Electrocatalytic oxidation of hydrazine with pyrogallol red as a mediator on glassy carbon electrode

doi:10.1016/j.jelechem.2005.01.042

Journal of Electroanalytical Chemistry

Volume 583, Issue 2, 15 September 2005, Pages 176-183

https://doi.org/10.1016/j.jelechem.2005.01.042 Get rights and content

Abstract

The anodic oxidation of hydrazine has been studied on a glassy carbon electrode by electrocatalytic effect of pyrogallol red as a homogenous mediator, using cyclic voltammetry, linear sweep voltammetry and chronoamperometry as diagnostic techniques. Using cyclic voltammetry study showed that, the catalytic current of the system depends on the concentration of hydrazine. The magnitude of the peak current for pyrogallol red increased sharply in the presence of hydrazine, and proportional to hydrazine concentration. The diffusion coefficient of hydrazine was also estimated using chronoamperometry. The chronoamperometry studies also were used to determine the catalytic rate constant for catalytic reaction of pyrogallol red with hydrazine. The experimental results showed that the peak current varied in the presence of different metal cations, but these effects were omitted in the presence of EDTA, while almost all of anions had no effect on the peak current of hydrazine. The proposed method was used for analysis of hydrazine in real samples.

Introduction

Hydrazine is a substance anticipated to be carcinogenic, colorless, oily, and liquid, (H₄N₂), and a powerful reducing agent or electron donor. Derivatives of hydrazine are used as a rocket fuel, as corrosive inhibitors and as an oxygen scavenger in boilers [1]. They have been found application in industry, agriculture and other fields including the manufacture of metal films, photographic chemicals, explosives, insecticides and blowing agents for plastic [1]. Hydrazine can be absorbed through skin; effects blood production, causes liver and kidney damages [2]. Also hydrazine is very important in pharmacology, because it has been recognized as a carcinogenic and hepatotoxic substance [3]. In industrial applications, hydrazine is commonly used in place of sulfite in boilers as an oxygen scavenger and removes dissolved oxygen. Because the products of this reaction are water and nitrogen, the reaction adds no solid to the boiler water [4]. Therefore, the determination of hydrazine is of practical importance. Satisfactory techniques for the determination of specialty chemicals such as methods have been proposed for the determination of hydrazine must ideally be specific, reproducible, rapid, simple and sensitive. These include coulometry [5], titrimetry [6], amperometry [7], [8], ion-selective electrode [9], [10] and spectrophotometry [11]. Various experimental hydrazine sensors have been reported based on the detection of resistance change due to heat generated by catalytic oxidation of hydrazine [12]. Other methods such as spectrophotometric methods [13], [14], [15], [16] are based on the reaction of hydrazine with dimethylbenzaldehyde and n-dimethyl aminobenzaldehyde [14], [15] have been reported. These methods have a high limit of detection and low precision. The other methods use expensive instrumentation (diode array detectors) [16]. Hydrazine compound have a large oxidation overpotential at ordinary carbon electrodes and one approach for minimizing overvoltage effects is through the use of electrocatalytic process at chemically modified electrodes (CMEs) [3], electrochemically pretreated glassy carbon electrodes [17], carbon paste containing cobalt phthalocyanines [18], and inorganic mixed oxidation state Prussian blue [19], [20]. Macrocyclic transition metal complexes such as metal phthalocyanines [21], hemines [22] and tetra aza annulenes [21] have been proved to be efficient catalysts for the oxidation of hydrazine [23]. Despite the sensitivity and selectivity observed with chemically modified electrodes, the electrodes require regeneration to obtain a reproducible response [24].

Using linear sweep voltammetry [LSV] at fast scan rates is suitable for study of rapid electrochemical reactions. Pyrogallol red is known as a mediator at glassy carbon electrode. It has been found that pyrogallol red can catalysis the oxidation of hydrazine at surface of glassy carbon electrode, and the catalytic current depends on the concentration of hydrazine, though the magnitude of peak current for pyrogallol red (7.5 × 10⁻⁵ M) that occurs near 200 mV vs. SCE increased sharply in the presence of hydrazine, proportional to hydrazine concentration in the range of 5.0 × 10⁻⁶ to 5.0 × 10⁻⁴ M with a detection limit of 1.98 × 10⁻⁶ M.

Section snippets

Reagents

All chemicals used were reagent grade and doubly distilled water was used in preparation of all the solutions.

Pyrogallol red stock solution, (7.5 × 10⁻⁴ M), was prepared by dissolving 0.0157 g of the dye (Merck) in 50:50 ethanol/water in a 50-ml volumetric flask.

Hydrazine stock solution was prepared by dissolving 1.0497 g N₂H₄ · 2HCl (Merck) in water in a 50-ml volumetric flask.

A universal buffer (boric acid, phosphoric acid, acetic acid/sodium hydroxide) with different pH value was used for the

Electrocatalytic oxidation of hydrazine

Our experiments showed that pyrogallol red acts as a suitable intermediate for electron transfer in the oxidation of hydrazine at the surface of glassy carbon electrode. The pyrogallol red peak current increases sharply in the presence of hydrazine, and the peak potential of pyrogallol red is in lower potential than that of a hydrazine. Therefore, pyrogallol red was considered as a suitable homogenous electrocatalyst for hydrazine by electrochemical determination.

The proposed LSV method for the

Interference studies

The influence of various substances as potential interference compounds on the determination of hydrazine was studied under the optimum conditions with 4.0 × 10⁻⁵ M of hydrazine concentration. The tolerance limit was defined as the maximum concentration of the potential interfering substance causes an error less than 3% for determination of 4.0 × 10⁻⁵ M of hydrazine concentration. The results are given in Table 1, shows that the peak potential and peak current varies with different metal cations,

Real sample

To evaluate the applicability of proposed method, the recovery of hydrazine was determined in drinking and river water. The standard addition method was used for the analysis of prepared samples. The data given in Table 2, shows the satisfactory results.

Conclusion

The new voltammetric method for the determination of hydrazine is very rapid (less than 1 min per sample solution), reproducible, selective and sensitive and can be used for real sample analysis. The importance of the technique is its ability to electrocatalytic determination of hydrazine with pyrogallol red as homogenous electrocatalyst, while it does not need to prepare as for modified electrode. The independency of the system from the interferences, and the ability of removing the effect of

Acknowledgement

The authors wish to thank Isfahan University of Technology (IUT) Research Council and Center of Excellence in Chemistry (IUT) for support of this work.

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The adsorption behaviors and properties of hydrazine (N₂H₄) molecules on pristine and Li-decorated graphene sheets were investigated by means of first-principles based on density functional theory. We systematically analyzed the optimal geometry, average binding energy, charge transfer, charge density difference and density of states of N₂H₄ molecules adsorbed on pristine and Li-decorated graphene sheets. It is found that the interaction between single N₂H₄ molecule and pristine graphene is weak physisorption with the low binding energy of −0.026 eV, suggesting that the pristine graphene sheet is insensitive to the presence of N₂H₄ molecule. However, it is markedly enhanced after lithium decoration with the high binding energy of −1.004 eV, verifying that the Li-decorated graphene sheet is significantly sensitive to detect N₂H₄ molecule. Meanwhile, the effects of the concentrations of N₂H₄ molecules on two different substrates were studied detailedly. For pristine graphene substrate, the average binding energy augments apparently with increasing the number of N₂H₄ molecules, which is mainly attributed to the van der Waals interactions and hydrogen bonds among N₂H₄ clusters. Li-decorated graphene sheet has still a strong affinity to N₂H₄ molecules despite the corresponding average binding energy emerges a contrary tendency. Overall, Li-decorated graphene sheet could be considered as a potential gas sensor in field of hydrazine molecules.
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In another approach, conducting polymer modified electrodes have been prepared for sensitive determination of hydrazine [20–22]. Moreover, one of the most effective approaches is also the preparation of CMEs with various organic redox mediators which enhance electron transfer rate between electrode and hydrazine [23–33]. In the electrocatalytic oxidation of hydrazine using organic redox mediator modified electrodes, firstly hydrazine reacts with the oxidized redox mediator and it reduces to N2.
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Electrocatalytic oxidation of hydrazine with pyrogallol red as a mediator on glassy carbon electrode

Abstract

Introduction

Section snippets

Reagents

Electrocatalytic oxidation of hydrazine

Interference studies

Real sample

Conclusion

Acknowledgement

Anal. Chim. Acta

J. Electroanal. Chem.

Talanta

Anal. Chim. Acta

Anal. Chim. Acta

Microchem. J.

Anal. Chim. Acta

Electrochim. Acta

J. Electroanal. Chem.

Synth. Met.

J. Electroanal. Chem.

J. Electroanal. Chem.