'Y an ds Principles and nh foations Avcc-98710007614Chemical Thermodynamics ‘The study of heat or any other form of energy into or out of a system, due to physical or chemical transformations is called chemical thermodynamics. System and Surroundings A system is the specific portion which is under thermodynamic studies. tom, the rest of the universe, i. all other matter that can interact stem is ealled surroundings. ‘The real (like, beaker or test tube) or imaginary (like coordinate axis) surfaces or lines separating two oF more systems ora system from ite surrounding called boundary, The boundary may be diathermic (ie. allow passage of heat) or adiabatic (1. does not allow passage of heat). System 3 bouncy Representation of sytorr sunoundg end bourdary ‘Types of System Depending upon the nature of boundary, the system ean be of fellowing types @) Open system An open system can exchange matter as well as energy with its surroundings. The boundary here is not sealed and non-insulated thermally. For such a system, Am # 0, AH #0. IN THIS CHAPTER... «system and Suroundings + Work + Zercih Law of Thermodynamics « First Law of Thermodynamics Enthalpy and Enthalpy Change Heat Capacity + Hess's La of Constant Heat Summation Eniropy + Second Law of Thermodynamics Third Laws of Thermodynamics + Gibbs Pree Energy(ii) Closed system A closed system does not exchange matter with its surroundings. However, it can exchange energy in the form of heat, work or radiations, ie. the boundary is sealed but not insulated, e.g. hot water kept in a closed container. For such a system, Am = 0, AE #0. (iii) Isolated system An isolated system neither exchange matter nor energy with urroundings, or we can SAY the boundary of this system is sealed as well as insulated, e.g. thermosflask. For such a system, Am = 0,AE = 0, Macroscopic Properties The properties of the system which arises from the collective behaviour of large number of species are called macroscopic properties. These properties are pressure, temperature, volume, mass, refractive index, surface tension, viscosity, density etc. These are of two types (i) Intensive properties The properties which do not depend upon the quantity of matter are called intensive properties, e.g. pressure, temperature, density, concentration, surface tension, viscosity, refractive index etc. (i) Extensive properties The properties which depend upon the quantity of matter are called extensive properties, e.g. volume, number of moles, enthalpy, entropy, mass, work etc, ‘The above properties can be best understood by the following example. If at a certain temperature, a solution is taken in a beaker. Then a partition is inserted in the beaker in such a way that it divides the solution into two halves. In that case, the volume of the solution becomes half while temperature of cach part remains the same. It is obvious, temperature is an intensive property while volume is an extensive property. It may be noted that the ratio of the two extensive properties becomes intensive in nature, e.g. mass and volume are extensive properties, but the ratio of mass and volume, i.e. density is intensive. It is independent of quantity of matter. Similarly, heat capacity is extensive, but molar heat capacity is intensive. In general, if xis any extensive property of n moles of system, the molar property of the system x» is intensive. This is so because it refers to the property of 1 mole of the system and is independent of the quantity of matter x,, = x/n. Intensive properties cannot be added or subtracted directly. Only extensive properties can be added or subtracted. State Variables A thermodynamic system is said to be in certain state when all of its properties are fixed. These properties are measurable and have a definite value. If any of such properties changes, then the state of system also changes.The measurable properties here are called state variables, e.g. temperature, pressure, volume, composition, number of moles, internal energy, entropy, enthalpy, free energy, etc. State and Path Functions (State Functions The functions of a system whose value depends only upon the state of the system initial and final state). These are independent of the path or manner by which the state is reached are called the state function. Thus, most of the common variables are infact state functions. Examples of state functions are pressure, volume, temperature, internal energy. enthalpy, entropy etc. (i) Path Functions The functions that depend upon tht path followed are called path functions, e.g. work done, heat etc. Thermodynamic Processes ‘The state of a variable can be changed via a thermodynami: process. These processes are of the following types (@ Adiabatic process In this process, the system does not exchange heat with its surroundings, ie. no heat can flow in or out of the system. For an adiabatic process, dq = 0 Gi) Isothermal process This process is carried out at constant temperature. For an isothermal process, dT=0 and thus, AE =0 Here, heat can flow from the system to surroundings and vice-versa in order to keep the temperature of thi ‘stem constant. dq = 5W (iii) Isobaric process In this process, change of state is brought about at constant pressure, ie. dp= 0 (iv) Isochoric process In this process, volumes of the system remains constant, i.e. dV=0 ‘The above four basic thermodynamic processes can be represented in a graph as, Isobaric o Isothermal Isochoric v— pV graph for various thermodynamic processes (v) Cyclic process When a system is undergone a number of different states and finally returns to its initial state, the process is called cyclic. For such a process, change in internal energy (dE or dV) and change in enthalpy is zero. i.e. dE = 0and dH = 0For example, in a process shown below, the system returns to the original state A after successive changes. A(p,,V,.7,) — Bl p,.Ve,T,) —> Clpy.Vq.T2) — A(p,.Vi.T;) (vi) Reversible and irreversible processes Reversible process are the process which takes place infinitesimally slowly or an ideal process which takes infinite time for its completion. The direction of these process can be reversed at any point of time. Such a process is an ideal process where every intermediate state is in equilibrium with others. This means in the reversible process, system can be brought back to initial state without leaving any effect on the surroundings. Irreversible process whose direction cannot be reversed by small change in variables. All naturally occurring processes are irreversible. Difference between Reversible and Irreversible Process Reversible process Irreversible process Itis an ideal process which _It take finite time for completion. takes infinite time for completion. ‘At any stage during the Equilibrium exists enly in the process equilibrium is not begining and at the completion disturbed. stage. Work obtained is maximum in Work obtained in the process is this process. ot maximum. In this process the opposing _In this process, there is large force and driving force differ _ difference between the driving only by infinitesimally small and opposing force. magnitude. ‘These processes are only ‘These processes actually occur in imaginary and can not be native. achieved in actual practice. Example I. identify the adiabatic steps in the following cyclic process. Temperature at A, B and F is T, and at C, D and Eis T. Given, T, > T, @WFrADGE O)B>CGE>F (B>GC>+D @A>BESE Sol, (b) (i) A + B (Temperature and pressure are constant). Its isothermal and isobaric process. Gi) B + C Mis adiabatic expansion in which temperature falls from T, and T,. (iii) C > D Clemperature and volume are constant) =. This process is isothermal and isochoric.(iv) D > E (Temperature and pressure are constant) + Itis isothermal and isobaric contraction. (v)_ E> F (tts adiabatic compression in which temperature increases from T, to T,). (vi) F > A (Temperature and volume are constant). « Itis isothermal and isochoric process. Thermodynamic Equilibrium A system is said to be in a state of thermodynamic equilibrium if its macroscopic properties do not change with time. There is no exchange of matter and energy with in the system or at its boundaries. It is if thermodynamic equilibrium following three equilibria exists simultaneously + Mechanical equilibrium, i.e. when net work is done on the system or by the system is zero. + Thermal equilibrium, i.e. temperature remains constant throughout the system including the surroundings. + Chemical equilibrium, i.e. change in the composition of the system remains constant and definite. Work + Ifan object is displaced through a distance dx by a force F, the amount of work done is given by, W=Fxdx i.e. work is the product of two factors (i) Intensity factor, F (i) Capacity factor, dx + Work done is a path function, not a state function, as it depends upon the path followed. + Work done on the system increases the energy of the system and is taken as positive while work done by the system is taken as negative. i.e. work done by the system = - ve work done on the system = + ve Work Done in Isothermal Irreversible Expansion or Compression + Inan isothermal irreversible expansion, the total work done by the system can be obtained by integrating - pdV when its volume changes from V, to V, at constant external pressure, i.e. v Wa-fi Pex dV + Geometrically, the magnitude of work done represents the area bounded between the curve p= f(V)and volume axis from V, to V..+ The mechanical work is considered as expansion GfAV > O)or contraction (if AV< 0). Thus, Wespansion i8 negative and Weoniraction i8 positive. pay >. Yaka Imeversible work dore: Work Done in Isothermal Reversible Expansion or Compression of an Ideal Gas Work done, when gas expands through a small (volume) dV against the external pressure py is given by ‘for ‘% y For isothermal expansion, T = constant So, W =~ nRT In¥2 Y, W =- pydV =- av or = - 2303 ART log ¥2 v or =~ 2903nRT log 2 Pr Also, reversible work of expansion is the maximum work and reversible work of compression is the minimum work, (because no frictional losses are considered and hence no loss of energy). In an expansion process, the external pressure is always less than the pressure of the system, ie. Pe.)=(Ant dp). Such processes are called reversible processes. W,., is Maximum Work Work done during isothermal expansion of an ideal g: given by the equation, W=- py AV Now, for a given change of volume (AV), W can be maximum if pex: is maximum. But for expansion pox has to be smaller than pq. This means that for getting maximum work, the external pressure has to be infinitesimally smaller than the internal pressure of the gas. These conditions are nearly close to reversibility. Thus, for a given change of volume Werey = Winx Free Expansion Expansion of a gas in vacuum (px: = 0) is callled free expansion. No work is done during free expansion (i.e.W = 0) of an ideal gas whether the process is reversible or irreversible.Remember + The magnitude of work in isothermal irreversible expansion increases as the number of step involved increases. ‘The magnitude of work will be more in isothermal irreversible compression than isothermal reversible compression, for the same change in volume. The magnitude of work decreases as the number of steps involved increases. Work Done in Adiabatic Expansion or Compression Processes In adiabatic expansion, no heat is allowed to enter or leave the system, hence dq = 0. .. From first law of thermodynamics AE = W. The molar heat capacity at constant volume of an ideal gas is given dE ty «= (3), or dE=C,-dT and for finite changes, AE = Cy x AT = W @ Work done in reversible a¢ Let work done by the system is, W=- pdv For very small change in a reversible process and for ‘one mole of a gas, batic expansion Here, p= internal pressure AV = increase in volume AT = fall in temperature Cy = heat capacity at constant volume R= gas constant Y=C,/C, C, = heat capacity at constant pressure (ii) Work done in irreversible adiabatic expansion In free expansion, the external pressure is zero, i.e. work done is zero. AE=W=0 In intermediate expansion, suppose the pressure is suddenly released to 1 atm and the gas expands adiabatically against the constant pressure. Since, this is not a reversible expansion, above ‘equation. dq=0,AE=W W =C,(T; - T,)(can be used)Let the volume changes from V, to V2 against external Pressure, Pose, W =- Pow (V.-V) - (42 Rn) sey s| PP :, Work done, W =~ Rpext (22 = Za) Pr Remember + The temperature of gas decreases in adiabatic expansion, i.e. cooling occurs and increases in adiabatic compression G.e., the system gots warmed). + In any adiabatic process (expansion or compression), the final temperature of the gas in reversible process is lower than that in irreversible process. + Isobaric process, W = ~ Peg (V2 ~ V;) Example 2. The pressure-volume work for an ideal gas can be calculated by using the expression W =~ [" p.., dV. The work can also be calculated from the pV-plot by using the area under the curve within the specified limits. When an ideal gas is compressed (a) reversibly and (b) irreversibly from volume V, to V;, choose the correct option. (NCERT Exemplar) (a) W (reversible) = W (irreversible) tb) W (reversible) < W (irreversible) (C) W (reversible) > W (irreversible) (d) W (reversible) = W (irreversible) + py" AV ‘Sol. (b) W (reversible) < W (irreversible) This is because area under the curve is always more in irreversible compression as can be seen from Fig. (a) and (b). Pressure Pressure Vi Volume —> V, Vy volume —> v, (a) Reversible compression () Irreversible compression Example 3. A system consisting of 1 mole of an ideal gas undergoes an isothermal expansion at 25°C from 1.0 bar to a lower pressure while generating 100 } of work. What is the final pressure of the system if the external pressure is constant at 0.1 bar? (a) 1.23 bar (b) 0.712 bar (c) 0.958 bar (d) 0.664 barle Sol. (b) W =—Pex(V2— Yi) (= nRT) =— Peal ——-——} Pr op) -- tna =) Pr Pi) (2 1) or, —100 =-1 x8.314 x 298 x0.1| —-- pv p; =0.712 bar Example 4. When 50 g iron reacts with hydrochloric acid in an open beaker at 25°C, work done is (a) + 2212.2) (b) 22.122) (-2212.2) (d) — 221.22) Sol, (c) Fe(s) + 2HCI(aq) —> FeCl,(aq) + H,(g) Vol Vmod No. of moles of iron = We know, W =~ Pa:AV AV = Vinat — Virtiat AV =Vpnay (Here, Vinnis =O) Va ae Pp. =~ 0.8929 x 8.314x 298 = 2212.2) Heat Heat is defined as, the quantity of energy, which flows between system and surroundings on account of temperature difference. It is also a path function, i.e. depends upon the path followed. It is given as, Q= msAt where, m = mass of substance, s = specific heat At = temperature difference Heat flowing into the system is taken as positive and heat flowing out of the system is taken as negative. When heat is produced or evolved, the system is called exothermic system and when heat is absorbed, the system is called endothermic system. Heat is expressed in terms of Joules or calories. 1 calorie = 4.18 Joules} Difference between Heat and Work When heat is supplied to a gas in a system, the molecules start moving faster with greater randomness in different directions.However, when work is done on the system then the molecules start moving down in the direction of the piston. Thus, work is an organised form of energy while heat is a random form of energy. Zeroth Law of Thermodynamics According to this law, “when two objects (maintained at different temperatures) are brought in thermal contact, they exchange heat with each other until they reach a state of thermal equilibrium”. The heat flows always from the object of higher temperature to the object of lower temperature. At thermal equilibrium, the temperature of both of them became same. This idea of thermal equilibrium is called zeroth law of thermodynamics or law of temperature or law of thermal equilibrium. This law is also applicable for more than two objects. In such a condition, it states “if each of the two objects is in thermal equilibrium with a third object then they are also in thermal equilibrium with each other.” Internal Energy Every system is associated with a definite amount of energy, called the internal energy of the system. + Itis the sum of all forms of kinetic and potential energies that it can have under specified conditions, ie. translational, vibrational, rotational, chemical bond energy, etc. The gravitational energy is usually neglected. + Internal energy is a state function, i.e. depends only upon the state of the system. + It is independent of the method by which state has been attained. + The absolute value of internal energy can't be determined. However, change in internal energy can be determined experimentally using a bomb calorimeter. + The change in internal energy is the difference between the internal energies of the products E, or E, and that of reactants, E, or Eg AE=E, -E; + Internal energy of a system depends upon the quantity of substance contained in the system. Hence, it is an extensive property. + The internal energy of ideal gases is a function of temperature only. Hence, in isothermal processes, as the temperature remains constant, there is no change in internal energy, i.e. AE=0+ By convention the internal energy of an element, in most stable form, is zero. + Unit of E The units of energy are ergs (CGS units) or Joules (SI units). TeV = 1602x105 Leal = 4.1844 Lcal = 4.184x 10" erg 1 J= 0.2390 cal 1d= 10" erg 1J= 1N m (Newton-metre), 1Latm= 101.3) = 24.206 cal, thus, 1 cal > 1joule > lerg > 1 eV + The change in internal energy can be brought about in following two ways (i Either by allowing the heat to flow into the system (absorption) or out of the system (evolution). (ii) By doing work on the system or the work is done by the system. First Law of Thermodynamics The first law of thermodynamics given by Helmholtz and Robert Mayer is similar to the law of conservation of energy. The law states “energy can neither be created nor be destroyed although it can be changed from one form to another”. + It is impossible to construct a perpetual motion machine which could produce work without consuming energy. + The total energy of an isolated system remains constant though it may change from one form to another. + Whenever a quantity of one kind of energy disappears, an exactly equivalent quantity of energy in some other form must appear. + Total energy of the universe in constant. + Limitation The major limitation of first law of thermodynamics is that it does not provide any information about the feasibility of a reaction on process. Mathematical Expression of First Law of Thermodynamics Suppose a system consumes heat (q) and work (W) is done on the system. In this process, the internal energy changes from E, to E, then AE=q+W — where, AE=(E, - &)It is the mathematical expression of first law of thermodynamics. + When a system undergoes isothermal change AE = 0, i.e. there is no increase or decrease in the internal energy of the system, then the first law of thermodynamics reduces to O=qg+W or q=-W i.e. heat absorbed from surroundings = Work done by the system or W=-q Heat given to the surroundings = work done on the system + If no work is done, W = Oand the first law reduces to AE=q i.e. increase in internal energy of the system is equal to the heat absorbed by the system or decrease in internal energy of the system is equal to heat lost by the system. + If there is no exchange of heat between the system and surroundings, q=0, the first law reduces to AE=W ite. work is done at the expense of internal energy. + In case of gaseous system, if a gas expands against the constant external pressure, p, let the volume change be AV, the mechanical work done by the gas is equal to ~ px AV + For cyclic process AV = 0, since system returns to its original position. Here, q = - W. Remember According to old conventions AE = q-W , but according to latest convention, by first law of thermodynamics AE = q+ W (Work done on the system is taken as positive). Example 5. A system undergoes a certain change in state by path J and the corresponding heat absorbed and work done are 10 kcal and 0 erg, respectively. For the same change in state by path il, the respective quantities are 11 kcal and 0.5 Wrax, Where Wrax represents the work done if the change were reversibly carried out. Find the magnitude of Wrrax if erg. fa) 2 (b) 8.4x107 (©) 8.4x10'° (d) 8.41077 Sol. (c) As internal energy is a state function, its change is independent from path and hence, AU, = AU, or, a + Wi =ay + or, 10 +0 =11+0.5Way | Wax | = 2 keal = 2 x1000 x 4.2 x107 =8.4x10" ergEnthalpy (H) and Enthalpy Change (AH) The total heat content of a system at constant pressure is called the enthalpy of the system. Indeed, it is the sum of internal energy and the product of pressure-volume, ie. work. It is an extensive quantity and represented by the symbol H. “ H=E+ pv @) Its units are keal or kJ/mol. Enthalpy change (AH) of a system is equal to the heat absorbed or evolved by the system at constant pressure. Enthalpy change accompanying a process may also be defined as the sum of the increase in internal energy of the system and pressure-volume work done. Like internal energy. The absolute value of enthalpy of a substance or system cannot be measured. However, in thermodynamic processes, change in enthalpy can be measured experimentally. ‘Suppose a system absorbs heat, q, and its volume changes from V, to V, against a constant pressure, p, the work done by the system, IfAV = 0,80 AH and as oH Hence, AE=q,, Here, qy = heat supplied at constant volume ‘Thus, we can say that “heat supplied at constant pressure is the measure of enthalpy change, while the heat supplied at constant volume is the measure of internal energy change.” Relationship between AH and AE The difference in AH and AE is insignificant for solids and liquids. However in the case of gases, if pressure and temperature remain constant, then for a given thermochemical equation, (i.e. the chemical reactions in which heat of the reaction and state of the substance taking part are mentioned) change in number of moles, An =n, — So, the above equation, i.e. AH = AE + pAV can be converted to If, Case 1 when An, = Othen AH = AE Case I when An, < Othen AH < AE Case III when An, > Othen AH > AE Enthalpy of Reaction “The enthalpy change of a reaction can be defined as the amount of heat absorbed or evolved at constant AH =AE+ 4n,RT — (: pSV = An, RT)pressure when the quantities of substance indicated by thermochemical equation have completely reacted.” e.g. In the reaction, CH,(g) + 20,(g¢) —> CO,(g) + 2H,0(g); AH = - 890.3 kJ Thus, heat of reaction for the above reaction is -890.3 kJ or in other words if 1 mole of CH, combines with 2 moles of O, in gaseous state, 890.3 kd of energy is liberated Enthalpy can also be defined as “the energy stored in the system which is available for conversion into heat.” If AH is positive, + the process will be endothermic. + or process is accompany with the absorption of heat. + or the heat content of the product (Hp) is lesser than that of the reactant (Hg). + or product is more stable than the reactant... IfAH is negative, + the process will be exthermic. + or the process proceeds with the evolution of heat. + or the heat content of the reactant (Hg) is lesser than that of the product (Hp). Example 6. The reaction of cyanamide, NH;CN(s), with dioxygen was carried out in a bomb calorimeter, and AU was found to be -742.7 k| mol" at 298 K. Calculate the enthalpy change for the reaction at 298 K (R= 8.314107 kK) K! mol") NH,CNO + 30412) —> Nig) + CO,(g) + 1,00) (a) -741.46 (b) -743.9 (©) +741.46 (d) + 743.9 ‘Sol. (a) Use the following steps to solve out such problems Step 1 Write the balanced equation NH,CN9) + 3048) — Nig) + CONg) + HOW) Step Mt Calculate An, Difference of moles of gaseous products and reactants, 301 An, np -9, #2-3 = 5 =0.5mol Step IML Calculate AH by using the formula AH = AE + AnRT AH = AE + AnRT AH =-742.7k)mol" + (0.5 mol x 8.314 x10- Kimo!” 298K) AH =(-742.7k) + 1238.786 x10™ kj) mol =-741.46kjmol" During calculation always remember the units of different quantities, i.e. AH, AE and R must be the same. Note In the laboratory most of the reactions are carried ‘out at constant pressure, so AH is more significant than A.Example 7. Given : Coaptise + Ox(¢)—> CO,(8); AH?= - 393.5 kj mol 30,00+ H,(g)—> HOU); AH? = - 2858 kJ CO,(g) + 2H,01!) —s CH,(g)+ 20g); AH® = + 8903 kj Based on the above, the value of AH® at 298 K for the reaction : Cegraphito + 2H3(] —> CH,(g) will be (a) 78.8 kJ mol" (b) + 144.0 kJ mol (= 74.8 kj mol” (-144.0 Sol, (c) AHeo, =~ 393.5 M mol”, Ayo =~ 285.8 ki mol ' HG, = 0 (Element formation) 2 AH? for CH, 890.3 = [AHoy, + 24HG,1-[4He0, + 24Hi,o] 890.3 = [AH¢n, + 0]-[-3935 + 2x 2855] * AHey, = - 748 kV/mol Standard Enthalpy of Reaction At 1 bar pressure and 298 K, a substance is said to be in its standard state. Hence, when the reaction is carried out at standard conditions, its enthalpy change is called standard enthalpy of the reaction. It is denoted by 4,1". ‘The sign of A,H® gets reversed on reversing a chemical ‘equation. Factors Affecting Enthalpy of Reaction The heat or enthalpy of reaction depends upon the following factors + Physical state of reactants and products. + Allotropic forms of elements involved. + Chemical composition of reactants and products. + Amount of reactants, + Temperature. + Medium of reaction. ‘The variation of enthalpy of reaction with temperature is given by Kirehhoff's equation. Case I When AC, is constant between two temperature T, andT, AH, ~ AH, = AC,(T.-T,) wl) AE, ~ AE, = ACy -(T, ~ T) == ii) Eqs. (i) and (ii) are known as Kirchhoff's equations. Case II AC, varies with temperature AH = AHy + [Ac, dT we. (iii) where, AH, refers to the enthalpy change at absolute zero. Pt ; or AH =AHg +00 +B +> wiv) Eqs. Gi) and (iv) are another forms of Kirchhoff equation.Calculation of Enthalpy of the Reaction Calorimeter is the apparatus which is used to measure the heat of the reaction experimentally. If we know water equivalent of the calorimeter (W), mass (m) and specific heat (s) of liquid and initial and final temperature of the calorimeter, the heat of the reaction is calculated as Q=W + m)xsx(T)-T) ‘Two common types of calorimeters are water calorimeter and bomb calorimeter. + In water calorimeter pressure remains constant, thus it gives the heat at constant pressure, i.e. AH. + In bomb calorimeter, the volume remains constant, thus the heat, measured by it, is called the heat at constant volume (i.e. gy) or AE. Ag = W+ mT, -T)xs oa x M kcal Here, w, = mass of substance taken and M = molecular mass of the substance a Ags CXAT XM uy where, C = thermal capacity of calorimeter Example 8. 0.16 g of methane is subjected to combustion at 27°C in bomb calorimeter system. The temperature of the calorimeter system (including water) was found to rise by 0.5°C. Calculate the heat of combustion of methane (in k} mol”) at constant volume. The thermal capacity of the calorimeter system is 17.7 kj K7'. (a) -695 (b) -1703 (c) -890 (d) -885 Sol. (d) For bomb calorimeter, AE =Car (In bomb calorimeter V remains constant) 7.7% 0.5x 16 0.16 Thus, the heat produced is qy, ie. qy = ~ 885K) Enthalpy of Formation ‘The enthalpy change when one mole of a compound is formed from its elements in their most stable state of aggregation, is called enthalpy of formation. It is denoted by A,H, e.g. C(graphite) + 2H.(g) —> CH,(g); 4,H =-74.8kd ‘The above enthalpy change under standard conditions (1 atm and 298 K) is called standard heat of formation and is denoted by A,H®. Enthalpy of formation of an element at standard state (or in its most stable state) by convention is taken as zero, e.g. enthalpy of formation of Mg, Al, NaH», O2, F,,etc., is taken as zero. = 885 k)/molExample 9. Given, KOH{(aq) + HCl’aq) —>KCl(aq) + H,0() AH = -57.3kjmol" ... () H.@ + $0218) — HO) AH = ~ 286.2 ki mol"... (i) tH + ic,@ —, HClaq)AH = - 1644 kj mol” ...(i) Kis + $0.08)+3 H, (g) + ag —> KOH (aq; AH = - 487.4kI mol” ..(iv) KCI(s) + ag—> KCl (aq), AH = + 18.4 kj mol wo W) Heat of formation of KCI will be (a) ~ 44.13 kJ mol" (b) - 441.3 Ki mol! (c)+ 441.3 kJ mol"! (d) - 4413 kj mol"! Sol. (b) Adding given equation (iii) and (iv) and subtracting equation (v), we get Kig+ 5cue) + HAg)+ ; Ofg) —> KCI(s) + HCliaq) + KOH - KCI(aq) ...vi) AH =~ 487.4 + (- 164.4)- (18.4) =~ 670.2 kj mol! We have to find, K(9) + 3ol48) —> KCH(9) (7); AH =? ‘Add equation (i) to (vii) and subtract eq. (ii) from their sum : This will give, K (3) + 30h (g)— KCI (9 SH = - 6702 +573 -(-2862) =— 441.3 kj mol” Enthalpy of Fusion The enthalpy change when one mole of a solid substance is converted into its liquid state at its melting point is called the enthalpy of fusion (A,,,H). Ionic solids have high values of A,,,H as compared to molecular solids. Enthalpy of Vaporisation The enthalpy change that accompanies vaporisation of one mole of a liquid at its boiling point is called the enthalpy of vaporisation (4,,,#). High value of enthalpy of vaporisation shows the presence of stronger forces of attraction. Enthalpy of Sublimation It is defined as “the enthalpy change when one mole of a solid sublimes (i.e. converts directly into gaseous state) at a temperature below its melting point”. It is represented by A, yl. sav = Stull + Mvp Enthalpy of Combustion The amount of heat evolved or absorbed when one mole of the substance is completely burnt in oxygen or air, is called enthalpy of combustion. It is denoted by A.H,e.g. CH,(g) + 20,(g) —> CO,(g) + 2H,0(I); A.H = -192 kcal ‘The value of A.H is always negative. This is because heat is always evolved during combustion. The grading of food articles and various fuels can be done on the basis of the values of enthalpies of combustion. If heat of combustion is measured in keal/g or kd/g (ie. calculated for one gram of a substance), it is called the calorific value. In other words, the amount of heat produced in calorie or joule when one gram of a substance (food or fuel) is ‘completely burnt or oxidised, is called calorific value. Mathematically, Calorific value = Calorific Value of Important Food Stuffs and Fuels Calorific value Calorifc value Fuel sie) Food lo Wood wv Milk 31 Charcoal " ke 67 Kereetse “ Rice 167 Methane 35 Sugar 173 LPG 55 Butter 30.4 Hydrogen 150 Ghee 37.6 Out of the fuels listed, hydrogen has the highest calorific value. However, it is not used as domestic or industrial fuel due to some technical problems. Of the various constituents of our food, fats and carbohydrates serve as the main sources of energy. The calorific value of proteins is quite low. Example 10. AH for combustion of ethane and ethyne are 341.1 and -310.0 kcal respectively. Which is better gas welder? (a) Ethane (b) Ethyne (c) Both have equal capacity (d) Data insufficient Sol. (b) Calorific value = heat produced by 1 ¢ of fuel. Given, AH for CH, = 341.1 kcal 341.1 Calorific value= = -11.37 keal/g Given, 4H for CH, =-310.0 kcal Calorific value= As the calorific value of CH, is high as compared to CH, therefore CH, is a better gas welder. Enthalpy of Neutralisation + The enthalpy change when one equivalent of an acid is neutralised by one equivalent of a base in a fairly dilute solution is called the heat or enthalpy of neutralisation. It is denoted by 4, H.e.g. HCI(aq) + NaOH (aq) —+ NaCl(ag)+ H,0; 4, H = -13.7 kcal« The heat of neutralisation of a strong acid against a strong base is always constant, ie. 13.7 keaV/equivalent or 57.1 kJ. This is because heat of formation of water in case of dilute solution, i.e. H* +OH” —> H,0; AH =-13.7kcal « Fora weak acid against a strong base or a strong acid against a weak base or a weak acid against a weak base, its numerical value is always less than 13.7 keal. This is because here some heat is used up in the ionisation of acid or base. However, for HF, 4,H is higher due to high heat of hydration of fluoride ion. + Neutralisation reactions are always exothermic, thus, it always have a negative value. + The heat of neutralisation of an acid or base can be easily determined in the laboratory with the help of polythene or polystyrene bottle. Calculation @= mass of the solution x specific heat (T, - T,) Enthalpy of neutralisation = -2 x 1000% 1 100 x where, T, = initial temperature of acid and base T, = final temperature of solution after mixing Ty - T, =rise in temperature @ = heat change in reaction jormality of the acid or base. Example Tl. When 50ml of | MHCl(aq) with 50 mL of 1 MNaQH (aq), the enthalpy of neutralisation will be (4571k) (4.2K ()-57.1K (29K Sol. (d) HCl + NaOH —> NaCl+H,O (50N000)x 1" (50/1000) x 1 0.05 moll 0.05 mo. When 1 mole HCl is neutralised by 1 mole NaOH, the enthalpy of neutralisation = —57.1 kJ :. When 0.05 mole HCI is neutralised by 0.05 mol NaH, A,H =-57.1x0.05 =2.85 ~2.9 k} Enthalpy of Solution ‘The enthalpy change when one mole of solute is dissolved completely in excess of solvent is called enthalpy or heat of solution. The solvent used here is usually water. It is denoted by A, H. e.g. NH,Cl(s)+H,0() —> NH,Cl(aq);A,,H = + 3.90 keal A,H = hydration energy - lattice energy Enthalpy of Hydration The enthalpy change or heat of hydration when one mole of substance combines with required number of moles of water to form a specific hydrate. Its symbol is AyyoH-eg. CuSO,(s) + 5H,0(2) —> CuSO, - 5 H,0(s); gyal = 78.22 kTIn general cases, hydration is an exothermic process. However, there are some cases also where hydration is an endothermic process. Example 12. Ai 298 K, the enthalpy of solution of solid magnesium sulphate is -91.21 kj mol and that of hydrated magnesium sulphate is 13.81 kj mol". The heat of hydration of solid magnesium sulphate is (a)-91.21 (b) 105.02 (c) +105.02 (d) +91.21 Sol. (b) Given, (i) MgS0,(3) + 7H,0 E25, meso, -7H,01aq); AH, = -91.21 kj mot" MgSO, -7H,013) + H,0 (excess) —> MgSO, -7H,0(aqi gut =13.81 kj mor Eq. (i) is infact, involves the following two steps MgSO4(s) +7H,O —> MgSO,-7H,0(5)5 Aig =? MgSO, -7H,0(3) + H,Ofexcess) —> MgSO, -7H,0taq): SoH, =13.81 kj mot Thus, oth = BH + Bids or Aiyds = Avot — Aso = -91.21-13.81 =-105.02 kj mor" Enthalpy of Dilution The enthalpy change when the solution containing one mole of a substance is diluted from one concentration to another is called enthalpy or heat of dilution. e.g. KC1(200H,0) —> KC\300 H,0); Ag,H = xkJ If heat of solution of the hydrated and anhydrous salt is known, the heat of hydration is obtained by subtracting Ajga H of hydrated salt from A,,,3 H of anhydrous salt, eg. CuSO, (anhydrous) + a H,O() —> CuSO, - al1,0; Aga antysy = ~66.50 kJ CuSO, - 5H.0 +(a- 5)H,O() —> CuSO,-aH,0 Anya HH gayérated) = 11.71 kd Thus, A,,H of solution = AyyaH anny ~ Saya taydrated Enthalpy of Ionisation + The enthalpy change when one mole of a weak acid or a weak base is completely ionised into its constituents, is called the enthalpy or heat of ionisation. It is represented by AyaH,e-8. CH,COOH(ag) = CH,COO"(aq) + H*(aqy; AionsH = -55.43 kJ mol Heat of ionisation can also be obtained by subtracting the heat of neutralisation of weak acid or a weak base from the heat of neutralisation of strong acid and strong base. Since, heat is required for ionisation process. Therefore, the enthalpy of ionisation is usually negative.Enthalpy of Transition The enthalpy change when one mole of a substance changes from its one allotropic form into another is called enthalpy of transition. It is represented by Atransition/? or A,H. eg. Srrombio —? Simonoctine) A¢H = -13.14 kd Enthalpy of Atomisation The enthalpy change that accompanies the total separation of all the constituent atoms in a chemical substance (either element or molecule or compound) is called the enthalpy of atomisation. It is denoted by AGH. e.g. () CH) — C@)+ 4H (2): AH = 1665 kJ mol" (i) Na(s) —> Na(g);A,H = 108.4 kJ mol In this case, enthalpy of atomisation is same as that of sublimation. (iii) Hyg) —> 2 H(g) A, H = 435.0 kd mol™ Here, enthalpy of atomisation is same as the bond dissociation enthalpy. Bond Energy and Bond Dissociation Energy When a bond is formed between two atoms in gaseous state to form a molecule, some heat is always evolved which is called bond energy or bond formation energy. + Bond dissociation energy is the amount of energy required to break/dissociate bond of a particular type, i.e. between same two types of atoms present in one molecule of the compound. + Bond energy is taken as the average value of dissociation energies of same type of bonds present in one mole. In case of diatomic molecules, bond energy is equal to the enthalpy of bond dissociation. H— CKg) —> H(g)+Cl(g);AH = +431 kJ mol However, in case of polyatomic molecules, as CH.) —> C(g)+ 4H(g);AH = 1664 kJ mol C—H bond energy = fot bond dissociation energy (as there are four C—H bonds in CH,) = = = 416 kJ mol As a chemical reaction involves the breaking of old bonds in reactants and formation of new bonds in products, the enthalpy change of a reaction can also be calculated by, the following formula, [A,H = sum of BE of reactants — sum of BE of products Factors affecting bond energy are (@ Size of the atom Smaller the size of the atom, higher will be the bond energy and vice-versa.(ii) Electronegativity The bond formed between atoms having large difference in their electronegativity values are more polar and more ionic. Hence, their bond energy will be larger. (iii) Bond length Shorter the bond length, higher is the bond energy. (iv) The bond energy order for different type of bonds will be C= C>C=C>C—C Example 13. Bond energy of H—H bond is 430 kj mol~' and that of Cl—CI bond is 242 kj mol”. If the heat of formation of HCL is -91 kj mol” then the bond energy of H—CI will be (a) 427 Kj mol (b) 490k) mor {c) 245 kj mor (¢) 290k} mor" Sol. (a) Given, H, + Cl; —> 2HCE A,H = -91 kj mot"! .: In this reaction, two moles of HCI are produced, O,H =2xA,H =2x-91=-182 kJ mot Let the bond energy of H—CI bond is x :. The bond energy for 2 moles of HCl = 2x For the reaction, H-H +Cl—cl —> 2H—CI 4H # EBEpascunty ~ 2 BE prod 182 = 430 + 242-2 -182 =672-2« x0 S42 227 mor Hess's Law of Constant Heat Summation “The total heat change (AH ) accompanying a chemical reaction is the same whether the reaction takes place in one or more steps” or “Enthalpy change in a particular reaction is always constant and is independent of the path in which the reaction takes place.” The above statements are called Hess's law of constant heat summation. e.g. For the process given alee ; J, aN Enthalpy change (AH) according to Hess's law, = AH, + AH, + OH, Here, H,, H, and H, are the enthalpy change, when Bis prepared from Athrough intermediate C and D. When a compound shows resonance, there is considerable difference between the heat of formation as calculated from bond energies and that determined experimentally. =. Resonance energy = Experimental or actual heat of formation — Calculated heat of formation. caeThermochemical Calculations The following points are to be kept in mind while writing down the required thermochemical equation. For example, if heat of formation of methane is to be determined, write down the following equation : C(s) + 2Hy(g) —> CH,(g);AH =? Try to obtain the required equation from the given dat There are two ways for doing this. () First way By adding, subtracting and multiplying various the thermochemical equation. (ii) Second way Enthalpy of reaction = Eventhalpoe of prniucts) ~ Lienthalpios of reactants) Example 14. Calculate the standard enthalpy of formation of CH,OHU) from the following data (NCERT) CH,OH + 2 ozs) —> COAg) + 2H,00); At =-726kjmor Coaphite + O18) —> COAg); AH® =-393kjmol! Hyg) + $048) — > H,00); 4)He =-286k}mor (@) -239(b) #239) +1195 @) -119.5 Sol. (a) Firstly we write the required chemical equation for the formation of 1 mole of methanol () and then calculate A, H° for the formation of methanol by adding all the equation in such a way so that it give the required equation (i.e. apply Hess's law) Required reaction for the formation of methanol is as follows Cs) + Hyg) + $048) —> CHOH); A/HP =? Given, enthalpy for the combustion of methanol () CHO) + 204g) —+ CO4g) + 2H,00; 2 we Enthalpy for the formation of 1 mole of CO,(8); (ii) Coraphnes + O38) —> COAg); AH? = -393kI mol! Enthalpy for the formation of 1 mole of HOU); (ii Ag) + 30u8) — H,000; A/H" =- 286k) mor 726k)mol"! Multiplying Eq, (iii) by 2 [because 2 moles H,0() are formed in Eq. i] we get, (iv) 2Hg) + Og) —> 2H,OU); A,H® = - 572 kimol' ‘Summing up the Eqs. (ii) and (iv), we get () Os) + 2Hig) + 204g) —> CO4g) + 2H,00); A,H® =-965 kjmol Reversing Eq.(i). we get 3 (vi) CO{g) + 2H,OW) —> CH,OH)) + 3 Og); A;H? = +726kimol! ‘Adding Eqs. (v) and (vi) we get required equation Cla + 2HAg) + $048) —> CHOHY); 4,4 =-239kjmorExample 15. Given, CCl,(g) —> Cig) + 4Ckg) Calculate the bond enthalpy of C—Cl in Chg). Aug H? (CCl,) = 30.5 kjmol" A, HP (CCl,) = -135.5 kl mol" A,HP(C) = 715.0 kJmor!, where, 4,H° is enthalpy of atomisation, AH? (Cl,) = 242 kj mol"'. (a) +1304 (b) -1304 (cd -326 =) + 326 Sol (d) Step 1 Write the balanced equation for all the enthalpy, changes. @ CCL —> CChig); A,.,H? = + 30.5kI mort (ii) C9 + 2Clg) —+ CCI; 4,H® =-135.5k)mor (iil) 9. —> Cig); A,HP =715.0K)mor (iv) Clg) —+ 2CKg); 4,H* = 242k) mor" Step \I Apply Hess's law to obtain the AH for the required equation CC,(g) — Cig) + 4Ckg) Multiply Eq. (iv) by 2, we get (v) 2Cl{g) —> 4Clig); A,H° = 484.0 kl mor" ‘Add Eqs. (ii) and (v), we get (vi) Cs) + 2Cl4g) —+ Cig) + 4Ckg); AH =1199 mor" Reversing Eqs. (i) and (ii), we get (ii) CClyig) —+ CCIy(); AH =-30.5 kJmol" (iil) CC) —4 Clo + 2Cl4g); AH = + 135.5 mol" ‘Add Eqs. (vi), (vii) and (viii), we get CClig) —> Cig) + 4Ckg); AH #1304 Kimo!" Step Il Since bond enthalpy is average of all the bonds. Bond enthalpy of C—CI bond in CCl, = Bot = 326k) mor"! cl I (2 There are four C—CI bonds in CCl,, capo a Heat Capacity, Specific Heat Capacity and Molar Heat Capacity + The quantity of heat required to raise the temperature of system by one degree is called heat capacity of that system. This is denoted by C. Heat capacity is a path function. ‘Thus, in general we can say ity, c= 4 Heat capacity, C = ar + The magnitude of heat capacity depends upon the size, composition and nature of the system. Heat capacity varies directly with the amount of substance. It also affects temperature. If the magnitude of heat capacity is large, there is only a small rise intemperature by a given amount of heat. e.g. Heat capacity of HO is large, thus a large amount of heat is required to raise its temperature. In chemical calculations we often use specific heat capacity and molar heat capacities. Specific heat is defined as “the heat required to raise the temperature of one unit mass by 1 degree (either celsius or Kelvin)”. When the definition is given in terms of mole, it is considered as molar heat capac’ ». the heat capacity of one mole of a substance. + The specific heat capacity and can be calculated with the help of following formula, q=exmxal| where, q = heat required to raise the temperature by 1°C pecific heat capacity m= mass At= temperature change (in °C) + If Cis the heat capacity of n mol of the system, then its molar heat capacity C,, is given by C,, + The specific heat capacity of water is 1 cal g? K"'or 4.18 dg K7. Heat Capacity at Constant Volume (C,) The amount of heat change of a system at constant volume, i.e. change in the heat of a system with per unit rise in a temperature at constant volume (AV = 0) -(# dT From the first law, dq=dU + pdV at dV =0,dg=dU dU = & (Sr), ‘Thus, heat capacity at constant volume represent rate of increase of internal energy of the system with temperature. Heat Capacity at Constant Pressure (C,) The amount of change in heat of system with per unit rise in temperature at constant pressure, is called heat capacity at constant press From thermodynamics first law, dq = dU + pdV Also, dH = dU + pdV «-(34),-(z7), ‘Thus, heat capacity at constant pressure also represents the rate of increase of enthalpy of system with temperature.Relation between C, and Cy Enthalpy of the system, H=E+pv From ideal gas equation, pV =nRT where, n =1 pV =RT or H=E+RT On differentiating with respect to 7, aH GE LR aT aT or Cy=Cp +R or (C, - Gy) = R= 1.99 cal K"' mol” = 8.314 JK™ mol The difference between C, and Cy is equal to the work done by 1 mole of a gas in expansion when heated through 1°C. C, is Always Greater thanC, When gas is heated at constant volume, the pressure of a gas has to increase. As the gas is not allowed to expand, therefore in case of Cy whole heat is required for raising the temperature of one mole of a gas through one degree. When gas is heated at constant pressure it expands. Thus, in case of C, heat is required for two purpose. + to increasing temperatures of one mole of gas through one degree and + for increasing the volume of the gas against external pressure. Thus, C, is always than C,. C,/Cy Ratio The ratio of molar heat capacities at constant pressure to that at constant volume is represented by y. The value of y gives information about the atomicity of gases. Gy GQ From the ratio of C, and C,, we get idea of atomicity of a gas. For any hypothetical process, if type of gas is given (.e. monoatomic, diatomic etc.) then specific heat can be calculated by the expression RF Ce Y provided gas follows pV" = constant Example 16. One mole of an ideal gas with Cy = 3/2R is heated at a constant pressure of 1 atm from 25°C to 100°C. The AE and AH are respectively. (a) 300, 225 (b) 225, 375 (©) 375, 225 (d) 225, 300Sol, (b) For ideal gas, AE=n-Gy ar=tx(3x2}x1000 ~25)=225 cal 3 5 Now, C,=Cy +R =SR+R==R low, pay 2 ; Now, AH = nicyAT mtx (32) «(000-29 0:75 ca Example 17 4 moles of an ideal gas having y = 1.67 are mixed with 2 moles of another ideal gas having y = 1.40. Find the equivalent values of y for the mixture. (a) 1.33 (b) 1.54 (1.67 (d) 1.23 (sha tnGn) Cc +7, Sob (b) Yong = meee TC ea Fey men Ry RY, 4 natn . R = MY 2- 1+ ny, (4-0 2-424 -D w4xt 67 x(1.40 -1) + 21.40 x(1.67=1) 4x(1.40 -1) + 201.67 -1) #1547 Entropy It is defined as, the property of a system which measures the degree of randomness in a system. It is generally denoted by S. It is a state fun .. i.e. change in entropy (4S) depends only on the initial and final states of the system. Thus, AS = Sonat ~ Spitial Units of entropy are joule per kelvin per mole. For a given substance, the crystalline solid state is most ordered and therefore, has the lowest entropy. However, gaseous state is most disordered, therefore, has the highest entropy. The liquid state is the intermediate between two. Thus, the order of randomness and thus, the entropy is gas > liquid > solid. Some examples in which entropy either increases or decreases are + A molecule if kept in a larger volume container will have higher entropy. + Decomposition of a compound increases entropy while combination results to decrease in entropy. « Incase of atoms or molecules belonging to different elements, the one with higher mass have greater entropy, i.e. for inert gases Site < Se < Sar < Sip < Se < Stn+ The molecules with more atoms of given type or with greater number of chemical bonds or greater capacity to take up energy means greater thermal disorder thus, have greater entropy. e.g. Sacetylene < Sethytene 0. This means that there is increase in entropy of universe in spontaneous change. + If AS,cua1 OF AS universe i8 positive, the process is spontaneous. + If AS tat OF AS universe 18 negative, the direct process is non spontaneous. + If ASyeea1 OF ASyniverse i8 2erO, the proces equilibrium. Entropy Change in Reversible Process Consider an isothermal reversible process. In this process, let the system absorbs q amount of heat from surroundings at temperature 7’,The increase in the entropy of the system will be q ASgutem = + On the other hand, surroundings lose the same amount of heat at the same temperature. The decrease in the entropy of the surroundings will be AS, =-t armundings = ~ 7 Total change in entropy of the process = entropy change in system + entropy of change in surroundings Sl * Speen *4Spmanang £220 When the reversible process is adiabatic, there will be no heat exchange between system and surroundings, ie. q = 0 MS.yuom = 0 Surroundings = 0 Scout = System + ASyurroundings =0 Entropy Change in Irreversible Processes T, Syne * See * Sine” [ZT Here, 7, = temperature of system T, = temperature of surrounding and T, > Ty, ie. T, ~T, = +¥e OF ASpyccou > 0 As, system = a4 ASyurrounding ‘7, In an irreversible process entropy is increased. Remember + A thermodynamically irreversible process is always accompanied by increase in entropy of the universe while in case of reversible process, entropy remains constant. + Most of the natural phenomenon are irreversible in nature. Entropy and Spontaneity + Positive and negative values of AS shows the spontaneous and non-spontaneous processes respectively. + 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. + As q = 0 for adiabatic process, for reversible adiabatic process AS = ie and hence, their will be no change in entropy. Such processes are called isoentropic. However, for adiabatic free expansion AS #0.Entropy Change During Phase Transition The change of matter from one state to another is called phase transition. The entropy changes at the time of phase change can be summarised as, AS acing = “8 where, T,, = melting point of substance. AS. = AA vaporization \vaporisation T, where, 7, = boiling point of substance Similarly, ASjyhfimation where, T,,,, = sublimation temperature Entropy Change for Ideal Gases Change in entropy for an ideal gas under different conditions may be calculated as + When the gas changes from initial state (1) ta final state (2) AS = 2.303 nC, tee 2) +2303 nRlog (#) Tq, vy (when T and V are variables) AS = 2.303 nC, log (2) +2303 nR log (2) 1, Pr (when T and pare variables) For isothermal process, AS = nRIn Vy 1 =nRIn (2 AT = 0) Pz For isobaric process, SS = nCyInZ2 (= p) ; ee th For isochoric process, AS = nGy InZ ; (Vi =Ve) Entropy change in mixing of two ideal gases AS =~ 2.303 R [n, logs, + n, logy) AS/mol = - 2.303 R [x, log x, + x, log x] Here, xx) are mole fractions of gases A and B, x n n. ie. x =— a eae tt. 7, + Ny my + My n,,n, are mole of gas A and B respectively. Entropy change in adiabatic expansion will be zero, AS =0.Standard and Molar Entropy Change + Ifentropy change is measured under standard conditions, it is called standard entropy change (AS° ). Once, we know the entropies of a variety of substances participating in a reaction, we can calculate the standard entropy change, AS° as, = sum of of product: e.g. In a general reaction, aA+bB —+ xX+y¥ AS® = [xS? for X + yS° for ¥} - [aS* for A+ bS* for B] + The standard entropy of a substance can be calculated with the help of following formula S$ = 2.303C, logT + If entropy is defined per unit amount of substance, it is called molar entropy (S,, }. Example 18. When 36 g of liquid water evaporates at 373 K (A,apH = 40.63 Kj mol), the entropy change is (a) 218 JK-'(b) 315 JK~"—() 185 JK~"_(d) 268 JK™" ‘sum o1 of reactants Sob, (a) AvagH = 40.63 kj mot", T, =373 K Map 63 «1000 Jmol" Beg Sse OE LOE, wer 373K =109 Jk" mor" Entropy change for evaporation of 36 g of water 2 108 36 = 218 JK"! 18 Second Law of Thermodynamics The second law of thermodynamics can be stated as, + Whenever a spontaneous process takes place, it is always accompanied by an increase in total entropy of the universe. + It is impossible to take heat from a hotter reservoir and completely convert into work by a cyclic process without transferring a part of heat to a cooler reservoir. This statement of second law is called Kelvin’s statement. It is impossible for a cyclic process to transfer heat from a body at lower temperature to one at a higher temperature without converting some work to heat. ‘This statement of the second law of thermodynamics is known as Clausius statement. The entropy of the universe is continuously increasing and tends toa maximum. AS univ = ASiye + ASpureThird Law of Thermodynamics ‘This law was proposed by German chemist Walther Nernst. According to this law, “The entropy of a perfectly crystalline substance approaches zero as the absolute zero of temperature is approached”. It forms the basis from which entropies at other temperatures can be measured. lim S=0 Ea) In case of CO and NO molecules in solid state, there is randomness even at 0 K due to their dipole moment hence, entropy in such cases is not zero even at 0 K. As the temperature is raised, the molecules begin to vibrate. The number of ways in which the vibrational energy can be distributed increases with increase in temperature. + Therefore, the entropy of the solid increases steadily as the temperature increases. + At the melting point (m.p.) of a solid, there is a discontinuous jump in entropy because there are many more ways of arranging the molecules in the liquid than in the solid. + An even greater jump in entropy is observed at the boiling point (b.p.) because molecules in the gas are free to occupy a more larger volume and hence randomness increases. Gibbs Free Energy + The maximum amount of energy available to a system, during a process, that can be converted into useful work is called free energy or Gibbs free energy or Gibbs energy. It was called Gibbs free energy in early literature. Howerver, in accordance with IUPAC recommendations we shall use the term free energy for it. + Gibbs energy is the measure of capacity of a system to do useful work. It is denoted by G and given as G=H-TS @ Similarly, change in free energy is expressed as AG = AH - TAS Gi) where, H = enthalpy of system, S = entropy of system T = absolute temperature, AH = enthalpy change of system, AS = entropy change of system The above Eq. (ii) is called Gibbs Helmholtz equation and is very useful in predicting the spontaneity of a process. (IAG is negative, the process is spontaneous Gi) If AG is positive, the process is non-spontancous (ii) If AG is zero, the process is in equilibrium stateWe know, 9 = AU + Wexpacsion + Woonvexpansion U + PAV + W, -W, AG = ~ Wrooexpansion OF Wusetut Gibbs Free Energy as Criteria for Spontaneity Spontaneity of a process is decided by the value of AG. A negative value of AG shows a spontaneous process and a positive value shows a non-spontaneous proces: Since, the value of AG depends upon AS and AH, these two also play an important role for deciding spontaneity of a process. [AG = AH - TAS, Gibbs Helmholtz equation]. For negative value of AG, several conditions exist that are mentioned in the table given below Relationship between AG and Spontaneity of a Process Spontancous/ Non-spontancous AS AH AG process > Sueetall Spontaneous at all temperature temperitures mee - = sve at low Spontaneous at low temperature but temperiture _non-spontaneous at high temperature but +e at high temperature - + +veatlow Spontaneous at high temperature temperature and =ve at high tempemture + + +veatall Non-spontaneous at all temperature temperatures We know AG is positive for non-spontaneous reactions. However, such a reaction can be made spontaneous by coupling it with another reaction having large negative value of AG. Example 19. For the reaction at 298 K, 2A4+B —9C SH = 400 kj mol“! and AS =0.2 kJ K"' mol"? At what temperature will the reaction become spontaneous considering AH and AS to be constant over the temperature range? (a) 1000 K (b) 1900 K (© 2000 k (a) 2200 K Sol. (d) In order to solve out such problems following steps are involved.Step | Write the given information e.g. In the above question, we have AH = 400 kj mol", AS =0.2k) K"' mol" Process spontaneous, so AG < 0. Step It Think which formula you can use for the information given so that you can find spontaneity. AG ishelpful in finding spontaneity and is also related to AH and AS as. AG = AH=-TAS ‘Step Ill Calculate the value of T by putting the values of AH, AS and AG. 0>AH-TAS 4H ,_ 400 TAS > AH, T > —, T > ——, T > 2000K as 0.2 Standard Free Energy Change ‘The free energy change for a process at 298 K and 1 atm pressure in which the reactants in their standard state are converted into products in their standard state, is called standard free energy change. It is denoted by AG°. Free energy change when! mole of the compound is made from its elements in their standard states is called standard molar free energy of formation of a compound. Efficiency of a i a sting oc total useful wo a ——=—w x 100=—— x 100 total heat given xd AH a Remember + The dependence of free energy on temperature is given by Gibbs-Helmholtz equation aGxansT| a(aG) ar + For isothermal expansion or compression of an ideal gas, AG = nRT In 2 A + Process with negative AG is called exo-ergonic and positive AG, endo-ergonic. + 4,H? and AG? of an clement is taken as zero but AS? of an element never be equal to zero. Relation between Gibbs Free Energy and Equilibrium Constant AG = AG? + RT InQ ‘Thus, the standard free energy (AG?) is related to equilibrium constant K as, AG? = - RT InK, ie. AG® = -2.303 RT log K As, at equilibrium, AG=Oand Q=KRelationship between the Standard Free Energy Change and the Equilibrium Constant aG logK K Comment AG*=0logX=0 1 — The equilibrium mixture contains comparable amounts of reactants and products. AG*<0 logK >0 K>1 The equilibrium mixture is mainly products. AG*>0 logK <0 K<1 The equilibrium mixture is mainly reactants. Relation between Gibbs Free Energy and EMF of the Cell Any process that occurs spontaneously can be utilised for performance of work. The greater the Gibbs energy change, the greater is the amount of work that can be obtained from the process. The free energy change (AG) is related to the electrical work done in the cell as, AG = - nFE,.1, where, E = emf of the cell n= number of moles of electrons involved F = Faraday’s constant, ie. 96500 C If reactants and products are in their standard state, AG* = - nFE* where, E° = standard cell potential Example 20. The standard Gibbs energy change at 300K for the reaction, 2A —= B + C is 2494.2. Ata given time, the composition of the reaction mixture is [l= + [8] = 2 and{C] = + The reaction proceeds in the [R=8314 JK/mol, e = 2.718} (QE Main 2015) (a) forward direction because Q > Ke (b) reverse direction because Q > Ke (0 forward direction because Q < Kc (d) reverse direction because Q < Kc Sol. (b) Given, AC? =24942} 1 ANN PF ay “@ 2 AC? = 24942 (given) 24942 300x8.314 Q>K therefore, reaction shifts in reverse direction