The d-Block Elements
Definition: The d-block elements are the elements with electronic configurations in which the d-orbitals are being partially filled. General features of the d-block elements from Sc to Zn 1. electronic configuration. Element Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Atomic number 21 22 23 24 25 26 27 28 29 30 [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] electronic configuration 3d 4s
2. d-block elements as metals The d-block elements are typical metals. They are also called transition metals. They are good conductors of heat and electricity. They have high melting points and boiling points.
3. Comparison of some physical and chemical properties between d-block and s-block elements. i) Atomic radius
Features: a) d-block metals have smaller atomic radius than s-block elements. This is because the screening effect of d-subshell electrons is poor. The increase in effective nuclear charge when the electron is added to the same d-subshell makes the electrons contract. b) d-block metals have similar atomic radius across the series. - The atomic radius at first decreases, then remains unchanged in the middle of the series. At the end, the atomic radius increases again. Because at the beginning, the increases in effective nuclear charge pulls in the electron, resulting in a reduction of atomic size. In the middle, since electrons are added to the inner 3d-subshell, the increasing screening and repulsive effects of the electrons in the 3d subshell cancel out the increase in effective nuclear charge. Hence there is a little change in atomic radius. At the end, as more electrons are added to the same d-subshell, the screening and repulsive effects reach a maximum. Hence the electron explands. ii) Density
The densities of d-block elements are higher than those of s-block elements. Because d-block elements have close-packed structure and with smaller atomic radius while s-block metals may not have close-packed structure. The densities increase generally increase across the series. This is in agreement with the change in atomic radius across the series.
iii) Ionization enthalpies
Trend: The 1st ionization enthalpies increase gradually across the series. - Across the series, electrons are added to the inner 3d subshell. The inner d-eelctrons can shield the outer 4s electrons less effectively, hence the effective nuclear charge increases and 1st ionization enthalpies increase gradually. Trend: The 1st ionization enthalpies only increase slowly. - It is because the increase in repulsion of 3d electrons cancels out the increase in effective nuclear charge to a certain extent. Trend: The successive ionization enthalpies exhibit a similar increase. - The reason is the same as that for 1st ionization enthalpies. Some irregularities in the variation: 1) The 1st ionization enthalpy of zinc is exceptional high because it has a full- filled 3d subshell. 2) The 2nd ionization enthalpy of chromium is higher than manganese. It is because it has a half- filled 3d subshell which has extra stability. 3) The 3rd ionization enthalpy of iron is smaller than manganese. It is because the removal of the 3rd electron from iron gives a stable half- filled 3d subshell. Hence less energy is required.
The electronegativity of d-block elements are higher than those of s-block elements. It is because the d-block elements have smaller atomic radii and hence the nucleus of the d-block elements can attract the electrons in a bond more tightly. Moreover, the electronegativity of d-blocks increase gradually across the series because the increase in effective nuclear charge. v) Melting point
The melting points of d-block elements are higher than those of s-block elements. This is because the d-block elements have a close-packed structure. Moreover d-block elements have smaller atomic radii and this means the d-block metallic ions have a higher charge density. And both the 3d and 4s electrons of d-block elements delocalize to participate in the formation of metallic bond. All these mean that the metallic bonds in d-block elements are stronger than those in s-block elements. Hardness of a metal is dependent on the strength of the metallic bonds. As the metallic bond strength of d-block elements is stronger than that of s-block elements, the d-block metals are harder than s-block elements.
vi) Reactions with water s-blocks elements often react vigorously with water. d-block elements usually react very slowly with water. Zn(s) + H2 O(g) ---à ZnO(s) + H2 (g) 3 Fe(s) + H2 O(g) ---à Fe3 O4 (s) + 4 H2 (g) Characteristic properties of the d-block elements and their compounds The d-block elements have the following characteristic properties when compared with the s-block metals 1. Variable oxidation states The 3d and 4s electrons are of similar energy so that both levels of electrons are available for bonding.
* According to the syllabus, studies limited to common oxidation states of vanadium V (+2, +3 +4, +5) and manganese Mn (+2 , +4 , +7) For vanadium, Vanadium(V) ions can be reduced to vanadium(II) ions by zinc metal and acid.
For manganese, MnO2 (s) is an oxidizing agent.
MnO4 -(aq) is an common strong oxidizing agent. Its oxidizing power depends on the pH of the solution.
2. Complex formation A complex is formed when a central metal atom or ion (usually a d-block metal/metal ion) is surrounded by other molecules or ions which form dative covalent bonds with the central metal atom or ion. The molecule or ion which form the dative covalent bonds are called ligand.
* According to the syllabus, studies limited to complexes of Fe2+ , Fe3+ , Co2+ , Cu2+ with the following ligands: H2 O , NH3 , Cl- ,CNstructure of some commpn ligands:
To act as a ligand, a molecule or ion should have a lone pair electrons so that it can form dative covalent bond with the central metal atom or ion.
Nomenclature of complexes Complexes are named according to the IUPAC rules. 1. Ligands have special names: H2 O : aqua NH3 : ammine Cl- : chloro CN- : cyano 2. The cation is named before the anion K2 [CoCl4 ] potassium tetrachlorocabaltate(II) [Co(NH3 )6 ]Cl3 hexaamminecobalt(III) chloride 3. If the complex ion is anionic, the ending –ate is attached to the name of the metal and this is followed by the oxidation state of the metal. Metal Name in anionic complex Iron ferrate Cobalt cobaltate Copper cuprate K2 [CoCl4 ] potassium tetrachlorocabaltate(II) K3 [Fe(CN)6 ] potassium hexacyanoferrate(III) [CuCl4 ]2tetrachlorocuprate(II) ion If the complex is cationic or neutral, then the name of metal is unchanged. K[CoCl2 (NH3 )4 ] potassium dichlorotetraamminecobalt(III) 4. If the complex compound is neutral, the complex is named in one word. [CoCl3 (NH3 )3 ] trichlorotriamminecobalt(III) Formation of complex The d-block metals can form complexes because they have vacant, low lying (low energy) 3d orbitals to form dative covalent bonds with the lone pair electrons of the ligand. Because s-block metals do not have these vacant, low lying (low energy) 3d orbitals, they normally do not form complexes.
Displacement of ligands and relative stability of complex ions Some ligands may form stronger dative covalent bonds than other ligands with the central metal ion. Hence some ligands may be displaced by other ligands. Stronger lgands: CN- , ClWeaker ligand: H2 O e.g.
e.g. When concentrated hydrochloric acid is added to copper(II) sulphate solution, the colour of solution change from pale blue to yellow.
The equilibrium constant Kst of the reaction is called the stability constant of the complex.
The larger the stability constant, more stable is the complex.
Stereo-structures of 4- and 6-coordinated complexes 1) 4-coordinated (tetra-coordinated) complexes The shape of complex is either tetrahedral or square planar. a) tetrahedral
b) square planar
2) 6-coordinated (hexa-coordinated) complexes The shape of complex is octahedral.
Structural isomers in complex Isomers that have different ligands bonded to the central metal atom or ion. e.g. [Co(NH3 )5 Br]SO4 and [Co(NH3 )5 SO4 ]Br e.g.
Geometrical isomers in complex Isomers that have different arrangement of ligands in space. 1) square planar i) Ma2 b2
ii) Ma2 bc
2) octahedral i) Ma4 b2
e.g. dichlorotetraamminecobalt(III) ion [CoCl2 (NH3 )4 ]+ has two geometrical isomers.
ii) Ma3 b3 fac-isomer means three ‘a’ligands are in adjacent positions on one triangular face of the octahedral structure. mer-isomer means three ‘a’ ligands are located in a plane that contains the metal atom or ion.
e.g. trichlorotriamminecobalt(III) ion [CoCl3 (NH3 )3 ] has two geometrical isomers.
* Remember that geometrical isomers mentioned above have different physical properties, e.g. melting points and colours,..
Coloured ions - Studies are limited to hydrated ions of Fe2+ , Fe3+ , Co2+ , Cu2+ . - A substance appears coloured because it absorbs some of the light in the visible region. - A substance appears to have a colour complementary to that of the absorbed light. e.g. [Cu(H2 O)4]2+(aq) appears blue because it absorbs yellow light. [CuCl4 ]2-(aq) appears yellow because it absorbs yellow blue.
For a free, isolated transition metal ion, all its five 3d orbitals are degenerate (have the same energy level). Under the influence of the ligands, these five 3d orbitals split into two groups with small energy difference. And the difference in energy falls into the visible region of light.
When some light energy is absorbed, the unpaired 3d electrons is promoted from its lower 3d energy level to the higher 3d energy level. Because of the d-d transition and the absorption of light, the transition metal ions usually appear coloured. Ions Fe2+ Fe3+ Co2+ Cu2+ colour green yellow pink blue electronic configuration
Catalytic properties of transition metals and their compounds - The d-block transition metals and their compounds are important catalysts in industry. - Catalyst provides an alternative reaction pathway which has a lower activation energy for the reaction. Hence the number of particles having energy higher than the activation energy increases and the reaction rate increases. a) Iron used in Haber process N2 (g) + 3 H2 (g) 2 NH3 (g) £GH = -92.3 kJmol-1
Finely divided iron is used as the heterogeneous catalyst (catalyst in different phase from the reactants and products).
b) Fe2+ or Fe3+ in the reaction between peroxodisulphate(VI) and iodide ions 2 I-(aq) + S2 O82-(aq) ---à I2 (aq) + 2 SO4 2-(aq) The reaction is catalysed by small amount of Fe2+ or Fe3+ ions. Fe2+ or Fe3+ is a homogeneous catalyst ( catalyst, reactants and products are in same phase). In the cayalytic process, the Fe2+ or Fe3+ ions take part in the reaction. e.g. 2 I-(aq) + 2 Fe3+(aq) ---à I2 (aq) + 2 Fe2+(aq) 2 Fe2+(aq) + S2 O8 2-(aq) ---à 2 Fe3+(aq) + 2 SO42-(aq) overall: 2 I-(aq) + S2 O82-(aq) ---à I2 (aq) + 2 SO4 2-(aq)
c) MnO 2 used in the decomposition of hydrogen peroxide 2 H2 O2 (l) ---à 2 H2O(l) + O2 (g) The above reaction occurs very slowly at room temperature. However, if small amount of manganese(IV) oxide is added, it proceeds quickly.