Lanthanide and Actinide Chemistry

1. Lanthanide and Actinide Chemistry Dr. P. S. BhaleAsst. ProfessorDepartment of ChemistryY. C.Mahavidyalaya, Tuljapur

2. Session Objectives • f-Block elements • Introduction to lanthanides • Oxidation state • lanthanide contraction • Chemical reactivity • Introduction of Actinides • Comparison of actinides with lanthanides

3. Inner transition elements The elements in which the additional electrons enters (n-2)f orbitals are called inner transition elements. The valence shell electronic configuration of these elements can be represented as (n – 2)f0-14(n – 1)d0-1ns2. 4f inner transition metals are known as lanthanides because they come immediately after lanthanum and 5f inner transition metals are known as actinoids because they come immediately after actinium.

4. Electronic Configuration Element name Symbol Z Ln Ln3+ Radius Ln3+/ pm Lanthanum La 57 [Xe]6s25d1 [Xe]4f0 116 Cerium Ce 58 [Xe]4f16s25d1 [Xe]4f1 114 Praesodymium Pr 59 [Xe]4f36s2 [Xe]4f2 113 Neodymium Nd 60 [Xe]4f46s2 [Xe]4f3 111 Promethium Pm 61 [Xe]4f56s2 [Xe]4f4 109 Samarium Sm 62 [Xe]4f66s2 [Xe]4f5 108 Europium Eu 63 [Xe]4f76s2 [Xe]4f6 107 Gadolinium Eu 64 [Xe]4f76s25d1 [Xe]4f7 105 Terbium Tb 65 [Xe] 4f96s2 [Xe]4f8 104 Dysprosium Dy 66 [Xe] 4f106s2 [Xe]4f9 103 Holmium Ho 67 [Xe] 4f116s2 [Xe]4f10 102 Erbium Er 68 [Xe] 4f126s2 [Xe]4f11 100 Thulium Tm 69 [Xe] 4f136s2 [Xe]4f12 99 Ytterbium Yb 70 [Xe] 4f146s2 [Xe]4f13 99 Lutetium Lu 71 [Xe] 4f146s25d1 [Xe]4f14 98

5. Atomic and ionic sizes: The Lanthanide Contraction As the atomic number increases, each succeeding element contains one more electron in the 4f orbital and one proton in the nucleus. The 4f electrons are ineffective in screening the outer electrons from the nucleus causing imperfect shielding. As a result, there is a gradual increase in the nucleus attraction for the outer electrons. Consequently gradual decrease in size occur.This is called lanthanide contraction.

6. Illustrative Example Explain the cause and two consequences of lanthanoid contraction. Solution: The poor shielding effect of f-electrons is cause of lanthanoid contraction. Consequences There is close resemblance between 4d and 5d transition series. Ionization energy of 5d transition series is higher than 3d and 4d transition series. Difficulty in separation of lanthanides

7. Illustrative Example Why Zr and Hf have almost similar atomic radii? Solution Zr and Hf have almost similar atomic radii as a consequence of lanthanide contraction due to which their properties becomes similar.

8. Illustrative Example Size of trivalent lanthanoid cation decreases with increase in atomic number. Explain. Solution It is due to poor shielding effect of f-electrons, valance electrons are strongly attracted towards nucleus, therefore, effective nuclear charge increases, hence ionic size decreases.

9. Ionization Enthalpies First ionization enthalpy is around 600 kJ mol-1, the second about 1200 kJ mol-1 comparable with those of calcium. Colours: Colours of these ions may be attributed to the presence of f electrons. Neither La3+ nor Lu3+ ion shows any colour but the rest do so. Absorption bands are narrow, probably because of the excitation within f level.

10. Magnetic properties The lanthanoid ions other then the f 0 type (La3+ and Ce3+) and the f14 type (Yb2+ and Lu3+) are all paramagnetic. The paramagnetism rises to the maximum in neodymium. Lanthanides have very high magnetic susceptibilities due to their large numbers of unpaired f-electrons. The strongest known magnets contain lanthanides (eg. Nd-Fe-B, Sm-Fe-N, and Sm-Co). Lanthanide complexes are used in MRI (medical resonance imaging), eg. [Gd(III)(dtpa)]2-

11. Oxidation States Predominantly +3 oxidation state. This irregularity arises mainly from the extra stability of empty, half filled or filled f subshell. Occasionally +2 and +4 ions in solution or in solid compounds are also obtained.

12. Illustrative Example Why Sm2+, Eu2+, and Yb2+ ions in solutions are good reducing agents but an aqueous solution of Ce4+ is a good oxidizing agent? Solution The most stable oxidation state of lanthanides is +3. Hence the ions in +2 oxidation state tend to change +3 state by loss of electron acting as reducing agents whereas those in +4 oxidation state tend to change to +3 oxidation state by gain of electron acting as a good oxidising agent in aqueous solution.

13. Luminescence of lanthanoid complexes Irradiation of some Lanthanide(III) complexes with UV light causes them to fluoresce The origin of fluorescence is 4f-4f transitions. –the excited state produced decays to the ground state with emission of energy. Some examples are Eu3+ (red) and Tb3+ (green) They can be used as phosphors in television sets and fluorescent lighting. These applications are specific to lanthanoid ions because of the sharp transitions observed.

14. Properties Silvery white soft metals, tarnish in air rapidly Hardness increases with increasing atomic number, samarium being steel hard. Good conductor of heat and electricity.

15. Chemical Properties Metal combines with hydrogen when gently heated in the gas. The carbides, Ln3C, Ln2C3 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 and hydroxides, M2O3 and M(OH)3, basic like alkaline earth metal oxides and hydroxides.

16. Uses Best single use of the lanthanoids is for the production of alloy steels for plates and pipes. A well known alloy is misch metal which consists of a lanthanoid metal (~95%) and iron (~5%) and traces of S, C, Ca and Al. A good deal of misch metal is used in Mg based alloy to produce bullets, shell and lighter flint. Mixed oxides of lanthanoids are employed as catalysts in petroleum cracking.

17. The Actinides Result from the filling of the 5f orbitals. All isotopes are radioactive, with only 232Th, 235U, 238U and 244Pu having long half-lives. Only Th and U occur naturally-both are more abundant in the earth’s crust than tin. The others must be made by nuclear processes.

18. Some characteristic properties of actinides The dominant oxidation state of actinides is +3. Actinides also exhibit an oxidation state of +4. Some actinides such as uranium, neptunium and plutonium also exhibit an oxidation state of +6. The actinides show actinide contraction (like lanthanide contraction) due to poor shielding of the nuclear charge by 5f electrons. All the actinides are radioactive. Actinides are radioactive in nature. So the study of their chemistry is difficult in the laboratory. Their chemistry is studied using tracer techniques.

19. Electronic configuration Element name Symbol Z Ln Ln3+ Radius Ln3+/ pm Actinium Ac 89 [Rn] 6d17s2 [Rn]4f0 111 Thorium Th 90 [Rn ]5d27s2 [Rn]4f1 Protactinium Pa 91 [Rn]5f26d17s2 [Rn]4f2 Uranium U 92 [Rn]5f36d17s2 [Rn]4f3 103 Neptunium Np 93 [Rn]5f46d17s2 [Rn]4f4 101 Plutonium Pu 94 [Rn]5f67s2 [Rn]4f5 100 Americium Am 95 [Rn]5f77s2 [Rn]4f6 99 Curium Cm 96 [Rn]5f76d17s2 [Rn]4f7 99 Berkelium Bk 97 [Rn]5f97s2 [Rn]4f8 98 Californium Cf 98 [Rn]5f107s2 [Rn]4f9 98 Einsteinium Es 99 [Rn]5f117s2 [Rn]4f10 Fermium Fm 100 [Rn]5f127s2 [Rn]4f11 Mendelevium Md 101 [Rn]5f137s2 [Rn]4f12 Nobelium No 102 [Rn]5f147s2 [Rn]4f13 Lawrencium Lr 103 [Rn]5f146d17s2 [Rn]4f14

20. Ionic sizes Actinide contraction of trivalent ions is similar to that of the lanthanides, and is caused again by the increasing nuclear charge. Magnetic properties Magnetic properties are more complex than those of lanthanoids. Susceptibility is roughly parallel to the lanthanoids.

21. Physical and chemical reactivity Silvery in appearance but display a variety of structures due to the irregularity in metallic radii which are far greater than are found in lanthanoids. Highly reactive metals, especially when finely divided. Action of boiling water gives mixture of oxides and hydroxides. Combination with most non-metals takes place at moderate temperature. HCl attacks all metals but most are slightly affected by HNO3 owing to the formation of protective oxide layers. Alkalies have no effect.

22. Comparison of Lanthanides and Actinides Similarities Lanthanides and actinides involve filling of f-orbitals and thus are similar in many respects. The most common oxidation state is +3 for both lanthanides and actinides. Both are electropositive in nature and thus very reactive. Magnetic and spectral properties are exhibited by both lanthanides and actinides. Actinides exhibit actinide contraction just like lanthanides.

23. Differences Besides +3, lanthanides also show oxidation states of +2 and +4 while actinides show higher oxidation states of +4, +5, +6 and + 7 as well. Lanthanide ions are colourless while most of the actinide ions are coloured. Actinides have a greater tendency towards complex formation as compared to lanthanides. Lanthanide compounds are less basic while actinide compounds have appreciable basicity Actinides form few important oxocations such as UO22+, PuO22+, etc, while such oxocations are not known for lanthanides. Almost all actinides are radioactive while lanthanides, except promethium, are non-radioactive. The magnetic properties of actinides can be easily explained while it is difficult to do so in the case of lanthanides.

24. Illustrative Example Why do lanthanoids and actinoids have same physical and chemical properties? Solution They have similar electronic configuration and f-orbital is progressively filled.

25. Thank you