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# Lab One Grades

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## Lab Two Grades

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Chemistry 314
Experiment 5: Boiling Points of Mixtures

Objectives
Measure the boiling point of a mixture of volatile liquids Measure the boiling point of a mixture of immiscible liquids Use the observations to determine physical and chemical properties of the various liquids

## Vapor Pressure of Liquids

The pressure of a gas in equilibrium with its liquid is the vapor pressure of the liquid. It depends on the tendency of liquid to convert into a gas. DHvap: the energy necessary to convert a mole of a pure liquid into a mole of gas always positive why? The equilibrium vapor pressure, P, of a pure liquid at external pressure, Pex, increases with temperature until P = Pex At this point, the liquid boils; that is, the boiling point of a pure liquid is the temperature at which P = Pex. If Pex =1 atm, the boiling temperature is the normal boiling point.

## Vapor Pressure of Liquid Mixtures

A liquid mixture can consist of several volatile substances. The vapor pressure of a liquid mixture is the sum of the vapor pressures of the individual components. With increasing temperature, the vapor pressure of each component in a liquid mixture increases. When the total vapor pressure of a mixture reaches Pex, the mixture boils.

## Four Physical-Chemical Relationships Related to Boiling Point

I. Clausius-Clapeyron Equation Relates the vapor pressure and temperature of a pure liquid II. Dalton's Law of Partial Pressures Relates the partial pressures of each gas in a mixture III. Raoult's Law Treats the vapor pressure of a solvent with added solute

IV. Henry's Law Relates the vapor pressure of a volatile solute to its equilibrium concentration in solution Also treats the vapor pressure of a solution with volatile solute

Clausius-Clapeyron
The Clausius-Clapeyron Equation relates the vapor pressure of a pure compound, P, to temperature, T: ln (P1/P2) = - (DHvap/R)( 1/T1 - 1/T2 ) (1) Pn is the equilibrium vapor pressure at temperature Tn DHvap is the enthalpy change for the vaporization process (liquid gas) R is the universal gas constant (8.31 J/molK) The equation incorporates three assumptions: (a) DHvap is essentially independent of temperature. (b) The volume of a mole of liquid, compared to that of a mole of vapor, is insignificant. (c) The vapor behaves as an ideal gas. Since DHvap is positive, vapor pressure always increases as temperature increases.

Clausius-Clapeyron
The vapor pressure for any one liquid increases exponentially with increasing T The vapor pressure of one liquid compared to another depends inversely on DHvap The boiling point of any liquid depends on the external pressure

If we plot ln P vs. 1/T, a line is obtained If the normal boiling point and DHvap is known, the pressure at any other T can be trivially calculated

Daltons Law
If two or more gases (which do not react with each other) are enclosed in a vessel, the total pressure exerted by them is equal to the sum of their partial pressures In a mixture composed of two substances, A and B, PA + PB = Ptot (2) PA is the vapor pressure of A PB is the vapor pressure of B and Ptot is the total vapor pressure of the mixture Consequence: A mixture boils when: PA + PB = Ptot = Pext

Raoults Law
When a nonvolatile solute is added to a volatile solvent, the vapor pressure of the solution will be lower than that of the pure solvent The net vapor pressure is proportional to the solvents mole fraction PA = cAPA (3) PA is the vapor pressure of the solvent in the solution cA is the mole fraction of solvent (solvent moles divided by total moles solution) PA is the pure solvent's vapor pressure at the same temperature Equation 3 represents "ideal behavior Raoults Law is accurately obeyed if the mole fraction of the solvent is near 1 (the solvent is nearly pure)

Raoults Law
When a nonvolatile solute is added to a solvent, the vapor pressure of the solution will be lower than that of the pure solvent Why?

At equilibrium, there is a balance between the rate at which molecules evaporate and condense rate of vaporization = kvap x SA rate of condensation = kcon x PA At equilibrium, kcon x PA = kvap x SA PA = (SA) kvap/kcon But when we add solute molecules, some fraction of the surface becomes unavailable for evaporation while remaining available for condensation Assuming that the solute is evenly distributed, the fraction of surface area still available is cA

Raoults Law
Boiling Behavior of Solutions with a Non-volatile Solute The boiling point of a solution containing non-volatile solutes is higher than the boiling point of a pure solvent. Why? According to Raoult's Law, vapor pressure of the solution is less than vapor pressure of the pure solvent (at constant temperature) because csolvent < 1. Thus, a higher temperature is required for P to reach Pext

Raoults Law
Raoults Law also governs the vapor pressure of mixtures of two or more volatile components The vapor pressure of each is determined by its mole fraction and the vapor pressure of the pure component The total vapor pressure always lies between the vapor pressures of the pure components, and is determined by the mixture composition
1

Mole fraction of B

Henrys Law
Deals with the dissolution of soluble gases in a liquid solvent The vapor pressure of a dissolved solute is proportional to its concentration pA = kH[A] (4) pA = kccA pA = kmmA Henrys Law holds for any sufficiently dilute solution

Henrys Law
The vapor pressure is proportional to the concentration, as in Raoults Law, but the proportionality constant is different Why?

How does the chemical environment of the solvent compare to the chemical environment of the pure liquid? How does the chemical environment of the solute compare to the chemical environment of the pure gas?

## Raoults Law and Henrys Law

Note that both Laws are in play in any real mixture.

The vapor pressure of nearly pure solvents is described by Raoults Law, and that of very dilute solutes is described by Henrys Law.
In between those two regimes, the vapor pressures of most real solutions differ dramatically from ideal behavior particularly if the two components have significant attractive or repulsive forces

## Mixtures of Immiscible Liquids

A mixture consisting of two separate liquid phases insoluble in one another is not governed by these laws As each liquid exists in its own pure state, each contributes its pure vapor pressure to the total pressure of the system The vapor pressure of the mixture is the sum of the vapor pressures of each component The mixture boils when the total vapor pressure reaches Pex Hence, the mixture always boils at a lower temperature than either component! The boiling point does not depend on relative quantities of immiscible phases, since the vapor pressure of a component only depends on its being present