Chem 5

Chapter 14

Solutions and Their Physical Properties

Part 1

December 9, 2002
The Unit Cell of Methane

A face-centered cubic unit cell. The spheres represent

CH4 molecules. What is the intermolecular interaction?
Can large molecules such as proteins
be crystallized?

M. C. Escher, Dutch, 1898 - 1972

Structure Biology
Crystal structure of 50S large ribozysomal subunit

Ban, et al, Science, 289, 905 (2000) MW ~ 3 x106 Da

 SODIUM CHLORIDE

Cl-

Na+

The black dots form a fcc lattice! Cubic certainly, but which one?
Bring in another unit cell

The red dots form a fcc unit cell!

Now put these back together...
 The NaCl structure is two interpenetrating fcc
lattices, one of Na+ ions and one of Cl- ions.

Cl-

Na+

The Na+ ions sit in the holes of the Cl- ion lattice.
 IONIC SOLIDS
consist of two interpenetrating lattices of the
cations and anions.

We describe an ionic solid as a lattice of the

larger ions with the smaller ions occupying holes
in the lattice.

NOTE:
The anion is usually larger than the cation.
There are octahedral holes in the fcc lattice.

Cl-
The holes:

There is one at the center…

and 12 holes on the edges of the fcc unit cell.

1 Na+ ion 1/4 Na+ion

How many Na+ ions per unit cell?

Number of Na+ ions = 1 + 12 x (1/4) = 4

 NaCl

Remember the number of Cl- ions in the unit cell?

8x(1/8) + 6x(1/2) = 4
Na+ Cl-

Therefore 4 Cl- and 4 Na+.

So stoichiometry is OK!
 IONIC SOLIDS
The stability of the ionic compound results from
the electrostatic interactions between the ions:

There is both attraction Na+ Cl– Na+ Cl–

and repulsion.
Cl– Na+ Cl– Na+

The attractions are stronger

Na+ Cl– Na+ Cl–
than the repulsions, so the
crystal is stable.
Cl– Na+ Cl– Na+

Na+(g) + Cl-(g) → NaCl (s) ∆H =LATTICE ENERGY

Calculation of Lattice Energy by the Born-Haber Cycle

Lattice energy
Na(s) + ½ Cl2(g)→ NaCl (s) Enthalpy of formation, -411kJ
Solutions
Most of the materials that we encounter in everyday life are
mixtures. Many mixtures are homogeneous; that is, their
components are uniformly intermingled on a molecular level.
Homogeneous mixtures are called solutions.
 Solution Concentration

• Parts per million, parts per billion, and parts per trillion
• Mole fraction
• Molarity (M) = amount of solute (in moles) / volume of solution (in L)
• Molality (m) = amount of solute (in moles) / mass of solvent (in kg)

Let’s Seek Molecular Level Understanding

• Intermolecular forces
• Ionic solution
• Solubility of gases
 Intermolecular Forces in Mixtures

Enthalpy of Solution:
∆Hsoln for pure solvent + pure solute → solution

• For ideal solution ∆Hsoln = 0, the intermolecular forces are equal in strength
(D2O in H2O, toluene in benzene).

• For non ideal solution ∆Hsoln < 0, the exothemic reaction arises from stronger
interactions between solvent and solute molecules.

• For non ideal solution ∆Hsoln > 0, the endothemic reaction arises from weaker
interactions between solvent and solute molecules.

• Dissolution does not occur if attractions between unlike molecules are much
weaker than between like molecules.

“Like dissolves like!”

Na+ and Cl- ions are solvated by water molecules.

The force is ion-dipole interaction.

 Enthalpy of Solution for NaCl
H2O
NaCl (s) → Na+(aq) + Cl-(aq) ∆Hsoln

NaCl (s) → Na+(g) + Cl-(g) ∆H1=-lattice energy of NaCl = 787kJ/mol > 0

H2O
Na+ (g) → Na+(aq) ∆H2 = hydration energy of Na+ = - 444kJ/mol < 0

HO
Cl- (g) →
2
Cl-(aq) ∆H3 = hydration energy of Cl- = - 340kJ/mol < 0

H2O
NaCl (s) → Na+(aq) + Cl-(aq) ∆Hsoln

∆Hsoln = ∆H1 + (∆H2 + ∆H3) = 787 kJ/mol – 784 kJ/mol = 3 kJ/mol

- Lattice Enthalpy Enthalpy
Enthalpy of hydration of solution
Endothermic
DEMO: Instant Coldpack
H2O

NH4NO3 (s) → NH4+ (aq)+ NO3- (aq) ∆Hsoln > 0

An endothermic reaction
An instant ice pack, containing ammonium nitrate, used to treat
athletic injuries. To activate the pack, the container is kneaded,
breaking the seal separating solid NH4NO3 from water. The heat of
solution of NH4NO3 is positive, so the temperature of the solution
decreases.

Instant Hotpack
A super-saturated solution of sodium acetate is mixed with
sodium acetate crystals, causing crystallization.

CH3COO- (aq) + Na+ (aq) → CH3COONa (s) ∆H < 0

An exothermic reaction
 Dynamic Equilibrium for Saturated Solution

First dissolution After a while, the rate The solution becomes

occurs. of crystallization becomes saturated when the rates
significant. of dissolution and
crystallization become equal.
 Ionic solids usually have higher solubility at higher temperatures.

Recrystallization of KNO3
Solubility of Gases NH3(g)

DEMO:

The Fountain Effect

H2O

Effect of temperature on gas solubility:

Lower solubility at high temperature

Effect of pressure on gas solubility:
Lower solubility at lower pressure

Henry’s Law

C = k Pgas

C: solubility of gas
k: proportionality const.
 Deep-sea divers breath compressed air.

N2 is soluble in blood under high

pressure, but the dissolved N2
comes out of solution rapidly when
the diver returns to the surface.
Small bubbles form in the blood
stream, bursting and blocking blood
vessels, causing the dangerous
condition called “the bends”.