Cyclic voltammetry and spectroelectrochemical study of nickel and cobalt diphenyltetraazaannulene complexes

The absorption spectra. cyclic voltammetry and spectroelectrochemistry of [Ni(II)DPTAA] and [Co(II)DPTAA] (DPTAA = 6,13-diphenyldibenzo[b,i][1,4,8,11] tetraaza[14]annulene) complexes in DMF are reported in detail. The ligand oxidation is observed for [Ni(II)DPTAA] at +0.70 V vs. SCE whereas Ni2(+/+) occurs at - 1.60 V. For [Co(II)DPTAA], a ligand oxidation redox couple is seen at +0.56 V while the Co2+/+ and Co2+/3+ redox couples appear at -1.21 and +0.24 V, respectively. All observed redox couples are assigned to reversible one-electron processes on account of peak separations and scan-rate dependency. These processes were further investigated by spectroelectrochemistry for [Co(II)DPTAA]. For [Co(II)DPTAA], axial ligation of pyridine was found to shift the Co2+/3+ redox couple more negative. while the ligand oxidation was shifted to more positive potentials. From a spectrophotometric titration of [Co(II)DPTAA] with pyridine an equilibrium constant, K-f, was determined for the binding of pyridine to [Co(II)DPTAA]. This was found to be 10.2 dm(3) mol(-1), slightly lower than that of [Co(II)TAA], indicating the influence of the phenyl groups. From this value and shifts in the Co2+/3+ redox couple upon ligation, an equilibrium constant for the binding of pyridine to [Co(III)DPTAA], K'(f), was found to be 5.06 x 10(6) dm(3) mol(-1). (c) 2007 Elsevier B.V. All rights reserved.

Examining the effect of exit separation on aircraft evacuation performance using evacuation modelling techniques: "Is the 60 foot rule relevant?"

This paper examines the influence of exit separation, exit availability and seating configuration on aircraft evacuation efficiency and evacuation time. The purpose of this analysis is to explore how these parameters influence the 60 foot exit separation requirement found in aircraft certification rules. The analysis makes use of the airEXODUS evacuation model and is based on a typical wide-body aircraft cabin section involving two pairs of Type-A exits located at either end of the section with a maximum permissible loading of 220 passengers located between the exits. The analysis reveals that there is a complex relationship between exit separation and evacuation efficiency. Indeed, other factors such as exit flow rate and exit availability are shown to exert a strong influence on critical exit separations. A main finding of this work is that for the cabin section examined under certification conditions, exit separations up to 170 feet will result in approximately constant total evacuation times and average personal evacuation times. This practical exit separation threshold is decreased to 114 feet if another combination of exits is selected. While other factors must also be considered when determining maximum allowable exit separations, these results suggest it is not possible to mandate a maximum exit separation without taking into consideration exit type, exit availability and aircraft configuration. This has implications when determining maximum allowable exit separations for wide and narrow body aircraft. It is also relevant when considering the maximum allowable separation between different exit types on a given aircraft configuration.