PERIODIC TABLE AN ATOMIC PROPERTIES — The eighteenth and nineteenth centuries witnessed rapid development of chemistry in all directions. During this period, several new elements were discovered. These elements were found to have numerous properties. It was realised that instead of studying the properties of all these elements individually, it would be more convenient to divide them into a few groups or families such that each group contains a number of elements with similar properties. The first important attempt to divide elements on the basis of their physical and chemical properties was made by Mendeleeff, a Russian chemist, who observed that when elements are arranged in the order of increasing atomic weights, elements with similar properties appear at regular intervals. In 1869, he enunciated a law, known as the periodic law, which states : The physical and chemical properties of elements are periodic functions of their atomic weights. Henry Moseley, a brilliant young British physicist, in 1912, discovered a new property of elements, called atomic number, which provided a better basis for the periodic arrangement of the elements. As is well known, atomic number of an element is equal to the number of protons present in the nucleus (or the number of electrons present outside the nucleus) of the atom of the element. The periodic law was, therefore, modified. The modern periodic law may thus be stated as : The properties of elements are periodic functions of their atomic numbers. Periodic Table. A table in which elements are arranged in the order of increasing atomic number in the manner that the clements with similar properties fall in the same vertical column is known as the periodic table. The elements which fall in the same column and resemble one another in their properties are said to belong to the same group or family of elements. Thus, elements belonging to one particular group or family resemble one another quite closely but differ from the elements belonging to the other groups quite appreciably. Various forms of periodic table have been put forth from time to time. The fundamental principle in each case, however, has been the same as enunciated in the modern periodic law. We shall consider only the modern form, known as the long form of the periodic table. LONG FORM PERIODIC TABLE ‘The objective of the periodic table is to organise and systematise the chemistry of the elements. The long form periodic table serves this objective very well. It may be recalled that the number of clements known at present is 118 including those prepared artificially through nuclear reactions in recent limes. A broad study of the characteristics of various groups gives us a fairly good insight into the Seneral behaviour and important properties of most of the elements. The long form periodic table also helps us to understand the reason why certain elements resemble ohe another and why they differ from other elements in their properties. The arrangement of elements in this table is also in keeping with their electronic configurations. © scanned with OKEN ScannerPRINCIPLES OF INORGANIC CHEM er 60 Y jodi ¢ at it helps us to understany Another significant feature of the long form periodic ube us aa ie meee cause of periodicity of properties and the reason why similar a Oe eae rene * te, after 2, 8, 8, 18, 18 and 32 elements. The numbers, 2, 8, i maggie numbers. : ee dof the book. This is constructed by array. rhe horizontal rows constitute periods while g! ‘The long form periodic table is given at the elements in the order of increasing atomic number. vertical rows constitute groups. : Periods. There are seven periods or horizontal rows in the table. The ee eon Up of only 2 elements, namely, hydrogen and the noble gas helium. The Properties of hydrogen meh Similar to those of alkali metals (Group 1) and also similar to those of the hal oe it sone respects. However, it is more reasonable, though not entirely logical, to place it in Group 1. Helium ig ‘ypical noble gas and belongs to Group 18, The second period contains 8 elements, It starts with lithium, an alkali metal of Group 1, The oiler elements placed in succeeding groups are : beryllium, boron, carbon, nitrogen, oxygen, fluor, and lastly, nean, a noble gas. Thus, this period also ends with a noble gas placed in Group 18, The third period which begins with sodium also contains 8 elements, These are : sodium Clemente minium silicon, phosphorus, sulphur, chlorine and the noble gas argon. The fitst sever elements are placed in Groups 1, 2, 13-17 while argon is placed in Group 18. This period, like the first ‘wo periods, also ends with a noble gas. ‘The fourth period begins, again, with an alkali metal, potassium, We have to pass now seventeen cer cfements before we come across a noble gas (krypton). This period. therefore, consicas hc shemnents from potassium (Z = 19) tothe noble as, krypion (Z = 36). The first wo elenente potassium and calcium, show recurrence of properties. Thus, potassium resembles lithium and cache of Group | itch it falls while calcium resembles eryllium and magnesium of Group 2 in-air falls, The Wer gly arses aller calcium because the next element, scandium, has very litle in conn ye aluminium We have to pass through 10 elements, from scandium to zinc, before ve get an element, gallium, which shows resemblance with aluminium of Group 13. Gallium, therefore, is Placed under aluminium in Group 13. The succeeding five elements, namely, ermanium, arsenic, selenium, bromine krypton, are placed, correctly, in Groups 14, 15, 16, 17 and 18, respectively. Of the 18 elemens belonging to the fourth Period. 8 elements, namely, potassium, calcium, gallium, germanium, arsenic selesioe bromine and krypton (Z= 19, 20 and 31 to 36) are said to be normal or main group or representati se clements of the first three perio to zine (Z = 21 to 30) are called transition elements. The difference beta ye elements lies in the manner of the entrance of electron. Since chemical proper determined largely by the number of electrons in the outermost shell, the properties of transition elements, in ‘which the outermost shell (4s) continues to have the same number of electrons, do not change radically. In the case of normal elements, on the ather hand, the gradation of properties on moving across a eriods is well pronounced. The transition elements difer from the norma elements in sever sat respects alsa for example, in showing variable valency, forming coloured ions and being Paramagnetic. The fourth — period is said to be the first long period. ‘The fifth period, like the fourth period, also consists of 18 elements (237 19 54), 4 begins with Tubidium (Z = 37) and ends with xenon (Z= 54) which, again, is a noble gas. OF the 1¢ elements, eight (2 37, 38 and 49 to $4) are normal elements and the remaining ten (Z=39 to 49) 4. pin elements, : The sixth period is also a long period. It consists of 32 elements (2~ 55 10 46). 1 normal elements (Z = 55, 56 and 81 to 86), 10 transition elements (Z = $7 ee 72 80) and tg vere earth elements (Z = $8 to 71). ‘The rare earth elements begin with cerium (Z = 58) and contin, 7 wrely. The rare earths are upto Jutetium (Z= 71). They are so called because they occur very rarely S BF $0 similar to hey include 8 © scanned with OKEN ScannerPERIODIC TABLE AND ATOMIC PROPERTIES 61 one another and also to lanthanum that they are called collectively as lanthanoids. If these elements are placed horizontally in the same group, there will be undue expansion of the table. To avoid this, they are placed as a separate series below the periodic table, as shown. The seventh period, as shown, consists of radioactive elements with atomic numbers 87 and beyond. Recently, elements upto atomic number 118 have been discovered. As mentioned above, elements beyond atomic number 92 have been prepared artificially through nuclear reactions. Just as the elements after lanthanum are called lanthanoids, similarly, the clements after actinium, i.e, from thorium to lawrencium (Z = 90 to 103) are called actinoids. These elements, too, are placed as a separate series below the periodic table, as shown, The elements beyond uranium which have been prepared artificially by nuclear reactions are called transuranic elements, The common names of elements with atomic numbers 93 to 112 are : neptunium, plutonium, americium, curium, berkeylium, californium, einsteinium, fermium, mendelevium, nobelium, lawrencium, rutherfordium, dubnium, seaborgium, bohrium, hassium, meitnerium, darmstadium, roentgenium and copernicium. The elements with atomic numbers 113 to 118 are named nihonium, flerovium, moscovium, livermorium, tennessine and oganesson respectively. Groups. The elements arranged in vertical columns of the periodic table are called groups. In the recent long form periodic table, the transition clements are also taken into account while numbering the groups. All the groups are numbered in Arabic numerals. The groups headed by H and Be are numbered as Groups 1 and 2, respectively. The groups headed by Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn are numbered as Groups 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12, resectively. The groups headed by B, C, N, O, F and He are numbered as Groups 13, 14, 15, 16, 17 and 18, If the transition elements are taken out, the rest of the elements (the normal elements), excluding hydrogen and helium, arrange themselves in various groups as shown below : The elements of each group are now analogous to one another, For example, lithium and sodium °f Group 1 resemble the elements potassium, rubidium, cesium and francium while beryllium and magnesium °f Group 2 resemble the elements calcium, strontium, barium and radium. Likewise, fluorine and chlorine ©f Group 17 have properties in common with bromine, iodine and astatine, and so on. ‘The elements of aid 18 (noble gases) lie in between the most electronegative halogens and the most electropositive metals. Cause of Periodicity, We have seen already that elements with similar properties occur at regular intervals in the periodic table, Such elements fall in the same vertical column, ie, the same group. The TUTTence of similar properties of elements after certain regular intervals when they are arranged in the order of increasing atomic numbers is called periodicity. A question arises : What is the cause of this periodicity 2 © scanned with OKEN ScannerPRINCIPLES OF Derr SAE Mg, and 18. 62 ider elements of Groups 1, 17 The che consi is question, we may cOnSEY To answe these elements ae given configurations ge a Groups 1, tronic Configurations of Elements of a semens of | Elements of Grou Ne : Is? 2s%p$ 1:2, 8, 18, 18, Sstp$ At: 2, 8, 18, 32, 18, 65% eee Ar: 1s? 2s?p8 3s%p6 | Ks 1s2 28 ph 392p6 dst | crs 1st 2s%ph3s4p5 : + 1s? 2s2p® 3e2pl0 4stps | ag F fl0dghyh $y) | Br : 1s?2s%p83s2phdl dstp® 1: : | eel Xe : 2, 8, 18, 18, Ss%p° | C52, 8, 18,18, Ssiph 6s! Rn : 2, 8 18, 32, 18, 6s%p6 £2, 8 18, 32, 18, 6s%p* 7st ‘The elements belonging to cach group have similar properties but they ne ve et ied belonging to the other groups. For example, all the alkali metals belonging to Group strongly metallic and electropositive as they form cations (e.g., Li*, Na*) very readily. The halogens belonging to Group 17 are strongly non-metallic and electronegative as they form anions (e.g., F-, Cl-) very readily. The elements of Group 18 which connect the two extreme types of elements are chemically inert (least reactive). We may now look at their electronic configurations (Table 1). Since electrons in the inner shells do not, ordinarily, take part in any chemical combination, we have to examine only the outermost elecironic configurations of these elements. We find that all the elements belonging to a particular family (or group) have similar outer electronic configuration. Thus, (All the elements of Group 1 have one electron in the outermost s orbitals : receded by the conti fns*p® ; for Li, 132). i x Pr : i gas configuration (ns*p° ; for Li, 1s). Their outer electronic configuration may thus be written as (ii) All the elements of Group 17 have seven electrons in the out : ; ; ermo: electrons are present in the orbitals while the remaining five ate present nthe pikes Two of these electronic configuration is ns2p°, P orbitals, Their outer (iii) All the elements of Group 18, except helium, have eiehr A Which are accommodated in the s orbitals and the remaining six fil ep ins outer level, two af there are only two electrons both of which are present in Is orbital wires Completely. In helium, filled. Thus, all the orbitals are fully occupied in these elements, which ae enetefore, completely chemically ne. Their outer electronic configuration sn excep for hun anges, Ne mONed, ae is 1s2, The eause of periodicity in properties of elements appears to lie, therefo, similar outer electronic configurations of their atoms at certain regular imemen fervals. Cause of Recurrence of Properties at Regular Intervals of Atomic Numbers that elements with similar properties recur at certain regular atomic number intervals j c These intervals are : 2, 8, 8, 18, 18, 32 and 32. In other words, we have t pass >. g [ tend Periodic table. as the case may be before we come across an element with similar properties. 4. ist 32 elements do we have these particular numbers called magic numbers ? The answer is ag ayes” *¥ises : Why in the recurrence of We have seen already AAs has been discussed in the previous pages and as has been shown clearly in the affixed atthe end of the book, each period begins wih a new major energy eve)” fe Petiodie table ergy level © scanned with OKEN Scannerenj00i0 TABLE AND ATOMIC PROPERTIES 63 jam of various orbitals belonging iagtterent major energy levels is shown in 0 Fig. | can be seen, for m= 1, there is only one | 2-— oo 4 lial) Nem wealtntead atid | FCO BSSSS @ageees) oon have a maximum of two electrons. We may 65 Pr teeage can recall that one electron is added at a time s ‘as we move from one element to the next in the # _ r 9 orbitals Ta elements jodic table. It is evident, therefore, that since § ay? a re is only one orbital associated with n= 1, p= 0eeeess 5600 4 there can be only 2 elements in the frst period. 2) @ > orbitals Te clemen When =2, there are four orbitals (one 2s} ap ST ae ed eG peewee wn mber of elements in the second period & tails —— Fae wil be 8. g| = When n=3, there are nine orbitals (one 06 3s, three 3p and five 3d orbitals). However, | = See 2 the 3d obitals are associated with higher energies | Torbals Telements than even the 4s orbitals. These orbitals, therefore, cannot be occupied before the complete filling of the 45 orbitals. The result is that corresponding to n=3, only four orbitals (one | (. ! is Torbital Telements Energy sand three p orbitals) can be occupied. Hence, Enerpy the number of elements in the third period is also 8. Fig. 1. The energy level diagram depicting energies of various Following the sani’ liné of argunscat, t ca orbitals belonging to different major energy levels. be seen on reference to Fig. 1, that when 1 =4, there are nine orbitals (one 4s, five 3d and three 4p orbitals) to be filled up and hence the number of elements in the fourth period is 18. This is the first long period. Similarly, when n= 5, there are, again, only nine orbitals (one 5s, five 4d and three Sp orbitals) to te filled up and hence the number of elements in the fifth period is also 18. Finally, when = 6 and = 7, there are sixteen orbitals to be filled in each case (Fig. 1). Therefore, there are 32 elements in the sixth period and seventh period as recently four new elements have got Place in 7p subshell. The above discussion clearly explains why the number of elements in the successive periods of the periodic table happens to be 2, 8, 8, 18, 18, 32 and 32. The elements with similar propertics, therefore, ‘also appear after intervals of 2, 8, 8, 18, 18, 32 and 32, as we move along the periodic table in the order of increasing atomic numbers. Division of Elements into s, p, d and f Blocks en The elements, as arranged in the long form periodic table, can also be divided into four blocks what 285, p, d and f blocks. This classification depends upon the type of the orbitals (s, p, d or /) into "ch the last electron of the atoms of the elements enters. ca SBlock Elements. The elements whose atoms receive the last electron in the s orbital of their in ae, energy shell are called s block elements. This block consists of elements of Groups | and 2 State a the s orbitals are being progressively filled. The elements of Group 1 have the general ground genes j°°tFOnic configuration ns!, These are called alkali metals. The elements of Group 2 have the ‘al ground state electronic configuration ns?. These are called alkaline earth metals. © scanned with OKEN ScannerPRINCIPLES OF INORGANIC Chas i, . the last electron in their i anil orbitg Black Elements The elements whote atoms recive the ag electra in having i called p block elements. The atoms of elements ponital (vile » orbitals ate already i etree ge and sx electrons, reqpectively in iectronic configurations for the atoms ot the ele outermost shells, constitute p block. The general elect of this block may be written as ns? np6, ving between s and p sade ceemente The sons of elements of Grou 3 to 12 lying between + and Stet ha the s and p orbitals (of their outermost principal energy shell) ca mr periodic table). The lasa yi th Penultimate (inner to the outermost) shell, however, are still empty ( a progressively filled 4°88 1m these elements, therefore, enters the d orbitals which, thereby, aos the d orbitets of their lag across a period. Thus, the elements in which the last electron euler the aor configu th Le Penultimate) energy shells are called d block elements. The general ns called transition’ on og block elements may be written as (n~ I)d'="0 ng! These slements are also calle which meta Ais block consists of three rows called First, Second and Thind transition ser He vole filling of 3, 4d and Sd orbitals, respectively. The elements from scandium (Z 2 oD) to zine (4 1) im the fourth period constitute the First Inansition series ; from yttrium (Z~ 39) to cadmium (= 48) in the fifth period constitute the Second transition series and from hafnium (Z= 72) to mercury (Z = 80) jn the th period constitute the Third transition seria Ff Block Elements.* The elements in which the last electron enters the f orbitaly of their atoms are called f block elements, In these elements, the last electron enters the third to the outermost (ante Penultimate), i.¢., (n~2)f energy shell. It Consists of two series of 14 elements cach placed at the bot iodic table. The first series follows lanthanum, La (Z= 57) and the second +8 follows inium, Ac (2= 89) in the order of increasing atomic numbers. These series are on led Janthanotds (fron and in aeyAutetium) and aetinoids (trom thorium to favTencium), respectively. In lanthanoids, 4f orbitals and in actinoids, S/orbitals are being Progressively filled, These four blocks are distinctly sh bw, }own in the periodic table, ATOMIC PROPERTIES Before we are in a position to understand such topies as chemical } 1 stand s Sas al bonding between atoms an Feet and shapes of molecules, its necessary to hea aedaiuae knowledge of certain storie opera: hse properties are: ()) Sizes of dioms nag to (©) lonisation Energy Git) WP ‘afin and (iv) Electronegativity, meetron Affinity The sizes of atoms and ions are generall radius of an atom or an ion may be taken. i the nucleus and the outermost shell of electrons If the atomic or ionic radius corresponds to the radius of the 's difficult to define because of the following reasons () ‘According to quantum mechanics, there is ng certainty with Gccupied by electrons at any time. Theoretically an clecion while at other times it may be far away from the muctene ede Of their respective radii, The Sense, as the ¢ 0 ‘ » thowted to be spherical, the sphere. However, thes bsolute sine o atom 10 the @, M, al times, 1 © Vey exact in other wordy. XY chose tothe nucleus en tot Possible to dhe ' Very large distances position {i} It is not possible to have isolated atoms and the probabil arom i appreciably influenced by the presence of other atom i ae ofan atom or an ion would change with change in the enviromer Despite these limitations, we need to have some operational definition of the ragig and an ion. This is necessary in order to get comparative valucy ha MOMS and ions of gins OF an atom and also to explain a number of chemical phenome erent elena There are three operational concepts of these radii. These are : () Covalent Radius (2) Van der Waals Radius and (3) onic Radius. Y distributio, 0 OF lee Vironment. acy *leetrons in an “ Tesult, the size * According to TUPAC, the ending ide normally indicates negative ion and therefine ‘anthanoig nd preferred to lanthanide and actinide. © scanned with OKEN ScannerpeRIODIC TABLE AND ATOMIC PROPERTIES 65 1, Covalent Radius One half of the distance between the nuclei of two covalently bonded atoms of the same element in amolecule, is taken as the covalent radius of fake the atom of that element. While defining the covalent radius as above, it is assumed that atoms are hard, incompressible spheres which are touching cach ciher in normal covalent bond formation. However, atoms are neither fully incompressible nor do they touch each other in a covalent molecule. Therefore, the covalent radii calculated on the basis of the above definition cannot be regarded as exact. The distance between the centres of an can be measured by X-ray diffraction or spec data that the distance between the nuclei of this distance, viz., 0-37 A, gives the covalent 'y Wo neighbouring atoms (viz., the internuclear distance) ‘troscopic studies. For instance, we know from spectroscopic two hydrogen atoms in a Hz molecule is 0-74 A. Half of radius of the hydrogen atom. Similarly, the internuclear distances in Cly and Bry molecules are 1-98 A and 2-28 A, respectively. Accordingly, the covalent radii of chlorine and bromine atoms would be 0-99 A and 1-14 A, respectively. Once we know the covalent radii of some of the elements, we can calculate the covalent radii of other elements from the internuclear distances between the elements whose covalent radii are known and those whose covalent radii are to be determined. For this purpose, the covalent radii are taken to be additive. For instance, the covalent radius of carbon is known to be 0-77 A and the internuclear distance between C and H atoms in CH, is found to be 1-14 A. Therefore, the covalent radius of H atom is 14~ 0-77= 0-37 A. This value is the same as obtained spectroscopically. However, the length of a bond between two unlike atoms, e., atoms differing appreciably in their electronegativities, is shorter than the sum of their covalent radii. The shortening of bond length is due to the polarity developed in the bond because of difference in electronegativities of the two atoms forming the covalent bond. Consider a covalent bond A—B. If A is more electronegative than B, the electronic charge between A and B which is responsible for bond formation, would be shifted nearer to A resulting in the accumulation of excess negative charge on A and a corresponding excess positive charge on B. This would result in additional electrostatic attraction between A and B which would bring A and B further nearer to each other. In other words, the bond between A and B gets shortened. The greater the electronegativity difference between A and B, the shorter would be the bond distance and the smaller would be the covalent radii of A and B as obtained from the bond length, ie., the internuclear distance. According to Shoemaker and Stevenson, the actual bond distance between A and B is given by the relation ra-B= Tat r-0-09 (X4-Xn) 1) where r is the normal covalent radius of A (equal to half the bond distance A — A), ry is the normal Covalent radius of B (equal to half the bond distance B-B) in A and 7 and 7p are the electronegativities « of A and B, respectively, Several modifications of this equation have been suggested to improve upon the evaluation of ry. The one suggested by Porterfield is ra-p= Tatra -0-07 (4-45) 2) The covalent radius of an element determined from a double or a triple bond is shorter than the Gomal covalent radius of the same element determined from a single bond, Thus, the covalent radius fC in ethane is 0:77 A, in ethylene 0-67 A and in acetylene it is 0-60 A. This is due to the fact that in 8 double or a triple bond, in addition to overlapping of sigma orbitals, there is overlapping of pi orbitals the tlt The additional overlapping of pi orbitals results in bringing the two atoms closer thereby reducing * bond length and the covalent radius. thi The electron charge cloud around a singly bonded atom is taken as spherically symmetrical. But, ae not so in the case of a multiple bonded atom. The electron charge cloud is so much cannot be called spherical by any stretch of imagination. In the absence of a symmetrical ibution of charge, it is not proper to call the covalent radius determined for a doubly or a atom as ‘radius’ at all. When there is no sphere, there is no radius, evidently. spherical disteil “ply bonded © scanned with OKEN ScannerPRINCIPLES OF INORGANIC 66 1 ta Although the covalent radii are not always constant, yet the average one Be ae calculat, non-polar single covalent bonds are quite helpful in determining approxtm: nd distances jn or hypothetical compounds. : Most of the metals do not form covalent compounds except for those forming covale; I hy and organometallic compounds. It is, therefore, not possible to determine the covalent radii of Miah However, atomic volumes of metal atoms can be easily determined by dividing their atomic Masses their respective densities. The radii calculated from atomic volumes are called metallic radii, _ In most cases, the size of an atom in free state and its size determined from a single, NON-pola, covalent bond are almost the same. Therefore, the terms covalent radii and atomic radii have been uses synonymously in many books. i i tee covalent radii of elements belonging to various groups of the periodic table are given a ‘able 2, TABLE 2 Covalent Radii (A) of Various Elements (A= 104 em = 10-19 my Group 2 | Group 13 | Group 14 | Group 15 Group 16 | Group 17 Ge Sn Sb ran 138 Ba Tl Pb Bi 1-98 1-48 147 1-46 ts “The radii for noble gases are only the van der Waals radi, (see page 66) It may be emphasised here that the noble gases which consist o| do not form any covalent bonds. In erystals of noble gases, therefore, no chem between the atoms. ‘The van der Waals forces are the only attractive forces oa atomic radii of noble gas atoms are only the van der Waals radii whie closest approach of the two adjacent atoms of the noble gas concerned in i Hence Molecules, ordinarily, J forces are operating h Fepresent Hence, the he Solid we Mistance of Periodic Trends in Covalent Radi, Generally speaking, the covalent radi decy Left 10 right in any given period and increase in moving from top to bottom sn ne moving from Explanation for these variations is given below. "Y Sven group. Variation of covalent radii in a period, ‘The variation of covalent radi ina perio ey easily on the basis of electronic configurations and the effective nuclear charges, Table explained effective nuclear charges, electronic configurations and covalent radii of the elements or 3 8i¥es the period. The effective nuclear charges (Zenecive) given in the table are calculated with the Second Slater’s rules, as discussed in Chapter 1. P of the © scanned with OKEN ScannerpeRi00ic TABLE AND ATOMIC PROPERTIES a TABLE 3 Effective Nuclear Charges, Electronle Confi z igurations and Covalent Radil of Elements of t Second Period of the Periodic Table an Flement ul Be b ry me 4 3 6 7 8 9 TFenctve fo" K — electrons a8 47 6-80 79 469 Zenecune OF L : F electrons 130 195 2-60 325 3:90 455 5:20 F ptectronie 1525! 292 | 2 | configuration | 12° 1s?2s2 | as? astpt | ts? asep? | ts? 2s2p? | as? 20%" | 1s? 2s%p Covalent [ radius (A) a 0-90 0-82 077 075 0-73 0-72 Since the last electron in all these elements is added to L shell, one would expect their sizes (and hence their covalent radii) to be the same. But a glance at Table 3 reveals that the covalent radii are not the same, They go on decreasing with increase in the atomic number within the period. This can be explained as follows : The greater the effective nuclear charge, the greater would be the force with which the electron is pulled towards the nucleus. It is clear from Table 3 that effective nuclear charge felt by both K and L shell electrons goes on increasing from Li to F. As a consequence, the K as well as L shell electrons tend to lie closer and closer to the nucleus. Thus, there is more and more contraction of both K and L shells and hence there is more and more reduction in the covalent radii in moving from left to right across the period (i.e., from Li to F). The same trend is shown TABLE 4 ty the elements of the third and subsequent periods as well Atomic Radit of Alkali’ Metals (Table 2). Since effective nuclear charge felt by K electrons is — more than that felt by L electrons, K shell will get contracted to a greater extent than the L shell. Alkali ‘Atomic | Atomic | Variation of covalent radii in a group. In order to understand the change in the size of the atoms in the same group, the atomic radii of the alkali metals, reproduced in Table 4, may be considered. Itis seen that there is increase in atomic radius on moving from top to bottom. This may be explained as follows : In moving down a group, the number of the Principal shell increases and, therefore, the size of the atom 7 Increases. This effect, no doubt, is partly annuled by the van der Was drawing in of the electron shells on account of the increasing Cpt suclear charge. But the effect of adding a new shell is so large ( “[Link] that it overcomes the contractive effect of the increased nuclear molecules charge. Hence, the radius of the atom increases in moving top 10 bottom in a group. 2 van der Waals Radius The van der Waals radius is defined as one half of the distance benween the nuclei of two adjacent identical atoms element in the Fig. 2. The van der ‘Waals radius of chlorine, ‘longing to nwo neighbouring molecules of an ig © scanned with OKEN ScannerPRINCIPLES OF INORGANig CHE. Th, -| led atoms of ty n two non-bond: oF O49 68 It is essentially the distance Laer atom when the element ij Sate molecules and freed tothe effective pecking size 0 isting between the molecules gS The are an der Wael aus i ued because the Forces €X ee ee aN The nae 7 ar aut The van der Waals ae between 860 chlorine ato my der Waals forces the internuclear dista : ine. th fore, : ~ pice te eciee Jen k fe) The van der Waals radius of chlorine therefore, is gp neighbouring molecules is 3 2. ements are given in Table §, ‘The van der Waals and covalent radii of some common elemer a TABLE 5 nt ‘The van der Waals and Covalent Radii of Some Elements (in A F br 1 Flement " N oO F cl 1 | i | 9% | 9 | der Waals radius | 1 29 Vso) 140 | 13s 180 V9 | aus | Covatent radius 937 | 075 | 073 | on 099 bid | 13 t L As can be seen, covalent radius is smaller than va formation of a covalent bond, the der Waals radius. The Feason is that in the oms have to come closer to cach other. Thi 8 also explains wby covalent bonds are much stronger than van der Waals forces, 3. Tonic Radius The ioni radius corresponds to the ton in an ionic crystal distance from the nucleus of an ion up to which it has influence on in clectron charge cloud, no doubs, May extend theo important to characterise each ion by some value tonic compound is determined from Xen, Of the bea ions involved. Knowing the the distance between the nuclei of Nae and F taken as the sum of the radii of Nae and F determined by of Na’ ion thus obtaine radius of an It may be defined as the elt electron charge cloud. The 4 Very large distance, However, it is incmuclear distance in any ‘aken as the sum Of the ral Hance is 4 other ¢ from x. » that of the tons is determined ions, ton may be used to calculate tf distances in KCL and LiCl crystals. Radii of Cations and Anions, slectrons from the outer shell called 1 of the whole of the outer ‘outer (L) shell. “ring internuclear the valence; shell of electrons. For example, ie iS Causes in WS "985 Of one or more This electron is removed in th any « © is oniy ¥ S#€S the removal ¥ OME electron in the "0 electrons in the Both these electrons are removed Mg? + 2e- 1s? 2s3p6 (065 Ay disappears in this case also. The M shell, therefor © scanned with OKEN ScannerPERIODIC TABLE AND ATOMIC PROPERTIES 69 Thus, in the formation of a positive ion, the outer shell of electrons is generally removed completely. The cation, therefore, is much smaller than the corresponding atom, At the same time, with the elimination of one or more outer electrons from an atom, the number of electrons decreases while the nuclear charge remains the same. The nuclear charge now acts on a lesser number of electrons. In other words, the effective nuclear charge per electron increases and the electrons are, therefore, pulled in more towards the nucleus than before. This effect also fends to decrease the radius of the cation. The decrease in radius when an atom changes into a cation is shown below in the case of sodium, lead, aluminium, iron and manganese, Atomic radius of Na = 1-54 A Atomic radius of Pb= 1-47 A Ionic radius of Na* =0-95 Tonic radius of Pb?* = 1-20 Atomic radius of Al = 1-18 Tonic radius of Pb** = 0-84 onic radius of AB* Atomic radius of Mn = Ionic radius of Mn?* Ionic radius of Mn‘* Atomic radius of Fe = 1-26 Tonic radius of Fe?* = 0-76 Tonic radius of Fe3* = 0-64 It is evident that radius of a cation is invariably smaller than that of the corresponding atom. The size decreases further with the loss of subsequent electrons when cations of higher valencies are formed. During the change of an atom into a negative ion, ie., an anion, one or more electrons are added to the valency shell of the atom. As a result, the same nuclear charge acts on a larger number of electrons. In other words, effective nuclear charge per electron is reduced and, therefore, the electrons are held less tightly by the nucleus and the electron charge cloud expands. Thus, the radius of a negative ‘on is invariably larger than that of the corresponding atom. This is shown below in the case of chlorine, bromine, iodine, oxygen, sulphur and nitrogen. Atomic radius of Cl = 0:99 A Atomic radius of O = 0:73 A Tonic radius of Cl- = 1-81 onic radius of 02 = 1-45 Atomic radius of Br = 1-14 Atomic radius of S = 1-02 onic radius of Bro = 1-95 Tonic radius of S- = 1-84 Atomic radius of |= 1-33 Atomic radius of N = 0-75 onic radius of - =2:16 lonic radius of N}- = 1-71 ation of ionic radii in iso-electronic ions. Iso-electronic ions are those which have the same ‘number of electrons but which differ in the charge on their nuclei (Table 6). The effect of nuclear charge on ionic size is best illustrated by considering the radii of these iso- clectronie species. All of them contain the same number of electrons. They differ only in the charge on the nucleus. It is evident that as the nuclear charge increases, the electrons are heid more and more Uehtly by the nucleus with the result that the ionic radius decreases. TABLE 6 Radii of Iso-electronic Ions lon Ne oO e ‘Nat Number of electrons | 10 | 10 io io Charge on the nucleus) +7 | +8) }o+u Radius (A) Pt ae 133, | 09s | © scanned with OKEN ScannerPRINCIPLES OF INORGANIC CHEMiSy,, 2 ¢ ionic radii increase in movi i the ae ae m Periodic Trends in Tonic Radii. Generally speaking, the ionic ros SAT&CRS 7 some com i ri to bottom in any given group and decrease in moving along a pe! ions are given in Table 7. TABLE 7 Tonic Radii (A) of Some Common te one frou a Group 1 Group 2 Group 13 y Lit | Be? Be 0-60 | 031 | 0-20 Nat | Mg? | ADs 9-98 | 0-65 | 0-50 oe Kr ca | Gat 1:33 | 0-99 | 0-61 Rov se In> 148 110 0-81 | ‘ cs Ba? 1 1-67 129 | 091 . Variation in a group. tis evident from the data given in Table 7 that tonic radii increase with increase in atomic number within a group. This is easily understandable. Since the atomic size increases 5 we move down the group, therefore, increases as we go down the group. It can also be seen that within a Sroup, there is a rapid increase in joni, i ase in ionic radius as we move Gne clement to another amongst the first few elemene (op the increase is m id were tove from ra Ot So rapid when we the increase in ionic radius ig dite rapid aera hen we do so to Na” and from Na* to K* but the increase i S entry of the he same, their POSE the expected i 7 of electron charge move from K* to Rb* and from Rb* to Cs"_ evease in the ionic radio ee vif, Period. Within a period, the radii of cations of norm: 1. deerease with inerease in atomic number and so do the Fadii of anions of gjen'® Of Groups 1, 2 and i 7. This is again easily understandable. Since the atom Size decreases as we ret" Of Groups 16 ond ionic radius also decreases correspondingly. be Ove along a Period, the mired 10 remove n atgiulting in the tom can change M@Q)+IE —» M*(g)t+e- ‘The energy required to bring about the above change is called i ‘smaller the ionisation energy, the easier it is for the neveal aan to © scanned with OKEN ScannerC TABLE AND ATOMIC PROPERTIES j00! pen i through the rl ius a corresponding to this voltage is known as the first ionisation energy (iB). The sudden rise in the current is due to the liberation of an electron from each neutral atom producing an ion, M". at the applied voltage is in . ie pe 7 ohege 7 creased further, there may again be a stage when the current shows a sudden rise. This is due ¢ elimination of another electron from each positively charged ion (M") produced ea ier. : energy corresponding to this stage is known as the second ionisation energy, (En. At h ‘a : Be, loubly “ warged ions, M?*, are produced. If the potential is increased even beyond this pit, there again be sudden and sharp rises in the current at certain points. These points correspond to the loss of three or more electrons and give the third (IE); o higher ionisation energies ofthe element. These changes may be represented as follows : (Ey, M—> Mite (UE) M*—> M+ (iB) Met Mt te Jonisation energy is measured in electron-volts (¢V) as well as in joules or kilojoules. It may be remembered that 1 eV = 1:602*10-!9 joule or 1-602x107 kilojoule. The values presented in electron-volts give ionisation energy per atom while those expressed in kilojoules represent ionisation energy per mole (i.e., per Avogadro's number of atoms) of the clement. Thus, ionisation energy of hydrogen is 13-595 eV per atom of hydrogen and 13-595%1-602 10°22 x 6-022 x 10% = 1312-0 kJ per mole of hydrogen. Let us consider the first and the second ionisation energies for lithium and sodium given below : Li —> Li + © 5 (Ey = 520:1 KJ mol"! Lit —> Li? +e 5 (EB), = 7297-2KI mot! Na —> Nat +e; (JE), = 495-2kJ mol Nat—> Na+ e> 5 (JE), = 4563-5 kJ mol"! are very much higher than the first ionisation energies. As can be seen, the second ionisation energies ‘The successive ionisation energies of some common elements are listed in Table 8. TABLE 8 Successive Fonisation Energies (in kJ per mole) of Some Common Elements “Element | Electronic (er Wr we, | configuration | Li 1322s! 520-1 7297 11810 Be 1s? 25? 899:3 1758 14810 B 1s? 2s%p! 800-1 2428 3660 c 1s? 2s?p? 1086-2 2353 4618 N 1s? 2s%p? 1402-1 2855 4877 ° 1s? 2s%p4 1313-7 3388 5297 F 1s? 2s2p5 1680°8 3375 6045 Ne 1s? 252° 2080-4 3963 6130 © scanned with OKEN ScannerPRINCIPLES OF INORGANIC CHE, ae i : ctron has been taken out of an atom, it becomes ee ee oe these ctsequemt electrons fom th resulting positively charged fon on seeount of cleo aga Ree estes are eco de a miei charge remains the same. Consequently, the remaining (cea Helle ry fahty be nucleus and it becomes difficult to remove the second electron. 7 aia mn energy is greene” ne is greater than the first ionisation energy and, similarly, the thirc a the second ionisation energy and so on. Thus, (/E); > (IE); > (IE);- ; ae The first ionization energies obtained spectroscopically for the various elements belonging to ity groups are presented in Table 9, ‘TABLE 9 First Ionisation Energies of Various Elements (kJ mol!) Group 1 | Group 2) Group 13 | Group 14 | Group 15) Group 16 | Group 17 | : 1520-3 1350-6 Factors Det following factors. I {Atomic size. The larger the atomic size, the ilonteca this is that as the size of the atom increases, ae a af ees Tie farther gc"“8Y- The reason for Hence, according to Coulomb’s law, the attractive pull oa and it becomes easier to knock out an electron from th 2. Nuclear charge. The force of attraction betwe With increase in nuclear charge, Thus, the ervater th to Bull out an electron from the atom. Hence, charge. fe nuclear charge, the TMOSt elegy r eater ig yel°tOn increases ionisation energy increases win), incre, MEY needed ease in nuclear 3. Number of electrons in the inner shells. The larger the number of ete thells, the smaller is the ionisation energy: The electrog in the inner shells act se "S tn rhe inner between the nucleus and the electrons i the Cutermost shell. This is knowns sere’ or shield shielding effect. The larger the number of electrons in the inner shells, the greate, “e8ing effect or effect. Consequently, the electrons in the valency shell experience less attraction from the nytt® Screening the ionisation energy would be low. Msleus. ‘Hence, 4, Penetration effect or the effect of removal of 5, p,d and L electrons trom the « shell. The s electrons in theit motion around the nucleus have greater probability of comin@® ener, the nucleus than the p, d or f electrons of the same principal eweree hell. In other woru" cl penetrate more (owards the nucleus than p electrons and the penetrating power of the elegy el © scanned with OKEN ScannerpeRIODIC TABLE AND ATOMIC PROPERTIES 73 given principal energy shell varies as s > p > d> f. Thus, the s electrons experience more attraction from the nucleus than the p, d or f electrons of the same principal energy shell. It follows, therefore, that the energy required for pulling out an s electron is maximum and it decreases in pulling out a p electron, a d electron or an f electron of the same principal energy shell in the order of their mention. We may thus say that ionisation energy corresponding to the elimination of an electron from a given energy level varies in the order s > p > d>f electron, 5. Electronic configurations. Certain electronic configurations are more stable than others. For example, if an atom has fully filled or exactly half-filled orbitals in the valency shell, its ionisation energy is higher than expected normally from its position in the periodic table. For example, beryllium and nitrogen in the second period and magnesium and phosphorus in the third period, have slightly higher ionisation energies than would be expected. This is due to the extra stability of the fully completed s orbitals in beryllium and magnesium and that of the exactly half-filled p orbitals in nitrogen and phosphorus. Further, itis seen that He, Ne, Ar, Kr, Xe and Rn have highest ionisation energies in their respective periods. This shows that an atom with s?p® configuration (the so-called octet configuration) in its outer shell is highly stable. In this connection it may also be noted that Li* and Na* ions, which also have sip? configurations, require very high energies, viz., 7297-2 and 4563-5 kJ per mole, to permit pulling out of an extra electron from them to give Li2* and Na** ions, respectively. Variation of Ionisation Energy in the Periodic Table. The following periodic trends in ionisation energy are observed, a. Variation in a group. Jn general. the ionisation energy decreases in going from top to bottom ina group. This is evident from Table 9. On moving down a group (i the nuclear charge increases (i) there is gradual increase in atomic size due to increase in the number of the principal energy shell, : (iii) there is increase in the number of inner electrons which shield the valence electrons from the nucleus, The overall effect of increase in atomic size and the shielding effect is much more than the overall effect of increase in nuclear charge. Consequently, the outermost electron is less and less tightly held to the nucleus as we move down the group. Hence, ionisation energy decreases as we go down from top to bottom in any group. There are some exceptions, however. For example, the first ionization energy of indium is less than that of thallium in Group 13 and first ionization energy of Sn is less than that of Pb in Group 14. We shall discuss these exceptions in adequate details while considering the Properties of the main group elements in Chapter 12, 2500 b. Variation along a period. In Seneral, the ionisation energy increases as we move along a period from left to right (Tae 9) 1% a period from left to rig ‘The above variation can be explained 4 follows : On moving across a period, the Pog size decreases and nuclear charge atreaatt® nd, therefore, the force of in thet f*etted by the nucleus on electron aenty, waTmOst shell increases. Conse- remax jt becomes increasingly difficult to mat électron from the outer shell of wcto™ and hence ionisation energy T 2000: 150 1000- FIRST IONISATION ENERGY (kJ mol!) 3 increase 23°65 607 8 9 WO Taxinn THe ionisation energy becomes ATOMIC NUMBERS clog gut” for the noble gas which has stable : Fora tonic configuration, ns2p°, Fig. 3. Variation of ionisation energy with atomic number, © scanned with OKEN Scanner% PRINCIPLES OF INORGANIC CHEMIgyp a 4 on energy along a period is not smooth (Table a wns ru, However, the variation in ionizatio the fact that atomic size is not the only fae 7 he rnin are distinetly observed, This is due Faas energy with increase in atomic number fr the lem ot seme pad dae in Fig 3. The elerncenfiguatns of the elements ar alse of second period is depict Fig. 3 Wn ip the figure. inate e: id oxygen are une: Pectedly fo Us clear ffom the figure that ionization energies of boron and oxy Seon rea than the ionisation energies of their preceding elements beryllium ar eat ie aa ta tee anomalies are explained as follows : Electronic configuration of boron (1s? 2 ° ee ha ta of beryllium (1s? 2s?) which has completely filled s orbitals. Moreover, in boron = : . ' a is Present in 2p orbital which is at a slightly higher energy level than the outermost elec ron in berlin The 2p electron of boron is thus less tightly held by the nucleus and hence the ionisation en boron is less than that of beryllium, Electronic configuration of nitrogen (1822s? ppl p! ine p orbitals are exactly halffilled, is more stable than the electronic confi 2 Therefore, ionisation energy of oxygen is less than that of nitrogen, ELECTRON AFFINITY (E4) energy measures the tendency of an atom to change into a cation the electron affinity (EA) gives a measure of the tendency of an atom to change into ~~ X°). Electron affinity is defined as she amount of energy released when an or ion X®Mte —5 xX ‘Atom The greater the energy released in the clectron affinity. The electron affinity of an at clectron to itself. The electron affinities are expressed in eV per at The electron affi nities of various elements belonging to di given in Table 10, ergy of Just as ionisation M—> r+), an anion (X + & () + Energy (£4) Anion iP the extra electron, the is s » the greater is the fom measures the tightness with “hich it binds an additional fom oF kJ mol-1, erent groups of the Periodic table are © scanned with OKEN ScannerPERIODIC TABLE AND ATOMIC PROPERTIES 75 Variation of Electron Affinity in the Periodic Table. In general, electron affinity decreases in going ym top t0 bottom in a group and increases in going from left to right across a period. This can be easily explained. On moving down a group, the atomic size increases and, therefore, the effective nuclear attraction for the electron decreases. Consequently, the atom will have less tendency to attract additional electron towards itself, é.c,, its electron affinity would decrease, On moving across a period, on the other hand, the atomic size decreases and hence the force of attraction exerted by the nucleus on the electrons increases. Consequently, the atom has a greater tendency to attract the additional electron, i.e., its electron affinity increases. Thus, as expected, electron affinities of metals are low while those of non- metals are high. It is seen that halogens have high electron affinities. This is due to their strong tendency to gain an additional electron to acquire the stable s?p° configuration. The electron affinity decreases from Cl —> Br -> I, i.e., on moving down the group, as discussed above. However, electron affinity of fluorine is unexpectedly low. It cannot be explained by any simple mechanism. It is probably due to small size of the atom. The addition of an extra electron produces high electron charge density in a relatively compact 2p subshell resulting in strong electron-electron repulsion. The repulsive forces between electrons imply low electron affinity. Apart from the size of the atom discussed above, the electronic configurations of the elements also influence their electron affinities considerably. This is illustrated below. Electron affinities of noble gases are zero. This is because their atoms have stable s*p$ configurations in their valency shells and there are no chances for the addition of an extra electron. Electron affinities of beryllium, magnesium, calcium and nitrogen are also practically zero. This is antibuted to the extra stability of the fully completed s orbitals in Be (2s2), Mg (3s2) and Ca (452) and of the exactly half-filled 2p orbitals in N(2s*p!p) p!). Thus, if an atom has fully filled or exactly half- filled orbitals, its electron affinity would be practically zero. The trends in electron affinities within a period are also irregular indicating once again that atomic size is not the only criterion for determining electron affinity. Thus, electron affinity of Be is less than that of Li although the atomic size of Be is less than that of Li. Similarly, electron affinity of N is less than that of O although the atomic size of O is less than that of N. Successive Electron Affinities. Like the second and higher ionisation energies, the second and higher electron affinities are also possible. However, after the addition of one electron, the atom becomes negatively charged and the second electron is to be added to a negatively charged ion. The addition of second electron is opposed by the coulombic force of repulsion and energy has 10 be supplied for the addition of the second electron. If an atom has a spontaneous tendency, ie., a positive tendency, to gain an electron, then, Conventionally, its electron affinity is said to be positive and if an atom is reluctant to gain an electron. ie it has a negative tendency to gain an electron and is forced to accept it, its electron affinity is said to be negative. Thus, in the case of oxygen, the first electron affinity (EA), is positive since 140-9 kJ of ‘nergy is released when a mole of O atoms get converted to O- ions. In other words, O atom has prrutive tendency to accept electron. However, the second electron affinity (EA), is negative since 770 of energy has to be supplied to convert 1 mole of O- ions to O> ions. Similarly, in the case of sulphur, while the first electron affinity (EA); is positive since 200-7 1d of ‘nergy is released when 1 mole of S atoms get converted to S~ ions, the second electron affinity (E4)» 'S negative since 333-2 kJ of energy has to be supplied to convert one mole of S~ ions to $?- ions. Thermodynamically, however, the energy released is given a negative sign and energy absorbed is tet,2 Positive sign. Accordingly, when a species has a positive electron affinity, AH, accompanying © addition of an electron to the species, is negative and if it has a negative electron affinity, AH is (sitive. Thus, for the reaction Cl + e-—> Cr, while EA (= 348-5 kJ) is positive, AH for the Process Negative. © scanned with OKEN ScannerPRINCIPLES OF INORGANIC 76 Be, ELECTRONEGATIVITY aS i i t investigators and each oy ¢ ity has od differently by differen : fey maeeel Chee the cee sae olectranegatriies of different elements. The appa has suggested a method of his own to calcul appre of some of the investigators are discussed below. vit tom in & molec: ing’ ir tivity as the power of an ai Necate » Pauting’s Approach. Pauling defined electronegatis ! cas a eal attract lecrons 0 itself. He calculated electronegativities of different elem rermodynam,. data, He considered that in a reaction of the type W2(A-A) + 1/2(B-B) —> A-B the bond dissociation energy of A ~ B is higher than the mean of the bond dissociation energies of 4 _ nd (B ~ B) bonds and that their difference (A) is related to the difference in the electronegatisine OFA and B according to the following empirical equation « A= Eq Ep -V2(Eq 4 + En) = 2374-70? Tae denote the mseons dissociation energies of AB, A~ A. and B - B bends, ‘ty denote the electronegativites of A and B, respectively. Thus, A= 234 ~ 4p)? 0:208VA = x,-7p Pauling later took the geometric mean inst where Exp, Ex_s and E, respectively and yq and or ‘ead of the arithmetic the following empirical correlation + mean of Ea. and Ey y and Fan -Exca*Ea.9)! = a 230, ag) or 0-182 Va" = x4 yp TABLE 11 Flectronegativitis of the Main Group Elements (Pauling’s Values) Grp t ] coop? | Gear | Gow poor | se fi A if { Li Be B 10 1s 20 1 K ca Ga Rb Ss In 2 e © scanned with OKEN Scanner¢ TABLE AND ATOMIC PROPERTIES = oT pen 1, Caleulate the electronegativity of rar _Galeate tig clctronegativity of fluorine from the following data : Ey. = 1042 sot : seal ion + According to Ea. 6, Ene ~ (Ena * Epp)! = 1346 ~ (104-2 * 36:6)!2 = 72-85 keal according 10 EQ. 7. Hy ~My = (0°182) (72-85)!2 = 1-55 p= 1°55 + yy = 155 +21 = 3-65 ple 2. Calculate the electronegativity of carbon from the following data : Ey. = 104-2 keal oe mrt gil keal mot, Ec-y = 98-8 keal mot, following data : En-1 i Solution : According to Eq. 6, 4 = Eon ~ (En ‘According to Eq. 7, * Ecc)!? = 98-8 - (104-2 * 83-1)!? = 5:75 kcal Ye- Ny = 0-182 (5-75)!2 = 0-44 Xe Allred and Rochow’s Approach. Allred and Rochow defined electronegativity as the electrostatic jirce of atraction exerted by the nucleus of an atom on the valency electrons. Making use of the ‘ecive nuclear charge at the periphery of the atom, Zeqecrive, 8 calculated by Slater's rules, they proposed te following empirical relation for caiculating the electronegativity : 7, = 0°359 * Zettive/? + 0-744 (8) where 7 is the electronegativity and r is the covalent radius of the atom in angstrom units. The detonate a calculated with the help of Eq. 8 are found to be remarkably close to those reported ty Pauling. 0-44 + yy = 0-44 + 2-1 = 2-54 Example 3. Calculate the electronegativity of carbon atom following Allred-Rochow’s approach. The (walest radius of carbon atom is 0-77 A. Solution : According to Slater's rules (Chapter 1), = Zany 5 = 6 ~ (0°35 *4 + 0°85 * 2) .Sective at the periphery of C atom According to Eq. 8, ae. = 0-359 * 2900-77)? + 0-744 = 2°50 Example 4. Calculate the electronegativity of silicon following Allred-Rochow approach. Covalent nM of Si = 1-195 A. Solution : Electronic configuration of Si is 1s? 2s%p* 387 “Scording to Slater's rules (Chapter 1), Zettativa = Zea 5 = 14— (035 «44085 x8 +102) ~ 580 Ace on 0 Eq. 8, qi = 0-359 = 3801-175 + 0-744 = 2°50 liken’ the ization energy (IE) and eestliken's Approach. Mulliken suggested that the average of the fonizakon tte ” Any (EN) of ate ahd bere measure ofthe electronegativity (Za) ofthe atom, that i, Ho ty = WQUIE + EA) : = te gl WEVer the joni f in Mulliken’s definition are not Sap, i an atom in a “ne ionisation energy and the electron affinity of an. its ground state. These are instead “culated CLIY Observed values for the isolated gaseous atom in its gr Sor molecile or 4 Nalues forthe atom in its valence state, £¢., when the atom forms a part o| ; “hh tan Be atom used in Mt ne Be atom having | e, in BeF, the ionisati : tulliken’s formula is not the one n BeF;, the jonisation enerey of 522s? configuration but is the “mentally observed for an isolated © scanned with OKEN ScannerPRINCIPLES OF INORGANIg Ch, Nig, hybrid orbital of Be atom, In 78 Jectron from an SP on dal 2p eleven ‘ 7 y ired to remove an ¢! ired to remove 2s and

ee (promoted valence state) (ground state of Be) IE | ew 1s25!2p0 ‘The JE and EA used in Mulliken’s formula can be calculated by a complicated mathematical Prose, which does not concem us here. iri i ists to bring Mulliken’s values at Par yj Several empirical equations have been proposed by chemist 1 i the values of x on Pauling’s scale. One such equation which attempts to give x4 nearly at Par With, value of x on Pauling’s scale is : JE+EA iM = oars -0ss| oll, In this equation, JE and EA are in electron volts, One advantage of using Muliken’s approach is thatthe clectronegativities of an element, which Present in different oxidation or hybridisation states can be calculated. For instance, xy of C in sp}, 9° @ hvbridised states, calculated by Mullken’s approach, nc 2-48, 2-66, 2-99, respectively, whereas (Pauling’s values) of C in all its states was Teported to be 2-55, id 7 7 Factors influencing Electronegativity, Although the electronepativi a ic assigned a definite value, yet it may differ fom ne molecule 10 aie an ¢lement is conventional molecule to attract electrons towards itself de The ability of an atom int ends upon its enviro is nm Pend upon the nature of the ent in the mol jecule. The * The factors which largely determine the elect other atom with which its follows, onegativity of an atom ate & Charge on the atom. An atom which acquires a Positive eh vr ettat electrons more strony than a neta alg, “he 2 eae" integral or partial, woul than the parent atom which, in tur, would be more electronegative ta" ill be more ef fectronegaiv Positive oxidation state of an atom in a species, 3 the greater would be nes SiON. Also, the higher the hence the greater would be its electronegativty, “Fer example, the a lectron- attr te hie! ing power and atom is +1 in HCIO and +5 in HCIOs. Hence, the chore Atom will be gi” State of gene Sue than in HCIO. Accordingly, the release of hydrogen as Hor HCIO, wee clettonepatine ie cyclo, similar change in HCIO. In other words, HCIO3 behaves cv ¢ stronger acid yall Be much easing Hybridisation. We know that s electrons are more Penetrating than qo” HClO. a an atom has hybrid orbitals with a greater s character, the electro’ charge 4°? lectrons it closer to the nucleus of that atom. This means that the ectronegativiy gg Wh Orbital MeretOre with increase in s character ofits hybrid orbitals... For exampler te than, © atom "ould remais sp? hybridisation of its orbitals so that the hybrid orbitals have 2S0, s character" ©atbon and eves atom involves sp? hybridisation of its orbitals and ‘consequently the s ch; : Ih en m involve : athe § character of 1° ethylen to 33%. In acetylene, the carbon atom involves sp hybridisation of its of tale id on ‘he carbon character of hybrid orbitals increases to 50%. Accordingly, the electroneya ity as ahd, increases carbo, ref, ¥ lectronegativity oy “atbon re, the S as we move from CH, to CH, and to CzHz. Due to greater el atvity orcas ae : and acetylene the electron pair of C ~ H bond is pulled more towards the carbon atom om eases the release of H atom as H* ion. Thus, while methane is neutral, ethylene is wylen TERY acide OY fag is considerably acidic. ei © scanned with OKEN Scannerpeniovic TABLE AND ATOMIC PROPERTIES similarly, the basicity of amines also varie 79 y 's with the type of the hybridisation of the orbitals of th: en atom. The higher the 5 character of the hybrid orbitals, the greater would be the ‘clectronegativity id the Jower ben eet ectron-donating power of the nitrogen atom and hence the lower would the ae vend 9 me : esau oo poe RCN, CsHsN (pyridine) and CgHsNH, involve, ively, SP 5 P on of the orbitals of the nitrogen atom. Accordingly, the s character the hybrid orbitals of nitrogen atom is 50% in RCN, 33% in pyridine and 25% in anilige. Accordingly, ine is a stronger base than pyridine which, in turn is a stronger base than RCN. : Effect of substituents. The electronegativity of an atom depends considerably upon the nature of the substituents Cee to that atom. For example, the carbon atom in CFsI acquires a greater positive charge than in CH3I. Hence, the carbon atom in CF3I is more electronegative (i.e., more electron pulling) in CHl. The difference in the electronegativities of an atom caused by the substituents results in siflerent chemical behaviour of that atom, For instance, CFI and CH31 yield different products on hydrolysis = of anili CF3l + OH" —> CFH + 10- CH3I + OH" = —> CH;OH + Role of ionization energies and electron affinities. According to Mulliken, electronegativity is related to the average of the ionization energy and electron affinity of the atom (Eq. 9). Evidently, the higher the ionization energy and electron affinity, the greater would be the clectronegativity of the atom. Effective nuclear charge. Variation of electronegativity in the periodic table. Allred and Rochow reasoned that the electron attracting power of an atom in a molecule is proportional to the effective nuclear charge, Zefrective. Thus, any factor which increases Zeffective, Should also increase the electronegativity of the atom. For example, Zopfective decreases as we go down a group in the periodic table. This is because with increase in atomic number within a group, the atomic size increases. Hence, electronegativity decreases as we move down a group. Thus, the electronegativity of the halogens decreases in the order: F(4-0) > CIG-1) > Br2-9) > 1(2°6) Zemeaive increases with decrease in size of the atom and the size of the atom decreases as move along a period from left to right in the periodic table. Accordingly, electronegativity goes on increasing with increase in atomic number as we move along a period. Thus, electronegativities of the elements of the second period increase in the order : Li(1-0) < Be(1-5) < B(2-0) < C(2'5) < NGO) < OG'5) < F4-0) Zctective also depends upon the number of inner electrons which screen the last electron. The larger the number of inner electrons, the greater would be the screening and the lesser would be the effective tuclear charge. Thus, electronegativity would decrease with increase in the number of inner electrons in atoms of the elements in the same group. This is an additional reason why the electronegativity of alkali metals decreases in the order : Li(1-0) > Na(0-9) > K(0-8) > Rb(O'8) > Cs(0-7) ie Applications of Electronegativities. Electronegativities have very wide range of applications. Some ‘he important applications are given below. 1. Calculation of partial ionic character arovalent bond between two atoms, say, A an B. The greater the difference in the electroneg: of a covalent bond. The development of ionic character in d B, is due to the difference in the electronegativities of ativities, the greater would be the development of ‘nie character and consequently the higher would be the stability of the resulting bond. Pauling suggested the following correlation between the electronegativity difference %Zq—%p and * Pet cent ionic character of the covalent bond : -025(t,-%g) Alt Per cent ionic character = [I-e “4 “® J x 100 (1) © scanned with OKEN ScannerPRINCIPLES OF INORGANig Chey My = in HF is 1-9 Cateuy, » Fxample S. The electronegativity difference of the elements in HF is culate Example $, y ionic character of the H-F bond. © Pe Solution : According to Pauling’s equation (Eg. 11), 92519) 100 = 37-77 Pet cent ionic character of H-F bond = (1 ~¢-2509)]y : he per cent ion; ae iting the T Cel 10ni¢ Pauling suggested an altemative empirical equation for calculating the p hata, according to which Id Per cent ionic character = BG, ~ 4) “fly According to this “Auation, the per cent ionic character of HF comes out to be 44-12. this Val 'S quite close to the one (viz., 44:8) obtained by Pauling from dipole moment of HF (Chapter 4), 2. Calculation of enthalpies of formation of compounds. It is possible to calculate enthalpies o formation of compounds from clectronegativities making use of the following empirical equation put forth by Pauling : AHy= 2B (Ln ~4p)?~554 My; ~ 260 ng (13) where AH; is the Enthalpy of formation, ny and pein {he numbers of nitrogen and oxygen atoms in the molecule, The value of © would be 1, 2,3, ete., depending spon the number of bonds in the molecule. For instance, -< for HCl, ¢ = 2 for BeCl and so on, The valu SDove are, however, approximate, BeCls, There are two Be-C] bonds in 3-1 and 15 (Table My, ‘cal moll) 3. Calculation of bond length, It the two atoms A and bonded bond differ in their clectronegativities, then the covalon bond wo illustrated above c ire at through a covalent the bond acquires pos i aeauite some ionic characters ] Shoemaker ang Steven, Polarity, the shorter would ch cases : PrOPOSed the following = TA* 13- 0-09 (44 ~ 4g) i id BS; is the actual bond distance between A an : a and oe is the electronegativity difference. The noma length of ine and B would have been equal to 7, + rq. Evidently, the shorten’ {2 clectronegativity difference is equal to 0-09( 7, ~%y). Due to be more stable. dn 4) d fl Ts and ry are ovAlent rai 4 A and B B Of the bona co bond between A Teduction in length the i B oe 0 ‘ance N-O with the help of Eq. 14, covalent radio os oes ae 0-75 and 0-74 A and the electronegativinias °f Nang a oxygen ; 3-5, respectively. Thus, trogen and te 3-0 and dy.0 = 0-75 + 0-74 ~ 0-09 (3:5 ~ 3-0) = 1-445 A The actual N-O bond length is 1-46 A. Similarly, the length of the C-O bond is given by deg = 0-77 + 0-74 - 0-09 (3°5 —2°5) = 1-42 A is the same. The experimental value is exactly the © scanned with OKEN ScannerND ATOMIC PROPERTIES 81 nd angles. The lesser th ivi a or bone dat magnitude a 7 flcctronegativity of the central atom in a polyatomic oye : Ss, it »€ able to hold the bonding electron pairs easton Therefore, the bonding electron pairs would shift more towards the other atoms attached ek : ji , Pes gn Ths wonld Fel in @deerease inthe bond par-bond par fepulsion and Hense 8 ptt oa the bond angle. oO on, the bond angles and electronegatvities of triuorides ofthe Group 15 elements are or illus in vars ras expected, the decrease in electronegativity of the central atom results in a decrease of Compound | | | of Central Atom le. bond # 3 "Bead Ax ve Electronegativity T Bond Angle 5, Rationalisat au pucleophile [Mn(CO)s}°, the following reaction takes place CHyl + Na*[Mn(CO)s]-—> Nal + CH3Mn(CO)s ‘The formation of the above reaction products may be explained as follows : lodine in CH3l is rerechetonegative than carbon. ‘This creates a partial positive charge on the carbon atom. The negatively faced mecleophile, thus, attacks the positive site resulting in the formation of CHsMn(CO)s. nthe other hand, if' we carry out a similar reaction with CF3l, a totally different product is obtained. Thus, 2CFy1 + Na*[Mn (CO)s]> —> Nal + Mn(CO)st + CoFe Because of the presence of highly electronegative F atoms, the electron charge cloud of carbon tos pulled towards the former. This creates electron charge deficiency at the carbon atom which is "2: w by the pulling of the electron charge cloud of iodine atom towards the carbon atom (the electron shut of iodine is easily polarisable). This creates a partial positive charge on iodine atom. Therefore, ‘acleophile [Mn(CO).]- now attacks the iodine site leading to the formation of Mn(CO)s. 'nasinilar way, we can explain the acidic or basic nature of some hydroxy compounds. Consider, rhe a taet +. ght, HOC. ‘The chlorine atom in this molecule is in +1 oxidation state. It is, therefore, more ‘ctstacting than oxygen, The chlorine atom, thus, pulls the electron pair of the O-Cl bond towards sya electronic charge deficiency on the oxygen atom. In order to make up this deficieney, the ip jg ot Pulls the elect it ‘wards itself, This facilitates the release of H atom ion by th ron pair of O-H bond towar ss bbe UU of the O-H bond. Hence, the hydroxide HO-CI behaves as an acid. Sojgo lbs the electronegativity of Be is less than that of oxygen. Therefore, the electron pair of “Ohad ed more towards oxygen. This facilitates the release of OH" group with the rupture of © tigge ES BXOH). behaves asa base ; v5) (anaato” of diagonal relationship. The electronegativity increases as WY Bo from Li (1-0) to 13) (ston of electronewetictiy ine period) but it decreases as we move from Be (1-0) 10 eatvity pe two opposite changes (one Varia + the ion of ele Dds It of these Petiog ctronegativity in a group). As @ nist these two effects partly cancel 4 ber the other diagonally ; down thi , as we move diagonally, nt gE IS no marked ct a lectronegatviy This is the reason why Li (1-0) and Mg ‘alues of clectronegativities. © scanned with OKEN ScannerPRINCIPLES OF INORGANig ChE 82 . i i? Because of similar values of electronegativities and hence of clectron-attracting Powers, 1) *4, have similar chemical properties, nee two atoms would, evidently, depo 7. Types of bonds. The type of bond formed between Pend the differenee in their electronegativities. If this difference is zero or very nail the pon form, wt be covalent and if the difference exceeds 2-5, the bond formed would be electrovalent, 1p hover the clectronegativity difference is less than 2:5 but otherwise quite appreciable, the bond fe formed voy be polar covalent, QUESTIONS the cause of periodicity in the properties of elements ? jfrst period, 8 elements in each of the second and third Periods Jith Periods and 52 elements in the sixth period of the period table + State the modem periodic law. What is (@) “There are only 2 elements in the clements in each of the fourth and Why is it s0? () Which of the following elements exhibit similar properties and why ? ALIS2S 631 Bs 1P2a—6 scpb,0ggt Cz 1st ast TAns. A and ¢) - wed in the long form periodic table. What is meant by a group and a Period? (a) 132 2s2p6 35296 451 ®) 12 2s%pf 352960 gy1 © W296 30 4 7 P (@) 227638 phal04,2p10f satgg2 (©) 1222 D 182 2526 35296,110452 TAns. (a) 5 id; + 18, 32 and 32, How would you account far $. (@) What are main group, transition and inner transition from the main group elements on the basis of electronic cont (6) Would you eall Zn (Z following series > Meth nie 7. Explain the following : Nat > Mg?* > AD*] (2) van der Waals radius of chlorine is greater than the covalent radius of chlorine (0) The atomic radii decrease in moving fiom lef to right in ANY Biven period and ‘ ‘op to bottom in any given group. increase in Moving from (©) The radius of a eation is invariably smaller and that of an anion invatiably larger than tha g atom: MOF the corresponding 8 (@) Explain the term ionisation energy of an element. On what facton does it depend (©) ‘he ionisation encrgy of Na* is more than that of Ne although both have the same electronic i Explain, Configuration. % (a) Explain the term ionisation energy ? low is it measured ? How do thet Vary #s we move (i) along a period (ii) down a group and why is i if ionisation energy and third ion (6) What is meant by the terms : First ionisation energy, secon: : ny a Why are second ionisation energies so much higher than the first ionisation enenses tion ener "eBies OF elements sation energy? © scanned with OKEN Scanner¢ TABLE AND ATOMIC PROPERTIES 83 penioo! yo. co Ean the term electron affinity. Why are electron affinities of the halogens so high ? (9) Predict whieh element in each of the following pairs has higher ionisation energy and why : {p SP Be B GDN. C GH) Ne, FO) 1 Br (RCL (vi) Na, K lAns. (i) P (ii) Be (iii) N (iv) Ne (v) Br (vi) F (vii) Na} Define ionisation energy and electron affinity. How do these vary in the periodic table as the atomic ‘number increases (p) Account for the following trend in the electron affinities of the halogens ? F a Br 1 332'6 kJ mol! 348:S kJ mole! 324-7 kJ mol"! 295-5 kJ mol! (©) The electron affinities of noble gases are zero. Why ? (a) Explain the term electronegativity. How is it related to electron affinity and ionisation energy ? 1 @ (8) Why is the radius of an atom not defined precisely ? 5, Give reasons for the following : () The second ionisation energy of sodium is very high as compared to its first ionisation energy. (6) Electron affinity of fluorine is less than that of chlorine, (6) lonic radius of K* is smaller than that of Cr. (@ Electron affinity of N is almost zero while that of F is very high. (¢) Size of Clr ion is greater than that of Cl atom while that of Na* ion is smaller than that of Na atom. () Flectronegativity increases along a period. (6) lonisation energies of C, N and O follow the order : C < N > O. |4, Define the following and explain their trends in a period and in a group : (@) Electron affinity (6) Electronegativity (c) Atomic radius (¢)_Ionisation energy 1S. (0) “Atomic radius is a measure of the effective size of an atom and it has different values in different environments.’ Discuss this statement. (6) Which of the two has higher ionic radius and why ? Al’ or Al (9) The ionisation energy of Al to form Al* is less than that of Mg to form Mg ion. Explain, 141 kJ mol! and -770 kJ mol"!, respectively. Pt ‘9 The first and second electron affinities of oxygen are Account for this. : (0) The electron in i in keal is released when 2 g of chlorine is affinity of chlorine is 3:7 eV. How much energy in ka 8 Completely converted to CI- ion in the gaseous state ? [Ans. 4:86 keal) « : i ‘The electronic configurations of some neutral atoms are given below : As 22096302, BB; 1sbasipbast; C + Is? 2stph; Dt 1s?2s%pA ee i Ans. Bi ih is Of these will have the lowest ionisation energy ? (Ans, B] Dieu Cecronegativity has been defined differently by different investigators: 1 oe factors which influence the electronegativity of an atom. 2 \s 3S the term electronegativity defined by Pauling, Allred & Rochow and Mulliken ? seu SS the ig Important applications of electronegal Comment on this statement. © scanned with OKEN Scanner