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Transition Elements&Catalysts

Transition Elements&Catalysts http://www.chem.ox.ac.uk/vrchemistry/complex/allbottlesmsiedefault.html http://www.gcsescience.com/pt21.htm. TRANSITION METALS. High densities , melting and boiling points Ability to exist in a variety of oxidation states Formation of colored ions

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Transition Elements&Catalysts

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  1. Transition Elements&Catalysts http://www.chem.ox.ac.uk/vrchemistry/complex/allbottlesmsiedefault.html http://www.gcsescience.com/pt21.htm

  2. TRANSITION METALS • Highdensities,meltingandboilingpoints • Ability to exist in a varietyofoxidation states • Formationofcoloredions • Ability to formcomplexions • Ability to act as catalysts Zn andSc do notsharetheseproperties.

  3. THE FIRST ROW TRANSITION ELEMENTS DefinitionD-block elements forming one or more stable ions with partially filled (incomplete) d-sub shells. The first row runs from scandium to zinc filling the 3d orbitals. Properties arise from an incomplete d sub-shell in atoms or ions

  4. THE FIRST ROW TRANSITION ELEMENTS Metallic properties all the transition elements are metals strong metallic bonds due to small ionic size and close packing higher melting, boiling points and densities than s-block metals K Ca Sc Ti V Cr Mn Fe Co m. pt / °C 63 850 1400 1677 1917 1903 1244 1539 1495 density / g cm-3 0.86 1.55 3 4.5 6.1 7.2 7.4 7.9 8.9

  5. 4f 4d 4 4p ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS POTASSIUM INCREASING ENERGY / DISTANCE FROM NUCLEUS 3d 4s 3 3p 1s2 2s2 2p6 3s2 3p6 4s1 ‘Aufbau’ Principle In numerical terms one would expect the 3d orbitals to be filled next. However, because the principal energy levels get closer together as you go further from the nucleus coupled with the splitting into sub energy levels, the 4s orbital is of a LOWER ENERGY than the 3d orbitals so gets filled first.

  6. 4f 4d 4 4p ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS CALCIUM INCREASING ENERGY / DISTANCE FROM NUCLEUS 3d 4s 3 3p 1s2 2s2 2p6 3s2 3p6 4s2 As expected, the next electron in pairs up to complete a filled 4s orbital. This explanation, using sub levels fits in with the position of potassium and calcium in the Periodic Table. All elements with an -s1 electronic configuration are in Group I and all with an -s2 configuration are in Group II.

  7. 4f 4d 4 4p ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS SCANDIUM INCREASING ENERGY / DISTANCE FROM NUCLEUS 3d 4s 3 3p 1s2 2s2 2p6 3s2 3p6 4s2 3d1 With the lower energy 4s orbital filled, the next electrons can now fill p the 3d orbitals. There are five d orbitals. They are filled according to Hund’s Rule. BUT WATCH OUT FOR TWO SPECIAL CASES.

  8. 4f 4d 4 4p ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS TITANIUM INCREASING ENERGY / DISTANCE FROM NUCLEUS 3d 4s 3 3p 1s2 2s2 2p6 3s2 3p6 4s2 3d2 The 3d orbitals are filled according to Hund’s rule so the next electron doesn’t pair up but goes into an empty orbital in the same sub level. HUND’S RULE OF MAXIMUM MULTIPLICITY

  9. 4f 4d 4 4p ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS VANADIUM INCREASING ENERGY / DISTANCE FROM NUCLEUS 3d 4s 3 3p 1s2 2s2 2p6 3s2 3p6 4s2 3d3 The 3d orbitals are filled according to Hund’s rule so the next electron doesn’t pair up but goes into an empty orbital in the same sub level. HUND’S RULE OF MAXIMUM MULTIPLICITY

  10. 4f 4d 4 4p ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS CHROMIUM INCREASING ENERGY / DISTANCE FROM NUCLEUS 3d 4s 3 3p 1s2 2s2 2p6 3s2 3p6 4s1 3d5 One would expect the configuration of chromium atoms to end in 4s2 3d4. To achieve a more stable arrangement of lower energy, one of the 4s electrons is promoted into the 3d to give six unpaired electrons with lower repulsion.

  11. 4f 4d 4 4p ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS MANGANESE INCREASING ENERGY / DISTANCE FROM NUCLEUS 3d 4s 3 3p 1s2 2s2 2p6 3s2 3p6 4s2 3d5 The new electron goes into the 4s to restore its filled state.

  12. 4f 4d 4 4p ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS IRON INCREASING ENERGY / DISTANCE FROM NUCLEUS 3d 4s 3 3p 1s2 2s2 2p6 3s2 3p6 4s2 3d6 Orbitals are filled according to Hund’s Rule. They continue to pair up. HUND’S RULE OF MAXIMUM MULTIPLICITY

  13. 4f 4d 4 4p ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS COBALT INCREASING ENERGY / DISTANCE FROM NUCLEUS 3d 4s 3 3p 1s2 2s2 2p6 3s2 3p6 4s2 3d7 Orbitals are filled according to Hund’s Rule. They continue to pair up. HUND’S RULE OF MAXIMUM MULTIPLICITY

  14. 4f 4d 4 4p ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS NICKEL INCREASING ENERGY / DISTANCE FROM NUCLEUS 3d 4s 3 3p 1s2 2s2 2p6 3s2 3p6 4s2 3d8 Orbitals are filled according to Hund’s Rule. They continue to pair up. HUND’S RULE OF MAXIMUM MULTIPLICITY

  15. 4f 4d 4 4p ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS COPPER INCREASING ENERGY / DISTANCE FROM NUCLEUS 3d 4s 3 3p 1s2 2s2 2p6 3s2 3p6 4s1 3d10 One would expect the configuration of copper atoms to end in 4s2 3d9. To achieve a more stable arrangement of lower energy, one of the 4s electrons is promoted into the 3d. HUND’S RULE OF MAXIMUM MULTIPLICITY

  16. 4f 4d 4 4p ELECTRONIC CONFIGURATIONS OF THE FIRST ROW TRANSITION METALS ZINC INCREASING ENERGY / DISTANCE FROM NUCLEUS 3d 4s 3 3p 1s2 2s2 2p6 3s2 3p6 4s2 3d10 The electron goes into the 4s to restore its filled state and complete the 3d and 4s orbital filling.

  17. ELECTRONIC CONFIGURATIONS K 1s2 2s2 2p6 3s2 3p6 4s1 Ca 1s2 2s2 2p6 3s2 3p6 4s2 Sc 1s2 2s2 2p6 3s2 3p6 4s2 3d1 Ti 1s2 2s2 2p6 3s2 3p6 4s2 3d2 V 1s2 2s2 2p6 3s2 3p6 4s2 3d3 Cr 1s2 2s2 2p6 3s2 3p6 4s1 3d5 Mn 1s2 2s2 2p6 3s2 3p6 4s2 3d5 Fe 1s2 2s2 2p6 3s2 3p6 4s2 3d6 Co 1s2 2s2 2p6 3s2 3p6 4s2 3d7 Ni 1s2 2s2 2p6 3s2 3p6 4s2 3d8 Cu 1s2 2s2 2p6 3s2 3p6 4s1 3d10 Zn 1s2 2s2 2p6 3s2 3p6 4s2 3d10

  18. Sc Ti V Cr Mn Fe Co Ni Cu Zn +7 +6 +6 +6 +5 +5 +5 +5 +5 +4 +4 +4 +4 +4 +4 +4 +3 +3 +3 +3 +3 +3 +3 +3 +2 +2 +2 +2 +2 +2 +2 +2 +2 +1 VARIABLE OXIDATION STATES Arises from the similar energies required for removal of 4s and 3d electrons maximum rises across row to manganese maximum falls as the energy required to remove more electrons becomes very high all (except scandium) have an M2+ ion stability of +2 state increases across the row due to increase in the 3rd Ionisation Energy THE MOST IMPORTANT STATES ARE IN RED When electrons are removed they come from the 4s orbitals first Cu 1s2 2s2 2p6 3s2 3p63d10 4s1 Ti 1s2 2s2 2p6 3s2 3p63d2 4s2 Cu+ 1s2 2s2 2p6 3s2 3p63d10Ti2+ 1s2 2s2 2p6 3s2 3p63d2 Cu2+ 1s2 2s2 2p6 3s2 3p63d9 Ti3+ 1s2 2s 2p6 3s2 3p63d1 Ti4+ 1s2 2s2 2p6 3s23p6

  19. COLOURED IONS A characteristic of transition metals is their ability to form coloured compounds Theory ions with a d10 (full) or d0 (empty) configuration are colourless ions with partially filled d-orbitals tend to be coloured it is caused by the ease of transition of electrons between energy levels energy is absorbed when an electron is promoted to a higher level the frequency of light is proportional to the energy difference ions with d10 (full) Cu+,Ag+ Zn2+ or d0 (empty) Sc3+ configuration are colourless e.g. titanium(IV) oxide TiO2 is white colour depends on ... transition element oxidation state ligand coordination number

  20. 3d ORBITALS There are 5 different orbitals of the d variety xy xz yz x2-y2 z2

  21. COLOURED IONS The observed colour of a solution depends on the wavelengths absorbed Copper sulphate solution appears blue because the energy absorbed corresponds to red and yellow wavelengths. Wavelengths corresponding to blue light aren’t absorbed. WHITE LIGHT GOES IN SOLUTION APPEARS BLUE ENERGY CORRESPONDING TO THESE COLOURS IS ABSORBED Absorbed colour nm Observed colour nm VIOLET 400 GREEN-YELLOW 560 BLUE 450 YELLOW 600 BLUE-GREEN 490 RED 620 YELLOW-GREEN 570 VIOLET 410 YELLOW 580 DARK BLUE 430 ORANGE 600 BLUE 450 RED 650 GREEN 520

  22. COLOURED IONS a solution of copper(II)sulphate is blue because red and yellow wavelengths are absorbed blue and green not absorbed white light

  23. CoordinationCompound • Go to Power PointCoordinationChemistry

  24. COMPLEX IONS - LIGANDS Formationligands form co-ordinate bonds to a central transition metal ion Ligandsatoms, or ions, which possess lone pairs of electrons form co-ordinate bonds to the central ion donate a lone pair into vacant orbitals on the central species Ligand Formula Name of ligand chloride Cl¯ chloro cyanide NC¯ cyano hydroxide HO¯ hydroxo oxide O2- oxo water H2O aqua ammonia NH3 ammine some ligands attach themselves using two or more lone pairs classified by the number of lone pairs they use multidentate and bidentate ligands lead to more stable complexes

  25. COMPLEX IONS - LIGANDS some ligands attach themselves using two or more lone pairs classified by the number of lone pairs they use multidentate and bidentate ligands lead to more stable complexes Unidentate form one co-ordinate bond Cl¯, OH¯, CN¯, NH3, and H2O Bidentate form two co-ordinate bonds H2NCH2CH2NH2 , C2O42-

  26. COMPLEX IONS - LIGANDS some ligands attach themselves using two or more lone pairs classified by the number of lone pairs they use multidentate and bidentate ligands lead to more stable complexes Multidentate form several co-ordinate bonds EDTA An important complexing agent

  27. d orbitals

  28. http://www.chemguide.co.uk/inorganic/complexions/colour.html • When the ligands bond with the transition metal ion, there is repulsion between the electrons in the ligands and the electrons in the d orbitals of the metal ion. That raises the energy of the d orbitals. • However, because of the way the d orbitals are arranged in space, it doesn't raise all their energies by the same amount. Instead, it splits them into two groups

  29. http://www.chemguide.co.uk/inorganic/complexions/colour.html • The diagram shows the arrangement of the d electrons in a Cu2+ ion before and after six water molecules bond with it.

  30. Whenever 6 ligands are arranged around a transition metal ion, the d orbitals are always split into 2 groups in this way - 2 with a higher energy than the other 3. • The size of the energy gap between them (shown by the blue arrows on the diagram) varies with the nature of the transition metal ion, its oxidation state (whether it is 3+ or 2+, for example), and the nature of the ligands.

  31. When white light is passed through a solution of this ion, some of the energy in the light is used to promote an electron from the lower set of orbitals into a space in the upper set. • http://www.chemguide.co.uk/inorganic/complexions/colour.html

  32. SPLITTING OF 3d ORBITALS Placing ligands around a central ion causes the energies of the d orbitals to change Some of the d orbitals gain energy and some lose energy In an octahedral complex, two go higher and three go lower In a tetrahedral complex, three go higher and two go lower Degree of splitting depends on theCENTRAL ION and theLIGAND The energy difference between the levels affects how much energy is absorbed when an electron is promoted. The amount of energy governs the colour of light absorbed. OCTAHEDRAL TETRAHEDRAL 3d 3d

  33. Complexion - Iron • Becauseoftheirsize, transitionmetalsattractspeciesthat are rich in electrons. Ligands. • Water is a commonligand as in hexaaquairon (III) ion, [Fe(H2O)63+

  34. COMPLEX IONS - LIGANDS some ligands attach themselves using two or more lone pairs classified by the number of lone pairs they use multidentate and bidentate ligands lead to more stable complexes Multidentate form several co-ordinate bonds HAEM A complex containing iron(II) which is responsible for the red colour in blood and for the transport of oxygen by red blood cells. Co-ordination of CO molecules interferes with the process

  35. COMPLEX IONS - LIGANDS some ligands attach themselves using two or more lone pairs classified by the number of lone pairs they use multidentate and bidentate ligands lead to more stable complexes Multidentate form several co-ordinate bonds

  36. CO-ORDINATION NUMBER & SHAPE the shape of a complex is governed by the number of ligands around the central ion the co-ordination number gives the number of ligands around the central ion a change of ligand can affect the co-ordination number Co-ordination No. Shape Example(s) 6 Octahedral [Cu(H2O)6]2+ 4 Tetrahedral [CuCl4]2- Square planar Pt(NH3)2Cl2 2 Linear [Ag(NH3)2]+

  37. ISOMERISATION IN COMPLEXES GEOMETRICAL (CIS-TRANS) ISOMERISM Square planar complexes of the form [MA2B2]n+ exist in two forms trans platin cis platin An important anti-cancer drug. It is a square planar, 4 co-ordinate complex of platinum.

  38. 13.2.7 CatalyticActionofTransitionElements • Catalystsincreasethe rate of a chemicalreactionwithoutthemselvesbeingchemicallychanged(lower EA). • Theycanbeheterogeneous( catalyst is in a differentphasefromthereactants) orhomogeneous( samephase)

  39. Transitionmetals are goodatadsorbing small molecules. • Read CC page 59,60. OutlinedueMonday.

  40. 13.2.7. CATALYTIC PROPERTIES Transition metals and their compounds show great catalytic activity It is due to partly filled d-orbitals which can be used to form bonds with adsorbed reactants which helps reactions take place more easily Transition metalscan both lend electrons to and take electrons from other molecules. By giving and taking electrons so easily, transition metal catalysts speed up reactions Examples of catalysts IRON Manufacture of ammonia - Haber Process NICKEL Hydrogenation reactions - margarine manufacture MANGANESE IV OXIDE Hydrogen peroxide VANADIUM(V) OXIDE Manufacture of sulphuric acid - Contact Process http://www.gcsescience.com/pt21.htm

  41. Co in Vitamin B12 Vitamin B12, also called cobalamin, is a water-soluble vitamin with a key role in the normal functioning of the brain and nervous system, and for the formation of blood. It is one of the eight B vitamins. It is normally involved in the metabolism of every cell of the human body, especially affecting DNA synthesis and regulation, but also fatty acid synthesis and energy production.

  42. Contact Process • Vanadium pentoxide is used in different, industrial processes as catalyst: In the contact process it serves for the oxidation of SO2 to SO3 with oxygen at 440°C. • Sulfur dioxide and oxygen then react as follows: • 2 SO2(g) + O2(g) ⇌ 2 SO3(g) : ΔH = −197 kJ mol−1 • To increase the reaction rate, high temperatures (450 °C), medium pressures (1-2 atm), and vanadium(V) oxide (V2O5) are used to ensure a 96% conversion. Platinum would be a more effective catalyst, but it is very costly and easily poisoned.[citation needed] • The catalyst only serves to increase the rate of reaction as it has no effect on how much SO3 is produced. The mechanism for the action of the catalyst is: • 2SO2 + 4V5+ + 2O2- → 2SO3 + 4V4+ 4V4+ + O2 → 4V5+ + 2O2- • http://www.chemguide.co.uk/physical/equilibria/contact.html

  43. 13.2.8. EconomicSignificanceofcatalysts in Contactand Haber processes • Thecatalyticpropertiesofthesemetals are due to theirability to exist in a numberofstableoxidation states andthepresenceofemptyorbitals for temporarybondformation. • Thecatalyst is usually a powderedsolidandthereactants a mixtureof gases.

  44. Decomposition of Hydrogen Peroxide – MnO2 Hydrogen peroxide decomposes to oxygen and water when a small amounts of manganese dioxide is added. Catalase enzyme from potato also decomposes hydrogen peroxide. 2 H2O2 → 2 H2O + O2

  45. Catalytic Converter http://auto.howstuffworks.com/catalytic-converter2.htm

  46. catalytic CO + Unburned Hydrocarbons + O2 CO2 + H2O converter catalytic 2NO + 2NO2 2N2 + 3O2 converter Catalytic Converters 13.6

  47. 4NH3(g) + 5O2(g) 4NO (g) + 6H2O (g) 2NO (g) + O2(g) 2NO2(g) 2NO2(g) + H2O (l) HNO2(aq) + HNO3(aq) Hot Pt wire over NH3 solution Pt-Rh catalysts used in Ostwald process Ostwald Process Pt catalyst 13.6

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