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Substitution of Mercury Electrodes by Bismuth-Coated ScreenPrinted Electrodes in the Determination of Quinine in Tonic Water
Arstides Alberich, Nur ia Serrano, Jose Manuel Daz-Cruz, Cristina Arino, and Miquel Esteban*
Departament de Qumica Analtica, Facultat de Qumica, Universitat de Barcelona, Mart i Franques 1-11, E08028 Barcelona, Spain
S Supporting Information *

ABSTRACT: The bismuth-coated screen-printed electrode is shown to be a suitable and safe alternative to the classical mercury electrode in the voltammetric determination of quinine in tonic water. This experiment is appropriate for undergraduate analytical courses as it helps students understand the fundamentals of electroanalysis using preplated screenprinted electrodes and the importance of green electrochemistry. Student interest is piqued by using a familiar real-world sample, tonic water.

KEYWORDS: Upper-Division Undergraduate, Analytical Chemistry, Laboratory Instruction, Safety/Hazards, Hands-On Learning/Manipulatives, Electrochemistry, Food Science, Green Chemistry, Instrumental Methods, Quantitative Analysis

uantitative analysis by voltammetry is a typical experiment that can help undergraduate chemistry students understand the fundamentals and the analytical applications of electrochemistry. However, most academic institutions are reticent to maintain these experiments in their curricula because mercury electrodes are used. The risk of toxicity that working with mercury entails has led to proposals for the removal of mercury-containing devices, ranging from thermometers to vacuum lines, from educational laboratories.15 In the case of working electrodes, many compounds can be measured using nontoxic electrodes such as glassy carbon, gold, platinum, and so forth, and these electrodes are particularly useful for designing Hg-free voltammetry experiments. Although these electrodes are well suited to the oxidation of analytes, they are not suited for reduction processes, that is, the main application of the mercury electrodes. The quantication of quinine in tonic water by means of voltammetric analysis employing a static mercury drop electrode (SMDE) has been successfully carried out at our institution for many years.6 In addition to the primary goal of teaching the procedures of voltammetric quantication, quinine provides a good example of the electrochemical reduction mechanisms of organic substances, and the results can also be compared with those obtained from uorometric analysis.7 With the objective of making our laboratories safe, a number of nal-year undergraduate students conducted the quantication of quinine using a screen-printed carbon electrode coated with a bismuth lm (Bi-SPCE). The overall goal was to incorporate the procedure within an experimental course for advanced students in analytical chemistry. Bismuth lm
2013 American Chemical Society and Division of Chemical Education, Inc.

electrodes have the advantage of being environmentally friendly while providing electrochemical features that are very similar to those of mercury, which accounts for their use over the past decade.8 Various attempts have been made to use bismuth in the determination of metals typically measured with a mercury electrode,5,9 but to the best of our knowledge its use for quantifying organic compounds has not been recommended before by any article in the science education literature. Screenprinted electrodes have been used in low-cost cyclic voltammetry experiments10 and for examining metal electrodeposition and Faradays law.11 The proposed changesthe electrode type and the electrode materialare not trivial as is evidenced by the fact that in both the educational and the scientic literature phenolic compounds are the only organic substances analyzed using a Bi-SPCE.12 The experiment proposed here provides students with three learning outcomes: Learning how to coat the electrode substrate with a bismuth lm, thereby gaining rsthand experience in the preparation of preplated electrodes. Introducing the use of screen-printed electrodes, carrying out the determination with a single strip comprising an integrated three electrode (working, counter, and reference) device. This outcome is important as screenprinted electrodes allow measurements to be taken in the eld, which is an increasingly important trend in electroanalysis.
Published: November 15, 2013
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dx.doi.org/10.1021/ed400288a | J. Chem. Educ. 2013, 90, 16811684

Journal of Chemical Education Scheme 1. Reduction Mechanism of Quinine

Laboratory Experiment

Acquiring knowledge about the reduction mechanisms of organic substances. In addition, it should be noted that the modication proposed for this laboratory experiment does not represent an increase in costs, as the instrumentation used with an SMDE can also be used for the SPCE measurements simply by connecting the electrode to the potentiostat via a new exible cable. Furthermore, the initial outlay (not great) in purchasing the disposable screen-printed carbon electrodes is counterbalanced by the savings made from not having to acquire mercury and to treat the toxic waste.

Preparation of the Bismuth Film

THEORY Quinine is a natural alkaloid with a bitter taste that can be added to certain beverages, including tonic water and bitter lemon. Given the numerous reports detailing health problems related to quinine intake, its use is regulated in some countries. For example, the U.S. Food and Drug Administration (FDA) limits the quinine content in tonic water to 83 ppm.13 The determination of quinine has been previously described in this Journal using such methods as molecular uorescence spectroscopy,1416 capillary electrophoresis,17,18 and even visually.19 As the quinine molecule contains an aromatic quinoline fused ring, it can be reduced electrochemically at pH values that are not too high (Scheme 1) and then determined by voltammetry. This reaction is favored by the subsequent equilibrium in which a water molecule is split o by elimination.

A 0.2 mol L1 acetic acid/acetate buer (pH = 4.5) with 100 ppm Bi(III) solution was used to deposit the lm on the carbon disk of the screen-printed sensor. The SPCE was connected to the potentiostat and immersed in 20 mL of the solution in an electrochemical cell. Care was taken to ensure that the liquid just covered the three electrodes but did not come into contact with the exible cable (which was further protected by wrapping it in a paran lm). After deaerating the solution for 5 min, the bismuth lm was prepared in accordance with the procedure shown in Table 1. Once the bismuth lm was deposited, the screen-printed was rinsed carefully with water. This methodology provided very high repeatability and reproducibility.22 Table 1. Experimental Parameters
preparation of the bismuth lm parameter value deposition potential 0.80 V deposition time 300 s (with stirring) rest time 20 s (without stirring) dierential pulse voltammetry parameter value initial potential 1.10 V nal potential 1.65 V step increment 0.005 V step amplitude 0.050 V pulse time 0.05 s voltage step time 1s

EXPERIMENTAL SECTION

Reagents and Instrumentation

Concentrated sulfuric acid, concentrated acetic acid, sodium hydrogen phosphate, sodium dihydrogen phosphate, and sodium acetate were obtained from Fluka. Quinine sulfate and bismuth(III) nitrate pentahydrate were obtained from Sigma-Aldrich. Reagent grade chemicals were used for the bulk of the work as this quality provides good results. Deposition of the bismuth lm and measurements by dierential pulse voltammetry (DPV) were performed on a 757 VA Computrace (Metrohm) attached to a personal computer with data acquisition software also obtained from Metrohm. Bismuth screen-printed electrodes were prepared by coating a bismuth lm on the carbon disk (4 mm diameter) of a three-electrode screen-printed sensor (ref DPR-110, Dropsens). Each Bi-SPCE consists of a bismuth lm working electrode, a silver reference electrode, and a carbon counter electrode. The electrode was connected to the potentiostat using a exible cable (ref CAC, Dropsens). Both the screenprinted carbon electrodes and the exible cable can be purchased at the Dropsens web site,20,21 although other brands are available. All measurements were conducted in a glass cell at room temperature, and deaeration was achieved with nitrogen.
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Voltammetry

Prior to performing the measurements, the following steps were conducted: (i) the tonic water was degassed by magnetic stirring, thus eliminating the CO2 in the sample, (ii) a 0.2 mol L1 phosphate buer solution was prepared with a pH value of 7.0, and (iii) a 100 ppm standard solution of quinine in 0.05 mol L1 sulfuric acid was prepared. Once the electrode had been coated, the Bi(III) solution was removed from the cell and 20 mL of the phosphate buer solution was transferred via a class A transfer pipet. As usual, when bismuth electrodes are employed, there is no need to degas the cell solution. After adjusting the experimental parameters listed in Table 1 and ensuring the blank measure was satisfactory, 2 mL of the tonic water sample was added to the buer solution in the cell (also an exact volume) and a voltammogram was recorded. Standard additions of 0.4 mL of quinine solution and data collection were repeated until the desired number of additions (typically 34) was completed. A micropipet was used to make the additions, but a microsyringe would work equally well. Ideally, at least three determinations for the same sample of quinine should be performed and dierent tonic waters brands can be analyzed.
dx.doi.org/10.1021/ed400288a | J. Chem. Educ. 2013, 90, 16811684

Journal of Chemical Education

Laboratory Experiment

Figure 1. (A) Voltammograms from a quinine tonic water sample and four successive standard additions of quinine. (B) A representative data set of quinine peak height vs the total concentration of quinine added to the sample.

HAZARDS Sulfuric acid and acetic acid can cause severe skin burns and eye damage. Quinine sulfate and bismuth nitrate can cause skin, eye, and respiratory irritation. Moreover, acetic acid is ammable and bismuth nitrate may intensify re. RESULTS The Bi-SPCE exhibits a well-behaved response to quinine in tonic water samples. A single peak was clearly identied at 1.44 V (Figure 1A), the intensity of which increased with subsequent standard additions. No other peaks were observed in the working potential range used. The determination of quinine in tonic water was performed using the standard addition method (Figure 1B), plotting the absolute value of the individual peak current (y axis) against the total concentration of quinine added and adjusting the dilution factor (x axis). The peak height values were automatically measured by the software, but alternatively, the baseline can be drawn by hand and the peak heights then measured. The quinine concentration in the sample was determined from the absolute value of the x intercept of the linear t. Note that the standard addition was performed with just one screen-printed electrode. However, the screen-printed electrode is replaced for every replicate. In fact, the same Bi-SPCE might be reused for dierent replicates, but given that the surface of the electrode is a source of variability, we think that it can be minimized when preparing a new bismuth lm, in a new screen-printed electrode, for each determination. The quinine concentration data obtained by an undergraduate student from the determination of three replicates performed using a Bi-SPCE can be seen in Table 2. Here, the average content of quinine in the tonic water was 73 (3) ppm, a value comparable to the results obtained with a static mercury drop electrode.

Table 2. Student Data of the Determination of Quinine Performed with a Bi-SPCE


current (A) for each replicate Vquinine added (mL) 0 0.4 0.8 1.2 1.4 quinine content R2 Cquinine added (ppm) 0 1.83 3.60 5.31 6.96 1 0.60 0.81 0.96 1.11 1.26 73 0.997 2 0.58 0.79 0.90 1.07 1.24 71 0.993 3 0.62 0.82 0.94 1.10 1.27 76 0.995

DISCUSSION To evaluate the substitution of mercury electrodes with bismuth-coated screen-printed electrodes in the determination of quinine in tonic water, the experiment was performed by a pilot group of three pairs of students who compared the main analytical features of the Bi-SPCE and the SMDE. The average quinine contents determined were very similar for both electrodes (74 ppm for Bi-SPCE and 73 ppm for SMDE); however, the average relative standard deviation was somewhat
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higher for the Bi-SPCE (4.1% vs 2.5%, respectively). This dierence could be attributed to the greater variability introduced when dierent bismuth lms are coated in comparison to the mercury drop electrode, which is always more regular in its characteristics. Despite the slightly worse standard deviation, the use of the nontoxic electrodes provides considerable advantages. Determination of quinine in tonic water using a Bi-SPCE could be implemented in a course in which 2024 students (working in pairs) rotate through a set of established laboratories in dierent branches of analytical chemistry. In our institution, the course is recommended for third-year undergraduates. For classes in which instructors do not prepare any solutions beforehand, a four-hour period is sucient to complete the set of three determinations, including the bismuth lm formation step. Even though the use of a Bi-SPCE in substitution of an SMDE requires completing this preliminary stage, the experimental procedures are otherwise similar in the time requirements. Moreover, students are given the chance to learn how to prepare a preplated electrode. Thus, students are exposed to some of the essential problems of experimental analytical chemistry, including the application of dierent electrochemical techniques and the undertaking of a determination by standard addition with a real-world sample, which makes the experiment more attractive and relevant to the students. Finally, the experiment presents new educational values regarding the replacement of classical methods with a greener electrochemistry and shows students how screenprinted electrodes can facilitate on-site measurements for a realworld problem.
dx.doi.org/10.1021/ed400288a | J. Chem. Educ. 2013, 90, 16811684

Journal of Chemical Education

Laboratory Experiment

ASSOCIATED CONTENT

S Supporting Information *

Notes for the instructors; student handout. This material is available via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION

Corresponding Author

*M. Esteban. E-mail: miquelestebanc@ub.edu.


Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS The authors acknowledge nancial support from the Spanish Ministerio de Ciencia e Innovacion (MICINN, project CTQ2009-09471) and from the Spanish Ministerio de Economia y Competitividad (MCOC, project CTQ201232863). REFERENCES

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