1.

[6 points] What is the correct name for the compound [Mn(en)

2
(OH)
2
]Cl
2

a. Bis(ethylenediamine)dihydroxymanganese(II) dichloride
b. Bis(ethylenediamine)dihydroxymanganese(IV) chloride
c. Diethylenediaminedihydroxymanganese(IV) chloride
d. Diethylenediaminedihydroxidemanganese(II) dichloride
e. Bis(ethylenediamine)dihydroxidemanganese(IV) chloride



Figure 1

2. [6 points] The neutral molecule shown in Figure 1 has the formula CoBr
2
N
4
C
4
H
16
.
What is the name of this molecule?
a. cis-bis(ethylenediamine)dibromocobalt(II)
b. cis-dibromobis(ethylenediamine)cobalt(II)
c. trans-dibromobis(ethylenediamine)cobalt(IV)
d. trans-dibromobis(ethylenediamine)cobalt(II)
e. None of the above

3. [7 points] Consider the following coordination complexes:

I. [Co(en)
3
]
2+
II. trans-[Nb(C
2
O
4
)
2
(NH
3
)
2
]
+

III. cis-[Nb(C
2
O
4
)
2
(NH
3
)
2
]
+
IV. cis-[Pt(en)Cl
2
]

Which of these complexes have an optical isomer (an enantiomer)?
a. I only b. I and II c. I and III d. I, II and III e. III and IV
4. [6 points] During the formation of a coordination compound, ligands act as
___________.

(a) Lewis bases
(b) Arrhenius bases
(c) Bronsted bases
(d) Lewis acids
(e) Arrhenius acids

5. [6 points] In the compound K
3
[Co(CN)
6
] how many unpaired electrons are there
on the cobalt atom?

(a) 0
(b) 2
(c) 4
(d) 5
(e) 6

6. [7 points] How many of the following transition metal ions would you expect to
be colorless in aqueous solution?

Cu
2+
Zn
2+
Ru
4+
Cu
+
Cr
3+

(a) zero
(b) one
(c) two
(d) three
(e) four

7. [7 points] Determine the number of unpaired electrons for each of the
following coordination complexes:
[RhCl
6
]
2
[MnCl
6
]
2
[Ni(H
2
O)
6
]
2+
[Pt(CN)
4
]
2

Arrange these complexes in order of increasing number of unpaired electrons (in
the answers below an = sign is used if two complexes have the same number of
unpaired electrons).
a. Fewest [Ni(H
2
O)
6
]
2+
= Pt(CN)
4
]
2
< [MnCl
6
]
2
< [RhCl
6
]
2
Greatest
b. Fewest [Pt(CN)
4
]
2
< [Ni(H
2
O)
6
]
2+
< [MnCl
6
]
2
< [RhCl
6
]
2
Greatest
c. Fewest [Pt(CN)
4
]
2
< [RhCl
6
]
2
< [Ni(H
2
O)
6
]
2+
< [MnCl
6
]
2
Greatest
d. Fewest [MnCl
6
]
2
< [RhCl
6
]
2
< [Ni(H
2
O)
6
]
2+
= [Pt(CN)
4
]
2
Greatest
e. Fewest [Pt(CN)
4
]
2
< [Ni(H
2
O)
6
]
2+
< [RhCl
6
]
2
< [MnCl
6
]
2
Greatest

8. [6 points] If two molecules have the same number and type of atoms as well as
the same bonds they could be either ___________________?
(a) Optical isomers or linkage isomers
(b) Geometric isomers or linkage isomers
(c) Optical isomers or coordination sphere isomers
(d) Optical isomers or geometric isomers
(e) Geometric isomers or coordination sphere isomers

9. [6 points] How much lead carbonate (FW = 267.2 g/mol) is needed to make
10.00 g of Pb
3
(VO
4
)
2
(FW = 851.5 g/mol) from the reaction between lead (II)
carbonate and vanadium (V) oxide?
(a) 9.414 g
(b) 3.138 g
(c) 2.388 g
(d) 8.928 g
(e) None of the above

10. [6 points] What is the coordination number of cobalt in [Co(NH
3
)
5
Cl](NO
3
)
2
?

(a) 12
(b) 8
(c) 4
(d) 2
(e) 6

11. [7 points] The complex [Zn(NH
3
)
2
Cl
2
]F
2
does not exhibit cis-trans-isomerism.
The geometry of the complex must be _________________.

(a) tetrahedral
(b) trigonal bypyramid
(c) octahedral
(d) square planar
(e) either tetrahedral or square planar

12. [7 points] Which of the following complexes will be diamagnetic?


I. [AuF
4
]

II. [ZnCl
4
]
2
III. [Fe(CN)
6
]
4
IV. [CoCl
6
]
3

(a) Only II (b) II and III
(c) I and II (d) I, II and III
(e) All of these complexes are diamagnetic.


Figure 2

13.[7 points] The absorbance spectrum for [V(NH
3
)
6
]
4+
is shown in Figure 2. The
absorption maximum falls at 470 nm. Which of the following diagrams represents
the d-orbital filling and energy splitting?


14.[7 points] What is the color of a solution containing [V(NH
3
)
6
]
4+
?
(a) Blue (b) Orange (c) Violet (d) Green (e) Colorless


15.[7 points] What is the most likely color of a solution containing [V(en)
3
]
4+
?
(a) Blue (b) Orange (c) Violet (d) Yellow (e) Red


A series of samples with compositions Ti
1x
Zr
x
O
2
have been prepared by solid state
reaction. The end members, TiO
2
and ZrO
2
have different structures. TiO
2
is
orthorhombic while ZrO
2
is monoclinic. The X-ray diffraction patterns for samples
with x = 0, 0.3, 0.5, 0.7 and 1.0 are shown in Figure 3 below.


Figure 3

16. [7 points] Based on the diffraction patterns shown in Figure 3 which of the
following statements is true?
a. One can substitute more TiO
2
into ZrO
2
than one can substitute ZrO
2

into TiO
2

b. TiO
2
and ZrO
2
form a homogeneous solid solution for all compositions
c. The Ti
0.7
Zr
0.3
O
2
sample is a heterogeneous mixture
d. The Ti
0.5
Zr
0.5
O
2
sample is a heterogeneous mixture
e. From the shifts of the peaks between TiO
2
and Ti
0.7
Zr
0.3
O
2
we can
see that Zr
4+
is smaller than Ti
4+
.


Four potential phase diagrams for the TiO
2
-ZrO
2
system are shown below.

17. [7 points] Which one of the phase diagrams for the TiO
2
-ZrO
2
system is
consistent with the X-ray diffraction patterns shown in Figure 3?
(a) I (b) II (c) III (d) IV

18. [7 points] For each of the following substances assign the electronic
excitation that responsible for the color to one of the following types: (i) d-
to-d transitions, (b) charge transfer transitions, (c) band to band
transitions, or (d) pi bonding to pi antibonding transitions.
Cu(ClO
4
)
2
ZnSe SnS
2
chlorophyll
BiVO
4
RuO
4
[Ni(NH
3
)
6
]
2+
AgI

How many examples of each type of transition are present among these eight
compounds?
a. d-to-d = 2 charge transfer = 2 band to band = 2 to
*
= 2
b. d-to-d = 2 charge transfer = 2 band to band = 3 to
*
= 1
c. d-to-d = 3 charge transfer = 2 band to band = 2 to
*
= 1
d. d-to-d = 3 charge transfer = 1 band to band = 2 to
*
= 1
e. d-to-d = 1 charge transfer = 3 band to band = 2 to
*
= 1

19. [7 points] Which of the following colors is never observed in a
semiconductor where the color comes from electronic transitions between
the valence and conduction band?
(a) Blue (b) Yellow (c) White (d) Red (e) Black


20. [7 points] Both aluminum and copper have a cubic close packed arrangement
of atoms. Aluminum bronzes are valuable alloys that from between the two
elements. They contain 4.0-9.0% aluminum by mass and the remainder is
copper. What type of alloy are the aluminum bronzes?
a. Interstitial
b. Substitutional
c. Heterogeneous
d. Intermetallic compound
e. Refractory

21. [7 points] Which of the following statements about X-ray diffraction is
false?
a. As a general rule highly symmetric crystals (i.e. cubic) give simpler
diffraction patterns than low symmetry crystals (i.e. monoclinic)
b. As the unit cell size increases the diffraction peaks shift to
higher 2 angles.
c. Amorphous solids do not diffract X-rays.
d. Each peak in the powder diffraction pattern corresponds to
scattering between different planes of atoms in the crystal
e. Both homogeneous and heterogeneous mixtures can diffract X-rays.

22. [7 points] The coordination complex [Cr(NH
3
)
4
(SCN)
2
]
+
has an octahedral
coordination sphere around the Cr
3+
center. How many possible (linkage,
geometric and/or optical) isomers are there for this coordination complex?

a. 2
b. 4
c. 6
d. 8
e. 10

23. [7 points] From Experiment 25 III, when you add concentrated ammonia to
Co
2+
you formed Co(NH
3
)
6
2+
and observed the color of the solution to be pink (pink is
essentially light red). Based on the color of this solution, what color would you
expect for Co(CN)
6
3
, CoCl
6
3-
, and Co(H
2
O)
6
3+
respectively?

(a) [Co(CN)
6
]
3
= violet, [CoCl
6
]
3
= orange-yellow, [Co(H
2
O)
6
]
3+
= blue-green
(b) [Co(CN)
6
]
3
= orange-yellow, [CoCl
6
]
3
= violet, [Co(H
2
O)
6
]
3+
= blue-green
(c) [Co(CN)
6
]
3
= orange-yellow, [CoCl
6
]
3
= blue-green, [Co(H
2
O)
6
]
3+
= violet
(d) [Co(CN)
6
]
3
= violet, [CoCl
6
]
3
= blue-green, [Co(H
2
O)
6
]
3+
= orange-yellow

24. [7 points] Consider the following equations:

[Ni(H
2
O)
6
]
2+
(aq) + 6 NH
3
(aq) [Ni(NH
3
)
6
]
2+
(aq) + 6 H
2
O (l) (1)

[Ni(H
2
O)
6
]
2+
(aq) + 3 en (aq) [Ni(en)
3
]
2+
(aq) + 6 H
2
O (l) (2)

where en = the bidentate ligand ethylene diamine, NH
2
CH
2
CH
2
NH
2
.

Which of the following statements is/are true?

I The equilibrium constant for Equation 2, K
2
, is larger than the
equilibrium constant for Equation 1, K
1
.
II The entropy change for Equation 1, S
1
, is more positive than the
entropy change for Equation 2, S
2
.
III The addition of heat to both equations favors the formation of the
products.
IV The d-d transitions in [Ni(en)
3
]
2+
are higher in energy than those in
[Ni(H
2
O)
6
]
2+
.


(a) I, II, and III only
(b) I, III, and IV only
(c) II, III, and IV only
(d) II and IV only
(e) I and IV only


25. [6 points] Aluminium phosphide, AlP, has a band gap of 2.2 eV. What color
would you expect AlP to be?

(a) yellow
(b) violet
(c) blue
(d) green
(e) red

(Actually orange might be a more logical choice than red. So I will give partial
credit, 3 points for answer (a) yellow).

26. [7 points] The two lowest energy excitations for the permanganate (MnO
4
-
) ion
are shown below in the absorption spectra. Based on the energies of these two
peaks estimate the tetrahedral field splitting (
tetr
) for MnO
4
-
.



(a) 2.3 eV
(b) 4.0 eV
(c) 5.4 eV
(d) 3.1 eV
(e) 1.7 eV

(Depending upon where you choose for the center point of the peaks you may get
slightly values ranging from 1.4-1.8 eV, but for any of these values answer (e) is the
best answer)
Physical Constants & Conversion Factors

h = 6.626 10
-34
J-s
c = 2.998 10
8
m/s
R = 8.314 J/K-mol
1 = 10 pm = 1 10
-10
m
1 eV = 1.602 10
-19
J

Approximate Wavelengths and Energies of the Visible Spectrum

Violet 400-425 nm 3.10 - 2.92 eV
Blue 425-492 nm 2.92 - 2.52 eV
Green 492-575 nm 2.52 - 2.15 eV
Yellow 575-585 nm 2.15 - 2.12 eV
Orange 585-647 nm 2.12 - 1.92 eV
Red 647-700 nm 1.92 - 1.77 eV

Equations
E = hc/ = {(6.626 x 10-34 J-s)(2.998 x 10
8
m/s)}/

Spectrochemical Series

Weak Field I

< Br

< Cl
-
< F
-
< H
2
O < NH
3
< en < NO
2
-
< CN
-
< CO Strong Field
Ligands Ligands