Cl Isotope Research Articles

Schwingungsspektren und Kraftkonstanten symmetrischer Kreisel—XI Die IR-Spektren von HGeCl 3 und DGeCl 3

The gas phase i.r. spectra of HGeCl 3 and DGeCl 3 have been reexamined and recorded between 100 and 4000 cm −1 with grating instruments. All fundamentals have been measured to 0.5 cm −1, and approximate Coriolis ζ constants have been deduced from band contours. The influence of Ge and Cl isotopes haa been elucidated. A seven parameter force field which reproduces all observed frequencies with satisfactory accuracy is reported and compared with those of other HE IVCl 3 and chlorogermane molecules.

Persistence of organochlorine insecticides on different substrates under different environmental conditions. I. The rates of loss of dieldrin and aldrin by volatilisation from glass surfaces

AbstractThe losses of dieldrin and aldrin by volatilisation from crystalline deposits on glass surfaces in different environments were studied by using these insecticides labelled with the radioactive isotope 36CL as a tracer.Volatilisation rates were very sensitive to changes in temperature and to a lesser extent to air movement, but not to change in relative humidity (the effect of which was measurable only on porous glass surfaces).All rates of loss from glass surfaces could be described mathematically in terms of single or double exponential equations, although many were better described by simple sigmoid (logistic) equations.

The permeability of mammary ducts.

1. The permeability of the teat mucosa of the goat has been studied in vitro and, as an isolated teat pouch, in vivo. In vivo the mucosa was found to be impermeable to radioactive Na, K, Cl and Rb isotopes and to labelled lactose, but permeable to (3)HOH, and to a lesser extent, urea.2. The permeability of the intramammary ducts has been assessed by comparison of the rates of passage from the blood of ions and urea relative to (3)HOH into various fractions of milk in different parts of the gland.3. Negligible quantities of ions were detected in the milk present in large ducts after an I.V. infusion or during a close arterial infusion to keep the venous blood concentrations constant. However, after approximately 25 min, milk in the alveoli had fully equilibrated with (3)HOH, and (24)Na(+) and was almost fully equilibrated with urea but not with (42)K(+) and (36)Cl(-).4. The quantity of milk in a fraction of milk was directly related to the amount of (3)HOH present in that fraction but not to the amounts of the other indicators (urea, labelled Na, K, Rb and Cl). Comparison of the concentration of these substances with (3)HOH in different milk fractions indicates that the mammary ducts are probably impermeable to ions and only slightly permeable to urea.5. The injection of [(14)C]lactose into the teat showed that after 10 and 20 min, 7 and 14% respectively of the radioactivity had reached the residual (alveolar) milk. Thus diffusion within the milk in the ducts could account for the small quantities of labelled ions found in milk within the ducts following intravascular injection.6. It is concluded that the large and medium-sized ducts in the mammary gland are impermeable to lactose and to the monovalent ions studied.7. In non-lactating animals, the ducts are more permeable to Na(+) and Cl(-) than in the lactating animals.8. The relative rates of passage of ions into residual (alveolar) milk was Na > Cl > K.

Schwingungsspektren und kraftkonstanten symmetrischer kreisel—II HSiCl3 und DSiCl3

Zusammenfassung The infrared spectra of gaseous HSiCl 3 ahd DSiCl 3 down to 140 cm −1 are reported. A force field reproduced by Table 6 has been computed using frequencies, 35 Cl/ 37 Cl isotope splittings and ζ constants from band contours. f SiCl is calculated to be 2·918, f SiCl/SiCl, being 0·068 mdyn/A.

Analysis of S and Cl wave functions by direct reactions

The deuteron energy spectrum and the angular distributions to the ground and 2.13 and 3.31 MeV excited states of34S have been measured for the reaction35Cl(n, d)34S. These results and the available experimental data of stripping and pick-up reactions on S and Cl isotopes are analysed using the DWBA and spectroscopic factors for several transitions are obtained. These factors are then compared with those predicted on the basis of the shell and collective rotational models. A good agreement is found with the predictions of the shell model in which phenomenological two-body matrix elements are used.

A High-Resolution, Far Infrared Double-Beam Lamellar Grating Interferometer

A high-resolution, far ir lamellar grating interferometer that operates in either a single-beam or a double-beam differencing mode of operation is described. The instrument covers a frequency range of 10 cm(-1) to 125 cm(-1) (1000 micro to 80 micro). To illustrate the general performance of the instrument the pure rotational spectrum of water vapor between 15 cm(-1) and 115 cm(-1) is presented. It is estimated that the absorption line centers of strong isolated lines are measured to within +/-0.008 cm(-1). To illustrate the resolution of the instrument, low wavenumber portions of the pure rotational spectrum of DCl are shown. The Cl(35)-Cl(37) isotope splitting of the J = 2 --> 3 transition (32.3 cm(-1)) is clearly resolved. The calculated separation of these two lines is 0.094 cm(-1).

ION AND WATER TRANSPORT IN ISOLATED INTESTINE OF THE MARINE TELEOST, COTTUS SCORPIUS.

ABSTRACT The unidirectional sodium fluxes from mucosa to serosa and from serosa to mucosa have been studied in the isolated small intestine of Cottus scorpius, bathed in Ringer and sulphate Ringer, by use of the isotope 22Na. In addition the unidirectional chloride fluxes have been studied in Ringer and choline Ringer using the isotope 36Cl. In Ringer the mean ± S.E. values of these fluxes have been found to be: for sodium, 8·4+ 0·6 (serosa to mucosa) and 23·9+0·7 (mucosa to serosa) /μequiv. cm. -2 hr. -1 and for chloride, 10-5 ± 0-9 (serosa to mucosa) and 21·9 ± 0·9 (mucosa to serosa) μequiv. cm. -2 hr. -1. In sulphate Ringer the mean ± s.E. values for sodium were 4‘5 ± 0·3 (serosa to mucosa) and 6·8 ± 0·6 (mucosa to serosa) /μequiv. cm. -2 hr. -1 and in choline Ringer the mean ±S.E. values for chloride were 5·1 ± 1·0 (serosa to mucosa) and 5·94 + 0·9 (mucosa to serosa) /μequiv. cm. -2 hr. -1. The respiration rates of pieces of intestine placed in Ringer, sulphate Ringer, choline Ringer and artificial sea water have been measured in a Warburg apparatus. The mean ±S.E. values of oxygen consumption in these media have been found to be 0·4 ± 0·2 (Ringer), 0·3 ± 0·2 (sulphate Ringer), 0·3 ± 0·2 (choline Ringer) and 0·1 ±0·2 (artificial sea water) μ1. O 2/mg. dry weight.hr. The electric potential differences between identical serosal and mucosal media bathing isolated intestines have been measured. The mean + s.E. values of the potential difference in Ringer, sulphate Ringer, choline Ringer and artificial sea water have been found to be +0·6 ± 0·3, +2·2 ± 0·2, + 0·8 ±0·3 and +1·3+ 0·2 mV., respectively (mucosal medium taken as reference). The hydraulic conductivity of the isolated intestine has been found by measuring the change in net water flux arising from the creation of an osmotic gradient across this tissue. Net water flux was measured by the change in weight of normal filled sacs. The mean + s.E. value for this parameter has been found to be 0·22 ± 0·05 μ1/cm. 2 mosmolar. hr. (or 2·4+0·6 cm. sec. -1 atm. -1). It has been found that, when artificial sea water is placed in the lumen of the intestine bathed in Ringer, a net flow of water into the lumen occurs. This net water flux falls to zero at a time dependent on the luminal volume (to be diluted) and, thereafter, a net water flux (mucosa to serosa) is established. The net water movement across isolated intestines bathed on both sides by identical media has been studied. The mean ± s.E. values for net water flux (mucosa to serosa) have been found to be: in Ringer, 8·1±0·8, in sulphate Ringer, 3·6±0·5 and in choline Ringer, 6·7 ± 0·6 µ. cm. -2 hr. -1. The results are interpreted as showing that the net transfer of sodium and chloride ions between identical Ringer solutions is achieved by some process whereby these ions are ‘pumped’ in the form of electrically neutral sodium chloride. It is considered that there is some evidence for the existence of a frictional interaction between sodium chloride and water as they pass across the intestine.

Cross Sections for the Production of Cl, K, Ca, and Sc Isotopes in the Bombardment of Pb and U with 3.0-Bev Protons

Cross sections for the formation of some nuclides in the mass number range 38-48 in the bombardment of Pb and U with 3.0-Bev protons have been measured. The maximum of the isobaric yield distributions for the nuclides from the Pb bombardment occurs at the stability line, while that from U is somewhat on the neutron-excess side. Total cross sections of 4-5 mb per mass number are deduced from the Pb data leading to a revision of the mass-yield curve in this region as proposed by Wolfgang et al. The cross sections from uranium are approximately twice as large as those from Pb. The data are shown to be consistent with a cascade-fission-evaporation mechanism.

XXXVIII. Diffusion of the chloride ion in NaCl

Abstract The rate of diffusion of 24Na in NaCl has been measured (Mapother, Crooks and Maurer 1950) by evaporating a film of 24NaCl on to the surface of a crystal of NaCl and subsequently determining the concentration of 24Na as a function of the distance from the surface. Two diffusion processes have been found-diffusion by vacancies created thermally at higher temperatures (intrinsic range) and by vacancies produced by positive divalent impurities at lower temperatures (structure sensitive range). Some problems of interpretation raised by the experiments have been discussed by the above authors and by Seitz (1954). The study of the diffusion of the chloride ion using the same technique with the isotope 36Cl (Chemla 1952) has been limited to temperatures exceeding 650°c by the low mobility of the chloride ion. The present note describes a different tracer method which allows diffusion of the chloride ion to be studied at much lower temperatures. Preliminary results for the diffusion coefficient and activation energy of chloride ion diffusion at 510°c and below are compared with data from the above mentioned papers.

Microwave Spectra of the Alkali Halides

Data from the microwave spectra of all alkali halides excepting LiF, NaF, KF, RbF, and LiCl are given and analyzed in terms of molecular and nuclear constants. These yield internuclear distances and ionic radii for the gaseous alkali halides, molecular dipole moments, potential constants including four constants for some molecules, amount of covalent character from quadrupole coupling constants and from rotational effects, and mass ratios for isotopes of Li, K, Rb, Cl, and Br.

Nuclear Quadrupole Resonance of the Stable Gallium Isotopes

Eight absorption lines have been observed in a sample of polycrystalline Ga${\mathrm{Cl}}_{3}$. Of these, six are ascribed to the Cl isotopes. The remaining two, which are due to the stable gallium isotopes ${\mathrm{Ga}}^{69,71}$, allow us to determine the ratio of their quadrupole moments. $\frac{{Q}_{{\mathrm{Ga}}^{69}}}{{Q}_{{\mathrm{Ga}}^{71}}}=1.5867\ifmmode\pm\else\textpm\fi{}0.0004$, in agreement with earlier atomic beam measurements.

Microwave Spectra of CsF, CsCl, and CsBr

Molecular constants for CsF, CsCl, and CsBr have been determined from measurements of their pure rotational spectra in the microwave region. These and other data allow a test of the constancy of ionic bonding radii. Measurements of isotopic species of these molecules give the mass ratios of the stable Cl and Br isotopes.

On the Nuclear Magnetic Moments of Several Stable Isotopes

The nuclear induction spectrometer which has previously been described was used to measure the magnetic moments of a number of nuclei. These values are without corrections of any kind and are based upon a value for the magnetic moment of the proton of (2.79348\ifmmode\pm\else\textpm\fi{}0.00034) nuclear magnetons. The experience gained from the observation of a large variety of nuclei has made it possible to discuss in a general way the selection of a suitable sample compound. Various interesting phenomena which have turned up in the course of these measurements are discussed; some of these are the following. (a) Nuclear resonance frequencies have been found to depend upon the compound used for the sample in some cases. This has been noted for the isotopes of Cl and N, and for Co, the latter having resonances over a region as large as 1.3 percent. This effect has been demonstrated to be of molecular rather than nuclear origin, and it is responsible for our listing the chemical compounds used for each measurement. (b) The magnetic moments of both ${\mathrm{In}}^{113}$ and ${\mathrm{In}}^{115}$ have been found to be 0.64 percent greater than their respective atomic beam values, a discrepancy very similar to that noted for ${\mathrm{Ga}}^{69}$ and ${\mathrm{Ga}}^{71}$. (c) An hfs anomaly for the isotopes of chlorine has been observed, which is notable, because the atomic beam experiments deal with the ${\mathrm{P}}_{3/2}$ state of atomic chlorine. (d) An unusual structure for the ${\mathrm{Sb}}^{121}$ and ${\mathrm{Sb}}^{123}$ resonances in aqueous solution of NaSb${\mathrm{F}}_{6}$ has been observed and is qualitatively explained.

Efficiency of the Electrolytic Separation of Chlorine Isotopes

The electrolytic separation coefficient α has been determined for the chlorine isotope separation in the electrolysis of sodium chloride solutions at a platinum anode. Flotation of purified NaCl crystals in ethylene dibromide was employed as the analytical procedure in determining the isotopic composition of samples. Densities of the ethylene dibromide as a function of temperature were separately determined. The electrolytic separation factor for Cl isotopes was found to be 1.0060±0.0005 for the temperature range 25° to 40°C. No significant dependence on either temperature or current density was observed. The coefficient on platinum (1.0060±0.0005) agrees with the value on Acheson graphite (1.0068±0.0014) which may be computed from the data of Yacouban.

The Band Spectrum of Silver Chloride

Analysis of vibrational structure. ---The electronic band system of AgCl extending from $\ensuremath{\lambda}3124$ to $\ensuremath{\lambda}3400$ has been obtained in emission and absorption, the latter under high dispersion. A complete vibrational quantum analysis has been carried out, giving the following formula for the heads of the bands of the molecule ${\mathrm{Ag}}^{107}$${\mathrm{Cl}}^{35}$: $\ensuremath{\nu}=31574.4+275.0{v}^{\ensuremath{'}}\ensuremath{-}6.20{v}^{\ensuremath{'}2}\ensuremath{-}0.130{v}^{\ensuremath{'}3}\ensuremath{-}342.4{v}^{\ensuremath{'}\ensuremath{'}}+1.163{v}^{\ensuremath{'}\ensuremath{'}2}$The data give $\ensuremath{\omega}_{e}^{}{}_{}{}^{\ensuremath{'}}=343.6$ ${\mathrm{cm}}^{\ensuremath{-}1}$, $\ensuremath{\omega}_{e}^{}{}_{}{}^{\ensuremath{'}}=281.0$, and ${\ensuremath{\nu}}_{e}=31606.9$ ${\mathrm{cm}}^{\ensuremath{-}1}$. Vibrational quantum numbers have been assigned to Franck and Kuhn's data for AgBr and AgI.Isotope effects. ---The vibrational isotope effect was observed for both the Cl and the Ag atoms. The complete spectrum consists of four overlapping systems due to the four possible isotopic molecules. The order of magnitude of the isotope shift for the Cl isotope effect was 1 to 30 ${\mathrm{cm}}^{\ensuremath{-}1}$; for the Ag isotope effect, 1 to 4 ${\mathrm{cm}}^{\ensuremath{-}1}$. The agreement of observed shifts with those calculated from the equations recently derived by Birge (not yet published) is close.Energies and products of dissociation. The heats of dissociation of the AgCl molecule are $D_{0}^{}{}_{}{}^{\ensuremath{'}\ensuremath{'}}=3.11$ volts in the normal state, $D_{0}^{}{}_{}{}^{\ensuremath{'}}=0.31$ volt in the excited state. The energy of excitation of the atoms resulting by dissociation from the excited state is 1.10\ifmmode\pm\else\textpm\fi{}0.12 volt. This value can be explained if it is assumed that $^{2}D^{\ensuremath{'}}$ states exist in Ag as in Cu and Au. It is concluded that the silver halides dissociate from the excited state into a silver atom in a $^{2}D^{\ensuremath{'}}$ state and a halogen atom in the metastable $^{2}P_{\frac{1}{2}}$ state.