The kinetics of the reaction between mesityl oxide and chloramine-T (CAT) in aqueous sulphuric acid in the presence of KHSO4 has been studied. The results indicate a radical chain mechanism to be operative which is quite novel in CAT kinetics

Sanmuganathan, S. P.

Santappa, M.

Venkatarao, K.

Vivekanandan, S.

English

Publications of the IAS Fellows

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li.it1clil's &. I\lcchat1islll of Ilah'gt'l1:1tiv(' 
OIi;~nl1lerizalinJl of l\h,silyl Oxide. hy 
Chlonlll1ine-T: EvideJlce fOI' a Novt'J I'ath"'ay 
. in i\ljueolls SlIll'hlldc Acid" 
\'I\""~,\N:~rJl"\N: 1\. V1'.J'.'I,\r.\I·:.,'q & 1\1. S.\r-.;T,\I'I':\ 
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;Illct 
1)"1';111111':111. til ("wllli:;',y, 11;,l'!ltI.iyapl':":' C "lIq:'1 
1\1:101 r;"i (,1100.\0 
TIt(. Idllt,ti('s of II H.' I"('actinn h\~I,,"cl'n "H~-~·dtyl oxide. 
,,,,,I chlonllninc-T (CAT) in' aqucnUS sull'hudc acid 
111 thc pn'srllcc of KIISO, hilS hl'cn stlldied. The 
n,,.nl1s Indicate 1\ nldie,,1 chain mechanism to he 
lIpcnltivc whkh ,Is 'Illite novel ill GAT kinetics. 
e" '-' Ii, ,\ ~11 N L T ('AT) I,;' ,";1. ,.Ii,·"''' il,;,,11 
;0', ;011 ,'lli"i"1I1 ;01111 d,']'"".!"loI,, ,,\i.\;.111 ::1111 :I 
\.""',;>lil,. ,100"lill;;lill/: ;'/:"'" ill .. I'('llI.i, "I ;'1,,,h'~T ,,'., 
'11111 ill 1(:;I,(li"lI kil1,:li,:<' " .. \ lilly .':ill1\.I1' 1",,,111 1 I·· 
h;tV" Iwell lIoliced so far ill iI's reactioll willi 
~ 1.'Il'~~(,lIt!'d ;lS ,a pl'l'Iilllil1;lry lI'l,prJ. ;d. III(' ,\11 I,"d;;\ 
. 1'111111.11 nil , ),ridoliulI.,.(d/((filll/ I/',/{'Iillll.'; 1 ... ld :11. IljI' lll1l\ cr·· ~,it\. 'fIr !'I:tdr;I~, 1:1I111;HV ".fiX ;11111 ;.vilh ftlrllU:1" rt'~~lIl\:; 
\'''''':1'1I1t.-:I ;1:', ;t p'aper .~I. lhe (:/i, /li' ..... lI'y !;y;lIl"}~';1flll held 
at lhe 11'1'. ;'[atlras. MardI 1978. 
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.,,,1., 11;1((': .. ;1 n. \VI.' It'IIO!t ill tlli~ f'(J1l1l1ll1l1ic';llillll 11111 
k illl"l ic cvi<lenn: for " nuvel h .. logt:1la I iv,' "I i~:,,­
lil,'n7- I Iioll of J1H'~ilvl oxide (l\10) by c1i1or;l1l1illc-T 
ill <I'I'lt',,"S (O<!75M) ~lIll'llnri( acid . 
111 Ihe pr,'Sdlce of K II SO.' lhe re;.Iclioll 111;;lIif"!;ls 
" 11·I,i .. ,,1 frlll:lioll;,1 ordel behaviollr, i.e. " de;'"-
.) order ill IC;\TI "lid :t 0·5 urder ;Il low I.~IUI 
«11. 11 \':;1\1) \\·llich cil;:ngcs to 7-ern ordel 1I11dl'I 
1";",111" (,,,"dili()!l~ (I :15).- Tilis is 'Illite f"llIili;;r ill 
-Ire,' rl1llic:II 1'01~'l1l1'riz:l I iOIl kindir~;. l:h,~idcs tllis 
~li"II;o"li,;.M"III"1I IVl'c .. f 1",lravi()lIr, tI", rc .. C'lioll i" 
",,,,""I;l"',J willi VI'I\' 1;,,;1 t:'Jllilillria durilll: lire 
illil i:ll slages. This kinetic cvi(h;ncc for COllll'lc-X 
forl11;:liO(l is s\1pported_by tire large sllifls ill lhe 
A""" v,dues for lhl! reaclioll mixture when COJl1-
p:lI,'d In those of Ihe rc;1(;lanls. A Ill'gligil,le s;dt 
dl' .... (II.: 11-477111 .n n'777l1l; II ili_ 40": lUI') 10 
()'2C>7,ll·(I·r, sec-1) and a margin,d incre;\sG ill r;lIe 
wilh inc.-c;,sill/{ 111,0+1 (0·113111 10 (J'375M: kat· 
,100 : (l'2'H lo O·32()il/-"·6 s,,("-J) have beell )Iolin:d . 
This hehaViO\1r indic;:\rs Ihat Ihe ionic mecll:l1tism 
1",SIIlI;dc(\ ill rc:!ctiolls involvil'g CAT" may 1iOt he 
IIper:llivl' ullder OIl r kind it: conditiulls. The rC;lcl inll 
is "ol'sider'lI,ly f""I"r ill the ahsellce of ad.kcl 
lI,il"'''.1 acids Sll/:I:,'~.:lill/: all :tltogt:lh(,r diff..r"lIl 
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its (lxid:l\ion lo CI- lir;d helps f;)ster propagation 
of till, <:h:lills. 'I'll,: ,jver;"1 :'ctiV;llioll ('ling\" is" 
("j.7 \;,1 11101- 1 (15-50°; ,,: ()'254 10 (l,')5HJlJ-o.6 s .. :c- J ) • 
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ill"I't';~"s slighlly willi iP('I',';!sillg inilially. ;·.ddcd 
jJ-tollicllcsulphonamiue (PIS) which is one of the 
INII! IN .I ,111"1,, V,,,,, 1(,,\, lIJNI': 1'17~ 
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1'lII'llic(', illclll('cd pOIYlIlCriz;ltioll of :lcr\'l,",ilr i lc 
shOll'S Ih(, illl'nll'cilleid of f('(,(' r:I."icals III II«~ 
s,\',I:(:lII, /\/1 ,,,'.-',,: t'-"perill)I'III,,, f,\(:t~ 1(,;,.1 I!S I" :t 
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'iI,v"l ill ,'/\'1" ki,,1'/ ic:;" 
1\1,: ! r,I,;, ' ;- T.,: rll Ii 11;( I iOIl 
Tit,: Ct)IIIPJ,.X 111:1.1' III,: f"rllit'd loy tilt,' """rdl. 
id III'.' 111/1(' 1';ljr IIf (·II',·lllIlIS (jll ·lIi'''''I.;1 
1\:",11/'1(111) I" IIII' (I ,./ I\I() i,,' ii' ,'I,,,li, /. 
I ! It ' IJ if.":: I "~ i I. i I; ;1/' .. :.-1 !\I' ' •. t:·:; Il1"', ,;; . '.11 III 
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ill sf, i' (6). J\ssllllIillli s[c:~dy Sf"'(:(,OlldiliIJIIS, :," 
1'.\:1'1" ;11111 of lIi(! f.,VPI' (11)_ ('fI:,;ld IJ(~ III'[aill,'d, 
"II \'II kIHj(:A'rl,JJVII, 
dt -'(]I:II\II," 
k I ('AT/ 'I I .I, fu I'I,(A, TII,I\lI}I/!' 
I'll,' 'tl"7' II/I'lill/. 
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leAl/Ii ~II, 
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'" (12) 
1111:'/;/" 1',('\) 
Si"c" I lil" III"illr CAT ('(JII~llilli.llg s(,,/' is Ilidy (I)), 
I/'l' lil'~t fernl Oil (lte rigid h:lllli :-idc "f (II) \l'il/ 
11,,1 I", "il"lilit'; III \l'liirli' is ill dgrC('III"I'( \l'il/I 'lie (lh~"'I\'('/1 ':lllllT fl.lI' the' J"t.'acliul1, 
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11,(, 1',,11.:';/ i;.lill' of <:,\ T "" all illil i" llor jlJ 1'1"'(' 
r,:di/;;, Il'olvlIlt:rlzal ion, I'1I1'11\('r illvesl jgaliOl;>; (i);)" 
Sill'll l'ol.l'r;,,:riz;;li()l S, (ii) lI'illi ollter (l.0'"l1s:llllra l0'1 
sy,;I'.'JII<' :llId (iii) ill diH,'r(:1I1 soh'elll (:lIviI'OI'JIIt.'lIh 
i' I"{' i" progTCSS, ' 
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;\'''/':;/','1''..-/0, :nB (1'172), 11101, 
6. i'·,\TAIU.iI\N; 1\1. 1'1. & TIlJAGAU'\JAN, V" J. chem. ~""()C. 
1'",1,.,/1. 11, (1'175), 15')0, 
7. J\ Clllllp"-'Ir' ;11111 dcl.a.iII'fJ di:~I:IIS:·,i"lI flf IIIf' product 
:l1I:t1\":.i·; :,"d id':lllilif'al.illll ,,"dIT filiI" liin"';.: :III" ,dill'/" 
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I\".,;i·; :lIlti I ;V, 11<, N,\/I, :11111 III;"~,:'; :;i',:dl"al :,l.udic:1 
;Q ll1l';lrs dscw.III.'.rt.,. 
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Kinetics and mechanism of hallogenative oligomerization of mesityl oxide by Chloramin-T. Evidence for a novel pathway in aqueous sulphuric acid

http://repository.ias.ac.in/88822/1/88822_%28519-520%29.pdf

Kinetics and mechanism of hallogenative oligomerization of mesityl oxide by Chloramin-T. Evidence for a novel pathway in aqueous sulphuric acid

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