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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.
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.
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
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
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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)
Coloured ions
1. Common complexes of transition metals
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2. Effect of adding NaOH (aq) and NH3 (aq) on transition metal ions.
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.
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.
White blue
This reaction involves the displacement of water molecules from [Cu(H 2O)6]2+ by the stronger
NH3 ligand.
3. Examples:
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
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]-
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)
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Square-planar (Ma2b2)
a b a b
M M
a b b a
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)
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Example: [Co(NH3)4Cl2]+ Cl- , tetramminedichlorocobalt (III) chloride
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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
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.
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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]-
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
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)
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
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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.
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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