CHAPTER Gaseous State Introduction Under a specific condition of temperature and pressure most of the substances can exist in any one of the three states of matter —solid, liquid or gas. For example, ‘water can be in the solid (ice), liquid and in gaseous states (steam). Physical properties of a substance depends upon its state Understanding properties of gasoous state of matter is rather simple (the subject-matter of this chapter) than, the liquid or solid states in several ways. Molecular motion in ga8es, is totally random. The force of attraction between the gas molecules is negligibly small due to large separation between them and therefore, a olecule moves freely and essentially independently of the another molecule. The effect of change in state parameters, e.g. temperature, pressure etc, on the behaviour can easily be Predicted for gaseous state than for other states of matter. Various laws, e.g, ideal gas law, kinetic theory of gases te, have played a significant role in the development of the atomic theory of matter, which further simplified the study of this state of matter, Discrepancy observed between the measured value of state parameters and the same calculated from mentioned Learning Signposts P * Temperature and pressure *The ‘Ideal’ gas * Lifting capacity of a gas-filled balloon *Gas density "Molar volume of a gas = Mixture of gases : Dalton’s law of partial pressure Effusion/diffusion of gases and Graham's law = Kinetic molecular theory of gases = Maxwell's distribution of molecular speeds = The ‘teal’ gas van der Waals’ equation of state — “An analytical view" Scanned with CamScannerjt Jaws were explained after the advent of a os oat and several modiiations a air i er to teed ave ‘and calculated values of the same perma Smoot tho genoral characteristics gaseous Dato of maltr are as fllows Gases ie fa) assume the volume and shape of conta {b) romost compressible ofthe states of mater {6} will mix evenly and completely when confined to the same container = (a) have much lover densities than liquids and solids Temperature & Pressure Temperature Gelsius scale of temperature divides the range between freezing point (0°C) and boiling point (100°C) of water into 100 degrees. The SI unit of temperature is Kelvin. Kelvin scale isthe absolute temperature scale. By absolute, we mean that the zero on Kelvin scale is the lowest temperature that can be attained theoretically. On the other hand zero on any other scale is based on the behaviour of arbitrarily chosen substance e.g., water, Both the celsius and the Kelvin scales have units of equal magnitude that is one degree of celsius equivalent {0 one Kelvin. Experimental studies have shown that absolute zero on Kelvin scale is equivalent to -273,18°C, on the celsius scale. Thus, these two temperature units are related by the expression, K=(C-+273.15) 41) Pressure of a gas. Gases exert pressure on the surface with which they ‘ome in contact because gaseous molecules are moving randomly and when they strike to the surface in contact, exert pressure. We human beings have adapted so well Phystologically to atmospheric pressure that we are ‘usually unaware of it, perhaps as fish are not conscious of tho water pressure on them. To ‘demonstrate the existence of atmospheric ‘Pressure, Jet us consider a common example from évery day life, our ability to drink.a liquid through a strav. Sucking air out of the straw reduces the pressure inside the straw. The greater atmospheric pressure on the liquid phase pushes itup into the straw enabling us to drink that Tiquid. its of Pressure: Pressure is one, of the moat yuently required properties of gas which we wish to femurs oriuelen cringe amy ie as force applied on unit surface ares: >>| Pressure = Fotee ‘Area i From the above equation (4.2), the ung derived using ST unit of force and ara ig nt “ay, P= Newton (N)/(meter)? = Nm? The SI unit of pressure is the pascal he ‘one Newton per square metre: 1.0 Pa = 1 Ny Atmospheric Pressure: Atmospherig equal to the pressure exerted by the earth’s atnoget The actual value of atmospheric pressure depend temperature, location and weather conde Atmospheric pressure is measured using an intra called barometer. The most common ang tig barometer consists of a long glass tube, closed toma and filled with mercury. Ifthe tube is carefully inverted in a dish of, 0 thet no air enters into the tube, some mex Come out ofthe tube into the dish creating vacuum at top as shown in the Fig. 4.1. Atmospheric Pressure acy on the surface of mercury dish supports the weight ot ‘mercury remaining in the tube. cy, cu i Fig-441, Barometer, measuring atmospheric pressure Standard atmospheric pressure (1.0 atm) ison the pressure that supports a column, of mercury exactly £2 (760 mm) helgh at O° at sea level. The mum unit pressure is also called “torr”, thus, 10 atm = 760 mm of ig Atmospheric pressure if pressure) as 1.0 atm atmospheric prsrue wheres ee ‘sed to measure pressure above atmosry manometer i eric pressure, Essential Physical Chemistry Scanned with CamScanner~—_ 71! ! os ind Manometer Fig. 4.2(b) Open-end Manometer ised ) ck "Here Pooe™ Ph Pare e429) ore Dyn = Ph all barometers and most of the manometers mercury as te working fluid, despite the fact that it is ssomoreutfance with a hermful vapour. The reason ‘oxi puss that mercury has a vory high density (13.6 eh compared 10 most other liquids. Since, height of umn holding liquid is inversely proportional to the cong density, this property enables the construction of lat agoably small barometers ‘and manometers. 1. Dibuty! phthalate is an alternative liquid to stance 2 Pe dme manometer. What pressure is uy nee toa contimetre of this Tiuid if density i Nearly explanation P = hpg = (10°? m) x (1.0465 x 10° kg m™) x10 = 102.63 Nm* Pressure Variation with Altitude |sparometric Distribution Law” ‘The pressure of atmosphere ‘decreases with altitude. Boltzmann's tistrbution law allows us to derive a simple but useful relationship beeen pressure and altitude jsssuming temperature to be constant. |Alongh temperature does not remain constant with altitude, this theory fumed out to be useful one giving @ ough estimate of pressure at different ‘ltude, To understand it let, us consider an imaginary vertical column | ftirabove an area on the surface of |arth as described in the Fig. (4.3) ag peal energy “U" of a molecule fy bit from the sunface is given U=mgh Whore mi i lon is mass of a molecule and g is the acceleration fen? S8vily. Let there bo NV air molecules present in bet increment, Since, 4 is infinitesimally enough. s0 stant betwoon hand potential enorgy is essentially c (hah. From Boltzmann's laws, Nengrnett 4.3) where N, is the total number of molecules between hoight 0 (ground) to A, Since, pressure is directly: proportional to the number of molecules at a fixed tomporature and prossur: p= pelt = pet [: @-S) ‘nivna gas constant] og vaf.A) Instance 2 Determine atmospheric pressure at a height of 3.00 km from the earth's surface assuming temperature to be Constant, and it is 298 K. Average molar mass of air is 28.8 u. g = 9.78ms~. Explanation p= p, exp(-mgh/RT) po exp[-26.8 x 107 x9.78 x 2000/8.314 298) .71P Note : since temperature of atmosphere aso varies with altitude, the Dredictions of the above equation should be accepted with ‘caution The ‘Ideal’ Gas Inorder to describe a gas, four variables e.g., pressure, temperature, volume and ‘amounts’ are required. Several scientists have studied the effect of changing one of the above-mentioned variebles on other as demonstrated in the form of certain experimentally derived laws. Important contributions in this regard are by Boyle, Charles, Gay-Lussac and Avogadro. A combination of their observations establishes relationship among the above-mentioned variables as pV = nRT (4.9) Eq, (4.5) is the common Ideal gas equation and the gases obying above equation of state are known as ideal gasos. R in the above equation is @ constant, called ‘universal gas constant and its value in different units are (R= 8.314 JK tol”? (i R= 0.0821 L. atm K* mol (iif) R = 2.0 cal K* mol Boyle’s Law Robert Boyle showed that the volume of air trapped by a liquid in the closed short limb of a J-shaped tube decreased in exact proportion to the pressure produced by cannoe @ Scanned with CamScannerJiquid mercury in the long part of the tube as shownin the Fig. 4.4. Gas Gas Gas Goof h a ae) Oo) @ @ Fig. 44 Apparatus used by Boyle for studying the relationship between pressure and volume ofa fixed amount of gas at a given temperature. (a) The pressure of gas is equal to atmospheric pressure. The pressure exerted by the gas increases from (a) to (4) as mercury is added and the volume of ‘gas decreases In the Boyle's experiment, the trapped air acted like a spring, exerting a force opposing its compression. On the basis of the above observations, the Boyle stated his law as “Fora fixed amount of gas, at a constant temperature, the product of pressure and volume is constant”. Boyle's Law: pv=K (4.8) and K = f(T, n), where T is temperature and n is amount of gas expressed in mole unit. Eq, 4.6 is an equation of inverse proportionality; any change in the pressure is exactly compensated by an opposing change in volume. As the pressure decreases towards zero, volume will increase infinitely and vice versa, A plot of pressure of an ideal gas as a function ofits volume yields a plot whose form is that of a rectangular hyperbola. There will be a separate p-V plot for each temperature and a single p-V plot is called an isotherm as shown in the Fig. 4.5 vom Fig. 4.5. Variation of volume with pressure at different temperature intext Q.1 Make plots ofp vs Vfor1.0 mol Nj(g) at same temperature. IntextQ.2 For a given amount of gas, at @ Answer. (a) PY es > Intext Q. 3 If the long arm of a closed end manomtt Answer The observed pressure obtained from height df| column of mercury, 8.00 cm long in a capillary tube of uniform. temperature, make the following plots (a) PV sp) pry (@)log pvs Tog (xox) &) P 4 () er me jog V ‘contains some water droplets adhered to the inner wall what wil be its effect on observed pressure? Hig would be less than the actual pressure. Instance 3. A 10.00 cm Jong column of air is trapped by 2 bore when the tube is held horizontally in a room at 1.0 ait pressure as shown below: [Ss on Sam What will be the length of air coh ! of air column when the tube i held (a) vertically with the open end up? (b) with the open end down? (Catan anglof45 fro vertical with the open endept Explanation The laboratory pressure is ie Oat = 760mm If the cross-sectional area of the bore of tube i the volume of trapped airof length Iwill be ney Now applying Boyle's law: aM =P = PLA = pba S Bah = Pal, Scanned with CamScannerdifferent situations are Te ealy inthe following Figur om ‘ ae" L. described 5 a] l= g é 3| (e)por= Pom * Pi (©) Pac= Pan Pr (©)Por= Pam Pra Incase of (8) ‘pressure on air column = 760 + 80/= 840 mm Pil, = Paley and 760 x10 =840 1, s 1, =9.047¢m Hence, length of air column in (a) is 9.047 cm. Incase of), plait) = 760-80 = 680mm = 1, =760 x 10/680 =11.18 cm Incase (0), fective height of Hg coluinn = 8 sin 45 = 6.657 cm ait) =760 + 56.57 =816.57 mm = 1, =760 x 10/816.57 =9.3 em Instance 4 A device used for measuring low pressure in vacuum stem is shown inthe figure below. As the mercury is drawn nto the gauge, a fed volume of gas (V bul) is trapped inthe bulb and compressed into a capillary tube at the top of Seta The wo distance h and hs are measured be 3 ‘and 82 mm, respectively. If Viyy is 100 cm® and radius of tecipryis 28 nen desea pressure gos eld 0 te bulb originally. Explanation Initial volume of gas = Volume of bulb: (a) = 100 em? Volume of gas when prosent in capillary = nth, = n(0.026 ci) 9.9 cm =6.87 «10° on? Applying Boyle's law to the gas, 100% Py =6.87 107 (h, +) 117 x 6.87 x10 kee =8.0379 x 10 mm_ 101325 760 ‘P(gas) = =1.07 Pa 3.0379 x10"? x Instance 5 A commercial gas cylinder contains 75 L of He at 15 bar (Gauge pressure). Assuming idea! gas behaviour for the isothermal expansion, how many 3.0 L balloons at 1.1 bar ‘pressure can be filled by the gas in the cylinder? Explanation Assuming atinospheric pressure to be one bar, initial pressure and final pressure of He gas present in cylinder will py=15+1=16bar and py 1-1 bar ‘Volume of He gas when expanded isothermally to 1.1 gine: a0 7804 at 1a Out of 1001, 781 of gas will remain in eylinder since at this point pressure equilibrium will be established. 100-75 _ 349 3 Instance 6 A.diverat a depth of 50 m exhales a bubble of air that is 1.0 cm in radius. Assuming ideal gas behaviour, what will be the radius of air bubble as it bursts atthe surface of water? Explanation Volume of air bubble at the depth of 50 m =p =4i8en. Pressure acting on alt bubble at a depth of $0 will be equal to the pressure exerted by water plus atmospheric pressure: (60 m) = hpg +1 =50 x10" 10 x = No. of balloons 41 101325 9346 atm Now apply AV (at 80 m) = pi (atthe suiface) : 4 410 x6.0340 71%; =¥ = 24.8 on? =n? oor = 8m Instance? A 1.1 L flask containing nitrogen at a pressure of 710 mm is connected to an evacuated flask of prknown volume. The nitrogen, which acts ideally is Sllowed to expand into the combined system of both the asks isothermally. If the final pressure of nitrogen is J33 mm, determine the volume of evacuated flask. Explanation Applying Boyle's law: | pV; = Pa¥s 3 7ioxid=5890.1+V)=V=0.24L Gasedus State © Scanned with CamScannerCharles’ law Charles studied the effect of temperature on volume of a given amount of gas under a constant pressure. According to Charles’ law, “Volume of a fix mass of gas in a container at constant Pressure is directly proportional to the absolute temperature” Charles’ law or V (@+273) where® the temperature is in °C. or VeT; (T=0+273) ofA.) Fig. 4.6 shows two aspects of the Charles’ be law. According to the ih above graphical Presentation, all gases must contract to zero Volume at absolute zero, which is not true, since ‘gases can be liquefied as ‘well as solidified and hence, occupy some volume even at absolute zero. The dotted lines in Fig. 4.6 clarify this ambiguity. ‘As we decrease the temperature, the volume of gas contracts and acquires minimum value at some temperature and pressure, shown by the end of solid lines in the above figure. Volume corresponding to the beginning point of solid lines in the above figure is the minimum volume, which a fixed amount of gas can occupy at a given pressure. On further lowering of the temperature, volume doesn’t change below this temperature, i.e., gases have become incompressible. One such case shown in Fig. 4.6 the variation of volume of a fixed amount of gas at pressure ps, against temperature, indicates that Vo is the minimum volume of gas at Tp. Below this temperature To, volume remains practically unchanged. At this point, if the line is extrapolated, it would meet to 0°K on x-axis as shown by dotted lines. OK To OC T—> Fig. 4.6 Variation of volume vs temperature Avogadro's hypothesis Accor to Avogadro's hypothesis, “at same ici pressure, equal volume of gases contain equal number of gas molecules, irrespective of their nature" i.e., V «nat same Tand p 4.8) ave) eure) (uTe) SOG) (wp) Gy Combined gas law The observations made by poy), Avogadro together (equations 4.6, 47) Chay, combined to give the following qn) ®™ 1) combined gas equation for ideal gasox. ha } pV =nkT ' Fig 48. p, Vand Thehaviout of an ides! gas. Boch it the surface reprosents a possible combinaton of p, Vandre ‘an ideal gas. The three sets of lines inscribed on the comespond to states in which one of these variables anh constant. The curved lines being lines of constant tempenay ‘isotherms. The long dashed lines are isobars at co presrure. The short dashed lines are isochores at en ee | es Q.4 Explain why a gas filled balloon contnud) night? Answer The temperature at night is usually lowertin the day temperature. Volume of a fixed amount of gas, given pressure is linearly related to temperature, there) ime of a balloon decreases in night. | Intext Q. 2. State whethe wit i moter a gaat ether each ofthe following sampled (@) Amaterial is in steel tank at 100 t ; eel tank at 100 atm pressuze. Wheat, eran Bete" 16 atmosphere, the material immed ere i etesing ts volume many fold. | ad Fate fal on being emitted ‘from. an_ industid) clear sky, it hess eeu 10 m into the aix, Viewed agai :ithas a white appearance, (G10. ofmateril weighs 2.6 evel of ake oil 2lease from a point 10 m below ak nbn et tee rapidly to the surface ali (e) A material is troy Sf He (One cubic take parent and, Pale green in colour jnolecutes ag am? og ry Of ne, material contains as ml pressure. f ait at the same temperature Answer (a) Gas (1 nsuthicient (2 Rete rata Intext Q.3 Could the a formation (6) Gas uted fora defining ot ei ted for ‘a definite ‘mass jt ‘number of moles't '¢ statement of Boy! Answer ee volt same Tand| Fig. 4.7. Variation of volume with amgunt at same T and P _ Yes, 8 definite SSINOI as detinte oe Essential Physical Chemisty Scanned with CamScannerat_mass of ammonia will exer sam ‘whe 00 8 S(g) is the sam tance on of HSE) container Inte ons of tomperature? inde the aro ! ation Under identical conditions of and ¥, pw» 7 explant al moles of ammonia as that of H,S(g) will exe, is - ,,when confined in the same contaings 88 Pe joles of H,S = 12/34 = moles of ammonia > s4ass of ammonia = (12/34) x17 = 6 g 9 5g ofa gaseous mixture of He and Ar conta a stance 8 Jat 27°C exert a pressure of 1.0 toate 503000 Tass percentage of He in the mixture, janation Lotthemixture containsxg of He and (5 xjg oe ane ‘Moles of gases W452, BV 1x10 “4" 40 — RT 0.082 x300 soling x=1.25 > welght of Ho = 25 .ce10 12.00 g of @ gaseous mixture of He and sta was token in a container and to the mixture 8.00 g of 's was added at same temperature. The pressure ihe container increased by a factor of 7/8, What was the einepercentage of methane in the original mixture? gxplanation Since, volume and temperature are constant thre and after addition of oxygen gas, nep Let if'x moles of gases were present in the 12.00 g nivtur of methane and helium at pressure p,, then x= Dp and = Hence, x =1.5 Now, ifthe mixture contains m g of methane, then 46° 4 3 m=B and weight percentage of 8 + x100=66.67 CH, = 5 x Instance 11 Two flasks of equal volume, connected by a ‘anow tube of negligible volume contain 1.0 mol of H, gas 41300 K and 0.5 atmosphere. Now one of the flasks is ‘nnersed into a thermostat maintained at 400 K and other smalntained at constant 300 K temperature. Determine «pressure and amount of H, gas in each flask. epanation Initially, both the flasks contained equal OfHA() ie, 0.5 mol each, (Avogadro's law). On heating one of the flasks, keeping other at constant ‘enperature, Kinetic ‘energy of the gas molecule present in the hotter flash colder feak atk ll crouse and they wil migrate towards aks ase eatin will bo re-established when the two quire a constant uniform pressure and at equilibri In hotter Nag tf Bas Wil bo more in colder flask than Inlalconditons : 0.6 mol, 0,6 atm 0.5 mol, 0.6 atm 300K 300K Final conditions: emo, p atm mol p atm 300K 400K (On applying gas equations in final conditions: 300x = 4009 Also, = Now, apply gas laws on flask A in its initial and final conditions : 9598 . paxadatm Realy Instance 12 A flask containing some Hé gas at 1.5 atm and 300 K is connected to another flask, four times larger in volume containing nitrogen gas at same temperature and pressure by means of a narrow tube of negligible volume. The ‘bigger flask was then kept in a thermostat bath maintained at 500 K; while other flask was maintained at constant 300 K. Determine the final pressures. Explanation Since, initially gases are at sainé temperature and pressure, if there is x mol of He gas, moles of N,(s) = 4x (Avogadro's law) ¥ ay \ i Final conditions: my, 300 Kp ra, 800K. p Applying ideal gas laws Ge), - Ga) at), at), 5 v ( av. ) me i xa00); “| x800),, 12m _17 Also, me ment dense + 20 91 25x = ae 7 Now, applying ideal gas law on flask I, before and after heating. Gaseous State @ Scanned with CamScanner18x ox ne Bx, fod 25x Pon 25 X25 7 w 25 Pp 2.2 Instance 13 A flask containing air was heated to 400 K, sealed and cooled to 300 K. The flask was then immersed in water bath and picked up so that 80 mL. of water was sucked ‘in. Determine the volume ofthe flask. Explanation Once the flask is sealed at 400 K, both frlume and moles become constant. On cooling the scaled Sask, pressure inside the flak will decrease, When a holes made in the flask by pricking, some water will be socked inside to decreaso the available volume for air, so that it Tegains the original pressure, Therefore, 7 =Constant V__v~so 400 “300 Instance 14 A gaseous mixture density of 0.846 git at 300 K and Percentage of Ar in the mixture. = V=300mL of CH, and argon has 1.0 atm. Detormine weight Explanation Let us consider 10 L of the mixture ‘Weight of mixture = 8.46 g.Ifmixture contains xg of Ar, then, *,848-x_ 10 40°46 “0082x300 => X=3.26g and weight 9 of Ar 100=38.53 Instance 15 40 g of an ideal gas was confined in a 1.0 L Alask at 1.0 atm. Increasing temperature of flask by 30°C increases gas pressure by 8 9. Determine molar mass of gas, Explanation Let the initial temperature be, TK. Since, n and Vare constants Leo ra as = 7=357K Peri Pat = Aad yas M 0082x375 Instance 16 A compound of P and F was analyzed as follows: Heating 0.2325 g of compound in a 378 ml. container ‘umed all ofitinto gas, which had a pressure of97.3 mm of Hg at 77°G. Then the gas was mixed with calcium chloride solution which tamed all the F to 0.2631 g CaF, Determine the molecular formula of compound. Explanation Number of moles of gas = BY ,_973x0378 5 a6 5.19 RT ~ 760 x0.082 x350 0.2324 = Molar mass of gas 2197.84 1.686 x10" 3 ‘Also weight of F in 0.2631 gCak, = x08 oo, ty => Weight of P in 0.2324 g of gas 4 .2324- 0.128. Empirical formula of gas P F Weight 0.1044 0.2044 Moles = Simple ratio 1 a 19 “Ong” Empirical formulais PF, and empirical formula wig, =H No, of empirical formula unit in a molecule 137.84 = 19784, 62 Hence, molecular formula = PF, Instance 17. Determine the volume of air in izes ring at 35°C and 790 mm of Fig to burn completely 250 g of ethane, Assume that air is 21 per cent O, by volume. Explanation The balanced . chemical reaction ie combustion of ethanol is CaHOH+ 30,(g) —s 2C0,(g) + 34,010) Males ethanol tobe buat = 282 4 Moles of oxygen required for combustion = 3 xmolesal ethanol = =O Volume of O,(g) required = 750 *0.082 5308 x76 468x790 96.14 Volume of air, which will contain the above volume of oxygen =396,14 x » =1886.38L Instance 18 (a) What volume of ai lume of ar at 1.0 atm and 22°C needed to fil « 0.98 L bicycle tye tn theseme erga E BIC te toa pressure of 80 aim (©) The tre is pumped by fi rato etc ofeondgc compressing the gas inthe cylinder, adding all the air in cylinder eg oe oe 828 Explanation (a) Here, 5.0 atm is the a ‘which is difference between the pres? in th Gre. and atmospheric pressure. Before filing pest oe 40 athe ptey snes Gat i de tee pressure is 5.0 atm, is 6.0 atm, Bat 98 x8 =5.88 1, (Volume of hand pump cylinder ~ 0 9.93 = 0.32941 After thro comploto stoke, volume of ar sige = 0.8234%3 = 0.970, Essential Physical Chemistry Scanned with CamScannerjifting Capacity of a Gas-Filled \palloon when balloon is filled with a gas lighter then airit due to difference in the density of gas and air, capacity of a balloon is determined as é ing capacity (pay-load) = Weight of air — (weight of gas present in same volume at same T’and p) ~ weight of balloon. (4.9), ise 119 Determine payload of a 100,000 L balloon stan (Balth He goat 27°C and 1.0 ot. Composition of air can pe onsidered to be 70% Nz and 219% O, by volume and falloon is massless. Explanation Moles of gas present in balloon wil pV __1000000 RT ~ 0.082 x300 ‘m{(payload) =Waie —W gas = 40850.4 (Mase ~ Miss) 8 0850.4 = SOSSE (28.84 - 4) kg = 1009.71 ooo dks 19.75 kg 40650.4 Instance 20 What temperature difference should be ‘maintained in a hot air balloon to lift 1.0 kg of mass? Volume sftheballoon is 100m, the temperature of ambient airis 27°C and pressure is 1.0 atm. Average molar mass of air is 29 g. Explanation. For a hot air balloon, payload (Am), is determined by subtracting the mass of hot air from the mass cfcold ar that is displaced by the balloon. ‘Am = mig ~ Mo = (aa ~ Prot) M __1x6.314 __ 300 10° x100 x29 x10" =3.3x10° Tat = 302.6 K = 29.6" gga 302.8 K =20.6°C, required temperature Gas density k anideal gas, py = nar = “AE Instance 21 Dotermino the density of carbon dioxide gas at the sublimation temperature of -78°C and 1.0 atm, assuming ideal behaviour of the gas. Explanation p= 2M ._1%44 1X44 75 git AT ~ 9082x105 ~*7° 8 Molar Volume of a Gas Standard Temperature and Pressure (STP) ‘The set of conditions 7'= 0°C, (273K) and p = 1.0atm is known as standard temperature and pressure, denoted as STP, Substituting these conditions into ideal gas equation and solving for volume of 1.0 mol of an ideal gas, yields 22.414 L (= 22.41). The standard molar volume of an ideal gas, 22.4 L mol”, is a value worth memorising but remember also that itis valid only at STP. Instance 22 Estimate the average distance between the centres of the molecules in a gas at 1.0 atm pressure and 0°C. Explanation Consider a 1.0 cn? volume of the gas, which will contain £:023%20" 4 9 22400 given sot of conditions. The effective volume occupied tne gas molecule is just reciprocal ofthis or 3.72 x10 cur. Considering that molecules are uniformly distributed, so that each occupies an imaginary box having this volume. The average distance between the centres of molecules will now be defined by the length of this box, which is the cube root of the volume per molecule. d= (6.7210) =3.98 x10 em=3.38 nm. 169 x 10"® molecules ‘under Mixture of Gases : Dalton’s Law of Partial Pressure ‘The ideal gas equation pV = nRT applies to mixtures just as to pure gases. It was in fact with a gas mixture, ordinary air, that Boyle, Gay-Lussac and Charles did their arly experiments, The only new concept we need in order to deal with gas mixtures is the partial pressure. ‘The pressure exerted by a gas depends on the force exerted by each molecular collision with the walls of the Container and on the number of such collisions in a unit of area per unit time. If a gas contains two types of molecules, each species will engage in such collisions tad thus, make a contribution to the total pressure, in exact proportion to its abundance in the mixture. The contribution that each species makes to the total pressure Gf gas is known as the “partial pressuro” of that spacies. Therefore, in other words, “partial pressure of a ‘component gas, in a gaseous mixture, is the pressure that crould have been exerted, had the said component Sreupied the entie volume alone under identical conditions of temperature.” An illustration of partial Scanned with CamScannerB “A+B+O goed he —> { 45mol Hore are shown, A, B and C, the three different gases contained in three container of equal volume at same temperature, with their individual pressure 1.0, 1.5 and 2.0 atm, respectively. When these gases are mixed and confined in.another container of same volume at same temperature, their individual pressure are added to give a total pressure of 4.5 atm. Therefore, the partial pressures of components A, B and C in the mixture are 1.0, 1.5 and 2.0 atm, respectively. Dalton’s law is based on this observation and states “In a non-reacting gaseous mixture, the total gas pressure is the sum of the partial pressure of. individual components". Thus, if a gaseous mixture contains “n” different types of gases and exert a total pressure p, then 2, Pi P=Pit Prt Pat 4 Pa= 2, 4.11) Also, according to ideal gas equation, pen => pen, = Pe = t= mole fraction (x) pon = Pi= MP (4.12) “partial pressure of a component = Mole fraction of that component (x,)x total pressure.” ‘Also, according to Avogadro's law: ne V at same temperature and pressure. as Vi = volume fraction (Vj) nV oxy piaVp ss (418) Mixing of non-reacting gases at same temperature (4 pu T ‘As shown in the above diagram, A ae Q shasta different types of non-reacting gases, present at pres ‘pi and pz in containers of volume V; and Vz respetivoly, but at same temperature, When gases or allowec ie raix-up by opening the stop clock, available volume ot each gases A and B increases to Vi + Vv, and teetaate, {hoir partial pressure in the mixture decreasos according to Boyles’ law as piVi= PalVs+¥2)» and PVs = palVs ae ap of Aan Where p4 and pp are the partial pressures nthe mixture, respectively. Now the total gs Ps=7° ‘ill be the sum of these two partial pressures 2 Pes Vas iV; P= Pat Pp = Pt V,4V, Hence, in general for mixing of gases pressures and volumes but at same temper PV = Pav + PV + PVs +..+ py, = pv= 2 pM m| where p is the total gas pressure in the combined, gna Vis sum of the volume of gases to be mie, "* righ = lel leo, , La T 7 PV = PaVa + PaVo + PcVe + PoVo ——___ Pa Intext Q.1 How, molar volumes of different goes related at any fixed temperature and pressure? Answer They ‘will be same because molar tc: depends on temperature and pressure, not on seen gas. Intext Q.2 Why Dalton’s law is applicable on non-reacting gaseous mixtiire? Answer Dalton’s law uses ‘conservation of principle which is non-applicable in case*of chenia) reactions, | Intext Q. 3 Why it is difficult to immerse vertical vi ‘open end down, a beaker into a bucket full of water? Answer Ai is | ponmeitiie gma oem Instance 23 “Calculate partial pressure of nitrogen #! oxygen in air assuming it to be composed of mostly nite and oxygen. Volume percentage of oxygen and nitrogen ie! are 20nd 80 respectively, and atmospheric pressure tobe! Explanation Volume fract and of 0; (g) = 0.2 Partial pressure of Na(g) = Partial pressure of O,(g) tion of N, (g) = 0.8 0.8%1 = o.8 atm =02x1=0.2 atm Instance 24 0. mol 08 are taken in a fosk nine 828 and 0.3 mol of 8% sealed. Now the flask is heated to 1000 on re reaction occurs quantitatively: Eartha follow Gik# Os 2004 (a) Caloutate partial pressure of oa end of reaction. (0) If tho reaction vessel was coon - completion of reaction, \Wwhat was the preset 4 77 Ignore the vapour pressure of itater at 27, explanation ‘The balanced chemical reaction (with states Adis 38,0 ich component at ht afer ure in the flsk Scanned with CamScanner— cyte) + £ 0x8) 20048) + 31400) at 2000 x 10 08 ° ° pst 0 wasnt gos aaa eden te Total moles n= 0.55 ying gas laws at constant voluitio bupiod Ba BaD nl) 24,0 (0:55x1000 4 a-a(22) ‘.4xa00,) = *58atm 0.05 (228) x 4.58 = 0.416 atm » m-(ise) 0.20 4.58 = 1.665 atm and wo-(6ss) 0.30 = (232) 4.58 =2.5 atm owo-(6as) ‘AMter cooling to 27°C, number of moles of gases left = 25 fe#,0(#) condenses into liquid water] Bom Poh 2 7 12) 1.0 (222) 0.025 aim nza(a}-20(%5)=08 Instance 25 A 20 L steel cylinder containing N,{g) at atm and 300 K is placed in a big jar containing air at 40 atm and 300 K and finally sealed. Now the N,(g) was alimed to leak into the jar at constant temperature, till the mesure equilibrium was established. Final pressure in the jar as ound to be 1.2 atm. Determine the volume of jar. Eplanation When cylinder is placed into the’ jar, it ‘laced equal volume of air maintaining constant pressure as Now, Var = (V—20) L Air + No P= 1.0tm petzetm Cylinder “aie opens APplying Dalton’s law, PW, + PV; = PV 202041 (V -20)=1.2 V v 2 =1900L he : ima®28 4 100 1, jan, filled with air at 1.0 ati and "ains an un-biown rubber balloon with its opening fon gull taco of jan. Air is pumped into the balloon ‘Woo Gialdes at constant temperature till. it develops Pag igs inside the balloon and finally bursts, Pressure of 1.5 atm inside the jar. Determine the volume of batloon just bofore it bursted and air prossure inside the jar just before bursting of balloon. Explanation Volume of air in jar before balloon blowing = 1001, Initial prossure of air in the jar = 1.0 atm IfVis the volume of balloon just before it burst, then 100 x4.0-+ 10 = 100x1.5 = 150 =» V=5L Also, volume of original air just before bursting of balloon = 100-5 = 95 L Air pressure in the jar before bursting of balloon = 100 20 aim. (Boyle's ke Oy ig 8m Boyle’ law) Instance 27 Aspherical glass bulb of radius 1.0 m contains ‘a concentric rubber balloon that contains some N, gas and the remaining space in the flask contains 50 g H. In the given conditions, radius ofthe rubber balloon was found to be 40 cm. Now the seal of glass bulb was opened and 25 g H,(s) was further added and resealed. Determine radius of the rubber balloon in the new conditions. Assume constant temperature throughout. Explanation ts 475 9 Hea) 2250) 7 From the above illustration, it is obvious that pressure inside and outside the balloon is same in both the cases. “Applying the gas law on I to N, (g) and H,(@); p and Tare same: Vous _ Youn Ata) PO) 4 x00? - 402) Sx x40 a aA _ 2 Aan 25 x (40)° {200}? - (40)") “Applying the gas law on IL to N,(g): 4a 4, (oo? =r} _ 3 3" 978 17 375 coor =P (xy iy a7 a: r Ly 37.5 5 122 = T 17 a7 7=35.13!om = aN)= =1,7 mol Scanned with CamScannerinstan 00 mb flask containing oxygen gos at {Zotmand 0 cached wate fk sing NOlg) at 0.6 atm and 300 K, by means'of a see negligible volume, where they combine pipette Nay at NO,, Finally NO,(g) dimerized partially into N,Oj an Pressure inside the flask was found to be 0.41 atin at the same temperature, Determine the percentage dimerization of NO, 2NO.(8) = N,0,(8) Explanation Before reaction Partial pressure of O; in the combined system, 712x100 <9 3428 atm 350 Partial pressure of NO in the combined system 250 $0.6 x 250 _ 9.4085 at 8x Fp 704285 atm 250 mu(7) 100m. (7) Also; in the combined ‘can directly be used to solve: system P,« ny; the stoichiomet Fel lens ‘try of reaction as BO + ob wo: & ip, tnistpentp: oars" ase ; Taalpetrentie pea, i wide ° sass Port presiue ser seaton 0012856» oaes-p 2 ‘Total ressure.p at the end of reaction I, P= 058705 -2=0.41 > P=0.2941 atm 0.2941 = %d tion =: 100 =68.63 % dimerization = Poo Effusion/Diffusion of Gases and Graham’s Law 5 tnirggety ole is/made in. the wall of vessel Took Zing @ gas, then the rate at which ges molecules Jeak out of vessel ‘will Proportional to the number of ‘molecules that collide with, i time, square speed of the gas “orinis, Process, when carried out unde ‘dealised conditions, is known a8 “effete, English Chemist “Thomas Gr the relative rates at which two different Bases at the same. Pressure, will ef fuse through identical "sely proportional to square root of ite @ Essential Physical Chemistry » 1 Rate sion: ii Ma My The above Eq. (4.15) is applicable, only i tg gases are at same temperature and Pressure, eff. through openings of identical geometry, The may bein the combined system if they are non’ and at the same’ partial pressure. Above elation ig, simple consequence'of the square root relation behing the velocity of a body and its kinetic energy. Acconingy Kinetic theory of gases, molecules of two gases ata temperature, possess the same average kinetic energy. ¥, and 7, are the ‘average -velocit molecules, then at any given temp => volt a, Be Hes of the two kins erature, KE, = KE, jAlthough the conditions under which Graham's applies exactly are very the law, neverthles Provides significant in a wide range of Phenomena that depeid on the Telative average velocities of molecules of different masses, A-seneral views of effusion Ifa. => vie , 1 Yag’ 2te of effusion is linearly related ‘oils partial pressure, ‘Vader the ahove condition, BaP. fg [owes| a 2 (4.18) DE (4.18), vs and va 7 P of two type of gased pat Rate the initiay rates of effusion renee 8 Pa tespectoa nu, initially at pat Instantaneous te of ffs srettaneous partial prema decreases continuously we Considering, instan TeSs_ of effusion. ns Pressure . dpidt) to pe, Teo f dec Tease of partial instantaneous gas pressure dine”, Proportional to ‘squate toot af molar mass, iistantanee Préportional to time cai be solved as vO'S Pressure at any Scanned with CamScannerBe 4 where Kis constant of proportionality, nd Kp ; pre eee ia a1) Kt 2 p2) YM 7) Kt In p, =n p,— Also. YM Kt Pa = Pi exp ( ) fe i Ww nce, partial pressure decreases exponentially with ine 35 t t inp. ’ tT = ig 49 Variation of gns pressure vs time during its effusion id Wiy a heavier gas from a gas mixture effuses rates? In a ges mixture, the average kinetic energy of G m?) is the same, Hence, heavier gas has speed. \ Instance 29 In what molar ratio He and Git, should be nnivdso that when the mixture is allowed to effuse through a pinhole, initially both gases come out at equal rate? Explanation Since, rate of effusion (r) from a ture, H(te) _ nite) _ fib, 7CH,) n(CH,) V4 = Ton, Pig =221 Instance 20 Rate of effusion of ethane is 1.53 times faster ‘han rate of a hydrocarbon containing 13.27% hydrogen by ‘eight under identical conditions. Deduce the molecular fama of hydrocarbon Explanation __“(ethane) {hydrocarbon M Empirical formula. = C H Wie 85.73 13.27 Mol % 05.73/12) 13.27 sR 1 2 Empirical formula =CH, Molecular weight = 70.23 = Empirical formula weight xn =147 nee, molecular formula of hydrocarbon is CH AS 5chy I rpstd 31. A flask containing He, CH, and heptane gas in through fal of (a) 4: 2:3 (b) 3: 251 ae allowed to offs ‘fine onfice in the flask. What will ba the initial molar Composition of the gaseous mixture coming out ls us mixture coming out In each case? Explanation : AUite): CH,) cig = re) Ae Meath (@) The oe above ratio = molar c 24°10 Tatio of gases. coming out initially. (H) | The ratio of rates with these compositions ea 5 $18 :5:1 410 Instance 32 Ammonia gas and HCl gas from the two flasks, ‘at same temperature and pressure were injected Simultaneously “through pinholes of similar geometry, attached at the two ends of a 1.0 m long glass tube. At what distance from the ammonia end, the first flash of white fume would be observed? Explanation since, the two gases are injected at same pressure, their rates of effusion will depend only on molar ‘mass and ammonia being the lighter than HCl, will move at faster rate as illustrated in the following diagrams : |985 = x =59.43em 1w0-x Vaz Fu Instance 33. Nitric oxide (NO) gas at 2.0 atm and oxygen at 1 atm are injected simultaneously through ‘pinholes of identical geometry, attached atthe two ends ofa semi-circular discharge tube made up of glass. The arc radius of discharge tube is 1.0 m and gases are at same temperature. Determine the distance from oxygen end at which first flash of brown fame would be observed. Explanation Here, the two gases being injected are at different pressures, their rates of effusion will depend on both molar mass and gas pressure as a 2 HINO) Ao _ [82 22 132 2 065 1(0,) &, 30 1130 xm Point of 1" collision NO 1.0. atm 20am Gaseous State @ Scanned with CamScannerArc length of tube = nr =3.14m =) oe cezaim Yo) dld=x Instance 34 Difiusion of a certain volume of Nila) at 1.0 atm and 300 K, takes 25 »8 while same volume of an unknown gas of Xenon and Fluorine at 2.0 atm and 300 K takes 34 s for difusion through the same pinhole. Deduce the ‘molecular formula of the unknown gas, Explanation Rate « —1_ Time > Me 28 = M=207.15, Since atomic ‘mass of Xe = 131, the gas cannot contain ea than one Xe atom per molecule. Hence the moloenice formula of unknown gas could be Xef = 207.15 =131 + 19% x= and gas is Xer, Instance 35 Pressure of nitrogen gas falls from 4000 mmo inthe ia. 30:min, when allowed tofuse trough aintels cyuntes @inder: Ifthe, same cylinder is fied van oe Explanation Since, initially equal moles of Bases are eee x itial partial pressure of both N, and He is 2000 nme of Hg. Also, ~P eS in (Bt) - ame (Be or aoe , HBO pad o From mixture For N, 1n (2000) _ 90% i Px) 28 For Hs hs (2m) 298 (8) Psy Solving Eqs. (i), (ii) and = 51 mmofiig ‘Molar ratio after 1.0 h(N, : He) Instance 36 A 50.00 ft Jong classroom has twenty rows of seats and the adjacent rows are separated by 2.5 ft each A N,0 cylinder on the front door and a CH, cylinder on the rear «door were opened simultaneoushy so that gases start fusing into the classroom. Student of which row will frst experience the teared laughing? Assume both the cylinders have gases at same temperature and pressure and valves have similar dimensions. Explanation Since, CH,(16) i lighter thay y Fray (4) fomer wil dif at atest hl front door, two types of gases meot first Ty eat Graham's law: 50-x 7 row from front 8" row front eg, from front ‘The above distance i lying between 7 and 84g, the front as shown: Since, CH, is moving at faster rate then N,0, th will cover distance of 1.3 f (of 74 row) earlier than telag will cover adistance of1.2t(of row). Hence, thexuday seating in 7 row wil first experience smell of bolhN Gat Gri, simultaneously and they will tear and lah tpg first. Dissociation and association of gas and diffusion studies A polyatomic gas may remain in either pure former may remain in partially dissociated or associated fam, Dissociation or association alter the average molar mand 26 mixture compared to its pure form and hence, thir Zales of effusion. To illustrate, let us consider one moled PCs) confined ina flask. I itis considered tobe 100% dissociation products PCI, (g) and Cl, () as PCLA(g) = PCly(g) +Cla(g) 1a @ « Total mole = 14> 4 Due to the above dissociation, moles have changed from 1.0% to (144), but the mass remains same, 2085 g Now, molar mass of mixture =_ Weight of mixture ‘Total moles of mixture ~ 14a. pure gas. 1n case of association, number of moles decreases and hhonce, molar mass of partially associated gaseous mixture always greater than molar mass of pure gas as Scanned with CamScanner2NO, = N,Q, 1-0 an mole =1-%< ‘Total m: Sst Mux > Meo.) undergoes partial association, it ‘Th ye less than the rate of effusion of meee aftsion wonsidering any association) rtially ga Giar weight of some pa: ] alec yr d/associated gas mixtures } ways advisable to start with one mole of is al ° It ie as, 0 that mass of mixture will always be equal apolar mass of starting PUre gos as ‘0 7 (@,0, eC +50 1-a Cabecg & ‘otal mole= 1+ Za-and total mass = Mass of 1.0 mol of CLO, } Myo, Magix = — SE o 1 2 | nitialy one mmole of NOz was considered] i 18 no pre er Instance 37 Rate of effusion of ethane gas is 1.9 times, the me: ‘effusion of a partially decomposed Cl,0; (g) mixture. mine the degree of dissociation of C10, (8): Inst ay Be Male o,fcon if a sample of oxonized Doe Imes the rate of effusion of pure oxygen. Caplets Percentage of ozone inthe oxonleed sample Planation For ozonation: 30, = 20, 1-a waa Total mole at equilibrium = 1 = a = Magmndt 1-2 “ = Flozohised mix) foconlsed mix) 5.95 * (oxygen) is = «=0.2925 * Wolght of ozone in the mixture = Weight of oxygen ‘ozonised 320.2025 g. = Weight percentage of O, in mixture 0.2075 x32 = 0:2975 x92 199-28 ee (00 =29.75 Instance 39 Cl,(g) and F,(g) are mixed in molar rato of 1:3, in a flask and soaled where they combine partially to produce some CIF,(g). The rate of effusion of equilibrium mixture was found to be 43 tines slower than the rte of efusion of pare ‘oxygen gas. Determine the mole fraction of each ent in the equltoriummstue fae mpon Explanation The equilibrium reaction is Gl, + 3F, = 2c, =a 3-30 a (Total moles at equilibrium = 4~2c) = Molecular weight of equilibrium mixture = MCh) +3M(R)__ 185 4-20 4-20 = Also, 110s) 29/185" tay Taw) \(@=20)* 32 > a=0.289 =Total moles = 4-20 =3.422 Instance 40 PCl.(g) was (aken in a flask, sealed and heated {0 500 K where the following equilibrium was established: PCI(g) => PCh{g) + Chia) Fquilirium mixture was allowed to effuse by making a pinhole in the flask and the gaseous mixture coming out ‘tially was analyzed. Analysis revealed the mole fraction of PCI) inthe mixture coming out initially to be 0.3. Determine degree of dissociation of PCl(g) in the given experimental conditions. Gaseous State @ Scanned with CamScannerExplanation Here, the mole fractions of gases coming out tally will not be equal to the equilibrium mole fractions of Bases inside the flask since, they will effuse a different rates Mole fractions of gases outside the flask will depend on their relative rates of effusion, a. hyn [+ Ina gas mixture, mole ratio = ‘mole fractions ratio} Now let us assumea to be the degree of dissociation and xbe the mole fraction of Cig) outside the flask PCLIg) = PCL(g)+Ch(g) 1-a oe adil Frclyy ie ag, soar ‘> Mole fraction of PCI,(g) outside the flask 1=(03 + 0.417) 23 Also: S04, oan tra) 83 Instance 41 A 100 mL ask containing 0,6) at 1.0 atm {i400 Kis connected to a 300 ml. flask containing NO) at Panwa and 400 K by means of a narow tube of negli bia reeuie where they react quantativelyto fom NO, TheND. then partially dimerized into. N, 04(8) in’ the given tarp mental conditions. Rate of effusion of CH,(g) wos found to be 1.68 times rate of diffusion of the above equilisrima Traits under similar conditions. Determine the degree of dimerization, Explanation In the combined syst. tem, volume forall gases is 400-mL. Before any reaction occurs 125 atm Reaction: 2NO + 0, —+ 2NO, = N,0, Initial P: 1.32805, ° 0 FinalP: 0123 9 1-a ai Average molar mass of this mixture 92 0.125 x30++46(1-a) + 2 025 +4-% 125+1~$ ‘Also, £(CH,) _ F(x) = @=0.393 a Successive diffusion and enrichment g lightier components When a gaseous mixture containing lgyg heavier components is allowed to pass throute™ 8 diffusion chambers connected in series, enrichment of lighter component in each succes, By carrying out diffusion of a gaseous 1 , specific number of steps in Succession, @ spec enrichment of lighter component can be aching follows : a From the 1 chamber: (2) -s) FE -) From the 2=! chamber: C2) fC) ea From the 3" chamber: Ch (6) (2) ("= ( Similarly, from (n-1)4 chamber: (3). -@) > (8) =) (ey (is) 0m np Ea (4:8) Indicates that aftr (n Aiffasion a specific enrichment (2y/ng), 3 = 1)" step of in the n'* chamber, “an be achieved Lnstanee 42 A empleo Nee ogy ep and rang ae Ne ny 10% by ain spe afeiaon ste. Po We eachment ep ee Bo may Explanation ‘ntiay (i) <3 Desired ratio: Scanned with CamScanneri gat stop of effusion, 25 chamber will have thy ie et tar ratio di aes Molecular Theory of Gases je oa such as temperature, prossure and ‘the Prther with other properties related to them ‘ ‘thermal poauctivay) are own as. (densi. properties of matter, these are the pro od ic Pfswed in bulk matter, without reference ey Us a ying structure ot molecular behaviour, isu lato 19" century, the atomic theory of matter ‘ufficiently well accepted, and the that scientists was sulfiotate these macroscopic properties to the im eof the individual molecules, which were “hed by the microscopic properties of matter. The saa this effort was Kinetic theory of gases: Kinetic ety of gases applies strictly only to the hypothetical the sea nown as ‘ideal gas’. We shall see, however, sat itdescribes the behaviour of real gases as well, but in tna iied range of temperature and pressure, and serves seh extremely useful model for treating gas under fon-ideal conditions as well, Therefore, kinetic theory of gases, in absolute, is a hworetical model of ideal gas described by Boyle, Charles {od Avogadro, Since, it is a theoretical model; it is based. sporrtain assumptions, known as “Postulates of kinetic theory’ Basie Wenets of Kinetic Molecular Theory 4. A gas is composed of molecules, which are ‘spherical in shape. For a pure gas, all its molecules are identical in shape, size and masses. 2. Molecules are separated by an average distance that are much grater than the size of the molecules themselves. The volume occupied by the molecules of a gas is negligible in comparison to the volume of the gas itself. Hence, volume of the gas molecules was ignored in comparison to the gas volume in deriving the kinetic gas equation. 3, Ges molecules are in constant random motion, and. ‘5 material body, they obey Newton's law of motion. This means, molecules move in straight lines until they collide with the other molecule or _Wwith the walls of the container. 4 Collisions among the gas molecules are perfectly lastic in nature, When the two molecules collide, they change their directions and kinetic energies but the total kinetic energy is also conserved. The average kinetic onergy of gos molecules #8 fectly proportional to the absolute temperature. {implies that velocities and kinetic energies of an idual molecules will span a wide range of Tates: some may have very high kinetic endrsy Ds teciave @ may have very low kinetic energy, but the __ Begekinetic energy will remain constant as/0n8 Temperature is maintained constant. Thus, accordiny Thus, 18 10 this theory, most of th wn ry, 16 space Aas a by gas is empty; this is the main feature th alee ‘Bases form other states of matter in which fie malgadre constantly in contact with each other, The eee nclecules are in rapid and continuous motion, at the catty temperature and pressure, their velocities are of spit Ae “1.0 km/s and each molecule experiences pete ely 10" collisions with other molecules every Kinetic interpretation of gas pressure ‘The kinetic molecular theory makes it easy to see why gases oxert pressure on the walls of container. Any surfaco in contact with the gas is constantly bombarded y the molecules. At every collision, a molecule moving with momentum ‘mv’ strikes the surface. Since, the Collision is elastic, a molecule bounces back with same velocity in the opposite direction, According to Newton's second law of motion, force is defined as rate of change of momentum as pa? = maa dim). mav at dt dt Momentum of the molecule in x-direction, when it strikes the wall is mv,. Since collision is assumed to be perfectly elastic, the molecule bounces back with the same velocity but in opposite direction as described in the following diagram © ) Fig, 4.10 (a) _X-component of the speed of a gas molecule in a box (b) X-component of speed just before collision isu, and after collision itis —u, ‘Therefore, change in velocity of the molecule in each collision is ‘Avy =~ Vx (after collision) ~ vx (before collision) = 2, Hence, the corresponding change in momentum is —amvg, Since each collision with the wall occurs only afer the molecule travels at distanco 2x, the number of {ollisions, @ molocule makes in unit time may be GSleulated by dividing the velocity v, ~ the molecule els in unit time by 2x. ‘Thus, the number of collisions per unit time = = tray => Change in momentum per unit time (Cav, m De == BF Scanned with CamScannerwall on the gas Is the force exerted by the oe in unt tne, Therefore, fore experianced by wall in x-direction, in unit time will be-F. mn, = Fa =~ B= Since, pressure is force per unit area (A) and area Ais vw KET of pm Kr vil kinetic Bas Ke In deriving, the (ag translational motion of the molecule ta‘ account, Henc, the translational energy cag os views. 10 Jn terms of mean square velocities, x-direction can be expressed as Ne W,) = pressure in De as (4.19) Eq. (4.19) gives the pressure of aone di For the components of velocitios in Yand Would obtain expression similar ¥; and 72, respectively, limensional gas, Z directions we {0(4.19)by involving v, With this assumption, average pressure in all three directions will be Px=Py=p,=p Ssecnass = PV = mNe (4.20) Eaq4.20 is known as Kinetic gas equation for an ideal as. Some aspects of kinetic gas equation At) Bffect of temperature One of the postulate of Kinetic theory” states ‘that average kinela energy roportional to absolute temperature, Hence Where, X= Boltzmann's constant = 1,98 xg! Besides translational motion, molecule Possesses rotational and vibrational. moti @f Contributes o the total energy of the gas molecule @ {2) Rotational Motion in order to descibe& Gienlation of a linear molecule in. space, we nel specify two angles about the: two axes while it Teusinear molecule, three angles are required Maia these coordinates ‘corresponds to the rotational motion. Tie ‘SHer8Y associated with the rotational motion is givenas Tot +t het for linear molecile ' Ey 1 nop we AS heat +1 ot .- for non-linear rmoleit Where ,, 1, and T, are the moment of inertia abt Gide asad, a, and, are the angular veldiis to aptaeh term in thé above expression is propo sauare of the velocity, ‘component, it contributes 012 1 STREET: towards the average rotational ener! Therefore, 1 aa ir flag aaa 3 kr. for nomlinet 2 molectlé assum tion Motion: If the vibrational moti m conn tEtonic, each ofthe vbeetonal sears ‘vibrational enengy® 8 SVetage of KT to the total a iy foyle's rh ‘ using kinetic th ee ort Bove law can be verified PV = 2 mnt 2 yf act) 2 NE | eae i Gse)z3 2.2) : eae 2 inp el @ Essential Physi al Chemistry | Scanned with CamScanner5 age kinetic ene, _ isthe average Kinetic energy wher ed amount of gas, Nis constant. At constant, rorofen erage Kinetic enersy is also constant at . oP” ; pes = constant .- Boyle's law; from Ba, 4.22 opares’ Zane ® At-constant Pressure, for 4 fixed ya ENE and Bar ora fixed omount N = constant, then V «T... Charles’ law ' pv ee Ne avogadro’s law: pV == nf xr) @) reonstantp and 7: V = N ... Avogadro's law 43 Calculate the pressure exerted by 10% gas tance ef mass 10% g in a container of wold srg ot mean square speed is 10 cs. ! explanation 1107 kg x 107° x (10° ms“! x —1__ 2 p=zxio ke t Ta = i x10°Pa ce 44. Atwolitre bulb contains 3x10 gas molecules Mixer 10° Pa pressure. Calculate translational energy per Jokeule and total translational energy. aplanation pV = nAT pV _ 10° x2 x10" x6,023 x10 3x10" x8.314 83 K Ky = 3 1.916 x10 x 489 0-* J/molecule K, IN =3000.25 J Exgys (Total) = Maxwell’s Distribution of Molecular Speeds Spied ofa gas molecule wos otinuously due cae’, intermolecular Sligo yg their tinge nt the wall of Mindi et Seed of D4 gplual molecule is or ature are ith time. It is expected to be applicable to the pressure and tempel Gaseous State disteibution of Statistical avec Molecular speed and we consider a age of tho speod of whi Cray speed of whole of the collection frac ctles to remain constant with time, That te the dofinita st? al molecules having speed betwoen ans of the nee st be constant, even though the Molecular coin en eetes may be changing a aresult of Distribution of molecul i M ular speed over a possible range ae investigated by Maxwell using the theory of for drei: Results were expressed as the Maxwell law °F distribution of molecular speed as dN, = 4nN ( M ) ann 9/2 =m eet da ae, anN GS) eM du (4.23) The above expression gives the number of molecules AN, having speeds between u and u + du in term of total ‘umber of molecules present (/), molar mass (M) of gas and temperature (7). According to expression (4.23), the fraction of molecules (dNJ/N) having the speeds in the Tange of u and u + du, fora gas of molar mass (M) depends only on temperature. Hence, fora given temperature, this fraction is constant. A plot of fraction of molecules in the speed range wand u + du, 2 () vs u is described in Fig. 4.11. iw) 1 (an Nw Fig. 4.11. Plot of fraction of molecules vs molecular speeds at different temperatures, ‘The peaks in the curves correspond to a speed, which is possessed by maximum fraction of molecules, called “most probable speed’. As we increase the temperature, distribution of molecular speeds broadens and a fraction of molecules lying in a given range decreases, hence the fraction of molecules possessing the most probable speed hat th absolute value of most probable speed increases ith temperature. van er maat probable speed can be derived mathmatical sing ho contin of masa by setting I) it . st derivative of 5 (= swith respect to speed equal t zero. Scanned with CamScanner, olh24) Intext Q.1 What happens to the fraction of molecules [possessing most probable speed as temperature is increased? Answer As temiperature is increased, disttibution of moleculat speeds broaden, £e., some new types of speeds emerge. This lowers the fraction of molecules possessing, ‘mps. IntextQ. 2 What happens to the fraction ‘of molecules [possessing mps as molar mdsss increases “at constant temperature? ! Answer It increases. i Intext Q. 3 Which principle of classical mechanics is used to derive the kinetic gas equation? Answer Perfect elastic collision of gas molecules with other gas molecules as well as with wall of container, Intext Q.4 Why gases have same\ mognitude of components of pressure in all three directions, vi. x,y and Answer Molecules of gas. are in constant random motion. Intext Q.5 At a constant temperature, make a plot of| ‘square of momentum versus molar mass of gas. Answer = =Constant (6) = stem Average Speed : Average value of speed is given by the relation: gotta ty +b N Ny ; substituting for 5°?” the above exprestgg 3/2 Ma M ” e TaT s-u(ie)" Conta Integrating the right side of the above ag yields a ; 7 RT ean( M4)” (Zh one 2RTR M)| VaM = 8 Root mean square speed: The root mean ue 2 2) tate Ns | ‘The kinetic gas equation is pV = nT = speediis given by mNe 3nRT mN | zs locoil hon Uist a Some conclusive points for distribution molecular speeds (i) The fraction of molecules having either very high Gr ery low speeds is very small. Majority ol ‘molecules have speed near tou. in the middle the range of molecular speeds. me {olal area‘ under the curve in Fig, 4.11 84 collet eats total number of molecules i coe “se in temperature ‘raises the kinetic ners) molecules ewes, it follows that fractions fractions opts lower speed range decreases increases. a wolecules having higher speed rang? = 1000%G, A180 the curve at higher temperature Value bur eed C etc) has its tgs shifted to hight ve dante Corresponding fractions of molecule broken at tet: Also, the curve near tay his molecules posegn; mPerature indicating mor speed, The S8°88ing speeds near to:most prol 45 wider 4, 2 8eReral, the distribution of speeds ‘temperature, 12H? temperature. than at lower Essential Physical Chemistry Scanned with CamScannerana lighter gas molecule as shown in the) ethan ile in tho| Bowing 120 He = a oC A ol Vaca rig 412 Deal constant fomperature ainsi aveiaes: seulate average translational energy and 45 Cal instance Tore speed of He at 25°C. To wit temperature, se th Sold c0 thal es the Same rms as He ot 25°C7 ost 2 asd pation Bian = AT =3 xO.914%208 =3716.35 J mol __ SAE _ Bxesiax296 Bene VM 4x10" =1363.15 ms _ BRR238 _ ail ko, tm (0) = gs Mess OY os irae 2 instance 46 Derive an expression relating to increase in Ig ofa gas for o relatively small temperature rise ond ‘dlulle increase in’ U,,, for a sample of Ne(g) as the engeratare fs increased from 100 K to 101K? ie = (ese dT M o2T 3R Miya 2 me Oe 2M Bn dite, p3E. iT 2M tiga, 3 [BRE = 8%8.314%100 _ 959 ms 20x10 =—3 8314 491-100 2x20 «107 x353 =1.766 ms i Jastance 47 Derive oxpression rotating fo change In Ems a Sefer mall temperature change and eatulate ‘hange nme fOF a samplo of No(g) as tho tompurature fe incred Explanation Fs, 3 9.314% 100 In 2% 2 100 =12.4J mol Instance 4B tow much energy is needed to increase the miperature of Ar(g) from 0°C to 25°C? Explanation Evans x8,314%25 =912) mol Instance 49 ‘foot mean square speed of N,(g) in alr is 515 ms“. What isthe average speed of He gas in the same air? Explanation ‘ig eaer My and iy aa “SEM Both are at same temperature: = — ite, [8Mn,. 8x28 x10" Ummstss) V9 V3R x4 x10 4375 x515 = 1255.3 ms” A375, ae Tie Instance 50 Density of a sample of air was found to be 1.17 glLat 10 atm, Determine average speed of gas molecules present in oir in the given conditions. Explanation. 7= [92% and PM=phT = [BP = [PXA01B25 NO 66,6 ms mp Vn x1.07 kgm The ‘Real’ Gas ‘The ideal gas law pV'= nFtTholis fairly true for most gases but over a limited range of temperature and pressure. Howoves, when the fange and accuracy of Piasurements were extended and improved, real gases were found to deviate from expected behaviour of an ideal os For instance pV (Va, = molar volume of a gas) does eet have same value for all gases ata given temperature. ‘Aso plot of ply ¥s pare not same forall gases at a given ainperature. The graph in Fig. 418 describes the real tssure dependence of volume for one mole of different gases at samo temperature. Gaseous State @ Scanned with CamScannerFig.419. Plots ofp ve Vfor real gas and ‘comparison with ideal gas curve. Amagat’s curves Since, pV = nT, pV should be constant at any temperature and the plot of pV versus p should be # straight line parallel to p-axis. Amagats found that for ‘most of the gases. The value of pV decreases at frst as the Pressure is increased from very low values, reaches ‘minima, then increases at higher pressure forN, CO, et The above-mentioned behaviour is described in the following Fig. 4.14 > Fig. 44 Amaga’s curves, pV veeu pfor diffrent gises and at diferent temperature ‘The above behaviour of gases indicates that gases are ‘more compressible at low pressure than what can be expected from Boyle's law and become less compressible, at higher pressure, With oxygen, there: has been a continuous studied. With H, and He, the curves show a ise right from the low pressure, ‘Another important feature noticed in this connection with the gases like N,, CO, ef, is that as the temperature is raised, the pV curves represent less pronounced minima i.e, the depth of minima diminishes os the temperature is increased and the position of minima gradually shifts towards pV axis. f the temperature is increased to @ high value, itis easy to visualize that ate certain temperature the depth of minima eventually vanishes and the minimum will coincide with the pV axis aie | itself. When this happens, pV p curve topeaxis over certain range andit cope temperature obeys Boyle's law for a cena mk pressure, im This particular temperature where th mis the pV-p diagram coincides with the pV-axisjs mt the Boyle's temperature (Tz). Thus itis evidens ‘gas obeys Boyle's law at least at one temperate one a Boylés temperature) and under eating pressure, For Hz and He gases, where there is tendons on ast of graph to show increas right from being gases may be looked upon as being above this fet tomperature and the minima are, as it were, on i, by side (an imaginary case) of the pV-axis, Simla, ont for ,may be looked upon, as one in which theming isso faravay onthe pressure axis that we may gute tninimum occurring at a high pressure, which steya our practical realization. Compression factor (Z) It is the measure of deviation form ideal behavion and is defined as ae Vai Vp, (ideal) For an ideal gas Z Vn a (427) = 1 and for a non-ideal gas 2 #1 departure from unity indicates noniel 88 will have different intracticas the: behavior of Z om te * different gases, The following ¥s p for several gues served. behaviour, since each, amongst their molecu expected tobe different fa joeram (Fig 4.15) showing plot of Z, depicts the variations in obs sess tm ata ste it ts fone oe 8 alt Prevalent among the molecules 1 ‘ean be illustrated in the following manner. Z:measure of deviation fy ‘nt ideal behaviour = Real value of any vari 1 Behviow able = ‘ same variable keeping other parami = ofthe = 2 = Paw Psat (428) © Essential Physical Chemistry a = Scanned with CamScannerjf there exists attractive forces ‘THU “oy will be attracted towards on poloo¥leS 5 tho wall of container with loss flee in lowering of obsorved ‘his revithout this consideration. “eo Prot 1) indicates that ro the gas molecules dominate, goes am Fas molecules will collide to th sie with greater effective momentum a cottpondent collision and a greater value ‘ol woe served- mong the we another and * momontam, Prossure than 2 5 snitial Post \ tepulsive ‘a In caso of © walls of 's compared of pressure (i Pra > Pitear and Z>1 ‘nl gases, at sufficiently high pressure will have z > iice molecules come closer and ropulsive forovs stxt 18 todominate. ‘asp 0, curves forall gases approaches Z = i, with sent slopes. Hence, 08 2 ~> 0 (low pressure and high Utpaature) gases approaches to ideality, easons for deviation from ideality Gases deviate form ideal behaviour because the assumptions made in deriving kinetic gas equation, do tot hold true under all conditions of pressure and teupureture. Two assumptions, which are mainly responsible for deviation form ideal behaviour, are (i) Molecular volume : According to kinetic theory of gases, gas molecules have negligible volume. In actual practice, gases can be liquefied and solidified, the volume occupied by gas molecules are finite and its contribution to the total volume becomes significant under specific conditions of temperature and pressure. (i) Intermolecular interactions : In'kinetic theory of gases, gas molecules were assumed to be independent of attractive or repiilsive forces by other molecules. In real situation, gasos exert either attractive or repulsive force on one another depending upon conditions of temperature and Pressure, Correction for molecular volume and Messure (van der Waals’ equation of state) ida] &* Waals modified the equation of state of the lings 8Y Modifying two of the assumptions of the lg 2 He assumed (i) that in a real gas, the thee jg T° NOt without effect on one another but that eran att€téction (attraction or repulsion) between Pee ge ES and (i) that molecules are not geometrical dinapsgg 28824 in the kinetic theory of gases but have cg MICA must be taken into account for explaining their behaviour. in cer Waals’ pointed out that th ointed 0 ressure to whic 1,84 18 subjected fs not me exter resure p, oroly tho external pressure p, ae xcoss prossure p" due tothe mutual attraction inverse cules, which he proposed, would vary Pressure (ny th? Sauare of the volume. ‘Thus, the excose sven by pte 10 attraction was regarded by him to be sneha qthero “ota constant depending upon the system jo, ats Hence, the total pressure in the gaseous vai 8 I a P+p=p+% paptry Here, P is the observed pressure. As to the volume Somection, van der Waals believed that the molecules do possess some volume on account of which the molecules ‘#0 nol freo to move inthe entire volume at their disposal. ‘Tho volume (total) ofthe molecule is unavailable for the molecular movement. van det Weals assumed this Correction to be “b”, so that volume available to one mole of molecules for their free movement is not V but V-b. Hence, the corrected equation of state for one mole of a real gas would be (+ 2)w-» aT (4.29) For n mole of gas the van der Waals equation is (0-82) — mw a RT ..(4.30) Eq. 4.20 is the well known van der Waals’ equation of state. van der Waals’ equation of state is obeyed by most of ‘the gases in a broad range of temperature and pressure. ‘The magnitude of deviations from ideal gas behaviour can be illustrated by comparing the results of calculations using ideal gas equation and the van der ‘Waals’ equation for 1.00 mol of CO, at 0°C in a container of different volumes. (@) Lot us start with 22.4 L container. According to the law of ideal gas, the pressure of this gas should be 1.00 atmosphere. ART _ 10.082 x273 _ ie 224 The van det Waals’ constant for CO, are .592atm L’ mol, and b =0.04267L mol" 00 atm, a Substituting the above constants in van der Waals, equation [ + 2882 |a4-oosas7=d.etxars (22.4 Solving p = 0.995 atm Scanned with CamScannerv— Fig. 443 Plots ofp vs Vfor eal gas and comparison with ideal gas cuve, Amagat's curves PV dectoases at first as the Pressure is increased from ‘minima, then increases at higher p The above-mentioned behaviou following Fig. 4.14 ressure for Nz, CO, eto, is doscribed in the > Fig.4.24 Amagats curves, pV versus p for different ‘gases and at different temperature ‘The above behaviour of gases indicates that gasos are more compressible at low pressure than what can be cxpected from Boyle's law and become less compressibl, at higher pressure, With oxygen, there hae been continuous studied. With H, and He, the curves show a ise right from the low pressure Another important feature noticed in this connection with the gases like N,, CO, ete, is that asthe temperature is ‘raised, the pV curves. represent less pronounced minima i.e, the depth’ of minima diminishes as tho temperature is increased and the position of minima towards pV axis: If the temperature is | itself, When this happens, PV-p curve becon, to praxis overa cortain range and it appear, tha temperature obeys Boyle's law for « coma! mK pressure, This particular temperature where tho ny in the pV- p diagram coincides with the pais shag’ the Boyle's temperature (7). Thus it seve that gas obeys Boyle's law at least at one lemperatie jg as Boyle's temperature) and under certain Tap, pressure, : For H, and He gases, where there is tendon ag part of graph to show increase right from begin fases may bo looked upon as being above ths aye temperature and the minima are, as it were, on eg fide (on imaginary case) ofthe pV-axis. Simi of for 0, may be looked upon, as one in which the minins is so far away on the pressure axis that ‘We may rege ‘inimum occuring at a high pressure, which iste) ‘our practical realization, By Compression factor (Z) if the measure of deviation form ideal kaon and is defined as, Ze (425) For en ideal gas Z = 1 and fora non-ideal gas Z #1 Therefore, departure from unity indicates nonidal behaviour, ie 22ch ges will have different interacts amongst their moles, les, the i be expected to be ditieeoe the behavior of Z can Went for different gases. The follow wing plot of Z vs p for several 6 ‘ons typically observed, diagram (Fig. 4.15) sho depicts the variat Zs AAS ian acne ‘Presere for several gases at 275% 1, Begative slope of some of thes? that 10 the attractive forces (2 <2) *Viation from ideal behaviour. 82Y variable = Z (Ideal value of th? "8 other parameter similar) 2 = Pea Prat Essential Physical Chemistry = Real value of, same variable keep = (4.28) Scanned with CamScanners.mhere exists attractive forces amo, hos Uy wil be attracted towards one, oe, the wall of container with less sities ie jowering of observed pressure than this consideration. =. c Prat < Pint ond Z<1, _spative slope (Z > 1) indicates that ropulsi ii 7 po gas molecules dominate ae fuces Bo gas molecules will collide to the walls of fits greater effective momentum as compared ollision and a greater value of pressure fei an without of inet rependent ered: Poa > Piso and Z>1 «, at suificiently high pressure will have 2 > come closer and repulsive forces stat iedomina. Gurves forall gases approaches Z = 1, with ‘Hence, as p — 0 (low pressure and high rent SIOpeS: & ;proaches to ideality. tenperature) gas @P exons for deviation from ideality ‘Gases deviate form ideal behaviour because the ssunptions made in deriving kinetic gas equation, do sinuld te under all conditions of pressure and ture. Two assumptions, which are mainly sspnsite for deviation form ideal behaviour, are {) Molecular volume : According to kinetic theory of gases, gas molecules have negligible volume- In actual practice, gases can be liquefied and solidified, the volume occupied by gas molecules arefinite and its contribution to the total volume becomes significant under specific conditions of __ temperature and pressure. (i) Intermolecular interactions : In kinetic theory of gases, gas molecules were assumed to be independent of attractive or repulsive forces by other molecules, In real situation, gases exert either attractive or repulsive force on one another depending upon conditions of temperature 2m! Pressure, ‘erection for molecular volume and wue(van der Waals’ equation of state) pi ae modified the equation of state of the lage ge’ Modifying two of the assumptions of the Nigar”, Hevassumed (f) that in @ real gas, the gan in hot without effect on.one another put that pees ea (attraction or repulsion) betwee gi) that molecules are not get ion age i the kinetic theory of gases “Senge ch must be taken into, 200 laining their behaviour. but have nt for van dor Waals’ ign mee poled out that the prewar to ich Ica Stbleted ts not merely the external pressure p, a tne ets rosea p" duet the mutual arcton fnvcreagimgcules, wich he proposed, would vary ee square of the volume. Thus, the excess ie (0) die to attraction was regarded by him to be = a where “a” isa constant depending upon the ‘aso ofthe gs, Hence he tl pressure nthe gaous pepapes pra sont: the observed presure, As to the volume rection, van der Waals believed that the molecules do ‘possess some volume on account of which the molecules genot fret mow inte entire volume at thei disposal. e volume (total) of the molecule is unavailable for the molecular movement. van der Waals assumed this correction to be “b”, so that volume available to one mole ‘of molecules for their free movement is not V but V-b. Henco, the corrected equation of state for one mole of @ real gas would be i +) v oar (o+2)0-9 For n mole of gas the van der ‘Waals equation is 2, (> Z2)u =nb)=nRT (4.30) (4.29) 2, 4.80 is the well known van der Waals’ equation of state. van der Waals’ equation of state is obeyed by most of the gases in abroad range of temperature and pressure. ‘The magnitude of deviations from ideal gas behaviout ean be illustrated by comparing the results of caloulations using ideal gas equation and the van der Waals equation for 1.00 mol of CO> at 0°C in @ container ‘of difforent volumes. (i) Let us start with 22.4 the law of ideal gas, the pressure ‘should be 1.00 atmosphere. AT _ 1%0.082 278 _ 1.99 atm Vv 22.4 ier Waals’ constant for CO2 are and b=0.042671 mol” L container. According to of this gas ‘The van di q=3.so2atm Lt mol’, stating the above constants in-van der Waals, subst equation (2ay p = 0.995 atm eon ere ; solving, Gaseous State @ Scanned with CamScanner