32 ATOMIC STRUCTURE INTRODUCTION Jobn Dalton 1808, believed that matter is made up of extremely minute indivisible particles, called atom which takes part in chemical reactions. These particle can neither be created nor be destroyed. However, modem researches have conclusively proved that stom is no longer an indivisible particle. Modem structure of atom is based on Rutherford's scattering experiment, quantization of energy and ‘wave mechanical model. COMPOSITION OF ATOM ‘The works of J.J. Thomson and Emst Rutherford actually laid the foundation of the modem picture of the atom. It isnow verified that the atom consists of several sub-atomic particles like electron, proton, neutron, positron, neutrino, meson etc. Out of these particles, the electron, proton and the neutron are called fundamental subatomic particles. ELECTRON (_,e°, e) Electron was discovered by J.J. Thomson (1897) and itis a negatively charged particle» Cathode rays were discovered by William Crooke & J.J. Thomson using a cylindrical hard glass tube fitted with two metallic electrodes. This tube was known as discharge tube. They passed electricity (10,000V) through a discharge tube at very low pressure! Blue rays emerged from the cathode. These rays were termed as Cathode rays. Cataderays — Gmat low Discharge tube experiment for production of cathode rays Properties of Cathode rays @ Cathode rays travel in straight line, @ Cathode rays produce mechanical effect, as they can rotate the wheel placed in their path. (ii) Cathode rays consist of negatively charged particles known as electron. (@) Cathode rays travel with high speed. (¥) Cathode rays can cause fluorescence. (vi) Cathode rays heat the object on which they fall duc to transfer of kinetic energy to the object. (i) When cathode rays fall on heavy metals, X-rays are produced. (vill) Cathode rays possess ionizing power i.c., they ionize the gas through which they pass. (&)_—_Thecathode rays produce scintillation on the photographic plates. (x) Theycan penetrate through thin metallic sheets. (i) The nature of these rays does not depend upon the nature of gas or the cathode material used in discharge tube.Note : The television picture tube is a cathode ray tube in which a picture is produced due to fluorescence on 34 35 36 4. 42 43 44 45 46 Sl $2 53 54 55 the television screen coated with suitable material. Similarly, fluorescent light tubes are also cathode rays, tubes coated inside with suitable materials which produce visible light on being hit with cathode rays. RS, Mullikan measured the charge on an electron by oil drop experiment. The charge on each electron is -1.602 x 10°C. ‘The specific charge (c/m) on electron was first determined by JJ, Thomson. efm= 1.758 x 10"! Chkg Rest mass of electron is 9.109 « 10°! kg or, 0.00054 amu PROTON (H!, H", P) Proton was discovered by Goldstein and itis positively charged particle. Itis a component particle of anode rays. Goldstein (1886) used perforated cathode in the discharge tube and repeated cathode fayrexperinen nd cherved the Riemationofamadernys These ay wee so tse es pete or canal rays. Properties of anode rays (@Anode rays travel in straight line. i) Anode rays are matérial particles. (iii) Aftlode rays are positively charged. (iv) Anode rays may get deflected by external magnetic field. (w)Anode rays also affect the photographic plate. (vi) The e/m ratio of these rays is smaller than that of electrons, (vii) Unlike cathode rays, their e/m value is dependent upon the nature of the gas taken in the tube. It is ‘maximum when gas present in the tube ishydrogen. (viii) These rays produce flashes of light on ZnS screen. Charge on proton = 1.602 * 10-'? coulombs Mass of proton = 1.673 1077kg= 1.00728 amu Protonis ionized hydrogen atom H* Specific charge of proton is 9,58x10" Coulombykg NEUTRON (,n!, n) ‘Neutron was discovered by James Chadwick (1932) according to the following nuclear reaction, 4Be® + ,He’ > ,C” + ,n'or .B!' + He! +N" + n! ‘The reason for the late discovery of neutron was its neutral nature. Mass of neutron = 1.675x107kg = 1.00866 amu Specific charge of aneutron is zero. ‘Neutronis fundamental particle ofall the atomic nucleus, except hydrogen or protium.Mlustration ‘The mass to charge ratio for A” ion is 1.97 x 107 kg C*. Calculate the mass of A atom. Sol Given 2 =1,97* 107 (since e = 1.602 « 10°C) 2 m= 1.97 107 « 1.602 x 10" kg. Exercise ‘Arrange the following particles in increasing onder of values of e/m ratio : Electron (c), proton (p), neutron (n) and a-particle (a) - (A) a, p, ea (B) a, a, p, & (Cyn, p, a, € Oepaa Ans. (B) 6. THOMSON'’S MODEL ‘After discovery of electron and proton atiettipts were made to find out their arrangement in an atom. The first simple model was proposed by J.J. Thomson known as Thomson's atomic model. He proposed that the positive chafge is spread over a sphere of the size of the atom (i.e. 10-* em radius) in which electrons are embedded to make the atom as whole neutral. This model could not explain the experimental results of Rutherfords a-particle scattering, therefore it was rejected. Pastner spend hmaghe fe ephae 7. RUTHERFORD'S MODEL Rutherford carried out a-particles scattering experiment by the bombardment of high speed a-particle on thin foil of gold, emitted from radium and gave the following observations, which was based on his experiment.@® ® © 12 @ ® © 13 0 @ @) ) 14 Observations : ‘Mostof the a.- particles (nearly 99%) continued with their straight path. ‘Some of the «.- particles passed very close to the centre of the atom and deflected by small angles. ‘Very few particles thrown back (180°). ‘Nom of meta ot Boom of o-portises Very Majocky ome ‘Atom of metal tou FO ‘Main features : Most of the a. - particles were continued their straight path that means most of the space inside the atom is empty. The centre of an atom has a positively changed body called nucleus which repel positively charged @.- particles and thus explained the scattering phenomenon. Almost all mass of an atom is concentrated in its nucleus. ‘The size and volume of the nucleus is very small as compared to the total size and volume of atom. Properties of the Nucleus ‘Nucleus is a small, heavy, positively charged part of the atom and is located at the centre of the atom. Alll the positive charge of atom (i.e. protons) are present in nucleus. ‘Nucleus contains neutrons and protons, and hence these particles collectively are also referred to as nucleons. The size of nucleus is measured in Fermi (1 Fermi = 10"? cm = 10'S m). Generally, the radius of the nucleus (r,) is given by the following relation : nerxal where rg is a constant and A is the mass number. The Volume of the nucleus is about 10 m? and that of atom is 1077 m’ , i. nucleus is 10°' times that of an atom. volume of the Distance of closest approach : When the a-particle approaches the nucleus to made a head- on collision with a the nucleus, the a-particle approaches the nucleus until coulombic potential energy of repulsion , bee, becomes equal to its initial K.E., 4 my. 2 Tis 5 env 22 7 Hence, the distance of closest approach, r=“ 22:¢— :) ‘The nucleus must be further smaller than the distance of closest approach.7S — Drawbacks of Rutherford's model @ _Itdoes not obey the Maxwell theory of electrodynamics. According to this theory a small charged particle moving around an oppositely charged centre continuously loses its energy. Ifan electron does 50, it should also continuously lose its energy and should set up spiral motion ultimately falling into the ucleus. Nucleus Etecron @__Itcould not explain the line spectra of atom. Mlustration 1. Atomic radius is of the order of 10 * cm and nuclear radiusis of the order of 10" cm. Calculate what fraction of atom is occupied by nucicus ? Sol Volume ofnucieus $ar= $2009 Ge ‘Volume ofatom = 5% (10%) cm’, Viton = 10 Va 2. With what velocity should an particle travel towards the nucleus of a Cu atom so as toarriveata distance 10-? m. k(2e) (63e) z Sol. as Exercise Assuming spherical shape for fluorine nucleus, calculate the radius and the nuclear density of fluorine nucleus of mass number 19. Ans. 3.73 « 10" cm, 7.616 = 10" gem” MOSELEY EXPERIMENT (DISCOVERY OF ATOMIC NUMBER) Moseley (1912-1913), investigated the X-rays spectra of 38 different elements, starting from aluminium ‘and ending in gold. Ile measured the frequency of principal lines of a particular series (the a-lines in the K series) of the spectra. It was observed thatthe frequency of a particular spectral line gradually increased with the increase of atomic mass ofthe element. But, it was soon realised thatthe frequency Of the particular spectral line was more precisely related with the serial numberof the element in the periodic table which he termed as atomic number (Z). He presented the following relationship : WW sa(Z-b) where, v= frequency of X-rays, Z=atomic number, ‘a’ and “b’ afé constants, When the values of square root of the frequency were plotted agains! atomic numberof the lements producing X-rays, a straight line was obtained. 2 Vwit0'st 15 50-30-3040 ‘Atomic number (Z) Mlastration Ifthe straight line is at an angle 45° with b= | calculate frequency when atomic number Zis 50. (A)2000 (B) 2010 (C)2401 (D) None Ans, (C) Sok Jv =tan45°= b= fe= tan 8 AW =50-1=49 vst] 4 v= 2401s". —~ Exercise ‘What is atomic number Z when v= 2500s“! and value ofa= | andb=1 (A)50 @)40 os! (033 Ans. (C) 9. SOME ATOMIC TERMS 9.1 Atomic number = Number of unit positive charge on nucleus = Number of protons in nucleus = Number of electrons in neutral atom. ‘Two different elements can never have identical atomic number. 9.2 Mass number(A)=Number of protons + Number of neutrons or Atomic number (Z) Hence Number of neutrons = A -Z . “The atom of an element X having mass number (A) and atomic number (Z) maybe represented by a symbol, net rn AS semen 9 eg oF”. 0". ,N™ ate. 9.3 Apartofan atom up to penultimate shell is a kernel or atomic core. 9.4 Negative ton (anion)is formed BY gaining electrons and positive ion (cation) by the loss of electrons. 9.5 Isotopes ¥Atomsof an element with the same atomic number but different mass number. e aw we we Protonium deuterium Teun 9.6 — Isodiapheres : The elements which have same value of (n — p) is called Isodiapheres. ca aN s0'* Values of (n- p) 0 0 9.7 Isotome : Elements which contain same no. of neutron is called Isotone. % us? wet 6S? number of neutrons 16 16 16 98 Isobar: Thetwo different atoms which have same mass number but different atomic number is called Isobar. C7 Are wk wca 9.9 _Isoelectronic : lon or tom or molecule which have the same number of electron is called Isoelectronic species. e ycl- wAr wk" aca’? No. of electrons 18 18 18 9.10 Isosters : Substance which have same number of electrons and the same number of total atoms are called Isosters. e CO, N,0 No.of electrons 2a 2 No. of atoms 303a Mustration 1. Fromthe following list of atoms, choose the isotopes, isobars and isotones - $0. 3K. BU. GK. YN, 80. SC. SCa, BU Sol, Isotopes: ("30,30 ),(BK 19K), (78U,72U) Isobars: (RK. $Ca).C4N, YC) Isotones: (33K. Ca), ('8C. 80) Total number of electrons, protons and neutrons present in the nucleus of ,U?** is (A)e= 92, p=92, n= 146 (B)e=92, p=92, n= 148 (Che=0,p=92, n= 146 (D) None of these Ans. (C) Sol There isnoelectron in the nucleus. n, = 0,n, = 92, n, = 238-92 = 146 Exercise ‘Nitrogen atom has Atomic number7 & oxygen has Atomic number 8. Calculate the total number of electrons innitratcion- Ans, 32 10. WAVE A.wave motion isa means of transferring energy from one point to another point without any actual transportation of matter between these points. When we throw a piece of stone on the surface of water ina pond, we observe circles of ever increasing radius, till they strike the wall of the pond. When we put apicce of cork on the surface of this water, we observe thal the cork moves up and down as the wave passes, but the piece does not travel along with the waves. The water waves carries the energy but there is no transfer of matter. Thus ina wave motion, disturbance travels through the medium, but the medium. does not travel along with the disturbance. ‘Some important terms related with wave motion. Crest ,,Wavelength ‘source ‘Trough @ Wave length (1): The distance between two adjacent crestor trough of the wave (or the distance between two similar neighbouring points) OR (@) Time period (1): Time for one complete oscillation of wave is called the period (1). ‘Time taken by the wave to travel a distance equal to one wavelength. If Cis the a speed of wave, then C= =10.1 (il) Frequency (v): Number of oscillations per unit time is called frequency. c vee a (iv) Wave number (¥) : Number of wavelength per unit length. (¥) Amplitude (A): It is the height of crest or depth of a trough of a wave. Electromagnetic Wave : Light is also a type of wave which is known as electromagnetic wave i.e. wave consisting of oscillating clectric and magnetic field. ‘There are various types of electromagnetic waves (fadiation) which differs from one another in wavelengths eg. Visible light, ultraviolet rays, X-rays, infra-red rays, radio waves etc. Characteristics of electromagnetic radiations: ® &) © 10.2 All electromagnetic waves move or travel with the same speed equal to that of light. They do not require any medium to propagate. These consist of electric and magnetic field that oscillate in the’ direction perpendicular to cach other and to the direction in which the wave propagates (as shown in above diagram) Electromagnetic Spectrum ‘Arrangement of various types of electromagnetic radiations in order oftheir increasing (or decreasing) ‘wavelengths or frequencies is known as electromagnetic spectrum. 2 increases ——————_—> SPECTRUM ‘When light coming from a source is dispersed by a prism, light of different wavelength are deviated through different angles and get separated. This phenomenon is called dispersion and such a dispersed light may be received on a photographic plate or it may be viewed directly by eye. Acollection of dispersed light giving its wavelength composition is called a spectrum.40 Wt @ © 12. 0} ™ very high temperature or by giving energy and subsequently radiations are emitted. These radiations when analysed with the help of spectroscope, spectral lines are obtained. A substance may be excited- By heating at a higher temperature. By passing electric current at a very low pressure in a discharge tube filled with a gas. By passing electric current into metallic filament. Emission spectra may be classified as : ‘Continuous spectrum : When sunlight is passed through a prism, it gets dispersed into continuous bands of different colours. If the light of an incandescent object is resolved through prism or spectroscope, it also gives continuous spectrum of colours. i oils Indra Coen prem cte Line spectrum : If the radiations obtained by the excitation of a substance are analysed with the help of a spectroscope, a series of thin bright lines of specific colours are obtained. There is dark space in between two consecutive lines. This type of spectrum is called line spectrum or atomic spectrum. For example on heating sodium chloride or any other salt of sodium in Bunsen flame bright yellow light is emitted. The emitted light when viewed through a spectroscope two isolated yellow line spared by dark space are obined. The wave lenge of these lines are S890A. and 5896A. Absorption spectrum ‘When the white light of an incandescent substance is passed through any other substance, this substance absorbs the radiations of certain wavelength from the white light. On analysing the transmitted light we obtain a spectrum in which dark lines of specific wave lengths are observed. ‘These lines constitute the absorption spectrum. The wave length of the dark lines correspond to the wavelength of light absorbed. MAXWELL THEORY OF ELECTROMAGNETIC WAVE Allthe radiations have wave nature which explains interference (linear superposition) and diffraction. ‘They consist of oscillating electric and magnetic field perpendicular to each other and tothe direction of Propagation. Al the radiations (radio waves, micro waves, infra red waves, visible, UV, X-rays, y-rays) travel at the speedoflight in vaccum. Energy of electromagnetic wave is proportional to amplitude and not linked with frequency of waves.13. 4 Draw backs: This theory could not explain the following (a) Phenomenon of black body radiations (b)Photoelectriceffect _(c) Line spectra of atoms PLANCK'S QUANTUM THEORY According to this theory atoms or molecules could emit or absorb energy only in discrete quantities, (small packets) and notin any arbitrary amount. Planck gave the name quantum to the smallest quantity of energy that can be emitted in the form of E.M. radiation. ‘The energy of a photon is proportional toits frequency and is given by E=hv where h = 6.626 * 10" Isec. ‘A body can emit or absorb energy only in terms ofthe integral multiples of quantum, ie. E=n. hu, where n= 1, 2, 3, i.e. abody can emit orabsorb energy as values of hu such a 1.5 hv, 2.5hu. + 2D wun: but itcan not emit or absorb energy in fractional Einstein supported the planck’s theory and explained the photdelectrie effect considering that ic radiations also propagate in the form of photon..Energy of each photon depends on frequency oti (E =ho= *), ‘Since wave character of light explains the interference and diffraction phenomenon while the particle character explains, black body radiations and photoelectric effect, the light was considered to have wave as wells particle character | Dual character oflight] 3) Whatisthe energy and wavelength of photons of frequency 3.4 MHz? 3 —_Alsocalculate the energy per mole of photons of the same wavelength. v= 34MHZ = 34x10°HZ = 34x10°s _3x10%mst _ vo 3axl0st Energy, E=hv = 6.626 10™ 3.4 x 10°) =2.253« 107) Energy per mole of photon =6.02 x 10 x 2.53 10 J mol! = 1.356% 10° J mot" a ‘The vapours of Hg absorb some electrons accelerated by a potential diff. of 4.5 volt as aresult of which light is emined. Ifthe full energy of single incident e” is supposed to be converted into light emitted by single Hg atom, find the wave no. of the light. he he EreV= > = A= cy 33.63 x10tmrt42 Exercise Calculate the number of photons emitted in 10 hours by a 60 W(J/s“!) sodium lamp (Aofphoton= 5893 A) Ans. 6.43 x 10 14, PHOTOELECTRIC EFFECT Emission of electrons from a metal surface when exposed to light radiations of appropriate wavelength is called photoelectric effect. The emitted electrons are called photoelectrons. Electron’ Metal ‘Work function or threshold energy may be defined as the minimum amount of energy required to eject electrons from a metal surface. According to Einstein, Maximum kinetic energy ofthe ejected electron = absorbed energy - work function 1 3 ghey te [EF] where, vj and’, are threshold frequency and threshold wavelength respectively. ‘Stopping potential : The minimum potential at which the photocloctric current becomes 2er0 is called stopping potential. If Va sthe stopping potential then hiv- KE, €V_=h(v-%) oF Vo= Neate) Ea, ‘Some facts of Photoclectric Effect a @ @ wy) ‘There is no time lag between incidence of light and emission of photoelectrons. For emission of photoelectrons, the frequency of incident light must be equal to or greater than the threshold frequency. Rate of emission of photoclectrons from a metal surface is directly proportional to the intensity of incident light. “The maximum kinctic energy of photoctectrons depends on the froquency of incident radiation; but, itis independent ofthe intensity of light used.Ilustration. L ‘The minimum energy required to overcome the attractive forces clectron and surface of Ag metal is 7.52 x 10°" J. Calculate the maximum K.E. of electron ejected out from Ag which is being exposed to U.V. light of = 360 A Sol. Energy absorbed =" = 662 x 10°77 x 30 «10° 360 x 107° "5.52.10" erg = 5.52%10-" Joule Maximum kinetic energy of electron="(7.52 « 10-19) — (0, 552 » 10-9) = 6.968 x 10 Joule 2 ‘A metal was irriadated by light of frequency 3.2 « 10'S S~!. The photoelectron produced had its KE, 2 times the KE of the photoelectron which was produced when the same metal was irriadated with a light of frequency 2.0%10!5 S~. What is work function. Sol E,=hy-ty E,=hv; ~¢y _ hx3.2x10"- 6, $5 = 319.2 KJ/Mol Exercise Light of wavelength 4000 A falls on the surface of cesium. Calcutate the maximum kinetic energy of the ‘emitted. The critical wavelength for photoelectric effect in cesium is 6600 A Ans. 1.95 « 10"'9 Joule 15. BOHR'S ATOMIC MODEL This model was based on the quantum theory of radiation and the classical law of physics. It gave new idea of atomic structure in ordet to explain the stability of the atom and emission of sharp spectral ines.44 1 0 @ @ mo o ow wi) Postulates ‘The atom has a central massive core nucleus where all the protons and neutrons are present. The size of thenucleusis very small. ‘The electron in an atom revolve around the nucleus in certain discrete orbits. Such orbits are known as stable orbits or non - radiating or stationary orbits. Anclectron can move only in those permissive orbits in which the angular momentum (mvr) of the electron s an integral multiple of b/2n Thus, h arent 2x where, m = mass of the electron, r= radius of the electronic orbit, v= velocity of the electron in its orbit. h 2h 3h nh ‘The angular momentum can! 222 This principals known.s quantization of angular ‘momentum. In the above equation ‘n'is positive integer which has been called as principal quantum number. Itcan have the values n=1,2.3, -— (from the nucleus). Various energy levels are designed as K(n=1), L(n=2), M(n=3) —-— cte. Since the electron present in these orbits is associated with some ‘energy, these orbits are called energy levels. ‘The emission or absorption of radiation by the atom takes place when an€éleétron jumps from one stationary orbit to another. “The radiation is emitted or absorbed asa single quanturn (photon) whose energy is equal to the difference in energy of the electron in the two orbits involved. Thus, AE = hy. where h=Planck's constant and v, frequency of the radiant energy. Hence the spectrum of the atom will have certain fixed frequency. ‘The lowest energy state (n=1) is called the ground state. When an clectron absorbs energy, it gets ‘excited and jumps to an outer orbit. It has to fall back toa lower orbit with the release of energy. Advantage of Bohr’s theory - Bob's theory satisfactorily explains the spectra of species having one electron, viz. hydrogen atom, He*,Li?* ete. Calculation of the radius of the Bobr’s orbit: Suppose that an electron having mass ‘m’ and charge *e" revolving around the nucleus of charge ‘atomic number & e is charge) with a tangential / linear velocity of ‘v’. Further consider45 ‘According to Coulomb's law, the electrostatic force of attraction (F) between the moving electron Gy and nucleus is - K2e? F 7 Where : K = constant = <1 = 9 x 10° Nm?/C? Am From the postulate of Bobr, fh m= 2 _ wht = mae +2) From equation (1) and (2): nth? So Gatranzet (On putting the value or e, h, m, r=0s205%A Calculation of velocity of an electron in Bohr's orbit : Velocity of the revolving electron in n** orbit is given by — =m ye th mr On 2amnr Putting the value ofr in above equation rine Ante? ten emt? ya 2ezet nh on putting the values of ¢ and h, 2.188x10" xof energy of an electron ‘The total energy of an electron revolving in a particular orbit TE K.E.+PE. The KE. of anelectron = Jmv? and the PE. ofan electron = —"2#" Hence, TE. = Jae 22 nea @) mv? _ Ke? KZe? Bm Substituting the value of mv? in the equation (3) TE tae? So, TE = Substituting the value of *r’in the equation of TE, KZe? 4n?Ze'mk _.28'Ze'mk? Berd ah? oh ‘Thus, the (otal energy of an électron in n" orbit is given by 2n'Z?e‘mk* ar a z =~ 13.6 eV / atom 21810" 2 3) - 21 7 atom 2 =~ 313.6 « 7 Keal/ mole (¥) Relation between P. E., K. E. & T. E. : (i) Calculation of the number of revolutions of the electron in an orbit per second velocity of the electron Number of revolutions pet sec.= Circumference of the orbil[On substituting the value of v from mvr= 4x°mr* - nh nh 4n?mae?k No. of revolutions per second = 33 = Go * | a3? 4x?mze'k? oh 4x°mr* n’h? nh 4xtmz'e"k* ‘Time taken for one revolution (Time period) = Mlustration L ‘The radius of the an orbit of hydrogen atom is 0.85 nm. Calculate the velocity of electron in this orbit. So r=rn? n?=16, a=4 v=ve= 2.186 x toot 5.44 x 105 m/s 2 ‘The energy of an excited H-atom is -3.4 eV. Calculate angular momentum of ¢” in the given orbit. z 136 2 =- =—=4 So E=-136 77 >= 37> n=2 oh _ bh ‘Angular momentum =mvr= = = = Tonisation energy of hydrogen atom is 13.6 eV. Calculate the ionisation energy for Be™” in the first excited state. Sol. Ionization energy of hydrogen -E, ( Energy of fist Bohr orbit ) » n=2 (for I“ excited state) a 1s-(1365) S44eV 248 Exercise ‘The ionization energy of H-atom is 13.6 eV. Calculate the ionization energy of Li’? ion - 1224eV Hydrogen Spectrum Hydrogen spectrum is an example of line or atomic emission spectrum. When an electric discharge is passed through hydrogen gas a low pressure, a bluish light is emitted. This light shows discontinuous line ‘spectrum of several isolated sharp lines through prism. All these lines of H-spectrum have Lyman, Balmer, Paschen, Barckett, Pfund and Humphrey series. These spectral series were named by the name of scientist discovered them. To evaluate wavelength of various H-lines Rydberg introduced the following, ‘expression, ‘Where R is a constant known as Rydberg's constant its value\is 109, 67800 ar" . ‘Although H- atom consists only one electron yet its spectta cofisist of many spectral lines because electrons in different hydrogen atoms absorb different amoiint of energies and are excited to different energy levels. Since life time Of electrons’ in these excited states is very small, they retum. to some lower energy level of éven to the ground state in one or more jumps P. i hme Maximum oumbeotines produced when n eeoronjunps fom aiheeli ground eel ==)“a oO @) 19 Lyman Series (a) Itisa first series of spectral series of H. (®) Itwas found out in ultraviolet region in 1898 by Lyman. (© It’s value of n, = 1 and n, = 2, 3, 4 where ‘n," is ground state and ‘n, electron present ina H-atom. @ Ifthe electron goeston, =! fromn, =2 — first Lyman series Ifthe electron gocston, =I fromn,=3 — Second Lyman series Ifthe electron goeston, = I fromn,=4 —third Lyman series — soon. called excited state of 1 1 © pen{i-zs] where n,> always, 2 (0 Formarginal line o imiing line ny =o. Hence the wavelength of marginal line= 5 forall sres. So, for lyman series itis — Balmer series : (a) Itisthe second series of H-spectral series. (b) Iwas found out in 1892 in visible region by Balmer. (©) Balmer series was found out before all series because it was found in visible region. @ It’s value of n, =2 and n, = 3.4, (©) Ifthe electron goes ton, = 2 from n, = 3 First Balmer series Ifthe electron goes ton, = 2 from n, = 4 Second Balmer series Ifthe electron goes ton, #2 from n,= 5— third Balmer series... soon Paschen series : (@) It is the third series of H - spectrum. (®) It was found out in infra red region by Paschen. (© It’s value of n, = 3 and n, = 4, 5, 6 .. (@ If the electron goes to n, = 3 from n, = 4 — First paschen series If the electron goes to n, = 3 from n, = 5 — second paschen series If the electron goes to n, = 3 from n, = 6 — third paschen series —— so on. al Fo (©) The wavelength of marginal line of paschen series = RRR. w Ry Ry 1 o a | where n, > 3 always. Brackett series : (a) Itis fourth series of H- spectrum. (b) Itwas found out in infra red region by Brackett. (© It’s valucofn, =4 and n, = 5,6,7184 (@) Ifthe electron goes to n, = 4 from n, = 5 — first brackett series Ifthe electron goes ton, = 4 from n, = 6 — second brackett series If the electron gocs ton, =4 from n, =7— third brackett series -—-- soon. (€) The wavelength of marginal line of bracken series = R= oa 1 1a © t-n[z-3] Where n, > 4 always. Pfund series : (@) tis fifth series of H - spectrum. (®) Itwas found out in infra red region by Pfund. (© W's value of, =5 andn,=6, 7, @ Ifthe electron goes to: fromn,=6 —first Pfund series Itheelectron goeston,=5 — fromn,= —second Pfund series Ifthe clectron gocsion,=5 fromn,-8 — — third Pfundscrics, so on. 2 3 (©) The wavelength of marginal line of Pfund series = woes iw Ry Ry 1 1 oO ioe where fi, > Svalways: Humfrey series : (@) ltisthe sixthscries of H- spectrum. (b) Itwas found out in infra-red region by Humfrey. © It's value of n, = 6 and n, = 7, 8, 9 @ Ifthe electron goes to: from, —first Humfrey series Ifthe electron goes to! from, —second Humirey series Ifthe electron goes ton,=6 — fromn, —third Humfrey series ... soon. 2 (©) The wavelength of marginal line of Humfrey series = ge -2 “2 where n, > 6. Note :a - line = first line of series. Similarly For example : First line (a-line) of Paschen series will be from n, = 4 to n, = 3 ine = second line of series Calculation of Rydberg Constant from bobr’s atomic model ‘Suppose that an electron transist from first energy level to second energy level. Then, the change of energy is given by sE-E,, - E,[eae] [eae] or,= |r | -|— ata Tae TRE nih nih A 2nimz'etk? (1 a(t oe [at at | *Rn2* (nF ae 2x’me'k? oF, Ry = —" 55 = Rydberg constant Mlustration Calculate the wavelength of radiation emitted, producing a line in Lyman series, when an electron falls from fourth stationary state in hydrogen atom. ral (For H-atom, Z= 1, Lyman series; n, = 1) 2= 9.710% m Calculate the wave no forthe shortest wavelength transition in the Balmer series of atomic hydrogen. For shortest wavelength n,—> 20 R 4 727419.25 enw! Calculate the energy emitted when electrons of 1.0 gmatom of Hydrogen undergo transition givingthe spectral lines of lowest energy in visible region ofitsatomic spectra. Given that ,R,.= 1.1% 107 m',c =3 * 10" m/sec, h=6. 625 * 10™ J sec. Visible region of H-spectrum correspond to Balmer series n, = 2, n,~3 (for minimum energy transition ) J eaxto| tt x Jo f-1 [i -1] [RH = 109677 cm = 109677 « 100 m= 1.1 10° m"] A= 655x107 m 3.03 = 10" Joule .. Energy released by I gm atom of H(1 mol ) = 3.03 x 10 «6.023 «10 = 18.25x 10'S = 182. Sk)22 Exercise (Calculate ratio of wavelength of limiting line of Balmer and Paschen scrics for an atom . Ans, 4/9 15.5 Failure of Bohr Model ()_Bobrthoory was very successful in predicting and accounting the energies of lin spectra of hydrogen i.e.one electron system. It could not explain the line spectra of atoms containing more than one electron. (@ This theory could not explain the presence of multiple spectral lines. (ii) This theory could not explain the spitting of spectral lines in magnetic field (Zeeman effect) andin electric field (Stark effect). The intensity of these spectral lines was also not explained by the Bohr atomic model. (iv) This theory could not explain uncertainty principle. PARTICLE AND WAVE NATURE OF ELECTRON: In 1924, de Broglie proposed that an electron, like light, behaves both as material particle and as a ‘wave. This proposal gave a new theory, known as wave mechanical theory of matter. According to this theory, the electrons, protons and even atoms, when in motion, posses wave properties. ‘dc Broglic derived an expression for calculating the wavelength of the wave associated with the clectron. ‘According to Planck's equation E=Ww=hy l) “The energy ofa photon on the basis of Einstein's mass-energy relationship is E=me cnn) where, c is the velocity of the electron. From (1) and (2) equation © hx t =me* | Meee 3) ‘Momentum of the moving electron is inversely proportional o its wavelength. Let kinetic energy of the particle of mass ‘m’ is E. 1 E-5 mv? 2Em=m'v* 2Em =mv=p(momentum) re)23 mv?=2qVm mv= /2qVm h and, = gv (A) _ deBroglie wavelength associated with charged particles 12.27 Forelectron: ae “WA For proton: a= EA 0.101 For a- particles: hana where, V = accelerating potential of these particles, (B) _ deBroglie wavelength associated with neatron = __ 6.62107 0.286 Torresen: i= Fo © Y2x1. 67x10 XE *VEeA ‘The wavelength decreases if the value of mass (m) increases .<. de Broglie equation is applicable inthe ‘case of smaller particles like electron and has no significance for larger particles. Derivation of Angular Momentum from de Broglie Equation: ‘According to Boht’s model, the electron revolves around the nucleus in circular orbits. Acconding tode Broglie concer, the electron is not only a panicle but also has a wave character. Ifthe wave is completcly in phase, the circumference of the orbit must be equal to an integral multiple of wave length (A). 2nr= nd where‘ is an integer and’? isthe radius of the orbit Buth=himv ©. 2nr=nh/mv oc mvr=nh/2n which is Bohr’s postulate of angular momentum, where nis the principal quanturn number. "Thus, the number of waves an electron makes in a particular Bohr orbit in one complete revolution is ‘equal to the principal quantum number ofthe orbit”. Iitustration What is de Broglie wavelength fora hydrogen stom moving with a velocity of 2000 ms" ? (Atomic mass ofhydrogen = 1.00797am.u) 0097 Sol, Mass of a hydrogen atom= <0 jg37 B= 1.68 * 10% g= 1.68 x 107" kg L 02x 1 uM = 1.97 10 nnn. 1.97= 10m17. @® ® © @ © o ® HEISENBERG'S UNCERTAINTY PRINCIPLE While treating e~ as a wave it is not possible to ascertain simultancously the exact velocity of the e- more precisely at a given instant since the wave is extending throughout a region of space As the photons of longer wavelengths are less energetic, hence they have less momentum and cannot be located exactly In 1927, Warmer Heisenberg presented a principle known as Heisenberg’s uncertainty principle According to this principle it is impossible to measure simultaneously the exact position and exact momentum of a body as small as an electron. If uncertainty of measurement of position is Ax and uncertainty of measurement of momentum is ap or may, then according to Heisenberg, ax.sp2 or Ax.mav2 where h is planck’s constant For other conjugates of motion the equation for Heisénberg's uncertainty principle may be given as AE. At 7 (for energy and'time) Like de Broglie equation, this principle has significance only for microscopic particles. HMlustration Anelectron having velocity 2 x 10° m/s has uncertainty in kinetic energy is 2 x 10-7'J, then calculate the uncertainty in position (in Angstrom, A) of the electron. [Given : h=6.62 10 J-sec] h 0) Bu AK= Gonay ~-@) 6.6210" x2x10° a> — ay a SODA 4nm nx © 197! my ®Exercise Ameasurement establishes position of a proton with an accuracy of + 10" m. Find the minimum uncertainty in proton's position I second later. x= 210m <- According to Heisenbery's Uncertainty Principle h 6.6210" AV" em(BR) ” Ba. 14d 67x10 10 O16 * 1 Av=Ax/At hence Ax (minimum uncertainty in position after one sec.) = Av * At = 0.3156 x 10°x 1 =3.15 « 10?m Ans. WAVE MECHANICAL MODEL OF ATOM ‘The atomic model which is based on the particle and wave nature of the electron is known as wave mechanical model ofthe atom. This was developed by Erwin Schrodinger in 1926. This model describes the electron asa three-dimensional wave in the electronic field of positively charged nucleus. Schrodinger ‘derived an equation which described wave motion of an electron. The differential equation is : fy 4 dy ey Sx'm ax? dy? de? a? (E-V)y=0 Where x,y and z are cartesian coordinates of the electron; m = mass of the electron; E=total energy of the electron; V= potential energy of the electron; h = Planck's constant and (psi) = wave function of the electron. Significance of y : The wave function may be regarded as the amplitude function expressed in terms of ‘coordinates x, y and z. The wave function may have positive or negative values depending upon the values of coordinates. ‘The main aim of Schrodinger equation is to give a solution for the probability approach. When the equation is solved, itis observed that for some regions of space, the valuc of y is positive and for other regions the value of y is negative. But the probability must be always positive and cannot be negative. It is, thus, properto use y” in favour of y. Significance of y*: yisa probability factor. It describes the probability of finding an clectron within a small space. The space in which there is maximum probability of finding an electron is termed as orbital. “The important point ofthe solution ofthis equation is that it provides a set of number, called quantum numbers, which describe energies of the electrons in atoms, information about the shapes and orientations of the most probable distribution of electron around the nucleus. ‘Wave function y can be plotted against distance ‘r” from nucleus 2s,Forhydrogen wave function, number of nodes can be calculated as, (i) Number of radial nodes = (n—/—1) (i) Number of angular nodes = / (Gi) Total number of nodes = (n-1), 1,/=0, it will have no radial or angular node it will have only one radial node (iv) For 2p-orbital, (¥)For 3p-orbital, n= 3,1= 1, itwill have one radial and one angular node ‘Solution of Schrodinger wave equation : In spherical co-ordinates w(x, y,z) is represented by y (r, 8, @) such that complete wave function can begivenas Shy RO cee us Radial part Angular part Dependance of the wave function on quantum number can be given as, Yim (6.0.4) =Rys (0) Om 4) Ou (4) ‘The function R depend only on , therefore they describe the distribution of the electronas a function of + from the nucleus. These functions depend upon two quantum numbers, n and /. The two functions @ and ¢ taken together give the angular distribution of the electron. ‘The radial part the wave function for some orbitals may be given as, (yea slay ee where, Z=atomic number, a, = radius of first Bohr orbit of hydrogen.27 1 1 | Sf ‘Atnode, the value of “R” changes from positive to negative. Plot of Radial Probability Density ‘R® : { | a! 4 ‘The plotof probability ie, R? or ¥? are more meaningful than the plots of function themselves. Itcan be seen that forboth Is and 2s orbitals, the probability has a maximum value at = 0, i¢. inthe nucleus. In case of 2s orbital, one more maximum in the probability plotis observed. Plot of Radial probability Function (4nr7R?) : Inorder to visualize the electron cloud within a spherical shell is placed at radii‘r' and ‘r+ dr’ from the nucleus. Thus radial probability function describes the total probability of finding the electron in a spherical shell of thickness “dr’ located atthe distance r from the nucleus. RPE. = (Volume of spherical shell) x Probability density = (411? dr) x R? Ane —> nek’ —> — Inthe plot of radial probability against *r', number peaks, ic. region of maximum probability =n — 1.Mlustration an Fla AN Distance fom muclens —e Ifthe above radial probability curve indicates ‘2s* orbital, the distance between the peak points X & Y is (A)2.07A (B)1.59A (C)053A (D)2.12A Ans. (A) Sol. X=0.53A, 6A Y-X=26- 053= 207A Exercise Plots for 2s orbital are : hawt tha X,Y andZ.are respectively (A)R, R? and 4nP7R? (B)R?,R and 4ar°R? (C)4x°R?, R? and (D)R?,4aP7-R? and: Ans. (B) 19.1 (a) ) QUANTUM NUMBERS ‘The measurement scale by which the orbitals are distinguished, can be represented by sets of numbers called as quantum number, Quantum numbers are to specify and display to complete information about size, shape and orientation of the orbital. These are principle, azimuthal and magnetic quantum number, which follows directly from solution of schrodinger wave equation. Except to these quantum numbers, one additional quantum number designated as spin quantum number, which specify the spin of electron in an orbital. Each orbital in an atom is specified by a set of three quantum numbers and each electron is designated by a set of four quantum numbers. Principal quantum number (0 It was proposed by Bohr and denoted by ‘n’. It determines the average distance between electron and nucleus, means it is denoted the size of©) @ © © 19.2 @ © ae 193 @ © @ © oO ) It determine the energy of the electron in an orbit where electron is present. ‘The maximum number of an electron in an orbit represented by this quantum number as 2n?. It gives the information of orbit K, L, M, N, ... ‘The value of energy increases with the increasing value of n. It represents the major energy shell from which the electron belongs. Azimuthal quantum number or angular quantum number (4- It was proposed by Sommerfield and denoted by *¢. It determines the number of subshells or sublevels to which the electron belongs. Ittells about the shape of subshells, It also expresses the energies of subshells s < p “841-9 Sg <> S#4=9 Of + 643-9 a —> 74259 correct order —> 8s 5g 6f 7d 8p Which ofthe following sct of quantum number s validénvalid. Incase of valid set write the symbol of the orbital itrepresents [may have more than one answers] & in case itis invalid mention the reason, A 1 m @ 3 not known: 0 (but ess than 3) @ 2 3 + @ 4 -1 (Valid, 3839/3, /3p/34_,_ 4/30 /34,/34,3d,, rai ean Pee (ili)Valid 44 2! Add, / 4d, Exercise How many electrons ina given atom can have the following quantum numbers — () n=4,¢=1 (b)n=2, é=1,m=-1,s=+% @)n=3 (c) 18a4 20. 20.1 202 20.3 SHAPE AND SIZE OF ORBITALS ‘An orbital is the region of space around the nucleus within which the probability of finding an electron of given energy is maximum (90-95%). The shape of this region (electron cloud) gives the shape of the orbital. It is basically determined by the azimuthal quantum number /, while the orientation of orbital depends on the magnetic quantum number (m). s-orbital (I= 0) : These orbitals are spherical and symmetrical about the nucleus. The probability of finding the electron is maximum near the nucleus and keeps on decreasing as the distance from the nucleus increases. There is vacant space between two successive s-orbitals known as radial node. But there is no radial node for 1s orbital since itis starting from the nucleus. The size of the orbital depends upon the value of principal quantum number (n). Greater the value of n, larger is the size of the orbital. Therefore, 2s-orbital is larger than 1s orbital but both of them are non-directional and spherically symmetrical in shape. P-orbital (J = 1): The probability of finding the p-clectron is maximuim in tW® lobes on the opposite sides of the nucleus. This gives rise to a dumb-bell shape for the p-orbital. For p-orbital / = 1. Hence, m= -1, 0, +1. Thus, p-orbital have three different 6rientations. These are designated as Py» Py & P, depending upon whether the density of clectron is, maximum along the x y and z axis respectively. As they are not spherically symmetrical, they have directional character. The two lobes of p-orbitals are separated by.a.nddal planeywhere the probability of finding electron is zero. The three p-orbitals belonging'to a paflicular energy shell have equal energies and are called degenerite orbitals. d-orbital (= 2): For d-orbitals, ] = 2. Hence m = -2,-1, 0, +1, +2. Thus there are 5d orbitals. They have relatively complex geometry. Out of the five orbitals, the three (4, d,,,.d,,) project in between the axis and the othertwo d,, and 4):_,: liealong the axis. ‘Spherical nodes : The spherical surface where probability of finding the clectron is zero, is called fical nodes. spherical No. of spherical nodes in any orbital =n—!—1 ‘Nodal Plane : This isa plane passing through the nucleus where the probability of finding the electron iszero. ‘Number of nodal plane in a orbital = £21. 24 o @ 21.2 ELECTRONIC CONFIGURATION ‘The distribution of electrons in different orbitals of atom is known 2s electronic configuration of the atoms. Filling up of orbitals in the ground state of atom is governed by the following rules: ‘Aufbau principle ‘Auf bau is a German word, meaning ‘building up. According to this principle, "Inthe ground state the atomic orbitals are filled in order of increasing. energies i. in the ground state the electrons first occupy the lowest energy orbitals available”. In fact the energy of an orbital is determined by the quantum number n and I with the help of (a+!) rule or Bohr Bury rule. According to this rule (@) Lower the value of n + J, lower is the energy of the orbital and such an orbital will be filled up first. (b) When two orbitals have same value of (n + 2) the orbital having lower value of "n" has lower energy and such an orbital will be filled up first . Thus, order of filling up of orbitals is as follows: Is<2s<2p<3s<3p<4s<3d<4p SX HIS ya rey 16x10" KE,g@3.1- 11 =) 2ev We know that Stoppingpotential © =KE,../e Magnitude ofslopeofcure =h rH - ees 10's Intercepton x-axis = Threshold fiequency Lev 1 TN" heV—-s ~ 414x107 =2.66x10"Hz Ans. How many electrons in a given atom can have the following quantum numbers — @)n=4/=1 (b)n=2, [= 1,m=-1,s=+% ( n=3 @n=4, [=2,m=0 (2) 1=1 refers top -subshell which has three orbitals (p,..p, and p,) each having two electrons. ‘Therefore, total number of electrons are 6. (b) [= refers top-subshell, m= 1 refers to p, or p, orbital whereas, s = +44 indicate for only electron. (©) Number of electrons for any energy level is given by 2ntic. 2x 3?= 18 electrons (4) = 2 means d-subshell and m= 0 refer to dz? orbital :. Number of electrons are 2.Qs Sol. Qs ‘Sol. ‘Sol. qu Sot. Qi2 ‘What designation will you assign to an orbital having following quantum number — @a=3, 0 [=1, m=-1 ()n=5, f=0, m=0 @n=2, é1, m=0 (@) Since ¢= | corresponds to p-orbital andm=-1 shows orientation either in x or y axis, thus this orbital refers to 3p, or 3p, or 3p, ) 5s (©) 2p, oF 2p, or 2p, ‘cho Slowing of quan manip espe (@)n=3,¢=2,m= (Qn=2¢=2,m=415=-12 (a) This set of quantum number is permitted. (®) This set of quantum number is not permitted as value of 's" cannot be zero. (©) This set of quantum number is not permitted as the value of‘ cannot be equalito‘n’. (@) _ Forany mukiclectron specie, compare the energies of following orbitals) Justify [External magnetic & electric fields are absent] Orbitals to be compared 34,25, 4p,.4p, (©) Compare the "average distance” ofthe following orbitals from the nucleus. Also comment on their ‘Chances of closeness to the nucleus” if they have same average distance” Orbitals to be compared Is, 2s, 3s; 3p;s3d,, (@) 2s@3dy=4p,= 4p, Justification compare (n+ 1) & if (n+) same then ‘n’ (&) Average distance (on the basis of n) 18<2s<3s= 3p, =3dy, ‘Closeness comparison 3swill be more close as compared to 3p, as compared to 34, (Calculate energy of electron which is moving inthe orbit that has its radius, sixtsen times the radius of first Bobr orbit for H-atom. rergn =r=16 =nn4 0° E=——— = - 1.36 10°" Jiatom Wavelength of the Balmer H, line is 6565 A. Calculate the wavelength of Hy, line of same hydrogen like atom. Foradine of Balmer SeriesQu Q.4 p= 4.863 x 1077 m _ 2 “The electron energy in hydrogen atom is givenby E, = ~24-7*10"" ergs. Calculate the energy required 7 toremove ane” completely from n= 2 orbit . What is the largest wavelength in cm of light that can be used to cause this transition. For complete removal from n=2 ta age s21nw2[5-2] = 5.425 x 10-7 erg he * nae, 7 = Calculate the threshold frequelicy of metal if the binding energy is 180.69 KJ mof" of electron. ine” 1.80.69 10° in} 2 __1:80.69%10__ ae( i) 6.0210” x1.6x10™ v=45x10! U.V. light of wavelength 800 A & 700 A falls on hydrogen atoms in their ground state & liberates electrons with kinetic energy 1.8 eV and 4 eV respectively. Calculate planck’s constant.a Sol d= tw” Jimev ¥ (ys 6.63x10) TAG) 2me” 610 F «29.0110 1.6210 = 6.03 104V Q.17 Calculate magnitude of orbital angular momentum of an ¢* that occupies 1s,2s , 2p, 34 ,3p. {Ans.0;0 v8 2 vet wid) Sol, Orbitalangularmomentum h “2 (ep) for Is, 2s,/=0 O.A.M.= 0, for2p,1=1 OAM= for 3d, /=2 OAM. us fe oF WAM.= 5, V6 h for3p,1=1, OAM.=5~ 2 2x