Talanta 59 (2003) 253 /259 www.elsevier.

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Kinetic spectrophotometric determination of trace manganese (II) with dahlia violet in nonionic microemulsion medium
Qin Wei a,b,1, Liangguo Yan a, Guohua Chang a, Qingyu Ou b
a

School of Chemistry and Environmental Engineering, Jinan University, Jinan 250022, Peoples Republic of China b Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, Peoples Republic of China Received 18 May 2002; received in revised form 11 September 2002; accepted 11 September 2002

Abstract A new catalytic kinetic spectrophotometric method has been developed for the determination of trace amount of manganese (II) in nonionic microemulsion medium. The method is based on the catalytic effect of manganese (II) on the oxidation of dahlia violet by potassium periodate with nitrilotriacetic acid as an activitor in the presence of nonionic microemulsion. Under the optimum conditions, the calibration graph is linear in the range of 0.0004 /0.0056 mg ml (1 of manganese (II) at 580 nm. The detection limit achieved is 3.75 )/10 (5 mg ml (1. Manganese (II) in foodstuff samples was determined with satisfactory results. # 2002 Elsevier Science B.V. All rights reserved.
Keywords: Microemulsion medium; Manganese (II); Catalytic kinetic method; Dahlia violet

1. Introduction Manganese is both micronutrient as well as toxic element for living beings, depending on the concentration level. The metal plays important roles in biological system. It contributes to the formation of anterior pituitary hormone, vitamin B1 and C, affecting hematopoiesis, oxidation and proteometabolism in the body. Besides, many enzymes such as dipeptidase, arginase and phosphatase require manganese for proper function. However, an excess of manganese in food or pharmaceutics will be hazardous to human health.

1 Corresponding author. Tel./fax: '/86-531-712-0774 E-mail address: sdjndxwq@263.net (Q. Wei).

Therefore, it is necessary to establish sensitive and accurate analytical methods for quantitative determination of manganese. There are several methods available for manganese (II) determination including atomic absorption spectroscopy (AAS), flow-injection analysis (FIA), spectrofluorimetry [1] and spectrophotometry. In routine analysis, spectrophotometric methods are versatile and economical especially for developing countries. Such oxidants as potassium periodate and ammonium persulfate are commonly used for determination of manganese (II) by spectrophotometry [2 /6]. However, the methods mentioned above are time consuming or less sensitive. Catalytic kinetic methods have received considerable attention because of the significant advantages in the determination of

0039-9140/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved. PII: S 0 0 3 9 - 9 1 4 0 ( 0 2 ) 0 0 4 9 8 - 8

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many analytes at trace levels. At present, catalytic methods [7 /10] for the determination of manganese (II) in water systems have been frequently reported. Whereas, in microemulsion medium, the reaction dahlia violet /potassium periodate has never been reported for manganese (II) determination. Microemulsions are transparent or translucent, low viscosity, homogeneous and thermodynamically stable systems that are composed of surfactant, water, oil and cosurfactant at appropriate ratios. Compared with micellar system, microemulsion has lower surface tension and strong solubilization power to organic and inorganic substances [11]. In previous research, we introduced microemulsions for the first time into gasoline and directly determined additive elements in gasoline by spectrophotometry and flame AAS [12 /15]. In addition, we have first resolved the problem of stability in nephelometric analysis in microemulsion medium [16,17]. In the work, microemulsion with Tween-20 was efficiently used to enhance sensibility and stability of Mn(II)/dahlia violet /potassium periodate /nitrilotriacetic acid reaction system. Different variables that affect the reaction of dahlia violet with potassium periodate catalyzed by Mn(II) in microemulsion as well as detailed description of procedures are presented below. The proposed method is highly sensitive, selective and simple for the determination of trace Mn(II) without extraction and separation.

(1.0 mg ml (1) was prepared by dissolution of MnSO4 / H2O and further dilutions as required were employed. Nonionic microemulsion of polyoxyethene-20-sorbitan monolaurate (Tween-20) was prepared according to the mass ratio given as: Tween-20:n -butanol:n -heptane:H2O 0/ 4.75:4.75:0.5:90. Dahlia violet solution: 3.4 )/10(4 mol l (1. Nitrilotriacetic acid solution: 1.2 )/10(2 mol l (1. Potassium periodate solution: 5.0 )/10(3 mol l (1. KSCN solution: 1.0 mol l (1. Buffer solution of pH 4.6 was made by mixing appropriate volume of 0.2 mol l (1 acetic acid and 0.2 mol l (1 sodium acetate (1.4:1). 2.3. Recommended procedure Transfer 1.0 ml of 0.1 mg ml (1 manganese (II) solution into a 25 ml test tube and add 2.0 ml of buffer solution (pH 4.6), 3.0 ml of 1.2 )/10(2 mol l(1 nitrilotriacetic acid, 5.0 ml of 5.0 )/10(3 mol l(1 KIO4 solution, 2.0 ml of Tween-20 microemulsion and 2.0 ml of 3.4 )/10 (4 mol l (1 dahlia violet solution. Next, The volume was made up to 23 ml approximately with doubly distilled water and mixed well. Heat the solution for 14 min at 709/0.5 8C in a thermostat bath, then add 1.0 ml of 1.0 mol l (1 KSCN solution (reactive inhibitor). The solution was diluted to the mark with water and shaken the mixture thoroughly. Last, the solution was cooled to room temperature by running tap water, the absorbance of the solution in the catalytic system (A ), in which manganese (II) was added, was determined at 580 nm against water by using 1 cm quartz cell. A noncatalytic system was prepared in the same manner replacing manganese (II) solution with doubly distilled water. The absorbance of the noncatalytic system was labeled as A0. The log(A0/A ) value was calculated from A0 to A of the two determinations.

2. Experimental 2.1. Apparatus Absorbance measurements were made with a Shimadzu Model UV-3000 spectrophotometer using 1 cm quartz cells. A Model PHS-3C digital pH meter with a combined glass/calomel electrode was used for pH measurements. 2.2. Reagents All reagents used were of analytic grade unless specified otherwise. Solutions were made in doubly distilled water. A stock solution of manganese (II)

3. Results and discussion Dahlia violet is a dye and can be oxidized by KIO4. In the experiment, it was found that dahlia violet was slowly oxidized by KIO4 in acid media, whereas, the rate of oxidation strongly increased in

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Fig. 1. Absorption spectra of noncatalytic and catalytic reactions in different media against water; (1) noncatalytic reaction in Tween-20 microemulsion; (2) catalytic reaction in Tween-20 microemulsion; (3) noncatalytic reaction in Tween-20 micelle medium; (4) catalytic reaction in Tween-20 micelle medium; (5) noncatalytic reaction in water; (6) catalytic reaction in water. Condition: 1.2)/10 (3 mol l (1 nitrilotriacetic acid; 2.72)/10 (5 mol l(1 dahlia violet; 1.0)/10 (3 mol l (1 KIO4; 2.0 ml of buffer solution at pH 4.6; 2.0 ml of Tween-20 microemulsion and 0.004 mg of manganese (II) solution.

Fig. 3. Effect of amounts of KIO4 on reaction. Other conditions are the same as in Fig. 1.

quent experiments, since it enhanced the sensitivity and stability. 3.1. Effect of pH Buffer solutions of HAc /NaAc covering the range from 2.0 to 6.0 were used as the buffer media to investigate the effect of pH on the catalytic and noncatalytic systems as can be seen from Fig. 2. The log(A0/A ) increased with increasing pH up to about 3.8, whereas for pH/4.9 the log(A0/A) decreased. The log(A0/A ) was maximal and constant for pH values between 3.8 and 4.9. Thus, a pH of 4.6 was chosen in subsequent experiments. 3.2. Effect of amount of potassium periodate In terms of the experimental procedure, the amount of potassium periodate added was varied to find the optimum amount of the oxidant KIO4. The result was given in Fig. 3. The reaction rate log(A0/A ) of noncatalytic and catalytic reaction increased up to 4.0 ml and after that it was level over the range of 4.0 /7.0 ml. Greater amount of the reagent decreased the sensitivity. Thus, 5.0 ml of 5.0 )/10 (3 mol l (1 KIO4 was used in the rest of the study. 3.3. Inuence of amount of nitrilotriacetic acid The influence of nitrilotriacetic acid (1.2 )/10(2 mol l (1) as an activitor was studied in the volume range of 1.0 /5.0 ml. Fig. 4 indicates that the

Fig. 2. Effect of pH on reaction. Other conditions are the same as in Fig. 1.

the presence of trace amounts of manganese (II), and nitrilotriacetic acid as an activitor. Fig. 1 shows the absorption spectra of catalytic and noncatalytic systems in different media. From Fig. 1, it was found that the absorbance of each system reached maximum at 580 nm. Hence, 580 nm was selected for further studies. At the maximum wavelength 580 nm, the log(A0/A ) values of catalytic reactions in microemulsion, micelle and water were 0.48, 0.32 and 0.18, respectively. Microemulsion was used in subse-

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In Fig. 5, the maximum and constant log(A0/A ) value was obtained between 1.0 and 2.5 ml of 3.4 )/10 (4 mol l (1 dahlia violet. Hence, an addition of 2.0 ml was selected for further studies. 3.5. Reaction time, rate constant and half-life Under the optimum conditions used, the influence of reaction time on both catalytic and noncatalytic reaction was examined carefully. The results showed that the log(A0/A ) value between noncatalytic and catalytic reactions had a linear relationship with time (from 4 to 14 min). The corresponding linear regression equation was calculated:   A log 0 00:0284)t (min)'0:0824 A (r00:992) Therefore, the reaction time selected was 14 min. The rate constant and half-life were, respectively:   1 A K 0 ln 0 0 0:0790 (min(1 ) (t: min) (1) t A t1=2 0ln
Fig. 5. Effect of amounts of dahlia violet on reaction. Other conditions as in Fig. 1.

Fig. 4. Effect of amounts of nitrilotriacetic acid on reaction. Condition: 2.72)/10 (5 mol l (1 dahlia violet; 1.0)/10 (3 mol l (1 KIO4; 2.0 ml of buffer solution at pH 4.6; 2.0 ml of Tween20 microemulsion and 0.004 mg of manganese (II) solution.

2 0 8:78 (min): K

oxidation reaction was accelerated obviously by nitrilotriacetic acid and the log(A0/A ) remained constant and maximal after the addition of 2.0 /4.0 ml of nitrilotriacetic acid. Thus, 3.0 ml of 1.2 )/ 10(2 mol l (1 nitrilotriacetic acid was recommended. 3.4. Effect of amounts of dahlia violet According to the above procedure, the effect of amounts of dahlia violet (3.4 )/10(4 mol l (1) was studies by varying the volume of dahlia violet (Fig. 5). It was observed that the reaction rate of catalytic and noncatalytic reaction increased with increasing dahlia violet volume, however, for catalytic reaction the influence was more pronounced.

3.6. Reaction temperature and apparent activation energy Under the conditions described above, the influence of temperature on the two reactions (catalytic and noncatalytic reactions) was investigated and the results showed that the sensitivity increased quickly upon 35 8C. During 45/80 8C, the reaction rate increased linearly with increasing temperature. In order to ensure enough the sensitivity and make experimental manipulation easier, 70 8C was thus selected for all experiments. According to a reported method [18], using Arrhnius equation, a line was constructed by plotting (/log[log(A0/A )] versus 1/T (T is the temperature) at temperature between 45 and 80 8C and its linear regression equation was expressed as:

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Table 1 Tolerance limit of foreign ions in the determination of 0.1 mg manganese (II) Foreign ions Zn2' Cu2' Ni2' Pb2' Hg2' Ag ' PO3( 4 Ca2' 2' Co Cd2' W6' Cr6' Ti6' Ba2' Al3' Mg2' Fe3' Tolerance limits (mg) 250 250 250 250 250 250 250 265 7 380 100 70 70 70 20 20 20

and b is the slope of the linear calibration equation. 3.8. The method of terminating reaction In most cases, running water was usually used to terminate reaction. However, in the experiment, running water could not control the reaction. On the basis of many experiments, we found that KSCN as a termination agent could effectively terminate the reaction. The system remained stable for no less than 70 min after the addition of 1.0 ml of 1.0 mol l(1 KSCN solution. 3.9. Interference study The possible influence of the other ions on the catalytic determination of Mn(II)/(0.1 mg) by this method was investigated. With a relative error of less than 5%, the tolerance limits for various foreign ions are listed in Table 1. The results indicated that metallic ions frequently encountered in samples were tolerated on the whole in relatively high concentration. The sample analysis could be carried out without any masking reagent. Thus the proposed method is highly selectivity.

  A 1 (log log 0 00:053)104 ) (1:23 T A  (T: 4580  C) r0 0:995: Then, from its slope, the apparent activation energy calculated was 10.2 kJ mol (1. 3.7. Calibration graph, precision and detection limit After optimization of the experimental parameters, a series of standard manganese solutions were tested. A linear calibration graph was obtained within the concentration range of 0.0004 / 0.0056 mg ml(1 Mn2'. The corresponding regression equation was as follows:   A log 0 0 120:75rMn2' (mg ml(1 )'0:0144 A (r 00:993) where rMn2' is the manganese (II) concentration expressed in mg ml (1. The standard deviation (s) was 1.51 )/10(3 obtained from a series of 11 replicate determinations of the blanks. The detection limit (c ) of the method calculated from the equation c0/3s/b was 3.75 )/10(5 mg ml(1, where c is the detection limit

4. Analytical application 4.1. Analysis of vegetable samples Prior to the determination, the vegetable samples were pretreated in the following way. An edible portion of vegetable was firstly washed clean with tap water and then rewashed with deionized water. After removing deionized water on the surface of vegetable, the sample was cut into small pieces and dried at 65 8C in oven. Then the sample was ground and passed through a 60mesh sieve. The powdered sample (0.5 g) was accurately weighed and placed in a 100 ml beaker followed by the addition of nitric acid and excess of hydrochloric acid (1:3), 10 ml of concentrated nitric acid (1:1). The mixture was digested by heating and evaporated carefully nearly to dryness, a little of water was added, and evaporated again. Finally, the residue was dissolved in water

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Table 2 Determination of manganese (II) in vegetable samples Sample Potato Cucumber Eggplant Lettuce Found (n0/7, mg g (1) 6.24 3.18 8.47 4.20 R.S.D. (%) 2.5 2.8 3.4 1.8 Mn added (mg) 0.0200 0.0200 0.0200 0.0200 Mn recovered (mg) 0.0208 0.0192 0.0190 0.0206 Recovery (n0/5, %) 104 96.0 95.0 103

Table 3 Determination results of manganese (II) in some foodstuff samples Sample AAS (n0/7, mg g (1) 2.62 1.60 7.24 8.30 12.20 11.80 285.20 1.21 Found (n 0/7, mg g (1) 2.62 1.64 7.30 8.31 12.80 11.30 283.40 1.25 R.S.D. (%) Mn added (mg) Mn recovered (mg) Recovery (n 0/5, %) 101 99.5 94.3 95.0 103 107 103 95.7 Ft -testa valuea 1.96 3.26 3.45 2.49 1.30 1.56 1.78 1.98 0 1.43 0.538 0.0745 1.77 2.07 0.476 1.92

Wheat Rice Mung bean Horsebean Earthpea Chinese date Tea Charqui

2.4 2.2 1.9 2.3 3.2 3.5 2.1 3.6

0.0200 0.0200 0.0300 0.0300 0.0300 0.0300 0.0200 0.0300

0.0202 0.0199 0.0283 0.0285 0.0310 0.0320 0.0206 0.0287

a The t - and F -values refer to comparison of the proposed method with AAS. The theoretical values at 95% confidence limits: F 0/ 4.28, t 0/2.18.

and the pH value of the solution was adjusted to 4. The solution was brought to 50 ml in a calibrated flask with water. A portion of the solution and the stock solution of Mn(II) were transferred into a 25 ml test tube, then the absorbance was measured at 580 nm for manganese (II). 4.2. Analysis of foodstuff samples All foodstuff samples were dry. Each sample was first ground in a mortar. Then 1.0 g of sample (0.1 g of tea) was weighed accurately and placed in a porcelain crucible. After being charred on an electric furnace, the sample was ashed at 550 8C in a muffle furnace. Then 2 ml of HCl and 10 ml of water were added into the ash. The sample was heated below the boiling point for a moment. The solution was cooled and diluted to 100 ml with water in a

calibrated flask and mixed well. At last, a suitable amount of the sample solution and the stock solution of Mn(II) were added into 25 ml test tube for the determination of manganese (II) by the recommended procedure. The recovery studies were performed for each sample by adding the standard Mn(II) solution to the test tube. The samples were also analyzed without microemulsion by atomic absorption spectrometry (AAS). As can be seen from Tables 2 and 3, the recovery of manganese (II) was 94/107% and the relative standard deviations were in all instances less than 3.6%. Comparing the results obtained by the proposed method with those of the AAS using the t- and F -values, the calculated values did not exceed the corresponding theoretical values, indicating insignificant differences between the results. The results are in good agreement with those obtained by AAS performed for comparison.

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5. Conclusion The new approach proposed in this paper is simple, selective and very sensitive for the determination of low ranges of manganese (II) in the presence of Tween-20 microemulsion without the need for preconcentration step. The method can be satisfactorily applied to the determination of Mn(II) in various foodstuff samples.

Acknowledgements The comments of the unknown reviews are great helpful. The nancial support of Shandong Provincial Natural Science Foundation (Y 2000B09) is gratefully acknowledged.

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