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Liquid and Gaseous State

This pdf tells about states of matter

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Liquid and Gaseous State

This pdf tells about states of matter

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tejapyla036
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© © All Rights Reserved
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GASEOUS STATE Gas Laws (1) Boyle’s Law:- At constant temperature the volume of given mass of gas is inversely proportional to its pressure. Vx 1/p(At constant T ) V=K/p | PV =K ‘Let us consider Vt volume of gas , pressure is Pi and V2 volume of a gas, pressure is P2at constant temperature then PLV.= PY, P, /P, = V,/ V, (2) Charle’s law :- At constant pressure, the volume of a given mass of a gas is. directly proportional to its absolute temperature. Weel (At constant P) © V=KT V/T=K Let us consider at Ti temperature the volume of gas V1 and at T, temperature the volume of gis| is V, then av, V./ T= V,/7] ©» [¥/V,=7/ 7] Op [Wh= Vi, (3) Avagadro’s law :- At constant temperature and pressure the volume of a given mass of a g:| is directly proportional to no. of molecules of that gas , therefore ‘Van (At constant T, P) V=Kn VV _/n=K) Let us consider V1 is the volume of gas contains 1 molecules and V2 is the volume of a ges contains N2 molecules. V,/ a= Vj/n,] © [V,/V,=n,/n,] OD [Va,= Vin, Ideal gas equation ‘The Ideal gas equation derived according to Boyle’s law, Chatles’s law and Avagadro’s law. : Vat/P_____(1) (Boyle's law) VaT ______ (2) Chatles law) Van _____)_—(Avagadro’s law) From equations (1), (2), (3) Vant/P zy Where P= Pressure of gas V = Volume of gas R = Gas constant n= No. of moles T= Temperature jr 1 mole of gas, the Ideal equation is, PV = RT (Or)PV/T =R T, temperature V, volume of gas exerts pressure P, and T, temperature V, volume of gas pressure P2 According to Ideal gas equation P,V,/T,=R, P,V,/T,=R PV, /T, = P,V,/T, lical gas The gas which obeys the all gas laws (Boyle's, Charle’s, Avagadro’s laws) :ll temperatures and pressures is known'as Ideal gas. (Or) The gas which obeys the Ideal gas equation (PV =nRT) at all temperatures and pressures ns|known as Ideal gas. leviations from Ideal behaviour PV =nRT PV /RT=0 If n= 1 then, gl PV/RT=1 "ut means for one mole of Ideal gas at all temperatures and pressures PV/ RT is always equal ‘xe. This is known as compressibility factor and denoted by “Z”. Z=PV/RT=1 (PV=RT) If gas shows + ve deviation from Ideal behaviour PV/RT>1 (PV>RT) If gas shows ~ ve deviation from Ideal behaviour PV/RT<1 (PV fot one mole of gas Videal= V — nb] > for ‘a’ moles of gas 0 Pressure Correction (Inter molecular attraction wor ion ):- __ Consider a gas molecule in the intetior of vessel, it is attracted by remaining molecules jomall sides. There fore net fotce of attmcan ~ A on such molecule is zero. ie same molecule when appioaches to wall of th P Real < P Ideal P Ideal=PReal + PAdded| (ty The added pressure depends upon the two factors. .q\) The no. of molecules present pet unit volume which are striking the wall of vessel. 2) The no. of molecules present per unit volume which are attracting the striking molecules, The above two factors depends upon the density of the gas. Padded ot Striking x d Attracting Padded qd? ______(2) : Consider ‘n’ moles of gas taken in volume of ‘V’ Lt then density propoitional ton /v . dan/y (d=1/V) 2 a nt / V2 Gy From e q (2) and (3) 2/ ye ae e oy va (4) For ‘n ‘ mole of gas) Padded =a / V? (For one mole of gas) Substitute the eq (4) ineq (1) P Ideal = P Real + an? / V? for ‘n’ moles of gas. P Ideal P Real + a / V? for one mole of gas PV = RT Bu, P=P+a/V?, V=V-b (Peal Vv? )(V- )= RT| (For one mole of gas) PV=nRT - i Pp =p+ant/V?, V=V-9b as ‘n’ mole of gas. Kh (P+ an? 7 Vv? )(V —nb) = RT) ______ For ‘n’ mole of gas) — iy Where a and b are known as vander waals constants whose values depends upon the nature of the gas. Units of ‘b’ :- ‘b’ is the excluded volume of one mole gas in volume of ‘V’ Lt. Litre / mole} Units of ‘a’:- P Added = a n? / V? a= P Added x V? / nn? =atm. Lt? /mole* =atm. Lt®. mole’. Significance of ‘a’ and - The easily liquefiable gases like CO, , HCl, NH, , SO, hav€ value of ‘a’ is high than the permanent gases like H,,N,,0, — The value of ‘a’ increases with case of liquification of gases. Now since the value of ’ is the inter molecular forces of attractions. The value of ‘a’ is said to be the measure of inter molecular forces of attraction. — As ‘b’ is the effective volume of gas molecule. The constant value of ‘b’ for any Bas over a wide range of pressures and temperatures indicates the gas molecule is incompressible. idrew’s isotherms of co: and critical phenomenan Pressure -——— - Volume. ~ Andrew conducted an experiment to determine, the critical temperature (Ic) of CO,. P-V curves (isotherms) are drawn at different temperatures. a) Isotherm at 13.1°c :- oy At 13.1%, increase in pressure, decrease volume from A to B. 7 ; At B’ at the same pressure CO, liquifies and reaches ‘C’, \ After ‘C’ inctease in pressure does not changes volume. ~) (b) 1 em _at 21,5% > At 21.5%, iner ame pressure CO, liquifie ¢ volume from Hi tot in pressure, dec > AtP at th and reaches G. oA (Isotherm at 31.1% 5 > At 31.1%e , increase in pressure, decreases volun liquetied. This point *X’ is called critical point/critical state oT 3 At above 31.1% (ie. at 35.5% , 48.1% ete) even at high pressures T° 1, can not Meh et G inetease in pressure does not changes nd reaches point X. Where gas is Continuity of ym the gaseous state by the application of pressure after subs ¢ liquefied fre i \ substance can be liquefied fr oe a _ cooling the substance below its critical temperature is known a | Critical phenomena | Critical stater= | [At critical point volume of gas is equal to volume of liquid. At these circumstances not | observed difference between gas and liquid. This state is known as critical state. Critical constants :- For every gas they are 3 important critical constants ie. critical temperature, critical presse) "and critical volume. a) Critical temperature ‘The temperature above which a gas con not become liquid what ever high pressure may be "applied is known as critical temperature. Ex: - The critical temp. of CO, gas (Ic) = 31.1% b) Critical pressure (Pc) :- The minimum amount of pressure is require to liquefy a gas at its critical temperature is known as critical pressure. Ex: - critical pressure of CO, gas (Pc) =72.1 atm. | At critical temperature the pressure required to liquify the gas is the critical pressure. Buti the gas is cooled below its critical temperature. The gas becomes liquid even with out applying the critical pressure. ; Ex: - at 31.1% the pressure required to liquify the CO, gas is 72.1 atm. But the same if cooled to 12° it becomes liquid by applying the 42 atm pressure. ©) Critical volume _(Ve):- ‘The volume occupied by one mole of gas at its critical temperature and critical _ Pressure is known as critical volume. Ex: critical volume of co, gas (Vc) = 95.6 ml /mole For a particular gas eritical temp, critical pressure and critical volume are constants, “Therelo these are called critical constants. Relationship between critical constants and vanderwaal’s constants For one mole gas vanderwaal’s equation (P + a/V2) (Vb) = RT (PV + aV/ V? - pb —ab/ V?=RT Multiply through out by V? we gy (PV + aV/ V?- pb —ab/ V3) v2 = PV! +a V¥/ V?- Pb V?—ab = RT'V2 PV’ +aV-Pb V? - ab = RT V2 Divide through out by pressure P eat PV? /P + aV/P- Ph? /P—ab / P= RT V?/P Vit aV /P-bV?~ ah /P=RTV?/P Arrangé in descending order of V V3-bV? - RT V2 /P +aV /P—ab/P=0 under critical conditions P=p, T=f, V*-bV? -RTe V?/ Pe +aV / Pe —ab/ Pe= 0 V?- V? (b + RTe /Pc) + aV / Pc -ab/ Pe=0 —— () elow critical temperature there are three values of V , for every value of P. At critical emperature there is only one value of V for every value of P V=Ve V-Ve=o0 (V-Ve)3= (a—b)' = a 3a°b + 3ab?—b? V? ~3VeV? +3VEV-Ve = 0 2 At critical temperature eq (1)-and (2) must be identical. There fore the coefficients of similar powers of ‘ V ‘ must be equal. 3Vc =b+RTe/Pc : (3) 3Vc? =a/ Pc (4) Ve3 = ab / Pc 2 (5) Divide equation (5) by equation (4) Ve} / 3Vc? = ab/Pc/ a/Pc Ve / 3V2=b Ve/3=b Ve = 3b Substitute Ve in equation (4) 3.x (3b)? =a/Pe 3x 9b?=a/ Pc 27b? =a / Pc Pe = a/ 27b° Substitute Ve and Pe values in (3 ) 3x3b=b+RTc/a/ 27 9b =b+RIc x 27b*/ a 9b—b=RTe x 27b*/a sb = RTc 27b?/a Te = 8bxa‘/ 27b°R a /276R Te NM tes (Vander equation the constan ure, volume and temperatu ‘nd critical temperature ('e) law of cortes s reduced equation of state) nd b can not be measured directly pressed in terms of critical pressure spectively, then it is possible to atte Law of corresponding | Inthe vandeew: Is shows if pre Vanderw: (Po) , critical volume (Ve) at an important generalisation is known as N=P/Pe,O=V/Ve O=T/Te Where , ponding states. T= Reduced pressure © = Reduced volume © = Reduced temperature * P=Pe, V=OVe, T=0'Te For one mole gas vanderwaal’s equation (P+a/V?) (V—b)=RT Substitute the P, V, T values in the above equation. We get (Pe +a/(@ Vo?) (Ve—b) = ROTe ( TPc + a/ @'Vc?) ( OVc-b) = RO Te Further we know that Pe = a / 27b, Ve = 3b, Te = 82 / 27bR . Substitute Pc , Ve, Te values in the above equation we get, Mla/ 27? +a/ ©?(3b)?) (G3b—b) = ROBa'/ 27bR Ma / 27 b+ ax3/ 30°?) (30 b-b)= 8ROaxb/27bRxb (Mla / 27b? + 3a /27b*O?) (30 b—b)= BROab / 27b°R a/27b* (I+ 3/@*) (30 -1)b= 8ROab /27b°R (+3 / 0°) (30-1 )=80 The equation is known as vanderwaals reduced equation of state. It involves reduced Pressure, reduced volume and reduced temperature since it does not involves the constants a, b, Te, Pe Ve. Which ate characteristics of the gas. So this equation is applicable to all gases irrespective of their nature. From the equation it is clear that if the two gases have same reduced temperature and reduced pressure. They will have the same reduced volume. This statement is known as Law of corresponding states. joule Thomson effect (ZC When a gas is allowed to expand adiabatically from the region of high pressure to the region of extremely low pressute, itis accompanied by cooling is known as Joule Thomson effect.) ; When a gas allowed to expand from the region of high pressute to region of low pressure the gas molecules moves apart. The inter molecular distance increaies’ Some Work is done in the separating of gas molecules. This work is done in the cost of kinetic thus decreases and thus leads to fall in temperature. = But hydrogen, Helium gases exp: these gases are cooled to a particular temperature hey behave like other gases. This particular temperature is known as inversion temperature. ) Inversion temperature (Ti) ‘The temperature below which a gas is cooled he jown af ga when allowed to expand is kni ee Ti = 2a/bR Ex: Tiof H, =~ 80% Tiof He = - 240% a ee energy which ands they are heated instead of cooling. How-everf Below Inversion temperature if a gas is allowed to expand it jis cooled. Above inversion temperature if a gas is allowed to expand it is heated. LI ID STATE ste molecular forces in liquids, TWo types of inter molecular forces exists in liquids whi Yona lecular forces exists in liquids which are very weak. | 2arogen bonding it) Vanderwaal forces:- ees i= These are again two t ' : pes 2) Dipole-Dipole attractions » b) London forces (dispersion forces) Dil pole-Dipole attractions:- > Polar molecules have partial Positive and partial negative charges. > The intermolecular attraction between partial positive charge of a molecule and partial negative charze~ ofanother molecule is called Dipole-Dipole attractions. Ex:-H*5 Crd + Partial positively charged hydrogen of one Helis attracted by partial negative charged chlorine of another Hel. These are called Dipole-Dipole attractions. +8 8 ay 8 8 HO H-O a be 3° H-C + Dipole-Dipole attractions increases by the increase in EN. difference. ) London (dispersion) forces:- + Innon-polar molecules there can be no Dipole-Dipole force. These are temporary attraction forces induced in non-polar molecules due to mutual interactions in liquid state. These are called London forces, > These are very weak vanderwaals attractions, generally observed in non-polar molecules like Noble | gases, Alkanes etc. | > Electron cloud in a molecule, may concentrate one side of the molecule, making the molecule as |_ instantaneous dipole, which makes other molecule as induced dipole, > The attractions between instantaneous dipole and induced dipole is called London forces, | 6 6 +8 | Ne Ne . Ne |> London forces increases with increase in molecular weight due to more polarisability. Qn rogen bondin: : > The weak electrostatic attraction between Hydrogen atom and high E.N. atom (F,0,N) of the Same (or) another molecule is called hydrogen bonding, » Hydrogen bond was shown by dotted Pines (,..025++e-rnceree) ) ' | S The a one bond is 3-10 K.calimole. Hence hydrogen bond is weaker than covalent bond, Ducto Febonding, molecules exists in liquid state. — H-bonding is strongest in HF. —> H-bonding is two types. a) Intermolecular H-bond b) Intramolecular H-bond Inter molecular H-bond:- The H- bond between two molecules of same type (or) different is called Inter molecular H-bond. Ex:- H,O, HF, NH,, H,SO,, CH,-COOH, P-nitro phenol, p- chloro phenol etc. Str be & & & §& H—O- --H—O---H-—O h &t & bh hee bt & H—F- -- H~F-- H—F b) Intra molecular H-bond:- The H-bond formed with in a molecule is called Intra molecular H-bond. Ex:- O Nx Z So6 . 1 Yas SS HH. oO” O- nitro phenol 4X, 3H “Sos OG H® oO O - hydroxy benzaldehyde Structural differences between solids, liquids | _-_—srases i: — Property Solids Liguids | Weak 1) Inter molecular Strongest Intermediate Forces of attraction Molecules moves 2) Motion of molecules. Not possible. There is only vibrational motion. Molecules moves Randomly hence Liquids flows. But, the speed is Less than in gases Ieregularly with hi speeds. | 3) Randomness of molecules. Least. (Molecules ard arranged in orderly aj fixed manner) Intermediate —— Randomness is maximum in gases, | 4) Crystal lattice Crystal lattice exists. Semi crystalline. No crystal lattice. 5) Shape and volume Have definite shape and volume. Have definite volume but, no Have no definite | shape and volume. definite shape. Liquid crystals (or) Mesomorphic states state having some crystal properties and some liquid proj Transition temperature The intermediate state (mesomorphic state) between crystalline solid state and liquid Ex:- Cholesteryl benzoate perties is called liquid crystal. The temperature , at which crystalline solid changes into liquid crystal is called transition temperature. —_ Ex:- P-cholesteryl benzoate Solid —— Liquid Crystal <> Liquid Transition temperature = 145° M.P = 178°C Classification of Liquid crystals Liquid crystals have been classified into 3 types. a) Smectic Liquid crystal b) Nematic Liquid erystal c) Cholesteric Liquid crystal 4) Smectic Liquid erystal (Smeetic= soap like):- + These are more near to solid crystals with some liquid properties. + These are highly ordered among liquid crystals and exists in the form of layers with molecules aligned in one direction, ~ These layers can slide over one another on applying pressure and on a clean glass plate smectic liquid crystals forms a series of terraces (or) strate (steps like structure) > Smectic liquid crystals also gives X-ray diffraction patterns like solid crystals but only in one direction. AMM) Mmmm J structure Pressure Smectic liquid structure TEN Terraces (o1) steps Ex: (1) Ethyl-p-azoxy benzoate Transition temperature MP 114°c 121% (2) Ethyl-p-azoxy cinnamate Transition temperature MP 140% 249°C ) Nematic Liquid Crystal (Nematic= Thread like):- ~ InNematic liquid crystals molecules are parallel to each other and they are free to slide over individually, There is no layered structure in Nematic liquid crystals. : ‘ ~ These are more near to liquids, but scatters light like solids. Ex: (1) P-methoxy cinnamic acid (2) P- azoxy anisol Hunn uuu | unit wun : HELIA No layered structure ummm uuu Munn AW | PT Nematic liquid crystal (3) Cholesteric liquid crystal: —» These are similar to Nematic liquid crystals, but shows strong colour effect (optical property) in polarized light. Hence, these have some layered structure. —» Cholesteric liquid crystals have both the properties of Nematic and smectic liquid crystals. —> In these liquid crystals, The molecules are parallel, but are arranged in layer. Ex:- (1) Cholesteryl benzoate Transition temperature 145°C Structure of liquids : The liquid state may be considered as an intermediate state between the solid and gaseous states of matter because liquids may be obtained either by cooling gases under pressure (or) by melting solids. Athigh temperature and low pressure gas molecules are distributed completely at random with the inter molecular forces almost absent. On the other hand solids will be present as the most orderly arrangement units. The properties of liquids lie in between the properties of gases and solids. Aliquid may be regarded as an extremely non-Ideal gas_This is quite reasonable postulate because near the critical point there is no distinction between the liquid and the gas. Differences between liquid crystal and solids, liquids The main differences between liquid crystals, solids and liquids can be understood by comparing the following properties. In solids, the constituent particles are arranged in a perfect order, where as in liquids there is short range order but there is no perfect order. Insolids, the constituent particles have neither translational (or) rotational motions, they can have vibrational motions only, but in liquids the particles posses translational, rotational and vibrational motions, In solids, as the particles are closely packed; they have very strong inter molecular forces of attractions hence they are rigid and definite in shape. In liquids though there are inter molecular attractions, but they are weak when compared to in solids. Hence they have fluidity and no definite shape. Liquid crystals are entirely different from the above properties. In this state they have different physical properties in different directions i.e anisotropy. They behave like crystals showing double refraction giving interference pattems of polarized light and show liquid properties like viscosity, surface tension and mobility etc. Applications of Liquid Crystals (1) Liquid crystals are used as commercial lubricants. (2) These are used for detecting tumours in the body by employing amethod called thermography. (3) Due to the electrical and mechanical properties, liquid crystals are used in gas-liquid chromatography. (4) Liquid crystals are used in digital displays like pocket calculators, digital wrist watches ete. (5) L.C.D_Devices:- The short form of liquid crystal display is LCD. These are generally used in watches, calculators and in industry. This device records the image, stores it and displays. This image can be projected ona screen. Coloured LCD devices are used in Lap top computers, Television, vedio games etc. LCD devices consumeless amount of electrical energy when compared with other instruments. InLCD display, liquid crystal is arranged in between two transparent electrodes. The thickness of the liquid layer is ofthe order 6-25 micrometers. This is controlled by chemically inactive substances. This LCD cell is perfectly sealed so that it is not affected by oxygen (or) moisturey

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