University Chemistry II Spring 2006

Instructor: Office: Phone: Email address: Office hours: Dr. Sarah A. Green Chem Sci. 607 487-2048 sgreen@mtu.edu Wednesday 1:003:00 pm Place: DOW 641

Class time: MWF 11:05-11:55

Lab Supervisor: Lorri Reill y, Chemical Sci. 508B, lareill y@mtu.edu ; 7-2044 Learning Center Coordinator: Lois Blau, Chem Sci. 206A lablau@mtu.edu; 7-2297 Textbook: Chemistry: The Central Science, 10th edition, by Brown, LeMay, and Bursten. Week 1 2 3 4 5 6 EXAM 1 7 8 BREAK 9 10 EXAM II 11 12 13 EXAM III 14 Dates Jan 9-13 Jan 16-20 Jan 23-27 Jan 30-Feb 3 Feb 6-8 Feb 13-15 Feb 15, 6:00 pm Feb 20-24 Feb 27-March 3 March 6-10 March 13-17 March 20-22 March 22, 6:00 pm March 27-31 April 3-7 April 10-12 April 12, 6:00 pm April 17-21 Chapter 13 14 15 16 17 17, Review 13-16 18 19 20 Review 17-20 21 22 23 21-23 25 Topic Solutions Chemical Kinetics Chemical Equilibrium Acid-Base Equili bria No class Friday: Winter Carnival No class Friday, Feb 17 Environmental Chemistry Thermodynamics Electrochemistry No class Friday, March 24 Nuclear Chemistry Nonmetals Metals No class Friday, April 14 Organic/Biochem

FINAL EXAM: Wednesday, April 26 from 10:15 am - 12:15 pm

This schedule is subject to modification. Any changes will be announced in class and posted to the class via WebCT.

Solutions

Chemistry, The Central Science, 10th edition Theodore L. Brown; H. Eugene LeMay, Jr.; and Bruce E. Bursten

Chapter 13 Properties of Solutions

Adapted by SA Green from: John D. Bookstaver St. Charles Community College St. Peters, MO 2006, Prentice Hall, Inc.

Solutions

Solutions
Solutions are homogeneous mixtures of two or more pure substances. In a solution, the solute is dispersed uniformly throughout the solvent.

Solutions

Solutions
How does a solid dissolve into a liquid?
What drives the dissolution process? What are the energetics of dissolution?
Solutions

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

Solutions

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.

Solutions

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.
Solutions

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.
Solutions

Enthalpy Changes in Solution

The enthalpy change of the overall process depends on DH for each of these steps.
Start

End

Solutions

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

Solutions

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.
Solutions

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 (more on this in chap 19)
Solutions

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.
Solutions

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?

Solutions

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.
Solutions

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.
Solutions

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.
Solutions

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?

More on this in Chap 17 (solubility products, p 739)

Solutions

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.

Solutions

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.
Solutions

Factors Affecting Solubility

Glucose (which has hydrogen bonding) is very soluble in water. Cyclohexane (which only has dispersion forces) is not watersoluble.
Solutions

Factors Affecting Solubility

Vitamin A is soluble in nonpolar compounds (like fats). Vitamin C is soluble in water.

Solutions

Which vitamin is water-soluble and which is fat-soluble?

Solutions

Gases in Solution
In general, the solubility of gases in water increases with increasing mass. Why? Larger molecules have stronger dispersion forces.
Solutions

Gases in Solution

QuickTime and a TIFF (LZW) decompressor are neede d to see this picture.

Solutions

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.
Solutions

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.

Solutions

Henrys Law
k for N2 at 25 =6.8 x 10-4 mol/L atm

Sg = kPg
Solutions

Temperature
Generally, the solubility of solid solutes in liquid solvents increases with increasing temperature.

Solutions

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.
Solutions

Chap 13:
Ways of Expressing Concentrations of Solutions
Solutions

Mass Percentage

mass of A in solution 100 Mass % of A = total mass of solution

Solutions

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
Solutions

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!
Solutions

Molarity (M)
M=

mol of solute L of solution

You will recall this concentration measure from Chapter 4. Because volume is temperature dependent, molarity can change with temperature.
Solutions

Molality (m)
m=

mol of solute kg of solvent

Because neither moles nor mass change with temperature, molality (unlike molarity) is not temperature dependent.
Solutions

Solutions

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.

Solutions

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

Solutions

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.
Solutions

Vapor Pressure
Therefore, the vapor pressure of a solution is lower than that of the pure solvent.

Solutions

Raoults Law PA = XA P A
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 25 C. 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?

Solutions

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.

Solutions

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.
Solutions

DTb is added to the normal boiling point of the solvent.

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.
Solutions

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

Solutions

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.

Solutions

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.

Solutions

vant Hoff Factor

One mole of NaCl in water does not really give rise to two moles of ions.

Solutions

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.
Solutions

The vant Hoff Factor

Reassociation is more likely at higher concentration. Therefore, the number of particles present is concentration dependent.
Solutions

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
Solutions

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.
Solutions

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.
Solutions

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.

Solutions

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.
Solutions

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.
Solutions

Solutions

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.

Solutions

Colloids:
Suspensions of particles larger than individual ions or molecules, but too small to be settled out by gravity.

Solutions

Tyndall Effect
Colloidal suspensions can scatter rays of light. This phenomenon is known as the Tyndall effect.

Solutions

Colloids in Biological Systems

Some molecules have a polar, hydrophilic (water-loving) end and a nonpolar, hydrophobic (waterhating) end.

Solutions

Colloids in Biological Systems

Sodium stearate is one example of such a molecule.

Solutions

Colloids in Biological Systems

These molecules can aid in the emulsification of fats and oils in aqueous solutions.

Solutions

END Chap 13

Solutions