13 resultados para High Performance liquid chromatography coupled with mass spectrometry (LC-MS)

em Universidade Federal do Rio Grande do Norte(UFRN)


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Hancornia speciosa Gomes (Apocynaceae), popularly known as ‘mangabeira’, has been used in folk medicine to treat inflammatory disorders, hypertension, dermatitis, diabetes, liver diseases and stomach disorders. Regarding the Hancornia speciosa fruits, the ethnobotany indicates its use especially for treating inflammation and tuberculosis. However, no study has been done so far to prove such biological activities. The objective was evaluation anti-inflammatory activity from the fruits of Hancornia speciosa Gomes (mangabeira). Aqueous extract was prepared by decoction, subsequently submitted the liquid-liquid fractionation. The secondary metabolites were identified by high performance liquid chromatography coupled with detector diode array (HPLC-DAD) and liquid chromatography diode array detector coupled with mass spectrometry (LC-DAD-MS). The anti-inflammatory properties of the aqueous extract, dichloromethane (CH2Cl2), ethyl acetate (EtOAc) and n-butanol (n-BuOH) fractions of the fruits from H. speciosa, as well as rutin and chlorogenic acid were investigated using in vitro and in vivo models. In vivo tests comprised the xylene-induced ear edema that was measured the formation of edema, carrageenan-induced peritonitis was evaluated the total leukocytes at 4h and zymosan-induced air pouch was measured the total leukocytes and differential cell count at 6, 24 and 48 hours, whereas in vitro tests were evaluated levels of cytokines IL-1β, IL-6, IL-12 and TNF-α using ELISA obtained of carrageenan-induced peritonitis model. The results showed the presence of rutin and chlorogenic acid were detected in the aqueous extract from H. speciosa fruits by HPLC-DAD and LC-DAD-ME. Furthermore, the aqueous extracts and fractions, as well as rutin and chlorogenic acid significantly inhibited the xilol-induced ear edema and reduced cell migration in the animal models such as carrageenan-induced peritonitis and zymosan-induced air pouch. In addition, reduced levels of cytokines IL-1β, IL-6, IL-12 and TNF-α were observed. This is the first study that demonstrated the anti-inflammatory effect of aqueous extract from Hancornia speciosa fruits against different inflammatory agents in animal models, suggesting that their bioactive molecules, especially rutin and chlorogenic acid contributing, at least in part, to the anti-inflammatory effect of aqueous extract. These findings support the widespread use of Hancornia speciosa in popular medicine and demonstrate that this aqueous extract has therapeutic potential for the development of a herbal drugs with anti-inflammatory properties.

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Estuaries are environments prone to the input of chemical pollutants of various kinds and origins, including polycyclic aromatic hydrocarbons (PAHs). Anthropogenic PAHs may have two possible sources: pyrolytic (with four or more aromatic rings and low degree of alkylation) and petrogenic (with two and three aromatic rings and high degree of alkylation). This study aimed to evaluate the levels, distribution and possible sources of polycyclic aromatic hydrocarbons in the estuary of the Potengi river, Natal, Brazil. Samples of bottom sediments were collected in the final 12 km of the estuary until its mouth to the sea, where the urbanization of the Great Natal is more concentrated. Sampling was performed on 12 cross sections, with three stations each, totaling 36 samples, identified as T1 to T36. The non alkylated and alkylated PAHs were analyzed by gas chromatography coupled to mass spectrometry (GC / MS). PAHs were detected in all 36 stations with total concentration on each varying 174-109407 ng g-1. These values are comparable to those of several estuarine regions worldwide with high anthropogenic influence, suggesting the record of diffuse contamination installed in the estuary. PAHs profiles were similar for most stations. In 32 of the 36 stations, low molecular weight PAHs (with 2 and 3 ring: naphthalene, phenanthrene and their alkylated homologues) prevailed, which ranged from 54% to 100% of the total PAH, indicating that leaks, spills and combustion fuels are the dominant source of PAH pollution in the estuary. The level of contamination by PAHs in most stations suggests that there is potential risk of occasional adverse biological effects, but in some stations adverse impacts on the biota may occur frequently. The diagnostic ratios could differentiate sources of PAHs in sediments of the estuary, which were divided into three groups: petrogenic, pyrolytic and mixing of sources. The urban concentration of the Great Natal and the various industrial activities associated with it can be blamed as potential sources of PAHs in bottom sediments of the estuary studied. The data presented highlight the need to control the causes of existing pollution in the estuary

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Estuaries are environments prone to the input of chemical pollutants of various kinds and origins, including polycyclic aromatic hydrocarbons (PAHs). Anthropogenic PAHs may have two possible sources: pyrolytic (with four or more aromatic rings and low degree of alkylation) and petrogenic (with two and three aromatic rings and high degree of alkylation). This study aimed to evaluate the levels, distribution and possible sources of polycyclic aromatic hydrocarbons in the estuary of the Potengi river, Natal, Brazil. Samples of bottom sediments were collected in the final 12 km of the estuary until its mouth to the sea, where the urbanization of the Great Natal is more concentrated. Sampling was performed on 12 cross sections, with three stations each, totaling 36 samples, identified as T1 to T36. The non alkylated and alkylated PAHs were analyzed by gas chromatography coupled to mass spectrometry (GC / MS). PAHs were detected in all 36 stations with total concentration on each varying 174-109407 ng g-1. These values are comparable to those of several estuarine regions worldwide with high anthropogenic influence, suggesting the record of diffuse contamination installed in the estuary. PAHs profiles were similar for most stations. In 32 of the 36 stations, low molecular weight PAHs (with 2 and 3 ring: naphthalene, phenanthrene and their alkylated homologues) prevailed, which ranged from 54% to 100% of the total PAH, indicating that leaks, spills and combustion fuels are the dominant source of PAH pollution in the estuary. The level of contamination by PAHs in most stations suggests that there is potential risk of occasional adverse biological effects, but in some stations adverse impacts on the biota may occur frequently. The diagnostic ratios could differentiate sources of PAHs in sediments of the estuary, which were divided into three groups: petrogenic, pyrolytic and mixing of sources. The urban concentration of the Great Natal and the various industrial activities associated with it can be blamed as potential sources of PAHs in bottom sediments of the estuary studied. The data presented highlight the need to control the causes of existing pollution in the estuary

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The aim of this work is the treatment of produced water from oil by using electrochemical technology. Produced water is a major waste generated during the process of exploration and production in the oil industry. Several approaches are being studied aiming at the treatment of this effluent; among them can be cited the biological process and chemical treatments such as advanced oxidation process and electrochemical treatments (electrooxidation, electroflotation, electrocoagulation, electrocoagulation). This work studies the application of electrochemical technology in the treatment of the synthetic produced water effluent through the action of the electron, in order to remove or transform the toxic and harmful substances from the environment by redox reactions in less toxic substances. For this reason, we used a synthetic wastewater, containing a mixture H2SO4 0,5M and 16 HPAs, which are: naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo (a) anthracene, chrysene, benzo(b)fluoranthene, benzo(k) fluoranthene, benzo(a)pyrene, indeno(1,2,3-cd)pyrene, dibenzo(a, h)anthracene, benzo(g, h, i)perylene. Bulk electrochemical oxidation experiments were performed using a batch electrochemical reactor containing a pair of parallel electrodes, coupled with a power supply using a magnetic stirrer for favoring the transfer mass control. As anodic material was used, a Dimensionally Stable Anode (DSA) of Ti/Pt, while as cathode was used a Ti electrode. Several samples were collected at specific times and after that, the analysis of these samples were carried out by using Gas Chromatography Coupled to Mass Spectrometry (GC - MS) in order to determine the percentage of removal. The results showed that it was possible to achieve the removal of HPAs about 80% (in some cases, more than 80%). In addition, as an indicator of the economic feasibility of electrochemical treatment the energy consumption was analyzed for each hour of electrolysis, and based on the value kWh charged by ANEEL, the costs were estimated. Thus, the treatment costs of this research were quite attractive

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With the new discoveries of oil and gas, the exploration of fields in various geological basins, imports of other oils and the development of alternative fuels, more and more research labs have evaluated and characterized new types of petroleum and derivatives. Therefore the investment in new techniques and equipment in the samples analysis to determine their physical and chemical properties, their composition, possible contaminants, especification of products, among others, have multiplied in last years, so development of techniques for rapid and efficient characterization is extremely important for a better economic recovery of oil. Based on this context, this work has two main objectives. The first one is to characterize the oil by thermogravimetry coupled with mass spectrometry (TG-MS), and correlate these results with from other types of characterizations data previously informed. The second is to use the technique to develop a methodology to obtain the curve of evaluation of hydrogen sulfide gas in oil. Thus, four samples were analyzed by TG-MS, and X-ray fluorescence spectrometry (XRF). TG results can be used to indicate the nature of oil, its tendency in coke formation, temperatures of distillation and cracking, and other features. It was observed in MS evaluations the behavior of oil main compounds with temperature, the points where the volatilized certain fractions and the evaluation gas analysis of sulfide hydrogen that is compared with the evaluation curve obtained by Petrobras with another methodology

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With the new discoveries of oil and gas, the exploration of fields in various geological basins, imports of other oils and the development of alternative fuels, more and more research labs have evaluated and characterized new types of petroleum and derivatives. Therefore the investment in new techniques and equipment in the samples analysis to determine their physical and chemical properties, their composition, possible contaminants, especification of products, among others, have multiplied in last years, so development of techniques for rapid and efficient characterization is extremely important for a better economic recovery of oil. Based on this context, this work has two main objectives. The first one is to characterize the oil by thermogravimetry coupled with mass spectrometry (TG-MS), and correlate these results with from other types of characterizations data previously informed. The second is to use the technique to develop a methodology to obtain the curve of evaluation of hydrogen sulfide gas in oil. Thus, four samples were analyzed by TG-MS, and X-ray fluorescence spectrometry (XRF). TG results can be used to indicate the nature of oil, its tendency in coke formation, temperatures of distillation and cracking, and other features. It was observed in MS evaluations the behavior of oil main compounds with temperature, the points where the volatilized certain fractions and the evaluation gas analysis of sulfide hydrogen that is compared with the evaluation curve obtained by Petrobras with another methodology

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In last years it has talked a lot about the environment and the plastic waste produced and discarded. In last decades, the increasing development of research to obtain fuel from plastic material, by catalytic degradation, it has become a very attractive looking, as these tailings are discarded to millions worldwide. These materials take a long time to degrade themselves by ways said natural and burning it has not demonstrated a viable alternative due to the toxic products produced during combustion. Such products could bring serious consequences to public health and environment. Therefore, the technique of chemical recycling is presented as a suitable alternative, especially since could be obtain fractions of liquid fuels that can be intended to the petrochemical industry. This work aims to propose alternatives to the use of plastic waste in the production of light petrochemical. Zeolites has been widely used in the study of this process due to its peculiar structural properties and its high acidity. In this work was studied the reaction of catalytic degradation of high-density polyethylene (HDPE) in the presence HZSM-12 zeolites with different acid sites concentrations by thermogravimetry and pyrolysis coupled with GC-MS. The samples of the catalysts were mixed with HDPE in the proportion of 50% in mass and submitted to thermogravimetric analyses in several heating rates. The addition of solids with different acid sites concentrations to HDPE, produced a decrease in the temperature of degradation of the polymer proportional the acidity of the catalyst. These qualitative results were complemented by the data of activation energy obtained through the non-isothermal kinetics model proposed by Vyazovkin. The values of Ea when correlated to the data of surface acidity of the catalysts indicated that there is a exponential decrease of the energy of activation in the reaction of catalytic degradation of HDPE, in function of the concentration of acid sites of the materials. These results indicate that the acidity of the catalyst added to the system is one of the most important properties in the reaction of catalytic degradation of polyethylene

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This work aims to detect polycyclic aromatic hydrocarbons (PAHs) through optimized analytical techniques, such as gas chromatography with flame-ionisation detector (CGFID), gas chromatography coupled to mass spectrometry (CGMS), Fluorescence Spectroscopy of Molecular and Purpot of oils and greases (POG). Apply to chemometrics, Factorial Planning 23, in the preparation of samples by liquid-liquid extraction. The sample preparation was used for liquid-liquid extraction and factors in this sample was used for the application of factorial planning 23, such as the use of ultrasound, solvents (dichloromethane, hexane and chloroform) and ratio of solvent / synthetic sample. These factors were assigned two types of levels: positive and negative. It was used to form the cube to better analyze the answers. The responses of the eight combinations were obtained in reading the spectrofluorimetric. The optimization of equipment were used, and they served in the HPA's identification of the samples collected in Rio Potengi. The optimization of the equipment was observed every 16's and PAH in the samples was found that the HPA's came from contamination of the Rio Potengi. The contamination comes through organic household waste, hospital waste, and among other contamination that comes from industries that are installed around the River The factorial design of high validity, it was observed a more effective sample preparation. The factorial design of liquid-liquid extraction showed a way to spend less solvent in less time using an ideal solvent, but also a way to extract more analyte from the matrix itself is water. In planning a smaller form factor extraction was the use of ultrasound, the ratio 1:3 corresponding to a solvent and sample 3 and the best solvent was dichloromethane who presented a viable extraction, not discarding the possibility of using also the hexane. The chloroform and may be toxic not had a good extraction

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The MCM-41 mesoporous synthesis was done using rice hulls ash and chrysotile as natural alternative silica sources. For the using of these sources, chemical and thermic treatments were done in both materials. After chemical and thermic treatments, these materials were employed on the MCM-41 mesoctructures synthesis. The natural materials treated and employed in the synthesis were characterized by several techniques such as X-ray diffraction, N2 adsorption and desorption, scanning electronic microscopy and thermogravimetric analysis. MCM-41 standart samples synthetized with aerosil 200 commercial sílica were used to evaluation. The formed material from rice hulls ash showed values from BET specific area about 468 m².g-1, N2 adsorption and desorption isotherms and loss mass similar to reference materials. The silica from chrysotile calcined and leached was employed to mesoporous materials synthesis. The BET specific area showed values about 700 m².g-1, N2 adsorption and desorption isotherms type IV and loss mass similar to mesoporous materials. The formed material from calcined and leached chrysotile, without calcination, applied to phenol remotion carried high performance liquid chromatography and evaluated with organophilic clays with different treatments. By the characterization techniques were proved that mesoporous materials with lesser order that reference samples. The material formed from rice hulls ash without the calcination step achieved better adsorption results than organophilic clays

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Kalanchoe brasiliensis Cambess (Crassulaceae), commonly known as saião , coirama branca , folha grossa , is originally from Brazil and commonly found in São Paulo to Bahia, mainly in the coastal zone. Regarding of biological activities, most preclinical studies were found in the literature, mainly about the anti-inflammatory activity of extracts obtained from leaves and / or aerial parts of K. brasiliensis. As regards the chemical constitution, it has been reported mainly the presence of flavonoids in the leaves of the species, but until this moment did not knows which are the active compounds. Although it is a species widely used in traditional medicine in Brazil, there is no monograph about the quality parameters of the plant drug. In this context, this study aims to characterize and quantify the chemical markers of hydroethanolic extract (HE) from the leaves of K. brasiliensis, which can be used in quality control of plant drug and derivatives obtained from this species. The methodology was divided into two parts: i. Phytochemical study: to fractionate, isolate and characterizate of the chemical (s) marker (s) of the HE from the leaves of K. brasiliensis; ii. To Developed validate of analytical method by High Performance Liquid Chromatography (HPLC)-diode array detector (DAD) to quantify the chemical (s) marker (s) of the EH. i. The EH 50% was prepared by turbo extraction method. It was then submitted to liquid-liquid partition, obtaining dichloromethane, n-butanol and ethyl acetate (AcOEt) fractions. The AcOEt fraction was selected to continue the fractionation process, because it has a chemical profile rich in flavonoids. The acOEt fraction was submitted to column chromatography using different systems for obtaining the compound Kb1. To identify this compound, it was submitted to UV analysis ii. For quantitative analysis, the EH was analyzed by HPLC, using different methods. After selecting the most appropriate method, which showed satisfactory resolution and symmetrical peaks, it was validated according to parameters in the RE 899/2003. As result, it was obtained from the AcOEt fraction the compound Kb1 (2.7 mg). Until this moment, the basic nucleus was characterized by UV analysis using shift reagents. The partial chemical structure of the compound Kb1 was identified as a flavonol, containing hydroxyls in 3 , 4 position (ring A), 5 and 7 free (ring B) and a replacement of the C3 hydroxyl by a sugar. As the analysis were performed in the HPLC coupled to a DAD, we observed that the UV spectrum of the major peaks of EH from K. brasiliensis shown similar UV spectrum. According to the literature, it has been reported the presence of patuletin glycosydes derivatives in the leaves of this species. Therefore, it is suggested that the compound Kb1 is glycosylated patuletin derivative. Probably the sugar (s) unit(s) are linked in the C3 in the C ring. . Regarding the development of HPLC analytical method, the system used consists of phase A: water: formic acid (99,7:0,3, v / v) and phase B: methanol: formic acid (99,7:0,3, v / v), elution gradient of 40% B - 58% B in 50 minutes, ccolumn (Hichrom ®) C18 (250x4, 0 mm, 5 μm), flow rate 0.8 mL / min, UV detection at 370 nm, temperature 25 ° C. In the analysis performed with the co-injection of thecompound Kb1 + HE of K. brasiliensis was observed that it is one of the major compounds with a retention time of 12.47 minutes and had a content of 15.3% in EH of leaves from K. brasiliensis. The method proved to be linear, precise, accurate and reproducible. According to these results, it was observed that compound Kb1 can be used as a chemical marker of EH from leaves of K. brasiliensis, to assist in quality control of drug plant and its derivatives

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Algaroba (Prosopis juliflora) is a typical legume from arid and semi arid regions, which is composed by sugar-rich pods and high protein seeds. Phenolic compounds are secondary metabolites recognized as potent bioactive compounds, found in several vegetables.Therefore, the objective of this work is to characterize the algaroba flour in terms of its physicalchemical composition, total phenolic content, antioxidant activity by DPPH and ABTS methods, a-amylase and a-glycosidase inhibition, as well as to analyze its organic compounds by high performance liquid chromatography (HPLC). Three experimental groups were investigated (seeds, seeds and pod together and only pod), which were prepared by oven drying and posterior grinding. Water and ethanol extracts (70, 80, 100% v/v) were prepared and used for functional studies. Organic compounds were detected by using HPLC equipment coupled to mass spectrometer. Results show important physical-chemical differences among the experimental groups, seeds, seeds and pod together and only pod. The algarroba seed flour is high in protein (49.49%) and fat (3.10%), while the pod flour is especially rich in sugar (60.3% to 67.9%). Algaroba phenolics are concentrated in pod flour, mainly in water extracts (1.30 mg GAEQ/100g sample). All seed extracts showed high DPPH activity and maximum antioxidant activity was registered for ethanol 80% extracts (19.81 μM Trolox/g sample). The ABTS activity ranged from 9.73 to 12.74 μM Trolox/g sample. Nearly all the extracts were able to inhibit α-amylase activity mildly (30.50% to 48.80%), while the maximum α-glycosidase inhibition was observed for pod water extracts (81.03%). Algaroba water extracts proven to be especially rich in organic compounds, observed by the high number of chromatographic peaks. Results demonstrate that algaroba is a potential candidate for further investigations concerning its possible functional applications

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Studies show the great influence of free radicals and other oxidants as responsible for aging and degenerative diseases. On the other hand, the natural phenolic compounds has shown great as antioxidants to inhibit lipid peroxidation and lipoxygenase in vitro. Among these, is highlighted trans-resveratrol ( 3,5,4 `- trihydroxystilbene ) phenolic compound , characterized as a polyphenol stilbene class. The vegetables popularly known as "Azedinha" (Rumex Acetosa) has trans-resveratrol in its composition and from this, the present work aimed to study on the supercritical extraction and conventional extraction (Soxhlet and sequential) in roots of Rumex Acetosa, evaluating the efficiency of extractive processes, antioxidant activity, total phenolic content and quantification of trans-resveratrol contained in the extracts. Extractions using supercritical CO2 as solvent, addition of co-solvent (ethanol) and were conducted by the dynamic method in a fixed bed extractor. The trial met a 23 factorial design with three replications at the central point, with the variable reply process yield and concentration of trans-resveratrol and pressure as independent variables, temperature and concentration of co-solvent (% v/v). Yields ( mass of dry extract / mass of raw material used ) obtained from the supercritical extraction ranged from 0,8 to 7,63 % , and the best result was obtained at 250 bar and 90 °C using the co-solvent 15% ethanol (% v/v). The value was calculated for YCER a flow rate of 1,0 ± 0,17 g/min resulting in 0,0469 CO2 ( g solute / g solvent ). The results of the mass yield varied between conventional extractions 0,78 % ( hexane) and 9,97 % (ethanol). The statistical model generated from the data of the concentration of trans-resveratrol performed as meaningful and predictive for a 95% confidence. GC analysis on HPLC (High Performance Liquid Chromatography), transresveratrol was quantified in all extracts and concentration values ranged between 0,0033 and 0,42 ( mg / g extract) for supercritical extracts and between 0,449 and 17,046 (mg / g extract) to conventional extractions and therefore, the Soxhlet extraction with ethanol for more selective trans-resveratrol than the supercritical fluid. Evaluation of antioxidant (radical method to sequester 2,2- diphenyl-1- picryl - hydrazyl - DPPH) the supercritical extracts resulted in EC50 values (concentration effective to neutralize 50% of free radicals) of between 7,89 and 18,43 mg/mL , while resulting in a Soxhlet extraction with EC50 values in the range of 6,05 and 7,39 mg/mL. As for quantification of the phenolic compounds (Method Spectrophotometer Folin-Ciocalteau) the supercritical extracts resulted in values between 85,3 and 194,79 mg GAE / g extract, whereas values derived from the Soxhlet extract resulted in values between 178,5 and 237,8 mg GAE / g extract. The high antioxidant activity can not be attributed solely to the presence of phenolic compounds, but the presence of other antioxidants in the existing Rumex acetosa

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The wet oxidation of organic compounds with CO2 and H2O has been demonstrated to be an efficient technique for effluent treatment. This work focuses on the synthesis, characterization and catalytic performance of Fe-MnO2/CeO2, K-MnO2/CeO2/ palygorskite and Fe/ palygorskite toward the wet oxidative degradation of phenol. The experiments were conducted in a sludge bed reactor with controlled temperature, pressure and stirring speed and sampling of the liquid phase. Experiments were performed on the following operating conditions: temperature 130 ° C, pressure 20.4 atm, catalyst mass concentration of 5 g / L initial concentration of phenol and 0.5 g / L. The catalytic tests were performed in a slurry agitated reactor provided with temperature, pressure and agitation control and reactor liquid sampling. The influences of iron loaded on the support (0.3; 7 and 10%, m/m) and the initial pH of the reactant medium (3.1; 6.8; 8.7) were studied. The iron dispersion on the palygorskite, the phase purity and the elemental composition of the catalyst were evaluated by X-Ray Difraction (XRD), Scanning Electron Microscopy (SEM) and X-Ray Flourescence (XRF). The use of palygorskite as support to increase the surface area was confirmed by the B.E.T. surface results. The phenol degradation curves showed that the Fe3+ over palygorskite when compared with the other materials tested has the best performance toward the (Total Organic carbonic) TOC conversion. The decrease in alkalinity of the reaction medium also favors the conversion of TOC. The maximum conversion obtained from the TOC with the catalyst 3% Fe / palygorskite was around 95% for a reaction time of 60 minutes, while reducing the formation of acids, especially acetic acid. With products obtained from wet oxidation of phenol, hydroquinone, p-benzoquinone, catechol and oxalic acid, identified and quantified by High Performance Liquid Chromatography was possible to propose a reaction mechanism of the process where the phenol is transformed into the homogeneous and heterogeneous phase in the other by applying a kinetic model, Langmuir-Hinshelwood type, with evaluation of kinetic constants of different reactions involved.