4.11 Explain giving reasons: (i) Transition metals and many of their compounds show paramagnetic behaviour. (ii) The enthalpies of atomisation of the transition metals are high. (iii) The transition metals generally form coloured compounds. (iv) Transition metals and their many compounds act as good catalyst.

4.2 Ionic or Electrovalent Bond other factors. The crystal structure of sodium chloride, NaCl (rock salt), for example isFrom the Kössel and Lewis treatment of the shown below.formation of an ionic bond, it follows that the formation of ionic compounds would primarily depend upon: • The ease of formation of the positive and negative ions from the respective neutral atoms; • The arrangement of the positive and negative ions in the solid, that is, the lattice of the crystalline compound. The formation of a positive ion involves ionization, i.e., removal of electron(s) from the neutral atom and that of the negative ion involves the addition of electron(s) to the Rock salt structure neutral atom. In ionic solids, the sum of the electron gain M(g) → M+(g) + e– ; enthalpy and the ionization enthalpy may be Ionization enthalpy positive but still the crystal structure gets X(g) + e– → X – (g) ; stabilized due to the energy released in the Electron gain enthalpy formation of the crystal lattice. For example: the ionization enthalpy for Na+(g) formation M+(g) + X –(g) → MX(s) from Na(g) is 495.8 kJ mol–1 ; while the electron The electron gain enthalpy, ∆egH, is the gain enthalpy for the change Cl(g) + e–→ enthalpy change (Unit 3), when a gas phase Cl– (g) is, – 348.7 kJ mol–1 only. The sum of the atom in its ground state gains an electron. two, 147.1 kJ mol-1 is more than compensated The electron gain process may be exothermic for by the enthalpy of lattice formation of or endothermic. The ionization, on the other NaCl(s) (–788 kJ mol–1). Therefore, the energy hand, is always endothermic. Electron released in the processes is more than the Reprint 2025-26 Chemical Bonding And Molecular Structure 107 energy absorbed. Thus a qualitative measure of the stability of an ionic compound is provided by its enthalpy of lattice formation and not simply by achieving octet of electrons around the ionic species in gaseous state. Since lattice enthalpy plays a key role in the formation of ionic compounds, it is important that we learn more about it. 4.2.1 Lattice Enthalpy The Lattice Enthalpy of an ionic solid is defined as the energy required to completely separate one mole of a solid ionic compound into gaseous constituent ions. For example, the lattice enthalpy of NaCl is 788 kJ mol–1. This means that 788 Fig. 4.1 The bond length in a covalent kJ of energy is required to separate one mole molecule AB. of solid NaCl into one mole of Na+ (g) and one R = rA + rB (R is the bond length and rA and rB are mole of Cl– (g) to an infinite distance. the covalent radii of atoms A and B respectively) This process involves both the attractive forces between ions of opposite charges in the same molecule. The van der Waals and the repulsive forces between ions of radius represents the overall size of the like charge. The solid crystal being three- atom which includes its valence shell in a dimensional; it is not possible to calculate nonbonded situation. Further, the van der lattice enthalpy directly from the interaction Waals radius is half of the distance between of forces of attraction and repulsion only. two similar atoms in separate molecules in Factors associated with the crystal geometry a solid. Covalent and van der Waals radii of have to be included. chlorine are depicted in Fig. 4.2.

3.3 MODERN PERIODIC LAW AND THE physical and chemical properties of elements PRESENT FORM OF THE PERIODIC and their compounds. TABLE Numerous forms of Periodic Table have We must bear in mind that when Mendeleev been devised from time to time. Some developed his Periodic Table, chemists forms emphasise chemical reactions and knew nothing about the internal structure valence, whereas others stress the electronic of atom. However, the beginning of the 20th configuration of elements. A modern version, century witnessed profound developments the so-called “long form” of the Periodic in theories about sub-atomic particles. In Table of the elements (Fig. 3.2), is the most 1913, the English physicist, Henry Moseley convenient and widely used. The horizontal observed regularities in the characteristic rows (which Mendeleev called series) are X-ray spectra of the elements. A plot of called periods and the vertical columns, (where is frequency of X-rays emitted) groups. Elements having similar outer against atomic number (Z) gave a straight electronic configurations in their atoms are arranged in vertical columns, referredline and not the plot of vs atomic mass. to as groups or families. According to theHe thereby showed that the atomic number recommendation of International Union ofis a more fundamental property of an element Pure and Applied Chemistry (IUPAC), thethan its atomic mass. Mendeleev’s Periodic groups are numbered from 1 to 18 replacingLaw was, therefore, accordingly modified. This the older notation of groups IA … VIIA, VIII,is known as the Modern Periodic Law and IB … VIIB and 0. can be stated as : There are altogether seven periods. The The physical and chemical properties period number corresponds to the highest of the elements are periodic functions principal quantum number (n) of the elements of their atomic numbers. in the period. The first period contains 2 The Periodic Law revealed important elements. The subsequent periods consists of analogies among the 94 naturally occurring 8, 8, 18, 18 and 32 elements, respectively. The elements (neptunium and plutonium like seventh period is incomplete and like the sixth actinium and protoactinium are also found period would have a theoretical maximum in pitch blende – an ore of uranium). It (on the basis of quantum numbers) of 32 stimulated renewed interest in Inorganic elements. In this form of the Periodic Table, Chemistry and has carried into the present 14 elements of both sixth and seventh periods with the creation of artificially produced (lanthanoids and actinoids, respectively) are short-lived elements. placed in separate panels at the bottom*. You may recall that the atomic number 3.4 NOMENCLATURE OF ELEMENTSis equal to the nuclear charge (i.e., number WITH ATOMIC NUMBERS > 100of protons) or the number of electrons in a neutral atom. It is then easy to visualize The naming of the new elements had been the significance of quantum numbers and traditionally the privilege of the discoverer electronic configurations in periodicity of (or discoverers) and the suggested name was elements. In fact, it is now recognized that the ratified by the IUPAC. In recent years this has Periodic Law is essentially the consequence led to some controversy. The new elements of the periodic variation in electronic with very high atomic numbers are so unstable configurations, which indeed determine the that only minute quantities, sometimes only * Glenn T. Seaborg’s work in the middle of the 20th century starting with the discovery of plutonium in 1940, followed by those of all the transuranium elements from 94 to 102 led to reconfiguration of the periodic table placing the actinoids below the lanthanoids. In 1951, Seaborg was awarded the Nobel Prize in chemistry for his work. Element 106 has been named Seaborgium (Sg) in his honour. Classification of Elements and Periodicity in Properties 79 0 B VII This B VI electronic B outer V B state IV recommendations. elements. B ground IUPACthe III and for B 0 1984 II theand numbers B I with IB–VIIB atomic VIII, → their accordance VIII withinIA–VIIA, ← of Elements1-18 A scheme the VII ofnumbered A are VI Table numbering A old groups V Periodic the A The the IV of A replaces III form Longconfigurations.notation IIA 3.2 IA Fig. 80 chemistry a few atoms of them are obtained. Their digits which make up the atomic number and synthesis and characterisation, therefore, “ium” is added at the end. The IUPAC names require highly sophisticated costly equipment for elements with Z above 100 are shown in and laboratory. Such work is carried out with Table 3.5. competitive spirit only in some laboratories in the world. Scientists, before collecting the Table 3.4 Notation for IUPAC reliable data on the new element, at times Nomenclature of Elements get tempted to claim for its discovery. For example, both American and Soviet scientists Digit Name Abbreviation claimed credit for discovering element 104. 0 nil n The Americans named it Rutherfordium 1 un u whereas Soviets named it Kurchatovium. To 2 bi b avoid such problems, the IUPAC has made 3 tri t recommendation that until a new element’s 4 quad q discovery is proved, and its name is officially 5 pent precognised, a systematic nomenclature be 6 hex hderived directly from the atomic number of 7 sept sthe element using the numerical roots for 8 oct o0 and numbers 1-9. These are shown in 9 enn eTable 3.4. The roots are put together in order of Table 3.5 Nomenclature of Elements with Atomic Number Above 100 Atomic Name according to IUPAC IUPAC Symbol Number IUPAC nomenclature Official Name Symbol 101 Unnilunium Unu Mendelevium Md 102 Unnilbium Unb Nobelium No 103 Unniltrium Unt Lawrencium Lr 104 Unnilquadium Unq Rutherfordium Rf 105 Unnilpentium Unp Dubnium Db 106 Unnilhexium Unh Seaborgium Sg 107 Unnilseptium Uns Bohrium Bh 108 Unniloctium Uno Hassium Hs 109 Unnilennium Une Meitnerium Mt 110 Ununnillium Uun Darmstadtium Ds 111 Unununnium Uuu Rontgenium Rg 112 Ununbium Uub Copernicium Cn 113 Ununtrium Uut Nihonium Nh 114 Ununquadium Uuq Flerovium Fl 115 Ununpentium Uup Moscovium Mc 116 Ununhexium Uuh Livermorium Lv 117 Ununseptium Uus Tennessine Ts 118 Ununoctium Uuo Oganesson Og Classification of Elements and Periodicity in Properties 81 Thus, the new element first gets a be readily seen that the number of elements temporary name, with symbol consisting in each period is twice the number of atomic of three letters. Later permanent name orbitals available in the energy level that is and symbol are given by a vote of IUPAC being filled. The first period (n = 1) starts with representatives from each country. The the filling of the lowest level (1s) and therefore permanent name might reflect the country has two elements — hydrogen (ls1) and helium (or state of the country) in which the element (ls2) when the first shell (K) is completed. The was discovered, or pay tribute to a notable second period (n = 2) starts with lithium and the scientist. As of now, elements with atomic third electron enters the 2s orbital. The next numbers up to 118 have been discovered. element, beryllium has four electrons and has Official names of all elements have been the electronic configuration 1s22s2. Starting announced by IUPAC. from the next element boron, the 2p orbitals are filled with electrons when the L shell is Problem 3.1 completed at neon (2s22p6). Thus there are 8 elements in the second period. The third What would be the IUPAC name and period (n = 3) begins at sodium, and the added symbol for the element with atomic number 120? electron enters a 3s orbital. Successive filling of 3s and 3p orbitals gives rise to the third Solution period of 8 elements from sodium to argon. The From Table 3.4, the roots for 1, 2 and 0 fourth period (n = 4) starts at potassium, and are un, bi and nil, respectively. Hence, the added electrons fill up the 4s orbital. Now the symbol and the name respectively you may note that before the 4p orbital is filled, are Ubn and unbinilium. filling up of 3d orbitals becomes energetically favourable and we come across the so called 3d