Thermodynamics and Kinetics

Take Home Exam

1. Consider molecules that are confined to move in a plane (a two dimensional gas). Calculate the distribution of speeds
and determine the mean speed of the molecules at a temperature T.

2. A specially constructed velocity-selector accepts a beam of molecules from an oven at a temperature T but blocks the
passage of molecules with a speed greater than the mean. What is the mean speed of the emerging beam, relative to
the initial value, treated as a one-dimensional problem?

3. Derive the integrated form of a third-order rate law v = k[A]2[B] in which the stoichiometry is 2 A + B→P and the
reactants are initially present in (a) their stoichiometric proportions, (b) with B present initially in twice the amount.

4. Consider the following mechanism for renaturation of a double helix from its strands A and B:
A + B ↔ unstable helix (fast)
Unstable helix →stable double helix (slow)
Derive the rate equation for the formation of the double helix and express the rate constant of the renaturation
reaction in terms of the rate constants of the individual steps.

5. The half-life for the (first-order) radioactive decay of 14C is 5730 y (it emits β rays with an energy of 0.16 MeV). An
archaeological sample contained wood that had only 72 per cent of the 14C found in living trees. What is its age?

6. Calculate the fractions of molecules in a gas that have a speed in a range Δv at the speed nc* relative to those in the
same range at c* itself? This calculation can be used to estimate the fraction of very energetic molecules (which is
important for reactions). Evaluate the ratio for n = 3 and n = 4.

7. Two products are formed in reactions in which there is kinetic control of the ratio of products. The activation energy
for the reaction leading to Product 1 is greater than that leading to Product 2. Will the ratio of product concentrations
[P1]/[P2] increase or decrease if the temperature is raised?

8. A very expensive gas is sold by the molecule, and the price is proportional to the velocity of the individual molecule:
price in $ = 𝜗 <𝜗>. If I buy a bulb of these gaseous molecules, what is the average price per molecule, and does the
price depend on the temperature of the bulb?

9. In a group of molecules all traveling in the positive z direction, what is the probability that a molecule will be found
with a z-component speed between 400 and 401 m/s if m/(2kT) = 5.62x10-6 s2/m2? (Hint: You need to find and
normalize a one-dimensional distribution function first!)

10. What is the ratio of the probability of finding a molecule moving with the average speed to the probability of finding a
molecule moving with three times the average speed? How does this ratio depend on the temperature?

P.S. Questions are google proof. But there’s no harm in trying. Enjoy!

Bonus: Explain why you should pass the subject.