Hydrocarbon ions in fuel-rich, CH4–C2H2–O2 flames as a probe for the initiation of soot: interpretation of the ion chemistry

1982 ◽  
Vol 60 (22) ◽  
pp. 2766-2776 ◽  
Author(s):  
John M. Goodings ◽  
Scott D. Tanner ◽  
Diethard K. Bohme
Keyword(s):  
Charge Transfer ◽  
Proton Transfer ◽  
Reaction Zone ◽  
Negative Ions ◽  
Negative Ion ◽  
Ion Chemistry ◽  
Soot Precursors ◽  
Ion Profiles ◽  
Three Body ◽  
Positive Ion

The ion chemistry is discussed for fuel-rich, nearly sooting, methane–oxygen flames at atmospheric pressure with added acetylene. Different types of ion–molecule reactions, both positive and negative, which can contribute through chemical ionization (CI) processes are summarized including their dependence on temperature, pressure, and equivalence ratio [Formula: see text]. Extensive data were presented previously involving ion concentration profiles measured with a mass spectrometer as a function of distance along the axis of conical flames. An understanding of the dominant CI processes provides insight into the early chemical stage of soot formation associated with the flame reaction zone. The negative ion profiles show moderately unsaturated hydrocarbon ions upstream formed by proton transfer followed by progressive dehydrogenation; the highly unsaturated, carbonaceous ions observed downstream appear to arise by two- and three-body electron attachment, charge transfer, and H-atom stripping. The negative hydrocarbon ions can all be explained in terms of polyacetylene derivatives. The same build-up of carbonaceous species downstream is evident from the positive ion profiles. A major role is ascribed to proton transfer reactions with lesser contributions from charge transfer and ion–molecule condensation; three-body association is probably insignificant. Experiments with added acetylene indicate extensive fuel pyrolysis early in the reaction zone. There is no evidence that an ionic mechanism is dominant in forming soot precursors compared with neutral condensation reactions. Because of complexities in the positive ion chemistry, the negative ions appear to provide the more straightforward probe of the underlying neutral chemistry.

Hydrocarbon ions in fuel-rich, CH4–C2H2–O2 flames as a probe for the initiation of soot: an experimental approach

1981 ◽  
Vol 59 (12) ◽  
pp. 1760-1770 ◽  
Author(s):  
Scott D. Tanner ◽  
John M. Goodings ◽  
Diethard K. Bohme
Keyword(s):  
Reaction Zone ◽  
Soot Formation ◽  
Unsaturated Hydrocarbon ◽  
Ion Concentration ◽  
Negative Ion ◽  
Ion Chemistry ◽  
Positive Ions ◽  
Total Ionization ◽  
Ion Profiles ◽  
Positive Ion

The natural hydrocarbon ions CnHx± (n ≥ 2, x ≥ 0) present in premixed, fuel-rich, nearly sooting, CH4–C2H2–O2 flames at atmospheric pressure were studied as a probe of the early chemical stages of soot formation. Ion concentration profiles were measured mass-spectrometrically along the flame axis through the reaction zone into the burnt gas downstream. Total ionization profiles were examined for their dependence on both temperature and equivalence ratio, [Formula: see text] Families of individual CnHx− negative ion profiles exhibit concentration peaks in three distinct regions; predominantly oxygenated ions occur upstream, giving way to moderately unsaturated hydrocarbon ions near the end of the reaction zone, leading to highly unsaturated carbonaceous ions further downstream. The concentrations of the downstream ions alternate with the parity of n, the even-n species being larger. Series of CnHx+ positive ion profiles, for a given n, show profile peak positions which move steadily downstream with decreasing x, indicative of progressive dehydrogenation. The positive ion chemistry of these series is essentially independent of n. As [Formula: see text] is increased at constant temperature towards the sooting point, the concentrations of CnHx± ions increase while those of the oxygenated ions decrease; the positive ions show a relative enhancement of species having high values of n.

Note on radiationless transitions involving three-body collisions

1936 ◽  
Vol 32 (3) ◽  
pp. 482-485 ◽  
Author(s):  
R. A. Smith
Keyword(s):  
Continuous Spectrum ◽  
Negative Ions ◽  
Bound State ◽  
Excess Energy ◽  
Negative Ion ◽  
Positive Ions ◽  
Continuous State ◽  
Direct Formation ◽  
Three Body ◽  
Positive Ion

When an electron makes a transition from a continuous state to a bound state, for example in the case of neutralization of a positive ion or formation of a negative ion, its excess energy must be disposed of in some way. It is usually given off as radiation. In the case of neutralization of positive ions the radiation forms the well-known continuous spectrum. No such spectrum due to the direct formation of negative ions has, however, been observed. This process has been fully discussed in a recent paper by Massey and Smith. It is shown that in this case the spectrum would be difficult to observe.

Negative chlorine ion chemistry in the upper stratosphere and its application to an artificially created dense electron cloud

1995 ◽  
Vol 13 (3) ◽  
pp. 296-304 ◽  
Author(s):  
S. S. Prasad
Keyword(s):  
Major Ions ◽  
Negative Ions ◽  
Electron Cloud ◽  
Negative Ion ◽  
Cluster Ions ◽  
Aerosol Formation ◽  
Ion Chemistry ◽  
Catalytic Destruction ◽  
Three Body ◽  
Chlorine Ion

Abstract. This paper discusses new potential reactions of chlorine-bearing anions (negative ions) in the upper stratosphere. These reactions are then applied to the negative-ion chemistry following the injection of an electron cloud of very high density, of the order of 106-107 e- cm-3, in the 40-45-km region. The idea is to evaluate the recently proposed scheme to mitigate ozone depletion by converting the reactive chlorine atoms at these altitudes into Cl- ions which are unreactive towards ozone, i.e., electron scavenging of Cl. We find that the previously neglected photodetachment from Cl- is fast. For an overhead sun, this process may have a rate coefficient of 0.08 s-1 when multiple scattering is included. The rate could be even higher, depending on the ground albedo. Switching reaction between Cl-·H2O and HCl might lead to the formation of Cl-·HCl anion. Possible reactions of Cl-·H2O and Cl-·HCl with O atoms could produce ClO- and Cl-2. The production of ClO- in this manner is significant because Cl- having a high photodetachment rate constant would be regenerated in the very likely reactions of ClO- with O. When these possibilities are considered, then it is found that the chlorine anions may not be the major ions inside the electron cloud due to the rapid photodetachment from Cl-. Furthermore, in such a cloud, there may be the hazard that the Cl--Cl-·H2O-ClO--Cl- cycle amounts to catalytic destruction of two O atoms. Thus, the scheme could be risky if practised in the altitude region where atomic oxygen is an important constituent. Similar conclusions apply even if the ClO- species forms ClO-3 by three-body association with O2, instead of reacting with O. It must be emphasized that the present study is speculative at this time, because none of the relevant reactions have been investigated in the laboratory as yet. Nevertheless, it is very safe to say that the scheme of ozone preservation by electron scavenging of the upper stratospheric Cl is much less certain than implied in the studies reported by its original proponents, because those studies neglected the photodetachment from Cl- and made the highly unlikely assumption that the Cl-·H2O anion neither photodissociates nor reacts any further. The situation at the lower altitudes could be even more complex due to the formation of large cluster ions and the ion-induced aerosol formation. The lower atmospheric situation, therefore, requires much more study. The uncertainties in the scavenging scheme due to the electrostatic repulsion in the cloud should also be addressed. Despite the uncertainties about its environmental engineering usefulness, the emerging technology for artificial creation of plasmas, with any desired density and charge in the stratosphere, could have significant pure scientific values in the studies of stratospheric ion chemistry and ion-induced aerosol formation. Such studies have perennially suffered from the extremely low densities of the naturally occurring plasma.

Sulphurous negative ions in a fuel-rich, CH4–O2 flame with OCS additive

1983 ◽  
Vol 61 (8) ◽  
pp. 1703-1711 ◽  
Author(s):  
John M. Goodings ◽  
Kamal Elguindi ◽  
Diethard K. Bohme
Keyword(s):  
Reaction Zone ◽  
Atmospheric Pressure ◽  
Negative Ions ◽  
Ion Concentration ◽  
Quadrupole Mass ◽  
Ion Chemistry ◽  
Naturally Occurring ◽  
Pressure Profiles ◽  
Ion Profiles ◽  
Carbonyl Sulphide

Sulphurous negative ions S • SH • SO • SO2/S2• SO3• HSO3• SO4• and HSO4 were observed when 0.2% of carbonyl sulphide (OCS) was added to a conical, laminar, premixed. fuel-rich (equivalence ratio [Formula: see text]) CH4–O2 flame burning at atmospheric pressure. Profiles were obtained of ion concentration vs. distance along the flame axis by sampling the flame through a pinhole into a quadrupole mass spectrometer. Some of the ion signals observed in the flame reaction zone are very large, particularly that for HSO4. None of the sulphurous ions detected contain carbon. Of those listed above, only S−,•SH, • SO • and SO2 persist downstream through the burnt gas. The sulphurous ions are formed by chemical ionization processes of neutral sulphurous intermediates reacting with the naturally-occurring ions present in any hydrocarbon flame. The ion chemistry is discussed, as is the underlying neutral chemistry of sulphur relevant to the flame environment. The ion profiles show the rapidity with which OCS is oxidized through SH and SO to SO2 even within the reaction zone of this fuel-rich flame. No evidence was obtained for the presence of sulphuric or sulphurous acids, and the presence of S2: was not confirmed.

THE ELECTRON SPIN RESONANCE SPECTRA OF THE POSITIVE AND NEGATIVE IONS OF DIPHENYLENE

1960 ◽  
Vol 38 (4) ◽  
pp. 503-507 ◽  
Author(s):  
C. A. McDowell ◽  
J. R. Rowlands
Keyword(s):  
Electron Spin Resonance ◽  
Hyperfine Interaction ◽  
Electron Spin ◽  
Negative Ions ◽  
Negative Ion ◽  
Spin Resonance ◽  
Hyperfine Splittings ◽  
Positive Ion

The electron spin resonance spectra of the positive and negative ions of diphenylene have been measured. It has been found that these spectra consist of five lines showing that the observed hyperfine interaction is caused by four equivalent protons. The over-all extent of the positive ion spectrum is 18 gauss compared with that of 12.9 gauss for the negative ion. The hyperfine splittings observed are 4.0 gauss and 2.75 gauss respectively.

scholarly journals Sunset transition of negative charge in the D-region ionosphere during high-ionization conditions

2006 ◽  
Vol 24 (1) ◽  
pp. 187-202 ◽  
Author(s):  
P. T. Verronen ◽  
Th. Ulich ◽  
E. Turunen ◽  
C. J. Rodger
Keyword(s):  
Nitric Oxide ◽  
Negative Charge ◽  
Negative Ions ◽  
Solar Proton ◽  
Negative Ion ◽  
Proton Event ◽  
Minor Role ◽  
Cosmic Radio ◽  
Ion Chemistry ◽  
Visible Wavelengths

Abstract. The solar proton event of October 1989 and especially the sunset of 23 October is examined in this study of negative ion chemistry, which combines measurements of nitric oxide, electron density, and cosmic radio noise absorption with ion and neutral chemistry modelling. Model results show that the negative charge transition from electrons to negative ions during sunset occurs at altitudes below 80 km and is dependent on both ultraviolet and visible solar radiation. The ultraviolet effect is mostly due to rapid changes in atomic oxygen and O2(1Δg), while the decrease in NO3- photodetachment plays a minor role. The effect driven by visible wavelengths is due to changes in photodissociation of CO3- and the subsequent electron photodetachment from O-, and at higher altitudes is also due to a decrease in the photodetachment of O2-. The relative sizes of the ultraviolet and visible effects vary with altitude, with the visible effects increasing in importance at higher altitudes, and they are also controlled by the nitric oxide concentration. These modelling results are in good agreement with EISCAT incoherent scatter radar and Kilpisjärvi riometer measurements.

scholarly journals Dissociation, recombination and attachment processes in the upper atmosphere II. The rate of recombination

1939 ◽  
Vol 170 (942) ◽  
pp. 322-340 ◽  
Keyword(s):  
Negative Ions ◽  
Neutral Molecule ◽  
Upper Atmosphere ◽  
The Other ◽  
Negative Ion ◽  
Neutral Atoms ◽  
Attachment Rate ◽  
Additional Advantage ◽  
Positive Ions ◽  
Positive Ion

The ionized regions of the upper atmosphere include, not only neutral atoms and molecules, electrons and positive ions, but also negative ions. Of these, electrons are alone effective in producing reflexion of wireless waves; so that an electron attached to a neutral molecule to form a negative ion is as effectively removed from active participation in these phenomena as one recombined with a positive ion to form a neutral molecule. The decay of electron density at night has been attributed by some authors to recombination with positive.ions and by others to attachment by neutral molecules. The first process is in agreement with the observed law of decay and has the additional advantage of making it easily possible to understand the formation of layers of concentrated ionization; on the other hand, the chance of attachment to a molecule per impact would have to be extremely small for the attachment rate to be negligible, since the number of collisions per second with neutral atoms is very much greater than with positive ions.

scholarly journals A new process of negative-ion formation. IV

1938 ◽  
Vol 168 (932) ◽  
pp. 103-122 ◽  
Keyword(s):  
Negative Ions ◽  
Senior Author ◽  
Negative Ion ◽  
The Past ◽  
Ion Formation ◽  
Positive Ions ◽  
New Process ◽  
The Difference ◽  
To Come ◽  
Positive Ion

The three previous papers of this series (Arnot and Milligan 1936 b ; Arnot 1937 a, b ) contain an account of experimental work which led the senior author to propose a new process of negative-ion formation. This process is the formation of negative ions at metal surfaces by bombardment of the surface with positive ions, the negative ion being formed by the positive ion capturing two electron from the surface. Further work carried out during the past year, which is described in this paper, has revealed a new variation of the above process. In this latter process the impinging positive ion causes an adsorbed atom on the surface to come off as a negative ion. It is believed that this newer process is essentially similar to the process previously reported, the difference being due merely to the transference of excitation energy from the incident positive ion, after its capture of an electron, to the atom adsorbed on the surface. The discovery of this second effect was made independently by Sloane and Press (1938), although they attribute it to a different process.

Negative ion – molecule reactions

1969 ◽  
Vol 47 (10) ◽  
pp. 1815-1820 ◽  
Author(s):  
E. E. Ferguson
Keyword(s):  
Charge Transfer ◽  
Rate Constants ◽  
Reaction Rate ◽  
Reaction Rate Constant ◽  
Negative Ion ◽  
Transfer Reactions ◽  
Ion Molecule Reactions ◽  
Charge Transfer Reactions ◽  
Three Body ◽  
Interchange Reactions

Laboratory reaction rate constant measurements for negative ion – atom interchange reactions, negative ion charge transfer reactions, and negative ion three-body association reactions of aeronomic interest are reviewed and the available data tabulated. The present experimental techniques in use are briefly summarized. Most of the rate constants have been measured only at 300 °K; in a few cases data is available at energies [Formula: see text] as well as at 300 °K, so that an indication of the energy dependence of the rate constants is available.

scholarly journals The formation of negative ions by positive-ion impact on surfaces

1938 ◽  
Vol 168 (933) ◽  
pp. 284-301 ◽  
Keyword(s):  
Ionization Chamber ◽  
Metal Surfaces ◽  
Negative Ions ◽  
Negative Ion ◽  
Distribution Analysis ◽  
Positive Ions ◽  
Mass Spectrograph ◽  
Quantal Theory ◽  
Double Mass ◽  
Positive Ion

The quantal theory of negative ions has now been developed considerably (Massey and Smith 1936; Massey 1938), but on account of difficulties of computing it is usually necessary to assume rather than to prove that a given ion exists, and then to discuss the probability of its formation by different processes. The work described here is a contribution to the experimental side of this subject. It had its origin in a projected attempt to measure the capture cross-section of mercury atoms for electrons, as a verification of Massey and Smith's (1936) then unpublished theory of this process. In considering this it became clear that the experiment would be one of unusual difficulty. Before proceeding with it, therefore, it was decided to verify the existence of Hg - as a stable entity, which is assumed in the quantal theory. this was in doubt since Stille (1933), in some careful experiments, had recently failed to obtain it from the plasma of various forms of discharge through mercury vapour, although it is known that negative ions tend to accumulate in such regions (Emeleus and Sayers 1938). Whilst one of us was repeating his experiments, with modifications which led to essentially the same results and will be describes elsewhere, Arnot and Milligan (1936 b ) reported that they had obtained Hg - by bombardment of metal surfaces with Hg + . A comparison of their work with our own showed only one essential point of difference, namely that the construction of their apparatus did not permit of degassing in situ , a condition satisfied with our tubes. Both for this reason and because of the intrinsic importance of their discovery it was thought desirable to repeat part of their work, with apparatus geometrically similar in electrode construction, but capable of being degassed in a furnace under vacuum. We were again unable to obtain Hg - after the apparatus had been degassed and in operation for a short of that of Hg - was obtained. There were, however, always present several light negative ions, which had the excess energies found by Arnot and Milligan (1936 b ) with Hg - . The conditions under which these were formed led us to suppose that they were produced by bombardment of the metal surfaces by mercury positive ions (Press 1937; Sloane 1937) and not capture of electrons by positive ions of the same species, the process suggested by Arnot and Milligan (1936 b ). The existence of a process of this type, which may be conveniently termed "sputtering" (Sloane and Press 1938), is also implied by some earlier work by J. S. Thompson (1931) which has, so far as we know, never been published in detail. It is, however, impossible to decide definitely ion (e. g. CO - ) when it hits the surface, so long as one is producing the negative ions on a metal surface in a plasma or ionization chamber. One cannot overlook the possibility of the negative ion being formed from its own positive ion, since the latter may be present in the plasma or ionization chamber, and CO + , for example, was in fact shown in our work to be there from the positive-ion mass spectra, although in quantity only a fraction of 1% of Hg + . An unambiguous decision on this point can only be reached by first isolating a particular positive ion by a mass spectrograph, then bombarding a surface by this in a high vacuum , and finally making a mass spectrographic and energy distribution analysis of the resultant negative ions. We have built a double mass spectrograph for this purpose and find that negative ions of one kind possessing energies in excess of that imparted to them by the accelerating fields can be produced by bombardment with positive ions of another kind (Sloane and Press 1938). An account of the experiments with the single mass spectrograph is given in 1. the experiments with the double mass spectrograph are described in 2.

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