Raman spectra of single crystals of adipic and sebacic acids and a study of the hydrogen bond vibrations in carboxylic acid dimers

Raman spectra of single crystals of adipic and sebacic acids have been photographed for the first time using λ 2537 excitation. The spectra have been divided into four regions: (a) internal frequencies; (b) summations and overtones; (c) external vibrations; and (d) low-frequency hydrogen bond oscillations. Tentative correlations have been given for all the internal frequencies and summations and overtones. A series of diffuse weak bands observed in the spectra of both these acids in the not, vert, similar2400–2800 cm−1 have been explained as a superposition of O---H frequencies lowered due to hydrogen bond formation over the summations and overtones of fundamentals mainly in the not, vert, similar1000–1500 cm−1 region. Rotatory type of external oscillations of the two formula units of these molecules in their unit cells have been identified at 76, 99, 118 and 165 cm−1 in adipic acid and 66, 95, 117 and 177 cm−1 in the spectrum of sebacic acid. A brief discussion of the low frequency hydrogen bond vibrations in these acids has been made. Making use of the Lippincott—Schroeder potential and assuming a highly anharmonic potential curve for the hydrogen bond, the vibrational frequencies of the bond have been theoretically evaluated. There is very good agreement between these and the experimental values. The results for adipic acid in cm−1 are: 304 (0 → 1), 270 (1 → 2), 241 (2 → 3), 222 (3 → 4) 201 (4 → 5), 183 (5 → 6). In the case of sebacic acid some of the intermediate and higher transitions are absent in the spectrum recorded by the author. From the above data for adipic acid the dissociation energy of the hydrogen bond was evaluated as 5·9 kcal/mole in fair agreement with the values derived from conventional methods.

Electron spin resonance in cupric acid fluoride

The electron spin resonance in undiluted single crystals of cupric acid fluoride has been investigated at room temperature with microwaves of frequency 9625 Mc/s. The anisotropy in the g value has been measured in three orthogonal planes. The principal g values gave gshort parallel = 2.410 ± 0.010, gperpendicular = 2.090 ± 0.010. The linewidth shows anisotropy with orientation. The exchange frequency has been estimated to be approximately 0.08 cm-1.The powdered specimen shows asymmetry in the line shape.

Mechanism of the addition of alcohols to substituted phenylisothiocyanates : Electrical effects of the substituents on the reaction

The addition reaction of alcohols to substituted phenylisothiocyanates is found to be a second-order reaction. The reaction is catalysed by triethylamine. First-order rate constants of the addition reaction have been determined in excess of ethanol, for a number of substituted phenylisothiocyanates and the rate data give a satisfactory linear correlation with Hammett σ constants of groups. While the energies of activation vary randomly with substitution, the entropies of activation bear a linear relationship to the energies of activation. Infra-red spectra indicate that the thiourethanes which are the products of the addition reaction exist in the thioamide form. The most prominent resonance form which can satisfactorily explain both the kinetic and infrared data, has been suggested.

Raman spectra of crystalline double sulphates Part II. Ammonium double sulphates

Raman spectra of single crystals of (NH4)2M(SO4)2·6 H2O where M=Mg, Zn Ni or Co have been recorded using λ 2537 excitation. Interesting results concerning the substitution of the divalent atoms in the double sulphate lattice on the sulphate and ammonium frequencies are observed. The spectra of these double sulphates are discussed in the light of the known crystal structure details and in relation, to the spectra of the corresponding potassium double sulphates, reported recently by the author. The Raman spectrum of NaNH4SO4·2 H2O has also been recorded for the first time and the results obtained are also included.

Polarisation studies on the Raman spectra of cubic crystals - Part II: Calcium fluoride and potassium aluminium sulphate

Polarisation characters of the Raman lines of calcium fluoride (fluorspar) and potassium aluminium sulphate (alum) were investigated under the following conditions. Unpolarised light was incident normally on a face of the crystal making an angle 22.5° with a cubic face and the light scattered transversely along a cubic axis was analysed by a double image prism kept with its principal axes inclined at 45° to the vertical. Under these conditions the depolarisation factors of the Raman lines belonging to the totally symmetric (A), the doubly degenerate (E) and the triply degenerate (F) modes should be respectively =1, >1 and <1. The characteristic Raman line of CaF2 at 322 cm-1 exhibited a depolarisation value less than 1, showing thereby that the corresponding mode is a triply degenerate one (F). The Raman lines observed in the spectrum of K-alum were also classified and the results were compared with those given by previous investigators using standard crystal orientations.

Infrared spectra of trichloroacetates of copper, calcium, strontium and barium

Infrared spectra of trichloroacetates of Cu, Ca, Sr and Ba were studied in order to investigate the effect of coordination on the vibration spectra of the ligand. The shifts of the antisymmetric and symmetric COO- stretching frequencies are explained on the basis of the type of co-ordination of the COO- group to the metal ion. From the spectra it is established that the coordination of the COO- group to metal is different for trichloroacetates and monochloroacetates.