Chemistry 1312
Exam 2, Spring, 2004

I.   Multiple Choice (90 points)  Select the best response for each of the following and record on the scantron.  Do not erase; erasures may result in a misgrading of your response.

1.       Identify the coordinates of a data plot for the 1st order kinetic reaction of “A” that yields a linear relationship.
a.     [A] vs. time                                                                          d.    ln [A] vs. time
b.     1/[A] vs. time                                                                        e.     ln 1/[A] vs. time
c.     ln [A] vs. 1/T

2.       The specific rate constant, k, is 2.3 x 10-4 L/mol•sec for a chemical reaction.  What is the overall order of the reaction?
a.     zero                                                                                        d.    third
b.     first                                                                                        e.     unknown, need more data
c.     second

3.       Consider the rate law, rate = k[A]2[B].  If the concentrations of both A and B are doubled, what happens the rate of the reaction?
a.     Increases by a factor of 2                                                 d.    Increases by a factor of 8
b.     Increases by a factor of 4                                                 e.     unknown, need more data
c.     Increases by a factor of 6

4.       Which of the following relationships is always correct for a spontaneous  reaction?
a.    
DSsys > 0 and DSsurr > 0                                                      d.    DSsys > 0 and DSsurr < 0
b.     DSsys < 0 and DSsurr > 0                                                      e.     DSsys = 0 and DSsurr = 0
c.     DSsys > 0

5.       The rate of a chemical reaction can be affected by which of the following conditions?
a.     changing the concentration of a reactant                  d.    changing the surface area of reactants
b.     adding a catalyst to the reaction system                    e.     all of the above affect reaction rates
c.     changing the temperature of the reaction system

6.       A catalyst
a.     increases the activation energy for a reaction
b.     alters the mechanism of a reaction
c.     increases the average kinetic energy of the reactants
d.    increases the surface area of the reactants
e.     increases the collision frequency of the reactants

7.       Consider the reaction, N2(g)  +  3 H2(g)  ®  2 NH3(g)  H° = –92.6 kJ, ∆S° = –199 J/K
At standard conditions this reaction
a.     is a spontaneous reaction at all temperatures
b.     can only be spontaneous at high temperatures
c.     can only be spontaneous at low temperatures
d.    can never be spontaneous at any temperatures
e.     can only be spontaneous at high pressures

8.       The standard free energy of formation, ∆G°f, for CS2(l), a common solvent, is +65.27 kJ/mol.  This means that
a.     CS2(l) has a negative entropy                                         d.    CS2(l) is thermodynamically stable
b.     CS2(l) has a positive entropy                                          e.     CS2(l) has a negative enthalpy of formation
c.     CS2(l) is thermodynamically unstable

9.       Which of the following statements best describes the second law of thermodynamics?
a.     the total entropy change, ∆S°total, always increases for all spontaneous reactions
b.     all exothermic reactions are spontaneous
c.     all reactions for which the entropy change of the system, ∆S°sys, increases are spontaneous
d.    the free energy change, ∆G°, always becomes more positive for all spontaneous reactions
e.     the standard entropy, S°, for all pure substances is zero

10.    The activation energy of a chemical reaction can be calculated from the slope of a linear data plot of
a.     ln [A] vs. time                                                                     d.    ln k vs. 1/T
b.     1/[A] vs. time                                                                        e.     ln rate vs. ln T
c.     [A] vs. 1/T

11.    A 32 mg sample of a thermally unstable compound decomposes via 1st order kinetics with a half-life of 30s.  How much of the sample will remain after 2 minutes?
a.     0.5 mg                                                                                   d.    4.0 mg
b.     1.0 mg                                                                                   e.     8.0 mg
c.     2.0 mg

12.    Which of the following quantities is least affected by temperature?
a.     free energy change,
DG°                                                   d.    rate constant, k
b.     kinetic energy of molecules                                            e.     the pressure of a gas
c.     activation energy, Ea

13.    Which of the following equations represents the greatest entropy change in the chemical reaction?
a.     PCl3(g)  +  Cl2(g) 
®  PCl5(g)                                            d.    2 N2(g)  +  O2(g) ®  2 N2O(g)
b.     CO2(g) ®  O2(g)  +  C(gr)                                                  e.     2 CO2(g) ®  2 CO(g)  +  O2(g)
c.     H2O(g) ®  H2O(l)

14.    The calculated value of DS° is +314.1 J/K for the exothermic reaction,
2 CH3OH(l)  +  3 O2(g) ®  2 CO2(g)  +  3 H2O(g)
Therefore this reaction is
a.     spontaneous only at high temperatures                    d.    nonspontaneous at all temperatures
b.     spontaneous only at low temperatures                      e.     spontaneous at all temperatures
c.     nonspontaneous only at high temperatures

15.    For the reaction, PCl5(g)  ®  PCl3(g)  +  Cl2(g), DH° = +92.5 kJ and DS° = 182 J/K.  Assuming DH° and DS° do not change with temperature, this reaction is spontaneous
a.     if T > 0.508 K                                                                       d.    T > 508 K
b.     if T > 1.97 K                                                                         e.     T > 197 K
c.     if T < 274 K


II.  Exercises (75 points).  The organization of all exercises must be shown clearly and legibly in order to receive any partial credit.  Answers without a logical problem setup will receive only 10% credit.

1.     (37 points)  Methanol, used int he production of plastics, is prepared industrially by the reaction:  CO(g)  +  2 H2(g®  CH3OH(g)

Given the following data:

 

CO(g)

H2(g)

CH3OH(g)

H°f(kJ/mol)

–110.5

0

–201.2

S°(J/K•mol)

197.6

130.6

238

        R = 8.314 J/mol•K

a.     (8 pts)  Calculate the enthalpy change for the reaction at 25°C.  What does your answer indicate about the reaction?

H°rxn = -90.7 kJ, an exothermic reaction

b.     (8 pts)  Calculate the entropy change for the reaction at 25°C.  What does your answer indicate about the reaction?

S°sys = -220.8 J/K, a decrease in disorder of the system

c.     (6 pts)  Calculate the free energy change for the reaction at 25°C.  What does your answer indicate about the reaction?

G°rxn = -24.9 kJ, reaction occurs spontaneously at 25°C

d.    (5 pts)  Calculate the entropy change for the surroundings at 25°C.

S°surr = + 304 J/K

e.     (10 pts)  Calculate the equilibrium constant for the reaction.

K = 2.32 x 104

2.     (19 points)  Consider the following initial rate data for the reaction NO(g)  +  Cl2(g)  ®  NOCl2(g):

[NO]o                     [Cl2]o              Initial rate (mol/L•s)
0.010                      0.05                0.050
0.010                      0.10                0.20
0.020                      0.15                0.90
0.030                      0.15                1.35
0.037                      0.14                ???

a.     (3 pts) The order of the reaction with respect to NO is __
1___.

b.     (3 pts) The order of the reaction with respect to Cl2 is __
2__.

c.     (3 pts) Write the rate law for the reaction.

rate = k[NO][Cl2]2


d.    (10 pts) What is the predicted reaction rate for the 5th reaction listed?

k = 2.0 x 103 L2/mol2 s

rate = 1.45 mol/L s

3.     (19 points)  The highly toxic pesticide parathion decomposes in the soil via 1st order kinetics with a rate constant of 0.0495 days-1.
a.     (3 pts)  What is the half-life for the decomposition of parathion?

14 days

b.     (8 pts)  How many days will lapse for a sample of parathion to be 88% decomposed?

42.8 days

c.     (8 pts)  How many milligrams of a 20.0 mg sample will remain after 30.0 days?

4.53 mg