In the Classroom
edited by
Resources for Student Assessment
The Right Shift? A Problem in Chemical Equilibrium
João C. M. Paiva*
Department of Chemistry, University of Porto, R. Campo Alegre 687, 4169-007 Porto, Portugal; jcpaiva@netcabo.pt
Victor M. S. Gil
Department of Chemistry, University of Coimbra, Portugal
António Ferrer Correia
Department of Chemistry, University of Aveiro, Portugal
The Problem
The understanding of chemical equilibrium is sometimes
clouded by uncritical application of concepts and mechani-
zation (particularly in the case of numerical calculations) (1, 2).
With this in mind, we devised the following problem appro-
priate to a physical chemistry course or to an honors general
chemistry course. At this level, a surprising result is obtained,
which can be explored to promote critical thinking and to
acknowledge the importance of reference states when Kc and
Kp are being used. Here is the problem.
Consider a generic chemical reaction A(s) + 2B(g) C(s)
for which Kp = 1.0 at 298 K and Kp = 0.36 at 600 K.
1. From the effect of temperature on the value of Kp do you
expect the reaction to be exothermic or endothermic?
2. Apply the van’t Hoff equation, ln Kp = ᎑∆H°/RT + ∆S°/R,
to find that ∆H° = ᎑5.0 kJ/mol (of A or C).
3. Using Kc = Kp(RT )᎑∆ng, show that Kc,600 K/Kc,298 K = 1.5
and compare with Kp,600 K/Kp,298 K = 0.36/1.0 = 0.36.
How can the former ratio be larger than 1 whereas the
latter is smaller than 1?
4a. Taking account only the change of gas pressure with
temperature, show that p B600 K /p B298 K = 2.0.
4b. In reality, the equilibrium position will also shift. Show
that p B e,600 K /p B e,298 K = 1.7.
5. On the basis of 3 and 4, conclude that, on going from
298 K to 600 K at constant volume, the equilibrium
is shifted to the right.
6. Comment on this conclusion, which seems strange
considering that the reaction is exothermic. Would you
expect the same result if Kp varied more drastically with
T (a larger magnitude of ∆H°)?
Discussion
Step 1 addresses a basic piece of knowledge. The answer
is confirmed quantitatively in 2 by making use of the van’t
Hoff equation, which is given to show that no emphasis is
placed on memory. A similar approach is adopted in step 3 to
calculate Kc from Kp. The comparison required in 3 can be
made at different levels: (i) the ratios are not the same, (ii) the
ratio Kc,600 K /Kc,298 K is larger than 1, whereas Kc,600 K /Kc,298 K
is smaller than 1, and (iii) Kc increases with temperature whereas
Kp decreases. In step 4 the ratio pB600 K /pB298 K is calculated using
the ideal gas equation and the ratio pBe,600 K /pBe,298 K is to be
JChemEd.chem.wisc.edu • Vol. 79 No. 5 May 2002 • Journal of Chemical Education
John Alexander
University of Cincinnati
Cincinnati, OH 45221
obtained from Kp,600 K /Kp,298 K together with the expression
for Kp. Step 5 considers either the result Kc,600 K /Kc,298 K > 1 or
the fact that pBe,600 K /pBe,298 K < pB600 K /pB298 K to conclude that the
equilibrium shifts to the right on going from 298 K to 600 K.
Finally, in step 6 such a conclusion conflicts with the generic
statement that equilibria shift to the left when the temperature
is increased if the reaction is exothermic. This same step offers a
rationalization for such a deviation from the expected result
(small absolute values for ∆H °).
It has been stressed (3) that if ∆H ° is small, Kp and Kc can
vary in opposite ways with temperature (except if ∆ng = 0).
This stems from the use of two different reference states for
the equilibrium constants: 1 atm for Kp and 1 mol dm᎑3 for Kc.
Should the reference state for Kc be the same as for Kp (1.0 atm
is equivalent to 0.041 mol dm᎑3 at 298 K and to 0.020 mol dm᎑3
at 600 K), then Kc = Kp for any temperature. For example, in
the expression for Kc, the value to be used instead of 0.041
corresponding to the concentration of B at 298 K (pB = 1.0
atm) would be 0.041 atm/0.041 atm = 1.0 (activity of B);
hence Kc = 1.0. Similarly, for 600 K ( pB = 1.7 atm), instead
of 0.034 it would be 0.034 atm/0.020 atm = 1.7 (activity of
B); hence Kc = 0.35 (which is the same as Kp, considering the
number of significant figures used). Otherwise, by referring
∆H ° to a reference state of 1 atm, the way Kc varies with T is
given by (see, e.g., ref 4 )
d(ln Kc)/dT = (∆H ° – RT∆ng)/RT 2
to be compared with (van’t Hoff equation)
d(ln KP)/dT = ∆H °/RT 2
The same discussion would apply should we use the SI
unit for pressure (bar instead of atm), in spite of small changes
in the equilibrium constants (5).
Acnowledgments
We thank the referees for their helpful suggestions.
Literature Cited
1. Gil, Victor M. S.; Paiva, J. C. Chem. Educator 1999, 4 (4),
128–130.
2. Huddle, Benjamin P. J. Chem. Educ. 1998, 75, 1175.
3. Allsop, E.; George, N. Educ. Chem. 1984, 3, 54.
4. Glasstone, S. Thermodynamics for Chemists; Van Nostrand:
New York, 1952; p 289.
5. Treptow, R. S. J. Chem. Educ. 1999, 76, 212.
583