Chem 5

Chapter 14

Solutions and Their Physical Properties

Part 3

Review
Part 1

December 13, 2002

Summary of Colligative Properties
- four properties of dilute solutions which are dependent only
on the collective effect of the number of solute molecules
rather than on the nature of the particular solute.

• The lowering of the vapor pressure Raoult’s law PA= xAPAo

• The elevation of the boiling point ∆Tb = i Kb m

• The depression of the freezing point ∆Tf = - i Kf m

• The phenomenon of osmotic pressure π = nRT/V = MRT

Raoult’s Law

Raoult’s law PA= xAPAo xA , mole fraction of the solvent

For nonelectrolyte solution of B: xA= nA/(nA+ nB)

For electrolyte solution of B: xA= nA/(nA+ i nB)
Liquid-Vapor Equilibrium: Ideal solution of two volatile species
(Toluene and Benzene)
Raoult’s law Ptolal = Pbenz + Ptol
Pbenz = xbenzPobenz

Ptol = xtolPotol

xbenz + xtol = 1

When xbenz = xtol = 0.5

The mole fractions in the
vapor phase are

xbenz = Pbenz/Ptotal = 0.77

xtol = Ptol/Ptotal = 0.23

 At a const. pressure
Fractional Distillation

Boiling points for benzene-toluene

mixtures at 1 atm are plotted as a
function of solution and vapor
compositions.
Colloidal Suspensions

A colloid is a mixture of two or more substances in which one phase is

suspended as a large number of very small particles in a second phase.

Demo: Tyndall effect – light scattering of colloidal particles

2H+(aq) + S2O32-(aq) → H2S2O3 (aq) → H2SO3 (aq) + Colloidal sulfur

Diameter 1-1000 nm Stablized by surface charges

 Demo: Brownian Motion of Colloidal particles

Suspended particles are in constant state of motion, called Brownian

motion after Robert Brown, a Scottish botanist who used a microscope
to observe the motion of pollen particles in water. Brownian motion
results from the constant random buffeting of the particles by solvent
molecules. In 1905 Albert Einstein showed how the motion of Brownian
particles could be described on a microscopic level; his work provided
one of the most striking and convincing verifications of the molecular
hypothesis and of the kinetic theory of matter and led to a fairly accurate
determination of Avogadro’s number.
Brownian Motion Trajectory

Einstein’s result:

< ∆x2>ave = (RT/3a η NA) t

∆x= x(t) - <x>

< ∆x2>ave is the mean square displacement. R is the ideal gas

constant, a is the radius of the Brownian particle. η is the viscosity
of the liquid and t is the elapsed time.

NA is the Avogradro number: The number of elementary entities

(atom, molecules, …) in a mole, the same number as in exactly
12 g of carbon-12 atoms.
NA = 6.02214199 x1023
Chemical Bonds - Covalent bond, Ionic bond, Metallic bond
Weak Bonds - Dipole-dipole interaction, Hydrogen bond,
Ion-dipole interaction, Dispersion force
Lewis Structure – Formal Charge - Resonance Structure

Wavefunctions – Orbitals – Filling Rules

• AOs
• Hybrid AOs (sp,sp2,sp3, sp3d, sp3d2) and VSPER
• MOs, diatomic, bonding and anti-bonding MOs
• Delocalized MO, bands and band gaps

Bonds and Bond Properties • Paramagnetism

• σ and π bond • Conductivity
• Bond length
• Bond order
• Dipole moment (Electronegativity)
• Potential energy curve
• Bond energy
• Weak bonds, reflected by melting, boiling point, ∆Hvap
 H-H Potential Energy Surfaces

Dispersion Force

He - He

Covalent Bond

Ar - Ar
Strengths of intermolecular forces are reflected by boiling and melting
temperatures, as well as by enthalpies of vaporization and fusion.

The higher the MW, the higher the dispersion force.

MO of Diatomic Mol.
NO2 is a free radical.

Total number of valence electrons=5+6+6=17

O N O

Form double bond to get N close to octet

O N O O N O

-1 +1 0 0 +1 -1
RESONANCE
Delocalized MOs for NO2

N
π∗ Anti-bonding

σ framework

N
sp2 π Non-bonding

sp2 sp2
N

N
π Bonding

3 p electrons to fill 3 MOs

Bond order = 1 for the delocalized MO
Let’s look at the energy.

Calculate ∆Hf for NO2 (g) from average bond energies

1/2 N2(g) + O2(g) → NO2(g)

with N≡N : 946 kJ/mol; O=O : 498; N-O : 222; N=O : 590
∆Hf = 1/2(946) + 498 - 222 - 590 = +159 kJ/mol

The actual value is +33 kJ/mol!

NO2 is more stable than predicted from average bond
energies because of delocalization.