SIMULTANEOUS VOLTAMMETRIC DETERMINATION OF PERACETIC ACID AND THE COEXISTENT HYDROGEN PEROXIDE USING CARBOSITALL ROTATION ELECTRODEHTML Full Text
SIMULTANEOUS VOLTAMMETRIC DETERMINATION OF PERACETIC ACID AND THE COEXISTENT HYDROGEN PEROXIDE USING CARBOSITALL ROTATION ELECTRODE
Olena O. Mozgova *, Mykola Ye. Blazheyevskiy, Svitlana P. Karpova and Anatoly D. Gordienko
Department of Physical and Colloid Chemistry, National University of Pharmacy 53, Pushkinska Str., Kharkiv, Ukraine.
ABSTRACT: The aim of the present work is to determine the feasibility of peracetic acid (PAA) and the coexistent hydrogen peroxide (HP) simultaneous quantitative determination in disinfectant solution by voltammetry using carbositall rotation electrode (CE) as indicating electrode. It has been experimentally proved that the optimum pH for analysis is approximately 3.6. The linear relationship has been observed in the PAA concentration range (3.12–12.50)´10–5 mol L–1, the calibration curve equation was Iр = (3.78 ± 0.46)´103с (r = 0.995); in the HP concentration range of (0.94–3.76)´10–4 mol L–1, the calibration curve equation was Iр = (3.57 ± 0.26)´103с + (0.11 ± 0.07) (r = 0.998). Determining PAA in the working solution with the concentrations of 6.24´10–5, 7.80´10–5 and 9.36´10–5 mol L–1 the RSDs were 0.035, 0.028 and 0.022 respectively (δ = +0.30...+0.90%), determining HP in the working solution with the concentrations of 1.88´10–4, 2.35´10–4 and 2.82´10–4 mol L–1 the RSDs were 0.028, 0.018 and 0.011 respectively (δ = –0.77…+0.92%). Determining PAA in the test solution of "Delakson" disinfectant with the concentrations of 0.1%, the RSD was 0.024 (δ = +0.9%). Determining HP in the test solution of "Delakson" disinfectant, the RSD was 0.012 (δ = +1.69%). Thus, a new voltammetric method of simultaneous determination of peracetic acid and the coexistent hydrogen peroxide in disinfectant on CE has been developed, and the possibility of its quantitative determination has been shown.
Peracetic acid, Hydrogen peroxide, Voltammetry, Carbositall electrode, Disinfectant
INTRODUCTION: Peracetic acid (PAA, CAS Number 79-21-0) was introduced as an antibacterial agent in 1955. It has a broad spectrum of activity, including bacteria, spores, molds, yeasts, algae, and viruses. PAA, a possibly safe oxidizing agent.
It is increasingly used, especially as a high-level disinfectant in hospital establishments 1-2. Hydrogen peroxide (HP, H2O2, CAS Number 7722-84-1) is a widely used antimicrobial chemical. It is used for preservative, disinfection, and sterilization applications 3-4. It also has advantages concerning its toxicity and environmental profile 5.
HP presence in PAA solutions is imminent according to several reasons: so as the synthesis of PAA is carried out by HP reaction and acetate acid - that is why the hydrogen peroxide is a constant technological admixture, and also, due to the course of the hydrolysis reaction, in aqueous solutions, there is a continuous unilaterally hydrolytic decomposition of PAA into HP and acetate acid.
PAA in combination with HP is used in certain disinfectants such as "Delakson", “Nukdez” (Ukraine), "Septacid", "Dezynfektor", "Steridial W" (Poland), "Sterisyl", "Sterioks" (Estonia) etc. This mixture shows bactericidal, tuberculocidal, virucidal, sporicidal and fungicidal properties 6-8 and intended for the final, flow-line and preventive object disinfection in health care institutions and nidus of intestinal and respiratory infections of bacterial and viral etiology, tuberculosis, dermato-phytes and Sibirian plague, as well as for the sterilization of medical products (including rigid and flexible endoscopes) and suture material 9-11.
The extensive literature survey reveals various methods of PAA with HP determination 12, such as titration 13-14, electrochemical 15-20, chromato-graphic 21-23, and spectroscopic 24-25 methods have been used. It is obvious that two stepped titration method is not suitable for continuous monitoring because it is very time-consuming. Conductivity measurements are rapid and convenient, but their common disadvantage is their low selectivity. Spectroscopic methods have often been used for direct determination of a few species in aqueous solutions. Near-infrared (NIR) spectroscopy has recently been of keen interest as a practical technique for a variety of water and aqueous solution analyses. So far, a UV spectroscopic method for the direct determination of HP has not been reported probably because its UV absorption maximum is located at a very short wavelength (below 180 nm) and the extinction coefficients, obtained by ordinary UV-visible spectrometer, are very low. But all these methods are not sufficiently sensitive and furthermore require conducting of many chemicals, complicated cleaning and extraction procedures, and the use of cumbersome equipment may interfere with the whole procedure.
"Delakson" (“Delana”, Kyiv, Ukraine) is a complex disinfectant in the form of granulated water-soluble powder, which contains PAA (5-15%), HP (10-22%), acetate acid (22-26%) and stabilizing agents. The preparation is used in the form of water working solutions, and it’s prepared straight before the usage. It is allowed to store unused working solution for 5 days after producing in a container with a tightly closed lid at room temperature. The solution is used for disinfection during the day. The daily necessity of working solution concentration control is evident. The determination (mass fraction) of PAA in "Delakson" disinfectant is carried out by redox titration 26. The usage of carbositall electrode for electrochemical determination of some peroxides in preparations has been studied in our previous works 27-31.
The aim of the present work is to determine the feasibility of peracetic acid and the coexistent hydrogen peroxide simultaneous quantitative determination in disinfectant solution by voltammetry using carbositall rotation electrode (CE) as indicating electrode.
MATERIALS AND METHODS: The stock solution of PAA with HP. The stock solution was prepared by accurately commercial preparation dissolving, and it is standardized by the recommended procedure 26. 10.00 mL of obtained PAA solution was diluted in 100 mL volumetric flask with double distilled water to obtain 1.56×10–3 mol L–1 solution of PAA.
The solution of acetate buffer (pH = 3.6) was prepared by diluting of 425 mL of 1.00 mol L–1 solution of acetic acid and 50.0 mL 1.00 mol L–1 solution of NaOH in 500 mL volumetric flask with double distilled water at 20 °С.
The solution of ice acetic acid, 17.5 mol L−1 (AA) was prepared by diluting of 28.6 mL of concentrated (ice) solution of acetic acid in 500 mL volumetric flask with double distilled water at 20 °С.
The solution of sodium sulfate, 1 mol L−1 (NaSO4) was prepared by dissolving of 142.0 g of NaSO4 in 1000 mL volumetric flask by double distilled water.
The background solution consists of a mixture of the acetate buffer solution background (pH 3.6) and 0.1 mol L-1 Na2SO4.
The sample preparation which was subjected to the analytical procedures for the analysis of HP was "Delakson" disinfectant (“Delana”, Kyiv, Ukraine).
The test solution of "Delakson" disinfectant (0.1 % PAA, 0.9% HP) was prepared by dissolving 1.0 g of preparation in 1000 mL volumetric flask by double distilled water (standardized by 26).
The pH was measured by using an ion meter of І-160М type (Belarus) with a glass electrode of ESL-43-07 type paired with Ag, AgCl/KСl (sat) electrode.
The electrochemical measurements have been carried out in АVS-1.1 analyzer (Volta, St. Petersburg) with a three-electrode scheme by alternating the current mode with a square wave modulation in the potential range of +1.0…–1.0 V, W = 1000 rpm, the amplitude of 40 mV, ν = 65 Hz. The values of potential peaks directly at the maximum have been measured by the electrochemical sensor “Module EM-04” with the accuracy of ±5 mV. The CE has been used as a working and auxiliary electrode, and Ag, AgCl/KСl(sat) electrode type EVL-1М4 as a reference electrode.
The procedure of obtaining results for the calibration graph. Working solutions have been prepared by diluting different volumes of stock solution (1.00-4.00 mL) and 5 mL 1 mol L-1 Na2SO4 in 50 mL volumetric flask by the acetate buffer solution. 25 mL of the working solution was transferred to the cell. The voltammograms have been recorded by scanning the potential towards the negative direction in the potential range from +1.0 V to –1.0 V (vs. Ag, AgCl/KСl(sat)).
The graph was positioned in the following coordinates: the height of peaks Ip in μA at Ep = +0.15 V for PAA and Ep = –0.65 V for HP on the ordinate axis and corresponding concentration of PAA and HP respectively, c in mol L–1 on the abscissa axis. The graph equation coefficients have been calculated by the least square method.
The procedure of PAA and HP quantitative determination in "Delakson" disinfectant. Working solutions have been prepared by diluting different volumes (10.00-15.00 mL) of the stock solution and 5 mL 1 mol L-1 Na2SO4 in 50 mL volumetric flask by the acetate buffer solution. The voltammograms have been recorded by scanning the potential towards the negative direction in the potential range from +1.0 V to –1.0 V (vs. Ag, AgCl/KСl (sat)). The concentration of the test solution Cx has been calculated by the equation:
Cx = (Ip – b / a
Where Ip – the current peak of the working solution; a, b – graph equation coefficients.
PAA and HP mass fraction, % in the test solution has been calculated by the equation:
X% = Cx×M×100×V0 × 100% / m×1000×10×V
Where M – molar weight; V0 – volumetric flask capacity; V – test solution volume; m – sample weight; 10 – stock solution volume; 100, 100 – volumetric flask capacities.
RESULTS AND DISCUSSION: Effect of nature and pH of background solution. The effect of pH on the reduction process has been investigated by recording voltammograms of stock solution (c(PAA) = 3.12´10–5 mol L–1; c(HP) = 9.36´10–5 mol L–1) at several pH values ranging from 2.15 to 4.78.
FIG. 1: THE INFLUENCE OF pH ON THE CURRENT PEAK INTENSITY (A) AND ON THE PEAK POTENTIAL (B) OF PAA REDUCTION PROCESS AT THE CE (vs. Ag, AgCl/KСl (sat))
A mixture of 1 mol L-1 Na2SO4 with acetate buffer solution has been used as a background solution, and the pH of the solution has been changed gradually by adding NaOH 0.2 mol L–1. Two well-separated peaks (Ip) are observed at pH approximately 2.5-3.7, and at pH, about 4.78 analytical signal almost disappears. The effect of pH on the peak potential (Ep) shows the following: when pH value increases in the interval from 3 to 4, Ep remains almost constant, but Ep decreases markedly to the negative value with pH increasing over 4 Fig. 1, 2. That is why the optimum pH for analysis is approximately 3.6.
FIG. 2: THE INFLUENCE OF pH ON THE CURRENT PEAK INTENSITY (A) AND ON THE PEAK POTENTIAL (B) OF HP REDUCTION PROCESS AT THE CE (vs. Ag, AgCl/KСl (sat))
For quantitative determination of PAA and HP in working solutions the calibration curve method was used. The calibration curve equation in the PAA concentration range (3.12-12.50)´10–5 mol L–1 was Ip = (3.78 ± 0.46)´103´с (r = 0.995) Fig. 3; in the HP concentration range (0.94–3.76)´10–4 mol L–1 was Iр = (3.57 ± 0.26)´103с + (0.11 ± 0.07) (r = 0.998) Fig. 4. Analytical characteristics of the calibration graph of the PAA and HP voltammetric determination procedure are given in Table 1.
TABLE 1: ANALYTICAL CHARACTERISTICS OF THE CALIBRATION GRAPH OF PAA AND HP VOLTAMMETRIC DETERMINATION PROCEDURE (y = ax+b)
|Concentration ranges (mol L–1)||(3.12-12.50)´10–5||(0.94-3.76)×10–4|
|Regression equation||Ip = (3.78±0.46)´103с||Ip = (3.57±0.26) ×103с + (0.11±0.07)|
|Correlation coefficient (r)||0.995||0.998|
|LOD (mol L–1)||1.19×10–6||2.15×10–5|
|LOQ (mol L–1)||3.97×10–5||7.18×10–5|
The high sensitivity of this method is accompanied by very good reproducibility. The reproducibility was evaluated from 5 repeated electrochemical signal measurements of working solutions with PAA concentrations of 6.24´10–5, 7.80´10–5 and 9.36´10–5 mol L–1 and with HP concentrations of 1.88´10–4, 2.35´10–4 and 2.82´10–4 mol L–1.
Precision of the method developed with reference to the relative standard deviations (RSDs) were 0.035, 0.028 and 0.022 respectively (δ = +0.30...+0.90%) for PAA; and 0.028, 0.018 and 0.011 (δ = –0.77…+0.92%) for HP. The results obtained are summarized in Table 2.
TABLE 2: EVALUATION OF ACCURACY AND PRECISION OF PAA AND HP VOLTAMMETRIC DETERMINATION PROCEDURE IN WORKING SOLUTION (n = 5; P = 0.95%)
|Taken (mol L–1)||Found (mol L–1)||Reproducibility (%±SD)||RSD||ε (%)||δ* (%)|
|PAA||6.24×10–5||(6.30 ± 0.28) ×10–5||100.90 ± 4.41||0.035||4.37||+0.90|
|7.80×10–5||(7.86 ± 0.28) ×10–5||100.73 ± 3.53||0.028||3.50||+0.73|
|9.36×10–5||(9.39 ± 0.26) ×10–5||100.34 ± 2.78||0.022||2.75||+0.30|
|HP||1.88×10–4||(1.87 ± 0.06) ×10–4||99.23 ± 3.42||0.028||3.45||-0.77|
|2.35×10–4||(2.34 ± 0.05) ×10–4||99.53 ± 2.34||0.018||2.35||-0.47|
|2.82×10–4||(2.85 ± 0.04) ×10–4||100.92 ± 1.41||0.011||1.40||+0.92|
* In relation to the average reference method 26
The high sensitivity of this method is accompanied by a very good reproducibility. The reproducibility has been evaluated from 5 repeated electrochemical signal measurements of test solutions of "Delakson" disinfectant. The precision of the developed method in terms of the relative standard deviation (RSD) was 0.024 (δ = +0.90%) for PAA and 0.019 (δ = +1.69%) for HP respectively. The obtained results have been summarized in Table 3.
TABLE 3: THE RESULTS OF HP VOLTAMMETRIC DETERMINATION IN "DELAKSON" DISINFECTANT (n = 5; P = 0.95%)
|Taken (mol L–1)||Found (mol L–1)||Reproducibility (%±SD)||RSD||ε (%)||δ* (%)|
|PAA||0.100||0.101 ± 0.003||100.90 ± 2.99||0.024||2.97||+0.90|
|HP||0.900||0.915 ± 0.013||101.69 ± 1.50||0.019||1.47||+1.69|
* The calculation has been made according to the average content established using standard procedure 26
CONCLUSION: Thus, a new voltammetric method of simultaneous determination of peracetic acid and the coexistent hydrogen peroxide in disinfectant on CE has been developed, and the possibility of its quantitative determination has been shown. The linear relationship has been observed in the PAA concentration range (3.12–12.50)´10–5 mol L–1, the calibration curve equation was Iр = (3.78 ± 0.46)´103с (r = 0.995); in the HP concentration range of (0.94–3.76)´10–4 mol L–1, the calibration curve equation was Iр = (3.57 ± 0.26)´103с + (0.11 ± 0.07) (r = 0.998). Determining PAA in the working solution with the concentrations of 6.24´10–5, 7.80´10–5 and 9.36´10–5 mol L–1 the RSDs were 0.035, 0.028 and 0.022 respectively (δ = +0.30...+0.90 %); LOD = 1.19´10–6 mol L–1, LOQ = 3.97´10–5 mol L–1. Determining HP in the working solution with the concentrations of 1.88´10–4, 2.35´10–4 and 2.82´10–4 mol L–1 the RSDs were 0.028, 0.018 and 0.011 respectively (δ = –0.77…+0.92%); LOD = 2.15´10–5 mol L–1, LOQ = 7.18´10–5 mol L–1. Determining PAA in the test solution of "Delakson" disinfectant with the concentrations of 0.1%, the RSD was 0.024 (δ = +0.9%. Determining HP in the test solution of "Delakson" disinfectant, the RSD was 0.012 (δ = +1.69%).
CONFLICTS OF INTEREST: Nil
- Henn SA, Boiano JM and Steege AL: Precautionary practices of healthcare workers who disinfect medical and dental devices using high-level disinfectants. Infect Contr Hosp Epidemiology 2015; 36(2): 180-85.
- Boyce JM: Modern technologies for improving cleaning and disinfection of environmental surfaces in hospitals. Antimicrobial Resistance & Infection Control 2016; 5(1): 10.
- McDonnell G: The use of hydrogen peroxide for disinfection and sterilization applications. PATAI'S Chemistry of Functional Groups 2009: 34.
- Møretrø T, Fanebust H, Fagerlund A and Langsrud S: Whole room disinfection with hydrogen peroxide mist to control Listeria monocytogenes in food industry related environments. International Journal of Food Microbiology 2019; 292: 118-25.
- Carter Y and Barry D: Tackling C difficile with environmental cleaning. Nurs Times 2011; 107(36): 22-25.
- Thevenin T, Lobert PE and Hober D: Inactivation of an enterovirus by airborne disinfectants. BMC Infectious Diseases 2013; 13(1): 177-79.
- Montazeri N: Virucidal activity of fogged chlorine dioxide-and hydrogen peroxide-based disinfectants against human norovirus and its surrogate, feline calicivirus, on hard-to-reach surfaces. Frontiers in Microbiology 2017; 8: 1031.
- March JK, Pratt MD and Lowe CW: The differential effects of heat-shocking on the viability of spores from Bacillus anthracis, Bacillus subtilis, and Clostridium sporogenes after treatment with peracetic acid- and glutaraldehyde-based disinfectants. Microbiology Open 2015; 4(5): 764-73.
- Sevidova EK, Roi ID and Stepanova II: The effect of disinfecting agents on the contact corrosion of medical instruments. Protection of Metals 2006; 42(3): 303-05.
- Rutala WA, Weber DJ: Disinfection of endoscopes: review of new chemical sterilants used for high-level disinfection. Infection Control & Hospital Epidemiology 1999; 20(1): 69-76.
- Kampf G, Fliss PM and Martiny H: Is peracetic acid suitable for the cleaning step of reprocessing flexible endoscopes? World Journal of Gastrointestestinal Endoscopy 2014; 6(9): 390-06.
- Blazheyevskiy МY and Mozgova OO: Determination of the peroxides by electrochemical methods. Proc Shevchenko Sci Soc Chem Biochem 2015; 40: 121-41.
- Bodiroga M and Ognjanović J: Determination of peracetic acid and hydrogen peroxide in the mixture. Vojnosanitetski Pregled 2002; 59(3): 277-79.
- Sode F: Simultaneous determination of peracetic acid and acetic acid by titration with NaOH. Analytical Methods 2014; 6(7): 2406-09.
- Awad MI, Harnoode C and Tokuda K: Simultaneous electroanalysis of peracetic acid and hydrogen peroxide using square-wave voltammetry. Electrochemistry 2000; 68(11): 895-97.
- Awad MI, Harnoode C and Tokuda K: Simultaneous electroanalysis of peroxyacetic acid and hydrogen peroxide. Analytical Chemistry 2001; 73(8): 1839-43.
- Awad MI, Harnoode C and Tokuda K: Electroanalysis of peracetic acid in the presence of a large excess of hydrogen peroxide. Anal Letters 2001; 34(7): 1215-21.
- Awad MI, Oritani T and Ohsaka T: Simultaneous potentiometric determination of peracetic acid and hydrogen peroxide. Analytical Chemistry 2003; 75(11): 2688-93.
- Awad MI and Ohsaka T: Potentiometric analysis of peroxyacetic acid in the presence of a large excess of hydrogen peroxide. Journal of Electroanalytical Chemistry 2003; 544: 35-40.
- Awad MI: Selective electronalysis of peracetic acid in the presence of a large excess of H2O2 at Au (111)-like gold electrode. Analytical Chimica Acta 2012; 730: 60-65.
- Fatunmbi H and Fatunmbi B: HPLC separation and simultaneous analyses of peroxyacetic acid and acetic acid coexisting with hydrogen peroxide in the equilibrium mixture. SMT Separation Journals 2017; 01: 233-38.
- Pettas IA and Karayannis MI: Simultaneous spectra-kinetic determination of peracetic acid and hydrogen peroxide in a brewery cleaning-in-place disinfection process. Analytical Chimica Acta 2004; 522(2): 275-80.
- Effkemann S, Pinkernell U and Karst U: Peroxide analysis in laundry detergents using liquid chromatography. Analytical Chimica Acta 1998; 363: 97-103.
- Xiao J, Wang M, Pang Z, Dai L, Lu J and Zou J: Simultaneous spectrophotometric determination of peracetic acid and the coexistent hydrogen peroxide using potassium iodide as the indicator. Analytical Methods 2019; 11(10): 1039.
- Higashi N, Hiraki S and Ozaki Y: Direct determination of peracetic acid, hydrogen peroxide, and acetic acid in disinfectant solutions by far-ultraviolet absorption spectroscopy. Analytical Chemistry 2005; 77(7): 2272-77.
- Guidelines on using of Delakson for disinfection and sterilization. CSES MHU 2008: 26.
- Blazheyevskiy MY and Mozgova OO: Voltammetric determination of potassium hydrogen peroxomonosulfate in pure substance and disinfectant «Ecocid S». Journal of Chemical and Pharmaceutical Research 2013; 5(11): 489-96.
- Blazheyevskiy MY and Mozgova OO: Quantitative determination of potassium hydrogen peroxomonosulfate in disinfectant Ecocid S» by cathodic voltammetry. News Pharmacy 2014; 2: 78.
- Blazheyevskiy МY and Mozgova OO: Voltammetric determination of magnesium monoperoxyphthalate in pure substance and disinfectant “Dismozon pur”. Manage Econom Qual Assur Pharm 2015; 4: 4-11.
- Blazheyevskiy МY and Mozgova OO: The quantitative determination of hydrogen peroxide by voltammetry on the carbositall electrode. News Pharmacy 2016; 4: 9-13.
- Karpova, SP, Mozgova OO, Blazheyevskiy MY and Oleksienko TO: Quantitative assay of peracetic acid in disinfectant “Delakson” by cathodic voltammetry. Asian Journal of Pharmaceutics 2018; 12(03): S1002.
How to cite this article:
Mozgova OO, Blazheyevskiy MY, Karpova SP and Gordienko AD: Simultaneous voltammetric determination of peracetic acid and the coexistent hydrogen peroxide using carbositall rotation electrode. Int J Pharm Sci & Res 2020; 11(6): 3003-08. doi: 10.13040/IJPSR.0975-8232.11(6).3003-08.
All © 2013 are reserved by the International Journal of Pharmaceutical Sciences and Research. This Journal licensed under a Creative Commons Attribution-NonCommercial-ShareAlike 3.0 Unported License.
O. O. Mozgova *, M. Y. Blazheyevskiy, S. P. Karpova and A. D. Gordienko
Department of Physical and Colloid Chemistry, National University of Pharmacy, Kharkiv, Ukraine.
18 July 2019
06 December 2020
11 February 2020
01 June 2020