Thermodynamics of the In|In+3 Electrode in HCl + InCl3 Solutions

Electromotive force measurements have been made using the cell $$\mbox{In(s)}|\mbox{HCl }(m_{\mathrm{A}}),\mbox{InCl}_{3}(m_{\mathrm{B}}),\mbox{H}_{2}\mbox{O}|\mbox{AgCl, Ag}$$ in the ionic strength range of I=0.05, 0.1, 0.25, 0.5, 1.0, 1.5, 2.0, 2.5 and 3.0 mol?kg^?1 at 25?°C. The value of E ^o, the standard potential of the In/In³⁺ electrode, has been determined at 25?°C. Our value of E ^o (?0.3371 V) at 25?°C obtained from our measurements is in good agreement with ?0.336 (Hakomori, J. Am. Chem. Soc. 52: 2372–2376, 1930) and ?0.3382 V (Covington et al., J. Chem. Soc. 4394–4401, 1963). The activity coefficients of InCl₃ as well as Harned interaction coefficients have been determined at 25?°C for each of the experimental ionic strengths at ionic strength fractions of 0.1, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 and 0.9 of HCl. Harned’s rule for the salt is obeyed at I=0.05,0.1 and 0.25 mol?kg^?1 but the quadratic terms are needed for higher ionic strengths. These data, together with others for the activity coefficient of HCl in the same solutions, have been treated by the ion-interaction (Pitzer, Activity Coefficients in Electrolyte Solutions, CRC Press, 1991) equations in a previous publication.     

Effects of hydrogen bonding on the ring stretching modes of pyridine

The effects of hydrogen bonding on the ring stretching modes (both ring breathing and triangle) of pyridine are experimentally investigated using noisy light based coherent Raman scattering spectroscopy. Three systems, pyridine/formamide, pyridine/water, and pyridine/acetic acid, provide varying degrees of strength for the diluent-pyridine hydrogen bond complex. Formamide forms a relatively weaker hydrogen bond, while acetic acid essentially fully transfers a proton to pyridine. Both dilution studies and temperature studies are performed on the three systems. Together, these provide a broad context in which a very simple model for the electronic behavior of pyridine is formulated. This model is based on a molecular orbital picture and electrostatic arguments, and it well explains the observed experimental results. Additionally, a new mechanism for the line broadening of the ring breathing mode for the pyridine-water hydrogen bonded complex is proposed.