Chemistry, The Central Science, 10th edition Theodore L. Brown; H. Eugene LeMay, Jr.; and Bruce E.
Bursten
Properties of Solutions
Adapted by SA Green from: John D. Bookstaver St. Charles Community College St. Peters, MO 2006, Prentice Hall, Inc.
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Solutions
Solutions are homogeneous mixtures of two or more pure substances. In a solution, the solute is dispersed uniformly throughout the solvent.
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How does a solid dissolve into a liquid?
What drives the dissolution process? What are the energetics of dissolution?
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How Does a Solution Form?
1. Solvent molecules attracted to surface ions. 2. Each ion is surrounded by solvent molecules. 3. Enthalpy (DH) changes with each interaction broken or formed.
Ionic solid dissolving in water
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How Does a Solution Form?
1. Solvent molecules attracted to surface ions. 2. Each ion is surrounded by solvent molecules. 3. Enthalpy (DH) changes with each interaction broken or formed.
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How Does a Solution Form
The ions are solvated (surrounded by solvent). If the solvent is water, the ions are hydrated. The intermolecular force here is iondipole.
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Energy Changes in Solution
To determine the enthalpy change, we divide the process into 3 steps.
1. Separation of solute particles. 2. Separation of solvent particles to make holes. 3. Formation of new interactions between solute and solvent.
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Enthalpy Changes in Solution
The enthalpy change of the overall process depends on DH for each of these steps.
Start
End
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Start
End
Enthalpy changes during dissolution
DHsoln = DH1 + DH2 + DH3
The enthalpy of solution, DHsoln, can be either positive or negative.
DHsoln (MgSO4)= -91.2 kJ/mol --> exothermic DHsoln (NH4NO3)= 26.4 kJ/mol --> endothermic
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Why do endothermic processes sometimes occur spontaneously?
Some processes, like the dissolution of NH4NO3 in water, are spontaneous at room temperature even though heat is absorbed, not released.
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Enthalpy Is Only Part of the Picture
Entropy is a measure of: Dispersal of energy in the system. Number of microstates (arrangements) in the system. b. has greater entropy, is the favored state
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Entropy changes during dissolution
Each step also involves a change in entropy.
1. Separation of solute particles. 2. Separation of solvent particles to make holes. 3. Formation of new interactions between solute and solvent.
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SAMPLE EXERCISE 13.1 Assessing Entropy Change
In the process illustrated below, water vapor reacts with excess solid sodium sulfate to form the hydrated form of the salt. The chemical reaction is
Does the entropy of the system increase or decrease?
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Dissolution vs reaction
Ni(s) + HCl(aq)
NiCl2(aq) + H2(g)
dry
NiCl2(s)
Dissolution is a physical changeyou can get back the original solute by evaporating the solvent. If you cant, the substance didnt dissolve, it reacted.
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Degree of saturation
Saturated solution
Solvent holds as much solute as is possible at that temperature. Undissolved solid remains in flask. Dissolved solute is in dynamic equilibrium with solid solute particles.
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Degree of saturation
Unsaturated Solution
Less than the maximum amount of solute for that temperature is dissolved in the solvent. No solid remains in flask.
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Degree of saturation
Supersaturated
Solvent holds more solute than is normally possible at that temperature. These solutions are unstable; crystallization can often be stimulated by adding a seed crystal or scratching the side of the flask. Solutions
Degree of saturation
Unsaturated, Saturated or Supersaturated?
How much solute can be dissolved in a solution?
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Factors Affecting Solubility
Chemists use the axiom like dissolves like:
Polar substances tend to dissolve in polar solvents. Nonpolar substances tend to dissolve in nonpolar solvents.
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Factors Affecting Solubility
The stronger the intermolecular attractions between solute and solvent, the more likely the solute will dissolve.
Example: ethanol in water Ethanol = CH3CH2OH
Intermolecular forces = H-bonds; dipole-dipole; dispersion Ions in water also have ion-dipole forces.
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Factors Affecting Solubility
Glucose (which has hydrogen bonding) is very soluble in water. Cyclohexane (which only has dispersion forces) is not watersoluble.
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Factors Affecting Solubility
Vitamin A is soluble in nonpolar compounds (like fats). Vitamin C is soluble in water.
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Which vitamin is water-soluble and which is fat-soluble?
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Gases in Solution
In general, the solubility of gases in water increases with increasing mass. Why? Larger molecules have stronger dispersion forces.
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Gases in Solution
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Gases in Solution
Increasing pressure above solution forces more gas to dissolve.
The solubility of liquids and solids does not change appreciably with pressure. But, the solubility of a gas in a liquid is directly proportional to its pressure.
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Henrys Law
Sg = kPg where Sg is the solubility of the gas; k is the Henrys law constant for that gas in that solvent; Pg is the partial pressure of the gas above the liquid.
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Temperature
Generally, the solubility of solid solutes in liquid solvents increases with increasing temperature.
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Temperature
The opposite is true of gases. Higher temperature drives gases out of solution.
Carbonated soft drinks are more bubbly if stored in the refrigerator. Warm lakes have less O2 dissolved in them than cool lakes.
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Ways of Expressing Concentration of Solutions
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Mass Percentage
mass of A in solution 100 Mass % of A = total mass of solution
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Example
Find the concentration of a solution made by dissolving 30.0 g of alcohol in enough water to make 100.0 g solution.
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Parts per Million and Parts per Billion
Parts per Million (ppm)
mass of A in solution 106 ppm = total mass of solution
Parts per Billion (ppb)
mass of A in solution 109 ppb = total mass of solution
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Example
Infant formula is often prepared from evaporated milk. In 1972, it was reported that canned evaporated milk contained up to 3.2 ppm of lead. At this concentration, how many grams of lead are present in 8 oz (470.0 mL) of evaporated milk?
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Mole Fraction (X)
moles of A XA = total moles in solution
In some applications, one needs the mole fraction of solvent, not solute make sure you find the quantity you need!
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Example
A gas mixture contains 50.4 g of dinitrogen monoxide (N2O) and 65.2 g of oxygen gas (O2). What is the mole fraction of dinitrogen monoxide?
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Molarity (M)
M=
mol of solute L of solution
Because volume is temperature dependent, molarity can change with temperature.
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Example
What is the molarity of a solution with 3.6 g of HCl in enough water to make 500.0 mL of solution?
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Molality (m)
m=
mol of solute kg of solvent
Because neither moles nor mass change with temperature, molality (unlike molarity) is not temperature dependent.
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Example
Suppose that 0.25 mole of sugar is dissolved in 1.0 x 103 g of water. What is the molal concentration of this solution?
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SAMPLE EXERCISE 13.4 Calculation of Mass-Related Concentrations
(a) A solution is made by dissolving 13.5 g of glucose (C 6H12O6) in 0.100 kg of water. What is the mass percentage of solute in this solution? (b) A 2.5-g sample of groundwater was found to contain 5.4g of Zn2+ What is the concentration of Zn2+ in parts per million?
PRACTICE EXERCISE
(a) Calculate the mass percentage of NaCl in a solution containing 1.50 g of NaCl in 50.0 g of water. (b) A commercial bleaching solution contains 3.62 mass % sodium hypochlorite, NaOCl. What is the mass of NaOCl in a bottle containing 2500 g of bleaching solution?
PRACTICE EXERCISE
A commercial bleach solution contains 3.62 mass % NaOCl in water. Calculate (a) the molality and (b) the mole fraction of NaOCl in the solution.
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Colligative Properties
Colligative properties depend only on the number of solute particles present, not on the identity of the solute particles. Among colligative properties are
Vapor pressure lowering Boiling point elevation Melting point depression Osmotic pressure
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Vapor Pressure
As solute molecules are added to a solution, the solvent become less volatile (=decreased vapor pressure). Solute-solvent interactions contribute to this effect.
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Vapor Pressure
Therefore, the vapor pressure of a solution is lower than that of the pure solvent.
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Raoults Law PA = XAPA
where
XA is the mole fraction of compound A PA is the normal vapor pressure of A at that temperature
NOTE: This is one of those times when you want to make sure you have the vapor pressure of the solvent. Solutions
SAMPLE EXERCISE 13.8 Calculation of Vapor-Pressure Lowering
Glycerin (C3H8O3) is a nonvolatile nonelectrolyte with a density of 1.26 g/mL at 25C. Calculate the vapor pressure at 25C of a solution made by adding 50.0 mL of glycerin to 500.0 mL of water. The vapor pressure of pure water at 25C is 23.8 torr (Appendix B).
PRACTICE EXERCISE
The vapor pressure of pure water at 110C is 1070 torr. A solution of ethylene glycol and water has a vapor pressure of 1.00 atm at 110C. Assuming that Raoults law is obeyed, what is the mole fraction of ethylene glycol in the solution?
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Boiling Point Elevation and Freezing Point Depression
Solute-solvent interactions also cause solutions to have higher boiling points and lower freezing points than the pure solvent.
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Boiling Point Elevation
The change in boiling point is proportional to the molality of the solution: DTb = Kb m where Kb is the molal boiling point elevation constant, a property of the solvent.
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DTb is added to the normal boiling point of the solvent.
Example
Determine the boiling point elevation of one mole of table sugar dissolved in one kilogram of water.
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Freezing Point Depression
The change in freezing point can be found similarly: DTf = Kf m Here Kf is the molal freezing point depression constant of the solvent.
DTf is subtracted from the normal freezing point of the solvent.
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Example
How much will the freezing point be lowered if enough sugar is dissolved in water to make a 0.5 molal solution?
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Boiling Point Elevation and Freezing Point Depression
In both equations, DT does not depend on what the solute is, but only on how many particles are dissolved.
DTb = Kb m
DTf = Kf m
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Colligative Properties of Electrolytes
Because these properties depend on the number of particles dissolved, solutions of electrolytes (which dissociate in solution) show greater changes than those of nonelectrolytes. e.g. NaCl dissociates to form 2 ion particles; its limiting vant Hoff factor is 2.
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Colligative Properties of Electrolytes
However, a 1 M solution of NaCl does not show twice the change in freezing point that a 1 M solution of methanol does. It doesnt act like there are really 2 particles.
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vant Hoff Factor
One mole of NaCl in water does not really give rise to two moles of ions.
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vant Hoff Factor
Some Na+ and Cl reassociate as hydrated ion pairs, so the true concentration of particles is somewhat less than two times the concentration of NaCl.
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The vant Hoff Factor
Reassociation is more likely at higher concentration. Therefore, the number of particles present is concentration dependent.
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The vant Hoff Factor
We modify the previous equations by multiplying by the vant Hoff factor, i
DTf = Kf m i
i = 1 for non-elecrtolytes
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Osmosis
Semipermeable membranes allow some particles to pass through while blocking others. In biological systems, most semipermeable membranes (such as cell walls) allow water to pass through, but block solutes.
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Osmosis
In osmosis, there is net movement of solvent from the area of higher solvent concentration (lower solute concentration) to the are of lower solvent concentration (higher solute concentration). Water tries to equalize the concentration on both sides until pressure is too high.
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Osmotic Pressure
The pressure required to stop osmosis, known as osmotic pressure, , is
=(
n )RT = MRT V
where M is the molarity of the solution
If the osmotic pressure is the same on both sides of a membrane (i.e., the concentrations are the same), the solutions are isotonic.
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Osmosis in Blood Cells
If the solute concentration outside the cell is greater than that inside the cell, the solution is hypertonic.
Water will flow out of the cell, and crenation results.
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Osmosis in Cells
If the solute concentration outside the cell is less than that inside the cell, the solution is hypotonic.
Water will flow into the cell, and hemolysis results.
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Molar Mass from Colligative Properties
We can use the effects of a colligative property such as osmotic pressure to determine the molar mass of a compound.
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Colloids:
Suspensions of particles larger than individual ions or molecules, but too small to be settled out by gravity.
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Tyndall Effect
Colloidal suspensions can scatter rays of light. This phenomenon is known as the Tyndall effect.
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Colloids in Biological Systems
Some molecules have a polar, hydrophilic (water-loving) end and a nonpolar, hydrophobic (waterhating) end.
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Colloids in Biological Systems
Sodium stearate is one example of such a molecule.
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Colloids in Biological Systems
These molecules can aid in the emulsification of fats and oils in aqueous solutions.
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