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Simple photometric determination of free cyanide ion in aqueous solution with 2,6-dichlorophenolindophenol

100%
Yari A., Kargosha K.
Open Chemistry
|
2006
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vol. 4
|
issue 2
329-337
EN
In this work, a simple photometric method with high accuracy and precision for measuring trace amounts of free cyanide ion in aqueous solution is demonstrated. Under the evaluated conditions, we could determine CN− concentration in the range of 5–70 ppm easily. The work is based upon the photometric titration of CN− with Co(II) in the presence of 2,6-dichlorophenolindophenol (DCPIP) at λmax = 602 nm in aqueous solution. The optimal conditions, such as pH, ionic strength, and concentration of chromopher were evaluated. The interence effect of many other cations and anions studied and the results are given here. The optimized titration was successfully used to determine the concentration of free cyanide ion in aqueous solutions.
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Trans influence of triphenylphosphines and pseudohalogens on Ni-S bonds: Synthesis, spectral and single crystal X-ray structural studies on NiS2PN and NiS2PC chromophores

88%
Ramalingam K., Thiruneelakandan R., Bocelli G., Righi L.
Open Chemistry
|
2012
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vol. 10
|
issue 4
1199-1207
EN
Trans influence of triphenylphosphines and pseudohalogens on Ni-S bonds of NiS2PN and NiS2PC chromophores has been investigated by synthesizing and characterizing them. The complexes show the characteristic thioureide IR band at ∼ 1530 cm−1. Electronic spectrum of the cyanide analogue shows a strong blue shift relative to others. X-ray structures of [Ni(pipdtc)(4-MP)(NCS)] (1), [Ni(pipdtc)(PPh3)(NCS)] (2) and [Ni(pipdtc)(PPh3)(CN)] (3) (pipdtc = piperidinecarbodithioate anion, 4-MP = tri(4-methylphenyl)phopshine) are reported. Ni-S bond distance trans to 4-MP(1) is longer than the distances in (2) and (3) and Ni-S bond distances trans to Ni-NCS/CN decrease as follows: (3) > (2) > (1). Particularly, 4-MP shows a highly significant trans influence than triphenylphosphine on Ni-S bond. Similarly, CN− exerts a marginally significant trans influence compared to NCS-. Thioureide C-N distances are relatively very short due to the drift of electron density towards the metal. The Ni-N-C angle (163.5(2)°) observed in (2) indicates deviation from linearity to a larger extent compared to that in (1) (176.3(3)°) due to the steric effect of the 4-methyl group. The reduction potentials (CV) for the mixed ligand complexes are much less compared to that of the parent NiS4 chromophore due to the π-acidic phosphines. [...]
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