Determination of Cu (II) ions using sodium salt of 4-phenylsemicarbazone 1,2-naphthoquinone-4-sulfonic acid in natural and industrial environments
© Zagurskaya-Sharaevskaya and Povar. 2015
Received: 22 July 2015
Accepted: 8 December 2015
Published: 14 December 2015
The copper content in natural waters usually range from 0.2 to 30 μg/L. The higher concentrations are habitually found in industrial effluents and other contaminated waters.
This work develops the spectrophotometric method of determination of copper (II) microgram amounts with a new reagent - sodium salt of 4- phenylsemicarbazone 1,2-naphthoquinone-4-sulfonic acid (L), used as a ligand for a new coordination compound of copper (II). The complex formation is accompanied by color change, allowing use of this property for quantitative determination of copper (II) ions in various objects such as: alloys, superconducting ceramics and tap water. The determination of copper (II) ions has been carried out by voltammetric and spectrophotometric methods.
The complex of composition CuL is stable within the pH range from 5.74 to 6.51. Its stability constant is logβ = 4.53. The molar absorption coefficient of the complex has been found. Both methods give the same concentration of about 0.0400 mg/L of copper (II) in tap water, ceramics, and alloys. The detection limit of the spectrophotometric determination of copper (II) ions in the presence of the main metal ions in tap water is 0.012 mg/mL.
The advantages of this method are the simplicity of the synthesis of reagent, its ease of recrystallization from water-ethanol solution, and stability in the crystalline state.
The diversity of chemical industries, a large number of chemical products (initial, intermediate, and final) used and produced in manufacturing processes, cause the formation of wastewater contaminated with organic and inorganic substances of very different composition and volume (Qadir et al. 2015). Among heavy metals, despite its less-significant toxicity, copper has become a widely distributed pollutant in natural water as a result of the dumping of electronic trash and mining residues (Zhang et al. 2014).
Cu constitutes an essential micronutrient for plants (photosynthetic electron transport, metabolism of carbohydrates) and animals (pigmentation, nucleic acid, protein metabolism, integrity of immune system) (Courchesne et al. 2006). Concomitantly, copper belongs to the trace elements necessary for human life. Cu (II) is the third most abundant transition-metal ion in the human body (after Fe (III) and Zn (II) and is essential for many biochemical and physiological functions (Chandrasekhar et al. 2012). Its excess and deficiency lead to serious consequences such as: malfunction of the liver, neurological disorders, deterioration of connective and bone tissues, and heart diseases (Yee and Goodwin 1974). At high concentrations, the essential trace metal Cu can become highly toxic to plants and microorganisms (e.g., Aoyama and Nagumo 1997, Hattori 1992, Kraal et al. 2006). The toxicity of Cu in soils depends on the mobility and thus (bio) availability of the metal. The high copper concentration can also cause acute disorder of the gastrointestinal tract, which is accompanied by nausea, vomiting, and diarrhea. The concentration of copper in lakes and rivers ranges from 0.5 to 1.000 ppb with an average concentration of 10 ppb. The average copper concentration in groundwater (5 ppb) is similar to that in lakes and rivers; however, monitoring data indicate that some groundwater contains levels of copper (up to 2.783 ppb) that are well above the standard of 1.300 ppb for drinking water (ATSDR 2004). Supplementary data can be found in the papers (Pesavento et al. 2004, Shengbiao et al. 2003).
The sodium salt of 4-phenylsemicarbazone 1,2-naphthoquinone-4-sulfonic acid reactant is an original synthesized reagent, used as a ligand for obtaining new coordinative compounds, which is important for the life ions as copper (II). Complex formation is accompanied by a color change, allowing the use of this property for analytical purposes for quantitative determination of copper (II) ions in various objects such as: alloys, superconducting ceramics as well as tap water.
Currently, for the determination of copper (II) ions, a variety of reagents and techniques is used (Ulmanu et al. 2007; Dharmarajan et al. 2004). According to the literature (Ramanjaneyulu et al. 2008), the existing reagents for the photometric determination of copper permit detection of 0.025 to 30 μg/mL Cu. For example, one of the most frequently used reagents for the determination of copper (II) ions is diethyldithiocarbamate, which the detection limit is 0.1 μg/L.
This paper deals with the application of a novel reagent, the sodium salt of 4-phenylsemicarbazone 1,2-naphthoquinone-4-sulfonic acid, for determination of copper (II) ions in tap water, copper containing alloys and superconducting ceramics. The aim of this work is the use of a new reagent for quantitative determination of copper (II) ions in water and industrial objects, establishing optimum conditions for complex formation of copper (II) ion with a synthesized ligand, as well as the elucidation of the detection limit of copper (II) ions in tap water, and superconducting ceramics. This new reagent has proved to be suitable for quantitative spectrophotometric determination of copper (II) ions in objects of natural and industrial environments.
The solution of the organic reagent, the sodium salt of 4-phenylsemicarbazone 1,2-naphthoquinone-4-sulfonic acid (L), was prepared by dissolving its necessary sample amount in a small volume of 96 % ethanol and then diluting it in distilled water; the concentration of the reagent in solution was 2°10−3 mol/L. Solutions of copper (II) were prepared by dissolving samples of Cu(NO3)2°3H2O of analytical grade of purity in distilled water and subsequent dropwise adding a solution of nitric acid for suppression of hydrolysis (pH ≈ 1). Working solutions were prepared from batches of superconducting ceramics and bronze alloys, dissolving them in nitric acid and diluting with distilled water. The titers of solutions were adjusted by complexometric method in the presence of xylenol orange and iodometric method. The acetate buffer was prepared from CH3COOH and CH3COONa (pH ≈ 5.5). The optical density was measured with the use of spectrophotometer SF-46 (LOMO, Russia); the pH of solutions was measured by the potentiometer—121 with a glass electrode.
For the selection of the pH range, in which the absorbance value was maximal, different pH buffers were tested (bi-phthalate, acetate, oxalate, and borate). The maximum yield of the complex matched the use of acetate buffer solution with pH from 5.74 to 6.51. In strongly acidic solutions, the complexes do not reach their maximum output, since the value of the absorption decreases.
Calculation of error for the calibration curve (P = 0.95, t = 3.18)
C · 10−5, mol/L
Mass m i , g
Confidence interval d i
Standard error (SE) of arithmetic mean S
Mean square error Δ
m m ± δ
0.0027 ± 0.0002
Analytical version of the method
The Komar method for Cu:L relative to L for acetate buffer
V Cu, mL
C Cu × 10−5, mol/L
V L , mL
C L × 10−5, mol/L
ε (L mol−1cm−1) × 105
Determination of amount of Cu2+ in superconducting ceramics
The solution of superconducting ceramic was prepared by accurately weighing and dissolving in a small volume of nitric acid and diluting with acetate buffer; a portion of solution (10.0 mL) was diluted in a 50.0-mL flask, then a 10-fold excess of ligand was added. The absorbance was measured relative to ligand solution in acetate buffer at a wavelength of 520 nm.
Determination of Cu2+ in bronze BrAZhMts (used standard on the chemical composition is GOST 18175–78)
Composition of bronze: 83–88 % Cu, 9–11 % Al, 2–4 % Fe, 1–2 % Mn.
The solution of bronze is prepared by the accurate mass measurement. For determination, a series of solutions with different contents of copper, and the same concentration of the ligand (a 10-fold excess) in acetate buffer mixture was prepared. The absorbance was measured relative to ligand solution in acetate buffer at a wavelength of 520 nm.
Determination of amount of Cu2+ in tap water
Content of copper in objects (Р = 0.95)
0.2720 ± 0.0041 g
0.1037 ± 0.0053 g
0.0396 ± 0.0004 mg/L
The content of copper (II) ions was determined by the spectrophotometric method. The maximum of absorption of the complex (1:1) is observed at a wavelength of 500 nm. The complex Cu:R is stable in the pH range from 5.74 to 6.51. Using the Komar method, the logarithm of the stability constant, logβ = 4.53, was calculated. The molar attenuation coefficient is of 3 · 104 L · mol−1 cm−1. The Beer–Lambert–Bouguer law complied within the concentration range of 0.3 · 10−6 to 4.0 · 10−5 mol/L (A = 30094.2 Ci + 0.07). The data are presented in Table 3.
The spectrophotometric determination of the copper content using the sodium salt of 4-phenylsemicarbazone 1,2-naphthoquinone-4-sulfonic gives 0.0396 mg/L. In this case, the detection limit is 0.012 mg/mL. The obtained results allow recommending this reagent for the spectrophotometric determination of copper (II) ions in tap water. The ions of iron, magnesium, calcium, sodium, and potassium (at concentrations not exceeding 1.0 · 10−2 mol/L) do not interfere with these measurements. The ions lead, bismuth, and mercury (II) at concentrations of 1.0 · 10−5 mol/L and above have been found to affect measurements.
In conclusion, we have reported a spectrophotometric method of the determination of copper (II) microgram amounts with a new compound, sodium salt of 4- phenylsemicarbazone 1,2-naphthoquinone-4-sulfonic acid (L), used as a ligand for an original coordination compound of copper (II). The stability constant of the complex of composition CuL has been determined. The molar absorption coefficient of the complex has been established.
Data obtained by the spectrophotometric measurement of copper (II) amounts have been compared with those obtained by voltammetric method. Both methods give the same concentration of about 0.0400 mg/L of copper (II) in tap water, ceramics, and alloys. The detection limit of the spectrophotometric determination of copper (II) ions in the presence of the main metal ions in tap water has been found to be 0.012 mg/L. The main advantages of the developed method are the simplicity of the synthesis of reagent, its ease of recrystallization from water-ethanol solution, and stability in the crystalline state.
In the next work, we are also going to examine if the synthesized reagent has no detrimental effect in biological systems, which would allow its potential use for in vivo applications.
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- Aoyama M, Nagumo T (1997) Comparison of the effects of Cu, Pb, and As on plant residue decomposition, microbial biomass, and soil respiration. Soil Sci Plant Nutr 43:613–622View ArticleGoogle Scholar
- ATSDR (2004) Toxicological profile for copper (update). Agency for Toxic Substances and Disease Registry, Atlanta, GeorgiaGoogle Scholar
- Bulatov МI, Kalinkin IP (1986) Practical guide of photometric methods of analysis. Khimiya, Leningrad (in Rus)Google Scholar
- Chandrasekhar V, Das S, Yadav R, Hossain S, Parihar R, Subramaniam G, Sen P (2012) Novel chemosensor for the visual detection of copper (II) in aqueous solution at the ppm level. Inorg Chem 51(16):8664–8666View ArticleGoogle Scholar
- Courchesne F, Kruyts N, Legrand P (2006) Labile zinc concentration and free copper ion activity in the rhizosphere of forest soils. Environ Toxicol Chem 25(3):635–642View ArticleGoogle Scholar
- Dharmarajan S, Yogeeswari P, Thirumurugan R (2004) Antituberculous activity of some aryl semicarbazone derivatives. Bioorganic Med Chem Lett 14(15):3923–3924View ArticleGoogle Scholar
- Hattori H (1992) Influence of heavy-metals on soil microbial activities. Soil Sci Plant Nutr 38:93–100View ArticleGoogle Scholar
- Kraal P, Jansen B, Nierop KG, Verstraten JM (2006) Copper complexation by tannic acid in aqueous solution. Chemosphere 65(11):2193–2198View ArticleGoogle Scholar
- Maslyuk V.A., Kayuk V.G., Smirnov V.P. (1992) ‘The effect of adhesion-active substrates on the structure formation and properties of laminated materials consisting of the hard alloy KKhNF15 and steel’ In: Science and Technology, Central Eurasia: Materials Science, JPRS Report, p.11.
- Pesavento M, Biesuz R, Alberti G, Profumo A, D’Agostino G (2004) Speciation of copper(II) in natural waters in the presence of ligands of high and intermediate strength. Chem Speciat Bioavailab 16(1–2):35–43View ArticleGoogle Scholar
- Qadir M, Javier MS, Blanca J (2015) Environmental risks and cost-effective risk management in wastewater use systems. In: Wastewater. Springer, Netherlands, pp 55–72Google Scholar
- Ramanjaneyulu G, Reddy PR, Reddy VK, Reddy TS (2008) Direct and derivative spectrophotometric determination of copper (II) with 5-bromosalicylaldehyde thiosemicarbazone. Open Anal Chem J 2:78–82View ArticleGoogle Scholar
- Shengbiao H, Zijian W, Mei M (2003) Measuring the bioavailable/toxic concentration of copper in natural water by using anodic stripping voltammetry and Vibrio-qinghaiensis sp. Nov.-Q67 bioassay. Chem Speciat Bioavailab 15(2):37–45View ArticleGoogle Scholar
- Ulmanu M, Matsi T, Anger I, Gament E, Olanescu G, Predescu C, Sohaciu M (2007) The redemial treatment of soil polluted with heavy metals using fly ash. U P B Sci Bull Series B 69(2):109–116Google Scholar
- Yee HY, Goodwin JF (1974) Simultaneous determination of copper and iron in a single aliquot of serum. Clin Chem 20(2):188–191Google Scholar
- Zhang Z, Chen Z, Qu C, Chen L (2014) Highly sensitive visual detection of copper ions based on the shape-dependent LSPR spectroscopy of gold nanorods. Langmuir 30(12):3625–3630View ArticleGoogle Scholar