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Atomic Structure

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Atomic Structure

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Concept of Nuclear Atom ‘Anatom is the smallest particle of matter which takes part in chemical combination and is made up of smaller particles like electrons, protons, neutrons etc. At present, about 35 different subatomic particles are known but the three particles namely electron, proton and neutron are regarded as the fundamental particles. Electron, proton and neutron Electron is the fundamental particle of an atom having one unit—ve charge equal to — 1.6 x 107! coulomb and negligible mass of 9.1 x 108 g. Proton is the fundamental particle of an atom having one unit +ve charge equal to +1.6 x 1071? coulomb and mass of 1.67 x 104 g. Neutron is the fundamental particle of an atom having no charge and mass equal to 1.675 x 10 g Atomic number (Z) and mass number (A) Atomic number of an element is the number of positive charges (or the number of protons, p) present in the nucleus of the atom. Since the atom as a whole is electrically neutral, therefore the number of positively charged particles, i.e., protons present in the atom must be equal to the number of negatively charged particles, ‘c., electrons present in it Atomic number of an element (Z) = Total number of protons present in the nucleus = Total number of electrons present in the atom. Z=p=e ‘mass number of an element is the sum of the protons (p) and neutrons (n) in the nucleus of an atom. A=p+n=Ztn Rutherford’s Model of Atom From q-ray scattering experiment Rutherford observed that’ ‘© Most of the a-particles passed through the gold foil undeflected, ‘© Some a-particles were deflected at wide angles, @ Avery few (one in about 10°) were deflecteyp in their own path. tan, On the basis ofthese observations, Rutherford pu his nuclear model of atom. According to which ‘Atom is spherical and consists of two, cextranuclear part. Parmley Most of the mass and +ve charge of an gy concentrated ata very small region, whichis ag centre or nucleus of the atom. ts The nucleus is very small in the size of 10°! gm which is surrounded by electrons revolving sounds Extranuclear part is an empty space around thease, | where electrons are revolving ina circular orbit win high speed. This nuclear model is comparable to ou ie system in which planets are revolving around thes ‘© The electrostatic force between nucleus and ins is counter balanced by centrifugal force ating et revolving electron, | Limitations of Rutherford’s model | © Rutherford’s model failed to explain the stability an atom, as well as the existence of numberof insit hydrogen spectrum, | ‘© This model also failed to explain the arangenet electrons in the orbits, Line Spectra of Hydrogen Atom Hydrogen atom has only one electron but its specu | found to be made up of several lines, forming®! ine sper This was explained due to excitation of eles dl : large number of hydrogen atoms, to higher enev™ | absorbing energy from the electric discharge The excited state is shor lived (10 to 10") the electron falls back to lower energy levels radiant energy as well defined lines or bands) No two atoms can have identical line spec ‘atomic or line spectrum is regarded as finger POMS | a ey is emitted or absorbed not continuously but discontinuously in the form of small discrete packets of Each such packet of energy is called a quantum. ~ jpense oflight, the quantum of energy is called photon, ‘the enery, F of each quantum is directly proportional the frequency v of the radiati jeEXd 0% ‘shere fis a proportionality constant called Planck’s constant and its value is approximately equal to 6626 « 10° Js. 4 The total amount of energy emitted or absorbed by a body will be some whole number quanta, Hence, E=nhv, where n is any integer. + The energy possessed by one mole of quanta (or photons), ie, Avogadro’s number (Ng) of quanta is called one Finstein of energy. ie., +1 Einstein of energy (£) = Noirv = Noh a Bohr's Model of Hydrogen Atom | Thismodelis based on quantum theory of radiation and only ‘plicable for single electron species like H, He’, Liz”, etc. Postulates of Bohr’s model * The electron in an atom can move around the nucleus indefinite circular paths; called as shells or orbits, ic. KLMN, ete, * een can move in that circular path for which angular Momentum of electron is either “or integral multiple on 874 which means angular momentum of electron is ‘Quantized or fixed nh 26, mvp = rm there h = Planck’s constant 4112.3, represents K, L, M.. shells. {F< 00g asthe electron moves in a particular orbit, its of se) Temains unchanged, But emits energy inthe form. when it jumps from higher energy level to electron and m is mass of an electron, ‘The velocity of an electron in the state (,) 2nkZe* th © Theenergy ofan electron in the n'" orbital, E,, is given by =2.18«10° Zs a eee 1810782? 6.023210" yy on Ey ee area Also £, =13:9%22 oy atom (1eV =1.6x107! 3) n ‘© When an electron jumps from one outer orbit (higher energy) 1, to an inner orbit (lower energy) n,, then the nergy emitted in the form of radiation is given by 2 metZ? ( lal } AE=E,,~E,, Tee => se=21bsi0 | Also, AE =13.6 2? (5-4 Joao nom # B=hy; e=vA and D=7 2k met oh and ) = wave number. R= Rydberg constant and its value is 1.097 « 107 mo! 1 Z } where R= _ Limitations of Bohr’s model * Itcouldnot explain the spectra of multi-eleetron species, __& Modern researches revealed that electrons move in three dimensional and elliptical paths, while according to Bohr, electron moves in cireular path. Itis an extension of Bohr’s model, To account for the fine spectrum of hydrogen atom, Sommerfeld proposed that the electrons in an atom revolve around the nucle! in elliptical orbit. The circular path is a special case of ellipse. Association of elliptical orbits with circular orbits explain the fine line spectrum of atoms. 3k=3 88 3s, 3p and 3d with 50,1 andy ‘The th shell (n = 4) has four subshel ae ak? with values 0, 1,2 oat Alay ‘and 3. The total number ‘of — tia any shell is same as the principal quaint 5 Magnetic quantum number (m) This gives the number of orbitals in, a sub. shell takes integral values fro + ee: Fig Sommerfeld orbits in hydrogen atom Fee OF ah aay toueh zero, No.of oa _ Vales of m = 21+ for any val The model has following features m dele he orien fe subset * The motion of electron in closed circular orbits isis only one orbital. (Sine /=0,Q/ 1) <4 influenced by its own nucleus and is set pinto closed In p sub-shell there are 3 orbitals 1, 0 andy Ay elliptical paths of definite energy levels = 1,14 1)=3)-THe3 orbitals are designatedasp, ag Pog ‘The nucleus is one of the focii for all these orbits, , where x,y and z refer othe axes perpendicular eeah oe © The angular momentum of electron in closed elliptical other in spac a s also quantized, xe. k(i/2m), where kis another Ind sub-shells there are S orbitals 2, 1,0, + tanger, et except zero. [/=2, 21+ 1)=5}. The five orbitals are representedasd,,d_ 9 doo dss andd.s paces Inf sub-shells there are 7 orbitals 3, 2,10, #1, 2and3 possible number of sub-shells in a shell [=3, 0+ 1)=7) e '* Possible values of k for =4 are 1, 2,3, 4 respectively. Spin quantum number (s) Forany given value ofn, k cannot be zero as in that case, the ellipse would degenerate into a straight ine passing through the nucleus. When =f, path becomes circular When an electron rotates around a nucleus, it also spins jh about its own axis. Ifthe spin is clockwise, its spin quantum by number is +1/2 and it is represented by 1. Ifthe spits ig anticlockwise, its value is 1/2 and is represented by }.185 44 Quantum Numbers value is +1/2, then by convention, we take that electron 3s 3) the first electron in that orbitals and if's value is 1/2, is 4) taken as the s It is defined as, a set of four numbers which gives complete | information about the electron in an atom i.e. energy, orbital | occupied, size, shape and orientation of that orbital and the direction of electron spin, There are four quantum numbers: Eleetronie Configuration of Elements t .cond electron, Principal quantum number (n) The filing up of electrons in different orbitals is efe@lO Itrepresents the main electronic energy shells fom nucleus. as electronic configuration, The filling up of eleevuns'® It can have only integral values like 1, 2, 3,4...etc. The different orbitals is based on the following rules. \ -orresponding shells are also known as K, L, M, N shells a eee ih the absence of any external field, it mainly _ Aufbau’s principle teen decides the energy ofthe electron inthe orbit, It also gives Am electron enters the sub-shell that has the TT the number of the electrons that may be accommodated in The sub-shell are filled in the increasing owe, ‘ach shell, the capacity of each shell being given as 2n?, | Is <2s <2p<3s<3p<4s <3d<4p<59 >rincipal quantum number decides the size of a shell 3d" or that in 3d! > 349, Hlectronic configurations of cations and anions Cations are formed by loss of electrons by atoms. First, #esttonic configuration of atom is written and then electrons ate removed equal to the units of +ve charge, starting from the outermost shell, Anions are formed by gain of electrons byetoms. Electrons equal to the units of -ve charge are added ito the electronic configuration of atom. Dual Behaviour of Matter In 1924, de Broglie proposed that an electron, like light, behaves both as a material and as a wave. This proposal Heisenberg’s Uncertainty Principle According to this principle, it is impossible to measure simultaneously the position and momentum of a small particle with absolute accuracy or uncertainty, ‘The product of the uncertainty in the position (Ax) and the uncertainty in the momentum (Ap =m - Av) where m is the ‘mass of the particle and Av as the uncertainty in velocity is always constant and is equal to or greater than hi4, where ‘his Planck’s constant, ie., Ax Ap > h/4r Atomic Orbital The three dimensional space around the nucleus within which the probability of finding an electron of given energy is maximum, is called atomic orbital. Atomic orbital is the spatial description of the motion of an electron corresponding to a particular energy level. The energy of electron in an atomic orbital is always the same. ‘Shapes of atomic orbitals Shape of an orbital is given by total probability density ‘y? including both radial part as well as angular part. Shape of s-orbital : Shape of s-orbital must be spherical since probability of finding electron is equal in all directions at a distance from nucleus. Shape of p-orbital : The probability of finding p-electron is maximum in two dumb-bell type lobes on the two opposite sides of nucleus. Thus, porbital has dumb-bell shape. In the three p-orbitals, p,. p, and p. the probability lies maximum along x-axis, y-axis an; ia tal ‘The point where there is zero probability of finding an electron is called nodal point or node, prorbitals possess one nodal plane passing through the nucleus. y orbital xis respectively. Which of the following is not correct for electronic distribution in the ground state? dy 3d. (@) Co=far] [tl] [NIT tt @ ni=taq [1] [ulna |t (©) Cu=fAar] ty) [tint tl t (@) dn= far) tl] [raied nent Which one of the following sets of quantum numbers Tepresents an impossible arrangement ? Tope me Le: (a) 3 2 7. V2 4 0 0 12 Oe tieeg e 1) (d) 5 3 0 12. Ina set of degenerate orbitals, the electrons distribute themselves to retain like spins as far as possible. The ‘Statement is attributed to (a) Pauli exclusion principle (b) Aufbau principle (c) Hund’s rule of maximum multiplicity (d) Slater’s rule. When the value of the azimuthal quantum number is 3, the magnetic quantum number can have values (a) +1,-1 () +104 (©) +2,+1,0,-1,-2 (d) +3, +2, +1, 0, -1,-2,-3. A tansition metal X’has a configuration [Ar] 3d4 in its + 3 oxidation state. Its atomic number is (a) 25 (b) 26 (c) 22 @ 19 The orbital angular momentum of an electron in 2s orbital is 1 O55 a (b) zero. hh h © > @ V2 10. u. 2 1B. 14. In Balmer series of hydrogen atom electronic transition causes third line ? (a) Fifth Bohr orbit to second one (b) Fifth Bohr orbit to first one (c) Fourth Bohr orbit to second one (d) Fourth Bohr orbit to first one A photon of radiation of wavelength 4000 A has y energy E. The wavelength of photon of radiation having energy 0.5 E will be (a) 2000A (b) 80004 (c) 4000A (d) 6000 A. Among the following groupings which represents te collection of isoelectronic species ? (a) NO*,C},03,CO__(b)_N», C3, CO,NO (©) CO,NO",CN,C}, () NO,CNN?0; The number of d-electrons in Ni (at. no. = 28) is equal to that of the (@)_pelectrons in F (b) pelectrons in Ar (c) delectrons in Ni?* (d) total electrons in N. Which is the isotone of 7$Ge? 7, Mees () BGe () HSe (© Per @ fee ‘The first emission line in the H-atom spectrum in the Balmer series will have wave number Beene Se f@) Seem % 5 (c) oem! (d) aan! If the ionisation energy of hydrogen atom is 136e¥ the energy required to exeite it from ground salt the next higher state is nearly (@) 34e0V (b) 10.2eV (©) 11eV (@) 15eV. : The one electron species having ionisation ene)" J 54.4 eVis (@) H &) He @ BY @ ee ‘m/s, The uncertainty in its position will be rsa) @ Saree () 1.05% 102% m o 1,05 «107m (@) 5.25% 107% m of the following expression gives the ge Broglie relationship ? b om Si lis @) am=* | P the values of m and ny in the ‘my For the Paschen series 1 1 (|) fi @ m=4m Y8§ 31, Proton was discovered by (@) Chadwick (b) Thomson (@) Goldstein (@)_ Bohr. | 22 Forprincipal quantum number n = 4, the total number | of orbitals having != 3 is PF @3 ®5 O7 9. 23. Consider the ground state of Cr atom (Z = 24). The number of electrons with the azimuthal quantum Oe » sperinsiis numbers = 1 and 2 are respectively (a) I2and4 (b) 12 and 5 (©) 16and 4 (@) Wands 4, Aspecieshas 16 protons, 18 electrons and 16 neutron Find the species and its charge. a OS ws @ PH aad ji The number of d-electrons retained in Fe** (At. no. of pos Fe=26) ion is eeeyase (c) (6 (a), 3 i HP Which of the following ions has the maximum | Magnetic moment? (@ Mn (b) Fe (c) Ti (d) Cr” 27. The spectrum of He is expected to be similar to that of @) Hb) Nae) Het (@) Li’. 30, Which of mathematical uncertainty principle? (a) Avdp2 hin) () AvAmv2 hin) |. The ratio of the difference in energy between the first ‘and the second Bohr orbit to that between the second and the third Bohr orbit is I 1 os mens Oo mC ies 32, The orbital diagram in which both the Pauli’s exclusion principle and Hund’s rule are violated is @ (ij fh co (1) {r[it © Wil @ [my] (ful 33. If electron, hydrogen, helium and neon nuclei are all moving with the velocity of light, then the wavelengths associated with these particles are in the order (a) electron > hydrogen > helium > neon (b) electron > helium > hydrogen > neon (©)_ electron < hydrogen < helium < neon (d)_neon < hydrogen < helium < electron. Which one of the following set of quantum numbers is, not possible for 4p electron ? 44 @ The nucleus of an atom can be assumed to be spheric: ‘The radius of the nucleus of mass number 4 is given by 1.25 « 10-13 « 41 cm. Radius of atom is one A. If the mass number is 64, then the fraction of the atomic volume that is occupied by the nucleus is (@) 1.0 «10% (b) 50x 10% (c) 25x 107 @ 1.25* 10-9 36. Assuming Rydberg constant (Rj;) to be 109670 cm! the longest wavelength line in the Lyman series of the hydrogen spei (a) 121584 (©) 97264 35. (b) 1025.8 A (d) 949.8 A. b) y: nain and z) (©) both y and will be doubled (@)_ywill be doubled but z will remain same, 38. A particle 4 moving with a certain velocity has a de Broglie wavelength of 1A. If particle B has mass 25% of that A and velocity 75% of that of 4, the de Broglie wavelength of B will be approximately (a 1A) 53A (©) 3A (a) O2A 39. In and J are respectively the principal and azimuthal ‘quantum numbers, then the expression for the calculation of the total no, of electrons in any energy (gy level is (b) The product of velocity of principal quantum number e 2? 3 Fi f shui equeney, of revolution of the electoy fy. ro st tect | orbit @ L20l+p © ¥ 221+ a 3 el ‘a | @)_ Velocity ofthe electron « © 7) (a) | 48. Which of the following statements are eo (@) For all values of m, the p orbitals have the say shape but the overall size increases a inne for a given atom. 40. Which of the following element outermost orbit’s last electron has magnetic quantum number m = 0? @N 60 @©A @Nn. (b) The fact that there is a particular diecton 41. Correct energy value order is which each p-orbital has maximum eleny (a) ns np nd (n—1)f | density, plays an important role in detemizy eee iGo molecular geometries, ROP canta en iy | © The charge cloud of a single elcron in ERGs CaN omic evil consis of two lobes of da 42. The value of Planck’s constant is 6.63 104 Js. The @) Nae ee Sslociy of light is 30 «108 psy. WhichNAIUE is’ | 49, Wich of me following saa closest to the wavelength in nanometers of a quantum ‘electron that has n= ae ae of light with frequeney of 8 x 10!% 5-1? (a) The electron may be in a p-rbital. (@ 2«10% @) 5x10" | (b). The electron is in the fourth principal eestn: © 37.5 (a) 26.7 shell, (c) The electron may be in a d-orbital 43. In Bohr series of lines of hydrogen spectrum, the third line from the red end corresponds to which one of the (d) The electron must have the spin “— following inter-orbit jumps of the electron for Bohr number = -1/2, orbit in an atom of hydrogen? | 50. Which of the following is/are not correct? (a) 532 () 451 (2) Isotones differ inthe number of neurons (©) 295 @) 332 (b)_ Isobars contain the same number of neu! 44, Inthe Bohs ori, what i the aio af total Kinetic | Neen eee 4 energy and the total energy of the electron (@). Density of nucleus is much greater tan @-1 & 2 © @ +2 son 45. The frequency of the radiation emitted when the —§1, For which of the following species the & sao falls from = 4 t0 n= 1 in a hydrogen atom | for the energy of electron inn rit will be (Given ionization energy of H= 2.18 * 10-'8J atom! («, 3.6 and h = 6.625 * 10° Js) (a) 1.54 10!5 5" (b) 1.03 « 10!5 st (a) He? (ce) 3.08 « 10! 5! (d) 2.0 105s. | (¢) Deuterium 3B electrons have a spin of one type. of a es opposite type. (Atomic number of F a) umber of orbitals in a. shell with Eel number is 2n? __tjal probability cistibution curves which om owing isfare correct? x enunber of nodes in any orbital Fpemumber of radial nodes is n= [— 1 hte 439 shell, energy increases in the order; | 45 p< i. ig Trenumber of angular noes ofthe following pats of electrons, identify the pairs of electrons present in degenerate orbitals. 1 () @n=3,!=2,m,=-2, m,=-5 =i =3,1=2,m)=-I,m, = ees = 1m = |, moth | (in=3,1=2, m=2, m, =+ (i)n=3,1=2, m= @ 1=2,m=+2, m, = ()n=3,122,m=+9 m= sts 58. hy is (al (a) -34eV (©) -6.8eV a Which of the following statemer (a) The mass of neutron is slightly proton. (b) e/m ratio of particle in anode rays di upon the nature of the gas taken in the disc tube. (0) InH-atom, the electron revolves ata fixed distance: 0f 0.53 A. (4) Angular momentum of all s-electrons is same. The sum of the number of neutrons and protons in the isotope of hydrogen is (a) 6 (b) 2 (c) 4 (d) 3 According to Bohr’s theory, (a) when the atom gets the required energy from the outside, electrons jump from lower orbits to higher orbits and remain there when the atom gets the required energy from outside, electrons jump from lower orbits to higher orbits and remain there for very short intervals of time and return back to the lower orbit, radiating energy. angular momentum of the electron is proportional to its quantum number angular momentum of the electron is independent ofits quantum number, 0) (c) @ . For a d-electron the orbital angular momentum is @ 2 © CL fr @ Ver . Which of the following configurations are correct in the first excited state? (a) Cr: [Ar] 35 4s! (b) Mn?" : [Ar] 3a5 (©) Fe: [Ar] 35 4s! (4) Co* : [Ar] 35 4s! HINTS & SOLUTION 2013-2019 CATEGORY 1: Single Option Correct Type (1 Mark) The emission spectrum of hydrogen discovered first and the region of the electromagnetic spectrum in which it belongs, respectively are (a) Lyman, ultraviolet (b) Lyman, visible (c) Balmer, ultraviolet (d) Balmer, visible. (2014) 2. As per de Broglie’s formula a macroscopic particle of mass 100 g and moving at a velocity of 100 cm s' will have a wavelength of (a) 6.6% 107% cm (b) 6.6 10% em (©) 6.6107! em (4) 66% 10°? em (2014) ‘The electronic configuration of Cu is (a) [Ne]3s73p°3d94s? (b) [N p°3d!%4s! (©) [N °3d*4s*4p° (d)_ [Ne]3s73p°3d°4s74p* (2014) 4, The energy required to break one mole of hydrogen- hydrogen bonds in H, is 436 kJ. What is the longest wavelength of light required to break a single hydrogen-hydrogen bond? (@) 68.5nm (b) (0) 274mm (d) 137 nm 548 nm. (2016) Which one of the following corresponds to a photon of highest energy? (a) 4=300nm (b) (© 0 =30cm" (@) 3x 108s! 6.626 x 10 °7J (2017) WB JEE Previous Years Question 6. Ifthe given four electronic configurations @) n=4/=1 (i) n=4,1=0 (iit) n=3,1=2 (iv) =] are arranged in order of increasing ener, the i order will be €@) ivy

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