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Methanol-Water Mixtures
S.Z. MlKHAlL and W.R. KIMEL
Department of Nuclear Engineering, Kansas State University, Manhattan, Kan.
HYDROGEN
RESULTS
Tables I and I1 summarize the experimental results obtained. Empirical equations relating the different parameters follow.
Density of the mixtures, d:, as a function of weight percentage methanol, W.
5
cG ( g . / d . in vacuo) =
C a, W
(2)
I-0
533
Table I. Densities, db, and Molal Volumes, V,of Methanol-Water Mixtures a t Different Temperatures
30" c.
25" C.
Wt. %
Methanol
Mole Yo"
Methanol
d,
g./ml.
Vol.,
ml.
0
0.9971
18.068
5.88
0.9802
19.221
12.33
0.9647
20.468
19.43
0.9492
21.852
27.27
0.9315
23.447
25.293
35.99
0.9119
0.8904
27.442
45.76
29.951
56.75
0.8673
69.22
0.8426
32.905
36.468
83.50
0.8152
91.44
0.8006
38.524
40.720
100
0.7869
' Molecular weight = 32.043. ' Reference (8).
Ob
10
20
30
40
50
60
70
80
90
95
100
35" c
d,
g./ml.
Vol.,
0.9957
0.9786
0.9628
0.9467
0.9285
0.9096
0.8870
0.8637
0.8381
0.8110
0.7962
0.7819
18.094
19.253
20.508
21.909
23.523
25.357
27.548
30.076
33.081
36.657
38.737
40.981
ml.
d,
g./ml.
0.9941
0.9768
0.9606
0.9440
0.9254
0.9060
0.8835
0.8595
0.8333
0.8057
0.7911
0.7771
40" c.
d,
g./ml.
0.9923
0.9747
0.9582
0.9410
0.9220
0.9022
0.8795
0.8553
0.8291
0.8014
0.7864
0.7723
Vol.,
ml.
18.123
19.288
20.555
21.972
23.602
25.457
27.657
30.223
33.272
36.898
38.987
41.234
50" C.
Vol.,
ml.
18.156
19.330
20.607
22.042
23.689
25.565
27.783
30.371
33.440
37.096
39.220
41.490
Vol.,
ml.
18.233
19.424
20.728
22.174
23.876
25.787
28.057
30.687
33.795
37.498
39.669
42.013
(Millipoise) =
4
=o
a, W
, = I
c a, N'
5
(3)
=a
In this equation a0 is the same as an of Equation 2. Constants an through a5 are given in Table 111.
Figure 2 graphically illustrates the closeness of fit between
Equation 3 and typical experimental density data.
Molal volumes of mixtures, V, as functions of mole fraction
methanol, N.
v (ml.) =
a, N'
(4)
,=O
(5)
(6)
for
mixtures,
d: =
,=o
a, t'
(7)
d,
g./ml.
0.9881
0.9700
0.9526
0.9354
0.9148
0.8944
0.8709
0.8465
0.8204
0.7928
0.7775
0.7627
Viscosity, Millipoises
Wt. 'X
Mole %
Methanol Methanol" 25C. 30C. 35C. 40C.
50C.
0'
0
8.95
8.00
7.21
6.54
5.49
10
5.88
11.55
10.15
8.94
8.00
6.56
13.92
12.06
10.62
20
12.33
9.41
7.59
30
19.43
15.40
13.36
11.72
10.34
8.23
40
27.27
15.95
13.81
12.13
10.74
8.54
50
35.99
15.34
13.37
11.80
10.46
8.41
60
45.76
14.01
12.39
10.98
9.81
7.95
70
56.75
12.18
10.85
9.74
8.76
7.22
80
69.22
10.05
9.07
8.29
7.52
6.30
90
83.50
7.82
7.14
6.67
6.12
5.22
95
91.44
6.59
6.12
5.66
5.32
4.58
5.41
5.07
100
100.00
4.74
4.50
3.96
a Molecular weight = 32.043.
'Values of water viscosity are reported by Dorsey (4).
Since Dorsey's value for viscosity of water at 20" C. is
10.09 millipoises, correction of all his values to the new National
Bureau of Standards basis of 10.02 millipoises was given some
consideration. The following are pertinent points:
Dorsey's values were obtained "from a consideration of all
pertinent data available" (4, p. 182). He adds, "They are the
results of an entirely independent study of the recorded data,
and involve many complete recomputations." This led us to believe
that his values for 30", 35", 40", and 50" C. are not necessarily
based on his 10.09-millipoisevalue for 20" C.
Comparison between Dorsey's values and those of Bingham and
Jackson (4, p. 184) reveals that Dorsey's values at 30", 35", 40",
and 50" C. are lower than the corresponding Bingham and Jackson's
values, although the latter values are based on 10.05 millipoises
for water a t 20" C.
Hardy and Cottington [ J . Research Natl. Bur. Standards 42, 573
(1949)] reported a value of 6.551 millipoises for water at 40" C.
based on 10.05 millipoises for water at 20" C. Correction of this
value to 10.02 basis gives 6.531 millipoises compared to Dorsey's
value of 6.536 millipoises without correction.
In view of this lack of agreement, it was decided to keep Dorsey's
values as they are. Whether Dorsey's values will, in the light of
future investigations, need to be corrected or not, the viscosity
values recorded in Table I1 will not be affected because those are
based on 10.02 millipoises for water at 20" C.
Max.% Mean.%
Error
Error
Temp.,
c.
25
30
35
40
50
25
30
35
40
50
al
a0
a2
0.9971
0.9957
0.9941
0.9923
0.9881
-1.8527
-1.8577
-1.8278
-1.8409
-1.9417
0.9971
0.9957
0.9941
0.9923
0.9881
-2.8930
-2.9883
-3.0331
-3.0601
-3.1257
x
x
x
x
x
x
x
x
Equation 2: Density,
2.2013 x
+1.9615 x 10-j
1.3727 x
1.2424 x
1.7956 x
a5
a4
a3
x
x
x
x
x
-2.0581
-2.7269
-2.3385
-1.9397
-2.0748
-0.05
+0.05
-0.04
-0.03
-0.06
0.02
0.01
0.01
0.01
0.02
-0.08
-0.07
-0.05
-0.06
+0.09
0.04
0.03
0.02
0.03
0.04
+0.08
+0.05
-0.04
+0.05
-0.08
0.04
0.03
0.02
0.02
0.04
+0.27
-0.33
-0.19
-0.32
+0.33
0.10
0.10
0.08
0.11
0.10
+1.80
+1.41
+1.96
+1.66
+1.34
0.72
0.56
0.78
0.61
0.47
lo-
lo-
lo-
lo-
lo-
19.324
19.623
19.756
19.791
19.951
25
30
35
40
50
18.068
18.094
18.123
18.156
18.233
25
30
35
40
50
8.95
8.00
7.21
6.54
5.49
0.24099
0.20233
0.15417
0.13139
0.10196
25
30
35
40
50
8.95
8.00
7.21
6.54
5.49
0.54929
0.44634
0.36936
0.30680
0.22387
-7.6821
2.0494
-0.39832
9.3660
-14.873
5.0875
15.192
-2.1367
-12.394
3.7326
-1.7467
13.767
2.4280
10.244
-8.7175
-0.40699
3.2833
8.8399
-9.1047
0.81614
Equation 8: Viscosity, 7 in Millipoises, us. Weight 70Methanol, W
3.8479 x
-2.1872 x
2.3409 x
-8.1493 x lo-
1.6602 X 10
-5.6258 X lo-
2.6359 x
-1.5929 X lo-
1.8071 X 10
-6.4851 X 10 4
3.4838 x
-1.6859 x lo-
1.3872 x
-4.8712 x lo-
2.7079 x
-1.3226 x
1.3259 x
-7.6409 x 10-j
7.8579 x lo-
-2.7156 x lo-
Equation 9: Viscosity, 7 , in Millipoises, us. Mole So Methanol, N
-
-
-1.2468
-9.7573
-7.7954
-6.1310
-4.6508
4.0795 x lo-
2.5606 x
1.4103 x IO-
1.4968 X lo-
1.1518 x
x
x
x
X
7.2924 x
6.3434 X
5.9862 x
6.0250 X
2.8063 x
lo-
lo-
lo-
lo-
lo-
-4.7553 x lo-
-3.9059 X lo-
-3.5458 X lo-
-3.3182 X lo-
-1.7008 X lo-
ss
.
I
9c
rn
L
.
*
t
z
0!
0c
7!
0
10
20
30
PERCENTAGE
40
METHYL
50
60
70
00
A L C O H O L BY W E I G H T , W
90
20
30
40
\
1
50
60
70
80
90
100
IO
MOLE % METHANOL
535
Wt. 70
Methanol
0
10
20
30
40
50
60
70
80
90
100
0
10
20
30
40
50
60
70
80
90
100
a0
1.1648
1.1117
8.8852
8.5160
9.6817
9.6206
9.9612
9.3393
8.9900
9.9865
8.6237
a1
lo-'
x lo-'
x lo-'
x lo-'
X lo-'
x lo-'
x lo-'
x lo-'
x lo-'
X
25.503
29.880
19.832
24.914
27.385
23.126
30.371
16.780
41.483 X lo-'
55.288 x lo-'
16.429
-1.9364
-1.4933
9.7838
1.2585
-3.4993
-4.5013
-1.0699
-6.1523
-4.7077
-1.9995
-7.1042
Equation7: Density,
lo-'
8.2879
x lo-'
6.3450
x
-4.3998
x lo-'
-5.6522
x
1.3800
x
1.6846
x lo-'
4.1849
x
2.2865
X
1.5801
X lo-'
8.3439
x
2.6727
X
Max. %
Error
a4
a3
a2
(Millipoises) =
I
=o
a, N'
(9)
Mean Yo
Error
-0.05
-0.01
+0.01
+0.02
0.00
0.00
0.00
-0.01
-0.02
-0.07
-0.01
0.02
0.01
0.01
0.01
0.00
0.00
0.00
0.00
0.01
0.03
0.00
+0.25
-0.30
+0.31
+0.19
+0.19
+0.25
-0.13
+0.18
+0.54
-0.54
-0.57
0.14
0.15
0.15
0.09
0.09
0.12
0.06
0.09
0.27
0.50
0.28
analysis, since the data in the two cases are different and
the number of parameters is identical. The closeness of
fit in such analyses of experimental data, with a given
number of parameters generally becomes better as the
number of inflection points in the data decreases. Inspection
of Figure 4 reveals one additional inflection point compared with Figure 2; therefore, for our six parameter
least squares fits, the closeness of fit is expected to be
better in the relation represented by Equation 8 than that
represented by Equation 9. Readers interested in computing viscosity values for solution mixtures of known mole
percentages are therefore advised to calculate the corresponding weight percentages and use Equation 8, rather
than using Equation 9 directly unless i 1.96% maximum
error is tolerable.
Temperature dependence of viscosity, 7,
between t = 25' and 50' C.
for
mixtures,
IS
13
F:
w
L"
3~
10
20
40
PERCENTAGE
536
50
METHYL
60
ALCOHOL EY
10
WEIGHT.
(Millipoises) =
,=o
a, t
(10)
CORRECTION
537