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Full-Text Articles in Chemistry

Spectrophotometric Analysis Of Stability Of Gold Nanoparticles During Catalytic Reduction Of 4-Nitrophenol, Farhat Saira, Samia Saleemi, Humaira Razzaq, Rumana Qureshi Jan 2021

Spectrophotometric Analysis Of Stability Of Gold Nanoparticles During Catalytic Reduction Of 4-Nitrophenol, Farhat Saira, Samia Saleemi, Humaira Razzaq, Rumana Qureshi

Turkish Journal of Chemistry

Spectrophotometric monitoring of 4-nitrophenol (4-NP) reduction by sodium borohydride (NaBH4) using gold nanoparticles (GNPs) as a catalyst has been extensively studied, but the stability of GNPs in terms of change in the surface plasmon resonance (SPR) at different temperatures has not been explored. In the present investigation, our aim was to evaluate the SPR stability of GNPs as a catalyst during the reduction of 4-NP at different elevated temperatures (i.e. 30-60 °C) and sodium borohydride concentrations. Sensitivity of this degradation process toward concentration of GNPs at a range of temperatures is also evaluated. The spectrophotometric results reveal that up to …


Sensitive Determination Of Hydrogen Peroxide In Real Water Samples By High Spin Peroxo Complex, Tuğba Yavuz, Levent Peli̇t Jan 2020

Sensitive Determination Of Hydrogen Peroxide In Real Water Samples By High Spin Peroxo Complex, Tuğba Yavuz, Levent Peli̇t

Turkish Journal of Chemistry

In this paper, a fast, cheap, simple, sensitive and selective spectrophotometric method based on high spin peroxo-Fe(III)-EDTAcomplexinthealkalinemediumwasdevelopedforthedeterminationofhydrogenperoxide(H$_{2}$O$_{2}$) in real water samples. The purple-coloured complex with a maximum absorbance at a wavelength of 525 nm was formed. Various parameters such as type of stabilizer reagent and its concentration, reaction time, Fe(III), EDTA and NH3 concentration were optimized. The method was confirmed with the Beer?s law with a molar absorption coefficient of267.36Lmol$^{-1}$ cm$^{-1}$ in the 8.3×10$^{-6}$ -4.08×10$^{3}$ mol/L concentrationrange. Sandell's sensitivityoftheproposed method was also calculated as 0.188 µg/cm2. LOD and LOQ were determined as 2.5 ×10$^{-6}$ and 8.3 ×10$^{-6}$ mol/L, respectively. Intraday …


Spectrophotometric Detection Of Rhodamine B In Tap Water, Lipstick, Rouge, And Nail Polish Samples After Supramolecular Solvent Microextraction, Nebi̇ye Özkantar, Mustafa Soylak, Mustafa Tüzen Jan 2017

Spectrophotometric Detection Of Rhodamine B In Tap Water, Lipstick, Rouge, And Nail Polish Samples After Supramolecular Solvent Microextraction, Nebi̇ye Özkantar, Mustafa Soylak, Mustafa Tüzen

Turkish Journal of Chemistry

A simple and sensitive supramolecular solvent-based dispersive liquid--liquid microextraction method was described for the separation/preconcentration and spectrophotometric detection of rhodamine B. The microextraction method, which was realized at ambient temperature for the detection of rhodamine B, was carried out by using supramolecular solvents such as tetrahydrofuran and decanoic acid. The method was based on analyses of rhodamine B by using UV-Vis spectrophotometry at 558 nm. The influences of some parameters such as pH, sample volume, eluent solutions, centrifugation time, and ultrasonic bath time were optimized. The effects of various matrix ions were also investigated. Moreover, the limit of detection and …


Spectrophotometric Determination Of Mercury Using Vortex-Assisted Liquid-Liquid Microextraction, Tatiana Antolova, Serhii Zaruba, Jana Sandrejova, Livia Kocurova, Andriy B. Vishnikin, Yaroslav Bazel, Vasil Andruch, Ioseph S. Balogh Jan 2016

Spectrophotometric Determination Of Mercury Using Vortex-Assisted Liquid-Liquid Microextraction, Tatiana Antolova, Serhii Zaruba, Jana Sandrejova, Livia Kocurova, Andriy B. Vishnikin, Yaroslav Bazel, Vasil Andruch, Ioseph S. Balogh

Turkish Journal of Chemistry

A novel method for the determination of mercury(II) is suggested. The procedure is based on the formation of an ion associate between the bromide complex of Hg(II) and Astrazon Red 6B dye and vortex-assisted liquid-liquid microextraction of the ion associate formed, with subsequent spectrophotometric detection. The variables that affect the procedure, such as pH, the concentration of ligand and dye, the type and volume of extraction solvent, and the rate and time of vortex mixing, were optimized. Under optimum conditions (pH 2.0, 0.01 mol L$^{-1}$ KBr, 2 $\times $ 10$^{-4}$ mol L$^{-1}$ AR6B, 50 $\mu $L of the extraction mixture …


Spectrophotometric Determination Of Iron Species Using Ionic Liquid Ultrasound Assisted Dispersive Liquid--Liquid Microextraction, Alireza Bazmandegan, Ali Mohammad Haji Shabani, Sayessteh Dadfarnia, Mahboubeh Saeidi, Masoud Rohani Moghadam Jan 2015

Spectrophotometric Determination Of Iron Species Using Ionic Liquid Ultrasound Assisted Dispersive Liquid--Liquid Microextraction, Alireza Bazmandegan, Ali Mohammad Haji Shabani, Sayessteh Dadfarnia, Mahboubeh Saeidi, Masoud Rohani Moghadam

Turkish Journal of Chemistry

A simple and efficient method for speciation and determination of iron in different water samples was developed. The method is based on ionic liquid ultrasound assisted dispersive liquid--liquid microextraction (IL-USA-DLLME) followed by spectrophotometric determination. Fe(II) is complexed with 2,4,6-tri(2'-pyridyl)-l,3,5-triazine (TPTZ{)}, neutralized through ion pair formation with sodium dodecyl sulfate (SDS) and extracted into 1-hexyl-3-methylimidazolium hexafluorophosphate [C$_{6}$MIM][PF$_{6}$]. Total iron amount was determined after reduction of Fe(III) to Fe(II) with hydroxylamine hydrochloride. The concentration of Fe(III) was determined from the difference of concentration of total iron and Fe(II). The important parameters such as the type and volume of the extraction solvent, pH, …


Spectrophotometric Determination Of Molybdenum Using Surfactant-Mediated Liquid--Liquid Extraction, Rameshwar Dass, Jitander Kumar Kapoor, Sunita Gambhir Jan 2014

Spectrophotometric Determination Of Molybdenum Using Surfactant-Mediated Liquid--Liquid Extraction, Rameshwar Dass, Jitander Kumar Kapoor, Sunita Gambhir

Turkish Journal of Chemistry

A new spectrophotometric method has been developed for determination of molybdenum using surfactant-mediated liquid--liquid extraction. Molybdenum(V) obtained by ascorbic acid reduction in 2.5 M H_2SO_4 reacted spontaneously with thiocyanate and cetyl trimethyl ammonium bromide (CTAB), forming an intense orange yellow complex that was extracted quantitatively into 1,2-dichloroethane and absorbed at 460 nm. The absorbance of the extract was found to be stable for more than 24 h. Beer's law was obeyed over the concentration range 0.1--4.2 \mu g Mo mL^{-1} of the extract. The linear range for an accurate determination was found to be 1.2--2.6 \mu g Mo mL^{-1}. The …


Determination Of Pb(Ii) In Natural Water With Dibromo-P-Methyl-Sulfonazo By The Light-Absorption Ratio Variation Approach, Jie Zhang Jan 2013

Determination Of Pb(Ii) In Natural Water With Dibromo-P-Methyl-Sulfonazo By The Light-Absorption Ratio Variation Approach, Jie Zhang

Turkish Journal of Chemistry

Pb ions can react sensitively with dibromo-p-methylsulfonazo (DMSA) to form a blue complex, whose absorption is maximal at 630 nm. By means of the light-absorption ratio variation approach (LARVA), the direct determination of Pb was developed in 0.3 M nitric acid and plots of \Delta A_r^{-1} vs. c_{Pb}^{-1} are linear where \Delta A_r is the light-absorption ratio variation and c_{Pb} Pb(II) concentration is between 0 and 5.0 mg/L. The limit of detection (3\sigma) of Pb(II) is only 0.02 mg/L. This method was applied to direct analysis of natural water with satisfactory results.


Surfactant-Sensitized Spectrophotometric Determination Of Hg(Ii) In Water Samples Using 2-(2-Thiazolylazo)- P-Cresol As Ligand And Cetylpyridinium Chloride As Cationic Surfactant, Ramazan Gürkan, Tuğba Çepken, Hali̇l İbrahi̇m Ulusoy Jan 2012

Surfactant-Sensitized Spectrophotometric Determination Of Hg(Ii) In Water Samples Using 2-(2-Thiazolylazo)- P-Cresol As Ligand And Cetylpyridinium Chloride As Cationic Surfactant, Ramazan Gürkan, Tuğba Çepken, Hali̇l İbrahi̇m Ulusoy

Turkish Journal of Chemistry

A new, reliable, surfactant-sensitized method is described for the spectrophotometric determination of total and dissolved inorganic mercury at trace levels. The method is based on the ternary complex formation of Hg(II) with 2-(2-thiazolylazo)-p-cresol and a cationic surfactant, cetylpyridinium chloride, at pH 9.5. The detection and quantification limits of the method with surfactant were 6 and 19 \mu g L^{-1}, while those of the method without surfactant were 22 and 67 \mu g L^{-1}, respectively. The method obeys Beer's law at up to approximately 10 mg L^{-1} Hg(II) in an aqueous surfactant medium. The relative errors and relative standard deviations of …


Determination Of Ni(Ii) With Picolinaldehyde-4-Phenyl-3-Thiosemicarbazone Used As A Chromogenic Reagent In A Nonionic Micellar System, Aamna Balouch, Muhammad Iqbal Bhanger, Farah Naz Talpur, Willie L. Hinze Jan 2011

Determination Of Ni(Ii) With Picolinaldehyde-4-Phenyl-3-Thiosemicarbazone Used As A Chromogenic Reagent In A Nonionic Micellar System, Aamna Balouch, Muhammad Iqbal Bhanger, Farah Naz Talpur, Willie L. Hinze

Turkish Journal of Chemistry

Spectrophotometric determination of Ni(II) was carried out using picolinaldehyde-4-phenyl-3-thiosemicarbazone (PAPT) as a complexing/chromogenic reagent. The possibility of using a micellar system was explored to enhance the degree of detection and allow a more sensitive spectrophotometric method for the determination of nickel ions. The anionic surfactant Triton X-100 greatly enhanced the molar absorptivity and limit of detection relative to that observed with bulk water or an organic solvent. The linear calibration graphs were obtained for 0.5-2.0 mg L^{-1} and 0.001-1.0 mg L^{-1} of Ni(II) in aqueous and surfactant media, respectively. Using this approach, the limit of detection for the PAPT-Ni(II) complex …


Determination Of Stability Constants Of 5-(2-Hydroxybenzylidene)-2-Thioxodihydropyrimidine-4,6(1h,5h)-Dione With Copper(Ii) And Mercury(Ii) Ions, Morteza Bahram, Nader Noroozi Pesyan, Abdolhossein Naseri, Masomeh Tasbihforosh Jan 2011

Determination Of Stability Constants Of 5-(2-Hydroxybenzylidene)-2-Thioxodihydropyrimidine-4,6(1h,5h)-Dione With Copper(Ii) And Mercury(Ii) Ions, Morteza Bahram, Nader Noroozi Pesyan, Abdolhossein Naseri, Masomeh Tasbihforosh

Turkish Journal of Chemistry

In this work, a hard model chemometric method was used to determine the stability constants of copper(II) and mercury(II) complexes with the newly synthesized ligand 5-(2-hydroxybenzylidene)- 2-thioxodihydropyrimidine-4,6(1H,5H)-dione in acetonitrile by UV-Vis spectrophotometry. The ligand forms stable complexes with both metal cations. The protonation constants of the ligand were also measured in an ethanol-water (1:1) mixture.


Solidified Floating Organic Drop Microextraction And Spectrophotometric Determination Of Vanadium In Water Samples, Shayessteh Dadfarnia, Ali Mohammad Haji Shabani, Akram Mirshamsi Jan 2011

Solidified Floating Organic Drop Microextraction And Spectrophotometric Determination Of Vanadium In Water Samples, Shayessteh Dadfarnia, Ali Mohammad Haji Shabani, Akram Mirshamsi

Turkish Journal of Chemistry

Solidified floating organic drop microextraction (SFODME) was used as a sample preparation method prior to spectrophotometric determination of trace amounts of vanadium in water samples. 8-Hydroxyquinoline (oxine) was used as the chelating agent. The main parameters affecting the performance of SFODME, such as pH, concentration of oxine, extraction time, sample and organic phase volume, extraction temperature, and the nature of the organic solvent, were optimized. Under the optimized conditions, an enhancement factor of 38, detection limit of 0.97 \mu g L^{-1}, and good relative standard deviation of \pm 3.9% at 10 \mu g L^{-1} were obtained. The method was successfully …


Color Reaction Of 2-(2-Quinolylazo)-5-Dimethylaminoaniline With Palladium And Its Application, Yunsen Si, Qiufen Hu, Zhangjie Huang, Guangyu Yang, Jiayuan Yin Jan 2005

Color Reaction Of 2-(2-Quinolylazo)-5-Dimethylaminoaniline With Palladium And Its Application, Yunsen Si, Qiufen Hu, Zhangjie Huang, Guangyu Yang, Jiayuan Yin

Turkish Journal of Chemistry

A new chromogenic reagent, 2-(2-quinolylazo)-5-dimethylaminoaniline (QADMAA) was synthesized. A sensitive, selective and rapid method for the determination of palladium based on the rapid reaction of palladium(II) with QADMAA was developed. In the presence of 0.5-2.5 mol L^{-1} of hydrochloric acid solution and cetyl trimethylammonium bromide medium QADMAA reacts with palladium to form a violet complex with a molar ratio of 1:2 (palladium to QADMAA). The molar absorptivity of the chelate is 1.35x10^5 L mol^{-1} cm^{-1} at 600 nm. Beer's law is obeyed in the range of 0.01 to 0.6 \mu g mL^{-1}. The detection limit is 1.2 \mu g L^{-1}. …


Spectrophotometric Study Of The Interaction Between Aza-15-Crown-5 And Some \Pi-Acceptors In Chloroform Solution, H. R. Pouretedal, A. Semnani, Mohammad Hossein Keshavarz, A. Firooz Jan 2005

Spectrophotometric Study Of The Interaction Between Aza-15-Crown-5 And Some \Pi-Acceptors In Chloroform Solution, H. R. Pouretedal, A. Semnani, Mohammad Hossein Keshavarz, A. Firooz

Turkish Journal of Chemistry

A spectrophotometric study concerning the interaction between A15C5 as n-donor and TCNE, DDQ, TCNQ and bromanil as \pi -acceptor was been performed in chloroform at 25 °C. The results of TCNE indicate the formation of a 1:1 charge-transfer complex through a nonequilibrium reaction. In the case of DDQ, the formation of 1:2 (A15C5/DDQ) and 1:1 charge-transfer complexes through equilibrium and nonequilibrium reactions is confirmed. The formation constant of the equilibrium step was evaluated from the computer fitting of the absorbance-mole ratio data as logK_f = 5.14 \pm 0.09. The [A15C5^+ (DDQ)_2^- ] and [A15C5^+DDQ^- ] are suggested as the possible …


A Sensitive Spectrophotometric Assay For Tinidazole And Metronidazole Using A Pd-C And Formic Acid Reduction System, Nandipura Dyavegowda Dinesh, Padmarajaiah Nagaraja, K. Subbegowda Rangappa Jan 2004

A Sensitive Spectrophotometric Assay For Tinidazole And Metronidazole Using A Pd-C And Formic Acid Reduction System, Nandipura Dyavegowda Dinesh, Padmarajaiah Nagaraja, K. Subbegowda Rangappa

Turkish Journal of Chemistry

A simple, sensitive and rapid spectrophotometric method for the determination of tinidazole (TZ) and metronidazole (MZ) in pure as well as in dosage form is described. The method is based on the reduction of the nitro group of drugs using a novel and versatile reduction system comprising 10% Pd-C and formic acid. The resulting amine was then subjected to a condensation reaction with sodium 1,2-naphthaquinone-4-sulfonate (NQS) to form red Schiff base with an absorption maximum at 510 nm. Beer's law was obeyed in the concentration ranges 2.0 to 45.0 \mu g mL^{-1} and 1.5 to 37.0 \mu g mL^{-1} with …


Study On The Solid Phase Extraction And Spectrophotometric Determination Of Cobalt With 2-(2-Quinolylazo)-5-Diethylaminoaniline, Qiufen Hu, Guangyu Yang, Xuechang Dong, Jiayuan Yin Jan 2004

Study On The Solid Phase Extraction And Spectrophotometric Determination Of Cobalt With 2-(2-Quinolylazo)-5-Diethylaminoaniline, Qiufen Hu, Guangyu Yang, Xuechang Dong, Jiayuan Yin

Turkish Journal of Chemistry

A sensitive, selective and rapid method for the determination of cobalt based on the rapid reaction of cobalt(II) with QADEAA and the solid phase extraction of the Co(II)-QADEAA chelate with C_{18} membrane disks was developed. In the presence of pH = 5.5 buffer solution and cetyl trimethylammonium bromide (CTMAB) medium, QADEAA reacts with cobalt to form a violet complex with a molar ratio of 1:2 (cobalt to QADEAA). This chelate was enriched by the solid phase extraction with C_{18} membrane disks. An enrichment factor of 50 was obtained by elution of the chelate from the disks with a minimal amount …


Atomic Absorption And Spectrophotometeric Determinations Of Salicylhydroxamic Acid In Its Pure And Pharmaceutical Dosage Forms, Alaaeldin Abdelaziz Salem, Mohamed Mohamed Omar Jan 2003

Atomic Absorption And Spectrophotometeric Determinations Of Salicylhydroxamic Acid In Its Pure And Pharmaceutical Dosage Forms, Alaaeldin Abdelaziz Salem, Mohamed Mohamed Omar

Turkish Journal of Chemistry

A new method for the indirect determination of salicylhydroxamic acid (SHAM) using atomic absorption spectrometry (AAS) was proposed. The method is based on precipitating the ion associate complex of SHAM with [Cu (NH_{3})_{4}]^{2+}. The excess, unreacted, Cu^{2+} ions were determined using AAS. Another spectrophotometric method based on measuring the absorbance of the formed [Cu (NH_{3})_{4}]-SHAM complex in dioxane was proposed. The green color of the complex formed was measured at 330 nm. The two methods were successfully used for determining SHAM in its pure and pharmaceutical dosage forms. Using AAS, the drug was determined over a concentration range of 3.06 …


Cerimetric Determination Of Propranolol In Bulk Drug Form And In Tablets, Kanakapura Basavaiah, Umakanthappa Chandrashekar, H. Chandrashekar Prameela Jan 2003

Cerimetric Determination Of Propranolol In Bulk Drug Form And In Tablets, Kanakapura Basavaiah, Umakanthappa Chandrashekar, H. Chandrashekar Prameela

Turkish Journal of Chemistry

Two simple, accurate and precise methods are described for the determination of propranolol hydrochloride with cerium(IV) sulphate. The titrimetric method is based on the oxidation of the drug by a known excess amount of cerium(IV) sulphate and back titration of the unconsumed oxidant with ammonium ferrous sulphate. In the spectrophotometric method, the unreacted cerium(IV) sulphate is treated with iron(II) sulphate, and the iron(III) sulphate produced is complexed with thiocyanate and measured at 480 nm, thereby permitting the determination of the amount of unreacted cerium(IV) sulphate. In both procedures, the amount of the reacted oxidant corresponds to the drug content. Different …


Application Of Potassium Chromate-Diphenylcarbazide In The Quantitative Determination Of Ascorbic Acid By Spectrophotometry, Meissam Noroozifar, M. Khorasani Motlagh Jan 2003

Application Of Potassium Chromate-Diphenylcarbazide In The Quantitative Determination Of Ascorbic Acid By Spectrophotometry, Meissam Noroozifar, M. Khorasani Motlagh

Turkish Journal of Chemistry

A spectrophotometric procedure for the determination of ascorbic acid in pure form and in a number of pharmaceutical preparations and real samples has been developed that offers the advantages of simplicity, accuracy, precision and sensitivity over many other methods. The method is based on the oxidation of ascorbic acid by a known excess amount of potassium chromate followed by the estimation of the unreacted amount of chromate by reactions with sym-diphenylcarbazide. The reacted oxidant corresponds to the ascorbic content. At the maximum absorption of 548 nm, Beer's law is obeyed up to 5 \mu g/mL of ascorbic acid. Statistical treatment …


A Spectrophotometric Method For The Determination Of Prazosin Hydrochloride In Tablets, Mahmure Üstün Özgür, Sidika Sungur Jan 2002

A Spectrophotometric Method For The Determination Of Prazosin Hydrochloride In Tablets, Mahmure Üstün Özgür, Sidika Sungur

Turkish Journal of Chemistry

A rapid and sensitive analytical method was developed for the spectrophotometric assay of prazosin hydrochloride. The method is based on the formation of a coloured derivative between the drug and 1,2-naphthoquinone-4- sulphonic acid sodium salt (NQS). The reaction proceeds quantitatively at pH 4.5 and 70°C for 40 min. After the extraction of the derivative with chloroform: n-butanol (3:1), the absorbance was measured at 400 nm. The method was applied to commercially available tablets and the results were statistically compared with those obtained by ultraviolet spectrophotometric and differential pulse polarographic methods using t- and F-tests.


Spectrophotometric Determination Of Mexiletine Hydrochloride In Capsules Using Bromothymol Blue, Zeynep Aydoğmuş, S. Müge Çeti̇n, Sedat Tosunoğlu Jan 2002

Spectrophotometric Determination Of Mexiletine Hydrochloride In Capsules Using Bromothymol Blue, Zeynep Aydoğmuş, S. Müge Çeti̇n, Sedat Tosunoğlu

Turkish Journal of Chemistry

A new spectrophotometric method based on the formation of an ion-pair using bromothymol blue as ion-pair complexing reagent was developed for the determination of mexiletine hydrochloride in capsules. The ion-pair formed was highly coloured and easily extracted with dichloromethane. The calibration curve was linear over the concentration range 1.08--10.8 \mu g.ml^{-1} at \lambda_{max} = 408 nm (r = 0.9999). The results obtained from the developed method were compared statistically with those obtained by the British Pharmacopeia method.


Novel Method For The Spectrophotometric Determination Of Isoniazid And Ritodrine Hydrochloride, Padmarajaiah Nagaraja, Kallanchira Sunitha, Ramanathapura Vasantha, Hemmige Yathirajan Jan 2002

Novel Method For The Spectrophotometric Determination Of Isoniazid And Ritodrine Hydrochloride, Padmarajaiah Nagaraja, Kallanchira Sunitha, Ramanathapura Vasantha, Hemmige Yathirajan

Turkish Journal of Chemistry

A simple, rapid and sensitive spectrophotometric method for the determination of isoniazid (INH) and ritodrine hydrochloride (RTH) in pure form as well as dosage forms is described. The method is based on the diazotisation of 4,4'-sulphonyldianiline (dapsone, DAP) followed by a coupling reaction with either INH or RTH in sodium hydroxide medium. Beer's law is obeyed in the concentration range of 0.5-20 \mu g ml^{-1} for INH at 440 nm and 0.5-18 \mu g ml^{-1} for RTH at 460 nm. The method is successfully employed for the determination of INH/RTH in pharmaceutical preparations and the results agree favourably with the …


Determination Of Thermodynamic Parameters Of Some Complexes Of 9-Ethyl-3-Carbazolecarboxaldehyde 4-Phenyl-3-Thiosemicarbazone (Eccapt), E. Güler Akgemci̇, Tevfi̇k Atalay Jan 2000

Determination Of Thermodynamic Parameters Of Some Complexes Of 9-Ethyl-3-Carbazolecarboxaldehyde 4-Phenyl-3-Thiosemicarbazone (Eccapt), E. Güler Akgemci̇, Tevfi̇k Atalay

Turkish Journal of Chemistry

The complexes of Cu(II), Co(II), Zn(II), and Cd(II) with 9-ethyl-3-carbazolecarboxaldehyde 4-phenyl-3-thiosemicarbazone were synthesized and their stability constants were determined using a spectrophotometric method at different temperatures (25, 30, 35 and 40 \pm 0.1°C) and ionic strengths (0.05, 0.01 and 0.20 M KNO_3) in 50% (v/v) aqueous DMF. From these constants, the thermodynamic stability constants and thermodynamic parameters (\Delta G°, \Delta H° and \Delta S°) were calculated.