Phase diagrams

advertisement

Solutions

A homogeneous mixture in which all of the particles have the sizes of atoms.

Driving forces for solution formation

(i) Spontaneous tendency for increasing disorder (entropy!)

(ii) Intermolecular forces

Sugar or alcohol in water

Water and ethyl alcohol are completely "miscible". Both water and ethanol are polar molecules with hydrogen bonding. The similarity of the two molecules results in solutions where the water and alcohol molecules are interchangeable. Note that hexanol is only partially soluble in water (miscible with hexane though!).

Glucose dissolves in water because polar water molecules attach to the glucose molecules by dipole-dipole (H-bond) forces. When the attractive forces of the water molecules for the glucose exceeds the attractive forces between the glucose and its neighbouring glucose molecules the water can rip the sugar molecule out of the crystal. The glucose is "solvated" when it surrounded solvent molecules. The solvent has "dissolved" the molecule.

Solution formation

Alcohol (ethanol) in water

Engine coolants

• We can now explain why car radiator coolants dissolve in water. The coolants typically contain either ethylene glycol or propylene glycol, which, like ethanol and water, contain hydrogen-bonding O-H bonds.

Solublility & Miscibility

(like dissolves like)

How do stain removers work?

• Like dissolves like dry cleaning, surfactants and oxidizing agents

(and enzymes!)

Energy Changes and Solution Formation

Heat of solution: The enthalpy change between system and surroundings when 1 mole of a solute dissolves in solvent at constant pressure

In general, solutions form when

H soln is negative.

-When

H soln is too positive, a solution will not form.

-Heat of solution is zero for an ideal solution

Examples:

MgSO

NH

4

4

NO

3 added to water has

H soln added to water has

H soln

= -91.2 kJ/mol.

= + 26.4 kJ/mol.

MgSO

4 is used in hot packs and NH

4

NO

3 is used in cold packs.

Ideal dilute solutions-effect of pressure on solubility

P

B

= x

B

K

B

Pressure and Solubility

• “The Bends” - deep sea divers

– N

2 in compressed air has low solubility in blood. At great depths, partial pressure of N

2 increases and solubility increases. After returning to surface, solubility decreases substantially and N

2 come out of blood causing small bubbles in the capillaries which may rupture the blood vessels - fatal - risk reduced if He is used since it has lower Henry’s constant.

• Soft drinks and champagne

– produced by dissolving CO

2 in a liquid under pressure

– opening bottle reduces the partial pressure of CO

2 solubility reduced, CO

2 above solution, leaves solution (effervescence)

Colligative Properties of Solutions

Physical properties that depend only upon the populations of particles in a mixture

Effect of solutes on the vapour pressure of solutions

P soln

= x solvent

P * solvent

Raoult’s Law

Molecular interpretation of Raoult’s Law

Volatile solutes and Raoult’s Law

Each component contributes its own partial pressure to the solution vapour pressure

(Dalton’s Law)

Real mixtures

Deviations because of intermolecular attractions

Application:

Distillation

Distillation

Boiling point elevation

Freezing point depression

Entropy effect (see later): when a solute is added to a pure liquid, the entropy

(disorder) is increased relative to the vapour phase. Therefore there is a weaker tendency to form a vapour (boiling point elevation). A similar molecular interpretation explains freezing point depression. The effect shifts the s-l and l-g vp curve of a phase diagram down.

T f

T b

K f m

K b m

Applications:

Cooking

 De-icing and anti-freeze

Molar mass determination

Osmotic pressure

Osmotic membrane: semi-permeable membrane that allows passage of only solvent molecules

Dialysis membrane: membrane that allows passage of solvent and small solutes.

Van’t Hoff equation

 

MRT

Applications:

Reverse osmosis

Crenation and hemolysis of red blood cells

Molar Mass determination

Colligative properties of solutions of electrolytes

1.00 m NaCl : F.P= -3.37C (not –1.86C as expected)!

Colligative properties depend on the concentration of particles

Remember: NaCl  Na + + Cl -

We have 2.00m

of particles and should get F.P: -(2x1.86C) = -3.72C

Effect of interionic attractions account for discrepancy between actual and calculated

F.P. for ionic species.

Van’t Hoff Factor compares degrees of dissociation of electrolytes i

T mea su red

T ca lcu la ted

Download