Defining equation (physical chemistry)

Theoretical chemistry requires quantities from core physics, such as time, volume, temperature, and pressure. But the highly quantitative nature of physical chemistry, in a more specialized way than core physics, uses molar amounts of substance rather than simply counting numbers; this leads to the specialized definitions in this article. Core physics itself rarely uses the mole, except in areas overlapping thermodynamics and chemistry.

Entity refers to the type of particle/s in question, such as atoms, molecules, complexes, radicals, ions, electrons etc.[1]

Conventionally for concentrations and activities, square brackets [ ] are used around the chemical molecular formula. For an arbitrary atom, generic letters in upright non-bold typeface such as A, B, R, X or Y etc. are often used.

No standard symbols are used for the following quantities, as specifically applied to a substance:

• the mass of a substance m,
• the number of moles of the substance n,
• partial pressure of a gas in a gaseous mixture p (or P),
• some form of energy of a substance (for chemistry enthalpy H is common),
• entropy of a substance S
• the electronegativity of an atom or chemical bond χ.

Usually the symbol for the quantity with a subscript of some reference to the quantity is used, or the quantity is written with the reference to the chemical in round brackets. For example, the mass of water might be written in subscripts as m_H2O, m_water, m_aq, m_w (if clear from context) etc., or simply as m(H₂O). Another example could be the electronegativity of the fluorine-fluorine covalent bond, which might be written with subscripts χ_F-F, χ_FF or χ_F-F etc., or brackets χ(F-F), χ(FF) etc.

Neither is standard. For the purpose of this article, the nomenclature is as follows, closely (but not exactly) matching standard use.

For general equations with no specific reference to an entity, quantities are written as their symbols with an index to label the component of the mixture - i.e. q_i. The labeling is arbitrary in initial choice, but once chosen fixed for the calculation.

If any reference to an actual entity (say hydrogen ions H⁺) or any entity at all (say X) is made, the quantity symbol q is followed by curved ( ) brackets enclosing the molecular formula of X, i.e. q(X), or for a component i of a mixture q(X_i). No confusion should arise with the notation for a mathematical function.

The defining formulae for the equilibrium constants K_c (all reactions) and K_p (gaseous reactions) apply to the general chemical reaction:

$${\displaystyle {\ce {{\nu _{1}X1}+{\nu _{2}X2}+\cdots +\nu _{\mathit {r}}X_{\mathit {r}}<=>{\eta _{1}Y1}+{\eta _{2}Y2}+\cdots +\eta _{\mathit {p}}{Y}_{\mathit {p}}}}}$$

and the defining equation for the rate constant k applies to the simpler synthesis reaction (one product only):

$${\displaystyle {\ce {{\nu _{1}X1}+{\nu _{2}X2}+\cdots +\nu _{\mathit {r}}X_{\mathit {r}}->\eta {Y}}}}$$

where:

• i = dummy index labelling component i of reactant mixture,
• j = dummy index labelling component i of product mixture,
• X_i = component i of the reactant mixture,
• Y_j = reactant component j of the product mixture,
• r (as an index) = number of reactant components,
• p (as an index) = number of product components,
• ν_i = stoichiometry number for component i in product mixture,
• η_j = stoichiometry number for component j in product mixture,
• σ_i = order of reaction for component i in reactant mixture.

The dummy indices on the substances X and Y label the components (arbitrary but fixed for calculation); they are not the numbers of each component molecules as in usual chemistry notation.

The units for the chemical constants are unusual since they can vary depending on the stoichiometry of the reaction, and the number of reactant and product components. The general units for equilibrium constants can be determined by usual methods of dimensional analysis. For the generality of the kinetics and equilibria units below, let the indices for the units be;

$${\displaystyle S_{1}=\sum _{j=1}^{p}\eta _{j}-\sum _{i=1}^{r}\nu _{i}\,,\quad \,S_{2}=1-\sum _{i=1}^{r}\sigma _{i}\,.}$$

Click here to see their derivation

For the constant K_c;

Substitute the concentration units into the equation and simplify:,

$${\displaystyle {\begin{aligned}K_{c}&={\frac {\prod _{j=1}^{p}\left[{\ce {Y}}_{j}\right]^{y_{j}}}{\prod _{i=1}^{r}\left[{\ce {X}}_{i}\right]^{x_{i}}}}\\\left[K_{c}\right]&={\frac {\prod _{j=1}^{p}[{\ce {M}}]^{y_{j}}}{\prod _{i=1}^{r}[{\ce {M}}]^{x_{i}}}}\\&={\frac {[{\ce {M}}]^{y_{1}}[{\ce {M}}]^{y_{2}}\cdots [{\ce {M}}]^{y_{p}}}{[{\ce {M}}]^{x_{1}}[{\ce {M}}]^{x_{2}}\cdots [{\ce {M}}]^{x_{r}}}}\\&={\frac {[{\ce {M}}]^{\sum _{j=1}^{p}y_{j}}}{[{\ce {M}}]^{\sum _{i=1}^{r}x_{i}}}}\\&=[{\ce {M}}]^{\sum _{j=1}^{p}y_{j}-\sum _{i=1}^{r}x_{i}}\end{aligned}}\ ({\ce {M=mol\;dm^{-3}}})}$$

The procedure is exactly identical for K_p.

For the constant k

$${\displaystyle {\begin{aligned}k&={\frac {\frac {\mathrm {d} [{\ce {Y}}]}{\mathrm {d} t}}{\prod _{i=1}^{r}\left[{\ce {X}}_{i}\right]^{\sigma _{i}}}}\\\left[k\right]&={\frac {[{\ce {M}}]s^{-1}}{\prod _{i=1}^{r}[{\ce {M}}]^{\sigma _{i}}}}\\&={\frac {[{\ce {M}}]s^{-1}}{[{\ce {M}}]^{\sum _{i=1}^{r}\sigma _{i}}}}\\&=[{\ce {M}}]^{1-\sum _{i=1}^{r}\sigma _{i}}s^{-1}\end{aligned}}}$$

Quantity (Common Name/s)	(Common) Symbol/s	Defining Equation	SI Units	Dimension
Reaction progress variable, extent of reaction	ξ	${\displaystyle \xi }$	dimensionless	dimensionless
Stoichiometric coefficient of a component i in a mixture, in reaction j (many reactions could occur at once)	νi	${\displaystyle \nu _{ij}={\frac {\mathrm {d} N_{i}}{\mathrm {d} \xi _{j}}}\,}$ where Ni = number of molecules of component i.	dimensionless	dimensionless
Chemical affinity	A	${\displaystyle A=-\left({\frac {\partial G}{\partial \xi }}\right)_{P,T}}$	J	[M][L]2[T]−2
Reaction rate with respect to component i	r, R	${\displaystyle R_{i}={\frac {1}{\nu _{i}}}{\frac {\mathrm {d} \left[\mathrm {X} _{i}\right]}{\mathrm {d} t}}}$	mol dm−3 s−1 = 10−3 mol m−3 s−1	[N] [L]−3 [T]−1
Activity of a component i in a mixture	ai	${\displaystyle a_{i}=e^{\left(\mu _{i}-\mu _{i}^{\ominus }\right)/RT}}$	dimensionless	dimensionless
Mole fraction, molality, and molar concentration activity coefficients	γxi for mole fraction, γbi for molality, γci for molar concentration.	Three coefficients are used; ${\displaystyle a_{i}=\gamma _{xi}x_{i}\,}$ ${\displaystyle a_{i}=\gamma _{bi}b_{i}/b^{\ominus }\,}$ ${\displaystyle a_{i}=\gamma _{ci}\left[\mathrm {X} _{i}\right]/\left[\mathrm {X} _{i}\right]^{\ominus }\,}$	dimensionless	dimensionless
Rate constant	k	${\displaystyle k={\frac {\mathrm {d} \left[\mathrm {Y} \right]/\mathrm {d} t}{\prod _{i=1}^{r}\left[\mathrm {X} _{i}\right]^{\sigma _{i}}}}}$	(mol dm−3)(S2) s−1	([N] [L]−3)(S2) [T]−1
General equilibrium constant[2]	Kc	${\displaystyle K_{c}={\frac {\prod _{j=1}^{p}\left[\mathrm {Y} _{j}\right]^{\eta _{j}}}{\prod _{i=1}^{r}\left[\mathrm {X} _{i}\right]^{\nu _{i}}}}}$	(mol dm−3)(S1)	([N] [L]−3)(S1)
General thermodynamic activity constant [3]	K0	${\displaystyle K_{0}={\frac {\prod _{j=1}^{p}a\left(\mathrm {Y} _{j}\right)^{\eta _{j}}}{\prod _{i=1}^{r}a\left(\mathrm {X} _{i}\right)^{\nu _{i}}}}}$ a(Xi) and a(Yj) are activities of Xi and Yj respectively.	(mol dm−3)(S1)	([N] [L]−3)(S1)
Equilibrium constant for gaseous reactions, using Partial pressures	Kp	${\displaystyle K_{p}={\frac {\prod _{j=1}^{p}p\left(\mathrm {Y} _{j}\right)^{\eta _{j}}}{\prod _{i=1}^{r}p\left(\mathrm {X} _{i}\right)^{\nu _{i}}}}}$	Pa(S1)	([M] [L]−1 [T]−2)(S1)
Logarithm of any equilibrium constant	pKc	${\displaystyle \mathrm {p} K_{c}=-\log _{10}K_{c}=\sum _{j=1}^{p}\eta _{j}\log _{10}\left[\mathrm {Y} _{j}\right]-\sum _{i=1}^{r}\nu _{i}\log _{10}\left[\mathrm {X} _{i}\right]}$	dimensionless	dimensionless
Logarithm of dissociation constant	pK	${\displaystyle \mathrm {p} K=-\log _{10}K}$	dimensionless	dimensionless
Logarithm of hydrogen ion (H+) activity, pH	pH	${\displaystyle \mathrm {pH} =-\log _{10}[\mathrm {H} ^{+}]}$	dimensionless	dimensionless
Logarithm of hydroxide ion (OH−) activity, pOH	pOH	${\displaystyle \mathrm {pOH} =-\log _{10}[\mathrm {OH} ^{-}]}$	dimensionless	dimensionless

Notation for half-reaction standard electrode potentials is as follows. The redox reaction

$${\displaystyle {\ce {A + BX <=> B + AX}}}$$

split into:

• a reduction reaction: ${\displaystyle {\ce {B+ + e^- <=> B}}}$
• and an oxidation reaction: ${\displaystyle {\ce {A+ + e^- <=> A}}}$

(written this way by convention) the electrode potential for the half reactions are written as ${\displaystyle E^{\ominus }\left({\ce {A+}}\vert {\ce {A}}\right)}$ and ${\displaystyle E^{\ominus }\left({\ce {B+}}\vert {\ce {B}}\right)}$ respectively.

For the case of a metal-metal half electrode, letting M represent the metal and z be its valency, the half reaction takes the form of a reduction reaction:

$${\displaystyle {\ce {{M^{+{\mathit {z}}}}+{\mathit {z}}e^{-}<=>M}}}$$

Quantity (Common Name/s)	(Common) Symbol/s	Defining Equation	SI Units	Dimension
Standard EMF of an electrode	${\displaystyle E^{\ominus },E^{\ominus }\left({\ce {X}}\right)}$	${\displaystyle \Delta E^{\ominus }\left({\ce {X}}\right)=E^{\ominus }\left({\ce {X}}\right)-E^{\ominus }\left({\ce {Def}}\right)}$ where Def is the standard electrode of definition, defined to have zero potential. The chosen one is hydrogen: ${\displaystyle E^{\ominus }\left({\ce {H+}}\right)=E^{\ominus }\left({\ce {H+}}\vert {\ce {H}}\right)=0}$	V	[M][L]2[I][T]−1
Standard EMF of an electrochemical cell	${\displaystyle E_{\mathrm {cell} }^{\ominus },\Delta E^{\ominus }}$	${\displaystyle E_{\mathrm {cell} }^{\ominus }=E^{\ominus }\left(\mathrm {Cat} \right)-E^{\ominus }\left(\mathrm {An} \right)}$ where Cat is the cathode substance and An is the anode substance.	V	[M][L]2[I][T]−1
Ionic strength	I	Two definitions are used, one using molarity concentration, $${\displaystyle I={\frac {1}{2}}\sum _{i=1}^{N}z_{i}^{2}\left[{\rm {X}}_{i}\right]}$$ and one using molality,[4] $${\displaystyle I={\frac {1}{2}}\sum _{i=1}^{N}z_{i}^{2}b_{i}}$$ The sum is taken over all ions in the solution.	mol dm−3 or mol dm−3 kg−1	[N] [L]−3 [M]−1
Electrochemical potential (of component i in a mixture)	${\displaystyle {\bar {\mu }}_{i}\,\!}$	${\displaystyle {\bar {\mu }}_{i}=\mu -zeN_{A}\phi \,\!}$ φ = local electrostatic potential (see below also) zi = valency (charge) of the ion i	J	[M][L]2[T]−2

• Physical chemistry, P.W. Atkins, Oxford University Press, 1978, ISBN 0-19-855148-7
• Chemistry, Matter and the Universe, R.E. Dickerson, I. Geis, W.A. Benjamin Inc. (USA), 1976, ISBN 0-8053-2369-4
• Chemical thermodynamics, D.J.G. Ives, University Cchemistry Series, Macdonald Technical and Scientific co. ISBN 0-356-03736-3.
• Elements of Statistical Thermodynamics (2nd Edition), L.K. Nash, Principles of Chemistry, Addison-Wesley, 1974, ISBN 0-201-05229-6
• Statistical Physics (2nd Edition), F. Mandl, Manchester Physics, John Wiley & Sons, 2008, ISBN 978-0-471-91533-1

• Quanta: A handbook of concepts, P.W. Atkins, Oxford University Press, 1974, ISBN 0-19-855493-1
• Molecular Quantum Mechanics Parts I and II: An Introduction to QUANTUM CHEMISTRY (Volume 1), P.W. Atkins, Oxford University Press, 1977, ISBN 0-19-855129-0
• Thermodynamics, From Concepts to Applications (2nd Edition), A. Shavit, C. Gutfinger, CRC Press (Taylor and Francis Group, USA), 2009, ISBN 978-1-4200-7368-3
• Properties of matter, B.H. Flowers, E. Mendoza, Manchester Physics Series, J. Wiley and Sons, 1970, ISBN 978-0-471-26498-9