Thermodynamics of the Second Dissociation Constant and Standards for pH of 3-(NMorpholino) Propanesulfonic Acid (MOPS) Buffers from 5 to 55°C

The second dissociation constant pK2 of 3-(N-morpholino)propanesulfonic acid (MOPS) has been determined at eight temperatures from 5 to 55°C by measurements of the emf of cells without liquid junction, utilizing hydrogen electrodes and silver–silver chloride electrodes. The pK2 has a value of 7.18 ± 0.001 at 25°C and 7.044 ± 0.002 at 37°C. The thermodynamic quantities ΔG°, ΔH°, ΔS°, and ΔCpo have been derived from the temperature coefficients of the pK2. This buffer at ionic strength I = 0.16 mol-kg−1 close to that of blood serum, has been recommended as a useful secondary pH standard for measurements of physiological fluids. Five buffer solutions with the following compositions were prepared: (a) equimolal mixture of MOPS (0.05 mol-kg−1) + NaMOPS, (0.05 mol-kg−1); (b( MOPS (0.05 mol-kg−1) + NaMOPS (0.05 mol-kg−1) + NaCl (0.05 mol-kg−1); (c) MOPS (0.05 mol-kg−1) + NaMOPS (0.05 mol-kg−1); + NaCl (0.11mol-kg−1); (d) MOPS (0.08 mol-kg−1) + NaMOPS (0.08 mol-kg−1); and (e)MOPS (0.08 mol-kg−1) + NaMOPS (0.08 mol-kg−1) + NaCl (0.08 mol-kg−1).The pH values obtained by using the pH meter + glass electrode assembly are compared with those measured from a flow–junction calomel cell saturated with KCl (cell B), as well as those obtained from cell (A) without liquid junction at 25 and 37°C. The conventional values of the liquid junction potentials Ej have been obtained at 25 and 37°C for the physiological phosphate reference solution as well as for the MOPS buffers (d) and (e) mentioned above.