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Energy accounted for through a system's chemical composition and state. A galvanic cell can convert part of the change associated with a redox into electrical work; the system boundaries determine which thermal losses also enter the balance.

A galvanic cell whose reversible electromotive force arises from different reactant activities at otherwise corresponding interfaces. The Nernst equation relates the measured voltage to the activity ratio, provided the transported charge and reaction stoichiometry are specified.

An electric battery converts the available chemical Gibbs free energy of one or more galvanic cells into electrical work delivered to an electrical load. The reacting materials are a finite reservoir: a battery can sustain a terminal electric potential difference while discharging, but cannot supply energy indefinitely. Unlike a capacitor, whose capacitor energy resides in an electric field, a battery chiefly stores its available energy in the chemical state of its materials. The detailed half-reactions and apparatus of a Daniell cell explain this conversion at the electrode level.

During discharge, electrons move through metallic wires from the negative anode, through the electrical load, to the positive cathode; external conventional current points the other way. Inside the battery, ions carry electric current through the electrolyte, and redox chemical reactions connect ionic transport to electronic transport at the electrodes. The same electron does not make a lap through both wire and electrolyte. Electric charge conservation closes the circuit; changing chemical composition supplies the energy. See galvanic cell for the two transport paths and electrolyte for how oppositely moving ions contribute to one net electric current.

The source's electromotive force $\mathcal{E}$ measures its driving work per unit electric charge, in volts; the loaded terminal electric potential difference $V_L$ measures the electrical work per unit electric charge delivered outside the battery. They agree in an ideal lossless source, or approximately near open circuit, but generally differ during discharge.^[ref]

In the ideal fixed-voltage model used in fixed-voltage capacitor energy balance, a battery maintains a prescribed terminal electric potential difference while electric charge flows to or from the capacitor. This is a constraint for that calculation, not an inexhaustible reservoir. The fixed-voltage capacitor energy balance also accounts for electrical energy returned to the source; an actual cell can accept sustained charging only if its chemistry and operating conditions permit it.

Electrochemistry studies how chemical reactions, transport, and chemical equilibrium couple to electric charge and electric potential. In a cell, electrons travel through the external circuit, while mobile ions carry electric current through the electrolyte. At the electrodes, redox reactions connect these two forms of electric charge transport. This connection makes it possible both to obtain electrical work from a chemical reaction and to use electrical work to drive a chemical reaction.

An anode is an electrode where oxidation occurs; a cathode is an electrode where reduction occurs. These definitions refer to the chemical reactions, rather than universal positive or negative terminal signs. In a galvanic cell delivering electrical work, the anode is negative and the cathode positive. In an electrolytic cell driven by an external source, the anode is positive and the cathode negative. See Pingarrón et al., Terminology of electrochemical methods of analysis (IUPAC Recommendations 2019), §§3.1 and 3.4 and Flowers et al., Chemistry 2e, §17.2: galvanic cells.

For a worked example, consider an electrolytic cell containing molten sodium chloride, with the anode connected to the positive terminal and the cathode to the negative terminal of an external source. At the cathode, sodium cations gain electrons; at the anode, chlorine anions lose electrons:The first line has net electric charge zero on each side; the second has $-2e$ on each side. Adding the lines cancels the transferred electrons and preserves both chemical atom counts and net electric charge. The sodium product is neutral, and the chlorine product is a diatomic molecule. These equations specify molten sodium chloride; aqueous chemical solutions introduce competing water reactions. See 17.7 Electrolysis (§17.7: electrolysis of molten sodium chloride).

Electrochemistry underlies battery charging and the manufacture of chemicals by electrolysis. Its particularly useful idea is that an electron inventory in a balanced chemical equation also accounts for transported electric charge. Transport alone is a different question from an electrode chemical reaction: an ion may carry electric current through the electrolyte without itself being consumed at an electrode.

Historically, Michael Faraday introduced the terms electrode, electrolyte, anion, cation, and ion in the terminology section of his 1834 paper, Experimental Researches in Electricity, Seventh Series by Michael Faraday (§§662–667). His §667 explicitly treats the direction assigned to electric current as a convention. His ion language predates the modern electron and atomic nucleus picture used in the charge-counting example above.

For an electrolyte near chemical equilibrium, a Poisson-Boltzmann equation can approximate the distribution of ions in an electric potential. Such an equilibrium model does not by itself describe a cell carrying sustained electric current.

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.

Electrolysis uses an external source of electrical work to drive redox chemical reactions at the electrodes of an electrolytic cell. Its characteristic application is forcing a chemical reaction in a direction that is nonspontaneous under the specified conditions: a discharging galvanic cell supplies electrical work, whereas electrolysis consumes electrical work. This makes electrolysis useful for producing otherwise difficult-to-obtain chemical substances, charging a rechargeable battery, and depositing a metal coating on a conducting object.^[ref]

Always identify the anode by oxidation and the cathode by reduction. In ordinary driven two-terminal operation, the source withdraws electrons from the positive anode and delivers electrons to the negative cathode. In a discharging galvanic cell, the anode is negative and the cathode positive. Thus terminal signs change with operating mode, while the reaction definitions remain valid. Through the electrolyte, ions transport electric charge; they need not all be consumed at an electrode. The electrolyte and electrolytic cell articles explain this transport and its conventional current direction.

For a net chemical equation transferring $z$ electrons per reaction event, the molar reaction Gibbs free energy obeyswhere $F$ is the Faraday constant and $E_{\mathrm{chem}}$ is the reversible cell electromotive force for the reaction in the written direction. A nonspontaneous direction has ${\Delta }_{r}G>0$ and $E_{\mathrm{chem}}<0$ at fixed temperature and pressure. The ideal opposing voltage magnitude is ${\Delta }_{r}G/(zF)$; sustaining a finite electric current generally needs additional drive because of electrical resistance and finite electrode reaction rates. This thermodynamic voltage concerns the actual composition, rather than necessarily standard conditions.^[ref] Not every use of electrolysis increases bulk chemical Gibbs free energy: transferring copper between equivalent surfaces can have zero bulk ${\Delta }_{r}G$ while the source still supplies dissipated electrical work. See the existing electrolytic cell example.

A particularly revealing experiment measures copper transfer instead of merely looking for a coating. Two separated copper electrodes stand in aqueous $\mathrm{CuS}{\mathrm{O}}_4$ electrolyte in a vessel, with insulated leads to a regulated direct-current power supply, a series ammeter and a switch. A balance reads each electrode's mass before and after a timed run. The Institute of Physics describes copper cells with ammeters, adjustable current and removable cathodes; its comparison uses three similar cells at $1\mathrm{A}$ for ten minutes, $0.5\mathrm{A}$ for ten minutes, and $0.5\mathrm{A}$ for twenty minutes. The specified observation to test is that deposited copper mass is proportional to electric current times time. These are documented experimental settings, not measurements generated here.^[ref]

The ideal half-reactions areEach deposited copper chemical atom requires two electrons, so $z=2$. The anode loses copper and the cathode gains it; ideally their mass changes have equal magnitudes, and the bulk copper cation inventory stays constant. Local concentrations near the electrodes can nevertheless differ. The sulfate anions participate in ionic transport without appearing in these net half-reactions; electronic electric current in the wires becomes ionic electric current in the electrolyte through the two interfaces.^[ref]

Clean, rinse, dry and identify the electrodes before their initial weighing. After interrupting the electric current, rinse away adhering electrolyte, dry again and weigh without rubbing off the deposit. KIT's university practical explicitly calls for distilled-water rinsing, careful drying and weighing both electrodes; it warns that loose copper grains can be lost during handling.^[ref] Useful additional controls are repeated drying and weighing until the reading stabilizes, and a matched unpowered immersion followed by the same rinse/dry cycle. These controls test retained liquid, residual dissolved salts, handling loss and chemical changes unrelated to passed electric charge; they are proposed checks, not additional observations reported by KIT. Keep immersed electrode area, spacing, electrolyte composition and temperature comparable across runs, and keep the electrodes from touching.

Record the electric current as a function of time, together with the exact switch-on and switch-off times. Taking $I(t)\ge 0$ in the chosen deposition direction, the transported electric charge isFor constant electric current, $Q=I(t_1-t_0)$; with sampled readings, use numerical integration rather than assuming that one ammeter reading remained constant. The two equal-charge Institute of Physics settings each give $600\mathrm{C}$, while its shorter $0.5\mathrm{A}$ setting gives $300\mathrm{C}$. With $M_{\mathrm{Cu}}=63.546\mathrm{g}\mathrm{mo}{\mathrm{l}}^{-1}$, the mass per amount of substance tabulated by KIT, and $F\approx 96485.33212\mathrm{C}\mathrm{mo}{\mathrm{l}}^{-1}$, ideal Faraday's laws of electrolysis predictThese are calculated predictions for complete conversion of the measured electric charge into retained copper, not experimental results. For a stable process, doubling the electric charge doubles the deposited mass; equal electric charge gives equal deposited mass even when the electric current and duration differ.

The balance reading is a test of the whole model. Competing reduction of water or other chemical species can divert electric current from copper deposition; transient electrode capacitance can also consume part of a short pulse without producing copper. A fragile deposit can detach even when its formation used the expected electric charge. Conversely, retained electrolyte or salts can increase an apparent mass gain. Comparing anode loss with cathode gain helps detect such problems but does not identify every cause. A slope below $M_{\mathrm{Cu}}/(2F)$ alone cannot distinguish competing chemical reactions from lost deposit. Current efficiency measures the fraction of transported electric charge assigned to a specified electrode reaction, rather than the fraction of electrical energy stored chemically.^[ref]

The beautiful connection is that an electrical measurement counts chemical events: integrating electric current and reading a balance provide two ways of following the same electron stoichiometry. This makes electrolysis useful for controlling coating quantity and for testing a charge-to-amount of substance relation. It does not determine coating uniformity, adhesion or the required voltage, which depend on transport and electrode chemical kinetics as well.

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.

An oxidation increases an oxidation state, recording loss from the formal electron assignment. For $\mathrm{Zn}\to {\mathrm{Zn}}^{2+}+2e^{-}$, the increase is $0\to +2$. Oxidation need not involve oxygen.^[ref]

In the electrochemistry examples here, oxidation is loss of electrons by a chemical species; it occurs at the anode. That electrode definition holds in both a galvanic cell and an electrolytic cell; it does not fix terminal polarity. The oxidized chemical species serves as the reducing agent in the coupled redox.

The more negative standard reduction potential identifies iron as the species more readily oxidized. Combining $\mathrm{Fe}\to \mathrm{F}{\mathrm{e}}^{2+}+2{\mathrm{e}}^{-}$ with $\mathrm{S}{\mathrm{n}}^{2+}+2{\mathrm{e}}^{-}\to \mathrm{Sn}$ gives the spontaneous standard galvanic cell reactionThe electron balance is two per reaction, and the activities of the pure metals are unity.

For a galvanic cell, subtract the standard anode reduction potential from the standard cathode reduction potential:A reduction potential is not multiplied by the number of transferred electrons.

Iron is the negative anode and tin is the positive cathode of this spontaneous galvanic cell. electrons travel through the external circuit from iron to tin. An intact tin coating protects iron mainly by physically excluding the corrosive medium. If a defect exposes iron while the metals remain electrically connected, tin is not a sacrificial coating: the exposed iron can become the anodic corrosion site. A small exposed iron area coupled to a large cathodic tin area can be especially damaging; this distinction follows from the electrode-potential order rather than the appearance of the coating.

In a galvanic cell, a spontaneous oxidation-reduction reaction supplies electrical work: ${\Delta }_{r}G<0$ for discharge, the anode is negative, and the cathode positive. A discharging electric battery and a hydrogen–oxygen fuel cell are two practical examples. The first stores its reactants internally; the second is supplied continuously with fuel and oxidant.

An electrolytic cell consumes externally supplied electrical work to drive electrode reactions or material transfer under an applied potential. Its anode is positive and cathode negative. water electrolysis for hydrogen production and metal electroplating are two practical examples. oxidation always occurs at the anode and reduction at the cathode in both cell types; the electrode signs change. The electrolyte conducts ions, while electrons flow through the external circuit. A rechargeable battery can operate in either regime depending on whether it is discharging or being charged.

Consider the reacting zinc and copper species in the zinc-copper displacement experiment. Split the net chemical equation into two half-reactions:

The zinc oxidation state rises from $0$ to $+2$; the copper oxidation state falls from $+2$ to $0$. Add the half-reactions: two released electrons match two accepted electrons. Cancelling $2e^{-}$ from both sides gives^[ref]Thus the closed net chemical reaction has zero net production of free electrons. Cancellation does not destroy electrons: it removes a matched internal exchange from the written chemical equation. The half-reactions alone are incomplete descriptions of the whole reacting system. In a galvanic cell, the exchange can pass through a wire; in the zinc-copper displacement experiment, the reacting materials meet at the same metal surface. The equations do not require a reservoir of free electrons in the bulk chemical solution.

Check both kinds of balance. The oxidation line has net electric charge $0$ on the left and $(+2-2)e=0$ on the right; the reduction line has $(+2-2)e=0$ on the left and $0$ on the right. The net chemical equation contains one zinc and one copper chemical atom on each side and has net electric charge $+2e$ on each side, where $e$ is the positive elementary charge. The written reacting species need not be electrically neutral as a group: the bulk chemical solution also contains compensating anions.

There is an even more literal check. Zinc has atomic number $30$ and copper $29$, so the initial pair contains $30+(29-2)=57$ electrons. The final pair contains $(30-2)+29=57$ electrons. Only their distribution has changed. Conserved chemical element counts give the usual chemical mass conservation inventory; changing the counts of neutral and charged species does not create or remove their atomic nuclei.

Matching electrons is necessary but does not replace balancing every chemical element. The acidic permanganate-iron balance illustrates unequal one- and five-electron exchanges, with water and protons also needed. Conversely, a balanced chemical equation alone establishes neither a reaction rate nor a detailed mechanism. Its usefulness is that it fixes the stoichiometry even when those additional questions remain open.

A reduction decreases an oxidation state, recording gain in the formal electron assignment. For ${\mathrm{Cu}}^{2+}+2e^{-}\to \mathrm{Cu}$, the decrease is $+2\to 0$. The reduced chemical species serves as the oxidizing agent in the coupled redox.^[ref]

In the electrochemistry examples here, reduction is gain of electrons by a chemical species; it occurs at the cathode. That electrode definition holds in both a galvanic cell and an electrolytic cell; it does not fix terminal polarity.