Application of the reaction system methylene blue B–(NH4)2S2O8 for the kinetic spectrophotometric determination of palladium in citric buffer media

Sofija M. Rančić, Snežana D. Nikolić-Mandić, Aleksandar Lj. Bojić, Snežana M. Đorić-Veljković, Aleksandra R. Zarubica, Predrag Lj. Janković


A new, simple, rapid, sensitive and selective kinetic spectrophotometric method for Pd(II) traces determination was elaborated in this paper. It is based on the catalytic effect of palladium ions upon the oxidation of methylene blue B (MBB) by (NH4)2S2O8 (APS) in citric buffer (BUF) solution. At the working temperature of 25 °C and the wavelength of 662.4 nm, the optimal conditions for palladium determination were found. RSD value was found to be 2.6 to 4.9% for the investigated concentration range of Pd(II). Limit of detection (LD) was found to be 2.0 ng cm–3 Pd(II), and limit of quantification (LQ) is 6.9 ng cm–3 Pd(II). Only the presence of Pb2+, Hg2+ and Sn2+ in the reaction mixture interferes the deter­mination of palladium by this method, while Au3+ and Ag+ have the catalytic effect upon the reaction rate. By this method, it is possible to determine the Pd(II) traces in the con­centration range of 3.3´10–8 to 1.0´10–6 g cm–3. The method was confirmed by deter­mination of Pd(II) traces in alloy PtRhG as well as in the  powder of Pt. The obtained results were compared to those obtained by ICP-OES method and good agreement of results was found.


Pd(II) determination, catalyst, kinetic spectrophotometric method

Full Text:

PDF (394 kB)


C. Sanchez-Pedreno, M. Hernandez-Cordoba, G. Mar-tinez-Tudela, Kinetic determination of palladium(II) while catalyzing the reaction of toluidine blue and hypo-phosphite, Anal. Chim. 75 (1979) 536–539.

C. Sanchez-Pedreno, M.J. Albero-Quinto, M. Hernandez-Cordoba, Kinetic determination of palladium(II) by its catalytic effect on the reaction between phenosafranine and hypophosphite, Afinidad 37 (1980) 313–316.

C. Sanchez-Pedreno, M.J. Albero-Quinto, M.S. Garsia-Garsia, Stydy of the reaction of Pyronine G with hypophosphite anion. Kinetic determination of palladium (II), silver(I) and iodide ion, Quim. Anal. 4 (1985) 168–176.

G. Miletić, S. Mitić, Catalytic determination of palladium by oxidation of purpurin using hydrogen peroxide, Zh. Anal. Khim. 49 (1994) 508–511.

A. Esnafi, M. Keyvanfard, Kinetic–spectrophotometric determination of palladium in hydrogenation catalyst by its catalytic effect on the oxidation of pyrogallol red by hydrogen peroxide, Spectrochim. Acta, A 58 (2002) 1567–1572

R. Montes, J. Laserna, Coupling of redox and complex formation processes for the kinetic determination of palladium, Analyst 110 (1985) 1339–1341.

Y.A. Bankovskii, M. Vircava, O. Veveris, A. Pelne, D. Vircava, Preconcentration of microamounts of elements in natural waters with 8-mercaptoquinoline and bis(8-quinolyl) disulphide for their atomic-absorption determination, Talanta 34 (1987) 179–182.

L.P. Tihonova, V.P. Goncharik,V.P. Kozhara, I.P. Svarovs-kaya, Kinetic determination of palladium, Zh. Anal. Khim. 46 (1991) 2009–2013.

A. Niazi, B. Jafarian, J. Ghasemi, Kinetic spectrophoto-metric determination of palladium by whole kinetic curve and a fixed time method using resazurine sulfide reaction, Spectrochim. Acta, A 71 (2008) 841–846.

F. Garcia Montelongo, V. Gonzales-Dias, C.R. Tallo Gon-zales, Analytical application of 3-(2′-thiazolylazo)-2,6-diaminopyridine:spectrophotometric determination of palladium, Microchem. J. 27 (1982)194–199.

A.G. Asuero, M.J. Navas, J.M. Bautista, D. Rosales, Spectrophotometric determination of palladium by sol-vent extraction as the Pd(II)-biacetylmonoxime 2-pyr-idyl¬hydrazone complex, Microchem. J. 28 (1983)183–197.

B. Keshavan, P. Nagaraja, A rapid method for the spectrophotometric determination of palladium (II) and osmium (VIII), Microchem. J. 31 (1985) 124–129.

A. Kumar, M. Gautam, B.K. Puri, Spectrophotometric determination of palladium by adsorption on its n-but-ylxantate complex on microcrystalline naphtalene, Mic-rochem. J. 33 (1986) 256–263.

K. Uesugi, M. Miyawaki, A sensitive spectrophotometric method for the determination of palladium with Erio-chromeazurol G and cetyltrimethylammonium chloride, Microchem. J. 41 (1990) 78–83.

P.M. Shiundu, P.D. Wentzell, A.P. Wade, Spectrophotometric determination of palladium with sulfochlorophe-nolazorhodanine by flow injection, Talanta 37 (1990) 329–336.

A. Safavi, A. Massoumi, Some observations on the solvent extraction and spectrophotometric determination of palladium using 3,4-dihydro-4,4,6-trimethyl-2(1H)-pyrimidine-thione as a selective reagent, Microchem. J. 42 (1990) 314–318.

X. He, Y. Cai, Z. Hu, Flow injection spectrophotometric determination of palladium with DCS-arsenazo, Anal. Chim. Acta 256 (1992) 113–116.

A.K. Chhakkar, L.R. Kakkar, Extractive-spectrophotometric method for the determination of palladium using thiosalicylic acid and hexylamine, Fres. J. Anal. Chem. 347 (1993) 483–485.

O. Hernandez, A.J. Jimenez, F. Jimenez, J.J. Arias, J. Havel, Highly specific spectrophotometric method for Pd(II) determination with 3-(5′-tetrazolylazo)-2,6-diam-ino¬toluene in the presence of chlorides, kinetic and equilibrium study of reactions, Talanta 41 (1994) 775–782.

Y. Xu, X. Chen, Z. Hu, Dispersion behaviour of chromo-genic reagents in a microwave field in a flow system, Application to the spectrophotometric flow-injection determination of palladium and rhodium, Anal. Chim. Acta 292 (1994) 191–199.

L. Elci, S. Isildar, M. Dogan, Spectrophotometric determination of gold and palladium in anode slimes after separation with Amberlite XAD-7 resin, Anal. Chim. Acta 293 (1994) 319–324.

P.S. More, A.D. Sawant, Isonitroso-4-Methyl-2-Pentanone for Solvent Extraction and Spectrophotometric Determination of Palladium(II) at Trace Level, Anal. Lett. 2 (1994) 1737–1748.

S. Sakuraba, K. Oguma, Spectrophotometric determination of palladium(II) with phenylfluorone in the pre-sence of hexadecylpyridinium bromide, Fres. J. Anal. Chem. 349 (1994) 523–526.

A.K. Chhakkar, L.R. Kakkar, Extractive spectrophoto-metric determination of palladium using 2–(2–hydroxy-imino-1-oxoethyl)furan, Fres. J. Anal. Chem. 350 (1994) 127–131.

R. Sahu, S.M. Sondhi, B. Gupta, Extraction and spectrophotometric determination of Pd(II) with 3,4,4a,5-tetrahydro–3,3,4a-trimethyl-7-(substituted)-pyri-mido(1,6-a)-benzimidazole-1-thiol(PBT), Talanta 42 (1995) 401–405.

H. Yang, G. Zhang, L. Zhang, G. Liu, X. Zhang, Synthesis of 5-(5–nitro-2-pyridylazo)-2,4-diaminotoluene and its application to spectrophotometric determination of microamounts of palladium, Talanta 43 (1996) 747–753.

S. Hoshi, K. Higashihara, M. Suzuki, Y. Sakurada, K. Sugawara, M. Uto, K. Akatsuka, Simultaneous determination of platinum(II) and palladium(II)by reversed phase high-performance liquid chromatography with spectrophoto-metric detection after collection and elution from resin coated with dimethylglyoxalbis(4-phenyl-3-thiosemicarbazone), Talanta 44 (1997) 571–576.

J. Gao, B. Peng, H. Fan, J. Kang, X. Wang, Spectrophoto-metric determination of palladium after solid–liquid extraction with 1-(2-pyridilazo)-2-naphtol at 90 °C, Talanta 44 (1997) 837–842.

J. Mori, T. Kawakatsu, Y. Fujita, T. Matsuo, Selective spectrophotometric determination of Pd(II) with 2(5-nitro-2-pyridylazo)-5-(N-propyl-N-3-sulfopropyl¬amino)-phe¬nol(5-NO2.PAPS) and tartaric acid with 5-NO2 .PAPS–niobium(V) complex, Talanta 48 (1999) 1039–1044.

M.A. Kabil, M.A. Akl, M.E. Khalifa, Selective flotation-spectrophotometric procedure for the trace analysis of palladium(II) in different matrices, Anal. Sci. 15 (1999) 433–438.

A.K. Malik, A.L. Rao, Spectrophotometric determination of cobalt, nickel, palladium, copper, ruthenium and molybdenum after extractionof their isoamyl xanthate complex into molten naphtalene, Zh. Anal. Khim. 55 (2000) 746–749.

A.N. Anthemidis, D.G. Themelis, J.A. Stratis, Selective stopped-flow injection spectrophotometric determin-ation of Pd(II) in hydrogenation and automobile exhaust gas converter catalysts, Anal. Chim. Acta 412 (2000) 161–167.

S. Igarashi, N. Ide, Y. Takagai, High-performance liquid chromatographic-spectrophotometric determination of copper(II) and palladium(II) with 5,10,15,20-tetrakis(4N-pyridyl)porphine following homogeneous liquid–liquid extraction in the water–acetic acid–chloroform ternary solvent system, Anal. Chim. Acta 424 (2000) 263–269.

M.B. Gholivand, N. Nozari, Extraction and spectro-photometric determination of trace amount of Pd (II) with 2,2′-dithiodianiline, Talanta 52 (2000) 1055–1060.

F. Salinas, A. Espinosa-Mansilla, L. Lopez-Martinez, P.L. Lopez de Alba, Selective extraction–spectrophotometric determination of microamounts of palladium in cat-alysts, Chem. Anal.(Warsaw) 46 (2001) 239–248.

A.N. Anthemidis, D.G. Themelis, J.A. Stratis, Stopped flow injection liquid–liquid extraction spectrophoto-metric determination of palladium in airborne particulate matter and automobile catalysts, Talanta 54 (2001) 37–43.

D. Ma, F. Cui, D. Xia, Y. Wang, Spectrophotometric determinatin of copper and palladium using a new reagent, Anal. Lett. 35 (2002) 413–421.

M.C. Bruzzoniti, C. Mucchino, E. Tarasco, C. Sarzanini, On-line preconcentration ion chromatographic separ-ation and spectrophotometric determination of palla-dium at trace level, J. Chromatogr., A 1007 (2003) 93–


M. Arndt, I. Zadrozna, A. Dybko, W. Wroblewski, K. Kasiura, Palladium determination using flow–through spectrophotometric sensing phase, Sens. Actuators, B 90 (2003) 332–336.

H. Eskandari, H-point standard addition method-First derivative spectrophotometry for simultaneous deter-mination of palladium and cobalt, Spectrochim. Acta, A 63 (2006) 391–397.

A. Niazi, A. Azizi, M.Ramezani, Simultaneous spectro-photometric determination of mercury and palladium with thio-Michler′s ketone using partial last squares regression and orthogonal signal correction, Spectro-chim. Acta, A 71 (2008) 1172–1177.

R. Ruhela, J.N. Sharma, B.S. Tomar, R.C. Hubli, A.K. Suri, Extractive spectrophotometric determination of palla-dium with N,N,N′,N′-tetra(2-ethylhexyl)-thioglycolamide T(2EH)TDGA, Talanta 85 (2011) 1217–1220.

S. Sacmaci, S. Kartal, Determination of palladium by on–line flow–injection direct spectrophotometry in environmental samples using 2,2′–furyldioxime as a chelator, Talanta 109 (2013) 26–30.

G. Absalan, A. Safavi, A. Massoumi, Extraction–atomic absorption spectrophotometric determination of palla-dium with 4,6-diamino-3,5-dicyano-2H-1-thiopyran-2-thione, Microchem. J. 37 (1988) 212–215.

P. Di, D.E. Davey, An optimized on-line preconcentration system for analysis of trace gold in ore samples, Talanta 42 (1995) 1081–1088.

S. Lin, C. Zheng, G. Yun, Determination of palladium by flame atomic absorption spectrometry combined on-line with flow-injection preconcentration using a micro-column packed with activated carbon fibre, Talanta 42 (1995) 921–926.

K. Jankowski, Determination of small amounts of palladium in wastes from reworking of spent catalysts by microwave induced plazma atomic emission spectrometry, Anal. Chim. Acta 317 (1995) 365–369.

H.W. Zhang, L. Jia, Z.D. Hu, Determination of palla-dium(II) as chloro complex by capillary zone electro-phoresis, J. Chromatogr. 704 (1995) 242–246.

G.E.M. Hall, J.C. Pelchat, Determination of palladium and platinum in fresh waters by inductively coupled plasma mass spectrometry and activated charcoal pre-concentration, J. Anal. At. Spectrom. 8 (1993) 1059–1065.

D. Perez-Bendito, M. Silva, Kinetic Methods in Analytical Chemistry, John Wiley & Sons, Chichester, 1988.



  • There are currently no refbacks.

Copyright (c) 2017 HEMIJSKA INDUSTRIJA

Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.