Thermodynamics of the Second Dissociation Constants (pK2) of Piperazine-N,N′-bis-2-hydroxypropanesulfonic Acid (POPSO Sesquisodium Salt) and Associated Thermodynamic Functions from (278.15 to 328.15) K

R. Roy, L. N. Roy, Katherine E. Hundley, Taylor R. Wehmeyer, Lucas S. Tebbe
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Abstract

The second acidic dissociation constants of protonated piperazine-N,N′-bis-2-hydroxypropane-sulfonic acid (POPSO sesquisodium salt) have been determined at 12 different temperatures from (278.15 to 328.15) K including 310.15 K. Electromotive-force measurement technique was used employing hydrogen-silver chloride cells without liquid junction. The results of pK2 are given by the equation: pK2 = -1041.77/T + 51.0459 - 6.97646lnT. The uncertainty of the fit is ±0.0008. At 289.15 K, pK2 = 7.8029; whereas, at 310.15 K (body temperature), pK2 = 7.6862. Thus, the buffer solutions of POPSO and its sodium salt are useful for pH control in the physiological pH region of (7.0 to 8.5). The changes of Gibbs free energy (G°), enthalpy (H°), entropy (S°) and heat capacity Cp° were computed from the temperature derivative of the pK2 for the dissociation of the zwitterionic acid POPSO±-3 = POPSO-4 + H+ in the standard state. At 298.15 K, these results are compared with those of similar components, which are the derivatives of the parent compounds TAURINE, PIPERAZINE and MORPHOLINE.
(278.15 ~ 328.15) K范围内哌嗪-N,N ' -双-2-羟基丙磺酸(POPSO倍半钠盐)第二解离常数(pK2)的热力学及相关热力学函数
测定了质子化哌嗪-N,N ' -双-2-羟基丙烷磺酸(POPSO倍半钠盐)在(278.15 ~ 328.15)K (310.15 K) 12种不同温度下的第二次酸解常数。采用无液结的氯化氢银电池进行电动势测量。pK2的结果由等式给出:pK2 = -1041.77/T + 51.0459 - 6.97646lnT。拟合的不确定度为±0.0008。289.15 K时,pK2 = 7.8029;而在310.15 K(体温)时,pK2 = 7.6862。因此,POPSO及其钠盐缓冲液可用于控制pH值在(7.0 ~ 8.5)的生理pH范围内。由双离子酸POPSO±-3 = POPSO-4 + H+在标准状态下解离时pK2的温度导数计算了吉布斯自由能(G°)、焓(H°)、熵(S°)和热容Cp°的变化。在298.15 K下,这些结果与类似成分的结果进行了比较,这些成分是母体化合物牛磺酸,哌嗪和MORPHOLINE的衍生物。
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