SUGHOM ‘Thermodynamics is related with energy and its transformation in ‘various forms in different physical and chemical processes. ‘Thermo + dynamics Study of change due to a driving force ‘Thermal which is related to temperature or energy, ‘The laws of thermodynamics deal with energy changes of macroscopic systems involving a large number of molecules rather than microscopic systems containing a few molecules. ‘Thermodynamics is not concerned about how and at what rate these energy transformations are carried out, but is based on initial and final states of a system undergoing the change. Laws of thermodynamics apply only when a system is in equilibrium or moves from one equilibrium state to another equilibrium state, Macroscopic properties like pressure and temperature do not change with time for 2 system in equilibrium state ‘The branch of science which deal with the study of heat energy and its transformation is known as thermodynamics. ‘Thermodynamics Dynamics Thermo = ; ‘Thermodynamics FirstIswof ‘Thermochemistry Second law of Third law of. ‘Thermodynamics (application of law in Themodyoamies Thermodynamics ‘chemical resctions) Basic Terms + System: Part of the universe which is under study for energy changes. > P=1atm Volume «—, IL >> T=300K Ex. Air ina room, water in a bottle, any living body. + Surrounding: Rest of the universe. ‘ Universe: Universe = System + Surroundings system] surroundings, Universe + Boundary: Anything which separates system & surrounding, is called boundary. 4 Boundary can be real or imaginary. 4 Boundary can be flexible or rigid ‘egg: Air in a flexible balloon (flexible boundary) Airin a room (fixed boundary). © Boundary can be adiabatic(non-conducting) or diathernis (conducting). Classification of System on the Basis of Nature @ Homogeneous systems: A system having uniform nature throughout, (made up of one phase only). (@ Heterogeneous system: A system not uniform throughos, (consists of more than one phase). Classification of System on the Basis of Boundary 4 Open system: System which can exchange both energy & matter with the surroundings. e.g: Living systems (any living organism) are open systems, air in an open room. Closed system: System which can exchange only energy but cannot exchange matter with the surroundings is called closed system. eg: Any matter in a closed container. + Isolated system: System which cannot exchange both enerzy as well as matter both with the surroundings. ‘e.g: Water in thermos flask. (Though not a perfectly isolated system but can be taken as isolated system for small interval of time as the energy exchanges are negligible). renee 4 Whole of universe is a perfect isolated system. ® Anlisolated system can be taken as small universe.‘Universe Closed System Isolated system (GREOFASYSTEM) ‘Open System « Itmeans the condition in which the system is present « It can be specifed/defined. by measuring/specifying some cbserablemeasurble properties ofthe system like pressure, volume, temperature, amount of substance, elastin a elasticity, heat eg For an ideal gaseous system, state of the system defined by specifying volume, temperature and pressure, : @ We may have to specify more properties of the sy depending on the complexity of the system, state Function + Property of system which is dependent only on the initial & final state ofthe system ic. itis a point function + Itis independent ofthe path followed to attain a particular state, Condition for a function to be a state function: ( 1fGis state function, fdb= 05 by (i) If is state function, $4b=0 For any thermodynamic system, Temperature, Pressure, Volume, Total intemal energy (Er U), Enthalpy(#), Gibbs free energy (G), Entropy (S) are all state functions. Path Function + Quantities which are dependent on the path/way, the system hhas achieved a particular state. e.g. Heat, work, Heat capacities (Molar heat capacities, specific heat capacities etc.) + These quantities are defined when there isa process going on. Extensive Properties + Functions or properties of the system which are dependent ‘on mass or size of the system are called Extensive Properties. ‘ Extensive functions are additive in nature e.g. The addition of the volumes of the two parts equals the volume of the whole of the room. eg Mass, Total heat capacity, Total internal energy (E), Enthalpy(#), Gibbs Free Energy(@), Entropy(S)- Chemical Thermodynamics and Energetics Intensive Properties i ‘& Functions or properties which are mass independent or size independent, are called intensive function. Intensive properties are not additive in nature.” eg: Temperature, pressure, molar heat capacity, specific heat capacity, density, concentration, vapour pressure How to identify extensive or intensive properties: if @ system in a particular state is divided into two equal or ‘unequal parts, the properties which have value equal to the original value of that property for the whole of the system is called an Intensive property. While the properties which have ‘values different from the values for whole of the system are called Extensive Properties. Example 1: Classify the following into open, closed or isolated systems: (® Animals and plants (i) Arefrigerator ora fridge (iii) A solar cooker Sol. i) Open system (ii) Closed system ii) Closed system Example 2: Which of the following are open, closed or nearly isolated systems? (0. Human beings (ii) The Barth (iit) Can of tomato soup (W) Iee-cube tray filled with water (0) A satellite in a orbit (°9 Coffee ina thermos flask and (vi) Helium fitted balloon, Sol. Open: Human beings, Barth, Ice eube tray Close: Can of Tomato soup, A satellite in an orbit, Helium filled balloon. Isolated: Coffee in thermos flask. Example 3: Separate out the following into extensive and intensive, ‘Volume, Temperature, Pressure, Boiling point, Free energy. Sol. Volume and free energy are extensive, others, are inten Example 4: A thermally isolated gaseous system can exchange energy with the surroundings. What is the mode of transference of energy? Sol. Workeee 1, Which amongst the following isan extensive property of the system? (@) Temperature (8) Volume (©) Viscosity (@) Refractive index Which of the following is not a state function of thermodynamic system? (@) Internal enerey(E) (©) Enthalpy(H) (@ Work(w) . What is true fora eyelie process (E=internal energy]? @ w-0 © AE=0 © aH (@ Both (6) and (6) |. The internal energy change when a system goes from state A to B is 40 ki/mole. If the system goes from ‘Ato B by a reversible path and retums to state A by an irreversible path what would be the net ehange in internal energy? @ <4 © 40m (©) Free energy(G) (© Zero @ >400 Types of Processes (® sothermal process: A process in which temperature ofthe system remains coastant i called isothermal process. P Isothermal TT, (i Isobaric process: A process in which pressure of the system remains constant is called isobaric process P. “i Isobarie P2=Pi 72 Jsotherms 1, >T, Jsobar ions or processes taking place in open vessel like boiling of water in open vessel, burning of charcoal, ‘melting of wax take place at constant pressure (1 atm.) (id) Adiabatic process: A process in which no heat exchange takes place is called adiabatic process. P rerms Adiabatic Jrotherms Adtabat Pressure Vy 1¥j_ Volume (o) Isochorie process: The process for which volume og system remains constant is called is0choric proces heating of gas in rigid vessel. Pressure Volume (0) Cyclic process: It is combination of two or more proc in which the final state of system, becomes identical w initial state. The net change in all thermodynamic prope of system must be zero. ©... AT=AP=AV=At BG = 0 However Q,,, or W,., may or may not be zero. "TYPES OF THERMODYNAMIC PROCESSES ON BASIS OF THE WAY TH PROCESSES ARECARRIEDOUT —__ Reversible Process # The process that ean be reversed by a very small change known as reversible process # Reversible process is carried out in such a manner sot the system is always in thermodynamic equilibrium witht surroundings at every stage ofthe process + Reversible process is carried out such thatthe difference driving force and opposing force is infinitesimally small that process takes pluce at infinitesimally slow rate F esviog— Foppesing = AF and dF —> 0 © An ideal reversible process will take infinite time to & completed ® Strictly speaking there is no ideal reversible process i To get an idea of a reversible process we can consider t following system An ideal gas is enclosed in a container and a massless pistoo puton the gason which apile of sands placed having patel of negligible mass, To carry out a reversible expansion ** @® ce dropper Module-1 CHEMIST!irs Sects hd ca te eee sand, tet cil ae ates ene by eo eee fate lcs a infinitesimally ana arn #8 %, assure the system in thermodynamic equilitaig al the expansion will be of reversible type, cy versie Process revit ooess which can not be reversed The Pye imeversible process, ve owes carted ota sch a manner 2 eM permodynamic equilibrium 5 only at initial & final state of the jntormediate stages. system may be in thermodynamic equiity oS a etn satin for example - step ireversble expansion of a gas sreurng the process there is a finite diference in divin orce and opposing force so that process takes place with faite rate. 1g Ineversible processes will get completed in finite time. 2 ial veal process are irreversible, zi by a small change is © that the system Process but not at the ‘work dynamically, Work may be defin form of ern only when, there is cones tbe fee ‘Jae sjstem. Such work is called mechanical or PV work, Week Mals-be nox-mechanical like electric work, trae, we will seuss only mechanical work {p [tisnot thermodynamic property of system, {o Sign convention, work on system = (sve. 5 py ta Hat is defined as the energy that flows in or out of a system tecause of a difference in temperature between the system and ‘issurounding. According to TUPAC convention: Heat lost by system is expressed with -ve sign. Heat given to system is expressed with +e sign. 4 Gy. Cy =R (for ideal gas) Units of heat & work: Heat and work both are forms of energy. Hence, their SI unit is Joule (3). Nm = 1J = 107 erg = 0.239 cal leal= 4.184 J=4.27 4,206 cal = 101.3 * 107 erg 1 L-atm = 101.3 UL-atm > 1 cal. > 13.> 1 erg hemical Thermodynamics and Energetics (INTERNAT ENERGYIE&U) Every system having some quantity of matter is associated with a definite amount of energy, called internal energy. U=Uxseies + Upoteniat * Urtecrovie * Unters Uisa state function & is an extensive property. AU = Una = Ujniiat Characteristics of LE. (1) Intemal energy of a system is an extensive property. 2) Internal energy is a state function. @) AU=0 (for cyclic process). % First law of thermodynamics: This law was given by Helmholtz and this law can be expressed as follows: (), Bnergy can neither be created nor be destroyed: (Gi) The total energy of the universe is always a constant, i.e. the sum of energies of a system and its surrounding is always constant. (Git) Whenever a particular form of energy disappears during a process, an equivalent amount of some other form of energy appears. AU=a+w HEAT CAPACITY/MOLAR HEAT CAPACITY/SPECIF! Heat Capacity [C]: The amount of heat required to raise the temperature of a system by 1°C is called heat eapacity of system, Heatrequired __ dq Tise intemperature dT Units: JK, cal K-!, J°C*, cal °C + Heat capacity is extensive property. ‘Molar heat capacity: Amount of heat required to raise the temperature of 1 mole substance by 1°C. Molar heat capacity = heat capacity/mole. Heat capaci Heateapacity dq moleof substance ndT aT Molar heat capacity (C,) =(éq Units: Jmot K+, cal molt K-!, mot °C“, cal mot! Ct + Molar heat capacity is an intensive property. Specific heat capacity: Amount of heat required to raise the temperature of 1 gm. of substance by 1°C. Specific heat capacity = heat capacity/lg of substance. eae Corea | ada molecular weight|~ maT Cat] Usiits: Je! K*, cal KY, Fg! °C, cal g-t Ct + Specific heat capacity is an intensive property. 95+ Calorie: Amount of heat required to raise temperature of 1g of water by 1°C (145°C to 15.5%C) is called as calorie. + If heat is da) _ att c, =(48) -2 @) (@)-t : If heat is supplied at c (2) =38 at), “ar supplied at constant pressure, then constant volume, then Relation Between C, and C, for 1 mole of an ideal gas He E+ PV Cplalways) > C, H=E-+nkT (for ideal gas) an ae (28)-() carencymavencyen = GeG+R © R] Mayer's formula (i) |S 4], Poisson's ratio om |Peessetle, (2a. (42)6|-i)] ame Monstnic} 3 fe | | none Dee | (ote | ee P| Nos oe | gr ix Z| coger Neots |g | ae | ae | frome Chemical reactions are generally carried out at constant pressure (atmospheric pressure) so it has been found useful to define a new state function Enthalpy (H) as. H=U+PV; AH=AU+A@V) at constant pressure AH=AU+P AV combining with first law. 7 anna, Hence transfer of heat at constant pressure brings tonsa jn the enthalpy of the system q Penn Tf substance is not undergoing chemical reaction or py, change. : AH = AU + aRAT (during heating) Rice cic lLe Example 5: Calculate the internal energy change in each the following cases (system absorbs 5 KT of heat and does 1 KT of way, (ii) 5 kd of work is done on the system and 1 KI of bey is given out by the system. Sol. ( Hereg=+5kJandw=-11T “According to first law of thermodynamics, A £ = gtwes+Cl=4Kt (i) Here w= + Ski and =~ IKI ‘According to first law of thermodynamics A E= qtwa-1+(+5)=410 i.e. the intemal energy of the system increases by 4 kin each case, Example 6: Represent the following observations in tems of proper IUPAC symbol? (@) Heat absorbed by a system is 20 Joule. (@) Work done by a system is 40 Joule. (©) Work done on a system is 5 Joule. (@) Heat given out by system is 50 Joule. Sol. It is standard practice to represent both types of heat ‘and work (in/out or on/by) by single symbols q and we (@) q=+20Joule (6) w=~40 Joule © w=+5 Joule @ q=-S0 Joule Example 7: Predict sign of work done in following reactions at constant pressure, Initial state Final state Gi) H,0() > #00) Gi) HL0@) > H,0@) (i) HO} > H,0(9) (iv) CaCOys) Ca0(s) + CO,() Sol. (i) +ve; (ii) -ve; (iii) -ve; (iv) -ve @ JEE Dropper Module-1 CHEMISTR!ey 5. Ifwork doe by the system is 300 joule when 100 cal heat is supplied to it. The change in during the process is reat (@ +200 Joule (©) 720 Joute (@ 120 oute 6, Asystem has intemal energy equal to, 450 Jof is taken out oft and 600 J of work is done on it wing final energy of the system will be @ ©,+150). _@) U,+ 1050 (© (U,~1503) @ (10505) 7, The work done by a system is 8 J when 40 J hest is supplied to it. The change in internal en system during the process is: ae @ 325 ® 403 (2 483 @ -321 8. Therelation between AU and AH at constant pressures (@ AH=AU-Pav —() aN=au+pay (Q AU=AV+aH @ aU-an+ap ©) 400 Joute 1.|sothermal Expansion or Compression of Ideal Gas Forisothermal process 2 AU=RCyp Al and q= AU -w=—w Now, w depends on path (reversible or imeversible). (@ Reversible process T= 0,P,V, =P,V, =constant (RT) ,AH= nC, AT=0 w, 2 Wey MRT ASL = RT in 24 i @Irreversible Process against a Constant External Pressure (Reversible) (Single step irreversible) Chemical Thermodynamics and Energetics Py Z ZZ. S Vi eevee (lwo step irreversible) (a step irceversible) order off a) Rev> S97? 2p Ange OR eee ‘ Compression Pea vi (Two step irreversible) (a step irreversible) Onder of value Of Wang) REV 5 w=-P(V,-V,)=-2R.AT Let the energy given to system is q and wo done by the system is W, then Internal enemy AU=4,- Here, ¢, = energy given to system at constant pressure So g,=AU+W “A Gp Wy U)+ P=) 4,7 Uz + PV,)—(U, + PY) 9,7 H,-H, {: H=U+PV= enthalpy, 4,~AH= nC, AT AU=n.C,y.AT 5. Isochoric Process For an Ideal Gas ‘Thus during isochoric process, heat supplied tothe system is equal to change in internal energy. 6. Polytropic Process For an Ideal Gas and q=n.C,.AT ‘The molar heat capacity, Cyy = Cy + CHEMISTRY @ 2 orepper Moduy dic oe process Unde i tem i “oe done system is equal to heat absorb orbed by the system, pu ie P(t) isobaric a q=AH=2¢,,AT | aU=nC,,AT | AH=nCp,,AT “Isochoric a ! eee we qn UenCy,AT | AU=nCy,AT | AH=nC,,AT | 3 Reversible | W~"Cya(T-™) adiabatic PY.-RY AU=nCygAT Process ree TV! = constant ane TP'4= constant q=0 nC y(TT)) if (2 et) AU=nCy,,AT eR hemical Thermodynamics and Energetics 0) Atconstant pressure, AIT = (Hp—Hy)=*ve (Hp? Hy) ‘Atconstant volume, AE = (E—B,)=#+¥e_(* Er? Ea) Like any other transfer of heat, th heat change of chemiea! ‘aston depends upon the conditions during the Process PY ‘which ‘Scartied out. hemical Thermodynamics and Energetics LAU=ay This condition is excellently approximated when the reaction ig carried out in 2 bomb calorimeter, where the volume remains constant. Ti: During the course of an experiment under ordinary bench-top conditions, the pressure is Kept constant. Many calorimeters operate at constant atmospheric pressure. Then, webave H=q, : The heat of reaction measured at constant pressure is ‘exactly equal tothe change in enthalpy of the reaction system. Constant pressure processes are much common if chemistry. Therefore, usvally whea ever we speak of heat o reaction, it implies enthalpy change at constant pressure. It is often necessary to use data obtained with bomb calorimeter which give AE in order to calculate AH. ‘We know that, AH = AU + A(PV) + If.all the reactants and products are liquids or solids, the PV values change only slightly so dU dH. + For reactions in which gases are involved, the values of A(PV) depends on the change in the number of moles of gas as result of reaction. +: A@V) = An, RT) AH = AU+An,RT Enthalpy of a Substance ‘& Every substance has a fixed value of enthalpy under any particular state. Though, its exact value cannot be ealeulated but ithas some finite fixed value. Only the change in enthalpy can be calculated when substance is taken from one state to other, & The enalpy of one mole afa substance called molar enthalpy inany paricular sae can be assigned symbol (substance) + For example molar enthalpy of water vapours at 398 K and U atm pressure may be represented a9 Hy (HO. 398 Key 1 atm). In very siniple words, enthalpy Gan be considered as heat cont (amount of substance, and during reaction this heat is being released or absorbed © Molar enthalpy of substance under standard conditions is calle standard mola enthalpy of substance Standard State of any Substance Means + For a GAS, standard state means ideal gas at 1 bar partial pressure at any give temperature. ‘© For a LIQUID ~ pure liquid at 1 bar pressure at any given temperature For a PURE CRYSTALLINE SOLID ~ pure crystalline solid at | bar pressure and at any given temperature For any SUBSTANCE or ION IN SOLUTION — the species should be in unit molality, at one bar pressure and at any given temperature, 401 UaITHALP Caw OF THERM jO CHEMISTRY) INTHALPY OF REACTION (CAWS OF THERMO CHEMIS Itis defined as the amount of heat evolved or absorbed when the | (q) Lavosier and Laplace’s pe Eatalpy of decomosig reacting species, as represented by a balanced chemical equation ofa compound is numerically €4 oF ae have completely reacted. Compound and only sign changes. Enthalpy or heat of reaction is given by: ts Law: The total amount of heat evolved or bsorbeg, © eee ther the reaction iscara” AB toa = POH posit HAH cat a chemical reaction isthe same whether ioniscani - ‘out in one or several steps (by one or more methods), Italso does not depend upon the manner in which the cheng, reaction is carried out. © Physical state of Reactants and Products: Physical oe state always affects the heat of reaction as heat energy is | Ex.Sinele step reaction A~> Pi ; involved in changing the physical state of a substance. For ‘Multi step reaction to produce B ne is given example, AH, an, SH, ph B AH, chs D a ee ees According to Hess's law Hg) + 4 O,(g) —> H,0(); AH i = AH, + AH, + AH, + AH, Difference in the value of AH is observed because heat is Be eat eee evolved when steam condenses. Allotropic forms of The Elements: The value of AH also depends on the allotropie form used in the reaction. For | 74. amount of heat evolved or absorbed when one mole of : substance is formed from its constituent elements in their moy example, Cldiamond) + 0,(g)—> CO,(2) ; AH =— 94.3 keal’mol | stabje state is called heat of formation. ‘C(amorphous) + 0,(¢) —> CO,(@); AH =~ 97.6 keaV/mol HG) + Ch(¢)—> 2HCI(g); AH =~ 44 keamol ee eee een Ce re ee ‘Thus, enthalpy of formation of HCl is ~22 keal/mol absorbed when 12 g of diamond is converted into 12 g of , trmorpovs carbon. Tiss called hen of tans, ‘The formation reaction of « compound has only one mle of ena the compound and nothing else on the product side. Only elements ‘ fataipie Foe ee oe cata giter | 2 BO Sable states of aggregation sppear onthe reactant sie (i) Enthalpies of Solution: Enthalpies of solution differ + depending on whether the substances react together in dry Hy =H, + f cjar slate oF in solution. For example, H,S(@) +1,(@) —> 2HI(solution) + S(6) AH'=— 17.2 kealmol H,S(g) + 1,olution) —> 2HI (solution) + S(3) is zero. AH =~21.93 kcal/mol (ii) Temperature: Enthalpy change of reaction also depends Enthalpy of Reaction from Enthalpies of Formation: The con temperature at which the reaction is carried out. This | enthalpy of reaction can be calculated by is doe ovation nthe hea capacity of he syste with AN? =E vq AH? ona) E Ya SAP, ext) sperature. where vg denotes corresponding stoichiometric coefficient This expression holds good for both elements as well as compounds. For elements, the first term on the right hand side Enthalpy of Formation of Elements + “By convention, the standard enthalpy of formation of every # Relation between or AE and temperature ar given by element ints stable state of aggregation atone bar presse Kirchoff’s equation. and at specified temperature is assigned a zero value.” The (AH, AH) = AC, T-) specified temperature is usually taken as 25°C. A few examples are AH, (O,, g)= AH (C, graphite AHS (Br, liquid) =0 This equations wed to find heat change of reaction a | AHH, S-Fhombie)=0 AH (8, monoctns) #0 4 temperature when it is known at another temperature, AH,’ (P, white) = 0 Gbe, (Ee lack) = 0 2 “The standard enthalpy of formation of a compound is the change in the standard Enthalpy when one mole ofthe compound is formed starting from the requisite amounts of clements in their stable state of aggregation.” i @ cE dropper Modul CHEMISTRYxample 14: For the reaction : C, > 2C0;(@) + 3H,0(9) if AU" = ~1373 kJ mot! Sol. —1368 kl mol"! AH? = AU? + An, RT aH OH(6) + 30,() at 298 K. Caloulate AH® ari =-1973 + 28.314%205 1000 AH =~ 1368 kd mor" Example 15: Classify the followin or endothermic: (@) Buming of a match stick () Melting of ice (©) Molten metal solidifies (@ Reaction between Na and H0 © Rubbing alcohol evaporates, Sol. Exothermic a, c, d; Endothermie : be Example 16: Calculate heat change of reaction at constant pressure, : F,0(e) + H,0(e) — 0, (@) + 2HF(@) The heats of formation of F,O (g), mol 20 (@), mol H,0(g) and HE gate 5 kelimol,-STkcanol andi respectively. Sol. Given that AF cation = EOOHD product ~ LOH pace ZHection = [SH (O,) + 24H(HE)] — (A110) + AH,(H,0)] : = [0+ 64) x2] - [5.557] =-65.5 Keal/mol \BProcessesas exothermic inge of the following * ee |. A mixture of 2 mole of CO and 1 mole of O,, in a closed vessel is ignited to convert the CO to COs. If AH is the enthalpy change and AU is the change in internal energy then: (@) AH>AU (®) AH=aU (©) AH 0,2) (UD) NH, “(g) + Cr(g)—> NH,Cls) (IV) P,(black) + 50,(¢)—> P,O,0(s) Which of the above does not represent AH” yrnarion OF the product? @ im © 1.0,m (LIV @ 1,uLV Chemical Thermodynamics and Energetics ENTHALPY It is the enthalpy change when one mole of a compound Combines with the requisite amount of oxygen to give products in thei stable forms. CHi(g) +20,(g) > CO,(@) +2H,0 (0 att 890 kJ mot"! ‘& Calorific value: The amount of heat produced in calorie or joule when one gram of a substance (food or ful) is. completely burnt or oxidised is called calorific value of food for fuel. ‘When one mole of methane burns, 890.3 kJ of energy is released, Example 17: The standard heats of formation of CH,(s) CO,(g) and H,O(¢) are ~76.2, -398.8 and ~241.6 kJ mot! respectively. Calculate the amount of heat evolved by burning 1 m of methane measured under normal conditions. Sol. The required equation for the combustion of methane is: CH, +20, —> CO, +2H,0; AH =? AH = AH yyrpancey ~ AH gpeacans) ‘AHgcon)* 2 * AHgn.0)~ AA ncn ~ 24Hg03) 398.8 -2 «241.6 -(-76.2)-20 805.8 kJ mot"! Heat evolved by burning 22.4 litre (1 mole) methane = 805.8 KJ, So, heat evolved by buming 1000 (im?) methane. 805.8 1000 = 35973. Fg *1000 = 35973.2k3 Concept Application! . The heat of combustion of ethyl alcohol is -300 keal/ ‘mol. Ifthe heats of formation of CO} (g) and H,0(6) are 94,3 and -68.5 keal/mol respectively, calculate the heat of formation of ethyl alcohol (@ ~94.1 kcal/mol (©) -96.1 keal/mot (®) ~ 64.1 keal/mol (@) =59.1 keal/mol 103,17, The standard heat of combustion of solid boron is equal to (@) aH; (B,05) (©) 2AH;6,0)) (6) (12) B11; (B203) @ (@)AN,@B:0)) Which one of the following expresses Q as the heat of combustion? (@) 21, +0, —> 240+ & c+40,—+00+9 (©) CH, +20, —> CO, +2H,0 +Q @ 20,H, +150, —> 12CO, + 6H,O+Q [/ENTHALPY OF SOLUTION ‘The integral enthalpy of solution at the given concentration is the enthalpy change when one mole of the solute is dissolved in 2 definite quantity of solvent to produce @ solution of a desired concentration. While recording integral enthalpies of solution it is a general practice to state the amount of the solvent in which I mole of solute is dissolved; Thus HCI(g) + 10H,0(6 -+ HCI10H,0 AH =-69.5 kJ mol"! indicates that when 1 mole of hydrogen chloride gas is dissolved in 10 mol of water, there is an evolution of 69.5 kJ of heat. Other values are () HCI(g) +25 HOC) > HC125H,0 723 kJ mor (@ HC\(g) + 40 H,O( > HCI 40H,0 73.0 kJ mot" (i) HCI(g) + 200 H,0( > HC1 200H,0 74.2 KS mor (>) HCU(g) + ag HCI (aq) 75.0 KI mot! © Whenever amount of solvent is not specified then take its amount to be very large just like in equation no. (iv). Enthalpy of hydration is used in following two ways. a. Enthalpy of hydration of anhydrous or partially hydrated salts: Enthalpy of hydration of a given anhydrous or partially hydrated salt is the enthalpy change when it combines with the requisite amount of water to form a new hydrated stable salt 104 y For example, the hydration of anhydrous cupric sul eprsentedby a CuSO, (8) + 11,0 (F) > CuSO, . 5 H,0(8) There is almost invariably a liberation of heat in reactions, ic. the value of AH is negative. CuSO,(3) + 800 1,0 (6) -+ CuSO, 800 H,0 AH, = ~ 68 kI mot"! CuSO, . SH,O (5) + 795 11,0 (4) > CuSO, 800 1,0, AH,°=+ 10 kJ mol by subtraction, we get CuSO,(s) + SH,O (2) > CuSO, - 5 H,0(5):AH,? =~ 78 kd mops b. Enthalpy of hydration of gaseous fons. Enthalpy of hydration of any gaseous ion is the entha, change when 1 mole of the gaseous ion is hydrated in lap, amount of water to form aqueous ion. Sg, By convention, the standard enthalpy of formation of (ay is taken to be zero. eg, Enthalpy of hydration of CI” gaseous ions will py represented by = CI(e) +29. > CI (aq), AHS = AH (CI, aq) (ENTHALPY. ‘The amount of heat evolved or absorbed when solution containing one mole of soluie is diluted from oné concentration to another For example, HCI.10H,0 + 1SH,0—> HCL25H,0 ; AH =~3.02 ki/mol ‘This value of AH is the heat of dilution. The heat of dilution of a solution is dependent on the original concentration of the solution and on the amount of the solvent added ‘# The amount of heat released when one gram equivalent of. acid is neutralised by one gram equivalent of a base. + The amount of heat released in formation of one mole of water when an acid is neutralised by a base. + Enthalpy of neutralization is defined as the enthalpy change when one mole of H* in dilute solution combines with one mote of OH” to give rise to undissociated water, Le. H'G@q) + OH (aq) > H,0(0);, AH=-57.1 kiimole=—13.7kealel Remember + For Strong Acid + Strong Base, heat of neutralisation is always equal to 13.7 kcal/mole or -$7.1 ki/mole. ® Forany other combination of acid and base this heat released is less than 13.7 keal/mole or 57.1 ki/mole. @ ce dropper Module-1 CHEMISTRYined. ieee ofthe substance, Examples ere: HON+Na* OH Na+ CN-+ #0; aH = 19 eS mot! COOH + NaOH" Nat + : one as CH,COO- + H,0; aH ‘The enthalpy of ionization can be caleu pevtralization of a weak acid, say Hi ja two steps, namely, tonization HCN > H" + ON; ae, ax ‘Neutralization H” + OH” > 1.0; AHP, =_ 57.1 kimole The complete reaction is obtained by adding the abov steps. Thus 2 HCN+ OH” > H,0 + CN~ ai? =- 12ei/mole Obviously, AH? = AH®, + ane, AHP, = OH? ~ BH = [-12- 57.19) = 45.1 tSimole +» Greater the enthalpy of ionization of any weak acid or weak base, weaker will be the acid or base. lated as follows. The ICN, may be represented ENTHALPY OF TRANSITION Entlpy of transition is the enthalpy change when one mole of one allotropic form changes to another. For example: C(graphite) -> C(diamond); AH, 90k mort Cigraphite) + O,(g) > CO,(g); AH,2 = 393.51 kd mot! (diamond) + 0,(¢) > CO,(g); AH, =~395.41 kd mot! ‘Subtracting, we have, C(graphite) > C(diamond) (AH,,°= 1.90 k mol [ENTHALPY OF FORMATION OF IONS ‘The enthalpy change when one mole of hydrated ions is obtained from element in its standard state as (A) CL, (g) + aq > Cl (aq); AH,? = AH (Clr, aq) By convention, the standard enthlpy of formation of ‘H(aq) is taken to be zero. Chemical Thermodynamics and Energetics We have seen that H° (aq) + OH (aq) > H,0(0} AH? = ~ 57.1 kd mol! For this reaction, AH,? = 4H? (H,0.) ~ {AH (H*, aq) + AH? (OH aq) Hence, at 25°C, we get AH,? (H*, aq) + AH? (OH, 8a) = aH (H,0, )- 4H? 50 AH? (OHaq) = (- 286.1 ~ (~57.1)} KJ mol 229,00 kJ mot"? Enthalpy of Phase Change (a) The enthalpy change that accompanies melting of one mole of a solid substance in standard state is called standard enthalpy of fusion or molar enthalpy of fusion, By, H°- H,0(8) — H,0(); 4,,,H?= 6.00 1 mot! (®) Amount of heat required to vaporize one mole of a liquid at constant temperature and under standard pressure (Ibat) is called its standard enthalpy of vaporization or molar enthalpy cof vaporization, AgH?. H,0() > H,0(@); A,,,H?=+ 40.79 kJ mol"? (© Standard enthalpy of sublimation, 4,,,H° is the change in enthalpy when one mole of a solid substance subi constant temperature and under standard pressure (Iba). Sublimation is direct conversion of a solid into its vapour. Solid CO, or ‘dry ice? sublimes at 195K with A,yH® = 25.2 kJ mol; naphthalene sublimes slowly and for this AggH? =73.0 KI mol". Enthalpy of Hydrogenation ‘The enthalpy change when one mole of given compound is hydrogenated. e.g. C,H,(g) + 2H,(¢) > CH,(e); AHS 30 keal/mol Resonance Energy It can be calculated as difference between enthalpy of formation (or combustion) (or hydrogenation) of actual molecule (ie., resonance hybrid) & most stable resonating structure. AF sesonance ~ AH sferperimenta)~ Ay (catcalatea) ane cocstion cess) Enthalpy of Atomisation ‘The enthalpy charge when one mole of given compound is converted into gaseous atoms. €.8., Na(s) > Na(g) CH(e) > Cig) + 4H(@) 105MC Ca Dt Example 18: The enthalpies of solution of anhydrous CuSO, and hydrated CuSO, 5H,O are ~66.5 and 11.7 kd mol" respectively. Calculate the enthalpy of hydration of Cuso, to CuSO,.511,0. Sol. Given that @ CuSOA(s) + aqueous —+ CuSO, (aqueous); AH, = ~ 66.5 ki/mol (i) CuSO,,5H,0(5) + aqueous —> CuSO, aqueous); AH, = 11.7 ki/mol CuSO,(s) + 5H,0() —> CuS0,.5H,0(8): SH=? SH = AH, - AH, =~66.5 —11.7=- 78.20 Example 19: 150 ml of 0.5 Nnitric acid solution at 25.35°C ‘was mixed with 150 ml of 0.5 N sodium hydroxide solution at the same temperature. The final temperature was recorded to be 28.77°C. Calculate the-heat of neutralisation of nitric acid with sodium hydroxide, Sol, Total mass of solution = 150+ 150 = 300 gm. Q= 300 x (28.77 ~ 25,35) = 300 x 3.42 = 1026 cal Q 1 Heat of neutralisation = <2. x1000x—+- sation = 750 os 1026 = 128, 1000%: cal. feo 9g 71368 keal Since, the enthalpy of neutralisation is always —ve, 80, heat of neutralisation =~ 13.68 keal. Example 20: Calculate the enthalpy change when one mole of HCI(g) is dissolved in a very large amount of water at 25°C. The change in state is: HCI(g) + aq H"(aq) + CI (aa) A,H°(HCL, g) =~ 92 kI mot? and A,H° (CT-, ag) =~ 167 kJ mot Sol. For the reaction, HC\g) + ag > H"(aq) + CI"(ea) we have AH? = AH*(CI”, aq) — 4,H°(HCL, g) AH? = [-167 - (-92)] kJ mol"! =—75 kJ mol! Example 21: Calculate AH? for the reaction, Ag*(aq) + CI"(aq) > ABC) at 25°C, Given AH? (Ag’, aq) = 105 KI mot, A? (CE aq) =-167 KF mot" and 4,H°(AgCI, s)=— 127 kd mot! Sol. For the reaction Ag*(aq) + CI (eq) + AgCIG) wwe have AH? =A,H? (AgCI, s)— AH°(Ag*, aq) —A,H(CT", a) = [127-105 - 167 J} I mot ~65 kJ molt Given: Sol. Rea 19. 20. 21. 106 Example 22: Ent 57.1 kS/mnol and b} ceathalpy of dissociation of 2. hay of neutralization of HClby Nag a,OH is51-1 mol. Calas tNH,OH. N Given that ’ H"(aq) + NH,OH(2q) > NH,"(@a) + H,0(0) ait =-51.1 Kimole : ‘We may consider neutralization in two steps, (9 Tonization NH,OH(aq) > NH, (a) + OF" (a9) aH, =? (i) Neutralization H‘(eq) + OH (aq) > 0) AH, =~ 57.1 kiimole ‘Thus, AH = 4H, + 4H, Therefore, Alf, = AH—AH, =~ 51.1 mol +57.1 Ki nghs cee 10mLof each 1 MHCland IMH9SO4 are neutralize, by 1 M NaOH solution that liberate the heat of 2 & b ki/mol respectively. What is relation betweea aand b? @ a=b @ a=» (©) 2a=b (@ a=4b ‘The standard enthalpy of neutralization of KOH with HCN and HC in dilute solution is ~2480 cal.mot™ ani 13.68 kcalmot™ respectively. Find the enthalpy of dissociation of HCN at the same temperature, (@) 52keal () 1.2 keal (©) 15 keal @ 224 keal ‘The neutralisation of a strong acid by a strong base liberates an amount of energy per mole of H”that- (@) Depends upon which acid and base are involved, () Depends upon the temperature at which the reaction takes place. (©) Depends upon which catalyst is used. @ Isalways the same Find heat of reaction for the given acid-base reaction, HA +NaOH —> NaA + Hg0 ; AH =~ 4.7 kcal/mol the heat of dissociation of HA: (@) 9 kcal/mol (®) 18.4 keal/mot (© +184 keal/mol @ -9 kcal/molond encbalDy is the average of enthalpies required to soe Pete said bond presen in diferent gaseous compounds soci roms oF radicals in the gaseous state. While boos inte Nation enthalpy is the enthalpy required to dissociate soem pond of some specific compound.for example the veo 0 wy of dissociation of the O-H bond depends on the nature at ‘ies from which the H: i lecular SpEcics atom is being separat ee ample, in the water molecule. Mahila FO 7 HE) +OH@) —AH,S= 501.87 I mot! sowever, to break the O-H bond in the hydroxyl radical required a different quantity of heat : Hl@) -> OC) + (2) AH) = 423.38 kg mot? ‘The bond enthalpy, AH, is defined as the average of these ‘wo values, that is: 501.87kImol” + 423.38kImot" 2 = 462.625 kJ mot! In the case of diatomic molecules, such as H,, the bond enthalpy and bond dissociation enthalpy are Tieden Thus, the bond enthalpy given for any particular pair of atoms is the average value of the dissociation enthalp ies of the bond for a number of molecules in which the pair of atoms appears. » Estimation of Enthalpy ofa reaction frombond Enthalpies: Let the enthalpy change for the gaseous reaction CH) + HCI@) > CH,C\(g) be required from the bond enthalpy data, This may be calculated as follows : ‘Enthalpy required to break reactants into gaseous atoms _{Enthalpy required to break products into gaseous atoms = [44H ¢ tA o.ct Hy oil + 58H yA, AH gi] = QHleag + AH yc) ~ (Oe y+ Ae c+ beg) Migs Glue icc \: The standard molar enthalpies of formation of cyclohexane (f) and benzene (f) at 25°C are-156 and + 49 ki mol" respectively. The standard enthalpy of hydrogenation of cyclohexene (f) at 25° is~119 kJ mol. Use these data to «stimate the magnitude of the resonance energy of benzene. Sol, Enthalpy of hydrogenation of 3 carbon-carbon double bonds Chemical Thermodynamics and Energetics 4#,(C)-s%. ©) 1-156 - (+49) kJ = -205 ki/mol Given that, CQ) +H, —> C48 ‘Theoretical enthalpy of bydrégenation of 3 double bonds in benzene ring 3x (119) kJ =- 357 kJ/mol . resonance energy of benzene — 357 — (205) kI = -152 kJ. mole Example 24: Using the bond enthalpy data given below, calculate the enthalpy change for the reaction CH) + (8) > CH.) Data: Bond enthalpy 336 kJ mol 606 kJ mol! 410 kJ mol! 431 kJ molt Sol. Diagrammatically, we represent the given reaction as follows: A, H > ae errant ee HH AH gion DB B)seuet~ DBE podot BE. (C-H)] + B.E. (C=C) + B.E(H-H)] -[6BE.(C-H)+BE(C-C] [4 * 410 + 606 + 431] — [6 x 410 + 336] =-119 ki/mal. ‘Example 25: Using the bond enthalpy data given below, estimate the enthalpy of formation of gascous isoprene CH, = C-CH=CH, hn 19 kJ/mol Data: Bond enthalpy of C—H bond = 413.38 kJ mol Bond enthalpy of C - C bond = 347.69 kJ mol Bond enthalpy of C = C bond ~ 615.05 kJ mot“! Enthalpy of sublimation of carbon (graphite) = 718.39 I mot Enthalpy of dissociation of H(g) = 435.97 KI molt Sol. sc(graphite) +4 14(@) “8. CH= G—cuecHy, cH, AH =(S*718.39+4%435,97-2%615.05-2*347.69 8x 413.38) mor = 103.31 KJ mol" 107Coit aeaieeea . Estimate the average S-F bond enthalpy in SF. The values of standard enthalpy of formation of SI4(t), S(g) and F(g) are: -1100, 274 and 80 ki mol! respectively, (@) ~746 ks mot! (0) 309 kd mol! (©) 618k molt (d) 154.5 ki mol Calculate the enthalpy change (AFI) ofthe following seection: 2CaHla(e) + 503(4) —> 4COp(e) + 211;0(6) given average bond enthalpies of various bonds, ic, C-H, C=C, O= 0, C= 0, 0-H as 414, 814, 499, 724 and {640 kd mol respectively. @ 2573 ks mol! (b) +2573 kd mot! (©) 1286.5 KS mol! (a) 1087 KS mol! 25. Bond energies of N= N; HH and NH bonds are 945, 463 & 391 KJ mot! respectively, the enthalpy change of the following reaction is Nae) + 3Ha(g) > ANTI (e) (a) +93 ki/mol (6) -93 kilo! (©) ~46.5 ki/mol (@ +46 ki/mot 26, Enthalpy change ofthe reaction 21(g) -> H1,() is ~ 104 Keal The 1 ~ H bond dissociation energy is: (@ 104 kcal/mol (b) 104 keal/mol (0) ~52 kcal/mol (@ 452 keal/mol 27, For the equations C(diamond) + 2H,(g) + CH,(g); AH, Clg) + 4H(g) > CHHy(e); AH, Predict whether (@ AH, = 4H, () AH, > 4H, (© AH, < aH, (@) At, = AH, +A, (©) + Ag HC) Importance of Second Law What is the driving force for a process which takes system from one state to other on its own? Why such processes (ealled spontaneous process) take place at all? Answers to these questions are given by second law. (SPONTANEOUS PROCESS | A spontaneous process is the one witich takes place on its own & can drive some other process as well. However, in some cases, initiation may be required. Example: () Mixing of two gases. (it) Cooling of a hot object by transferring heat to surrounding. (ii) Water flowing down the bill 108 » (iv) Rusting of iron, ; (») Burning of coal, coke, hydrocarbons, (x) Voleanic eruptions. The synonyms of spontaneous processes are BALUPAL Proceyy, and irreversible processes. Iisa common observation that natural processes occur With jg rate, All spontaneous processes take place duc to a finite divin force (which can be temperature difference, height differen, potential eneruy difference, etc). Also the change brought shay by aspontancous process can notbe restored without making emp effort (which brings about permanent change in surrounding) Hence it is quite natural to call these processes as irreversite processes. The term ‘éisorder” is related to randomness. Any macroscopic property ofasystem isan average of large nurmber of microscopis forces which are random in nature. Greater the randomess associated with microscopic forces, greater is the uncertainty about exact microscopic description of a macroscopic state and greater will be the disorder associated with the macroscopis state As arule: (Greater the number of molecules in which a given energy | is distributed, greater isthe disorder. (i) Greater the spread of given number of molecules with given energy in space, greater will be the disorder. For any spontaneous process (irreversible process): AS vive = AS yen t ASyarouning” 0 During a reversible process: as o ‘Thus during ireversible process, entropy of universe increases while during reversible process, entropy of universe remeis ‘constant Entropy Entropy is a measure of disorder. The entropy is a state function and a basic quantity directly defined by second law. ‘There are three types of entropy changes: © AS. ? Entropy change of system (4 A8ssrouning! Entropy change of surrounding (8) AS BS caroundig ~ ASwrivese™ AS t= Sie ‘The change in entropy of a system is given by: dg, dS = 1 where; dij = heat exchanged by system ia a Vey small step (reversibly). @ JEE Dropper Module-1 CHEMISTRY(iv) Reversible adiabatic process Ty orn Cin 7 snysical Significance of Quantity “= 24S" ae, aie _r=abolute temperature at which heat is absorbed. (@) Dating reversible adiabatic expansion: suppose, Similar quantity of heat is absorbed at two different 1, V) temperatures T, and T, (TT, >> T,). When heat is supplied = Sign of two terms are opposite and magnitudes are samme at high temperature, the % increase in kinetic energy is bss compared to heat supplicd at low temperature, Hevce, isorder will increase by greater value, when heat is J oar in| supplied at lower temperature, i hens bent nCy.q In: v ‘because for reversible adiabatic process ~ = tive and —ive term cancel out each other and hence, as=0 ; ‘Thus, decrease in entropy during expansion duc to system decrease in temperature is exactly cancelled out by oo a acne jnorease in entropy due to increase in volume of systema S yu 0 in reversible adiabatic expansion. die (&) During reversible adiabatic compression: Pests Peete 1,>T, and V, ico pec ntl | t ar’. Thus, increase in entropy due to increase in temperature fr yor is compensated by decrease in entropy due to decrease in ‘volume of system in reversible adiabatic compression. 'Sgumn = 8Cyq 2 saxuo(%) Hence. AS =0 for reversible adiabatic compression. y vy, (¥) Irreversible adiabatic process % B Since process is ireversible, AS yy > 0. Cg ne aR In FBS pg 0 ts ‘The physical interpretation is - (@) During irreversible adiabatic compression, large quantity Ideal Gas Processes ‘of heat is produced while decrease is volume is less. (0 For isothermal change ‘Thus increase in entropy due to rise in temperature exceeds the decrease in entropy due to decrease in volume. Hence net entropy change is positive, y, (&) During irreversible adibatic expansion, due to sudden A challenged dutiag expansion. Hence system do less ‘This formula is applicable to all ideal gas process, (Ce T= constant) (0 Yorimchosic change work-resulting in lesser decrease in temperature. day _ tC, dT pat. ‘The increase in volume of system is relatively larger. ase fe = [Pa anc. | Thus increase in entropy due to increase in volume exceeds 1 65 day AC yy AD) decrease in entropy due to decrease in temperature. The net change in entropy is positive in both processes 3 881g to Sup, = 0 (¥ no heat is exchanged with surrounding) and T AS > 0. CO) abate amass (vi) Free expansion of an ideal gas against vacuum Froc expansion of an ideal gas is an example of irreversible adiabatic as wel as irreversible isothermal process, During free expansion, the P,. = 0. Hence, the ideal gas is not challenged at all during expansion. The kinetic energy of ‘deal gas remains constant. Hence, no temperature difference + is created during expansion between system and surrounding, hemical Thermodynamies and Energetics mePvgT © AT=0, the heat absorbed during the proses = 0 Since V,>V, and T= constant, AS,,, The fiee expansion is an example’ Ten eras = 0, stil S.ssem 70: This is reasonable, because: AS, system = jae T This; example clearly shows that even if g,.,4 between two states is zero, this does not means that ja between two states is zero, This outlines the importance of reversible path and 4,,, in calculation of entropy of system. Entropy Calcul Tees Isothermal reversible 7 AR in( 22 v Isothermal ineversible 2a (Vs-¥) Da y Adiabatic reversible AS,,=0 BSsur= | ‘Adiabatic imeversible Buna Tsobarie reversible om 8," 2G, \ Isochoris reversible TL ms AS yp Cy 9 | Entropy Change of Solids and Liquids Upon | at, Heating ar Tanai | iT Soo =O as- [Se - [et nln (= sesh oF st | " , a rhs AS, at boiling point = <== liquid NAS pan 8 oiling point = p= For molar change in entropy, m= M(g/mole); where M = molar Atha ce Suing at melting point . : a au, Sie 8 S0limation point = Si SF einen 8S soecpiemsiiiction Rn sible Phase Transition: bi ae Entropy Calculation for Solid or Liquid Systems -versible phase i isobaric, Reversible phase transition are always isothermal & isobaric. (@) ‘Cur bloc kept in open atmosphere 1, = = ms In MSorsem ims tne ae @ JEE Dropper Module-1 CHEMISTRYSag SSeS ‘ ean m m but dar = aye =~ M15 (Ty ~7,) = ms (T, ~T;) AS, Sorc + Sup ASciyce=me én Be 4 GB), y T, it (8) Two copper block kept in contact in thermostat ‘Two blocks are of same mass sunny 3 cay ST T, ‘Thermostat AS... 0 (since no heat is lost to surrounding) AS yer = AS, + AS System will reach a common temperature (T,) and T>1>2, oe} + Spontaneity ofa process in terms of total entropy change If, AS = +ve => spontaneous process TEAS. If, AS.) 0. = process is at equilibrium -ve => non spontaneous process Chemicat Thermodynamics and Energetics Pi (CRI en Cheeta he Example 26: What are the signs of AS for the system and for the surrounding in each of the following processes? (a) Water boils ina tea kettle on a hot stove. (B) Ice in an ice cube tray left on a table melts. (© Acup of coffee is reheated in a microwave oven. Sol. (a) AS.yg is positive ; ASzur is negative. (0) AS sya is positive, ASsur is negative. (©) ASsye is positive, ASwur is negative, Example 27: State the thermodynamic condition of spontaneous occurance of a process? Sol. AG= (2) ve oF AS py: > 0 Example 28: The entropy of vaporization of benzene is 853K"! mol"!. When 117 g benzene vaporizes at it’s normal boiling point, calculate the entropy change of surrounding. Sol. 15 * 85 J/K Example 29: Three moles of an ideal gas is expanded isothermally from 2L to 10L, at 27°C. Calculate AS,,, and AS... nd AS, ifthe process is performed. (O Reversibly (Gi) leversibly, against a constant extemal pressure of | atm, (itl) As free expansion. Sol.) AS ppg = 0, BS gure “AS, and AS,,,= oof oa v on = Rin 2 40.14 (ip) AS,,,= 40.14 7K as__- Pa T =-2.7K and AS yi, = AS 5 + AS 37.44 JK Gi) 88,,=40.14 51K et) and AS yyy = ASyye + AS p= 40.14 JK ee = © bath out ae 28. One mole of an ideal diatomic gas (C, = 5 cal) was transformed from initial 25°C and I Lto the state when temperature is 100°C and volume 10 L. The entropy change of the process can be expressed as: (R=2 calories/molK) 298 373 @ 3m] #210 B) SInS = +210 313 1 323 1 rin B20 10 sin Bey 1 © Tm p77 GG SB Det? TG or29. Calculate the entropy change in surroundings when 1.00 mol of 1,0 (€) is formed under standard conditions at 298 K, Given AH*=~286 kJ mol", (@) 989.731" (b) ~959.73 IK (©) 766.75 3K (@ 166,15 1K" 8) isexpanded Tone mole of an ideal gas, (Cun 7 ‘sothermally at 300 K until e's volume is tripled, then change in entropy of gas is: (@) zero Rin3 (6) Infinity @ Rin3 LAW OF THERMODYNAMICS) “At absolute zero, the entropy of a perfectly crytalline substance is zero”, which means that at absolute zero, every crysfalline solid is ina state of perfect order and its entropy should be zero, By virtue of the-third law, the absolute value of entropy (unlike absolute value of enthalpy) for any pure substance can be calculated at room temperature, = fae Since Syqy=0 ‘The variation of entropy of a substance with temperature is given by graph: At L, entropy of substance is zero. + from 1-2; The temperature of solid increases upon heating - (i) Temp. Change in entropy of a pure substance with temperature at constant pressure. ‘® from 2-3; The temperature remains constant during phase transition 85-8," 8S ag i) + from 3-4; The temperature of liquid increases Crea dT ao He = 8,-8,- [a Cit) 12 '¢ from 4-5; Reversible vaporisation takes place at constany temperature: tiv) 6) -G,-8) absolute entropy at 6= AGy sigs | AH % a car eo ae J Standard Absolute Molar Entropy It is the entropy of one mole of substance at standard temperature at 1 bat tis calculated assuming that substance is heated isobarically ang reversibly at 1 bar from 0 K to standard temperature. Comparing Absolute Entropies of Substance (i) The absolute entropies of substance follow the order, S(g) >> S() > Sis) (ii) Entropy increases when solid and liquid is dissolved into solvent, eg, CHOHO $°= 127 JK-mole CHOH(oq) $° = 1323 YK-mole NaCls) S*= 72.4. /K-mole NaClaq.) $°=115.4.1/K-mole (lid) The entropy of dissolved gas is less than pure gas. eg. HCWg) — $*= 186.7 /K-mole HClaq) $°= 55.2 J/K-mole (iv) Entropy rises with increasing molar mass, (if other factors are similar). eg. F@) S°=203 /K-mole Clie) $°=223 /K-mole Br(g) $°=245 1/K-mole (0) Entropy is lower in covalently bonded solids, with strong directional bonds, than in solids with partial metallic character. eg. C(diamond) $= 2.44 /K-mole (graphite) $°= 5.69 1K-mole Sn(gray) $°= 44.8 /K-mole Sn(white) S°=51.5 /K-mole (vi) Entropy increases with increasing softness and with ‘weakness of bonds between atoms. €g C(diamond) Be(s) SiO(s) POs) Hat) 244 954 418 649 TTA diamond hardmetal quartz softmetal liquid @ JEE Dropper Module-1 CHEMISTRY(oi#) Entropy increases with chemical complexity. NaCl MgCl,” AICI, 4 895 167 For CuSO,.nH,0 n=O, n=l, n=3, nes S°=113, 150 225, 305 Entropy Change (AS) of a Chemical Reaction ‘The change in entropy when reactants tum into products according, to a balanced chemical reaction with specified physical ato cach reactant and product is called entropy change of sco Consider a reaction: aA(m) + bB(n) —* + eC(o) + dD) where m,n, 0, p are physical states at temperature T and pressure P, AS, = ZS (products) ~ F§ (reactants) AS=6S, + dS, ~a8, bs, Spo Spy Scand Sp are absolute molar entropies at temperature: ‘Tand pressure P (from third law) So, 4, is evaluated from table of data of third law entropies of various substances, Example 30: Predict which of the following reaction(s) have a positive entropy change? 1. Ba (aq) +S02- (aq)—> BaS0,s) I. CaCO,(s) —> Ca0 () + CO,(g) IL. 280,(¢)—> 280, (g) + 0,(¢) (and 11) 4n, value for (I= 0) for (11, ‘An, is + ve for HI oD) CE cece + Identify the correct statement rogar process: 1g spontancous (@) For a spontaneous process in an isolated system, the change in entropy is positive, (b) Endothermic processes are never spontaneous, (©) Exothermic processes are always spontaneous, (d) Lowering of energy in the reaction process is the only criterion for spontaneity. 32. AS for the reaction ; MgCO,(s) -» MgO(s) + CO,(g) will be: (@ 0 (&) -ve © +e @o Chemical Thermodynamics and Energetics 33. Change in entropy is negative for: (@) Bromine (2) -» Bromine (g) @) CG)+H,0(@) > COW) + He) © Nie, 10 atm. 298 K) > Ny (g, 1 atm. 298K) (@) Fe(at 400 K) — Fe (at 300 K) |. For which reaction from the following. AS will be maximum? (@) Cals) + 40,(¢) -> Ca0(s) @ CaCO,s) + Ca0(s) + CO,(e) © CG) + 04g) > CO,(@) @ Nye) + Og) > 2NO(®) For the process, CO,(s) > CO,(g): (@) Both AF and AS are +ve. () AW is—ve and AS is +ve. (©) AW is +ve and AS is-ve. (@ Both AH and AS are ve. Gibb's free energy “G' is defined as G = H-TS. itis a state function and is an extensive property. Gibb’s free energy provide a very useful criteria for spontanity of a process taking place at constant temperature and pressure (isobaric, isothermal process) ‘The entropy of universe is also a very useful eriteria of spontanity, but itis based on properties of system as well as surrounding. ‘The Gibb’s free energy provides criteria for spontaneity based only on the properties of system. AG = AH-a(TS); AG = AH ~ TAS (at constant temperature) AG, aNd ASyriverse Decrease in Gibb's free energy at constant temperature and Pressure i related 19 AS (ol entropy change of system and surrounding). AG = TAs, mT iCAG <0 = spontaneous process. iCAG > 0 > non-spontancous process if AG = 0 => reversible process. Calculate AG for Various Processes @ Ideal gas subjected to isothermal compression or ‘expansion: For isothermal change: AG= AH-Tas For ideal gas, AH = nC,,,AT = 0 (As AT = 0, for isothermal change) ual) Atco sts-ann(%) erie) 13iy (it y, AG -nkT In{ Ye (i) Hence, during isothermal expansion Gibb's free energy decreases while during isothermal compression Gibbs function increases. Isothermal and isobaric phase transitions: At transition temperature, the stability (or Gibb's free energy) of two phases are equal. Hence, there is no driving. force for conversion of one phase into other. This means phase transitions are examples of reversible processes at transition temperature. Now, for reversible isothermal and isobaric change, AG ~ 0 = AG = 0, for phase transitions at transition temperature. ‘Thus, AG 0 at boiling point. ‘Also, AG,,, = 0 at melting point: AH aion ™ Tien Staion BH Thaion™ AS, 4,G for a chemical reaction, Consider a reaction : aA +bB > eC+ dD ‘The change in Gibbs free energy for @ chemical reaction is change in AG when reactants react according to @ given balanced chemical reaction with specified physical state of ‘each reactant and product at given temperature and pressure. AG = 0G, + dGy~aG,— dG, : Where Gq, Gy, Ge and Gy are molar Gibb's free energy of A,B, C and D respectively at given T and P. also, G, =H, -TS, G, =Hy-TS, Ge =H, -TS. G, =H, -TS, Substituting Gi) in i) A,G= (CH, + dH, —aH,—bH,)~TUeS, + 4S, ~ aS. Sy) =ve | tye | Always-ve Reaction is __ spontaneous Hye [ove | Always +ve ‘Reaction non- spontaneous ve | +ve | Atlow temperature, | Non-spontancous AG=+ve ‘Spontaneous Tye | —ve | Atlow temperature. | Spontaneous AG=-ve Athigh temperature, | Non spontaneous AG=+ve_ 14 (is) Gibb’s energy functions of pure substances: Consider a pure substance having « Gibb’s energy function as follows: GeH-TS=U+PV-1S Let, the pressure and. temperature are varied py infinivesimally small value: dG = dU + PAV + VéP -TaS ~ SAT ‘As, dU = dg ~ PAV and TAS = dq [Assume only PY- voy, and reversible provess.] aG = var - Sat (a) If pressure is varied keeping temperature constane. (dG c= var = ($2) =v “ ®) “The physical significance of above relation is when pressure over substance is increased, it's Gibpy function increases & the increase is proportional tg molar volume. Since molar volume of gas, liquid ang solid are in order, as follows: Von Vitesa” Virus Hence, Gibb’s function of gases increases most rapidly on increasing pressure. “That's why, gas phase becomes unstable at high pressure Sus Gigi P Variation of Gibb's function of pure substance with pressure at constant ie Store som sit (32) =-s Since entropy of pure substances are always positive, the slope of G vs T curve is negative. Also since, Spo? Sigua” Sona = the slope is more negative for gas ‘Thus, on increasing temperature, the Gibb's function of pure substances decreases, but this decrement is ‘maximum for gaseous phase. Thus, gas phase acquire stability on increasing temperature. ‘Variation of Gibb's function of pure substances with temperature at constant pressure. @ EE Dropper Module-1 CHEMISTRplication of Gibb’s Energy (as Measure of ie py Work) wears : dG = dULTS) = dl tas sar ait dU PuV + vap BU PAV Way (mast HOH-PY Work done by system) ora general easton, MAEM SA PCF gD, js given by- fo AG? #2.303 RT og Jinere AG = GibD's Free energy change Yor Standard Gibb's Pree 1 Q=K, AG 2.303 RT low gK nergy change, Q = reaction quotient ° iacesiibe ae? Nee ciel Example 31: 3 moles of N, (8) originally at 1 atm pressu sue mixed isotherm; Pressure ly with 5 moles of 11,(g) also at 1 atm pressure to yicld a mixture whose total pressure is 1 tne Assuming ideal behaviour, calculate entropy of mixing. Sol. Total pressure of mixtur T atm ‘inal pressure of N, = (1) = 0.375 atm Final pr No gpg = 0.375 at Final pressure of H, = | ~ 0,375 = 0.625 atm. For N;, entropy change BR 2 2.303 «3 x x log Ba 3x 8.314 x log | &) Sy, =—nR = 28.03 VK For H,, entropy change by, =a tal 58.314 2.30% fp MS veaa me Toil eno change die to mining AS, + AS, arin Example 32: Calculate free energy change for the esterification reaction, CH,COOH + C,1,0H <— CH,COOC,H, + 11,0. ‘The equilibrium constant for the reaction at 25°C: is Sol AG? =~2.303 RT log K = ~ 2.303 x 8.314 298 log 4 = (2.303 « 8.314 x 298 x 0.6020) =~ 3434.92 J/mol Chemical Thermodynamics and Energetics -xample 33: Calculate AG, for the following process: ( 11,0 (L, 100°C 1 atm) —> H,0 (@, 100°C, 1 atm) to 140 U, 100%, 1 sim) —> HO (. 100°C, 05 atm) H. ) AG=0(Ea (i) 11,0 (1, 100°C, 1 atm) —+ H,0(8, 100°C, 1 atm)—2-+ H,0 (g, 100°C, 0.5 atm) jum condition) AG, = AG=AG, +G, =-2149 5 Example 34: The correct relationship between free enerey change in a reaction and the corresponding equilibrium constant K, is Sol. -AG?= RT Ink Example 35: The enthalpy of vaporization of a liquid is 30 kJ mo and entropy of vaporization is 75 mol”. The boiling point of the liquid at 1 atm is: (@) 250K () 400K (©) 450K @ 600K. Example 3 Sol. The system becomes more disordered Example 37: For a perfectly crystalline solid, (Cpa, = aT, where a is a constant. If (Cp), at 10K is 0.375 1/K-mol, then find the value of molar entropy at 20K (in J/K-mol). 3 Sol. (Cj)q =a». 0375 =a lop 2. a= S10 80000 _ 80003, 19-3 J/K -mol iConcepiyApplication ie 36. Which of the following pairs of a chemical reaction is certain to result in a spontaneous reaction? (@) Endothermic and decreasing disorder () Exothermic and increasing disorder (©) Endothermie and increasing disorder (@) Bxothermic and decreasing disorder 11537. Fora particular reversibl revenible reaction at temperature T, AH and AS were found to be both ve. IfT, is the femperature at equilibrium, then reaction would be spontaneous when: @ T=1, © T>T, ® tT @ Tis $ times T . For a reaction at 25°C, enthalpy change (AH) and entropy change (AS) are -11.7 10 J mol and 105 J mot K+ respectively. The reaction is; (@ Spontaneous @ Non spontancous © Atequilibrium @ Can't say anything 139, Identify the corrects tement forchange of Gibbs ong ene onal constant Fempeatste and pressing, (@) WAG yen ™ Ot is spontaneous, (Gp race =O. the system has atained equity, eaGe ey = the system is still moving gy partietiar direction. : (a) TEAG yaya <0 the process is non spontaneoys Inatmevomieproesttoking pac scOston Tyg, sa ireysenich only pressure-volume Work isha Fa gen Gibbs fee oney (@O) andchan $eeSeropy (4S) satisty the etna Go) See 0- Or, ©) Wye= 0. Dee (ESE =. EDee <0 GN E> O.EDe

2HI(g) Sol. AG? = EG; (products) ~ G; (reactants) =2x(13)-0+0) 6-0=26 ki/mol 118 12. Calculate the value of K, at 25°C for an equilibrium reaction, if AG? = - 20 ki/mole, : Sol, AGp= -2.303 RT log K, 20 x 1000 =~ 2.303 x 8.314 298 log K, ee 108K, ~ 3303%8.314%298 K, = antilog (3.505) = 2.91 10? 13. Work done in expansion of an ideal gas from 4 litre to 6 litre against a constant external pressure of 2.1 atm was used to heat up 1 mole of water at 295 K. If specific heat of water is 4.2 J g-! K-!, what is the final temperature of water? Sol. W=-2.1 [6-4] -21¥2 =4.2 atm * fit, == 4.2 * 101.325 ‘This work is used to heat up the water = 3.505 Specific heat of H,0 = 4.2 ae Heat required for increasing temperature by 1°C of 1 mole= 42x 18 =75.63 4.2 x 101.325 = 75.6 (T-293] 5.63=T-293 T= 298.63 K 14, Following graph shows a single stage expansion process, then workdone by the system is, (atm) 2 4 va) (a) ~ 9104 (6) ~ 202.65 (¢) ~5063 (a) ~ 101.3 Sol, W=~P,. (Vp~V,) =~ 1 %2* 101.325 J =-202.6 3 — oH ‘Therefore, option (b) isthe correct answer. One mole of an ideal monoatomic gas expands isothermally against constant external pressure of 1 atm from initial volume of IL to a state where its final pressure becomes equal to external pressure, If initial temperature of gas is 300 K then total entropy change of system in the above process is: [R= 0.082 L atm mot! K+ = 8.3 J mol] @ ce Dropper Module-t CHEMISTRYSol. 16. Sol. 1. Sol. @o (2) Ren (2490) ® Rms) @ 32Ren 24.6) ‘Therefore, option () is the correct answer. Given the following data: Substance AH? (kJ/mol) $°(J/mol K) AG%(ky/mol) FeO(s) = 266.3 57.49 245.12 C (Graphite) 0 5.74 0 Fe(s) 0 27.28 0 core) 110.5 197.6 -13715 Determine at what temperature the following reaction is spontaneous ? FeO(s) +C (Graphite) —+ Fe(s) +CO(@) (@ 298K (6) 668K (©) 966K @ ac is tve, hence the reaction will never be spontaneous FeO (5) + C (graphite) —> Fe (6) +CO@) AH =0+[-1105]- (266.3) ==110.5-+ 2663 = + 155.8 ki/mole AS = 27.28 + 197.6 57.49 ~5.74= 161.65 Iimole AG = AH = TAS =0 = 155.8—T x 161.65 * 107 Tx 161.65 x 109= 155.8 => T=963.8K Therefore, option (c) isthe correct answer. What is the work done against the atmosphere when 25 grams of water vaporizes at 373 K against a constant extemal pressure of 1 atm? Assume that steam obeys perfect gas laws. Given that the molar enthalpy of vaporization is 9.72 kcal/mole, what is the change of internal energy in the above process? V,=0.025L w= 1(42.53 — 0.025) « 101.325 3 Chemical Thermodynamics and Energetics = 1025.4 cal AU=AH-Pav= (om 1o00%25) 1025.4 2474.6 cal 18. If AH? for Ag* (infinitely diluted), NO, (infinitely iluted),,CI (infinitely diluted) and AgCKs) are 105.579, 207.36, -167.159 and -127.068 ki/mol respectively. Calculate the enthalpy change for the reaction AgNO,(aq.) + HCl(aq.) —> AgCl(s) + HNO, (aq.) (@) 21.471 K/mol (®) 145.688 Ki/mol (©) -65.488 Ki/mol (a) None of these SOL. AH eyjog = [AH®, (AgC)) + AH®,(H) + AH? (NO,)] [AH (Ag')] + AHP, (NO, + ABE, (CI) + AFY, (2) 127.068 ~ {105.579 ~167.159] =~ 65.488 KI / mol. Therefore, option (c) isthe correct answer. 19. Calculate the heat of formation of benzene from the following data, asstiming no resonance. Bond energies: C-C= 83kcal, C= C= 140 keal, C-H = 99 keal/mol Heat of atomisation of C= 170.9 keal ‘Heat of atomisation of H = 52.1 keal Sol. We have to calculate AH for the reaction 6C(s) + 311,(@) —> CH de) B,B —> C and CA respectively corresponding to ‘Temperature-> (a) Isochoric, Isobaric, Isothermal (®) Isobaric, Isochoric, Isothermal (©) Isothermal, Isobaric, Isochoric (d) Isochoric, Isothermal, Isobaric 5. The P-T graph as given below was observed for a process on an ideal gas, which of the following statement is true? fl Fen aes % To (@) w=4ve, AH= 4ve 120 Work Calculation 6, A thermodynamic system goes from state (i) Py, V to 2P,,y (i P, V, to P, 2V, in two different processed. Then worg done in the two cases is: (@) Zero, Zero (®) Zero, -PV, (©) -PV,, Zero @ PV, PY, 7. The work done in ergs for the reversible expansion of ong mole of an ideal gas from a volume of 10 litres to 20 lites at 25°C, is (@ -2.303 x 298 * 0.082 log 2 (®) -298 x 107 x 8.31 x 2.3031 log 2 (©) -2.308 298 0.082 log 0.5 (@ 8.31 * 107 x 298 x 2.303 log 0.5 Heat, Internal Energy, First Law of Thermodynamics, Types of Process 8, In an isochorie process, the increase in internal energy is; (a) Equal to the heat absorbed. (0) Equal to the heat evolved. (©) Equal to the work done. (@ Equal to the sum of the heat absorbed and work done, 9. In an isothermal expansion of an ideal gas, select wrong statement: (@) There is no change in the temperature of the gas, (®) ‘There is no change inthe intemal energy of th (©) The work done by the gas is equal to the heat suppli to the gas, (d) The work done by the gas is equal to the change in its internal energy. 10. Asystem undergoes a process which absorbed 0.5 kd of heat and undergoes an expansion against external pressure of 1 atm, during the process change in its internal energy is 3001: Then, predict the change in volume (lit) @1 2 ©3 @4 11. When two moles of hydrogen atoms join together to forma mole of hydrogen molecules in a rigid vessel H@)+H (2) —> Hyg) then: (@) w<0 (©) AU=negative © Gysum™ Positive ©) Aeron = EEAivE @ JEE Dropper Module-1 CHEMISTRY