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In the Classroom

edited by
Resources for Student Assessment John Alexander
University of Cincinnati
Cincinnati, OH 45221

The Right Shift? A Problem in Chemical Equilibrium

Joo C. M. Paiva*
Department of Chemistry, University of Porto, R. Campo Alegre 687, 4169-007 Porto, Portugal;

Victor M. S. Gil
Department of Chemistry, University of Coimbra, Portugal

Antnio Ferrer Correia

Department of Chemistry, University of Aveiro, Portugal

obtained from Kp,600 K /Kp,298 K together with the expression

The Problem
for Kp. Step 5 considers either the result Kc,600 K /Kc,298 K > 1 or
The understanding of chemical equilibrium is sometimes the fact that pBe,600 K /pBe,298 K < pB600 K /pB298 K to conclude that the
clouded by uncritical application of concepts and mechani- equilibrium shifts to the right on going from 298 K to 600 K.
zation (particularly in the case of numerical calculations) (1, 2). Finally, in step 6 such a conclusion conflicts with the generic
With this in mind, we devised the following problem appro- statement that equilibria shift to the left when the temperature
priate to a physical chemistry course or to an honors general is increased if the reaction is exothermic. This same step offers a
chemistry course. At this level, a surprising result is obtained, rationalization for such a deviation from the expected result
which can be explored to promote critical thinking and to (small absolute values for H ).
acknowledge the importance of reference states when Kc and It has been stressed (3) that if H is small, Kp and Kc can
Kp are being used. Here is the problem. vary in opposite ways with temperature (except if ng = 0).
Consider a generic chemical reaction A(s) + 2B(g) C(s) This stems from the use of two different reference states for
for which Kp = 1.0 at 298 K and Kp = 0.36 at 600 K. the equilibrium constants: 1 atm for Kp and 1 mol dm3 for Kc.
1. From the effect of temperature on the value of Kp do you Should the reference state for Kc be the same as for Kp (1.0 atm
expect the reaction to be exothermic or endothermic? is equivalent to 0.041 mol dm3 at 298 K and to 0.020 mol dm3
at 600 K), then Kc = Kp for any temperature. For example, in
2. Apply the vant Hoff equation, ln Kp = H/RT + S/R,
the expression for Kc, the value to be used instead of 0.041
to find that H = 5.0 kJ/mol (of A or C).
corresponding to the concentration of B at 298 K (pB = 1.0
3. Using Kc = Kp(RT )ng, show that Kc,600 K/Kc,298 K = 1.5 atm) would be 0.041 atm/0.041 atm = 1.0 (activity of B);
and compare with Kp,600 K/Kp,298 K = 0.36/1.0 = 0.36. hence Kc = 1.0. Similarly, for 600 K ( pB = 1.7 atm), instead
How can the former ratio be larger than 1 whereas the of 0.034 it would be 0.034 atm/0.020 atm = 1.7 (activity of
latter is smaller than 1? B); hence Kc = 0.35 (which is the same as Kp, considering the
4a. Taking account only the change of gas pressure with number of significant figures used). Otherwise, by referring
temperature, show that p B600 K /p B298 K = 2.0. H to a reference state of 1 atm, the way Kc varies with T is
4b. In reality, the equilibrium position will also shift. Show given by (see, e.g., ref 4 )
that p B e,600 K /p B e,298 K = 1.7. d(ln Kc)/dT = (H RTng)/RT 2
5. On the basis of 3 and 4, conclude that, on going from
to be compared with (vant Hoff equation)
298 K to 600 K at constant volume, the equilibrium
is shifted to the right. d(ln KP)/dT = H /RT 2
6. Comment on this conclusion, which seems strange The same discussion would apply should we use the SI
considering that the reaction is exothermic. Would you unit for pressure (bar instead of atm), in spite of small changes
expect the same result if Kp varied more drastically with in the equilibrium constants (5).
T (a larger magnitude of H)?
We thank the referees for their helpful suggestions.
Step 1 addresses a basic piece of knowledge. The answer
is confirmed quantitatively in 2 by making use of the vant Literature Cited
Hoff equation, which is given to show that no emphasis is
placed on memory. A similar approach is adopted in step 3 to 1. Gil, Victor M. S.; Paiva, J. C. Chem. Educator 1999, 4 (4),
calculate Kc from Kp. The comparison required in 3 can be 128130.
made at different levels: (i) the ratios are not the same, (ii) the 2. Huddle, Benjamin P. J. Chem. Educ. 1998, 75, 1175.
ratio Kc,600 K /Kc,298 K is larger than 1, whereas Kc,600 K /Kc,298 K 3. Allsop, E.; George, N. Educ. Chem. 1984, 3, 54.
is smaller than 1, and (iii) Kc increases with temperature whereas 4. Glasstone, S. Thermodynamics for Chemists; Van Nostrand:
Kp decreases. In step 4 the ratio pB600 K /pB298 K is calculated using New York, 1952; p 289.
the ideal gas equation and the ratio pBe,600 K /pBe,298 K is to be 5. Treptow, R. S. J. Chem. Educ. 1999, 76, 212. Vol. 79 No. 5 May 2002 Journal of Chemical Education 583