TUGAS KIMIA ANORGANIK 3

OLEH

NAMA : ANNISA RAHMAH

NIM : 1205690
DOSEN : Sherly Kasuma Warda Ningsih, S.si, M.si

JURUSAN KIMIA
FAKULTAS MATEMATIKA DAN ILMU PENGETAHUAN ALAM
2014
20.1 Write balanced equations for (a) the reaction between titanium(IV) chloride and
oxygen gas; (b) sodium dichromate with sulfur at high temperature; (c) the warming of
copper(II) hydroxide.

Answer :

(a) TiCl4(l) + O2(g) TiO2(s) + 2 Cl2(g)

(b) Na2Cr2O7(s) + S(l) Cr2O3(s) + Na2SO4(s)
(c) Cu(OH)2(s) CuO(s) + H2O(l)

20. 2 Write balanced equations for (a) the reduction of vanadyl ion by zinc metal in acidic
solution (two equations); (b) the oxidation of chromium(III) ion to dichromate ion by
ferrate ion, which itself is reduced to iron(III) ion in acid solution (write initially as two
half-equations); (c) the addition of excess hydroxide ion to copper(II) hydroxide; (d) the
reaction between copper(II) ion and iodide ion.

Answer :

(a) 2 VO2+ (aq) + Zn(s) + 4 H+ (aq) 2 V3+ (aq) + Zn2+ (aq) + 2 H2O(l)
2 V3+ (aq) + Zn(s) 2 V2+ (aq) + Zn2+ (aq)

(b) 2 Cr3+ (aq) + 7 H2O (l) Cr2O7 2- (aq) + 14 H+(aq) + 6 e-

FeO4 2- (aq) + 8 H+(aq) + 3 e- Fe3+ (aq) + 4 H2O(l)
2 Cr3+ (aq) + 2 FeO4 2- (aq) + 2 H+(aq) Cr2O7 2- (aq) + 2 Fe3+ (aq) + H2O(l)

(c) Cu(OH)2(s) CuO(s) + H2O(l)

(d) 2 Cu 2+ (aq) + 4 I- (aq) 2 CuI(s) + I2(aq)

20.3 Discuss briefly how the stability of the oxidation states of the 3d transition metals
changes along the row.

Answer :

Jika dilihat dari diagram frost stabilitas oksidasi dari logam transisi 3d perubahan di
sepanjang baris adalah

Pada diagram frost ini, dapat dilihat bahwa pada titanium bilangan oksidasinya adalah 0 is
strongly reducing, pada baris selanjutnya yaitu tembaga, logam ini adalah yang paling stabil
secara termodinamik bilangan oksidasinya. Pada baris selanjutnya, pada Chromium bilangan
oksidasi tertinggi tidak disukai, Bilangan oksidasi yang paling stabil secara termodinamika
adalah +3 untuk titanium, vanadium, dan kromium, sedangkan +2 disukai oleh unsur-unsur
lain. Untuk besi, kestabilan bilangan oksidasinya +3 dan +2 sangat mirip. Selanjutnya,
tembaga memilki keunikan, tembaga memilki kestabilan pada bilangan oksidasi +1. Namun,
jika dilihat pada diagram, tembaga rentan terhadap disproporsionasi ke +2 dan
0. Bilangan oksidasi maksimum adalah sama dengan jumlah kelompok (yaitu, jumlah 4s dan
3d elektron). Untuk anggota kemudian, keadaan oksidasi +2 mendominasi.
20.4 Identify uses for (a) titanium(IV) oxide; (b) chromium (III) oxide; (c) silver nitrate.

Answer :

(a) White pigment was white lead, Pb3(CO3)2(OH)2

(b) green pigment
(c) starting material for making other silver compounds (and as a laboratory reagent).

20. 5 What evidence do you have that titanium(IV) chloride is a covalent compound?
Suggest why this is to be expected.

Answer :

Bukti yang menunjukkan bahwa titanium (IV) klorida merupakan senyawa kovalen adalah
dimana daya tarik antara ikatan Ti Cl sangat lemah yang dipengaruhi oleh gaya van der
waals, karena interaksi yang sangat lemah ini mengakibatkan titik didih dan titik lelehnya
rendah. Sehingga senyawa titanium tetraklorida ini mudah menguap.

20.6 The equation for the fi rst step in the industrial extraction of titanium is

Which element is being oxidized and which is being reduced in this process?

Answer :

Chlorine is being reduced (from 0 to -1), and carbon is being oxidized (from 0 to +2).

20.7 Write balanced half-equations for the reduction of permanganate ion in (a) acidic
solution; (b) basic solution.

Answer :

(a) MnO4 - (aq) + 8 H+(aq) + 5 e- Mn2+ (aq) + 4 H2O(l)

(b) MnO4 - (aq) + 2 H2O(l) + 3 e- MnO2(s) + 4 OH- (aq)
20.8 Aluminum is the most abundant metal in the Earths crust. Discuss the reasons why
iron, not aluminum, is the more important metal in the worlds economy.

Answer :

1. Iron is the second most abundant metal in the Earths crust, and concentrated deposits
of iron ore are found in many localities, thus making it easy to mine.
2. The common ore can be easily and cheaply processed thermochemically to obtain the
metal.
3. The metal is malleable and ductile, whereas many other metals are relatively brittle.
4. The melting point (1535C) is low enough that the liquid phase can be handled
without great difficulty.
5. By the addition of small quantities of other elements, alloys that have exactly the
required combinations of strength, hardness, or ductility for very specific uses can be
formed.

20.9 Contrast how iron(II) chloride and iron(III) chloride are synthesized.

Answer :

Iron(II) chloride is prepared under comparatively reducing conditions as a result of the

hydrogen gas production:
Fe(s) + 2 HCl(g) FeCl2(s) + H2(g)
Iron(III) chloride is prepared using highly oxidizing chlorine gas:
2 Fe(s) + 3 Cl2(g) 2 FeCl3(s)

20. 10 In the purification of nickel metal, tetracarbonylnickel(0) is formed from nickel at a

lower temperature, while the compound decomposes at a higher temperature. Qualitatively
discuss this equilibrium in terms of the thermodynamic factors, enthalpy, and entropy.

Answer :

The chemical equation is

Ni(s) + 4 CO(g) Ni(CO)4 (g)
Formation of this compound requires a net decrease of three moles of gas, resulting in a
decrease
in entropy. Hence the forward reaction must be enthalpy driven (that is, exothermic). The
decomposition reaction is favored at higher temperatures. This is logical when the relationship
G = H - TS is considered. For the reverse reaction, both H and S are positive,
thus as the temperature increases, ( -TS) will become increasing negative, to the point
where the term exceeds H and the reverse reaction becomes spontaneous (negative G).

20.11 Identify each metal from the following tests and write balanced equations for each
reaction: (a) Addition of chloride ion to a pink aqueous solution of this cation gives a deep
blue solution. (b) Concentrated hydrochloric acid reacts with this metal to give a colorless
solution. On dilution, a white precipitate is formed. (c) Addition of acid to this yellow anion
results in an orange-colored solution.

Answer :

(a) Cobalt: [Co(OH2)6]2+ (aq) + 4 Cl- (aq) [CoCl4]2- (aq) + 6 H2O(l)

(b) Copper: 2 Cu(s) + 2 H+(aq) + 4 Cl- (aq) 2 [CuCl2] - (aq) + H2(g)
[CuCl2] - (aq) CuCl(s) + Cl- (aq)
(c) Chromium: 2 CrO4 2- (aq) + 2 H+(aq) Cr2O7 2- (aq) + H2O(l)

20. 12 Identify each metal from the following tests and write balanced equations for each
reaction: (a) Acidifying a solution of this cation gives a pale violet solution and, on addition
of chloride ion, a yellow solution is formed. (b) Addition of ammonia to this pale blue
cation gives a deep blue solution. (c) Addition of thiocyanate solution to this almost
colorless cation gives a deep red color.

Answer :
a. Cobalt: [Co(OH2)6]2+ (aq) + 4 Cl- (aq) [CoCl4]2- (aq) + 6 H2O(l)
b. copper
NH3(aq) + H2O(l) <==> NH4+(aq) + OH-(aq)
[Cu(H2O)6]2+(aq) + 2 OH-(aq) <==> Cu(OH)2 * 2 H2O(s) + 2 H2O(l)
Cu2+(aq) + 2 OH-(aq) <==> Cu(OH)2 (s)
[Cu(H2O)6]2+(aq) + 4 NH3 (aq) <==> [Cu(NH3)4(H2O)2]2+(aq) + 4
H2O(l)
Cu2+(aq) + 4 NH3 (aq) <==> Cu(NH3)42+(aq)(l)
c. Chromium: 2 CrO4 2- (aq) + 2 H+(aq) Cr2O7 2- (aq) + H2O(l)
20.13 A solution containing a colorless anion is added to a cold solution containing a pale
yellow solution of a cation. A violet solution is formed that becomes colorless on warming
to room temperature. Identify the ions and write a balanced chemical equation for each
step.

Answer :

The two reactants are the hexaaquairon(III) ion and thiosulfate ion:
Fe3+ (aq) + 2 S2O32- (aq) [Fe(S2O3)2]- (aq)
[Fe(S2O3)2]- (aq) + Fe3+ (aq) 2 Fe 2+ (aq) + S4O62- (aq)

20.14 You wish to prepare a tetrahedral complex of vanadium(II). Suggest the best choice
of a ligand (two reasons).

Answer :

A halide ion is an obvious choice because a large negative weak field ligand will favor
a tetrahedral arrangement. Iodide would be the specific choice because it is the largest
of the halides. Also, vanadium(II) is in a very low oxidation state for the metal. To
stabilize it, a reducing anion is preferableand iodide is strongly reducing

VCl4
The 4s and 4p atomic orbitals of vanadium can be used to form sigma molecular
orbitals. Although, the overlap patterns are rather complicated the 3dxz, 3dyz and 3dxy
valence orbitals also are situated properly to form sigma molecular orbitals.

The ligand field splitting diagram for a tetrahedral complex such as VCl4 is shown
below.
 1. The anti bonding molecular orbitals derived from the 3d valence orbitals are divided
into two sets.
2. The orbitals formed from the 3dxz, 3dyz and 3dxy orbitals are of higher energy than those
formed from the 3dz2and 3dx2-y2 orbitals.
3. Thus, the change from octahedral to tetrahedral geometry exactly reverses the role and
the energies of the d valence orbitals of the central metal ion.
4. t is the energy difference between the t2 and e in tetrahedral complex.
5. From ligand field theory we can predict that the t 2 orbitals in a tetrahedral complex
will not form as strong sigma bonds with ligand sigma orbitals as will the e g
octahedral orbitals thereby resulting in a much less energetic t 2 level and a relatively
small value.
6. Because of the small values all tetrahedral transition metal complexes have high spin
ground state configurations.

20. 15 The highest oxidation state for nickel in a simple compound is found in the hexafl
uoronickelate(IV) ion, [NiF6]2. (a) Why would you expect fl uoride to be the ligand? (b)
Would you expect the complex to be high spin or low spin? Give your reasoning.
Answer :

(a) Fluoride stabilizes high oxidation states since it is a -donor ligand. To maximize
interaction, the metal ion should have empty d orbitals and hence be in the highest possible
oxidation state.

(b) The value of the crystal-field splitting,, is very dependent upon oxidation state, so the
nickel(IV) complex should have a very large value. Thus, even though fluoride is very low
in the spectrochemical series, the complex is most likely to be low spin.
20.16 When iron(III) salts are dissolved in water, a yellowbrown color is observed. Only
after addition of a few drops of dilute nitric acid can the very pale purple color of the
hexaaquairon(III) ion be seen. Explain.
Answer :

The aqueous iron(III) ion hydrolyses in aqueous solution:

[Fe(OH2)6]3+ (aq) + H2O(l) [Fe(OH2)5(OH)]2+ (aq) + H3O+ (aq)

thus the yellow color of the hydroxy-species predominates unless acid is added to drive the
equilibrium to the left to give the pale purple color of the hexaaquairon (III) ion.
20.17 The ferrate(VI) ion, FeO42, is such a strong oxidizing agent that it will oxidize
aqueous ammonia to nitrogen gas, itself being reduced to iron(III) ion. Write a balanced
equation for the reaction.
Answer :

FeO42- (aq) + 8 H+(aq) + 3 e- Fe3+ (aq) + 4 H2O(l)

2 NH3(aq) N2(g) + 6 H+(aq) + 6 e-

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

20.18 When iron(III) forms a complex with dimethylsulfoxide, (CH 3)2SO, is the ligating
atom likely to be the oxygen or the sulfur? Explain your reasoning.
Answer :
Oxygen. Iron (III) is a hard acid, while oxygen is a hard base (and sulfur is a soft base).

20.19 Of the two common oxides of chromium, chromium- (VI) oxide and chromium(III)
oxide, which should have the lower melting point? Explain your reasoning.
Answer :
Chromium(VI) oxide. The very high charge density of the chromium metal ion will cause
sufficient polarization of the electrons on the oxygens to result in covalent bond formation.
Covalently bonded compounds have much lower melting points than ionic compounds

20.20 Of the two common oxides of chromium, chromium- (VI) oxide and chromium(III)
oxide, which should be acidic? Explain your reasoning.
Answer :

Chromium(VI) oxide should be acidic. It is the metal in the higher oxidation state (that is,
with the more oxygens) that will exhibit the more acidic properties.

20.21 Suggest why chromium(III) nitrate dissolves in water to form an acidic solution.
Answer :

Like aluminum and iron(III) ions, the chromium(III) ion will lose a hydrogen ion to a water
molecule.

[Cr(OH2)6]3+ (aq) + H2O(l) [Cr(OH)(OH2)5]2+ (aq) + H3O+(aq)

20.22 There is only one simple anion of cobalt(III) that is high spin. Identify the likely
ligand and write the formula of this octahedral ion.
Answer :

Fluoride ion; [CoF6]3-

20.23 Suggest why copper(I) chloride is insoluble in water.

Answer :

The insolubility of copper (I) chloride can be argued for reasons similar to those arguing why
silver chloride is insoluble According to Fajans Rules, cations with non-noble-gas
configurations are likely to have a more covalent character (in this case, the filled 3d orbitals
can be polarized towards the anions). If the ionic charge in the crystal lattice is decreased by
partial electron sharing, then the ion-water interaction will be less and the tendency to
dissolve will, in turn, be less.

20.24 Taking the Jahn-Teller effect into account, how many absorptions would you expect
from d electron transitions for the octahedral copper(II) ion?
Answer :
Three.
20.25 Use the Pourbaix diagrams in Figures 8.6 and 20.12 to suggest what is the most
likely form of iron in (a) a wellaerated lake; (b) a lake suffering from the effects of acid
rain; (c) bog water.
Answer :

(a) In a well-aerated lake, the partial pressure of dioxygen would lead to a high positive
potential, while the pH should be near neutral. FeO(OH) is the most likely species.

(b) In acid oxidizing conditions, Fe3+ is the most probable species.

(c) Fe2+ is most likely in these acid, reducing conditions.

20.26 Identify each of the following ions and write net ionic equations for each reaction:
(a) A pale pink cation that gives a deep blue color with chloride ion. The cation gives a blue
solid with hydroxide ion. (b) A yellow anion that gives a yellow precipitate with barium ion.
Addition of acid to the anion causes a color change to orange. The orange anion is reduced
by sulfur dioxide to give a green cation; the other product is a colorless anion that gives a
white precipitate with barium ion. (c) A pale blue cation that reacts with zinc metal to give a
red-brown solid. Addition of the pale blue cation to excess ammonia gives a deep blue
color.
Answer :(a) Cobalt(II):

[Co(OH2)6]2+ (aq) + 4 Cl- (aq) [CoCl4]2- (aq) + 6 H2O(l)

Co2+ (aq) + 2 OH (aq) Co(OH)2(s)

(b) Chromate:

CrO42- (aq) + Ba2+ (aq) BaCrO4(s)

2 CrO42- (aq) + 2H+(aq) Cr2O72- (aq) + H2O(l)

CrO42- (aq) + 8 H+(aq) + 3 e Cr3+ (aq) + 4 H2O(l)

SO2(aq) + 2 H2O(l) SO42- (aq) + 4 H+(aq) + 2 e-

(c) Copper(II):

Cu2+ (aq) + Zn(s) Cu(s) + Zn2+ (aq)

[Cu(OH2)6]2+ (aq) + 4 NH3(aq) [Cu(NH3)4]2+ (aq) + 6 H2O(l)

20.27 What are the similarities and differences between aluminum and iron(III)
chemistry?
Answer :

They both form anhydrous chlorides that react with water to release hydrogen chloride gas
while their hexahydrates are water soluble. The anhydrous chlorides both function as Friedel-
Craft catalysts. In the gas phase, their chlorides exist as dimers, Al 2Cl6 and Fe2Cl6,
respectively. On the other hand, iron(III) oxide is basic, while the oxide of aluminum is
amphoteric. Also, iron(III) compounds are colored, while those of aluminum are white.

20.28 Identify which transition metal(s) is(are) involved in each of the following
biochemical molecules: (a) hemocyanin; (b) ferrodoxin; (c) vitamin B12.
Answer :

(a) Copper

(b) iron

(c) iron and molybdenum

(d) cobalt.
20.29 Write balanced chemical equations corresponding to each transformation in the
element reaction fl owcharts for titanium, vanadium, chromium, manganese, iron, cobalt,
nickel, and copper (pages 572573).
Answer :