rhe d-block of the periodic table contains the elements of the groups 3-12 in which the d orbitale are progressively filled in each of the four long periods. The f-block consists of elements in which 4 f and 5 f orbitals are progressively filled. They are placed in @ separate panel at the bottom of the periodic table. The names transition metals and inner transition metals are often used to. refer to the elements of d-and -blocks respectively. There are mainly four series of the transition metals, 3d series (Sc to Zn), 4d series (Y to Cd), Sd series (La and Hf to Hg) and 6d series which has Ac and elements from Rf to Cn. The two series of the inner transition metals; 4f (Ce to Lu) and 5f (Th to Lr) are known as lanthanoids and actinoids respectively. ly the name transition metals was derived from the fact that their chemical properties were rransitional between those of s and p-block elements. Now according to IUPAC, transition metals are defined 1s metals which have incomplete d subshell either in neutral atom or in their tone. Zinc, cadmium and y of group 12 have full d’’ configuration in their as well as in their common oxidation states series, respectively, their the chemistry of the transition metals, ‘ese ¢ of partly filled d or f orbitals in their nsition elements different from that ofeae eaten formula (n-Ijd’ns*. The orbitals in their common oxidatio: "iia Sats ded a Miia they are not regarded as The d orbitals of the transition elements protrude to the periphery of va than the other orbitals (Le., s and p), hence, they are more nluenced by the surroundings a wel as alec he some or mole ions and entering into complex formation with a variety of ligands. The transition metals and their compounds also exhibit catalytic Sema a8 soramagnctic bebrviowy Ait Case cheesesssstet > been in detail later in this Unit. ‘There are greater similarities in the properties of the transition of a horizontal row in contrast to the non-transition elements. , some group similarities also exist. We shall first study the ‘characteristics and their trends in the horizontal rows 3d row) and then consider some group similarities. tint anandinum (Z = 21) is a transitionIntext Question Siives 1 8.1 r atom has completely filled d orbitals (449) in its groung . How can you say thet it is a transition element? late ~ We will discuss the properties of elements of first transition ee only in the following sections. Teg 85 General 8.3.1 Physical Properties of Nearly all the transition elements display typical metalic Properties ere teg the Transition such as high tensile strength, ductility. malleability, high tn he Elements electrical conductivity and metallic lustre. With the exceptions “and a we one or more c struc 7 |. Hg and Mn, they hat typical metallic st; are —_@-Block) normal temperatures, Lattice Structures of Transition Metals X bee (bee, cep) (hep) (hep) = centred cubic; hcp = ral © paci eases x ipa ‘The transition metals (with the exception of Zn, Cd and Hg) are very hard and have low volatility. Their melting and boiling points are high. Fig. 8.1 depicts the melting points of transition metals belonging to 3d, 4d and 5d series. 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 interatomic metallic bonding. In any row the melting points of these metals rise to a maximum at except for anomalous values of Mn and Tc and {all regularly as the atomic number increases. ‘They have high enthalpies of atomisation which are shown in Fig. 8.2. The maxima at about the middle of each series indicate that one unpaired electron ner 4 arhital ic nortionlarivof the lanthanotd contraction fs that the second and the tna" exhibit similar radi (e.g., 2 160 pr, ME 159 pen) and have yey! Physical and chemical properties much more than that expecgt tlle the basis of usual family relationship, tet og, 19 The fuctor responsible for the any eg increase in atomic size with Increasing atomtc number. 1, ie Contraction Je somewhat similar to thay in an ordinary transition series and ig aj," 17 to atenilar cause 1... the imperfect shied 16 gone electron by another in the same set of 8 of However, the shielding of one 4/ ej.) "als another is less than that of one d elec,” 14 another, and as the nuclear charge jn..." 13 along the series, there is fairly regular yo." gin the size of the entire 4f° orbitals, — F ‘The decrease in metallic radius coupieg Increase in atomic mass results ing go." increase in the density of these elements jy" from titantum (2 = 22) to copper (z = 30) \* significant increase in the density may be no:.', (Table 8.2). Configurations and some other Properties of the First Series of Transition Elements 21 22 ao eeos 5 27 _——) Sia? sass? sd'ad ad's! 3d°4s* 3d°4s' Sd'ts' 34s 34°46! 33 Sd'4s' 3d'4s' 3d'4s! 3d° 3d'4s' 3°48! Sd'4s' Sd4s' 3 stad aed! dk > ue wi ad aad of atomisation, 41° /kJ mol* (326 473° «(515 397) 281 416 425 430 339 enthalpy /4,Hf°/k3 mot" 631 656 ~~ 650 1235 13091414 2393 2657 2833 164 147-135 Z 79 ger oe r 1 m M ou ue ene 717 762 «758 736 745 905 -1.63 Sig sesgea- :PeAeNEVEL CLOMECr [) Py ED ee ee es harge which Oia left to right due ‘to an increaae in nuclear 1.2 gives the values then the filling of the inner d orbitals. Table eries of transition ele he first three lonisation enthalpies of the first mthalpies of these eee These values show that the successive aon-tran sitio; e ‘ements do not increase as steeply as in the case 4 cments. The variation in jonisation enthalpy along . transition elements. The first ionisation enthalpy. in general, increases, but the magnitude of the increase in the second and third ionisation enthal aigher along a series, alpies for.the successive elements. is much The irregular trend in the first ionisation enthalpy of the metals of E care sug of little chemical significance, conte accounted for een ae ‘at the removal of one electron alters the relative energies orbitals. You have learnt that when d-block elements form ions, ns electrons are lost before (n- 1) d electrons. As we move along the ‘period in 3d series, we see that nuclear charge increases from scandium to zinc but electrons are added to the orbital of inner subshell, ie., 3d orbitals. These 3d electrons shield the 4s electrons from the increasing nuclear charge somewhat more effectively than the outer shell electrons can shield one another. Therefore, the atomic radii decrease less rapidly. Thus, ionization energies increase only slightly along the 3d series. The doubly or more highly charged ions have & configurations with no 4s electrons. A general trend of increasing values of second ionisation enthalpy is expected as the effective nuclear charge increases because one d electron does not shield another electron from the influence of nuclear charge because d-orbitals differ in direction. However, the trend of steady increase in second and third ionisation enthalpy breaks for the formation of Mn” and Fe* respectively. In both the cases, ions have d° configuration. Similar breaks occur at corresponding elements in the later transition series, The interpretation of variation in ionisation enthalpy for an electronic ation d" is as follows: ‘The three terms responsible for the value of ionisation enthalpy are of each electron towards nucleus, repulsion between the Me The d- and f Block Elements