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What are the transition elements?
The transition elements are d-block elements which form one or more stable ions with incomplete d sub-shell electrons.
A transition element forms at least one ion with a partially-filled d-subshell
Ac Rf Db Sg Bh Hs Mt Ds Rg
La Hf Ta W Re Os Ir Pt Au Hg
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
Sc Ti V Cr Mn Fe Co Ni Cu Zn
?
Here, the word ‘transition’ is used to mean ‘in-between’.
group 2 group 3
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Uses of coloured trans. metal compounds
The coloured compounds of transition metals can also be used in many ways, for example:
as coloured glazes on pottery.
to colour paints
to colour stained glass windows
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What are the uses of the transition metals?
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Prentice-Hall © 2002
General Chemistry: Chapter 24
Slide 6 of 47
Catalysis
• Catalysis plays an essential aspect in about 90% of all chemical manufacturing.
• Ni and Pt are very heterogeneous catalysts.
• Pt, Rh, and Pd are used in catalytic converters.
• V2O5 is used in conversion of SO2 to SO3.• Polyethylene is formed catalytically.
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First row d-block elements
Elements Atomic num. Electronic Configuration[Ar] …
Sc 21 [Ar] 3d1 4s2Ti 22V 23Cr 24Mn 25Fe 26Co 27Ni 28Cu 29Zn 30
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Most common oxidation state
Elements Electronic Configuration
Known oxidation state
Sc [Ar] 3d1 4s2 +3Ti [Ar] 3d2 4s2 +3, +4V [Ar] 3d3 4s2 +2, +3, +4, +5Cr [Ar] 3d5 4s1 +3, +6Mn [Ar]3d5 4s2 +2, +4, +6, +7Fe [Ar] 3d6 4s2 +2, +3Co [Ar] 3d7 4s2 +2, +3Ni [Ar] 3d8 4s2 +2Cu [Ar] 3d10 4s1 +1, +2Zn [Ar] 3d10 4s2 +2
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Write the electron configuration of
•Cr3+
•Cu2+
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exercise
• Explain why scandium (III) and zinc (II) cations are not called transition elements.
• Why is the maximum oxidation state of manganese +7?
• In the higher oxidation states, the elements exist as covalently bonded oxo-compounds rather than atomic ions. Explain this phenomenon
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Characteristic of transitional metals on their compounds
• Variable oxidation stateDue to similar energy of 4s and 3d
• Formation of coloured ions / complex ionsDue to electrons transition between d-orbitals
• Catalytic activityProvide alternative reaction mechanism with
lower activation energy• Paramagnetism
Unpaired or odd electrons
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The transition metals are known as ‘typical’ metals because of their physical properties. They are:
What are the properties of the transition metals?
lustrous (bright and shiny).
high density.
good conductors of heat and electricity.
high melting and boiling points (except mercury, which is liquid at room temperature).
hard and strong.
malleable (can be bent and pressed into different shapes) and ductile (can be drawn into wires).
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Prentice-Hall © 2002
General Chemistry: Chapter 24
Slide 13 of 47
Color and Magnetism
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Comparing properties of different metals
How do the properties of transition metals compare with those of alkali metals?
are more dense. This means that in a fixed volume of metal there are more atoms of a transition metal than there are of an alkali metal.
have higher melting and boiling points – except mercury.
are harder and stronger. They cannot be cut with a knife.
Compared to the alkali metals, the transition metals:
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Comparing densities of metals
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Comparing melting points of metals
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True or false?
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Redox reactions
• A positive Ecell indicates a thermodynamically feasible reaction
• A negative Ecell indicates a thermodynamically non-feasible reaction
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• Judging from Ecell [ data booklet ]oPredict the outcome of mixing aqueous
iron(II) with chlorine.oPredict the outcome of mixing acidified
tin (II) with hydrogen peroxide (H2O2)oWhich one is the better oxidising agent
in acidified solution : KMnO4 or K2Cr2O7
to oxidized solution of iron(II)
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Complex ions
• A compound in which ligand molecules form (dative) co-ordinate bonds to a centre metal atom or ion.
• Ligand :a ion or molecule that has at least a lone pair of electrons available for donation to the central metal atom or ion.
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How to write a complex structure
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Features of complex ions
• Net charge on complex ions
Knowing the charge on a complex ion and the charge on each ligand, one can determine the
oxidation number for the metal.
Net charge
Ligand’s
Charge
Oxidation number
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Features of complex ions
• In a compound, complex ion attaches to a counter ion.
K4[Fe(CN)6]
Na2CuCl4[Cu(NH3)4]SO4
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Features of complex ions
• Co-ordination number(number of dative bonds attached)
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Ligands
• NeutralH2O, NH3, CO, amines, etc
• IonicCl-, CN-, etc
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Types of ligands
• Based on number of dative bonds:oMonodentate [ one dative bond ]
oH2O, NH3, halide, CN-, CO
o Bidentate [ two dative bonds ]oEthylenediamine, oxalate ions
o Polydentate [ more than two dative bonds ]oEDTA (EthyleneDiamineTetraAcetate ion)
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chelate• Bidentate or polydentate ligands that form
ring in a complex ion.– Ethane-1,2-diamine [“en”]– Ethanedioate ions [“ox”]– EDTA
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Rule for naming complex ions
• Complex cation– Names of ligands are given first, then the
central ion with its oxidation state in brakets– Ligands are named in alphabetical order with
suitable prefix to indicate number of ligand present [di, tri, tetra, etc]
– The ligand and central ion are named without space
• Complex anion– Similar method, except central metal ion is
altered to end in -ate
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Ligands H2O NH3 F- Cl- CN- SCN- OH-Name aqua ammine fluoro chloro cyano thiocyanate Hydroxo
Cationic complexes Anionic complexesTitanium Titanatevanadium VanadateManganese ManganateIron FerrateCopper Cuprate
These are strong ligands
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Prentice-Hall © 2002
General Chemistry: Chapter 25
Slide 32 of 55
Table 25.2 Some Common Monodentate Ligands.
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Give names
• Cu(en)22+
• Fe(Ox)33-
• [Cu(H2O)6]2+
• [Cr(NH3)5Cl]2+
• [Fe(CN)6]4-
• [Fe(H2O)6]2+
• [Cu(H2O)6]SO4
• [Cr(NH3)5Cl]Cl2• K4[Fe(CN)6]
• [Fe(H2O)6](NO3)2
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General Chemistry: Chapter 25
Slide 34 of 55
Ethylene Diamine
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Copper complex in ligand substitution
add ammonia solution
Cu(H2O)62+ Co(NH3)4(H2O)2
2+
blue deep blue / violet
CuCl42- Cu(OH)2 yellow-green pale blue
Add NaOH or NH3 (aq)
Add conc
HCl
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Substitution of ligands
• Ligands can be exchange in the complex ions.
Cu(H2O)62+ + 2OH- Cu(OH)2(H2O)4(s) + 2H2O
pale blueCu(OH)2(H2O)4(s) + 4NH3 [Cu(H2O)2(NH3)4]2+ +
2H2O + 2OH-
Deep blue
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General Chemistry: Chapter 24
Slide 37 of 47
Metal Carbonyls
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Shape of complex ions
Coordination number
Shape Hybridization Examples
2 Linear sp [CuCl2]-
4 Tetrahedral sp3 [CuCl4]-
4 Square planar
dsp2 [Ni(CN)4]2-
6 Octahedral sp3d2 [Fe(H2O)6]2+
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Orbital d
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General Chemistry: Chapter 24
Slide 40 of 47
Oxidation States
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Colour of complexes
• Depends on:– The nature of the central metal ions– Oxidation state of the central metal ions– Types of ligands
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Splitting of d orbitals
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• The two d-orbitals [dx2-y2, and dz2] locate along axes causing a repulsion by the coming electron from the ligans, as to compare with the other d-orbitals [dxy, dyz, dxy] which locate in between axes having lower repulsion.
• This causes d-orbitals to separate into 2 different energy levels.
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General Chemistry: Chapter 25
Slide 44 of 55
Octahedral Complex and d-Orbital Energies
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General Chemistry: Chapter 25
Slide 45 of 55
Electron Configuration in d-Orbitals
Hund’s rule
Δ > Plow spin d4
Δ < P high spin d4
pairing energy considerations
ΔP
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The effect of types of ligand
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CN- > NO2- > en > py NH3 > EDTA4- > SCN- > H2O >
ONO- > ox2- > OH- > F- > SCN- > Cl- > Br- > I-
Large ΔStrong field ligands
Small ΔWeak field ligands
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Transition between d-d* electron
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General Chemistry: Chapter 25
Slide 51 of 55
Geometric Isomerism
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conclusion
• A substance appears coloured when certain wavelength of white light is absobed. The complementary wavelength [white light minus the colour absobed] gives the colour of the substance
• Transition of electron(s) d-d* transition
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General Chemistry: Chapter 25
Slide 53 of 55
Effect of Ligands on the Colors of Coordination Compounds
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Homework
• Explain the term homogeneous and heterogeneous catalyst.
• Give examples and reactions for homogeneous and heterogeneous catalyst.
• Compare, qualitatively, the melting point, density, atomic radius, ionic radius, first ionization energy and conductivity of the transition elements with those of calcium as a typical s-block element.
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Glossary (1/2)alloy – A mixture of a metal and at least one other element.
catalyst – A substance that increases the speed of a chemical reaction without being used up.
corrosion – Damage to a metal caused by a chemical or reaction such as rusting.
density – A measure of mass in a given volume. Often expressed in g/dm3.
ductile – The ability of metals to be drawn into wires.
lustrous – Bright and shiny.
malleable – Capable of being bent and pressed into a different shape.
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Glossary (2/2)precipitate – A solid that forms in a solution as a result
of a physical or chemical reaction.
thermal decomposition – The process by which a substance is broken down into two or more products by heating it.
transition metal – An element located in the block between groups 2 and 3 of the periodic table.
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Anagrams
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Properties of transition metals
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Multiple-choice quiz