CHAPTER 4 The First Law of Thermodynamics PROBLEMS AND SOLUTIONS 4.1 Explain the term state function. Which of the following are state functions? P, V, 7, w, A state function is a property that is determined only by the state of a system. P,V, and 7 are state functions. q and w are not. 4.2. What is heat? How does heat differ from thermal energy? Under what condition is heat transferred from one system to another? Heat is the transfer of energy from one object to another as a result of a temperature difference between the two objects. Heat is only transferred between systems when they are at different temperatures. ‘Thermal energy is that part of the energy of a system that is associated with the random motion (translational, vibrational, and rotational) of atoms and molecules. 4.3 Show that 1 L atm = 101.31. The units conversion can be performed using R expressed in L atm and J, respectively. R = 0.08206 Latm K~' mol“! = 8.314 JK~! mol” 44 A 7.24-g sample of ethane occupies 4.65 L at 294 K. (a) Calculate the work done when the gas expands isothermally against a constant external pressure of 0.500 atm until its volume is 6.87 L. (b) Calculate the work done if the same expansion occurs reversibly. 6970 Chapter (a) 101.33 w = —P,, AV = — (0.500 atm) (6.87 L — 4.65 L) ( a) =-1123 o) _ V, 1248 at 687L wa ART ne = rT (8314.1K-! mol”) (294 K) In 77== = ~2301 Note that work done in the reversible process in (b) is greater in magnitude than that in the irreversible process in (a) 4.5 A 19.2-g quantity of dry ice (solid carbon dioxide) is allowed to sublime (evaporate) in an apparatus like the one shown in Figure 4.1. Calculate the expansion work done against a constant external pressure of 0.995 atm and at a constant temperature of 22°C. Assume that the initial volume of dry ice is negligible and that CO, behaves like an ideal gas. Because the initial volume of dry ice is negligible, V, pressure is the same as the external pressure, that is, P, CO, can be calculated using the ideal gas law: Expansion occurs until the internal >. The final volume, V,, occupied by nRT _ RT Py Py ‘The work done can now be calculated. w=-P,AV Pag (Va — Va) = —PexVa =p, (82) =-wnr == (a - 28 = ) (8.314 K~! mol") (295 K) 01 gmo =-1.07 x 10°J 4.6 Calculate the work done by the reaction Zn(s) + H,S0,(ag) + ZnSO,(aq) + H,(2) when 1 mole of hydrogen gas is collected at 273 K and 1.0 atm, (Neglect volume changes other than the change in gas volume.) ‘The gas expands until its pressure is the same as the external pressure of 1.0 atm. Furthermore, since volume changes other than gas are neglected, the change in volume of the system is nRT _ nRT Py‘The First Law of Thermodynamics 71 P. (SE) =-er alee ‘The work done is PAV = —P,V, = (1 mol) (8.314 JK“! mol~') (273 K) = —2.27 x 10°3 4.7 A truck traveling 60 kilometers per hour is brought to a complete stop at a traffic light. Does this, change in velocity violate the law of conservation of energy? ‘The mechanical (kinetic) energy of the truck is converted to thermal energy as its brakes are warmed through friction. The loss of one form of energy is always balanced by an increase in some other form. 48 Some driver’s test manuals state that the stopping distance quadruples as the velocity doubles. Justify this statement by using mechanics and thermodynamic arguments. The kinetic energy of a moving vehicle is given by E,,, = jmv*. If the velocity doubles, the kinetic energy quadruples. If v = 2v,, then E, = 4m (2v,)” = 4£,. Assuming kinetic energy is dissipated at a constant rate in the brakes and between the tires and the road as heat through friction, then the stopping distance is proportional to the energy. The doubling in velocity ‘quadruples the kinetic energy and thus the stopping distance. 4.9 Provide a first law analysis for each of the following: (a) When a bicycle tire is inflated with a hand pump, the temperature inside rises. You can feel the warming effect at the valve stem. (b) Artificial snow is made by quickly releasing a mixture of compressed air and water vapor at about 20 atm from a snow-making machine to the surroundings. In both cases it is assumed that the process is occurring rapidly enough so that there is no transfer of heat between the system and the surroundings. That is, the process is adiabatic and q = 0. (a) Work is done on the gas (the system) when it is compressed by the bicycle pump. AU = q + w =w, since q = 0. The internal energy of the gas is increased. For a diatomic, ideal ‘gas, such as N, or O,, which are the major components of air, AU = $n RAT, where n is the number of moles of gas. Since AU > 0, AT > 0, also. is just the opposite of part (a). The expanding gas does work on the surroundings, so AU <0,and AT <0, or the system cools. 4.10 An ideal gas is compressed isothermally by a force of 85 newtons acting through 0.24 meter. Calculate the values of AU andChapter4 AU = 0 for an ideal gas undergoing an isothermal process. Using this information, g can be calculated from w, the work done on the system. = (force) (distance) = (85 N) (0.24 m) = 203 Because AU =0=4 + w,g =-w=-201. 4.11 Calculate the internal energy of 2 moles of argon gas (assuming ideal behavior) at 298 K. Suggest two ways to increase its internal energy by 10 J. The only internal energy that argon gas possesses is translational energy. Argon has 3 translational degrees of freedom. Therefore, 3 U==nRT 3 (2 mol) (8.314 JK-! mol”) (298 K) = 7.43 x 10° J The internal energy of argon gas can be increased by doing work on the gas or heating the gas or a combination of these two processes. The first process can be achieved by compressing the gas adiabatically such that w = 10J and q = 0. The second process can be achieved by heating the gas at constant volume such that = 10J and w = 04. 4.12 A thermos bottle containing milk is shaken vigorously. Consider the milk as the system. (a) Will the temperature rise as a result of the shaking? (b) Has heat been added to the system? (©) Has work been done on the system? (4) Has the system’s internal energy changed? The thermos bottle ensures that g = 0, since it prevents the transfer of heat to or from the surroundings. (a) Energy (mechanical) has been added to the system by shaking. The random motion of the molecules in the milk is increased, and the temperature rises. (b) The insulation of the thermos bottle prevents the transfer of heat between the system and surroundings. (©) Work has been done on the system through shaking (@) The internal energy of the system has increased. 4.13 A 1,00-mole sample of ammonia at 14.0 atm and 25°C in a cylinder fitted with a movable piston expands against a constant external pressure of 1,00 atm. At equilibrium, the pressure and volume of the gas are 1.00 atm and 23.5 L, respectively. (a) Calculate the final temperature of the sample. (b) Calculate the values of g, w, and AU for the process. (a) Assume ammonia is an ideal gas. The final temperature is lL) abe (1.00 atm) (2: ~ “mR ~~ (1.00 mol) (0.08206 Latm (b) The problem provides enough information to calculate w and AU directly. Consequently, ¢ can be determined using the first law of thermodynamics.w is related to the change in volume of the system. The final volume is given, but the initial volume needs to be calculated from the ideal gas law: nRT, _ (1.00 mol) (0.08206 LatmK~! mol") (298 K) B 14.0 atm =LI5L ‘The work done is J > AV = — (1.00 atm) (23.5L — 1.75 v(t S ) = 2.20 x 10°J TLatm, AU is related to C,, which can be calculated from C , = 35.66 JK~' mol” listed in Appendix B. Itis assumed that C, and C, are independent of temperature. Cy = Cp — mR = (1.00 mol) (35.66 JK~! mol!) — (1.00 mol) (8.314 JK~! mol™') = 27.35 JK7! ‘The change in internal energy is AU = CyAT = (27.35 JK~') (286 K — 298 K) = —3.3 x 10°J Using the first law of thermodynamics, =AU-w= 3 x 10? J — (2.20 x 10° J) = 1.87 x 10° J 4.14 An ideal gas is compressed isothermally from 2.0 atm and 2.0 L to 4.0 atm and 1.0 L. Calculate the values of AU and AH if the process is carried out (a) reversibly and (b) irreversibly. AU and AH of an ideal gas depend only on T. Therefore, for any isothermal process [either process (a) or (b)], AU = O and AH = 0. 4.15 Explain the energy changes at the molecular level when liquid acetone is converted to vapor at its boiling point. The thermal energy supplied as heat is used to overcome the attractive, intermolecular forces between the acetone molecules. The molecules then break free of the condensed, liquid phase and enter the gas phase. Since the added energy is converted to potential and not kinetic energy of the molecules, the temperature remains constant. 4.16 A piece of potassium metal is added to water in a beaker. The reaction that takes place is 2K(s) + 2H,O() > 2KOH(aq) + H,(¢) Predict the signs of w,q, AU, and AH. w is negative because the hydrogen gas produced expands and does work on the surroundings.@ is negative because thermal energy is generated in this reaction. Since AU = q + w, it must be negative also. The process takes place at constant pressure, therefore q = gp = AH. Thus, AH is negative. 4.17 At373.15 K and | atm, the molar volume of liquid water and steam are 1.88 x 1075 m? and 3.06 x 10? m’, respectively. Given that the heat of vaporization of water is 40.79 kJ mol~', calculate the values of AH and AU for 1 mole in the following process: H,O(, 373.15 K, 1 atm) > H,O(g, 373.15 K, 1 atm) AH for the above process is the heat of vaporization, that is, AH = 40.79 kJ for 1 mole of water. It is necessary to calculate w and before determining AU. Since the process occurs at constant pressure, q = AH = 40.79 kJ when | mol liquid H,O vaporizes. In the same process, w=-P,AV 10001) / 101.33 = \-2 om? 5 m3 101.37 = — (1.00 atm) (3.06 x 10-? m3 — 1.88 x 10 m) (28) (SS) = —3.098 x 10°F Note that we could have safely ignored the volume of liquid H,O, since it is negligible compared with that of gaseous HO above. Using the first law, AU = q+ w = 40.79 ki — 3.098 kI = 37.69 kt 4.18 Consider a cyclic process involving a gas. If the pressure of the gas varies during the process but returns to the original value at the end, is it correct to write AH = 9p? No, it is not correct. For a cyclic process, AH = 0, since H is a state function, but the heat, or g, associated with a process is not a state function and depends on the path. Depending on the path used to achieve the cyclic process it may take on a variety of values. 4.19 Calculate the value of AH when the temperature of 1 mole of a monatomic gas is increased from 25°C to 300°C. AH is directly related to change in temperature of a system: AH =C,ATAssuming that the gas is ideal, Cy tnR A monatomic gas has only translational degrees of freedom, Cy, and nR. Therefore, Cp AH =ja mol) (8.314 JK~! mol") (573 K — 298 K) = 5.72 x 10°J 4.20 One mole of an ideal gas undergoes an isothermal expansion at 300 K from 1,00 atm to a final pressure while performing 200 J of expansion work. Calculate the final pressure of the gas if the external pressure is 0,20 atm. w=-P,(¥,-V) = 1 =—P,nrT (— aM RT pe 1 w ae P, = =2003 1 Se = 1.401 atm™! @20 atm) (1 moh (B314IK mol) GOOK) * 1.00atm as P,=0.71 atm 4.21 A 6.22-kg piece of copper metal is heated from 20.5°C to 324.3 °C. Given that the specific heat of Cu is 0.385 Jg~'°C~', calculate the heat absorbed (in kJ) by the metal. q =msAT = (6.22 x 10° g) (0.385 J g~! °C~!) (324.3 °C — 20.5 °C) = 7.28 x 10°F 4.22 A 10.0-g sheet of gold with a temperature of 18.0°C is laid flat on a sheet of iron that weighs 20.0 g and has a temperature of 55.6°C. Given that the specific heats of Au and Fe are 0.129 Jg7!°C! and 0.444 J g~! °C, respectively, what is the final temperature of the combined metals? Assume that no heat is lost to the surroundings. (Hint: The heat gained by the gold must be equal to the heat lost by the iron.) The final temperature of the sheet of gold is the same as that of the sheet of iron when thermal equilibrium is reached, and is denoted by T,. Furthermore, the amount of heat gained by gold is the same as that lost by iron, that is, Ina = — We‘The “—” sign is used to indicate that g,, and gy, are of opposite sign. The above relation gives M nSau4T ay = —PpeSpeA Tre (10.0 g) (0.129 g-" °C") (7, ~ 18.0°C) = ~ (20.0 g) (0.444 3 ~*~) (T, ~ 55.6°C) (1.29 3°¢"!) (1, ~ 18.0°C) = ~ (8.88 5°C~') (7, ~ 55.6°C) 8.88J°C"! 18.0°C = -——_—_—__ (7, — 55.6" 1297ee* @ a5.6 c) = ~6.884 (7, ~55.6°C) = 6.8847, + 382.8°C 7.8847, = 400.8°C = 50.8°C 4.23 It takes 330 joules of energy to raise the temperature of 24.6 g of benzene from 21.0°C to 28.7°C at constant pressure. What is the molar heat capacity of benzene at constant pressure? From the relationship C,pAT =nC,AT C, of benzene can be determined: 3303 = 136 Jmol“! °c“ ) (28.7°C — 21.0°C) 4.24 The molar heat of vaporization for water is 44.01 kJ mol~! at 298 K and 40.79 kJ mol! at 373 K. Give a qualitative explanation of the difference in these two values. At the higher temperature, the water molecules have more kinetic energy and are moving faster. ‘Thus, there are on average fewer hydrogen bonds holding the individual water molecules together. ‘Consequently at the higher temperature, less thermal energy must be supplied to break the remaining intermolecular attractions and allow the molecules to enter the gas phase. 4.25 The constant-pressure molar heat capacity of nitrogen is given by the expression (27.0 + 5.90 x 10-7 ~ 0.34 x 10-67) JK"! molCalculate the value of AH for heating 1 mole of nitrogen from 25.0°C to 125°C. Since C,, is temperature dependent, it has to be integrated over T to yield AH: 398K AH= nC,dT how. 398K = (1 mol) [(27.0 + 5.90 x 10-*7 — 0.34 x 10°67?) JK~! mol~"] dT ase K 398K 47? QP =] 27.07 + 5.90 x 10° — 0.34 x 10° J 298K 2 2 = [»0 (398) + 5.90 x 10 SE — 0.34 x wt] J 2 2 - [0 (298) + 5.90 x 10 — 0.34 x oe] J = 2.90 x 10°F 4.26 The heat capacity ratio (y) for a gas with the molecular formula X,Y is 1.38. What can you deduce about the structure of the molecule? The molecule X,Y is either linear or bent (e.g. H,0 or CO,). Since C, capacity ratio may be rewritten as Cy +R, the heat This may be solved for Cy to give R 31 26R At typical temperatures the vibrational contribution to the heat capacity is negligible, and for a linear molecule Cy = 2.5R, while for a bent molecule, C,, = 3.0R. Better agreement between prediction and measurement is obtained in the case of the linear molecule, and thus the molecule is most likely linear.4.27 One way to measure the heat capacity ratio (y) of a gas is to measure the speed of sound in the gas (c), which is given by _ (z RT y" “VM where M is the molar mass of the gas. Calculate the speed of sound in helium at 25°C. First calculate y. Since helium is a monatomic gas with only translational degrees of freedom, Cy = 3nR. Assuming helium is ideal, Cp = Cy +nR= Therefore, the heat capacity ratio is a ee cy 2 3 ¥ Substitute y into the expression for c: wn Ts ee in c= (42) | Ga ee et) OT ae teh et mM 4.003 x 10 kgmol 4.28 Which of the following gases has the largest C, value at 298 K? He, N,, CCl, HCI. A gas composed of non-linear, polyatomic molecules is predicted to have a larger Cy than monoatomic gases or those made up of linear molecules. In the list above, only CCl, is a non-linear molecule, so it should have the largest Cy. 4.29 (a) For most efficient use, refrigerator freezer compartments should be fully packed with food. ‘What is the thermochemical basis for this recommendation? (b) Starting at the same temperature, tea and coffee remain hot longer in a thermal flask than soup. Explain. (a) The heat capacity depends on both the mass and the specific heat, C = ms. The more tightly packed the freezer, the greater the mass of food in it. Since the food has a greater heat capacity than the air it displaces, it will take more thermal energy to raise the temperature of the tightly packed freezer. This will require a greater time for the temperature of the freezer contents to rise a given amount. (b) Water has a larger heat capacity than most solids, such as the meat, vegetables, etc. in soup. Coffee and tea are mostly water, so to the extent that these other ingredients take the place of some water in the soup, coffee or tea would have a larger heat capacity than soup and thus would need to lose more thermal energy for the same temperature change. To the extent that the rate of thermal energy loss from the thermal flask is constant, it will take longer for the coffee or tea to cool down than the soup (unless the soup is a clear broth).4.30 _In the nineteenth century, two scientists named Dulong and Petit noticed that the product of the molar mass of a solid element and its specific heat is approximately 25 J°C~!. This observation, now called Dulong and Petit’s law, was used to estimate the specific heat of metals. Verify the law for aluminum (0.900 J g~! °C"), copper (0.385 J g~! °C™'), and iron (0.444 J g~!°C~'). The law does not apply to one of the metals. Which one is it? Why? Al: (26.98 g) (0.900 J g~'°C~') = 24.3 °C"! Cu (63.55 g) (0.385 Jg7'°C"') = 24.5 3°C! Fe: (55.85 g) (0.444 Je7!°C-!) = 24.83°C! Therefore, Dulong and Petits law applies to Al, Cu, and Fe. However, since this law applies only to solids, it does not apply to mercury, a liquid. In fact, the product of the molar mass of Hg and its specific heat is (200.6 g) (0.1395 g7!°C"') = 27.93°C"! 4.31. The following diagram represents the PV changes of a gas. Write an expression for the total work done.The total work done is the sum of the work done against the constant external pressure P, when the system expands from V, to V,, and that against the constant external pressure P, when the system expands from V, to V; w= —P,(V,—V,) — Ps (Vs — Ya) 4,32 The equation of state for a certain gas is given by P ((V/n) — b] = RT. Obtain an expression for the maximum work done by the gas in a reversible isothermal expansion from V, to V,. Write P in terms of n, V, and T: nRT. V=nb ‘The maximum work done by the gas undergoing an isothermal expansion is M, Yo _nRT. rave-[ Top tY = -nRT In(V — nb)? 4.33. Calculate the values of g, w, AU, and AH for the reversible adiabatic expansion of 1 mole of a monatomic ideal gas from 5.00 m° to 25.0 m’. The temperature of the gas is initially 298 K. For an adiabatic process, q = 0. AU can be calculated once Cy and the final temperature, Te are determined. For an ideal monatomic gas, Cy = 3nR, Cp = Cy +nR = $nR, y = Z = §. 7, is calculated using the relationship between V and T appropriate for an adiabatic reversible expansion: (a) = 1019K AU is therefore AU =CyAT = (x8) (4-1) = ; (1 mol) (8.314 JK~! mol~') (101.9 K ~ 298 K) = 2.45 x 10°3According to the first law, w= AU —g =-245 x 10° J—0 = —2.45 x 10° AH is found from C, and AT: AH =C,AT = Snrar | ; (1 mol) (8.314 JK-! mol") (101.9 K — 298 K) = —4.08 x 10° J 4.34 A quantity of 0.27 mole of neon is confined in a container at 2.50 atm and 298 K and then allowed to expand adiabatically under two different conditions: (a) reversibly to 1.00 atm and (b) against a constant pressure of 1.00 atm. Calculate the final temperature in each case. (a) For a reversible adiabatic process, P and V are related as follow: i (#) Py Va, Assuming neon to be an ideal gas, write V in terms of n, P, and T: aRT,\ ax) -(@) @ EA 7) \P, Rearrange the equation to give an expression relating T and P: TY’ _ (7! T AP, 1 %_(%\™" qT, P Utilizing the last equation and the fact that y for an ideal monatomic gas is $, the final temperature can be calculated: BP A (3) Pern ( 1.00 Ci —oonk Pi 2.50 atm, (b) The process is adiabatic with q = 0. Thus, AU = w. Since AU = Cy (I, -T,), and -v).The expansion occurs until P, = P.,. Therefore, the above expression simplifies to ) (298K) = 226 K 4.35 One mole of an ideal monatomic gas initially at 300 K and a pressure of 15.0 atm expands to a final pressure of 1.00 atm. The expansion can occur via any of four different paths: (a) isothermal and reversible, (b) isothermal and irreversible, (c) adiabatic and reversible, and (d) adiabatic and irreversible. In irreversible processes, the expansion occurs against an external pressure of 1.00 atm, For each case calculate the values of g, w, AU, and AH. (a) When an ideal gas undergoes an isothermal process, AU = 0 and AH =0. P one, 15.0atm : w nRT In P, (1 mol) (8.314 J K~! mol™') (300 K) In 0 sma 6.75 x 10°F q=AU-w 75 x 10°F (b) When an ideal gas undergoes an isothermal process, AU = 0 and AH =0. w=-P,(¥.—¥%,) V, and V, can be determined using the ideal gas law: % nRT _ (1 mol) (0.08206 LatmK~! mol~') (300 K) ree P, 15.0 atm tl saart aRT _ (1 mol) (0.08206 L atm K~! mol') (300 K) oven P, 1.00 atm Therefore, 101.33 w= = (1.00 aim 2462 ~ 1.6411) ( ) 2.33 x 10° J TLatm and g=AU-w= 33 x 1073 (©) q = 0 for an adiabatic process.To determine AU and AH, T, needs to be calculated. Using the same procedure as Problem 4.34(@), o-by 9) = Now the rest of the quantities can be calculated: AU =CyAT = 3 {1 mol) (8.314 JK~! mol") (101.6 K — 300 K) = —2.47 x 10° w = AU —q=AU =-2.47x 10° SH=C,AT= ; (1 mol) (8.314 JK~' mol’) (101.6 K — 300 K) = —4.12 x 10° J (@) q = 0 for an adiabatic process. To determine AU and AH, T, needs to be calculated, Using the same procedure as Problem 4.34(b), 2 (Px 3 Ti (= cs 3) n 2 (1.00 atm 15.0.atm +3) (300 K) = 188K Now the rest of the quantities can be calculated: AU =CyAT 3a mol) (8.3143 K~! mol”) (188 K ~ 300 K) = ~1.40 x 10° J w= AU —q=AU =-1.40x 10°J AH =C,AT = ; (1 mol) (8.314 JK~! mol) (188 K — 300 K) = -2.33 x 10° 4.36 A 0.1375-g sample of magnesium is bumned in a constant-volume bomb calorimeter that has a heat capacity of 1769 J°C~. The calorimeter contains exactly 300 g of water, and the temperature increases by 1.126°C. Calculate the heat given off by the burning magnesium, in kI g~! and in kJ mol~'. The specific heat of water is 4.184 J g~'°C-!. Heat given off by the burning magnesium is absorbed by the calorimeter and water. The heat absorbed is calculated using the heat capacity of the calorimeter, specific heat of water, and the temperature rise. Heat gained by calorimeter and water = (1769 J°C-') (1.126 °C) + (300 g) (4.184 J g-!°C~) (1.126 °C) = 3.405 x 10° JTherefore, heat given off by Mg is 3.405 x 10° J coon T= 1 4gkrg! 0.13758 2.48 x 10° Ig 24.8 kT g or (2.48 x 108 Jgé') (24.31 gmol™') = 6.03 x 105 Jmol“! = 603 kJ mol"! 4,37 The enthalpy of combustion of benzoic acid (C,H,COOH) is commonly used as the standard for calibrating constant-volume bomb calorimeters; its value has been accurately determined to be —3226.7 kJ mol~!. (a) When 0.9862 g of benzoic acid was oxidized, the temperature rose from 21.84°C to 25.67°C. What is the heat capacity of the calorimeter? (b) In a separate experiment, 0.4654 g of a-D-glucose (C,H,,0,) was oxidized in the same calorimeter and the temperature rose from 21.22°C to 22.28°C. Calculate the enthalpy of combustion of glucose, the value of A, U for the combustion, and the molar enthalpy of formation of glucose. (a) In a constant-volume calorimeter, the energy of combustion of benzoic acid, A,U®, is the same as heat given off by the reaction, g, which is absorbed by the calorimeter. Therefore, the given value for the enthalpy of combustion must be converted to the energy of combustion. The combustion reaction for benzoic acid is CAH{COOH) + F0,(@) + 160, + 31,000 and has An 0.5 mol, From this, A,U° is found. A,U® = A, H — RTAn 1k a he 1 mol a a = —3226.7 kJ mol! — (8.314 JK~! mol~")(298.15 K)(—0.5 mol) Ge 7) = —3225.46 kJ mol“! Therefore, eatorimeer = ~Toensic nid Catorimeter (25-67 °C — 21.84 °C) = (ess) (-3225.46 kJ mol~') C, 26.0521) _ 6 02 15°C! ‘calorimeter = “3. g3 °C (b) In this experiment, the calorimeter absorbs heat transferred from the combustion of glucose. Gessner = ~Yghcone 6.802 kI°C~! (22,28 °C — 21.22°C) Tote) (4,0") 4A,U° = 2.79 x 10° kJ mol™!To calculate the enthalpy of combustion, the change in number of moles of gases in the reaction has to be determined. The reaction is CH 20¢(s) + 60,(¢) > 6CO,(g) + 6H,00), s0 An = 0. Therefore, 2.79 x 10° kI mol~! A,H° = A,U° + RT An = A,U° = The molar enthalpy of formation is related to A, H° of the combustion reaction. A, H® = 6,1 [CO,(g)] + 64,” [H,0(0] — 4,” [C,H,0,(5)] -64,H°[0,(@)] A,H? [CoH,,0¢(s)] = 6A, [CO,(g)] + 64,” [H,0()] — 64,7 [0,(@)] — 4,H° = 6 (-393.5 kJ mol~') + 6 (—285.8 kJ mol~') — 6 (0 kJ mol~') — (-2.79 x 10° kJ mol") = -1.29 x 10° kJ mol“! 4,38. A quantity of 2.00 x 10 mL of 0.862 M HCl is mixed with 2.00 x 10? mL of 0.431 M Ba(OH), in a constant-pressure calorimeter having a heat capacity of 453 J°C~!. The initial temperature of the HCI and Ba(OH), solutions is the same at 20.48°C. For the process H*(aq) + OH” (aq) + H,0(), the heat of neutralization is 56.2 kJ mol"!. What is the final temperature of the mixed solution? The final temperature of the solution can be determined once the heat capacity of the calorimeter plus solution is known as well as the number of moles of reaction that occurs. First determine the number of moles of reactants. yr = (2.00 x 107! L) (0.862 mol L~") = 0.1724 mol Noy~ = 2 (2.00 x 107! L) (0.431 mol L“') = 0.1724 mol ‘There is just enough of each reactant to completely react with the other to form 0.1724 mol of the product, H,O. The thermal energy released by this reaction, under constant pressure, is Gp = (—56.2 kJ mol™') (0.1724 mol) = —9.689 k} This same thermal energy is used to increase the temperature of the calorimeter and its contents, but since these items are gaining thermal energy, the sign is switched. 9.689 15 = (Costorinser + Machin ction) AT‘Two assumptions are now made. Namely, that the densities of the solutions are the same as pure water, and likewise that the specific heat of the solution is the same as that of water. (These assumptions are good to 3-5%.) Under these assumptions, Ssoinion = 4-184 Ig"! °C~!, and ™ tation = Muci + ™p aon, = (2.00 x 10? mL) (1.00 gmL~") + (2.00 x 10? mL) (1.00 gmL~!) = 4.00 x 10° g This allows the determination of AT, 9.689 kJ = [453 ]°C~! + (4.00 x 10” g) (4.184 Fg"! °C-')] (EL) AT 9.689 = (2.127 °C-!) AT AT, = 4.555°C The final temperature of the mixed solution is found from AT = T, — T,, or 4.555°C = T, — 20.48°C which gives T, = 25.04°C, although the assumptions made limit the accuracy of our answer to T, = 25.0°C. 4.39 When | mole of naphthalene (C,,H,) is completely burned in a constant-volume bomb calorimeter at 298 K, 5150 kJ of heat is evolved. Calculate the values of A,U and A,H for the reaction. Since volume is constant, w = 0, and therefore, A,U = q = —5150 kJ mol™'. ‘The change in number of moles of gases needs to be determined before A, H can be evaluated. From the combustion of 1 mole of naphthalene, CigHg(s) + 120,(g) > 10C0,(g) + 4H,0(/) An = 10-12 = —2. Thus, A,H =A,U + RT An = —5150kJ mol™! + (8.314 J K~' mol~') (298 K) (-2) (zaas) = —5155 kJ mol"! 4.40 Consider the following reaction: 2CH,OH() + 30,(g) > 4H,0(1) +2CO,(g) A, H = —1452.8kJ mol"! ‘What is the value of A, H° if (a) the equation is multiplied throughout by 2, (b) the direction of the reaction is reversed so that the products become the reactants and vice versa, (c) water vapor instead of liquid water is the product? (a) A, H® = 2 (-1452.8 kJ mol”) = -2905.6 kI mol“! (b) A, H° = = 1452.8 kJ mol~! (-1452.8 kJ mol“(©) The reaction 2CH,OH()) + 30,(g) > 4H,0(g) + 2CO,(g) is a sum of the following equations: 2CH,OH() + 30,(g)+4H,0(!) + 2CO,(¢) A, Hf = -1452.8 kJ mol"! 4H,0() +4H,0(8) HS The standard enthalpy of reaction for vaporization of H,O is A, Hg = 4A,H° [H,0(@)] - 44,7 [H,00)] = 4 (—241.8 kJ mol“) — 4 (-285.8 kJ mol“') = 176.0 kI mol"! The standard enthalpy of reaction of 2CH,OH() + 30,(g) > 4H,O(g) + 2CO,(g) is A,H® = A, He + A, Hf = —1452.8 k mol™! + 176.0kJ mol™! = —1276.8 kJ mol™! 4.41 Which of the following standard enthalpy of formation values is not zero at 25°C? Na(s), Ne(g), CH, (8), Sp(s), Hg, H(g). H(g) is not the stable allotropic form of hydrogen at 25°C. Therefore, A, H° (H(g)] ¥ 0. [The stable form is H,(g).] 4.42 The standard enthalpies of formation of ions in aqueous solution are obtained by arbitrarily assigning a value of zero to H* ions; that is, AH” (H* ag)] = 0. (a) For the following reaction, HCI(g) > H*(aq)+CI"(aqg) A, H® = -74.9 kJ mol™! calculate the value of A, H® for the CI” ions. (b) The standard enthalpy of neutralization between a HC! solution and a NaOH solution is found to be —56.2 kJ mol~'. Calculate the standard enthalpy of formation of the hydroxide ion at 25°C. @) A,H® = -74.9 kJ) mol”! =A, [H*(aq)] + A,” [Cl(aq)] — 4,7 TAC\(g)) A/F [Ci (aq)] = - 74.9 kI mol"! — A, [H*(aq)] + 4,7 [HCI(g)] =— 74.9 kJ mol™! — 0 kJ mol"! + (-92.3 kI mol) =— 167.2 kI mol"! (b) The neutralization reaction for 1 mole of H,O is H*(aq) + OH"(aq) + H,0() A, H® = -56.2 kJ mol™4, H® = —56.2kI mol"! =A,H° [H,0()] — 4,” [H*(aq)] - 4, [OH~(aq)] 4, [OH™(aq)] =A,” [H,0()] — 4,” [H*(aq)] + 6.2 kI mol"! = — 285.8 kJ mol”! — 0 kJ mol™! + 56.2 kJ mol~! = — 229.6 kJ mol"! 4.43 Determine the amount of heat (in kJ) given off when 1.26 x 10° g of ammonia is produced according to the equation —92.6 kJ mol~! N,(g) + 3H,(g) > 2NH,(¢) 4, H® Assume the reaction takes place under standard-state conditions at 25°C. ‘The equation gives standard enthalpy of reaction (or, since P is constant, the amount of heat given off) when 2 moles of NH, are produced. When 1.26 x 10* g of ammonia is produced, the amount of heat given off is 92.63 1.26 x 10* g NH, ees | | eek BS | = 3a yt ( See) (ee 349x108 4.44 When 2.00 g of hydrazine decomposed under constant-pressure conditions, 7.00 kI of heat were transferred to the surroundings: 3N,H,() 4NH,(g) +N,(¢) What is the A, H® value for the reaction? The reaction describes the decomposition of 3 moles of hydrazine. Therefore, the amount of heat given must be scaled to this amount of reactant. =7.00 kd A,H° = qp = (3.00) = —337 kJ mol“ 32.05 pmol NH, 4.45 Consider the reaction N,(g) + 3H,(g) > 2NH,(g) A, H® = -92.6kI mol"! If 2.0 moles of N, react with 6.0 moles of H, to form NH,, calculate the work done (in joules) against a pressure of 1.0 atm at 25°C. What is the value of A,U for this reaction? Assume the reaction goes to completion,Under a constant external pressure, w=—P,,(V,—V,) where V, and V, are the volumes occupied by the reactants (8.0 moles) and products (4.0 moles), respectively. Using the ideal gas law, caus RT RT ol [products — Mreactans’ “ a P P ) Pp [tot] where P is the pressure at which the reaction takes place, that is, the same as P,,. Therefore, w = —(—4.0) RT = — (—4.0) (8.314 JK"! mol") (298 K) = 9.9 x 10° Jmol" The first law can be used to obtain A,U once q is calculated. At constant pressure, q = A, H. A, H given above is for the reaction between 1 mole of N, and 3 moles of H,. The reaction of interest involves twice the amounts of reactants. Therefore, 2 (-92.6 kJ mol 185.2 mol! Thus, A,U =q +w = ~185.2 kJ mol! + 9.9 kJ mol"! = —175.3 kJ mol"! 446 The standard enthalpies of combustion of fumaric acid and maleic acid (to form carbon dioxide and water) are —1336.0 kJ mol”! and —1359.2 kJ mol", respectively. Calculate the enthalpy of the following isomerization process: HOOC COOH H COOH Nee \—/ /\ /, H H H HOOC maleic acid fumaric acid ‘The chemical equations and the standard enthalpies of combustion of 1 mole of fumaric acid and 1 mole of maleic acid are given below: fumaric +30, > 4CO,+2H,O A, H® = —1336.0kJ mol"! maleic +30, > 4CO,+2H,0 A, H® = ~1359.2 kJ mol“! ‘The isomerization reaction (maleic acid > fumaric acid) can be obtained as a combination of these two reactions: 4CO, +2H,O + fumaric+30, A, H® = 1336.0k) mol"! maleic +30, > 4CO,+2H,O A, H® = -1359.2 kJ mol"!‘Therefore, the enthalpy of the isomerization process is A, H = 1336.0 kJ mol~! — 1359.2 kJ mol! = —23.2 kJ mol”! 4.47. From the reaction CyoHs(s) + 120,(¢) > 10CO;(g)+4H,0(@) A, H® = —5153.0 kJ mol! and the enthalpies of formation of CO, and HO (see Appendix B), calculate the enthalpy of formation of naphthalene (C,H). A,H® = 104,” [CO,(g)] +44,A” [HOO] - A/F? [CyoH,(5)] -12,F° [0,(g)] A/H [C,gH,(s)] = 104, [CO,(g)] + 44,” [H,0(] - 124,77” [0,(g)] - 4,H° = 10 (-393.5 kJ mol~') + 4 (-285.8 kJ mol") — 12 (0 kJ mol") +5153.0k mol"! =74.8k) mol" 4.48. The standard molar enthalpy of formation of molecular oxygen at 298 K is zero. What is its value at 315 K? (Hint: Look up the Cp value in Appendix B.) Let AH, and AH, be the enthalpies of formation of molecular oxygen at 298 K and 315 K, respectively. AH, = AH, +T,AT =0Jmol"! + (29.4 JK-! mol”) (315 K - 298 K) = 500 J mol" 4.49 Which of the following substances has a nonzero A,H° value at 25°C? Fe(s), 1,(0), H,(g), Hg(/), O,(g), C(graphite). 1,(0 is not the stable allotropic form of iodine at 25°C. Therefore, A/F [1,(] # 0. [The stable forms 1(s).] 4.50. The hydrogenation for ethylene is C,H,(s) + H,(g) > C,Hg(g)Calculate the change in the enthalpy of hydrogenation from 298 K to 398 K. The values of Cp for ethylene and ethane are 43.6 J K~'mol~! and 52.7 J K~'mol™", respectively. Assume the heat capacities are temperature independent. A, Hygg — A, Hyog = AC} (398 K — 298 K) = {Cp [cHe@)] -7 [C.H,@)] - 7 [H,@)]} 10% = (52.7 K"! mol"! — 43.6 JK"! mol“! — 28.8 JK~! mol~') (10 K) = -197kJ mol"! 4.51 Use the data in Appendix B to calculate the value of A, H® for the following reaction at 298 K: N,0,(8) > 2NO,(8) ‘What is its value at 350 K? State any assumptions used in your calculation. At 298 K, A, Hig = 24," [NO,(g)] — 4,7” [N,O,(8)] = 2 (33.9 kJ mol”) — 9.7 kJ mol™ = 58.1 kI mol"! Assuming heat capacities to be temperature independent, the enthalpy of reaction is A, H359 = A, Higg + AC? (350 K — 298 K) = A, Hie + {2C> [NO,(@)] - T> [N,O4(8)]} 62K) va - = ~ = kJ = 58.1 kImol™! + [2 (37.9 }K-! mol“) — 79.1 JK! mol~'] (52 K) (sis) = 57.9 kJ mol" 4.52 Calculate the standard enthalpy of formation for diamond, given that Cigraphite) + 0,(g) + CO,(g) A, H® = -393.5 kT mol! C(diamond) + 0,(g) > CO,(g) A, H® = —395.4kI mol"!The formation reaction of diamond is (graphite) > C(diamond), which can be thought of as a sum of the reactions: C(graphite) + 0,(g) > CO,(g) A,H® = -393.5 kJ mol"! CO,(g) > C(diamond) +0,(g) A, H® = 395.4kI mol Therefore, the standard enthalpy of formation for diamond is the sum of the standard enthalpies of reaction of the two reactions above: A, H® (diamond) = —393.5 kJ mol”! + 395.4 kJ mol"! = 1.9 kJ mol™* 4.53 Photosynthesis produces glucose, C,H,,0,, and oxygen from carbon dioxide and water: 6CO, + 6H,0 > CgH,,0, + 60 (a) How would you determine the A, H° value for this reaction experimentally? (b) Solar radiation produces approximately 7.0 x 10" kg glucose a year on Earth. What is the corresponding change in the A, H° value? (@) The most straightforward method of determining the A, H° value for this reaction would be to measure the A, H° for the reverse reaction, which is the enthalpy of combustion for glucose, in a bomb calorimeter. The desired value is just the negative of the value so determined. (b) Use standard enthalpies of formation to calculate A, H°, A,H® = A, H [C.H,,0,(s)] + 64, H? [0,(g)] — 64, H° [CO,(g)] — 64° [H,00] —1274.5 kJ mol~! + 6 (0 kJ mol~') — 6 (-393.5 kJ mol") — 6 (—285.8 kJ mol”) = 2801.3 kJ mol"! where the value for a-D-glucose is used. This is the enthalpy change for the reaction forming 1 mole of glucose. For each kilogram of glucose, 4,H° 801.3 KI mol”! (seqresteicb:) (PEE) = 1.5549 x 104 ki kg7! With 7.0 x 10'* kg of glucose produced by photosynthesis, the total A, H° involved is A,H? = 7.0 x 10! kg) (1.5549 x 10° kIkg™!) = 1.1 x 10! ky 4.54 From the following heats of combustion, CH,OH() + 30,(¢) + CO,(g)+2H,O() A, H® = -726.4 kJ mol! C(graphite) + 0,(g) + CO,(g) A, H? = ~393.5 kJ mol H,(g) + $0,(g) + H,O) A,H® = ~285.8 kJ mol~!calculate the enthalpy of formation of methanol (CH,OH) from its elements: C(graphite) + 2H,(g) + $0,(g) + CH,OH(1) ‘The formation reaction of methanol can be thought of as a sum of the reactions: CO,(g) + 2H,O()) > CH,OH() + 30,(¢) 4, H® = 726.4 KI mol! C(graphite) + O,(g) > CO,(g) A, H° = —393.5 kJ mol~! 2H,(g) + 0,(g) + 2H,0() A, H® = 2(-285.8 kJ mol”) = -571.6 kJ mol”! Therefore, the standard enthalpy of formation of methanol is the sum of the standard enthalpies of reaction of the three reactions above: A, H® [CH,OH())] = 726.4 kJ mol~! — 393.5 kJ mol“ — 571.6 kJ mol“! = —238.7 kJ mol~ 4.55 The standard enthalpy change for the following reaction is 436.4 kJ mol~!: H,(g) > H(g) + H(g) Calculate the standard enthalpy of formation of atomic hydrogen (H). 4,H® = 2A,/H" (H(@)] — 4,7? [H,(g)] = 24,H° [H@)] Note that A, H° [H,(g)] = 0 because H,(g) is the stable allotrope of hydrogen. Therefore, hy A, A [H@))] = 5 (4,H°) = = (436.4 kI mol!) = 218.2 kJ mol“! ue 2 Nin 4.56 Calculate the difference between the values of A, H® and A, U° for the oxidation of @-D-glucose at 298 K: CH20¢(s) + 60,(g) + 6CO,(g) + 6H,0(!) A, H® and A,U° differ from each other if the number of moles of gases after the reaction is not the same as that before the reaction. A,H = A,U°+ RTAn = A,U°,or A,H® — A,U° =0.4.57 Alcohol fermentation is the process in which carbohydrates are broken down into ethanol and carbon dioxide. The reaction is very complex and involves a number of enzyme-catalyzed steps. The overall change is CH 20,(8) > 2C,H,OH( + 2CO, (2) Calculate the standard enthalpy change for this reaction, assuming that the carbohydrate is, a-D-glucose. A, [C,H,OH()] + 24,H” [CO,(@)] — 4,7? [C.H,,0,(8)] = 2(-277.0 kJ mol") + 2 (-393.5 kJ mol”) — (—1274.5 kJ mol™') ALR? = = -66.5 I mol" 4.58 (a) Explain why the bond enthalpy of a molecule is always defined in terms of a gas-phase reaction. (b) The bond dissociation enthalpy of F, is 150.6 kJ mol. Calculate the value of A, H° for F(g).. (a) In the gas phase, molecules are far apart and not affected by intermolecular interactions. The bond dissociation enthalpies so determined thus refer only to the chemical bond between specific atoms and are not influenced by intermolecular interactions. (b) Its given that A, H® = 150.6 kJ mol™! for the reaction F,(g) > 2F(g). A, H® is related to the enthalpies of formation of F,(g) (which is 0) and F(g) in the following manner: 4, H? = 24,F? [F(g)] - 4, [F,(g)] = 24,7? FF@)) Therefore, 75.3 kJ mol r 1 1 2 A, [F@)] = zhi = 3 (150.6 kJ mol 4.59 From the molar enthalpy of vaporization of water at 373 K and the bond dissociation enthalpies of H, and O, (see Table 4.4), calculate the average O-H bond enthalpy in water given that H,(g)4 1/20,(g) > H,O() A, H° = —285.8 kJ mol™! First calculate the enthalpy of vaporization of H,O at 298 K (A, Hig). Then assuming heat capacities are temperature independent, calculate the enthalpy of vaporization of H,O at 373 K (4,573) 4, His = 4H [H,06)] - 4,7” [2,00] = —241.8 kJ mol! — (—285.8 kJ mol = 44.0 kI mol"!A, Hiq3 = A, Hig + AC, (373 K — 298 K) = A, Hig + {Ci [H,008)] - 7} [H,00)]} (75 &) = 44.0 kImol™! + (33.6 JK7! mol”! — 75.3 JK~! mol~') (75 K) (5) = 40.9 kI mol”! To calculate the average O-H bond enthalpy in water, the enthalpy of reaction for H,O(g) > 2H(e) +0(g) must first be obtained. This reaction can be expressed as a sum of the following reactions: H,0(g) > H,0(!) A, H3;; = —40.9 kT mol~! H,(g) + 2H) A, H? = 436.4 ki mol 20,(8) + O(g) A, Ho = #84 ki mol" H,O() > H,(@)+$0,(@) A, H® = 285.8 kJ mol"! Thus, the enthalpy of reaction for 2H(g) + O(g) + H,O(g) is 249.4 kJ mol! A, H® = —40.9 kJ mol! + 436.4 kJ mol”! + 249.4 kJ mol! + 285.8 kJ mol“! = 930.7 kJ mol" This enthalpy of reaction represents the bond enthalpy of two moles of O-H bonds. Therefore, the average bond enthalpy is, 930.7 kI mol! 7 = 465.4 mol"! 4.60 Use the bond enthalpy values in Table 4.4 to calculate the enthalpy of combustion for ethane, 2C,H,(g) + 703(g) > 4CO,(g) + 6H,0(0) Compare your result with that calculated from the enthalpy of formation values of the products and reactants listed in Appendix B. Calculation of the enthalpy of combustion using bond enthalpies: ‘Type of Number of bonds broken bonds broken Bond enthalpy /kJ-mol”'_Enthalpy change / kJ-mol~! cH 12 aid 4968 cc 2 347 694 o=0 7 4988 3491.6 ‘Type of Number of bonds formed bonds formed Bond enthalpy /kJ-mol~!_Enthalpy change / kJ-mol~! c=0 8 799 6392 on 2 460 3520 A,H? = (4968 + 694 + 3491.6) kJ mol~! — (6392 + 5520) kJ mol”! = —2758 kJ mol™!Calculation of the enthalpy of combustion using enthalpies of formation: A,H® AH” [CO,(g)] +64,” [H,0()] — 24,7” [C,H,(@)] - 74,7? [0,(6)] 4 (393.5 kJ mol”) + 6 (285.8 kJ mol~!) — 2 (-84.7 kJ mol~') — 7 (0 kJ mol~') 3119.4kJ mol™ The value of A, H° so calculated is 13% greater than that calculated using bond enthalpies. The value determined using enthalpies of formation is the correct value, since it relies on the first law of thermodynamics. Bond enthalpies are averages determined for similar bonds in many molecules and provide estimates that are typically within 10% of the experimental value for any given, particular reaction. 4.61 A 2.10-mole sample of crystalline acetic acid, initially at 17.0°C, is allowed to melt at 17.0°C and is then heated to 118.1°C (its normal boiling point) at 1.00 atm. The sample is allowed to vaporize at 118.1°C and is then rapidly quenched to 17.0°C, so that it recrystallizes. Calculate the value of A, H® for the total process as described. Since the process described is cyclic (that is, the initial and final states are identical), A, H° = 0. 4.62. Predict whether the values of g, w, AU, AH are positive, zero, or negative for each of the following processes: (a) melting of ice at 1 atm and 273 K, (b) melting of solid cyclohexane at 1 atm and the normal melting point, (c) reversible isothermal expansion of an ideal gas, and (a) reversible adiabatic expansion of an ideal gas. For most substances, the volume increases upon melting, but for ice melting to water under the conditions given, the volume decreases. In all cases, the volume change between the solid and liquid phases is small as is the value of the work associated with the melting. For ideal gases, both internal energy, U, and enthalpy, H, depend only on temperature. Keeping these points in mind results in the following predictions. q w au AH (@) positive positive positive positive (b) positive negative positive positive (©) positive negative zero. zero (@) zero negative negative negative 4.63 Einstein's special relativity equation is E = mc?, where E is energy, m is mass, and c is the velocity of light. Does this equation invalidate the conservation of energy, and hence the first law of thermodynamics? No, special relativity enlarges the definition of energy to include the mass, that is, each mass m has an associated energy E = mc*. Likewise all energy has an associated mass equal to E/c*. The total energy of the system plus the surroundings is still conserved according to the theory of special relativity, but one needs to include the energy associated with mass as well as the more usual forms of energy. Similarly, the total mass of the system plus surroundings is still conserved,as long as the mass associated with energy is included. Under conditions where it is not necessary to account for effects due to special relativity, energy and mass are separately conserved. 4.64 The convention of arbitrarily assigning a zero enthalpy value to all the (most stable) elements in the standard state and (usually) 298 K is a convenient way of dealing with the enthalpy changes of chemical processes. This convention does not apply to one kind of process, however. What process is it? Why? In a nuclear process, there are different elements on both sides of the chemical equation, and this convention would not apply. 4.65 Two moles of an ideal gas are compressed isothermally at 298 K from 1.00 atm to 200 atm. Calculate the values of g, w, AU, and AH for the process if it is carried out (a) reversibly and (b) by applying an external pressure of 300 atm. (a) When an ideal gas undergoes an isothermal process, AU = 0 and AH =0. Pp oe 1.00 atm w= Santi = ~ (2 mol) (8.314 JK™! mol") (298 K) In 00am = 263% 10° q = AU — w= —w = -2.63 x 10° (b) When an ideal gas undergoes an isothermal process, AU = 0 and AH =0. w=—-P,,(V,-V,) V, and V, can be determined using the ideal gas law: 1 mol! 2 mol) (0.08206 Latm K"! mol!) 298K) _ 4g g5 1 1.00 atm =! mot? _ 2 mol) (0.08206 L atm K-! mol") (298 K) = 0.24451, 200atm Therefore, 101.33 7 w = — (300 atm) (0.2445 L — 48.91 L) (; z =) = 1.48 x 10°F and q = AU ~ w= —w = ~1.48 x 1063 4.66 The fuel value of hamburger is about 3.6 kcal g~'. If a person eats 1 pound of hamburger for lunch and if none of the energy is stored in his body, estimate the amount of water that would have to be lost in perspiration to keep his body temperature constant. (1 lb = 454 g.)The fuel value of 1 pound of hamburger is 6.84 x 10° kJ 454g ary (4-184 ot (FRE) (.6toae D( =r) For the vaporization of water at 298 K, H,O(!) —> H,O(g), A,,,H = 44.01 kImol”!. (A,,,H is appropriate, since the vaporization is taking place at constant, atmospheric pressure.) Assuming that the entire fuel value of the hamburger is used to vaporize water, it will require that 6.84 x 10° KI (8 a) 44.01 kImol™ / \ 1 mol HO. 2.8 x 105g HO. be vaporized. 4.67 A quantity of 4.50 g of CaC, is reacted with an excess of water at 298 K and atmospheric pressure: CaC,(s) + 2H,O(!) > Ca(OH),(ag) + C,H, (g) Calculate the work done in joules by the acetylene gas against the atmospheric pressure. ‘The work done depends on the external pressure and the change in volume of the system. Because the volumes of compounds in the solid and liquid (or aqueous) phases are negligible compared with those in the gas phase, the volume change of the systei Ney, RT AV =, Var 7 Hy , 2 where P, = P., because the gas expands until it has the same pressure as the external pressure. The amount of acetylene produced is no, = 450 8CaC, ‘clk 64.10 g mol"! CaC, 0.07020 mol The work done by acetylene is Ney RT PAV =-P., (=") (0.07020 mol) (8.314 JK-! mol"') (298 K) = -174 3 4.68 An oxyacetylene flame is often used in the welding of metals. Estimate the flame temperature produced by the reaction 2C,H,(g) + 50,(g) + 4CO,(g) + 2H,0(@) Assume that the heat generated from this reaction is all used to heat the products. (Hint: First calculate the value of A, H® for the reaction. Next, look up the heat capacities of the products. ‘Assume that the heat capacities are temperature independent.)The enthalpy of reaction for the oxidation of acetylene is A,H® = 4A,F° [CO,(g)] +24, [H,0(g)] - 24, [C,H,(g)] — 54,7” [0,(8)] = 4 (—393.5 kJ mol™) + 2 (—241.8 kJ mol!) — 2 (226.6 kI mol”') — 5 (0 kJ mol") = —2510.8 kJ mol~! Because the reaction takes place at constant pressure, the enthalpy of reaction is the same as heat released by the reaction, and this heat is absorbed by the products. The initial temperature, 7,, is assumed to be 298 K, and the final temperature of the products, T, is q = 2510.8 KI mol” = {4C [CO,(8)] + 27% [H,0)]} (7, - 7) = [4 (37.1 Jmol~! K~') + 2 (33.6 Jmol“! K"')] (7, — 298 x) (sioos) T, — 298 K = 1.165 x 10*K T, = 1.19 x 10*K if The value of Cy for H,O(g) may be found in a standard reference. 4.69 The A,” values listed in Appendix B all refer to 1 bar and 298 K. Suppose that a student wants to set up anew table of A,” values at 1 bar and 273 K. Show how she should proceed on the conversion, using acetone as an example. The enthalpy of formation of a compound at 1 bar and 273 K, A,” (273) can be calculated from that at 1 bar and 298 K, A,’ (298) and C,p of the compound by assuming that the heat capacity is temperature independent. Using acetone as an example, A/H? (273) = A,H” (298) + C, (273 K — 298 K) 1k == - =! mot!) (=! pis = 246.8 kI mol! + (126.8 K7! mol) ( a (a) = —250.0 kJ mol"! 4.70 The enthalpies of hydrogenation of ethylene and benzene have been determined at 298 K: 132k} mol“! 246 kJ mol CyHy(8) + Hy(8) > CyHg(s) 4, H® CoH os) + 3H,(8) > CoHi(s) A, H® = ‘What would be the enthalpy of hydrogenation for benzene if it contained three isolated, unconjugated double bonds? How would you account for the difference between the calculated value based on this assumption and the measured value?If benzene contained three isolated, unconjugated double bonds, its enthalpy of hydrogenation could be estimated as three times that for the single double bond in ethylene, or A, HS. = 3 (— —396 kJ mol”. The difference is —246 kJ mol”! — (~396 kJ mol™!) = 150 k mol~!. This implies that benzene is 150 kI mol”! more stable than the hypothetical molecule with three isolated, unconjugated double bonds. This is attributed to the resonance (electron delocalization) energy of benzene. 4.71 The molar enthalpies of fusion and vaporization of water are 6.01 kJ mol~! and 44.01 kJ mol”! (at 298 K), respectively. From these values estimate the molar enthalpy of sublimation of ice. The sublimation process can be considered a sum of the following processes: H,0(5) + H,0) Ag, H® = 6.01 k mol“ H,0) + H,0@) —A,,,H® = 44.01 I mol"! Thus, AgyyH? = 6.01 kJ mol™! + 44.01 kJ mol~! = 50.02 kJ mol! This value is an approximation, since the value of A,,p f° is given at 298 K, whereas ice would not typically be found above 273 K. 4.72 The standard enthalpy of formation at 298 K of HF(aq) is 320.1 kJ mol~'; OH™ (aq), —229.6 kJ mol~!; F-(ag), ~329.11 kJ mol”!; and H,O(/), —285.84 kJ mol~'. (a) Calculate the enthalpy of neutralization of HF(aq), HF(aq) + OH" (aq) > F (aq) + H,0()) (b) Using the value of —55.83 kJ mol~! as the enthalpy change from the reaction H*(aq) + OH™(aq) > H,0() calculate the enthalpy change for the dissociation HF(aq) > H*(aq) + F(a) @ A,H° = A/F? [F-(aq)] + 4,7 [H,0(] - 4,7? (HF(aq)] — 4,H° [OH (aq)] 329.11 kJ mol“! + (285.8 kJ mol™') — (320.1 kJ mol~') — (229.6 kJ mol“) = -65.2 I mol (b) The dissociation of HF can be considered as a sum of the following equations: HF(aq) + OH™(aq) > F-(ag) + H,0() A, H® = -65.2kI mol! H,0() + H*(aq) +OH"(aq)— A, H® = $5.83 I mol”!The enthalpy change for the dissociation reaction is therefore A, H? = —65.2k mol”! + 55.83 kJ mol! = —9.4 kJ mol“! 4,73 It was stated in the chapter that for reactions in condensed phases, the difference between A, H and A, U is usually negligibly small. This statement holds for processes carried out under atmospheric conditions. For certain geochemical processes, however, the external pressures may be so great that A, H! and A,U values can differ by a significant amount. A well-known example is the slow conversion of graphite to diamond under Earth’s surface. Calculate the value of the quantity (A, H —A,U) for the conversion of 1 mole of graphite to 1 mole of diamond at a pressure of 50,000 atm. The densities of graphite and diamond are 2.25 gem? and 3.52 gem_®, respectively. At constant pressure, A,H—A,U = A(PV) = PAV. Thus, the change in volume, AV, for the conversion process is required to find A, H — A,U. ‘The volume of 1 mole, or 12.01 g of graphite is ot v _ 12.01 gmol ( IL ) = ( —— ) = 5.338 x 107? L mol" graphite “2.25 gem \ 1000 cm 7 i The volume of 1 mole, or 12.01 g of diamond is ae ‘eotenct” ( 1b = ——, } = 3.412 x 107° Lmol"! Giamond 3.52.gem™> oa) Therefore, —9.78 x 10°3 4,H — A,U = (50000 atm) (3.412 x 10-> — 5.338 x 10-*) Lmol-! ( mz) TLatm, 4.74 Metabolic activity in the human body releases approximately 1.0 x 10* KI of heat per day. Assuming the body is 50 kg of water, how fast would the body temperature rise if it were an isolated system? How much water must the body eliminate as perspiration to maintain the normal body temperature (98.6°F)? Comment on your results. The heat of vaporization of water may be taken as 2.41 kJ g™!. If the body absorbs all the heat released and is an isolated system, then the temperature rise, AT is related to q in the following fashion: Faoortea = Cp [HOD] AT q (1.0 x 10* kg) (499 > [H,00, (2227) (75.3 3K-! mol™ aT 7.8 KIf the body temperature is to remain constant, then the heat released by metabolic activity must be used for the evaporation of water as perspiration, that is, 1.0 x 108 KI = my aree (2.41 kT 7!) Myater = 4-1 x 10? g The actual amount of perspiration is less than this because part of the body heat is lost to the surroundings by convection and radiation. 4.75 An ideal gas in a cylinder fitted with a movable piston is adiabatically compressed from V, to V,. As a result, the temperature of the gas rises. Explain what causes the temperature of the gas to rise, The unidirectionally moving piston transfers linear momentum to the gas molecules as they collide with it. Consequently, the molecules are moving faster after their encounter with the piston. Thus, their kinetic energy is increased, and the temperature of the gas rises. 4.76 Calculate the fraction of the enthalpy of vaporization of water used for the expansion of steam at its normal boiling point. ‘Treating the steam as an ideal gas, the molar volume of steam at 373 K is calculated as, = _ RT Vac P (0.08206 L atm K~! mol") (373 K) latm = 30.61 Lmol™ ‘The work done in the expansion from liquid water to this volume of steam is then found having made the assumption that the volume of the condensed phase is negligible. (One mole of liquid water has a volume of 18 mL, so the approximation is a good one.) w=—P,,AV — (1 atm) (30.61 Lmol~') (79432) (3485) -101 kJ mol" At 373 K the molar enthalpy of vaporization of water is A,,,H1” = 40.79 kJ mol, so the fraction ap used for the expansion of steam is 3.101 kJ mol”! 7.60% 40.79 kJ mol 4.77 The combustion of what volume of ethane (C,H,), measured at 23.0°C and 752 mmHg, would be required to heat 855 g of water from 25.0°C to 98.0°C?The combustion reaction is 7 CH(a) + 50,(8) — 2CO,(g) +3H,000 Use ethalpies of formation to determine the enthalpy of combustion. 7 4, H® = 2A, H® [CO,(g)] +34, H° [H,00)] ~ 4, H° [C,H,(@)] ~ 74, H° [0,(8)] = 2(-393.5 kJ mol™!) + 3 (—285.8 kJ mol (-84.7 kJ mol“!) — i (0k mol“!) = —1559.7 kJ mol"! Thus each mole of ethane provides 1559.7 kJ of thermal energy upon combustion at constant pressure. ‘The thermal energy required to heat the water is, = my,o5y,04T = (855 8) (4.184.337! °C71) (98.0 — 25.0) °C (aan) 261.1 KI Clearly a fraction of a mole of ethane is required. The actual number of moles is Amol ethane n= (261.1kJ) er ) = 0.1674 mol ethane ‘The volume of the ethane at the stated conditions is _ ART _ (0.1674 mol) (0.08206 LatmK~' mol~') (23 +273) K ae (752 mmbig) (2-224 ) Tat v =411L 4.78 Calculate the internal energy of a Goodyear blimp filled with helium gas at 1.2 x 10° Pa (compared to the empty blimp). The volume of the inflated blimp is 5.5 x 10° m?. If all the energy were used to heat 10.0 tons of copper at 21°C, calculate the final temperature of the metal. (Hint: 1 ton = 9.072 x 10° g.) The internal energy of a monoatomic (ideal) gas is $n RT-. Likewise for an ideal gas, PV = nRT ‘Thus, for an ideal gas, U = 3 PV. For the blimp, U = 5 (1.2 x 10° Pa) (5.5 x 10° m?) 9.90 x 10° J If all this energy is used to heat copper, the temperature change is related to the amount of energy used via g = mg,Sq,AT, giving 9.072 x 10° g 1 mol Cu s °c“! mol! 9.90 x 108 1= c00u0 ( Tia (24.47 °C“! mol (ars) AT 9.90 x 108 = 3.49 x 108 °C“1AT. 283.7°C = AT = T, ~ 21°C Thus, T, = 305°C4.79 Without referring to the chapter, state the conditions for each of the following equations: (@) AH = AU + PAV, (b) Cp = Cy +R, (©) y = 5/3, @) P,VY = P,Vz, (©) w =n, (T, - 7,), (O) w = —PAV, (g) w = —nRT In(V,/V,), (h) dH = dq. (a) Constant pressure, (b) ideal gas, (©) monoatomic, ideal gas, (@) adiabatic, ideal gas, reversible process, (©) constant Volume, Cy, independent of temperature, © constant external pressure, (g) ideal gas, isothermal, reversible process, (h) constant pressure. 4.80 An ideal gas is isothermally compressed from P,, V, to P,, V>. Under what conditions would the work done be a minimum? a maximum? Write the expressions for minimum and maximum work done for this process. Explain your reasoning, The conditions are opposit to those for the isothermal expansion of an ideal gas. The minimum work is done in an reversible process because the opposing (intemal) pressure is only infinitesimally smaller than the external pressure causing the compression. The work done under these conditions is Ke Whig = —ART In Since V, < V,, the work is positive as expected for a compression. ‘The maximum work would be done in an irreversible process and an external pressure of P,, giving a value of 2(Ya- Vi) 4,81 Construct a table with the headings q, w, AU, and AH. For each of the following processes, deduce whether each of the quantities listed is positive (+), negative(—), or zero(0). (a) Freezing of acetone at 1 atm and its normal melting point. (b) Irreversible isothermal expansion of an ideal gas. (¢) Adiabatic compression of an ideal gas. (4) Reaction of sodium with water. (e) Boiling of liquid ammonia at its normal boiling point. (f) Irreversible adiabatic expansion of a gas against an external pressure. (g) Reversible isothermal compression of an ideal gas. (h) Heating of a gas at constant volume. (i) Freezing of water at 0°C. For most substances, the volume increases upon melting. (Ice melting to water is a notable exception.) In all cases, the volume change between the solid and liquid phases is small as is the value of the work associated with the melting. The volume change upon vaporization, however, isvery large. For ideal gases, both internal energy U and enthalpy H depend only on temperature. Keeping these points in mind results in the following predictions. 4 w AU AH (@) negative positive negative negative (b) positive negative zero zero (© ze positive positive positive (@) negative negative negative negative (©) positive negative positive positive () zero negative negative negative @ negative positive zero. zero (h) positive zero positive positive (@ negative negative negative negative 4.82 State whether each of the following statements is true or false: (a) AU © AH except for gases or high-pressure processes. (b) In gas compression, a reversible process does maximum work. (©) AU isa state function. (4) AU = q + w for an open system. (e) Cy is temperature independent for gases. (f) The internal energy of a real gas depends only on temperature. (a) True (b) False (c) False (U is a state function, AU is not.) (d) False (It is true for a closed system.) (e) False (f) False 4.83 Show that (8C, /9V), = 0 for an ideal gas. CH), -(H), - Leo). fae 1, Since the internal energy of an ideal gas depends only on temperature, au G),-° acy GH), -° 4.84 Calculate the work done during the isothermal, reversible expansion of a van «icr Waals gas. Account physically for the way in which the coefficients a and b appear in the final expression. Hint: You need to apply the Taylor series expansion: In(1 - x) for |x| «1 to the expression In (V — nb). Recall that the a term represents attraction and the b term repulsion.Assume the volume occupied by the gas molecules is much greater than the volume of the molecules, both before and after the expansion, that is, V, >> nb and V, > nb, then § « 1 and #8 & 1. Under these condition, the Taylor expansion described in the question can telsed in efonpity the In terms. V, 11) wet od 1 w=-nRT in =n (fF) - (- Jee -aont (E- 7 [ vy, YY 2 \w Vs 11), MeRT (1 1 = ART Inge + ORT —a)nt G-7)+ 5 (a-w)t- ‘The first term in this last equation is just the result for the ideal gas. It is modified by the succeeding terms to account for intermolecular interactions. The second term shows the balance between attractive and repulsive forces. In an expansion, V, > V, so (f — 4) <0. If attractive forces dominate, a > bRT and the entire second term is positive, which cancels some of the (negative) work done in the expansion. Because of the attractive forces, some energy must be used to overcome the intermolecular interactions, and not as much work can be done as in the case of the ideal gas.‘On the other hand, if a < bRT, the entire second term is negative and enhances the (negative) work done in the expansion. In this case the repulsive forces dominate, and the energy released as the molecules move farther apart from each other is available to do more work than the ideal gas could. The higher order terms reinforce this effect for high densities where the repulsive forces are most significant. 4.85 Show that for the adiabatic reversible expansion of an ideal gas From the text, Therefore,