INORGANIC CHEMISTRY: An Introduction To The Chemistry of d-Block Elements

CHEMICAL PROPERTIES OF d-BLOCK ELEMENTS (Ti, Mn, Cr AND Fe)

1. A d-block element or transition element is defined as an element that forms at least a simple ion
with partially-filled d orbitals.

2. Electronic configuration of the first d-block series (period 4)

Element Symbol Proton Electronic configuration
number Structure 3d 4s
Scandium 21 [Ar]
Titanium 22 [Ar]
Vanadium 23 [Ar]
Chromium 24 [Ar]
Manganese 25 [Ar]
Iron 26 [Ar]
Cobalt 27 [Ar]
Nickel 28 [Ar]
Copper 29 [Ar]
Zinc 30 [Ar]

3. The electronic configuration of Cr: [Ar] ____________ is more stable than [Ar] ________________
while that Cu: [Ar] _______________ is more stable than [Ar] _____________
Explanation:
Cr has only one electron in the 4s subshell because the other electron is used to form a half-
filled 3d subshell which is more stable.
Cu is energetically more favourable to fill the 3d subshell completely, leaving the 4s
subshell with an unpaired electron.
4. Scandium and zinc are not transition elements.
Sc: [Ar] 3d14s2Sc3+: _____________ (empty 3d subshell)
Zn: [Ar] 3d104s2 Zn2+: _____________ (full 3d subshell)
5. Electrons are lost first form the 4s subshell rather than from the 3d subshell. WHY?
Energies of the 3d and 4s orbitals are relatively close. The 4s level is energetically more
stable than the empty 3d level.
Once the 3d level is occupied by electrons, the 4s electrons are repelled further from the
nucleus and to a higher energy level.
When forming ions, electrons from the higher energy 4s level are lost before the 3d level.

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6. All transition elements have the unique characteristics:
1. variable oxidation states
2. forming coloured ions and compounds
3. forming complex ions
4. acting as catalysts
Variable oxidation state
1. Transition elements show variable oxidation states because of the small energy difference
between the 3d and 4s orbitals.
2. Thus, both 3d and 4s electrons can be removed during ionisation, resulting in the transition
elements exhibiting more than one oxidation states.

Element Common oxidation state Examples

Ti +2, +3, +4 TiO, TiCl3 , TiCl4
V +2, +3, +4, +5 VO, V2O3 , VO2 , V2O5
Cr +2, +3, +4, +5, +6 CrO, Cr2O3 , CrO42-
Mn +2, +3, +4, +5, +6, +7 MnO, Mn2O3 , MnO2 , K2MnO4 , KMnO4
Fe +2, +3, +4, +5, +6 FeCl2 , FeCl3
Co +2, +3, +4 [Co(H2O)6]2+ , [Co(NH3)6]3+ , [CoF6]2-
Ni +2, +4 NiO, K2NiF6
Cu +1, +2 Cu2O , CuO

3. The more common oxidation states are normally +2 , +3 or both.

4. The stable oxidation state in aqueous solution and in the present of oxygen is Ti 2+ , V2+ , Cr3+ ,
Mn2+ , Fe3+ , Co2+ , Ni2+ , Cu2+ .
5. Across period, stability of +2 oxidation state increases, stability of +3 oxidation state
decreases. WHY?
The increasing nuclear charge binds the d subshell electrons more strongly, thereby increasing
the difficulty of removing the third electron from the orbitals.

6. Stability of the oxidation state in complex ion depends on the ligand that bond to the central
ion and pH value of the solution.
7. From Ti to Mn, the highest oxidation state correspond to the total number of 3d and 4s
electrons. In other words, from Ti to Mn, the highest oxidation state increases from +4 to +7.
This implies that all these elements use both the 3d and 4s electrons for reactions.
8. After Mn, the oxidation number decreases from +6 (Cr) to +2 (Cu) because the increasing of
nuclear charge that hold d electrons.
9. Generally, increasing of oxidation state will show the increasing of covalent character. Metal
oxides with lower oxidation state are basic oxides. The acidity of the oxide increases when the
oxidation state of the metal increases. (amphoteric to acidic)

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 Oxide Oxidation state Property
MnO +2 Basic
Mn2O3 +3 Basic
MnO2 +4 Amphoteric
MnO3 +6 Acidic
Mn2O7 +7 Acidic

Cations and Oxo Ions of Transition Elements

1. Transition elements in lower oxidation states (+1, +2, +3) exist as simple ions.
2. No simple ions are formed in higher oxidation states (+4 to +7). WHY?
- Too much of energy would be required to remove so many electrons and would result
in ions of extremely high charge denstity.

3. Oxo ion (oxoanion): polyatomic ions combined with oxygen.

4. Compounds or ions containing transition elements in higher oxidation states are usually
bonded covalently to electronegative elements like oxygen or fluorine, forming oxo ions.
5. Examples:
Oxidation Ti V Cr Mn Fe Co Ni Cu
state
1
2
3
4
5
6
7

6. Transition metal ions in higher oxidation states have covalent characteristics and tend to make
good oxidising agents.
Eg: The purple manganate (VII) ion and the orange dichromate (VI) ion are familiar oxidising
agent, high positive standard electrode potentials.
MnO4- + 8H+ + 5e- Mn2+ + 4H2O ; E = + 1.52 V
Cr2O72- + 14H+ + 6e- 2Cr3+ + 7H2O ; E = + 1.33 V

7. The relative stabilities of oxidation states

The standard electrode potentials (E) of the M3+ (aq) / M2+ (aq) system for the transition
elements from Ti to Co is shown in figure below.

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 The more positive the E value, the greater the
tendency for the M3+ (aq) ion to be reduced to M2+
(aq).
M3+ (aq) + e- M2+ (aq)

Thus, the low E values for Ti, V, Cr and Fe

shows that the oxidations state +3 is relatively more
stable for these elements than Mn and Co that have
higher E value.
The Mn2+ ion is more stable than the Mn3+ ion, but
Fe ion is more stable than Fe2+ ion. This is because
3+

both Mn2+ and Fe3+ have stable half-filled d orbitals.

Mn: [Ar] 3d5 4s2 Mn2+: [Ar] 3d5

Ti V Cr M n Fe C o
Fe: [Ar] 3d6 4s2 Fe3+: [Ar] 3d5

8. Stability of oxidation state may affected by the pH of a solution.

MnO42- is stable in alkaline solution, MnO4- is stable in acidic solution.
CrO42- is stable in alkaline solution, Cr2O72- is stable in acidic solution.

Coloured ions
1. Common complexes of transition metals

Element Oxidation Ions Colour

state
Ti +3 Ti3+ Purple / violet
V +2 V2+ Violet
+3 V3+ Green
Cr +2 Cr2+ Blue
+3 Cr3+ Green
+6 CrO42- Yellow
+6 Cr2O72- Orange
Mn +2 Mn2+ Pink
+6 MnO42- Green
+7 MnO4- Purple
Ni +2 Ni2+ Green
Cu +2 Cu2+ Blue
Fe +2 Fe2+ Green
[Fe(H2O)5(SCN)]2+ Dark red
+3 Fe3+ Yellow
[Fe(CN)6]3- Red-brown
Co +2 Co2+ Pink

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 2. Effect of adding NaOH (aq) and NH3 (aq) on transition metal ions.

Ion Effect of adding NaOH (aq) Effect of adding NH3 (aq)

until in excess until in excess
Cr3+ (aq) Green ppt. Green ppt.
Cr(OH)3 dissolves to give green Cr(OH)3 dissolves to give green
solution of [Cr(OH)6]3- solution of [Cr(NH3 )6]3+
Mn2+ (aq) White ppt. White ppt.
Mn(OH)2 darkens with oxidation Mn(OH)3 darkens with oxidation
Fe2+ (aq) Dark green ppt. Dark green ppt.
Fe(OH)2 turns brown on oxidation Fe(OH)2 turns brown on oxidation
to Fe(OH)3 to Fe(OH)3
Fe3+ (aq) Brown ppt of Fe(OH)3 Brown ppt of Fe(OH)3
Co2+ (aq) Blue ppt, Co(OH)2 Blue ppt.
Co(OH)2 dissolves to form pale
brown solution of [Co(NH3)6]2+
Ni2+ (aq) Green ppt, Ni(OH)2 Green ppt.
Ni(OH)2 dissolves to form pale blue
solution of [Ni(NH3)6]2+
Cu2+ (aq) Blue ppt, Cu(OH)2 Blue ppt.
Cu(OH)2 dissolves to give deep blue
solution of [Cu(NH3)4]2+

Complex Ions
1. A complex is formed when a central metal ion is surrounded by other ions or molecules that
donate lone pairs of electrons. These ions or molecules are called ligands.
2. A ligand is any species (ion or molecule) which donates a lone pair of electrons to forma a
dative covalent bond with a metal ion.
3. Examples of ligands:
a. Neutral molecule: NH3 , H2O , CO
b. Anion: CN- , F- , Cl- , Br - , OH- , SCN- , C2O42- , EDTA4-
4. The number of dative bonds surrounding the metal ion is called the coordination number.
5. Types of ligands:
a. Monodentate ligands: are species that can form only one dative bond with the central
metal ion.
Examples:
Ligand Formula Name of ligand in the
complex
Ammonia Ammine
Bromide ion Bromo
Chloride ion Chloro
Fluoride ion Fluoro
Cyanide ion Cyano
Thiocyanate ion Thiocyanato
Hydroxide ion Hydroxo
Water Aqua
Carbon monoxide Carbonyl

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 b. Bidentate ligands: have two donor atoms that can form two dative bonds with each
transition metal ion.
Examples:
Ligand Formula Name of ligand in the
complex
Oxalate ion Oxalato (ox)
(ethanedioate ion)
Ethylene diamine Ethylenediamine (en)
(ethane-1,2-diamine) (ethane-1,2-diamine)

c. Polydentate ligands: ligans can form more than two dative bonds with the metal ion.
Example: hexadentate EDTA (ethylenediaminetetraacetic acid)

Each EDTA4- has 6 donor atoms and form 6 dative bonds with a transition metal ion.

Examples of complex ions

Monodentate, [Fe(CN)6]3- Bidentate , [Fe(C2O4)3]3-

Hexadentate , [Ca(EDTA)]2-

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Transition metal tends form complex ion compared to simple ion, because:
- atom loss electron easily to form small cation
- metal atom has half filled 3d orbital that can fill with electron pairs coordinated from
ligand.

Formation of complex ions by exchange of ligands

1. Examples: Anhydrous copper (II) sulphate dissolves in water,

White blue

2. If other ligand is added, ligand exchange or ligand substitution will occur.

This reaction will change the colour of the complex ion.

Blue dark blue

This reaction involves the displacement of water molecules from [Cu(H 2O)6]2+ by the stronger
NH3 ligand.

3. Examples:

Hexaaquacobalt (II) tetrachlorocobaltate (II)

Pink blue

Hexaaquaferrum (II) hexacyanoferrate (II)

Green yellow brown

Type of complexes
Classified into 3 classes: i) anionic complex: [FeF6]3-
ii) cationic complex: [Ni(NH3)6]2+
iii) neutral complex: Fe(CO)5

NOMENCLATURE OF COMPLEXES
1. [ ]: enclose a complex ion or neutral coordination species.
2. Ligands are named first followed by the metal ions without any gap.
3. ( ): The oxidation state of central metal ion.
4. Neutral and cationic complexes, normal name of the metal is used.
5. Anionic complexes, the suffix ate
Name of Name of metal in anionic Name of metal Name of metal in
metal complex anionic complex
Aluminium Vanadium
Chromium Iron
Cobalt Manganese
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 Nickel Copper
Silver Platinum

6. The number of each ligand di, tri, tetra

7. The ligands are named in alphabetically, ignore numerical prefixes.
8. If the ligand already has prefixes, use bis, tris and tetrakis, name of ligand enclosed in ( ).
Example, bis(ethylenediamine).
9. Examples of complexes
Formula Name
3+
[Co(NH3)6]
[Cr(H2O)6]3+
[CuCl4]2-
[Fe(CN)6]3-
[CrCl2(H2O)4]+
K2[CoCl4]
[Ag(NH3)2]+
[PtCl2(NH3)4]2+
[Co(H2NCH2CH2NH2)3]2(SO4)3
(NH4)2[Ni(C2O4)2(H2O)2]

BONDING IN COMPLEX IONS

1. In complex compounds, transition metals ions use empty orbitals to form
coordinate bonds with ligands.
2. Ligand like chloride ion donates its lone pair of electrons and occupies the
available empty orbitals.
3. Example: [CuCl4]2-
2+
Cu has 4 empty 4s and 4p orbitals to accommodate the 4 lone pair of electrons from the chloride
ions.

Cu : ___ ___ ___ ___ ___ ___ ___ ___ ___

Cu2+ : ___ ___ ___ ___ ___ ___ ___ ___ ___

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STEREOISOMERISM OF COMPLEX IONS AND COMPOUNDS
1. The most common coordination numbers of complexes are 2, 4 and 6.
Coordination Geometrical structure Examples
number
2 Linear [Ag(NH3)2]+, [Ag(CN)2]-, [Cu(CN)2]-, [CuCl2]-

4 Tetrahedral [CuCl4]2-, [Ni(NH3)4]2+, [NiCl4]2-, Ni(CO)4, [Cu(CN)4]2-,

[FeCl4]-

Square planar [Cu(NH3)4]2+, PtCl42-, PdCl42-

6 Octahedral [Cu(H2O)6]2+, [Fe(CN)6]3-, [Fe(CN)6]4-, [Ni(NH3)6]2+,

[Co(NH3)6]3+, [Cr(CN)6]4-, [Cr(H2O)6]3+,
[Ni(H2NCH2CH2NH2)3]2+

2. There are two types of stereoisomers, geometric isomers and optical isomers. Coordination
compounds can show one or both types of isomerism or none at all.

Geometric Isomers
Occurs in
square-planar (general formula Ma2b2)
octahedral (Ma2b4, M(X X)2b2 and Ma3b3)

(M = central ion; a, b = monodentate ligands; X X = bidentate ligands)

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Square-planar (Ma2b2)
a b a b

M M

a b b a
cis isomer trans - isomer

Example: cis and trans diamminedichlorplatinum (II) , PtCl2(NH3)2

cis isomer trans - isomer

Octahedral
i) Ma2b4
a a
b a b b
o
90
M M 180 o

b b b b
b a
cis isomer trans isomer

ii) Ma3b3
a a
b a a b
o
90 o 180

M M

b a b a
b b
cis isomer (fac isomer) trans isomer (mer isomer)

Example: [Cr(NH3)4Cl2]+ , tetraamminedichlrochromium (III) has 2 isomers

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Example: [Co(NH3)4Cl2]+ Cl- , tetramminedichlorocobalt (III) chloride

Example: mer and fac [Cr(NH3)3Cl3] , tetraamminetrichlorochromium (III)

or mer and fac [Co(NH3)3(NO2)3]

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iii) M(X X)2b2

X b
b X X X

M M

b X X
X
X b
cis-isomer trans-isomer

Example: cis and trans CoCl2(en)2

Optical Isomers
- Shown by comples ions which do not have any plane or point of symmetry.
- The enantiomers (dextro, D and levo, L) differs in the effect towards plane polarised light.
- The enantiomers are not superimposable.
- Occurs in octahedral complex with bidentate or polydentate ligands.

Example: dextro (d) and levo (l) [Cr(C2O4)3]3- , trisoxalatochromate (III)

Example: [Cr(C2O4)2(H2O)2]- , diaquabisoxalatochromium (III)

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Structural isomerism
Example: hydrated complex of chromium with molecular formula, CrCl3 6H2O has 3 isomers
which is different in colour.
Isomer Colour Reaction with AgNO3(aq)
[Cr(H2O)6]Cl3 Purple All 3 moles of Cl- ions are precipitated
[Cr(H2O)5Cl]Cl2 H2O Light green Only 2 moles of the Cl- ions are
precipitated

[Cr(H2O)4Cl2] Cl 2H2O Dark green Only 1 mole of the Cl- ions is precipitated
Graphically, the structures of the 3 isomers are shown below:

Example: For the following compounds, give the oxidation state of the metal ion, state the type of
isomerism that exist and draw the isomers.
a) [Cr(NH3)4Cl2]+
b) [Cu(NH2CH2CH2NH2)3]2+
c) [CoCl3(NH3)3]
d) [Cr(C2O4)2(H2O)2]-

Example: The neutral complex PtCl2(NH3)2 has two isomers.

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 a) Name the complex
b) State the structure of the complex. Explain your answer.
c) State the type of isomers for the complex. Draw the isomers.

Example: A coordination compound triamminetrichlorocobalt (III) exists as two isomers.

a) What is the chemical formula of triamminetrichlorocobalt (III)?
b) Draw the structures of the two isomers and name them.

Catalytic Actvity
1. A catalyst is a substance that alters the rate of a chemical reaction, but itself
remains chemically unchanged at the end of the reaction.
2. Transition metals in the d-block series are good catalyst due to 2 factors:
Specific ability to exist in different oxidation state
Availability of empty orbitals which provides alternative mechanism
of reaction with lower activation energy
3. Examples of processes catalysed by transition elements or their compounds.
Industrial process Catalyst
Haber process production of ammonia

Ostwald process produce nitric acid from ammonia

Contact process production sulphuric acid

Hydrogenation of alkenes and hydrogenation of fats in the margarine

industry.
Polymerisation of ethane.

Catalytic converters fitted in car exhaust.

Reaction of persulphate ions and iodide ions.

Homogeneous Catalysis
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1. The reactants and the catalyst exist in the same phase.
2. Catalyst exists as an intermediate species in the reaction.
3. The catalyst is remains unchanged before and after the reaction.
4. Reactivity of catalysis depends on the ability of transition metals to exist in
different oxidation state.
5. Example: the catalytic reaction between iodide ion, I- (aq) and the
peroxodisulphate ion, S2O82- (aq) catalysed by Fe3+ (aq)
Overall equation: I- ion oxidised by S2O82- ion
2I- (aq) + S2O82- (aq) 2 SO42- (aq) + I2 (aq)

Step 1: oxidation of I- ion by the catalyst, Fe3+

2 I- (aq) + 2 Fe3+ (aq) 2 Fe2+ (aq) + I2 (aq)
The catalyst Fe3+ is reduced to Fe2+

Step 2: Oxidation of Fe2+ by S2O82-

2 Fe2+ (aq) + S2O82- (aq) 2Fe3+ (aq) + 2 SO42- (aq)
The Fe2+ is oxidised to Fe3+

Fe3+ ion acts as an intermediate.

Heterogeneous Catalysis
1. The reactants and the catalysts are in different phases.
2. Reactions normally occur on the surface of the solid catalyst through adsorption process.
Adsorption refers to the adhering of a species to the surface of a solid.
3. Transition elements are effective heterogeneous catalysts as they have many empty or
partially filled 3d and 4s orbitals to form temporary bonds with the reactant molecules.
4. Mechanism in three steps:
a. Adsorption of reactants onto the surface of the catalyst.
b. Breaking and formation of bonds.
c. Desorption of products from the surface of the catalyst

The reactants are adsorbed (physically or weakly bonded chemically) to the

surface of the catalyst.
The reaction is activated through adsorption.
Concentration of the reactants at the surface increases and allows correct
orientation for effective collisions to occur.
The intramolecular bonds within the reactant molecules are weaken.
Thus, the activation energy for the reaction is lowered, more effective collisions,
higher rate of reaction.
The strength of adsorption is essential to have an effective catalysts surface.
The bonding onto the catalysts surface (chemisorption / adsorption) must be
strong enough to weaken reactant molecule bonds but weak enough to allow new
bonds to form and the products to escape form its surface (desorption).
If the catalyst reactant bonding is too strong, most reactant or product
molecules will be too strongly chemisorbed, thus inhibiting the reactions
progress.
If the catalyst reactant bonding is too weak, many reactants are not
chemisorbed strongly enough to allow the initial bond breaking process to begin.

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5. Examples of reaction:
(A) Hydrogenation of ethene (catalyst: Ni or Pt)
CH2 = CH2 + H2 CH3CH3

i: both ethane and hydrogen molecules are adsorbed onto the Ni surface.

ii: The H H and C = C bonds are weakened to form bonds with the metal surface.

iii: one H atom diffuses close to the bonded carbon, C H bond is formed. That end of the
original ethene now breaks free of the metal surface.

iv: another C H bond is formed. The product ethane desorbs from the metal surface.

(B) Haber process (catalyst: Fe / Fe2O3)

N2 + 3H2 2NH3
i: N2 and H2 molecules adsorb onto the surface of Fe catalyst.

ii. The interaction weakens the covalent bonds and causes the molecules to dissociate.

iii. The highly reactive atoms migrate on the surface, eventually combine to form NH3 which
then absorb from Fe.

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