Thermodynamic

activity

In chemical thermodynamics, activity

(symbol a) is a measure of the "effective
concentration" of a species in a mixture, in
the sense that the species' chemical
potential depends on the activity of a real
solution in the same way that it would
depend on concentration for an ideal
solution.
By convention, activity is treated as a
dimensionless quantity, although its value
depends on customary choices of
standard state for the species. The activity
of pure substances in condensed phases
(solid or liquids) is normally taken as unity
(the number 1). Activity depends on
temperature, pressure and composition of
the mixture, among other things. For
gases, the activity is the effective partial
pressure, and is usually referred to as
fugacity.

The difference between activity and other

measures of composition arises because
molecules in non-ideal gases or solutions
interact with each other, either to attract or
to repel each other. The activity of an ion is
particularly influenced by its surroundings.

Activities should be used to define

equilibrium constants but, in practice,
concentrations are often used instead.
The same is often true of equations for
reaction rates. However, there are
circumstances where the activity and the
concentration are significantly different
and, as such, it is not valid to approximate
with concentrations where activities are
required. Two examples serve to illustrate
this point:
In a solution of potassium hydrogen
iodate [KH(IO3)2] at 0.02 M the activity is
40% lower than the calculated hydrogen
ion concentration, resulting in a much
higher pH than expected.
When a 0.1 M hydrochloric acid solution
containing methyl green indicator is
added to a 5 M solution of magnesium
chloride, the color of the indicator
changes from green to yellow—
indicating increasing acidity—when in
fact the acid has been diluted. Although
at low ionic strength (< 0.1 M) the
activity coefficient approaches unity, this
coefficient can actually increase with
ionic strength in a high ionic strength
 regime. For hydrochloric acid solutions,
the minimum is around 0.4 M.[1]

Definition
The activity of a species i, denoted ai, is
defined[2][3] as:

where μi is the chemical potential of the

species i in under the conditions of
interest, μoi is the chemical potential of
that species under some defined set of
standard conditions, R is the gas constant,
T is the thermodynamic temperature and e
is the exponential constant.
Alternatively, this equation can be written
as:

In general, the activity depends on any

factor that alters the chemical potential.
Such factors may include: concentration,
temperature, pressure, interactions
between chemical species, electric fields,
etc. Depending on the circumstances,
some of these factors may be more
important than others.

It is important to note that the activity

depends on the choice of standard state
such that changing the standard state will
also change the activity. This means that
activity is a relative term that describes
how "active" a compound is compared to
when it is under the standard state
conditions. In principle, the choice of
standard state is arbitrary; however, it is
often chosen out of mathematical or
experimental convenience. Alternatively, it
is also possible to define an "absolute
activity", λ, which is written as:

Activity coefficient

The activity coefficient γ, which is also a

dimensionless quantity, relates the activity
to a measured amount fraction xi (or yi in
the gas phase), molality bi, mass fraction
wi, amount concentration ci or mass
concentration ρi:

The division by the standard molality bo or

the standard amount concentration co is
necessary to ensure that both the activity
and the activity coefficient are
dimensionless, as is conventional.[3]

The activity is the same regardless of the

ways to express composition and the
standard state chosen so the above
expressions are equal.

When the activity coefficient is close to

one, the substance shows almost ideal
behaviour according to Henry's law. In
these cases, the activity can be
substituted with the appropriate
dimensionless measure of composition xi,
bi/bo or ci/co. It is also possible to define
an activity coefficient in terms of Raoult's
law: the International Union of Pure and
Applied Chemistry (IUPAC) recommends
the symbol f for this activity coefficient,[3]
although this should not be confused with
fugacity.
 .

Standard states
Gases

In most laboratory situations, the

difference in behaviour between a real gas
and an ideal gas is dependent only on the
pressure and the temperature, not on the
presence of any other gases. At a given
temperature, the "effective" pressure of a
gas i is given by its fugacity fi: this may be
higher or lower than its mechanical
pressure. By historical convention,
fugacities have the dimension of pressure,
so the dimensionless activity is given by:
where φi is the dimensionless fugacity
coefficient of the species, yi is its fraction
in the gaseous mixture (y = 1 for a pure
gas) and p is the total pressure. The value
po is the standard pressure: it may be
equal to 1 atm (101.325 kPa) or 1 bar
(100 kPa) depending on the source of
data, and should always be quoted.

Mixtures in general

The most convenient way of expressing

the composition of a generic mixture is by
using the amount fractions x (written y in
the gas phase) of the different
components, where

The standard state of each component in

the mixture is taken to be the pure
substance, i.e. the pure substance has an
activity of one. When activity coefficients
are used, they are usually defined in terms
of Raoult's law,

where fi is the Raoult's law activity

coefficient: an activity coefficient of one
indicates ideal behaviour according to
Raoult's law.

Dilute solutions (non-ionic)

A solute in dilute solution usually follows

Henry's law rather than Raoult's law, and it
is more usual to express the composition
of the solution in terms of the amount
concentration c (in mol/L) or the molality b
(in mol/kg) of the solute rather than in
amount fractions. The standard state of a
dilute solution is a hypothetical solution of
concentration co = 1 mol/L (or molality
bo = 1 mol/kg) which shows ideal
behaviour (also referred to as "infinite-
dilution" behaviour). The standard state,
and hence the activity, depends on which
measure of composition is used.
Molalities are often preferred as the
volumes of non-ideal mixtures are not
strictly additive and are also temperature-
dependent: molalities do not depend on
volume, whereas amount concentrations
do.[4]

The activity of the solute is given by:

Ionic solutions
When the solute undergoes ionic
dissociation in solution (a salt e.g.), the
system becomes decidedly non-ideal and
we need to take the dissociation process
into consideration. One can define
activities for the cations and anions
separately (a+ and a–).

It should be noted however that in a liquid

solution the activity coefficient of a given
ion (e.g. Ca2+) isn't measurable because it
is experimentally impossible to
independently measure the
electrochemical potential of an ion in
solution. (One cannot add cations without
putting in anions at the same time).
Therefore, one introduces the notions of

mean ionic activity

ν ν+ ν−
a± = a+ a−
mean ionic molality
ν ν+ ν−
b± = b+ b−
mean ionic activity coefficient
ν ν+ ν−
γ± = γ+ γ−

where ν = ν+ + ν– represent the

stoichiometric coefficients involved in the
ionic dissociation process

Even though γ+ and γ– cannot be

determined separately, γ± is a measureable
quantity that can also be predicted for
sufficiently dilute systems using Debye–
Hückel theory. For electrolyte-solutions at
higher concentrations, Debye–Hückel
theory needs to be extended and replaced,
e.g., by a Pitzer electrolyte solution model
(see external links below for examples).
For the activity of a strong ionic solute
(complete dissociation) we can write:

ν ν ν
a2 = a± = γ±m±

Measurement
The most direct way of measuring the
activity of a volatile species is to measure
its equilibrium partial vapor pressure. For
non-volatile components, such as sucrose
or sodium chloride(NaCl), this approach
will not work since they do not have
measurable vapor pressures at most
temperatures. However, in such cases it is
possible to measure the vapor pressure of
the solvent instead. Using the Gibbs–
Duhem relation it is possible to translate
the change in solvent vapor pressures with
concentration into activities for the solute.

The simplest way of determining activity

of a component is by measurement of
densities of solution, knowing that real
solutions have deviations from the
additivity of (molar) volumes of pure
components compared to the (molar)
volume of the solution. This involves the
use of partial molar volumes.

Another way to determine the activity of a

species is through the manipulation of
colligative properties, specifically freezing
point depression. Using freezing point
depression techniques, it is possible to
calculate the activity of a weak acid from
the relation,

where b′ is the total equilibrium molality of

solute determined by any colligative
property measurement (in this case ΔTfus,
b is the nominal molality obtained from
titration and a is the activity of the species.

There are also electrochemical methods

that allow the determination of activity and
its coefficient.

The value of the mean ionic activity

coefficient γ± of ions in solution can also
be estimated with the Debye–Hückel
equation, the Davies equation or the Pitzer
equations.

single ion activity measurability

revisited

The prevailing view that single ion

activities are unmeasurable, 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. For example, pH is defined as
the negative logarithm of the hydrogen ion
activity. By implication, if the prevailing
view on the physical meaning and
measurability of single ion activities is
correct it relegates pH to the category of
thermodynamically unmeasurable
quantities. For this reason the
International Union of Pure and Applied
Chemistry (IUPAC) states that the activity-
based definition of pH is a notional
definition only and further states that the
establishment of primary pH standards
requires the application of the concept of
'primary method of measurement' tied to
the Harned cell.[6] Nevertheless, the
concept of single ion activities continues
to be discussed in the literature, and at
least one author purports to define single
ion activities in terms of purely
thermodynamic quantities. The same
author also proposes a method of
measuring single ion activity coefficients
based on purely thermodynamic
processes.[7]

Use
Chemical activities should be used to
define chemical potentials, where the
chemical potential depends on the
temperature T, pressure p and the activity
ai according to the formula:

o
where R is the gas constant and µi is the
value of µi under standard conditions.
Note that the choice of concentration
scale affects both the activity and the
standard state chemical potential, which is
especially important when the reference
state is the infinite dilution of a solute in a
solvent.
Formulae involving activities can be
simplified by considering that:

For a chemical solution:

the solvent has an activity of unity
(only a valid approximation for
rather dilute solutions)
At a low concentration, the activity
of a solute can be approximated to
the ratio of its concentration over
the standard concentration:

Therefore, it is approximately equal to its

concentration.
 For a mix of gas at low pressure, the
activity is equal to the ratio of the partial
pressure of the gas over the standard
pressure:

Therefore, it is equal to the partial

pressure in bars (compared to a
standard pressure of 1 bar).
For a solid body, a uniform, single
species solid at one bar has an activity
of unity. The same thing holds for a pure
liquid.

The latter follows from any definition

based on Raoult's law, because if we let
the solute concentration x1 go to zero, the
vapor pressure of the solvent p will go to
p*. Thus its activity a = p/p* will go to
unity. This means that if during a reaction
in dilute solution more solvent is
generated (the reaction produces water
e.g.) we can typically set its activity to
unity.

Solid and liquid activities do not depend

very strongly on pressure because their
molar volumes are typically small.
Graphite at 100 bars has an activity of only
1.01 if we choose po = 1 bar as standard
state. Only at very high pressures do we
need to worry about such changes.
Example values
Example values of activity coefficients of
sodium chloride in aqueous solution are
given in the table.[8] In an ideal solution,
these values would all be unity. The
deviations tend to become larger with
increasing molality and temperature, but
with some exceptions.

Molality (mol/kg) 25 °C 50 °C 100 °C 200 °C 300 °C 350 °C

0.05 0.820 0.814 0.794 0.725 0.592 0.473

0.50 0.680 0.675 0.644 0.619 0.322 0.182

2.00 0.669 0.675 0.641 0.450 0.212 0.074

5.00 0.873 0.886 0.803 0.466 0.167 0.044

See also
Fugacity, the equivalent of activity for
partial pressure
 Chemical equilibrium
Electrochemical potential
Excess chemical potential
Partial molar property
Thermodynamic equilibrium
Thermal expansion
Virial expansion
Water activity
Non-random two-liquid model (NRTL
model) - Phase equilibrium calculations
UNIQUAC model - Phase equilibrium
calculations

References
1. McCarty, Christopher G.; Vitz, Ed (2006),
"pH Paradoxes: Demonstrating that it is not
true that pH ≡ −log[H+]", J. Chem. Educ., 83
(5): 752, Bibcode:2006JChEd..83..752M ,
doi:10.1021/ed083p752
2. IUPAC, Compendium of Chemical
Terminology, 2nd ed. (the "Gold Book")
(1997). Online corrected version:  (2006–)
"activity (relative activity), a ".
3. International Union of Pure and Applied
Chemistry (1993). Quantities, Units and
Symbols in Physical Chemistry, 2nd edition,
Oxford: Blackwell Science. ISBN 0-632-
03583-8. pp. 49–50. Electronic version.
4. Kaufman, Myron (2002), Principles of
thermodynamics, CRC Press, p. 213, ISBN 0-
8247-0692-7
5. Guggenheim, E. A. (1929). "The
Conceptions of Electrical Potential
Difference between Two Phases and the
Individual Activities of Ions". J. Phys. Chem.
33: 842–849. doi:10.1021/j150300a003 .
6. IUPAC, Compendium of Chemical
Terminology, 2nd ed. (the "Gold Book")
(1997). Online corrected version:  (2006–)
"pH ".
7. Rockwood, A.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: 1978–1991.
doi:10.1002/cphc.201500044 .
8. Cohen, Paul (1988), The ASME Handbook
on Water Technology for Thermal Systems,
American Society of Mechanical Engineers,
p. 567, ISBN 0-7918-0300-7

External links
Equivalences among different forms of
activity coefficients and chemical
potentials
Calculate activity coefficients of
common inorganic electrolytes and their
mixtures
 AIOMFAC online-model : calculator for
activity coefficients of inorganic ions,
water, and organic compounds in
aqueous solutions and multicomponent
mixtures with organic compounds.

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