CHAPTER 15 ‘THE LAWS OF THERMODYNAMICS OBJECTIVES ‘After studying the material ofthis chapter, the student should be able t: + explain what is meant by a physical system and distinguish between an open system and a closed system. + state the first law of thermodynamics and use this law to solve problems. * distinguish between an isothermal process, isobaric process, isochoric process, and adiabatic process and draw a PV diagram for each proces. ‘+ calculate the work done by a gas from a PV diagram. Use the equations for an ideal gas and for the intemal energy of a gas to calculate the change in intemal energy of « gas and the heat added or removed during a thermodynamic + calculate the amount of heat which must be added or removed to change the temperature ff a gas held in a closed container under conditions of constant volume or constant pressure, ‘+ Write ftom memory and explain the meaning of three equivalent ways of stating the second law of thermodynamics. ‘+ use the first and second laws of thermodynamics to solve problems involving a Camot engine ‘+ distinguish between a reversible process and an imeversible process. Give examples of ‘each type of process * determine the change in entropy for a system in which the thermodynamic process is ither reversible or imeversible. istinguish between macrostate and microstate and solve problems involving the statistical interpretation of entropy. KEY TERMS AND PHRASES thermodynamics is the study of energy transformations in natural processes and involves relations between heat, work, and energy. system is any objector sets of objects which are under consideration; everything else in the universe is called the environment. In thermodynamics, a closed system is one where mass may not enter oF leave. In an open system mass may be exchanged with the environment. first law of thermodynamics is a statement of the law of conservation of energy. The first law states that the change in the intemal energy (AU) of a closed system is due to heat added ot Isremoved from the system (Q) and/or work done on or by the system (W). AU = Q-W. pressure-volume diagram or PV diagram is used to determine the work done by a gas undergoing expansion or compression in a closed system, isothermal process occurs when the temperstute ofthe gas remains constant. Isobarie process occurs when the pressure is constant, the work done on or by the gas can be determined by using W = P AV. isochorie process occurs at constant volume, AV = 0; therefore, W = P AV = Oand Q= AU. Adiabatic process occurs when no heat flows into or out of the system. An adiabatic process. ‘usualy occurs when a gas is compressed or expands so rapidly that there is no time forthe heat to flow in or out ofthe system, ‘heat engine is a device that is capable of changing thermal energy (Q,), also known as the input, heat or heat of combustion ofthe fuel, into useful work (W). ‘Carnot engine is an idealized engine where energy losses due to intemal fiction, turbulence. present inthe fuel after ignition, etc, are not considered. Camot determined thatthe maximum efficiency that can be realized from a heat engine depends on the temperature of the input heat and the exhaust heat refrigerators and air conditioners operate by removing heat from a low temperature (cold) reservoir and exhausting the heat tothe higher temperature (hot) reservoir. In orde to accomplish, this task, work is done to cause heat to travel opposite from its normal direction. entropy is a quantitative measure ofthe disorder in a system. second law of thermodynamis can be stated in several equivalent ways, three of which ar: 1) Heat energy flows spontaneously from a hot object to a cold object bu not vice vers. 2) Itisimpossible to construct a heat engine which is 100% efficient. Thus a heat engine can ‘convert some of the input heat into useful work, but the rest must be exhausted as wast heat. 3) The entropy of an isolated system never decreases. It can only stay the same or increase. SUMMARY OF MATHEMATICAL FORMULAS “The first law of thermodynamics is a statement of the law of conservation of energy. The first law states thatthe change in the intemal energy (AU) of a closed system is due to heat added or removed from the system (Q) andjor work done on or by the system (W), 182,‘A heat engine isa device that converts thermal energy (Q,) to useful work (W). ‘The heat energy not converted to useful ‘work is ejected to the environment as exhaust heat (Q,) “The maximum efficiency or Camot efficiency (e) of a heat engine is equal to the ratio of the useful work (W) to the input heat (Q,). ‘The Camot efficiency can be written in terms of the input temperature (Ty) and the exhaust temperature (T, ). eat engine Q=Wea WG maximum c= WIQu et ny © Qi QI e=d-Q0) oy TT e*(1-T/Tw) octicien of [P= QW evformance (CP) CP QMQ-a) for refrigerators or sir conditioners Paes (TL MT) “The CP fora refrigertor is the aio ofthe hea emoved from the cold region (Q,) © the work (W) performed to remove the het ‘The CP for an “ideal” refrigerator in terms of the temperatures ofthe low temperature reservoir (T,) and the high temperature reservoit(T). Entropy (S) is a quantitative measure of the disorder in a system. The change in entropy (AS) for a reversible process is directly proportional to the heat (Q) added to the system and inversely related to the temperature of the system (1). The unit of entropy is keal/K, where the heat is ‘measured in kcal and T in degrees Kelvin. Entropy as QT Statistical S=kinW Interpretation of or entropy S=23klog W CONCEPTS SUMMARY “The entropy of the system (S) is proper- tonal to the number of ways oF micro- states that can occur. k= 1.38 x 10" J/K (Boltsman’s constant), In i the logarithm. to the base e, € = 2.718, log is the Togarthm to the base 10, and W is the ‘number of microstates corresponding 10 to the given macrostate. ‘Thermodynamics is the study of energy transformations in natural provesses and involves. relations between heat, work and energy. In this chapter we shal study the first and second laws of thermodynamics, their significance, and application. 153,Physical Systems A system is any objector sets of objects which are under consideration, everything else in the univers is called the environment. In thermodynamics, a elosed system is one where mass may not enter or leave. In an open system mass may be exchanged with the envionment. First Law of Thermodynamics ‘The First Law of Thermodynamics is a statement of the law of conservation of energy. The first law states thatthe change in the intemal energy (AU) of a closed system is due to heat added or removed from the system (Q) andjor work done on or by the system: (W). aU=Q-W ‘Asa sign convention, heat added to a closed system is positive (Q = +), while heat removed is negaive (Q =. If work is done on the closed system, the intemal energy and temperature increase and W is negative (W = ). Ifan ideal gas is compressed in a cylinder with # moveable piston, the temperature and internal energy increase. I the system does work on the surroundings (environment), the ideal ges pushes the piston outward and the gas expands, the intemal energy and temperature decrease and W is positive (W ~ +), PY Dicgrams ‘The work done by a gas undergoing expansion or compression in a closed system can be ‘determined through use of a pressure-volume diagram (PV disgram). ‘The work done during ‘an incremental volume change (AV) equals the area under the PV curve. This area may be determined using the process of graphical integration. The following figures represent typical PY processes on an ideal gas. ‘In an isothermal process, (AB) in Fig. A, the temperature of the gas remains constant, AU = 0, Q = W. Based on the general gas law, PV = nRT, ifn and T are ccnstant, then, PV'= constant, Inn isobarie process, (DB) in Fig. A, the pressure is constant. The work done on or by the gas can be determined by using W = P AV. and P are constant; therefore ¥/T = constant. ‘An isoehoric process, (AD) in Fig. A, occurs at constant volume, AY = (therefore, W=PAV=Oand Q= AU. For this provess, P/T = constant In en adiabatic process, (AC) in Fig. B, no heat flows into or out of the system, Q-= 0, and W=- AU. An adiabatic process usually occurs when a gas is compressed or expands so rapidly that there is no time forthe heat to flow in or out of the system. It should be noted that an adiabatc process is quite different from an isothermal process, although the PV diagram for each process appears similar. 134— TEXTBOOK QUESTION Sinan Isoerial process, 3700 J of work Ts done by an ideal ga: is this enough information to tell how much heat has been added to the system? If so, how| mich? we ANSWER: The first law of thermodynamics can be written as Q= AU + W. In an isothermal process the temperature remains constant. Since the temperature remains constant, the intemal ‘energy remains constant and AU = 0. Therefore, all ofthe heat added during the process went io the wark done by he ideal gas (Q= W)- The amount of het aed 1 he system is 700 J [EXAMPLE PRORIEM Ia) Hw rmich enerpy me he adied to a 0.200 ke fee cube at 000°C] in order to change it to water at 0.00°C. Determine b) the work done on the system during th| [change and ¢) the change in the intemal energy of the system, art a, Step L. Solution: (Sections 15-1 and 15.2) Determine the energy | “The ice cube is undergoing a change of phase. Use the methods of required to melt he Section 14-6 to solve for the energy required to melt the ice cube. Q- me = (0.200 kg)(80 keal/kgy(4180 Weal) Q= 669 x 10) Part b. Step 1. ‘The change in volume of an ice cube when it melts is negligible. ‘The extemal air pressure can be considered to be constant. There- Determine the work fore, dene on the system uring the change. W-PAv W = P (lites) = 0 titer atm + 0 joules Parte. Step 1 ‘The work done on the system is zero joules; therefore, all ofthe heat energy added increases the intemal energy of the system. Determine the change in | However, the temperature of the system does not change during the the intemal energy of the | melting process and this indicates that the increase in the internal ‘stem, ‘energy cannot be inthe form of Kinetic energy. The increase in the internal energy is inthe form of potential energy as the molecules ‘overcome Ue aluaetive foices whic hold them in the solid phase. The increase in the internal energy may be determined as follows: Q-au+w 669x 10'S AU +07 AU = 669x104) 155[EXAMPLE PROBLEM 2 ‘One mole of an Weal gas ‘allowed to expand isochermally al -29.3%C from a volume of 4.0 liters and pressure 5.0 atm to a volume of 10.0 liters and pressure [2.0 aun. a) Draw a P-V diagram for the process, b) determine the work dore by the gas during| Ithe expansion. Part a Step 1. Solution: (Section 15-2) ‘The process is iso- sample calculation PL Ve= Pa Ve thermal, ie, PY = cconstani. Complete a data table for P'vs V ‘with enough data points so that & Teasonably accurate ‘raph may be crawn, Pant b. Step 1. Determine the work done by the as during the expansion. (60 atm)(4.0 liters) » (3.0 atm) V, V, = 67 liters data table Pum) —_-V liters) lies) ‘The work done by the gas dung the expansion is represented b the aea under the curve stween points A and B. The work dont can be estimated by graphical integration, ‘e. counting the omplete and parial blocks under the curve ad muliplying inthe work represented by the sre of | block. This methed ‘was previously sed in chapter 2. 10am CD 20liter ‘Work represented by one Block = (1.0 atm)2.0 iter) = 2.0 liter atm sum of complete blocks = 9.0 sum of partial blocks = 04 + 06 + 05 + 0.1 = 16 “Total numberof blocks under the uve = 9.0 + 1.6 = 10.6 156work done = (10.6 blocks)(2.0 titer aumjblock) = 21.2 liter atm. Because of significant figures, the answer is 21 liter aum = 2100 J. The Second Law of Thermodynamics ‘The Second Law of Thermodynamics can be stated in several equivalen: ways, three of which are: 1) Heat energy flows spontaneously from a hot object to a cold object but not vice vers. 2) Iki impossible to construct @ heat engine which is 100% efficient. Thus, heat engine can ‘convert some of the input heat into useful work, but the rest must be exhausted as waste heat, The entropy of an islated system never decreases. It ean only say the sume of increase. If the system is not isolated, then the change in entropy of the system (S,) plus the change in entropy of the environment (S,.) must be greater than or equal to zero. ‘The total entropy of any system plus that ofits environment increases as a result of any natural process BS= aS * ASm >0. First Statement of the Second Law ‘The fist statement of the second law is a statement from common experience. When two ‘objects, one hot and the other cold, come into contact, heat energy willbe transfered from the ‘system at higher temperature to the system at lower teinperature, but not vice versa. While the first law states that energy must be conserved, ie, the sum of the energy los and gained in any process must equal zero, it does not say that heat must flow from the hot object to the cold ‘object. The first law would not be violated ifthe hot object becatne hotter while the cold object became colder. The second law states that the direction of the heat flow mus: be from hot to cold Second Statement of the Second Law: Heat Engines ‘A beat engine is a device which is capable of changing thermal energy (Q,), also known 1a the input heat or heat of combustion of the fuel, into useful work (W). Heat engines cannot ‘be made to be 100% efficient and while part of the heat energy is converted to useful work, the remaining heat energy will be rejected to the environment of surroundings as waste heat (Q.), gi, exhaust from a car engine. Therefore, aw Q In an idealized engine, known as a Carnot engine, energy losses due to intemal friction, turbulence present in the fuel after ignition, etc. are not considered. Carnot determined that the ‘maximum efficiency (e) that could be realized from a heat engine depends on the temperature of the input heat (Ty) and the exhaust heat (T,), where Ty and ‘Tare expressed in degrees Kelvin. ‘ihe maximum efficiency or Carnot eMetency of a heat engine is dees following formulas: © * WiQy but since W = Qy-Qu, then wed by the 157© = (Qu QUNQ) and €= (1 - QQ Using the input and waste heat temperatures: = My Tyyw) ande= (1 -TyT) In onder for a Carnot engine tobe 100% efficeny, it would be necessary for the temperature of the exhaust heat to be at absolute zero (zero degrees Kelvin). This is & practical as well as 1 theoretical impossibility [EXAMPLE PROBLEM 3, A Camot engine takes in 3000 calories of input heat and rejects 2000] [calories as waste heat. The temperature ofthe waste heat is 600°C. Determine the a efficiency lof the engine and b) useftl work done by the engine Part a Sep 1 Solution: (Section 15) Completes data y= 300 cat 1 = (60 +27) K lomaton teh = 2000 ea = iMke poole 5, Pan a Step 2. €= Qa QQ) Detemine the = 600 cal - 2000 ca(300 ca) oo +003 or 333% Pat b Sep 1 = Wi alemate solution Solve for he 01333 = w/300 cl W=Q,-2 bythe engine, W100 ct = 000 cal - 2000 ca W= 1000 ca Pat. Sep ‘The efceney and tempenture of the waste heat ate krown, Save for he mee ey TOT) eens (0.333 » (Ty - 873 KIT 1 =1310K a [EXAMPLE PROBLEMA. The acual work done by aleat engine in I hour is 27x 10°F while fictional losses within the engine are 6,0 x 10° J. The engine operates between temperatures of| 1500 K and 1000 K. Determine the a) Camot efficiency of the engine, b) number of joules of| input heat taken in per hour by the engine and c) overall efficiency of the engine, 158Part a. Step 1 Complete a data table using the Information both ven and implied fn the problem. Determine the ota, work done by the machine. Part a. Step 3 Determine the Canot efficiency of tie engine, Pat. Step 1 Determine the inp et per how. ba Par: 0, Step 1. Determine the overall efficiency, ie the ‘efficiency’ afte’ frietional fosses are taken to account, Solution: (Section 15-5) Qa? T= 50K Qet en? Ty = 1000 K Waa = Wana * Wiss = 27 x 101 + 60x 10°) Woo ® 3.3 x 10°) Both the input heat temperature and waste heat temperature are known, therefore, = Ty TMT) = (1000 K - 500 Ky1000 K 2+ 050 or 50% Tn order to determine the input heat, itis necessary to use the total work output during 1 hou. = Wells) 0.50 = (3.3 x 10° NVQ = 66x 10's ‘The overall efficiency is related to the actual work done. eo MauidQ) = 2.7 x 10F 1/66 x 10°) ex 041 or 41% Refrigerators and Air Conditioners Reftigerators and air conditioners operate by removing heat from a low temperature (cold) reservoir and exhausting the heat othe higher temperature (hot) reservoir. In order to accomplish this task, work is done to cause heat to travel opposite from its normal direction. ‘The effectiveness of particular refrigerator or air conditioner in accomplishing the removal of heat from the low t ature reservoir is measured by the coefficient of performance (CP). ‘The CP for a refrigerator is the ratio ofthe heat removed from the cold region (Q,) to the work 159(OW) performed to temove the heat, Le, CP = (QW) bur W= Qu Q so that CP = Qu -Q) ‘The coefficient of performance for an “ideal” reftigerator can be writen in terms of the temperature of the low temperature reservoir and the temperature of the high temperature reservoir as follows Pas TT -T) [TEXTBOOK QUESTION 7, Can you warm the Kitchen in winter by leaving the oven doat en? Can you con! the kitchen on a hot summer day by leaving the refrigerator door open? ANSWER: Yes, you can warm the kitchen in winter by leaving the oven door open. Inthe case of an electric oven, electrical energy is converted to heat energy inthe heating coils. The heating coils warm the airin the oven and the warm air will warm the room. If the oven is a gas over, the gas flame heats the air and this warm air will warm the room, ‘You cannot cool the kitchen on a hot summer day by leaving the refrigerator door open. A reftigerator operates by removing heat from inside the refrigerator and. releasing it into the ait behind the refrigerator. Ifthe door i left open, the arin front ofthe refrigerator would be cooled but the air behind the reftigerator would be warmed. The additional heat generated by the ‘compressor would cause the overall temperature of the room to increase, ‘The author of ths study guide remembers the house ofa friend where the builder had cut a hole in the kitchen wall and inserted the refrigerator. The front of the reftigerator was in the ‘Kitchen while the back portion was in the garage. Therefore, the heat generated warmed the a inthe garage while the air inthe ktchen was cooled. Reversible and Irreversible Processes In an ideal gas, a reversible process is one in which the values of P, V, T, and U will have the same values inthe reverse order ifthe process is returned to its original state. In this type of process, the ideal gas can be retumed to is original sate with no change in the magnitude of the work done or the heat exchanged. To be reversible, the process must be done very slowly, ‘with no loss of energy due to dissipative forces such as friction and no heat conduction due to 4 temperature diffeence. In reality, these conditions cannot be met and all real processes are inreversibe, ‘Third Statement of the Second Law: Entropy Entropy (S) is a quantitative measure of the disorder in a system. The change in entropy (AS) for a reversitle process is directly proportional to the heat (Q) added to the system and inversely related to the temperature of the system (1) as-ar ‘The unit of entropy is keal/K, where the heat is measured in keal and TT in degrees Kelvin, 15410‘The Kelvin temperature at which heat is added must remain constant for a process 10 be reversible. [As heat is added to a system, the average kinetic energy of the molecules increases and the ‘motion becomes more disordered. At low temperatures we would expect to find a high degree of order while at high temperatures the system is likely to be very disordered. ‘Thus, energy ‘added while the system is at low temperature would introduce considerably more disorder than the same amount of energy introduced when the system is ata high temperature. Therefore, the ‘change in entropy is inversely proportional to the temperature at which the heat is added. Statistical Interpretation of Entropy ‘An equivalent definition of entropy can be given from a detailed analysis of the position and velocity (ie. microstate) of every molecule which makes up the system. The entropy of the system is proportional to the number of ways thatthe microstates can occur and is given by the following formula: SekinW=23 klog W where k is Boltzmann's constant, k = 1.38 x 10 J/K. In is the logarithm to the base e, where ‘¢ = 2.718. log is the logarithm tothe base 10. W is the number of mierostates corresponding to the given macrostate The state of highest entropy is the state that can be achieved in the largest number of ways and is therefore the most probable. —_—_——_—_—— TEXTBOOK QUESTION 16, (@) What happens if you Temove the lid of a Botte conteining| chlrine gas? (b) Does the reverse process ever happen? Why or why not? (c) Can you think| lof cher examples of imreversibility? ANSWER: (#) Once the lid is removed, chlorine gas would gradually diffuse throughout the room, The gas molecules tend to move in random directions reaching a state of maximum See Wau Waa Woe where W= PAV = 03+ (4 atm. L- 68 L) Wou= (35 liter stmX101.3 Jflter atm) = 350 J Part b. Step 1. Based on the information provided in the problem, the final femperature equals the original temperature. ‘There is no change in, Determine the change | temperature; and therefor, there is no change in the internal energy in the internal energy. | of the gas, ive., AU = OJ. Part c. Step 1. ‘The total heat flow (Q) is given by Determine the total Q-w+au heat flow into or ‘out of the gas. Q= 350 +03 = +3501 (into the gas) [TEXTBOOK PROBLEM 26. A Carnot engine wiles a heat source at 350°C and has an Ideal] |(Camot) efficiency of 28%. To increase the ideal efficiency to 35%, what must be the| temperature of the heat source? 1stdPatt a. Step 1 Convert the temper- ature of the heat source to Kelvi Part a, Step 2 Use the equation for Carnot efficiency to solve for the exhaust temperature. Part a, Step 3. ‘Use the equation for Carnot efficiency tosolve forthe new temperate of the heat source Solution: (Section 155) TK) = TCC) + 273 | eK) = $800 + 27310 = Ty TOT 028 = (623 K - 7.1623 K) (0:28,829 K) = 823 KT, 230 K = £23 KT, 1,=593K (Ty T VT, where © = 0:35 BK e 0.35 = (Ty ~ 593 KTy, Note: ‘, doesnot change (038) Ty = Ty - 593K 0465 Ty = 593 K Ty 910K = 637C Part a. Step 1 Complete a data table Part a. Step 2. Determine the coefficient of performance. Pat a. Step 3 Determine the work performed, [TEXTBOOK PROBLEM 32, A heat pump is used fo keep @ house warm at 22°C. How mush work is required of the pump to deliver 2800 J of heat into the house ifthe outdoor temperature lis (a) O°C, and (b) -1S*C1 Assume ideal (Camot) behavior. Solan: (Section 15.6) Tac +279C= 23K Ty +2204 2750 = 295K | y= 280) _Q>? crn? Coeticent of perfomance (CP) for the heat pump is given by P= (Ty (Ty - Th) CP = 095 KyRIS K -273 o ce = Qa /W 134 = 800 nyw 2103 Is.1sPart b, Step 1 Complee 3 aa Ty = ASC + 273°C = 258K Ty = NC + 27VC = 295 K Qy* 28001 Qa? c=? Par b, Step 2 Coefficient of performance (CP) for the heat pump is given by Determine the CP (Ty MT = TL) coeicient of peforms 1095 K - 258 art b. Step 3 Determine the ‘work performed, 7.97 = (2800 5) W w= 350) [TEXTBOOK PROBLEM 35. What isthe change in entropy of 250 g of Seam at 1OPC when| it is condensed to water at 100°C? Part a. Sep 1 AQ=mLy Note: from Table 14-3, for water, Ly = 22.6 x 10* kg = (250 g)[(1 kgy(1000 g)](- 22.6 x 10° Jkg) AQ=-5.65 x 10° Determine the heat released by the steam as it changes to water. Part a. Step 2. AQMT where T = 100°C = 373 K = 565 x 10° 873 K) 15110 YK Determine the ‘change in entioy. TEXTBOOK PROBLEM 41, An aluminum rod conducts 750 calls from @ heat source] intnined at 240°C oa lage body of water a 27°C, Determine [changes per uit time in rate at which entropy| Part a. Step 1 Solution: (Section 15-7) Somplee a Tae ZFC + 273°C ™ 300 K Tages = 240°C + 279°C = 513K, ata table. oe Qh = 7.50 cas = 31.4 Is___ (BS wallt= 7 ae Part a. Step 2 (AS uilt = (Soult + (ASiualft but AS = QIT Determine the ate of = (314 Spsy(513 K) + (431.4 499300 K) change of entiopy per unit time. (ASpulft = -6.12 x 10° J/sK + 1.05 x 10" JsK = + 4,35 x 10° JisK 15.16