140 XVTI.-Action of Sodzum upon Iodide of Methyl mixed with Ether. F.R.S.E. AND IF. BUGHEISEN, BYJ. A WANKLYN PH.D. PUREmethyl has not yet been obtained. Kolbe's method viz. electrolysis of an acetate yields methyl always contaminated by some foreign body probably oxide of methyl which cannot be conipletely removed. Frankland's method viz. decomposition of iodide of methyl by zinc also gives a mixture which in this case consists of bydride of methyl and free methyl. This hydride of methyl Frankland regards as a secondary product foymed after the gas has left the production tube and due to decomposition of moisture by some zinc-methyl with which the gas as it issues forth is invariably accompanied. Bearing this circ\Jlmstance in mind we determined to try the action of sodium upon iodide of methyl Since sodium-methyl cannot be prepared by such a process we expected to obtain pure methyl.Our expectation mas not realized as will appear in the course of the paper. The iodide of methyl used in our experiments boiled constantly at 43" C. We enclosed in a glass tube some sodium along with a few grammes of iodide of methyl and ether. In order to insure the absence of moisture we next made a short preliminary digestion in the water-bath. Then we let out the first portion of gas which was no doubt contaminated with products due to traces of water adhering to the materials employed in the experiment. After-wards we resealed the tube heated again to 100"C. and collected the gas over boiling water.After having stood in contact with water during a night the gas was analysed according to the method employed by Bunsen. We give the particulars of the analyses :-The gas was divided into two portions one of which was placed in the combustion eudiometer and the other in the absorption tube. WANKLYN AND BUCKEISEN ON IODIDE OF METHYL. 141 I.-h the Eudiometer. I 1 I Volume re- meter ----26*9"C. 0'15085 --Volume of gas taken . . . . . . 72'00 --19.8876 Volume after addition of oxygen . . 180.96 27.1" 0,25844 42.547 ---_ ------Volume after addition of air.. . . 340 90 26.2" 0.41561 159.28 .--.-,---c_-___I_ --308.54 26 '7" 0 38336 1075'4 Volume after explosion . . . . --_II-____.----Volume after absorption of CO ,.276.42 25 5" 0.378 95-221 ----..--L______----Volume after addition of Hydrogen.. 375'0 26.7" 0.4717 161'13 --l__l_-_--Volume after explosion ,. . . 253.98 273" 0 3575 82.23 I 1 &-.In the absorption tube. Volume re- Volume Tempe-Pressure duced to 0°C. sature and 1 meter pressure -___I--meter Volume of gas taken . . . . . . 93-70 26.9" 0.65305 559'06 I Volume after the action of potash 90.63 26.6" 0.6781 55.591 and pyrogallic acid.. . . Volume after the absorption of oleflnes Some gas after the removal of Cd2 oxygen and olefines was transferred from the absorption tube to the eudiometer Its analysis gave the numbers following :- 142 WANRLYN AND BUCKEISEN ON THE ACTION OF SODIUX 1x1.-In ti%e Eudiorneter.26*?"C. 0'16676 12.809 Volume taken ........ -84-32 --- ---.---_I ---.I-26.70 171.12 177-12 Volume after the addition of oxygen . . 399.36 26.7" 0.48686 - ---I-----_I--_ Volume after explosion .... 364.95 27.8" 0.45242 150.11 ---__I_-----__I_-Volume after the absorption of car-} 330.25 car-2S*lo 0.4463 134.99 bonia acid ...... Another analysis of the same gas yielded 2-IV.-Tiz the Eudiornete r. Corrected at 0" C. and one meter pressure Volume taken ................ 10-365 1Volume after the addition of oxygen .......... 260.75 1Volume after explosion .............. 138.40 Volume after absorption of CO ............125.60 I A third analysis of the same gas gave :-V.-.h the Eudiomejeer Corrected at 0' C.and one meter pressure I 1Volume taken ................18.037 IVolume after the addition of oxygen .......... 85.611 I Volume after the addition of air ............198'04 Volume after explosion and absorption of CO ........ 137'05 ---__.--___.---Volume after addition of hydrogen ..........258.61 -----.----Volume after explosion ..............114.73 UPON IODIDE OP METHYL MIXED WITH ETHER 143 Analysis 11. shows that the gas was free from carbonic acid and oxygen. It also shows that 55.706 volumes of the gas contained 5.155 vol. of olefines. In percentage C,H . 9.3 b Gas freed from C,H . . 90.7 _I_ 100.0 Analysis I. shows that 9.8876 vols. of gas contain 0.368 pol. of nitrogen. In percentage nitrogen = 3.7.Analysis V. of the gas free from C,H shows that 18.037 vols. contain 0.21 vol. of nitrogen or 90.7 vols. contain 1.05 vols. of nitrogen. But 100 vols. of the original gas contain 90.7 vols. of gas free from C,H,. Therefore 100 vols. of the original gas contain 1.05 vols. of nitrogen. The determination of nitrogen at the end of a hydro-carbon gas analysis is subject to a little irregularity inasmuch as the small quantities of air introduced in the course of the analysis tell in the aggregate upon the final nitrogen determination. Adopting the mean of our two results we have 2.4 for the per- centage of nitrogen. From Analysis I. we obtain :-In percentage. Original gas . 9.8876 10o'o Nitrogen . . . 0.237 2.4 Combustible gas .. 9.6506 97.6 Oxygen consumed . . 24*4084 246.9 Carbonic acid formed . 12.519 126.6 Analyses III. IV, and V. all of the residual gas after removal of C,H give :-III. Iv. V. Mean. Combustible gas . 12.507 10.091 17.560 88.3 Oxygenburnt . 29.623 25.059 43.430 215.7 Carbonic acid formed 15.120 12.80 __. 109.1 To arrive at the condensation of the olefines we make use of the following data :-100 vols of the original gas are composed of 9.3 vols. of C,H,. 2.4vols. of nitrogen. 88-3vols. of residual hydro-carbon. 144 WANKLYN AND BUCKEISEN ON THE ACTION OF $ODIUM And on combustion furnish 246.9 voh oxygen consumed. 126.6 vols. carbonic acid. 88.3 vols. of the residual hydro-carbon gas furnish 215.7 vols. oxygen consumed.109.1 vols. carbonic acid. Hence the 9.3 vols. of C,H furnish 31.2 vols. oxygen consumed. 17.5 vo1s. carbonic acid. The C,H, therefore has the condensation of ethylene which requires Vol. taken . . 1.0 Oxygen burnt . 3.0 Carbonic acid . 2.0 With so low a percentage of CnHn as is present in the gas under examination great accuracy in the determination of its con-densation is not to be expected; the very indirect manner of arriving at the result having the effect of concentrating the errors of the whole analysis upon the small percentage of olefine. The 88.3 vols. of hydro-carbon must consist for the most part of marsh gas. Some other more complex hydro-carbon is also present ;but what other cannot be revealed by a mere combustion analysis.If the hydro-carbon be very complex then the percent- age of marsh gas must be high ; if less complex then the percent- age of marsh gas falls. Assuming that the accompanying hydro-carbon is methyl in which case the proportion of marsh gas reaches its lowest we have for the composition of the gas C** ' 9-8 0 Nitrogen . . 2.4 Hydride of methyl 65.0 Methyl * . 23.3 1oo*o As ie well known a combustion cannot distinguish marsh gas from a mixture in equivalent quantities of methyl and hydrogen. UPON IODIDE OF' METHYL MIXED WITH ETHER 145 That our marsh gas was such a mixture was highly improbable. Direct proof we have rieverttrieless sought in another experiment We made a fresh quantity of gas collected it over strong alcohol (previously boiled) and shook it up therewith.Since methyl is very tnuch more soluble in alcohol than is hydrogen the gas discharged from this alcohol by boilinr should have been very rich in methyl. After washing with water however it yielded 011 combustion numbers agreeing with the composition of hydride of methyl viz. :-Contraction Carbonic A cid. 10.31 5-27 Wydride of methyl requires contraction to carbonic acid in the ratio of 2 :1. This gas also contained hardly my olefine viz. only 2.7 per cent. We have thus established the fallowing conclusions :-At 100°C. sodium decomposes iodide of methyl in presence of dry ether yielding a large quantity of hydride of methyl. The equation expressing the production of the hydride is neither of the following :-Na + Z(C,H,I) = 2NaI + C,H 4-C,H Na + 4(C,H,I) = 4NaI + C,H + 2(C,H,) because the amount of C,H is too small for the hydride of methyl.What the product complementary to the hydride of methyl really consists of we have not yet been able to determine. In conclusion we have to add that we have repeated the experi- ment and obtained similar resiilts to those which we have described in the paper With potassium likewise the same peculiarity has bceri observed as with sodium. The further ivvestigation 9f the subject viill be made by one of us. 14,L.XIIL.