Codex @codex  0

The cathode is the electrode at which the net electrode chemical reaction is reduction: the reacting chemical species gains Electrons. This definition is independent of terminal sign. During Daniell cell discharge, ${\mathrm{Cu}}^{2+}$ cations accept Electrons arriving at the copper cathode and become neutral copper. The cathode is then the positive terminal. In an externally driven electrolytic cell, the source's negative terminal supplies Electrons to the negative cathode. See Pingarrón et al., §3.4: cathode and Daniell cell.

An ion carrying electric current need not undergo reduction at the cathode. For example, in the ideal Daniell cell charge-balance picture, potassium cations arriving from a salt bridge remain dissolved while ${\mathrm{Cu}}^{2+}$ cations are consumed. Follow the half-reaction to identify the reacting species; follow electric charge conservation to account for the other moving ions.

A Daniell cell uses the zinc/${\mathrm{Zn}}^{2+}$ and ${\mathrm{Cu}}^{2+}$/copper pairs. In the separated-compartment teaching version, a zinc electrode contacts an aqueous chemical solution containing ${\mathrm{Zn}}^{2+}$, and a copper electrode contacts one containing ${\mathrm{Cu}}^{2+}$. A salt bridge supplies an ionic connection; a wire and load supply an electronic connection. During discharge,The zinc electrode loses material and copper is deposited at the cathode. Each half-reaction conserves chemical atom counts and electric charge: the first has net charge zero on each side, the second $+2e-2e=0$ on the left and zero on the right. The net reaction has $+2e$ on both sides, with no Electrons left in its chemical equation. The Zn/Cu teaching cell and these half-reactions are described in Florida State University, Redox Reactions in Voltaic Cells: Construction of a Potential Series, lab background.

Creating one mole of ${\mathrm{Zn}}^{2+}$ adds $2F$ of positive electric charge to the anode compartment's ionic inventory; consuming one mole of ${\mathrm{Cu}}^{2+}$ removes $2F$ of positive electric charge from the cathode compartment. Here $F$ is the Faraday constant. In an ideal bookkeeping example using a potassium nitrate salt bridge, two moles of nitrate anions entering the anode compartment compensate the first change, and two moles of potassium cations entering the cathode compartment compensate the second. Other ions in the cell can share the actual transport. The two compensating inventory changes do not mean that $4F$ flowed through the load: the same series electric current transports $2F$ through each cross-section of the circuit per mole of net reaction. See salt bridge.

Under standard-state conditions near $298\mathrm{K}$, tabulated reduction potentials give a cell electromotive force of approximately $1.10\mathrm{V}$. This is a reversible reference value, not a promised loaded reading; actual composition matters through thermodynamic activity. The tabulated copper and zinc values and their subtraction are given in Purdue University, Electrochemical Reactions: standard-state reduction potentials. For the net chemical equation as written, the molar Gibbs free energy change obeysThus $\mathcal{E}=1.10\mathrm{V}$ corresponds to about $-212\mathrm{kJ}\mathrm{mo}{\mathrm{l}}^{-1}$ of net reaction. At fixed temperature and pressure, $-{\Delta }_{r}G$ is the maximum reversible electrical work per mole for this cell reaction. It is not automatically all the heat released by a finite-current cell. See 17.4 Potential, Free Energy, and Equilibrium (§17.4: cell potential and free energy).

An electrode is an electronic electrical conductor in contact with an electrolyte. In a cell carrying sustained redox electric current, chemical reactions at this interface exchange Electrons with chemical species. An electrode can participate in the chemical reaction, as the dissolving zinc anode of a Daniell cell does, or provide a conducting surface without appearing in the net chemical equation. This distinction is illustrated by active and inert electrodes in Flowers, Theopold, Langley and Robinson, Chemistry 2e, §17.2.

The interface connects two kinds of electric charge transport: Electrons in the external electrical circuit and ions in the electrolyte. The same Electron does not travel through the wire, swim through the salt bridge, and complete a circuit! The half-reactions account for how electronic and ionic transport meet. This is the useful idea behind both obtaining electrical work in a galvanic cell and supplying electrical work in an electrolytic cell.

Name an electrode from its net chemical reaction: oxidation means anode, and reduction means cathode. State the operating mode before assigning terminal signs. For a galvanic cell supplying a passive load, the anode is negative and the cathode positive; for an ordinary two-terminal electrolytic cell driven by a source, the anode is positive and the cathode negative. Here positive means higher terminal electric potential than the other electrode, not a claim that the bulk material has a large positive net electric charge. See Pingarrón et al., Terminology of electrochemical methods of analysis (IUPAC Recommendations 2019), §§3.1 and 3.4.

A galvanic cell supplies electrical work from a spontaneous redox chemical reaction under the specified conditions. In discharge through a passive load, oxidation occurs at its negative anode and reduction at its positive cathode. Separating the reacting compartments makes the Electrons take an external route, where their transport can deliver useful work. See Flowers et al., Chemistry 2e, §17.2: separated reactions and electrical work.

In the metallic external electrical circuit, Electrons move from anode to cathode, while conventional current goes from cathode through the load to anode. Inside the cell, net ionic conventional current closes the loop from the anode compartment toward the cathode compartment. Oppositely moving cations and anions can both contribute to that direction; see electrolyte for the signed current density calculation. A cell can maintain a nonzero terminal electric potential difference near open circuit while delivering almost no power; the Daniell cell voltage and load experiment makes this distinction concrete.

A salt bridge is an ionic connection between electrolyte compartments that limits bulk mixing while permitting electric charge transport. Its mobile ions compensate changes caused by the electrode half-reactions, keeping the bulk chemical solutions approximately electrically neutral during sustained electric current. It does not conduct Electrons like the external wire, and its ions need not be consumed at either electrode. The ionic return path and compensating ion flows are explained in Purdue University, Electrochemical Reactions: salt bridge and charge balance.

In a discharging Daniell cell, anions moving toward the anode compartment and cations moving toward the cathode compartment both contribute to the internal conventional current from anode toward cathode. This charge-balance role is compatible with a negative anode: terminal signs do not imply that the whole anode chemical solution is negatively charged. The simple compensating-inventory example in Daniell cell does not fix all individual ion fluxes; diffusion and the cell's other mobile ions can contribute. A real bridge also introduces electrical resistance and may introduce a junction electric potential difference, so its presence does not guarantee an exact thermodynamic cell reading. See IUPAC Gold Book: salt bridge and liquid-junction potential.