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Results for “Bimolecular reactions”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1978

On the possibility of negative activation energies in bimolecular reactions

The temperature dependence of the rate constants for model reacting systems was studied to understand some recent experimental measurements which imply the existence of negative activation energies. A collision theory model and classical trajectory calculations are used to demonstrate that the reaction probability can vary inversely with collision energy for bimolecular reactions occurring on attractive potential energy surfaces. However, this is not a sufficient condition to ensure that the rate constant has a negative temperature dependence. On the basis of these calculations, it seems unlikely that a true bimolecular reaction between neutral molecules will have a negative activation energy.

Jaffe, R. L.↗
NASA NTRS1990

Simple model for lambda-doublet propensities in bimolecular reactions

A simple geometric model is presented to account for lambda-doublet propensities in bimolecular reactions A + BC - AB + C. It applies to reactions in which AB is formed in a pi state, and in which the unpaired molecular orbital responsible for lambda-doubling arises from breaking the B-C bond. The lambda-doublet population ratio is predicted to be 2:1 provided that: (1) the motion of A in the transition state determines the plane of rotation of AB; (2) the unpaired pi orbital lying initially along the B-C bond may be resolved into a projection onto the AB plane of rotation and a projection perpendicular to this plane; (3) there is no preferred geometry for dissociation of ABC. The 2:1 lambda-doublet ratio is the 'unconstrained dynamics prior' lambda-doublet distribution for such reactions.

Bronikowski, Michael J.↗
NASA NTRS1991

Association reactions at low pressure. IV - The HC3N(+)/HC3N system

Ion cyclotron mass spectrometry is used here to study the reactions between HC3N(+) and HC3N and between HC5N(+) and HC3N at pressures from 1 x 10 to the -7th to 0.001 Torr. The former reaction has both a bimolecular reaction path and a termolecular reaction path. The overall bimolecular reaction rate coefficient is 1.3 x 10 to the -19 cu cm/s. The primary product HC5N(+) represents 90 percent of the product ions, while HC6N2(+) and H2C6N2(+) each represent 5 percent. The termolecular association rate coefficient is 3.7 x 10 to the -24th cm exp 6/s, with He as the third body. The mean lifetime of the collision is 180 microsec. HC5N(+) reacts with HC3N to form the adduct ion H2C8N2(+) through both bimolecular and termolecular reactions. The bimolecular rate coefficient is 5.0 x 10 to the -10th cu cm/s and the termolecular one is 1.2 x 10 to the -22nd cm exp 6/s, with HC3N as the third body.

Sen, Atish D.↗
NASA NTRS1983

Pulsed laser photolysis study of the reaction between O(3P) and HO2

It is pointed out that bimolecular reactions involving two free radicals are of great interest because both reactants have unpaired electrons and hence could interact at distances longer than those typical of radical-molecule encounters. A method based on laser photolysis is being developed to produce selectively free radicals in the homogeneous gas phase. This is to be done in such a way as to isolate the reaction of interest and subsequently follow the course of the reaction using spectroscopic techniques. The present investigation is concerned with a study in which the rate coefficient for the reaction of O(3P) with HO2, has been measured at N2 pressures ranging from 10 to 500 torr, taking into account the reaction O(3P)+HO2 yields OH-O2. In the described study, O(3P) and HO2 were produced by cophotolysis of O3 and H2O2 in N2 at 248.5 nm using a KrF excimer laser.

Ravishankara, A. R.↗
NASA NTRS1974

Shock tube measurements of specific reaction rates in the branched chain CH4-CO-O2 system

Rate constants of two elementary bimolecular reactions involved in the oxidation of methane have been determined by monitoring the exponential growth of CO flame band emission behind incident shocks in three suitably chosen gas mixtures. The data do not support a mechanism which invokes the four center process CH3 + O2 yields CH2O + OH for the reaction of methyl with oxygen.

Brabbs, T. A.↗
NASA NTRS1974

Reactions of ions in excited electronic states - Excited N2/+/ ion reacting with N2 to yield N3/+/ and N

Study of the mechanism of formation of the N3(+) ion from the bimolecular reaction of excited N2(+) ions in gaseous N2. Using ion cyclotron resonance spectroscopy, an attempt is made to inquire more deeply than hitherto into the origin of the N3(+) ions and to determine the rate constant for their formation and the limits on the lifetime of the reactant excited N2(+) ions.

Bowers, M. T.↗
NASA NTRS1975

Shock tube measurements of specific reaction rates in the branched chain CH4-CO-O2 system

Growth constants, obtained by measuring the blue CO flame band emission behind incident shock waves, were obtained for two elementary bimolecular reactions involved in the oxidation of methane. Gas mixtures containing small amounts of CH4 with varying amounts of CO, O2, and in one case CO2, diluted with argon, were investigated, and exponential growth constants were derived from plots of the logarithm of observed light intensity versus gas time. The rate constant for the reaction O + CH4 yields CH3 + OH was found to be 1.9 times 10 to the 14th exp(-5900/T) cu cm per mole per sec in the range 1300-2000 K; for the reaction CH3 + O2 yields CH3O + O, the rate constant was determined to be 2.4 times 10 to the 13th exp(-14,500/T) cu cm per mole per sec in the range 1200 to 1900 K.

Brabbs, T. A.↗
NASA NTRS1978

Chemiluminescence Study of the Autoxidation of cis-1,4-Polyisoprene

The free-radical mechanism for the autoxidation of cis-1,4-polyisoprene (natural rubber or its synthetic counterpart) has been investigated extensively. An important feature of this mechanism, and indeed also of the autoxidation of hydrocarbons generally, is that it is a chain process propagated by alkyl and peroxy radicals and terminated through bimolecular reactions involving these same radicals. In the usual oxidation situation, that is, at all oxygen pressures greater than a few torr, the alkyl radicals are rapidly converted to peroxy radicals, and the termination step proceeds almost exclusively through the latter radicals. The bimolecular decay of the peroxy radicals is accompanied by a weak emission of light or chemiluminescence. Kinetic evidence is consistent with an electronically excited ketone produced in the termination reaction as the source of the emission. The first observation of chemiluminescence from the oxidative degradation of polymers was reported by Ashby, who dealt mainly with polypropylene but made passing mention of several other polymers. Subsequently, a number of papers have appeared dealing with oxidative chemiluminescence from a variety of polymers. In this paper we report the first detailed study of the chemiluminescence emitted in the autoxidation of cis-1,4-polyisoprene. The chemiluminescence technique is extremely sensitive and can follow rates of oxidation that are too slow to be measured conveniently by other means. This work thus offered the potential of throwing new light on the autoxidation of cis-1,4-polyisoprene, especially in the very early stages or under ambient conditions where conventional spectroscopic procedures are rather insensitive.

Mendenhall, G. David↗
NASA NTRS1977

Isothermal degradation of poly-2,2'-/m-phenylene/-5,5'-bibenzimidazole

The isothermal degradation of poly-2,2'-(m-phenylene)-5,5'-bibenzimidazole in vacuo has been studied. Measurement of the increase in pressure with time, coupled with infrared analysis, was used to determine the distribution of the degradation products. Processes A and B with different second-order rate laws were determined to be significant in the temperature range of 550-700 C. Process A leads to the formation of equimolar quantities of hydrogen and ammonia and has an activation energy of 68 kcal/mole. Process B leads to the production of HCN, NH3, and H2 in the ratio of 1:1:2.5 and has an activation energy of 77 kcal/mole. The activation energies and the rate laws are consistent with a mechanism in which the initial degradation step is the bimolecular reaction of two aromatic rings.

Lerner, N. R.↗
NASA NTRS1978

Semiclassical theory of unimolecular dissociation induced by a laser field

A semiclassical nonperturbative theory of direct photodissociation in a laser field is developed in which photon absorption and dissociation are treated in a unified fashion. This is achieved by visualizing nuclear dynamics as a representative particle moving on electronic-field surfaces. Methods are described for calculating dissociation rates and probabilities by Monte Carlo selection of initial conditions and integration of classical trajectories on these surfaces. This unified theory reduces to the golden rule expression in the weak-field and short-time limits, and predicts nonlinear behavior, i.e., breakdown of the golden rule expression in intense fields. Field strengths above which lowest-order perturbation theory fails to work have been estimated for some systems. Useful physical insights provided by the electronic-field representation have been illustrated. Intense field effects are discussed which are amenable to experimental observation. The semiclassical methods used here are also applicable to multiple-surface dynamics in fieldfree unimolecular and bimolecular reactions.

Yuan, J.-M.↗
NASA NTRS1980

Ion chemistry in interstellar space

The temperature dependence of the bimolecular reactions of Cl(+), HCl(+), CH(+), CH2(+), N(+), NH(+), and NH2(+) reacting with H2 have been investigated. For Cl(+) and HCl(+) rate constants have been determined over the temperature range of 150 to 400 K. Preliminary data have been obtained for the other systems. The Cl(+)/H2 system shows a weak, but significant positive temperature dependence that could be important in interstellar modeling studies. The HCl(+)/H2 system shows a substantial negative temperature dependence with the rate constant approaching the collision rate at low temperatures. The association reaction CH3(+) + HCN yields CH3 HCN(+) has been theoretically modeled using statistical phase space theory. Both radiative and collisional stabilization have been included. The results are compared with experiment with good agreement obtained over wide variations in T and p. This system is potentially important in the mechanism of large molecule synthesis in interstellar space.

Bowers, M. T.↗
NASA NTRS1988

Analysis of homogeneous turbulent reacting flows

Full turbulence simulations at low Reynolds numbers were made for the single-step, irreversible, bimolecular reaction between non-premixed reactants in isochoric, decaying homogeneous turbulence. Various initial conditions for the scalar field were used in the simulations to control the initial scalar dissipation length scale, and simulations were also made for temperature-dependent reaction rates and for non-stoichiometric and unequal diffusivity conditions. Joint probability density functions (pdf's), conditional pdf's, and various statistical quantities appearing in the moment equations were computed. Preliminary analysis of the results indicates that compressive strain-rate correlates better than other dynamical quantities with local reaction rate, and the locations of peak reaction rates seem to be insensitive to the scalar field initial conditions.

Leonard, A. D.↗
NASA NTRS1992

Chemistry and kinetics of I2 loss in urine distillate and humidity condensate

Time-resolved molecular absorption spectrophotometry of iodinated ersatz humidity condensates and iodinated ersatz urine distillates across the UV and visible spectral regions are used to investigate the chemistry and kinetics of I2 loss in urine distillate and humidity condensate. Single contaminant systems at equivalent concentrations are also employed to study rates of iodine. Pseudo-first order rate constants are identified for ersatz contaminant model mixtures and for individual reactive constituents. The second order bimolecular reaction of elemental iodine with formic acid, producing carbon dioxide and iodine anion, is identified as the primary mechanism underlying the decay of residual I2 in ersatz humidity concentrate.

Atwater, James E.↗
NASA NTRS1988

Adiabatic criteria for outer-sphere bimolecular electron-transfer reactions

A model is presented for outer-sphere bimolecular electron-transfer reactions which is correct in the adiabatic, nonadiabatic, and intermediate dynamical regimes for an overdamped solvent coordinate. From this model, the conditions for the transfer to be adiabatic or nonadiabatic are deduced. The time-scale separations needed to adequately describe the process as an average over (distant dependent) unimolecular rates are described.

Onuchic, Jose Nelson↗