CHM 3609 Inorganic Chemistry: Homework 10

Practice Questions:
100 points total
Note: Answers should be neatly written in separate papers with question number clearly
indicated
1. The most intense absorption band in the visible spectrum of [Mn(H2O)6]2+ is at 24,900 cm-1
and has a molar absorptivity of 0.038 L mol-1 cm-1. What concentration of [Mn(H2O)6]2+ would
be necessary to give an absorbance of 0.10 in a cell of path length 1.00 cm?

L
Answer e = 0.038 A = 0.10 l = 1.00cm
mol cm
A 0.10 mol
A = elc; c = = = 2.6
el æ L ö L
ç 0.038 ÷ (1.00cm)
è mol cmø

2. For each of the following free-ion terms, determine the values of L, and S, and draw a possible
d-orbital electron configuration that is consistent with the free-ion term:
a. 2D (d3) b. 3G (d4) c. 4F (d7)

a. L = 2, S = 1/2, b. L = 4, S = 1,

c. L = 3, S = 3/2,

3. Determine the ground terms for the following configurations:

a. 3F b. 6S
c. 5D d. 2D

4. From the following spectral data, and using Tanabe–Sugano diagrams, calculate Δo for the
following:
a. [Cr(C2O4)3]3-, which has absorption bands at 23,600 and 17,400 cm-1. A third band occurs
well into the ultraviolet.
b. [Ti(NCS)6]3-, which has an asymmetric, slightly split band at 18,400 cm-1. (Also, suggest a
reason for the splitting of this band.)
c. [Ni(en)3]2+, which has three absorption bands: 11,200, 18,350, and 29,000 cm-1.

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 d. [VF6]3-, which has absorption bands at 14,800 and 23,250 cm-1, plus a third band in the
ultraviolet. Also calculate B for this ion.
e. The complex VCl3(CH3CN)3, which has absorption bands at 694 and 467 nm. Calculate Δo
and B for this complex.

a. [Cr(C2O4)3]3– is Cr(III), d 3. o is equal to the lowest energy band, so o = 17,400 cm–1.

b. [Ti(NCS)6]3– is Ti(III), d 1. o is the energy of the single band; o = 18,400 cm–1.

c. [Ni(en)3]2+ is Ni(II), d 8. The lowest energy band corresponds to o; o = 11,200 cm–1.

d. [VF6]3– is V(III), d 2. Following the example on Miessler pp. 427 - 428, we find the ratio
2/1
and then o /B: 2/1 = 1.57 at o /B = 26. From the Tanabe-Sugano diagram at
o /B = 26,
1: E/B = 24.1 E = 24.1 B = 14,800 cm–1 B = 614 cm–1
2: E/B = 37.0 E = 37.0 B = 23,250 cm–1 B = 628 cm–1
Average B = 621 cm–1, o = 26 B = 16,100 cm–1 (On the basis of the data in this and
following problems, the values of B and o should be rounded to two significant digits;
additional digits are shown here to assist in checking calculations.)

e. V(III) is a d 2 ion. Again following the example on Miessler pp. 427 - 428, 2 = 21,413 cm–1
and 1 = 14,409 cm–1, 2/1 = 1.49. From the Tanabe-Sugano diagram at o/B = 34.5,
1: E/B = 29 E = 29 B =14,409 cm–1 B = 497 cm–1
2: E/B = 44 E = 44 B = 21,413 cm–1 B = 487 cm–1
Average B = 492 cm–1, o = 34.5 B = 16,970 cm–1

5. [Co(NH3)6]2+ has absorption bands at 9,000 and 21,100 cm-1 . Calculate Δo and B for this ion.
(Hints: The 4T1g → 4A2g transition in this complex is too weak to be observed.)

[Co(NH3)6]2+, d 7. As in Problem 4d:

2/1 = 2.34 at o/B = 11. From the Tanabe-Sugano diagram at o = 11,

1: E/B = 10 E= 10 B = 9,000 cm–1 B = 900 cm–1

2: E/B = 22.5 E= 22.5 B = 21,100 cm–1 B = 938 cm–1

Average B = 919 cm–1, o = 11 B = 10,100 cm–1

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6. An aqueous solution of Ni(NO3)2 is green. Addition of aqueous NH3 causes the color of the
solution to change to blue. If ethylenediamine is added to the green solution, the color
changes to violet. Account for the colors of these complexes. Are they consistent with the
expected positions of these ligands in the spectrochemical series?

Aqueous solutions of Ni(NO3)2 contain the green [Ni(H2O)6]2+ ion; nitrate is the counterion.
Addition of aqueous NH3 replaces the H2O ligands in [Ni(H2O)6]2+ to give blue [Ni(NH3)6]2+.
As a bidentate ligand, en can replace two NH3 ligands; three en ligands can therefore
replace all six NH3 ligands to form violet [Ni(en)3]2+:

NH3 en
[Ni(H2O)6 ]2+ [Ni(NH3)6 ]2+ [Ni(en)3]2+
observed color: green blue violet
complementary color: red orange yellow

The complementary colors in this series have increasing energies, indicating that en has
the strongest effect on o, and H2O has the weakest effect. This is consistent with the
positions of these ligands in the spectrochemical series.

7. MnO4‒ is a stronger oxidizing agent than ReO4‒. Both ions have charge-transfer bands;
however, the charge transfer band for ReO4‒ is in the ultraviolet, whereas the corresponding
band for MnO4‒ is responsible for its intensely purple color. Are the relative positions of the
charge-transfer absorptions consistent with the oxidizing abilities of these ions? Explain.

The 5d orbitals of Re are higher in energy than the 3d orbitals of Mn, so an LMCT
excitation requires more energy for ReO4–. In addition, since the molecular orbitals
derived primarily from the 3d orbitals of MnO4– are lower in energy than the
corresponding MO’s of ReO4–, MnO4– can accept electrons more easily; it is a better
oxidizing agent.

8. The complexes [Co(NH3)5X]2+ (X = Cl, Br, I) have charge transfer to metal bands. Which of
these complexes would you expect to have the lowest-energy charge-transfer band? Why?

The order of energy of the charge transfer bands is I < Br < Cl. LMCT in low-spin d6
[Co(NH3)5X]2+ can be approximated (since this complex does not have Oh symmetry) as
excitation into the LUMO (empty eg orbitals of high dz2 and dx2-y2 character) from lower
energy, relatively nonbonding (or weakly bonding π-donor) orbitals with high halide
valence orbital character. It is reasonable to approximate the LUMO energies as very
similar for this series of Co(III) cations. However, the lower-energy orbitals with high
halide valence orbital character will be lowest for the most electronegative chloride, and

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 highest for the least electronegative iodide. This difference results in [Co(NH3)5I]2+ having
the lowest-energy predicted LMCT band. From an HSAB perspective, iodide is softer and
can lose an electron most easily in an LMCT process.

9. For compound [Co(bipy)3]2+, do the following:

a. These are both high-spin d 7 complexes, for which the ground-state term symbol is 4F

b. There are three possible transitions, all originating from the 4T1(4F) and going to the
4T , 4A , and 4T (4P) levels.
2 2 1

n 2 22,000 cm–1
= = 1.95
c. For [Co(bipy)3]2+, the ratio n1 11,300 cm
–1
. From Figure 11.14 in Miessler’s
Inorganic Chemistry textbook, this

Do
= 17
comes at B , at which:

E 22,000 cm-1
= 28 and B = = 786 cm-1
for the 22,000 cm–1 band: B 28

E 11,300 cm-1
= 15 and B = = 754 cm-1
for the 11,300 cm–1 band: B 15

Do
= 17
Average B = 770 cm–1; B ; o = 13,100 cm–1

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– D o = –10,500 cm–1
For a d 7 complex, LFSE = 5