CHEM 18 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. II. Radioactivity - chemical reactions versus nuclear reactions Radioactive Decay 1. Radioactive Series 2. Nuclear Reactions and Artificially Induced Radioactivity 3. Nuclear transmutation 4. Electron Capture 5. Transuranium Elements Kinetics of Radioactive Decay Mass Defect and Nuclear Binding Energy 1. Nuclear Stability Nuclear Fission and Nuclear Fusion

III. IV. V.

VI. VII. I.

Effects of Radiation on Matter - units used for measuring radiation Application of Radioisotopes 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. If the quantity in Column I is greater If the quantity in Column II is greater If the two quantities are equal If the relationship cannot be determined from the given information Column I Column II
P is a first order reaction

1.

t of reaction at 25 C 2. Ea of Rxn I 3. Rxn I: H = -25 kJ Rxn II: H = +25kJ

t of reaction at 50oC

Ea of Rxn II

The half life of the second order reaction A B is 10 sec. At constant temperature. Rate constant when [A]0 = 5M Rate constant when [A]0=10M Rate constant = 50s-1 for the reaction Ea when [X]0=10 atm 2C + Rate of disappearance of C B2 Z Rate of formation of Z

4.

Ea when [X]0 = 20 atm

5.

II.

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 What is/are the catalyst/s? I. SO2 II. H2SO4 III. HI IV. I2

I2 + H2 H2O + SO2 + O2

A) I, II

B) II, III, IV

C) I, IV

D) II, III

3. Which of the following energy profiles corresponds to the following mechanism? A + B AB (slow) AB + C ABC (fast)

I. E E

II.

Progress of reaction

Progress of Reaction

III. E

IV. E

Progress of reaction A) I B) III C) II, IV

Progress of Reaction 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

6. Why does rate increase when the reaction is heated? I. The activation energy is lowered when the temperature is increased. II. The frequency of collision 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, 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

10. A first order reaction: AP, has a half-life of 100 s. Which of the following is TRUE for any quantity of substance involved in the reaction? A) The reaction goes to completion of 200 s. B) The quantity of A remaining after 200 s is half of what remains after 100 s C) The same quantity of A is consumed for every 100 s for the reaction. D) 100 elapses before reaction begins E) None of the above. 11. It is found that the decomposition reaction: 2 HI H2 + I2, at 508 K has a half-life of 135 min when the initial pressure of HI is 0.1 atm and 27 min when the pressure is 0.5atm. What is the order of the reaction? A) zero B) first C) second D) third E) insufficient data 12. Identify the process described by the reaction 83 214 Bi 84 214 Po + -10e A) alpha decay B) beta decay C) gamma decay D) position decay E) fission 13. This reaction describes electron capture by tungsten 181. A) 74 181W + -1 0e 73 181 Ta B) 74 181W + +1 0 e 75 181Re 181 181 0 C) 74 W 73 Ta + 1 e D) 74 181 W 75 181 Re + -1 0e 14. Which nuclear reaction will produce 1838 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 16. Identify the particle emitted in the given decay process. 16.1 sodium-24 decays to magnesium-24 A) beta particle B) positron C) alpha 16.2 mercury-188 decays to gold-188 A) beta particle B) positron 5.3. radon-222 decays to polonium-218 A) beta particle B) positron C) alpha C) alpha

D) neutron D) neutron D) neutron D) neutron

5.4. thorium-230 decays to a radium isotope A) beta particle B) positron C) alpha 17. Supply the missing particle. 17.1. 98 252 Cf + 210 B 3 01 n + _________ A) 103 260Li B) 100 259Fm 17.2. 17.3 17.4.
1

C) 100 260Fm C) 0 1 N C)
1

D) 103 259 Lr D) 1 0e D) 1 0e D) 27 58Co

H + 2 3He 2 4He + ________ A) 1 1H B) 2 4He

122 54 122

55

I A) 1 1H
26 59

Xe + _________ B) 2 4He

Fe -1 0e + _________ A) 26 60Fe B) 27 59Co

C) 25 59Mn

III. Solve the following problems. 1. The rate of the reaction: D F, is 0.030 M min-1 when the concentration of D is 0.150M. 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 25oC for the reaction: 2 A + B + 2C 3D. Experiment 1 2 3 4 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 Initial Rate (M min-1) 4.0 x 10-4 1.2 x 10-3 4.0 x 10-4 3.6 x 10-3

A) What is the rate equation?

B) What is the value of the rate constant?

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

Determine the activation energy graphically. 8. Rearrange and label the following reaction steps in the order of chain-initiation, and chain-propagation steps: ClO + Cl + O2 CF2Cl2 + uv CF2Cl + Cl Cl + O3 ClO + O2 Suggest a possible chain-termination step. What is the over-all reaction? 9. At temperature below 5000C, the rate dimerization of: C2H4 C4H8 follows second order kinetics. At 140oC, the rate constant for this reaction is 3.42 x 10-3 M-1s-1. Suppose we start with 0.20 M of C2H4, what fraction of the original concentration would remain after one hour? 10. It takes 165 min for a 1.000-g sample of 39Cl to decay to 0.125g. What is the half-life of 39Cl? 11. A 65-kg person is accidentally exposed for 95 s to a 28-mCi source of beta radiation coming from a sample of 90SR. 11.1. What is the activity of the radiation source in disintegration per second (dps)? 11.2. What is the activity of the radiation source in becquerels? 11.3 Each beta particle has an energy of 8.75x10-14 J, and 50% 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 sieverts? END