Of molecular ions

Gruebele M H W 1988 Infrared Laser Spectroscopy of Molecular Ions and Clusters (Berkeley University of California)... 

Mass spectrometric investigations of the ionosphere show an abundance of molecular ions such as NO and watercluster ions [4T ]. This is an indication of the result of ion-molecule reactions which change the chemical state of the ions in this plasma ... 

Comparison of basic El and Cl processes showing different types of molecular ions and the formation of fragment ions in El. 

In general, FAB and LSIMS will give excellent molecular mass information in the range (approximately) of m/z 100-2000. Above this value, the abundance of molecular ions tends to diminish until, in the region of m/z 4000-5000, they become either nonexistent or very difficult to... 

Finally, note that the ions produced by the combined inlet and ion sources, such as electrospray, plasmaspray, and dynamic FAB, are normally molecular or quasi-molecular ions, and there is little or none of the fragmentation that is so useful for structural work and for identifying compounds through a library search. While production of only a single type of molecular ion may be useful for obtaining the relative molecular mass of a substance or for revealing the complexity of a mixture, it is often not useful when identification needs to be done, as with most general analyses. Therefore,... 

There are ill-defined limits on EI/CI usage, based mostly on these issues of volatility and thermal stability. Sometimes these limits can be extended by preparation of a suitable chemical derivative. For example, polar carboxylic acids generally give either no or only a poor yield of molecular ions, but their conversion into methyl esters affords less polar, more volatile materials that can be examined easily by EL In the absence of an alternative method of ionization, EI/CI can still be used with clever manipulation of chemical derivatization techniques. 

Ionization Method Type of Molecular Ion Formed Good Molecular Mass Information Abundant Fragment Ions MS/MS Needed for Structural Information Accurate Values for Isotope Ratios... 

The relationship between what is recorded in a SSIMS spectrum and the chemical state of the surface is not as straightforward as in XPS and AES (Chap. 2). Because of the large number of molecular ions that occur in any SSIMS spectrum from a multi-component surface (e. g. during the study of a surface reaction), much chemical information is obviously available in SSIMS, potentially more than in XPS. The problem in using the information from a molecular ion lies in the uncertainty of knowing whether or not the molecule represents the surface composition. For some materials. 

Furthermore, about 1920 the idea had become prevalent that many common crystals, such as rock salt, consisted of positive and negative ions in contact. It then became natural to suppose that, when this crystal dissolves in a liquid, the positive and negative ions go into solution separately. Previously it had been thought that, in each case when the crystal of an electrolyte dissolves in a solvent, neutral molecules first go into solution, and then a certain large fraction of the molecules are dissociated into ions. This equilibrium was expressed by means of a dissociation constant. Nowadays it is taken for granted that nearly all the common salts in aqueous solution are completely dissociated into ions. In those rare cases where a solute is not completely dissociated into ions, an equilibrium is sometimes expressed by means of an association constant that is to say, one may take as the starting point a completely dissociated electrolyte, and use this association constant to express the fact that a certain fraction of the ions are not free. This point of view leads directly to an emphasis on the existence of molecular ions in solution. When, for example, a solution contains Pb++ ions and Cl- ions, association would lead directly to the formation of molecular ions, with the equilibrium... 

The Dissociation Constant of Nitric Add. Alodcrately Weak Acids. The Variation of J with Temperature. Proton Transfers between Solute Particles. A Proton Transfer in Methanol Solution. Proton Transfers with a Negative Value for. / . The Hydrolysis of Salts. Molecules with Symmetry. Substituted Ammonium Ions. Deuteron Transfers in D2(). The Dissociation of Molecular Ions. 

Table 18. Dissociation of Molecular Ions in Aqueous Solution at 25°C...

It is of interest to compare the values of AF and AH in Table 34 with the values of AF and AH given in Table 18 for the dissociation of molecular ions. We notice that in the dissociation of the ions (FeCl)++ and (FeBr)++ the value of AF is relatively small and is accompanied by a AH that is negative on the other hand, in the dissociation of (FeOH)++ the value of AF is very large and is accompanied in Table 18 by a AH... 

Neutral Loss Only a limited number of neutral fragments of low mass which are eliminated in decompositions of molecular ions. Examples are H, H2, CH3 and OH. Therefore, the presence of a major ion below the molecular ion at an improbable interval (eg, loss of 4 to 14, 21 to 25 amu) will indicate that the latter is not the molecular ion Postulation of Molecular Structures The. postulation of the structure of an unknown molecule is based on several major kinds of general structural information available in the mass spectmm. McLafferty (Ref 63) suggests the following systematic approach ... 

Verification of the molecular weight of thiirene dioxides by mass spectrometry, employing the conventional electron-impact (El) ionization method, has been unsuccessful due to the absence or insignificant intensity of molecular ion peaks in their mass spectra. The base peak is rather characteristic, however, and corresponds to the formation of the disubstituted acetylene ion by loss of sulfur dioxide91 (equation 3). 

Electrospray is the softest mass spectrometry ionization technique and electrospray spectra therefore usually consist solely of molecular ions. Electrospray is unique, however, in that if the analyte contains more than one site at which protonation (in the positive-ion mode) or deprotonation (in the negative-ion mode) may occur, a number of molecular ions with a range of charge states is usually observed. For low-molecular-weight materials (< 1000 Da), the number of sites... 

Consequently, the only pseudomolecular ions produced are [M+Na]" species. These are usually abundant, permitting the observation of molecular ions up to at least 6000. 

Fig. 9.—Schematic Representation of Molecular-ion Signals That May Be Formed in the Positive-ion Mode, Showing Commonly Observed Mass Differences.

A mass spectrometer provides an example of a molecular beam, in this case a beam of molecular ions. Molecular beams are used in many studies of fundamental chemical interactions. In a high vacuum, a molecular beam allows chemists to study the reactions that take place through specifically designed types of collisions. For example, a crossed-beam experiment involves the intersection of two molecular beams of two different substances. The types of substances, molecular speeds, and orientations of the beams can be changed systematically to give detailed information about how chemical reactions occur at the molecular level. Chemists also have learned how to create molecular beams in which the molecules have very little energy of motion. These isolated, low-energy molecules are ideal for studies of fundamental molecular properties. 

Figure L Narrow range mass spectral scan of molecular ion region during GC elution of NDMA, A, Recorded at retention time of NDMA beer sample con-taining 0.6 fig/kg NDMA (0.15 ng). B. Background 1 min before elution of NDMA. C. Standard solution containing 0.4 ng NDMA. D. Background.

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