Mass Spectrometry a text book Ch Isotopes质谱法一本教科书.pdfVIP

3 Isotopes Mass spectrometry is based upon the separation of charged ionic species by their mass-to-charge ratio, m/z. Within the general chemical context however, we are not used to taking into concern the isotopes of the elemental species involved in a reaction. The molecular mass of tribromomethane, CHBr3, would therefore be cal- culated to 252.73 g mol–1 using the relative atomic masses of the elements as listed in most periodic tables. In mass spectrometry we have to leave this custom behind. Because the mass spectrometer does not separate by elements but by iso- topic mass, there is no signal at m/z 252.73 in the mass spectrum of tribromometh- ane. Instead, major peaks are present at m/z 250, 252, 254 and 256 accompanied by some minor others. In order to successfully interpret a mass spectrum, we have to know about the isotopic masses and their relation to the atomic weights of the elements, about isotopic abundances and the isotopic patterns resulting therefrom and finally, about high-resolution and accurate mass measurements. These issues are closely related to each other, offer a wealth of analytical information, and are valid for any type of mass spectrometer and any ionization method employed. (The kinetic as- pect of isotopic substitution are discussed in Chap. 2.9.) 3.1 Isotopic Classification of the Elements An element is specified by the number of protons in its nucleus. This equals the atomic number of the respective element, and thus determines its place within the periodic table of the elements. The atomic number is given as a subscript preced- ing the elemental symbol, e.g., 6C in case of carbon. Atoms with nuclei of the same atomic number differing in the number of neutrons are termed isotopes. One isotope differs from another isotope of the same element in that it possesses a dif- ferent number of neutrons, i.e., b