Thermodynamic Functions for Nitrosyl Chloride JOHN S. GORDON Thiokol Chemical Corp., Denville, N . J.
LANDAU
AND FLETCHER (5) have determined the vibrational fundamentals and the six anharmonicity terms. Rogers and others ( 7 ) have determined the rotational constants, and these were recently confirmed by Millen and Pannell (6). No information on vibration-rotation interaction or rotational stretching was found in the literature. Nine vibration-rotation coefficients (a,,) would be expected for a nonlinear molecule. If such coefficients were available, consideration of them might increase : C at 6000" K. (the most sensitive function) by 3 to 4%. Determination of these
coefficients is difficult-indeed, they are not available for the commonly studied gas SOz. Thermodynamic functions were computed by the IBM 650 E D P M using a program described previously (3). I n these calculations, R is 1.98726 cal. per mole degree, hc/k is 1.4388, and the Sackur-Tetrode constant K s is -7.28353 ( 2 ) .For nitrosyl bromide, the functions computed by Burns and Bernstein ( I ) were checked and found satisfactory. Data for nitrosyl fluoride have been given in another article ( 4 ) .
Table I. Thermodynamic Functions for CINO ( 9 )
T
HF - H b ,
G,Cal.
Mole-' Deg. -' 10.680 10.694 11.311 11.790 12.196
Kcal. Mole-'
Mole-' Deg.
Kcal. Mole-'
53.415 53.471 56.163 58.348 60.199
9.112 9.122 9.596 9.989 10.324
So 62.527 62.593 65.759 68.336 70.523
700 800 90P 1000 1100
61.813 63.248 64.543 65.724 66.811
10.617 10.875 11.106 11.312 11.498
72.429 74.123 75.648 77.035 78.309
12.535 12.827 13.069 13.273 13.446
4.7147 5.9832 7.2781 8.5953 9.9313
1200 1300 1400 1500 1600
67.818 68.758 69.640 70.469 71.253
11.667 11.820 11.961 12.089 12.208
79.485 80.578 81.600 82.558 83.461
13.597 13.726 13.841 13.943 14.035
11.2835 12.6496 14.0279 15.4170 16.8158
1700 1800 1900 2000 2100
71.997 72.704 73.378 74.022 74.639
12.318 12.420 12.515 12.605 12.688
84.314 85.123 85.893 86.626 87.327
14.120 14.195 14.266 14.335 14.396
18.2235 19.6391 21.0623 22.4923 23.9288
2200 2300 2400 2500 2600
75.231 75.800 76.349 76.871 77.387
12.767 12.842 12.913 12.980 13.044
87.998 88.642 89.261 89.857 90.431
14.458 14.515 14.570 14.623 14.675
25.3715 26.8201 28.2742 29.7338 31.1985
2700 2800 2900 3000 3100
77.881 78.359 78.821 79.271 79.707
13.106 13.164 13.220 13.274 13.326
90.986 91.522 92.041 92.545 93.033
14.724 14.771 14.820 14.866 14.910
32.6682 34.1429 35.6223 37.1064 38.5951
T , K. 298.15 300 400 500 600
HF - Hu,
q,Cal.
T, K
9
... 0.0197 1.1217 2.2776 3.4776
3200 3300 3400 3500 3600
80.131 80.543 80.944 81.336 81.717
13.377 13.425 13.472 13.517 13.561
93.507 93.968 94.416 94.853 95.278
14.957 14.997 15.044 15.083 15.126
40.0882 41.5858 43.0877 44.5939 46.1044
3700 3800 3900 4000 4100
82.089 82.453 82.808 83.155 83.494
13.604 13.646 13.687 13.726 13.765
95.693 96.098 96.494 96.880 97.258
15.169 15.210 15.251 15.292 15.333
47.6190 49.1378 50.6607 52.1877 53.7188
4200 4300 4400 4500 4600
83.826 84.151 84.470 84.782 85.088
13.803 13.840 13.876 13.911 13.946
97.628 97.990 98.345 98.693 99.034
15.371 15.411 15.454 15.491 15.530
55.2539 56.7930 58.3360 59.8830 61.4340
4700 4800 4900 5000 5100
85.389 85.683 85.973 86.257 86.536
13.980 14.013 14.046 14.079 14.111
99.368 99.696 100.018 100.335 100.646
15.570 15.608 15.647 15.688 15.721
62.9888 64.5476 66.1102 67.6768 69.2472
5200 5300 5400 5500 5600
86.810 87.080 87.345 87.606 87.863
14.142 14.173 14.203 14.233 14.263
100.952 101.252 101.548 101.839 102.125
15.766 15.798 i5.838 15.878 15.911
70.8214 72.3995 73.9814 75.5671 77.1566
5700 5800 5900 6000
88.115 88.364 88.609 88.851
14.292 14.321 14.350 14.378
102.407 102.685 102.959 103.228
15.951 16.002 16.027 16.066
78.7500 80.3470 81.9480 83.5527
LITERATURE CITED Table II. Molecular Constants of CINO, Cm.-' (Natural isotopic mixture) Molecular Weight = 65.465 (11
u* us
= 1800.0 =
=
Ao = Bo = Co =
82
594.9 331.5 2.847 0.19028 0.17835
-Xu
= 18.3
-Xn =
-xu
= -XI*= -Xa = =
-xm
8.0 2.0 8.0 4.9 3.9
(1) Bums, W.G., Bemstein, J.J., J . Chem.Phys. 18, 1669 (1950). (2) Cohen, E.R., DuMond, J., Layton, T.W., Rollett, J.S., Reu. Mod. Phys. 27, 363 (1955). (3) Gordon, J.S., J. CHEM.ENG.DATA6, 390 (1961). (4) Gordon, J.S., "Thermodynamics of High-Temperature Gas Mixtures and Application to Combustion Problems," Wright Air Development Center Tech. Rept. 57-33,1957. (5) Landau, L., Fletcher, W.H., J . Mol. Spectroscopy 4, 276 (1960). (6) Millen, D.J., Pannell, J., J. Chem. SOC.1961, 1322. (7) Rogers, J.D., Pietenpol, W.J., Williams, D., Phys. Reu. 83, 431 (1951).
RECEIVED for review August 7, 1961. Accepted October 11, 1961. JOURNAL OF CHEMICAL AND ENGINEERING DATA
