Simple Distillation
Distillation of a Miscible Mixture
Some liquids will evaporate entirely over time if left in an open container at room temperature. However, this evap…
As a liquid is heated, it gains energy until the increased disorder of the gas phase outweighs the intermolecular interactions in the liquid phase. Once enough molecules are in the gas phase, they escape the liquid in the form of bubbles. This effect, called boiling, occurs when the total vapor pressure of the substance is equal to the atmospheric pressure.
Vapor pressure is the pressure of the vapor in equilibrium with its condensed phase, and it varies with temperature. In a mixture of liquids, each component has its own vapor pressure, which we call its partial pressure. The total vapor pressure of the mixture is equal to the sum of the partial pressures. If the liquids are miscible, meaning that they always form a homogeneous solution, the partial pressure of each component is the vapor pressure of the pure compound at that temperature times its mole fraction in the liquid.
The temperature at which the first bubble of vapor starts to form in a liquid mixture is called the bubble point. For a pure liquid, both the bubble point and the temperature at which vapor starts to condense, or the dew point, are the same as the boiling point. However, for a mixture of two miscible liquids, both the bubble point and the dew point will be between the boiling points of the components.
When the mixture first boils, the vapor is rich with the compound with the lower boiling point, or the more volatile compound. This increases the proportion of the compound with the higher boiling point, or the less volatile compound, in the liquid mixture.
Distillation is a separation technique that takes advantage of this phenomenon. In a simple distillation, a homogeneous liquid mixture is boiled. The rising vapor then enters the inner chamber of a water-cooled condenser. The vapor condenses to a liquid, called the distillate, which is then collected in a separate vessel.
As the boiling continues, the compositions of the liquid and the vapor change as the more volatile component is removed. So, if we collect the distillate in small fractions, we'll see that each fraction contains the compounds in a different molar ratio.
As the proportion of the less volatile component in the liquid mixture increases, so do the bubble point and dew point. Plotting the mixture's bubble and dew points versus the mole fractions of the components makes a boiling point diagram. Once we have this diagram, we can use the dew point curve to determine the composition of the vapor at a given temperature.
In this lab, you will set up and perform the simple distillation of a mixture of cyclohexane and toluene and record the temperature of the vapor throughout the experiment. You'll then use the published boiling point diagram for cyclohexane and toluene to determine the composition of the vapor, allowing you to estimate the composition of the liquid mixture throughout the distillation.
As a liquid is heated, it gains energy until the increased disorder of the gas phase outweighs the intermolecular interactions in the liquid phase. Once enough molecules are in the gas phase, they escape the liquid in the form of bubbles. This effect, called boiling, occurs when the total vapor pressure of the substance is equal to the atmospheric pressure.
Vapor pressure is the pressure of the vapor in equilibrium with its condensed phase, and it varies with temperature. In a mixture of liquids, each component has its own vapor pressure, which we call its partial pressure. The total vapor pressure of the mixture is equal to the sum of the partial pressures. If the liquids are miscible, meaning that they always form a homogeneous solution, the partial pressure of each component is the vapor pressure of the pure compound at that temperature times its mole fraction in the liquid.
The temperature at which the first bubble of vapor starts to form in a liquid mixture is called the bubble point. For a pure liquid, both the bubble point and the temperature at which vapor starts to condense, or the dew point, are the same as the boiling point. However, for a mixture of two miscible liquids, both the bubble point and the dew point will be between the boiling points of the components.
When the mixture first boils, the vapor is rich with the compound with the lower boiling point, or the more volatile compound. This increases the proportion of the compound with the higher boiling point, or the less volatile compound, in the liquid mixture.
Distillation is a separation technique that takes advantage of this phenomenon. In a simple distillation, a homogeneous liquid mixture is boiled. The rising vapor then enters the inner chamber of a water-cooled condenser. The vapor condenses to a liquid, called the distillate, which is then collected in a separate vessel.
As the boiling continues, the compositions of the liquid and the vapor change as the more volatile component is removed. So, if we collect the distillate in small fractions, we'll see that each fraction contains the compounds in a different molar ratio.
As the proportion of the less volatile component in the liquid mixture increases, so do the bubble point and dew point. Plotting the mixture's bubble and dew points versus the mole fractions of the components makes a boiling point diagram. Once we have this diagram, we can use the dew point curve to determine the composition of the vapor at a given temperature.
In this lab, you will set up and perform the simple distillation of a mixture of cyclohexane and toluene and record the temperature of the vapor throughout the experiment. You'll then use the published boiling point diagram for cyclohexane and toluene to determine the composition of the vapor, allowing you to estimate the composition of the liquid mixture throughout the distillation.
Q1: What is vapor pressure and how does it relate to boiling?
Vapor pressure is the pressure exerted by vapor in equilibrium with its liquid phase. Boiling occurs when the total vapor pressure of a substance equals atmospheric pressure. As temperature increases, vapor pressure rises, allowing more molecules to escape the liquid as bubbles. This relationship is fundamental to understanding when and how liquids transition to gases.
Q2: How do partial pressures work in a mixture of miscible liquids?
In a miscible mixture, each liquid component contributes its own partial pressure to the total vapor pressure. According to Dalton's law, the total vapor pressure equals the sum of individual partial pressures. Each component's partial pressure is calculated using Raoult's law: the pure liquid's vapor pressure multiplied by its mole fraction in the mixture.
Q3: What is the difference between bubble point and dew point in a liquid mixture?
The bubble point is the temperature at which the first vapor bubbles form when a mixture is heated. The dew point is the temperature at which the first liquid drops condense from vapor. For a pure liquid, both temperatures equal the boiling point. For a miscible mixture, both occur between the boiling points of the pure components.
Q4: Why does the composition of distillate change during simple distillation?
During distillation, the more volatile component (lower boiling point) vaporizes first and enters the condenser, enriching early distillate fractions with it. As this component is removed, the liquid becomes richer in the less volatile component, raising the boiling temperature. Collecting distillate in small fractions reveals changing molar ratios as the mixture composition shifts throughout the process.
Q5: How is a boiling point diagram used to track distillation progress?
A boiling point diagram plots bubble and dew point temperatures against mole fractions of mixture components. The lower curve shows the liquid's boiling point at each composition; the upper curve shows the vapor temperature and distillate composition. By recording vapor temperature during distillation and referencing the diagram, you can determine the liquid and vapor compositions at any point in the separation.
Q6: What conditions are necessary for simple distillation to effectively separate two liquids?
The two liquids must be miscible, forming a homogeneous solution. They must have a significant boiling point difference of at least 20 degrees Celsius. This difference ensures that the more volatile component vaporizes preferentially, allowing effective separation. Without sufficient boiling point difference, the vapor composition remains too similar to the liquid, reducing separation efficiency.
Q7: What role does the condenser play in the simple distillation process?
The condenser is a water-cooled glass tube with inner and outer chambers. Rising vapor enters the inner chamber where cold water circulating in the outer chamber cools it, causing condensation. The condensed liquid, called the distillate, drips into a collection vessel. This cooling step is essential for converting vapor back to liquid form for collection and analysis.