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Reversible Chemical Reaction
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The concept of a reversible chemical reaction is illustrated by the decomposition of calcium carbonate, which when heated forms calcium oxide and carbon dioxide gas At equilibrium, this system exerts a definite decomposition pressure of C 0 2 for a given temperature When the pressure falls below this value, CaC03 decomposes Assume that a cylinder is fitted with a frictionless piston and contains CaC03, CaO, and C 0 2 in equilibrium It is immersed in a constant-temperature bath, as shown in Fig 23, with the temperature adjusted to a value such that the decomposition pressure is just sufficient to balance the weight on the piston The system is in mechanical equilibrium, the temperature of the system is equal to that of the bath, and the chemical reaction is held in balance by the pressure of the C02 Any change of conditions, however slight, upsets the equilibrium and causes the reaction to proceed in one direction or the other If the weight is differentially increased, the C 0 2 pressure rises differentially, and COz combines with CaO to form CaC03, allowing the weight to fall slowly The heat given off by this reaction raises the temperature in the cylinder, and heat flows to the bath Decreasing the weight differentially sets off the opposite chain of events The same results are obtained if the temperature of the bath is raised or lowered If the temperature of the bath is raised differentially, heat flows into the cylinder and calcium carbonate decomposes The C 0 2 generated causes the pressure to rise differentially,which in turn raises the piston and weight This continues until the
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28 The Reversible Process
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Figure 23 Reversibility of a chemical reaction
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CaC03 is completely decomposed The process is reversible, for the system is never more than differentially displaced from equilibrium, and only a differential lowering of the temperature of the bath causes the system to return to its initial state Chemical reactions can sometimes be carried out in an electrolytic cell, and in this case they may be held in balance by an applied potential difference If such a cell consists of two electrodes, one of zinc and the other of platinum, immersed in an aqueous solution of hydrochloric acid, the reaction that occurs is: Zn + 2HC1+ Hz + ZnC12 The cell is held under fixed conditions of temperature and pressure, and the electrodes are connected externally to a potentiometer If the electromotive force produced by the cell is exactly balanced by the potential difference of the potentiometer, the reaction is held in equilibrium The reaction may be made to proceed in the forward direction by a slight decrease in the opposing potential difference, and it may be reversed by a corresponding increase in the potential difference above the emf of the cell
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Summary Remarks on Reversible Processes
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A reversible process: Is frictionless Is never more than differentially removed from equilibrium Traverses a succession of equilibrium states Is driven by forces whose imbalance is differential in magnitude Can be reversed at any point by a differential change in external conditions When reversed, retraces its forward path, and restores the initial state of system and surroundings The work of compression or expansion of a gas caused by the differential displacement of a piston in a cylinder is derived in Sec 17: d w =-pdvt (12)
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CHAPTER 2 The First Law and Other Basic Concevts
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The work done on the system is given by this equation only when certain characteristics of the reversible process are realized The first requirement is that the system be no more than infinitesimally displaced from a state of internal equilibrium characterized by uniformity of temperature and pressure The system then always has an identifiableset of properties, including pressure P The second requirement is that the system be no more than infinitesimallydisplaced from mechanicalequilibrium with its surroundingsIn this event, the internal pressure P is never more than minutely out of balance with the external force, and we may make the substitution F = P A that transforms Eq (11) into Eq (12) Processes for which these requirements are met are said to be mechanically reversible, and Eq (12) may be integrated:
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The reversible process is ideal in that it can never be fully realized; it represents a limit to the performance of actual processes In thermodynamics, the calculation of work is usually made for reversible processes, because of their tractability to mathematical analysis The choice is between these calculations and no calculations at all Results for reversible processes in combination with appropriate eficiencies yield reasonable approximations of the work for actual processes
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