Kinetic Spectrophotometric Determination of Trace Iron (III) with p-Amino-N,N-Dimethylaniline Dihydrochloride and Hydrogen Peroxide

A new, simple and highly sensitive kinetic method for the determination oftrace iron (III) has been developed based on the catalytic effect of iron (III) on colorreaction of p-amino-N, N-dimethylaniline dihydrochloride (p-DMA) oxidated by hydrogenperoxide. The reaction is followed spectrophotometrically by measuring the absorbanceat 510 nm. The detection limit is 4.47×10-11 g/ml, and the calibration curve is linear inthe range of 0-0.10μg Fe(III) /25 ml with a relative standard deviation of ±3.25%. Themethod has been applied to the determination of iron in tap-water, chemical reagents andhuman hair.

Kinetic Investigation of Ce,Y-CPAmA Systems and Simultaneous Determination of Sc,Y,Ce via Complementary Tristimulus Spectrophotometry

In the past ten years the eomplementary tristimulus speetrophotometryll],eTs,has seen its diverse appli-eations{2一61 though most researehes remain in relatively simpe systems,and less work has been involvinkinetie reaetions. An attemPt has been made on the investigation of some comPlieated systems eontainingrare earths and meta一acetylchloroPhosPhonaz

Spectrophotometric Study for the Reaction of Pentoxifylline Hydrochloride with 1,2-Naphthoquinone-4-Sulphonate: Kinetics, Mechanism and Application for Development of High-Throughput Kinetic Microwell Assay for Pentoxifylline in Quality Control Laboratory

Spectrophotometric study was carried out, for the first time, to investigate the reaction between the vasodilator pentoxifylline hydrochloride (POX) and 1,2-naphthoquinone-4-sulphonate (NQS) reagent. The reaction occurs in alkaline medium to activate the nucleophilic substitution reaction producing an orange-colored product measured spectrophometrically at λmax 472 nm. The variables affecting the reaction were carefully studied and the conditions were optimized. The kinetics of the reaction was investigated and its activation energy was found to be 0.262 cal/mol. Owing to its low activation energy, the reaction proceeded easily and was successfully used for simple and rapid assay of POX. The stoichiometry of the reaction was determined (1:1), and the reaction mechanism was suggested. To develop a high-throughput methodology used in quality control laboratory, a comparative study of the reaction using the conventional spectrophotometric versus microwell assay was applied. Under the optimum reaction conditions, the initial rate and fixed time methods were utilized for constructing the calibration graphs for determination of POX concentrations. The linear range was 10 - 120 μg/ml with good correlation coefficients (0.9987 - 0.9998). The LOD was 2.5 and 3.4 μg/ml for initial rate and fixed time methods, respectively. The intra- and inter-day accuracy and precision of the developed methods were satisfactory, where RSD was ≤3.94%. The present methods have been successfully applied to the determination of POX in its pharmaceutical tablets, and the percentage recovery values were 97.9% - 101.9%. Therefore, we strongly recommend the proposed methods for determination of POX in quality control laboratories.

Kinetic spectrophotometric method for the determination of cerium(IV) with naphthol green B

A simple and sensitive spectrophotometric method was described for the determination of cerium（IV） based on its catalytic effect on the oxidation of naphthol green B by potassium periodate in the medium of sulfuric acid. The influences of acidity, concentration of reactants, reaction time, reaction temperature, and foreign ions were discussed, and the optimum reaction conditions were established. The reaction was monitored spectrophotometrieally by measuring the decrease in absorbance of naphthol green B at 710 nm after a fixed time （8 min）. The proposed method allowed the determination of cerium（IV） in the range of 0.08-2.4 μg·mL^-1 with good precision and accuracy, and the detection limit was 0.012 μg·mL^-1. The method was applied successfully for the determination of trace cerium in hair samples without previous separation. Recovery experiments were also performed, and the recovery was between 95.7%-111.0%.

Kinetic spectrophotometric determination of vanadium in steels based on the catalytic oxidation of thionine by potassium bromate

A sensitive and selective kinetic spectrophotometric method for the determination of V（V） was developed based on the catalytic oxidation of thionine by KBIO3 in 0.6 mol·L^-1 HaPO4 medium. The linear calibration range and detection limit at 25℃ were 0-0.5 μg·mL^-1 and 0.01 μg·mL^-1, respectively. In the presence of NaF and urea, most of the common ions did not interfere with the determination of V（V）. The proposed method was applied for the determination of vanadium in steels and satisfactory results were obtained.

Simultaneous kinetic spectrophotometric determination of cephalexin and trimethoprim in pharmaceutical preparation and human urine with the aid of chemometrics

A procedure for the simultaneous kinetic spectrophotometric determination of cephalexin and trimethoprim was described. It was based on the different reaction rate of oxidation of these compounds with yellow ammonium cerous （Ⅳ） sulfate in acidic medium and colorless cerous （Ⅲ） sulfate was produced. The overlapped kinetic data was quantitatively resolved by the use of chemometric methods, partial least squares （PLS）, principal component regression （PCR） and radial basis function-artificial neural network （RBF-ANN）. The proposed method was also applied to the simultaneous determination of cephalexin and trimethoprim in pharmaceutical preparation and human urine with satisfied results, which compared well with those obtained by HPLC.

A Kinetic Spectrophotometric Method for the Determination of Iron (Ⅲ) in Water Samples

A new kinetic spectrophotometric method has been developed for the determination of iron （Ⅲ）. The method is based on the catalytic effect of iron （Ⅲ） on the oxidation of weak acid brilliant blue dye （RAWL） by KIO4 in acid medium. The advantages of the proposed method are that it is sensitive, accurate, rapid, inexpensive, can be operated under room temperature and has a large determination concentration range compared to other techniques. The obtained optimum conditions are： pH 3.15, RAWL （200 mgL^-1） 5.00mL, Potassium periodate solution （0.01 molL^-1） 0.30mL, phenanthroline （0.02 molL^-1） 1.00mL, reaction temperature 25℃ and reaction time 7 min. With this method iron could quantitively be determined in the range 0.00-0.02 mgL^-1, the detection limit being 4.10 × 10^10gmL^-1. The relative standard deviations （RSD） in five replicate determinations for 3 μgL^-1and 5 μgL^-1 iron （Ⅲ） are 3.1% and 1.9%, respectively. The method has been applied to the determination of iron （Ⅲ） in tap water samples and seawater samples （from the South China Sea）, the recovery rates being 98.0% and 100.5%, respectively.

Kinetic Spectrophotometric Determination of Trace Titanium(Ⅳ) Based on Oxidation Discoloration of Acid Chrome Blue K with Hydrogen Peroxide

A simple and sensitive kinetic spectrophotometric method for the determination of trace amounts of titanium(IV),based upon the catalytic effect of Ti(IV) on the oxidation of acid chrome blue K (ACBK) by hydrogen peroxide in 0.002 mol/L sulfuric acid,is described. The reaction rate is monitored spectrophotometrically by measuring the decrease in absorbance of ACBK at 524 nm. The detection limit of the method is 1.01×10?9 g/mL,and the linear range is 0-0.048 mg/L. The influence of acidity,concentration of reactants,reaction time,reaction temperature and for-eign ions is also discussed. The optimum reaction conditions were established and some kinetic parameters determined. The apparent activation energy of the catalytic reaction is 5.32 kJ/mol. The relative standard deviation for the determi-nation of titanium(IV) at the concentration of 0.048 mg/L is calculated to be 1.31% (n = 11). In combination with sol-vent extraction separation,the method has been successfully applied to the determination of trace titanium(IV) in human hair,plant matter,tea and rock samples. The results are in good agreement with the certified values with the relative standard deviations (RSD) of 1.4%-3.5%.

Mechanistic Study and Kinetic Determination of Cu(Ⅱ) by the Catalytic Kinetic Spectrophotometric Method

A highly sensitive and selective catalytic kinetic spectrophotometric method for the determination of Cu(Ⅱ) is proposed. It is based on the catalytic effect of Cu(Ⅱ) on the oxidation of glutathione(GSH) by potassium hexacyanoferrate(Ⅲ) in acidic medium at 25.0℃. The reaction is monitored spectrophotometrically by measuring the decrease in absorbance of oxidant at 420 nm using the fix-time method. Under the optimum conditions, the proposed method allows the determination of Cu(Ⅱ) in a range of 0-35.0 ng m L^(-1) with good precision and accuracy and the limit of detection is down to 0.04 ng m L^(-1). The relative standard deviation(RSD) is 1.02%. The reaction orders with respect to each reagent are found to be 1, 1/2, and 1/2 for potassium hexacyanoferrate(Ⅲ), glutathione and Cu(Ⅱ) respectively. On the basis of these values, the rate equation is obtained and the possible mechanism is established. Moreover, few anions and cations can interfere with the determination of Cu(Ⅱ). The new proposed method can be successfully used to the determination of Cu(Ⅱ) in fresh water samples and seawater samples. It is found that the proposed method has fairly good selectivity, high sensitivity, good repeatability, simplicity and rapidity.

Kinetics of Asymmetric Reduction of Phenylglyoxylic Acid to R-(-)-Mandelic Acid by Saccharomyces Cerevisiae FD11b

The kinetics of asymmetric production of R-（-）-mandelic acid （R-MA） from phenylglyoxylic acid （PGA） catalyzed by Saccharomyces cerevisiae sp. strain FD11b was studied by fed-batch cultures. The concentrations of glucose and PGA were controlled respectively with a dual feeding system. When the electron donor glucose was supplied at the rate of 0.0833mmol·gdw^-1·h^-1, the specific production rate （qp） and the enantiomeric excess of R-MA reached the maximum 0.353mmol·gdw^-1·h^-1 and 97.1%, respectively. The apparent reduction activity of yeast FD 11 b was obviously affected by both substrate PGA and product MA. The qp value reached the maximum 0.36-0.38mmol·gdw^-1·h^-1 when the PGA concentration was controlled between 25 and 35mmol·L^-1. The obvious substrate inhibition of bioconversion was observed at the PGA concentrations higher than 40mmol·L^-1. The accumulation of product MA also caused a severe feed-back inhibition for its production when the product concentration was above 60mmol·L^-1. The kinetic model with the inhibition effect of both substrate and product was simulated by a computer-based least-square arithrnatic. The established kinetic model was in good agreement with the experimental data.

Kinetic spectrophotometric method for determination of amlodipine besylate in its pharmaceutical tablets

A simple and sensitive kinetic spectrophotometric method has been developed and validated for determination of amlodipine besylate （AML）. The method was based on the condensation reaction of AML with 7-chloro-4-nitro-2,1,3-benzoxadiazole in an alkaline buffer （pH 8.6） producing a highly colored product. The color development was monitored spectrophometrically at the maximum absorption λmax 470 nm. The factors affecting the reaction were studied and the conditions were optimized. The stoichiometry of the reaction was determined, and the reaction pathway was postulated. Moreover, both the activation energy and the specific rate constant （at 70 ℃） of the reaction were found to be 6.74 kcal mole-1 and 3.58 s -1, respectively. The initial rate and fixed time methods were utilized for constructing the calibration graphs lbr the determination of AML concentration. Under the optimum reaction conditions, the limits of detection and quantification were 0.35 and 1.05 ug/mL, respectively. The precision of the method was satisfactory; the relative standard deviations were 0.85-1.76%. The proposed method was successfully applied to the analysis of AML in its pure form and tablets with good accuracy; the recovery percentages ranged from 99.55 ± 1.69% to 100.65 ±1.48%. The results were compared with that of the reported method.

Kinetic spectrophotometric determination of certain cephalosporins using iodate/iodide mixture

A simple, precise and accurate kinetic spectro-photometric method for determination of ce-fradine anhydrous, cefaclor monohydrate, ce-fadroxil monohydrate, cefalexin anhydrous and cefixime in bulk and in pharmaceutical formula-tions has been developed. The method based on a kinetic investigation of the reaction of the free carboxylic acid group of the drug with a mixture of potassium iodate and potassium iodide at room temperature to form yellow coloured triiodide ions. The reaction was followed up spectrophotometrically by measuring the increase in absorbance at 352 nm as a function of time. The initial rate, fixed time, variable time and rate-constant methods were adopted for constructing the calibration curves but fixed time method has been found to be more applicable. The analytical performance of the method, in terms of accuracy and precision, was statistically validated;the results were satisfactory. The method has been successfully applied to the determination of the studied drugs in commercial pharmaceutical formulations. Statistical comparison of the results with a well established reported method showed excellent ag- reement and proved that there is no significant difference in the accuracy and precision.

Kinetic Modeling the Formation of Low-mature Gases and Analysis of the Possibility to Be Accumulated

At present, shallow gases have received much attention due to low cost in exploration and production. Low-mature gases, as one significant origin to shallow gas, turns to be an important research topic. The present understanding of low-mature gases is confined within some geological cases, and few laboratory studies have been reported. Therefore, the potential and characters of low- mature gases are not clear up to now. Here, two premature samples （one coal and the other shale） were pyrolyzed in a gold confined system. The gaseous components including hydrocarbon gases and non-hydrocarbon gases were analyzed. Based on kinetic modeling, the formation of low-mature gases was modeled. The results showed that during low mature stage, about 178 mL/gTOC gas was generated from the shale and 100 mL/gTOC from the coal. Two third to three fourth of the generated gases are non-hydrocarbon gases such as H2S and CO2. The total yields of C1-5 for the two samples are almost the same, 30-40 mL/gTOC, but individual gaseous hydrocarbon is different. The shale has much lower C1 but higher C2-5, whereas the coal has higher C1 but lower C2-5. Hydrocarbon gases formed during low-mature stage are very wet. The stable carbon isotope ratios of methane range from -40‰ to -50‰ （PDB）, in good consistence with empiric criterion for low-mature gases summed up by the previous researchers. The generation characters suggest that the low-mature gases could be accumulated to form an economic gas reservoir, but most of them occur only as associated gases.

Kinetic Study of Atom Transfer Radical Polymerization of 2-(N,N-Dimethylamino)ethyl Methacrylate

A kinetic model was developed to describe the atom transfer radical polymerization (ATRP) of 2(N,N-dimethylarnino) ethyl methacrylate (DMAEMA). The model was based on a polymerization mechanism, which included the atom transfer equilibrium for primary radical, the propagation of growing polymer radical, and the atom transfer equilibrium for the growing polymer radical. An experiment was carried out to measure the conversion of monomer, the number-average molecular weight of polymer and molecular weight distribution for the ATRP process of DMAEMA. The experimental data were used to correlate the kinetic model and rate constants were obtained. The rate constants of activation and deactivation in the atom transfer equilibrium for primary radical are 1.0 x 10(4) L(.)mol(-1.)s(-1) and 0.04 L(.)mol(-1.)s(-1), respectively. The rate constant of the propagation of growing polymer radical is 8.50 L(.)mol(-1.)s(-1), and the rate constants of activation and deactivation in the atom transfer equilibrium for growing polymer radical are 0.045 L(.)mol(-1.)s(-1) and 1.2 x 10(5) L(.)mol(-1.)s(-1), respectively. The values of the rate constants represent the features of the ATRP process. The kinetic model was used to calculate the ATRP process of DMAEMA. The results show that the calculations agree well with the measurements.

Thermal Decomposition Kinetics of Lead 2,4,6-Trinitroresorcinate Monohydrate

The non-isothermal decomposition of lead 2,4,6-trinitroresorcinate monohydrate, Pb(TNR)·H\-2O, was investigated by means of TG-DTA, DSC and IR. The thermal decomposition mechanism and the dissociated kinetics were also investigated. The kinetic parameters were obtained from the analysis of the DSC curves by integral and differential methods. The most probable kinetic model function of the dehydration reaction of \{Pb(TNR)·H\-2O\} was suggested by the comparison of the kinetic parameters.

Preparation and spectroscopic, and thermal decomposition kinetic studies of europium(Ⅲ) complex [Eu(HNBD)_3] (HNBD: 1-(6-hydroxy-1-naphthyl)-1,3-butanedione)

The complex of Eu（IH） with 1-（6-hydroxy- 1-naphthyl）- 1,3-butanedione （HNBD） was prepared for the first time and characterized by elemental analysis, IR, UV, fluorescence spectrum, and DTA-TG-DTG techniques. The IR and UV-visible spectra showed that Eu（Ⅲ） ion was coordinated to the HNBD ligand. The fluorescence spectrum showed the presence of Eu^3＋ characteristic emission. The TG-DTA-DTG curves showed that the thermal decomposition of the anhydrous complex was a two-stage process and the final residue was Eu2O3. The thermal decomposition kinetic parameters of the complex were evaluated from TG-DTG data by using three kinds of integral methods （Coat-Redfem equation, Horowitz and Metzger equation, Madhusudanan-Krishnan-Ninan equation）. The kinetic parameters of the first stage are E^＊ = 164.02 kJ.moll, A = 1.31 × 10^15 s^-l, AS^＊= 42.27 J·K^-l·mol^-l, △H^＊ = 159.51 kJ·mol^-l, △G^＊= 136.54 kJ·mol^-l, and n = 3.1, those of the second stage are E^＊= 128.52 kJ·mol^-l, A = 1.44× 106 s^-1, △S^＊= - 136.89 J·K^-l·mol^-l, △H^＊ = 120.41 kJ·mol^-l, △G^＊= 283.85 kJ·mol^-l, and n = 1.1.

NON-ISOTHERMAL KINETICS OF THERMAL DECOMPOSITION OF A NOVEL ANTITUMOR AGENT 4-{5-[3,4-DIMETHYL-5-(3,4,5-TRIMETHOXYPHENYL)THIOPHEN-2-YL]-2-METHOXYPHENYL}MORPHOLINE

The thermal decomposition of a new antitumor agent,4-{5-[3,4-dimethyl-5-(3,4,5-trimethoxyphenyl)thiophen-2-yl]-2-methoxyphenyl}morpholine was studied by Differential Scanning Calorimetry(DSC)and Thermogravimetry(TG)/Derivative Thermogravimetry(DTG)methods at a flow rate of nitrogen gas of 120 mL/min,The kinetic parameters were obtained from the analysis of the corresponding curves by Kissinger's method,Ozawa's method and the integral method,The results indicate that the apparent activation energy and pre-exponential constants of the decomposition reaction are 106.67 kJ/mol and 10^6.19s^(-1),respectively.

Procedure for Sensitive Kinetic Determination of Silver Based on Catalytic Effect on Ligand Substitution Reaction

A kinetic procedure for determination of trace silver was established based on the catalytic effect of Ag(Ⅰ) on the ligand substitution reaction between hexacyanoferrate (Ⅱ) and urea in acidic medium under the optimized conditions of [hexacyanoferrate]=8.0×10 -4 mol·L -1 , [CO(NH 2) 2]=6.0×10 -4 mol·L -1 , [CH 3COOH]=0.12 mol·L -1 , 80℃, 720 nm. The calibration curve is linear for 10～100 ng·ml -1 , and the detection limit is 0.4 ng·ml -1 Ag. The active energy of catalytic reaction is 18.12 kJ·mol -1 . The selectivity of this procedure is much better than that of other kinetic methods. Equal amount of mercury does not interfere with the determination of silver, and its sensitivity was also improved.

A novel kinetic procedure for the determination of iron in environmental samples

A novel kinetic procedure for the determination of trace iron(Ⅲ) was proposed based on the aerial oxidation of Gallocyanine by oxygen dissolved in water at pH 7 0. The calibration graph is linear for 0 05—0.6 μg/ml, and the detection limit is 0 01μg/ml (Fe). The present procedure is selective for iron(Ⅲ) and very easy to control compared with kinetic procedures for iron. It had been used to the determination of trace iron in environmental samples, and the results were satisfactory.