Thermochemistry__ 14 When a substance is heated, the energy of its constituent particles is increased. If the kinetic energy is increased, the result is an increase in the temperature of the substance. If the increase is in potential energy, the physical state of the substance will change. The change, or combi- nation of changes, that will take place, depends upon the starting temperature of the substance. Similar considerations can be applied to removing heat from (cooling) a substance. 14:1 Changes of State The changes of state from solid to liquid and liquid to solid take place at the same temperature which is labeled the melting point or freezing point. The changes from liquid to gas and gas to liquid take place at the same temperature which is labeled the boiling point or condensing point. The amount of heat required for a state change depends on the specific substance and the amount of that substance. If we use AH to represent the quantity of heat needed to melt a substance, then AH = m(H) where m is the mass of the substance and H, is a property of a substance called its heat of fusion. Similarly, to boil a substance, the relationship is AH = m(H,) where H, is a property of a substance called its heat of vaporization. A table of H, and H, values is included in the Appendix of this book and should be used for the solution of problems in this chapter. 134132 Thermochemistry CO — ———— How much heat is required to melt 86.3 grams of iron at its melting point? Solving Process: The heat required for a phase change depends upon the mass (86.3 g) and heat of fusion or vaporization. In the present case the heat of fusion of iron is 15.4 kJ/mol. To make use of the H, value, the quantity of iron must be in units of moles. Thus, the solution is 863.gFe|imetFe |154kI 4, 31 55.8grelimerre ~~~ Example 2 How much heat is released when 79.1 grams selenium vapor condense to selenium liquid at its boiling point? Solving Process: The heat involved in the condensation depends upon the mass (79.1 g) and the heat of vaporization of selenium (86.2 kJ/mol). The solution requires the conversion of the quantity of selenium from grams to moles. 29198e| imerse| 862K) 4.3.) 79.0.¢8e|imerse” ~” Problems 1. How much heat is released upon the solidification of 387 grams of arsenic at its freezing point? 2. How much heat is required to boil 47.5 grams of helium at its boiling point? 14:2 Changes of Temperature The amount of heat required to change the temperature of a sub- stance depends upon the amount and nature of the substance as well as the extent of the temperature change. In symbols AH = m(AT)C, where AH is the heat added (or removed), m is the mass of the substance, AT is the change in temperature, and C, is a property of the substance called its specific heat capacity. The specific heat capacity of a substance varies with the temperature. However, the variation for liquids andThermochemistry 133 solids is small enough to be neglected in elementary work. For gases, the variation is greater, but for simple calculations an average value for the temperature range of interest is sufficient. Values of specific heat ca- pacities are given in the Appendix. Example 3. How much heat is required to raise the temperature of 68.0 grams of tin from 25.0°C to 80.0°C? Solving Process: In addition to the temperature change and mass given in the statement of the problem, we must consult the table in the Appendix to obtain the specific heat capacity of tin, 0.222 J/g-C°. AH = m(AT)C, 68.0.9 | (80 — 25)G"| 0.222 J AH = = ee Oe — Example 4 How much heat is released by 147 grams of water cooling from 100.0°C to 27.0°C? Solving Process: From the table in Appendix A, the specific heat capacity of water is 4.18 J/g+C°. Thus, 147.g| 73.02*| 4.184 Bar| a4 900 J aa aoe Problems 3. How much heat is required to raise the temperature of 789 grams of acetic acid from 25.0° to 82.7°C? 4, How much heat is released when 432 grams of water cool from 71.0°C to 18.0°C? 14:3 Combination Changes Many times problems are encountered that involve both tempera- ture and state changes. For such problems, each step (temperature or state change) is solved as in the preceding examples. The sum of the heat changes for all the steps is the solution to the original problem. The most complex case would be to start with a solid substance below its melting point and change that substance to a gas above its boiling point. Consider the steps to be taken in such a change:434 Thermochemistry Heat the solid to its melting point. Melt the solid. Heat the liquid to its boiling point. Boil the liquid. Heat the gas to the required temperature. Steps 1, 3, and 5 are solved in the usual manner with the relationship AH = m(AT)C,. Steps 2 and 4 require H, and H,, respectively, as well as m. The sum of the heat changes in steps 1 through 5 would then be the answer to the original problem. YReNe Example 5. How much heat is required to heat 25.6 grams of indium from 100.0°C to 200.0°C? Solving Process: Reference to a table of elementary properties shows that indium melts at 155.0°C. Thus, solid indium must be heated from 100.0°C to 155.0°C. Second, the indium must be melted. Finally, the liquid indium is heated from 155.0°C to 200.0°C. References show that the specific heat capacity of solid indium is 0.238 J/g+C° and of liquid indium 0.216 J/g+C°. The heat of fusion of indium is 3.27 kJ/mol. Step 1: To heat the indium to the melting point. 25.6.2°| 55.0 &* | 0.238 J — = 335 J ee Step 2: To melt the indium. 25.6.4 | LmeHrr| 3.27 kJ 115 g4r | LmeHr Step 3: Heat the liquid indium to 200.0°C. 25.6.g°| 45.06"| 0.216J ee = 249 war = 7494 The heat required is the sum of steps 1, 2, and 3. 335 J + 728 J + 2495 = 13125 = 0.728 kJ = 7280 Example 6 How much heat is released when 42.5 grams of aluminum are cooled from 5000 K to 298 K? Solving Process: Step 1: The Al gas is cooled to the condensing point, 2600 K or 2327°C.Thermochemistry 135 42.52 | 2127.6" | 0.9034 _ 51 699 = 81.6 kd Be Step 2: The Al gas is condensed. 42.5.g'| Lmof | 284 kJ 27.08 Step 3: The liquid Al is cooled to the freezing point, 933 K or 660°C. 42.5.4 | 1667.27 | 0.903 J | "~~ = 63 975 J = 63.9 kd we Step 4: The liquid Al is frozen. 42.5.4| Lerof | 10.8 kJ 27.04 | Lmor Step 5: The solid Al is cooled to 298 K or 25°C. $25.8 | 005 eee 24 400 J = 24.4 kd ae The total heat released is the sum of all steps. 81.6 + 447 + 63.9 + 17.0 + 24.4 = 634 kJ = 447 kd = 17.0kd Chapter Review Problems 5. Compute the heat changes associated with the following transitions: a. melting 55.8 grams Ti at 167°C. b. condensing 14.2 grams H,0 at 100°C. c. boiling 53.5 grams C,H, at 80.1°C. d. freezing 27.3 grams Al at 660°C. e. melting 76.4 grams Au at 1065°C. 6. Compute the heat changes associated with the following transitions: a. 49.2 grams acetic acid from 24.1°C to 67.3°C. b. 9.61 grams toluene from 19.6°C to 75.0°C. c. 2.47 grams kerosene from 17.1°C to 46.7°C. d. 31.9 grams chalk from 83.2°C to 55.5°C. e. 63.6 grams glass from 95.5°C to 42.3°C. 7. How much heat must be removed from 6.81 kilograms of steel to cool it from 2720°C to 625°C? Assume a freezing point of 1300°C. 8 Howmuch heat is required to change 344 grams of ice at —5.44°C to steam at 249°C?Table A-2 Molar Heats of Fusion and Vaporization for Some Substances Fusion (H,) Vaporization (H,) aluminum — 10.8 kJ/mol aluminum 284 kJ/mol arsenic 93.7 kJ/mol benzene 30.8 kJ/mol gold 12.4 kJ/mol helium 0.0182 kJ/mol indium 3.27 kJ/mol selenium 86.2 kJ/mol iron 15.4 kJ/mol water 40.7 kJ/mol steel 15.4 kJ/mol titanium 18.8 kJ/mol water 6.02 kJ/mol Table A-3 Specific Heat Capacities of Some Substances acetic acid 2.05 J/g +C° steel(c) 0.450 J/g C? aluminum 0.903 J/g*C° steel(l) 0.719. J/g G° chalk 0.920 J/g C° tin 0.222 J/g -C° glass 0.753 J/gC° toluene 4.615 J/g-C° indium(c) 0.238 J/g +C° water(c) 2.06 J/g C® indium(!) 0.216 J/g-C° water() 4.18 J/g +C° kerosene 2.09 J/g C° water(g) 2.02 J/g-C? methylbenzene 1.80 J/g C° Table A-4 Thermodynamic Properties ace AH? s° Ag(c) 0 0 42.6 Ag,SO,(aq) —590 —698 33.4 Br,(! 0 0 152 c0,(g) 394 304 214 Clg) 0 0 223 CaCl,(aq) —815 -878 54.8 Ca(OH),(c) —897 -987 76.1 Cu(c) ° 0 33.4 Cu(NO,),(aq) —157 350 193 CuSO,(aq) —679 844 109 H.(g) 0 0 131 HBr(g) -36.4 53.4 199 HCI(g) ~95.3 —92.3 187 HCl(aq) -131 —167 56.5 HI(g) 26.5 1.72 206 HNO,(aq) 556 —119 46.1 HNO,(aq) 111 207 53.3 H,0() —237 —286 69.9 H,80,(1) —690 814 139 1,(0) 0 0 116 Ici(l) -13.6 =239 135 KBr(c) -379 ~392 96.4 257KCl(aq) -413 419 158 K,SO,(aq) =1409 Mg(c) 0 oO 32.5 Mg,N,(c) —422 —461 Mg(NO,),(aq) -677 —875 175 Mg(OH),(c) 834 925 63.1 NA(g) 0 0 192 NH3(g) —16.5 46.1 192 NH,Ci(aq) 211 300 170 NH,NO,(c) 256 NH,NO,(c) -184 366 151 N,0(g) 104 82.0 220 NO(g) 86.6 902 211 NO,(g) 51.3 33.2 240 N,O.(9) 115 11.3 356 Naci(c) —384 -411 72.4 NaCl(aq) 393 —407 115 NaNO,(aq) -372 —446 207 NaOH(aq) 419 —470 11.9 Na,SO,(aq) —1266 -1387 138 0,(9) 0 0 205 Si0,(c) 857 -511 418 Sn(c) 0 0 51.5 Sn0,(c) 520 —581 52.3 Zn(c) 0 0 41.6 Zn(OH),(0) 554 —642 81.2 Zn(NO,),(aq) -370 —569 181 Appendix B Using Logarithms A log or logarithm is an exponent. In our work, the log or exponent of a number will always be given in terms of the base 10. Read the following discussion carefully if you do not understand logarithms. The mathematical equation defining a log is N =b* exponent or log log of N to the base b equals a number base log,N =a Logs are simply exponents and they can be added to multiply the numbers they represent and subtracted to divide the numbers they represent. If we define pH to be the negative log of the hydronium ion concentration, we get the following: if [H,0*] 0-7 mol/L; — then log [H,0*] = —7 and if pH = —log[H,O*]; then pH =7 The pOH is defined as the negative log of the hydroxide ion con- centration. The concentrations of the H,O* and OH- must be expressed in moles per liter which is indicated by the brackets. pH = —log[H,O*] | pOH = —log[OH™] 258Chapter 13 1, NaOH limiting — ¢. 6940 cm3 a. 102g 2. AgNO; limiting — d, 7000 cm3 e, 3560cm3 3. NaBr limiting 8, a. 20,0dm3 f. 337L 4. a. 0.114mol b. 393g 13, a 37.48 b. 3.862 c 321g b. 0.556 ec, 5090cm? 9, a, 0.134 mol ce. 6170cm? d, 5580 cm} b. 482g d. 6820 cm} 5. a. 3.60gCaCl, c. 398g e. 16200 cm! air in excess 10. 10.1g from MgCrO, 14, 17.5dm3 b. 0.206 mol 13.9 g from MgSO, 15, red c 169g 11, _N, limiting 16. 200 cm? H,0 vapor 6. N, limiting 7.99 g NH. 3, remaini 20dmPNH, 12 = 244g excess HPO, © O2 temalning 7. a 0.274 mol b. 2.868 17. 60cm3N, in excess b. 1.65 x 108 c. 0.106 mol 40 cm? NO Chapter 14 1, 484kI 5. a 2193 e. 4.81 KI d. 8133 2. 0.216 kd b. 321kJ 6. a 4360] e. 25503 3. 93.3kI ce 211KI B. 9583 7: 109005 4 1430 d. 10.9k3 ce 6193 8 1142003 Chapter 15 - Loa -3kKJ 2 a 822k) 3 a ISIS 4 a —456KT b. 14kI b. —690kT b. —4515 b. —140k3 ce. —30kT c —124kI ce. 1675 c. —245KI d. —422k3 0d. — 114K d. -557J ds —42.9kT e —358kJ e —I317KJ 1285 e —192kI Chapter 16 1. a, 0.625M 3. 7.85g,0.048M b. 3.0 7. a 0.400N, 0.200M b. 0.250M 4 a 1.00dm? 10 b. 2.00N, 2.00M © 121M b. 4.00dm3 d. 3.0 c. 0.400N, 0.200M a. 100M c. 0.333dm3 eg, 1.0 d. 3.00N, 1.00M e. 0800m 4 20.0dm> =, 3.9 e. 1.33N, 0.667M f 0500M & 0.200dm3 2 a 416g 12.8dm3 8 a 2.00N g, 200M b. 421g 3. 417g Al(NO,),-9H,0 b. 0.200M bh, 4.50N © 710g 0.741M c. 0.200N i, 0.500M d. 134g o74iM AB+ d. 150M j. 0.600N e. 489g 2.22M NO;- e, 150M kk. 150M f. 630g 6 a 10 £ 0.500N 274