Catalyst X (X = H2O, (H2O)2and (H2O)3) is incorporated into the channel of H2S +3O2formation and the catalytic effect of water, water dimers and water trimers is mainly taken from the contribution of a single water vapor molecule.
On the basis of the work done by Darling and Dennison on the water vapor molecule, the vibrational constants of acetylene are calculated, taking into account the resonance interaction arising from the near equality of the fundamentals ν1 and ν3. Seventeen band centers are known experimentally. The band centers depend on the 10 constants χi, χik and γ which are functions of the potential constants. The expressions for the vibrational energies of the band centers are set up, those for interacting doublets or triplets being found by perturbation methods. The 10 constants are determined and the positions of eight bands calculated to check the results. The agreement is very satisfactory. The positions of 10 other bands not yet observed are predicted.
The spectra of normal and heavy water vapor have been observed under high resolution in the region 1220–1240 Å. One band of H2O and two bands of D2O have been measured and analyzed. The spectra were taken in the ninth order of a 35-ft concave-grating spectrograph and the accuracy of measurement of the sharper lines is estimated to be about ± 0.005 Å. The results of the analyses are summarized below.[Formula: see text]These bands have been assigned as belonging to the first member of one of the two np Rydberg series.
In the incorporation of the catalyst (H2O)n (n = 1–3) into the HO2 + HO2 → H2O2 + 3O2 reaction, the catalytic effect of water, water dimers and water trimers is mainly derived from the contribution of a single water vapor molecule by a stepwise route.
The infra-red absorption spectrum of liquid deuterium oxide (“heavy water”) has been investigated by Ellis and Sorge (1934) and, in the region 2·5-9
μ
, by Plyler and Williams (1936). In the course of some other investigations at the Imperial College the absorption spectrum of this substance was remeasured between 0·9 and 2·1
μ
, but the results obtained did not fully confirm those of Ellis and Sorge. In view of the importance of heavy water as a solvent for absorption spectroscopy in the infra-red, it is necessary that its spectrum should be known as accurately as possible, and it therefore seems desirable to publish the new results for comparison with the earlier ones, and to reconsider the theoretical origin of the spectrum.
The near infra-red absorption spectrum of heavy water