Application of Asymmetric Marcus-Hush Theory to Voltammetry in Room-Temperature Ionic Liquids

Asymmetric MarcusHush (AMH) theory is applied for the first time in ionic solvents to model the voltammetric reduction of oxygen in 1-butyl-1-methylpyrrolidinium bis-(trifluoromethylsulfonyl)-imide and of 2-nitrotoluene (2-NT), nitrocyclopentane (NCP), and 1-nitro-butane (BuN) in trihexyltetradecylphosphonium tris(pentafluoroethyl)trifluorophosphate on a gold microdisc electrode. An asymmetry parameter, gamma, was estimated for all systems as -0.4 for the reduction of oxygen and -0.05, 0.25, and 0 +/- 0.05 for the reductions of 2-NT, NCP, and BuN, respectively, which suggests equal force constants of reactants and products in the case of 2-NT and BuN and unequal force constants for oxygen and NCP where the force constants of the oxidized species are greater than the reduced species in the case of oxygen and less than the reduced species in the case of NCP. Previously measured values for a, the Butler-Volmer transfer coefficient, reflect this in each case. Where appreciable asymmetry occurs, AMH theory was seen to parametrize the experimental data better than either Butler-Volmer or symmetric Marcus-Hush theory, allowing additionally the extraction of reorganization energy. This is the first study to provide key physical insights into electrochemical systems in room-temperature ionic liquids using AMH theory, allowing elucidation of the reorganization energies and the relative force constants of the reactants and products in each reaction.

Equalising opportunities for women in electoral politics in Ireland: The Views of Women Members of Parliament

This paper examines the attitudes of women political elites in Ireland toward positive action initiatives that would assist in increasing women's legislative presence. An earlier study isolated family responsibilities and lack of finance as significant barriers for Irish women wishing to enter, and stay in, political life. In addition, scholarly and policy debates on boosting women's parliamentary representation focus on manipulating electoral or party selection rules along with strategies for making a political career more compatible with women's socially determined responsibilities. This paper examines how Irish women politicians respond to various suggestions for positive action in these three arenas: combining legislative and family responsibilities, funding a political campaign and getting elected. The paper highlights the broad consensus among women politicians, irrespective of party, self-interest, or length of service, favoring certain positive action initiatives, as well as their reluctance to support other options. It also illustrates the complexity of implementing some of these reforms. In addition, the paper emphasizes how cultural expectations and values act to inhibit women's political agency.