IUPAC-NIST Solubility Database
NIST Standard Reference Database 106


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

Components:
   (1) Nitromethane; CH3NO2 ; [75-52-5]  NIST Chemistry WebBook for detail
   (2) 1-Hexanol; C6H14O; [111-27-3]  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 solubility and equilibrium of coexisting liquid phases for the system nitromethane + 1-hexanol + water is given in Table 1.

Solubility data

     All three binary pairs of components, nitromethane + 1-hexanol, nitromethane + water and 1-hexanol + water, are partially miscible. The data for first two systems were compiled and critically evaluated (Sazonov et al.4). The values of UCST (upper critical solution temperature) of the binary systems are reported in Zhuravleva et al.1 and Sazonov et al.2, and presented in Table 2. The 1-hexanol + water system was critically evaluated in Barton.5
     The solubility temperatures of the liquid phases were determined by the synthetic method in ternary mixtures with constant mass relationship of (1) and (2), and also in ternary mixtures with a constant mass content of (3) (Zhuravleva et al.1). The solubility curves at 293.2 K, 294.2 K, 303.2 K and 313.2 K were determined by the titration method (Sazonov et al.2). Experimental errors were not reported, but are estimated by the evaluator to be ± 0.1 K (temperature) and ± 0.001 mass fractions (solubility). The system nitromethane + 1-hexanol + water includes a three-phase region. Depending on temperature the system nitromethane + 1-hexanol + water forms a miscibility gaps of Type I to III, Treybal.6 In the temperature range 273 K to 308.6 K, where three binary systems are partially miscible, the solubility curves correspond to Type III (Treybal6). A three-phase region occurs below 294.4 K (Zhuravleva et al.1). Maximal temperature of the three-phase liquid equilibrium was reported to be 294.2 K (Zhuravleva et al.1) and 294.5 K (Sazonov et al.2). Thus, the recommended value is Tc = (294.4 ± 0.2) K. Two separate regions of immiscibility exist above 294.4 K, one of these can be described by band type curves. In the temperature range 308.6 K to 377.7 K (Zhuravleva et al.,1 Sazonov et al.2 and Sazonov et al.3), where two binary systems (nitromethane + water and 1-hexanol + water) are partially miscible, the solubility curves are Type II (Treybal6). Above 377.7 K, this ternary system has only one partially miscible region, Zhuravleva et al.1 Solubility data at 313 K and 333 K (Zhuravleva et al.1 and Sazonov et al.2) both separately and in common (only organic-rich branch) are described by an algebraic equation in the form:

x1 = a + b·x2 + c·(x2)2 + d·(x2)1/2 + e·(x2)3/2.

     This smoothing equation gives a smaller standard deviation than any other tested equation. The equation parameters (a, b, c, d and e) were calculated by the least squares method and presented in Table 3.
     The solubilities, calculated by the proposed equations, are presented in Fig. 15 and in Table 4. Experimental solubility data, Zhuravleva et al.1 and Sazonov et al.2, are presented in Fig. 15 for comparison.

Liquid-liquid equilibrium (LLE) data

     LLE data for the ternary system nitromethane + 1-hexanol + water were reported at 283 K, 291 K, 293 K and 298 K (Zhuravleva et al.1) in graphical form and at 294.2, 296.2 and 313.2 (Sazonov et al.3). Composition of each phase (Zhuravleva et al.1) was calculated from the index of refraction-composition curve of saturated mixtures prepared at the time of saturation curve measurements and by gas chromatography (Sazonov et al.3). The compositions of three coexisting liquid phases at 283 K, 291 K and 293 K (Zhuravleva et al.1) are also reported in graphical form. These data and data from Sazonov et al.3 at 294.2 K are presented in Table 5. Experimental errors were not reported. All experimental data are considered tentative.



Experimental Data:   (Notes on the Nomenclature)

Table 1. Summary of experimental data for the system nitromethane + 1-hexanol + water
AuthorT/KDataTypeReference
Zhuravleva et al.280 to 379Solubility curve liquid phase (120)1
Zhuravleva et al.283Equilibrium (8)1
Zhuravleva et al.291Equilibrium (8)1
Zhuravleva et al.293Equilibrium (8)1
Zhuravleva et al.298Equilibirum (10)1
Sazonov et al.293Solubility curve (24)2
Sazonov et al.294Solubility curve (37)2
Sazonov et al.303Solubility curve (30)2
Sazonov et al.313Solubility curve (19)2
Sazonov et al.294Equilibirum (13)3
Sazonov et al.296Equilibirum (12)3
Sazonov et al.313Equilibirum (9)3
Table 2. UCST (T/K) binary systems
Chemical NameT/KReference
nitromethane + 1-hexanol308.8Ref. 1
nitromethane + water377.7Ref. 1
1-hexanol + water-Ref. 1
nitromethane + 1-hexanol308.7Ref. 2
nitromethane + water-Ref. 2
1-hexanol + water-Ref. 2
nitromethane + 1-hexanol308.6 ± 0.3 (Ref. 4)Recommended
nitromethane + water376.3 ± 0.2 (Ref. 4)Recommended
1-hexanol + water495.4 (Ref. 5)Recommended
Table 4. Calculated solubility data (organic-rich branch only) of nitromethane, 1-hexanol and water
T/KMass Fraction w1Mass Fraction w2Mass Fraction w3Mole Fraction x1Mole Fraction x2Mole Fraction x3
313.20.0000.9290.0710.0000.6980.302
313.20.0290.8950.0760.0350.6500.315
313.20.0650.8540.0810.0760.6000.324
313.20.1050.8090.0860.1200.5500.330
313.20.1520.7590.0890.1680.5000.332
313.20.2050.7040.0910.2200.4500.330
313.20.2650.6430.0920.2760.4000.324
313.20.3310.5770.0920.3360.3500.314
313.20.4040.5070.0890.4010.3000.299
313.20.4850.4310.0840.4710.2500.279
313.20.5710.3500.0790.5460.2000.254
313.20.6640.2660.0700.6260.1500.224
313.20.7620.1790.0590.7120.1000.188
313.20.8630.0900.0470.8030.0500.147
313.20.9650.0000.0350.8900.0000.110
333.20.0000.9140.0860.0000.6520.348
333.20.0030.9110.0860.0040.6500.346
333.20.0390.8700.0910.0450.6000.355
333.20.0800.8250.0950.0890.5500.361
333.20.1250.7750.1000.1350.5000.365
333.20.1770.7200.1030.1850.4500.365
333.20.2350.6600.1050.2380.4000.364
333.20.2980.5950.1070.2940.3500.356
333.20.3700.5240.1060.3550.3000.345
333.20.4480.4470.1050.4190.2500.331
333.20.5330.3660.1010.4880.2000.312
333.20.6260.2790.0950.5630.1500.287
333.20.7260.1890.0850.6430.1000.257
333.20.8310.0950.0740.7310.0500.219
333.20.9440.0000.0560.8300.0000.170
Table 5. Compositions of three coexisting liquid phases system nitromethane + 1-hexanol + water
T/KMole Fraction x1Mole Fraction x2Comment(s)
283.2, Ref. 10.8210.062nitromethane-rich phase
291.2, Ref. 10.6840.131nitromethane-rich phase
293.2, Ref. 10.6040.203nitromethane-rich phase
294.2, Ref.30.6200.183nitromethane-rich phase
283.2, Ref. 10.2300.511alcohol-rich phase
291.2, Ref. 10.3700.349alcohol-rich phase
293.2, Ref. 10.4180.305alcohol-rich phase
294.2, Ref.30.4460.296alcohol-rich phase
283.2, Ref. 10.0320.002water-rich phase
291.2, Ref. 10.0330.002water-rich phase
293.2, Ref. 10.0330.002water-rich phase
294.2, Ref.30.0340.001water-rich phase
View Figure 15 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  Zhuravleva, I. K.; Zhuravlev, E. F. and Rudakova, N. A.; Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol. 18, 333 (1975); Deposited Doc., VINITI 1587 (1974).
   2  Sazonov, V. P.; Markuzin, N. P. and Filippov, V. V.; Zh. Prikl. Khim. (Leningrad) 49, 784 (1976).
   3  Sazonov, V. P.; Markuzin, N. P. and Filippov, V. V.; Zh. Prikl. Khim. (Leningrad) 50, 1524 (1977).
   4  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).
   5  Barton, A. F. M.; Alcohols with Water, IUPAC Solubility Data Series. Vol. 15. Pergamon Press, Oxford, 1984.
   6  Treybal, R. E.; Liquid Extraction, McGraw-Hill, New York, 1963.