5. States of Matter Sitio | ———— To study about intermolecular forces, various gas laws p-V=T relationship, kinetic theory of gases, behaviour of n der Waals equation for pour pressure, boiling point, surface tension, vi Introduction ‘The characteristics of any of the three states of ater depend on the energies of molecules and the manner in which molecules of the substance aggregate, Therefore, it is necessary for a chemist to know the physical Jaws which govern the behaviour of the matter in different states, particularly liquid and gaseous states. To is necessary to understand the nature of intermolecular forces, molecular interactions and effect, begin with, i of thermal energy on the motion of particles. Intermolecular forces ‘The forces of attraction and repulsion that exist between the interacting particles i.e., between atoms, molecules or both are known as intermolecular forces. van der Waals forces ‘The electrostatic attractive forces that exist between atoms, molecules or ions of substances, when they are brought sufficiently close to each other are called van der Waal’s forces. They are much weaker than chemical forces. Example: van der Waals attractive forces are responsible for the existence of substances in solid or liquid states. Greater the van der Waals force of attraction, higher the melting and boiling point of the substance. Dependence of van der Waals forces on molecular mass and physical state In a homologous series, with increase in molecular mass, the size of the molecule increases. This increases the magnitude van der Waals forces of attraction between the molecules. Therefore, melting point and boiling point increases. Example: Among the alkanes, lower members are gases (C; to C,), higher members (Cs to C12) are liquids and solids (Cts onwards). van der Waals forces are very strong in solids since the particles are very close to each other. It is weaker in the gaseous state as the gas molecules are far apart and intermediary in the liquid state. rs of carbon atoms are held together by van der Waals forees of attraction, This makes graphite soft and possesses lubricating properties. i | Tn graphite, the hexagonal Scanned with CamScannerDispersion forces or London forces atoms or non-polar molecules due to induced polarity These are the fore ion existing between when they approach cach other. b) in elose vieinit (a) far away from (by inet Z one another — U® ©. © © 6 “1 with induced ‘Mom “A° with induced dipole vom ced dipole A 0 Ai ” , oY Polar Non-potar Dispersion forces between stoms Dipole-Dipole forces These are the forces of attraction which exist between two polar molecules. In this case, positive pole of the ve pole of another molecule. Se H—C / Dipole-Dipole attraction molecule attracts the neg be H-Ci Dipole-Induced Dipole forces These are the forces of attraction existing between a polar molecule and a non-polar molecule (or atom) due to induced polarity in non-polar molecule (or atom) when a polar molecule comes in its close vi (a) Molecules away from one another ak © Polar molecule Non-polar molecule (b) Molecules in close vicinity Polar molecule Induced dipole in non-polar molecule Dipole ~ induced dipole attraction fs | This is known as dipole-induced dipole interaction because the polar molecule induces the polarity in the { non-polar molecule. Hydrogen bonding These are the forces of attraction existing between hydrogen atom attached to a highly electronegative atom in a molecule and the electronegative atom of the neighbouring molecule or atom or group in the same molecule. bee H- H-F Hydrogen bond Scanned with CamScannerup pea ABx0Ua 40 99401 ‘aynsajour Supnoqysiou 30 dnosd Suynoqysiou payoene st ue yuouoyo ‘wore uafiosphy sanesouan299 Tow yoryss 0 Audigy ‘suon>eso1Ut quatua|9 atp Jo pur pews: ajodip ‘wD AuaneBou0ns9p2 1 paysene : uuafospéy Surpu0q, soseaisut |-sjodip ue | ad wd uy aseauout spo aud Suyjoq | s93uons ‘O'H'd-H | _yntm sosvozouy usemieg | —_uaSorpsH aynoayour sejod-uow ssa0u0} Jo Aaiqezuejod uorsiedsp 10 9218 vwoyy s2800ns soouoy asaqn | pur anoajour mnq samo} | oy anp st sem UF sajno9jour $9010 soseaiout | 2jodsp-ojodip | susZojey pue sase8 { ‘ABs9u9 awjod-tou pur | afodip paonpuy Arpgnyos | wom s2xe24\ | a[gou jo Arpiqnjog | — ym saseaxout 1 OINUT aejod usaaog -sjodiq, 2 (sojnoouu sod) 0 Ayzejod pue ssvut sejno9jour (Spujos ur se) wd 0S OHO-¥"YHO-4 | ur asvarout 2 £32902 | froyeunrxosdde | saynoajou 1ejod $9010} Je3uong N-O-W "XU | __ ya sasvarour T | vonserauy | aourisip oyg | om —uaamog | afodiq-ajodiq ST SO canada esas) seu sejno9jout wd os Jo swore soo10y 30 spinbyy u aseazout Ajareunxoxdde anjod-uou | wopuoy (30) Suyoq MOT asayea,y | sase® aiqou‘uadopey | tM soseazour tsounstp woys | omy uoomiog, uorsiadsiq. im uonesado peaysdqd yduang aqduexg ao19j Jo yuorxg | usoMIoq 29UEIIP =A) | A omsiC wonsezaquy ana04 Scanned with CamScannerThermal Energy The energy that arises duc to the motion of atoms or molecules in a system is known ay thermal ener. eis the m ic energy of the particle of the matter and is responsible for the movement of particles away from one ion, asure of average nother, ‘This movement of particles is called thermal me ‘Thermal energy a Intermolecular forces, Comparison between thermal enorgy and intermolecular forces, 4 | Repulsive forces Attractive forces | Mav Strength | Solid > tiquid > gas Decreases with tempera Results due to decrease in kinetic ¢ _| Maximum in Strength Gas > liquid > solid_ fl Tnereases with temperature 7 Res in kinetic energy | jum in solids ts due to incr Gaseous state tis the state of matter in which the intermolecular forces are the least between the atoms or molecules and thermal energy is highest and the particles are far away from one another. Physical properties of gases Irrespective of the nature of the constituent particles, all gases possess some common properties. They are: + Gases are highly compressible. + Gases exert pressure equally in all directions. + Gases have much lower density than solids and liquids. + Gases do not have definite shape and volume. + When different gases are mixed, they form homogeneous mixture. + Gases possess high diffusibility. At normal temperature and pressure, some of the non-metallic elements and their compounds exist in the gaseous state. Gas Laws To explain the behaviour of gases with respect to the effect of pressure and temperature, Various laws were proposed based on experimental facts and are known as gas laws. (a) Boyle’s law (p-V relationship) Statement: Ar constant temperature, the pressure exerted by a fixed amount of gas is inversely proportional to its volume, pes (at constant T and n) ; is proportionality con at constant temperature, the product of pressure and volume of a fixed mass of gas is constant. Sxeimts Scanned with CamScannerIfa fixed amount of gas at constant temperature , occupying volume Vj at pressure py undergoes expansion, such that votume by V, and pressure becomes pp, then according to Boyle's law, piVs = p2V2 = constant ox Pressure (p) -» ! } ] 40R a Volume (1) > vakanet i) (ant) > Graph of pressure of a gas, p vs + Graph of pressure. p vz. Volume, Vof raph of pr gas,pvs + Spas at dffrent tnperanare. The value of ky for each curve is different because for a given mass of a gas, it varies only with temperature, Each curve corresponds to a different constant temperature and is known as isotherm. m iid Density, — => — Ay vm Substituting in Boyle's law, pok, 2 m m d=px are d=pk’ or dep i.e. at constant temperature, density of a fixed mass of the gas is directly proportional to the pressure. (b) Charles’ law (V-T relationship) Statement: Ar constant pressure, the volume of a fixed mass of the gas is directly proportional to its absolute temperature. VexT (at constant pressure) v T Vv T If V; is the volume of the gas at temperature T, and keeping pressure constant, temperature is changed v,_V, tee Fora fixed mass of gas at constant pressure, for every 1 degree rise in temperature, the volume of the (constant) to T;, then volume will change to V; so that aus increases by a factor of = 1 73.15 of the original volume of the gas at 0°C. Scanned with CamScannertC) 273.15 temperature 0 °C view uc al Vos where V, = V+ 273.15} Origin of Kelvin scale is Charles” law. Kelvin temperature se volume of the gas at temperature (°C and Vo 8 also called thermodynamic scale or absolute scale. volume of the gas at _ |. A plot of volume against temperature at different pressures is given below. Volume (in Ly 300 -200 -100 0 100 Temperature (°C) V=T Isobar Each line of the volume vs temperature graph is called isobar. When th the temperature axis at is zero ice. Absolute Zero Pi A plot of pressure against temperature at different volumes is given alongside: From the graph, it is observed that at zero Kelvin, sis zero. raph is called isochore. the pressure of the ach line of this xed amount of the gas is directly proportional to the My V2 100 200 300 400 ‘Temperature (K) > a p-T Isochore Scanned with CamScanner(@) Avogadro's law (Volume - amount relationship) Statement: Equal volumes of all gases under the same conditions of temperature and pressure contain equal number of molecules (n). Voc n_ where n is number of moles of the gas The number of molecules in one mote of a gas is determined to be Avogadro constant. A gas which obeys Boyle's, Charles law at all conditions of temperature and pressure 6.022 x 10" and is known as is known as ideal gas. Such a gas is hypothet (@) Ideal gas equation The combined gas equation which follows Boyle's law. Charles law and Avogadro's law is known as ideal gas equation, Boyles law; Vee at constant T and n P Charles law; V & T at constant p and n ; Ve nat constant p and T is the same for all gases. This is ideal gas equation, where R is universal gas constant, pV =nRT. ‘The value of R depends on the units in which p, Vand T ¢ measured Calculation of numerical value of R Volume occupied by one mole of an ideal gas under STP conditions (273.15 K and 1 atm pressure) is 22.4 L mol"! The value of R for one mole of an ideal gas is calculated as follows: R x wv Latmx 22.4107 m* 1 molx273.15 K R=8.214 x 107 atmL KT mol! R=8314) K"' mol Units of R . (i) 83145 K mort Gi) 0.0821 L atm Kt mor (iii) 1.987 calorie K" mot (iv) 8.314 x 10 erg K' mol | (9) 0.083 bar LK mot () Combined gas law For a fixed amount of gas, at two different temperatures T, and T., pressures p; and p; and volume V, and V; respectively, the gas law is written as piV, =nRT, p.Vz=nRT: Scanned with CamScannerAR (constant) AR (constant) The above equation is known as combined gas equation Relationship between density and molecular mass of a gaseous substance For an ideal gas, pV=nRT; n= where m= mass of the gas, M = Molecular mass of the gas pV=rT (oy M=™ RT Ls P RT Mea where a=% ie., density of the gas (g) Dalton’s law of partial pressures Statement: The total pressure exerted by a mixture of non-reactive gases is equal t0 the sum of the s, the pressure exerted by the individual gas is Partial pressures of individual gases, In a called partial pressure, Ia cylinder contains ‘n’ type of non-reactive ganes. then the total Pressure inside the cylinder is equal to ture of ga the sum of the partial pressures of individual gases, 1.0.5 Prott = Pa + Pp +... Po (at constant T, Vy Where pa. Pa. Pyare the partial pressures ofthe gases A, B..cn respectively. At constant temperature and volume, partial pressure exerted by a gaseous component in a mixture of sen ctve gases is directly proportional to the mole fraetion of that gaseous component, EER, PLN, Pras of dry g P sty eas = P tor — Aqueous tension ‘The pressure exerted by saturated water vapour is called aqueous tension, Ina - : 1. 6 L of a gas at 2 atmosphere is compressed at constant temperature till the pressure in the cylinder increased to 3.5 atmosphere, Find its volume, Solution Given: pp=2atm Vv, =6L pr=3Satm V;=? According to Boyle's law (at constant temperature), Pressu sis the dference between the pressure exerted by gas and its aqueous tension, pV = constant =3.43L, © prVi= Pz Scanned with CamScannerthis balloon will burst if the volume exceeds 5.5 dm’. 2. A balloon is filled with 3.0 dm’ of air at 27 Find the maximum temperature at which the balloon will not burst Solution Given: V,=3.0dm', T, =27°C=300K, V2=5.Sdm’, Ty= According to Charles lav (at constant pressure), & constant ¥ coms The balloon will burst if the temperature exceeds 50 K. by a gas at 0 °C is 2500 cm’. Calculate the volume of the gas at 300 K. Solution Given: T, = 273.15 K, V; = 2500. cm’ T=? 300K, Vi=? According to Charles law, wee + ann 747 cm? 747.1 cm? = 2747.25 cm? 273 4. 1.5 L of an ideal gas is filled in a cylinder at 1 bar pressure and 310 K. The cylinder will explode if the pressure exceeds 1.75 bar. Find the maximum temperature at which the cylinder will not explode, Solution Given: T= 310K, pr=lbar, Vj=15L, T. p2= 1.75 bar According to Gay-Lussae’s law (at constant volume), P constant T T:=542.5K nperature exceeds 542.5 K, then the cylinder will explode. Scanned with CamScanner400 mL of an ideal gas is filled ina cylinder at 250 K and 50 mm of Hg pressure. What volume woulg this gas occupy at STP? Solution Given: V, = 400 mL. STP: Standard temperature and pressure T1=250K T.=273 K P=50 mm of Hg Po = 760 mm of Hg According tothe combined gas eq PoV. _ PAV, tT V, =50%400, 273 x 250 "760 Vo = 28.74 mL, Calculate the volume occupied by 2.2 8 of CO; at 27 °C and | bar pressure, Solution Given: p=1 bar, R= 0.083 bar L K™ mol" (because pressure is given in bar) =™, RT Pp 0.083% 300 eee | (+ R= 0.083 bar LK mor) =1.245L 8:8 g of gas occupies a volume of 5.05 L at 308 K and | atmospheric pressure, Calculate the molecular mass of the gas, Solution Given 8.8, V=5.05L, T=308K, p=latm R= 0.0821 L atm K™ mol” (because Pressure is given in atm) From ideal gas equation, m V=—RT year R 8 x 0.0821 x 308 m=™ RTL pectzs0e) Vp 5.05x1 nit ye M =44.06 g mol" ye a7 The molecular formula of red phosphorus is P: (Z = 31). Calculate the density ofits vapours at 300°C at 760 torr. Solution Given: Molecular formula Ps Scanned with CamScannerp= 760 torr R= 0.0821 La 0.0821 «573, = 2.64 gL" (or) 2.63 gdm” 9, Acylinder is filled with 0.02 moles of O; and 0103 moles of Hat 100 °C. The volume occupied by the gaseous mixture is 1500 em’, Calculate the partial pressures of O2 and H; and also calculate the total pressure inside the cylinder. Solution Given: Number of moles of 0; = 0.02 moles Number of moles of H; = 0.03 moles Volume of the gaseous mixture = 1500 em? From ideal gas equation, PV = nRT. (i) Partial pressure of Or ng, RT. Vv 02 x 0.0821x 373 150010" Po, =0.4083 atm (because volume is in litres) (ii) Partial pressure of He ny, RT Pisa 0.03%0.0821 x373 1500x 107 Py, = 0.6125 atm (iii) Total pressure Prout =Po, + Pu Protai = 1.0208 atm 0.4083 + 0.6125, 10, A2 L flask contains 4 g of H; and 2.8 g of Ny at STP. The total pressure of the cylinder is 0.8 atm. Calculate the partial pressures of Hz and Nz. Solution Given: Mass of Hz Total pressure Partial pressure 4.g, Mass of Ny =3 8 0.8 atm Scanned with CamScanner8 3g (Partial pressure of Hy Pu, = ol x08 0.7619 atm Gi) Partial pressure of N, Py, 08 0.1420" “Ty, iy, .0381 atm (or) Pras = Py, +Pu, =0.8 -0.7619 0.0381 atm Px, ~ Pa, Kinetic molecular theory of gases Kinetic molecular theory is based on the following postulat © A Bas consists ofa large number of tiny particles of identical size, shape and mass known as molecules, * The volume of gas molecules is negligible compared to the total volume of the gas. 1¢ molecules collide with each other and * Molecules of a gas are always in constant random motion and th also with the walls of the container. * The pressure exerted by the gas is due to the collision of the gas molecules with the walls of the container. * The collisions are perfectly elastic and there is no loss in energy during collisions. ° The average kinetic energy of the gas molecules is directly proportional to the absolute temperature i.e., average kinetic energy absolute temperature. f There is no force of attraction between the molecules of the gas at ordinary ter T On the basis ofthe various assumptions made in the kinetic theory of gas mper: derived from which all the gas laws can be deduced, This equation is kn , pV = tmne® where p = pressure exerted by the gas, V = Volume of the gas, m = Root mean square velox number of molecules present in volume V, Scanned with CamScannerRelation between Average kinetic energy of gas and temperature czas equation, pV = mine ass of the gas. According to kine! as, mx n= M, the mo energy xe} pV for I mole of the gas But pV =RT RT for 1 mole of the gas or KE=2nRT for n moles of the gas ‘Average kinetic energy « absolute temperature Different types of molecular speed The molecular motion can be described in three different types of speed. They are (i) Most probable speed (a): This is the speed which is possessed by the maximum fraction of the gas molecules at a given temperature. Mis the molecular mass of the gas. (ii) Average Speed (t,,): This is the average of the speed of the different molecules in a gas at a particular temperature. IFV,, Vo, Va. are the speeds of my, n2, ns... molecules of gas, then a RAMEY, +MY tee 6a en tnt SRT Average speed is also given by the expression u,, = |= Es (ii) Root mean Square speed (¢): It is the square root of the mean of the squares of the speed of the different molecules in a gas at a given temperature, ny +n, +n, +. FN; +My Root mean square speed is given by the expression c= at ory zF Relation between the different types of speeds 21.128 : 1.224 G@iuyicezl Additional information Graham's law of diffusion: Rate of diffusion of a gas | ae etic energy per molecule = 2N Scanned with CamScannerfa 11. Calculate the average kit =RT T mole is given by E Solution T=298 KR =8.314J mol K 348314298 = 37164 J mot! Substituting we get, E= 12. Calculate (a) root mean square (b) average speed ml agel (c) most probable speed of methane gas at 300 K (R = 8.314 J mol! K"') Solution Given: T= 300K,M= 16g mol" (a) Root mean square speed c= [ERE «(FESTA «655 M 0.016 (b) Average speed V,, fos = [88314300 63991 mst ™M. 3.140.016 J2RT _[2%8.314%300 «559 97 mq 5 M 0.016 average velocity of oxygen becomes equal to that of hydrogen at 1.016 kg mol” (©) Most probable speed V,, 13. Calculate the temperature at which 20K, Solution 20K Vay (Given) SRT _ [8R20 x32 Vanx2 2 T 20 yx 322 14. Calculate te temperature at which root mean square velocity of O; gas is eq Solution ah R=8314JK' mol, Mg, 32, 3x8.314xT. = 2887 K 2x107 Scanned with CamScannerroot inean square velocity of gas whe 15, By how many folds the temperature of a gas would ince molecules in a container of fixed volume is increased from 5% 10% em st 15% 10% em» Solution Since the root mean square velocity, v,,, av Vv, We can write, —) Behaviour of real gases (Deviation from ideal gas behaviour) Based on the facts given by kinetic theory of gases, all gases should follow the ideal gas equation pV = nT at all conditions of pressure and temperature. But none of the known gases follow the ideal gas equation. This is because of the following facts: (i) Based on Boyle’s law, a plot of pV vs p at constant temperature should be a straight line parallel to x-axis. For real gases, two types of curves are observed as shown in the graph. co cH, Hy He t Hdcal gas, z oO p> Plot of pV vsp for real gas and ideal gas Case (I): For gases like helium and hydrogen, the value of pV increases with increase in pressure. Case (I): For gases like carbon dioxide and methane, pV value decreases with increase in pressure, reaches a minimum and then increases. (ii) A plot of p vs V for real gases does not coincide with those drawn based on Boyle’s law. For real gases, the following deviations are observed as shown in the graph. 1. At very high pressures, the measured volume is more than the calculated volume. 2. At low pressures, the measured and the calculated volumes approach each other. Plot of pressure vs volume for real gas and ideal gas Scanned with CamScannerCauses for the deviations Following are the causes for the dev 1. Intermolecular forces between molecules: Accor Eases, there are no intermolecular forces between molecules. This i nie closer to one another and exert intermolecular force, due on / 1 to one of the postulates of kinetic theory of true, when the pressure is low. Byt when the pressure is high, the molecules to which they deviate from id Volume occupied by molecules: Ac ding to one of the postula negligible compared to the total volume of the gas. ‘This is true when the pressure is Tow and volume is high, Compared to large volume of the gas, the volume occupied by the molecules can be neglected. But when the pressure is high and volume is low, the volume occupied by the molecules has to be considered. This is another reason for deviation of real gases from ideal behavior. es of kinetic theory of gases, the volume of molecuk van der Waals equation of state van der Waals applied pressure correction and volume correction over pV = RT and derived the equation a ( p+ Je V—b)=RT known as van der Waals equation of state. ve (a) Pressure correction: At high pressure, the molecules move closer and start attracting each other due to which the pressure exerted by the gas is less than expected pressure. So, he applied a correction term p, to the observed pressure to get actual pressure. ve (b) Volume correction: Volume of the gas implies the actual free space available for the free movement of gas molecules. When the pressure is high, a part of the volume of the gas is occupied by the molecules. This volume has to be subtracted from observed volume to get actual volume. ‘Vacwat = Vobserned — Ve= (V - b) Substituting in pV = RT, we get (0 + Jo —b)=RT where a and b are van der Waals constants of gas and are characteristic of the gas. Forn moles, (> ++ Pactual = Pobserved + Pe = (e+ a } a ve Jo-n0)=a T units “| a: atm L? mol” (or) Kg m’ s* mol i b: L mol" (or) m’ mol" Compressibility factor ‘2’ Compressibility factor ‘2’ is the ratio of product pV to nRT for a given gas. Tt is a measure of deviation of real gas from ideal behaviour. Scanned with CamScannermpressibility factor 2" | Compressibitity ible Compre Dilficult to compress Easily compressible | Conditions for real gas to show Ideal behaviour aviour when the volume occupied by the gas is so large that the volume occupied ble. This is possible at very low pressure. © Gases show ideal be by each molecule of the gas is Gases show ideal behaviour at high temperature because at high temperature, the molecules possess eal \d hence the intermolecular attractive forces are negligible. more kinetic e1 Thus, real gases behave ideally at a very low pressure and high temperature. (a) Boyle’s temperature / Boyle’s point The temperature at which a real gas obeys the ideal gas law over an appreciable range of pressure is called Boyle's temperature or Boyle’s point. a Ty =< where a, b are van der Waals constants. bility factor ‘Z? for real gases (b) Relationship between Boyle’s temperature and compr: Temperature Z Pressure Compressibility Z>1 | Atall pressures | Difficult to compress (i) Greater than Boyle’s temperature (ii) Less than Boyle’s temperature Z<1 | Atlow pressure | Easily compressible Z>1 | Athigh pressure | Difficult to compress | (c) Relationship between compressibility factor and the volume of real and ideal gas Consider a gas A. Let the volume occupied by A is Vyea and Viseni at given temperature and pressure: when it behaves as real and ideal gas respectively. Then VY, P's (hen A behaves as real gas) . oRT = PM (when A behaves as ideal gas) nRT V. yo J Scanned with CamScanner5 supy a volume of 1.32 Titre | 16. One mole of CO; was found to occupy using van der Waal’ equation. 9 atm L? mol 27 x 107 L molt at 48 °C. Calculate the pressure exergy” y the g 1.082 L atm K! mol Solution jon we can write For one mote of an ideal gas using van der Waal’s equation Wee P+ )(yvenye ( 7 ee) by=RT ak V = 1.32 litre oPeg gy 0,0821%321___3.59 ee ek =(32-0.0427) (1.32)* R= 0.0821 L atm K™ mol” = 20.63 — 2.06 P= 18.57 atm 17. One mole of SO; occupies a volume of 350 mL at 27 °C and 50 atm pressure. Calculate the compressibility factor of gas. Comment on the type of deviation shown by the gas from ideal behaviour. Solution pV =nRT for ideal gas p= 50 atm aes P R = 0.0821 L atm K" mol = RODEN 492.6 ml Compressibility factor, Z=Y= = 359 _9.711 Ven 492.6 ‘des! As Z < 1, the gas shows negative deviation from ideal behaviour. . Calculate the volume correction and pressure correction in 4.4 g of co: (a= 3.6 atm L’ mol™, b = 0.04 L mol" for CO; gas) ~ Solution 44 Number of moles of CO, aaa Volume correction = nb =0.1 x 0.04 = 0.004 L 2 Pressure correction = ve 3.6x (0.1) = — = 0.036 w? atm Scanned with CamScannerLiquefaction of gases Andrew's isotherm A plot of pressure against volume at constant temperature (isotherm) based on experimental observation done for carbon dioxide is given by Thomas Andrews. The abs as follow 1. At high temperature, isotherm is same as that of an ideal p temperature even at very high presstre. At 30.98 SC, CO; remains as gas upto 73 atm pressure. Liquid CO; appears exactly at 73 atm at 30.98 °C. This 75] temperature is called critical temperature of CO3. This is the yest temperature at which liquid carbon dioxide is observed. Further increase in pressure simply compresses the liquid CO; and the curve represents the compressibility of the liquid CO:. ‘At 21.5 °C, CO; remains as a gas only upto the point B. At point B, liquid of a particular volume appears. On further compression, the pressure remains constant till the point C is reached. This is because liquid and gaseous CO; coexist at equilibrium and more gas condenses. Further compression results in steep rise in pressure. Point D represents liquid state and any point under the dome shaped area represents existence of liquid 4 and gaseous CO> in equilibrium. 5. All the gases upon compression at constant temperature (isothermal compression) show the same behaviour as shown by CO}. 6. It can be observed that gases should be cooled below their critical temperature for liquefaction. Liquefaction of permanent gases requires cooling as well as considerable compression. iy and cooling slows down the movement of molecules. Compression brings the molecules in close Therefore, intermolecular interactions may hold them closely and the gas liquefies. 0 liquid and vice versa by a process in which always a single phase 7. It is possible to change a gas int exists. This can be done by compression at critical temperature. liquid passes into gaseous state continuously and the surface separating the two 8. At critical temperature, phases disappear. In this state, the component is said to be in fluid state, It is that state of a substance where liguid and gascous form of the substance cannot be distinguished. In the fluid state liquid and easeous form of the substance exists in equilibrium, The area under the dome in the graph represents fluid state. Liquefaction of a gas is possible only below its critical temperature. Critical phenomena (a) Critical temperature (Tc) Critical temperature is the minimum temperature above which the gas cannot bbe liquefied however high the pressure may be. Scanned with CamScannerPressure (pe) speed 0 Hie 1 mole of the gas at ig, Cig essure 14 Ci ‘al pressure is the mininnan pre temperature (©) Critical volume (Ve) rhe gas ar its evitied Critical volume is the volume ovcupied by Emote af the 8 iL weniperature, Pmenetete conottuent particles a6 REM BETHEE by ay Liquid state is the sta which the of the subst attractive intermolecular forces. General properties of liquids * Liquids have definite volume but no definite shape. * The molecules of a liquid are mobile, so liquids flow. ditions, liquids are denser than * The molecules in liquids are quite close so that under normal conditions, Bases, Special properties of liquids (a) Vapour pressure lib i oni ibrium at The pressure exerted by the vapours over the surface of the liquid at equilibrium at a given temperaryy, is known as equilibrium vapour pressure or saturated vapour pressure. * Boiling does not occur in a closed vessel aes | * When a liquid is heated in a closed vessel, with increase in vapour pressure a homogeneous mixture of obtained. This state is called fluid state. | liquid and gaseous form of the substanc {_* _In fluid state, there is no clear boundary between the liquid and gaseous form of the substance, g point The temperature at which the vapour pressure of the liquid is equal to atmospheric pressure is called boiling Point. At I atm pressure, boiling temperature is called normal boiling point. If the pressure is 1 bar, then the boiling point is called standard boiling point of the liquid. Boiling point of water Pressure unit Boiling point of water Terms used 1, Atmospheric pressure 100°C Normal boiling point oe 2. 1 bar pressure 99.6°C Standard boiling point aoe | bar. Therefore, normal boiling point is alvaya gher 013 atm Ts Water boils at a lower temperature in hill stations, This is because at h the vapour ‘ | pressure is low. Therefore, even at low temperature, |} external pressure and the liquid boils, | © Food gets cooked in lesser time in a pressure cooker because insi higher and the water boils at higher temperature, So, Scanned with CamScanner(b) Surface tension (;) + Surface tension is the downward force experienced by the molecule of a liquid perpendicular to the plane of its surface. © Surface tension is a so defined as the energy required to increase the surface area of the liquid by one unit. © Unit of surface tension (y) : kg s or Nm” ‘The phenomenon of surface tension may be explained as follows: The molecule A in the interior of the liquid is equally attracted on all sides and net effect is zero. Whereas, the molecule B near the surface is attracted inwards, This unbalanced attractive forces acting downwards tend to reduce the surface to a minimum It is well known that forces of attraction tend to decrease the energy of the system. In the present case, the attractive forces are more in the bulk of the liquid than at the surface, Therefore, the molecules in the bulk are associated with lower energy than those at the surface. The molecules tend to move from a state of higher energy to a state of lower energy. As a consequence of this transfer, the molecule at the surface is less than that in the bulk. The distance between any two molecules at the surface becomes greater than that in the bulk. Consequently, the surface molecules tend to move closer to one another in order to acquire normal distance between them as before. It is for this reason that drops of a liquid are spherical in shape. As a result of the tendency to contract, surface of a liquid behaves as if it were in a state of tension. The force that tends to contract the surface of a liquid is known as surface tension. Surface molecules are ot attracted ‘equally from all directions 1» Interior molecules experience same force of attraction from all directions. Factors affecting surface tension (y) ‘* The magnitude of surface tension of a liquid depends on (i) Attractive forces between the molecules When these forces are large, the surface tension is large. Gi) Temperature Increase in temperature results in increase in kinetic energy of the molecules, The intermolecular forces of attraction decreases and hence surface tension also decreases. Some characteristic features of surface tension * Surface tension gives spherical shape to drops of a liquid because spheres occupy minimum surface area and hence minimum energy and maximum stability. * The tendency of a liquid to rise into narrow pores is called capillary action. The liquid rises in the capillary tube due to surface tension. This phenomenon is observed in the plants where water raises through the bark and reaches the leaves. * Stretching property of the liquid is due to surface tension. Scanned with CamScannersis known as viscosity, (c) Viscosity we Liquid over the successive lay resistance offered by one moving layer of the liquid Jes in the immediate contact of the surf, Ma WS Ove! st 1¢ layer of the mole 'en a liquid flows over a fixed surface, the lay Ste erode ee Te accelerates its NOW Wheres, is stationary. There is a regular increase in velocity i Known as laminar flow. When a particular layer is considered, the I the layer below it retards its flow. layer abow' ou The force responsible jg dz Let the velocity of the layer at a distance dz is du, then velocity gradient is I ‘maintain the flow of the layers is directly proportional to the area (A) of contact of layers and velociny du dient onsen (3) du faa OAs where 1] = coefficient of viscosity. Coefficient of viscosity 9 is defined as the force acting per unit area of the liquid when the velocity gradieny is one unit, Coefficient of viscosity (n) [vse units of coefficient of viscosity (n) * Nam's ct gt s * Kem * Pascal second | | Poise => kgm”! Factors affecting viscosity The magnitude of viscosity is directly proportional to the intermolecular ee ores te hydrogen bonding, van der Waals forces and is inversely proportional to temperature. Intermolecular attractive forces pull the molecules closer so that viscosi temperature, kinetic energy of the molecules increases. This results in det decreases. forces. Therefore, viscosit =! Thickness of windowpanes of old buildings is because glass is as ce the lower parts of glass become thick. _flows slowly and h Scanned with CamScannerBae | | oni Very Short Answer questions (VSA) force exists between non-polar molecules? «duced dipole fore What type of intermote Which one is stronger: dipole-dipole forces or dipole Write two types of forces which determine the physical state of substances. [May 2015] Give one example for a repulsive force. n for one mole of a gas. [May 2016, Feb 2019] s equa Write ideal gas equation for ‘n’ moles of a gas. Write the equation for the relation between molar mass and density of a gas. [March 2017] ‘What is the meaning of absolute zero temperature? [March 2014] [March 2014] What is an ideal gas? ). Write the mathematical expression of (i) Boyle’s law [Feb 2018] [Mareh 2015] CRNA wee De (ii) Charles’ law Gi (iv) Avogadro's law[March 2016] Gay-Lussae’s law (v) Ideal gas equation Short Answer questions (SA) 11. Define (i) London forces. (ii) Dipole - Dipole forces. 12. Distinguish between thermal energy and intermolecular forces. 13. State and explain (i) Boyle's law [March 2013, May 2016] (ii) Charles law [March 2013] (iii) Gay - Lussac’s law [March 2013} (iv) Avogadro’s law [May 2016] (May 2016] (v) Dalton’s law of partial pressure Long Answer questions (LA) 14. What is hydrogen bond? Write the necessary conditions for hydrogen bonding. 15, Write the physical properties of gases. 16. Derive the relationship between density and molecular mass of a gas. [Feb 2019} 17. Derive an ideal gas equation using gas laws. [March 2013, May 2015] Scanned with CamScannerwea Very Short Answer questions (VSA) ‘a’ and ‘b’. 1. Write the units of van der Waal’s constants 2. Write van der Waal's equation for real gas. [Maren 2013) 3. What is the value of boiling point of water at | atm? 4. Which among the following is more viscous: water or ethane-1, 2-diol? 5. Write the value of critical temperature for COs. [Feb 2015) ‘Short Answer questions (SA) 6. Differentiate between ideal gas and non-ideal gas. 7. Define ( Boyle's temperature Gi) Compressibility factor 8. What is the mathematical expression for compressibility factor? How does it vary with pressure? [March 2016) 9. Define (i) Critical temperature [March 2015) Gi) Critical pressure [March 2015) [Mareh 2017] (iii) Critical volume 10. What is a fluid? Long Answer questions (LA) 11. Write the postulates of kinetic theory of gases. [March 2013, 2014, 2017 Feb 2018, 2019] 12. Real gases deviate from ideal gas behaviour. Give reason, 13. Calculate the numerical value of gas constant, R in S.L. system. [March 2016] (March 2013] 14. Represent the behaviour of real gases and ideal gas graphically. 15. With the help of Andrew's curves, explain p-V isotherms of carbon dioxide, Very Short Answer question (VSA) 1, Which of the following physical states possess stronger intermolecular fo Solid, liquid and gas Short Answer questions (SA) Define (i) Vapour pressure (iii) Surface tension (v) Coefficient of viscosity (vi) Aqueous tension Scanned with CamScannerfaster in a pressure cooker Gil) Water drops are sphe! cc tension [May 2015] Mention the factors whic 4. Gi) Viscosity Long Answer questions (LA) Define viscosity. Derive a relationship between intermolecular force and coefficient of viscosity 5 6. Define liquid state. Write its common properties ress 250 dm’ of air at 2 bar to 200 dm’ at 300 K. °C, a balloon is filled with 2L air. What s 26.1 °C? Problems 7. Calculate the minimum pressure required to compr 8. Ona ship sailing in Pacific Ocean where temperature is 23.4 will be the volume of the balloon when ship reaches Indian Ocean where the temperature i 9. For nitrogen gas, the van der Waals constant b is 0.032 L mot ', Caleulate the radii of nitrogen molecule (Assume it to be spherical). 10, The density of a gaseous oxide at 2 bar is same as that of oxygen at 4 bar at 300 K. Calculate the molecular mass of the oxide. If the formula of the oxide is MO, calculate the atomic mass of the xV) wntains 35% by weight of hydrogen. Calculate element M. (Given: b = 11. A mixture of hydrogen and oxygen at 2.5 bar pressure cor the partial pressure of oxygen. s and 8.375 mol of neon gas. Calculate 12. A mixture of gases contains 2.21mol of dioxygen ga (i) mole fraction i) partial pressure of dioxygen. Given, total pressure of this mixture is 25 bar. [May 2016] at 2 bar (R = 0.0825) [March 2015] 13. Calculate the temperature of 6 mol of a gas occupying 4dm° .d into a2 L vessel at 273 K. Calculate the 14, 04 L of Np at 0.5 bar and 2.0 L of Hy at 0.7 bar are introduce total pressure of the gaseous mixture. methane and ammonia are 191.0 K suit 405° seapetsively. What does it lecular forces? 15. Critical temperature of 2 Indicate which one has stronger intermo signify Scanned with CamScanner