By Paul M. Mayer, Christiane Aubry, John Holmes
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Extra info for Assigning Structures to Ions in Mass Spectrometry
In general it is not satisfactory to extend AE measurements much beyond the lowest energy fragmentations of the ionized molecule or radical being studied. Such AE data will be too high as a result of the internal energy necessary for the chosen reaction to compete kinetically with the much faster lower energy processes. The competitive shift is therefore the excess energy above the threshold, for a given high energy reaction, required for the products to be observed on the mass spectrometer timescale.
60 The molecule of interest (B) is allowed to exchange protons with molecules (A) having known PA values that bracket that of the unknown B. The result is to give an upper and lower limit for PA(B); careful selection of molecules A will narrow the bracket to better than, say, 15 kJ=mol. Measurement of Proton Affinities; the Kinetic Method This approach94 measures the product ion peak ratios for the competing dissociations of proton-bound pairs: AHþ B ! AHþ þ B þ AH B ! A þ BH þ (1:11) (1:12) and then equates (AHþ)=(BHþ) to k11=k12.
By combining these values, DfH for the ion is obtained. 3. 3 Plots of adiabatic ionization energy (IEa) vs the reciprocal of the number of atoms in the species (1=n) for some homologous series: (a) alkanes (RH), primary alkanols (ROH) and bromides (RBr); (b) di-n-alkyl ethers (ROR), cyclic ethers (cy-ROR) and alkylamines (RNH2). ß 2006 by Taylor & Francis Group, LLC. The lines have different slopes and these are in keeping with the relative abilities of the ionized functional group to localize the charge; the gentler the slope, the stronger the charge localization.
Assigning Structures to Ions in Mass Spectrometry by Paul M. Mayer, Christiane Aubry, John Holmes