(3) Everett, A. J., Mintoff, G. J., Trans. Faraday SOC.49, 410 I 1953). (4),Gigu$re, P. A., Olmos, A. W.,Can. J . < hem. 30, 821 (1952). ( 5 ) Jefi'rey, G., Univereity of Pittsburgh, Pittsburgh, Pa., unpL blished data. (ti) Kitsatoclikin, V., Pe,-lina,S., Ablesova, I< , ('ompt. Rend. A c c d . Scz. CRSS 47, :%ti (1945'). (T) Lobunez, W.,Rittenhouse, J. R., )Tiller. J. G.. J . Ani. Chem. SOC.80. :3.505 ('19581. ' ( 8 ) Parker, J?. E., Ricciuti, C , Ogg, C. L., dwern, D., Ibid., 77, 4037 (1955). ( 9 ) Penney, W.G., Sutherland, G. B. B. AI., Trans. Faraday SOC.30, 898 (1934); J . Chevz. Phys. 2,-492 (1934).
(10) Redington, R. L., Olson, IT. B., Cross, P. C., Zhzd., 36, 1311 (1962). (11) Rittenhouse, J. It., Lobunez, W., Swern, D., Miller, J. G., J . Am. Chem. SOC.80, 4850 (1958). (12) Rogers, hl. T., Campbell, T. W,, Ibad., 74, 4742 (1952). (13) Silbert, L. S., J . -4m.Oil Chcmisls' SOC.39, 480 (1962). (14) Silbert, L. S., Lutz, D., Siegel, E., unpublished data from this laboratory. (15) Silhert, L. P.,\Vitnauer, L. P., Swern, I)., Ilicciuti, C., J . -4m. Chem. SOC.81, 3244 (1959). (16) Swern, I)., Chpm. Revs. 45, l(1949). (17) Swern, D., JYitnauer, L. P., Eddy,
C. R., Parker, IT;. E., J . Am. Chent. SOC. 77, 5537 (1955). (18) Walsh, A. D., J . Chem. SOC.1948,331. (19) Wolf, R., Bull. SOC.Chim. France 1954, 644. RECEIVED for review December 7 , 1962. Accepted February 19, 1963. Symposium on Organic Peroxides, Division of Analytical Chemistry, 142nd Meeting, ACS, Atlantic City, N. J., September 1962. The Eastern Regional Research Laboratory is a Laboratory of the Eastern Utilization Research and Development Division, Agricultural Research Services, U.S. Department of Agriculture.
Gas Chromatography of Organic Peroxides S. W. BUKATA, L. L. ZABROCKI, and M. F. McLAUGHLlN lucidol Division, Wallace & Tiernan, Inc., Buffalo 5, N. Y.
b Gas chromatographic methods for the separation and estimation of organic peroxides are! discussed. For quantitative analysis the internal standa r d technique i s used. The relaiive standard deviation for the determination of high purity di-tert-butyl peroxide i s *0.3%. The peroxides, 2,5-dimer hyl-2,5- di(tert-butylperoxy)hexane, fert-butyl peracetate!, and 2,5-dimethyl- 2 3 - d i ( tert- b u t y l p e r o x y ) - 3 hexyne can b e determined with a re1 .Oy;. lative error of
-
*
G
IvroYidc- hau been tlc-cribcd in the literature (1-3, 5 , 6 , 9, I O ) Di-terthut1 1 peroxide ( 2 , 'f), tert-but! l-tertIicntyl pcrouitlc ( Z ) , tert-pentyl hvdroIicroxide ( Z ) , all! 1 h? dropciouide ( 5 ) . a i d the 1-oineric iutT 1 hydroperoxides (1-3, I O ) h a r e been successfully .rimrated by GLC. Previous investigators have used columns of Celite, diatomaceous earth, Flrebrick, or kieselguhr impregnated n ith a silicone oil or a phthalate eqter in the temperature range of 38" to E5" C. However, a n evaluation of GLC of organic peroxides a i t h regard i o accuracy and reproducibility is lacking. I n this paper GLC data for other organic pcioxidcs are g i w n and quantitatil e analysis data ire discussed. EXPERIMENTAL
Apparatus. A Perhin-Elmcr, Model 134C, T'apor Fractometcr with a tlicrmistor detector n'is u d . I n thr, noriixil operation of t h e instrument t h e injcction port temperature is considerably higher 1h a n t h e column tcmperaturr to olhtiii better chromatogram- ( 7 ) 1Jntk.r suc~hcondition, t h e I)ero\itle frequeiitl~ decomposes a t the port because of the higher port tcm1)ciature n h e n tlie column tem-
perature is 70" C. or greater. T o avoid ?t.comno-ition, the cartridge heater leads for the injection port block were discmnectpd from the instrument's S'ariac. Helium a a. used as the carrier gar at a flow rate of about 230 cc. per minute a t 70" F. Sample size was about 1 11. One- and 2-meter PerkinElmer A (didecvl phthalate on diatomaceous earth) and 0 (silicone grease on diatomaceouq earth) columns n ere used. Procedure. For quantitative analw i s t h e inttrnal standard method usinq peak heights was used. T h e standard and sample solutions mere prenared with t h e internal standard w c h t h a t the peak heights of t h e perouide and internal standard were cioqe t o t h e same height. DI-teTt-BUTYL PEROXIDE.Samldes of high purity di-tert-butyl peroxide n ere analyzed uqing n-heptane as the internal standard a t 80" C. on a 2-meter .A column u i t h a rccorder range of 0 to 5 mv. Llixtureq of approximately 1 8 parts by neight of peroxide and 1.0 part of n-heptane were used for analysis. Triply distilled di-tertbutyl peroxide was used for preparation of the calibration standards Its purity n-as assumed to be 99.9%, based on the gas Table 1.
chromatogram of the material. Only the peak attributable t o di-tert-butyl peroxide was observed. tertBuTYL PERdCETATE. SolUtiOns of tert-butyl peracetate i n benzene were analyzed b y GLC using a 1-meter A column at 100' C. and a recorder response of 0 t o 5 mv. The internal standard was n-nonane. GLC mixtures consisted of 2.6 parts of peroxide solution and 1.0part of n-nonane. A 75.6% solution of tert-butyl peracetate in benzene was used for preparation of the calibration standards. The samples of tert-butyl peracetate were also analyzed b y a hydrolysis procedure. A 0.7- t o 0.8-gram sample was weighed into a 250-ml. glass-stoppered Erlenmeyer flask containing exactly 25 ml. of standard 0.3N sulfuric acid. The mixture was refluxed for 1 hour a n d cooled, and to this was added b y pipet 50 ml. of standard 0.25N NaOH. The solution n-as then titrated to the phenolphthalein end point with 0.1N KaOH, or 0.1N HC1 if the solution was alkaline. The difference betveen the equivalents of base added and the equivalents of acid (HZSO, HCl) represented the equivalents of acetic acid formed by hydrolysis of tert-butyl peracetate. One
+
Retention Times for Some Organic Peroxides
Cornpound tcrt-Butyl hydropcro\ide tert-Pentyl hydroperoxide tcrt-Butyl peracetate t r rt-Butyl peroxyiso bu tyrate 13-tert-butyl peroxide I )i-tert-pentvl peroxide 2,5-I)imeth~I-2,5-di(tert-
Columna
Temp., C.
2m-.\ I rn-.\ 1m-Al 1m-Ll
80 80 100 100 80
2n1-h 1m-A
but\ lpwoxy)-:Hare, .)I G , . White, R. F. &I.,J . Chein. Sgc. 1960, 1040.
(4) Dickey, F. If., Rnley, J. H., Jiust. F. F., Treseder, It. S.,1-aughan, \ \ . E., Ind. Eng. ( ' h e m . 41, 1673 (1949). ( 5 ) Ihkstra, P..llosher, H. S.,J . A m . Chem. SOC.79, 3474 (1957). ( 6 ) Martin, 1.J., "Organic .4nnlysis," \lrham, 1,. ,J.. M ) s l i e l ~ 11. , S , , /hi(/.,80, 327 (19.58).
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