The amine carbamate related equilibrium (RNHCOO − + H 2 O ⇆ RNH 2 + HCO 3 − ) has been investigated with 13 C NMR (Nuclear Magnetic Resonance) spectroscopy for a series of linear primary alkanolamines, and the apparent carbamate decomposition equilibrium constants have been estimated. A quantitative NMR method for the calculation of the concentration of the species formed in solution has been provided, including the assessment of each of the fast exchanging proton species (whose nuclei resonate at the same chemical shifts in the NMR spectra). For this purpose, NMR-based calibration curves were utilized and an alternative method was applied for validation. The overall results showed that the amount of carbamate found at the equilibrium decreased as the length of the carbon chain increased, while the corresponding apparent carbamate decomposition equilibrium constants featured the same order of magnitude (10
−2).
The objective of this work is to suggest a mathematical model for mass-transfer of a paramagnetic electrolyte, nickel(ii)chloride solution, through an inert, thin membrane from one chamber to another under the influence of magnetic fields which are applied perpendicular to the membrane. The model is based on the magnetic concentration gradient force, the Fick’s law of diffusion, and the Hagen-Poiseuille law for paramagnetic ion transport in the membrane. The magnetic concentration gradient force is found to be elusive and points in the direction of the magnetic field, in our case, the direction of the Fick diffusion flux. The reason is the gradient of the magnetic volume susceptibility for the electrolyte in the membrane, which decreases in the direction of the magnetic field. This is in accordance with the variable-reluctance principle. Mass balances for transport of Ni ions in distilled water through the membrane are derived and governed by a partial differential equation in one-dimensional space and time with specified initial and boundary conditions. The associated flux is superimposed on the pure Fick diffusion flux. The total flux is described by a nonlinear partial differential equation, which has not previously been used to describe transfer phenomena in paramagnetic solutions in magnetic fields. The simulated results were compared with experimental results and coincide approximately in all points for unstirred solutions. In stirred solutions, where the mass transfer coefficient at the membrane inlet approaches infinity if the mixing is ideal, no experimental or simulated effect was observed of the magnetic field.
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