Chapter 19

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(a) Sc: [Ar]4s²3d¹; (b) Ti: [Ar]4s²3d²; (c) Cr: [Ar]4s¹3d⁵; (d) Fe: [Ar]4s²3d⁶; (e) Ru: [Kr]5s²4d⁶

(a) La: [Xe]6s²5d¹, La³⁺: [Xe]; (b) Sm: [Xe]6s²4f⁶, Sm³⁺: [Xe]4f⁵; (c) Lu: [Xe]6s²4f¹⁴5d¹, Lu³⁺: [Xe]4f¹⁴

Al is used because it is the strongest reducing agent and the only option listed that can provide sufficient driving force to convert La(III) into La.

The CaSiO₃ slag is less dense than the molten iron, so it can easily be separated. Also, the floating slag layer creates a barrier that prevents the molten iron from exposure to O₂, which would oxidize the Fe back to Fe₂O₃.

11.

2.57%

13.

0.167 V

15.

E° = −0.6 V, E° is negative so this reduction is not spontaneous. E° = +1.1 V

17.

(a) $Fe (s) + 2 H_{3} O + (a q) + {SO}_{4}^{2} − (a q) ⟶ {Fe}^{2} + (a q) + {SO}_{4}^{2} − (a q) + H_{2} (g) + 2 H_{2} O (l);$ (b) ${FeCl}_{3} (a q) + {3Na}^{+} (a q) + {3OH}^{−} (a q) ⟶ Fe {(OH)}_{3} (s) + {3Na}^{+} (a q) + {3Cl}^{+} (a q);$ (c) $Mn {(OH)}_{2} (s) + 2 H_{3} O + (a q) + {2Br}^{−} (a q) ⟶ {Mn}^{2} + (a q) + {2Br}^{−} (a q) + 4 H_{2} O (l);$ (d) $4Cr (s) + 3 O_{2} (g) ⟶ 2 {Cr}_{2} O_{3} (s);$ (e) ${Mn}_{2} O_{3} (s) + 6 H_{3} O + (a q) + {6Cl}^{−} (a q) ⟶ 2 {MnCl}_{3} (s) + 9 H_{2} O (l);$ (f) $Ti (s) + x s F_{2} (g) ⟶ {TiF}_{4} (g)$

19.

(a) ${Cr}_{2} {({SO}_{4})}_{3} (a q) + 2Zn (s) + {2H}_{3} O + (a q) ⟶ {2Zn}^{2} + (a q) + H_{2} (g) + {2H}_{2} O (l) + {2Cr}^{2 +} (a q) + {3SO}_{4}^{2} − (a q);$ (b) ${4TiCl}_{3} (s) + {CrO}_{4}^{2} − (a q) + {8H}^{+} (a q) ⟶ {4Ti}^{4} + (a q) + Cr (s) + {4H}_{2} O (l) + {12Cl}^{−} (a q);$ (c) In acid solution between pH 2 and pH 6, ${CrO}_{4}^{2} −$ forms ${HCrO}_{4}^{−},$ which is in equilibrium with dichromate ion. The reaction is ${2HCrO}_{4}^{−} (a q) ⟶ {Cr}_{2} O_{7}^{2} − (a q) + H_{2} O (l) .$ At other acidic pHs, the reaction is ${3Cr}^{2 +} (a q) + {CrO}_{4}^{2} − (a q) + {8H}_{3} O + (a q) ⟶ {4Cr}^{3} + (a q) + {12H}_{2} O (l);$ (d) ${8CrO}_{3} (s) + 9Mn (s) \overset{Δ}{⟶} {4Cr}_{2} O_{3} (s) + {3Mn}_{3} O_{4} (s);$ (e) $CrO (s) + {2H}_{3} O + (a q) + {2NO}_{3}^{−} (a q) ⟶ {Cr}^{2} + (a q) + {2NO}_{3}^{−} (a q) + {3H}_{2} O (l);$ (f) ${CrCl}_{3} (s) + 3NaOH (a q) ⟶ Cr {(OH)}_{3} (s) + {3Na}^{+} (a q) + {3Cl}^{−} (a q)$

21.

(a) $3Fe (s) + {4H}_{2} O (g) ⟶ {Fe}_{3} O_{4} (s) + {4H}_{2} (g);$ (b) $3NaOH (a q) + Fe {({NO}_{3})}_{3} (a q) \overset{H_{2} O}{\to} Fe {(OH)}_{3} (s) + {3Na}^{+} (a q) + 3 {NO}_{3}^{−} (a q);$ (c) $MnO^{4−} + 5 {Fe}^{2+} + 8 H^{+} ⟶ Mn^{2+} + 5 {Fe}_{3} + 4 H_{2} O;$ (d) $Fe (s) + {2H}_{3} O^{+} (a q) + {SO}_{4}^{2−} (a q) ⟶ {Fe}^{2+} (a q) + {SO}_{4}^{2−} (a q) + H_{2} (g) + {2H}_{2} O (l);$ (e) ${4Fe}^{2+} (a q) + O_{2} (g) + {4HNO}_{3} (a q) ⟶ {4Fe}^{3+} (a q) + {2H}_{2} O (l) + {4NO}_{3}^{−} (a q);$ (f) ${FeCO}_{3} (s) + {2HClO}_{4} (a q) ⟶ Fe {({ClO}_{4})}_{2} (a q) + H_{2} O (l) + {CO}_{2} (g);$ (g) $3Fe (s) + {2O}_{2} (g) \overset{Δ}{⟶} {Fe}_{3} O_{4} (s)$

23.

As CN⁻ is added,
${Ag}^{+} (a q) + {CN}^{−} (a q) ⟶ AgCN (s)$
As more CN⁻ is added,
$\begin{array}{l} {Ag}^{+} (a q) + 2 {CN}^{−} (a q) ⟶ {[Ag {(CN)}_{2}]}^{−} (a q) \\ AgCN (s) + {CN}^{−} (a q) ⟶ {[Ag {(CN)}_{2}]}^{−} (a q) \end{array}$

25.

(a) Sc³⁺; (b) Ti⁴⁺; (c) V⁵⁺; (d) Cr⁶⁺; (e) Mn⁴⁺; (f) Fe²⁺ and Fe³⁺; (g) Co²⁺ and Co³⁺; (h) Ni²⁺; (i) Cu⁺

27.

(a) 4, [Zn(OH)₄]²⁻; (b) 6, [Pd(CN)₆]²⁻; (c) 2, [AuCl₂]⁻; (d) 4, [Pt(NH₃)₂Cl₂]; (e) 6, K[Cr(NH₃)₂Cl₄]; (f) 6, [Co(NH₃)₆][Cr(CN)₆]; (g) 6, [Co(en)₂Br₂]NO₃

29.

(a) [Pt(H₂O)₂Br₂]:

(b) [Pt(NH₃)(py)(Cl)(Br)]:

(d) [Pt(NH₃)₃Cl]⁺ :

(e) [Ni(H₂O)₄Cl₂]:

(f) [Co(C₂O₄)₂Cl₂]³⁻:

31.

(a) tricarbonatocobaltate(III) ion; (b) tetraaminecopper(II) ion; (c) tetraaminedibromocobalt(III) sulfate; (d) tetraamineplatinum(II) tetrachloroplatinate(II); (e) tris-(ethylenediamine)chromium(III) nitrate; (f) diaminedibromopalladium(II); (g) potassium pentachlorocuprate(II); (h) diaminedichlorozinc(II)

33.

(a) none; (b) none; (c) The two Cl ligands can be cis or trans. When they are cis, there will also be an optical isomer.

35.

This figure shows eight structures, each inside brackets in three rows. The first row contains three structures, the second row contains three structures, and the third row contains two structures. These structures are described in increasing order moving left to right and top to bottom in the figure. Each includes a central C o atom with line segments indicating bonds above and below the central atom. Above and to both the left and right, dashed wedges with vertices at the C o atom widening as they move out from the atom indicates single bonds. Similarly, solid wedges below and to both the left and right indicate single bonds. Outside each structure in brackets, to the right, an element or group is identified in brackets as a superscript. In the first structure, the C atom of a C N group is bonded to the C o atom. All 5 remaining bonds are with C l atoms. C N appears in brackets as a superscript outside the structure. In the second structure, the N atom of a C N group is bonded to the C o atom. All 5 remaining bonds are with C l atoms. C N appears in brackets as a superscript outside the structure. In the third structure, the C atom of two C N groups are bonded to the C o atom at the top and bottom of the structure. All 4 remaining bonds are with C l atoms. C l appears in brackets as a superscript outside the structure. In the fourth structure, the C atom of a C N groups is bonded to the C o atom at the top and the N atom of a C N group which is bonded at the bottom of the structure. All 4 remaining bonds are with C l atoms. C l appears in brackets as a superscript outside the structure. In the fifth structure, the N atom of two C N groups are bonded to the C o atom at the top and bottom of the structure. All 4 remaining bonds are with C l atoms. C l appears in brackets as a superscript outside the structure. In the sixth structure, the C atom of two C N groups are bonded to the C o atom at the top and upper right of the structure. All 4 remaining bonds are with C l atoms. C l appears in brackets as a superscript outside the structure. In the seventh structure, the C atom of a C N group is bonded to the C o atom at the top of the structure and the N atom of a C N group is bonded at the upper right of the structure. All 4 remaining bonds are with C l atoms. C l appears in brackets as a superscript outside the structure. In the eighth structure, the N atom of two C N groups are bonded to the C o atom at the top and upper right of the structure. All 4 remaining bonds are with C l atoms. C l appears in brackets as a superscript outside the structure.

37.

39.

[Co(H₂O)₆]Cl₂ with three unpaired electrons.

41.

(a) 4; (b) 2; (c) 1; (d) 5; (e) 0

43.

(a) [Fe(CN)₆]⁴⁻; (b) [Co(NH₃)₆]³⁺; (c) [Mn(CN)₆]⁴⁻

45.

The complex does not have any unpaired electrons. The complex does not have any geometric isomers, but the mirror image is nonsuperimposable, so it has an optical isomer.

47.

No. Au⁺ has a complete 5d sublevel.

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