Sample Physical Science
Passage
Directions: Read the following passage and answer the
questions below.
Sample Passage
Several techniques have been developed to determine the order
of a reaction. The rate of a reaction cannot be predicted on the
basis of the overall equation, but it can be predicted on the
basis of the rate-determining step. For instance, the following
reaction can be broken down into three steps.
A + D —> F + G
| Step 1 |
A —> B + C |
(slow) |
| Step 2 |
B + D —> E + F |
(fast) |
| Step 3 |
E + C —> G |
(fast) |
Reaction 1
In this case, the first step in the reaction pathway is the
rate-determining step. Therefore, the overall rate of the
reaction mus equal the rate of the first step, k1[A]
where k is the rate constant. (Rate constants of the different
steps are denoted by kx, where x is the
step number.)
In some cases, it is desirable to measure the rate of a
reaction in relation to only one species. In a second-order
reaction, for instance, a large excess of one species is included
in the reaction vessel. Since a relatively small amount of this
large concentration is reacted, we assume that the concentration
essentially remains unchanged. Such a reaction is called a
pseudo first-order reaction. A new rate constant, k', is
established, equal to the product of the rate constant of the
original reaction, k, and the concentration of the species in
excess. This approach is often used to analyze enzyme
activity.
In some cases, the reaction rate may be dependent on the
concentration of a short-lived intermediate. This can happen if
the rate-determining step is not the first step. In this case,
the concentration of the intermediate must be derived from teh
equilibrium constant of the preceding step.
For redox reactions, the reaction rate at equilibrium can be
correlated with the voltage produced by two half-cells by means
of the Nernst equation. This equation states that any given
moment:
E = Eotot -
(RT/nF)IN([C]c[D]d/[A]a[B]b)
Equation 1
When
a A = b B —> c C + d D
Reaction 2
(Note: R = 8.314 J/K . mol;
F = 9.6485 X 104
Sample Questions
- 1. In a test of the rate of Step 3 of Reaction 1, a
solution is prepared containing a 0.1 M, concentration
of E and a 50 M concentration of C. The rate is
calculated after the reaction has gone 50% to completion. By
what percent will the calculated rate differ from the true rate
if we treat the reaction as pseudo first-order?
- (A) 0.02%
- (B) 0.05%
- (C) 0.1%
-
(D) 0.2%

-
2. Which of the following is true of a reaction at
equilibrium?
I. k1/k-1 = 1
II. E = Eo
III. In([C]c[D]d /
[A]a[B]b) =
nFEo/RT
- (A) I only
- (B) III only
- (C) I and II only
-
(D) I, II, and III

- 3. Catalysts are effective in increasing the rate of a
reaction because they:
- (A) increase the energy of the activated
complex.
- (B) increase the value of the equilibrium
constant.
- (C) decrease the number of collisions between reactant
molecules.
-
(D) lower the activation energy.
