Measurement of atmospheric HO by a chemical method

The parameters for a chemical technique can be outlined from the following set of desirable goals: (1) sufficient conversion of tracer species A to product B that B can be measured quantitatively in the presence of A and a great excess of air; (2) specificity of reaction such that A is converted to B only by reaction with HO; and (3) sufficient sensitivity for detection that the ambient concentration of HO is not seriously perturbed by the presence of A and B. This proposed study involves finding a chemical reaction specific enough for OH, and a measurement of the product formed. What one wants is a rate constant of about 10 to the -10th power cu cm/s, so that 0.1 percent of the OH will be converted in 100 s. Laboratory studies are needed to find a reaction which will fill this bill, yielding a product in quantity sufficient for precise measurement. This is an extremely fast constant and the search may be difficult. Again there is a question of perturbing the local environment, while still providing a sensitive measurement. Also the temperature and pressure dependence of the reaction rate is a complicated function for many of these species (that is, one must use a RRKM or Troe-based picture), and must be taken into account

A significant upper limit for the rate of formation, of OCS from the reaction of OH with CS2

The rate of reaction of OH with CS2 to form OCS by reaction (1) has been measured through observation of O14CS following 254 nm equation image photolysis of mixtures of H2O2 with 14CS2. The OH concentrations have been monitored through simultaneous measurement in the same cell of either (a) the oxidation of CO to CO2, or (b) the removal of a hydrocarbon such as C3H8 or iso-C4H10. The upper limit for the formation of OCS based on (a) corresponds to a rate constant k1 < 0.3 × 10−14 cm³ molecule−1 sec−1. Other chemical reactions in the system have led to the formation of both 14CO and 14CO2, indicating the existence of a complex combination of reactions such that the observed O14CS need not have been formed by (1). The rate of reaction (1) is sufficiently slow that it is neither an important atmospheric sink for CS2 nor an important source for atmospheric OCS. The reaction of OH with OCS has not been measured in these experiments, but by analogy with k1 it is probably not an important atmospheric sink for OCS nor an important source of SO2

Origin of impurities formed in the polyurethane production chain. 1: conditions for chlorine transfer from an aryl isocyanide dichloride byproduct

Phenyl and 4-methylphenyl isocyanide dichlorides are models for byproduct that may be formed in the later stages of certain polyurethane production chains. Photochemical electron paramagnetic resonance (EPR) studies (λ &gt; 310 nm), using the spin trap, N-tert-butyl-α-phenylnitrone, confirm a previously made suggestion that ArN═CCl2 can behave as a chlorine radical source. EPR spectra recorded during and after irradiation and supported by simulations evolve over time and indicate formation of the short-lived spin trap–Cl• adduct and a longer lived benzoyl-N-tert-butylnitroxide radical. Photolysis of C6H5N═CCl2, either alone or mixed with methylene diaryl isocyanate species, in o-C6H4Cl2, a polyurethane process solvent, led to the formation of mixtures containing dichloro- and trichlorobiphenyl isomers