1348
J. Chem. Eng. Data 2005, 50, 1348-1352
Thermal Properties of Ethyl Undecanoate and Ethyl Tridecanoate by Adiabatic Calorimetry J. C. van Miltenburg* and H. A. J. Oonk Chemical Thermodynamics Group, Debye Institute, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands
The heat capacity of ethyl undecanoate was measured between 110 K and 365 K; the compound crystallized in a metastable form, which recrystallized slowly to the stable crystalline state during heating. The triplepoint temperature of the stable form was found to be (259.17 ( 0.04) K, and the enthalpy of fusion was (36.1 ( 0.1) kJ‚mol-1. The purity calculated from the fractional melting curve was 97.5 mol %. The metastable form crystallized at 251.3 K. The heat capacity of ethyl tridecanoate was measured between 175 K and 320 K; the compound also crystallized in a metastable form, which recrystallized during heating to the stable form. The triple-point temperature was found to be (272.4 ( 0.1) K, and the enthalpy of fusion was (40.7 ( 0.1) kJ‚mol-1.
Introduction publication,1
In a recent the available vapor pressure data of a series of methyl esters of the linear carboxylic acids were assessed. The consistency of the data was checked using the “arc-method”, in which, by applying a linear contribution to the Clapeyron fit, irregularities in the data are easily spotted. When the vapor pressure measurements of van Bommel2 on the ethyl esters were checked, the measurements of the two compounds mentioned in the title clearly did not show the expected correlation. This was probably due to impurities in the samples. New samples, of the highest quality available, were purchased. A new series of vapor pressure measurements did not improve the results, so it was decided to measure the purity by adiabatic calorimetry. In this article, we present the heat capacity data and the enthalpies of fusion of the two ethyl esters, ethyl undecanoate and ethyl tridecanoate. No heat capacity data were found for these compounds in the literature. Experimental Section Ethyl undecanoate (C13H26O2, CAR RN: 627-90-7) was purchased from Sigma; the stated purity was “approx. 99 mass %”. Ethyl tridecanoate (C15H30O2, CAS RN: 28267-29-0) was purchased from Lancaster Synthesis; the stated purity was 99 mass %. The compounds were used as received. The calorimeter used for ethyl tridecanoate, CAL V (laboratory indication), has been described.3,4 Oxford Instruments calibrated the thermometer with a precision of 0.001 K using the ITS-905 temperature scale. The uncertainties of the heat capacity measurements were checked with n-heptane6 and synthetic sapphire7,8 and found to be within 0.2%. Below 30 K, the reproducibility of this calorimeter is about 1%, between 30 K and 100 K, it is (0.05 to 0.1) %, and above 100 K, it is 0.03%. The calorimeter vessel was filled in a glovebox under a nitrogen atmosphere and evacuated for about 5 min before closing the measuring vessel. A helium pressure of about 1000 Pa * Corresponding author. E-mail:
[email protected].
was admitted before closing in order to promote the heat exchange within the vessel. Measurements were made in the intermittent mode using stabilization periods of about 600 s and heat input periods of about 500 s. The temperature increase was generally about 2 K for each measurement outside the transition region. For the measurements on ethyl undecanoate, CAL 8 was used.9 This calorimeter was specially designed for small samples and was used because only a limited amount of material was available. This calorimeter was described recently; it uses about 0.5 g of sample. The measurement on n-heptane and synthetic sapphire showed that the accuracy of the heat capacity measurements was on the order of 0.5% and for latent heat effects such as the enthalpy of fusion it was on the order of 0.2%. Ethyl undecanoate (molar mass 214.34 g‚mol-1) was measured in CAL 8. About 0.5 g was used. The experimental data are given in Table 1. First the sample was quickly cooled to about 140 K, and a measurement was made to 300 K. In this measurement, exothermic effects took place (Figure 1) between 200 K and 220 K and during the melting process between 255 and 259 K, indicating the transition to the stable crystalline form. The sample was cooled again to 160 K; this cooling was controlled by setting the control temperature of the shield regulation about 10 K below the vessel temperature without breaking the vacuum. The cooling curve is given in Figure 4. From this curve, it is clear that the compound crystallizes at 253.2 K with only a very small undercooling, implying that this temperature can also be taken as the melting temperature of the metastable form. This means that the double peak in the heat capacity curve given in Figure 2 is not caused by a solid-solid transition followed by melting, as it appears at first sight, but is caused by the melting of the metastable crystal form, whereas during the melting process recrystallization to the stable crystal form takes place. This recrystallization is slow and is not directly visible in the heat capacity curve but manifests itself in the positive temperature drift during the stabilization periods. After equilibrating for 36 h at 252 K, a measurement to 257 K was made. No exothermic effects occurred, indicating that the
10.1021/je050065n CCC: $30.25 © 2005 American Chemical Society Published on Web 05/13/2005
Journal of Chemical and Engineering Data, Vol. 50, No. 4, 2005 1349 Table 1. Experimental Data Series for Ethyl Undecanoate T
Cp
H(T) - H(start)
K
J‚K-1‚mol-1
J‚mol-1
T
Cp
H(T) - H(start)
K
J‚K-1‚mol-1
J‚mol-1
T
Cp
H(T) - H(start)
K
J‚K-1‚mol-1
J‚mol-1
23 385 23 968 24 425 24 869 25 433 26 121 26 901 27 746 28 631 29 544 30 481 31 450 32 464 33 551 34 768 36 235 38 174 40 594 43 440 46 917 50 961
253.80 254.12 255.70 257.82 258.64 259.44 261.58 264.49 267.39 270.29 273.18 276.07 278.95 281.82 284.68 287.54 290.39 293.24 296.08 298.92
14892 12654 480 2171 18871 2260 419.55 420.55 421.02 422.21 423.35 424.79 425.66 425.14 426.82 428.33 429.39 430.72 431.60 433.20
55 259 59 599 62 434 64 633 68 371 72 131 74 286 75 509 76 732 77 953 79 176 80 399 81 623 82 843 84 063 85 284 86 508 87 732 88 957 90 185
1a
139.88 143.35 146.22 149.10 151.98 154.87 157.77 160.66 163.55 166.44 169.36 172.28 175.19 178.11 181.02 183.93 186.85 189.76 192.68 195.60 198.55
207.52 212.19 216.66 220.22 223.45 227.20 230.26 236.92 242.00 242.39 239.53 242.64 244.71 247.80 251.81 254.69 258.17 261.13 263.19 260.74 246.06
8629 9347 9963 10 590 11 231 11 883 12 544 13 219 13 912 14 613 15 314 16 018 16 727 17 445 18 176 18 912 19 659 20 415 21 180 21 946 22 694
201.57 204.69 207.94 211.21 214.35 217.39 220.36 223.29 226.21 229.11 232.01 234.90 237.78 240.62 243.39 246.01 248.31 250.26 251.84 252.88 253.45
series 212.99 161.31 120.20 152.71 206.94 247.39 278.18 297.94 309.76 318.55 328.11 342.23 363.87 402.06 477.14 650.51 1069 1451 2257 5347 10293
111.58 113.84 116.71 119.57 122.42 125.29 128.15 131.02 133.86 136.66 139.44 142.19 144.90 147.59 150.26 152.89 155.51 158.10 160.67 163.21 165.73 168.24 170.74 173.23 175.70 178.15 180.59 183.01 185.42 187.81 190.18 192.55 194.90 197.24 199.56
173.66 175.94 178.91 181.88 185.27 187.91 190.48 194.47 198.69 198.56 201.64 204.69 207.94 211.29 213.75 217.30 220.97 224.09 229.12 233.25 236.15 230.57 232.17 234.76 236.78 239.40 242.15 244.19 245.75 248.17 251.89 256.43 257.21 257.78 262.12
339 740 1248 1764 2286 2821 3362 3914 4472 5029 5585 6143 6703 7266 7832 8401 8974 9550 10 132 10 720 11 312 11 897 12 475 13 056 13 638 14 222 14 809 15 398 15 987 16 577 17 171 17 772 18 376 18 978 19 583
201.88 204.18 206.47 208.75 211.01 213.26 215.50 217.73 219.95 222.16 224.36 226.54 228.71 230.87 233.01 235.14 237.26 239.36 241.44 243.49 245.51 247.49 249.42 251.26 252.97 254.50 255.75 256.70 257.35 257.78 258.08 258.29 258.44 258.55 258.64
series 2b 266.33 269.86 268.45 272.25 276.09 279.59 279.55 283.48 287.50 290.42 293.74 297.69 302.05 307.08 312.10 318.94 327.12 337.32 349.15 366.65 390.29 425.06 480.50 571.99 727 1039 1661 2825 4810 7790 11784 16860 23291 30126 38815
20 194 20 811 21 427 22 043 22 664 23 289 23 916 24 543 25 177 25 814 26 456 27 101 27 752 28 409 29 073 29 745 30 428 31 125 31 839 32 574 33 339 34 147 35 017 35 982 37 090 38 419 40 066 42 085 44 446 47 065 49 851 52 743 55 703 58 705 61 737
258.71 258.78 258.87 259.64 261.33 263.28 265.23 267.18 269.12 271.06 272.99 274.93 276.86 278.79 280.72 282.65 284.57 286.49 288.42 290.34 292.25 294.17 296.09 298.00 299.92 301.84 303.75 305.67 307.58 309.50 311.41 313.32 315.24 317.15 319.06
48322 41751 27850 994 414.49 418.61 419.66 419.56 420.55 421.01 421.34 422.40 423.50 424.54 424.74 425.25 425.82 426.92 427.56 427.60 429.47 430.48 431.30 431.45 432.30 434.20 436.09 436.86 437.94 438.69 439.51 440.63 441.69 443.16 444.40
64 790 67 845 70 874 73 091 74 204 75 019 75 835 76 652 77 466 78 282 79 098 79 914 80 731 81 549 82 368 83 187 84 005 84 826 85 647 86 467 87 289 88 114 88 940 89 767 90 594 91 424 92 258 93 094 93 930 94 769 95 609 96 451 97 295 98 144 98 991
292.35 293.82 295.74 297.65 299.55 301.45 303.35 305.23 307.12 309.00 310.87 312.74 314.61 316.48
429.73 430.15 431.35 432.04 433.51 434.67 436.03 437.30 438.29 438.55 439.73 440.36 441.72 441.83
87 323 87 954 88 781 89 606 90 429 91 253 92 077 92 902 93 727 94 551 95 375 96 198 97 023 97 849
318.35 320.22 322.09 323.96 325.83 327.70 329.57 331.44 333.31 335.19 337.06 338.94 340.81
series 3c 443.44 444.36 445.90 447.60 448.49 449.50 450.40 451.66 453.33 455.41 456.14 456.81 458.35
98 676 99 506 100 338 101 173 102 010 102 850 103 692 104 536 105 383 106 234 107 088 107 945 108 803
342.69 344.57 346.45 348.34 350.22 352.11 354.00 355.90 357.80 359.70 361.60 363.51 365.42
459.47 461.00 462.31 463.75 465.10 466.34 467.34 468.59 469.50 471.05 472.21 473.69 475.18
109 665 110 530 111 399 112 271 113 147 114 027 114 910 115 797 116 687 117 581 118 479 119 381 120 288
a
Series 1: metastable crystal to the liquid phase. b Series 2: annealed crystal to the liquid phase. c Series 3: liquid phase.
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Journal of Chemical and Engineering Data, Vol. 50, No. 4, 2005
Figure 1. Experimental heat capacity data of ethyl undecanoate: b, first run; O, second run after equilibration close to the melting point.
Figure 2. Enlarged view of Figure 1 around the melting point. In the first run, given by b, the melting process takes place in two steps.
Figure 4. Cooling curve of ethyl undecanoate. Crystallization started at 251.3 K, and the temperature rose to 253.2 K. The cooling rate just before crystallization was 1.8 × 10-3 K‚s-1.
Figure 5. Equilibrium temperature in the melt against the reciprocal of the melted fraction for ethyl undecanoate. b, Data points calculated from the run with the annealed sample. Calculated purity, 97.5 mol %; triple-point temperature, 259.17 K; and enthalpy of fusion, 36.05 kJ‚mol-1. Table 2. Reciprocal of the Melted Fraction (1/F) and the Equilibrium Temperatures (Teq) in the Melt of Ethyl Undecanoate
Figure 3. Enthalpy curves of ethyl undecanoate around the melting point: 2, first run; 4, second run with the annealed sample.
product had transformed completely to the stable crystalline form. The next measurement was made from 110 K to 320 K (series 2 in Table 1 and given in Figure 1). The enthalpy curves of the quenched and the annealed compound are given in Figure 3. The curves were shifted so that the enthalpies in the liquid phase corresponded at 300 K. From the measurement on the annealed sample, the enthalpy of fusion was calculated to be (36.0 ( 0.1) kJ‚mol-1. The calculation was made between 200 K and 264 K; the heat capacity of the solid used was Cp,s(170 K to 200 K) ) {50.45 + 1.0604T/K} J‚K-1‚mol-1, and that of the liquid was Cp,l(263 K to 280 K) ) {323.79 + 0.3595‚T/
1/F
Teq/K
9.375 6.491 4.680 3.540 2.799 2.294 1.935 1.668 1.464 1.303 1.174
255.754 256.695 257.347 257.784 258.079 258.287 258.438 258.553 258.642 258.713 258.781
K} J‚K-1‚mol-1. The enthalpy of fusion was calculated by constructing a sigmoid baseline. In the first calculation, the aforementioned fits were used to calculate the enthalpy increment of the solid and liquid only, thus without the fusion process, the difference in total enthalpy being the first approximation of the enthalpy of fusion. Then the melted fractions were calculated by constructing a new baseline using the contributions of the solid and liquid phases to the heat capacity, and a new enthalpy of fusion was found. This process was repeated until a stable baseline was found. Three iterations were needed. The triple-point temperature was found to be (259.17 ( 0.04) K, and the calculated purity according to the van’t Hoff plot was 97.5 mol %. The error margin in the triple-point
Journal of Chemical and Engineering Data, Vol. 50, No. 4, 2005 1351 Table 3. Experimental Data Series for Ethyl Tridecanoate T
Cp
H(T) - H(start)
T
Cp
H(T) - H(start)
T
Cp
H(T) - H(start)
K
J‚K-1‚mol-1
J‚mol-1
K
J‚K-1‚mol-1
J‚mol-1
K
J‚K-1‚mol-1
J‚mol-1
281.19 283.11 285.04 288.42 291.56 294.94 298.28 301.62 305.04 308.53 312.04 315.60 319.25 323.04 326.79 330.79 334.71 338.31 341.95 345.12 347.77 349.71 350.93 351.32 351.20 350.67 349.28 346.31 343.21 342.53 350.24 387.68 550.06 1448 4663 10682 18329 27817
0 171 680 1528 2383 3246 4119 5004 5897 6800 7714 8639 9574 10 519 11 477 12 447 13 428 14 419 15 424 16 439 17 463 18 497 19 540 20 592 21 648 22 708 23 772 24 842 25 915 26 992 28 078 29 202 30 472 32 146 34 322 36 777 39 325 41 909
271.90 271.96 272.00 272.03 272.06 272.08 272.11 272.15 272.20 272.28 273.17 275.34 278.01 280.68 283.33 285.99 288.64 291.29 293.93 296.56 299.20 301.82 304.44 307.06 309.67 312.27 314.87 317.47 320.06 series 2b 203.72 204.30 206.07 209.03 211.98 214.92 217.87 220.82 223.77
40 847 57 663 76 091 92 057 100 985 98 382 85 465 65 481 42 791 24 659 1079 486.33 487.34 488.58 489.10 489.40 490.72 492.03 493.00 494.67 496.00 497.42 498.94 500.72 502.48 503.98 505.99 507.58 509.22
44 512 47 127 49 749 52 375 55 004 57 633 60 261 62 885 65 502 68 103 70 300 71 853 73 153 74 453 75 752 77 051 78 351 79 651 80 951 82 253 83 557 84 861 86 167 87 474 88 783 90 094 91 407 92 722 94 039
303.18 304.48 306.99 310.71 314.26 318.07 321.89 325.88 329.74
5757 5931 6475 7389 8310 9241 10 185 11 141 12 108
226.72 229.65 232.57 235.47 238.34 241.19 244.03 246.84 249.63 252.40 255.15 257.88 260.57 263.19 265.70 267.99 269.83 270.96 271.50 271.75 271.90 271.99 272.05 272.10 272.15 272.19 272.23 272.26 272.30 272.34 272.39 272.46 272.58 273.13 274.84 277.28 279.73 282.18 284.62
334.00 338.41 342.70 347.41 352.35 357.30 362.39 368.11 374.08 380.86 387.34 398.08 413.23 439.48 495.53 628.88 1076 2812 6749 13133 21540 32070 43573 49770 57072 60 211 66 847 67 665 68 212 55 061 41 856 27 902 16 184 1987 493.67 486.51 487.34 488.17 489.23
13 085 14 073 15 066 16 065 17 071 18 083 19 102 20 129 21 164 22 211 23 269 24 339 25 429 26 546 27 717 28 995 30 497 32 352 34 508 36 803 39 153 41 530 43 920 46 317 48 717 51 119 53 523 55 928 58 333 60 736 63 134 65 521 67 886 70 029 71 597 72 794 73 987 75 179 76 373
1a
series 176.54 177.15 178.94 181.89 184.84 187.78 190.73 193.68 196.62 199.57 202.51 205.46 208.41 211.35 214.30 217.25 220.19 223.14 226.10 229.05 232.00 234.97 237.95 240.94 243.95 246.97 250.01 253.09 256.20 259.34 262.48 265.53 268.28 270.21 271.15 271.52 271.71 271.83
a Series 1: Measurement of the metastable crystalline phase to the liquid phase. b Series 2: Measurement of the annealed crystalline phase to the liquid phase.
temperature was taken as twice the standard error calculated for the first coefficient of the linear fit. The small hump around 166 K is probably due to an impurity and will be the eutectic transition. The heat effect of this transition was not included in the calculation of the enthalpy of fusion. When integrated separately, the enthalpy of transition of the eutectic effect was 108 J‚mol-1. A likely candidate for the impurity is ethanol, whose melting point of 159 K is close to the transition temperature. This would give an impurity of 0.021 mol of ethanol in 0.9955 mol of ethyl undecanoate, leading to a purity for the ethyl undecanoate of 97.9 mol %, quite close to the measured value. The corrected enthalpy of fusion of ethyl undecanoate than becomes 36.16 kJ‚mol-1. The van’t Hoff plot is given in Figure 5; the calculated values of the reciprocal of the melted fraction at the equilibrium temperatures in the melt are given in Table 2. Measurements of the heat capacity of the liquid phase were extended to 365 K (series 3). Reference 10 gives a value for the melting temperature of the stable phase of 258.5 K, 0.7 K lower than our value. For the metastable phase, a melting temperature of 253.9 K was reported. This value is close to the crystallization temperature, which we measured to be 253.2 K (Figure 4). The enthalpy of fusion of the stable phase was given, assuming that the value cited was in kcal‚mol-1, as 31.9 kJ‚mol-1, about 4 kJ lower than our value. Taking into account that this value was measured
Table 4. Reciprocal of the Melted Fraction (1/F) and the Equilibrium Temperatures (Teq) in the Melt of Ethyl Tridecanoate 1/F
Teq/K
12.558 7.852 5.520 4.212 3.391 2.834 2.432 2.129 1.893 1.704 1.549 1.420 1.311 1.219 1.138
270.963 271.496 271.752 271.896 271.988 272.052 272.104 272.149 272.190 272.228 272.264 272.299 272.339 272.389 272.460
indirectly by using the freezing-point depression, the difference is reasonable. Ethyl tridecanoate (molar mass 242.4 g‚mol-1) was measured in CAL V; 4.4 g was transferred to the calorimeter vessel in a glovebox under a nitrogen atmosphere. Before closing, the vessel was evacuated, and 1000 Pa of helium pressure was admitted to enhance the heat transfer in the vessel. The experimental data are given in Table 3. The sample was cooled to 175 K, and a continuous
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Journal of Chemical and Engineering Data, Vol. 50, No. 4, 2005
Figure 6. Experimental heat capacity data for ethyl tridecanoate. O, Heat capacity and 4, enthalpy of the first measurement. b, Heat capacity and 2, enthalpy after relaxation close to the melting point.
measurement to the liquid phase was made. Between 240 K to 260 K, an exothermic effect took place (Figure 6). Next, the sample was cooled again to 150 K, heated to 269 K, and stabilized overnight at this temperature. Series 2 was measured after cooling the annealed sample to 200 K. No exothermic effects were found in this series. Calculation of the Enthalpy of Fusion. The calculation was made between 220 K and 278 K. First the heat capacity of the stable solid phase was fitted between 200 K and 220 K. This gave Cp,s(200 K to 220 K) ) {43.85 + 1.27665T/K} J‚K-1‚mol-1. The heat capacity of the liquid phase was fitted between 275 K to 300 K, the fit result being
Cp,l(275 K to 300 K) ) {401.74 + 0.3079T/K} J·K-1·mol-1 The enthalpy of fusion was calculated using the same procedure as for ethyl undecanoate. The enthalpy of fusion was found to be (40.7 ( 0.1) kJ‚mol-1. In Figure 7, the equilibrium temperatures in the melt are plotted against the reciprocal of the melted fraction. Using the van’t Hoff relation for the calculation of the impurity level, thus assuming that the impurity formed an eutectic system with the main component, resulted in a purity of 99.3 mol %, the triple-point temperature being (272.4 ( 0.1) K. The assumption that the system is eutectic seems to be reasonable because a large part of the plot in Figure 2 is linear; however, the increase in temperature near the end of the melting process might indicate that the impurity does form a solid solution with the main component. It is for this reason that we have given a larger error margin for the triple-point temperature. The melting temperature of the stable form of ethyl tridecanoate was reported by van Bellinghen10 to be 272.3 K, and for the metastable form he found a value of 269.7 K. We did not measure the melting temperature of the metastable phase. For the
Figure 7. Equilibrium temperature in the melt against the reciprocal of the melted fraction for ethyl tridecanoate. b, Data points calculated from the measurement series on the annealed sample. Calculated purity, 99.3 mol %; triple-point temperature, 272.4 K; and enthalpy of fusion, 40.7 kJ‚mol-1.
enthalpy of fusion of the stable form, he reported 10.20 cal; if we assume that this should be kcal, then his value (42.6 kJ‚mol-1), measured indirectly by the use of the freezing-point depression, is close to our value. Literature Cited (1) van Genderen, A. C. G.; van Miltenburg, J. C.; Blok, J. G.; van Bommel, M. J.; van Ekeren, P. J.; van den Berg, G. J.; Oonk, H. A. J. Liquid-Vapour Equilibria of the Methyl Esters of Alkanoic Acids: Vapour Pressures as a Function of Temperature and Standard Thermodynamic Functions Changes. Fluid Phase Equilib. 2002, 202, 109-120. (2) van Bommel, M. J. Thermodynamic Behaviour of Methyl Esters of Long Chain Linear Carboxylic Acids. Thesis, Utrecht University, 1986. (3) van Miltenburg, J. C.; van den Berg, G. J. K.; van Bommel, M. J. Construction of an Adiabatic Calorimeter. Measurements of the Molar Heat Capacity of Synthetic Sapphire and of n-Heptane. J. Chem. Thermodyn. 1987, 19, 1129-1137. (4) van Miltenburg, J. C.; van Genderen, A. C. G.; van den Berg, G. J. K. Design Improvements in Adiabatic Calorimetry. The Heat Capacity of Cholesterol between 10 and 425 K. Thermochim. Acta 1998, 319, 151-162. (5) Preston-Thomas, H. The International Temperature Scale of 1990 (ITS-90). Metrologia 1990, 27, 3-10. (6) Douglas, J. P.; Furukawa, G. T.; McCloskey, R. E.; Ball, A. F. Calorimetric Properties of Normal Heptane from 0 to 520 K. J. Res. Natl. Bur. Stand. 1954, 53, 139-153. (7) N.B.S. Standard Reference Material 720, Washington, DC, 1982. (8) Archer, D. G. Thermodynamic Properties of Synthetic Sapphire (R-Al2O3). Standard Reference Material 720 and the Effect of Temperature-Scale Differences on Thermodynamic Properties J. Phys. Chem. Ref. Data 1993, 6, 1441-1453. (9) van Miltenburg, J. C.; van den Berg, G. J. K.; van Genderen, A. C. G. An Adiabatic Calorimeter for Small Samples. The SolidLiquid System Naphthalene-Durene. Thermochim. Acta 2002, 383, 13-19. (10) van Bellinghen, R. La Conge´lation des Solutions Comme Me´thode d’Investigation de Quelques Proble`mes de Chimie Pure. Bull. Soc. Chim. Belg. 1938, 47, 640-688.
Received for review February 14, 2005. Accepted April 11, 2005.
JE050065N
