Effect of processes at the reactor surface on the low-pressure hydrogen f lame

The interaction of the low-pressure flame of a 2H₂-O₂ mixture with a quartz reactor surface was studied by the resonance fluorescence technique. The results confirmed the fundamental statement of N. N. Semenov’s theory concerning chain propagation in the gas and termination on the surface in the kinetic region of chain termination (quadratic decay in the heterogeneous negative chain interaction) and in the diffusion region (linear decay). The kinetic curves observed in the kinetic and diffusion chain termination regions on the wall were well matched using N. N. Semenov’s theory, taking into account the heterogeneous catalytic chain initiation and interaction processes occurring on the wall with a variable “rate constant.” The interaction of chains on the wall markedly retards ignition in the gas in the kinetic region and has almost no influence on chain propagation in the gas in the diffusion region of the heterogeneous chain termination. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1301–1308, August, 2006.     

The thermal explosion of the detonating mixture is impossible without a chain avalanche

The fundamental regularities of hydrogen/oxygen combustion are considered, which unambiguously indicate the branched chain character of the process at atmospheric pressure. It is noted that, in the general case, the ignition conditions are determined by the competition between chain termination and both chain branching and chain propagation reactions. Some publications ignoring this important point are considered.     

The constancy of the concentration of an inhibitor preventing the ignition of gases

Mechanisms of consumption of inhibitors in gas mixtures in different combustion modes—ignition prevention and suppression of flame propagation and detonation—have been revealed. It has been found that no more than a few hundredths of a percent of the initial reagents, including the inhibitor, are consumed for the prevention of ignition. In suppression of flame propagation and detonation, the inhibitor is consumed only in chain termination reactions. Oxygen is additionally consumed only in reactions with the products of incomplete oxidation of the inhibitor. The results have been interpreted in the framework of the theory of nonisothermal chain processes.     

High-speed color cinematography of chain self-ignition in the hydrogen,methane, and isobutylene oxidation reactions

The spatial development of chain self-ignition in the oxidation of stoichiometric mixtures of hydrogen, methane, and isobutylene with oxygen at total pressures of 10–100 Torr and T = 750–1000 K has been investigated by high-speed color cinematography. The spatial development of the chain process is governed by the properties of the reactor surface and by the heating time of the combustible mixture. A numerical simulation of the process has been carried out.     

The chain character of the third self-ignition limit of hydrogen-oxygen mixtures and flame propagation at atmospheric pressure

It is shown that the characteristic time of the hydrogen-oxygen reaction without the participation of reaction chains is thousands of times longer than the characteristic time of heat removal from the reactor under third self-ignition limit conditions. As a result, reaction mixture self-heating does not exceed several degrees and, contrary to commonly accepted views, cannot cause thermal ignition. It is also shown that the reason for self-ignition under these conditions is the excess rate of chain branching compared with chain termination responsible for the formation of chain avalanches. For the same reason, layer-by-layer ignition during laminar flame propagation is also a chain process. Self-heating arises as a result of the development of chain combustion and strengthens chain avalanches. Explosion and detonation inhibition shows that chain avalanches play an important role in these processes.     

Isothermal waves of hydrogen oxidation

It is analytically shown that the chain ignition region is extended in the reaction of hydrogen oxidation due to the nonlinear interaction H + HO₂ = 2 OH. As a result, the reaction propagates isothermally under the isothermal conditions outside the ignition region, which is calculated by the scheme taking into account only linear reactions with respect to radicals, if the reaction is initiated by additives of hydrogen atoms. The ignition limits were calculated with allowance for the above interaction, and the mathematical modeling of propagation of the hydrogen oxidation reaction under the isothermal conditions was performed.     

Simulation of the inhibition of hydrogen-air flame propagation

The results of simulation and experimental data presented here demonstrate that the competition between chain branching and chain termination is the key factor in hydrogen-air flame propagation, including the temperature regime of the process and the formation of concentration limits. Self-heating becomes significant in developed combustion. It enhances the chain avalanche and ensures the temperature necessary for layer-by-layer chain ignition. By varying the ratio between the chain branching and termination rates by means of an inhibitor makes it possible to control the flame propagation process.     

Interaction of a low-pressure gas flame and heterogeneous catalytic processes on the reactor surface

Conclusions (1) It was shown that the Semenov theory in various modes of chain termination quantitatively describes oxyhydrogen combustion near the first ignition limit with allowance for the interaction between the flame and the catalytic processes on the reactor wall. (2) Numerical modeling of oxyhydrogen ignition in the diffusion-controlled chain-termination mode detected the dependence of the rate “constant” for heterogeneous chain initiation on the model of the reaction in the gas. (3) For the first time, the change in the specific rate of heterogeneous chain initiation during a single ignition was determined. (4) method for controlling the low-pressure flame mode by affecting tubes far from the reactor was proposed and applied. Original Russian Text ? E.N. Aleksandrov, S.N. Kozlov, N.M. Kuznetsov, 2006, published in Doklady Akademii Nauk, 2006, Vol. 407, No. 5, pp. 630–633. Presented by Academician A.E. Shilov October 5, 2005     

Conformational statistics of polymer chain terminally attached to wall (III) —NRW model loop chain

When the two end groups of a linear polymer chain are absorbed on a solid surface, the polymer chain forms the “loop” conformation. Investigation has been made on the conformational statistics of a model loop chain by the normal random walk (NRW) on a lattice confined in the half-infinite space. Based on the conformational distribution function of the NRW model tail chain, it is easy to deduce an analytical formula expressing the conformational number of the model loop chain. It was found that the ratio of the conformational number of the model loop chain to that of the free chain varies with the power functionN ^-2/3 when the chain lengthN→οο. The same result -was obtained by means of the recursion equation. The ratio of the mean square end-to-end distanceh ² for the model loop chain to its mean square bond lengthl ² is 2N/3. Compared with the free chain with the same lengthN, the mean square end-to-end distance of the model loop chain contracts to a certain extent. The basic relationships deduced were supported by the exact enumeration and Monte Carlo simulations. Project supported by the National Natural Science Foundation of China.     

Spectroscopic investigations on II–VI-semiconductor nanocrystals and their assemblies

This review points out that (magneto-)optical measurements may help to shine light on the recombination processes taking place in semiconductor nanocrystals. The surface capping with thiols creates a CdS shell around CdTe cores and forms a Cd site that is not fourfold-coordinated at the surface. It is pointed out how specific cappings such as thio-amines and thio-acids assist in coupling NCs and how we may distinguish between NC–NC interactions via electrostatic and covalent linking with the aid of the optical measurements. Furthermore, with static and time-resolved ODMR studies on IR-active core-shell HgTe/Hg _x Cd_1−x Te(S) particles it is demonstrated how the nature of the recombination emission being associated with a Cd–Hg mixed site is elucidated and by this yielding structural information on the NC core-shell interface. With these examples we show that and how nanomaterials of probable technological interest are studied beneficially with advanced spectroscopic techniques.     

Theory of non-local (pair site) reactivity from model static-density response functions

Activation is a fundamental and well-known concept in chemistry. It may be qualitatively defined as an increase in the chemical reactivity pattern of a molecule at a given site k when the system is locally perturbed at a different site l, say. This external perturbation arise from a localized molecular rearrangement, a substitution, a selective solvation or simply by the approach of a reagent of variable hardness. This work presents a theoretical approach intending to quantify this activation concept in the density functional framework. This is done here by first calculating the fluctuation of the electron density at a given site k for the ground state of the isolated substrate (static reactivity model) and then incorporating the substrate and model electrophile reagents in a spatial disposition related to a virtual transition structure for the parent system. This perturbation is assumed representable by local changes in the external potential. It is shown that a local approximation to the softness kernel s(r, r′) yields a simple expression for the fluctuation of the electron density δρ(r _k ), which shows that this change becomes proportional to the variation of an effective potential δu(r _k ), containing the information on the variation in the chemical potential and the external perturbing potential at site k; the proportionality constant being the local softness s ⁰(r k) at that site. The strong local approximation made to the kernel s(r, r′) causes the second reactivity site (l) to implicitly appear in the formulation through the changes in the electronic chemical potential term. It is shown that the introduction of a less restrictive approach to the linear response function, obtained from a model Kohn-Sham one-electron density matrix, leads to the same result. Non-locality is therefore self-contained in the electronic chemical potential contribution to the modified potential, and may be associated with an intramolecular charge transfer between the active sites of the ambident nucleophilic/electrophilic substrate, promoted by the presence of the reagents. The resulting formulation of pair-site reactivity is illustrated for the electrophilic attack on the CN⁻ ion by different model electrophile agents of variable hardness. It is shown that correct reactivity indexes are obtained only when the topology of the transition structure is used as a vantage point to perturb the CN⁻ ion. The calculations were performed at both density functional theory and ab-initio Hartree-Fock levels. The results show that the proposed model is independent of the method used to obtain ρ(r). Received: 30 September 1997 / Accepted: 30 December 1997     

The dependence of the rules governing gas-phase combustion on the competition between chain propagation and chain termination reactions

The competition between chain propagation and chain termination reactions was shown to play an important role in gas-phase combustion. Conditions under which this competition to a substantial extent determined the critical ignition conditions and the rate of the process were analyzed. Examples that showed that ignoring the role played by chain propagation, chain termination, and chain branching reactions in branched-chain processes led to conclusions that contradicted experimental data were considered.     

Chain mechanism of the reactions of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′-diphenyl-1,4-benzoquinone diimine with thiophenol and 1-decanethiol

The kinetics of the reactions of N,N′-diphenyl-1,4-benzoquinone diimine with thiophenol and 1-decanethiol in chlorobenzene at 343 K has been investigated spectrophotometrically in an argon atmosphere with monitoring of the disappearance of quinone diimine as its absorbance in the visible range. The acceleration of the reactions in the presence of initiators—tetraphenylhydrazine and azobisisobutyronitrile—indicates that the reactions proceed via a chain mechanism under the chosen experimental conditions. The chain length of the reactions in the absence of an initiator is estimated: ν ≈ 10 units in the reaction of quinone diimine with thiophenol and ν ≈ 100 units in the reaction with 1-decanethiol at a quinone diimine concentration of about 10⁻⁴ mol/L and thiol concentrations of about 10⁻³ mol/L. The dependence of the kinetic parameters of the initiated reaction on the thiophenol concentration suggests that the reaction of the thiyl radical with quinone diimine is the rate-determining step of chain propagation. The rate constant of this reaction is estimated at k _pr = 3.2 × 10⁵ L mol⁻¹ s⁻¹. The rates of chain initiation due to the direct interaction of the initial reactants are estimated. In these reactions, the homolytic cleavage of the S-H bond occurs in the thiol, due to which, other conditions being equal, the radical formation rate in the quinone diiminethiophenol system is at least two orders of magnitude higher than that in the quinone diimine-1-decanethiol, in which the strength of S-H bond is higher. A radical chain mechanism is proposed for the reaction of quinone diimine with the thiols on the basis of the data obtained.     

The role of oxygen in the ignition of polystyrene by a small flame

The ignition of slabs of high-impact polystyrene by a lean hydrogen–oxygen flat flame was studied. The ignition delays and inital rates of flame development after ignition are reported as functions of gas temperature and the separation between flame and polymer surface. The delays follow an Arrhenius-type expression with an activation energy of 98 ± 18 kJ mol^?1. The rates of flame development drop as the gas temperature increases. During long ignition delays the apparent heat transfer coefficient at the sample surface dropped from about 100 W m^?2 K^?1 to values close to that expected for a hot gas impinging at right angles on a cold surface. For short delays it was higher and more constant at about 100 W m^?2 K^?1. Although the surface temperature reached before ignition exceeded that required for nonoxidative pyrolysis, the polymer surface charred only when oxygen was present. It is concluded that both oxidative and nonoxidative pyrolysis contribute to the ignition of polystyrene.     

Kinetic aspects of chemical control over flame propagation in combustible gases

Kinetic aspects of controlling ignition and flame propagation parameters in the gas phase by chemical methods are considered. The efficiency of the chemical methods is due to the branched chain character of gas-phase combustion reactions and the dominant role of the competition between chain branching and chain termination in these processes.     

The influence of short‐chain branching on the morphology and structure of polyethylene single crystals

The influence of short‐chain branching on the formation of single crystals at constant supercooling is systematically studied in a series of metallocene catalyzed high‐molecular‐weight polyethylene samples. A strong effect of short‐chain branching on the morphology and structure of single crystals is reported. An increase of the axial ratio with short‐chain branching content, together with a characteristic curvature of the (110) crystal faces are observed. To the best of our knowledge, this is the first time that this observation is reported in high‐molecular‐weight polyethylene. The curvature can be explained by a continuous increase in the step initiation—step propagation rates ratio with short‐chain branching, that is, nucleation events are favored against stem propagation by the presence of chain defects. Micro‐diffraction and WAXS results clearly indicate that all samples crystallize in the orthorhombic form. An increase of the unit cell parameter a₀ is detected, an effect that is more pronounced than in the case of single crystals with ethyl and propyl branches. The changes observed are compatible with an expanded lattice due to the presence of branches at the surface folding. A decrease in crystal thickness with branching content is observed as determined from shadow measurements by TEM. The results are in agreement with additional SAXS results performed in single crystal mats and with indirect calorimetry measurements. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1751–1762     

Effect of amines on the controlled synthesis of poly(methyl methacrylate) catalyzed by ruthenacarboranes

The effects of amines on the activity of ruthenium catalysts in the controlled synthesis of poly(methyl methacrylate) are reported at 80°C. The introduction of tert-butylamine or triethylamine into the polymerization system raises the polymerization rate by 1–2 orders of magnitude without reducing the high degree of control over the chain propagation step. The “living” character of methyl methacrylate polymerization in the presence of ruthenacarboranes and amines is proved by the fact that, as the monomer conversion increases, the molecular weight of the resulting polymer increases linearly and the polydispersity index decreases. The polymer can serve as a macroinitiator for postpolymerization and block copolymer synthesis.     

Electrical conductivity of magnesium oxide as a catalyst for radical chain hydrocarbon pyrolysis reactions

The electrical conductivity of polycrystalline MgO between 350 and 750°C is determined by the transport of surface electronic and hole defects and depends on the applied voltage. Near 620°C at low applied voltages, the conductivity decreases by 1–2 orders of magnitude in a narrow temperature range (ΔT = 75°C), and this is accompanied by a change of the sign of the surface charge carriers. The “ignition” of the catalytic activity of magnesium oxide in free radical generation in radical chain hydrocarbon pyrolysis is observed in the same temperature range. It is assumed that the change of the sign of the charge carriers is due to the existence of an isoelectric temperature T _i and that, at T > T _i , O_O^· defects come out to the magnesium oxide surface.     

Spatially Directed Pyrolysis via Thermally Morphing Surface Adducts

Combustion is often difficult to spatially direct or tune associated kinetics—hence a run-away reaction. Coupling pyrolytic chemical transformation to mass transport and reaction rates (Damköhler number), however, we spatially directed ignition with concomitant switch from combustion to pyrolysis (low oxidant). A ‘surface-then-core’ order in ignition, with concomitant change in burning rate,is therefore established. Herein, alkysilanes grafted onto cellulose fibers are pyrolyzed into non-flammable SiO₂ terminating surface ignition propagation, hence stalling flame propagating. Sustaining high temperatures, however, triggers ignition in the bulk of the fibers but under restricted gas flow (oxidant and/or waste) hence significantly low rate of ignition propagation and pyrolysis compared to open flame (Liñán's equation). This leads to inside-out thermal degradation and, with felicitous choice of conditions, formation of graphitic tubes. Given the temperature dependence, imbibing fibers with an exothermically oxidizing synthon (MnCl₂) or a heat sink (KCl) abets or inhibits pyrolysis leading to tuneable wall thickness. We apply this approach to create magnetic, paramagnetic, or oxide containing carbon fibers. Given the surface sensitivity, we illustrate fabrication of nm- and μm-diameter tubes from appropriately sized fibers.