Amalgamation energy

The decrease in free energy (—AG) which provides the driving force in a cell may ensue either from a chemical reaction or from a physical change. In particular, one often studies cells in which the driving force is a change in concentration (almost always a dilution process). These cells are called concentration cells. The alteration in concentration can take place either in the electrolyte or in the electrodes. As examples of alterations in concentration in electrodes, mention may be made of amalgams or alloy electrodes with different concentrations of the solute metal and in gas electrodes with different pressures of the gas. 

In the decomposer, deionized water reacts with the amalgam, which becomes the anode to a short-circuited cathode. The caustic soda produced is stored or evaporated, if higher concentration is required. The hydrogen gas is cooled by refrigeration to remove water vapor and traces of mercury. Some of these techniques are employed in different facilities to maximize the production of chlorine, minimize the consumption of NaCl, and also to prevent the buildup of impurities such as sulfate in the brine.26 The production of pure chlorine gas and pure 50% sodium hydroxide with no need for further concentration of the dilute solution is the advantage that the mercury cell possesses over other cells. However, the cell consumes more energy and requires a very pure brine solution with least metal contaminants and above all requires more concern about mercury releases into the environment.4... 

The effective hamiltonian in formula 29 incorporates approximations that we here consider. Apart from a term V"(R) that originates in nonadiabatic effects [67] beyond those taken into account through the rotational and vibrational g factors, other contributions arise that become amalgamated into that term. Replacement of nuclear masses by atomic masses within factors in terms for kinetic energy for motion both along and perpendicular to the internuclear axis yields a term of this form for the atomic reduced mass. 

Tab. 6 Standard potentials (in V versus SHE) and free energies of amalgamation (in kj mol ) for alkali metal amalgams and their monovalent cations in water...

Various potentiometric indicator electrodes work as sensors for ion solvation. Metal and metal amalgam electrodes, in principle, respond in a thermodynamic way to the solvation energy of the relevant metal ions. Some ion-selective electrodes can also respond almost thermodynamically to the solvation energies of the ions to which they are sensitive. Thus, the main difficulty in the potentiometric study of ion solvation arises from having to compare the potentials in different solvents, even though there is no thermodynamic way of doing it. In order to overcome this difficulty, we have to employ a method based on an extra-thermodynamic assumption. For example, we can use (1) or (2) below ... 

Eley BM, Garrett JR. 1983. Tissue reactions to the separate implantation of individual constituent phases of dental amalgam, including assessement by energy dispersive x-ray microanalysis. Biomaterials 4 73-80. 

McGinnis JP Jr, Greer JL, Daniels DS. 1985. Amalgam tattoo Report of an unusual clinical presentation and the use of energy dispersive x-ray analysis as an aid to diagnosis. J Am Dent Assoc 110 52-54. 

The first step in this multistage reaction is the nucleophilic addition of sulfone anion 28 to aldehyde 8 (Scheme 14.6). This produces a p-alkoxysulfone intermediate 29 which is trapped with acetic anhydride. The resulting P acetoxysulfone mixture 22 is then subjected to a reductive elimination with Na/Hg amalgam to obtain alkene 23. The tendency of Julia-Lythgoe-Kocienski olefinations to provide ( )-1,2-disubstituted alkenes can be rationalised if one assumes that an a-acyloxy anion is formed in the reduction step, and that this anion is sufficiently long-lived to allow the lowest energy conformation to be adopted. Clearly, this will... 

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