- Email: [email protected]
Isotherms of carbon monoxide between 0°C and 150°C and at pressures up, to 3000 atmospheres
Physica XVIII, no 2
Februari 1952
ISOTHERMS OF CARBON MONOXIDE BETWEEN 0°C AND 150°C AND AT PRESSURES UP TO 3000 ATMOSPHERES by A. MICHELS, J. M. LUPTON, T. WASSENAAR and W. DE GRAAFF 120th publication of the Van der Waals Fund Van der Waals Laboratorium, Gemeente-Universiteit, Amsterdam
Synopsis The compressibility isotherms of carbon monoxide are given for temperatures between 0°C and 150°C and at pressures up to 3000 atmospheres.
§ I. Introduction. Using the technique described in previous publications :) measurements of the P V T - d a t a of carbon monoxide have been carried out between 0 ° and 150°C and pressures up to 3000 atmospheres. An interesting feature of this gas is its similarity to nitrogen. Although carbon monoxide has a very small dipole moment of about 0.11 D, its compressibility and its thermal properties are only slightly different from those of nitrogen. Carbon monoxide was prepared by thermal decomposition of purified nickel carbonyl. By scrubbing at liquid air temperature the total concentration of impurities was reduced to about 5 ppm. § 2. The results. Nine series of measurements were carried out with normal volumes of 354.053 (b) ; 808.834 (c) ; 1242.26 (a).; 1693;70 (e) : 1719.91 (d); 1770.72 (/); 2005.69 (h); 2465.91 ([) and 2470.39 (g) cm 3. The experimental results, adjusted to equal densities and temperatures, are given in table I. Pressures are expressed in international atmospheres, densities and PV-products in Amagat units (1 Amagat unit of density is equal to 4.4643 • 10-5 mole/cm3, whereas 1 Amagat unit of P V is equal to 2269.7 joules/mole.) The temperature of the ice point is assumed to be 273.15°K. - -
121
--
122
A. M I C H E L S , J. M. L U P T O N , T. W A S S E N A A R A N D W. DE G R A A F F
I
TABLE
Carbon monoxide isotherms-- experimental data. (d and PV-values in Amagat units, P in int. atm.) No,
~t at at a6 de
b, a7 b2
aa b, b4
bs b, c1 b7 c~ b, ca
q ¢6 ¢1
dl
h Ce e2
h, ¢; d,
h Ce e3 h2
d, eL d4
h, £5
ds h,
/,
gt ee
d, h6 ~7
d7
h /, ea
d,
i,
h7
/,
d in Amagat units 18.7000 23.4392 28.1822 32.7938 37.6284 42.4398 42.4553 47.0792 50.2442 51.9234 59.5192 69.4499 80.6238 93.4936 97.0052 106.1679 ] 14.8060 118,5901 136.0050 ] 58.7050 184.2508 203.208 206.357 212.534 213.681 240.525 241,044 242.671 244.253 251.584 271.095 284,988 285.306 289.407 332.637 337.802 338.048 350.444 386.331 392.337 394.583 415.403 415.991 448.333 455.322 458.336 485.216 485.947 509.653 517.632 53-~:080 . 533.605 564.310 570.143 579.127 597.195 605.267 656.578
0°C
vv
{
25°C
e
Pv
50°C
ev
I
I
75°C
e
0.98997 0.98765 0.98557 0.98368 0,98188 0.98012 0.98012 0.97866 0.97770 0.97723 0.97513 0.97320 0.97189 0.97147 0.97[60 0.97233 0.97363 0.97435 0.97935 0.98982 1.00747
18.5124 23.1497 27.7755 32.2586 36.9466 41.5961 41.6113 46.0745 49.1238 50.7411 58.0390 67.5886 78.3575 90.8262 94.2503 I03.2302 III.7786 115.5483 133.1965 157.0894 [85.6272
1.08590 1.08471 1.08373 1.08293 1.08217 1.08164 1.08168 1.08127 1.08106 1.08104 1.08082 1.08133 1.08284 1.0857 ~ 1.08677 1.09000 1.09359 1.09538 1.10529 1.12252 1.14826
20.3063 25.4247 30.5419 35.5134 40.7203 45.9046 45.9230 50.9053 54.3170 56.1313 64.3295 75.0983 87.3027 I01.5097 105.4223 115.7230 125.5507 129.9012 150.3250 178.1495 211.5678
1.18169 1.18160 1.18172 1.18[98 1.18238 1.18288 1.18302 1.18368 1.18427 1.18454 1.18622 1.18916 1.19343 1.19967 1.20157 1.20721 1.21311 1.21595 1.23069 1.25460 1.28831
22.0976 27.6958 33.3035 38.7616 44.4911 50.2012 50.2255 55.7267 59.5027 61.5053 70.6029 82.5870 96.2189 I12.1615 I16.5585 128.1670 139.2723 144.1996 167.3800 199.1113 237.3721
1.02829
212.195
1.03646
221.472
1.17666 1.18549 1.18735
242.812 251.957 253.714
1.32408 1.33517 1.33734
273.233 283.769 285.764
1.07273 1.07535 1.07762
258.575 260.956 263.212
1.12473
304.909
1.23700 1.24005 1.25465 1.29804
300.184 302.886 315.650 351.892
1.39764 1.40130 1.41882 1.47004
339.167 342.272 356.952 398.520
1.15416 1.16330
329.289 336.667
1.34479
389.192
1.52470
441.259
PV 1.27764 1.27852 1.27975 1.28096
1.28257 1.28414 1.28425 1.28591 1.28730 1.28792
1.29144 1.29677 1.30365 1.31313 1.31602 1.32401 1.33221 1.33607 1.35558 1.38604 1.42760 1.46415 1.47073 1,48406 1.4864| 1.55151 1.55721 1.56151 1.58183 1.64076 1.68732 1.70318 1.88029
1.29623 1.29705
437.869 438.465
1.51249 1.52340
593.406 601.I08
1.88055 1.90203
856.256 871.769
2.41177 2.56334
1248.409 1363.902
1.50136
507.162
1.70412
575.655
1.55144
543.693
1.76064
617.006
1.74842
685.970
1.98087
777.169
1.88097
781.361
2.12743
883.741
2.15789
982.535
2.43010
II06.478
2.63482 2,69752
2.70269
1311.388
2.99074
1.90475 2.17163 2.21039
2.73550
1415.982
3.05223
1579.932
3.26530 3.36227
2.91655 3.31009
1556.286 1867.917
3.24604
1732.103
3,56831
3.52340 3.80284
2040.496 2271.037
4.10149 3.14900
1823.671
3.54353
2144.782 I
4.90763
3222.242
4.18453 , 2498.980 I
i
4,55839
I S O T H E R M S OF CARBON M O N O X I D E
12 3
T A B L E I (continued) Carbon monoxide i s o t h e r m s - - e x p e r i m e n t a l data. (d and P V - v a l u e s in A m a g a t units, P i n int. arm.) No.
P
gS //3 //e b, a7 b.* as b8 b, /'s b6 C1 /'7 C2 be Cs C4 Czl ¢* d,
h
C6 eS h, C./ d2
h
C8 ea h2 ds e~ d4 hs
h
e6 d~
IO0°C
75°C PV
i
150oc
125°C
p
P
27.4720
PV
23.8919 29.9675 36.0662 42.0075 48.2611 54.4986 54.5232 60.5396 64.6794 66.8732 76.8655 90.0605 I05.1052 122.7693 127.6608 140.5674 152.9457 158.4447 184:3657 219.9715 263.0364 297.527 303.495 315.413 317.618 373.177
1.37349 1.37537 1.37755 1.37983 1.38239 1.38510 1.38516 1.38794 1.38998 1.39108 1.39624 1.40389 1.41345 1.42612 1.42994 1.44017 1.45069 1.45551 1.47974 1.51662 1.56593 1.60868
25.6843 32.2376 38.8224 45.2499 52.0171 58.7834 58.8074 65.3431 69.8384 72.2296 83.1031 97.5000 I13.9577 133.3331 138.7116 152.8998 166.5479 172.6091 201.2520 240.6952 288.5239 326.897
1.46909 1.47203 1.47523 1.47849 1.48212 1.48586 1.48584 1.48971 1.49238 1.49392 1.50070 1.51062 1.52292 1.53865 1.54329 1.55590 1.56856 1.57442 ! .60327 1.64650 1.70350 1.75194
34.5032 41.5752 48.4853 55.7698 63.0596 63.0818 70.1344 74.9834 77.5694 89.3205 104.9124 122.7836 143.8539 149.7072 165.1866 180.0801 186.7106 218.0527 261.3078 313.8712 356.008
1.56456 1.56852 1.57282 1.57706 1.58175 1.58654 Ii58664 1.59148 1.59483 1.59673 1.60533 1.61740 1.63230 1.65114 1.65659 1.67153 1.68631 1.69317 1.72659 1.77612 1.84063 1.89495
29.2573 36.7649 44.3255 51.7178 59.5187 67.3324 67.3613 74.9256 80.1310 82.9077 95.5480 112.3283 131.6022 154.3710 160.6978 177.4628 193.5985 200.7932 234.8249 281.8791 339.1376 385.069
1.63175 1.63432 1.70906
346.802 349.223 411.072
1.77829 1.78133 1.86518
377.947 380.636 448.622
1.92406 1.92781 2.02070
408.928 411.936 486.029
377.890 381.404 397.963 444.802 480.866
1.71542
416.283
1.87245
454.389
2.02888
492.350
1.74357 1.80984 1.86216
438.654 490.639 530.693
1.90386 1.97757 2.03510
478.981 536.109 579.979
2.06313 2.14447 2.20761
519.050 581.355 629.142
2.07617
690.611
2.26953
754.930
2.46227
819.042
2.39459
925.104
2.61409
1009.904
2.83233
1094.217
2.61381 2.89312
I087.321 1297.081
2.84875 3.14688
1185.054 1410.850
3.08218 3.39863
1282.159 1523.718
3.55790 3.85708
1728.951 1965.772
3.83184 4.14613
1862.071 2113.088
492.912 625.454 643.428 838.968 867.218
h,
],
g, e6 d6
1181.277 1228.240
h
1451.155
3.27257
1587.903
e:, d, h,
1664.170 1740.419
3.56391
1816.357
1904.068
3.88399 .4.34890 4.44540
2072.516 2454.128 2534.514
4.19406
2237.971
4.49745
2399.862
2338.436
4.78138
2726.070
5.10926
2913.009
2722.248
4.92420
2940.708
5.28200
3154.384
h~ gm
o i•
J!7,
h
124
A. MICHELS, J. M. LUPTON, T. W A S S E N A A R AND W. DE GRAAFF
TABLE II P V - a n d P - v a l u e s of CO
o
40 80 120 160 200 240 280 320 360 400 440 480 520 560 600
PV
PV
1.00062 1.00000 0.98098 0.97192 0.97468 0.99056 1.02177 1.07122 1.14276 1.24166 1.37465 1.54989 1.77735 2.06816 2.43529 2.89350 3.45887
50°C
25°C
0°C
d Amagat units
1.09220 1.09180 1.08188 1.08272 1.09607 1.12364 1.16785 1.23187 1.32001 1.43771 1.59180 1.79043 2.04391 2.36310 2.76095 3.25131 3.84873
0
1.00000
39.2392 77.7536 116.962 158.490 204.354 257.093 319.973 397.331 494.874 619.956 782.034 992.717 1266.35 1620.36 2075.32
75°C p [/
PV 0
1.09180 43.2752 86.6176 131.528 179.782 233.570 295.649 369.603 460.067 573.048 716.172 899.320 1134.29 1435.69 1820.73 2309.24
1.18379 1.18361 1.18258 1.19315 1.21699 1.25613 1.31310 1.39154 1.49579 1.63171 1.80612 2.02752 2.30587 2.65221 3.08002 3.60226 4.23299
0 1.18361 47.3032 95.4520 146.039 200.981 262.620 333.970 418.821 522.147 650.203 811.008 1014.58 1273.06 1601.61 2017.27 2539.79
A power series of the form: P V = A + B d + Cd 2 + Zd ~ + Dd 4 + Y d s + Ed 6 + F d 7
was. fitted to each isotherm by a least-squares, technique. The coefficients of this series, given in table III, provide a convenient means of calculating P V at any density and temperature within the experimental range. The residues of these series (PVca~c,,~atea---PV*xp~ri ..... tat) are given in table IV. Since these residues are no greater than the expected experimental error (1 : 10 000) it was unnecessary to construct a supplementary deviation curve. Table II gives interpolated P V and P values for integral values of density and temperature. TABLE I I I Series c o e f f i c i e n t s for c a r b o n m o n o x i d e Coeff.
a. B. C. Z. D. y. E. F.
l0 s l0 s l0 s
10't 10t4 10 '7 l 0 st'
0°C
25°C
1
50°C
I
75°C
I
1°°°c
I
125°c
1.09220 1.18379 1.27537 1.36695 1.45853 1.00062 --0.60957( --0.387728--0.173710 +0,060129 +0.279123 +0.49924 2.74732 3.13199 3.60123 3.26131 3.26204 2.99544 2.81560 - - I . 0 8 1 9 4 / 4.59805 / 5.87388 10.7319 6.10453 --2.23472 0.029516] 2.47553 [--0.281361[--0.421188--2 60066 7.66630 1.36450 l--5.13513 / 2.52046 ] 2.46871 I 7.94417 1.15574 9.52599 /--0.953864{--0.587082[--7.37101 --7.38468 3.20596 i--1.37431 --5.60470 {--0.069931{--0.358606I 2.91011
lS°°C 1.55011 +0.70339~ 3.31613 8:29195 --0.77089~ 2.50096 0.32244~ --1.32504
1.27537 1.27542 1.28333 1.30324 1.33752 1.38796 1.45758 1.55012 1.67018 1.82374 2.01799 2.26125 2.56355 2.93625 3.39184 3.94432 4.60908
ISOTHERMS
OF CARBON MONOXIDE
125
ntegral densities
PV 0 1.27542 51.3332 04.259 60.502 ~22.074 !91.516 172.029 ~67.650 i83.597 '26.476 t04.500 27.96 ~09.40 '63.76 !08.82 '65.45
125°C
100°C
75~C
1.36695 1.36723 1.38372 1.41293 1.45733 1.51890 1.60089 1.70739 1.84297 2.01378 2.22703 2.49131 2.81666 3.21456 3,69777 4.28018 4.97718
PV 0 1.36723 55.3488 113.034 174.880 243.024 320.178 409.774 516.032 644.410 801.731 996.524 1239.33 1542.99 1922.84 2396.90 2986.31
I
1.45853 1.45902 1.48395 1.52220 1.57659 1.64918 1.74338 1.86337 2.01398 2.20144 2.43322 2.71791 3.06557 3.48797 3.99813 4.60896 5.33726
150°C
v
PV
0 1.45902 59.3580 121.776 189.191 263.869 348.676 447.209 563,914 704.461 875.959 1087.16 1348.85 1674.23 2079.03 2581.02 3202.36
1.55'011 1.55081 1.58412 1.63142 1.69569 1.77913 1.88544 2.01882 2.18443 2.38858 2.63855 2.94298 3.31234 3.75838 4.29337 4.92997 5.68470
I
d
P 0 1.55081 63.3648 130.514 203.483 284.661 377.088 484.517 611.640 764.346 949.878 1177.19 1457.43 1804.02 2232.55 2760.78 3410.82
Amagat units 0 I
4O 80 1"20 160 200 240 280 320 360 400 440 480 520 56O 600
In addition a quadratic power series was fitted to each isotherm at low densities (20 to 50 Amagat). These virial coefficients are given in table V.
§ 3. Discussion. The long-range forces due to the dipole moment of the carbon monoxide should be considered in the intermolecular field of force as has been described by several authors 2). However, for the determination of the second virial coefficient the contribution of the (small) dipole forces was found to be negligible in the temperature range considered here. Therefore the following formula a) for the intermolecular potential was assumed =
[(olr) 1 2 -
( lr6)]
The parameters e and a were determined from the B-values of the low density series, using the 1948 values of D uM o n d and C o h e n 4) for the constants N and k. The results are e = 140. 3 × 10-16 erg a = 3.793 × 10-8 cm A comparison with previous P V T measurements is given in table VI. The P V data given here are approximately the mean of those etal.,andby T o w n e n d and B h a t t e ) given by B a r t l e t t S ) The maximum differences are of the order of 2 : 1000, agreeing well
126 A. M I C H E L S , J. M. L U P T O N , T. W A S S E N A A R A N D W. D E G R A A F F T A B L E IV (PVcah:--PVe.,:p)
No.
al a2 as a4 a5 ae
b, a7
b,
a8 b3
b, b~ be
Cl
b7 C2
b, C3 C4 C~ el
dx
i, 6e g2
h,
C7
d,
J, C8 e3
h, ds g4
d, hs
A
gS
d~ h, /2
g* ee
d, hs /, g, B~
d, he
i, /, g8
d,
J,
h,
/5
d in Amagat uifits 18.7000 23.4392 28.1822 32.7938 37.6284 42.4398 42.4553 47.0792 50.2442 51.9234 59.5192 69.4499 80.6238 93.4936 97.0052 106.1679 114.8060 118.5901 136.0050 158.7050 184.2508 203.208 206.357 212.534 213.681 240.525 241.044 242.671 244.253 251.584 271.095 284.988 285,306 289.407 332,637 337.802 338,048 350,444 386.331 392.337 394,583 415.403 415.991 448.333 455.322 458.336 485.216 485.947 509.653 517.632 532.080 533.605 564.310 570.143 579.127 597.195 605.267 656.578
10~
.
0°C
25°C
50°C
75°C
+ 25 +26 +18 + 9
+10 +10 + 3 --3
d 2
--4
- - 8
+ 2 --12 --9 --12 --5 + 3 + 9 +11 + 6 +10 + 3 + 6 + 4
--
--
I
+17 +16 + 9 + 2 + 2
--
I
--4
--2 --I0 --12 --13 + I --3 --6 --5 --7 --7 --5 --2 + 3 +I0 + !.5
--7 --9 --7 --13 0 + 2 0 + 2 + 2 --5 --
1
0 --2 0 + 3
1
1
--17 --lO --14
--3 --2 + 6 + 1
--9 --7 --3 + 6
+15
--5 +13
+
--
9
---8 --8
100°C
125°C
150°C
--14 -1
w 9
+ 6 --11
--I0 --2 --3 --2 --3 0 + 4 --3 + I --5 +14 +13 + 9 + 4 --2 --II --9 --II --6 0 + 7 + 20
--23 +11 --6
--14 +I0 + 5
+II + 2 +15
1
+10
+ 7
+
--5 --2 + 4 +I0
--10 +23 +18
--20 --2 +13
+17 + 7 +I0
+12 + 2
+16
--12
--20
+48 +I0
+ 26
--13
m21
--17 +24
--4
+30
+13 +13
+22 --21
+21 --47
I
+II +
0 5 I
--II 0 --II --
I
+ I + 3 +15 + 9 + 3 --3 0 --3 + 2 0 + 6 --6 --9 --15 + 2 - - 4
+ 6 --I0 + 6 --14
--
--1 --
1
--2 + 2 --4 --2 --5 --5 --
1
+ 9 +18 +10 --
I
0 --7 --5 --4 --
1
+ I --7 --3 --5 --
I
--9 --6 0 --5 + 7 +19 +19 + 9 + 5 - - 8
--2 --9 - - 8
--6 --
1
+18
2
--9
0
- - 8
--12 --15 +22 +I0
+19 +15
--60
+
6
--9
+13
--24
+
+11
+18
+
--13
8
- - 8
1
--43
+ 26 --II
+38
--7
+
1
d
1
d54
--16
--6 + 2
+ 6 +20
+13
--15
--45
+22
+28
0 +56 +
+46
--2
+35
--11
--15
m18
--4
+55
--60 +45
--23 --4
+42
ISOTHERMS OF CARBON MONOXIDE
]2.7
with the estimates of experimental error given by these authors. Recently 7) direct measurements have been made of the ratio (PV)o..n/(PV)I ... at 22°C, yielding values of 1.000348 and 1.000358 whereas interpolation in the present data gives a ratio of 1.000369. The agreement is about 1 : 106. TABLE V Virial coefficients of carbon monoxide
Coeff I
o°c
I
25°c
I
50°c
I
75°c
100°c
I
125°c
A. 1,00062 1.09220 1.18379 1.27537 1.36695 I 1.45853 B. 103 --0.633991 --0.403802--0.1797051+0.051373 0,274208 [ 0.489526 C. 108
3.55228
3.64460
3.75360
i
3.67000
3.64751
3.67394
150°c 1.55011 0.695124 3.88893
TABLE VI Comparison of compressibility data P atm
0 I
100 400 600
Townend Bh at t
& B a r t Ie t t
c.s.
present measurements
0°C
25°C
0°C
25°C
150°C
0°C
25°C
150°C
1.0007, l.O000' 0.9710 1.2423 1.5242
1.0918 s 1.0915 1.0838 1.3565 1.6252
1.0004 1.0000 0.9745 1.2487 1.5256 2.0827
1.0920 1.0918 1.0864 1.3625 1.6317 2.1857
1.5498 1.5504 1.6151 1.9178 2.1757 2.7142
1.00062 1.00000 0.97195 1.24520 1.52175 2.07808
1.09220 1.09183 1.08536 1.35862 1.62905 2.18159
1.55011 1.55056 1.60854 1.91315 2.16898 2.70592
1000
The authors wish to express their appreciation to E. I. du Pont de Nemours & Company, Incorporated, for their support of this work and for enabling one of the authors (JML) to participate. The authors are also indebted to Dr R. J. L u n b e c k and Mr. G. J. W o 1 k e r s for the discussion and the assistance in the computational work. Received 13-I 1-51. REFERENCES 1) M i c h e l s , A., W o u t e r s , H. and B o e r , J. d e , Physica ! (1934) 587; Miehels, A., M i c h e l s , C. and W o u t e r s , H., Proc. roy. Soc. A 153 (1935) 214); M i c h e l s , A. and W o u t e r s , H., Physica 8 (1941) 923. 2) S t o c k m a y e r , W. H., J. chem. Phys. 9 (1941) 398. H i r s c h f e l d e r , J.O., Mc C l u r e , F . T . and W e e k s , I . F . , J . chem. Phys. 10(1942) 201. 3) B o e r , J. d e and M i c h e l s , A . , P h y s i c a 5 (1938) 945. 4) D u M o n d , J . W . M . and C o h e n , E . R . , R e v . mod. Phys. 20 (1948) 82, 21 (1949) 651; Phys. Rev. 82 (1951) 555. 5) B a r t l e t t , E.P., Hetherington, H.C., Kvalnes, H. M. and T r e mearne, J. H., J. Am. chem. Soc. 52 (1930) 1374. 6) T o w n e n d , D . T . A . and B h a t t, L . A . , P r o c . roy. Soc. A 134(1931)502. 7) B o t t o m l e y , G.A., M a s s i e , D . S . and W h y t l a w - G r a y , R.,Proc. roy. Soc. A 200 (1950) 201.
Februari 1952
ISOTHERMS OF CARBON MONOXIDE BETWEEN 0°C AND 150°C AND AT PRESSURES UP TO 3000 ATMOSPHERES by A. MICHELS, J. M. LUPTON, T. WASSENAAR and W. DE GRAAFF 120th publication of the Van der Waals Fund Van der Waals Laboratorium, Gemeente-Universiteit, Amsterdam
Synopsis The compressibility isotherms of carbon monoxide are given for temperatures between 0°C and 150°C and at pressures up to 3000 atmospheres.
§ I. Introduction. Using the technique described in previous publications :) measurements of the P V T - d a t a of carbon monoxide have been carried out between 0 ° and 150°C and pressures up to 3000 atmospheres. An interesting feature of this gas is its similarity to nitrogen. Although carbon monoxide has a very small dipole moment of about 0.11 D, its compressibility and its thermal properties are only slightly different from those of nitrogen. Carbon monoxide was prepared by thermal decomposition of purified nickel carbonyl. By scrubbing at liquid air temperature the total concentration of impurities was reduced to about 5 ppm. § 2. The results. Nine series of measurements were carried out with normal volumes of 354.053 (b) ; 808.834 (c) ; 1242.26 (a).; 1693;70 (e) : 1719.91 (d); 1770.72 (/); 2005.69 (h); 2465.91 ([) and 2470.39 (g) cm 3. The experimental results, adjusted to equal densities and temperatures, are given in table I. Pressures are expressed in international atmospheres, densities and PV-products in Amagat units (1 Amagat unit of density is equal to 4.4643 • 10-5 mole/cm3, whereas 1 Amagat unit of P V is equal to 2269.7 joules/mole.) The temperature of the ice point is assumed to be 273.15°K. - -
121
--
122
A. M I C H E L S , J. M. L U P T O N , T. W A S S E N A A R A N D W. DE G R A A F F
I
TABLE
Carbon monoxide isotherms-- experimental data. (d and PV-values in Amagat units, P in int. atm.) No,
~t at at a6 de
b, a7 b2
aa b, b4
bs b, c1 b7 c~ b, ca
q ¢6 ¢1
dl
h Ce e2
h, ¢; d,
h Ce e3 h2
d, eL d4
h, £5
ds h,
/,
gt ee
d, h6 ~7
d7
h /, ea
d,
i,
h7
/,
d in Amagat units 18.7000 23.4392 28.1822 32.7938 37.6284 42.4398 42.4553 47.0792 50.2442 51.9234 59.5192 69.4499 80.6238 93.4936 97.0052 106.1679 ] 14.8060 118,5901 136.0050 ] 58.7050 184.2508 203.208 206.357 212.534 213.681 240.525 241,044 242.671 244.253 251.584 271.095 284,988 285.306 289.407 332.637 337.802 338.048 350.444 386.331 392.337 394.583 415.403 415.991 448.333 455.322 458.336 485.216 485.947 509.653 517.632 53-~:080 . 533.605 564.310 570.143 579.127 597.195 605.267 656.578
0°C
vv
{
25°C
e
Pv
50°C
ev
I
I
75°C
e
0.98997 0.98765 0.98557 0.98368 0,98188 0.98012 0.98012 0.97866 0.97770 0.97723 0.97513 0.97320 0.97189 0.97147 0.97[60 0.97233 0.97363 0.97435 0.97935 0.98982 1.00747
18.5124 23.1497 27.7755 32.2586 36.9466 41.5961 41.6113 46.0745 49.1238 50.7411 58.0390 67.5886 78.3575 90.8262 94.2503 I03.2302 III.7786 115.5483 133.1965 157.0894 [85.6272
1.08590 1.08471 1.08373 1.08293 1.08217 1.08164 1.08168 1.08127 1.08106 1.08104 1.08082 1.08133 1.08284 1.0857 ~ 1.08677 1.09000 1.09359 1.09538 1.10529 1.12252 1.14826
20.3063 25.4247 30.5419 35.5134 40.7203 45.9046 45.9230 50.9053 54.3170 56.1313 64.3295 75.0983 87.3027 I01.5097 105.4223 115.7230 125.5507 129.9012 150.3250 178.1495 211.5678
1.18169 1.18160 1.18172 1.18[98 1.18238 1.18288 1.18302 1.18368 1.18427 1.18454 1.18622 1.18916 1.19343 1.19967 1.20157 1.20721 1.21311 1.21595 1.23069 1.25460 1.28831
22.0976 27.6958 33.3035 38.7616 44.4911 50.2012 50.2255 55.7267 59.5027 61.5053 70.6029 82.5870 96.2189 I12.1615 I16.5585 128.1670 139.2723 144.1996 167.3800 199.1113 237.3721
1.02829
212.195
1.03646
221.472
1.17666 1.18549 1.18735
242.812 251.957 253.714
1.32408 1.33517 1.33734
273.233 283.769 285.764
1.07273 1.07535 1.07762
258.575 260.956 263.212
1.12473
304.909
1.23700 1.24005 1.25465 1.29804
300.184 302.886 315.650 351.892
1.39764 1.40130 1.41882 1.47004
339.167 342.272 356.952 398.520
1.15416 1.16330
329.289 336.667
1.34479
389.192
1.52470
441.259
PV 1.27764 1.27852 1.27975 1.28096
1.28257 1.28414 1.28425 1.28591 1.28730 1.28792
1.29144 1.29677 1.30365 1.31313 1.31602 1.32401 1.33221 1.33607 1.35558 1.38604 1.42760 1.46415 1.47073 1,48406 1.4864| 1.55151 1.55721 1.56151 1.58183 1.64076 1.68732 1.70318 1.88029
1.29623 1.29705
437.869 438.465
1.51249 1.52340
593.406 601.I08
1.88055 1.90203
856.256 871.769
2.41177 2.56334
1248.409 1363.902
1.50136
507.162
1.70412
575.655
1.55144
543.693
1.76064
617.006
1.74842
685.970
1.98087
777.169
1.88097
781.361
2.12743
883.741
2.15789
982.535
2.43010
II06.478
2.63482 2,69752
2.70269
1311.388
2.99074
1.90475 2.17163 2.21039
2.73550
1415.982
3.05223
1579.932
3.26530 3.36227
2.91655 3.31009
1556.286 1867.917
3.24604
1732.103
3,56831
3.52340 3.80284
2040.496 2271.037
4.10149 3.14900
1823.671
3.54353
2144.782 I
4.90763
3222.242
4.18453 , 2498.980 I
i
4,55839
I S O T H E R M S OF CARBON M O N O X I D E
12 3
T A B L E I (continued) Carbon monoxide i s o t h e r m s - - e x p e r i m e n t a l data. (d and P V - v a l u e s in A m a g a t units, P i n int. arm.) No.
P
gS //3 //e b, a7 b.* as b8 b, /'s b6 C1 /'7 C2 be Cs C4 Czl ¢* d,
h
C6 eS h, C./ d2
h
C8 ea h2 ds e~ d4 hs
h
e6 d~
IO0°C
75°C PV
i
150oc
125°C
p
P
27.4720
PV
23.8919 29.9675 36.0662 42.0075 48.2611 54.4986 54.5232 60.5396 64.6794 66.8732 76.8655 90.0605 I05.1052 122.7693 127.6608 140.5674 152.9457 158.4447 184:3657 219.9715 263.0364 297.527 303.495 315.413 317.618 373.177
1.37349 1.37537 1.37755 1.37983 1.38239 1.38510 1.38516 1.38794 1.38998 1.39108 1.39624 1.40389 1.41345 1.42612 1.42994 1.44017 1.45069 1.45551 1.47974 1.51662 1.56593 1.60868
25.6843 32.2376 38.8224 45.2499 52.0171 58.7834 58.8074 65.3431 69.8384 72.2296 83.1031 97.5000 I13.9577 133.3331 138.7116 152.8998 166.5479 172.6091 201.2520 240.6952 288.5239 326.897
1.46909 1.47203 1.47523 1.47849 1.48212 1.48586 1.48584 1.48971 1.49238 1.49392 1.50070 1.51062 1.52292 1.53865 1.54329 1.55590 1.56856 1.57442 ! .60327 1.64650 1.70350 1.75194
34.5032 41.5752 48.4853 55.7698 63.0596 63.0818 70.1344 74.9834 77.5694 89.3205 104.9124 122.7836 143.8539 149.7072 165.1866 180.0801 186.7106 218.0527 261.3078 313.8712 356.008
1.56456 1.56852 1.57282 1.57706 1.58175 1.58654 Ii58664 1.59148 1.59483 1.59673 1.60533 1.61740 1.63230 1.65114 1.65659 1.67153 1.68631 1.69317 1.72659 1.77612 1.84063 1.89495
29.2573 36.7649 44.3255 51.7178 59.5187 67.3324 67.3613 74.9256 80.1310 82.9077 95.5480 112.3283 131.6022 154.3710 160.6978 177.4628 193.5985 200.7932 234.8249 281.8791 339.1376 385.069
1.63175 1.63432 1.70906
346.802 349.223 411.072
1.77829 1.78133 1.86518
377.947 380.636 448.622
1.92406 1.92781 2.02070
408.928 411.936 486.029
377.890 381.404 397.963 444.802 480.866
1.71542
416.283
1.87245
454.389
2.02888
492.350
1.74357 1.80984 1.86216
438.654 490.639 530.693
1.90386 1.97757 2.03510
478.981 536.109 579.979
2.06313 2.14447 2.20761
519.050 581.355 629.142
2.07617
690.611
2.26953
754.930
2.46227
819.042
2.39459
925.104
2.61409
1009.904
2.83233
1094.217
2.61381 2.89312
I087.321 1297.081
2.84875 3.14688
1185.054 1410.850
3.08218 3.39863
1282.159 1523.718
3.55790 3.85708
1728.951 1965.772
3.83184 4.14613
1862.071 2113.088
492.912 625.454 643.428 838.968 867.218
h,
],
g, e6 d6
1181.277 1228.240
h
1451.155
3.27257
1587.903
e:, d, h,
1664.170 1740.419
3.56391
1816.357
1904.068
3.88399 .4.34890 4.44540
2072.516 2454.128 2534.514
4.19406
2237.971
4.49745
2399.862
2338.436
4.78138
2726.070
5.10926
2913.009
2722.248
4.92420
2940.708
5.28200
3154.384
h~ gm
o i•
J!7,
h
124
A. MICHELS, J. M. LUPTON, T. W A S S E N A A R AND W. DE GRAAFF
TABLE II P V - a n d P - v a l u e s of CO
o
40 80 120 160 200 240 280 320 360 400 440 480 520 560 600
PV
PV
1.00062 1.00000 0.98098 0.97192 0.97468 0.99056 1.02177 1.07122 1.14276 1.24166 1.37465 1.54989 1.77735 2.06816 2.43529 2.89350 3.45887
50°C
25°C
0°C
d Amagat units
1.09220 1.09180 1.08188 1.08272 1.09607 1.12364 1.16785 1.23187 1.32001 1.43771 1.59180 1.79043 2.04391 2.36310 2.76095 3.25131 3.84873
0
1.00000
39.2392 77.7536 116.962 158.490 204.354 257.093 319.973 397.331 494.874 619.956 782.034 992.717 1266.35 1620.36 2075.32
75°C p [/
PV 0
1.09180 43.2752 86.6176 131.528 179.782 233.570 295.649 369.603 460.067 573.048 716.172 899.320 1134.29 1435.69 1820.73 2309.24
1.18379 1.18361 1.18258 1.19315 1.21699 1.25613 1.31310 1.39154 1.49579 1.63171 1.80612 2.02752 2.30587 2.65221 3.08002 3.60226 4.23299
0 1.18361 47.3032 95.4520 146.039 200.981 262.620 333.970 418.821 522.147 650.203 811.008 1014.58 1273.06 1601.61 2017.27 2539.79
A power series of the form: P V = A + B d + Cd 2 + Zd ~ + Dd 4 + Y d s + Ed 6 + F d 7
was. fitted to each isotherm by a least-squares, technique. The coefficients of this series, given in table III, provide a convenient means of calculating P V at any density and temperature within the experimental range. The residues of these series (PVca~c,,~atea---PV*xp~ri ..... tat) are given in table IV. Since these residues are no greater than the expected experimental error (1 : 10 000) it was unnecessary to construct a supplementary deviation curve. Table II gives interpolated P V and P values for integral values of density and temperature. TABLE I I I Series c o e f f i c i e n t s for c a r b o n m o n o x i d e Coeff.
a. B. C. Z. D. y. E. F.
l0 s l0 s l0 s
10't 10t4 10 '7 l 0 st'
0°C
25°C
1
50°C
I
75°C
I
1°°°c
I
125°c
1.09220 1.18379 1.27537 1.36695 1.45853 1.00062 --0.60957( --0.387728--0.173710 +0,060129 +0.279123 +0.49924 2.74732 3.13199 3.60123 3.26131 3.26204 2.99544 2.81560 - - I . 0 8 1 9 4 / 4.59805 / 5.87388 10.7319 6.10453 --2.23472 0.029516] 2.47553 [--0.281361[--0.421188--2 60066 7.66630 1.36450 l--5.13513 / 2.52046 ] 2.46871 I 7.94417 1.15574 9.52599 /--0.953864{--0.587082[--7.37101 --7.38468 3.20596 i--1.37431 --5.60470 {--0.069931{--0.358606I 2.91011
lS°°C 1.55011 +0.70339~ 3.31613 8:29195 --0.77089~ 2.50096 0.32244~ --1.32504
1.27537 1.27542 1.28333 1.30324 1.33752 1.38796 1.45758 1.55012 1.67018 1.82374 2.01799 2.26125 2.56355 2.93625 3.39184 3.94432 4.60908
ISOTHERMS
OF CARBON MONOXIDE
125
ntegral densities
PV 0 1.27542 51.3332 04.259 60.502 ~22.074 !91.516 172.029 ~67.650 i83.597 '26.476 t04.500 27.96 ~09.40 '63.76 !08.82 '65.45
125°C
100°C
75~C
1.36695 1.36723 1.38372 1.41293 1.45733 1.51890 1.60089 1.70739 1.84297 2.01378 2.22703 2.49131 2.81666 3.21456 3,69777 4.28018 4.97718
PV 0 1.36723 55.3488 113.034 174.880 243.024 320.178 409.774 516.032 644.410 801.731 996.524 1239.33 1542.99 1922.84 2396.90 2986.31
I
1.45853 1.45902 1.48395 1.52220 1.57659 1.64918 1.74338 1.86337 2.01398 2.20144 2.43322 2.71791 3.06557 3.48797 3.99813 4.60896 5.33726
150°C
v
PV
0 1.45902 59.3580 121.776 189.191 263.869 348.676 447.209 563,914 704.461 875.959 1087.16 1348.85 1674.23 2079.03 2581.02 3202.36
1.55'011 1.55081 1.58412 1.63142 1.69569 1.77913 1.88544 2.01882 2.18443 2.38858 2.63855 2.94298 3.31234 3.75838 4.29337 4.92997 5.68470
I
d
P 0 1.55081 63.3648 130.514 203.483 284.661 377.088 484.517 611.640 764.346 949.878 1177.19 1457.43 1804.02 2232.55 2760.78 3410.82
Amagat units 0 I
4O 80 1"20 160 200 240 280 320 360 400 440 480 520 56O 600
In addition a quadratic power series was fitted to each isotherm at low densities (20 to 50 Amagat). These virial coefficients are given in table V.
§ 3. Discussion. The long-range forces due to the dipole moment of the carbon monoxide should be considered in the intermolecular field of force as has been described by several authors 2). However, for the determination of the second virial coefficient the contribution of the (small) dipole forces was found to be negligible in the temperature range considered here. Therefore the following formula a) for the intermolecular potential was assumed =
[(olr) 1 2 -
( lr6)]
The parameters e and a were determined from the B-values of the low density series, using the 1948 values of D uM o n d and C o h e n 4) for the constants N and k. The results are e = 140. 3 × 10-16 erg a = 3.793 × 10-8 cm A comparison with previous P V T measurements is given in table VI. The P V data given here are approximately the mean of those etal.,andby T o w n e n d and B h a t t e ) given by B a r t l e t t S ) The maximum differences are of the order of 2 : 1000, agreeing well
126 A. M I C H E L S , J. M. L U P T O N , T. W A S S E N A A R A N D W. D E G R A A F F T A B L E IV (PVcah:--PVe.,:p)
No.
al a2 as a4 a5 ae
b, a7
b,
a8 b3
b, b~ be
Cl
b7 C2
b, C3 C4 C~ el
dx
i, 6e g2
h,
C7
d,
J, C8 e3
h, ds g4
d, hs
A
gS
d~ h, /2
g* ee
d, hs /, g, B~
d, he
i, /, g8
d,
J,
h,
/5
d in Amagat uifits 18.7000 23.4392 28.1822 32.7938 37.6284 42.4398 42.4553 47.0792 50.2442 51.9234 59.5192 69.4499 80.6238 93.4936 97.0052 106.1679 114.8060 118.5901 136.0050 158.7050 184.2508 203.208 206.357 212.534 213.681 240.525 241.044 242.671 244.253 251.584 271.095 284.988 285,306 289.407 332,637 337.802 338,048 350,444 386.331 392.337 394,583 415.403 415.991 448.333 455.322 458.336 485.216 485.947 509.653 517.632 532.080 533.605 564.310 570.143 579.127 597.195 605.267 656.578
10~
.
0°C
25°C
50°C
75°C
+ 25 +26 +18 + 9
+10 +10 + 3 --3
d 2
--4
- - 8
+ 2 --12 --9 --12 --5 + 3 + 9 +11 + 6 +10 + 3 + 6 + 4
--
--
I
+17 +16 + 9 + 2 + 2
--
I
--4
--2 --I0 --12 --13 + I --3 --6 --5 --7 --7 --5 --2 + 3 +I0 + !.5
--7 --9 --7 --13 0 + 2 0 + 2 + 2 --5 --
1
0 --2 0 + 3
1
1
--17 --lO --14
--3 --2 + 6 + 1
--9 --7 --3 + 6
+15
--5 +13
+
--
9
---8 --8
100°C
125°C
150°C
--14 -1
w 9
+ 6 --11
--I0 --2 --3 --2 --3 0 + 4 --3 + I --5 +14 +13 + 9 + 4 --2 --II --9 --II --6 0 + 7 + 20
--23 +11 --6
--14 +I0 + 5
+II + 2 +15
1
+10
+ 7
+
--5 --2 + 4 +I0
--10 +23 +18
--20 --2 +13
+17 + 7 +I0
+12 + 2
+16
--12
--20
+48 +I0
+ 26
--13
m21
--17 +24
--4
+30
+13 +13
+22 --21
+21 --47
I
+II +
0 5 I
--II 0 --II --
I
+ I + 3 +15 + 9 + 3 --3 0 --3 + 2 0 + 6 --6 --9 --15 + 2 - - 4
+ 6 --I0 + 6 --14
--
--1 --
1
--2 + 2 --4 --2 --5 --5 --
1
+ 9 +18 +10 --
I
0 --7 --5 --4 --
1
+ I --7 --3 --5 --
I
--9 --6 0 --5 + 7 +19 +19 + 9 + 5 - - 8
--2 --9 - - 8
--6 --
1
+18
2
--9
0
- - 8
--12 --15 +22 +I0
+19 +15
--60
+
6
--9
+13
--24
+
+11
+18
+
--13
8
- - 8
1
--43
+ 26 --II
+38
--7
+
1
d
1
d54
--16
--6 + 2
+ 6 +20
+13
--15
--45
+22
+28
0 +56 +
+46
--2
+35
--11
--15
m18
--4
+55
--60 +45
--23 --4
+42
ISOTHERMS OF CARBON MONOXIDE
]2.7
with the estimates of experimental error given by these authors. Recently 7) direct measurements have been made of the ratio (PV)o..n/(PV)I ... at 22°C, yielding values of 1.000348 and 1.000358 whereas interpolation in the present data gives a ratio of 1.000369. The agreement is about 1 : 106. TABLE V Virial coefficients of carbon monoxide
Coeff I
o°c
I
25°c
I
50°c
I
75°c
100°c
I
125°c
A. 1,00062 1.09220 1.18379 1.27537 1.36695 I 1.45853 B. 103 --0.633991 --0.403802--0.1797051+0.051373 0,274208 [ 0.489526 C. 108
3.55228
3.64460
3.75360
i
3.67000
3.64751
3.67394
150°c 1.55011 0.695124 3.88893
TABLE VI Comparison of compressibility data P atm
0 I
100 400 600
Townend Bh at t
& B a r t Ie t t
c.s.
present measurements
0°C
25°C
0°C
25°C
150°C
0°C
25°C
150°C
1.0007, l.O000' 0.9710 1.2423 1.5242
1.0918 s 1.0915 1.0838 1.3565 1.6252
1.0004 1.0000 0.9745 1.2487 1.5256 2.0827
1.0920 1.0918 1.0864 1.3625 1.6317 2.1857
1.5498 1.5504 1.6151 1.9178 2.1757 2.7142
1.00062 1.00000 0.97195 1.24520 1.52175 2.07808
1.09220 1.09183 1.08536 1.35862 1.62905 2.18159
1.55011 1.55056 1.60854 1.91315 2.16898 2.70592
1000
The authors wish to express their appreciation to E. I. du Pont de Nemours & Company, Incorporated, for their support of this work and for enabling one of the authors (JML) to participate. The authors are also indebted to Dr R. J. L u n b e c k and Mr. G. J. W o 1 k e r s for the discussion and the assistance in the computational work. Received 13-I 1-51. REFERENCES 1) M i c h e l s , A., W o u t e r s , H. and B o e r , J. d e , Physica ! (1934) 587; Miehels, A., M i c h e l s , C. and W o u t e r s , H., Proc. roy. Soc. A 153 (1935) 214); M i c h e l s , A. and W o u t e r s , H., Physica 8 (1941) 923. 2) S t o c k m a y e r , W. H., J. chem. Phys. 9 (1941) 398. H i r s c h f e l d e r , J.O., Mc C l u r e , F . T . and W e e k s , I . F . , J . chem. Phys. 10(1942) 201. 3) B o e r , J. d e and M i c h e l s , A . , P h y s i c a 5 (1938) 945. 4) D u M o n d , J . W . M . and C o h e n , E . R . , R e v . mod. Phys. 20 (1948) 82, 21 (1949) 651; Phys. Rev. 82 (1951) 555. 5) B a r t l e t t , E.P., Hetherington, H.C., Kvalnes, H. M. and T r e mearne, J. H., J. Am. chem. Soc. 52 (1930) 1374. 6) T o w n e n d , D . T . A . and B h a t t, L . A . , P r o c . roy. Soc. A 134(1931)502. 7) B o t t o m l e y , G.A., M a s s i e , D . S . and W h y t l a w - G r a y , R.,Proc. roy. Soc. A 200 (1950) 201.