CBSE-12 D-BLOCK ELEMNTS MOHAMMED.

ILIAS(CHEMISTRY TEACHER)

The elements lying in the middle of periodic table belonging to groups 3 to 12 are known as d block elements. Their general electronic configuration is (n 1)d1-10 ns1-2 where (n 1) stands for penultimate (last but one) shell Four transition series: a. 3d transition series. The transition elements with atomic number 21(Sc) to 30(Zn) and having incomplete 3d orbitals is called the first transition series. b. 4d transition series. It consists of elements with atomic number 39(Y) to 48 (Cd) and having incomplete 4d orbitals. It is called second transition series c. 5d transition series. It consists of elements with atomic number 57(La), 72(Hf) to 80(Hg) having incomplete 5d orbitals. It is called third transition series. d. 6d transition series. It consists of elements with atomic number 89(Ac), 104(Rf) to 112(Uub) having incomplete 6d orbitals. It is called fourth transition series.

1. Define d-Block elements Ans: The elements in which the valence electrons are progressively filled in d orbitals each of the four long periods are called d-block elements 2. Define transition element Ans: A transition element is defined as the one which has incompletely filled d orbitals in its ground state or in any one of its oxidation states 3. What are the transition elements? Ans: The elements, which have the properties in between those of s-block and p-block elements, are called the transition elements. 4. Why are the transition elements called d-block elements? Ans: In transition elements, the last electron enters in the d-orbital.So they are called d block Elements 5. Zinc,cadmium and mercury are not regarded as transition metals. Why? Ans: Zinc, cadmium and mercury have full d10 configuration in their ground state as well as in their common oxidation states and hence, are not regarded as transition metals 6. Write general electronic configuration of d-block elements Ans: In general the electronic configuration of these elements is (n-1)d110 ns12. (The (n 1) stands for the inner d orbitals which may have one to ten electrons and the outermost ns orbital may have one or two electrons.)

7. Write general electronic configuration of transion elements Ans: In general the electronic configuration of these elements is (n-1)d19 ns12 8. On what ground can you say that scandium (Z = 21) is a transition element but zinc (Z = 30) is not? Ans: On the basis of incompletely filled 3d orbitals in case of scandium atom in its ground state (3d1), it is regarded as a transition element. On the other hand, zinc atom has completely filled d orbitals (3d10) in its ground state as well as in its oxidised state, hence it is not regarded as a transition element 9. Silver atom has completely filled d orbitals (4d10) in its ground state. How can yousay that it is a transition element? (imp) Ans: Silver (Z = 47) can exhibit +2 oxidation state wherein it will have incompletely filled d orbitals (4d), hence a transition element. 10. Give reason a) Cr (z=25) the configuration has 3d5 4s1 instead of 3d44s2; b) Cu(29) the configuration is 3d104s1 and not 3d94s2 The energy gap between the two sets (3d and 4s) of orbitals is small enough to prevent electron entering the 3d orbitals. Cr (z=25) acquires has extra stable half filled 3d5 4s1 the configuration Cu(29)acquires has extra stable half filled 3d10 4s1 the configuration 11. In what way is the electronic configuration of the transition elements different from that of the non-transition elements

Transition metals have a partially filled dorbital. Therefore, the electronic configuration of transition elements is (n 1)d1-10 ns0-2. The non-transition elements either do not have a dorbital or have a fully filled dorbital. Therefore, the electronic configuration of non-transition elements is ns1-2 or ns2 np1-6.

TOPIC : PHYSICAL PROPERTIES Metallic character: All transition elements are metallic in nature, i.e. they have strong metallic bonds. This is because of presence of unpaired electrons. This gives rise to properties like high density, high enthalpies of atomization, and high melting and boiling points. Atomic radii: The atomic radii decrease from Sc to Cr because the effective nuclear charge increases. The atomic size of Fe, Co, Ni is almost same because the attraction due to increase in nuclear charge is cancelled by the repulsion because of increase in shielding effect. Cu and Zn have bigger size because the shielding effect increases and electron electron repulsions repulsion increases. 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 effectivenuclear charge when the electron is added to the same d-subshell makes the electrons contract.

Lanthanoid Contraction: The steady decrease in the atomic and ionic radii of the transition metals as the atomic number increases. This is because of filling of 4f orbitals before the 5d orbitals. This contraction is size is quite regular. This is called lanthanoid contraction. It

is because of lanthanoid contraction that the atomic radii of the second row of transition elements are almost similar to those of the third row of transition elements. Ionisation enthalpy: Trend: The 1st ionization enthalpies increase gradually across the series. Across the series, electrons are added to the inner 3d subshell. The inner deelctrons 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. Some irregularities in the variation: The 1st ionization enthalpy of zinc is exceptional high because it has a full- filled 3d subshell. The 2nd ionization enthalpy of chromium is higher than manganese. It is because it has a half- filled 3d subshell which has extra stability. 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 There is slight and irregular variation in ionization energies of transition metals due to irregular variation of atomic size. The I.E. of 5d transition series is higher than 3d and 4d transition series because of Lanthanoid Contraction. 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 sblock 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.

Density

1. The transition metals (with the exception of Zn, Cd and Hg) are very much hard and have low volatility and brittle than s- block elements. Give reason Ans: Reason for their hardness : The hardness of these metals suggests the presence of strong bonding due to overlap of unpaired electrons between different metal atoms. 2. Why do the transition elements exhibit higher enthalpies of atomisation? Because of large number of unpaired electrons in their atoms they have stronger interatomic interaction and hence stronger metallic bonding between atoms resulting in higher enthalpies of atomization. 3. Why Cr, Mo, and W very hard metals and have greater enthalpy of atomization? Ans: Cr, Mo, and W have maximum no of unpaired electrons and, therefore these are very hard metals and have greater enthalpy of atomization. 4. Why Zn,Cd,Hg soft and has lower enthalpy of atomization.? (imp) Ans Zn,Cd,Hg soft and has lower enthalpy of atomization because weak inter atomic bond due to fully filled d-orbital 5. Melting and boiling points of transition metals are high. Ans: The high melting points of these metals are attributed to the involvement of greater

number of electrons from (n-1)d in addition to the ns electrons in the strong inter-atomic metallic bonding 6. In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomization of zinc is the lowest, i.e., 126 kJ mol1. Why? Ans: In this series all the elements have one or more unpaired electrons except zinc its outer electronic configuration is 3d104s2. So atomic intermetallic bonding in zinc is weakest so enthalpy of atomization is lowest 7. Why Mn and Tc (technetium) metals have abnormally low melting points Ans: because of poor packing pattern and extra stability of half and fulfilled d- orbitals 8. The atomic radii of the third (5d) series are virtually the same as those of the corresponding members of the second series (4d) give reason Ans Reason: due to Lanthanide contraction due to poor shielding effect by Intervening 4f electron and increased nuclear charge size decreases 9. How would you account for the irregular variation of ionization enthalpies (first and second) in the first series of the transition elements? Ans: Irregular variation of ionisation enthalpies is mainly attributed to varying degree of stability of different 3d-configurations (e.g., d0, d5, d10 are exceptionally stable 10. Why The first I.E of third transition series are higher than those of second transition series Reason: in the atoms of third transition series, there are filled 4f- orbitals. The 4forbitals have very poor shielding effect. As a result the effective nuclear charge on the outer valence electrons increases. Hence their I.E are higher (or ) due lanthanide contraction the effective nuclear charge on the outer valence electrons increases. Hence their I.E are higher 11. Transition elements have high density and it increases along the period Reason: as atomic radius decreases (due to increase in nuclear charge) and increase in atomic mass results in increases in density The general characteristics of transition elements 1) They have high melting and boiling points

2) They have high enthalpies of atomization.

3) They display a variable of oxidation states. 4) Most of them form coloured ions 5) They from alloys with other metals 6) They forms complex formation with a variety of ligands. 7) The transition metals and their compounds also exhibit catalytic property. 8) Their compounds are generally paramagnetic in nature.

9) 9) They from interstitial compounds with elements such as H, B, C, N, etc

Magnetic Properties.

Many of the transition metal ions are paramagnetic nature due to the presence of unpaired electrons.

The magnetic moment is determined by the number of unpaired electrons and is calculated by
using the spin-only formula, i.e., = n(n + 2) where n is the number of unpaired electrons and is the magnetic moment in units of Bohr magneton (BM).

The magnetic moment increases with the increasing number of unpaired electrons.
One unpaired electron-------- magnetic moment = 1.73 BM 1. Transition metal ions are paramagnetic in nature.Why? Ans: Many of thetransition metal ions are paramagnetic due to the presence of unpaired electrons. 2. Calculate the magnetic moment of a divalent ion in aqueous solution if its atomic number is 25. 3. Calculate the spin only magnetic moment of M2+(aq) ion (Z= 27).

. 4. Among the first transition metals which divalent metal ion has maximum paramagnetic character and why? Ans: Mn2+. because of maximum number of unpaired electrons Formation of Coloured Ions. Most of the transition metal ions are coloured due to d-d transition i.e transition of electron from lower d level(t2g) to higher d level(eg) Metal ion with incomplete d orbital (d1 d9) is coloured (having unpaired electron) Mn2+ is coloured .( electronic configuration is [Ar] 3d5). Zn2+ is colourless(electronic configuration is [Ar] 3d10) 1. Most of the transition metal ions are coloured.Why? Ans: Transitional metals due to their incompletely filled d orbitals posess no of unpaired electrons which on absorption of light particular weave length undergo d-d transition and thus exhibit colour (or )Presence of unpaired electron d-d transition i.e transition of electron from lower d level(t2g) to higher d level(eg) 2. Copper I compounds are white and diamagnetic but copper II compounds are coloured and paramagnetic. Why? Ans: In copper I ion all orbitals are completely filled so its compounds are white and diamagnetic. The electronic configuration of copper II ion is 1s22s22p63s23p63d9. it has one unpaired electron so it is paramagnetic and forms coloured compounds. 3. Why Ti(H2O)6]3+ ion shows The purple colour ? Ans: In[Ti(H2O)6]3+ electronic configuration of . The presence of one unpaired electron makes the ion coloured 4. What happens when Ti(H2O)6]3+ ion heated ? give reason for your observation ? Ans: Ti(H2O)6]3+ ion shows the purple colour, on heating looses water molecules in coordination sphere , this causes no splitting of d-orbital results in clours less. 5. Why Zn+2 shows white clour ?

5 Ans: Zn+2 ion does not have umpired electron therefore does not cause d-d transition 6. Ans Predict which of the following will be coloured in aqueous solution? Ti3+, V3+, Cu+, Sc3+, Mn2+, Fe3+ and Co2+. Give reasons for each. Only the ions that have un paired electrons in d-orbital will be coloured. The ions in which d-orbital is empty will be colourless.

From the above table, it can be easily observed that only Sc3+ has an empty d-orbital. All other ions, except Sc3+, will be coloured in aqueous solution because of dd Transitions Formation of Complex Compounds. 1. The transition metals form a large number of complex compounds.Why? The transition metals form a large number of complex compounds. This is due to The comparatively smaller sizes of the metal ions,

Their high ionic charges The availability of d orbitals for bond formation with ligands
A few examples are: [Fe(CN)6]3, [Fe(CN)6]4, [Cu(NH3)4]2+ and [PtCl4]2 Catalytic Properties.. 1 Transition metals and their many compounds act as good catalyst. Explain.

6
Ans It is due to the following reasons: -

1. Due to the presence of vacant d- orbitals.. 2. Due to the varying oxidation states some of transition elements form
intermediate compound with one of the reactants. 3. More surface area Vanadium(V) oxide (in Contact Process), finely divided iron (in Habers Process), and

nickel (in Catalytic Hydrogenation) are some of the examples. 2 Explain with an example The transition metal ions can change their oxidation states; they become more effective as catalysts. Ans For example, iron (III) catalyses the reaction between iodide and persulphate ions. 2 I + S2O8
22-

>I2 + 2 SO4

An explanation of this catalytic action can be given as: 2 Fe3+ + 2 I ----------------> 2 Fe2+ + S2O8
2- ---------2-

2 Fe2+ + I2

> 2 Fe3+ + 2SO4

3 Vanadium pentaoxide acts as a good catalyst. Why? Ans Vanadium shows different-different oxidation states because it has vacant d-orbitals,so vanadium pentaoxide acts as a good catalyst Formation of Interstitial Compounds 1. Ans What are interstitial compounds? Why are such compounds well known for transition metals? Transition metals are large in size and contain lots of interstitial sites. Transition elements can trap atoms of other elements (that have small atomic size), such as H, C, N, in the interstitial sites of their crystal lattices. The resulting compounds are called interstitial compounds example, TiC, Mn4N, Fe3H, VH0.56 and TiH1.7, etc 2 What are the properties of Interstitial compounds ? Ans : The principal physical and chemical characteristics of these compounds are as follows: (i) They have high melting points, higher than those of pure metals. (ii) They are very hard, some borides approach diamond in hardness. (iii) They retain metallic conductivity. (iv) They are chemically inert. Alloy Formation 1 Transition metals form alloys. Why? Ans :Transition metals form alloys because of similar radii and other characteristics of transition metals. * The alloys so formed are hard and have often high melting points. *Eg brass (copper-zinc), bronze (copper-tin), chromium, vanadium, tungsten, molybdenum and manganese are used for the production of a variety of steels and stainless steel

OXIDATION STATES