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Tutorial on Properties of Transition Metals, Complex ions and splitting of 3d orbitals by ligands. Review Lessons.

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Presentation on theme: "Tutorial on Properties of Transition Metals, Complex ions and splitting of 3d orbitals by ligands. Review Lessons."— Presentation transcript:

1 Tutorial on Properties of Transition Metals, Complex ions and splitting of 3d orbitals by ligands. Review Lessons

2 Transition Metals (d block elements) Ca 4s 2 K 4s 1

3 Transition Metals (d block elements) Across period Cr - 4s 1 3d 5 half filled more stable Cu - 4s 1 3d 10 fully filled more stable Ca 4s 2 K 4s 1

4 Transition Metals (d block elements) Across period Cr - 4s 1 3d 5 half filled more stable Cu - 4s 1 3d 10 fully filled more stable Ca 4s 2 K 4s 1 Transition metal have partially filled 3d orbitals 3d and 4s electrons can be lost easily electrons filled from 4s level first then 3d level

5 Transition Metals (d block elements) Across period Cr - 4s 1 3d 5 half filled more stable Cu - 4s 1 3d 10 fully filled more stable Ca 4s 2 K 4s 1 Transition metal have partially filled 3d orbitals 3d and 4s electrons can be lost easily electrons filled from 4s level first then 3d level electrons lost from 4s level first then 3d level Filling electrons- 4s level lower, filled firstLosing electrons- 4s higher, lose first 3d 4s

6 Transition Metals (d block elements) Across period Cr - 4s 1 3d 5 half filled more stable Cu - 4s 1 3d 10 fully filled more stable Ca 4s 2 K 4s 1 Transition metal have partially filled 3d orbitals 3d and 4s electrons can be lost easily electrons filled from 4s level first then 3d level electrons lost from 4s level first then 3d level 3d and 4s energy level close together (similar in energy) Filling electrons- 4s level lower, filled firstLosing electrons- 4s higher, lose first 3d 4s

7 Transition Metals d block elements with half/partially filled d orbitals/sublevels in one or more of its oxidation states Transition Metals (d block elements) Incomplete filled d orbitals Lose Ions Electrons formation

8 Transition Metals d block elements with half/partially filled d orbitals/sublevels in one or more of its oxidation states Transition Metals (d block elements) Incomplete filled d orbitals Lose Ions Electrons formation Sc 3+ 4s 0 3d 0 Zn 2+ 4s 0 3d 10 Zn not transition elements. Zn → Zn 2+ - (fully filled d orbital) 4s 2 3d 10 4s 0 3d 10 Sc not transition elements. Sc → Sc 3+ - (empty d orbital) 4s 2 3d 1 4s 0 3d 0

9 Transition Metals d block elements with half/partially filled d orbitals/sublevels in one or more of its oxidation states Transition Metals (d block elements) Incomplete filled d orbitals Lose Ions Electrons formation Sc 3+ 4s 0 3d 0 Zn 2+ 4s 0 3d 10 Zn not transition elements. Zn → Zn 2+ - (fully filled d orbital) 4s 2 3d 10 4s 0 3d 10 Sc not transition elements. Sc → Sc 3+ - (empty d orbital) 4s 2 3d 1 4s 0 3d 0

10 / Properties of Transition metals Formation of complex ions Formation coloured complexes Variable oxidation states Catalytic activity Transition Metals (d block elements) Formation coloured complexes Formation complex ions Variable Oxidation states Catalytic activity Sci-Media/Images/Catalytic-converter-catalyst

11 Oxidation state +2 more common on right (Co → Zn) Harder to lose electron as Nuclear charge of Co - Zn is getting higher (NC ↑) Oxidation state +3 more common on left (Sc → Fe) Easier to lose electron as Nuclear charge of Sc – Fe is lower (NC ↓) Oxidation state for Mn is highest +7 Higher oxidation state exist when elements bond to oxygen – oxides/oxyanions Transition Metals (d block elements) – Variable Oxidation States ScCI 3 TiCI 3 VCI 3 CrCI 3 MnCI 3 FeCI 3 CrCI 2 MnCI 2 FeCI 2 CoCI 2 NiCI 2 CuCI 2 ZnCI 2 TiCI 4 MnCI 4 V2O5V2O5 Cr 2 O 7 +2 (VO 2 ) 2+ (MnO 4 ) 2- (MnO 4 ) - oxides oxyanion chlorides

12 Oxidation state +2 more common on right (Co → Zn) Harder to lose electron as Nuclear charge of Co - Zn is getting higher (NC ↑) Oxidation state +3 more common on left (Sc → Fe) Easier to lose electron as Nuclear charge of Sc – Fe is lower (NC ↓) Oxidation state for Mn is highest +7 Higher oxidation state exist when elements bond to oxygen – oxides/oxyanions Transition Metals (d block elements) – Variable Oxidation States ScCI 3 TiCI 3 VCI 3 CrCI 3 MnCI 3 FeCI 3 CrCI 2 MnCI 2 FeCI 2 CoCI 2 NiCI 2 CuCI 2 ZnCI 2 TiCI 4 MnCI 4 V2O5V2O5 Cr 2 O 7 +2 (VO 2 ) 2+ (MnO 4 ) 2- (MnO 4 ) - oxides oxyanion chlorides Oxidation number increases +2 oxidation state more common+3 oxidation state more common

13 Transition Metals (d block elements) – Formation Complex Ions Transition Metal ion High charged density metal ion, partially filled 3d orbital Attract ligand (neutral, anion with lone pair electron) Form dative/co-ordinate bond – lone pair from ligands [Cu(H 2 O) 4 ]CI 2 [Cu(H 2 O) 4 ] CI - Ligands Neutral/anion species that donate lone pair/non bonding electron pair to metal ion Lewis base, lone pair donor – dative bond with metal ion Coordination number – number of ligands around central ion Transition Metal ion + Ligands = Complex Ions +2

14 Transition Metals (d block elements) – Formation Complex Ions 2+ 2CI - Complex ion – [Cu(H 2 O) 4 ]CI 2 also written as CuCI 2 Transition Metal ion High charged density metal ion, partially filled 3d orbital Attract ligand (neutral, anion with lone pair electron) Form dative/co-ordinate bond – lone pair from ligands CI 2 Complex ion 4 water ligands attached 4 dative bonds Coordination number = 4 + water [Cu(H 2 O) 4 ]CI 2 [Cu(H 2 O) 4 ] CI - Ligands Neutral/anion species that donate lone pair/non bonding electron pair to metal ion Lewis base, lone pair donor – dative bond with metal ion Coordination number – number of ligands around central ion Transition Metal ion + Ligands = Complex Ions Anion +2

15 Transition Metals (d block elements) – Formation Complex Ions 2+ 2CI - Complex ion – [Cu(H 2 O) 4 ]CI 2 also written as CuCI 2 Transition Metal ion High charged density metal ion, partially filled 3d orbital Attract ligand (neutral, anion with lone pair electron) Form dative/co-ordinate bond – lone pair from ligands CI 2 Complex ion 4 water ligands attached 4 dative bonds Coordination number = 4 Drawing complex ion Overall charged on complex ion Metal ion in the center (+ve charged) Ligands attached Dative bonds from ligands + water [Cu(H 2 O) 4 ]CI 2 [Cu(H 2 O) 4 ] CI - Ligands Neutral/anion species that donate lone pair/non bonding electron pair to metal ion Lewis base, lone pair donor – dative bond with metal ion Coordination number – number of ligands around central ion Transition Metal ion + Ligands = Complex Ions Anion +2

16 Coordination number Shape Complex ion (metal + ligand) Ligand (charged) Metal ion (Oxidation #) Overall charge on complex ion 2linear[Cu(CI 2 )] - CI = -1+1 [Ag(NH 3 ) 2 ] + NH3 = 0+1 [Ag(CN) 2 ] - CN = Square planar [Cu(CI) 4 ] 2- CI = [Cu(NH 3 ) 4 ] 2+ NH 3 =0+2 [Co(CI) 4 ] 2- CI= [Ni(CI) 4 ] 2- CI= Tetrahedral[Zn(NH 3 ) 4 ] 2+ NH 3 =0+2 [Mn(CI) 4 ] 2- CI= Octahedral[ Cu(H 2 O) 6 ] 2+ H 2 O =0+2 [Fe(OH) 3 (H 2 O) 3 ]OH =-1 H 2 O = 0 +3o [Fe(CN) 6 ] 3- CN = [Cr(NH 3 ) 4 CI 2 ] + NH 3 = 0 CI = Types of ligands: Monodentate – 1 lone pair electron donor – H 2 O, F -, CI -, NH 3, OH -, CN - Bidentate – 2 lone pair electron donor –1,2 diaminoethane H 2 NCH 2 CH 2 NH 2, ethanedioate (C 2 O 4 ) 2- Complex ions with different metal ions, ligands, oxidation state and overall charged

17 Naming Complex ions Step in naming complex ion - [Co(NH 3 ) 4 CI 2 ] + CI - Tetraamine dichloro cobalt (III) (cation part) 1.Cation part first → anion part later 2.Within a complex metal – ligands named first followed by metal ion 3.Name - Tetraamine dichloro cobalt (III) chloride Chloride (anion part)

18 Naming Complex ions Step in naming complex ion - [Co(NH 3 ) 4 CI 2 ] + CI - Tetraamine dichloro cobalt (III) (cation part) 1.Cation part first → anion part later 2.Within a complex metal – ligands named first followed by metal ion 3.Name - Tetraamine dichloro cobalt (III) chloride Chloride (anion part) Step in naming complex ion - [Cu(H 2 O) 4 ] 2+ CI 2 Tetraaqua copper (II) (cation part) 1.Cation part first → anion part later 2.Within a complex metal – ligands named first followed by metal ion 3.Name - Tetraaqua copper(II) chloride Chloride (anion part)

19 Naming Complex ions Step in naming complex ion - [Co(NH 3 ) 4 CI 2 ] + CI - Tetraamine dichloro cobalt (III) (cation part) 1.Cation part first → anion part later 2.Within a complex metal – ligands named first followed by metal ion 3.Name - Tetraamine dichloro cobalt (III) chloride Chloride (anion part) Step in naming complex ion - [Cu(H 2 O) 4 ] 2+ CI 2 Tetraaqua copper (II) (cation part) 1.Cation part first → anion part later 2.Within a complex metal – ligands named first followed by metal ion 3.Name - Tetraaqua copper(II) chloride Chloride (anion part) Step in naming complex ion - [Co(H 2 O) 6 ] 2+ SO 4 Hexaaqua cobalt(II) (cation part) 1.Cation part first → anion part later 2.Within a complex metal – ligands named first followed by metal ion 3.Name – Hexaaqua cobalt (II) sulphate Sulphate (anion part) Step in naming complex ions with TWO different ligands 1. Name ligand (alphabetical order) 2. [Cu(NH 3 ) 4 (H 2 O) 2 ] 2+ - tetraammine diaqua copper(II) ion. (1 st ligand- ammine, 2 nd ligand aqua) 3. [Al(H 2 O) 2 (OH) 4 ] - - diaqua tetrahydroxo aluminate ion. (1 st ligand – aqua, 2 nd ligand hydroxo)

20 Tetrachloro copper (II) ion CI - displace H 2 O Stronger ligand displace weaker ligand Ligand displacement [Cu(H 2 O) 4 ] CI → [Cu(CI) 4 ] 2- Tetraaqua copper (II) ion

21 Tetrachloro copper (II) ion CI - displace H 2 ONH 3 displace H 2 O Tetraamine copper (II) ion 2+ Stronger ligand displace weaker ligand Ligand displacement [Cu(H 2 O) 4 ] NH 3 → [Cu(NH 3 ) 4 ] 2+ [Cu(H 2 O) 4 ] CI → [Cu(CI) 4 ] 2- Tetraaqua copper (II) ion

22 Tetrachloro copper (II) ion CI - displace H 2 ONH 3 displace H 2 O Tetraamine copper (II) ion 2+ Stronger ligand displace weaker ligand Ligand displacement [Cu(H 2 O) 4 ] NH 3 → [Cu(NH 3 ) 4 ] 2+ [Cu(H 2 O) 4 ] CI → [Cu(CI) 4 ] 2- Tetraaqua copper (II) ion [Co(H 2 O) 6 ] CI → [Cu(CI) 4 ] 2- Tetrachloro cobalt(II) ionHexaaqua cobalt (II) ion CI - displace H 2 O Tetrachloro copper (II) ion Hexaaqua iron (III) ion

23 Taken from: Why transition metals ion complexes have different colour? Transition Metals (d block elements) – Coloured Complexes

24 Taken from: Why transition metals ion complexes have different colour? Why Titanium (III) ion is violet ? Transition Metals (d block elements) – Coloured Complexes

25 Colour formation due to splitting of 3d orbitals of metal ion by ligands Transition Metals (d block elements) – Coloured Complexes Absence of ligands 3d orbitals same energy level five 3d orbitals are equal in energy Five 3d orbitals

26 Colour formation due to splitting of 3d orbitals of metal ion by ligands Transition Metals (d block elements) – Coloured Complexes Absence of ligands 3d orbitals same energy level five 3d orbitals are equal in energy Presence of ligands 3d orbitals split five 3d orbitals unequal in energy Five 3d orbitals Splitting 3d orbitals

27 Colour formation due to splitting of 3d orbitals of metal ion by ligands Transition Metals (d block elements) – Coloured Complexes Absence of ligands 3d orbitals same energy level five 3d orbitals are equal in energy Presence of ligands 3d orbitals split five 3d orbitals unequal in energy Five 3d orbitals Splitting 3d orbitals No ligands No splitting of 3d orbitals 3d orbitals equal energy Why Titanium (III) ion solution is violet ? violet

28 Colour formation due to splitting of 3d orbitals of metal ion by ligands Transition Metals (d block elements) – Coloured Complexes Absence of ligands 3d orbitals same energy level five 3d orbitals are equal in energy Presence of ligands 3d orbitals split five 3d orbitals unequal in energy Five 3d orbitals Splitting 3d orbitals No ligands No splitting of 3d orbitals 3d orbitals equal energy With ligands Splitting of 3d orbitals 3d orbitals unequal energy Splitting 3d orbitals 3d orbitals split into different energy level Electronic transition possible Photon of light absorbed to excite electrons Why Titanium (III) ion solution is violet ? violet

29 Why Titanium (III) ion solution is violet ? Transition Metals (d block elements) – Coloured Complexes Ti 3+ transmit blue/violet region BUT absorb green/yellow/red

30 Why Titanium (III) ion solution is violet ? Transition Metals (d block elements) – Coloured Complexes Ti 3+ transmit blue/violet region BUT absorb green/yellow/red Light in vis region Ground state Ti 3+ (3d 1 ) Ti 3+ absorb green/yellow/red photons to excite electrons to higher level Ti 3+ transmit blue/violet region Electron excited

31 Cu 2+ transmit blue/violet BUT absorb /orange/red region Transition Metals (d block elements) – Coloured Complexes Why Copper (II) ion solution is blue ?

32 Cu 2+ transmit blue/violet BUT absorb /orange/red region Transition Metals (d block elements) – Coloured Complexes Why Copper (II) ion solution is blue ? Light in vis region Ground state Cu 2+ (3d 9 ) Cu 2+ absorb orange/red photons to excite electrons to higher level Cu 2+ transmit blue/violet region Electron excited Cu 2+ appears blue Complementary colour (Red/Orange) are absorbed to excite electron Blue colour is transmitted

33 Transition metal have different colours due to splitting of 3d orbitals by ligands partially filled 3d orbitals for electron transition Why some are colourless ? Cu 2+ anhydrous – colourless Cu 1+ hydrous – colourless Zn 2+ hydrous – colourless Sc 3+ hydrous – colourless Transition Metals (d block elements) – Coloured Complexes

34 Transition metal have different colours due to splitting of 3d orbitals by ligands partially filled 3d orbitals for electron transition CuSO 4 (anhydrous) without ligands - Colourless Why some are colourless ? Cu 2+ anhydrous – colourless Cu 1+ hydrous – colourless Zn 2+ hydrous – colourless Sc 3+ hydrous – colourless Transition Metals (d block elements) – Coloured Complexes No ligands No splitting of 3d orbitals No electron transition No colour NO Colour

35 Transition metal have different colours due to splitting of 3d orbitals by ligands partially filled 3d orbitals for electron transition CuSO 4 (anhydrous) without ligands - Colourless Why some are colourless ? Cu 2+ anhydrous – colourless Cu 1+ hydrous – colourless Zn 2+ hydrous – colourless Sc 3+ hydrous – colourless Transition Metals (d block elements) – Coloured Complexes No ligands No splitting of 3d orbitals No electron transition No colour Ground state Cu 2+ (3d 9 ) Ligands split the 3d orbitals Electron transition from lower to higher level by absorbing ∆E CuSO 4 (hydrous) with H 2 O ligands – Blue Colour NO Colour Colour [Cu(H 2 O) 6 ] 2+ SO 4 – splitting 3d orbitals by ligand – Blue colour

36 Transition Metals (d block elements) – Coloured Complexes Sc 3+ ion with ligands - Colourless Ground state Sc 3+ (3d 0 ) Ligands split the 3d orbitals No electrons in 3d orbital No electron transition NO Colour [Sc(H 2 O) 6 ] 3+ CI 3 Empty 3d orbitals No colour

37 Transition Metals (d block elements) – Coloured Complexes Sc 3+ ion with ligands - Colourless Zn 2+ ion with ligands - Colourless Ground state Sc 3+ (3d 0 ) Ligands split the 3d orbitals No electrons in 3d orbital No electron transition NO Colour [Sc(H 2 O) 6 ] 3+ CI 3 Empty 3d orbitals No colour Ground state Zn 2+ (3d 10 ) Ligands split the 3d orbitals Fully filled in 3d orbital No electron transition NO Colour [Zn(H 2 O) 6 ] 2+ SO 4 Filled 3d orbitals No colour

38 Transition Metals (d block elements) – Coloured Complexes Cu 1+ ion with H 2 O ligands - Colourless Ground state Cu 2+ (3d 10 ) Ligands split the 3d orbitals Fully filled in 3d orbital No electron transition [Cu(H 2 O) 6 ] 1+ CI Filled 3d orbitals No colour NO Colour

39 Transition Metals (d block elements) – Coloured Complexes Cu 1+ ion with H 2 O ligands - Colourless Ground state Cu 2+ (3d 10 ) Ligands split the 3d orbitals Fully filled in 3d orbital No electron transition [Cu(H 2 O) 6 ] 1+ CI Filled 3d orbitals No colour NO Colour Cu 2+ ion without H 2 O ligands – Colourless No ligands No splitting of 3d orbitals No electron transition No colour NO Colour

40 Transition Metals (d block elements) – Coloured Complexes Cu 1+ ion with H 2 O ligands - Colourless Ground state Cu 2+ (3d 10 ) Ligands split the 3d orbitals Fully filled in 3d orbital No electron transition [Cu(H 2 O) 6 ] 1+ CI Filled 3d orbitals No colour NO Colour Ground state Cu 2+ (3d 9 ) Ligands split the 3d orbitals [Cu(H 2 O) 6 ] 2+ SO 4 – splitting 3d orbitals by ligand – Blue colour Cu 2+ ion with H 2 O ligands – Blue Colour Electron transition from lower to higher level by absorbing ∆E Colour Cu 2+ ion without H 2 O ligands – Colourless No ligands No splitting of 3d orbitals No electron transition No colour NO Colour

41 Transition Metals (d block elements) – Catalytic Activity Catalytic Properties of Transition metal Variable oxidation state - lose and gain electron easily Acts as Homogeneous or Heterogenous catalyst – lower activation energy Homogeneous catalyst – catalyst and reactants are in the same phase Heterogeneous catalyst – catalyst and reactants are in different phase Heterogenous catalyst- Metal surface provide active site (lower Ea ) Surface catalyst bring molecule together (close contact) -bond breaking/making easier Transition metal work as a catalyst with diff oxidation states 2 H 2 O 2 + Fe 2+ → 2H 2 O + O 2 + Fe 3+ H 2 O 2 + Fe 2+ → H 2 O + O 2 + Fe 3+ Fe 3+ + I - → Fe 2+ + I 2 Fe 2+ ↔ Fe 3+ Reaction is slow if only I- is added H 2 O 2 + I - → I 2 + H 2 O + O 2 Reaction speeds up if Fe 2+/ Fe 3+ added Fe 2+ changes to Fe 3+ and is change back to Fe 2+ again 3+ recycle

42 Haber Process – Production of ammonia for fertilisers and agriculture 3H 2 + N 2 → 2NH 3 Contact Process – Sulphuric acid for fertilisers, detergent, paints and batteries 2SO 2 + O 2 → 2SO 3 Hydrogenation Process- Margerine and trans fats C 2 H 4 H 2 → C 2 H 6 Hydrogen peroxide decomposition – Oxygen production 2H 2 O 2 → 2H 2 O + O 2 Catalytic converter – Convertion of CO and NO to CO 2 and N 2 2CO + 2NO → 2CO 2 + N 2 Biological enzymes Hemoglobin – transport oxygen Vitamin B 12 – RBC production Uses of transition metal as catalyst in industrial processes

43 Haber Process – Production of ammonia for fertilisers and agriculture 3H 2 + N 2 → 2NH 3 Contact Process – Sulphuric acid for fertilisers, detergent, paints and batteries 2SO 2 + O 2 → 2SO 3 Hydrogenation Process- Margerine and trans fats C 2 H 4 H 2 → C 2 H 6 Hydrogen peroxide decomposition – Oxygen production 2H 2 O 2 → 2H 2 O + O 2 Catalytic converter – Convertion of CO and NO to CO 2 and N 2 2CO + 2NO → 2CO 2 + N 2 Biological enzymes Hemoglobin – transport oxygen Vitamin B 12 – RBC production Uses of transition metal as catalyst in industrial processes Iron, Fe Vanadium (V) oxide, V 2 O 5 Nickel, Ni Manganese (IV) oxide, MnO 2 Platinum/Palladium, Pt/Pd Cobalt, Co Iron, Fe

44 Click here to view nickel ion complexeshere Click here to view vanadium ion complexeshere Click here to view iron in hemoglobinhere Click here to view oxidation states here Video on transition metal


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