The Faraday constant, denoted by the symbol F, is a fundamental physical constant in electrochemistry defined as the electric charge carried by one mole of electrons.[1][2] Its value is exactly 96 485.332 123 310 0184 coulombs per mole (C mol⁻¹), as established by the 2019 redefinition of the International System of Units (SI), under which it is the product of the exact Avogadro constant (N_A = 6.022 140 76 × 10²³ mol⁻¹) and the exact elementary charge (e = 1.602 176 634 × 10⁻¹⁹ C).[1][3]Named after the British scientist Michael Faraday (1791–1867), who pioneered the study of electrolysis in the early 1830s, the constant quantifies the relationship between electrical charge and chemical change in electrochemical reactions.[4][5] It is central to Faraday's laws of electrolysis, which state that the mass of a substance altered at an electrode during electrolysis is directly proportional to the quantity of electricity transferred and to the substance's equivalent weight.[6][7] In practice, one faraday (ℱ) of charge corresponds to the transfer of one mole of singly charged ions or electrons, enabling precise calculations in applications such as batteries, electroplating, and corrosion analysis.[2][8] The constant also appears in key equations, including the Nernst equation for cell potentials (E = E° − (RT/nF) ln Q) and the relation between Gibbs free energy and cell potential (ΔG = −nF E), where n is the number of moles of electrons transferred.[2]
Definition and Value
Definition
The Faraday constant, denoted by the symbol F, is a fundamental physical constant defined as the electric charge carried by one mole of singly charged ions or, equivalently, by one mole of electrons.[9][1] This constant quantifies the molar elementary charge, linking the amount of substance in moles to the total electric charge in coulombs.[10]It plays a crucial role in electrochemistry by connecting macroscopic quantities, such as the electric current and time involved in electrolytic processes, to atomic-scale properties, including the discrete charges of electrons or ions.[11]The constant is named after the English physicist and chemist Michael Faraday (1791–1867), who established the foundational laws of electrolysis that revealed the proportional relationship between electricity and chemical decomposition.[12]In the context of the International System of Units (SI), the Faraday constant is a derived constant; since the 2019 redefinition of the SI base units, it has an exactly defined value as the product of the fixed Avogadro constant and the elementary charge.[13][1]
Numerical Value and Precision
The Faraday constant F has an exact value of $96\,485.332\,123\,310\,0184 C mol^{-1} in the International System of Units (SI), established following the 2019 redefinition of the SI base units.[1] This precise numerical value is derived directly from the product of the elementary charge e and the Avogadro constant N_\mathrm{A}, both of which were fixed as exact constants in the revision. Specifically, e = 1.602\,176\,634 \times 10^{-19} C (exact) and N_\mathrm{A} = 6.022\,140\,76 \times 10^{23} mol^{-1} (exact), making F = N_\mathrm{A} \times e exact without uncertainty.[14][15]The precision of F is thus inherently tied to the CODATA-recommended values for e and N_\mathrm{A}, which serve as the foundational constants in the revised SI framework adopted on 20 May 2019 by the General Conference on Weights and Measures (CGPM).[13] Prior to this redefinition, F was a measured quantity with associated uncertainty, reflecting experimental determinations of e and N_\mathrm{A}; the 2019 change eliminated this by anchoring the ampere and mole to these constants, ensuring F remains invariant and exact for all practical purposes in physics and chemistry.Historically, the uncertainty in F has decreased dramatically through improved measurements. In the 1970s, CODATA adjustments reported values around $96\,485 C mol^{-1} with relative uncertainties on the order of 0.0027% (27 ppm), based on electrochemical and related experiments.[16] Subsequent refinements, including those from the 2014 CODATA evaluation, reduced the uncertainty to approximately $6 \times 10^{-9} (6 ppb) before the 2019 exact fixation, demonstrating a progression from ~0.01% in earlier decades to the current exact status. Standards bodies such as NIST and the International Union of Pure and Applied Chemistry (IUPAC) maintain these values, ensuring consistency across scientific literature.[17]
Historical Background
Michael Faraday's Contributions
Michael Faraday conducted a series of pioneering experiments on electrolysis between 1832 and 1834, investigating the chemical effects produced by passing electric currents through various electrolytes.[18] These studies built on earlier qualitative observations of electrolysis and aimed to quantify the relationship between electrical action and chemical decomposition. Faraday used voltaic batteries and electrical machines to decompose substances such as water, acids, and metal salts, carefully measuring the volumes of gases evolved and masses of metals deposited or dissolved at the electrodes.[19]In 1833, Faraday published his two laws of electrolysis in the fifth and sixth series of his Experimental Researches in Electricity, appearing in the Philosophical Transactions of the Royal Society. The first law states that the mass of a substance altered at an electrode during electrolysis is directly proportional to the quantity of electricity transferred through the circuit.[19] This proportionality held across different sources of electricity, including voltaic batteries and frictional machines, demonstrating that the chemical action depends solely on the total charge passed, not its intensity or the arrangement of the apparatus.[18] The second law asserts that the masses of different substances deposited or liberated by the same quantity of electricity are proportional to their chemical equivalent weights.[20]Faraday's 1834 work, detailed in the eighth series of his researches, provided quantitative validation of these laws through precise measurements involving silver and other metals. He electrolyzed solutions of silver nitrate and chloride of silver, finding that the mass of silver deposited was consistently proportional to the electricity employed; for instance, experiments with a voltaic apparatus showed deposition rates aligning with the total charge from a defined number of battery pairs.[21] Similar results were obtained with copper, zinc, tin, and lead, where Faraday calculated electrochemical equivalents— the mass of each element decomposed per unit of electricity— relative to hydrogen (set at 1) or oxygen (set at 8). For example, the equivalent for tin was approximately 58.43, and for lead around 103.5, confirming the laws' applicability across metals.[18]These findings introduced the concept of electrochemical equivalents, revealing that a definite quantity of electricity is associated with each chemical equivalent, suggesting a universal unit of charge per equivalent of matter. Faraday recognized electricity as a conserved quantity analogous to matter or momentum, stating that "the chemical power of a current of electricity is in direct proportion to the absolutequantity of electricity which passes."[18] This insight laid the empirical foundation for what would later be termed the Faraday constant, representing the charge required to deposit one equivalent of a substance.Early approximate values for these equivalents were refined by Faraday and contemporaries like Jöns Jacob Berzelius, who integrated Faraday's data with chemical analyses to estimate atomic weights and equivalents more accurately; Berzelius, for instance, used silver electrolysis results to corroborate his dualistic theory while acknowledging the proportionality in decomposition masses.[22]
Modern Measurements and Standardization
In the late 19th and early 20th centuries, measurements of the Faraday constant relied primarily on electrochemical deposition methods, such as the silver coulometer, where the mass of silver deposited by a known quantity of electricity was weighed to determine the charge per mole of substance.[23] These techniques achieved accuracies on the order of 0.01% by the 1910s, with Edward B. Rosa and George W. Vinal reporting a value consistent within 10 parts per million (ppm) in 1916.[24] By the mid-20th century, refinements addressed systematic errors like isotopic fractionation and occlusions in deposits, leading to electro-dissolution methods that dissolved high-purity silver anodes in perchloric acid solutions; a 1960 study by Donald N. Craig and colleagues using this approach yielded a value of 96,516.5 ± 2.4 C/equiv, corresponding to roughly 25 ppm uncertainty, though subsequent 1970s experiments improved reproducibility to 10 ppm by minimizing side reactions and enhancing current efficiency.[25]Further advancements in the 20th century incorporated absolute current balances to establish the ampere in mechanical units, enabling precise calibration of electrical standards for coulometric measurements.[26] At the National Bureau of Standards (now NIST), Louis W. McK. Saunders and colleagues in 1942 used helical and spiral coil balances to determine that 1 international ampere equaled 0.999850 absolute amperes, reducing uncertainties in charge quantification for Faraday determinations to below 10 ppm when combined with electrochemical data.[26] Concurrently, X-ray crystallography linked the Faraday constant to the Avogadro constant by measuring lattice parameters of silicon crystals, allowing computation of the number of atoms per unit volume; this X-ray crystal density (XRCD) method, refined in the 1970s and 1980s with synchrotron sources and enriched ^{28}Si spheres, achieved 1 ppm accuracy for N_A, and thus for F via F = N_A e.[27]Key milestones in standardization occurred through international recommendations, with the International Union of Pure and Applied Chemistry (IUPAC) and CODATA issuing adjusted values in the 1960s and 1970s based on least-squares analyses of global measurements; for instance, the 1973 CODATA adjustment gave F = 96 485.3 ± 0.27 C/mol (2.8 ppm uncertainty), refined to 96 485.309 ± 0.029 C/mol (0.30 ppm) by 1986.[16][28] The Bureau International des Poids et Mesures (BIPM), alongside NIST and CODATA, coordinated these efforts to ensure consistency across metrological institutes, evaluating inputs from coulometry, watt balances, and particle physics experiments.[29]The 2019 redefinition of the SI fixed the elementary charge e at exactly 1.602 176 634 × 10^{-19} C and the Avogadro constant N_A at exactly 6.022 140 76 × 10^{23} mol^{-1}, rendering F = N_A e exactly 96 485.332 123 310 018 4 C/mol with zero uncertainty.[30] This shift eliminated reliance on artifact standards, with BIPM, CODATA, and NIST now focusing on experimental verifications to confirm the fixed values; for example, Johnson noise thermometry measures thermal voltage fluctuations to independently assess e via comparisons with quantum voltage noise sources, achieving relative uncertainties below 10^{-8} in recent NIST setups.[31] Such methods ensure ongoing consistency between the theoretical definition and practical realizations in electrochemistry.
Theoretical Basis
Relation to Fundamental Constants
The Faraday constant F is defined as the product of the elementary charge e, which is the charge of a single electron, and the Avogadro constant N_A, which represents the number of particles in one mole of substance:F = e \times N_AThis relationship establishes F as a fundamental link between the quantized nature of electric charge at the atomic level and the macroscopic quantities used in chemistry and physics.[23]This connection bridges the microscopic scale, governed by the discrete charge e, with the molar scale defined by N_A, enabling the translation of single-particle properties to bulk material behaviors in electrochemical processes.[23] Historically, e was first precisely measured through Robert Millikan's oil-drop experiment in 1909, which demonstrated that electric charges occur in integer multiples of this fundamental unit.[32] Similarly, N_A has been determined using methods like the International Avogadro Project, which involved counting atoms in highly pure silicon-28 spheres of approximately 1 kg mass to achieve high precision.[33]The 2019 redefinition of the International System of Units (SI) fixed the values of both e and N_A, rendering F an exact constant and eliminating uncertainties in its measurement. This exactness has implications for electrochemical standards, as it provides a precise conversion factor between electrical charge and amounts of substance, enhancing consistency in fields like electrochemistry and metrology.Furthermore, F unifies key SI base units by relating the ampere—defined through the fixed value of e—to the mole, which is tied to N_A, thereby integrating electrical and chemical measurement systems.
Derivation
The Faraday constant arises from Michael Faraday's first law of electrolysis, which states that the mass m of a substance deposited or liberated at an electrode is directly proportional to the total electric charge Q passed through the electrolyte.[34] This charge Q is given by the product of the current I and the time t for which it flows:Q = I \times twhere Q is in coulombs (C), I in amperes (A), and t in seconds (s).[34]To relate this to chemical quantities, consider an electrochemical reaction where n electrons are transferred per formula unit of the substance, with molar mass M. The first law can be expressed asm = \frac{M}{n F} Q,where F is the Faraday constant. Rearranging yields the basic definition: F = Q / n, with n now representing the moles of electrons transferred to produce one mole of substance under ideal conditions.[34] This assumes ideal electrolysis without side reactions or overpotentials, and for simplicity, reactions involving singly charged species (n = 1).Fundamentally, the Faraday constant represents the charge carried by one mole of electrons. Since one mole contains the Avogadro constant N_A particles and each electron bears an elementary charge e, the full expression isF = N_A \times e.This relation links electrochemistry to atomic-scale properties.Following the 2019 redefinition of the SI units, both e and N_A are exact, making F exact as well:F = (1.602176634 \times 10^{-19} \, \mathrm{C}) \times (6.02214076 \times 10^{23} \, \mathrm{mol}^{-1}) = 96485.3321233100184 \, \mathrm{C \, mol^{-1}}.This value is adopted internationally and confirms the constant's role in precise electrochemical stoichiometry.[1]
Units and Expressions
SI Units
The Faraday constant is expressed in the SI unit of coulombs per mole (C/mol), quantifying the electric charge associated with one mole of elementary charges.[35] This unit reflects its role as charge per amount of substance, aligning with the SI base units of electric current (ampere, A), time (second, s), and amount of substance (mole, mol).Dimensionally, the Faraday constant has the form [F] = \mathrm{A \cdot s \cdot mol^{-1}}, derived from the coulomb as the product of ampere and second divided by mole. This dimensional consistency ensures its integration within the SI framework for electrochemical quantities.Following the 2019 redefinition of the SI units, the ampere is fixed by the elementary charge e = 1.602176634 \times 10^{-19} C, rendering the Faraday constant F = N_A e coherent with the exact definitions of the ampere and mole.[36] This redefinition eliminates prior measurement uncertainties tied to the ampere, stabilizing F in SI expressions.In practical SI calculations, such as determining molar ionic conductivity \lambda, the Faraday constant facilitates conversions between charge and mobility, where \lambda = z F \mu and the conductivity unit is siemens meter squared per mole (S m² mol⁻¹), though S cm² mol⁻¹ is commonly used for convenience.[37]Within the SI system, the Faraday constant equates to joules per volt per mole (J V⁻¹ mol⁻¹) via the relation 1 C = 1 J/V, enabling its use in energy-related electrochemical computations without unit conversion.
Alternative Units
In electrochemistry, the Faraday constant is sometimes expressed in energy units per volt per gram-equivalent, reflecting its role in calculating electrochemical work. One common form is 96.485 kJ per volt per gram-equivalent, derived directly from the charge value where 1 C·V equals 1 J.[38] Another equivalent expression is 23.061 kcal per volt per gram-equivalent, using the conversion factor of 1 kcal = 4.184 kJ.[38]In battery engineering and capacity calculations, the Faraday constant is often given as 26.801 A·h/mol, obtained by dividing the SI charge value by 3600 (since 1 A·h = 3600 C).[39] This unit facilitates direct computation of charge storage in ampere-hours for one mole of electrons, aiding practical designs in electrochemical cells.[39]Historically, before the widespread adoption of SI units, the Faraday constant appeared in cgs-based systems such as electrostatic units (esu) and electromagnetic units (emu). In esu, it equals approximately 2.893 × 10^{14} statcoulombs per mole, convertible via the factor 1 statcoulomb ≈ 3.336 × 10^{-10} C.[40] In emu, the value is about 9.649 × 10^3 abamperes-seconds (or emu of charge) per mole, using the relation 1 emu charge = 10 C.[41] These expressions were prevalent in early 20th-century physics and chemistry texts for electromagnetic calculations.[42]The gram-equivalent basis ties these units to older chemical notation, where one equivalent represents 1 mol divided by the charge number z of the ion (e.g., 1 equiv = 1 mol for z=1, or 0.5 mol for z=2).[43] The Faraday constant thus denotes the charge or energy needed to process one gram-equivalent, maintaining consistency across valences in electrolytic processes.[43] Such units remain useful in specialized engineering contexts, like corrosion rate assessments or legacy battery specifications, where molar quantities are less emphasized than equivalent weights.[43]
The Faraday as a Unit
Definition and Properties
The faraday is a unit of electric charge that represents the total electric charge carried by one mole of singly charged particles, such as electrons or protons. Symbolized as F (or occasionally ℱ), one faraday is defined as the product of the Faraday constant and one mole of substance, such that 1 F = ℱ × 1 mol.[1] Following the 2019 revision of the International System of Units (SI), this yields an exact value of 1 F = 96 485.332 123 310 0184 C.[1]A key property of the faraday is its equivalence to exactly N_A elementary charges, with N_A being the Avogadro constant (6.022 140 76 × 10^{23} mol^{-1}).[44] This makes it a convenient scale for quantities involving molar amounts of charge carriers, though it is not an SI base unit; instead, it is a derived unit based on the coulomb (the SI unit for charge) scaled to the mole (an SI base unit for amount of substance).[45] Physically, the faraday quantifies the charge required to electrochemically reduce or oxidize one mole of monovalent ions, linking electrical energy transfer to stoichiometric changes in chemical reactions.[46]The faraday unit is numerically equal to the Faraday constant ℱ when the latter is expressed in coulombs per mole (C mol^{-1}), but it specifically denotes an absolute charge quantity rather than a charge-to-mole proportionality factor.[1] This distinction facilitates its use in contexts where total charge for a molar process is emphasized, without altering the underlying dimensional relationship ℱ = N_A e, where e is the elementary charge.[44]
Usage in Electrochemistry
In electrochemistry, the faraday unit quantifies the charge required to deposit or liberate one equivalent of a substance, serving as a key parameter in calculations involving redox processes. It is prominently featured in Faraday's first law of electrolysis, which relates the mass m of a substance altered at an electrode to the electric charge Q passed through the electrolyte:m = \frac{Q \cdot M}{z \cdot F},where M is the molar mass of the substance, z is the number of electrons transferred per ion (or the ion's valence), and F is the Faraday constant.[8] This formula enables the prediction of material yields in electrolytic cells, such as the amount of metal plated during electrodeposition. The electrochemical equivalent Z, defined as the mass deposited per unit charge, is derived as Z = \frac{M}{z \cdot F}, allowing direct computation of m = Z \cdot Q.The faraday also appears in expressions for electrochemical cell potentials, particularly through the Nernst equation, which describes the potential E of a cell under non-standard conditions:E = E^\circ - \frac{RT}{n F} \ln Q,where E^\circ is the standard cell potential, R is the gas constant, T is temperature, n is the number of moles of electrons transferred in the balanced equation, and Q is the reaction quotient. Here, F converts the molar scale of electron transfer into electrical charge, facilitating the link between thermodynamics and measurable voltage. In battery design, the unit expresses capacity; for instance, the theoretical capacity of an electrode material is calculated as \frac{n \cdot F}{M \cdot 3600} in ampere-hours per gram, where n reflects the electrons per formula unit.[47]A practical example is the electrodeposition of silver from Ag⁺ ions, where depositing one mole of Ag requires exactly one faraday of charge, as z = 1.[8] For divalent ions like Cu²⁺, two faradays (2F) are needed per mole deposited. In electrochemical literature, the faraday is denoted as \mathfrak{F} or simply F to distinguish it from other symbols, with multiples like nF used for multi-electron processes.[48] This notation streamlines stoichiometric analyses in redox reactions by equating charge passage directly to equivalents of reactants and products, reducing complex charge-mole conversions to simple multiples of F.[7]
Applications
In Electrolysis and Faraday's Laws
The Faraday constant plays a central role in Faraday's laws of electrolysis, which describe the quantitative relationship between electrical charge and chemical change during electrolytic processes. Faraday's first law states that the mass m of a substance deposited or liberated at an electrode is directly proportional to the total electric charge Q passed through the electrolyte. Mathematically, this is expressed asm = \frac{Q \cdot M}{z F},where M is the molar mass of the substance, z is the number of electrons transferred per ion (valence factor), and F is the Faraday constant. Equivalently, the charge required to deposit n moles of the substance is Q = n z F, highlighting that one mole of electrons (corresponding to one faraday of charge) effects the reduction or oxidation of one equivalent of substance.[6]Faraday's second law extends this by asserting that, for a fixed quantity of electricity passed through different electrolytic cells in series, the masses of substances deposited or liberated are proportional to their chemical equivalent weights, defined as M / z. This implies a universal constant relating charge to chemical equivalents, with one faraday of charge liberating one gram-equivalent of any substance, regardless of the element.[4] The law underscores the stoichiometric consistency across electrolytes, enabling precise predictions of yields in multi-component systems.[8]In practical applications like electroplating, the Faraday constant quantifies material deposition. For copper electroplating from Cu²⁺ solution, the half-reaction Cu²⁺ + 2e⁻ → Cu requires two faradays of charge to deposit one mole (63.55 g) of copper, allowing calculation of plating thickness from current and time via Q = I t.[49] Similarly, in the industrial Hall-Héroult process for aluminum production, the reduction Al³⁺ + 3e⁻ → Al demands three faradays per mole (26.98 g) of aluminum, with theoretical yields of approximately 0.335 kg Al per kAh of charge passed, though actual efficiencies reach 90-96% due to side reactions.[50]The Faraday constant also informs energy efficiency in electrolysis through its role in electrochemical thermodynamics. The standard cell potential E^\circ relates to the Gibbs free energy change via \Delta G^\circ = -n F E^\circ, where n = z, providing the minimum voltage for spontaneous or driven reactions; deviations under non-standard conditions are captured by the Nernst equation E = E^\circ - \frac{RT}{n F} \ln Q.[51] In modern rechargeable batteries, such as lithium-ion systems, F calculates theoretical specific capacity, for example, via C = \frac{z F}{3.6 M} in mAh/g for the intercalation reaction Li⁺ + e⁻ + host → Li-host, guiding electrode material design for high-energy-density storage.[52]
In Broader Physical and Chemical Contexts
In physical chemistry, the Faraday constant plays a key role in relating electrical conductivity to ionic transport properties, particularly through the expression for molar conductivity, defined as \Lambda = \kappa / c, where \kappa is the specific conductivity and c is the electrolyte concentration. This quantity incorporates the Faraday constant F when expressing ionic mobilities, as the molar ionic conductivity \lambda_i = F |z_i| u_i, with u_i being the ionic mobility and z_i the charge number, enabling the analysis of ion dynamics in solution.[53] Kohlrausch's law of independent migration of ions further utilizes this framework, stating that at infinite dilution, the molar conductivity \Lambda^0 = \sum \nu_i \lambda_i^0, where the contributions from cations and anions are additive, and F scales the transport numbers to electrochemical equivalents.[54]In physics applications, such as photoelectrochemistry, the Faraday constant bridges the generation of charge carriers in semiconductors to the moles of reactants produced, quantifying the efficiency of processes like water splitting under illumination. For instance, in semiconductor-based photoelectrochemical cells, the photocurrent I relates to the rate of electron-hole pair separation, and the amount of evolved gas (e.g., hydrogen) is given by n = I t / (n_e F), where n_e is the number of electrons per molecule, linking quantum efficiency to stoichiometric yields.[55] This connection is essential in devices like dye-sensitized solar cells or tandem photoanodes, where F ensures accurate conversion between electrical charge and chemical turnover, optimizing energy storage and conversion.[56]In materials science, the Faraday constant is integral to calculating corrosion rates, where the rate can be derived from the corrosion current density using Faraday's laws. Similarly, in electropolishing, Faraday efficiency \eta is defined as \eta = m_{\text{actual}} / m_{\text{theoretical}}, with the theoretical mass m_{\text{theoretical}} = (M \cdot Q) / (n F) based on passed charge Q, valence n, and molar mass M, enabling control of surface smoothing and improved corrosion resistance in metals like stainless steel.[57][58]In geochemistry, the Faraday constant finds applications in modeling electrochemical processes within natural systems, such as ion transport in subsurface electrolytes. In simulations of reactive transport in porous media, F scales electrochemical potentials to quantify charge transfer in mineral dissolution.[59] In hydrogen-dominated exoplanet atmospheres, it supports models of photochemical redox reactions by relating electron fluxes to molecular abundances.[60]Since the 2019 redefinition of the SI units, the Faraday constant is exactly 96 485.332 123 310 0184 C mol⁻¹, as the product of the exact Avogadro constant and elementary charge. Prior to this, precise values (e.g., approximately 96 485.3321 C mol⁻¹ from the 2018 CODATA adjustment) were determined experimentally, such as through silver coulometry with relative uncertainties around 1 × 10^{-6}. These measurements linked F to the elementary charge e via F = N_A e, supporting quantum-based electrical units. Quantum electrochemistry extends this to nanoscale interfaces, using F to model single-electron transfers in molecular junctions, advancing sensor calibration and fundamental constant verification.[46][3]