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Unit 10
Section 10.1
1Electronic configurations
d-block elements lie in between the s-block and p-block elements in the fourth, fifth and sixth periods of the Periodic Table. The fourth period begins with two s-block elements : 19K ([Ar]4s1) and 2 The next ten d-block elements from 21Sc to 30Zn are remarkably similar to one another in 20Ca ([Ar]4s ). their properties and are all metals. The reason for the similarity is that, considering from Sc to Zn., while the nuclear charge increases by 1 unit, each additional electron is entering the inner 3d orbitals, it helps to shield the 4s electrons from the increased nuclear charge, with the result that the effective nuclear charge remains fairly constant across the ten d-block elements. The sizes of the atoms ,the magnitudes of the first ionization enthalpies and electronegativities are therefore very similar. The d-block elements are frequently referred to as transition elements because they are in transition from the electropositive elements of the s-block to the electronegative elements of the p-block. The electronic configurations of the d-block elements from Sc to Zn are given below : Element Sc Ti V Cr Mn Fe Co Ni Cu Zn 21 22 23 24 25 26 27 28 29 30 At. No. Z [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] Electronic Configuration 3d14s2 3d24s2 3d34s2 3d54s1 3d54s2 3d64s2 3d74s2 3d84s2 3d104s1 3d104s2 [Ar] = 1s22s22p63s23p6
" a Write down the electron configurations from Sc to Zn by using electron-in-boxes notation for the
3d and 4s orbitals. 3d Scandium Titanium Vanadium Chromium Manganese Iron Cabalt Nickel Copper Zinc [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] 4s
bSuggest reasons why atoms of chromium and copper have only one 4s electron while the other d-elements have two 4s electrons. For chromium, the 3d54s1 configuration is at a lower energy level than 3d44s2 because the former has more unpaired electrons. The extra repulsion between paired electrons, as compared to unpaired electrons, outweighs the small energy difference between the 3d and 4s level. For copper, the 3d104s1 is more stable than 3d94s2 because there appears to be extra stability associated with a full 3d subshell.
Unit 10 - 2
Unit 10 - 3
3Comparison of physical properties and reactions with water between d-block and s-block metals
Atomic radii Element Atomic radius /nm K Ca Sc 0.16 Ti 0.15 V 0.14 Cr 0.13 Mn 0.14 Fe 0.13 Co 0.13 Ni 0.13 Cu 0.13 Zn 0.13
0.24 0.20
There is a general decrease in atomic radii from K to Zn. In traversing the series of d-block metals from scandium to zinc, the nuclear charge is increasing, but electrons are being added to an inner 3d subshell. These inner d electrons shield the outer 4s electrons from the increasing nuclear charge much more effectively than outer shell electrons and consequently the decrease in radius is much less rapidly than s-block metals. For example, atomic radius varies from 0.16 nm (Sc) to 0.15nm (Ti), a difference of only 6.3%. In s-block metals, atomic radius varies from 0.24 nm (K) to 0.20 nm (Ca), a difference of 16.7%. Ionization enthalpies Element K First ionization 420 enthalpy kJmol-1 Ca 590 Sc 630 Ti 660 V 650 Cr 650 Mn 720 Fe 760 Co 760 Ni 740 Cu 750 Zn 910
The trends in ionization enthalpies and electronegativity depend largely on atomic radius. The closer an electron shell is to the nucleus, the more energy is required to remove an electron from it and the higher the ionization enthalpy. For the d-block metals, as the effective nuclear charge increases only slightly from Sc to Zn and the decrease in radius is less marked than in s-block metals, their first ionization enthalpies increase only slightly.
"
The first, second and third ionization enthalpies of d-block metals are given below : Element Sc Ti V Cr Mn Fe Co Ni Cu Zn 630 660 650 650 720 760 760 740 750 910 First ionization enthalpy kJmol-1 Second I.E. kJmol-1 1240 1310 1410 1590 1510 1560 1640 1750 1960 1700 Third I.E. kJmol-1 2390 2650 2870 2990 3260 2960 3230 3390 3560 3800
Discuss and explain any irregularities in the values of ionization enthalpies. aThe first ionization enthalpy of zinc is exceptionally greater than that of copper. The electronic configuration of zinc is probably more stable in having full 3d and 4s subshells. bThe second ionization enthalpy of Chromium is slightly greater than that of its preceding and succeeding neighbours. The second ionization enthalpy involves the removal of an electron from a half-filled subshell (3d5), which has extra stability : The case is similar for copper which possesses a full 3d subshell : cThe third ionization enthalpy of manganese is greater than its preceding and subsequent neighbours. The third ionization enthalpy involves the removal of an electron from a half-filled subshell (3d5), which has extra stability :
Unit 10 - 4
Melting points and hardness Element K Melting point 64 0.5 Hardness Ca 850 1.5 Sc Ti V Cr Mn Fe Co Ni Cu Zn 1540 1680 1900 1890 1240 1540 1500 1450 1080 420 3.0 4.5 6.1 9.0 5.0 4.5 2.8 2.5
Melting points Most of the d-block metals have a close packed metallic lattice structure, in which each atom has 12 nearest neighbours. The atomic radius of these elements is relatively small. The d-block metals have therefore much higher melting points than s-block metals, since these small sized atoms are closely-packed in the metal lattice, with 3d and 4s electrons participating in metallic bonding by delocalizing into the electron sea. The strength of metallic bond in d-block metals is thus very strong, as reflected in high melting points. Chromium, manganese and zinc have lower melting points, corresponding to weaker metallic bonding. Chromium has half-filled 3d and 4s subshells, whereas manganese has a half-filled 3d subshell and a full 4s subshell. Moreover, zinc has completely filled 3d and 4s subshells. These electronic configurations have extra stability and make the outer electrons less available for delocalization. As a result, metallic bonding is weakened, and these elements have lower melting points. In the s-block metals metallic bonding is weaker because the atomic radius is larger. The difference is most marked when comparing d-block metals with Group I metals, which have the largest atomic radii and do not have close-packed structures. In addition, they have only one valency electron per atom to contribute to the electron sea. Hardness Hardness measures the ability of the substances to scratch, abrade or indent one another. The hardness of the metals is again a reflection of the strength of the metallic bonds. Therefore, a comparison of the hardness between d-block and s-block metals parallels what has been described in the comparison of melting points. On the Mohs scale, hardness of diamond is 10 while that of finger-nail is 2.5. Reactions with water s-block metals usually react vigorously with water. e.g. K(s) + H2O(l) KOH(aq) + 1 H2(g) d-block metals react only very slowly with cold water. The rusting of iron is a slow process requiring both water and air. Other elements (e.g. Ti and Cr) often have an inherent oxide layer on its surface that resists corrosion by water and air. Iron, chromium and zinc react with steam at elevated temperatures to yield hydrogen. e.g. 3 Fe(s) + 2 Cr(s) + 4 H2O(g) 3 H2O(g)
Cr2O3(s) +
3H2(g)
Unit 10 - 5
Section
10.2
Characteristic properties of the d-block elements and their compounds Variable oxidation states
Section
10.2 A
1Interpretation of variable oxidation states in terms of electronic structures and successive ionization enthalpies
d-block elements have electrons of similar energy in both 3d and 4s subshells. Thus one particular element can form ions of roughly the same stability by losing different number of electrons. Transition elements from titanium to copper exhibit two or more oxidation states in their compounds. For example, the common oxidation states of iron are iron(II) and iron(III) : 3d 4s 6 2 Fe [Ar]3d 4s 2+ Fe [Ar]3d6 Fe3+ [Ar]3d5 Note that once the 3d orbitals are occupied by electrons, they repel the 4s electrons further from the nucleus, to an energy level higher than the 3d orbitals now occupied. Thus d-block elements lose electrons from the 4s subshell first, before the 3d subshells, during the formation of ions. The oxidation states occurring in compounds of d-block elements from Sc to Zn are given : Sc Oxidation states that occur in compounds (common oxidation states are in bold print) Ti V Cr 6 5 3 4 3
2 1 4 5 4
Mn 7
6 5
Fe
6 5 4
Co
Ni
Cu
Zn
4
3
5 4
3
2 1
3
2 1
2
1
3 2
1
3 2
1
4 3
2
1
2 1
Generalizations : aThe common oxidation states for each element include +2 or +3 or both. +3 states are relatively more common at the beginning of the series, whereas +2 states are more common towards the end. bThe highest oxidation states up to manganese correspond to the involvement of all the electron outside the argon core : 4 for Ti, 5 for V, 6 for Cr and 7 for Mn. After this, the increasing nuclear charge binds the d electrons more strongly and so one of the common oxidation states is that which involves the weakly held in the outer 4s shell only : 2 for Fe, 2 for Co, 2 for Ni and 1 for Cu. cTi, V, Cr and Mn never form simple ions in their highest oxidation state since this would result in ions of extremely high charge density. Hence the compounds of these elements in which they exhibit their highest oxidation state are either covalently bonded or contain complex ions, e.g. VO3-, CrO3, Cr2O72-, Mn2O7, MnO4-. dThe stability of Mn(II) and Fe(III) can be explained by the fact that both of their electronic structure is 3d5. This half-filled subshell in these ions has a particular stability. The Cu(I) ion with its full 3d10 electronic structure, is less stable than the Cu(II) ion (3d9) in aqueous solution because the following disproportionation reaction takes place readily :
Unit 10 - 6
Name Colour
Vanadium(V) oxide is used mainly as a catalyst in the industrial conversion of SO2(g) to SO3(g) (the Contact Process) for the manufacture of sulphuric(VI) acid. The activity of V2O5 as a heterogeneous catalyst may be linked to its reversible loss of oxygen that occurs at high temperatures. In alkaline medium the stable species of vanadium(V) is VO3-(aq). The solution of vanadium(V) can be made by dissolving about 3g of ammonium trioxovanadate(V) in 40 cm3 of 2M NaOH and then adding 80 cm3 of 1M H2SO4. The white solid (NH4VO3) turned red and dissolved to form a yellow solution owing to the presence of dioxovanadium(V) ions, VO2+, in acid solution : VO3-(aq) + 2H+(aq) VO2+(aq) is an oxidizing agent and can be reduced to oxovanadium(IV) ion in acidic medium : VO2+(aq) + 2H+(aq) + e- VO2+(aq) + H2O(l) EO = +1.00 V
Vanadium(IV) The stable oxidation state of vanadium(IV) is oxovanadium(IV) ion, VO2+(aq), which is blue in aqueous solution. VO2+(aq) can be reduced to vanadium(III) ion in acidic medium : V3+(aq) + H2O(l) EO = +0.337 V VO2+(aq) + 2H+(aq) + e-
Vanadium(III) and vanadium(II) In aqueous solution, vanadium(III) and vanadium(II) exist as hydrated ions, V3+(aq) and V2+(aq). Oxidation state Ion Electronic structure Colour in aqueous solution +3 V3+ [Ar] 3d2 +2 V2+ [Ar] 3d1
The half-equations for the conversion of vanadium(III) to vanadium(II) and vanadium(II) to vanadium are as follows : EO = -0.255 V V3+(aq) + e- V2+(aq) 2+ V (aq) + e V(s) EO = -1.18 V In its lowest oxidation states, vanadium (as V2+) is a good reducing agent.
Unit 10 - 7
+5
+4
+3
+2
VO2+(aq)
+0.337V
V3+(aq)
-0.255V
V2+(aq)
-1.18V
V(s)
2.
Unit 10 - 8
Solutions of potassium manganate(VII) are kept in brown bottles because in the presence of light they slowly oxidizes water to oxygen : 4MnO4-(aq) + 4H+(aq) Potassium manganate(VII) is a powerful oxidizing agent, its oxidizing power in solution depends on the pH of the solution. Under acidic condition it is reduced to pink manganese(II) ions : MnO4-(aq) + 8H+(aq) + 5e- Mn2+(aq) + 4H2O(l) EO = +1.51V purple pink In neutral and alkaline solution the manganate(VII) is reduced to brown manganese(IV) oxide : MnO4-(aq) + 2H2O(l) + 3e- MnO2(s) + 4OH-(aq) EO = +1.67V purple brown In more strongly alkaline solution, manganate(VII) is reduced to green manganate(VI) ions : MnO4-(aq) + e MnO42-(aq) EO = +0.56V purple green Potassium manganate(VII) is used widely as an oxidizing agent in volumetric analysis. It is used, for example, to estimate iron(II) and ethanedioates : MnO4-(aq) + 5Fe2+(aq) + 8H+(aq) Mn2+(aq) + 5Fe3+(aq) + 4H2O(l) 2MnO4-(aq) + 5C2O42-(aq) + 16H+(aq)
The colour change is from purple to colourless, because the Mn2+(aq) concentration is too low to colour the solution pink. Titration with potassium manganate(VII) requires no indicator, as the end point is shown by the appearance of its purple colour. Dilute sulphuric(VI) acid is usually used to acidify manganate(VII) because hydrochloric acid is oxidized to chlorine and nitric(V) acid is an oxidizing agent. Manganese(VI) Potassium manganate(VI), K2MnO4 , is a dark green solid. It is only stable in alkaline solution. In acidic solution it disproportionates to manganate(VII) and manganese(IV) oxide. MnO42-(aq) + 4H+(aq) + 2e- MnO2(s) + MnO42-(aq) MnO4-(aq) + eoverall equation: 2H2O(l) EO =+2.26V EO =-0.56V
Unit 10 - 9
Manganese(IV) The most important manganese(IV) compound is manganese(IV) oxide, MnO2 . This is a dark brown compound which is insoluble in water. MnO2 is a powerful oxidizing agent in acidic medium : MnO2(s) + 4H+(aq) + 2e- Mn2+(aq) + 2H2O(l) EO =+1.23V This is sometimes used as a laboratory preparation chlorine from conc. hydrochloric acid : MnO2(s) + 4HCl(aq)
Manganese(III) Manganese(III) only occurs in complexes. It is unstable. Under acid conditions manganese(III) disproportionates to manganese(II) and manganese(IV) oxide. Mn3+(aq) + e- Mn2+(aq) EO =+1.51V 3+ + Mn (aq) + 2H2O(l) MnO2(s) + 4H (aq) + e EO =-0.95V overall equation: Managanese(II) This is the most stable form of manganese. It has the outer electron configuration 3d5. Each of the five 3d orbitals contains one electron. Manganese(II) ions are hydrated in aqueous solution forming the pale pink hexaaquamanganese(II) complex ion, [Mn(H2O)6]2+(aq) , which is usually simplified as Manganese(II) ions are formed by the reaction between manganese metal and dilute Mn2+(aq). hydrochloric acid : Mn(s) + 2H+(aq) Mn2+(aq) + H2(g) Addition of alkali to manganese(II) solution gives a white precipitate of manganese(II) hydroxide : Mn2+(aq) + 2OH-(aq) Mn(OH)2(s) pale pink white Manganese(II) can be oxidized to manganate(VII) by the very powerful oxidizing agent such as bismuthate(V), BiO3-, in dilute nitric acid : 2Mn2+(aq) + pale pink Summary : Oxidation state Ion/oxide Colour 5BiO3-(aq) + 14H+(aq) purple
+7 deep purple
+6 green
+4 dark brown
+3 red
"Predict the feasibility of making Mn(III) from Mn(II) and Mn(VII) in acid conditions.
electrode potentials are : Mn3+(aq) + e- Mn2+(aq) MnO4-(aq) + 8H+(aq) + 5e- Mn2+(aq) + Combining the two half-equations gives : 4H2O(l)
EO =+1.51V EO = +1.51V
EOcell =0.00V means that the reaction is in equilibrium under standard condition. It should be possible to make the EOcell value positive by increasing the hydrogen ion concentration. This will shift the equilibrium to the right.
Unit 10 - 10
Section
10.2 B
Complex formation
Complexes are formed by the dative covalent bonds from the lone pairs of electrons on the ligands to the vacant, low energy orbitals on the central d-block metal ion or atom. The central metal ion or atom uses empty hybrid orbitals formed by its vacant s, p and d orbitals to accept lone pairs of electrons. The ligand is an anion or molecule containing lone pair of electrons that can be donated to the central metal ion or atom with the formation of a dative covalent bond. A ligand which can only form one bond to a central metal ion or atom is called a monodentate ligand, e.g. H2O, NH3, Cl- and CN-.
A polydentate ligand can form more than one bond. Examples are the bidentate ligands ethanedioate ion, 1,2-diaminoethane (en) and the multidentate ligand edta.
For instance, in the hexacyanoferrate(II) ion, [Fe(CN)6]4-, cyanide ions form dative covalent bonds with Fe2+ ion. The electronic configurations of Fe2+ and the complex ion are as follows : 3d 4s 3p 2+ Fe Hybridized d2sp3 2+ Fe [Fe(CN)6]4d2sp3 The unpaired d electrons pair up to vacate orbitals in Fe2+ which can be occupied by lone pairs of electrons. Six hybrid d2sp3 orbitals are formed. They are directed to the apices of an octahedron. Lone pairs of electrons from the cyanide ions coordinate into the empty hybrid orbitals.
Unit 10 - 11
The coordination number is the number of dative covalent bonds forming between the ligands and the central metal ion or atom. 2, 4 and 6 are the common coordination number. 2-coordinated complexes Complexes with a coordination number of 2 have a linear arrangement of ligands. Example : [Ag(NH3)2]+
4-coordinated complexes Complexes with a coordination number of 4 usually have a tetrahedral arrangement of ligands. Example : [CoCl4]2-
A few complexes with a coordination number of 4 have a square planar arrangement of ligands. Example : [Cu(NH3)4]2+
6-coordinated complexes Complexes with a coordination number of 6 have an octahedral arrangement of ligands. Example : [Fe(CN)6]3-
Example : [Fe(C2O4)3]3-
Unit 10 - 12
2Nomenclature of complexes
In the formula of a complex, the symbol for the central ion or atom appears first and is followed by the anionic ligands and then by neutral ligands. The formula for the complex may be enclosed in square brackets. Example : [CoCl2(NH3)4]+ central ion : ligands :
The complex can be cationic, neutral or anionic. 1. If the complex is neutral or a cation, its name gives the name and oxidation state of the central metal ion or atom preceded by the number and name of ligands attached to it. The name of ligands are as follows : Ligand H2O NH3 ClCNOHCO edta Name aqua ammine chloro cyano hydroxo carbonyl edta The prefixes : di, tri, tetra, penta and hexa are used to show the number of ligands. If several different ligands are present, they are listed a. in order of anionic ligand before neutral ligand, and b. in alphabetical order, and the prefixes, di, tri, etc., are not allowed to change this order. Example : [Co(NH3)6]2+ Example : [CoCl2(NH3)4]+ Example : [FeCl2(H2O)4]+ Example : Ni(CO)4 2. If the complex is an anion, the suffix -ate follows the name of the metal, e.g. zincate and chromate. If the metal has a Latin name, then in the complex anion the Latin name of the metal is used, followed by the suffix -ate. Fe Co Cu Ag Pt Pb
Examples are given in table : Formula of complex Name of complex 4[Fe(CN)6] [Fe(CN)6]3[CuCl4]2[CoCl3(H2O)3][Fe(OH)2(H2O)4]+ [Fe(OH)2(H2O)4] [Cu(NH3)4]2+ [Zn(OH)4]2[Zn(edta)]2-
Unit 10 - 13
bK2[CoCl4]
Example 2 When hydrogen chloride is passed into cold chromium(III) nitrate solution, violet crystals A, CrCl3.6H2O, are obtained. These lose no water when stood over concentrated sulphuric acid in a desiccator, and 1 mol of A gives 3 mol of AgCl immediately, on addition of silver nitrate to the solution. On cooling a hot solution of chromium(III) chloride, green crystals B, CrCl3.6H2O, are formed. B loses water over concentrated sulphuric acid to give CrCl3.4H2O. On addition of silver nitrate, 1 mol of B gives 1 mol of AgCl at once. By treatment of a solution of B successively with sulphuric and hydrochloric acids, the green crystals C, also with the formula CrCl3.6H2O, can be made. 1 mol of C loses 1 mol of water over concentrated sulphuric acid, gives 2 mol of AgCl at once. a Suggest structures for compounds A, B and C.
b Suggest a structure for yet another compound with the formula CrCl3.6H2O. behaviour with silver nitrate and with concentrated sulphuric acid ?
A solution of this compound would not react with silver nitrate. However, 1 mol of this compound would readily lose 3 mol of water over conc. sulphuric acid. Example 3 Complete the following table which gives the range of cobalt(III) chloride/ammonia complex compounds : Molecular formula CoCl3.6NH3 CoCl3.5NH3 CoCl3.4NH3 CoCl3.5NH3.H2O Colour Structural formula Complex ion No. of moles of AgCl precipitated per mol of complex compound
Unit 10 - 14
is known as the stability constant of the complex MLm at that temperature. Water is usually present in such large quantity that its concentration is relatively unaffected. The term [H2O(l)] is therefore incorporated into the stability constant. Such a stability constant measures quantitatively the extent of formation of the complex in the above reaction, so that if Kst has a large magnitude, the complex is formed in large amount, i.e., it is relatively more stable. For example, Copper(II) sulphate dissolved in water forms the hexaaquacopper(II) ion, [Cu(H2O)6]2+(aq), which is responsible for the pale blue colour of the solution. Addition of chloride ions in high concentration (e.g. concentrated hydrochloric acid) leads to the stepwise replacement of H2O ligands by Cl- ligands : K at 25(mol-1dm3) pale blue [Cu(H2O)6]2+(aq) + [Cu(H2O)5Cl]+(aq) + green [Cu(H2O)4Cl2](aq) + yellow [Cu(H2O)3Cl3]-(aq) + Cl-(aq) [Cu(H2O)3Cl3]-(aq) + H2O(l) K3 = 5.4 K4 = 3.1 Cl-(aq) [Cu(H2O)5Cl]+(aq) + H2O(l) K1 = 6.3 x 102
Cl-(aq) [Cu(H2O)4Cl2](aq) +
Cl-(aq) [CuCl4]2-(aq) +
3H2O(l)
Adding the above four equations together gives the over reaction : [Cu(H2O)6]2+(aq) + 4Cl-(aq) [CuCl4]2-(aq) + 6 H2O(l) It can be shown that the overall stability constant of [CuCl4]2-(aq) , Kst =
Note that the [CuCl4]2-(aq) complex is yellow in colour but when mixed with the blue [Cu(H2O)6]2+(aq) ion a yellow-green solution is often formed. Kst reflects the stability of the complex formed. is the complex. The larger the stability constant, the more stable
Unit 10 - 15
Displacement of ligands Ammonia is an even stronger ligand than Cl-. It will displace both water from [Cu(H2O)6]2+(aq) and Cl- from [CuCl4]2-(aq) , forming the deep blue tetraamminecopper(II) ion, [Cu(NH3)4]2+(aq) : [Cu(H2O)6]2+(aq) + 4NH3(aq) [Cu(NH3)4]2+(aq) + 6 H2O(l) Kst = The stability constant for [Cu(NH3)4]2+(aq) is larger than that for [CuCl4]2-(aq) , showing that NH3 is a stronger ligand than either Cl- or H2O. When ammonia solution is added to a solution of [CuCl4]2-(aq) , NH3 molecules displace Cl- from [CuCl4]2- forming [Cu(NH3)4]2+ and the colour change from yellow to deep blue. [CuCl4]2-(aq) + 4NH3(aq) [Cu(NH3)4]2+(aq) + 4Cl-(aq) Kc = The equilibrium constant for the displacement is large. Thus, complexing reactions usually involve competitions between different ligands for metal ions. In this case, ammonia acts as a stronger ligand than Cl-.
Relative stability of complex ions Factors affecting the stability of complexes are : aLigand strength If a ligand can donate its lone pair of electrons more readily, the greater will be the stability of complexes formed by it. In general,
bCharge density of central metal ion The higher the charge density of the central metal ion, the greater is the electrostatic attraction for the lone pairs of electrons from the ligands and thus the more stable a complex tends to be formed. Example : [Fe(CN)6]3[Fe(CN)6]4Kst = 1.0 x 1031 mol-6dm18 Kst = 2.0 x 108 mol-6dm18
The extraordinary difference between two stability constants demonstrates the fact that Fe3+ has a higher charge and smaller ionic radius than that of Fe2+. cChelate effect A polydentate ligand tends to form more stable complexes than monodentate ones. It is because the coordination of one end of a polydentate ligand will greatly enhance the chance for the coordination of the other ends. Example : [Co(NH3)6]2+ Kst = 2.3 x 104 mol-6dm18 [Co(edta)]2Kst = 1.26 x 1016 mol-1dm3
Unit 10 - 16
" One of the most fascinating and intriguing demonstration of the relative stability of complexes is
outlined in the tests shown in table : Ligand H2O ClNH3 Complex ion Blue yellow deep blue Colour 5 1.1 x 1013 3.9 x 10 Stability -4 12 mol dm mol-4dm12 constant Test = displacement (change of colour) Add H2O Add ClAdd NH3 Add edta4edta4light blue 6.3 x 1018 mol-1dm3 8 = none
One of the ligand exchange reactions appeared to be readily reversible. Which one was this ? H2O and Cl- ligands appear to be readily interchangeable when concentrations are changed. Adding water to [CuCl4]2-(aq) will reduce the concentration of Cl- ions sufficiently to convert a significant proportion of [CuCl4]2- ions to [Cu(H2O)6]2+ ions and so change of the colour. [CuCl4]2-(aq) + 6 H2O(l) [Cu(H2O)6]2+(aq) + 4Cl-(aq)
Unit 10 - 17
Section
10.2 C
1Introduction
Transition metals and their compounds are important catalysts in industry and in biological systems. Some of the transition metals including copper, manganese, iron, cobalt, nickel and chromium are essential for the effective catalytic activity of various enzymes. One of the most important enzymes containing copper is cytochrome oxidase. This enzyme is involved in the process energy is obtained from the oxidation of food. In the absence of copper, cytochrome oxidase is completely inhibited and the animal or plant is unable to metabolize food effectively. Numerous transition metals and their compounds are important industrial catalysts. of the more important examples is shown in table : Transition metal Ti V Fe Ni Cu Pt Pt Substance used Reaction catalysed as catalyst TiCl3 Polymerization of ethene : V2O5 or vanadate(V) Fe or Fe2O3 Ni Cu or CuO Pt Pt Contact Process : Haber Process : Manufacture of margarine : Oxidation of ethanol to ethanal : Contact Process : Manufacture of nitric acid : A list of some
Transition metal and their compounds can catalyse reactions because they are able to introduce an entirely new reaction mechanism with a lower activation energy than the uncatalysed reaction. Since the activation energy of the catalysed reaction is lower, the reaction rate is faster. Chemist believe that the catalytic activity of transition metals and their compounds depends on their ability to exist in various oxidation states.
Unit 10 - 18
2Heterogeneous catalysis
In the heterogeneous catalysis, the presence of partly filled d orbitals in the transition metals and their compounds enables it to accept electrons from reactant particles on one hand and donate electrons to the reactants particles on the other. Use of Fe in Haber Process In the absence of a catalyst, the formation of gaseous ammonia from nitrogen and hydrogen depends on the simultaneous collision of four gaseous molecules, the probability of which is extremely small. The synthesis of ammonia with iron as a catalyst in Haber Process provides an example of heterogeneous catalyst : N2(g) + 3H2(g) 2NH3(g) The iron metal is in the solid phase, whereas the hydrogen and nitrogen are in the gaseous phase. The catalytic process actually occurs at the interface between these two phases, with the iron metal providing an active reaction surface for the reactants. The catalytic reaction occurs in a sequence of steps : 1. N2(g) and H2(g) diffuse to the surface of the catalyst iron metal. 2. The gases are then adsorbed on the iron metal surface. The iron metal owes its catalytic effect by having numerous 3d electrons and many vacant 3d orbitals. It is therefore capable of temporarily donating or accepting electrons from species adsorbed on its surface. This results in a sort of chemisorption, with weak bonds forming between the catalyst surface and the reactant particles. 3. Chemisorption weakens significantly the NN bond, thus providing a different reaction path with lower activation energy for the reaction. Specifically, N2 dissociates into weakly adsorbed N atoms at a moderate temperature of around 500, whereas H2 dissociates at temperatures as low as -196 into weakly adsorbed H atoms. These atoms are highly reactive, and meet each other quite readily to result in the formation of NH3. 4. The NH3 molecules desorb easily as a result of the weak interaction with the iron surface. The energy profile for the synthesis of ammonia in the presence of iron and in the absence of a heterogeneous catalyst is shown as follows : Potential energy
Reaction Co-ordinate
Unit 10 - 19
Use of MnO2 in the decomposition of hydrogen peroxide The decomposition of hydrogen peroxide as catalysed by manganese(IV) oxide is another example of heterogeneous catalysis. 2H2O2(aq) O2(g) +
MnO2(s)
2H2O(l)
Under normal conditions, this reaction is very slow. It can be speeded up by using more concentrated hydrogen peroxide or by heating it. A much easier way of speeding it up is to add manganese(IV) oxide. MnO2 is a fine, black powder. Even it is cold and dilute, the hydrogen peroxide starts to decompose rapidly in the presence of MnO2(s). The catalytic process occurs at the interface between the solid phase of MnO2 and the aqueous phase of H2O2. Once the reactants H2O2 molecules are adsorbed on the active surface of MnO2, they can be decomposed via a new pathway that proceeds at a much higher rate. Active catalyst surfaces are regenerated once the product molecules of O2 and H2O diffuse away. The energy profile for the decomposition of hydrogen peroxide in the presence of MnO2 and in the absence of a heterogeneous catalyst is shown as follows : Potential energy
Reaction Co-ordinate
Unit 10 - 20
3Homogeneous catalysis
In homogeneous catalysis, the transition metals and their compounds can exhibit variable oxidation states, thus allowing electron transfer between reactants and products by means of the catalyst changing between two oxidation states. Use of Fe3+ or Fe2+ in the reaction between iodide and peroxodisulphate(VI) ions The oxidation of I-(aq) by peroxodisulphate(VI) ions, S2O82-(aq) , is catalysed homogeneously by small concentrations of aqueous Fe(III), Fe(II) or Cu(II) ions. 2I-(aq) + S2O82-(aq) I2(aq) + 2SO42-(aq) The rate of this reaction can be measured conveniently by adding a little starch solution and a fixed amount of sodium thiosulphate. As soon as sufficient iodine has been formed to react with the thiosulphate present, a blue colour is formed with the starch, and the time for the appearance of the colour is inversely proportional to the average reaction rate. Alternatively the rate of the reaction can be followed by a colorimeter, as the colour intensity of I2(aq) will increase when iodine is being formed during the reaction. In the catalytic process, the Fe3+(aq) ion takes part in the reaction by oxidizing the I-(aq) ions to I2(aq), itself being reduced to Fe2+(aq) ion : The Fe2+(aq) ion is subsequently oxidized by the S2O82-(aq) ion, so that the original Fe3+(aq) ion is regenerated. The overall process is the sum of these two stages : 2I-(aq) + S2O82-(aq) I2(aq) + 2SO42-(aq) The energy profile for the reaction in the presence of iron(III) ion and in the absence of a homogeneous catalyst is shown as follows : Potential energy
Reaction Co-ordinate Fe2+(aq) ions can also catalyse the same reaction by another mechanism, the Fe2+(aq) ions being regenerated unchanged at the end of the reaction : Fe2+(aq) + S2O82-(aq) Fe3+(aq) + 2SO42-(aq) Fe3+(aq) + 2I-(aq) Fe2+(aq) + I2(aq) 2I-(aq) + S2O82-(aq) I2(aq) + 2SO42-(aq)
Unit 10 - 21
Section
10.2 D
Coloured ions
To account for the particular colour of a transition metal complex, Ligand Field Theory is proposed. Under the influence of a ligand, the 3d orbitals of the central metal ion split into two groups with slightly different energy levels, and the energy difference that it causes depends on the nature of the ligand and the shape of the complex. The promotion of an electron from the lower to the higher of these d orbitals just happens to require energy within the range of visible light. For instance, the energy difference between the two groups of d orbitals for the [Cu(H2O)]2+ ion is of just the right magnitude for promotion of an electron by the absorption of red light. That is why the ion appears to be blue. Energy ___ ___ two groups of split 3d orbitals ___ ___ ___
In [Cu(NH3)4]2+ , the energy between two groups of d orbitals is larger, the absorbed light is orange, and the ion appears deep blue in colour. I.R. Red Orange Yellow Green Indigo Blue Violet U.V.
increasing frequency
" Why do you think that the following compounds are colourless - ScCl3, ZnSO4, CuCl ?
Scandium(III) ions, Sc3+, have no electrons in the 3d orbitals. Therefore, electronic transitions involving such electrons are not possible. Zinc ions, Zn2+, and copper(I) ions, Cu+, have completely filled 3d subshell (3d10). As the electronic transitions responsible for the colour always involve partly filled orbitals, such electronic transitions cannot occur in Zn2+ and Cu+ ions.
Unit 10 - 22
Upon addition of alkali, hydrated iron(II) ions give a dirty green precipitate of hydrated iron(II) hydroxide : [Fe(H2O)6]2+(aq) + 2OH-(aq) [Fe(OH)2(H2O)4](s) + 2H2O(l) green dirty green precipitate The hexaaquairon(II) ion is stable in acidic solution. In neutral or alkaline solution, it is unstable and is oxidized by oxygen to form the yellow hexaaquairon(III) ion, [Fe(H2O)6]3+(aq) . Upon addition of alkali, hydrated iron(III) ions give a reddish brown precipitate of hydrated iron(III) hydroxide : [Fe(H2O)6]3+(aq) + 3OH-(aq) [Fe(OH)3(H2O)3](s) + 3H2O(l) yellow reddish brown precipitate Hydrated iron(III) ions form a blood-red complex with thiocyanate ions, SCN-(aq) : [Fe(H2O)6]3+(aq) + SCN-(aq) yellow The blood-red colour only fades when excess NaF(aq) solution is added : [FeSCN(H2O)5]2+(aq) + 6F-(aq) blood-red
Unit 10 - 23
On dilution the above equilibrium shifts to the left, the solution turns green and finally blue due to the formation of hydrated Cu(II) ions, [Cu(H2O)6]2+(aq). The green colour results from the presence of both the yellow [CuCl4]2-(aq) ions and the blue [Cu(H2O)6]2+(aq) ions in solution. When ammonia solution or NaOH(aq) is added to a solution containing hydrated Cu(II) ions, a blue precipitate of hydrated copper(II) hydroxide is produced : [Cu(H2O)6]2+(aq) + pale blue 2OH-(aq)
[Cu(OH)2(H2O)4](s) + 2H2O(l)
blue ppt.
Copper(II) hydroxide dissolves in excess ammonia, forming the deep blue tetraamminecopper(II) ion : [Cu(OH)2(H2O)4](s) + blue ppt. 4NH3(aq)
"The following tests can be used to distinguish a hydrated iron(II) ion from a hydrated iron(III) ion.
Write the observations for the tests. Test Add NaOH(aq) Add potassium thiocyanate Fe2+(aq) Fe3+(aq)
"The following tests can be used to distinguish a hydrated Zn(II) ion from a hydrated Cu(II) ion.
Write the observations for the tests. Test Add NaOH(aq) Add excess NaOH(aq) Add NH3(aq) Add excess NH3(aq) Zn2+(aq) Cu2+(aq)