In the Classroom

Equilibria That Shift Left upon Addition of More Reactant W

Jeffrey E. Lacy
Department of Chemistry, Shippensburg University, Shippensburg, PA 17257; jelacy@wharf.ship.edu

Students of chemistry who have studied Le Châtelier’s
principle in any general chemistry textbook (1, 2) and most
physical chemistry textbooks (3, 4)1 are familiar with the re-
sult of adding more reactant to a reaction at equilibrium: the
position of equilibrium shifts so that more of the product is
formed. This result occurs for an isothermal system at con-
stant volume. However, by reading the same textbooks no
student will learn that a different result is possible if the iso-
thermal system is at constant pressure instead of constant
volume. For example, consider
N2(g) + 3H2(g) 2NH3(g) (1)
At a constant temperature and pressure, if the number of
moles of nitrogen is increased to the extent that it is greater
than one-half of the total number of moles of all species,
rather than forming more product the equilibrium shifts to-
ward the reactants and ammonia will decompose (5).
We propose presentations that will enable students to
perform a side-by-side comparison of these two conditions
and, thereby, gain a better understanding of reactions at equi-
librium. In addition, we have derived novel stoichiometric
criteria for identifying equilibria that shift left upon addi-
tion of more reactant.
General Chemistry
At this level, descriptions of the constant volume con-
dition are usually based on an algebraic analysis of the mag-
nitude of the reaction quotient QC relative to that of the
equilibrium constant KC for which both expressions are writ-
ten in terms of molar concentrations. Using eq 1 as an ex-
ample, the necessary expressions have the form
Q C or KC =
[NH3 ]2
(2)
[ N 2 ][H2 ]3
However, to analyze the system at constant pressure, we must
write these expressions in terms of mole fractions Xi and to-
tal pressure Pt such that KP = KX Pt∆ν, where ν is the stoichio-
metric coefficient. This is analogous to the expression KP =
KC(RT )∆ν, with which most students will already be famil-
iar.
Given the expression for the equilibrium constant at con-
stant pressure for eq 1
For constant total pressure, only KX will vary with added re-
actant. By substituting the explicit expressions for the mole
fraction of each species Xi, as well as the definition for the
total number of moles nt, we obtain
n NH3 2
nt (
n NH32 n N + n H + n NH
2 2 3
)2
KX = 3
=
n N2 n H2 nN2 nH23 (5)
nt nt
The number of moles of nitrogen appears in both the nu-
merator and denominator. Since the numerator is squared,
addition of N2 will cause it to increase faster than the de-
nominator so that at some point QX will become larger than
KX (see the discussion of eq 9 below to quantify this point.)
Thus, NH3 will need to decompose to return QX to equality
with KX. On the other hand, adding H2 does not cause de-
composition of the product: even though the numerator is
squared, the number of moles of H2 in the denominator is
cubed and QX will always decrease upon addition of H2.
Physical Chemistry
The reaction quotient QX could serve as the basis for
presentation of the constant pressure condition at this more
advanced level as well. By taking the partial derivative of eq
5 with respect to the number of moles of added reactant (6,
7), students can derive a formula for determining the rela-
tive number of moles of a reactant that would be needed to
shift the equilibrium toward the reactants. However, we failed
in our attempt to derive a general expression based on this
method.
To derive a general expression and to ground this con-
cept on a firm theoretical basis, the thermodynamic principle
of Gibbs energy must be employed. Such an approach can
be found as part of two extensive analyses of Le Châtelier’s
principle (5, 8). In the following, we use the approach out-
lined in ref 5 as the more direct and facile basis for simplify-
ing and extending the results. Given that the spontaneous
change is to reduce the chemical potential of the added reac-
tant µi, we express it in terms of partial pressure, pi,
pi
µ i = µ i° + RT ln (6)
pi°

PNH32 Since we must know how the chemical potential will change
KP = as the extent of reaction ξ changes, we derive (see the Supple-
PN PH 3 (3)
2 2
mental MaterialW)

we substitute Pi = Xi Pt and simplify to obtain ∂ pi Pt

= (nt νi − ni ∆ν ) (7)
X NH32
∂ξ T, P, µ j
n t2
KP = (4)
X N2 X H23 Pt2 where ∆ν = Σνi. For a spontaneous change, the numerator

1192 Journal of Chemical Education • Vol. 82 No. 8 August 2005 • www.JCE.DivCHED.org


of the slope on the left hand side of eq 7 will be negative. If
the equilibrium shifts toward reactants, then the denomina-
tor also will be negative; thus, overall the slope will be posi-
tive. The right hand side of eq 7 will be positive only when
n t νi > ni ∆ν (8)
Recall that νi is negative when it is the stoichiometric coeffi-
cient of a reactant, so for eq 8 to be true ∆ν must also be
negative. We proceed one step farther by rearranging to get
nt νi
ni > (9)
∆ν
We emphasize that this result was specifically derived for the
reaction to proceed right to left from products to reactants
in order to decrease the chemical potential of the added re-
actant, and so it applies only in that instance. If the desired
result is for the equilibrium to shift from left to right, then
the inequality in eq 8 must be reversed.
Applying eq 9 to eq 1 we obtain
nt
n N2 > (10)
2 1. Chang, R. Chemistry, 6th ed.; McGraw-Hill: New York, 1998.
that is, the position of equilibrium will shift to the left when
the added number of moles of nitrogen exceeds half of the
total number of moles. On the other hand, in order for added
hydrogen to shift the equilibrium to the left eq 9 yields
3 nt
n H2 > (11)
2 6. Levine, I. N. Physical Chemistry, 5th ed.; McGraw-Hill: New
which is clearly impossible so that adding hydrogen at a con-
stant pressure will always produce more ammonia. In sim-
www.JCE.DivCHED.org • Vol. 82 No. 8 August 2005
In the Classroom
plest terms, the following criteria must be met for the reac-
tion to shift left upon addition of reactant
νi < ∆ν and ∆ν < 0 (12)
Acknowledgments
We thank all reviewers, but most especially reviewer #3,
for the recommended revisions that improved the quality of
this article.
W
Supplemental Material
The derivation of eq 7 is available in this issue of JCE
Online.
Note
1. We list only a few of the textbooks that we reviewed.
Literature Cited
2. Petrucci, R. H.; Harwood, W. S.; Herring, F. G. General Chem-
istry; Prentice Hall: Upper Saddle River, NJ, 2002.
3. Barrow, G. M. Physical Chemistry, 6th ed.; McGraw-Hill: New
York, 1996.
4. Alberty, R. A.; Silbey, R. J. Physical Chemistry, 2nd ed.; John
Wiley & Sons, Inc.: New York, 1997.
5. de Heer, J. J. Chem. Educ. 1957, 34, 375–380.
York, 2002.
7. Katz, L. J. Chem. Educ. 1961, 38, 375–377.
8. Canagaratna, S. G. J. Chem. Educ. 2003, 80, 1211–1219.
• Journal of Chemical Education 1193