Thermodynamics Thermodynamic Terms, Properties, Processes and Internal Energy * Thermodynamic Terms ‘+ ThermodynamicProperties of a System ‘+ ThermodynamicProcesses + Internal Energy 1 Enthalpy Changes during Physical and Chemical Processes + Enthalpy Changes during Physical Processes (Phase Transformation) * Enthalpy Changes during Chemical Processes 1 Spontaneous and Non-spontaneous Processes Scanned with CamScannertS a ce ee 2 GRB + Topper’s Choice Chemistry Class-x1 (such as chemical, mechanical, electrical area characteristic fea reactions. Vari of energy ( Energy changes ture of chemical reactions. Various forms of energy eal withthe study of thee etc) are inter-related and may be transformed from one form into another. Thermodynamics transformations. + Thermodynamicsis concemed with the study of macroscopic systems involving a large number of molecules. ft cloes not deal with the properties of individual molecules. * Thermodynamics can predict the feasibility or spontaneity of a process. ‘¢ Thermodynamics isnot concerned with the methods and rate of the energy transformations. It is states ofa system undergoing the change. based on the initial and final Topic 1\ thermodynamic ‘Terms, Properties, Processes and Internal Energy ‘Thermodynamic Terms Universe consists of system and surroundings. System It isthe part of universe that is under thermodynamic consideration. A system may be homogeneous or heterogeneous. Surrounding Its the part of the universe other than system which can interact with the system. Boundary It is the real or imaginary surface that separates system from surroundings. If boundary is sealed, matter cannot be exchanged with surroundings. It may be: '* Diathermic which permits energy transfer as heat. * Adiabaticlinsulated which does not permit energy transfer as heat. ‘Types of System (On the basis of exchange of energy and matter, chemical systems can be classified as: + Open system * Closed system + Isolated system = Open System ‘Assystem which can exchange matter as well as energy with the surroundings is called as an open system. Boundary + ‘Neither sealed nor insulated Example + Reaction in an open vessel. = Closed System Assystem that con exchange energy but not matter with the surroundings is called closed system. Boundery + ‘Sealed but not insulated Example Reaction ina closed vessel made of conducting material. # Isolated System “Assystem that can neither exchange energy nor matter with the surroundings is called as an isolated system, Boundary + Sealed and perfectly insulated Example + Teain perfectly insulated thermos flask. Scanned with CamScannerState of the is the condi Properties include: "°° I" Which t exist ree ists. 1 Pressure (p) 's described by the measure Amount / num i Change in any one of Extensive Properties * Intensive Properti Extensive Properties operties System which depend on the quantity of s heat capacity, ete, Pend on the quantity of substance present. For ne nay, Intensive Properties men enthal of substance present. For ex ton, bp. and mp, refractive index, specific heat apace vr p wy Each port ete partion has awoke) temperature Is an intensive property. Thermodynamic Processes Isothermal Process A process in which temperature remains constant is called an isothermal process, ie, AT =0, Adiabatic Process ‘A process in which there is no heat exchange between the system andthe surroundings is called an adiabatic process ie, Isobaric Process cos : A process in which pressure remains constant is called an isobaric process, i, AP = 0 Scanned with CamScanner2S a GRB + Topper’s Choice Chemistry Class.x) \sochoric Process A process in which volume remains constant is called an isochoric process, ic, AV =0 Cyclic Process ‘When a system returs to its initial state after undergoing a number of different processes, itis termed a Process, change in all state functions will be zero. s acyclic process. Ina cyclic Reversible Process If. process occurs infinitely slowly and the direction of process can be reversed at any instant, the process is called reversible. For a reversible process, Peyternal = Pingernal t 4P For expansion : Pexsemat = Pigterat “4P For contraction Pesternat = Pinternat + 4P Irreversible Process If a process takes place in short duration and the direction of process cannot be reversed at any instant by small changes in variables, the process is called irreversible. For an irreversible process, Pernt = constant Internal Energy ‘The total energy of the system is called its internal energy (U). Internal energy is completely determined by the variables such as temperature and pressure. When there is a change in physical state ofa system (for example, liquid changing toa gas), the internal energy changes even ifthe temperature remains constant. ‘When the physical state of a system remains same (for example, gas remains as gas), the internal energy will change only if the temperature changes. Thus, for isothermal (T'= constant) expansion of an ideal gas, AU =0. Internal energy (LI) of the system may change by Transfer of heat between system and surroundings = Doing work on or by the system i AU=q+w Heat (q) Itis the quantity of energy which is transferred between the system and its surroundings as a result of temperature difference. We can change the internal energy of a system by transfer of heat between the surroundings and the system. ‘Sign convention = When heat is gained by the system q is +ve = When heat is lost by the system q i In order to measure the heat changes the heat capacity is used. Heat transfer results in change of temperature. The change in temperature is proportional to the heat transferred, ie, qe aT q=CAT where, =heat capacity ‘The heat capacity is the heat needed to raise the temperature ofa substance by 1K (or 1°C). Unit of heat capacity :J aod. Scanned with CamScannerThermodynamics 229 ‘Specific heat capacity is the heat needed to raise the temperature of a unit mass ofa substance by 1K (oF 1°C). Specific heat capacity (C,) = Quantity of heat supplied Mass of substance x Temperature rise 2 Cunt xT 2 49=CjmaT Unit of specific heat capacity : J g™* Kor} kg"! KE ‘When heat capacity is defined in terms of moles, it is known as molar heat capacity (Cy) Is the quantity of heat needed to raise the temperature of one mole of a substance by 1 K (or 1°C) Quantity of heat supplied 50, Molar heat capacity = : ‘Amount of substance in moles x temperature rise = co, -—4 ™ nx aT md 4 = Cyn dT Unit of molar heat capacity : J mol"! Kt 1 Heat capacity is an extensive property while specific heat capacity and molar heat capacity are intensive properties. 1% Different substances have different values of heat capacities. So, heating different substances with the same amount | of heat energy does not give the same temperature change. ‘ For gases, the value of heat capacity depends on whether the measurement is carried out at constant pressure (Cp)or at constant volume (Cy). Cp and Cy refer to molar heat capacities. ‘Work (w) Ifthe boyndary between system and surrounding is adiabatic, there isno transfer of heat (q = O)between system and surroundings. 7 AU =4+0=040 = tyastaue - ‘Thus, the internal energy of the system can also be changed without exchange of heat, ie,, by work done. ‘Sign Conventions = Work done on the system is +ve. 1 Work done by the system is -ve. A system can do two types of work, i2, electrical work (no change in volume) and mechanical work or pressure-volume work (volume changes). In thermodynamics, we consider only mechanical work, i.e., pressure-volume work, Pressure-Volume work Consider a cylinder containing‘one mole of gas fitted with a frictionless piston. Let the cross-sectional area of piston = A During expansion piston moves a distance = dx Work = force x displacement of piston dw = Fxdr Ry Axde i = dy = Pay dV Scanned with CamScanner230 : GRO * Topper’s Cholce Chemistry Class-xy Integrating both sides ¥, a ao fra av ; vy y, we fp, dv 4 In case of expansion, 1¢ of compresslon, ‘+ Work is done by the system, ‘* Work is done on the system, * Volume increases(V, > V;) Volume decreases (V; < V4) = dVistve = dV is-ve. = Ry dVisalso+ve = Py dV isalso-ve But according tosign conventions’w’ mustbe-ve. | But according tosign conventions w/ must be+ve. ‘Therefore, ~ sign is used to make work -ve. ‘Therefore, ~ sign is used to make work + ve, Hence, wa -f/ hy dV Hence, wan fy at av = Ye AV 1 ‘Under irreversible conditions, ‘Under isothermal reversible conditions, Pay = Constant Pat Pat * dp wan Pay ftv wen fl? Py dV 7 = Pal Vy? i RC Va - fe Py AV f dp =H f3P av [being small, dpdV is neglected] Va nT =f eT ay Inv =n f)2% av [nT is constant for an isothermal process] PV =nkT] s =-nRT [In Vg~InVj) Scanned with CamScannerThermodynamics 234 * tnespeson oa g38(¥,> Vi), work daneby the system, Hence, work is -ve, 7 ee | compression ofa 828 (V, <4), work is done on. the system, Hence, work is +ve, ‘+ When system changes from one sate to * Some useful energy convers eae ‘out undergoing change in volume, no work is done, iz,, w= 0. ion factors are: 1Latm=1013) 1Lbar= 100) First Law of Thermodynamics. Iso known as the principle of conservation of ener BY which states that energy can neither be created nor destroyed. It can only pliner (one form tothe other, i, the total energy of universe (the sum of energies ofa system and surrounding) is Mathematically, first law of thermodynamics can be expressed as: AU=q+w Let a system in state A has internal energy U, {heat (q)is supplied tothe system, internal energy of state A becomes Uy +4 {Let work (w)is done on the system, internal energy of final state B (Ls) becomes Uy +4 +1 2 Us =U, + q+ Up-U, = q+ = AU =q+w ‘Note : Put the value of q and w with sign conventions. = In am isolated system, there is no exchange of matter or energy with the surrounding, So, 9-0, w=0 > au=0 ic, the energy of an isolated system is constant. ‘The change of state may be isochoric, isobaric, isothermal or adiabatic, (Foranisolated system) = If change of state is isochoric, Wavy = AV =0 = mnt Pay AV] = AU =9/ +0 > AU =ay i.e, during isochoric process heat supplied to the system (qy) is equal to the change in internal energy (AU). = If change of state is isobaric, ie, ap =0 Most chemical reactions in laboratory are cartied out in open system so, the reactions occur at constant pressure (ie,, atmospheric pressure). : Heat evolved or absorbed in a process at constant pressure (qp){s known as enthalpy change, SH. i At constant pressure: AU =9,+w=AH+w AH = AU-w = AH = AU-(-PAV) = ait =auls Pav We know that, ‘BH = Heat change at constant pressure(q,) f AU = Heat change at constant volume (,) oo cmmemmmemaeeemememe Scanned with CamScanner_- : ras, Gp =%0+ PAV. Mp4 = PAV ie, difference between energy at constant pressure and energy at constant volume is equal to work done, In reactions : — Where all the components are liquids, solids or in solutions (ie, in systems containing no gases), volume changes are very small and PAV can beneglectéd. | — a o aH =u — When gases are involved, volume changes can be large. Then, PV=nRT AtconstantT and P, PY, = mR (jmmolesofresctant) PY; =m RT (%=moles of product) _ PVg~ PV, = mRT—mRT PUW2- M4) = (mq~m RT PAV = An RT ‘here, isthe change in number of moles of gases Quug (AH = AU+ PAV = AH = AU+AngRT (Substituting the value of PAV) « Or 4p = 4+ AngRT ‘An, is the change in number of moles only for gases not for solid and liquid. For example, Zn (5) +2HINO, (ag) —> Hy(G)+Zn(NOs)2 (9) Arig = E gascns prcacts ~ E Mgucous reactants =(-0)mol [only gaseous moles are considered] =+1mol SH=AU ie, 95=4y If, An,>0 AH> AU ie, 45> ay If ang<0 AH< AU nies Gp Vy ve work ‘+ Work done on the gas when both pressure and volume vary : Work done on the gas, w= wy +102 +105 +104 +105 (ie,, Shaded area) '* Work done by the gas when both pressure and volume vary : Work done by the gas = Shaded area th | by / . V Vr vo # Cyclic process : — Work done in a cyclic path ABCA Work done = Area of A ABC 1 Xx ACK BC 1 7A AVY-v) Scanned with CamScannerSSR i ‘Thermodynamics *# Graphical proof that work is not a state function : State function depends upon the intial and final state ofthe system irrespective ofthe path choosen for the change: “@) Work done, w_ = PAV =Shaded area a 4 Work done A-> C = Zero (as AV =0) © tol. 7 Work done C-» B = PAV Ghaded area) e LL => Work done A-» B= PAV LZ vO v— t f--4 7 © e Work done =Shaded area vi Ve vo In above graphs, gases passes A—> Bin 3 ways. The work done by gas is represented by the shaded area. ‘Work done in all three cases is different. Therefore, work isnot a state function. f {Topic 2 \ enthalpy Changes during Physical and Chemical Processes During any physical or chemical process, new interactions are set up and old interactions break. Breaking of interactions requires energy while energy:is released during the setting up of new interactions. So, the processes are accompanied by evolution or absorption of energy. The difference in energy between the breaking of old interactions and formation of new interactions determines the overall change in energy ofthe process. ‘Thus, the processes are of two types + “Exothermic «* Endothermic Tn exothermic processes, heat is evolved In endothermic processes, heat is absorbed | Ro P+ heat E R + heat > P. The enthalpy change, AH fra process isthe heat transfered between the reacting system and the surroundings at constant | pressure (4p) Than exothermic process, Hpyeauce< Hrescats AH= Hpeducs~ Hreacants ‘Therefore, the overall enthalpy change (7, or AH) is-ve. nan endothermic process, Hewauas> Hhesauna AH = Horoducts ~ Hpeactants ‘Therefore the overall enthalpy change (9, or AH) iseve, “The enthalpy change for various processes is denoted by A H. The subscript‘ represents the type of proces. ‘components. es Scanned with CamScanner ‘The value of A, H depends upon the temperature and pressure at which the process occurs as well as the physical state of the |”GRB + Topper’s Choice Chemistry Class-K1 symbol ® i described to allow comparison between the values. These ‘Thus, a setof standard conditions (denoted by superscript standard conditions are: © A pressure of 1 bar. i 3 «The reactants and products in their standard state, i, pure form at 1 bar pressure or 1 M concentration for a solution, “The values of A, H® are written ata specific temperature, usually 298 K (25°C) and always have a +ve or -ve sign to show whether the process is exothermic or endothermic. ‘Changes during Physical Processes (Phase Transformations) Enthi ‘There are three common states of matter, ic, solid, liquid and gas. Transitions between these states of matter a Transformation. Enthalpy changes accompany these phase transformation and the values refer to one mole of the substance. are known as Phase sublimation Seu H? Fuslonimeting = Veporzation “ae wr Uiguid Standard Enthalpy of Fusion, A jy,H® Itis the enthalpy change accompanying transformation of one mole of a solid substance into its liquid state at its melting point and at 1 bar pressure. It s also called molar enthalpy of fusion. Standard Enthalpy of Vaporization, AyapH® Its the amount of heat required to convert one mole of a liquid into its vapour state at its boiling point and at 1 bar pressure. Itis also called molar enthalpy of vaporization. ‘Standard Enthalpy of Sublimation, A.4° Enthalpy of sublimation of a substance isthe enthalpy change accompanying the conversion of 1 mole of a solid directly into ‘vapour phase at a given temperature and at 1 bar pressure below its melting point. Fusion, vaporisation and sublimation processes described above involve breaking of interactions, Thus, are endothermic. Reverse sublimationtdepositon Sreverse sao H® Gap | me condensation? Liquid ; freezing, condensatic ination (eonen The ees pres feng condensation and reversion esto) repel vale the sting po interactio thermic. 5 4 pg? =~Meecring® Soap? = ~Beondenaston H® Sap? = ~S revere sapH® Ss a Scanned with CamScannerThermodynamics. 27) a Enthalpy Changes during Chemical Processes: ‘The enthalpy change in a chemical reaction is described in a thermochemical equation. For example, Ng (9)+3H3 (g) —+2NH3 (9) 4,H® =-9221) A thermochemical equation must be a balanced chemical equation. ' I also indicates the amount of heat evolved or absorbed, lene The thermochemical equations can be added, subtracted, multiplied or divided like algebraic equations. For example, Me AB &,H=x KJ mol and c—4D 4,H=y mol then, AtC—> B+D A,H=xty Kimol™ ‘= When a thermochemical equation is reversed, the value of &,H is reversed in sign. For example, Ie A—B A,H=4x Kj mot then, Boa A,H=-x Kj molt When a thermochemical equation is multiplied or divided by some number, 4H is also multiplied or divided by the same number. For example, I, AB A, H=x kj mol then, nA—onB 4,H=nx Kmol™ tis sometimes dificult to measure the enthalpy change ofa reaction directly. In such cases, Hess's law is very useful. Hess’s Law of Constant Heat Summation ‘Hess's law states that, “The total amount of heat evolved or absorbed in the reaction is same whether the reaction takes place in one step or in a number of steps.” In other words, the total amount of heat change in a reaction depends only upon the nature of the initial reactants and the final products and is independent ofthe path by which this change is brought about . : a (ee ats 8 Ate . Path: aD ‘Total enthalpy change= 4, H Path 2 A> B—>C—>D__Totalenthalpy change= 4, Hy +4,Hy+4,H Thus, b,H=O,H,+4,H+4,Hy (Hess's Law) . Ifthis is nots, the frst lc of thermodynamics is violated. Enthalpy of Formation ‘The enthalpy of formation of a substances defined as the heat evotved or absorbed when 1 mole of substance is formed from its constituent elements under given conditions of temperature and pressure, Itis represented by 4 yH. Scanned with CamScanner[fall the substances inthe reaction are in their standard state (298 K, 1 ba), itis knowns standard enthalpy of formation (a) ofthat substance, For example,” Nz (8) +3, (@) —92NH,(g)' A, H® =-92.2 kJ ‘But standard enthalpy of formation is defined for 1 mole of NH, FM) +3446) nH @ ia HE = A, H® (NHy) =~ 46.1 KJ an 4, H can be calculated for any reaction if the enthalpies of formation of each reactant and product is known. 4, H = EAs Heproducs)~ 2A s Heeeacant) i, fora general reaction : 2A+bB—> eC + dD A, H® = EA Hiprducts) EA jHiracans) . = {eA pH9(C)+ da pH°(D))~ (ad pH®(A)+ 64 ,H°(B)) Enthalpy of Combustion (AH) ‘Treenthalpy of combustion ofa substance i defined asthe heat evolved when Tinole of substances completely But in oxygen ‘Under standard conditions (298K, 1 bar pressure), its known as standard enthalpy of combustion, #7 Since combustion is exothermic, A: His always ve. For example, (CHa) +203 (8) —> CO ()+2H,0() "A, H® = A,H®(CH,)=~8903 Kj mot Enthalpy of Atomization (AH) ‘When one mole of a given substance dissociates into gaseous atoms, the enthalpy change accompanying the process is called enthalpy of atomization. Under standard conditions (298 K, 1 bar pressure), itis knowin as standard enthalpy of atomization, 4, H® For example, 1 @) — 2H@) 4, HP = 435.0 mol"! CHy@) —> C@) +4H@ A, H®=166501J molt “| In case of a monoatomic species in solid state, A, H® = A,ysH® For example, b Na (6) —+ Na (g) ‘Ag H® = 108.44) mol” Enthalpy of Allotrople Transformation (A trans) - knowns allotropes and the pheniomenionis known asallotropy For example: ‘arbor, sulphurana phosphorous shew alto) © Allotropes of carbon : ‘Diamond, graphite and buckminster ee. Allotropes of Sulphur + Rhombic and monoclinic ‘Allotropes of phosphorous? White, red and black Scanned with CamScannerThermodynamics 239 wel | | | | | When one mole of an allotropic form changes to another, the enthalpy change that takes place is called enthalpy of sllotropic transformation. Forexample, (Graphite) —s C Diamond) ; BransHt = +191) Enthalpy of Hydration (Ajjératonf) Itis the enthalpy change when one mole of the anhydrous salt is changed into the hydrated salt. Forexample,, CuSO, (s) +5 H,0 (1) —+ CuS0,5 H,0 (s) Ayiteaion H =- 78-1 KI mol ‘ia s generally negative as the hydration process is generally exothermic.! Enthalpy of Solution (Asouuton) ‘The enthalpy of solution of substance ina particular solvent is defined asthe enthalpy change wien 1 mole ofthe substance is dissolved in a Specified amouitt of the solvent. , Under standard conditions (298 K, 1 bar pressure), itis known as standard enthalpy of solution (AseusionH°) However, if such a large volume of the solvent is taken that further addition of the solvent does not produce any moreheat change, itis called entlialpy of solution at infinite dilution, Forexample, 72.4 kj mol HCI (g) +excess of water —+HC1(aq) —Asoutan However, when HCI (g) reacts with smaller quantity, a different enthalpy change is observed. For example, for its 0.5 M solution ~ 7S HCI (g) —> HCI (aq) Asouton ti? =-49.0 kJ mol™ The value of Asan may be positive or negative i, dssoltion process may be endothermic or exothermic. _Alfen any ionic compound dissolves ina solvent (ike water atic reaks into gaseous tons that undergo solvation (hydration in case of water). s ie, dissolution is exothermic, i AsciatonH® = +ve i.e, dissolution is endothermic, Factors favouring the solubility of any ionic compound in water: 1. Low Avice H® 2. High Aryan a eee Scanned with CamScannerGRB * Topper’s Choice Chemistry Class-x) Lattice enthalpy of an ionic compound is determined by Born-Haber cycle which is based on Hess's Law. For example, For the formation of NaCl, Born-Haber cycle is represented as: . Na) + tenw - es Nae) ag FS ‘Na’ @) cr) i ae i . Na'Cr (s) -- 2 According to Hess's Law Spec = Snot igh 8 (H+ Og H+ Oamcall + Bond Enthalpy (B.E. oF Ayonal) Energy is required in breaking of bonds and is released when new bonds are formed. Energy required to break a bond is exactly the ‘same as released in its formation. ‘The amount of energy required to break one mole dissociation enthalpy. of bond of a particular type between the atoms in gaseous state is called bond For example, Hal) — 2H@); by -4H? = 435.06 mol When a molecule contains more than one bond of the same type (like H,0, CH, etc), the average value of bond dissociation enthalpies is taken which is known as mean bond enthalpy. For example, = HO@—H@+OH®@; — 4H, =5020%) mot OH @) — H @) +0); AH, = 427.0 Kj mol ‘Mean bond enthalpy of OH bond = 220% 227 4) mot ‘As chemical reactions involve the breaking and formation of chemical bonds, the enthalpy of reaction can be associated with breaking and making of chemical bonds. = 46454) mot" 2 A,H =EBE @escants~EB-E Products) | For example, : CH, = CH, +30, —+2CO, +2H,0 or H-C=C-H + 30=0 —+20=C=0+2H-0-H 1 HOH 4/H=ZBE qacans)-EBE rots) = UXBEc wt XBEcac+3xBEowg)-l4xBE cio 4xBEn-o} 2 Scanned with CamScanner —<$Thermodynamics 2ar ‘The above relationship is valid when all : For example, : ¥,()+ 20, — 1,00) In this case, heat required to convert H,O (I) into H,0 (g) is also added. First law of thermodynamics has certain limitations + It puts no restriction onthe direction of heat flow. * Itisnotin position to tell that heat energy cannot be completely converted into work However, heat flow from higher temperature to lower temperature, ie, the flow of heat is unidirectional. In fact, all naturally occurring processes tend to proceed spontaneously in one direction only. Spontaneity of a natural process means that process proceeds in one direction without the assistance of an external influence, A spontaneous process is generally accomplished by decrease in energy! enthalpy, ie, all exothermic processes are generally + spontaneous. But some endothermic processes (like evaporation of water) also proceed spontaneously. ‘Also some processes like isothermal expansion of a gas are spontaneous although the process is neither exothermic nor endothermic, ie, there s no change in enthalpy. ‘Thus, the decrease in energy/ enthalpy is not the sole criterion for the spontaneity of a process. There is some criterion other than the enthalpy change for explaining the spontaneity ofa process. This factor is called entropy which i defined.as the degree of randomness or disorder. : Moreover, the spontaneity of a process also depends on the conditions. For example, melting of ice is spontaneous above 0°C but below 0°C it isnot spontaneous. fropi \\ spontaneous and Non-Spontaneous Processes once started, will continue under given set of conditions without any outside intervention. Spontaneous processes are those that, Ifa process does not occur under specified conditions, tis said tobe a non-spontancous process, {A spontaneous process may occur with or without initiation. For example, ‘Without initiation With initiation . Dissolution of salt in water ‘Burning of candle Evaporation of water Decomposition of calcium carbonate Mixing of different gases Reaction of hydrogen gas and oxygen gas to form water. Examples of non-spontaneous processes : = Flow of heat from cold body to hot body. «Diffusion of gases from low pressure region to high pressure region, : = Decomposition of water to hydrogen gas and oxygen 62s. renzo dot me cer mat fis Haag of Fa oar bal Te Pree: Criteria for a Spontaneous Process Spontaneous processes occur due to two factors: Tendency to acquire a state of minimum energy/enthalpy. Tendency to acquire a state of maximum randomness or disorder (Entropy), Scanned with CamScannera Soe aie GRB + Topper’s Choice Chemistry Class-xi State of Minimum Energy and Spontaneity ‘Minimum energy corresponds to maximum stabilit . So, all spontaneous processes tend to acquire the state of minimum energy, ie, ~ve value of enthalpy change (AH) should be the criterion for spontaneity. ‘Thu; exothermic reactions occu spontaneously on account of decrease in enthalpy (AH = ve). For example the formation of ammonia in Haber's process is exothermic and spontaneous a Nj(g)+3H4(¢) — 2NEG(s) 4, H® =-922 Kj mol But, some reactions are spontaneous despite of being endothermic. For example, 3Nas)+ Og) — NOs) 4,H® =+332 KJ mol ‘Therefore, its obvious that decrease in enthalpy is a contributory factor for spontaneity, but itis not true for all the cases. State of Maximum Randomness and Spontaneity ‘There are certain cases, where there is no change in enthalpy (AH =0} but sill the processes are spontaneous. For example, mixing Of gases in isothermal condition. ‘When two gases separated by a partition in an insulated container are allowed to mix, both the gases tend to acquire larger volume by diffusing into each other. Due to increase in volume, the randomness or disorder of gas molecules increases. Gases were diffused at their own without any external agency. Thus, diffusion of gages isa spontaneous process. So, it may be concluded from the above example that a process tend to Proceed in that direction where randomness or disorder increases. lomness or disorder of the stem is measured in term of entropy (5). eater the randomness or disorder of the system, higher is its entropy. Solid Liquid Gas Envoy ieaces * If entropy of the system increases, AS>0 and if it decreases, AS<0, * Its an extensive property as its value depends on the quantity of substance 1 Iti assate function as AS is independent of the path and given by present in the system. 45 = Sena ~Siassa During a reaction, if ‘number of moles of gases increase = entropy increases number of moles of gases decrease = entropy decreases ‘Quantitative Measure of Entropy Change Whenever heat is added to the system ‘Thus, heat (q) has randomizing influence on the system, ie, Asa] — Butthe distribution of heat also depends onthe temperature a which eat is added tothe system Heat ad z temperature causes greater randomness than when the same quantity of heat is added ec toa aystem at : Ps it at higher temperature. This suggest® that the entropy change is inversely proportional to the temperate at which heat is ada led to the system. ie} ase. Scanned with CamScannerThermodynamics 28. Sill thg ond Tartar [as -= ‘where, qis the heat supplied to the system at temperature, T. 7 } ‘applied only when the heat 1s transferred fae ane 5 sferred reversibly. Entropy Changes during Phase Transformation ‘The phase transformation is reversible since it taki i i sible since it takes place at equilibrium and reversible heat change at constant pressure is the enthalpy change, ie, gq = AH. me : Entropy of Fusion Itis the change in entropy when one mole of solid substance changes into liquid form at its melting point. Basen $= Mtsion H Entropy of Vaporization Its the entropy change when one mole of liquid change into vapours at its boiling point. aap Sep = Entropy of Sublimation Its the entropy change when one mole of solid changes directly into vapours at a particular temperature. J ‘fag £ Bay = AB Fusion, vaporization and sublimation are endothermic. So, tain H Aap H, Aan have positive values. Therefore, AS wil be positive for these changes «The entropy changes for the revere processes (freeing, condensation and deposition) have the opposite sign but the same magnitude as those for fusion, vaporization and sublimation. Second Law of Thermodynamics Second law of thermodynamics states that for any spontaneous process, the entropy of universe is constantly increasing, For all spontaneous process: Stee $= Apystem $+ Asure S > 0(+¥E) * If Agus $>0, the process is spontaneous ‘Aaai $<0, the process is non-spontaneous Aigai $=0, the process is at equilibrium Gibbs Energy (G) ‘The two thermodynamic quantities enthalpy (H) and entropy (S) affect the spontaneity ofa process. Therefore, both AH and AS should be considered simultaneously. Gibbs introduced a thermodynamic function that takes both these factors into consideration called Gibbs free energy (G). The change in free energy (AG)of the system alone can give the criterion for spontaneity. ’ ir lable. to obtain the maxim. ful Gibbs free energy (G) of the system is the maximum energy avallable.{0.obtain the maximum useful work. But the of maximum om = ysem is only idealization. In any real situation, less than this maximum work is obtained. Thus, ecrease in the ffee energy during a process is the measure ofthe useful work done by the system. a Whena system reaches an equilibrium state all observable properties become constant and the system loses the capacity todo the external work. Thus, free energy ofa systém isthe dilference between the initial state energy (H) and the equilibrium state energy (which is given by the product of Tand $). This amount of energy: isavailable| for doing external woik. The equilibrium state energy of the system is also regarded as non-available energy. = ee Scanned with CamScannerbe GRB + Toppers Choice Chemistry Class-Ki Matera (tcostnt Tad (Git Halts eunton Free Energy Change and Spontaneity Bi Ina system which is not isolated from its surroundings, total entropy change (Ay..a1 5)is given by : Aiort S = Sytem $+ Bae S - Boon H = Scat S = Aspten $+ EE = Acct S = Aystem 5 [gure H = ~Seystem H] Santen H - Beat S = yen 5 1S = Baten $= = T Arta S = T Agystem S~ Asystem A = TAyaat $=~(Aaysem HT gym S) = Tia S=~Bytem G = Soutien 6 = =P oat For any spontaneous process Bia $>0 {Second law of thermodynamics] = Téa $>0 = TA yaa S<0 = Agutem G<0 Auyton G 65 -ve fora spontaneous proces. Second law of thermodynamics can be restated as, “in any spontaneous process at re open oi tame ane in any spor Process at constant temperature and pressure, the free | According to this definition Sgysem G-<0; the process is spontaneous ‘Sgyten G>0; the process is non-spontaneous Ayaan G =0; the processis at equilibrium Effect of temperature on the spontaneity of a process For any spontaneous process, AG= AH ~TAS<0. See Spontaneous at all T Non-spontancous at all T Non-sy Spentreo rie ne Spontaneous (at high T) Non-spontaneous (at low T) ve (Exothermie) ‘4ve (Endothermic) ve (Exothermic) ve (at all T) +tve (at all T) ve( AH Tas) wve(AH< TAS) +ve(AH > TAS) +-ve (Endothermic) Scanned with CamScanner: : esl Thermodynamics Gibb's Energy Change and Equilibium Constant ‘The standard Gibbs energy. ‘change, aG® (t298 K and 1 bar pressure) is related to the ‘equilibrium constant (K) as: | AG® = ~2.303 RTlogKk Third Law of Thermodynamics ‘The third law of thermodynamics is related with substance is zero at absolut ‘determination of entropy. According to it, entropy of perfectly crystalline te zero temperature (0K), Atabsolute zero, constituents in. ‘Perfect crystalline substance are atthe proper crystal lattice ste, Thus, there is zero disorder and hence zero entropy, However there are certain ‘substances which possess certain entropy even at absolute zero. This entropy is known as residual entropy. Partect crystal ‘Actual crystal AB OB OAB ag BBA ARAB ABABA ‘BAB OBA AB AB ABABA BBA ARAB AB AB OAR AB BA ABABA . Has some residual Zero entropy at 0K moma resi (an Scanned with CamScanner