# Chapter 19 The Second Law of Thermodynamics

Conceptual Problems
1 • Modern automobile gasoline engines have efficiencies of about 25%. About what percentage of the heat of combustion is not used for work but released as heat? (a) 25%, (b) 50%, (c) 75%, (d) 100%, (e) You cannot tell from the data given. Determine the Concept The efficiency of a heat engine is the ratio of the work done per cycle W to the heat absorbed from the high-temperature reservoir Qh. The percentage of the heat of combustion (heat absorbed from the hightemperature reservoir) is the ratio of Qc to Qh. We can use the relationship between W, Qh, and Qc ( W = Qh − Qc ) to find Qc/ Qh. Use the definition of efficiency and the relationship between W, Qh, and Qc to obtain: Solving for Qc/ Qh yields:

ε=

Q W Qh − Qc = = 1− c Qh Qh Qh

Qc = 1− ε Qh

Substitute for ε to obtain:

Qc = 1 − 0.25 = 0.75 Qh

and

(c )

is correct.

2 • If a heat engine does 100 kJ of work per cycle while releasing 400 kJ of heat, what is its efficiency? (a) 20%, (b) 25%, (c) 80%, (d) 400%, (e) You cannot tell from the data given. Determine the Concept The efficiency of a heat engine is the ratio of the work done per cycle W to the heat absorbed from the high-temperature reservoir Qh. We can use the relationship between W, Qh, and Qc ( W = Qh − Qc ) to express the efficiency of the heat engine in terms of Qc and W. Use the definition of efficiency and the relationship between W, Qh, and Qc to obtain:

ε=

W W = = Qh W + Qc

1 Q 1+ c W

1779

1780 Chapter 19 Substitute for Qc and W to obtain:

1 = 0.2 400 kJ 1+ 100 kJ and (a ) is correct.

ε=

3 • If the heat absorbed by a heat engine is 600 kJ per cycle, and it releases 480 kJ of heat each cycle, what is its efficiency? (a) 20%, (b) 80%, (c) 100%, (d) You cannot tell from the data given. Determine the Concept The efficiency of a heat engine is the ratio of the work done per cycle W to the heat absorbed from the high-temperature reservoir Qh. We can use the relationship between W, Qh, and Qc ( W = Qh − Qc ) to express the

efficiency of the heat engine in terms of Qc and Qh. Use the definition of efficiency and the relationship between W, Qh, and Qc to obtain: Substitute for Qc and Qh to obtain:

ε=

Q W Qh − Qc = = 1− c Qh Qh Qh

480 kJ = 0.2 600 kJ and (a ) is correct.

ε = 1−

4

Explain what distinguishes a refrigerator from a ″heat pump.″

Determine the Concept The job of a refrigerator is to move heat from its cold interior to the warmer kitchen environment. This process moves heat in a direction that is opposite its ″natural″ direction of flow, analogous to the use of a water pump to pump water out of a boat. The term heat pumps is used to describe devices, such as air conditioners, that are used to cool living and working spaces in the summer and warm them in the winter.

An air conditioner’s COP is mathematically identical to that Q of a refrigerator, that is, COPAC = COPref = c . However a heat pump’s COP is W Q defined differently, as COPhp = h . Explain clearly why the two COPs are W defined differently. Hint: Think of the end use of the three different devices.
5 • [SSM]

Determine the Concept The COP is defined so as to be a measure of the

The Second Law of Thermodynamics 1781 effectiveness of the device. For a refrigerator or air conditioner, the important quantity is the heat drawn from the already colder interior, Qc. For a heat pump, the ideas is to focus on the heat drawn into the warm interior of the house, Qh.
• Explain why you cannot cool your kitchen by leaving your refrigerator 6 door open on a hot day. (Why does turning on a room air conditioner cool down the room, but opening a refrigerator door does not?) Determine the Concept As described by the second law of thermodynamics, more heat must be transmitted to the outside world than is removed by a refrigerator or air conditioner. The heating coils on a refrigerator are inside the room, so the refrigerator actually heats the room in which it is located. The heating coils on an air conditioner are outside one’s living space, so the waste heat is vented to the outside. 7 • Why do steam-power-plant designers try to increase the temperature of the steam as much as possible? Determine the Concept Increasing the temperature of the steam increases its energy content. In addition, it increases the Carnot efficiency, and generally increases the efficiency of any heat engine. 8 • To increase the efficiency of a Carnot engine, you should (a) decrease the temperature of the hot reservoir, (b) increase the temperature of the cold reservoir, (c) increase the temperature of the hot reservoir, (d) change the ratio of maximum volume to minimum volume. Determine the Concept Because the efficiency of a Carnot cycle engine is given T by ε C = 1 − c , you should increase the temperature of the hot reservoir. (c ) is Th

correct.
9 •• [SSM] Explain why the following statement is true: To increase the efficiency of a Carnot engine, you should make the difference between the two operating temperatures as large as possible; but to increase the efficiency of a Carnot cycle refrigerator, you should make the difference between the two operating temperatures as small as possible. Determine the Concept A Carnot-cycle refrigerator is more efficient when the temperatures are close together because it requires less work to extract heat from an already cold interior if the temperature of the exterior is close to the temperature of the interior of the refrigerator. A Carnot-cycle heat engine is more efficient when the temperature difference is large because then more work is done by the engine for each unit of heat absorbed from the hot reservoir. A Carnot engine operates between a cold temperature reservoir of 10 ••

1782 Chapter 19 27°C and a high temperature reservoir of 127°C. Its efficiency is (a) 21%, (b) 25%, (c) 75%, (d) 79%.
Determine the Concept The efficiency of a Carnot cycle engine is given by ε C = 1 − Tc Th where Tc and Th (in kelvins) are the temperatures of the cold and hot

reservoirs, respectively. Substituting numerical values for Tc and Th yields:

εC = 1−

300 K = 0.25 400 K (b ) is correct.

11 •• The Carnot engine in Problem 10 is run in reverse as a refrigerator. Its COP is (a) 0.33, (b) 1.3, (c) 3.0 (d) 4.7. Determine the Concept The coefficient of performance of a Carnot cycle engine Q run in reverse as refrigerator is given by COPref = c . We can use the relationship W between W, Qc, and Qh to eliminate W from this expression and then use the Q T relationship, applicable only to a device operating in a Carnot cycle, c = c to Qh Th

express the refrigerator’s COP in terms of Tc and Th. The coefficient of performance of a refrigerator is given by:
Qc W or, because W = Qh − Qc , COPref = COPref = Qc Qh − Qc

Dividing the numerator and denominator of this fraction by Qc yields:
For a device operating in a Carnot cycle: Substitute in the expression for COPref to obtain:

COPref =

1 Qh −1 Qc

Qc Tc = Qh Th

COPref, C =

1 Th −1 Tc

Explain your answer. ΔEint. C = 12 •• On a humid day. water vapor condenses on a cold surface. COPref. During condensation. Pf Pi P B Ti B f i A Vi Vf A Tf V (a) Because Eint is a state function and the initial and final states are the same for the two paths. (c) ΔSA < ΔSB. It is not dependent on the process by which the change occurs. Ti to the final state Pf. B .The Second Law of Thermodynamics 1783 Substitute numerical values and evaluate COPref. C: 1 = 3. Determine the Concept The two paths are shown on the PV diagram to the right. Determine the Concept When water vapor condenses. (b) ΔSA > ΔSB. Figure 19-12 shows a thermodynamic cycle for an ideal gas on an ST 14 •• diagram. Vi. (d) (d ) is correct. its entropy decreases (the liquid state is a more ordered state than is the vapor state). Vf. like Eint. . Tf.0 400 K −1 300 K (c ) is correct. (b) remains constant. (c) is correct. Two possible paths are (A) an isothermal expansion followed by an adiabatic compression and (B) an adiabatic compression followed by an isothermal expansion. the entropy of the water (a) increases. (d) None of the above. (a) ΔEint A > ΔEint B. For these two paths. (d) may decrease or remain unchanged. A = ΔEint. is a state function and its change when the system moves from one state to another depends only on the system’s initial and final states. (b) and (c) S. (c) decreases. Thus ΔS A = ΔS B . We can use the concept of a state function to choose from among the alternatives given as possible answers to the problem. Identify this cycle and sketch it on a PV diagram. 13 •• An ideal gas is taken reversibly from an initial state Pi.

The points A. To determine how S depends on T along b→c and d→a. from c→d S is constant while T decreases. C→D is an adiabatic compression and D→A is a constant-volume process that returns the gas to its original state. c→d is an adiabatic expansion and d→a is a constant-volume cooling. and from d to a both S and T decrease. consider the entropy change of the gas from point b to an arbitrary point on the path b→c where the entropy and temperature of the gas are S and T. Therefore. B. the cycle is the Carnot cycle shown in the adjacent PV diagram. because heat is entering the system. and D in Figure 19-13 correspond to points c. C. b→c is a constant volume heating. respectively: Because Won = 0 for this constantvolume process: Substituting for Q yields: Q T where. d. ΔS = ΔEint = Qin = Q = C V ΔT = C V (T − Tb ) C V (T − Tb ) ⎛ T ⎞ = C V ⎜1 − b ⎟ T ⎝ T ⎠ ΔS = . from a to b. and b. The cycle is that of the Otto engine (see Figure 19-3). Determine the Concept Note that A→B is an adiabatic expansion. a. Q is positive. Refer to Figure 19-3. heat is added to the system and both S and T increase. in Figure 19-3. from b to c. There a→b is an adiabatic compression. Identify the type of engine represented by this diagram.1784 Chapter 19 Determine the Concept The processes A→B and C→D are adiabatic and the processes B→C and D→A are isothermal. Sketch an ST diagram of the Otto cycle. S is constant and T increases. P B C A D V 15 •• Figure 19-13 shows a thermodynamic cycle for an ideal gas on an SV diagram.) Determine the Concept The Otto cycle consists of four quasi-static steps. (The Otto cycle is discussed 16 •• in Section 19-1. respectively. B→C is a constant-volume process in which the entropy decreases. So.

. and S is constant while V decreases. the slope of the path is positive and the slope decreases as T increases.The Second Law of Thermodynamics 1785 On path b→c the entropy is given by: ⎛ T ⎞ S = S b + ΔS = S b + C V ⎜1 − b ⎟ ⎝ T ⎠ T dS = C V b2 dT T 2 T d S = −2C V b3 2 dT T The first and second derivatives. The concavity of the path is negative for all T. isentropic. that is. dS dT and d 2 S dT 2 . along path d→a. An ST diagram for the Otto cycle is shown to the right. give the slope and concavity of the path. process 1→2 is an isothermal expansion. the slope of the path is positive and the slope decreases as T increases. In this process heat is added to the system and the entropy and volume increase. The concavity of the path is negative for all T. (For an ideal gas CV is a positive constant. process 4→1 is adiabatic.): These results tell us that. Calculate these derivatives assuming CV is constant. Following the same procedure on path d→a gives: ⎛ T ⎞ S = S d + C V ⎜1 − d ⎟ ⎝ T ⎠ T dS = C V d2 dT T 2 T d S = −2C V d3 2 dT T These results tell us that. Finally. S d c a b T 17 •• [SSM] Sketch an SV diagram of the Carnot cycle for an ideal gas. Process 2→3 is adiabatic. along path b→c. so S is constant as V increases. Process 3→4 is an isothermal compression in which S decreases and V also decreases. Determine the Concept Referring to Figure 19-8.

the work done by the gas. and thus the heat added to the gas.) .1786 Chapter 19 During the isothermal expansion (from point 1 to point 2) the work done by the gas equals the heat added to the gas. (The Otto cycle is discussed in Section 19-1. The change in entropy of the gas from point 1 (where the temperature is T1) to an arbitrary point on the curve is given by: For an isothermal expansion. are given by: Substituting for Q yields: ΔS = Q T1 ⎛V ⎞ Q = W = nRT1 ln⎜ ⎜V ⎟ ⎟ ⎝ 1⎠ ⎛V ⎞ ΔS = nR ln⎜ ⎟ ⎜V ⎟ ⎝ 1⎠ ⎛V ⎞ S = S1 + nR ln⎜ ⎜V ⎟ ⎟ ⎝ 1⎠ Since S = S1 + ΔS . S 2 3 1 4 V 18 •• Sketch an SV diagram of the Otto cycle. S V An SV graph for the Carnot cycle (see Figure 19-8) is shown to the right. This graph establishes the curvature of the 1→2 and 3→4 paths for the SV graph. we have: The graph of S as a function of V for an isothermal expansion shown to the right was plotted using a spreadsheet program.

and freezer. basement.kit Qc.kit Wc.basement and Qc. It is true that order will not come about from the disordered chaos of his room – unless he applies some elbow grease.basement Q − Qc.basement −1 Qc. Estimation and Approximation Estimate the change in COP of your electric food freezer when it is 21 • removed from your kitchen to its new location in your basement.kit = Qh.1788 Chapter 19 required is an agent doing work – for example.basement Qc.basement −1 Qc.basement = 1 Qh.kit Qh. His cleanup efforts will be rewarded with an orderly system after a sufficient time for him to complete the task.basement W = c. then we can use the proportion Qh Qc = Th Tc to express the ratio of the coefficients of performance in terms of the temperatures in the kitchen.basement = h.kit 1 COPbasement COPkit Qh.kit − Qc. which is 8°C cooler than your kitchen.basement COPbasement COPkit Because W = Qh − Qc for a heat engine or refrigerator: COPbasement COPkit Divide the numerators and denominators by Qc.kit −1 Qc. The ratio of the coefficients of performance in the basement and kitchen is given by: Qc. your friend – on the system in order to reduce the level of chaos and bring about order.basement Qc.kit and simplify to obtain: .kit −1 Qc. If we further assume that the freezer operates in a Carnot cycle.kit Qh. Picture the Problem We can use the definition of the coefficient of performance to express the ratio of the coefficient of performance in your basement to the coefficient of performance in the kitchen.

you need to provide her with the following estimates: (a) the highest COP possible for a household refrigerator. She decides to return the next day to buy the most efficient refrigerator.4. and (b) and the highest rate possible for the heat to be released by the refrigerator if the refrigerator uses 600 W of electrical power.252×10 27 = 27 1 101.0)1.252×10 27 ≈ 10 −10 23 •• [SSM] Estimate the maximum efficiency of an automobile engine that has a compression ratio of 8. she asks you about the efficiencies of the available models. (The Otto cycle is discussed in Section 19-1. Assume the engine operates according to the Otto cycle and assume γ = 1. Wanting to buy the most efficient refrigerator possible.4 for diatomic gases) and evaluate εC: 1 ≈ 56% (8.0:1. To make the sale. . One day.252×10 27 = 10 −1. We can use the expression for the Carnot efficiency and the equation relating V and T for a quasi-static adiabatic expansion to express the Carnot efficiency of the engine in terms of its compression ratio.4−1 24 •• You are working as an appliance salesperson during the summer.0.1790 Chapter 19 Substitute for N in equation (1) and evaluate p: ⎛1⎞ p=⎜ ⎟ ⎝ 10 ⎠ 1. your physics professor comes into your store to buy a new refrigerator. Express the Carnot efficiency of an engine operating between the temperatures Tc and Th: Relate the temperatures Tc and Th to the volumes Vc and Vh for a quasistatic adiabatic compression from Vc to Vh: Substitute for Tc to obtain: Th εC = 1 − Tc Th T V γ −1 ⎛ Vh ⎞ ⇒ c = hγ −1 = ⎜ ⎟ ⎜V ⎟ Th Vc ⎝ c⎠ γ −1 TcVc γ −1 = ThVh γ −1 ⎛ Vh ⎞ εC = 1 − ⎜ ⎟ ⎜V ⎟ ⎝ c⎠ γ −1 Express the compression ratio r: r= Vc Vh 1 Substituting for r yields: εC = 1 − ε C = 1− r γ −1 Substitute numerical values for r and γ (1. ) Picture the Problem The maximum efficiency of an automobile engine is given by the efficiency of a Carnot engine operating between the same two temperatures.

for the sake of finding the upper limit on the COP.65 ≈ 14 293 K −1 273 K (2) Substitute numerical values and evaluate COPmax: COPmax = (b) Solve equation (1) for Qc: Differentiate equation (2) with respect to time to obtain: Substitute numerical values and dQc evaluate : dt Qc = W (COP ) dQc dW = (COP ) dt dt dQc = (13. We can use the definition of the COP of a refrigerator and the relationship between the temperatures of the hot and cold reservoir and Qh and Qc to find an upper limit on the COP of a household refrigerator.2 kW dt . then the refrigerator must be able to maintain a temperature difference of 20 K.The Second Law of Thermodynamics 1791 Picture the Problem If we assume that the temperature on the inside of the refrigerator is 0°C (273 K) and the room temperature to be 20°C (293 K). (a) Using its definition. express the COP of a household refrigerator: Apply conservation of energy to the refrigerator to obtain: Substitute for W and simplify to obtain: COP = Qc W (1) W + Qc = Qh ⇒ W = Qh − Qc Qc 1 = Qh − Qc Qh −1 Qc COP = Assume. In (b) we can solve the definition of COP for Qc and differentiate the resulting equation with respect to time to estimate the rate at which heat is being drawn from the refrigerator compartment. that the refrigerator is a Carnot refrigerator and relate the temperatures of the hot and cold reservoirs to Qh and Qc: Substitute for Qh Th = Qc Tc Qh to obtain: Qc COPmax = 1 Th −1 Tc 1 = 13.65)(600 J/s ) = 8.

one on one side and one on the other.12 s ≈ 5 s 2 100 s −1 ( ) (b) Evaluate t for N = 100 molecules: t= 2100 2 100 s −1 ( ) 1y 3.0 L of air at a pressure of 10−12 torr and an assumed temperature of 300 K.022×10 let 23 10 x = 26.The Second Law of Thermodynamics 1793 chance of it being on one side or the other.022 ×1023 molecules: To evaluate 26. With two molecules. the probability of N molecules all being on one side of the box is P = 2/2N.5 × 10 299 s × ≈ 2 × 10 291 y (d) Evaluate t for N = 1. both on the other.156 × 10 7 s = 0.022×10 and take the logarithm of both sides of the equation to obtain: 23 26. or a 50% chance of them both being on either side. which means that.022 ×10 )ln 2 = x ln10 ⇒ x ≈ 10 23 23 . so there is a 25% (1 in 4) chance of them both being on a particular side. there are four possible combinations (both on one side. In (e) we can apply the ideal gas law to find the number or the other is t = 2(100 ) of molecules in 1.156 × 10 7 s = 6. and the reverse). Extending this logic.34 × 10 27 s × ≈ 2 × 10 20 y (c) Evaluate t for N = 1000 molecules: t= 21000 2 100 s −1 ( ) To evaluate 21000 let 10 x = 21000 and take the logarithm of both sides of the equation to obtain: (1000)ln 2 = x ln10 ⇒ x = 301 Substitute to obtain: t= 10 301 2 100 s −1 ( ) 1y 3.0 mol =6. the time it would take them to cover all the combinations and all get on one side 2N . (a) Evaluate t for N = 10 molecules: t= 210 = 5. if the molecules shuffle 100 times a second.022×10 t= 2(100 s −1 ) 23 (6.

22×10 t= 2(100 s −1 ) 7 (3.156 × 10 7 s 7 ( ) ≈ 1010 y 7 Express the ratio of this waiting time to the lifetime of the universe tuniverse: t tuniverse or 7 1010 y = 10 ≈ 1010 10 y 7 t ≈ 1010 tuniverse 7 Heat Engines and Refrigerators 27 • [SSM] A heat engine with 20.100 kJ of work during each cycle. (a) How much heat is absorbed from the hot reservoir during each cycle? (b) How much heat is released to the cold reservoir during each cycle? .0 L ) (1.22×107 molecules: To evaluate 23.22 × 107 molecules 2 3.156 ×10 s ⎠ 23 ( ) ≈ 1010 y 23 (e) Solve the ideal gas law for the number of molecules N in the gas: Assuming the gas to be at room temperature (300 K).22×10 let 7 10 x = 23. substitute numerical values and evaluate N: Evaluate t for N = 3.1794 Chapter 19 Substituting for x yields: 1010 1y ⎛ ⎞ t≈ 7 ⎟ −1 ⎜ 2 100 s ⎝ 3.22×10 and take the logarithm of both sides of the equation to obtain: Substituting for x yields: 7 N= PV kT −12 (10 N= torr )(133.0% efficiency does 0.22 × 10 )ln 2 = x ln10 ⇒ x ≈ 10 7 7 1010 1y × t= −1 2 100 s 3.381×10−23 J/K )(300 K ) = 3.32 Pa/torr )(1.

(a) What is its efficiency? (b) How much heat is released to the cold reservoir during each cycle? Picture the Problem (a) The efficiency of the engine is defined to be ε = W Qh where W is the work done per cycle and Qh is the heat absorbed from the hot reservoir during each cycle. Qh = W + Qc . (b) Because. (a) Qh absorbed from the hot reservoir during each cycle is given by: (b) Use Qh = W + Qc to obtain: Qh = W = 100 J = 500 J 0.50 s. (b) We can apply conservation of energy to the engine to obtain Qh = W + Qc and solve this equation for the heat Qc released to the cold reservoir during each cycle. (a) What is its efficiency? (b) If each cycle takes 0.400 kJ of heat from the hot reservoir and does 0. (a) The efficiency of the heat engine is given by: ε= Q W Qh − Qc = = 1− c Qh Qh Qh . from conservation of energy.The Second Law of Thermodynamics 1795 Picture the Problem (a) The efficiency of the engine is defined to be ε = W Qh where W is the work done per cycle and Qh is the heat absorbed from the hot reservoir during each cycle. we can express the efficiency of the engine in terms of the heat Qc released to the cold reservoir during each cycle.200 ε Qc = Qh − W = 500 J − 100 J = 400 J 28 • A heat engine absorbs 0. Picture the Problem We can use its definition to find the efficiency of the engine and the definition of power to find its power output. (a) The efficiency of the heat engine is given by: (b) Apply conservation of energy to the engine to obtain: Substitute numerical values and evaluate Qc: ε= W 120 J = = 30% Qh 400 J Qh = W + Qc ⇒ Qc = Qh − W Qc = 400 J − 120 J = 280 J 29 • A heat engine absorbs 100 J of heat from the hot reservoir and releases 60 J of heat to the cold reservoir during each cycle. find the power output of this engine.120 kJ of work during each cycle.

(a) Find the coefficient of performance of the refrigerator. (b) The refrigerator is reversible.1796 Chapter 19 Substitute numerical values and evaluate ε: (b) The power output P of this engine is the rate at which it does work: Substitute numerical values and evaluate P: ε = 1− 60 J = 40% 100 J P= dQh dW d = ε Qh = ε dt dt dt ⎛ 100 J ⎞ P = (0. If it is run backward as a heat engine between the same two reservoirs.7 8. what is its efficiency? Picture the Problem We can apply their definitions to find the COP of the refrigerator and the efficiency of the heat engine.0 kJ = 1.0 kJ = 38% 8.0 kJ .0 kJ of heat from a cold reservoir and releases 8.40 )⎜ ⎜ 0.0 kJ ε= W Qh Qh − Qc Q = 1− c Qh Qh ε= ε = 1− 5.500 s ⎟ ⎟ = 80 W ⎝ ⎠ 30 • A refrigerator absorbs 5. (a) The COP of a refrigerator is defined to be: Apply conservation of energy to relate the work done per cycle to Qh and Qc: Substitute for W to obtain: COP = Qc W W = Qh − Qc COP = Qc Qh − Qc Substitute numerical values and evaluate COP: (b) The efficiency of a heat pump is defined to be: Apply conservation of energy to the heat pump to obtain: Substitute numerical values and evaluate ε : COP = 5.0 kJ to a hot reservoir.0 kJ − 5.

3. find the work done by the gas. The gas is heated at constant volume to P2 = 2.The Second Law of Thermodynamics 1797 31 •• [SSM] The working substance of an engine is 1. For each step of the cycle. We can use the 1st law of thermodynamics to find the change in internal energy for each step of the cycle. The gas is then cooled at constant volume until its pressure is again 1. We can then find the work done on the gas during each process from the area under each straight-line segment and the heat that enters the system from Q = CV ΔT and Q = CP ΔT . It then expands at constant pressure until its volume is 49. and 4.00 mol)⎛ ⎜ 8.00 atm and V1 = 24. (a) Show this cycle on a PV diagram. and the change in the internal energy of the gas. Hence: T2 = 2T1 = 600 K T3 = 2T2 = 1200 K . (a) The cycle is shown to the right: Apply the ideal-gas law to state 1 to find T1: T1 = P1V1 = nR (1. Picture the Problem To find the heat added during each step we need to find the temperatures in states 1.6 L ) − 2 L ⋅ atm ⎞ (1. It is then compressed at constant pressure to its original state.206 ×10 ⎟ mol ⋅ K ⎠ ⎝ = 300 K The pressure doubles while the volume remains constant between states 1 and 2. we can find the efficiency of the cycle from the work done each cycle and the heat that enters the system each cycle. Hence: The volume doubles while the pressure remains constant between states 2 and 3. The cycle begins at P1 = 1. (b) Find the efficiency of the cycle. All the steps are quasi-static and reversible.00 atm )(24.2 L. Finally. the heat absorbed by the gas.00 atm. 2.6 L.00 mol of a monatomic ideal gas.00 atm.

34 = CV ΔT34 = 3 RΔT34 = 3 8.1798 Chapter 19 The pressure is halved while the volume remains constant between states 3 and 4.314 ⎟ (600 K − 300 K ) = 3.6 L )⎜ ⎟ = − 4.325 J ⎞ Won = −W23 = − PΔV23 = −(2. 34 = −7.2 L − 24. Hence: For path 1→2: W12 = PΔV12 = 0 T4 = 1 T = 600 K 2 3 and J ⎞ ⎛ Q12 = CV ΔT12 = 3 RΔT12 = 3 8.5 kJ and J ⎞ ⎛ Q34 = ΔEint.48 kJ .74 kJ 2 2⎜ mol ⋅ K ⎠ ⎝ The change in the internal energy of the system as it goes from state 1 to state 2 is given by the 1st law of thermodynamics: Because W12 = 0 : For path 2→3: ΔEint = Qin + Won ΔEint.5 kJ 2⎜ 2 mol ⋅ K ⎠ ⎝ Apply ΔEint = Qin + Won to obtain: For path 3→4: W34 = PΔV34 = 0 ΔEint.74 kJ ⎛ 101.5 kJ − 4. 23 = 12.00 atm )(49.12 = Q12 = 3.99 kJ ⎝ L ⋅ atm ⎠ J ⎞ ⎛ Q23 = CP ΔT23 = 5 RΔT23 = 5 8.99 kJ = 7.48 kJ 2 2⎜ mol ⋅ K ⎠ ⎝ Apply ΔEint = Qin + Won to obtain: ΔEint.314 ⎟ (600 K − 1200 K ) = − 7.314 ⎟ (1200 K − 600 K ) = 12.48 kJ + 0 = − 7.

00 atm and a volume of 20. the results of the preceding calculations are summarized in the following table: Process Won .The Second Law of Thermodynamics 1799 For path 4→1: ⎛ 101.49 kJ ⎝ L ⋅ atm ⎠ and J ⎞ ⎛ Q41 = CP ΔT41 = 5 RΔT41 = 5 8. . as expected because the system returns to its initial state. and (3) heating at constant volume to its original pressure.5 −7. 41 = −6.6 L − 49.99 0 2. Find the efficiency of this cycle. kJ 1→2 2→3 3→4 4→1 0 −4.74 kJ + 12. (2) a compression at constant pressure to its original volume of 10.24 3.74 12.00 mol of a diatomic ideal gas.75 kJ For easy reference. the sum of the changes in the internal energy for the cycle is zero.49 kJ ≈ 15% 3.0 L.48 −3. 32 •• The working substance of an engine is 1.24 kJ + 2. kJ Qin .0 L to a pressure of 1. kJ ΔEint (= Qin + Won ) .0 L. Note also that.314 ⎟ (300 K − 600 K ) = − 6.48 −6. The engine operates in a cycle consisting of three steps: (1) an adiabatic expansion from an initial volume of 10.325 J ⎞ Won = −W41 = − PΔV41 = −(1.99 kJ − 2.49 3.75 (b) The efficiency of the cycle is given by: Substitute numerical values and evaluate ε: ε= Wby Qin = − W23 + (− W41 ) Q12 + Q23 ε= 4.24 kJ 2⎜ 2 mol ⋅ K ⎠ ⎝ Apply ΔEint = Qin + Won to obtain: ΔEint.2 L )⎜ ⎟ = 2.49 kJ = − 3.5 −7.5 kJ Remarks: Note that the work done per cycle is the area bounded by the rectangular path.00 atm )(24.74 7.

0 atm ⋅ L Won = ΔEint − Qin = −Qin = Q12 + Q23 + Q31 = 0 − 35.0 L ) = 41.639 atm − 1.0 atm ⋅ L Q31 = C V ΔT31 = 5 RΔT31 = 5 ΔPV31 2 2 = 5 2 (2.0 L ⎠ 1.0 atm ⋅ L = 15% 41atm ⋅ L . P (atm) 2.1800 Chapter 19 Picture the Problem The three steps in the process are shown on the PV diagram.639 2 1 1 3 2 0 0 10.00 atm) = 2.0 L ) = −35.0 L ⎞ P1 = ⎜ ⎟ ⎝ 10.0 atm ⋅ L Substitute numerical values in equation (1) and evaluate ε : ε= 6.00 atm )(10.4 (1.0 20.0 V(L) The pressures and volumes at the end points of the adiabatic expansion are related according to: Substitute numerical values and evaluate P1: Express the efficiency of the cycle: ⎛ V2 ⎞ P1V1 = P2V2 ⇒ P1 = ⎜ ⎟ P2 ⎜V ⎟ ⎝ 1⎠ γ γ γ ⎛ 20.639 atm (1) ε= W Qh No heat enters or leaves the system during the adiabatic expansion: Find the heat entering or leaving the system during the isobaric compression: Find the heat entering or leaving the system during the constantvolume process: Apply the 1st law of thermodynamics to the cycle ( ΔEint.0 atm ⋅ L = 6. We can find the efficiency of the cycle by finding the work done by the gas and the heat that enters the system per cycle.0 L − 20. cycle = 0 ) to obtain: Q12 = 0 7 Q23 = CP ΔT23 = 7 2 RΔT23 = 2 PΔV23 = 7 2 (1.00 atm )(10.0 atm ⋅ L + 41.

2 + Qh. 2 + Qh. 4 (1) Because steps 2 and 4 are constantvolume processes. 3. 2. A.6 L and a temperature of 400 K performs a cycle consisting of four steps: (1) an isothermal expansion at 400 K to twice its initial volume. and because the internal energy does not change during step 1 while work is done by the gas. Assume that Cv = 21.3 + Qh.0 J/K. and D identify the four states of the gas and the numerals 1. 2 P (atm) 1.5 1 0. and (4) heating at constant volume to its original temperature of 400 K. Picture the Problem We can find the efficiency of the cycle by finding the work done by the gas and the heat that enters the system per cycle.1 + Qh.5 0 0 10 20 4 D A 1 3 C B 2 400 K 300 K 30 40 V (L) 50 60 Express the efficiency of the cycle: ε= W1 + W2 + W3 + W4 W = Qh Qh.00 mol of an ideal gas initially at a volume of 24. 4 W + W3 W = 1 Qh Qh. The PV diagram of the cycle is shown to the right. C.1 + Qh. (2) cooling at constant volume to a temperature of 300 K (3) an isothermal compression to its original volume.The Second Law of Thermodynamics 1801 33 •• An engine using 1. Sketch the cycle on a PV diagram and find its efficiency. B. W2 = W4 = 0: Because the internal energy of the gas increases in step 4 while no work is done. 4 W1 + 0 + W3 + 0 W = Qh Qh. heat enters the system only during these processes: The work done during the isothermal expansion (1) is given by: The work done during the isothermal compression (3) is given by: ε= ε= ⎛ VB W1 = nRT ln⎜ ⎜V ⎝ A ⎞ ⎟ ⎟ ⎠ ⎛ VD ⎞ W3 = nRTc ln⎜ ⎜V ⎟ ⎟ ⎝ C⎠ .1 + Qh.3 + Qh. and 4 represent the four steps through which the gas is taken.

substitute and simplify to obtain: VA VC 2 ⎛1⎞ Th ln (2 ) + Tc ln⎜ ⎟ Th − Tc ⎝ 2 ⎠ = Th ln (2) − Tc ln (2) = ε= C CV C (Th − Tc ) Th ln (2) + V (Th − Tc ) Th ln (2) + V (Th − Tc ) Th + nR nR nR ln (2) Substitute numerical values and evaluate ε: ε= 400 K − 300 K = 13. Because the change in internal energy is zero for the isothermal process.00 mol of an ideal monatomic gas initially at a volume of 25. All the processes are quasi-static.1% J 21. Picture the Problem We can use the ideal-gas law to find the temperatures of each state of the gas and the heat capacities at constant volume and constant pressure to find the heat flow for the constant-volume and isobaric processes. (b) the heat transfer for each part of the cycle. the heat that enters the system during this isothermal expansion is given by: The heat that enters the system during the constant-volume step 4 is given by: Substituting in equation (1) yields: ⎛ VB Q1 = W1 = nRTh ln⎜ ⎜V ⎝ A ⎞ ⎟ ⎟ ⎠ Q4 = C V ΔT = C V (Th − Tc ) ⎛ VD ⎞ ⎛ VB ⎞ nRTh ln⎜ ⎜V ⎟ ⎟ + nRTc ln⎜ ⎜V ⎟ ⎟ A ⎠ ⎝ ⎝ C⎠ ε= ⎛ VB ⎞ nRTh ln⎜ ⎜V ⎟ ⎟ + C V (Th − Tc ) ⎝ A⎠ Noting the VB V 1 = 2 and D = .0 K (400 K − 300 K ) 400 K + J ⎞ ⎛ (1.314 ⎟ ln (2) mol ⋅ K ⎠ ⎝ 34 •• Figure 19-15 shows the cycle followed by 1.0 L. we can use the expression for the work done on or by a gas during an isothermal process .00 mol)⎜ 8.1802 Chapter 19 Because there is no change in the internal energy of the system during step 1. and (c) the efficiency of the cycle. Determine (a) the temperature of each numbered state of the cycle.

0 L ⎟ ⎟ = 3.24 kJ = 0.74 kJ + 3.74 kJ 2 2⎜ mol ⋅ K ⎠ ⎝ Find the heat entering or leaving the system for the isothermal process from 2 → 3: ⎛ V3 ⎞ ⎛ 50.00 mol)⎛ ⎜ 8. (a) Use the ideal-gas law to find the temperature at point 1: T1 = P1V1 = nR (100 kPa )(25.0 L ⎞ J ⎞ ⎛ Q23 = nRT2 ln⎜ ⎜ 25.The Second Law of Thermodynamics 1803 to find the heat flow during such a process.00 mol)⎜ 8.24 kJ 2 2⎜ mol ⋅ K ⎠ ⎝ (c) Express the efficiency of the cycle: Apply the 1st law of thermodynamics to the cycle: ε= W W = Qin Q12 + Q23 (1) W = ∑ Q = Q12 + Q23 + Q31 = 3.314 ⎟ (601 K − 301 K ) = 3.314 ⎟ mol ⋅ K ⎠ ⎝ = 601 K (b) Find the heat entering the system for the constant-volume process from 1 → 2: J ⎞ ⎛ Q12 = C V ΔT12 = 3 RΔT12 = 3 8. .0 L ) = J ⎞ (1. ΔEint = 0 . for the cycle. we can find the efficiency of the cycle from its definition.0 L ) (1.00 mol)⎛ ⎜ 8.314 ⎟ (301 K − 601 K ) = − 6.46 kJ ⎜V ⎟ ⎟ = (1.96 kJ because.314 mol ⋅ K ⎟ (601 K )ln⎜ ⎝ ⎠ ⎝ ⎠ ⎝ 2⎠ Find the heat leaving the system during the isobaric compression from 3 → 1: J ⎞ ⎛ Q31 = C P ΔT31 = 5 RΔT31 = 5 8. Finally.314 ⎝ J ⎞ ⎟ mol ⋅ K ⎠ = 301 K Use the ideal-gas law to find the temperatures at points 2 and 3: T2 = T3 = P2V2 nR (200 kPa )(25.46 kJ − 6.

0 atm ) 600 K ε= W Qin (1) Use the area of the rectangle to find the work done each cycle: W = ΔPΔV = (300 L − 100 L )(3.0 atm − 1.74 kJ + 3.96 kJ = 13% 3. The temperature of state 1 is 200 K. We can find the efficiency of the cycle from its definition.0 atm ) = (3.46 kJ 35 •• An ideal diatomic gas follows the cycle shown in Figure 19-16.0 atm ) = (1. using the area enclosed by the cycle to find the work done per cycle and the heat entering the system between states 1 and 2 and 2 and 3 to determine Qin.0 atm ) 600 K T3 = T2 P3V3 V = T2 3 P2V2 V2 T3 = (600 K ) (300 L ) = (100 L ) 1800 K T4 = T3 P4V4 P = T3 4 P3V3 P3 T4 = (1800 K ) (1. Picture the Problem We can use the ideal-gas law to find the temperatures of each state of the gas. Determine (a) the temperatures of the other three numbered states of the cycle and (b) the efficiency of the cycle. (a) Use the ideal-gas law for a fixed amount of gas to find the temperature in state 2 to the temperature in state 1: Substitute numerical values and evaluate T2: Apply the ideal-gas law for a fixed amount of gas to states 2 and 3 to obtain: Substitute numerical values and evaluate T3: Apply the ideal-gas law for a fixed amount of gas to states 3 and 4 to obtain: Substitute numerical values and evaluate T4: (b) The efficiency of the cycle is: PV P P PV 1V1 = 2 2 ⇒ T2 = T1 2 2 = T1 2 T1 T2 P P 1V1 1 T2 = (200 K ) (3.0 atm ) = 400 atm ⋅ L .1804 Chapter 19 Substitute numerical values in equation (1) and evaluate ε : ε= 0.

The cycle of a Stirling engine is as follows: (1) isothermal compression of the working gas (2) heating of the gas at constant volume. (b) We can show that the entropy change during one Stirling cycle is zero by adding up the entropy changes for the four processes.0 atm )(100 L ) = T1 200 K = 0. (3) an isothermal expansion of the gas. P S 2 (2) (3) Th (1) Tc (4) ΔV = 0 3 Th Tc 4 V ΔV = 0 1 T .50 L ⋅ atm/K Noting that heat enters the system between states 1 and 2 and states 2 and 3.The Second Law of Thermodynamics 1805 Apply the ideal-gas law to state 1 to find the product of n and R: nR = P1V1 (1. an old design for a heat engine. known as the Stirling engine has been promoted as a means of producing power from solar energy. (b) Find the entropy change of the gas for each step of the cycle and show that the sum of these entropy changes is equal to zero. and (4) cooling of the gas at constant volume. (a) Sketch PV and ST diagrams for the Stirling cycle. express Qin: Qin = Q12 + Q23 = C V ΔT12 + C P ΔT23 =5 nRΔT12 + 7 nRΔT23 2 2 = (5 ΔT12 + 7 ΔT23 )nR 2 2 Substitute numerical values and evaluate Qin: L ⋅ atm ⎞ ⎛ 7 Qin = [5 1800 K − 600 K )]⎜ 0. Picture the Problem (a) The PV and ST cycles are shown below.50 ⎟ = 2600 atm ⋅ L 2 (600 K − 200 K ) + 2 ( K ⎠ ⎝ Substitute numerical values in equation (1) and evaluate ε : ε= 400 atm ⋅ L = 15% 2600 atm ⋅ L 36 ••• Recently.

. Life’s Devices. and a general knowledge of the conditions under which most warm-blooded organisms exist. because V2 = V3 and V1 = V4. the entropy change for the isothermal process from state 3 to state 4 is: ⎛ V2 ⎞ ΔS12 = nR ln⎜ ⎜V ⎟ ⎟ ⎝ 1⎠ ⎛ V4 ⎞ ΔS 34 = nR ln⎜ ⎜V ⎟ ⎟ ⎝ 3⎠ or. (a) Calculate the efficiency of a heat engine operating between body temperature (98. ⎛ V1 ⎞ ⎛ V2 ⎞ ΔS 34 = nR ln⎜ ⎜V ⎟ ⎟ = − nR ln⎜ ⎜V ⎟ ⎟ ⎝ 2⎠ ⎝ 1⎠ The change in entropy for a constantvolume process is given by: ΔS isochoric dQ f nCV dT =∫ =∫ T T Ti ⎛ Tf = nC V ln⎜ ⎜T ⎝ i ⎞ ⎟ ⎟ ⎠ T For the constant-volume process from state 2 to state 3: For the constant-volume process from state 4 to state 1: Substituting in equation (1) yields: ⎛ Tc ΔS 23 = C V ln⎜ ⎜T ⎝ h ⎛ Th ΔS 41 = C V ln⎜ ⎜T ⎝ c ⎞ ⎟ ⎟ ⎠ ⎞ ⎛ Tc ⎟ ⎜T ⎟ = −C V ln⎜ ⎝ h ⎠ ⎞ ⎟ ⎟ ⎠ ⎛ V2 ⎞ ⎛ Tc ⎞ ⎛ V2 ⎞ ⎛ Tc ⎞ ΔS cycle = nR ln⎜ ⎜V ⎟ ⎟ + CV ln⎜ ⎜T ⎟ ⎟ − nR ln⎜ ⎜V ⎟ ⎟ − CV ln⎜ ⎜T ⎟ ⎟= 0 ⎝ 1⎠ ⎝ h⎠ ⎝ 1⎠ ⎝ h⎠ 37 •• ″As far as we know.1806 Chapter 19 (b) The change in entropy for one Stirling cycle is the sum of the entropy changes during the cycle: ΔS cycle = ΔS12 + ΔS 23 + ΔS 34 + ΔS 41 (1) Express the entropy change for the isothermal process from state 1 to state 2: Similarly. give a reason why no warm-blooded organisms have evolved heat engines to increase their internal energies. and compare this to the human body’s efficiency for converting chemical energy into work (approximately 20%). Nature has never evolved a heat engine″—Steven Vogel.6ºF) and a typical outdoor temperature (70ºF). Does this efficiency comparison contradict the second law of thermodynamics? (b) From the result of Part (a). Princeton University Press (1988).

Process ab is an adiabatic compression. we eat food to get the energy that we need. Heat enters the system during the isobaric process bc and leaves the system during the isovolumetric process da. Note that no heat enters or leaves the system during the adiabatic processes ab and cd. Vb and Vc. Picture the Problem The working fluid will be modeled as an ideal gas and the process will be modeled as quasistatic. Find the efficiency of this cycle in terms of the volumes Va. 38 ••• The diesel cycle shown in Figure 19-17 approximates the behavior of a diesel engine. internal body temperatures would have to be maintained at an unreasonably high level.16% 310 K The fact that this efficiency is considerably less than the actual efficiency of a human body does not contradict the second law of thermodynamics.The Second Law of Thermodynamics 1807 Picture the Problem We can use the efficiency of a Carnot engine operating between reservoirs at body temperature and typical outdoor temperatures to find an upper limit on the efficiency of an engine operating between these temperatures. (b) Most warm-blooded animals survive under roughly the same conditions as humans. To make a heat engine work with appreciable efficiency. process bc is an expansion at constant pressure. process cd is an adiabatic expansion. (a) Express the maximum efficiency of an engine operating between body temperature and 70°F: Use T = 5 9 εC = 1 − Tc Th (tF − 32) + 273 to obtain: Tbody = 310 K and Troom = 294 K Substitute numerical values and evaluate ε C : ε C = 1− 294 K = 5. The application of the second law to chemical reactions such as the ones that supply the body with energy have not been discussed in the text but we can note that we don’t get our energy from heat swapping between our body and the environment. Rather. To find the efficiency of the diesel cycle we can find the heat that enters the system and the heat that leaves the system and use the expression that gives the efficiency in terms of these quantities. and process da is cooling at constant volume. Express the efficiency of the cycle in terms of Qc and Qh: Express Q for the isobaric warming process bc: ε= Q W Qh − Qc = = 1− c Qh Qh Qh Qbc = Qh = C P (Tc − Tb ) .

Qda (the constant-volume cooling process) is given by: Substitute for Qh and Qc and simplify using γ = C P C V to obtain: Using an equation for a quasistatic adiabatic process. relate the temperatures Tc and Td to the volumes Vc and Vd: Use equations (1) and (2) to eliminate Ta and Td: Qda = Qc = C V (Td − Ta ) ε = 1− (T − Ta ) C V (Td − Ta ) = 1− d C P (Tc − Tb ) γ (Tc − Tb ) Vbγ −1 (1) Vaγ −1 TaVaγ −1 = TbVbγ −1 ⇒ Ta = Tb TcVcγ −1 = TdVdγ −1 ⇒ Td = Tc Vcγ −1 (2) Vdγ −1 ⎛ Vcγ −1 Vbγ −1 ⎞ ⎜ T T − ⎜ c V γ −1 b V γ −1 ⎟ ⎟ d a ⎝ ⎠ ε = 1− γ (Tc − Tb ) ⎛⎛ V ⎜⎜ c ⎜⎜ V ⎝⎝ a ⎞ ⎟ ⎟ ⎠ γ −1 Because Va = Vd: ε = 1− T ⎛ Vb − b⎜ Tc ⎜ ⎝ Va Tb ⎞ ⎟ Tc ⎟ ⎠ ⎞ ⎟ ⎟ ⎠ γ −1 ⎞ ⎟ ⎟ ⎠ γ⎜ ⎜1 − ⎝ Noting that Pb = Pc. apply the idealgas law to relate Tb and Tc: Tb Vb = Tc Vc ⎛ Substitute for the ratio of Tb to Tc and simplify to obtain: ⎛ Vc ⎜ ⎜V ε = 1− ⎝ a ⎞ ⎟ ⎟ ⎠ γ −1 ⎛ Vb ⎜ ⎜V ⎝ a ⎛ Vb ⎞ γ⎜ ⎟ ⎜1 − ⎟ ⎝ Vc ⎠ V − b Vc γ ⎞ ⎟ ⎟ ⎠ γ −1 ⎛ Vc Vc ⎜ ⎜V Va ⋅ = 1− ⎝ a Vc Va ⎞ ⎟ ⎟ ⎠ ⎛ Vb ⎜ ⎜V ⎝ a ⎛ Vc Vb ⎞ γ⎜ ⎜V − V ⎟ ⎟ a ⎠ ⎝ a V − b Vc γ −1 ⎞ ⎟ ⎟ ⎠ γ −1 ⎛ Vc ⎞ ⎛ Vb ⎞ ⎜ ⎜V ⎟ ⎟ −⎜ ⎜V ⎟ ⎟ Vcγ − Vbγ a ⎠ a ⎠ ⎝ ⎝ = 1− = 1 − γ −1 γVa (Vc − Vb ) ⎛ Vc Vb ⎞ γ⎜ ⎜V − V ⎟ ⎟ a ⎠ ⎝ a γ . relate the temperatures Ta and Tb to the volumes Va and Vb: Proceeding similarly.1808 Chapter 19 Because CV is independent of T.

and show how a perfect engine working with this refrigerator can violate the refrigerator statement of the second law of thermodynamics. a cycle could be completed by an isothermal path between the two adiabatic curves shown in Figure 19-18. Assume that the heat-engine statement of the second law of thermodynamics is false. transferring 500 J of heat from the cold reservoir to the hot reservoir without requiring any work (see (c) in the diagram). without exhausting any heat to a cold reservoir. Suppose the heat-engine statement of the second law is false. the combination of the perfect heat engine and the ordinary refrigerator would be a perfect refrigerator. Determine the Concept The following diagram shows an ordinary refrigerator that uses 300 J of work to remove 500 J of heat from a cold reservoir and releases 800 J of heat to a hot reservoir (see (a) in the diagram). Then a ″perfect″ heat engine could remove energy from the hot reservoir and convert it completely into work with 100 percent efficiency. Thus. It is only in this expansion that heat is extracted from a reservoir.The Second Law of Thermodynamics 1809 Second Law of Thermodynamics 39 •• [SSM] A refrigerator absorbs 500 J of heat from a cold reservoir and releases 800 J to a hot reservoir. we would completely convert heat to mechanical energy.This violates the refrigerator statement of the second law. We could use this perfect heat engine to remove 300 J of energy from the hot reservoir and do 300 J of work on the ordinary refrigerator (see (b) in the diagram). Determine the Concept The work done by the system is the area enclosed by the cycle. There is no heat transfer in the adiabatic expansion or compression. Then. Hot reservoir at temperature Th ⇓ Ordinary refrigerator 300 J 300 J 500 J (a) Cold reservoir at temperature Tc (b) (c ) If two curves that represent quasi-static adiabatic processes could 40 •• intersect on a PV diagram. Show that such a cycle violates the second law of thermodynamics. where we assume that we start with the isothermal expansion. ⇓ 500 J Perfect heat engine Perfect refrigerator ⇓ ⇓ 800 J 300 J 500 J ⇓ ⇓ ⇓ . in violation of the second law of thermodynamics.

3 J = 66. how much work does it do each cycle? (c) How much heat does it release during each cycle? (d) What is the COP of this engine when it works as a refrigerator between the same two reservoirs? Picture the Problem We can find the efficiency of the Carnot engine using ε = 1 − Tc / Th and the work done per cycle from ε = W / Qh .1810 Chapter 19 Carnot Cycles 41 • [SSM] A Carnot engine works between two heat reservoirs at temperatures Th = 300 K and Tc = 200 K. (a) What is its efficiency? (b) How much additional work per cycle could be done if the engine were reversible? Picture the Problem We can find the efficiency of the engine from its definition and the additional work done if the engine were reversible from W = ε CQh . We can find the COP of the engine working as a refrigerator from its definition. where εC is the Carnot efficiency. We can apply conservation of energy to find the heat rejected each cycle from the heat absorbed and the work done each cycle.7 J = 67 J COP = Qc 66. relate the work done each cycle to the heat absorbed from the hot reservoir: (c) Apply conservation of energy to relate the heat given off each cycle to the heat absorbed and the work done: (d) Using its definition. (a) What is its efficiency? (b) If it absorbs 100 J of heat from the hot reservoir during each cycle.3 J An engine absorbs 250 J of heat per cycle from a reservoir at 300 K 42 • and releases 200 J of heat per cycle to a reservoir at 200 K.3% Th 300 K W = ε C Qh = (0. (a) The efficiency of the Carnot engine depends on the temperatures of the hot and cold reservoirs: (b) Using the definition of efficiency.7 J = = 2.333)(100 J ) = 33. express and evaluate the refrigerator’s coefficient of performance: ε C = 1− Tc 200 K = 1− = 33.0 W 33.3 J Qc = Qh − W = 100 J − 33. .

then Qh2. Then it will remove 140 J from the cold reservoir.3 J ⎝ ⎠ ΔW = 83.3 J − 50 J = 33 J 43 •• A reversible engine working between two reservoirs at temperatures Th and Tc has an efficiency of 30%. thus replacing the heat removed by the refrigerator. Show that if the second engine has an efficiency greater than 30%. the heat removed from the hot reservoir by this engine. in violation of the second law. the efficiency of this engine. Working as a heat engine. The two systems working together then convert heat into mechanical energy without rejecting any heat to a cold reservoir. and let it eject 140 J into the cold reservoir. is greater than 30%. and do additional mechanical work. Working as a heat engine. 44 •• A reversible engine working between two reservoirs at temperatures Th and Tc has an efficiency of 20%. A second engine working between the same two reservoirs also releases 140 J per cycle to the cold reservoir.The Second Law of Thermodynamics (a) Express the efficiency of the engine in terms of the heat absorbed from the high-temperature reservoir and the heat exhausted to the lowtemperature reservoir: (b) Express the additional work done if the engine is reversible: Relate the work done by a reversible engine to its Carnot efficiency: Substitute numerical values and evaluate W: Substitute numerical values in equation (1) and evaluate ΔW: 1811 ε= Q W Qh − Qc = = 1− c Qh Qh Qh 200 J = 20. Now take the second engine and run it between the same reservoirs. The end result of all this is that the second engine can run the refrigerator. A second engine working between the same two reservoirs also does 100 J of work per cycle. If ε2. it releases 140 J per cycle of heat to the cold reservoir. deliver 200 J to the hot reservoir. is 140 J/(1 − ε2) > 200 J. and require 60 J of energy to operate. Determine the Concept Let the first engine be run as a refrigerator.0% 250 J (1) = 1− ΔW = WCarnot − WPart (a ) ⎛ Tc W = ε C Qh = ⎜ ⎜1 − T h ⎝ ⎞ ⎟ ⎟Qh ⎠ ⎛ 200 K ⎞ W =⎜ ⎜1 − 300 K ⎟ ⎟ (250 J ) = 83. it does 100 J of work per cycle. replacing the heat taken from the cold reservoir. the two engines working together would violate the heat-engine statement of the second law. and the work done by this engine is W = ε2Qh2 > 60 J. Show that if the efficiency of the second engine is greater .

00.0 K. this engine will remove less than 500 J from the hot reservoir in the process of doing 100 J of work. but a finite amount of heat is transferred from the cold reservoir to the hot reservoir. operate between the same two heat reservoirs and use it to drive the refrigerator. the two engines working together would violate the refrigerator statement of the second law. The net result is then that no net work is done by the two systems working together. it will require 100 J of mechanical energy to take 400 J of heat from the cold reservoir and deliver 500 J to the hot reservoir. with ε2 > 0. then 50 J of work will remove more than 100 J of heat from the cold reservoir and put more than 150 J of heat into the hot reservoir.2. So running the engine described in Part (a) to operate the refrigerator with a COP > 2 will result in the transfer of heat from the cold to the hot reservoir without doing any net mechanical work in violation of the second law.2. 100 J of heat are absorbed and 150 J are released to the hot reservoir. how much work does it do? (c) How much heat does it release to the low-temperature reservoir during each cycle? (d) What is the coefficient of performance of this engine when it works as a refrigerator between these two reservoirs? . Because ε2 > 0. During each cycle. (a) What is the efficiency of the Carnot engine when it works as a heat engine between the same two reservoirs? (b) Show that no other engine working as a refrigerator between the same two reservoirs can have a COP greater than 2. Determine the Concept If the reversible engine is run as a refrigerator. (a) The efficiency of the Carnot engine is given by: εC = W 50 J = = 33% Qh 150 J (b) If the COP > 2. Now let the second engine.1812 Chapter 19 than 20%. Picture the Problem We can use the definition of efficiency to find the efficiency of the Carnot engine operating between the two reservoirs. (a) What is its efficiency? (b) If it absorbs 100 J of heat from the hot reservoir during each cycle. 46 •• A Carnot engine works between two heat reservoirs at temperatures Th = 300 K and Tc = 77. 45 •• A Carnot engine works between two heat reservoirs as a refrigerator. in violation of the refrigerator statement of the second law.

volumes. (a) The efficiency of a Carnot engine depends on the temperatures of the hot and cold reservoirs: (b) Express the work done each cycle in terms of the efficiency of the engine and the heat absorbed from the high-temperature reservoir: (c) Apply conservation of energy to obtain: (d) Using its definition. we can use its definition to find the efficiency of the cycle and the definition of the Carnot efficiency to find the efficiency of a Carnot engine operating between the extreme temperatures.0 K = 1− = 74. (c) the efficiency of this cycle. Picture the Problem We can use the ideal-gas law for a fixed amount of gas and the equations of state for an adiabatic process to find the temperatures.35 W 74. express and evaluate the refrigerator’s coefficient of performance: ε C = 1− Tc 77. (b) the heat absorbed or released by the system during each step.00 atm and a temperature of 0.743)(100 J ) = 74.0ºC. and pressures at the end points of each process in the given cycle.3 J COP = 47 •• [SSM] In the cycle shown in Figure 19-19.3 J = 26 J Qc 26 J = = 0. 1. We can use Q = C V ΔT and Q = C P ΔT to find the heat entering and leaving during the constant-volume and isobaric processes and the first law of thermodynamics to find the work done each cycle. It is then compressed at constant pressure back to its original state.3% Th 300 K W = ε C Qh = (0.The Second Law of Thermodynamics 1813 Picture the Problem We can use the definitions of the efficiency of a Carnot engine and the coefficient of performance of a refrigerator to find these quantities. and (d) the efficiency of a Carnot cycle operating between the temperature extremes of this cycle.00 mol of an ideal diatomic gas is initially at a pressure of 1. Find (a) the temperature after the adiabatic expansion.3 J Qc = Qh − W = 100 J − 74. The gas is heated at constant volume to T2 = 150ºC and is then expanded adiabatically until its pressure is again 1. Once we’ve calculated these quantities.00 atm. The work done each cycle by the Carnot engine is given by W = ε CQh and we can use the conservation of energy to find the heat rejected to the low-temperature reservoir. .

1814 Chapter 19 (a) Apply the ideal-gas law for a fixed amount of gas to relate the temperature at point 3 to the temperature at point 1: P PV 1V1 = 3 3 T1 T3 or.6 L ⎝ ⎠ Substitute numerical values in equation (1) and evaluate T3 and t3: T3 = (273 K ) 30.12 kJ Q23 = 0 Q31 = C P ΔT31 = 7 RΔT12 2 J ⎞ ⎛ =7 8.4 L and t 3 = T3 − 273 = 100°C (b) Process 1→2 takes place at constant volume (note that γ = 1.55 atm ⎞ 1.91 kJ .55 atm T1 273 K 1 Apply an equation for an adiabatic process to relate the pressures and volumes at points 2 and 3: Noting that V1 = 22. evaluate V3: ⎛P ⎞γ γ γ 1 ⎜ ⎟ V V ⇒ = P V = P V 3 1⎜ 1 1 3 3 ⎟ ⎝ P3 ⎠ 1 ⎛ 1.4 L )⎜ ⎜ 1atm ⎟ ⎟ = 30.4 L.4 corresponds to a diatomic gas and that CP – CV = R): Process 2→3 takes place adiabatically: Process 3→1 is isobaric (note that CP = CV + R): Q12 = CV ΔT12 = 5 RΔT12 2 J ⎞ ⎛ =5 8.00 atm ) = 1. because P1 = P3.6 L = 373 K 22.4 V3 = (22. V T3 = T1 3 V1 PV T P PV 1V1 = 2 2 ⇒ P2 = 1 1 2 T1 T2 V2T1 (1) Apply the ideal-gas law for a fixed amount of gas to relate the pressure at point 2 to the temperatures at points 1 and 2 and the pressure at 1: Because V1 = V2: P2 = P1 T2 423 K = (1.314 ⎟ (273 K − 373 K ) 2⎜ mol ⋅ K ⎠ ⎝ = − 2.314 ⎟ (423 K − 273 K ) 2⎜ mol ⋅ K ⎠ ⎝ = 3.

300 = ε max ε max ε max = 1 − Tc 323 K = 1− = 40.The Second Law of Thermodynamics (c) The efficiency of the cycle is given by: Apply the first law of thermodynamics to the cycle: 1815 ε= W Qin (2) ΔEint = Qin + Won or.12 kJ Tc 273 K = 1− = 35. (a) The efficiency of the steam engine as a percentage of the maximum possible efficiency is given by: The efficiency of a Carnot engine operating between temperatures Fc and Th is: ε steam engine 0.21 kJ Substitute numerical values in equation (2) and evaluate ε : (d) Express and evaluate the efficiency of a Carnot cycle operating between 423 K and 273 K: ε= 0.21kJ = 6.00 h. We can apply the definition of efficiency to find the heat discharged to the engine’s surroundings in 1. how much heat does the engine release to its surroundings in 1. because ΔEint. cycle = 0 (the system begins and ends in the same state) and Won = −Wby the gas = Qin . Your team has measured its efficiency to be 30.0%.91 kJ = 0.52% Th 543 K . Evaluating W yields: W = ∑ Q = Q12 + Q23 + Q31 = 3. Your team built a steam engine that takes in superheated steam at 270ºC and discharges condensed steam from its cylinder at 50. (a) How does this efficiency compare with the maximum possible efficiency for your engine? (b) If the useful power output of the engine is known to be 200 kW.12 kJ + 0 − 2.00 h? Picture the Problem We can find the maximum efficiency of the steam engine by calculating the Carnot efficiency of an engine operating between the given temperatures.0ºC.7% 3.5% Th 423 K εC = 1− 48 •• You are part of a team that is completing a mechanical-engineering project.

05% ε max 0. The temperature of the air in the air handler inside the house is to be 40ºC.68 GJ s ⎠ ⎝ 0.740ε max (b) Relate the heat Qc discharged to the engine’s surroundings to Qh and the efficiency of the engine: Using its definition.300 = = 74. relate the efficiency of the engine to the heat intake of the engine and the work it does each cycle: Substitute for Qh in the expression for Qc and simplify to obtain: ε= W Qh − Qc = ⇒ Qc = (1 − ε )Qh Qh Qh PΔt Qh = W ε = ε Qc = (1 − ε ) PΔt ε ⎛1 ⎞ = ⎜ − 1⎟ PΔt ⎝ε ⎠ Substitute numerical values and evaluate Qc (1.1816 Chapter 19 Substituting for εmax yields: ε steam engine 0. (a) What is maximum possible COP for a heat pump operating between these temperatures? (b) What must the minimum power of the electric motor driving the heat pump be? (c) In reality. What is the minimum power of the electric motor when the COP is 60 percent of the ideal value? Picture the Problem We can use the definition of the COPHP and the Carnot efficiency of an engine to express the maximum efficiency of the refrigerator in terms of the reservoir temperatures. the COP of the heat pump will be only 60 percent of the ideal value. We can apply the definition of power to find the minimum power needed to run the heat pump.00 h ) : kJ ⎞ ⎞⎛ ⎛ 1 Qc (1. .00 h ) = ⎜ − 1⎟ ⎜ 200 ⎟ (3600 s ) = 1. in January.4052 or ε steam engine = 0.300 ⎠ ⎝ *Heat Pumps 49 • [SSM] As an engineer. The house is located where. the average outside temperature is –10ºC. you are designing a heat pump that is capable of delivering heat at the rate of 20 kW to a house.

how much heat can it absorb from the food compartment in 1.3 kW (0. P.26 dQc dt ε (COPHP. By expressing the COP in terms of Tc and Th we can write the amount of heat removed from the refrigerator as a function of Tc. (a) Express the amount of heat the refrigerator can remove in a given period of time as a function of its COP: Qc = (COP )W = (COP )PΔt .26) 50 • A refrigerator is rated at 370 W.0ºC and it releases heat into a room at 20. Th.0ºC? (b) If the COP of the refrigerator is 70% of that of a reversible refrigerator.max ) ε HP where ε HP is the efficiency of the heat pump.00 min if the foodcompartment temperature of the refrigerator is 0. Pmin dQc = dt = Substitute numerical values and evaluate Pmin: Pmin = 20 kW = 5.The Second Law of Thermodynamics (a) Express the COPHP in terms of Th and Tc: COPHP = = Qh Qh = W Qh − Qc Th 1 1 = = Q T Th − Tc 1− c 1− c Qh Th 1817 Substitute numerical values and evaluate COPHP: COPHP = 313 K = 6. (a) What is the maximum amount of heat it can absorb from the food compartment in 1. and Δt.60)(6.2 kW 6.26 313 K − 263 K = 6.00 min under these conditions? Picture the Problem We can use the definition of the COP to relate the heat removed from the refrigerator to its power rating and operating time.3 (b) The COPHP is also given by: COPHP = Pout Pout ⇒ Pmotor = COPHP Pmotor Substitute numerical values and evaluate Pmotor: (c) The minimum power of the electric motor is given by: Pmotor = 20 kW = 3.

and Δt.70 )(303 kJ ) = 0. By expressing the COP in terms of Tc and Th we can write the amount of heat removed from the refrigerator as a function of Tc. how much heat can it absorb from the food compartment in 1.21 MJ 51 • A refrigerator is rated at 370 W.30 MJ min ⎠ ⎝ 293 K − 273 K ⎠ ⎝ (b) If the COP is 70% of the efficiency of an ideal pump: ' Qc = (0.0ºC and it releases heat into a room at 35ºC? (b) If the COP of the refrigerator is 70% of that of a reversible pump. Picture the Problem We can use the definition of the COP to relate the heat removed from the refrigerator to its power rating and operating time.00 min × ⎟ = 303 kJ = 0.00 min if the temperature in the compartment is 0.1818 Chapter 19 Express the COP in terms of Th and Tc and simplify to obtain: COP = = Qc Q Q −W = c = h W ε Qh ε Qh 1− ε ε = 1 ε −1 = 1 −1 Tc 1− Th = Tc Th − Tc Substituting for COP yields: ⎛ Tc ⎞ Qc = ⎜ ⎜T −T ⎟ ⎟ PΔt ⎝ h c⎠ Substitute numerical values and evaluate Qc: 273 K 60 s ⎞ ⎛ ⎞ ⎛ Qc = ⎜ ⎟ (370 W )⎜1. (a) What is the maximum amount of heat it can absorb for the food compartment in 1. (a) Express the amount of heat the refrigerator can remove in a given period of time as a function of its COP: Qc = (COP )W = (COP )PΔt .00 min? Is the COP for the refrigerator greater when the temperature of the room is 35ºC or 20ºC? Explain. Th. P.

The air temperature should increase from 63°F to 68°F.12 MJ Because the temperature difference increases when the room is warmer. ceilings and floors. Also assume that the heat capacity of the floor.70 )(173 kJ ) = 0. If the pump’s electric power consumption is 750 W. ceiling. The outside temperature is 35°F .17 MJ ⎟ (370 W )⎜1. and the temperature at the air handler in the room is 112°F. Picture the Problem We can use the definition of the coefficient of performance of a heat pump and the relationship between the work done per cycle and the pump’s power consumption to find your waiting time.00 m × 3. how long will you have to wait in order for the room’s air to warm (take the specific heat of air to be 1.005 kJ/(kg·°C)? Assume you have good window draperies and good wall insulation so that you can neglect the release of heat through windows. You will use the pump on chilly winter nights to increase the air temperature in your bedroom. walls and furniture are negligible. walls. whose COP is half the COP of a reversible heat pump.50 m × 2. the COP decreases. Your bedroom’s dimensions are 5. 52 ••• You are installing a heat pump. .The Second Law of Thermodynamics 1819 Express the COP in terms of Th and Tc and simplify to obtain: COP = = = Qc Q Q −W = c = h W εQh εQh 1− ε ε = 1 ε −1 Tc 1 −1 = T Th − Tc 1− c Th Substituting for COP yields: ⎛ Tc ⎞ Qc = ⎜ ⎜T −T ⎟ ⎟ PΔt ⎝ h c⎠ Substitute numerical values and evaluate Qc: 273 K 60 s ⎞ ⎛ ⎞ ⎛ Qc = ⎜ ⎟ = 173 kJ = 0.00 min × min ⎠ ⎝ 308 K − 273 K ⎠ ⎝ (b) If the COP is 70% of the efficiency of an ideal pump: ' Qc = (0.50 m.

50 m )⎜ 1005 ⎜ 5 F° × ⎟ ⎜ ⎟ kg ⋅ C° ⎠ ⎝ 9 F° ⎠ m ⎠ ⎝ ⎝ Δt = = 56 s 317 K ⎛ ⎞ ⎜ ⎟ (750 W ) ⎝ 317 K − 275 K ⎠ Entropy Changes 53 • [SSM] You inadvertently leave a pan of water boiling away on the hot stove. the density of air. P is the power consumption of the heat pump.00 L of boiling water. The pan originally held 1.00 m × 3.293 3 ⎟ (5. COPHP = We’re given that the coefficient of performance of the heat pump is half the coefficient of performance of an ideal heat pump: COPHP = Qh 1 = COPmax W 2 ⎛ Th ⎞ ⎜ ⎟ =1 2⎜ ⎟ − T T ⎝ h c⎠ 2Qh Substituting for COPHP yields: Δt = ⎛ Th ⎞ ⎜ ⎜ T −T ⎟ ⎟P ⎝ h c⎠ The heat required to warm the room is related to the volume of the room.50 m × 2.1820 Chapter 19 The coefficient of performance of the heat pump is defined as: Qh Q Qh = h ⇒ Δt = (COPHP )P W PΔt where Qh is the heat required to raise the temperature of your bedroom. You return just in time to see the last drop converted into steam. What is the change in entropy of the water associated with its change of state from liquid to gas? . and the desired increase in temperature: Substitute for Qh to obtain: Qh = mcΔT = ρVcΔT where ρ is the density of air and c is its specific heat capacity. and Δt is the time required to warm the bedroom. Δt = 2 ρVcΔT ⎛ Th ⎞ ⎜ ⎜ T −T ⎟ ⎟P ⎝ h c⎠ Substitute numerical values and evaluate Δt: ⎛ kg ⎞ J ⎞⎛ 5 C° ⎞ ⎛ ⎟ 2⎜1.

because m = nM H 2 O . The change in entropy of the water is given by: ΔS H 2 O = Qabsorbed by H 2 O T The heat absorbed by the water as it vaporizes is the product of its mass and latent heat of vaporization: Substituting for Qabsorbed yields: by H 2 O Qabsorbed = mLv = ρVLv by H 2 O ΔS H 2 O = ρVLv T Substitute numerical values and evaluate ΔS H 2O : ΔS H 2 O ⎛ kg ⎞ kJ ⎞ ⎛ 2257 ⎟ ⎜1. Because heat is removed from liquid water when it freezes.05 K 54 • What is the change in entropy of 1. See Table 18-2 T for the latent heat of vaporization of water. See Appendix C for the molar mass of water and Table 18-2 for the latent heat of fusion of water.00 ⎟ (1. the change in entropy of the liquid water is negative.00 L )⎜ ⎜ L⎠ kg ⎟ ⎝ ⎝ ⎠ = 373 K kJ = 6.0ºC that freezes to ice at 0. The change in entropy of the water is given by:: The heat removed from the water as it freezes is the product of its mass and latent heat of fusion: ΔS H 2 O = Qremoved T from H 2 O Qremoved = −mLf from H 2 O or.00 mol of liquid water at 0.The Second Law of Thermodynamics 1821 Picture the Problem Because the water absorbed heat in the vaporization process Qabsorbed by H 2 O its change in entropy is positive and given by ΔS H 2 O = . Qremoved = − nM H 2 O Lf from H 2 O .0°C? Picture the Problem We can use the definition of entropy change to find the change in entropy of the liquid water as it freezes.

Show that even though the entropy of the water decreases. The change in entropy of the universe resulting from this freezing and cooling process is given by: Express ΔS water : Express ΔS freezing : ΔS u = ΔS water + ΔS freezer (1) ΔS water = ΔS freezing + ΔS cooling ΔS freezing = − Qfreezing Tfreezing (2) (3) where the minus sign is a consequence of the fact that energy is leaving the water as it freezes. while the entropy of the water decreases. Picture the Problem The change in the entropy of the universe resulting from the freezing of this water and the cooling of the ice formed is the sum of the entropy changes of the water-ice and the freezer. initially liquid at 0. the net entropy of the universe increases.0 g of water once it is placed in the freezer compartment of a refrigerator.0 J = K 273 K ΔS H 2O 55 •• Consider the freezing of 50. the entropy of the freezer increases. Relate Qfreezing to the latent heat of fusion and the mass of the water: Substitute in equation (3) to obtain: ΔS freezing = − mLf Tfreezing ⎞ ⎟ ⎟ ⎠ ⎞ ⎟ ⎟ ⎠ Qfreezing = mLf Express ΔS cooling : ⎛ Tf ΔS cooling = mC p ln⎜ ⎜T ⎝ i ΔS water = Substitute in equation (2) to obtain: ⎛ Tf − mLf + mCp ln⎜ ⎜T Tfreezing ⎝ i . is frozen into ice and cooled to –10ºC. Note that.0ºC. The water.1822 Chapter 19 Substitute numerical values and evaluate ΔS H 2O : g ⎞⎛ J⎞ ⎛ − (1.5 ⎟ ⎟⎜ ⎜ mol ⎠ ⎝ g⎟ ⎝ ⎠ = − 22.015 333. Assume the walls of the freezer are maintained at –10ºC.00 mol)⎜18.

because ΔSu > 0.40 J/K + ⎥ 263 K ⎥ ⎦ and.5 ×10 3 56 • In this problem.00 mol of an ideal gas at 400 K expand quasistatically and isothermally from an initial volume of 40. the entropy of the universe increases. (a) What is the entropy change of the gas? (b) What is the entropy change of the universe for this process? Picture the Problem We can use the definition of entropy change and the 1st law of thermodynamics to express ΔS for the ideal gas as a function of its initial and final volumes. 333.The Second Law of Thermodynamics 1823 Noting that the freezer gains heat (at 263 K) from the freezing water and cooling ice. express ΔS freezer : ΔS freezer = = ΔQice ΔQcooling ice + Tfreezer Tfreezer mCp ΔT mLf + Tfreezer Tfreezer Substitute for ΔS water and ΔS freezer in equation (1): ΔS u = ⎛ Tf − mLf + mCp ln⎜ ⎜T Tfreezing ⎝ i mCp ΔT ⎞ mLf ⎟ + + ⎟ T Tfreezer ⎠ freezer ⎞ Lf + C p ΔT ⎤ ⎟ ⎥ ⎟+ T ⎥ freezer ⎠ ⎦ ⎡ − Lf ⎛ Tf = m⎢ + C p ln⎜ ⎜T ⎢ Tfreezing ⎝ i ⎣ Substitute numerical values and evaluate ΔSu: ⎡ 3 J ⎢ 333. (a) The entropy change of the gas is given by: ΔS gas = Q T (1) .0 L to a final volume of 80. 2.5 ×10 kg ⎛ J ⎞ ⎛ 263 K ⎞ ⎟ ⎟ ln⎜ +⎜ 2100 ΔS u = (0.0 L.0500 kg ) ⎢− ⎜ ⎜ ⎟ kg ⋅ K ⎟ 273 K ⎢ ⎝ ⎠ ⎝ 273 K ⎠ ⎢ ⎣ ⎤ J ⎞ J ⎛ ⎟ ( ) +⎜ 273 K − 263 K 2100 ⎥ kg ⋅ K ⎟ kg ⎜ ⎝ ⎠ ⎥ = 2.

00 mol)⎜ 8. 57 •• [SSM] A system completes a cycle consisting of six quasi-static steps. and during step 5 it absorbs heat from a reservoir at temperature T3. we can find the temperature T3 from the entropy changes during the 1st two processes and the heat released during the third. During step 1 the system absorbs 300 J of heat from a reservoir at 300 K. and because the system’s final state is identical to its initial state: ΔS system = 0 1 complete cycle . Q = −Won ⎛ Vi Won = nRT ln⎜ ⎜V ⎝ f ⎛ Vi ⎞ ⎜ ⎟ = − ⇒ ln Q nRT ⎜V ⎟ ⎝ f ⎠ ⎞ ⎟ ⎟ ⎠ ⎞ ⎟ ⎟ ⎠ The work done on the gas is given by: Substitute for Q in equation (1) to obtain: ⎛ Vi ΔS gas = −nR ln⎜ ⎜V ⎝ f Substitute numerical values and evaluate ΔS: J J ⎞ ⎛ 40. during which the total work done by the system is 100 J. (a) Because S is a state function of the system. (During steps 2. Because the entropy change for the complete cycle is the sum of the entropy changes for each process.1824 Chapter 19 Apply the first law of thermodynamics to the isothermal process to express Q in terms of Won: Q = ΔEint − Won or.5 ΔS gas = −(2.314 ⎟ ln⎜ ⎜ ⎟ K mol ⋅ K ⎠ ⎝ 80. 4 and 6 the system undergoes adiabatic processes in which the temperature of the system changes from one reservoir’s temperature to that of the next.) (a) What is the entropy change of the system for the complete cycle? (b) If the cycle is reversible.0 L ⎠ ⎝ (b) Because the process is reversible: ΔS u = 0 Remarks: The entropy change of the environment of the gas is −11. during step 3 the system absorbs 200 J of heat from a reservoir at 400 K. because ΔEint = 0 for an isothermal expansion of a gas.0 L ⎞ ⎛ ⎟ = 11. what is the temperature T3? Picture the Problem We can use the fact that the system returns to its original state to find the entropy change for the complete cycle.5 J/K.

The Second Law of Thermodynamics 1825 (b) Relate the entropy changes for each of the three heat reservoirs and the system for one complete cycle of the system: Substitute numerical values. Heat is rejected by the two high-temperature reservoirs and absorbed by the cold reservoir: Solving for T3 yields: ΔS1 + ΔS 2 + ΔS 3 + ΔS system = 0 or Q1 Q2 Q3 + + +0 = 0 T1 T2 T3 − 300 J − 200 J 400 J + + =0 300 K 400 K T3

T3 = 267 K

58 •• In this problem, 2.00 mol of an ideal gas initially has a temperature of 400 K and a volume of 40.0 L. The gas undergoes a free adiabatic expansion to twice its initial volume. What is (a) the entropy change of the gas and (b) the entropy change of the universe? Picture the Problem The initial and final temperatures are the same for a free expansion of an ideal gas. Thus, the entropy change ΔS for a free expansion from Vi to Vf is the same as ΔS for an isothermal process from Vi to Vf. We can use the definition of entropy change and the 1st law of thermodynamics to express ΔS for the ideal gas as a function of its initial and final volumes.

(a) The entropy change of the gas is given by: Apply the first law of thermodynamics to the isothermal process to express Q:

ΔS gas =

Q T

(1)

Q = ΔEint − Won or, because ΔEint = 0 for a free expansion of a gas, Q = −Won
⎛ Vi Won = nRT ln⎜ ⎜V ⎝ f ⎞ ⎛ Vi ⎟ ⎜ ⇒ ln Q nRT = − ⎟ ⎜V ⎠ ⎝ f ⎞ ⎟ ⎟ ⎠ ⎞ ⎟ ⎟ ⎠

The work done on the gas is given by: Substitute for Q in equation (1) to obtain:

⎛ Vi ΔS gas = −nR ln⎜ ⎜V ⎝ f

Substitute numerical values and evaluate ΔS:
J ⎞ ⎛ 40.0 L ⎞ J ⎛ ⎟ ΔS gas = −(2.00 mol)⎜ 8.314 = 11.5 ⎟ ln⎜ ⎟ ⎜ mol ⋅ K ⎠ ⎝ 80.0 L ⎠ K ⎝

1826 Chapter 19 (b) The change in entropy of the universe is the sum of the entropy changes of the gas and the surroundings: For the change in entropy of the surroundings we use the fact that, during the free expansion, the surroundings are unaffected: The change in entropy of the universe is the change in entropy of the gas: ΔS u = ΔS gas + ΔS surroundings

ΔS surroundings =

Qrev 0 = =0 T T

ΔS u = 11.5

J K

59 •• A 200-kg block of ice at 0.0ºC is placed in a large lake. The temperature of the lake is just slightly higher than 0.0ºC, and the ice melts very slowly. (a) What is the entropy change of the ice? (b) What is the entropy change of the lake? (c) What is the entropy change of the universe (the ice plus the lake)? Picture the Problem Because the ice gains heat as it melts, its entropy change is positive and can be calculated from its definition. Because the temperature of the lake is just slightly greater than 0°C and the mass of water is so much greater than that of the block of ice, the absolute value of the entropy change of the lake will be approximately equal to the entropy change of the ice as it melts.

(a) The entropy change of the ice is given by: Substitute numerical values and evaluate ΔSice :

ΔS ice =

mLf T kJ ⎞ ⎜ (200 kg )⎛ ⎜ 333.5 ⎟ ⎟ ⎝ 273 K kg ⎠

ΔS ice =

= 244

kJ K

(b) Relate the entropy change of the lake to the entropy change of the ice: (c) The entropy change of the universe due to this melting process is the sum of the entropy changes of the ice and the lake:

ΔS lake ≈ −ΔS ice = − 244

kJ K

ΔS u = ΔS ice + ΔS lake

The Second Law of Thermodynamics 1827 Because the temperature of the lake is slightly greater than that of the ice, the magnitude of the entropy change of the lake is less than 244 kJ/K and the entropy change of the universe is just slightly greater than zero. The melting of the ice is an irreversible process and ΔS u > 0 .
60 •• A 100-g piece of ice at 0.0ºC is placed in an insulated calorimeter with negligible heat capacity containing 100 g of water at 100ºC. (a) What is the final temperature of the water once thermal equilibrium is established? (b) Find the entropy change of the universe for this process. Picture the Problem We can use conservation of energy to find the equilibrium temperature of the water and apply the equations for the entropy change during a melting process and for constant-pressure processes to find the entropy change of the universe (the entropy change of the piece of ice plus the entropy change of the water in the insulated container).

(a) Apply conservation of energy to obtain:

∑Q
i ice

i

=0

or Qmelting + Qwarming − Qcooling = 0
water water

Substitute to relate the masses of the ice and water to their temperatures, specific heats, and the final temperature of the water:
⎛ kJ ⎞ ⎜ (100 g )⎛ ⎜ 333.5 ⎟ ⎟ + (100 g )⎜ ⎜ 4.18 ⎝ kg ⎠ ⎝ kJ ⎞ ⎟t kg ⋅ C° ⎟ ⎠

⎛ kJ ⎞ − (100 g )⎜ ⎜ 4.18 kg ⋅ C° ⎟ ⎟ (100°C − t ) = 0 ⎝ ⎠

Solving for t yields: (b) The entropy change of the universe is the sum of the entropy changes of the ice and the water: Using the expression for the entropy change for a constant-pressure process, express the entropy change of the melting ice and warming icewater:

t = 10.1°C

ΔS u = ΔSice + ΔS water

ΔSice = ΔS melting ice + ΔS warming water = ⎛ Tf mLf + mcP ln⎜ ⎜T Tf ⎝ i ⎞ ⎟ ⎟ ⎠

1828 Chapter 19 Substitute numerical values to obtain:

ΔS ice =

kJ ⎞ ⎜ (0.100 kg )⎛ ⎟ ⎜ 333.5 ⎟ ⎝ 273 K kg ⎠

⎛ J kJ ⎞ ⎛ 283 K ⎞ + (0.100 kg )⎜ ⎟ ln⎜ ⎜ 4.18 kg ⋅ K ⎟ ⎟ = 137 K ⎜ 273 K ⎟ ⎠ ⎝ ⎝ ⎠

Find the entropy change of the cooling water:
⎛ J kJ ⎞ ⎛ 283 K ⎞ ΔS water = (0.100 kg )⎜ ⎜ 4.18 kg ⋅ K ⎟ ⎟ ln⎜ ⎜ 373 K ⎟ ⎟ = −115 K ⎝ ⎠ ⎝ ⎠

Substitute for ΔSice and ΔSwater and evaluate the entropy change of the universe:

ΔS u = 137

J J J − 115 = 22 K K K

Remarks: The result that ΔSu > 0 tells us that this process is irreversible. 61 •• [SSM] A 1.00-kg block of copper at 100ºC is placed in an insulated calorimeter of negligible heat capacity containing 4.00 L of liquid water at 0.0ºC. Find the entropy change of (a) the copper block, (b) the water, and (c) the universe. Picture the Problem We can use conservation of energy to find the equilibrium temperature of the water and apply the equations for the entropy change during a constant pressure process to find the entropy changes of the copper block, the water, and the universe.

(a) Use the equation for the entropy change during a constant-pressure process to express the entropy change of the copper block: Apply conservation of energy to obtain:

⎛ Tf ΔS Cu = mCu cCu ln⎜ ⎜T ⎝ i

⎞ ⎟ ⎟ ⎠

(1)

∑Q
i

i

=0

or Qcopper + Qwarming = 0
block water

00 kg )⎜ ⎜ 0.386 kg ⋅ K ⎟ ⎟ln⎜ ⎜ 373 K ⎟ ⎟ = − 117 K ⎝ ⎠ ⎝ ⎠ (b) The entropy change of the water is given by: ⎛ Tf ΔS water = mwater c water ln⎜ ⎜T ⎝ i ⎞ ⎟ ⎟ ⎠ Substitute numerical values and evaluate ΔS water : ⎛ J kJ ⎞ ⎛ 275. Picture the Problem Because the mass of the water in the lake is so much greater than the mass of the piece of lead. specific heats.386 ⎝ kJ ⎞ ⎟ (Tf − 373 K ) kg ⋅ K ⎟ ⎠ kg ⎞ ⎛ kJ ⎞ ⎛ ⎟ (Tf − 273 K ) = 0 + (4. the water in the lake.18 kg ⋅ K ⎟ ⎟ ln⎜ ⎜ 273 K ⎟ ⎟ = 138 K ⎝ ⎠ ⎝ ⎠ (c) Substitute for ΔS Cu and ΔS water and evaluate the entropy change of the universe: ΔS u = ΔS Cu + ΔS water = −117 = 21 J K J J + 138 K K Remarks: The result that ΔSu > 0 tells us that this process is irreversible. find the entropy change of the universe.26 K Substitute numerical values in equation (1) and evaluate ΔS Cu : ⎛ J kJ ⎞ ⎛ 275.00 ⎟ ⎜ 4. .26 K ⎞ ΔS Cu = (1.00 kg )⎜ ⎜ 4. the temperature of the lake will increase only slightly and we can reasonably assume that its final temperature is 10°C.26 K ⎞ ΔS water = (4. 62 •• If a 2.00-kg piece of lead at 100ºC is dropped into a lake at 10ºC. We can apply the equation for the entropy change during a constant pressure process to find the entropy changes of the piece of lead. and the universe.00 kg )⎛ ⎜ 0.18 ⎜ L ⎠⎝ kg ⋅ K ⎟ ⎝ ⎠ Solve for Tf to obtain: Tf = 275.The Second Law of Thermodynamics 1829 Substitute to relate the masses of the block and water to their temperatures.00 L )⎜1. and the final temperature Tf of the water: ⎜ (1.

41 J/K Substitute numerical values in equation (1) and evaluate ΔSu: ΔS u = −70. (a) The entropy change of the universe is the sum of the entropy changes of the two reservoirs: ΔS u = ΔS h + ΔSc = − ⎛1 1⎞ = −Q⎜ ⎟ ⎜T − T ⎟ c ⎠ ⎝ h Q Q + Th Tc .41 = 11 K K K Entropy and ″Lost″ Work 63 •• [SSM] A a reservoir at 300 K absorbs 500 J of heat from a second reservoir at 400 K. (a) What is the change in entropy of the universe.00 kg )⎛ ⎜ ⎜ 0. express and evaluate the entropy change of the lead: ⎛ Tf ΔS Pb = mPb cPb ln⎜ ⎜T ⎝ i ⎞ ⎛ J kJ ⎞ ⎛ 283 K ⎞ ⎟ ⎜ 0.69 K ⎟ = (2.1830 Chapter 19 Express the entropy change of the universe in terms of the entropy changes of the lead and the water in the lake: ΔS u = ΔS Pb + ΔS w (1) Using the equation for the entropy change during a constant-pressure process.00 kg )⎜ ⎝ ⎠ ⎝ ⎠ ⎠ The entropy change of the water in the lake is given by: Substitute numerical values and evaluate ΔSw: ΔS w = Qw QPb mPb cPb ΔTPb = = Tw Tw Tw ΔS w = (2. and (b) how much work is lost during the process? Picture the Problem We can find the entropy change of the universe from the entropy changes of the high. The maximum amount of the 500 J of heat that could be converted into work can be found from the maximum efficiency of an engine operating between the two reservoirs.69 J J J + 81.128 kg ⋅ K ⎟ ⎟ ln⎜ ⎜ 373 K ⎟ ⎟ = −70.128 kJ ⎞ ⎟ (90 K ) kg ⋅ K ⎟ ⎠ ⎝ 283 K = 81.and low-temperature reservoirs.

(a) What is the entropy change of the universe for the complete cycle? (b) How much work is lost in this cycle? (c) Show that the work lost is TΔSu. Consequently.3 L to V2 = 24. the net entropy change is the negative of that of the gas in the isothermal compression. In the isothermal reversible process that returns the gas to its original state. However. because the process is reversible. 1. Picture the Problem Although no energy is lost by the gas in the adiabatic free expansion. .The Second Law of Thermodynamics 1831 Substitute numerical values and evaluate ΔSu: ⎛ 1 1 ⎞ ΔS u = (− 500 J ) ⎜ ⎜ 400 K − 300 K ⎟ ⎟ ⎝ ⎠ = 0.00 mol of an ideal gas at 300 K undergoes a free adiabatic expansion from V1 = 12. the process is irreversible and the entropy of the gas (and the universe) increases. the gas releases energy to the surroundings. the entropy change of the universe is zero.6 L.42 J/K (b) Relate the heat that could have been converted into work to the maximum efficiency of an engine operating between the two reservoirs: The maximum efficiency of an engine operating between the two reservoir temperatures is the efficiency of a Carnot device operating between the reservoir temperatures: Substitute for εmax to obtain: W = ε max Qh ε max = ε C = 1 − Tc Th ⎛ Tc ⎞ W =⎜ ⎜1 − T ⎟ ⎟Qh h ⎠ ⎝ ⎛ 300 K ⎞ W =⎜ ⎜1 − 400 K ⎟ ⎟ (500 J ) = 125 J ⎝ ⎠ Substitute numerical values and evaluate W: 64 •• In this problem. It is then compressed isothermally and reversibly back to its original state.

0 cycles/s. because ΔSgas during ΔS u = ΔS gas during = = 0.73 kJ ⎛ Vi ⎞ Wby gas. f →i = −nRT ln⎜ ⎟ ⎜V ⎟ ⎝ f⎠ ⎛ ⎛ Vf ⎞ ⎞ ⎛ Vf ⎞ ⎟ ⎜ = nRT ln⎜ ⎟⎟ ⎜V ⎟ ⎟ = T ⎜ nR ln⎜ ⎜V ⎟ i ⎠ ⎝ ⎝ i⎠ ⎠ ⎝ = TΔS u General Problems 65 • A heat engine with an output of 200 W has an efficiency of 30%.3 L ⎞ ⎛ ⎟ = 5. f →i = −Won gas. isothermal compression free expansion Q T ⎞ ⎟ ⎟ ⎠ The work done by the gas during its isothermal compression is given by: Substituting for Q in the expression for ΔS u and simplifying yields: ⎛ Vf Wby = −Won = −Q = −nRT ln⎜ ⎜V ⎝ i ⎛ Vf ΔS u = − nR ln⎜ ⎜V ⎝ i ⎞ ⎟ ⎟ ⎠ (1) Substitute numerical values and evaluate ΔSu: J J J ⎞ ⎛ 12.00 mol)⎜ 8. Application of the first law of thermodynamics will yield the heat given off each cycle. .763 = 5. the work done on the gas is: J⎞ ⎛ Wlost = TΔS u = (300 K )⎜ 5. In the adiabatic compression. (a) How much work is done by the engine during each cycle? (b) How much heat is absorbed from the hot reservoir and how much is released to the cold reservoir during each cycle? Picture the Problem We can use the definition of power to find the work done each cycle and the definition of efficiency to find the heat that is absorbed each cycle.1832 Chapter 19 (a) Relate the entropy change of the universe to the entropy changes of the gas during 1 complete cycle: ΔS u = ΔS gas during + ΔS gas during free expansion isothermal compresion or. It operates at 10.314 ⎟ln⎜ ⎜ ⎟ K K mol ⋅ K ⎠ ⎝ 24.763 ⎟ K⎠ ⎝ = 1.76 ΔS u = −(1.6 L ⎠ ⎝ (b) Use Equation 19-22 to find the amount of energy that becomes unavailable for doing work during this process: (c) No work is done in the free expansion.

30 Qh.The Second Law of Thermodynamics 1833 (a) Use the definition of power to relate the work done in each cycle to the frequency of each cycle: Substitute numerical values and evaluate Wcycle: (b) Express the heat absorbed in each cycle in terms of the work done and the efficiency of the engine: Apply the 1st law of thermodynamics to find the heat given off in each cycle: Wcycle = PΔt = P f where f is the frequency of the engine. Its efficiency is 85 percent of that of a Carnot engine working between the same reservoirs. a heat engine operating between two heat reservoirs absorbs 150 J from the reservoir at 100ºC and releases 125 J to the reservoir at 20ºC. Wcycle = 200 W = 20.777 ε C 21.cycle − W = 67 J − 20 J = 47 J 66 • During each cycle. (a) What is the efficiency of this engine? (b) What is the ratio of its efficiency to that of a Carnot engine working between the same reservoirs? (This ratio is called the second law efficiency.45% 67 • [SSM] An engine absorbs 200 kJ of heat per cycle from a reservoir at 500 K and releases heat to a reservoir at 200 K.0 J 10.45% Th 373 K εC = 1− ε 16. (a) What is the .) Picture the Problem We can use their definitions to find the efficiency of the engine and that of a Carnot engine operating between the same reservoirs.cycle = Qh.67% = = 0.7% 150 J Tc 293 K = 1− = 21.0 s −1 Wcycle = 20.0 J = 67 J 0.cycle = ε Qc.67% = 16. (a) The efficiency of the engine is given by: Substitute numerical values and evaluate ε: (b) Find the efficiency of a Carnot engine operating between the same reservoirs: Express the ratio of the two efficiencies: ε= Q W Qh − Qc = = 1− c Qh Qh Qh ε = 1− 125 J = 16.

The change in entropy of the universe associated with a dive is given by: Qadded to water Twater where Qadded to water is the energy entering ΔS u = ΔS water = the water as a result of the kinetic energy of the diver as he enters the water. (a) Express the efficiency of the engine in terms of the efficiency of a Carnot engine working between the same reservoirs: Substitute numerical values and evaluate ε : (b) Use the definition of efficiency to find the work done in each cycle: (c) Apply the first law of thermodynamics to the cycle to obtain: ε = 0.85ε C = 0.cycle = Qh.10 MJ Qc. The energy added to the water in the pool is the change in the gravitational potential energy of the diver during the dive.85⎜ ⎜1 − ⎝ ⎛ Tc Th ⎞ ⎟ ⎟ ⎠ ε = 0. Picture the Problem Assume that the mass of the diver is 75 kg and that the temperature of the water in the pool is 25°C.cycle − W = 200 kJ − 102 kJ = 98 kJ 68 • Estimate the change in entropy of the universe associated with an Olympic diver diving into the water from the 10-m platform.510 = 51% 500 K ⎟ ⎠ W = ε Qh = (0.85⎜ ⎜1 − ⎝ ⎛ 200 K ⎞ ⎟ = 0. The energy added to the water is the change in the gravitational potential energy of the diver: ΔS u = mgh Twater .1834 Chapter 19 efficiency of this engine? (b) How much work is done in each cycle? (c) How much heat is released to the low-temperature reservoir during each cycle? Picture the Problem We can use the definition of efficiency to find the work done by the engine during each cycle and the first law of thermodynamics to find the heat released to the low-temperature reservoir during each cycle.510)(200 kJ ) = 102 kJ = 0.

located on the Hobbes River. liquid sodium circulates between the reactor core and a heat exchanger located in the superheated steam that drives the turbine. Entropy is a state function. Heat is released into the river.81 m/s 2 )(10 m ) ΔS u = (25 + 273)K ≈ 25 J K 69 • To maintain the temperature inside a house at 20ºC.0 kW on a day when the outside temperature is –7ºC.0 kW W = = 113 K Δt 266 K 70 •• Calvin Cliffs Nuclear Power Plant. and released by the liquid sodium (and into the superheated steam) in the heat exchanger. because ΔS house = 0 . and the state of the house does not change. ΔS u = ΔS surroundings Q Tsurroundings RΔt Tsurroundings ΔS surroundings = = ΔS u = RΔt Tsurroundings ⇒ ΔS u R = Δt Tsurroundings Substitute numerical values and evaluate ΔSu/Δt: ΔS u 30.The Second Law of Thermodynamics 1835 Substitute numerical values and evaluate ΔS u : ( 75 kg ) (9. At what rate does this house contribute to the increase in the entropy of the universe? Picture the Problem The change in entropy of the universe is the change in entropy of the house plus the change in entropy of the environment. We can find the change in entropy of the house by exploiting the given information that the temperature inside the house is maintained at a constant temperature. the electric power consumption of the electric baseboard heaters is 30. In this plant. generates 1. (a) What is the highest efficiency that this plant can have? (b) How much heat is released into the river every second? (c) How much heat must be released by the core to supply . We can find the change in entropy of the surrounding by dividing the heat added by the temperature. The temperature of the superheated steam is 500 K.00 GW of power. Therefore the entropy of the house does not change: Heat is absorbed by the surroundings at the same rate R that energy is delivered to the house: Substitute for ΔSsurroundings yields: ΔS u = ΔS house + ΔS surroundings or. and the water in the river flows by at a temperature of 25ºC. Heat is absorbed by the liquid sodium in the core.

00 GW of electrical power? (d) Assume that new environmental laws have been passed to preserve the unique wildlife of the river.48 GW − 1. the plant is not allowed to heat the river by more than 0.48 GW dQ dm d = cΔT = cΔT (ρV ) dt dt dt dV = cΔTρ dt dV dQ dt = dt cΔTρ Solve for the flow rate dV/dt of the river: .404 500 K Poutput = 1. We can then use this efficiency to find the power that must be supplied to the plant to generate 1. Because of these laws.00 GW 0. The rate at which heat is being released to the river is related to the requisite flow rate of the river by dQ dt = cΔTρ dV dt .00 GW is given by: ε max = ε C = 1 − Tc Th ε max = 1 − 298 K = 0.1836 Chapter 19 1. from this value. at 40.4% efficiency.48 GW Pwasted = Psupplied − Pgenerated (b) Relate the wasted power to the power generated and the power supplied: Substitute numerical values and evaluate Pwasted : (d) Express the rate at which heat is being dumped into the river: Pwasted = 2.00 GW = 1. What is the minimum flow rate that the water in the Hobbes River must have? Picture the Problem We can use the expression for the Carnot efficiency of the plant to find the highest efficiency this plant can have.404 Psupplied = ε max = 2. to produce an output of 1. (a) The Carnot efficiency of a plant operating between temperatures Tc and Th is given by: Substitute numerical values and evaluate εC: (c) The power that must be supplied. the power that is wasted.00 GW of power and.50ºC.

It is a novel heat engine using water vapor as the working substance.The Second Law of Thermodynamics 1837 Substitute numerical values (see Table 19-1 for the specific heat of water) and evaluate dV/dt: J dV s = dt ⎛ J ⎞ ⎛ 3 kg ⎞ ⎜ ⎜ 4180 kg ⎟ ⎟ (0.0 W. Setting the efficiency of his steam engine equal to half the Carnot efficiency of the engine yields: dW dW dt 1 ε = dt = 2 C dQh dW dQc + dt dt dt . What is the minimum rate of exhausting heat that would make you consider believing him? Picture the Problem We can use the inventor’s data to calculate the thermal efficiency of his steam engine and then compare this value to the efficiency of a Carnot engine operating between the same temperatures. (a) The Carnot efficiency of an engine operating between these temperatures is: The thermal efficiency of the inventor’s device.50 K )⎜10 m 3 ⎟ ⎝ ⎠ ⎝ ⎠ 1.0 W You should explain to him that. you decide he has made an error in the measurement of his exhausted-heat value. in terms of the rate at which it expels heat to the air and does work is: ε C = 1− Tc 298 K = 1− = 20. He must have made a mistake in his analysis of his data−or he is a con man looking for suckers to swindle.1× 10 5 L/s 71 •• An inventor comes to you to explain his new invention.48 × 10 9 = 7. and releases heat to the air at the rate of only 25. when the air temperature is 25°C. He claims that the water vapor absorbs heat at 100°C.3% 125 W + 25.1% Th 373 K dW dW dt ε = dt = dQh dW dQc + dt dt dt 125 W = = 83. (b) After careful analysis of the data in his prospectus folder. does work at the rate of 125 W. (a) Explain to him why he cannot be correct. (b) The maximum efficiency of a steam engine that has ever been achieved is about 50% of the Carnot efficiency of an engine operating between the same temperatures. his data is not consistent with what is known about the thermodynamics of engines. because the efficiency he claims for his invention is greater than the efficiency of a Carnot engine operating between the same two temperatures.

let’s assume that his device does take in energy at the rate of 150 W each cycle and find how much work it would do with an efficiency half that of a Carnot engine: Substituting numerical values yields: dW = dt 1 2 (0.201 ⎠ a value totally inconsistent with the inventor’s claims for his engine.1838 Chapter 19 Solve for dQc/dt to obtain: ⎞ dW dQc ⎛ 2 =⎜ − 1⎟ ⎜ ⎟ dt ⎝ ε C ⎠ dt Assuming that the inventor has measured the work done per cycle by his invention correctly: dQc ⎛ 2 ⎞ =⎜ − 1⎟ (125 W ) ≈ 1100 W dt ⎝ 0. Hint: How much of the 1.00 kJ of heat could be converted into work by an ideal cyclic process? (b) What is the change in entropy of the universe for each process? .201)(150 W ) ≈ 15 W Because dQc dQh dW = − .00 kJ of heat to a reservoir at 300 K? Explain your choice.a dt dt dt reasonable value for dQc/dt is: dQc = 150 W − 15 W = 135 W dt 72 •• The cycle represented in Figure 19-12 (next to Problem 19-14) is for 1. its efficiency is that of a Carnot engine operating between the temperatures of its isotherms. The temperatures at points A and B are 300 and 750 K.00 mol of an ideal monatomic gas. dW dW 1 dQh 1 ε = dt ⇒ = 2 εC 2 C dQh dt dt dt Ignoring his claim that 125. What is the efficiency of the cyclic process ABCDA? Picture the Problem Because the cycle represented in Figure 19-12 is a Carnot cycle. The Carnot efficiency of the cycle is given by: Substitute numerical values and evaluate εC: εC = 1− εC = 1− Tc Th 300 K = 60.0% 750 K 73 •• [SSM] (a) Which of these two processes is more wasteful? (1) A block moving with 500 J of kinetic energy being slowed to rest by sliding (kinetic) friction when the temperature of the environment is 300 K. or (2) A reservoir at 400 K releasing 1.0 W of work are done per cycle. respectively.

is initially at a pressure of 16 atm.The Second Law of Thermodynamics 1839 Picture the Problem All 500 J of mechanical energy are lost. Process (1) produces more waste heat. (a) Sketch this .0 L.00 kJ to find the energy that is lost. (a) For process (2): The efficiency of a Carnot engine operating between temperatures Th and Tc is given by: W2. and a temperature of 600 K.. For process (2). It is quasi-statically expanded at constant temperature until its volume is 4. i. transformed into heat in process (1). a volume 74 •• of 1. a monatomic gas.00 kJ )⎜ ⎜ 300 K − 400 K ⎟ ⎟ ⎝ ⎠ = 0.e.00 kJ ) = 250 J ⎝ 400 K ⎠ or 750 J are lost.0 L and is then quasi-statically compressed at constant pressure until its volume and temperature are such that a quasi-static adiabatic compression will return the gas to its original state.max = Wrecovered = ε CQin ε C = 1− Tc Th ⎞ ⎟ ⎟Qin ⎠ and hence ⎛ Tc Wrecovered = ⎜ ⎜1 − T h ⎝ Substitute for ε C to obtain: ⎛ 300 K ⎞ Wrecovered = ⎜1 − ⎟(1. (b) Find the change in entropy of the universe for process (1): Express the change in entropy of the universe for process (2): ΔS1 = ΔQ 500 J = = 1. we can find the heat that would be converted to work by a Carnot engine operating between the given temperatures and subtract that amount of work from 1.67 J/K T 300 K ΔQ ΔQ + Th Tc ΔS 2 = ΔS h + ΔSc = − ⎛1 1⎞ = ΔQ ⎜ ⎜T − T ⎟ ⎟ h ⎠ ⎝ c Substitute numerical values and evaluate ΔS2: ⎛ 1 1 ⎞ ΔS 2 = (1. Process (2) is more wasteful of available work. In Part (b) we can use its definition to find the change in entropy for each process.833 J/K Helium.

we can use the equations for the work done during isothermal. Finally. 2. To find the work done during each cycle.0 atm ⎟ ⎟ ⎝ ⎠ = 2.3 L 1 1. and 3. volumes. (a) The PV diagram of the cycle is shown to the right.1840 Chapter 19 cycle on a PV diagram.294 L Apply an equation for an adiabatic process (γ =1.0 L ⎞ V1 = (16 atm )⎜ ⎜ 4. (d) Find the efficiency of the cycle. we find the efficiency of the cycle from the work done each cycle and the heat that enters the system during the isothermal expansion. and pressures at points 1. and 3 with 1 being the initial state. isobaric. and adiabatic processes.67 = 2.0 atm V2 ⎝ ⎠ 1γ ⎛P ⎞ ⎜ 1⎟ P 1V1 = P 3V3 ⇒ V3 = V1 ⎜ ⎟ ⎝ P3 ⎠ γ γ ⎛ 16 atm ⎞ V3 = (1. (c) Find the work done during each step of the cycle. (b) Find the volume and temperature after the compression at constant pressure.67) to relate the temperatures and volumes at 1 and 3: T3V3 γ −1 = T1V1 γ −1 ⎛ V1 ⎞ ⇒ T3 = T1 ⎜ ⎜V ⎟ ⎟ ⎝ 3⎠ γ −1 . 2. (b) Apply the ideal-gas law to the isothermal expansion 1→2 to find P2: Apply an equation for an adiabatic process to relate the pressures and volumes at 1 and 3: Substitute numerical values and evaluate V3: P2 = P1 ⎛ 1. Picture the Problem Denote the three states of the gas as 1. We can use the ideal-gas law and the equation of state for an adiabatic process to find the temperatures.0 L ⎟ ⎟ = 4.0 L )⎜ ⎜ 4.

and heat is released to a reservoir at a temperature Tc.18 atm ⋅ L − 6.0 atm )(2. The volume of the balloon increases by 4.24 atm ⋅ L = 5.00 kJ from a reservoir at 120ºC.00 atm absorbs 4.824 atm ⋅ L − 10.0 L ) − (4.0 atm )(2.4 ×10 2 K (c) Express the work done each cycle: For the process 1→2: W = W12 + W23 + W31 (1) 1.24 atm ⋅ L Substitute numerical values in equation (1) and evaluate W: W = 22.18 atm ⋅ L ε= 75 •• [SSM] A heat engine that does the work of blowing up a balloon at a pressure of 1.0 L ⎞ = (16 atm )(1.0 L )ln⎜ ⎜ 1. where Tc < 120ºC.0 L ⎞ T3 = (600 K )⎜ ⎜ 2. find the temperature Tc.294 L − 4.67 −1 = 344 K ⎛ V2 ⎞ ⎛ V2 ⎞ ⎟ ⎜ W12 = nRT1 ln⎜ = P V ln 1 1 ⎜V ⎟ ⎜V ⎟ ⎟ ⎝ 1⎠ ⎝ 1⎠ ⎛ 4.0 L ⎟ ⎟ ⎝ ⎠ = 22.00 L ) = −6.824 atm ⋅ L For the process 3→1: 3 W31 = −C V ΔT31 = − 3 1V1 − P 3V3 ) 2 nR (T1 − T3 ) = − 2 (P =−3 16 atm )(1.116 atm ⋅ L ≈ 20% 22.The Second Law of Thermodynamics 1841 Substitute numerical values and evaluate T3: ⎛ 1.116 atm ⋅ L = 5 atm ⋅ L (d) Use its definition to express the efficiency of the cycle: Substitute numerical values and evaluate ε: ε= W W W = = Qin Q12 W12 5.18 atm ⋅ L For the process 2→3: W23 = P2 ΔV23 = (4.00 L.294 L )] 2 [( = −10. .294 L ⎟ ⎟ ⎝ ⎠ = 3. If the efficiency of the heat engine is 50% of the efficiency of a Carnot engine working between the same two reservoirs.

00 atm )(4.00 kJ ⎜ ⎟ ⎝ ⎠ Show that the coefficient of performance of a Carnot engine run as a 76 •• refrigerator is related to the efficiency of a Carnot engine operating between the same two temperatures by ε C × COPC = Tc Th . relate the heat removed from the cold reservoir to the work done each cycle: COP = Qc W . relate the efficiency of a Carnot engine working between the same reservoirs to the temperature of the cold reservoir: Relate the efficiency of the heat engine to that of a Carnot engine working between the same temperatures: Substitute for ε C to obtain: εC = 1− Tc ⇒ Tc = Th (1 − ε C ) Th ε= 2W W =1 2 εC ⇒ εC = Qin Qin ⎛ 2W Tc = Th ⎜ ⎜1 − Q in ⎝ ⎞ ⎟ ⎟ ⎠ The work done by the gas in expanding the balloon is: W = PΔV = (1. Using its definition. Picture the Problem We can use the definitions of the COP and εC to show that their relationship is ε C × COPC = TC Th . relate Tc to the work done by and the heat input to the real heat engine.00 atm ⋅ L Substitute numerical values and evaluate Tc: ⎛ 101. Using the definition of the COP.1842 Chapter 19 Picture the Problem We can express the temperature of the cold reservoir as a function of the Carnot efficiency of an ideal engine and.00 L ) = 4. given that the efficiency of the heat engine is half that of a Carnot engine.00 atm ⋅ L × ⎟⎟ atm ⋅ L ⎠ ⎟ ⎝ ⎜ Tc = (393 K ) 1 − = 313 K ⎜ ⎟ 4.325 J ⎞ ⎞ ⎛ ⎜ 2 ⎜ 4.

The Second Law of Thermodynamics 1843 Apply energy conservation to relate Qc. The air in the kitchen has a temperature Th = 27ºC. The freezer is not perfectly insulated and some heat leaks through the walls of the freezer at a rate of 50 W. Qh. relate the heat that must be removed from the freezer to the work done by the motor: Differentiate this expression with respect to time to express the power of the motor: Express the maximum COP of the motor: COP = Q Qc ⇒W = c W COP P= dW dQc dt = dt COP COPmax = Tc ΔT . Differentiation of this expression with respect to time will yield an expression for the power of the motor that is needed to maintain the temperature in the freezer. Using the definition of the COP. Find the power of the motor that is needed to maintain the temperature in the freezer. and W: Substitute for Qc to obtain: Qc = Qh − W Qh − W W 1− COP = Divide the numerator and denominator by Qh and simplify to obtain: W Q −W Qh COP = h = W W Qh ⎛ Tc 1− ⎜ ⎜1 − T 1− ε C h = ⎝ COPc = ⎞ Tc ⎟ ⎟ T ⎠= h Because ε C = T W = 1− c : Qh Th εC εC εC and ε C × COPc = Tc Th 77 •• A freezer has a temperature Tc = –23ºC. Picture the Problem We can use the definition of the COP to express the work the motor must do to maintain the temperature of the freezer in terms of the rate at which heat flows into the freezer.

pressures.325 kPa 5.00 atm and 600 K.00 mol of a diatomic gas are taken through the cycle ABCA as shown in Figure 19-20.4 L (2.00 atm × atm 1L = 1.7 L (b) We’re given that VB = 2VA . (a) What is the volume of the gas at A? (b) What are the volume and temperature of the gas at B? (c) What is the temperature of the gas at C? (d) What is the volume of the gas at C? (e) How much work is done by the gas in each of the three segments of the cycle? (f) How much heat is absorbed or released by the gas in each segment of this cycle? Picture the Problem We can use the ideal-gas law to find the unknown temperatures. 2. and C and then find the work done by the gas and the efficiency of the cycle by using the expressions for the work done on or by the gas and the heat that enters the system for the constantpressure.38 L = 39.1844 Chapter 19 Substitute for COPmax to obtain: P= dQc ΔT dt Tc Substitute numerical values and evaluate P: ⎛ 50 K ⎞ P = (50 W )⎜ ⎜ 250 K ⎟ ⎟ = 10 W ⎝ ⎠ 78 •• In a heat engine. B.969 ×10 − 2 m 3 × −3 3 = 19. The segment BC is an adiabatic expansion and the segment CA is an isothermal compression. Hence: Apply the ideal-gas law to this constant-pressure process to obtain: VB = 2(19. (a) Apply the ideal-gas law to find the volume of the gas at A: VA = nRTA PA J ⎞ ⎟ (600 K ) mol ⋅ K ⎠ ⎝ = 101.69 L ) = 39. and volumes at points A.314 TB = TA VB 2V = (600 K ) A VA VA = 1200 K .00 mol)⎛ ⎜ 8.69 L 10 m = 19. adiabatic. (The PV diagram is not drawn to scale. and isothermal processes of the cycle. The volume at B is twice the volume at A.) At A the pressure and temperature are 5.

9754 ×10 3 J = 9.4) to find the volume of the gas at C: Substitute numerical values and evaluate VC: TC = TA = 600 K 1 ⎛ TB ⎞ γ −1 γ −1 TBVB = TCVCγ −1 ⇒ VC = VB ⎜ ⎜T ⎟ ⎟ ⎝ C⎠ ⎛ 1200 K ⎞ 1.314 600 K ln ⎜ ⎟ ⎜ 222.00 mol 8.314 ⎟ (600 K − 1200 K ) = 2.494 ×10 J 2 mol ⋅ K ⎠ ⎝ = 24.9 kJ The work done by the gas during the isothermal compression CA is: ⎛ VA WCA = nRTC ln⎜ ⎜V ⎝ C ⎞ ⎛ 19.69 L ⎞ J ⎞ ⎛ ⎟ ⎜ ( ) ( ) = 2.325 J atm ⋅ L = 9.20 kJ = − 24.98 kJ Apply the first law of thermodynamics to express the work done on the gas during the adiabatic expansion BC: WBC = ΔEint.00 mol)⎛ WBC = − 5 ⎜ 8. BC − Qin.77 L ⎟ ⎟ ⎟ mol ⋅ K ⎠ ⎝ ⎝ ⎠ ⎠ = −24. BC = ΔEint.45 atm ⋅ L × 101.77 L ⎝ ⎠ = 223 L 1 (e) The work done by the gas during the constant-pressure process AB is given by: Substitute numerical values and evaluate WAB: WAB = PA (VB − VA ) = PA (2VA − VA ) = PAVA WAB = (5.38 L )⎜ ⎜ 600 K ⎟ ⎟ = 222. BC = −ncV ΔTBC =−5 nRΔTBC 2 Substitute numerical values and evaluate WBC: J ⎞ 4 (2. BC − 0 = ΔEint.The Second Law of Thermodynamics 1845 (c) Because the process C→A is isothermal: (d) Apply an equation for an adiabatic process (γ = 1.69 L ) = 98.00 atm )(19.4 −1 VC = (39.2 kJ .

325 kPa = 253.00 atm and 600 K.00 atm. and D. 79 •• [SSM] In a heat engine.2 kJ because ΔEint. and volumes at points B. The pressure and temperature at A are 5. the segment BC an adiabatic expansion. C. We can then find the work done by the gas and the efficiency of the cycle by using the expressions for the work done on or by the gas and the heat that enters the system for the various thermodynamic processes of the cycle.314 ⎝ J ⎞ ⎟ (1200 K − 600 K ) mol ⋅ K ⎠ QBC = 0 Use the first law of thermodynamics to find the heat absorbed during the isothermal compression CA: QCA = WCA + ΔEint.) The segment AB represents an isothermal expansion. The pressure at D is 1.1846 Chapter 19 (f) The heat absorbed during the constant-pressure expansion AB is: QAB = ncP ΔTA − B = 7 nRΔTA − B = 2 = 34. CA = WCA = − 24.00 mol)⎛ ⎜ 8.9 kJ The heat absorbed during the adiabatic expansion BC is: 7 2 (2. 2. (a) Apply the ideal-gas law for a fixed amount of gas to the isothermal process AB to find the pressure at B: PB = PA VA V = (5.50 atm × = 253 kPa (b) Apply the ideal-gas law for a fixed amount of gas to the adiabatic process BC to express the temperature at C: TC = TB PCVC PBVB (1) .00 atm ) A VB 2VA 101. pressures.3 kPa 1atm = 2. (a) What is the pressure at B? (b) What is the temperature at C? (c) Find the total work done by the gas in one cycle. The volume at B is twice the volume at A. (The PV diagram is not drawn to scale.00 mol of a diatomic gas are carried through the cycle ABCDA shown in Figure 19-21.92 kJ = 34. Picture the Problem We can use the ideal-gas law to find the unknown temperatures. CA = 0 for an isothermal process.

39 L Use the equation of state for an adiabatic process and γ = 1.00 atm )(19.915 kJ ⎠ The work done during the adiabatic expansion BC is: J ⎞ (2.00 mol)⎛ WBC = −C V ΔTBC = − 5 nRΔTBC = − 5 ⎜ 8.78 L) (2.The Second Law of Thermodynamics 1847 Use the ideal-gas law to find the volume of the gas at B: VB = nRTB PB (2.09 atm ⋅ L × = −5.50 atm )(39.314 mol ⋅ K ⎟ (600 K ) ln⎜ ⎜ V ⎝ ⎠ ⎠ ⎝ A ⎞ ⎟ ⎟ = 6.314 = = 39.39 L )⎜ ⎜ 1.737 kJ The work done during the isobaric compression CD is: WCD = PC (VD − VC ) = (1.314 ⎟ (462 K − 600 K ) 2 2 mol ⋅ K ⎠ ⎝ = 5.00 atm ⎟ ⎟ ⎝ ⎠ 1 1.4 to find the volume occupied by the gas at C: Substitute numerical values in equation (1) and evaluate TC: ⎛ PB ⎞ VC = VB ⎜ ⎜P ⎟ ⎟ ⎝ C⎠ = 75.00 atm )(75.7 L − 75.50 atm ⎞ = (39.00 mol)⎜ 8.4 TC = (600 K ) = 462 K (1.325 J atm ⋅ L Express and evaluate the work done during the constant-volume process DA: WDA = 0 .78 L 1γ J ⎞ ⎟ (600 K ) mol ⋅ K ⎠ ⎝ 253.3 kPa ⎛ 2.00 mol)⎛ ⎜ 8.680 kJ 101.78 L ) = −56.39 L ) (c) The work done by the gas in one cycle is given by: W = WAB + WBC + WCD + WDA The work done during the isothermal expansion AB is: ⎛ VB WAB = nRTA ln⎜ ⎜V ⎝ A ⎞ ⎛ 2VA J ⎞ ⎛ ⎟ ⎟ = (2.

00 mol of a monatomic gas are taken through the cycle ABCA as shown in Figure 19-20.39 L = 39. The segment BC is an adiabatic expansion and the segment CA is an isothermal compression.) At A the pressure and temperature are 5.1848 Chapter 19 Substitute numerical values and evaluate W: W = 6. (The PV diagram is not drawn to scale.00 mol)⎛ ⎜ 8.00 atm and 600 K. and volumes at points A. pressures.4 L Apply the ideal-gas law to this isobaric process to find the temperature at B: (c) Because the process CA is isothermal: (d) Apply an equation for an adiabatic process (γ = 5/3) to express the volume of the gas at C: TB = TA VB 2V = (600 K ) A VA VA = 1200 K TC = TA = 600 K ⎛ TB ⎞ γ −1 ⇒ VC = VB ⎜ ⎜T ⎟ ⎟ ⎝ C⎠ 1 TBVB γ −1 = TCVC γ −1 . B.737 kJ − 5. adiabatic.7 L (b) We’re given that: VB = 2VA = 2(19.69 L = 19.314 = J ⎞ ⎟ (600 K ) mol ⋅ K ⎠ ⎝ 101. 2.00 atm × atm = 19. and C and then find the work done by the gas and the efficiency of the cycle by using the expressions for the work done on or by the gas and the heat that enters the system for the isobaric. and isothermal processes of the cycle.69 L ) = 39.325 kPa 5. (a) What is the volume of the gas at A? (b) What are the volume and temperature of the gas at B? (c) What is the temperature of the gas at C? (d) What is the volume of the gas at C? (e) How much work is done by the gas in each of the three segments of the cycle? (f) How much heat is absorbed by the gas in each segment of the cycle? Picture the Problem We can use the ideal-gas law to find the unknown temperatures.680 kJ + 0 = 6. (a) Apply the ideal-gas law to find the volume of the gas at A: VA = nRTA PA (2.972 kJ = 6.97 kJ 80 •• In a heat engine. The volume at B is twice the volume at A.915 kJ + 5.

BC = −(ncV ΔTBC ) = −17.4 L = 111 L (e) The work done by the gas during the isobaric process AB is given by: Substitute numerical values and evaluate WAB: WAB = PA (VB − VA ) = PA (2VA − VA ) = PAVA WAB = (5.314 ⎟ (600 K − 1200 K ) = 14.4 L ⎟ ⎟ ⎟ mol ⋅ K ⎠ ⎝ ⎝ ⎠ ⎠ = ΔEint. BC − 0 =−3 nRΔTBC 2 Substitute numerical values and evaluate WBC: J ⎞ (2.314 ⎝ J ⎞ ⎟ (1200 K − 600 K ) mol ⋅ K ⎠ .00 atm )(19.9 kJ 5 2 (2.The Second Law of Thermodynamics 1849 Substitute numerical values and evaluate VC: ⎛ 1200 K ⎞ 2 VC = (39.00 mol)⎛ ⎜ 8.29 kJ − 17.3 kJ (f) The heat absorbed during the isobaric expansion AB is: Qin. AB = ncP ΔTAB = 5 nRΔTAB = 2 = 24. BC = ΔEint.00 mol)⎛ WBC = − 3 ⎜ 8.39 L )⎜ ⎜ 600 K ⎟ ⎟ ⎝ ⎠ = 111.314 600 K ln ⎜ ⎟ ⎜ 111.975 kJ = 9.0 kJ The work done by the gas during the isothermal compression CA is: ⎛ VA WCA = nRTC ln⎜ ⎜V ⎝ C ⎞ ⎛ 19.98 kJ Apply the first law of thermodynamics to express the work done by the gas during the adiabatic expansion BC: WBC = ΔEint.00 mol 8.69 L ) = 98. BC − Qin.45 atm ⋅ L × 101.325 J atm ⋅ L 3 = 9.69 L ⎞ J ⎞ ⎛ ⎟ ⎜ ( ) ( ) = 2.97 kJ 2 mol ⋅ K ⎠ ⎝ = 15.

pressures. (a) Apply the ideal-gas law for a fixed amount of gas to the isothermal process AB: PB = PA VA V = (5. and volumes at points B.00 atm and 600 K.3 kPa . the segment BC an adiabatic expansion. The volume at B is twice the volume at A. 2. CA = WCA = − 17.39 L J ⎞ ⎟ (600 K ) mol ⋅ K ⎠ ⎝ 253.314 = = 39.00 mol)⎛ ⎜ 8.1850 Chapter 19 Express and evaluate the heat absorbed during the adiabatic expansion BC: Use the first law of thermodynamics to express and evaluate the heat absorbed during the isothermal compression CA: QBC = 0 QCA = WCA + ΔEint. (a) What is the pressure at B? (b) What is the temperature at C? (c) Find the total work done by the gas in one cycle. The pressure and temperature at A are 5.50 atm × = 253. 81 •• In a heat engine. and D and then find the work done by the gas and the efficiency of the cycle by using the expressions for the work done on or by the gas and the heat that enters the system for the various thermodynamic processes of the cycle.00 atm ) A 2VA VB 101. Picture the Problem We can use the ideal-gas law to find the unknown temperatures.00 mol of a monatomic gas are carried through the cycle ABCDA shown in Figure 19-21.325 kPa 1atm = 2. C. The pressure at D is 1.3 kPa = 253 kPa (b) Apply the ideal-gas law for a fixed amount of gas to the adiabatic process BC: Use the ideal-gas law to find the volume at B: TC = TB PCVC PBVB (1) VB = nRTB PB (2. (The PV diagram is not drawn to scale.3 kJ because ΔEint = 0 for an isothermal process.00 atm.) The segment AB represents an isothermal expansion.

325 J atm ⋅ L The work done during the constantvolume process DA is: Substitute numerical values in equation (2) to obtain: WDA = 0 W = 6.50 atm )(39. (The Otto cycle is discussed in Section 19-1.26 L ) (2.9 K = 416 K (c) The work done by the gas in one cycle is given by: W = WAB + WBC + WCD + WDA (2) The work done during the isothermal expansion AB is: ⎛ VB WAB = nRTA ln⎜ ⎜V ⎝ A ⎞ ⎛ 2VA J ⎞ ⎛ ⎟ ⎟ = (2.26 L ) = −48.920 kJ 101.920 kJ + 0 = 6.915 kJ ⎠ The work done during the adiabatic expansion BC is: WBC = −C V ΔTBC = − 3 nRΔTBC 2 J ⎞ (2.50 atm ⎞ = (39.9 K − 600 K ) 2 mol ⋅ K ⎠ ⎝ = 4.592 kJ The work done during the isobaric compression CD is: WCD = PC (VD − VC ) = (1.00 mol)⎜ 8.26 L TC = (600 K ) 1γ ⎛ 2.00 atm )(19.592 kJ − 4.915 kJ + 4.59 kJ 82 •• Compare the efficiency of the Otto cycle to the efficiency of the Carnot cycle operating between the same maximum and minimum temperatures.7 L − 68.00 mol)⎛ =−3 ⎜ 8.39 L )⎜ ⎜ 1.) .56 atm ⋅ L × = −4.00 atm ⎟ ⎟ ⎝ ⎠ 35 (1.00 atm )(68.39 L ) = 415.The Second Law of Thermodynamics 1851 Use the equation of state for an adiabatic process and γ = 5/3 to find the volume occupied by the gas at C: Substitute numerical values in equation (1) and evaluate TC: ⎛ PB ⎞ VC = VB ⎜ ⎜P ⎟ ⎟ ⎝ C⎠ = 68.314 ⎟ (415.314 mol ⋅ K ⎟ (600 K ) ln⎜ ⎜V ⎝ ⎠ ⎠ ⎝ A ⎞ ⎟ ⎟ = 6.

. we can compare the efficiencies by examining their ratio. We can apply the relation TV γ −1 = constant to the adiabatic processes of the Otto cycle to relate the end-point temperatures to the volumes occupied by the gas at these points and eliminate the temperatures at c and d. Substitute to obtain: ⎛ Va ⎞ Tb = Ta ⎜ ⎜V ⎟ ⎟ ⎝ b⎠ ⎛ Vd Tc = Td ⎜ ⎜V ⎝ c γ −1 ⎞ ⎟ ⎟ ⎠ γ −1 ⎛ Vd Tc − Tb = Td ⎜ ⎜V ⎝ c ⎞ ⎟ ⎟ ⎠ γ −1 ⎛ Va ⎞ − Ta ⎜ ⎜V ⎟ ⎟ ⎝ b⎠ γ −1 ⎛ Va ⎞ Tc − Tb = Td ⎜ ⎜V ⎟ ⎟ ⎝ b⎠ γ −1 ⎛ Va ⎞ − Ta ⎜ ⎜V ⎟ ⎟ ⎝ b⎠ γ −1 γ −1 ⎛ Va ⎞ = (Td − Ta )⎜ ⎜V ⎟ ⎟ ⎝ b⎠ Substitute in equation (1) and simplify to obtain: ε Otto = 1 − Td − Ta ⎛ Va (Td − Ta )⎜ ⎜V ⎝ b γ −1 ⎞ ⎟ ⎟ ⎠ γ −1 ⎛ Vb ⎞ Ta = 1− ⎜ ⎟ = 1− T ⎜V ⎟ b ⎝ a⎠ Note that. while Ta is the lowest temperature of the cycle. We can use the ideal-gas law to find the highest temperature of the gas during its cycle and use this temperature to express the efficiency of a Carnot engine. Va = Vd and Vc = Vb. The efficiency of the Otto engine is given in Example 19-2: ε Otto = 1 − Td − Ta Tc − Tb (1) where the subscripts refer to the various points of the cycle as shown in Figure 19-3.1852 Chapter 19 Picture the Problem We can express the efficiency of the Otto cycle using the result from Example 19-2. Finally. Apply the relation TV γ −1 = constant to the adiabatic process a→b to obtain: Apply the relation TV γ −1 = constant to the adiabatic process c→d to obtain: Subtract the first of these equations from the second to obtain: In the Otto cycle. Tb is not the highest temperature.

is the Brayton cycle. Assume the system begins the adiabatic compression at temperature T1.The Second Law of Thermodynamics 1853 Apply the ideal-gas law to c and b to obtain an expression for the cycle’s highest temperature Tc: The efficiency of a Carnot engine operating between the maximum and minimum temperatures of the Otto cycle is given by: Express the ratio of the efficiency of a Carnot engine to the efficiency of an Otto engine operating between the same temperatures: P Pc Pb = ⇒ Tc = Tb c > Tb Pb Tc Tb ε Carnot = 1 − Ta Tc ε Carnot ε Otto Ta Tc > 1 because Tc > Tb. Because the adiabatic transitions in the cycle do not have heat flow associated with them. can be written as ε = 1 − r (1− γ ) γ . The paths 1→2 and 3→4 are adiabatic. P 2 Qh ⇓ 3 1 ⇓ 4 V Qc . Picture the Problem The efficiency of the cycle is the ratio of the work done to the heat that flows into the engine. which involves (1) an adiabatic compression. often used in refrigeration. (c) Show that this (T3 − T2 ) efficiency. where r is the pressure ratio Phigh/Plow of the maximum and minimum pressures in the cycle. (a) The Brayton heat engine cycle is shown to the right. = Ta 1− Tb 1− Hence. ε Carnot > ε Otto 83 ••• [SSM] A common practical cycle.(3) an adiabatic expansion. (a) Sketch this cycle on a PV diagram. (b) Show that the (T − T ) efficiency of the overall cycle is given by ε = 1 − 4 1 . and transitions to temperatures T2. T3 and T4 after each leg of the cycle. Heat Qh enters the gas during the isobaric transition from state 2 to state 3 and heat Qc leaves the gas during the isobaric transition from state 4 to state 1. (2) an isobaric (constant pressure) expansion. all we must do is consider the heat flow in and out of the engine during the isobaric transitions. and (4) an isobaric compression back to the original state.

1854 Chapter 19 (b) The efficiency of a heat engine is given by: During the constant-pressure expansion from state 1 to state 2 heat enters the system: During the constant-pressure compression from state 3 to state 4 heat enters the system: Substituting in equation (1) and simplifying yields: ε= Q − Qc W = h Qin Qin (1) Q23 = Qh = nC P ΔT = nC P (T3 − T2 ) Q41 = −Qc = −nC P ΔT = −nC P (T1 − T4 ) ε= = (T3 − T2 ) + (T1 − T4 ) (T3 − T2 ) (T − T ) = 1− 4 1 (T3 − T2 ) (c) Given that. for the adiabatic transition from state 3 to state 4: nC P (T3 − T2 ) − (− nC P (T1 − T4 )) nC P (T3 − T2 ) Tγ = constant P γ −1 ⎛P T1γ T2γ ⇒ T1 = ⎜ low = γ −1 γ −1 ⎜P Plow Phigh ⎝ high ⎞ ⎟ ⎟ ⎠ γ −1 γ T2 ⎛P T4 = ⎜ low ⎜P ⎝ high ⎞ ⎟ ⎟ ⎠ γ −1 γ T3 γ −1 γ γ −1 γ Subtract T1 from T4 and simplify to obtain: ⎛P T4 − T1 = ⎜ low ⎜P ⎝ high ⎛P = ⎜ low ⎜P ⎝ high ⎞ ⎟ ⎟ ⎠ ⎞ ⎟ ⎟ ⎠ ⎛P T3 − ⎜ low ⎜P ⎝ high ⎞ ⎟ ⎟ ⎠ T2 γ −1 γ (T3 − T2 ) . use the ideal-gas law to eliminate V and obtain: Let the pressure for the transition from state 1 to state 2 be Plow and the pressure for the transition from state 3 to state 4 be Phigh. for an adiabatic transition. TV γ −1 = constant . Then for the adiabatic transition from state 1 to state 2: Similarly.

0 h each day. Picture the Problem The efficiency of the Brayton refrigerator cycle is the ratio of the heat that enters the system to the work done to operate the refrigerator. Assume 15 cents per kWh of electric energy and thirty days in a month. until its temperature is T3. What is the coefficient of performance for your refrigerator? (d) To absorb heat from the food compartment at the rate of 120 W. The pressure ratio r = Phigh/Plow for the cycle is 5. .0. (T4 − T1 ) . the volume and temperature are 75 mL and –25°C. Because the adiabatic transitions in the cycle do not have heat flow associated with them. After the expansion at constant pressure. (b) Show that the coefficient of performance is COPB = (T3 − T2 − T4 + T1 ) (c) Suppose your ″Brayton cycle refrigerator″ is run as follows. how much does it add to your monthly electric bill. what is the rate at which electrical energy must be supplied to the motor of this refrigerator? (e) Assuming the refrigerator motor is actually running for only 4.The Second Law of Thermodynamics 1855 Dividing both sides of the equation by T3 − T2 yields: P T4 − T1 ⎛ = ⎜ low ⎜ T3 − T2 ⎝ Phigh ⎞ ⎟ ⎟ ⎠ γ −1 γ Substitute in the result of Part (b) and simplify to obtain: ⎛P ε = 1 − ⎜ low ⎜P ⎝ high = 1 − (r ) γ where r = ⎞ ⎟ ⎟ ⎠ γ −1 γ ⎛ Phigh = 1− ⎜ ⎜P ⎝ low ⎞ ⎟ ⎟ ⎠ 1−γ γ 1−γ Phigh Plow 84 ••• Suppose the Brayton cycle engine (see Problem 83) is run in reverse as a refrigerator in your kitchen. The cylinder containing the refrigerant (a monatomic gas) has an initial volume and pressure of 60 mL and 1. all we must do is consider the heat flow in and out of the refrigerator during the isobaric transitions. Then the gas is adiabatically compressed. In this case. And then it is compressed at constant pressure until its temperature T2. the cycle begins at temperature T1 and expands at constant pressure until its temperature T4. Finally.0 atm. it adiabatically expands until it returns to its initial state at temperature T1. (a) Sketch this cycle on a PV diagram.

Heat Qc enters the gas during the constantpressure transition from state 1 to state 4 and heat Qh leaves the gas during the constant-pressure transition from state 3 to state 2. We’re given that the temperature in state 4 is: For the constant-pressure transition from state 1 to state 4.1856 Chapter 19 2 1 Qc W where W = Q32 − Q14 COPB = (b) The coefficient of performance of the Brayton cycle refrigerator is given by: During the constant-pressure compression from state 3 to state 2 heat leaves the system: During the constant-pressure expansion from state 1 to state 4 heat enters the system: Substituting in equation (1) and simplifying yields: Q32 = −Qh = −nC P ΔT = − nC P (T2 − T3 ) Q14 = Qc = nC P ΔT = nC P (T4 − T1 ) COPB = = = (T4 − T1 ) − (T4 − T1 ) − (T2 − T3 ) T4 − T1 T3 − T2 − T4 + T1 nCP (T4 − T1 ) − nCP (T2 − T3 ) − nCP (T4 − T1 ) (c) The COPB requires the temperatures corresponding to states 1. The paths 1→2 and 3→4 are adiabatic. 2. P Qh 3 4 V (1) Qc . and 4. 3. the quotient T/V is constant: Substitute numerical values and evaluate T1: T4 = −25°C + 273 K = 248 K ⎛ V1 ⎞ T1 T4 = ⇒ T1 = ⎜ ⎜V ⎟ ⎟T4 V1 V4 ⎝ 4⎠ ⎛ 60 mL ⎞ T1 = ⎜ ⎟ (248 K ) = 198 K ⎝ 75 mL ⎠ ⇓ ⇓ (a) The Brayton refrigerator cycle is shown to the right.

67 −1 ⎛ P2 ⎞ γ 1.The Second Law of Thermodynamics 1857 Given that.67 −1 γ −1 γ T4 Substitute numerical values and evaluate T3: Similarly. for an adiabatic transition.67 ( ⎟ ( ) T2 = ⎜ = T 5 198 K ) 1 ⎜P ⎟ ⎝ 1⎠ = 378 K Substitute numerical values in the expression derived in Part (a) and evaluate COPB: (d) From the definition of COPB: COPB = 248 K − 198 K 473 K − 378 K − 248 K + 198 K = 1. for the adiabatic transition from state 2 to state 1: T3 = (5) 1. use the ideal-gas law to eliminate V and obtain: For the adiabatic transition from state 4 to state 3: Tγ = constant P γ −1 ⎛ P3 ⎞ T3γ T4γ ⇒ T3 = ⎜ = γ −1 γ −1 ⎜P ⎟ ⎟ P3 P4 ⎝ 4⎠ 1. TV γ −1 = constant . fQc dW = dt COPB Express the heat Qc that is drawn from the cold reservoir: Substituting for Qc yields: Qc = nC P ΔT = nC P (T4 − T1 ) fnC P (T4 − T1 ) dW = COPB dt n= P4V4 RT4 Use the ideal-gas law to express the number of moles of the gas: .1 W= Qc COPB The rate at which energy must be supplied to this refrigerator is given by: 1 dQc dW = dt COPB dt or. if the frequency of the AC power input is f.67 (248 K ) = 473 K γ −1 1.

Substitute for n and CP to 2 obtain: 5 2 dW = dt = f 5 2 fP4V4 (T4 − T1 ) (COPB )T4 P4V4 R(T4 − T1 ) RT4 COPB Substitute numerical values and evaluate dW/dt: 5 2 dW = dt (60 s ) −1 ⎛ 10 −3 m 3 ⎞ ⎜ ⎟ (101.15 4.T2) is zero. T2). γ = CP CV . Picture the Problem We can use nR = CP − CV .21 kW (e) The monthly cost of operation is given by Monthly Cost = Cost Per Unit of Power × Power Consumption = rate × daily consumption × number of days per month Substitute numerical values and evaluate the monthly cost of operation: Monthly Cost = \$0.207 kW × × 30 d ≈ \$4 kWh d 85 ••• Using ΔS = CV ln (T2 T1 ) + nR ln (V2 V1 ) (Equation 19-16) for the entropy change of an ideal gas. and TV γ −1 = a constant to show that the entropy change for a quasi-static adiabatic expansion that proceeds from state (V1.325 kPa )⎜ 75 mL × ⎟(248 K − 198 K ) L ⎝ ⎠ = 207 W (1. Express the entropy change for a general process that proceeds from state 1 to state 2: For an adiabatic process: ⎛ T2 ⎞ ⎛ V2 ⎞ ΔS = CV ln⎜ ⎜T ⎟ ⎟ + nR ln⎜ ⎜V ⎟ ⎟ ⎝ 1⎠ ⎝ 1⎠ T2 ⎛ V1 ⎞ =⎜ ⎟ ⎟ T1 ⎜ ⎝ V2 ⎠ γ −1 . T1) to state (V2. CP = 5 R .0 h × 0.11)(248 K ) = 0. show explicitly that the entropy change is zero for a quasi-static adiabatic expansion from state (V1.T1) to state (V2.1858 Chapter 19 Because the gas is monatomic.

. The entropy change of the universe is then ΔSu = Qc/Th − Qc/Tc. Su < 0. . then the entropy of the universe could decrease.e. heat Qh is taken from the hot reservoir and no heat is rejected to the cold reservoir. the entropy of the universe would decrease.The Second Law of Thermodynamics 1859 Substitute for T2 and simplify to obtain: T1 γ −1 ⎡ ⎛ V1 ⎞ ⎤ ⎢ CV ln⎜ γ −1 ⎜V ⎟ ⎟ ⎥ ⎛ V1 ⎞ ⎛ V2 ⎞ ⎛ V2 ⎞ ⎢ ⎥ 2 ⎠ ⎝ ΔS = CV ln⎜ ⎜V ⎟ ⎟ + nR ln⎜ ⎜V ⎟ ⎟ = ln⎜ ⎜V ⎟ ⎟ ⎢nR + ⎥ V ⎝ 2⎠ ⎝ 1⎠ ⎝ 1 ⎠⎢ ln 2 ⎥ V1 ⎢ ⎥ ⎣ ⎦ ⎡ ⎛ V1 ⎞ ⎤ (γ − 1)CV ln⎜ ⎢ ⎜V ⎟ ⎟⎥ ⎛ V2 ⎞ ⎛ V2 ⎞ ⎢ 2 ⎠⎥ ⎝ = ln⎜ = ln⎜ ⎜V ⎟ ⎟ [nR − (γ − 1)CV ] ⎜V ⎟ ⎟ ⎢nR + V1 ⎥ 1 ⎝ ⎠ ⎝ 1⎠ − ln ⎢ ⎥ V 2 ⎢ ⎥ ⎣ ⎦ Use the relationship between CP and CV to obtain: Substituting for nR and γ and simplifying yields: nR = CP − CV ⎛ Cp ⎞ ⎤ ⎛ V2 ⎞ ⎡ ⎜ ⎟ ⎟ ΔS = ln⎜ C − C − − 1 ⎢ P V ⎜V ⎟ ⎜C ⎟CV ⎥ ⎝ 1 ⎠⎣ ⎝ V ⎠ ⎦ = 0 86 ••• (a) Show that if the refrigerator statement of the second law of thermodynamics were not true. the entropy of the universe would decrease. i. (b) Show that if the heat-engine statement of the second law were not true. then the entropy change of the universe is ΔSu = −Qh/Th + 0. then the entropy of the universe could decrease. which is negative. Because Th > Tc. (b) In this case. Again. that is. (c) A third statement of the second law is that the entropy of the universe cannot decrease. Have you just proved that this statement is equivalent to the refrigerator and heat-engine statements? Picture the Problem (a) Suppose the refrigerator statement of the second law is violated in the sense that heat Qc is taken from the cold reservoir and an equal amount of heat is transferred to the hot reservoir and W = 0. Qc = 0.

as shown in Figure 19-22. Show that the net efficiency of the combination is given by ε net = ε 1 + ε 2 − ε 1ε 2 . W2.1860 Chapter 19 (c) The heat-engine and refrigerator statements of the second law only state that some heat must be rejected to a cold reservoir and some work must be done to transfer heat from the cold to the hot reservoir. Express the net efficiency of the two heat engines connected in series: Express the efficiencies of engines 1 and 2: Solve for W1 and W2 and substitute to obtain: Express the efficiency of engine 1 in terms of Qm and Qh: Substitute for Qm/Qh and simplify to obtain: ε net = W1 + W2 Qh ε1 = W1 W and ε 2 = 2 Qh Qm ε net = ε1Qh + ε 2Qm Qh = ε1 + Qm ε2 Qh ε1 = 1 − Qm Q ⇒ m = 1 − ε1 Qh Qh ε net = ε 1 + (1 − ε 1 )ε 2 = ε 1 + ε 2 − ε 1ε 2 88 ••• Suppose that two heat engines are connected in series. Qh. such that the heat released by the first engine is used as the heat absorbed by the second engine. such that the heat released by the first engine is used as the heat absorbed by the second engine as shown in Figure 19-22. Picture the Problem We can express the net efficiency of the two engines in terms of W1. (Note that this result means that two Th . Suppose that each engine is an ideal reversible heat engine. The heat-engine and refrigerator statements in conjunction with the Carnot efficiency are equivalent to ΔSu ≥ 0. and Qh and then use ε1 = W1/Qh and ε2 = W2/Qm to eliminate W1. 87 ••• Suppose that two heat engines are connected in series. Engine 1 operates between temperatures Th and Tm and Engine 2 operates between Tm and Tc. respectively. The efficiencies of the engines are ε1 and ε2. where Th > Tm > Tc. but these statements do not specify the minimum amount of heat rejected or work that must be done. The statement ΔSu ≥ 0 is more restrictive. W2. Show that the net efficiency of T the combination is given by ε net = 1 − c . and Qm.

they would produce all of Shakespeare’s works. Express the efficiencies of ideal reversible engines 1 and 2: ε1 = 1 − and Tm Th Tc Tm (1) ε2 = 1− The net efficiency of the two engines connected in series is given by: Express the efficiencies of engines 1 and 2: Solve for W1 and W2 and substitute in equation (3) to obtain: Express the efficiency of engine 1 in terms of Qm and Qh: Substitute for Qm to obtain: Qh (2) ε net = ε1 = W1 + W2 Qh (3) W1 W and ε 2 = 2 Qh Qm ε net = ε1Qh + ε 2Qm Qh = ε1 + Qm ε2 Qh ε1 = 1 − Q Qm ⇒ m = 1 − ε1 Qh Qh ε net = ε1 + (1 − ε1 )ε 2 Substitute for ε1 and ε2 and simplify to obtain: ε net = 1 − Tm ⎛ Tm ⎞ ⎛ Tc ⎞ +⎜ ⎟ ⎟⎜ ⎜1 − T ⎟ ⎟ Th ⎜ T h m ⎠ ⎝ ⎠⎝ T T T T = 1− m + m − c = 1− c Th Th Th Th 89 ••• [SSM] The English mathematician and philosopher Bertrand Russell (1872-1970) once said that if a million monkeys were given a million typewriters and typed away at random for a million years. W2. W2. we can substitute the expressions for the efficiencies of the ideal reversible engines to obtain ε net = 1 − Tc Th . and Qh and then use ε1 = W1/Qh and ε2 = W2/Qm to eliminate W1. and Qm.The Second Law of Thermodynamics 1861 reversible heat engines operating ″in series″ are equivalent to one reversible heat engine operating between the hottest and coldest reservoirs. Qh.) Picture the Problem We can express the net efficiency of the two engines in terms of W1. Finally. Let us limit ourselves to the following fragment of Shakespeare (Julius Caesar III:ii): .

it were a grievous fault.) Picture the Problem There are 26 letters and four punctuation marks (space. I come to bury Caesar. so we have a grand total of 30 characters to choose from.16 × 107 s ⎟ ⎟ ⎝ ⎠ ( ) ≈ 10484 y T TRussell or T ≈ 10 478 TRussell = 10484 y = 10478 6 10 y . We can use this number of possible arrangements to express the probability that one monkey will write out this passage and then an estimate of a monkey’s typing speed to approximate the time required for one million monkeys to type the passage from Shakespeare. and exclamation point) used in the English language. Even with this small fragment. And grievously hath Caesar answered it . .30 × 10 491 s ⎜ ⎜ 3. it would take about 330 s to write a passage of length equal to the quotation from Shakespeare. This fragment is 330 characters (including spaces) long. The good is oft interred with the bones. if so.5 )(330 ) 1 = 1 = 10 −495 495 10 T= (330 s )(10495 ) 106 ⎛ ⎞ 1y = 3. (You can even assume that the monkeys are immortal. So let it be with Caesar. And. it will take a lot longer than a million years! By what factor (roughly speaking) was Russell in error? Make any reasonable assumptions you want. The evil that men do lives on after them. . not to praise him. countrymen! Lend me your ears. Romans. there are then 30330 different possible arrangements of the character set to form a fragment this long. comma. disregarding capitalization. express the probability P that one monkey will write out this passage: Use the approximation 30 ≈ 1000 = 101. Assuming the monkeys type at random. period. The noble Brutus hath told you that Caesar was ambitious. Find the time T required for a million monkeys to type this particular passage by accident: Express the ratio of T to Russell’s estimate: P= 1 30330 P= 10 (1.5 to obtain: Assuming the monkeys can type at a rate of 1 character per second.1862 Chapter 19 Friends.