General Chemistry Course

Course 5-6

Disperse systems
Definition A system in which one substance (particulate matter), the disperse phase, is dispersed as particles throughout another, the dispersion medium or the continuous phase.

1. Molecular dispersions

2. Colloidal dispersions
3. Coarse dispersions

Definitions

A solution is a homogeneous mixture A solute is dissolved in a solvent. solute is the substance being dissolved solvent is the liquid in which the solute is dissolved an aqueous solution has water as solvent A saturated solution is one where the concentration is at a maximum - no more solute is able to dissolve. A saturated solution represents an equilibrium: the rate of dissolving is equal to the rate of crystallization. The salt continues to dissolve, but crystallizes at the same rate so that there appears to be nothing happening.

Dissolution of Solid Solute What are the driving forces which cause solutes to dissolve to form solutions? 1. Covalent solutes dissolve by H-bonding to water or by LDF 2. Ionic solutes dissolve by dissociation into their ions.

Dilution
Suppose you have 0.500 M sucrose stock solution. How do you prepare 250 mL of 0.348 M sucrose solution ? Concentration 0.500 M Sucrose

When a solution is diluted, solvent is added to lower its concentration. The amount of solute remains constant before and after the dilution: moles BEFORE = moles AFTER C1V1 = C2V2

250 mL of 0.348 M sucrose

A bottle of 0.500 M standard sucrose stock solution is in the lab.

Give precise instructions to your assistant on how to use the stock solution to prepare 250.0 mL of a 0.348 M sucrose solution.

3 Stages of Solution Process

Separation of Solute must overcome IMF or ion-ion attractions in solute requires energy, ENDOTHERMIC ( + DH) Separation of Solvent must overcome IMF of solvent particles requires energy, ENDOTHERMIC (+ DH) Interaction of Solute & Solvent attractive bonds form between solute particles and solvent particles Solvation or Hydration (where water = solvent) releases energy, EXOTHERMIC (- DH)

Dissolution at the molecular level? Consider the dissolution of NaOH in H2O

Factors Affecting Solubility 1. Nature of Solute / Solvent. - Like dissolves like (IMF) 2. Temperature i) Solids/Liquids- Solubility increases with Temperature Increase K.E. increases motion and collision between solute / solvent. ii) gas - Solubility decreases with Temperature Increase K.E. result in gas escaping to atmosphere. 3. Pressure Factor i) Solids/Liquids - Very little effect Solids and Liquids are already close together, extra pressure will not increase solubility. ii) gas - Solubility increases with Pressure. Increase pressure squeezes gas solute into solvent.

Solubilities of Solids vs Temperature

Solubilities of several ionic solid as a function of temperature. MOST salts have greater solubility in hot water. A few salts have negative heat of solution, (exothermic process) and they become less soluble with increasing temperature.

Temperature & the Solubility of Gases The solubility of gases DECREASES at higher temperatures

Ways of Expressing Concentrations of Solutions

Mass Percentage

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

% Concentration: % Mass Example

3.5 g of CoCl2 is dissolved in 100mL water. Assuming the density of the solution is 1.0 g/mL, what is concentration of the solution in % mass?

%m = 3.5 g CoCl2 100g H2O = 3.5% (m/m)

Parts per Million and Parts per Billion

Parts per Million (ppm)

ppm = mass of A in solution 106 total mass of solution

Parts per Billion (ppb)

ppb =

mass of A in solution 109 total mass of solution

Mole Fraction (X)

moles of A XA = total moles in solution

In some applications, one needs the mole fraction of solvent, not solutemake sure you find the quantity you need!

Molarity (M)

M=

mol of solute L of solution

Because volume is temperature dependent, molarity can change with temperature.

Concentration: Molarity Example If 0.435 g of KMnO4 is dissolved in enough water to give 250. mL of solution, what is the molarity of KMnO4? As is almost always the case, the first step is to convert the mass of material to moles. 0.435 g KMnO4 1 mol KMnO4 = 0.00275 mol KMnO4 158.0 g KMnO4 Now that the number of moles of substance is known, this can be combined with the volume of solution which must be in liters to give the molarity. Because 250. mL is equivalent to 0.250 L . Molarity KMnO4
=

0.00275 mol KMnO4 = 0.0110 M 0.250 L solution

Molality (m)

m=

mol of solute kg of solvent

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

SAMPLE EXERCISE

Calculation of Mass-Related Concentrations

(a) A solution is made by dissolving 13.5 g of glucose (C6H12O6) 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 5.4 g 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.

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.

Degree of saturation

Unsaturated, Saturated or Supersaturated? How much solute can be dissolved in a solution?

Properties of Solutions

Vapor Pressure Ideal and non-ideal solutions Raoults Law and Henrys Law Colligative Properties Vapor Pressure Lowering Freezing point depression (cryoscopy) Boiling point elevation (ebullioscopy) Osmotic Pressure (Osmosis)

Henrys Law The effect of partial pressure on solubility of gases At pressure of few atmosphere or less, solubility of gas solute follows Henry Law which states that the amount of solute gas dissolved in solution is directly proportional to the amount of pressure above the solution. c = k P c = solubility of the gas (M) k = Henrys Law Constant P = partial pressure of gas Henrys Law Constants (25C), k N2 8.42 10-7 M/mmHg O2 1.66 10-6 M/mmHg CO2 4.4810-5 M/mmHg

Henrys Law & Soft Drinks

Soft drinks contain carbonated water water with dissolved carbon dioxide gas. The drinks are bottled with a CO2 pressure greater than 1 atm. When the bottle is opened, the pressure of CO2 decreases and the solubility of CO2 also decreases, according to Henrys Law. Therefore, bubbles of CO2 escape from solution.

Henrys Law Application The solubility of pure N2 (g) at 25oC and 1.00 atm pressure is 6.8 x 10-4 mol/L. What is the solubility of N2 under atmospheric conditions if the partial pressure of N2 is 0.78 atm? Step 1: Use the first set of data to find k for N2 at 25C

c 6.8 x10 4 M k 6.8 x10 4 M atm 1 P 1.00 atm

Step 2: Use this constant to find the solubility (concentration) when P is 0.78 atm:

c kP (6.8 x104 M atm 1 )(0.78 atm ) 5.3 x10 4 M

Raoults Law Describes vapor pressure lowering mathematically. The lowering of the vapour pressure when a non-volatile solute is dissolved in a volatile solvent (A) can be described by Raoults Law: PA = cAPA

only the solvent (A) contributes to the vapour pressure of the solution

PA = vapour pressure of solvent A above the solution cA = mole fraction of the solvent A in the solution PA = vapour pressure of pure solvent A

What is the vapor pressure of water above a sucrose (MW=342.3 g/mol) solution prepared by dissolving 158.0 g of sucrose in 641.6 g of water at 25 C? The vapor pressure of pure water at 25 C is 23.76 mmHg. mol sucrose = (158.0 g)/(342.3 g/mol) = 0.462 mol mol water = (641.6 g)/(18 g/mol) = 35.6 mol

mol water 35.6 Xwater = = = 0.987 (mol water)+(mol sucrose) 35.6+0.462

Psoln = Xwater Pwater = (0.987)(23.76 mm Hg)
= 23.5 mm Hg

The following graph shows the vapor pressure for water (solvent) at 90oC as a function of mole fraction of water in several solutions containing sucrose (a non-volatile solute). Note that the vapor pressure of water decreases as the concentration of sucrose increases.

Raoults Law: Mixing Two Volatile Liquids Since BOTH liquids are volatile and contribute to the vapour, the total vapor pressure can be represented using Daltons Law: PT = PA + PB The vapor pressure from each component follows Raoults Law:

PT = cAPA + cBPB
Also, cA + cB = 1 (since there are 2 components)

Mixtures of Volatile Liquids Both liquids evaporate & contribute to the vapor pressure

Colligative Properties

Dissolving solute in pure liquid will change all physical properties of liquid, Density, Vapor Pressure, Boiling Point, Freezing Point, Osmotic Pressure Colligative Properties are properties of a liquid that change when a solute is added. The magnitude of the change depends on the number of solute particles in the solution, NOT on the identity of the solute particles.

Vapor Pressure Lowering for a Solution

The diagram below shows how a phase diagram is affected by dissolving a solute in a solvent. The black curve represents the pure liquid and the blue curve represents the solution. Notice the changes in the freezing & boiling points.

Vapor Pressure Lowering

The presence of a non-volatile solute means that fewer solvent particles are at the solutions surface, so less solvent evaporates!

Application of Vapor Pressure Lowering Describe what is happening in the pictures below. Use the concept of vapor pressure lowering to explain this phenomenon.

Normal Boiling Process

Extension of vapor pressure concept: Normal Boiling Point: BP of Substance @ 1atm When solute is added, BP > Normal BP Boiling point is elevated when solute inhibits solvent from escaping.

Elevation of B. pt.

Express by Boiling point Elevation equation

Boiling Point Elevation

DTb = (Tb -Tb) = i m kb Where, DTb = BP. Elevation Tb = BP of solvent in solution Tb = BP of pure solvent m = molality , kb = BP Constant

Some Boiling Point Elevation and Freezing Point Depression Constants

Solvent Normal bp (C) pure solvent Kb (C/m) Normal fp (C) pure solvent Kf (C/m)

Water Benzene Camphor Chloroform

(CH3Cl)

100.00 80.10 207 61.70

+0.5121 +2.53 +5.611 +3.63

0.0 5.50 179.75 - 63.5

1.86 4.90 39.7 4.70

Freezing Point Depression

Normal Freezing Point: FP of Substance @ 1atm When solute is added, FP < Normal FP FP is depressed when solute inhibits solvent from crystallizing. When solution freezes the solid form is almost always pure.

Solute particles does not fit into the crystal lattice of the solvent because of the differences in size. The solute essentially remains in solution and blocks other solvent from fitting into the crystal lattice during the freezing process.

Osmotic pressure

Osmosis is the spontaneous movement of water across a semi-permeable membrane from an area of low solute concentration to an area of high solute concentration Osmotic Pressure - The Pressure that must be applied to stop osmosis

P = i CRT
where P = osmotic pressure i = vant Hoff factor C = molarity R = ideal gas constant T = Kelvin temperature

Osmosis and Blood Cells

(a) A cell placed in an isotonic solution. The net movement of water in and out of the cell is zero because the concentration of solutes inside and outside the cell is the same.
(b) In a hypertonic solution, the concentration of solutes outside the cell is greater than that inside. There is a net flow of water out of the cell, causing the cell to dehydrate, shrink, and perhaps die. (c) In a hypotonic solution, the concentration of solutes outside of the cell is less than that inside. There is a net flow of water into the cell, causing the cell to swell and perhaps to burst.

Summary

Microscopic mechanism of solution (energetics) Physical factors affecting solubility

Temperature Pressure (Henrys law)

Ideal and nonideal solutions

Raoults law

Colligative properties (nonelectrolytes)

boiling point elevation freezing point depression osmotic pressure electrolytes and vant Hoff factor

Types of disperse systems

A. On the basis of particle size

Types of disperse systems

B- On the basis of the physical state

Dispersed phase:

Stability of disperse systems

Colloidal dispersions are more stable than suspensions and emulsions, due to: - Smaller particle size - Brownian movement

Size of colloidal particles Large area to volume ratio Specific surface area: Surface area / unit weight, or Surface area / unit volume Properties due to large specific surface area: 1- Catalysis (adsorption): e.g.: platinum black 2- Colour 3- Dialysis: separation from molecular and ionic particles

Shape of colloidal particle:

Extended particles: interaction with dispersion medium Rolled particles: poor interactions with dispersion medium

Types of colloids:
A- On the basis of the interaction of the dispersed particles with the dispersion medium.

1-Lyophilic colloids : (hydrophilic) - Solvent loving solvent sheath - Mostly organic molecules e.g. : Acacia, tragacanth and insulin in water Rubber and polystyrene in benzene. 2-Lyophobic colloids : (hydrophobic) - Solvent - hating - Mostly inorganic particles e.g.: gold, silver, sulfur and silver iodide. 3-Association colloids : amphiphilic - Surfactant micelles

Preparation of colloids: Lyophilic colloids Spontaneous, e.g.: gelatin soaked in water Lyophobic colloids A- Dispersion methods: breakdown of coarse particle Colloid mill Electric dispersion Ultrasonic irradiation Peptisation: addition of preferentially adsorbed ions. B Condensation method: aggregation off subcolloidal particles 1- Chemical reaction Reduction: e.g.: colloidal Ag Oxidation: e.g.: H2S S Hydrolysis: Fe2O3 Double decomposition: colloidal AgI 2- Change of solvent: Precipitation of colloidal S from alcoholic solution by addition of water

Purification of colloids 1. Dialysis Colloidal particles Ions Stirring or renewal of the outer liquid hasten dialysis Semipermeable membrane

Applications: - Membrane filters - Membrane diffusion - Study of drug/protein binding - Heamodyalysis

Purification of colloids 2. Electrodialysis:

Application of an electric potential across the semipermeable membrane

3. Electrodecantation:

Concentration of charged colloidal particles at one side and at the base of the membrane
4. Ultrafiltration: Application of a pressure or suction across a filter