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    22 views20 pages

    States of Matter

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    Anushree
    notes along with PYQs for states of matter

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    <4 Qa! | pyppRMOLECULAR FORCES: | “tte foes of attraction existing among the molecular a substance (gaseous, liquid or solid) are called [ino lecular forces. | inefntermolecuar forces arise due to any one ofthe following interactions: Dipole-dipole Jon-dipole Ton-induced dipole Dispersion forces, and 5 en bonding, _piptle-ipote,dipole-induced and dispersion forces are collectively called as vam der Walls forees in honour ihe Dutch scientist, van der Waals who studies about these fores. iy Dis interactions. These forces of attraction occur among the polar molecules. Polar ‘molecules have permanent dipoles. The positive pole of one molecule is thus attracted by the negative pole of the other molecule. A. simple example is that of HCI in which chlorine being, mot PRetronegative aquires a slight negative charge whereas the hydrogen end becomes slightly positively Sharged. The dipole-dipole interactions then take place among the HCI molecules as follows: aoe stg St h—-O ag aod OTHER EXAMPLES. s ? Heer, H-L, +S, PHg ete Dipole Dipsle attrachms on-Dipole Interactions. This is the attraction between an ion (cation or anion) and a polar melequle. For example, when NaCI is dissolved in water, the polar water ‘molecules are attracted towards Na’ ion ‘as well as towards CI ion (a process called hydration of ions) - ° Paral eye wi ay oy har Fit) “ | ry ye Yr vm duced dipole Interactions, A non polar molecule may be polarized by the presence of an ion i eeromes an indaes dipole. The interaction between them are called ion-induced dipole interactions. Forex. In the presence of nitrate ion (NO'3), iodine molecule (.), which is non-polar, gets polarized ae tion ad-p (er) Dipole-Induced dipole Interactions. A non-polar molecule may ‘be polarized by the presence of a polar molecule (dipole) near it, thereby making it an induced dipole. The interactions between them are then called dipole-induced dipole interactions. r i s+ a : Polar moleusle, Hobe garaton 31 Scanned with CamScanner : the above types of attractions, Howey ! Itiseay to coneive the above type of . Howevey Landon forces or dinerson forest ntemoleculr forces aact nonpolar molecules ie rete ot monoatomse gates like He, Ne, Arte to ech Other rue my be de oa believed that at any instant of time, the electron cloud of Short wil 2 pedal a instantaneous dipole or momentary dipole («diol fr Shon A ® Protos in par f the molecule i sighly more nen th ecalyin te sane ace the neighbouring molecules, These are then attracted to each other exactly in the same way 9g 8 Tween the induced momentary dipoles ae called dipersion forees, Condon feria) He atom 4 We shorn Momenauy anduasd dip Syrimelrice) cleok®h clout % Ai pble ha elas toe tion: Formobim ah monentery dipole hao te alow om whdueed dipsle. i Bonding. 4 Hydrogen ng. ; i lohes aver a meleule eontaia a Hratom inked fo lghly electronegative atom (Life F, O/N), this atom attrects Me chaved poiv of, ebecbeme rrove amd $0 thic end ob tre mole perme slightly negative while the other end Cie, H~end) hermes slightly positive s The megattye evd di one mo! atback the poshve end 5 the athey ond at a retulh, a weak bod ix formed betutem them. This bond ve “4 hydrogen bod, Tt is veproented by dotted pein, Examples vp He berding.— e HE, HO, NM, Choon, . e ou wa \ ” Pe ee e me at Woy 4 fag yalregeon etton, and Bali peje? Tre, compos hah ty Bollieg, Pam Tho abetmally, atgn meltug oud Boley 5 Solabilily, Compomnas which cam fem hydregein bend usdr are colubl +4 8udy 40/Y enbs 32 Scanned with CamScanner Gas ——> Uquid——> solid Predominance of intermolecular interactions Gas <— Uquid<— solid Predominance of thermal energy 1.3 Gas Laws 13.1 Boyle's Law (Pressure-Volume Relationship): At constant temperature, pressure of a fied amount of a gas varies inversely with the volume of the Bas. Pay (0, Tconstant) or Var (o,Teonstant) he. vet P ‘Where V is the volume, p is the pressure of the gas and kx isa Boyle’s constant of proportionality whose vale depends yon onthe amount ofthe gs an temperatre v= ky eonsant When he presse i chnge PV.=paVeeConsant or Bett $ (ara) ‘The curves obtained by plotting (pV) against pressure (p) at different temperature are known as isotherms. 33. Scanned with CamScanner Temperature ToT 5 a ty (bar) —> ‘m od=(FIp therefore, d= k’p a te ae a This shows that at a constant temperature, pressure is directly proportional to the density fixed mass of the gas. Practical Significance of Boyle’s Law: For example, air at sea level is dense, but the density as well as the pressure decrease with increase altitude, For example, the atmospheric pressure at Mount Everest is only about 0.5 atm. Asa result oxygen in air becomes insufficient for normal breathing. This causes what is commonly know altitude sickness (general uneasiness, sluggish feeling, headache, etc). Therefore, mountain cite adapt thei bodies to low oxygen pressure or they carry oxygen cylinder for an emergency. . 1.3.2 Charles’ Law (Volume Temperature Relationship) ‘At constant pressure, the volume of a given mass of a gas increase or decreases by 1/273 ofits va at 0°C for each one degree rise or fall in temperature. Let Vo be the volume of a given mass of a gas 0°C and Vt is its volume at any temperature t°C, then the volume, Vz may be written in terms of law. For 1 degree rise in temperature, volime increases V, Fort degree rise in temperature, volume increases Vo Volume at t°C, V= Initial volume + Increase in volume = Vp + 22** t 773 Vo ht or; 34, Scanned with CamScanner Absolute or Kelvin seale of Temperature; me ennetine at which volume becomes zero has been found to be =273°C (or exactly -273.15°C). u ie re, he proposed that ~273°C Is the lowest possible temperature It may noted that this value, ~ ‘Coes not depend upon the nature of gas or the pressure at which the experiment i performed, Att=-273°C; =p [1-23 ]= 3°C; Volume Vi= Vo [1 2] =0 . Thus, -273°C is the lowest possible temperature because below this temperature, the volume will become negative. This is meaningless. This lowest temperature Is called absolute zero temperature. A ‘new scale of temperature based on this choice of temperature known as absolute scale of temperature or Kelvin temperature scale, vote (ans Extrapolation --** BC zt pat ‘calsus-ale Kelvinscale 0 7317327, Alternative Form of Charles’ Law: ate Ve = Vo(1+555) =Vol“5 But, 273 +t =T (K) and 273 = To (say) which corresponds to 0°C on absolute temperature scale. iT open neo zok Thus, Z= constant shy. 300-200-100 1000100 Témperatue (t)—>, ‘The curves showing the volume temp. behaviors plotted at different fixed pressures are called isobars. 35. Scanned with CamScanner Volume tam) 0, a0 200 so eS Femperature (Kj —> + Laws on the principle, hydrogen balloons (which rise higher © Practical Significance of Charles’ Lav: Onn er ransporation because of lower censtyof hydrogen] were develo verature Relationship): 's Law (Pressure “Tem rries directly with temperature. ‘Lussac’ Ree pressure of @ ‘fixed amount of gas vat ‘At constant volume, pat 4 or 2 econstant = Ks or not Temperature [K)—> “The curves showing the pressure temperature behavior plotted at fixed volumes are called isochors. Physical Significance of Gay-Lussae’s Law: Pressure in a well inflated of automobiles is almost constant. But on hot summer day this increases considerably and tyre may burst, if pressure is not adjusted properly. Similarly, during winters, on a cold morning we find the pressure in the tyre of a vehicle decreased considerably. 1.3.4 Avogadro’s Law (Volume-Amount relationship): ‘Ata given temperature and pressure, the volume of a gas is directly proportional to the amount of gas. Van(pandT constant) or Ve hyn Where ‘nis the amount of substance (moles). 36, Scanned with CamScanner temperature aid ‘lgpsscontalning equal amount of substance occupy the same volume at the same feme pressure Mass of gas _m "Molar mass ~ Mi Thus, V= keg This can be rearranged as:M=kyd : ‘The density of a gus is direetly proportional to its molar mass. 1.4 Ideal Gas Equation According to Boyle’s law, Ves (constant T and 1) wm ‘According to Charles’ law, VarT (constant p and n) . ‘According to Avogadro's aw, Varn (constant p and) (il) Combining equations (i) (i) and (ii), vam or pV ant or pV = nkT Where R is a constant of proportionality and known as molar gas constant or universal gas constant. For one mole of gas (n= 1), pV = RT, equation is known as ideal gas equation. Nature of Universal Gas Constant ‘R’: _PXV (atm) x (22.41) = ee 1 molt aT © Cmole) x OTA) = 20S21L atm K-* mot Or 82.1 atmL Kt mol~* or 8.314 J mol"? K* or 0.0831 bar dm? mol"? K~? 1 Dalton’s Law of Partial Pressure: The ota pressure exerted bya mixture of wo or more nonteactng gases ina definite volume i equal to the sum of the individual pressures which each gas would exert if occupies the sa ‘ constant temperature. eevee neo Protal = Pa + Pz + 3 + ~~ Fora mixture of two substances A & B having moles n, & ny respectively, then their mole fractions are 34 Scanned with CamScanner Xn ea tat Me ‘exert partial pressure py, SuDb0se at temperature’ T, three gases enclosed in te volume ¥ Pra et Fespectively, Then, i" = ART mkt, met } Ret, MR ye n+ Pat Pa or Rr rT) Rt Prom = my St may ts Wp On dividing p, by Peta. we Bet OF Pi =X Procatt P2 = X2Procat and Ps = 3 Peotat Application of Dalton's Law: Onygengosis collected over water. When the water level inside the Container becomes equal to outside level, then, Prem = Poti (equal to pressure of gas and water vapours) Pan= Por Bao pressure due to water vapours (commonly called aqueous tension] perature is known, pressure of dry gas can be easily calculated. ). Since aqueous tension a, Scanned with CamScanner 15 Kinetic Molecular Theory of Gases Postulates of Kinetic Molecular Theory: 1. Allgases are made up of a very large number of minute particles. 2. The molecules are separated from one another by large distances. The empty spaces among the molecules are so large that the actual volume of the molecules is negligible as compared to the total volume of the gas. 3, The molecules are in a state of ceaseless and random motion in all the directions. They keep on colliding with one another and also with the walls of the container and thus, change their directions. 4, Molecular collisions are perfectly elastic, with one another or with the walls of the container. However, energy during the collisions. 5, There are no forces of interaction (attractive or repulsive) between molecules at ordinary temperature and pressure. 6. The pressure exerted by the gas is due the collision of its molecules on the walls of the container per unit area. 7. The average kinetic energy of the gas mol ecules is directly proportional to absolute temperature. .5.1 Kinetic Gas Equation: yee gy WENO Rw BP! v =2 NCE... () eta caked Wy ™ “= ye cafe dead A 44 - By =$mNC? ni) anecTed woe A ww\eads \prenad m wv: ce ak va m. Bled Ap. ) 3 35-6 ce Va “ys - Aaa Ae pV = RT for one mole of gas, i.e. no loss of energy occurs when the molecules collide there may be redistribution of pV =2 Ey . (vi) ands called Boltzmann constant, a Thus, Ex {kinetic energy) & 7. 3% Scanned with CamScanner | eee ee cular Speeds: 1.5.2 Maxwell-Boltzmann Distribution of Moh Tpeedsis very smal 52 Mametion of molecules With VET cere The fraction of molecules poste ie! oe a oe : peakand then it starts decreas! sec ped corer N8 Paki The maximum fraction of ‘molecules vos carve sPiferred t0 a8 Most probable speed a i ‘The speed correspondint peeds goes on Increasing tii It reaches, esl gto the pet speed posses by the maximum fraction of gs molecu ‘The most probable speed of 2 628 given temperature. “wit probable “speed (Une) Sea ee 1 molecularspeed (em: jure on the Distribution of Speeds: ith the rise in temperature. Meee aoat from most probable speed (discussed above) there are two other terms which a ‘commonly used for the gaseous molecules. The 3 types of speeds are (i) most i average speed and (iii) root mean square speed. uw probable spe + Most Probable Speed (tmp): Its the s i i speed possessed by mi ic 2s ee ¥y maximum fraction of molecules pAb gt 1.53 Eifect of Temperat ‘The curve becomes flatter wit + Average S} th ve speed: Iti imple of gan ETRE of ferent speed s of all the molecul a les present in a give” Scanned with CamScanner 2 Bitters ee Uy = ES; ty = MRtNawat Nau 4 lv Ny#N2#Ngb + Root Mean Square § peed: It Is the squ: seeds ofthe molecules tf aas tg see ft of te mean of the squares of ferent aPa urate PS ee ee Us = A = eet Nat Nah yt 1.5.4 Relationship between Diffe rent Types of Speeds: The root i, probable speed (tmp) and average speed (tg) are given Spends The rot ry sate (rms), most ier 7 Most probable speed, tmp = [77 ; Average speed, u RT ET Root mean square speed, trms = The three speeds are related as: 9213 X Root mean square speed (ttrms ) ‘Average speed (tay ) = Most probable speed (ump) = 0.816%Root mean square speed (tlrms) 11.128: 1.224 OF tmp: Yay? Urms = The root mean square speed is commonly used and can be calculated from the following relations: SPV /3P Fron Fe 1.6 Behavior of Real Gases: Deviations from Ideal gas Behavior: A gas which obeys nRT) and other gas laws at all temperatures and pressure is called an none of the actually known gases obey this equation over the entire hich does not obey general gas equation and other gas gas or real gas. To test the behavior of real pV will be the general gas equation (pV = ideal gas or perfect gas. However, range of temperatures and pressures. The gas w/ laws at all temperatures and pressures is called non-ideal gases, we plot pV versus p plot of gases at constant temperature. ‘According to Boyle’s law, constant and pV versus p plots at all pressures will be straight line parallel to x-axis. Scanned with CamScanner carves wre chore . © Fox gases such 25 ditytrogen (Mtg) 2nd heleem (He) 25 the presuure increases the vale of gy, noe. © Reg art ascaton merosite (CO) 20d methane (CH) first these is 2 negztine Cetztion ited betcnier 20 that pidecreases with tocreath in presse. tt reaches to a minions vel tet BV edice starts increasieg, Detations ftom ideal tetaticr alta become deat when gre were welume picts ae teown. nis deze that they Co nic coincide. bs high presuure the weme ig mare than the cHakaed ware. Howere, 2 lon pressures massed and, woes AOR BIL CAE A OLE, SAS Mecawoting Stevistions Srom Ideal ebavior UMfeet of Pressure: Scanned with CamScanner Asimple way to study de samen e M leviations of real gases from ideal behavior is to plot a graph between © and p. nar '$ called compressibility factor and is denoted by Z. ae Compressibility factor, z=?” For ideal gases, Z= 1 underall f 7 ler all conaiti Pro frtenlpeeoer ions of temperature and pressure, This means that, In other words, pV is always ‘ ; a be atheists ane sequal to nRT and this corresponds to Ideal behavior. For real gases Zmay pV #nRT for real gases: 4 “ : Es S ait E called negative deviation. ans that the gas is mor : ay rear atia the sore compressible than expected from ideal behavior. Itme i : ans that the gas is less compressible than expected from idea behavior. ghee i 4 soo “400-500-800 00 (bay ie figure that dips in ‘the curves goes on becoming n from ideal behavior It is clear from th 1.6.2 Effect of Temperature: smaller and smaller as the temperature increases. This means that the deviatior becomes less and less with increase in temperature, a Scanned with CamScanner P q 1 temperature at which areal gas obeys deal gas law over an appreciable range of pressure Boyle temperature or Boyle point, nar the gas shows ideal behavior, then, Viger® = Substituting the value of “in the above equation, we get, Z Vreat Viaeat 1.6.3 Compressibility Factor: s the ratio of actual moler volume of a 25 to the molar volume of it were an ideal gas at that temperature and pressure. Thus, we conclude: ()) At best the real gases show ideal behavior at low Pressure and fairly high temperatures, (i) Atlow temperature and high pressures, the gases ciffr significantly from ideal behavier. 1.6.4 Causes of Deviations from Ideal Behavi ()) Why do gases deviate from ideality? {1} Why does the ideal gas law fil at high pressures and low temperatures? In order to explain the deviations from ideality, Vander Waal pointed out that the following assumptions in kinetic theory are fouity, 1.6.5 Faulty Assumptions in (i) The molecules ‘were cor is negligible in compari (il) tt was assumed that independently. Kinetic Theory of Gases: sidered as point masses ison to the total volume of there are no interactioy and the volume oc the gas, m forces between and the molecules m ‘Cupied by the gas moler Scanned with CamScanner (ii) According to kinetic ic theory, the forces of Fe Eee f attraction between the gas molecules ore negligible. If Tea reine gases will never liquefy. However, we know that gases get Hauetied oiecoet eee Moreover liquids formed are difficult to compress. This ns are strong enough and prevent inti fost i : prevent squashing of molecules in ti es Ee ; However, ie assumation is also valid at low pressure and high temperature teeause je far apart from one another. Thus, thi i ine cesta ear , this postulate is also invalid at low 1.6.6 Corrections of Deviations-Yander Waal’s Equation for Real Gases: © Correction Due to Volume: The volume occupied by the molecules cannot means that the molecules are not free to move than the observed volume. Thus, ifV be the volume occupied by svalable to the molecules for the movement, Le, corrected volume i: Veorreetea = (Vb) for one mole For n moles of the gas, the correct (V-nb) for n moles t be neglected in comparison to the total volume. This in whole of volume V but the free volume is less jole of the gas, then the volume tion term is nb so that corrected volume is given by: Veorrected = yn Due to Inter Molecular Forces: ces exist between the molecules of the real gases. The molecule is being by the neighboring molecules. The attractive forces neutralize one another and to the molecule. On the other hand, when 2 molecule approaches the wall of the container, it experiences an inward pull as 2 result of the attractive forces oni) by oS neighboring molecules inside vessel. Thus, the molecule strikes the wall with a lesser force than i would have done if there were no attractive forces. © Correctio! some attractive fo attracted uniformly there is no resultant pull Scanned with CamScanner Therefore, the observed pressure Is less than the ideal pressure. Hence, corrected pressure, Deorrected's given by? Peorrected P+ P’ where pis the observed pressure and’ Is the correction term. Peorrected = P +r for n moles Thus, Peorrected= P + px for one mole; © Significance and Units of a and b: The constant ‘a’ measures the forces of attra between the molecules of a gas. Greater the value of ‘a’ greater is the strength of Va Waal's interaction. ‘(moles)® The units of ‘a’ are atm L? mol-?, Similarly, b is the measure of effective size of the gas particle. It is four times the actual volume of the gas molecule. It is excluded or co-volume. The units of ‘b’ are b=V/n ie. Lmot® 1.6.7 Differences between Ideal Gas and Real Gas (p-+2%)ivenb) = nt forn motes; (p +f) (V-b)= RT for 1 mole Molecule in the middle Nonet force Ideal gas ; i sea Real gas Ideal gas obeys all gas laws under allconditions of | 1. Real gas ob eys Bas laws onl\ temperature and pressure. pressure and igh cme under low in ideal gas, the volume occupied by the molecules is negligible molecules is negligible as compared to the total volume occupied by the gas. In eal gas, the volume occupied by the Tpelecules isnot negligible as compared to the tal volume occupied by the gas, | The forces of attraction among the molecules of the gas are negligible. The forces of attractio are not ~negligible at pressures, Teobeys ideal gas equation: pV=nkT obeys Vander Waals equations (b+ 5¥)(v-nb) = nat Scanned with CamScanner Ms Me Mo gs ME Volime’ > * ‘At 50°C, the isotherm for COs is very similar to that for ideal gas. It was observed that at 30.98°, Carbon dioxide remains gas up to 73 atmospheric pressure. At 73 atmospheric pressure, iqud carbon dioxide Sppears for the first time. This is the highest temperature at which liquid carbon dioxide is observed. above this temperature, itis gas. Iti called critical temperature. Further Increase in pressure simply compresses the liquid carbon dioxide and the curve represents the compressibility of the liquid. tt is Sheerved that even a slight compression results in steep rise In pressure indicating very low compressibility of the liquid. Below 30.98°C, the behavior of the gas on compression Is quite different. For example, at 21.5°C the isotherm ABCD consists of three parts, At point A, carbon dioxide is ges. The volume of the 635 decreases along AB as the pressure increases up to B. At point B, liquid of a particular volume appea's. Further compression does not change the pressure. Liquid and gaseous carbon dioxide co-exist and farther application of a pressure results in the condensation of more B25 until the point Cis reached. So, the horizontal portion BC Indicates that there Is considerable change in volume with a change in At Scanned with CamScanner indicat faction. In other words the gas condenses to ¢o yressure indicating process of lique! r mace f condensation would be completed at C. The reduction in boli fom € EB D corresponas vot, pressure required to compress a liquid into a smaller volume. Generally, the gases bel tin temperatures are called vapours. | ; Critical temperature is the temperature above which as gas cannot be liquefied howe “a pressure may be. For example, the critical temperature of carbon dioxide is found to be sue Ven at pressure gp Ty means that carbon dioxide cannot be liquefied above this temperature e hundred atmospheres. Similarly, critical pressure (pe) and critical volume (V) may be defined ay (i) Critical pressure is the minimum pressure required to liquefy the gas at the critical tempe ii) Critical volume is the volume occupied by one mole of the gas at critical ‘emerate Pressure, * Kinetic Molecular Model for Liquids: Liquids are composed of molecules. Ai) The molecules of iquids ae held together by appreciable intermolecular forces, Ai) Due to weak intermolecular forces, molecules are in constant random motion, (@) The average kinetic energy of riolecules in a given sample is proportional to the absolute temp, 1.7.1 Properties of Liquids © Evaporation: The process of conversion of a li Overcome the attractive forces Process of escaping of molecules fro! quid into its vapours at room temperature. Molecules can readiy the liquid and escape from the liquid surface into vapours. This m liquid to vapour state is called evaporation, Fraction ofiolecles having a given ke, {Factors on which Rate of Evapora . tion Depends; » Pemberton Evaporation increases as the tempers in ii) Strength of inte 7 enses, raat ermolecular Forces: The exge of evaporation of a ligui a Hauid related to the strength of the attractive forces, The interm ole Ether

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