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Abstract, .I he thcrrllal deco11ll)ositioll of r l~r * xa.; t l i~c l l p h u r tlccaflu~~r-ide Ilas 0ec11 stutlicrl i l l a rlletal reactor. :\i~aly~ical c\.irlellce silo\\-etl t l~a t tile r-ctnrliou proceccls accordillg to tile ccll~ation S~FI,, = SF6 + SF.,. 7.11~ reaction \\-as io~crltl to I)c largely I~onrogr~lc~~~s, as t h e hcrcrojicllco~rs rcac.~irr~l accol~rlted for l e x i tllilll 5C; of ~I L C totill process. ?'he ~O I I I O~C I I~O L I S r l~; l ( . t i~l l was sho\\.~l to be lil-st ortlcr, anti in tile tculpcriltl~re rarlge ir~\.cst-ignted the rate is ci\.cl~ 1 ) . 111 k = -k7.O<) --10,20O/RT. : \ chair) r c a c t i o~~ ii p o~t t l l n t c t l LO cxl~laill tllc obsert-cd rate oi the reacriorl. 'File eliect of nit[-ic o\irlc alicl ,~c-ct>.leilc: rlichlol-icle o n thc rate ancl [~rotluctj: oi the r-cacti011 \\its illvesrig-atccl. It is apparent t h a t tlicsc sull~holl~~ot-ides Iia1.e a st~.ucture coinpn~;tblc to . ~ that ol the l~y t l~-o c a r l~o~~s ant1 thc f1~1oroc;rrbons. The!. are similar a s well in that the 11e1-ip11ernl bontls (S-F, C-1-1, C-F) al-c con side^-nblg. strorlgcl-t-ha11 t-he central bontl (S-S, C-C) in each t!.pe. Significant tliffel-ei~ces berween the series arc the ~~ossibilities of u~l s a t i~~-n t i o n i i i tlie carbon compountls, ant1 the facilit!. with ~vhich SLIIPIILI~ forllis stable com[~otintls in difereut valence states.This combi,nation of siinilai-ity ailel tlissin1ilarity suggested t h a t a study of the thermal decomposition of t l i s~r l p l i~~r tlecafliioridc nlight be a n-ortll\vhile extension ol experimental kinetics. For personal use only.TROST AND AlciSTO.5I-I: I I I E R J I . I L UECOdlPOSITlOI1; OF DIS[~LPIIC'R I!EC.ll:LL'ORIDE 50:) Experimental AlnterialsT h e crude gas was purihed 1131 passage through co~lcentratcd caustic ancl n7as then fractio11:lrecl rlntil n 1)rocluct \\.it-h a vapor pressure ol 2.13 mm. at 0°C. and a m o l e c~~l a r weight of 256-257 a t 180 mm. pressure was obtained.Compared with I-cported d a t a (3), these values i~lclicatc t h a t t h e tinal product \\;as 99-100% pure. A pjaratz~sSince disulphur clccafluoride rcacts \:igorousl). \\it11 glass or niel-c~~r); a t higher ten1perat~11-cs a n inert metal reactor ancl nietal 1)ressul-c measuring instrument were rccluired (1;ig. 1). The assemblj-corisistccl of n copper c~~linclcr I< closecl a t the bottom entl 115' a [)ressure sensitive co[-~-~rgatkcl brass dia11li1-agrn D. A licl~~id filler ancl manorncter system tl-anslatecl the [)I-cssure of the membrane into a pressu~-c reacling. 'The 0.003 in. ~llcmbranc D, -L in. in dinmeter, coxrered the oil-tilled clia1)Iiragnl c h a m l~e r C . In .\, the mercur\-used in the U-tube I; came into rontnct with the clibut>-1 l)l~tlialate used ill C. Tlie level of the mercury in I;, as read from the scale N, was ~~tilizccl a s (-he null indicator. T h e pressures ~-ccl~~il-ecl to reproduce the null Ic\.cl \\.crc measured on the absolute ~nanonieter 13. A slightly clc\rated ring L, ancl lcacl gaslcets, provided a n eficcti\-c vacuum seal \\,he...

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Addition compounds formed between silicocl tetrachloritle and some amines have been prepared and analyzed. IVIolecular ratios of 4 / 1 , 2 / 1 , and 1/1 were established for amilie to silicon tetrachloride in these compounds. I t is suggested that these molecular conipou~lds use Is, 3d, 4p orbitals only, in forming the coordinate bonds that establish the compound, and that the configuration of the silicoll tetrachloride remaills essentially undisturbed. Use of these assumptions perrnits,definite structural predictions to be made about the compounds.