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PROBLEM SET 1
CHEMICAL KINETICS
I. Reaction Rates
1. Meaning of reaction rates
2. Factors affecting rates of reaction
2.1. Nature of reactants
2.2. Concentration of reactants
2.2.1. Rate equation or rate law
2.2.2. Law of Mass Action (Equilibrium Constant)
2.2.3. Rate constant
2.2.4. Order of reaction
2.2.5. Half-life of a reaction
2.3. Temperature
2.3.1 Arrhenius Equation
2.3.2 Energy of activation
2.4. Catalyst
2.4.1. Homogeneous catalysis
2.4.2. Heterogeneous catalysis
3. Theories on reaction rates
3.1. Collision Theory
3.1.1 Activation energy
3.1.2. Orientation (Steric) Factor
3.1.3. Frequency of collision
3.2. Transition State Theory
II. Reaction Mechanism
1. Stepwise reactions
- Elementary step and rate-determining step
2. Chain reactions
- chain-initiation, propagation, termination steps
NUCLEAR CHEMISTRY
I.
Radioactivity
- chemical reactions versus nuclear reactions
II.
Radioactive Decay
1. Radioactive Series
2. Nuclear Reactions and Artificially Induced Radioactivity
3. Nuclear transmutation
4. Electron Capture
5. Transuranium Elements
III.
IV.
V.
VI.
VII.
Application of Radioisotopes
I.
Each of the following numbers consists of the following quantities, one in column I and another in
column II. You are to compare the two quantities and choose
A.
B.
C.
D.
1.
Column II
t of reaction at 25 C
2.
t of reaction at 50oC
Rxn I: H = -25 kJ
Rxn II: H = +25kJ
Ea of Rxn I
Ea of Rxn II
3.
4.
2C +
Rate of disappearance of C
Rate of formation of Z
5.
II.
B2
Each of the question or incomplete statements below is followed by suggested answers. Select
the answer which is best in each case.
1. The half-life of a first order reaction is 5 sec. How long will it take to reduce the reactant to of its
original value?
A) 5 sec
B) 10 sec
C) 15 sec
D) 20 sec
E) 25 sec
2. The following sequence of reaction has been proposed for the catalyzed production of H2O:
2 H2O + SO2 + I2 H2SO4 + 2 HI
2 HI
H2SO4
I2 + H2
H2O + SO2 + O2
II. H2SO4
III. HI
IV. I2
A) I, II
B) II, III, IV
C) I, IV
D) II, III
I.
II.
Progress of reaction
Progress of Reaction
III.
IV.
Progress of reaction
A) I
B) III
Progress of Reaction
C) II, IV
D) II
E) I, II
4. Which of the following causes a candle wax to burn faster in an atmosphere of O2 than air?
I.
An increase in the concentration of the wax
II.
An increase in the concentration of O2
III.
An increase in the surface area of the wax
IV.
Addition of a catalyst
A) III
B) II, IV
C) I, II
D) II
E) I, II, III, IV
5. In the reaction: A + 2 B P, it is found that doubling the concentration of both A and B increases the
rate by four times. What is the possible order of the reaction?
I.
first order in A, first order in B
II.
second order in A, zero order in B
III.
zero order in A, second order in B
IV.
first order in A, second order in B
V.
second order in A, first order in B
A) I, II, IV
B) I, II, III
C) I, II
D) III, IV
E) II, III, V
B) I, III, IV
C) II, III
D) II, IV
E) I, IV
7. Which of the following equations is applicable for the net reaction: A + B 2 C, which proceeds by a
single step, bimolecular mechanism?
A) half-life = 0.693/k
B) rate of disappearance of A = k [A][B]
C) rate of appearance of C = rate of disappearance of A
D) log [A] = (-k/2.303) t + log [A]0
E) all of the above
8. A and B, both of which are gases, were mixed in a rigid container. No reaction was observed. What
could possibly account for the observation?
I.
The energy of all reacting molecules is far below the energy barrier.
II.
The reacting molecules are not properly oriented.
III.
No catalyst was added
IV.
Not enough amounts of A and B were added
A) I, IV
B) I, II
C) III, IV
D) I, II, III
E) I, II, III, IV
9. Which of the following statements is CORRECT about the second order reaction:
2 A B + C?
I.
The rate of the reaction decreases as more B and C are formed.
II.
If the half-life of the reaction is 10 min, then the concentration of A will be
reduced to of its original value after 20 min.
III.
A plot of [A] versus time yields a straight line.
IV.
The rate of formation of C is one-half the rate of disappearance of A.
V.
The rate of consumption of A quadruples when [A] is doubled.
A) I, II, III
B) I, IV
C) I, IV, V
D) II, III
E) III, IV, V
D) neutron
C) alpha
D) neutron
C) alpha
D) neutron
D) neutron
D) 103 259 Lr
C) 0 1 N
D) 1 0e
17.2.
17.3
55
17.4.
C) 100 260Fm
122
I
A) 1 1H
54
122
Xe + _________
B) 2 4He
Fe -1 0e + _________
A) 26 60Fe
B) 27 59Co
26
C)
D) 1 0e
59
C) 25 59Mn
D) 27 58Co
Initial [A], M
0.20
0.20
0.20
0.60
Initial [B],M
0.10
0.30
0.10
0.30
Initial [C],M
0.10
0.20
0.30
0.40
3. Many biological reactions are acid-catalyzed. A typical mechanism consistent with the experimental
rate equation
Rate = k [X] [HA]1/2
in which HA is the acid and X is the reactant is given as follows:
HA H+ + A (fast)
X + H+ XH+
(fast)
XH+ P
(slow)
HA is the only source of H+ and A-.
A) Show that the mechanism is consistent with the rate law using:
a) Equilibrium approach; b) steady-state principle
B) Sketch the reaction profile
4. For the first order reaction: A P, H = -20 kJ. If the activation energy of the reaction: P A, is 60
kJ and the half-life of the reaction: A P, at 25oC is 4.25 min, what is the half-life of the reaction:
A P, at 50oC?
5. The half-life of the first order gas-phase reaction: A 2B, is 35 min. Enough A is placed in a
container so that its pressure is 725 mm Hg. What is the total pressure after 140 min?
6. Propose a plausible mechanism consistent with the observed rate law,
Rate = [NO2Cl] for the reaction:
2NO2Cl 2 NO2 + Cl2
7. The rate constant at several temperatures have been reported for the reaction of acetamide with
nitrous acid in aqueous solution:
k (L mol- s-)
t (oC)
0.152
25.0
0.182
27.5
0.233
30.0
0.263
32.0
0.299
34.0