Chapter 17: Properties of Solutions

17.1 Solution Composition 17.2 The Thermodynamics of Solution Formation 17.3 Factors Affecting Solubility 17.4 The Vapor Pressure of Solutions 17.5 Boiling-Point Elevation and Freezing-Point Depression 17.6 Osmotic Pressure 17.7 Colligative Properties of Electrolytic Solutions 17.8 Colloids

Definitions for Solutions

Solute - The smaller (in mass) of the components in a solution, the material dispersed into the solvent. Solvent - The major component of the solution, the material that the solute is dissolved into. Solubility - The maximum amount that can be dissolved into a particular solvent to form a stable solution at a specified temperature. Miscible - Substances that can dissolve in any proportion, so that it is difficult to tell which is the solvent or solute!

Solution Composition
Mass percent: weight percent Mass percent = grams of solute x 100% grams of solution

Mole fraction: symbolized by the Greek letter, chi = X nA mole fraction of component A = XA = n + n A B Molarity: M ; (chapter 4) moles of solute M = liter of solution Molality: m m= moles of Solute Kg of solvent

Like Dissolves Like

Polar molecules - dissolve best in Polar solvents. Polar molecules can hydrogen bond with polar solvents, such as water, hence increasing their solubility. Non-polar molecules - dissolve best in non polar solvents. Hydrocarbons, non - polar molecules, do not dissolve, or mix with water!

Fig 13.4 (P 486)

The structure and function of a soap

Predicting Relative Solubility's of Substances -I

Problem: Predict which solvent will dissolve more of the given solute. (a) Sodium Chloride in methanol (CH3OH) or in propanol (CH3CH2CH2OH). (b) Ethylene glycol (HOCH2CH2OH) in water or in hexane (CH3CH2CH2CH2CH2CH3). (c) Diethyl ether (CH3CH2OCH2CH3) in ethanol (CH3CH2OH) or in water. Plan: Examine the formulas of each solute and solvent to determine which forces will occur. A solute tends to be more soluble in a solvent which has the same type of forces binding its molecules.

Predicting Relative Solubility's of Substances - II

Solution: (a) Methanol - NaCl is an ionic compound that dissolves through iondipole forces. Both methanol and propanol contain a polar hydroxyl group, and propanols longer hydrocarbon chain would form only weak forces with the ions, so it would be less effective at replacing the ionic attractions of the solvent. (b) Water Ethylene glycol molecules have two -OH groups, and the molecules interact with each other through H bonding. They would be more soluble in water, whose H bonds can replace solute H bonds better than can the dispersion forces in hexane. (c) Ethanol Diethyl ether molecules interact with each other through dipole and dispersion forces and could form H bonds to both water and ethanol. the ether would be more soluble in ethanol because the solvent can form H bonds and replace the dispersion forces in the solute, whereas the H bonds in water must be partly replaced with much weaker dispersion forces.

An Energy Solution? Solar Ponds

Solar ponds are shallow bodies of salt water ( a very high salt content) designed to collect solar energy as it water the water in the ponds, and then it can be used for heating, or converted into other forms of energy. Sufficient salt must be added to establish a salt gradient in a pool 2-3 meters deep, with a dark bottom. A salt gradient will be established in which the upper layer, called the conductive layer, has a salt content of about 2% by mass. The bottom layer, called the heat storage layer has a salt content of about 27%. The middle layer called the nonconvective layer has an intermediate salt content, and acts as an insulator between the two layers. The water in the deepest layer can reach temperatures of between 90 and 100oC, temperatures as high as 107oC have been reported. A 52 acre pond near the Dead sea in Israel can produce up to 5 mega watts of power.

Three Steps in making a Solution

Step #1 : Breaking up the solute into individual components: (expanding the Solute) Step #2 : Overcoming intermolecular forces in the solvent to make room for the solute: (expanding the solvent) Step #3 : Allowing the solvent and solute to interact and form the solution.

Figure 17.1: The formation of a liquid solution can be divided into three steps

Figure 17.2: (a) Enthalpy of solution Hsoln has a negative sign (the process is exothermic) if Step 3 releases more energy than is required by Steps 1 and 2. (b) Hsoln has a positive sign (the process is endothermic) if Steps 1 and 2 require more energy than is released in Step 3.

H of solution for Sodium Chloride

NaCl(s) Na +(g) + Cl (g) Ho1 = 786 kJ/mol Na+(aq) + Cl (aq) Ho2 + Ho3 = - 783 kJ/mol

H2O(l) + Na+(g) + Cl (g) Hohyd =

Hhyd = enthalpy (heat) of hydration Hosoln = 786 kJ/mol 783 kJ/mol = 3 kJ/mol The dissolving process is positive, requiring energy. Then why is NaCl so soluble? The answer is in the Gibbs free energy equation from chapter 10, G = H T S The entropy term T S is Negative, and the result is that G becomes negative, and as a Result, NaCl dissolves very well in the polar solvent water.

Solution Cycle
Step 1: Solute separates into Particles - overcoming attractions Therefore -- Endothermic Step 2: Solvent separates into Particles - overcoming intermolecular attractions Therefore -- Endothermic solvent (aggregated) + heat solvent (separated) Hsolvent > 0 Step 3: Solute and Solvent Particles mix - Particles attract each other Therefore -- Exothermic solute (separated) + solvent (separated) solution + heat Hmix < 0 The Thermochemical Cycle Hsolution = Hsolute + Hsolvent + Hmix If If HEndothermic Rxn < HEndothermic Rxn > HExothermic Rxn HExothermic Rxn solution becomes warmer solution becomes colder

Solution Cycles and the Enthalpy Components of the Heat of Solution

Figure 17.3: Vitamin A, C

A Fat Soluble Vitamin A Hydrophobic Vitamin

A Water Soluble Vitamin A Hydrophilic Vitamin

Figure 17.4: (a) a gaseous solute in equilibrium with a solution. (b) the piston is pushed in, which increases the pressure of the gas and the number of gas molecules per unit volume. (c) greater gas

Henrys Law of Gas solubilities in Liquids P = kHX

P = Partial pressure of dissolved gas X = mole fraction of dissolved gas kH = Henrys Law Constant

Henrys Law of Gas Solubility

Problem: The lowest level of oxygen gas dissolved in water that will support life is ~ 1.3 x 10 - 4 mol/L. At the normal atmospheric pressure of oxygen is there adaquate oxygen to support life? Plan: We will use Henrys law and the Henrys law constant for oxygen in water with the partial pressure of O2 in the air to calculate the amount. Solution: The Henrys law constant for oxygen in water is 1.3 x 10 -3 mol liter atm and the partial pressure of oxygen gas in the atmosphere is 21%, or 0.21 atm.

Soxygen = kH x PO2 = 1.3 x 10 -3 mol x ( 0.21 atm) liter atm

SOxygen = 2.7 x 10 - 4 mol O2 / liter This is adaquate to sustain life in water!

Figure 17.5: The solubilities of several solids as a function of temperature.

Predicting the Effect of Temperature on Solubility - I

Problem: From the following information, predict whether the solubility of each compound increases or decreases with an increase in temperature. (a) CsOH Hsoln = -72 kJ/mol (b) When CsI dissolves in water the water becomes cold (c) KF(s) H2O K+(aq) + F -(aq) + 17.7 kJ Plan: We use the information to write a chemical reaction that includes heat being absorbed (left) or released (right). If heat is on the left, a temperature shifts to the right, so more solute dissolves. If heat is on the right, a temperature increase shifts the system to the left, so less solute dissolves. Solution: (a) The negative H indicates that the reaction is exothermic, so when one mole of Cesium Hydroxide dissolves 72 kJ of heat is released.

Predicting the Effect of Temperature on Solubility - II

(a) continued CsOH(s) H2O Cs+(aq) + OH -(aq) + Heat

A higher temperature (more heat) decreases the solubility of CsOH. (b) When CsI dissolves, the solution becomes cold, so heat is absorbed. H2O CsI(s) + Heat Cs+(aq) + I -(aq) A higher temperature increases the solubility of CsI. (c) When KF dissolves, heat is on the product side, and is given off so the reaction is exothermic. H2O K+(aq) + F -(aq) + 17.7 kJ KF(s) A higher temperature decreases the solubility of KF

Figure 17.6: The solubilities of several gases in water as a function of temperature at a constant pressure of 1 atm of gas above the solution.

Figure 17.9: The presence of a nonvolatile solute inhibits the escape of solvent molecules from the liquid

Figure 17.10: For a solution that obeys Raoults law, a plot of Psoln versus xsolvent yields a straight line.

Fig. 13.15

Vapor Pressure Lowering -I

Problem: Calculate the vapor pressure lowering when 175g of sucrose is dissolved into 350.00 ml of water at 750C. The vapor pressure of pure water at 750C is 289.1 mm Hg, and its density is 0.97489 g/ml. Plan: Calculate the change in pressure from Raoults law using the vapor pressure of pure water at 750C. We calculate the mole fraction of sugar in solution using the molecular formula of sucrose and density of water at 750C. Solution: molar mass of sucrose ( C H O ) = 342.30 g/mol
12 22 11

175g sucrose = 0.51125 mol sucrose 342.30g sucrose/mol 350.00 ml H2O x 0.97489g H2O = 341.21g H2O ml H2O 341.21 g H2O = 18.935 molH2O 18.02g H2O/mol

Vapor Pressure Lowering - II

Xsucrose = Xsurose = mole sucrose moles of water + moles of sucrose 0.51125 mole sucrose = 0.2629 18.935 mol H2O + 0.51125 mol sucrose

P = Xsucrose x P 0H2O = 0.2629 x 289.1 mm Hg = 7.600 mm Hg

Like Example 17.1 (P 841-2)

A solution was prepared by adding 40.0g of glycerol to 125.0g of water at 25.0oC, a temperature at which pure water has a vapor pressure of 23.76 torr. The observed vapor pressure of the solution was found to be 22.36 torr. Calculate the molar mass of glycerol! Solution: Roults Law can be rearranged to give: Psoln 22.36 torr = = 0.9411 = o P H2O 23.76 torr 125.0 g mol H2O = = 6.94 mol H2O 18.0 g/mol XH2O = 0.9411 = mol gly = mol H2O mol gly + mol H2O 6.94 mol mol gly + 6.96 mol

6.94 mol (6.94 mol)(0.9411) = 0.4357 mol 0.9411 40.0 g = 91.81 g/mol (MMglycerol = 92.09 g/mol) 0.4357 mol

Figure 17.11: Vapor pressure for a solution of two volatile liquids.

H-O - - -

- - -

HOH H-C-C-C-H H H Acetone + Water

HHHHHH H-C-C-C-C-C-C-H HHHHHH HH H-C-C-O-H HH

Hexane + Ethanol

Figure 17.12: Phase diagrams for pure water (red lines) and for an aqueous solution containing a nonvolatile solution (blue lines).

Like Example 17.2 (P 845-6)

A solution is prepared by dissolving 62g of sucrose in 150.0g of water the resulting solution was found to have a boiling point of 100.61oC. Calculate the molecular mass of sucrose. Solution: T = kbmsolute
oC Kg kb = 0.51 m solute

T = 100.61oC 100.00 oC = 0.61oC 0.61oC = = 1.20 mol/Kg msolute = oC Kg kb 0.51 m solute mol solute Msolute = mol solute = (0.150 kg)(1.2 mol/kg) kg solvent 62g mol solute = 0.18 mol MM = 0.18 mol = 344g/mol T
(MMsucrose = 342.18 g/mol)

Like Example 17.3 (P847)

What mass of ethanol (C2H6O) must be added to 20.0 liters of water to keep it from freezing at a temperature of -15.0oF? Solution: oC = (oF 32)5/9 = (-15 32)5/9 = -26.1oC T = kf msolute msolute = T kf -26.1oC = 1.86 oC kg = 14.0 mol/kg mol

14.0 mol/kg(20 kg H2O) = 280 mol ethanol Ethanol = 2x12.01 + 6x 1.008 + 1x16.0 = 46.07 280 mol ethanol (46.07 g ethanol/mol) = 12.9 kg ethanol

Determining the Boiling Point Elevation and Freezing Point Depression of an Aqueous Solution
Problem: We add 475g of sucrose (sugar) to 600g of water. What will be the Freezing Point and Boiling Points of the resultant solution? Plan: We find the molality of the sucrose solution by calculating the moles of sucrose and dividing by the mass of water in kg. We then apply the equations for FP depression and BP elevation using the constants from table 12.4. Solution: Sucrose C12H22O11 has a molar mass = 342.30 g/mol 475g sucrose = 1.388 mole sucrose 342.30gsucrose/mol molality = 1.388 mole sucrose = 2.313 m 0.600 kg H2O 0C 0.512 0 Tb = Kb x m = (2.313 m)= 1.18 C BP = 100.000C + 1.180C m BP = 101.180C
0 Tf = Kf x m = 1.86 C (2.313 m) = 4.300C FP = 0.000C - 4.300C = -4.300C m

Determining the Boiling Point Elevation and Freezing Point Depression of a Non-Aqueous Solution
Problem: Calculate the effect on the Boiling Point and Freezing Point of a chloroform solution if to 500.00g of chloroform (CHCl3) 257g of napthalene (C10H8, mothballs) is dissolved. Plan: We must first calculate the molality of the cholorform solution by calculating moles of each material, then we can apply the FP and BP change equations and the contants for chloroform. Solution: napthalene = 128.16g/mol chloroform = 119.37g/mol molesnap = 257g nap =2.0053 mol nap 128.16g/mol molarity = moles nap =2.0053 mol= 4.01 m kg(CHCl3) 0.500 kg 0C 3.63 Tb = Kb m = (4.01m) = 14.560C normal BP = 61.70C m new BP = 76.30C
0 Tf = Kf m =4.70 C (4.01m) =18.850C m

normal FP = - 63.50C new FP = - 82.40C

Figure 17.15: The normal flow of solvent into the solution (osmosis) can be prevented by applying an external pressure to the solution.

Figure 17.16: A pure solvent and its solution (containing a nonvolatile solute) are separated by a semipermeable membrane through which solvent molecules (blue) can pass but solute molecules (green) cannot.

Osmotic pressure calculation

Calculate the osmotic pressure generated by a sugar solution made up of 5.00 lbs of sucrose per 5.00 pints of water. Solution: 1 kg 5.00 lbs ( ) = 2.27 kg 2.205 lbs Molar mass of sucrose = 342.3 g/mol 2,270g = 6.63 mol sucrose 342.3g/mol

1.00 gallon )( 3.7854 L ) = 2.36 liters 5.00 pints H2O ( 8 pints 1.00 gallon L atm = MRT = ( 6.63 mol )(0.08206 )(298 K) = 68.7 atm mol K 2.36 L

Like example 17.4 (P 848-9)

To determine the molar mass of a certain protein, 1.7 x 10-3g of the protein was dissolved in enough water to make 1.00 ml of solution. The osmotic pressure of this solution was determined to be 1.28 torr at 25oC. Calculate the molar mass of the protein. Solution: 1 atm = 1.28 torr( ) = 1.68 x 10-3 atm 760 torr T = 25 + 273 = 298 K M= 1.68 x 10-3 atm = 6.87 x 10-5 mol/L 0.08206 L atm(298 K) mol K xg mol x = 2.47 x 104g/mol

1.70 g = 6.87 x 10-5mol

Determining Molar Mass from Osmotic Pressure - I

Problem: A physician studying a type of hemoglobin formed during a fatal disease dissolves 21.5 mg of the protein in water at 5.00C to make 1.5 ml of solution in order to measure its osmotic pressure. At equilibrium, the solution has an osmotic pressure of 3.61 torr. What is the molar mass(M) of the hemoglobin? Plan: We know the osmotic pressure (),R, and T. We convert from torr to atm and T from 0C to K and use the osmotic pressure equation to solve for molarity (M). Then we calculate the moles of hemoglobin from the known volume and use the known mass to find M. Solution: P = 3.61 torr x 1 atm = 0.00475 atm 760 torr Temp = 5.00C + 273.15 = 278.15 K

Molar Mass from Osmotic Pressure - II

M= = RT 0.00475 atm 0.082 L atm (278.2 K) mol K = 2.08 x 10 - 4 M

Finding moles of solute:

-4 n = M x V = 2.08 x 10 mol x 0.00150 L soln = 3.12 x 10 - 7 mol L soln

Calculating molar mass of Hemoglobin (after changing mg to g): M = 0.0215 g -7 = 6.89 x 104 g/mol 3.12 x 10 mol

Example 17.5 (P 850)

What concentration of sodium chloride in water is needed to produce an aqueous solution isotonic with blood ( = 7.70 atm at 25oC). Solution: = RT M = RT 7.70 atm M = (0.08206 L atm) (298 K) = 0.315 mol/L mol K Since sodium chloride gives two ions per molecule, the concentration would be that value, or 0.158 M NaCl Na+ + Cl-

Figure 17.18: Reverse osmosis

Reverse Osmosis for Removal of Ions

Colligative Properties of Volatile Nonelectrolyte Solutions

From Raoults law, we know that: Psolvent = Xsolvent x P0solvent and Psolute = Xsolute x P0solute Let us look at a solution made up of equal molar quantities of acetone and chloroform. Xacetone = XCHCl3 = 0.500, at 350C the vapor pressure of pure acetone = 345 torr, and pure chloroform = 293 torr. What is vapor pressure of the solution, and the vapor pressure of each component. What are the mole fractions of each component? Pacetone = Xacetone x P0acetone = 0.500 x 345 torr = 172.5 torr PCHCl3 = XCHCl3 x P0CHCl3 = 0.500 x 293 torr = 146.5 torr PA From Daltons law of partial pressures we know that XA = P Total Pacetone 172.5 torr Xacetone = P = = 0.541 Total 172.5 + 146.5 torr 146.5 torr XCHCl3 = PCHCl3 = = 0.459 PTotal 172.5 + 146.5 torr Total Pressure = 319.0 torr

Colligative Properties
I ) Vapor Pressure Lowering - Raoults Law II ) Boiling Point Elvation III ) Freezing Point Depression IV ) Osmotic Pressure

Colligative Properties of Ionic Solutions

For ionic solutions we must take into account the number of ions present! i = vant Hoff factor = ionic strength, or the number of ions present For vapor pressure lowering: For boiling point elevation: For freezing point depression: For osmotic pressure: P = i XsoluteP 0solvent Tb = i Kb m Tf = i Kf m = i MRT

Figure 17.21: In a aqueous solution a few ions aggregate, forming ion pairs that behave as a unit.

Like Example 17.6 (P 853)

The observed osmotic pressure for a 0.10M solution of Na3PO4 at 25oC is 8.45 atm. Compare the expected and experimental values of i! Solution: Tri sodium phosphate will produce 4 ions in solution. Na3PO4 3 Na+ + PO4-3

Thus i is expected to be 4, now to calculate the experimental value of i from the osmotic pressure equation. = iMRT or i = 8.45 atm = mol (0.10 )(0.08206 L atm )(298 K) MRT L mol K

i = 3.45

This is less than the value expected of 4 so there must be some ion paring occurring in the solution.

Figure 17.22: The Tyndall effect

Source: Stock Boston

Figure 17.23: Representation of two colloidal particles