Raoult's Law

Key Concepts The escaping tendency of a solvent is measured by its vapor pressure, which is dependent on temperature. Vapor pressure measures the concentration of solvent molecules in the gas phase. Assuming the solute is nonvolatile, the only particles in the gas phase are solvent molecules. <p In a solution, fewer solvent molecules are at the surface compared to the pure solvent, so a smaller proportion of solvent molecules will be in the gas phase and the vapor pressure for the solution is lower than that for the pure solvent. </p

Raoult's Law states that for an ideal solution the partial vapor pressure of a component in solution is equal to the mole fraction of that component times its vapor pressure when pure: Pa = X a Pa Pa = vapor pressure of the solution o Pa = vapor pressure of pure solvent Xa = mole fraction of the solvent
o

The fractional vapor pressure lowering is equal to the mole fraction of the solute: Xb = (Pa - Pa) Pa Pa = vapor pressure of the solution o Pa = vapor pressure of pure solvent Xb = mole fraction of the solute
o o

Fractional vapor pressure lowering can be used to calculate molecular mass (formula weight) of a solute.

Example 1: Calculating the Vapor Pressure of a Solvent 1.00g of nonvolatile sulfanilamide, C6H8O2N2S, is dissolved in 10.0g of acetone, C3H6O. The vapor pressure of pure acetone at the same temperature is 400 mmHg. Calculate the vapor pressure of the solution. a. Calculate moles of solute: n (C6H8O2N2S) = mass MM n(C6H8O2N2S) = 1.00g (6 x 12 + 8 x 1 + 2 x 16 + 2 x 14 + 32.1) g/mol = 1.00 172.1 = 0.0058 mol Calculate moles of solvent: n(C3H6O) = mass MM n(C3H6O) = 10.0g (3 x 12 + 6 x 1 + 16) g/mol = 10.0 58 = 0.172 mol Calculate the mole fraction of the solvent: Xsolvent = nsolvent (nsolute + nsolvent) Xa = n(C3H6O) [n(C3H6O) + n(C6H8O2N2S)] = 0.172 [0.172 + 0.0058] = 0.967 o Calculate the vapor pressure: Pa = XaPa Pa = 0.967 x 400 mmHg = 386.8 mmHg = 387 mmHg

b.

c.

d.

Example 2: Calculating the Molecular Mass (Formula Weight) of a Solute

5.00g of a nonvolatile compound was dissolved in 100g of water at 30 C. The vapor pressure of the solution was measured and found to be 31.20 Torr. o The vapor pressure of pure water at 30 C is 31.82 Torr. Calculate the molecular mass (formula weight) of the unknown solute. a. b. c. Calculate the mole fraction of the solute: Xb = (Pa - Pa) Pa Xb = (31.82 - 31.2) 31.82 = 0.0195 Calculate moles of solvent: n(H2O) = mass molecular mass n(H2O) = 100g (2 x 1 + 16)g/mol = 5.556mol Calculate moles of solute: Xsolute = nsolute (nsolute + nsolvent) 0.0195 = nsolute (nsolute + 5.556) 0.0195(nsolute + 5.556) = nsolute 0.0195(nsolute) + 0.108 = nsolute 0.108 = nsolute - 0.0195(nsolute) 0.108 = 0.9805(nsolute) (nsolute) = 0.108 0.9805 = 0.11 mol Calculate molecular mass (formula weight) of solute: MM = mass moles MM = 5.00g 0.11 mol = 45.45 g/mol
o o

d.

1. Calculate the vapor pressure of a mixture containing 252 g of n-pentane (Mw = 72) and 1400 g of n-eptane (Mw = 100) at 20oC. The vapor pressure of n-pentane and n-eptane are 420 mm Hg and 36 mm Hg respectively. According to Raoult's law, the vapor pressure exercised by a component of a mixture can be calculated as follows P = Po x where P is the vapor pressure of the component in the mixture. Po is the vapor pressure of the pure component. x is the molar fraction of the component in the mixture. Calculation of molar fractions (x) moles n-pentane = 252/72 = 3.5 moles n-eptano = 1400/100 = 14 Totals = 3.5 + 14 = 17.5 moles xn-pentane = 3.5/17.5 = 0.2 xn-eptane = 14/17.5 = 0.8 Thus Pn-pentane = 0.2 x 420 = 84 mm Hg Pn-eptane = 0.8 x 36 = 28.8 mm Hg and the vapor pressure of mixture is Pmixture = 84 + 28.8 = 112.8 mm Note: Although the Raoult's law is valid for diluted (ideal) solution, its application to concentrated (non-ideal) solutions does not lead to variation of the order of magnitude of the calculated vapor pressure.

2. Calculate the boiling point (at 1 atm) of a solution containing 116 g of acetone (Mw = 58) and 72 g of water (Mw = 18) by using the following table:

Temperature o C 60 70 80 90

Vapor pressure (atm) Acetone 1.14 1.58 2.12 2.81

Vapor pressure (atm) Water 0.198 0.312 0.456 0.694

A liquid starts to boil when its vapor pressure matches the atmospheric pressure (1 atm in this case). Thus, according to Raoult's law P = xacetone Po acetone + xwater Powater = 1 atm From the given data we can calculate the molar fractions molesacetone = 116/58 = 2 moleswater = 72/18 = 4 total moles = 6 xacetone = 2/4 = 1/3 xwater = 4/6 = 2/3 thus P = 2/3 Po acetone + 1/3 Powater= 1 atm By trials, using the table, we can find the values of vapor pressure which satisfies the above equation. The best result is obtained by using the values at 80oC : P = 2/3 0.456 + 1/3 2.12 = 1.01 atm then the boiling point is about 80oC.

3. A mixture of water and acetone at 756 mm boils at 70oC. Calculate the percentage composition of the mixture using the following table:

Temperature o C 60 70 80 90

Vapor pressure (atm) Acetone 1.14 1.58 2.12 2.81

Vapor pressure (atm) Water 0.198 0.312 0.456 0.694

According to Raoult's law P = xacetone Po acetone + xwater Powater = 756/760 =0.995 atm by substituting the values at 70oC we have P = xacetone 1.58 + xacqua 0.312= 0.995 and remembering that the sum of molar fractions is 1

xacetone + xacqua = 1

xacqua = 1 - xacetone

thus xacetone 1.58 + 0.312 (1 - xacetone) = 0.995 xacqua 1.58 + 0.312 - 0.312 xacetone = 0.995 xacetone 1.26+ 0.312 = 0.995 xacetone = (0.995 - 0.312)/ 1.26 = 0.54 from which xwater = 1 - 0.54 = 0.46 considering 100 moles of solution we have

54 moles of acetone corresponding to 54x58 =3132 grams and 46 moles of water corresponding to 46x18 = 828 grams. Eventually, % water = (828)(100)/3132 + 828) = 21% % acetone = 100-21 = 79%

4. The addition of 114 grams of sucrose to 1000 grams of water lowers the vapor pressure of water from 17.540 to 17.435. Calculate the molecular weight of sucrose. The variation in pressure is 17.540 - 17.435 = 0.105 then 0.105 = 17.540 x2 = nsolute/(nsolvent + nsolute) nsolvent = 1000/mw water = 1000/18 = 55.55 moles 0.105 = 17.540 x2 = 17.540 nsolute/(55.55 + nsolute) by solving this equation we obtain nsolute = 0.335 moles and thus MW = 114/0.335 = 340 The calculated molecular weight (340) is very close to the true molecular weight of sucrose (342).

5. Calculate the osmotic pressure at 20o of a suspension containing 60g/l of solid particles each particle having a mass of 10-9 grams (1 nanogram). = MRT T = 278 + 20 = 298 oK R = 0.0823 The number of particles in one liter of solution is 60/10-9 = 6 x 1010 Remembering that one mole contains an Avogadro number of particles (6 x 1023), the number of moles in one liter of suspension is

6 x 1010/6 x 1023 = 10-13 which corresponds to the molarity of the suspension. Thus = (0.0823)(298) (10-13) = 24.5 x 10-13 atm

6. Calculate the osmotic pressure of a solution 0.1 molale of sucrose (Mw = 342) at 20oC. To solve the problem we need to convert the molality in molarity Molality = moles/kilogram of solvent Molarity = moles/liter of solution The grams of sucrose in the solutions are 34.2 and the total weight of the solution is 34.2 + 1000 grams of solvent = 1034.2 Assuming a density = 1 for the solution we can write: 0.1 moles : 1034.2 = M : 1000 grams of solution M = 100/1034.2 = 0.097 = (0.097)(0.0820578 liter atm mol-1 K-1)(293) = 2.34 atm

This example problem demonstrates how to use Raoult's Law to calculate the of vapor pressure of two volatile solutions mixed together. Problem: What is the expected vapor pressure when 58.9 g of hexane (C6H14) is mixed with 44.0 g of benzene (C6H6) at 60.0 C? Given: Vapor pressure of pure hexane at 60 C is 573 torr. Vapor pressure of pure benzene at 60 C is 391 torr. Solution Raoult's Law can be used to express the vapor pressure relationships of solutions containing both volatile and nonvolatile solvents. Raoult's Law is expressed by Psolution = solventP where Psolution is the vapor pressure of the solution solvent is mole fraction of the solvent P
0 solvent is the vapor pressure of the pure solvent 0 solvent

When two or more volatile solutions are mixed, each pressure component of the mixed solution is added together to find the total vapor pressure. PTotal = Psolution A + Psolution B + ... Step 1 Determine the number of moles of each solution From the periodic table: C = 12 g/mol H = 1 g/mol molar weight of hexane = 6(12) + 14(1) g/mol molar weight of hexane = 72 + 14 g/mol molar weight of hexane = 86 g/mol

nhexane = 58.9 g x 1 mol/86 g nhexane = 0.685 mol molar weight of benzene = 6(12) + 6(1) g/mol molar weight of benzene = 72 + 6 g/mol molar weight of benzene = 78 g/mol nbenzene = 44.0 g x 1 mol/78 g nbenzene = 0.564 mol Step 2 - Find mole fraction of each solution hexane = nhexane/(nhexane + nbenzene) hexane = 0.685/(0.685 + 0.564) hexane = 0.685/1.249 hexane = 0.548 Since there are only two solutions present and the total mole fraction is equal to one: benzene = 1 - hexane benzene = 1 - 0.548 benzene = 0.452 Step 3 - Find the total vapor pressure PTotal = hexaneP
0 hexane

+ benzeneP

0 benzene

PTotal = 0.548 x 573 torr + 0.452 x 391 torr PTotal = 314 + 177 torr PTotal = 491 torr Answer: The vapor pressure of this solution of hexane and benzene at 60 C is 491 torr.

his example problem demonstrates how to use Raoult's Law to calculate the change in vapor pressure by adding a nonvolatile liquid to a solvent. Problem: What is the change in vapor pressure when 164 g of glycerin (C3H8O3) is added to 338 mL of H2O at 39.8 C. The vapor pressure of pure H2O at 39.8 C is 54.74 torr The density of H2O at 39.8 C is 0.992 g/mL. Solution Raoult's Law can be used to express the vapor pressure relationships of solutions containing both volatile and nonvolatile solvents. Raoult's Law is expressed by Psolution = solventP
0 solvent where

Psolution is the vapor pressure of the solution solvent is mole fraction of the solvent P
0 solvent is the vapor pressure of the pure solvent

Step 1 Determine the mole fraction of solution molar weightglycerin (C3H8O3) = 3(12)+8(1)+3(16) g/mol molar weightglycerin = 36+8+48 g/mol molar weightglycerin = 92 g/mol molesglycerin = 164 g x 1 mol/92 g molesglycerin = 1.78 mol molar weightwater = 2(1)+16 g/mol molar weightwater = 18 g/mol densitywater = masswater/volumewater masswater = densitywater x volumewater masswater = 0.992 g/mL x 338 mL masswater = 335.296 g

moleswater = 335.296 g x 1 mol/18 g moleswater = 18.63 mol solution = nwater/(nwater + nglycerin) solution = 18.63/(18.63 + 1.78) solution = 18.63/20.36 solution = 0.91 Step 2 - Find the vapor pressure of the solution Psolution = solventP
0 solvent

Psolution = 0.91 x 54.74 torr Psolution = 49.8 torr Step 3 - Find the change in vapor pressure Change in pressure is Pfinal - PO Change = 49.8 torr - 54.74 torr change = -4.94 torr Answer: The vapor pressure of the water is reduced by 4.94 torr with the addition of the glycerin.