Research: Science and Education

The Definition and Unit of Ionic Strength

Theodros Solomon
Department of Chemistry, Addis Ababa University, P.O. Box 1176, Addis Ababa, Ethiopia; t.solomon@hotmail.com

Ionic strength was defined by Lewis and Randall (1) to
reflect the effect of charges and interionic interactions on elec-
trolyte activities, and hence on ionic activity coefficients. The
original definition for ionic strength (symbol I or µ) was given
as
I = µ = 1⁄2 ∑m i zi2 (1)
where mi is the ionic concentration in units of molality or
mol kg
1, and zi is the number of charges on the ion. Accord-
ing to this definition, ionic strength has units of mol kg
1.
Many textbooks (e.g. 2–4) use this definition.
However, ionic strength is defined in several other text-
books and monographs (5–9) as
I = µ = 1⁄2 ∑c i zi2 (2)
where ci is the ionic concentration in units of molarity
(mol L
1 or mol dm
3). Some textbooks (10) add a qualifying
phrase to distinguish between the two definitions by referring
to the former as the molality-scale ionic strength. The under-
standing is thus that ionic strength will have the same unit
as the concentration unit used in its definition.
Either of the two definitions above may successfully be
used in the Debye–Hückel theory to arrive at the following
expression for the mean ionic activity coefficient (3):
N A e 2b NA e2
ln γ± =
z +z
=
z +z
BI 1/ 2 (3)
8πεRT 8πεRT
where the Debye length or the “thickness of the ionic atmo-
sphere” 1/b is defined through the relation
1/ 2 1/ 2
N A2 e 2 N A2 e 2ρ0
b=
εRT
Σ c izi2 =
εRT
Σ m izi2 = BI 1/ 2 (4)
NA is the Avogadro number, e is the electronic charge, ε is
the permittivity of the medium (ε = εr ε0, εr is the dielectric
constant and ε0 is the vacuum permittivity), ρ0 is the density
of the solvent, and R and T have their customary significance.
The approximation ci = mi ρ0 is used for a very dilute solution.
For an aqueous solution, substitution of the numerical values
of the constants yields the following results (3, 10):
B = 3.28 × 109 (kg mol
1 m
2)1/ 2
1000 g
1)(1 g cm
3), and hence the magnitude of ci may be
substituted for mi without introducing any numerical con-
version factor. Hence eq 5 is still valid when ionic strength is
expressed in mol L
1 (or mol dm
3) but the constant 0.509
now has the unit of (dm3 mol
1)1/2.
If, however, concentration is expressed in the SI unit
mol m
3, then the constant will have a value different by a
factor of 1000
1/2. Equation 5 then becomes
log γ± =
0.0161|z+ z
| I 1/2 (6)
and 0.0161 has the unit (m3 mol-1)1/2. One can therefore see
that students, in their desire to convert mol L
1 to SI units
and hence express concentrations in mol m
3, would arrive at
completely different values for mean ionic activity coefficients
on using eq 5.
A further difficulty appears in using either eq 1 or eq 2
in the following simplified form of the extended Debye–
Hückel expression for the activity coefficient:
0.509 z +z
I 1/ 2
log γ± =
(7)
1 + I 1/ 2
If ionic strength has a unit, there appears to be a problem in the
denominator (unless one tries to convince students that the
second term in the denominator is actually dimensionless).
In fact, eq 7 is a simplification of the equation
0.509 z +z
I 1/ 2
log γ± =
(8)
1 + B a I 1/ 2
where a is the effective diameter of the ion in solution. If a is
taken as 3 × 10
10 m, then the product Ba in the denominator
is close to 1, but with a unit of (kg mol
1)1/2. The second
term in the denominator is thus dimensionless. To overcome
this apparent confusion, Levine (10) wrote eq 7 as
1/ 2
0.509 z +z
I
m°
log γ± =
(9)
I 1/ 2
1+
m°

log γ± =
A|z+ z
|I 1/2 =
0.509|z+ z
| I 1/2 (5) where m° = 1 mol kg
1. The factor I/m° thus becomes dimen-
where, if ionic strength is defined in terms of mol kg
1, the sionless; however, 0.509 has a unit, and the problem still exists.
constant 0.509 has the unit of (kg mol
1)1/2. The quantity Although the original definition for ionic strength (eq 1,
on the right-hand side is thus dimensionless, as it should be. with a unit of mol kg
1) is used in the 5th edition of Atkins’s
It is not immediately obvious to students why this same textbook (4 ), eq 5 is written in this reference as
equation is valid when ionic strength is defined in terms of 1/ 2 1/ 2
the non-SI unit mol L
1. The reason is, of course, that the log γ± =
A′ z +z
I =
0.509 z +z
I
(10)
approximation ci = mi ρ0 yields ci (mol 1000 cm
3) = mi (mol m° m°

JChemEd.chem.wisc.edu • Vol. 78 No. 12 December 2001 • Journal of Chemical Education 1691

 Research: Science and Education
Multiplication of eq 5 by (m°/m°)1/2 yields eq 10, where A′ =
A(m°)1/2 = 0.509 and is dimensionless. The ionic strength
term, I /m°, is also dimensionless. Furthermore, the extended
Debye–Hückel law is written in ref 4 as
1/ 2
0.509 z +z
I simplicity not only in activity coefficient calculations but also
m°
log γ± =
(11)
1/ 2
1 + B′ I
m°
where, in the denominator, a dimensionless B′ = Ba(m°)1/2
multiplies a dimensionless ionic strength term.
In an earlier edition, however, Atkins (11) had defined
a dimensionless ionic strength as
mi 2
I =µ= 1
2 m° i
Σ z (12)
(where m° = 1 mol kg
1). This definition actually is the same
as the original definition of ionic strength divided by m°, that
is, I /m°, and it is seen that this may be taken as the precursor
for the usage of the dimensionless ionic strength terms in
eqs 9–11. It is not clear why this definition was abandoned
in later editions of the textbook. In any case, it offers con-
siderable advantages, since all terms in eq 5, including the
constant 0.509, are now dimensionless. The reciprocal of
the Debye length, b, and the constant B will both have the
correct unit of m
1. Furthermore, the apparent problem of
unit in the use of eq 7 now disappears.
As seen above, it appears as if a consensus has not been
reached on how to define ionic strength and how to use it in
activity coefficient calculations. The rather variable definition
1692 Journal of Chemical Education • Vol. 78 No. 12 December 2001 • JChemEd.chem.wisc.edu
of ionic strength, with units of mol kg
1 or mol dm
3, with
or without dimensions as the case may be, creates unnecessary
confusion. Unless a case is made to retain eq 1 for historical
reasons, it is therefore recommended that eq 12 be used
consistently to define ionic strength and thereby attain
in expressing concentrations of electrolyte solutions.
Literature Cited
1. Lewis, G. N.; Randall, M. Thermodynamics; revised by Pitzer,
K. S.; Brewer, L.; McGraw Hill: New York, 1961.
2. Alberty, R. A.; Silbey, R. Physical Chemistry, 2nd ed.; Wiley:
New York, 1996.
3. Moore, W. J. Physical Chemistry, 5th ed.; Longmans: London,
1972.
4. Atkins, P. W. Physical Chemistry, 5th ed.; Oxford University
Press: New York, 1994.
5. Maron, S. H.; Lando, J. B. Fundamentals of Physical Chemistry;
Macmillan: New York, 1974.
6. Barrow, G. Physical Chemistry, 4th ed.; McGraw Hill: New
York, 1979.
7. Robinson, R. A.; Stokes, R. H. Electrolyte Solutions;
Butterworths: London, 1968.
8. Bockris, J. O’M.; Reddy, A. K. N. Modern Electrochemistry;
Plenum: New York, 1977.
9. Riegel, P. H. Electrochemistry; Prentice Hall: Englewood Cliffs,
NJ, 1987.
10. Levine, I. N. Physical Chemistry, 3rd. ed.; McGraw Hill: New
York, 1988.
11. Atkins, P. W. Physical Chemistry, 3rd ed.; Oxford University
Press: New York, 1986.