= f-block elements (JEE-Mains only) Differentiating electrons enters in (n — 2)f subshell. f-block elements lie on the Bottom portion of periodic table. [Link]. Properties — DISCRIPTION General _| Allthe block elements are heavy metals. « 1. faractar’s. | it shows high melting and boiling point. ‘The most common oxidation state of these elements is +3. No. of 2 elements | Total number of f-block elements ~ (28) IIIB/3rd group is called longest group having 32 elements including 14 Lanthanides and 14 Actinides. mI B/ 3rd sf Groups Sc Y la Lanthanides (14) Cese — Lurs ‘Ac Actinides (14) Theo — Lrios A Ee Lanthanide series 4f'- 4 5901 32 ws Actinide series 5f'~ "4 6d°o' 7s? Period | Il B/ 3rd Sc 5. Period Y 6" period La Lanthanides (14) Cess — Lur: 7® period ‘Ac ‘Actinides (14) Theo — Lrios6. The elements in which all the three shells that is ultimate (n) penultimate (n— 1) and pre or antipenultimate (n — 2) shell are incomplete are called inner transition [Link] = [Xe] 682, 5d', 4f" Inner transition elements are divided into two series. Cess — Lu7; 14 elements re ae de _| Lanthanides are found rarely on earth so these are called rare earth metals. aerlce ore The first element ofthis series is Cerium and not Lanthanum. Rareearth | in these elements, last electron enters into 4f subshell. They are present in IIIB group and 6" period of the periodic table. elements oF | Bromethium (c;Pm) is the only lanthanide which is synthetic and radioactive in Lanthenones nature. Theo — Lr,,14 elements. All the actinides are radioactive elements. The first element of this series is Thorium and not Actinium. In these elements, last electron enters into 5f subshell. (ii) Actinide | They are present in IIIB group and 7°” period of the periodic table. series or | All the actinides are radioactive in nature. Man made | First three elements (Th, Pa, U) are found in nature while others are synthetic elements or | in nature. Actinones | Transuranic actinides are man-made elements (Npss — Lwics) After Use i.e. from Npss onwards elements are called transuranic elements because (i) They are heavier than uranium. (ii) They are derived from uranium by nuclear reactions.The Lanthanides : The names, symbols, electronic configurations of atomic and some ionic states and atomic and ionic radil of lanthanum and lanthanide (for which the general symbol Ln is used) are given in Table. Electronic Configurations : It may be noted that atoms of these elements have electronic configuration with 6s? common but with variable occupancy of 4f level (Table). However, the electronic configurations of all the tripositive ions (the most stable oxidation state of all the lanthanides) are of the form 4 (n = 4 to 14 with increasing atomic number). 11-1 ‘Atomic and lonic Sizes : The overall decrease in atomic and ionic radii from lanthanum to lutetium (the lanthanide contraction). The shielding of one 4 f electron by another is less than one d electron by another with the increase in nuclear charge along the series. There is fairly regular decrease in the sizes with inoreasing atomic number. The cumulative effect of the contraction of the lanthanide series, known as 109} lanthanide contraction, causes the radii of the ‘members of the third transition series to be very similar to those of the corresponding members of the second series. The almost identical radi of Zr (160 prq) and Hf (159 pm), a consequence of the lanthanide contraction. Oxidation States : In the lanthanides, La(lll) and = 90 ~ Ln(l) compounds are predominant species. However, occasionally +2 and +4 ions in solution or in solid compounds are also obtained. This. imegularity (as. in ionisation enthalpies) arises ‘mainly from the extra stablity of empty, halt-filed or filled f subshell. Thus, the formation of Ce" is favoured by its noble gas configuration, but itis a strong oxidant reverting to the common +3 state. The E® value for Atomic number —e Cet) Ce is + 1.74 V which suggests that it can oxidise water. However, the reaction rate is very slow and hence Ce(IV) is a good analytical reagent. Pr, Nd, Tb and Dy also exhibit +4 state but only in oxides, MOz. Eu is formed by losing the two s electrons and its 1” configuration accounts for the formation of this ion However, Eu is a strong reducing agent changing to the common +3 state. Similarly Yb* which has f 414 configuration is a reductant. Tb" has haif-filed f-orbitals and is an oxidant. The behaviour of samarium is very much like europium, ‘exhibiting both +2 and +3 oxidation states. or 63 65 G7 Go 71Table :- Electronic Configurations and Radii of Lanthanum and Lanthanides: Radii/pm Number Neu symbol in La te in ‘$7, Lanthanum La__| Sd'6s? 187_|_ 106 58 | Cerium Ce | afteaiés® | ar af a 1a3__| 103 59 Praseodymium Pr 46s? 4p 4e 4fi 182 101 60 | Neodymium Nd | 46s? | af ae 4P 181 99 61__| Promethium Pm___|46s?__| 46 ae 181_| 98 62___| Samarium ‘Sm___| 46s? af a6 180_| 96 63__| Europium Eu | 4rer__| af” ae 199__| 95 64 | Gadolinium Gd | afea'Gs? | aed | af" 180 | 94 65 | Terbium To | 4P6s?__| a? af a 178| 92 66 | Dysprosium Dy | ates? [arto ae 4 17 | 91 67 Holmium Ho 4M 6s? af ane 176 89 68__| Erbium er 46s? | af? af 175 | 88 69 Thulium Tm 4f"6s? af 4f? 174 87 70 Ytterbium Yb 416s? aft ars 173 86 71__| Lutetium Lu [arses | areat_ | at f= : .General Characteristic: All the lanthanides are silvery white soft metals and tarnish rapidly in air. The hardness increases with increasing atomic number, samarium being steel hard. Their melting points range between 1000 to 1200 K but samarium melts at 1623 K. They have typical metallic structure and are good conductors of heat and electricity. Density and other properties change smoothly except for Eu and Yb and occasionally for Sm and Tm. Many trivalent lanthanide ions are coloured both in the solid state and in aqueous solutions. Colour of these ions may be attributed to the presence of f electrons. Neither La** nor Lu** ion shows any colour but the rest do so. However, absorption bands are narrow, probably because of the excitation within f level. The lanthanide ions other than the f° type (La and Ce**) and the f¥ type (Yb% and Lu**) are all paramagnetic. The paramagnetism rises to maximum in neodymium.The first ionisation enthalpies of the lanthanides are around 600 kJ molt, the second about 1200 kJ mol-' comparable with those of calcium. A detailed discussion of the variation of the third ionisation enthalpies indicates that the exchange _ enthalpy consideration (as in 3d orbitals of the first transition series), appear to impart a certain degree of stability to empty, half- filled and completely filled orbitals f level. This is indicated from the abnormally low value of the third ionization enthalpy of lanthanum, gadolinium and lutetium. Pax. ‘e In their chemical behaviour, in general, the earlier members of the series are quite reactive similar to calcium but, with increasing atomic number, they behave more like aluminium.Values for E- for the half-reaction: Ln®* (aq) + 3e + Ln(s) are in the range of -2.2 to -2.4 V except for Eu for which the value is — 2.0 V. This is, of course, a small variation. The metals combine with hydrogen when gently heated in the gas. The carbides, LnaC, LnaCs and LnC2 are formed when the metals are heated with carbon. They liberate hydrogen from dilute acids and burn in halogens to form halides. They form oxides M2Os and hydroxides M (OH)s. The hydroxides are definite compounds, not just hydrated oxides. They are basic like alkaline earth metal oxides and hydroxides. The best single use of the lanthanides is for the production of alloy steels for plates and pipes. A well known alloy is mischmetall which consists of a lanthanide metal (~ 95%) and iron (~ 5%) and traces of S, C, Ca and Al. A good deal of mischmetall is used in Mg-based alloy to produce bullets, shell and lighter flint. Mixed oxides of lanthanides are employed as catalysts in petroleum cracking. Some individual Ln oxides are used as phosphors in television screens and similar fluorescing surfaces. The Actinides : The actinides include the fourteen elements from Th to Lr. The names, symbols and some properties of these elements are given in Table.Table : Electronic Configurations and Radii of Actinium and Actinoids ‘Atomic Name abel Electronic configurations* Radii/pm Number M Me M* Ms Ma 89 Actinium Ac 6d'7s? Sf 111 90 Thorium Th 6d?7s? 5ft Sf 99 91 Proctactiniium Pa Sf6d"7s? Sf of 96 92 Uranium U 5P6d'7s? 5f of? 103 93 93 Neptunium Np 5f6d'7s? 5f Se 101 92 94 Plutonium Pu 5f°7s? 5f Sf 100 90 95 Americium Am Sf!7s? Sf Sf 99 89 96 Curium Cm 5f6d'7s? 5f? Sf” 99 88 o7 Berkelium Bk 5fP7s* Sf Sf” 98 87 98 Californium Cf 5f°7s? 5f? 5f 98 86 99 Einstenium Es 5f''7s2 of'? Sf? * 4 100 Fermium Fm 5f27s? Sf"? fe - * 101 Mendelevium Md. SFS7s? Sf2 Sf? S - 102 Nobelium No Size? 5fs Sft2 : : 103 Lawrencium ur Sf™6s'7s? fis SF's sf =The actinides are radioactive elements and the earlier members have relatively long half-lives, the latter ones have halt-life values ranging from a day to 3 minutes for lawrencium (Z =103). The latter members could be prepared only in nanogram quantities. These facts render their study more difficult. Electronic Configurations : All the actinides are believed to have the electronic configuration of 7s? and variable occupancy of the 5f and 6d subshells. The fourteen electrons are formally added to 5f, though not in thorium (Z = 90) but from Pa onwards the 5f orbitals are complete at element 103. The irregularities in the electronic configurations of the actinides, like those in the lanthanides are related to the stabilities of the f°, f” and f"* occupancies of the 5f orbitals. Thus, the configurations of Am and Cm are [Rn] 5f’7s? and [Rn] 517 6d‘ 7s. lonic Sizes : The general trend in lanthanides is observable in the actinides as well. There is a gradual decrease in the size of atoms or M°* ions across the series. This may be referred to as the actinide contraction (like lanthanide contraction). The contraction is, however, greater from element to element in this series resulting from poor shielding by 5f electrons.we )xidation States : There is a greater range of oxidation states, which is in part attributed to the fact that the 5f, 6d and 7s levels are of comparable energies. The known oxidation states of actinides are listed in Table. Table : Oxidation States of Actinium and Actinides Np | Pu | Am | Cm | Bk | Cf | Es | Fm | Md | No | Lr 3 3 3 3 3 3 3 [3 4 4 Ac | Th | Pa 4 a] | 0) ala} a} ol 3 4 5 6 ~) aa] a] | ~) oa] a] 0)The actinides show in general +3 oxidation state. The elements, in the first half of the series frequently exhibit higher oxidation states. For example, the maximum oxidation state increases from +4 in Th to +5, +6 and +7 respectively in Pa, U and Np but decreases in succeeding elements. The actinides resemble the lanthanides in having more compounds in +3 state than in the +4 state. However, +3 and +4 ions tend to hydrolyse. Because the distribution of oxidation states among the actinides is so uneven and so different for the earlier and latter elements, it is unsatisfactory to review their chemistry in terms of oxidation states.General Characteristics and Comparison with Lanthanides : The actinide metals are all silvery in appearance but display a variety of structures. The structural variability is obtained due to irregularities in metallic radii which are far greater than in lanthanides. The actinides are highly reactive metals, especially when finely divided. The action of boiling water on them, for example, gives a mixture of oxide and hydride and combination with most non metals takes place at moderate temperatures. Hydrochloric acid attacks all metals but most are slightly affected by nitric acid owing to the formation of protective oxide layers; alkalies have no action. The magnetic properties of the actinides are more complex than those of the lanthanides. Although the variation in the magnetic susceptibility of the actinides with the number of unpaired 5 f electrons is roughly parallel to the corresponding results for the lanthanides, the latter have higher values. It is evident from the behaviour of the actinides that the ionisation enthalpies of the early actinides, though not accurately known, but are lower than for the early lanthanides. This is quite reasonable since it is to be expected that when 5f orbitals are beginning to be occupied, they will penetrate less into the inner core of electrons. The 5f electrons, will therefore, be more effectively shielded from the nuclear charge than the 4f electrons of the corresponding lanthanides. Because the outer electrons are less firmly held, they are available for bonding in the actinides. *A comparison of the actinides with the lanthanides, with respect to different characteristics as discussed above, reveals that behaviour similar to that of the lanthanides is not evident until the second half of the actinide series. However, even the early actinides resemble the lanthanides in showing close similarities with each other and in gradual variation in properties which do not entail change in oxidation state. The lanthanide and actinide contractions, have extended effects on the sizes, and therefore, the properties of the elements succeeding them in their respective periods. The lanthanide contraction is more important because the chemistry of elements succeeding the actinides are much less known at the present time. Some Applications of d- and f-Block Elements : Iron and steels are the most important construction materials. Their production is based on the reduction of iron oxides, the removal of impurities and the addition of carbon and alloying metals such as Cr, Mn and Ni. TiO for the pigment industry and MnOz for use in dry battery cells. The battery industry also requires Zn and Ni/Cd. The ‘silver’ UK coins are a Cu/Ni alloy.