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Introduction
When a liquid mixture begins to boil, the vapour does not normally have the same composition as the liquid. The components with the lowest boiling point (i.e. the more volatile) will preferentially boil off. Thus, as the liquid continues to boil, the concentration of the least volatile component drops. This results in a rise in the boiling point. The temperatures over which boiling occurs set the bubble and dew points of the mixture. The bubble and dew points can be defined as: 1. The bubble point is the point at which the first drop of a liquid mixture begins to vaporize. 2. The dew point is the point at which the first drop of a gaseous mixture begins to condense. For a pure component, the bubble and dew point are both at the same temperature - its boiling point. For example, pure water will boil at a single temperature (at atmospheric pressure, this is 100oC). For ideal mixtures (i.e. mixtures where there are no significant interactions between the components), vapour-liquid equilibrium is governed by Raoult's Law and Dalton's Law.
Raoult's Law
Raoult's Law states that the partial pressure of a component, PA, is proportional to its concentration in the liquid. So for component A,
Where: PA PoA xA - Partial pressure of component A - Vapour pressure of component A - Liquid mole fraction of component A
Dalton's Law
Dalton's Law states that the total pressure is equal to the sum of the component partial pressures. Thus for component A, its partial pressure, PA, is proportional to its mole fraction in the gas phase:
Calculating the dew point is iterative. Firstly we guess a temperature which allows us to calculate the vapour pressure Po for each component (the vapour pressures of pure components can be calculated using the Antoine Equation - Antoine Coefficients for many components are presented elsewhere on this site). The pure component vapour pressures can then be used to calculate the liquid mole fraction for each component, x, using the above equation. The sum of all the liquid mole fractions should add up to 1 at the dew point. If the sum is greater than 1, the temperature guess is too low. If the sum is less than 1, the temperature guess is too high. Adjust the temperature until the liquid mole fractions add up to 1.
Assuming ideal behaviour, the liquid mole fractions at the dew point can be calculated using:
Thus
Adding the liquid mole fractions together gives: 0.655 + 0.542 + 0.409 = 1.606. This is greater than 1, meaning that 40oC is below the dew point. Re-guessing the temperature at 50oC, 58oC, 53oC and 54oC: Temperature xPentane xHexane xHeptane Total 40oC 0.655 0.542 0.409 1.606 50oC 0.475 0.374 0.267 1.116 58oC 0.374 0.283 0.194 0.851 53oC 0.434 0.336 0.237 1.006 54oC 0.421 0.325 0.227 0.972
Table 1: Dew Point Calculation temperature iteration As can be seen in the table above, the dew point for this mixture at atmospheric pressure is just over 53oC.
Again, as with the dew point, calculating the bubble point is iterative. Firstly we guess a temperature which allows us to calculate the vapour pressure Po for each component. This is then used to calculate the vapour mole fraction for each component, y, using the above equation. The sum of all the vapour mole fractions should add up to 1 at the bubble point. If the sum is greater than 1, the temperature guess is too high. If the sum is less than 1, the temperature guess is too low. Adjust the temperature until the vapour mole fractions add up to 1.
Assuming ideal behaviour, the vapour mole fractions at the bubble point can be calculated using:
Thus
Adding the vapour mole fractions together gives: 0.857 + 0.074 + 0.006 = 0.937. This is less than 1, meaning that 40oC is below the bubble point. Re-guessing the temperature at 50oC, 45oC, 42oC and 41oC: Temperature yPentane yHexane yHeptane Total 40oC 0.857 0.074 0.006 0.937 50oC 1.183 0.107 0.009 1.299 45oC 1.011 0.089 0.008 1.108 42oC 0.918 0.080 0.007 1.005 41oC 0.888 0.077 0.006 0.971
Table 2: Bubble Point Calculation temperature iteration As can be seen in the table above, the bubble point for this mixture at atmospheric pressure is just under 42oC.
Non-ideality
As noted above, this calculation method assumes that the mixture obeys Raoults Law and Daltons Law. This is not always the case. In particular, Raoults Law is often not followed when the components are polar or dissimilar. Where the solution is not ideal, more complicated calculation methods are required. This is outside the scope of this short article.