Buffer standards for the physiological pH of the zwitterionic buffer 3-[<i>N</i>-tris(hydroxymethyl)methylamino]-2-hydroxypropanesulfonic Acid (TAPSO) From (278.15 to 328.15) K

The second dissociation constant, pK2, and related thermodynamic quantities for TAPSO have been previously determined and reported from the temperatures (278.15 to 328.15) K. In the current study there are five buffer solutions without NaCl and five buffer solutions with NaCl present which yield an ionic strength (I = 0.16 mol·kg-1) similar to that of blood plasma. These buffer solutions have been evaluated in the temperature range of (278.15 to 328.15) K using the extended Debye-Hückel equation, due to the limitations of the Bates-Guggenheim convention such that it is only valid when I -1. The liquid junction potential (Ej) values between the TAPSO solution and the saturated KCl calomel electrode solution have been estimated at (298.15 and 310.15) K using a flowing junction cell measurement. The previously mentioned Ej values have been used in determining the operational pH values at (298.15 and 310.15) K. These TAPSO buffer solutions are recommended as reference solutions for pH measurements in saline media with an ionic strength of I = 0.16 mol·kg-1.

Buffer Standards for the Biochemical pH of the Zwitterionic Buffer <i>N</i>-Tris-(Hydroxymethyl) Methyl-2-Aminoethanesulfonic Acid (TES) from 5℃ to 55℃

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.

Calculation of the pH of Buffer Solution of 2-[<i>N</i>-Morpholino]ethanesulfonic Acid (MES) from 5°C to 55°C

This paper reports the results for the pH of three buffer solutions free of chloride ion. The remaining six buffer solutions have saline media of the ionic strength I = 0.16 mol.kg-1, matching closely to that of the physiological sample. Conventional paH values for the three buffer solutions without the chloride ion and six buffer solutions with the chloride ion at I = 0.16 mol.kg-1 from 5°C to 55°C have been calculated. The operational pH values for five buffer solutions at 5°C and 55°C have been determined based on the difference in the values of the liquid junction potentials between the blood phosphate standard and the experimental buffer solutions. Five of these buffers are recommended as standards for the physiological pH range 7.5 to 8.5.

Dissociation Constant of N-(2-Acetamido)-Iminodiacetic Acid Monosodium (ADA) from (278.15 to 328.15) K

The acidic dissociation constant of N-(2-acetamido)-iminodiacetic acid monosodium (ADA) has been determined at 12 temperatures from 278.15 to 328.15 K by electromotive-force (emf) measurements of hydrogen-silver chloride cells without liquid junction. At 298.15 K, the value of the dissociation constant (pK2) is 6.8416 ± 0.0004. In response to the need for new physiological pH standards, buffer solutions of NaADA and its disodium salt, Na2ADA would be useful for pH control in the biological region of pH 6.5 to 7.5. The pK2 values over the experimental temperature range are given as a function of the thermodynamic temperature (T) by the equation pK2 = 2943.784/T - 47.05762 + 7.72703 ln T. At 298.15 K, standard thermodynamic quantities for the dissociation process have been derived from the temperature coefficients;ΔH° = 12,252 J·mol-1, ΔS° = -89.9 J·K-1·mol-1 and = -148 J·K-1·mol-1. The results are interpreted and compared with those of structurally related derivatives of GLYCINE.

Buffer Standards for Physiological pH of the Buffer N-(2-Acetamido)-2-aminoethanesulfonic Acid from 5°C to 55°C

Electromotive force (emf) measurements of the Cell Pt(s), H2(g)|ACES(m1) + NaACES(m2) + NaCl (m3)| AgCl, Ag(s) have been carried out from 5°C to 55°C . The agreement of pH values between two calculated (extended Debye-Hückel and liquid junction correction) is very good. Two buffer solutions without the chloride ion and seven buffer solutions with NaCl, at an ionic strength (I = 0.16 mol.kg-1) similar to that of physiological fluids, have been studied. The pH values for these buffer solutions have been evaluated in the temperature range of 5°C to 55°C using the extended Debye-Hückel equation of the Bates-Guggenheim convention. Values of the residual liquid junction potential (δEj) between the ACES solutions and the saturated KCl calomel electrode solution have been estimated at 25°C and 37°C from the previously determined Ej values using the flowing junction cell to determine the operational pH values at 25°C and 37°C. These ACES buffer solutions are recommended as secondary standard reference solutions for pH measurements in the range of physiological applicati on at I = 0.16 mol.kg-1.

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

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.

Thermodynamics of the Second Stage Dissociation Step (pK₂) of Buffer Monosodium 1,4-Piperazinediethanesulfonate from (278.15 to 328.15) K

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.

Acid Dissociation Constants and Related Thermodynamic Functions of Protonated 2,2-Bis(Hydroxymethyl)-2,2’,2”- Nitrilotriethanol (BIS-TRIS) from (278.15 to 328.15) K

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+.