. Crossloy C.M.G. folr suggesting the above investigation and for much valuable help and advice throughout; t'hanks are1 also due to the Raelarch Fund Committee of the Chelmical Society for a grantl which has in part defrayed the! expensea of this investigation, CHEMICAL DEPARTMENT, KINCI'S COLLEGE LONDON. [Rcceived September 241h 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701296

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

BARKER AND PORTER THE EFFECT OF ASYMMETRY. 1303 CXL1.-The Efect of Asymmetry. A Study in Crystal Structure. By THOMAS VIPOND BARKER and MARY WINEARLS PORTER. COMPARATIVE stludies of more or less closely rellatled olrganio mm-pounds abound in the literature of oryst(a1lography ; in fact( the attempt to trace sol-Galled " morphotropio resemblanaes " may be regarded as one of the distinotive features of crystallographio investigation during the last fifty years. Whilst such investiga-tions have added elxtelnsively ta the! general stmk of knowledgel, they cannot unfortunately be said t o have led to the formula 1304 BABEER AND PORTER THE EFFEOT OF ASYMMETRY4 tion of any general laws correlating chemical compmition and q s t a l l i n e form. A t least one of the caum of this general fdlure has been reoently rewaled as the result of the invwtigation of urystal struoture by means of X-rays.It is now clear that the Bravais space-lattice do not always represent completely the atruc-ture of a crystal for something like 70 per cent. of the structures already elucidated by X-ray methods consist of several inter-penetrating space-lattices that is of “point system~ ” i n the sense of Sohncke Fedcrrov and Schonflies. Crystal structure is thereby proved to be a subject of great complexity and much further investigation is evidently needed before general laws oan be f ormulatd. The object of the present research was to ascertain whether a definite similarit<y may exist between the orystalline forms of two closely related organio substanw one of which differs from the other in p-sing an asymmetric atom.The kind of similarity sought was of that definite degree which exists between isomorphous substances rat,her than that vaguely implied by a “morphotropio resembl an 08. ” I n selecting materials for examination i t was necessary to find a series of compounds in which the replacement of one radicle by another is not incompatible with an isomorphous relationship (at least so long as the molecule remains symmetrical) before proceed-ing to inquire whether a further replacement of radiclea by which the molecule becomes asymmstric is compatible with the survival of isomorphism. Now experience shows that in series involving the replacement of organio radiclea isomorphism is only ta be found where the molecule is relatively large in proportion t o the ohange of composition and i t therefore seamed probable that com-pounds of the type R,NHgI (that is “double oompunds” of a quaternary ammonium iodide with mercuric iodide in the ratio 1 l) in which R may represent either identical or different organic radioles should be suitable for the end in view.Such compounds, having a pale to deep lemon-yellow colour am known to crystallise well from acetone solutions. A commencement was therefore made with a series of compounds in which R is wholly represented by alkyl groups (compare table I) but no definite cam3 of isomorphism were encountered. This is a fact of some significance as illus-trating the highly sensitive character of the relationship between form and composition in spite of the high molwular weight the replaoement of even a single methyl by an ethyl radicle brings about a fundamental change of crystalline form and structure.The investigation of a still more complex group then became ncmtissary. The phenylalkylanimonium ocunpuunds of the general No 1 2 3 4 5 6 7 Substance. Me,NHgI, MeEt.,NHgI, Et,NHgI, PrEt,NHgI, MePr,NHgI, EtPr,NHgI, Pr,NHgI, TABLE I. The AIkylamrndum Group of Crnpyun&.* Crystallographic cons tan ts. I e \ Axial System. a b c . angles. Rhombic 0-5777 1 0.5199 -Anorthic 1.1202 1 0.5578 a= 102' p= 93'56' y = 108' Monoclinic 1.4826 1 0.8192 p=107'55' Y9 1-1350 1 0.7359 p= 97'11' Y Y 1.0749 1 0.6542 j3= 93'22' Rhombic 0*6:90 1 0.5106 -Monoclinic 1.4965 1 0.7328 p=113'16' The corresponding trimethylethyl and trimethylpropyl compounds were also prepared, In addition to the 1 1-compound tetraethylammonium A description of in a form suitable for measurement.substance with mercuric iodide in the molecular proportions 2 3. part (p. 1314) 1306 BARKER AND PORTER THE EFFECT OF ASYMMETRY. formula R,PhNHgI, furnished clear cases of isomolrphism. I n the annexed table the first member is noh isomorphous wit$ the s u m d i n g compounds. The nextl threel compounds howeveir are dearly isomorphoas and moreover exhibit the following peculiarity. Although the compound Me,EtPhNHg13 (No. 9) differs frolm the compound MeEhPhNHgI (No. 11) by an amount expressible by CH, it is much more olosely isomorphous with it than is tlhe compound M+PrPhNHgI (No.lo) in spite of the fact thatl the last two compounds are isomerides. The similarity of angles between the first two mentioned compounds is indeed com-parable with the olose isomorphism melt with in the sulphates of potassium rubidium wsium and ammonium. The isomorphism of the t h e cornpounds numbered 9-11 was confirmed by a met!hod which has been espeaially developed by olne of us (T. 1906, 89 1120). Crystal fragmelnts of any one of the1 three substances continue to grow when p l a d in a saturateld solution of either of t h O others and thus satisfy one of the mostl rigid testa for isomorphism. Proweding with the table it is seen that there is a marked change of form in passing from Nor.11 to No. 12 differ-ing in composition by CH, but t,hatl the two compounds Et,PhNHgI (No. 12) and Et,PrPhNHgI (No. 13) also differing by CH, am olosely isomorphoius-a colnolusion whiclh was confirmed by the formation oC regular growths when a crystal of one is immersed in a satnrated solution of thel other. The choice olf the final materials was of course dictlated by practical oonsidma tions . Asymmetry of mole oular configuration is most easily proldud by the inclusion of a beinzyl radide and the phenylbenzylalkylammonium group of compounds represented by the general formula R,(CH,Ph)PhNHgI, in which asymmetry is involved by the seleotion of different R-groups was Berefore elxamined. The results of the crystallographia examination are summarised in table 111.A glance a t the values of tlha axial ratios is sufficlielnt to show that the fir& substance has no relally close1 relationship to the second and third oompounds ; morelover the largel discrepanay in the axial ratio b c of the fourth substance sholws that it aIw stands alone. The relationships of the second and third com-pounds (No. 15 and No 16 of the1 table) deserve further notice. The axial ratios and angle /3 differ by rejlativeily small amounts, thus indicating the possibility that the two substances are isomorphous. A comparison of the f orm-development points tthe same way. I n the1 methylethyl derivative we have b{010} al{lOO}, m{llO) a{001} p{O11} and r{ZOl} with the forms b m d a developed as small facets whilst! in the diethyl derivative we hav TABLE 11.The Phenylullcylammoniwn G ~ o u p of Compowds Crystallographic constants. , K O Substance. System. a b c . B. 8 Me,PhNHgT Monoclinic 2.2400 1 0.6783 104'54' 10 Me,PrPhNHgI 0.7775 1 0-6711 96'34' 9 Me,EtPhNHgI 9 9 0.7391 1 0.6783 94" 9 9 11 MeEt,PhNHgJ 9 9 0.7319 1 0.6976 93'24' 9 ) 12 E t,PhNHg13 1.1250 1 1.3490 101 '2 13 Et,PrPhNHgI 1.1185 1 1.3440 100'57' * Phenyltriethylammonium iodide also forms a second type of compound with A description of this substance is included in the experimental 9 Y 2 1. TABLE 111. The Ph eny I b enz y lalk y lunanz on iu m G r ozi p of Crystallographic constants . v-N O . Substance. System. a b c . P. 14 Me,( CH,Ph)PWHgI Monoclinic 0.7386 1 0.5105 92"26' 16 MeEt(CH,Ph)PhNHgT 99 0.9878 1 0.5797 106' 16 Et,(CH,Ph)PhNHgI 77 1.0301 1 0.6354 108' 17 MePr(CH,Ph)PhNHgT 1.1060 1 0-7766 102'55' Y I308 BARKER AND PORTER THE EFFECT OF ASYMMETRY.the1 same1 forms but without b(010) and a(100). Since in the former compound thew two forms were but slightly developed, their absence in the latter has no particular signifioanm merely indioating that om compound tmds to preseint a rioher form-development than the other. The mincidenm of all the remaining farms and more especially tlhei occurrence in common od the form (ZOl) point to1 an idelntical space-lattice and prove the substancea to h isomorphous in so far as purely geometrical characters can do so. This conclusion is strengthened by the olbservation that a brokeln fragment of the diet~hyl oompolund when plaid in a saturated solution of the methylethyl derivative immedia;tely begins t o grow and eventually becomes a prfeot arystal.The wle remaining question relata to1 the speoial chemical nature of phenylbenzylme~thylelthylamolnium merouri-iodide whether the crystals a,re dextrol- and lzvo-enmtionmrphs or are rsmmio or pseudo-rammia. As no trace1 of optical inhomogeneity was ever observed in crystals selleated from various crops and a,s tlhe measure ments gavel no indioatiolns of tihe wide variations of angle charaoter-istia of pseudo-racemic crystlals it follows that the wystals axel eitlhelr truly raceania or on the otheir hand a conglomerate of the two erzantiomolrphs. I n ordelr to decide this queBtion thrw of the1 largest orystlals weighing approximately 2 1.5 and 1 gram respmtively were powdered and as rapidly as possible dissolved separakelly in about 20 C.C.of amtone and the1 solutions immdia,tely exmind in the polarimekr. I n no o m was an appreoiable rotation observed ; the crystals theref ore presumably repreenti a tlrrue rawmate. This conclusioln was suppolrtd by &ah-figures on the crysbal fa,oes for they were in accordanw with holohedral symmetry. The main result1 olf this investigation is to prove that racelmia cryst a,ls olf phelnylbelnzyhet hylethylammolnium merauri-iodide are isomorphous with the corresponding diethyl derivative although the raaemio crystals contain two kinds of asymmetrio rnoledes, whilst in the diethyl derivative all the moleaulee are newssarily idelntioally similar and symmetrioal.E x P E R I M E N TAL. Preparation of CompoyuncEs. The general method of preparing tqhe compounds was as follows. The proper mohxular proportions ojf the tertiary mine alkyl iodide and mercuric iodide1 were warmed tlogetsher with acetone until the whole was dissolved and the solution allowed to remain olvernight. Crystals were usually obtained the following day A STUDY IN CRYSTAL STRUCTURE. 1300 adthough two1 o r three rmrystallisations weire somethes nelcasary before really good crystals were formed. Some of the1 ccmpoands prepamred werel found to be unsuitable for orysta#llographia inve& gation ; t,he t,rimethyletjhyl and tri-metbylprolpyl compounds for example cryst,aJlise in needles. On the olther hand in some1 cases morel t h n one oompoand is foamed ; thus tetrad,hylamoniu.m io.dide unit,es with melrcurio iodide in the prolportions 1 1 and 2 3.Wit'h regard tlol the phenyldkyl group it wa,s observed thattj increla5sei of molelcular weight lowereid the crystxadlisability of the coimpoands ; somelt,imes five or six rmryst~allisations we98 nec,essa.ry bef orel suffioielntlly goold crystlals welre obtaineld. The phenyldimethylpropyl a.nd phelnyldimethyl-elt3hyl compounds have1 at stmng telnde!ncy tlol folrm needle's but after repateld remysta'llisatiolns t.hey finally yieilded some meiasurable crystlals. I n one a<nd the same so;lutJo8n phelnylt'riethyla~olnium ioldidtr folrrms with melrouria ioidide two1 CompoIunds which on analysis proved t o be1 the 2 1- and 1 I-compounds respeotively ; t'hese were1 separated by hand.I n tlhe phenylbenzylalkyl group, thel chemical cormbinastion olf t,hel va,rious components was relativelly slow; seve1ra.l afAempta t.o prepare1 phenylbenzylet.hylpropy1-ammo'nium me,rauri-ioldidel welre! madel but a pure product could no't he isolated. Mrthod of Analysis. The method employed for the quantitative estimation of the1 mercury was that dewribsd by Marsh and Lye (Analyst 1917, 42 84). The prolaem is a modificatioa of the method of estimating mercury by combustion with quicklime. Calcium olxalate is placed a t the close& elnd of the tube! and after this a few grams of dry caloium sulphate and quicklime; next comes about 1 gram of the substance grolund up with abolut the same weight of potassium cyanidel and a few grams of calcium salphatlet aad quicklimel.* After this 5 olr 6 grams of a mixture1 of oalcium sulphata and quiaklime are packed in and the remainder of the tube is filled with quicklime.The1 vapolriseld melrcury is collected in EL small flask of water. No calcium sulphatef was meld with the teltra-meithyl phenyl limethylpropyl and phenyldiethylpropyl com-pounds. It may be noted that more satisfactory results were obtained with a t u b longer than that remmmendeld by Marsh and Lye(; the length of the tube beifore drawing olutl should be about1 50 am. * In the case of the phenylbenzylalkylammonium group about a gram of black copper oxide was mixed with the substance and the potassium cyanide waa placed nearer the drawn-out end of the tube 1310 BARKER AND PORTER THE EFFECT OF ASYMMETRY.Method of CrystaUograpFyic Esanthaitimt. A Fedojrov tlwoLcirclel goiiiometer was exclusivelly employeld in the measurement of the crystals. Apart from its other advantages a two(-circle instrument> is especially useful for the measurement of laboratory products the crystals of which are frer quently od microscopic dimensions since it nelceesitates only one adjustment of the crystal. The raults were plotted on a Fedorov stereographic netl and the crystal systelm if not immediately olbvious was deduced from zonal angles graphically determined by tlhe help of the1 three-polint compass and stelreographic netl and latelr ooafirmed by an elxamination of the optioal propelrties. The crystlallographia indices were deftermined graphiodly in every case by the help 04 the1 gnomonic projeotion.I n order to1 avoid powible errors the axial ratios havs belen calculateld in two1 independent ways for evelry compound. First by the melthod in common use, depending on the1 sollutioln of spherical triangles and secondly by Goldschmidt’s melthod (Zeitsch. I f r y s t . Mirt. 1893 21 210) based on the gnomonic projection. The crystal drawings were made directly from the! gnomonic projection by the1 method delvised by Goldsohmidt (Zeitsch. Kryst. Min. 1891 19 352). Attention is especially called to1 this point because1 the method does not appear to have come1 into! gelneral use although elxperience proves it to bO superior to all the other melthods olf drawing crystals.In the descriptions of the crystals the convelntional rules have been adopted [in the molnoclinic system f o r instance\ the indices (010) have beeln uniformly assigned to1 the planel of symmetry]; but in addition the (( correct setting ” of the crystal according to Feidorolv’s melthobds and his (‘ complex-symbol,” have been woirked out in ewelry case and the “transformation elquations,” by which the1 indices corresponding with Fedorov’s theoretical ideas may be obtained from the conventional indices are also given. The dewriptions consequently contain everything necelssary for an absolute idelntification of any of the1 compounds on any future occasion by the melthod now genelrally known as ‘( crystallo-ohemicd analysis,” a descriptive1 outline of which has already been given elsewheas ( A m .Reports 1913 10 245; 1914 11 248; 1917 (14 227). An explanation of the1 meaning olf thel terms ( ( transfolrmatioa equations ” and ‘I complex-symbol1 ” may well1 be appended here as not having been previously given. The1 oonnexian between the indices representing any face of a crystal when refelrred to twol different sets of axes is most con-venienttly expressed by means of “ transformation equations,” by which one set of indices can be immetdiately delduced from th A STUDY IN CRYSTAL STRVCTURE. 1311 other. Thus ;In the1 case1 of the1 anolrthic melthyltlriethylammolnium mercuri-iodide (p. 1313) the new indices (pyr) of any face referred to the axes chosen by Fedorov on structural grounds can be obtained from its indices ( h k l ) when referreld to the conventional axes by the equations p = - l h + O k + 21 y = l h + Ok + 21, r=lh+22k+01.Thel numerioal colefficients of hkl in these equa-tiolns are 102 102 and 120 respectively and the1 equatiolns oan be abbrelviated to “ trans. T02/102/ 120 ”-a form which is adopted in this papes. The1 Fedorov “ complex-symbol ” is an expression which indicates simultaneously both the1 type of structlural arrangementl and the characteristic angles of the crystal (if necessary after a suitable homogeneous defolrmation or shear). The initial term of the symbol is the number 6 4 or 3 according as the crystal is helld to1 approximate most closely t o a hexagonal tetragolnal o r trigonal (rhombohedral) folrm respectively. When necemary this number is immeldiately follloweld by a letter h 01 or d respectively indicating in Feidolrov’s phraseology that the arrangelment is ( ( helxahedral ” (that is thatl of a simple space-lattice) ( I octa-hedral ” (that of a centred lattice) or “ dodecahedra1 ” (that of a facel-centred lattice).Thus 4h signified that the type of the struc-tural arrangement is that of a simple tetragonal spacerlattice!, whilstl 3d indicates the face-centred trigonal lattice as being the structural typei. All remaining terms of the complex-symbol are numerical const ants representing degree& of arc which serve to characterise each crystal species. As described below one of these numerical telrms expressing in genetral the vadue of the angle (after a shejar) beltween the correct basal plane and primary pyramid is especially important in Feldorov’s classification so by way of cant-rast he1 elncloses in brackets all other terms as are necessary to1 express the1 angular delviatiolns of the1 lattice from an ideal hexagonal tetragonal o r trigonal folrm.Thus in the symbol “ (6)37$(+3),” the1 first term means thatl the crystal approaches ideal heixagonal symmekry the selcond that the principal angle is 37i0 and the1 third thatl the prism angle has the value 6 O o + 3 O instead of the value 60° proper to1 an ideal hexagonal lattice. The abselnce of any furthes term indicates that the system is ortho-rhombic. On the1 other hand in the symbol1 ‘‘ ( 3 h ; + 2)58(0) ” we have a new kind of numerical term namely + 2 immeldiately following thel structural term 3h.This means that the1 angle between two1 of the1 structural planes is not 90° but 9O0+2O in other words thatq the1 crystal is monoclinic with a value P=92O. The last term (‘(O),” refers as beforei t o the1 prism angle and means that the deviation (from the ideal value olf 60°) is neare I312 BARKER AND PORTER THE EFFECT OF ASYMMETRY. Oo than +O. The1 anglea in the cornplelx-symbolls are olnly given to the nearest half degrele since this is the limit of accuraay of the graphioal methods employeld . The Fedorov cornplex-symbol derive6 its immense importance from two facts first unlike axial ratios i t is an unambiguous constant f o r each crystal-species and secondly such symbolls can be reladily dasifield in ordelreld form. I n his " Diotionary of the Crystal-Kingdom," the publiclation of which by the Petrograd Aaademy of Scielnce has been delayed by ciroumstanws beyond its control the late Profasor Fedorolv has classified all the1 existing data.All clrystals bellonging to the same1 type (say 4h or 3d and SQ on) are1 first broaght together and then arranged in olrder accolrding to1 tlhe value1 of the1 principal angle melntioned abmel. Any well-delvelopd crystalline1 substance which has once beein melasureld and placeid in the1 dictionary in the place relquird by itis complejx-symbol can be identified on any future olcmsioln for it is only neicessary to1 measure the1 crystal to1 be identifield deduce itk; complex-symbol from the form-development, and refer to the dictionary for a statement olf the ohemical composition.A naly tical and Crystal I ograp hic De'tails . Folllowing is ay detailed summary of the! reaults sb chemioal analysis and Crystallographic measurement of the various substances prepared. Although measured angles only are1 reproduced in this paper (the angles which served as a basis folr calculation being markeld with an asterisk) i t may be1 rnentioneld thah the1 correot-neas of the various indices was checked by the logarithmic cojm-putation of the angular values demanded by the! law of simples, rational indices and thatl these computed angles were in evesy case1 satisfactorily do= to1 the1 meamred angles. The1 omission of these computed angles results in a grelatl saving of space and does nok seem to1 us to1 involve1 tlhel loss of anything essential t o the future usefulness of the crystallographic descriptions.Tetramethy2ammonium Mercziriiodide MqNHgI,.-M. p. above 200° (Found Hg=30.43. Calc. Hg= 30.53 pelr cent.). Ortho-rhombic a;:h:c=0*5777:1:0*5199. Fosrms b{010} al{lOO), m{110} m{120} e{001} e{101} ~ { l l l } C(121). Two distinct habits were observeld on crystals from acetonel. The more usual habit is sholwn in Fig. 1. The seciond habit is bipyramidal and tabular pasallell to h(010). Following are the1 mean angular values olbtained from five crystals : b(OIO',. a{1OO). m{11O). n{12O}. eilO1). p{lll). t(121). Azimuth (+) ...... 0" 0' 90' 4' "59'59' 40'50' 89'53' 59'59' 40"54' Polar distance (p) 89'59' 89'59' 90" 0' 90" 2' "41'59' 46" 3' 53"57 A STUDY IN CRYSTAL STRUCTURE.1313 Clela;vages a { loo} fair; c{OOl) imprfeati Optic axid plane, a{ 100) ; acute bisectrix pelrpeindicrulax t'ol (001) ; wide axial angle; biredringenml strolng ; dispersion p>w. Trans. lOO/OOl/OlO. Complex-symbol (4d)69( + 3). Met hybtket hylamrnonium Mercuri-iodide MeEt3NHgI,.-M. p . 104O (Found Hg = 28.67. C,H,,NI,HgI requires Hg = 28.73 per cent.). Anolrtlhic ai:b :e=1*1202:1:0-5578; c~=102~55/ ,8= 93O56/ ~ = 1 0 8 ~ 2 5 / . Forms b{010} a{100} m{110} ,{liO>, k(iZo} 1{2i0) g { o i i } t { o i l ) r{ioi}. FIG. 1. FIG. 2. The' commo8n habit is FIG. 3. Tetramethylammonium Meth,yltriethylammonium Tetraethylammonium rnercuri-iodide. mercuri-iodide. mercuri -iodide. slender prismatic as shown in Fig. 2. angular values obtained from nine1 crystals : b(010j.a{1001. millo). n{iio). k{lZO). Azimuth (q) ......... 0" 0' *70" 5' *32"18' 130'40' 154'17' Polar distance ( p ) ... 90" 0' 90" 0' 90' 0' 90" 0' 90" 0' Following are the mean z(2io). q{ol I). t{oii]. r{iolj. Azimuth ( q ) ......... 104" 5' *4"29 *190 168"32' 3 28 23041' 1'43' Polar distance ( p ) ... 90" 0' *41"21 Clea#vagea m(110) and n(liO} good. Trans. 102/102/120. Complex-symbol (4d; *21)62(0 ; 0 1 ) . Tetra e t h yla;mnz o n izi nc M ercuri-iodide E t,NHg I,. -M . p . 1 1 Oo (Found Hg= 27.95. Calc;. Hg=28*13 per cent.). Monoclinic, a:b:a=1*4826:1:0.8192; P=107O55/. Porms. al{lOO} m{110}, c(OOl} T { 901 o{T11}. The common habit is stout' prismatic as shocwn in Fig. 3. Follolwing ase the mean angular values obtained from five crystals: a(100).m(1lOt. C ~ O O ~ ] . r(701). 0{111). Azimuth ( q ) . . . . . . . . . 90" 0' *35"20' 89"46' 269"58' *342"34' Polar distance ( p ) ... 90" 0' 90" 0' 17"54' 39'56' *40"39' Optics All the prism faces give1 oblique extinction. 1314 BARKER AND PORTER THE EFFECT OF ASYMMETRY. Cleavages a { 100 1 pelrfect,; c { 001 } imperfectl. Opt'io axial plane b(010). An optic axis emerges nearly pelrpendicular to c(OO1). Trans. O l l / O l i /101. Complex-symbol (4d; - 144)55( - 64). Tetraethylammornim Memiiri-iodide 2Et4NI,3HgI,.-M. p. 1 5 4 O (Found Hg=31.94. Calc. Hg=31*98 per cent.). Tetra-gcmal c:a=0.8186:1. Forms n{100} m{110} e{101} d{20l}, ~ { l l l } ~ ( 2 2 1 ) . The common habit of the crystlals is shown in Fig. 4. Following are1 the mean angular value8 obtained from four cryst,a,ls : FIG.4. FIG. 5. FIG. 6. Tetraethylammonium mercuri-iodide. Triethylpropylammonium mercuri-iodide. I I 1 I I ml rn I I I I I Methyltriprop yl-. ammonzum mcrcurm-iodide. a{1001. mfllO}. e j l O l i . d{201}. p(ll1). sI22l). Azimuth (q) ............ 0' 0' 45" 0' 0' 3' 0" 3' 45" 3' 45" 2' Polar distance ( p ) ...... 90" 0' 90" 8' 39'13' *58'35' 49' 9' 66'35' Cleia,vagel a{ loo} goo,d. Donble redraction very strong ; posit ive . Com plex-sym bol (4 h) 4 9 O 9 I . Triethyl-a-propylmmonium Mercwi-iodide Etq3PraNHg13.-M. p. 85O (Found Hg= 27.33. C,H,,NI,HgI requires Hg = 27.58 per oent.). Monoclinic a b c = 1.1350 1 0.7359 /3=97O11'. Forms n'{100} m{110} c{OOl} e{101} r{iOl} ~ { l l l } .Two habite were) observeld one ot which is shown in Fig. 5. The second habit sholws the pyramid p{111) and n { l O O } is much narrower. Following are the metan angular valueis obtained from six crystals : a{100}. m(110). c@01]. e(1011. T { i O i ) . ~ ( 1 1 1 ) . Azimuth ($) ... ..... ,. .. 90" 0' *41"36' 89'58' 89'59' 270" 4' 46"39' Polar distance ( p ) ...... 90" 0' 90" 0' 7' 5' *37'51' 27'58' *46"59 A STUDY IN CRYSTAIJ STRIJCTURE 1315 Cleavage n ~ { 11O} perfect. Optic axial planel b(010). An optio axis is visible! through a{100} on the! extreme edge of the field. Trans. ~lO/TTO/OO2. Complelx-symbol (3h ; + 2)58(0). Me t h y 1 t ri-a-p-oljyl LC nz m o n i 1 ( m Me r c 11 1.i- iodide Me P r a,N H g I .-&I. p. 1 2 3 O (Found Hg = 26.55. Cl,,H,,NI,Hg12 requirw Hg = 27.06 per cent.).Monoclinic a b c = 1.0749 1 0.6542 ; P= 93'22'. Forms nz{llO} p{Oll} r{TOl} p{111} o{T11}. Two1 disttbnct habits were olbserveld one of which is shown by Fig. 6. The second habit is stout prismatic with large pyramidal faoes. Following are1 the) mean angular values obtained from five crystals : r n { l l O j . q(o11). r(iO1;. p{Ili). o { i i i j . Azimuth (q) ......... *42"59' 4'59' 269'53' *45"37' 319'50' Polar distance ( p ) ... 90" 1' 33'24' 28'56' *43" 5' 40'26' Cleavages q { 01 1 } fair ; 712. { 1 l o } imperfect. Optic axial plane, b(010) and an optio axis is visiblel tlhrough a(100) on the1 ledge of the1 field. Trans. TlO/T~O/OO2. Complex-symbod (40; + 3$)50( - 2). FIG. 7. FIG. 8. Ethyltriprop yEamrnoi&m rnercuri -iodide.n FIG. 9. I I m m . I I ,", Tetraprop y~ammoniurn Phenyltrimethyl -mercuri-iodide. arnmonwm mercuri-iodide. Ethyltri-a-popylammonium rVercuri-iodide EtPrn3NHg13.-M. p. 135O (Found Hg=26.43. C,,H~NI,Hgf requires Hg= 26.56 per cent..). Ortborhombio a b c = 0.6890 1 0.5106. Forms b { 0 1 0 } m{110} p(O11). The common habit' is sholwn in Fig. 7. A second habit was observed much shortemd along the vertical axis. Following are the mean angular values obtained from six orystads : bt010). rnfl10). q{Ol I}. Azimuth (q) ......... 0" 0' *55'26' 0" 0' Polar distance ( p ) ... 89"58' 90" 0' *27" 3 1316 BARKER AND PORTER THE EFFECT OF ASYMMETRY. Cleta,vage,s g { 01 I } perfect ; c { 001 } imperfect. Optic axial Trans.100/011 /OO% planel a(100) and tbel c-axis is the negative acute bisectrix. Complex-symbol (6)37+( + 3). T e trara-popylanzmo niu m M erc wi-iodide Pra,NHgI,.-M. p. 178O (Found Hg = 25-75. C,,H,,NI,HgI requires Hg= 26.07 per cent,.). P = 113'16'. Forms b{010} a{100} m{110} n{120} c{OOl} r{2Ol}, ~ { l l l } . Folllowing are the1 mean angular vaJues obtained from five crystals : Molnoclinic, The habit is prismatic as shown in Fig. 8. a b c = 1.4965 1 0-7328; b{010}. a(100',. m(110). 74120). c(OO1). Azimuth ( q ) ......... 0" 0' 90" 0' *36' 2' 20' 1' 89"58' Polar distance ( p ) ... 90" 0' 90" 2' 90' 2' 90" 0' *23"16' rpo1;. p{l11). Polar distance (p) ... 32"19' *50'26' Azimuth (+) ......... 270" 0' 52'45' Clelavages m { 110 1 and r{ 201 f good.OptJa axial plane, b(010). An optic a,xis emerges nearly peIrpendicular to ~(301) and the1 acute! negative bisecbrix nearly ooincyidefi with the c-axis. Dispe,rsion moderatel p>v. Trans. O T l / O l l l ~ O ~ . Ph emy l t rim e t h yla,mnz mizc nz Complelx-symbol (3d; - 14)50( + 18). Mercur i-iodid e P hM%NHgI .-M. p. 135O' (Found Hg=27.80. C,H,,NI,Hg12 requires Hg= 27.89 per cent .). Monoolinia al b c = 1.2400 1 0.6783 ; P = 104O'54'. Folrms a{100} m{110} 721{210} q{Oll} e{101}, r{FOl} ~ { l l l } ~ ( I l l } . The habit is prismatic as shown in Fig. 9. Following asel thel mean angular values as obtained from five crystals : a(100;. m(110). 42101. q(0llj. eflOl}. Azimuth ( q ) ......... 90" 0' "39'51' 59" 6' 21'28' 90' 0' Polar distance (p) ...90" 1' 90" 0' 90" 0' 36" G' *39'46' T ( ~ o I } . p f i i i ) . o(Ti1). Azimuth ($) ......... 269'59' 50"54' 336" 4' Polar distance ( p ) ... 55" 7' *47' 2' 36'34' Clelavagei a{ loo} good. Optic axial plane b(010). Through Tram. llO/Tl0/002. Complex-symbol (401; + 15)48&( - 5). P h en. y 1 dim e t h y t e t h y la mm omium M e r c u ?% - iodide P h Me E tN Hg I,. -M. p. 95O (Folund Hg =27-21. C,,H,GNI,Hg12 requires Hg= 27-36 per cent.). Monoclinio a( b c = 0.7391 1 :0'6783 ; P = 94O6'. The common habit is that of unmeasura(b1e radiating needles. A few measurable1 crystals were obtained of the type shown in Fig. 10. a(100) an optic axis is visible on thel edge of the fiedd. A STUDY 13' CRYSTAL STRUCTURE. 1317 Forms m{110} q{Oll} e { l O l } r(TOl} ~ ( 0 0 1 ) .Following are the1 mean angular values obtained from seven crystals (no1 trust-wolrthy results welrel obtainable from thel face1 c which was always curved) : m(110). q ( 0 l l J . e(101;. r { i o i ) . Azimuth ( q ) ......... *53'36' *6' 2' 89'59' 270' 0' Polar distance ( p ) ... 90" 1' *34'18' 44'43' 40'22' Cleavage1 c { 001 } perfect). Optic axial planel b(010). An The1 optic axis is visible1 through c{OOl} on the1 edge od the field. dispelrsion of t3hel opticl axes is strong. Trans. lOl/TOT/OlO. Complefx-symbol (46; 4)53( - 24). P~en~yldimethyl-a-yurolr?/lumm~~~~~na Merczwi-iodide, -PhM%PraNHgI,. -M. p. 880 (Found Hg = 26.54. C11H,8NI,IEgI requires Hg = 26-84 per cent.). Molnoclinic a b c = 0.7775 1 0.6711 ; P= 96O34'.Forms m{110) q{O11} e{101} y(TOl}. Thei common FIG. 10. . FIG. 11. FIG. 12. Phenyldimethylethyl- Phenyldimethylpropyl- Phe?aylTethyldiethy!-anmwnzum mercwz- ammonium mercuri - arnmonwm mercum-iodide. iodide. iodide. form is t h a t of radiating neadlee. A feiw measurablel crystals welrei obtaineld of the habit shown in Fig. 11 with p r i m faces much curved. Follotwing are the mean angular values obtained from setvein Crryshls : m(110). q{Oll). e.1101). T p o i ) . Azimuth ( q ) ......... "53'19' "9'44' 89'52' 269"57' Polar distance (p) ... 90' 0' "34'14' 44"44' 36'58' Cle,a,vage c { 001 } perfect. Optic axial plane perpendicular t o The acute1 negative bisectrix is nearly perpendicular to Dispersion strong p>v. b(010). c { 001 }. -Trans. 101/lOT/OlO.Complex-symbol (4d; 64)52&( - 4). Ph.enyZmetTLy2diethyk~mnaoiii~m Mercwi-iodide PhMeEt2NHgI,. -M. p. 9 6 O (Found Hg- 26.63. Cl~H18NI,HgI~ requires Hg 1315 BARKER AND PORTER THE EFFECT O P ASYMMETRY. 26.84 per cent?.). Monoclinio a b c = 0.7319 1 0.6976 ; P =a 93O24'. Forms b{010} m{110) r2.{120} c{OOl} p{O11) a(101)-r(101). The common habit is shown by Fig. 12. Following are' the mean angular values obtained from five crystals: Azimuth (q) ......... 0" 0' *53"51' 34'18' 89'54' *4"52' bfOlOl. m{llO). n1120). cj001;. q{Oll]. Polar distance ( p ) ... 90" 0' 90" 0' 90" 0' 3'25' "34'57' eC1OI). r(ioi;. Azimuth ($) ...... 90" 2' 269' 57' Polar distance ( p ) 45"19 41O42' Cleavages c { 001 } perfect; m { 110 f impelrfect. plane b(O10). The double retfraction is negakive with sbrong dispelrsioln p<v.Optic axia' 1 An optio axis is inclined at abolut 20" to c{OOlj ' -_ Trans. l O l / l O l / O l O . Complex-symbol (4d; 3)55( + 2 ) . Ph erhy I t rie t h y lam m om ium M e 4-c u ?.i-iodidle Ph E hN Hg I,. -&I. p , C,2H,,NI,Hg12 requires Hg = 26-35 per 9 8 O (Folund Hg = 25-94. FIG. 13. Phenyl triethyl-ammonzum mercuri-iodide (1 1). Fm. 14. Fra. 15. Phenyltriethyl- Phen yld iethylpropyl-ammonzum mercuri- ammonium mercurz-iodide (2 1). iodide. a Ir c = 1.1250 1 1.3490; /3 = 101O20'. Forms a{100} m{110) r(T02} y(O11} p{lll}. The common habit is shown by Fig. 13. Following are the mean angular values obtained from five crystals : a{100;. m{110). rf102). q{OlI). p(ll1;.Azimuth (+) ......... 90" 0' *42'12' 269'58' 8" 5' *46"33' Polar distance ( p ) ... 90" 0' 90" 1' 22'48' 53"39' *62"59' Clea,vagei a{ 1001 perfect. Optic axial plane is b(010). Inclineid dispersioln strong. Trans. OOl/~OO/OlO. Complex-symbol ( 4 h ; 9&)46( - 5+). Plt e n yl t r ie t by la mm omium ill e ~ C Z L ri-iodide 2 Ph E t ,NI Hg I .-&I. p. 144O (Found Hg = 19.21. (CI2H,,NI),HgI2 require A STUDY IN CRYSTAL STRUCTURE. 1311) Hg=18.80 per miit.). Orthmhmbic a b c=0*8G42 1 1.1605. Forms at{lOO} m{llO) c{OOl) s{104) ~(111). The habit is shown by Fig. 14. Following are the1 mean angular value? obtaineld from five crystals : Azimuth (+) ......... 90' 0' *49"10' - 89'58' 49"IO' a{100}. nt(1lOf. ~(0011. ~ ( 1 0 4 ) . p:lllt. Polar distance ( p ) ...90" 0' 90" 0' 0" 0' 18'38' *60"36' Cleavage c { 001 } imperfect. Optic axial plane! b (010) ; the The optic axial angle is acute biselctrix is pespendicular to c{OOl). wide. Trans. OlO/lOO/OOl. Complex-symbol (4d)60&( + 4). Ph en y ldie t h yl- a- proipy lam mom'um Merczcri-iodide, PhEtgPraNHgI,. -M. p. 93O (Found Hg == 26.33. C,,H,NI,BgI requires Hg = 25.87 per cent.). Monoclinic n h c = 1.1185:1:1*3440; /3= ~ { l l l ) . Another habit was observeld t'abular to! a{ 100). Following arel the melan angular values obtained from five crystals: Azimuth (+) ...... 90" 0' *42'19' 90" 4' 8'10' 270'16' "46'31' Polar distance ( p ) 90' 1' 90" 1' 1l0 0' 53'43' 22'45' *62"53' 100057'. F O ~ S ~{Ioo) ?n{iio) c{ooi} q { o i i ) T { i o q , The1 common habit is shown by Fig.15. a{100]. mfiiof. ciooi;. 9:oii;. ~p02:. p;iii;. Clelavagee a{ loo} perfect ; m { 11O} imperfect. Optio axial plane perpendicular to b(010). The1 po'sitive acute bisedris is visible through a{ loo} on the edge of the fielld. Dispersion strong, P C V . Trans. OOl/lOO/OlO. Complex-symbol (4k; 11)50( + 6). Z'h eny llb enzy Zdim e t Ii y lam moniu m iMercuriiodide, Ph( CH,Ph) MekNHg I,. -M. p. 1 4 3 O (Found Hg = 24.74. C,,H,,NI,Hg12 requires Hg = 25-22 per cent).). Monoclinic a b c = 0.7386 1 0.5105, j3=92O26/. Forms b { 0 1 0 } a{lOO} ?n{110} p{O11) r{lOlt, s(121} u{T4l} t ( 3 3 1 ) . The commoii habit4 is shown in Fig. 16. Following are the mean angular values obtained from five orystals : b(O10;. a,'100). m(110;. q(0ll;.T l i o i ) . Azimuth (q) ......... 0' 0' 89'59' "53'34' 4'44' 270" 1' 4121]. ~ ( i 4 i ) . t1321). Polar distance ( p ) ... 90' 0' 90" 0' 90" 0' 27" 7' 32'57' Azimuth (+) ......... *35"43' 342'24' 296"41' Polar distance ( p ) .. 32"31' 65" 1' 66"15' Cleavage uI{ l O O } fair. Optic axial plaue b(010). Trans. oT'o/ioi/ios. CompIels-symbol ( 4 d ; - 7+)69( I 4 1320 BARKER AND PORTER THE EFFECT OB' ASYMMETRY. Phee?tylbenz?/lmeth!/lethylan,Ln2onizcita Merciie?*i-iodide, Ph( CH,Ph) MelEt NHg I,. -M. p. 127' (Found M g - 24.68. Clfj~LoNI,Hg12 reqiiires Hg = 24.78 per cent .). Monoclinic a b c = 0.9878 1 0.3'797, P=106O9/. Forms h ( O l O ) a{100} m{llO] c{O01) y(O11], r{901). Following are the mean angular values obtaineld from seven crystals : b{010;.a;100!. r r ~ ; 1 1 0 f . c{OOl;. qi0lli. ri201;. Azimuth ($) ............ 0" 0' 90" 1' *46"30' 90" 8' 46'37' 269"58' Polar distance (p) ...... 90" 0' 90" 0' 90" 0' 16" 9' 32'57' 42"51' A n optic The! habit is shown in Fig. 17. Cleavage m{ 110} good. Trans. O l O / l O O / O O l . Optdc axial plane1 is b(010). Complex-symbol (4h ; - 16)40(1&). axis is visible through r { 201 } . The dispersion is strong. FIG. 16. FIG. 1 7 Phenytbenzyldimethylamr~,~iu?n PiLenyllberLzylnaethylethyE-mercuri -iodide. ammonium mercuri-iodide. Phenyl b enzyl~ieth~lnnanaoniit tit Merczcri-iodide, Ph(CH,Ph)EhNHgI,. -M. p. 138.5' (Found Hg= 23'71. CI7H2,NI,HgI requires Hg = 24.36 per cwnt .). Monoclinic a h c = 1.0301 1 0.6354, @=108O7/. Forms n t { l l O ) c{001} q{O11} r(ZO1).The crystals are curved and distorted. The com.momn habit is shown in Fig. 18. Following are the mean angular values obtained from seven cryst a'ls : m.(110:. c{O01). q(011). r(z01;. Azimuth (+) ......... *45"36' 90" 0' *27"14' 270" 0' Polar distance ( p ) ... 90" 0" 18"25' 35'33' 43'49' Cleavage6 c{001} imperfect; r { 201 1 perfectl. Optic axial r(2011 plane, h(010) and thelre is an optic axis visible1 through on the edge of t\he field. Trans. O l O / l O O / O O l . Complex-symbol (4h ; - 18)42(&). There is strong dispersion ri STUDY TN CRYSTAL STRUTCTIJRE. 1321 l'h ethyl b enz ylm e t I~yl-a-pro yylam~noiLium Mer curi-iodide, Ph(CH,Ph)E t,NHgI,. -M. p. 134O (Found Hg = 24.34. C,,H,,NI,HgI requires EIg = 24.36 per cent.). Monoclinic a 0 c= 1.1060 1 0.7766, p- 102O5V. Forins u { loo} m{110} c{OOl} r{lOl} s{221}, ~ ( 2 2 1 ) . Following are the mean angular values obtlaineld from seven crystals : The common habit is sholwn by Fig. 19. a{100]. m(110]. Azimuth (9) . . . . . . 90" 0' Polar distance ( p ) 90" 0' *42O5 1' 90" 0' FIG. 18. . - - - - & - - - . - - I - - -I Pheizylbeiazyldiet~yla7nmoniu?n mercuri-iodide. ~ ( o o i f . qioi;. ~{221',. 4221) 89'52' 270" 0' *47" 4' 321'45' 12'36' 26'45' 66'19' 63' 1' FIa. 19. Phenylbsnzy lmetlzylpropyl-ammonium mercuri-iodidc . Cleavage, a { l O O } . The optio axial plane is perpendicular to the plane of symmetry and an optic axis is visible1 t'hrough m{ l l O } . Tra,ns. lOO/Ol0/002. Complelx-symbol (4d; + 13)64%( + 2). Our thanks are due to! the Research Fund Committee of the Chemical Society and to the Scielntific and Industrial Research Department for grants in aid of this work and also to Professor N. L. Bolwman Mr. J. E. Marsh and Professor W. H. Perkin for much help and advice. MINERALOGICAL DEPARTMENT, UNIVERSITY &$USEUM OSI'ORD. [Receiced September 14th 1920.] VOL. CXVII. 3

ISSN:0368-1645    

DOI:10.1039/CT9201701303

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

1322 MITCHELL STUDIES ON CXLII.-&udies o n Hypophosphorous Acid. Part 11. Its Reaction with Iodine. By ALE'C DUNCAN MITCHELL. IN eat.imating hypolphoaphoiroas acid by mea'ns of merouric chloride aomrding to then met'hod given by Treadwdl (" Qua,nt,it,ative Ana(lysis," p. 2S9) i t was found tha.t the1 oxida.tion procmedeld rela.dily to pholsphorous acid but rellaLivdy slo,wly t o phosphomric acid. It was tjhelrefo,re de.cide,d t,ol investigate the1 progress of the i-elact'ion and c.ert.ain f a.c8ts werei netted in t,ha firstl s8tla.ge-the oLxidatbon t'ol phosphoro'us acid-which arel b'rielfly : (1) The coiioetnt'r adiojn o.f mercuric c,hlo,ride a,ppeiarecl trot ha,vel no inflimnoel 0111 t'he reectdoln vellocity eixcept whe'n velry dilutei. (2) The reactiotn was a,cceleratsd b.y the1 addition of hydrolchlosic acid.(3) It was the'retforei autowat,alyt\io owing t,o tlhel hydrochloric acid proiducetd. (4) The initia(1 vellolcity wa,s approxima,teily pro~portional t,oi the pro'ducti olf t$e concentra,tliom oC the1 hydrogeln ions and the1 hypo-phosphoroas a'cid. From them fact,s it wa,s conoluded t,hat the oixidat'ioii t.0 phosphorolus aaid involved tlwol suceeIssive reia,ctions the! first, of melasura8blel vellocity in which t,hhe> mercuric chloride1 t-oak no1 patr.t, a,nd t'hel secolnd o,f relat'ively p a t ,ve,loclit,y in which the1 melrcuric cihloiridei f unct'io'ned . No coinventiona,l hypot.helsis appeared adequa.telly t'o explain them facts. I n o'rder ta investiga,te certain points inolre fully an ana.logous reaction was soughtl in which the analytica,l rneltho'd used would be of grelat'es a,pplicab,i!ity.The. relactio'n with iodine was found to be acc,ura,tely colrnpa,rable and is here delscrihd. That wit$ rnelrouric chlojridel will be communicateld la.ter but itl may bet melntdoneld that compara8tivs e,:iperimelnts with iofdinel and meircuric chloride!, respeot.ively showeld that the melasurable8 velocity was identical in the two ca.ses t,hus lending a.dditiona1 support tot the! vielw that, only hypolphosphorous acid functions in the slolwer raction. Stredel (T. 1907 9 1 1641) ha8d already invc8stigateid the reaction svit,h iodinel and o'btaineld the1 same1 gelneral res,ult.s a.s alsoive. For the1 relactio8n H,PO + I + II,Q = H,PQ + 2131 he 0Eere.d t,hel follo3w-ing ex-planabion the slo'w stage is represented by which procselds libelrating free1 ionia chargee if thejrel is also preselntl BYPOPHOSPHOROUS ACID.PART II. 1323 substance capable of utilising them as rapidly as t,hey are formed: (2) 1,+2(')=21'. He poinb out that several hypoithetical sche~~es may be substitutd for (1) in orde'r to1 a.ccount for tha product,iojn 0.f free electrons but that int8elrmediate compounds cont'aining iodine cannot be formed in t'his st,age. Any equilibrium between hypophosphorous acid a,nd a,n " active" form would noh agree with t'iie fa& if it be assumed t'hat equilibrium is in&antaneo,usly reatmed; but i t is now shown t'hah if equilibrium is reststred ah ;I finite ra,te the existence of an inklrmediate " ac,tive" form adequatedy agrees with the facts and renders unnecessary the a.bolve unoonveatioaal hypolthwis.The relaction has now been studield under more diverse1 conclitiioins, and Gelriain nelw aspecix have been investigated. Stelele ignoreld two factors which are here shown to have an important bearing on the problem: (1) The deprelssioln by minerd acids of the1 iolnisation of hypo-phosphorous a>aid which he regarded as '' prolbably slight." Taking this into account by utilising data obtaine8d in the anihor's paper on tlhe subjeot (this vol. p. 957) it is shown clelarly t'hat t,he effect is considerable and that hypophospholroas a,cid f unct,ions as undis-solcia,ted molleaulea. Steelle obtained higher c1onstant.s in stroager acid solutions than in weaker but insbead of a,thribut,ing this to the inoreased propolrtion of mojleculea he ascribed it to the fact that he was using rno,re dilute hypophosphorous acid solutions the beha,viour of which he thought ammalous and suggested hhe idela thak its ions welre the aotive partl od the acid.(2) The past playsd by the ioldine which is appamntly negligible o'velr small ranges a t modera,t,e co~ncentration b,ut becornea. relat6vely grea't 8,s the conc,entration decreases. Stelele suggested tha,t it played no past in t,he reection untJl a.bout ninei-tenths of it had bees used up but tha,t it' theln tolok part in a.n appamntly bimole-ouhr reachion. Also he was led t40 a,scribe cert'ain cliscre1pa.nciea to1 the abotvementioned anolmaloas behaviour of hypophosphorous acid in dilut,e solution, but thew are now shown to be reg-ulasiseid when the function of t,lm iodine is colnsideired.From the datla obt'ained from abboat thirty expetriments nolw deacribeld actaal rates of de'cretase (dsldt) of hypopholsphorous a,oid were calcula4teld a,t the beginning middle asd end of e,ach elxpelri-m a t 4 and when these were divided by the concentrations at time t of hypo~pho~spho8rolus acid I?, and hydroge'n ioas ht and by the propoation of undissocia.te,d hypophosphorous acid mollec.ules 1 - at, ninety va\luea were obtaineld for the expressioln (ds / d t ) / htZt( 1 - at> which we,rel a.lm& const'ant wheln the corresponding concentratioas This is nojw sholwn tot be elrroneous. 3 c 1324 MITCHELL STUDIES ON of iodine eKceeded N / 5 0 but which decreased more and more rapidly with decreasing concentrations of iodine.This behaviour was ultimately found to be repreaented by the formula [1 + r ~ t / a t ] ( ~ / d t ) = k U t ( 1 - at), where at repreisents the concentration of the iofdine molecules and r and k are constants. It will be noltieed that this equation takes the form & / d t =kZ,(l -at)htat/(at+rht) which the reaction would give if i t werel simply bimolecul~r between hypophosphorous acid molecules and iodine being accelerated by hydrogen ions and retarded by a function at+rht of the iodine. Meymhoffer (Zeitsch. physikal. Chem. 1888 2 585) found that iodine had a retarding effect proportional to1 its concentration plus a constant on tIhe reaction HBr03+ 6 H I = HBr + 3H,O + 31 ; but the slightly modifield form melntioned above has not been regarded as a valid explanation oif the prelsent reaction since it is difficult t o understand why iodine should elxert a reltarding effect when its coacentxation is zero and its acceptance would imply that the hydrogen ioas had simultlaneously both awderating and inhibiting etff acts.The following hypothe& is found to require the same mathe-matical expression and to fulfil all the other requiremelnts previously postulated. Hypophosphorous acid molecules are originally in equilibrium with a very small quantity y of an " active" foirm, say H,PO in which the action of the hydrogen ions is to amelelrate reestablishment of equilibrium : . . . . . . H,PO,+H',O f H,PO (3) H,P03+I,' -+ H,PO,+BH'+31 (4) ds/dt = k,y,a .. . . . . . ( 5 ) kZ,(l -a,)h,=kly,h (6) and the iodine relacting its shown later as the I,' ion takea part : . . . . . The rate of formation of phosphorous acid according to (4) will be : 12 being a very large reaction velocity-constant . in (3) is k and k being the reaction velocity-constants in the1 two directions, k being large but not infinite and the) amount yt being so small as noit appreciably to affect the amount of hypophosphorous acid. Then the rate of inerelase in y owing to the tendency to restore equilibrium is k,?,(l- at)ht - klytht from ( 6 ) and its rate of decrease is d s l d t ; hence The equilibrium . . . . . . dyldt = klt(l - ut)hc - kly,h - ds/dt . . . (7 HYPOPHOSPROROUS ACID. PART 11. 1326 Eliminating yt from (5) and (7) we have (d”/dP)/k + (ds/dt)2/k2c + [a + k,h+/k,]ds/dt = ka,Z,(I - a,)h (8) This elxpression can bei simplified for most’ relactions as follows.Since k2 is very largel and kl moderateily large compared with k, and d%/dt2 and- ( c l s / d t ) ~ arel of a lower ordelr of magnitude than the othelr terms and moreover are of opposite1 sign (except in certlain cases) the f i r s t two terms may be mglected as a first approixiniation and one1 has or [l +k,h,/k,a,]ds]dt=kl,~l -a,)h . . . (9) which is identical with the formula obtained experimentally when the constantl k,/k2 is replaced by the1 constantl T . As the best valuel of r is found to1 bet 0*012 this explains why the iodine appears not to function until it becomes dilute when at is small.Now It=Z-s at=a-s and ht=h+ms since1 ht is foand to be a linear funotion of s. If therefolrre a is a simple function of s, thel expression can be integrate’d. I n some1 cases it is a linear function co that’ a t = a -ns. Letters without suffixes denotg initJal valnes and m and n are constants f o r any particular expelriment. The1 expression simplifies to k . dt = ds[ I/( 1 - s)(h + ms)( 1 - a + ns) + r / ( I - s)(a - s)( 1 - a t ns)] (9a) and one obtains o a integration, [a + k,h,/k,]ds/dt = ka,7,( 1 - a,)h, + m( 1 - a + 1 7 2 ) log ___ h 1 -++Is 1 - a n( h + mZ) log . 0.01 2 a -_-( l - ~ ) ( l -a+In>(l a - s I 1 - (1 -a+na) log - +n(Z-a) log I - s I n cases whetre at is not sufficiently nelarly a linear function of s i t is be81,telr t’o put n=O regarding a as constant, and subselquently to emploiy the average value1 of (1 - a) for the1 period concerned in obtaining the value of the constant.Thus one has (1 -n)k~-[logz-z-s+log - h+ms]/(h+?nl)+ h The elxaeptiolnal caees mentioneid when simplifying (8) to (9) are those in whioh the initial hydrogen-ion concentration is relativel 1326 MITCHELL STUDIES ON small and the rea,ction veiloIc&y increla.ses a t first? tot a maximum so tha.t @s/dtz is not nelgativel until t8hatl ma,ximum is passed. These cases give! results in fair agreejmeat8 with the1 ot8helrs when formula , (11) is usetd so that elvein whejn both the1 ne,gleiot<eid twms in (8) are poaitivet thelir combined effectl is very slight!. Itl is int)eirezsting to note that if hydrogen ions a.ctually tlook part in t8hel react,io*n (3) in olnet direlctioa only and were not metrely oa;tlalytsic h wojuld disappear from the secolnd telrm on t,he left oif qua,tion (9) and the1 thelory wo8uld require resnlta not consisteint with pra.ctqicel.I n the calculations itl is assumed that a fo,r the hypolphmpholrous a.cid delpelnds oinly on the1 initial amount present1 and on tlhe con-centratJon of the hydrogen iolng; and is nolt a'ffecteld by the replace-melnt of hypophoaphorous acid by phosphorous a.cid. This assumption is justified because the ionisine; powers of the two aclids a,ra ve'ry similar a.nd the1 total of the t l w s acids remains uncha.ngeld so th& acc.ordinq t'o the1 (' total ion " hpot.heeis (Arrhelnius Zeitsch,. plhysilcal. Chem,.1888 2 285 ; 1899 31 218 ; Bray and WLmtl. J . Rm'er. Ghe!m3. S'olc. 1911 33 781; and Mitchelll, this vol. p'. 957) for any definite hydrogein-ioln concent,ratioa tlhe,re is a definite valuel ocf a for each initdal co'ncelnt.ra;t.ioa od hypo-phospho'rous acid. Also it' does not appe8a4r t4hat the1 undistsolciateld mo81ec,uleB oQ the mineral aaids have1 any appreciable1 catt,a81ytic influe8nce in the concmt.ra,tio,ns used, I n several eixperimeliits (Nos. I 11 and V) po,saible oxida.tlon to phosphoric acid was checked alkalimetrically (see p. 1332) and found t.01 be1 negligible.. It1 has indeed been shown to1 be inhibited in an acid medium (Royer and Ba,uzil J . Ph,mm. Chim. 1918, [vii] 18 321) a'nd Fede'rlin (Zeitsch,. physikal. Chem,. 1902 41, 565) c.ould only olb8t'aiii melasurab3e vellocities for t,he re:a.dtion beltlwee8n phosphorsolus a.cid and iodine by using oonc,e,ntaateld solu tions .I n olna phase1 olf this work in ordelr to obtain small yet constant coaceintlraftioins ,oQ hydropn ions at '' regulat,olr " solutIon was use8d, consisting of equimo~lsoular proportions of phosphoric acid a.nd potassium dihydrogen phosphattel so tlha,t in the1 rea.otion-mixture elaBch warns prelselnt in mo1a.r coinc!eint'ration. Since the colncrelntra,t,ioln olf hydrogea ions was Coiist8antl the degrelei of iolnisatqio,n of hypol-phosphorous acid was a h const8ant a.nd f ojr these e8xpelrimelnts, (9) beaomes where T I and am constlank rl being assigned the1 value 2.0 as giving most coasistent remlts. Attempts t,ol relate r' to rh and li' to Ic(l-a)h whioh they replacel are co,mplic.a;ted by lasok of (1 +r'/a,)d~/dt = Elt .. . . (12 HYPOPHOSPHOROUS ACID. PART 11. 1327 sufficient data for such eolncentrated solutions but h is of the order N / 5 0 and (1 -a) about 0.4 so that it. is concludeid that both k / and rI are1 sevelral times greater than would bet expecteld. Owing to the) form of equations (11) and ( l a ) in many cases they gavel extrernelly cloncordant value6 of a constant based on the equation &/dt =7;'/Ztda; which was found not to hold when applield to ioldinei conoeintrations of a differeintl order. I n experiments XI XX and XXV tlhis constant is given as well as k o r k' as an interesting example of the danger of relying oln what happens to be1 melrelly a matThelmatical coinclidence .Tho integrarteld form od (12) is . . (13) E't =log - I + 2.0(log - a - log-) I I - s 1-a a-s I - s The 1,' Ion.-Considering t.he equilihrium Tti/ I + 1' investi-ga.ted by Jakowkin (Zeitsch. physi,kaZ. Chewt.. 1896 20 19) it' can I w slmwn thatl folr any st'age .of€ t.he relaction, [I.] = q a ' - s) / ( p + s - a') to a c10,se degree of a.pprolximatioa where pi is the molar mncen-tmtion of t'he potassium iodidel (assumed compleltely ionised) and tlhat [I3/] = (a - s)[l - K / (p + s - a)] sinm p increlasea by 2s and n delcreesels by s whe'ii s molecules o t iodine1 have beeln cha'ngeld to iodids ions. At' the! beginning olf an etxperimentl wheln s is zelro, [I,] = K a / ( p - a) and is thesefolrel independeint olf the co'ncelnt'ra-tio.11.It wa.s a t firstl tqhought thatl this woluld amount' for the peculiar belha,viour of the iodine in appareat'ly not a,ffecting t'he velocity olf the rea.eti0.n; but [I2] decrelasm molrel rapidly than ai- s with inorease of s sol tlhatl i f the iodine reacteld as such its appa.rent active maSs should fall o,ff morel rapidly than a - s whelrema.s adually it chaagee fa.r less ra,pidly. More,ov.er a colmparison wae made in expelrimeinta XI1 and I which were ideintdcal elxcept t<ha.t in XI1 pota,ssium iodide was a,dded so tlha,tl p wa,s equa.1 t'o 9*78a whelrelas in I it was 3.76a; if molle8culas iodine1 welrel the active1 faotolr the initial resot.ioln velocit8ies shoald be in the1 ra,t,io 2.76 t'o 8.78 whelrelas they were a81mo.st identioal. Errpeil-ime'nts XXV a.nd XXVI a'lso illustrate this in presence of the " regula,t,or " solution.The iodine therefore does nolt reactl as molecules. Thus it is t<he I,' ion whioh funchioins a'nd using t'hel const'ant 0.00135 giveln by Jalrowkin for the1 equilibrium i t is found tlha,t this ion constit,utes 99 per cent. of the available iodine in N/10-s,olut,iolns b,utq is le'ss in wela,kker solutions bsing olnly a'boiut 65 pe'r aent.. in N/400-solutio~ns a t the beginning of reactions a.nd increas-ing somewha,t' as the! relactio'n pro,aeeds. This change in t,hel rellatsive conmatmtion of tlhe I,' ion has been ignolreid t,hro,ughouh a.s th 1328 MITCHELL STUDIES ON correictiion involvetd only affect?s the smaller term and is more? o w r less at the elnd of a reaction than a t the1 beginning since the increase of iodide1 ions outweighs the! effect olf dilution and thus increases the proportion of 1,’ ions.Itl would unnecessarily complicate equations which are evidelntly sufficiently accurate to demonstrate the validity of the hypothelsis. I n conclusion it may be said that whatever the nature1 of the supposed active! ’’ form of hypophosphorous acid ita existence could probably nob bet detected by ohemical melans and as thel indications are that it is less than 1 per cent. of (and in constant proportion to() the1 acid mollecules its dchection by physical means would ba difficult. It is also possible! that another hypothesis coluld be1 found which would relquirs similar mathematical expression but if so i t is certainly more complicated than that devellopeld herel.E X P E R X M E N T A L . The reactions were carried out in stoppereid brown glass bobtlea in a theamoatat at 25+0*05O. The1 iodine solution and hydro(-chloric acid or “ regulator ” soJiitions. when used were made) up t o 400 c.c. and when they had acquired the1 temperaturel of the thermostat< 1.013 2.000 or 4.000 C.C. of a concentrated solution of hypopholsphorous acid were added from stlandardised pipettes. Atl definite times quantitieis were withdrawn and run into1 a large volume1 of watelr containing the volume1 of standard sodium thio-sulphatlei solution estimateid to1 bet necessary and the1 final adjustr ment made ati once. Check experiments showed that the hypo-phosphorous acid did not1 affect the1 titrations.The1 stlock iodine1 solution was accuratetly decinormal. As it was subsequently required t o know the potassium iodide content of this solution i t was found tot be 31.2 grams per litrel (or 3.76 mole\-mles per mdeculei of iodine) by an adaptatioin of the method with potassium iodate1 described by Sutton (“ Volumetrio Analysis,” p. 133). The stock hypophospholrous acid solution was a chemically pure artiole of commerce (D 1.14) which sholwed no impurities other than a little1 phosphorous acid. Its composition was checked by two metholds 25 C.C. of a one-tenth solution gave 1.5124 grams olf Mg,P,Q, therefore H,PQ + H,PO,= 5-45 moles. per litre ; 20 0.0. of cme-fiftieltlh solution required 21.80 C.O. of N/lO-NaQ€I with methyl-orange and 22.60 C.C. with phenolphthalein.Since hypophosphorous acid is monobasic t o both indicators and phw-phorous acid is monobasic to the1 former and dibaaic to the latter, tahe former is 5.25 molar and the latter is 0.20 molar thus givin HYPOPHOSPHOROUS ACID. PART 11. 1329 a total identical with the gravimetrio value. For obtaining the value1 of I the! solution was regardetd as 5*25N and the values of the hydrogen ions were based oa a normality of 5.45 since the seoond hydrogeln ion of phosphorous acid can be ignored. CaJculajtiom of ResztZts.-Thel degrees of dissociation of hydro-chlolrio aoid are taken from the reisults of Bray and Hunt (J. Amer. Chem. Soc. 1911 33 781) and the hydriodic acid is reckoned as hydraohloric aoid for this purposel. The degree of dissociation of the hypophosphorous acid in the presence of the mineral acids is obtained by methods based on the) autholr's recent ciommunication on the subject (this vol.p. 957). From table I givea therein a curve is constructetd showing the relation beltween a and the con-centration of hydrogen ions a/v when no extraneous acid is preeent. From hhis it is possible to obtain a series of curves one for eaoh value of I showing the rellation betwesn a and the con-centIration of extraneous hydrogen ions (El',) as follows for a delfinite concentration of hypophosphorous acid I the value of a when H' is zero can be1 obtainetd at once. A slightly lower value, al is then selected and the concentration of hydrogen ions in equilibrium with the1 acid alone1 a t that delgree of ionisation is found from the! first curve; this must also be1 the concentratioa of hydrogen ions in the1 equilibrium if foreign aoid is present as shown in the paper quoted; from this is thelrefore deducted lal due to the hypophosphorous acid itself and the remainder is H*,.A selries of corre6ponding values of a and H' is obtained in this way for elach value of I and from the resulting curve the value of a oan be obtaineld for a known Hez. This melthod is simpler and of wider applicability than solving the] equation developed in the former communication. I n order to avoid small decimals all conceiitratioiis are multi-plied by 200 and the value of X shoald therefore bet multiplied by 200 in order t o give1 absolute units. Time t is in minutes; a - s shows the iodine concentration in molecules; s shows the! number of moles.reduced ; I - s the hypophosphorous acid remaining. The column HI shows the original hydroehlorio acid (when uwd) pluq 2s the hydriodic acid folrmed. H*=[ are the1 corresponding hydrogen-ion concentrations of the1 mineral acids the degree of ionisation (not recorded) being assumed t o be unaffected by the prese,nm s f the weaker acids. a gives the degree of dissociation of ths hypophosphorous and phosphorous acid and under H' is recordetd la the hydrogen ions deriveld from them the slight correc-tion neceissary f o r the phosphorous acid initially present having been made throughout. Then follow the1 total hydrogen-ion ooln-cwntrat,ion it and 1 -a, the mean value1 o l 1 - a fur the period 3 c 1330 MITUHELL STUDIES ON (or 1-+ the value at the middle of the period) for which the constant k is odoulated.Farmula (11) is used except where otherwise stated and in any one experiment the deviations of k from the mean rarely e x d 3 per oent. The six following experimenta wer0 without original hydroohloric acid. Experiment 1. t. a- s. s. 1 - s. HI. H'H~. 0 4.99 - 10.52 - -5 4-82 0.17 10.35 0.34 0.34 20 4.34 0.65 9.86 1-31 1-28 50 3.29 1.70 8.82 3.40 3-27 80 1.96 3.03 7.48 6-07 5.77 105 0.98 4.01 6-51 8.02 7.58 125 0.19 4.80 5.72 9.59 9.02 145 0.03 4.96 6.56 9.93 9.34 a. 0.645 0.640 0.625 0-590 0.553 0.530 0.513 0,510 H'P. 7.10 6-99 6.77 6.44 6-00 9-79 5.58 5-57 m = h. 7.10 7.33 8-05 9.71 11.77 1.3.37 14.60 14.91 1.543.l-aM. k x lo5 0.355 118 0.365 114 0-382 112 0.400 117 0.413 118 0.421 120 0.422 113 Mean = 116 - -The data of the other five experiments gave constants of the Expt. a. 1. U. Hey= h. rn. k x lo5. 11. 9-80 20.62 0.552 11-81 1.546 148 IV. 9.92 5-34 0.735 4.07 1.651 134 V. 9.86 10-44 0.645 7.05 1.606 124 VI. 2-43 25-50 0.525 13.91 1-425 139 VII. 2.46 13.00 0.622 8.40 1.607 120 [In experiment VII the complete formula (10) was usad with n.= 0*030.] The following experiment is comparable with I and shows the negligible effect of adding more potassium iodide (see p. 1327) : XII. 4.97 10.44 0.650 7.05 1.506 114 same order of agreement and are here summarissd. The next thirteen experiments were with initial hydroshloric wid.Only experiments I11 and XVI are given in detail the latter showing the accuracy of the constant at very low conmn-trations of iodine. t. 0 6 10 15 20 25 30 35 40 45 50 65 60 Experiment IZI. a - s. s. 1 - s. HI. H'HI- a. H'p. h. 1-aar. k x lo", 4.93 - 10.44 11.30 10.59 0.496 5.38 15.97 - -4-33 0.60 9.84 12.51 11.68 0.485 5-26 16.94 0.510 (139) 3-89 1-04 9.40 13.38 12.47 0.478 6.18 17.65 0.513 126 3.34 1.59 8.85 14.48 13.47 0.470 5.10 18.57 0.517 129 2.80 2.13 8-31 15-56 14.44 0.463 5.02 19.46 0.620 130 2.31 2.62 7.82 16-55 15.35 0.45% 4.95 20.30 0.524 129 1.81 3.12 7.32 17.55 16.24 0.450 4.88 21.12 0.527 130 1-40 3.53 6.91 18.37 16.97 0.445 4.82 21.79 0.530 127 0.95 3.98 6.46 19-25 17.75 0.439 4.76 22.51 0.533 128 0.57 4.36 6.08 20.02 18.44 0.434 4.70 23.14 0.535 128 0.28 4.65 5-79 20.60 18.95 0.430 4.66 23.58 0.537 128 0.11 4.82 562 20.94 19.26 0.428 4.64 23.90 0.538 128 0.04 4.91 5-53 21.12 19-41 0.426 4.62 24.03 0.639 130 nz = 1.644.Mean = 12 t . 0 7 12 16 22 38 44 9 I a - s. 0.499 0.460 0.389 0.319 0.267 0.196 0-141 0.043 HYPOPHOSPHOROUS ACID. PART 11. S. -0.039 0.110 0.180 0.232 0.303 0.358 0.456 Expt. a. XIV. ...... 9.76 XV. ...... 0.250 XVlI. ...... 0.250 XVIII. ...... 0.986 XIX. ...... 9.58 XX. ...... 0.985 XXI. ... . .. 0.985 XXII. ...... 0.493 VIII. ...... 4.97 IX. ...... 2.485 XI. ...... 2.485 1 - s. 2.670 2.631 2.560 2.480 2.438 2.367 2.312 2.214 m. 14.10 14-18 14.32 14.46 14.57 14.71 14-82 16.01 1.2.670 2-670 1-040 2.080 2.080 1.040 2.67 2.67 2.67 10.30 20.20 H‘HI. 13-13 13-20 13.33 13.47 13-56 13.68 13.79 13.96 a. H‘p. 0.515 1-43 - 1.42 - 1.42 - 1.42 - 1.41 - 1-40 - 1.40 0.503 1.39 412 H.I. 11.10 28-20 14-10 2 8.0 10-86 28.0 11.20 28.0 113.0 56.5 113.0 H’HI. 10-41 25-66 13.13 25.5 10-19 25.5 10.47 25.5 96.0 51-0 96.0 a. 0.498 0-409 0.515 0.415 0.459 0.412 0.550 0.41 5 0-25 0.30 0.25 I&. 14.56 14.62 14.75 14.89 14.97 15.08 3.5.19 15.35 = 1.73. H’P. 5.33 1.13 1.43 0.45 9.64 0.9 1.20 0.44 ---1331 1-ua,71. k x 10s - -0.486 (135) - 116 - 116 - 116 - 116 - 116 0.491 116 Mean = 116 m.k x lo5 1.647 128 1.830 136 1.764 132 1-66 123 1.572 145 - 122 1-81 112 - 137 - 137 - 129 - 131 Where no1 value is given for m h is regarded as constant and in thei lastl tjhreo elxperimelnts thei value of has been neglected, as not apprelciably aflecting tho total value of h. Also in the last three elxpelrimmts a was obtained by extrapolation and is there-fore only approximate. I n expelrhent XI eight values all between 300 and 312 were obtained for the constant k”xlO4 mentioned on p. 1327. In experiment XX similarly all ten values were between 107 and 112. The following Seveln experiments were in a solution molar with respect ta both phosphoric acid and potassium dihydrogen phos-phate as ‘‘ regulator ’’ (see p.1326). Formula (13) is used in each easel. Experiment SXITI is given in detail. Experinmat X X T I I . t . 0 2 6 10.2 15 20 25 33 45 a - s. 4.996 4.596 3,898 3.246 2.578 1.996 1.622 0.950 0.432 S. -0.400 1.098 1-750 2.418 3.000 3.474 4.046 4.564 1 - s. 10.50 10-10 9.40 8-75 8-08 7-50 7.03 6-40 5.04 k’ x 10’. -2 74 267 268 272 274 274 276 276 Xcan 272 3 o* 1332 MITCHELL STUDIES ON Expt. a. I. I;‘ x 104. XXIV. ......... 4- 970 5.224 271 XSV. 2.494 5250 254 XXXI. ......... 0.4992 1.050 364 XXXI1. 0.2496 1 -050 29 1 XXXIIJ. 0.4992 0.525 266 ......... ......... ......... ......... XXXIV. 0.4994 5.250 240 For XXV all eight values of liN x lo* (p.1327) are between 600 and 626. Experiment XXVI was exactly comparable with XXV except that i t contained potassium iodide in the proportion of 15-8 mole,-cules to elach molleculel 6f iodinei; XXV and all othes experiments except XII have tthe proportion 3.76. The1 constant 1;’ x 104 was 255; the1 agreement with 254 obtaineld in XXV shows that iodine funations as the 1,’ ion. Experimelnt XXVII atl l l * G o gave a constant k/ x lO4=54*8, and as it is exacltly parallel with XXV the temperaturecoefficient is 4-64 for 13.4 degrees. Logarithmic! proportion reduces this t o 3-14 for 10 degrees and 2.22 for 7 degrees. Steelel found 3.1 for 10 degreles for solutions without added acid or “ regulator.” Since the term involving r! the ratio beltween two rapid reaction veloci-ties (sea formula 12) accounts for morel than half the1 value1 of the constants it appears that this ratio is practically unaltered over the rangel of temperature employed.The agreement beitween the oonstants obtained in this seiries of “ regulator ” experiments shows clearly that the1 iodine must func-tion in the manner shown in the equations useld. Tho effect of iiegleoting itl is velry much more apparentl in this series than in the1 earlier experiments. In order t o detect possiblel oxidation to phosphoric acid the following procedure was adopted. If phosphorous acid only is producied each molecule o€ iodine reduced gives rise1 to 2 mole-cules of hydriodio acid and also changes 1 molecule of inonobasic hypophosphorous acid to 1 molecule1 of dibasic phosphorous acid, phenolphthalein being used as indicator ; whereas i f phosphoric acid is produceld 2 molecules of iodine give rise t o 4 molecules of hydriodic acid and still only raise1 the basicity by unity.There-fore in thel former case the1 increase of acidity should be 1.5 times the1 numbex of equivalents of iodine consumed and in the latter case the ratJo should be 1.25. I n every case tested the ratio has been very Close to 1.5 so that the production of phosphoric acid is very slight. Expt. I.-At tI4‘, 20 C.C. relquired 14.84 C.C. of NIlO-NaOH more than a t f,; iodine consumed=9*93 C.O. of iV/lO-Na,S,O,; r a h = 1 *495 HYPOPHOSPHOROUS ACID. PART 11. 1333 Expt. I1 -Increase of alkali titre a t t,,=14.63 C.C. ; iodine consume)d=9-75 C.G.; ratiol=l.501.Expt. V.-Inorease of alkali titre a t t,,,=19*58 c.c.; iodine consumed = 13.10 0.0. ; ratio= 1.495. For the samel purpose in the (‘ regulator ” series an elxperhent (XXVIII) was carried out exactly parallel with XXV except that hypophoisphorous acid was replacwd by the same concentration of phosphorous acid. I n three hours less than ons-half per cent. of the ioldine was reduced whereas in experiment XXV 50 per cent. was relducetd in twenty-two minutes. Experiment X was earrieid out’ with hypophosphoroius acid which was previoasly neutralised (to methyl-orange) and is comparable with I. I n five hours less than 5 per cent. of the iodine was re#ducmd; as the second hydrogen ion of the phosphorous acid, originally present to a slight exteat would be1 sufficient to1 start the reaction and so1 provide more hydrogen ions it< is probable, that reaction in neutral solution is etxtremdy slow and that1 the H,PO,’ ion does not relack except possibly in the presence of hydrogen ions in which case reaction is elvidently so slow as not qreatly to1 affect the1 constancy of values obtained on the1 assumption ;hat8 i t does not take place at all.The following experiments of Steele’s are quoted after con-version to1 the units used herein tol show how the irregularities oherveld by him are largely accounted for in the light of the preselnt work. The first two columns are derived from his data; the remaindelr are obtained as in the author’s rwults. The constants obtained by each method are shown those of Steele being designated by Ks.The letter S after the Roman numerals indicates his experiments. Tha value 119 obtainetd f o r lc x 105 in X(S) is in agreement with the author’s results and shows less falling off with time than does K,. Moreover for the thrw experiments the resulte are far more concosdant than those obtained on Steele’s hypothesis. The fact that Steele used a very pure specimen of hypophosphorous acid may account f o r the slightly lower values in his elxperiments. Expt.. a. E. a. H p = h. k x 10’. Ks x 10’. X(S) 2-00 20.00 0.555 11.10 119 94 XI(S) 0.500 5.00 0-734 3.67 92 45 XII(S) 0.200 2-00 0.841 1.68 83 24.5 Altqhough the agreement is not so good as in tdhe other results, it is evidefntly far beltter than in the results obtained by Steelel’s melthod so that t h s present hypothesis which attributes a definite part to t’he iodine! molecules is apparently more justified by reeults than that’ which ignofree the ioldine and attributee the great decreas 1334 HYPOPROSPHOROUS ACID.PART 11. in the1 conshnt t'ol a delarelase,d a,ctivity of hypopho'sphorous aaid a.t low concelntrat,iolns. This is further suppolrteld by a recoasidera,tion of S,t,eele's experi-meat 11 for which he1 co1ul.d nolt olbtain a. constIantl witholut assuming the degree olf ioiiisaflio.n t,o b,e 0-20 inst8eamd of the a.otua3 0.775 whioh was aga.in supposeld to be! due tlo dscrelased activity. Aclcolrding to the! premnt melthold one o'bt'aJns modera,te constmanay. Experim,ent I I ( S ) nt lao. t. 0 390 570 1440 1710 1830 2805 3240 a - 9.s. 1 - s. H'"'. 4.50 - 4.00 -4.20 0.30 3.70 0.60 3.98 0.52 3.48 1-02 2.42 2-08 1.92 4-00 2.04 2.46 1-54 4.68 1.84 2.66 1.34 5-04 0.80 3.70 0.30 6.96 O.G8 3.82 0.18 7.24 a. 0.775 0-750 0.735 0.660 0-643 0.636 0.597 0.592 H'p. h. 3.11 3.11 3.00 3-60 2.94 3-9G 2.64 6-64 2.56 7.24 2-54 7.58 2-38 '3.34 2.36 9.GO m = 1.675. 1 -aH. k x 109. - -0.235 (25.3) 0.245 (28.1) 0.280 38.3 0.290 37.7 0.295 39.2 0.340 41-5 0.355 39.8 Mean = 39.3 I f the temperature-aolesfficient for sewn degrees is t'aken ass 2.22 (see p. 1332) this gives the low value of 87 for 25O but that the elxperiments correispolnd in geaeral is sewn from the fo'llowing summary of expelrirnenk for which the dat'a can be utilieed: Experiment.III(S). IV(S). V(S). VIII(S). XIII(S). XV(S). XXI(S) 11 x lo6 108 115 119 105 107 113 119 K S S lop 355 400 425 430 425 505 555 Steele's .Es x 104 give'n folr cornpasison clearly shows tqhO ina,delqualcy od his hypolt,hesis. The1 me,thod of trelat.tmentj nolw presenteld obviously p l a m t,he qu,es,t,ion o'n a molrel systma.t,ic basis a,lthoagh tlhe slight variation of tlhel " const,a.nt< " fro'm one elxperiment tol anothe,r is not a,ocount;eid for ; but tlhel sevelral small a.ppro.xima't,ions maBdet t'ogethe'r wit,h the unclert<aint!y in the ohoice; olf the value] of the constant' T th0 large influelncsel in wrtaJn ca,ses olf a. differelnc,el I - a whiclh is somet8imes very mall and t*het adtelration in t'he pro'portioln of the iodine whioh is preselnt as the! I,' ion may easily a,coount forr the variaikm of 10 per cent'. from the ineta,n valuel 128 x 10-5. It is. also1 probable t,hhat the H,PO,' ions reactl slowly and a,ccount pastly for the va,ria,tiolns8 since t'hel three higheet constant.8 are! given by t'hel three great eat' con (3en tqr ahi on s of h y p c~p h osp h or ou s' acid . Su!mmuay. (1) The1 previous a;tltemptt to explain the reladim had suggwted an hypothesis involving tthe preselncs of free ioai,u aharges. By takin PRIEDEL AND CRBFTS' REACTION. PART I. 1335 into consideration certain factors which had beea ignored this is shown t'ol be unnelaewary and most discrepancries disappelar. (2) The:se fa,ctors were (i) the influence 04 the ioldinel concen-taation oln the me:asurab,le vellocity t,his influesnoe being slight. at moldemte dilut,ion but rellatlively lasge akt grea'telr dilution and (ii) hhe eE& of hydrolchlolric and hydriodic acids on the ionisation of hypophosphorous a,oid. (3) The following hypotheisis is a,dvanmd ts elxplain all the anoma.lies f omelrly notleld. The hypophosphorous a,cid molecules a,rt?l in equi1ib'riu.m with a very small proipolrtion of an '' active" form (say H,P03) which rea,cts rapidly wit,h the iodine, The restmatioln olf the eiquilibrium thus displaaed is accellerat3ed hy hydrorgen ions a.nd forms the' me.a.surable! react.ion, H,PO,+ I,' -+ €I,PO,+ 2I-I'+ 31'. H3P02+ H,O - H,PO,. UNIVERSITY OF LONDON, SOUTH KICNSINCTON S.W. [Received Xeptembw 13th 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701322

出版商:RSC    

年代:1920

数据来源: RSC