In the Classroom
The Physical Meaning of the Mathematical Formalism Present
in Limiting Chemical Equations; Or, How Dilute Is Dilute?
C. Contreras-Ortega,* N. Bustamante, J. L. Guevara, C. Portillo, and V. Kesternich
Facultad de Ciencias, Universidad Católica del Norte, Casilla 1280‚ Antofagasta, Chile; *ccontrer@ucn.cl
In teaching and research, we frequently talk about solu-
tions being concentrated or dilute, or gases being at low or
high pressures or temperatures. But, just how “dilute” is di-
lute? And just how “low” is a low pressure or temperature?
Consider a 0.001 M solution: While a physical chemist teach-
ing a general chemistry laboratory might consider this to be
dilute, an analytical chemist working with trace levels might
consider this extremely concentrated. Similar complications
exist when discussing the usefulness or limitations of a given
algorithm. To one chemist an equation that is functional to
within 1.0% of accepted values might be considered a good
equation, but the same equation may not be acceptable to
another chemist.
Key to understanding the important dialectic illustrated
in the above examples is the realization that physical condi-
tions that control or limit the behavior of the phenomenon
or system also control the mathematical representations gen-
erated to describe it. While professional chemists understand
the important link between the conditions and limitations
of the phenomenon and its algorithm, students typically do
not understand that link. Let’s take, for example, some com-
monly used algorithms such as the ideal gas law, Nernst’s
equation, and Raoult’s and Henry’s laws. The mathematical
formalisms present in these algorithms are commonly ex-
pressed as mathematical tendencies and limits. Unfortunately,
the general nature of these formalisms is a source of ambiguity
and confusion for students because the exact physical mean-
ing of the mathematical tendencies and limits is not always
denoted. This problem is compounded by the fact that gen-
l
eral chemistry textbooks tend to include only equations that
are strictly valid only for systems behaving under limiting
physical conditions (1–6).
In this article, we propose a general mathematical treat-
ment for chemical systems to help overcome the problems
outlined above, while providing students a better understand-
ing of the real scope of the mathematical equations they will
encounter.
Tendencies and Limits
Let us start by considering some important terms needed
in the larger discussion. Tendency is the behavior of an inde-
pendent mathematical variable to approach a limiting value.
For example, the physical phenomenon of pressure can tend
toward a low, high, or constant value. Thus, pressure is com-
monly expressed as a value tending to zero, infinity, or a con-
stant, respectively. The limiting value of the tendency (zero,
infinity, or a constant) fixes the boundary conditions of the
algorithm in use.
l
A limit is the particular limiting value or the particular
limiting expression of an equation, a numerical limit and an
equational limit, respectively. Consider the following examples
for clarification. The unity value for the activity coefficient
788 Journal of Chemical Education • Vol. 84 No. 5 May 2007
of a solute as its concentration tends to a low value is an ex-
ample of a numerical limit. An example of an equational limit
is the concentration-based expression for the chemical equi-
librium constant as the concentrations of the chemical spe-
cies (solutes) tend to low values.
Limit Validity
A fundamental question that should now be raised is:
When does the numerical limit or the equational limit become
valid or apply? Limits become valid at those values of their
respective tendency where the difference between (concor-
dance) an accepted result (an experimentally or theoretically
reliable result) and the obtained experimental result is accept-
ably small.
This concordance can be expressed as a mathematical
tolerance, such as, for example, a linear regression index, a
deviation (an arithmetical quotient or difference) or percent
variation, and so forth. We will name any one of these crite-
ria a concordance criterion.
Values of Numerical Limits and Tendencies
When the limit of an equation (a function) is a numeri-
cal value (a numerical limit), the explicit mathematical rela-
tionship between the function, its limit, and the tendency of
its independent variable is frequently expressed as:
lim f ( x ) = k (1)
x →
In the above expression, k is the theoretical numerical limit
for the expression f ( x) (a mathematical function) as x (its
independent variable) tends to its value l. Values l and k can
be any two constants from zero to infinity. While f ( x) ap-
proaches the limit k in the mathematical sense (it is infinitely
close to the limit, but it is never at that value), x is not obli-
gated to reach its limit l. The fact is that in most of the physi-
cal cases, f ( x) moves towards its limit much more rapidly
than x moves toward l. Therefore, while f ( x) approaches k
as a limit, x appears only as a tendency moving toward the
limiting value l (as an example, see eq 5 below).
The differences between the accepted value and the ex-
perimental result can be examined using the concordance
criteria mentioned above and the concordances expressed as
general equations, which we will name as the concordance
equations. An analysis of these concordance equations starts
with the equation for the arithmetical difference:
lim f (x ) − kexp = k − kexp = 0cc (2)
x →
In the above equation, kexp is the experimental value for f ( x)
at x ⫽ lexp, and lexp is an experimental value of x at which it
is expected that the concordance equation result is close
• www.JCE.DivCHED.org
 In the Classroom

enough to zero to be acceptable for the experimenter. The Real gases obey this law at normal laboratory conditions quite
zero in eq 2, an absolute value, is not a real zero value; rather well. Therefore, in real gas systems the quotient PVnT, com-
it is an acceptably small value of the chosen concordance cri- puted with pressure values of about 1 atm and temperature
terion. This is the reason for the subscript cc. We will name values of about 298 K, for any given volume and number of
that symbol as the concordance criterion zero. Alternatively, if gas moles, differs from the R value to within a few percent
kexp ⫽ 0, the expression for the arithmetical quotient can be (see Table 1). In general, the ideality of the gas and its agree-
used: ment with the ideal gas law improve as the pressure goes down
and temperature goes up. The agreement should be absolute
f (x ) k in the limiting values of both pressure and temperature.
lim = = 1cc (3) Analogous to eq 1, eq 5 describes the limiting situations cor-
x → l kexp kexp
responding to an ideal gas:

Here, the symbol 1cc is similar to the symbol 0cc in eq 2. As PV

such, we will name it as the concordance criterion unity. The lim = R
P → 0 nT (5)
concordance equation for the deviation percent from the ac- T → ∞
cepted value, as derived from eq 2, is as follows: deviation%
⫽ (0cc
k) ⫻ 100. Equation 5 raises a fundamentally important point: the
mathematical notation used for a tendency demands that a pa-
Ideal-Gas Limiting Behavior rameter must move in the direction indicated until it reaches
Let us consider a common limiting case: the relationship the magnitude that makes possible the value of the limit. The
between the volume, pressure, and temperature of a gas when tendency must fit with an appropriate limit. Tendency values
it behaves as an ideal gas. By definition, ideal gases are those that lead to limits of no physical sense or that are mathemati-
that at any pressure and temperature obey the equation known cally contradictory must be ruled out even if they are math-
as the ideal gas law. This law is expressed as: ematically allowed. For example, one can obtain an absurd
result (undetermined value) ⫽ R (a fixed number) from eq 5
PV if the limiting values of the tendencies are taken exactly as
= R (4)
nT written. The only meaningful values for pressure and tem-

Table 1. Concordance Values for the Gas Constant for Helium and Water at a Fixed Temperature, by Pressurea

P, atm 0.1 0.2 0.3 0.4 0.5 1 2 5 10 50

He

R e xp 0.08206 0.08207 0.08208 0.08209 0.08209 0.08213 0.08221 0.08243 0.08281 0.08582

0 cc 0 0.00001 0.00002 0.00003 0.00003 0.00007 0.00015 0.00037 0.00075 0.00376

1 cc 1.000 1.000 1.000 0.9996 0.9996 0.9991 0.9981 0.9955 0.9909 0.9561

b
Deviation % 0 0.01 0.02 0.04 0.04 0.09 0.18 0.45 0.91 4.58

Degree of Excellent Very good Good Poor Bad

acceptabilityc

Qualitative Extremely low Very low Low Moderately Very high

values d low

H 2O

R e xp 0.08199 0.08193 0.08186 0.08180 0.08173 0.08140 0.08074 0.07868 0.07499 0.006095

Deviation %b 0.09 0.16 0.24 0.32 0.40 0.80 1.61 4.12 8.62 92.57

Degree of Good Poor Bad Bad Unacceptable

acceptabilityc

Qualitative Low Moderately High Very high Extremely high

values d low

aCalculated from eqs 6 and 7, where R ⫽ 0.082056 (atm L)/(mol K) and (PV/nT )
exp are the values named as Rexp in the table. Rexp values were
calculated at any given pressure with n ⫽ 1 mole, T ⫽ 298 K, and corresponding V values obtained from the van der Waals equation and data from
reference 5.
bDeviation % ⫽ (0 /R) ⫻ 100; a deviation value of 0.1% was considered acceptable: this was arbitrarily selected for the purposes of this article.
cc
cDegree of acceptability of results conveys how well the equation and the result correspond for the experimenter, ranging from unacceptable to excellent.
dQualitative pressure values range from low to extremely high.

www.JCE.DivCHED.org • Vol. 84 No. 5 May 2007 • Journal of Chemical Education 789

 In the Classroom

perature are those found at that point where pressure reaches Thus, T∞ and P0 are not infinite temperature and zero
a value small enough (P → 0) to make product PV decrease, pressure without physical meaning, nor are they necessarily
and simultaneously temperature reaches a value high enough an extremely high temperature (many millions of degrees)
(T → ∞) to make the product nT increase. The concurrent and an extremely low pressure (a few millionths of an atmo-
decrease of pressure and increase of temperature occur until sphere). Note also that the same temperature and pressure
the quotient of both products becomes equal to R. values can be considered high for one system and low for
Concordance eq 2 or 3 can be applied to eq 5. They another. Therefore, the limiting values of the tendencies are
are, respectively, real experimental values that define equations, to the extent
that equations define real chemical systems. Concordance val-
PV PV PV ues provide magnitudes for values of tendencies that are low
lim − = R − = 0cc or high and values for limits, as well as equations that are
P → 0 nT nT exp nT exp (6) useful, acceptable, good, or bad. In that regard, qualitative
T → ∞
values and acceptability degree scales are proposed as shown
in Tables 1 and 2.
PV For another application of eq 1, we now discuss the re-
lationship between the activity, a, and the concentration of a
nT R
lim = = 1 cc species in a solution as it becomes “infinitely dilute.” For a
P → 0 PV PV (7) solute i and a solvent j, that relationship is expressed in the
T → ∞
nT exp nT exp
mole fraction composition scale as:

These equations show that the pressure must be so low
(its value so small) and the temperature must be so high (its
value so high) that the value for the expression (PVnT)exp
becomes so close to the R value that the difference between
(PVnT)exp and R is nonsignificant to the experimenter.
Therefore, “low pressure” and “high temperature” must be
understood as pressures and temperatures fulfilling the above
conditions. Table 1 shows the results for two gases when eq
5 is analyzed with eqs 6 and 7 for pressure variations. Ob-
serve that at 298 K, pressures for He can be considered as
“zero” (P0) from 1 atm and lower, while pressures for H2O
can be considered “zero” (P0) from 0.1 atm and lower. The
same analysis made for temperature variation shows that at
1 atm pressure, temperatures for He can be considered as “in-
finite” (T∞) from 298 K and higher, while temperatures for
H2O can be considered as “infinite” (T∞) from 750 K and
higher.
lim (ai /xi) ⫽ lim γi ⫽ 1
and
lim (aj /xj) ⫽ lim γj ⫽ 1 as xj → 1
This is the infinitely dilute boundary condition for solute and
solvent in their standard states, respectively. The γ’s are the
activity coefficients. Let us take a brief look at the mercury–
thallium amalgam system. We will assume arbitrarily that an
acceptable concordance criterion for the γ values in that sys-
tem is a deviation less than 3%. According to reported values,
γHg ⫽ 0.986 and γTl ⫽ 1.80 at xHg ⫽ 0.95 and 20 °C (7).
This implies that deviation percents are 1.4% and 80% for
mercury and thallium, respectively. It is interesting to note
that this same system may be considered as dilute or very
dilute relative to the solvent behavior (mercury), while it may
simultaneously be considered as very or highly concentrated
relative to the solute behavior (thallium).

Table 2. Concordance Values for the Dissociation Constant of Dinitrophenol in Pure Watera

Ci,exp ⫻ 104, moles L᎑1 7.018 5.505 3.991 2.395 1.5364 0.9245 (……...)e

K(Ci,0) ⫻ 105 8.152 8.152 8.152 8.152 8.152 8.152 8.152

K exp ⫻ 1 0 5 8.449 8.435 8.377 8.325 8.310 8.289 (8.15…)e

0 cc ⫻ 1 0 5 0.297 0.283 0.225 0.173 0.158 0.137 (0.00…)e

1 cc 0.9648 0.9664 0.9731 0.9792 0.9810 0.9835 (1.00…)e

Deviation % b 3.66 3.47 2.76 2.12 1.94 1.68 (0.00 ...)e

Degree of acceptability c Acceptable Good Very good Excellent

Qualitative values d Moderately dilute Dilute Very dilute Highly dilute

aCalculated from eqs 16 and 17. Values for K(C ) and K

i,0 exp for any of the Ci,exp values shown in the table were obtained with data from reference 9;
Ci,exp ⫻ 104 are undissociated acid concentrations.
b
Deviation % ⫽ (0cc /Ci,0) ⫻ 100; a deviation value of 3% was considered acceptable: this was arbitrarily selected for the purposes of this article.
cDegree of acceptability of results conveys how well the equation and the result correspond for the experimenter, ranging from acceptable to excellent.

dQualitative concentration values range from moderately dilute to highly dilute.

e
All values in parenthesis are hypothetical limiting values.

790 Journal of Chemical Education • Vol. 84 No. 5 May 2007 • www.JCE.DivCHED.org


Values of Equational Limits and Tendencies
When the limit of an equation (a function) is a particular
expression (an equational limit), the explicit mathematical
relationship of the function, its limit, and the tendencies of
their respective independent variables can be expressed as:
lim f ( y ) = g (x l )
y →
x →
l scale and the exponents are the respective reaction stoichio-
In the above equation, g ( x l ) is the equational limit of
function f (y) when its variable y becomes equal to a new vari-
able x, as x tends to value l, namely, xl. The value l can be
any constant from zero to infinity. As in eq 1, while f (y) must
reach the limiting expression g( x l ), x is not obligated to reach
its limiting value l. As before—in most of the physical cases—
f (y) moves toward the limiting expression g ( x l ) much more
rapidly than x does to its limiting value l. Therefore, while
f (y) appears as an equational limit, x appears only as a ten-
dency. (As an example, see eq 14 below for the chemical equi-
librium constant.) Having to write both tendencies in eq 8
Ci →
0 aAa aBb CA CB (14)
is redundant because the tendency of x toward its limiting
j
constant
value l obligatorily implies the tendency of y towards the new
variable x. Therefore, this equation can be rewritten as fol-
lows:
lim f ( y ) = g ( x l )
x →
l
Normally, we work with the expression for g ( x l ) in the form
g ( x), where the implicit presence of tendencies and limits in
the results are not obvious. (See eq 13 below.)
The concordance or difference between the theoretical
prediction and the experimental result can be examined with
the following concordance equation:
(
lim f ( y ) − g x l exp
x →
l
) = g ( x l ) − g x l exp(
In the above equation, g(xl,exp) is the value for g ( x l ) at the
experimental value of xl ⫽ xl,exp. As before, xl,exp is an experi-
mental value of x at which the concordance equation should
show a value acceptable for the experimenter. Alternatively,
if g ( xl,exp) ⫽ 0, the following expression can be used:
0
f (y) g ( xl )
lim = = 1 cc
x →
l (
g x l exp ) (
g x l exp ) stant usually introduced in general chemistry courses and
Concentration-Based Equilibrium Constants
Let us consider the concentration-based expression for
the chemical equilibrium constant that is valid, as it is usu-
ally said, at “dilute” to “highly dilute” concentrations of the
chemical reaction participants. Thus, for the general chemi-
cal reaction equilibrium
aA + bB cC + dD
www.JCE.DivCHED.org
In the Classroom
the expression for the equilibrium constant is:
c d
CC CD
K (Ci ) = a b (13)
CA CB
In the above expression, Ci represents the concentration of
(8) each of the species in the reaction in a given concentration
metric coefficients.
In eq 13, the infinitely dilute solution boundary condi-
tion was taken for all the chemical reactants in its deduction.
This condition is not explicitly shown in the expression. We
say that the relationship between the equational limit and
the concentration limiting values is intrinsically contained
in the result. We can explicitly show this relationship as fol-
lows:
c d
a Cc aDd CC CD
lim = a b
ai →
∀ i ≠
C j →
The quotient in the brackets on the left side of eq 14 is
the expression for the equilibrium constant in terms of the
activities of the reaction species, which we will name as K(ai).
(9) In that equation, i is any of the solutes, j is the solvent if it
participates as reactant; the molar concentration scale has
been used. With the boundary condition of an infinitely di-
lute solution, the concentration of the solvent—as one of the
reaction species—normally does not explicitly appear on the
right side of the above expression, because the solvent con-
centration is almost a constant value and, as such, it is taken
as part of the equilibrium constant value. The same thing
happens with the solvent activity on the left side of that ex-
pression.1
) = 0cc (10)
Replacing the quotients in eq 14 for K(ai) and K(Ci),
but making explicit in the concentration equilibrium con-
stant the limiting values for the concentrations of the solutes
and omitting solvent terms as well, eq 14 can be rewritten in
the general form of eq 9 as:
lim K (ai ) = K (C i ,0 )
Ci →
(15)
Equation 13 is the expression for the equilibrium con-
(11)
simply indicated as K(Ci). The activity concept is needed to
work with the canonic expression given at the left side of eq
14, a concept that is not generally introduced in first-year
chemistry courses. Artificially, all the equilibria studied in
first-year courses involve equilibria and concentrations where
activities can be replaced by concentration values and accept-
able values for K are obtainable. It is experimentally found
that the more dilute the concentration of species in solution,
the more acceptable are the values for K. These particular
concentrations are normally referred to as “very dilute con-
(12) centrations”. For other situations, eq 13 is valid just as an
• Vol. 84 No. 5 May 2007 • Journal of Chemical Education 791
 In the Classroom
estimate, since it is only an approximation of the general ex-
pression.
In the above case, equations of the form 10 and 11 apply
to analyze the concordance criterion. Hence:
lim K (ai ) − K exp = K (C i ,0 ) − K exp = 0cc
Ci →
0
(16)
or
K ( ai ) K (C i ,0 )
lim = = 1 cc (17)
Ci →
0 K exp K exp or “concentrated”.
As shown in eqs 10 and 11, Kexp in the above equations
is the value for K(Ci,0) calculated with eq 13 and the equilib-
rium concentration values of each one of the chemical spe-
cies participating in the reaction: Ci,0 ⫽ Ci,exp. The Ci,exp terms
are the experimental values of the species concentrations at
which concordance equations are expected to show accept-
able concordance values. In eqs 15–17, K(Ci,0) is numerically
equal to K(ai) obtained at any concentration value because
the equilibrium constant value, as such, must be the same in
the whole concentration range of the reaction participants.
This value can be obtained by means of many experimental
procedures depending on the chemical nature of the system.
Once K(ai) has been determined, it can be used with either
eq 16 or 17 to determine when Kexp becomes acceptable.
Concentration values in these equations need to be small
enough (approaching zero) to make both values for K closely
equal, such that their differences cannot be experimentally
detectable or their differences are insignificant. Therefore, a
“dilute solution” must be understood as providing an acceptable
low concordance value, while a “non-dilute” or “concentrated
solution” must be understood as having the opposite meaning.
Depending on the nature and the concentration of the
participants, it is possible for a concentration value to be con-
sidered low (dilute) for one system and high (concentrated)
for another. For example, a concordance of 5–8% is observed
for the dissociation constant of 3-nitrobenzoic acid at a con-
centration range of 2 ⫻ 10᎑3 to 4 ⫻ 10᎑3 mol L᎑1 (8), while a
concordance value of 2% and 4% is observed for the disso-
ciation constant of dinitrophenol in the range of 1 ⫻ 10᎑4 to
7 ⫻ 10᎑4 mol L᎑1 (9). Both equilibria were in pure water at
25 ⬚C. Details for the latter system are given in Table 2.
Conclusions
While expressed in formal mathematical terms as limits
of tendencies, the limiting values of practical chemical vari-
ables are not abstract, undetermined values. Limiting values
are as understandable as concrete values: measurable, deter-
mined, and bound by experiment. These practical limits of
variables can be used to fully understand the limits of equa-
tions that define chemical phenomena.
A zero-value tendency (e.g., P → 0) must be understood
as the need of a parameter to diminish its magnitude so that
the expression it is involved in reaches its limiting form. In
such a regard, a zero-tendency value (P0) is understood as the
largest experimental value of a given parameter that produces
acceptable concordance criterion values for the experimental
result and the predicted result. Smaller experimental values
792 Journal of Chemical Education • Vol. 84 No. 5 May 2007
produce smaller concordance criterion values and smaller per-
cent deviations. An infinite-value tendency (e.g., T → ⬁) must
be understood as the need of a parameter to increase its mag-
nitude with the same purpose as above. Thus, an infinite-ten-
dency value (T⬁) is understood as the smallest experimental
value of a given variable that produces acceptable concordance
criterion values for the experimental result and the predicted
result. Larger experimental values produce smaller concor-
dance criterion values and smaller percent deviations. An un-
derstanding of these limits helps experimenters correctly
consider variables such as pressures and temperatures that are
“low” or “high” or solution concentrations that are “dilute”
The concordance criterion values between theoretical and
experimental results are determined from limiting values of
tendencies. The extent to which an equation acceptably de-
scribes a chemical system is determined from the limiting
values of practical chemical variables and the concordance
value defined by given experimenters. An understanding of the
role of these limits and their relationship to experimental val-
ues allow experimenters to label equations as applicable or
non-applicable. While sounding theoretical, an understanding
of tendencies, limiting values of tendencies, and the limits
of equations is absolutely practical.
Acknowledgments
The authors wish to thank Mickey Sarquis, Director of
the Center for Chemistry Education at Miami University
(OH, USA), and Susan Hershberger, Amy Hudepohl, and
Amy Stander, also with the Center for Chemistry Education,
for their helpful suggestions to this article. The authors also
wish to thank Ana Tejeda, from the Faculty of Humanities
at the Universidad Católica del Norte, for helpful assistance
in editing this article. Financial support from DGIP/UCN
is gratefully acknowledged.
Note
1. If the solvent is water, the value for Cj is 55.5 mol L᎑1 at
25 ⬚C.
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