MS-intoduction.ppt

Bromine 2 intense peaks for the molecular ion, spaced by 2 daltons. 79Br and 81Br 79Br 79Br 81Br 81Br 遵迂澈攘局酵夺发肇吊诬宾联甭酷剃良盛洱粘闺店钒蚁蚜诅啥永育洱垢诌MS-introductionMS-introduction Chlorine 35Cl (P= .75) 37Cl (P= .25) Ratio 3:1 Probability : [M+] / [M + 2] = 0.75 / 0.25 = 3 / 1 100 : 33 艺彬鞍邀声庶酶毯褂扭迢党览挡邀筑淹暂叠眠模夺砌眼呼歪眺蛀里锣稗掂MS-introductionMS-introduction Calculation of isotope pattern: 2 Cl 1 Cl 2 Cl C2H235Cl2 C2H235Cl 37Cl C2H2 37Cl2 P (2 35Cl) = (0.75 )2 = 0.563 P (35Cl 37Cl) + P (37Cl 35Cl ) = (0.75 ) (0.25 ) + (0.25 ) (0.75 ) = 0.375 P (2 37Cl) = (0.25 )2 = 0.063 [M+] / [M + 2] / [M + 4] = 100 / 66 / 11 C2H237Cl 35Cl 纵耽涧蹈豺裴翁尚醚曾够祸涅辜澎蜀油挑物怀挝绅炕跟幅废统零婪闷佯谈MS-introductionMS-introduction Calculation of isotope pattern: ClBr 35Cl = .75 37Cl = .25 79Br = 51% 81Br = 49% [RClBr]+ can exist as 4 isotopic forms: 35Cl 79Br M 0.75 x 0.51 = 38% 35Cl 81Br M+2 0.75 x 0.49 = 37% 37Cl 79Br M+2 0.25 x 0.51 = 13% 37Cl 81Br M+4 0.25 x 0.49 = 12% 50% At very high resolution, the 2 (M + 2) peaks can be distinguished (separated by 0.001 Dalton) 膏匣午娃瑰风缮姆突迟券粹薄靡襟仅夏射螟肥赣骸扳颤凸手潍搔譬虹旱济MS-introductionMS-introduction Chlorine and Bromine The Molecular ion M+ is always the lowest mass peak in the ion cluster (regardless of it’s relative intensity) 亢趾想挽齿卡袁死招熄戈哆妥镀适俘隔孺剃辐鸟毛讨渡厉需婪敦唇糯闪递MS-introductionMS-introduction Isotopic abundances for Carbon containing compounds M+ = p(M) = p(n 12C) = (0.989)n [M+1]+ = p(M+1) = p(n -1) 12C + 1 13C = n p[n-1] 12C x p(13C) The probability of finding 1 13C among n carbons is: = n(0.989)n-1 (0.011) Relative ratio: [M+1]+ / [M+ ] = n(0.989)n-1 (0.011) / (0.989)n = n (0.011) / (0.989) = n (0.0111) In percentage: n x 1.1 % 虑尧涅劝捡屏讥职龄足扇泣停惹过话惋山坍胀架琳遂花侥霄九唉阳煌汲绽MS-introductionMS-introduction Isotopic abundances for Carbon containing compounds When comparing calculated abundances with observed intensities: We see that the ratio is not identical: due to experimental error The relative abundance of the larger peaks are reproducible to ±10% For smaller peaks, relative intensity is