BOHR’S ATOMIC MODEL © . Q. Whatare the main points of Bohr’s atomic model? With the-help of.Bohr’s atomic model, how would you determine the radius and energy ' of hydrogen atom? fe (R.U. 2008) - - Or : Q What is Bohr’s theory of atomic structure?- What are its (R.U. 2005) limitations? Ans. ‘In atomic physics, the Bohr model, devised by Niels Bohr, depicts the atom as a small, positively charged nucleus surrounded by electrons that travel in circular orbits around the nucleus—similar in structure to the solar system, but with electrostatic forces providing attraction, rather than gravity. This was an improvement on the earlier cubic model (1902), the plum-pudding model (1904), the Saturnian model (1904), and the Rutherford model (1911). Since the Bohr model is a quantum physics-based modification of the Rutherford model, many sources combine the two, referring to the Rutherford—Bohr model. . satoduced by Niels Bohr in 1913, the model’s key success lay in explaining the Rydberg formula for the spectral emission lines of atomic hydrogen. While the Rydberg formula had been known experimentally, it did not gain a theoretical underpinning until the Bohr model was introduced, Not only did the Bohr model explain the reason for the structure of the Rydbergformula, it also provided a justification for its empirical results in terms of fundamental physical constants. The Bohr model is a primitive model of the hydrogen atom. Asa theory, it can be derived as a first-order approximation of the hydrogen atom using the broader and much more accurate quantum mechanics, and thus may be considered to be an obsolete scientific theory. Niels Bohr proposed, in 1913, what is now called the Bohr model ofthe atom. He suggested that electrons could only have certain classical motions: 1... The electrons can only. travel in special orbits: at a certain discrete set of distances from the nucleus with specific energies. 2. The electrons do not continuously lose energy as they travel. They can only gain-and lose energy by jumping from.one allowed orbit to another, absorbing or emitting electromagnetic radiation witha frequency v determined by the energy difference of the levels according to'the Planck relation: AE =E,-E,=In, a where / is Planck’s constant. 3° The frequency of the radiation emitted at an orbit of period Tisas it would be in classical mechanics; it is the reciprocal of the classical orbit period: ve— T The significance of the Bohr model is.that the laws of classical mechanics apply to the motion of the electron about the nucleus only when restricted by a quantum rule. Although rule 3 is not completely well defined for small orbits, because the emission process involves two orbits with two different periods, Bohr could determine the energy spacing between levels using rule 3 and come to an exactly correct quantum rule: the angular momentum Z is restricted to be an integer multiple of a fixed unit: h ‘L=n—=nh 2a where n = 1, 2, 3, ... is called the principal quantum number, and h= n/ 27 . The lowest value of n is 1; this gives a smallest possible orbital Tadius of 0.0529 nm known as the Bohr radius. Once an electron is in this lowest orbit, it can get no closer to the proton. Starting from the angular Momentum quantum rule Bohr was able to calculate the energies of the allowed orbits of the hydrogen atom and other hydrogen-like atoms and ions. Bohr’s condition, that the angular momentum is an integer multiple of ‘Was later reinterpreted by de Broglie as a standing wave condition: theelectron is described by a wave and a whole number of wavelenjths must fit along the circumference of the electron’s orbit: vd na=2ar . Substituting de Broglie’s wavelength reproduces Bohr’s tule. Bohr justified his rule by appealing to the correspondence principle, without providing a wave interpretation. ELECTRONENERGYLEVELS ° The Bohr model gives almost exact results only for a system where two charged points orbit each other at speeds much less than that of light. This not only includes one-electron systems such as the hydrogen atom, singly- ionized helium, doubly ionized lithium, but it includes positronium and Rydberg states of any atom where one electron is far away from everything else.It can be used for K-line X-ray transition calculations ifother assumptions are added. In high energy physics, it can be used to calculate the masses of heavy quark mesons. 3 oa To calculate the.orbits requires two assumptions: a Classical mechanics The electron is held in a circular orbit by electrostatic attraction. The centripetal force is equal to the Coulomb force. 2 2 mv _ ke . pears where m, is the mass, e is the charge of the electron and k, is Coulomb’s constant. This determines the speed at any radius: The total energy is negative and inversely proportional to r. This means that it takes. energy to pull the orbiting electron away from the proton. For infinite values of r, the energy is zero, corresponding to a motionless electron infinitely far from the proton. The total energy is half the potential energy, which is true for non circular orbits.too by the virial theorem.Forlarger nuclei, the ont Zk ¢? where Zis the number of reduced mass (u = m2). a Quantum rule ly change is that ke is everywhere replaced b: Protons. For positro i e nium, 1, is replaced by its The angular momentum L = m,yris an integer multiple of ft: m.vr =nh Substituting the expression for the velocity gives an equation forr in terms of: ker =h so that the allowed orbit radius'at any nis: 24.2 wh: ” bre 2 ke*m, The smallest possible value of ris called the Bohr radius and is equal to: fe 2 eee ca oe "Ge 0.529x10-"°m ‘The energy of the -th level is determined by the radius: 2\ % ke (ke) m, -13.6ev 2r, » hn? v An electron in the lowest energy level of hydrogen (n = 1) therefore has 13.6 eV less energy than a motionless electron infinitely far from the nucleus. The next energy level (m = 2) is -3.4 eV. The third (7 = 3) is -1.51 eV, and so on. For larger values of 2, these are also the binding energies of a highly excited ~ atom with one electron in a large circular orbit around the rest of the atom. The combination of natural constants in the energy formula is called ~~ the Rydberg energy (R,): (ke y m, 2h? This expression is clarified by interpreting it in combinations which form more natural units: E= R= m,c? is the rest mass energy of the electron (511 keV)ke —— = @ & —— is the fine structure constant he 137 R + (me2)a? 2 Since this derivation is with the assumption that the nucleus is Orbiteg by one electron, we can generalize this result by letting the nucleus have g charge q = Ze where Zis the atomic number. This will now give us energy levels for hydrogenic atoms, which can serve as a rough order-of-magnitude approximation of the actual energy levels. So, for nuclei with Z protons, the energy levels are (toa rough approximation): DR, nr E, =~ When the electron moves from one energy level to another, a photon is emitted. Using the derived formula for the different ‘energy’ leve 1s of hydrogen one may determine thé ‘wavelengths’ of light that a hydrogen atom can emit, The energy of a photon emitted by a hydrogen atom is given by the difference of two hydrogen energy levels: “ where nis the final energy level, and n,is the initial energy level. Since the energy ofa photon is s eat Me as i the wavelength of the photon given offis given by Por Pesities : a aon) ; ’ Ps This is knownas the Rydberg formula, and the Rydberg constant Risk. he, or. R,/ 27 in natural units, Jn fact, Bohr’s derivation of ‘the E J Rydberg constant, as well as the concomitant agreement of Bohr’s formula with experimentally observed spectral lines of the Lyman (= 1), Balmer (1,= 2), and Paschen (7, = 3) series, and successful theoretical prediction of other lines not yet observed, was one reason that his model was immediately accepted,LIMITATIONS The Bohr model also has difficulty with, or else fails to explain: Much of the spectra of larger atoms. At best, it can make predictions about the K-alpha and some L-alpha X-ray emission spectra for larger atoms, if nvo additional ad hoc assumptions are made (see Moseley’s law above). Emission spectra for atoms with a single outer-shell electron (atoms in the lithium group)’ can also be approximately predicted. Also, if the empiric electron-nuclear screening factors for many atoms are known, many other spectral lines can be deduced from the information, in similar atoms of differing elements, via the Ritz-Rydberg combination principles (see Rydberg formula). All these techniques essentially make use of Bohr’s Newtonian energy- potential picture of the atom. The theory does not predict the relative intensities of spectral lines; although in some simple cases, Bohr’s formula or modifications of it, was able to provide reasonable estimates (for example, calculations by Kramers for the Stark effect). : " The existence of fine structure and hyperfine structure in spectral lines, which are known to be due to a variety of relativistic and subtle effects, as well as complications from electron spin. . The Zeeman effect - changes in spectral lines due to external magnetic fields; these are also due to more complicated quantum principles interacting with electron spin and orbital magnetic fields. . The model also violates the uncertainty principle in that it considers electrons to have known orbits and definite radius, two things which can not be directly known at once.QUANTUM NUMBERS © Q. What are the four quantum numbers? Explain the significance of each quantum number. State and explain Pauli’s exclusion principle. (R.U. 2007) Or Q. Discuss quantum numbers. (R.U. 2006) ‘Ans, Orbitals of electrons in atoms differ in size. shape and orientation. Definite energies and angular movements characterize atomic orbitals. The state of an electron in any atom is defined by certain permissible values of energy and angular momentum, which describe its location with respect to its nucleus and its energy level. These permissible states are called orbitals and are expressed by a set of four numbers ‘n’, ‘|’, ‘m’ and ‘s’ called quantumOE SE ne ee gaat Spee numbers. These numbers serve as the signature of the electrons, uni describing its position in the atom. The ‘n’, ‘I’ and ‘m’ indicate the g distribution while ‘s’ indicates the spin orientation of the electrons, PRINCIPAL QUANTUM NUMBER This quantum nimber determines the main energy shell or energy lev in which the electron is present, The principal quantum number gives the average distance of the electron from the nucleus and energy associated with it. quely Patial Itis denoted by the letter ‘n’ that can take whole number values Starting from 1, 2,3, 4, ...... The shell with n= 1 is called first shell or ‘K’ shell, The shell with n = 2 is the ‘L’ shell and so on. The first shell is closest to the nucleus. As the value of ‘n’ increases, the distance from the nucleus as well as the energy of the electrons increases. AZIMUTHAL QUANTUM NUMBER OR ANGULAR QUAN- TUM NUMBER The Azimuthal quantum number determines the angular momentum of the electron, denoted by the letter ‘I’. The value of ‘I? gives the sub level or sub shell in a given principal energy shell to which the electron belongs. It can have only positive integral values from zero to (n-1) where ‘ quantum number. The various sub shell values of | are.also designated by the letters s, p, d, f,..:... For any main energy level, the energies of the sub shell follow the order s> p>d>f. ’ The different sub shells are represented by first writing the value of ‘n’ and then the letter designated for the value of ‘I’. To illustrate, n’ is the principal n=11=0 onesubshell Is n= 0,1 two sub shells 2s, 2p n=31=0,1,2 three sub shells 3s, 3p, 3d n= 0,1,2,3 four sub shells 4s, 4p, 4d, 4f Thus for each value of ‘n’ there are ‘n’ values of ‘I’, The value of azimuthal quantum number gives the shape of the sub shell or orbital. So it is also called as orbital quantum number, MAGNETIC QUANTUM NUMBER The magnetic quantum number describes the behaviour of electron ina magnetic field. In the absence of external magnetic field electrons / orbitals having same values of ‘n’ and ‘’ but different values on ‘m’ have the same energies. They are called degenerate orbitals. However, in the presence of: an external magnetic field the orbitals vary in their energies slightly. This isOO because the preferred orientation of the orbital in space is a result of interaction ofits own magnetic field with that of the external magnetic field, Itis denoted by the letter ‘ny’ the values of which depends on ‘I’, This quantum number can have all integral values from *-1° to “H1" including 0. Thus for given ‘I’ value there are (21+ 1) values of ‘m’. Two orbitals in the same shell can have identical ‘n’ and ‘1? values but they must have different fixed values of ‘m’, The number of orbitals in enc! ssub shell 1=0m=0 only psub shell l= 1 m= +1,0, -1 three orientations three orbitals dsub shell l= 2 m= +2,+1,0,-1,-2 five orientations five orbitals SPIN QUANTUM NUMBERS The orientation of spin of an electron is di number ‘s’, The spin orientation is an intrinsic characteristic of the electron connected more with its magnetic behaviour rather than rotation ofan electron about its own axis. This number can have only two values corresponding to clockwise and anticlockwise spins i.e., +¥% and -Y, The clockwise spin is represented by an arrow (h) pointing upwards. The anti clockwise spin is tepresented by an arrow (i) pointing downwards. Each orbital can accommodate a maximum of two electrons provided they have opposite spins. h sub shell are given below: One orientation one orbital lesignated by its spin quantum 3d d — oF aeons Peeve Se remem. (Five) - ‘ =—= n=3orM << ‘ 2. 3p 4 % : meena Eo einem as 3p (three) ~, : Ar 35 mecca mo om tenn 3S (ONE) oneness (tire) n= 2ort o-" — ToS ceca al 25 (one) n= lork is aan een 15 (ON) —— ~“SUBSHELL ory ORBITAL SHELL SUBSHELL Fig: Number of subshells and orbitals in the KL and M shellsa PAULI’S EXCLUSION PRINCIPLE © Q State Pauli’s exclusion principle. i Ans. One expression of the Pauli Exclusion Principle is that “no two electrons in the same atom can be in the same quantum state.” This means that no two electrons can have the same set of quantum states of: 1. Energy, 2. Angular momentum magnitude, 3. Angular momentum orientation, and 4 Orientation of intrinsic spin. . Pauli’s Principle is based on the fact that: any. two given electrons are indistinguishable from one another and thus changing the designations between two or more electrons in different quantum states should have no observable effect. This apparently esoteric principle is the very basis for the existence of the Periodic Table of the Elements. The Pauli Exclusion Principle allows for the distinction between different elements. Furthermore, the Principle also effects the way molecules form in the bonding of atoms, for the way molecules interact to form gases, liquids, or solids, and/or how the molecules aggregate themselves in living organisms. In effect, the Pauli Exclusion Principle “is the basis for the observable order of the universe; including the existence of life.” Margenau has said:”*Pauli’s Exclusion Principle‘accounts for atomic structure. Without this structure, every atom would collapse into a Positive nucleus surrounded by an unorganized mass of negative charges.” DE BROGLIE’S WAVE EQUATION. © Q. _ Derive De Broglie’s wave equation. . (R.U; 2004) (V.B.U. 2009) Or Discuss Broglie’s equation. (R.U. 2006, 10) (V.B.U. 2007) i Or.” | What is meant by de Broglie’s matter wave? Derive de Broglie’s equation for matter wave. (V.B.U. 2005, 06) Ans. In 1924, Louis de Broglie, a french physicist suggested that electrons can also possess a dual character of wave and particle. Thus According to de- Broglie, all material particles in motion possess wave characteristics, According to de-Broglie, the wavelength 4 associated with a particle of mass m, moving with velocity vis given by the relationh Mea (i) Where, h=Planck’s constant mv= momentum of particle The waves associated with the material particles are cal led the matter waves. The equation 1 is known as the de- Broglie equation. DERIVATION OF DE-BROGLIE RELATIONSHIP According to Plank, a photon of light having energy E is associated with the wave of frequency vas E=hv ww (ii) According to Einstein, mass and energy are related as E='me? - (ii) where c= velocity of light equating the equations 2.& 3,:we get hy = me" Since mc. This equation is valid for a photon. De-Broglie suggested that on substituting the mass of the particle m and its velocity vin place of velocity of light c, the equation can also be used in case of the material particles. Thus, the wavelength of the material particles is evn mc This equation is known as the de-Broglie equation. or in other wordsrl Plank 'sconstant momentum Since h is a constant I Ga momentum Itmeans that the wavelength is inversely proportional to the momentum of the particles, SIGNIFICANCE OF DE-BROGLIE RELATIONSHIP | The dual nature of matter is applicable to all material objects but itis é significant for the microscopic bodies only. For large bodies, the wavelength of the associated waves are very small and connot be measured. Therefore, Practically all the large bodies are said to have no wavelength. Thus any material body can have the wavelength but itis measurable or significant only for the microscopic bodies such as electrons, * protons, atoms or the molecules. Qa Explain Heisenberg’s uncertainty Principle. Show that it is valid only for small particles and not for large objects, (R.U. 2004) Or Q. State and explain Heisenberg’s uncertainty Principle. (R.U. 2006, 10) (V.B.U. 2009) Ans. In 1927 werner Heisenberg pointed out that one cannot measure accurately both the position and velocity (momentum) of a microscopic particle. On the basis of this observation Heisenberg put forward a principle, Heisenberg’s uncertainty principle. According to this principal:- “It is not possible to determine precisely both the Position and the momentum (velocity) of small moving particles with accuracy.” MATHEMATICAL EXPRESSION FOR THE UNCERTAINTY PRINCIPLE IS : : known as the h Ax)( Ap) = — (ax)(ap)e se where Ax is uncertainty in position and Ap is uncertainty in momentum. _h The sign > means that the uncertainty can never be less than anee eee ee eneral) | 10 4 at age RITE a poeaee The constancy of the product of uncertainty means that : (i) If Ax is small i.e. the position of particle is measured accurately, then Ap would be large and thus the uncertainty in momentum will be large. (ii) On the other hand, if Ap is small the momentum of the particle can be measured accurately and the uncertainty in the position (i.e. ax ) will be large. In brief, it is impossible to determine simultaneously the position and momentum ofa microscopic particle with absolute accuracy or certainty. EXPLANATION OF UNCERTAINTY PRINCIPLE To explain the uncertainty principle, let us consider an object moving ina circular path. In order to determine the position of an object, we should shine light on the object when a beam of light falls on the object, the photons. of the incident light strikes the object and the reflected- photons are seen by our eyes. If the object is large, its position and velocity will not change by the impact of the striking photons. Asa result, one can measure the position and velocity of the object simultaneously. However, in case of microscopic objects such as electroris, protons, neutrons etc. striking photon of light will disturb the position as well as the velocity of the particle from its normal path. Due to change of path of electron, its velocity also changes and thus the determination of its exact velocity becomes impossible, although the position of the electron has been pinpointed in the microscope. ae, sacroscore Change of momentum and position of electron on impact with a photon.5 Above figure clearly demonstrates how the position of the electro, I changes by the impact of photon. Thus, It is not possible to determine simultaneously the exact posit, and momentum of the microscopic objects.ATOMIC ORBITALS Q..° Define Atomic orbitals. Or Write short note on atomic orbitals. Ans. An orbital can be defined as the- i “Region in space around the nucleus where the Probability of finding the electron is maximum.” ‘ ; Ifa boundary is drawn which encloses the region where the Probability ‘of finding electron is high, the resultant picture gives the general outline of the orbital. . Ae ORBIT ORBITAL. os Representation of an orbit and orbital. GENERAL CHARACTERISTICS OF ORBITALS 1: An orbital represents the region where the probability of finding + electronis maximum. s : 2: The electron exhibits the three dimensional motion: ° 3. The shapes of orbitals are different e.g. s-orbital is spherical while p- orbital are dumb-bell shaped and d-orbitals are double dumb-bell:- 4. Except s-orbital, all remaining orbitals are directional in nature. An orbital can have a maximum of two electrons. 5. s, p & d- ORBITALS Q Draw the shape of s, Pp & d-orbitals. : Or ¢ 3 ; © Discuss.the shapes of s, p; d orbitals ; CV.B.U. 2008)Ans. ¥ fy 4. SHAPEOFs-ORBITAL © For s orbital, when ¢= 0, the value of m is 0 ie, there is only one possible orientation. This means that the probability of finding an electron is the same in all directions at a given distance from the hucleus, Itshould therefore be spherical in shape because a sphere can be defined’ completely by a single value. The size of orbital depends upon the value of principal quantum number. The larger the value of ‘n’ the larger is the size of the orbital. Therefore, 2s- orbital is larger than the 1s orbital. 1s orbital 2s orbital Shapes of 1s and 2s orbitals 2. SHAPE OF p-ORBITAL (2 For p-orbital ( ¢= 1), there are 3 value of m namely -1, 0, +1. It means psubshell can have 3 possible orientations. These are represented by Px»Py>Pz- These three orbitals are equal in energy. Each p-orbital consist of 2 lobes symmetrical about a particular axis. Depending upon the orientation of the lobe these are denoted as 2p,.2p, and2p, according as they are symmetrical eae Shapes of p-orbital.tte, . about x, y andz axis is respectively. poe re orbital, ‘thsi is sdumb- bell shaped and has a directional character. 3. - SHAPE OF d-ORBITAL oO" For d-orbitals, the value of azimuthal number ‘¢ is 2 thus When fx); there are five possible orientatioris gor! responding to the allowed values ofm, these are m= -2,-1, 0, +1 and +2. Thus, there are fivé orbitals in each d- sit Shell. For 3d subshell, these are designated as Bdyys3dyz 134.34 92 and 3d. All these orbitals are ‘ degenerate i.e. they possess the same energy, Sry Shapes of d-orbitals.ELECTRONIC CONFIGURATIONS OF ATOMS IN Typ GROUND STATE Electronic Configuration Nameof Atomic merit ines Complete Onter Electronic Configuration Scandium a 15225? 2p8 3s? 3p 4s? 3a! i Titanium n 1st ap63e2aph4s23 | (EY je] ‘Vanadium 2B 15225? 2p°3523p% 4523 | [Fl] Chmanium 4 1322s? 2p8 35? 3p8 4s! 3 Manganese pay 1322s? 2p635? 3p 4230 | [A] Iron % 12252 2p8323p8423e | TY GTI Cobalt 0 1522s? 2p63s? 3p8 4s?3d? (RTT) Nickel B 122top83stzpactz8 | CY Great Copper e 1s22522p8 35? 3pf 4s! 3¢° RS Zine x 1s?2s?ap83s23p'4523q"° | [EY PatyQO Q Write short notes on Fajan’s Rule. ° . | Ans. The type of bond between two ions x+and y= depends on the effect of one ion on the other. The Positive ion distorts the negative ion as the Positive tion attracts the electrons on the negative-ion and repels the + vely charged | -nucleus.the Power of an ion to distort the other is its polarizing power and the | susceptibility of an ion to distortion is its polarizability. The ion distortion | " depends on both the polarizing power and the polarizability. Fajan’s rule states that co-valent bonding is favoured by (i) Small+ve ion ae Ee (ii) Large-ve ion (iii) Large charges on either of the ion | ‘If degree of polarization between’ y+ and 7 is small the bonds ionic. | If degree of polarization between ions is high, covalent character arises. Q Whatare Valence Bond Theory ? | : : Or What is VBT? What are its limitations? __(‘V,B.U. 2007,2009) Boe a Oe ceed . Write notes on VBT. Hoss a t Or i | Write the basic assumptions of V.B.T. 2] ’ hybridisation 5p3 hybrid orbitals Formation of methane molecule. . 4, sp°d hybridisation :- Inter mixing of 1s, 3p & 1d hybrid. orbitals is known as spd hybridisation.got PR P in Ground state TS] [tlt 3s 3p P in Excited state 3s 3p 3d TT EAN fo Se Sp’d hybridisation 7] aa Zz ¢ x Thre sp? orbitals a A Zz £ Y Five sp3d orbitals: a ve re X Two dp orbitals {2) The formation of five spd bybeid orbitals Sa spd hyfrid orbitals F ‘Tigonal Bipyracidal (b) spd hybrid orbitals 3. sp?d? hybridisation :- Intermixing of one s, three p and two d-hybrid orbitais 3s knownas sp*d* hybridisation.i ey EEE (0) Electron comtgutatlon of suiphur atom gro Ma, +Ttl el] (b) Sulphur atom ~ excited state. , Formation of sulphur hexafluoride molecule. ° i i i s ot 6. sp°d? hybridisation : - Intermixing of Is, three p and 3d hybrid orbitals is known as sp°d° hybridisation. ; | eg. :- IF, molecule | 5s 5p 5d t | PRTNTA) TTT] @ Ground state electronic configuration of dine aon. fF) AGTH GET (b) Excited state electronic configuration of iodine atom. rrr, ‘sP20 hybridisation F F F Shape of IF, molecule.TYPE OF HYBRIDISATION WITH SHAPE 3 EXAMPLES mm Naof Geometrical Sheleo wit bonds arrangement * Examples r a 2 reat ty Be, 2 3 Tea vy tr, a ae Tat 2S eet 2 dsp} 4 Square planar < DKON sd! 5 Tri i — pd rigonal bipyramidal PF, pe 6 Octahedral > SF, gd 7 Pentagonal bipyramidal xK F, Q. Determine the structure and shape of the simple inorganic molecules and ions. (i) NH, molecule. (ii) H,O molecule. ©) (iii) SnCl, molecule. (iv) SF, molecule. (V.B.U. 2006, 10) ) CIF, molecule.) (V.B.U. 2004, 06) (vi) -XeF, molecule. _(V.B.U. 2006, 10) (vii) XeF, molecule. (V.B.U. 2010) (viii) IF; molecule. (ix) BF, ion. &) PRE ion. ‘AMS (i) NH; molecule :- Ground state electronic configuration ofN ‘Atom (z= 7) is “is 2d 2p N (] ATTA) titit] = - ® ef hybridisation sp3 tal_[+T+[ 4) [H]_ aT) }»—lL— at TT wo A ibicmacall ii te bcidised Fe tion of ieee congetin eh rtgeton ents Shape of NH, molecule Jat ho bonded | lect pair tev , Pyramidal structure of ammonia molecule (ii) H,O molecule: (= 8)js Ground state electronic configuration of O atom Is 2s : 2p RT * sp [NT#T4] 1 Is Ground state ? Hybridised state electronic configuration electronic configurationShape of water molecule ? 4 : The outer electronic configuration of the central atom tir (z=50),in the ground state is : - 5s 5 Sd Ground state, Sn wl 4it ] sp? hybridisation (iii) SnCl, ‘molecule :- SHAPE OF sncl, (STANNOUS CHLORIDE) Formation of SnCl, molecule (iv) (sulphur tetrafluoride) molecule :- The outer electronic configuration of the central atom is (z= 16) is :- *+ 3s » gad (Ground State) () (AT I (exit Ss) ‘} : SEASHAPE OF sr, MOLECULE Shape of SF, molecule. (vy) CI, (Chlorine trifluoride) molecule :- The outer electronic configuration of Cl (z = 17) is 3s 3p 3d — ews A) TTT ETT ) catewy (UU! QUERY CLL | spd CF; iff SHAPE OF cir, MOLECULE \ F le =f F T-shaped Geometry of CIF, molecule. (vi) XeF, (Xenon difluoride) molecule :- The outer electronic configuration of xe (z = 54) is3 ——eeneral) [ 42] + Sp Sd Goundsiey ET] (AT ‘Excited Sate) ] fl Xe, St & WW Gory | F f | 2 R. 4 F Formation of XeF, molecule by sp’d' hybridisation (vii) XeF, (Xenon tetrafluoride) molecule :- The outer electronic configuration of xe (z= 54) is :- 5s Sp. Sd ewe 1 AD COO (Gert St) fy(viii) IF; (Iodine Pentafluoride) molecule :- The Outer lecttg : ii i nik configuration of Iodine (z= 53) is :- it Ss Sp Sd, cousin [1 (INTE a excited State) t ft t] t (tt 1 spd bybritiaion 1 AFs Formation of IF, by sp’d? hybridisation (ix) BF," ion :- The outer electronic configuration of B is (@=5) 2s 2» (Ganga (tH MEE] (Excited Stats) [f] TES] sp? hybridisation BF,Formation of BF;ion. (x) PF” ion :- The outer electronic configuration of P (z= 15) is :- 3s yp 3d (Gent Sun) Lo a Pe Shape of PF;ion.Q. — Writea note on Inductive effect. (2 (R.U. 2007) : Or Q. Explain Inductive effect. (R.U. 2005) Ans. It is an intrinsic effect that arises out of the tendency of a substitute bonded to carbon atom in general to either release the electrons involved in its bond to the carbon atom away from it or to withdraw the electrons involved in its bond towards itself. It is so termed as it is generally observed ina chain of minimum three carbon atoms where the present of a substituent at any part of the chain induces the effect along the chain. This effect in short arises out of the electro negativity of the atoms involved. Obviously this effect will be seen induced along a chain of carbon atoms bonded to one another through sigma bonds only and though it is a permanent effect it can never cleave any bond that is involved in it. . Measurement of Inductive Effect- Inductive effect cannot be measured in terms of any numerical values, but is always studied by comparison. | |Ger es ir ae Se a he ey ee a epee py this itis meant the standard bond is the C-H bond ofa R,C-H molecule, That is to say if we have a R,C-X molecule the substituent X which may be either one atom like Cl or a group of atoms like CH, may either attract the electrons in the C-X bond of the R,C-X molecule strongly towards itself or release the electrons of the C-X bond towards the 3 Rs that are bonded to the Cas R,C-X as compared to H in the C-H bond of R,C-H molecule. . Notations or Symbols of Inductive Effect- The inductive effect is indicated by an arrow along the bondas X —C < H. ifthe substituent X is more electro negative then the arrowhead will point towards X and if the substituent X is less electro negative than'H then the arrowhead will point towards Cas X > C>H.- Types - According to the nature of the substituent that is if more electro-ve than or less electro negative than two types of inductive effect denoted as -I effect and +I effect respectively where I indicates thus a substituent showing _Jeffect will attract the electron pairs in the chain of covalent bonds strongly towards itself for example, “NH,, NO, CN, Cl, Br, I, Thus, CH,-CH,- CH,-X then can be written as “|, CH, CH, >CH, >Cl (propylchloride) 2, . CH, >CH, CH, > NO,( propyl nitrate) 3. CH, >CH CH, CH X> CH x Tertiary > Secondary > Primary > Methyl” ° (iii) Relative strength of the acids : @ Any group or atom showing +1 effect decreases the acid strength as it increases the negative charge on the carboxylate ion which holds the hydrogen firmly. Alkyl groups havetl effect. Thus, acidic nature is, HCOOH > CH,COOH > C,H,COOH > C ;H,COOH > C,H,COOH > C,H,COOH “1 effect increases, so acid strength decreases Formicacid, having no alkyl group, is the most acidic among these acids. (b) — The group or atom having ~ | effect increases the acid strength as it decreases the negative charge on the carboxylate ion: Greater is the number of such atoms or groups (having ~I effect), greater is the acid strength. Thus, acidic nature is, sites: CC1,COOH > CHCI,COOH » CH, CCQOH > CH COOH Tkhby Tile Mermelor Aouts act aqutic acid sauitic ach cuts ach Inductive effect increases, so acid strength increases) (c) Strength of aliphatic carboxylic acids and benzoic acid Hence benzoic acid is stronger acid than aliphatic carboxylic acids but exception is formic acid. Thus, HCOOH =>. C,H,COOH — >RCOOOH Acid strength in decreasing orderalconut. Q Write a note on Electromeric effect. (7) Or , Explain Electromeric effect. © Ans. This isa temporary effect and takes place between two atoms joined by amultiple bond, i.e., a double or triple bond. It occurs at the requirements of theattacking reagent, and involves instantaneous transfer of a'shared pair of electrons of the multiple bond to one of the linked atoms. It is temporary in nature because the molecule acquires-its original electronic condition upon removal of the attacking reagént. : For example, consider the carbonyl group, >C=O; present in aldehydes and ketones. When a negatively charged reagent say : approaches the molecule seeking positive site, it causes instantaneous shift of electron pair of carbonyl group to oxygen (more electronegative than carbon). The carbon thus becomes deprived of its share in this transferred-pair of electrons and acquires positive charge. In the meanwhile oxygen takes complete control of the electron pair and becomes negatively charged. Therefore, in the presence of attacking reagent, one bond is Jost and this negatively charged attacking reagent links to the carbon having positive charge. : ae | a + —+ *¢ fi x ce, A \ Oo ~ . Attacking species ent of electrons from one atom to another Itibonded atoms is called electromeric ic shift of electrons takes place ductive effect, the electromeric This phenomenon of movem: at the demand of attacking reagent in mu! effect, denoted as E effect. The electromer only at the moment of reaction. Like the in effect is also classified as +E and E: ; * When the transfer of electrons takes place towards the attacking reagent, itis called+E (positive electromeric) effect. For example, se¢ \ Ce + Nee a fos H P. \ H ‘ When the transfer of electrons takes place away from the attacking reagent, it is called, -E (negative electromeric) effect. For example, \ Ne Ce Oy ee Nc Ce ay \ Write a note on Resonance or Mesomeric effect. (RU. 2007) CN Q Or ig) Q Explain Resonance. . = (R.U. 2006) Or 3 Q Explain Mesomeric effect. (R.U.2005) Ans, Iftwo or more structures can be assigned toa molecule, none of which is capable of describing all the known properties of the compound, then the actual structure is known to be a resonance hybrid or an intermediate of these structures. The various structures written are called resonating structures and” this phenomenon is called resonance. The phenomenon of Tesonance can be explained with the help of co, molecule. It has been represented by the structural formula: C 3 Or. O=C=0 The formula satisfies the conventional valency requirements, but it fails to explain some experimental facts, The actual carbon-oxygen bond in CO has been found to be 1.15 A whereas the normal carbon-oxygen double bond is 1.22 A and that for triple bond is 1/10 A. This means that carbon-oxygen bond in carbon dioxide is intermediate between a double and triple bond. To account for this, two other structures were proposed: * = + 5O:Ci:0: or O-CeO: LD: or. The actual molecule is said to be a resonance hybrid of these three giructures: O2620:, Saag” Des | 020-07 Benzene molecule is also regarded as a resonance hybrid of the following two structures: Q. Give an account of similarities and dissimilarities between Inductive effect and Mesomeric effect. (R.U. 2005) Ans, The similarities are as follows — (i) - Both inductive effect and mesomeric effect are. permanent effects happening in some of the organic compounds. (i) Both The differences between Inductive effect and mesomeric effect are as given in the table below- Inductive effect Mesomeric effect 1. The effect operates in saturated | I. It is found mainly in and unsaturated compounds. conjugated systems. 2#Partial charges are developed on 2. Electron pair is completely » Atoms, ; displaced and full +ve and -ve charges are developed. 3. It involves the displacement of | 3. It involves _the ct electrons: delocalisation of 71 electrons and one pairs. 4 It lasts over Jong distances dueto conjugation, 4. It lasts only for a short distance.[85 ] PROFESSORSNOTES CUM GUESS SERIES : Q Write notes on Resonance, “7 (RU, 2004) Ans, “The concept of hybridisation of two or more conventional valence structures to yield a new stable hybrid form less energy is termed Resonance» The resonance structures/cononical structures/contributing structures are hypothetical and individually do not represent any real molecule, Resonance really involves the delocalization of electrons in the molecule $0 as to give a new stable form which explains its behaviour. The CoC = bond in benzene and several other organic compounds behaves as stronger than the normal ethylene linkage. This is explained by the fact that one of the e* pair between the two carbons is delocalized or displaced to give a stable resonance hybrid form as :- - Pet SEEK. eS DE-ES Resonance structures CIO C-C distance in ethane molecule — 1.544 eg :- Benzene molecule C=C distance in ethylene molecule > 1.334 but, In benzene all C—C bonds has value as 1 394. indicating clearly their hybrid nature. (a) _ Resonance involves only a shift of es. z (b) _ In case of Resonance, only one molecular form exists which is an intermediate arrangement between the two possible forms. The energy of actual structures of the molecule is lower than that of any of the cononical structures. The difference in energy between the actual structures and the lowest energy resonance stress is called the resonance stabilisation energy or simply‘called resonance energy, : Resonance Energy Or Energy of Energy of Resonance actual any conenical stabilisation structures structures energyaR Write notes on types of Reagents. ) -sOr : s ‘Z what do you mean electrophiles and nucleophiles illustrate wit suitable examples. ek Shes (R.U. 2003 Or- : ; Write notes on electrophiles & Nucleophiles, (R.U. 2006 Ans. The starting materials or compounds taking part in'a chemical reactior are called reactants, Reactants can be broad ly classified into reagents and substrate. In general, A more reactive reactant which initiates the chemical process is called attacking reagent, “on the other handa 8eneralized term used for the molecule which undergoes the attack of, attacking species is called subsrate. Substrate + Attacking reagent —» Prodcucts Classification of, Attacking reagents :- : There are three different types of attacking reagents which take part in organic reactions. They are free radicals, electrophiles or electrophilic reagents and nucleophile or Nucleophollic reagents. :1 Free radical ¢- * Anatom oF electically neutral group of atoms containing unpaired ron is known as free radical. Due to presence of an unpaired electron, they are paramagnetic. Generation of free radicals The free radicals are formed by thermal or photochemical cleavage of chlorine and organic peroxide etc. cici—acr" +. Cr orS20K — Freeracialsor ‘chlorine atoms elec Electrophilic reagents or Electrophiles (Electro = electron; phile = loving) The species which are electron-dificient and are capable of ‘accepting a electrons are called electrophilic reagents. They have lust for electrons and attack the negative or electron rich centres of subsrate. ASelectrophiles are electron pair acceptors therefore, they arealso called Lewis acids. pair of These are of two types : (i) Positive electrophilies. e.g. foe ; H-C NO; °R oh H,O Praon—” Chloronienion | ‘ironivmion ‘ipbotanton H Aeylium ion Methyl carbocation y charge but are electron (i) Neutral electrophiles. These do not carry an} deficient. e.g. CO,,BF,, AICI S0,,FeCh. le of an electrophile in which central atom has SnCl, is an exampl complete a octet yet it can coordinate with more electrons due to the availability of vacant d-orbitals. Electrophile can attack the electron-rich substrate, ion or molecule, as follows: 4 1 \ See Be Page ; Suosire Positive Neutral product electrophile \ [ace ore B = Ge t ‘gubsteate. ; Neutral Negative product E ‘electrophilea3 Wig: iva BES (3). - Nueleophilic reagents or Nucléophiles. (Nucleo = nucleus ;. phfle = loving) i ‘ A negatively charged or neutral specles with lone pair of elecions ay capable of donating a pair of electrons is called a nucleophile. nd They are electron-rich 1reagents and will always attack Posey cha a or electron-deficient centres of a'subsrate. Nuclephile is called Lewis base because ofits tendency to donate a pair of electons. 7 These are of two types : - . (i), Negatively charged nuclephiles e.g. : a tr =t RS Ont R—COOM > or Bromide on Catbusion >» Cyanide fan Cutuinylate lon 20H RGF HCed: SHydeoxyl ion anon Asselin o (ii) Neutral nucleophiles. These species do not have negative charge but : have one or more lone Paits'0 of electrons. i Aleohol Water RNK:, RNH, RN RSH Amines’ Thioatcoho! Nueciephile can attack. the positively charged or electron dificient substrate ion or molecule to form neutral or positively charged product. ey sitira Tage + Nu- —> tu f Substrate ion Negatively chargedNeutral. product | * —Ch + Nu —» Ah | | Substrate ion Neutral Positively charged nucleophile Productee differences betwe: what ar Fucleophiles (Nucleophilic entities) en Nucleophiles & Electrophites? Elccrophiles (Electrophilic entities) They are electron-rich. They rovide an electron pair. They are Lewis bases. They possess an unshared pair of electrons in an orbital. They are usually anions. They attack regions of low electron density. For example- H,0.ROH,: OH «NH, CN-, Br ,OH” , Explain about ns, The minimum energy converted toa product inac The energy of activation tobe changed toa cont atthe transition state is cal Areaction that involves both possibilities. () Either bond cleavage and: (i) Bond cleavage occurs priol If bond cleavage al described by an energy diagram. Transition state => Progress of reaction. (Exethermic reaction) dition called transiti led an activates bond cleavage and bo! bond formati 1 to bond formation. ind bond formation 0c They are electron-deficient. They accept an electron pair. They are Lewis acids. They possess an empty orbital to receive the electron pair. They are usually cations. They attack regions of high electron density. For example- H” Br’ ,NO,'etc. ene Energy consideration in organic reaction. y that must be hemical reaction is called the attained by areactant before itcan be energy of ‘activation. js the energy necessary for a reactant ‘on state and the reactant (or reactants) .d complex for the reaction. nd formation has two limiting jon occur: simultaneously oF cur simultaneously, the reaction ‘Transition state Eq(AID* + Products on Reactants Progress of reaction (ndotherintc reaction)ge ee Ww) Free radical. What is carbocation ? Discuss the (i) Formation (ii) Strucc’ re (ili) Relative stability of carbocations. (R.U. 2010) Or Give an account of the mode of formation of carbonium ion. How many types of carbonium ions are there? Explain the stability of carbonim jon on the basis of inductive effect & resonance. , (R.U. 2004) Or Give an account of the mode of formation and Relative stability of carbonium ions. (R.U. 2008) . Or Write notes on Carbocation or Carbonium ions © Ans. Carbocations or Carbonium ions :- A group of atoms with carbon atom carrying positive charge and having only six electrons is known asa carbocation. The carbocations are also known ascarbonium ions. In general, itis represented as R | R—- ‘ [R=Horany alkyl oraryl group] R : : GENERATION OF CARBOCATIONS The carbocations are produced during organic reactions in many ways such as :- () Byheterolysis of a covalent bond (C- X) of organic hallides in highly polar medium (direct ionisation) 5 Foreg, R = 5 ee + x (CHC -Cl—(CH,),C'+ tert~buyl chloride yert=buly cation CH, =CH - CH,CI—> CH, = CH-CH,+Cl Allyl chloride, Allyleation i) By addition ofa proton to unsaturated compound (pio! tonation) such as alkenes, carbonyl compounds and nitriles. For example, 8G :+ recn Sen, + Ht —» R—CH-CHy Nes * NS ba PEED + HY > > C-OH (iii) By protonation of compounds containing an atom with lone Pair of electrons followed elimination of a simple molecule carrying this atom, For, example, RHO-H +H! —> RAO -H—» Rt + 0! Alcohol H Carbocation Protonated atcottol Rt +R-O-H Cathocation ** RHE a> Ether Protonated ether STRUCTURE OF CARBOCATIONS 1 C ion :1s }2 px’ 2py' 2pz? (5e) sp’- hybridization Inacarbocation, positively charged carbon is sp”-hybridised. The three sp2-hybrid orbitals are used in the formation of sigma bonds with three other atoms or groups and the remaining unused p-orbital remains.vacant. Since the three sp2-orbitals lie in one plane and are directed towards the corners of an equilateral triangle, the carbocation has flat planar strucure with electron - _ deficient carbon and the three.atoms attached to it lying in the same plane and the bond angle around the positively charged carbon is 120° each. The evidence for the planar structure is that carbocations are difficult to be formed at bridgeheads, where they cannot be planar. Nee ie Noss b fe) me o Fig. (a) A carbocation (only o-bonds shown); (b) an empty p-orbital above and below plane of the o-bonds.(68 OF ALKYL CARBOCATIONS ending upon the nature of carbon carrying the Dep Positi - i ri sitive charge, i, ns may be classified as primary, se ‘ ‘ge, alkyl x stato ys edcondary and tertiary. y H u d i t mf Ra i nels ae a h t I Methyl Primary Secoodary ey OH eas geLATIVE STABILITY OF CARBOCATIONS ‘According to the laws of electrostatics the stability ofa charged system isincreased by dispersal of charge. Therefore any factor tends to spread out hepositive charge of the electron-deficient carbon (field effect) and distribute joverthe rest of the ion, must stabilise a carbocation. Consider a substituent G, attached to the electron-deficient carbon. following two situations may arise as a result of field effect. 62- I. where G is electron- releasing, it disperses charge and stabilises cation I, : ° - c- R-Mg—X —— RH + Mg¢ Alby! halide Alkane Nou Jenson Xx RH + me : Alkane ‘OC2Hs 2 oe ae — Alkane e.g., CoHsBr+Mg.—— > CoHsMeBr x her ah Ethyl bromide... Ethyl magnesium bromide “ (Grignard’s reagent) Br Ethane The whole sequence of reaction of result in the reduction of alkyl halides. The yieds of perparation of alkanes by means-of grignard’s reagent are very high (almost 100%) _ (iii) “Catalytic hydrogenatoin. with molecular hydrogent in the presence of a catalyst, alkyl halides are reduced to alkanes. CH, Br + H, 43 C,H, + HBr 200°C Ethlyl bromide Ethane Cl. . rs Po CHj—CH—CH, + Hj —— > CH3CH,CH; +. HCl Isopropyl chloride Propane (iv) With Hydroidic acid. ‘otit _ Alkyl iodies are reduced to alkanes when they are heated with hydrio acid at high temperature in the presence of red phosphorus. ~~ iISO°C RI + HI BOCs Rog 1, some other clasess of compunds such and carboxylic acids are also reduced to a: By wurtz reaction when two molecules of in dry ether, a higher alkane is as aldehydes. ketones, alcohols alkanes with this method. Ikyl halides react with two atoms of sodium obtained. This is called wurtz reaction. Tipe pa Dry ether R4X + 2Na + Ro) R-R + 2NaX Alkyl halide ah Alkane tees Dry cher CHyfcr 4 2Na Cin, “2S. CHy—CH; + 2Nact Ethane ther ~— br CoHsfBr ENA E BEG H, CallyCiHy + 2Hade jane Other metals like Cu, Ag ina finely. divided state may also be used in place of sodium. This reaction is used increase the length of carbon chain (i.e,.Ascent of series). Utility: This mehtod hepls in creating a new carbon- carbon bond. so it can be used in prepairing compounds having larger number of carbon atoms from the compounds containing smaller number of carbons atoms. In conversions, wurtz reaction may thus be used to step up the series. : Limitations: (#) _ This reaction is not suitable for the preparation of unsymmetrical alkanes because when we take mixture of two alkyl halides, mixture of products are formed. e:g., As . ee : Dry ether cHs-for + aNa + CI}QHs ——> CHy-CHy=—CH, + 2Nacl Methyl chloride Ethyl chloride Propane Side reactions : i Dry ether fo). CHy-|er + 2Na $CICH; > CHy—CHy + 2NaCcl y Ethane 2 Dry ether : ish. CH3CH2Cl+2Na+CICH,—CH;-——_ CH3CH2CH2CH + 2NaCl n-Butane Thus in the preparatoin of propane, ethane and butane are also formed as. Side products. i | (ii) ~ This method cannot bé used for the preparation of methane. | iy Tertiary alkyl hadlides cannot be used for this purpose.