Activity coefficient

An activity coefficient is a factor used in is Henry’s law for the solvent. These relationships are re-
thermodynamics to account for deviations from ideal lated to each other through the Gibbs–Duhem equation.[2]
behaviour in a mixture of chemical substances.[1] In an Note that in general activity coefficients are dimension-
ideal mixture, the microscopic interactions between each less.
pair of chemical species are the same (or macroscopically
In detail: Raoult’s law states that the partial pressure of
equivalent, the enthalpy change of solution and volume component B is related to its vapor pressure (saturation
variation in mixing is zero) and, as a result, properties of pressure) and its mole fraction xB in the liquid phase,
the mixtures can be expressed directly in terms of simple
concentrations or partial pressures of the substances
present e.g. Raoult’s law. Deviations from ideality are
accommodated by modifying the concentration by an pB = xB γB pσB ,
activity coefficient. Analogously, expressions involving
with the convention limxB →1 γB = 1 . In other words:
gases can be adjusted for non-ideality by scaling partial
Pure liquids represent the ideal case.
pressures by a fugacity coefficient.
At infinite dilution, the activity coefficient approaches its
The concept of activity coefficient is closely linked to that
limiting value, γB∞ . Comparison with Henry’s law,
of activity in chemistry.

1 Thermodynamic definition pB = KH,B xB for xB → 0 ,

immediately gives
The chemical potential, μB, of a substance B in an ideal
mixture of liquids or an ideal solution is given by
KH,B = pσB γB∞ .
µB = µ⊖
B + RT ln xB In other words: The compound shows nonideal behavior
where μo in the dilute case.
B is the chemical potential in the standard state and xB is The above definition of the activity coefficient is imprac-
the mole fraction of the substance in the mixture. tical if the compound does not exist as a pure liquid.
This is generalised to include non-ideal behavior by writ- This is often the case for electrolytes or biochemical com-
ing pounds. In such cases, a different definition is used that
considers infinite dilution as the ideal state:

µB = µ⊖
B + RT ln aB
γB† ≡ γB /γB∞
when aB is the activity of the substance in the mixture
with with limxB →0 γB† = 1 , and

aB = xB γB
µB = µ⊖ + RT ln γB∞ +RT ln(xB γB† )
|B {z }
where γB is the activity coefficient, which may itself de-
µ⊖†
pend on xB. As γB approaches 1, the substance behaves B

as if it were ideal. For instance, if γB ≈ 1, then Raoult’s

The † symbol has been used here to dinstinguish between
law is accurate. For γB > 1 and γB < 1, substance B the two kinds of activity coefficients. Usually it is omit-
shows positive and negative deviation from Raoult’s law, ted, as it is clear from the context which kind is meant.
respectively. A positive deviation implies that substance But there are cases where both kinds of activity coeffi-
B is more volatile. cients are needed and may even appear in the same equa-
In many cases, as xB goes to zero, the activity coefficient tion, e.g., for solutions of salts in (water + alcohol) mix-
of substance B approaches a constant; this relationship tures. This is sometimes a source of errors.

1
2 3 THEORETICAL CALCULATION OF ACTIVITY COEFFICIENTS

Modifying mole fractions or concentrations by activity
coefficients gives the effective activities of the compo-
nents, and hence allows expressions such as Raoult’s law
and equilibrium constants to be applied to both ideal and
non-ideal mixtures.
Knowledge of activity coefficients is particularly impor-
tant in the context of electrochemistry since the behaviour
of electrolyte solutions is often far from ideal, due to the
effects of the ionic atmosphere. Additionally, they are
particularly important in the context of soil chemistry due
to the low volumes of solvent and, consequently, the high
concentration of electrolytes.[3]
drogen ion activity places the quantity squarely in the un-
measurable category. Recognizing this logical difficulty,
International Union of Pure and Applied Chemistry (IU-
PAC) states that the activity-based definition of pH is a
notional definition only.[6] Despite the prevailing nega-
tive view on the measurability of single ion coefficients,
the concept of single ion activities continues to be dis-
cussed in the literature, and at least one author presents a
definition of single ion activity in terms of purely thermo-
dynamic quantities and proposes a method of measuring
single ion activity coefficients based on purely thermody-
namic processes.[7]

1.1 Ionic solutions 2 Experimental determination of

For solution of substances which ionize in solution the
activity coefficients of the cation and anion cannot be ex-
perimentally determined independently of each other be-
cause solution properties depend on both ions. Single ion
activity coefficients must be linked to the activity coeffi-
cient of the dissolved electrolyte as if undissociated. In
this case a mean stoichiometric activity coefficient of the
dissolved electrolyte, γ±, is used. It is called stoichio-
metric because it expresses both the deviation from the
ideality of the solution and the incomplete ionic dissocia-
tion of the ionic compound which occurs especially with
the increase of its concentration.
For a 1:1 electrolyte, such as NaCl it is given by the fol-
lowing:
√
γ± = γ+ γ−
activity coefficients
Activity coefficients may be determined experimentally
by making measurements on non-ideal mixtures. Use
may be made of Raoult’s law or Henry’s law to provide a
value for an ideal mixture against which the experimental
value may be compared to obtain the activity coefficient.
Other colligative properties, such as osmotic pressure may
also be used.
2.1 Radiochemical methods
Activity coefficients can be determined by radiochemical
methods.[8]

where γ₊ and γ₋ are the activity coefficients of the cation 3 Theoretical calculation of activity
and anion respectively. coefficients
More generally, the mean activity coefficient of a com-
pound of formula ApBq is given by[4] Activity coefficients of electrolyte solutions may be cal-
culated theoretically, using the Debye–Hückel equation
√ or extensions such as the Davies equation,[9] Pitzer equa-
p q
γ± = p+q
γA γB tions[10] or TCPC model.[11][12][13][14] Specific ion inter-
action theory (SIT)[15] may also be used.
Single-ion activity coefficients can be calculated theoret-
For non-electrolyte solutions correlative methods such
ically, for example by using the Debye–Hückel equation.
as UNIQUAC, NRTL, MOSCED or UNIFAC may be
The theoretical equation can be tested by combining the
employed, provided fitted component-specific or model
calculated single-ion activity coefficients to give mean
parameters are available. COSMO-RS is a theoretical
values which can be compared to experimental values.
method which is less dependent on model parameters as
The prevailing view that single ion activity coefficients required information is obtained from quantum mechan-
are unmeasurable independently, or perhaps even physi- ics calculations specific to each molecule (sigma profiles)
cally meaningless, has its roots in the work of Guggen- combined with a statistical thermodynamics treatment of
heim in the late 1920s.[5] However, chemists have never surface segments.[16]
been able to give up the idea of single ion activities, and
For uncharged species, the activity coefficient γ0 mostly
by implication single ion activity coefficients. For exam-
follows a salting-out model:[17]
ple, pH is defined as the negative logarithm of the hydro-
gen ion activity. If the prevailing view on the physical
meaning and measurability of single ion activities is cor-
rect then defining pH as the negative logarithm of the hy- log10 (γ0 ) = bI
 3

5 Dependence on state parameters

The derivative of an activity coefficient with respect to
temperature is related to excess molar enthalpy by

∂
H̄iE = −RT 2 ln(γi )
∂T
Similarly, the derivative of an activity coefficient with re-
spect to pressure can be related to excess molar volume.

∂
V̄iE = RT ln(γi )
∂P

6 Concentrated solutions of elec-

trolytes
For concentrated ionic solutions the activity coefficient
UNIQUAC Regression of activity coefficients
of the electrolyte is split into electric and statistical com-
(chloroform/methanol mixture)
ponents.
The statistical part includes hydration index number h ,
This simple model predicts activities of many species the number of ions from the dissociation and the ratio r
(dissolved undissociated gases such as CO2 , H2 S, NH3 , between the apparent molar volume of the electrolyte and
undissociated acids and bases) to high ionic strengths (up the molar volume of water and molality b.
to 5 mol/kg). The value of the constant b for CO2 is 0.11
at 10 °C and 0.20 at 330 °C.[18] Concentrated solution statistical part of the activity coef-
ν ln(1 + 55.5 ) − ν ln(1 − 55.5 ) +
ficient is: lnγs = h−ν br h br
For water as solvent, the activity a can be calculated br(r+h−ν) [19]
using:[17] br
55.5(1+ 55.5 )

−νm 7 Application to chemical equilib-

ln(aw ) = φ
55.51 rium
where ν is the number of ions produced from the dis-
sociation of one molecule of the dissolved salt, m is the At equilibrium, the sum of the chemical potentials of the
molality of the salt dissolved in water, φ is the osmotic co- reactants is equal to the sum of the chemical potentials
efficient of water, and the constant 55.51 represents the of the products. The Gibbs free energy change for the
molality of water. In the above equation, the activity of reactions, ΔᵣG, is equal to the difference between these
a solvent (here water) is represented as inversely propor- sums and therefore, at equilibrium, is equal to zero. Thus,
tional to the number of particles of salt versus that of the for an equilibrium such as
solvent.
αA+βB⇌σS+τT
∆r G = σµS + τ µT − (αµA + βµB ) = 0
4 Link to ionic diameter
Substitute in the expressions for the chemical potential of
The ionic activity coefficient is connected to the ionic each reactant:
diameter a by the formula obtained from Debye-Huckel
theory of electrolytes:
∆r G = σµ⊖ ⊖ ⊖ ⊖
S +σRT ln aS +τ µT +τ RT ln aT −(αµA +αRT ln aA +βµB +β
√
Azi2 I Upon rearrangement this expression becomes
log(γi ) = − √
1 + Ba I
where A and B are constant, zi is the valence number of ( ) aσS aτT
∆r G = σµ⊖ ⊖ ⊖ ⊖
S + τ µT − αµA − βµB +RT ln α β = 0
the ion, and I is ionic strength. aA aB
4 8
The sum σμo
S + τμo
T − αμo
A − βμo
B is the standard free energy change for the reaction,
ΔᵣGo . Therefore,
∆r G⊖ = −RT ln K
K is the equilibrium constant. Note that activities and
equilibrium constants are dimensionless numbers.
This derivation serves two purposes. It shows the rela-
tionship between standard free energy change and equi-
librium constant. It also shows that an equilibrium con- [9]
stant is defined as a quotient of activities. In practical
terms this is inconvenient. When each activity is replaced
by the product of a concentration and an activity coeffi-
cient, the equilibrium constant is defined as [10]
[S]σ [T]τ γσ γτ
K= α β
× S Tβ
[A] [B] γAα γB
where [S] denotes the concentration of S, etc. In practice
equilibrium constants are determined in a medium such
that the quotient of activity coefficient is constant and can
be ignored, leading to the usual expression [12] Ge, Xinlei; Zhang, Mei; Guo, Min; Wang, Xidong (2008).
[S]σ [T]τ
K=
[A]α [B]β
which applies under the conditions that the activity quo- [13] Ge, Xinlei; Zhang, Mei; Guo, Min; Wang, Xidong (2008).
“Correlation and Prediction of Thermodynamic Proper-
tient has a particular (constant) value.
8 References
[1] IUPAC, Compendium of Chemical Terminology, 2nd ed.
(the “Gold Book”) (1997). Online corrected version:
(2006–) "Activity coefficient".
[2] DeHoff, Robert (2006). Thermodynamics in materials sci-
ence (2nd ed.). Boca Raton, Fla.: CRC Taylor & Francis.
pp. 230–231. ISBN 9780849340659.
[3] Ibáñez, Jorge G.; Hernández Esparza, Margarita; Doría
Serrano, Carmen; Singh, Mono Mohan (2007). Environ-
mental Chemistry: Fundamentals. Springer. ISBN 978-0-
387-26061-7.
[4] Atkins, Peter; dePaula, Julio (2006). “Section 5.9, The ac-
tivities of ions in solution”. Physical Chemisrry (8th ed.).
OUP. ISBN 9780198700722.
[5] Guggenheim, E. A. (1928). “The Conceptions of Elec-
trical Potential Difference between Two Phases and the
Individual Activities of Ions”. The Journal of Physical
Chemistry. 33 (6): 842–849. doi:10.1021/j150300a003.
ISSN 0092-7325.
REFERENCES
[6] IUPAC, Compendium of Chemical Terminology, 2nd ed.
(the “Gold Book”) (1997). Online corrected version:
(2006–) "pH".
[7] Rockwood, Alan L. (2015). “Meaning and Measurability
of Single-Ion Activities, the Thermodynamic Foundations
of pH, and the Gibbs Free Energy for the Transfer of Ions
between Dissimilar Materials”. ChemPhysChem. 16 (9):
1978–1991. doi:10.1002/cphc.201500044. ISSN 1439-
4235.
[8] Betts, R. H.; MacKenzie, Agnes N. “Radiochemical
Measurements of Activity Coefficients in Mixed Elec-
trolytes”. Canadian Journal of Chemistry. 30 (2): 146–
162. doi:10.1139/v52-020.
King, E. L. (1964). “Book Review: Ion Association, C.
W. Davies, Butterworth, Washington, D.C., 1962”. Sci-
ence. 143 (3601): 37. doi:10.1126/science.143.3601.37.
ISSN 0036-8075.
Grenthe, I.; Wanner, H. “Guidelines for the extrapolation
to zero ionic strength” (PDF).
[11] Ge, Xinlei; Wang, Xidong; Zhang, Mei; Seetharaman,
Seshadri (2007). “Correlation and Prediction of Ac-
tivity and Osmotic Coefficients of Aqueous Electrolytes
at 298.15 K by the Modified TCPC Model”. Journal
of Chemical & Engineering Data. 52 (2): 538–547.
doi:10.1021/je060451k. ISSN 0021-9568.
“Correlation and Prediction of Thermodynamic Proper-
ties of Nonaqueous Electrolytes by the Modified TCPC
Model”. Journal of Chemical & Engineering Data. 53 (1):
149–159. doi:10.1021/je700446q. ISSN 0021-9568.
ties of Some Complex Aqueous Electrolytes by the Modi-
fied Three-Characteristic-Parameter Correlation Model”.
Journal of Chemical & Engineering Data. 53 (4): 950–
958. doi:10.1021/je7006499. ISSN 0021-9568.
[14] Ge, Xinlei; Wang, Xidong (2009). “A Simple Two-
Parameter Correlation Model for Aqueous Electrolyte So-
lutions across a Wide Range of Temperatures”. Jour-
nal of Chemical & Engineering Data. 54 (2): 179–186.
doi:10.1021/je800483q. ISSN 0021-9568.
[15] “Project: Ionic Strength Corrections for Stability Con-
stants”. IUPAC. Archived from the original on 29 Oc-
tober 2008. Retrieved 2008-11-15.
[16] Klamt, Andreas (2005). COSMO-RS from quantum chem-
istry to fluid phase thermodynamics and drug design (1st
ed.). Amsterdam: Elsevier. ISBN 978-0-444-51994-8.
[17] N. Butler, James (1998). Ionic equilibrium: solubility and
pH calculations. New York, NY [u.a.]: Wiley. ISBN
9780471585268.
[18] Ellis, A. J.; Golding, R. M. (1963). “The solubility of car-
bon dioxide above 100 degrees C in water and in sodium
chloride solutions”. American Journal of Science. 261 (1):
47–60. doi:10.2475/ajs.261.1.47. ISSN 0002-9599.
 5

[19] Kortüm, G. (1960). “The Structure of Electrolytic Solu-

tions, herausgeg. von W. J. Hamer. John Wiley & Sons,
Inc., New York; Chapman & Hall, Ltd., London 1959. 1.
Aufl., XII, 441 S., geb. $ 18.50”. Angewandte Chemie. 72
(24): 97. doi:10.1002/ange.19600722427. ISSN 0044-
8249.

9 External links
• AIOMFAC online-model An interactive group-
contribution model for the calculation of activity co-
efficients in organic-inorganic mixtures.

• Electrochimica Acta Single-ion activity coefficients

6 10 TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES

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