| ie hich atom in each of the following pairs has the greate a0 Propiems FoR PRACTICE jowing in the order of increasing fonization enthalpy : 2 on? the following in the order of increasing ionization enthi MP ay 222 Ot (yy 1s? 287 range th de Wipe 2s 2p6 Be? (i) 15825? 2p6 3s) i) As? 2s? 2p® (P felectronic configurations of some neutral atoms are given Below : pies (ii) 122282 2p! Ti) Le 2c Opto) 192 2 (rich ofthese electronic configuration would be expected to have the highest ” woth (b) AHy (0) SH, (@) dy sinalpy 7 Which has the 4, Among the elements Lis K. ‘Ca, and Kr, which one has the lowest frst ionization & » Fighest first ionization enthalpy ? Explain. Wen ofthe following pairs of elements would you expect to have es ower first ionization enthalP) aw © qclorF i) Clors (iii) K or At (iv) Kr or Xe, 4. For each ofthe following pairs, predict which one has lower Ys jonization enthalpy ? (Nor (ii) Naor Nat (ii) Be* or Mg? (i) Tor > 6 Theft (,) and the second (4,H,) ionization enthalpies (kd Pag) of tree elements I, Il, TI are given telow : I 1 in aH, 403 549 1a 2640 1060-2080 ‘dentfy the element which is likely to be (a) non-metal (b) an alkali metal (c) an alkaline earth metal. + first ionization enthalpy and explain your swer. (a) B and C (b) N and O (c) F and Ne 4, From each set, choose the atom which has the largest ionization en (@F,0,N (6) Mg, P, Ar (c) B, Al, Ga SEs 1 i <() < (i) <0) Cl > Br > I. Comment upon the statement. 1 O<()< (i) < (iti) 2.N,B,C,0 3.()O->S 4, The statement is wrong. The actual order is | > Br > F > Cl S-> 0 (i, O-> S () N->P (1s? 2s? 2p® 3s? 3p4), only N because moving from B —> C—> O, therefor C—O. Thus, the overall decreasing 0 )Due to repulsions between the electrons on | “enthalpy of O is positive while that O a—ve- (ii) On similar grounds, the electron gain entt Due to small size, repulsions between O- ‘lectron gain enthalpy of O~ is more +ve than th ‘(») Due to repulsions between N~ and the incomin3.19, Electronegativity Electronegativity of an element is the tendency towards itself in a covalent bond. It is represented b): * if It differs from electron gain enthalpy and ionisation & 7 F'.5, atom in the in their isolated states, whereas electronegativity 18 9 por ctronegativity is not 4 m esa eae Unlike ionization enthalpy and electron gain enthalPy, 1 Cee aaa PAcooighs Although a number of numerical scales of electronegalivity © SP ios Muar Allred-Rochow scale have been developed, yet the Pauling 8 egativities of two Bom eaa Linus Pauling, an American Scientist, the difference 0 the el bonded together is given by the relationship. finn Eoe E,* hy —%p = 01017 VA where A= E,p vA scdeertitsicsetanpes mol.) Of he tones 5B, Here, Ey yEy_ and Ep g represent bond dissociation ential TT cous a and B respectively A-A and B-B tapestiely and and represent electonegatiities 1° 0 iy o attract electron), By arbitrarily assigning a value of 4-0 to fluorine (the element havin © 5.) the electronegativity values of other elements were calculated (Table 21°) Electronegativities of representative elements (on rac the shared pair Of electron to kii). ed as A gense tht these relate 10 atoms thal etc. in theisr™ ponded state. the Pauling scale) H 2 Li Be B c NY io ci 10 15 20 25 30 el ee Na Mg Al Si Pp s so 09 12 si 18 2 25 30 K Ca Ga Ge As Se Br 08 10 16 18 20 24 28 Rb Sr In Sn Sb Te i | 08 10 17 18 19 2.01 25 | cs Ba T Pb Bi Po At | 07 09 18 19 19 1.76 22 The electronegativity of any given element is not constant but depends upon the following factors ses, the electronegativity d to that of-Fe* (1-83). | earbon atom in CF31 acquires etronegative than in CH;l. © move along the period as when we move down theen "ii. Applications of Electronegativity 4 ‘the concept of electronegativity is ver ey. of bonds. Ty useful in predicting metallic, non metallic character of elements {) Metallic and non-metallic charactey Conversely, as the eléctonepatey As the clectronegativty increases, the non-metallic character Se he highest clectOncecta tn coeteases the metallic characte increases For example, { electronegativity of 0-7 is the mee 0 is the most non; metallic element and caesium with the PGs ec tee racine metallic element in the periodic table. * pared ait of electrons is equally agin rs two similar atoms is said to be non-polar since the y the t "Thus, Hy, Cly, > and Ny molecules are ae os as the electronegativity of the atoms is the th ive es a ene electronegativity of the two atoms forming a bond is different, the shared Se areal sedi ne towards the more electronegative atom. Asa rest the more electronegative ae tatrolee ara - e charge and the less electronegative atom acquires a partial positive charge. Asares -veloped and the molecule is said to be polar. Thus, H-F, HCI, HBr, HI etc., are polar molecules. The polarity PI the molecules is measured in terms of its dipole moment. Higher the difference in electronegativity of the two binding atoms, the more is the dipole moment of the molecule. For example, the dipole moment of HF (1-86 D), HC! (1-11 D), HBr (0-79 D) and HI (0:38 D) decreases as the sectronegativity difference between the two atoms decreases. Further, a polar covalent bond is said to possess some partial ionic character. If the electronegativity difference between the two atoms is 19, the bond is said to have SO% ionic and 50% covalent character and ifthis difference increases further, the ionic character further increases as shown below : Electronegativity difference 0:6 08 12 19 22 28 32 15 30 50 70 86 92 jt pio Partial ionic character 10 ZA, however, the electronegativity difference between the two bonded atoms is less than _1:9.she bond {s said to be predominantly covalent. tivity. The main points of difference Difference between electron gain enthalpy and electronegat ae summed up below :( What is common in them ? (i) Ar (a) Each one of these ions contains 10 (b) The ionic radii of isoelectronic ions charge. For example, consider the isoe haye 10 electrons but their nuclear2 Q. 3.20 ionization enthalpy values (in kJ mot™) of group 13 elements are : ‘ve i 3.49. The first , B Al Ga In 1 801 577 579 558 589 1u explain this deviation from the general trend ? own the group 13 from B to Al, the ionization enthalpy decreases as expected due to an mie size and screening effect (of s- and p-electrons of the 2nd shell) which outweigh the ‘d nuclear charge. However, 4; H, of Ga is only slighly higher (2 kJ mot) than that of h higher than those of Al, Ga and In, These deviations can be explained as How will yo (On moving di increase in effect of increase ‘Al while that of T1 is mucl follows ‘A follows immediately after s-block elements while Ga and In follow after d-block elements and TI ater d_ and block elements. Since d- and f-lectrons shield the valence electrons from the nucleus less ‘vrectively than s~ and p-electrons, therefore, valence electrons remain fairly strongly attracted by the sie cus. As a result, effective nuclear charge increases and consequently ionization enthalpy increases ‘Thus, as we move from Al to Ga, due to ineffective shielding of the valence electrons by 3d-electrons, dhe elfective nuclear charge on Ga is slightly more than that on Al. As a result, AjH; of Ga is slightly to In, the nuclear charge increases by higher than that of Al. Further, on moving down the group from Ga t Jectrons outweighs the effect of the 18 units (49 — 31 = 18). Here, the shielding effect of all the inner el er than that of Ga. On further moving from Into TI, increased nuclear charge and hence A;H, of Ins low sper clear charge further increases by 32 units (B1 -49 = 32). Ths increased nuclear charge outweighs the chielding effect of all the electrons present in the inner shells including those of 4f and Sd-clectrons and-bence A\H, of TI is higher than that of In. ‘Which of the following pairs of elements would have a more (i) O or F (ii) F or Cl . (i) Both O and F lie in 2nd period. As we charge increases. Both these factors tend to increase Ans. negative electron gain enthalpy ? ni6ve from O to F, the atomic size decreases and the nuclear the attraction of the nucleus for the incoming electron ov henoe electron gain enthalpy becomes more negative. Further, gain of one electron by F gives F ion avich has stable inert gas configuration while the gain of one electron by O gives O" ion which does not hive stable inert gas configuration. Consequently, the energy released is much higher in going from F we F than in going from 0 —> O-. In other words, electron gain enthalpy of F is much more negative (- 328 kJ mot") than that of oxygen (-141 J mol). (i) In general, the electron gain enthalpy becomes less negative on moving down the group. But the tlectron gain enthalpy of chlorine (~ 349 KJ mot") is more negative than that of fluorine (— 328 ky mol"), The reason for this deviation is the small size of F atom. Due to its small size, the electron- 2 ‘2p-subshell are comparatively large and hence the incoming 22 electron repulsions in the relatively compact citron itraot accepted with the same ease as is the case with larger C1 atom. Consequently, electron gain enthalpy of Cl is more negative than that of F 3.21. Would you expect the second electron gain enthalpy of © as postive more negative or les negative ~~ than the first ? Justify your answer. positive as explained below : form O- ion, energy is released. Thus, first electron gain (0) ‘Ans. The second electron gain enthalpy of O is ‘When an electron is added to O atom to enthalpy of O is negative. 0(g) + 6 P.O) i Ag H=~ {0 O- to form O* ion, energy is absorbed to overcome the strong charged O- ion and the’ second electron being added. as a Tea he second elecrron gain enthalpy of oxygen is postive “ © @) 467 @)—? OF ©) i byy H= + 7801 mot! between ‘gain enthalpy and electronegativity ? ‘the atom of an element. The elements of group 1 have only one electron in their respective valence shells and thus have a strong {© Identify the element that would tend to gain two electrons, (4) Identify the group having metal, non-metal, liquid as well as gas at room temperature, ‘ ® ‘The general electronic configuration of the elements having five electrons in the outer subshell is ns? 5. This electronic configuration is characteristic of elements of group 17, ie., halogens and their edie are F, Cl, Br, I, At, etc. (b) The elements which have a tendency to lose two electrons must have two electrons in the valence shell. Therefore, their general electronic configuration should be m s*, This electronic configuration is characteristic of group 2 elements, i.e., alkaline earth metals and their examples are Mg, Ca, Sr, Ba, etc. (c) The elements which have a tendency to accept two electrons must haye six electrons in the valence shell. Therefore, their general electronic configuration is ns? np*. This electronic configuration is characteristic of group 16 elements and their examples are O and S. (d) A metal which is liquid at room temperature is mercury. It is a transition metal and belongs to group 12 ‘A non-metal which is a gas at room temperature is hydrogen (group 1), nitrogen (group 15), oxygen (group 16), fluorine, chlorine (group 17) and inert gases (group 18). A non-metal which is a liquid at room temperature is bromine (group 17). |. The increasing order of reactivity among group 1 elements is Li < Na < K < Rb < Cs whereas that of group 17 is F > Cl > Br > I. Explain. tendency to lose this electron. The tendency to lose electrons, in turn, depends upon the ionization enthalpy. Since the ionization enthalpy decreases down the group, therefore, the reactivity of group 1 elements increases in the same order : Li < Na < K < Rb Cl (+ 1-36 V), Br (1-08 V) and 1 (+ 0-53 V), therefore, their reactivities also decrease in the same order : F > Cl > Br >I. : Alternatively, tendency to accept electrons can be linked to electron gain ). Since electron gain enthalpy becomes less and less negative as we move from Cl to I, therefore, 1 y tol, F, however, is the most reactive due to its low bond dissociation energy. ctroni oo Gare f-block elements :_ at teeoe aot pn anoanve tes aeVmIeNCE element with a valence of 8-5 = 3. Thus, the formula of the compound (magnesium nitride), of 2. Nitrogen is a group 15 formed would be MgsN, ( Aluminium is group 13 element with a valence of 3 while i lence of 1. Therefore, the formula of the compound formed would be All (aluminium iodide), sili ‘ygen is a group 16 element with a val of 2. Hence the formula of the compound formed is SiO, (silicon dioxide), ka (€) Phosphorus is a group 15 element with a valence of 3 or $ while fluorine is a group 17 element with a valence of 1. Hence, the formula of the compound formed would be PF; or PFs. (f) Element with atomic number 71 is a lanthanoid called lutetium (Lu). Its common valence is 3, Fluorine is a group 17 (halogen) element with a valence of 1. Therefore, the formula of the compound formed would be LuF; (lutetium fluoride). |, 3.33. In the modern periodic table, the period indicates the value of (a) atomic number (b) mass number (c) principal quantum number (d) azimuthal quantum number ‘Ans. In the modern periodic table, each period begins with the filling of a new shell. Therefore, the period indicates the value of principal quantum number. Thus, option (c) is correct. ). 3.34. Which of the following statements related to the modern periodic table is incorrect ? (a) The p-block has six columns, becaue a maximum of 6 electrons can occupy all the orbitals in a p- subshell. (b) The d-block has 8 columns, because a maximum of 8 electrons can occupy all the orbitals in a d- subshell. (©) Each block contains a number of columns equal to the number of electrons that can occupy that subshell. (d) The block indicates value of azimuthal quantum number (1) for the last subshell that received electrons in building up the electronic configuration. ‘Ans. Statement (b) is incorrect while other statements are correct. The correct statement (b) is : the d-block hhas 10 columns, because a maximum of 10 electrons can occupy all the orbitals in a d-subshell. ). 3.35. Anything that influences the valence electrons will affect the chemistry of the element. Which one of the following factors does not affect the valence shell ? (a) Valence principal quantum number (n) (b) Nuclear charge (Z) (©) nuclear mass (@) Number of core electrons. ‘Ans. Nuclear mass does not affect the valence shell because nucleus consists of protons and neutrons. Whereas proton, ie., nuclear charge affects the valence shell but neutrons do not. Thus, option (c) is wrong. ‘The size of isoelectronic species - F-, Ne and Na* is affected by (a) nuclear charge (Z) (b) valence principal quantum number (n) (c) electron-electron interaction in the outer orbital peponecr ibe cia wuclear charge (Z). As the nuclear charge increases : isoelectronic ions depends upon the nuclear . i pers "For example, F- (+ 9) > Ne (+ 10) > Na* (+ 11). Therefore, statement (a) is correct ‘hile all other statements are wrong. 1. Which of the following statements is incorrect in relation to ionization enthalpy ? (@) ionization enthalpy increases for each successive of electrons from core "(b) The greatest increase in ionization enthalpy is experienced on removal “noble gas configuration. fs ‘odine is a halogen (group 17) with anape nenng ete nc electron gain enthalpy and electronegativity. The main points of difference a het