Electrochemical Oxidation Of Organic Compounds Research Articles

Selective electrochemical oxidation of organic compounds in a mass transfer-enhanced electrochemical flow reactor (e[sbnd]NETmix)

eNETmix stands as an electrochemical flow reactor engineered to enhance mass transfer. This study aimed at assessing the performance of the eNETmix reactor in the realm of organic electrosynthesis. Specifically, the research focused on the selective electrochemical oxidation of 4-methoxybenzyl alcohol (4-MBA) to p-anisaldehyde (PAA) using a bare fluorine-doped tin oxide (FTO) anode. The efficiency of the process was assessed for distinct current densities (j), Reynolds numbers (Re), supporting electrolyte contents, and substrate initial contents. The eNETmix reactor was extensively compared to a commercial electrochemical flow reactor (MicroFlowCell from ElectroCell, Denmark). eNETmix facilitated the use of a broader range of j (0.8–2.0 mA cm−2versus 0.8 mA cm−2) together with smaller Re (≥190 versus >1750), supporting electrolyte contents (≥1 mM versus ≥30 mM), and substrate initial contents (≥2.0 mM versus ≥3.0 mM) with no loss of PAA production or energy consumption. These findings underscore a remarkable suitability of eNETmix as a reactor for organic electrosynthesis.

Trace Br- Inhibits Halogenated Byproduct Formation in Saline Wastewater Electrochemical Treatment.

The electrochemical technology provides a practical and viable solution to the global water scarcity issue, but it has an inherent challenge of generating toxic halogenated byproducts in treatment of saline wastewater. Our study reveals an unexpected discovery: the presence of a trace amount of Br- not only enhanced the electrochemical oxidation of organic compounds with electron-rich groups but also significantly reduced the formation of halogenated byproducts. For example, in the presence of 20 μM Br-, the oxidation rate of phenol increased from 0.156 to 0.563 min-1, and the concentration of total organic halogen decreased from 59.2 to 8.6 μM. Through probe experiments, direct electron transfer and HO• were ruled out as major contributors; transient absorption spectroscopy (TAS) and computational kinetic models revealed that trace Br- triggers a shift in the dominant reactive species from Cl2•- to Br2•-, which plays a key role in pollutant removal. Both TAS and electron paramagnetic resonance identified signals unique to the phenoxyl and carbon-centered radicals in the Br2•--dominated system, indicating distinct reaction mechanisms compared to those involving Cl2•-. Kinetic isotope experiments and density functional theory calculations confirmed that the interaction between Br2•- and phenolic pollutants follows a hydrogen atom abstraction pathway, whereas Cl2•- predominantly engages pollutants through radical adduct formation. These insights significantly enhance our understanding of bromine radical-involved oxidation processes and have crucial implications for optimizing electrochemical treatment systems for saline wastewater.

Electrochemical Oxidation of Organic Compounds and the Creation of Metal Oxide Nanocomposites

Electrochemical regeneration suffers from low regeneration efficiency due to side reactions like oxygen evolution, as well as oxidation of the adsorbent. Utilizing the solution cast method, we three alternative strategies for producing Cr2O3 nanoparticle-laden polyvinyl alcohol (PVA) solid polymer films. The peaks in the FTIR spectrum at molecular vibration and chemical bonding frequencies indicate that Cr2O3 is present in the PVA polymer structure.

Ultra-fast synthesis of Ti/Ru0.3Ti0.7O2 anodes with superior electrochemical properties using an ionic liquid and laser calcination

Abstract Here, we combine CO2 laser heating and an ionic liquid solvent (i.e., methylimidazolium hydrogensulfate HMIM+ HSO4–) as an innovative route to produce Ti/Ru0.3Ti0.7O2 anodes. For comparison purposes, the anodes were also prepared using conventional thermal treatment (in a furnace), and by the standard polymeric precursor method (also known as the Pechini method). For the laser heating, the anodes were heated at a power density of 0.4 W mm−2 up to 550 °C and kept at this temperature for 40 s, followed by instantaneous cooling. Using these conditions, the total time spent to produce an anode (considering cooling) is just 9.7 min. It represents a remarkable reduction in 446-fold and 359-fold when compared with the conventional heating for Pechini and IL methods, respectively. The laser-prepared anodes presented an increase of 63.4% and 53.8% in the voltammetric charge, while the charge transfer resistance decreases 9.6-fold and 17.3-fold using IL and Pechini methods, respectively, when compared with their correspondent furnace-made ones. Finally, superior electrocatalytic activity toward the removal of the model pollutant atrazine is observed for the laser-prepared anodes. The anode produced using laser and the IL method is the most efficient, removing 81% of atrazine in 60 min, and presents the highest kinetic rate (0.062 min−1) at the lowest energy consumption (0.179 kWh L–1). The excellent electrocatalytic response of the anodes innovatively synthesized in this study characterizes them as an encouraging advance in the search for efficient materials to be applied in the electrochemical oxidation of organic compounds.

Treatment of Leachate by Electrochemical Oxidation using Graphite and Titanium Electrodes

Leachate originating in landfills where municipal solid wastes are disposed is a wastewater with a complex composition that could have a high environmental impact.The study aims to treat the landfill Leachate by electrochemical oxidation process in order to render the Leachate reasonable for inland disposal. Electrochemical oxidation of organic compounds from Leachate is a compelling method of breaking down pollutants which are resistant to biological degradation. The electrodes used in the process are graphite and titanium electrodes. At optimum conditions, the percentage removal by Graphite electrodes areCOD, TDS, Ammonia and Chloride were 52%, 57%, 60% and 45% respectively. The percentage removal by Titanium electrodes are COD, TDS, Ammonia and Chloride were 68%, 80%, 65% and 58% respectively.

Comparative investigation of electrochemically synthesized (α+β) layered nickel hydroxide with mixture of α-Ni(OH)2 and β-Ni(OH)2

Nickel hydroxides, owing to their high electrochemical activity are promising materials for chemical power sources (alkaline accumulators, lithium accumulators and hybrid supercapacitors), electrochromic devices, electrochemical oxidation of organic compounds. The most promising is nickel hydroxide that contains both α-Ni(OH)2 and β-Ni(OH)2. The aim of the research was to determine the properties of model mechanical mixtures with different ratios between α-Ni(OH)2 and β-Ni(OH)2 and to prove the hypothesis about the layered structure of nickel hydroxide samples synthesized in the slit diaphragm electrolyzer by means of comparative study.The XRD patterns of samples composed of α-Ni(OH)2 and β-Ni(OH)2 mixture show peaks corresponding to separate phases. By means of cyclic voltamperometry, it was discovered, that mixture samples do not show an oxidation peak during the first cycle, while two reduction peaks that correspond to reduction of α and β components are observed on the cathodic curve. A synergetic effect, which results in significant improvement in electrochemical activity of α-Ni(OH)2 and β-Ni(OH)2 mixture was discovered – specific reduction peak current values are 2.3 A/g (20 % α-phase), 3.5 A/g (30 % α-phase), 6.9 A/g (50 % α-phase), which exceed those of initial β-Ni(OH)2 (1.5 A/g) and α-Ni(OH)2 (2.0 A/g). By means of XRD analysis, it was discovered, that Ni(OH)2 samples synthesized in the SDE are composed of α and β and a series of intermediate structures. These samples demonstrate high electrochemical activity: presence of a defined oxidation peak during the first cycle, single reduction peaks with high specific currents of 6.5–11.7 A/g. The comparative analysis has revealed that electrochemically synthesized samples are composed of α-Ni(OH)2 and β-Ni(OH)2, but are not a mixture of these phases, owing to significantly different electrochemical behavior from mixture samples. Using mechanical modeling, the layered (α+β) structure of samples electrochemically synthesized in the slit diaphragm electrolyzer has been proved by contradiction.

Electrode materials used for electrochemical oxidation of organic compounds in wastewater

Electrochemical oxidation (EO) of organic compounds is an outstanding technology capable of oxidizing organic pollutants to simple inorganic compounds such as H2O and CO2. Moreover, EO can be attributed to an energy-efficient process, since it requires only insignificant amount of energy in the form of an applied current or a potential to activate the electrodes. There is a vast variety of electrodes used in EO processes for organic compounds degradation. They are noble metal electrodes, such as Pt and Au, boron-doped diamond (BDD) electrodes, mixed metal oxide (MMO), graphite and carbon electrode, etc. In this regard, it becomes difficult to focus on existing electrode properties and characteristics and choose an anode material for a particular application. The aim of this study was to review information on existing anodes used in EO processes, their advantages and disadvantages, performance and application area. Thus far, MMO electrodes along with BDD electrodes are leading materials used in the processes of EO of dyes, pesticides, pharmaceuticals, industrial wastewaters, etc. This is due to their excellent catalytic properties and resistance to both corrosion and dissolution. The catalytic activity of MMO electrodes strongly depends not only on their composition but also on fabrication methods. Thus, a correlation was made between the methods of manufacturing, efficiency and cost in the MMO electrodes. Despite the wide variety of anodes, most of them are either relatively expensive to be used for large volumes of wastewater, or they consist of potentially toxic metals. Moreover, none of them are sufficiently efficient and stable. Therefore, cost-effective, efficient and “green” anodic materials are still under development.

Bio-Inspired Design of Electrocatalysts for Oxidation of Small Organic Compounds

Electrochemical oxidation of organic compounds is a widely used approach for wastewater purification, energy production, and synthesis of value added products. In all cases listed noble metals are used as catalysts due to their high activity and lack of selectivity. Unfortunately these catalysts are expensive, which hinders their large-scale application for wastewater purification. At the same time Nature not only found the right answer for pollutants removal, but uses these electrochemical oxidation processes to gain energy. Numerous redox enzymes (mainly oxidases and dehydrogenases) are capable of fast, efficient, and selective oxidation of complex and simple organic compounds. The enzyme high redox activity is a result of years of evolutionary improvements of enzymes’ structure and function. A key moment is the specific design of their active center supported by the surrounding amino acid residues and enzyme tertiary structure. The main problem with utilization of enzymatic systems is their short life and limited range of environmental conditions they are able to operate in. Thus, the development of more robust inorganic catalysts by mimicking the enzyme active center provides a new avenue in the development of electrochemical catalysis for oxidation of organic compounds. An inorganic catalyst mimicking the Mn-binding site of oxalate oxidase and oxalate decarboxylase has been developed under this study. Oxalate oxidase and oxalate decarboxylase were chosen as enzyme models since they are capable of oxidation of small organic acids, more specifically oxalic acid. The importance of oxalic acid, especially for clinical diagnosis and in food and water technology, is now widely recognized. Small carboxylic or dicarboxylic acids (such as formic, maleic, and acetic acids) are intermediate products in catalytic oxidation of aromatic compounds present in wastewater. At the same time oxalic acid is a compound that is toxic to almost all organisms. The accumulation of oxalic acid cause hyperoxaluria, formation of calcium oxalate stones in the kidney, renal failure, cardiomyopathy, and cardiac conductance disorders. The developed catalyst, abbreviated here as MnAAPyr, is a non-platinum based catalyst. It has been synthesized using sacrificial support method [1], which was developed in our group mainly to synthesize materials with high activity towards oxygen reduction reaction. Along with its low cost, the main advantage of this catalyst is its high catalytic surface area i.e. the active sites of the material are situated within its own structure, turning it into a highly porous framework incorporating plenty of accessible active sites. The performed XPS analyses of the synthesized MnAAPyr show the presence of Mn-Nx coordination. Furthermore, DFT calculations were used to study the structure and the formation energy of the various Mn-Nxactive sites in which Mn is assumed to be coordinated with two, three, or four nitrogen atoms [2]. The activity of the MnAAPyr catalyst towards oxalate oxidation was studied using cyclic voltammetry at pH 4 and pH 7.5 (Fig. 1). MnAAPyr demonstrated similar catalytic activity at both pHs. The influence of the nature of the possible active sites was further evaluated using DFT approach by looking into the adsorption energy of oxalic acid and oxalate anion since this step was found to be the rate-limiting step in oxalate oxidation (Table 1 and Figure 2). As predicted by DFT oxalic acid and oxalate anion have the highest adsorption energy on Mn-N3, which implies higher activity of this active site in comparison to the other Mn-Nxcomposites. The mechanism of oxalate oxidation was experimentally studied through FTIR and RRDE measurements. We were interested in CO2 production as well as in the possibility of H2O2 generation as a by-product in a similar fashion to the mechanism occurring when oxalate oxidase is used. The activity of the MnAAPyr catalyst towards other small organic compounds was also tested. Along with the oxidation of small organics, it was established that this material shows electrocatalytic activity even towards oxidation of complex sugars such as glucose and sucrose. The broad range of organic compounds the catalyst can covert confirms its applicability in wastewater treatment and energy harvesting, where non-selectivity of the catalyst is beneficial. 1. Pylypenko, S., et al., Non-platinum oxygen reduction electrocatalysts based on pyrolyzed transition metal macrocycles. Electrochimica Acta, 2008. 53: p. 7875–7883. 2. Svedruzic, D., et al., The enzymes of oxalate metabolism: unexpected structures and mechanisms. Archives of Biochemistry and Biophysics, 2005. 433: p. 176–192. Figure 1

Electrochemical oxidation of organic compounds containing C[dbnd]N double bonds

Hydrazones from aromatic aldehydes (ArCH=NNH2, I–III) and acetophenones (ArC(Me)=NNH2, IV–X), oxime (ArC(Me)=NOH, XI) and oxime ether ArC(Me)=NOCH3, XII), were synthesized according to known procedures. An azine derivative (ArC(Me)=NN=C(Me)Ar, XIII) was prepared by anodic oxidation of the corresponding hydrazone. Their redox properties were studied in acetonitrile by cyclic voltammetry. They all show 1–3 irreversible oxidation waves and 1–2 irreversible reduction waves. Also, as expected, electron-donating groups attached to a phenyl ring at the para position decrease the anodic peak potentials with respect to the non-substituted molecule, whereas electron-withdrawing substituents increase the anodic peak potentials.Controlled potential electrolyses (CPE) at the onset of the measured oxidation potentials of hydrazones of acetophenones were carried out in acetonitrile (or methanol) and gave mainly azines and acetophenones. Anodic oxidation of hydrazones derived from aldehydes in different media did not form the desired nitriles but instead, gave the corresponding azines. CPE of oxime XI in acetonitrile (or methanol) gave the corresponding acetophenone whereas the oxime ether derivative XII gave both acetophenone and azine in acetonitrile. Electrolysis of azine XIII under similar conditions afforded mostly acetophenone (and unreacted substrate).Constant current electrolysis of hydrazones of acetophenones (IV–X) in methanol yielded four types of products: α-methoxyarylethane (1), acetophenone dimethylacetal (2), acetophenone (3) and azine (4). Their relative ratio was highly dependent on the nature of the aryl group.

Electrochemical Oxidation of Organic Compounds using Boron-Doped Diamond Electrodes

Boron-doped diamond (BDD) electrodes prepared by chemical vapor deposition were used to determine if phenol could be oxidized to CO2 and if biofilms could be oxidized and "cleaned" from a surface. Cyclic voltammetry showed that phenol and biofilms were electrolyzed by the BDD electrodes and that the oxidation products did not foul the electrodes. Experiments were also run with a flow cell in which a liter of 10 mM phenol in 0.1M H2SO4 was circulated through the cell and the total organic carbon (TOC) was monitored as a function of time and cell current. The total carbon in solution was reduced from ~1% to <0.1% with no observable decrease in decomposition rate. This low, total organic carbon content supports that the reacted phenol was converted completely to CO2.

Energy consumption of electrooxidation systems with boron-doped diamond electrodes in the pulse current mode

A pulse current technique was conducted in a boron-doped diamond (BDD) anode system for electrochemical wastewater treatment. Due to the strong generation and weak absorption of hydroxyl radicals on the diamond surface, the BDD electrode possesses a powerful capability of electrochemical oxidation of organic compounds, especially in the pulse current mode. The influences of pulse current parameters such as current density, pulse duty cycle, and frequency were investigated in terms of chemical oxygen demand (COD) removal, average current efficiency, and specific energy consumption. The results demonstrated that the relatively high COD removal and low specific energy consumption were obtained simultaneously only if the current density or pulse duty cycle was adjusted to a reasonable value. Increasing the frequency slightly enhanced the COD removal and average current efficiency. A pulse-BDD anode system showed a stronger energy saving ability than a constant-BDD anode system when the electrochemical oxidation of phenol of the two systems was compared. The results prove that the pulse current technique is more cost-effective and more suitable for a BDD anode system for real wastewater treatment. A kinetic analysis was presented to explain the above results.

Characterization of fluid dynamics and mass-transfer in an electrochemical oxidation cell by experimental and CFD studies

Flow and mass-transfer in a widely used commercial electrochemical flow cell (DiaCell ®) were investigated by computational fluid dynamics (CFD) simulations and validated by experimental measurements. Both qualitative and quantitative comparisons were made for distinct flow regimes in the Reynolds range between 25 and 2500 (based on the inter-electrode distance and on the superficial velocity in the cell middle cross-section area). A mono-phasic CFD methodology was applied for describing the rather complex bi-phasic phenomena taking place in the electrochemical oxidation of organic compounds, where gases are being formed at both electrodes. The adequacy of this assumption was subjected to validation with experimental results. Transient CFD simulations showed that the flow becomes unsteady at a rather low R e (in the range from 65 to 100) mainly due to the observed flow separation upstream the electrodes region. The pressure-drops determined by CFD agreed very well with the experimental measurements. Good agreement was also obtained between the Sherwood values calculated through CFD and experimentally determined by the limiting current technique. Mono-phasic CFD and experimental limiting current data were used for deriving mass-transfer correlations for the DiaCell ®. These correlations were found to correctly describe S h values determined from galvanostatic (electric current density of 332 A/m 2) electrochemical oxidation of selected organic compounds under mass-transfer controlled operating conditions and a turbulent-developing flow regime. These results suggest that turbulent-developing flow in an electrochemical cell can be sufficiently well described by mono-phasic CFD simulations.

Electrochemical Oxidation of Organic Compounds Using Boron-Doped Diamond Electrode

This paper presents the application of a boron-doped diamond (BDD) electrode in the electrochemical oxidation of stable organic compounds. The BDD electrode exhibits a high anodic potential, generating high oxidation state radicals that facilitate the oxidation of tough organic compounds. In this study, the electrochemical oxidation approach is tested in the cleaning of residual organics left on a liquid crystal display (LCD) device. Results indicate that residual organic compounds adhered on an LCD device are decomposed completely in the experiment. It has been shown that the electrolyte temperature and concentration strongly affect the oxidation of tough residual organics such as phenylcyclohexane. Optimal cleaning performance is obtained at an electrolyte concentration of and a temperature between 50 and . The stability test of a BDD electrode measured by means of X-ray diffraction indicates that the BDD electrode remains unchanged after of operation. Moreover, the electrochemical oxidation technique has dramatically minimized the use of the ozone depleting substance commonly used as the organic solvent in the LCD manufacturing process.

Kinetics of the electrochemical oxidation of organic compounds at BDD anodes: modelling of surface reactions

This paper presents the results of a numerical study of the kinetics of electrochemical oxidation of different organic substances at boron doped diamond (BDD).

Electrochemical Oxidation of 4-Chlorophenol for Wastewater Treatment: Definition of Normalized Current Efficiency (ϕ)

The electrochemical behavior of lead dioxide and synthetic boron-doped diamond thin film electrodes (BDDs) has been studied in acid media containing 4-chlorophenol (4-CP) by bulk electrolysis under different experimental conditions. In order to quantify the electrochemical activity of a given electrode, for the electrochemical oxidation of organic compounds (4-CP), the current efficiency of the anodic oxidation has been normalized taking into consideration mass-transport limitations. The normalized current efficiency (ϕ) has been defined as the ratio between the current efficiency of the investigated anode to the current efficiency of an ideal anode which has a very fast oxidation rate, resulting in a complete combustion of organics to carbon dioxide. The results have shown that even if the complete combustion of 4-chlorophenol has been achieved at both lead dioxide and boron-doped diamond anodes, the latter give higher ϕ. The difference in reactivity of the electrogenerated hydroxyl radicals on the anode surface, has been proposed to explain the high ϕ values obtained using boron-doped diamond anodes. © 2001 The Electrochemical Society. All rights reserved.

ChemInform Abstract: Electrochemical Oxidation of Organic Compounds in Fluorosulfonic Acid. Part 13. Oxidation of Aromatic Compounds in Acidic Systems on the Basis of FSO3H and CF3COOH.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Water post-treatment without expendables — proton exchange membrane based electrolysis system

Abstract An electrochemical reactor which utilizes a proton exchange membrane (PEM) as the electrolyte is demonstrated for removal of organic and bacterial contaminants from reclaimed water. Electrochemical oxidation of organic compounds was carried out using the following procedures: (i) potentiostatic control of the anode below the potential for oxygen evolution at room temperature; (ii) galvanostatic control of the anode in the region of oxygen evolution at room temperature; and (iii) use of a regenerative electrochemical unit — a water electrolyzer/fuel cell operating in the electrolysis mode at 90°C. The rates of oxidation of the organic compounds and their current efficiencies were estimated. The oxidation of the organic carbon compounds was quite effective in the regenerative fuel cell (water electrolyzer/fuel cell) when operated in electrolyzer mode. This result thus reveals that the same electrochemical system can be used for three functions in space stations and space vehicles — hydrogen and oxygen production, electricity generation and oxidative removal of organic compounds and bacterial species from reclaimed water.

Elektrochemische Oxydation organischer Verbindungen in Fluorsulfonsäure. X. Effekt der Aciditätserhöhung auf das anodische Verhalten einiger aromatischer Verbindungen im System HSO3FSbF5

Electrochemical Oxidation of Organic Compounds in Fluorsulfuric Acid. X. Effect of the Increase in Acidity on the Anodic Behavior of Some Aromatic Compounds in the HSO3FSbF5‐SystemThe effect of the acidity on the anodic behavior of some aromatic nitrils, nitro compounds, amines, sulfonyl fluorides, carbonyl compounds, hydrocarbons, benzylic acetates and methoxy compounds is investigated by cyclic voltammetry in HSO3F and HSO3FSbF5 (molecular ratio 15:1 and 3:1) at −76°C and in some cases in HSO3FSbF5 (1:1) at −40°C. With increasing content of SbF5 in most cases a positive shift of the anodic half‐peak potentials Δ Ep/2 is found, which depends on the type and on the strength of the interaction with the superacidic solvent. Δ Ep/2 increases from the protonated functional groups in the series NH3⊕ (0.00 V), CN (0.05–0.10 V), SO2F (0.10–0.20 V), COR (0.20–0.40 V), NO2 (0.30–0.60 V), OCH3 (&gt;0.8 V) to benzoylium ions (0.45–0.60 V), benzyl cations (0.60–0.80 V) and arenium ions (1.10–1.30 V). Besides, the anodic behavior depends to a large extent on the deprotonation rate of the substrate, which occurs precedingly to, simultaneously with or subsequent to the electron transfer.

Electrochemical oxidation of organic compounds in fluorosulfuric acid—III. Voltammetric investigation of aromatic carboxylic acids and acylium ions

The anodic behavior of a series of substituted benzoic acids 1a – 1w and of the corresponding benzoylium ions 5 is investigated by cyclic voltammetry in fluorosulfuric acid at −76°C. The acids are oxidized to cation radicals, the stability of which decreases with decreasing number of alkyl substituents. As a subsequent reaction the functionalization of one of the methyl groups to the fluorosulfonyloxymethyl group is found. After dissolving at room temperature of the acids with one o-alkyl group are between 80 and 100% and the acids with two o-alkyl groups are completely transformed into benzoylium ions 5 , which are between 450 and 560 mV more positively oxidized than the acid. The main reaction of the dication radical formed is the addition of SO 3F − to the carbonylium C-atom. As the number of alkyl substituents decreases this reaction competes with the functionalization of a methyl group. The difference between the voltammetric data in HSO 3F and acetonitrile is discussed in terms of a protonation of the benzoic acids and their oxidation products.

Elektrochemische Oxidation organischer Verbindungen in Fluorsulfonsäure. V. Anodisches Verhalten aromatischer Nitroverbindungen, Nitrile, Amine, Acetamide und Oxime

Electrochemical Oxidation of Organic Compounds in Fluorosulfuric Acid. V. Anodic Behaviour of Aromatic Nitrocompounds, Nitriles, Amines, Acetamides, and OximesThe anodic behaviour of a series of methyl substituted nitrobenzenes, benzonitriles, aniline derivatives, acetanilides and acetophenone oximes was investigated by cyclic voltammetry at platinum electrodes in HSO3F at −76°C. With the exception of the parent compounds and partly of the monomethyl derivatives relatively stable cation radicals could be detected. In a second anodic wave in many cases the functionalization of a CH3‐group to CH2‐OSO2F took place. From a comparison of the peak potentials and from the dependence of the voltammetric curves on the scan rate follows that the aniline derivatives are oxidized without deprotonation of the −NH3+ group, whereas for the nitrocompounds, nitriles and acetanilides a deprotonation of the functional group is coupled with the oxidation, and the cation radicals are stable onyl in the deprotonated state. A kinetic study of the subsequent reaction of some nitrocompounds was made and the deviating behavior of some acetanilides was found to be due to the anodic dimerization to benzidine derivatives.