1960Supplement096oaeoomHseBuosoeaaooaraueuHocoHoueoHueenocoHe()easeaetneearsasaee16679806suroa)eSE)TOTONHeNSATO(I)ounoreeeeuoieneisisssteo Hos'H'Ho-4(")saeuis"MOTSBM20
Homogeneous Reaction Kinetics 302.440 COMMENTS Reaction: (.1) Added salts NaHCO , Nad, KC1, CH COONa and HC1 and CH GOOH had no effect on exchange so long as PH was Idw. (.2) Rate dependence upon CNO~ very slight so that value of k is limited by experimental errors but au thors consider It significant. (.3) Rate constant listed Is one half observed rate constant for approach to equili brium which is sum of rate constants for forward and reverse reactions. (.15) (.16) (.17) Equivalence of rates for all three reactions considered by authors to be consistent with rearrangement occurlng by carbonlum Ion intermediate with lifetime long enough to permit equilibration. Exchange data indicates reaction is probably first order with respect to p-CE C H SO H catalyst. 364 3 <p LITERATURE C 1) A. R. Amell, C. 0. Houle, W. A. Cilley, ACS 1959, 81, 4504. (*) W. A. Bonner, C. J. Colllns, ACS 1955, 77, 99. ( 3) F. Kalberer, H. Schmid, H.C.A. 1957, 40, 13, 255. ( 4) R.U. Lemleux, C. Brice, CJC 1955, 33, 109. ( 5) R.U. Lemieux, C. Brlce, G. Huber, CJC 1955, 33, 134. National Bureau of Standards- National Research Council December, I960
SUPPLEMENT19600961i8 suesog 012-i/n ul oie shunouy2CseT (joqwoopoF00s Puu1/WsaenotO1aal Jo aouasqe pre71xCKob&46EIT233544tII+A432aaidueoeiins sseraaeso1502e-16910555344Essen oienpueppe0901JounonyTOHPueppyoaaoaro22-9-g0 2-6-gor(a)e22-8001 16-2-V0EEEE310sosunowyHOHOTgAosresenoseoiaensaersearo+*t0to+rIR*1"5n()+e"tous7*ON60611ee'ON2
Homogeneous Reactions 302.474 ISOTOPIC EXCHANGE Halogen on IVth group halide Liquid phase Amounts are in M/ I. Rate constants are i n M/I and sec. No. .2 0) c £ £ o z — CT\ 0- r-l Q. 3 O5 .1 React i on sncis + Sn*Cir» 3n*Cl 2 ^ SnCl 4 -H C 0 CO ' H 20 CH 0 OH J Amount of reactant 10 3A=9-77; 10 3B=5-32 10 2A=3-9; 10 2B=3-13 "O c: (D "° HC1 0 -o 3 "XJ E 10 9 10 11 i£ * E — "S o c — 03 «J 0 feAB A;AB <D «J DL 1— 0 25 25 25 33 40 47 k = k° x I0n k° 1.74 6.3 9.2 1.22 7.1 1.57 3.2 n -3 -3 -3 -2 -5 -4 -4 £ 11 21 A = .0 x 10^ ^4 0 4 6 n 7 10 - « c E E O O Q> cri (D -H f 1) ( 2 ) COMMENTS Reaction shown to proceed at same rate in presence of added glass surface and in presence and absence of light. LITERATURE (*) C.I. Browne, R.P. Craig, N. Davidson, ACS 1951, 73, 1946. ( 2) E.G. Meyer, M. A. Melnlck, JPC 1957, 61, 367. National Bureau of Standards - National Research Council December, I960
SUPPLEMENT1960096t1oqwe00gGle ssurisuog otnyPl/w ul ele stunowy23C525asou4 panb1T0os pe1/wu!****srenOT4t8"x21LOL08图50用Oo16554354+5r"x0'90'23304-8'2-7H3964aO525125555G554o&840253MIOTOpougoossee31-9-,01:2-0-V,0129-90 t--gom2-1-8g01 :6-8-Ve01a-9:08-46.1-9*0(e saoreee)9'1-g0m 8'T-Vg0m221-9°06-2-g01 t-,01522gosuonyee iuamag aa o uo0'%8-9L-fo0311ndir n%OS aurEXOTG+"onN'Ho%090RBOS QueXOId+"on'Ho0"'o"auexouonioaoril uexoId+"on'HoniaonAOs"ON'HO""n:E:ETon'(0) ++(01(t'0)n() + t'C)o*() + s()s"10 + *T0T8()on'() ++0"'0-01个* on'(0) + 101s "'0-010k0)on'(t0) ++101s'[m0*(0)]on'(W0) +ote(*"o-1)on 1s [0(]R*(0) + 08(0-t) 0nC0) + 1018"(%)eee个1+8++TOs(HO)2100224502!
Homogeneous Reactions 302.475 ISOTOPIC EXCHANGE Halogen isotope exchange between IVth group and Vth group atoms Liquid phase Amounts are f n M/l. Rate constants are i n M/ I and sec. No. .1 .2 .3 .4 .5 .6 React i on (CH ) S1C1 + SbCl * — > (CH ) S1C1* + SbCl 33 3 33 3 (CH ) S1C1 + (C H ) NC1* —— »(CH ) SiCl* + (CH ) NCl 33 254 33 254 [(CH ) CH] SiCl + (C H ) MCI*— > 323 2 o 4 [(CH ) CH] SiCl* + (C H ) NC1 323 254 (c>cio-C H LS1C1 + (CH) NCl* —— > Olio £ O 4 (cyclo-C H ) S1C1* + (C H ) NCl 6113 254 < C6V 3 S1C1 + ( C2H5 ) 4NC1 *~>(C6H 5) 3S1C1*^ 'W 4NC1 (1-C H ) S1C1 + (C H ) NCl* 10 7 3 254 (1-C, H ) S1C1*+ (CH ) NCl 10 7 3 254 So 1 vent hexane,C6 H 14 Amount of reactant 10 2A=2-74J 10 3B=5-57 (unlabeled reactants p re- equilibrated) C H6 6 CH3N02 +Dloxane 50% CH NO 3 2 CHgNOg+Dloxane 25% " " 50% n " 75% CH.NO +Dioxane 50% o « CH 0NO +Dloxane 50% o « CHgN0 2 -»-Dloxane 50% » " 75% 10 2A=1. 8; 10 2B=1.6 4.0 9.5 11 27 11 2.2 11 2.2 10 3A=8-9; 10 2B=l-2 6-8 0.6-2 8 0.6-1 8 0.6-1 10 3A=4; 10 3B=2-9 10 3A=6-7; 10 3B=6-12 4-7 7-8 i m » i i e ~" ~° ~ o o .c ^ *»- ^ V OJ 0 kAB feAB feAB feAB feAB 0) u 3 <d i_ c Q. E <u h- 20 30 40 40 25 25 25 25 40 25 25 25 25 25 25 25 25 25 k = k° x ion k° 1.4 3.0 9.1 6.3 9 3.8 4.3 2.3 1.6 very 7 1.1 1.7 1.6 5.0 n -5 -5 -5 -4 -3 -5 -5 -4 -3 fast 0 + 1 + 1 + 1 0 very fast 4.2 2.0 + 1 + 1 E 1 R J-O 24 ^ = >4 0 x ion ^° 2 1 n 8 14 0) -H C o E E O O * * * * 9 i_ 3 •*-* «f L. « +J _J ( 8) t 1) ( lj (») C 1 ) t 1 ) National Bureau of Standards - National Research Council December, I960
1960Supplement0961 4eqwe080a2aareesenao senreeeeeeeeireeetOTsoaaoa(6")02sporas o im areion aueatenGIAoGeaEA(9)oSEE（g)(")1Ooesee'T292e96118onnreoaav()C1B "0TOn'('h'0) 10seesJo
Homogeneous Reaction Kinetics 302.475 COMMENTS Reaction: (.1) Initial rate only as usual plot of log(l-F) versus time was not linear. In hexane all curves were concave downward and In benzene at 25 curves were concave downward but at 40 they were concave upward. In one case where unlabeled reactants were pre-equllIbrated In hexane at 40 the plot was linear over 90% of exchange with an exchange rate about seven times that for freshly mixed reactants. (.2) Exchange complete within 0.3 seconds. (.3) Addition of (CH)NC10 at 0.1M had no measureable effect on rate of exchange. (.5) Exchange complete within 0.3 seconds. LITERATURE A. D. Alien, G. Modena, CSL 1957, 3671. ( 2 ) A. F. Re id, R. Mills, CSL 1960, 703, 708. i § CO National Bureau of Standards - National Research Council December^ I960