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Charged Particles
1 q1 • q2
E potential =
4π ∈0 r
1A 2A 3A 4A 5A 6A 7A 8A
Li Be B C N O F Ne
- + -
Tro, Chemistry: A Molecular Approach
+ - + - + - 18
Ionic Bonding
Model vs. Reality
• ionic compounds conduct electricity in the liquid state
or when dissolved in water, but not in the solid state
• to conduct electricity, a material must have charged
particles that are able to flow through the material
• in the ionic solid, the charged particles are locked in
position and cannot move around to conduct
• in the liquid state, or when dissolved in water, the ions
have the ability to move through the structure and
therefore conduct electricity
Tro, Chemistry: A Molecular Approach 19
Covalent Bonding:
Bonding and Lone Pair Electrons
• Covalent bonding results when atoms share pairs
of electrons to achieve an “octet”
• Electrons that are shared by atoms are called
bonding pairs
• Electrons that are not shared by atoms but belong
to a particular atom are called lone pairs
aka nonbonding pairs
••
•• O •• •• • •• •
Bonding Pairs •• S • O
•• •
Lone Pairs
•• •• ••
F • • F H• • O •H
••
•
••
•• •• ••
•• ••• •••
H O H
••
F F
••
••
•
•
•• •• ••
F F
•
•• ••
•
•O •• O•
•
•• •• ••
·· ·
·· O
··O ·
Tro, Chemistry: A Molecular Approach 22
Triple Covalent Bond
• two atoms sharing 3 pairs of electrons
6 electrons
•• ••
•N • •N
•
• •
••
N ••
•• N
••
••
··N N ··
Tro, Chemistry: A Molecular Approach 23
Covalent Bonding
Model vs. Reality
• molecular compounds have low melting points and
boiling points
MP generally < 300°C
molecular compounds are found in all 3 states at room
temperature
• melting and boiling involve breaking the attractions
between the molecules, but not the bonds between
the atoms
the covalent bonds are strong
the attractions between the molecules are generally weak
the polarity of the covalent bonds influences the strength of
the intermolecular attractions
Tro, Chemistry: A Molecular Approach 24
Ionic Bonding
Model vs. Reality
• some molecular solids are brittle and hard, but
many are soft and waxy
• the kind and strength of the intermolecular
attractions varies based on many factors
• the covalent bonds are not broken, however, the
polarity of the bonds has influence on these
attractive forces
B C N O F
Tro, Chemistry: A Molecular Approach 31
Exceptions to the Octet Rule
• expanded octets
elements with empty d orbitals can have more
than 8 electrons
• odd number electron species e.g., NO
will have 1 unpaired electron
free-radical
very reactive
• incomplete octets
B, Al
Tro, Chemistry: A Molecular Approach 32
Bond Energies
• chemical reactions involve breaking bonds in reactant
molecules and making new bond to create the products
• the ∆H°reaction can be calculated by comparing the cost
of breaking old bonds to the profit from making new
bonds
• the amount of energy it takes to break one mole of a
bond in a compound is called the bond energy
in the gas state
homolytically – each atom gets ½ bonding electrons
93
Factors Affecting Surface Tension
• the stronger the intermolecular attractive forces,
the higher the surface tension will be
• raising the temperature of a liquid reduces its
surface tension
raising the temperature of the liquid increases the
average kinetic energy of the molecules
the increased molecular motion makes it easier to
stretch the surface
Tro, Chemistry: A Molecular Approach 94
Viscosity
• viscosity is the resistance of a liquid to flow
1 poise = 1 P = 1 g/cm∙s
often given in centipoise, cP
• larger intermolecular attractions = larger viscosity
• higher temperature = lower viscosity
• can also be used to predict the vapor pressure if you know the
heat of vaporization and the normal boiling point
remember: the vapor pressure at the normal boiling point is 760 torr
P2 − ∆H vap 1 1
ln = −
P1 R T2 T1
Tro, Chemistry: A Molecular Approach 109
Supercritical Fluid
• as a liquid is heated in a sealed container, more vapor collects
causing the pressure inside the container to rise
and the density of the vapor to increase
and the density of the liquid to decrease
• at some temperature, the meniscus between the liquid and vapor
disappears and the states commingle to form a supercritical
fluid
• supercritical fluid have properties of both gas and liquid states
sublimation
solid gas
deposition
Tro, Chemistry: A Molecular Approach 112
Melting = Fusion
• as a solid is heated, its temperature rises and the
molecules vibrate more vigorously
• once the temperature reaches the melting point,
the molecules have sufficient energy to
overcome some of the attractions that hold them
in position and the solid melts (or fuses)
• the opposite of melting is freezing
Tro, Chemistry: A Molecular Approach 113
Energetics of Melting
• when the high energy molecules are lost from
the solid, it lowers the average kinetic energy
• if energy is not drawn back into the solid its
temperature will decrease – therefore, melting
is an endothermic process
and freezing is an exothermic process
• melting requires input of energy to overcome
the attractions between molecules
115
Phase Diagrams
• describe the different states and state changes that
occur at various temperature - pressure conditions
• areas represent states
• lines represent state changes
liquid/gas line is vapor pressure curve
both states exist simultaneously
critical point is the furthest point on the vapor pressure
curve
• triple point is the temperature/pressure condition
where all three states exist simultaneously
• for most substances, freezing point increases as
pressure increases
Tro, Chemistry: A Molecular Approach 116
Water – An Extraordinary Substance
• water is a liquid at room temperature
most molecular substances with small molar masses are gases at room
temperature
due to H-bonding between molecules
• water is an excellent solvent – dissolving many ionic and polar
molecular substances
because of its large dipole moment
even many small nonpolar molecules have solubility in water
e.g., O2, CO2
• water has a very high specific heat for a molecular substance
moderating effect on coastal climates
• water expands when it freezes
at a pressure of 1 atm
about 9%
making ice less dense than liquid water
4 3
• Volume of a Sphere = π r
3
Tro, Chemistry: A Molecular Approach 123
Cubic Unit Cells -
Simple Cubic
• 8 particles, one at each corner
of a cube
• 1/8th of each particle lies in the
unit cell
each particle part of 8 cells
2r
1 particle in each unit cell
8 corners x 1/8
• edge of unit cell = twice the
radius
• coordination number of 6
Tro, Chemistry: A Molecular Approach 124
Cubic Unit Cells -
Body-Centered Cubic
• 9 particles, one at each corner of
a cube + one in center
• 1/8th of each corner particle lies
in the unit cell 4r
2 particles in each unit cell 3
8 corners x 1/8 + 1 center
• edge of unit cell = (4/√ 3) times
the radius of the particle
• coordination number of 8
Tro, Chemistry: A Molecular Approach 125
Cubic Unit Cells -
Face-Centered Cubic
• 14 particles, one at each corner of a
cube + one in center of each face
• 1/8th of each corner particle + 1/2
of face particle lies in the unit cell
4 particles in each unit cell 2r 2
8 corners x 1/8 + 6 faces x 1/2
• edge of unit cell = 2√ 2 times the
radius of the particle
• coordination number of 12
Tro, Chemistry: A Molecular Approach 126
Classifying Crystalline Solids
• classified by the kinds of units found
• sub-classified by the kinds of attractive forces holding
the units together
• molecular solids are solids whose composite units are
molecules
• ionic solids are solids whose composite units are ions
• atomic solids are solids whose composite units are
atoms
nonbonding atomic solids are held together by dispersion
forces
metallic atomic solids are held together by metallic bonds
network covalent atomic solids are held together by
covalent bonds
Tro, Chemistry: A Molecular Approach 127
Molecular Solids
• the lattice site are occupied by molecules
• the molecules are held together by
intermolecular attractive forces
dispersion forces, dipole attractions, and H-bonds
• because the attractive forces are weak, they tend
to have low melting point
generally < 300°C
151
Henry’s Law
• the solubility of a gas (Sgas) is
directly proportional to its
partial pressure, (Pgas)
Sgas = kHPgas
• kH is called Henry’s Law
Constant
moles of solute
molality, m =
kg of solvent
Tro, Chemistry: A Molecular Approach 155
Percent
• parts of solute in every 100 parts solution
• mass percent = mass of solute in 100 parts
solution by mass
if a solution is 0.9% by mass, then there are 0.9
grams of solute in every 100 grams of solution
or 0.9 kg solute in every 100 kg solution
Mass of Solute, g
Mass Percent = ×100%
Mass of Solution, g
Mass of Solute + Mass of Solvent = Mass of Solution