Documente Academic
Documente Profesional
Documente Cultură
16.5 16.5 18.5 19.5 21 21 21.25 21.55 23.25 23.65 23.75 24 25.15 25.25
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
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?
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