activity
Definition
The activity of a species i, denoted ai, is
defined[2][3] as:
Activity coefficient
Standard states
Gases
Mixtures in general
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–).
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.
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:
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.
Retrieved from
"https://en.wikipedia.org/w/index.php?
title=Thermodynamic_activity&oldid=818597140"