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CHEM0902/C06K

INORGANIC CHEMISTRY
First row transition metals
Catalysts and coloured compounds
(continued)
Ainka Brown
ainka.brown02@uwimona.edu.jm
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Transition metals
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Electronic
configuration
Catalytic ability
Coloured
compounds
and complexes
Orbital shapes and energies
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1
2
3
4
nucleus
Orbital shapes and energies
Filling electrons:
- minimise energy
- minimise repulsion
- when a shell is filled with electrons it raises
energy of shell above (HOW???)
4
What is meant by a low energy shell?
Assumption:
Sub-orbitals have same energy in all elements.
Generally true, but not always
Orbital shapes and energies
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Period 4: unexpected electron configurations
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K [Ar] 3d
0
4s
1

Ca [Ar] 3d
0
4s
2

Sc [Ar] 3d
1
4s
2

Ti [Ar] 3d
2
4s
2

V [Ar] 3d
3
4s
2

Cr [Ar] 3d
5
4s
1

Mn [Ar] 3d
5
4s
2

Fe [Ar] 3d
6
4s
2

Co [Ar] 3d
7
4s
2

Ni [Ar] 3d
8
4s
2

Cu [Ar] 3d
10
4s
1

Zn [Ar] 3d
10
4s
2

*
*
4s orbitals have a
slightly lower energy
than 3d orbitals)
1s
2s
2p
3s
3p
4s
3d
4p
Unexpected electron configurations
Predicted
Actual
2 out of 3 e
-
are in lower E
sub-orbital
Lower E outweighs
electronic replusion
All the e
-
are in higher E
sub-orbital
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R
E
Unexpected electron configurations
Similar trend for Ti and V
Predicted
Actual
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E
R
Unexpected electron configurations
Predicted
Actual
1 of the e
-
is in lower E sub-
orbital plus no repulsion
All e
-
are in higher E sub-orbital,
plus repulsion
OR
Four of the e
-
are in higher E sub-
orbital, plus repulsion
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E R
Unexpected electron configurations
Predicted
Actual
2 of the e
-
are in lower E sub-
orbital plus less repulsion
All e
-
are in higher E sub-orbital,
plus repulsion
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Similar trend for Fe and Co
E R
Unexpected electron configurations
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Predicted
Actual
OR
All e
-
are in higher E sub-orbital,
plus repulsion
2 of the e
-
is in lower E sub-
orbital plus less repulsion
Lower energy arrangement
In both there is repulsion
and a half-filled orbital
Remembering configurations
(Exceptions Cr and Cu)
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4s
3d
Think 2 10
What is configuration of Co
3+
?

Characteristics of transition metals
Criteria:
variable oxidation state
ions with partially-filled d-orbitals
catalytic activity
formation of complex ions
coloured complexes/compounds
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Oxidation states of transition metals
Lose 4s electrons first (shielding by 3d)

Can lose/share both 3d and 4s

Readiness to be oxidised decreases left to right
(correlation with I.E and Z
eff
)


Oxidation potentials show will readily form +2 and +3
cations in H
+

(Except Cu. Needs something stronger)


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Oxidation potentials
E

/V

Oxidation eqn.

E

/V

Oxidation eqn.
0.45 Fe
(s)
Fe
2+
+ 2 2.08 Sc
(s)
Sc
3+
+ 3
0.28 Co
(s)
Co
2+
+ 2 1.63 Ti
(s)
Ti
2+
+ 2
0.26 Ni
(s)
Ni
2+
+ 2 1.18 V
(s)
V
2+
+ 2
-0.34 Cu
(s)
Cu
2+
+ 2 0.91 Cr
(s)
Cr
2+
+ 2
0.76 Zn
(s)
Zn
2+
+ 2 1.18 Mn
(s)
Mn
2+
+ 2
H
2(g)
H
+
+ 2 E

= 0.00 V

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Oxidation states of transition metals
High oxidation state = good oxidizing agents,
(e.g. Cr
2
O
7
2-
,
MnO
4
-
)

Low oxidation state in early part of series = good
reducing agent
(e.g. V
2+
, Cr
2+
)

Later in series poor reducing agent (high Z
eff
)
(e.g.Co
2+
, Ni
2+
, Cu
2+
and Zn
2+
)
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Catalytic activity
A catalyst is a substance which speeds up a reaction, but
is chemically unchanged at the end of the reaction

Characteristics:
ability to change oxidation state.
ability to adsorb substances unto their surface
(helps to activate them)

Two types:
heterogenous
homogenous


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HOW ?
Heterogenous vs. homogenous
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Heterogenous
Homogenous
Some heterogenous catalysts
Catalysts Reaction
MnO
2
Decomposition of H
2
O
2

V
2
O
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Contact Process
Fe Haber Process
Pt/Rh Ostwald Process
Ni/Pd/Pt Hydrogenation
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Heterogenous catalysts
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Heterogenous catalysts
Reading Assignment!!!!!!

How does V
2
O
5
catalyse the Contact Process?
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Homogenous Catalysis
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Peroxodisulfate + Iodide
What are the
changes in oxidation
state?
Formation of complex ions
Trasition Metal ions can undergo dative covalent
bonding
(Empty 3d, 4s, 4p and 4d orbitals can accommodate)

Examples in nature
(hemoglobin, vitamin B
12
)

Do not need to know how bonding
occurs in depth


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Bonding in Complex ions
Ligands molecule or ions surrounding metal ion
(have lone pair or negative charge)
e.g. H
2
O, Cl
-
, NH
3
etc.

Donor atom atom that does the actual bonding

Coordination number number of donor atoms around
the metal ion
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Bonding in Complex ions
25 Taken from: www.chemguide.co.uk
Note charge on
metal is not
quenched!!!
Just re-distributed!!
Coloured ions/compounds
In complexes d-orbitals have different energies
Ligands cause electron-electron repulsions
d-orbital splitting occurs
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E E
Which +2
transition metal
cation does this
represent ? OR
Coloured ions/compounds
Can have d d transitions
(absorb visible light)

Colour is dependent on E



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E
600 nm
560 nm
490 nm
430
400 nm
800 nm
650 nm
Coloured ions/compounds
E is affected by:
- oxidation state of ion
- ligands
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CuSO
4
Co(NO
3
)
2

K
2
Cr
2
O
7

K
2
CrO
4

NiCl
2
KMnO
4

E
There are
anomalies.
Colour not
due to
dd
Coordination Chemistry
The colours of Chemistry and the
Chemistry of colours
Ainka Brown
ainka.brown02@uwimona.edu.jm
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Transition metal complexes
Also known as coordination compounds
Used as catalysts, medicines and pigments

Objectives
applying the IUPAC rules for naming
determining and drawing isomers
geometric (cis, trans)
optical

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Transition metal complexes
May be neutral compounds, cations or anions
(Depends on the ligand)
Terms to know:
- ligand
- donor atom
- coordination number
- chelate


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Ligand Name Name Molecule
Ammine Ammonia :NH
3

Aqua Water H
2
O:
Carbonyl Carbon monoxide :CO
Nitrosyl Nitrogen oxide :NO
Phosphine Phosphine :PH
3

ethylenediamine ethylenediamine en
Neutral ligands
What is the
structure of en?
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Anionic ligands
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Ligand Name Name Ion
Chloro Chloride Cl
-

bromo bromide Br
-

Fluoro Fluoride F
-

Cyano Cyanide
-
CN
Hydroxo Hydroxide
-
OH
Nitro Nitrite NO
2
-

Carbonato Carbonate CO
3
-

Oxalato Oxalate C
2
O
4
2-

Oxo Oxide O
2-
What is the structure of oxalate?
Nomenclature
Please read the relevant section in McMurray
and Fay!!!!!

We will discuss briefly

Practice, practice and practice some more
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Nomenclature
For salts name cation before the anion, with a space
between the names.

Ligands are named in alphabetical order (prefixes
ignored)
Use di-, tri-, tetra-, etc if more than one monodentate
ligand.
For chelates use bis-, tris- etc. if more than one

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6 ammonias? 2 waters and 4 chlorides ?
2 oxalates and 2 waters? 2 oxalates and 2 chlorides?
Nomenclature
No space between ligand names, no space between
last ligand and metal

Roman numerals in brackets to show oxidation state
of metal

If metal is part of anionic complex it has a metallate
name


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Metallate names
Metal Anion name
Titanium titanate
Vanadium vanadate
Chromium chromate
Manganese manganate
Iron ferrate
Cobalt cobaltate
Nickel nickelate
Copper cuprate
Zinc zincate
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Nomenclature
[Co(NH
3
)
6
]Cl
3

[Fe(C
2
O
4
)
3
]
3-
[Cu(NH
3
)
4
]SO
4
Na[Cr(OH)
4
]
Hexaamminecobalt(III) chloride
Trisoxalatoferrate(III) ion
Tetraamminecopper(II) sulfate
Sodium tetrahydroxochromate(III)
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