HOCH2CH2NH2 – TROPEOLIN OOO – H2O SYSTEM ACID-BASIC PROPERTIES IN THE PRESENCE OF HCl, HClO4, H2SO4 AND SO2H2O

R. Khoma, A. Ennan, T. S. Ben’kovs’ka, E. Y. Bugova, L. T. Osadchiy, E. M. Menchuk
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引用次数: 1

Abstract

The influence of hydrochloric, chloric, sulfuric and sulfurous acids (HCl, HClO4, H2SO4 and SO2×H2O, respectively) on protolytic equilibria in the system monoethanolamine (MEA) – tropeolin OOO (TrOOO) – water (CMEA = 0.1 M; pH = 1.0 ÷ 9.5) was studied by pH-metric, spectrophotometric and colorimetric methods. The acid-base behavior of the HOCH2CH2NH2 – TrOOO – H2O system was investigated at CTrOOO = 1,12 ×10-4 М, CMEA = 1,0×10-4  ÷ 1,0 М (pH = 8,25 ÷ 12,05), T = 293 K. TrOOO in this system exists in two tautomeric forms due to acid-base dissociation of the 4-OH group and associates formed by H-bonding with MEA molecules. There is a direct ratio between the pH values ​​of solutions and the total color difference (ΔE76), in contrast to the specific color difference (SCD). The difference in the behavior of the H2SO4 – HOCH2CH2NH2 – TrOOO – H2O system from the systems with HCl and HClO4 is due to the fact that the interaction of the first acid with MEA (8,0 £ pH) forms an ionic associate [HOCH2СH2NH3]2(SO4), which is more stable than ionic pairs [[HOCH2СH2NH3](HSO4), [HOCH2СH2NH3](ClO4), [HOCH2СH2NH3]Cl и [HOCH2СH2NH3](O3S-C­10H6-N=N-C6H4-SO3)[H3NCH2СH2OH]. Acid-base dissociation constants in systems significantly depend on the structure and physicochemical parameters of the mineral acid. In the electronic absorption spectra of the SO2 – MEA – TrOOO – H2O system (pH £ 7,5), there is a pronounced isobestic point at 415 nm, due to the dynamic equilibrium between ion-molecular forms. The coincidence of the maxima on the curves ΔE76 = f(pH) and SCD = f(pH) for the indicated system, in contrast to others studied in this work, was stated. The difference between the spectrophotometric and colorimetric behavior of the SO2 – MEA – TrOOO – H2O system from behavior of the systems with HCl, HClO4, and H2SO4 systems is due to the sulfur(IV)oxyanions with an azo indicator redox interaction.
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在HCl、HClO4、H2SO4和SO2存在下的酸碱性质
盐酸、氯酸、硫酸和亚硫酸(HCl、HClO4、H2SO4和SO2×H2O)对单乙醇胺(MEA) - tropeolin OOO (TrOOO) -水(CMEA = 0.1 M;pH = 1.0 ÷ 9.5),分别用pH法、分光光度法和比色法研究。在CTrOOO = 1,12 ×10-4 М, CMEA = 1,0×10-4 ÷ 1,0 М (pH = 8,25 ÷ 12,05), T = 293 K条件下,研究了HOCH2CH2NH2 - TrOOO - H2O体系的酸碱行为。该体系中的TrOOO以两种互变异构形式存在,这是由于4-OH基团的酸碱解离和与MEA分子的氢键形成的结合。溶液的pH值与总色差(ΔE76)成正比,而不是特定色差(SCD)。H2SO4 - HOCH2CH2NH2 - TrOOO - H2O体系与HCl和HClO4体系的行为差异是由于第一种酸与MEA(8,0£pH)相互作用形成离子缔合物[HOCH2СH2NH3]2(SO4),该离子缔合物比离子对[[HOCH2СH2NH3](HSO4), [HOCH2СH2NH3](ClO4), [HOCH2СH2NH3]Cl * [HOCH2СH2NH3](O3S-C-10H6-N =N-C6H4-SO3)[H3NCH2СH2OH]更稳定。体系中的酸碱解离常数在很大程度上取决于矿物酸的结构和物理化学参数。在SO2 - MEA - TrOOO - H2O体系(pH = 7,5)的电子吸收光谱中,由于离子-分子形态之间的动态平衡,在415 nm处存在明显的等容点。与本工作中研究的其他系统相比,所指示系统的曲线ΔE76 = f(pH)和SCD = f(pH)上的最大值是重合的。SO2 - MEA - TrOOO - H2O体系的分光光度和比色行为与HCl、HClO4和H2SO4体系的不同是由于硫(IV)氧离子与偶氮指示剂氧化还原相互作用。
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