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.

What is the order of a reaction, if the graph of In[A] versus time gives a straight line?

A.     There is not enough information to answer this question.

B.     zero order

C.     first order

D.     second order

E.      third order (2 minutes)

Question A2.

Consider the reaction:

4PH3(g)   ®  P4(g)  +  6H2(g)

If the reaction rate of consumption of PH3 is 2.4 ´ 10–3 mol L– 1 s– 1, determine the rate of formation of P4 and H2 respectively?

P4 H2

A.          2.4 ´ 10–3 mol L– 1 s– 1 2.4 ´ 10–3 mol L– 1 s– 1

B.          6.0 ´ 10–4 mol L– 1 s– 1 3.6 ´ 10–3 mol L– 1 s– 1

C.        –6.0 ´ 10–3 mol L– 1 s– 1 –3.6 ´ 10–3 mol L– 1 s– 1

D.          6.0 ´ 10–4 mol L– 1 s– 1 2.4 ´ 10–3 mol L– 1 s– 1

E.          None of the above are correct. (2 minutes)

Question A3.

What are the units for a rate constant of a second order reaction and a zero order reaction, respectively? Note: concentration is in mol L– 1 and time is in seconds.

Second Order Zero Order

A.

B.

C.

D.

E.

mol L– 1 s– 1

1

s–

mol– 1 L s– 1

mol– 1 L s– 1

mol– 1 L– 1 s– 1

Question A4.

A first order reaction is 75% complete in 320 seconds.  Determine the first and second half lives for this reaction (consecutive half lives)?

1st half Life 2nd Half Life

A.

B.

C.

D.

E.

160 s

320 s

320 s

80 s

160 s

320 s

160 s

640 s

160 s

160 s (3 minutes)

Question A5.

A certain reaction has an activation energy of 54.0 kJ mol– 1 .  As the temperature for this          reaction is increased from 22°C to a higher temperature, the rate constant increases by a factor of 7.0. Calculate the higher temperature?

A.     51°C            B.    75°C              C.   42°C               D.    32°C             E.      122°C (3 minutes)

A proposed mechanism for a reaction is given below.       C4H9Br(aq) C4H9+(aq)   +  Br–(aq)

C4H9+(aq)  +  H2O(l) C4H9OH2+(aq)                 C4H9OH2+(aq)  +  H2O(l) C4H9OH(aq)  + H3O+(aq)

What is the expected rate law for this mechanism?

A.     k1 [C4H9+][ Br–]

B.     k2 [C4H9+][H2O]

C.     k3 [C4H9OH2+][H2O]

D.     k1 [C4H9Br]

E.      none of the above

Question A7.

F

How many signals would you expect in the 13C NMR

spectrum for meta-difluorobenzene shown to the right?

F

A.     2                   B.     3                C.     4                  D.      5 (2 marks)

Question A8.

A compound has the molecular formula C6H10O and shows a strong absorption in its IR          spectrum at 1715 cm– 1 . Which of the following compounds is the most likely structure for this compound?

O                                   OH OCH3 OH                               O

H

A.                          B.                           C.                            D.                            E. (2 marks)

The information below is required to answer questions A9-A13.

Ibuprofen is a nonsteroidal anti-inflammatory drug used for treating pain, fever, and inflammation. The following scheme for the synthesis of Ibuprofen is referred to in

questions A9 – A13.

step 1

CH3COCl

AlCl3

O

step 2

(1) NaBH4

(2) H3O+

OH

step 3

CO2H

Ibuprofen

step 5

(1) NaOH

(2) H3O+

CN

step 4

NaCN

Br

Question A9.

Which of the following statements is/are true for Step 1 of the scheme shown above?

A.     It is an example of a Friedel-Crafts acylation reaction.

B.     The isobutyl group is an electron donating group.

C.     The ortho product will also be formed.

D.     All of the above.

E.     None of the above.

Question A10.

What type of reaction is occurring in Step 2 of the scheme shown above?

A.     a Grignard reaction

B.     a nucleophilic addition/elimination reaction

C.     a reduction reaction

D.     an oxidation reaction

E.      none of the above (2 marks)

Question A11.

Which of the following statements is/are TRUE for Step 3 of the scheme shown above?

A.     The hydroxide leaving group is a poor leaving group.

B.     PBr3 could be used as a reagent to convert the alcohol into the alkyl bromide.

C.     When HBr is used as the reagent, the likely mechanism of the reaction is SN 1 since a resonance stabilized benzyl cation is formed.

D.     None of the above.

E.      All of the above. (3 marks)

Question A12.

What type of reaction is occurring in Step 4 of the scheme shown above?

A.     a Grignard reaction

B.     a nucleophilic addition/elimination reaction

C.     a SN2 reaction

D.     a Markovnikov addition reaction

E.      none of the above (2 marks)

Question A13.

Which one of the following statements is TRUE for Step 5 of the scheme shown above?

A.     The nitrile functional group is hydrolysed to a carboxylic acid functional group.

B.     The nitrile functional group is hydrolysed to an ester functional group.

C.     The amide functional group is hydrolysed to a carboxylic acid functional group.

D.     None of the above. (2 marks)

Which of the following is the strongest acid?

A. CH2FCO2H           B. CHF2CO2H         C. CF3CO2H

D. CH3CO2H

E. CH3OCH3 (2 marks)

Question A15.

Which one of the following Newman projections of (1S, 2S)- 1-bromo- 1,2-diphenylpropane represents the conformation associated with the anti-periplanar E2 transition state?

Me

Ph

H

H

Ph

A

(3 marks)

Which one of the following is the most stable carbocation?

A B C

O

D

E

(3 marks)

The following scheme for the synthesis of 3-chlorobenzoic acid is referred to in questions

sequence 1:

sequence 2:

sequence 3:

reagents A

reagents B

reagents A

A17 – A20.

CH3

reagents B

reagents A

Cl

CH3

reagents C

CH3

reagents C

Cl

CH3

reagents C

Cl

CO2H

reagents B

Question A17.

Which one of the following would be used as Reagents A in the sequences shown above?

A.     CH3OH and sodium hydroxide

B.     CH4 and strong acid

C.     CH3Cl and AlCl3

D.     CH4 and Cl2

E.      None of the above (2 marks)

Question A18.

Which one of the following would be used as Reagents B in the sequences shown above?

A.     Cl2

B.     PCl5

C.      SOCl2 and AlCl3

D.     FeCl3 and Cl2

E.     None of the above

Question A19.

Which one of the following would be used as Reagents C in the sequences shown above?

A.     CO2 and sodium hydroxide

B.     KMnO4 and H3O+

C.     H2 and Pd

D.     HNO3 and H2 SO4

E.     None of the above (2 marks)

Question A20.

By considering the directing effects of various groups, the most likely sequence of the three reactions to produce 3-chlorobenzoic acid is:

B.      Sequence 2

C.      Sequence 3

D.      None of the above (3 marks)

Question A21.

Which one of following has the strongest conjugate base?

A.

B.

C.

D.

E.

Hydrochloric acid

Ethane

Ethylene (ethene)

Acetylene (ethyne)

Acetic acid (2 marks)

Question A22.

Consider the concentration cell shown below. The concentrations are listed under each compartment.

[Ag+] = 0.10 M                       [Ag+] = 1.0 M

The cell potential for the above cell at 25oC is closest to:

A.     0.30 V            B.    0. 18V          C.    0.060V          D.   0.78 V

E. –0.060V

(2 marks)

Question A23.

The Mond process is used to purify nickel. The reactions involved are listed below:

NiO(s)  +  H2(g)  ® Ni(s)  +  H2O(g)

Ni(s)  +  4CO(g)  ® Ni(CO)4(g)

Ni(CO)4(g)  ® Ni(s)  +  4CO(g)

Which of the following contains statements that are ALL correct?

A.     Nickel oxide is oxidised with hydrogen gas to give crude nickel metal. Reaction of the crude nickel solid with carbon monoxide at low temperatures produces Ni(CO)4(g)     and the volatility of this organometallic complex allows isolation of the pure gas. The pure nickel is then recovered by heating at a hotter temperature to decompose the        Ni(CO)4(g).

B.     Nickel oxide is reduced with hydrogen gas to give crude nickel metal. Reaction of the crude nickel with carbon monoxide at low temperatures re-oxidises the nickel and      forms Ni(CO)4(g). The volatility of this organometallic complex allows its isolation   from the crude mixture. The pure nickel is then recovered by heating at a hotter          temperature to decompose the Ni(CO)4(g).

C.     Nickel solid is reduced with carbon monoxide gas to give crude nickel metal but also  other metal contaminants. Reaction of the crude nickel with carbon monoxide at low   temperatures re-oxidises the nickel and forms Ni(CO)4(g). The volatility of this           organometallic complex allows its isolation from the crude mixture. The pure nickel is then recovered by heating at a hotter temperature to decompose the Ni(CO)4(g).

D.     Nickel oxide is reduced with hydrogen gas to give crude nickel metal. Reaction of the crude nickel with carbon monoxide at low temperatures produces Ni(CO)4(g). The     volatility of this organometallic complex allows isolation of pure Ni(CO)4 . The pure  Ni(CO)4 is decomposed by heating at a hotter temperature to yield pure nickel. (3 marks)

Question A24.

Consider the following half reaction:

[MnO4]–(aq) + 8H+(aq) +  5e– ®  Mn2+(aq) + 4H2O(l) E°cell = 1.51 V                 The potential (E) at 298 K when [Mn2+] = 0.00500 M; [MnO4]– = 0.500 M at pH 2.5 is closest to:

A.     1.51 V           B.    1.25 V            C.   0.440 V          D.    1.50 V            E.     1.30 V (3 marks)

Question A25.

Use the following reduction potentials to calculate the DG0 for the decomposition of hydrogen peroxide (at 298 K):

O2(g) + 4H+(aq) + 4e– ®   2H2O(l)     H2O2(aq) + 2H+(aq) + 2e– ®  2H2O(l)

E0 = 1.23 V

E0 = 1.78 V

A. –212 kJ mol– 1

B.     – 106 kJ mol– 1

C.     –580 kJ mol– 1

D.     –529 kJ mol– 1

E.        106 kJ mol– 1 (3 marks)

Question A26.

How many 3d-electrons are present in manganese(II)?

A.    6                    B.   5                     C.   4                     D.   3                     E.    2 (2 marks)

Question A27.

Which one of the following molecules is neither an ambidentate nor polydentate ligand?

A.     Ethylenediaminetetraacetate (edta)

B.     Cyanide

C.     Porphyrin

D.     Ammonia

E.      Oxalate (2 marks)

Question A28.

How many isomers are possible for the octahedral coordination complex [Fe(SCN)3(OH2)3]?

A.    2                    B.   4                     C.   6                     D.   8                     E.     10 (3 marks)

Question A29.

Which one of the following ions does not represent a common oxidation state for the specified metal?

A.    Co4+                       B.   Cr6+                          C.   Cr2+                          D.   V4+                            E.    Zn2+ (2 marks)

Question A30.

How many unpaired electrons will be associated with the metal ion in (NH4)3 [Fe(CN)6]?

A.     1                    B.   2                     C.   3                     D.   4                     E.    5 (2 marks)

Question A31.

Which one of the following statements is NOT TRUE for the permanganate ion?

A.     The ion has tetrahedral coordination geometry.

B.     The manganese centre has no unpaired electrons.

C.     The ion is dianionic.

D.     The ion is purple.

E.      The ion is a good oxidising agent. (2 marks)

Question A32.

Which one of the following statements is INCORRECT?

A.     The crystal field stabilisation energies are the same for octahedral Ni2+ and V2+ .

B.     The compounds cis- and trans-[PtCl2(NH3)2] have identical anti-cancer properties.

C.     Iron is typically in the +3 oxidation state at the surface of lakes.

D.     Aqueous Fe3+ is a stronger Bronsted acid than acetic acid.

E.      Amino acids can be ligands for transition metals. (2 marks)

Question A33.

Which one of the following possibilities correctly ranks the ligands (coordinating atoms in     bold) in order of DECREASING crystal field strength as given by the spectrochemical series:

A. F– > H2O > Br–

B. NCS– > H2O > NH3

C. NO > Cl– > NH3

D. CN– > pyridine > H2O

E. Br– > Cl– > F– (2 marks)

Question A34.

Consider the ionic solids, Na2 SO4, K2 SO4, MgSO4 and CaSO4 .

Which of the options below (A-E) lists the solids in order of INCREASING lattice energy.

A.     Na2 SO4 < K2 SO4 < MgSO4 < CaSO4

B.     K2 SO4 < Na2 SO4 < CaSO4 < MgSO4

C.     MgSO4 < CaSO4 < Na2 SO4 < K2 SO4

D.     Na2 SO4 < MgSO4 < K2 SO4 < CaSO4

E.      K2 SO4 < CaSO4 < Na2 SO4 < MgSO4 (2 marks)

Question A35.

According to Molecular Orbital Theory the bond order in He2+ is:

A.  -0.5                 B.  0                      C.  0.5                    D.  1.0                    E.   1.5 (3 minutes)

Question A36.

Tremolite possesses an infinite double chain silicate structure, part of which is indicated below:

What is the formula of the silicate anion in tremolite?

A.   Si2O54–                    B.  Si4O104–                       C.   Si4O116–                     D.   Si2O52–                    E.    Si2O64–

(2 marks)

Question A37.

The compound Na2O can be described as consisting of cubic close packed oxide ions with the sodium ions occupying tetrahedral holes.  Within the structure what fraction of tetrahedral      holes are occupied by sodium ions.

A.      1/8 of the tetrahedral holes are occupied.

B.      1/4 of the tetrahedral holes are occupied.

C.      1/2 of the tetrahedral holes are occupied.

D.