James D. Ray

Analysis of the proton nuclear magnetic resonance spectrum of formamide by the double resonance technique

Abstract The proton magnetic resonance spectrum of formamide, DCONH2, HCOND2 and HCONHD are analyzed, spin-spin couplings are determined. The method of analysis utilizes selective decoupling of the N14 nucleus while observing the proton resonance. The complete relaxing of the N14 nucleus eliminates the smearing effect of the electric quadrupole relaxation over the proton resonance spectrum.

Preparation and Proton Magnetic Resonance Studies of Anhydrous Ammonia

Comparison of high‐resolution proton magnetic resonance spectra of anhydrous N14H3 and N15H3 (99.8% N15) leads to the conclusion that the line width in N14H3 is due to quadrupole relaxation. A new method of preparation of anhydrous, sodium‐free ammonia is described. The natural abundance of N15H3 in N14H3 is shown to be observable by magnetic resonance technique.

Proton and Nitrogen Magnetic Resonance Spectra and Structure of Nitramide and Nitrourethane

Nuclear magnetic resonance spectra of both protons and N14 nuclei in nitrourethane and nitramide have been studied. Spectra are interpreted in terms of the structures R–NHNO2 and H2NNO2 for nitrourethane and nitramide, respectively. Protons have been established as all being of amino type.

Structural Isomer Discrimination between Cyanamides and Carbodiimides by Nitrogen Nuclear Magnetic Resonance

The structural isomers diethylcyanamide and N,N′‐dicyclohexylcarbodiimide were studied by both proton and nitrogen NMR techniques. The structures R2N–C≡N and R–N=C=N–R have been shown to apply to cyanamides and carbodiimides, respectively.

Kinetics of the Nitrogen Dioxide Catalyzed Oxidation of Nitric Oxide

The rate constant for the reverse reaction of the rate controlling step (NO+O2+NO2=NO2+NO3) of high pressure nitrogen pentoxide decomposition has been determined to be 6.58×107 cc2 mole—2 sec—1. This reaction was found to be the rate‐controlling step in the nitrogen dixoide catalyzed oxidation of nitrosyl chloride to nitryl chloride. The equilibrium constant at 25° for the reaction ClNO+NO2=ClNO2+NO as evaluated from the kinetic data was found to be 1×10—4.

Heat of Water Vaporization as a Chemical Calibration Standard for Solution Calorimetry

A simple method for calibration of calorimeters used in solution calorimetry has been devised. The heat of vaporization of water is taken as a chemical standard for this process and shown to be unaffected by the speed and pressure employed in pumping it out of the evaporator described.

New Low‐Holdup High‐Efficiency Laboratory Distillation Column

A new type distillation column similar to a Vigreau column is described which has the indentations perpendicular to the wall of the tube. It was found that the indentations gave optimum performance if at an angle of 90° to the axis of the column. A jig is described which facilitates making indentations in glass tubing so as to result in a high precision of indentation spacing.