© a2 043 20-jul-12. electron structures 4s fills and empties before 3d fe [ar] 4s 2 3d 6 fe 3+...
TRANSCRIPT
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ELECTRON STRUCTURES
4s fills and empties before 3d
Fe [Ar] 4s2 3d6
Fe3+ [Ar] 3d5
Sc [Ar] 4s2 3d1
Sc3+ [Ar]
V [Ar] 4s2 3d3
V2+ [Ar] 3d3
Cu [Ar] 4s1 3d10
Cu+ [Ar] 3d10
Cu2+ [Ar] 3d9
Zn [Ar] 4s2 3d10
Zn2+ [Ar] 3d10
Cr [Ar] 4s1 3d5
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WHAT ARE TRANSITION METALS?
Transition metals are metals that contain an incomplete d sub shell in atoms or ions.
Top row transition metals: Sc – Cu
Zn is not a transition metal (Zn & Zn2+)
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PROPERTIES OF TRANSITION METALS?
1) They form coloured ions.
photo by Ian Geldard
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PROPERTIES OF TRANSITION METALS?
2) They form complexes (ligands form co-ordinate bonds to the metal ion).
[Cu(H2O)6]2+
OH2
Cu
OH2
H2O OH2
H2O OH2
2+
[CuCl4]2-
Cl
CuCl
Cl
Cl
2-
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PROPERTIES OF TRANSITION METALS?
3) They exhibit variable oxidation states.
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PROPERTIES OF TRANSITION METALS?
4) They show catalytic activity.
e.g.
Ni margarine productionV2O5 making SO3 for H2SO4
Fe Haber process to make NH3
Pt, Pd catalytic converters
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COMPLEX FORMATION
Ligand atom / ion with a lone pair that forms co-ordinate bond to metal
Complex metal ion with ligands co-ordinately bonded to it
Co-ordination number
number of co-ordinate bonds from ligand(s) to metal ions
Lewis base
lone pair donor (ligands are Lewis bases)
Lewis acid lone pair acceptor
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COMPLEX FORMATION
Lewis base
lone pair donor (ligands are Lewis bases)
Lewis acid lone pair acceptor
H+ + :OH- → H2O
Lewisbase
Lewisacid
Ligands form co-ordinate bonds via lone pairs
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COMPLEX FORMATION
Unidentate ligands – form one co-ordinate bond e.g. H2O:, :OH-, :NH3, :CN-, :Cl-
[Cu(H2O)6]2+
OH2
Cu
OH2
H2O OH2
H2O OH2
2+
[CuCl4]2-
Cl
CuCl
Cl
Cl
2-
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COMPLEX FORMATION
Bidentate ligands – form two co-ordinate bonds
[Cr(en)3]3+ [Cr(C2O4)3]3-
1,2-diaminoethane
(en)
ethanedioate(C2O4
2-)CH2 CH2
H2N NH2
C C-O
O O
O-
O
Cr
NH2
O O
O O
CC
C
CC O
O
O
O
O
O
C
3-NH2
Cr
NH2
H2N NH2
H2N NH2
3+
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COMPLEX FORMATION
Multidentate ligands – form several co-ordinate bonds EDTA4-
:N CH2
CH2:OOC
CH2:OOC
CH2 N:
CH2 COO:-
CH2 COO:-
-
-
e.g. [Cu(EDTA)]2-
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COMPLEX FORMATION
Multidentate ligands – form several co-ordinate bonds porphyrin
e.g. haem
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COMPLEX FORMATION
Multidentate ligands – form several co-ordinate bonds haemoglobin
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V2O5 Catalyst in Contact process
USES OF SOME COMPLEXES
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V2O5 Catalyst in Contact process
Mn2+ Autocatalyst in MnO4- / C2O4
2- titrations
USES OF SOME COMPLEXES
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V2O5 Catalyst in Contact process
Mn2+ Autocatalyst in MnO4 / C2O42- titrations
haemoglobin Contains Fe2+ – allows O2 to bond and carried to where needed
USES OF SOME COMPLEXES
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V2O5 Catalyst in Contact process
Mn2+ Autocatalyst in MnO4 / C2O42- titrations
haemoglobin Contains Fe2+ – allows O2 to bond and carried to where needed
[Pt(NH3)2Cl2] cis platin – anti-cancer drug
USES OF SOME COMPLEXES
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V2O5 Catalyst in Contact process
Mn2+ Autocatalyst in MnO4 / C2O42- titrations
haemoglobin Contains Fe2+ – allows O2 to bond and carried to where needed
[Pt(NH3)2Cl2] cis platin – anti-cancer drug
[Ag(NH3)2]+ Used in Tollen's reagent to distinguish
aldehydes and ketones
5.4.7 – USES OF SOME COMPLEXES
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V2O5 Catalyst in Contact process
Mn2+ Autocatalyst in MnO4 / C2O42- titrations
haemoglobin Contains Fe2+ – allows O2 to bond and carried to where needed
[Pt(NH3)2Cl2] cis platin – anti-cancer drug
[Ag(NH3)2]+ Used in Tollen's reagent to distinguish
aldehydes and ketones
[Ag(CN)2] - Used in silver electroplating
USES OF SOME COMPLEXES
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V2O5 Catalyst in Contact process
Mn2+ Autocatalyst in MnO4 / C2O42- titrations
haemoglobin Contains Fe2+ – allows O2 to bond and carried to where needed
[Pt(NH3)2Cl2] cis platin – anti-cancer drug
[Ag(NH3)2]+ Used in Tollen's reagent to distinguish
aldehydes and ketones
[Ag(CN)2] - Used in silver electroplating
[Ag(S2O3)2] 3- Formed in photography to remove
unreacted AgX from the film
USES OF SOME COMPLEXES
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SHAPES OF COMPLEX IONS
Co-ordination number
2 4 4 6
Shape
linear tetrahedral square planar
octahedral
Bond angles
Occurrence
e.g.
M M M M
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SHAPES OF COMPLEX IONS
Co-ordination number
2 4 4 6
Shape
linear tetrahedral square planar
octahedral
Bond angles 180º 109½º 90º 90º
Occurrence
e.g.
M M M M
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SHAPES OF COMPLEX IONS
Co-ordination number
2 4 4 6
Shape
linear tetrahedral square planar
octahedral
Bond angles 180º 109½º 90º 90º
Occurrence Ag+
complexes
e.g. [Ag(NH3)2]+
M M M M
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SHAPES OF COMPLEX IONS
Co-ordination number
2 4 4 6
Shape
linear tetrahedral square planar
octahedral
Bond angles 180º 109½º 90º 90º
Occurrence Ag+
complexes
Large ligands (e.g.
Cl-)
e.g. [Ag(NH3)2]+ [CuCl4]2-
M M M M
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SHAPES OF COMPLEX IONS
Co-ordination number
2 4 4 6
Shape
linear tetrahedral square planar
octahedral
Bond angles 180º 109½º 90º 90º
Occurrence Ag+
complexes
Large ligands (e.g.
Cl-)
Pt2+ complexes
e.g. [Ag(NH3)2]+ [CuCl4]2- [PtCl4]2-
M M M M
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SHAPES OF COMPLEX IONS
Co-ordination number
2 4 4 6
Shape
linear tetrahedral square planar
octahedral
Bond angles 180º 109½º 90º 90º
Occurrence Ag+
complexes
Large ligands (e.g.
Cl-)
Pt2+ complexes
Commonest
e.g. [Ag(NH3)2]+ [CuCl4]2- [PtCl4]2- [Cu(H2O)6]2+
M M M M
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SHAPES OF COMPLEX IONS
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SHAPES OF COMPLEX IONS
For each of the following complexes:
• Draw the complex.• Name the shape.• Show bond angles.• Give the metal oxidation state.• Give the co-ordination number.
1)[Ag(CN)2]-
2)[Cr(NH3)6]3+
3)[Ni(en)3]2+
4)[Co(en)2Cl2 ]+
5)[Pt(NH3)2Cl2]
6)[Fe(C2O4)3]4-
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SHAPES OF COMPLEX IONS
NC Ag CN
_
1 Linear
180º
Ag +1
Co-ordination number = 2
2 Octahedral
90º
Cr +3
Co-ordination number = 6
CrH3N NH3
H3N NH3
NH3
NH3
3+
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SHAPES OF COMPLEX IONS
3 Octahedral
90º
Ni +2
Co-ordination number = 6
4 Octahedral
90º
Co +3
Co-ordination number = 6
NH2
Cr
NH2
H2N NH2
H2N NH2
3+
Ni
2+
Cl
Cl
NH2H2N
NH2H2NCo
+
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SHAPES OF COMPLEX IONS
5 Tetrahedral
90º
Pt +2
Co-ordination number = 4
6 Octahedral
90º
Fe +2
Co-ordination number = 6
PtCl NH3
Cl NH3
O
Cr
NH2
O O
O O
CC
C
CC O
O
O
O
O
O
C
3-
Fe
4-
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SHAPES OF COMPLEX IONS
Geometric Isomerism e.g. [PtCl2(NH3)2]
cis trans
PtH3N Cl
Cl NH3Pt
Cl NH3
Cl NH3
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SHAPES OF COMPLEX IONS
Geometric isomerism
e.g. [CoCl2(NH3)4]+
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SHAPES OF COMPLEX IONS
e.g. [Co(en)3]3+
Optical Isomerism
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SHAPES OF COMPLEX IONS
Optical Isomerism
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FORMATION OF COLOURED IONS
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FORMATION OF COLOURED IONS
Once ligands bond, the five d orbitals are no longer have the same energy.
Energy = h
Energy is absorbed to excite electrons from the lower d orbitals to the higher d orbitals.
This energy is in the uv/visible region.
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FORMATION OF COLOURED IONS
Energy
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FORMATION OF COLOURED IONS
The colour you see is what is left after some colours are absorbed by the metal to excite electrons.
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FORMATION OF COLOURED IONS
The size of the energy gap between the d-orbitals, and so the colour is affected by changes in:
1) the metal
[Cu(H2O)6]2+
blue
[Fe(H2O)6]2+
green
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FORMATION OF COLOURED IONS
The size of the energy gap between the d-orbitals, and so the colour is affected by changes in:
2) the oxidation state
[Fe(H2O)6]3+
pale violet
[Fe(H2O)6]2+
green
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FORMATION OF COLOURED IONS
The size of the energy gap between the d-orbitals, and so the colour is affected by changes in:
3) the ligands
[Cu(H2O)6]2+
blue
[Cu(H2O)2(NH3)4 ]2+
deep blue
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FORMATION OF COLOURED IONS
The size of the energy gap between the d-orbitals, and so the colour is affected by changes in:
4) the co-ordination number
[Cu(H2O)6]2+
blue
[CuCl4 ]2-
yellow
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FORMATION OF COLOURED IONS
UV/Visible spectroscopy
• Frequencies at which complexes absorb can be measured by uv/visible spectroscopy.
• Light is passed through complex and the amount passing through measured.
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FORMATION OF COLOURED IONS
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FORMATION OF COLOURED IONS
Colorimetry
• The more concentrated the solution, the more it absorbs.
• This can be used to find the concentration of solutions – this is done in colorimeters.
• For some ions, a ligand is added to intensify the colour.
• The strength of absorption of solutions of known concentration is measured and a graph produced.
• The concentration of a solution of unknown concentration can be found by measuring the absorption and using the graph.
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FORMATION OF COLOURED IONS
Colorimetry