Research: Science and Education

The Definition and Unit of Ionic Strength

Ionic strength was defined by Lewis and Randall (1) to 1000 g
1)(1 g cm
3), and hence the magnitude of ci may be
reflect the effect of charges and interionic interactions on elec- substituted for mi without introducing any numerical con-
trolyte activities, and hence on ionic activity coefficients. The version factor. Hence eq 5 is still valid when ionic strength is
original definition for ionic strength (symbol I or ) was given expressed in mol L
1 (or mol dm
3) but the constant 0.509
as now has the unit of (dm3 mol
1)1/2.
If, however, concentration is expressed in the SI unit
I = = 12 m i zi2 (1)
mol m
3, then the constant will have a value different by a
where mi is the ionic concentration in units of molality or factor of 1000
1/2. Equation 5 then becomes
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. log =
0.0161|z+ z
| I 1/2 (6)
Many textbooks (e.g. 24) use this definition.
and 0.0161 has the unit (m3 mol-1)1/2. One can therefore see
However, ionic strength is defined in several other text-
that students, in their desire to convert mol L
1 to SI units
books and monographs (59) as
and hence express concentrations in mol m
3, would arrive at
I = = 12 c i zi2 (2) completely different values for mean ionic activity coefficients
on using eq 5.
where ci is the ionic concentration in units of molarity
A further difficulty appears in using either eq 1 or eq 2
(mol L
1 or mol dm
3). Some textbooks (10) add a qualifying
in the following simplified form of the extended Debye
phrase to distinguish between the two definitions by referring
Hckel expression for the activity coefficient:
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. 0.509 z +z
I 1/ 2
Either of the two definitions above may successfully be log =
(7)
1 + I 1/ 2
used in the DebyeHckel theory to arrive at the following
expression for the mean ionic activity coefficient (3): If ionic strength has a unit, there appears to be a problem in the
denominator (unless one tries to convince students that the
N A e 2b NA e2 second term in the denominator is actually dimensionless).
ln =
z +z
=
z +z
BI 1/ 2 (3)
8RT 8RT In fact, eq 7 is a simplification of the equation
where the Debye length or the thickness of the ionic atmo- 0.509 z +z
I 1/ 2
sphere 1/b is defined through the relation log =
(8)
1 + B a I 1/ 2
1/ 2 1/ 2
N A2 e 2 N A2 e 20
b=
RT
c izi2 =
RT
m izi2 = BI 1/ 2 (4) 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
NA is the Avogadro number, e is the electronic charge, is term in the denominator is thus dimensionless. To overcome
the permittivity of the medium ( = r 0, r is the dielectric this apparent confusion, Levine (10) wrote eq 7 as
constant and 0 is the vacuum permittivity), 0 is the density
of the solvent, and R and T have their customary significance. 1/ 2
The approximation ci = mi 0 is used for a very dilute solution. 0.509 z +z
I
For an aqueous solution, substitution of the numerical values m
log =
(9)
of the constants yields the following results (3, 10): I 1/ 2
1+
B = 3.28 109 (kg mol
1 m
2)1/ 2 m

log =
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 Atkinss
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 =
A z +z
I =
0.509 z +z
I
(10)
approximation ci = mi 0 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

Multiplication of eq 5 by (m/m)1/2 yields eq 10, where A = of ionic strength, with units of mol kg
1 or mol dm
3, with
A(m)1/2 = 0.509 and is dimensionless. The ionic strength or without dimensions as the case may be, creates unnecessary
term, I /m, is also dimensionless. Furthermore, the extended confusion. Unless a case is made to retain eq 1 for historical
DebyeHckel law is written in ref 4 as reasons, it is therefore recommended that eq 12 be used
1/ 2
consistently to define ionic strength and thereby attain
0.509 z +z
I simplicity not only in activity coefficient calculations but also
m in expressing concentrations of electrolyte solutions.
log =
(11)
1/ 2
1 + B I Literature Cited
m
where, in the denominator, a dimensionless B = Ba(m)1/2 1. Lewis, G. N.; Randall, M. Thermodynamics; revised by Pitzer,
multiplies a dimensionless ionic strength term. K. S.; Brewer, L.; McGraw Hill: New York, 1961.
In an earlier edition, however, Atkins (11) had defined 2. Alberty, R. A.; Silbey, R. Physical Chemistry, 2nd ed.; Wiley:
a dimensionless ionic strength as New York, 1996.
3. Moore, W. J. Physical Chemistry, 5th ed.; Longmans: London,
mi 2
I == 1
2 m i
z (12) 1972.
4. Atkins, P. W. Physical Chemistry, 5th ed.; Oxford University
Press: New York, 1994.
(where m = 1 mol kg
1). This definition actually is the same 5. Maron, S. H.; Lando, J. B. Fundamentals of Physical Chemistry;
as the original definition of ionic strength divided by m, that Macmillan: New York, 1974.
is, I /m, and it is seen that this may be taken as the precursor 6. Barrow, G. Physical Chemistry, 4th ed.; McGraw Hill: New
for the usage of the dimensionless ionic strength terms in York, 1979.
eqs 911. It is not clear why this definition was abandoned 7. Robinson, R. A.; Stokes, R. H. Electrolyte Solutions;
in later editions of the textbook. In any case, it offers con- Butterworths: London, 1968.
siderable advantages, since all terms in eq 5, including the 8. Bockris, J. OM.; Reddy, A. K. N. Modern Electrochemistry;
constant 0.509, are now dimensionless. The reciprocal of Plenum: New York, 1977.
the Debye length, b, and the constant B will both have the 9. Riegel, P. H. Electrochemistry; Prentice Hall: Englewood Cliffs,
correct unit of m
1. Furthermore, the apparent problem of NJ, 1987.
unit in the use of eq 7 now disappears. 10. Levine, I. N. Physical Chemistry, 3rd. ed.; McGraw Hill: New
As seen above, it appears as if a consensus has not been York, 1988.
reached on how to define ionic strength and how to use it in 11. Atkins, P. W. Physical Chemistry, 3rd ed.; Oxford University
activity coefficient calculations. The rather variable definition Press: New York, 1986.

1692 Journal of Chemical Education Vol. 78 No. 12 December 2001 JChemEd.chem.wisc.edu