CXLII.—Studies on hypophosphorous acid. Part II. Its reaction with iodine

Abstract

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 0 1 1 1 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$e concentra,tliom oC the1 hydrogeln ions and the1 hypophosphoroas a'cid. From them fact,s, it wa,s conoluded t,hat the oixidat'ioii t.0 phosphorolus aaid involved tlwol suceeIssive reia,ctions, : the! first,, of melasura8blel vellocity, in which t,hhe> mercuric chloride1 t-oak no1 patr.t, a,nd t'hel secolnd, o,f relat'ively p a t , ,ve,loclit,y, in which the1 melrcuric cihloiridei f unct'io'ned. No coinventiona,l hypot.helsis appeared adequa.telly t'o explain them facts. I n o'rder ta investiga,te certain points inolre fully, an ana.logous reaction was soughtl in which the analytica,l rneltho'd used would be of grelat'es a,pplicab,i!ity. The. relactio'n with iodine was found to be acc,ura,tely colrnpa,rable, a n d is here, delscrihd. That wit$ 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 follo3wing ex-planabion : the slo'w stage is represented by which procselds, libelrating free1 ionia chargee, if thejrel is also preselntl a

Kinetics and mechanism of oxidation of hypophosphorous acid with silver(I) in aqueous perchloric acid solutions

“…S. Son, R. Kanno, and M. Koizumi* Received January 3,1980 Many layered inorganic compounds are known to act as host lattices and react with a variety of guest atoms or molecules to give intercalation compounds in which the guest is inserted between the host layers. Recently these materials have attracted considerable attention for such different reasons as the observation that the superconducting transition temperature of some hosts increases on intercalation of amines1 and the…”

Synthesis of 1-Phenyl-2-methyl-4-ethylpyrazol-5-one

“…Triiodide ion is at least one of the reacting molecular species in the oxidations of phosphorous acid,2 of ferrous iron,4 and of hypophosphorous acid. 6 It seems probable that some relation may be found between the molecular species of iodine involved and the nature of the reducing species or of its transformation, after a larger number of kinetic studies has been made.…”

Oxidation of hypophosphorous acid by peroxydisulfate. Kinetics mechanism

“…Phosphorous acid has only one P-H bond and is a dibasic acid with the structure HP(0)(0H) 2.3 The two acids are strong reducing agents, and their reactions with a host of oxidizing agents have been investigated. [4][5][6][7] In the majority of cases the reactions where (acid) represents the concentration of either H3P02 or H3PO3, and (ox.) that of the oxidizing agent.…”