NOTES
2458
Nitrogen-containing products were not detected, perhaps because of the analytical method used. However, in a system of CH3 and S O , products like HCN, HzO, SH3, CO, Nz, COZ, and CH3CN were detected by mass spectrometry.22
Acknowledgment. We are grateful to the National
Research Council and to the Petroleum Research Fund of the American Chemical Society for financial support. We are also greatly indebted to Dr. G. B. Porter for many valuable discussions. (22) W. A. Bryce and K. U. Ingold, J . Chem. Phys., 23, 1968 (1955).
NOTES
Structure of Aluminum Cations in Aqueous Solutions by J. J. Fripiat, F. Van Cauwelaert, and H. Bosmans
noticeable modifications in vibration frequencies but indicated a progressive decrease of the band intensities. It will be therefore tentatively assumed that conclusions deduced from spectroscopy in the concentration 0.5 F may be extrapolated to more dilute solutions.
Laboratoire de Chimie M i n l r a l e , Institut Agronomique de 1' UniversitC de Louvain, HtverlC-Louvain, Belgium (Received November SO, 1964)
Structural data on polynuclear complexes in solution may be obtained from potentiometric and spectroscopic methods. Theoretical treatment developed by SillBn leads to the calculation of average condensation degrees p and p for A,B, complexes.' Moreover. if parallel curves Z(1og [A])B are obtained, S i l l h has shown that these complexes have the structure B(AIB)l, where t and n may be derived according to different hypothese~.~,3 Z is the average number of OH- bound to aluminum. (See Figure 1.) The attenuated total reflectance technique developed by Fahrenfort4s5 makes possible observation of the infrared spectrum of an ion in solution since the strong absorption bands due to the solvent are weakened materially. The method has been applied already by Katlafsky arid I'
m
teneityb
m 1960
Department of Chemistry, Cornell University, Ithaea, New Y O T ~ (Received February 16, 1966)
In-
m
Ys
(log)
S
Ys
("B)
m,w
YS
B1 IOB-Br asymmetric stretch Bl llB-Br asymmetric stretch B1. 'OB-Br asymmetric stretch B1 llB-Br asymmetric stretch B1 'OB-H in-plane bend Bl "B-H in-plane bend B1 B-D in-plane bend
Band centers measured from band contour. medium, w = weak.
*s
=
strong,
=
six infrared active bands are observed. One or two bands probably lie below our spectral cutoff at 400 Crn-1. The bands at 2620 and 1965 Cm,-l are readily (1) Work supported by Army Research Office (Durham) and the Advanced Research Projects Agency. (2) (a) T. D. Coyle, J. J . Ritter, and T. C . Farrar, Proc. Chem. SOC., 25 (1964); (b) L. Lynds and C . D. Bass, Bull. A m . Phys. S O C . , [61 9 , 661 (1964).
(3) R. F. Porter and S. K. Wason, J . Phys. Chem., 69, 2208 (1965). (4) L. Lynds and c. D. Bass, Inorg. Chem., 3 , 1063 (1964). (5) D. Brieux de Mandirola and J. F. Westerkarnp, Spectrochim. Acta., 2 0 , 1633 (1964). (6) L. Lynds and C. D. Bass, J . Chem. Phys., 40, 1590 (1964). (7) C. D. Bass, L. Lynds, T. Wolfram, and R. E. DeWames, J . Chem. p h y s , , 40, 3611 (1964). (8) (a) For HBFz see ref. 2b and 3 ; (b) for HBCl? see ref 4, 5, and 7 .
Volume 69, ,Vumber 7
July 1966
