Beruflich Dokumente
Kultur Dokumente
edited by
John Alexander
University of Cincinnati
Cincinnati, OH 45221
The Problem
The understanding of chemical equilibrium is sometimes
clouded by uncritical application of concepts and mechanization (particularly in the case of numerical calculations) (1, 2).
With this in mind, we devised the following problem appropriate 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 vant 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 vant
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
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