Salts atomic spectra

Excitation of the outer ns electron of the M atom occurs easily and emission spectra are readily observed. We have aheady described the use of the sodium D-line in the emission spectrum of atomic Na for specific rotation measurements (see Section 3.8). When the salt of an alkali metal is treated with concentrated HCl (giving a volatile metal chloride) and is heated strongly in the non-luminous Bunsen flame, a characteristic flame colour is observed (Li, crimson Na, yellow K, lilac Rb, red-violet Cs, blue) and this flame test is used in qualitative analysis to identify the M ion. In quantitative analysis, use is made of the characteristic atomic spectrum in flame photometry or atomic absorption spectroscopy. 

That the ind-N atom in the anhydro-bases is the basic center is also obvious from a consideration of the ultraviolet absorption spectra of the anhydro-bases. In aqueous 0.1 A hydrochloric acid as well as in neutral alcoholic solutions each carboline anhydro-base gives rise to an ultraviolet absorption spectrum identical with that of the parent carbolinium salt. In alkaline solutions (pH above 11.5 in the case of the... 

The asymmetrical anhydrobase (20) constitutes the first step of the formation of trimethine thiazolocyanine when a 2-methylthiazolium salt reacts either with a benzothiazolium or its opened form [which is bis-o-(formylmethylamino)(diphenyl disulfide] (Scheme 26). In a second step, 20 is protonated by a second molecule of 2-methylthiazolium. It results in cleavage of the benzothiazoline ring, which gives 21 together with the formation of the monomeric anhydrobase (22). Cleavage of the C-S bond of 20 can be explained by the important electronic desaturation of the C atom observed in NMR spectrum and the great polarizability of the C-S bond in this type of ring (48). 

In the presence of an alkali salt, strong metal atom emission can be seen both in the emission spectrum and visually. This form of emission is described in detail in Chapter 13. Long-time exposure photographs comparing sonoluminescence and luminol and Na sonochemical luminescence are shown in Fig. 15.5a-c. 

In practical terms, it is invariably a nitrogen atom that is protonated in salt formation. This always leads to a downfield shift for protons on carbons both alpha and beta to the nitrogen concerned. In alkyl amines, the expected shifts would be about 0.7 and 0.3 ppm respectively. Remember that some heterocyclic compounds (e.g., pyridine) contain nitrogen atoms that are basic enough to protonate and comparable downfield shifts can be expected (Spectrum 5.9). 

The 1 R,6R,7R,8S-as-fused structure and conformation of 102 were elucidated on the basis of their NMR spectroscopic data. The observed formation of only one sulfonium salt in this cyclization reaction was remarkable in that either sulfur atom might have been expected to participate in tosylate displacement. The H NMR spectrum of salt 102 shows a large three-bond scalar coupling of 10.6 Hz between H-6 (5 = 4.736) and H-7 (5 = 4.606) this indicates that they have an almost antiperiplanar relationship. The equatorial orientation of H-6 and the 3C6 conformation of its six-membered cycle are consistent with the strong NOEs observed between H-7 and both H-2axja and and... 

The intriguing radical cation [Te N(SiMe3)2 2]+ is formed (as the blue AsF6 salt) by oxidation of Te[N(SiMe3)2]2 with AsF5. This deep blue salt is monomeric in the solid state with d(Te-N) = 1.97 A, consistent with multiple bonding. The broad singlet in the ESR spectrum indicates that the unpaired electron is located primarily on the tellurium atom.181... 

The EPR spectrum of 7 (R=CF3) AsFr, salt in S02, consisted of a central binomial septet due to coupling of 6 equivalent F atoms with one set of weak 33S satellites. Although trithiolylium cations contain two inequivalent sets of sulfur nuclei, only one set of 33S satellites were observed. Further studies with 7 (R=C02Me) however managed to resolve the 33S satellite into two components in 1 2 intensity ratio, consistent with the structure of a 1,2,3-trithiolylium radical cation.92... 

As indicated later (see Section VI,8), on addition of the chloride of praseodymium, europium, or other lanthanides to mono- or poly-sac-charide phosphates in D20, the signals of carbon atoms substituted with phosphate groups are recognizable, as they are displaced, relative to the rest of the 13C-n.m.r. spectrum.155 However, this diagnostic method is not applicable to sulfated polysaccharides, as signal displacements were not observed on addition of praseodymium or europium chloride to a solution of a,/3-D-galactose 6-sulfate or its sodium salt.156... 

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