Unit 5.

2: Transition metal chemistry: derive the electronic configurations of atoms of the d-block elements (Sc to Zn), and their simple ions, from their position in the Periodic Table recall the transition metals as d-block elements forming one or more stable ions which have incompletely filled d-orbitals Transition metal D block elements which form ions which have partially filled d-orbitals Scandium and zinc are not transition elements Element atomic Symbol Electronic structure of atom number 21 22 23 Sc Ti V Cr Mn Fe Co Ni Cu Zn (Ar)3d14s2 (Ar)3d 4s
2 2

Common ion(s) Electronic structure of ion Sc3+ Ti Ti3+ V3+ Cr3+ Mn2+ Fe2+ Fe3+ Co2+ Ni2+ Cu+ Cu2+ Zn2+
4+

Scandium Titanium Vanadium

(Ar) (Ar) (Ar)3d1 (Ar)3d2 (Ar)3d3 (Ar)3d5 (Ar)3d6 (Ar)3d5 (Ar)3d7 (Ar)3d8 (Ar)3d10 (Ar)3d9 (Ar)3d10

(Ar)3d34s2 (Ar)3d54s1 (Ar)3d54s2 (Ar)3d64s2 (Ar)3d74s2 (Ar)3d84s2 (Ar)3d104s1 (Ar)3d104s2

Chromium 24 Manganese 25 Iron Cobalt Nickel Copper Zinc 26 27 28 29 30

recall appropriate parts of the chemistry of chromium, iron and copper to illustrate the properties of transition elements described in c, d and e. recall characteristic properties of the transition elements, such as (i) the formation of coloured aqueous ions, and other complex ions Transition metal compounds are coloured, d orbitals are normally of similar energy but when surrounded by ligands the orbitals are split into higher and lower energy sets. absorbs light (in visible region) d-orbitals split by ligands electron moves to a higher energy level [Cr(H2O)6]3+(aq) blue hexaaquachromium(III) dichromate Cr2O72-(aq) orange in acid chromate [CrO4]2-(aq) yellow in alkali Fe2+(aq) green Fe3+(aq) yellow/brown Cu(H2O)6]2+(aq) blue hexaaquacopper(II) Managnate(VII) MnO4-(aq) purple Tetraamminecopper(II) Cu(NH3)42+(aq) deep blue/purple Tetrachlorocuprate(II) CuCl42-(aq) yellow hydrated thiocyanate complex of iron (III) [Fe(SCN)(H2O)5]2+ blood red [Co(H2O)6]2+(aq) pink hexaaquacobalt(II) [CoCl4]2-(aq) blue tetrachlorocobalte(II) (ii) the formation of a range of compounds in which they are present in different stable oxidation states Transition metals show the following characteristic properties: 1. Variable oxidation states:Transition metals have electrons of similar energy in both the 3d and 4s levels. This means that one particular element can form ions of roughly the same stability by losing different numbers of electrons. Thus, all transition metals from titanium to copper can exhibit two or more oxidation states in their compounds. When Transition Metals form positive ions they loose their electrons from the 4s sub-shell first, then the 3d sub-shell. Oxidation states of some Transition Metals: Titanium- +2, +3, +4 Vanadium- +2, +3, +4, +5 Chromium- +2, +3, +6 Manganese- +2, +3, +4, +5, +6, +7 Iron- +2, +3 Cobalt- +2, +3

2. 3.

4.

Nickel- +2, +3, +4 Copper- +1, +2 Formation of complex ions:- As a lot of the transition metals have some empty spaces in their 3d-orbitals, they can receive lone pairs of electrons and form dative covalent bonds thus producing complex compounds. Coloured compounds:- When electrons move from a d-orbital (with lower energy) to another d-orbital (with higher energy), energy is taken in. This energy in the form of light is missing from the reflected light thus producing coloured compounds. Catalytic properties:- As Transition Metals have variable oxidation states, they tend to have catalytic properties. The small differences in ionisation energies make variable oxidation numbers possible. The reversible redox reactions involving transition metal ions make lower energy routes for other reactions.

Understand the bonding, shape and cause of colour in complex ions and aqua ions stereoisomerism in such complex ions will not be examined colour should be related to a simple transfer of electrons between d-orbitals Bonding between the ligand and the metal ion is DATIVE COVALENT and this CAUSES A SPLITTING OF D-ORBITALS Complex ions (cationic or anionic) A central metal ion surrounded by ligands/anions (species donating electron(s) In transition metal complexes, non-bonded pairs of electrons on the ligand form co-ordinate/dative covalent bonds to the central ion by donating these unshared electron pairs into vacant orbitals Co-ordination number Shape Octahedral tetrahedral Linear The number of co-ordinate bonds from ligands to the central ion [Fe(H2O)6]3+ [Ni(CO)4]2+ [CuCl2]-

Octahedron [CrCl(H2O)5]+2 pentaaquachlorochromium (III) [NiCl4]2- tetrachloronickelate(II) [Cr(OH)6]3- hexahydroxochromate(III) Writing formulae: Central atom first, then negative ions, then follow any neutral molecules. Everything is then put in square brackets and the charge added. For example, tetraaquachlorocopper (II) would be written as [CuCl(H 2O)4]+ Naming: For a positive complex ion: prefix, ligands (alphabetical order), then metal, then oxidation number. For a negative complex ion: the name of the metal is changed. Iron-ferrate, copper-cuprate, chromium-chromate, cobaltcobalate, nickel-nickelate, zinc-zincate Di Tri Tetra Penta Hexa Name of molecule or ion Symbol Ligand name Water Ammonia Chloride ion Hydroxide ion Cynide ion Ethane- 1,2- diammine EDTA H 2O NH3 Cl
-

Aqua Ammine Chloro Hydroxo Cyano Ethane- 1,2- diammine

OH CN EN

EDTA EDTA

understand simple ligand exchange processes the concepts of deprotonation and ligand exchange should be applied to these reactions

recall colours of the OH ppts and complexes on addition of excess alkali or ammonia solution, limited to Cr3+, Mn2+, Fe2+, Fe3+, Co2+, Ni2+, Cu2+, Zn2+ Ligand exchange- This involves the replacement of one ligand by another [ Cu(H2O)4 ]2+(aq) + 4Cl- <----> [ CuCl4 ]2-(aq) + 4H20(l) blue green colour changes as the different ligands create a different amount of splitting between d orbitals in the copper ion.

Deprotonation H+ removed by (NH3/OH-) from (H2O) ligands H2O 2H2O 3H2O Cr3+ Cr(OH)3(s) grey green Mn2+ Mn(OH)2(s) white/brown Fe3+ Fe(OH)2(s) muddy/green

[Cu(H2O)6]2+ + OH-

[Cu(OH)(H2O)5]+ + Ni(OH)2 + 2H2O [Zn(OH)4]2-(aq) +

[Ni(H2O)6]2+ + 2OH Zn(OH)2(H2O)2(s) + 2OH-(aq)

Cr(OH)3(H2O)3(s) + 3OH-(aq) ---> [Cr(OH)6]3-(aq) + Fe3+ Fe(OH)3(s) rust brown Co2+ Co(OH)2(s) light blue Ni2+ Ni(OH)2(s) green Cu2+ Cu(OH)2 light blue Zn2+ Zn(OH)2 white

Deprotonation with NaOH (aq) Or ligand exchange with NH3 (aq)

For Vanadium, ox state[+2, +3, +4, +5] in its compounds, Recall colours of aqueous solutions, And given E values, work out the reagents for the interconversion of the metal ions, oxo anions and oxo cations Describe reactions for the interconversion of the oxidation states of vanadium in aqueous solution Oxidation state Colour in aqueous solution Ion Name +5 yellow VO3- or VO2+ +4 blue VO2+ oxovanadium (IV) ion +3 green V3+ vanadium (III) +2 violet V2+ vanadium (II)

vanadate(V) or dioxovanadium(V)ion

Vanadium oxidised from (+2 to +5) V2+ to VO2+, add acidified manganate (VII) to the vanadium (II) V 2+ -----> VO2+ Vanadium is reduced from (+5 to +2) VO2+ to V2+, add zinc to the dioxovanadium VO2+ -----> V2+ Vanadium can be reduced from the +5 states right through to the +2 state by zinc. recall that transition elements and their compounds are important catalysts in industrial processes, and that their catalytic activity is often associated with the variable oxidation states of the elements recall examples of catalytic action by vanadium, iron and nickel and/or their compounds.

2. (a) Complete the following electronic configurations.

Ni

Ni2+

(b) Explain why nickel is classified as a transition metal. Forms ions which have partially filled d-orbitals (c) Consider the following reaction scheme. (i) What types of bond are present in the [Ni(H2O) 6] 2+ ion?

Dative covalent/co-ordinate (ii) Write an equation for the formation of the pale green precipitate. OR OR OR (iii) Explain why Step 1 is a deprotonation reaction. NH3 OR OH-) from (H2O) ligands (iv) Name the type of reaction occurring in Step 2. exchange/replacement/substitution (v) Give an equation for the reaction in Step 2. OR OR H+ removed (by

Ligand

(d) Explain why the hexaaquanickel(II) ion, [Ni(H 2O) 6] 2+ is coloured. ligands absorbs light (in visible region)

d-orbitals split (in energy) by

electron moves to a higher energy level 3. (a) The elements from scandium to zinc belong to the d-block. Some, but not all, of these elements are transition elements. (i) What is meant by the term transition element? Forms ions which have partially filled d-orbitals (ii) Which of the elements, from scandium to zinc inclusive, are in the d-block but are not transition elements? Scandium / Sc and Zinc / Zn (b) (i) Complete the electronic configurations of the Fe 2+ and Mn2+ ions
2+ 6 2+ 5

Fe [Ar] 3d

Mn [Ar] 3d
3+ 5

(ii) Suggest why Fe2+ ions are readily oxidised to Fe3+ ions, but Mn2+ ions are not readily oxidised to Mn3+ ions. Fe is 3d / half
6

filled d-subshell which is more stable than 3d Mn is (already) 3d

4 2+ 5

(which is more stable than 3d ) (c) Draw a diagram to show the three-dimensional structure of the [Fe(CN)6]4 complex ion.

(d) A solution of potassium manganate(VII), KMnO 4, can be standardised by titration with arsenic(III) oxide, As2O3. In this reaction, 5 mol of arsenic(III) oxide are oxidised to arsenic(V) oxide, As 2O5, by 4 mol of manganate(VII) ions, MnO4 Calculate the final oxidation number of the manganese Two As atoms oxidised from

+3 to +5 per mole of As O (loss of 4e )

2 3

if 5 moles oxidised, total 4 moles MnO reduced, total 20e gained / change in oxidation no. 20 each
4 -

20e lost / change in oxidation no. = 20

Mn(VII) gains 5e /change in oxidation no. 5 Mn(II) / Mn2+ (e) Ammonium vanadate(V), NH4VO3, reacts with dilute sulphuric acid to form a solution containing yellow VO 2 + ions. (i) Write an ionic equation for the reaction of the anion in NH4VO3 with dilute sulphuric acid. + + + VO3 + 2H /2H3O VO2 + H2O/3H2O (ii) Is the reaction in (i) a redox reaction? + VO2 / Oxidation no. of V unchanged (at +5) No because oxidation no. of V is +5 in

(iii) Addition of zinc to the solution containing VO2+ ions causes the colour to change from yellow to green then to blue, followed by green again and finally violet. State the formulae of the ions responsible for each of these colours. The first green colour The second green colour The violet colour
+ 2+ 3+ 3+ 2 6

First green colour : VO and VO

2+ 2+ 2 6 2

Second green colour : V / [V(H O) ]

Violet colour : V / [V(H O) ]