Kinetics and oxidation of thiocarbohydrazide by hexacyanoferrate(III) in aqueous perchloric acid medium
Abstract
Hexacyanoferrate(III) [HCF(III)] was used to oxidize thiocarbohydrazide (TCH) in an aqueous perchloric acid (HClO4) medium, and the reaction kinetics were studied spectrophotometrically at 420 nm while keeping a constant ionic strength of 1.0 mol dm−3 and modulating the temperature between 298K–318K. The stoichiometry of the reaction among TCH and HCF in the HClO4 medium is 1:2. The reaction has a lower than unit order in both TCH and HClO4 and is of the first order in HCF. The impact of varying the ionic strength and dielectric constant of the medium on the rate has been investigated. The effect of temperature on the reaction rate was studied, and different activation parameters of reaction Ea, ΔH#, ΔS#, ΔG#, and log10 A were calculated. The products of oxidation were analyzed by simple qualitative analysis. On the basis of the collected data, the rate law has been derived, and a probable mechanism has been proposed.
References
[1] Metwally MA, Khalifa ME, Koketsu M. Thiocarbohydrazides: Synthesis and reactions. American Journal of Chemistry 2012; 2(2): 38–51. doi: 10.5923/j.chemistry.20120202.09
[2] Praphulla C, Satish C. A new method for the preparation of thiocarbohydrazide: Mono- and di-thio-p-urazine. Journal of the Chemical Society, Transactions 1924; 125: 1215–1218.
[3] Nesynov EP, Grekov AP. The chemistry of 1,3,4-oxadiazole derivatives. Russian Chemical Reviews 1964; 33(10): 508. doi: 10.1070/RC1964v033n10ABEH001476
[4] Kása I, rösi JK. Spectrofluorometric investigation of salicylal- dithiocarbazinic acid esters. Journal of Luminescence 1973; 6(4): 264–269. doi: 10.1016/0022-2313(73)90022-7
[5] Burns GR. Metal complexes of thiocarbohydrazide. Inorganic Chemistry 1968; 7(2): 277–283. doi: 10.1021/ic50060a022
[6] Dixon JFP, O'Brien RL, Parker JW. Periodate-induced lymphocyte transformation: V. Inhibition of periodate-induced transformation of human peripheral lymphocytes with aldehyde-blocking agents. Experimental Cell Research 1975; 96(2): 383–387. doi: 10.1016/0014-4827(75)90271-2
[7] Dixon JFP, Parker JW, O'Brien RL. Transformation of human peripheral lymphocytes by galactose oxidase. Journal of Immunology 1976; 116(3): 575–578. doi: 10.4049/jimmunol.116.3.575
[8] Chattopadhyay SK, Mak TCW. Study of Cu2+ mediated oxidation of thiosemicarbazide, thiocarbohydrazide and thiourea. Inorganic Chemistry Communications 2000; 3(3): 111–113. doi: 10.1016/S1387-7003(00)00017-4
[9] Albert A. Chemistry of 8-azapurines (1, 2, 3-triazolo[4, 5-d]pyrimidines). Advances in Heterocyclic Chemistry 1986; 39: 117–180. doi: 10.1016/S0065-2725(08)60764-3
[10] Abu-Nawwas AAH, Abdel Hameed RS, Eissa FM. Outer-sphere mechanism in the oxidation of pyrrole-2- carboxaldehyde by hexacyanoferrate(III) complex. International Journal of Engineering Research and Applications 2014; 4(1): 82–88.
[11] Sharma M, Sharma G, Agrawal B, et al. Kinetics and mechanism of electron transfer reactions. Osmium(VIII) catalyzed oxidation of mannitol by hexacyanoferrate(III) in aqueous alkaline medium. Transition Metal Chemistry 2005; 30: 546–551. doi: 10.1007/s11243-005-0396-8
[12] Stolle R, Bowles PE. Uber thiocarbohydrazid. Chemistry Europe 1908; 41: 1099.
[13] Amlathe S, Gupta VK. Spectrophotometric determination of trace amounts of hydrazine in polluted water. Analyst 1988; 113(9): 1481–1483. doi: 10.1039/AN9881301481
[14] McKennis H, Yard AS. Determination of methylhydrazine. Analytical Chemistry 1954; 26(12): 1960–1963. doi: 10.1021/ac60096a029
[15] McBride WR, Henry RA, Skolnik S. Potentiometric titration of organic derivatives of hydrazine with potassium iodate. Analytical Chemistry 1953; 25(7): 1042–1046. doi: 10.1021/ac60079a013
[16] Ravindra KS, Shastry VA, Kumar M, et al. Ruthenium(III) catalysed and uncatalysed oxidation of torsemide by hexacyanoferrate(III) in aqueous alkaline medium: A kinetic comparative approach. Journal of the Indian Chemical Society 2021; 98(8): 100104. doi: 10.1016/j.jics.2021.100104
[17] Ravindra KS, Shastry VA, Shashidhar S, Kumar M. Comparative kinetic study of palladium(II) catalyzed and uncatalyzed oxidation of ambroxol hydrochloride with potassium permanganate in an aqueous alkaline medium: A mechanistic approach. Physical Chemistry Research 2023; 11(4): 865–875. doi: 10.22036/PCR.2022.361486.2191
[18] Patil RK, Chimatadar SA, Nandibewoor ST. Oxidation of thiosulphate by hexacyanoferrate(III) in aqueous perchloric acid medium—A kinetic and mechanistic study. Indian Journal of Chemistry 2009; 48A(3): 357–361.
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