Electronic configuration of Atom Lecture 7 Week 4Wave Mechanics From previous lecture we know that, Light as well as heat energy exhibits both wave and particle nature under suitable conditions = Wave mechanical theory | A | AL L. de Broglie (1892-1987) In 1924, de Broglie proposed that if energy is particle like, perhaps matter is wavelike According to his theory, e", p* and even atom, when in motion possessed wave properties and could be associated with A, v and A = this is WAVE MECHANICS For light: E=hv=hce/a For particles: E = mc? (Einstein) Therefore, |mc=h / and for particles (mass)x(velocity) =h / 2* If particle travel in waves, e should exhibit diffraction & interference - in 1927, Davisson & Germer guided a beam of electrons at nickel crystal and obtain a diffraction pattern. Ex: see Fig. 7.14 of page 271 of your reference Silberg Chemistry book Do a math: a) a stone of mass 100gm moving with a velocity 10m/s. What is the de Broglie’s 4 for the stone? b) ane in H atom has a mass 9.1091<107* gm and moves with a velocity 2.188x10* cm/s. what is the de Broglie’s 4? Wave length of X-rays is Inm = 110° m. Compare X-rays ) with de Broglie’s A.Uncertainty Principle So, in . macroscopic world, a moving particle has a definite location . at any instant and a wave is spread out in space. W. Heisenberg 1901-1976 Ifan e has the properties of both a particle and a wave, so we should be able to determine the location of e in the atom. In 1927, W. Heisenberg postulated, The Uncertainty principle, which states that it is impossible to know simultaneously the exact position and momentum (velocity) of a particle/ electron. Heisenberg’s relationship is: Ax.m Au2>h/2a This uncertainty product is negligible in case of large objects It means that we can not assign fixed path for e, such as circular orbits of Bohr’s model At best we can do is find the probability of finding an e with a probable velocity.¢ Using this idea, Schrodinger developed a mathematical model based on wave mathematics to describe the position of e in an atom=calculation of the probability of finding e at various points at atom. ¢ For a given atom, Schrodinger's Equation has many solutions, and each E, Schrodinger solution is associated with a given wave 1887-1961 functions, ¥, a mathematical description of electron’s motion, also called Atomic YW does NOT Orbital. describe the exact location of the electron, but ¥ 7 is proportional to dy dy a vy the probability + of finding an e- de ay “ at a given pointORBITAL The three dimensional region within which there is higher probability that an e having certain energy will be found is called ORBITAL, The energy of e in an orbital is always same Zz (a)Dot mttrnofan ekctonvritha & 1 atomic orbital Bach dot presents the (b).A plotod the probability density asa ‘position of the election at a diferent fiction of distance: for a one-electron mstantin time. atom vritha 1a electron, Ye is proportional to the probability of finding an e- at a given point.Quantum number of an atomic Orbital By examining the probabilities given by a particular orbital, a "shape" of the orbital can be seen. This shape represents a space around the nucleus that the electron is most likely to be found. The many solutions to Schrodinger's equation can be classified by the shape that is from their probability distributions, called orbital, like s, p, and d-type, as shown above. Most orbital types have several possible orientations too. An atomic orbital is specified by three quantum numbers. One is related to orbital’s size, another its shape third its orientation in spaceThose are principal (7), angular (J), and magnetic (m) quantum numbers nim magnetic -l, 0,1 orientation ‘angular momentum 0, 1,2, ...,(- 1) shape principal 1,2,3,... size and energyQuantum number of an atomic Orbital * Those are the principal (7), angular momentum(), and magnetic (m) quantum numbers. ¢ The principle quantum number (n): It actually denotes the principal shell/energy level to which electrons belongs at the atom. It represents the avg. size of atom. /ncase of H atom it represents the only orbital of it. n is a positive integer (1,2,3,....... 7) In n’th energy level, atom can have only 2n? number of electrons Max. number of electrons in n’th shell/level 2 8 18 32Angular momentum quantum number (/) It is an integer from 0 to (n-1) It is related to the shape of the orbital 1=0= (Is) 1=0, 1 = (2s, 2p) 1=0, 1,2 = (3s, 3p, 3d) 1= 0,1, 2, 3 = (4s, 4p, 4d, 4f) designated by letters 1=0 — s orbital 1=1_— porbital 1=2 = dorbital 1=3 = forbitalMagnetic quantum number (/) It is an integer from —/ through 0 to +/ It is prescribes the orientation of the orbital in space around nucleus n=1 1=0 m=0 1 n=3 1=0 m=0 | s P n=2 1=0 m=0 1 /=1 m=-l p I=1 m=-1, m=0 \3 = =1 m=0 3 d m m=1 1=2 m=-2 m=-l m=0 > PeShells and Subshells An atomic orbital is defined by 3 quantum numbers: = nim Electrons are arranged in shells and subshells of ORBITALS . n— shell 1 ~ subshell m— designates an orbital within a subshell For, n= 1,1=0 andm= 0 There is only one subshell and that subshell has a single orbital (m has a single value ---> 1 orbital) This subshell is labeled Ss and we call this orbital Is Each shell has 1 orbital labeled s. It is SPHERICAL in shape.p Orbital For, n=2, 1=0 and 1 There are 2 types of orbitals — 2 subshells Forl=0 m=0 this is a s subshell Forl=1 m,=-1,0,+1 this is a p subshell with 3 orbitals & d Orbital For n=3, what are the values of 1? 1=0, 1,2 and so there are 3 subshells in the shell. + Forl!=0,m,=0 — s subshell with single orbital ¢ Forl=1,m,=-1,0, +1 — p subshell with 3 orbitals ¢ For!l=2, ¢ m, = -2,-1,0,+1, +2 — dsubshell with 5 orbitalsShape of Atomic Orbital 1s orbital spherical Q Q Is 2 Re Nodes ) Is 2s ay ‘ig-’ f Silberg Chemistr Page 278Shape of 2p Orbital dumbbell shape mx -x -x 2p, orbital 2p, orbital 2p, orbital B 3p, 4p, 5p etc. are similar shapes but larger sizen= 3,1=1 Orbitals (3p, 3p, 3p, ) Tuy yryrTyy . aeneee vy yvyy vryyy y y y aan soon ’ hoy ow = Lin ao = a) . i t3d orbitals x ne cloverleaf z z y y y * 7 dy, largern same shapes but size larger ) ~ dyRepresentation of 4f Orbitals Ire foe hyaay HEHE Sie-2) Lie-19 Sie1 Sh Also see Fig - 7.17 & Fig - 7.18 & Fig — 7.19 and Fig - 8.9of your reference Silberg Chemistry BookSpin Quantum Number (s) * The spin quantum value indicates that the electron is spinning on its axis in one direction (clockwise/anti clockwise) or the opposite. * It can have a value of-1/2 or +1/2 only * The value of s does not depend on any other quantum number * These spins are also designated by arrows pointing upwards and downwards as | |Do this math * Which of the following sets of quantum numbers are not allowable and why? a) n= 2, l=2, m=0, s=+1/2 b) n=2, I=0, m=-2, s=-1/2 c) n=3, I=2, m=+2, s=-1/2 + What designation are given to the following orbital? a) n=4, 1=3 b) n=5, I=0 c) n=2, I= 1 * Write the missing quantum numbers & sublevel names mm name | a) 2 0 Ap 2 b) 2 1 0 2 ) 3 2 2D 2 d) 2 2 2sPauli’s exclusion principle * In 1925, Wolfgang Pauli discover the principle that governs the arrangements of electrons in many electron atoms * The Pauli exclusion principle states that no two electrons in an atom can have the same set of four quantum numbers n, |, m, s. * For a given orbital, thus e value of n, I,m are fixed * Thus if we want to put more than one e in an orbital and satisfy the Pauli exclusion principle, our only option is to assign different values of s to those two e * We know that their can be only two s value possible for e * We conclude that, an orbital can hold a max. of two e, and they must have opposite spin.Example of Pauli’s Exclusion Principal: * Consider the second shell (n=2) * There are 4 orbitals, one s orbital (I=0) and three p orbitals (I=1) NNN NN NNN Ss -_ e -ecoke +1/2 2e are in 2s -1/2 orbital a 2 e are in 2p, -1/2 orbital +2 2 e are in 2p, -1/2 if orbital +1/2 2 e are in 2p, -1/2 orbitalElectronic configuration Numberof | No of | Electronic Subshel Orhitasinthe, Sy | CCmfiguration o | mt Notation Subshel shell of shell 1s? |) ) ly | Z > 0 0 4 | 2 2s'2p r | -1,0,+1 » j 6 30 0 4 | 2 3s°3p3d"° 31 “1041 yp 3 6 Sa -2,-1,0,t1,+2 M 5 10 4 0 0 4s | 2 4s°4p°4d"° 4] -1,0,41 4p 3 e af 4 2 -2-1041,42 Ml j uy $9 ARM HAB F 7 M4Rules of electronic configuration of atom « Each e shell can hold max. 2n? electrons * Pattern of e entering in shell: — b>? — 3 — 4 — 5 — 6 —>7 * Pattern of e entering in subshell: —S—»p>d —f * Entering of e in orbital/ Hund’s rule: Electrons are distributed among the orbitals of a subshell in such a way as to give the max. number of unpaired e and have the same direction of pairRules of electronic configuration of atom Aufbau or Building up rule Electrons tend to occupy the available orbitals in increasing order of energies, the orbital of lower energy being filled first. This is building up/Aufbau principle (n+) rule The energy of an orbital is determined by the sum of principle quantum number (n) & the angular quantum number (1), this is (n+1) tule «If in case of two orbital having the same (n+l) value, the orbital with with lower value of n has lower energy.The relation between orbital filling and the periodic table ‘sthck flock abock pbockWrite electron configuration of the following elements * 0(8)=? * K(19)=? * C(I) =? * Fe (26) =? * Zn (30) =? * Pb (82)=?Electron configurations in the first three periods. He PeriodOrbital occupancy for the first 10 elements, H through Ne.Atomic Number/ Element 1/Na 12/Mg 13/Al 14/Si ISP 16/S 17/Cl 18/Ar Partial Orbital Diagram (3s and 3p Full Electron Sublevels Only) Configuration 38 3p [1s?2s?2p°] 30! [1s°2s?2p"] 3° Lb Hund's, “fis'2e22p") 3 3p! [1s°20?2p"] 3s°3p? [1s°20?2p"] 39°3p3 [Is°2s°2p°] 3°34 [1s°2s?2p"] 39°3p5 BE SEEBSES8B 2 BREEFH| [ly°2s?2p5] 35°3p° Condensed Electron Configuration [Ne] 3s! [Ne] 3s? [Ne] 35°3p! [Ne] 35°3p? [Ne] 35°3p° [Ne] 3s°3p* [Ne] 35°3p* [Ne] 35°3p°Atomic Partial Orbital Diagram Full Electron Condensed Electron Number Element (i Shand dp Salve nh) Configuration Configuration 4s Md 4p 9 K a [1s?22p°3923p9] 4s! {Anas » Ca a LTT] [1372s?2p35%3p5) 4s? [ar 4? 11 Se a ny (Is?22%p%9ep5]42sd! anya 2 Ti a [tht] [Is?2eap Pap ]4rae [Ardea B v a inn [| CLL] tare aripsiate —— tanarut u c fi GA {1233p Asuras 5 Mn a [tLtTtTt Tt] (Is?2eapS3Pap] 428 [Arp 4a 6 ke a Mel) LTT] tsaraprtisrt adr u Co a Math) (Isa 2p%aeapS] atid? an} 4seaa? 8 Ni fj eT") (IsP2s?apSep asta? arpaAtomic y 0 31 2 3% Br BE EB EB BBE: grams and Electron Config Partial Orbital Diagram Number Element (4s, 3d, and 4p Sublevels Only) = BAG: Full Electron Configuration {1s?2s?2p%3s°3p* 4s'ad"® [1s?25?2p°3?3p5] 45230” [1s?25°2p°3?3p°]4s°30%4p! [1s?20P2p%993p°|45°34!4p? [1s?25°%p°3?3p°]4s°3a4y* [1s?25°%p°3e°3p°]45°3a%4y* {1s?2s?2p"3?3p*] 423d! {1s?2s?2p%8s?3p"| 4s°3d!%p6 Condensed Electron Configuration far] 4st3d!® (Ar) 42x [Ar] 40°3d!%4p! [Ar] 45°34!4p? [Ar] 45°34! [Ar] 4°3d!%p4 (Ar) 4?3d!%4p8 [Ar] 4°3d!%4p6Period number: highest cccupied energy level A periodic table of partial ground-state electron configurations eae MairGroup Elements eek (peck tA aA dw (te) 1s rae mm aA] A] A] A] 7A ae c13i_| v4) | 5) | 6) | 17) a? 70g | ro apr ro a 6 | 7 | 6 4 3 | —s—] 18 | 2 i s | ci | ar «) oH | —@ c0)} on) | aa) a fay “Lanthanioos 7 "Astinioes gealtze| baaligeAssignment 1 * Questions number 5, 9, 12, 16 & 23 to 33. * Among these 14 questions answer any 7 questions * Clearly write your name & ID no in the front cover of your assignment sheet * You can submit the assignment in hand written or as printed form, as you like * Last date of submission of Assignment 1 is November 15, 2008. * Ifanyone submit the Assignment | before November 8, 2008 then he/she will be given Bonus 2 marks at the final * If anyone answers all 14 questions correctly and submit his/her Assignment copy then he/she will be rewarded with Bonus 5 marks at the final