CHAPTER 21

TRANSITION METALS AND COORDINATION CHEMISTRY

Questions

5. The lanthanide elements are located just before the 5d transition metals. The lanthanide
contraction is the steady decrease in the atomic radii of the lanthanide elements when going
from left to right across the periodic table. As a result of the lanthanide contraction, the sizes
of the 4d and 5d elements are very similar. This leads to a greater similarity in the chemistry
of the 4d and 5d elements in a given vertical group.

6. Only the Cr3+ ion can form four different compounds with H2O ligands and Cl− ions. The Cr2+
ion could form only three different compounds, while the Cr4+ ion could form five different
compounds.

The Cl− ions that form precipitates with Ag+ are the counterions, not the ligands in the
complex ion. The four compounds and mol AgCl precipitate that would form with 1 mol of
compound are:

Compound Mol AgCl(s)

[Cr(H2O)6]Cl3 3 mol
[Cr(H2O)5Cl]Cl2 2 mol
[Cr(H2O)4Cl2]Cl 1 mol
[Cr(H2O)3Cl3] 0 mol

7.
Cl + Cl + Cl +

H3 N Cl NH3 H3 N Cl
NH3
Co Co Co
H3 N NH3 H3 N NH3 H3 N NH3

Cl NH3 H3 N

mirror
trans cis
(mirror image is The mirror image of the cis
superimposable) isomer is also superimposable.

No; both the trans and the cis forms of Co(NH3)4Cl2+ have mirror images that are superim-
posable. For the cis form, the mirror image only needs a 90° rotation to produce the original
structure. Hence neither the trans nor cis form is optically active.

837
838 CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY

8. The transition metal ion must form octahedral complex ions; only with the octahedral
geometry are two different arrangements of d electrons possible in the split d orbitals. These
two arrangements depend on whether a weak field or strong field is present. For four
unpaired electrons, the two possible weak field cases are for transition metal ions with 3d4 or
3d6 electron configurations:

small ∆ small ∆

d4 d6

Of these two, only d6 ions have no unpaired electron in the strong field case.

large ∆

Therefore, the transition metal ion has a 3d6 arrangement of electrons. Two possible metal
ions that are 3d6 are Fe2+ and Co3+. Thus one of these ions is present in the four coordination
compounds, and each of these complex ions has a coordination number of 6.

The colors of the compounds are related to the magnitude of ∆ (the d-orbital splitting value).
The weak-field compounds will have the smallest ∆, so the λ of light absorbed will be
longest. Using Table 21.16, the green solution (absorbs 650-nm light) and the blue solution
(absorbs 600-nm light) absorb the longest-wavelength light; these solutions contain the
complex ions that are the weak-field cases with four unpaired electrons. The red solution
(absorbs 490-nm light) and yellow solution (absorbs 450-nm light) contain the two strong-
field case complex ions because they absorb the shortest-wavelength (highest-energy) light.
These complex ions are diamagnetic.

9. Fe2O3(s) + 6 H2C2O4(aq) → 2 Fe(C2O4)33−(aq) + 3 H2O(l) + 6 H+(aq); the oxalate anion

forms a soluble complex ion with iron in rust (Fe2O3), which allows rust stains to be removed.

10. a.

Low Spin, large ∆ High Spin, small ∆

A d6 octahedral crystal field diagram can either be low spin (0 upaired electrons) or high
spin (4 unpaired electrons). The diagram in the question is for the low spin d6 crystal
field.
CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY 839

b.

Low Spin, large ∆ High Spin, small ∆

There is only one possible crystal field diagram for a d8 species. Hence, one cannot tell
from the diagram whether it is low spin or high spin; both have 2 unpaired electrons in
the eg orbitals.

c.

Low Spin, large ∆ High Spin, small ∆

There are two possible octahedral crystal field diagrams for a d4 species. Low spin has 2
unpaired electrons and high spin has 4 unpaired electrons. The diagram in the question is
for a high spin d4 crystal field.

11. a. CoCl42−; Co2+: 4s03d7; all tetrahedral complexes are a weak field (high spin).

CoCl42− is an example of a weak-field case

having three unpaired electrons.

small ∆

b. Co(CN)63−: Co3+ : 4s03d6; because CN− is a strong-field ligand, Co(CN)63− will be a

strong-field case (low-spin case).

CN− is a strong-field ligand, so Co(CN)63− will be

a low-spin case having zero unpaired electrons.

large ∆

12. Transition compounds exhibit the color complementary to that absorbed. From Table 21.16,
Ni(H2O)6Cl2 absorbs red light and Ni(NH3)6Cl2 absorbs yellow-green light. Ni(NH3)6Cl2
absorbs the shorter wavelength light which is the higher energy light (E = hc/λ). Therefore, Δ
is larger for Ni(NH3)6Cl2, which means that NH3 is a stronger field ligand than H2O. This is
consistent with the spectrochemical series.
840 CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY

13. From Table 21.16, the red octahedral Co(H2O)62+ complex ion absorbs blue-green light (λ ≈
490 nm), whereas the blue tetrahedral CoCl42− complex ion absorbs orange light (λ ≈ 600
nm). Because tetrahedral complexes have a d-orbital splitting much less than octahedral
complexes, one would expect the tetrahedral complex to have a smaller energy difference
between split d orbitals. This translates into longer-wavelength light absorbed (E = hc/λ) for
tetrahedral complex ions compared to octahedral complex ions. Information from Table
21.16 confirms this.

14. Co2+: [Ar]3d7; the corresponding d-orbital splitting diagram for tetrahedral Co2+ complexes
is:

All tetrahedral complexes are high spin since the d-orbital splitting is small. Ions with two or
seven d electrons should give the most stable tetrahedral complexes because they have the
greatest number of electrons in the lower-energy orbitals as compared with the number of
electrons in the higher-energy orbitals.

15. Linkage isomers differ in the way that the ligand bonds to the metal. SCN− can bond through
the sulfur or through the nitrogen atom. NO2− can bond through the nitrogen or through the
oxygen atom. OCN− can bond through the oxygen or through the nitrogen atom. N3−,
NH2CH2CH2NH2, and I− are not capable of linkage isomerism.

16. Cu2+: [Ar]3d9; Cu+: [Ar]3d10; Cu(II) is d9 and Cu(I) is d10. Color is a result of the electron
transfer between split d orbitals. This cannot occur for the filled d orbitals in Cu(I). Cd2+,
like Cu+, is also d10. We would not expect Cd(NH3)4Cl2 to be colored since the d orbitals are
filled in this Cd2+ complex.

17. Sc3+ has no electrons in d orbitals. Ti3+ and V3+ have d electrons present. The color of
transition metal complexes results from electron transfer between split d orbitals. If no d
electrons are present, no electron transfer can occur, and the compounds are not colored.

18. The maximum number of unpaired electrons is 5. This would be the case for a weak-field
(high spin) d5 transition metal ion. The crystal field diagram would be:

↑ ↑

↑ ↑ ↑

Some potential d5 ions would be Mn2+: [Ar]3d5 and Fe3+: [Ar]3d5. For a weak field, the Mn2+
ion is the better choice because it has the smaller charge. A good choice for the ligands would
be I− because it is a weak-field ligand. A potential formula for an octahedral complex ion
with 5 unpaired electrons would be MnI64−.

19. The compound is composed of CO and Ni. From the name, the formula would be Ni(CO)4.
Since the CO ligands are neutral in charge, nickel has an oxidation state of zero in Ni(CO)4.
CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY 841

20. Metals are easily oxidized by oxygen and other substances to form the metal cations. Because
of this, metals are found in nature combined with nonmetals such as oxygen, sulfur, and the
halogens. These compounds are called ores. To recover and use the metals, we must separate
them from their ores and reduce the metal ions. Then, because most metals are unsuitable for
use in the pure state, we must form alloys with the metals in order to form materials having
desirable properties.

21. At high altitudes, the oxygen content of air is lower, so less oxyhemoglobin is formed, which
diminishes the transport of oxygen in the blood. A serious illness called high-altitude sickness
can result from the decrease of O2 in the blood. High-altitude acclimatization is the
phenomenon that occurs with time in the human body in response to the lower amounts of
oxyhemoglobin in the blood. This response is to produce more hemoglobin and hence,
increase the oxyhemoglobin in the blood. High-altitude acclimatization takes several weeks
to take hold for people moving from lower altitudes to higher altitudes.

22. CN− and CO form much stronger complexes with Fe2+ than O2. Thus O2 cannot be
transported by hemoglobin in the presence of CN− or CO because the binding sites prefer the
toxic CN− and CO ligands.

Exercises
Transition Metals and Coordination Compounds
23. a. Sc: [Ar]4s23d1 b. Ru: [Kr]5s24d6*

c. Ir: [Xe]6s24f145d7 d. Mn: [Ar]4s23d5

*This is the expected electron configuration for Ru. The actual is [Kr]5s14d7.

24. Transition metal ions lose the s electrons before the d electrons.

a. Sc3+: [Ar] or [Ne]3s23p6 b. Ru2+: [Kr]4d6; Ru3+: [Kr]4d5

c. Ir+: [Xe]6s14f145d7 or [Xe]4f145d8 d. Mn2+: [Ar]3d5

Ir3+: [Xe]4f145d6

25. Transition metal ions lose the s electrons before the d electrons. Also, Pt is an exception to
the normal filling order of electrons (see Figure 7.29).

a. Co: [Ar]4s23d7 b. Pt: [Xe]6s14f145d9 c. Fe: [Ar]4s23d6

Co2+: [Ar]3d7 Pt2+: [Xe]4f145d8 Fe2+: [Ar]3d6

Co3+: [Ar]3d6 Pt4+: [Xe]4f145d6 Fe3+: [Ar]3d5

26. Cr and Cu are exceptions to the normal filling order of electrons.

842 CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY

a. Cr: [Ar]4s13d5 b. Cu: [Ar]4s13d10 c. V: [Ar]4s23d3

Cr2+: [Ar]3d4 Cu+: [Ar]3d10 V2+: [Ar]3d3

Cr3+: [Ar]3d3 Cu2+: [Ar]3d9 V3+: [Ar]3d2

27. a. With K+ and CN− ions present, iron has a 3+ charge. Fe3+: [Ar]3d5

b. With a Cl− ion and neutral NH3 molecules present, silver has a 1+ charge. Ag+:
[Kr]4d10

c. With Br− ions and neutral H2O molecules present, nickel has a 2+ charge. Ni2+:
[Ar]3d8

d. With NO2− ions, an I− ion, and neutral H2O molecules present, chromium has a 3+ charge.
Cr3+: [Ar]3d3

28. a. With NH4+ ions, Cl− ions, and neutral H2O molecules present, iron has a 2+ charge.
Fe2+: [Ar]3d6

b. With I− ions and neutral NH3 and NH2CH2CH2NH2 molecules present, cobalt has a 2+
charge. Co2+: [Ar]3d7

c. With Na+ and F− ions present, tantalum has a 5+ charge. Ta5+: [Xe]4f14 (expected)

d. Each platinum complex ion must have an overall charge if the two complex ions are
counterions to each. Knowing that platinum forms 2+ and 4+ charged ions, we can
deduce that the six coordinate complex ion has a 4+ charged platinum ion and the four
coordinate complex ion has a 2+ charged ion. With I− ions and neutral NH3 molecules
present, the two complex ions are [Pt(NH3)4I2]2+ and [PtI4]2− .

Pt2+: [Xe]4f145d8; Pt4+: [Xe]4f145d6

29. a. molybdenum(IV) sulfide; molybdenum(VI) oxide

b. MoS2, +4; MoO3, +6; (NH4)2Mo2O7, +6; (NH4)6Mo7O24•4H2O, +6

30. a. 4 O ions on faces × 1/2 O/face = 2 O ions, 2 O ions inside body; total: 4 O ions

8 Ti ions on corners × 1/8 Ti/corner + 1 Ti ion/body center = 2 Ti ions

Formula of the unit cell is Ti2O4. The empirical formula is TiO2.
+4 −2 0 0 +4 −1 +4 −2 +2 −2
b. 2 TiO2 + 3 C + 4 Cl2 → 2 TiCl4 + CO2 + 2 CO; Cl is reduced, and C is oxidized.
Cl2 is the oxidizing agent, and C is the reducing agent.
+4 −1 0 +4 −2 0
TiCl4 + O2 → TiO2 + 2 Cl2; O is reduced, and Cl is oxidized. O2 is the oxidizing
agent, and TiCl4 is the reducing agent.
CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY 843

31. NH3 is a weak base which produces OH− ions in solution. The white precipitate is
Cu(OH)2(s).

Cu2+(aq) + 2 OH−(aq) → Cu(OH)2(s)

With excess NH3 present, Cu2+ forms a soluble complex ion, Cu(NH3)42+.

Cu(OH)2(s) + 4 NH3(aq) → Cu(NH3)42+(aq) + 2 OH−(aq)

32. CN− is a weak base, so OH− ions are present that lead to precipitation of Ni(OH)2(s). As
excess CN− is added, the Ni(CN)42− complex ion forms. The two reactions are:

Ni2+(aq) + 2 OH−(aq) → Ni(OH)2(s); the precipitate is Ni(OH)2(s).

Ni(OH)2(s) + 4 CN−(aq) → Ni(CN)42−(aq) + 2 OH−(aq); Ni(CN)42− is a soluble species.

33. Only [Cr(NH3)6]Cl3 will form a precipitate since only this compound will have Cl− ions in
solution. The Cl− ions in the other compounds are ligands and are bound to the central Cr3+
ion. The Cl− ions in [Cr(NH3)6]Cl3 are counter ions needed to produce a neutral compound,
while the NH3 molecules are the ligands bound to Cr3+.

34. BaCl2 gives no precipitate, so SO42− must be in the coordination sphere (BaSO4 is insoluble).
A precipitate with AgNO3 means the Cl− is not in the coordination sphere. Because there are
only four ammonia molecules in the coordination sphere, SO42− must be acting as a bidentate
ligand. The structure is:
+
NH3
H 3N O O

Co S Cl -

H 3N O O
NH3

35. To determine the oxidation state of the metal, you must know the charges of the various
common ligands (see Table 21.13 of the text).
a. hexacyanomanganate(II) ion
b. cis-tetraamminedichlorocobalt(III) ion
c. pentaamminechlorocobalt(II) ion

36. To determine the oxidation state of the metal, you must know the charges of the various
common ligands (see Table 21.13 of the text).
a. pentaamminechlororuthenium(III) ion b. hexacyanoferrate(II) ion
c. tris(ethylenediamine)manganese(II) ion d. pentaamminenitrocobalt(III) ion
e. tetracyanonicklate(II) ion f. tetraamminedichlorochromium(III) ion
g. tris(oxalato)ferrate(III) ion h. tetraaquadithiocyanatocobalt(III) ion
844 CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY

37. a. hexaamminecobalt(II) chloride b. hexaaquacobalt(III) iodide

c. potassium tetrachloroplatinate(II) d. potassium hexachloroplatinate(II)
e. pentaamminechlorocobalt(III) chloride f. triamminetrinitrocobalt(III)

38. a. pentaaquabromochromium(III) bromide b. sodium hexacyanocobaltate(III)

c. bis(ethylenediamine)dinitroiron(III) chloride d. tetraamminediiodoplatinum(IV)
tetraiodoplatinate(II)

39. a. K2[CoCl4] b. [Pt(H2O)(CO)3]Br2

c. Na3[Fe(CN)2(C2O4)2] d. [Cr(NH3)3Cl(H2NCH2CH2NH2)]I2

40. a. FeCl4− b. [Ru(NH3)5H2O]3+

c. [Cr(CO)4(OH)2]+ d. [Pt(NH3)Cl3] −

41. a.

O
C O
C O OH 2 O
O O O
O C C
H 2O Co
Co C C
H 2O O O O
O OH 2 O
O
C
C O

cis trans

Note: C2O42− is a bidentate ligand. Bidentate ligands bond to the metal at two positions
that are 90° apart from each other in octahedral complexes. Bidentate ligands do not
bond to the metal at positions 180° apart.

b.
2+ 2+
I I
H 3N I H 3N NH3
Pt Pt
H 3N NH3 H 3N NH3
NH3 I

cis trans
i t
CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY 845

c.
Cl Cl
H 3N Cl H 3N Cl
Ir Ir
H 3N Cl H 3N NH3
NH3 Cl

d. i t

+ + +
N N N
H 3N N I N I N
Cr Cr Cr
I NH3 H 3N I H 3N NH 3
I NH3 I

Note: en = N
are abbreviations for the bidentate ligand ethylenediamine (H2NCH2CH2NH2).
N
42. a. b.

H 2C H 2N H 2C H 2N Cl
Cl NH2 CH 2
Pt Co
Cl
H 2C H 2N H 2C H 2N NH2 CH 2
Cl

c. d.
NH3 Cl
H3N Cl H3N NH3
Co Co
H3N NO2 H3N NH3
NH3 ONO

e.
2+
OH 2
H 2C H 2N NH2 CH 2
Cu
H 2C H 2N NH2 CH 2
OH 2
846 CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY

43. monodentate bidentate bridging

O O M O
M O C M C O C O
O O M O

44.
O
O C
M = transition metal ion
M
CH2
H2N

O O O

C O NH2 CH2 C O O C
Cu and Cu

H2C H2N O C H2C H2N NH2 CH2

45. a. 2; forms bonds through the lone pairs on the two oxygen atoms.

b. 3; forms bonds through the lone pairs on the three nitrogen atoms.

c. 4; forms bonds through the two nitrogen atoms and the two oxygen atoms.

d. 4; forms bonds through the four nitrogen atoms.

46. M = transition metal ion

CH2OH CH2SH

HS CH HS CH HS CH2

M M M CH SH
HS CH2 HO CH2 HO CH2
CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY 847

47. NO2 NO2 ONO

H3N NH3 O2N NH3 H3N NH3
Co Co Co
H3N NH3 H3N NH3 H3N NH3
NO2 NH3 ONO

ONO ONO ONO

ONO NH3 H3N NH3 O2N NH3
Co Co Co
H3N NH3 H3N NH3 H3N NH3
NH3 NO2 NH3

48.
H 3N SCN H 3N SCN H 3N N CS
Pt Pt Pt
N CS NH3 SCN NH3 SCN NH3

H 3N SCN H 3N N CS H 3N N CS
Pt Pt Pt
H 3N SCN H 3N SCN H 3N N CS

49. Similar to the molecules discussed in Figures 21.16 and 21.17 of the text, Cr(acac)3 and cis-
Cr(acac)2(H2O)2 are optically active. The mirror images of these two complexes are
nonsuperimposable. There is a plane of symmetry in trans-Cr(acac)2(H2O)2, so it is not
optically active. A molecule with a plane of symmetry is never optically active because the
mirror images are always superimposable. A plane of symmetry is a plane through a molecule
where one side reflects the other side of the molecule.

50. There are five geometrical isomers (labeled i-v). Only isomer v, where the CN−, Br−, and
H2O ligands are cis to each other, is optically active. The nonsuperimposable mirror image is
shown for isomer v.

i CN ii OH2 iii Br
Br OH2 Br CN H2O CN
Pt Pt Pt
Br OH2 Br CN H2O CN
CN OH2 Br

iv OH2 v CN NC
Br CN Br CN NC Br
Pt Pt Pt
NC Br Br OH2 H2O Br
OH2 OH2 H2O
optically mirror mirror image of v
active (nonsuperimposable)
848 CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY

Bonding, Color, and Magnetism in Coordination Compounds

51. NH3 and H2O are neutral charged ligands, while chloride and bromide are 1− charged ligands.
The metal ions in the three compounds are Cr3+: [Ar]d3, Co3+: [Ar]d6, and Fe3+: [Ar]d5.

a. With five electrons each in a different orbital, this diagram is for the weak-field
[Fe(H2O)6]3+ complex ion.

b. With three electrons, this diagram is for the [Cr(NH3)5Cl]2+ complex ion.

c. With six electrons all paired up, this diagram is for the strong-field [Co(NH3)4Br2]+
complex ion.

52. The metal ions are both d5 (Fe3+: [Ar]d5 and Mn2+: [Ar]d5). One of the diagrams (a) is for a
weak-field (high-spin) d5 complex ion while the other diagram (b) is for a strong-field (low-
spin) d5 complex ion. From the spectrochemical series, CN− is a strong-field ligand while
H2O is in the middle of the series. Because the iron complex ion has CN− for the ligands as
well as having a higher metal ion charge (+3 vs. +2), one would expect [Fe(CN)6]3− to have
the strong-field diagram in b, while [Mn(H2O)6]2+ would have the weak-field diagram in a.

53. a. Fe2+: [Ar]3d6

↑ ↑

↑↓ ↑ ↑ ↑↓ ↑↓ ↑↓

High spin, small ∆ Low spin, large ∆

b. Fe3+: [Ar]3d5 c. Ni2+: [Ar]3d8

↑ ↑
↑ ↑
↑ ↑ ↑

↑↓ ↑↓ ↑↓
High spin, small ∆

54. a. Zn2+: [Ar]3d10

↑↓ ↑↓

↑↓ ↑↓ ↑↓
CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY 849

b. Co2+: [Ar]3d7

↑
↑ ↑

↑↓ ↑↓ ↑ ↑↓ ↑↓ ↑↓

High spin, small ∆ Low spin, large ∆

c. Ti3+: [Ar]3d1

55. Because fluorine has a −1 charge as a ligand, chromium has a +2 oxidation state in CrF64−.
The electron configuration of Cr2+ is [Ar]3d4. For four unpaired electrons, this must be a
weak-field (high-spin) case where the splitting of the d-orbitals is small and the number of
unpaired electrons is maximized. The crystal field diagram for this ion is:

small ∆
↑ ↑ ↑

56. NH3 and H2O are neutral ligands, so the oxidation states of the metals are Co3+ and Fe2+.
Both have six d electrons ([Ar]3d6). To explain the magnetic properties, we must have a
strong-field for Co(NH3)63+ and a weak-field for Fe(H2O)62+.

Co3+: [Ar]3d6 Fe2+: [Ar]3d6

↑ ↑
large ∆ small ∆
↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑

Only this splitting of d-orbitals gives a diamagnetic Co(NH3)63+ (no unpaired electrons) and a
paramagnetic Fe(H2O)62+ (unpaired electrons present).

57. To determine the crystal field diagrams, you need to determine the oxidation state of the tran-
sition metal, which can only be determined if you know the charges of the ligands (see Table
21.13). The electron configurations and the crystal field diagrams follow.
850 CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY

a. Ru2+: [Kr]4d6, no unpaired e- b. Ni2+: [Ar]3d8, 2 unpaired e-

↑ ↑

↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

Low spin, large ∆

c. V3+: [Ar]3d2, 2 unpaired e-

↑ ↑

Note: Ni2+ must have 2 unpaired electrons, whether high-spin or low-spin, and V3+ must
have 2 unpaired electrons, whether high-spin or low-spin.

58. In both compounds, iron is in the +3 oxidation state with an electron configuration of [Ar]3d5.
Fe3+ complexes have one unpaired electron when a strong-field case and five unpaired
electrons when a weak-field case. Fe(CN)62− is a strong-field case, and Fe(SCN)63− is a weak-
field case. Therefore, cyanide (CN−) is a stronger-field ligand than thiocyanate (SCN−).

59. All have octahedral Co3+ ions, so the difference in d orbital splitting and the wavelength of
light absorbed only depends on the ligands. From the spectrochemical series, the order of the
ligands from strongest to weakest field is CN− > en > H2O > I−. The strongest-field ligand
produces the greatest d-orbital splitting (largest ∆) and will absorb light having the smallest
wavelength. The weakest-field ligand produces the smallest ∆ and absorbs light having the
longest wavelength. The order is:

Co(CN)63− < Co(en)33+ < Co(H2O)63+ < CoI63−

shortest λ absorbed longest λ absorbed

60. Replacement of water ligands by ammonia ligands resulted in shorter wavelengths of light
being absorbed. Energy and wavelength are inversely related, so the presence of the NH3
ligands resulted in a larger d-orbital splitting (larger ∆). Therefore, NH3 is a stronger-field
ligand than H2O.

61. From Table 21.16 of the text, the violet complex ion absorbs yellow-green light (λ ≈ 570 nm),
the yellow complex ion absorbs blue light (λ ≈ 450 nm), and the green complex ion absorbs
red light (λ ≈ 650 nm). The spectrochemical series shows that NH3 is a stronger-field ligand
than H2O, which is a stronger-field ligand than Cl−. Therefore, Cr(NH3)63+ will have the
largest d-orbital splitting and will absorb the lowest-wavelength electromagnetic radiation (λ
≈ 450 nm) since energy and wavelength are inversely related (λ = hc/E). Thus the yellow
solution contains the Cr(NH3)63+ complex ion. Similarly, we would expect the Cr(H2O)4Cl2+
complex ion to have the smallest d-orbital splitting since it contains the weakest-field ligands.
CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY 851

The green solution with the longest wavelength of absorbed light contains the Cr(H2O)4Cl2+
complex ion. This leaves the violet solution, which contains the Cr(H2O)63+ complex ion.
This makes sense because we would expect Cr(H2O)63+ to absorb light of a wavelength
between that of Cr(NH3)63+ and Cr(H2O)4Cl2+.

62. All these complex ions contain Co3+ bound to different ligands, so the difference in d-orbital
splitting for each complex ion is due to the difference in ligands. The spectrochemical series
indicates that CN− is a stronger-field ligand than NH3 which is a stronger-field ligand than F−.
Therefore, Co(CN)63− will have the largest d-orbital splitting and will absorb the lowest-
wavelength electromagnetic radiation (λ = 290 nm) since energy and wavelength are
inversely related (λ = hc/E). Co(NH3)63+ will absorb 440-nm electromagnetic radiation, while
CoF63− will absorb the longest-wavelength electromagnetic radiation (λ = 770 nm) since F− is
the weakest-field ligand present.

63. CoBr64− has an octahedral structure, and CoBr42− has a tetrahedral structure (as do most Co2+
complexes with four ligands). Coordination complexes absorb electromagnetic radiation
(EMR) of energy equal to the energy difference between the split d-orbitals. Because the
tetrahedral d-orbital splitting is less than one-half the octahedral d-orbital splitting, tetrahedral
complexes will absorb lower energy EMR, which corresponds to longer-wavelength EMR (E
= hc/λ). Therefore, CoBr62− will absorb EMR having a wavelength shorter than 3.4 × 10 −6 m.

64. In both complexes, nickel is in the +2 oxidation state: Ni2+: [Ar]3d8. The differences in
unpaired electrons must be due to differences in molecular structure. NiCl42− is a tetrahedral
complex, and Ni(CN)42− is a square planar complex. The corresponding d-orbital splitting
diagrams are:

↑↓
↑↓ ↑ ↑

↑↓ ↑↓ ↑↓

↑↓ ↑↓

NiCl42− Ni(CN)42−

65. Because the ligands are Cl−, iron is in the +3 oxidation state. Fe3+: [Ar]3d5

↑ ↑ ↑
Because all tetrahedral complexes are high spin,
↑ ↑ there are 5 unpaired electrons in FeCl4−.

66. Pd is in the +2 oxidation state in PdCl42−; Pd2+: [Kr]4d8. If PdCl42− were a tetrahedral
complex, then it would have 2 unpaired electrons and would be paramagnetic (see diagram
below). Instead, PdCl42− has a square planar molecular structure with the d-orbital splitting
852 CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY

diagram also shown below. Note that all electrons are paired in the square planar diagram;
this explains the diamagnetic properties of PdCl42−.

↑↓
↑↓ ↑ ↑

↑↓ ↑↓ ↑↓

↑↓ ↑↓

tetrahedral d8 square planar d8

Metallurgy
67. a. To avoid fractions, let’s first calculate ΔH for the reaction:
6 FeO(s) + 6 CO(g) → 6 Fe(s) + 6 CO2(g)

6 FeO + 2 CO2 → 2 Fe3O4 + 2 CO ΔH° = −2(18 kJ)

2 Fe3O4 + CO2 → 3 Fe2O3 + CO ΔH° = −(−39 kJ)
3 Fe2O3 + 9 CO → 6 Fe + 9 CO2 ΔH° = 3(−23 kJ)
6 FeO(s) + 6 CO(g) → 6 Fe(s) + 6 CO2(g) ΔH° = −66 kJ
− 66 kJ
So for: FeO(s) + CO(g) → Fe(s) + CO2(g) ΔH° = = −11 kJ
6
b. ΔH° = 2(−110.5 kJ) − (−393.5 kJ + 0) = 172.5 kJ

ΔS° = 2(198 J/K) − (214 J/K + 6 J/K) = 176 J/K

ΔH o 172.5 kJ
ΔG° = ΔH° − TΔS°, ΔG° = 0 when T = = = 980. K
ΔS o
0.176 kJ/K
Due to the favorable ΔS° term, this reaction is spontaneous at T > 980. K. From Figure
21.36 of the text, this reaction takes place in the blast furnace at temperatures greater than
980. K, as required by thermodynamics.

68. a. ∆H° = 2(−1117) + (−393.5) − [3(−826) + (−110.5)] = −39 kJ

∆S° = 2(146) + 214 − [3(90.) + 198] =38 J/K

b. ∆G° = ∆H° − T∆S°; T = 800. + 273 = 1073 K

∆G° = −39 kJ − 1073 K(0.038 kJ/K) = −39 kJ − 41 kJ = −80. kJ

CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY 853

69. Fe2O3: iron has a +3 oxidation state; Fe3O4: iron has a +8/3 oxidation state. The three iron
ions in Fe3O4 must have a total charge of +8. The only combination that works is to have two
Fe3+ ions and one Fe2+ ion per formula unit. This makes sense from the other formula for
magnetite, FeO•Fe2O3. FeO has an Fe2+ ion, and Fe2O3 has two Fe3+ ions.

70. 3 Fe + C → Fe3C; ΔH° = 21 − [3(0) + 0] = 21 kJ; ΔS° = 108 − [3(27) + 6] = 21 J/K

ΔG° = ΔH° − TΔS°; when ΔH° and ΔS° are both positive, the reaction is spontaneous at high
temperatures, where the favorable ΔS° term becomes dominant. Thus, to incorporate carbon
into steel, high temperatures are needed for thermodynamic reasons but will also be
beneficial for kinetic reasons (as the temperature increases, the rate of the reaction will
increase). The relative amount of Fe3C (cementite) that remains in the steel depends on the
cooling process. If the steel is cooled slowly, there is time for the equilibrium to shift back to
the left; small crystals of carbon form, giving a relatively ductile steel. If cooling is rapid,
there is not enough time for the equilibrium to shift back to the left; Fe3C is still present in the
steel, and the steel is more brittle. Which cooling process occurs depends on the desired
properties of the steel. The process of tempering fine-tunes the steel to the desired properties
by repeated heating and cooling.

71. Review Section 4.11 for balancing reactions in basic solution by the half-reaction method.

(2 CN− + Ag → Ag(CN)2− + e−) × 4

4 e− + O2 + 4 H+ → 2 H2O
8 CN− + 4 Ag + O2 + 4 H+ → 4 Ag(CN)2− + 2 H2O

Adding 4 OH− to both sides and canceling out 2 H2O on both sides of the equation gives the
balanced equation:

8 CN−(aq)+ 4 Ag(s) + O2(g) + 2 H2O(l) → 4 Ag(CN)2−(aq) + 4 OH−(aq)

72. Mn + HNO3 → Mn2+ + NO2

Mn → Mn2+ + 2 e− HNO3 → NO2
HNO3 → NO2 + H2O
(e− + H+ + HNO3 → NO2 + H2O) × 2

Mn → Mn2+ + 2 e−
2 e− + 2 H+ + 2 HNO3 → 2 NO2 + 2 H2O
2 H+(aq) + Mn(s) + 2 HNO3(aq) → Mn2+(aq) + 2 NO2(g) + 2 H2O(l)

Mn2+ + IO4− → MnO4− + IO3−

(4 H2O + Mn2+ → MnO4− + 8 H+ + 5 e−) × 2 (2 e− + 2 H+ + IO4− → IO3− + H2O) × 5

8 H2O + 2 Mn2+ → 2 MnO4− + 16 H+ + 10 e−

10 e + 10 H+ + 5 IO4− → 5 IO3− + 5 H2O
−

3 H2O(l) + 2 Mn2+(aq) + 5 IO4−(aq) → 2 MnO4−(aq) + 5 IO3−(aq) + 6 H+(aq)

854 CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY

Additional Exercises
73. Hg2+(aq) + 2 I−(aq) → HgI2(s), orange precipitate

HgI2(s) + 2 I−(aq) → HgI42−(aq), soluble complex ion

Hg2+ is a d10 ion. Color is the result of electron transfer between split d orbitals. This cannot
occur for the filled d orbitals in Hg2+. Therefore, we would not expect Hg2+ complex ions to
form colored solutions.

74. a. The coordination compound has the formula [Co(H2O)6]Cl2. The complex ion is
Co(H2O)62+, and the counterions are the Cl− ions. The geometry would be octahedral,
and the electron configuration of Co2+ is [Ar]3d7.

b. The coordination compound is Na3[Ag(S2O3)2].The compound consists of Na+ counter-

ions and the Ag(S2O3)23− complex ion. The complex ion is linear, and the electron
configuration of Ag+ is [Kr]4d10.

c. The reactant coordination compound is [Cu(NH3)4]Cl2. The complex ion is Cu(NH3)42+,

and the counterions are Cl− ions. The complex ion is tetrahedral (given in the question),
and the electron configuration of Cu2+ is [Ar]3d9. The product coordination compound is
[Cu(NH3)4]Cl. The complex ion is Cu(NH3)4+ with Cl− counter ions. The complex ion is
tetrahedral, and the electron configuration of Cu+ is [Ar]3d10.

304.0 g Eu 0.0967 g
75. 0.112 g Eu2O3 × = 0.0967 g Eu; mass % Eu = × 100 = 33.8% Eu
352.0 g Eu 2 O 3 0.286 g

Mass % O = 100.00 − (33.8 + 40.1 + 4.71) = 21.4% O

Assuming 100.00 g of compound:
1 mol 1 mol
33.8 g Eu × = 0.222 mol Eu; 40.1 g C × = 3.34 mol C
152.0 g 12.01 g
1 mol 1 mol
4.71 g H × = 4.67 mol H; 21.4 g O × = 1.34 mol O
1.008 g 16.00 g
3.34 4.67 1.34
= 15.0, = 21.0, = 6.04
0.222 0.222 0.222
The molecular formula is EuC15H21O6. Because each acac− ligand has a formula of C5H7O2-,
an abbreviated molecular formula is Eu(acac)3.

76. The complex ion is PtCl42−, which is composed of Pt2+ and four Cl− ligands. Pt2+:
[Xe]4f145d8. With square planar geometry, geometric (cis-trans) isomerism is possible.
Cisplatin is the cis isomer of the compound and has the following structural formula.

Cl NH3
Pt
Cl NH3
CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY 855

77. (Au(CN)2− + e− → Au + 2 CN−) × 2 E° = −0.60 V

Zn + 4 CN− → Zn(CN)42− + 2 e− −E° = 1.26 V
2 Au(CN)2−(aq) + Zn(s) → 2 Au(s) + Zn(CN)42−(aq) o
E cell = 0.66 V

ΔG° = − nFE cell

o
= −(2 mol e−)(96,485 C/mol e−)(0.66 J/C) = −1.3 × 105 J = −130 kJ
0.0591 nE o 2(0.66)
E° = log K, log K = = = 22.34, K = 1022.34 = 2.2 × 1022
n 0.0591 0.0591
Note: We carried extra significant figures to determine K.

78. a. In the following structures, we omitted the 4 NH3 ligands coordinated to the outside
cobalt atoms.

6+ 6+
Co Co
H H
OH HO
HO O O OH

Co Co Co Co

HO O O OH
OH HO
H H
Co Co

mirror

b. All are Co(III). The three “ligands” each contain 2 OH− and 4 NH3 groups. If each cobalt
is in the +3 oxidation state, then each ligand has a +1 overall charge. The 3+ charge from
the three ligands, along with the 3+ charge of the central cobalt atom, gives the overall
complex a +6 charge. This is balanced by the 6− charge of the six Cl− ions.

c. Co3+: [Ar]3d6; there are zero unpaired electrons if a low-spin (strong-field) case.

large ∆
↑↓ ↑↓ ↑↓

79. There are four geometrical isomers (labeled i-iv). Isomers iii and iv are optically active, and
the nonsuperimposable mirror images are shown.
856 CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY

i. + ii. +
Br NH3
H 3N NH2 CH 2 Br NH2 CH 2

Cr Cr

H 3N NH2 CH 2 Cl NH2 CH 2
Cl NH3

iii. + +
Br Br
Cl NH2 CH 2 H 2C H 2N Cl

Cr Cr

H 3N NH2 CH 2 H 2C H 2N NH3
NH3 H 3N

optically active mirror mirror image of iii

(nonsuperimposable)

iv. + +
Cl Cl
Br NH2 CH 2 H 2C H 2N Br

Cr Cr

H 3N NH2 CH 2 H 2C H 2N NH3
NH3 H 3N

optically active mirror mirror image of iv

(nonsuperimposable)

80. a. Be(tfa)2 exhibits optical isomerism. A representation for the tetrahedral optical isomers
is:
CH3 CF3 CF3 CH3

C O O C C O O C

HC Be CH HC Be CH

C O O C C O O C

CF3 CH3 CH3 CF3

mirror
CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY 857

Note: The dotted line indicates a bond pointing into the plane of the paper, and the
wedge indicates a bond pointing out of the plane of the paper.

b. Square planar Cu(tfa)2 molecules exhibit geometric isomerism. In one geometric isomer,
the CF3 groups are cis to each other, and in the other isomer, the CF3 groups are trans.

CF3 CF3 CF3 CH3

C O O C C O O C

HC Cu CH HC Cu CH

C O O C C O O C

CH3 CH3 CH3 CF3

cis trans

81. Octahedral Cr2+ complexes should be used. Cr2+: [Ar]3d4; high-spin (weak-field) Cr2+ com-
plexes have 4 unpaired electrons, and low-spin (strong-field) Cr2+ complexes have 2 unpaired
electrons. Ni2+: [Ar]3d8; octahedral Ni2+ complexes will always have 2 unpaired electrons,
whether high or low spin. Therefore, Ni2+ complexes cannot be used to distinguish weak-
from strong-field ligands by examining magnetic properties. Alternatively, the ligand field
strengths can be measured using visible spectra. Either Cr2+ or Ni2+ complexes can be used
for this method.

82. a. sodium tris(oxalato)nickelate(II) b. potassium tetrachlorocobaltate(II)

c. tetraamminecopper(II) sulfate

d. chlorobis(ethylenediamine)thiocyanatocobalt(III) chloride

83. a. [Co(C5H5N)6]Cl3 b. [Cr(NH3)5I]I2 c. [Ni(NH2CH2CH2NH2)3]Br2

d. K2[Ni(CN)4] e. [Pt(NH3)4Cl2][PtCl4]

84. a. Ru(phen)32+ exhibits optical isomerism [similar to Co(en)33+ in Figure 21.16 of the text].

b. Ru2+: [Kr]4d6; because there are no unpaired electrons, Ru2+ is a strong-field (low-spin)
case.

large ∆
↑↓ ↑↓ ↑↓
858 CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY

85. Because each compound contains an octahedral complex ion, the formulas for the compounds
are [Co(NH3)6]I3, [Pt(NH3)4I2]I2, Na2[PtI6], and [Cr(NH3)4I2]I. Note that in some cases the I−
ions are ligands bound to the transition metal ion as required for a coordination number of 6,
while in other cases the I− ions are counter ions required to balance the charge of the complex
ion. The AgNO3 solution will only precipitate the I− counterions and will not precipitate the
I− ligands. Therefore, 3 moles of AgI will precipitate per mole of [Co(NH3)6]I3, 2 moles of
AgI will precipitate per mole of [Pt(NH3)4I2]I2, 0 moles of AgI will precipitate per mole of
Na2[PtI6], and l mole of AgI will precipitate per mole of [Cr(NH3)4I2]I.

86. a. Major species: Co(H2O)63+ (Ka = 1.0 × 10 −5 ), Cl− (neutral), and H2O (Kw = 1.0 × 10 −14 );
Co(H2O)63+ will determine the pH because it is a stronger acid than water. Solving the
weak acid problem in the usual manner:

Co(H2O)63+ ⇌ Co(H2O)5(OH)2+ + H+ Ka = 1.0 × 10 −5

Initial 0.10 M 0 ~0
Equil. 0.10 – x x x

x2 x2
Ka = 1.0 × 10 −5 = ≈ , x = [H+] = 1.0 × 10 −3 M; assumptions good.
0.10 − x 0.10
pH = –log(1.0 × 10 −3 ) = 3.00

b. As the charge on the metal ion increases, acid strength increases. Because of the lower
charge, Co2+(aq) will not be as strong an acid as Co3+(aq), so a solution of cobalt(II)
nitrate will be less acidic (have a higher pH) than a solution with the same concentration
of cobalt(III) nitrate.

c. As the charge on the metal ion increases, the splitting of the d orbitals increases. Co3+
ions ([Ar]d6) produce a strong-field case (low spin) and have 0 unpaired electrons as
shown below. The lower charged Co2+ ions ([Ar]3d7) produce a weak-field case (high
spin) and have 3 unpaired electrons.

d6 low spin, large ∆ d7 high spin, small ∆

87. HbO2 → Hb + O2 ΔG° = −(−70 kJ)

Hb + CO → HbCO ΔG° = −80 kJ
HbO2(aq) + CO(g) → HbCO(aq) + O2(g) ΔG° = −10 kJ
 − ΔG o   − (−10 × 10 3 J) 
ΔG° = −RT ln K, K = exp   = exp 
  = 60
 RT   (8.3145 J/K • mol)(298 kJ) 
CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY 859

88. Cl 2+

H3N NH3
Co
H3N NH3
NH3

To form the trans isomer, Cl− would replace the NH3 ligand that is bold in the structure
above. If any of the other four NH3 molecules are replaced by Cl−, the cis isomer results.
Therefore, the expected ratio of the cis:trans isomer in the product is 4 : 1.

ChemWork Problems
89. a. [Ar]4s13d10 is correct for Cu. b. correct; c. correct

d. [Xe]6s25d1 is correct for La. e. correct

90. a. The structure of cis-Pt(NH3)Cl2:

Cl NH3
Pt
Cl NH3

Its mirror image will be superimposable, so cis-Pt(NH3)Cl2 is not optically active.

b. Similar to the trans isomer examined in Figure 21.17a of the text, trans-Ni(en)2(Br)2 will
not be optically active because its mirror image is superimposable.

c. Similar to the cis isomer examined in Figure 21.17b, cis-Ni(en)2(Br)2 will be optically
active because its mirror image is not superimposable.

d. When a tetrahedral central atom has four different groups bonded to it, the molecule or
ion will always be optically active. So yes, this tetrahedral ion with Co2+ bonded to F−,
Cl−, Br−, and I− will be optically active (the mirror image will not be superimposable).

91. Zn2+: [Ar]3d10; Cu2+: [Ar]3d9; Mn3+: [Ar]3d4; Ti4+: [Ne]3s23p6; color is a result of the
electron transfer between split d orbitals. This cannot occur for the filled d orbitals in Zn2+.
This also cannot occur for Ti4+ which has no d electrons. So Zn2+ and Ti4+ compounds/ions
will not be colored. Cu2+ and Mn3+ do have d orbitals that are partially filled, so we would
expect compounds/ions of Cu2+ and Mn3+ to be colored.
860 CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY

92. The oxidation state of iron in Fe(CNS)64− and Fe(CN)64− is +2. The electron configuration of
Fe2+ is [Ar]3d6. The two possible crystal field diagrams for octahedral d6 ions are:

↑ ↑

↑↓ ↑ ↑ ↑↓ ↑↓ ↑↓

High spin, small ∆ Low spin, large ∆

Because both Fe(CNS)64− and Fe(CN)64− have 0 unpaired electrons, they both are strong field
(low spin) cases.

CoCl42− is a tetrahedral complex ion. All tetrahedral complex ions are weak field. In this
complex ion, cobalt has a +2 oxidation state with a [Ar]3d7 electron configuration. The
tetrahedral d7 crystal field diagram showing 3 unpaired electrons is:

Fe(H2O)63+ has iron in the +3 oxidation state with an [Ar]3d5 electron configuration. In order
for this complex ion to have 5 unpaired electrons, this must be a weak field (high spin) case.
The crystal field diagram is:

↑ ↑

↑ ↑ ↑

High spin, small ∆

93. a. Zn2+ has a 3d10 electron configuration. This diagram is for a d10 octahedral complex ion,
not a d10 tetrahedral complex as is given. So this diagram is incorrect.

b. This diagram is correct. In this complex ion, Mn has a +3 oxidation state and an [Ar]3d4
electron configuration. This strong field diagram for a d4 ion is shown.

c. This diagram is correct. In this complex ion, Ni2+ is present which has a 3d8 electron
configuration. The diagram shown is correct for a diamagnetic square planar complex.

94. a. False; the coordination number is 6.

b. False; all tetrahedral complex ions are high-spin (weak field).

c. True; d. False; [Xe]4f145d2 is the correct electron configuration for Hf2+.

e. False; hemoglobin contains Fe2+ ions, not Fe3+ ions.

CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY 861

Challenge Problems
95. Ni2+ = d8; if ligands A and B produced very similar crystal fields, the cis-[NiA2B4]2+
complex ion would give the following octahedral crystal field diagram for a d8 ion:

This is paramagnetic.

Because it is given that the complex ion is diamagnetic, the A and B ligands must produce
different crystal fields, giving a unique d-orbital splitting diagram that would result in a
diamagnetic species.

96. Cr3+: [Ar]d3; looking at Figure 21.20 of the text, the d z 2 orbital will be destabilized the most
when stronger field ligands are on the z-axis. The dxy orbital will be destabilized the least by
this arrangement of ligands. Assuming the A ligands produce a significantly stronger field
than the B ligands, we will assume the dxz and dyz orbitals will be destabilized the second
most of all the orbitals due to the lobes of these orbitals lying in the z-axis plane. This leaves
the d x 2 − y 2 orbitals, whose relative position is very difficult to predict. We will assume the
d x 2 − y 2 orbital is destabilized more than the dxy orbital because the lobes point directly at the
B ligands, but is not destabilized as much as the other orbitals which all have lobes in the z-
plane. Making these assumptions, the d-orbital splitting diagram is (assuming a low-spin
case):
dz2

d xz , d yz

dx2 − y2

d xy

Note: It could be that the relative positions of the d x 2 − y 2 with the dxz and dyz orbitals are
switched.

97. a. Consider the following electrochemical cell:

Co3+ + e− → Co2+ E° = 1.82 V

Co(en)32+ → Co(en)33+ + e− −E° = ?
Co3+ + Co(en)32+ → Co2+ + Co(en)33+ E ocell = 1.82 − E°
862 CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY

The equilibrium constant for this overall reaction is:

Co3+ + 3 en → Co(en)33+ K1 = 2.0 × 1047

Co(en)32+ → Co2+ + 3 en K2 = 1/1.5 × 1012
2.0 × 10 47
Co3+ + Co(en)32+ → Co(en)33+ + Co2+ K = K1K2 = = 1.3 × 1035
1.5 × 1012
From the Nernst equation for the overall reaction:
0.0591 0.0591
E ocell = log K = log(1.3 × 10 35 ), E ocell = 2.08 V
n 1
E ocell = 1.82 − E° = 2.08 V, E° = 1.82 V − 2.08 V = −0.26 V

b. The stronger oxidizing agent will be the more easily reduced species and will have the
more positive standard reduction potential. From the reduction potentials, Co3+ (E° =
1.82 V) is a much stronger oxidizing agent than Co(en)33+ (E° = −0.26 V).

c. In aqueous solution, Co3+ forms the hydrated transition metal complex Co(H2O)63+. In
both complexes, Co(H2O)63+ and Co(en)33+, cobalt exists as Co3+, which has 6 d electrons.
Assuming a strong-field case for each complex ion, the d-orbital splitting diagram for
each is:
eg

↑↓ ↑↓ ↑↓ t2g

When each complex gains an electron, the electron enters a higher energy eg orbital.
Since en is a stronger-field ligand than H2O, the d-orbital splitting is larger for Co(en)33+,
and it takes more energy to add an electron to Co(en)33+ than to Co(H2O)63+. Therefore, it
is more favorable for Co(H2O)63+ to gain an electron than for Co(en)33+ to gain an
electron.

II III III II
98. (H2O)5Cr‒Cl‒Co(NH3)5 → (H2O)5Cr‒Cl‒Co(NH3)5 → Cr(H2O)5Cl2+ + Co(II) complex

Yes; after the oxidation, the ligands on Cr(III) won't exchange. Since Cl− is in the
coordination sphere, it must have formed a bond to Cr(II) before the electron transfer
occurred (as proposed through the formation of the intermediate).

99. No; in all three cases, six bonds are formed between Ni2+ and nitrogen, so ΔH values should
be similar. ΔS° for formation of the complex ion is most negative for 6 NH3 molecules
reacting with a metal ion (7 independent species become 1). For penten reacting with a metal
ion, 2 independent species become 1, so ΔS° is least negative of all three of the reactions.
Thus the chelate effect occurs because the more bonds a chelating agent can form to the
metal, the less unfavorable ΔS° becomes for the formation of the complex ion, and the larger
the formation constant.
CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY 863

100. ____ ____ dx2 , d xy

− y2
z axis
L (pointing out ____ dz2
of the plane
M L of the paper)
L ____ ____ d xz , d yz

The d x 2 − y 2 and dxy orbitals are in the plane of the three ligands and should be destabilized the
most. The amount of destabilization should be about equal when all the possible interactions
are considered. The d z 2 orbital has some electron density in the xy plane (the doughnut) and
should be destabilized a lesser amount than the d x 2 − y 2 and dxy orbitals. The dxz and dyz
orbitals have no electron density in the plane and should be lowest in energy.

101. ____ dz2

L z axis
L (pointing out ____ ____ d x 2 − y 2 , d xy
M L of the plane
L of the paper)
____ ____ d xz , d yz
L

The d z 2 orbital will be destabilized much more than in the trigonal planar case (see Exercise
100). The d z 2 orbital has electron density on the z axis directed at the two axial ligands. The
d x 2 − y 2 and dxy orbitals are in the plane of the three trigonal planar ligands and should be
destabilized a lesser amount than the d z 2 orbital; only a portion of the electron density in the
d x 2 − y 2 and dxy orbitals is directed at the ligands. The dxz and dyz orbitals will be destabilized
the least since the electron density is directed between the ligands.

102. For a linear complex ion with ligands on the x axis, the d x 2 − y 2 orbital will be destabilized
the most, with the lobes pointing directly at the ligands. The dyz orbital has the fewest
interactions with x-axis ligands, so it is destabilized the least. The dxy and dxz orbitals will
have similar destabilization but will have more interactions with x-axis ligands than the dyz
orbital. Finally, the d z 2 orbital with the doughnut of electron density in the xy plane will
probably be destabilized more than the dxy and dxz orbitals but will have nowhere near the
amount of destabilization that occurs with the d x 2 − y 2 orbital. The only difference that would
occur in the diagram if the ligands were on the y axis is the relative positions of the dxy, dxz,
and dyz orbitals. The dxz will have the smallest destabilization of all these orbitals, whereas the
dxy and dyz orbitals will be degenerate since we expect both to be destabilized equivalently
from y-axis ligands. The d-orbital splitting diagrams are:
864 CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY

a. b.
dx2 − y2 dx2 − y2
dz2 dz2

d xy , d xz d xy , d yz
d yz d xz

linear x-axis ligands linear y-axis ligands

103. Ni2+: [Ar]3d8; the coordinate system for trans-[Ni(NH3)2(CN)4]2− is shown below. Because
CN− produces a much stronger crystal field, it will dominate the d-orbital splitting. From the
coordinate system, the CN− ligands are in a square planar arrangement. Therefore, the
diagram will most likely resemble the square planar diagram given in Figure 21.28. Note that
the relative position of d z 2 orbital is hard to predict. With the NH3 ligands on the z axis, we
will assume the dz2 orbital is destabilized more than the dxy orbital. However, this is only an
assumption. It could be that the dxy orbital is destabilized more.

NH3 y dx2 − y2
NC CN
Ni dz2
NC CN
dxy
NH3 x
dxz dyz
z

104. We need to calculate the Pb2+ concentration in equilibrium with EDTA4-. Because K is large
for the formation of PbEDTA2-, let the reaction go to completion; then solve an equilibrium
problem to get the Pb2+ concentration.

Pb2+ + EDTA4− ⇌ PbEDTA2− K = 1.1 × 1018

Before 0.010 M 0.050 M 0
0.010 mol/L Pb2+ reacts completely (large K)
Change −0.010 −0.010 → +0.010 Reacts completely
After 0 0.040 0.010 New initial condition
x mol/L PbEDTA2− dissociates to reach equilibrium
Equil. x 0.040 + x 0.010 − x
(0.010 − x ) (0.010)
1.1 × 1018 = ≈ , x = [Pb2+] = 2.3 × 10 −19 M; assumptions good.
( x)(0.040 + x) x (0.040)
CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY 865

Now calculate the solubility quotient for Pb(OH)2 to see if precipitation occurs. The
concentration of OH− is 0.10 M because we have a solution buffered at pH = 13.00 (pOH =
14.00 − 13.00 = 1.00, [OH−] = 10−1.00).

Q = [Pb 2+ ]0 [OH − ]0 2 = (2.3 × 10 −19 )(0.10)2 = 2.3 × 10 −21 < Ksp (1.2 × 10 −15 )

Pb(OH)2(s) will not form because Q is less than Ksp.

105. AgBr(s) ⇌ Ag+ + Br- Ksp = 5.0 × 10−13

Ag+ + 2 NH3 ⇌ Ag(NH3)2+ Kf = 1.7 × 107
AgBr(s) + 2 NH3(aq) ⇌ Ag(NH3)2+(aq) + Br-(aq) K = Ksp × Kf = 8.5 × 10−6

AgBr(s) +
2 NH3 ⇌ Ag(NH3)2+ + Br−
Initial 3.0 M 0 0
If 0.10 mol of AgBr dissolves in 1.0 L, then the concentration changes would be:
Change −0.10 −0.20 → +0.10 +0.10
After 2.8 M 0.10 M 0.10 M
To check to see if all of the solid dissolves, let’s see what the reaction quotient indicates
using these concentrations.
[Ag(NH 3 ) 2+ ] o [Br − ] o (0.10)(0.10)
Q= = = 1.3 × 10−3
[NH 3 ] O2
(2.8) 2

Since Q > K (8.5 × 10−6), the reaction will shift left to establish equilibrium, causing AgBr(s)
to form. No, 0.10 mol of AgBr will not dissolve in 1.0 L of 3.0 M NH3.

Integrative Problems
106. a. Because O is in the −2 oxidation state, iron must be in the +6 oxidation state. Fe6+:
[Ar]3d2.

b. Using the half-reaction method of balancing redox reactions, the balanced equation is:

10 H+(aq) + 2 FeO42−(aq) + 2 NH3(aq) → 2 Fe3+(aq) + N2(g) + 8 H2O(l)

0.243 mol FeO 4 2− 1 mol N 2

0.0250 L × × 2−
= 3.04 × 10 −3 mol N2
L 2 mol FeO 4
(if FeO42− limiting)
1.45 mol NH 3 1 mol N 2
0.0550 L × × = 3.99 × 10 −2 mol N2 (if NH3 limiting)
L 2 mol NH 3

Because the FeO42− reagent produces the smaller quantity of N2, FeO42− is limiting and
3.04 × 10 −3 mol N2 can be produced.
866 CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY

0.08206 L atm
3.04 × 10 −3 mol N 2 × × 298 K
nRT K mol
VN 2 = =
P 1.50 atm

VN 2 = 0.0496 L = 49.6 mL N2

52.00 g Cr 0.0106 g
107. i. 0.0203 g CrO3 × = 0.0106 g Cr; % Cr = × 100 = 10.1% Cr
100.0 g CrO 3 0.105 g

0.100 mmol HCl 1 mmol NH 3 17.03 mg NH 3

ii. 32.93 mL HCl × × × = 56.1 mg NH3
mL mmol HCl mmol

56.1 mg
% NH3 = × 100 = 16.5% NH3
341 mg
iii. 73.53% + 16.5% + 10.1% = 100.1%; the compound must be composed of only Cr, NH3,
and I.

Out of 100.00 g of compound:

1 mol 0.194
10.1 g Cr × = 0.194 mol; = 1.00
52.00 g 0.194
1 mol 0.969
16.5 g NH3 × = 0.969 mol; = 4.99
17.03 g 0.194
1 mol 0.5794
73.53 g I × = 0.5794 mol; = 2.99
126.9 g 0.194
Cr(NH3)5I3 is the empirical formula. If we assume an octahedral complex ion, then
compound A is made of the octahedral [Cr(NH3)5I]2+ complex ion and two I− ions as
counterions; the formula is [Cr(NH3)5I]I2. Let’s check this proposed formula using the
freezing-point data.

iv. ΔTf = iKfm; for [Cr(NH3)5I]I2, i = 3.0 (assuming complete dissociation).

0.601 g complex 1 mol complex
Molality = m = −2
× = 0.116 mol/kg
1.000 × 10 kg H 2 O 517.9 g complex
ΔTf = 3.0 × 1.86 °C kg/mol × 0.116 mol/kg = 0.65°C

Because ΔTf is close to the measured value, this is consistent with the formula
[Cr(NH3)5I]I2. So our assumption of an octahedral complex ion is probably a good
assumption.

hc 6.626 × 10 −34 J s × 2.998 × 108 m / s

108. a. λ = = − 23
= 5.72 × 10 −7 m = 572 nm
E 1.986 × 10 J
1.75 × 10 4 cm −1 ×
cm −1
CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY 867

b. There are three resonance structures for NCS−. From a formal charge standpoint, the
following resonance structure is best.

N C S

The N in this resonance structure is sp hybridized. Because the sp hybrid orbitals are
180° apart, one would expect that when the lone pair in an sp hybrid orbital on N is
donated to the Cr3+ ion, the 180° bond angle would stay intact between Cr, N, C, and S.

Similar to Co(en)2Cl2+ discussed in Figure 21.17 of the text, [Co(en)2(NCS)2]+ would

exhibit cis-trans isomerism (geometric isomerism), and only the cis form would exhibit
optical isomerism. For [Co(en)2(NCS)2]+, NCS− just replaces the Cl− ions in the isomers
drawn in Figure 21.17. The trans isomer would not exhibit optical isomerism.

Marathon Problem
109. CrCl3•6H2O contains nine possible ligands, only six of which are used to form the octahedral
complex ion. The three species not present in the complex ion will either be counterions to
balance the charge of the complex ion and/or waters of hydration. The number of counter-
ions for each compound can be determined from the silver chloride precipitate data, and the
number of waters of hydration can be determined from the dehydration data. In all
experiments, the ligands in the complex ion do not react.

Compound I:
1 mol
mol CrCl3•6H2O = 0.27 g × = 1.0 × 10−3 mol CrCl3•6H2O
266.5 g
1 mol
mol waters of hydration = 0.036 g H2O × = 2.0 × 10−3 mol H2O
18.02 g
mol waters of hydration 2.0 × 10 −3 mol
= = 2.0
mol compound 1.0 × 10 −3 mol
In compound I, two of the H2O molecules are waters of hydration, so the other four water
molecules are present in the complex ion. Therefore, the formula for compound I must
be [Cr(H2O)4Cl2]Cl•2H2O. Two of the Cl− ions are present as ligands in the octahedral
complex ion, and one Cl− ion is present as a counterion. The AgCl precipitate data that
refer to this compound are the one that produces 1430 mg AgCl:
0.100 mol [Cr(H 2 O) 4 Cl 2 ]Cl • 2H 2 O
mol Cl− from compound I = 0.1000 L ×
L
−
1 mol Cl
× = 0.0100 mol Cl−
mol [Cr(H 2 O) 4 Cl 2 ]Cl • 2H 2 O

1 mol AgCl 143.4 g AgCl

mass AgCl produced = 0.0100 mol Cl− × −
× = 1.43 g
mol Cl mol AgCl
= 1430 mg AgCl
868 CHAPTER 21 TRANSITION METALS AND COORDINATION CHEMISTRY

Compound II:
1 mol
0.018 g H 2 O ×
mol waters of hydration 18.02 g
= = 1.0
mol compound 1.0 × 10 −3 mol compound
The formula for compound II must be [Cr(H2O)5Cl]Cl2•H2O. The 2870-mg AgCl
precipitate data refer to this compound. For 0.0100 mol of compound II, 0.0200 mol Cl−
is present as counterions:
1 mol AgCl 143.4 g
mass AgCl produced = 0.0200 mol Cl− × −
× = 2.87 g
mol Cl mol
= 2870 mg AgCl
Compound III:

This compound has no mass loss on dehydration, so there are no waters of hydration
present. The formula for compound III must be [Cr(H2O)6]Cl3. 0.0100 mol of this
compound produces 4300 mg of AgCl(s) when treated with AgNO3.
1 mol AgCl 143.4 g AgCl
0.0300 mol Cl− × −
× = 4.30 g = 4.30 × 103 mg AgCl
mol Cl mol AgCl

The structural formulas for the compounds are:

Compound I

Cl + Cl +
H2O OH2 H2O Cl
Cr Cl • 2 H2O Cr Cl • 2 H2O
or
H2O OH2 H2O OH2
Cl OH2

Compound II Compound III

2+ OH2 3+
Cl
H2O OH2 H2O OH2
Cr Cr
Cl2 • H2O H2O OH2
Cl3
H2O OH2
OH2 OH2

From Table 21.16 of the text, the violet compound will be the one that absorbs light with the
shortest wavelength (highest energy). This should be compound III. H2O is a stronger-field
ligand than Cl−; compound III with the most coordinated H2O molecules will have the largest
d-orbital splitting and will absorb the higher-energy light.

The magnetic properties would be the same for all three compounds. Cr3+ is a d3 ion. With
only three electrons present, all Cr3+complexes will have three unpaired electrons, whether
strong field or weak field. If Cr2+was present with the d4 configuration, then the magnetic
properties might be different for the complexes and could be worth examining.