This work involved the measurement of the viscosities of pure organic liquids at temperatures ranging from 353.15 K to 463.15 K and at the corresponding vapour pressures. A rolling ball viscometer was used where considerable emphasis was given to achieve simplicity and rapidity in obtaining results, without sacrificing the accuracy. Considering the forces affecting the motion of the ball inside the viscometer tube, an equation for the calibration of the viscometer at the same working temperature was derived. The constants of this equation were determined using benzene as the reference liquid, and the dependency of the constants on the temperature was also established. Comparing the derived equation with published ones demonstrated its adequacy in both the streamline and transition flow conditions. The liquids studied were toluene, methanol and n‐hexane. In some cases, the results compared reasonably well with published data while in others, deviations of up to 15% were found. Nine equations were tested with the experimental results for the prediction of the viscosity of these liquids. It was found that the 3‐constant Agrawal and Thodos empirical equation gave the least average deviation.

The total pressure and the compositions of the vapour and liquid phases of the methanol–benzene system have been determined under equilibrium conditions at 100°, 120°, 140°, 160°, 180°, 200° and 220° for ten levels of concentration. The corresponding activity coefficients of methanol and benzene are reported; their values indicate that the equilibrium data are thermodynamically consistent. An azeotrope is found at all temperatures, its methanol content increasing as the temperature is increased. The relationship log Paz = 6·5098—(1,766/T) expresses the interdependence of the azeotrope vapour pressure Paz(lb/in2 abs.) and temperature T(°K). Estimates of integral heat of mixing (HE) and entropy change due to mixing (SE) as functions of liquid composition (xmeth) have been made from the excess free energy of mixing GE,(T) xmeth functions. Both HE and SE at a given x are positive increasing functions of temperature. These phenomena are discussed in terms of the dissociation of methanol ‘polymer’ and the formation of benzene–methanol ‘complexes’.

The total vapour pressure and the composition of the liquid and vapour phases of the benzene and n-heptane system have been experimentally determined under equilibrium conditions at 110, 125, 140, 155, 170, 185, 200 and 215 "C. The corresponding composition of the vapour phase was also estimated using an expression for the liquid phase activity coefficient as a function of the composition of the liquid phase. Several expressions were compared and it has been found that the three-constant Redlich and Kister equation gave the best fit of the experimental vapour pressure data than the other equations.Comparison between the calculated and measured vapour compositions has shown a discrepancy of ymeas. -ycalc. of the order of 0.02 mol fraction or 10 times the experimental tolerance. Nevertheless, the experimental values were reasonably thermodynamically consistent.The low values of the liquid phase activity coefficients indicated that the behaviour of this particular system was not far from ideality. Also, it was found that the degree of non-ideality decreased with the increase in temperature. The behaviour of the vapour phase was shown also to be nearly ideal.The excess Gibbs free energy of mixing was calculated, and it was found to be non-symmetrical with mole fraction. On increasing the temperature of the system, the liquid composition corresponding to the maximum GE tended to shift to a higher benzene concentration, whilst at a fixed liquid composition, GE initially decreased and then remained stationary or increased again. This was thought to be due to differences in the molar volumes of the two components. 113?

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Viscosities of -hexane and benzene liquid mixtures of different composition levels at temperatures of 363.15, 383.15, 403.15, 423.15, 443.15, and 463.15 K and the corresponding vapor pressures using a rolling ball viscometer have been measured. Six different equations were tested for the prediction of viscosity at these particular conditions and the McAllister equation was found to fit the experimental data better than the others.