Difluoramine: an Infrared Study of the Complexes between Difluoramine and the Alkali Metal Fluorides

Abstract

The symbol An, for example, means A3 X A2, the A, values being those of eq. 4.) This equation is solved for the ß values by inverting the matrix A and multiplying A by A-1. One manipulative detail which may be troublesome is that the matrix elements cover a wide range of values-in the work reported here, 10-31 to 10~9-and the weights may have to be multiplied by some constant to keep the numbers within the capacity of the computer used. This constant can be factored out later.The least-squares procedure gives not only a set of ß values but also their standard deviations if the weights are on an absolute basis, i.e., if the terms in eq. 9 are all known and the proper estimates of and V are used. If this is done, the standard deviations of the ß values are equal to the square roots of the corresponding diagonal elements of the inverse matrix [i.e., ß2The last information available is the "goodness of fit,'' x, described in the text. This is calculated by evaluating F (eq. 6) at each point («, [L]) using the calculated ß values. These quantities are called the residuals; they would be zero if there were no errors in ñ, [L], or the ß values. The residual at each point is multiplied by the weight calculated for that point;where N is the number of observations (number of points) minus the number of parameters determined (3 in this case: ß , ß2, and ß ). The interpretation of X is described in the text.Contribution from the Chemistry Research Sect ion, Rocketdyne,

Silicon Imidazolidines

“…Elucidation of the structure of these complexes by low-temperature infrared techniques has been completed in this laboratory and will be reported separately. 7 Reproducible dissociation pressures for KF • HNF2 and RbF-HNF2 were measured and, as predicted from the relative basicities of the alkali fluorides, the stability of the complexes formed varied as follows: CsF > RbF > KF > NaF. In fact, no evidence was found for any interaction of difluoramine with NaF, CaF2, or NiF2 down to -80°.…”

Derivatives of Nitrogen Fluorides

“…The cesium fluoride complex explodes on warming to 0°. An infrared study of these complexes indicates that hydrogen bonding is probably responsible for complexation (KF-»-HNF2) (37). The infrared spectrum of the cesium fluoride complex gave indications for the presence of another species which was postulated to be CsNF2-HF (37), but further data are needed to confirm this.…”