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Advanced Inorganic Chemistry

Total questions: 100

Worksheet time: 2hrs 40mins

Name
Class
Date
1.

An improper rotation axis, S, arises from which of the following situations?

a)

A mirror plane combined with an inversion

b)

Two proper rotation axes combined

c)

Identity combined with a mirror plane

d)

A proper rotation axis combined with a mirror plane

e)

The combination of two mirror planes

2.

Choose the best answer to fill in the blanks. Raman activity is dictated by a change in the _____________ of a molecule, while IR activity is related to a change in the ____________.

a)

Polarizability, dipole moment

b)

Magnetism, dipole moment

c)

Symmetry, magnetism

d)

Dipole moment, polarizability

e)

Magnetism, symmetry

3.

Dodecaborate (B12H12) does NOT contain which of the following symmetry elements?

a)

E

b)

C5

c)

i

d)

S10

e)

C6

4.

Fill in the blank. The character table for a C3v molecule, such as PCl3, lists three symmetry labels: A1, A2, and E. The A1 mode transforms z, z2, and x2 + y2. This means that the A1 mode is ________________.

a)

IR active only

b)

Raman active only

c)

Both IR and Raman active

d)

Neither IR or Raman active

e)

The only spectroscopically active mode in the molecule

5.

Fill in the blank. The character table for a D3h ion, such as CO32-, lists six symmetry labels: A1', A2', E', A1'', A2'', and E''. The A2' mode transforms Rz. This means that the A2' mode is _________________.

a)

IR active only

b)

Raman active only

c)

Both IR and Raman active

d)

Neither IR or Raman active

e)

The only spectroscopically active mode in the molecule

6.

In symmetry terms, which of the following MUST be true for an allowed transition?

a)

Both the electronic and vibrational representations must be symmetric.

b)

Both the electronic and vibrational representations must be asymmetric.

c)

Only the electronic representations must be symmetric.

d)

Only the vibrational representations must be symmetric.

e)

Symmetry does not matter, as long as there is a change in dipole or polarizability.

7.

Symmetry elements within a group must display which of the following?

a)

Closure (If A and B belong to the group, and A x B = C, then C also belongs to the group.)

b)

Associativity (A(BC) = (AB)C )

c)

Identity (The symmetry element times its identity, E, remains unchanged.)

d)

Inverses (There must be an inverse symmetry element that returns the molecule to its original state; A x A-1 = E.)

e)

Continuity (If a molecule contains an n axis, then it also contains axes of n-1, n-2...)

8.

Using the flow chart provided, determine which point group a tennis ball would belong to.

a)

D2d

b)

Cs

c)

C2h

d)

S4

e)

D4

9.

Which of the following has C4v symmetry?

a)

H2O

b)

BrF5

c)

BH3

d)

PCl6

e)

W(CO)6

10.

Which of the following does NOT contain an inversion center?

a)

SF6

b)

O2

c)

BF3

d)

C2Cl4

e)

All of the choices

11.

Hydrogen and helium both have two electrons (completely filled) bonding molecular orbitals. Hydrogen exists as a diatomic molecule; helium does not. Why?

a)

Helium also has electrons in antibonding orbitals, resulting in a bond order of zero.

b)

Helium also has electrons in non-bonding orbitals, resulting in a bond order of zero.

c)

Helium is a noble gas and never forms bonds.

d)

Hydrogen also has electrons in nonbonding orbitals, resulting in a bond order of two.

e)

Hydrogen has no antibonding orbitals, resulting in a bond order of two.

12.

The bond order of a molecule is given by the equation: ½ (bonding electrons – antibonding electrons). What accounts for the ½?

a)

The amount of magnetic character is reduced in bonds.

b)

The electrons are shared between two elements.

c)

Nonbonding electrons decrease bond ability.

d)

The antibonding electrons interfere with bonding.

e)

None of the choices

13.

What is the bond order for dinitrogen, N2?

a)

5

b)

1

c)

1.5

d)

2

e)

3

14.

When drawing the MO diagram of a heteronuclear diatomic molecule, at what relative positions should the atomic orbitals appear?

a)

They should be at the same energy to indicate bond formation.

b)

They should be at the same energy to indicate allowed symmetry.

c)

They should be at different energies, relative to their difference in electronegativities.

d)

They should be at different energies, relative to their atomic radii.

e)

They should be at different energies, relative to the number of lone pairs of electrons.

15.

When filling molecular orbitals, which of the following is FALSE?

a)

A maximum of two electrons per orbital is allowed.

b)

The orbitals with the lowest energy are filled first.

c)

Orbitals of the same energies are half-filled first; then electrons are allowed to pair up.

d)

Non-bonding orbitals are filled first.

e)

All of the choices

16.

Which of the following minimizes nucleus-nucleus repulsion and promotes electron-nucleus interaction?

a)

Nonbonding molecular orbitals

b)

Antibonding molecular orbitals

c)

Bonding molecular orbitals

d)

All of the choices

e)

Nonbonding molecular orbitals and bonding molecular orbitals only

17.

Which of the following must be true when atomic orbitals combine to form molecular orbitals?

a)

They must have constructive net interaction.

b)

They must have the correct symmetry to overlap

c)

They must be similar in energy

d)

There will be the same number of resultant molecular orbitals as atomic orbitals

e)

All of the choices

18.

Which of the following statements concerning sigma and pi molecular orbitals is FALSE?

a)

Sigma interactions occur along the internuclear axis.

b)

Pi interactions occur above and below the internuclear axis.

c)

Sigma bonds form first, followed by the subsequent formation of pi bonds.

d)

Two pi bonds are involved in a double bond.

e)

All of the choices

19.

Which of the following statements is true of nonbonding molecular orbitals?

a)

They are responsible for the formation of pi bonds.

b)

They are similar in energy to the atomic orbitals.

c)

They counteract bond formation in a molecule.

d)

They help hold the molecule together, once it is formed.

e)

They are responsible for the formation of sigma bonds.

20.

What compound is represented by this MO diagram? (Pay attention to the number of electrons and their respective energies.)

a)

CO2

b)

H2O

c)

CN-

d)

Cl2

e)

N2

21.

1s22s22p63s23p63d5 is the electron configuration for which element/ion?

a)

Mn2+

b)

V

c)

Fe3+

d)

All of the choices

e)

Mn2+ and Fe3+ only

22.

According to valence bond theory(VBT), O2 has no unpaired electrons. MO theory shows two unpaired electrons in a 2π* molecular orbital. Which of the following experiments supports the correct electron configuration?

a)

An EPR spectrum shows that oxygen is paramagnetic; MO theory is correct.

b)

An EPR spectrum shows that oxygen is paramagnetic; VBT is correct.

c)

Infrared spectroscopy shows a double bond stretch; MO theory is correct.

d)

Infrared spectroscopy shows a double bond stretch; VBT is correct.

e)

There is no way to know which theory is correct in this matter.

23.

According to valence bond theory, what is the difference between a complex with d2sp3 hybridization and sp3d2 hybridization?

a)

There is no actual difference; the orbitals involved are the same, only listed in a different order.

b)

The complex having d2sp3 hybridization is an “inner shell” complex, while the complex with sp3d2 hybridization is an “outer shell” complex.

c)

The complex having d2sp3 hybridization is an “outer shell” complex, while the complex with sp3d2 hybridization is an “inner shell” complex.

d)

The complex having sp3d2 hybridization does not exist; the electrons must fill the lowest energy orbitals first.

e)

The complex having d2sp3d2 hybridization does not exist; the electrons must fill the orbitals with the same principle quantum number.

24.

Analysis of a high spin d6 complex reveals that it is diamagnetic. What is the probable molecular geometry of the complex?

a)

Octahedral

b)

Tetrahedral

c)

Square planar

d)

All of the choices

e)

Both Octahedral and Square planar

25.

Compounds with octahedral molecular geometries sometimes elongate or compress through Jahn-Teller distortion. In doing so, which of the following occurs?

a)

They increase their ionization potential, rendering them most useful electrochemically.

b)

They reduce degenerate molecular orbitals, allowing a more stable molecule to exist.

c)

They undergo a strong magnetic transition, allowing easier detection by NMR and EPR.

d)

They increase their transition state energy, making them useful catalysts.

e)

They decrease shielding, allowing spectroscopically forbidden transitions to occur.

26.

Do high spin d5 octahedral complexes experience Jahn-Teller distortion? Why, or why not?

a)

Yes. The five electrons distribute themselves evenly in the five molecular orbitals, causing them to be degenerate. Axial elongation reduces this degeneracy.

b)

Yes. The five electrons distribute themselves evenly in the five molecular orbitals, causing them to be degenerate. Axial compression reduces this degeneracy.

c)

No. The five electrons distribute themselves evenly in the five molecular orbitals; no degeneracy exists.

d)

No. Four of the electrons are paired. Only one electron is unpaired and can only fill the one remaining orbital. No degeneracy exists.

e)

Yes. Four electrons are paired in the lower energy orbitals. The fifth electron can position itself into any of the remaining three orbitals, making it triply degenerate.

27.

Ferrocene consists of two cyclopentadienyl rings bound through 5 carbons to an iron center. What is the IUPAC name for ferrocene?

a)

mer-bis(cyclopentadienyl)iron(II)

b)

fac-bis(cyclopentadienyl)iron(II)

c)

bis(η5-cyclopentadienyl)iron(II)

d)

µ-bis(cyclopentadienyl)iron(II)

e)

(η5-cyclopentadienyl)iron(II)

28.

How would the complexes Λ-[Co(en)3]3+ and Δ-[Co(en)3]3+ differ?

a)

One would be a solid at room temperature, while the other would be a liquid.

b)

One would be highly colored, while the other would be colorless.

c)

One would be paramagnetic, while the other would be diamagnetic.

d)

One would rotate plane-polarized light clockwise, while the other would rotate it counterclockwise.

e)

All of the choices

29.

In chromium and copper, the 3d orbital fills before the 4s orbital is filled. Why?

a)

Because the stability gained from having a fully-filled or evenly, half-filled set of d orbitals is greater than the need to fill all lower energy orbitals first

b)

Because the 3d orbital is actually lower in energy than the 4s, so it fills first

c)

Because copper and chromium only exist as ions; never as neutral elements

d)

Because the atomic radii are so large that no effect is felt by the nucleus

e)

None of the choices

30.

Phosphines are often used as molecular bridges between two metal centers. How should these phosphines be notated according to IUPAC nomenclature?

a)

mu (µ)

b)

eta (η)

c)

chi (χ)

d)

xi (ξ)

e)

zeta (ζ)

31.

Transition metals exhibit all of the following general characteristics, EXCEPT:

a)

They are malleable and ductile.

b)

They have high melting points.

c)

They conduct heat and electricity.

d)

They are lustrous.

e)

They undergo irreversible oxidation.

32.

Using ligand field theory, which of the following would you predict to be the most paramagnetic?

a)

A low spin, d5 octahedral complex

b)

A high spin, d8 octahedral complex

c)

A low spin, d3 octahedral complex

d)

A d2 tetrahedral complex

e)

A d5 square planar complex

33.

Using the valence bond theory and the 18 electron rule, which of the following would you predict to be the most stable?

a)

Fe(CO)5

b)

Ni(CO)5

c)

Mo(CO)6

d)

Re(CO)6

e)

Ir(CO)5

34.

What happens when the electron pairing energy is larger than the octahedral field splitting energy?

a)

The result is a low-spin complex, where electrons will pair up and fill the lowest energy level.

b)

The result is a high-spin complex, where electrons will be promoted to the next energy level before pairing.

c)

The result is an unstable complex, where electrons can either pair or be promoted to the next energy level.

d)

The result is a high-spin complex, where electrons will pair up and fill the lowest energy level.

e)

The result is a low-spin complex, where electrons will be promoted to the next energy level before pairing.

35.

Which of the following has T-shaped molecular geometry?

a)

BF3

b)

ClF3

c)

PF6

d)

IF5

e)

SbF5

36.

Which of the following influences the amount of crystal field splitting in a metal complex?

a)

Charge of the metal ion

b)

Nature of the ligands

c)

Geometry of the complex

d)

Size of the ligands

e)

All of the choices

37.

Which of the following sets of complexes represents a set of stereoisomerism (not structural isomerism)?

a)

[PtCl(H2O)3]Br and [Pt(Br)(H2O)3]Cl

b)

cis-[PtCl2(NH3)2] and trans-[PtCl2(NH3)2]

c)

[CrCl2(H2O)4]Cl•2H2O and [CrCl3(H2O)3]•3H2O

d)

[Co(NH3)6] [Cr(ac)3] and [Co(ac)3] [Cr(NH3)6]

e)

[Co(SCN)(NH3)5]- and [Co(NCS)(NH3)5]-

38.

Which of the following would have the largest ionization energy?

a)

Copper

b)

Iron

c)

Gold

d)

Titanium

e)

Tungsten

39.

You discover a new metal complex that exhibits high spin characteristics. What ligand properties can you predict?

a)

It is highly polarizable.

b)

The ligand is relatively large.

c)

The ligand exhibits π donor ability.

d)

The ligand is acidic.

e)

All of the choices

40.

Which of the following would have the highest melting point?

a)

Silver

b)

Rhodium

c)

Cadmium

d)

Molybdenum

e)

The melting points would be equivalent, because they are in the same period.

41.

If a complex has a maximum absorption at 423 nm, what color would the complex appear to the human eye?

a)

Violet

b)

Blue

c)

Green

d)

Yellow

e)

Red

42.

Some tetrahedral metal complexes exhibit weak electronic transitions even though they are symmetry forbidden. Why?

a)

Jahn-Teller distortion

b)

Mixing of the p and d orbitals

c)

MLCT

d)

LMCT

e)

All of the choices

43.

The UV spectrum of metal complex A has a strong absorption at 412 nm. The UV spectrum of metal complex B has a strong absorption at 654 nm. If equal quantities of the two solutions of metal complexes are mixed, what would the resulting UV spectrum look like?

a)

The spectrum would show one very broad absorption band at 533 nm.

b)

The spectrum would show two weak absorption bands, one at 412 nm and the other at 654 nm.

c)

The spectrum would show two strong absorption bands, one at 412 nm and the other at 654 nm.

d)

The spectrum would show two weak absorption bands, one at 472 nm and the other at 594 nm.

e)

The spectrum would show two strong absorption bands, one at 472 nm and the other at 594 nm.

44.

The vertical line (located at Δ/B = 2 for a d6 system) in the Tanabe-Sugano diagram corresponds to which of the following?

a)

The ligand field stabilization energy (LFSE) is insufficient to allow transitions to the left of the line.

b)

The transitions to the left are symmetry allowed, while the transitions to the right are spin allowed.

c)

The transitions to the left are spin allowed, while the transitions to the right are symmetry allowed.

d)

The transitions to the left are low-spin complexes, while the transitions to the right are high-spin complexes.

e)

The transitions to the left are high-spin complexes, while the transitions to the right are low-spin complexes.

45.

Using the spin selection rules and the Tanabe-Sugano diagram provided, how many electronic transitions would you expect to see in the spectrum of a d8complex if Δ/B = 1.5?

a)

Two

b)

Three

c)

Nine

d)

Six

e)

Zero

46.

Which of the following is true with regard to charge transfer (ligand-to-metal or metal-to-ligand) absorption bands in relation to d-d transition bands?

a)

CT absorptions occur at higher wavelengths than d-d transitions.

b)

CT absorptions are less intense than d-d transitions.

c)

CT transitions are symmetry and spin allowed; d-d transitions are symmetry forbidden.

d)

CT transitions are spin allowed; d-d transitions are spin forbidden.

e)

CT transitions are symmetry and spin forbidden; d-d transitions are symmetry forbidden but spin allowed.

47.

Which of the following would be a spin allowed transition?

a)

3T11T1

b)

5E → 2E

c)

3T13A2

d)

1A23A2

e)

4T22T4

48.

Why are the hexaaqua complexes of Sc3+ and Zn+2 colorless, while the hexaaqua complexes of Fe2+, Cr3+, Co2+, Ni2+, and Cu2+ are intensely colored?

a)

Zn2+ has a completely filled d orbital, and Sc3+ has a completely empty d orbital.

b)

Zn2+ and Sc3+ always form high spin octahedral complexes.

c)

Zn2+ and Sc3+ always form low spin octahedral complexes.

d)

Zn2+ and Sc3+ are diamagnetic; the others are paramagnetic.

e)

Zn2+ and Sc3+ are paramagnetic; the others are diamagnetic.

49.

Why does a high spin d5 octahedral complex exhibit a very pale color, while a low spin d5 octahedral complex is more highly colored?

a)

The transition in the high spin complex is symmetry and spin forbidden. The transition in the low spin complex is symmetry allowed.

b)

The transition in the high spin complex is symmetry and spin forbidden. The transition in the low spin complex is spin allowed.

c)

The transition in the high spin complex is symmetry forbidden but spin allowed. The transition in the low spin complex is symmetry and spin allowed.

d)

The transition in the high spin complex is spin forbidden but symmetry allowed. The transition in the low spin complex is symmetry and spin allowed.

e)

The transition in the high spin complex is symmetry and spin forbidden. The transition in the low spin complex is symmetry and spin allowed.

50.

You have two solutions of chromium ions. Your lab partner has added potassium thiocyanate to one and potassium cyanide to the other, but does NOT remember which one contains which anion. Just by appearance, how can you tell them apart?

a)

The solution containing cyanide ion will give a larger crystal field splitting, causing a blue shift in the color of the complex. The complex with thiocyanate ion will appear as more red shifted.

b)

The solution containing cyanide ion will give a smaller crystal field splitting, causing a blue shift in the color of the complex. The complex with thiocyanate ion will appear as more red shifted.

c)

The solution containing cyanide ion will give a larger crystal field splitting, causing a red shift in the color of the complex. The complex with thiocyanate ion will appear as more blue shifted.

d)

The solutions will both be similar in color; however, the complex with thiocyanate will be more intense.

e)

You cannot tell them apart; the experiment would need to be restarted.

51.

A 19F NMR spectrum at room temperature reveals on well defined peak. When cooled slightly, the peak becomes broadened. At N2(l) temperatures, two well defined peaks are apparent. What is responsible for these observations?

a)

Dynamic fluxionality

b)

Spin-spin coupling interactions

c)

Integer quantum spin numbers (I = 1,2,3…)

d)

Fractional quantum spin numbers (I = 1/2, 3/2, 5/2)

e)

Low natural abundances of the 19F nucleus

52.

Carbon dioxide is a linear molecule with no dipole moment. Which of the following interactions is responsible for the observed IR spectrum of CO2?

a)

The asymmetric stretch of the C-O bonds creates a dipole moment that is IR active.

b)

The symmetric stretch of the C-O bonds creates a dipole moment that is IR active.

c)

The non-linear bending mode crates a net dipole, which is IR active.

d)

All of the choices

e)

The asymmetric stretch of the C-O bonds creates a dipole moment that is IR active and the non-linear bending mode crates a net dipole (which is IR active) only

53.

In NMR spectroscopy, what happens to the chemical shift and resonance frequency of a compound when the spectrometer frequency changes?

a)

The chemical shift and resonance frequency also change.

b)

The chemical shift changes; the resonance frequency remains constant.

c)

The chemical shift remains constant; the resonance frequency changes.

d)

The chemical shift and resonance frequency remain constant.

e)

There is no way to predict the effect.

54.

The splitting of energy levels in the presence of a magnetic field is caused by which of the following?

a)

The Zeeman effect

b)

Pauli exclusion principle

c)

Symmetry degeneracy

d)

Fermi contact interaction

e)

Bose-Einstein effect

55.

What is the most likely cause of fluxional behavior in the NMR spectrum of Fe(CO)5, iron pentacarbonyl?

a)

Dissociation and recoordination of the carbonyl ligands

b)

Rotation of a hindered carbonyl bond

c)

Opening and closing of bridging carbonyls

d)

Isomerism between trigonal bipyramidal and square pyramidal configurations

e)

Monmer-dimer formation with a bridging carbonyl

56.

What molecule most likely produced this EPR spectrum?

a)

NO2 radical

b)

CH3 radical

c)

CH2Cl radical

d)

CH2CH2 radical

e)

OH radical

57.

Which of the following cannot be studied by EPR?

a)

Paramagnetic transition metal complexes

b)

Diamagnetic transition metal complexes

c)

Free radicals in the solid state

d)

Free radicals in the liquid or gas state

e)

Complexes containing more than one unpaired electron

58.

Which of the following conditions does NOT result in a nonzero quantum spin number (I)?

a)

An odd mass number and odd atomic number, such as 1H

b)

An odd mass number and an even atomic number, such as 13C

c)

An even mass number and an even atomic number, such as 16O

d)

An even mass number and an odd atomic number, such as 14N

e)

All of the mentioned situations will result in a nonzero quantum spin number.

59.

Which of the following would be predicted to have a g-factor value close to 2?

a)

A free electron

b)

An unpaired electron in an organic molecule

c)

An unpaired electron in a transition metal complex

d)

All of the choices

e)

A free electron and an unpaired electron in an organic molecule only

60.

Why does Re(CO)5Cl exhibit lower carbonyl stretching frequencies (νco) than [Re(CO)5(py)]+?

a)

Cationic metal complexes experience less π backbonding than their neutral or anionic analogs.

b)

Pyridine is a good π acceptor and contributes to increased π backbonding.

c)

The carbonyl to metal bond strength is increased in the chloro complex.

d)

All of the choices

e)

Cationic metal complexes experience less π backbonding than their neutral or anionic analogs and pyridine is a good π acceptor and contributes to increased π backbonding only

61.

EDTA4- is a polydentate ligand. How many coordination sites does it contain and through what moieties?

a)

Two; through the lone pairs on the two nitrogen atoms

b)

Two; through the lone pairs on two of the oxygen atoms

c)

Four; through the lone pairs on the four oxygen atoms

d)

Four; through the anion on the four oxygen atoms

e)

Six; two through the lone pairs on the two nitrogen atoms and four through the lone pairs of the four oxygen atoms

62.

How do Cp complexes and derivatives of metal ions undergo ligand substitution reaction?

a)

Associative mechanism, aided by a ring slip

b)

Dissociative mechanism, in which the Cp ring is lost

c)

Inversion of stereochemistry and loss of the Cp ring

d)

Dissociation of the Cp ligand, followed by re-association of Cp

e)

All of the choices

63.

How is it possible to form different transition metal complexes when mixed with the same two ligands?

a)

It is dependent on which ligands are a part of the primary valence and which ones are a part of the secondary valence.

b)

It depends on the charge of the metal ion present.

c)

It depends on the number of empty d orbitals.

d)

It depends on the nature of the ligands involved and whether they are mono or multi-dentate.

e)

All of the choices

64.

Using the neutral (covalent) method of electron counting, how many electrons are donated to a metal center by a cyclopentadiene ring?

a)

2

b)

5

c)

6

d)

8

e)

10

65.

What is the coordination number of [Cu(NH3)4][Cl-]2?

a)

2

b)

3

c)

4

d)

5

e)

6

66.

What is the oxidation state of chromium in [Cr(NH3)2(C2O4)2]- ?

a)

+3

b)

+2

c)

+4

d)

+7

e)

+6

67.

What is true about coordinative unsaturation?

a)

It plays an important role in insertion, polymerization, and metathesis reactions.

b)

It describes a complex with a coordination number less than 4.

c)

It generally means another ligand can be accommodated.

d)

All of the choices

e)

It plays an important role in insertion, polymerization, and metathesis reactions and it generally means another ligand can be accommodated only

68.

Which compound will react with Ag+ ion in water: [Co(NH3)6]Cl3 or [Co(Cl3)](NH3)6? What is formed?

a)

[Co(Cl3)](NH3)6; AgCl is formed.

b)

[Co(Cl3)](NH3)6; NH4Cl is formed.

c)

[Co(NH3)6]Cl3; AgCl is formed.

d)

[Co(NH3)6]Cl3; NH4Cl is formed.

e)

Both will react with silver in water; AgCl and NH4Cl are formed.

69.

Which of the following is an ambidentate ligand?

a)

EDTA

b)

SCN-

c)

NH3

d)

Hemoglobin

e)

Cl-

70.

The interaction between the metal and ligands in coordination complexes can best be described as which of the following?

a)

Hydrophilic interactions

b)

Hydrophobic interactions

c)

Van der Waals interactions

d)

Lewis acid-base interactions

e)

Hydrogen bonding interactions

71.

A natural spring containing manganese is found to be highly acidic. Using this diagram, what form of iron would you predict to be most abundant?

a)

Fe(s)

b)

Fe3+(aq)

c)

Fe(OH)2(s)

d)

Fe2+(aq)

e)

Fe(OH)3(s)

72.

In Latimer diagrams, what does a large positive standard reduction potential indicate?

a)

The species on the left is readily reduced to the species on the right side of the arrow.

b)

The species on the lef tis a good reducing agent.

c)

The species under goes diproportionation.

d)

All of the choices.

e)

None of the choices.

73.

Marcus theory is used to approximate which of the following?

a)

The heat of formation of the precursor complex

b)

The heat of fission of the successor complex

c)

The solvation energy of the transition complex

d)

The free energy of electron transfer

e)

All of the choices

74.

What happens to an outer sphere redox reaction, if the spin multiplicity is different?

a)

The reaction does not proceed.

b)

The reaction is drastically slowed, requiring a spin flip to occur.

c)

The reaction proceeds quicker, because different spin states allow faster electron transfer.

d)

The reaction will proceed as inner sphere instead, because electrons with different spin will pair and form a bond.

e)

None of the choices

75.

What implication does overpotential have on a redox reaction?

a)

Even though a reaction is thermodynamically favorable, the reaction may be slow kinetically.

b)

All redox reactions are favorable at in alkaline media.

c)

All thermodynamically favorable reactions occur quickly on a kinetic scale.

d)

If a reaction is kinetically favorable, it will proceed even if it is thermodynamically unfavorable.

e)

No redox reactions occur in highly acidic media.

76.

What is considered the rate determining step in an outer sphere redox reaction?

a)

Formation of the bridging ligand complex

b)

Formation of the precursor (cage) complex

c)

Electron transfer

d)

Solvent entering the coordination sphere

e)

Fission of the successor ligand complex

77.

What is considered the rate determining step in an outer sphere redox reaction?

a)

Formation of the bridging ligand complex

b)

Fission of the successor ligand complex

c)

Electron transfer

d)

Solvent entering the coordination sphere

e)

Both fission of the successor ligand complex and electron transfer

78.

Which of the following is a properly balanced half reaction in acidic media?

a)

Cr2O72- + 8 H+ + 3 H2C2O4 → 2 Cr3+ + 7 H2O + 6 CO2

b)

12 H+ + 5 I- + IO3- → 3 I2 + 6H2O

c)

2 Fe(OH)2 + H2O2 → 2 Fe(OH)3

d)

3 Cd + 8 H+ + 2 NO3- → 3 Cd2+ + 2 NO + 8 H2O

e)

2 Au3+ + 6I- → 2 Au + 3 I2

79.

Which of the following is a properly balanced half reaction in basic media?

a)

Cr2O72- + 8 H+ + 3 H2C2O4 → 2 Cr3+ + 7 H2O + 6 CO2

b)

12 OH- + 5 I- + IO3- → 3 I2 + 6H2O

c)

Fe(OH)2 + OH- → Fe(OH)3

d)

2 Cr(OH)3 + ClO3 + 4 OH → 2 CrO42− + Cl + 5 H2O

e)

2 Au3+ + 6I → 2 Au + 3 I2

80.

Given the Frost diagram for phosphorus and nitrogen in acidic conditions, which of the following species is the most thermodynamically favored?

a)

H3PO4

b)

NH4+

c)

HNO3

d)

PH3

e)

P & N (elemental)

81.

Cr2+ (d4 system) and Cu2+ (d9 system) are kinetically labile with respect to substitution reactions. Why?

a)

They experience Jahn-Teller distortion, making their axial bonds longer and easier to break.

b)

Their ground state structure resembles their transition state structure.

c)

Their electrons are distributed equally among the d-orbitals.

d)

Their large radii can accommodate a larger coordination sphere.

e)

They experience Jahn-Teller distortion, making their axial bonds longer and easier to break and their ground state structure resembles their transition state structure.

82.

In D or Id mechanisms for substitution in octahedral metal complexes, stereochemistry is retained when the intermediate’s molecular geometry is which of the following?

a)

Tetragonal

b)

Trigonal bipyramidal

c)

Square pyramidal

d)

Both Tetragonal and Square pyramidal

e)

All of the choices

83.

The effect of a coordinated ligand upon the rate of substitution of ligands opposite it is referred to as which of the following?

a)

The trans influence

b)

The trans effect

c)

The biphilic effect

d)

The solvolysis effect

e)

The anation effect

84.

What is responsible for the increased stability of formation of a complex containing two chelating ligands as compared to four monodentate ligands?

a)

Enthalpy of reaction

b)

Decreased activation energy

c)

Formation of dimeric species (bridging ligands)

d)

Entropy of reaction

e)

Outer sphere electron transfer

85.

When hexaaqua complexes of cobalt react with chloride ion, they undergo a change in the coordination chemistry. Why is this NOT the case when they react with ammonia?

a)

The chloride ions are larger than the water molecules, only allowing four to coordinate around the central metal ion; ammonia is similar in size to water, so six will coordinate.

b)

The chloride ions are anionic, and the metal centers cannot accommodate a larger negative charge; ammonia is a neutral species.

c)

Chloride ions precipitate the metals out of solution; ammonia complexes do not.

d)

The addition of excess chloride ions will actually result in hexa-chloro compounds.

e)

Chloride additions occur in acidic media; ammonia is alkaline.

86.

Which of the following affects substitution at square planar metal centers?

a)

The entering group

b)

The leaving group

c)

Other ligands in the coordination sphere

d)

The metal center itself

e)

All of the choices

87.

Which of the following is about the trans influence is FALSE?

a)

It is a kinetic phenomenon.

b)

It can influence M-L bond lengths.

c)

It can result in changes in NMR coupling constants.

d)

It can affect the vibrational frequency.

e)

It is purely thermodynamic.

88.

Which of the following is true of substitutions at square planar metal centers?

a)

They occur via an associative mechanism with a five coordinate intermediate.

b)

They only proceed when bond formation is the rate determining step.

c)

They only proceed when bond breaking is the rate determining step.

d)

They only proceed when the transition energies of bond formation and bond breaking are similar.

e)

They occur via a dissociative mechanism with a three coordinate intermediate.

89.

Which of the following rate laws indicates a dissociative mechanism?

a)

k = [A][B]

b)

k = [A]

c)

k = [A]2[B]

d)

Both k = [A][B] and k = [A]2[B]

e)

The mechanism cannot be determined from the rate law.

90.

Fill in the blank to complete the following analogy. Thermodynamics : free energy :: kinetics : ________________.

a)

Activation energy

b)

Thermal energy

c)

Electron transfer

d)

Entropy

e)

Enthalpy

91.

Fill in the blank. The Haber process is used for the production of _______________.

a)

Ammonia

b)

Sulfur trioxide

c)

Sulfuric acid

d)

Margarine

e)

Nitric acid

92.

What is the end product of the Contact Process?

a)

Ammonia

b)

Sulfur trioxide

c)

Sulfuric acid

d)

Margarine

e)

Nitric acid

93.

What is the role of a catalyst in a reaction?

a)

It shifts the equilibrium toward the products based on LeChatlier’s principle.

b)

It provides an alternate route with a lower activation energy for the reaction to proceed.

c)

It donates electrons to break or form bonds as needed until it is entirely consumed.

d)

It forms bridging complexes which align the molecular orbitals of the reactants.

e)

All of the choices

94.

Which of the following is an example of a homogeneous catalysis?

a)

The hydrogenation of vegetable oil in the presence of nickel to make margarine

b)

The use of Pt, Pd or Rh in catalytic converters

c)

The destruction of ozone in the atmosphere

d)

The use of vanadium(V)oxide in the conversion of sulfur dioxide to sulfur trioxide

e)

All of the choices

95.

The anticancer drug cisplatin is a platinum based complex, which works by destroying the DNA within cancer cells. Which of the following transition metals have anticancer applications?

a)

Ru

b)

Ti

c)

V

d)

Fe

e)

All of the choices

96.

What advantage does doping an LED with a transition metal have?

a)

Doping allows the LED to harvest light from triplet states, increasing quantum efficiency.

b)

Doping increases the overall number of singlet to singlet emission pathways.

c)

It reduces the overall cost of producing an LED; the inorganic dopants are inexpensive.

d)

All of the choices

e)

None of the choices

97.

Which of the following describes a challenge in the production of effective metal-based dye-sensitized solar cell?

a)

Metal ion complexes are unable to harvest light energy.

b)

The cost of the metal ion complexes is prohibitive.

c)

The storage of energy occurs by thermal or chemical means.

d)

The energy produced can only be utilized in electrical grids.

e)

All of the choices

98.

Which of the following is NOT an application of a secondary cell battery?

a)

Nickel-cadmium in portable electronics and toys

b)

Lead acid batteries in automobiles

c)

Silver-zinc button cells in hearing aides

d)

Silver-cadmium batteries in satellites

e)

Zinc-carbon dry cell batteries in flashlights

99.

Why are organometallic vanadium complexes being used to treat diabetes instead of the inorganic vanadium salts?

a)

The organometallic complexes are easier to synthesize than the inorganic salts.

b)

The organometallic complexes are less toxic and more effective in lowering blood glucose levels.

c)

The organometallic complexes are less expensive to synthesize and cost less on the market.

d)

The effect of the inorganic salts was discovered after the organometallic complexes had established a successful history.

e)

The FDA will not approve medicinal use of purely inorganic compounds for biological applications.

100.

Which of the following is true of organometallic pharmaceuticals as antimicrobials?

a)

Metals are nontoxic to humans.

b)

Harmful stereoisomers do not exist.

c)

They are soluble in water and easily administered.

d)

They counteract drug resistance that has been built to purely organic molecules.

e)

There are no current organometallic applications to antimicrobials.