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Mass Spectra of Octanes by Evelyn G

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Mass Spectra of Octanes by Evelyn G U. S. Department of Commerce Research Paper RP1912 National Bureau of Standards Volume 41, August 1948 Part of the Journal of Research of the National Bureau of Standards Mass Spectra of Octanes By Evelyn G. Bloom, Fred L. Mohler, J. H. Lengel, and C. Edward Wise Mass spectra of the 18 isomers of octane have been measured. The sensitivity at the maximum peaks in each spectrum relative to n-butane is computed as well as the total ionization relative to n-butane. Tables and plots of relative intensities in the mass spectra are given, and some correlations with structure are found. All isomers with a tertiary butyl radical have similar spectra. The other isomers tend to dissociate at carbon atoms with one or two side chains attached to them. This determines whether the loss of two or three carbon groups in dissociation is probable. Loss of four carbon groups is probable whenever the molecule ion can break in half in a single dissociation process. I. Introduction Relative intensities of mass peaks are expressed in terms of the maximum peaks taken as 100 Mass spectra of the 18 isomers of- octane have percent and include intensities down to 0.01 been obtained as part of a systematic survey of x percent. The sensitivity at the maximum peaks mass spectra of pure hydrocarbons. It is of is measured in terms of the scale divisions of interest to compare the spectra of these isomers galvanometer deflection per micron pressure in and look for possible correlations between the the gas reservoir. The sensitivity at the mass structure- of the molecules and the mass spectra. 43 peak of n-butane is recorded for each octane These octanes are the highest molecular weight spectrum, and the ratio of sensitivity of an saturated hydrocarbons for which pure samples of octane to that of n-butane is a molecular property all the isomers are available. nearly independent of the arbitrary units used. Unpublished mass spectra of the octanes have Details of the mass spectral data are given in the also been computed by the Consolidated Engineer- API mass spectral catalog (see footnote 1). ing Corporation for users of their mass spectrom- The compounds used were with one exception eter. A paper on mass spectrometer analyses of 2 National Bureau of Standards standard samples of some liquid hydrocarbon mixtures describes the specified purities between 99.5 and 99.94 mole practical problems of analysing mixtures contain- percent. Tetramethylbutane (the only solid ing octanes by means of these mass spectra. octane) was a sample of better than 98 mole percent purity obtained from the Ethyl Corpo- II. Experimental ration by API Research Project 6. Mass spectra have been obtained on a 180° Consolidated mass spectrometer equipped with III. Results automatic control of the electron current and Sensitivity and total ionization.—Table 1 gives automatic temperature control of the ionization data on the sensitivity and total ionization of the chamber. Standard procedures have been fol- octanes as compared with n-butane. Column 1 lowed, and these are given in detail in the API lists the 18 isomers in the order of increasing com- Catalog (see footnote 1). Mass spectra were plexity of side chains. Column 2 gives the max- measured with 50- and 70-v ionization potential, imum mass peak in each spectrum, and in most and the values at 50 v are quoted here. cases it is mass 43. Four isomers have the max- 1 Catalog of mass spectral data, American Petroleum Institute, Research imum at 57, and these are the isomers that have a Project 44, National Bureau of Standards, Washington 25, D. C. tertiary butyl radical C(CH3)3, and in the case of 2, 2 R. A. Brown, R. C. Taylor, F. W. Melpolder, and W. S. Young. Anal. Chern. 20, 5 (1948). 2,3,3-tetramethylbutane, both halves of the mole- Mass Spectra of Octanes 129 cule have this structure. Evidently molecule ions TABLE 1. Octane mass spectral sensitivity containing this grouping have a high probability of splitting in half. Sensi- tivity at Total Column 3 gives values of the ratio of sensitivity Maxi- maximum ionization Compound mum peak (relative at the maximum octane peak to the sensitivity at peak (relative to n- + to 7i- butane) the 43 peak of 7i-butane. This ratio ranges in butanea) value from 1.40 to 2.76 with no obvious relation w-Octane 43 2.46 3.12 between the value and the molecular structure. 2-Methylheptane 43 1.87 2.52 The sum of all the mass peaks in a spectrum 3-Methylheptane 43 1.60 2.42 4-Methylheptane 43 2.13 2.29 multiplied by the sensitivity gives the total ioniza- 2,2-Dimethylhexane 57 2.76 2.14 tion in arbitrary units, and this number divided 2,3-Dimethylhexane 43 L. 63 1.94 2,4-Dimethylhexane 43 L. 42 2.07 by the total ionization of ^-butane is a molec- 2,5-Dimethylhexane 43 1.56 2.08 ular property nearly independent of instrumental 3,3-Dimethylhexane 43 L. 58 1.97 factors. This ratio given in column 4 of table 1, 3,4-Dimethylhexane 56 L. 40 1.84 3-Ethylhexane 43 2.45 2.43 is 3.12 for n-octane and 1.86 for 2,2,3,3-tetra- 2,2,3-Trimethylpentane-.. 57 2.24 2.09 methylbutane with most other values intermedi- 2,3,3-Trimethylpentane... 43 1.80 2.15 2,3,4-Trimethylpentane 43 1.99 2.15 ate. It is evident that total ionization depends 2,2,4-Trimethylpentane.. _ 57 2.53 2.03 on molecular structure though the correlation 2-Methyl, 3-ethylpentane. 43 1.98 2.20 3-Methyl, 3-ethylpentane. 43 2.14 2.25 with structure is again not obvious. 2,2,3,3-Tetramethylbutane 57 2.44 1.86 Relative intensities.—Table 2 lists the relative peak heights of 17 mass peaks in the octane spectra Corrected to 0.675 A magnet current from 0.535 A values. TABLE 2. Mass spectra of octanes Percentage of maximum peak at m/e values indicated Compound 114 112 99 85 84 71 70 69 57 56 43 42 41 29 27 15 (1) 7i-Octane __. 6.9 0.02 0.1 30.0 6.0 23.5 12.2 1.3 34.2 18.1 10.2 100 15.8 34.5 26.2 2.2 (2) 2-Me heptane 4.9 .04 12.6 1.8 0.8 12.9 17.2 1.3 73.3 8.1 11.1 100 41.9 38.2 27.7 25.3 3.1 (3) 3-Me heptane 3.0 .02 0.8 49.0 27.3 3.1 2.5 2.7 67.5 38.3 11.2 100 7.9 45.9 40.7 27.8 2.8 (4) 2,4-Me2 hexane 1.7 1.1 46.1 9.0 14.9 9.8 4.2 72.8 29.6 9.9 100 11.0 43.4 32.4 24.2 3.6 (5) 2,5-Me2 hexane-_ 3.8 2.02 17.3 0.7 0.2 18.8 9.7 1.4 80.2 7.6 10.9 100 34.0 38.2 21.1 23.3 4.4 (6) 3,4-Me2 hexane 2.2 0.3 18.1 7.3 1.5 1.9 3.3 79.2 100 9.9 68.1 4.0 56.5 48.0 24.5 2.7 (7) 3-Et hexane 1.6 .1 28.5 22.6 13.5 12.9 2.5 12.4 5.9 11.6 100 6.7 22.8 19.8 19.3 1.7 (8) 2-Me,3-Et pentane.. 1.3 .1 18.1 4.3 24.7 50.0 3.3 14.8 2.9 17.9 100 14.2 27.0 18.7 19.2 2.2 (9) 3-Me,3-Et pentane_. 0.00 1.9 64.3 16.8 0.5 0.6 5.8 27.0 2.6 8.0 100 2.4 25.0 21.2 17.5 1.7 (10) 2,2-Me2 hexane 5.6 0.02 0.01 .7 .3 0.8 100 32.2 4.6 15.9 1.8 26.3 18.6 11.3 2.4 (11) 2,2,3-Me3 pentane. 0.01 3.0 2.9 .2 .4 .5 1.2 100 57.5 5.8 22.8 2.2 33.4 23.0 11.4 2.9 (12) 2,2,4-Me3 pentane-_ 4.7 0.01 .05 .8 .2 0.5 100 32.7 4.0 23.1 2.0 27.4 15.4 10.7 3.6 (13) 2,2,3,3-Me4 butane. .03 6.2 .03 .3 .3 .1 1.3 100 27.3 4.5 17.7 1.5 28.2 16.2 7.0 4.7 (14) 3,3-Me2 hexane .01 36.1 7.6 47.0 17.1 3.5 40.7 5.3 11.9 100 3.7 29.4 22.8 20.8 3.0 (15) 2,3,3-Me3 pentane. 3.5 25.0 3.5 45.3 35.5 3.5 35.8 1.5 15.7 100 5.4 16.0 18.2 3.2 (16) 4-Me heptane 3.1 .02 0.9 4.5 3.0 52.7 46.1 1.3 14.4 2.4 15.3 100 13.5 26.6 22.8 22.5 2.4 (17) 2,3-Me2 hexane 1.7 .4 1.5 0.4 46.4 58.3 1.6 16.7 1.6 19.8 100 18.9 28.6 19.0 21.6 2.9 (18) 2,3,4-Me3 pentane- 0.3 .2 0.2 1 61.9 40.6 0.9 16.3 2.0 17.1 100 7.4 24.5 13.6 18.2 3.3 and figures 1,2, and 3 show graphically 15 of the structural formulas that omit the hydrogen atoms.
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