12.3 BEHAVIOUR OF GASES where M is the mass of the gas containing N Properties of gases are easier to understand than molecules, M0 is the molar mass and NA the those of solids and liquids. This is mainly Avogadro’s number. Using Eqs. (12.4) and (12.3) because in a gas, molecules are far from each can also be written as other and their mutual interactions are PV = kB NT or P = kB nT negligible except when two molecules collide. Gases at low pressures and high temperatures much above that at which they liquefy (or solidify) approximately satisfy a simple relation ) between their pressure, temperature and volume –1 given by (see Chapter 10) K –1 PV = KT (12.1) mol Jfor a given sample of the gas. Here T is the ( temperature in kelvin or (absolute) scale. K is a T pV µ constant for the given sample but varies with the volume of the gas. If we now bring in the idea of atoms or molecules, then K is proportional to the number of molecules, (say) N in the sample. We can write K = N k . Observation tells P (atm) us that this k is same for all gases. It is called Fig.12.1 Real gases approach ideal gas behaviour at Boltzmann constant and is denoted by k B. low pressures and high temperatures. P1V1 P2 V2 where n is the number density, i.e. number ofAs = = constant = kB (12.2) N 1 T1 N 2 T2 molecules per unit volume. kB is the Boltzmann constant introduced above. Its value in SI unitsif P, V and T are same, then N is also same for all is 1.38 × 10–23 J K–1.gases. This is Avogadro’s hypothesis, that the Another useful form of Eq. (12.3) isnumber of molecules per unit volume is ρRT the same for all gases at a fixed temperature and P = (12.5) pressure. The number in 22.4 litres of any gas M 0 Reprint 2025-26 KINETIC THEORY 247 where ρ is the mass density of the gas. etc. in a vessel of volume V at temperature T and A gas that satisfies Eq. (12.3) exactly at all pressure P. It is then found that the equation of pressures and temperatures is defined to be an state of the mixture is : ideal gas. An ideal gas is a simple theoretical PV = ( µ1 + µ2 +… ) RT (12.7)model of a gas. No real gas is truly ideal. Fig. 12.1 shows departures from ideal gas RT RT i.e. P = µ1 + µ2 + ... (12.8)behaviour for a real gas at three different V V temperatures. Notice that all curves approach = P1 + P2 + … (12.9)the ideal gas behaviour for low pressures and high temperatures. Clearly P1 = µ1 R T/V is the pressure that At low pressures or high temperatures the gas 1 would exert at the same conditions of molecules are far apart and molecular volume and temperature if no other gases were interactions are negligible. Without interactions present. This is called the partial pressure of the the gas behaves like an ideal one. gas. Thus, the total pressure of a mixture of ideal If we fix µ and T in Eq. (12.3), we get gases is the sum of partial pressures. This is Dalton’s law of partial pressures. PV = constant (12.6) i.e., keeping temperature constant, pressure of a given mass of gas varies inversely with volume. This is the famous Boyle’s law. Fig. 12.2 shows comparison between experimental P-V curves and the theoretical curves predicted by Boyle’s law. Once again you see that the agreement is good at high temperatures and low pressures. Next, if you fix P, Eq. (12.1) shows that V ∝ T i.e., for a fixed pressure, the volume of a gas is proportional to its absolute temperature T (Charles’ law). See Fig. 12.3. Fig. 12.3 Experimental T-V curves (solid lines) for CO2 at three pressures compared with Charles’ law (dotted lines). T is in units of 300 K and V in units of 0.13 litres. We next consider some examples which give us information about the volume occupied by the molecules and the volume of a single molecule. ⊳ Example 12.1 The density of water is 1000 kg m–3. The density of water vapour at 100 °C and 1 atm pressure is 0.6 kg m–3. The volume of a molecule multiplied by the total Fig.12.2 Experimental P-V curves (solid lines) for number gives ,what is called, molecular steam at three temperatures compared with volume. Estimate the ratio (or fraction) of Boyle’s law (dotted lines). P is in units of 22 the molecular volume to the total volume atm and V in units of 0.09 litres. occupied by the water vapour under the Finally, consider a mixture of non-interacting above conditions of temperature and pressure.ideal gases: µ moles of gas 1, µ moles of gas 2, 1 2 Reprint 2025-26 248 PHYSICS Answer For a given mass of water molecules, number of molecules and (ii) mass density the density is less if volume is large. So the of neon and oxygen in the vessel. Atomic volume of the vapour is 1000/0.6 = 1/(6 × 10 -4 ) mass of Ne = 20.2 u, molecular mass of O2times larger. If densities of bulk water and water = 32.0 u. molecules are same, then the fraction of molecular volume to the total volume in liquid Answer Partial pressure of a gas in a mixture is state is 1. As volume in vapour state has the pressure it would have for the same volume increased, the fractional volume is less by the and temperature if it alone occupied the vessel. same amount, i.e. 6×10-4. ⊳ (The total pressure of a mixture of non-reactive ⊳ gases is the sum of partial pressures due to its Example 12.2 Estimate the volume of a constituent gases.) Each gas (assumed ideal) water molecule using the data in Example obeys the gas law. Since V and T are common to 12.1. the two gases, we have P1V = µ 1 RT and P2V = Answer In the liquid (or solid) phase, the µ2 RT, i.e. (P1/P2) = (µ1 / µ2). Here 1 and 2 refer to neon and oxygen respectively. Since (P1/P2) =molecules of water are quite closely packed. The (3/2) (given), (µ1/ µ2) = 3/2.density of water molecule may therefore, be (i) By definition µ1 = (N1/NA ) and µ2 = (N2/NA)regarded as roughly equal to the density of bulk where N1 and N2 are the number of moleculeswater = 1000 kg m–3. To estimate the volume of of 1 and 2, and NA is the Avogadro’s number.a water molecule, we need to know the mass of Therefore, (N1/N2) = (µ1 / µ2) = 3/2.a single water molecule. We know that 1 mole (ii) We can also write µ1 = (m1/M1) and µ2 =of water has a mass approximately equal to (2 + 16)g = 18 g = 0.018 kg. (m2/M2) where m1 and m2 are the masses of 1 and 2; and M1 and M2 are their molecular Since 1 mole contains about 6 × 1023 masses. (Both m1 and M1; as well as m2 andmolecules (Avogadro’s number), the mass of a molecule of water is (0.018)/(6 × 1023) kg = M2 should be expressed in the same units). If ρ1 and ρ2 are the mass densities of 1 and3 × 10–26 kg. Therefore, a rough estimate of the 2 respectively, we havevolume of a water molecule is as follows : Volume of a water molecule ρ1 m 1 / V m 1 µ1  M 1  = (3 × 10–26 kg)/ (1000 kg m–3) = = = × ρ2 m 2 / V m 2 µ2  M 2  = 3 × 10–29 m3 = (4/3) π (Radius)3 3 20.2 Hence, Radius ≈ 2 ×10-10 m = 2 Å ⊳ = × = 0.947 2 32.0 ⊳ ⊳ Example 12.3 What is the average distance between atoms (interatomic distance) in water? Use the data given in 12.4 KINETIC THEORY OF AN IDEAL GAS Examples 12.1 and 12.2. Kinetic theory of gases is based on the molecular picture of matter. A given amount of gas is a Answer : A given mass of water in vapour state collection of a large number of molecules has 1.67×103 times the volume of the same mass (typically of the order of Avogadro’s number) that of water in liquid state (Ex. 12.1). This is also are in incessant random motion. At ordinary the increase in the amount of volume available pressure and temperature, the average distance for each molecule of water. When volume between molecules is a factor of 10 or more than increases by 103 times the radius increases by the typical size of a molecule (2 Å). Thus, V1/3 or 10 times, i.e., 10 × 2 Å = 20 Å. So the interaction between molecules is negligible and average distance is 2 × 20 = 40 Å. ⊳ we can assume that they move freely in straight lines according to Newton’s first law. However,⊳ Example 12.4 A vessel contains two non- occasionally, they come close to each other, reactive gases : neon (monatomic) and experience intermolecular forces and their oxygen (diatomic). The ratio of their partial velocities change. These interactions are called pressures is 3:2. Estimate the ratio of (i) collisions. The molecules collide incessantly against each other or with the walls and change Reprint 2025-26 KINETIC THEORY 249 their velocities. The collisions are considered to the wall. Thus, the number of molecules with be elastic. We can derive an expression for the velocity (vx, vy, vz ) hitting the wall in time ∆t is pressure of a gas based on the kinetic theory. ½A vx ∆t n, where n is the number of molecules We begin with the idea that molecules of a per unit volume. The total momentum gas are in incessant random motion, colliding transferred to the wall by these molecules in against one another and with the walls of the time ∆t is: container. All collisions between molecules Q = (2mvx) (½ n A vx ∆t ) (12.10) among themselves or between molecules and the The force on the wall is the rate of momentum walls are elastic. This implies that total kinetic transfer Q/∆t and pressure is force per unit energy is conserved. The total momentum is area : conserved as usual. P = Q /(A ∆t) = n m vx 2 (12.11) Actually, all molecules in a gas do not have 12.4.1 Pressure of an Ideal Gas the same velocity; there is a distribution in velocities. The above equation, therefore, standsConsider a gas enclosed in a cube of side l. Take for pressure due to the group of molecules withthe axes to be parallel to the sides of the cube, speed vx in the x-direction and n stands for theas shown in Fig. 12.4. A molecule with velocity number density of that group of molecules. The (vx, vy, vz ) hits the planar wall parallel to yz- total pressure is obtained by summing over theplane of area A (= l2). Since the collision is elastic, contribution due to all groups:the molecule rebounds with the same velocity; its y and z components of velocity do not change P = n m v x2 (12.12) in the collision but the x-component reverses where v 2x is the average of vx 2 . Now the gas sign. That is, the velocity after collision is is isotropic, i.e. there is no preferred direction (-vx, vy, vz ) . The change in momentum of the of velocity of the molecules in the vessel. molecule is: –mvx – (mvx) = – 2mvx . By the Therefore, by symmetry, principle of conservation of momentum, the momentum imparted to the wall in the collision v 2x = v y2 = v z2 = 2mvx . 2 2 2 2 = (1/3) [ v x + v y + v z ] = (1/3) v (12.13) where v is the speed and v 2 denotes the mean of the squared speed. Thus P = (1/3) n m v 2 (12.14) Some remarks on this derivation. First, though we choose the container to be a cube, the shape of the vessel really is immaterial. For a vessel of arbitrary shape, we can always choose a small infinitesimal (planar) area and carry through the steps above. Notice that both A and ∆t do not appear in the final result. By Pascal’s law, given in Ch. 9, pressure in one portion of Fig. 12.4 Elastic collision of a gas molecule with the the gas in equilibrium is the same as anywhere wall of the container. else. Second, we have ignored any collisions in To calculate the force (and pressure) on the the derivation. Though this assumption is wall, we need to calculate momentum imparted difficult to justify rigorously, we can qualitatively to the wall per unit time. In a small time interval see that it will not lead to erroneous results. The ∆t, a molecule with x-component of velocity vx number of molecules hitting the wall in time ∆t will hit the wall if it is within the distance vx ∆t was found to be ½ n Avx ∆t. Now the collisions from the wall. That is, all molecules within the are random and the gas is in a steady state. volume Avx ∆t only can hit the wall in time ∆t. Thus, if a molecule with velocity (vx, vy, vz ) But, on the average, half of these are moving acquires a different velocity due to collision with towards the wall and the other half away from some molecule, there will always be some other Reprint 2025-26 250 PHYSICS molecule with a different initial velocity which P = (1/3) [n1m1 v1 2 + n2 m2 v 22 +… ] (12.20) after a collision acquires the velocity (vx, vy, vz ). In equilibrium, the average kinetic energy of If this were not so, the distribution of velocities the molecules of different gases will be equal. would not remain steady. In any case we are That is, finding v x2 . Thus, on the whole, molecular ½ m1 v1 2 = ½ m2 v 22 = (3/2) kB Tcollisions (if they are not too frequent and the so thattime spent in a collision is negligible compared to time between collisions) will not affect the P = (n1 + n2 +… ) kB T (12.21) calculation above. which is Dalton’s law of partial pressures. From Eq. (12.19), we can get an idea of the12.4.2 Kinetic Interpretation of Temperature typical speed of molecules in a gas. At a Equation (13.14) can be written as temperature T = 300 K, the mean square speed PV = (1/3) nV m v 2 (12.15a) of a molecule in nitrogen gas is : PV = (2/3) N x ½ m v 2 (12.15b) M N 2 28 –26 where N (= nV) is the number of molecules in m = = 26 = 4.65 × 10 kg. N A 6.02 × 10the sample. The quantity in the bracket is the average v 2 = 3 kB T / m = (516)2 m2s-2 translational kinetic energy of the molecules in 2 The square root of v is known as root mean the gas. Since the internal energy E of an ideal square (rms) speed and is denoted by vrms,gas is purely kinetic*, 2 ( We can also write v 2 as < v2 >.) E = N × (1/2) m v (12.16) vrms = 516 m s-1 Equation (12.15) then gives : The speed is of the order of the speed of sound PV = (2/3) E (12.17) in air. It follows from Eq. (12.19) that at the same We are now ready for a kinetic interpretation temperature, lighter molecules have greater rms of temperature. Combining Eq. (12.17) with the speed. ⊳ideal gas Eq. (12.3), we get Example 12.5 A flask contains argon and E = (3/2) kB NT (12.18) chlorine in the ratio of 2:1 by mass. The or E/ N = ½ m v 2 = (3/2) kBT (12.19) temperature of the mixture is 27 °C. Obtain i.e., the average kinetic energy of a molecule is the ratio of (i) average kinetic energy per proportional to the absolute temperature of the molecule, and (ii) root mean square speed gas; it is independent of pressure, volume or vrms of the molecules of the two gases. the nature of the ideal gas. This is a fundamental Atomic mass of argon = 39.9 u; Molecular result relating temperature, a macroscopic mass of chlorine = 70.9 u. measurable parameter of a gas (a thermodynamic variable as it is called) to a Answer The important point to remember is thatmolecular quantity, namely the average kinetic the average kinetic energy (per molecule) of anyenergy of a molecule. The two domains are connected by the Boltzmann constant. We note (ideal) gas (be it monatomic like argon, diatomic in passing that Eq. (12.18) tells us that internal like chlorine or polyatomic) is always equal to energy of an ideal gas depends only on (3/2) kBT. It depends only on temperature, and temperature, not on pressure or volume. With is independent of the nature of the gas. this interpretation of temperature, kinetic theory (i) Since argon and chlorine both have the same of an ideal gas is completely consistent with the temperature in the flask, the ratio of average ideal gas equation and the various gas laws kinetic energy (per molecule) of the two gasesbased on it. is 1:1. For a mixture of non-reactive ideal gases, the total pressure gets contribution from each gas (ii) Now ½ m vrms2 = average kinetic energy per in the mixture. Equation (12.14) becomes molecule = (3/2) ) kBT where m is the mass * E denotes the translational part of the internal energy U that may include energies due to other degrees of freedom also. See section 12.5. Reprint 2025-26 KINETIC THEORY 251 of a molecule of the gas. Therefore, v 2 ( rms ) Ar (m )Cl ( M )Cl 70.9 = = 2 v rms (m ) Ar ( M ) Ar = 39.9 =1.77 ( )Cl where M denotes the molecular mass of the gas. (For argon, a molecule is just an atom of argon.) Taking square root of both sides, v ( rms ) Ar ( vrms )Cl = 1.33 You should note that the composition of the mixture by mass is quite irrelevant to the above calculation. Any other proportion by mass of argon and chlorine would give the same answers to (i) and (ii), provided the temperature remains Fig. 12.5 Molecules going through a porous wall. unaltered. ⊳ ⊳ ⊳ Example 12.7 (a) When a molecule (or an Example 12.6 Uranium has two isotopes elastic ball) hits a ( massive) wall, it of masses 235 and 238 units. If both are rebounds with the same speed. When a ball present in Uranium hexafluoride gas which hits a massive bat held firmly, the same would have the larger average speed ? If thing happens. However, when the bat is atomic mass of fluorine is 19 units, moving towards the ball, the ball rebounds estimate the percentage difference in with a different speed. Does the ball move speeds at any temperature. faster or slower? (Ch.5 will refresh your Answer At a fixed temperature the average memory on elastic collisions.) energy = ½ m <v2 > is constant. So smaller the (b) When gas in a cylinder is compressed mass of the molecule, faster will be the speed. by pushing in a piston, its temperature The ratio of speeds is inversely proportional to rises. Guess at an explanation of this in the square root of the ratio of the masses. The terms of kinetic theory using (a) above. masses are 349 and 352 units. So (c) What happens when a compressed gas v349 / v352 = ( 352/ 349)1/2 = 1.0044 . pushes a piston out and expands. What ∆ V would you observe ? Hence difference = 0.44 %. (d) Sachin Tendulkar used a heavy cricket V bat while playing. Did it help him in [235U is the isotope needed for nuclear fission. anyway ?To separate it from the more abundant isotope 238U, the mixture is surrounded by a porous cylinder. The porous cylinder must be thick and Answer (a) Let the speed of the ball be u relative narrow, so that the molecule wanders through to the wicket behind the bat. If the bat is moving individually, colliding with the walls of the long towards the ball with a speed V relative to the pore. The faster molecule will leak out more than wicket, then the relative speed of the ball to bat the slower one and so there is more of the lighter is V + u towards the bat. When the ball rebounds molecule (enrichment) outside the porous (after hitting the massive bat) its speed, relative cylinder (Fig. 12.5). The method is not very to bat, is V + u moving away from the bat. So efficient and has to be repeated several times relative to the wicket the speed of the rebounding for sufficient enrichment.]. ⊳ ball is V + (V + u) = 2V + u, moving away from the When gases diffuse, their rate of diffusion is wicket. So the ball speeds up after the collision inversely proportional to square root of the with the bat. The rebound speed will be less than masses (see Exercise 12.12 ). Can you guess the u if the bat is not massive. For a molecule this explanation from the above answer? would imply an increase in temperature. Reprint 2025-26 252 PHYSICS You should be able to answer (b) (c) and (d) to the axis joining the two oxygen atoms about based on the answer to (a). which the molecule can rotate*. The molecule (Hint: Note the correspondence, pistonà bat, thus has two rotational degrees of freedom, each of which contributes a term to the total energycylinder à wicket, molecule à ball.) ⊳ consisting of translational energy tε and rotational energy εr.12.5 LAW OF EQUIPARTITION OF ENERGY The kinetic energy of a single molecule is εt + εr = 1 mv x2 + 1 mv y2 + 1 mv z2 + 1 I 1ω12 + 1 I 2ω22 (12.25) 2 2 2 2 2 1 2 1 2 1 2 εt = mv x + mv y + mv z (12.22) 2 2 2 For a gas in thermal equilibrium at temperature T the average value of energy denoted by < tε > is 1 2 1 2 1 2 3 εt = mv x + mv y + mv z = k B T (12.23) 2 2 2 2 Since there is no preferred direction, Eq. (12.23) implies 1 2 1 1 2 1 mv x = k B T , mv y = k B T , 2 2 2 2 Fig. 12.6 The two independent axes of rotation of a diatomic molecule 1 2 1 mv z = k B T (12.24) 2 2 where ω1 and ω2 are the angular speeds about A molecule free to move in space needs three the axes 1 and 2 and I1, I2 are the corresponding coordinates to specify its location. If it is moments of inertia. Note that each rotational constrained to move in a plane it needs two; and degree of freedom contributes a term to the if constrained to move along a line, it needs just energy that contains square of a rotational one coordinate to locate it. This can also be variable of motion. expressed in another way. We say that it has We have assumed above that the O2 molecule one degree of freedom for motion in a line, two is a ‘rigid rotator’, i.e., the molecule does not for motion in a plane and three for motion in vibrate. This assumption, though found to be space. Motion of a body as a whole from one true (at moderate temperatures) for O2, is notpoint to another is called translation. Thus, a always valid. Molecules, like CO, even at molecule free to move in space has three moderate temperatures have a mode of translational degrees of freedom. Each vibration, i.e., its atoms oscillate along the translational degree of freedom contributes a interatomic axis like a one-dimensional term that contains square of some variable of 2 oscillator, and contribute a vibrational energymotion, e.g., ½ mvx and similar terms in term εv to the total energy:vy and vz. In, Eq. (12.24) we see that in thermal equilibrium, the average of each such term is 1  d y  2 1 2 εv = m + ky½ kBT . 2  d t  2 Molecules of a monatomic gas like argon have only translational degrees of freedom. But what ε = εt + εr + ε v (12.26) about a diatomic gas such as O2 or N2? A where k is the force constant of the oscillator molecule of O2 has three translational degrees and y the vibrational co-ordinate. of freedom. But in addition it can also rotate Once again the vibrational energy terms in about its centre of mass. Figure 12.6 shows the Eq. (12.26) contain squared terms of vibrational two independent axes of rotation 1 and 2, normal variables of motion y and dy/dt . * Rotation along the line joining the atoms has very small moment of inertia and does not come into play for quantum mechanical reasons. See end of section 12.6. Reprint 2025-26 KINETIC THEORY 253 At this point, notice an important feature in where Cp is the molar specific heat at constant Eq.(12.26). While each translational and pressure. Thus, rotational degree of freedom has contributed only 5 one ‘squared term’ in Eq.(12.26), one vibrational Cp = R (12.30) mode contributes two ‘squared terms’ : kinetic 2 and potential energies. C p 5 The ratio of specific heats γ = = (12.31) Each quadratic term occurring in the C v 3 expression for energy is a mode of absorption of energy by the molecule. We have seen that in 12.6.2 Diatomic Gases thermal equilibrium at absolute temperature T, As explained earlier, a diatomic molecule treated for each translational mode of motion, the as a rigid rotator, like a dumbbell, has 5 degrees average energy is ½ kBT. The most elegant of freedom: 3 translational and 2 rotational. principle of classical statistical mechanics (first Using the law of equipartition of energy, the total proved by Maxwell) states that this is so for each internal energy of a mole of such a gas is mode of energy: translational, rotational and 5 5 vibrational. That is, in equilibrium, the total U = k B T × N A = RT (12.32) 2 2 energy is equally distributed in all possible The molar specific heats are then given by energy modes, with each mode having an average energy equal to ½ kBT. This is known as the law 5 7 Cv (rigid diatomic) = R, Cp = R (12.33)of equipartition of energy. Accordingly, each 2 2 translational and rotational degree of freedom 7 of a molecule contributes ½ kBT to the energy, γ (rigid diatomic) = (12.34) while each vibrational frequency contributes 5 If the diatomic molecule is not rigid but has 2 × ½ kBT = kBT , since a vibrational mode has in addition a vibrational mode both kinetic and potential energy modes.  5  7 The proof of the law of equipartition of energy U =  k B T + k B T  N A = RT is beyond the scope of this book. Here, we shall  2  2 apply the law to predict the specific heats of gases 7 9 9 theoretically. Later, we shall also discuss briefly, C v = R , C p = R , γ = R (12.35) 2 2 7 the application to specific heat of solids. 12.6.3 Polyatomic Gases 12.6 SPECIFIC HEAT CAPACITY In general a polyatomic molecule has 3 12.6.1 Monatomic Gases translational, 3 rotational degrees of freedom and a certain number ( f ) of vibrational modes.The molecule of a monatomic gas has only three According to the law of equipartition of energy,translational degrees of freedom. Thus, the it is easily seen that one mole of such a gas hasaverage energy of a molecule at temperature 3T is (3/2)kBT . The total internal energy of a mole  3 U = kBT + kBT + f kBT  NA of such a gas is  2 2 3 3 U = k B T × N A = RT (12.27) i.e.,Cv = (3 + f ) R, Cp = (4 + f ) R, 2 2 ( 4 + f ) γ = (12.36) The molar specific heat at constant volume, ( 3 + f ) Cv, is Note that Cp – Cv = R is true for any ideal d U 3 gas, whether mono, di or polyatomic. Cv (monatomic gas) = = RT (12.28) d T 2 Table 12.1 summarises the theoretical For an ideal gas, predictions for specific heats of gases ignoring Cp – Cv = R (12.29) any vibrational modes of motion. The values are Reprint 2025-26 254 PHYSICS in good agreement with experimental values of Answer Using the gas law PV = µRT, you can specific heats of several gases given in Table 12.2. easily show that 1 mol of any (ideal) gas at Of course, there are discrepancies between standard temperature (273 K) and pressure predicted and actual values of specific heats of (1 atm = 1.01 × 105 Pa) occupies a volume of 22.4 several other gases (not shown in the table), such litres. This universal volume is called molar volume. Thus the cylinder in this exampleas Cl2, C2H6 and many other polyatomic gases. contains 2 mol of helium. Further, since heliumUsually, the experimental values for specific is monatomic, its predicted (and observed) molar heats of these gases are greater than the specific heat at constant volume, Cv = (3/2) R,predicted values as given in Table12.1 suggesting and molar specific heat at constant pressure, that the agreement can be improved by including Cp = (3/2) R + R = (5/2) R. Since the volume of vibrational modes of motion in the calculation. the cylinder is fixed, the heat required is The law of equipartition of energy is, thus, well determined by Cv. Therefore, verified experimentally at ordinary temperatures. Heat required = no. of moles × molar specific heat × rise in temperature Table 12.1 Predicted values of specific heat = 2 × 1.5 R × 15.0 = 45 R capacities of gases (ignoring vibrational modes) = 45 × 8.31 = 374 J. ⊳ 12.6.4 Specific Heat Capacity of Solids Nature of Cv Cp Cp - Cv g Gas (J mol-1 K-1) (J mol-1 K-1) (J mol-1 K-1) We can use the law of equipartition of energy to determine specific heats of solids. Consider a Monatomic 12.5 20.8 8.31 1.67 solid of N atoms, each vibrating about its mean Diatomic 20.8 29.1 8.31 1.40 position. An oscillation in one dimension has average energy of 2 × ½ kBT = kBT . In three Triatomic 24.93 33.24 8.31 1.33 dimensions, the average energy is 3 kBT. For a mole of solid, N = NA, and the total energy is Table12.2 Measured values of specific heat U = 3 kBT × NA = 3 RT capacities of some gases Now at constant pressure ∆Q = ∆U + P∆V = ∆U, since for a solid ∆V is negligible. Hence, ∆Q ∆ U C = = = 3 R (12.37) ∆T ∆T Table 12.3 Specific Heat Capacity of some solids at room temperature and atmospheric pressure As Table 12.3 shows the prediction generally ⊳ Example 12.8 A cylinder of fixed capacity agrees with experimental values at ordinary 44.8 litres contains helium gas at standard temperature (Carbon is an exception). temperature and pressure. What is the amount of heat needed to raise the 12.7 MEAN FREE PATH temperature of the gas in the cylinder by Molecules in a gas have rather large speeds of 15.0 °C ? (R = 8.31 J mo1–1 K–1). the order of the speed of sound. Yet a gas leaking Reprint 2025-26 KINETIC THEORY 255 from a cylinder in a kitchen takes considerable are moving and the collision rate is determined time to diffuse to the other corners of the room. by the average relative velocity of the molecules. The top of a cloud of smoke holds together for Thus we need to replace <v> by <v r> in Eq. hours. This happens because molecules in a gas (12.38). A more exact treatment gives have a finite though small size, so they are bound 2 2 nπd (12.40)to undergo collisions. As a result, they cannot l = 1/ ( ) move straight unhindered; their paths keep Let us estimate l and τ for air molecules with getting incessantly deflected. average speeds <v> = ( 485m/s). At STP 0.02 × 1023 ( ) n = –3 22.4 × 10 ( ) = 2.7 × 10 25 m -3. Taking, d = 2 × 10–10 m, τ = 6.1 × 10–10 s t and l = 2.9 × 10–7 m ≈ 1500 d (12.41) v As expected, the mean free path given by d Eq. (12.40) depends inversely on the number density and the size of the molecules. In a highly evacuated tube n is rather small and the mean d free path can be as large as the length of the tube. ⊳ Example 12.9 Estimate the mean free path for a water molecule in water vapour at 373 K. Use information from Exercises 12.1 and Eq. Fig. 12.7 The volume swept by a molecule in time ∆t (12.41) above. in which any molecule will collide with it. Answer The d for water vapour is same as that Suppose the molecules of a gas are spheres of of air. The number density is inverselydiameter d. Focus on a single molecule with the proportional to absolute temperature.average speed <v>. It will suffer collision with any molecule that comes within a distance d 25 273 25 –3 So n = 2.7 × 10 × = 2 × 10 mbetween the centres. In time ∆t, it sweeps a 373 volume πd2 <v> ∆t wherein any other molecule –7 Hence, mean free path l = 4 × 10 m ⊳will collide with it (see Fig. 12.7). If n is the number of molecules per unit volume, the Note that the mean free path is 100 times the molecule suffers nπd2 <v> ∆t collisions in time interatomic distance ~ 40 Å = 4 × 10-9 m calculated ∆t. Thus the rate of collisions is nπd2 <v> or the earlier. It is this large value of mean free path that time between two successive collisions is on the leads to the typical gaseous behaviour. Gases can average, not be confined without a container. τ = 1/(nπ <v> d2 ) (12.38) Using, the kinetic theory of gases, the bulk The average distance between two successive measurable properties like viscosity, heat collisions, called the mean free path l, is : conductivity and diffusion can be related to the l = <v> τ = 1/(nπd2) (12.39) microscopic parameters like molecular size. It is In this derivation, we imagined the other through such relations that the molecular sizes molecules to be at rest. But actually all molecules were first estimated. Reprint 2025-26 256 PHYSICS SUMMARY 1. The ideal gas equation connecting pressure (P), volume (V) and absolute temperature (T ) is PV = µ RT = kB NT where µ is the number of moles and N is the number of molecules. R and kB are universal constants. R R = 8.314 J mol–1 K–1, kB = N A = 1.38 × 10–23 J K–1 Real gases satisfy the ideal gas equation only approximately, more so at low pressures and high temperatures. 2. Kinetic theory of an ideal gas gives the relation 1 2 P = n m v 3 where n is number density of molecules, m the mass of the molecule and v 2 is the mean of squared speed. Combined with the ideal gas equation it yields a kinetic interpretation of temperature. 1 2 3 2 1/2 3k B T m v = k B T , v rms = v = 2 2 ( ) m This tells us that the temperature of a gas is a measure of the average kinetic energy of a molecule, independent of the nature of the gas or molecule. In a mixture of gases at a fixed temperature the heavier molecule has the lower average speed. 3. The translational kinetic energy 3 E = kB NT. 2 This leads to a relation 2 PV = E 3 4. The law of equipartition of energy states that if a system is in equilibrium at absolute temperature T, the total energy is distributed equally in different energy modes of absorption, the energy in each mode being equal to ½ kB T. Each translational and rotational degree of freedom corresponds to one energy mode of absorption and has energy ½ kB T. Each vibrational frequency has two modes of energy (kinetic and potential) with corresponding energy equal to 2 × ½ kB T = kB T. 5. Using the law of equipartition of energy, the molar specific heats of gases can be determined and the values are in agreement with the experimental values of specific heats of several gases. The agreement can be improved by including vibrational modes of motion. 6. The mean free path l is the average distance covered by a molecule between two successive collisions : 1 l = 2 2 n πd where n is the number density and d the diameter of the molecule. Reprint 2025-26 KINETIC THEORY 257 POINTS TO PONDER 1. Pressure of a fluid is not only exerted on the wall. Pressure exists everywhere in a fluid. Any layer of gas inside the volume of a container is in equilibrium because the pressure is the same on both sides of the layer. 2. We should not have an exaggerated idea of the intermolecular distance in a gas. At ordinary pressures and temperatures, this is only 10 times or so the interatomic distance in solids and liquids. What is different is the mean free path which in a gas is 100 times the interatomic distance and 1000 times the size of the molecule. 3. The law of equipartition of energy is stated thus: the energy for each degree of freedom in thermal equilibrium is ½ k T. Each quadratic term in the total energy expression of a molecule is to be counted asB a degree of freedom. Thus, each vibrational mode gives 2 (not 1) degrees of freedom (kinetic and potential energy modes), corresponding to the energy 2 × ½ k T = k T. B B 4. Molecules of air in a room do not all fall and settle on the ground (due to gravity) because of their high speeds and incessant collisions. In equilibrium, there is a very slight increase in density at lower heights (like in the atmosphere). The effect is small since the potential energy (mgh) for ordinary heights is much less than the average kinetic energy ½ mv2 of the molecules. 5. < v2 > is not always equal to ( < v >)2. The average of a squared quantity is not necessarily the square of the average. Can you find examples for this statement. EXERCISESEXERCISESEXERCISESEXERCISESEXERCISES 12.112.112.112.112.1 Estimate the fraction of molecular volume to the actual volume occupied by oxygen gas at STP. Take the diameter of an oxygen molecule to be 3 Å. 12.212.212.212.212.2 Molar volume is the volume occupied by 1 mol of any (ideal) gas at standard temperature and pressure (STP : 1 atmospheric pressure, 0 °C). Show that it is 22.4 litres. 12.312.312.312.312.3 Figure 12.8 shows plot of PV/T versus P for 1.00×10–3 kg of oxygen gas at two different temperatures. y T1 PV –1 T2 (J K ) T x P Fig.Fig.Fig.Fig.Fig. 12.812.812.812.812.8 (a) What does the dotted plot signify? (b) Which is true: T1 > T2 or T1 < T2? (c) What is the value of PV/T where the curves meet on the y-axis? Reprint 2025-26 258 PHYSICS (d) If we obtained similar plots for 1.00×10–3 kg of hydrogen, would we get the same value of PV/T at the point where the curves meet on the y-axis? If not, what mass of hydrogen yields the same value of PV/T (for low pressure high temperature region of the plot) ? (Molecular mass of H2 = 2.02 u, of O2 = 32.0 u, R = 8.31 J mo1–1 K–1.) 12.412.412.412.412.4 An oxygen cylinder of volume 30 litre has an initial gauge pressure of 15 atm and a temperature of 27 °C. After some oxygen is withdrawn from the cylinder, the gauge pressure drops to 11 atm and its temperature drops to 17 °C. Estimate the mass of oxygen taken out of the cylinder (R = 8.31 J mol–1 K–1, molecular mass of O2 = 32 u). 12.512.512.512.512.5 An air bubble of volume 1.0 cm3 rises from the bottom of a lake 40 m deep at a temperature of 12 °C. To what volume does it grow when it reaches the surface, which is at a temperature of 35 °C ? 12.612.612.612.612.6 Estimate the total number of air molecules (inclusive of oxygen, nitrogen, water vapour and other constituents) in a room of capacity 25.0 m3 at a temperature of 27 °C and 1 atm pressure. 12.712.712.712.712.7 Estimate the average thermal energy of a helium atom at (i) room temperature (27 °C), (ii) the temperature on the surface of the Sun (6000 K), (iii) the temperature of 10 million kelvin (the typical core temperature in the case of a star). 12.812.812.812.812.8 Three vessels of equal capacity have gases at the same temperature and pressure. The first vessel contains neon (monatomic), the second contains chlorine (diatomic), and the third contains uranium hexafluoride (polyatomic). Do the vessels contain equal number of respective molecules ? Is the root mean square speed of molecules the same in the three cases? If not, in which case is vrms the largest ? 12.912.912.912.912.9 At what temperature is the root mean square speed of an atom in an argon gas cylinder equal to the rms speed of a helium gas atom at – 20 °C ? (atomic mass of Ar = 39.9 u, of He = 4.0 u). 12.1012.1012.1012.1012.10 Estimate the mean free path and collision frequency of a nitrogen molecule in a cylinder containing nitrogen at 2.0 atm and temperature 17 0C. Take the radius of a nitrogen molecule to be roughly 1.0 Å. Compare the collision time with the time the molecule moves freely between two successive collisions (Molecular mass of N2 = 28.0 u). Reprint 2025-26 CHAPTER THIRTEEN OSCILLATIONS 13.1 INTRODUCTION In our daily life we come across various kinds of motions. You have already learnt about some of them, e.g., rectilinear 13.1 Introduction motion and motion of a projectile. Both these motions are non-repetitive. We have also learnt about uniform circular13.2 Periodic and oscillatory motions motion and orbital motion of planets in the solar system. In 13.3 Simple harmonic motion these cases, the motion is repeated after a certain interval of 13.4 Simple harmonic motion time, that is, it is periodic. In your childhood, you must have and uniform circular enjoyed rocking in a cradle or swinging on a swing. Both motion these motions are repetitive in nature but different from the 13.5 Velocity and acceleration periodic motion of a planet. Here, the object moves to and fro in simple harmonic motion about a mean position. The pendulum of a wall clock executes 13.6 Force law for simple a similar motion. Examples of such periodic to and fro harmonic motion motion abound: a boat tossing up and down in a river, the

4.3 Bond Parameters c = 99 pm 1984.3.1 Bond Length r pmBond length is defined as the equilibrium distance between the nuclei of two bonded atoms in a molecule. Bond lengths are measured by spectroscopic, X-ray diffraction and electron-diffraction techniques about which you will learn in higher classes. Each atom of the bonded pair contributes to the rvdw= bond length (Fig. 4.1). In the case of a covalent 180 bond, the contribution from each atom is pm called the covalent radius of that atom. pm 360 The covalent radius is measured approximately as the radius of an atom’s Fig. 4.2 Covalent and van der Waals radii incore which is in contact with the core of an a chlorine molecule. The inner circles adjacent atom in a bonded situation. The correspond to the size of the chlorine covalent radius is half of the distance between atom (rvdw and rc are van der Waals and two similar atoms joined by a covalent bond covalent radii respectively). Reprint 2025-26 108 chemistry Some typical average bond lengths for Table 4.2 Average Bond Lengths for Some single, double and triple bonds are shown in Single, Double and Triple Bonds Table 4.2. Bond lengths for some common Covalent Bondmolecules are given in Table 4.3. Bond Type Length (pm) The covalent radii of some common O–H 96elements are listed in Table 4.4. C–H 107 4.3.2 Bond Angle N–O 136 C–O 143It is defined as the angle between the orbitals C–N 143 containing bonding electron pairs around the C–C 154 central atom in a molecule/complex ion. Bond C=O 121 angle is expressed in degree which can be N=O 122 experimentally determined by spectroscopic C=C 133 methods. It gives some idea regarding the C=N 138 distribution of orbitals around the central C≡N 116 atom in a molecule/complex ion and hence it C≡C 120 helps us in determining its shape. For Table 4.3 Bond Lengths in Some Commonexample H–O–H bond angle in water can be Moleculesrepresented as under : Molecule Bond Length (pm) H2 (H – H) 74 F2 (F – F) 144 4.3.3 Bond Enthalpy Cl2 (Cl – Cl) 199 It is defined as the amount of energy required Br2 (Br – Br) 228 to break one mole of bonds of a particular I2 (I – I) 267 type between two atoms in a gaseous state. N2 (N ≡ N) 109 The unit of bond enthalpy is kJ mol–1. For O2 (O = O) 121 example, the H – H bond enthalpy in hydrogen HF (H – F) 92 molecule is 435.8 kJ mol–1. HCl (H – Cl) 127 HBr (H – Br) 141H2(g) → H(g) + H(g); ∆aH = 435.8 kJ mol–1 HI (H – I) 160 Similarly the bond enthalpy for molecules Table 4.4 Covalent Radii, *rcov/(pm)containing multiple bonds, for example O2 and N2 will be as under : O2 (O = O) (g) → O(g) + O(g); ∆aH = 498 kJ mol–1 N2 (N ≡ N) (g) → N(g) + N(g); ∆aH = 946.0 kJ mol–1 It is important that larger the bond dissociation enthalpy, stronger will be the bond in the molecule. For a heteronuclear diatomic molecules like HCl, we have HCl (g) → H(g) + Cl (g); ∆aH = 431.0 kJ mol–1 In case of polyatomic molecules, the measurement of bond strength is more complicated. For example in case of H2O * The values cited are for single bonds, except where molecule, the enthalpy needed to break the otherwise indicated in parenthesis. (See also Unit 3 for two O – H bonds is not the same. periodic trends). Reprint 2025-26 Chemical Bonding And Molecular Structure 109 H2O(g) → H(g) + OH(g); ∆aH1 = 502 kJ mol–1 OH(g) → H(g) + O(g); ∆aH2 = 427 kJ mol–1 The difference in the ∆aH value shows that the second O – H bond undergoes some change because of changed chemical environment. This is the reason for some difference in energy of the same O – H bond in different molecules like C2H5OH (ethanol) and water. Therefore in polyatomic molecules the term mean or average bond enthalpy is used. It is obtained by dividing total bond dissociation enthalpy by the number of bonds broken as explained below in case of water molecule, 502 + 427 Fig. 4.3 Resonance in the O3 molecule Average bond enthalpy = 2 (structures I and II represent the two canonical = 464.5 kJ mol–1 forms while the structure III is the resonance hybrid) 4.3.4 Bond Order In the Lewis description of covalent bond, In both structures we have a O–O single the Bond Order is given by the number bond and a O=O double bond. The normal of bonds between the two atoms in a O–O and O=O bond lengths are 148 pm molecule. The bond order, for example in and 121 pm respectively. Experimentally H2 (with a single shared electron pair), in O2 determined oxygen-oxygen bond lengths in (with two shared electron pairs) and in N2 the O3 molecule are same (128 pm). Thus the (with three shared electron pairs) is 1,2,3 oxygen-oxygen bonds in the O3 molecule are respectively. Similarly in CO (three shared intermediate between a double and a single electron pairs between C and O) the bond bond. Obviously, this cannot be represented order is 3. For N2, bond order is 3 and its by either of the two Lewis structures shown is 946 kJ mol–1; being one of the highest above. for a diatomic molecule. The concept of resonance was introduced Isoelectronic molecules and ions have to deal with the type of difficulty experienced identical bond orders; for example, F2 and in the depiction of accurate structures of O22– have bond order 1. N2, CO and NO+ have molecules like O3. According to the concept bond order 3. of resonance, whenever a single Lewis structure cannot describe a molecule A general correlation useful for accurately, a number of structures withunderstanding the stablities of molecules is that: with increase in bond order, similar energy, positions of nuclei, bonding bond enthalpy increases and bond length and non-bonding pairs of electrons are decreases. taken as the canonical structures of the hybrid which describes the molecule 4.3.5 Resonance Structures accurately. Thus for O3, the two structures It is often observed that a single Lewis structure shown above constitute the canonical is inadequate for the representation of a structures or resonance structures and molecule in conformity with its experimentally their hybrid i.e., the III structure represents determined parameters. For example, the the structure of O3 more accurately. This is ozone, O3 molecule can be equally represented also called resonance hybrid. Resonance is by the structures I and II shown below: represented by a double headed arrow. Reprint 2025-26 110 chemistry Some of the other examples of resonance structures are provided by the carbonate ion and the carbon dioxide molecule. Fig. 4.5 Resonance in CO2 molecule, I, II Problem 4.3 and III represent the three canonical Explain the structure of CO32– ion in forms. terms of resonance. Solution In general, it may be stated that The single Lewis structure based on • Resonance stabilizes the molecule as the the presence of two single bonds and energy of the resonance hybrid is less one double bond between carbon than the energy of any single cannonical and oxygen atoms is inadequate to structure; and, represent the molecule accurately as it • R e s o n a n c e a v e r a g e s t h e b o n d represents unequal bonds. According characteristics as a whole. to the experimental findings, all carbon to oxygen bonds in CO32– are equivalent. Thus the energy of the O3 resonance Therefore the carbonate ion is best hybrid is lower than either of the two described as a resonance hybrid of the cannonical froms I and II (Fig. 4.3). canonical forms I, II, and III shown below. Many misconceptions are associated with resonance and the same need to be dispelled. You should remember that : • The cannonical forms have no real existence. • The molecule does not exist for a certain fraction of time in one cannonical form and for other fractions of time in other Fig. 4.4 Resonance in CO32–, I, II and III cannonical forms. represent the three canonical • There is no such equilibrium between forms. the cannonical forms as we have Problem 4.4 between tautomeric forms (keto and enol) in tautomerism. Explain the structure of CO2 molecule. • The molecule as such has a single Solution structure which is the resonance The experimentally determined carbon hybrid of the cannonical forms and to oxygen bond length in CO 2 is which cannot as such be depicted by 115 pm. The lengths of a normal a single Lewis structure. carbon to oxygen double bond (C=O) and carbon to oxygen triple bond (C≡O) 4.3.6 Polarity of Bonds are 121 pm and 110 pm respectively. The existence of a hundred percent ionic or The carbon-oxygen bond lengths in covalent bond represents an ideal situation. CO2 (115 pm) lie between the values for C=O and C≡O. Obviously, a single In reality no bond or a compound is either Lewis structure cannot depict this completely covalent or ionic. Even in case of position and it becomes necessary to covalent bond between two hydrogen atoms, write more than one Lewis structures there is some ionic character. and to consider that the structure of When covalent bond is formed between CO2 is best described as a hybrid of two similar atoms, for example in H2, O2, the canonical or resonance forms I, II and III. Cl2, N2 or F2, the shared pair of electrons is equally attracted by the two atoms. As a result Reprint 2025-26 Chemical Bonding And Molecular Structure 111 electron pair is situated exactly between the In case of polyatomic molecules the dipole two identical nuclei. The bond so formed is moment not only depend upon the individual called nonpolar covalent bond. Contrary to dipole moments of bonds known as bond this in case of a heteronuclear molecule like dipoles but also on the spatial arrangement HF, the shared electron pair between the two of various bonds in the molecule. In such atoms gets displaced more towards fluorine case, the dipole moment of a molecule is the since the electronegativity of fluorine (Unit 3) vector sum of the dipole moments of various is far greater than that of hydrogen. The bonds. For example in H2O molecule, which resultant covalent bond is a polar covalent has a bent structure, the two O–H bonds are bond. oriented at an angle of 104.50. Net dipole As a result of polarisation, the molecule moment of 6.17 × 10–30 C m (1D = 3.33564 possesses the dipole moment (depicted × 10–30 C m) is the resultant of the dipole below) which can be defined as the product of moments of two O–H bonds. the magnitude of the charge and the distance between the centres of positive and negative charge. It is usually designated by a Greek letter ‘µ’. Mathematically, it is expressed as follows : Dipole moment (µ) = charge (Q) × distance of separation (r) Dipole moment is usually expressed in Net Dipole moment, µ = 1.85 D Debye units (D). The conversion factor is = 1.85 × 3.33564 × 10–30 C m = 6.17 ×10–30 C m 1 D = 3.33564 × 10–30 C m The dipole moment in case of BeF2 is zero.where C is coulomb and m is meter. This is because the two equal bond dipoles Further dipole moment is a vector quantity point in opposite directions and cancel the and by convention it is depicted by a small effect of each other. arrow with tail on the negative centre and head pointing towards the positive centre. But in chemistry presence of dipole moment is represented by the crossed arrow ( ) put on Lewis structure of the molecule. The In tetra-atomic molecule, for example in cross is on positive end and arrow head is on BF3, the dipole moment is zero although thenegative end. For example the dipole moment B – F bonds are oriented at an angle of 120o of HF may be represented as : to one another, the three bond moments give a net sum of zero as the resultant of any two H F is equal and opposite to the third. This arrow symbolises the direction of the shift of electron density in the molecule. Note that the direction of crossed arrow is opposite to the conventional direction of dipole moment vector. Peter Debye, the Dutch chemist received Nobel prize in 1936 for Let us study an interesting case of NH3 his work on X-ray diffraction and and NF3 molecule. Both the molecules have dipole moments. The magnitude pyramidal shape with a lone pair of electrons of the dipole moment is given in Debye units in order to honour him. on nitrogen atom. Although fluorine is more electronegative than nitrogen, the resultant Reprint 2025-26 112 chemistry dipole moment of NH3 (4.90 × 10–30 C m) is • The smaller the size of the cation and the greater than that of NF3 (0.8 × 10–30 C m). This larger the size of the anion, the greater is because, in case of NH3 the orbital dipole the covalent character of an ionic bond. due to lone pair is in the same direction as • The greater the charge on the cation, the the resultant dipole moment of the N – H greater the covalent character of the ionic bonds, whereas in NF3 the orbital dipole is in bond. the direction opposite to the resultant dipole • For cations of the same size and charge,moment of the three N–F bonds. The orbital the one, with electronic configurationdipole because of lone pair decreases the effect (n-1)dnnso, typical of transition metals, isof the resultant N – F bond moments, which more polarising than the one with a noble results in the low dipole moment of NF3 as gas configuration, ns2 np6, typical of alkalirepresented below : and alkaline earth metal cations. The cation polarises the anion, pulling the electronic charge toward itself and thereby increasing the electronic charge between the two. This is precisely what happens in a covalent bond, i.e., buildup of electron charge density between the nuclei. The polarising power of the cation, the polarisability of the anion and the extent of distortion (polarisation) of anion are the factors, which determine the per Dipole moments of some molecules are cent covalent character of the ionic bond. shown in Table 4.5. Just as all the covalent bonds have 4.4 The Valence Shell Electron some partial ionic character, the ionic Pair Repulsion (VSEPR) Theory bonds also have partial covalent character. As already explained, Lewis concept is unable The partial covalent character of ionic to explain the shapes of molecules. This bonds was discussed by Fajans in terms of theory provides a simple procedure to predict the following rules: the shapes of covalent molecules. Sidgwick Table 4.5 Dipole Moments of Selected Molecules Dipole Type of Molecule Example Geometry Moment, µ(D) Molecule (AB) HF 1.78 linear HCl 1.07 linear HBr 0.79 linear Hl 0.38 linear H2 0 linear Molecule (AB2) H2O 1.85 bent H2S 0.95 bent CO2 0 linear Molecule (AB3) NH3 1.47 trigonal-pyramidal NF3 0.23 trigonal-pyramidal BF3 0 trigonal-planar Molecule (AB4) CH4 0 tetrahedral CHCl3 1.04 tetrahedral CCl4 0 tetrahedral Reprint 2025-26 Chemical Bonding And Molecular Structure 113 and Powell in 1940, proposed a simple theory result in deviations from idealised shapes and based on the repulsive interactions of the alterations in bond angles in molecules. electron pairs in the valence shell of the For the prediction of geometrical shapes atoms. It was further developed and redefined of molecules with the help of VSEPR theory, by Nyholm and Gillespie (1957). it is convenient to divide molecules into The main postulates of VSEPR theory are two categories as (i) molecules in which as follows: the central atom has no lone pair and • The shape of a molecule depends upon (ii) molecules in which the central atom the number of valence shell electron pairs has one or more lone pairs. (bonded or nonbonded) around the central Table 4.6 (page114) shows the atom. arrangement of electron pairs about a • Pairs of electrons in the valence shell repel central atom A (without any lone pairs) and one another since their electron clouds are geometries of some molecules/ions of the type negatively charged. AB. Table 4.7 (page 115) shows shapes of some simple molecules and ions in which the central• These pairs of electrons tend to occupy atom has one or more lone pairs. Table 4.8 such positions in space that minimise (page 116) explains the reasons for the repulsion and thus maximise distance distortions in the geometry of the molecule. between them. As depicted in Table 4.6, in the• The valence shell is taken as a sphere compounds of AB2, AB3, AB4, AB5 and AB6, with the electron pairs localising on the the arrangement of electron pairs and the spherical surface at maximum distance B atoms around the central atom A are : from one another. linear, trigonal planar, tetrahedral, • A multiple bond is treated as if it is a single trigonal-bipyramidal and octahedral, electron pair and the two or three electron respectively. Such arrangement can be seen pairs of a multiple bond are treated as a in the molecules like BF3 (AB3), CH4 (AB4) and single super pair. PCl5 (AB5) as depicted below by their ball and • Where two or more resonance structures stick models. can represent a molecule, the VSEPR model is applicable to any such structure. The repulsive interaction of electron pairs decrease in the order: Lone pair (lp) – Lone pair (lp) > Lone pair (lp) – Bond pair (bp) > Bond pair (bp) – Bond pair (bp) Fig. 4.6 The shapes of molecules in which central atom has no lone pair Nyholm and Gillespie (1957) refined the VSEPR model by explaining the important The VSEPR Theory is able to predict difference between the lone pairs and bonding geometry of a large number of molecules, pairs of electrons. While the lone pairs are especially the compounds of p-block elements localised on the central atom, each bonded accurately. It is also quite successful in pair is shared between two atoms. As a result, determining the geometry quite-accurately the lone pair electrons in a molecule occupy even when the energy difference between more space as compared to the bonding pairs possible structures is very small. The of electrons. This results in greater repulsion theoretical basis of the VSEPR theory regarding between lone pairs of electrons as compared the effects of electron pair repulsions on to the lone pair - bond pair and bond pair - molecular shapes is not clear and continues bond pair repulsions. These repulsion effects to be a subject of doubt and discussion. Reprint 2025-26 114 chemistry Table 4.6 Geometry of Molecules in which the Central Atom has No Lone Pair of Electrons Reprint 2025-26 Chemical Bonding And Molecular Structure 115 Table 4.7 Shape (geometry) of Some Simple Molecules/Ions with Central Ions having One or More Lone Pairs of Electrons(E). Reprint 2025-26 116 chemistry Table 4.8 Shapes of Molecules containing Bond Pair and Lone Pair Molecule No. of No. of Arrangement Shape Reason for the type bonding lone of electrons shape acquired pairs pairs AB2E 4 1 Bent Theoretically the shape should have been triangular planar but actually it is found to be bent or v-shaped. The reason being the lone pair- bond pair repulsion is much more as compared to the bond pair-bond pair repulsion. So the angle is reduced to 119.5° from 120°. AB3E 3 1 Trigonal Had there been a bp in place of lp the shape would have pyramidal been tetrahedral but one lone pair is present and due to the repulsion between lp-bp (which is more than bp-bp repulsion) the angle between bond pairs is reduced to 107° from 109.5°. Bent The shape should have been AB2E2 2 2 tetrahedral if there were all bp but two lp are present so the shape is distorted tetrahedral or angular. The reason is lp-lp repulsion is more than lp-bp repulsion which is more than bp-bp repulsion. Thus, the angle is reduced to 104.5° from 109.5°. AB4E 4 1 See- In (a) the lp is present at axial saw position so there are three lp—bp repulsions at 90°. In(b) the lp is in an equatorial position, and there are two lp—bp repulsions. Hence, arrangement (b) is more stable. The shape shown in (b) is described as a distorted tetrahedron, a folded square (More stable) or a see-saw. Reprint 2025-26 Chemical Bonding And Molecular Structure 117 Molecule No. of No. of Arrangement Shape Reason for the type bonding lone of electrons shape acquired pairs pairs AB3E2 3 2 T-shape In (a) the lp are at equatorial position so there are less lp- bp repulsions as compared to others in which the lp are at axial positions. So structure (a) is most stable. (T-shaped).

4.5 Valence Bond Theory of the valence bond theory is based on the knowledge of atomic orbitals, electronicAs we know that Lewis approach helps in configurations of elements (Units 2), thewriting the structure of molecules but it overlap criteria of atomic orbitals, thefails to explain the formation of chemical hybridization of atomic orbitals and thebond. It also does not give any reason for the principles of variation and superposition. Adifference in bond dissociation enthalpies and rigorous treatment of the VB theory in termsbond lengths in molecules like H2 (435.8 kJ of these aspects is beyond the scope of this mol-1, 74 pm) and F2 (155 kJ mol-1, 144 pm), book. Therefore, for the sake of convenience,although in both the cases a single covalent valence bond theory has been discussed in bond is formed by the sharing of an electron terms of qualitative and non-mathematical pair between the respective atoms. It also treatment only. To start with, let us consider gives no idea about the shapes of polyatomic the formation of hydrogen molecule which is molecules. the simplest of all molecules. Similarly the VSEPR theory gives the Consider two hydrogen atoms A and B geometry of simple molecules but theoretically, approaching each other having nuclei NA it does not explain them and also it has limited and NB and electrons present in them are applications. To overcome these limitations represented by eA and eB. When the two atoms the two important theories based on quantum are at large distance from each other, there mechanical principles are introduced. These is no interaction between them. As these two are valence bond (VB) theory and molecular atoms approach each other, new attractive orbital (MO) theory. and repulsive forces begin to operate. Valence bond theory was introduced Attractive forces arise between: by Heitler and London (1927) and developed (i) nucleus of one atom and its own electron further by Pauling and others. A discussion that is NA – eA and NB– eB. Reprint 2025-26 118 chemistry (ii) nucleus of one atom and electron of together to form a stable molecule having the other atom i.e., NA– eB, NB– eA. bond length of 74 pm. Similarly repulsive forces arise between Since the energy gets released when the bond is formed between two hydrogen atoms,(i) electrons of two atoms like eA – eB, the hydrogen molecule is more stable than (ii) nuclei of two atoms NA – NB. that of isolated hydrogen atoms. The energy Attractive forces tend to bring the two so released is called as bond enthalpy, which atoms close to each other whereas repulsive is corresponding to minimum in the curve forces tend to push them apart (Fig. 4.7). depicted in Fig. 4.8. Conversely, 435.8 kJ of energy is required to dissociate one mole of H2 molecule. H2(g) + 435.8 kJ mol–1 → H(g) + H(g) Fig. 4.8 The potential energy curve for the formation of H2 molecule as a function of internuclear distance of the H atoms. The minimum in the curve corresponds to the most stable state of H2. 4.5.1 Orbital Overlap Concept In the formation of hydrogen molecule, there is a minimum energy state when two hydrogen atoms are so near that their atomic orbitals undergo partial interpenetration. ThisFig. 4.7 Forces of attraction and repulsion partial merging of atomic orbitals is called during the formation of H2 molecule overlapping of atomic orbitals which results in Experimentally it has been found that the pairing of electrons. The extent of overlap the magnitude of new attractive force is decides the strength of a covalent bond. Inmore than the new repulsive forces. As a general, greater the overlap the stronger is theresult, two atoms approach each other and bond formed between two atoms. Therefore,potential energy decreases. Ultimately a stage is reached where the net force of attraction according to orbital overlap concept, the balances the force of repulsion and system formation of a covalent bond between two acquires minimum energy. At this stage atoms results by pairing of electrons present two hydrogen atoms are said to be bonded in the valence shell having opposite spins. Reprint 2025-26 Chemical Bonding And Molecular Structure 119 4.5.2 Directional Properties of Bonds As we have already seen, the covalent bond is formed by overlapping of atomic orbitals. The molecule of hydrogen is formed due to the overlap of 1s-orbitals of two H atoms. In case of polyatomic molecules like CH4, NH3 and H2O, the geometry of the molecules is also important in addition to the bond formation. For example why is it so that CH4 molecule has tetrahedral shape and HCH bond angles are 109.5°? Why is the shape of NH3 molecule pyramidal ? The valence bond theory explains the shape, the formation and directional properties of bonds in polyatomic molecules like CH4, NH3 and H2O, etc. in terms of overlap and hybridisation of atomic orbitals. 4.5.3 Overlapping of Atomic Orbitals When orbitals of two atoms come close to form bond, their overlap may be positive, negative or zero depending upon the sign (phase) and direction of orientation of amplitude of orbital wave function in space (Fig. 4.9). Positive and negative sign on boundary surface diagrams in the Fig. 4.9 show the sign (phase) of orbital wave function and are not related to charge. Fig.4.9 Positive, negative and zero overlaps ofOrbitals forming bond should have same sign s and p atomic orbitals(phase) and orientation in space. This is called positive overlap. Various overlaps of s and p hydrogen. The four atomic orbitals of carbon, orbitals are depicted in Fig. 4.9. each with an unpaired electron can overlap with the 1s orbitals of the four H atoms which The criterion of overlap, as the main factor are also singly occupied. This will result in the for the formation of covalent bonds applies formation of four C-H bonds. It will, however, uniformly to the homonuclear/heteronuclear be observed that while the three p orbitals of diatomic molecules and polyatomic molecules. carbon are at 90° to one another, the HCH We know that the shapes of CH4, NH3, and angle for these will also be 90°. That is three H2O molecules are tetrahedral, pyramidal C-H bonds will be oriented at 90° to one and bent respectively. It would be therefore another. The 2s orbital of carbon and the 1s interesting to use VB theory to find out if these orbital of H are spherically symmetrical and geometrical shapes can be explained in terms they can overlap in any direction. Therefore of the orbital overlaps. the direction of the fourth C-H bond cannot Let us first consider the CH4 (methane) be ascertained. This description does not fit molecule. The electronic configuration of in with the tetrahedral HCH angles of 109.5°. carbon in its ground state is [He]2s2 2p2 which Clearly, it follows that simple atomic orbital in the excited state becomes [He] 2s1 2px1 2py1 overlap does not account for the directional 2pz1. The energy required for this excitation is characteristics of bonds in CH4. Using similar compensated by the release of energy due to procedure and arguments, it can be seen that in overlap between the orbitals of carbon and the the case of NH3 and H2O molecules, the HNH Reprint 2025-26 120 chemistry and HOH angles should be 90°. This is in above and below the plane of the disagreement with the actual bond angles of participating atoms. 107° and 104.5° in the NH3 and H2O molecules respectively. 4.5.4 Types of Overlapping and Nature of Covalent Bonds The covalent bond may be classified into two types depending upon the types of overlapping: (i) Sigma(σ) bond, and (ii) pi(π) bond (i) Sigma(σ) bond : This type of covalent 4.5.5 Strength of Sigma and pi Bonds bond is formed by the end to end (head- Basically the strength of a bond depends on) overlap of bonding orbitals along the upon the extent of overlapping. In case of internuclear axis. This is called as head sigma bond, the overlapping of orbitals takes on overlap or axial overlap. This can be place to a larger extent. Hence, it is stronger formed by any one of the following types as compared to the pi bond where the extent of combinations of atomic orbitals. of overlapping occurs to a smaller extent. • s-s overlapping : In this case, there is Further, it is important to note that in the overlap of two half filled s-orbitals along formation of multiple bonds between two the internuclear axis as shown below : atoms of a molecule, pi bond(s) is formed in addition to a sigma bond. 4.6 Hybridisation In order to explain the characteristic geometrical shapes of polyatomic molecules • s-p overlapping: This type of overlap like CH4, NH3 and H2O etc., Pauling introduced occurs between half filled s-orbitals of one the concept of hybridisation. According to him atom and half filled p-orbitals of another the atomic orbitals combine to form new set of atom. equivalent orbitals known as hybrid orbitals. Unlike pure orbitals, the hybrid orbitals are used in bond formation. The phenomenon is known as hybridisation which can be defined as the process of intermixing of the orbitals of • p–p overlapping : This type of overlap slightly different energies so as to redistribute takes place between half filled p-orbitals their energies, resulting in the formation of of the two approaching atoms. new set of orbitals of equivalent energies and shape. For example when one 2s and three 2p-orbitals of carbon hybridise, there is the formation of four new sp3 hybrid orbitals. Salient features of hybridisation: The main (ii) pi( ) bond : In the formation of π bond features of hybridisation are as under : the atomic orbitals overlap in such a 1. The number of hybrid orbitals is equal to way that their axes remain parallel to the number of the atomic orbitals that get each other and perpendicular to the internuclear axis. The orbitals formed hybridised. due to sidewise overlapping consists 2. The hybridised orbitals are always of two saucer type charged clouds equivalent in energy and shape. Reprint 2025-26 Chemical Bonding And Molecular Structure 121 3. The hybrid orbitals are more effective in vacant 2p orbital to account for its bivalency. forming stable bonds than the pure atomic One 2s and one 2p-orbital gets hybridised to orbitals. form two sp hybridised orbitals. These two sp hybrid orbitals are oriented in opposite4. These hybrid orbitals are directed in direction forming an angle of 180°. Each of space in some preferred direction to have the sp hybridised orbital overlaps with the minimum repulsion between electron 2p-orbital of chlorine axially and form two Be- pairs and thus a stable arrangement. Cl sigma bonds. This is shown in Fig. 4.10. Therefore, the type of hybridisation indicates the geometry of the molecules. Important conditions for hybridisation (i) The orbitals present in the valence shell of the atom are hybridised. (ii) The orbitals undergoing hybridisation Be should have almost equal energy. (iii) Promotion of electron is not essential condition prior to hybridisation. (iv) It is not necessary that only half filled orbitals participate in hybridisation. In some cases, even filled orbitals of valence shell take part in hybridisation. Fig.4.10 (a) Formation of sp hybrids from s and 4.6.1 Types of Hybridisation p orbitals; (b) Formation of the linear There are various types of hybridisation BeCl2 molecule involving s, p and d orbitals. The different (II) sp2 hybridisation : In this hybridisationtypes of hybridisation are as under: there is involvement of one s and two (I) sp hybridisation: This type of hybridisation p-orbitals in order to form three equivalent involves the mixing of one s and one p orbital sp2 hybridised orbitals. For example, in resulting in the formation of two equivalent BCl3 molecule, the ground state electronicsp hybrid orbitals. The suitable orbitals for configuration of central boron atom is sp hybridisation are s and pz, if the hybrid 1s22s22p1. In the excited state, one of the 2s orbitals are to lie along the z-axis. Each sp electrons is promoted to vacant 2p orbital as hybrid orbitals has 50% s-character and 50% p-character. Such a molecule in which the central atom is sp-hybridised and linked directly to two other central atoms possesses linear geometry. This type of hybridisation is also known as diagonal hybridisation. The two sp hybrids point in the opposite direction along the z-axis with projecting positive lobes and very small negative lobes, which provides more effective overlapping resulting in the formation of stronger bonds. Example of molecule having sp hybridisation BeCl 2: The ground state electronic configuration of Be is 1s22s2. In the exited Fig.4.11 Formation of sp2 hybrids and the BCl3 state one of the 2s-electrons is promoted to molecule Reprint 2025-26 122 chemistry a result boron has three unpaired electrons. ground state is 2S 2 2 p 1x 2 p 1y 2 p 1z having threeThese three orbitals (one 2s and two 2p) unpaired electrons in the sp3 hybrid orbitalshybridise to form three sp2 hybrid orbitals. and a lone pair of electrons is present in theThe three hybrid orbitals so formed are fourth one. These three hybrid orbitals overlaporiented in a trigonal planar arrangement with 1s orbitals of hydrogen atoms to formand overlap with 2p orbitals of chlorine to three N–H sigma bonds. We know that the form three B-Cl bonds. Therefore, in BCl3 force of repulsion between a lone pair and a(Fig. 4.11), the geometry is trigonal planar bond pair is more than the force of repulsionwith ClBCl bond angle of 120°. between two bond pairs of electrons. The (III) sp 3 hybridisation: This type of molecule thus gets distorted and the bond hybridisation can be explained by taking the angle is reduced to 107° from 109.5°. The example of CH4 molecule in which there is geometry of such a molecule will be pyramidal mixing of one s-orbital and three p-orbitals as shown in Fig. 4.13. of the valence shell to form four sp3 hybrid orbital of equivalent energies and shape. There is 25% s-character and 75% p-character in each sp3 hybrid orbital. The four sp3 hybrid orbitals so formed are directed towards the four corners of the tetrahedron. The angle between sp3 hybrid orbital is 109.5° as shown in Fig. 4.12. Fig.4.13 Formation of NH3 molecule In case of H2O molecule, the four oxygen orbitals (one 2s and three 2p) undergo sp3 hybridisation forming four sp3 hybrid orbitals out of which two contain one electron each and the other two contain a pair of electrons. These σ four sp3 hybrid orbitals acquire a tetrahedral geometry, with two corners occupied by σ σ hydrogen atoms while the other two by the lone pairs. The bond angle in this case is reduced to 104.5° from 109.5° (Fig. 4.14) σ and the molecule thus acquires a V-shape or angular geometry. Fig.4.12 Formation of sp3 hybrids by the combination of s, px , py and pz atomic orbitals of carbon and the formation of CH4 molecule The structure of NH3 and H2O molecules can also be explained with the help of sp3 hybridisation. In NH3, the valence shell (outer) electronic configuration of nitrogen in the Fig.4.14 Formation of H2O molecule Reprint 2025-26 Chemical Bonding And Molecular Structure 123 4.6.2 Other Examples of sp3, sp2 and sp used for making sp2–s sigma bond with two Hybridisation hydrogen atoms. The unhybridised orbital (2px sp3 Hybridisation in C2H6 molecule: In or 2py) of one carbon atom overlaps sidewise ethane molecule both the carbon atoms with the similar orbital of the other carbon assume sp3 hybrid state. One of the four atom to form weak π bond, which consists of sp3 hybrid orbitals of carbon atom overlaps two equal electron clouds distributed above axially with similar orbitals of other atom to and below the plane of carbon and hydrogen form sp3-sp3 sigma bond while the other three atoms. hybrid orbitals of each carbon atom are used Thus, in ethene molecule, the carbon-in forming sp3–s sigma bonds with hydrogen carbon bond consists of one sp2–sp2 sigmaatoms as discussed in section 4.6.1(iii). bond and one pi (π ) bond between p orbitalsTherefore in ethane C–C bond length is 154 which are not used in the hybridisation andpm and each C–H bond length is 109 pm. are perpendicular to the plane of molecule; thesp2 Hybridisation in C2H4: In the formation bond length 134 pm. The C–H bond is sp2–sof ethene molecule, one of the sp2 hybrid sigma with bond length 108 pm. The H–C–Horbitals of carbon atom overlaps axially with bond angle is 117.6° while the H–C–C anglesp2 hybridised orbital of another carbon atom is 121°. The formation of sigma and pi bondsto form C–C sigma bond. While the other two sp2 hybrid orbitals of each carbon atom are in ethene is shown in Fig. 4.15. Fig. 4.15 Formation of sigma and pi bonds in ethene Reprint 2025-26 124 chemistry sp Hybridisation in C2H2 : In the formation 4.6.3 Hybridisation of Elements of ethyne molecule, both the carbon atoms involving d Orbitals undergo sp-hybridisation having two The elements present in the third period unhybridised orbital i.e., 2py and 2px. contain d orbitals in addition to s and p orbitals. The energy of the 3d orbitals are One sp hybrid orbital of one carbon atom comparable to the energy of the 3s and 3poverlaps axially with sp hybrid orbital of the orbitals. The energy of 3d orbitals are also other carbon atom to form C–C sigma bond, comparable to those of 4s and 4p orbitals. while the other hybridised orbital of each As a consequence the hybridisation involving carbon atom overlaps axially with the half either 3s, 3p and 3d or 3d, 4s and 4p is filled s orbital of hydrogen atoms forming possible. However, since the difference in σ bonds. Each of the two unhybridised p energies of 3p and 4s orbitals is significant, no orbitals of both the carbon atoms overlaps hybridisation involving 3p, 3d and 4s orbitals sidewise to form two π bonds between the is possible. carbon atoms. So the triple bond between the The important hybridisation schemes two carbon atoms is made up of one sigma involving s, p and d orbitals are summarised and two pi bonds as shown in Fig. 4.16. below: Shape of Hybridisation Atomic molecules/ Examples type orbitals ions Square dsp2 d+s+p(2) [Ni(CN)4]2–, planar [Pt(Cl)4]2– Trigonal sp3d s+p(3)+d PF5, PCl5 bipyramidal Square sp3d2 s+p(3)+d(2) BrF5 pyramidal Octahedral sp3d2 s+p(3)+d(2) SF6, [CrF6]3– d2sp3 d(2)+s+p(3) [Co(NH3)6]3+ (i) Formation of PCl5 (sp3d hybridisation): The ground state and the excited state outer electronic configurations of phosphorus (Z=15) are represented below. Fig.4.16 Formation of sigma and pi bonds in sp3d hybrid orbitals filled by electron pairs ethyne donated by five Cl atoms. Reprint 2025-26 Chemical Bonding And Molecular Structure 125 Now the five orbitals (i.e., one s, three six sp3d2 hybrid orbitals overlap with singly p and one d orbitals) are available for occupied orbitals of fluorine atoms to form hybridisation to yield a set of five sp3d hybrid six S–F sigma bonds. Thus SF6 molecule has orbitals which are directed towards the five a regular octahedral geometry as shown in corners of a trigonal bipyramidal as depicted Fig. 4.18. in the Fig. 4.17. sp3d2 hybridisation Fig. 4.17 Trigonal bipyramidal geometry of PCl5 molecule It should be noted that all the bond angles in trigonal bipyramidal geometry are not equivalent. In PCl5 the five sp3d orbitals of phosphorus overlap with the singly occupied p orbitals of chlorine atoms to form five P–Cl sigma bonds. Three P–Cl bond lie in one plane and make an angle of 120° with each other; these bonds are termed as equatorial Fig. 4.18 Octahedral geometry of SF6 moleculebonds. The remaining two P–Cl bonds–one lying above and the other lying below the equatorial plane, make an angle of 90° with 4.7 Molecular Orbital Theory the plane. These bonds are called axial bonds. Molecular orbital (MO) theory was developed As the axial bond pairs suffer more repulsive by F. Hund and R.S. Mulliken in 1932. The interaction from the equatorial bond pairs, salient features of this theory are : therefore axial bonds have been found to (i) The electrons in a molecule are present be slightly longer and hence slightly weaker in the various molecular orbitals as the than the equatorial bonds; which makes PCl5 electrons of atoms are present in the molecule more reactive. various atomic orbitals. (ii) Formation of SF6 (sp3d2 hybridisation): (ii) The atomic orbitals of comparableIn SF6 the central sulphur atom has the energies and proper symmetry combineground state outer electronic configuration to form molecular orbitals.3s23p4. In the exited state the available six orbitals i.e., one s, three p and two d are (iii) While an electron in an atomic orbital singly occupied by electrons. These orbitals is influenced by one nucleus, in a hybridise to form six new sp3d2 hybrid molecular orbital it is influenced by orbitals, which are projected towards the six two or more nuclei depending upon the corners of a regular octahedron in SF6. These number of atoms in the molecule. Thus, Reprint 2025-26 126 chemistry an atomic orbital is monocentric while ψA and ψB. Mathematically, the formation of a molecular orbital is polycentric. molecular orbitals may be described by the linear combination of atomic orbitals that can(iv) The number of molecular orbital formed take place by addition and by subtraction of is equal to the number of combining wave functions of individual atomic orbitals atomic orbitals. When two atomic as shown below : orbitals combine, two molecular orbitals are formed. One is known as bonding ψMO = ψA + ψB molecular orbital while the other is Therefore, the two molecular orbitals called antibonding molecular orbital. σ and σ* are formed as : (v) The bonding molecular orbital has σ = ψA + ψB lower energy and hence greater stability σ* = ψA – ψB than the corresponding antibonding The molecular orbital σ formed by the molecular orbital. addition of atomic orbitals is called the bonding (vi) Just as the electron probability molecular orbital while the molecular orbital distribution around a nucleus in an σ* formed by the subtraction of atomic orbital atom is given by an atomic orbital, the is called antibonding molecular orbital as electron probability distribution around depicted in Fig. 4.19. a group of nuclei in a molecule is given by a molecular orbital. (vii) The molecular orbitals like atomic orbitals are filled in accordance with the aufbau principle obeying the Pauli’s exclusion principle and the Hund’s rule. 4.7.1 Formation of Molecular Orbitals Linear Combination of Atomic σ* = ψA – ψB Orbitals (LCAO) According to wave mechanics, the atomic ψA ψBorbitals can be expressed by wave functions (ψ ’s) which represent the amplitude of the σ = ψA + ψBelectron waves. These are obtained from the solution of Schrödinger wave equation. However, since it cannot be solved for any system containing more than one electron, molecular orbitals which are one electron wave functions for molecules are difficult Fig.4.19 Formation of bonding (σ) and antibonding (σ*) molecular orbitals by the linearto obtain directly from the solution of combination of atomic orbitals ψA andSchrödinger wave equation. To overcome this problem, an approximate method known ψB centered on two atoms A and B respectively.as linear combination of atomic orbitals (LCAO) has been adopted. Qualitatively, the formation of molecular Let us apply this method to the orbitals can be understood in terms of the homonuclear diatomic hydrogen molecule. constructive or destructive interference of the Consider the hydrogen molecule consisting electron waves of the combining atoms. In the of two atoms A and B. Each hydrogen atom formation of bonding molecular orbital, the in the ground state has one electron in 1s two electron waves of the bonding atoms orbital. The atomic orbitals of these atoms reinforce each other due to constructive may be represented by the wave functions interference while in the formation of Reprint 2025-26 Chemical Bonding And Molecular Structure 127 antibonding molecular orbital, the electron as the molecular axis. It is important to note waves cancel each other due to destructive that atomic orbitals having same or nearly interference. As a result, the electron density in the same energy will not combine if they do a bonding molecular orbital is located between not have the same symmetry. For example, the nuclei of the bonded atoms because of 2pz orbital of one atom can combine with 2pz which the repulsion between the nuclei is very orbital of the other atom but not with the less while in case of an antibonding molecular 2px or 2py orbitals because of their different orbital, most of the electron density is located symmetries. away from the space between the nuclei. 3. The combining atomic orbitals must Infact, there is a nodal plane (on which the overlap to the maximum extent. Greater electron density is zero) between the nuclei the extent of overlap, the greater will be the and hence the repulsion between the nuclei is electron-density between the nuclei of a high. Electrons placed in a bonding molecular molecular orbital. orbital tend to hold the nuclei together and 4.7.3 Types of Molecular Orbitalsstabilise a molecule. Therefore, a bonding molecular orbital always possesses lower Molecular orbitals of diatomic molecules are energy than either of the atomic orbitals that designated as σ (sigma), π (pi), δ(delta), etc. have combined to form it. In contrast, the In this nomenclature, the sigma ( ) electrons placed in the antibonding molecular molecular orbitals are symmetrical around orbital destabilise the molecule. This is the bond-axis while pi ( ) molecular orbitals because the mutual repulsion of the electrons are not symmetrical. For example, the linear in this orbital is more than the attraction combination of 1s orbitals centered on two between the electrons and the nuclei, which nuclei produces two molecular orbitals which causes a net increase in energy. are symmetrical around the bond-axis. Such It may be noted that the energy of the molecular orbitals are of the σ type and are antibonding orbital is raised above the designated as σ1s and σ*1s [Fig. 4.20(a), page energy of the parent atomic orbitals that 124]. If internuclear axis is taken to be in have combined and the energy of the bonding the z-direction, it can be seen that a linear orbital has been lowered than the parent combination of 2pz- orbitals of two atoms orbitals. The total energy of two molecular also produces two sigma molecular orbitals orbitals, however, remains the same as that designated as 2pz and *2pz. [Fig. 4.20(b)] of two original atomic orbitals. Molecular orbitals obtained from 2px and 4.7.2 Conditions for the Combination of 2py orbitals are not symmetrical around the Atomic Orbitals bond axis because of the presence of positive lobes above and negative lobes below theThe linear combination of atomic orbitals to molecular plane. Such molecular orbitals,form molecular orbitals takes place only if the are labelled as π and =π* [Fig. 4.20(c)]. Afollowing conditions are satisfied: π bonding MO has larger electron density1. The combining atomic orbitals must above and below the inter-nuclear axis. Thehave the same or nearly the same energy. π* antibonding MO has a node between theThis means that 1s orbital can combine with nuclei.another 1s orbital but not with 2s orbital because the energy of 2s orbital is appreciably 4.7.4 Energy Level Diagram for Molecular higher than that of 1s orbital. This is not true Orbitals if the atoms are very different. We have seen that 1s atomic orbitals on two 2. The combining atomic orbitals must atoms form two molecular orbitals designated have the same symmetry about the as σ1s and σ*1s. In the same manner, the 2s molecular axis. By convention z-axis is taken and 2p atomic orbitals (eight atomic orbitals Reprint 2025-26 128 chemistry Fig. 4.20 Contours and energies of bonding and antibonding molecular orbitals formed through combinations of (a) 1s atomic orbitals; (b) 2pz atomic orbitals and (c) 2px atomic orbitals. on two atoms) give rise to the following eight The energy levels of these molecular molecular orbitals: orbitals have been determined experimentally from spectroscopic data for homonuclearAntibonding MOs σ∗2s σ∗2pz π∗2px π∗2py diatomic molecules of second row elements Bonding MOs σ2s σ2pz π2px π2py of the periodic table. The increasing order of Reprint 2025-26 Chemical Bonding And Molecular Structure 129 energies of various molecular orbitals for O2 The rules discussed above regarding the and F2 is given below: stability of the molecule can be restated in terms of bond order as follows: A positive bond1s <  ∗1s <  2s <  ∗2s < 2pz < (π 2px=π 2py) order (i.e., Nb > Na) means a stable molecule < (π ∗2px= π∗ 2py) <  ∗2pz while a negative (i.e., Nb<Na) or zero (i.e., However, this sequence of energy levels Nb = Na) bond order means an unstable of molecular orbitals is not correct for the molecule. remaining molecules Li2, Be2, B2, C2, N2. For Nature of the bond instance, it has been observed experimentally Integral bond order values of 1, 2 or 3 that for molecules such as B2, C2, N2, etc. correspond to single, double or triple bonds the increasing order of energies of various respectively as studied in the classical molecular orbitals is concept. 1s <  ∗1s < 2s <  ∗2s < (π 2 px = π 2 py) Bond-length < 2pz < (π ∗2px =π∗2py) <  ∗2pz The bond order between two atoms in a The important characteristic feature molecule may be taken as an approximate of this order is that the energy of 2pz measure of the bond length. The bond length molecular orbital is higher than that decreases as bond order increases. of 2px and 2py molecular orbitals. Magnetic nature 4.7.5 Electronic Configuration and If all the molecular orbitals in a molecule are Molecular Behaviour doubly occupied, the substance is diamagnetic (repelled by magnetic field). However if one orThe distribution of electrons among various more molecular orbitals are singly occupied itmolecular orbitals is called the electronic is paramagnetic (attracted by magnetic field),configuration of the molecule. From the e.g., O2 molecule.electronic configuration of the molecule, it is possible to get important information about 4.8 BONDING IN SOME HOMONUCLEAR the molecule as discussed below. DIATOMIC MOLECULES Stability of Molecules: If Nb is the number In this section we shall discuss bonding in of electrons occupying bonding orbitals and some homonuclear diatomic molecules. Na the number occupying the antibonding 1. Hydrogen molecule (H2 ): It is formed byorbitals, then the combination of two hydrogen atoms. Each (i) the molecule is stable if Nb is greater hydrogen atom has one electron in 1s orbital. than Na, and Therefore, in all there are two electrons in (ii) the molecule is unstable if Nb is less hydrogen molecule which are present in σ1s than Na. molecular orbital. So electronic configuration of hydrogen molecule is In (i) more bonding orbitals are occupied and so the bonding influence is stronger and a H2 : (σ1s)2 stable molecule results. In (ii) the antibonding The bond order of H2 molecule can be influence is stronger and therefore the calculated as given below: molecule is unstable. N b  N a 2  0 Bond order Bond order =   1 2 2 Bond order (b.o.) is defined as one half the This means that the two hydrogen atoms difference between the number of electrons are bonded together by a single covalent bond. present in the bonding and the antibonding The bond dissociation energy of hydrogen orbitals i.e., molecule has been found to be 438 kJ mol–1 and bond length equal to 74 pm. Since no Bond order (b.o.) = ½ (Nb–Na) Reprint 2025-26 130 chemistry unpaired electron is present in hydrogen vapour phase. It is important to note that molecule, therefore, it is diamagnetic. double bond in C2 consists of both pi bonds 2. Helium molecule (He2 ): The electronic because of the presence of four electrons in configuration of helium atom is 1s2. Each two pi molecular orbitals. In most of the other helium atom contains 2 electrons, therefore, molecules a double bond is made up of a in He2 molecule there would be 4 electrons. sigma bond and a pi bond. In a similar fashion the bonding in N2 molecule can be discussed.These electrons will be accommodated in σ1s and σ*1s molecular orbitals leading to 5. Oxygen molecule (O2 ): The electronic electronic configuration: configuration of oxygen atom is 1s2 2s2 2p4. Each oxygen atom has 8 electrons, hence, He2 : (σ1s)2 (σ*1s)2 in O2 molecule there are 16 electrons. The electronic configuration of O2 molecule, Bond order of He2 is ½(2 – 2) = 0 therefore, is He2 molecule is therefore unstable and does not exist. O2 : (1s)2 ( ∗1s)2 ( 2s)2 ( ∗ 2s)2 (2pz)2 Similarly, it can be shown that Be2 molecule (π2px2 ≡ π2py2) (π∗2p1x ≡ π ∗2py1) (σ1s)2 (σ*1s)2 (σ2s)2 (σ*2s)2 also does not exist. 3. Lithium molecule (Li2 ): The electronic O2 :configuration of lithium is 1s2, 2s1. There are six electrons in Li2. The electronic configuration of Li2 molecule, therefore, is From the electronic configuration of O2 molecule it is clear that ten electrons are Li2 : (σ1s)2 (σ*1s)2 (σ2s)2 present in bonding molecular orbitals and six The above configuration is also written electrons are present in antibonding molecular as KK(σ2s)2 where KK represents the closed orbitals. Its bond order, therefore, is K shell structure (σ1s)2 (σ*1s)2. From the electronic configuration of Li2 Bond order = [Nb – Na] = [10 – 6] =2 molecule it is clear that there are four electrons So in oxygen molecule, atoms are heldpresent in bonding molecular orbitals and two by a double bond. Moreover, it may be notedelectrons present in antibonding molecular that it contains two unpaired electrons inorbitals. Its bond order, therefore, is ½ (4 – π∗2px and π∗2py molecular orbitals, therefore,2) = 1. It means that Li2 molecule is stable and since it has no unpaired electrons it O2 molecule should be paramagnetic, a prediction that corresponds toshould be diamagnetic. Indeed diamagnetic experimental observation. In this way, theLi2 molecules are known to exist in the theory successfully explains the paramagneticvapour phase. nature of oxygen. 4. Carbon molecule (C2 ): The electronic Similarly, the electronic configurationsconfiguration of carbon is 1s2 2s2 2p2. There of other homonuclear diatomic molecules of [ ]are twelve electrons in C2. The electronic the second row of the periodic table can be configuration of C2 molecule, therefore, is written. In Fig. 4.21 are given the molecular C2 : (1s)2 ( ∗1s)2 ( ∗ 2s)2 (π2p2x = π2p2y) orbital occupancy and molecular properties for B2 through Ne2. The sequence of MOs and or KK (2s)2 ( ∗ 2s)2 (π2p2x = π2p2y) their electron population are shown. The bond energy, bond length, bond order, magnetic The bond order of C2 is ½ (8 – 4) = 2 properties and valence electron configurationand C2 should be diamagnetic. Diamagnetic appear below the orbital diagrams.C2 molecules have indeed been detected in Reprint 2025-26 Chemical Bonding And Molecular Structure 131 Fig. 4.21 MO occupancy and molecular properties for B2 through Ne2.