IUPAC-NIST Solubility Database
NIST Standard Reference Database 106


Glass Ball as Bullet Solubility System: Nitromethane with 1-Butanol and Water

Components:
   (1) 1-Butanol; C4H10O; [71-36-3]  NIST Chemistry WebBook for detail
   (2) Nitromethane; CH3NO2 ; [75-52-5]  NIST Chemistry WebBook for detail
   (3) Water; H2O; [7732-18-5]  NIST Chemistry WebBook for detail

Evaluator:
   V. P. Sazonov, Technical University, Samara, Russia, May, 1999

Critical Evaluation:

        A survey of reported compositions along the solubility curve and compositions of coexisting phases in equilibrium for the system nitromethane + 1-butanol + water is given in Table 1.

Solubility data

     All three binary pairs of components, nitromethane + 1-butanol, nitromethane + water and 1-butanol + water, are partially miscible. The data for first two systems were compiled and critically evaluated (Sazonov et al.3) and for 1-butanol + water system in Barton.4 The values of UCST (upper critical solution temperatures) of the binary systems are reported in Zhuravlev et al.1 and Marigliano et al.2 and presented in Table 2.
     The solubility curve for the ternary system at 303.15 K was obtained by the titration method (Ref. 2) with an estimated accuracy in composition and temperature within ± 0.0005 of mass fractions and ± 0.05 K, respectively. The solubility temperatures of the liquid phases were determined (Refs 1 and 2) by the synthetic method in ternary mixtures with constant mass relationship of (1) and (2). The solubility curves at 283 K, 323 K, 343 K and 353 K (Ref. 1) and at 333.15 K, 340.15 K, 341.15 K, 348.15 K, 363.15 K and 388.15 K (Ref. 2) were constructed by graphical interpretation of the cloud-point data. Experimental errors were reported in Ref. 2 to be ± 0.1 K (temperature) and ± 0.001 mass fractions (solubility). Depending on temperature the system nitromethane + 1-butanol + water forms a miscibility gaps of Type I to III, Ref. 5. In the temperature range 273 K to 290.5 K (Ref. 1), where the three binary systems are partially miscible, the solubility curves correspond to Type III (Ref. 5). A three-phase region occurs below 281 K (Ref. 1). Above 281 K two separate regions of immiscibility exist, one of which can be described by band type curves. In the temperature range 290.5 K to 377.7 K (Ref. 1) or at 384 K (Ref. 2), where two binary systems nitromethane + water and 1-butanol + water partially miscible, the solubility curves correspond to Type II (Ref. 5), while 2 separate solubility curves can be clearly observed above 341 K.
     Below this temperature there are band type curves. Above 384 K this ternary system has only one partially miscible region, Ref. 2. Solubility data at 303.15 K, 333.15 K, 348.15 K and 388.15 K are described by corresponding algebraic equations (Table 3). These smoothing equations give smaller standard deviations than any other tested equation. The equation parameters were calculated by the least squares method.
     The solubilities calculated by the proposed equations are presented in Figs. 13 and 14 and in Table 3. Experimental solubility data, Refs 1 and 2, are presented in Figs. 13 and 14 for comparison.
     LLE data for the ternary system nitromethane + 1-butanol + water were reported at 273.2 K, 281.2 K and 323.2 (Mel'nikova1) in graphical form and at 303.15, 333.15, 341.15, 348.15 and 363.15 (Marigliano et al.2). Composition of each phase (Mel'nikova1 and Marigliano et al.2) was calculated from the index of refraction-composition curve of saturated mixtures prepared at the time of the saturation curve measurements and also from the density-composition curve in Marigliano et al.2 The compositions of three coexistent liquid phases at 273 K (Mel'nikova1) are presented in graphical form. Plait points were reported in Marigliano et al.2 at 340.5 K, 341.15 K, 348.15 K and 363.15 K. Experimental errors were reported in Marigliano et al.2 as ± 0.005 of mass fractions.

Recommended or tentative data

     Solubility and liquid-liquid equilibrium data measured by different methods are in agreement with one another. Experimental data on solubility at some temperatures Mel'nikova1 and Marigliano et al.2 are presented in Figs. 13 and 14 in mole fractions. In view of the inaccurate results obtained in Mel'nikova1 and Marigliano et al.2 for the binary nitromethane + water, nitromethane + 1-butanol and 1-butanol + water systems, the evaluator considers the ternary system data to be tentative and concludes that new studies on the ternary system would be of value.



Experimental Data:   (Notes on the Nomenclature)

Table 1.  Summary of experimental data for the system nitromethane + 1-butanol + water
AuthorT/KDataTypeReference
Zhuravlev et al.274 to 371Solubility curve (132)1
Zhuravlev et al.273Equilibrium (13)1
Zhuravlev et al.281Equilibrium (13)1
Zhuravlev et al.323Equilibrium (13)1
Marigliano et al.303.15Solubility curve (24), Equilibrium (13)2
Marigliano et al.333.15Solubility curve (24), Equilibrium (13)2
Marigliano et al.340.15Solubility curve (24),2
Marigliano et al.341.15Solubility curve (24), Equilibrium (8)2
Marigliano et al.348.15Solubility curve (22), Equilibrium (8)2
Marigliano et al.363.15Solubility curve (15), Equilibrium (8)2
Marigliano et al.388.15Solubility curve (6)2
Table 2. UCST (T/K) binary systems
Chemical NameT/KReference
nitromethane + 1-butanol290.5Ref. 1
nitromethane + water377.7Ref. 1
water + 1-butanol398Ref. 1
nitromethane + 1-butanol-Ref. 2
nitromethane + water384Ref. 2
water + 1-butanol403Ref. 2
nitromethane + 1-butanol290.9 ± 0.3 (Ref. 3)recommended
nitromethane + water376.3 ± 0.2 (Ref. 3)recommended
water + 1-butanol397.55 K to 398.5 K (Ref. 4)recommended
Table 3. Calculated mutual solubilities of nitromethane, 1-butanol and water
T/KMass Fraction w1Mass Fraction w2Mass Fraction w3Mole Fraction x1Mole Fraction x2Mole Fraction x3Comment(s)
303.20.0000.7940.2060.0000.4840.516x1 = 1.0025 –3.94×x2 +3.8311×(x2)2 (organic-rich branch)
303.20.0070.7670.2260.0050.4500.545
303.20.0560.7040.2400.0390.4000.561
303.20.1360.6230.2410.0930.3500.557
303.20.2400.5300.2300.1650.3000.535
303.20.3640.4300.2060.2570.2500.493
303.20.4980.3290.1730.3680.2000.432
303.20.6350.2320.1330.4980.1500.352
303.20.7670.1440.0890.6470.1000.253
303.20.8900.0660.0340.8150.0500.135
303.20.9740.0000.0260.9170.0000.083
303.20.0000.0710.9290.0000.0180.982x1 = 0.0369 +1.682×x2 –162.6898×(x2)2 (water-rich branch)
303.20.0430.0680.8890.0140.0180.958
303.20.0680.0600.8720.0220.0160.955
303.20.0880.0520.8600.0290.0140.953
303.20.1030.0440.8530.0340.0120.952
303.20.1120.0370.8510.0370.0100.953
303.20.1210.0290.8500.0400.0080.954
303.20.1240.0220.8540.0410.0060.957
303.20.1250.0150.8600.0410.0040.962
303.20.1230.0070.8700.0400.0020.968
303.20.1180.0000.8820.0380.0000.962
333.20.0000.7630.2370.0000.4390.561x1=[0.8018-9.8109×x2+39.749(x2)2-50.2742×(x2)3]/[1-10.1633×x2+32.5541×(x2)2] (organic-rich branch)
333.20.0130.7260.2610.0090.4000.591
333.20.0870.6470.2660.0570.3500.593
333.20.1400.5750.2850.0890.3000.611
333.20.1630.5120.3250.0970.2500.653
333.20.1850.4410.3740.1020.2000.698
333.20.4270.2940.2790.2640.1500.586
333.20.7050.1580.1370.5430.1000.357
333.20.8410.0720.0870.7050.0500.245
333.20.9440.0000.0560.8300.0000.170
348.20.0000.7370.2630.0000.4050.595x1=-0.1204-1.423×x2-0.0264×(x2)2+1.107×(x2)1/2 (separate solubility curve)
348.20.0090.7280.2630.0060.4000.594
348.20.0520.6640.2840.0330.3500.617
348.20.0930.5960.3110.0570.3000.643
348.20.1310.5250.3440.0760.2500.674
348.20.1640.4480.3880.0890.2000.711
348.20.1880.3650.4470.0940.1500.756
348.20.1940.2710.5350.0870.1000.813
348.20.1470.1600.6930.0560.0500.894
348.20.0000.0690.9310.0000.0180.982
348.20.2120.0000.7880.0740.0000.926x2=-1.7995-15.7222×x3-5.221×(x3)2+8.557×(x3)1/2+14.144×(x3)3/2 (other separate solubility curve)
348.20.2270.0530.7200.0840.0160.900
348.20.3210.1520.5270.1440.0560.800
348.20.4200.1850.3950.2200.0800.700
348.20.5220.1810.2970.3110.0890.600
348.20.6210.1570.2220.4140.0860.500
348.20.7290.1090.1620.5340.0660.400
348.20.8500.0380.1120.6750.0250.300
348.20.9110.0000.0890.7500.0000.250
388.20.0000.5750.4250.0000.2480.752x1=-0.4182-1.3623×(x2)1/2+1.5564×(x2)1/4
388.20.0020.5770.4210.0010.2500.749
388.20.0270.4970.4760.0130.2000.787
388.20.0510.4050.5440.0230.1500.827
388.20.0640.2990.6370.0260.1000.874
388.20.0370.1730.7900.0130.0500.937
388.20.0000.1300.8700.0000.0350.965
View Figure 13 for this Evaluation

View Figure 14 for this Evaluation

Notes:
Table 1a  Number of experimental points in parentheses.

References: (Click a link to see its experimental data associated with the reference)

   1  Mel'nikova, I. K.;, Dissertation, Voronezh University, 1966; Zhuravlev, E. F.; Mel'nikova, I. K.; Zh. Fiz. Khim. 1, 1580 (1967).
   2  Marigliano, A. C. G.; Gramajo de Doz, M. B. and Solimo, H. N.; Fluid Phase Equilib. 149, 309 (1998).
   3  Sazonov, V. P.; Marsh, K. N.; and Hefter, G. T.; Nitromethane with Water or Organic Solvents: Binary Systems, IUPAC-NIST Solubility Data Series. Vol. 71, J. Phys. Chem. Ref. Data 29 (2000).
   4  Barton, A. F. M.; Alcohols with Water, IUPAC Solubility Data Series. Vol. 15. Pergamon Press, Oxford, 1984.
   5  Treybal, R. E.; Liquid Extraction, McGraw-Hill, New York, 1963.