—_—_———— : MODERN COLLEGE CHEMISTRY SEM"LC.B.0-S (THEORY) Electronic Configuration of Elements Ttis governed by following rules : an ing rules : @ Aufbau principle, Gi) Pauli’s exclusion, oe (iii) Hund’s rule of maximum multiplicity. (iv) Stable configuration. 1. Aufbau principle (German ; aufbau means building uP) orbitals in the order of their increasing According to this principle. “The electrons are filled in various eee f the two sub-shell can Thus an orbital with lowest energy will be filled first. The energy content of be compared by means of (n + /) rule as explained below. id ta hited ene (@ The sub-shell with lower (n +2) value will possess lower energy and will be 8 4s-sub-shell is filled first than 3d. a] ef Subshell] ts | 28] 2p] 3s] 3p ]3d] 4s | 4p | 4d | 4f | 5 | Sp | 5d | Sf | 6s | SP. Ts mn {1f2}2]3/3/314/41414) 51> oe 3 : : t Jofofajoj1|2}o/1) 2) 3,0 eae a+r |il2 als{o{7{516|7181617) 819 @ Fords-subshell: (©) For 3d-subsheil:n + 1 = 3+2=5. Since (n + #) value for 4s-sub-shellis less than 3d, the 4s-subshell has lower energy and filled first. (@ The subshell with lower value ofn possesses lower energy if (n +2) values for both the sub-shells are equal, e.g, 3p-subshell is filled first than 4s. (@) For 3p-subshell : n +/=3 + 1 = 4,(b) For 4s-subshell : n+1=44+0=4 The value of n (= 3) is less for 3p-subshell as compared to n (=4) for 4s-sub-shell. Hence, 3p-subshell has lower energy than 4-subshcll and is filled first. Calculation of energy of various subshells. The above rules are applied to calculate the energy of various sub-shells. It is evident from the following table. The increasing order of energy of various energy subshells is as follows : Is < 2s < Ip < 3s < 3p < 4s < 3d < 4p < 5s < Ad < Sp Fig. 1.36. increasing order of energy of <659< Y< 5d < 6p <1 < $< 6d orbitals. The order is diagrammatically illustrated in Fig, 1.36, Limitations of Aufbau Principle 1. In the build up, although the number of electrons increases increases, ye, on ionisation the number of clectrons devrearee hate Teena same [in Na*, number of protons, i.e., nuclear charge = 11 while inuabet of close, imge remains the atoms are ionised, the electrons get removed first from 4s than Advorbita, Ie exe ee a 10). Also, when of combined effect of factors like nucleus-leciron attraction, interelectronie repmln enone P eleciron by another and exchange forces which determine the stability of elect ee ae shielding of onc be remembered tha during onion the fis! elcron sox from tat uta eto SS mand ifn same the he est clecuon st om thatsbahll whch has gaan Eas eT ee For example saat he first electron from Cr-atom [(1s4t) 34° 45) is lost during ioniesr; oes lectron as mee ‘onisation from 4s (n=4, 1=0) and no!ng be 1 a = 5 eva sh fe) 2 ATOMIC STRUCTURE 5 (6) the first electron from N-atom (15225? 2p}, 2p}, 2p!) is lost during ‘oni from 2p (n = 2,1 = 1» Py 2p3) is lost during ionisation from faeces 9» 2P:) is lost during ionisation from 2p (n = 2,1 = 1) 2. In third, fourth and fifth sub-shells, the (1 1) d and ns-sub-shells are ver 2 es, shes ont ih sub-shell, the (1-1) d and shells are very close in energy, But Thus, the predicted outer electron configuration of yoCu a not 3d" 4s! (found experimentaity) 3_Although 4f and Sd-sub-shells in the sixth period lie very, fose together yet the last electron does not enter in 4-orbital of lanthamum, s7La [(jgKr) 4d" 4f! 552 599 5? 607] as predicted by aufbau principle but in 5d Coe [s6Kr] 4a"? 55? Sp 5a 63%), On the other hand, cerium, saCe has two electrons in 4f-sub-shell (scKe] 44° 55? Sp 47 Sa° 6s?) instead of one (sgCe—[36Kr] 4c!° 5s? 4f! Sp° Sa! 6s), Here, the el previously present in Sd of s7L.a also gets shifted to 4f, 4. According to aufbau principle, the outer electronic configuration of technecium (,sTe ) should be $5? 4d° and not 5s! 4¢® (experimentally observed). This shows that preference of half or fully filled configuration is not the sole criterian for the stable configuration of an atom. On the other hand, some complex inter-clectronic repulsive forces and nucleus-electron attractive forces also contribute to decid about the correct configuration of atoms. 5. According to aufbau principle, the outer electron configuration of palladium 4,Pd should be Ss? 4° and not 5s° 4d" (found experimentally). This is the only element in which the experimentally found electron configuration has two misplaced electrons, Electronic Energy Levels Variation of orbital energy (@ Electronic energy levels for H-atom and monoelectron ions (He*, Li*?, ete.). cording to aufbau principle is...34° 4s? and Schrodinger determined the energy values for) —— hydrogen, He* and Li*?, etc., with the help of wave |e -G90-COCCcO—-8880082 equation. These values agreed well with the values 4s id at | found experimentally from hydrogen spectra. 2-000 These values have been shown in the encrgy level |-e-oco diagram for H-atom (Fig. 137). cet 2 ‘Observations. (a) All the orbitals with a given 8 Principal quantum number of shell ‘n’ have the Fig. 137, Electron Energy lovers for ator same energy, eg, in case of second shell (n= 2), 25, 2p,, 2py, 2p orbitals have the same energy, (0) The energy of different orbitals depends upon the value of ‘fn’, Greater the value of n, greater will be the energy of its orbitals. (ii) Electronic energy level for multi-electron atoms, The solution of Schrodinger wave equation is very complicated for multi-clectron atoms. Thus, the encrgies associated with various orbitals. could not be determined accurately. The energy ae Li be a determined experimentally from the fine spe Benes slic hee been shown in the encrgy level diagram for multi-electron atoms (Fig. 138) i ‘Observations. (i) All the sub-shells with a given principal quantum number ‘n’ do not have the same* MODERN COLLEGE CHEMISTRY SEM. C.8.C.S (THEORY, (ii) The various orbitals present in the same sub-shell possess equal energy. Thus, the energy of all the three orbitals (p,, p,,p,) of any level is the same. These are called degenerate orbitals. (ii) The sub-shells with greater value of (n + 2) possess more energy, ¢g, 34-sub-shell (n+ 1=3 + 2=5) possesses more energy than 4s-sub-shell (n + / = 4 + 0 = 4). (jv) The sub-shell with higher value of ‘n’ possesses more energy if (n + 1) value for both sub-shells is same eg, 4s-sub-shell (n + 1=4+0 = 4) possesses more energy than 3p-sub-shell (n +/=3 + 1=4) (v) Each energy level constitutes one electron shell, e.g, 1s ; 2s, 2p ; 3s, 3p 5 4s 3d, 4p; 5s, 4d, Sp and 6s, 4f, 5d, 6p constitute first, second, third, fourth, fifth and sixth electron shell respectively. (i) Each electron shell represents a period in the periodic table. Total number of electrons in each electron shell represent total number of elements in that period, e.g, Second electron shell (2s 2p' ») represents second period and contains, 2 + 6 = elements, ‘ Reason for different energies of orbitals in multi-clectron atoms. In multi-electron atoms (say y1Na = Is? 2s? 2p®3s1), the inner energy. levels (1s,2s, 2p) act as screens between nucleus and electron present in outermost energy level (351). These screening orbitals reduce the effect of attraction of nucleus for the electron in the outermost orbital, This effect is called screening or shielding effect. This effect is different on different types of orbitals. Hence electrons possess different energies in different sub-shells. Ditference of energy level diagram of hydrogen atom from that of multi-electron atom H-atom Multi-electron atom 1. |The energy of electron in one electron atom (H-atom) depends upon the value of ‘1’ (principal quantum number). 2. |All the orbitals present in a given energy level hhave same energy because there is only one. Ihe energy of electron in multi-electron at (ay Na-atom) depends upon the values of » land / (azimuthal) quantum numbers JAll the orbitals present in a given energy level lhave different energies duc to the shielding effect lof inner electrons. lectron and shielding effect does not take place, (I) Pauli’s Exclusion Principle (see page 45). (iD Hund’s rule of maximum multiplicity. According to this rule, “‘no electron pairing takes place in the orbitals of p, dand f-sub-shells until each orbital is singly filled with electrons having payallel spins.” Explanation of Hund’s Rule. In order to understand this rule, consider the electron. configuration of carbon atom, C(As* 2s? 2p%), Carbon atom has two electrons in its 2p-sub-shell, These two electrons can be distributed in p, ,p, and p orbitals of same energy as follows : Ps Pe Mere? Paik. Py rem Pa Py’ “Pe Ada = t ‘ teat: = @ i) (iii) Since electrons are negatively charged, these repel each other. Out " 2 configurations, the electron repulsions’ in. the state (il) are BLN SS, ef ero minimum where electrons are as far apart as possible with parallel spine. Thus the state (i) hs minimum repulsion’ which corresponds to minimum energy and maximum stability. Hund rule can be summed up into two rules, erie @ No pairing of electrons in omitals of same energy 2esPy Dosstaken placenniess each vial is segnfteds (i) When different orbitals of same energy are half or less than ‘half filled, the electrons should have parallel spins. It is because the parallel arrangement of spins is more stable than anti-parallel! arrangement. This rule is based upon the magnetic effect of electron spins, Importance. It is used to assign the clectron configuration of atoms. Applying Hund’s rule, the electron configuration of a few elements is given in fig. 1,39, Fig. 1.39 Application of Hund’s rule.STRUCTURE ii) Stable Configuration. Exactly half filled e 3 psn, nd!snf? and np and fully filled orbitals are most stable, configurations are most stable, d fully filled orbitals is given below: eg, let us understand some 5. Promotional energy, AE. Symmetrical and unsymmetrical ch: i cal charge distributi bi ae 8 ds onthe shape of orbitals and distribution of electron in varia bicge oe eae® Aistbution (i) s-orbitals. s' and s? orbitals bei i ical i orb Htals being spherically symmetrical in shape, have symmetrical charge (i) p-orbitals. Electronic charge distribution in halt-filled (p!, .},p3) and fully filled (p2 ls, is symmetrical while the rest arrangements (p!, p?, p* and p’) are unsymmetrical. i a. Electronic charge distribution in half-filled @y a, di, dle _,? and a!) and fully filled pten di _ y2 and d,2) d-orbitals is symmetrical while the rest arrangements (d}, d?, d°, d',d°, a’, d® Py P2) ) forbitals. Electronic charge distribution in half-filled ((”) and fully filled (4) f- orbitals is while the rest arrangements (FPP, f°/5, 7,942 andf) are unsymmetrical nt. Since half-filled and fully-filled orbitals have symmetrical electronic charge distribution, ‘more stable than other orbitals. : pt of Exchange energy ge energy = — E x (number of exchange pair of electrons) energy, P (or destabilizing energy). The encrgy required to pair up two electrons in the same ‘opposite spins (_) is called pairing energy. The pairing encrgy that corresponds to one electron ‘ons is denoted by letter, P. Pairing energy is shown by positive sign because the presence of rs increases the energy in a given clectronic arrangement and the arrangement becomes less energy for n electron pairs = nP. Where P isthe pairing energy for one electron pair mast stable We know that exchange energy stabilises and pairing energy destabilises the given system of ement of electrons. So, greater value of exchange energy than pairing energy would stabilise the given .For example, the decreasing order of stability of a given system having sum total ‘of exchange energy energy as (a) — E+ P (6) — 3E + OP and (c) — E+ OP is, @) > ©) > @). i omotional Energy, AE. The energy needed to promote an electron from lower energy orbital to ergy orbital is called promotional energy. ngement will be more stable if, AE arangements. l+Itit1 end (6) 4s" gement (a), there is one electron pair of 452, So, its pairing energy is = 1 x P =P. But AE = 0

P, arrangement (b) is more > P. For example, consider 24Cr-atom with outermost Iygh tit itil, ig one electron from lower 4s~ orb Shot or Qnertesyay