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Saturn GC/MS MASS SPECTRAL INTERPRETATION QUICK REFERENCE GUIDE 03-914351-00:R2 GRAPHICAL REPRESENTATION OF RELATIVE ISOTOPE PEAK INTENSITIES FOR ANY GIVEN ION CONTAINING THE INDICATED NUMBER OF HALOGENS CHLORINE-BROMINE ISOTOPE ABUNDANCE RATIOS Cl-Br X X+2 X+4 X+6 X+8 X+10 Cl 100 32.5 Cl2 100 65.0 10.6 Cl3 100 97.5 31.7 3.4 Cl4 76.9 100 48.7 10.5 0.9 Cl5 61.5 100 65.0 21.1 3.4 0.2 Cl6 51.2 100 81.2 35.2 8.5 1.1 ClBr 76.6 100 24.4 Cl2Br 61.4 100 45.6 6.6 Cl3Br 51.2 100 65.0 17.6 ClBr2 43.8 100 69.9 13.7 Cl2Br2 38.3 100 89.7 31.9 3.9 Cl3Br2 31.3 92.0 100 49.9 11.6 ClBr3 26.1 85.1 100 48.9 8.0 Cl2Br3 20.4 73.3 100 63.8 18.7 Br 100 98.0 Br2 51.0 100 49.0 Br3 34.0 100 98.0 32.0 Br4 17.4 68.0 100 65.3 1.7 16.0 1.0 2.0 EXACT MASSES AND NATURAL ISOTOPIC ABUNDANCE RATIOS Element Symbol Intg. Mass Exact Mass Abundance X+1 Factor* X+2 Factor* Hydrogen H D or 2H 1 2 1.0078 2.0141 99.99 0.01 12C 12 13 12.0000 13.0034 98.91 1.1 1.1nC 0.0060nC2 14N 14 15 14.0031 15.0001 99.6 0.4 0.37nN 18O 16 17 18 15.9949 16.9991 17.9992 99.76 0.04 0.20 Fluorine F 19 18.9984 100 Silicon 28Si 30Si 28 29 30 27.9769 28.9765 29.9738 92.2 4.7 3.1 Phosphorus P 31 30.9738 100 Sulphur 32S 32 33 34 31.9721 32.9715 33.9679 95.02 0.76 4.22 Carbon Nitrogen 13C 15N Oxygen 16O 17O 29Si 33S 34S 0.04nO 0.20nO 5.1nSi 3.4nSi 0.8nS 4.4nS Chlorine 35Cl 35 37 34.9689 36.9659 75.77 24.23 32.5nCl Bromine 79Br 79 81 78.9183 80.9163 50.5 49.5 98.0nBr Iodine I 127 126.9045 100 1. 2. 3. 37Cl 81Br The integer mass of the most abundant naturally-occurring stable isotope is the nominal mass of the element. The exact mass of the most abundant naturally occurring stable isotope is the mono-isotopic mass of the element. The atomic weight is the average mass of the element. *Assume X = 100%; X represents the relative intensity of the first peak in a cluster of peaks corresponding to isotopic variants of a given ion. The factor is multiplied by the number (n) of atoms of the element present to determine the magnitude of the intensity contribution for a given isotope. For example, the contribution at “X+1” due to 15N for an ion containing three nitrogens would be 0.37 x 3 = 1.11 relative to 100 at “X”. ISOTOPIC CONTRIBUTIONS FOR C AND H C# (X+1)+ (X+2)+ C# (X+1)+ (X+2)+ C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 1.1 2.2 3.3 4.4 5.5 6.6 7.7 8.8 9.9 11.0 12.1 13.2 14.3 15.4 16.5 17.6 18.7 19.8 20.9 22.0 0.01 0.02 0.05 0.10 0.15 0.22 0.29 0.38 0.49 0.60 0.73 0.86 1.0 1.2 1.3 1.5 1.7 1.9 2.2 2.4 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 23.1 24.2 25.3 26.4 27.5 28.6 29.7 30.8 31.9 33.0 34.1 35.2 36.3 37.4 38.5 39.6 40.7 41.8 42.9 44.0 2.6 2.9 3.2 3.4 3.7 4.1 4.4 4.7 5.0 5.4 5.8 6.1 6.5 6.9 7.3 7.8 8.2 8.7 9.1 9.6 The isotopic contributions for other elements is additive. UNREASONABLE SUGGESTED LOSS FROM THE MOLECULAR ION M–7 M–3 M–6 These do not correspond to the mass of groups of atoms likely to be lost from most common organic molecules; they probably result from noise spikes or ions from an impurity. As a general rule, 3 to 14 and 21 to 26 is not a reasonable loss. TYPES OF POSITIVE-ION CI REACTIONS Gas-phase analytes can undergo four different types of reactions with the reagent ions in positive-ion CI. It should be noted that only “charge transfer” results in the formation of an OE+. ion. All the other reaction mechanisms result in the formation of EE+ ions. CHARGE TRANSFER CH4+. + RH → RH+. CH4 (M+.) + PROTON TRANSFER CH5+ + C2H5+ + RH → RH2+ + RH → RH2+ + CH4 (M + 1)+ C2H4 HYDRIDE ABSTRACTION CF3+ + RH → R+ CF3H (M − 1)+ + COLLISION-STABILIZED COMPLEXES C2H5+ + RH → (C2H5:RH)+ (M + 29)+ C3H5+ + RH → (C3H5:RH)+ (M + 41)+ Acetonitrile and methanol along with other reagents that exist as a liquid under normal pressure and temperatures, can be used easily in the internal ionization ion-trap mass spectrometer. Reagent Reagent Ion Proton Affinity (kcal mol-1) CH4 H2O CH3OH C2H5OH CH3CN iC4H10 NH3 CH3NH2 CH5+ H3O+ CH3OH2+ C2H5OH2+ CH3CNH+ iC4H9+ NH4+ CH3NH3+ 132 167 182 186 188 196 204 211 STEPS IN THE INTERPRETATION OF A MASS SPECTRUM 1. Note general appearance of spectrum to see if it is interpretable. 2. Select a candidate peak for the molecular ion (M+. ). 3. Examine spectrum for peak clusters of characteristic isotopic patterns. 4. Test M+. candidate by searching for peaks corresponding to reasonable loss. 5. Look for characteristic low-mass fragment ions. 6. Compare spectrum to reference spectra: a. Using compilations in published references b. Using computerized search of reference spectra 7. Spectral interpretation must be reconciled with all other information about the sample. 8. Check interpretation by obtaining spectrum of putative compound under some instrumental conditions. CRITERIA FOR RECOGNIZING AND PROVING VALIDITY OF MOLECULAR ION 1. If compound is known, molecular ion will have an m/z value equal to the sum of the atomic masses of the most abundant isotope of each element that comprises the molecule. 2. The M+. peak must be the highest m/z value peak of significance (non-background, non isotope). 3. The nominal molecular weight or m/z value for the molecular ion will be an even number for any compound containing only C, H, O, S, Si, P and halogens. • Fragment ions derived via homolytic fission from these ions will have an odd m/z value. • Fragment ions derived from these molecular ions (even mass) via expulsion of neutral components (e.g., H2O, CO, ethylene, etc.) will themselves have an even value of m/z. 4. Nitrogen Rule: A compound containing an odd number of nitrogen atoms in addition to C, H, O, S, Si, P and halogens will have an odd molecular weight. 5. No fragment ion may contain a larger number of atoms of any particular element than the M+.. McLAFFERTY REARRANGEMENT FORMATION OF TROPYLIUM ION RINGS PLUS DOUBLE BONDS For a proposed molecular formula, the rings plus double bonds can be calculated by adding the number of carbons plus 1 to the number of nitrogens divided by 2, and subtracting the number of hydrogens divided by 2. If the value ends in 1/2, round down to obtain the applicable value. SOME COMMON AND REASONABLE LOSSES FROM THE MOLECULAR ION M-1 M - 15 M - 29 M - 31 M - 43 M - 45 M - 57 M-2 M - 18 M - 28 M - 32 M - 44 M - 60 M - 90 loss of hydrogen radical loss of methyl radical loss of ethyl radical loss of methoxyl radical loss of propyl radical loss of ethoxyl radical loss of butyl radical loss of hydrogen loss of water loss of CO or ethylene loss of methanol loss of CO2 loss of acetic acid loss of silanol: HO-Si(CH3)3 • M-H • M - CH3 • M - CH2CH3 • M - OCH3 • M - CH2CH2CH3 • M - OCH2CH3 • M - CH2CH2CH2CH3 M - H2 M - H2O M - CO or M- C2H4 M - CH3OH M - CO2 M - CH3CO2H M - HO-Si(CH3)3 NEUTRAL FRAGMENTS EXPELLED BY SIMPLE CLEAVAGE Mass 1 15 16 17 19 26 27 29 30 31 33 35 40 41 43 44 45 46 • Fragment (OE ) H • CH3 • NH2 • • OH, NH3 • F • CN • C2H3 • • C2H5, CHO • • CH3NH, CH2NH2 • • CH3O, CH2OH • • SH, CH2F; • (H2O + CH3) • Cl • CH2CN • C3H5 • • C3H7, CH3CO • C2H5N H • • C2H5O, COOH • NO2 • • Mass 47 49 51 54 55 57 58 59 61 65 69 71 77 79 81 91 105 127 • Fragment (OE ) CH2SH • CH2Cl • CHF2 • CH2CH2CN • • C4H7, C3 H3O • • C4H9, C3 H5O • C3H8N • • C3H7O, COOCH3; • CH2COOH • C2H5S • C2H5 • CF3 • C4H7O • C6H5 • • Br, C6H7 • • C6H9, C5H5O • C7H7 • • C7H5O, C8H9 • l • NEUTRAL FRAGMENTS EXPELLED BY MULTICENTERED FRAGMENTATIONS Mass 2 17 18 20 27 28 30 31 32 34 36 42 44 Fragment (EE) H2 NH3 H2O HF HCN CO, C2H4 CH2O CH5N CH4O H2S HCI C3H6, C2H2O CO2 Mass 45 46 48 54 56 58 59 60 62 74 76 78 80 Fragment (EE) C2H7N C2H6O, or H2O+C2H4 CH4S C4H6 C4H8, or C3H4O C3H6O C3H9N C3H8O, or C2H4O2 C2H6S C3H6O2 C6H4 C6H6 HBr Learn about all the GC/MS Techniques offered by Varian • Full Scan EI • Selected Ion Storage (SIS) • Chemical Ionization (with Gas and Liquid Reagents) • MS/MS and MSn • Multiple Reaction Monitoring (MRM) • ChromatoProbe • Multi Inlet CI manifold (Gas and Liquid) For more information, contact your Varian Representative or one of the locations listed below: In North America In Europe 2700 Mitchell Drive Walnut Creek, CA 94598 USA Tel: 1 800 926 3000 Tel: 1 925 939 2400 Fax:1 925 945 2334 Herculesweg 8 4330 EA Middelburg The Netherlands Tel: +31 118 67 1000 Fax: +31 118 62 3193 In South America In Australia/Asia Ave. Dr. Cardoso de Mello, 1644 04548- 005 Sao Paulo, Brazil Tel: +11 820 0444 Fax: + 11 820 9350 679 Springvale Rd. 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