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# I.

Reaction Rates
1. Meaning of reaction rate
PROBLEM SET 1
CI-I Efv'IJCAL KINETICS
2. Factors affecting rates of reaction
2.1. Nature of reactants
2.2. Concentration of reactants
2.2.1. Rate equation or rate liJw
2.2.2. Law of Mass Action
2.2.3. Rate constant
2.2.4. Order of reaction
2.25. Half- life of a react ion
2.3. Temperature
2.3.1. Arrhenius Equation
2.3. 2. Energy of acti vation
2. 4. Catalyst
2.4.1. Homogeneous catal ysis
2.4.2. Heterogeneous catalysis
3. Theories on reaction rates
3 .1. Collision Theory
3 .1.1. Activation energy
3.1.2. Steric factor
3.1.3. Frequency of collision
3.2. Transition State Theory
I. 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. Nudear Transmutation
4. Electron Capture
5. Transuran.ium Elements
IlL Kinetics of Radioactive Decay
IV. Mass Defect and Nuclear Binding Energy
1. Nucli:!ar Stability
V. Nucl ear Fission and Nuclear Fusion
\II. Effect of Radiation 0! 1 r"l atter
- Units used for measuring radiation
VII. Applications of Radioisotopes
I. Each of t he following numbers consists of the following quantities, one in column 1 and
another in column II. You are to compare the two quantities and choose
A if the quantity in Column I is greater
B if the quantity in Column II is greater
C if the two quantities are equal
D if the relationship cannot be determined from the given information
Column I Column II
1. R ----? P is a first order reaction
2.
.,
.J ,
4.
t::2 of reaction at t 1
12
of reaction at SO"C
Rxn I: nH = - 25 kJ
R.xn II: ...lH = + 25 kJ
Ea of Rxn I
The of the second order reaction
A-----+ B is 10 sec.
At constant temperature.
Rate constant when ;;;:: 5 M Rete eo.nstant when [A]c = 10 M
Rate const ant ;;;:: 50 s-
1
for the reaction
Ea when [X]o = 10 at m Ea when [X]o = 20 at; n
5. 2C + B2 Z:
Rate of disappearance of C Rate of formation of Z
II. Each of the questions 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
1
A 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 H20:
2 H20 + SOz + I2 ---+ + 2 HI
2 HI ----? h + Hz
----? HzO + so2 + 1/2 02
What is/are the catalyst/s?
I. S02 II. H2S04 III. HI
A) I; II B) II, III, N C) I, N
3. Which-of the following energy profiles corresponds to the following mechanism?
A + B ----? AB (slow)
AB + C .:=:=> ABC (fast )
I. II.
'

I
I
E
I
E
;v
I , ___

Progress of reaction Progress of reaction
II. IV.
'-/\
/\ (
) j \_
I '---- - --
__./
Progress of reaction Progress of reaction
A) I B) Ill C) II, IV D) II E) I, II
4. Which of the following causes a candle wax to burn faster in an atmosphere of 02 them in alr?
I. An increase in the concentration of the wax
II. An increase in the concentration of 02
III. An increase in the surface area of the
IV. Addition of a catalyst
III B) II, IV C) I, II D) II E) I, II, III, IV
5. In thA reaction: A + 2 B P, it is found that doubling the concentration of both A and 8
increases the rate by four times. What is the possible order.of the reaction?
I. first order in A, first order in B rv. first order in A, second order i1 B

II. second order in A, zero order in 8 V. second order in A, first order in 8
Ill. zero order In A, second order in B
A) I, II, V B) I, II, III C) I, II D) III, IV E) II, Ill, V
6. Why does rate increase when the reaction is heated?
I. The activation energy Is lowered when the temperature Is increased.
II. The f requency of collisions among the reacting molecules increases.
III. There Is an increase in the number of molecules with sufficient energy to cross the
barrier.
A) I, II, III B) I, Ill, 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) of disappearance of A = k [A][B]
I) rate of appearance of C = rate of disappearance of A
D) log [A] = ( - k I 2.303) t + log [A]o
E) all of the above
8. A and B, both of which are gases, were mixed in a rigid container. No reaction w..:1s ouserved.
What cuuld possibly account for the observation?
I. The energy of all reacting molecules is far below the energy barri e1.
II. The reacting molecules are are not properly oriented.
III. No was added.
IV. Not enough amounts of A and B were added.
A) I, IV B) I, II C) III, N D) I, II, III E) I, II, III, IV
9. Which of the following statements is CORRECT about the second order--reaction: 2A -7 B + C 7
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 red,1ced
to V4 of its original value after 20 min.
A plot of [A] versus time yields a straight line. Ill.
N.
v.
The rate of formation of C is one-half the rate of disappearance of A.
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
10. A first order reaction: A-t P, has a ha!f- life of 100 s. Which of the following is TRUE for
any quantity of substc:nce involved in the reaction?
A) The reaction goes completion in 200 s.
6) The quantity of A remaining after 200 sis half of what re1r2:ns 2fter 100 s
C) The same 'of A is consumed for every 100 s for th: reaction.
L) 100 s elapses before reaction begins.
E) of the above.
11. It is found that the d'2composition reaction: 2 HI --r H
2
+ h, at 508 K has a
of 135 min when the initial pressure of HI is 0.1 atm and 27 min when the pressure is 0.5 atm.
What is the order of the reaction?
A) zero B) first C) second D) third
I:) insufficient data
12. Identify the process described by the reaction: alHBi ---+

+ _
1
e
A) alpha decay B) beta decay C) gamma decay
D) positron decay E) fission
13. This reaction describes electron capture by tungsten-181.
A) 74
181
W + -1e -t n
181
Ta B) 11
181
W + 1e ---t 1s
181
Re
C) 74
181
W -t n
181
Ta + -1e D) 74
181
W 1s
181
Re + +J
0
e
14. Which nudear reaction will produce IB
38
Ar?
A) potassium-38 decay by proton emission
B) potassium-38 decay by positron emission
C) positron capture by potassium-38
D) neutron capture by potassium-38
15. What type of emission will produce U-238 from Pu-242?
A) alpha emission B) beta emission
C) positron emission D) proton emission
.L6; Identify the particle emitted in the given decay process.
16.1. sodium-24 decays to magnesium-24
A) beta particle B) positron C) alpha D) neutrcn
16.2. mercury-188 decays to gold-188
A) beta particle B) positron C) alpha D) neutron
5.3. radon-222 decays to polonium-218
A) beta particle B) positron C:) alpha D) neu'""on
5.4 thorium-230 decays to a radium isotope
A) beta particle B) positron C) ulpha D) neutron
17. Suoply the missing particle.
1.7.1. 9s
252
Cf + s
1
ct3 ----+ 3 o
1
n + _
A) JOJ
260
lr
B)
loo2S9Fm
17.2. 1
2
H + 2
3
He ----+
2
4
He + _
A) 1
1
H B) 2
4
He
1.7.3 sgl2'J ----+ s4
122
Xe +
A) 1
1
H B) 2 ~ H e C) o
1
n
17.4 2&
59
fe ----+ -1e +
A) 2.&
60
Fe B) n
59
Co
IV. Solve the following problems.
1. The rate of the reaction: D ---+ F, is 0.030 M min-1 when the concentration of D .is 0.150 M.
What are the rate constant and half-life if the reaction is: (A) zero order; (B) first order; (C)
second order; (D) third order.
2. The following data obtained at 25C for the reaction: 2 A + B + 2 C ---t 3D.
Experiment Initial [A], M Initial [B], M Initial [C], M Initial Rate (M min:-
1
)
1 0.20 0.10 0.10 4.0 X 10_..
2 0.20 0.30 0.20 1.2 X 10-
3
3 0.20 0.10 0'.'30 4.0 X 10-"
4 0.60 0.30 0.40 3.6 X 10-
3
A) What is the rate equation? B) What is the value of tbe rate constant?
J . Many biological reactions are acid-catalyzed. A typical mechanism consistent with the
experimental rate equation
Rate = k [X] [HA]11
2
In which HA is the acid and X is the reactant is given as follows:
HA < = = ~ W + A- (fast)
X + W === XW (fast)
XW ---. P (slow)
HA is the only source of W and A-.
A) Show that the mechanism is consistent with t he rate law using: a) Equilibrium approach;
b) steady-state principle.
B) Sketch the reaction profile.
4. For the first order reaction: A ----+ P, LlH = - 20 kJ . If the activation energy of the rear:t"io11: P
---+ A, is 60 kJ and the half-life of the reaction: A ---+ P, at 25C is 4.25 min, what is the
half-life of the reaction: A---+ P, at 50C?
t;; ll1e half-life of the first order gas-phase eaction: A ----+ 2 B, 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?
'- Propose a plausible mechanism consistent ,;ith the observed rate lav.,r,
Rate = [N02CI] for the reaction: 2 NO,,Cl --t 2 N02 + Cb
7. The rate constant at several have been reported for the reaction of acPtamide
with nitrous acid in aqueous solution:
k (L mol- s-) 0.152 0.182 0.233 0.263 0.299
t ec) 25.0 27.5 30.0 32.0 34.0
Determine the activatlon energy graphic:; .-'
8. Rearrange and label he following steps in the ordEr of chain-initiation, nr.r-1 r.hr.in-
steps:

CF202 + u: CF2CI + Cl
Cl + 0 :: CIO + 02
Suggest a possible chain-termination stt:p. What is the over-all reaction?
9. At temperatures below SOOOC, the rate. dimerization of:

follows second
order kinetics. At 140oC, the rate constant for this reaction is 3.42 x 10-
3
M-
1
s-
1
Suppose we
start with 0.20 M of what fraction of the original concentration would remain after one
hour?
lO.It takes 165 min for a 1.000-g sample of
39
CI to decay to 0.125 g. What is the half-life of
39
CI?
11. A 65-kg person is acddentally exposed for 95 s to a 28-mO source of beta radiation coming
from a sample of
90
Sr.
11.1. What is the activity of the radiation source in disintegrations per second (dps)?
11.2. What is the activity of the radiation source in becquerels?
11.3. Each beta particle has an energy of 8.75 x 10-
14
J, and 5.0% of the radiation is
absorbed by the person. Assuming that the absorbed radiation is spread over the
person's entire body, calculate the absorbed dose in rads and in grays.
11.4. If RBE of the beta particles is 1.0, what is the effective dose in mrem and in siPVE>rts?