Chemical reversibility, thermodynamics

The design of chemical reactors encompasses at least three fields of chemical engineering thermodynamics, kinetics, and heat transfer. For example, if a reaction is run in a typical batch reactor, a simple mixing vessel, what is the maximum conversion expected This is a thermodynamic question answered with knowledge of chemical equilibrium. Also, we might like to know how long the reaction should proceed to achieve a desired conversion. This is a kinetic question. We must know not only the stoichiometry of the reaction but also the rates of the forward and the reverse reactions. We might also wish to know how much heat must be transferred to or from the reactor to maintain isothermal conditions. This is a heat transfer problem in combination with a thermodynamic problem. We must know whether the reaction is endothermic or exothermic. 

Reversibility — This concept is used in several ways. We may speak of chemical reversibility when the same reaction (e.g., -> cell reaction) can take place in both directions. Thermodynamic reversibility means that an infinitesimal reversal of a driving force causes the process to reverse its direction. The reaction proceeds through a series of equilibrium states, however, such a path would require an infinite length of time. The electrochemical reversibility is a practical concept. In short, it means that the -> Nernst equation can be applied also when the actual electrode potential (E) is higher (anodic reaction) or lower (cathodic reaction) than the - equilibrium potential (Ee), E > Ee. Therefore, such a process is called a reversible or nernstian reaction (reversible or nerns-tian system, behavior). It is the case when the - activation energy is small, consequently the -> standard rate constants (ks) and the -> exchange current density (jo) are high. 

With many electrode reactions, the adsorption of reactants, products, and/or intermediates controls the pathways as well as the reaction rates. Electrochemical reactions are part of the general field of heterogeneous catalysis (31). By controlling the chemical and structural features of the electrode surface (32) as well as electrolyte composition and potential, it is possible to achieve selectivity and specificity for electrochemical reactions. For example, the rate of generation of hydrogen on platinum is 9 to 10 orders of magnitude faster than on lead or mercury at potentials near the reversible thermodynamic value. 

A cell that is chemically irreversible cannot behave reversibly in a thermodynamic sense. A chemically reversible cell may or may not operate in a manner approaching thermodynamic reversibility. 

For polymer surface properties controlled by the chemical composition, thermodynamic (equihbrium), non-equihbrium, and technical terms and definitions play an important role. These are not always used in a consistent way, hence a short recapitulation seems appropriate. The thermodynamic work of adhesion (Wa) is defined as the reversible work (the free energy change) required to separate two phases with unit area of contact, from contact to infinity. The corresponding work of adhesion (and cohesion for similar bodies) can be easily expressed with surface tension values. In general, for surfaces of two intimately contacting solids ( l and 2 , respectively) each with a unit area, are separated in a medium ( 3 ), a work VT132 is required which can be expressed as ... 

Consider the cyclic voltammetry trace of electrically activated iridium oxide (the so called AIROF) which features reversible reactions (Fig. 3.3). The scan rate is very slow, so the dynamic behavior of the Helmholtz capacitance has a negligible effect on the measured trace. The positive peaks A and B correspond to two distinct oxidation reactions at the surface of the electrode, pertaining to different electrode potentials. The negative peaks C and D correspond to reduction reactions. C matches A and D matches B, as they have similar shape. The reduction potential peak (for example at C, Epc) does not happen at a negative electrode-electrolyte voltage drop, but at a positive one even near to the potential where oxidation potential peak (at A, Epa) is located. If the surface redox reactions are fast and the reaction rate is limited by the diffusion of the reactants in the solution, the difference between the oxidation and reduction peaks is only 59 mV/n for a reaction where n electrons are transferred in the stoichiometry of the reaction. This state is called electrochemical reversibility, which means that the thermodynamic equilibrium in the redox reaction at the surface is established fast at every applied electrode potential. Note that this concept is not the same as the chemical reversibility explained before. A system can be electrochemically irreversible but chemically reversible. As seen in Fig. 3.3, iridium oxide is already electrochemically irreversible even at the very slow potential ramp of 50 mV/s, as the , 4 — is already larger than 59 mV. 

These physical separation methods are often reinforced by chemical reactions, which are usually reversible. An elementary treatment of the role of chemical reactions in enhancing separation across a broad spectrum of phase equilibrium driven processes and membrane based processes has been included. The level of treatment in this book assumes familiarity with elementary principles of chemical engineering thermodynamics and traditional... 

Define the roles of kinetics and thermodynamics in chemical engineering. Answer While chemical kinetics is concerned with the rate of a chemical reaction, thermodynamics determines the extent to which reactions occur, that is, to find the yield at eqnilibrinm. In a reversible reaction, chemical equilibrium is reached when the rates of the forward and reverse reactions are equal (the principle of detailed balance) and the concentrations of the reactants and products no longer change. 

Bond and Scholz (606) calculated thermodynamic data for solid mercury bis(dithiocarbamate) complexes mechanically attached to the surface of a paraffin-impregnated graphite electrode. Two-electron reduction generates mercury and the soluble dithiocarbamate anions in a chemically reversible couple during the second and subsequent scans. The formal potential of the reaction has been measured, which enables the calculation of conventional stability constants (P2) for 17 mercury complexes, and a previously unrecognized correlation between log p2 and molecular weight is found (see Section III.G). 

Cell Volta.ge a.ndIts Components. The minimum voltage required for electrolysis to begin for a given set of cell conditions, such as an operational temperature of 95°C, is the sum of the cathodic and anodic reversible potentials and is known as the thermodynamic decomposition voltage, is related to the standard free energy change, AG°C, for the overall chemical reaction,... 

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