Table VI. Ultraviolet Analysis of Known Chloramine and Chlorine Mixtures
Mixture NCh C18
+ Clr + NCli
Concn., lo-’ G./MI. % Present Found Recovery 0.06 0.048 96 0.45 0.43 95.6 95.6 0,110 0,106 0.205 0.207 100.9
c1*+
:;;!:::;!:‘ti:
NCls
+ c12 + NCla c11 NCI,
NH&l NCI,
+
0.133 0.149
0.135 0.152
101.5 102
0.067 0.037
0.068 101.5 0.040 108.1
0.040 0.089
0.038 0.088
95.0 98.9
a n aliquot of the solution is extracted with several successive portions of carbon tetrachloride and the combined extracts are dried, diluted to known volume, and analyzed by the ultraviolet method. Analysis of Mixtures of NCls and Clz. A common mixture encountered is a mixture of NCls and chlorine,
since chlorine is a product of decomposition of NCls. The chlorine absorption peak at 335 mh does not interfere with the 265 NCls peak so that the NCla content can be determined directly from the 265 absorbance. It is then a simple matter to correct for NCla and determine the chlorine by difference from the reading a t either 336 or 345 mh. Mixtures were prepared from standard solutions of chlorine and NCls in carbon tetrachloride and analyzed by ultraviolet. All solutions used in these mixtures were dried and assayed prior to mixing. Some quantitative results are shown in Table VI. The results were arrived at by graphic solution rather than by calculation using simultaneous equations. The recoveries range from 95 t o 108%. Other Mixtures. Carbon tetrachloride solutions containing various chloramines were mixed and ultraviolet scans were taken of t h e mixtures. No quantitative analyses were attempted. A mixture of monochloramine and chlorine showed dichloramine formation. The pattern changed with time. A mixture of mono- and trichloramine also showed dichloramine formation and the reaction appeared to progress with time. A mixture of
di- and trichloramine showed no ultraviolet pattern change. A mixture of mono- and dichloramine appeared to form a stable system, initially, but one which appears to be time limited. LITERATURE CtTED
(1) Audrieth, I,. F., Colton, E., Jonea M. M., J. Am. Chem. boc. 76, 1428-31 (1954). (2) Chapin, R. M., Ibid., 51, 2112-17 (1929). (3) Coleman G. H.,Nitrogen Trichloride Studies, Ofhe of Scientific Research and -I, .^.^ RePt- No. 858, August Development, lY4L. (4) Coleman, G. H., Johnson, H. L., “Inorganic Syntheses,” Vol. 1, p. 69, McGraw-Hill, New York, 1939. (5) Corbett, R. E.,Metcalf, W. S., Soper, F. G., J. Chent. SOC.1953, 1927-9. (6) Dowell, C. T., Bray, W. C., J. Am. Chem. SOC.39,896(1917). (7) Kleinberg, J., Tecotzky, M., Audrieth, L. F., ANAL.CHEW26, 1388-9 (1954). (8) Metcalf, W. S., J. Chem. SOC.1942, 148-50. (9) Noyes, W..A., “Inorganic Syntheses ’’ Vol. 1,. *D. 65, . McGraw-Hill, New York, 1939. (10) Williams, D. B., Water and Sewage Works 1951,475-7. RECEIVED for review November 16, 1960. Accepted February 23, 1961. Pittsburgh Conference on Analytical Chemistry & Applied Spectroscopy, Philadelphia, Pa., February-March 1960
Mass Spectra of Aliphatic Thiols and Sulfides E. J. LEVY, The Atlantic Refining Co., Philadelphia, Pa. W. A. STAHL,’ U . S. Quartermaster Research and Engineering Center, Natick, Mass.
b Mass spectra molecular structure correlations for thiols and sulfides were developed during an investigation of the components responsible for odor changes in irradiated beef. By using these correlations a compound can b e identified as a thiol or a sulfide. The thiols can b e further classified as primary, secondary, or tertiary, and the sulfides can b e identified as to the carbon number of the alkyl substituents and the degree of cy branching. The major fragmentation ions of the thiols can b e classified into four types: the molecular ion less CnHgn+l and the molecular ion less each of the groups, SH(CH2),, SH*(CH2),, and SH3(CH2),. The sulfides show similar fragment ion series plus two additional types, R-SHf, and R-SHzf, formed by the loss of C,H*, and C,,H~,-I, respectively, from the molecular ion. Cleavage of the /3 carbon-carbon bond to
Present address, McCormick & Co., Baltimore, Md.
yield sulfur-containing fragment ions is most prevalent in the thiols and lower molecular weight - sulfides, but a-bond cleavage becomes important in the symmetrical sulfides of higher molecular weight.
results of an investieation into components of irradiated beef demonstrated the importance of sulfur-containing compounds as odor constituents (16). To aid in the identification of thiols (mercaptans) and sulfides for which calibration compounds may not be available, mass spectra molecular structure correlation rules were sought. The correlations resulting from this study enable a compound to be identified as either a thiol or a sulfide and then assigned to a structural class within each sulfur compound type. Previous correlation studies have been made for many classes of compounds. These include alcohols (4,II), aliphatic acids ( 7 ) ,acetals (S),ald-hydes -HE
1 the off-odor
(6), ethers (9), esters (Id),thiophenes ( 8 ) , lactones (6), ketones (IS),halides (IO), and hydrocarbons (1, 12). It
has been shown that a molecular ion aftcr formation will dissociate into fragment ions in a random statistical manner whm no weak bonds or directing functional groups arc present. For thiols and sulfides, dissociations are very strongly influenced by the sulfur atom and generally occur a t bonds a,8, and y to the functional group, often with rearrangement. EXPERIMENTAL
The mass spectra of 29 mercaptans and 31 sulfides were examined. The spectra of compounds containing up to eight carbon atoms were either from API Project 44 or obtained from samples run a t the Quartermaster Research and Engineering Center using a Consolidated 21-103B mass spectrometer. These samples included compounds purchased from Eastman and purified by gas chromatography or API standard VOL. 33, NO. 6, MAY 1961
707
Table 1. Mass 22322MethylMethylMethyl- Methyl- MethylCom1211221231-bul-buZbupound Methane Ethane Propane Propane Butane propane Butane propane Pentane Pentane Pentane tene tane tane E E Bourc@ E E A A 911 E A 967 921 A 1413 1882 Carbon 2 4 No. 1 3 4 4 3 4 5 6 6 5 6 6 76 02 Mol. wt. 48 90 70 90 90 90 104 104 104 104 104 104 12 13 14 15 16 23 24 25 20 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59
80
61 62 63 64 65 66 67 08 ' 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89
708
2.4 3.6 4.8 11.5
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0.0 0.9
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0.8 3.4 22.4 79.0 38.0 89.5 2.2
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...
6.3 6.6 1.6 0.3
...
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9.6 56.7 13.0 100.0 77.5 5.8 3.4
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0.2 0.2 9.2 57.2 24.0 39.0 1 .o 0.6 3.9 4.3 4.0 10.6 0.7 2.4 3.9 22.2 5.4 92.2 8.4 26.1 1.9 17.1 10.9 48.3 7.5 4.1 2.1 1.8 0.5 2.4 1.6 14.7 -100.0 . 18.7 5.6 5.1 3.5 21.3 1.8 1.2 0.2 0.1 0.2 0.2 0.2 0.9 0.3 0.7 0.1 0.7 0.2 0.2 0.1 0.2 0.1 0.1
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0.4 4.7 44.6 2.4 28.4 0.7 0.3
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0.6 9.2 55.4 11.5 81.3 1.9
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Spectra of Thidr 32,2,1-Di24 4 22 22Methyl- methylMethyl- Methyl- Methyl- MethylEthyl- Methyl1-Dec- 1-Undeo-Zundes MeihylZbu11-pen- 1-pen- %pen- %pen111-hex- Z h e p 1Eexane tane tam tan0 tane Heptane Octane SILe tali0 Nonane m e tune ane ane P 1242 1235 1244 918 1243 C C P C 943 1384 BM P C 6 104
6 104
6 118
6 118
118
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6 118
7 132
8 140
8 140
8 146
9 160
10 174
11 188
12 202
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0.1 0.2 3.1 43.4 4.3 18.9 0.6 0.1 1.2 3.5 2.8 6.5 0.2 1.7 3.5 38.3 5.3 82.6 19.1 100.0 3.4 9.7 1.4 13.2 0.4 1.0 1.4 2.2 0.7 4.3 0.9 11.4 8.6 14.1 4.2 9.1 11.o 80.7 2.9 3.3 0.2 0.8 0.3 0.3 0.9 89.9 5.0 1.o 0.1 0.6 2.7 11.3 1.3 0.7 0.1 0.1
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0.9 2.4 37.9 5.8 88.2 22.0 59.7 2.6 11.1 3.3 29.2 1.5 1.7 1.9 3.6 1.7 10.2 5.5 72.9 35.2 100.0 4.7 2.2 1.6 4.1 0.5 0.8 0.2 1.3 0.6 4.4 2.9 17.7 52.9 8.4 0.4 1.4 0.5 0.9 0.1 0.8 0.2 0.7 0.2 1.2 2.3 18.9 8.9 2.7 0.4 0.4 0.4 2.6
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0.7 1.3 16.8 2.7 42.0 3.8 18.4 2.3 2.2 0.8 4.2 0.4 0.5 1.o 1.6 0.6 1.0 0.9 24.7 15.6 100.0 6.9 3.1 0.5 2.2 2.0 0.4 0.2 0.6 0.3 1.3 0.4 5.7 2.5 1.6 0.2 0.4 2.7 20.6 1.2 1.6 0.3 0.6 0.1 1.0 0.3 1.6 0.4 0.3
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0.7 1.6 39.2 6.3 100.0 36.6 76.2 2.6 12.6 4.8 39.3 1.7 1.9 0.8 1.9 1.0 7.8 8.5 70.0 72.1 31.9 1.8 3.4 4.8 16.5 1.2 1.0 0.1 0.9 0.5 5.7 16.3 43.8 46.1 10.7 0.5 1.3 0.5 0.8 0.2 0.6 0.1 0.6 0.1 1.5 6.4 24.8 21.9 5.1 0.3 1.3 0.7 10.3
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0.6 1.3 32.1 5.9 100.0 33.0 79.8 2.7 11.0 4.0 36.7 1.5 1.8 0.6 1.5 0.8 7.7 8.9 73.4 54.8 37.6 1.8 2.9 4.6 15.3 1.o 1.0 0.1
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0.5 1.o 29.1 6.2 100.0 30.0 87.2 3.0 8.5 3.2 31.4 1.2 1.5 0.5 1.3 0.8 7.5 9.3 73.6 50.4 44.4 2.1 2.4 4.2 13.7 1.o 0.8 0.1 1.0 0.7 8.2 17.3 45.0 41.2 15.6 0.8 1.3 0.5 0.8 0.1 0.6 0.2 0.8 0.3 2.6
... ...
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...
...
0.7 1.4 36.4
- - - 100:0 11.9
1
.o
0.7 6.9 17.3 42.6 50.5 12.0 0.6 1.2 0.5 0.7 0.1 0.5 0.2 0.6 0.1 1.7 9.3 31.6 22.0 6.2 0.4 1.5 1.1 11.3
71.7 2.5 0.8 0.1 1 .o 0.1 0.1 1.1 3.5 2.0 4.0 5.6 84.9 28.2 60.4 2.8 0.6 0.6 1.6 0.3 0.8 0.2 3.0 1.5 13.3 6.0 82.6 43.6 21.1 1.1 0.2 0.7 0.7 0.1 3.2 0.7 3.3 0.7 7.5 4.3 11.1 48.7 33.9 31.2 25.8 11.2 8.3 0.7 0.5 0.2 1.7 0.2 i.2 10.9 0.4 (C o d n u e d )
VOL 33, NO. 6, MAY 1961
709
~~
Table 1. Mass 322MethylMethyl- Methyl- MethylCom12 1122 1231-bu1-buZbutane pound Methane Ethane Propane Propane Butane propane Butane propane Pentane Pentane Pentane tane tane 1382 A E A 911 E A 1413 E 967 921 A E Sourcefli’ E Carbon 4 4 4 5 5 5 4 5 5 1 2 3 3 5 No. Mol. wt. 104 90 104 104 90 90 90 104 104 104 76 48 62 76 mle 0.1 ... , . 51.6 60.8 50.4 ... ... ... ... ... 51 3 0.1 4.G 90 0.2 ... , . . ... 3.2 2.9 2.6 2.8 0.3 ... 0.3 91 , . . ... 2.4 2.4 ... , . 2.3 ... ... ... 0.1 ... 0.2 2.8 92 ... ... , . . 0.1 0.1 ... ... , , . , . . ... ... 0.1 , . . ... 93 ... ... . . .. ... ... ... ... ... ... ... ... . . , 94 ,.. ... ... .. ... , . ... , . . ... ... ... ... ... 95 ... ... , . ... ... .. ... . . ... ... ... ... ... ... 96 0.1 0.1 ... ... ... . . ... ... 97 ... ... 0.1 0.2 ... ... , . ... ... ... ... ... ... ... ... 98 0.4 ... ... . . ... ... ... ... . . ... 99 ... ... 0.2 ... 0.1 ... ... . , . . ... ... ... . . ... ... ... ... 100 , . ... ... 101 ... ... ... ... ... ... . , ... 0.1 ... ... 102 ... ... . . ... ... ... ... ... ... ... 0.1 ... 0.2 103 , . ... ... ... ... ... ... 0.2 0.5 0.1 21.1 43.2 ... ... ... ... ... ... 104 ... ... 39.7 40.4 32.2 40.9 1.3 2.8 ... ... ... ... ... 2.7 ... 105 2.2 2.6 2.5 1.0 2.1 1.9 ... . , . ... ... ... ... ... ... 106 1.9 1.9 1.5 0.1 *.. ... , . ... ... 0.1 107 , . . ... ... ... ... 0.1 0.1 ... ... . . . ... ... , . . ... ... ... ... ... 108 ... ... ... , . . ... 109 ... ... ... ... ... ... ... ... ... . .. ... 110 ... ... ... .. ... . . ... .. ... ... ... ... ... ... ... ... , . . 111 ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... , . . 112 ... ... ... ... . . . ... ... ... 113 ... ... ... ... ... ... ... ... ... ... ... , . . ... .. ... 114 ... ... ... ... ... ... ... ... ... ... ... ... ... ... . . ... ... 115 ... ... ... ... 116 ... ... ... ... . . ... ... ... ... ... ... ... ... ... ... ... ... ... ... 117 ... ... ... ... ... ... ... *.. ... ... ... ... , . . ... ... ... ... ... ... 118 ... ... ... ... ... 119 ... ... ... ... ... . . ... ... ... , . . ... ... ... ... ... ... ... ... ... 120 ... ... ... ... ... ... ... ... , . . ... ... ... ... ... 121 ... ... ... ... ... ... 122 ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... 123 ... , . ... ... ... ... ... ... ... ... ... ... ... 124 ... ... ... ... ... ... , . . ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... . . ... ... ... ... ... , . . ... ... ... ... ... ... ... . . ... ... . . ... ... ... ... ... ... ... ... ... ... , . . ... ... ... ... ... ... ... , . . ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... , . . ... ... ... ... ... ... ... ... ... ... 132 ... ... ... ... ... ... ... ... ... ... 133 ... ... ... ... ... ... ... ... . , . ... ... ... ... ... ... ... ... ... 134 ... ... ... ... ... ... ... ... ... ... ... ... 135 ... ... ... ... , . . ... ... ... ... ... , . . 136 ... ... ... ... ... ... ... ... ... . . ... ... ... ... ... ... 137 ... ... ,.. ... ... , . . ... ... ... ... ... ... ... ... ... ,.. 138 ... ... ... ... ... ... ... ... ... 139 ... ... ... ... ... ... ... ... 140 , . . ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... 141 ... ... ... ... ... ... ,.. ... . .. . . . ... ... ... 142 ... ... ... ... ... ... ... ... ... ... ... ... ... ... 143 ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... 144 ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... 145 ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... 146 ... , . ... ... ... ... ... ... ... ... ... ... ... 147 ... ... . . ... ... , . . ... ... ... ... ... ... 148 ... ... ... ... ... ... ... ... ... ... ... ... ... ... 149 ... ... ... ... . . ... ... ... ... ... ... ... ... ... 151 ... ... ... ... ... ... ,.. ... ... *.. ... ... ... 152 ... ... ... ... . .. ... ... ... ... ... ... ... ... ... ... ... ... ... 153 , . ... ... ... ... ... ..* ... ... ... ... ... ... ... 154 ,.. ... ... ... ... ... ... ... ... ... ... 155 ... ... ... ... .*. ... ... ... ... ... ... ... 156 ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... 157 ... ... ... ... ... ... ... *.. *.. ... ... ... ... ... 158 ... ... ... ... ... ... ... *.. *.. ... ... ... ... 159 ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... 160 ... ... ... ... ... ... ... ... ... ... ... 161 ... ... ... , . . ... ... ... ... ... ... ... ... ... ... ... 162 ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... 163 ... ... ... ... ... ... ... ... ... ... ... ... 165 ... ,.. , . . ... ... ... ... ... ... ... ... ... ... ... ... ... 166
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ANALYTICAL CHEMISTRY
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of Thiols (Continued) 2,2-Di24 42222methylMethyl- Methyl- Methyl- MethylEthyl- MethylMethyl:1-prol-pen- l-pen- >pen- Spen1111-hex- 2-hep11-Dec- 1-Undec- 2-undecpane Hexane tsne tine tane Heptane Octane and tane tank Nonsne me ane ane 1242 918 1243 P 1235 1244 1384 C C P C BM C P 5 104 0.9 0.7
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0.3 (Continued)
VOL 33, NO, 6, MAY 1961
7 11
~~~~
Table 1. Mass 2222MethylMethyl- Methyl- Methyl Coni12112 - 2 1231-bu1-buZbupound Methane Ethane Propane Propane Butane propane Butane propane Pentane Pentane Pentane tsne tsne tane A A Sourceolb E E E E 911 A E 967 921 A 1413 1382 Carbon 2Methyl-
No. hlol. wt. m/e 167 168 169 170 171 172 173 174 175 176 177 179 180 182 183 185 186 187 188 189 190 191 194 197
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Thiols. T h e spectra of the thiols shown in Table I all have significant parent ions, except for the higher tertiary compounds such as %methyl2-undecanethiol. I n the plot of molecular ion intensity us. carbon number for the straighbchain primary thiols (Figure 1) the molecular ion is still 7% of the base peak a t (311. In a manner similar to that employed by Brown ( I ) for hydrocarbon types and McLafferty for alcohols and ethers (9, II), all the major ions of the thiol fragmentation pattern can be classified into four series: M-14N-1, M-14N-6, M14N-5, and M-14N-7. The M-14N-1 series results from the loss of the alkyl
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