Article

pubs.acs.org/jchemeduc

Thermodynamics on the Molality Scale

Sebastian. G. Canagaratna*,† and M. Maheswaran‡
†
Department of Chemistry and Biochemistry, Ohio Northern University, Ada, Ohio 45810, United States
‡
Department of Mathematics, University of Wisconsin Marathon County, Wausau, Wisconsin 54401, United States
*
S Supporting Information

ABSTRACT: For physical measurements, the compositions of solutions, especially electrolyte solutions, are expressed in terms
of molality rather than mole fractions. The development of the necessary thermodynamic equations directly in terms of molality
is not common in textbooks, and the treatment in the literature is not very systematic. We develop a methodical treatment of this
topic and define a new reference solution that can be used for solutions whose composition is described in terms of molality.
Thermodynamic quantities per mass of solvent appear naturally in the derivation. We discuss how these quantities may be used
to analyze experimental data.
KEYWORDS: Upper-Division Undergraduate, Graduate Education/Research, Physical Chemistry, Textbooks/Reference Books,
Thermodynamics

W hen the thermodynamics of mixtures is discussed at the

upper level, students have already been introduced to
the differentials of internal energy U, enthalpy H, Helmholtz
energy A, and Gibbs energy G in terms of the differentials of
the corresponding characteristic variables. Of particular interest
is the derivation of the differential of G, because it affords an
opportunity for the introduction of the concept of partial molar
Gibbs energies or chemical potentials μi of species i in the
mixture. Also, we can extend the idea to partial molar quantities
of other extensive quantities such as volume V, enthalpy H, and
heat capacity Cp. The independent variables of interest are the
temperature T, the pressure p as well as the extensive variables
n1, n2, ..., which denote the amounts of species 1, 2 ... .
Changing the relative amounts will change the composition of
the mixture.
Although the composition and changes in it can be
adequately described in terms of the amounts n1, n2, ..., it is
more convenient to use intensive composition variables such as
mole fractions x1, x2, ..., or molalities m2, m3, ..., where mi = ni/
W1, the amount of i per mass of solvent, species 1. Many
experiments directly determine intensive quantities such as
density. Even in cases where extensive quantities are
determined, comparison of the results of different investigators
requires the calculation of intensive quantities. Because
intensive quantities may be expressed entirely in terms of
© XXXX American Chemical Society and
Division of Chemical Education, Inc.
intensive variables only, it is convenient to develop the
necessary thermodynamic equations entirely in term of
intensive variables.
Although many texts develop equations in terms of mole
fractions, especially in connection with mean molar Gibbs
energy, the treatment of the thermodynamics of solutions in
terms of molalities appears to be neglected. For physical
measurements molalities are used widely to describe the
composition of solutions, especially when the components do
not mix in all proportions. Molalities have the useful property
that when the mass of solvent is constant, the addition of
species i to a solution changes mi only, whereas such an
addition changes all the mole fractions. In this respect, working
with molalities as variables closely parallels the use of amounts
as variables when the amount of solvent is held constant. The
purpose of this article is to show how thermodynamics on the
molality scale may be developed in a systematic way and to
explore the thermodynamic consequences of this approach. We
show that thermodynamic quantities per mass of solvent play
an important role in these equations in the same way that
thermodynamic quantities per mole play an important role
when the equations are developed in terms of mole fractions.
A dx.doi.org/10.1021/ed300127n | J. Chem. Educ. XXXX, XXX, XXX−XXX