Activity coefficient

An activity coefficient is a factor used in

thermodynamics to account for deviations
from ideal behaviour in a mixture of
chemical substances.[1] In an ideal
mixture, the microscopic interactions
between each pair of chemical species are
the same (or macroscopically equivalent,
the enthalpy change of solution and
volume variation in mixing is zero) and, as
a result, properties of 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 activity coefficient.
Analogously, expressions involving gases
can be adjusted for non-ideality by scaling
partial pressures by a fugacity coefficient.

The concept of activity coefficient is

closely linked to that of activity in
chemistry.

Thermodynamic definition
The chemical potential, μB, of a substance
B in an ideal mixture of liquids or an ideal
solution is given by

o
where μB is the chemical potential of a
pure substance and xB is the mole
fraction of the substance in the mixture.

This is generalised to include non-ideal

behavior by writing

when aB is the activity of the substance in

the mixture with
where γB is the activity coefficient, which
may itself depend on xB. As γB approaches
1, the substance behaves as if it were
ideal. For instance, if γB ≈ 1, then Raoult's
law is accurate. For γB > 1 and γB < 1,
substance B shows positive and negative
deviation from Raoult's law, respectively. A
positive deviation implies that substance B
is more volatile.

In many cases, as xB goes to zero, the

activity coefficient of substance B
approaches a constant; this relationship is
Henry's law for the solvent. These
relationships are related to each other
through the Gibbs–Duhem equation.[2]
Note that in general activity coefficients
are dimensionless.

In detail: Raoult's law states that the

partial pressure of component B is related
to its vapor pressure (saturation pressure)
and its mole fraction xB in the liquid phase,

with the convention In

other words: Pure liquids represent the
ideal case.

At infinite dilution, the activity coefficient

approaches its limiting value, γB∞.
Comparison with Henry's law,

immediately gives

In other words: The compound shows

nonideal behavior in the dilute case.

The above definition of the activity

coefficient is impractical if the compound
does not exist as a pure liquid. This is
often the case for electrolytes or
biochemical compounds. In such cases, a
different definition is used that considers
infinite dilution as the ideal state:
with and

The symbol has been used here to

dinstinguish between the two kinds of
activity coefficients. Usually it is omitted,
as it is clear from the context which kind is
meant. But there are cases where both
kinds of activity coefficients are needed
and may even appear in the same
equation, e.g., for solutions of salts in
(water + alcohol) mixtures. This is
sometimes a source of errors.

Modifying mole fractions or

concentrations by activity coefficients
gives the effective activities of the
components, 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 important 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]

Ionic solutions

For solution of substances which ionize in

solution the activity coefficients of the
cation and anion cannot be experimentally
determined independently of each other
because solution properties depend on
both ions. Single ion activity coefficients
must be linked to the activity coefficient 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 stoichiometric because it expresses
both the deviation from the ideality of the
solution and the incomplete ionic
dissociation 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 following:

where γ+ and γ− are the activity

coefficients of the cation and anion
respectively.
More generally, the mean activity
coefficient of a compound of formula ApBq
is given by[4]

Single-ion activity coefficients can be

calculated theoretically, for example by
using the Debye–Hückel equation. The
theoretical equation can be tested by
combining the calculated single-ion
activity coefficients to give mean values
which can be compared to experimental
values.

The prevailing view that single ion activity

coefficients are unmeasurable
independently, or perhaps even physically
meaningless, has its roots in the work of
Guggenheim in the late 1920s.[5] However,
chemists have never been able to give up
the idea of single ion activities, and by
implication single ion activity coefficients.
For example, pH is defined as the negative
logarithm of the hydrogen ion activity. If
the prevailing view on the physical
meaning and measurability of single ion
activities is correct then defining pH as the
negative logarithm of the hydrogen ion
activity places the quantity squarely in the
unmeasurable category. Recognizing this
logical difficulty, International Union of
Pure and Applied Chemistry (IUPAC) states
that the activity-based definition of pH is a
notional definition only.[6] Despite the
prevailing negative view on the
measurability of single ion coefficients, the
concept of single ion activities continues
to be discussed in the literature, and at
least one author presents a definition of
single ion activity in terms of purely
thermodynamic quantities and proposes a
method of measuring single ion activity
coefficients based on purely
thermodynamic processes.[7]

Experimental determination
of 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.

Radiochemical methods

Activity coefficients can be determined by

radiochemical methods.[8]

Theoretical calculation of
activity coefficients

UNIQUAC Regression of activity coefficients

(chloroform/methanol mixture)

Activity coefficients of electrolyte

solutions may be calculated theoretically,
using the Debye–Hückel equation or
extensions such as the Davies equation,[9]
Pitzer equations[10] or TCPC
model.[11][12][13][14] Specific ion interaction
theory (SIT)[15] may also be used.

For non-electrolyte solutions correlative

methods such as UNIQUAC, NRTL,
MOSCED or UNIFAC may be employed,
provided fitted component-specific or
model parameters are available. COSMO-
RS is a theoretical method which is less
dependent on model parameters as
required information is obtained from
quantum mechanics calculations specific
to each molecule (sigma profiles)
combined with a statistical
thermodynamics treatment of surface
segments.[16]
For uncharged species, the activity
coefficient γ0 mostly follows a salting-out
model:[17]

This simple model predicts activities of

many species (dissolved undissociated
gases such as CO2, H2S, NH3,
undissociated acids and bases) to high
ionic strengths (up 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]

For water as solvent, the activity aw can be

calculated using:[17]
where ν is the number of ions produced
from the dissociation of one molecule of
the dissolved salt, b is the molality of the
salt dissolved in water, φ is the osmotic
coefficient of water, and the constant
55.51 represents the molality of water. In
the above equation, the activity of a
solvent (here water) is represented as
inversely proportional to the number of
particles of salt versus that of the solvent.

Link to ionic diameter

The ionic activity coefficient is connected
to the ionic diameter a by the formula
obtained from Debye-Huckel theory of
electrolytes:

where A and B are constant, zi is the

valence number of the ion, and I is ionic
strength.

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

Similarly, the derivative of an activity

coefficient with respect to pressure can be
related to excess molar volume.

Concentrated solutions of
electrolytes
For concentrated ionic solutions the
hydration of ions must be taken into
consideration, as done by Stokes and
Robinson in their hydration model from
1948[19]. The activity coefficient of the
electrolyte is split into electric and
statistical components by E. Glueckauf
who modifies the Robinson Stokes model.

The statistical part includes hydration

index number h , the number of ions from
the dissociation and the ratio r between
the apparent molar volume of the
electrolyte and the molar volume of water
and molality b.

Concentrated solution statistical part of

the activity coefficient is:
[20],[21][22]

The Stokes Robinson model has been

analyzed and improved by other
investigators as well[23][24].

Application to chemical
equilibrium
At equilibrium, the sum of the chemical
potentials of the reactants is equal to the
sum of the chemical potentials of the
products. The Gibbs free energy change
for the reactions, ΔrG, is equal to the
difference between these sums and
therefore, at equilibrium, is equal to zero.
Thus, for an equilibrium such as

α A + β B ⇌ σ S + τ T

Substitute in the expressions for the

chemical potential of each reactant:

Upon rearrangement this expression

becomes
 o o o o
The sum σμS + τμT − αμA − βμB is the
standard free energy change for the
reaction, ΔrGo. Therefore,

K is the equilibrium constant. Note that

activities and equilibrium constants are
dimensionless numbers.

This derivation serves two purposes. It

shows the relationship between standard
free energy change and equilibrium
constant. It also shows that an equilibrium
constant 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 coefficient, the equilibrium
constant is defined as

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
which applies under the conditions that
the activity quotient has a particular
(constant) value.

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 science (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). Environmental
Chemistry: Fundamentals. Springer.
ISBN 978-0-387-26061-7.
4. Atkins, Peter; dePaula, Julio (2006).
"Section 5.9, The activities of ions in
solution". Physical Chemisrry (8th ed.). OUP.
ISBN 9780198700722.
5. Guggenheim, E. A. (1928). "The
Conceptions of Electrical 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 .
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 Electrolytes" .
Canadian Journal of Chemistry. 30 (2):
146–162. doi:10.1139/v52-020 .
9. King, E. L. (1964). "Book Review: Ion
Association, C. W. Davies, Butterworth,
Washington, D.C., 1962". Science. 143
(3601): 37. Bibcode:1964Sci...143...37D .
doi:10.1126/science.143.3601.37 .
ISSN 0036-8075 .
10. 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 Activity 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 .
12. Ge, Xinlei; Zhang, Mei; Guo, Min; Wang,
Xidong (2008). "Correlation and Prediction
of Thermodynamic Properties of
Nonaqueous Electrolytes by the Modified
TCPC Model". Journal of Chemical &
Engineering Data. 53 (1): 149–159.
doi:10.1021/je700446q . ISSN 0021-9568 .
13. Ge, Xinlei; Zhang, Mei; Guo, Min; Wang,
Xidong (2008). "Correlation and Prediction
of Thermodynamic Properties of Some
Complex Aqueous Electrolytes by the
Modified 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 Solutions across a
Wide Range of Temperatures". Journal of
Chemical & Engineering Data. 54 (2): 179–
186. doi:10.1021/je800483q . ISSN 0021-
9568 .
15. "Project: Ionic Strength Corrections for
Stability Constants" . IUPAC. Archived from
the original on 29 October 2008. Retrieved
2008-11-15.
16. Klamt, Andreas (2005). COSMO-RS from
quantum chemistry 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 carbon dioxide above 100
degrees C in water and in sodium chloride
solutions". American Journal of Science.
261 (1): 47–60.
Bibcode:1963AmJS..261...47E .
doi:10.2475/ajs.261.1.47 . ISSN 0002-
9599 .
19.
http://pubs.acs.org/doi/10.1021/ja01185a
065
20.
http://pubs.rsc.org/en/content/articlelandin
g/1955/tf/tf9555101235#!divAbstract
21.
http://pubs.rsc.org/en/content/articlelandin
g/1957/tf/tf9575300305#!divAbstract
22. Kortüm, G. (1960). "The Structure of
Electrolytic Solutions, 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
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doi:10.1002/ange.19600722427 .
ISSN 0044-8249 .
23.
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43a034
24.
https://link.springer.com/article/10.1007/B
F00649040

External links
AIOMFAC online-model An interactive
group-contribution model for the
calculation of activity coefficients in
organic-inorganic mixtures.
Electrochimica Acta Single-ion activity
coefficients

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