The authors have undertaken the determination of pH values for one buffer solution of TES without NaCl and nine buffer solutions with NaCl yielding an ionic strength I = mol.kg-1. similar to that of blood. These buffe...The authors have undertaken the determination of pH values for one buffer solution of TES without NaCl and nine buffer solutions with NaCl yielding an ionic strength I = mol.kg-1. similar to that of blood. These buffer solutions have been evaluated in the temperature range of 5℃ to 55℃ using an extended version of the Debye-Hückel equation. The pH values are reported using 1) the Debye-Hückel extension of the Bates-Guggenheim convention in the tempera- ture range 5℃ to 55℃ and 2) with and without liquid junction correction at 25℃ and 37℃. These TES buffer solutions are recommended as secondary standard references for pH measurements in the range of pH 7.2 to 7.5 for physiological application with an ionic strength of I = 0.16 mol.kg-1.展开更多
Values of the second thermodynamic dissociation constant pK2 of the protonated form of monosodium 1,4-piperazinediethanesulfonate (PIPES) have been determined at twelve different temperatures in the temperature range ...Values of the second thermodynamic dissociation constant pK2 of the protonated form of monosodium 1,4-piperazinediethanesulfonate (PIPES) have been determined at twelve different temperatures in the temperature range from (278.15 to 328.15) K including the body temperature 310.15 K by measurement of the electromotive-force for cells without liquid junction of the type: Pt (s), H2 (g), 101.325 kPa|Na-PIPES (m1) + Na 2-PIPES (m2) + NaCl (m3)|AgCl (s), Ag (s), where m1, m2 and m3 indicate the molalities of the corresponding species at 1 atm = 101.325 kPa in SI units. The pK2 values for the dissociation of Na-PIPES are represented by the equation: pK2 = -1303.76/T + 48.369 - 6.46889 lnT with an uncertainty of ± 0.001. The values of pK2 for Na-PIPES were found to be 7.1399 ± 0.0004 at 298.15 K and 7.0512 ± 0.0004 at 310.15 K, respectively, and indicate that this buffer would be useful as pH standard in the range of physiological application. Standard thermodynamic quantities for the acidic dissociation process of Na-PIPES have been derived from the temperature coefficients of the pK2. These values are compared with those of structurally related N-substituted PIPERAZINE and TAURINE at 298.15 K.展开更多
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 includin...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.展开更多
Thermodynamic dissociation constants pKa of 2,2-bis(hydroxymethyl)-2,2’,2”-nitrilotriethanol have been determined at 12 temperatures from (278.15 to 328.15) K including the body temperature 310.15 K by the electromo...Thermodynamic dissociation constants pKa of 2,2-bis(hydroxymethyl)-2,2’,2”-nitrilotriethanol have been determined at 12 temperatures from (278.15 to 328.15) K including the body temperature 310.15 K by the electromotive-force measurements (emf) of hydrogen-silver chloride cells without liquid junction of the type: Pt(s), H2(g), 101.325 kPa|BIS-TRIS (m) + BIS-TRIS·HCl (m)| AgCl(s), Ag(s), where m denotes molality. The pKa values for the dissociation process of BIS-TRIS·H++ H2O = H3O+ + BIS-TRIS given as a function of T in Kelvin (K) by the equation pKa = 921.66 (K/T) + 14.0007-1.86197 ln(T/K). At 298.15 and 310.15 K, the values of pKa for BIS-TRIS were found to be 6.4828 ± 0.0005 and 6.2906 ± 0.0006 respectively. Thus buffer solutions composed of BIS-TRIS and its hydrochloride would be useful as secondary pH buffer standards and for control of acidity in the pH range 6 to 8. At 298.15 K the thermodynamic functions G°, H°, S° and Cp° for the dissociation process of BIS-TRIS·H+ are G°=37,005 J·mol-1, H° = 28,273 J·mol-1, S°= 29.3 J·K-1·mol-1 and Cp° = 36 J·K-1·mol-1. These results are compared with the dissociation of protonated bases structurally related to BIS-TRIS·H+.展开更多
文摘The authors have undertaken the determination of pH values for one buffer solution of TES without NaCl and nine buffer solutions with NaCl yielding an ionic strength I = mol.kg-1. similar to that of blood. These buffer solutions have been evaluated in the temperature range of 5℃ to 55℃ using an extended version of the Debye-Hückel equation. The pH values are reported using 1) the Debye-Hückel extension of the Bates-Guggenheim convention in the tempera- ture range 5℃ to 55℃ and 2) with and without liquid junction correction at 25℃ and 37℃. These TES buffer solutions are recommended as secondary standard references for pH measurements in the range of pH 7.2 to 7.5 for physiological application with an ionic strength of I = 0.16 mol.kg-1.
文摘Values of the second thermodynamic dissociation constant pK2 of the protonated form of monosodium 1,4-piperazinediethanesulfonate (PIPES) have been determined at twelve different temperatures in the temperature range from (278.15 to 328.15) K including the body temperature 310.15 K by measurement of the electromotive-force for cells without liquid junction of the type: Pt (s), H2 (g), 101.325 kPa|Na-PIPES (m1) + Na 2-PIPES (m2) + NaCl (m3)|AgCl (s), Ag (s), where m1, m2 and m3 indicate the molalities of the corresponding species at 1 atm = 101.325 kPa in SI units. The pK2 values for the dissociation of Na-PIPES are represented by the equation: pK2 = -1303.76/T + 48.369 - 6.46889 lnT with an uncertainty of ± 0.001. The values of pK2 for Na-PIPES were found to be 7.1399 ± 0.0004 at 298.15 K and 7.0512 ± 0.0004 at 310.15 K, respectively, and indicate that this buffer would be useful as pH standard in the range of physiological application. Standard thermodynamic quantities for the acidic dissociation process of Na-PIPES have been derived from the temperature coefficients of the pK2. These values are compared with those of structurally related N-substituted PIPERAZINE and TAURINE at 298.15 K.
文摘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.
文摘Thermodynamic dissociation constants pKa of 2,2-bis(hydroxymethyl)-2,2’,2”-nitrilotriethanol have been determined at 12 temperatures from (278.15 to 328.15) K including the body temperature 310.15 K by the electromotive-force measurements (emf) of hydrogen-silver chloride cells without liquid junction of the type: Pt(s), H2(g), 101.325 kPa|BIS-TRIS (m) + BIS-TRIS·HCl (m)| AgCl(s), Ag(s), where m denotes molality. The pKa values for the dissociation process of BIS-TRIS·H++ H2O = H3O+ + BIS-TRIS given as a function of T in Kelvin (K) by the equation pKa = 921.66 (K/T) + 14.0007-1.86197 ln(T/K). At 298.15 and 310.15 K, the values of pKa for BIS-TRIS were found to be 6.4828 ± 0.0005 and 6.2906 ± 0.0006 respectively. Thus buffer solutions composed of BIS-TRIS and its hydrochloride would be useful as secondary pH buffer standards and for control of acidity in the pH range 6 to 8. At 298.15 K the thermodynamic functions G°, H°, S° and Cp° for the dissociation process of BIS-TRIS·H+ are G°=37,005 J·mol-1, H° = 28,273 J·mol-1, S°= 29.3 J·K-1·mol-1 and Cp° = 36 J·K-1·mol-1. These results are compared with the dissociation of protonated bases structurally related to BIS-TRIS·H+.
