The kinetics of the chromic acid oxidation of diphenylmethane

The kinetics of the chromic acid oxidation of diphenylmethane in aqueous acetic acid solution has been studied. The rate law is v = k[φCH₂φ][CrO₃]h₀ a kinetic isotope effect, k_H/k_D = 6·4 at 30°, was noted, and electron releasing groups were found to moderately facilitate the reaction (⁺ = −1·17). These, and related data, suggest that the initial reaction is the abstraction of a hydrogen atom forming a benzhydryl radical. The latter may then be further oxidized to give the product, benzphenone. It is noted that the chromic acid oxidations which must involve hydrogen abstraction all show a kinetic dependence on the total chromium (VI) concentration, whereas those which are believed to proceed via an ester mechanism have a kinetic dependence on only the acid chromate ion. This difference is suggested as a possible method of distinguishing between these two mechanisms. The effect of the water content of the solvent on the rate of the reaction is discussed, and a tentative, relative, H₋ scale for some of these solutions is suggested. This may permit one to determine the number of molecules of water which are involved in a reaction.     

Temperature dependence of the rate constant for reactions of hydrated electrons with H, OH and H2O2

The temperature dependence of the rate constants, for the reactions of hydrated electrons with H atoms, OH radicals and H₂O₂ has been determined. The reaction with H atoms, studied in the temperature range 20–250°C gives k(20°C) = 2.4 × 10¹⁰M^-1s¹ and the activation energy E_A = 14.0 kJ mol^-1 (3.3 kcal mol^-1). For reaction with OH radicals the corresponding values are, k(20°C) = 3.1 × 10¹⁰M^-1s^-1 and E_A = 14.7 kJ mol^-1 (3.5 kcal mol^-1) determined in the temperature range 5–175°C. For reaction with H₂O₂ the values are, k(20°C) = 1.2 × 10¹⁰M^-1s^-1 and E_A = 15.6 kJ mol^-1 (3.7 kcal mol^-1) measured from 5–150°C. Thus, the activation energy for all three fast reactions is close to that expected for diffusion controlled reactions. As phosphates were used as buffer system, the rate constant and activation energy for the reaction of hydrated electron with H₂PO₄^- was determined to k(20°C) = 1.5 × 10⁷M^-1s^-1 and E_A = 7.4 kJ mol^-1 (1.8 kcal mol^-1) in the temperature range 20–200°C.     

Far-UV laser flash photolysis in solution. A study of the chemistry of 1,1-dimethylsilene in hydrocarbon solvents

The far-UV (193 nm) laser flash photolysis of nitrogen-saturated isooctane solutions of 1,1-dimethylsiletane allows the direct detection of 1,1-dimethylsilene as a transient species, which (at low laser intensities) decays with pseudo-first-order kinetics (τ 10 μs) and exhibits a UV absorption spectrum with λ_max 255 nm. Characteristic rapid quenching is observed for the silene with methanol (k_McOH = (4.9 ± 0.2) × 10⁹ M⁻¹ s⁻¹), tert-butanol (k_BuOH = (1.8 ± 0.1) × 10⁹ M⁻¹ s⁻¹) and oxygen (k_O2 = (2.0 ± 0.5) × 10⁸ M⁻¹ s⁻¹). The Arrhenius activation parameters for the reaction with methanol have been determined to be E_a = −2.6 ± 0.6 kcal mol⁻¹ and log A = 7.7 ± 0.3.     

Kinetics of formation of intermediates in silver ion assisted aquations

There is kinetic evidence of the formation of [Co(NH₃)₅NCSAg₃]⁵⁺ in the interaction of [Co(NH₃]⁵NCS]²⁺ with Ag⁺ in aqueous solution, with pseudo-first-order formation rate constant k = 0.158 s⁻¹ for the forward reaction in the following equation at 25°C and [Ag⁺] in the range of 1.23–5.0 × 10⁻² mol dm⁻³ and 0.10 ionic strength (NaClO₄):

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Additionally, the formation constant, β₂, for [Co(NH₃)₅NCSAg₂]⁴⁺ has been determined to be log β₂ = 4.717. For the [Rh(NH₃)₅I]²⁺-Ag⁺ reaction there is evidence of an outer-sphere interaction with rate constants of k₂ = 670 dm³ mol⁻¹ s⁻¹ at 25°C and 0.10 ionic strength. This outer-sphere species undergoes further reaction to give the silver ion containing intermediates of the aquation reactions.     

Substituent effects on ultrafast excited-state proton transfer of protonated aniline derivatives in aqueous solution

Substituent effects on the proton dissociation of protonated aniline derivatives upon femtosecond laser pulse excitation are investigated for m- and p-cyanoanilines and m- and p-methoxyanilines in aqueous solution. The cyano substitution at the meta-position increases the rate significantly (k_dis=3.7 × 10¹¹ s⁻¹) compared to aniline (k_dis=1.3 × 10¹⁰ s⁻¹), while the methoxy substitution reduces the rate remarkably. Either substituent at the para-position shows only slight influences on the rate. The strong dependences of the k_dis value on the substituent and the substituted position are reasonably explained on the basis of the free energy change.     

The kinetic isotope effect in the photochlorination of methane

The kinetic isotope effect for the photochemically initiated chlorination of methane-d₂ has been determined. The value is k_H/k_D = 12·1 at 0°C., and the variation with temperature is given by k_H/k_D = 1·09 exp (1300/RT. The results are considered in terms of a semiempirical potential energy surface, and the general subject of the magnitudes of primary kinetic isotope effects is discussed.     

Direct kinetic studies of the reactions of 2-butoxy radicals with NO and O2

This Letter reports the first kinetic study of 2-butoxy radicals to employ direct monitoring of the radical. The reactions of 2-butoxy with O₂ and NO are investigated using laser-induced fluorescence (LIF). The Arrhenius expressions for the reactions of 2-butoxy with NO (k₁) and O₂ (k₂) in the temperature range 223–311 K have been determined to be k₁=(7.50±1.69)×10⁻¹²×exp((2.98±0.47) kJmol⁻¹/RT) cm³ molecule⁻¹ s⁻¹ and k₂=(1.33±0.43)×10⁻¹⁵×exp((5.48±0.69) kJmol⁻¹/RT) cm³ molecule⁻¹ s⁻¹. No pressure dependence was found for the rate constants of the reaction of 2-butoxy with NO at 223 K between 50 and 175 Torr.     

Temperature dependence of the reaction C2H (C2D) + O2 between 295 and 700 K

The rate coefficients for the reactions of C₂H and C₂D with O₂ have been measured in the temperature range 295 K T 700 K. Both reactions show a slightly negative temperature dependence in this temperature range, with k_C2H+O2 = (3.15 ± 0.04) × 10⁻¹¹ (T/295 K)^{−(0.16 ± 0.02)} cm³ molecule⁻¹ s⁻¹. The kinetic isotope effect is k_C2H/k_C2D = 1.04 ± 0.03 and is constant with temperature to within experimental error. The temperature dependence and the C₂H + O₂ kinetic isotope effect are consistent with a capture-limited metathesis reaction, and suggest that formation of the initial HCCOO adduct is rate-limiting.     

Time-resolved vibrational cemiluminescence: Rate constants for the reaction F + HC1 → HF + Cl and for the relaxtion of HF(v = 3) by HCl, CO2, N2O, CO, N2 and O2

The reaction: F + HCl→ HF (v 3) + Cl (1), has been initiated by photolysing F₂ using the fourth-harmonic output at 266 nm from a repetitively pulsed Nd: YAG laser By analysing the time-dependence of the HF(3,0) vibrational chemiluminescence, rate constants have been determined at (296 ± 5) K for reaction (1), k₁ = (7.0 ± 0.5) × 10⁻¹² cm³ molecule⁻¹ s⁻¹, and for the relaxation of HF(v = 3) by HCl, CO₂, N₂O, CO, N₂ and O₂: k_HCl = (1.18 ±0.14) × 10⁻¹¹ k_CO2 = (1.04 ± 0. 13) × 10⁻¹², k_N2O = (1.41 ± 0.13) × 10⁻¹¹ k_CO = (2.9 ± 0.3) × (10⁻¹², k_N2 = (7.1 ± 0.6) × 10⁻¹⁴ and k_O2 = (1.9 ± 0.6) × 10⁻¹⁴ cm³molecule⁻¹s⁻¹.     

Interconversion kinetics and ordering of 1,4- and 1,1-dimethylcyclohexane in liquid-crystalline solutions by 1D and 2D deuterium NMR

Deuterium NMR spectra of perdeuteriated 1,4-dimethylcyclohexane-d₁₆ and 1,1-dimethylcyclohexane-d₁₆ dissolved in the nematic solvent ZLI 2452 are reported for the temperature range -40 to +80°C. Between -30 and +60°C the spectra exhibit characteristic exchange broadening and coalescence due to the ring inversion process. In the extreme slow exchange regime, peak assignment and determination of relative signs of the deuterium quadrupole interactions were made using 2D exchange spectroscopy and structural parameters derived from molecular mechanics calculations. In the intermediate temperature range the lineshapes were interpreted quantitatively in terms of the ring interconversion kinetics yielding the kinetic equations, k = 1.38 × 10¹³ exp (-45.2/RT)s^-1 for 1,4-dimethylcyclohexane, and k = 4.05 × 10¹³ exp (-49.0/RT)s^-1 for 1,1-dimethylcyclohexane, where R is in kJ mol^-1. The complete ordering matrix of both compounds was determined over the whole temperature range of the measurements.     

Regioselective addition of protic acids to tricarbonyliron complexes of 2,3,5,6-tetrakis(methylene)-7-oxabicyclo[2.2.1]heptane. Crystal structure of (C10H10O)Fe2(CO)6

The main product of the thermal reaction between the title oxatetraene (I) and Fe₂(CO)₉ in ether/pentane is the bimetallic complex (C₁₀H₁₀O)Fe₂(CO)₆-diexo (II), which has C_2υ symmetry both in the solid state (X-ray analysis) and in solution. Whereas the protonation of the free ligand leads usually to polymerisation, the addition of a protic acid such as CF₃CO₂H to II proceeds cleanly at 0°C giving first a (η 3-allyl)Fe(CO)₃O₂CCF₃ complex (III). The intermediate III adds a second equivalent of acid in a slower step (k₂/k₁ = 0.1, CF₃CO₂D/CHCl₃, 0°C) giving the trans-bis(η³-allyl) isomer IV with high regioselectivity. The addition of CF₃CO₂D yields the corresponding deuteriomethylallyliron tricarbonyl trifluoroacetates III′ and IV′. No further deuterium incorporation is observed at 0°C, thus confirming the kinetic control of the regioselective double addition of protic acid to II.     

Kinetics and mechanisms of the redox reaction of hexaaquotitanium(III) and the ethylenediamine tetraacetato titanium(III) complex by aqueous solutions of bromine

At 25°C, I = 1.0 M (CF₃SO₃⁻Li⁺+CF₃SO₃H), [H⁺] = 0.034–0.274 M and λ = 453 nm, the rate equation for the oxidation of Ti(H₂O), ₆³⁺ by bromine was found to be: −d/[Br₂]T/dt=kK/[Br₂][Ti^III]/[H⁺]+K+kK/[Br₃⁻][Ti^III]/[H⁺+K, where k = 9.2 × 10⁻³ M ⁻¹ s ⁻¹ and K = 4.5 × 10⁻³ M. At [H⁺] = 1.0 M, [Br⁻] = 0.05–0.4 M, the apparent second-order rate constant decreases as [Br⁻] increases.

The pH-dependence of the oxidation of Ti^III-edta by bromine is interpreted in terms of the change in identity of the Ti^III-edta species as the pH of the reaction medium changes. The second-order rate constants were fitted using a non-linear least-square computer program with (1/k₀^edta)² weighting into an equation of the form: k₀^edta =k₁+k₂K₁[H⁺]⁻¹+k₃K₁K₂[H⁺]^−2/1+K₁[H⁺[H⁺⁻¹+K₁K₂[H⁺]⁻², with K₁ and K₂ fixed as earlier determined at 9.55 × 10⁻³ and 2.29 × 10⁻⁹ M, respectively, for the oxidation of bromine. k₁=k₂=(3.1±0.32)×10³M⁻¹s⁻¹ k₃=(2.3±0.45)×10⁶N⁻¹s⁻¹.

It is proposed that these electron transfer reactions proceed by univalent changes with the production of Br₂^.− as a transient intermediate. An outer-sphere mechanism is proposed for these reactions. The homonuclear exchange rate for Ti^III-edta+Ti^IV-edta is estimated at 32 M⁻¹ s⁻¹.     

Kinetics and mechanism of the reaction between silver(III) and thiourea in aqueous alkaline media

The tetrahydroxoargentate(III) ion, Ag(OH)₄⁻, is rapidly reduced by thiourea (tu) in accordance with the three term rate law RATE = {k₁+(k₂+k₃[OH⁻])[tu]}[Ag^III] where k₁ = 1.08 s⁻¹, k₂ = 1.46 x 10³ M⁻¹ s⁻¹, and k₃ = 2.02 x 10³ M⁻² s⁻¹. The k₁ path occurs via the rate-determining aquation of Ag(OH)₄⁻ while the other two paths involve axial attack of thiourea on silver. The higher values of k₂ and k₃ compared to the ethylenediamine reaction, which obeys the same rate law, is a reflection of the greater nucleophilicity of tu.

Following the redox reaction, solutions become brown in a reaction that obeys pseudo-first-order kinetics. Similar behaviour is observed when tu is replaced by Na₂S or thio-acetamide and when Ag^I reacts with any of these sulphur containing compounds. We attribute this process to the Ag^I promoted formation of sulphide species which eventually precipitate as Ag₂S.     

First steps in radiation-induced hydrogel synthesis: radical formation and oligomerization in dilute aqueous N-isopropylacrylamide solutions

The reactions of hydroxyl radical, hydrogen atom and hydrated electron intermediates of water radiolysis with N-isopropylacrylamide (NIPAAm) were studied by pulse radiolysis in dilute aqueous solutions. OH, H and e_aq⁻ react with NIPAAm with rate coefficient of (6.9±1.2)×10⁹, (6.6±1)×10⁹, and (1.0±0.2)×10¹⁰ mol⁻¹ dm³ s⁻¹. In OH and H radical addition to the double bond mainly -carboxyalkyl type radicals form, (OHCH₂CH^√C(N-i-C₃H₇)O and CH₃CH^√C(N-i-C₃H₇)O). In reaction of e_aq⁻ oxygen atom centered radical anion is produced (CH₂CHC^√(N-i-C₃H₇)O⁻), the anion undergoes reversible protonation with pK_a=8.7. There is also an irreversible protonation on the β-carbon atom that produces the same radical as forms in H atom reaction (CH₃CH^√C(N-i-C₃H₇)O). The -carboxyalkyl type radicals at low NIPAAm concentration (0.1–1 mmol dm⁻³) mainly disappear in self-termination reactions, 2k_t,m=8.4×10⁸ mol⁻¹ dm³ s⁻¹. At higher concentrations the decay curves reflect the competition of the self-termination and radical addition to monomer (propagation). The termination rate coefficient of oligomer radicals containing a few monomer units is 2k_t≈2×10⁸ mol⁻¹ dm³ s¹.     

Efficient regioselective labelling of the CFC alternative 1,1,1,2-tetrafluoroethane (HFC-134a) with fluorine-18

Efficient chemistry is described for the regioselective labelling of the CFC alternative 1,1,1,2-tetrafluoroethane with cyclotron-produced positron-emitting fluorine-18 (t_1/2 = 109.7 min). [1-¹⁸F]1,1,1,2-Tetrafluoroethane was prepared by nucleophilic addition of no-carrier-added [¹⁸F]fluoride to trifluoroethylene and [2-¹⁸F]1,1,1,2-tetrafluoroethane by nucleophilic displacement of tosylate with [¹⁸F]fluoride in 2,2,2-trifluoroethyl p-toluenesulphonate. Each reaction was mediated by a potassium cation-Kryptofix^® 2.2.2 complex, with or without acetonitrile as solvent, in a sealed glassy carbon vessel. The selectivities were 97.2±0.4% for labelling in the 1-position by nucleophilic addition and 91.2±1.2% for labelling in the 2-position by nucleophilic substitution. GC separation afforded each labelled tetrafluoroethane in high radiochemical purity (>99.995%) and high chemical purity (>99.6%). Specific radioactivities of about 37 MBq (1 mCi) per μmol were obtained. Each synthesis was fully automated to cope safely with the high initial radioactivity and delivered purified product within one physical half-life of the fluorine-18 The products are suitable for pharmacokinetic studies in man.     

HS+HO2气相反应机理及主通道速率常数的理论研究

采用CCSD(T)/6-311++G(3df, 2pd)//B3LYP/6-311+G(2df, 2p)双水平计算方法构建了HO₂+HS反应体系的单、三重态反应势能面,并对该反应主通道的速率常数进行了研究。研究结果表明,标题反应经历了八条反应通道,其中三重态反应通道R1是标题反应主通道。此通道包含路径Path 1 (R → ³IM1 → ³TS1 → P1(³O₂+H₂S))和Path 1a (R → ³IM1a → ³TS1a → P1(³O₂+H₂S))两条路径。利用经典过渡态理论(TST)与变分过渡态理论(CVT)并结合小曲率隧道效应模型(SCT),分别计算了主路径Path 1和Path 1a在200-800 K温度范围内的速率常数k^TST、k^CVT和k^CVT/SCT,在此温度区间内路径Path 1和Path 1a具有负温度系数效应。速率常数计算结果显示,对主路径Path 1和Path 1a而言,变分效应在计算温度段内有一定影响,与此同时量子力学隧道效应在低温段有显著影响。路径Path 1和Path 1a的CVT/SCT速率常数的三参数表达式分别为k₁^CVT/SCT(200-800 K) = 1.54×10^-5T^-2.70exp(1154/T) cm³ ·molecule^-1·s^-1和k_1a^CVT/SCT(200-800 K) = 5.82×10^-8T^-1.84exp(1388/T) cm³·molecule^-1·s^-1。     

Experimental and theoretical investigation of the reaction CF3 + NO + M → CF3NO + M from 0.5 to 12 Torr and from 253 to 373 K

The kinetics of the association reaction of CF₃ with NO was studied as a function of temperature near the low-pressure limit, using pulsed laser photolysis and time-resolved mass spectrometry. CF₃ radicals were generated by photolysis of CF₃I at 248 nm and the kinetics was determined by monitoring the time-resolved formation of CF₃NO. The bimolecular rate constants were measured from 0.5 to 12 Torr, using nitrogen as the buffer gas. The results are in very good agreement with recent data published by Vakhtin and Petrov, obtained at room temperature in a higher pressure range and, therefore, the two studies are quite complementary. A RRKM model was developed for fitting all the data, including those of Vakhtin and Petrov and for extrapolating the experimental results to the low- and high-pressure limits. The rate expressions obtained are the following: k₁(0) = (3.2 ± 0.8) × 10⁻²⁹ (T/298)^{−(3.4±0.6)} cm⁶ molecule⁻² s⁻¹ for nitrogen used as the bath gas and k₁(∞) = (2.0 ± 0.4) × 10⁻¹¹ (T/298)^(0±1) cm³ molecule⁻¹ s⁻¹. RRKM calculations also help to understand the differences in reactivity between CF₃ and other radicals, for the same association reaction with NO.     

Collisional quenching of electronically excited germanium atoms, Ge[4p(S0)], by small molecules investigated by time-resolved atomic resonance absorption spectroscopy

The collisional quenching of electronically excited germanium atoms, Ge[4p²(¹S₀)], 2.029 eV above the 4p²(³P₀) ground state, has been investigated by time-resolved atomic resonance absorption spectroscopy in the ultraviolet at λ = 274.04 nm [4d(¹P₁⁰) ← 4p²(¹S₀)]. In contrast to previous investigations using the ‘single-shot mode’ at high energy, Ge(¹S₀) has been generated by the repetitive pulsed irradiation of Ge(CH₃)₄ in the presence of excess helium gas and added gases in a slow flow system, kinetically equivalent to a static system. This technique was originally developed for the study of Ge[4p²(¹D₂)] which had eluded direct quantitative kinetic study until recently. Absolute second-order rate constants obtained using signal averaging techniques from data capture of total digitised atomic decay profiles are reported for the removal of Ge(¹S₀) with the following gases (k_R in cm³ molecule⁻¹ s⁻¹, 300 K): Xe, 7.1 ± 0.4 × 10⁻¹³; N₂, 4.7 ± 0.6 × 10⁻¹²; O₂, 3.6 ± 0.9 × 10⁻¹¹; NO, 1.5 ± 0.3 × 10⁻¹¹; CO, 3.4 ± 0.5 × 10⁻¹²; N₂O, 4.5 ± 0.5 × 10⁻¹²; CO₂, 1.1 ± 0.3 × 10⁻¹¹; CH₄, 1.7 ± 0.2 × 10⁻¹¹; CF₄, 4.8 ± 0.3 × 10⁻¹²; SF₆, 9.5 ± 1.0 × 10⁻¹³; C₂H₄, 3.3 ± 0.1 × 10⁻¹⁰; C₂H₂, 2.9 ± 0.2 × 10⁻¹⁰; Ge(CH₃)₄, 5.4 ± 0.2 × 10⁻¹¹. The results are compared with previous data for Ge(¹S₀) derived in the single-shot mode where there is general agreement though with some exceptions which are discussed. The present data are also compared with analogous quenching rate data for the collisional removal of the lower lying Ge[4p²(¹D₂)] state (0.883 eV), also characterized by signal averaging methods similar to that described here.     

Photocatalytic bleaching of p-nitrosodimethylaniline in TiO2 aqueous suspensions: A kinetic treatment involving some primary events photoinduced on the particle surface

The photocatalytic bleaching of p-nitrosodimethylaniline (P) has been investigated in aqueous suspensions of TiO₂. It was found that both charge carriers (hole and electron) were reactive to P to result in a bleaching. The roles of O₂ and several hole scavengers (HCOO⁻, EDTA, I⁻) have also been examined. A reaction mechanism has been proposed with consideration of several primary processes photoinduced on TiO₂ surface. The results of the kinetic analysis fit fairly well to those of the experiments. The rate constant (k^h_p) of the reaction between P and the adsorbed hydroxyl radical was estimated to be in the order 10¹⁰ M⁻¹ s⁻¹, which is in good agreement with that obtained from the homogeneous reaction of P with free OH radicals. Of particular interest is the pH dependence of the photobleaching rate. Around both pK_a of P and pH_ZPC of TiO₂, the photobleaching of P was steeply enhanced. This can be reasonably attributed to the mutual interaction (repulsion versus attraction) between P and TiO₂ particles in different pH ranges.