By Paul M. Mayer, Christiane Aubry, John Holmes
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Additional info for Assigning Structures to Ions in Mass Spectrometry
8) raises the value for the C5H10O species from 822 to 828 kJ=mol, ß 2006 by Taylor & Francis Group, LLC. 7 Plots of proton affinity (PA) vs 1=n for a variety of homologous molecules: (a) primary alkylamines (RNH2), alkanols (ROH) and bromides (RBr); (b) di-n-alkyl ethers (ROR) and cyclic ethers (cy-ROR). See text for discussion of the open square in (b). mol, placing the data point (dark square) on the (now slightly steeper) line. This provides a good example of the utility of such graphs. 8a: Df H(MHþ ) ¼ Df H(M) þ Df H(Hþ ) À PA(M) ß 2006 by Taylor & Francis Group, LLC.
2006 by Taylor & Francis Group, LLC. 1 Potential energy diagram for ionization showing vertical (IEv) and adiabatic (IEa) ionization energies. Also shown are dissociations involving a reverse energy barrier (Erev) and none for the lowest energy dissociation of the ions. , no nuclear displacement. In general, for many molecules, IEa % IEv is not an unreasonable first assumption. The heats of formation of many organic ions are to be found in Chapter 3, which describes individual ion structures.
These bond strengths are a measure of the electrostatic forces that hold the species together. The appropriate competing dissociations of AHþB are thus to AHþ and BHþ. , oxygen or nitrogen, or even mixed pairs containing these atoms. For O–Hþ–O-bound species, the bond dissociation energy relationship is as follows:100 D(AHþ À B) ¼ 0:46(PA(B) À PA(A) ) þ 129 Æ 8 kJ=mol (1:14) and for O–Hþ–N systems the equation is as given below:101 D(AHþ À B) ¼ 0:26(PA(B) À PA(A) ) þ 126 Æ 6 kJ=mol (1:15) Note that these equations also permit estimates to be made for ions in which the proton binds a molecule and a free radical, provided that the required free ß 2006 by Taylor & Francis Group, LLC.