Absolute Rate Constants For Reaction Research Articles

One-Bond-Nucleophilicity and -Electrophilicity Parameters: An Efficient Ordering System for 1,3-Dipolar Cycloadditions.

Diazoalkanes are ambiphilic 1,3-dipoles that undergo fast Huisgen cycloadditions with both electron-rich and electron-poor dipolarophiles but react slowly with alkenes of low polarity. Frontier molecular orbital (FMO) theory considering the 3-center-4-electron π-system of the propargyl fragment of diazoalkanes is commonly applied to rationalize these reactivity trends. However, we recently found that a change in the mechanism from cycloadditions to azo couplings takes place due to the existence of a previously overlooked lower-lying unoccupied molecular orbital. We now propose an alternative approach to analyze 1,3-dipolar cycloaddition reactions, which relies on the linear free energy relationship lg k2(20 °C) = sN(N + E) (eq 1) with two solvent-dependent parameters (N, sN) to characterize nucleophiles and one parameter (E) for electrophiles. Rate constants for the cycloadditions of diazoalkanes with dipolarophiles were measured and compared with those calculated for the formation of zwitterions by eq 1. The difference between experimental and predicted Gibbs energies of activation is interpreted as the energy of concert, i.e., the stabilization of the transition states by the concerted formation of two new bonds. By linking the plot of lg k2 vs N for nucleophilic dipolarophiles with that of lg k2 vs E for electrophilic dipolarophiles, one obtains V-shaped plots which provide absolute rate constants for the stepwise reactions on the borderlines. These plots furthermore predict relative reactivities of dipolarophiles in concerted, highly asynchronous cycloadditions more precisely than the classical correlations of rate constants with FMO energies or ionization potentials. DFT calculations using the SMD solvent model confirm these interpretations.

Temperature-Resolved Proton Transfer Reactions of Biomolecular Ions.

Temperature-resolved proton transfer reactions of multiply-protonated angiotensin I, disulfide-intact and -reduced lysozyme, and ubiquitin ions to primary, secondary and aromatic amines were examined in the gas phase. Absolute reaction rate constants for the proton transfer were determined from the intensities of the parent and product ions in mass spectra. Dramatic changes were observed in the distribution of product ions and the reaction rate constants. In particular, the rate constants for disulfide-intact lysozyme ions changed more drastically with the change in charge state and temperature compared to the corresponding values for disulfide-reduced ions. Proton transfer reactions were enhanced or suppressed as the result of the formation of complexes between the ions with gaseous molecules, which is related to changes in their conformation with changing.

Efficient removal of diuretic hydrochlorothiazide from water by electro-Fenton process using BDD anode: a kinetic and degradation pathway study

Environmental contextHydrochlorothiazide, a common diuretic pharmaceutical, occurs in environmental waters because current treatment technologies are unable to eliminate it from wastewater. To remove this environmentally hazardous chemical from water, we developed an advanced electrochemical oxidation process to efficiently degrade and mineralise the compound. Wider application of the process holds the promise of general, efficient destruction of pharmaceuticals in aqueous media. AbstractThe degradation and the mineralisation of the diuretic hydrochlorothiazide were studied by an advanced electrochemical oxidation process, ‘electro-Fenton’, which generates in situ hydroxyl radicals that are able to successfully oxidise or mineralise organic pollutants. In this study, a 0.1mM (29.8mgL−1) hydrochlorothiazide solution was completely oxidatively degraded in 15min under constant current electrolysis at 500 mA. The absolute kinetic rate constant of the oxidation reaction was also determined as (4.37±0.04)×109M−1s−1. The quasi-complete mineralisation of the solution was obtained with electrolysis for 6h under the same applied current. Several oxidation reaction intermediates were identified using gas chromatography-mass spectrometry (GC-MS). The formed carboxylic acids during the mineralisation process were also studied; oxamic, oxalic, acetic and maleic acids were identified and their concentrations were monitored throughout the electrolysis. The ions released during the treatment were also considered. Based on these data and the total organic carbon (TOC) removal results, a possible mineralisation pathway was proposed. These findings enable the conclusion that the electro-Fenton process is an efficient and environmentally-friendly method to eliminate the hazardous drug hydrochlorothiazide from an aqueous environment.

The reaction of hydrated iodide I(H2O)- with ozone: a new route to IO2- products.

We report on an experimental characterization of the isolated reaction of hydrated iodide I(H2O)- with ozone O3 at room temperature performed using a radio-frequency ion trap combined with a quadrupole mass spectrometer. Contrary to the oxidation reaction of the bare I- ion, the hydrated iodide I(H2O)- primarily reacts to form I- and IO2- with significant absolute reaction rate constants of 2.0 ± 0.3 × 10-10 cm3 molecule-1 s-1 and 2.5 ± 0.3 × 10-10 cm3 molecule-1 s-1 while direct pathways to IO- and IO3- are much weaker. Quantum chemical calculations indicate that in aqueous phase and for atmospherically relevant temperatures, the presence of hydrated iodides are favored over bare I- ions, thus suggesting that the chemistry of the hydrated ions is relevant for understanding and modeling atmospheric processes at the air-water interface.

Kinetics of the CH3 + C5H5 Reaction: A Theoretical Study.

Formation of fulvene and benzene through the reaction of cyclopentadienyl (C5H5) with methyl radical (CH3) and consequent dissociation of its primary C6H7 products has been studied using ab initio and theoretical kinetics calculations. The potential energies and geometries of all involved species have been computed at the CCSD(T)-F12/cc-pVTZ-f12//B2PLYPD3/aug-cc-pVDZ level theory. Multichannel/multiwell RRKM-Master Equation calculations have been utilized to produce phenomenological pressure- and temperature-dependent absolute and individual-channel rate constants for various reactions at the C6H8 and C6H7 potential energy surfaces. The kinetic scheme combining the primary and secondary reactions has been used to generate the overall rate constants for the production of fulvene and benzene and their branching ratios. Analyses of the kinetic data revealed that at low pressures (0.01 atm) benzene formation prevails, with branching ratios exceeding 60%, whereas at the highest pressure (100 atm) fulvene formation is prevalent, with the branching ratio of benzene being lower than 40%. At intermediate pressures (1 and 10 atm) the two product channels compete and fulvene formation is preferable at temperatures above 1600 K. The results demonstrate that a five-member ring can be efficiently transformed into an aromatic six-member ring by methylation and corroborate the potentially important role of the methyl radical in the mechanism of PAH growth where CH3 additions alternate with H abstractions and acetylene additions.

Reaction mechanism, rate constants, and product yields for the oxidation of Cyclopentadienyl and embedded five-member ring radicals with hydroxyl

Potential energy surfaces for the C5H5 + OH and C15H9 + OH reactions have been studied by ab initio calculations at the CCSD(T)-F12/cc-pVTZ-f12//B3LYP/6-311G(d,p) and G3(MP2,CC)//B3LYP/6-311G(d,p) levels of theory, respectively, in order to unravel the mechanism of oxidation of the cyclopentadienyl radical and five-member-ring radicals embedded in a sheet of six-member rings with OH. The VRC-TST approach has been employed to compute high-pressure-limit rate constants for barrierless entrance and exit reaction steps and multichannel/multiwell RRKM-ME calculations have been utilized to produce phenomenological pressure- and temperature-dependent absolute and individual-channel reaction rate constants. The calculations allowed us to quantify relative yields of various products in a broad range of conditions relevant to combustion and to generate rate expressions applicable for kinetic models of oxidation of aromatics. The C5H5 + OH reaction is shown to proceed either by well-skipping pathways without stabilization of C5H6O intermediates leading to the bimolecular products ortho-C5H5O + H, C5H4OH (hydroxycyclopentadienyl) + H, and C4H6 (1,3-butadiene) + CO, or via stabilization of the C5H6O intermediates, which then undergo unimolecular thermal decomposition to ortho-C5H5O + H and C4H6 + CO. The well-skipping and stabilization/dissociation pathways compete depending on the reaction conditions; higher pressures favor the stabilization/dissociation and higher temperature favor the well-skipping channels. For the C15H9 + OH reactions, the results demonstrate that embedding decreases the oxidation rate constants and hinder the decarbonylation process; the removal of CO grows less likely as the number of common edges of the five-member ring with the surrounding six-member rings increases.

Reactivity of sulfate radicals with natural organic matters

Advanced oxidation processes based on sulfate radicals (SO 4 ·− ) are capable of efficiently degrade organic pollutants from ground, surface and wastewaters. However, this degradation may be limited by aqueous natural organic matter (NOM). Here we measured the absolute rate constants of reaction of SO 4 ·− with four types of organic matter: two fulvic acids and two lake organic matter. We used laser flash photolysis technique to monitor the SO 4 ·− decay and the formation of the transients from organic matters. Reaction rate constants comprised between 1530 and 3500 s−1 mgC−1 L were obtained by numerical analysis of differential equations and the weighted average of the extinction coefficient of the generated organic matters radicals between 400 and 800 M−1 cm−1.

Degradation of artificial sweetener saccharin in aqueous medium by electrochemically generated hydroxyl radicals

The removal of artificial sweetener saccharin (SAC) in aqueous solution by electrochemical advanced oxidation using electro-Fenton process was performed. Experiments were carried out in an undivided cylindrical glass cell with a carbon-felt cathode and a Pt or boron-doped diamond (BDD) anode. The removal of SAC by electrochemically generated hydroxyl radicals followed pseudo-first-order kinetics with both Pt and BDD anode. The absolute rate constant of the SAC hydroxylation reaction was determined for the first time using the competition kinetic method and found to be (1.85 ± 0.01) × 10(9) M(-1) s(-1). The comparative study of TOC removal efficiency during electro-Fenton treatment indicated a higher mineralization rate with BDD than Pt anode. The identification and evolution of short-chain carboxylic acids and inorganic ions formed during oxidation process were monitored by ion-exchange chromatography and ion chromatography, respectively. The assessment of toxicity of SAC and/or its reaction by-products during treatment was performed using Microtox® method based on the Vibrio fischeri bacteria luminescence inhibition. Results showed that the process was able to efficiently detoxify the treated solution.

Electro‐Oxidation of the Pharmaceutical Furosemide: Kinetics, Mechanism, and By‐Products

Furosemide is a widely prescribed diuretic whose unambiguous presence in water appointed it as an emerging pollutant. This work focuses on the electrochemical degradation of this drug in aqueous solutions by electrochemical advanced oxidation processes, electro‐Fenton and anodic oxidation, using Pt/carbon‐felt and boron doped diamond (BDD)/carbon‐felt cells with H2O2 electrogeneration. The higher oxidation power of the electro‐Fenton process using a BDD anode was demonstrated. The oxidative degradation of furosemide by electrochemically generated •OH radicals follows a pseudo‐first order kinetics. The absolute rate constant of the oxidation reaction of furosemide by •OH was determined using a competition kinetics method and found to be 3.4 × 109 M−1 s−1. The evolution of the total organic carbon removal during the treatment as a mineralization efficiency parameter was investigated. It was found that the electrochemical degradation of furosemide yields formation of aromatic by‐products which are oxidized afterwards to aliphatic carboxylic acids before their conversion to CO2 and inorganic ions (NH4+, NO3–, Cl–, and SO42–). The toxicity assessment by the Microtox® method revealed formation of oxidation reaction intermediates more toxic than the parent molecule. Nevertheless, the overall results confirm the high effectiveness of anodic oxidation and electro‐Fenton processes for the removal of furosemide and its by‐products from aqueous media.

Photocatalytic degradation of three amantadine antiviral drugs as well as their eco-toxicity evolution

Abstracts Advanced oxidation processes (AOPs) relying on in situ generated highly reactive OH are successfully applied to water purification. The absolute reaction rate constants for OH with three antiviral drugs were first reported through pulsed radiolysis experiments. Results found that OH reacted quickly with these substrates, with bimolecular reaction rate constants of 6.31 × 10 9 , 5.13 × 10 9 , and 7.05 × 10 9 M −1 s −1 for 1-amantadine, 2-amantadine, and rimantadine, respectively. The photocatalytic degradation kinetics of substrates were followed pseudo-first-order kinetics according to Langmuir–Hinshelwood model in TiO 2 suspensions, and the apparent rate constants were obtained as 0.076, 0.084, and 0.102 min −1 for three antiviral drugs, respectively. Scavenger experiments revealed that OH was the major reactive species involved in antiviral drugs degradation. To probe the photocatalytic degradation mechanism, the fate of nitrogen elements and the change of total organic carbon were also examined, and the data showed that all three drugs could be completely mineralized into CO 2 , H 2 O, and inorganic ions (NO 3 − and NH 4 + ) without generating any detectable products with enough degradation time. To further insight into the potential adverse effect of three antiviral drugs and their degradation products, the acute aquatic toxicity of degradation solutions were evaluated at three different trophic levels, and the toxicities first increased slightly and then decreased rapidly as the total organic carbon decreased.

Conformations of disulfide-intact and -reduced lysozyme ions probed by proton-transfer reactions at various temperatures.

Proton-transfer reactions of disulfide-intact and -reduced lysozyme ions (7+ through 14+) to 2,6-dimethylpyridine were examined in the gas phase using tandem mass spectrometry with electrospray ionization. By changing temperature of a collision cell from 280 to 460 K, temperature dependence of reaction rate constants and branching fractions was measured. Absolute reaction rate constants for the protein ions of specific charge states were determined from intensities of parent and product ions in the mass spectra. Remarkable change was observed for the rate constants and distribution of product ions. The rate constants for disulfide-intact ions changed more drastically with change of charge states and temperature than those for disulfide-reduced ions. Observed branching fractions for parent and product ions were represented by calculated reaction rate constants with a scheme of sequential process. The reaction rate constants are closely related to conformation changes with change of temperature, which are profoundly influenced by amputation of disulfide bonds.

The Measurement of the Rate Parameters for the Reactions i‐C3H and n‐C3H + HI → C3H8 + I• over the Temperature Range 293–623 K: Implications for the Standard Heat of Formation of the Propyl Radicals

ABSTRACTAn investigation of the absolute rate constants of the metathesis reactions i‐C3H + HI → C3H8 + I• (1) and n‐C3H + HI → C3H8 + I• (2) was performed using a newly developed apparatus. The obtained Arrhenius expressions are k1 = 1.94 (±0.42) × 10−11 exp(−6.190 (±0.855)/RT) and k2 = 6.49 (±1.86) × 10−11 exp(−11.084 (±0.913)/RT) (R = 8.314 J K−1 mol−1) over the temperature range 293–623 K (A in cm3 molec−1 s−1, Ea in kJ mol−1). Two Knudsen reactors of different geometry coupled to single‐photon (VUV) photoionization mass spectrometry (SPIMS) were successively used. The two propyl isomers were generated externally to and upstream of the reactor and led to thermalized i‐ and n‐C3H free radicals. A minor correction to k2 for the wall loss of n‐C3H (kw) was applied throughout the temperature range, whereas no significant wall loss of i‐C3H could be measured. The obtained results are based on the disappearance of propyl radicals with increasing amounts of HI. Thermochemical parameters of propyl free radicals resulting from the present kinetic measurements are discussed and point toward a slightly lower value for the standard heat of formation of Δf(i‐C3H) compared to the currently accepted value, whereas no significant adjustment for n‐C3H seems to be necessary. The recommended values are Δf(i‐C3H) = 86.6 ± 2.1 kJ mol−1 and Δf(n‐C3H) = 101.1 ± 2.1 kJ mol−1 resulting from a third law evaluation using (i‐C3H) = 289.9 and (n‐C3H) = 290.3 J K−1 mol−1, both values being very close to the values measured by W. Tsang, namely 88 ± 2 and 100 ± 2 kJ mol−1, respectively.

Free radical destruction of haloacetamides in aqueous solution

Haloacetamides are disinfection byproducts (DBPs) formed through chlorine/chloramine disinfection processes in drinking waters and have been recently highlighted in the US national Reconnaissance Survey. These species occur at low concentrations, but have been determined to have high cytotoxicity and mutagenicity and therefore may represent a human health hazard. Advanced oxidation/reduction processes (AO/RPs) which utilize free radical reactions are new alternatives to degrade these species. This study reports the absolute bimolecular reaction rate constants for 12 haloacetamides with •OH radical and hydrated electron. The •OH radical reaction rates varied from 5.18 × 107 to 1.14 × 1010 M−1 s−1, and hydrated electron reaction rates varied from 5.00 × 109 to 3.64 × 1010 M−1 s−1. Results obtained using an ion chromatograph indicated that ARPs are suitable for dehaloliazation of haloacetamides. These data are required for both evaluating AO/RPs for the destruction of these compounds and for studies of their fate and transport in surface waters where radical chemistry may be important in assessing their lifetime.

Proton transfer and complex formation of angiotensin I ions with gaseous molecules at various temperature

Proton transfer reactions of angiotensin I ions for +2 charge state, [M+2H]2+, to primary, secondary and aromatic amines were examined in the gas phase. Absolute reaction rate constants for proton transfer were determined from intensities of parent and product ions in the mass spectra. Temperature dependence of the reaction rate constants was measured. Remarkable change was observed for distribution of product ions and reaction rate constants. Proton transfer reaction was enhanced or reduced by complex formation of [M+2H]2+ with gaseous molecules. The results relate to conformation changes of [M+2H]2+ with change of temperature, which are induced by complex formation and or by thermal collision with He. Proton transfer reactions of angiotensin I ions for +3 charge state, [M+3H]3+, were also studied. The reaction rates did not depend on temperature so definitely.

Radiation chemistry of salicylic and methyl substituted salicylic acids: Models for the radiation chemistry of pharmaceutical compounds

Salicylic acid and its derivatives are components of many medications and moieties found in numerous pharmaceutical compounds. They have been used as models for various pharmaceutical compounds in pharmacological studies, for the treatment of pharmaceuticals and personal care products (PPCPs), and, reactions with natural organic matter (NOM). In this study, the radiation chemistry of benzoic acid, salicylic acid and four methyl substituted salicylic acids (MSA) is reported. The absolute bimolecular reaction rate constants for hydroxyl radical reaction with benzoic and salicylic acids as well as 3-methyl-, 4-methyl-, 5-methyl-, and 6-methyl-salicylic acid were determined (5.86±0.54)×109, (1.07±0.07)×1010, (7.48±0.17)×109, (7.31±0.29)×109, (5.47±0.25)×109, (6.94±0.10)×109 (M−1s−1), respectively. The hydrated electron reaction rate constants were measured (3.02±0.10)×109, (8.98±0.27)×109, (5.39±0.21)×109, (4.33±0.17)×109, (4.72±0.15)×109, (1.42±0.02)×109 (M−1s−1), respectively. The transient absorption spectra for the six model compounds were examined and their role as model compounds for the radiation chemistry of pharmaceuticals investigated.

Degradation of Diclofenac by Advanced Oxidation and Reduction Processes: Kinetic Studies, Degradation Pathways and Toxicity Assessments

Many pharmaceutical compounds and metabolites are found in surface and ground waters suggesting their ineffective removal by conventional wastewater treatment technologies. Advanced oxidation/reduction processes (AO/RPs), which utilize free radical reactions to directly degrade chemical contaminants, are alternatives to traditional water treatment. This study reports the absolute rate constants for reaction of diclofenac sodium and model compound (2, 6-dichloraniline) with the two major AO/RP radicals: the hydroxyl radical (•OH) and hydrated electron (eaq−). The bimolecular reaction rate constants (M−1 s−1) for diclofenac for •OH was (9.29 ± 0.11) × 109, and for e−aq was (1.53 ± 0.03) ×109. To provide a better understanding of the decomposition of the intermediate radicals produced by hydroxyl radical reactions, transient absorption spectra are observed from 1 – 250 μs. In addition, preliminary degradation mechanisms and major products were elucidated using 60Co γ-irradiation and LC-MS. The toxicity of products was evaluated using luminescent bacteria. These data are required for both evaluating the potential use of AO/RPs for the destruction of these compounds and for studies of their fate and transport in surface waters where radical chemistry may be important in assessing their lifetime.

Kinetic model for the radical degradation of tri-halonitromethane disinfection byproducts in water

The halonitromethanes (HNMs) are byproducts of the ozonation and chlorine/chloramine treatment of drinking waters. Although typically occurring at low concentrations HNMs have high cytotoxicity and mutagenicity, and may therefore represent a significant human health hazard. In this study, we have investigated the radical based mineralization of fully-halogenated HNMs in water using the congeners bromodichloronitromethane and chlorodibromonitromethane. We have combined absolute reaction rate constants for their reactions with the hydroxyl radical and the hydrated electron as measured by electron pulse radiolysis and analytical measurements of stable product concentrations obtained by 60Co steady-state radiolysis with a kinetic computer model that includes water radiolysis reactions and halide/nitrogen oxide radical chemistry to fully elucidate the reaction pathways of these HNMs. These results are compared to our previous similar study of the fully chlorinated HNM chloropicrin. The full optimized computer model, suitable for predicting the behavior of this class of compounds in irradiated drinking water, is provided.

Theoretical and experimental investigation of the C 2H + SO 2 reaction over the range T = 295–800 K

Absolute rate constants for the gas-phase reaction C 2H + SO 2 are experimentally determined over the temperature range 295–800 K. C 2H radicals are generated by pulsed 193-nm photolysis of C 2H 2 in the presence of SO 2 and He or N 2 buffer gas. The temperature dependence of the rate constants is established as k SO 2 ( T) = (0.86 ± 0.08) T 3.80±0.13 exp[−(1222 ± 79)/ T] cm 3 s −1. The rate constants are moderately high at these temperatures and show negative temperature dependence. CCSD(T)/6-311++G(3df,2p) calculations of the potential energy surface confirm experimental findings and show that the reaction products are HCCO + SO.

Silanones and Silanethiones from the Reactions of Transient Silylenes with Oxiranes and Thiiranes in Solution. The Direct Detection of Diphenylsilanethione.

The transient silylenes SiMe(2) and SiPh(2) react with cyclohexene oxide (CHO), propylene oxide (PrO), and propylene sulfide (PrS) in hydrocarbon solvents to form products consistent with the formation of the corresponding transient silanones and silanethiones, respectively. Laser flash photolysis studies show that these reactions proceed via multistep sequences involving the intermediacy of the corresponding silylene-oxirane or -thiirane complexes, which are formed with rate constants close to the diffusion limit in all cases and exhibit UV absorption spectra similar to those of the corresponding complexes with the nonreactive O- and S-donors, tetrahydrofuran and tetrahydrothiophene. The SiMe(2)-PrO and SiPh(2)-PrO complexes both exhibit lifetimes of ca. 300 ns, and are longer-lived than the corresponding complexes with CHO, which are both in the range of 230-240 ns. On the other hand, the silylene-PrS complexes are considerably shorter-lived and vary with silyl substituent; the SiMe(2)-PrS complex decays with the excitation laser pulse (i.e., τ ≤ 25 ns), while the SiPh(2)-PrS complex exhibits τ = 48 ± 3 ns. The decay of the SiPh(2)-PrS complex affords a long-lived transient product exhibiting λ(max) ≈ 275 nm, which has been assigned to diphenylsilanethione (Ph(2)Si═S) on the basis of its second order decay kinetics and absolute rate constants for reaction with methanol, tert-butanol, acetic acid, and n-butyl amine, for which values in the range of 1.4 × 10(8) to 3.2 × 10(9) M(-1) s(-1) are reported. The experimental rate constants for decay of the SiMe(2)-epoxide and -PrS complexes indicate free energy barriers (ΔG(‡)) of ca. 8.5 and ≤7.1 kcal mol(-1) for the rate-determining steps leading to dimethylsilanone and -silanethione, respectively, which are compared to the results of DFT (B3LYP/6-311+G(d,p)) calculations of the reactions of SiH(2) and SiMe(2) with oxirane and thiirane. The calculations predict a stepwise C-O cleavage mechanism involving singlet biradical intermediates for the silylene-oxirane complexes, and a concerted mechanism for silanethione formation from the silylene-thiirane complexes, in agreement with earlier ab initio studies of the SiH(2)-oxirane and -thiirane systems.

Treatment of statin compounds by advanced oxidation processes: Kinetic considerations and destruction mechanisms

This study examined the use of advanced oxidation/reduction processes (AO/RPs) for the destruction of cholesterol lowering statin pharmaceuticals. AO/RPs which utilize the oxidizing hydroxyl radical ( OH) and reducing aqueous electron (e − aq), to degrade chemical contaminants are alternatives to traditional water treatment methods, and are alternatives as water reuse becomes more generally implemented. Four major statin pharmaceuticals, fluvastatin, lovastatin, pravastatin and simvastatin, were studied, and the absolute bimolecular reaction rate constants with OH determined, (6.96±0.16)×10 9, (2.92±0.06)×10 9, (4.16±0.13)×10 9, and (3.13±0.15)×10 9 M −1 s −1, and for e − aq (2.31±0.06)×10 9, (0.45±0.01)×10 9, (1.26±0.01)×10 9, and (0.69±0.02)×10 9 M −1 s −1, respectively. To provide additional information on the radicals formed upon oxidation, transient spectra were measured and the overall reaction efficiency determined. Radical-based destruction mechanisms for destruction of the statins are proposed based on the LC-MS determination of the stable reaction by-products formed using 137Cs γ-irradiation of statin solutions. Knowing the reaction rates, reaction efficiencies and destruction mechanisms of these compounds is essential for the consideration of the use of advanced oxidation/reduction processes for the destruction of statins in aqueous systems.