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Relative rate experiments were used to measure the rate constant and temperature dependence of the reaction of OH radicals with 2-fluoropropane (HFC-281ea), using ethane, propane, ethyl chloride as reference standards.
We report steady-state voltammetry of outer-sphere redox species at back-gated ultrathin ZnO working electrodes in order to determine electron transfer rate constants k ET as a function of independently-controlled gate bias, V G . We demonstrate that k ET can be modulated as much as 30-fold by application of V G ≤ 8 V. Key to this demonstration was integrating the ultrathin (5 nm) ZnO on a high dielectric constant (k) insulator, HfO 2 (30 nm), which was grown on a Pd metal gate. The high-k HfO 2 dramatically decreased the required V G values and increased the gate-induced charge in ZnO compared to previous studies. Importantly, the enhanced gating power of the Pd/HfO 2 /ZnO stack meant it was possible to observe a non-monotonic dependence of k ET on V G , which reflects the inherent density of redox acceptor states in solution. Furthermore, this work adds to the growing body of literature demonstrating that electrochemical kinetics (i.e., rate constants and overpotentials) at ultrathin working electrodes can be tuned by V G , independent of the conventional electrochemical working electrode potential.
Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br have been measured by a relative rate technique in which the reaction rate of each compound was compared to that of HFC-152a (CH3CHF2) and (for CH2Cl2) HFC-161 (CH3CH2F). Using absolute rate constants for HFC-152a and HFC-161, which we have determined relative to those for CH4, CH3CCl3, and C2H6, temperature dependent rate constants of both compounds were derived. The derived rate constant for CH3Br is in good agreement with recent absolute measurements. However, for the chloromethanes all the rate constants are lower at atmospheric temperatures than previously reported, especially for CH2Cl2 where the present rate constant is about a factor of 1.6 below the JPL 92-20 value. The new rate constant appears to resolve a discrepancy between the observed atmospheric concentrations and those calculated from the previous rate constant and estimated release rates.
Relative rate experiments are used to measure rate constants and temperature dependencies of the reactions of OH with CH3F (41), CH2FCl (31), CH2BrCl (30B1), CH2Br2 (3OB2), CHBr3 (2OB3), CF2BrCHFCl (123aBl(alpha)), and CF2ClCHCl2 (122). Rate constants for additional compounds of these types are estimated using an empirical rate constant estimation method which is based on measured rate constants for a wide range of halocarbons. The experimental data are combined with the estimated and previously reported rate constants to illustrate the effects of F, Cl, and Br substitution on OH rate constants for a series of 19 halomethanes and 25 haloethanes. Application of the estimation technique is further illustrated for some higher hydrofluorocarbons (HFCs), including CHF2CF2CF2CF2H (338pcc), CF3CHFCHFCF2CF3 (43-10mee), CF3CH2CH2CF3 (356ffa), CF3CH2CF2CH2CF3 (458mfcf), CF3CH2CHF2 (245fa), and CF3CH2CF2CH3 (365mfc). The predictions are compared with literature data for these compounds.
Rate constants of 15 OH reactions with halogen-substituted alkanes, C1 to C3, were studied using a relative rate technique in the temperature range 283-403 K. Compounds studied were CHF2Cl (22), CHF2Br (22B), CH3F (41), CH2F2 (32), CHF3 (23), CHClFCCl2F (122a), CHCl2CF3 (123), CHClFCF3 (124), CH3CF3 (143a), CH3CH2F (161), CF3CHFCF3 (227ea), CF3CH2CF3 (236fa), CF3CHFCHF2 (236ea), and CHF2CF2CH2F (245ca). Using CH4, CH3CCl3, CF3CF2H, and C2H6 as primary reference standards (JPL 92-20 rate constants), absolute rate constants are derived. Results are in good agreement with previous experimental results for six of the compounds studied, including CHF2Cl, CHF2Br, CH2F2, CH3CF3, CHFClCFCl2, and CF3CHFCF3. For the remainder the relative rate constants are lower than those derived from experiments in which OH loss was used to measure the reaction rate. Comparisons of the derived Arrhenius A factors with previous literature transition-state calculations show order of magnitude agreement in most cases. However, the experimental A factors show a much closer proportionality to the number of H atoms in the molecule than is evident from the transition state calculations. For most of the compounds studied, an A factor of (8 +/- 3)E-13 cm(exp 3)/(molecule s) per C-H bond is observed. A new measurement of the ratio k(CH3CCl3)/k(CH4) is reported that is in good agreement with previous data.
Current models of turbulent reacting flows frequently use Arrhenius reaction rate constants obtained from static or laminar flow theory and/or experiments, or from best fits of static, laminar, and turbulent data. By treating the reaction rate constant as a continuous random variable which is temperature-dependent, the present study assesses the effect of turbulent temperature fluctuations on the reaction rate constant. This model requires that a probability density function (PDF) describing the nature of the fluctuations be specified. Three PDFs are examined: the clipped Gaussian, the beta PDF, and the ramp model. All the models indicate that the reaction rate constant is greater in a turbulent flow field than in an equivalent laminar flow. In addition, an amplification ratio, which is the ratio of the turbulent rate constant to the laminar rate constant, is defined and its behavior as a function of the mean temperature fluctuations is described
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.
Determination of accurate rate constants for OH abstraction is of great importance for the calculation of lifetimes for HCFCs and their impact on the atmosphere. For HCFC-141b there has been some disagreement in the literature for absolute measurements of this rate constant. In the present work rate constant ratios for HCFC-141b were measured at atmospheric pressure in the temperature range of 298-358 K, with CH4 and CH3CCl3 as reference gases. Ozone was photolyzed at 254 nm in the presence of water vapor to produce OH radicals. Relative depletions of 141b and the reference gases were measured by FTIR. Arrhenius expressions for 141b were derived from each reference gas and found to be in good agreement with each other. The combined expression for HCFC-141b which we recommend is 1.4 x 10 exp -12 exp(-1630/T) with k at 298 K being 5.9 x 10 exp -15 cu cm/molec-s. This value is in excellent agreement with the JPL 92-20 recommendation.
Rate constants for the dissociation/recombination reaction N 2 H 4 (+ M) $^→_←$ NH 2 + NH 2 (+ M) are determined by a combination of quantum-chemical calculations and statistical unimolecular rate theory. Between 1100 and 2500 K, limiting low-pressure rate constants for hydrazine dissociation in the bath gas Ar of k 0 = [Ar] 6.1 × 10 20 (T/1000 K) –7.3 exp (-34490 K/T) cm 3 mol –1 s –1 , limiting high-pressure rate constants of k ∞ = 7.6 × 10 16 (T/1000 K) –1.0 exp(-33600 K/T) s –1 , and center broadening factors of the falloff curves (between 1100 and 1600 K in Ar) of F cent = 0.71 exp(- T/1460 K) + 0.29 exp(- T/21 K) + exp(-13400 K/T) were calculated. Using equilibrium constants K C = 1.7 × 10 3 (T/1000 K) –1.5 exp(-33,460 K/T) mol cm –3 , between 300 and 600 K limiting low-pressure rate constants for the reverse recombination of NH 2 radicals in the bath gas N 2 of k rec,0 = [N 2 ] 4.4 × 10 20 (T/400 K) –6.9 exp (-1630 K/T) cm 6 mol –2 s –1 , limiting high-pressure rate constants of k rec,∞ = 4.4 × 10 13 (T/1000 K) 0.44 exp(-140 K/T) cm 3 mol -1 s –1 , and center broadening factors (between 300 and 600 K in N 2 ) of F cent = exp(- T/1130 K) + exp (-10340 K/T) were obtained. A comparison with experimental results for hydrazine dissociation from the literature suggests incomplete falloff extrapolations toward k ∞ and experimental problems in the determination of k 0 at temperatures above about 1600 K. Finally, implications of the present re-evaluated rate constants for the modeling of high temperature ammonia oxidation kinetics are discussed, showing an only small influence of their precise values on the overall properties of the process.
Measurements of rate constants for HFC-134 (CF2HCF2H) relative to CH3CCl3, HFC-125, and HFC-134a are reported. The measurements were made in a slow-flow, temperature controlled photochemical reactor, and were based on relative rates of disappearance of the parent compounds as measured by FTIR spectroscopy. Hydroxyl radicals were generated by 254-nm photolysis of O3 in the presence of water vapor. NASA/JPL rate constants for the reference compounds are used to derive temperature-dependent rate constants of both compounds. Rate constants obtained from the different reference compounds are in excellent agreement. The presently recommended rate constant for HFC-134a is about 25 percent too high.
In 1922, Lindemann proposed the now-well-known mechanism for pressure-dependent rate constants for unimolecular reactions: reactant molecules with sufficiently high energies dissociate more quickly than collisions can reestablish the Boltzmann distribution of the internal energies of the molecule during its dissociation at low pressures – yielding pressure-dependent rate constants for unimolecular reactions due to the preferential depletion of the high energy states capable of dissociation. In the last century, incredible progress has been made in achieving a far greater understanding of and quantitative predictions for unimolecular and association reactions. In the modern era, pressure-dependent phenomenological rate constants are now nearly universally used to describe the rates of unimolecular and associative reactions in phenomenological kinetic modeling. However, there is a second, more indirect, implication of Lindemann’s mechanism that relates to how these dissociation-induced non-equilibrium distributions impact bimolecular reactions, including non-associative bimolecular reactions – which are generally not considered to have pressure-dependent rate constants. Yet, as we show herein, the same high energy states depleted due to dissociation would otherwise react most rapidly in high-activation-energy bimolecular reactions – yielding a mechanism for pressure-dependent rate constants for bimolecular reactions (including non-associative reactions). Here, we present results from a case study for CH 2 O dissociation, isomerization, and bimolecular reaction with O2 to explore this question. Results from our master equation calculations indicate that the effect of dissociation-induced non-equilibrium distributions on bimolecular reactions can be substantial – even when chemical timescales are well separated from internal energy relaxational timescales (i.e. when the traditional rate constant description would be thought to apply). This effect is found to be more pronounced – and more complex – for bimolecular reactions involving molecular entities whose chemical timescales are merged with the internal energy relaxational timescales. Lastly, we present some ideas for discussion regarding what should be considered as “chemical species” in phenomenological kinetic models.
Rate constant estimates accuracy assessed for differential equations in connection with kinetics of enzymatic reaction
Rate constants and temperature dependencies for the reactions of OH with CF3OCH3 (HFOC-143a), CF2HOCF2H (HFOC-134), and CF3OCF2H (HFOC-125) were studied using a relative rate technique in the temperature range 298-393 K. The following absolute rate constants were derived: HFOC-143a, 1.9E-12 exp(-1555/T); HFOC-134, 1.9E-12 exp(-2006/T); HFOC-125, 4.7E-13 exp(-2095/T). Units are cm(exp 3)molecule(exp -1) s(exp -1). Substituent effects on OH abstraction rate constants are discussed, and it is shown that the CF3O group has an effect on the OH rate constants similar to that of a fluorine atom. The effects are related to changes in the C-H bond energies of the reactants (and thereby the activation energies) rather than changes in the preexponential factors. On the basis of a correlation of rate constants with bond energies, the respective D(C-H) bond strengths in the three ethers are found to be 102, 104, and 106 kcal/mol, with an uncertainty of about 1 kcal/mol.
Relative rate experimental data are used to derive rate constants and temperature dependencies of the reactions of OH with several halocarbons. Rate constants for additional similar compounds are estimated. The experimental data, estimated data, and previously reported data are used to illustrate the effects of F, CL and Br substitution on OH rate constants for a series of 19 halomethanes and 25 haloethanes, as well as some higher HFCs.
A new scheme for relating the absolute value for the kinetic rate constant k to the thermodynamic constant Kp is developed for gases. In this report the forward and reverse rate constants are individually related to the thermodynamic data. The kinetic rate constants computed from thermodynamics compare well with the current kinetic rate constants. This method is self consistent and does not have extensive rules. It is first demonstrated and calibrated by computing the HBr reaction from H2 and Br2. This method then is used on other reactions.
The absolute rate constants for the reaction between the NH2 free radical and acetylene and ethylene is measured experimentally using a flash photolysis technique. The constant is considered to be a function of temperature and pressure. At each temperature level of the experiment, the observed pseudo-first-order rate constants were assumed to be independent of flash intensity. The results of the experiment indicate that the bimolecular rate constant for the NH2 + C2H2 reaction increases with pressure at 373 K and 459 K but not at lower temperatures. Results near the pressure limit conform to an Arrhenius expression of 1.11 (+ or -) 0.36 x 10 to the -13th over the temperature range from 241 to 459 K. For the reaction NH2 + C2H4, a smaller rate of increase in the bimolecular rate constant was observed over the temperature range 250-465 K. The implications of these results for current theoretical models of NH2 + C2H2 (or H4) reactions in the atmospheres of Jupiter and Saturn are discussed.
Charge transfer rate constants were calculated for the carotenoid-porphyrin-C 60 (CPC 60 ) molecular triad dissolved in explicit tetrahydrofuran. The calculation was based on mapping the all-atom anharmonic Hamiltonian of this system onto the spin-boson Hamiltonian. The mapping was based on discretizing the spectral density from the time correlation function of the donor–acceptor potential energy gap, as obtained from all-atom molecular dynamics simulations. Different spin-boson Hamiltonians were constructed for each of the possible transitions between the three excited electronic states in two different triad conformations. The rate constants of three possible transitions were calculated via the quantum-mechanically exact Fermi’s golden rule (FGR), as well as a progression of more approximate expressions that lead to the classical Marcus expression. The advantage of the spin-boson approach is that once the mapping is established, the quantum-mechanically exact FGR and the hierarchy of approximations are known in closed form. The classical Marcus charge transfer rate constants obtained with the spin-boson Hamiltonians were found to reproduce those obtained from all-atom simulations with the linearized semiclassical approximation, thereby confirming the equivalence of the two approaches for this system. Furthermore, within the spin-boson Hamiltonian, we also found that the quantum-mechanically exact FGR rate constants were significantly enhanced compared to the classical Marcus theory rate constants for two out of three transitions in one of the two conformations under consideration. The results confirm that mapping to the spin-boson model can yield accurate predictions for charge transfer rate constants in a system as complex as CPC 60 dissolved in tetrahydrofuran.
Rate constants for excitation of CO by collisions with H2O are needed to understand recent observations of comet spectra. These collision rates are closely related to spectral line shape parameters, especially those for Raman Q-branch spectra. Because such spectra have become quite important for thermometry applications, much effort has been invested in understanding this process. Although it is not generally possible to extract state-to-state rate constants directly from the data as there are too many unknowns, if the matrix of state-to-state rates can be expressed in terms of a rate-law model which depends only on rotational quantum numbers plus a few parameters, the parameters can be determined from the data; this has been done with some success for many systems, especially those relevant to combustion processes. Although such an analysis has not yet been done for CO-H2O, this system is expected to behave similarly to N2-H2O which has been well studies; modifications of parameters for the latter system are suggested which should provide a reasonable description of rate constants for the former.