ot FT dd] Thermodynamics & ThermochemistryCONTENT JEE Syllabus Overview Terminology of Thermodynamics Types of Systems, Processes and their Types First Law of Thermodynamics . Work-Done in Reversible Isothermal Expansion Work-Done in Irreversible isothermal Expansion Adiabatic Expansion Solved Problems Subjective Objective Exercise - 4 Disorder, Entropy & Second Law of Thermodynamics Gibbs Energy & Spontaneity Solved Problems Subjective Objective Exercise - 2 Thermochemistry Laws of Thermochemistry Lattice Energy of an lonic Crystal Bond Energies Variation of Heat of Reaction with Temperature Bomb Calorimeter Solved Problems Subjective Objective Exercise - 3 Answers to Exercises Formulae and Concepts at a Glance Chapter practice problems Assignments Section-l Section-Il Answers to chapter practice problems Answers to Assignments a pol) Poa 1 2 aor wd 5 a) 40 48 50 1THERMODYNAMICS & THERMOCHEMISTRY Scale. [EES Sc First ti work and heat, pressure ~ volume v of thermodynamics; Internal ener ork; Enthalpy, Hess's law; Heat of reaction, Second law of thermodynamics; Mla Toyey any ed Thermodynamics deals with energy changes accompanying all types of physical and chemical processes. It helps to lay down the criteria for predicting feasibility or spontaneity of a process, including a chemical reaction, under a given set of conditions, It also helps us to determine the extent to which a process, including a chemical reaction, can proceed before attainment of equilibrium. Duele Ome cecal System: A system is defined as any specified portion of matter under study which is separated from the rest of the universe with a bounding surface. ‘Surroundings: The rest of the universe which might be in a position to exchange energy and matter with the system is called the surroundings. System + Surroundings = Universe Types of System (i) Isolated system: A system which can exchange neither energy nor matter with its surroundings is called an Isolated system. Closed system: A system which can exchange energy but not matter with its surroundings is called a closed system. (ii) Open system: A system which can exchange matter as well as energy with its surroundings is called a open system.2 Oe, Puree An extensive property of system is that which depends upon the gy. unt of the substance present in viscosity, refractive index, Extensive and intensive properties: amount of the substance present in the system like mass, volume a pie ‘An intensive property ofa system is that which is independent of the artont the system. For instance, temperature, pressure, density, concer : Surface tension and specific heat are the intensive properties. ye, temperature, inter State function and state variable: The fundamental properties pregsire, Your stale funtion or slate energy enthalpy, entropy etc. which define the state of a system are kné Variable Processes and their Types ‘The operation by which a system changes from one state to another is called a process. ‘The following types of processes are known: {sothermal process: A process is said to be isothermal ifthe temperature of the system remains constant during each stage of the process. Adiabatic process: A process is said to be adiabatic if no heat enters or leaves the system during any Step of the process. {sobarie process: A process is said to be isobaric ifthe pressure of the system remains constant during each step ofthe process, ‘sochoric process: A process is said to be isochorc ifthe volume ofthe system remains constant during each step of the process. Reversible and irreversible processes: A process is caried out infinitesimally slowly so that the driving force is only infinitesimally greater than the opposing force, i called a reversible process {ARY Process which does not take pace inthe above manne. i.e. & process which doss not take place infinitesimally slowly, is said to be an ireversible process, Process of energy ‘transformation is studied in terms of work, heat and internal eneray. All three Properties are interrelated in terms of first law of thermodynamics. Fi Definition of Terms: Work IY an object is displaced through a distance dx against a force F, then the amount of work done is defined as dW=F xdx When @ cylinder contains a gas with @ movable piston, the the work done by the gas or on the gas is Pressure — Volume work. pe Ea eto etn If a gas contained in a cylinder expands and the piston moves by a distance dx the work done by the gas (without any sign convention) is dW = F x dx, If the Pressure of the gas is P then dW = PxAxdx where A is the surface area of the piston. dW = P x dV where dV represents the change in volume of the cylinder. Now, according to work - energy theorem, the total work done by all forces on the piston is equal to the change in kinetic energy of the piston. Therefore the sum of ‘work done by the internal pressure and external pressure is equal to the change in kinetic energy of the piston. Since the piston started from rest and ended at rest the change in kinetic eneray is zero. Therefore, Pr: dV = Pox dV. x | dW = PadV = Ped Kol Sora Serveptiva Vika, Mew Delh-110016, Email: enquiy@megacosmcogniions com Website: www megacosmcognlions com Megacosm Cognions Pid.TT Heat I\'s defined as the energy that flows across the boundary of a system during @ change in its state by Aitue of @ difference in temperature between the system and its surroundings and flows from a point of higher to a point of lower temperature, Heat absorbed or evolved by solid or liquid, q= ms At Heat anne", ™=mass of substance, s = specific heat and At = temperature difference. ‘eat absorbed or evolved for phase transition, q = mL. here L = latent heat Internal Energy Every substance possesses a definite amount of energy which depends upon factors such as composition of the substance, temperature and pressure, This is called intrinsic or internal energy (E). E=E;+Ea+Ey+Es +E. Where t= Translational energy, Ex = Rotational energy, Ey = Vibrational energy, i Es = Bonding energy and E¢ = Electronic energy. nternal energy of a system is state function and its absolute value can not be calculated but its change bal be determined. When the system undergoes a change in its state, the internal energy change is y aE =E-€, Where E; = Internal energy in the initial state and €, = Internal eneray in the final state. |na chemical reaction, AE = Ep - Eq where Ep = Internal energy of products and Ex = Internal energy of reactants. Relationship between AE, Wand q. Let us consider an ideal gas in a cylinder fitted with a movable piston. Let the temperature of the system be T,, Pressure be P, and Volume be V;. Let us give q amount of heat to the system after which the system is insulated so that heal is not transferred by it. What happens now? The gas initially absorbs the heat and attains a higher temperature T>. Now the gas expands What will be the final temperature? Will it be T;, less than T,, or in between T, and 7;? To answer this, consider why the gas expands. It expands because when its temperature momentarily becomes 7, its pressure increases to Pz which is Pi VisTs higher than the initial Pressure P, (or the external ioe pressure). Since the internal pressure is more than the external pressure the gas will expand. It will expand till the internal pressure becomes equal to the external pressure. Therefore the initial pressure of the gas is ‘equal to its final pressure. Moreover the number of mole of the gas remained constant. It follows that since the final volume is more than the initial volume, the final temperature must be more than the initial temperature T; (because V/T is constant). But since the gas has done work it must have used some of the energy given to it in the form of heat. So the final temperature must be ess than T:. Therefore the final temperature of the gas is in between T; and To. This leads us to,dE=q+dW.. This does not include the signs. According to this equation the change in ternal energy is equal to the sum of work done and heat exchanged. This is the First law of thermodynamics. Tis states that ‘the heat supplied to a system is distributed between the work done and the change in internal energy’ which in other words is the law of conservation of energy. Sign Convention: The sign convention used in chemistry is the SI sign convention for thermodynamic quantities. According to this any process that increases the internal energy is considered positive and any process that TMegecosm Cogntions Pv. Ud, 57 aly Sra, Servoprva Vihar New Deh -110014, Emel: enquey@megacosmcagntions com i Websie ww megacosmeogniions comani AAT, idered positive and when th toa system it is consi . oiena by the system is negative while work done on the Vis +ve (meaning expansion) dW will be negative ang decreases it is negative. Therefore, when heat is heat is released by a system it is negative. Work system is positive. dW = - PdV. This is because if d when dV is negative (compression) dW will be positive. Therefore, dE = dq - PaV . essere (1) If dV=0, then dE = da, or change in internal energy is the he: Lets add d(PV) to both sides of the equation. zat exchanged at constant volume. == d (E+ PV) = dq- VdP The function E + PV is called H, the enthalpy function ie, H d 'f dP=0, then dH = q, or enthalpy change is the heat exchanged at constant pressure. Or dH = dé +d (Pv) = dH = dE +d (nRT) = dH =dE + nRdT The amount of heat required to raise the tem) 1 degree is called specific heat. Specific Heat perature of 1 gm of a substance by . = Heat capacity _ Heat absorbed Srecite heat = ase in gmk. Roe In lomperahire xmmase (ing) Heat capacity Moles Units of specific heat & molar heat capacity are JK g! and J K"' mol"* respectively. Now, heat supplied = Mass x specific heat x rise in temperature. ie.q=mxC,x AT son) ZThe heat capacity of a system, especially in a gaseous system determined al constant volume is different from that at constant pressure. At constant volume, q, = AE. So, heat capacity at constant volume per mole, gE cy =} soni »+(F), ww At constant pressure, gp = AH. ‘So, heat capacity at constant pressure per mole, gH) c, =|— so (Fl ae where Cr & Cy are molar heal capacities at constant pressure & constant volume respectively. The heat Capacity at constant pressure (Cr) is “generally” larger than that at constant volume (C.) because at Constant pressure, a part of heat added to the substance may be used in work of expanding whereas at Constant volume all the added heat produces a rise in temperature. The term “generally” has been used because substances generally expand with increase of temperature at constant pressure, but in exceptional cases, there may be a contraction, e.g. water between 1° & 4°C. Molar heat capacit ened Let us consider a non-insulated cylinder fitted with a weightless and frictionless piston containing an ideal gas. Let P be the pressure of the gas which equals external pressure, Po Poa=P An infinitesimal expansion in volume, dV, results from an infinitesimal decrease in the external pressure, say dP. Consequently, the pressure of the gas inside the cylinder falls to (Pzx -dP) ie. it equals again to the external pressure and the piston come to rest again. a ‘Megacosm Cognitons Pv. id. 57, Kalu Sarl, Sorvapriya Viner, New Delhi 110016, Emel: enquryémegacesmeogntions. com Website: war megacosmcagnifons comCs LET (Pox dP) lav \(P - dP) ‘The workdone by the gas in each step of expansion is given as AW = ~ (Poy — dP) dV = ~ Pay. dV = - PAV GP.dV is the product of two infinitesimal quantities and hence neglected. ZThe total amount of workdone during the isothermal reversible expansion of the gas from volume V; to Vz is given by dW= Pav Slav ( PV=nkT), faw= -aRT f bie Wrov = 2.303 nRT loge vt vill) At constant temperature, for given moles of gas PAV, = PAV, ev =~ 2.303 ART loos (x) For isothermal compression, work done on an ideal gas is same as isothermal expansion but with positive sign. Thus equation (vii) & (ix) is the maximum work done in an expansion, or the minimum work needed to effect a compression. This equation tells us that the work required to compress a gas from 10 atm to 100 atm is just the same as that required to compress a gas from 1 atm to 10 atm. Maer Irreversible isothermal expansions observed are (i) Free expansion (ii) Intermediate expansion. Since the external pressure is zero in free expansion, the work done is zero e.g. expansion of a gas in vacuum. The external pressure is less than gas pressure in the case of intermediate expansion. Thus, the workdone when volume changes from V; to Vo is Weer =~ Pes(V2- Vi) Since, Pox is less than the pressure of the gas, the work done during intermediate expansion is numerically less than that during reversible isothermal expansion in which Pas is almost equal to P. WSR iace eeu From first law of thermodynamics, AE = q+W Inan adiabatic expansion, q=0, :.AE=Wo ; The molar heat capacity at constant volume of an ideal gas is given by Del 110016, Emot : enauryBmegacosmcogniions.com Hegocovm Cogewons . = Websile : www.megacosmeognitions.comor dE = Cy, oT ®) and for finite changes, AE =C,x AT=W aati imavétsibie.) ‘The value of AT depends upon the nature of process (i.e. reversible or irrev Reversible Adiabatic Expansion P bathe eral ens ad AV be te inzeseinvaune, hen wade by re sys is Ww PAV AT is the fallin temperature, then CAT =—PaV For very small change in a reversible process and for one mole of a gas, Cat = -Pay (oy 2 process that takes the gas from a volume V; at a temperature T; to a new volume Vp at a temperature Ta, we have eft 7c, 8 We know that. Ce-Cy=R Dividing it by Cy gives & (xi) (ai) Ty" =v," or TV= constant PM (%) or PM =P,V} PV, (YW) or PV’ = constant The above integration assumes that Cy is a constant and not a function of T. We know, for an isothermal expansion, PV = constant, -Megacoim Cognitens| Ud, 57, Kal Sere, Soveprive 0016. Emat : engury@megacosmcogntions com ‘Webstle www megacosmeegntiLc ET On plots of P versus V, curves for reversible adiabatic process are steeper than those for isothermal Process as given below. 2 10 bar, °C) 10 PRESSURE, bar \\\ IsoTHERMaL| 2 t bar, t= 19f¢) (ee re) MOLAR VOLUME, L For n moles of a gas, work done Ra, 1) a Irreversible Adiabatic Expansion In free expansion, the external pressure is zero, i.e. work done is zero, &AT=08AH=0. In intermediate expansion, suppose the pressure is suddenly released to 1 atm and the gas expands ‘adiabatically against this constant pressure. Since this is not a reversible expansion equation (xi) cannot be used. Since, q , a=W W=Cy(T2-T) (xiv) Let the volume changes from V; to V2 against external pressure, Pox W=— Pex (Vo- V1 Pal Be i) -raa( SE) sean) P, P, PP, Equating equations (xiv) & (xv), we get W=C(TrT;)=-R Pa (xvi) (For one mole) foam Cognions MUS, 57, Kol Sarat Sarvapriya Vine, New Del 110016, Emel ‘Websie: www megacosmeagatons.com® —auapaica (eT aay TTA e) eS) LLL TE SE LA EN TI ; , hat its volume becom, Problem 1: A gas occupies 2 litre at STP. It is provided 300 J heat so th es 2.5 litre at constant external pressure of 1 atm. Calculate change in internal energy. Solution: As AU=q+W Here, q= +300 J W=-Pav =-1x(25-2) 0.5 Latm 5 x 10° x 1.01325 x 10° J 50.6625 J So, AU = 300 ~ 50.6625 = 249.3375 J ‘SITES ARE SES RR STG | Problem 1: An ideal gas having initial pressure P, volume V and temperature T is allowed to expand adiabatically unti its volume becomes 5.66 V while its temperature falls o T/2. The correct expression for the maximum work done by the gas during the expansion as a function of the initial pressure P and volume V. (A) 1.25 PV (B) 3.55 PV (C) 2PVv (0) 3.56 PV Solution: For an adiabatic process, TV" = constant Ty = Ty Hence, 2 = (5.66)"* or log 2= (y~ 1) log 5.66 ye 14 The gas is, therefore a diatomic gas. The work done by a gas during an adiabatic process is w= 1, A O6. yt q (6:66 4) 7s Since Py =P,Vy =P, (6.66 Vy! =[P6-66¥)_ py] wel (6.66) we Hence, (A) is correct. Megacosm Cogntions Pi Ud, §7, Kalu Sera, Sarvapiva Vihar, New Delhi-110016. Emal: enqutyamegacoumcogniions com Website wiv. megacaemeogniions.comCL 1. Define system, types of system and extensive properties with example, 2. Define the following terms: (i). State variables of a system (i) Internal energy of a system 3. Derive the value of C» ~ Cy | 4. ‘2aas present in a cylinder fitted with a frictionless piston expands against a constant pressure of (1 atm from a volume of 2 litre to a volume of 6 litre. In doing so, it absorbs 800 J heat from surroundings. Determine increase in internal energy of process. 5. How much heat is required to change 10g ice at 0°C to steam at 100°C? Latent heat of fusion LU and vapourisation for H,O are 80 cal/g and 540 cal/g respectively. Specific heat of water is 1 callg Two moles of an ideal gas at 2 bar and 27°C expand isothermally against a constant pressure of “7 1 bar. The work done by the gas is equal to (A) 35 kJ (8) 25kJ (yisis (0) 45k (One mole of a perfect gas expands isothermally to ten times its original volume. The change in entropy is (A) 01R Ue 2508 F R ) 10.0R &> Ia certain mass of gas is made to undergo separately adiabatic and isothermal expansion to the Y same pressure, starting from the same initial condition of temperature and pressure, then, as compared to that of isothermal expansion, in the case of adiabatic expansion, the final (A) volume and temperature will be higher (8) volume and temperature will be lower (C) temperature will be lower but the final volume will be higher (D) volume will be lower but the final temperature will be higher orn 57, KW S10 Sarvapiva Vihar. New Det 110016, mal: enguiy Webtse www megacormcognitoncom, Thermodyna ‘ond Law aul ie Aes mui rty called entropy and is represented by The disorder is the manifestation of another thermodynamic proper fh as internal ener the symbol (S). Obviously, entopy, tke any cher thermodynamic bagel tte a «) and enthalpy (H) should be a state function. The entropy change, 4S Is gI Ag = Ge A) ’ out reversibly and isothermally (ie, at state function. be justified on the grounds that the of the molecules due to increaseq Here, day is the heat absorbed when the process is carried Constant T). The AS defined by eq. (i) is independent of path, as itis a GieJT is a measure of increase in disorder of the system. This oa absorption of heat into a system leads to the vigorous movem kinetic energy. In other werd, the more heat the system absorbs, the more aaegiraet aie Eurherore, if heat is absorbed at low temperature it becomes more disordered ‘nan When eee ‘amount of heat is added at higher temperature. This is obvious as T is placed in denor am, the chan flgeful form oF the second law is that, “for a spontaneous process in an isolated system oo {otal entropy of universe is positive’. We already know that for an isolated system, energy temas Constant. Therefore, increase in entropy in such a system is the natural direction @ spontaneous change - Entropy of vaporisation 4 4 Sola que Gas @ Temperature, T > ) (2) As a sample changes from solid to liquid to gas, its particles become increasingly less ordered, and its entropy increases. (>) The entropy of a solid increases as its temperature is raised. The entropy increases sharply when the solid melts to form the more disordered liquid and then gradually increases again up to the boiling point. A second larger jump in entropy occurs when the liquid turns into vapour For a spontaneous process in an isolated system, the change in entropy is positive. However, if a system is not isolated, e.g. ‘a cup of hot tea’, we have to consider entropy changes of the system and the surroundings which together constitute the isolated system. Thus the total entropy changes (4S. is sum ofthe change in entropy change (8,n4q) and the change in entropy ofthe surroundings (ASsuinoge) AS. = AS oem + DS yurcundrge For a spontaneous process AS,,.,, must be positive, i.e, AS.) = AS pen + ASprcinangs ? 0 When an isolated system is in equilibrium, the entropy is maximum. The mathematical condition for entropy (S) to be maximum is that the change in entropy (AS)is zero, ie, AS = 0 (at equilibrium for an isolated system) Entropy Changes for an Ideal gas. Isothermal process Megacoim Cognition: Pls. 57, Kol Sara, Sarvapriya Vika, New Doth -110016, Emel. enqukyimegacosmcagnifons com Webs wien megecoemcogntions comSEL rg For any process, ds dq,, = dE - dw = dq,, = dE +Pav da.., = =dS= sag =MCudT , nav T Vv = AS =nCy In 2 +nRin 1 Y For reversible isothermal process AT = 0 Therefore, AS =nRin. V, +-ASunverso = ASuy In Isothermal Irreversible process we consider that the system goes through the ibly. Since the initial and final states of reversible and irreversible process can irreversible process reversit cH-TpaTe it n+ ASsurounding = 0, BECAUSE AS. peundng = a ial to final states of the be same, the change in entropy will be the same as in reversible isothermal process (Vz =Vs) T as, Since the magnitude of work involved in the irreversible expansion is smaller than that in the reversible Process, it is obvious that Gir O- Adiabatic Process Since in adiabatic process q ASsur = 0. Since in an adiabatic process, is given es A8_q2NCy In , therefore nRInwz For, ASuniverse = ASsystem + ASzurounding = 0. SINCE ASsurounting = 0, it follows that ASsyetem 2+ nRInz V, This follows that the decrease in entropy due to decrease of tem) of entropy due to increase of volume. In the Adiabatic irreversible process, ASgurrouncing = 0 85 Aqacat = 0. V, AS, =NCy nZenkin vee This is because in a adiabatic irreversible process the if the initial P,T,V matches wi versible and irreversible match the final T will not match. Since for then if the final P & V match between re\ both temperature and volume change, the expression for the molar entropy perature is compensated by the increase ith reversible process reversible process AS.ysiom = 0 it will not be so for irreversible process. This can be illustrated if we consider the entropy changes in the conversion of water to ice at three different temperatures. The relevant entropy changes for the system, surrounding 1g and total changes are given in table. We find that at 272 K, freezing is spontaneous because AS,,,,is positive. At 274 K Megacosm Cognitions Pvt.Ltd. 57, Kely Sora lya Vihar, New Dethi-110016, Email: enquky@megacosmcognitions com Website: www. megacormeognitions comMegacosm Cognitions Pvt. Liq, melting is spontaneous, a, reverse change, i.e. i onigngcus ut sar meting is spontaneous. At this temperature, AS gayi8 negative and freezing is not sp ° 273K, AS,,i8 zero which means that neither freezing water and ice are in equilibrium and no net change is obser ved. Thus we note that AS, iS a criterion fo, spontaneity of a change. Entropy change for the transformation H,0(/) > H,0(s) at a 1 bar — Sioa Temperature 1S ASirmsroe z= =e c K ‘JAK mol) JAK mol) fe eu ei 272 ~21.85 421.93 [ | = $21.99 0 o | 273 21.99 = 1 [27a ~22.13 $22.05 x 7 iroundings |n exothermic reactions, heat released by the reaction increases the deorder fitie ae - as Overall entropy change is positive. In some exothermic reactions, ent chy exh = decrease due to conversion of a gas into a solid product. However, if rea il be spontaneous. Let ue increase in entropy of the surroundings is very high, the total entropy change wi n into oxide results in {ake oxidation of magnesium which is highly exothermic. Conversion of oxyger decrease of entropy. 2Mg(s) +0, (g) > 2Mg0(s) 4,8" =-217 JK "mor! 4\H’ = ~1202 kJmor" Heat released will increase the entropy ofthe surroundings and therefore G (-1202x 10° Jmol") set iene ae = $$ 44.0310? JK“mol 298 K * Suu) = -217 JK 'mol" + 4.03 «10? JK"mol = 43.81% 410" JK. ‘mol* Since AS,,.. is positive, reaction will be’ spontaneous. {2 endothermic reactions, reactants on conversion into products go to higher energy state and temperature of the system falls. As @ consequence, heat flows from surroundings into the system, the entropy of the surroundings decreases. If the disorder of the system rises Sufficiently high and overall entropy increase is positive, the reaction will be spontaneous. Mlustration 1: Predict in which ofthe following, entropy increases/decreases. (i) A liquid crystallizes into a soli, (ii) Temperature of a crystalline solid is raised from 0 K to 118 K. (il) 2NaHCO, (s) + Na,CO, (s) +CO, (g)+H,0(g) (iv) H, (g) > 2H(9) Solution: (i) After crystallization molecules attain decreases. (ii) AtO K, the nuclei of all atoms are static and entropy is minimum. if temperature is raised to 115 K, molecules begin to move and oscillate about their equilbvum Positions in the lace and system becomes more disordered, therefore entiopy increases. (i) Reactant, NaHCO; is a solid and it has low entropy. Among products there are one Solid and two gases. Therefore, the products representa condition of higher entropy, (W) Here one molecule gives two atoms i... number of paticles increases leading to more disordered state. Two moles of H atoms have higher entropy than one mola ot hydrogen molecule. an ordered state and therefore, entropy ‘Megacosm Cogntions Pt. ld. 57 Kalu Sora, Sevaptva Via New Deft 110016, Emel ‘enquryaimegacosmcognitons com ‘Website www megacesmcogniions com -LC ET Mustration 2: In which of the following entropy decreases, (A) H2Qice > HzO water (B) HeOvater > Hie (C) HzO ater > HeOvasour (D) HQ ce > HeOvapou: Solution: After crystallization molecules atlain an ordered state and therefore, entropy decreases Hence, (B) is correct. Entropy Change during Phase Transformations Phase changes occur at constant temperature at a given pressure and process is reversible. For example, H,0(s) > H,0(¢); 4,,H’ = 6.0 kJmol (takes place at 273 K at 1 bar) H,0(¢) > H,O(vap); A,gH’ = 40.79 kJmot (takes place at 373 K at 1 bar) es ‘When solid melts, there is an equilibrium between the solid and the liquid at the freezing or melting point The process involves latent heat which is equal to standard enthalpy of fusion, 4,,H'at constant temperature and pressure. For water, AgeH = 6.0 kJmot" byyS’ = See = Saat eT, 8.0 kJmot’ _ 6.01000 Jmol* K-41 273K 73K 21.978 Jmol'K Similarly, when a liquid is transformed into vapour at constant pressure and temperature, Avg! an MoS > (Tis boiling point) Standard enthalpy of vaporization for water is 40.79 kimol". oe AvagH _ 40.79 kimol _ 40.7910 Jmor-* — T 373K 373K = 109.356 JK ‘mol Mlustration 3: The enthalpy of vaporization of benzene (GeHe) is 30.8 kimol” at its boiling point (80.1°C). Calculate the entropy change in going from (i) liquid to vapour and (i) vapour to liquid at 80.1°C. Solution: —_Vaporization of a liquid is an endothermic process and therefore enthalpy of vaporization, AvapHt is positive. Contrary to this, condensation (i.e., from vapour to liquid) is exothermic process and therefore enthalpy of condensation is negative but magnitude of enthalpy in both the case is equal. That is, Brag’ =—AconiensHt For vaporization of benzene, vag _ 30.8 kJmol' _ 30.8x1000 Jmol” T 353K «383K = 87.252 JK"'mol For condensation of benzene, 87.252 JK“'mol Deb 110014, Em Website www megacasmeogniions com vkymegacosmeegniions.comAbsolute Entropy as the absolute zero of temperature jg The entropy of a perfectly crystalline substance approaches Zero ‘approached. This is thie law of thermodynamics. noted by Sm Standard molar entropy, the Molar entropy, the entropy per unit amount of a substance, Is der Foal geente Seed a entropy per unit amount of substance in its standard state at the species ‘The definition ofthe ent” The standard entropy ofa substance o on is also called absoiate eniony. NTE EAT, entropy Given by equation earlier helps in determination of entropy. The unit of ™ Entropy Change for a Reaction Entropy change for a chemical reaction (when reactants change COr with the help of data given for standard molar entropies ata gon fon entropy of a reaction, we can give qualitative information about i by subtr ‘work, we require standard entropy change, A,$’ for a reaction and it can be determined by subtracting the standard entropies of reactants from the standard entropies of products. Thus, P ‘Sx = Y.VpSq (Products) - J7v,S,, (reactants) (vp and vq are stoichiometric coefficient For example, in a general reaction 2A +B» cC+dD 4S, [cs, (C)+ 2Fe,0, (s), we can write ASq =28,,[Fe,0,]-[4xS,, (Fe) +3x8;,(0, Ni (2x 87.4 -(4x27.3 + 3%205.0)] Jk-'mol* = ~549.4 JK ‘mol As expected, there is a large decrease in entropy during the reaction, mostly because the highly dispersed oxygen gas reacts to form the compact solid FeOs. Now, we would like to understand that inspite of the negative entropy of the reaction, why is the reaction spontaneous. As already emphasized, MSs = (AS sytem + ASsunsuning } OMly decides the spontaneity of a reaction. In this case, heat evolved during the reaction increases the entropy of the surroundings. For calculating entropy changes in the surroundings, we have to consider the heat absorbed by the Surroundings which is equal to~d,H’. At temperature T, the entropy change of the surroundings is as? __AH (ssroecnge) =e 47 in equation (4.7), because -A,H is positive and so AS” (surroundings) is also positive, corresponding to an increase from its initial value. ~(-1648x10° Jmol) |. iateeaeitU aot) (4H for the reaction is - 1648 x 10° Jmol ‘) 238K = 5530.20JK “mol This high increases in entropy of the surroundings is due to release of energy (heat) into surroundings, Thus, total entropy change for the oxidation of iron, Sy pean, = 4S +48 on (t |ssrosnags) suroanrg (enten) =O HIT +A,S om) = (+5530.20 JK ‘mot") + (49.4 Jk ‘mor') = +4980.8 JK ‘mol This overall increase in the entropy makes the oxidation of iron 4Fe(s) +30, (g) -» 2Fe,0, (s) spontaneous. ‘Megacosm Cogntions Pt Lid. 57. Kal Sere. Savopriva Vihar, New Del 110014, Emal enguky@megac ou Webste: www megacosmeegntions comCec ONLY NT llustration 4: Calculate the change of entropy 4,S,, at 298 K for the reaction in which urea is formed from NHs and CO,, 2NH, (9) + CO, (g) -» NH,CONH, (aq)+H,0(!) The standard entropy of NHjCONH, is 174.0 JK-'mof'. For NHs, CO2 and H,0 it is 192.3, 213 and 69.9 JK"'mol" respectively. Solution: 4,8, = vp" (products) -Y.v,8 (reactants) = [(174.0 + 69.9) (2192.3 +213)] JK*mor" (243.9-597.6) JK“'mol" = -353.7 JK* Here, sign of the entropy change a,S"is according to expectation, By examining the equation for formation of urea from ammonia and carbon dioxide, we find that there is decrease in the number of moles when reactants are converted into products. Secondly, reactants go from gaseous state to aqueousiliquid state to which also favours decrease in entropy. bs Energy and Spontaneity We have that for a system which is not isolated from its surroundings, it is the total entropy change, AS,..,which decides the spontaneity of the process. AS.oat = ASoten + SS xrminings in our analysis for the reaction of oxidation of iron, we found that AS, knowledge of AHyrcunsigs and T, that is 4H gacundngs T= —AH yen IT svrountings COUN be calculated from the Therefore, AS soem + if we multiply this equation throughout by T, we have TAS stem + (AH, OF AH yum ~ TASaytem = TAS (4.8) The equation (4.8) is so important and so useful as a manifestation of the second law that a new thermodynamic function, the Gibbs energy or Gibbs function, G, has been defined as G = H — TS. (In earlier literature this was called Gibbs free energy but in accordance with IUPAC recommendations we shall use the term Gibbs energy.) Therefore, the change in Gibbs energy for the system, AG, AG rem = AH stem — TAS yam — Sopten dT ‘At constant temperature, AT = 0 lien orion iS AG satan = AHstm ~ TAS em (4.9) Usually the subscript ‘system’ is dropped and we simply write this equation as AG = AH-TaS, (4.10) Thus, Gibbs energy change = enthalpy change - (temperature x entropy change), and is referred to as the Gibbs energy equation, one of the most important equations in chemistry. Here we have considered both terms together for spontaneity: energy (in terms of AH) and entropy, AS (a measure of disorder) Dimensionally if we analysis, we find that AGhas units of energy because both AH and the TAS are energy terms [Since TAS = (K)J/(Kmol) = J/mot or mor). Now let us consider how AG is related to reaction spontaneity from eq. (4.11) obtained by combining eq. (4.8) and (4.9) ie., AG jaten = ~TAS on (4.11) ‘Megacosm Cognilons Pl. 57 Kelu Sera Sevapriya Viner, New Deth-110016, Emall:enaukymegacoimcognifions com Webste : www.megecosmeognttons. comtaneous process, and $0 it folloy in taneous process, live value in a spon ae on eq.(4.11). ve posite) in a spon The second law states that AS,,. increases (AS,,4 s postive) in 2 SPO! that a Should decrease i.e. AC should have a ne Let oe of spontaneity a at constant temperature and Pressure () if AG,,,...is negative (< 0), the process is spontaneous. (i) if 46,aoqi8 positive (> 0), the process is not spontaneous. (il) AG ug 0, the system has attained equilibrium that is the direction. system is not moving in any Gibbs ener Gibbs energy of formation We have. er (ana ee changes can be calculated for chemical reactions by using values of 4,H and S° for the substances in the reaction, ,G' can be found from the resulting values of 4\H and $° using eq, (4.10). Mlustration §: Calculate the standard free energy change forthe formation of methane at 298K. Cygephie) * 2H, (g) > CH, (9) eranm) * 2H, Fi Given that AH; of CH, = -74,81 Kdmot and S’ of Cyprite, Ha) and CHya) are 5.70 JK"'mot", 130.7 JK-'mol-" and 186.3 JK-'mol"' respectively. Solution: Let us first consider values of A,H and S°. Ci #,(9) CH,(9) AH Ikimot! 9 0 SIA81 S'1JK"mor 5,70 130.7 186.3 Now using the above data AH = A,HCH, (g)- {HC ce) +2A,HH, (o} =-74,81 kdmol" -(0+0) = -74.81 kimot CH, (8) {SiC gage) +28nH, (9)} ~=[1(186.3 Jk “mor)]-[4(5.70 Jk-'mor") + 2(130.7 JK “mot )]=-80.8 Jk*mor* ‘Substituting the values of 4\H’and_4,S"in Gibbs equation, we get 4,’ = 4H -Ta,S° = -74.81 kimol — (298K)(~80.8 10° JK*mot") =~74.81kImol" +24.07 kimot" =-50.73kJmol Mlustration 6: Silane, SiH, like methane, bums in air. The product silica (silicon dioxide) is solid quite unlike carbon dioxide. SiH, (g)+20, (g) > SiO, (s)+2H,0(g) Standard Gibbs energy of formation of SiQ., HO and SiH, are -805, -228.6 and +52.3 (ail in kimor-") respectively. Calculate the value of 4,6" Solution: Applying equation 4,6’ = vpA,G' (products) ~ J” v,4,G' (reactants) =[4,G" (SiO, )+24,6" (H,0)]-[4,6 (SiH) +24,6" (0, )] ‘Standard Gibbs energy of formation of elements being zero, we have — “Megoconm Cogniions Pld, $7. Kalu Sor Sarvapiya Vir, New Deh -110016, Ema enquryimegacoamcognion oe Websile wow megecosmcogntions comLS CC KT 4,6" =[(-805 kJmot ')+2(-2286 kumot)]-[1(+52.3 ksmot") +0] =(-1262,2 imo") [52.3 kimot"] = 1314.5 kimot" Negative value of 4,6’ supports spontaneity of the above reaction. Gibbs energy change and equilibrium constant We have seen that for a chemical re il change should be negative, peels acne! Direction of During the course of a reaction. Gibbs | “ : | Sra dateases nd compoiten of escton ure canges [| \ saaemss || with time and finally @ constant composition of the mixture is / §\ | |46 obtained. A curve composition of the mixture ig obtained. A curve 8 J al of the shape W is obtained 5 ay The composition at lowest point of the curve - point of minimum 3 SE] Gibbs energy - corresponds to equilibrium. For a system at ' cauilbrium, any change (either the forward or reverse reacion) 1 ncrease in Gibbs energy and therefore neither Reaclanis Products When minimum Gibbs energy lies Very close to the products, the equilibrium composition strongly favours Products and reaction goes near to completion. When minimum Gibbs energy lies very close to the Stucke te ,Sdulitrium composition favours the reactants and reaction ‘does not go. Both the situations are shown below in fig (a) and (b). ‘Sometimes minimum value lies approximately halfway 'y between products and reactants halfway between Products and reactants and in such situations, both reactants and products are in similar abundance and equilibrium constant, k is close to 1 Th I i & | 3) 8 | © o | Reactants Products Reaciants Products: fa) (b) 'n order to make these ideas quantitative we must consider Gibbs energy change. ,Gand standard Gibbs energy change, 4,G’. Here, A,G'is the difference in standard Gibbs ‘energies of formation of the Products and reactants both in their standard states. Similarly, Gis the reactions Gibbs energy change at 2 definite, fixed composition of the reaction mixture. Let us consider formation of ammonia where nitrogen and hydrogen are reactants. The Gibbs energy of reaction, ,G, is related to the composition of the reaction mixture and to standard reaction Gibbs energy, ,G’ by the equation: A,G=A,G'+RTINQ where Q is the reaction quotient and R is the gas constant, with the value 8.314 JK~'mol"' If the species are gases, these concentrations are expressed in partial pressure and reaction quotient will be Q, and species are in solution, reaction quotient will be expressed in terms of molar concentration as Q. At equilibrium, Q = K and therefore, above equation becomes 0=A,C +RTInK or, A,G’ =-RTInK or, AG =-2.303RTIog,,K (ata) 7. Kol Sora, Savapriya Vihar, New Del 110016, Emal: enqtymegecosmeognions com Wobste- www megacesmeagntions com- oT CTT The €9.(4.14) can also be written as K =e" _ 49-46 2207 We also know that AG =AH -Tas’ = -RTInK Qn ue of A,H , jons the value of AH’ may be Since 4,’ depends on the value of 4H’, for strongly endothermic ie and the reaction is unlikely tg large and positive. In such case, value of K will be much smaller eee eae sane i form much product. In case of exothermic reactions, \H is large an oe expect strongly exothennie large and negative too. In such cases, K will be much leper ten 4.We may ‘eactions to have a large K, and hence can go to near completion. ice versa) Using e¢.(4.14), we can determine the value of 4,G'if the value of K is shown (or vi t 298 K, if Mlustration 7: Calculate A,G’ for conversion of oxygen to ozone 3/20, (g) - 0, (a) Ky for this conversion is 2.47 x 10°. Solution: We know ,G'= -2.303 RTlogk, and R = 8.314 Ji(Kmol) 2 Therefore, 4,G° = -2.303(8.314 JK'mol") x(298K) (log2.47 x10) = 163.22 kJmol* Mlustration 8: Find out the value of equilbrium constant forthe following reaction at 298 K. 2NH, ()+ CO, (g) = NH,CONH, (aq) +H,0(/) ; Standard Gibbs energy change, A,G’ at the given temperature is -13.6 kJmol (A) 24 (B) 12 (C) 240 (D) 2400 Solution: We know, 4,6" = -2.303RTlog,,K log, K = 13.6x10°J mol 2.303 x8.314J K mol "x 298K logiok = 2.38 Hence K = antilog 2.38 = 10° = 2.4 10? Hence, (C) is correct Nea TNT e ey Problem The equilibrium constant at 25°C for the process Co” (aq) + BNH, (aq) = [Co(NH,), |" (aq) is 2.0 x 10". Calculate the value of AG’ at 25°C. [R = 8.314 JK mot"). In which direction {he reaction is spontaneous when reactants and products are under standard conditions? Solution: For the reaction Co” (aq)+ 6NH, (2q) = [Co(NH, Je)" (aa) k=2.0x 10" ‘Since AG ‘is negative the direction of the reaction will be forward. jegacosm Cogniions Pvt. Lid. 57, Kaly Sera Sorvoptve Vir New Deh 110016 ameter Website: www megacormeogntions com enqueyamegacosmcosntions comCC) KKK Problem 1: At constant temperatu : its is correct for Toman and pressure which one of the following statements is CO(Q) + 1/20:(6) 5 co,(Q) ial AH = AE (8) AH< AE (©) AH» ae (0) AH is independent physical state of reactant Solution: AS we know, AH = AE + anRT iets a Product moles ~ gaseous reactant moles CO(g) + 112 04) —s cog) AN 1-(1#4/2) = 1/2 AH= AE - 1/2 RT AHS AE Hence, (B) is correct. Agr Grn is the entropy of a perfectly crystalline solid zero? nay Why entropy of a perfectly crystalline substance is less than that of its imperfect crystals. (c) State the relation between stands \__ chemical reaction. Cc lard free energy change and equilibrium constant of a 5 b (@-N%(a)+0, (g)-> 2NO(g)is an endothermic reaction yet it is spontaneous. Explain the reaeon \farfora Teaction, K = 1.958 x 10° at 400K. What is the value of 4G’ at this temperature? = [R=8.314 JK mol] (c) What is meant by the term ‘Free Energy’? What is the necessity of introducing such a function? t = change in entropy with respect to temperature in case of sample is graphically represented (ae coy analyse the graph and answer the following. jt does T; and T2 indicate? ow does AB curve show? ii} What does BC curve show? Why temperature does not change? E a 8 ‘Temperature 4 The standard Gibbs energies (A,C') of formation of SOx(g) and SO,(g) are -300.0 and & \ 374.1 kJmol at 300 K respectively Calculate AG and equilibrium constant for the following reaction at 300 K. 280, (9}+ 02 (9) = 280, (9) ‘Megaccem Cognit Pv. Lt. §7, Kalu Saal, Serveptva Vihar, New Deh 110016, Emel enaurymegacoameognifons com Website www meaceosmcegniions coma ‘Megacosm Cognitions Pvt.Ltd, 5 t 400 K. x5. Calculate the value of equilibrium constant, K, for the reaction a! \ 2NOCI(g) = 2NO(9) +c, (g) mo oa = 80.0 kJmol", AS’ = 120 JK"'mot" at 400 K, R= 8.314 JK” mo 8. _/ For the reaction 4 1 \~9,0(3)-»289(9)+40, (0) cow AH is 30.86 kimol' andasis 66 JK"'mot” at one atmosphere pressire, Re a te temperature at which AG for it will be zero. What will be i direction is temperature and at temperatures below this temperature and why’ ar 2 reaction of aH <0 and AS < 0, the reaction proceeds furthest in the forward direction at: Ow temperature (8) High temperature (C) All temperatures (D) No temperatures The dissolution of NH.CI in water is endothermic even though NH,CI dissolves in water Spontaneously. Which one of the folowing best explain this behaviour? (A) The bonds in solid NHiCi are weak AB) The entropy driving force causes dissolution (C) Endothermic processes are energetically favourable The dissolving process is unrelated to energy Calculate the entropy change involved in the conversion of one mole of water at 373 K to vapour al the same temperature. (Latent heat of vaporization of water = 2.257 kJg"') 108.9 Jmol 'k? (B) 0.1089 KJmol"'k” (C) 25.9 Cal mor"k* (D) All of these Megacoim Cognition Pd 57, Kol Sora. Svpriva Vir, New Dah 10016, Ema: enqutyamegacosncograam con Webale ww megacotmcagntion comTi ae THERMOCHEMISTRY 1 ioe with the transfer of heat between a chemical system and its surroundings ’ Seithor 2,chemical reaction takes place within the system. in general, a ee aa be either exothermic or endothermic. In the former case, heat is released to the surrounding Nn the reactants at a the products at the same temperature and presey aso temperature and pressure are converted to the p le tem, from the ae re, and in the latter heat is absorbed by the syster Sign conventions: 6 the heat is endothermic and AE or absorbed by the system (q>0) then the reaction is said to be AH value is r Given a positive sign. If the heat is evolved (q<0) the reaction is said exothermic, and AE or AH values is given negative sign 'n the computation of ments in their stand; Standard Standard states: formation of ele and a constant temperature. “State heal of reactions it is a convention to assume that the heat of lard states is zero. The standard state is taken as 1 atm pressure States for various forms of matter are summarized below. ig Stable crystalline f se crystalline form at 4 atm old form of sulphur) At standard state the heat of reactions are denoled by AE® or AH” at given temperature. Various Types of Enthalpies of Reactions 0) Enthalpy of formation: Enthalpy change when one mole of a given compound is formed from its elements. Hag) + 1120:(g)—+ H,0(), al ~285.83 kJ / mol (\) Enthalpy of combustion: Enthalpy change when one mol le of a substance is bumt in oxygen CH, + 20,(g)—+ CO, + 2H,0(), 4H = ~890.36 kJ / mol (ii) Enthalpy of neutralization: Enthaipy change when one eauivalent of an acid is neutralized by a base in dilute solution. This is constant and its values is ~13.7 kcal for neutralization of any strong acid and strong base since in dilute solutions they completely dissociate into ions. H" (aq) + OH” (aq) —> H0(/) AH = ~13,7 kcal For weak acids and bases, heat of neutralizat ion is different because they are not dissociated Completely and during dissociation some heat is absorbed. So total heat evolved during neutralization will be less. e.g. HCN + NaQH —> NaCN + H,0 AH = -2.9 kcal Heat of ionization in this reaction is equal to (-2.9 + 13.7) kcal = 10.8 kcal (v)_Enthalpy of hydration: Enthalpy of hysration of a given anhydrous or partially hydrated salt is the enthalpy change when it combines with the requisite no. of mole of water to form a specific hydrate. For example, the hydration of anhydrous copper sulphate is represented by CuSO,(s) + 51,0 () —+ CuSO,5H,O(s), AH? = -18.69 kcal wv Enthalpy of transition: Enthalpy change when one mole of a allotropic form to another allotropic form. C (graphite) —> C(diamond), AH? = 1.9 kilmol substance is transformed from one (vi) Enthalpy of sublimation: It is the enthalpy change involved in the solid directly into its vapour at a given temperature below its meltin, L{s)— l(a) ; AH= 14.9 kcalimol AH, Conversion of one mole of a 1g point, For example, ton = AHtusion + AHyapouraation ns Pid, 57. Kalu Sarl Sarvariya Vor, New Debi -110016, Email: enauryemegacosmcogntiom com Websie www megecosmeognions comCc LTT cof one mote of ator (i) Enthalpy of atomisation: The amount of heat required for the (ora elon " gaseous state from its elements is known as heat of, atomizal Cs) Cg) ; AH= 171.7 kealimol (a) —» 2H(g); AH = 104 kcal In this case, heat of atomization of hydrogen is (Vil) Enthalpy or heat of solution: The amount of heat evolved is dissolved in excess of solvent so that further addition of sol H,S0, (/) + aqueous H,80, (aq); aH = -20.2 Keal 52 keallmol or absorbed when one mole of solute vent makes no heat change. fefined as the amount of energy vi ice e is d (will) Lattice enthalpy: Lattice enthalpy of an ionic compound is on caiof remlred]cimybor released when one mole of ionic compound is formed by in Constituent gaseous cation and gaseous anion. LT cca For some reactions it is not convenient to measure the heat change in the laboratory. So conventional Procedure based on the principle of conservation of energy has been suggested which can be stated as lows: 1 The heat of formation of any compound is equal in magnitude and of opposite sign to the heat of dissociation of that compound at the given temperature and pressure For example, enthalpy of formation of liquid water from its elements hydrogen and oxygen is ~ 285.830kJ mol" and the enthalpy of dissociation is 285.830 kJ mol”. Thus the process can be represented by Hag) + 1/2 Ox(9)—> 1,0 (\), ‘AH(298 K) = -285.830 kJ H,0(l) — Hy(g) +% Org), AH (298 K) = + 285.890 kd 2, The total enthalpy change of a reaction is the same, regardless of whether the reaction is completed in one step or in several steps. (Hess's Law of constant heat summation) It has been ‘experimentally verified and is also a consequence of the law of conservation of energy. It is of Particular utility in calculation of the heats of reactions which are difficult for practical calorimetric Measurements. For example: Carbon be converted into CO; in 1 step C(s) + OXg) —+ COA(g) AH = -94 kcal or in two steps G(s) + 1/2 O2(g)—> CO(g) CO(g) + 1/2 Ox(g)—> CO,(g) According to Hess's law: AH = AH, + AH 6.4 67.6 or AH = coxa) \en AH, "4 ‘CO(g) Mustration 1: t Aan ‘ ss ‘AH. In this case express AH in terms of AH;, AH, AHs \H, + AH2 + AH3, AH, AHy Solution: Lid, 57, Kel Sar, Sovoprve Vihar, New Det Websie. www megacosmcognitens.comCE ic 62s Mlustration 2: HO (I) > H,(g) + 4 2 Ox(9) AH = +285.83 kJ/mole ‘What is AH for formation of H,0 (|) from its constituent elements? 1 Solution: W200) Hefa)+ (a) aH = + 285.89 kJ/mole 1 Ha(s) + 2 029) > H,0() AH =~ 285.83 kJ/mole (AH, ),,. = -285.83 kJ mole Ee Genny Crystal (Born-Haber Mos) + 1x0) > MX(s) step1 | step2 M(g) Xia) Steps | Step 3 | Step 4 M@ + xig—_ Born ~ Haber cycle The change in enthalpy that occurs when 1 mole of a solid crystalline substance is formed from its gaseous ions, Step 1: Conversion of metal to gaseous atoms M(s)—> M@Q), AH, = sublimation Step 2: Dissociation of X; molecules to X atoms %(g) —> 2X (9), ‘AH: = Dissociation energy ‘Step 3: Conversion of gaseous metal atom to metal ions by losing electron M(g)—> M"(9)+e°, ‘AH, = (Ionization energy) Step 4: X(g) atoms gain an electron to form X ions X(g) +e" —> XQ), AH; = Electron affinity Step 5: M’ (g) and X" (g) get together and form the crystal lattice M’ (g) +X (g)—> MX(s)_AHs = lattice energy Applying Hess's law we get AH; + 112 AH + AH + AHy + AHs = AH, (MX) On putting the various known values, we can calculate the lattice energy. Ilustration 3: What is the expression of latice energy (U) of CaBr, using BornHaber cycle? Solution: Cale) + Bela) 8H, Cataty s o Calg) 2Br(g) Voss HE, +1E, 2E.A ca*Q) + 28r Gg = S +E, +1E)+D+2EA+U cy, ‘Megecosm Cognos Pt. Us, §7,Kaly Soro Soveptva Vihar, New Deh 110014 Email: enquy@megaccimcagniions.~ ion? Mlustration 4: Whatis the relation between AH and AE in his reaction CH4(g) + 20-{g) === CO.(g) + 2H20(!) (A) OH = AE- RT RT (8) aH=aE- = AE -2RT (C) AH= AE + 2RT Oe Solution: AH = AE + AnRT . tants = 1— An = no. of moles of gaseous products - no. of moles of gaseous reac AH = AE - 2RT Hence, (D) is corre Etna ah Whenever a chemical bond is formed energy is released. Conversely, energy is required to rupture a Chemical bond. The energy requred to break @ particular bond in a gaseous molecule is refered to as bond-dissociation eneray. Heo Hie) nore) OB)s ate O-H H(g) + Og) AH= i In such case, bond energy is crore or be 9) erage of the bond dissociation energies of various similar bonds 1 Ao.» = (498 + 430)/2 = 464 kJ mot Hence, bond energy may be defined as the average amount of energy required to break one mole bonds Of that type in gaseous molecules. Thus, the values given in bond energy data can help us in: (i) Calculating standard enthalpy of reactions (ii) Calculation of bond energies of some specific bond in the molecule Determination of Resonance Energy . Resonance Energy = (Experimental or actual heat of formation) ~ (Calculated heat of formation) Mlustration 5: The standard molar enthalpies of formation of cyclohexane (/) and benzene (/) at 25°C are ~ 186 and 49 kJ mol” respectively. The standard enthalpy of hydrogenation of cyclohexene (/) at 25°C is -119 kJ mol’. Use these data to estimate the magnitude of resonance energy of benzene. Solution: CoH of!) + Ho(g)——> CeHya(l) ; AH =-119 kd (This involves breaking up of one double bond and addition of one H, molecule), = $eHe(i) + SHe(g)—> CoHra() ; AH = (3 x -119) = - 387 Kd .......(i) (This involves breaking up of three double bonds and addition of three H, molecules). Calcuated AHiCeHs, /) = -156 + 357 = 201 kd ©. Resonance energy = Observed AH;~ calculated AH, of CsHe = 49-201 =~ 152kJ Variation of Heat of Reaction with Temperature The heat of reaction depends on the temperature. The relation between the two is known as Kirchot’s equation. AH, — AH, i = (ii) AC» = molar heat capacity of products ~ molar heat capacity of reactants (at constant pressure) ‘AGy = molar heat capacity of products ~ molar heat capacity of reactants (at constant volume) imal : enguirydmegacosmeognion: comBomb Calorimeter ‘The calorimeter used for determining enthalpic combustion known as the bomb calorimeter ie shown as Fig This apparatus was devised by Berthelot (1884) to measure the heat of ‘combustion of organic compounds. A modified form of the apparatus shown in Figure shown consists of a sealed combustion chamber, called a bomb, containing a | pe weighed quantity ofthe substance in a dish along | with oxygen under about 20 atm pressure. The bomb is lowered in water contained in an insulated Copper vessel. This vessel is provided with a stirer and a thermometer readi Ing up to 1/100" of a degree. It is also surrounded by an outer jacket to ensured complete insulation from the atmosphere. EE su srs | container | STEEL BOMB SAMPLE ‘Bomb Calorimeter re ,GraPerature of water is noted before the substance is ignited by an electric current. After combustion, the ise in temperature of the system is noted on the thermometer and heat of combustion can be calculated from the heat gained by water and he calorimeter. By knowing the heat capacty of calorimeter and also the rise in temperature, the heat of combustion can be calculated by using the expression Heat exchange =Z x AT Where Z-Heat capacity of calorimeter system AT=Rise in temp Heat changes at constant volumes are expressed in AE and Heat changes at constant pressure are expressed in AH. Also, AH = AE + AnRT An = gaseous product moles ~ gaseous reactant moles. SOLVED P| aS Problem 1; Calculate the enthalpy of vaporization for water from the following Hag) + 1/2 Ox{g)—» H.0 (a) AH = ~ 57.0 kcal He{g) + 1/2 O2{g) —> H20() 68.3 kcal Also calculate the heat required to change 1 gm HO (I) to HO (g). & Solution: H,(g) + 1/2 Ox(g) —> H,0 (a); A 87.0 kcal (1) H,(g) + 1/2 02g) —+ H,0 (I); AH = -68.3 kcal we(2) Subtracting (2) from (1) H,0 (I) —> H,0 (g) ; AH = 11.3 kcal Enthalpy of vaporization for H,O = 11.3 kcal mol’ Also 18 g H,O requires enthalpy of vaporization = 11. 3 kcal 1.9 H,0 requires “ kcal = 0.628 kcal Problem 2: The standard enthalpy of combustion of H2, CéHio and Cyclohexane (C;H;2) are — 241, ~ 3800, - 3020 kJ mole” at 25°C respectively. Calculate the heat of hydrogenation of cyclohexene. Pot Ue. $7, Kol Soro, Sorvaprya Vor. New Delhi 110014, Emel: engury@megacosmeopniion: com ‘Webs : wiv. megacorm:2gntions comSolution: Problem 3: Solution: Problem 4: Solution: Problem 5: Solution: We have tofind 4 H for CoHio + Hp—> Coie . rr Given H, + 1/20, H.0 AH= 241 kd : Catto + Zo, 60054 SHO aH =~ 3800 Kd 2) 5 (3) Cetra + 902 9600, + 6H,O AH = ~ 3920 Son @ ) ‘Adding equation (1) and (2) and then subtatng o CoHio + Hp —> CoH io AH=~ 12 124 kd Heat of hydrogenation of cylohexene tions. Calculate the heat of formation of KOH (s) using the sai a ; K(s) + H.0(I) + aq —» KOH (aq) + 1/2 x(q) AH =—- (t) Hag) + 112.0, (g)— H.0(1) AH =~ 68.4 kcal @) KOH (s) + aq—> KOH (aq) AH = 14.0 kcal Q) We have to evaluate aH for Kis) + ; Ox(9) + ; H.(g) —> KOH (s) Adding equation (1) and (2), we have Kis) + ; Hag) + $040) +.aq—» KOH (aq) AH = -116.4 kcal « ‘Subtracting (3) from (4) we have. K(s) + 1/2 Ha(g) + 1/2 O2(g)—> KOH (s) AH =~ 102.4 kcal A oylinder of gas is assumed to contain 11.2 kg of butane. If a normal family needs 20,000 kd of energy per day for cooking, how long will the cylinder last ifthe enthalpy of ‘combustion, AH = -2658 kJ/mol for butane. Given CsHio (g) + $ O2—> 4CO, (g) + SHO (g) AH = - 2658 kJ Molecular weight of Ho = 58 g / mol 58 9 of butane on combustion produces 2658 kJ heat 11.2 kg of butane wil produce 255° 11.2 10 ks The family needs 20,000 kd of energy per day 2658 x11.2x 10" ‘58 x 20,000 Number of days = = 25.66 days Jeno eat of solution of anhydrous CuSO, is ~ 15.9 kcal and that of CuSO,.5H,0 is 28 Kcal. Calculate the heat of hydration of CuSO,, CuSO,(s) + ag—> CuSO, (ag) aH CuS0,.5H,0(s) + aq—> CuSO,. (aq) aH Subtracting (2) from (1) CuSO,(s) + SHO —> CuSO,,5H,0(s) 15.9 kcal (1 8 kcal Heat of hydration of CuSO, = - 18.7 kcal Megacoum Cagnlans FU 7. ah Sx ervopiya Vr New Deh-11006 Enel: enguiyamegecommesgenen con Websie: www megacosmcegnions comProblem 6: Solution: Problem 7: Solution: Problem 8: Calculate the heat of Neutralization from the following data 200 ml of 1M HCI is mixed wit of 0.5 M NaOH, The temperature rise in calorimeter was found to be 4.4°C. Water equivalent of calorimeter s 12 g and specific heat is 1 cal / ml / degree for solution. Given total solution = 200 + 490 = 600 ml 200 mi of 1 M HCI neutralise 400 ml 0.5M NaOH, Meg = N xVq. Meg of acid and base = 200 'e., 200 Meq of HC] react with 200 Meq of NaOH to produce heat = AH. 10 Meq of NaOH wil give heat = 5 x AH ie, heat of neutralization. ring neutralization of 200 Meq of acid and base = Heat taken up by Calorimeter + solution = MSAT + M,S,AT =12x4.4+ 600% 1x44 = 2692.8 cal Heat of neutralization = ~ 5 2692.8 cal 13.464 kcal Caleulate the resonance energy of acetic acid from the following data {i)__Enthalpy of formation of water = -286 ki mol" {i)_Enthalpy of formation of CO,(g) = -393.5 kd mot-" (i) Enthalpy of formation of CHsCO.H() ~384.5 kJ mol" (iv) Enthalpy of vapourization of H,O = 168 kJ mol" (v) Enthalpy of dissociation of CHy(g) = 1652 kd mol’ (vi) Enthalpy of formation of CeHe(g) = 90 kJ mot-* (vii) Resonance energy of CsHs(g) = 150 kJ mol" (vii)Bond enthalpy of C = C bond = 617 kJ mol ' (ix) Bond enthalpy of C - 0 bond = 420 kJ mol-’ (x) Heat of atomization of carbon = 718.5 kJ mol’ (xi) Heat of atomization of gaseous oxygen = 248 kJ mol! (xii) Heat of atomization of gaseous hydrogen = 217 kJ mol RE. of benzene = AH(observed) - AH(theoretical) ~150 = 90 - AHi(theoretical) AH((theoretical) = 240 kJ mol 8619) + 3H) —» (S) AHi(theoretical) = [ 6 x AHstome) * BE¢.¢ = 348 kJ mol C(s) + Ox(g) —+ CO,(a) AHY(CO2) = AHatomiz cig) + 2AH tons 0) ~ 2BE con 393.5 = 718.5 + 496 ~ 2BEc-5 BE cso = 804 kJ mot’ 2C(s) + O2(g) + 2H-(g) —> CH,COOH(g) Hi(theoretical) = [(2 x 718.5) + 868+496] [1239 + 348 + 804 + 420 + 400] = -410 kJ mot R.E. of CHyCO;H = AH\(observed) ~ AHitheoretical) = -384.5 — (-410) = 25.5 kd mot’ 19) * 6AHsomHig] -[ 3BEc-c + 3BEc.c + 6BEc.c} Calculate the heat of reaction for the hydrogenation of acetylene to ethylene at constant volume at 25°C from the following data (i) Enthalpy of formation of water = -285.8 kJ mol 4 (i) Enthalpy of combustion of acetylene = -1299.6 kJ mol (ii) Enthalpy of combustion of ethylene = ~1410.8 kJ mot egacosm Cogritions Pt. Ud. 57 KGW Sorel Savopriya Vier, New Des 10014, Emel: enauyemegaceimcogniion: com Webste www megacoimeognitons comCC ED . Solution: (i) Halg)+ 12 Og) —>H.0 () AH = -285.8 Kd mol 4 = -1299.6 kJ mol (i) Cath(g) + 8.0, (g) > 2602 (g) + H20 (AH = 7” 2 1410.8 kJ mol (i) C3H4(Q) + 302 (g) —> 2C02{g) + 24.0 (1), AH = Eqn. (ii) + Eqn (i) - Eqn (ili), we get C2Ho(g) + Ha(g) —> CzH.(g) AH = ~1299.6 285.8 + 1410.8 174.6 kJ mol’ AH= AE + AnRT AE = AH—anRT AE = 174.6 (1) (8.314 x 10°) (298) 172.12 kJ mol” Problem 9: From the following data, calculate the bond enthalpies of C—C and C=N bonds: (i). Enthalpy of formation of CHsCN = 87.86 kd mol, (i) Enthalpy of formation of CsHs = (ii) Enthalpy of sublimation of graphit yi (iv) Enthalpy of dissociation of nitrogen = 945.58 kJ mol (v) Enthalpy of dissociation of hydrogen = 435.14 kJ mol (vi) C-H bond enthalpy = 414,22 kJ mol” Solution: 2C(s) + 3H-(g) —> CoHs(9), AH = -83.68 kJ mot’ AH = [2AH6(5) _,c(q) + 3AH}) ~ [AHc-c + 6AHc-x) 783.68 = [ 2x 719,65 + 3 (435.14) ]-[ AHc.c + 6 x 414.22] On solving we get, AHc-c = 343,08 kJ mol 2048) + $a) + No (g) — CHONG) , AH = 87.86 ks mor" AH = [2AHo6) sc) Satin + 5 Shad ~ [@He.c + 34He-# + AHean] 87.86 [2 x719.65+3 (436. yg (945.58) — [343.0843 x 414,22+ AHc-s] ‘On solving we get, AH¢.n = 891.2 kJ mol”. Problem 10: Calculate the heat of formation of acetone from the following data: Heat of atomization H= 5211 kcalimol = 170.9 kcal Imo! 0 = 59.6 kcal/mol Average Bond energies C-H = 99 kcal c 1 kcal CC = 80 kcal Solution: 3C(s) + 3H,(g) + F049 —> CH;COCH,(g) 7 AH = [3AHe%)—s cig) * SAH + 3 ‘AH-0] — [64Hc-+: + 2AHe.¢ + Aceo] = [3(170.9) + 6(62.1) + 59.6)] ~ [6x 99 + 2 x 80 + 81] = 884.9 — 835 = 49.9 kcal/mol ya Vint, New DI Ema enqukysimegacasmessrifons com ‘srw magacremcognons comCC Se Problem 1: Solution: Problem 2: Solution: Problem 3: Solution: For the given heat if iW) Ce)voxjccu C02(g) + 97 kcal (i) COxg) + Cls) = 260(q) - 39 kcal The heat of combustion of ¢ toi is. (A) 68 kcal (8) ~ 68 kcal (C) +48 kcal (D) None C,+0 6) * Ox, CO, +97K cal 260, —>60,.. +C(s)+39K cal 260,5) +02, 9260, +136 K cal OF, CO(Q) + 1/2 Ox(g) = COQ) + 68 kcal Heat of combustion of CO =a kcal Hence, (B) is correct The heat of combustion of su 1 lcrose, Cy2H220;,(s) at constant volume is - 1348.9 kcal mot" at 25°C, then the heat oy Of reaction at constant pressure, when steam is produced, is (A) ~ 1342.344 kcal (B) + 142.344 kcal (C) + 1250 kcal (D) None The combustion equation of sucrose is CrzH2011(8) + 120219) > 12C0,(g) + 11H,0 (g) Here, ‘An = sum of gaseous product moles ~ sum of gaseous reactant moles An=12+11-12 ans ‘As we know, AH = AE + An RT, Where AH = heat of reaction at constant pressure AE = heat of reaction at constant volume 1348.9 kcal 25+273 = 208 K (1348.9 x 1000) + 11% 2 x 298 1348900 + 6556 = ~ 1342344 cal 1342.34 kcal Hence, (A) is correct For the given reaction He(g) + Fa(g) —> 2HF(g) AH? H(g) —> 2H(g) AH’ F,(g) — 2F (a) AH then the value of AH? for the given reaction H(g) + F(g) —> HF(g) is (A) 142 kcal (8) ~132.9 kcal (C) 132 kcal (D) 134 kcal Now for the reaction, H,{g) + F2(g)———> 2HF(g); AH? =~ 124 kcal ‘AH? = 3B, (reactants) - 5B.E of (products) or, = 124 = AHyn + Hee -2AHwe = 104 + 37.8 - 2H 2AH ins = 104 + 37.8 + 124 = 265.8 kcal ee egocarm Cogriiors Pi. tk, $7, KON Sara, Savopriva Var, New Del 110014 Emel enguryémeyacc Webste wim mepecasmcagntions comProblem 4: Solution: Problem 5: Solution: Problem 6: Solution: 8 Bond energy of H-F = 2058 = 132.9 kcal AH! forthe given reaction = ~ 132.9 kcal Hence, (B) is correct. d red phosphorous are -9.19 kJ ang The heats of combustion of yellow Li: page phosphorus to red phosphorous is ~ 8.78 kJ respectively, then heat of vane +041 kd (A)- 18.69 kd (C) +18.69 kJ (0)-0.41 kd (i). Pa yellow) +502(g)—+ PiOro + 9.19 kd (ii) Pe(ted) + 502(g)—> P10 + 8.78 kd Subtracting, P.(yellow) ~ P, (red) = 0.41 kJ => Pulyellow) = P,(red) + 0.41 kJ So, heat of transition of yellow to red phosphorus is ~ 0.41 kd Hence, (D) is correct. Given that = 2H,(g) + O.(g) —» 2H;0(g) , AH = 115.4 kcal the bond energy of H-H and O = O bond respectively is 104 kcal a 1119 kcal, then the O-H bond energy in water vapour is (A) 110.6 kcal / mol (B) 110.6 kcal (C) 105 kcal / mol (D) None We know that heat of reaction 4H = EB.E. (reactant) ~ 2B.E (product) For the reaction, 2H-H(g) + O = O (g) > 2H- O-H(g) 4H = 115.4 kcal, B.E. of HH = 104 kcal B.E. of = 119 kcal Since one H,0 molecule contains two O-H bonds 115.4 = [ (2 x 104) + 119] {4 x BEjo4y } ABE jon) = (2« 104) +119+115.4 (2x 104) +119+115.4 i.e., 0-H bond energy = 4 = 110.6 kcal mol" Hence, (A) is correct. The heat of transition for Camara > Camonnaue from the following is Coiamons + O2(9) —> CO2(g) AH = ~ 94.3 kcal Camorphous + O2(g) —> CO2(g) Al 97.6 kcal (A)3.3kJ/ mol (B) 3.3 keal / mol (C)-3.3 kJ/mol (0)~ 3.3 kcal / mol Given Co + O2(g) —+ CO,(g) AH = -94.3 kcal (1) Cx + 0.(g) —> CO.(g) AH (2) Subtracting equation (2) from equation (1): Co-Ca—> 0; AH = +3.3 kcal Cree = 43.3 kcal Hence, (B) is correct. Megacosm Cognions Pvt It. 57, Kalv Soro, Sarvepriva Vio, New Delhi-110014, mall: enquiryémegacosmcognifons com Website : www.megacosmcogniions comProblem 7: — The heat of neutral lisation of HCl by NaOH is ~ 85.9 kJ mol”. If the heat of neutralisation Ay ody NaOH is - 12.1 kulmol, the energy of dissociation of HCN is (A)-43.8 kJ (B) 43.8 kJ (C)68 kJ (D)~68 kJ Solution: Since “neutralization is an exothermic process, so the sign of its heat is ie peste Know. for weak acid, some amount of heat is used to dissociate It Ege heal of dissociation (or weak acid) + heat of neutralisation = heat of neutralisation for strong acid with strong base, NaOH Heat of dissociation (for weak acid) + 12.1 = 55.9 Heat of dissociation (for weak = 55.9~- 12.1 = 43.8k, Honce, (Bis comect" ("Me Ad) = $5.9-12.1= 438K) 1 lustrate with an example what is meant by ‘standard free energy of formation’ of a ‘compound. (From the data given below at 298K for the reaction: CH, (a) +20, (9) > CO, (g) +2H,0(1) Calculate the enthalpy of formation of CH,(g) at 298K. Enthalpy of reaction = -890.5 kJ Enthalpy of formation of CO2(g) = -393.5 kJmot-* Enthalpy of formation H,0()) = -286.0 kimol"* \2_-How much heat is evolved using neutralization of HCN by a strong base? Heat of ionization of HCN is 10.8 Kcal. eon + s 02(g) > 3H-O(I) + 6CO.(g) AH = -3264.4 kJ mole’, What is the energy evolved N 7.8 gm of benzene is burnt in air at constant temperature and at constant pressure. 4 From the following data at 25°C CH, (9) +20, (9) > CO, (g)+2H,O(I); AH? =-890 kJ enthalpy of formation AH, of CO, is -393.5 kmol-", AH, of H,0 is ~285.9 and find the enthalpy of formation AH, of CH,(g) and AE" for its combustion reaction shown above. (R=8.31 JK’ ‘mot') 3G ©2 (g)-» COxg) em C(s)+ $.02(0)+ C01a) AH = -26.4 K cal CO(g) + 40. (g)+COAg) AH=? Le Starting with the thermodynamic relationships AE=q-PAV and H = E + PV derive the relationship AH= gy. ar (8) AH> aE a For a system C(s) + 02(g) = CO2(g) which of the following is correct: ai (C) aH < AE (0) aH=0COT? ae Sy Ve . For the reaction, CrHy(!) + 90.(g) > 7COAg) + 4Hz01"), the calculated heat of reaction is 232.6 kJ/mol ang observed heat of reaction is 50.4 kJ/mol, ‘hen the resonance enerOY is = 182.2 kJ / mol (6) + 182.2Ki/ mol (C) 172 kJ/ mot (0) ics wy Heat of neutralization of ual to AH of ‘strong acid by a strong base is ea UH + OFF > H.0 ° {@) H+ H+ HO UC) 2 2 Ors 220) (8) Ge co0H* NaOH = CHsCOONa + H,0 New Beth -110014, -gecosricogniions comANSWERS TO EXERCISES Exercise - 1 (i) State ve * 9 values tee 8 gas the variables P, V and T are called state variables because their (i) Internal energy Tit bi sand Of the system and not on how this state has been reached. of components (a) ename ent eneray of a system is called it internal energy. It is made up coulombic energy bene 3 ranslation (b) energy of rotation, (c) eneray of vibration, (e) the particl n the electrons and nuclei in atoms and (e) energy of interaction of Paricles ofthe system. tis expressed in kimot 3. R 4. 394.7 Joule 5. 7200 cal 6. (8) 7 @) 8. (8) Exercise - 2 (2) The entropy of perfectly crystalline solid is zero at zero K. (b) In perfect crystals there is no randomness, hence entropy is zero at absolute zero. In imperfect crystals there is always some disorder hence entropy of imperfect crystals is more than the entropy of perfect crystals. (©) Relation between standard free energy change and equilibrium constant of reaction AG’ = -2.303RTlog,,K where K is the equilibrium constant. 2. (a) N,(g)+0, (g) > 2NO(g)is spontaneous AG is - and AH = + (endothermic) AG negative = AH-TaS For -ve value of AG , -TAS should be negative and AS should be +ve and TAS > AH (b) AG'=-2.303 x RT log K 2.303 x 8.314 x 400 log 1.958 x 10" 2.303 x 8.314 x 400 x (-4 + 0.2917) = -2.303 « 8.314 x 400 x -3.7082 =28.4KI (c) (i) Free energy is the energy of a system which can be converted into useful work. It is defined by the relation. G = H - TS where H is enthalpy, S is entropy and T is temperature in Kelvin scale. The concept of free energy explains the spontaneity of reactions, (ii) Though the spontaneity of a process can be predicted on the basis of enthalpy and entropy changes. For a spontaneous process AH should be negative and aS should be positive. When AHand AS oppose each other spontaneity of a reaction can only be decided by considering the value of free energy change AG . For reactions in which either AHis +ve or AS has ~ve values, for spontaneity the net value of AG should be -ve Megocosm Cogniions Pt Ud. $7, Kelv Saal Sorvaptva Vor, New Deh -1700 Websle www. megacosm:ogntons.com zmal : enquiyeimegacosmcogntins com3 dicates the melting point of the solid and T, indicates the boiling of the liquid. hows the increase in entropy with increase in temperature, info liquid the temperature of system does noy \ting because of the requirement of latent heat of fusion during the meting (i), Tain {ii) AB part of the curve st (il) BC par of the curve shows the change of solid change during mel of solid into liquid, 280, (9) +O, (g) = 250; (9) . 4,G° = AG; (Products) - AG’, (reactants) = [2 x -371] - [2 x ~ 300] = -142 kJmo! AG =142x1000____ 94.79 Now lod =" 303xRT 2303x8314 x300 K = Antilog (24.72) = 5.248 x 10% AH’ = 80.0 kJmol" AS = 120 JK"'mol* T=400K AG? = AH ~ TAS? = 80 x 1000 - 120 x 400 = 80,000 ~ 48,000 = 32000 J AG = 2.303 «RT log,oK —— 8S ___—=92000___ 4.47 = -5 40.822 2308x8.314%400 _2,303x8.314% 400 K = antilog (5.822) = 6.64 x 10° or, log K = For the reaction, Ag,O(s) > 2Ag(s) + 30 (9) AH = 30.56 kJmol" AS = 6.6 JK“‘mol when AG =0= AH-TAS AH _ 30.56%1000 Joule mol’ or T= AE. ROB ATOON Noule mot” = 4630.3 K As 6.6 JK ‘mol (A) (8) ‘SH of H2O = 2.257 Kg” = 2.257 x 18 KJmol? H,0(¢) = H,0(g) at 373 as,, - Ste. _ 2:257»18%1000 T 373 By unit conversions, all the options are correct, Hence, (D) is correct. = 108.9 Jmol'k~* Exercise - 3 (i) Standard free energy of formation of a compound is th 'e change of free en: kes place when one mole of a compound is formed from its elements in their Prec lol on is represented as AG? lard states. Megacoom Cogetos Pt, 57. Kv Sao Sepa Vier Hew Dei a01 Enon, eosonr@mege : ;coxmeagnitons com \Webate: www. megacormcogntions comcee (ll) CH, (@)+ 20, (g) + CO, (g) +2H,0() at 298 K. Let, AH. of CH, = x Byrelation AH... = LAH, of products) aH; of reactants 890.5 kJ = [-303.5 ~ 2 x 286) [x + 0] X= [-393.5 - 572] + 890.5 = -965.5 + 890.5 = -75.0 kJ AH, of CH, = ~75.0 kimot 2 AHpeu -29K Cal 3. ~ 326.44 kJ mole” CH, (8) +20, (g) -» CO, (g) + 2H,0(¢); AH’ = -890 kJ AH (reaction) = AH, (Products) ~ AH; (Reactants) = [4H, of CO, + 24H, (H,0)]~[aH, of CH, (9)] 890 kJ = | -393.5 + (2x ~ 285.9) ] - [AH, of CH,(Q)] oF, AH, of CH, = [-383.5~ 574.8] + 890 = -965.3 + 890 = -75.3 kJ Also by the relation AH’ = AE’ + AnRT (for combustion of CH,(g)) or, AE = AH - AnRT(An = 1-3 =-2) ~890 — (-2) x 8.314 x 298 = -890000 + 4955.14 = -885.044 kJmol" 5. -676 6. H=E+PV For final stage H, = E2 + PV and for initial stage H; = E, + PV ‘Substracting Hz — Hy = (Ez + PV2) ~ (E; + PV;) or, = Hp-H: = (Ez — Ex) + P(Vz Vi) or, AH = AE +PAV (i) Also, AE =q-PaV or, AE+PAV=, (i) From (i) and (ii) AH=a, 7. (A) 8 Resonance energy = (50.4 ~ 232.6) kJ / mol == 182.2 kJ mol! Hence, (A) is correct, ‘Since heat neutralization of strong acid and strong base is equal to the formation of water. i.e., NaOH + HCI — NaCl + HO +Q where Q = heat of neutralization => Na’ +OH +H" + Cl Na‘ + Cr +HO+Q =H'+OH > H.0+Q Hence, (A) is correctNCEPTS AT A GLANCE FORMULAE AN the syste 1. Internal energy: tis sum of al forms of energy of all he particles present In the system at a particular temperature. 2. First law of thermodynamics. SE=q+W 3. Enthalpy or heat constant H=E+PV AH= AE +PAV = AE+ An,RT 4. Heat capacity: It is defined as the quantity of heat required to raise the temperatuer of the system by one degree. q a 5 o(S) atc, -() 6. Work done in isothermal reversible process: We2 S03RTloge VE = -2.303nRTlogio= P, 7. Work done in adiabatic reversible expansion: R W=C(T2~T1) Sage) 8. Adiabatic relations PV" = constant Tv" = constant PU) = constant Bey and Cp-Cy=R where y = molar heat capacity ratio of gas. 9. Kirchoff’s equation AH, -AH,=AC,(T,-T,) (at constant pressure) AE, - AE, = AC, (T, -T,) (at constant volume) AC, = 3) Coyotes) ~ 2 Crna AC, = DCs) ~ ZCvencen) —— ‘Megacosm Coprion: Pid, 7, Kol Sorat Sarvapiva Vinar, New De -11016, Email: enqueyemegacosmcogntions com Webeie wir megacosmeogniions.com10. Entropy: Entropy is thermodynamic quantity which is a measurement of the randomness or disorders of the molecules of the system a4 as=t Spontaneous process AS... >0 Non-spontaneous process AS... <0 At equilibrium AS)... =0 41. Second law of thermodynamics: It states that the entropy of universe is always increasing in the course of every spontaneous Process. 12, Gibb’s energy: G = H-TS 57. Kalu Sara Sarvoptiya Vihar, New Det -110016, Ema: enquryemegacosmcogntons com Website" www megacosmcegntons.com1d exoth 1 how that the reaction CO(g) + 40x(g) ——> CO2(g) at 300 K is spontaneous an = When standard entropy ate Food) or? She standard Gibbs free energy of format; forCO, and CO are -394.4 and -137.2 KJ mol’, respectively. { A 1.00 L sample of a mixture of methane gas and oxygen, measured at 25°C and 740 torr Pressure, was allowed to react at constant pressure in a calorimeter re ae with its contents, had a heat capacity of 1260 cal/K. The complete combustion of the methane to carbon dioxide and liquid water caused a temperature rise in the calorimeter of 0.667 K. What was the mol percent of CH. in the original mixture? [Heom» for CH4(Q) = -210.8 keal/mol,] LY Calculate the heat of following gaseous reaction CH, + 4F2 > CFs +4HF the bond energy OfC-H, F—F, C-F and H-F bonds are 99.3, 38, 116 and 135 KCal/mole respectively \ 4,” The heat of reaction for Nz + 3Hz ——> 2NH) at 27°C is -91.94 KJ. What will be its value at $8°C? The molar heat capacities at constant pressure and 27°C for Nz, Hz and NH; are ‘45, 28.32 and 37.07 joule respectively. Calculate W and g for the isothermal reversible expansion of one mole of an ideal gas from an injial pressure of 1.0 bar to a final pressure of 0.1 bar at a constant temperature of 273 K. ‘ingle Correct One mole of an ideal gas is allowed to expand reversibly and adiabatically from a temperature of 27°C. If the work done by the gas during the process is 3 kJ, the final temperature will be equal to (Gy =20JK") (A) 150K (8) 100K (C) 26.85 K (D) 295K When Zn dust is added to sufficiently large volume of aqueous solution of copper sulphate. 3.175 g of copper metal and 20 J of heat is evolved. The AH for the reaction Zn(s) + CuSO, (aq) ——> ZnSO,(aq) + Cu(s) is (at. Wt. of Zn = 65.3, at wt of Cu = 63.5) (A) 205 (B) 2004 (C)4000 (0) 65.35 wo Which has maximum intemal energy at 290k? (A) Neon gas (8) Nitrogen gas ‘Ozone gas (D) Equal Chloroform has AH,»5 = 29.2 Ki/ mol and boiling point 61.2°C. What is AS,a, of chloroform? (A)/977.1 Jk" mol” (B) 1242 Jk" mor" - 87.3" mor" 7.3. Jk! mol" (19 A 'system is provided 50 joule of heat and werk done on the system is 10 J. The change in L internal energy during the process is: wa 60J (A) 40d (C) 80d (0) 50J #8 PV Ud. 57 Kal Sel, Sarvapriva Vita, New Deb-11014, Emel: enguryemegecesmcogmmenrcom Megecosm Cognit Website: www: megacosmcognsions cam19 TNT thy VF oat done during the process when 1 mole of gas is allowed to expand freely into vacuum is: C (8) +ve (we (0) all of these An ideal gas expands against a to 40L SORDS 10K) of sane @ constant external pressure of 2.0 atmospheres from 20L (A) 4062 al from surrounding. What is the change in internal energy of the system? \(B)-5947 J (©) 140825 (0) 8940 J Ja” 1 mole of an ideal gas at 25°C is subjected to expand reversibly ten times of its intial volume. t Tho change in entropy of expansion is UA) 19.18 JK"! mot ' (B) 16.15 JK mol (C) 22.18 JK* mot (D) None of these Standard free energy changes at 2000 K are as shown below: Reaction AG°(kJ mol") [40 | 2Mg(s) + 0,49) —>2Mg0(s) 2Nis)+0,(g) 26048) 22Zn(s) + 0,(g)—>2Zn0(s) At 200 K, which of the following is/are feasible? (A) Reduction of MgO by Zn (8) Reduction of zinc oxide by nickel 4(C) Oxidation of magnesium by nickel oxide (D) Oxidation of nickel by zinc oxide Calculate the work done (in J) when 4.5 g HO; reacts against a pressure of taim at 25°C 2H,0, (¢) —0,(g)+H,0(6) (A) - 1.63 x 10? (B) 4.5 x 10° (C) 3.2 10? (D) - 6.1 x 107 snore Pt. $7, Kal Sara, Srvapriva Vihar, New Delhi -110016, Emil: enqury@megacosmcogniion: com Website: www magecosmeegniiens comSC WGUNRE OMI, 1/ Calculate the standard heat of fration of CS). Given thatthe standard heat of combustions of carbon(s), sulphur(s) & CS,(I) are -393,3, -293.72 & -1108.76 kmol 2 The bond dissociation energy of gaseous Hs, Cl and HCI are 104, 58, and 103 kcal mor! respectively. Calculate the enthalpy of formation for HC! gas. a AAn intimate mixture of FeO, and Al s used as solid rocket fuel, Calculate the fuel value per gram and per ml of mixture. AH... =399.0 kcal AH,,., = 199.0 kcal, density of FeO; and Al are _-52 alml and 2.7 giml respectively. \ A Find the enthalpy of S-S bond from the following data () CHs-S-CHs(g) AH? = ~147.2 kJ mol” Ml) CeHe-S-S-CoHe(a) AHP = -201.9 kJ mol (il) Enthalpy of atomisation of sulphur = +222.8 kJ mol”! 5. The enthalpy of formation of H,O(\) is -285.7 kJ mol” and enthalpy of neutralization of a strong iu acid and a strong base is ~57.6 kJ mol’. What s the enthalpy of formation of OH” ions? AHY = 0.0K Determine the enthalpy of the reaction - CHa) + Hag) > Coty) +CHyg) at 25°C, using the given enthalpy of combustion values under standard conditions. Compound Hag) CH) CoH) C(graphite) AHP /kJ mot ~285.8 -890.0 ~1560.0 -393.5 standard enthalpy of formation of CsHa) is 103.8 kJ / mole | 7/7 Calculate the heat of dissociation of NO, into NO» from the data ‘s Nz + Op > 2NO; AH = 43.1 kcal Not 202—>NzOx; AH = ~1.87 kcal 2 > 2NO + O; AH = 26.1 kcal 8. 7 At 400K, the standard enthalpies of formation of CxHsCOOH(s), CO,(g) and H,0(\) are ~408, 393 and -286 kJ mot" respectively. Caloulate the heat of combustion of benzoic acid at () stant pressure and (ii) constant volume (R = 8.31 J mole K") From the following data, calculate the enthalpy change for the combustion of cyclopropane at 298 K. The enthalpy of formation of CO,(g), H-0()) and propene (g) are - 393.5, — 285.8 and 20.42 kJ mpl" respectively. The enthalpy of isomerisation of cyclopropane to Propene is — 33.0 kJ mol” 10“ Heat of formation of propene is ~21 kcal/mol. Heat of sublimation C(graphite) is 170 kcal, Bond \ energies of C-H, H-H and C-C bonds are 99, 104 and 80 kcal respectively. Caloulate, bond energy of C=C in propene. The heat of combustion of acetylene is 312 kcal. If heat of formation of CO, and H,O are 94.38 and 68.38 kcal respectively, calculate C=C bond energy. Given that heat of atomization of C and Hare 150.0 and 51.5 kcal respectively and C-H bond energy is 93.64 kcal hi-110016, Emel: enguiysimegacosmcogniins com Websie- www.megacosmeognitons.com4 ae 7 snaximum calorific output, a burner should have an optimum fuel to oxygen ratio ean aa 7 . 3 times as much oxygen as is required theoretically for complete Of Chl and 6X Mee a ume® wihich has been adjusted for methane as fuel (with X ire / hour calorie output, what 1Our of O2) is to be readjusted for butane, CyH;o. In order to get the same to yncomplete cone Should be the rate of supply of butane and oxygen? Assume that losses due Shes Of com ereustion, etc are same for both the fuels and gases behave ideally y, ‘ombustion: CH, = 809 kJ / mol, C4Hyo = 2878 kJ / mol. / 13/_ The polymerization of ethylene to linear polyethylene is represented by the following reaction VV nCH, = CHa —» (-CH,—CH»~), (n= large integer value) Calculate the enthalpy of polymerization per mol of ethylene 298 K if average enthalpies of bond dissociation for C = C and C - C are §90 and 331 kJ mol” respectively. , 14 Determine the resonance energy of gaseous benzene from the following data HAH sos (Hes @) = 436.9 kd mol", AH’, (C, graphite) = 718.4 kJ mol’, AH; (Benzene, g) = 82.9 {J mot "| BEc 4 = 416.3 kd mol ', BEc.c = 331.4 kJ mol ' and BEo-c = 591.3 kJ mol” , 15. Dvd moles of a perfect gas undergo the following processes: \__-@) a reversible isobaric expansion from (1.0 atm, 20.0 L) to (1.0 atm, 40.0 L) ~~ (b) a reversible isochoric change of state from (1.0 atm, 40.0 L) to (0.5 atm, 40.0 L) (c) a reversible isothermal compression from (0.5 atm, 40.0 L) to (1.0 atm, 20.0 L) (i) Sketch with labels each of the processes on the same P-V diagram (i) Calculate the total work (w) and the total heat change (q) involved in the above processes. (ii) What will be the values of AU, AH and AS for the overall process? PART-B Multiple Choice Questions (Single Option Correct) 1 in which case mixing of a strong acid and a strong base each of 1 N concentration, temperature L--~increase is highest? (A) 20 ml acid — 30 mi alkali (8) 40 mi acid ~ 40 mi alkali (C) 25 ml acid — 25 mi alkali (D) 35 ml acid - 15 mi alkali / ate heat of combustion of carbon is 394 kJ/mol. The heat evolved in combustion of C 6.023 x 10” atoms of carbon is (a) 3 (8) 394.0 kJ _ bse (D) 0.394 kJ 3. {ual volumes of CH, & H, are combusted under identical condition. The ratio of heat evolved ) for Coty & He is i H,(g) + 1/2. O2{g) > H:0(9) AH = -241.8 kd C2HQ(g) + 5/2 O2(g) > 2CO2(g) + H20(9), AH = 1300 kJ (A) 5.37/1 (8) 115.37 (c)1n (D) None of these 4 Equal volume of 1M HCI and 1M H,SO, are neutralized by dil. NaOH solution liberating x and y “—~— Kcal heat. Then (A) xzy (B) x=05y (C)x=04y (D) None of these r Tosvovs Pv) tls. 57 Kalu Sorai Sorvoprya Vihar New Deh -110016, Email: enqukyémegacormcagniions com Webste www megacosm2gnitions com