PRESSURE - VOLUME ~ TEMPERATURE RELATIONSHIPS OF GASEOUS NORMAL DEUTERIUM AND THREE HYDROGEN-NITROGEN MIXTURES DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doetor of Philosophy in the Graduate School of The Ohio State University By Mex Trzeciak, B.S. The Ohio State University 1954 Approved by: Ee i. Sohnston, AdviserTABLE OF CONTENTS PART A - INTRODUCTION I. Equations of State for Gases eseeeee 2 II. Intermolecular Forces for Real Gases and the Lennerd-Jones Potential .... 7 PART B - P-V-T STUDIES OF THE HYDROGEN-NITROGEN MIXTURES AND DEUTERIUM I. Preparation of the Hydrogen-Nitrogen MAxtures .cccececceeccceccescosseess 15 II. Deuterium Purity seseessecesseceeees 15 TIT. Apparatus ss-eeeee 16 IV. Operating Procedure .ssseseseseveree 26 V. P-V-? Relationships of Hydrogen- Nitrogen Mixtures sesesssesessesesee 33 VI. P-V-T Relationships of Deuterium ... 37 PART C - APPLICATIONS OF THE DATA I. Applications of the Lennard-Jones Potential to the Mixtures .....++++- 105 , RRAIt. III. Prediction of the Second Viriel Coefficients of the Mixtures .+...+. Application of the Lennard-Jones Potential to the Deuterium Data .... Pugacities and Free Energies of Hydrogen, Nitrogen, and their WAXtUPOS secsececeecceneerereeserees Solubility of Hydrogen in Liquid Nitrogen ... ACKNOWLEDGEMENTS sessrececsceesscsccceerecee AUTOBIOGRAPHY ceecceceececesccccccceceecoees ii 123 127 140 143, 144PART A: INTRODUCTION The purpose of this investigation is the determination of accurate pressure-volume-temp- erature relationships of pure gaseous normal aeut- erium and three hydrogen-nitrogen mixtures. Pre- viously in this laboratory the P-V-T relationships of pure hydrogen, pure nitrogen and one hydrogen- nitrogen mixture had been determined?. Physical + 4A. S. Friedman, Ph. D. Dissertation, The Ohio State University (1950). constants are calculated from the P-V-T data and those of the mixtures are compared with those of the pure components.I. EQUATIONS OF STATE FOR GASES In 1662 Boyle observed changes in vol- ume of air with changing pressures and recorded his observations in what is known today as Boyle's Law: constant temperature the volume of a definite mass of gas is inversely proportional to the pressure," that is, V at » or PV = constant. The variation of the volume of a gas with tempera- ture was observed by Gay-Lussac and independently by Charles. Their law states that the volume of a gas is directly proportional to its temperature, that is, VT. From these laws, the ideal gas law, PV = RT can be derived. The ideal gas law can also be derived from simple kinetic theory”. This law was found 2. Mayer and Mayer, Statistical Mechanics (1940). to apply only at high temperatures and low pres- sures. It was necessary, in order to explain the behavior of gases at low temperatures and high pres- sures, to develop an equation of state which would account for the deviations from the ideal gas law. One of the best Imown equations of state is the Ven der Waal's equation,(P= -S)v- bd) eer. This equation makes allowances for the attractive and repulsive forces between the molecules of the gas. The correction term applied to the pressure, +r , is a measure of the attractive force of the molecules. The volume correction term b takes into account the finite size of the melecules and its effect 1s to reduce the effective volume of the mol- ecules. It is equal in magnitude to about four times the actual volume of the molecules. At ex- tremely low pressures V is large, which makes the term + very small, and b becomes negligible com- pared with V. The equation then reduces to that for the ideal gas, PV = RT. Although the Van der Waal's equation gives a satisfactory qualitative representation of the behavior of gases, 1t fails quantitatively in some aspects. It 1s found that the constants a end b change with temperature and b changes with pressure. R. Clausius (1880) made the following proposal to compensate for the change in a with temperature:[P+ awit] (vi-b) = RT. The introduction of four constants, a, bd, c, and R, into an equation of state mkes it difficult to deal with mathematically. For this reason the Clausius equation has found relatively little ap- plication. Berthelot eliminated the constant c from the Clausius equation, expanded it, and mod- ified it to include the eritical constants. His expression is PV = RE [a+ 2 tH a-6 3] 128 Rh T v This equation holds best at low pressures and is only applicable over 4 limited range. The Dieterici equation of state, -o% ps See e RTV , 4s © modification of the Van der Waal's equation in thet it introduces the concept of a difference in potential energy existing between the molecules in the bulk of a gas and those near the walls. At relatively low pressures, the exponential of theDieterici equation can be expanded and then reduced to the Van der Waal's equation. Various writers on the kinetic theory have suggested that the deviation of gases from the ideal gas lew was caused in part by molecular "ag- gregetion," which includes association involving valence or analagous forces as well as that asso- ciation resulting from prolonged contact between molecules on collision. The equation of Beattie and Bridgeman 1s an attempt to include this cor- rection and takes the form, Pe = (v + B) - + > where AP ACL + Ss BoB (2- 2B); -s- This equation has five empirical constants, Ao, Bos & by 0, in addition to R. The moat general equation of state re- lating pressure, volume, and temperature is that of H. Kamerlingh-Onnes®@ 3. H. Kamerlingh-Onnes, Comm. Phys. Lab. Univ. Leiden, No. 71, (1901). PV ERD + BOT) P + C(r) P* + Di) P+ or PV = RP + Am + Sp + Dep + ere The virial coefficients, Bir), C(T), DiT), are functions of temperature only. This is the equa- tion of state which has been used for expressing the results of this research. Tables XIV, XXVII, XL, and IXVI list the virial ceefficients of the mixtures and deuterium.IL. INTERMOLECULAR FORCES FOR REAL GASES AND THE LENNARD-JONES POTENTIAL The partition function for a system of N independent particles includes only the transla- tional energy and is given by HY ang ae [info Senate tacearkessd re with the Hamiltonian expression, —h 2 2 pe #(p,a) = ih 2 (ee Bre Be Integration of the expression for Q yields ae gh {aagen— vf”. For a system of N dependent particles, however, the expression for the Hamiltonian must be modi- fied to include the potential energy of attraction and thus becomes a H(p,a) = gi > (ae + B+ Br er) eetand the partition function is, €or) i gp ftsrgar of [fo da,+** ddsy sb [emer v] a The volume dependent part of the expression is called the configuration integral and can be solved by making the approximation that the potential en- ergy can be represented as the sum of the inter- actions €(r,;) between all possible pairs of mol- ecules 4 and j, depending only on their distance apart, rj; E(r) = €(r) . q With this approximation the expression for the con- figuration integral is, = Ee /4T ae [onfe ” dx, dy,dz, + AxyATydZ~ Mayer and Mayer? derive an approximate solution for the configuration integral:a, ev" fr-ar & | > where ° Lew, ran [o AT 24) v* ar The expression for the pressure of a ges in terms of the configuration integralt is 4. 8S. Glasstone, Theoretical Chemistry, Chapter IX. given by, ) AR (2-44) - The equation of state of a gas in the virial form? may be written as, « Jk r) ct. eee . ped (as Ae + e+ ) At moderate pressures whero gas imperfection 1s small, the third virial coefficient may be neglected so that,10 we (+ aD) and if the two expressions for pressure are set equal to one another, the second virial coefficient can be expressed in terms of the potential energy ef interaction; Ber) = -33N ~> p> Ey Mo 2-01X s-O1XE y0IXd z-01X D a dust (2"98 + €°TT) @# AUNLXIN NADOULIN-NFOOUGAH YO SLNAIOIAAAOD TVINLA AIX GTAVL52 P-V-T DATA FOR HYDROGEN-NITROGEN MIXTURE #5TABLE XV HYDROGEN -NITROGEN MIXTURE #3 DATA (79.3 : 19.7) RT = 24,616.5 T = 299,99°K Run No, Pressure PV 15 0.9922 24,621 14 3, 8446 24,668 13 7, 4503 24,691 12 11,4670 24,753 6 22,0088 24,911 5 41,2335 25,173 4 59,8516 25,401 131 No Good 3 84,4953 25,762 2 111, 4508 26,170 84 No Good 1 141, 8323 26,639 23 170, 2084 27,174Run No, 105 104 103 100 101 99 132 102 133 45 48 47 46 TABLE XVI HYDROGEN-NITROGEN MIXTURE #3 DATA RT = 22,414,1 (79.3 : 19.7) Pressure 2, 8680 5,0988 8, 5059 12, 0820 19,9219 29,4699 43,0136 60, 4188 87,7447 94,9770 125, 0060 157, 2587 180, 0483 T = 273,15°K PV 22,442 22,471 22,515 22,555 22,657 22,772 22,956 23,184 23,570 23,662 24,095 24,587 24,954 54TABLE XVII HYDROGEN-NITROGEN MIXTURE #3 DATA (79.3 +1927) RT = 20,513,7 T = 249,999 K Run No, Pressure PV 1 3, 4805 20,548 110 6.0274 20,572 109 8.9362 20,608 108 13, 2862 20,657 107 19,7100 20,725 106 29, 1394 20,829 112 50, 3343 21,093 140 No Good 134 72, 6058 21,379 44 81,3726 21,473 4l 110, 6683 21,881 40 137, 8532 22,276 43 159, 5883 22,607 42 185, 4703 23,004TABLE XVIII HYDROGEN-NITROGEN MIXTURE #3 DATA RT = 18,469,1 Run No, 114 113 115 116 117 118 (79.3 : 19.7) T = 225,08°K Pressure 3.2851 6, 1693 8.7802 13,2463 19,6786 28, 8660 PV 18,502 18,527 18,552 18,596 18,649 18,742 56TABLE XIX HYDROGEN-NITROGEN MIXTURE #3 DATA RT = 16,420 Run No, 55 119 120 54 53 52 51 50 49 135 39 38 37 36 35 (79.3 319.7) Pressure 2.8733 4.0212 4.0394 5, 1873 8, 2183 12,4613 20, 1007 30,0301 50, 2583 73,5022 81,0087 109.9762 139, 0900 163, 1527 191, 5283 T = 200,11°K PV 16,435 16,456 16,451 16,450 16,471 16,501 16,556 16,633 16,810 17,050 17,124 17,454 17,824 18,173 18,594 57TABLE XX HYDROGEN-NITROGEN MIXTURE #3 DATA RT = 14,362 Run No, 62 126 61 122 121 128 60 59 127 58 57 56 136 34 33 32 31 30 (79.3 19.7) Pressure 2.8302 3.1028 5, 1821 6.6559 No Good No Good 8.0344 12, 1101 No Good 18, 9685 29,9942 50, 1584 73,0382 81,3124 109. 4757 137, 4998 162, 3398 191, 4460 T = 175,03°K PV 14,378 14,381 14,377 14,397 14,386 14,403 14,431 14,485 14,607 14,798 14,866 15,152 15,489 15,825 16,254 58Run No, 125 123 69 68 67 125 66 65 64 63 29 28 25 27 26 TABLE XXI HYDROGEN-NITROGEN MIXTURE #3 DATA RT = 12,313 (79,3 : 20,7) Pressure 9.9910 12,9653 19,6091 30,1815 49,9289 80, 2485 110, 9847 136,7241 165, 3425 196, 3022 T = 150,06°K PV 12, 306 12,308 12,316 12,293 12,297 12,299 12,294 12,293 12,303 12,355 12,524 12,784 13,073 13,452 13,921 59TABLE XXII HYDROGEN-NITROGEN MIXTURE +3 DATA RT = 10,2597 (79.3 : 20.7) Pressure 2.7640 5.2482 8.8355 11,9277 19,6275 29,8759 49,0208 82, 1353 111, 1734 138,4141 170.7553 200, 4546 T = 125,03°K PV 10,232 10,214 10, 187 10,165 10,112 10,060 10,012 10,069 10,273 10,574 11,031 11,528 60TABLE XXIII HYDROGEN-NITROGEN MIXTURE #3 DATA (79.3 : 20.7) RT = 8207,4 T = 100,2°K Run No, Pressure PV 70 2,762 8154.6 2B 4, 6806 8115.3 72 6.7959 8080.4 71 9.2751 8025.2 77 12, 4096 7973,2 14 14, 8882 7924,0 75 22,6736 179549 76 29, 8483 7685.9 TABLE XXIV HYDROGEN-NITROGEN MIXTURE #3 DATA (79.3 : 20,7) RT = 7386,3 T = 90,04°K Run No, Pressure PV 78 3.1327 7297.7 83 5.3947 7245.0 719 7.2469 7195.4 82 9.7827 7128.9 80 13, 1382 7047.5 81 No Good 61TABLE XXV HYDROGEN-NITROGEN MIXTURE #3 DATA (79,3 : 20.7) RT = 6565,8 T = 80,02°K Run No, Pressure PV 86 No Good 129 2,0542 6492.1 130 No Good 85 3, 1683 6446.9 87 No Good 88 4,3124 6401.2 89 5, 1873 6371.2 90 6.3798 6328.0 91 No Good TABLE XXVI HYDROGEN-NITROGEN MIXTURE #3 DATA (79,3 : 20,7) RT = 6155,2 T= 75,01°K Run No, Pressure PV 138 6921 6121.6 95 1, 0065 6104.4 139 No Good 98 No Good 96 1, 4678 6077.1 137 17151 6050.3 94 No Good 93 No Good 92 No Good25,000 20,000}— 4 deap9-0—-0- 225.03 °K 18,000 Pv (cc. - atm.) 10,000. 100.02°K 90.01°K 80.019 K 750K 5,000 -- 4 ISOTHERMS FOR HYDROGEN-NITROGEN MIXTURE #3 (79.3: 20.7) 1 6 30 #0 ao ido PRESSURE (atm.) Fig. IV64 00z- 02's g*9S- To°sL S*66- 99°F Sh'ge- 20°08 0*e- oz*F B°Sz- 10°06 oF s6°E ¥8°SI- 20 *00T gtk 0*eE- £€°9 sg"e 0°s- €0°S2T s*8 o°re- 09°S L2°€ 2t- 90*0ST Le 6°82- 02z°s L0°€ Lye €0°SLT ovlt L°S2- or’ 16° Lg T1002 - “- ste 68°2 s" 80°SZ7z s*er Pele Be°z 18°2 Tut 66 "6bZ P°Il 0°9- vI'e Shee vel et ST°ELZ st 0's- oF oz over 66 "662 3 Po po zo 33 Mo OIX a s0UXE r01X T z-01X 9 q dwar ¢# FUNLXIN (z*0z ? €°62) NADOU LIN-NADOUGAH YOA SLNAINIAAAOD TVINIA IIAXX FIdvLTf DATA FOR HYDROGEN-NITROGEN MIXTURE 65 ‘4TABLE XXVIII HYDROGEN-NITROGEN MIXTURE *4 DATA (33.8 : 66.2) RT = 24,616 T = 299.99°K Pressure PY 3.1991 24, 638 5. 0774 24,655 7. 6818 24, 669 10. 3436 24, 689 12. 9584 24,703 15.5728 24,722 25.6112 24,780 43,2423 24,916 71.2942 25,181 99. 3660 25,508 129. 4595 25,899 158. 1181 25, 321 188. 9677 26, 827Run No, 62 61 60 59 58 57 56 55 50 54 51 52 53 TABLE XXIX HYDROGEN-NITROGEN MIXTURE “4 DATA RT = 22,414 (33,8 : 66,2) Pressure 3.2589 5, 1087 71,3307 10, 3665, 15,7010 26,9345 43,3406 75, 0897 No good 106, 8820 127, 8755 158.4140 188, 2138 T = 273,15°K PV 22,423 22,420 22,425 22,438 22,454 22,497 22,574 22,796 23,098 23,347 23,789 24, 223 67TABLE XXX HYDROGEN-NITROGEN MIXTURE “4 DATA Run No. 106 105 104 103 102 101 100 99 107 108 109 110 RT 20, 514 (33.8 : 66.2) Pressure 3. 1081 5.2748 7.5795 9. 8455 15, 1518 24. 5202 39. 5890 69, 8302 99. 1063 129. 0467 158. 6879 196. 8611 T = 249.99°K Eva 20,510 20, 507 20, 501 20, 501 20,498 20, 497 20,511 20, 628 20, 828 21,118 21, 487 22, 067 68TABLE XXXI HYDROGEN-NITROGEN MIXTURE *4 DATA (33.8 : 66.2) RT = 18,469 T = 225.08°K Run No. Pressure Pv 3 3.0179 18, 450 72 5. 0888 18, 438 7 7. 5894 18, 425 70 9. 8444 18, 409 69 14, 9469 18, 384 68 24. 0687 18, 337TABLE XXXII HYDROGEN-NITROGEN MIXTURE “4 DATA Run No. 49 48 47 46 45 44 43 42 38 39 40 41 ql 112 113 14 RT 16, 421 (33.8 : 66.2) Pressure 3. 0565 4, 8768 7, 5182 9. 4453 14, 6664 24, 1660 40.5165 69. 9244 No Good No Good No Good No Good 89, 8253 119. 0357 153, 8649 192. 0260 T 200. 11°K Ee 16, 382 16, 355 16, 326 16, 302 16, 240 16,135 15, 987 15, 838 70TABLE XXXIII HYDROGEN-NITROGEN MIXTURE *4 DATA aaa 35 34 33 32 31 30 29 28 24 25 26 27 RT 14, 363 (33.8 : 66.2) 3. 0870 5.1704 7. 5559 10. 1517 15. 3294 24, 8909 39.9657 70. 5334 99. 3037 No Good 159. 4923 188. 9951 T = 175.03°K Pv 14, 288 14, 251 14, 205, 14,146 14, 038 13, 850 13, 583 13, 200 13, 067 13, 498 13, 973 72TABLE XXXIV HYDROGEN-NITROGEN MIXTURE “4 DATA (33.8 : 66.2) RT = 12,313 T = 150. 06°K Run No. Pressure PV 78 3.0014 12, 204 77 4.9978 12,134 16 7.4222 12,048 75 9.4628 11,979 74 14. 8180 11,795 79 24. 0466 11, 483 80 39. 4315 11, 004 81 69. 4732 10,274 65 89. 4984 10, 035 66 97, 8454 9,989 67 No Good -- 121 118. 5925 10, 033 122 153. 5655 10, 482 123 189. 7291 11,240TABLE XXXxv HYDROGEN-NITROGEN MIXTURE #4 DATA (33.8 : 66.2) RT = 10,257 T = 125.03°K Run No Pressure PV 23 3. 1566 10,077 22 5.2816 9,965 21 7.7271 9, 828 20 10. 2847 9, 682 19 14. 9705 9,416 18 25, 0850 8, 827 17 No Good -- 16 No Good -- 63 No Good -- 64 No Good -- 12 No Good -- 13 No Good 7 14 No Good oo 15 No Good --TABLE XXXVI HYDRGOEN-NITROGEN MIXTURE #4 DATA (33.8 : 66.2) RT = 8,206 T = 100. 02°K Pressure Pv 2. 0037 8, 025 3. 0790 7,923 5. 0056 7, 748 7.3559 7, 521 10. 5748 7,175 No Good S10 TABLE XXXVIT HYDROGEN-NITROGEN MIXTURE “4 DATA (33.8 : 66.2) °. RT = 7,386.2 T = 90,01 kK 7415 TABLE XXXVIII HYDROGEN-NITROGEN MIXTURE *4 DATA (33.8 : 66.2) RT = 6,565.8 T = 80,01°K Run No. Pressure PV 96 No Good oo 95 No Good Bo 97 0. 6983 6, 442 94 0. 8215 6,427 98 0. 9423 6,411 116 0.7232 6, 443, 93 No Good -— 117 1, 0361 6,397 TABLE XXXIX HYDROGEN-NITROGEN MIXTURE *4 DATA (33.8 : 66.2) RT = 6,155 T = 75.01°K ee patil 0. 7168 5,990 0. 8029 5,973 No Good --25,000) 20,000] 15,000 Pv (cc.-atm ee Looe oe 16 T 299.997" 27318" 4 GAID-o—o- 225.08°K oo OOO Pm abo 150.0474 125.03°K ISOTHERMS FOR HYDROGEN-NITROGEN MIXTURE #4 (33.8:66.2) ° 40 80 120 160 PRESSURE (atm) Figure V17 922- To"s2 008 ‘or 991- 20°08 o0z- 0029 €1t- ¥0°06 oL- Oorr 06- 20°00T 9% 06- 9°S 6902 o*ss- €0°S2T s*92 6°98- ovtt STII o'se- ¥0 "OST €°6z 9°F8- ¥S “Or 088 o°ze- 20°SLT s*0€ gthe- 8L°6 TL 9°zt- 11002 -- oa 6 £99 T*9- 80°S2Z zor 8°IS- 26°8 erg ere 66 *6rZ 6°9- z"8e- Z*Or sz ez gt "eLz 9°be- 8Ez- Lm oo 6°9 66 667 > > > p> 39 Wo Ol XL s-OIXT y-0IX a 2-01X 9 a dwar (299? 8*€¢e) b+ FUNLXIW NFOOULIN-NFDOUGAH YOA SLNAIOIAAAOD TVIMTA IX FTavL-T DATA FOR DEUTERIUM 78Run No 159 36 38 157 167 158 35 166 39 19 37 233 234 417-R 439-R 322 321 413-R 412-R 411-R TABLE XLI DEUTERIUM DATA RT = 24,617,0 Pressure 1, 0382 1,0584 1, 8713 1, 8877 1.9027 2,8197 3.1093 3.3705 4, 3273 6.0940 6, 3452 10, 8053 16,0971 16,9055 18, 3330 24,5460 36,249 68, 539 76,7271 96.9677 130, 877 157,271 184, 338 T = 300°K PV 24,652 24,629 24,631 24,652 24,626 24,656 24,677 24,671 24,665 24,711 24,703 24,772 24,853 24,856 24,892 24,974 25,075, 25,555 25,718 26,003 26 , 500 26,927 27,345 79Run No, 163 161 32 164 12 1 10 165 160 TABLE XLII DEUTERIUM DATA RT = 22,414,6 Pressure 1.9662 2, 8923 2.8969 3.9448 40399 5.2759 7, 2838 7.3704 10, 4208 16, 1469 20, 0953 24,9814 T = 273, 16°K PV 22,428 22,472 22,479 22,469 22,492 22,522 22,521 22,510 22,550 22,634 22,687 22,756 80Run No, 18 42 232 41 15 231 25 230 406-R 40 28 13 405-R 404-R 400-R 311 403-R 399-R 402-R 401-R TABLE XLIII DEUTERIUM DATA RT = 20,514,2 Pressure 3.3126 4, 6606 4.7174 8, 4742 10,4001 12,5255 14,0404 17,7452 18,228 18,5269 20, 5386 25,1678 35, 892 52,713 68,089 99,0624 103, 228 133,746 169, 503 192, 100 T =250°K PV 20,549 20,578 20,565 20,607 20,638 20,668 20,710 20,734 20, 747 20,752 20,793 20,832 20,939 21,166 21,375 21,815 21,878 22,301 22,848 23,142 81Run No, 173, 172 171 170 169 168 TABLE XLIV DEUTERIUM DATA RT = 18,462,8 T =225°K Pressure 1, 8988 4.4761 7.6536 10,0370 14,4220 25, 8600 PV 18,476 18,508 18,547 18, 582 18,634 18,774Run No, 179 229 228 178 227 177 176 226 225 175 438-R 224 174 397-R 437-R 395-R 314 313 394-R 393-R 392-R 391-R RT TABLE XLV DEUTERIUM DATA = 16,411,3 T = 200°K Pressure 1.9145 1.9701 4.7261 5, 1152 7.6912 8.0819 10, 5108 10, 8566 13, 8262 14,6910 17,827 20, 5629 25,2700 35,409 52,406 69.946 70.7931 98,8135 99,457 138, 146 167.637 195,773 PV 16,436 16,440 16,469 16,471 16,489 16,499 16,525 16,526 16, 556 16,570 16,585 16,633 16, 683 16,756 16,957 17,173 17,221 17,557 17,555 18, 080 18,512 18,908 83Run No, 182 223 183 181 185 186 187 188 222 184 390-R 180 389-R 388-R 387-R 316 315 386-R 385-R 384-R 383-R, TABLE XLVI DEUTERIUM DATA RT = 14,3599 Pressure 1, 9661 1.9775 2,0090 2,0132 3.9909 4.0280 6.6720 8, 4600 11, 3636 14,4175 18, 388 24,6025 35,609 52,143 69, 604 70, 8289 98,7119 101,231 138, 461 165, 309 192,197 T =175°K PV 14,366 14,371 14,382 14,378 14,409 14,395 14,422 14,439 14,461 14,494 14,514 14,585 14,669 14,850 15,047 15,077 15,398 15,421 15,905 16,263 16,649 84Run N 154 195 196 153 155 156 152 151 194 150 149 148 147 318 369-R 368-R 367-R 366-R TABLE XLVIII DEUTERIUM DATA T = 10,257.1 Pressure 1,0233 1,0326 1,0781 1.9489 1,9883 2.0519 3.0361 5.0977 5, 8124 9,2494 11,4244 16, 8821 23,7940 61,6330 101, 584 133,797 166,697 200. 989 T = 125° PV 10,267 10,257 10,246 10,264 10,265 10, 268 10,259 10,273 10,269 10,271 10,285 10,303 10,335 10,558 10,924 11,292 11,726 12,208 86Run No. 154 195 196 153 155 156 152 151 194 150 149 148 147 318 369-R 368-R 367-R 366-R TABLE XLVIII DEUTERIUM DATA T = 10,257.1 Pressure 1,0233 1,0326 1, 0781 1,9489 1, 9883 2.0519 3,0361 5.0977 5, 8124 9.2494 11,4244 16, 8821 23,7940 61,6330 101, 584 133,797 166,697 200.989 T = 125°K PV 10,267 10,257 10,246 10,264 10,265 10, 268 10,259 10,273 10, 269 10,271 10,285 10,303, 10,335 10,558 10,924 11,292 11,726 12,208 86Run No. 52 53 207 55 220 54 205 197 219 51 218 206 365-R 203 436-R 362-R 361-R 360-R 358-R, 364-R, 363-R TABLE XLIX DEUTERIUM DATA RT = 8,205,7 Pressure 29721 1.9856 3.7614 5.7065 5.7405 8.4190 8, 5037 10,9848 11,7933 15,0742 17,9401 18, 5825 19,003 22,3206 31, 186 35,031 51,689 69.945 135,488 160,764 187,459 T = 100°K PV 8,198 8,194 8,194 8,187 8,186 8,174 8,183 8,172 8,171 8,154 8,160 8,158 8,155 8,154 8,152 8,154 8,196 8,274 8,886 9,217 9,605 87Run No, 49 48 47 202 46 45 201 200 44 349-R 351-R 348-R 354-R 353-R. 357-R. 356-R 352-R 347-R TABLE L DEUTERIUM DATA RT = 7,385.1 Pressure 0.9251 2.0526 2.8754 4,7848 4.9427 7.9212 10, 1613 16,2379 16,7701 17,003 26,224 42,873 51,638 71,201 88, 056 102, 950 134,717 166,155 T =90°K PV 7,385 7,370 7,364 7,354 7,359 7,333 7,319 7,286 7,282 7,271 7,243 7,225 7,224 7,294 7,397 7,504 7,859 8,309 88Run No, 128 127 209 126 125 124 208 123 303-R 122 423-R 302-R 433-R 428-R. 305-R 422-R 301-R 432-R 409-R 421-R 310-R TABLE LI DEUTERIUM DATA RT = 6,564, 5 Pressure 0.9899 1, 8975 1.9724 2.9813 4,6953, 7.5074 80584 12,4312 16,240 19,1429 26,142 33,210 35,389 45,280 53,109 64,659 81,803 101,960 139,977 168, 194 196,691 T = 80°K PV 6,554 6,551 6,530 6,533 6,513 6,483 6,478 6,424 6,397 6,370 6,320 6,281 6,272 6,219 6,207 6,212 6,277 4,430 6,905 7,353 7,855 89Run No, 133 132 131 217 130 216 346-R 129 339-R 426-R 341-R 338-R 430-R. 345-R 427-R 343-R 342-R 408-R TABLE LII DEUTERIUM DATA RT = 6,154,3 T =75°K Pressure 2.9040 4.6717 7, 0889 11,1421 13,3476 16,2431 18,377 19,7624 26, 568 37,939 43,891 50,778 53,672 66,757 68, 869 85,023 101,009 190,223 PV 6,115 6,089 6,056 6,000 5,973 5,937 5,908 5,897 5,822 5,736 5,698 5,671 5,667 5,663 5,671 5,738 5,881 7,258 90Run No, 142 215 140 139 138 214 251 213 333-R 136 335-R 249 424-R 334-R 332-R, 326-R. 292 331-R 291 330-R 325-R 324-R 407-R TABLE LIII DEUTERIUM DATA RT = 5,661.9 Pressure 00, 9307 1,9902 3.0504 4, 8048 6, 8194 9.0552 12, 3582 14, 7572 16, 932 20, 0411 25,935 25,9358 45,920 54,378 61,244 68, 883 71,7193 86,801 100, 4767 104, 547 141,472 172, 181 205,524 T 69°K PV 5,656 5,629 5,614 5,579 5,549 5,500 5,448 5,406 5,361 5,329 5,235 5,234 5,023 5,008 4,980 4,994 5,007 5,076 5,236 5,273 5,843 6,407 7,014 91Run No, 212 246 245 145 144 121 2il 143 248 210 120 247 314-R 312-R 317 290 320-R 289 322-R 319-R 316-R 315-R TABLE LIV DEUTERIUM DATA RT = 5,251.6 Pressure 1.8978 1.9636 2.8996 3.1129 4.6340 8.3067 11,5907 14,7485 17,8132 21,0881 23,5340 24,1518 38, 850 48, 260 52,433 67,9063 83,272 99,2813 106, 004 146, 272 177,204 189, 481 T =64°K PV 5,215 5,197 5,198 5,189 5,152 5,067 5,003 4,935 4,872 4,807 4,776 4,755 4,518 4,419 4,407 4,365 4,440 4,665 4,760 5,475 6,064 6,312 92Run No, 119 17 116 118 115 244 114 243 113 274 273 272 271 270 269 266 265 262 TABLE LV DEUTERIUM DATA RT = 4,923.4 Pressure 0.9324 2.0732 4.1652 5.2195 7.8768 10, 5610 14,9743 18, 1303 25,0405 30,8797 41,4416 51,4376 61,1615 82,6859 109, 1498 142, 7684 172, 9615 204, 8889 T =60°K PV 4,896.1 4,865.3 4,817.2 4,784.1 4,721,3 4,666,3 4,537.5 4,460.1 4,290.0 4,179.1 3,995.4 3,887.1 3,849.3 4,007.0 4,417.8 5,053.8 5,661.2 6,305,2 93Run No, ee 110 109 108 107 309 288 308 307 306 258 276 264 261 DEU' RT = 4513,1 TABLE LVI TERIUM DATA T = 55°K Pressure 1.9511 3.0451 5.3261 8, 2730 13,0715 31,7460 42,2606 50, 0498 60,5185 79, 8639 106, 4287 138, 3427 173, 4134 200, 9276 PV 4,446.0 4,408, 2 4,333.3 4,240.7 4,087.9 3,505, 3 3,272.9 3,190.9 3,189.4 3,402.8 3,920.2 4,559.4 5,293.1 5,866.5 94Run No, 105 104 103 102 101 100 99 305 304 287 284 283 282 257 256 255 TABLE LVII DEUTERIUM DATA RT = 4,102.8 T = 50°K Pressure 1,0007 2,0041 3, 3012 5.0215 8.9291 14,4311 22, 8428 31,1585 41,7391 42,9688 52, 2869 62,2928 82,6227 96, 5261 129, 5683 152, 8356 PV 4,049.1 4,019.6 3,963.7 3,899.9 3,738.5 3, 506,0 3,137.3 2,786.4 2,505.1 2,508, 5 2,478.3 2,622.1 3,004.6 3,306.6 4,022.8 4,525.3 95TABLE LVIII DEUTERIUM DATA RT = 3,692,6 Pressure 0.9620 1.9646 3.3791 6.6868 8.2301 13,2552 20,6481 30,2534 36,8750 42,1544 62,0883 84,6304 137, 2308 170, 2368 203, 5344 T =45°K PV 3,633.5 3,592,3 3,519.6 3,358.6 3,281.4 2,991.6 2,520,3 1,873.5 1,759.6 1,795.1 2,177.8 2,693.5 3,888.6 4,601.6 5,303.4 96Run No, 88 90 87 86 241 91 89 300 285 278 279 277 267 254 253 252 TABLE LIX DEUTERIUM DATA RT = 3,282.3 Pressure 0,9949 1, 8385 2, 8415 4, 8084 9.9023 13, 5233 19,2188 22,9729 35, 0222 50.4786 62,0842 83,9497 103, 5991 138, 2007 163, 3156 203, 4421 T = 40°C 97 PV 3,221.2 3,156.1 3,110.3 2,975.2 2,629.3 2,303.0 1,397.6 936.8 1,221.7 1,608, 1 1,895.9 2,420.7 2, 882.1 3,651.1 4,192.9 5,035.7Run No. 69 68 67 66 65 64 63 Run No, 70 74 62 73 72 TABLE LX DEUTERIUM DATA RT = 3,123.1 Pressure 0, 5396 0, 8887 1, 8557 3, 1002 4, 8186 7.9017 11, 8207 T = 38,06°K TABLE LXI DEUTERIUM DATA RT = 2,885.9 Pressure 1.0329 1, 8771 3.0399 4.9215 7, 5476 T = 35.17% PV 3,089.5 3,068.9 2,991.4 2,920.5 2,797.8 2,544.7 2,143.4 9899 TABLE LXII DEUTERIUM DATA RT = 2,504.4 T = 30,52°K Run No, Pressure PV 61 0, 5220 2,458.6 60 0.9890 2,414.3 59 2.0292 2,308.7 238 2.8155 2,231.3 TABLE LXIII DEUTERIUM DATA RT = 2,232,8 T = 27,21°% Pressure PV 78 0.4777 2,181.5 17 0.9928 2,121.4 76 1.4796 2,066.3 75 2.0209 1,994.9 TABLE LXIV DEUTERIUM DATA RT = 1,929.9 Run No, Pressure PV 19 0, 3148 1,890.6 80 0.4219 1,875.7 82 0.5925 1,851.8100 TABLE LXV DEUTERIUM DATA T = 1,667.4 T = 20,32°K Run No, Pressure PV 84 0.1212 1,658.6 83 0, 2253 1,640, 3101 200% 25,000 + oK ae 2501 Pv (cc.-atm)| 20900 | 15,000- 1 1 1 1 40 80 120 160 Pressure (atm.) Figure ¥Z102 ok ost 10,000 c- atm) 2raix 2352%K( b 203eKh cae Baie) seoerk \, 1 1 L 1 40 80 120 160 Pressure (atm) Figure VILos*T T*e- SOL* €5°s s*tl- 00°08 06° SP°e- To°t 98°F OrL- 00°06 oe” 0°z- oct SI'p e*e- 00 ‘00T P29" Lee se'r 69°E 9°2 00 "sz se° S*e- orl zere 1°9 00 "OST BT ZT LI"e 8°8 00°SLT Sze 20° T°ot 00*00z ert L6°Z 6°IT 00*szz Sovr $6°2 S°2T 00*0sz 00°T €6°% ove 9T Ele 56° 262 e°er 00"00€ 329 po pry > 33 Mo 101 XA s-01*F y-0Ix a 201% 9 a dway WATYALNAd YOd SLINFIOIAAIOO TWIUIA TAXI aIdvL104 0°2bI- ze "oz o*s2t- zs "ez O*Sot- T2°LZ s*L8- zg *0€ wz ss O°TL- LI*GE o'r 6th 0°29- 90°8¢ Ort 09°F Oe "F- 08 "8T E°19 00*Or TIT 'e PETTI- 59° 99°21 0°0S- 00°st 69TE "0- 06"zI Sze"Po ozt ‘Ft 8"0r- 00*os sT€*o 18°F 9ze"t- $09°6 s9°ze- 00°ss 6258 *O- 96°21 €20°e- LS2°OT 8°92 00°09 zece"o BIs*e ¥SG5°~ 9Sz°L ze "ez- 00°69 zL°T £0 °F S6r° 56°9 9S °8T- 00°69 09°T PETER zes* org S°hI- 00"S2 2? > > P? 39 Mo OLX s-01XE »01XC 2-019 @ dwar (penurqw09) IAXI @IaVL105 PART C: APPLICATIONS OF THE DATA I. APPLICATION OF THE LENNARD-JONES POTENTIAL TO THE MIXTURES In Part A - II the relationship between the second viriel coefficient and the intermolecular force constants was established; Bir) = 2/37a* Fly) , B(7) and y are functions of temperature only. This makes it possible to find values of n, m, A, and B which would make Br) agree with the observed result. A value of 6 may be assigned to m in order to adequately describe the force of attraction‘. If log /F(y)/ 1s plotted against arBur lee y on one sheet of graph paper and log /B(7)] against log T on another transparent106 sheet with the same scale, the two curves may be superimposed if a proper selection for the value of n 4s made. Tho shape of the curve determines mand n®. The horizontal and vertical transform- ations necessary determine the values of A, B, and 4, and hence, x, andé, since log /Bm/ - log /Fly)/ = log 2/s7 a? , and log T - log y = log (-&/c) t 2 log 2. The values of log /Bi7)/ vs log T for the three hydrogen-nitrogen mixtures were plotted and were found to fit a curve with the values m= 6 and n = 12 (see Figure VIII). ‘The hor- izontel and vertical transformations were obtained and from them the intermolecular force constants were calculated. The values are listed in Table IXVII. It 4s possible to calculate the Boyle temp- erature from a Imowledge of the values of the intermolecular force constants‘. Table LXVIIIMixture #2 #8 #4 Mixture #2 #3 #4 Hy % TABLE LXVII a(R), (8) (se Ae) (deg) 3.82 4.29 84.9 3.16 3.55 45.9 3.57 9 4.01 74.6 TABLE LXVIII T (°K) T (°K) (exptl.) (computed) 296 291 156 157 258 256 104 326 107 é (ergs) x 10% -11.72 - 6.34 =10.50 T (°K) (linear combination) 301 150 251108 liste a comparison of the Boyle temperatures thus computed with the Boyle temperatures obtained from Plots of the experimental Bir) 's vs temperature for the three mixtures. Included in the table are estimated Boyle temperatures obtained from a linear Combination of the Boyle temperatures of the com- Ponent gases. Figures IX, X, and XI give the mutuel Potential energies of hydrogen-nitrogen pairs as @ function of their molecular separation as deter- mined from the equation, ery ¢ fEBy (BR) - = a(BYYbog IF c ° T a T 109 Log IBI vs. log T of the hydrogen - nitrogen mixtures fitted to a 6, l2 Lennard-Jones plot. ° e He-Ne Mixture # 2 © He-Ne Mixture #3 © He- No Mixture #4 0 Os 10 -2 logy Fig. vraz€ (7) x 10'S (ergs) 110 +2-— ° 2 a 6 Mutual potential energies 8t— of He-Ne pairs of Mix- ture 22 as a function of their separation. tor— 2 4298 ° 2 6 to€ (7) x 10! (ergs) Mutual potential energies of He-Ne pairs of Mixture £3 as a function of their separation 8 7 (A) Fig. x€ (7) x 10! (ergs) 112 401k Mutue! potential energies of He-Ne pairs of Mixture #4 as a function of their separation. 6 7 (A) Fig. xx113 II. PREDICTION OF THE SECOND VIRIAL COEFFICIENTS OF THE MIX TURES Several attempts have been made to relate the second virial coefficient, B(7), of a mixture to those of the pure constituents!9»20,21,22,25,24,25 19. J. E. Lennard-Jones and W. R. Cook, Proc. Roy. Soc. (London), A115, 334 (1927). 20. R. D. Kleemen, J. Franklin Inst., 206, 511 (1928). 21. W. E. Deming and L. E. Shupe, J. Franklin Inst., 208, 389 (1930). 22. A. J. Perkins, J. Chem. Phys., 5, 180 (1937). 23. J. 0. Hirschfelder and W. E. Roseveare, J. Phys. Chem., 43, 15 (1939). 24, J. A. Beattie and W. H. Stockmayer, J. Chem. Phys., 10, 473, 476 (1942). 25. J. A. Beattie, Chom. Rev., 44, 141 (1949). with varying degrees of sucess. Most recently, D. White” of this lab- 26. D. White, A. S. Friedman, ahd H. L. Johnston, The Forces of Interaction in a Solution of Two Non-Polar Gases: Hydrogen and Nitrogen (in prep- aration).114 oratory has made a proposal concerning a relation- ship between the force constants of the mixture and those of the pure components. The second virial coefficient of the mixture is related to those of the pure compon- ents by, BO) mix M a a Ny Br), + 2N, Ny Bir), + NP Bir, where N, = mole fraction of hydrogen Nz = mole fraction of nitrogen B(7), = second virial coefficient of hydrogen B(7k, = second virial coefficient of nitrogen Bi, = the interaction virial. From the P-V-T data produced in this laboratory for hydrogen, nitrogen and hydrogen-nitrogen Mixture #1 (59.56% Hy, 40.44% N,)" white calculated the interaction virial from the equation, We ye B(7)_ = —Bitimia = Ni BO), = No BI 3 ea .115 He found that the hydrogen, nitrogen, and the hydrogen-nitrogen mixture fitted a 6,12-Lennard~ Jones potential curve (m= 6, n= 12). The values obtained for the interaction virial, B(7),,, were plotted against temperature and were also found to fit a 6,12-Lennerd-Jones potential curve. Using the value of B(r)z obtained in this manner, he computed the second virial coeffi- cients of mixtures at 0.2, 0.4, 0.6, and 0.8 mole fractions of hydrogen. These mixtures were found to fit a 6,12-Lennard-Jones plot. Table IXIX compares the second virial coefficients, Bcr),,, , obtained by this method with those obtained experimentelly in this research. The data from this table are plotted in Figures XII, XIII, and XIV. There is fair agreement between the theoretical B(7).,,,.'8 and the experimental BCr),,;,.18 at temperatures above 125°K. This may be @ satisfactory method of estimating the second virial coefficients of mixtures to a first approx- imation 1f the second viriel coefficients are mown for the pure gases and one mixture. It may be noted that the critical temperature of nitrogen116 $*2eI- gee- etLe- $*9S- 8 °66I~ bIe- se 6°LIL- 99T- 6*le- Sh °9E- L°6LI~ 0z- 08 9°96- €lI- 9*ez- 8°Sz- 6 °6FI~ 8sI- 06 0°6L- 06- okt #8 °8T- €°62T- Tet~ oot bezs- 0*ss- T*L- 0°8~ 8°28- ¥ 98 S2t 6*zE- o'se~ s"0- 2tI- L°9¢- 6Ls- ost 9*0z- 0*22- zr Lp 'e L*6E- 0 *6E- SLI Z°1I- 9°2T- o*s L°9 5 °92- 2*92- o0z gtr 19° T‘Or $6 LeLt- s"9T~ zz 2*0- wete orzt Ut Otrt- 9%6- 0sz re €°% Z°E1 PEL ZI 9°s~ oe OT Elz 9°9 69 €°6I o*eL BIH 9°0 00 Getceq)g — (dxa)g (et0am)gq — (I9dxa)q Gercem)g (84x) gq THYB EL by 2IMIXIW THEOL Cy ANTI TH%HEUEZ, 2M XI (Ho).L XIXI 3Tavi40 Boyle temperature = 296°K: -40 -t iy S. T B (the second virial coefficient) vs. temperature for hydrogen-nitrogen mixture #2 (11.3: 887) —o— Experimental B --O— Theoretical B 80 120 60 200 240. 280 TK) Figure XIT118 Boyle temperature = 156° K -1ok 20k a 3 é 3-30b 8 (The second virial coefficient) vs. 2 temperature for hydrogen - nitrogen ao mixture 23 (79.3: 20.7) & 6 —O— Experimental B --O--Theoretical B ~50} — =e 1 —1 ——1 80 120 160 200 240 280 T (°K) Figure XIII40- 119 40 B (cc/mole) “—— Boyle temperature = 258°K B (the second virial coefficient) vs. temperature for hydrogen- nitrogen mixture“4(33.8: 66.2) —o— Experimental B --O-- Theoretical B ————_L 4 4 -L —1_ 60 200 280 T (°K) Figure xv120 is 126°K and the gas imperfection increases greatly with decreasing temperature below 125°K. White computed values of (- € /c) and Yr, for his theoretical mixtures and found that, (eM) nig e N,Ceofr) + NCeo fc), , To mix. = Npro(1) + Nyro(2) . His results are listed in Table LXX. The agreement between the force constants of his "theoretical mixtures" and those derived from the linear com- bination of the pure components 1s good. However, the actual experimentgl values obtained from the data of this research for the mixtures do not give results which agree with those obtained using his combination rule. Table LXXI lists a comparison between the values from the experimental data and those from the linear combination rule. Although there is agreement between these two methods as to the order of magnitude of the intermolecular force constants, the agreement in general is poor compared with that which white calculated for his "theoretical mixtures." An ex- planation of White's apparent good agreement be-121 tween the calculated molecular force constants and those from the linear combination rule seems to lie in the fact that there is accidental good agreement between the force constants of Mixture #1. All the other "theoretical mixtures" are com- pletely dependent upon the values of this mixture. It is seon in Table LXXI thet Mixture #3 (Ny, = .2074) agreos well with White's linear combination rule proposal. When P-V-T data are lacking for mix- tures, it seems that, for a first approximation, one may apply the linear combination rule of White and obtain approximate intermolecular force con- stents. These in turn can be used to obtain the second virial coefficients of the mixtures.a, 1.00 0.80 0.60 0.4044 0.20 0.00 a 0.8870 0.6617 0.2074 Na 0.00 0.20 0.40 0.5956 0.80 1.00 My 0.1130 0.3383 0.7926 TABLE LXX (seo) (-€/e) n (mix) (cale) (mix) (deg) (deg) (8) 95.93 4.15 82.60 82.88 3.98 70.15 69.83 3.86 58.34 57.07 3.71 43.65 43.74 3.53 30.69 3.35 TABLE LXXI (-6fc) (= & fe) x (exptl) (calc) (mix) (deg) (deg) (R) 84.9 88.6 4.29 74.6 73.9 4.01 45.9 44.2 3.55 122 Tp) (cale) (a) 3.99 3.83 3.67 3.51123 IIL, APPLICATION OF THE LENNARD-JONES POTENTIAL AION OF THE LENNARD-JONES POTENTIAL TO THE DEUTERIUM DATA A treatment similar to that described for the mixtures has been made for deuterium with the results thet, % = 3.30 8 do = 2.94 8 - = 4.61 X10 ergs (+ @/c) = 33.42 deg. Figure XV is a plot of log /Bcr/ vs log T with the appropriate transformation coordinates. From the Plot of Bi) vs T, Figure XVI, the Boyle temperature was determined to be 112°K. The variation of poten- tial energy with intermolecular distance is plotted in Figure XVII.Log IF (y)| ee ° -2.0 Log IBI vs. Log T of Deuterium fitted to a 6, I2 Lennard - Jones plot Fig. xv125 ax aunbi4 (Me) L Og a os OO! winisajnag 404 Banfo1adwiay “SA (4UB!91}J909 |OI4IA Puooas ayj) g Modll = aNjosadway ajAog - Oo 09! - 4 Obl- 4 0d!- O0OlI- O8(a;0uW99) g 409- + Ob- 4 O2g- 40 Ode€ (7) x 10'S (ergs) Potential energies of D2 molecules as a function of their separation127 IV. FUGACITIES AND FREE ENERGIES O HYDROGEN, NITROGEN, AND THEIR MIXTURES The data available for treatment in this section consist of P-V-T relationships of pure hydrogen, pure nitrogen, and four hydrogen- nitrogen mixtures of the following compositions: Mixture Ny, #8 0.7926 #1 0.5956 #4 0.3383 #2 0.1130 The date for hydrogen, nitrogen, and Mixture #1 are teken from the dissertation of A. S. Friedman*. The data of Mixtures #2, #3, and #4 are part of this dissertation. Lewis and Rendall?” made the assumption 27. G.N. Lewis and M. Randall, Thermodynamics and the Free Energy of Chemical Substances, 1923. that, “until further experiments have been made we shall assume that every gaseous solution is a per-128 fect solution, and therefore that, at a given temp- erature and total pressure, the fugacity of each constituent is proportional to its mol fraction or to its partial pressure." Gibson and Sosnick”® tested the Lewis nN 28. Gibson and Sosnick, J. Am. Chem. Soc., 49, 2172 (1927). and Randall rule with mixtures of ethylene and argon at room temperature and found that at about 50 atmospheres, the error of the fugacity calculated by the rule ranges from zero to 20%. At 100 atmos- pheres the errors ranged from zero to about 100%. Merz and Whittaker® also made a test 29. Merz and Whittaker, J. Am. Chem. Soc., 50, 1522 (1928). of the rule with hydrogen-nitrogen mixtures at one temperature and found similar deviations. In this research the fugacities of hydrogen, nitrogen, and their mixtures were deter- mined by plotting « vs P and integrating graph- feally as indicated in the equation,129 P = 1 log f = log P - ay fac, where = BL. a4 Vv. The fugacities obtained in this manner are listed in Table LXXII. 30 Johnston” has developed a rigorous 30. H. L. Johnston, Abstracts of the Portland, Ore. Meeting (1948), A.C.S., page 33-0. equation relating the fugacities of the components in a gaseous mixture to the fugacity of the mixture: P in P - de famdP = In f= Nin (2) + win (2) re min, ® Nzin * ¥, in which £,(P) = fugacity of solute component in the gas mixture under total pressure P; = BL : Am BB = Vinin Vimix. = molal volume of the gas mixture. Johnston's equation is differentiated with respect to mole fraction and is used to deter-130 TABLE LXXII FUGACITIES OF HYDROGEN-NITROGEN MIXTURES #2, *3 AND *4 (°K) P(atm, ) Mixture #2 Mixture #3 Mixture *4 £ f £ 300 10 10,00 19.05 10, 03 25 25,02 25,32 25,17 50 50.14 51,32 50,70 75 75,44 78,04 76,63 100 101,01 105, 52 103, 02 150 153,31 162.96 157, 68 200 207.78 224,02 215,09 250 10 9.95 10,05 9.99 25 24,71 25,33 24,97 50 48,95 51,34 49,94 75 72,84 78,11 75,02 100 96.55 105,67 100, 32 150 144,08 163,43 152, 13 200 192,78 225,02 206,22 200 10 9.84 10, 23 9.92 25 24,04 25,25 24,53 50 46,33 51,07 48,27 75 67,21 77,55 71,43 100 87,01 104, 82 94,23 150 125,07 161,97 139,73 200 163,23 223,25 186, 57 150 10 9.54 9.99 9.72 25 22,20 24,93 23,28 50 39,26 49,87 43,53 75 52,22 75,04 61,40 100 62.76 100,65 77,72 150 82,23 153,91 108, 50 200 102,51 211,24 139, 89131 mine fugacities of hydrogen and nitrogen in the mixture: (BB) oe om ote nt - (in fx) . +™ ( a ),* Qa x ae he Since, a : % (BRA). + 2 (BRte) = 0, Cores then, mn ,(P) = an { (1 = 3, at] -%, on . Similarly, an £,(?) = an f (2 - dE} = My (Sate) |. ON Log fm was plotted against mole fraction and from the slope of the curve the fugacitie: 3 of the components in the mixtures were determined. Lewis and Randall's assumption that f, = N,£2 was tested by determining the ratio132 f; Ai £2 at various pressures. These ratios are listed in Tables LXXIII and LXXIV. Figures XVIII and XIX contain plots of the ratios. It is seen from the curves that Mixture #2 at 300°K behaves as a perfect solution to within 0.2%, whereas at 200°K it deviates from the Lewis and Randall rule by 30% at 200 atmospheres pressure. The Boyle temperature of Mixture #2 1s 296K. The free energies of the hydrogen, nitrogen, and their mixtures were calculated by multiplying log f by 2.3026 RT, end ere listed in Tables LXV, LXXVI, LXXVII, and LXXVIII.133 TABLE LXXIII DATA FOR TEST OF LEWIS AND RANDALL RULE Temp = 200°K Pressure Mixture *1 Mixture #2 Mixture #3 Mixture #4 (atm. ) (&:/N1f,°) (G/N14°) (6/Nih°) (&)/Nf°) 10 1,002 1,016 1,001 1,007 25 1,006 1,036 1,001 1,015 50 1,014 1,089 1,003 1,034 75 1,019 1,132 1,004 1,049 100 1,016 1,234 1,004 1,060 150 1,036 1,244 1,006 1 200 1,040 1,294 1,008 1144 TABLE LXXIV Temp = 300°K Pressure = Mixture *1 = Mixture #2 Mixture #3 Mixture #4 (atm, ) (f2/Naf2°) (f2/Nef2°) (t2/N2f2°) (£2/Naf2°) 10 1,003 1,000 1,005 1,002 25 1,007 1,001 1,010 1,002 50 1,013 1,001 1,019 1,005 75 1,018 1,001 1,025 1,006 100 1,021 1,002 1,030 1,008 150 1, 038 1,002 1,050 1,012 200 1,033 1,001 1,061 1,0164 Trax 3YNOI4 (‘wyd) aunsseig 002 0S! 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Mo0st = duay (2}0uW/29) ‘N3DOUGAH AO SAIOMANA FAUNA FHL TITAXX] aTavL140 V.__ SOLUBILITY OF HYDROGEN IN LIQUID NITROGEN OE EDROGEN IN LIQUID NITROGEN The ideal solubility of hydrogen in liquid nitrogen can be calculated from the satur- ation pressure, p®, with the aid of Raoult's lew, P, = N,p2. p, is the partial pressure of hydrogen over the liquid. At liquid nitrogen temperatures (64°K to 125°K), hydrogen is above its critical temperature and its saturation pressure cannot be measured experimentally. In this case the satur- ation pressure, which has no clear physical moan- ing, can be obtained by extrapolating the marly straight line in the plot of log p va 1/f. Then the reciprocal of the value thus obtained, with Pz, © 1 atmosphere., is a measure of the solubility of the gas in the liquid, N, = 1/p%. The vapor pressure data on hydrogen obtained in this laboratory! was used to determine the values of the saturation pressures in the liquid nitrogen range. Table LXXIX lists the ideal solubilities at various temperatures. Fuga- cities were also calculated at the saturation pres- sures. Solubilities calculated from these are also141 listed in this table. The differences between the two are not great enough to overcome the error arising from deviations from Raoult's law.142 TABLE LXXIX IDEAL HYDROGEN SOLUBILITIES 5 fat oo Na, x100 Np,x 100 T(°K) palatm) —pz=1 fat p from Tom 1/p° f/f 69 119 997-101 - 84 +99 75 141 +998 = 129 +71 +77 80 159 +999 153 63 = 65 90 194 +999 206 +52 48 100 228 1,000 259 44 39 125 303 -- -- +33 oc143 ACKNOWLEDGEMENTS I wish to acknowledge my indebted- ness to Dr. H. L. Johnston, my preceptor. Special thanks are due him for having accepted me as one of his students and for having proposed this prob- lem. Through his generous efforts he has obtained funds to support this project. Thanks are due to the many persons in the cryogenic laboratory who had in one way or another assisted in the accomplishment of this research, more particularly to Dr. David White who directed the project and Mr. Lester Cox, shop foreman, who maintained the apperatus.144 AUTOBIOGRAPHY I, Max Trzeciak, was born in Cleveland, Ohio, January 29, 1921. I received my elementary and secondary education in the public schools of Glevelend. ly undergraduate training was received at The Ohio State University from which I obtained the degree Bachelor of Science in Chemistry in 1948. Between my sophomore and junior years I spent 39 months in the U. 8. Army. During most of my time in the army I was a blood chemist in a hospital laboratory. Upon receiving the B.S. degree I en- tered the Graduate School of The Ohio State Univ- ersity end remained a graduate student working as @ research fellow in chemistry under Dr. H. L. Johnston until January, 1952. At this time I Joined Dr. Johnston's private firm working in the eryogenic field for one year. I was appointed a research assistant in the Chemistry Department and held this position while completing the require- ments for the degree Doctor of Philosophy.