CHAPTER-2 Gaseous State Gas is one state of matter. It has neither shape nor volume and has very much weaker molecular forces of attractions. The gaseous behaviour is more uniform and simple to understand. As gases are invisible, they are described through the use of four physical properties or macroscopic characteristics: Pressure, volume, number of particles (moles) and temperature. These four characteristics were repeatedly observed by scientists such as Robert Boyle, Jacques Charles, John Dalton, Joseph Gay-Lussac and Amedeo Avogadro for a variety of gases in various settings. Their detailed studies ultimately led to a mathematical relationship among these properties expressed by the ideal gas law. Gases are conveniently classified into two types a. Ideal gases b. Real gases, An ideal gas is one which obeys all gas laws under all conditions of temperature and pressure. The volume occupied by gas molecules is negligible when compar to the total volume of the container, There is no intermolecular force of attraction under all conditions, Real gas is one which obeys gas laws only at low pressure and high temperature Volume occupied by gas molecules and intermolecular force of attractions appreciable and the magnitude of each depends on temperature and pressure 0 and the nature of gas, 30 Scanned with CamScannerell-Boltzmann distribution, i ies of th IL a the one nysicst James Clack sg This distrbuage® tistical distribution of Se distribution of ey ¥ell in 1859, on tae y°3! Ht established by the Is generalised by foe ohn’ the molecules of 7 ey factors, finding Ww © . rman physici: ° Bas. Later 5, the distribution of energies among the mole 8 Boltzmann: (i a ee 's Allthe molecules of a particular ‘chemical com: mass, so their kinetic energy is only d, pound or ef € 8 ependent on th In any particular mixture of moving molecules lement have th peed of particles moving particles varies at a particular temperature, peed of a mixture of Inthe derivation of kinetic gas equation, it was considere of gas at a given temperature are moving with a constant a nee sate Thus they are continuously colliding with each other and with walls of the container During collision, momentum is transferred and velocity changes. It is very difficult toknow the individual velocities of molecules, One can only obtain a distribution of molecular velocities at a given temperature. Thus collision results in the redistribution of both energy and velocity. The speed will vary from zero to very high values. The velocity of molecule increases with temperature. Maxwell and Boltzmann distribution lawis helpful to understand the variation in molecular velocity, the different types of velocities, Maxwell and Boltzmann utilising probability considerations have shown thatthe actual distribution of molecular velocities depends on temperature and. molar mass of the gas. The expression derived by Maxwell and Boltzmann is written as 3 3 mc? 0, gq] _™_P Rr CAG .() en Sa When Se is the fraction of the total number of molecules having velocit ‘T=Temperature ‘R=gas constant. bet n ‘C’ and (C + dC), m = mass of gas molecule, Divide equation (1) by de @) a a pelen m [ee r n de 2mRT. oa Yao). ‘on of molecules in the velocity range al ae indicates the fraction 0 Jes having the velocities between q ; ‘i ul ©. and is thus the probability (P) of finding molec and(C + ac), Scanned with CamScannerThe distribution of molecular velocities is shown in Fig-2,1 inw, plotted against velocity at different temperatures Ti, Ts, Ts such that 7, shih » The area under the curve indicates the total number of Molecules 1! velocities between ‘C’ and (C + dC) and the height of curve correspon hey velocity is virtually a measure ofthe fraction of the molecules wes Blog velocity, Number of molecules having both very low and very hi vet thy highly improbable. Majority of molecules have velocities between ‘© Petey AC) corresponds to maximum of the curve. This velocity is called as mos! cy velocity (Cx). Probay, Special features of the curve are : @ Fraction of molecules with too high or too low speeds is very small, @_No molecules have zero velocity. Gi) Initially the fraction of molecules increases in velocity till the Peak of the which pertains to most probable velocity and thereafter it falls With increase, velocity. it As the temperature increases the distribution curve changes as shown inFig The maximum of the curve is shifted towards higher velocity at higher temper ‘The curve becomes broader near the maximum for higher temperature than for temperature indicating that the number of molecules Possessing higher velocitiests increased. : 9 200 "400600 8001000 1200 1400 Molecular velocity (mm/s) Fig-2.1. 3000 2500 3 é Probability distribution of molecules ay ae s 8 ° Scanned with CamScanner«state po The distribution of velocity depends on (m Value. At a pi vier Bases would have a Narrower distribution velocity th 8iven temperature nea ity than lighter gases jmann factor: nt ’s factor is @ 2RT which Boltzmann's : ich expresses the a1... » ogy, Kinetic energy telative to the Probability ofa re" probabil be used to introduce temperature into q Wide variety of 2er0 ¢ ten taken as a starting point, of physi . The most probable velocity increases With increas eseatn € in temperature as shown «,Fig-2.1. This can be readily understood from the Presence of a ee (1). The exponent has~ve sign and the temperature (T) is; his sae The factor therefore increases markedly with in i facie oe Crease in temperature, Thi: F called Boltzmann factor which is equal to 8aS constant, erature. This factor is Further 4 mc = kinetic energy of one molecule of cmt KE Thefictor e2°7 =e RT Hence, greater the temperature, greater the Kinetic en factor increases. It finds application in the theory of rea ty” Of a state of nergy. This factor ical problems, and Bas having ‘velocity ergy and hence Boltzmann ction rates. Mean free path (A): ‘Thekinetic theory of gases, developed by James C. Maxwell and Lu attempts to predict how the molecules ina gas behave. A thekinetic molecular 8as theory is the mean free path. Mis the mean distance traveled by the gas molecule between any two successive collisions, It depends on the molecular size and concentration of gas molecules. the molecular size, more frequent would be the collisions and consequently will be the mean free path. Also more the number of molecules, larger will umber of collisions and hence shorter will be the mean free path. idwig Boltzmann, ‘very important quantity in bethe is KT oO Nscaculated by using the following formula A=—FET— where K = Boltzmann ‘sant, P = Pressure of gas. o = collision diameter or molecular diameter, : “temperature, ‘Thus ial) i.e, mean free path is indirectly proportional to P ‘ : ssUre pire, Mean free path at any given temperature will be wreath ar re less frag lecules will be relatively far apart at these pressures anf tainer CV) increases, ‘ently. According to this equation, if the volume of the co Scanned with CamScanneri Vai, 34 { is travel (A) also increases, I¢ th distance that the molecules : i ke nenaatets or their size increases (or both), then the average distance t a8 travel (A) decreases. : Gus : Eg: Calculate the mean free path for a gas (0 = 2 x 101 m) at one Ato pressure. x273 ir lu KT _ 1,38x10™ x2’ == 20.9210, = TBrokP Ja x3.14Dx (2X10)? x1.01325%10 Thus under ordinary conditions, the molecules of gas travel only a shag distance of the order of 10° m between two successive collisions. Collision frequency or collision number: . Molecules of a gas are constantly colliding with each other many times y,; the course of their movement. These collisions do not change the net Momentum of the colliding molecules but involve transfer of momentum and energy from one art to another part in the gas. Itcan be shown from kinetic considerations that the number of molecules With which a single molecule will collide per unit time is given by Z,=(2n0°C,,p) where C,, = average velocity, p = number density, ie Number of molecules per unit volume. o = molecular diameter. This expression gives the number of collisions suffered by single molecule Per unit time per unit volume of the gas. This is known as collision number (2). The total number of molecules colliding per unit time per unit volume of gas is given by (2n0°C,,9? ). Since collision involves two molecules, number of collisions o like molecules per unit time Per unit volume of the gas is given by 2u= Ya(lins'c, 9" )= 5 (oC) Z1, gives the collision frequency of the i “ et 1e r 8as. It is defined as “The num of molecular collisions occurring per unit time per unit volume of the gas”. Rt 1 2 = Fy O°"C..PiP2) where p, and p, are number densities of molecules of ?*! and 2 respectively, For ideal gas, P = “se where N rae i = nN, total number of molecules it * moles of gas, Since ‘p’ is the number of molecules per unit volume Scanned with CamScannerr ® stat 35 N thus P=pKT or p=? =a" Pra P Z| Line Cw and Zu sd noo (_P , al "°C, a) } unit of Z, is S"! and that of Zy is Sms, lision frequency increases with j . ese per unit volume of gas, °#8€ iN molecular size ang umber of ni 5 i j ~ Calculate collision frequency of 0. i sm Presse (Cy = 444 mS"), molecule at 25°C (9 =, 10m) and 1 Py Zh (+(e) } 3.142% (3.61107)? x444x(1.01325x10°) ~ 1.4142x1.38x10™ x (298 =T1TX10"S'm?, Iypesof molecular velocities: There are three types of molecular. velocitites. 1. Most probable velocity (Coup) “tis the velocity possessed by maximum number of molecules of gas at a given temperature”. ‘Expression for Cy» is derived from Maxwell-Boltzmann distribution equation which isgiven by- 3 ict real m | BT Cac veel) n 2nRT. Differentiate the function on right hand side of equation with respect to iS a | *duating the result to zero. i.e apply condition for maximum and minimum, | a 2Ce > Cree ae —MC _ 9 eR reg mame HE | RT y cea [2 mC] _ i RT \ D Scanned with CamScannerUniversity Chem: ' em * SO Vy, Two possible solutions of this equation are for C = 0 and C= cory to the minimum as there are no molecules having speed equal to zero or int mC? . i ‘Therefore [2-22] must be equal to zero, This condition deterring, probable velocity. mC 2 < 2 mC? =2RT ele Fer)? » = PRT PR ee sented () = or 1.4, M 2. Root mean Square velocity (RMSV) (Com): “Tt is the square root of the mean of the squares of different velocities Possess by gas molecules at a given temperature.” 2 2 ¥ Cn + +Ch+ Co where CyC,C; ete are molecular velocities n n= number of molecules. BRT RT : Com = pet or Lr sevee(2) a) Forthe same gas at two different temperatures, the ratio of RMS velocities wil be, G_/h & VE b) ee on different gases at the same temperature, the ratio of RMS velocitis Wi Ie, - 9 Scanned with CamScannerys sate a . 37 A erage yelocity (Cw): . i 7 9 arithmetic mean of the ditre, f velocities are not i ethree types 0 ot very differe, oo 43. : nt from each other, Fro RT RT Capt Cop = 17 E16 (RE. 4 [RE Cogs? Cav ? Comp M 7 wae or 1.7:1.6:1.4 or 1:0,92:0,82 Cras ?Cor 2Cuy =1:0,92:0.82 1m equations Problems: 1. Calculate Cav, Crms and Cm for oxygen molecules at 298K. At. ‘What temperature would hydrogen have same values of these velocities? C,,=1.6 - T = 298K,M = 32 x 10°kg,R = 8314JK"'mol". =16, 32x10~ RT 8314x298 x C,,=1.7,/R2 21,7, |22 2 = 473.03ms". me EI L390" RT 8.314x298 4 C= sel 0.9 1GKET® = 389.55ms was M 14 32x10° The temperature at which Co, = Cu, 445.2ms*. To XMuy ELE] ehh eS M hn, M I, MJ, My = 298x2x107 _ 1.6K. 32x10" Scanned with CamScannerf 38 University Chery % ) The density of CO at 273K and 1 atm is 1.2504 kgm®. Calculate a) Crm, .b) Ca C) Crp. BRT _ BP 3 Re! y c= pete JE te: 1.2504 kg/m?, R=8.314K"'mott me ag Tg TPR dH125 kg ot Paty, 3x1.013x10° ‘ = [SxLOlSxt®" = 493ms". \ias00 749 IP, fi.013x10° 4 21.6 [P 1.6, eos = 455.4ms". Cu 16 16" 2504 P _ 1.4, -ousxio® a 21.42 21.4, [E02 = 398.48ms". Com =! Ee 1A 2504 | 3. Suppose that a gas contains 5 molecules with instantaneous velocity 2 mg, 10 molecules with 3 mS"! and 4 molecules with speed of 6 mS". Determine average, most probable and root mean square velocities. | Cy = ASHOSEIS | 5 368n5! . 2 2 2 Cu = 2?x5 +3° aoee x4 =3.66 mS" Cup = 0.92 x C,, = 0.92 x 3.38 = 3.1 mS" | 4. Calculate Cm ratio of Neon (M=20 gmol") and Helium (M = 4 gmot") oc RT BRT c= PEE o,=PRE oc, - PRE M * YMye “ YMye Cre _ con 2.236 5. Calculate Cims of CHi gas at 27°C. . At what t. i lee have the same Cis as CH molecules have at mre. ee BRT 3x8.31 Coa = PRE a .7, SX SHOT ms = = Ts = 683.62ms™. (BRT, Con, = 1c. q {3RT, Mn, Mon, Ca = Conn, Scanned with CamScanner d7 te = eae T= Man 20039 So Men, M, § Men 16 * 562.5K or 289 so alculate Crms, Crp, Cov Of CO2 at 270 C c. =1.6, 7. : RT _, , [83iaxa00 cate ETT» kr RT _, , [B3laxa00 coe = atm, critical phenomenon (Andrew’s experiment): During early part of nineteenth century, a number of es soe Nibetc. were liquefied by subjecting the gas to high pressure alow tea ae effect of temperature is rather more important than that Of pressure. ‘The essenti 1 conditions for liquefaction of gases were discovered by Andrews in 1869 as a result af his study of P-V-T relationships for COz, It was found that above c: the gas cannot be liquefied what ever the pressure applied. This temperature is ¢; alled critical temperature (Tc) the Pressure required to liquefy gas at its Tc is called critical pressure (Pc). The volume Occupied by one mole of substance at Tc and Pc is called critical volume (Vc). The &50r liquid is said to be in critical state. Te, Pc and Vc taken together are known Scitical constants, At Tc and Pe, physical properties of gas are indistinguishable its liquid form and they cannot be distinguished. The phenomenon of smooth it of a gas with its liquid form is called critical phenomenon. It is a reversible ertain temperature, . The Tesults of Andrew’s experiments are shown in Fig-2.2 pressure is plotted ‘ai Volume for CO: at various temperatures, Each P-V plot is called Shem iste Consider an isotherm at 13.1°C. At low pressure, COz is entirely gaseous 5 Dorp sented by apoint A. On increasing pressure, volume decreases as ae On AX of isotherm, At ‘X’, the liquefaction starts and ane ogi renaint Pointy’, CQ, has been completely liquefied. Between Tie "as the "stant and both the gas and the liquid phases are in eq ¥ iS Scanned with CamScanner'd increases as the gas condenses. The pr, i yunt of liqui pressure increases, the amor iq A apo aeee ‘ corresponding to horizontal portion "XY’ of isotherm is liquid at the temperature of the isotherm. genau coeptthee The P-V curve at 21.5°C shows a similar behavio} dUefact starts at higher pressure and horizontal portion MN ee As fen temp a increases, the horizontal portion becomes shorter an ne eae lec e reduced to point and above this temperature gas el 4 catleal ton at ever 4 high pressure is applied. This temperature 31.1°C is calle erature fy CO2, This isotherm at Tc is known as critical isotherm. o Supe the ——> Pressure (atm) Volume Fig-2.2., In the Fig-2.2, in the area left to the dotted line below critical isotherm, only liquid CO: exists. To the right of dotted line only gaseous CO: exists. Within the dotted area obtained by joining horizontal portions of isotherms, two phases (g8 and liquid) exist in equilibrium. Above T:, no horizontal portion of curve is obtain and it is parabolic. { Determination of critical constants: (Tc, P<) (Cagniard- de la Tour’s method): These constafts can be determined by a simple meth: i sed : ts can be 1 od. enerally v wheri thé substance is in liquid state at ordinary tempenrare ee , The principle in this method is at Te, the surfa 7 Liquid and vapour phases disappears. 4 ce of separation betwee! Scanned with CamScannerstate 41 . uid under examination j., e liquid un 10 is taken in ee temperature Src varied gradually pyr st (¥) enclosed in a place; n . The vessel (V) is attached t citcutatin Blass jacket ‘ eos tye temperature is first lowered soe mang rte able liquid from ee?) petween two phases becomes shar at the vessel ig Cooled and surf ‘ Surface of tion bE ally i M i eae sora y increased until the surface of weet is noted, ‘Then he we Pe Fig-2.3. ‘ b Then the jacket is cooled gradually until surface of separation reappears. The temperature is noted. The mean of two temperatures gives critical temperature. +t) ED . ‘The temperature above which a gas cannot be liquefied what ever ‘wplied is called critical temperature”. ae The pressures of these temperatures are recorded from monometer and their Teanistaken. It gives critical pressure. The pressure at critical temperature is called Sitical pressure, the high pressure and mathias method): ated vapours of a substance i satelite 3 ‘obtained Line VC gives density of liquid (Fig-2.4). Determination of critical volume (Cailletet The mean values ities of liquid a of the densities of lial i #ieasured and plotted against temperature. A straight ii nsity of saturated vapour and ‘CL’ Scanned with CamScannerTemperature Densities of saturated vapours Densities of liquid v Density a | Fig-2.4 | ‘The point ‘C’ where the two curves meet gives critical temperature, The mean densities are theri plotted against various temperatures which gives a line MC. 4, | point ‘C’ density of liquid becomes equal to that of vapour. Therefore it also gives the value of critical density. The critical volume is then obtained by dividing molar mass of the substance by critical density. van der Waal’s equation: Relation between van der Waal’s constants ‘a’ and y with critical constants (Tc, Pc, Vc): van der Waal’s equation for one mole of real gas is given by a [P+ |ev-» SRT we () PV+ | -Pb- & =RT Multiply by V2 PV3 + aV—PbV? -ab=RTV? Arrange in decending order of V, we get PV?—PbV? -RTV? +aV-ab = 0 (Divide by P) v [oF] 2B a ) ’ This is a cubic equation in the variable ‘V’ and therefore for any value of P and 4, it will have three values out of which all the three may be real or one may be and other two are imaginary. | If at constant temperature, the values of ‘V’ are plotted against ‘P’, then curves are obtained as shown in Fig-2.5 for CO2, Below-Tc, the horizontal portion i” shaped curve ABC. This curve predicts three values of ‘V’ corresponding t0 Scanned with CamScannerand C. As the temperature tow. Boi A Vv soproach one another and fina ally the isothy the three roots of van der wy, © iden Moves 1 ho ra tical and equal to critical vate es ion are nett ctl pot ose Oh a v=Voor(V- -VO=0 YY teal and Positive W-VP=0 3 -3V V2 + eV Vie 5 ——— Pressure (atm) Volume (m’)_ ———> Fig-2.5 Atcritical point, equations (2) and (3) must become identical. Comparing and. equaling the coefficients of like powers of V gives Mabe RE wet (4) 2a . ve a) Pao (5) ve ab a © Divide equation (6) by (5) 5 ¢= 3b’ Substitute the value of Ve in equation (©) 4) Re rsd substitute the values of V,and Pe in equation -( Scanned with CamScanner‘en RTT gy _ + 276RT) 3(3b)= b+ 9b= a _ 2TORT. _9_1=8 a 8a T"2Rb Ve g=P27b? =P.27% ge Therefore van der Waal’s constants b=~,* a= R27! = E27 a=3Py — 8a__ 8P.V. ~27eT, 37, ficabili i be tested by calculatin, The applicability and van der Waals equation may ; Be critical congas of gas for which ‘a’ and ‘b’ has been determined from pressure. volume or other measurements. Other equations used to calculate ‘a’ and ‘b’ as follows, Q7RT? , RT ERIS pe a GaP. BP, The behaviour of 1 mole.of CO: at ordinary temperature may be Tepresented with fair accuracy. For CO, - Ve = 0.154 liters/mole. Te = 306K Pc=6l atm. a, Problems: 1. The van der Waal’s constants for gaseous HCI are - a = 0.367 Nm mol? and b= 0.0408 x 10 mmol". Calculate critical constants of the gas. Solution: Ve = 3b Ve = 3(0.0408 x 103) = 0.1224 x 193 m,mot! a 0.367 270" ~ 270.0408 x10" ~ 817 x 10°Nm*, 8a 8x0.367 Te =—— 27Rb 27x8.314x0.0408x10> 7 320.6K. Scanned with CamScannerao _ ———nssnsSscssnstesentieenicnsinssisis d Po of . The Tc and P of a gas are 393 K ang 5 : er Waals constants, R = 8.314 Nin mosphere Tespectively, Calculate 7 : ~ Lat = 1.013 x (Q7RT.Y _ 27X(8.314%393» e BaD Rh eee a=" 64P. 64X50%1.013x10F = 9-889Nm‘mot-! RT, ___8.314x393 EE 2 Sete b="gp ~ Bx50x1.013x10° ~ 817 x 10> m'mott, sawof corresponding states and reduced equation of state: In 1881, van der Waal showed that instead of using vot emperature of @ gas, the ratio of these quantities to the coneprrde i e constants could be used. in the equation. Then an important aie critical uprinciple of corresponding states” is obtained, son oP Vv T P= Va T=— Let PF, Pp ON: aD Where Pr, Vs, and T; are known as reduced pressure, reduced volume and reduced temperature respectively. Substitute these values in van der Waal’s equation [P+Z-](v-»)= RT we get [re + al (V.V,-b)=RT.T, V,=3> T=38 5 a Since P, = 7] © O7Rb 'b? 8a a a a p—* +4 _ |(v,.3b—b)=RT, Parade ll RT TIRb -2 3 fal. ia [p+d lov» 7b = 3 bal, =a Bee |ov-D= 2b ered|ou-nem Scanned with CamScannerUniversity Chemisty " y Vo 46 us i own as reduced equation of state. . ion i it ‘Waals constants ‘a’ and ‘py is equation involves neither R nor van der ‘ He itisa eoera equation applicable to all substances. It aaa this equation - if two or more substances have the same reduced terns anes a reduce pressure, then they will have the same reduced volume. known’! principle of corresponding states. bend thes ing the same reduced temperal samme req oe a ced vane are said to be in corresponding state» p All gases behave nearly alike in terms of these variables. Gases having te same values of their reduced variables deviate almost equally from ideality, This equation is kn Liquefaction of gases: Liquefaction of gases is physical conversion of a gas into a liquid state, Th processes are used for scientific, industrial and commercial purposes. Many gases cay De put into a liquid state at normal atmospheric pressure by simple cooling. ‘While few gases such as carbon dioxide, require high pressure as well. Liquefaction is useq for analysing the fundamental properties of gas molecules (intermolecular forces), for storage of gases, for example: LPG, and in refrigeration and air conditioning. In this case, the gas is liquefied in the condenser. Ammonia was the first such refrigerant, but it has been replaced by compounds derived from petroleum and halogens. Liquid oxygen is provided to hospitals for conversion to gas for patients suffering from breathing problems, and liquid nitrogen is used in the medical field for cryosurgery, and by inseminators to freeze semen. Liquefied chlorine is transported for eventual solution in water, after which it is used for water purification, sanitation of industrial waste, sewage and swimming pools, bleaching of pulp and textiles and manufacture of carbon tetrachloride, glycol and numerous other organic compounds as well as phosgene gas, Gases like NH, SOz, CO: or Ch: etc. which have hi iti be easily liquefied by applying high pressure alone, Ott ae ee etc must be cooled below their Te and liquefied by applying high pressuve. ‘The principle involved in liquefaction of Gases is 1) Agas must be at or below its Tc, Lower the temperature below Te, easict would be the liquefacti cE liquefaction uquefaction and less would be the pressure required fot 2) The gas is cooled either by doing ext 5 i : the internal forces of molecular aration ony opening “ A force of attraction exists between two adi of attraction is called van der Waal’s force, One. molec oleules Paine ‘Its force of at Scanned with CamScannereaten molecule when they bro o oth than chemical forces, van cer gtoaether, These cn nc Can ea i en jo pen gas molecules are far e element; ott lived inter molecul: 180" tecules come closer b apart and are in rapid os t ese mol der Waals forces arene Pressure and Sines Pie: motion Wen polite olid state. Then a gas « apable of holding the mane 8 Withde oy jignd yn pressure. During exp; an be liquefied by af wre aules together tof fom th forces of attraction, by ute does some woke crea sud aes js liquefied. ng its energy. Hence temperate en Thomson effect: Joule and Thomson observed that when 5 + a i F d into a region of low pressure, it a er high Pressure is permitted henomenon is called Joule Thomson effect. This su m temperature. This Prattaction between gas molecules. As the gas expats, the the existence of force fom each other. Thus work has to be done in order to Ser tamer coe Work has done at the expense of kinetic energy of gas fetes neti energy decreases and since it is proportional to temperature, ‘emperatne fee For each gas there is a characteristic temy ic i i perature above expansion shows heating effect while below it, the gas woals ct eee ne temperature is known as “Inversion temperature” (T,). This is related to van der Waals constants by the relation i 2a Rb Allreal gases have an inversion point at which the sign of inversion temperature which depends on the pressure of the gas before expansion. Helium and hydrogen are two gases whose Joule-Thomson inversion temperatures at a pressure of one atmosphere are very low. ‘Thus, helium and Bitogen warm up when expanded at constant enthalpy at aire roe nai, have On the other hand, nitrogen and oxygen, the two most abundant gases #0 2°% inversion temperatures of 621 K (348°C) and 764K (491°C) peepee these gases can be cooled from room temperature by the JouleThomsonelfect : For an ideal gas, p is always equal to zero: ideal gases neither warm Pon being expanded at constant enthalpy. ; vature bave ity high Gases which sh Ling effect . s which show a coo! ling 8 Tand i: Gases like H, (T, = 93K) and He (T, = 31K) have low iting effect. AtT,, there isn ese gases are cooled below their T) th | 0 Joule Thomson effect. ie ae Scanned with CamScanner soule48 SS ction of gases: the liquefa e or ated that “There is fall in semperamte When ; is ide to low presst we plug from high pressure side Pressure siden fs Joule Thomson meth Joule and Thornso! a iS 4 is forced through Seth d is shown in Fig-2.6. oO apparatus used in this m Fig-2.6. . , ) at its centre. Itis Provided wig, indrical vessel is fitted with porous plug (O) at , ey A hearin either side of porous plug. A certain amount of gas is end, jn a volume Vi, at temperature T: and pressure Pi. The entire system is th insolated such that the process is adiabatic. When the gas is slowly forced through porous plug and allowed to expand into volume V2 at pressure P2, its temper, _ decreases. , ‘Then Work done on the gas = PV: Work done by the gas = PzV2 Net work done = (P:V2— PiVi) The change in internal energy AU =(U,—U,). U, and U, are internal energies before and after expansion. In adiabatic work is done at the expense of internal energy. see ‘Thus (U, -U,) = (P,V, -P,V,). But enthalpy H = (U + PV) Since H, = H,, H,-H,=AH=0 Enthalpy change during adiabatic change is zero, The change in temperature (dT) wit : 7‘ (4T) with pressure change (dP) at constant enthalpy dP adiabatic expansion of as results ji x ts i . then heating effect takes place, Sin cooling. .. 1 has +ve sign. If p has -ve sig The fall in temperature j i e fal € in-an adiabatic ion i: between initial and final Pressure is large, eae ’S greater when the differen* aes is given br = is given by # Where p is called Joule-Thomson co-efficient. Generally Scanned with CamScannert — a | z ratio of specific heats of the | ed on Joule-Thomso; 88S. All pases includ, ‘ ott? ES as expansion, the rene ’ oan Ha and helium are i puring 8 ia erin ne Pressure decreases, ‘so ihe «: on. With that in mind, the following ble es, So the sign of ap is nes jtion- te A Hi ifsc ols or warms a real gas: ‘able explains when the Joule“thonse C0 lone I Positive negative | always L____|negative | Fig-2.7 . Fi inary temperatures have fairly Gases which show a cooling effect under ee aeeraionl temperature, igh inversion temperatures. Gases like H, and Fi i ‘Thomson (I= 193K for H, pnd 33K for He) and they show ae pa their Spansion under ordinary temperatures. If aaect Joule-Thomson effect is the Wersion temperature, they also show cooling The apparaturs is shown in Fig- for the liquefaction of air by Linde’s process forces of attraction id Liquefaction of gas takes place when the inermoleo increased either by “ome high. The intermolecular forces of ata as, Flence a gas can be liquefied ‘easing temperature or by increasing presen rite ‘combined effect of both. Y cooling or by the application of pressure OF by a Scanned with CamScannerPure and dry air is co’ heat that is produced “EE f about 200 atmo; essed to a pressure 0} sph " y omnpression is removed by passing the gas 4° Any during expand suddenly through an, rug! i, cor fs mpressed air is allowed 10 CTP and the pressure ig rept, ing pipe C. CO! it gets c cooling Py large chamber whereby maa de to pass through the outer gype*'g valve V into a about 1 atmosphe sent back incoming re, The cooled air is tgoing air cools the incom; i nis way the outgoing a! ¢ Ming ai, 1° | tothe compressor. In this W ‘The process is continued untit aig j." The nsion. Pp air expal Tigues air further cools on | and is collected at the bottom. | Questions | ve Sw ws _ One mark questions. ‘What is inversion temperature? ‘Write the relationship between rms velocity, ‘What is the effect of temperature on molecular velocity? ‘What is Boltzmann factor? What is critical volume? ‘Write an expression for critical temperature in terms of van der Waals constants. What happens when gas is allowed to pass through nozzle from high pressure to low pressure side? average velocity and Most probable Two marks questions. vite Maxwell Boltzmann equation for molecular velocity and explain te What is mms velocity? Write the equation used to calculate rms velocity. Define critical temperature, State law of corresponding states, What is the effect i i ; i ee ct of dipole-induced dipole inter action on Jiquefaction © What is Joule-Thomson effect? Calculate critical Pressu; constants es a= 3.6 atm lit?/mol2 (P.) and critical volume (V.) Given van det wet! b= 4.28 x 1072 it mot". Scanned with CamScanner