SONCEPT SE i) ding Elements: The d-block elements are those elements in which the last electron enters the d-subshell * of penultimate shell. The general electronic configuration of these elements is (n 1) d'"° ns!™?, where n is outermost shell. The d-block consisting of groups 3-12 occupies the large middle section of the periodic table. 2, Transition Elements: The elements of d-block are known as transition elements as they possess properties thatare transitional between the s and p block elements. A transition element is defined as an element which tas incompletely filled d-orbitals in its ground state or any one of its oxidation states. There are four series of transition elements spread between group 3 and 12, First transition series or 3d-series: _ Scandium (,,Sc) to Zinc (j¢Zn) ‘oSecond transition series or 4d-series: Yttrium (;9Y) to Cadmium (4gCd) rd transition series or Sd-series: Lanthanum (5;La) and Hafnium ,,Hf to Mercury (gH) (Omitting sgCe to 7,Lu) “ourth transition series or 6d-series: Begins with Actinium (spAc) is still incomplete. Zinc, cadmium and mercury of group 12 have full d' configuration in their ground state as well as in their common oxidation states and hence, are not regarded as transition metals. However, being the end elements ‘ofthe three transition series, their chemistry is studied along with the chemistry of the transition elements, 2 pes Characteristics of Transition Elements (a) Atomic radii: The atomic radii of transition elements are smaller than those of s-block elements oo"and larger than those of p-block elements in a period. In a transition series, as the atomic number xebPjncreases, the atomic radii first decreases till the middle, becomes almost constant and then increases towards the end of the period. The decrease in atomic radii in the beginning is due to the increase in the effective nuclear charge with the increase in atomic number. However, with the increase in the ‘number of electrons in (n ~ 1) d-subshell, the screening effect of these d-electrons on the outermost ‘ns-electrons also increases. This increased screening effect counterbalances the effect of increased nuclear charge, therefore, the atomic radii remain almost constant in the middle of the series. Increase 39 atomic radii towards the end may be attributed to the electron-electron repulsion. The pairing of electrons in the d-orbitals of the penultimate shell occurs only after the d-subshell is half filled. The pulsive interactions between the paired electrons in d-orbitals (of the penultimate shell) become Yery dominant towards the end of the series and causes the expansion of the electron cloud and thus, esulting in increased atomic size. The atomic radii usually increase down the group. But the atomic radii of the elements of second and third transition series belonging to a particular group are almost equal. This is due to lanthanoid Sontraction, UF 0 nic radii: The ionic radii of the transitional elements follow the same order as their atomic radii, In wee the ionic radii decrease with increase in oxidation state. : ‘cnisation enthalpies: The first ionisation enthalpies of transition elements are higher than those“of S-block elements but lower than, p-block elements, In a particular transition series, ionisation enthalpy iereases gradually with increase in atomic number, though some irregularities are observed.ae ease in ionisation enthalpy is due to increase In nuciear charge with increage 5” atomic number which tends to attract the electron cloud with greater force. / ‘The addition of d-clectron in penultimate shell with increase in atomic number provides a effect and shield the outer s-electrons from inward nuclear pull. Thus, the effect of increased n ; charge and increased magnitude of screening effect tend to oppose each other. Consequently, increase in ionisation enthalpy along the series of transition element is very small. The irregul Variations of first and second ionisation enthalpies in the first transition series is mainly due to varying degree of stability of different 3d-configuration. For example, Cr has low first ionisation enth because loss of one electron gives stable 3d° configuration and Zn has very high first ioni enthalpy because the electron has to be removed from 4s-orbital ofthe stable 3d!°4s? configurat ‘The first ionisation enthalpies of Sd-transition elements are higher than those of 3d and 4d elem This is due to greater effective nuclear char; rge acting on the outer valence electrons in these element besause of the ineffective shielding of the nucleus by 4f-electrons, _ PA ati character: All the transition elements are metallic in nature, ‘They show gradual decrea clectropositive character in moving from left to right ina series. The metallic bond in transition meta ae Nery strong, This is due to greater effective nuclear charge, low ionisation energies and large umber of vacant orbitals in their outermost shell. Nearly, all the transition metals are hard, p high-density and high enthalpy of atomisation. This is due to Presence of strong metallic bonds, _ preg and boiling points: Except zinc, cadmium and mercury all the other transition elem generally have high melting and boiling poi partially filled d-orbitals in them. Because of some covalent bonds also ex between atoms of transition elements. As mercury and cadmium have fully filled do therefore, there is no covalent bonding amongst the atoms of these elements. This accounts low melting and boiling points, zine, ion elements in low nt, e, er states +2 and 4: in nature, higher oxidation stat 3 are mostly ionic and of hea and CaCl, are ionie whereas Cr,07 and MnO; are’ s en 8 shown in oxides and y "eher oxidation state due to higher elect n, aus metals also exhibit +1 And 0 oxidation states. For! NEG BMH (0S of metal ig oy i Ms Fe(CO), (OS of metal is 0) When the metal exhibit more than one OS, thei, relative stabitt tom tl electrode potential, abilities can be known trom nature of fluorine and oxyger Cu*(ag) + 2c” —+ Cus) Cur(ag) + & —+ Cu(s) é standard reduction potential indicates Cy2* Standard electrode potential: Electrode potential ig the electrode when itis in equilibrium with a solution of ‘There is irregular variation in electrode Potential due sublimation energy and energy of hydration. ‘The E> vy is d= 0.52 volt More stable th han Cut in aqueous electric potential develope Wi ions, taking electrons from © irregular variation in ionisn ‘alue decreases from lelt to rigseries; Mn, Niand Za have higher values than expected because oftheir half-filled or completely filled 3d.otitals in case of Mn” and Zn respectively and the highest negative enthalpy of hydration, Ni?*, WwAMagnetic properties: Substances containing unpaired electrons are said to be paramagnetic. A diamagnetic substance is one in which all the electrons are paired. Except the ions of (Sc™, Ti**) and @'° (Cu’, Zn™) configurations, all other simple ions of transition elements contain unpaired electrons in their (n ~ 1) d subshell and are, therefore, paramagnetic. The magnetic moments (i) of she elements of fist transition series ean be calculated with the unpaired electrons (n)by the spin only formula. . fn(a+2) BM (Bohr Magneton) fomplex formation: The tendency to form complex ions is due to (@ the high charge on the transition metal ions, i) the availability of d-orbitals for accommodating electrons donated by the ligand atoms, @ Gatéiytic property: Most of the transition metals and their compounds possess catalytic properties. ‘The catalytic activity of transition metal ions is attributed to the following two reasons: ~_, ( Variable oxidation states due to which they can form a variety of unstable intermediate products, (ii) Large surface area so that the reactants are adsorbed on the surface and come close to each other facilitating the reaction process par: Most of the transition metal ions in solution as well as in solid states are coloured. This is due {o the partial absorption of visible light. The absorbed light promotes the electron from one orbital to another orbital of the same d-subshell. Since the electronic transition occurs within the d-orbitals of the transition metal ions, they are called d-d transitions. It is because of these dd transitions occurring ina transition metal ion by absorption of visible light that they appear coloured. © Sty formation: The transition metals have similar radii and other characteristics. Therefore, these cant ‘can mutually substitute their position in their crystal lattices and form alloys. The alloys so formed are hard and often have high melting point. Various types of steel, brass, bronze are examples of this type of alloy. ~ (m) Jaterstitial compounds: Interstitial compounds are those in which small atoms occupy the interstitial re in the crystal lattice. Interstitial compounds are well known for transition metals because small- sized atoms of H, B, CN, etc., can easily occupy p of transition metals. 4. Some Important Compounds of Transition Elements: ‘Though the transition elements are sufficiently electropositive, yet they are not very reactive because of ‘ (® their high enthalpies of sublimation, and (@) their high ionisation enthalpies. Oxides: Transition metals form oxides of the general composition MO, M;0,, MO, M,O, and MO,, Oxides in the lower oxidation states are generally basic in nature and those in the higher oxidation states ‘are amphoteric or acidic in nature. For example, ions in the voids present in the crystal lattices 2 +3, +83 4 47 MnO Mn,0; MnOs MnO; Mn,0, Basie “Amphoterie Arophoterie Amphoteric Acie (@) Potassium Dichromate, K,Cr,0;; Itis prepared from the chromite ore, Different reactions involved in the preparation of potassium dichromate from chromite ore are: AFeCr,04 + 8NazCO +70, —W+ BNuyCrO, + 2Fe,0) + 8CO., Chromite ore 2Na,CrO, + HySO, —+ Na,Cr,0, + NaySO, + H,0 . NayCrg0, + 2KCL_ ——+ K,Cr0, + 2NaCl / K,Cr,0, is separated by fractional crystallisation, Properties: When potassium dichromate is heated with any ionic chloride and concentrated HySO,, red vapours of chromyl chloride are obtained, NaCl, BaCly, ete.)