Chemsheets AS006 (Electron arrangement)

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Presentation transcript:

Chemsheets AS006 (Electron arrangement) 21/04/2017 www.CHEMSHEETS.co.uk TRANSITION METALS © www.chemsheets.co.uk A2 043 20-Jul-12

ELECTRON STRUCTURES Fe [Ar] 4s2 3d6 Cu [Ar] 4s1 3d10 Fe3+ [Ar] 3d5 Cu+ 4s fills and empties before 3d Fe [Ar] 4s2 3d6 Cu [Ar] 4s1 3d10 Fe3+ [Ar] 3d5 Cu+ [Ar] 3d10 Sc [Ar] 4s2 3d1 Cu2+ [Ar] 3d9 Sc3+ [Ar] Zn [Ar] 4s2 3d10 V [Ar] 4s2 3d3 Zn2+ [Ar] 3d10 V2+ [Ar] 3d3 Cr [Ar] 4s1 3d5 © www.chemsheets.co.uk A2 043 20-Jul-12

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+) © www.chemsheets.co.uk A2 043 20-Jul-12

PROPERTIES OF TRANSITION METALS? 1) They form coloured ions. photo by Ian Geldard

PROPERTIES OF TRANSITION METALS? 2) They form complexes (ligands form co-ordinate bonds to the metal ion). [Cu(H2O)6]2+ [CuCl4]2- © www.chemsheets.co.uk A2 043 20-Jul-12

PROPERTIES OF TRANSITION METALS? 3) They exhibit variable oxidation states.

PROPERTIES OF TRANSITION METALS? 4) They show catalytic activity. e.g. Ni margarine production V2O5 making SO3 for H2SO4 Fe Haber process to make NH3 Pt, Pd catalytic converters © www.chemsheets.co.uk A2 043 20-Jul-12

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 © www.chemsheets.co.uk A2 043 20-Jul-12

Ligands form co-ordinate bonds via lone pairs COMPLEX FORMATION Lewis base lone pair donor (ligands are Lewis bases) Lewis acid lone pair acceptor H+ + :OH- → H2O Lewis acid Lewis base Ligands form co-ordinate bonds via lone pairs © www.chemsheets.co.uk A2 043 20-Jul-12

COMPLEX FORMATION [Cu(H2O)6]2+ [CuCl4]2- Unidentate ligands – form one co-ordinate bond e.g. H2O:, :OH-, :NH3, :CN-, :Cl- [Cu(H2O)6]2+ [CuCl4]2- © www.chemsheets.co.uk A2 043 20-Jul-12

COMPLEX FORMATION [Cr(C2O4)3]3- [Cr(en)3]3+ Bidentate ligands – form two co-ordinate bonds ethanedioate (C2O42-) 1,2-diaminoethane (en) [Cr(C2O4)3]3- [Cr(en)3]3+ © www.chemsheets.co.uk A2 043 20-Jul-12

COMPLEX FORMATION e.g. [Cu(EDTA)]2- Multidentate ligands – form several co-ordinate bonds EDTA4- e.g. [Cu(EDTA)]2-

COMPLEX FORMATION Multidentate ligands – form several co-ordinate bonds porphyrin e.g. haem

COMPLEX FORMATION Multidentate ligands – form several co-ordinate bonds haemoglobin

USES OF SOME COMPLEXES V2O5 Catalyst in Contact process © www.chemsheets.co.uk A2 043 20-Jul-12

USES OF SOME COMPLEXES V2O5 Catalyst in Contact process Mn2+ Autocatalyst in MnO4- / C2O42- titrations © www.chemsheets.co.uk A2 043 20-Jul-12

USES OF SOME COMPLEXES V2O5 Catalyst in Contact process Mn2+ Autocatalyst in MnO4 / C2O42- titrations haemoglobin Contains Fe2+ – allows O2 to bond and carried to where needed © www.chemsheets.co.uk A2 043 20-Jul-12

USES OF SOME COMPLEXES 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 © www.chemsheets.co.uk A2 043 20-Jul-12

5.4.7 – USES OF SOME COMPLEXES 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 © www.chemsheets.co.uk A2 043 20-Jul-12

USES OF SOME COMPLEXES 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 © www.chemsheets.co.uk A2 043 20-Jul-12

USES OF SOME COMPLEXES 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 © www.chemsheets.co.uk A2 043 20-Jul-12

SHAPES OF COMPLEX IONS Co-ordination number 2 4 6 Shape linear tetrahedral square planar octahedral Bond angles Occurrence e.g. © www.chemsheets.co.uk A2 043 20-Jul-12

SHAPES OF COMPLEX IONS Co-ordination number 2 4 6 Shape linear tetrahedral square planar octahedral Bond angles 180º 109½º 90º Occurrence e.g. © www.chemsheets.co.uk A2 043 20-Jul-12

SHAPES OF COMPLEX IONS Co-ordination number 2 4 6 Shape linear tetrahedral square planar octahedral Bond angles 180º 109½º 90º Occurrence Ag+ complexes e.g. [Ag(NH3)2]+ © www.chemsheets.co.uk A2 043 20-Jul-12

SHAPES OF COMPLEX IONS Co-ordination number 2 4 6 Shape linear tetrahedral square planar octahedral Bond angles 180º 109½º 90º Occurrence Ag+ complexes Large ligands (e.g. Cl-) e.g. [Ag(NH3)2]+ [CuCl4]2- © www.chemsheets.co.uk A2 043 20-Jul-12

SHAPES OF COMPLEX IONS Co-ordination number 2 4 6 Shape linear tetrahedral square planar octahedral Bond angles 180º 109½º 90º Occurrence Ag+ complexes Large ligands (e.g. Cl-) Pt2+ complexes e.g. [Ag(NH3)2]+ [CuCl4]2- [PtCl4]2- © www.chemsheets.co.uk A2 043 20-Jul-12

SHAPES OF COMPLEX IONS Co-ordination number 2 4 6 Shape linear tetrahedral square planar octahedral Bond angles 180º 109½º 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+ © www.chemsheets.co.uk A2 043 20-Jul-12

SHAPES OF COMPLEX IONS

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. [Ag(CN)2]- [Cr(NH3)6]3+ [Ni(en)3]2+ [Co(en)2Cl2 ]+ [Pt(NH3)2Cl2] [Fe(C2O4)3]4- © www.chemsheets.co.uk A2 043 20-Jul-12

SHAPES OF COMPLEX IONS Linear 180º Ag +1 Co-ordination number = 2 1 2 Octahedral 90º Cr +3 Co-ordination number = 6 © www.chemsheets.co.uk A2 043 20-Jul-12

SHAPES OF COMPLEX IONS Octahedral 90º Ni +2 Co-ordination number = 6 3 2+ Octahedral 90º Ni +2 Co-ordination number = 6 3 Ni 4 Octahedral 90º Co +3 Co-ordination number = 6 © www.chemsheets.co.uk A2 043 20-Jul-12

SHAPES OF COMPLEX IONS Tetrahedral 90º Pt +2 Co-ordination number = 4 5 6 Octahedral 90º Fe +2 Co-ordination number = 6 4- Fe © www.chemsheets.co.uk A2 043 20-Jul-12

SHAPES OF COMPLEX IONS Geometric Isomerism e.g. [PtCl2(NH3)2] cis trans

SHAPES OF COMPLEX IONS Geometric isomerism e.g. [CoCl2(NH3)4]+

SHAPES OF COMPLEX IONS Optical Isomerism e.g. [Co(en)3]3+

SHAPES OF COMPLEX IONS Optical Isomerism © www.chemsheets.co.uk A2 043 20-Jul-12

FORMATION OF COLOURED IONS

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. © www.chemsheets.co.uk A2 043 20-Jul-12

FORMATION OF COLOURED IONS Energy

FORMATION OF COLOURED IONS The colour you see is what is left after some colours are absorbed by the metal to excite electrons.

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+ [Fe(H2O)6]2+ blue green © www.chemsheets.co.uk A2 043 20-Jul-12

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+ [Fe(H2O)6]2+ pale violet green © www.chemsheets.co.uk A2 043 20-Jul-12

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+ [Cu(H2O)2(NH3)4 ]2+ blue deep blue © www.chemsheets.co.uk A2 043 20-Jul-12

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+ [CuCl4 ]2- blue yellow © www.chemsheets.co.uk A2 043 20-Jul-12

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.

FORMATION OF COLOURED IONS

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. © www.chemsheets.co.uk A2 043 20-Jul-12

FORMATION OF COLOURED IONS Colorimetry