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CHAPTER 2 TRANSITION METALS ( UNIT V )


A transition metal forms stable ion with incompletely filled d orbital.
Copper (I) 3d10, Zinc (II) 3d10 and Scandium (III) 3d0 are not transition metal ions.
Electronic configuration of Transition metals and ions:- Electrons are filled and removed in 4s before 3d.
Half or completely filled orbitals are more stable, so d4 & d9 takes one electron from 4s.
Scandium (21Sc):- [Ar] 3d1, 4s2
Scandium (III) ion (21Sc):- [Ar] 3d0, 4s0
chromium (24Cr):- [Ar] 3d5, 4s1
chromium (III) ion (24Cr):- [Ar] 3d3, 4s0
chromium (VI) ion (24Cr):- [Ar] 3d0, 4s0
Copper (29Cu):- [Ar] 3d10, 4s1

Typical properties of Transition metals:-


Transition metals forms color ions, variable oxidation states , complex ion formation, catalytic property and
paramagnetic.
Variable oxidation states of Vanadium:-
Ion Oxidation state of Vanadium Color of aqua ion
2+
V +2 Lilac
V3+ +3 Green
2+
VO +4 Blue
- +
VO3 & VO2 +5 Yellow in acid solution
Reaction of Ammonium vanadate (V) with Zinc and Sulphuric acid:- Zinc and Sulphuric acid acts as
reducing agents and color changes as Vanadium is steadily reduced from +5 to +2.
Yellow green (Yellow + blue) blue green Lilac
Concentrated Nitric acid acts as oxidizing agent and color would change as Vanadium (II) species oxidize
further. It is not possible to predict final oxidation state from available data.
Complex ion:- A complex transition metal ion has a transition metal ion as its centre with a number of other
molecules or ions surrounding it e.g., [Cu(H2O) 6]2+
Co-ordination number:- The number of dative covalent bonds to the central metal ion e.g., co-ordination
number of [Cu(H2O) 6]2+ is 6.
Ligands:- The ions or molecules that can form dative covalent bond to a transition metal ion by by donation of
an electron pair.
Bonding in Cyanide ion:-

How cyanide ion act as ligand:- The lone pair of electrons on Carbon or Nitrogen forms a dative covalent
bond to central metal ion.
Bidentate ligand:- It forms two dative covalent bonds to transition metal ion due to two lone pairs e.g., 1,2-
diaminoethane or ethylenediamine.
cant act as bidentate ligand because lone pairs on Nitrogen too close and repel. Bond angles too
acute and too much ring strain.
Color of Complex d-block ions:- Ligands cause d orbitals to split. Some frequencies of light energy are
absorbed to promote electrons within d level. Remaining light is transmitted resulting in color seen.
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Rule for Naming Coordination Complexes:-


1. Ligands are named first in alphabetical order.
2. The name of the metal comes next.
3. The oxidation state of the metal follows, noted by a Roman numeral in parentheses (II, & IV).
4. Ligands that act as anions which end in -ide are replaced with an ending -o e.g., chloride to chloro.
Anions ending with -ate are replaced with -ato e.g., sulphate to sulfato.

Anionic Monodentate Ligands


F- Fluoro OH- Hydroxo
- 2-
Cl Chloro SO4 Sulfato
- 2-
Br Bromo S2O3 - Thiosulfato
I- Iodo NO2- Nitrito-N-; Nitro
2- -
O Oxo ONO Nitrito-O-; Nitrito
CN- Cyano SCN- Thiocyanato-S-; Thiocyanato
-
NC- Isocyano NCS Thiocyanato-N-; Isothiocyanato

5. Most neutral molecules that are ligands carry their normal name. The few exceptions are the first four on the
chart: ammine (NH3), aqua (H2O), carbonyl (CO) and nitrosyl (NO).

If the overall coordination complex is an anion, the ending "-ate" is attached to the metal center. Copper
+2 will change into cuprate(II), Iron into ferrate, Tin into stannate, Silver into argentate, Lead into plumbate and
Gold into aurate.

The rest of the metals simply have -ate added to the end (cobaltate, nickelate, zincate, osmate, cadmate,
platinate, mercurate, etc.

Examples:-
1. [FeCl(CO)2(NH3)3]2+ triamminechlorodicarbonyliron(III) ion.
2. [CrCl2(H2O)4]+ tetraaquadichlorochromium(III) ion
3. [Cr(OH)4]- tetrahydroxochromate(III) ion
4. [CuCl4]2- tetrachlorocuprate(II) ion
5. [Pt(NH3)4)] tetraammineplatinum(II)
6. [Pt(Cl)4] tetrachloroplatinate(II)
7. :[CoCl(NO2)(NH3)4]+ tetraamminechloronitritocobalt(III)
8. [CrF4]Cl2 TetrafluoroChromium (VI) chloride
9. [Cr(H2O)4(NH3)]+2 Amminetetraaquachromium(II) ion
10. [Cr(SO4)(NH3)] Amminesulfatochromium(II)
11. [Cr(H2O)4(NH3)]SO4 Amminetetraaquachromium(II) sulfate
12. K3[Fe(CN)6] Potassium hexacyanoferrate(III)
13. Co(SCN)42- tetrathiocyanatocobaltate(II) ion.
14. [Cu(H2O)6]2+ hexaaquacopper(II) ion
15. [Al(H2O)6]3+ hexaaquaaluminium ion

16. [Cr(NH3)3(H2O)3]Cl3 triamminetriaquachromium(III) chloride

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17. [Pt(NH3)5Cl]Br3 pentaamminechloroplatinum(IV) bromide

18. [Pt(H2NCH2CH2NH2)2Cl2]Cl2 dichlorobis(ethylenediamine)platinum(IV) chloride

19. [Co(H2NCH2CH2NH2)3]2(SO4)3 tris(ethylenediamine)cobalt(III) sulfate

20. K4[Fe(CN)6] potassium hexacyanoferrate(II)

21. Na2[NiCl4] Sodium tetrachloronickelate(II)

22. Pt(NH3)2Cl4 diamminetetrachloroplatinum(IV)

23. Fe(CO)5 pentacarbonyliron(0)

24. (NH4)2[Ni(C2O4)2(H2O)2] ammonium diaquabis(oxalato)nickelate(II)

25. [Ag(NH3)2][Ag(CN)2] diamminesilver(I) dicyanoargentate(I)

26. [Fe(NH3)6](NO3)3 hexaammineiron(III) nitrate

27. (NH4)2[CuCl4] ammonium tetrachlorocuprate(II)

28. [Co(SO4)(NH3)5]+ sodium monochloropentacyanoferrate(III)

29. K3[CoF6] potassium hexafluorocobaltate(III)

30. [CoBr(NH3)5]SO4 pentaamminebromocobalt(III) sulfate

31. [Fe(NH3)6][Cr(CN)6] hexaammineiron(III) hexacyanochromate (III)

32. [Co(SO4)(NH3)5]+ pentaamminesulfatocobalt(III) ion


33. [Fe(OH)(H2O)5]2+ pentaaquahydroxoiron(III) ion
34.

Structure of Transition metal Complexes:-


1) Transition metal complexes with Coordination number 2 (linear complexes):-

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2) Transition metal complexes with Coordination number 4:-


i) Tetrahedral complexes:- It is common with 1st row metals having pi donor ligands.

ii) Square planar complexes:- It is common with transition metals having d8 electronic configuration and pi
acceptor ligands.

3) Transition metal complexes with Coordination number 6 (octahedral ):- 6 electron pairs repel to a
position of minimum repulsion.

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Structure of Complex ions:-

1. Co(NH3)6Cl3 hexaamminecobalt(III) chloride

2. [Co(NH3)5Cl]Cl2 pentaamminechlorocobalt(III) chloride

3. [Co(NH3)4Cl2]Cl

cis-tetraamminedichlorocobalt(III) chloride trans-tetraamminedichlorocobalt(III) chloride

Chemistry of Copper:-

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Color of Copper compounds:- Copper (II) compounds are coloured due to incompletely filled d sub-shell,
which allows electron transitions between split energy levels. Copper (I) compounds dont have any color due
to completely filled d sub-shell, which does not allow d-d transition. Anhydrous Copper (II) sulphate is white
because no ligands to split d orbitals.
Ligand exchange reactions:- The ligands that bond more effectively to transition metal ions give more stable
complexes. The reaction results in a color change due to different amount of splitting between d orbitals.

Pale blue deep blue


[Cu (H2O)6]2+ + 4Cl- [CuCl4]2- + 6 H2O
Blue green

Chemistry of Chromium:-

Step 3 is not a redox process because chromate and dichromate both have same oxidation number (+6).
Reaction 1 is ligand exchange and reagent needed in concentrated HCl.
In Reaction 4, green ppte reacts to form green solution because NaOH is a strong alkali and [Cr(OH) 3 (H2O)3]
loses three protons because it is amphoteric. To reverse reaction 4, add acid.
In Reaction 6, entropy increases due to increase in number of particles.

[Cr(H2O) 6]3+ ion react with water to form acidic solution.

The pH of aqueous solution of [Cu(H2O) 6]2+ ion is higher than [Cr(H2O) 6]3+ because concentration of oxonium
ion is less because Copper ion in Cu2+ and Chromium ion is Cr3+.

Color of Chromate and dichromate ions:-


Color of Chromate ion (CrO42-) is yellow and dichromate ion (Cr2O72-) orange.

Catalyst:- They provide alternative routes with lower activation energies. So, a greater proportion of paticles
have energy greater than activation energy.
Homogenous catalysts:- Transition metal ions can act as homogenous catalysts.
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Transition metals form various oxidation states. They are able to donate and receive electrons due to ions with
partially filled sub-shells of d electrons. The energy differences between the oxidation states are small.
Surface catalyst:- The gases adsorb to catalyst surface. They react and leave. Reaction could be faster because
these processes lower activation energy by providing alternative route, so a greater proportion of molecules
react. Bonds in reactants are weakened. Reactants may be positioned in more favorable orientations.
Advantages of heterogeneous catalysts:-
1) heterogeneous catalysts can be filtered off
2) do not appear in any liquid or gaseous products
3) are easy to separate
4) are stereospecific
5) suited to continuous processes rather than batch processes
TESTS AND OBSERVATIONS OF TRANSITION METAL IONS
Aqua Ion Ion Color Few drops of Excess NaOH(aq) Few drops of Excess NH3(aq)
NaOH(aq) NH3(aq)
Fe2+ Pale green Dark green ppte Insoluble in excess Dark green ppte Insoluble in excess
Fe(OH)2 Fe(OH)2
Fe3+ Yellow / Rusty red brown Insoluble in excess Rusty red brown Insoluble in excess
brown ppte Fe(OH)3 ppte Fe(OH)3
Mn2+ Pink Cream / brown Insoluble in excess Cream / brown Insoluble in excess
ppte Mn(OH)2 ppte Mn(OH)2
Cu2+ Blue / Blue ppte Insoluble in excess Blue ppte Deep blue solution
green Cu(OH)2 [Cu(OH)2(H2O) 4] [Cu(NH3)4 (H2O) 2]2+
Ni2+ Green Green ppte Insoluble in excess Green ppte Blue solution
Ni(OH)2 [Ni(OH)2 (H2O)4] [Ni(NH3)4 (H2O) 2]2+
Cr3+ Green Green ppte Green solution Green ppte Green solution
[Cr(OH) 3 (H2O)3] [Cr(OH) 6]3- [Cr(OH) 3 (H2O)3] [Cr(NH3) 6]3+
Zn2+ Colourless White ppte Colourless solution White ppte Colourless solution
Zn(OH)2 [Zn(OH)6]4- [Zn(OH)2 (H2O)4] [Zn(NH3)4 (H2O) 2]2+
Reverse Disproportionation:- Manganese (VI) in MnO42- can be prepared in a reverse disproportionation
reaction, by reacting manganate (VII) ions with Manganese (IV) oxide in alkali.

+7 +4 +6
The reverse reaction is a disproportionation in which same element reacts to give one higher and one lower
oxidation state.
Effect of concentration of hydroxide ions on electrode potential:- When the concentration of hydroxide ion
concentration is increased, the equilibrium of second half equation moves to left. E becomes decreases and Ecell
becomes positive. So, preparation of Manganate (VII) ions becomes more likely.
Two half equations.

Full ionic equation:-

Rust formation Iron (III) hydroxide:-

Ecell for reaction is +0.84V, so will work.


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Ecell for reaction is +0.96V, so will work.


Combining two half equations:-
1)

Multiply equation (i) by 2 to balance electrons and then add.


Overall ionic equation:-

2)

Overall ionic equation:- Multiply equation I by 6 and then add.

3)

Multiply equation (ii) by 2 to balance electrons and then add.


Overall ionic equation:-
Preparation of metal hydroxides:- To prepare Manganese (II) hydroxide, react Manganese (II) sulphate
solution with Sodium hydroxide.
Amphoteric behavior of Zinc:-

Zinc hydroxide is amphoteric because it reacts with both alkali and acid. Hydrated Zinc ions exchanged water
for ammonia, so it is a ligand exchange reaction.
Aqueous Hydrated Iron (III) ion (yellow solution):- The yellow ion has the formula
[Fe(H2O)5OH]2+.
[Fe (H2O)6]3+ + H2O [Fe (H2O) 6 (OH)]2+ + H3O+
Add excess acid to ensure that [Fe (H2O)6]3+ ion is present.
Ionic equation for reaction of [Fe (H2O)6]2+ with Sodium hydroxide:-
[Fe (H2O)6]2+ + 2OH- Fe(OH)2 + 6 H2O
If the mixture is left to stand in air, the mixture turns red-brown because Oxygen oxidizes Fe2+ to Fe3+.
Question 1:- A red, water-soluble compound, R, contains potassium, iron and oxygen only.
When 1.98g of R (molar mass 198 g mol1) is dissolved in water and acidified with dilute
sulphuric acid, the solution will oxidize 4.56 g of iron(II) sulphate (molar mass 152 g mol
1). All of the iron in the product mixture is present as Fe3+. Calculate the amount (moles)
of R reduced and the amount (moles) of the iron (II)
sulphate oxidized. Hence calculate the oxidation state of iron in compound R.
Amount R reduced = (1.98 198 ) = 0.010 mol
Amount Fe2+ oxidized = (4.56 152 ) = 0.030 mol
Oxidation state of R changes by 3 (1 mole of R gains 3moles of electron Fe(VI)
R contains one mole of iron per mole of compound. What is the formula of R? K2FeO4
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Question 2:- A green chloride of copper, CuCl2 was boiled with concentrated hydrochloric
acid and metallic copper. After addition of a large volume of water, a white precipitate, X,
was produced. The precipitate was washed with distilled water and dissolved in
concentrated ammonia solution, giving a colorless solution of a copper complex, Y. When
air was blown through the solution of Y, it turned dark blue producing a solution of a
different complex of copper, Z.

X is Copper (I) chloride. It is produced in a redox reaction. CuCl2 + Cu 2CuCl


+
Y is linear Copper (I) ion complex Cu(NH3)2 . It is not colored due to complete d orbital.
Z is [Cu(NH3)4(H2O)2]2+

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