The suggested timefor this section is 1.5 hours.

Note: a table of selectedphysical constants etc. are given in Appendix 1, and standard reduction potentials are given in Appendix 2 and the Periodic Table in Appendix 3.

Question A1.

Following consumption of excessive alcohol, the elimination of alcohol from the body follows zero order kinetics.  This means the rate is:

A.     Directly proportional to the concentration so doubling the concentration increases the rate by a factor of 2.

B.     Independent of concentration. Doubling the concentration has no effect on rate.

C.     The square of the concentration. Doubling the concentration increases the rate by a factor of 4.

D.     Directly proportional to the concentration so doubling the concentration increases the rate by a factor of 3. (2 marks)

The following information is required to answer questions A1 – A2

For the reaction:

2ClO2 + 2OH– ® ClO3– + ClO2– + H2O

the data concerning the reaction rate were obtained

Question A2.

What is the rate law?

A. k[ClO2]2  [OH–]2

B. k[ClO2][OH–]2

C. k[ClO2] [OH–]

D. k[ClO2]2 [OH–] (2 marks)

Question A3.

What is the value of the rate constant k?

A.     2.3 x 102 M–2s– 1

B.     3.2 x 102 M–3s– 1

C.     -3.2 x 102 M–3s– 1

D.     2.3 x 102 M– 1s– 1 (2 marks)

Question A4.

The following concentration time data were determined for the gas phase decomposition of a certain compound, X.

The rate constant for the decomposition reaction will be closest to?

A.     3.47 x 10-2 s- 1

B.      1.51 x 10-2 s- 1

C.     28.9 s- 1

D.     3.47 x 10-2 M- 1 s- 1

E.      3.3 s- 1 (2 marks)

Question A5.

Which one of the following equations below describes the temperature dependence of a rate constant, k?  T is the temperature in Kelvin; Ea is a constant; R is the Gas Constant.

A. k =  ln(A) + ln '(

B. k =  ln(A) + ln '(

C. k = Ae%&

D. k = Ae%& (2 marks)

Question A6.

Which one of the following statements about chemical kinetics is INCORRECT?

A.     At equilibrium, the rate constants of the forward and back reactions are equal.

B.     At equilibrium, the rate of a forward reaction equals the rate of the back reaction.

C.     Under “steady-state” conditions, the concentrations of each intermediate component in the system are constant.

D.     Phenomena other than temperature also affect the rate constant of a reaction. (2 marks)

Question A7.

Which one of the following compounds I – M, would exhibit the IR spectrum shown below?

O

I

OH

K

L

M

A.     Compound I

B.     Compound K

C.     Compound L

D.     Compound M

E.     None of these (2 marks)

Question A8.

Of the following isomeric dichloropropanes N – R, which isomer would give the following NMR spectra?

1H NMR: three signals

13C NMR: three signals

Cl      Cl

N

Cl

Cl

O

Cl

Cl

P

Cl                          Cl

Q

A.     compound N

B.     compound O

C.     compound P

D.     compound R

E.      none of these (3 minutes)

The following pKa values may assist you in answering questions A9 – A10.

pKa

CH3CH2OH                    15.9

CF3CH2OH                     12.5

CH3CO2H                       4.7

CF3CO2H –0.3

CH3 SO3H –2.6

Question A9.

Which one of the following is the strongest nucleophile?

CH3CH2O                   CF3CO2                       CH3SO3                        CH3CO2

A. B. C. D.

Question A10.

Which one of the following is the best leaving group?

CH3CH2O                   CF3CO2                       CH3SO3                        CH3CO2

A. B. C. D.

CF3CH2O

E.

(2 marks)

CF3CH2O

E.

(2 marks)

For Questions A11–A13 consider the following reaction with possible products I–IV.

CO2Et

O

N   K

O

O

N      CO2Et

O

I.

O

N

O

II.

CO2Et

III.

CO2Et

IV.

Question A11.

A.     I only           B.   II only          C.    III only          D.     IV only         E.        I and II (2 marks)

Question A12.

A.     I only           B.   II only          C.    III only          D.     IV only         E.        I and II (2 marks)

Which would be the major product formed from an E2 reaction?

A.     I only           B.   II only          C.    III only          D.     IV only

.

I and II

(2 marks)

Question A14.

What product(s) would be formed from the electrophilic addition reaction shown below?

CO2Et

Br2

BrCO2Et

Br

I.

BrCO2Et

Br

II.

BrCO2Et

Br

III.

Br

IV.

CO2Et

Br

A.      I only        B.   II only        C.   III and IV

D.   III

only

.

IV only

(3 marks)

For Questions A15–A18, consider the following reaction sequence used for the synthesis of

lenalidomide, a drug used for the treatment of multiple myeloma:

CO2CH3

step 1

CO2CH3

NO2

Br2

step 2

CO2CH3

Br

step

O

N

NH2        O       N

H

lenalidomide

step 5

O

O

step 4

NO2       O

CO2CH3

H

N

O

O

Question A15.

What reagent(s) are required for step 1.

A.       HNO3

B.        H2 SO4

C.        HNO3/H2 SO4

D.       NO2

E.        NaNO2 (2 marks)

Question A16. B

What other product is likely to form in step 1?

Question A17.

What reaction type occurs in step 3?

A.     Electrophilic addition

B.     Nucleophilic addition

C.     Electrophilic aromatic substitution

D.     Nucleophilic aromatic substitution

E.      Nucleophilic substitution (2 marks)

Question A18.

The best reagent for the reaction below is?

A.     LiAlH4

B.     NaBH4

C.     CrO3/H2 SO4

D.     KMnO4

E.      PCC (pyridinium chlorochromate)

CO2H

(2 marks)

Question A19.

The best reagent for the reaction below is?

CO2H

A.     LiAlH4

B.     NaBH4

C.     CrO3/H2 SO4

D.     KMnO4

E.      PCC (pyridinium chlorochromate)

Question A20.

The best reagent for the reaction below is?

OH

A.     LiAlH4

B.     NaBH4

C.     CrO3/H2 SO4

D.     KMnO4

E.      PCC (pyridinium chlorochrom