CHAPTER

19

Heat and the First Law of Thermodynamics

1 * Body A has twice the mass and twice the specific heat of body B. If they are supplied with equal amounts of heat, how do the subsequent changes in their temperatures compare? M A = 2M B; cA = 2cB; C = Mc; T = Q/C CA = 4CB; TA = TB/4 2 The temperature change of two blocks of masses M A and M B is the same when they absorb equal amounts of heat. It follows that the specific heats are related by (a ) cA= (MA / MB)cB . (b ) cA = (MB / MA)cB . (c ) c A = c B . (d ) none of the above. (b ) The specific heat of aluminum is more than twice that of copper. Identical masses of copper and aluminum, both at 20C, are dropped into a calorimeter containing water at 40C. When thermal equilibrium is reached, (a ) the aluminum is at a higher temperature than the copper. (b ) the aluminum has absorbed less energy than the copper. (c) the aluminum has absorbed more energy than the copper. (d ) both (a ) and (c) are correct statements. (c ) Sam the shepherd's partner, Bernard, who is a working dog, consumes 2500 kcal of food each day. (a ) How many joules of energy does Bernard consume each day? (b ) Sam and Bernard often find themselves sleeping out in the cold night. If the energy consumed by Bernard is dissipated as heat at a steady rate over 24 h, what is his power output in watts as a heater for Sam? (a) E = Q E = (4.184 2.5 106) J = 10.46 MJ (b ) P = E/t P = (10.46 106/8.64 104) W = 121 W

5* A solar home contains 105 kg of concrete (specific heat = 1.00 kJ/kgK). How much heat is given off by the concrete when it cools from 25 to 20C?

Chapter 19 Q = CT = mcT 6

Heat and the First Law of Thermodynamics Q = (105 103 5) J = 500 MJ

How many calories must be supplied to 60 g of ice at -10C to melt it and raise the temperature of the water to 40C? Q = CiceTice + mLf + CwaterTwater Q = 60(10 0.49 + 79.7 + 40) cal = 7.48 kcal How much heat must be removed when 100 g of steam at 150C is cooled and frozen into 100 g of ice at 0C? (Take the specific heat of steam to be 2.01 kJ/kgK.) Q = m(csteam Tsteam + Lv + cwTw + Lf) Q = 100(0.48 50 + 540 + 100 + 79.7) cal = 74.4 kcal A 50-g piece of aluminum at 20C is cooled to 196C by placing it in a large container of liquid nitrogen at that temperature. How much nitrogen is vaporized? (Assume that the specific heat of aluminum is constant and is equal to 0.90 kJ/kgK.) mNLvN = mAlcAlTAl; solve for mN mN = (50 0.9 216/199) g = 48.8 g If 500 g of molten lead at 327C is poured into a cavity in a large block of ice at 0C, how much of the ice melts? mw = [500(24.7 + 0.128 327)/333.5] g = 99.8 g mPb(Lf,Pb + cpbT) + mwLf,w = 0; solve for mw

9*

10 A 30-g lead bullet initially at 20C comes to rest in the block of a ballistic pendulum. Assume that half the initial kinetic energy of the bullet is converted into thermal energy within the bullet. If the speed of the bullet was 420 m/s, what is the temperature of the bullet immediately after coming to rest in the block? 2 Q = 1/2(1/2mv2) = mcPbT; T = v2/4c Pb; cPb in J/kg T = (420 /4 128) K = 344.5 K 11 A 1400-kg car traveling at 80 km/h is brought to rest by applying the brakes. If the specific heat of steel is 0.11 cal/gK, what total mass of steel must be contained in the steel brake drums if the temperature of the brake drums is not to rise by more than 120C? 1. Find Q = 1/2mv2 Q = 1/2 1400 22.22 J = 345.7 kJ = 82.6 kcal 2. M = Q/cT M = (82.6/0.11 120) kg = 6.26 kg 12 A 200-g piece of lead is heated to 90C and is then dropped into a calorimeter containing 500 g of water that is initially at 20C. Neglecting the heat capacity of the container, find the final temperature of the lead and water. In the solution of Problems 12 to 23 (Calorimetry) the fundamental relationship Qout = Qin is used. mPbcPb(tPb tf) = mwcw(tf tw); solve for tf tf(500 + 200 0.128)=(500 20 + 200 0.128 90); tf = 23.4 oC 13* The specific heat of a certain metal can be determined by measuring the temperature change that occurs when a piece of the metal is heated and then placed in an insulated container made of the same material and containing water. Suppose a piece of metal has a mass of 100 g and is initially at 100C. The container has a mass of 200 g and contains 500 g of water at an initial temperature of 20.0C. The final temperature is 21.4C. What is the specific heat of the metal? m1c(t1i tf) = m2c(tf t2i) + mwcw(tf t2i); find c 78.6c = 2.8c + 7; c = 0.093 cal/g.K

Chapter 19

Heat and the First Law of Thermodynamics

14 A 25-g glass tumbler contains 200 mL of water at 24C. If two 15-g ice cubes each at a temperature of 3C are dropped into the tumbler, what is the final temperature of the drink? Neglect thermal conduction between the tumbler and the room. (mgcg + 200)(24 tf) = 3micecice + mice (Lf + tf); find tf 205 24 205tf = 44.1 + 30(79.7 + tf); tf = 10.6 oC 15 A 200-g piece of ice at 0C is placed in 500 g of water at 20C. The system is in a container of negligible heat capacity and is insulated from its surroundings. (a ) What is the final equilibrium temperature of the system? (b ) How much of the ice melts? (a) To melt the ice requires 200 79.7 cal 16 kcal; reducing the temperature of the water to 0oC releases 10 kcal. Therefore, not all the ice melts, and the final temperature is 0oC. (b ) The mass of ice that melts is (10 kcal)/(79.7 cal/g) = 125 g. 16 A 3.5-kg block of copper at a temperature of 80C is dropped into a bucket containing a mixture of ice and water whose total mass is 1.2 kg. When thermal equilibrium is reached the temperature of the water is 8C. How much ice was in the bucket before the copper block was placed in it? (Neglect the heat capacity of the bucket.) mCucCutCu = mwtw + miceLf; solve for mice 3.5 0.0923 72 = 1.2 8 + 79.7mice; mice = 0.171 kg 17* A well-insulated bucket contains 150 g of ice at 0C. (a ) If 20 g of steam at 100C is injected into the bucket, what is the final equilibrium temperature of the system? (b ) Is any ice left afterward? (a), (b ) mstLv + mst(100 tf) = mice(Lf + tf); tf = 4.97oC; (b ) Since tf > 0oC, no ice is left. solve for tf 18 A calorimeter of negligible mass contains 1 kg of water at 303 K and 50 g of ice at 273 K. Find the final temperature T. Solve the same problem if the mass of ice is 500 g. 1. miceLf + micetf = mw(30 tf); solve for tf, mice = 50 g 50(79.7 + tf) = 1000(30 tf); tf = 24.8oC 2. For mice = 500 g, only 376 g will melt. tf = 0oC 19 A 200-g aluminum calorimeter contains 500 g of water at 20C. A 100-g piece of ice cooled to 20C is placed in the calorimeter. (a ) Find the final temperature of the system, assuming no heat loss. (Assume that the specific heat of ice is 2.0 kJ/kg. K.) (b ) A second 200-g piece of ice at 20C is added. How much ice remains in the system after it reaches equilibrium? (c) Would you give a different answer for (b ) if both pieces of ice were added at the same time? (a ) (mAlcAl + mwcw)(20 tf) = 20micecice + mice(Lf + tf) tf = 3.0oC (b ) Find Q released to lower Al and H2O to 0oC Q = (200 0.215 + 600)3.0 = 1929 cal o Find Qice required to raise 200 g of ice to 0 C Qice = 200 0.478 20 = 1912 cal Find the amount of ice melted by 17 cal m = 17/79.7 g = 0.21 g; ice remaining = 199.8 g (c) The initial and final conditions are the same No 20 The specific heat of a 100-g block of material is to be determined. The block is placed in a 25-g copper calorimeter that also holds 60 g of water. The system is initially at 20C. Then 120 mL of water at 80C are added to the calorimeter vessel. When thermal equilibrium is attained, the temperature of the water is 54C. Determine the specific heat of the block.

Chapter 19

Heat and the First Law of Thermodynamics

(mBcB + mCucCu + mw1)tB = mw2t2; here tB = 34 K, t2 = 26 K, mw1 = 60 g, mw2 = 120 g. Solve for cB.

cB = 0.295 cal/g.K

21* Between innings at his weekly softball game, Stan likes to have a sip or two of beer. He usually consumes about 6 cans, which he prefers at exactly 40F. His wife Bernice puts a six-pack of 12-ounce aluminum cans of beer (1 ounce has a mass of 28.4 g) originally at 80F in a well-insulated Styrofoam container and begins adding ice. How many 30g ice cubes must she add to the container so that the final temperature is 40F? (Neglect heat losses through the container and the heat removed from the aluminum and assume that the beer is mostly water.) 1. Convert to Celsius degrees. 40 oF = 4.44oC; 80oF = 26.67oC 2. mBcBtB = n icemice(Lf + 4.44); solve for n ice n ice = (6 12 28.4 22.2/30 84.14) = 18 22 A 100-g piece of copper is heated in a furnace to a temperature t. The copper is then inserted into a 150-g copper calorimeter containing 200 g of water. The initial temperature of the water and calorimeter is 16C, and the final temperature after equilibrium is established is 38C. When the calorimeter and its contents are weighed, 1.2 g of water are found to have evaporated. What was the temperature t? 1. 1.2Lv + (mw + mcalcCu)tcal = mCucCutCu; find tCu tCu = [1.2 540 + (200 + 150 0.0923) 22]/(100 0.0923) Co o o o 2. t = tf + tCu tCu = 578 C ; t = (578 + 38) C = 616 C 23 A 200-g aluminum calorimeter contains 500 g of water at 20C. Aluminum shot of mass 300 g is heated to 100C and is then placed in the calorimeter. (a ) Using the value of the specific heat of aluminum given in Table 19-1, find the final temperature of the system, assuming that no heat is lost to the surroundings. (b ) The error due to heat transfer between the system and its surroundings can be minimized if the initial temperature of the water and calorimeter is chosen to be
1 2

t w below room temperature, where tw is the temperature change of the calorimeter and water
1 2

during the measurement. Then the final temperature is

t w above room temperature. What should the initial

temperature of the water and container be if the room temperature is 20C? (a ) mshcAl(100 tf) = (mcalcal + mw)(tf 20); find tf 6450 64.5tf = 532.3tf 10645; tf = 28.6oC (b ) For the calorimeter, let ti = tr t0 and tf = tr + t0, mshcAl(100 - 20 t0) = (mcalcAl + mw)(2t0); o where tr = 20 C; write the calorimetry equation, 64.5 80 64.5t0 = 2 532.3t0; t0 = 4.57oC; solve for t0, ti. ti = 15.43oC. 24 Joule's experiment establishing the mechanical equivalence of heat involved the conversion of mechanical energy into internal energy. Give some examples of the internal energy of a system being converted into mechanical energy. Steam turbine; internal combustion engine; a person performing mechanical work, e.g., climbing a hill. 25* Can a system absorb heat with no change in its internal energy? Yes 26 In the equation Q = U + W (the formal statement of the first law of thermodynamics), the quantities Q and W represent (a ) the heat supplied to the system and the work done by the system.

Chapter 19

Heat and the First Law of Thermodynamics

(b ) the heat supplied to the system and the work done on the system. (c) the heat released by the system and the work done by the system. (d ) the heat rele ased by the system and the work done on the system. (a ) 27 A diatomic gas does 300 J of work and also absorbs 600 cal of heat. What is the change in internal energy of the gas? From Equ. 19-10, U = Q W U = (600 4.184 300) J = 2210 J 28 If 400 kcal is added to a gas that expands and does 800 kJ of work, what is the change in the internal energy of the gas? From Equ. 19-10, U = Q W U = (400 4.184 800) kJ = 874 kJ 29* A lead bullet moving at 200 m/s is stopped in a block of wood. Assuming that all of the energy change goes into heating the bullet, find the final temperature of the bullet if its initial temperature is 20C. Q = 1/2mv2 = mct = mc(tf ti); tf = ti + v2/2c tf = (20 + 2002/2 128)oC = 176oC 30 (a ) At Nia gara Falls, the water drops 50 m. If the change in potential energy goes into the internal energy of the water, compute the increase in its temperature. (b ) Do the same for Yosemite Falls, where the water drops 740 m. (These temperature rises are not observed because the water cools by evaporation as it falls.) (a ), (b ) Here U = mgh = mct; t = gh /c (a ) t = 9.81 50/4184 = 0.117 K; (b ) t = 1.74 K 31 When 20 cal of heat are absorbed by a gas, the system performs 30 J of work. What is the change in the internal energy of the gas? From Equ. 19-10, U = Q W U = (20 4.184 30) J = 53.7 J 32 A lead bullet initially at 30C just melts upon striking a target. Assuming that all of the initial kinetic energy of the bullet goes into the internal energy of the bullet to raise its temperature and melt it, calculate the speed of the bullet upon impact. Q = 1/2mv2 = mc(TMP Ti) + mLf; solve for v v = 2[c( T MP T i )+ L f ] = 354 m/s 33* A piece of ice is dropped from a height H. (a ) Find the minimum value of H such that the ice melts when it makes an inelastic collision with the ground. Assume that all the mechanical energy lost goes into melting the ice. (b ) Is it reasonable to neglect the variation in the acceleration of gravity in doing this problem? (c) Comment on the reasonableness of neglecting air resistance. What effect would air resistance have on your answer? (a ) To melt the ice (at t = 0oC), mgh = mLf; h = Lf/g h = 333.5/9.81 km = 34 km (b ) Yes. Since h << RE = 6370 km, one can neglect the variation of g . (c) The piece of ice (depending on its mass and shape) will reach its terminal velocity long before striking the ground, and some of the ice will melt before it reaches the ground. However, the relation U = mgh = mLf remains valid, so air resistance does not affect h . 34 On a cold day you can warm your hands by rubbing them together. (a ) Assume that the coefficient of friction

Chapter 19

Heat and the First Law of Thermodynamics

between your hands is 0.5, that the normal force between your hands is 35 N, and that you rub them together at an average speed of 35 cm/s. What is the rate at which heat is generated? (b ) Assume further that the mass of each of your hands is approximately 350 g, that the specific heat of your hands is about 4 kJ/kgK, and that all the heat generated goes into raising the temperature of your hands. How long must you rub your hands together to produce a 5C increase in their temperature? (a ) dQ/dt = P = f fv. dQ/dt = 35 0.5 0.35 J/s = 6.125 W 3 (b ) Q = (dQ/dt)t = mcT; t = mcT/(dQ/dt) t = 0.35 4 10 5/6.125 s = 1143 s = 19.0 min 35 A real gas cools during a free expansion, though an ideal gas does not. Explain. For the ideal gas, U is a function of T only. Since W = 0 and Q = 0 in free expansion, U = 0 and T is constant. For a real gas, U depends on the density of the gas because the molecules do exert weak attractive forces on each other. In free expansion these forces reduce the average kinetic energy of the molecules and, consequently, the temperature. 36 An ideal gas at one atmosphere pressure and 300 K is confined to half of an insulated container by a thin partition. The partition is then removed and equilibrium is established. At that point, which of the following is correct? (a ) The pressure is half an atmosphere and the temperature is 150 K. (b ) The pressure is one atmosphere and the temperature is 150 K. (c) The pressure is half an atmosphere and the temperature is 300 K. (d ) None of the above. (c ) 37* A certain gas consists of ions that repel each other. The gas undergoes a free expansion with no heat exchange and no work done. How does the temperature of the gas change? Why? The temperature of the gas increases. The average kinetic energy increases with increasing volume due to the repulsive interaction between the ions. 38 A gas changes its state reversibly from A to C (Figure 19-16). The work done by the gas is (a ) greatest for path A B C. (b ) least for path A C. (c) greatest for path A D C. (d ) the same for all three paths. (a ) In Problems 39 through 42, the initial state of 1 mol of an ideal gas is P1 = 3 atm, V1 = 1 L, and U 1 = 456 J, and final state is P2 = 2 atm, V2 = 3 L, and U 2 = 912 J. 39 The gas is allowed to expand at constant pressure to a volume of 3 L. It is then cooled at constant volume until its pressure is 2 atm. (a ) Show this process on a PV diagram, and calculate the work done by the gas. (b ) Find the heat added during this process.

Chapter 19

Heat and the First Law of Thermodynamics

(a ) The path from the initial state I to the final state F is shown on the PV diagram. Here, P is in atmospheres and V in liters. The work done by the gas is equal to the area under the path. W = 303 2 103 kJ = 606 J

(b ) Q = W + U = W + (Uf Ui)

Q = (606 + 456) J = 1062 J

40 The gas is first cooled at constant volume until its pressure is 2 atm. It is then allowed to expand at constant pressure until its volume is 3 L. (a ) Show this process on a PV diagram, and calculate the work done by the gas. (b ) Find the heat added during this process. (a ) The path from the initial state I to the final state F is shown on the PV diagram. Here, P is in atmospheres and V in liters. The work done by the gas is equal to the area under the path. W = 202 2 103 kJ = 404 J

(b ) Q = W + U

Q = (404 + 456) J = 860 J

41* The gas is allowed to expand isothermally until its volume is 3 L and its pressure is 1 atm. It is then heated at constant volume until its pressure is 2 atm. (a ) Show this process on a PV diagram, and calculate the work done by the gas. (b ) Find the heat added during this process. (a ) The path from the initial state I to the final state B is shown on the PV diagram. Here, P is in atmospheres and V in liters. The work done by the gas is equal to the area under the path. Here, the work (area under the curve) is given by Equ. 19-16. We replace nRT1 by P1V1. W = 303 ln(3) kJ = 333 kJ.

(b ) Q = W + U 42

Q = (333 + 456) J = 789 J

The gas is heated and is allowed to expand such that it follows a straight-line path on a PV diagram from its initial

Chapter 19

Heat and the First Law of Thermodynamics

state to its final state. (a ) Show this process on a PV diagram, and calculate the work done by the gas. (b ) Find the heat added during this process. (a ) The path from the initial state I to the final state F is shown on the PV diagram.Here, P is in atmospheres and V in liters. The work done by the gas is equal to the area under the path. Here, the work (area under the curve) is W = 5 atm.L = 505 J.

(b ) Q = W + U

Q = (505 + 456) J = 961 J

43 One mole of the ideal gas is initially in the state P0 = 1 atm, V0 = 25 L. As the gas is slowly heated, the plot of its state on a PV diagram moves in a straight line to the state P = 3 atm, V = 75 L. Find the work done by the gas. The path on a PV diagram is shown. Here P is in atmospheres and V in liters. The work done by the gas is the area under the curve in units of atm.L. W = 100 atm.L = 10.1 kJ

44 One mole of the ideal gas is heated so that T = AP2, where A is a constant. The temperature changes from T0 to 4T0. Find the work done by the gas. 1. From the ideal gas law, PV = RT = RAP2. If T changes from T0 to 4T0, the pressure increases from P0 to 2P0. The volume is given by V = RAP, so the volume increases linearly with pressure from V0 to 2V0. It now follows that the work done by the gas, the area under the straight line from P0, V0 to 2P0, 2V0 is W = P0V0 + 1/2P0V0 = 3P0V0/2. 45* One mole of an ideal gas initially at a pressure of 1 atm and a temperature of 0C is compressed isothermally and quasi-statically until its pressure is 2 atm. Find (a ) the work needed to compress the gas, and (b ) the heat removed from the gas during the compression. (a ) Use Equ. 19-16, and V2/V1 = P1/P2 W (on the gas) = 8.314 273 ln(2) = 1573 J (b ) T = 0, U = 0; Q = W (by the gas) Q (removed from the gas) = 1573 J 46 An ideal gas initially at 20C and 200 kPa has a volume of 4 L. It undergoes a quasi-static, isothermal expansion until its pressure is reduced to 100 kPa. Find (a ) the work done by the gas, and (b ) the heat added to the gas during the expansion. (a ) Use Equ. 19-16; nRT = PV W = 800 ln 2 J = 555 J (b ) For an isothermal process, U = 0, Q = W Q = 555 J

Chapter 19

Heat and the First Law of Thermodynamics

47 The heat capacity at constant volume of a certain amount of a monatomic gas is 49.8 J/K. (a ) Find the number of moles of the gas. (b ) What is the internal energy of the gas at T = 300 K? (c) What is the heat capacity of the gas at constant pressure? (a ) Monatomic gas, Cv = (3/2) nR n = 2 49.8/3 8.314 = 4 (b ) U = CvT U = 49.8 300 J = 14.9 kJ (c) Cp = Cv + nR = (5/2) nR Cp = 49.8 5/3 J/K = 83 J/K 48 The DulongPetit law was originally used to determine the molecular mass of a substance from its measured heat capacity. The specific heat of a certain solid is measured to be 0.447 kJ/kgK. (a ) Find the molecular mass of the substance. (b ) What element is this? (a ), (b ) C = 3nR; 3R = CM (M = molecular mass) (a ) M = 3 8.314/0.447 = 55.8; (b ) Iron 49* The specific heat of air at 0C is listed in a handbook as having the value of 1.00 J/gK measured at constant pressure. (a ) Assuming that air is an ideal gas with a molar mass M = 29.0 g/mol, what is its specific heat at 0C and constant volume? (b ) How much internal energy is there in 1 L of air at 0C and at 1 atm? (a ) For a diatomic gas, Cv = (5/7) Cp Cv = 0.714 J/g.K (b ) air = 1.29 g/L; U = CvT U = 1.29 0.714 273 J = 252 J 50 One mole of an ideal diatomic gas is heated at constant volume from 300 to 600 K. (a ) Find the increase in internal energy, the work done, and the heat added. (b ) Find the same quantities if this gas is heated from 300 to 600 K at constant pressure. Use the first law of thermodynamics and your results for (a ) to calculate the work done. (c) Calculate the work done in (b ) directly from dW = P dV. (a ) Q = CvT; W = 0 for constant volume; U = Q Q = (5/2)8.314 300 = 6.236 kJ = U; W = 0 (b ) Q = CpT; U = CvT; W = Q - U Q = (7/5) 6.236 kJ = 8.73 kJ;U = 6.236 kJ; Vf W = 2.49 kJ W = P dV = P( ) = R( ) (c ) V f Vi T f Ti W = 8.314 300 J = 2.49 kJ
Vi

51 A diatomic gas (molar mass M ) is confined to a closed container of volume V at a pressure P0. What amount of heat Q should be transferred to the gas in order to triple the pressure? (Express your answer in terms of P0 and V.) 1. Use the ideal gas law to find T. T0 = P0V/nR; Tf = 3P0V/nR = 3T0; T = 2T0 = 2P0V/nR 2. Q = CvT Q = (5/2) nR(2P0V/nR) = 5P0V 52 One mole of air (cv = 5R / 2) is confined at atmospheric pressure in a cylinder with a piston at 0C. The initial volume occupied by gas is V. Find the volume of gas V after the equivalent of 13,200 J of heat is transferred to it. 1. Find T and Tf; CpT = Q; Cp = 7R/2 T = 13200 2/7 8.314 K = 454 K; Tf = 754 K 2. V = 22.4 L; V = V(Tf/Ti) V = 22.4(754/300) L = 56.3 L

Chapter 19

Heat and the First Law of Thermodynamics

53* The heat capacity of a certain amount of a particular gas at constant pressure is greater than that at constant volume by 29.1 J/K. (a ) How many moles of the gas are there? (b ) If the gas is monatomic, what are Cv and Cp? (c) If the gas consists of diatomic molecules that rotate but do not vibrate, what are Cv and Cp? (a ) nR = 29.1 J/K n = 29.1/8.314 = 3.5 (b ) Cv = 3nR/2; Cp = 5nR/2 Cv = 1.5 29.1 J/K = 43.65 J/K; Cp = 72.75 J/K (c) Cv = 5nR/2; Cp = 7nR/2 Cv = 72.75 J/K; Cp = 101.85 J/K 54 One mole of a monatomic ideal gas is initially at 273 K and 1 atm. (a ) What is its initial internal energy? (b ) Find its final internal energy and the work done by the gas when 500 J of heat are added at constant pressure. (c) Find the same quantities when 500 J of heat are added at constant volume. (a ) U = CvT = 3RT/2 U = (3 8.314 273/2) J = 3405 J (b ) T = Q/Cp; U = CvT = QCv/Cp; W = Q - U U = 0.6 500 J = 300 J; U = 3705 J; W = 200 J (c) U = Q; W = 0 (constant volume) U = 500 J; U = 3905 J; W = 0 55 A certain molecule has vibrational energy levels that are equally spaced by 0.15 eV. Find the critical temperature Tc such that for T >> Tc you would expect the equipartition theorem to hold and for T << Tc you would expect the equipartition theorem to fail. Tc is approximately that temperture at which kTc = 0.15 eV = 2.4 10-20 J; Tc = 2.4 10-20/1.38 10-23 K = 1740 K 56 When an ideal gas is subjected to an adiabatic process, (a ) no work is done by the system. (b ) no heat is supplied to the system. (c) the internal energy remains constant. (d ) the heat supplied to the system equals the work done by the system. (b ) 57* One mole of an ideal gas ( =
5 3

) expands adiabatically and quasi-statically from a pressure of 10 atm and a

temperature of 0C to a pressure of 2 atm. Find (a ) the initial and final volumes, (b ) the final temperature, and (c) the work done by the gas. (a ) Vi = 22.4 1/Pi L; from Equ. 19-37, Vi = 2.24 L; Vf = 2.24(5) 0.6 L = 5.88 L Vf = Vi(Pi/Pf)1/ (b ) Tf = PfVf/R Tf = (202 5.88/8.314) K = 143 K (c) W = Q U = 0 CvT = CvT W = 1.5 8.314 130 J = 1.62 kJ 58 An ideal gas at a temperature of 20C is compressed quasi-statically and adiabatically to half its original volume.
3 2

Find its final temperature if (a ) Cv =

nR, and (b ) Cv =

5 2

nR.

(a ) Here, = 5/3; from Equ. 19-36, Tf = Ti(Vi/Vf)-1 (b ) Here, = 7/5. 59

Tf = 293(2) 0.67 K = 465 K Tf = 293(2) 0.4 K = 387 K

Two moles of neon gas initially at 20C and a pressure of 1 atm are compressed adiabatically to one-fourth of their

Chapter 19

Heat and the First Law of Thermodynamics

initial volume. Determine the temperature and pressure following compression. For Neon, = 5/3. Tf = Ti(Vi/Vf)-1; Pf = Pi(Vi/Vf) Tf = 293(4) 0.67 K = 738 K; Pf = 1(4) 1.67 atm = 10.1 atm 60 Half a mole of an ideal monatomic gas at a pressure of 400 kPa and a temperature of 300 K expands until the pressure has diminished to 160 kPa. Find the final temperature and volume, the work done, and the heat absorbed by the gas if the expansion is (a ) isothermal, and (b ) adiabatic. (a ) 1. Find Vi from the ideal gas law. Vi = (8.314 300/2 400) L = 3.12 L 2. For the isothermal case, Vf = Vi(Pi/Pf) Vf = 3.12(400/160) L = 7.8 L 3. Tf = Ti Tf = 300 K 4. Use Equ. 19-16; W = nRT ln(Vf/Vi) W = 0.5 8.314 300 ln(2.5) J = 1.14 kJ 5. Q = U + W; U = 0 Q = 1.14 kJ 1/ (b ) 1. From Equ. 19-37,Vf = Vi(Pi/Pf) Vi = 3.12 L; Vf = 3.12(2.5) 0.6 L = 5.41 L 2. Tf = PfVf/nR Tf = (160 5.41/0.5 8.314) K = 208 K 3. W = -U = CvT; Q = 0 W = (0.5 1.5 8.314 92) J = 574 J; Q = 0 61* Repeat Problem 60 for a diatomic gas. (a ) See Problem 60. (b ) 1. Here = 1.4; proceed as in Problem 60. 2. Tf = PfVf/nR 3. U = CvT; Q = 0; W = U

Vi = 3.12 L; Vf = 7.8 L; Tf = 300 K; W = Q = 1.14 kJ Vi = 3.12 L; Vf = 3.12(2.5) 0.714 = 6.0 L Tf = (160 6.0/0.5 8.314) K = 231 K W = (0.5 2.5 8.314 69) J = 717 J; Q = 0

62 One-half mole of helium is expanded adiabatically and quasi-statically from an initial pressure of 5 atm and temperature of 500 K to a final pressure of 1 atm. Find (a ) the final temperature, (b ) the final volume, (c) the work done by the gas, and (d ) the change in the internal energy of the gas. (a ) From Equs. 19-36 and 37, Tf = Ti(Pf/Pi)11/ For He, = 5/3;Tf = 500(0.2) 0.4 K = 263 K (b ) 1. Find Vi = nRTi/Pi Vi = (0.5 8.314 500/505) L = 4.12 L 1/ 2. Vf = Vi(Pi/Pf) Vf = 4.12(5) 0.6 L = 10.8 L (c), (d ) U = CvT; W = U U =-(0.5 1.5 8.314 237) J = 1.48 kJ; W = 1.48 kJ 63 A hand pump is used to inflate a bicycle tire to a gauge pressure of 482 kPa (about 70 lb/in2). How much work must be done if each stroke of the pump is an adiabatic process? Atmospheric pressure is 1 atm, the air temperature is initially 20C, and the volume of the air in the tire remains constant at 1 L. Consider the process to be accomplished in a single compression. The initial pressure is 1 atm = 101 kPa. The final pressure is (101 + 482) kPa = 583 kPa, and the final volume is 1 L. We can now determine the initial volume of the air. Since air is a mixture of diatomic gases, air = 1.4. 1. Find Vi = Vf(Pf/Pi)1/ Vi = 1(583/101) 0.714 L = 3.5 L 2. Use Equ. 19-39, where W is work done by the W (on the gas) = (3.5 101 583)/0.4 J = 574 J gas.

Chapter 19

Heat and the First Law of Thermodynamics

64 An ideal gas at initial volume V1 and pressure P1 expands quasi-statically and adiabatically to volume V2 and pressure P2. Calculate the work done by the gas directly by integrating P dV, and show that your result is the same as that given by Equation 19-39. For the adiabatic process, PV = constant = C.
V2

So, P = C/V and W = P dV = C V dV = V1 V1

V2

C (V 1 V1 ) 0. CV21 = P2V2 and CV11 = P1V1. With 2 1 1- 1

P1 V 1 P 2 V 2 these substitutions we obtain the desired result: W = .

65* One mole of N2 (Cv =

5 2

R ) gas is originally at room temperature (20C) and a pressure of 5 atm. It is allowed to

expand adiabatically and quasi-statically until its pressure equals the room pressure of 1 atm. It is then heated at constant pressure until its temperature is again 20C. During this heating, the gas expands. After it reaches room temperature, it is heated at constant volume until its pressure is 5 atm. It is then compressed at constant pressure until it is back to its original state. (a ) Construct an accurate PV diagram showing each process in the cycle. (b ) From your graph, determine the work done by the gas during the complete cycle. (c) How much heat is added or subtracted from the gas during the complete cycle? (d ) Check your graphical determination of the work done by the gas in (b ) by calculating the work done during each part of the cycle. (a ) 1. Find V at start of cycle, point A, from VA = nRT/P. VA = (8.314 293/505) L = 4.82 L. 2. Find VB. VB = VA(PA/PB)1/ = 4.82(5) 0.714 L = 15.2 L 3. Find VC = VD = (8.314 293/101) L = 24.0 L The complete cycle is shown in the diagram. Here P is in atmospheres and V in liters.

(b ) Note that for the paths A-B and B-C, W, the work done by the gas, is positive. For the path D-A, W is negative, and greater in magnitude than WA-C. The total work done by the gas is negative and its magnitude is the area enclosed by the cycle. Each rectangle of the dotted lines equals 5 atm.L. Counting these rectangles, the approximate work done by the gas is about 13 5 atm.L = 65 atm.L. (c) Since U is a state function, U = 0 for the complete cycle. Consequently, Q = W = -65 atm.L = -6.43 kJ (d ) 1. A-B is an adiabatic process. QA-B = 0 1 2. B-C, Q = CPT; CP = 7R/2; TB = TA(VA/VB) TB = 293(4.82/15.2) 0.4 K = 185 K; QB-C = 3.14 kJ 3. C-D, Q = CvT; Cv = 5R/2; TD = PDVD/R TD = (505 24/8.314) K = 1458 K; QC-D = 24.2 kJ 4. D-A, Q = CpT QD-A = [7 8.314 (1165)/2] J = 33.9 kJ 5. Qtot = QA-B + QB-C + QC-D + QD-A Qtot = (3.14 + 24.2 33.9) kJ = 6.54 kJ; fair agreement with 6.43 kJ of part (c).

Chapter 19

Heat and the First Law of Thermodynamics

66 Two moles of an ideal monatomic gas have an initial pressure P1 = 2 atm and an initial volume V1 = 2 L. The gas is taken through the following quasi-static cycle: It is expanded isothermally until it has a volume V2 = 4 L. It is then heated at constant volume until it has a pressure P3 = 2 atm. It is then cooled at constant pressure until it is back to its initial state. (a ) Show this cycle on a PV diagram. (b ) Calculate the heat added and the work done by the gas during each part of the cycle. (c) Find the temperatures T1, T2, and T3. (a ) The cycle is shown in the diagram. Here P is in atmospheres and V is in liters. (c) 1. Find T1 = P1V1/nR T1 = 24.3 K 2. Find T2; isothermal expansion, T2 = T1. T2 = 24.3 K 3. Find T3 = P3V3/nR T3 = 48.6 K (b ) 1-2: Q = W = nRT ln(V2/V1) Q1-2 = 280 J; W = 280 J 2-3: Q = CvT; Cv = 3R Q2-3 = 606 J; W = 0 3-1: Q = CpT; Cp = 5R; W = Q CvT Q3-1 = 1010 J; W = 404 J

67 At point D in Figure 19-17 the pressure and temperature of 2 mol of an ideal monatomic gas are 2 atm and 360 K. The volume of the gas at point B on the PV diagram is three times that at point D and its pressure is twice that at point C. Paths AB and CD represent isothermal processes. The gas is carried through a complete cycle along the path DABCD. Determine the total amount of work done by the gas and the heat supplied to the gas along each portion of the cycle. 1. Find the volume at D from V = nRT/P VD = (2 8.314 360/202) L = 29.6 L 2. Find VB, VC, PC, and PB VB = VC = 3VD = 88.8 L; PC = (2/3) atm, PB = (4/3) atm 3. Find TC, TB , and TA TC = TD = 360 K; TB = TA = 2TD = 720 K A 4 29.6 720 B 4/3 88.8 720 C 2/3 88.8 360 D 2 29.6 360

P (atm) V (L) T (K)

4. D-A: W = 0; Q = U = CvT A-B: W = nRT ln(VB/VA) = Q; U = 0 B-C: W = 0; Q = U = CvT C-D: W = nRT ln(VD/VC) = Q; U = 0 5. Wtot = WD-A + WA-B + WB-C + WC-D

WD-A = 0; QD-A = UD-A = 3 8.314 360 J = 8.98 kJ WA-B = 2 8.314 720 ln(3) J = 13.16 kJ; QA-B = 13.16 kJ WB-C = 0; QB-C = 3 8.314 360 J = 8.98 J WC-D = 2 8.314 360 ln(3) J = 6.58 kJ; QC-D = 6.58 kJ Wtot = 6.58 kJ

68 Repeat Problem 67 with the paths AB and CD representing adiabatic processes. 1. Find PC; PC = PD(VD/VC) PC = 202 (1/3) 1.67 kPa = 32.25 kPa

Chapter 19 2. Find TC; TC = PCVC/nR

Heat and the First Law of Thermodynamics TC = (32.3 88.8/2 8.314) K = 172 K

3. Use the information given to construct the table shown below. A B C D P (kPa) 404 64.5 32.25 202 V (L) 29.6 88.8 88.8 29.6 T (K) 720 344 172 360 4. D-A: W = 0; Q = U = CvT A-B: W = CvT; Q = 0 B-C: W = 0; Q = U = CvT C-D: W = CvT; Q = 0 5. Wtot = WD-A + WA-B + WB-C + WC-D QD-A = 8.98 kJ; WD-A = 0 QA-B = 0; WA-B = 3 8.314 376 J = 9.38 kJ QB-C = 4.29 kJ; WB-C = 0 QC-D = 0; WC-D = 3 8.314 188 = -4.69 kJ Wtot = 4.69 kJ

69* Repeat Problem 67 with a diatomic gas. Proceed as in Problem 67 with Cv = 5R. The pressures, volumes, and temperatures are as shown in the table of Problem 67. The results are as follows D-A: WD-A = 0; QD-A = (5/3) 8.98 kJ = 15.0 kJ A-B: WA-B = 13.16 kJ; QA-B = 13.16 kJ B-C: WB-C = 0; QB-C = 15.0 kJ C-D: WC-D = -6.58 kJ; QC-D = 6.58 kJ Wtot = 6.58 kJ. Note that the total work done is the same for the diatomic and monatomic gases. 70 Repeat Problem 68 with a diatomic gas. Proceed as in Problem 68 with Cv = 5R and = 1.4. The pressures, volumes, and temperatures are as shown in the table below. W and Q are calculated as in Problem 68, and the results are given below. A 404 29.6 720 B 86.8 88.8 464 C 43.4 88.8 232 D 202 29.6 360 WD-A = 0; QD-A = 15.0 kJ WA-B = 10.64 kJ; QA-B = 0 WB-C = 0; QB-C = 9.64 kJ WC-D = 5.32 kJ; QC-D = 0 Wtot = 5.32 kJ

P (kPa) V (L) T (K)

D-A: W = 0; Q = U = CvT A-B: W = CvT; Q = 0 B-C: W = 0; Q = CvT C-D: W = CvT; Q = 0 Wtot = WD-A + WA-B + WB-C + WC-D

71 An ideal gas of n mol is initially at pressure P1, volume V1, and temperature Th. It expands isothermally until its pressure and volume are P2 and V2. It then expands adiabatically until its temperature is Tc and its pressure and volume are P3 and V3. It is then compressed isothermally until it is at a pressure P4 and a volume V4, which is related to its

Chapter 19 initial volume V1 by T c V4

1

Heat and the First Law of Thermodynamics

1 = Th V 1 . The gas is then compressed adiabatically until it is back in its original state.

(a ) Assuming that each process is quasi-static, plot this cycle on a PV diagram. (This cycle is known as the Carnot cycle for an ideal gas.) (b ) Show that the heat Qh absorbed during the isothermal expansion at Th is Qh = nRT h ln( V2 / V1). 0 (c) Show that the heat Qc given off by the gas during the isothermal compression at Tc is
Qc = nRTc ln( V3 / V4). 0 (d ) Using the result that TV 1 is constant for an adiabatic expansion, show that V2 / V1 = V3

/ V4. (e) The efficiency of a Carnot cycle is defined to be tshe net work done divided by the heat absorbed Qh. Using the first law of thermodynamics, show that the efficiency is 1 Qc / Qh. (f ) Using your results from the previous parts of this problem, show that Qc / Qh = Tc / Th. (a ) The cycle is shown on the adjoining PV diagram. (b ) Since U = 0, and T1 = Th, Qh = Wh = nRTh ln(V2/V1) (c) U = 0; T3 = Tc, Q3-4 = W3-4 = nRTc ln(V4/V3); this is the heat absorbed by the gas. The heat released is Qc = nRTc ln(V3/V4). (d ) From Equ. 19-36, we have V1/V4 = (Tc/Th)1/(1) = V2/V3. It then follows that V2/V1 = V3/V4. (e) Since U is a state function, U = 0 for the complete cycle. Consequently, W = Q = Qh - Qc. By definition, = W/Qh, so = 1 Qc/Qh. (f ) Using the result of part (d ) it follows that Qc/Qh = Tc/Th. 72 After a potato wrapped in aluminum foil has been baked in an oven, it is taken out and its foil removed. The foil cools much faster than the potato. Why? Foil has a smaller mass, a smaller specific heat, and a larger surface area. 73* True or false: (a ) The heat capacity of a body is the amount of heat it can store at a given temperature. (b ) When a system goes from state 1 to state 2, the amount of heat added to the system is the same for all processes. (c) When a system goes from state 1 to state 2, the work done on the system is the same for all processes. (d ) When a system goes from state 1 to state 2, the change in the internal energy of the system is the same for all processes. (e) The internal energy of a given amount of an ideal gas depends only on its absolute temperature. (f ) A quasi-static process is one in which there is no motion. (g ) For any material that expands when heated, Cp is greater than Cv. (a ) False. (b ) False. (c) False. (d ) True. (e) True. (f ) False. (g ) True. 74 If a system's volume remains constant while undergoing changes in temperature and pressure, then (a ) the internal energy of the system is unchanged. (b ) the system does no work. (c) the system absorbs no heat. (d ) the change in internal energy equals the heat absorbed by the system. (b ) and (d )

Chapter 19

Heat and the First Law of Thermodynamics

75 When an ideal gas is subjected to an isothermal process, (a ) no work is done by the system (b ) no heat is supplied to the system (c) the heat supplied to the system equals the change in internal energy. (d ) the heat supplied to the system equals the work done by the system. (d ) 76 The 1-L fuel tank of a gas grill contains 600 g of propane (C3H8) at a pressure of 2MPa. What can you say about the phase state of the propane? 1. For C3H8, M = 44; find n n = 600/44 = 13.6 2. Find T = PV/nR T = (2 103/13.6 8.314) K = 17.7 K At this low temperature and high pressure, C3H8 is a solid. (The melting point of propane at 1 atm pressure is 83 K.) 77* An ideal gas undergoes a process during which P V = constant and the volume of the gas decreases. What happens to the temperature? PV = C V = nRT. If V decreases, the T decreases. 78 The volume of three moles of a monatomic gas is increased from 50 L to 200 L at constant pressure. The initial temperature of the gas is 300 K. How much heat must be supplied to the gas? Q = CpT; Tf = 4Ti; T = 3Ti; Cp =15R/2 Q = (15 8.314 900/2) J = 56.1 kJ 79 In the process of compressing n moles of an ideal diatomic gas to one-fifth of its initial volume, 180 kJ of work is done on the gas. If this is accomplished isothermally at room temperature (293 K), how many calories of heat are removed from the gas? Q = U + W; U = 0; Q (removed) = W (on gas) Heat removed = 180 kJ 80 What is the number of moles n of the gas in Problem 79? Equ. 19-16: W = nRT ln(V2/V1); n = W/[RT ln(V2/V1)] n = [180 103/(8.314 293 ln 0.2)] = 45.9 81* The PV diagram in Figure 19-18 represents 3 mol of an ideal monatomic gas. The gas is initially at point A. The paths AD and BC represent isothermal changes. If the system is brought to point C along the path AEC, find (a ) the initial and final temperatures, (b ) the work done by the gas, and (c) the heat absorbed by the gas. Although not required for this problem, we begin by determining pressures, volumes, and temperatures at points A, B, C, D, and E, and then list these as in the table below. (a ) Find TA = TD and TC = TB using T = PV/nR TA = (4 404/3 8.314) K = 64.8 K; TC = 81 K Find VB and VA using V = nRT/P VB = (81/64.8) 4.0 = 5.0 L; VD = 16.0 L A 4.0 4.0 B 4.0 5.0 C 1.0 20.0 D 1.0 16.0 E 1.0 4.0

P (atm) V (L)

Chapter 19 T (K) 64.8 81.0 81.0

Heat and the First Law of Thermodynamics 64.8 16.2 W = 16 atm.L = 1.62 kJ Q = (1.62 + 9 8.314 16.2/2) kJ = 2.23 kJ

(b ) WA-E = 0; WE-C = PEV; (c) Q = W + U; U = CvT; Cv = 3nR/2 82 Repeat Problem 81 with the gas following path ABC. Use the results shown in the table of Problem 81. (a ) See table of Problem 81. (b ) 1. WA-B = PAVA-B; WB-C = nRTB ln(VC/VB) 2. W = WA-B + WB-C (c) Q = W + U; U = 0.61 kJ (see Problem 81)

TA = 64.8 K; TC = 81.0 K WA-B = 0.404 kJ; WB-C = 3 8.314 81 ln(4) = 2.8 kJ W = 3.20 kJ Q = 3.81 kJ

83 Repeat Problem 82 with the gas following path ADC. Use the results shown in the table of Problem 81. (a ) See the table of Problem 81. TA = 64.8 K; TC = 81.0 K (b ) 1. WA-D = nRTA ln(VD/VA); WD-C = PDVD-C WA-D = 3 8.314 64.8 ln(4) J = 2.24 kJ; WD-C = 0.404 kJ 2. W = WA-D + WD-C W = 2.64 kJ (c) Q = W + U; U = 0.61 kJ (see Problem 81) Q = 3.25 kJ 84 Suppose that the paths AD and BC represent adiabatic processes. What then are the work done by the gas and the heat absorbed by the gas in following the path ABC? (a ) T is a state function. See Problem 81 for TA, TC TA = 64.8 K; TC = 81.0 K (b ) 1. Find VD and VB using PV = constant; = 5/3 VD = 4 40.6 L = 9.19 L; VB = 20/40.6 L = 8.71 L 2. Find TD and TB using ideal gas law. TD = 37.2 K; TB = 141 K 3. WA-B = PAVA-B; WA-B = 0.404 4.71 kJ = 1.90 kJ; WB-C = CvTB-C WB-C = 9 8.314 60/2 J = 2.24 kJ; W = WA-B + WB-C W = 4.14 kJ (c) Q = W + U; U = 0.61 kJ (see Problem 81) Q = 4.75 kJ 85* Repeat Problem 84 for the path ADC. (a ) See Problem 84. (b ) See Problem 84 for VD, TD; WA-D = CvTA-D; WD-C = PDVD-C; W = WA-D + WD-C (c) Q = W + U; U = 0.61 kJ

TA = 64.8 K; TC = 81.0 K WA-D = 9 8.314 27.6/2 J = 1.03 kJ; WD-C = 0.101 10.81 kJ = 1.09 kJ; W = 2.12 kJ Q = 2.73 kJ

86

3 At very low temperatures, the specific heat of a metal is given by c = aT + bT . For the metal copper,

a = 0.0108 J / kgK2 and b = 7.62 104 J / kgK4. (a ) What is the specific heat of copper at 4 K? (b ) How much heat is required to heat copper from 1 to 3 K?

Chapter 19 (a ) c = 0.0108T + 7.62 104T 3 J/kg.K (b ) Q = c(T) dT 0

Ti Tf

Heat and the First Law of Thermodynamics c(4) = 9.20 102 J/kg.K

Q = 0.0108T dT + 7.62 10 4 T 3 dT = 0.0584 J/kg

1 1

87 Two moles of a diatomic ideal gas are compressed isothermally from 18 L to 8 L. In the process, 170 calories escape from the system. Determine the amount of work done by the gas, the change in internal energy, and the initial and final temperatures of the gas. 1. W = nRT ln(Vf/Vi ) = Q + U; U = 0 W = 170 cal = 711 J; W (on gas) = 711 J 2. U = 0 in an isothermal process. U = 0 3. Ti = Tf = W/[nR ln(Vf/Vi)] Ti = Tf = 711/[2 8.314 ln(8/18)] K = 52.7 K

88 Suppose the two moles of a diatomic ideal gas in Problem 87 are compressed from 18 L to 8 L adiabatically. The work done on the gas is 820 J. Find the initial temperature and the initial and final pressures.

PfV W = Pi V i 1
find Pi

[ ( / ) ] = Pi V i V f V i V f ; 1

Pi =

0.4 820 Pa = 47.56 kPa 1.4 [(18 8)(18/8 ) ] 10 3

Find T1 = Ti from the ideal gas law Find T2 = Tf from W = CvT Find Pf from the ideal gas law

Ti = (47.56 18/2 8.314) K = 51.5 K T = 820/5 8.314 K = 19.7 K; Tf = 71.2 K Pf = 2 8.314 71.2/8 kPa = 148 kPa

89* Repeat Problem 87 with the diatomic ideal gas replaced by a monatomic ideal gas. The results are the same for the diatomic gas. See Problem 87. 90 Repeat Problem 88 with the diatomic ideal gas replaced by a monatomic ideal gas. Repeat Problem 88 with = 1.67. The results are: Pi = 42.3 kPa, Pf = 164 kPa; Ti = 45.8 K, Tf = 78.6 K. 91 How much work must be done to 30 grams of CO at standard temperature and pressure to compress it to a fifth of its initial volume if the process is (a ) isothermal; (b ) adiabatic? 1. Find n ; M = 28 30 g = 30/28 mol; n = 1.07 2. Find Vi; at STP 1 mol = 22.4 L; Vf = Vi/5 Vi = 22.4 10.7 = 24.0 L; Vf = 4.8 L (a ) W(on gas) = nRT ln(Vf/Vi) W(on gas) = 1.07 8.314 273 ln(0.2) = 3.91 kJ

Pi V i P f V (b ) W = 1
92

[ ( / ) ] = Pi V i V f V i V f ; 1

W(on gas) = 1(4.8 51.4 24)/0.4 atm.L = 54.2 atm.L = 5.48 kJ.

= 1.4 Repeat Problem 91 if the gas is CO2.

Chapter 19

Heat and the First Law of Thermodynamics

From Table 19-5, cv = 3.39R; cp = (3.39 + 1.02) R. Therefore, = 1.30; M (CO2) = 44, so n = 0.682. (a ) W(on gas) = -nRT ln(Vf/Vi); (see Problem 91) W(on gas) = (3.91 0.682/1.07) kJ = 2.49 kJ (b ) Find Vi and Vf = Vi/5 Vi = 0.682 22.4 L = 15.3 L; Vf = 3.06 L W(on gas) = (3.06 51.3 15.3)/0.3 atm.L = 3.2 kJ

[ ( / ) ] W = Pi V i P f V f = P i V i V f V i V f ; 1 1
= 1.3

93* Repeat Problem 91 if the gas is argon. For Ar, M = 40, so n = 0.75; = 1.67. Following the procedure of the two preceding problems we obtain: Vi = 16.8 L and Vf = 3.36 L. For (a ) W(on gas) = 2.74 kJ; for (b ) W(on gas) = 48.5 atm.L = 4.9 kJ. 94 A thermally insulated system consists of 1 mol of a diatomic ideal gas at 100 K and 2 mol of a solid at 200 K that are separated by a rigid insulating wall. Find the equilibrium temperature of the system after the insulating wall is removed, assuming that the solid obeys the Dulong-Petit law. 1. Determine Cv,solid and Cv,gas . Cv,solid = 2 3R = 49.9 J/K; Cv,gas = 2.5R = 20.8 J/K 2. Apply calorimetry equation, Qtot = 0 20.8( Tf 100) = 49.9(200 - Tf) 3. Solve for Tf Tf = 170.6 K

95 When an ideal gas undergoes a temperature change at constant volume, its energy changes by U = CvT (a ) Explain why this result holds for an ideal gas for any temperature change independent of the process. (b ) Show explicitly that this result holds for the expansion of an ideal gas at constant pressure by first calculating the work done and showing that it can be written as W = nRT, and then by using U = Q W, where Q = CpT. (a ) For an ideal gas, the internal energy is the sum of the kinetic energies of the gas molecules, which is proportional to kT. Consequently, U is a function of T only, and U = CvT. (b ) 1. At constant pressure, W = P(Vf Vi) = nR(Tf Ti) = nRT. 2. At constant pressure, Q = CpT. U = Q W = (Cp nR)T = CvT. 96 One mole of an ideal monatomic gas is heated at constant volume from 300 to 600 K. (a ) Find the heat added, the work done by the gas, and the change in its internal energy. (b ) Find these same quantities if the gas is heated from 300 to 600 K at constant pressure. (a ) Q = CvT; W = PdV = 0; Q = W + U Q = 1.5 8.314 300 J = 3.74 kJ = U; W = 0 (b ) Q = CpT; U = CvT; Q = 2.5 3.74/1.5 kJ = 6.23 kJ; U = 3.74 kJ; W = Q U W = 2.49 kJ 97* Heat in the amount of 500 J is supplied to 2 mol of an ideal diatomic gas. (a ) Find the change in temperature if the pressure is kept constant. (b ) Find the work done by the gas. (c) Find the ratio of the final volume of the gas to the initial volume if the initial temperature is 20C. (a ) T = Q/Cp; Cp = (7/2) nR T = (500/7 8.314) K = 8.59 K (b ) W = Q U = Q - (5/2) nRT = nRT W = 2 8.314 8.59 J = 143 J

Chapter 19 (c) Vf /Vi = Tf /Ti = (Ti + T)/Ti

Heat and the First Law of Thermodynamics Vf /Vi = 281.74/273.15 = 1.03

98 An insulated cylinder is fitted with a movable piston to maintain constant pressure. The cylinder initially contains 100 g of ice at 10C. Heat is supplied to the contents at a constant rate by a 100-W heater. Make a graph showing the temperature of the cylinder contents as a function of time starting at t = 0, when the temperature is 10C, and ending when the temperature is 110C. (Use c = 2.0 kJ / kgK for the average specific heat of ice from 10 to 0C and of steam from 100 to 110C.) 1. Find the energy to bring the ice to 0 oC. Q = 100 2 10 J = 2 103 J 2. Find t1, time required at energy input of 100 J/s t1 = 20 s 3. Time to melt ice = mLf/P, where P is power input t2 = 100 333.5/100 s = 333.5 s o 4. Find t3, time to heat water to 100 C = mcT/P t3 = 100 4.18 100/100 s = 418 s 5. Find t4, time to vaporize water = mLv/P t4 = 100 2257/100 s = 2257 s o 6. Find t5, time to heat vapor 10 C = mcT/P t5 = 100 2 10/100 s = 20 s The temperature T as a function of time t is shown below. Here T is in Celsius degrees and the times are as follows: t1 = 20 s, t2 = 353.5 s, t3 = 771.5 s, t4 = 3028.5 s, t5 = 3048.5 s.

99 For the winter festival, a sculptor creates a 20-kg statue of a skier made of ice at 0C. To show off the statue's stability, the sculptor hires someone to repeatedly slide the statue down a plane 8 m long and inclined at 30. Unfortunately, the sculptor forgot about the thermal energy produced by friction. If the coefficient of sliding friction between the ice and the plane is 0.05, how much ice melts due to the friction on the first run? (Assume that all the mechanical energy lost goes into melting the ice.) 1. Determine the mechanical work, W = kFnL. W = 0.05 (20 9.81 cos 30o) 8 J = 68 J 2. Find mass of ice that melts; m = W/Lf m = 68/333.5 g = 0.2 g 100 Two moles of a diatomic ideal gas expand adiabatically. The initial temperature of the gas is 300 K. The work done by the gas during the expansion is 3.5 kJ. What is the final temperature of the gas? 3 Use Equ. 19-38: W = CvT T = (3.5 10 /5 8.314) K = 84.2 K; Tf = 215.8 K

Chapter 19

Heat and the First Law of Thermodynamics

101* One mole of monatomic gas, initially at temperature T, undergoes a process in which its temperature is quadrupled and its volume is halved. Find the amount of heat Q transferred to the gas. It is known that in this process the pressure was never less than the initial pressure, and the work done on the gas was the minimum possible. The path for this process is shown on the PV diagram. Since PfVf = 4PiVi and Vf = Vi/2, the path for which the work done by the gas is a minimum while the pressure never falls below Pi is shown on the adjacent PV diagram. We can now determine W and U in terms of the initial temperature T, initial pressure Pi, and initial volume Vi. W = PiVi/2 = RT/2. U = CvT = (3/2) R(3T) = 9RT/2. Q = W + U = 4RT.

102 A vertical heat-insulated cylinder is divided into two parts by a movable piston of mass m. Initially the piston is held at rest. The top part is evacuated and the bottom part is filled with 1 mole of diatomic ideal gas at temperature 300 K. After the piston is released and the system comes to equilibrium, the volume, occupied by gas, is halved. Find the final temperature of the gas. Adiabatic process: T2 = T1(V1/V2)1; = 1.4 T2 = 300(2) 0.4 K = 396 K 103 According to the Einstein model of a crystalline solid, the internal energy per mole is given by

U=

3NAkT E eT E / T 1

where TE is a characteristic temperature called the Einstein temperature, and T is the temperature of the solid in kelvins. Evaluate the molar internal energy of diamond (TE = 1060 K) at 300 K and 600 K, and thereby the increase in internal energy as diamond is heated from 300 K to 600 K. 1. Determine U300 and U600 3 1060 8.314 J = 795 J ; U 300 = 1060/ 300

U 600
2. U = U600 U300

1 e 3 1060 8.314 = 1060/ 600 J = 5449 J 1 e

U = 4654 J

104 In an isothermal expansion, an ideal gas at an initial pressure P0 expands until its volume is twice its initial volume. (a ) Find its pressure after the expansion. (b ) The gas is then compressed adiabatically and quasi-statically back to its original volume, at which point its pressure is 1.32P0. Is the gas monatomic, diatomic, or polyatomic? (c) How does the translational kinetic energy of the gas change in these processes? (a ) Isothermal process: PV = constant P1 = P0/2 (b ) Adiabatic process: PV = constant P2 = P1(V1/V0) = 1.32P0 = 0.5P0(2) ; 2.64 = 2

Chapter 19

Heat and the First Law of Thermodynamics = ln(2.64)/ln(2) = 1.4; gas is diatomic. Translational kinetic energy is unchanged. Translational kinetic energy increases by a factor of 1.32.

Solve for . (c) In an isothermal process, T is constant. In an adiabatic process, T2 = 1.32T0

105* Prove that the slope of the adiabatic curve passing through a point on the PV diagram for an ideal gas is times the slope of the isothermal curve passing through the same point. The slope of the curve on a PV diagram is dP/dV. 1. For an isothermal process, PV = constant = C. So, P = C/V, and dP/dV = -C/V2 = P/V. 2. For an adiabatic process, PV = C, and dP/dV = P/V. We see that the slope for the adiabatic process is steeper by the factor . Note: Problems 106 through 109 involve non-quasi-static processes. Nevertheless, assuming that the gases participating in these processes approximate ideal gases, one can calculate the state functions of the end products of the reactions using the first law of thermodynamics and the ideal gas law. For T > 2000 K, vibration of the atoms contributes to cp of H 2O and CO2 so that cp of these gases is 7.5R at high temperatures. Also, assume the gases do not dissociate. 106 The combustion of benzene is represented by the chemical reaction 2(C6H6) + 15(O2) 12(CO2) + 6(H2O). The amount of energy released in the combustion of two mol of benzene is 1516 kcal. One mol of benzene and 7.5 mol of oxygen at 300 K are confined in an insulated enclosure at a pressure of 1 atm. (a ) Find the temperature and volume following combustion if the pressure is maintained at 1 atm. (b ) If, following combustion, the thermal insulation about the container is removed and the system is cooled to 300 K, what is the final pressure? For Problems 106-109, the specific heat of the combustion products depends on the temperature. Although cp increases gradually from (9/2) R per mol to (15/2) R per mol at high temperatures, we shall make the assumption that cp = 4.5R below T = 2000K and cp = 7.5R above T = 2000 K. We shall use R = 2.0 cal/mol.K. (a ) 1. Find Vi for 8.5 mol of gas at 300 K and 1 atm. 2. Find the total heat released. 3. Find Q needed to form the products at 100oC; there are 3 mol of H2O, 6 mol of CO2. 4. Find Q to heat 9 mol of gas to 2000 K 5. Find Q available to heat gases above 2000 K 6. Find final T of 9 mol of triatomic gases. 7. Find Vf from the ideal gas law. (b ) Since Tf = Ti, Pf = Pi(n f /n i)(Vi/Vf) Vi = (22.4 8.5 300/273) L = 209.2 L Q = (1516/2) kcal = 758 kcal Q to form steam = 3 18(73 + 540) cal = 33.10 kcal Q to heat CO2 = 6 4.5 2.0 73 cal = 3.94 kcal Q = 9 4.5 2.0 1627 cal = 131.79 kcal Q = (758 131.79 3.94 33.10) kcal = 589.2 kcal 3 T = 589.2 10 /(9 7.5 2.0) K = 4364 K; Tf = 6364 K Vf = (9 8.314 6364/101) L = 4715 L = 4.715 m3 Pf = (1 (9/8.5)(209.2/4715) atm = 0.047 atm

107 Repeat Problem 106, parts (a ) and (b ), using as the combustible substance 1 mol of acetylene for which the combustion reaction is 2(C2H2) + 5(O2) 4(CO2) + 2(H2O). The combustion of 1 mol of acetylene releases 300 kcal. (a ) 1. Find Vi of 3.5 mol at 300 K and 1 atm. Vi = (22.4 3.5 300/273) L = 86.15 L

Chapter 19

Heat and the First Law of Thermodynamics Q = 300 kcal Q to form steam = 18(73 + 540) cal = 11.03 kcal Q to heat CO2 = 2 4.5 2.0 73 cal = 1.31 kcal Q = 3 4.5 2.0 1627 cal = 43.93 kcal Q = (300 43.93 1.31 11.03) kcal = 243.7 kcal 3 T = 243.7 10 /(3 7.5 2.0) K = 5416 K; Tf = 7418 K Vf = (3 8.314 7416/101) L = 1831 L = 1.831 m3 Pf = 1(3/3.5)(86.15/1831) atm = 0.0403 atm

2. Find the total heat released. 3. Find Q needed to form products at 100oC; there are 1 mol of H2O and 2 mol of CO2. 4. Find Q to heat 3 mol of gas to 2000 K 5. Find Q available to heat gases above 2000 K 6. Find Tf of 3 mol of triatomic gases. 7. Find Vf using ideal gas law. (b ) Pf = Pi(n f /n i)(Vi/Vf)

108 Carbon monoxide and oxygen combine to form carbon dioxide with an energy release of 280 kJ/mol of CO according to the reaction 2(CO) + O2 2(CO2). Two mol of CO and one mol of O2 at 300 K are confined in an 80-L container; the combustion reaction is initiated with a spark. (a ) What is the pressure in the container prior to the reaction? (b ) If the reaction proceeds adiabatically, what are the final temperature and pressure? (c) If the resulting CO2 gas is cooled to 0C, what is the pressure in the container? (a ) 1. Find Pi of 3 mol at 300 K in 80 L Pi = (3 8.314 300/80) kPa = 93.53 kPa (b ) 1. Find Cv of combustion product below Cv = 2(7/2) 8.314 = 58.2 J/K 2000 K. 2. Find Q to raise 2 mol of CO2 to 2000 K Q = 58.2 1700 J = 98.94 kJ 3. Find Q to raise CO2 above 2000 K Q = (560 98.94) kJ = 461.1 kJ 3 4. Find Tf T = (461.1 10 /2 6.5 8.314) K = 4266 K; Tf = 6266 K 5. Find Pf = Pi(n f /n i)(Tf /Ti) Pf = 93.53(2/3)(6266/300) kPa = 1.30 MPa (c) Pf = Pi(n f /n i)(Tf /Ti) Pf = 93.53(2/3)(273/300) kPa = 54.7 kPa 109*Suppose that instead of pure oxygen, just enough air is mixed with the two mol of CO in the container of Problem 108 to permit complete combustion. Air is 80% N2 and 20% O2 by weight, and the nitrogen does not participate in the reaction. What then are the answers to parts (a ), (b ), and (c) of Problem 108? Note that for N2, cv at temperatures above 2000 K is (5/2) R + R since there is only one vibrational mode that contributes to the specific heat. (a ) 1. Write the reaction for 2 mol of CO 2(CO) + O2 + 4N2 2(CO2) + 4N 2 2. Find Pi of 7 mol at 300 K in 80 L Pi = (7 8.314 300/80) kPa = 218.2 kPa (b ) 1. Find Cv of product gases for T < 2000 K Cv = [2 (7/2) + 4 (5/2)]R = 141.3 J/K 2. Find Q to heat gases to 2000 K Q = 1700 141.3 J = 240.2 kJ 3. Find Q available to raise gases above 2000 K Q = (560 240.2) kJ = 319.8 kJ 3 4. Find Tf; note that Cv = 2 6.5 T = (319.8 10 /27 8.314) K = 1425 K; Tf = 3425 K 5. Find Pf = Pi(n f /n i)(Tf /Ti) Pf = 218.2(6/7)(3425/300) kPa = 2.135 MPa (c) Pf = Pi(n f /n i)(Tf /Ti) Pf = 2135(273/3425) kPa = 170.2 kPa 110 Use the expression given in Problem 103 for the internal energy per mole of a solid according to the Einstein model

Chapter 19

Heat and the First Law of Thermodynamics

to show that the molar heat capacity at constant volume is given by

/T TE eTE c v = 3R T E / T 2 T (e 1) 2

U=

3 RT E . The specific heat at constant volume is dU/dT and performing the indicated operation one eT E / T 1
2

T E eT E /T 3 R obtains cv = 2 . T ( eT E /T 1 )
111 (a ) Use the results of Problem 110 to show that the DulongPetit law, c v 3R , holds for the Einstein model when T > TE. (b ) For diamond, TE is approximately 1060 K. Numerically integrate U = c v dT to find the increase in the internal energy if 1 mol of diamond is heated from 300 to 600 K. Compare your result to that obtained in Problem 103. With TE = 1060 K, cv has the values shown below T, K cv, J/mol.K 300 9.65 400 14.33 500 17.38 600 19.35 The specific heat as a function of temperature is shown in the Figure. Integrating numerically one obtains U = 100[1/2(9.65) + 14.33 + 17.38) + 1/2(19.35)] = 4621 J in good agreement with the result of Problem 103.

112 A refinement of the Einstein model by Debye resulted in the following expression for the specific heat:

T cv = 9R T D

x e 2 dx x ( 1 ) e 0

where TD is called the Debye temperature and y = TD / T. (a ) Show that when T >> TD, the above expression reduces to the DulongPetit result cv = 3R. (Hint: When T >> TD, y << 1 and therefore x is always much less than 1. Then ex 1 + x.) (b ) When T << TD, the integral's upper limit may be approximated by infinity; the definite integral then has the
3 value 4 4 / 15. Show that at very low temperatures the specific heat is given by c v = (12 4 / 5) R(T / T D ) .

(a ) When T >> TD, e

T D /T

1 + (T D / T ) and the integral is approximately.

TD T

x 4 dx = x2

TD T

1T x dx = D . 3 T 0
2

The specific heat then reduces to cv = 3R. (b ) For T << TD, the upper limit of the integral approaches infinity, and the definite integral has the value 4 4/15. The specific heat is then as stated, namely cv = (12 4/5)R(T/TD)3.