Catalytic activity of transition elements

Transition metals and their compounds are often good catalysts. The small differences in ionization energies make variable oxidation numbers possible. When transition metals act as catalyst they use their empty orbitals to form temporary dative covalent bond with reactants molecules, weakening the bonds and hence provide low activation energy to break the bonds. There are two types of catalysts.

In a heterogeneous reaction, the catalyst is in a different phase from the reactants.

In a homogeneous reaction, the catalyst is in the same phase as the reactants.

Homogeneous catalyst

This has the catalyst in the same phase as the reactants.

Typically everything will be present as a gas or contained in a single liquid phase.

Transition metals can act as a homogeneous catalyst because they exhibit variable states.

The reaction between peroxodisulphate ions and iodide ions

The reaction needs a collision between two negative ions. The catalyst can be either iron(II)

The peroxodisulphate ions oxidise the iron(II) ions to iron(III) ions.

In the process the peroxodisulphate ions are reduced to sulphate ions. The iron(III) ions are strong enough oxidising agents to oxidise iodide ions to iodine. In the process, they are reduced back to iron(II) ions again.

Heterogeneous catalysis

This involves the use of a catalyst in a different phase from the reactants. Typical examples involve a solid catalyst with the reactants as either liquids or gases. Heterogeneous catalysis reactions occur on the surface of the catalyst. There are active sites on the surface of catalyst, where reactions occur. Transition metals act as heterogeneous catalysts due to vacant d-orbital.

How the heterogeneous catalyst works

Diffusion
Reactant molecules move to the active sites

Adsorption
The surface of the catalyst attracts the reactant molecules by intermolecular forces and form temporary dative covalent bonds. Adsorption is the surface process.

Weakening of the bonds

Hence the bonds which are the reactant molecules become weaker or some bonds might be broken. Due to weakness of bonds, energy is required to break the bonds is very weak. Thus activation energy is low.

Desorption
New bonds are formed on the surface of the catalyst to form product molecules and then product molecules move away from active sites of catalyst, that is products are desorbed and the diffuse away from the catalyst.

Autocatalysis

In autocatalysis, the reaction is catalysed by one of its products. The oxidation of ethanedioic acid by manganate(VII) ions

The reaction is very slow at room temperature.

It is used as a titration to find the concentration of potassium manganate(VII) solution and is usually carried out at a temperature of about 60C.

Substance Iron Nickel

Reaction catalysed

Haber process to convert nitrogen and hydrogen to ammonia Margarine production to hydrogenate unsaturated hydrocarbons Contact process to convert oxygen and sulphur dioxide to sulphur trioxide

Vanadium(V) oxide

Ligand Exchange Processes

It is possible for one type of ligand to be replaced by another type. Ligand exchange reactions often have a colour change associated with them.

Thiocyanate ions can replace one of the water ligands in [Fe(H2O)6]3+. [Fe(H2O)6]3+ + SCN- [Fe (H2O)5SCN]2+ + H2O An aqueous Copper(II) sulphate solution is blue in colour because of the presence of [Cu(H2O)6]2 ions. When concentrated hydrochloric acid is added to this solution the colour changes from blue to green. This happens because the [CuCl4]2- ion is produced. The Cl- ions have replaced the H2O molecules in a ligand exchange. [Cu(H2O)6]2+ + 4Cl- [CuCl4]2- + 6H2O When ammonia is added a further change from green to deep blue takes place as ammonia molecules replace the chloride ions. [CuCl4]2- + 4NH3 + 2H2O [Cu(NH3)4(H2O)2]2+ + 4ClIf EDTA is then added yet another ligand exchange takes place and the solution turns pale blue.

These changes take place because the complexes become more stable.

[Cu(H2O)6]2+

[CuCl4]2-

[Cu(NH3)4(H2O)2]2+

[Cu(edta)]2+

Increasing stability
The stability of the [Cu(edta)]2+ complex can be understood in terms of entropy. As the one edta molecule replaces the six smaller ligands, the small ligands are released into solution and therefore have greater freedom of movement, so greater disorder and consequently the entropy increases.

Deprotonation reactions

Deprotonation reactions involve water ligands losing hydrogen ions (proton) to a proton acceptor such as an hydroxide ion.

[Cu(H2O)6]2+ + OH- [Cu(OH)(H2O)5]+ + H2O

Deprotonation reactions often result in the formation of a precipitate.

Reaction of complex ions with sodium hydroxide and ammonia solutions

Sodium hydroxide and ammonia solutions contain hydroxide ions. When these are added to solutions containing transition metal ions a precipitate of the metal hydroxide is formed. If further quantities of these reagents are added to the mixture, the precipitate, in certain cases, dissolves

Ion in solution Cr3+ Mn2+ Fe2+ Fe3+ Ni2+ Cu2+ Zn2+

Reaction with a few drops of NaOH(aq) or NH3(aq) Pale green ppt Beige ppt Dirty green ppt Red-brown ppt Green gelatinous ppt Blue ppt White gelatinous ppt

Reaction with excess NaOH(aq) Ppt dissolves to form a deep green solution No further reaction No further reaction No further reaction No further reaction No further reaction Ppt dissolves to form a colourless solution

Reaction with exc NH3(aq)

No further reaction No further reaction Ppt dissolves to form blue solution Ppt dissolves to form deep blue solution

A simple way of looking at these is as hydroxide ions adding to the transition metal ion the number of hydroxide ions being equal to the charge on the ion. [M(H2O)x]y+ + yOH- [M(H2O)x-y(OH)y] + yH2O

In fact rather than a water molecule leaving and a hydroxide ion joining, the process actually consists of a hydrogen ion moving

Vanadium chemistry

Vanadium forms stable compounds in 4 different oxidation states, +2, +3, +4 and +5. In aqueous solution, the ions formed are:

Oxidation state Colour Ion

+5 Yellow VO2+

+4 Blue VO2+

+3 green V3+

+2 Violet V2+

+5 oxidation state is mildly oxidizing agent. +4 oxidation state is more stable oxidation state +3 oxidation state is unstable in the presence of oxygen +2 oxidation state is strong reducing agent.

V +4 and +5 oxidation states have small size and high charge, so they are highly polarizing and deprotonate aqua ligands. Thus they do not exist as simple ions such +5 2+ and as V4+ and V , instead exist as VO + VO2 ions.

The reduction from +4 to +2

The reduction from +5 to +4

Production of VO2+ in the laboratory

Dissolve about 2 g of ammonium metavanadate (NH4VO3) in about 50 cm3 of sodium hydroxide aqueous solution (1 M) in a 500 cm3 beaker. While stirring the solution formed, add 80 cm3of dilute sulphuric acid. Transfer the solution into a 250-cm3 volumetric flask and add distilled water to the calibration mark. Shake the volumetric flask vigorously and record the color of the solution. NH4VO3 + H2SO4
VO3 + 2H

NH4+ + H2O + VO2+ + SO42H2O + VO2+

++

Oxygen is expected to oxidize all the vanadium species t o VO2+ but it oxidize, V2+ to V3+. V3+ to VO2+ not V2+ due to kinetic stability of the VO2+

Question

When zinc power is added to aqueous Vanadium(V) ions, yellow green, blue, green and violet colours can be seen successively. Explain these observations.

VO2

+(aq)

Step 1

VO2+(aq)

Step 2

V3+

Step 3

V2+

Yellow.........greenblue..............green..violet

Step 1 = E red- Eoxid =(+1.00)-(-0.76) =+1.76V

Step 2 = E red- Eoxid =(+0.34)-(-0.76) =+1.10V

Step 3 = E red- Eoxid =(-0.26)-(-0.76) =+0.50V

Conclusion As E0cell value of each step is positive, all the three steps are feasible to occur spontaneously. Thus zinc can reduce VO2+ to V2+. Therefore colour change is from yellow to green to blue to green to violet. The final solution is violet. In between yellow and blue in the first step, green colour can be seen due to a mixture of VO2+ and VO2+ ions

COPPER

Copper [Ar]3d104s1
Copper, 3d10, is the only member of the transition series to have a significant +1 oxidation state, and even here the +1 state is only stable if in a complex ion, or in an insoluble compound in solution, it disproportionates. The +1 state, with a full d sub-shell, is not coloured (apart from Cu2O). The +2 state, with its familiar blue and green complexes, is the normal stable state.

Cu(I)

Cu2O, as made by reduction of Fehlings or Benedicts solution with a reducing sugar, is a red insoluble solid. CuCl and Cu2SO4 are white solids. Both of these, when dissolved in water disproportionate: 2Cu+(aq) Cu(s) + Cu2+(aq)

This can be understood in terms of the redox potentials:

Cu2+ + eCu+ + eCu+ Cu Eo = +0.15V Eo = +0.52V

There is a reaction between the two underlined species, i.e. the disproportionation. So when a copper(I) compound is dissolved in water a blue solution (Cu2+(aq)) and a red-brown solid (Cu(s)) are formed.

Many copper(I) compounds and copper(I) complex ions do not show the same variety of colour you see in copper(II) compounds and complex ions. The lack of scope for a variety of coloured compounds arises from the fundamental electronic configuration of the Cu+ ion, namely [Ar]3d10, giving a completely filled 3d sub-shell (identical to that of the zinc ion Zn2+, and zinc compounds and complex ions tend to be white or colourless).

ie there is no electron that can be promoted to a higher level when the 3d sub-shell is split when the central metal ion interacts with the ligands.

Cu(II)

Most copper(II) compounds are blue, and in solution they give blue Cu(H2O)62+ ions.

Reactions of copper(II) ions in solution

The reaction of hexaaquacopper(II) ions with hydroxide ions

Hydroxide ions (from, say, sodium hydroxide solution) remove hydrogen ions from the water ligands attached to the copper ion

Reactions of hexaaquacopper(II) ions with ammonia solution The ammonia acts as both a base and a ligand. With a small amount of ammonia, hydrogen ions are pulled off the hexaaqua ion exactly as in the hydroxide ion case to give the same neutral complex

That precipitate dissolves if you add an excess of ammonia The ammonia replaces water as a ligand to give tetraamminediaquacopper(II) ions.

A ligand exchange reaction involving chloride ions

Concentrated hydrochloric acid to a solution containing hexaaquacopper(II) ions, the six water molecules are replaced by four chloride ions. The reaction taking place is reversible.

Because the reaction is reversible, you get a mixture of colours due to both of the complex ions.

Using this reaction to find the concentration of copper(II) ions in solution

pipette a known volume of a solution containing copper(II) ions into a flask, and then add an excess of potassium iodide solution.

Find the amount of iodine liberated by titration with sodium thiosulphate solution.

As the sodium thiosulphate solution is run in from a burette, the colour of the iodine fades. When it is almost all gone, you add some starch solution. This reacts reversibly with iodine to give a deep blue starch-iodine complex which is much easier to see

the last few drops of the sodium thiosulphate solution slowly until the blue colour disappears
the reacting proportions through the two equations, you will find that for every 2 moles of copper(II) ions you had to start with, you need 2 moles of sodium thiosulphate solution. If you know the concentration of the sodium thiosulphate solution, it is easy to calculate the concentration of the copper(II) ions.

CHROMIUM

Chromium forms stable ions in three different oxidation states, +2, +3 and +6. In aqueous solutions, the ions formed are
Oxidation state Colour Ion +6 orange Cr2O72+3 Green Cr3+ +2 blue Cr2+

The actual formula of the +2 and +3 complex ions depends on the acid used (Cl- and SO42- will also behave as ligands).

In aqueous alkaline solutions, the ions formed are:

Oxidation state Colour Ion +6 yellow CrO42+3 Green Cr(OH)63-

The +6 chromium complexes can be readily interconverted using acid and alkali: 2CrO42-(aq) + 2H+(aq) Cr2O72-(aq) + H2O(l) Cr2O72-(aq) + 2OH-(aq) 2CrO42-(aq) + H2O(l)

a) In acidic solution

All chromium (VI) compounds can be reduced to the +3 and then the +2 oxidation state by strong reducing agents such as zinc in acid solution.

The chromium is first reduced to the +3 oxidation state:

Cr2O72-(aq) + 14H+(aq) + 6e == 2Cr3+(aq) + 7H2O(l) Zn(s) == Zn2+(aq) + 2e Overall : Cr2O72-(aq) + 14H+(aq) + 3Zn(s) 2Cr3+(aq) + 7H2O(l) + 3Zn2+(aq)

It is then further reduced: Cr3+(aq) + e == Cr2+(aq) Zn(s) == Zn2+(aq) + 2e Overall: Zn(s) + 2Cr3+(aq) Zn2+(aq) + 2Cr2+(aq)

The colour change observed on adding zinc in acid solution to dichromate ions is orange (Cr2O72-) to green (Cr3+) to blue (Cr2+).

Other, milder reducing agents will reduce the +6 oxidation state to +3 but no further. Fe2+ is an important example: Fe2+(aq) == Fe3+(aq) + e

Overall: Cr2O72-(aq) + 14H+(aq) + 6Fe2+(aq) 2Cr3+(aq) + 7H2O(l) + 6Fe3+(aq) This reaction can be used in titrations to determine the concentration of Fe2+ ions in a sample.

b) In alkaline solution

In alkaline solution, it is possible to oxidise the +3 oxidation state to the +6 oxidation state.

. Hydrogen peroxide, which is a reducing agent in acidic solution, is an oxidizing agent in alkaline solution.
[Cr(OH)6]3-(aq) + 2OH-(aq) == CrO42-(aq) + 4H2O(l) + 3e

H2O2(aq) + 2e == 2OH-(aq)
2[Cr(OH)6]3-(aq) + 3H2O2(aq) 2CrO42-(aq) + 8H2O(l) + 2OH-(aq)

The green [Cr(OH)6]3- ion is oxidised to the yellow CrO42- ion in alkaline solution.

In general, oxidation is favoured by alkaline conditions and reduction is favoured by acidic conditions.

Ligand exchange reactions involving chloride or sulphate ions

The hexaaquachromium(III) ion is a "difficult to describe" violet-blue-grey colour.

Replacement of the water by sulphate ions

One of the water molecules is replaced by a sulphate ion. Two of the positive charges are cancelled by the presence of the two negative charges on the sulphate ion.

Replacement of the water by chloride ions In the presence of chloride ions (for example with chromium(III) chloride), the most commonly observed colour is green. This happens when two of the water molecules are replaced by chloride ions to give the tetraaquadichlorochromium(III) ion - [Cr(H2O)4Cl2]+.

Uses of Cr

Chromium metal is used in making stainless steel is much more expensive than mild steel, resists corrosion effectively, but lacks some other useful properties (e.g strength, hardness) and so cannot always be substituted for normal steel. Chromium is added to iron in smaller amounts to make alloy steels which are very hard (used for example in ball bearings).

Other Uses of Transition Elements

Cancer involves cells dividing uncontrollably forming tumours. Cis Pt(NH3)2Cl2 was found to be able to inhibit cell division and could therefore be used as a treatment for cancer. Cisplatin as the material was called is now one of the most widely used anticancer drugs. One of the problems with it is its toxicity, so research continues and a new drug, carboplatin, has been developed.

Sunglasses

Photochromic sunglasses which become darker as the light intensity increases use a redox reaction.

The lenses contain silver(I) chloride and copper(I) chloride. Strong light causes the following reactions to take place:
Cu+ + Ag+ Ag + Cu2+ The silver produced in this reaction turns the glasses darker.

When the light intensity decreases, the reverse reaction takes place and the glasses become less dark.