Kinetics of the reaction of C6H5 with HBr

The rate constant for the reaction of phenyl radical with hydrogen bromide has been measured with the cavity-ring-down method at six temperatures between 297 and 523 K. The Arrhenius expression for the H abstraction reaction can be effectively given by: . The values of these parameters are similar to those for the H + HBr reaction, but are in sharp contrast to those for alkyl radical reactions. The gross difference between the alkyl radical reactions and the phenyl and H-atom reactions could be rationalized in terms of the inductive effects of these radicals as measured by Taft's σ* (polar) constants. © 1993 John Wiley & Sons, Inc.     

Kinetics of the reaction of C6H5 with HBr and DBr

The rate constants for the reaction of C₆H₅ with HBr and DBr have been measured with the cavity–ring–down method in the temperature range of 297 to 523 K and 297 to 500 K, respectively. These rate constants can be effectively represented, in units of cm³/s, by Both activation energies are similar and positive, contrary to those of alkyl radical reactions, all of which exhibit negative temperature dependencies. The difference, as pointed out before [1], could be accounted for by the electron-withdrawing effect of the phenyl vis-à-vis the electron-donating ability of the alkyls. © 1994 John Wiley & Sons, Inc.     

Kinetics of CN(v=0) and CN(v=1) with H2 HCl and HBr

CN radicals have been generated in their X ²Σ⁺ (v=0) and (v= 1 ) levels by pulsed laser photolysis of NCNO at 532 nm, and time-resolved laser-induced fluorescence has been used to measure the rates of their removal by H₂, HC1 and HBr. The rate constants for removal of CN(v= 1 ) by these three species are 1.2 ± 0.3, 1.1 ± 0.2 and 1.3 ± 0.1 times the rate constants for reaction of CN(v=0). The results can be interpreted in terms of vibrationally adiabatic theory and a CN vibrational frequency which is almost the same in the transition state as in the isolated radical.     

Kinetics of the reactions of O(3P) and Cl(2P) with HBr and Br2

A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of reactions (1)–(4) as a function of temperature. In all cases, the concentration of the excess reagent, i.e., HBr or Br₂, was measured in situ in the slow flow system by UV-visible photometry. Heterogeneous dark reactions between XBr (X = H or Br) and the photolytic precursors for Cl(²P) and O(³P) (Cl₂ and O₃, respectively) were avoided by injecting minimal amounts of precursor into the reaction mixture immediately upstream from the reaction zone. The following Arrhenius expressions summarize our results (errors are 2σ and represent precision only, units are cm³ molecule^?1 s^?1): ??₁ = (1.76 ± 0.80) × 10^?11 exp[(40 ± 100)/T]; ??₂ = (2.40 ± 1.25) × 10^?10 exp[?(144 ± 176)/T]; ??₃ = (5.11 ± 2.82) × 10^?12 exp[?(1450 ± 160)/T]; ??₄ = (2.25 ± 0.56) × 10^?11 exp[?(400 ± 80)/T]. The consistency (or lack thereof) of our results with those reported in previous kinetics and dynamics studies of reactions (1)–(4) is discussed.     

Kinetics and product branching ratios of the reaction of (1)CH2 with H2 and D2

The reactions of singlet methylene (a(1)A1 (1)CH2) with hydrogen and deuterium have been studied by experimental and theoretical techniques. The rate coefficients for the removal of singlet methylene with H2 (k1) and D2 (k2) have been measured from 195 to 798 K and are essentially temperature-independent with values of k1 = (10.48 +/- 0.32) x 10(-11) cm(3) molecule(-1) s(-1) and k2 = (5.98 +/- 0.34) x 10(-11) cm(3) molecule(-1) s(-1), where the errors represent 2sigma, giving a ratio of k1/k2 = 1.75 +/- 0.11. In the reaction with H2, singlet methylene can be removed by reaction giving CH3 + H or deactivated to ground-state triplet methylene. Direct measurement of the H atom product showed that the fraction of relaxation decreased from 0.3 at 195 K to essentially zero at 398 K. For the reaction with deuterium, either H or D may be eliminated. Experimentally, the H:D ratio was determined to be 1.8 +/- 0.5 over the range 195-398 K. Theoretically, the reaction kinetics has been predicted with variable reaction coordinate transition state theory and with rigid-body trajectory simulations employing various high-level, ab initio-determined potential energy surfaces. The magnitudes of the calculated rate coefficients are in agreement with experiment, but the calculations show a significant negative temperature dependence that is not observed in the experimental results. The calculated and experimental H to D ratios from the reaction of singlet methylene with D2 are in good agreement, suggesting that the reaction proceeds entirely through the formation of a long-lived methane intermediate with a statistical distribution of energy.     

Kinetic and mechanistic study of the reaction of O(1D) with CF2HBr

A laser flash photolysis–resonance fluorescence technique has been employed to investigate the kinetics and mechanism of the reaction of electronically excited oxygen atoms, O(¹D), with CF₂HBr. Absolute rate coefficients (k₁) for the deactivation of O(¹D) by CF₂HBr have been measured as a function of temperature over the range 211–425 K. The results are well described by the Arrhenius expression k₁(T) = 1.72 × 10^?10 exp(+72/T) cm³molecule^?1 s^?1; the accuracy of each reported rate coefficient is estimated to be ±15% (2σ). The branching ratio for nonreactive quenching of O(¹D) to the ground state, O(³P), is found to be 0.39 ± 0.06 independent of temperature, while the branching ratio for production of hydrogen atoms at 298 K is found to be 0.02_?0.02^+0.01. The above results are considered in conjunction with other published information to examine reactivity trends in O(¹D) + CF₂XY reactions (X,Y = H, F, Cl, Br). © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 262–270, 2001     

Reaction dynamics simulations of the identity S(N)2 reaction H(2)O + HOOH(2)(+)--> H(2)OOH(+)+ H(2)O. Requirements for reaction and competition with proton transfer

Despite the fact that the transition structure of the gas phase S(N)2 reaction H(2)O + HOOH(2)(+)--> HOOH(2)(+)+ H(2)O is well below the reactants in potential energy, the reaction has not yet been observed by experiment. Variational transition state RRKM theory reveals a strong preference for the competing proton transfer reaction H(2)O + HOOH(2)(+)--> H(3)O(+)+ HOOH due to entropy factors. Born-Oppenheimer reaction dynamics simulations confirm these results. However, by increasing the collision energy to around 7.5 eV the probability for nucleophilic substitution increases relative to proton transfer. These observations are explained by the presence of the key common intermediate HOO(H)[dot dot dot]H-OH(2)(+) which leads to effective proton transfer, but can be avoided with increasing collision energy. However, the S(N)2 probability remains below 0.2 since successful passage through the TS requires optimum initial orientation of the reactants, excitation of the relative translational motion and good phase correlation between the O-O vibration and the motion of the incoming water.     

A time-dependent quantum dynamical study of the H + HBr reaction

Time-dependent wave packet calculations were carried out to study the exchange and abstraction processes in the title reaction on the Kurosaki-Takayanagi potential energy surface (Kurosaki, Y.; Takayanagi, T. J. Chem. Phys. 2003, 119, 7838). Total reaction probabilities and integral cross sections were calculated for the reactant HBr initially in the ground state, first rotationally excited state, and first vibrationally excited state for both the exchange and abstraction reactions. At low collision energy, only the abstraction reaction occurs because of its low barrier height. Once the collision energy exceeds the barrier height of the exchange reaction, the exchange process quickly becomes the dominant process presumably due to its larger acceptance cone. It is found that initial vibrational excitation of HBr enhances both processes, while initial rotational excitation of HBr from j(0) = 0 to 1 has essentially no effect on both processes. For the abstraction reaction, the theoretical cross section at E(c) = 1.6 eV is 1.06 A(2), which is smaller than the experimental result of 3 +/- 1 A(2) by a factor of 2-3. On the other hand, the theoretical rate constant is larger than the experimental results by about a factor of 2 in the temperature region between 220 and 550 K. It is also found that the present quantum rate constant is larger than the TST result by a factor of 2 at 200 K. However, the agreement between the present quantum rate constant and the TST result improves as the temperature increases.     

Cocondensation reaction of disulphurdinitride with nickel atoms: The preparation of Ni(S2N2H)2

The utility of metal atom vapour synthesis in the preparation of metalla-sulphur-nitrogen compounds has been investigated. Reaction of nickel atoms with disulphurdinitride, S₂N₂, gave, after extraction with methanol, Ni(S₂N₂H)₂ in ca 15% yield.     

Nuclear spin dependence of the reaction of H(3)+ with H2. I. Kinetics and modeling

The chemical reaction H(3)(+) + H(2) → H(2) + H(3)(+) is the simplest bimolecular reaction involving a polyatomic, yet is complex enough that exact quantum mechanical calculations to adequately model its dynamics are still unfeasible. In particular, the branching fractions for the "identity," "proton hop," and "hydrogen exchange" reaction pathways are unknown, and to date, experimental measurements of this process have been limited. In this work, the nuclear-spin-dependent steady-state kinetics of the H(3)(+) + H(2) reaction is examined in detail, and employed to generate models of the ortho:para ratio of H(3)(+) formed in plasmas of varying ortho:para H(2) ratios. One model is based entirely on nuclear spin statistics, and is appropriate for temperatures high enough to populate a large number of H(3)(+) rotational states. Efforts are made to include the influence of three-body collisions in this model by deriving nuclear spin product branching fractions for the H(5)(+) + H(2) reaction. Another model, based on rate coefficients calculated using a microcanonical statistical approach, is appropriate for lower-temperature plasmas in which energetic considerations begin to compete with the nuclear spin branching fractions. These models serve as a theoretical framework for interpreting the results of laboratory studies on the reaction of H(3)(+) with H(2).     

Kinetics of the multichannel reaction of methanethiyl radical (CH3S*) with 3O2

The CH3S* + O2 reaction system is considered an important process in atmospheric chemistry and in combustion as a pathway for the exothermic conversion of methane-thiyl radical, CH3S*. Several density functional and ab initio computational methods are used in this study to determine thermochemical parameters, reaction paths, and kinetic barriers in the CH3S* + O2 reaction system. The data are also used to evaluate feasibility of the DFT methods for higher molecular weight oxy-sulfur hydrocarbons, where sulfur presents added complexity from its many valence states. The methods include: B3LYP/6-311++G(d,p), B3LYP/6-311++G(3df,2p), CCSD(T)/6-311G(d,p)//MP2/6-31G(d,p), B3P86/6-311G(2d,2p)//B3P86/6-31G(d), B3PW91/6-311++G(3df,2p), G3MP2, and CBS-QB3. The well depth for the CH3S* + 3O2 reaction to the syn-CH3SOO* adduct is found to be 9.7 kcal/mol. Low barrier exit channels from the syn-CH3SOO* adduct include: CH2S + HO2, (TS6, E(a) is 12.5 kcal/mol), CH3 + SO2 via CH3SO2 (TS2', E(a) is 17.8) and CH3SO + O (TS17, E(a) is 24.7) where the activation energy is relative to the syn-CH3SOO* stabilized adduct. The transition state (TS5) for formation of the CH3SOO adduct from CH3S* + O2 and the reverse dissociation of CH3SOO to CH3S* + O2 is relatively tight compared to typical association and simple bond dissociation reactions; this is a result of the very weak interaction. Reverse reaction is the dominant dissociation path due to enthalpy and entropy considerations. The rate constants from the chemical activation reaction and from the stabilized adduct to these products are estimated as functions of temperature and pressure. Our forward rate constant and CH3S loss profile are in agreement with the experiments under similar conditions. Of the methods above, the G3MP2 and CBS-QB3 composite methods are recommended for thermochemical determinations on these carbon-sulfur-oxygen systems, when they are feasible.     

Quinazolinone derivatives. Kinetics of the reaction of 2-chloromethyl-3-hydroxy-4-(3H)quinazolinone with nucleophiles

Reaction of 2-Chloromethyl-3-hydroxy-4(3H)quinazolinone ( 1 ) with aliphatic amines and hydroxide follows two different routes affording substituted methyl quinazolinones and a dimer 2 derived from 1 . The former were formed by S_N² reactions while the latter was formed by an inter-molecular nucleophilic displacement. Second-order and third-order rate constants, respectively, were determined, and the kinetic factors influencing both parallel reactions were analysed.     

Experimental and theoretical investigation of the reaction NH(X3Sigma-) + H(2S)-->N(4S) + H2(X1)Sigmag +)

The rate coefficient of the reaction NH(X (3)Sigma(-)) + H((2)S)-->(k(1a) )N((4)S) + H(2)(X (1)Sigma(g) (+)) is determined in a quasistatic laser-flash photolysis, laser-induced fluorescence system at low pressures (2 mbar< or =p< or =10 mbar). The NH(X) radicals are produced via the quenching of NH(a(1)Delta) (obtained by photolyzing HN(3)) with Xe whereas the H atoms are generated in a H(2)He microwave discharge. The NH(X) concentration profile is measured under pseudo-first-order condition, i.e., in the presence of a large excess of H atoms. The room temperature rate coefficient is determined to be k(1a) = (1.9 +/- 0.5) x 10(12) cm(3) mol(-1) s(-1). It is found to be independent of the pressure in the range considered in the present experiment. A global potential energy surface for the (4)A(") state is calculated with the internally contracted multireference configuration interaction method and the augmented correlation consistent polarized valence quadruple zeta atomic basis. The title reaction is investigated by classical trajectory calculations on this surface. The theoretical room temperature rate coefficient is k(1a) = 0.92 x 10(12)cm(3) mol(-1) s(-1). Using the thermodynamical data for the atoms and molecules involved, the rate coefficient for the reverse reaction, k(-1a), is also calculated. At high temperatures it agrees well with the measured k(-1a).     

Time-dependent quantum study of the kinetics of the H(2S) + FO(2II) OH(2II) + F(2P) reaction

Quantum mechanical wave packet calculations are carried out for the H((2)S) + FO((2)II) --> OH((2)II) + F((2)P) reaction on the adiabatic potential energy surface of the ground (3)A' triplet state. The state-to-state and state-to-all reaction probabilities for total angular momentum J = 0 have been calculated. The probabilities for J > 0 have been estimated from the J = 0 results by using J-shifting approximation based on a capture model. Then, the integral cross sections and initial state-selected rate constants have been calculated. The calculations show that the initial state-selected reaction probabilities are dominated by many sharp peaks. The reaction cross section does not manifest any sharp oscillations and the initial state-selected rate constants are sensitive to the temperature.     

Study of the reaction of MoOS2(S2CNR2)2 with PPh3 in 1,2-dichloroethane: Part I. Kinetics of the teaction of MoOS2(S2CNR2)2 with triphenylphosphine PPh3

The kinetics of the reaction of MoOS₂(S₂CNR₂)₂ (R = CH₃, C₂H₅, n-C₃H₇) with PPh₃ have been studied using a Stopped-flow method. It was found that these MoOS₂(S₂CNR₂)₂ complexes react with PPh₃ in the form of an irreversible second-order reaction. The rate constants at 25°C are respectively 48.4, 23.8, and 20.8 mol^?1 dm³ s^?1 and the activation energies are 4.8, 4.9, and 5.0 Kcal/mol with R = CH₃, C₂H₅, and n-C₃H₇.     

Kinetics of the reaction of C2H5O2 with NO at 295 K

The reaction of C₂H₅O₂ with NO in helium carrier gas at 295 K with [He] = 1.6 × 10¹⁷ cm^?3 has been studied using a gas flow reactor sampled by a mass spectrometer. Because no parent molecular ion or suitable fragment ion produced by C₂H₅O₂ could be detected, the reaction was followed by measuring the formation of NO₂. In so doing, account had to be taken of the small amount of HO₂ known to be present in the reaction mixture, which also leads to NO₂ on reaction with NO. The rate coefficient for the total reaction of C₂H₅O₂ with NO was found to be (8.9 ± 3.0) × 10^?12 cm³/s, and the path which produces NO₂ was found to account for at least 80% of all C₂H₅O₂.     

The reaction of C2F5 radicals with H2S

The reaction of C₂F₅ radicals with H₂S was studied over the range 1°?123°C using C₂F₅ radicals generated by photolysis of perfluoropropionic anhydride. The rate constant k_H for reaction (2) is given by where θ = 2.303RT/cal mole^?1. The relevance of this result to conflicting published data on the analogous reaction between CF₃ radicals and H₂S is discussed. It is concluded that there is little difference in the Arrhenius parameters for reaction of CF₃ and C₂F₅ radicals with H₂S.     

Theoretical study on the rate constants for the C2H5 + HBr --> C2H6 + Br reaction

The reaction C(2)H(5) + HBr --> C(2)H(6) + Br has been theoretically studied over the temperature range from 200 to 1400 K. The electronic structure information is calculated at the BHLYP/6-311+G(d,p) and QCISD/6-31+G(d) levels. With the aid of intrinsic reaction coordinate theory, the minimum energy paths (MEPs) are obtained at the both levels, and the energies along the MEP are further refined by performing the single-point calculations at the PMP4(SDTQ)/6-311+G(3df,2p)//BHLYP and QCISD(T)/6-311++G(2df,2pd)//QCISD levels. The calculated ICVT/SCT rate constants are in good agreement with available experimental values, and the calculate results further indicate that the C(2)H(5) + HBr reaction has negative temperature dependence at T < 850 K, but clearly shows positive temperature dependence at T > 850 K. The current work predicts that the kinetic isotope effect for the title reaction is inverse in the temperature range from 200 to 482 K, i.e., k(HBr)/k(DBr) < 1.