TACH YON Soumy Chakraborty (Ph, No. ~ 8420026932) 20.07.2022 ATOMIC STRUCTURE Billntaoovcrion “The word “atom 4 Greek wont meaning indivisible, ie,an ‘ubimaie paicle which cannot be father subdivided, The idea ‘hata matter imately consists of extremely smal ptces was conceived by ancient Indian and Greck philosophers. The old «concept was put on frm footing by John Dalton in the form of ‘atomic theory which he developed inthe years 1803-1808. Tis {heory was a Tandmark in the history of chemistry. It explained succesfully a number of experimental observations such ss las ‘of chemical combination bat filed to answer the questions such (0) Why do he elements show diferent chemical activity? {Gy Why do the elements posses itferent atomic masses? “Towards the end ofthe nineteenth century, it ‘thatthe atom itself might be composed of even staller, ‘This change in viewpoint was brought about by experiments with leceiciy. Davy, in 1807-1808, isolated ve. eleenis (potassium, Sodim, calcium, stomium and barium) by using electricity and proposed that the elements ae held together compounds by siactions that are electric in natu In 163, ‘Michael Faraday showed that there is relationship betwee ‘mater and electricity. This was the first mujor rekihrogt to suggest hat the flo was nota simple indiviible parle ef mater but was made up of small particles. On the basis of Fanaday's work, Stoney proposed tht unt of elec agp ‘az associated wit toms. It 189) be suggested tha thee ngs be called electrons lecron iv Geek worl caning amber, ' material whieh becomes eletisly charged when bed wh wool or si ‘The complenity of the stn was further reveled when the following discoveries were mde in ubvequent ya, ‘0 appear pasties, (Discovery of cathode rays. (i) Discovery of positive rays, Ui) Discovery of X-rays (Gv) Discovery of radioactivity (0) Discovery of isotopes and isobas. During the past 100 years, scientists have made contibutions Which helped in the development of modem theory of atone Siriture. The works of J.J. Thomson and Ernest Rutherford ‘sewaly laid the foundation ofthe modem picture ofthe atom: is now believed tha the atom consists of several panicles called subatomic particles like elecon, proton, neutron, poston. Dneutino, meson, ete. Out of these panicles, the electron, the Proton andthe neutron are called fundamental paticles and se the building blocks ofthe atoms Hédlcatione ravs—oiscovery of evecraov ‘The nature and existence of electron was established ty experiments on conduction of electiiy through gases. In 1853 Julius Plucker stared the study of conduction of elects {hrovgh gases at low pressure in a discharge tube, [A comes ischarge tbe consists of a hard glass eylingtealwbe about $0 mong) with to metal eletodes seated on bath the ends. is Connected ose tbe through which team be evacstd 9 2 ested pressure withthe hep ofa vacuom pnp) Ae was lest completely renived om the dsshagge tube (esse about ‘simvphete). When a high voltae ofthe onder of HOO) slo ‘ore was nypress acto he slevteaen. some srt of inv ays moved them (5g. 21, Sine, the ey electra th postive elctode vative electra i tefere to a cathe,Gas at low pressure ‘Vacuum pump Cathout rays Fig. 2.1 Production of cathode rays these rays were called cathode rays. Cathode rays are produced by field emission. A strong electric field pulls the electron, out of. material, Further investigations were made by W. Crookes, J. Perrin, J.J. Thomson and others. Cathode rays possess the following properties: (i) They travel in straight lines away from the cathode with very high velocities ranging from 10°—10"" em, per second, A shadow of metallic object placed in the path is cast on the wall ‘opposite to the cathode (Fig, 22) Fig. 22 (ii) They produce a green glow when they strike the glass wall beyond the anode. Light is emitted when they strike the zine sulphide screen. (ii) They produce heat energy when they collide with the ‘matter It shows that cathode rays possess kinetic energy which is converted into heat energy when stopped by matter. (iv) They are deflected by the electric and magnetic fields. ‘When the rays are passed between two electrically charged plates, these are deflected towards the positively charged plate (Fig. 2.3). ‘They discharge a positively charged gold leaf electrascope. It shows that cathode rays carry negative charge. Cathode rays ‘Vacuum pump Fig. 2.3 (©) The cathode rays possess kineti energy. Its shown by the experiment that when a small pin whee! is placed in ther path, the blades ofthe whee! are set in motion (Fig. 2.4). Thus, the eathode rays consist of material particles which have mass and velocity. ‘These panicles carrying negative charge were called electrons. The mame “electron” was given by Stoney. (wi) Cathode rays. produce X-riys. When they fall on a material having high atomie mas, new type of penetrating rays of ‘ery small wavelength are emitted which ate called X-rays. (iy These rays affect the photographic plate. Canodorays gg Pin whoo! sea (1 Kjon pe Cathode ACuNy ‘anode Fig. 24 (vill) These rays-can penetrate through thin foils of solid ‘materials and cause ionisation in gases through which they pass. ix) The nature of the cathode rays is independent of: {a) the nature of the cathode and (b) the gas in the discharge tube. In 1897, J.J. ‘Thomson determined the e/m value (chargelmass) of the electron by studying the deflections of cathode rays in electric and magnetic fields, The value of elm has ‘been found to be ~17588%10* coulomblg, By performing a series of experiments, Thomson proved that ‘whatever gas be taken in the discharge tube and whatever be the material of the electrodes, the value of e/m is always the same, Electrons are, thus, common universal constituents of all atoms. Electrons are also produced by the action of ultraviolet light oF X-rays on metal and from heated filaments. B-particles emitted by radioactive materials are also electrons “The first precise measurement of the charge on the electron .was made by Robert A. Millikan in 1909 by oil drop experiment. ‘The apparatus used is shown in Fig. 2.5. A spray of il drops is, =<) ‘Atomizer Oil spray 4 Keays Fig. 25. Milikan's ol 6rop method forthe determination of charge ofan electron produced by an atomizer. The oil drops enter the apparatus through a small hole and are allowed to fall in between two charged plates The space between the charged plates is irradiated by X-rays which ionise the molecules of air. The movement ofthe droplets is observed with a telescope. A droplet may absorb one ‘or more electrons, i... acquires a negative charge. By applying an electrical field on the droplet under study which balances the downward gravitational force, the droplet becomes stationary. From the magnitude of the charge applied on the plate and mass of droplet, the charge on the droplet was determined. The chargefon the electron was found to be ~1.6022 x 10” coulomb. Since, an electron has the smallest charge known, it was, thus, designated as unit negative charge. Mass of the electron: The mass of the electron can be calculated from the value of e/m and the value of e, = 9.1096 x10 gor 9.1096 x 107! kg. This is termed as the rest mass of the electron, i.¢., mass of the electron when moving with low speed. Mass of the electron rel Mass of hydrogen atom, 1.008 amu 008 x 166 x10 g =1673 x10" g (since 1 amu =166x 107 9) Mass of hydrogen atom _ 1673 x10 91096 x10 =1837 ve to that of a hydrogen atom: Mass of the electron ‘Thus, Mass of an electror 1 Jga7 “Mass of hydrogen atom 1008 — 01000549 amu 1837 An electron can thus, be defined as a sub-atomic particle which carries charge ~1.60x 10"! coulomb, ic., one unit negative charge and has mass 9.1 10° g, ie., 1th mass 7 of the hydrogen atom (0.000849 amu). Eilrositive ravs—piscovery oF PROTON With the discovery of electrons, scientists started looking for positively charged panicles which were naturally expected because matter is electrically neutral under ordinary conditions. ‘The first experiment that led to the discovery of the positive particle was conducted by Goldstein in 1886. He used a perforated cathode in the modified cathode ray tube (Fig. 2.6). It Cathode Fig. 2.6 ‘was observed that when a high potential difference was applied between the electrodes, not only cathode rays were produced but also a new type of rays were produced simultaneously from anode moving towards cathode and passed through the holes or canals Of the cathode. These rays were termed canal rays since these passed through the canals of the cathode. These were also named ‘anode rays as these originated from anode. When the properties Of these rays were studied by Thomson, he observed that these rays consisted of positively charged particles and named them ag positive rays. The following characteristics of the positive rays were recognised: (i) The rays travel in straight lines and cast a shadow ofthe ‘object placed in their path. (ii) Like cathode rays, these rays also rotate the whee! placeg in their path and also have the heating effect. Thus, the ayy possess kinetic energy. iv., mass particles are present. (iii) The rays produce flashes of light on zinc sulphide screen, (iv) The rays are deflected by electric and magnetic fields in g direction opposite to that of cathode rays. These rays are attracted towards the negatively charged plate showing thereby that these rays carry a positive charge. (¥) These rays can pass through thin metal foils. (vi) These rays can produce ionisation in gases. (vii) These rays are capable of producing physical and chemical changes (vii) Positive particles in these rays have e/m values much smaller than that of electron. This means either mis high or the value of charge is small in comparison to electron. Since, a Positive particle is formed by the loss of an electron of electtons, the charge on the positive particle must be an integral multiple of the charge present on the electron, Hence, for a smaller value of elm, itis definite that positive particles possess a high mass, (ix) efm value is dependent on the nature of the gas taken in the discharge tube, ie., positive particles are different in different gases. Accurate measurements of the charge and the mass of the particles obtained in the discharge tube containing hydrogen, the lightest of all gases, were made by J.J. Thomson in 1906. These Particles were found to have the e/m value as +9.579x10* coulomb/s. This was the maximum value of e/m observed for any Positive particle. It was, thus assumed that the positive particle given by hydrogen represents a fundamental particle of positive charge. This particle was named proton by Rutherford in 1911. Its charge was found to be equal in magnitude but opposite insign to that of electron. ‘Thus, proton carries a charge + 1.602 x 10-! coulomb, ie, one unit positive charge. ‘The mass of the proton, thus, can be calculated. Mass of the proton = = 19%? elm 9579x104 =1672x10~ g or 1.672 x10 kg 1.672 x10 Mass of the proton in amu 1.66107 A proton is defined as a sub-atomic particle which has @ ‘mass nearly 1 amu (1.672 107 9) and a charge of +1 (+ 1.602 x 107” coulomb), Protons are produced in « number of nuclear reactions. On the basis of such reactions, proton ha fundamental building unit of the atom. been recognised a8EB oMson woveL oF arom “After the discovery of lecuon and proton, the se aoe ov these ON ctietons qesramerpov tee / Seam © Osea ewer vas Bea BF eae Te Ffomson inthe form \© 6 O/ Betsy Aitast model of the atom. He proposed that the ive charge #8 spread wera sphere in which he {leon are embedded to maketh atom asa whole neu. This tmodel was much like raisin in a puding and is also known Thomson's plum pudding model. This model was discarded a i ts not consistent with the resus of furter investigations such as sattering of ecpariles by thin metal fois, Fig. 2.7 Thomson's model of atom RUTHERFORD'S SCATTERING EXPERIMENT (DISCOVERY OF NUCLEUS) Jn 1911, Ernest Rutherford and his co-workers carried out a series of experiments using o-partcles” (Fig. 2.8 and 29). A Movable Gold fil e-partcies Radioactive ‘substance i (Poioniurs) Lead plate Deflected ca-paricles Fig. 2.8 beam of a-particles was directed against a thin foil of about 0.0004 cm thickness of gold, platinum, silver or copper respectively, The foil was surrounded by a circular fluorescent zine sulphide sereen. Whenever an O-particle struck the screen, it produced a flash of light. ‘The following observations were made: (i) Most of the c-particles (nearly 999) went straight without suffering any deflection, ii) A few of them got deflected through small angles, (ii) very few (about one in 20,000) did not pass through the foil at all but suffered large deflections (more than 90°) or even came back in more or less the direction from which they had come, ie., a deflection of 180°. ‘The following conclusions were drawn from the above observations: Largely detected Nucleus Slightly deflected a-paticles te particles cepartcies “particles Sight dolectod Soares Fig. 29 ( Since, most of the ocparticles went straight through the ‘metal foil undeflected, it means that there must be a very large empty space within the atom or the atom is extraordinarily hollow. (ii) A few of the c-particles were deflected from their original paths through moderate angles; it was concluded that whole of the positive charge is concentrated and the space occupied by this positive charge is very small in the atom. When a-particles come closer to this point, they suffer a force of repulsion and deviate from their paths. ‘The positively charged heavy mass which occupies only a ‘small volume in an atom is called nucleus. It is supposed to be present at the centre of the atom. (iii) A very few of the a-particles suffered strong deflections or even returned on their path indicating that the nucleus is rigid and ocparticles recoil due to direct collision with the heavy positively charged mass. Rutherford's Model On the basis of scattering experiments, Rutherford proposed a ‘model of the atom which is known as nuclear atomic model. According to this model: () An atom consists of a heavy positively charged nucleus where whole of mass ofthe atom is concentrated. The magnitude of the positive charge on the nucleus is different for different atoms. i) The volume of the nucleus is very small and is only a te fraction of the total volume of the atom, Nucleus has a [he radiations emitted by radioactive substance consist of a-particles. These particles are positively charged. These particles are actally helium toms from which electrons have been removed. Each particle consists of mass equal to about 4 times that of hydrogen atom and caries positive charge of two units. ts represented by the symbol or He He — He we Helium atom ovparticle Electron ‘o-panticles are usually obtained from a natural isotope of polonium-214.aa diameter of the order of 10"? (0 107! em and the atom has a diameter of the order of 10°* em.* Diameter of the atom __ 0! jiameter of the nucleus 10 ‘Thus, diameter (size) ofthe atom is 100,000 times the diameter of the nucleus. (ii) There is an empty space around the nucleus called extranuclear part. In this part electrons re present. The number of| ‘electrons in an atom is always equal to the number of protons Present in the nucleus. As the nucleus part of the atom is responsible for the mass of the atom, the extranuclear part is responsible for its volume. The volume of the atom is about 10'S times the volume of the nucleus, Volume of the atom _ (1078)? Volume of the nucleus ~ 19-9)? o™ 10 (iv) Electrons revolve round the nucleus in closed orbits with, high speeds. The centrifugal force acting on the revolving electrons is being counterbalanced by the force of attraction between the electrons and the nucleus. This model was similar to the solar system, the nucleus representing the sun and revolving electrons as’ planets. The electrons are, therefore, generally refered to as planetary electrons. Dissimilarities between Nuclear Atomic Model and Solar System (@) The sun and the planets are very big bodies and uncharged while the nucleus and electrons are very small objects and charged. Gi) The revolution of the planets in the solar system is governed by gravitational forces, while the revolution of ‘electrons around the nucleus is governed by electrostatic forces. In the solar system, there is only one planet which revolves jn any particular orbit, but in the nuclear atomic model ‘more than one electron may rotate in any particular orbit. Drawbacks of Rutherford’s Model (@ According to classical electromagnetic theory, when a charged particle moves under the influence of an attractive force, it loses energy continuously in the form of electromagnetic radiations, Thus, when the electron (a charged particle) moves in an attractive field (created by protons Present in the nucleus), it must emit radiations. As a result of this, the electron should lose energy at every turn and move closer and closer to the nucleus following a spiral path (Fig. Electron 2.10). The ultimate result will be that it Fig. 2.10 will fall into the nucleus, thereby making the atom unstable. Bohr made calculations and pointed out that an atom would collapse in 10 second. Since, the atom is quite stable, it means the electrons Nucleus do not fall into the nucleus, thereby this model does not explain the stability of the atom. (ii) If the electrons lose energy continuously, the observeg spectrum should be continuous but the actual observed spectrum consists of well defined lines of definite frequencies. Hence, the loss of energy by the electrons is not continuous in an atom, EE Mose ey exPeRIMENT—ATOMIC NUMBER Roentgen, in 1895, discovered that when high energy electrons in a discharge tube collide with the anode, penetrating radiations are produced which he named X-rays (Fig. 2.11), ‘Cathode rays Cathode Difracted Nietal target Ditraction unit Fig. 2.11 X-rays are electromagnetic fadiations of very small wavelengths (0.1-20 A), X-rays are diffracted by diffraction gratings like ordinary light rays and X-rays spectra are thus, produced. Each such spectrum is a characteristic property of the element used as anode, Moseley (1912-1915), investigated the X-ray spectra of 38 4ifferent elements, starting from aluminium and ending in gold. He measured the frequency of principal lines of a particular series (the orlines 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 of the clement. But, it was soon realised that the frequency of the particular spectral line was more Precisely related with the serial number of the element in the Periodic table which he termed as atomic number (Z). He resented the following relationship. W=az-) where v = frequency of X-rays, Z = atomic number, a and b are Constants. When the values of square root of the frequency were plotted against atomic numbers ofthe elements producing X-rays, 2 straight line was obtained [Fig. 2.12 (b). A van den Broek (1913) pointed out that the atomic number of an element is equal to the total positive charge contained in the ‘nucleus of its atom, Rutherford was also having the same opinion + Radius ofthe nucleus =1.33%10"? BC + bn been” aan ee The mass of the neutron was. determined. Mt was 1675 10°", i.e, nearly equal to the mass of proton, ‘Thus, a neutron isa sub-atomic particle which has mass 1.675 x 107 g, approximately 1 amu, or nearly equal to the mass of a proton or hydrogen atom and carries no electrical ‘charge. The em value ofa neutron i thus 210 The discovery of neuron led to slight modification of the Rutherford atomic model, The nucleus of the atom consists of Peons and neutrons. These ae collectively called as nucleons. The mass ofthe stom due to total numberof nucleons presen in the nucleus, Neutron and proton are interconvertible in the lus halflife is 200 ms Conclusions (All atoms except hydrogen atom are composed of three fundamental particles: (a) Electron, (by Proton, (e) Neutron. ‘The hydrogen atom consists of one proton and does not contin any neuton, ‘The properties of three and one electron fundamental paces ae summarised i the alo Property teavon Proton Newton Symbol a ee Mass (e). 9.1096 107% 1.6726 107 1.675 x 10" Relative mass lama) 0000549 1.00727 1.00866, Charge (coulomb), =160x10 = +1.60x 107 0 Relative carte 4 a 0 cover Li thomson—_futherord Chad (i) All atoms are neutral in nature, i.e, total positive charge is equal 10 the negative charge in an atom. The positive charge is contributed by’ protons and the negative charge is contributed by electrons. Every proton and electron carries an equal and opposite charge, Thus, in an atom, Number of protons = Number of electrons ‘This number is termed atomic number and is represented by the symbol Z. The atomic number of sodium is 11. It indicates that every atom of sodium consists of 11 protons and L1 electrons. ‘Whenever a change is brought in the number of protons. i-e..in atomic number, the element changes into another element. This change is not possible by chemical changes but itis possible by nuclear reactions when one element can be transmuted into another element. Whenever a change is brought in the number of electrons in an ‘atom, charged particles come into existence. These charged Particles are called ions. The positively charged ion or cation contains fewer electrons than protons. The positive charge on the cation is equal to the number of elections lost by the atom or the X-rays > y-rays > Cosmic rays Ik is expressed in em” of my (x) Amplitude: Tis defined as the height of the erest or depth of the trough of a wave. It is denoted by the letter ‘a’. It and 7 for hydrogen like species (Ey = energy of hydrogen first orbit) Since, n ean have only integral values, it follows that total nergy of the electron is quantised. The negative sign indicates that the electron is under attraction towards nucleus, i.e. it is ‘bound to the nucleus. The electron has minimum energy in the first orbit and its energy increases as n increases, ie. it becomes, less negative. The electron can have a maximum energy value of zero when n=es. The zero energy means that the electron is no longer bound to the nucleus, ie, it is not under attraction towards nucleus, For hydrogen like species such. as E, =Z?xE, (for hydrogen atom), Tonisation Energy : ‘Amount of energy tequited to remove outermost electron from an isolated gaseous atom is called its ionisation energy. Electron ‘can be removed from an atom when it is excited to infinite (=) shell He’, Li*, etc. 222 as6ev/a0n ‘Theses ase Fry ogea ihe ps He*, Li?*, Be** etc. If ionisation energy is known for an element then it can be calculated for other element using following "36 6 peratom wie62a9xi0% ey) is 1 4 i “ef 336 sna (ev =2306 etm a2 , Teal fara 1 =~ Riis By KE) Ponta! Energy (PE) = 2 * Total EnergyInterpretation of hydrogen spectrum: The only electron in the hydrogen atom resides under ordinary conditions on the first orbit. When energy is supplied, the electron moves to higher energy shells depending on the amount of energy absorbed, When this electron returns to any of the lower energy shells, it emits energy. Lym is formed when the electron returns to the lowest energy state while Balmer series is formed when the electron retuims to second energy shell, Similarly, Paschen, Brackett and Pfund series are formed when electron returns to the third, fourth and filth energy shells from higher energy shells respectively (Fi ). Paschen series kee ZzOR Brackett Ptund Lyman saree Fig. 2.22 Maximum number of lines produced when an electron jumps from nth level to ground level is equal to = B For example, in the case of n= 4, number of lines produced is 6, G5 3,4—5 2,45 1,352,329, the electron comes back from energy level having energy E> to nergy level having energy Ej, then the difference may be expressed in terms of energy of photon: Ey ~E, =AE=hv or the frequency of the emitted radiation is given by AE yok hk Since, AE can have only definite values depending on the definite energies of Ey and E,, v will have only fixed values in an atom, cae he Rh aE Since, handc are constants, AE corresponds to definite energy’ thus, each transition from one energy level to another will produce a light of definite wavelength. This is actually observed asa line in the spectrum of hydrogen atom, ‘Thus, the different spectral lines in the spectra of atoms correspond to different transitions of electrons from higher energy levels to lower energy levels. Let m, and nz be the two energy shells in the hydrogen atom (ny 123 4 5 6 7 Designation of shell K LM NOP Q () Higher is the value of 'n’, greater is the distance of the shell from the nucleus NEEM ET STSS r= x0529A Z ii) Higher is the value of ‘n’, greater is the magnitude of energy. Ey Three-fold degeneracy d Five-fold degeneracy f Seven-fold degeneracy (i) All orbitals of the same subshel differ in the direction of their space orientation (ii) Total numberof orbitals in a main energy shells equal 10 n? (but not more than 16 in any of the main shells of the known elements). 14s) 4 (28, 2P1. 2p» 2Pe) No. of orbitals = (1)? No. of orbitals = (2)* No. of orbitals = 3) 85,304. 3P yr 3Per 3d yy 3dr Moy 34,2 234.2) n=4 No. of orbitals =(4)? =16 ‘The division of main shells into subshells and that of subshell into orbitals has been shown here: umber: When spectral lines of H, Li, Nay ‘observed by means of instruments of high resolving, power, each line was found consisting ofa pair of lines (known as doublets). To account for these doublets, it was suggested that the N s Magnetic fold 2at clectron while moving around the nucleus in an orbit is also spinning about its own axis either in clockwise or in ance dition The ar wo possi vas eter + 4 depending onthe direstion of spin, These spins are also shown by arrows: upwards (1) or downvsargs (. Spin +3 T clockwise 1 Spin-+ 1 anticlockwise cnr Spinning electron produces angular momentum equal to h aster) b= FD 5 Total spin =n x4 sumer of unpaired electrons ‘The electrons with the same sign of spin quantum numbers are said to have parallel spins while those having opposite signs of spin quantum numbers are said to have opposite spins or paired up spins. opposite or . parallel TL] paired spins 1 spins Since a spinning charge is associated with a magnetic feta, an electron must have a magnetic moment associated with it Spin magnetic moments given by hth 045 2nme ‘The pare electrons cance the magnetic moment and develop routual magnetic moment,