Scribd Logo
Upload

Welcome to Scribd!

  • 17 views

    Chem Ge4

    Uploaded by

    asish

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
    Flag for inappropriate content

    You might also like

    Chem Ge4

    Uploaded by

    asish
    17 views267 pages

    Original Title

    Chem ge4

    Copyright

    © © All Rights Reserved

    Available Formats

    PDF or read online from Scribd

    Did you find this document useful?

    Is this content inappropriate?

    Report this Document

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
    Flag for inappropriate content
    Download as pdf
    17 views267 pages

    Chem Ge4

    Uploaded by

    asish

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
    Flag for inappropriate content
    Download as pdf
    of 267
    phaly ur? Kole AS PER CBCS MODEL SYLLABUS MODERN COLLEGE CHEMISTRY SEMESTER-I (THEORY AND PRACTICAL) For Pass/Generic Elective Students of All Universities and Autonomous Colleges in Odisha (fansite cea comes Y.R. SHARMA Formerly Senior Lecturer in Chemistry, D.AV. College, Jalandhar. Author : Elementary Organic Spectroscopy, A Textbook of Complete Organic Chemistry “Text-Book of Modern Chemistry etc. etc. us KALYANI PUBLISHERS LUDHIANA - NEW DELHI - NOIDA (U.P.) - HYDERABAD CHENNAI - KOLKATA - CUTTACK - GUWAHATI - KOCHI-- BENGALURU SEMESTER-I For Pass/Generic elective students of All. Universities and autonomous Colleges in Odisha 'GE-I (THEORY) GE : Atomic Structure, Bonding, General Organic Chemistry. & Aliphatic Hydrocarbons (Credits : Theory-04, Practicals-02) End Sem. 60 marks Mid Sem. 15 marks Theory : 60 Lectures Time : 3 hrs. SECTION A : INORGANIC CHEMISTRY: UNIT-I ATOMIC STRUCTURE Review of Bohr’s theory and its limitations, dual behaviour of matter and radiation, de-Broglie's ?élation, Heisenberg Uncertainty principle. Hydrogen atom spectra. What is Quantum mechanics ? Time independent Schrodinger equation and meaning of various terms in it. Significance of y and 2. Schrodinger equation for hydrogen atom. Radial and angular parts of the hydrogenic wavefunctions (atomic orbitals) and their variations for 1s, 2s, 2p, 3s, 3p and 3d orbitals (Only graphical representation). Significance of-quantum numbers. Shapes of s, p and d atomic orbitals, nodal planes. Rules for filling electrons in various orbitals. Electronic configurations of the atoms. Stability of half-filled and completely filled orbitals, concept of exchange energy. Relative energies of atomic orbitals. Anomalous electronic configurations. UNIT-II CHEMICAL BONDING AND MOLECULAR STRUCTURE Ionic Bonding : General characteristics of ionic bonding. Energy considerations in ionic bonding, lattice energy and solvattoh energy and their importance in the context of stability and solubility of ionic compounds. Statement of Borti-Lande equation for calculation of lattice energy, Born-Haber cycle and its applications, polarizing power and polarizability. Fajan’s rules and its applications. Covalent bonding : the basis souding : VB Approach ; Shapes of some inorganic molecules and ions on | Square o10k VSEPR and hybridization with suitable examples of liner, trigonal planar, concept ei ashe ‘edral, trigonal bipyramidal and octahedral arrangements. Rompounds. and resonating structures in vairous inorganic and organic MO Ay ae ce arated : Rules for the LCAO method, bonding and antibonding MOs and their eesBiation Ge ea see, Por combinations: atomic orbitals, non-bonding Combination of orbitals, MO treatment of homonuclear diatomic molecules (Nz, O2) nuclear diatomic molecules (CO, NO) Comparison of VB and MO approaches. SECTION B : ORGANIC CHEMISTRY-I UNIT-IL FUNDAMENTALS OF ORGANIC CHEMISTRY physical Effects, “Electronic Displacements : Inductive Effect, Electromeric Effect, Resonance and Fiyperconjugation cleavage ‘of Bonds : Homolysis and Heterolysis. Structure, shape and reactivity of organic molecules : Keacleophiles and electrophiles. Reactive Intermediates : Carbocations, Carbanions and free radicals. Strength of organic acids and bases : Comparative study with emphasis on factors affecting pK values. Aromaticity : Benzenoids and Yuckel’s rule. STREOCHEMISTRY “1 Conformations ‘with respect to ethane, butane and cyclohexane, Interconversion of Wedge Formula, Newmann, Sawhorse and Fischer representations. Concept of chirality (upto two carbon atoms). Configuration : Geometrical ‘and Optical isomerism : Euuntiomerism, Diastereomerism and Meso compounds). D and Lj cis-trans nomenclature : CIP Rules R/S (for one-chiral carbon atoms) and E/Z Nomenclature (for upto two C = C systems). UNIT-IV ALIPHATIC HYDROCARBONS Functional group approach for the following reactions (preparations & reactions) to be studied in context to their structure. pa ‘alkanes : Upto 5 Carbons). Preparation : (Catalytic hydrogenation, Wurtz reaction, Kolbe’s synthesis, from Grignazd-teagent, Reactions : Free radical Substitution: Halogenation. Aa ‘Alkenes : (Upto 5 Carbons) Preparation: Elimination reactions : Dehydration of alcohols and dehydrohalogenation of alkyl halides Gaytzeff’s rule); ds alkenes (Partial catalytic hydrogenation) and trans-alkenes Birch seduction) Reactions : cis-addition (alk. KMnOs) and trans-addition (bromine), Addition of HX (Markownikoff's and anti-Markownikoff’s addition). Hydration, Ozonolysis. Le Alkynes : (Upto 5 Carbons) Preparation ; Acetylene from CaC, and conversion into higher alkynes: by dehalogenation of tetrahalides and dehydrohalogenation of vicinal- inhalides. Reactions : Formation of metal acetylides, addition of bromine and alkaline KMnOs, ozonolysis. PASS/GE-I LAB:ATOMIC STRUCTURE, CHEMICAL BONDING GENERAL ORGANIC CHEMISTRY & ALIPHATIC HYDROCARBONS (F.M = 25) (Expt.-15, Viva-6 & Lab. Record-4) Time : 3 hrs. SECTION A : INORGANIC CHEMISTRY-VOLUMETRIC ANALYSIS Estimation of sodium carbonate and sodium hydrogen carbonate present in a mixture. Estimation of oxalic acid by titrating it with KMnO,. Estimation of water of crystallization in Mohr’s salt by titrating with KMnOy. Estimation of Fe (I) ions by titrating it with KyCr,O; using internal indicator. . Estimation of Cu (Il) ions iodometrically using Na,SO3, SECTION B : ORGANIC CHEMISTRY gp ep Detection of extra elements (N, S, Cl) in organic compounds (containing upto two extra elements). . Separation of mixtures by Chromatography : Measure the Ry value in each case (combination of two compounds to be given). (a) Identify and separate the components of a given mixture of 2 amino acids (glycine, aspartic acid, glutamic acid, tyrosine or any other amino acid) by paper chromatography. (b) Identify and separate the sugars present in the given mixture by paper chromatogrpahy. 2. 3. SECTION A : INORGANIC CHEMISTRY-I ATOMIC STRUCTURE 3-54 CHEMICAL BONDING AND MOLECULAR STRUCTURE ; 55-108 FUNDAMENTALS OF ORGANIC CHEMISTRY 111-195 ALIPHATIC HYDROCARBONS. 196-255 SECTION C : LAB: EXPERIMENTS PASS/GE-I LABORATORY EXPERIMENTS 259-278 5 SECTION-A 2 INORGANIC CHEMISTRY-I _ y <> ATOMIC STRUCTURE <> CHEMICAL BONDING AND MOLECULAR STRUCTURE REVIEW OF BOHR’S THEORY AND ITS LIMITATIONS Bohr’s Theory of Atom: Neil Bohr (1913) postulated a theory on the basis of quantum theory of radiation. His main purpose was : (i) to overcome the drawbacks of Rutherford’s atomic model, and (ii) to explain the line spectra of hydrogen and hydrogen like monoelectronic atoms or ions (He*, Li). Main prostulates of this theory are as follows : 1. The electrons in an atom revolve around the nucleus only in certain permitted circular orbits or stationary states. These orbits are called energy shells or energy levels because these are associated with definite amount of energies. Different shells are K, L, M,N, O etc. When the number of the shells (n), is 1,2, 3,4, 5.. the shells are called K, L, M, N, O....respectively. (Fig. 1.1). (a) Energy of a shell (n), Fi energy levels, (b) Distance ‘r," of a shell from the nucleus is calculated by the relation ae 4x7e7mZ [where m and ¢ are mass and charge of electron, Z = atomic number ; Tn J = Planck's constant (= 6.625. 1077 ergs = 6.625 x 10-4 Js = 6.625 x 10 kg me? s~ [S.. unit] uy L4_] : "MODERN COLLEGE CHEMISTRY SEM. rieoR) 2. So long as the electron revolves in a particular orbit, it neither absorbs nor emits energy. That is, ‘why circular orbits are called stationary states. This explains the drawback of Rutherford's atomic model. 3. The revolving electron can absorb or emit energy only in fixed amount, ie. one photon or whole number multiple of it. ___,_* When an atom is associated with its normal energy, is electrons are said to be in ground state. When it absorbs energy. wt electrons get excited and jump to higher-onergy-level. The electron is unstable in the exeiied State. Thus, it jumps back to the ground state (either directly or in steps) by losing energy. (@) When an electron jumps from lower orbit (energy, E,) to higher orbit (energy E,), then difference of energy (Ey ~ Ey = hy) is absorbed. () When an electron jumps from higher orbit (energy, E:) to lower orbit (energy, E,), then difference Of energy (Ep ~ E, = /wv) is emitted as radiation. The facts given in (a) and (b) above explain the origin of spectral line in H-atom which corresponds to frequency, ». 5. Only those orbits are allowed for circular motion of electron for which the angular momentum (vr) of the electron is an integral multiple of h/2zr, Mathematically : mor = nh/2x where (j) m and v are mass and velocity of electron respectively. Gi rand n are radius and number of the orbit respectively. (ii) h = Planck's constant = 6.62 x 1027 erg. sec. When n = 1, 2, 3 etc., angular momentum of an electron will be h/2x, 2h/2x This principle is called quantisation of angular momentum Quantisation of Energy nhi2x. The word ‘quantisation’ means.that-a-quantity can-vary only-discontinuously to get a specific value. ‘The understand it, take the case of electric meter. Its reading always increases by whole number (i.e., one 12 unit) and not in fractions (i.e., 3 units) no matter at which speed the speedo-meter moves. Similarly, according to Bohr, the energy of an electron that revolves around the nucleus increases in whole number by absorption of a photon. In other words, the energy of the electron js quantised and has some specific value. Thus , quantisation is y note of Bohir’s theory. Ci APPLICATIONS AND LIMITATIONS OF BOHR’S ATOMIC MODEL @ Applications. Bohr’s atomic model is a modification over Rutherford’s concept of atom. The main achievements of Bohr’s theory are given below. Stability of atom. According to Bohr, the electron does not lose energy as long as it revolves in a parlicular orbit. Also, it cannot jump from first orbit to lower orbit as there is no orbit less than one. Thus, gradual loss of energy by the electron is not possible. Hence, atom is stable. Thus, it removes the limitation of Rutherford’s model of atom. 2, Explains emission spectrum. When an element is heated, its electrons absorb energy and jump to highéf energy levels. In the higher energy levels, the electrons are unstable. They jump back to the lower energy level within 10-5 seconds in one or more steps and release energy. The energy thus released gives emission spectra, Thus Bohr’s concept explains the emission spectra. ATOMIC STRUCTURE |” 7 5 “S-Explains absorption spectra, When an electromagnetic radiation is passed through the solution of chemical substance, some of its wavelengths are absorbed by the substance. The wavelengths absorbed are characteristic of that substance and cause the excitation of its electrons. The missing photons (from electromagnetic radiation) which are absorbed by the substance appear as dark lines in the spectrum. Thus, Bohr’s model explains absorption spectra. AC Explains Hydrogen Spectrum. Bobr’s Theory explains successfully the spectra hydrogen atom and hydrogen like ions. 5. Validity of Bohr’s theory for quantitative treatment to H-atom. (i) Rydberg (1890) studied experimental values of many spectral lines in H-atom and determined their frequency, ¥. ¥ =3.289 x 1015 sec"! (3 Z 4] np ny (i) Rite determined the wave number 7 of spectral lines by Ritz combination principle ee v= (5 “3 mony Here, R_= Rydberg constant = 109678 cm-!. 4 a qje Obtained for and 7 by Bobris approximately the same as that ‘The value of 22? me4/f3 and obtained by Rydberg and Ritz. This places Bohr’s atomic model on firm footing. 6. Determination of energy of one electron species. Energy of one electron species (He*, Li?) can be determined with the help of following expression derived by Bohr. 2x? me*2? apd Where Z= At. No. of element, E For Het (Z = 2) ; E= 8.716 X 10"! erg per atom. 7. Electrons in an atom are in motion and not stationary. An atom is electrically neutral. It means, the number of positive charges in its nucleus is equal to number of negative charges due to electrons around the nucleus. Let us suppose that the electrons around the nucleus are stationary. In this state, there is no force available to counterbalance the force of attraction between the nucleus and the electrons. Hence electrons will fall in the nucleus and atom is destroyed. But it is contrary to the facts. Hence electrons must be in motion. In such a case, the centrifugal force duc to motion of electrons will be balanced by the force of attraction between nucleus and electrons. It is also supported by Bohr’s postulates of atomic model. Limitations or Drawbacks of Bohr’s theory. Following are a few shortcomings of Bohr's atomic model: (O1. It fails to explain the spectra of multi-electron atoms. It only explains spectra of one electron species, e.g., H, Het, Li. } 2. According to Bohr, the circular orbits of the electrons are planar. But modem researches reveal that an electron moves around the nucleus in three dimensional space (X, Y, Z-axes). 3. It fails to explain the cause of chemical combination and shape of the molecules arising out of it. 4, Ithas been shown (Heisenberg’s uncertainty principle) that the exact position and exact momentum of a fast moving electron cannot be determined simultaneously. But Bohr stresses on stationary states. 5. It does not explain the splitting of Spectral line into a number of closely spaced lines. For example, when a sodium atom emitting radiations is Placed in a magnetic and electric field, each of the two yellow lines of sodium. @ = 5890 and 5896 A) further, split into two fine lines. It is called Zeeman effect and Stark effect respectively. Fig. 1.2. describes the effect of ‘SPECTRAL LUNES IN PRESENCE OF FIELD CLOSELY SPACED magnetic (or electric) field on a spectral SES SRUTING line. It does not explain the fine structure of spectral lines, e.g., when certain , single lines are seen under a powerful microscope, these are found to split into a number of closely related lines. According to Bohr, one and only one spectral line can be produced when an electron jumps from one orbit to another. Zeeman (and stark) effect. 7. It considers electron only as a particle. The wave nature of the electron is not explained. EMISSION SPECTRUM OF HYDROGEN When electric discharge is passed through hydrogen gas (low pressure) in a discharge tube, bluish glow is obtain fen this glow is analysed by means of.a prism,-a group of spectral lines are obtained in the infrared, visible and ultra violet region. (Fig. 1.3). The series of lines in various regions are named after the Hanes of their discoverers as follows: TEPEUND SERIES|(FAR INFRA RED REGION BRACKETT SERIES] INFRA RED REGION) HY PASCHEN SERIES (NEAR INFRA RED REGION) BALMER SERIES (VISIBLE REGION) VIOLET RED 4000 5000 60007000 LYMAN HYDROGEN SPECTRUM SERIES (VISIBLE REGION) ULTRA-VIOLET REGION Fig. 1.3 Series of lines of hydrogen spectrum. [ATOMIC STRUCTURE | Table 1.1 Series of lines in various regions. Names of serles | Discoverer, year Lines correspond to wavelength (A) ” 912, 931, 938, 950, 973, 1026, 1216 3668, 3970, 4101, 4340, 4861, 6563 8207, 10051, 10938, 12818, 18751 14590, 21660, 26280, 40570 22810, 56360, 74800 Lyman series Balmer series Paschen series Brackett series Pfund series Lyman, 1915 Balmer, 1835 Paschen, 1896 Brackett, 1922 Pfund, 1925 uy. Visible Near LR. LR. Far L.A. Bohr's atomic model is based on quantum theory. It provides a satisfactory explanation for various spectral lines in the hydrogen spectrum, ‘The energy possessed by an electron in an orbit is given as : ab Where (Z= 1) for H-atom Consider that an excited electron jumps from higher orbit (73) having energy, Ez to lower orbit () having energy, E}. The difference of energy (Ep - E = lv) is emitted as a spectral line corresponding to frequency, v. It is given by the relation amet 2a?met ) _ 22me = me h 2atmet (1 1 hy = —~—5 [Ey - Ey = by] late {- E,-E, =I] an?met (11 jill =? |5-s|=Rla-—z oli) © \@ oe) lee Here, R is called Rydberg constant = *3.289 x 10'5 sec (5 - 3) wwii) mm ‘The above equation can be used in terms of wave number ¥ also as given below : 2armet (1 1) {1 _ 1) = 1096778 em" ete susie ell at atl) cui eind = 1.09678 x 107 mt (5 - 3) nm om In S.1. System, the equation (i) would be expressed as ae 5} 9) neg) (nb 03 For calaulation of (Dv, use R= 3.289 x 10% s (ff) v, use R = 109677.8 cm” or 1.09678%107 mm \ or where (v). Similarly, wave number, ii), (iv) or (vi). It is explained in table 1.2. (4765)° 22?me4Z? TT MODERN COLLEGE CHE ” (#-3) Reciprocal of wavelength in metres. ¢ = Charge on electron ass of electron = Planck's constant Velocity of light = 3 108 ms factor whose numerical value is 1.11264 x 10-10 C N> nr y. V corresponding to each sj Line dan be determined by above equation (i), (ii) of ‘corresponding to each spectral line can be determined by above equations 1,602 x 101°C; 109 x 103! kg, 626 X10 Ts ony) svi) Table 1.2 Values of n, and n, for different lines in a series. Series} For ist line For 2nd line For 3rd line For 4th line Lyman Mat, m=2 | m=1,ms3 m=, mas Balmer my =2, m 4 =2, my Paschen 4 =3, ty 1, =3, ny Brackett m= 4, ny m= 4, Ny Pfund my=5, mm 1m, = 5, y= Large number of spectral lines Although, H-atom has one electron yet it gives large number of spectral lines. When electric discharge is passed through hydrogen gas, its electrons absorb energy and get excited to vacant higher orbits. These excited electrons fall back either directly or in steps to ground state, For energy jump of the electron to lower orbits, a photon of definite frequency is released which corresponds to a definite spectral line. Since large number of jumps are possible, so large number of spectral lines, are obtained Table 1.3 Frequencies in wave numbers (nr) of various lines of hydrogen spectrum Lyman series Balmer series Paschen Series “Calculated [Experimental | Calculated | Experimental | Calculated _ | Experimental values values values values values values 82,2105 82.2x105 18.21x10° 15.20x105 | 5.30x 105 5.32x 105 97.5 97.5 20.60 20.60 7.80 7.79 102.7 120.8 23.05 23.00 912 9.13 105.2 105.2 24,35 24.30 9.95 9.95 106.2 106.3 25.18 25.20 10.45 10.50 107.1 1072 25.55 25.70 107.9 108.0 sds The frequencies (in wave numbers) of spectral lines of Lyman, Balmer and Paschen series as calculated from above equation (iii) and those founded experimentally are given in table 1.3. [ATomrc stRUCTURE =o lenses Special features of hydrogen atomic spectra: These are given below : (i) There is no darkening between the lines of hydrogen spectrum. It indicates that hydrogen atom emits only specific and not all frequencies. ii) Hydrogen used for obtaining spectrum may be prepared from any source, the pattern of lines in the atomic spectrum is the characteristic of the hydrogen atom. This pattern is different from that of any other element. Thus, atomic spectra are generally referred as the finger prints of that atom. EXAMPLE 1. Find the frequency and wave number of first line in the Balmer series in C.G.S. units. SOLUTION. (i) Frequency : Here ny = 2, np = 3 (for first line) Substituting the value of ny and np in the equation 2 v = 3.289 x 10!5 (5 -3] sec!, we get mn y =3,289x 10!5 (s -3) sec 11 = 3.289 x 10!% ( - 5) = 4.56 X 10! sect (ii) Wave number > = wen Substituting the value of ny = 2 and mp = 3 in this equation = 1096778 ( - 3) em”! = 1523302. em", EXAMPLE 2. Find out the electronic state from which an electron jumps to emit radiations with wavelength 1212 A and give a line in the Lyman series of spectrum of hydrogen. (R = 109678 cm”). SOLUTION. Wavelength, 4 = 1212 A= 1212 x 10% cm We know, % = 109678cm™ ea mone we get, or 2 109678 em plane a mony But 2=1212 x 10cm and for Lyman series, m = 1 — 1, = 109678 en! (3 - 3) 1212 x 10 yom 1 1212 x 10° cm x 109678 em 301 -i= = y=? 75 m2 =4 orm Hence, the electronic state from which the electrons fall to the first orbit = 2. EXAMPLE 4. SOLUTION. ea r GE-T CREORD) (CGS. Units). Caleulate the energy of hydrogen atom in the first excitation oes re ASO X 10-0 esu ; mass of electon = 9.1 X 10% g. ‘The energy of hydrogen atom is given by the relation iz —)) State, The E,=- Thus, the energy of hydrogen atom in the first excitation state (11 = 2) is given ag follows: (2) B.1516 @.1x 107 9) (4.80% 107" esuy* (1) a (6.626% 107 ergs)? = - 5375 x 107 erg. Estimate the difference in energy between first and second Bohr orbit for a hydrogen atom. At what minimum atomic number, a transition from n= 2 to n = 1 energy would result in the emission of X-rays with 4 = 3.0 x 10° m ? Which hydrogen atom like species does this atomic number correspond to? (h = 6.62 x 104 Isec, c= 3 x 10! cms). E, = We know that E, =— 136 py. a For H-atom, Z = 13.6 For n=1,E,= ao eV.=- 13.6 eV. For 1=2,E)= 13.6 AE = E,-E; = =13.6e.V.-34e.V.=102eV. = 10.2 x 16 x1079J = 1632 x 10°95 But AE= hy = or AB=— ea) eV.- (-13.6e.V) Substituting the values in (1), we get ap = £826 10 Js) 3 x 108 ms” 18 (2) apes 6.626 x 10-18 J ( For any other atom, for the transition, n =2 ton=1 BS prey, - BES pv, 2 Fe 1365) 13.6 5 1 =- Gr wv.-(-Bha | as BS rev, +13.6Z7eV. =-34Z eV. +136 Zev. = 10.2 2? eV. = 102 x Z2 x 10-93 = 1632 x 10-1923 A EXAMPLE 5. SOLUTION. Equating equation (2) and (3), we get 1632 x 10°17 225 = 6.626 x 10-8 J 6.626 x 1078 3 1632x109 5 = Z =V4=2 ‘The element with atomic number 2 is helium. What transition in the hydrogen spectrum would have the same wavelength as the Blamer transition, n = 4 to n= 2 of He* spectrum ? (Rydberg constant = 109677 cm", Z.for He = 2) We know that for any atom : daze, (4-4 A ny on} (@) For helium atom, Z = 2. For the given transition, my = 2, my = 4, Substituting the values in relation (1), we get 4 k 182 x10” kg ms“ | EXAMPLE 13. Calculate the de-Broglie wave length of electron of mass 9.11 x 10"! kg and velocity | 3 x 108 ms Given h = 6.63 x 10 Js). | SOLUTION. — Mass of electron, m= 9.11 x 103) kg Velocity, v=3 x 10®ms!; h=6.63 x 10% Js f ty k Applying the relation, 2 = | im } 6.63 x 10 kg ms Z | oH 9.11 x 107! kg 3. 10% ms? = 0.2426 x 107" m E = 0.2426 x 107 x 10" = 0,02426 A Problem 1. Calculate the wavelength of an electron travelling at one third of the speed of light. (Ans. 7.27 x 10-2 m] Problem 2. Calculate the kinetic energy of an oxygen molecule which has a wavelength of 2.5 pm. [Ans. 6.58 x 10-9 J] Problem 3. A tennis ball of mass 6.02 x 107 kg is moving with a speed of 62 ms~!. Calculate the wavelength associated with this moving tennis ball. Will the movement of this ball exhibit the wave character ? Explain. [Ans. 1.78 x 10 m, No because the wavelength is very small] Problem 4. Calculate the wavelength of a-particles which are associated with an energy 10 MeV (1 MeV = 1.602 x 10° erg, h = 6.62 10-7 erg sec). [Ans. 4.54 10-5 m] Problem 5. What must be the velocity of a beam of electrons if they are to display a de-Broglie wavelength of 100 A, (mass of electron = 9.1 X 10! kg, = 6.6 x 10-34 Js). [Ans. 7.25 x 104 ms-!] ‘et _— —_ ‘V [ATOMIC STRUCTURE a HEISENBERG’S UNCERTAINTY PRINCIPLE One of the most important consequences of dual nature of an electron is the uncertainty principle deyploped by Wemer Heisenberg, According to uncertainty principle. “Itis impossible to measure simultaneously both the posi e ion and velo ‘or momentum) of a microscopic particle with absolute accuracy or certainty, oe Mathematically, according to this principle “The product of uncertainty in position (Ax) and uncertainty in momentum (Ap) of a microscopic particle is constant. The value of constant was later on found to be | Thus Heisenberg’s uncertainty principle may be expressed as : a A Ax.Ap> iP an or where Av is uncertainty in velocity. Aumdy = hid The constancy of the product of uncertainties means that two are inversely proportional to each other. ‘Thus, if the position of an electron is known with certainty, its momentum cannot be known with certainty and vice-versa. Physical concept of uncertainty principle. To understand this concept, one should study the effect of light on material objects. Exact position of an object can be determined i will be visible only if the light reflected by it falls inthe visible region, In order to observe an object, the wave length of light should be smaller than its size. If we use light radiations of higher wave length, these are not visible and exact position cannot be determined. When a beam of ordinary light falls on an object of reasonable size (Macto-semi-micro), it willbe visible with the naked eye. Its position or momentum (or velocity) will not change by the impact of light used. Thus, itis possible to know both the position and velocity of marco and semi micro object exactly. The situation is quite different in the case of microscopic objects like electrons. These objects. | !NCIDENT PHOTON. are not visible if ordinary light is used. Therefore, light radiations of short wavelength (high energy) are to be used. When such a photon of radiation strikes an electron, it transfers some of its energy to the electron. AS a result, velocity and momentum of the electron changes and it adopts a new path (Fig. 1.7). On the other hand if we use photons of radiation having longer wave length (low energy), the electron is not disturbed and hence will not be The Chane he GRINS visible, Thus the position of the electron cannot be known | ‘electron by the impact of incident with certainty. The velocity and momentum of the electron photon, will, however, not change appreciably and hence these can be known with certainty. Hence we cannot determine simultaneously both the position and momentum (or velocity) of a moving microscopic object like electron. It is important to note that the uncertainty is not due to lack of better technique for measurement of position and momentum. It is due to the fact that we cannot observe microscopic objects without disturbing them. s visible. An object MICROSCOPE [20 5 ERN COLLEGE CHEMISTRY SEM. I GE-T (THEOA Y)) Significance of Uncertainty Principle |. This principle has no significance for macroscopic objects I is because the product of uncertainty in position (Ax) and uncertainty in velocity (Av) for such objects is so small that it can be ignored. The Principle is not useful in daily life (and hence neglected in daily life) because the photons of light do not bring major changes in the position and momentum of massive objects, ¢.g., Ax X Av value for iron ball (m = 100) when found from the relation, Ax Av rod comes out to be = 5,25 x 107 cm? sec~, tm Which is very small and hence can be neglected. GO The principle cannot be neglected in case of microscopic particles. It is because, the product of ecctainty in position (Ax) and uncertainty in velocity (An) for such particles is appreciable and cannot be ignored. Thus, this principle is applicable to moving microscopic particles, ie., particles which cannot be seen with naked eye, e.g., Av X Av value for an electron (m= 9.1 x 10-2 gm) when calculated from Ax x Ay = piace gs oa it Principle is applicable to moving microscopic panicles which cannot be seen with naked eye. 2. Ithas introduced the idea. of probability of finding an electron in a particular position or in a particular volume of space. Uncertainty principle and idea of probability: According to Heisenberg’s uncertainty principle, itis not possible to know the exact position and path ofan electron. Bohs idea of definite energy (or velocity) ofan electron in a definite orbit has been hit hard by the principle of uncertainty. As we cannot observe the actual position of an electron, we cannot describe its path as done by Bohr. Bohr’s theory is, therefore, in direct clash with uncertainty principle. It now seems almost impossible to describe the exact position of an ¢lectron in an atom at any moment. The best we can do is to speak of the probability or relative chances of finding an electron with a probable velocity rather than a definite path for it. Thus, the electron levels in an atom can be imagined in terms of regions around the nucleus where the probability of finding the electrons ishigh (90-95%). Thus, Heisenberg’s uncertainty principle leads tothe idea of probability. Hence, uncertainty Principle has made the fundamental changes in the concept of atoms. is = 0.575 cm? sec”. It is appreciable value and hence cannot be ignored. Thus, this ppt Keeping in view the wave and particle nature of eletrons, a new model called wave mechanical model was developed by Erwin Schrodinger (1927). He considered the electron as three dimensional wave in clectric field of the positively charged nucleus. To describe the behaviour of electron waves, Schrodinger developed a mathematical equation called Schrodinger wave equation. The solutions of this equation are called orbital wave functions and are denoted by the symbol y (read y as psi). It represents the amplitude of an electron wave and y* represents the probability of finding an electron in a given region of space around the nucleus. Electrons cannot exist within the atomic nucleus: Proof. We know that the radius of an atom is about 10-4 m. For an electron to remain within the nucleus, Ax (uncertainty in the position of electron) must be 10-4 m. Knowing the value of Ax and using the uncertainty principle (4x-may = 4) the i magnitude of Av can be calculated h Ama Ax Thus av2 6.6 x 10 kgm? 57 Meenas ation: 4 x 3.142 x 9.108 x 107! kg x 107 m 25.77 X10 ms This value of Av (= 5.77 x 10° m 5-) is greater than that of velocity of light (= 3 x 10m s-), which is not possible. So, an electron cannot exist within nucleus. EXAMPLE 14. SOLUTION. EXAMPLE 15. ‘ SOLUTION. | EXAMPLE 16. | SOLUTION. What will be the minimum uncertainty in the position of electron, when the uncertainty in the momentum is 1 x 104 gm cm sec ? (Planck's constant is 6.6 x 10-27 erg sec). Uncertainty in momentum (Sp) =1 x 104 gm cm sec h=66 X 1077 erg sec = 6.6 X 10-27 gm cm? sec~ According to uncertainty principle. ok Ax Ap =e dr =f 66% 107 gon se" pane ge 4mAp 4x 3.142 x 10+ gmcmsec™ Find the uncertainty in the velocity of a bullet having mass equal to 25 grams and whose position at time (t) is known to be + 1.0 x 10 cm. (h = 6.62 x 1077 erg sec) (@ Mass (m) of the bullet = 25 grams (ii) Uncertainty in the velocity of the bullet = Av =? (ii) Uncertainty in the position of the bullet = Av= 0 x 102m But Ac x mAy = aa oh © 4am Ax _ 6.626 x 10? gm cm? sec~ . sec © 4x 3,142 x 25 gm x 10x 10 em (S.I. Units). If the velocity of an electron in the first orbit of hydrogen atom is 106 ms- and electron is located in the orbit within 0.1 A, what will be the uncertainty in its velocity ? Comment on your result also. (h = 6.626 x10-¥ Js, mass of electron = 9.1 x 107! kg). According to Heisenberg’s uncertainty principle, AxmAy =i or Av= cy i) Substituting the value of Ax (= 0.1 A or 10-1! m), m and h in (i), we get = 6.626 x 10 Js © 4X3,1416 x 9.1.x 107! kg x 107 mm 6.626 x 1074 kg m2s?.5 © 4X 3.1416 x 9.1 x 107! kg x 107M mt = 5.19 x 108 ms. Av = 21 x 1077 om sec. Av Ge Dakg m? s?] inp may, ishi pan was SU MODERN COLLEGE CHEMISTRY sey, ¢ oe, g Pet vm 1 ame { pitend roy) Ahowr dhata inchicates that uncertainty in Vel (5.79 X 108 mye Vie it poenn tenedty (208 ms} The etatement appears imelevant, Wis bey resem of the Electr ie specified with sufficient accuracy. it ig eaning Nhe eae hn $1 Vines) A weevden hall weizhing 100g ie tobe hecated within 0,1 Ae suncerieiny in ts welts Comment on your recall. (h = 6.626, x, ion eg my Using uncertainty principle b mar = a Wetwe ar = Ar= O01 A=01 X10 m= 10-1 aay mele ery =O Ag Sabstmnning the value of Ax, mand h in (2, we get 6626 x10" he mise ©3116 10 ag x 10 my = 827 X 103 mg The show value of uncer in vehi is so small that it is negligible, Sie macroscopic hades can te known accurtely. Since, uncertainty j fall (= 0.1 A) as also known to a reasonable degree of precision, the *slocity of a macroscopic body can be known accurately and simulta ‘The unceraumty in the position of a moving bullet of mass 10 em is 10-5 the uncerainty in the velocity. SOLUTION. = We inow thu, av ™ So, velocity Position of Position and ously, ™m. Caleulate 1] h eet | i (Anam (0) = or () * Sm (x) | 4 ‘Substituting the values, ay = 0626 * 10™ kg m? secu! | 5 7 i 28 mel 4% 3.142% 17 kg x 105m = 527 10° mst Ab e-particle (mass = 6.6 x 10° pm) bas kinetic energy 8 x 10 ° erg. Find the Wavelength of this particle. th = 6.62 x 10-27 erg. sec ) (1) Mass (m) of the panicle = 66 x 104 gm. 1 (KE of a-panicle = 5m? of Rx K. | ao | = [2%8x 105 Gong 7492 X 10 cm sec fe KEE = 8 x 10° erg or gm erie ATOMIC STRUCTURE aT? eee mT a EXAMPLE 20. SOLUTION. EXAMPLE 21. SOLUTION. EXAMPLE 22, SOLUTION. (ii) According to de-Broglie equation gm * 492 10% cm see! OF X10 em = 2.03 x 10-9 A Cateulate the product of uncertainties in position and velocity for an electron of mass OLX 10" kum, according to Heisenberg uncertainty principle (h= 66 x 10 ke m? sty, According to Heisenbere's uncertimy principle, (Ax) (Ay = or (Ax) m (Av) = AS mis constant. (Aw (Av) = tam Here m= 9.1 x 10°" kem 5h = 6.6 10-4 kg me? st 6.6.x" (Ax) (Av) = SS : 4x90 10 kg x 314 Ge = 3.14) 6.6 x 10 (Ax) (Av) = axel or (Ax) (Av) = 5.77 x 10% Hence, product of uncertainties in position and velocity of an electron is equal to or greater than 5.77 x 103) m? sl, - s {f 2.0 gm of a body is travelling along the x-axis at 100 cm s* within 1 cm sec"! What is the theoretical uncertainty in its position ? We know that (Ax. m (av) = 35 or AD) = nae As the uncertainty is within 1 cm sec7!, velocity varies between 99 em sec! to 100 cm seen! Av = 100 - 99 = | cm sec Substituting the values, 0.01 ms“. 26 x 1074 kg m’ 4x 3.142 x 0.01 ms“! x 2 x 107 Ac kg 26.36 x 107 = 2.636 x 10 m ‘The uncertainty in the position of a moving bullet of mass 10 gmis 10-5 m. Calculate the uncertainty in the velocity. We know that A (Ax). m (Av) = 4 or (AW) = Gm (aH) ‘Setllaeagy le bere, % es = Re eae | - RIP OH eet See ge ee EIB atone ths aehen warseenamtn oF deinen amd tea oan PONE ent ROE eR eT eH pee ey a Oh eke HR et 8) SAD bee Ty neering te leeeettenyy wmecetnaiten tree, > a tom tee ot rte ammtetsiitioe oi Biatiiasre wl relies ate! tera a oF ee 8FT 8 tee tit He Tee BE eR ay & seems © emirate etl Me mat of Kathe Sagppeva its wohwity can be RES ww BNCAHNON: Vt 9 TE ae eRe He We emeRAKOEY in peition * Wes haw we n{ 2 Vie), testo am) an ae Blew a pres = ral + AS ay Aang Go Hamme 5 umooTineNS yen, # Sam Bz ia afk == joe ed land a RAs x 1 Jy TB aU ag sagt ea 2B & Hire (Brebiem 6 6s cieane tas i speed sf 40 ne” accune gO IRS What is dhe uncertamey in Ahan te justia Hews ol eco =H) 8 air apy (tas, 145 «Lr nf Prose ¢ Fak macenses Haeerig Ihe spot it an euccieneied ciesmem is § 2 AUP saw! Rie setae te Saad fis aca whale Cas still ay mio, mm, 92 17 mp Using maton capemesie. te te uoRaNS ARTE Hine Abel the Hltanwan a Powis ais aaracim sa fancies abctute acer mo Hex proses % Calsaais Re amor the aeiucsly «jamie of aes 1 4 1! hy of the ee ed Wom, 672 x 1 naw *) MO Tx peat a erm mong 26 BO as co te acsanacy of (ASE m . ‘i thm, 193 x 195 mj come +00 aE | QUANTUM MECHANTES nie the (oemnelation oF quintany mectinies (oe the aan coate open a Roe poatitnter Some oF sivon (ooh fe imechanienl tremtmedt of he otrerstnres cof gtenee Uren For a avetorty moving ier ome imenaion (airy ¢ commeitenteny att Poatirtates: 1 (re hysient atnte of « eynterm at tin H4 described: by ihe wave finetion (4, 17 5. The wave Aimetion yp (x 0 anit ite fest and second derivatives OM Ce, Be ond ip Ce fe ape sontinnaouns (nite: vnc aingte: vated foe alt vnluee of © Also the raves Jule epee. nats Of Fimetion (4. 118 nbneniliaedd where yr" is the complex conjugate of yp formed by replacing ¢ with J whereowee it occins i the Fanon v@e Li \ The physically observable quantity con be represonted by Heemitian operator. An operator A ia eae to be Honmitian (Fit satistios the following conditions, [vlAp def where yy aml yp) are the wave fine particle, an lor oF a motocute 4. The allowe (Apr tde He Foproxenting the physical states of the quantury aysieur be. 1 vales of an observable A ate the cigew values, dj im the operator equation, \y “dane I known as eigen value equation. Here Ais the operator for the observable: physical quantity and yp bran eigen function of A with eigon value aj. In other words, measurement of the observable A yoke the yen value a, SCHRODINGER WAVE EQUATION (WAVE MECHANICAL MODEL OF ATOM)’ Jotirodingor (1926) made axe of the idcas at de-Broglic, Henvenberg’s uncertatary rine pte and Pote’'s Fixed orhity and developed «mathematical dittercntial equation, calledt Sutodingee uve equation. Che volute ol Miss wave oq Wis the cleciron ditiubution in pace. ae yell as he allowed cneagy levels ot 4 paarticte wilield. Keeping a view, the particte valige ot an cles tron, (otlowing fiunsival w/ve-cqation describing the wave moti ot a particle along the sexes can Die gpplicat io Hon) nvuviingy any yes Acne (otal waves eqquationy wt y= wave Tune, A= anaxinun value of ye As waves le (Hh of stanly waves (uct as vubrattng stein Feat AC te crue) avelling along vents andl 4 Ditanes of particle trom the auclets Difcnewnaniye y wal 0 (HEEL WW 6, We et dy de Difereaniasiny, aya, we wot 2 = Avy do | | +} 1 ; cox tn * ay ! A dae Wad ne de > fecdiaciseRecrsescces ‘This equation represents wave motion of any particle along x-axi as putticle character, the above equation also represents the wave motion mn of electron along x- If the electron is considered to move along x, y and z-axis, then ay dy dy. axty an? ay dy dy a a att art ge Too viy + teo jince electron has a wave as well (i) a a a where 77 rd ee ae (The Laplacian operator) 4xty 2 ead 4x? Vee or ae oid : ; h ‘According to de Broglie 4 = —— mv Squaring both sides, we get A a From equations (ii) and (iii), we get = Ey avi Wo vy =- apm FS eee oe So far we have assumed that the electron is present in a field free space. Thus its potential energy (PE,)is considered constant. But for most of the systems, such as an electron moving in afield of a positive nucleus, the P.E. can also vary. Thus, the total energy (E) of a system is equal to the sum total of potential energy (P.E.) and kinetic energy (KE.) E=KE.+PE;KE=E-PE Substituting the value of K.E. from (v) in (iv), we get 82m 2) Vip +22" E-PE)y=0 Avi) soe) 0 | [V = potential energy] This is known as the Schrodinger wave equation. Schrodinger wave equation for hydrogen atom: Consider that hydrogen atom has nuclear charge 2 and charge on the electron is ~e. Potential energy of the electron V =~ ¢%/r. Thus, the Schrodinger wave equation takes the following om. 82m : vps (e : Je “6 -a(vii) ay ay dy &x2m 7 Zz rey + ry + oe E+ | =0 [For H-atom, Z = 1]. ...(viii) It is the Schrodinger wave equation for hydrogen atom. Significance of Schrodinger wave equation 1. Eigen values and eigen functions. Schrodinger wave equation is a second order differential 2quation. So, it has many solutions for. Many of them are imaginary and have no significance. Only those values of yp will be significant which satisfy the following conditions: (® The wave function must be finite and continuous. (ii) The solution must be single valued i.e., at a given point, there can never be more than one value for the amplitude, yp. ay Gi) “Gedy a4 # must be continuous function of x, y and z respectively. (iv) The probability of finding an electron (around nucleus) over all the space from plus infinity to minus infinity must be equal to one. Thus, Where 1? represents the probability of finding an electron at a point x, y and z. Several wave functions, V2..which satisfy the above conditions have significant values and are called eigen functions. These significant values (called eigen values) are obtained by substituting proper values of total energy E in the wave equation, Each of the above wave functions has corresponding energy E), Ey... and is called an orbital. However, it differs from Bohr’s theory. According to Bohr, the circular orbits of the electron are Planar. According to Schrodinger wave equation, electrons move around the nucleus in three dimensional space (X, Y and Z~ axis). For an atom, these Eigen values correspond to discrete sets of energy values postulated by Bohr. Thus, we find that the concept of wave mechanics leads to the presence of definite energy levels in an atom. 2. Energy of an electron in hydrogen atom. In case of hydrogen atom, a single electron (charge, ~ e) moves around the nucleus (charge, + e). Thus, -@ Potential energy, PE. of the electron = —“— saéx) r MODERN COLLEGE CHEMISTRY SEI Substituting P.E. = — from equation (x) in equation (vi), we get 2, 2 2, Sa?m(_ Vip t ra (= Len Je =0 (viii) This is a Schrodinger equation for the hydrogen atom. This equation when solved, gives, ze 2x*me* wr? where E, = energy of the electron in the nth level in hydrogen atom. For H-atom, this energy is 13.6 eV or 1312 WJ. The above equation is identical with Bohr’s equation (derived from classical mechanics) for H-atom, The values calculated by classical as well as wave mechanics agree with experimental values. For atoms other than hydrogen, wave mechanical treatment is found to be better. 3. Ithas developed quantum numbers. When Schrodinger wave equation is solved for energy calculations, three constants (n, | and m) are involved. These three constants must signify three quantum numbers (n, 1 and m) of an electron. The solution also shows that these constants are related to one another as follows : (@ The values of ‘n’ must be integral while ‘I’ may have integral values, Oton-1. (ii) 'sn-1. (iii) The values of n +1 and 21 + 1 are both whole numbers i.c., integral. (iv) Values of m vary from —1 to +1. ‘The above relations (derived from wave equation) are exactly the same as derived from. spectroscopic measurements. 4, It helps to calculate the probability of finding an electron around nucleus in different energy states. Limitation of Schrodinger wave equation. This equation can be solved exactly for one electron systems like hydrogen atom, hydrogen like atoms (He*, Li? etc.) only. Significance of y @ It is a wave function which is solution to the Schrodinger wave equation. Gi) Itrepresents amplitude of wave and describes how this amplitude varies with distance and direction. ii) ‘The Schrodinger wave equation may have different values of y. All values may not be significant The significant values of wave functions, y are known as EIGEN functions. These functions give significant values of total energy (E) of the electron. These values are called Bigen values. Significance of y? i.e., square of amplitude (i) For light waves, it represents intensity of light. (ii) Forelectron waves, it represents intensity of electrons at any point, ie., itrepresents the probability of finding electron (of specific energy) at different regions in space. (iii) It Jeads to the idea of orbital. is more significant than y. Wave function i represents an orbital. It depends on the coordinates of the particle. In certain cases, W may tum out to be a complex function of the form, y = a + ib where i=(- 1)" and a and b are the real functions of coordinates. In such a situation, complex conjugate of is ¥* where y* = a — ib and yp* = (a + b) (a - ib) = a? = at [CP = at + Be [ATOMIC STRUCTURE) Sa eee 29 ~| Neither v nor y* has any physical significance but y* (writen also as) bas physical significance and is identical with ¥? when ip is tel. Thus to deal with ll waves (ike light, sound, matter or electrical et) the square of amplitude (1p*) at any point is interpretted as intensities of that wave or effect at that point. Since exact position of a wave or particle can not be known accurately (Heisenberg's uncertainty principle) at a point, we say that there is probability of finding that wave or particle at that point. It should be remeemered that y* (but not yp) must be associated with probability density. It is because when wave equation is solved, there are some regions in which y is positive and in some other regions 7 is negative. But probability can never be negative. It must be positive or zero. Hence * is more significant than yp. VY Radial and Angular paths of hydwrogenic wave function and their variation for 2s, 2p, 3s, 3p and 3d orbital The following Schrodinger wave equation for H-atom @y dy dy 82m 2 a ee El wae ae a ET TP nO can be solved by substituting the polar co-ordinates (r, @ and @) in place of cartesian coordinates (x, y and z). The co-relation between these two types of co-ordinates is illustrated in the adjoining figure 1.8. Radial line The method to convert cartesian co-ordinates into polar co-ordinates is explained below : Take a point A having co-ordinates x, y and z in space. Let OA = r and let 6 and @ be the angles as shown in the figure 1.8. Then, 2=ON=rcos @ and OL= AN=rsin 6 y = OM =LK = OL sin @ =r sin @ sing Projection of racal ine x= OK = OL cos $= rsin 0 cos @ Fig. 1.8 Co-relation ‘Thus, equation (1) can be written in terms of polar co-ordinates as between polar co- follows : ordinates (1, 6, @) and cartesian (x, ¥, 2)- 1 aap) | 1 [sind ap (7.8.9) rar ar r sin@ 00 a0 sind ag? In the above equation (2), we have written wy (r, 8, @) instead of w (x, y, 2) because y will now be a function of variable r, @ and . In order to evaluate yp (r, 6, ), the y function is written as follows: wlr, 8, 9) =R (7) © @) ® @) @) where R (7) isa function that depends upon the distance, r from the nucleus, which in turn depends upon the quantum numbers n and ! but independent of polar coordinates 6 and © (@) isa function of 6, which depends upon quantum numbers J and m but independent of polar coordinates rand 8 © (@) is a function of 8, which depends only on quantum number m but independent of polar coordinates r and 6. 1 #p(r.6,¢) 2 2m \vt-0.9=0 w@) _MODERN COLLEGE CHEMISTRY SEM. I GE-I (THEORY)! : 7 Si ] ‘Bguation (3) can be rewritten as follows : VER ihe Am This splits the wave functions into two parts which can be solved separately. 1 The fimetion R (r) is known as radial wave function which depends upon the quantum number, mand [ 2. The function Any [ie @ (@) . © (9)] in known as total angular wave function which depends upon the quantum numbers m and /. When we express y' (r, 8, 0) and R (r) © (4) (@). a complicated equation is obtained which can be split into following three equations. af sR] @ Stim ( S| Gl aR E+—|Rin=0 fA) This equation is a function of r only and when solved gives R (r). oa 770 (8) 6——— |- —— +e) = ol 8 sintg *FO)=0 oy This equation is a function of @ only and when solved gives © (6). (iii) ee) + nP(G) =0 (6) ag) ‘This equation is a function of @ only and when solved gives « (6). The total wave function is then written as given in equation (3). The angular part of wave function is 2 product of © (@) and ¢» (@) and gives the shape of the orbital, The radial part of wave function R(r) gives the energy and size of orbitals. Let us discuss these in detzils. 1. The Radial wave fanction (R(r)] or y(r). When equation (4) is solved for hydrogen and hydrogen like systems, two quantum numbers n and I are obtained. The quantum number ‘n’ is analogous to principal quantum number of Bohr theory end can have integral values 1, 2, 3 etc, The quantum number ‘Tis analogous to azimuthal quantum number of Bohr-Sommerfeld theory and can have integral values from Oto n~ 1, When J = 0, 1, 2 and 3, the orbitals are designated as s, p, d and f respectively. Thus the radial wave function is usually writen as Ry, (r) or Ra, 1 ‘The radial wave functions, R,, ; (r) for electrons in s and p states (orbitals) are described below : 32 El] “ aq [Represents radial wave function of electron in Is-orbital (n Rio or Ris 1 = 0 and o = Zr/nag)] 2" Ro, 9 or Ra, = 273? (2) Q-o)e%? a0 {Represents radial wave function of electron in 2s-orbital (n = 2, 1 = 0)]. zy Ro, 1 OF Roy 22-2602 (Z) gan 4% [Represents radial wave function of electron in p-orbital (n = 2, ! = 1)] | ATOMIC STRUCTURE Here, ag is Bohr's radius, Z is the ‘The radial dependence of an orbit (ie. ) and distance (r) from nu al can be expressed by plotting a graph between wave function Rr, 1 s for electrons belonging to different orbitals (fig. 1.9) The graph helps a distance ‘r’ from the nucleus. Graph between Rn, 1 (r) and (r) for electrons belonging to different orbitals. Graphs indicate that R,, ; cannot be related with probability density around any point at a distance r from the nucleus. It is due to following reasons. (i) Rp,zi8 maximum at r= 0. IER, represents the probability density, then the maximum probability of finding electron is maximum at nucleus, But it is not true because the actual probability of finding electron at the nucleus is zero. (ii) Inthe probability curves for 2s and 3s orbitals, R,, ; has both positive and negative values. But the probability density can never have negative value. The objection shown at number (ii) above can be removed to some extent by considering that ‘the probability density is related to R2,, (i. €. 2) instead of Ry, : (pn In this consideration, if Ry, is negative at some space, the square of negative will become positive. This situation is obvious when a plot is drawn between R2,, and r for electrons belonging to different orbitals (Fig. 1.10). Fig. 1.10 Graph between R,,? and r for electrons belonging to different orbitals. In these curves, the radial wave functions do not have any negative value at any distance. But, still R2,, cannot be related with the probability density because R?,, ; is again maximum at r= 0. It again shows that the probability of finding electron is maximum on the nucleus which is wrong. Thus, “neither R,,, nor R2,,; can be directly related with the probability of finding an electron at a point distance ‘r’ from the nucleus.” In order to remove above objection completely, radial probability distribution curves are helpful as described below. tiene He orn oe ie nena Ge ae etme hee flr genes nee ARS ests Moses ee en Panties oF erent Aelte Heettmen a T ee He tee OO tm siete Gee ame be oe eames hae a Nth of ath wath refi Ga & Nitta 90 eat wet saine ccs ome + se San preedbitis w Riitin: te theron, ten wel: eee remmnn ethowe of! renffl + and ee ee i SE Me A i SHRUT Patent gates af mith > ame ya le Nala: Peete Hei se, Hee wsesitene we. Tetons, * # 4 ® st ae eee ie = ne cae e eae e a? y 4 ‘ ; oT tees ce dtr Seam | = ie dem hae je set) 9 woe erp Seecmwe Ue cx very semall) ‘Tie, Re edhe pretattisy aRateteatins Aursre flo presetisllies Ee ee eis es i a otis VO ae ath he geeematitees Grmetts pe) Tor [5 eT! as yihotiad! wpains’ Anns 5 Kee Me items we BES SEETWE oo Strwwens WH TiguTe 1S een Be fypors 9 Sica das Oo MEAN be CIN Wa Te we did pore omy Secrets wl. Aersames Ths antist! tnee a Me Tipu ace eon Wieck, sain at is aie & Pate agains vatine dota on te made Ths vale of deel! gem o6 inmasing WATT Mea Be Bonsai ‘Ves goradiags af preahifiny density anti waturne sf shall gover veaname of she (V) versus ‘ie tae Desi sol serve catzunlatow, tae rachis) promt dustin cher [5 sieatron. ja lle: pocainily of Haag ctv teen 3 = 0 aud # = ¢ wall given ny the: aamamaa ta ae orotate chucritatens Yo OoceRE ca ste hy reOrar be Aer BE ya wituct a» equal wn axe R?, wher 5c uhsumer cf cinimus champs fram the Msiious, Pros the ata prahamis darian of clam, can be otienned ty Arawing 8 graph heewece the fuponen aur B-, , awl ¢ buck prapte as culled ruta) Auaciinainn curves or cabiad probability Giawtbotion carves ot ratiial carps Gematty cares, Thsoe wes conippiowly droite de vanation of Probability density af eect ee [arorre graven Vine radial prsdteateliny Harriton couevs Hep election wresont ane Ly an ys Canteigts aves showers a Bag EE tie cadtal ppeeebal tied AR is tlhe prenditet of ee Thtors fore’ and RO He this ftetiony (Ga) the Hietor Hee! increases a8 taereages ated (i) the fact RY dberensee as increases fhe omves obtained it Hig 182 a8 recannses oF those fave Helos (ed At ro Bc althongt the fietor RE ec mnaeinntnn (see Hig 113) yet hve factor oer is cere, Fits, che foalial probally Zoro aL yO, Le, metens, Similarly, (i) When 6 is very tnege, although the factor dar? is very large, yet the probability Metor Ri rogliyibly small Pins, tho racial prosbability is oxecedtinggly srnall when 1-18 very large: Those curves can he drawn by romemboring that (i) thes number of radial nodes in the curves is equal ion 2 E NODE. NODE Gb the curves start from origin UH) the area under the particular curve Frome felt to enght such that at nev naxtanunn ander the last velope of a (968 (oN INL FEASADN, envelupe The peak of the last oueye. given this distance from the auclews where the Probability of Hadiye election go masinn, Thin dintance ty called the cadtien af maaimum probability ti case of hydrogen atom when is clecicon ta pte (he, grommd otatey, nucleus where the probablity ab tadiog lection by magnon i W229 AC ED io tan: tn sari ay Hrokee"y salt ban fy hate Huatanes rome the [3a] TO wopern con From figure 1.15, itis clear that (a) 2s-orbital has two regions of high probability separated by a node (space where the probability of finding the electron is zero). The probability first rises to maximum and then falls steeply to zero. 1 again rises and then falls to minimum, So, there is one node between two maxima (high probability region). (b) 3s-orbital has three maxima (regions of high probability) and two nodes. 4s-orbital will similarly have four regions of high probability and three nodes. (©) In 2p-orbital, there is rapid increase in probability with increase in distance (from nucleus) till Tegion of high probability is reached. After this, there is gradual decrease with increase in distance, (@) 3p-orbital has two regions of high probability separated by one node. 4p-orbital will similarly have three regions of high probability separated by two nodes. (e) In 3c-orbital, there is rapid increase in probability with increase in distance (from nucleus) till tegion of high probability is reached. After this there is gradual decrease with increase in distance, 4¢-orbital will have two regions of maximum probability and one node. Radial probability distribution curves for s, p and d orbitals. Such curves for 3s, 3p and 3d have already been shown in figure 1.34. These curves are now drawn collectively in the same graph for comparison. From the graph, it is clear that : (H the radius of maximum probability for 3s electron is greater than 3p which in turn is greater than 3d electron. Thus, the order of radii of maximum probability is : 3s>3p>3d (ii) there is a small peak in the distribution curve for 3s electron. This peak is closer to the nucleus than a similar peak present in 3p electron curve. This shows that the probability of occurrence of 3s electron near the nucleus is more than that of 3p electron which in turn is more than that of 3a electron. Thus, 35 electron penetrates more towards the nucleus than 3p electron which in tum penetrates more than 3d electron. Hence the probability of occurrence of an electron nearest the nucleus is in the order 3s > 3p > 3d. Let us study the 35 electron curve again. The curve shows two minima. This indicates that the spherical 3s orbital consists of two spherical shells within it at certain radial distance where the probability of finding electron is almost zero. Such radial spaces are called radial nodes or radial nodal planes, These radial nodes in an orbital are equal ton —1— 1. For example : — (i the number of radial nodes in 3s orbital (n = 2, 1 = 0) = 3-0 — (ii) the number of radial nodes in 3p orbital (n = 3, (iii) the number of radial nodes in 3d orbital (n = 3, 1= 2) = 3-2-1 = zero Il, The angular wave function, © (6) ® (4). When equations (5) and (6) are solved, another quantum number called magnetic quantum number m is obtained. The maximum value of m can be + ‘Thus, m can have values from — I to 0 to + only. This restriction on the values of ‘m’ is the same as that found necessary for magnetic quantum number in the theory proposed by Bohr-Sommerfeld. ‘Thus wave function © (6) is written as Of, m(0) or O(l, m). Also, the wave function (9) is written as © m ) or & m. The product of wave functions ©!, m and gm is called angular wave function. So, angular wave function = © [, m dm ‘The complete wave function y (r, 8, @) is equal to the product of radial wave function and angular wave function. Thus w(r, 0, $) = Rn, © I, m @ m CHEMISTRY SEM, I GE-I (THEORY) | [atomc sTaucTURE) Angular wave functions ( (eo Myr m ®, mn) and shapes of orbitals In case of hydrogen atom, the wave function © 1, m and & m are given below : OLm 1,0 = [Reese Be = eos +i sing) Oj21 = Pano z weenie ®.0 - fe cos? 6-1) 2 —erg Faag (08 2h4i sin 29) Opt = [Excnecae O eh wi sin 2p) Ox22 = [Ex cin? Shapes of s, p and d-orbitals © Shape of s-orbitals. For an s-orbital, / = 0 and m = 0. The corresponding wave function can be written as = Inthe above relation, the angular wave function, @p, Pp value = oe is independent of 8 and . So s-orbital is symmetrical over all the directions. wa Hence, s-orbital has spherical shape. 1s, 2s and 3s orbitals have zero, one and two radial nodes respectively (Fig. 1.16). RADIAL al NODES z Zz 2s ORBITAL, 3s ORBITAL 8.5 FE ee a As wie hubnmuhgumbenedummenidkanedl eka Se Keane 0 Het Tem ew ome We vinnie Ch Me shen bent, fe engain yee eae See Ae emai (i ak Bee pty to! meee Newtson pahatuh he woe eenicetoe aps wm Nae eapsomsunet to amptine Uh an ise Bene hep mc en Penson: Siem eemminctin tae asians: Tees gre ae a a ee am FE. Te ree ana Sk FatnomaRy sms ee mtn is bi al sess pees Daten = et ee mr dea Pi cmatit ( whnons ha eal angus Hae Tussin = hos Poe The eta 5 a 7 apo 6 to fal wae Tata as putt towing f= bend wets 4 a, Maas sycticase Se ase AtiWs Kis ahem af Jowett a ee Papin Ma wows faacieas we ech ot ariasiad Sorusttiy, we got ow We Mane: poms Totus wat: 1 ab onte Lat ay 1 Vans 1 iss eer thom fig 127) ‘Sie Hoe & fawcna, at ¢ Wie called 7 weer Maaco, Whee Ihe tien 5 Roto ws Dares deci! epax 4 sania: Aue! stapes cu oe shang 5 atts bs obtained (Bg 1.17) ait - arr st pusitsns ai Megating tea gse tel ars Erometrical sigan 7, wil We pantie ot tepative wich J pouting 18 Maigatine Aan ert rue AID Caeeiter (he real vite ivetten eter My anetitation cae ecseati Uegqerreatg ia wove eet Hort neon tcarEeHERAte, se got sees et reo ote Mamethie oie 1 “ig Mt Mowe “Vay ts att owed T | cwany Shines (ier finetion afc itiecatled ys, wave Hinerion When thie fimedon: ss, ce pshorted ie ieee tlinemetcnith apace y evmimeteical dunmbell tripod cites eon tee eats es obtained ote Fay 11ND. 4, WT he postive oi notte whens 1k nitive oe negative respectively, ALI) Clonaiclor the real waree Ranctions represonted by casniination (Dy ayuentioen (09), EPepReoU THE Maye Tanetion dr Lofns of cartesian comcndtinites, we got that angatin pewave fnetior viet is ' a 5 “Vig Ome 1 on : sin ain Stree aoe fincton of y (his called ps, wave fincton Whee shie wave: function,» os ptotied in hres dimensional space, «symmetrical limbo chapedt gtrvo tong he eves ee obtained ace Aig 119), will be positive oF negatives when yi positive oF aegative respectively Hi onder (0 got mere oxaet sbapen of prorditals, me lot wave Tinction must be coneutorod. Tho shape of Sp and 4p cabitishs alse duunibell hut the decreasing order of alze of Uves poorbitite ie wep The number of radial nodes lor %p, fp anid ip orbitiabi an scan ancl aver rospoctively, (Hy | 20 because the number of nudess bv equal a 1 1. ae Ape orbital Why ots aN stati (ho nace ws nt Difference between 2p and 3p Subshella co hetwecn 4p and 4p wutishell is iver follows For Zpaubsnal, ns 2 and 1s | For Npaupanel, = an ba ih otailar if aize than Ip-substeal, it 8 larger in stem han 2yrsnabanell, ‘has fo pedal plane 1 Tess caine mAh pais Mt Ras lass anergy Man Speaubsiall, - { Ne i MODERN COLLEGE CHEMISTRY SEM. I GE-I (THEORY)] | Shape of d-orbital | Fora d-orbital, ! = 2 and m= 0, 1, 2,~1,-2 (:m=-1t00t0+ p, ‘The corresponding angular wave functions are written as: GB.cos? 0-1) = 32? = x5 Since the above d-wave function varies as z+, so it is called dz function. wi Fy ret 41 +0,404)= | ie sin 8 cos 8 cos $ = 45 | Since the above d-wave function varies as xz, itis called d,, function. | iii Fine 1+ On1o 104) = 22 sin acos0 sing = ed | Sine the above d wave fanetion va Varies as yz, it is called d,, function. (iv) $ 242 P2 + O29 P2) = Tee sim? 8 cos 2p = J— 15 sin? (cos - sin??) 15, = x 16x 16r Since the above d-wave function varies as x2 — y?, itis called d,2_ yz function. «) iy (Oo, Py - Op By sin? 92 sing cos p JAS 1 Tag % y % Sind cos p sinO sing x2 = Since the above d-wave function varies as xy, itis called dy “Tanction, From above discussion we conclude that d-orbitals have five real angular wave functions viz dd dy» dy and d2_ yo. When these wave functions are plotted in three dimensional space, we get curves as shown in Fig. 1.21. All these curves are three dimensional because these are dependent on r which is equal pose 2, d.2-orbital. The curve of d.2-orbital is of dumbell shape and is symmetric about the z-axis. It has a | circular collar in xy-plane and has a negative geometric sign. The geometric sign of the dumbell shaped part } of the curve is positive because z may have any sign, its square z” will always have a positive sign. | 4,,-orbital. The curve d,-orbital is of double dumbell shape. The quantity xy will be negative when either x or y is negative, xy will be positive when both x and y are either positive or negative. As a result, the sign of curve will be positive in the first and third quadrants (fig. 121) while itis negative in the second and fourth quadrant. 39 d,, and d,,-Orbitals. The curve of these orbitals is also of double dumbell shape. The explanation is same as that described for d,-orbital, d,a_ 2 orbital. The curve of d2_ ,2-orbital is of double dumbell shape. Its lobes lie on x and y axis. ‘The signs of lobes on x-axis will always be positive. It is because x may have any sign, its square, > will always be positive. The signs of lobes on y-axis will always be negative. It is because y may have any sign, —¥ will always be negative, For getting exact shapes of d-orbitals, one is to take into consideration the total wave function, So, the shape of 3d,, will be same as that of 4d, of Sdzy- Similarly, the shape of 3d,. will be same as that of 4d,, and Sd... 3d-orbital differs from 4d and Sd-orbitals in following respects. (i) 3d-orbital does not have radial node but 4d and Sd-orbitals have one and two radial nodes respectively. (ii) The space occupied by 3d- orbital is less than 4d which in 4 for 3dya = yar 4dy2 — yz and Sdy2 ~ yo s rbitals in three dimensional ‘space turn occupies less space than that of Sd-orbital (Fig. 1.22). NOTE | 1. dy, dye, day and dz ,2 have clover leaf shape. 2. dz has baby soother or dough nut shape. QUANTUM NUMBERS AND THEIR IMPORTANCE When spectra of different atoms were studied by the use of high resolving equipment, following informations were obtained. These informations led to the extension of Bohr’s theory about atoms. (i) A large number of single spectral lines were found to contain a number of very closely related lines. (ii) When a source of spectral lines was placed in a magnetic (or electric) field, several single lines were found to split into component lines. It is due to Zeer: From the above fine structure of spectra, it was concluded that Stark) effect respectively. iere must be more possible energy changes within. the atom. These energy changes are only possible if there are a number of orbitals (other than Bohr’s orbits) in which an electron can reside in an atom, The confirmation of above facts was available from the solution of wave equation to hydrogen and other atoms. The solution of this wave equation yielded three quantum numbers, namely. (i) Principal quantum number (1). (ii) Azimuthal (or angular, orbital or subsidiary) quantum number (J) and (iii) Magnetic quantum number (m). (iv) Spin quantum number (s) which does not follow from wave mechanics and arises from the spectral evidence that “an electron moving around the nucleus also rotates (or spins) about its own axis.” ‘These quantum numbers are thus constants which are used to solve Schrodinger ‘wave equation and explain the orbital concept of atomic model, ie., size, shape, orientation and spin of the electron [40°F BNE MODERN COLLEGE CHEMISTRY SEM. 1 GE-T (THEORY) cloud. The term quantum number is helpful to identify the various energy levels availabl | word quantum signifies that all the energy levels (orbitals) available to an electron are of quantum mechanics. | | eto an electron, Ty, governed by the lag The significant aspects of the four quantum numbers is given below : 1, Principal Quantum number (n). This quantum number designated as ‘n’ gives the nu | ‘major energy level (shell or orbit) to which the electron belongs. It can have any positive whole value excluding zero ie., n= 1, 2,3,4, .. 00, imber of | number | ‘Thus 1 can have infinite value and it has been called principal quantum number by Bohr, | Informations given by principal quantum number. () The value of n represents the shells. which are | designated by capital letters K, L, M, Ny w Thus, | Value of n 1 2 3 4 | Letter to K-shell — L-shell M-shell N-shell | represent (First) (Second) (Third) (Fourth) (ii) This principal quantum number also helps to determine the average distance of the electron from the nucleus. In terms of quantum mechanics, it gives the effective volume of the electron cloud, In case of hhydrogen atom, the approximate distance from the nucleus is given by | 252 | 4 h | SS @=1 for Ht atom) 4x76? Lower value of ‘n’ represents that electron is nearer to the nucleus. Thus, n represents the size of the electron orbits. Higher the value of n, larger is the size of the electron orbit or atom. | (ii ‘n* also determines the energy of the electron in an orbit. For hydrogen like particles, itis given by : 2x?me§Z? 202? met “+ and n= — 75> in SL. system, wh nh? (deo) | Where Z is the atomic number, m and e are the mass and charge of the electron respectively, h is the Planck's constant and 1 is the number of the orbit. Eq is a constant called permittivity of medium. Its numerical value is 8.8542 x 10-!2C? N~! nr? and 47: eq is the permittivity factor and its value is 1.1126410- | Ey = 10 CENT pr? | Substituting the values of m, e, z, n and h, we get E,=— ee kJ mol! ” The above relation shows that largest negative value of energy ~1312 kJ mol! (ie. maximum stability) is obtained when » = 1. Thus = I gives the lowest energy state (E,) of an elecron in H-atom. This state is called the ground state or stationary state of an electron in an atom. From above, itis also clear that +1312 kJ mol! energy (called ionisation energy) is needed to knock out an electron from H-atom. For n = 2, = - 328 J mol! q This reduced negative value indicates that the atom is less stable as compared to the ground state. Similarly, all states with higher value of ‘n’ are also less stable, Alll states with 1 values greater than one are called excited states. When energy called excitation energy (which is equal to the energy difference between two states) is provided, an electron makes a transition from the ground state to one of the excited states. The difference (AE) in energy between the two states is given by AE = E,, ~ Ep, For a transition from ground state (1, = 1) to the first excited state (nz = 2) AE = Ep E, = [- 328 KJ mol"! - (1312 J mol-) = 984 kJ mol The various energy states in an atom are commonly called its energy levels. With the increase in the value of ‘n’, energy associated with an electron increases and the energy difference between two successive energy states goes on decreasing, When n value is infinity, the energy becomes zero. (iv) ‘n’ value can also be used to calculate the maximum number of electrons that a shell can hold. ‘Maximum number-of electrons in an orbit with quantum number » can_haye 2n? electrons. Thu: The maximum number of electrons in K-shell (n = 1) =2 x I2=2 ‘The maximum number of electrons in L-shell (n = 2) =2 x 22=8 ‘The maximum number of electrons in M-shell (n = 3) = 2 x 32=18 ‘The maximum number of electrons in N-shell (n =2 x 42=32, Physical significance. This quantum number describes the energy and position of an electron ina shell 2. Azimuthal, subsidiary, orbital or angular quantum number (2). When hydrogen spectrum was observed by means of a spectroscope of high resolving power, the individual spectral lines were found to consist of a group of closely spaced lines. Such a spectrum consisting of closely spaced spectral line is called fine structure. The fine structure of a spectral line is explained by assuming that all electrons of a shell do not have same energy and cach shell is composed of a number of subshells which are specified by a secondary quantum number, designated as ‘, The value of ‘’ depends upon the value of ‘n’. For a given value of n, /can have values from zero to (n-1) where 1 is the value of principal quantum number. Informations given by ! values (®. This quantum number determines the angular momentum of the electron. (ii) The values of | for a given value of n determine the number of subshells. For example, when n= | the largest (and only) value of! is zero. Therefore, K-shell consists of only one subshell. When n= 2, 1 = 0 and I. Hence, L-shell is made up of two subshells. For n = 3, 1 = 0, 1,2 therefore, M-shell consists of 3-subshells, (iii) Different values of ‘1’ represent different subshells which are designated by small letters s, p, d, fon For example, Value of | 0 L 2 Bae Designation of subshell 5 P a f For the same value of n, the energies of sub-levels are determined by the values of for them. A sub- level with a higher value of / is associated with higher energy. Thus, s < op < do| 1s | 2s | 2p | 3s | 3p | aa | as | ap | aa] at | ss | Sp n 1, ), 2F laa) Se) a lino | 4 Rae ae 4 les ales ! Of Oo] 4 ]-0.) 1 {2} oF} 4) 2 fos: [ofa n+l Tepe Ea sipastes | a] s | exfaz.c| sate 1n< 2s < 2p <3s<3p<4s<3d<4p <55<4d

    You might also like