Chemistry 1st Paper New Egitio®‘Theoretical Lectures = 22 Class Activities = 10 Total Periods = 32 Chapter-2 Qualitative Chemistry Introduction : To the scientists, this bea iful world is “matter'and the other is| ‘radiantsenergy’; Material structure is composed of different atoms Te or unlike. fundamental particles, Qualitative chemistry includes all atom composed of two things— one is Atom is composed of some related topics like their discovery, identification and distribution of the fundamental particles in atoms. dadiant II types of radiant energies are ature and thessun\istheinyprime”source;| Light wave energy itself is invisible; but a portion of light electré nagnetic i energy having definite range of wave-length can make the Key Words : Electro magnetic waves, frequency and hertz, photon, quantum numbers, orbital, node, Pauli exclusion principle, Aufbau- rule, Hund’s rule, IR-ray, UV- ray, MRI-test, flame-test, solubility, solubility product, common-ion effect, crystallisation, sublimation, distillation, solvent extraction, material substances visible and hence that particular range of [chromatography. Gas Slit Prism discharge tube with Hy light is known as ‘visible-light'. Except that, im ible light includes IR-ray, UV-ray, radio- television waves etc. We use these waves in different ways. Different atoms absorb these wave energies and form different distinctive spectra which help to identify those atoms. Detection of inorganic ions; separation & purification of organic compounds are discussed in qualitative chemistry. Chemistry First Paper—1290 Chemistry- First Paper After reading this chapter, students will be able — 1, To compare between Rutherford's atom 12, To explain solubility, principle of model and that of Bohr. 2. To explain different atomic subshells and their capacity to contain electrons based on quantum numbers. 3. To describe quantum subshell-energy levels and their shapes. 4. To do electronic distribution in atoms according to Aufbau, Hund’s rules and Pauli's exclusion principle. 8 5. To explain the electro-magnetic spectrum. 6. To identify different elements from their solubility and solubility-product of ionic compounds. 13. Practical : To detect cations and anions in solution. 14. To explain method of crystallis: 15. Practical : To prepare pure crystals of sodium chloride from impure common salt by crystallization. To explain distillation, fractional distillation, steam distillation and sublimation. distinctive spectra, 17. To describe solvent extraction of 7. To explain H-spectrum according to different compounds from their Bohr's atom model. mixtures. 8, To explain the use of UV-ray to detect 18. To explain basic concept of fake currency notes and pass-ports. 9. To explain pain-relief by IR-ray 9, chromatography, . Practical : ‘To seperate compounds from application in medical treatment. mixture by chalk/filter paper 10. To describe principle of MRI test in chromatography. diagnosis of diseases. 20. To explain the importance of qualitative 11. Practical : To detect metal ions by fee analysis of substances in practical fields. 2.1 Atom Model and Primary Co In 1897, while experimenting o{ cathode rays, $a fundamental particle of an ato: ifferent scientists were engaged to know the atomic structure, After the discovery of electron, the realisation among the scientists was that atoms are divisible. From 1897-1932, different scientists forwarded their concepts about atomic structures, depending on their experimental observations together with theoretical arguments, which are known as atomic models. Here three prime atomic jels are to be discussed as follows : |. Rutherford's atom model forwarded in 1911 2. Bohr's atom model forwarded in 1913, 3. Quantum Mechanical atom model : forwarded in 1924-1927, therford forwarded his atom model after his experimental observations from his famous alpha (ct) particle scattering experiment.Qualitative Chemistry Ot 2.1.1 Rutherford’s alpha (0) particte Scattering Experiment(Nucleus ) discovery —__—— After the discovery of electron several scientists speculated about the structure of atom. To have some insight about the structure of atom, Ruutherfordjand his co-workers (Gieger and Marsden) carried) outsaniexperimentywithyalphayparticleyinyl91ls Before his experiment it was discovered that some elements like Radium (ggRa),Uranium (9U) emitisomelparticles. Oneiof 5 ne ‘Alpha particle is double positively charged helium nucle It is emitted from radioactive substance. It contains two protons and two neutrons-When two electrons are taken ut of a Helium atom, the resulting He®* ion is same as alpha particle. The alpha particle has very high velocity (1.0 x 107 ms"! to 2,510" ms). ‘Rutherford’s Experiment ; Rutherford:used 3 substances:for/his experiments GQ) a-pamictes emitted from radioactive substance like Radium, (2) Very thin gold foil (0.0004 cm), and (3) The screen covered with ZnS (zine sulphide) —— GEscription of the Expt. : Rutherford used fast moving alpha particles as 'bullets' which he fired at a very thin (0.0004 cm) sheet of gold atoms. He placed a circular screen covered with zinc sulphide (ZnS) behind the gold foil. It was known that "when the alpha particles fall on zinc sulphide, a minute bright flashes of light are emitted’. Observation ; Rutherford observed : () About 99% of a-particles passed in straight lines through the gold foil and then fell upon the ZnS layered screen making it bright by flashes of light. (ii) Only a few c-particles were deviated from their straight paths. ) Very few o-particles about I in 20,000 Fig 2.1: Scattering of a-particles in (twenty thousand), returned back. cuisine Here ‘onclusion ; From his experiment Rutherford drew following conclusions : ) Major part of an atom is empty or vacant. Electrons may be present in this space., Due to their negligible masses compared to O.-particle, they can not deflect the high speedy o-particles.92 Chemistry— First Paper (2) Since a few c-particles (positively charged) are deflected through some angles and a very few a-particles turn back on their opposite paths, atoms would have positively charged bodies which repel positively charged a-particles. Rutherford named this positively charged body as nucleus of atoms. (3) Returning back of c-particle in opposite direction suggests that the nucleus is heavy where all the masses and positive charges are concentrated centrally in a small region. (4) From the number of ct-particles deviated from their paths Rutherford calculated the size of the nucleus and found that the while that of the nucleus is 10-13 cm. It follows that diameter of an atom is about"{0®"timte? greater n that of the nucleus. This proves that major part of the atom is empty. ‘4G)'From the amount of deviation of a-particles Rutherford further showed that the amount of positive charge on an atomic nucleus is equal to the atomic number of that element, Rutherford knew that the mass of an G-particle is 7,000 times heavier than the mass of an electron and it is doublely positive charged. 2.1.2 Rutherford's Atom Model Based on a-particle scattering experiment, Rutherford forwarded his atom model in 1911. leliare'as follows’: (2) An atom has two parts : Two parts of an atom are (i) nucleus and (ii) extra nuclear part. Nucleus is a minute, massive positively charged body at the centre of the atom. All the positive charges and almost total mass of the atom are present in the nucleus, The volume of the nucleus is very small compared to that of the atom as a whole. <—— Centrifugal force ewan = Resultant Centripetal force nucleus Fig. 2.2 : Rutherford's atom model n Sey ae (2) Atom is electrically neutral : So a number of electrons equal to positive charges of the nucleus are present in an atom. Electrons are in constant motion around the nucleus in different circular orbits like the planets in a solar system. (3) Due to the constant motion of the electrons around the nucleus, the outward centrifugal force is exactly counter-balanced by the inward electrostatic attraction between the electrons and nucleus i, e. centripetal force.. Qualitative Chemistry 93 ince Rutherford's atom model resembles the solar system, it is also known as solar system atom model. Again since the concept of nucleus was first introduced in this atom * mosis also Frown as nuclear model of atom. Limitations of Rutherford's Atom Model ‘There are some limitations in Rutherford's atom model, which are stated below : (1) The Rutherford's atom model has been compared with the solar system. The rotating electrons are negatively charged and repel each other while the rotating planets are neutral and have force of gravitation acting between them. On the otherhand the force between nucleus and electrons is electrostatic. So here comparison between gravitational force and electrostatic force is not correct. =[—=- 2) According to Maxwell's ele lectromagnetic theory, any charged particle while revolving will emit radiation and lose energy: Thus rotating or revolving electrons round the — nucleus will lose energy and their orbits will become smaller and smaller and they will ultimately fall into the nucleus following a spiral path in about 10-8 second. But it does not occur practically. (3) Rutherford's atom model can not give any explanation of the atomic spectra. ' (4) Rutherford did not give any idea about the shape and size of the orbits of electrons in an atom. nf (5) There was no explanation about the rotation of many fj, 23. spinl pahora electrons in an orbit in Rutherford’s atom model. revolving electron’ erford used alpha (@) parti Jn. 2.3 : Prove that 2.1.3 Bohr's Atom Model 1913 Neils Bohr proposed his famous atom model, which not only described the new structure of an atom but also, eliminated the limitations of Rutherford's atom model like— (i) the shape and size of the orbits of electrons, — a]94 ‘Chemistry- First Paper (i) the limitation raised from Maxwell's electromagnetic theory and ii) gave an explanation about the origin of atomic spectra Bohr's Atom in definite circular paths or orbits containing definite energy around the nucleus, During the rotation the electrons will follow all rules of physics. But so long electron or electrons remain in a definite orbit, it will not absorb or radiate any energy. These circular paths are known as stationary orbits or energy levels of electrons. Each energy level has a definite or fixed energy. These energy levels are designated by n. For the nearest energy level or orbit n = 1, for second orbit _n = 2 and so on. (2) Concept of angular momentum of electrons : The permissible orbits or energy levels are those for which angular momentum of the revolving electrons are an integral multiple of h h 35 The angular momentum, mvr = n_x 333 where m = mass of an electron, v = linear velocity of electron, r= radius of orbit, vr = angular velocity, n = 1, 2, 3 ... represents the number of orbit, h = Plank's constant, (3) Gonceptofioriginiofiatomic:spectral ‘Mies+: An electron can jump from an orbit <---enernysbosorbed AE = EE, or energy level to another. When an electron jumps from lower energy level (E}) to higher energy level (E2), then it absorbs energy. On the other hand if an electron jumps from higher energy level (Ez) to lower energy level (E,), then it emits energy. The ape ay amount of energy emitted or absorbed is the Fig 24 : Bohr's atom model difference between the energies of the two levels such that (Ej — E,) =h®; where 8 (nu) ii ' the frequency of emitted or absorbed energy and 'h’ is the Plank's constant. Here the related radiation energy, AE = (E7— E}) will produce an atomic spectral line corresponding to frequency @ (nu). «. AE =(E)—Ej)=hd. : ——=+—wh Qualitative con Ta @ 95 v Limitations of Bobr's Atom Model - “@) Bohr’s atom model can explain spectral lines of H-atom and ions of one electron like Het, Li? ion. It can not explain spectral lines of atoms with many electrons, %@) According to Bohr's model when an electron jumps from Oneléiersy level folunothae level, a single line in spectrum is supposed to apear. But when a spectrograph is developed with resolving power, then two or more lines very close together are observed. Bohr's atom ‘model can not explain these multiple lines in atomic spectrum. "@) According to Bohr's atom model electrons revolve in circular orbits but modern research reveals that electrons revolve in space in three dimensional order. @)vAccording to Heisenberg's uncertainty principle the exact position in orbit and momentum of a very small particle like electron ie like electron can not be determined at the same time with good precision. But in Bohr's atom model that has been done. ))According to Bohr's 2nd postulate, the angular momentum of the revolving electrons, h md mvr =n x 7% But that postulate can not explain this type of angular momentum. (6) Under the influence of magnetic field, the atomic ah line spectrum is finely divided into multiple lines, which is eas called Zeeman_effect, Similar effect is found under sate electrical field, which is called Stark-effect. Zeeman-effect and Stark-effect are not explained by Bohr's atom model. dere What can we think about these two changes in spectral Stamm lines? Is there any fine splitting of a particular energy level in an atom under the influence of magnetic and electrical fields? 2.5 : Zeeman effect on ‘Na-line spectrum Achievements of Bohr's Atom Model “1s Stability of Bohr's atom mode! electron does not lose its energy till it is in a definite orbit. After the first orbit, no more : According to postulate of Bohr's model, moving lower energy level exists, hence electron can not enter into nucleus also. So revolving electron does not radiate any energy and thus Bohr's atom model attains stability. "28 Moreover, Bohr's atom model can explain H-spectrum successfully. Bohr determined the radius of Ist orbit of H-atom. It is known as Bohr radius (a9), —= which has a value, ag. 192 40"! im.96 @m value of Rydberg constant, Ry = 109737 cm Chemistry- First Paper Energy of a revolving electron in different orbits in Bohr's atom model are calculated. It makes easy to calculate the amount of energy absorbed or emitted, h® = (Ez ~ E;) relation, when an electron jumps from one orbit to another. Thus it can explain different: spectral lines of an atom in visible light. ie y calculated from a Owne is approximately equal to experimentaP-VMUETIRET09678 crn’! Qn ————— @88" Bohr's model, even with some limitations, is beyond doubt a successful atom model for the two matters such as— (i) an atom has different energy levels and (ii) energy radiates when electron jumps from one energy level to another with frequency, @ = (B2-E,)/h. For this causes, acceptance of Bohr's atom model is established. %* 2.1.4 Comparison between Rutherford's Atom Model and Bohr's Atom Model (A) Basic Concepts of two atom models : ‘Rutherford’seatomemodelsissbasedwonsthewobservation*oMhisiowparticle, scattering experiment and solar system phenomena. On the otherhand (Boht’statommmodeliceepis thetfacwofrexistancevoficentral:atomic-nucleus and adds quantum theory:of radiation“of~ ‘Tight'giveniby:Plancksand:Binstain. recur ianierets won nontinthe number and shape) of oruit for electrons are not defined well. On the otherhand the different stationary orbits for electrons are defined with definite radius. All these stationary orbits are associated with definite energy or quantised orbits. The electrons moving in these orbits are also quantised, In Rutherford's atom model, stability is due to electrostatic attraction between nuclear centripetal force and extra nuclear centrifugal force of the revolving electrons. On the otherhand, in Bohr's atom model, stability is due to existance of some quantised stationary orbits created by nucleus and revolving quantised electrons on those orbits. (B) The Limitations of both atom models os Rutherford's atom model is compared to solar system. The planets of solar system are attracted by gravitational force; whereas the negatively charged electrons repel each other. So it is unjustified to compare electrons to planets. On the otherhand there is no such discrepancy in Bohr's atom model. According to Maxwell's theory, revolving electrons of Rutherford's atom model gradually must radiate energy and hence their orbits will be decreased in size and finallyQualitative Chemistry 97 fall in the central nucleus. Hence the stability of Rutherford's atom model electrons wil is questionable. This limitation is removed in Bohr's atom model with the addition of the concept of stationary orbits for revolving electrons. = 0.5292 10-8cm. As there is no orbit after Ist orbit, there is no possibility of falling the revolving electrons into nucleus. So here is the ground of stability of Bohr's atom model. ‘The nearest Ist orbit has the radius, 3. Rutherford’s atom model can not explain the atomic spectrum. But Bohr's atom model can explain clearly the source of H-atom spectrum. As per Bohr's postulate, electron may jump from lower energy level (Ei) to higher energy level (E2) by the absorption of necessary quantum of energy. On returning back to lower energy level the absorbed energy radiates, which is AE = (B - E}). According to Planck's equation, if the frequency of radiation be 8, then AE = h8. Hence a spectral line with frequency # (neu) will be shown in the emission spectrum of an atom. (Fi, = t i T I Paschen ice (ex ine) 5, ? Balmer series Ga Visible tegion) ; -Lymen series (in UV region) Fig- 2.6 : H-atom Spectrum 4. Bohr’s atom model can explain the line spectrum of mono-electron atom or ions (H, He*,Li2+), but cannot explain spectrum of multiple electrons atom or ion. Because, in those cases, attractions between nucleus and electrons and repulsion between the electrons exist. The different spectral lines of H-atom obtained in different regions of light with different wavelengths (A) can be expresed in wave number (6) by following Rydberg equation : 1_= 1 i1y)-1 +5-Rux (3 2) 7 Here ¢ different spectral lines of H atom discovered by different scientists in different light- regions are named after their discoverer as follows : Lymen series : Electron jumps from higher energy level, nz =2, 3. 4, ...7. to lower level, ny Balmer series : Electron jumps from higher energy Tevel, ng = 3, 4, 5. to lower level, ny =2 Chemistry First Paper-—13 —98 Chemistry— First Paper S. Paschen series : Electron jumps from higher energy level, np = 4, 5, to lower level, ny =3 Brackett series : Electron jumps ftom higher energy level, nz = 5, 4. to lower level, ny =4 + Electron jumps from higher energy level, n2 = 6, 7 to lower level, n= 5 5. Pfund series Worked Example-2.1 energy level of H-atom? Strategy : From Bohr's atom model, mv: + Angular momentum, mvr = 3" x 6.626 x 10-4 J.s x7 * = 3.1624 x 1074 J's Worked Example-2.2 : Calculate angular momentum of the electron rotating in M-shell of an atom. If radius of that shell (or, orbit [mass of electron, me = 9.11x 108g] ) is 3.6 x 10-4em, what is that electron's velocity?Qualitative Chemistry 99 Strategy : Apply mvr ="; when value of 'h’ is in joule unit, then mass of electron will be in kg unit and radius of orbit will be in metre (m) unit. Solution : Angular momentum, mvr = 32; Here, shell, n =M = 3 3% 6.626% 104 I.sx7 Planck constant, h = 6.626 x 10-4,J.s Sea DDD Constant, 1 = 22/7 = 3.1624 x 1034 J.s mass of electron, me = 9.11 108 g Calculation of velocity of electron : =9.11x 107g mvr = 3.1624 10% J.s radius of orbit, r =3.6 x 10-em a sini e = 3.6 x 10-1m 3.1624 x 10-34 (kgm?s2).s angular momentum, myr =? = 9.11 1058 kg x 3.6.x 10-m velocity of electron, v =? = 9.64264 x 10-§ ms“! Worked Example — 2.3 : Radius of an orbit of H-atom is 8.5 x 108 cm and velocity of electron is 5.4452 x 107ems-!. In which orbit that electron is rotating? [mass of electron, me = 9.11 x 10-8g] - ah Here, Solution : Angular momentum, mvr = 377; 1 =85% 10-8cm EXO 85x 1019m | palin) y = 5.4452 x107 cms! 9.1 103 kg 5.4452 x 108m st 8.5 10m x 2x22, = SSZ EAS me Me = 9.11% 10-8 g 9.11 x 10-3!kg, h= 6.626 x 10-41.s h = 6.62x 10-34 kg m2.s-! n=? 6.626 x 10-4 kg mst x 7 . n = 399.99 x 10? = 3.99 = 4 (integer) v. Electron rotates in 4th orbit. Worked Example-2.4 : The radius of 3rd orbit of electron of H atom is 8.45 x 10°!9,,, Calculate velocity of the electron in its orbit. [mass of electron, 9.109 x 10-4! kg.] Strategy : From Bohr's atom model, myr = ah or, e < oh Qn x mr Solution : Here, n = 3, h = 6.626 x 10°34 Js (orskg m? sx!) 3x 6.626 x 10-34 kg m?s-! 22 o> o——rrre——ooaetrt 2x = x 9.109 10-1 kg x 8.45 x 10-10, 3.x 6.626 x 10-34 x 7 mst eee ee = ‘S ms-! i = Fm Dx 9.109 x BASH 10g, 7 20199 x10 ms100 ‘Chemistry- First Paper Worked Example- 2.5 : The energy difference between two energy levels of electron of Hatom is 245.9 kJ mol-!. Calculate the wave length and frequency of energy radiation when the electron of H-atom jumps from that higher energy level to lower energy level. Strategy :A B= hO = hx 5 and A=. (All terms in same unit] Solution : Here, AE = 245. 9 kJ mol-!. hh = 6.626 x 10-74 J.s x 6.022 x 10°? mol! = 3.99 x 107" ky. s. mot AE 245.9 kJ mol“! - =fE - ON ot __= 145-1 +. Frequency, 8="F~ = 5555. 10-13 kis, molt 7 ©1629 x 10!4s © 3% 108 10%nms-! + Waverlength, A=5 = “6 1629 x 10-5) = 4.867 x 102nmQualitative Chemistry 101 Know More : |For Advanced Students 2.1.5 Applications of Bohr's Atomic Theory From the concept of Bohr's H-atom, every atomic orbit is quantized with energy and different from each other. The electrons, revolving in these different stationary orbits, are also quantized similar to their present orbits. Bohr applied his concepts together with the laws of motion of particles of physics to deduce successfully the following mathematical equations for atomic particles like H atom and positive ions containing one electron similar to H atom like He* ion and Li?* ion ete. (i) To calculate radius of nth orbit (rn), (2) To calculate velocity of electron in nth orbit (Vn); and (3) To calculate total energy of an electron in nth orbit (En). (J) To calculate radius of nth orbit : Suppose total positive charge in a nucleus of H atom or any positive ion containing single electron like H atom, is Z x e [fig-2.6 (a)]; here ‘Z’ is atomic number and 'e' = positive charge of a proton. Again the negative charge of an electron of H-atom = e (here total amount of charge of a proton and an electron are same.) Here the electron of mass ‘m’ revolves round the nucleus in an orbit of radius ‘t’ with its velocity 'v'. Here according to Coulomb's law for a charged particle : (® Attractive force of nucleus on the revolving anv) ergelbaa! ‘ : Zexe Ze? ‘velocity of electron ie, centripetal force = 22H * = ZF | Ealong the tangent (ii) Again, the centrifugal force for the revolving pital force: my? electron of mass 'm' with velocity 'y’ will be = Now for stability of the revolving electron in a particular orbit the two forces like centripetal force and #26 (a) + Revolving electron ‘in Bohr's atom centrifugal force must be equal in magnitude. Then — * shies CD) i102 F Chemistry- First Paper Again from 2nd postulate of Bohr’s atom model, the angular momentum of an electron : h revolving in nth orbit is 'n' number of multiple of 37. Hence myr = — {here 1, 2, 3 .. ete integral number] So from equations (1) and (2) we get, ee = gee Hence, for nth orbit of an Bohr’s atom with atomic number the radius of it is, n2h? h2 n2 4n2mzZe2 ‘Gq2me2 * Z n2h2 For H atom, Z = 1, then for H atom, m= 7753 [See article-2.2,2, (1) Radius distance, rq and its calculation in CGS unit] * Calculation of Radius of Ist Orbit of H atom ; n2h? 4n?met We know, radius of nth orbit of H atom; m= In CGS unit : h = 6.626069 x 10-29 erg.s; m = 9.109382 x 10-28 g; e~ = 4.803 x 10-1 e.s.u; m = 3.141593; n= 1 for Ist orbit of H-atom; putting these values in above equation, we ge a (6.626069 x 10-27 erg.s)? x (1)? FL = 4x (9.141593)? x (9.109382 x 10-28 g) x (4.803 x 10-1 esuy? 43.90479039 x 10-54em 8296.098891 x 10-48 1 = 0.5292 x 10-8 cm; or, 0.5292 A [Here 10“ cm = 1A] Remember, radius of Ist orbit (¢;) of H atom is known as Bohr’s radius ~ (a,) = 0.5292x 10-* cm 2 ‘:. For atom with 'Z' atomic number, tp = 0.5292 x 10-8 cm x7.Qualitative Chemistry 103 Know and Remember : MATA "D Capen cesstner ane) * Relation between the radii of nth orbit and Ist orbit of H-atom : We know, the s 7h? radius of nth orbit of H atom is : ta = 327 my?, "Again the potential energy of electron at a distance 'r' from the nucleus with charge (Zx e) will be, ite distance from 2 = Its explanation is that, the potential energy of an electron at a its nucleus is supposed to be zero. Again the amount of work done to bring the electron from. infinite distance at a distance 'r’ with respect to its nucleus, is equal to potential energy of the s 5 . Zexe Ze? electron. Then attraction of the nucleus on electron at a distance 'r' form it is ; “5S =“5- +. The potential energy of the electron in an orbit at distance 'r' from the nucleus will be as : a7 6? ror 2 2 f 2g ‘i z2f 4 eee Ze’ aie ae ar os (rd +. Total energy of an electron revolving at nth orbit, 1 ~Zer 1 Zed Ze 2 . 2 En =z mv +(2); on ta ym xi; [here, v2 = 4 Ze? Ze?) _—Ze? =Ze2 1_— Ze? 4n?mZe? nth? on B= (22 - )- Be 10% En=—5 x == 5X ng — (because, r= 77) =2n?mZ2e4 + En=—,.3,2 This equation represents En for positive ion with single electron like H atom and proton number 'Z'. So for H atom, Z = 1, —27?met then total energy of H-atom, |En=—"3,2 | * Ratio of Ey and Ey of H atom : We know, Ey = =2n?met En 2nmet\) (__h2__ B= ay ne By nth?) “(2 ‘Worked Example-2.6 What is the radius of 2nd Bobr's orbit in Lithium atom? 2 Strategy = Here 1 = 0.5292 x 10-8 cm x 7 equation will be used.Qualitative Chemistry 105 Solution : For Lithium aera a =3, and n = 2; then : 12 = 0.5292 x 10-8em x45 on rz = 0.7056 x 10-8 cm (Ams). Worked Example- 2.7 : Calculate the velocity of the electron revolving in 3rd orbit of H-atom. 2m Strategy : Here Vn -( ae x = ‘equation will be used. Solution : For H-atom, Z = 1, for 3rd orbit, n = 3 Z =10 eu)? F yy te x 3.14 x 48x 10M es)? rere, hx3 26 x 10-27 erg.sx 3 ie Charge of e~ = 4.8 x 10-10 esu 6.28 x 23.04 x Pe cem2 .s-1/2 Plank const, h = 6.626 x 10-27 erg.s oye 6.626 x 10-27 (g.cm?.s~).s x 3 144.6912 x 10-20 g.cm3. s? OF, ¥3 = "79.878 x 10-27 g.cm?: } or v3 = 7.2789 x 107 cm.s“! (Ans). Worked Example-2.8 : Show that velocity of the electron of H atom in Ist orbit is equal to about 0.73 x 10-? times of the velocity of light. ced Strategy : Here Vp -( ae x2 equation will be used. Solution : For H atom, Z = 1, and for Ist orbit, n = 1, then— 2ne? x 3.14% (4.8 x 10-10 esu)? h 6.626 x 10-77 erg.s ee Here, Charge of e~= 4.8 x 10-10 esu Plank's const, h = 6.626 x 10-27 erg.s 144.6912 x 10-20 cm. sl OG SAG 6.626 x 10-27 = 2.1837 x 108 cm. Again velocity of light, ¢ = 3.0 x 10!0 em.s! vy _ 2:1837 x_108 om gl er Ge ao So the velocity of electron in Ist orbit of H atom is 0.73 x 10-? times of velocity of light) it is proved. : Worked Example-2.9 + If the velocity of electron of H-atom is 51 part of velocity of light; then in what orbit that cae is revolving? 2ne Strategy : Here, vn =[—7=- |x equation will be used. ‘Chemistry First Paper—14106 Chemistry- First Paper Solution : Suppose the electron is revolving in nth orbit. ‘Then as per question, v= (Velocity of light) x 543 3.0 x 101 ems!) x she = 1.091 x 108 ems! or, vn = 275 at) Zz h )*n Again, velocity of electron in nth orbit, vq -( : For H atom, Z = 1, e~ = 4.8 x 10-!0 esu, h = 6.626 x 10-27 erg.s. Putting these values we 2x 3.14 x (4.8% 10M esuy? 1 _ 2.18369 x _108em.s“! 6626x 10-27ergs Gs or, Ax. Ap > gis here, Ap=m x Au = momentum of moving particle; Where Ax = uncertainty in position; Au = uncertainty in speed. The more accurately we ‘know the position of the particle (smaller Ax), the less accurately we know its speed (larger Au), and vice versa. (D) Schrodinger Wave Equation ‘Acceptance of (i) the dual nature of ‘matter’ and ‘energy ' of moving particle and (ii) the . which examines the \ uncertainty principle culminated in the field of ‘quantum mechani we nature of particles on the atomic scale. In 1926 Erwin Schrodinger derived an equationQualitative Chemistry 109 which is the basis for the quantum-mechanical model of the H-atom. The model describes an atom which has certain allowed quantities of energy due to the allowed wave like behavior of an electron whose exact location is impossible to know. The electron's matter-wave occupies the three dimensional space near the nucleus and experiences a continuous, but varying, influence from the nuclear charge. The schrodinger equation is quite complex but is represented as : oy Sy By Sem G-wv=0 In this second’ orderdifferential’equation with three dimension (x, y, 2), (i) m = electron's mass, (ii) = electron’s total energy, i) u = electron's potential energy (= “<>, (iy) h = Plank's constant, (v) w (psi, pronounced 'sigh') is called a wave function of electron in three dimensions. The solutions of the wave equation are called wavesfunctionsior ‘orbitals, The best way to think about an electron’s wave function is to regard it as an expression whose square (1y2) defines the probability of finding the electron within a given volume of space around the nucleus. A wave function tells where the electron will most probably be found. [Wave equation] S°'N€ 5 7° Wave function Nie eee eat) ame Probability of finding electron. in a region of space (y2) ‘A wave function is characterised by three parameters called quantum numbers, represented as ni, /.m, which describe the energy level of the orbital and the three dimentional shape of the region in space occupied by a given electron, 2.2.1 Quantum Mechanical Atom Model PP" The Quantum Mechanical Atom model or Modern atom model is the final product of the following experimental observation and theoretical explanations : Concept of Central ‘nucleus’ of an atom as per Rutherford’s atom model (1911) 2. Concept of stationary orbits of electrons as per Bohr's atom model (1913) 3. Concept of particle-wave duality of electron as per De Broglie (1924). De Broglie equation is, 4 Tmomentum (my) of electron, Here A = wave length of “matter wave’, m = mass of particle, v = velocity of the particle. h h xa =2 22.» Angular momentum, myr= 1% 3 ad For orbit of an electron, 2nr110 Chemistry- First Paper ‘Theory of wave mechanics for dual properties of an electron, proposed by Schrodinger (1926) with a three dimensional general mechanics quadratic equation as — 2 a oy oe ee (E-u) = 0; here w (psi) = wave function (i.e. amplitude of the waye in space (x, y, 2); m = mass of the particle including electron, E = total energy 2 of the atomic system, u = potential energy at point (x, y. 2) = ©; h = Plank’s constant 5. The uncertainty principle for the position (Ax) and momentum {mass (m) times speed, ‘Au) of a revolving electron in orbit given by Heisenberg (1927) as : Ax xm Au> where Ax = uncertainty in position and Au = uncertainty in speed of an electron. The more accurately we know the position of the particle (smaller Ax), the less accurately we know its speed (larger Au) and vice- versa. In short Schrodinger Wave Mechanics equation is the basis of the modern atom model. On solving that equation, we can get different values of E and for every value of E, several equations for are obtained. Of them, only some values are for some special conditions; they are called eigan values (i.e. acceptable) related to atomic orbitals. The region on space where there is maximum probability of finding the electron-charge gfoud (90-95%)yis called orbital. Since a large number of solutions of are possible; hence Tiéaningful solution three integer or parameter n, /, m are introduced. These three integers n /, m, related to wave function y of electrons, are called quantum numbers. Thus each wave function (\) describes a possible state of the electron in an atom. 2.2.2 Quantum Numbers, Different Sub-Orbits and their Electron Capacities In an atom, the electrons are arranged different energy levels. These electrons not only rotate around the nucleus but also rotate around their own axes. Aécording to the quantum mechanics, three inter related numbers or parameters are required to express the size, shape and orientation of the orbitals of electrons in an atom. Moreover, there is a number to express the direction of spin of the electrons. These four co-related numbers are called uantum numbers which are as follows : T. Principal quantum number,@) 2, Azimuthal or subsidiary quantum number @) 3. Magnetic quantum number, 4, Spin quantum number)ayy Qualitative Chemistry 11 1. Pri cipal Guantout number : The quantum number that expresses the main energy level in which the electrons are moying.around the nucleus is the principal quantum number. It is expressed by n, where n= 1, 2, 3, 4, 5, 6, 7 etc. It also represents the average distance of the electron's orbit from the nucleus. As the value of n increases, the distance of the orbit from the nucleus, i.e. the size of the orbit increases. Bohr gave the idea of this quantum number. Whensni=ely 2e3y-4yiSvetor the energy" Tevelsare"KnOWH ae" Kp Ly MpNeOrshells eae 1nd =a ; Table 2.1 ferent orbits or shells & their maximum accothodated electrons: Orbit or shell in an atom. K L M N oO P ln Principal quantum number, n__| 1 2 3 4 5 6 7 Total number of electrons, 2n? | 2 8 1s |32__|s0 2 [os | ‘The value of principal quantum number determines, to a large extent, the energy of an electron and average distance of an electron from the nucleus. In case of H atom, the approximate distance from the nucleus and the energy of the electron are given as = 2 = (h? /4n2me2)X 7; For H-atom, Z = h. mand e*, the nth distance is as : Ty = 0.5292 x n? x 19"8 em; (2) Radius distance : , then putting the values of 2 (or A, or 104 pm) [1A = 1" em] ** For any atom, f= 5.292 x x 1071! m ie (2) Energy of nth orbit, En = (-2n? m e4/h?) x Fz, here putting values of h, m, m and © [ h = 6.626069 x 10°27 erg. s; m= 3.141593; m = 9.109382 x 19778 g% [e- = 4.803 x 197! esu]; the energy of the nth energy level is as : En =(- 2.18 10718) x &, At first orbit energy of H-atom, Ey = (- 2.18 1978 J And for | mole H-atoms, E} =-2.18x 10718 J x 6.022 x 19?3mol"! By =-1312 KI mot! . =1312 kK mol”. 1312 kJ mol? =_ 1 For 2nd Grbtyin 2) = eto ae Oe 328 kJ mol 7 ©. Difference of energies between 2nd and 1st orbit is, [Eo — Ej] = C328 kJ mol! ) — (1312 kJ mol!) = 984 kJ mot! ’112 Chemistry First Paper 4 When the electron of H-atom jumps from Ist orbit to its 2nd orbit then absorbed energy = (984 kJ mol! + 6.022 x 10?3mol-!) = 1.634 x 19°! 8J. 2. Angular Momentum or Secondary quantum number : Each principal shell is divided into several subshells. ‘astsubsidiangquantumenumberMt is denoted by ‘', It may have values from 0 to (x =L the value of ‘7, determines the shape of the subshells or orbitals. When = 0, 1, 2, 3, then the subshells are known as s, p, d and f orbitals respectively. The electrons rotating in these subshells are called s, p, d, f electrons respectively. For Ist shell, n=1,/=0, For 2nd shell, n= 2, 1=0, 1. For 3rd shell, i =3,/=0, 1,2 3rd shell has 3 types orbitals namely 3s, 3p. 3d For 4th shell, ie. 4th shell has 4 types orbitals namely 4s, 4p, 4d, 4f imum capacity of a1 Gm hold electrons is 2 x (2/ + 1); where 1 = 0, 1, 2,3 > eee ete, \4 \ 2 There may be s?, p®, dl0, £14 electrons. & z Ist shell has I type orbital namely 1s 2nd shell has 2 types orbitals namely 2s, 2p [The symbols for orbitals are taken as s for sharp, p for principal, d for diffused and f for fundamental corresponding to foutitypesiofispectrayobtained)from alkali metals of group —1 at the primary stage. In a particular orbit or shell, the vai us orbitals possess energy in the following order s

mporarysfundamentat ‘‘particless, —— Permanent Fundamental Particles of Atom : From the three atom models, it is known that nucleus is at the centre of an atom and electrons are rotating in different orbits outside the nucleus. Besides these two particles, scientist James Chadwick discovered (1932) chargeless neutron in the nucleus. Except ‘Hydrogen-l' isotope, neutron is present in all atoms of all elements. ‘These three particles like electron, proton and neutron are called the permanent fundamental particles. emporary fundamental particles : Besides the permanent fundamental particles, some other particles are also found in some atoms for a very short time. These short-time existance fundamental particles are called temporary fundamental particles. These are gabout200, in numbers. The most important ones are neutrino, antineutrino, gravitron, Positrion, positron, meson, boson, pion, muon etc. ‘Composite Particles : Except permanent and temporary fundamental particles, a class of heavy particles radiate from some heavy atoms, These heavy particles are known as composite particles, For example, alpha (0) particle (3 He?) and deuteron. Again, on the basis of similarity and dissimilarity in total number of protons and neutrons in different atoms of different elements, the atoms are classified into three classes : (i) isotopes, (ii) isobars, ( ) Isotopes : The atoms which have same number of ee ee Thequal number of Treutrons and hence masses become different, are called isotopes of same element. They have same position in groups of periodic table. Hence this name ‘isotope’ is attributed to them, ‘iso’ means same and ‘topos’ means position i.e. position in Periodic table. For example, hydrogen has 3 isotopes | H, 7H, }H. They have special names like protium 1 oe (ies nena ( jH ). Deuterium G HorD), and Tritium ¢ igor a), Isotopes of other elements do se not have special name, Isotopes have similar properties. a Wr se Isobars : The atoms whose mass numbers (p+n) are equal {but the proton number and neutron number are unequal ie different are called(isobars) gent elements. So their properties are different. For Examples, to one another. Isobars are are isobars to each other.0 ee Qualitative Chemistry 117 C sotones :,The atoms whose neutron numbers are same, but proton numbers and mass numbers (p +n) are different are called isotones to one another. Isotones are different in 30. 3 32, properties. For example, |,Si, jP and |S are isotones to each other. Here all of them have 16 neutrons; but their proton number and mass numbers are different, Description of Three Permanent Fundamental Particles (1) Electron : In 1897, while experimenting on cathode rays. Sir J. J. Thomson discovered electron. Electron is the smallest particle, (i) The mass of an electron is 9.1085 x 10-8 g, which is—>g57 part of the mass of a proton. (ii) Electron is negatively charged and the amount of its charge is - 1.6 x 10-!9 C (coulomb) or —4.8 x 10-10 e, s. u (electrostatic unit). This is the smallest charge ever recorded, hence this amount of charge is taken as one unit in atomic science. (iii) The symbol for electron is ‘e'. (iv) Electrons move outside the nucleus of an atom. (2) Proton : In 1919 Rutherford proved that of all elements. (i) The mass of a proton is 1.673 x 10-4 g, which is almost same as that of fe electron proton is also present in atoms hydrogen atom. In atomic mass scale it is equal to 1.007276 amu. So its mass is generally taken as one unit. (ii) Proton is positively charged and its amount is equal to that of an electron i. e. its charge is + 1.6 x 10-19 C. So the charge of a proton is also taken as + I unit. In fact when one electron is taken out of a hydrogen atom, one gets a proton. So it is also written as H+. (iii) The symbol for proton is (small) ‘p'. (iv) The protons remain in the nucleus of an atom. , (3) Neutron : Like electron and proton, neutron is also a fundamental particle. In 1920 Rutherford first postulated the existence of neutron. In 1932 Chadwick discovered neutron. (i) The mass of a neutron is 1.675 x 10-24 g which is 1839 times that of an electron and is slightly more than that of proton. In atomic mass ui scale, the mass of a neutron is 1,008665 amu. For practical purposes it is taken as one. (ii) Neutron is uncharged. (iti) The symbol for neutron is (small) ‘n’. (iv) Neutrons reside inside the nucleus of an atom. Except, ‘Hydrogen-1 isotope’ neutron is present in all atoms.118 Chemistry— First Paper vi Table 2.2 : jameand | Mass (in g) Charge {lative to. Proton | Position symbol. mass (amu) | Charge Electron, 9.1085x 10-8g }— 1.6 x 10-9C 1es7 -1 J outside Jeon of, 4.8 x 10-1 esu nucleus Proton, 1.673 x 104g |+1.6x10-19C 1 +1 inside 1p or,p on +4.8107esu nucleus Neutron, 1.675 x 10-74 g oO 1 0 inside gprs nucleus 2.2.5 Atomic Number and Atomic Mass Number (1) Atomic number : Definition : It is denoted by are 11 protons in the nucleus of a sodium atom. Hence the atomic number of sodium is 11. Characteristics : Dheeproperties*ofan "element depends" oi "the'atomicinumbers It may be mentioned that an uncharged atom contains also Z number of electrons. But electrons reside ‘or example there outside the nucleus and during chemical reactions and in the formation of compounds electrons play active role and its number changes. But protons reside in the nucleus and its number does not change. @ Jeomic ‘mass number : Definition : ‘TeutpralmumbersnfiprotonsandeneutronsHtHe | It is denoted by ‘A’, For example generally the nucleus of sodium atom contains 11 protons and 12 neutrons. Hence the atomic mass number of the sodium atom is (11 + 12) = 23. (3) Rule for writing atomic ferrfieesaee eae ehary anand cr ati The atomic number Z is written on the left side of the symbol of the element as subscript, the mass number A is written on the left side of the symbol as superscript. The charge (m +) is written on the right side of the symbol as superscript. The number of atoms (n) in a molecule/ion is written on the right side of the symbol as subscript. If the symbol of the element be X, then all the rules may be preQualitative Chemistry 119. 2.2.6 Mass of an atom and Relative Atomic mass Atoms are so tiny that they cannot be seen even by most powerful microscope and hence they can not be directly weighed. But scientists have determined their masses indirectly. For example. masses of elements shown above. For this reason, chemists chose the mass of a particular element as 'standard-value" to compare one atom of each element ‘how many times heavier’ than that atom of standard valued element. Thus the mass of each element's atom is known as ‘relative atomic mass’. For example, taking the mass of a hydrogen atom as standard value, then relative mass of carbon atom becomes 12 as follows : 9924 x 10-3 g 0.1673 x 10% g By this present time, different scientists chose Sistandardescalesstoymensuresthenrelative ‘mass of element; such as~-(1) Hydrogen Scale, (2) Oxygen Scale, (3) Carbon Seale oon hd ae brief amu to express relative mass of different elements. Relative Mass of C-atom = = 12 (approx) Definition of Atomic Mass Unit : One atomic mass unit is defined as b part of mass of mne §7C atom. It is that carbon scale; 9924 x 10-3 I 8 = 1.661024 Relative atomic mass is the ratio of the mass of an atom to that of this atomic mass unit isa) Hones fs «pure ume Ie eta cali stot ean ox ot oR 1 dalton = 1.6605 x 10 g Mass of one C-12 atom is taken as amu “G4 Qt —= \ Definition of gram-atom : When the atomic mass of an element is expressed in gram, mass of one ?C ator Lamy = BBss of one Sato then the amount is known as one gram-atom (or one mole) of that element. For example the atomic mass of chlorine is 35.46. So 1 gram-atom of chlorine means 35.46 g chlorine. ft ‘onesgram-atom element» 6:022/x"1 09 atoms)arespresentiThismumberissknowiassAvogRdro number120 Chemistry First Paper MAN 19-20 2.2.7 Relative Amount 6f Isotopes and Atomic Mass ‘The natural abundance pf isotopes of different clements are quite different. Fof example Their relative abundances ake 99.76% 0.037% and 0.204% respectively. In nature earbonshasitwoystablesisotopes™!2@rand!9@; their relative abundances are 99.89% and 1.11% respectively. —— If an element has several isotopes, whose atomic masses are Mj, M3, My ete. and whose relative aboundances are a;% a7% a3% etc., Then among 100 atoms of that element we get. Ayerage Atomic Mass of Elément = aM + agMo + aM Example 2.1 : In nature chlorine has two isotopes. their masses are 35 and 37 amu and their relative abundances are 75.53% and 24.47%. Calculate the atomic mass of chlorine. Solution : According to the question the masses of the isotopes are 35 and 37 amu, so their atomic masses My and Mp are 35 and 37 respectively. ‘Their abundances are : aj = 75.53% = “ahe> = 0.7553 and ; ap 24are = 2887 = o2447 ‘The atomic mass of chlorine = (35 x 0.7553 + 37 x 0.2447) = 35.45 Example 2.2 : In natural oxygen the amounts of 160, 170 and 80 are 99.76%, 0.037% ‘and 0.204% respectively. Calculate the atomic mass of oxygen. Solution : According to the question the atomic masses of the isotopes of oxygen Mi, Mo and M3 are 16, 17 and 18 respectively and their abundances are ay = 99.76% = 0.9976; ap = 0.037% = 0.00037; ay = 0.204% The atomic mass of oxygei 0024 = (16 x 0.9976 + 17 x 0.00037 + 18 x 0.0024) =15.999 2.2.8 Relations among Number of Protons, Electrons and Neutrons in an Atom (1) The atoms are, as a whole, electrically neutral. Since the neutrons are uncharged and since the charges of protons and electrons are opposite in sign, but equal in magnitude, the numbers of electrons and protons in uncharged atoms are equal. ‘ (2) On the otherhand the mass of an electron is negligible in comparision with those of proton and neutron, So the mass of an atom is practically determined by the number of protons and neutrons in it. () The atomic masses of all isotopes are very near to whole numbers, this number is known as mass number (A) of isotopes and this is equal to the total number of neutrons and protons in that isotope.Qualitative Chemistry 121 (4) Again the atomic number Z of an isotope is equal to the number of protons in that isotope. So it can be concluded that if the mass number of an isotope be A, and atomic number be Z, then there are Z protons, Z electrons and (A~Z) neutrons in the uncharged isotope. This can be seen in table 2.3. . From this table it is evident that (J) The only: difference-among:!60, 170 and-18O or between !2@-and"!3@:is\the numbenof neutrons. ‘The'difference:in:the numberof neutrons:isithe:only/reasombehinditheroccurencey ofisotopes. (2) Since the physical and chemical properties of all isotopes of an element are same, it can be concluded that the neutron has no effect on physical and chemical properties. Long before the discovery of neutron, Rutherford proved that there are two parts in an atom— (@ the central nucleus and (ii) the electrons moving around the nucleus. Now it is proved that protons and neutrons remain in the nucleus of an atom. ‘Table 2.3 : The number of protons, electrons and neutrons in some isotopes Totope| _|Nowotdifferentparticles! [Total Mass Number| _Total charge Projor” eo. Nepifon. Proton + Neutron. Proton + Electron = Total + Neutron = Total e 6 6 6 6462 [+6 +64 0 =0 ne 6 6 7 64+7=13 [+6 +640 By 7 7 7 74+7=14 447 +C2 +0=0 By 71 @ 8 748=15 |+7 + @7+0=0 3°o 8 8 8+8=16 +8 +(8)+0=0 16 8 9 84+9=17 |+8 +¢8)+0=0 #6 8 8 10 s+io=18 [+8 +C8)+0=0 Worked Example- 2.13 : Identification of Orbitals : Identify the shell and subshell of an orbit with the quantum numbers n =3,1=1, m= 1. Strategy : The principal Q.N (n) gives shell number, angular Q.N (2) gives subshell number, magnetic Q.N (m) gives spatial orientation of the orbital. Solution : A value of n = 3 indicates that the orbital is in the third shell, and a value of /=1 indicates that the orbital is of the p type. Thus, the orbital has the designation 3p. Chemistry. First Paper—16122 Chemistry— First Paper Calculate (a) Bohr’s radius, (b) velocity of 2s! electron and (c) energy of 2s! electron of second orbit of Li-atom. Solution : (a) Equation of Bobr's radius is as follows : ne ne Tn ® gtime? * Z here a, = 5.292 x 10-!1m For Li-atom, n = 2; atomic number, Z = 3. 2 ‘: Radius of 2nd orbit, rp = 5.292 x 10-1! ~ 2 = 7.056 x 10-2nm, ane? Z . (b) Velocity of electron on nth orbit, vn =F x © For Li-atom, n = 2; atomic number Z = 3; charge of am electron, e = 4.803 x 10-10 esu; h = 6.626 x 10-27 ergs. sec; x = 3.14 [Note : When charge of an electron is in esu; unit, then value of h = 6.626 x 10-27 er Putting the values in above equation, we get: vp = 2x 3.14 x (4.803% 10719)? oS 6.626 x 1077 z = 327.96x 108em s*123 Qualitative Chemistry 8 x 10-18 Ix Z2 = For Li-atom, orbit of 3rd electron, n = 2; atomic number, Z = 3; (©) Energy of electron on nth orbit, Ey Putting the values in above equation, we get : 2.18 x 10-18 Ix 3)? by = 2 LOGE = cs 10 QP Worked Example-2.15 : Calculate radius of orbit of 3s! electron or, Strategy : Equation for radius of atomie orbit n? 0 x Fp = ag x Fy here ag = 5.292 x 10" m Taf Ltr. ame - Solution ; For M-shell or, orbit of 3s! electron of Na-atom, n=3, atomic no = Z = IL ». Radius of 3rd orbit of'Na atom, r3 = 5.292 x 10-!t m xBE 292 « 10-1! x 10% nm x 775 OF, Fs = 4.3298 x 10% nm os one :. Radius of M-shell of Na atom = 4.3298 x 10 nm. Worked Example-2.16 : Calculate the speed of rotating electron in 3rd orbit of H-atom. How many times that electron rotates round the nucleus per second? 7 Strategy : Radius of orbit, rn = 5.292 x L0-!! mx zr and mvr = nh/2r will be used. 7 Solution : For 3rd energy level of H-atom, n = 3, Z = 1 sry = 5.292 x 10-1 mx = 5,292 x 10-M x 9m = 47.628 x 10-Hm h ‘Again, mve = "Jos ss me = 9.11% 107 'kg 3.x 6,626 x 10-41. Y=2y 314K 9.11x 10g x 47.628 10 ts = 47.628 10"'! m 19.878 x 1034J.s __ 19.878 108ms-! nh = 6626x104 5.5 On Y=9724.84™ 10-%kg.m 2724.84 nm =3.14 or v= 7.295 x 105 ms! Calculation of number of rotation : Circumference of 3rd energy level = 2nr For 2nr metre path, electron rotates = 1 time or, for 1.0 metre path, electron rotates = 54 times 7.295 x 10° mst z 10° ms~! path, el =e SS or, for 7.295 x 10° ms~! path, electron rotates = 357 a7 ene x JO mi = 24.3895 x 1013 st +, Number of rotation per second = 24.3895 x 10!124 eee First Paper ing electron in 3rd orbit of H-atom? [Ans : 2.422 x 10-19)] is 5.291 x 101m. What is the speed [Ans. 2.1867 x 106 ms-1] Fatom and speed of electron in it [Ans : 4.4564 = 10-9cm] it from nucleus of H-atom? [Ans : 4.763 x 10°8cm) 2.3 Energy Levels of Different Orbitals & Their Shapes Ip figure- 2.9, energy levels of different orbitals or subshells are shown. In discussion of spectrum of H-atom, energy levels of different orbitals depend on value of ‘n’ only ic all orbitals of a subshell contain same energy. But for multi-electron atoms energy levels of orbitals depend on both 'n' and '?. In other words, all the orbitals in a given shell have the same energy for H-atom, but slightly different energies for other atoms, depending on their ‘subshells. In fact, there is even some cross over of energies from one shell to another. A 3d orbital in some multi-electron atoms has a higher energy than a 4s orbital, For instance : aa 4s 'g 32a] 35 Z a s > 2s ae Pee - F some cross over of ene * from one shell to another: - ‘3d orbital has higher energy Ig ‘than 45 orbital 2 saa ee Ts F (a) Hydrogen (b) Mult electron atoms Energy levels of different orbitals in (a) H-atom and (b) multi-electron atoms.Qualitative Chemistry 125 Shapes of different Orbitals : Amsorbitalydescribessthes probability (about 90-95%) of finding, the:eiectronscloud —— within.a-specific. region, of, spacersurroundingsthemucleuse s@fanvatoinaThe shape of that spatial region is defined by the angular momentum quantum number, |, The shapes of Fig- 2.9 @) different orbitals depend on the value of subshell or second quantum number (I) and each subshell has a letter designation, such as with / = 0 called an s orbital, /= 1 a p- orbital, 1= 2 a d-orbital, J 3 an Forbital ete. Of the various possibilities, s, p, d, f orbitals are the most important because these are the only ones actually occupied in known elements. Let us look ually. © rare s-orbitals are spherical, meaning that the probability of —_ finding an s~ electron depends only on distance from the nucleus , not on“direction. Further at each of the four indi (1) Shape of s-Orbi more, because there is only one possible orientation of a sphere in space, an s orbital has m = 0 and there is only one s-orbital per shell. With the increase of the value of 'n’ the size of s- orbital increases but density of electron cloud decreases, stwouelectronsclouduspheressare) separated \byyamodevhaying:zerovelectron probability. All the s-orbitals are concentric. se arial a 2 y Lrcrbitl 5 ie A YY ode (atts 1s-orbital ed) \ Fig: 2.10 : Shapes of s-orbitals (2) Shape of p Orbitals : From second shell or orbit where n = 2, we get I= 1 (or p- orbitt}\and three possible values for m are ~ 1, 0, + 1. This means that there are thresyps They are identical in shape but they are situated along. Xeaxis, Y-axis and'Z-aits respectively and they are at right angles to each other. Thesshapeiof everyeplOrbitallisidumbebellishaped. The three p-orbitals are shown along their axes in Fig. 2.11 —=-126 ‘Chemistry First Paper ; = nodal plane Fig- 2.11 : Dumb-bell shape three p-orbitals (3) Shape 6f d-Orbitals : From third shell or orbit where n = 3, we get 1= 2 (or d- orbital) and five possible values for m are ~2, ~ 1, 0, + 1, + 2. This means that there are five The five "These are shown along three axes in Fig. 2.12. —_— z z z z x >. x : KC y 3 C g x dy TF y dy x ; ee da Fig. 2:12 : Double dumb-bell shape five d-orbitals |Know More : | Now a days three p-orbitals and five d- orbit jues of 'm' by some famous chemists in their books as follows : PPiroetieelprorwitals:: p, (m = 0), py (m=+ 1), pz (m=- D. & pPreerivecentiaten < 42 (m =0), 4, (m=+ Ny, (m= 1) 4,2 yal = + Dad, (m=-2) Ref : Modern Inorganic chemistry : Dr. R.D. Madan, S.Chand & Company Ltd. More Correct Values (4) From Internet Source : p, (m = 0), p, {m= +1(50%) or, ~1(50%)]; py [m = — 1(50%)) Is are designated with or, +1(50%) possible], This happens because p, and py orbitals are not eigen states of p, operator [or, Z axis component of orbital angular momentum, L] (2) From sme Internet Source : d,2 (m = 0); but for other d orbitals m’s values are uncertain and very complex to assign definite values. (3) From ‘Quantum Chemistry! : Ira N. Levine. Sth Edn. page 153, we get p, (m= 0), a(n = + 1 50%); py (m =F 50%), d,-42 (m= +2), dy (rm = 2) possible. ‘These values are more dependable and acceptable for all.Qualitative Chemistry 127 [Gratitude : I express my gratitude to Mr. Md. Rafiqul Istam (Lecturer, Joypurhat Govt. college aept. Orbits io) The word ‘orbit’ originates from Bohr atom model. According to this model, electrons revolve around the nucleus in definite cireular orbit. 2. The ‘orbit’ implies that electrons: revolve in a definite circular path. 3. The orbits are circular. The Ist orbit is nearest to nucleus and then 2nd, 3rd, 4th, orbits ete. are gradually away from nucleus.. orbit nucleus 4. Orbits are related to principle quantum number, n, Here n =I and 2 means Ist & 2nd orbit. 5. Orbits are designated by the letters K,L,M,N, O ete. When n = 1, itis i is L orbit; so on. 6. Each orbit maximum 2n? electron’ can accomodate 3 where n= principal quantum number. So K orbit can accomodate 2; L. orbit 8,M orbit 18, N orbit 32 electrons. 2019), for sending Photocopy of related topic of the above mention book.] Characteristics‘of Orbitsand Orbitaly ‘Orbitals The word ‘orbital’ originates from quantum mechanics. The regions where probability of finding electron cloud is high (90-95%) are ——" called orbitals. This also means definite energy level also. 2. The word ‘orbital’ does not imply any such definite region. 3, The shapes of different orbitals are different; s-orbitals are spherical, p-orbitals are dumb- bell shaped with two lobes; d-orbitals are! double dumb-bell with 4 lobes. a y soils peorbitals 4. Orbitals are related to 3 quantum numbers, n, 1, m. Example 3px, 3Py, 3P2- 5. For !=0,1,2,3 etc, the orbitals are designated as s, p, d, f. Here principal quantum number and orientation are mentioned for precision. Example, 3px, 3py. 3P2- 6. Each orbital can accomodate 2 electrons, with opposite spins. Example each s-orbital accomodates 2 electrons, 3 p-orbitals 6| electrons, 5 d orbitals contain 10 electrons.128 Chemistry- First Paper f AT: 19- 20; MAT The number o} tons present in the nucleus of an atom, is called its atomic number. Again outside the nucleus, same number of electrons, equals to proton-number, rotate in different orbits of the atom, Thus atom becomes electrically neutral. Electron Configuration : According to quantum mechanics the definite number of electrons of an atom get arranged in different energy levels or orbitals with some definites rules, The arrangement of the electrons in different orbitals is called electron configuration or electron distribution in an atom, A set of threesules called the aufbansprinciplesEromthexGermanword:forbuildingup! guides the filling order of orbitals. In general each successive electron added to an atom occupies the lowest-energy orbital available. The resultant lowest energy configuration is called the ground state electron distribution of the atom. Often, several orbitals like three p-orbitals, five d-orbitals have the same energy level. Orbitals that have same energy level are said to be ‘degenerate ' orbitals.Qualitative Chemistry 129 ‘Three Rules of the Aufbau Principle and its Summary : * 1, Lower-energy orbitals are filled up by electrons before high energy orbitals. The orderingiofienergy:levelstforlorbitalstistasifollows': 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p and 8s is shown in figure-2.9 and can be remembered by scheme shown in figure 2.13. * 2. An orbital can hold only two electrons with opposite spins. This is just a restatement of the Pauli exclusion principle, emphasizing that no two electrons in an atom can have the same four quantum numbers. + 3. If two or more degenerate orbitals are available one electron goes into each until all are half-full, a statement called Hund’s rule. The electrons in each of the singly occupied orbitals must have same spin. 1, Pauli Exclusion Principle and its Explanation Pauli exelusion!priniciplé : The values of four quantum numbers of two electrons in an atom cannot be identical; at least one value must be different. — It means that among the electrons in an atom value of at least one quantum number must be different. For example, there are 2 electrons in helium/atom. The two electrons have the following values for four quantum numbers, ‘Foristelectronyey : n= 1,1=0,m=0, ay For 2ndielectron, ep: : n=1,1=0,m=0,sG-!) ‘Among the values of four quantum numbers of these two electrons, three values are identical but the fourth value (i.e. spin quantum number) is different, Hence Pauli exclusion principle is supported by helium atom, 2, Hund’s Rule and its Explanation : Hund’s Rule : The electrons will distribute themselves in different degenerate orbitals in such @ way that maximum number of'electrons remain in unpaired state wilh «pin of same direction, ‘Degenerate orbitals’ having same energy are three p-orbitals, five d= orbitals and seven f-orbitals, Hund'sinileisinot'for'ssorbital: For example : The electronic configuration of N (1) = 1s? 2s? 2p*. In reality there are three 2p orbitals of same energy, which are designated as px. Py and Px. Chemisty Fist Paper—17130 Chemistry- First Paper According to Hund’s rule, here last three electrons will remain in three different p- orbitals with their spin in same direction. It is shown in box system as follows : Is2 952 2p3 na- fy] fy ttt Here the arrow sign (1) indicates the direction of spin of electrons. Similarly the electronic configuration of oxygen O(8) is 1s? 2s? 2p*. More precisely (8) = 1s? 2s? 2p,? 2py! 2p,'. It is shown in box system as follows. j Whatlis Ihe shape Of ps Is2 952 apt OB8= [11 TL i ital? ta “ yeircular jumbell shape eeetcaamet 4) two dimension Aufbau Pi le an Explanation Aufbau Principle : In an atom the electrons occufy different orbitals according to their increasing energy levels. That means electrons first fill up the more stable orbital of lowest energy and then gradually the orbitals of higher energy level Explanation of Aufbau Principle The energy of different orbitals are calculated from the values of (n + /) of those orbitals. Gradation of orbitals with their energies is as follows (see Fig-2.13): (att) = (40) =1 1s, 2s, 2p, 3s, 3p, 45, 3d, 4p, 5s, 4d, Sp, 6s, 4f, Sd, lem eciiae 6p, 7s, 5f, 6d, 7p, and 6s o (at =3 a (th=4 For Example : As per Aufbau Principle, the electron (at)=5 distribution of K(19) and Sc(21) are as follows : Se ip E " 17K(19) Is? 28? 2p6 3s? 3p yeee2d, —> 1s? 2s? 2p 3s? 3p6 As 4s orbital energy is less than 3d orbital energy, so the last or 19th electron of K-atom occupies 4s orbital “F915 . Order of energy levels instead of higher energy 3d orbital. of different orbitals ‘Again in scandium, after filling the lower energy 4s orbital, then the last or 21st electron of Sc atom occupies higher energy 3d orbital. Both the examples follow the Aufbau rule in filling orbitals by electrons,Qualitative Chemistry 131 %* Determination of order of orbitals : (n + 1) rule : To determine the comparative energy of different orbitals the following two rules are generally used. will be of lower Rule-1 energy. For example among 34, 4s, 4p orbitals : (Fig 2.13.) for 3d orbital : (n+) =@G+2) 45 = for 4s orbital : (n +1) = (4+ 0f <4) ae. for 5p orbital : (v+1) = +1) be ; ©) then 3d will be of So, higher energy and Sp will be of highest energy content. : If two or more orbitals possess same value of (n + 1), then the orbital whose value of 'n’ is less, will be of lower energy. For example, among 3d, 4p and 5s orbitals : 3d Ybital: (n+) =G+2) = ital: (n+) =(@+1) = for 4po for Ss orbital: (n+l) =(5+0) = For all these orbitals (n + 1) value is equal to 5. Since for 3d orbital the value of n is less than the others, it will be of lowest energy; then comes 4p orbital and then comes 5s orbital highest energy. 3d < 4p < 5s. That these calculations are havin} It must be remember guide lines. Sometimes it is not strictly followed. But it is’ a very useful rule. Rule of Writing electron configuration : ‘The electron configuration of any element is written in the ascending order of n. For example we can write the electron configuration of Zr (Z = 40) following the Aufbau principle using Fig 2.13 as follows : Zr (40) = 1s? 2s? 2pS 3s? pS [452] 3d!0 4p6 [5x7] 4a? But finally the above electron configuration should be written according fa value of n as follows : i Zr(A0) = 1s? 2s? 2p6 3s? 3p 340 4s24p6 ga 552, J |132 Chemistry— First Paper * Deviation of Electron Configuration from the General Rule : The electron configuration of almost all elements can be confirmed according to Aufbau principle using Fig. 2.13. But there are some deviations. Two beeugiees reasons behind these deviations are as follows : (1) More stability of half- filled and full - filled orbitals': ICis found that the degenerate ——-. orbitals (p, d and f) gain more stability, whensahoysaresexacty:halfcflled-or-fall=Ailledwith ‘electrons. That means ap3ynp*ndeynd!9pnf/andmnfl;configurationsjare;more!stable. For this reason thesconfiguration®(n=1)d> ns! becomes: more stable than (n — 1) d4ns?/and (n= 1Y'dlOe inslabecomessmore)stable:thans(n=l)d2ns* Therefore the electron configurations of 24Cr and 29Cu are as follows = = Is? 2s? 2p6 35? 3p CD) il Gu029) = 15? 25? 2p6 352 3p (3479) [but not 1s? 2s? 2p6 3s? 3p6 3a? 452] co (2) Very small difference of energy between n f and (n +1) d orbitals (but not 1s? 2s? 2pS 3s? 3p6 3d4 452) a 2 In cases of atoms of higher atomic number, the difference of energy between nf and (n + 1)d orbitals is very low. Therefore sometimes one or more electrons may go from n f orbitals to (n + 1) d orbitals. For example, the real electron configuration of Lanthanum (57) is : 57) = 1s? 2s? 2p6 3s? 3p8 3d'0 45? 4po Aat0 [4F°] 5s? Sp6 [Sd] 6s? Aithough according to general rule, it should have been— 4410 [AFT] 532 Sp 6s2 . Worked Example-2.17 : Justify orbital’s energy : t lower energy orbital in each pair of followings : (a) 4d, 5s; (b) 34, 4p; (c) 3p, 4s Strategy : Apply rule (n +1) in each case : Solution : (a) In 4d and 5s pair orbitals : For 4d orbital, n= 4,1=2; -. (n+1)=(4+2)=6 For 5s orbital, 0 (n+1)=(6+0)=5 So 5s orbital is of lower energy than 4d orbital. )) 3d and 4p pair orbitals : For 3d orbitals, n=3, F For 4p orbitals, n= 4, I= (2+) =G+2)=5 (@+D=@4+=5Qualitative Chemistry 133 The value of (n+ 1) for both orbitals is 5, then orbital of lower n's value will be of lower nergy. Hence 3d orbital is of lower energy than 4p orbital. (©) 3p and 4s pair orbitals : For 3p orbital, n= 3,1 .(a+D=G+1)=4 For 4s orbital, n= 4,1=0; « (a+) =(4 40) =4 The value of (n + 1) for both orbitals is 4; then 3p orbitals having lower n’s value is of er energy than 4s orbital. Worked Example-2.18 : Permitted quantum number sets : Whether the following quantum number set is permitted on not; explain. @)n=3,1=2,m=0,s=4) (b)n=3,! =1,m=-2,s=47 ()n=2,1=2,m= 1s @n=2,1 = 1,m=0,s=1 Strategy (n— 1),m=+l ands= Solution : (a) is permitted; because all values follow general rules. (b) not permitted; because here / = + 1, so m=, 0,-/ values are possible, but |= 2 not permitted. (©) not permitted; because values of n and / are same, which is not possible. (4) not permitted; because spin number may be +3 or —J; here s = 1 is not permitted. Worked Example-2.19 : To write symbols for permitted orbitals : Of the following orbitals which one is possible and which ure not; explain. (a) Ip (b) 2d (c) 3d Strategy :1=(n—J)and 1=0 =s orbital, ! = /= p orbital 1=2=4 orbital. Solution : (a) For Ip orbital, here n = I ie. here for Ist orbit only 1 = 0 possible or Is orbital is possible. Hene Ip orbital is not possible. 'b) For 2d orbital, here n = 2 i.e here for 2nd orbital 1 = 0,1 possible or 2s, 2p orbitals are possible . Here 2d orbital is not possible. . ~~ fc) For 3d orbital, here n = 3 i.e here for 3rd orbit only J = 0, 1,2, possible or 3s, 3p and 3d orbitals are possible. Here 3d orbital is possible.134 Chemistry First Paper Worked Example 2.20 : Electron distribution based : ‘Write the ground state electron distribution of the atom of the element with at. no, Z = 13 and also show the filling of its orbitals of valence shell with notation of spins. Strategy : Write gradation of orbitals with energy levels as per fig. 2.13. Each orbital can accomode two electrons with opposite spins. Write Hund's rule in box-form. Solution : Ground State electron distribution of atom with no. Z (13) is : 1s? 2s? 2p® 3s? 3p! = Valence-shell electron distribution in box method : For Z= 13: [Ne] fy re Worked Example-2.21 : How many maximum number of electrons can be accomodated in 5 g sub-shell for a newly invented element? Stfategy : Whem'subsidiaryequantummumbers:li=4y then:'g';subéshell:is:possibles Total “orbitals number in a sub-shell De ‘Solution : MOtalvorbitalsmumbersiny In each orbital two electrons with opposite spins will be accomodated. So |Syguisubshely | eantaeconiod ate ax iffibii number oflelectrony 9 2—18s —_ sub-shell (2x41) =9: - Worked ‘Example- 2.22 : Explain the cause of having electron distribution like 3d! 4s! instead of 3d? 4s? in valence-shell of Cu atom, ,Qualitative Chemistry 135 Strategy : d!° electron distribution is more stable than d Solution : The degenerate orbitals (or orbitals with equal energy) gain more stability, when they are exactly half-filled or full-filled with electrons. That means np3, np®, nd5, nd!®, nf7, nfl4 configurations are more stable. For this reason, 3d!9 4s! electron distribution for Cu-atom is practically happened but not 3494s? Worked Problem-2.23 : Write valence shell electron distribution of Ca~atom in box— form, Calculate the set of 4 quantum numbers permitted for valence-shell electron of Ca— atom. Strategy : Here Aufbau principle is followed. Solution : Atomic number of Ca is 20. Its electron distribution is : 42 Ca(20) > 1s? 2s? 2p* 3s? 3p* 4s. Valence-shell electrons in box-form, w The set of 4 quantum numbers for 4s? electrons + Quantum number —> |x] |m Istelectron,e, |4 | 0 2nd electron,e, [4 |0 |0 Worked Example-2.24 : To describe fully each electron of silicon atom (14! write the set of 4 quantum numbers. Strategy : With set of 4 quantum numbers, Aufbau rule will be applied. Solution : Electron distribution of Si (14) — 1s? 2s? 2p6 352 3p? This eléctron distribution may also be shown as follows : Electrons—> 1,2 3,4 5 - 10 112 13,14 sox fe) fe] fl) fe] fh Orbitals—> 1s? 2s? 2p,?2py?2p,2 3s? 3p! Spy! 3p.136 ‘Chemistry— First Paper Set of 4 quantum numbers for each electron : Electrons in orbitals | Electron serial | _n 1 m 1s? 1,2 1 0 0 232 3.4 2 0 0 2 2 +1 2p6 5-10 2 1 0 2 1 —1 oh 3st 11, 12 3 0 0 z 3px! 13 3 1 41% +4 3py! 14 3 1 -1e* +3 * Value of ‘m' may be any one of (+ 1, 0, — 1). * * When m = + 1 is used for 13th electron, then for 14th electron, any of rest two (0,-1) can be used. For's' any of +5 or —3 may be used Worked Example—2.25 : Some element has its valence shell electrons like ns? np*; here n= 2. Explaii Strategy degeneratevorbitals. ——— Solution : From question, electron distribution in valence-shell is ns? np* and n = 2. So that electron distribution is : 2s? 2p* and the element is O (8). So, O(8) > Is? 2s? 2p* Electron distribution in orbital method: 1s? 2s? 2p,?2p,! 2p, and electron distribution in boxmethod: [ib] [it] [tt [4] ‘whether Hund’s rule is applied in this element. [R.B. 2017] In the above electron distribution, the last 4 electrons of O-atom are in maximum unpaired stage in 3 degenerate p-orbitals. So oxygen atom follows Hund's rule. Worked Example-2.26 : Some element has electron distribution in its last two energy levels like, (n-1)s? (n=1)p® (n-1) 4? ns!; here n = 4. Explain why d-orbitals remain vacant here. [D. B. 2017) Solution ; From question, electron distribution in last two energy levels of the element is (-1) $? (n-1) pé (a-1)4° s!.Qualitative Chemistry 137 Putting n = 4, we get : (4-1)s? (4-1) pS (4-1) d° 4s! = 3s? 3p 3° 4st. So that element is K (19) with electron distribution : K (19) > 1s? 2s? 2p® [352 3p 3d 4s! Here as per gradation of orbital energies, 4s orbital has less energy than 3d-orbitals and this can be shown from formula (n + 1) : For 3d orbitals : n= 3, and/=2; ~ (n+) =(@+2)=5 For 4s orbital: n= 4, and 1=0; + (n+) =(44+0)=4 : 3d > 4s; hence according to Aufbau principle the last electron of K (19) occupies more stable lower energy 4As orbital. The electron distribution of K(19) in its last two energy levels in box form is: K (19) — [Ne] 3s? 3p® 34° 4st fe) fe }y [ 1c Worked Example-2.27 : Given Stem : Ar(n-1)d° [Ctg. B. 2015] (A) All electrons of d-subshell of given stem have same spin value; explain, (B) The given electron distribution is for a cation; Justify it. Solution : (A) In d-subshell (n = 2) of an atom, |/| ™ | Value & spin's magnetic quantum number (m) may have five values 22 = [+12 T (2. -1, 0, + 1, + 2). So with these five values total tT d-orbitals are dxy, dyz, dex, dy?2-y2,d2?. Asiper given stem |7 | 0| +12 |t | there are 5 electrons in d-orbitals (45). According to Hund's | [#1 | +12 tT rule five non-degenarate'd orbitals can accommodate 5 | [42] 412 [t | electrons with like or same spin value + 1/2. ‘Thus it is proved that d> electrons must have same value of spin quantum number. Solution : (B) As per given stem, the electron distribution is Ar(n-1)d5, Here Ar is argon with atomic number 18. Its electron distribution is : Ar (18) —> 1s? 2s? 2p® 3s? 3p®. Here n =4, (n=l) =3 ws Ar (n-1)d9 — 1s? 2s? 2p8 352 3p6 3d5. According to Aufbau principle, electrons enter into 4s orbital and filling it, remaining electrons enter in 3d orbitals, if possible, according to orbital order 3d > 4s. Chemistry First Paper—18138 ‘Chemistry— First Paper But as per given stem, there is no electron in 4s orbital, It means 4s electrons are already removed. So given electron distribution stands for a cation of 3d-transition elements and it is, as follows : 1s? 2s? 2p6 3s 3p 345 4s” Again no charge number is shown on cation. Generally, to form cation of transition metal, here 4s2 electrons are first removed and then one or two 3d electrons may be removed, if necessary or possible. So here possible cation may be Mn?* or, Fe** or, Co ion. {RB 2015; Cig. B. 2015) | | |¢ Qualitative Chemistry 139 2.4.1 Electron Configuration of first 30 elements With the application of Aufbau principle, Hund's rule and Pauli's exclusion principle, the electron configurations of first 30 elements . H (1) to Zn (30), are shown below = [ielement ‘SSconnGions e--configurations in Box method Orbital method Is is a ‘3p H(i) ist He(2) 1s? Li@) 1s?2s! wo Be(4) 1s? 2s? fal BO) —1s?2s% 2p! aa] | LO LG(6) > 1s?2s? ap? fa] | HT) N(7) 1s? 2s? 2p3 Hd (1) O®@ —1s?2s? apt fa) | Ga ‘ FQ) 1s? 2s? 2p> Ae (TT) Ne (10) -+1s?2s? 2p% [Na (11) —1s?2s? 2poast MATE fia) | ATA] Aa) | Aa) f] |} ooo Mg (12) —1s?2s? 2p%3<2 aa) | Walaaity | fa) | CO Al (13) —1s?2s? 2p8 3s? 3p! a] ) faa) | Aatatay | fia) | oo Si (14) 91s? 2s? 2p6 35? 3p? Md (ia) | Wavastry | (a) | AT P(15) —1s?2s? 2p 3s? 3p lid fa} | Astaalay | (4a) |) A S16) ls? 2s? 2p® 3s? spt ad) | fa) | atau | fy Wait 2 3p5 paT'l+17] Problem- 2.28 : The atomic number (2) papers ee ar ana ca, K(19) [Ne] 3s? 3p83d9 4s! | distribution as per Hund’s rule and write the values Ca (20) —s{Ne] 3s 3p6 3d° 4s? | of 4 quantum numbers of the valence shell electrons. Sc (21) [Ne] 3s? 3pS3d! 4s? _ | Solution :Z (8) > 1s? 2s? 2px? 2py! 2pz! Ti (22) [Ne] 3s? 3p6 ad? 4s? | Valence shell: > 2s? 2p,2 2py! 2pzt V(23) INe] 3s? 3p°Sd3 45? au) el fal ft CE (24) —INe] 3s? 3p 305 4s! _ | Valence shell contains six electrons; their Mn (25) [Ne] 3s? 3p$3d5 4s? | quantum number set areas follows : Fe (26) Ne] 3s? Sp®3d° 4s? | electrons n - m 8 orbitals C027) —INe] 8s? 3p$3d? 4s? ciwee? 0 Souls Ni (28) Ne] 3s 3p°3d® 4s? ey 2 0 0 Ll ChQ9 INE] 3s? 3p8salo ast | ce; 2 1 +1 42/2 2px! Zn (80) Ne] 3s? 3p°3d!0 ds? | ex 2 1 0 41 2pyt es 2 1 -1 412 pz! &% 2d ee ee140 yer Chemistry— First Paper 2.5 Electro-Magnetic Spectrum. Itis now established by scientist Maxwell that light of different types, visible and invisible are produced from clectromagnetic radiation. This radiant energy propagates in all directions with waves, Like ocean waves, electromagnetic radiant energy is characterised by a wavelength, frequency and an amplitude. Thesvelocitysofilightydepends:onsmediums..ne i ity )O%m/sP usually rounded off to 3.0 x 108 mvs. The velocity of light, being wave energy, is related with wave length (A in metre) and frequency (®, in hertz or, s!). These two term are related inversely as follows | Penn) Ssfrequencyin Hertzy\(Hz)ylHz="1s-!(reciprocal’second), Frequency (8) of a wave is the number of wave peaks that pass by a given point per unit time like second, Amplitude of the waye is the height of the wave, measured from the centre line between peak and trough of the wave. ain frequency (8), having large value, is alternately expressed as wave number per metre by dividing it by velocity (c) of light and denoted as nu-bar (8); 3 = 2 ek Frequency (v) is the number of ‘Wave length () "wave pea Kper unit time Peak eal ae (QR) radiation(v=3.75 10's") s) Sree eee 7 _} tte tics wave lengths (A) and freqencies (v) i ’ Fig 2.14: Electromagnetic waves, wave length, frequency and amplitude.Electromagnetic waves + are characterized by a wave length, a frequency & an amplitude i141 Light, the electro magnetic wave energy, consists of visible and invisible ranges in our scenses. Visible light itself is invisible, but it makes the substances visible to our eyes; hence it is called vi ht. Visible light consists of a very small range out of the .clro magnetic range. The remaining great range includes mainly gamma rays, X-ray, ultra-violet ray, infrared radiation, micro waves, radio waves etc, Collectively, they make up the electro magnetic spectrum. These different types of radiations are shown’ below differing in wave lengths in nanometre @nnt="10-%m). ‘osmic rays = <0.00005 nm Wave length of gamma (y) rays; 0,0005-0.01 nm Wave length of X-ray Wave length of UV ray whole ele fave lengths of VIBGYOR in vis Violet ; 380 —424 nm Indigo: 424 —450 nm Blue: 450- 500 nm Green: 500-575 nm 0.0inm — 10 nm 10 nm-380 nm Wave length of Visible Light \\ : 380nm — 780 nm Wave length of infrared rays Yellow = 575-590 nm Wave length of micro waves. Orange > 590-647 nm Wave length of Gale faery Y 2 647 — 780 nm “The Pemilar visible ragicn accounts fea Tap Pree On ice eer ram? ait Bacteria Dust Pinhead Fingernails Humans Wave length (2) in meters a hang 102 19-0 19* 104 10+ 10 1 py Na a Gammarays rays Ultraviolet Infrared Microwaves Radiowaves : Tl eae ee ti lal 10% 108 1016 104 102 1019 108 Frequency (V) inhertz 380 nm 500 nm 600m, 700nm 780mm 3.8 x10%m 7.8x107m ‘Waves in the X-ray region have a length ‘that is approximately the same as the ymeter of an atom (10-10 mm) Fig-2.15 : The electromagnetic spectrum consists of a continuous range of wavelengths and frequencies from radiowaves at the low frequency end to gamma rays at the high frequency end. .142 Chemistry- First Paper .5.1 Different Regions of Electro Magnetic Spectrum Flectromagnetic spectrum is mainly divided into following seven regions depending on the wave length (A) or frequency (8) or wave number (9), in order of increasing wave length of the radiation; [Fig-2.15]. 1. Gamma (¥) ray Region : The wave length of gamma rays lies between 0.0005 nm~ 0.01 nm, The waye length of the region is being small; the waves are more energized. Radioactive isotopes emit gamma rays. Gamma rays are used in Mossbaer spectroscopy and Neutron activation analysis. X-ray Region : The wave length of this region varies from 0.01nm — 10 nm. X-rays are used in the analytical instruments like X-ray Fluorescence, X-ray Emission and X-ray Crystallography. UV-ray Region : This region extends from 10 nm — 380 nm in total spectrum. Different wave lengths of this region are used in the following instruments and different applications. (i) 30nm - 200m Wave length: UV-photo electron spectroscopy, Gi) 230 nm = 365 nm Wave length: UV-ID, Label tracking Gii) 230 nm —380 nm Wave length —: Optical Sensors. (v) 240 nm 280 nm Wave length : Disinfection of surface water. (DNA absorption has a peak at 260 nm) 200 nm =400 nm Wave length: Drug detection, Forensic analysis. i) 270 nm ~360nm Wave length: Protein analysis, DNA sequencing, drug discovery. 9280 nm ~400:nm Wave length : Medical imaging of cells. *(Sueit) 300 nm — 320 nm Wave length : Light therapy in medicine. {. Visible Regio called VIBGYOR range. The valence electrons in atom or molecule absorb or radiate This region covers 380 nm~780 nm wave lengths. This region may be energy of this region and form different spectra. |. Infrared Region : This region begins from visible or ‘infia’. Its range is 780 nm to 1,0 mm or 1000 j1m, This infrared portion of the spectrum is divided into three smaller segments : near-IR, middle-IR and far-IR, Far-Infrared (FIR) is considered to the strongest healing frequency, emitting a wave length of 25 im -1000 jum {micrometers (um), Ium = 1 x 106m]. This rays are used to determine structures of organic ' compounds. It is also used for communication signals (mobile phones) including TVQualitative Chemistry 143 remote controls and DVD player, Optical fiber communications, night vision, thes phy tracking (missile guidance system). 0.78 m—2.5 um = [used in medical field] or Near-IR region Middle IR region ;N22S ames um + [orstleure er eeconpoural Far-IR region h=25um—1000 pm : Tused in medical fieta] 6. Miero-Wayes Region : Micro-waves Tegion has wave Tength from 1000 1 m to 100 cm. . Radio-Waves Region : This region covers the spectrum of wave lengths 10 km — Imm. ‘These waves are produced in radio-antena by high frequency AC (alternate current). Radiowaves are used in MRI (magnetic resonance imaging) machine to excite low energized proton or neutron in NMR atoms which contain odd number proton or neutron in nucleus (like 'H, 13C, !9F, 3!P etc). The NMR atoms haye weak magnetic moment and this property is used in MRI technique (see principle of MRI Test in icle—2. 10). 3kH2-3 x 1011 Hz 1 Radio-{EV signal. machine. Amm-im, 3x 108 Hz-3 x 101! Ha 2. Wi-Fi, mobile phone signal & micro-oven, tmm-780nm | 3 x 10!! Hz-385 x 10!? Hz 3, Remote control, used in Optical fibre. 780 m-880 nm | 385 x 1012 Hz -790 x 101? Hz| 4. Photosynthesis, Analytical experiments. . PAT!D4 ate Wim] iotE ata |e detection 10nm-001nm 13x 1016Hz—3x 1019 Hz | 6. Used in medical Science for internal skeleton-image. | Perey