Ozone Decomposition Data for Kinetics Exercises

The goal of this paper is to provide data that can be used in a variety of exercises ranging from kinetics in general chemistry to advanced problems in physical chemistry. The data provided relates to ozone-decay kinetics in various atmospheres (O₂, N₂, Ar) as measured by ultraviolet/visible absorbance spectroscopy (UV/vis) at 254 nm. The absorbance of ozone is monitored over a 75-min time period, and by using Beers law the concentration is calculated. Nine data sets, each repeated three times, of absorbance measurements are provided for student exercises, and prelaboratory and postlaboratory questions are suggested.     

Spectra and structure of small ring compounds. LIX

The Raman (3200 to 10 cm^–1) and far infrared (380 to 60 cm^–1) spectra of gaseous fluorocyclobutane,c-C₄H₇F, have been recorded. A series of Q-branches observed in both of these spectra beginning at 166 cm^–1 with successive transitions falling to lower frequencies have been assigned to the ring puckering vibrations of both the low energy equatorial and high energy axial conformers. These data have been fit to an asymmetric potential function of the form:V (cm^–1)=(1.76±0.05)10³X+(4.88±0.28)10⁴X²+(2.12 ±0.16)10³ exp(–5.66±0.41)10X² with a reduced mass function ofg ₄₄= 0.00386–0.00295X+0.03485X²+0.1228X³ +0.3459X⁴, whereX is the ring puckering coordinate. Utilizing this potential, the difference between the puckering angles for the two conformers was calculated to be 4° with the equatorial conformer having the larger value of 28°. This potential function is consistent with an energy difference between the equatorial and axial forms of 447 cm^–1 (1.28 kcal/mol) and a barrier to ring inversion from the equatorial to the axial conformation of 713 cm^–1 (2.04 kcal/mol). Experimental values for the enthalpy difference between the two conformers have been determined for both the liquid (400±30 c^–1) and gas (413±43 cm^–1) from investigations of the Raman spectra at variable temperatures. The conformational stability, enthalpy difference, structural parameters, and fundamental vibrational frequencies, which have been determined experimentally, are compared to those obtained from ab initio Hartree-Fock calculations employing the 3-21G, 6-31 G^*, and 6-31 G^** basis sets.For part LVIII, seeStruct. Chem. 1991,2, 195.Taken in part from the thesis of M. J. Lee, which has been submitted to the Department of Chemistry in partial fulfillment of the Ph.D. degree, May 1991.     

Sample indexed spatial orthogonal frequency division multiplexing

Optical spatial modulation(OSM) is a multiple-transmitter technique that can provide higher data rates with low system complexity as compared with single-input single-output systems. Orthogonal frequency division multiplexing(OFDM) is widely implemented to achieve better spectral efficiency in wireless channels. Asymmetrically clipped optical OFDM(O-OFDM) and DC-biased O-OFDM are two well-known O-OFDM techniques suitable for intensity-modulation direct-detection optical systems. In this work, sample indexed spatial OFDM(SIS-OFDM) is proposed to combine OSM and O-OFDM in a novel way and achieve significant performance gain. By assigning time-domain samples of the O-OFDM transmit symbol to different transmitters, SIS-OFDM achieves much better spectral efficiency and reduces computational complexity at the transmitter as compared with previous work that combines OSM with O-OFDM in the frequency domain. We also consider the impact of optical source biasing on overall performance, and the relative performance of imaging receiver(ImR) versus non-imaging receiver(NImR) design for our proposed SIS-OFDM technique. Results indicate that for an Ntx × Nrx multiple-input multiple-output configuration where Ntx = Nrx = 4, SIS-OFDM using ImR can achieve up to 135 dB of signal-to-noise ratio gain over comparable system using a NImR. Also, using Nsc number of O-OFDM subcarriers provides up to Nsc × log2(Ntx) additional bits per symbol of spectral efficiency over techniques that combine OSM and O-OFDM in the frequency domain.     

Partition of a directed bipartite graph into two directed cycles

Let D = (V₁, V₂; A) be a directed bipartite graph with |V₁| = |V₂| = n 2. Suppose that d_D(x) + d_D(y) 3n + 1 for all x ε V₁ and y ε V₂. Then D contains two vertex-disjoint directed cycles of lengths 2n₁ and 2n₂, respectively, for any positive integer partition n = n₁ + n₂. Moreover, the condition is sharp for even n and nearly sharp for odd n.     

Comparison of Curve Fitting Models for Ligand Binding Assays

In the case of ligand binding assays the relationship between instrumental response and analyte concentration is non-linear, usually either hyperbolic or sigmoidal. As it is not possible to calibrate an assay at all the levels to be measured a suitable method of constructing a concentration-response relationship (the standard curve), based on a limited number of carefully spaced standards is required. The method should be robust and operator independent. The two main approaches that have been used involve empirical and mechanistic (theoretical) models. Empirical models utilise any mathematical function(s) that appears to have the characteristics of the experimentally derived assay data. Empirical models require no understanding of the principles of the assay. Mechanistic models make assumptions about the physico-chemical processes involved in the assay procedure. In practice either single function or spline models are used. The curve fitting solution may be explicit (in the case of spline interpolation), or by least-squares curve fitting regression methods, including polynomial and logistic equations, the latter involving many iterations. Examples of good curve fitting selection are presented and contrasted with inappropriate models in a number of common assay formats.     

Structural and magnetic properties of nano-crystalline RuFe alloys prepared by organometallic synthesis

Nanoparticles of Ru_1-xFe_x (0≤x≤1) in a carbon matrix were synthesized over the entire composition range using organometallic precursors. For Fe concentrations with x<0.70, a hexagonal close-packed phase was formed whereas a body-centered cubic phase was observed for x>0.70. The crystallite sizes varied between 5–10 nm. In addition, multi-wall carbon nanotubes formed during the pyrolysis of the precursors. Increasing superparamagnetic order was observed with increasing Fe content.     

Planar integrated wavelength-drop device based on pedestal antiresonant reflecting waveguides and high-Q silica microspheres

Whispering-gallery modes in silica microspheres can be accessed very efficiently with the recently introduced stripline pedestal antiresonant reflecting optical waveguide (SPARROW) structure. This integrated-optics coupling technique creates novel application opportunities for the high-Q spherical cavities. We report the demonstration of a narrow-band wavelength-drop configuration utilizing SPARROW waveguides and a silica microsphere.