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The entire change of enthalpy in this process is converted to heat If, however, this reaction is carried out by immersing a zinc rod into a solution of zinc ions and a copper rod into a solution of copper ions and the solutions are brought into contact (eg across a porous diaphragm, to prevent mixing), then zinc will pass into the solution of zinc ions and copper will be deposited from the solution of copper ions only when both metals are connected externally by a conductor so that there is a closed circuit The cell can then carry out work in the external part of the circuit In the first arrangement, reversible reaction is impossible but it becomes possible in the second, provided that the other conditions for reversibility are fulfilled.

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In the reversible case, the total change of the Gibbs energy during the reaction occurring in the cell will be transformed into electrical work, while in the irreversible case the electric work will be smaller and can be zero For reversible behaviour in a galvanic cell two requirements need to be fulfilled; there must be material and energetic reversibility Most practical galvanic cells, however, show a certain degree of irreversibility Material reversibility can be demonstrated by balancing the EMF of the cell with an equal and opposite electrical potential difference from a potentiometer, and then causing the reaction in the cell (the cell reaction) to proceed, first in one direction and then in the reverse direction, by adjusting the balancing electrical potential difference to be greater than and then less than the cell EMF.

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The project office employs a skilled staff dedicated solely to working with the system builder and the team leaders to update the project plan and budget as work progresses The system builder is analogous to the general manager of a business unit, and the project office is like the accounting department The general manager does not have time to keep the business unit s books nor is that the general manager s job But if no one keeps the books, the general.

Energetic reversibility is achieved when the same amount of electrical work is supplied from the cell reaction proceeding in one direction as is gained from the reaction proceeding to the same degree in the opposite direction Reversible operation of the cell requires that no other process occurs in the cell than that connected with the current flow An electrochemical process that need not be always connected with the passage of current is the dissolution of a metal in an acid (eg zinc in sulphuric acid in the Volta cell) or the dissolution of a gas in an electrolyte solution (eg in a cell consisting of hydrogen and chlorine electrodes, hydrogen and chlorine are dissolved.

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159 and hydrogen chloride can be formed in solution even without current flow; this reaction, however, is strongly inhibited kinetically). Another process that can occur in the absence of current passage is diffusion. In a concentration cell (see Section 3.2.1), the concentrations of the two solutions can be equalized, even in the absence of current passage, through diffusion alone. However, this part will consider cells for which both of the criteria of thermodynamic reversibility are satisfied. The irreversible processes described must not occur even on open circuit. In a reversible cell, a definite equilibrium must be established and this may be defined in terms of the intensive variables in a similar way to the description of phase and chemical equilibria of electroneutral components. Further, the passage of a finite amount of charge corresponds to a certain degree of energetic irreversibility, as the electrical work is converted into Joule heat because of the internal resistance of the cell and also in the external circuit; in addition, electrode processes involve a certain overpotential (see 5). Thus, the cell can work reversibly only on passage of negligible current, i.e. when the difference between the balancing external voltage and the EMF of the cell approaches zero. It should be noted that the reversibility of the galvanic cell has so far been considered from a purely thermodynamic point of view. 'Reversible electrode processes' are sometimes considered in electrochemistry in a rather different sense, as will be described in 5. A galvanic cell is usually depicted in terms of chemical symbols. The phase boundary is designated by a vertical line. For aqueous solutions, the dissolved substances and their concentrations are indicated, and for non-aqueous solutions, also the solvent. For example, the cell Hg, Zn(12%) | ZnSO4(sat.), Hg2SO4(sat.) | Hg (3.1.37)

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