Extraction-Spectrophotometric Studies on the Ion-Pairing Between Some 2,3,5-Substituted Monotetrazolium Cations and Anions Deriving from 4-(2-Thiazolylazo)resorcinol or 4-(2-Pyridylazo)resorcinol

The ion-pairing between some 2,3,5-substituted monotetrazolium cations (T+) and anions deriving from 4-(2-pyridylazo)resorcinol (PAR) or 4-(2-thiazolylazo)resorcinol (TAR) was studied by water-chloroform extraction and spectrophotometry. The following tetrazolium salts (TS) were used as a source of T+: i) 2,3,5-triphenyl-2H-tetrazolium chloride (TTC); ii) 3-(4,5-dimethyl-2-thiazol)-2,5-diphenyl-2H-tetrazolium bromide (MTT); iii) 3-(2-naphtyl)-2,5-diphenyl-2H-tetrazolium chloride (Tetrazolium violet, TV); and iv) 2-(4-iodophenyl)-3-(4-nitrophenyl)-5-phenyl-2H-tetrazolium chloride (INT). The spectral characteristics of the extracted species were established at different pH and TS concentration. The composition and stability of the ion-pairs were determined at pH 9, where the extraction of neutral PAR (H2PAR) and TAR (H2TAR) species was negligible. The results showed that the ion-pairs can be expressed with the following formulae (T+)(HTAR–) (where T+ = TT+, MTT+, TV+ or INT+), (T+)(HPAR–) (where T+ = TT+, MTT+ or TV+) and [(INT+)(HPAR–)]2. Relationships involving the molecular masses of the ion-pairs (MIP) or T+ (MT+) and the values of the constants of association (b) or conditional molar absorptivities (e’) were examined, namely Log b = f(Log MIP) and e’ = f(Log MT+). Some practical aspects concerning the investigation of metal complexes with TS-PAR/TS-TAR were discussed

LIQUID-LIQUID EXTRACTION-SPECTROPHOTOMETRIC DETERMINATION OF MOLYBDENUM USING o-HYDROXYTHIOPHENOLS

27 liquid-liquid extraction-chromogenic systems containing Mo(VI), o-hydroxythiophenol derivative {HTPDs: 2-hydroxy-5-chlorothiophenol (HCTP), 2-hydroxy-5-bromothiophenol (HBTP) or 2-hydroxy-5-iodothiophenol (HITP)} and aromatic amine (AA) were studied. Aniline (An), N-methylaniline (mAn), N,N-dimethylaniline (dAn), o-toluidine (o-Tol), m-toluidine (m-Tol), p-toluidine (p-Tol), 3,4-xylidine (o-Xyl), 2,4-xylidine (m-Xyl), and 2,5-xylidine (p-Xyl) were the examined AAs. Optimization experiments for molybdenum extraction-spectrophotometric determination were performed and the following parameters were found for each of the systems: organic solvent (opt), pH (opt), CHTPD (opt), CAA (opt), shaking time (opt), l (max) and e (max). Under the optimum conditions, the molar ratio of the reacting Mo(V), HTPD and AA was 1:2:2 and the degrees of Mo extraction were R³98.4%. Linear relationships involving the spectral characteristics of the extracted complexes (lmax or emax) and some fundamental properties of the halogen substituent in the HTPD were discussed. The effect of foreign ions was examined and two sensitive, selective and precise procedures for extraction-spectrophotometric determination of molybdenum were proposed. The relative standard deviations for Mo content of (3-5)´10–4 mass % were 4% (HCTP-An procedure) and 3% (HBTP-An procedure)

Liquid-Liquid Extraction-Spectrophotometric Investigations of Three Ternary Complexes of Vanadium(V)

Complex formation and liquid-liquid extraction (LLE) were studied in systems containing vanadi-um(V), 5-methyl-4-(2-thiazolylazo)resorcinol (TAO), tetrazolium salt (TZS), water and chloroform. The following three TZSs were used: 3-(4,5-dimethyl-2-thiazol)-2,5-diphenyl-2H-tetrazolium bromide (MTT), 3-(2-naphtyl)-2,5-diphenyl-2H-tetrazolium chloride (Tetrazolium violet, TV), and 2-(4-iodophenyl)-3-(4-nitrophenyl)-5-phenyl-2H-tetrazolium chloride (INT). Concentration of the reagents (TAO and TZS), pH of the aqueous medium, and shaking time were subjects of optimization experi-ments. Formation of ternary complexes with a composition of 2:2:2 was demonstrated by a set of dif-ferent methods. Some key characteristics concerning the analytical application of the studied LLE-chromogenic systems were established as well

Extraction of Gallium(III) with a New Azo Dye in The Presence or Absence of Xylometazoline Hydrochloride

Complex formation between Ga(III) and 6-hexyl-4-(2-thiazolylazo)resorcinol (HTAR, H2L) was studied in a water-chloroform medium, in the presence or absence of xylometazoline hydrochloride (XMH). Optimum conditions for the extraction of Ga(III) were found. In the presence of XMH, the extracted ion-associate has the formula (XMH+)[GaIIIL2], where HTAR is in its deprotonated form L2–. Some key extraction-spectrophotometric characteristics were determined: absorption maximum (521 nm), apparent molar absorptivity (5.8 × 104 dm3 mol–1 cm–1), limit of detection (18 ng cm–3), limit of quantitation (60 ng cm–3), extraction constant (LogK = 4.44), distribution ratio (LogD = 2.2) and fraction extracted (99.3 %). In the absence of XMH, the extracted chelate contains one deprotonated and one monoprotonated HTAR: [GaIII(HL–)(L2–)]. It has an absorption maximum at 523 nm and a shoulder at 580–590 nm. The pKa of HTAR (H2L ⇄ H+ + HL– equilibrium) was calculated (5.4) and the effect of foreign ions was studied. This work is licensed under a Creative Commons Attribution 4.0 International License

Some Ternary Phenylmethoxybis(tetrazolium) Complexes of Vanadium(IV,V) and Their Constants of Association

Several liquid-liquid extraction systems containing vanadium {vanadium(IV) or vanadium(V)}, azoderivative of resorcinol {ADR: 4-(2-pyridylazo)-resorcinol (PAR) or 4-(2-thiazolylazo)-resorcinol (TAR)} and (phenylmethoxibis)tetrazolium salts {MBT: 3,3\u27-(3,3\u27-dimetoxy-4,4\u27-biphenylene)-bis(2,5-diphenyl-2H-tetrazolium) chloride (Blue Tetrazolium, BT) or 3,3\u27-(3,3\u27-dimetoxy-4,4\u27-biphenylene)-bis[2,5-di(4-nitrophenyl)-2H-tetrazolium] chloride (Tetranitroblue Tetrazolium, TNBT)} were studied. The optimum operating conditions and compositions of the extracted species were found. The constants of association (β) between MBT2+ and the anionic V–ADR chelates (Cheln–) were calculated. Previously re-ported negative linear relationship between log β and the number of nitro groups included in tetrazolium cation (Nnitro) was discussed taking into account the obtained results and literature data for V–ADR–MBT complexes of the same class, in which MBT is BT or 3,3\u27-(3,3\u27-dimetoxy-4,4\u27-biphenylene)bis[2-(4-nitrophenyl)-5-phenyl-2H-tetrazolium] chloride (Nitroblue Tetrazolium, NBT). (doi: 10.5562/cca1885

Does Sendivogius’ alchemy cancel the celebration of the 250th anniversary of the discovery of oxygen?

Most chemistry textbooks claim that oxygen was discovered almost simultaneously by Carl Scheele and Joseph Priestley about 250 years ago. Priestley obtained oxygen by heating mercuric oxide (1774), and Scheele by heating NaNO3, as well as by dissolving pyrolusite in sulfuric acid (1772). The name “oxygen” was given a few years later (1779) by Antoine Lavoisier. This great scientist, often accused of taking advantage of the discoveries of others, conducted experiments related to the decomposition of water vapour over heated iron, as well as the synthesis of water from hydrogen and oxygen. His work was of great importance because it revealed the elemental nature of oxygen and its role in the processes of combustion and respiration. The present article draws attention to the prehistory of the “oxygen theory”. It emphasises the natural philosophy of a forgotten alchemist, healer, and diplomat - Michael Sendivogius (1566-1636) - who popularised his belief that the substance (“Water of life that does not wet the hands”) obtained by heating the “Central Salt” (nitre, KNO3) is part of the air. It is the “secret food of life” used invisibly by every living thing

Ternary complexes of vanadium(IV) with 4-(2-pyridylazo)-resorcinol (PAR) and ditetrazolium chlorides (DTC)

AbstractComplex formation and liquid-liquid extraction have been studied for ternary complexes of vanadium(IV) with 4-(2-pyridylazo)-resorcinol (PAR) and ditetrazolium chlorides (DTC) in a water-chloroform medium. The specific ditetrazolium compounds investigated were i) 3,3′-(4,4′-biphenylene)-bis(2,5-diphenyl-2H-tetrazolium) chloride (Neotetrazolium chloride, NTC); ii) 3,3′-(3,3′-dimetoxy-4,4′-biphenylene)-bis(2,5-diphenyl-2H-tetrazolium) chloride (Blue Tetrazolium chloride, BTC); and iii) 3,3′-(3,3′-dimetoxy-4,4′-biphenylene)-bis[2-(4-nitrophenyl)-5-phenyl-2H-tetrazolium] chloride (Nitro Blue Tetrazolium chloride, NBT). Molar absorptivity coefficients and the composition of the complexes have been calculated. Association constants (β) have also been obtained for the interactions between the vanadium(IV) — PAR anionic chelates [VO(PAR)2]2− (I) and [VO(OH)2(PAR)2]4− (II), and ditetrazolium cations (DT2+). Some special features of NBT as an extraction-spectrophotometric reagent for vanadium(IV) have been discussed. Unlike NTC and BTC which form complexes with both I and II, NBT associates only with II. The pH interval for complete extraction of (NBT2+)2[VO(OH)2(PAR)2] is broader and allows work at lower pH values the other ion-associates of V(IV,V)-PAR that were studied. NBT is -therefore the appropriate reagent both for direct V(IV) determination and for V(IV)/V(V) separation. Some additional characteristics for the V(IV)-PAR-NBT-water-chloroform system have been determined: extraction constant, distribution constant, recovery factor, limit of detection and limit of quantification. Beer’s law is valid up to 1.4 μg mL−1 vanadium(IV) with molar absorptivity coefficient of 3.55×104 L mol−1 cm−1 at λmax=559 nm. </jats:p

Liquid–liquid extraction and cloud point extraction for spectrophotometric determination of vanadium using 4-(2-pyridylazo)resorcinol

AbstractLiquid-liquid extraction (LLE) and cloud point extraction (CPE) of vanadium(V) ternary complexes with 4-(2-pyridylazo)resorcinol (PAR) and 2,3,5-triphenyl-2H-tetrazolum chloride (TTC) were investigated. The optimal conditions for vanadium extraction and spectrophotometric determination were identified. The composition (V : PAR : TTC) of the extracted species was 1 : 2 : 3 (optimal conditions; LLE), 2 : 2 : 2 (low reagents concentrations; LLE), 1 : 1 : 1 (short heating time; CPE), and 1 : 1 : 1 + 1 : 1 : 0 (optimal extraction conditions; CPE). LLE, performed in the presence of 1,2-diaminocyclohexane-N,N,N’,N’-tetraacetic acid and NH4F as masking agents, afforded the sensitive, selective, precise, and inexpensive spectrophotometric determination of vanadium. The absorption maximum, molar absorptivity, limit of detection, and linear working range were 559 nm, 1.95 × 105 dm3 mol−1 cm−1, 0.7 ng cm−3, and 2.2-510 ng cm−3, respectively. The procedure thus developed was applied to the analysis of drinking waters and steels. The relative standard deviations for V(V) determination were below 9.4 % (4-6 × 10−7 mass %; water samples) and 2.12 % (1-3 mass %; steel samples).</jats:p