C6 - Thermodynamics 4 Heat lost = Heat gained by H,0 (ms) 6078) = 36x 4.18 x AT aT = ours 4.04. ~ 36% 4.18 > Ty = 290 + 4.04 = 294.04 PRE-READING EXERCISE Q1. system and its surroundings together make up the 2. Ina/an system, there is no exchange of energy or matter between the system and the surroundings. Q3.__ Intensive properties depend on the amount of the system whereas extensive properties do not. (True/False) Q4. Variables like PV, T are called state variables or state functions as they (depend /do not depend) on the path taken. Q5.__ Internal energy of a system is directly proportional to its Q6.__IFtwo systems A and B are in thermal equilibrium then it means that T, and 7p are (came/ different, If another body C is in thermal equilibrium with B, then by zeroth law of thermodynamics, Te is oT, Equal/ not equal) Q7._Hfasystem has an internal pressure P, volume V and temperature 7 and an external pressure Pe, is applied on it then the amount of work done on the system is calculated using the formula _ where compression work comes out to be (positive negative) and expansion work comes out to be (positive negative) QB. When heat is transferred from the surroundings to the system, the value of q for the system is considered to be (positive/ negative) IN CLASS EXERCISE LEVEL 1 QU. Which ofthe following is /are intensive thermodynamic properties? A) Volume B) Kinetic energy © Density D) Molality Q2. Which of the following is an extensive property? A) Surface tension B) Refractive index © Energy D) Temperature QB. Sites of an ideal gas at a pressure of 5 atm expands isothermaly into a vacuum until the total volume is 10 Uieres. How much work is done in the expansion? Qk The relation between magnitude of the work done on an ideal gas when itis expanded (a) reversibly or (b) irreversibly from volume ¥; to Vp is A) w (reversible) = w (irreversible) B)_w (reversible) < w (irreversible) ©) w (ceversible) > w (jereversible) D)_w (reversible) = w (irreversible) + Pexe 6V QS. _Astate function is path (dependent/ independent) and the change in value of a state function ina cyclic process is Scanned with CamScannerC6 - Thermodynat Q6. Calculate the work done when 1 mol of an ideal gas is compressed reversibly from 1 bar to 3 bar at a constant temperature of 300 K. Q7. _ Inthe pressure-volume diagram given below, the isochoric, isothermal, and isobaric parts, respectively, are: ° ¥ A) BAAD,DC B) DC.CB.BA © 48,Bc,cD D) CD,DA,AB Q8. Work done by an ideal gas in an isothermal process against constant pressure is A) -2303 RT logic! «BY —2303RT loge ©) ~Peee AV b) Pav Q9. The volume of a gaseous mixture changes from 10 x 10~? m? to 8 x 10-% m® against a constant external pressure of S x 10° Nm~2. The work of compression is A) 1000) B) 100) ©) 10000) D) 10) Q10. The expression for the maximum work of isothermal expansion of an ideal gasis A) Wiyax = ~2.303 nRT logyo% B) Wax = ~2:303 nRT logo st ©) Whar = ARP ogy D) Wax = ~nT Togo! Q11. The maximum work of expansion of 2 moles of an ideal gas at 300 K, occupying @ volume of 20dm®, isothermally and reversibly until the volume becomes 40 dm: is (R = 8314 JK~*mol™) A) -3457) B) -3.792) © 3.792) D) 3457 ky LEVEL 2 12. Asample of 8 g methane occupies 3 1 at 300 K. 1. Calculate the work done on the gas when the gas expands isothermally against a constant external pressure of 03 atm until its volume has increased by 3 L Calculate the work that would be done on the gas ifthe same expansion occurred reversibly. Express answers in the units off, atm. 13. Two moles ofa gas at 1 bar and 300 K are compressed at constant temperature by use of constant pressure of 5 bar. How much work is done on the gas? LEVEL 3 Q14. Five moles of a gas are put through a series of changes as shown graphically in a cyclic process. Figure out the type of processes A~ B,B > Cand C~ Aare. Also convert the V ~ T graph given below to a P ~ V graph i “Temperature a Scanned with CamScanner6 - Thermodynamics Q15. Onemole of monatomic ideal gasis enclosed under a frictionless piston. A series of processes occur, and eventually the state of the gas returns to its initial state with a P—V diagram as shown below. Answer the following in terms of Py, Vp and R. Assume all processes are carried out reversibly. |. Find the temperature at each vertex A, B and C 1, Find the work done by the gas for each process, Ve AV Q16. Derive a relation showing reversible work of expansion from volume V, to V; by ‘n’ moles of real gas obeying van der Waal's equation at temperature T where velume occupied by molecules may be taken as negligible in comparison to total volume of gas. HOMEWORK LEVEL1 QL. Fillinthe blanks, 1. 1F 100 mL benzene boils at 80°C then 40 mL benzene will boil at property. IL. Heatisa ‘Thus bp. is (a/an) function.(state/path) QZ LJisequal to A) Lkgm’s~* B) ©) Both A) and B) D) None of these Q3._ Ina closed system exchange of. (heat mass) is not possible. (heat/ mass) is possible whereas exchange of. Q4.__Inthermodynamics, a process is called reversible when: A) Surroundings and system change into each other B) There is no boundary between system and surroundings C)_ The surroundings are always in equilibrium with the system D) The system changes into the surroundings spontaneously QS. Which of the following groups includes two intensive properties and one extensive property of a system? A) Temperature, energy, mass B) Mass, volume, density €) Optical activity, volume, specific heat D) Boiling point, volume, energy Q6. Which of the following is/are state function(s)? A) Work done B) Heat ©) Distance D) Displacement Q7. The external pressure needed to compress an ideal gas from 22 dm* to 8 dm? if 4.2 kj of work is done is A) 3x 108 Nm? B) 203 x 10" Nm? ©) 1x 105 Nm-? D) -34% 105 Nm-? Q8.__The work done during expansion in vacuum is zero because there is A) No opposing force ie. P = 0 B) Nochange in volume ie. AV =0 ©) Nochange in internal energy ie. AU = 0 D)_Nochange in temperature ie. AT = 0 Scanned with CamScanner6 - Thermodynat Q9. When AV is negative then A). Work is done by the system on the surrounding B) Work is done on the system by the surrounding, ©) Noworkis done D) Maximum work is obtained Q10. ‘The work (in litre atm) done when 3 moles of an ideal gas expand from a volume of 15 litres to 30 litres against constant pressure of 76cm of Hg at 27°C is A) ~45 B) -15 ©) -450 D) ~76x 15 Q11. When Fe(s) is dissolved in aqueous HCl ina closed vessel the work done is, A) Positive B) Negative ©) Zero D) Cannot be defined Q12. The work done when an ideal gas is compressed isothermally by 1 litre against aconstant standard atmospheric pressure is a B) -1) c) +0.1013 &y b) -10137 LEVEL 2 Q13. Agas expands by 0.5 litres against a constant external pressure of 1 atm. Calculate the work done on the gas in joules. Q14. Ata constant temperature of 300 K, one mole of a gas expands reversibly from 2 L to 10 L. Calculate the work done by the gas in the process. (Use log 5 = 0.7) Q15. Find the maximum work obtained by an isothermal reversible expansion of 1 mol of an ideal gas at 27°C from 2.24 to.22.4 L.(R = 2 cal/mol K) Q16. One mole of an ideal gas is compressed from 500 cm? against a constant pressure of 1.216 x 105 Pa. The work involved in the process is 36.50 J. The final volume of the gas is 4) 400 em? B) 100m! ©) 300m? D) 20cm? LEVEL 3 Q17. One mole of an ideal gas is at pressure Py and volume, Vy. The gas then undergoes three processes: 1. The gas expands isothermal to 2¥o while heat Q flows into the gas. The gas is compressed at constant pressure back to the original volume. I. The pressure is increased while holding the volume constant until the gas returns to its intial state Find out the work done on the gas at every step in terms of P,Vo,To fo _______ 47a Scanned with CamScanner6 - Thermodynamics 9 Q3. Heat is supplied to a certain homogeneous sample of matter, at a uniform rate. Its temperature is plotted against time, as shown in the figure below. Which of the following { conclusions can be drawn? (Given, slope(0A) = slope(BC)) £ 1A) Total heat required (sold-tiquid) > Total heat required (liquid->gas) i co B) Total heat required (solid-liquid) = Total heat required (liquid-+gas) Flas ©) Matter’s latent heat of vaporization is greater than its latent heat of fusion. é D) Matter’s latent heat of vaporization is smaller than its latent heat of fusion, GES Ans.¢ Sal. AB represents change of state from solid to liquid whereas CD represents change of state from liquid to gas. OA and BC parts of the graph represent linear increase in temperature in solid and liquid state respectively. We can see that roughly the same amount of time has been taken in OA and BC for the same amount of temperature change whereas CD > AB, which implies that the latent heat of vaporization is greater than the matters latent heat of fusion. Hence, Cis correct. Also, if we look at heat absorbed from 0 to B and B to D, we can see total heat required (liquid -» gas) > total heat required (solid - liquid). Hence, A) and B) are incorrect. — PRE-READING EXERCISE QI. According to first law of thermodynamics, energy of an isolated system is (zero/constant/always changing) 2. Expansion of a gas in vacuum is called and Pex for such a process is equal to Q3. Foran isothermal reversible change, change in internal energy is equal to, (heat/work done/zero) and therefore the value of q is equal ta (zero/ ~w/ +w), given that w is work done on the system Q4. Quantity of heat needed to raise the temperature of one mole of a substance by one degree Celsius is known as specific heat capacity (T/F) Q5. Heat absorbed at constant volume is equal to Q6. For an deal gas, Cpis always (greater/smaller) than Cv. Sy IN CLASS EXERCISE LEVEL 1 QI. The work done on a gas when compressed in a cylinder is 462 J. During this process, there is a heat transfer of 128 J from the gas to the surroundings. Calculate change in internal energy of the process. 2. Agasabsorbs 100 / heat and is simultaneously compressed by a constant external pressure of 1.50 atm from 8 L to ZL in volume. What will be the change in internal energy? 3. Calculate the amount of heat that must be supplied to raise the temperature of 2 kg of water from 25°C to its boiling point at one atmospheric pressure. The average specific heat of water in the range 25 ~ 100°C is 42 JK-Ag u. What is the value of change in internal energy for one mole of a monoatomic ideal gas that changes temperature from 27 to T? Scanned with CamScannerC6 - Thermodynamics 10 Q5. 2 moles ofanideal gas expand from 6 litres to 20 litres at constant pressure of 2.5 atm. Ifthe system is supplied with 5000 J of heat, calculate AU. A) ~145K) B) -29%) © 14sky b) 294 Q6. A gasis expanded by supplying 2400 J of heat, the work done is found to be 1337 J.The internal energy change of the system is A) -3737) B) 1063) ©) +3737) b) ~1063) 7. Which ofthe following is correct option for free expansion ofan ideal gas under adiabatic condition? A) q=0.arz0w=0 B) 40,47 =0,w=0 © q=0,4r=0,w=0 D) q= 0.7 <0,w 20 LEVEL 2 QB. Which of the following graphs given below show(s) adiabatic process? A) mut B) LU © mv D) nv 9. Onemole of a monoatomie gas is expanded through path ABC as shown: BT ae ww Find the temperature at points A, B and C and heat exchanged in the overall process A-C Q10. A piston filled with 0.04 mot of an ideal gas expands reversibly from 50 ml. to 375 mL ata constant temperature 0f 370°C. Asitdoes so, it absorbs 208 J of heat. Find the values of q and w forthe process. Q11. Consider a 2 mo! sample of an ideal diatomic gas undergoing a reversible isothermal expansion at 300 K from 1.00 atm and 25 L to 0.33 atm and 75.00 L. Determine w (work done on gas),q, and AU for this process. Given: In3 = 11,1n2 = 0.693, Q12. During a reversible isothermal compression of 1.00 mole of an ideal gas originally at 27°C, 0.500 atm, and 43.2 L, 1750 J of heat was removed, What isthe final pressure ofthe gas? Q13. Consider a system consisting of 1 mole ofa diatomic gas contained in a piston. What is the temperature change of the gas fq = 50.0 and w = ~100.0)? Q14. A sample of benzene, C,H,, weighing 6 9 was burned in an excess of oxygen in a bomb calorimeter. The temperature of the calorimeter rose from 25°C to 38°C If the heat capacity of the calorimeter and contents was 12.4/°C, what is the value of q for burning 1.25 mol of benzene at constant volume and 25°C? QUIS. Calculate work done on an ideal diatomic gas that undergoes a reversible adiabatic compression from 11 atm, 298 K and 25.0 L to 1.00 L. Given that (25)°* = 3.624 and (25)'* = 90.6 Scanned with CamScannerC6 - Thermodynamics 8 6.2 The First law of thermodynamics CONCEPTS 1. Internal energy and its correlation with temperature 2. First law of thermodynamics 3, Heat capacity, specific heat (Cp and Cv) and molar heat capacity 4. Relate Cp and Cv and measure them using calorimetry 5. Adiabatic processes PRE-READING [Category Book Name Chapter Name Chapter Section REQUIRED NCERTXI ‘Thermodynamics 6 6.1Ac, 62.1, 6.2.2b. ILLUSTRATIONS QL. Inathermodynamic process, helium behaves asan ideal gas and obeys the law T/P#/* = constant. The heat given @. ton moles of He in order to raise the temperature from T to 27 is a) eer 8) 4er © 16Rr by Zero ans.D Sol T=KxPA = PV =RT=R-K + PHS = PME xVek = (Pv xvp = KF = PVs =k = PVY=K’ (y for He = 5/3) - We can say that the process is adiabatic. In an adiabatic process, q = 0. Hence, D) is correct. ‘A gas occupies 2 L at STP. It is provided with 300 J heat at 1 atm so that its volume becomes 2.5 L. Calculate the change inits internal energy. A) 350.65) B) 249.35) ©) 2995) b) 300.5) Ans: B Work done = ~P x AV = 1x (2.5 ~ 2.0) 0.5 L atm (Here, work is carried out at constant P and is therefore, irreversible) 1L. atm = 10-%m? x 1.013 x 108 Pa = 101.3) > w (in Joules) = 05 x 101.3) 50.65 J From the first law of thermodynamics, au =q+w > q=U-w 300 = AU + 50.65 «AU = 249.35) Scanned with CamScannerC6 ~ Thermodynamics u HOMEWORK LEVEL 1 a ‘A gas is cooled and loses 65 J in the form of heat. The gas contracts as it cools and work done on the system is equal to 22 J . What are the values of heat exchanged, work done by the gas and AU? QZ. fy isthe heat added to the system, xis the work done by the system and AU is the change in internal energy, then according to first law of thermodynamics A) aU =y+x © au =y+pav D) au =y+an 3. Foran deal gas, G, and y are related as a) G=a(4) B) 6 =R( ©) G=t dD) G=R(E) QF. A system absorbs 640 J heat and does work, The change in internal energy (QU) for the process is 380 J. The work done by the system is J A) 260 B) -260 © 1020 b) -380, Q5. system absorbs 520 J of heat and performs work of 210 J. The change in internal energy Is A) 620) B) 155) © s10y D) 4657 LEVEL? Q6. The pressure exerted on 1 mole an ideal gas at 2.00 atm and 300 K is reduced suddenly to 1.00 atm while heat 's tansferred to maintain the initial temperature of 300 K. Calculate q.w,and AU in the units of L. atm for this process 7. 28.9 oF N, gas at 300 K and 20 atm was allowed to expand isothermally against a constant external pressure of atm. Calculate AU, and w forthe gas. QB. An ideal gas changes from State A(2p,) through four different processes and finally returns to intial State A reversibly as shown below in the pV graph. ie o v Ww vo Calculate the total work done by the system and heat absorbed by the system in the cyclic process, Scanned with CamScanner2 6 - Thermodyna Q9. 10 g of argon gas is compressed isothermally and reversibly at a temperature of 27°C from 10 L to § L. Calculate q.w and AU for this process. R = 2.0 cal K-? mol”*,logio 2 = 0.30. Atomic wt. of Ar = 40. QUO. A system undergoes a continuous cyclic process as shown in figure. Calculate the heat absorbed during one cycle of the process, vin) 030 Prinra) QUL. Compute the ratio of slopesi.e. (2) ofa plot of P ~ V data for areversible adiabatic processand thatof reversible isothermal process of an ideal gas. Q12._ Work done in expansion of an ideal gas from 4 litres to 6 litres against a constant external pressure of 2.5 atm was used to heat up 1 mole of water at 293 K. If specific heat of water is 4.2/ 9°* K~!, what is the final temperature of water? QL3. Specific heat at constant pressure of a diatomic gas having molar mass M is approximately equal to ” en ® aw 9 or DD LEVEL 3 Q14. Amole of monoatomicideal gas at 1bar and 300 K is allowed to expand adiabatically against constant pressure of 05 bar. Now answer the following questions: 1. What is the final temperature? Il. Whats the final volume? IL, How much workiis done by the gas? 1V, Whatis the change in internal energy? Q15. Two moles of an ideal gas undergoes the following processes: ‘© Areversible isobaric expansion from {A} (1.0 atm, 20.0 L) to {B} (1.0 atm, 40.0 1). ‘+ Areversible isochoric change of state from {B} (1.0 atm, 40.0 L) to {C} (0.5 atm, 40.0 L). ‘+ Areversible isothermal compression from {C} (0.5 atm, 40.0 L) to (A) (1.0 atm, 20.0 L) 1. 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. ML, What will be the value of AU for the overall process? Express answers in the units ~ L.atm, Scanned with CamScanner6 - Thermodynamics 34 34 935, 036. 937. 38. 39 Oxidizing power of chlorine in an aqueous solution can be related to the ease with which chlorine gas gets reduced to form chloride ions, The energy involved in the conversion of $Clzcp) to Cliag) will be (Giver: Agus, Hey, = 240k) molt: Ag Hey = ~349 kj mol; AyygHl” = ~381 kj mol) A) +120 kj mol B) +152 kj mol" ©) -610 kj mol™ D) -850 kj mol Entropy change of the system and the surroundings in equilibrium A) increases B) decreases ©) isconstant D) either increases or decreases. Given that, € + 0, + C0,;AH® = ~a kj. 2€0 + 0; > 260;;AH* = —b ky The heat of formation of CO is A) b-2a 3) ° D) 20-0 ‘The table given below lists the bond dissociation energy (Eqiss) for single covalent bonds formed between C and atoms A,B, D and E. Bond Egias(keal mol) C-A 240 cB 382 c-D 276 C-E 486 Which ofthe atoms has smallest size? aD BE oa be The heat of combustion of C,H, carbon and hydrogen are a,b and ¢ cal respectively. The heat of formation of aH will be A) ~ (xb +4 —4) cal B) -(xb+%—a) cal ©) +(xb-2 48) cal Dy +(xb-2=$)cal In which of the following P ~ V diagrams for a gas, is the value of AU = 0? ! Ve A) s) | 4 Y - p ’ 9 >) Scanned with CamScanner6 - Thermodynamics 48 PRE-READING EXERCISE QL. Universe Q2. Isolated 3. False Q4. Donet depend QS. Kelvin Temperature Q6. Same, Equal Q7. —ParedV, positive, negative Q8. Positive IN CLASS EXERICSE LEVEL 1 q. cp ac Q3. Zero ac Q5. Independent, Zero. Q6. 275K) q. D ec a A qu. B qu. Db LEVEL2 Qi2. 09 Latm I. ~8.75.L.atm Q13. 20K) LEVEL3 Q14._Isochoric, Isobaric, Isothermal Answer Key C6.1 BASICS OF THERMODYNAMICS Qs. kt W Q16, w= -nkT Ins — nea HOMEWORK LEVEL 1 QL 80°C, intensive ML path wc QB. Heat, mass wc a. ¢ a D vA BoA @. B quo. B auc a2 ¢ LEVEL 2 qa. -505) qua. 4K QUS. 1380 cal qe D LEVEL3 q7. 1 ML, Zero 6.2 THE FIRST LAW OF THERMODYNAMICS PRE-READING EXERCISE Q1. Constant Q2. free expansion, zero 8. Zero, -w Qh False es. au Scanned with CamScanner‘Thermodynamics Q6. Greater IN CLASS EXERCISE LEVEL 1 Qi. +334) 2. 1009) 3. 630K) a 0. we B qv. ¢ LEVEL2 a8. A Q9. T= 273K,T, = 546K, Te q = +227 kj (heat absorbed) QUO. q = +208 j,w = -208) QU. w = -5500/,q = 5500j,AU =0 Q12. Latm QU3. The gas will cool by 2.4 K. Qu4. 2535 A QU5. 164 Latm 49 HOMEWORK LEVEL 1 QL. q = ~65/,Woygas = ~22) AU = ~43 Qa B QA a B wc LEVEL 2 Q6. q=123 Latm,w = ~12.3 Latm,aU = 0 Q7. AU =0,q=236j,w = -236) QB. Woy system = PV.g = PV Q9. w= 105 cal,g = —105 cal,AU = 0 QUO. q = 1007 Joules qu. y Qi. 300K a3. A LEVEL 3 Qu. L 240K Th 0.04 m® Ml. ~750J/mot IV. =750J/mot Q1S. L See Solution I. q=6Latm,w = ~6Latm Ml, zero. 6.3 ENTHALPY AND THERMOCHEMISTRY PRE-READING EXERCISE QL State, #=U + PV Q2.Exothermic, endothermic @. False Q4. standard state QS. True Q6. _Enthalpy of fusion Q7. Most stable or standard Q8. Summation JIN CLASS EXERCISE ‘LEVEL Qoob @ od @. BD wD GB 6 B Scanned with CamScanner