P. Harteck

Decomposition of Nitric Oxide and Nitrogen Dioxide by the Impact of Fission Fragments of Uranium‐235

A study was made of the decomposition of nitric oxide and nitrogen dioxide using the fission recoil energy of 5 mg of uranium‐235 oxide powder. The irradiations were conducted in a 23‐cc quartz vessel, at a flux of 3×1012 neutrons | cm2 second, and at a temperature of 70°C in the Brookhaven National Laboratory Reactor. With a dose of 2×109 r, the over‐all GNO is 9.5±1.0, using a radiation intensity of 1.0×107 r | min, a filling pressure of 500 mm at 21°C. With a dose of 108 r, the GNO is 13.8±1.4. Since three additional nitric oxide molecules are consumed for each nitric oxide molecule decomposed at 108 r, the GNO value calculated for the primary decomposition (including the dissociation due to ion‐recombination) is 3.45±0.35.The GNO2 value is 1.2 for a dose of 3×109 r and 0.5 for 5×107 r, conducted under a radiation intensity of 1.2×107 r | min and a filling pressure of 550 mm of the 2 NO2⇄N2O4 equilibrium at 21°C. For the principal reactions in the nitric oxide and nitrogen dioxide systems, when irradia...

SURFACE-CATALYZED EXCITATIONS IN THE OXYGEN SYSTEM,

A luminosity is produced over Ni maintained at approximately 20°C in a stream of O atoms. Spectroscopic investigation shows the strongly forbidden b 1Σg+ — X 3Σg— atmospheric system and A 3Σu+ — X 3Σg— Herzberg system of the O2 molecule plus four strong heads of the (0, 0) band of the OH A 2Σ+ — X 2Π interaction. Certain spectral features in the region of the (0, 0) atmospheric band could not be resolved for positive identification but are suggested to be the vibrational‐rotational bands of OH. The Herzberg and atmospheric bands appear to be primary products of the surface catalysis while the OH molecule can be either a surface product or the result of chemical reactions of certain excited species present.

A Spectroscopic Study of Alpha-Ray-Induced Luminescence in Gases: Part I

In radiation chemistry, an understanding of the primary processes induced by ionizing radiation and the kinetics of the ions, atoms, and excited species is of paramount importance. From this basic information, chemical systems under ionizing radiation may be directed to produce desired phenomena. The fixation of nitrogen by means of ionizing radiation is one of the major interests of our group at Rensselaer Polytechnic Institute. In our investigation of the behavior of fission fragments on the nitrogen system, a spectroscopic study of the luminescence was desired. Since it was not possible to study spectroscopically the fission fragment luminescence in a nuclear reactor,2 large polonium a-particle sources were used as the best substitute available.

Reaction of Oxygen Atoms with Nitric Oxide

The rate of reaction of oxygen atoms with nitric oxide has been studied at several pressures (0.62, 0.85, 1.11 mm Hg) by measuring the relative intensities of the oxygen afterglow. The consumption of O atoms was observed as a three‐body recombination (NO+O+M→NO2+M). At room temperature the reaction coefficient was found to be k2=7.6×10‐32 cm6 molecules‐2 sec‐1, with an average deviation of 6.5%. The third body was mainly argon.

Chemiluminescent Nitric Oxide—Oxygen‐Atom Reaction at Low Pressures

The light emitting reaction NO+O→NO2+hv is shown to be second order in the pressure region of 3 to 20 μ. This would indicate that the major source of emission is a simple radiative combination of nitric oxide and oxygen atoms. In addition, any excitation and emission mechanism involving a third body would be too small to account for the light emission observed.

Reaction of Carbon Monoxide and Ozone

The reaction between ozone and carbon monoxide has been investigated at 35°, 100°, 180°, and 258°C. It could be shown that there is an initial period where the reaction proceeds an order of magnitude faster than after some carbon dioxide is formed. Further oxidation of carbon monoxide by ozone proceeds in the order of magnitude of the thermal decomposition of ozone.

The Relative Abundance of HT and HTO in the Atmosphere

A kinetic discussion of the HT and HTO formation in the atmosphere indicates that the ratio of about 1 HT to 1000 HTO in nature and the very high T concentration of 4.10‐15 in atmospheric hydrogen compared with about 3.10‐18 in normal rain water can only be understood by means of a photochemical reaction. Since the tritium atoms are quickly removed by oxygen molecules in three‐body collisions and form the TO2 radical which in turn forms HTO, the TO2 must be photochemically dissociated. The T atoms thus set free collide repeatedly with hydrogen atoms and undergo to a certain extent the exchange reaction H2+T=HT+H. On the other hand, the T atoms or TO2 radicals may react with ozone to form a OT radical which combines with the hydrogen of the atmosphere into HTO. In low altitudes the reaction of TO2 with air polluting bodies form HTO predominately. The ratio of these reactions is responsible for the ratio of HT and HTO in nature with the HTO brought down into the surface waters by rainfall.

Weitere Versuche mit Parawasserstoff

Verteilbecken aus, das 25oocbm Inhalt hat, werden die einzelnen Versuchsgerinne mit Wasser versorgt. Als einziges ~estes Gerinne wurde zun~chst ein 6oo m langer gerader IZanal flit 4 cbm/sec, vorgesehen, der in seinem oberen Teil als Erdgerinne, in seinem unteren Teil als Betongerinne ausgeffihrt wird (s. Fig. 2). Am Ende des Versuchsgerinnes befindet sich zu genauen VCassermessungen ein Becken mit 15oo cbm Nutzinhalt (Fig. 3)Mit Hilfe dieser Anlagen ist das Forschungsinstitut in der Lage, nicht nur Versuche an groBen Bauten und mit groBen Wassermengen durchzufiihren, sondern auch hohe Genauigkeit zu erzielen. Die erw~hnten Bauten waren Ende 1928 zu etwa dreivierteI Iert iggestell t Von dieser Zeit ab muBte die Baut~tigkeit wegen der Schneeund Frostverhgltnisse eingestellt werden. Der AbschhB der Arbeiten wird im Juni dieses Jahres erwartet, so dab die Anstalt in den Sommermonaten dem Betrieb fibergeben werden kann. Die Versuchsanlagen sollen in erster Linie zur ]3earbeitung solcher hydraulicher Probleme dienen, ffir deren ertolgreiche L6sung groBe Versuchsbauten und Beobachtungen in der Natur selbst Voraussetzung sind. Deshalb wird die Anstalt anch eine wertvolle Erg~nzung zu den bereits bestehenden FluBbaulaboratorien biiden, die ihre Erkenntnisse in der Regel an Versuchsmodellen in kleinem MaBstab gewinnen. Neben der ]3earbeitung yon hydraulischen Problemen allgemeiner Art wird das Forschungsinsfitut auch Spezialaufgaben in Angriff Fig. 3. MeBbecken nehmen. Auf dem ausgedehnten Gel~nde der Versuchsanstalt kSnnen z. ]3. Modelle yon projektierten Wasserbauten in sehr grol3em Mal3stab nachgebildet und untersucht werden. Auch in diesen ]?Mien wird das Inst i tut in erster Linie solche Aufgaben fibernehmen, ffir welche grof3e Abmessungen, groBe Wassermengen und natfirliche Bedingungen (z. 13. Geschiebe) notwendig sind. Als Beispiel sei auf Projekte zur ttochwasserfrei-

Nitrogen Pentoxide Formation by Ionizing Radiation

An experiment to ascertain the formation of nitrogen pentoxide by reactor irradiation of nitrogen-oxygen mixtures is reported. (J.E.D.) The irradiations were carried out in N/sub 2/ atmosphere using the gamma radiation from spent fuel elements. Under the experimental conditions atmosphere exerted no significant influence on the total amount of cyclohexane reacted but did affect individual product yields. Neglecting gaseous products, 3.3 wt. % of the cyclohoxane reacted. Bicyclohexyl is the major individual product of radiolysist it is confirmed that the cyclobexyl ring is comparatively resistant to ring rupture. However extensive rearrangement of five-membered ring system occurs. (J.E.D.)

The role of phosphorus in the upper atmosphere of Jupiter

Abstract The reaction of elemental phosphorus and H atoms to form PH3 was observed and should be a major factor in the recycling of PH3 in the stratosphere of Jupiter. The formation of PH3 in this manner should predominate at high altitudes where, due to the very low temperatures, reactions that require higher activation energies than these atom reactions cannot occur. At lower altitudes, in the troposphere, the rapid formation of H atoms from the strong absorption of light by NH3 will contribute to phosphine production also in this same manner. Recent experiments have also shown that elemental phosphorus reacts readily with aqueous ammonia to form PH3. This reaction may also be important in the recycling of PH3 in the upper troposphere of Jupiter if water-ammonia clouds, as had been previously thought, exist. Considerations of the coloration of the Great Red Spot have been made based upon the nature of the phosphorus obtained by decomposition of phosphine.