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Other Physical Methods

Absorption methods are generally tedious and their accuracy is limited when high frequency ultrasound sources are used. [Pg.65]

Methods based on volume changes, erosion and surface cleaning, and dispersion are rapid but not very accurate and reproducibility is difficult to achieve. Data scattering may be up to 40%. However dosimetry based on erosion and surface cleaning are of particular interest in the study of systems involving of solid disruption. [Pg.65]

Optical methods have the distinct advantage that they are noninvasive in contrast with the other methods, and therefore do not disturb the ultrasonic field. The [Pg.65]

Mass transfer measurements using an electrochemical probe are still under investigation. They only allow local measurements and the system accuracy is not yet known. These methods do however allow interesting observations on acoustic streaming and standing waves conditions. [Pg.66]

In addition to methods employing nuclear magnetic resonance and optical rotation, numerous other physical methods have been applied to cyclitols or their derivatives. [Pg.64]

Solid-state measurements on cyclitols include melting-point studies, solubility studies, thermodynamic measurements, infrared spectra (potassium bromide window), x-ray powder patterns, and optical and x-ray crystallography.  [Pg.64]

Measurements in solution include those of infrared and ultraviolet spectra, infrared hydrogen-bonding, and dipole moments. Sometimes, suitable solvents for such measurements on cyclitols cannot be found. [Pg.64]

Among the methods which have, as yet, found little, if any, application [Pg.64]

Department of Chemistry, Birkbeck College, University of London, England [Pg.67]

A number of reversible changes were observed in the u.v. spectrum when frozen solutions of D-eryt/iro-pentulose (o-ribulose) 5-phosphate were allowed to thaw. Under the same conditions, the spectra of D-/Areo-pentulose(D-xylulose) 5-phosphate and D-ery//rro-pentulose 1,5-diphosphate were unchanged. [Pg.185]

Further Roumanian work is reported on the e.s.r. of iminoxy-radicals obtained from oximes with bicyclo[3,3,l]nonane and bicyclo[3,2,l]octane skeletons substituted in the 2- and 4-positions. The introduction of a bulky substituent in the exo-2-or exo,exo-2,4-positions in the [3,3,1] skeleton leads to a preference for a chair-boat conformation whereas endo-2-, endo,endo-2,4-, or en io,exo-2,4-substituents produce the chair-chair conformation. [Pg.356]

Kemp-Jones, N. Nakamura, and S. Masamune, J.C.S. Chem. Comm., 1974,109. [Pg.358]

Masamune, M. Sakai, and A. V. Kemp-Jones, Canad. J. Chem., 1974,52, 858. [Pg.359]

Olah has discussed the extent of r and n delocalization in 2-norbornyl cations and studied the l,2-diphenyl-2-norbomyl cation (102) by H and n.m.r. He concludes that it behaves as a rapidly equilibrating carbenium ion undergoing fast alkyl shift at -78°C. The cation (103) has also been prepared from several precursors in acidic media at —120 °C. Its spectra indicate rapid equilibration between carbenium forms. At — 60°C it rearranges to (104). The 8,9-dehydro-2-adamantyl cations (105 R = H or Me) have n.m.r. spectra which show that the tertiary cation is a static classical ion, whereas in the secondary case there is rapid equilibration making carbons 1, 8, and 9 equivalent. The analogous 2-substituted 2-adamantyl cations with R = Me, Et, Ph, OH, or halogen are simple ions which do not isomerize under the strong acid conditions used.  [Pg.360]

The cation (107), obtained when (106) is dissolved in SOj at -60°C, reveals an unusual effect addition of ethanol gives (108) while triphenylphosphine gives (109). This latter suggests delocalization protecting one face of the bridge carbon. [Pg.360]

Magnetic susceptibilities of 2-aminothiazole have been measured (139) in order to evaluate the aromatic character of the compound. [Pg.29]

The dipole moment of thiazole is increased by 2-amino group substitution (140). 2-lmino-4-thiazolines are more polar than their 2-aminothiazoles isomers (141). [Pg.29]

The crystal and molecular structures of 2-amino-4-phenylthiazole hydrobromide have been determined by radiocrystallography the angle between the thiazole and phenyl rings was found to be 19 . The major features are reported in Fig. VI-4 (142). [Pg.29]

Tirouflet et al. measured polarographic half-waves for a series of substituted thiazoles (143) in order to determine the ability of polarog-raphy for the selective determination of thiazoles mixtures. The values found for 2-amino-5-bromothiazole agree with the +M effect ot the NHj [Pg.29]

Grote s reagent is useful for the determination of 2-aminothiazoie in blood and wine (145), This thiazole may be extracted from its aqueous solution and then titrated in nonaqueous medium (MeOH) with HCIO4 in the presence of a mixed methyl red-methylene blue indicator (146). [Pg.30]

The spectrum of sucrose in aqueous solution has been studied to examine further the potential of F.t.i.r. spectroscopy for determining carbohydrate configurations. While bands characteristic of an a- rather than 6-linked D-glucopyranosyl unit were present, no criteria for discerning the stereochemistry of the fructose unit were found. Some bands in the hydroxyl stretching region of crystalline carbohydrates have been identified through a [Pg.228]

Microwave spectra of (52) and three isotopic species (1- C, 2- C, and 5- C) have been obtained and analysed. Stark effect measurements yield a dipole moment H = 0.299 0.008 D. The i.r. spectra of gaseous, liquid, and polycrystalline bicyclo-[2,2,2]octa-2,5,7-triene, and the Raman spectrum of the liquid, have been obtained. The observed frequencies are reproduced with an average error of +2.0 cm by a 37-parameter potential function. [Pg.250]

Mass spectrometry in relation to the stereochemistry of organic molecules has been reviewed. Mass spectral (and n.m.r.) compilations of data are reported for some bicyclo[3,2,l]octanes. The use of collision-activation mass spectrometry for determining the structure of ions in the gas phase is examined in a review. Ion [Pg.250]

The unusually large (22.49 G) bridgehead proton hyperfine splitting constant for the radical (53) is accounted for (INDO calculations) by through-space as well as through-bond spin-transfer from C-1 to the hydrogen atom at The dicyclopentadien- [Pg.251]

9-yl radical (54) has been characterized by its e.s.r. spectrum in comparison with the calculated proton h.f.s.c. s, using the INDO MO open-shell and closed-shell schemes.  [Pg.251]

Most ( 90%) of the unpaired electron results from a strong hyperconjugative interaction between the non-bonding combination of the C-7, C-8, and C-9 p O bitals and the (Isjj.i Isjj.g) group orbital, the remainder being delocalized in the norbornene section of the molecule. Perdeuteriated adamantane matrices have been found to provide superior resolution for e.s.r. spectra derived from radicals with a delocalized spin centre e.g. allyl).  [Pg.251]

An aneroid static-bomb combustion calorimeter has been employed to determine the standard enthalpy of formation of a small sample (ca. 20 mg) of bicyclo[3,3,3]nonane (— 36-4g + 0-42 kcal mol ), and a temperature-scanning technique makes use of a commercial gas chromatograph in the measurement of the vapour pressures of several adamantane and diamantane derivatives. Results were converted into heats of sublimation by employing the Clausius-Clapeyron equation doubt is cast on the accuracy of a previously recorded value for diamantane. [Pg.304]

Rearrangements involving the loss of small neutral molecules upon electron impact,and the applications of field-desorption mass spectrometry have been reviewed. Structural correlations are reported for the mass spectra of various alkyl- [Pg.304]

Microwave structural studies are reported for (34), (35), its dihydro-derivative and e.xo-5,6-dideuterio-(35), and 11 isotopic species of the tricyclohexane (36). The last paper offers an explanation of the mechanism of the conversion of (37) by LiAlH4 into the tricyclohexane (38) the bromine exo to the double bond is removed in the first of two steps which involve non-classical carbonium ion intermediates. [Pg.304]

The vibrational spectra of (39) and two deuterium-labelled derivatives are reported and thermodynamic functions at 50—100 K have been established. Further data [Pg.304]

Gergely, Z. Akhavin, and P. Vogel, Helv. Chim. Acta, 1975,58, 871. [Pg.305]

The carbonyl absorption of several O-methyl ketoses e.g, 5- and 6-O-methyl-L-sorbose and 5-O-methyl-D-fructose) has been used to determine the proportion of the acyclic forms present in the tautomeric equilibria in methanol.  [Pg.185]


The preferred quantitative deterrnination of traces of acetylene is gas chromatography, which permits an accurate analysis of quantities much less than 1 ppm. This procedure has been highly developed for air poUution studies (88) (see Airpollution control methods). Other physical methods, such as infrared and mass spectroscopy, have been widely used to determine acetylene in various mixtures. [Pg.377]

In the post-World War II years, synthesis attained a different level of sophistication partly as a result of the confluence of five stimuli (1) the formulation of detailed electronic mechanisms for the fundamental organic reactions, (2) the introduction of conformational analysis of organic structures and transition states based on stereochemical principles, (3) the development of spectroscopic and other physical methods for structural analysis, (4) the use of chromatographic methods of analysis and separation, and (5) the discovery and application of new selective chemical reagents. As a result, the period 1945 to 1960 encompassed the synthesis of such complex molecules as vitamin A (O. Isler, 1949), cortisone (R. Woodward, R. Robinson, 1951), strychnine (R. Woodward, 1954), cedrol (G. Stork, 1955), morphine (M. Gates, 1956), reserpine (R. Woodward, 1956), penicillin V (J. Sheehan, 1957), colchicine (A. Eschenmoser, 1959), and chlorophyll (R. Woodward, 1960) (page 5). ... [Pg.3]

Nondestructive Detection Using Other Physical Methods 2.5.1 Spectral Phenomena... [Pg.42]

Nondestructive Dection Using Other Physical Methods 43 Table 7. Nondestructive detection of lipophilic substances with water as detecting reagent. [Pg.43]

Nondestructive Dection Using Other Physical Methods... [Pg.45]

As explained in the preceding section, we will discuss the structure of aromatic diazonium salts on the basis of evidence from X-ray investigations. We will supplement those results with data obtained by other physical methods, in particular NMR and IR spectroscopy. Earlier experience with the more stable arenediazonium salts enabled those scientists who first obtained alkanediazonium ions in solution to characterize them by NMR spectroscopy (see Zollinger, 1995, Sec. 2.1). [Pg.66]

Other physical methods were also applied to the elucidation of the isomerism of diazocyanides, e. g., determination of diamagnetic susceptibility, the Faraday effect (optical rotation in a magnetic field), and electronic and infrared spectra. Hantzsch and Schulze measured ultraviolet spectra at a remarkably early date (1895 a). Unfortunately, their results and later work (Le Fevre and Wilson, 1949 Freeman and Le Fevre, 1950) did not allow unambiguous conclusions, except perhaps the observation that the molar extinction coefficients of the band at lowest frequency are consistently larger in all types of (i -compounds Ar — N2 - X than in the corresponding (Z)-iso-mers (Zollinger, 1961, p. 62). [Pg.146]

Electrochemical as well as nonelectrochemical techniques are used when studying these aspects. Electrochemical techniques are commonly used, too, in chemical analysis, in determining the properties of various substances and for other purposes. The nonelectrochemical techniques include chemical (determining the identity and quantity of reaction products), radiotracer, optical, spechal, and many other physical methods. Sometimes these methods are combined with electrochemical methods for instance, when studying the optical properties of an electrode surface while this is polarized. Nonelectrochemical techniques are described in more detail in Chapter 27. [Pg.191]

Chemical and other physical methods of ionization were also employed for the structural determination of dienes and polyenes. Such is the case for the recent investigation of aliphatic dienes and trienes by chemical ionization with nitric oxide (NO+)25. It has been known since 1975 that olefins can be chemically ionized by NO+ [CI(NO)]26. Two distinct processes may apparently occur (i) electrophilic addition of NO+ to the ene leading to [M + NO]+ ion and (ii) an oxidative cleavage (possibly catalysed by the... [Pg.494]

Determinations of epr fine structure and paramagnetic susceptibilities are most often used. For characterization of higher spin orders, neutron diffraction and other physical methods may be useful. On the other hand, a successful measurement of normal high-resolution nmr spectra would serve as good evidence for singlet ground states of the chemical entities at issue. [Pg.201]

As with any other physical methods, the CIDNP method is not universal and not immune to misinterpretation. It has certain drawbacks The polarization is weak and hardly detected in reactions involving extremely short-lived radicals and, if so, the polarization disappears quickly. It is often difficult to attribute the polarization to products of the main conversion, rather than the side or reverse conversions. The latter threat is most serious for the reactions with participation of ion-radicals—the formation of end products often proceeds concurrently with the restoration of the initial neutral molecules, due to a reverse electron transfer as in Scheme 4.29. [Pg.234]

In comparison with other physical methods, EXAFS has both advantages and limitations. It is always detectable, does not require the use of special isotopes, and provides unparalleled information regarding the stmcture of the absorbing site. [Pg.45]

The surface property of a solid changes even after one layer of lipid is formed as an LB film, such as, the contact angle decreases after LB deposition. Similarly, many other physical methods have shown that LB films change the surface characteristics (Gaines, 1966 Adamson and Gast, 1997 Birdi, 2002a). [Pg.99]

In 1960 Rex (22) first reported the use of electron paramagnetic resonance spectrometry as a method for demonstrating the presence of stable organic free radicals in humic acid. We felt that this technique might provide useful information about the structure of humic acid which was not readily available by other physical methods, particularly if relations between EPR spectra and chemically modified humic acids could be demonstrated. Our preliminary studies (26) confirmed this presumption. [Pg.87]

An important advantage in phosphorus systems is the fact that 31P, which is the only natural isotope, has a spin of and can be easily measured by NMR. Its characteristic chemical shifts 8 (p.p.m.) and its H and 13C coupling constants J (Hz) have influenced the development of the heterocyclic chemistry of phosphorus more than any other physical methods such as IR, UV, MS, dipole moment measurement and others. [Pg.496]


See other pages where Other Physical Methods is mentioned: [Pg.218]    [Pg.29]    [Pg.820]    [Pg.3]    [Pg.135]    [Pg.546]    [Pg.51]    [Pg.47]    [Pg.130]    [Pg.435]    [Pg.290]    [Pg.546]    [Pg.574]    [Pg.354]    [Pg.292]    [Pg.36]    [Pg.239]    [Pg.238]    [Pg.43]    [Pg.581]    [Pg.591]    [Pg.618]    [Pg.65]    [Pg.806]    [Pg.131]    [Pg.170]    [Pg.391]    [Pg.8]    [Pg.43]    [Pg.48]    [Pg.79]   


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