Evaluation of data for atmospheric models: master equation/RRKM calculations on the combination reaction, BrO+NO2 -> BrONO2, a conundrum

Experimental data for the title reaction were modeled using master equation (ME)/RRKM methods based on the Multiwell suite of programs. The starting point for the exercise was the empirical fitting provided by the NASA (Sander, S. P.; Finlayson-Pitts, B. J.; Friedl, R. R.; Golden, D. M.; Huie, R. E.; Kolb, C. E.; Kurylo, M. J.; Molina, M. J.; Moortgat, G. K.; Orkin, V. L.; Ravishankara, A. R. Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation Number 15; Jet Propulsion Laboratory: Pasadena, California, 2006)(1) and IUPAC (Atkinson, R.; Baulch, D. L.; Cox, R. A.: R. F. Hampson, J.; Kerr, J. A.; Rossi, M. J.; Troe, J. J. Phys. Chem. Ref. Data. 2000, 29, 167) 2 data evaluation panels, which represents the data in the experimental pressure ranges rather well. Despite the availability of quite reliable parameters for these calculations (molecular vibrational frequencies (Parthiban, S.; Lee, T. J. J. Chem. Phys. 2000, 113, 145)3 and a. value (Orlando, J. J.; Tyndall, G. S. J. Phys. Chem. 1996, 100,. 19398)4 of the bond dissociation energy, D-298(BrO-NO2) = 118 kJ mol(-1), corresponding to Delta H-0(circle) = 114.3 kJ mol(-1) at 0 K) and the use of RRKM/ME methods, fitting calculations to the reported data or the empirical equations was anything but straightforward. Using these molecular parameters resulted in a discrepancy between the calculations and the database of rate constants of a factor of ca. 4 at, or close to, the low-pressure limit. Agreement between calculation and experiment could be achieved in two ways, either by increasing Delta H-0(circle) to an unrealistically high value (149.3 kJ mol(-1)) or by increasing , the average energy transferred in a downward collision, to an unusually large value (> 5000 cm(-1)). The discrepancy could also be reduced by making all overall rotations fully active. The system was relatively insensitive to changing the moments of inertia in the transition state to increase the centrifugal effect. The possibility of involvement of BrOONO was tested and cannot account for the difficulties of fitting the data.

An on-line algorithm of uncertain time delay estimation in a continuous system

In this paper, we present an on-line estimation algorithm for an uncertain time delay in a continuous system based on the observational input-output data, subject to observational noise. The first order Pade approximation is used to approximate the time delay. At each time step, the algorithm combines the well known Kalman filter algorithm and the recursive instrumental variable least squares (RIVLS) algorithm in cascade form. The instrumental variable least squares algorithm is used in order to achieve the consistency of the delay parameter estimate, since an error-in-the-variable model is involved. An illustrative example is utilized to demonstrate the efficacy of the proposed approach.

Design and evaluation of intelligent classifier based intrusion detection system

We have discovered a novel approach of intrusion detection system using an intelligent data classifier based on a self organizing map (SOM). We have surveyed all other unsupervised intrusion detection methods, different alternative SOM based techniques and KDD winner IDS methods. This paper provides a robust designed and implemented intelligent data classifier technique based on a single large size (30x30) self organizing map (SOM) having the capability to detect all types of attacks given in the DARPA Archive 1999 the lowest false positive rate being 0.04 % and higher detection rate being 99.73% tested using full KDD data sets and 89.54% comparable detection rate and 0.18% lowest false positive rate tested using corrected data sets.

Performance statistics of a head-operated force-reflecting rehabilitation robot system

Researchers in the rehabilitation engineering community have been designing and developing a variety of passive/active devices to help persons with limited upper extremity function to perform essential daily manipulations. Devices range from low-end tools such as head/mouth sticks to sophisticated robots using vision and speech input. While almost all of the high-end equipment developed to date relies on visual feedback alone to guide the user providing no tactile or proprioceptive cues, the “low-tech” head/mouth sticks deliver better “feel” because of the inherent force feedback through physical contact with the user's body. However, the disadvantage of a conventional head/mouth stick is that it can only function in a limited workspace and the performance is limited by the user's strength. It therefore seems reasonable to attempt to develop a system that exploits the advantages of the two approaches: the power and flexibility of robotic systems with the sensory feedback of a headstick. The system presented in this paper reflects the design philosophy stated above. This system contains a pair of master-slave robots with the master being operated by the user's head and the slave acting as a telestick. Described in this paper are the design, control strategies, implementation and performance evaluation of the head-controlled force-reflecting telestick system.

A helmet mounted display system with active gaze control for visual telepresence

The objective of a Visual Telepresence System is to provide the operator with a high fidelity image from a remote stereo camera pair linked to a pan/tilt device such that the operator may reorient the camera position by use of head movement. Systems such as these which utilise virtual reality style helmet mounted displays have a number of limitations. The geometry of the camera positions and of the displays is generally fixed and is most suitable only for viewing elements of a scene at a particular distance. To address such limitations, a prototype system has been developed where the geometry of the displays and cameras is dynamically controlled by the eye movement of the operator. This paper explores why it is necessary to actively adjust the display system as well as the cameras and justifies the use of mechanical adjustment of the displays as an alternative to adjustment by electronic or image processing methods. The electronic and mechanical design is described including optical arrangements and control algorithms. The performance and accuracy of the system is assessed with respect to eye movement.

Judging size, distance and depth with an active telepresence system

A visual telepresence system has been developed at the University of Reading which utilizes eye tracing to adjust the horizontal orientation of the cameras and display system according to the convergence state of the operator's eyes. Slaving the cameras to the operator's direction of gaze enables the object of interest to be centered on the displays. The advantage of this is that the camera field of view may be decreased to maximize the achievable depth resolution. An active camera system requires an active display system if appropriate binocular cues are to be preserved. For some applications, which critically depend upon the veridical perception of the object's location and dimensions, it is imperative that the contribution of binocular cues to these judgements be ascertained because they are directly influenced by camera and display geometry. Using the active telepresence system, we investigated the contribution of ocular convergence information to judgements of size, distance and shape. Participants performed an open- loop reach and grasp of the virtual object under reduced cue conditions where the orientation of the cameras and the displays were either matched or unmatched. Inappropriate convergence information produced weak perceptual distortions and caused problems in fusing the images.

Evaluation of dichroic material for enhancing light pipe/natural ventilation and daylighting in an integrated system

Integration of natural ventilation and daylighting in a single installation would make both technologies more attractive. One method for the integration is the use of concentric light pipe and ventilation stack. By constructing the light pipe using dichroic materials, the infrared part of the solar radiation is allowed to be transmitted to the stack but the visible light is guided by the light pipe into a room. The heat gain to the interior can be reduced and the thermal stack effect strengthened. Work presented here involved the experimental and computational evaluation of dichroic materials for enhancing both natural stack ventilation and daylighting. The transmittance of a dichroic light pipe was found to be similar to that of a light pipe with a 95% specular reflectance. The infra-red radiation transmitted through the dichroic material into a passive stack was found to enhance the natural ventilation flow by up to 14%. The effect is greater in summer than in winter, which is highly desirable as there is often a lack of driving force for natural stack ventilation in summer.

Fit for planning? An evaluation of the application of development viability appraisal models in the UK planning system

The aim of this paper is to critically examine the application of development appraisal to viability assessment in the planning system. This evaluation is of development appraisal models in general and also their use in particular applications associated with estimating planning obligation capacity. The paper is organised into four themes: · The context and conceptual basis for development viability appraisal · A review of development viability appraisal methods · A discussion of selected key inputs into a development viability appraisal · A discussion of the applications of development viability appraisals in the planning system It is assumed that readers are familiar with the basic models and information needs of development viability appraisal rather than at the cutting edge of practice and/or academe

Change, rigidity & delay in the UK system of land-use development control

The British system of development control is time-consuming and uncertain in outcome. Moreover, it is becoming increasingly overloaded as it has gradually switched away from being centred on a traditional ‘is it an appropriate land-use?’ type approach to one based on multi-faceted inspections of projects and negotiations over the distribution of the potential financial gains arising from them. Recent policy developments have centred on improving the operation of development control. This paper argues that more fundamental issues may be a stake as well. Important market changes have increased workloads. Furthermore, the UK planning system's institutional framework encourages change to move in specific directions, which is not always helpful. If expectations of increased long-term housing supply are to be met more substantial changes to development control may be essential but hard to achieve.

Dynamic vergence telepresence system incorporating active gaze control

Visual Telepresence system which utilize virtual reality style helmet mounted displays have a number of limitations. The geometry of the camera positions and of the display is fixed and is most suitable only for viewing elements of a scene at a particular distance. In such a system, the operator's ability to gaze around without use of head movement is severely limited. A trade off must be made between a poor viewing resolution or a narrow width of viewing field. To address these limitations a prototype system where the geometry of the displays and cameras is dynamically controlled by the eye movement of the operator has been developed. This paper explores the reasons why is necessary to actively adjust both the display system and the cameras and furthermore justifies the use of mechanical adjustment of the displays as an alternative to adjustment by electronic or image processing methods. The electronic and mechanical design is described including optical arrangements and control algorithms, An assessment of the performance of the system against a fixed camera/display system when operators are assigned basic tasks involving depth and distance/size perception. The sensitivity to variations in transient performance of the display and camera vergence is also assessed.

Evaluation of drug physical form during granulation, tabletting and storage

An active pharmaceutical ingredient (API) was found to dissociate from the highly crystalline hydrochloride form to the amorphous free base form, with consequent alterations to tablet properties. Here, a wet granulation manufacturing process has been investigated using in situ Fourier transform (FT)-Raman spectroscopic analyses of granules and tablets prepared with different granulating fluids and under different manufacturing conditions. Dosage form stability under a range of storage stresses was also investigated. Despite the spectral similarities between the two drug forms, low levels of API dissociation could be quantified in the tablets; the technique allowed discrimination of around 4% of the API content as the amorphous free base (i.e. less than 1% of the tablet compression weight). API dissociation was shown to be promoted by extended exposure to moisture. Aqueous granulating fluids and manufacturing delays between granulation and drying stages and storage of the tablets in open conditions at 40◦C/75% relative humidity (RH) led to dissociation. In contrast, non-aqueous granulating fluids, with no delay in processing and storage of the tablets in either sealed containers or at lower temperature/humidity prevented detectable dissociation. It is concluded that appropriate manufacturing process and storage conditions for the finished product involved minimising exposure to moisture of the API. Analysis of the drug using FT-Raman spectroscopy allowed rapid optimisation of the process whilst offering quantitative molecular information concerning the dissociation of the drug salt to the amorphous free base form.