Engineering topics

Crosley, David R.

Publications and source records attributed to Crosley, David R..

14 records

NASA NTRS2001

Flame Chemiluminescence Rate Constants for Quantitative Microgravity Combustion Diagnostics

Absolute excited state concentrations of OH(A), CH(A), and C2(d) were determined in three low pressure premixed methane-air flames. Two dimensional images of chemiluminescence from these states were recorded by a filtered CCD camera, processed by Abel inversion, and calibrated against Rayleigh scattering, Using a previously validated 1-D flame model with known chemistry and excited state quenching rate constants, rate constants are extracted for the reactions CH + O2 (goes to) OH(A) + CO and C2H + O (goes to) CH(A) + CO at flame temperatures. Variations of flame emission intensities with stoichiometry agree well with model predictions.

Luque, Jorge↗

NASA NTRS1999

Quantitative Interpretation of Optical Emission Sensors for Microgravity Experiments

Microgravity flight experiments uniquely test our knowledge and understanding of the coupling between chemistry and fluid mechanics. However, compared to ground based laboratory experiments the number of useful diagnostic tools suitable for microgravity environments is severely limited by the space, weight, power consumption, and operator complexity requirements. One of the available tools is the observation of optical emission, and total emission has already proven useful for observations of stable "flame balls" on the space shuttle. Wavelength resolved tomographic measurements of flame emission offer the promise of diagnostics to test our understanding of flame chemistry and structure. Individual emissions from electronically excited radicals, e.g., CH*, OH*, and C2*, can be identified in a methane/air flame. Spatially resolved measurements of the intensity of this resolved optical emission from a specific excited molecule enable chemically resolved flame structure studies. Wavelength resolved emission measurements to determine such structure in diffusion flames are being readied for flight experiments by a group at Yale headed by Profs. Smooke and Long. A quantitative relationship between emission intensity and flame properties, as expressed by a flame model, is needed for species specific optical emission measurements to fulfill its promise. The Yale group compared models and measurements of optical emission in laboratory tests at 1-g. Unfortunately, these experiments show disagreement between measurement and state-of-the-art flame models by over a factor of 50. Therefore, an improved chemical mechanism for optical emission from flames is needed to enable quantitative tests of microgravity flame models. The connection between excited state emission and flame chemistry is not yet adequate.

Jeffries, Jay B.↗

NASA NTRS1995

Electronic transition moment for the B(2)II-X(2)II system of NO

The upsilon' = 0-3 and 7 vibrational levels of the NO B(2)II state have been selectively excited by laser radiation. The fluorescence spectra together with calculated Franck-Condon factors and r-centroids have been used to evaluate the electronic transition moment. The results for upsilon' = 0-3 are in very good agreement with recent chemiluminescence measurements and ab initio calculations. Furthermore, the data from upsilon' = 7 have been used to extend the empirically determined moment to limits 1.23 and 1.78 A, improving agreement with experimentally determined lifetimes.

Luque, Jorge↗

NASA NTRS1994

Local Measurement of Tropospheric HO(x)

In March of 1992 a workshop sponsored by NASA and NSF was held at SRI International to assess the current ability to measure atmospheric OH and HO2. The measurement techniques reviewed during the workshop for detection of OH included five laser-induced fluorescence schemes, five laser-based adsorption techniques, and four non-laser methods. Six instruments or instrument concepts for HO2 detection, including chemical amplification, conversion to OH with subsequent OH detection, or direct spectroscopic detection of the HO2 were also discussed. The conclusions from the workshop identify several measurement techniques for OH and HO2 that are ready for field tests. These have the ability to measure the radicals with sufficient sensitivity and accuracy to form meaningful comparison with atmospheric model predictions. The workshop conclusions also include recommendations for informal and formal intercomparison protocols.

Crosley, David R.↗

NASA NTRS1991

Parity propensities in rotational energy transfer of OH X 2Pi(i) with helium

Preliminary results of rotational energy transfer in ground state OH in collisions in He are reported. A surprising propensity is found: conservation of total parity is favored in collisions which change in spin-orbit component, the reversible reaction 2Pi3/2 yields 2Pi1/2. This has implications concerning the OH-He potential surface.

Wysong, Ingrid J.↗

NASA NTRS1991

Collisional effects in laser detection of tropospheric OH

The use of laser-induced fluorescence to measure OH in the troposphere is discussed. It is noted that quantitative laser detection of OH requires knowledge of collisional processes affecting the measurements and interference effects due to OH generated by laser photolytic processes. Collisions induce quenching of the excited A-state, as well as vibrational and rotational energy transfer in the excited and ground states. It is noted that the state-specific nature of these processes is important, especially the rotational level dependence of quenching and vibrational transfer in excited OH. Also important is the temperature dependence according to which quenching cross sections sharply increase with decreasing temperature. Laboratory experiments studying these collisional processes are described, and their implications for laser detection of tropospheric OH are examined.

Crosley, David R.↗

NASA NTRS1990

A photochemical model of ozone interference effects in laser detection of tropospheric OH

Laser-generated interference in the laser-induced fluorescence detection of tropospheric hydroxyl is addressed by a detailed photochemical model. This phenomenon arises through photolysis of ozone by the detection laser and subsequent reaction of O(1D) with H2O to form OH. The approach is direct time integration of the coupled differential equations describing the pertinent chemical reactions, collisional energy transfer, and photolytic and spectroscopic processes, including an assessment of limitations due to uncertainties in the input parameters. The goal is to use the model to quantitatively design OH detection methods so that the experimental results need not rely on such a model for interpretation. Previously reported measurements of tropospheric OH appear to have been contaminated by ozone interference effects and by optical saturation of the monitoring transition. However, suggested improvements can reduce the problem to interference levels below 200,000 OH molecules/cu cm, permitting measurements useful for testing theories of fast tropospheric photochemistry.

Smith, Gregory P.↗

NASA NTRS1990

Vibrational energy transfer in OH X 2Pi(i), v = 2 and 1

Using an IR-pump/UV-probe method in a flow discharge cell, vibrational energy transfer in OH X 2Pi(i) has been studied. OH is prepared in v = 2 by overtone excitation, and the time evolution of population in v = 2 and 1 monitored by laser-induced fluorescence. Rate constants for vibrational relaxation by the colliders H2O, NH3, CO2, and CH4 were measured. Ratios of rate constants for removal from the two states, k2/k1, range from two to five.

Raiche, George A.↗

NASA NTRS1990

Quenching of A 2Sigma(+) OH at 300 K by several colliders

Quenching cross sections, sigma(Q), were measured for A 2Sigma(+) OH for a variety of colliders, using the pressure dependence of time-resolved laser-induced fluorescence to obtain quenching cross sections. The OH radicals, produced in a discharge or by photolysis, were maintained in the excited state at 300 K by an Ar buffer bath. It was found that quenching by CF4 and C2F6 the cross sections are very small. For Kr and Ze, the sigma(Q) values were found to be 8 and 27 sq A, respectively. For O2, sigma(Q) was 18 sq A, and for H2O, sigma(Q) was 80 sq A.

Wysong, Ingrid J.↗

NASA NTRS1989

Vibrational relaxation of OH (X 2Pi sub i, v = 2)

A two-laser pump-and-probe technique is used to determine vibrational relaxation rates for the v = 2 level of the X 2Pi sub i state of the OH radical. In the present method, the time delay between the lasers is scanned at a given collider pressure, producing exponential decay whose rate as a function of collider pressure yields the rate constant. With the exception of ammonia, the values obtained are two to three orders of magnitude smaller than those found for relaxation of v = 1 in the A 2Sigma(+) excited state of OH.

Rensberger, Karen J.↗

NASA NTRS1988

Rotational and translational effects in collisions of electronically excited diatomic hydrides

Collisional quenching and vibrational energy proceed competitively with rotational energy transfer for several excited states of the diatomic radicals OH, NH, and CH. This occurs for a wide variety of molecular collision partners. This phenomenon permits the examination of the influence of rotational motion on the collision dynamics of these theoretically tractable species. Measurements can also be made as a function of temperature, i.e., collision velocity. In OH (sup 2 sigma +), both vibrational transfer and quenching are found to decrease with an increase in rotational level, while quenching decreases with increasing temperature. This behavior indicates that for OH, anisotropic attractive forces govern the entrance channel dynamics for these collisions. The quenching of NH (sup 3 pi sub i) by many (although not all) collision partners also decreases with increasing rotational and translational energy, and NH (sup 1 pi) behaves much like OH (sup 2 sigma +). However, the quenching of CH (sup 2 delta) appears to decrease with increasing rotation but increases with increasing temperature, suggesting in this case anisotropic forces involving a barrier or repulsive wall. Such similarities and differences should furnish useful comparisons with both simple and detailed theoretical pictures of the appropriate collision dynamics.

Crosley, David R.↗

NASA NTRS1986

Future directions for H sub x O sub y detection

The activities and recommendations of the NASA workshop on the Future Directions for H sub x O sub y detection are given. The objective of this workshop was to access future directions for the measurement of the OH radical as well as other H sub x O sub y species. The workshop discussions were focused by two broad questions: (1) What are the capabilities of potential measurement methods? and (2) Will the results from the most promising method be useful in furthering understanding of tropospheric chemistry?

Crosley, David R.↗

NASA NTRS1986

Transition probabilities in OH A 2 sigma + - X 2 pi i: Bands with v prime = 0 and 1, v double prime = 0 to 4

Experimental results for relative vibrational band transition probabilities for v prime = 0 and 1, and v double prime = 0 to 4 in the A-X electronic system of OH are presented. The measurements, part of a larger set involving v prime = 0 to 4 and v double prime = 0 to 6, were made using spectrally dispersed laser-induced fluorescence (LIF) in the burnt gases of a flame. These Einstein coefficients will be useful in dynamics experiments for quantitative LIF determinations of OH radical concentrations in high v double prime.

Copeland, Richard A.↗

NASA NTRS1986

Laser-induced fluorescence measurement of combustion chemistry intermediates

Laser-induced fluorescence (LIF) can measure the trace (often free radical) species encountered as intermediates in combustion chemistry; OH, CS, NH, NS, and NCO are typical of the species detected in flames by LIF. Attention is given to illustrative experiments designed to accumulate a quantitative data base for LIF detection in low pressure flow systems and flames, as well as to flame measurements conducted with a view to the detection of new chemical intermediaries that may deepen insight into the chemistry of combustion.

Crosley, David R.↗