Physical Properties of anol-Water J
CECIL CARR AND JOHN A. RIDDICIC Commercial Solaents Corp., Terre Haute, Ind.
The value of Wojciechowski ( 2 3 ) appears to be the most reliable. The methanol was prepared and tested in accordance with the method developed by S~vietos1au;skiand co-workers ( 1 7 - I Q ) . The temperature was measured with a platinum resistance thermometer furnished by Meycrs ( 1 Z ) of the National Bureau of Standards. It is believed that Wojciechowski's ($2)value for the boiling point should be 64.51 * 0.01 C. This conclusion is based on the fact that there are no accepted criteria of purity for methanol, as is evidenced by the disagreement of physical data in the literature, and that Wojciechowski based his criterion of purity on one test, the differential of the boiling and condenaing temperatures established by Swietoslawski (18). The methanol used for his measurement was undoubtedly of a high state of purity. The density data for water, given in Table 11, are those evaluated by the National Bureau of Standards (IS). These are the standard data used for calibrating apparatus used for density determinations.
Because of frequent requests from co-worlrers for information on common physical properties of methanolwater solutions, i t was considered advisable to determine the properties most requested. The density-composition and specific gravity-composition relationships were determined at about 10% composition intervals for methanol and water at 25", 30°, and 40' C. The shrinkage and viscosity-composition relationships were also determined at 25" C. The results were plotted on large scale graph paper and the relationships tabulated for 1% intervals in composition from 0 to 100%. The values for 20' C. were not determined because reliable data are available. These tables make available to laboratory workers and engineers the physical property-composition relationship in easy-to-use tabular form.
O
ETHANOL, as wood alcohol, was one of the first organic chemicals to find extensive laboratory and industrial use. The development of synthetic methanol has made the compound one of the most widely used solvents and chemicals. As methanol is often used as an aqueous solution, it is surprising that estensive data on the physical property-temperature relationship are not available in the literature for the methanol-water system. Many of the data on methanol and water and the methanolwater system in the literature are given a t 60" F., a temperatuie which often is not convenient to use. This paper presents data a t more commonly used temperatures for density, specific gravity, shrinkage, and viscosity. The data presented are considered to be those that will be most useful to chemical engineers and chemists. In order to evaluate published data on physical properties of the methanol-water system, and to determine additional phyaical property-temperature relationship data, the corresponding physical data for methanol and water must be evaluated. This is necessary because water is used as the standard for the calibration of most apparatus used to determine the more common physical properties. The most reliable physical property data for methanol are required to evaluate the purity of the methanol used and for the use of methanol as a secondary standard.
TABLE11. PHYSICAL PROPERTIES OF METHAXOL AND WATER Methanol Property Value Ref. Normal b.p., O C. 6 4 . 5 1 fZB) d t l d p , C./mrn. 0.0331
Viscosity, op. 0,"
15
200
0.8031 0.6405
0,5945
d d d
d 20,200 ..... d 250 0.5825 d 30' 0.5142 d 40" 0.4478 a Calculated from ( $ 0 ) . Interpolated from ( X I ) , graphical method. Calculated from (21). d Calculated from data in ( d ) , p. 136.
1.7921 1.1404 1,0050 1.0000 0.8937 0.8007
0.6560
Water
Rcf. Definition a
(2)
(2) (8) (2) (8)
(2) (1)
A mathematical and graphical analysis of density data for methanol indicated that those of Timmermans and HennautRoland ( 2 1 ) are probably the most reliable. The viscosity of water is not known to an exactness comparable to the other physical properties given in Table 11. Bingham and co-workers (9-4) made an extensive study of the viscosity data of outstanding workers. They evaluated the data and established the most probable values for the viscosity a t various temperatures. The reference temperature has been established at 20" C. and the viscosity of water calculated to be 1.0050 centipoise at this temperature. More recently Coe and Godfrey (7) reevaluated the viscosity data and substantially agreed with Bingham and co-workers. The American Society for Testing Materials ( I ) has defined the viscosity of water a t 20" C. as 1.005 cp. Cannon and Fenske
EVALUATION OF BOILING POINT, DENSITY, AND VlSCOSITY DATA FOR METHANOL AND WATER
The values obtained by different workers for the normal boiling point of methanol vary considerably. Some of these values are given in Table I. BOILISGPOINTS OF METHAXOL TABLE I. REPORTED Normal Boiling W d p Point, C. ca. 760 h l m . Hg 64,509 0.0331 337.74O K . a t 7 6 4 mm. 6 4 . 4 5 calcd. from d t / d p ( 2 8 ) 64.65 9.035 64.46 64.53
c.
Value 100.000 0.0368
Reference (22) (16)
(#I) (6) (8)
692
* INDUSTRIAL AND ENGINEERING CHEMISTRY
March 1951
693
% weight to % volume Eight
TABLE 111. DETERMINED COMPOSITION-DENSITY RELATIONSHIP OF METHANOL-WATER SYSTEM of Constituents, Grams
Methanol
4.235 15.972 4.637 9.380 9.327 35.155 46.795 15.460 15.495 13.428 71.244 15.768 19.395 88.982 19.396 102.101 19.401 19.421 117.900 32.395 39.074 136.817 38.a59 39.430 157,529 39.620
Methanol plus water
42,242 159,136 45,266 47.641 47.063 175.533 156.099 51,254 50.812 34.145 178.151 38,974 38,695 177.528 38.521 169.995 32.271 30.341 16a.176 43-821 49,909 170.987 48,199 44.866 175.068 43.611
Methanol Composition
MeOH % w. X d of soh. at tl d MeOH a t t1 MeOH % v. a t tl
Density, G./MI.
(Air Wt.), yo 10.03 10.04 10.24 19.69 19.82 20.03 29.98 30.16 30.49 39.33 39.99 40.46 50.12 50.12 50.35 60.06
250 0.98010
30'
...
0,97411
...
0.96219 0.94601
0.95725 0.94043
0.94890 0.94827 0,93284
... ...
...
0,92807
0.92i30
0 . 97998
0.97817
40'
% volume to yoweight
...
MeOH % v. a t ti X d MeOH at t1 sp. gr. of soh. at t l l t i X d H20 a t t l MeOH yo w.a t ti
0.96537 0.96514
...
where % w = per cent by weight, yo v. = per cent by volume, d = den-ity, and tl = some designated temperature. 0.93081 0.91186 0,90830 0.90059 Tables relating only density and per 0.90830 0.90059 o 9ii49 ... ... cent by w i g h t , or specific gravity and 0 . a8642 0.87869 per cent by volume, are generally un60.12 0,89070 ... ... satisfactory because of the often oc64.01 0.88160 70.11 0.86289 0,85465 ... curring need of interrelated data. Be73.93 0.85792 ... ... cause the density or specific gravity78.29 0.84694 80.02 0.83783 0.82940 composition data are considered the 80.62 0 . Siioo ... ... basic information for the methanol0.82156 87.88 water system, the moRt useful table 89.98 o.si083 0,80226 90,85 0.8i330 would correlate density, specific gravity, .. 100.00 0,7a674 o.7Siso 0 . 77iag and composition by weight and by volume. Tables of other properties relating the composition and the prop(6) used this value in their work, developing a practical routine erty would, therefore, correspond with the tables giving amount viscometer. Rossini and co-workers ( 1 4 ) also accepted the value of material per unit of capacity. of Bingham and Jackson a t 20' C. as adopted by the American Society for Testing TABLEIV. DENSITY,SPECIFICGRAVITY, AND COMPOSITION RELATIONSHIP OF MIXTURES OF Materials as their standard. METHANOL AND WATERAT 25" C. METHANOL- WATER S Y S T E M
Methanol,
%
*
Methanol-water s o l u t i o n s m a y b e c h a r a c t e r i z e d by density and specific gravity. Density as used herein refers t o grams per milliliter. Specific gravity is a dimensionless number and is the ratio of the density of the substance a t temperature tl to the density of w a t e r a t temperature 12. Temperatures tl and t z may or may not be the same. T w o common means in general use for expressing the composition of a methanolwater solution are per cent by volume and per cent by weight. Unfortunately the corresponding compositions are not simp l e l i n e a r f u n c t i o n s . The volume of the solution is always less than the sum of the volumes of the components. Most tables relating composition and density or specific gravity give per cent by weight and density, and per cent by volume and specific g r a vi t y , a s complementary f u n c t i o n s , The corresponding composition may be obtained by use of the following appropriate equations:
...
w.
0 1 2
3 4
5 6 7 8
9 10 11 12 13 14 15 16
17 18 19 20 21 22 23 24 25 26 27 28 29 30
31 32 33 34 35 36 37 38 39 40
41
42 43 44
45 46 47 48
49
Methanol,
% v. 0.00 1.27 2.53 3.78 5.04 6.28 7.53 8.77 10,oo 11.23 12.46 13.69 14.91 16.12 17.34 18.55
&$&12
.
.
I
Specific Gravity
25'/25'
C.
Methanol,
W.
19.75 20.95 22.15 23.34 24.53 25.72 26.90 28.08 29.25 30.42 31.58 32.74 33.90 35.05 36.20
66 67 68 69 70 71 72 73 74 75 76 77 78 79
37.34 38.47 39.60 40.73 41.84 42.96 44.07 45.17 46.27 47.37 48.45 49.53 50.61 51,68 52.74 53.ao 54.a6 55.90 56,94
81 a2 83 8.4 85 86 87
Methanol,
5% v. 57.98 59.01 60.03 61.04 62.05 63.05 64.05 65.04 66.02 67.00 67.96 68.91 69.86 70.79 71.72 72.64
89 90 91 92 93 94 95 96 97 9s 99 100
Specific Gravity
25'/25' C. 0.9149 0.9129 0,9109 0,9088 0,9066 0,9045 0.9024 0,9002 0.8981 0 . a959 0.8936 0.8913 0.a89o 0 , 8866 0.a842
o.ssia
0.8795 0.8772 0.8748 0.8724 0.8700 0.8676 0.8652 0,8628 0 . a603 0.8578 0 . a553 0.8527 0.a50i 0 . a475
80
sa
Density C.
25'/4'
0 . a449
86.48 a7.27 88.06
aa.84
a9.60 90.36 91.11 91.87 92.61 93.33 94.04 94.75 95.45 96.13 96.79 97.45 98.11 98.75 99.38 100.00
Vol. 43, No. 3
INDUSTRIAL AND ENGINEERING CHEMISTRY
694
TABLEv. DENSITY,SPECIFIC GRAVITY,AKI) COlIPOSITION RELATIOXSHIP O F MIXTURES O F METHANOL A N D llT'.4TERAT 30" c.
6 7 8 9 10 11 12 13 14 15
1.27 2.54 3.80 5.06 6.31 7.56 8.80 10.04 11.28 12.51 13.74 14.96 16.18 17.40 18.61
Density 30°/4' C. 0.9957 0.9939 0.9921 0.9903 0 9886 0.9868 0,9850 0.9832 0.9815 0,9798 0,9782 0,9765 0,9749 0.9733 0.9717 0,9701
Specific Gravity 30°/300 C 1,0000 0,9982 0.9964 0,9946 0 9929 0.9911 0,9893 0.9874 0.9857 0,9840 0.9824 0.9807 0.9791 0.9775 0.9759 0.9743
16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
19.82 21.02 22.22 23.42 24.61 26,80 26.98 28.16 29. 34 30.51 31.68 32, g4 34.00 35.15 36.30
0.9686 0.9670 0.9654 0.9638 0.9622 0.9606 0.9590 0,9574 0,9558 0,9542 0,9626 0,9510 0,9494 0,9477 0,9460
31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49
37,44 38.58 39.71 40.83 41.95 43.07 44.18 45.29 46.39 47.48 48.57 49.65 50.73 51.81 52.87 53.93 54.98 56.02 57.06
50 51 52
Nethanol,
%
w.
53
E;
66 a7 ,%
59 60 61 62 63 64 65 66 67 68 69 70
71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99
100
9 10 11 12 13 14 15
10.12 11.36 12.60 13.84 15.07 16.30 17.53 is. 74
0.9728 0.9712 0,9696 0.9680 0,9664 0.9647 0.9631 0.9616 0,9599 0.9583 0.9867 0.9551 0,9535 0.9518 0,9501
16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
19.96 21.17 22.38 23.58 24.77 25.97 27.16 28.34 29.52 30.70 31.87 33.03 34.20 35.35 36.50
0.9642 0.9625 0.9608 0,9590 0.9573 0.9557 0.9541 0.9524 0.9507 0.9490 0.9473 0,9456 0.9439 0.9422 0.9406
0,9717 0,9700 0,9683 0,9665 0 9647 0.9631 0.0615 0.9598 0.9581 0.9564 0.95+7 0,9529 0,9812 0,9495 0,9477
0,9443 0.9426 0.9408 0,9390 0.9372 0.9354 0.9336 0.9318 0.9300 0,9281 0.9263 0,9244 0,9225 0.9206 0.9186 0.9166 0.9146 0.9126 0.9106
0,9484 0.9467 0,9449 0 9431 0 9412 0 9394 0,9376 0 9358 0 9340 0 9321 n 9303 0,9284 0.9265 0.9246 0,9226 0,9206 0.9185
31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47
0.9i44
49
37.64 38.78 39.91 41.04 42.16 43.28 44.39 45.49 46.59 47.68 48.77 49.85 50.92 51.99 53.05 54.11 55.16 56.20 57.24
0.9383 0.9366 0.9348 0,9329 0.9311 0,9292 0.9272 0.9252 0.9233 0.9213 0.9194 0.9174 0.9153 0.9133 0,9112 0.9092 0.9071 0.9080 0.9029
0.9458 0,9439 0.9421 0.9402 0,9383 0 9364 0.9344 0.9324 0,9305 0.9285 0,9268 0.9245 0.9224 0.9204 0.9183 0.9162 0.9141 0.9120 0,9099
58.09 59.12 60.14 61,lZ 62.15 63.15 64.14 65,11 66 09 67.06 68.02 68 98 69.93 70.87 Zl.81 ,2.73
0.9084 0 9064 0.9043 0,9021 0,8999 0.8977 0.8955 0.8932 0,8910 0.8887 0.8864 0.8842 0.8819 0.8796 0.8773 0.8749
0.9123 0.9103 0,9082 0,9060 0.9038 0,9016
50 51 52 53 54 65
0.8971 0.8948 0.8925 0.8902 0,8880 0,8857 0.8834 0,8811 0.8787
57 58 59 60 61 62 63 64 65
58.27 59.29 60.32 61.33 62.33 63.33 64.32 63.30 66.28 67.25 68.21 69.17 70.12 71,06 71.99 72.92
0.9007 0,8986 0,8966 0.8943 0.8921 0,889Y 0.8877 0.8855 0.8832 0.8810 0.8764 0.8741 0.8718 0.8694 0.8671
0,9077 0.9056 0,9034 0,9012 0,8990 0.8968 0,8946 0.8924 0.8901 0.8878 0.8865 0.8832 0,8809 0.8785 0.8761 0.8738
73.66 74.57 75.47 76.37 77.26 78.15 79.02 79.88 80.73 81.58 82.43 83.25 84.09 84.90 8d. 72
0.8726 0.8702 0.8678 0.8654 0.8630
0.8764 0,8740
0.8581 0.8556 0.8539 0.8500 0.8480 0.8454 0.8429 0,8403 0.8378
0.8691 0.8667 0,8643 0.8618 0.8593 0,8567 0.8542 0.8517 0.8491 0.8468 0.8439 0.8414
66 67 68 69
80
73.83 74.76 75.66 76.55 77.44 78.31 79.18 80.05 80.90 81.74 82.58 83.41 84.23 85.04 85.85
0.8618 0.8624 0.8600 0.8575 0.8550 0.8525 0.8500 0,8475 0.8450 0.8424 0.8398 0,8372 0.8346 0,8320 0.8294
0.8716 0 8691 0 8667 0 8642 0 8616 0 8591 0.8566 0.8541 0.8516 0,8490 0.8463 0.8437 0.8411 0.8385 0 8359
'
86.52 87.32 88.10 88.87 89.63 90.39 91.14 91.88 92.61 93.33 94.04 94.73 9 z , 42 96. 08 96.74 97.40 98.05 98.70 99.36 100.00
0.8352 0.8326 0.8299 0.8272 0,8245 0.8218 0.8191 0.8164 0.8136 0.8108 0,8080 0,8051 0,8022 0 7992 0.7962 0,7933 0.7904 0.7878 0.7847 0.7819
0.8388 0.8362 0,8335 0,8308 0,8281 0.8253 0.8226 0.8199 0.8171 0.8143 0.8115 0.8086 0,8057 0.8027 0.7996 0.7967 0,7938 0.7909 0.7881 0.7853
81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100
86.66 87.45 88.23 89.00 89.76 90.52 91.27 92.00 92.72 93.42 94.13 94.83 95.52 96.19 96.84 97.49 98.14 98.77 99.38 100.00
0.8269 0.8243 0.8216 0.8189 0.8162 0.8135 0.8108 0,8080 0.8052 0,8023 0.7995 0,7967 0.7938 0.7909 0,7879 0,7849 0.7820 0,7790 0,7759 0.7729
0.8333 0.8307 0,8280 0,8253 0,8226 0,8198 0.8171 0 8143
0.8606
0 9166
0 8444
0.8716
Methanol,
%
w.
0 1 2 3
4 6 7
8
48
06
70
71 72 73
24 I0
76 77 78 74
Blethanol,
Specifio 10°/400 GravityC.
Density 400/40 c. 0.9923 0 9904 0.9886 0.9868 0.9850 0.9832 0.9814 0.9796 0.9778 0.9759 0.9741 0,9724 0.9708 0.9692 0.9676 0.9658
Blethanol, % IT.
0.00
0 1 2 3 4 5
TABLEVI. DENSITY,SPECIFICGR.IVITY, AS^ COMPOSITION RELATIONSHIP OF MIXTURES OF METHANOL A N D WATERAT 40' C. %
v.
0.00 1.28 2.56 3.83 5.10 6.36 7.62 8.87
0,8787
1 . 0000 0,9981 0,9963 0,9946 0,9926 0.9908 0,9890 0.9872 0.9854 0,9835 0.9817 0,9800 0,9783 0 9767 0,8750 0.8733
o.8ii4
0,8085 0.8057 0.8029 0.8000 0.7970 0.7940 0.7910 0.7880 0.7850 0.7819 0 7789
March 1951
I N D U S T R I A L A N D E N G I N E E R I N G CHEM'ISTRY TABLEVII.
4,235 9.380 15.460 13.428 19.395 19.401 32.395 39.074 39.430 39.620
38.007 38.261 35.794 20.717 19.300 12.870 11.426 IO.835 5.436 3.991
695
DETERMINED SHRINKAGES FOR METHANOGWATER SYSTEMAT 25" C.
OI98O1O 0 96537 0.94890 0.93284 0.91 186 0.89070 0,85792 0.84694 0.82156 0.81330
5.383 11.923 19.651 17.068 24.652 24,660 41,176 49.666 50.118 50.360
43.502 50.296 55.550 37.846 44.009 37.568 52,636 60.533 55.570 54,363
38.119 38.373 35.899 20.778 19.357 12.908 11.460 10.867 5.452 4.003
43,100 49.350 54.014 36.603 42.435 36.231 51.078 58.929 54.611 53.622
12.374 23.706 35,375 45.099 56.016 65.641 78.228 82.048 90.189 92.637
0.924 1.881 2.765 3.284 3.577 3.559 2.966 2.650 1.726 1.363
balance using a technique similar to that developed a t the National Density values for the methanol-water system are given for Bureau of Standards (11). The temperature was maintained Coneach per cent by weight methanol at 150 by the B~~~~~of Standards ( 1 3 ) and by Doroshevskil (9). Dunstan and Thole with water by ad(IO) determined the densities of the methanol-water System at justing to the density of water a t the several temperatures. The 20 ', 25", and 30" C. for each 20% methanol. density of methanol was determined. At 25' C. it is identical with the density of methanol given in Table 11; a t 30" C. it dif; Shun-ichi and Hirondo (16)give density data a t 15", 20°, fered from the accepted value by 0.0002 gram per ml., and a t 40 and 30" C. for each mole per cent methanol. The boiling point by 0.0001 gram per ml. The data are presented in Table 111. of the methanol used by them was 64.58" to 64.600 c., 0.1" c, higher than the value reported by Wojciechowski (22). They The composition in per cent by weight was calculated from the found the density of this methanol t o be 0.7961 at 15" c., 0.7915 air weights of methanol and water. The air weights a t 10, 50, at 20' C., and 0.7824 a t 30" C. These values correspond well and 90% methanol were calculated t o vacuum weights. The with those of Timmermans and Hennaut-Roland (21) given in maximum change in per cent composition from air weight t o Table 11, except the value a t 30" C., which is higher. Their density values for the methanol-water system average 0.0002 gram per ml. higher a t 15 C. than those of the Bureau TABLE VIII. SHRINKAGE-cO>lPOSITIONRELATIONSHIP O F METHANOtW.4TER SYSTEM AT 25 ' of Standards (13), and the Val. Loss Vol. Loss M1. o/Con100M1. M1./100 M1. density values a t 30" C. Val. of Constituents Vol. of Constituents Vol. of Vol. of of Conbefore Mixing, M1. before Mixing, M1. average 0.0005 gram per ml. filixture, stituenta Mixture, stituents M1. Mixed M1. Mixed Methanol Water Methanol Water higher than those given in this 96.54 3.46 100.00 0.00 50 50 0 100 paper. 96.51 3.49 99.93 0.07 51 49 1 99 96.48 3.52 99.86 0.14 52 48 2 98 The authors determined thc 96.45 3.55 99.79 0.21 53 47 3 97 density of methanol-water mix96.44 3.56 4 96 6Q 72 0 28 54 46 -. 96.43 3.57 55 45 5 95 tures at 25", 30", and 40" C. 96.42 3.58 56 44 6 94 96.41 3.59 57 43 7 93 for each 10% by weight. 96.41 3.59 58 42 8 92 methanol from 0 to 100%. 96.41 3.59 59 41 9 91 96.40 3.60 40 10 90 These values are presented 96.40 3.60 39 11 89 96.41 3.59 12 62 38 88 for practical use in table form 96.42 3.58 63 37 13 87 a t conveniently used tempera96.43 3.57 64 36 14 86 96.44 3.56 65 35 15 85 tures. The accuracy of the 3.55 96.45 16 98.78 1.22 66 34 84 determined densities n-as csti3.52 96.48 83 17 98.69 1.31 67 33 mated t o be 0.0002 gram per 3.49 96.51 1.40 68 32 98.60 82 18 3.46 96.54 69 31 81 19 98.52 1.48 ml. a t 25" and 30" C . and 3.42 96.58 70 80 20 98.43 1.57 30 3.39 96.61 1.65 29 71 79 21 98.35 *0.0003 gram per ml. a t 40" C. 3.34 96.66 28 72 1.73 78 22 98.27 The probable accuracy of the 3.30 96.70 27 73 1.81 77 23 98.19 3.25 96.75 1 . 9 0 26 74 76 24 98.10 calculated densities is 0.0003 3.19 96.81 1.99 25 25 75 75 98.01 3.12 96.88 24 76 2.07 26 74 97.93 and 0.0004, respectively. 3.05
c.
s ~ ~ ~ , " ~ p ~ ~ ~ ~ ~ ~ ~ ~ ~
c.
O
3.
P
The solutions were made by weight from purified "Middle Run" methanol estimated to have a urity pf 99.95+% and freshly boiled distilled water. T h e Middle Run m e t h a n o l u s e d was free of aldehyde and ester. It was purified further by drying with Drierite and by fractionally distilling in a closed system under dry nitrogen. No perceptible difference could be detected in the density of the original material and the purified product. The densities were determined with a Christian Becker Chainomatic specific gravity
27 28 29 30
41 42 43 44 45 46 47 48 49
73 72 71 70
97.86 97.78 97.70 97.62
2.14 2.22 2.30 2.38
77 78 79 80
23 22 21 20
96.95 97.02 97.09 97.18
2.98 2.91 2.82
59 58 57 56 55 54 53 52 51
97.55 97.48 97.41 97.34 97.27 97.21 97.14 97.08 97.02 96.96 96.91 96.86 96.81 96.76 96.72 96.68 96.64 96.60 96.57
2.45 2.52 2.59 2.66 2.73 2.79 2.86 2.92 2.98 3.04 3.09 3.14 3.19 3.24 3.28 3.32 3.36 3.40 3.43
81 82 83 84 85 86 87 88 89 90 91 92 93
I9 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0
97.25 97.36 97.46 97.57 97.68 97.79 97.92 98.03 98.16 98.30 98.43 98.59 98.73 98.90 99.07 99.23 99.40 99.59 99,79 100 00
2.75 2.64 2.54 2.43 2.32 2.21 2.08 1.97 1.84 1.70 1.57 1.41 1.27 1.10 0.93 0.77 0.60 0.41 0.21 0.00
95 96 97 98 99 100
INDUSTRIAL AND ENGINEERING CHEMISTRY
696
= = dz = dS =
g1
TABLE Ix.
\rISCOSITY O F
Methanol,
MIXTURES O F mi.4TER AT 25" C.
AND
METHANOL
% M'.
Centipoises
0.00 9.77 20.01 30.01 34.02 37,73 40.00 50.00 59.95 69.97 80,03 89,97 100.00
0 . 8937a (calibrating value)
grams of water density of methanol at 25" C., 0.78674 density of water a t 25 C., 0.99707 density of mixture at 25' C., determined
The composition density data at 25" C. were taken from Table I11 to cover the composition range. The shrinkages a t various concentrations were calculated from these data and are given in Table VII. The values from Table VI1 were plotted on a large scale and curves were drawn through the points. The shrinkage for each milliliter interval of methanol per 100 ml. of constituents n a s read from this graph and appears in Table VIII.
1.1724 1.4186 1.5816 1,6243
1.6601
1.6713 1,5760 1 ,4264 1,2335 1,0241 0.7885 0,5565
F r o m ( 2 ) , based on reference value of mater a t 20'
dl
Vol. 43, No. 3
c. as 1.0050cp.
VISCOSITY
vacuum weight bases was O . O l % , a difference too small t o \Tarrant the vacuum weight calculation for this paper. The data in Table I11 were plotted on a large scale and curves were drawn through the points. The density-per cent by weight values were read from these graphs t o *0.0002 gram per ml. for each per cent of methanol by weight. The corresponding per cents of methanol by volume and specific gravities were calculated (Tables IV, V, and VI). CONTRACTIOS OF METH4NOL-WATER M I X T U R E S
When methanol and water are mixed there is a contraction of volume. The contraction of volume, milliliter per 100 ml. of constituents, mas calculated a t 25 O C. from the experimental data.
The viscosit,ies of mixtures of methanol and wat,er were det,ermined at 25' * 0.01 C. using the Cannon-Fenske (6) viscometer. The solutions were prepared by air weights of methanol and water. h correction for end effect was not made. The viscosity of met,hanol calculated from daba of Bingham ( 2 ) is 0.552 cp.; the determined value is 0.5585. The est,imated error is not greater than +0.005 cp. The determined viscosities are given in Table IX. The values in Table IX were plotted on a large scale and a curve was drawn through the points. The viscosities for the methanol-water mixtures for each per cent methanol by weight were read from the graph and tabulated in Table X. LITERATURE CITED
(1) American Society for Testing Materials Standards, "A.S.T.hI.
Standards 1942," Part 111,pp. 983 ff., Philadelphia, 1942. (2) Bingham, E. C., "Fluidity a n d Plasticity," S e w York, RIcGrawHill Book Co., 1922. (3) Bingham, E. C., J . Rheol., 2 , 403 (1931) (4) B i n g h a m , E. C., a n d Jackson, R. E., BztZZ. Bur. Standards, 14, 59 (1919). (5) Butler, J. A. V., T h o m s o n , D. W., a n d M a c L e n a n , W.H . , J . loo (" ") = shrinkage, ml. per 100 ml. of constituents Chem. SOC.,136,674 (1933). vc (6) C a n n o n , >I. R., and Fenske, Xi. R., IND. ENG.CHEM.,- 4 s . k ~ . ED., 10, 297 (1938); Oil & Gas J . , 33,52 (1935). where 17) Coe. J. R.. a n d Godfrev. T . B . . J . AvaZied Phus., 15. 625 11944). V , = sum of volumes of constituents (volume of methanol (8) Doroshevskii, A. G., j . Rzlss. Phys: Chem. sbc., 41, 962 (1909). volume of water) (9) Ibid., pp. 977-96. V, = volume of mixture (10) D u n s t a n , A. E., a n d Thole, F. B., J . Chem. Soc., 95, 1556-61 g, = grams of methanol (1909). (11) Forziati, A. F., Mair, B. J., a n d Rossini, F. D., J . Research .Vatl. Bur. Standards. 35.513 (19451. (12) Meyers, C. H . , Ibid., 9 , 807 (1932). VISCOSITY O F hfETHANOL-\\TATER ?\IIXTT.RES A T 25' TABLE (13) National Bureau of Standards, C i ~ c . Methanol, Viscosity, Methanol, VlSO OS1 t y , Methanol, T'lsco*lty, 19,20-46 (1924). % W. CP. '/c w. CP. 70 TT. CP. (14) National B u r e a u of S t a n d a r d s , 35 0 0.894 1,255 "Selected Values of Properties of 1 36 0.923 1,234 2 37 Hydrocarbons," Am. P e t r o l e u m 0.952 1.214 3 38 0,981 1.194 I n s t . Project 44, Table 20, 1947. 4 1.010 39 1.174 (15) Shun-ichi, Uchida, a n d H i r o n d o , 5 40 1.039 1.153 40.3 6 1,067 1,134 Kato, J . SOC.Chem. Ind., Japan, 7 1,095 41 1.112 37, Suppl. Binding, 525-7 (1934). 42 8 1.123 1.091 43 9 1.151 1.070 (16) Stull, D. R., J . Am. Chem. SOC.,59, 1.178 44 10 1.048 2726 (1937). 45 11 1,206 1.025 (17) Swietoslawski, K.,"Ebuljomet,rja," 1,233 46 12 1.002 1.259 47 13 0.978 W a r s a w , 1935; "Ebulliometry," 1.284 48 14 0.954 New York. Chemical Publishing 49 1.308 15 0.931 50 1.332 16 0.908 Co., 1937. 51 1.355 17 0.884 (18) Swietoslawski, W., "Ebulliometric 1,550 52 1.377 87 Measurements," p. 79 ff., p. 123 0,860 1,536 53 88 1.398 0.836 ff., New York, Reinhold Publishing 1,522 54 89 1.419 0.812 Corp., 1945. 1,508 90 1.438 55 0.788 n 76.5 56 1.493 91 1.457 (19) Swietoslawski, ST., J . chim. phys., 27, 57 1.477 0.742 92 1.475 496 (1930). 68 93 1.461 1.492 0.719 1,444 59 94 1.509 0.696 J . Research Natl. (20) Swietoslarvski, W., 1.427 60 95 1.526 0.672 Bur. Standards. 20, 549 (1938). 61 96 1.410 0.649 1.540 (21) T i m m e r m a n s , J . , a n d H e n n a u t 1.392 62 97 1.554 0.626 1,373 63 98 1.567 0.603 Roland, M m e . , J . chim. phvs., 27, 1,354 1,581 64 0.580 99 401 (1930). 100 65 1.335 1.592 0.557 66 1.315 1.602 (22) Wojciechorvski, hI., J . Research Natl. 67 1.295 1.613 Bur. Standards, 17, 721 (1936). 1.275 68 1,624
-
+
x.
c.
RECEIVED hIarch 20, 1950
