Solutions

Youll Need to Know

how to determine molarity how to determine molality how to determine the density of a solution how to determine the concentration of a solution in percent how to determine either initial molarities or volumes involving dilution how to determine mole fraction and fractional distillation what are colligative properties how to work with problems involving boiling point elevation how to work with problems involving freezing point depression how to solve problems involving vapor pressure lowering (Raoults Law) how to determine the osmotic pressure of a solution

Solutions are homogenous mixtures of two or more substances. Most (although not all) solution problems on the AP Chemistry Exam will involve a water solvent. The solute is the item being dissolved and is usually the smaller amount. Solutions that contain the maximum amount of solute in a given amount of solvent are called saturated solutions. Solutions that contain less solute than they have the capacity to dissolve are known as unsaturated solutions. Supersaturated solutions are solutions that contain more solute than is present in the saturated condition. The lower the temperature and/or the higher the pressure, the more soluble a gas will be in a solution.

Molarity
Molarity is the molar concentration of a solution, which is usually expressed as the number of moles of solute per liter of solution. The symbol for molarity is M. M = moles of solute liter of solution

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Example
Q. 70. mL of a 2.0-molar Na2CO3 solution is added to 30. mL of 1.0-molar NaHCO3 solution. What is the resulting concentration of Na+? A. Na2CO3 2Na+ + CO32 (2 moles Na+ / mole Na2CO3) (2.0 mol Na2CO3 / L soln) = 4 moles Na+ / L soln
+ 70. mL 1L # 3 # 4 molesNa = 0.28 molesNa + in 70.0 mL 1 L soln 10 mL + NaHCO3 Na + HCO3 + 30. mL 1 L # 1mole Na = 0.030 molesNa + in 30.0 mL 3 1 10 mL L soln 3 0.28 molesNa + + 0.030 molesNa + # 10 mL = 3.1 M 70.0 mL + 30. mL 1L

Molality
Molality is the molal concentration of a solute, which is usually expressed as the number of moles of solute per 1,000 grams of solvent. The symbol for molality is m. m = moles of solute kg of solvent

Example
Q. What is the molality of an aqueous sucrose (C12H22O11, MM = 342 g mol1) solution that is 10.0% sucrose by mass? A. 10.0% sucrose soln = 90.0 g H2O + 10.0 g C12H22O11 10.0 g C 12 H 22 O 11 1mole C 12 H 22 O 11 10 3 g H 2 O # # = 0.325 m 90.0 g H 2 O 342 g C 12 H 22 O 11 1 kg H 2 O

Density and Percent

d = mass of solution volume of solution Solutions can be expressed as either % (w/w), which is a percentage based on mass, or % (v/v), which is a percentage based on volume. % (v/v) is typically used for mixtures of liquids. If 30 mL of ethanol is mixed with 70 mL of water, the percent ethanol by volume will be 30%, but the total volume of the solution will NOT be 100 mL (although it will be close because ethanol and water molecules interact differently with each other than they do with themselves). %] w/w g = mass of solute # 100% mass of solution %] v/v g = volume solute # 100% volume solute(s) + volume solvent

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Note: Dilution is the procedure for preparing a less concentrated solution from a more concentrated one. MiVi = MfVf

Examples
Q. What is the density (g mL1) of a 29.0%(w/w) H2SO4 solution that is 2.90 M? (MM H2SO4 = 98.08 g mol1). A. 98.08 g H 2 SO 4 2.90 molesH 2 SO 4 1 L soln 100. g soln # # # = 0.981g/mL 29.0 g H 2 SO 4 1 mol H 2 SO 4 L soln 10 3 mL

Q. What is the molarity of a solution that is made by diluting 15.0 mL of a 2.00 M H2SO4 (MM = 98.08 g mol1) solution to a volume of 60.0 mL? A. MiVi = MfVf (2.00 M) (0.015 L) = (Mf) (0.06 L) Mf = 0.500 M

Mole Fraction and Fractional Distillation

mol fraction of component A = X A = moles of A sum of moles of all components

thermometer

water outlet

distilling flask

condenser

mixture

cold water inlet distillate

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Example
Q. A mixture of 320.4 grams of methanol that boils at 64.6C at 1 atm of pressure is mixed with 18.02 grams of water (P = 184 mm Hg at 64.6C). If the mixture is distilled at 64.6C, what is the mole fraction of methanol in the distillate? A. 320.4 g CH 3 OH 1mol CH 3 OH # = 10.00 mol CH 3 OH 1 32.04 g CH 3 OH 18.02 g H 2 O 1mol H 2 O # = 1.000 mol H 2 O 1 18.02 g H 2 O 10.00 mol CH 3 OH = 0.9091 1.000 mol H 2 O + 10.00 mol CH 3 OH 1.000 mol H 2 O mol fraction water = X W = = 0.09091 1.000 mol H 2 O + 10.00 mol CH 3 OH mol fraction methanol = X M = Since distillation occurs at the boiling point, the vapor pressure of pure methanol is the atmospheric pressure. partial pressure of methanol = Pm = XmP = (0.9091) (760. mm Hg) = 691 mm Hg partial pressure of water vapor = Pw = XwP = (0.09091) (184 mm Hg) = 16.7 mm Hg total vapor pressure = 691 mm Hg + 16.7 mm Hg = 708 mm Hg The moles of methanol and moles of water in the vapor are proportional to the partial pressures. Therefore, the ratio of partial pressures will also be equal to the ratio of moles. 691mm Hg X m _ in vapor i = = 0.976 708 mm Hg

Colligative Properties
Colligative properties depend only on the number of dissolved particles in solution and not on their identity. The vant Hoff factor (i) is the number of moles of solute actually in solution per mole of solid solute added; i.e, a 1M solution of NaCl is actually 2M in total ions (1M NaCl(aq) 1M Na+(aq) + 1M Cl(aq).

Boiling Point Elevation

The boiling point of a solution made of a liquid solvent with a nonvolatile solute is greater than the boiling point of the pure solvent. The boiling point of a liquid is defined as the temperature at which the vapor pressure of that liquid equals the atmospheric pressure. Tb = iKb m

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Example
Q. What is the boiling point of a solution made by mixing 46.07 grams of ethanol and 500.00 grams of water? A. solute = 46.07 g ethanol solvent = 500.00 g H2O T = iKb m Kb = 0.52C / m i = 1 (ethanol is molecular)

46.07 g C 2 H 5 OH 1mol C 2 H 5 OH # = 1.000 mol C 2 H 5 OH 1 46.07 g C 2 H 5 OH kg H 2 O = 500.00 g H 2 O 1 kg H 2 O # = 0.50000 kg H 2 O 1 1000 g H 2 O m= 1.000 mol C 2 H 5 OH = 2.000 m 0.50000 kg H 2 O

2.000 m = 1.04cC T = K b $ m = 0.52cC # m 1 BP = 100.00C + 1.04C = 101.04C Recall that 100C is defined as the BP of water. It is therefore an exact number with infinite significant figures.

Freezing Point Depression

Freezing point depression occurs when a solute is added to a solvent and the freezing point lowers. Tf = iKf m

Example
Q. What is the freezing point of a 0.500 m aqueous solution of NaCl? A. i = 2 since NaCl ionizes into Na+ and Cl T = i $ K f $ m = ^ 2 h 1.86cC # m F.P. = 0.00C 1.86C = 1.86C 0.500 m = 1.86cC 1

Vapor Pressure Lowering (Raoults Law)

When a nonvolatile solute is added to a liquid to form a solution, the vapor pressure above that solution decreases. VPsolution = VPsolvent $ X solvent where X solvent = moles solvent total moles Xsolvent = (1 Xsolute) VPsolvent VPsolution = P = Xsolute VPsolvent

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Example
Q. What is the vapor pressure of a mixture 9.01 grams of water and 0.200 mol sugar at 29C? The vapor pressure of water at 29C is 30.0 torr. A. 9.01 g H 2 O 1mol H 2 O # = 0.500 mol H 2 O 1 18.02 g H 2 O mol fraction H 2 O = 0.500 mol H 2 O = 0.714 0.500 mol H 2 O + 0.200 mol sugar

VPsolution = VPsolvent XA = (30.0 torr) (0.714) = 21.4 torr

Osmotic Pressure
Osmosis refers to the flow of solvent molecules through a semi-permeable membrane. When a solution and the pure solvent used in making that solution are placed on either side of a semi-permeable membrane, it is found that more solvent molecules flow out of the pure solvent side of the membrane than solvent flows into the pure solvent from the solution side of the membrane. That flow of solvent from the pure solvent side makes the volume of the solution rise. When the height difference between the two sides becomes large enough, the net flow through the membrane ceases due to the extra pressure exerted by the excess height of the solution chamber. Converting that height of solvent into units of pressure (atmospheres) gives a measure of the osmotic pressure exerted on the solution by the pure solvent.
= solute particles = solvent particles

Pure Solvent

Solution

Semi-permeable Membrane

r = iMRT

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Example
Q. What is the osmotic pressure of 13.73 mg of PCl3 in 500.0 mL of an ethanol solution at 27C? (MM PCl3 = 137.30 g mol1) A. r = iMRT 13.73 mg PCl 3 1g 1mol PCl 3 # 3 # = 1.000 # 10 - 4 mol PCl 3 1 137.30 g PCl 3 10 mg 500.0 mL # 1 L = 0.5000 L 1 10 3 mL R = 0.0821 L atm mol1 K1 PCl3 does not ionize, i=1 M= 1.000 # 10 - 4 mol PCl 3 = 2.000 # 10 - 4 M PCl 3 0.5000 L

T = 27C + 273 = 300. K

r = iMRT = (1) (2.000 104 mol L1) (0.0821 L atm mol1 K1) (300. K) r = 4.93 103 atm

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