What is a transition metal?

 Can form 1 or more stable ions with incompletely filled d orbitals

Why is scandium not a transition metal?

 It always loses the outer 3 electrons [Ar]3d14s2
 Sc3+ has no d electrons
 Doesn’t meet the definition
 Doesn’t form a coloured compounds

Electronic Configurations:

 4s orbital has a lower energy level from 3d so is filled up first

 Exceptions Cu + Cr which have incomplete 4s
 When they lose electrons they lose it from 4s first
 Orbitals are filled unpaired initially
 1s<2s<2p<3s<3p<4s<3d<4p
Characteristics?
 Hard solids
 High melting and boiling points
 Act as catalysts
 Form colored ions
 Variable oxidation states
 Ions have incompletely filled d-orbitals

Why variable oxidation states?

 3d and the 4s orbital are close in energy
 can lose different amounts of electrons at similar amounts of energy
 those with higher oxidation states usually have an electronegative
element (usually O2)
Ligand definition:
 Species that uses a lone pair of electrons to form dative bond with a
metal
 Dative bond is when one element is the one suppling both electrons
 i.e Oxygen in water is the one contributing its lone pair in the bond

 H2O, OH− and NH3 act as monodentate ligands

 Since only 1 lone pair of electrons is involved
 Each can only form 1 dative bond with metal ion

What is a complex ion?

 Is a central transition metal ion surrounded by ligands (i.e water)
 The total number of dative bonds is called coordination number

Formation of Complex ions:

 Transition metals have a smaller radius than those in same period
 Enables them to attract electron rich species more strongly
 They are attracted so strongly that they form dative bonds
 So the transition metal is surrounded by electron rich species
 This structure is known as a complex (complex ion)
Naming a complex ion
 The number of ligands (coordination)
 The name of the ligand
 The name of the metal ion
 The oxidation number of metal ion
 i.e above example hexaaquairon(ll)
 If 2 ligands (put in alphabetical order)

Why transition metals form coloured ions in solution?

 Only those with incomplete 3d orbitals are coloured
 So zinc and Scandium ions are NOT coloured
 When a transition metal binds a ligand
 The 3d energy level is split into 2 different energies
 One with a lower energy level and one with a higher energy
 If one e- in lower level absorbs energy from visible spectrum
 It’s excited to the higher energy level
 Amount of energy absorbed depends on difference between levels
 Energy absorbed is proportional to frequency of absorbed light
 And inversely proportional to wavelength of the light
 Colour seen is complementary of the colour absorbed

Why is there a lack of colour in some aqueous ions?

 If wavelength is not in the visible light region we don’t see a colour
 The metal needs to be have an incomplete 3d orbital
 A ligand must be present to split the energy level of 3d orbital

How do colour changes in transition metal ions occur?

 The colour seen is complementary to that absorbed
 Depends on the wavelength absorbed (depends on energy absorbed)
 Difference in energy levels depends on how strong splitting is
 The stronger the splitting, the greater difference between energy
levels

The strength of the splitting depends on:

 Oxidation number of metal

 Ligand used
 Coordination number
Shape of Complex ions (monodentate ligands)
 Electron repulsion is used to explain shapes of compounds
 With complex ions we count the number of electrons donated
 According to the number we determine the shape
 Since the electron donors are group 2 elements they are
approximately of equal size

Tetrahedal Complexes:
 These are less common
 The one you will see is [CuCl4]2-
 Since Cl is a period 3 element it’s ion is bigger than H2O
 So there is insufficient room around the ion for 6 Cl

Linear Complexes:
 Ion present in tollen’s reagent
 Ammoniacal sliver nitrate
Square Planar Complexes:
 Occurs when there are 2 lone pairs + 4 covalent bonds
 Platinum is a transition metal in period 6
 It forms a square planar
 The Cis-platin is used in cancer treatment (testicular)
 Forms a bond between 2 strands of DNA
 Preventing DNA from separating + so cell can’t divide

Cis:
 identical ligands are next to each other

Trans:
 identical ligands are opposite each other
 Trans-platin is less effective in cancer treatment
 It is also more toxic

Bidentate Ligands:
 The molecule can use 2 lone pairs to form 2 dative bonds
 An example is 1,2 diaminoethane
 Each nitrogen contributes a lone pair to form a dative bond

 When reacts with hexaaqua metal ion displaces all water molecules
Multidentate Ligands:
 EDTA4- is an organic ion
 Forms several dative bonds with a metal ion
 Has 6 lone pairs

Complex Stability:
 When a monodentate is replaced by a bidentate
 [Cu(H2O)6]2+ + 3en  [Cu(en)3]2+ + 6H2O
 So total number of species increased from 4 to 7]
 So the system becomes more disordered & Ssystem increases
 So the products are more stable than reactants
 Product formation is favoured
 A greater increase is seen when a monodentate is replaced by a
multidentate

Haemoglobin:
 Haem contains 4 N forming dative bonds with Fe2+
 It’s a square planar structure
 When O2 is picked up it forms a dative bond with Fe2+
 The bond is not strong allowing oxygen to be easily released
 A stronger bond forms between CO + Fe2+
 This replaces O2 (ligand substitution)
 The bond is hard to break
Reactions

1) Redox
 Change in transition metal oxidation number
 A colour change occurs
 The type + number of ligands is the same
 i.e [Fe(H2O)6]2+ is green / [Fe(H2O)6]3+ is brown
 Occurs when complex is exposed to air

2) Acid-base
 A ligand gains or loses a H+
 [Cu(H2O)6]2+ + 2OH-  [Cu(H2O)4(OH)2] + 2H2O
 This is described as amphoteric behavior
 It is a reversible reaction

3) Ligand exchange
 Occurs with NH3 and H2O
 [Cu(H2O)6]2+ + 2NH3  [Cu(H2O)4(OH)2] + 2NH4+ (ACID-BASE)
 [Cu(H2O)4(OH)2] + 4NH3  [Cu(NH3)4(OH)2]2+ + 2H2O + 2OH-
 Pale blue to blue ppt to deep blue solution

4) Coordination number change

 Involves a change in ligand
 i.e reaction with HCl
 [Cu(H2O)6]2+ + 4Cl-  [CuCl4]2- + 6H2O
 Blue to Green to Yellow
 The green is due to a mixture of blue + yellow
 With NaOH With NH3 Excess NH3 With HCl
[Co(H2O)6]2+ [Co(H2O)4(OH)2] + [Co(H2O)4(OH)2] + [Co(NH3)6]2+ + 4H2O + [CoCl4]2- +
2H2O 2NH4+ 2OH- 6H2O

[Cr(H2O)6]3+ [Cr(H2O)3(OH)3] + [Cr(H2O)3(OH)3] + [Cr(NH3)6]3+ + 3H2O + ---------------

3H2O 3NH4+ 3OH-

[Cu(H2O)6]2+ [Co(H2O)4(OH)2] + [CU(H2O)4(OH)2] + [Cu(NH3)4(H2O)2] + 2H2O [CuCl4]2- +

2H2O 2NH4+ + 2OH- 6H2O

[Fe(H2O)6]2+ [Fe(H2O)4(OH)2] + [Fe(H2O)4(OH)2] + ----------------------- ---------------

2H2O 2NH4+
[Fe(H2O)6]3+ [Fe(H2O)6] + 3H2O [Fe(H2O)6] + 2NH4+ ----------------------- ---------------

[Fe(H2O)4(OH)2] IS OXIDISED to [Fe(H2O)3(OH)3] brown ppt

[Fe(H2O)6]3+ YELLOW-BROWN

Colour Of solutions depends on:

 The concentration of product
 The presence of dissolved O2

Chromate(6) and Dichromate(6):

 CrO42- are stable in alkaline solution yellow
 Cr2O72- are more stable in acidic solution orange
 CrO42- + 2H+  Cr2O72- + H2O

Reduction of Cr2O72-:
 Reduced by zinc in acidic conditions

Step 1:
Cr2O72- + 14H+ + 3Zn  2Cr3+ + 7H2O + 3Zn2+

Zn2+ + 2e-  Zn E= -0.76V

Cr2O72- + 14H+ + 6e-  2Cr3+ + 7H2O E= +1.33V

Ecell= +1.33 – (-0.76)

Ecell= +2.09V (so reaction thermodynamically feasible)
Step 2:
2Cr3+ + Zn  2Cr2+ + Zn2+

Zn2+ + 2e-  Zn E= -0.76V

Cr3+ + e-  2Cr2+ E= -0.41V

Ecell= -0.41 – (-0.76)

Ecell= +0.35V (so reaction thermodynamically feasible)

NOTE: can be oxidized from +3 to +6 using hydrogen peroxide in

alkaline conditions

Reactions of vanadium:

 The reduction is achieved through zinc

Reduction from +5 to +4
 VO2 + 2H+ + e-  VO2+ + H2O E= +1.00V
 Zn  Zn2+ + 2e- E= +0.76V
Reduction from +4 to +3
 VO2+ + 2H+ + e-  V3+ + H2O E= +0.34V
 Zn  Zn2+ + 2e- E= +0.76V

Reduction from +3 to +2
 V3+ + e-  V2+ E= -0.26V
 Zn  Zn2+ + 2e- E= +0.76V

Heterogeneous Catalyst
 In a different phase from the reactant
 Manganese(4) oxide catalyzes reaction of H2O2  O2 + H2
 Manganese oxide is a solid whilst H2O2 is a liquid
 Many transition metals + their compounds are used as solid catalyst
 Reaction occurs on the surface
 So most are finely divided to increase surface area

Surface adsorption theory

 Reactant/s attached to catalyst surface
 The bonds are weakened and reaction occurs
 Products deattach from surface

Surface adsorption theory

 Reactant/s attached to catalyst surface
 The bonds are weakened and reaction occurs
 Products deattach from surface

Contact Process
 Used to produce sulphuric acid (fertilizers)
 Vanadium(v) Oxide used V2O5
2SO2 + O2  2SO3
 Vanadium oxide reduces sulfur dioxide generating V2O4
 Oxygen reacts with V2O4 to regenerate V2O5
Why Catalytic Converters
 CO is toxic and interferes with O2 transport
 Incomplete combustion of hydrocarbons produces CO
 NO is easily oxidized in atmosphere to NO2
 NO2 is a lung irritant and contributes to acid rain
 Generated from reaction between N + O at high temperatures

Catalytic Converters
 Platinum + Rhodium used
 CO & NO adsorped onto catalyst surface
 Then, because their bonds are weakened
 They react together to form CO2 + NO2
 They are then desorbed from surface of catalyst

2CO + 2NO  2CO2 + N2

Homogeneous Catalyst
 Is in same phase as reactants
 They form an intermediate catalyst

S2O82- as an oxidizing agent

 Oxidises I- to I2
 Since both reactants are –ive they repel each other
 Thus reaction is slow at room temperature
 Fe2+ acts as a catalyst for this reaction

Step1:
 Fe2+ reacts with S2O82-
 2Fe2+ + S2O82-  2SO42- + 2Fe3+

Step2:
 Fe3+ reacts with I-
 2Fe3+ + 2I-  2Fe2+ + I2
Reaction between MNO4- + C2O42-
 Since both reactants are –ive they repel each other
 Thus reaction is slow at room temperature
 Mn2+ generated acts as a catalyst for this reaction
 It is referred to as autocatalysis

2MnO4- + 5C2O42- + 16H+  2Mn2+ + 5CO2 + 8H2O

Autocatalysis:
 When a reaction product acts as a catalyst for the reaction