Atomic Structure (a) (b) (c) (a) (b) © (a) (e) ATOM & MOLECULES ‘The smallest particle of a matter that takes part in a chemical reaction is called an atom. The atom of all gases except those of noble gases, cannot exist in free state. These exist in molecular form, The molecules of hydrogen, nitrogen, oxygen and halogens are diatomic (H,, N,). Phosphorus molecule is tetratomic and that of sulphur is octa atomic. The smallest particle of a matter that can exist in free state in nature, is known as a molecule Some molecules are composed of homoatomic atom, e.g., Hy, O,, N,, Cl, O, ete., while the molecules of compounds are made up of two or more heteroatomic atoms e.g., HCl, NaOH, HNO,, CaCO, ete. DALTON’S ATOMIC THEORY The coneepts put forward by John Dalton regarding the composition of matter are known as Dalton’s atomic theory. Its important points are as follows. Every matter is composed of very minute particles, called atoms that take part in chemical reactions. Atoms cannot be further subdivided. The atoms of different elements differ from each other in their properties and masses, while the atoms of the same element are identical in all respects. The atoms of different elements can combine in simple ratio to form compounds. ‘The masses of combining elements represent the masses of combining atoms ‘Atom can neither be created nor destroyed.o © @ © ® ) o @ CATHODE RAYS (DISCOVERY OF ELECTRON) Dry gases are normally bad conductors of electricity. But under low pressure, i, 0.1 mm of mereury of lower, electric current can passthrough the gases. Julius Plucker in 1859 found that a type of rays called cathode rays, emit from the cathode when electricity i passed through a discharge tube. William Crookes (1879), J.Thomson and many othe seientiss studied the properties of eathode rays and came to the conclu sion tat the cathode rays of same properties are obtained using any gas o any eathode material Tovacuum pump Production of cathode rays “The salen features of cathode ray areas follows, Cathode rays travel in a straight line, This indicates thatthe Formation ofa shadow when an opaque objects placedinits path Ifa light metal pinwheel is placed in the path of eathode rays, the wheel stars revolving. This proves thats cathode rays consis of tiny particles having momentum. Cathode rays get deviated in electrical and magnetic fields. This proves that they ae composed of charged particles. ‘Their derivation towards anode indicates their negatively charged nature. The direction of thei ‘deviation in magnete field depends on pole of the magnet which has been placed near the cathode ray tube Cathode rays produce green fluorescence onthe wall of the glas tube Cathode rays produce incandescence in at thin metal fil Cathoie rays effect the photographie plate Cathe rays ionize gases proving that heya Cathode rays penetrates across a thin metal foi Cathode rays produce X-rays when they hita pice of tungsten or any other metal having high melting point. 3.1 Nature of Cathode Rays 44. Thomson (1897) proved through experiments that Cathode rays are composed of extremely tiny negatively charged particles (electrons). ‘The ratio of negative charge (e) and mass (m) for cathode ray particle (electrons) is a constat, This ratio is independent of the material used in the preparation of the electrodes ofthe discharge tube or the gas filled in {it Thus, fm ofan electron isa universal constant charged. charge on electron ‘mass of electron ~ im 76 « 10 Coulombgm In addition othe sbove proof, photoelectric eft, thermionic eet and emission of beta particles from radioactive elements alo confi tht eletonis an cssental constituent of mate. These negatively charged tiny prices dacoverd by Thomon,ltis dented by €or ison eo(@ (b) © (d) (ce) (f) POSITIVE RAYS OR CANAL RAYS : DISCOVERY OF PROTON Eugene Goldstein in 1886 found that a dim glow is visible behind the cathode when an electric discharge is passed through a perforated cathode in a discharge tube filled with a gas at low pressure. These new type of 10 these rays because these rays cross the canals of the cathode and reach the other side. W.Wein in 1897 proved through experiments that the canal rays consist of positively charged particles. JJ. Thomson gave the name positive rays to them because they are composed of positively charged particles. rays travel from anode to that cathode. Goldstein gave the name canal rays 4.1 Properties of Positive Rays : Positive rays travel in the direction opp to that of cathode rays. Positive rays travel in straight line. Positive rays affect photographie plate. Positive rays are deviated in the electric and magnetic fields. ‘The direction of their deviation proves the presence of positive charge on their particles. Positive rays pass across a very thin sheet of metal. But their penetrating power is rays, Positive rays produce fluorescence and phosphorescence.6. ELECTRON (¢ or (a) Electron is a fundamental particle of an atom, which is an essential constituent of every matter. (b) The credit for discovery of cathode rays goes to Sir William Crookes while the credit for discovery of negatively charged electron goes to J.J. Thomson. The name ‘electron’ was first given by Stony. (©) Aunit negative charge is present on electron,@ (b) © @ © © ) ) @ DISCOVERY OF NEUTRON Penetrating rays are emitted on bombarding a-particles on the elements like beryllium, boron and aluminium, James Chadwick in 1932 studied the nature of these radiation and came to the conclusion that these rays are composed of very tiny electro neutral particles. The mass of these particles is almost equal to that of the hydrogen atom. This particle is called neutron and is denoted by the symbol, jn 7.1 Neutron (.n') It is a fundamental particle of atom that is present in the nuclei of all atoms except hydrogen or protium. It was discovered by James Chadwick in 1932. Itis an electro neutral particle, ic. it does not have any positive or negative charge on it. The mass of a neutron is almost equal to that ofa proton. Actually itis a little bit heavier than proton. Its mass (m) is as fallows : Mass (m) of a neutron = 1.6748 « 10 gram = Approximately mass ofa proton Neutro1 relatively hea out of the three fundamental particles of an atom. Molar mass of a neutron is obtained by multiplying the mass (m) of a neutron with Avogadro number (6.023 10°), Therefore the gram molecular mass of a neutron is 1.6748 * 10 ** x 6.23 x 10° = 1.00893. The atomic mass is equal to the total mass of all the protons and neutrons present in the atom. Isotopes are formed as a result of difference in the number of only neutrons in the nuclei of atoms. Itis assumed that a neutron is a result to joining together of an electron and a proton. A neutron, being unstable, decays as fallows : n> . P! +_e° + ,q° (antineutrino) Its half-life is 20 minutes.10. Some important definations 1, Atomic Number : Itis represented by Z. The number of protons present in the nucleus is called aton is also known as nuclear charge. ic number.of an element. It For neutral atom : Number of proton = Number of electron For charged atom: Number of = Z — (charge on atom) ‘Z= number of protons only 2. Mass Number : It is represented by capital A The sum of number of Neutrons and protons is called the mass number. of the element. It is also known as number of nucleons becuase neutron & proton are present in nucleus. A= number of protons + number of Neutrons Note : It is always a whole number. Atom: Inside the nucleus (Outside the nucleus bpd fe] An atom of the element is represented by ,X* Where, X = Symbol of element Atomic number = no. of proton = no. of e (If atom is neutral) A= Mass number = no.of neutron + Atomic no. eg. Nal F er sow (p> 1) (p> 9% (pr > 6) (p> 8) (© > 10) (© > 9+1=10) (€ 36) (€ 38) eg. oe or" p>6 pos n> 12-6=6 n> 16-8=8 e6 essMass no. [A] and atomic weight (a.m.u= atomic mass unit) Mass of Proton (m, ) ‘Mass of Neutron (m, ) ‘Mass of electron (m, ) 1.673 « 107" kg 1,675 « 107" kg. 9.1% 10°" kg. 1.673 x 10% grams 1.675 x 10% g. 9.1% 10° kg. 1.00750 a.m.u. 1.00850 a.m.u. 0.000549 a.m [m, =m] [m, > m,]Atomic Weight : The atomic weight of an element is the average of weights of all the isotopes of that element. An element have there isotopes y,, y, and y, and their isotopic weights are w,, w,, W, and their percentage/ possibility/probability/ratio of occurance in nature are x,, x,, x, respectively, then the ave, atomic weight of element is ~ ave. wt eg. crs cr Probability ratio 73% 25% 3 1 35x3437x1 _ 142 _ ye 341 4 Br: Brit 1 : 1 (Ratio of occurance) 79 x1+81x1 160 “Ter 7 27805. Isobar's : They are atoms with the same mass number but different atomic numbers. eg. oe, iF wAr*, yCa® Si, gP™11, THOMSON'S MODEL OF ATOM [1904] ‘Thomson was the first to propose a detailed model of the atom. ‘Thomson proposed that an atom consists of a uniform sphere of positive charge in which the electrons are present at some places. * This model of atom is known as "Plum-Pudding model" or "Raisin Pudding Model" or "Water Melon Model", sphere of He charge Drawbacks : * An important drawback of this model is that the mass of the atoms is considered to be evenly spread over that atom. * It isa static model. It does not reflect the movement of electron. 12. RUTHERFORD's a- SCATTERING EXPERIME! a-scattering experiment thin gold foil (,00001 em) strike here , k Zns Screen source (Ra) of slit system o-rays lead plate oan (ead plate) [doubly ionised He atom] | most of o—particles circular fluorescent screenRutherford observed that - @ Gi) (iii) a) Q) @) Most of the a-particles (nearly 99.9%) went straight without suffering any deflection. A few of them got deflected through small angles. Avery few a-particles (about one in 20,000) did not pass through the foil atall but suffered large deflections (more than 90°) or even come back in the direction from which they have come i.e. a deflection of 180°, largely deflected Slightly deflected a-particles particles Following conclusions were drawn from the above observations - Since few of the a-particles were deflected from their original path through moderate angles; it was concluded tha whole of the +ve charge is concentrated and the space occupied by this positive charge is very small in the atom ‘Whenever 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 i supposed to be present at the centre of the atom. Since most of the a-particle went straight through the metal foil undeflected, it means that there must be ver large empty space within the atom. Avery few of the a-particles suffered strong deflections or even retumed on their path indicating that the nucleus is rigi and a-particles recoil due to direct collision with the heavy positively charged mass.Drawbacks of Rutherford model - (1) This theory could not explain the stability of an atom. According to Maxwell electron loses iia Nucleus it's energy continuously in the form of electromagnetic radiations. As a result of thi € should loss energy at every turn and move closer and closer to the nucleus following a spiral path, The ultimate result will be that it will fall into the nucleus, thereby making the atom unstable, (2) Ifthe electrons loss energy continuously, the observed spectrum should be continuous but the actual observed spectrum consists of well defined lines of definite frequencies (discontinuous). Hence, the loss of energy by electron is not continuous in an atom.15. Bohr's Atomic Model Some Important formulae : a, Coulombic force = “= Centrifugal force =" T Angular momentum =mvr This model was based on quantum theory of radiation and Classical laws of physics. Bohr model is applicable only for single electron species like H, He", Li? ete, Bohr model is based on particle nature of electron. The important postulates on which Bohr's Model is based are the following : 1 Postulate : ‘Atom has a nucleus where all protons and neutrons are present. The size of nucleus is very small and it is present at the centre of the atom. 2™ Postulate = Negatively charged electron revolve around the nucleus in the same way as the planets revolve around the sun. The path of electron is circular. The attraction force (Coulombic or electrostatic force) between nucleus and electron is equal to the centrifugal force on electron. ie. Attraction force towards nucleus = centrifugal force away from nucleus. 3" Postulate : Electrons can revolve only in those orbits in which angular momentum (mvr) of electron i ah ie my = =*!= nh f= hash = 2x where: n= Whole number h = Planck's constant, p = Constant ‘Angular momentum ean have values such as 2 . but can not have fractional ra values such as 1.5 4" Postulate : ’ The orbits in which electron can revolve are known as stationary Orbits because in these orbits energy of electron is always constant.5* Postulat * Each stationary orbit is associated with definite amount of energy therefore these orbits are also called as «energy levels and are numbered as 1, 2,3, 4, 5, OF K, L, M, N, O, ww ftom the nucleus outwards, 6* Postulate + ‘The emission or absorbtion of energy in the form of photon can only ‘oceur when electron jumps from one stationary state to another & it is, DE = Bocce ~ Ena se ~ Energy of a quantum * Energy is absorbed when electron Jumps from inner to outer orbit and is emitted when electron moves from outer to inner orbit. Important Definations (Ionization energy : Minimum the energy required to liberate an electron from the ground state ofan isolated atom is called the ionization energy. (i) Separation energy : Minimum energy required to remove an electron from its excited state is called as separation, energy, (ili) Excitation energy : Amount of energy required to shift an electron from ground state to any excited state. Note : All these kinds of energy are always positive.18. Limitation of the Bohr's model : 1. Bohr's theory does not explain the spectrum of multi electron atom. oh 2. Why the Angular momentum of the revolving electron is equal to 5, has not been explained by Bohr's theory. 3. Bohr inter-related quantum theory of radiation and classical law of physics without any theoretical explaination. This, was the biggest drawback of this model. 4, Bohr’s theory does not explain the fine structure of spectral lines. Fine structure of the spectral line is obtained when spectrum is viewed by a spectroscope of high resolving power, 5. Bohr’s theory does not explain the splitting of spectral lines in the presence of magnetic field (Zeeman effect) or electric field (Stark effect)2. According to de Broglie, the wavelength 2 of an electron is inversely proportional to its momentum p. 1 L hot Die P * my Here h = Planck's constant p= momentum of electron Momentum (p) = Mass (m) * Velocity (ec) 3. Derivation of de-Broglie Relation The above relation can be derived as follows by using Einstein's equation, Planck's quantum theory and wave theory of light, i) E= me? (Einstein's equation) Where E is energy, m is mass of a body and c is its velocity. E=hv=hx : (Planck's equation) (v= combining (i) and (ii) E= mei hx > or me a= raat my P 4 It is clear from the above equation that the value of 4 decreases on increasing either m or v or both. The wavelength of many fast-moving objects like an aeroplane ora cricket ball, is very low because of their high mass.21, a i) Heisenberg uncertainity principle Bohr's theory considers an electron as a material particle. Its position and momentum can be determined with accuracy. But, when an electron is considered in the form of wave as suggested by de-Broglie, it is not possible to ascertain simultaneously the exact position and velocity of the electon more precisely at a given instant since the wave extends throghout a region of space. In 1927, Werner Heisenberg presented a principle known as Heisenberg uncertainity principle which states that :"Itis impossible to measure simultaneously the exaet position and exact momentum of a body as small as an electron." The uncertainity in measurement of position, Ax, and the uncertainity in momentum. Ap or mAv, are related by Heisenberg's relationship as : ( p= mv, Ap = mAv) i JAx.Ap 2 2— or = AX. mAv> or an an where h is Planck's constant. When Ax =0, Av = Re member} n When av=0, Ax = So, if the position is known quite accurately, i.e., Ax is very small, Av becomes large and vice-versa.22. (a) (b) (@) (b) © @ () o @® Ex.45 Sol. Ex.46 Sol. @) (b) © @ © © QUANTUM NUMBERS ‘The position of any electron in any atom can be ascertained with the help of quantum numbers. In an atom, the shell consists of sub-shells and the sub-shell consists of orbital can accommodate only two electrons, which are in opposite spins, 22.1 Principal Quantum Number (n) Principal quantum number indicates the shell or energy level or orbit. An atoms has K, L, M,N, 0, P, Q, ete. shells. Principal quantum number also gives information about the radius of size Principal quantum number also gives information about the distance of an electron from the nucleus in an atom Principal quantum number also given information about the energy of an electron, Principal quantum number also gives information about the velocity ofan electron. In any orbit, the number of orbitals is given by n? and number of electrons is given by 2n?. This is called Bohr-Bury rule. Which of the following is the principal quantum number for the last electron of Na? (3 [212 B14 (41 Ans. [1] )Na= 132, 25%, 2p, 3s! n=3 Which of the following should have greater size ? (is [2]2s [B)3s [4] 4s Ans. [4] n=4 fords 22.2, Azimuthal Quantum Number (0) Azimuthal quantum number gives information that a particular electron belongs to which sub-shell. In an atom the shells consist or sub-shells which are indicated as s, p, dand f. Azimuthal quantum number determines the shape of an orbital. ‘The value of n starts from 1, while that of / starts from 0. Therefore, the maximum value of /is n ~ 1 The values of n and / can never be equal. Sub shell s op da ff 1 o 1 2 3 ‘The number of orbitals in any sub orbit is determined by the expression 2/+ | and the number of electrons is determined by the expression 2(2/ + 1).(@) =O +s Subsshell-» Spherical I= 1 +p Subsshell-» Dumbsbell 2 -+dSubsshol-» Double dumbsbe 3 + Subshell-» Complex (8) The order of energy of various sub-shell present in any shells $< p-t Ble—1 ‘Ans. [2 Sol. All the energy states in which nis greater than I are called excited states. 23. Rules for filing of orbitals 23.1, Aufbau Principe: ‘Aufbau isa German word and its meaning is ilding up" Aufbau principle givesasequsncein which various subshell ar filled up depending on therelative onder of the energies of various subshels + Principle: The electrons ae filled up in increasing order ofthe energy of the subshels. The subshell with ‘minimum energy is filled up tt and when this subshell obtains maximum quota of electrons then the next subshel of higher energy startling. + ‘Thesequence in which varios subshell are isthe following.23.2. (nt) ule: According to tthe sequence in which various subsbel ar filled up can also be determined with the help of | (240 value fora given subsbel Principle of (n+/) rule : ‘The subshell with lowes( n+) valu is filled up first, but when two or more subshells have same (n+) value oer yps ] ef 23.3 Pauls Exclusion principle: {In 1925, Paul stated that no two electrons in an atom can have same values ofall four quantum numbers ‘An orbital ean accomodate maximum 2 electrons and that oo with oppsit spin 23.4, Hund's Rule of Maximum Multiplicity: (Muliplicity = Many ofthe same kind) According. to Hund’ rule electrons ae distributed among the Orbitals of subshell in such a way aso give ‘maximum number of unpaired electron with parallel spin. in asubshel paring of eletron will no star uni and unless all the orbitals ofthat subshell will get one electron each with same spa, Exceptions of Aufbau principal In gome case itis observed that the actual electoric configuration of an element is lightly different from the arrangement given by aufbau principal. simple resion behind this is thatthe al filled and full filled subsbell have go extra stability duc to symmetry and exchange ener. Example Nb, Mo, Ru, Rh, Pd, Au, Ag, Pl La, Ce, Pm, Ga, Ac, Th, Pa, U.Np, Cm, Bk Electronic Configur Hoist He > Mo sya Be Bo 1s: 28 2p! co iN 18,2829" o> Fo 8,28, 29° whe Na + Is*, 2s, 2p', 3s! aoAt a Si 18,28, 2930 wo 3p S182, 2936, ph “cl > a + 18,2029. 38, 39° Pst 18,28, 98,38, 3p at + i 43 “18, 26,236 3 a + 2.34 +1828, 29", 38, 3p 0b (Exception) 2Mn > Sif, d Sa “+18 26,29", 36 as 3 co 3483 “18.26, 2p 38, 3 as cu 3p48, 34" [Exception] Zn > 15,25, 2p 38, 3p 4, 3d 6a > 3 453 Ap! +828, 2p", 38, 3p 48 2 yA SO 18282936, 39% 48,30" sBr 2.394533" Ap Ke 9S 25,3, 3p a ph 24. DIFFERENCE BETWEEN ORBIT AND ORBITAL SNe. ‘Orbie ‘Orbiter 1 isdepced bya Tisdepicted by m 2 ‘thas maximum clecton | Ithas maximum electron capacity of 2? capacity of in accordance ith Paul's prince 3 Teisbiggeinsize Ieissmullerinsize * Omitconsistofaaboriis | Suborbitconssw of om 5 The phon clecron The space around the maslew around the mucous is where probability of iingan calleanorit elecwonis maximum, icaled an orbital 28. ORBITAL (2) Thespace around the nucleus where probability of finding an electron is maximum, i called an orbital (©) _An-lectron cloud is negatively charged and the nucleus is positively charge. Therefore, the probability of finding an electron is maximum around the nucleus. (©) Theprobablity of finding anlectron isan orbital is 98% 10 98%. 25.1 Orbis (2) Onlyone sorital is possible in an orbit because = O.and m= 0 fort (©) _lisspherical in shape and thus the electron density is uniform in all directions. (©) Thesize increases with increase inthe value of n. There i vacant space between 1s orbital and 2s orbital, were the probability of finding electron i minimum, its known as nodal surface. (@) _Thenodalsurfce is missing inside Is orbital because ofits proximity with he nucleus, (©) Thenumber of ndel surfaces in an obit is equal to (0 ~ 1)) o @ O) o © 0 a, “iy ww o 25.2 p-Orbital Forp orbitals, /= | and + I Ths, team have thre configurations, which ar distributed nx, yand, zanes. Therefore, there are three porbitals, which are dumbbell, shaped Each p-rbital has two lobes and the probsblity of finding electron inside these two lobes sequal. The plane perpendicular tothe axis wo lobes and passing through the pint where these two lobes oi, isthe nodal plane ‘portal because the probability of finding electron in this planes negligible or minimum. ‘The valu of nodal planes for each ofthe p,-p, and p, orbitals is same and these nodal planesare presenti xy, ead x planes, respectively. The three p-obitals ofa particular orbit (pp, and p,) have equal energy and therefore these are called degenerated orbitals 25.3 d-Orbitals Ford orbitals, /=2.nd m= 2,-1.0, 1, +2. Therefore there are ive orientations and thus five d-obitals i shapes ikea double dumbbell ‘The five orientations of d-orbitals areas follows ‘The double dumbbell of, orbital are situated between x and y axes. Thedouble dumbbell of orbital ate situated between y and 7 axes Thedouble dumbbell fd orbital are stated between x and 2 axes The double dumbbell of.» orbital ae directed on x and y anes «orbital is composed of one dumbbell and one ing. The dumbbell isstutedon axis andthe ings present Mytnia Sct — Mat Msn soi ‘Shape of Orbits 25.4 orbitals (@) They have complex shapes, (i) For these, /= 3 and m=~3,-2, (iy These have seven orientations, 1,0,+1,42,43) wocuee