Cu. 8 Heat Capacities of Solids 263 Taste 20. Hear Capactrres or Sour Inorcantc Compounps Cy = eal/(gram) (C*) Values for other elements and compounds given in Figs. 63-65. Compound Aluminum sulfate Asomonium cbloride Antimony Antimony trisulfide Arsenic “Arsenic oxide Barium carbonate Barium chloride Barium sulfate Bismuth Bismuth trioxide Boron Boron oxide Cadmium Cadmium sulfate Cadmium sulfide Calcium chloride Calcium fluoride Calcium sulfate Calcium sulfide Carbon (diamond) Cesium Chromium Chromium oxide Cobalt Cupric oxide Copper sulfate Ferrous carbonate Ferrous sulfate Gold Iodine Lead carbonate Lead chloride Lead nitrate Lead sulfate Lithium Magnesium chloride Formula Alz(SOx)s. Alz(SO,)318H20 NHCl sb Sb2S3 As As:Oz BaCO; BaCle BaSO. Bi BiOs B B,O3 Cd Cd80,-8H:0 CdS CaCle CaCly-6H:0 CaFs CaSO,-2H:0 CaS Pb(NOs): PbSO, Li MgCle ec SOSSooSoS OO OCOS SOS OSO SOD OOOO OOOOSSSOOSODOCOSDSOOSSSSSOSDC9000 Cy 184 353 357 05, 0830 0884 0796 17 110 Reference RO EDDIE ROR RDN ERD ER BD RROD ROAD BD NDE RO ED RRO RD DODO ND ERODE BD BD BD264 Compound Magnesium sulfate Manganese dioxide Manganese oxide Manganie oxide Mercuric chloride Mercurie sulfide Mercurous chloride Molybdenum Nickel sulfide Palladium Platinum: Potassium chloride Potassium chlorate Potassium chromate Potassium dichromate Potassium nitrate Potassium perchlorate Potassium sulfate Selenium Silver chloride Silver nitrate Sodium borate (Borax) Sodium carbonate Sodium chloride Sodium nitrate Sodium sulfate Sulfur (monoclinic) Titanium Titanium dioxide ‘Tungsten Water (ice) Thermophysics TaBLE 20-Continued Formula MgSO. MgS0.-H.0 MgS8O.-6H:0 MgS0,-7H:0 MnO: MnO hcl Bly HgS tga NS Pd Pt KCL KCl0s KeCr0« K2Cr.0; KNO; KCI. K:80. aecl AgNO; NesB.0; Na:B,0710H:0 Nagf NaCl NaNO; NaSO, 8 Ti TiO. Ww 20 eC Sesces0cccg0C900S 9990900 900990090000 8 & 0.492 Cu. 8 Reference DNPH RENN NUNN YN NNN NNN YYN ENE YY NNN NN NNN NEN NEN NUNN NNNYNNN Sources: 1. Selected Values of Chemical Thermodynamic Properties, as of July 1, an, National Bureau of Standards. 2. International Critical Tables (1929). 1953, edited by D. D. WagmiCu. 8 Miscellaneous Heat Capacities Taste 21. Hear Capacttis or Miscenanzous MaTERIALs C, = cal/(gram) (0°) Substance Alundum Asbestos Asphalt Bakelite Brickwork Carbon (gas retort) Cellulose Cement Charcoal (wood) Chrome brick Clay Coal Coal tar Coke Conerete Cryolite Fireclay brick Fluorspar Glass (crown) (fint) (@yrex) (silicate) (Wool) Granite Magnesite brick Pyrites (copper) (iron) Send Steel Cy 0.186 0.25 0.22 0.3 to 0.4 0.2 (approx,) 0.204 0.253 0.198 0.298 0.21 0.16 to 0.20 0.117 0.20 0.188 to 0.204 0.24 to 0.26 0.157 0.20 0.222 0.195 0.181 0.136 0.191 0.12 Temperature range, °c 100 200 21-400 21-800 21-1300 70-312 72-1472 16-55 100 1500 30 0-100 0-700 20-100 100 1500 19-50 15-98 Source: John H. Perry, Chemical Engineers Handbook, 3d ed., McGraw-Hill Book Co. (1950), with permission.268 Thermophysics Cx. 8 state from data on the gaseous state is discussed in Chapter 14. Since heat capacities of gases can be calculated by generalized methods based on spectroscopic data, these methods make it possible to esti- mate the heat capacity of a fluid at any conditions of the liquid or gaseous state from a minimum of experimental data. ‘Water has a higher specific heat than any other substance, with the exception of liquid ammonia and a few organic compounds. The heat capacity of water is a minimum at 30°C. The specific heats of aqueous solutions in general decrease with increasing concentration of solute. In dilute solutions the heat capacity of aqueous solutions is nearly equal to the heat capacity of the water present. The heat capacities of some common aqueous solutions of acids, bases, and salts at 20° C are shown graphically in Figs. 67 through 71. In Tables 22 and 23 are values of the specific heats of some common liquids. Tasue 22. Hear Capacrmes or Inorcanic Liquips Cy = heat capacity, g-eal/(gram)(C°) at «°C a = temperature coefficient in the equation C> = Co + at over the indicated temperature range. ee ° Te ti Liquid Formulat?C Cp, Cv @ fae, Ammonia NH; —40 1.051 0 1.098 60 1.215 100. 1.479 Mereury Hg 0 0.0335 60 0.0330 100 0.0329 200 0.0329 280 0.0382 Nitric acid HNO; 25 0.417 Silicon tetrachloride SiC 25 0.204 Sodium nitrate NaNO; 850 0.430 Sulfuric acid HSO, 0.839 0.00088 10° to 45°C H.S0, 25 0.369 Sulfuryl chloride SO.Cl, 25 0.234 z WO WW ODHHNMHENNNYNNNNY Sulfur dioxide SO. —20 0.3130 0.318 0.00028 10°to 140°C Water HO 0 1.008 15 1.000 100 1.006 200 1.061 300 1.155 Sources: 1. Selected Values of Chemical Thermodynamic Properties, National Bureau of Standards (1953). 2. International Critical Tables (1929). 3. Handbook of Chemistry and Physics, Chemical Rubber Publishing Co. (1953), with permission.270 Thermophysics Cu. 8 Tape 23. Hear Capacities or Orcanic Liquips Data from International Critical Tables unless otherwise indicated. Cy = heat capacity, calories per gram per O° at tC @ = temperature coefficient in equation: Cp = Cyo + at, applying over the indicated temperature range Liquid Formula | °C | C, |C»| a | Temp. Range Carbon tetrachloride | CCl 20 10.201 |0 198/0 000031] Oto 70° Carbon disulfide Se '0.235]0.000246|—100 to +150° Chloroform CHC); 15 |0.226 |0:221]0 000330] —30 to +60° Formic acid CH:0: 0 [0.496 |0.496|0.000709| 40 to 140° Methyl alcohol CHO 0 |o.566 40 0.616 Acetic acid CoH.O2 |0 468|0.000929] 0 to 80° Ethyl aleohol CoH.O —50 |0.473 0 0.535 25 (0.5 50 [0.652 100 [0.824 150 [1.053 Glycol CoH:O2 0 |0.544 jo.5440.001194) —20 to +200° ly] alcohol CsHO (0. 3860} 121 to 96 [0.665 Acetone CsH:0 10. 506|0.000764) —30 to +60° Propane He 0 [0.576 [0.576/0.001505| —30 to +20° Propyl aleohol C3H.O —50 (0.456 0 (0.525 +50 (0.654 Glycerol CsH303 —50 (0.485 0 0.540 +50 |0.598 +100 [0.668 Ethyl acetate CHO. 20 (0.478 n-Butane Hho 0 {0.550 |0.550]0.00191 | —15 to +20° Ether CHO 0 {0.529 30 [0.548 120 0.802 Isopentane CBs 0 {0.512 8 [0.526 Nitrobenzene CcHsNO2 10 0.358 50 0.329 120 |0.393 Benzene Cis 5 |0.389 20 {0.406 60 |o.44a i 90 0.473 Aniline CHLN 0 {0.478 50 {0.521 100 {0.547 n-Hexane CH. [20 to 100/0:600 Toluene GHe 0 0.386 50 [0.421 100 [0.470 n-Heptane CH Oto 50 [0.507 30 [0.518 |0.476|0.00142 | 30 to 80° Decane (BP 172°) CroHee 0to50 [0.502 n-Hexadecane CHa | Oto 50 0.496 Stearic acid CisHs02 175 to 137|0.550 Diphenyl* CisBio {0.3000.00120 | 80 to 300° +H. O. Forrest, E. W. Brugmann, and L, W. Cummings, Ind. Eng. Chem, 23, 240 (1931).272 Thermophysics Cu. 8 Taste 24, Heats or Fostow dy = heat of fusion, g-cal per g-atom or g-mole; ty = melting point, ° C; T, = melting point, °K ‘To convert heats of fusion to Btu per pound-mole, multiply table values by 1.8. Na °c A/T, ‘Reference Elements Ag 2,700 961 2.19 1 Al 2,600 660 2.79 1 Cu 3,110 1083 2.29 1 Fe 3,660 1535 2.02 2 Na 629 98 1.70 2 Ni 4,200 1455 2.43 1 Pb 1,220 327 2.08 1 S (hombic) 300 115 0.77 2 Sn 1,690 232 3.35 1 Zn 1,595 419 2.30 1 Compounds H.O 1,436.3 0.0 526 1 Sb8; 11,200 BAT 13.66 1 CO: 1,999 —56.2 9.21 1 CaCh 6,780 782 6.43 1 NaOH 1,700 318 2.88 1 NaCl 6,800 808 6 29 1 Carbon tetrachloride 600 —22.9 2.40 1 Methyl alcohol 187 —98 4,33 1 Acetic acid 2,800 16.6 9.65 1 Ethyl alcohol ~ 1,200 —114.6 7.58 1 Benzene 2,370 5.4 8.51 2 Aniline 1,950 -7.0 7.32 2 Naphthalene 4,550 80 12.88 2 Diphenyl 4,020 a 11.70 2 Stearic acid 13,500 70.5 39.35 2 Sources: 1. Selected Values of Chemical Thermodynamic Properties, as of July 1, 1953, edited by D. D, Wagman, National Bureau of Standards. 2, International Critical Tables (1929). Trouton’s Rule. According to Trouton’s rule, the ratio of the molal heat vaporization \, of a substance at its normal boiling point to the absolute temperature 7; is a constant. Thus Ae ee ateige T, Ga) where K is termed Trouton’s ratio. For many substances this ratio is equal to approximately 21 where the latent heat is expressed inCu. 8 Heats of Vaporization from Vapor Pressure 273 Taste 25. Hears or TRANSITION d: = heat absorbed in transition, g-cal per g-atom or Chu per Ib-atom or mole. To convert to Btu per Ib-mole, multiply by 1.8. 4, = temperature of transformation, ° C. ‘Transition a t, °C Sulfur Rhombie + monoclinic 7.0 114-151 Iron (electrolytic) (see also Fig. 121, p. 482) ae 363 770 Bor 318 910 yb 108 1400 Manganese a8 1325 1070-1130 Nickel ae 78 320-830 Tin White — gray 530 0 Source: International Critical Tables (1929). calories per gram-mole and the temperature in degrees Kelvin. For nonpolar liquids Trouton’s ratio increases slightly as the normal boiling point increases. For polar liquids values of this ratio are much greater than 21. Kistyakowsky Equation for Nonpolar Liquids. A thermo- dynamic equation was developed by Kistyakowsky for the calculation of Trouton’s ratio at the normal boiling point of nonpolar liquids: XN Fa = 8.75 + 4.571 logio Ts (28) s where \, = normal heat of vaporization in calories per gram-mole at TY K T» = normal boiling point in degrees Kelvin. This equation is in excellent agreement with experimental results for a wide variety of nonpolar liquids but is inapplicable to polar liquids. Heats of Vaporization from Vapor-Pressure Data and Compres- sibility Factors. The molal heat of vaporization of a substance may be calculated from data on its vapor-pressure-temperature relations and specific molal volumes of the liquid and gas by the rigorous equation 3, page 78, which may be written in terms of reduced properties as Lee (#) Gat 29) Any reliable equation for dp,/dT, or dp/dT may be used. For example,274 Thermophysics Cu. 8 Taste 26. Huars or VAPorIzaTion d = heat of vaporization at f° C, g-cal per g-mole t = temperature, °C, — t = normal boiling-point, °C To convert heats of vaporization to Btu per lb-mole, multiply table values by 1.8. Substance a 4°C Reference Ammonia 5,581 —33.4 2 Argon 1,500 = 185.8 2 Bromine 7,340 25.0 1 Carbon dioxide 6,030 -78.4 2 Carbon disulfide 6,400 46.25 1 Carbon monoxide 1444 =191.5 2 Carbon oxysulfide 4,423 —50.2 2 Carbon tetrachloride 7,170 16.7 1 Chlorine 4,878 —34.1 2 Dichlorodiftuoromethane 4,850 —30.5 1 Dichloromonofiuorometbane (Freon 21) 6,400 8.9 1 Helium 22 —268.9 2 Hydrogen 216 252.7 2 Hydrogen bromide 4,210 —66.7 2 Hydrogen chloride 3,860 —85.0 2 Hydrogen cyanide 6,027 25.7 2 Hydrogen fluoride 1,800 19.9 1 Hydrogen iodide 4,724 —35.35 1 Hydrogen sulfide 4,463 —60.3 2 Mercury 18,890 356.6 1 Nitric oxide 3,292 -151.7 1 Nitrogen 1,336 —195.8 2 Nitrous oxide 3,950 —88.5 2 Oxygen 1,629 —183.0 2 Silicon tetraftuoride 6,150 =95.5 1 Sulfur 25,000 444.6 1 Sulfur dioxide 5,950 —10.0 1 Sulfur trioxide 9,990 43.3 1 Trichloromonofiuoromethane (Freon 11) 5,960 23.6 1 Water 9,717 100.0 1 Sources: 1. Selected Values of Chemical Thermodynamic Properties, as of July 1, 1953, edited by D. D. Wagman, National Bureau of Standards. 2. John H. Perry, Chemical Engineers Handbook, 3d ed., McGraw-Hill Book Co. (1950). differentiation of equation 16, page 95, gives dp, A A —_—= — — —20(T-—) ap, = 2:303p-| aa + 40(P, — be (30) The compressibility factor z of a substance is defined as 2 = pu/RT. For ideal-gas behavior this factor is unity. Applying this factor to bothCu. 8 Heats of Vaporization from Vapor Pressure 275 gas and liquid states and rearranging gives vo — 9a = (to ~ 22) = (6g — aR 1) Pp Pe From vapor-pressure data on 95 different compounds Lydersen, Greenkorn, and Hougen® found that the term z¢ — zz of a saturated liquid-vapor system is a unique function of reduced pressure nearly independent of the nature of the compound as tabulated in Table 26A. Taste 26A. Vanuns or zg — z, as A Function or Repucep Pressure Pro tg 2b Pr Ge GLP GL 0 1.0 015 0.838, 0.60 0.542 0.95 0.210 0.01 0.983 0.20 0.802 0.65 0.506 0.96 0.192 0.02 0.968 0.25 0.769 0.70 0.467 0.97 0.170 0.03 0.954 0.30 0.738 0.75 0.426 0.98 0.142 0.04 0.942 0.35 0.708 0.80 0.382 0.99 0.106 0.05 0.930 0.40 0.677 0.85 0.335 1.00 0.000 0.06 0.919 0.45 0.646 0.90 0.280 0.08 0.899 0.50 0.612 0.92 0.256 0.10 0.880 0.55 0.578 0.94 0.226 Combining equations 29, 30, and 31 gives d= 2.303 (2¢ — 2r)RT.[A + 407,2(T, — be] (82) At high values of 7, and low values of b equation 32 reduces to = 2.303(z¢ — 21)RT.A (83) Values of A and b for specific compounds are given in Table 8, page 95, or may be calculated from equation 16, page 95, from accurate measure- ments of vapor pressure at two temperatures combined with reliable values of p. and T.. Illustration 2. Estimate the molal heat of vaporization of acetone at pressures of 1.0 and 8.0 atm, Boiling point at 1 atm 4 56.5° C (829.7° K) atSatm = 183.1° C (406.3°K) Te = 508.7°K;p. = = 46.6 atm At 1 atm, 7, = 329.7/508.7 = 0.648; p, = 1/46.6 = 0.0215 At 8 atm, 7, = 406.3/508.7 = 0.799; p, = 8/46.6 = 0.172 From Table 26A: At Latm, zo — en = 0,966 At 8 atm, 2 — 2p = 0.822 * A. L, Lydersen, R. A. Greenkorn, and O. A. Hougen, Private communication (1954).278 Thermophysics Cu. 8 The term s, is the slope of the line resulting when the logarithm of the vapor pressure of the given substance is plotted against the loga- rithm of the vapor pressure of a reference substance at the same reduced temperature. Values of s,(T./T’.) are given in Table 27 for various refrigerants with water as the reference substance. In Table 28 are given the heats of vaporization of water in Btu per pound-mole at various values of reduced temperature 7, and the corresponding vapor pressures. Taste 27. Hear or Varorization Factors AND CRITICAL ‘TEMPERATURES OF REFRIGERANTS” Reference substance is water. Refrigerant Formula s+ Critical Temp., °R sf Ammonia NH; 0.933 730.1 0.584 Benzene CHe 0.928 1012.7 0.803, Butyl alcohol CHLOH 1,397 1008.3 1.149 Carbon dioxide 0, 0.872 547.7 0.410 Carbon disulfide OS: 0.889 983.2 0.707 Carbon tetrachloride CCl, 0.869 1001.3 0.746 Chlorine Cl: 0.776 751.0 0.502 Chlorobenzene CHCl 0.983 1138 0.905 Chloroform CHCl, 0.916 965 0.749 Ethane OH 0.810 549.8 0.382 Ethyl aleohol C:HOH — 1.280 929.3 1,022 Ethyl chloride CHCl 0.885 824 0.625, Ethyl ether (CHs):0 0.952 841 0.687 Freon 11 CCLF 0.807 848.1 0.654 Freon 12 COLE 0.869 692.5 0.516 Freon 21 CHCLF 0,891 813.0 0.621 Freon 113 G:F; 0.962 877.1 0.724 Isobutane CB 0.879 734.7 0.551 Methane CH. 0.716 343.3 0.211 Methyl alcohol CHOH = 1.179 923 0.936 Methyl chloride CHCl 0.845 749.3 0.543 n-Butane CH 0.807 765.3 0.501 Nitrogen dioxide NO: 0.851 557.4 0.407 n-Propyl alcohol CH,OH 1,308 766.4 1,083 Propane C.Hs 0.851 665.9 0.486 Sulfur dioxide 80: 0.949 774.7 0.681 Toluene Gs 0.956 1069.2 0.877 Illustration 3. Estimate the heat of vaporization of Freon 12 (difluorodi- chloromethane) at 200° F. From Table 27 the critical temperature of Freon 12 is 232.5° F, and the valueCu. 8 Heat of Vaporization of sr (T./T'c) is 0.516. The molecular weight is 121. 660 T, = — = = 0.951 279 At T, = 0.951 the molal heat of vaporization of water from Table 28 is 7707 Btu per lb-mole. From equation 39, T. A=s8, (0.516) (7707) = 3977 Btu per lb-mole Tas 28. Motau Heats or Vaporization AND VAPOR PRESSURES oF WATER ’. = 1165.1° R, \ = Btu per Ib-mole, p = psi abs T, » 0.428 19,870 0.44 19,170 0.46 18,940 0.48 18,700 0.50 18,460 0.52 18,210 0.54 17,980 0.56 17,770 0.58 17,440 0.60 17,170 0.62 16,880 0.64 16,590 0.66 16,280 0.68 15,950 0.70 15,600 0.72 15,230 0.74 14,840 0.76 14,420 0.78 13,980 0.80 13,490 P 0.092 0.198 0.446 0.934 1.824 3.365 5.896 9.871 15.871 24.613 36.959 54.006 76.785, 106.65 145.08 193.68 254.1 328.3 418.4 526.1 a 12,970 12,400 1,70 11,070 10,290 9,684 9,401 8,907 8,365 1174 7,108 6,336 5,393 4,148 0 Pp 654.2 804.5 980.3 1184.7 1419.3 1548.7 1688.4 1836.0 1995.6 2164.3 2346.1 2538.6 2746.8 2967.5 3206.2 Gordon has studied the application of this method to much of the available data on heats of vaporization and found good agreement, with errors generally less than 5%. venient to use where a number of values of heats of vaporization are required at different conditions for a single substance. Another good method for the prediction of heats of vaporization at all conditions has been developed by Meissner. This method is particularly con- This method is applicable to all substances and has approximately the same accuracy as the methods herein described. u HL. P. Meissner, Ind. Eng. Chem., 33, 1440 (1941).280 Thermophysics Cu. 8 Heats of Vaporization of Hydrocarbons. Heats of vaporization of hydrocarbons and petroleum fractions under atmospheric pressure were calculated by Fallon and Watson® by differentiating equation 15, page 92, and substituting in the Clapeyron equation 3, page 78. The resultant correlation is plotted in Fig. 72 relating heat of vaporiza- tion to boiling point at various parameters of API gravity or molecular 180, el T 3 | I Ne wo DXSe le a Zuo} 1 a ie & = S109 | 2 ; { 80) i. Bory “Ae £ ae 7 i | See | | io m0 ao SSCS «SC S«SC SCO Average Boiling Point,"F Fic. 72. Heats of vaporization of hydrocarbons and petroleum fractions, Note: Use molecular weights if available rather than API gravities (Reproduced in CPP Charts) weight. In dealing with pure compounds use of the molecular weight parameter is preferable. Heats of vaporization at other temperatures may be obtained by means of equation 40. The values of Fig. 72 are in close agreement with the Kistyakowsky equation, page 273, for low-boiling compounds but are considerably higher for high-boiling materials. It is believed that these higher values represent a more reliable extrapolation than that of the Kist- yakowsky equation. Empirical Relationship between Heat of Vaporization and Temperature. The heat of vaporization of a substance diminishes as its temperature and pressure are increased. At the critical temper- ature, as pointed out in Chapter 4, the kinetic energies of translation of the molecules become sufficiently great to overcome the potential energies of the attractive forces which hold them together, and mole- cules pass from the liquid to the vapor state without additional energiza-