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Potential Energy Between

Charged Particles
1  q1 • q2 
E potential =  
4π ∈0  r 

Tro, Chemistry: A Molecular Approach 1


Bonding
• a chemical bond forms when the potential
energy of the bonded atoms is less than the
potential energy of the separate atoms
• have to consider following interactions:
nucleus-to-nucleus repulsion
electron-to-electron repulsion
nucleus-to-electron attraction

Tro, Chemistry: A Molecular Approach 2


Types of Bonds
Bond
Types of Atoms Type of Bond
Characteristic
metals to electrons
Ionic
nonmetals transferred
nonmetals to electrons
Covalent
nonmetals shared
metal to electrons
Metallic
metal pooled

Tro, Chemistry: A Molecular Approach 3


Ionic Bonds
• when metals bond to nonmetals, some electrons
from the metal atoms are transferred to the
nonmetal atoms
metals have low ionization energy, relatively easy to
remove an electron from
nonmetals have high electron affinities, relatively
good to add electrons to

Tro, Chemistry: A Molecular Approach 4


Covalent Bonds
• nonmetals have relatively high ionization energies, so
it is difficult to remove electrons from them
• when nonmetals bond together, it is better in terms of
potential energy for the atoms to share valence
electrons
 potential energy lowest when the electrons are between the
nuclei
• shared electrons hold the atoms together by attracting
nuclei of both atoms

Tro, Chemistry: A Molecular Approach 5


Determining the Number of Valence
Electrons in an Atom
• the column number on the Periodic Table will tell you
how many valence electrons a main group atom has
 Transition Elements all have 2 valence electrons; Why?

1A 2A 3A 4A 5A 6A 7A 8A

Li Be B C N O F Ne

1 e-1 2 e-1 3 e-1 4 e-1 5 e-1 6 e-1 7 e-1 8 e-1

Tro, Chemistry: A Molecular Approach 6


Lewis Symbols of Atoms
• aka electron dot symbols
• use symbol of element to represent nucleus and
inner electrons
• use dots around the symbol to represent valence
electrons
 pair first two electrons for the s orbital
 put one electron on each open side for p electrons
 then pair rest of the p electrons
• • • ••
Li • • • • • • • • •
• Be • B • • C • • N • • O • • F • • Ne •
• • • •• •• ••
Tro, Chemistry: A Molecular Approach 7
Lewis Symbols of Ions
• Cations have Lewis symbols without
valence electrons
Lost in the cation formation
• Anions have Lewis symbols with 8 valence
electrons
Electrons gained in the formation of the anion
−1
•  •• 
Li• Li+1 •
• F •

• F •
• •

••
 •• 
Tro, Chemistry: A Molecular Approach 8
Octet Rule
• when atoms bond, they tend to gain, lose, or share electrons to
result in 8 valence electrons
• ns2np6
 noble gas configuration
• many exceptions
 H, Li, Be, B attain an electron configuration like He
 He = 2 valence electrons
 Li loses its one valence electron
 H shares or gains one electron
 though it commonly loses its one electron to become H+
 Be loses 2 electrons to become Be2+
 though it commonly shares its two electrons in covalent bonds, resulting in 4
valence electrons
 B loses 3 electrons to become B3+
 though it commonly shares its three electrons in covalent bonds, resulting in 6
valence electrons
 expanded octets for elements in Period 3 or below
 using empty valence d orbitals

Tro, Chemistry: A Molecular Approach 9


Lewis Theory
• the basis of Lewis Theory is that there are
certain electron arrangements in the atom that
are more stable
octet rule
• bonding occurs so atoms attain a more stable
electron configuration
more stable = lower potential energy
no attempt to quantify the energy as the calculation
is extremely complex
Tro, Chemistry: A Molecular Approach 10
Energetics of Ionic Bond Formation
• the ionization energy of the metal is endothermic
 Na(s) → Na+(g) + 1 e ─ ∆H° = +603 kJ/mol
• the electron affinity of the nonmetal is exothermic
 ½Cl2(g) + 1 e ─ → Cl─(g) ∆H° = ─ 227 kJ/mol
• generally, the ionization energy of the metal is larger
than the electron affinity of the nonmetal, therefore the
formation of the ionic compound should be
endothermic
• but the heat of formation of most ionic compounds is
exothermic and generally large; Why?
 Na(s) + ½Cl2(g) → NaCl(s) ∆H°f = -410 kJ/mol
Tro, Chemistry: A Molecular Approach 11
Ionic Bonds
• electrostatic attraction is nondirectional!!
no direct anion-cation pair
• no ionic molecule
chemical formula is an empirical formula, simply
giving the ratio of ions based on charge balance
• ions arranged in a pattern called a crystal lattice
every cation surrounded by anions; and every anion
surrounded by cations
maximizes attractions between + and - ions

Tro, Chemistry: A Molecular Approach 12


Lattice Energy
• the lattice energy is the energy released when the
solid crystal forms from separate ions in the gas state
 always exothermic
 hard to measure directly, but can be calculated from
knowledge of other processes
• lattice energy depends directly on size of charges and
inversely on distance between ions

Tro, Chemistry: A Molecular Approach 13


Born-Haber Cycle
• method for determining the lattice energy of an
ionic substance by using other reactions
use Hess’s Law to add up heats of other processes
• ∆H°f(salt) = ∆H°f(metal atoms, g) + ∆H°f(nonmetal atoms, g)
+ ∆H°f(cations, g) + ∆H°f(anions, g) + ∆H°f(crystal lattice)
 ∆H°f(crystal lattice) = Lattice Energy
 metal atoms (g) → cations (g), ∆H°f = ionization energy
don’t forget to add together all the ionization energies to get to the
desired cation
M2+ = 1st IE + 2nd IE
 nonmetal atoms (g) → anions (g), ∆H°f = electron affinity
Tro, Chemistry: A Molecular Approach 14
Trends in Lattice Energy
Ion Size
• the force of attraction between charged
particles is inversely proportional to the
distance between them
• larger ions mean the center of positive charge
(nucleus of the cation) is farther away from
negative charge (electrons of the anion)
larger ion = weaker attraction = smaller lattice
energy

Tro, Chemistry: A Molecular Approach 15


Trends in Lattice Energy
Ion Charge
• the force of attraction between
oppositely charged particles is
directly proportional to the product
of the charges Lattice Energy =
-910 kJ/mol
• larger charge means the ions are
more strongly attracted
 larger charge = stronger attraction =
larger lattice energy
• of the two factors, ion charge Lattice Energy =
generally more important -3414 kJ/mol
Tro, Chemistry: A Molecular Approach 16
Ionic Bonding
Model vs. Reality
• ionic compounds have high melting points and boiling
points
 MP generally > 300°C
 all ionic compounds are solids at room temperature
• because the attractions between ions are strong,
breaking down the crystal requires a lot of energy
 the stronger the attraction (larger the lattice energy), the
higher the melting point

Tro, Chemistry: A Molecular Approach 17


Ionic Bonding
Model vs. Reality
• ionic solids are brittle and hard
• the position of the ion in the crystal is critical to
establishing maximum attractive forces –
displacing the ions from their positions results
in like charges close to each other and the
repulsive forces take over
+ +
- - -
+ + -+ -+ +- +- +- +
- -+ - +- + + +
- - -
+ -+ + -
-
+ - + - + - + - +

- + -
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

Tro, Chemistry: A Molecular Approach 20


Single Covalent Bonds
• two atoms share a pair of electrons
 2 electrons
• one atom may have more than one single bond

•• •• ••
F • • F H• • O •H
••


••

•• •• ••
•• ••• •••
H O H

••
F F
••
••


•• •• ••
F F

Tro, Chemistry: A Molecular Approach 21


Double Covalent Bond
• two atoms sharing two pairs of electrons
4 electrons
•• ••
•O• •O


•• ••

•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

Tro, Chemistry: A Molecular Approach 25


Ionic Bonding
Model vs. Reality
• molecular compounds do not conduct electricity in the
liquid state
• molecular acids conduct electricity when dissolved in
water, but not in the solid state
• in molecular solids, there are no charged particles
around to allow the material to conduct
• when dissolved in water, molecular acids are ionized,
and have the ability to move through the structure and
therefore conduct electricity
Tro, Chemistry: A Molecular Approach 26
Bond Polarity
• covalent bonding between unlike atoms results in
unequal sharing of the electrons
one atom pulls the electrons in the bond closer to its
side
one end of the bond has larger electron density than the
other
• the result is a polar covalent bond
bond polarity
the end with the larger electron density gets a partial
negative charge
the end that is electron deficient gets a partial positive
charge
Tro, Chemistry: A Molecular Approach 27
Electronegativity
• measure of the pull an atom has on bonding
electrons
• increases across period (left to right) and
• decreases down group (top to bottom)
fluorine is the most electronegative element
francium is the least electronegative element
• the larger the difference in
electronegativity, the more polar the bond
negative end toward more electronegative atom
Tro, Chemistry: A Molecular Approach 28
Electronegativity and Bond Polarity
• If difference in electronegativity between bonded atoms
is 0, the bond is pure covalent
 equal sharing
• If difference in electronegativity between bonded atoms
is 0.1 to 0.4, the bond is nonpolar covalent
• If difference in electronegativity between bonded atoms
0.5 to 1.9, the bond is polar covalent
• If difference in electronegativity between bonded atoms
larger than or equal to 2.0, the bond is ionic
Percent Ionic Character
4% 51% “100%”

0 0.4 2.0 4.0


Electronegativity Difference 29
Bond Dipole Moments
• the dipole moment is a quantitative way of describing the
polarity of a bond
 a dipole is a material with positively and negatively charged ends
 measured
• dipole moment, µ, is a measure of bond polarity
 it is directly proportional to the size of the partial charges and
directly proportional to the distance between them
 µ = (q)(r)
 not Coulomb’s Law
 measured in Debyes, D

• the percent ionic character is the percentage of a bond’s


measured dipole moment to what it would be if full ions
Tro, Chemistry: A Molecular Approach 30
Lewis Structures
• use common bonding patterns
 C = 4 bonds & 0 lone pairs, N = 3 bonds & 1 lone pair,
O= 2 bonds & 2 lone pairs, H and halogen = 1 bond, Be
= 2 bonds & 0 lone pairs, B = 3 bonds & 0 lone pairs
 often Lewis structures with line bonds have the lone
pairs left off
 their presence is assumed from common bonding patterns

• structures which result in bonding patterns


different from common have formal charges

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

Tro, Chemistry: A Molecular Approach 33


Using Bond Energies to Estimate ∆H°rxn
• the actual bond energy depends on the surrounding
atoms and other factors
• we often use average bond energies to estimate the ∆
Hrxn
 works best when all reactants and products in gas state
• bond breaking is endothermic, ∆H(breaking) = +
• bond making is exothermic, ∆H(making) = −
∆Hrxn = ∑ (∆H(bonds broken)) + ∑ (∆H(bonds formed))

Tro, Chemistry: A Molecular Approach 34


Bond Lengths
• the distance between the nuclei of
bonded atoms is called the bond
length
• because the actual bond length
depends on the other atoms around
the bond we often use the average
bond length
averaged for similar bonds from
many compounds
Tro, Chemistry: A Molecular Approach 35
Trends in Bond Lengths
• the more electrons two atoms share, the shorter the
covalent bond
 C≡C (120 pm) < C=C (134 pm) < C−C (154 pm)
 C≡N (116 pm) < C=N (128 pm) < C−N (147 pm)
• decreases from left to right across period
 C−C (154 pm) > C−N (147 pm) > C−O (143 pm)
• increases down the column
 F−F (144 pm) > Cl−Cl (198 pm) > Br−Br (228 pm)
• in general, as bonds get longer, they also get weaker
Tro, Chemistry: A Molecular Approach 36
Metallic Bonds
• low ionization energy of metals allows them to
lose electrons easily
• the simplest theory of metallic bonding involves
the metals atoms releasing their valence electrons
to be shared by all to atoms/ions in the metal
an organization of metal cation islands in a sea of
electrons
electrons delocalized throughout the metal structure
• bonding results from attraction of cation for the
delocalized electrons
Tro, Chemistry: A Molecular Approach 37
Metallic Bonding
Model vs. Reality
• metallic solids conduct electricity
• because the free electrons are mobile, it
allows the electrons to move through the
metallic crystal and conduct electricity
• as temperature increases, electrical
conductivity decreases
• heating causes the metal ions to vibrate
faster, making it harder for electrons to
make their way through the crystal
Tro, Chemistry: A Molecular Approach 38
Metallic Bonding
Model vs. Reality
• metallic solids conduct heat
• the movement of the small, light electrons
through the solid can transfer kinetic energy
quicker than larger particles
• metallic solids reflect light
• the mobile electrons on the surface absorb
the outside light and then emit it at the same
frequency
Tro, Chemistry: A Molecular Approach 39
Metallic Bonding
Model vs. Reality
• metallic solids are malleable and ductile
• because the free electrons are mobile, the
direction of the attractive force between the
metal cation and free electrons is adjustable
• this allows the position of the metal cation
islands to move around in the sea of
electrons without breaking the attractions
and the crystal structure

Tro, Chemistry: A Molecular Approach 40


Metallic Bonding
Model vs. Reality
• metals generally have high melting points and boiling
points
 all but Hg are solids at room temperature
• the attractions of the metal cations for the free electrons
is strong and hard to overcome
• melting points generally increase to right across period
• the charge on the metal cation increases across the
period, causing stronger attractions
• melting points generally decrease down column
• the cations get larger down the column, resulting in a
larger distance from the nucleus to the free electrons
Tro, Chemistry: A Molecular Approach 41
Structure Determines Properties!
• properties of molecular substances depend on
the structure of the molecule
• the structure includes many factors, including:
the skeletal arrangement of the atoms
the kind of bonding between the atoms
ionic, polar covalent, or covalent
the shape of the molecule
• bonding theory should allow you to predict the
shapes of molecules
Tro, Chemistry: A Molecular Approach 42
Using Lewis Theory to Predict
Molecular Shapes
• Lewis theory predicts there are regions of
electrons in an atom based on placing shared
pairs of valence electrons between bonding
nuclei and unshared valence electrons located
on single nuclei
• this idea can then be extended to predict the
shapes of molecules by realizing these regions
are all negatively charged and should repel
Tro, Chemistry: A Molecular Approach 43
VSEPR Theory
• electron groups around the central atom will be
most stable when they are as far apart as
possible – we call this valence shell electron
pair repulsion theory
since electrons are negatively charged, they should
be most stable when they are separated as much as
possible
• the resulting geometric arrangement will allow
us to predict the shapes and bond angles in the
molecule
Tro, Chemistry: A Molecular Approach 44
Electron Groups
• the Lewis structure predicts the arrangement of valence
electrons around the central atom(s)
• each lone pair of electrons constitutes one electron group
on a central atom
• each bond constitutes one electron group on a central
atom
 regardless of whether it is single, double, or triple

•• •• •• there are 3 electron groups on N


•O N O •• 1 lone pair

•• 1 single bond
Tro, Chemistry: A Molecular Approach
1 double bond 45
Molecular Geometries
• there are 5 basic arrangements of electron groups
around a central atom
 based on a maximum of 6 bonding electron groups
 though there may be more than 6 on very large atoms, it is very rare
• each of these 5 basic arrangements results in 5 different
basic molecular shapes
 in order for the molecular shape and bond angles to be a
“perfect” geometric figure, all the electron groups must be
bonds and all the bonds must be equivalent
• for molecules that exhibit resonance, it doesn’t matter
which resonance form you use – the molecular
geometry will be the same
Tro, Chemistry: A Molecular Approach 46
Linear Geometry
• when there are 2 electron groups around the central
atom, they will occupy positions opposite each other
around the central atom
• this results in the molecule taking a linear geometry
• the bond angle is 180°
•• •• •• ••
• •
• Cl Be Cl •

• O C O •

•• ••

Tro, Chemistry: A Molecular Approach 47


Trigonal Geometry
• when there are 3 electron groups around the central
atom, they will occupy positions in the shape of a
triangle around the central atom
• this results in the molecule taking a trigonal planar
geometry
• the bond angle is 120°
•• ••
• •
• F B F •
•• ••

• F •

••
Tro, Chemistry: A Molecular Approach 48
Not Quite Perfect Geometry

Because the bonds are


not identical, the
observed angles are
slightly different from
ideal.
Tro, Chemistry: A Molecular Approach 49
Tetrahedral Geometry
• when there are 4 electron groups around the central
atom, they will occupy positions in the shape of a
tetrahedron around the central atom
• this results in the molecule taking a tetrahedral
geometry
• the bond angle is 109.5°
••

• F •

•• ••

• F C F •

•• ••

• F •

••
Tro, Chemistry: A Molecular Approach 50
Trigonal Bipyramidal Geometry
• when there are 5 electron groups around the central atom, they
will occupy positions in the shape of a two tetrahedra that are
base-to-base with the central atom in the center of the shared
bases
• this results in the molecule taking a trigonal bipyramidal
geometry
• the positions above and below the central atom are called the
axial positions
• the positions in the same base plane as the central atom are
called the equatorial positions
• the bond angle between equatorial positions is 120°
• the bond angle between axial and equatorial positions is 90°

Tro, Chemistry: A Molecular Approach 51


Octahedral Geometry
• when there are 6 electron groups around the central
atom, they will occupy positions in the shape of two
square-base pyramids that are base-to-base with the
central atom in the center of the shared bases
• this results in the molecule taking an octahedral
geometry
 it is called octahedral because the geometric figure has 8
sides
• all positions are equivalent
• the bond angle is 90°

Tro, Chemistry: A Molecular Approach 52


The Effect of Lone Pairs
• lone pair groups “occupy more space” on the central
atom
because their electron density is exclusively on the
central atom rather than shared like bonding electron
groups
• relative sizes of repulsive force interactions is:
Lone Pair – Lone Pair > Lone Pair – Bonding Pair > Bonding Pair – Bonding Pair

• this effects the bond angles, making them smaller


than expected
Tro, Chemistry: A Molecular Approach 53
Derivative Shapes
• the molecule’s shape will be one of basic
molecular geometries if all the electron groups
are bonds and all the bonds are equivalent
• molecules with lone pairs or different kinds of
surrounding atoms will have distorted bond
angles and different bond lengths, but the shape
will be a derivative of one of the basic shapes

Tro, Chemistry: A Molecular Approach 54


Derivative of Trigonal Geometry
• when there are 3 electron groups around the central
atom, and 1 of them is a lone pair, the resulting shape
of the molecule is called a trigonal planar - bent
shape
• the bond angle is < 120°
•• •• •• •• •• •• •• •• ••
• • • • • •
• O S O • • O S O • • O S O •

Tro, Chemistry: A Molecular Approach 55


Derivatives of Tetrahedral
Geometry
• when there are 4 electron groups around the central
atom, and 1 is a lone pair, the result is called a
pyramidal shape
 because it is a triangular-base pyramid with the central
atom at the apex
• when there are 4 electron groups around the central
atom, and 2 are lone pairs, the result is called a
tetrahedral-bent shape
 it is planar
 it looks similar to the trigonal planar-bent shape, except the
angles are smaller
• for both shapes, the bond angle is < 109.5°
Tro, Chemistry: A Molecular Approach 56
Derivatives of the
Trigonal Bipyramidal Geometry
• when there are 5 electron groups around the central atom, and
some are lone pairs, they will occupy the equatorial positions
because there is more room
• when there are 5 electron groups around the central atom, and
1 is a lone pair, the result is called see-saw shape
 aka distorted tetrahedron
• when there are 5 electron groups around the central atom, and
2 are lone pairs, the result is called T-shaped
• when there are 5 electron groups around the central atom, and
3 are lone pairs, the result is called a linear shape
• the bond angles between equatorial positions is < 120°
• the bond angles between axial and equatorial positions is <
90°
Tro, Chemistry: A Molecular Approach 57
 linear = 180° axial-to-axial
Derivatives of the
Octahedral Geometry
• when there are 6 electron groups around the central
atom, and some are lone pairs, each even number lone
pair will take a position opposite the previous lone pair
• when there are 6 electron groups around the central
atom, and 1 is a lone pair, the result is called a square
pyramid shape
 the bond angles between axial and equatorial positions is < 90°
• when there are 6 electron groups around the central
atom, and 2 are lone pairs, the result is called a square
planar shape
 the bond angles between equatorial positions is 90°
Tro, Chemistry: A Molecular Approach 58
Tro, Chemistry: A Molecular Approach 59
Tro, Chemistry: A Molecular Approach 60
Multiple Central Atoms
• many molecules have larger structures with many
interior atoms
• we can think of them as having multiple central atoms
• when this occurs, we describe the shape around each
central atom in sequence
••

shape around left C is tetrahedral H O ••


| || • •
shape around center C is trigonal planar H − C −C −O −H
| ••
shape around right O is tetrahedral-bent H

Tro, Chemistry: A Molecular Approach 61


Polarity of Molecules
• in order for a molecule to be polar it must
1) have polar bonds
 electronegativity difference - theory
 bond dipole moments - measured
2) have an unsymmetrical shape
 vector addition

• polarity affects the intermolecular forces of attraction


 therefore boiling points and solubilities
 like dissolves like

• nonbonding pairs affect molecular polarity, strong


pull in its direction
Tro, Chemistry: A Molecular Approach 62
Valence Bond Theory
• Linus Pauling and others applied the principles
of quantum mechanics to molecules
• they reasoned that bonds between atoms would
arise when the orbitals on those atoms
interacted to make a bond
• the kind of interaction depends on whether the
orbitals align along the axis between the nuclei,
or outside the axis
Tro, Chemistry: A Molecular Approach 63
Orbital Interaction
• as two atoms approached, the partially filled or
empty valence atomic orbitals on the atoms
would interact to form molecular orbitals
• the molecular orbitals would be more stable
than the separate atomic orbitals because they
would contain paired electrons shared by both
atoms
the interaction energy between atomic orbitals is
negative when the interacting atomic orbitals
contain a total of 2 electrons
Tro, Chemistry: A Molecular Approach 64
Valence Bond Theory
Main Concepts
1. the valence electrons in an atom reside in
the quantum mechanical atomic orbitals or
hybrid orbitals
2. a chemical bond results when these atomic
orbitals overlap and there is a total of 2
electrons in the new molecular orbital
a) the electrons must be spin paired
3. the shape of the molecule is determined by
the geometry of the overlapping orbitals
Tro, Chemistry: A Molecular Approach 65
Hybridization
• some atoms hybridize their orbitals to maximize
bonding
hybridizing is mixing different types of orbitals to
make a new set of degenerate orbitals
sp, sp2, sp3, sp3d, sp3d2
more bonds = more full orbitals = more stability
• better explain observed shapes of molecules
• same type of atom can have different
hybridization depending on the compound
C = sp, sp2, sp3
Tro, Chemistry: A Molecular Approach 66
Orbital Diagrams with
Hybridization
• place electrons into hybrid and unhybridized
valence orbitals as if all the orbitals have equal
energy
• when bonding, σ bonds form between hybrid
orbitals and π bonds form between unhybridized
orbitals that are parallel

Tro, Chemistry: A Molecular Approach 67


sp3 Hybridization
• atom with 4 areas of electrons
tetrahedral geometry
109.5° angles between hybrid orbitals
• atom uses hybrid orbitals for all bonds and
lone pairs H
sp3 •• sp3
H C N H
s s
H H
Tro, Chemistry: A Molecular Approach 68
Types of Bonds
• a sigma (σ) bond results when the bonding atomic
orbitals point along the axis connecting the two
bonding nuclei
 either standard atomic orbitals or hybrids
 s-to-s, p-to-p, hybrid-to-hybrid, s-to-hybrid, etc.
• a pi (π) bond results when the bonding atomic
orbitals are parallel to each other and perpendicular
to the axis connecting the two bonding nuclei
 between unhybridized parallel p orbitals
• the interaction between parallel orbitals is not as
strong as between orbitals that point at each other;
therefore σ bonds are stronger than π bonds
Tro, Chemistry: A Molecular Approach 69
sp2 sp2
••
O ••
• atom with 3 areas of electrons ••
trigonal planar system H C O H
C = trigonal planar s sp2 •• 3 s
 sp
 N = trigonal bent
 O = “linear”
120° bond angles
flat
• atom uses hybrid orbitals for σ bonds and lone
pairs, uses nonhybridized p orbital for π bond
Tro, Chemistry: A Molecular Approach 70
sp
• atom with 2 areas of electrons
 linear shape
180° bond angle
• atom uses hybrid orbitals for σ bonds or lone
pairs, uses nonhybridized p orbitals for π bonds
π
H C σ N
π
s sp sp
Tro, Chemistry: A Molecular Approach 71
sp d
3
••
••
•• F •• •

O•
-1

• atom with 5 areas of electrons •• O I



around it •• ••
••O
trigonal bipyramid shape •• F •

See-Saw, T-Shape, Linear ••
120° & 90° bond angles
• use empty d orbitals from
valence shell
• d orbitals can be used to make
π bonds
Tro, Chemistry: A Molecular Approach 72
sp3d2
• atom with 6 areas of electrons
around it ••
•• F ••
octahedral shape
••F•• ••F••
Square Pyramid, Square Planar •• ••
90° bond angles Br •
••F •
• use empty d orbitals from •• •

valence shell •• F •

••
• d orbitals can be used to make
π bonds
Tro, Chemistry: A Molecular Approach 73
Molecular Orbital Theory
• in MO theory, we apply Schrödinger’s wave equation
to the molecule to calculate a set of molecular orbitals
 in practice, the equation solution is estimated
 we start with good guesses from our experience as to what
the orbital should look like
 then test and tweak the estimate until the energy of the
orbital is minimized
• in this treatment, the electrons belong to the whole
molecule – so the orbitals belong to the whole
molecule
 unlike VB Theory where the atomic orbitals still exist in the
molecule
Tro, Chemistry: A Molecular Approach 74
LCAO
• the simplest guess starts with the atomic orbitals
of the atoms adding together to make molecular
orbitals – this is called the Linear
Combination of Atomic Orbitals method
weighted sum
• because the orbitals are wave functions, the
waves can combine either constructively or
destructively

Tro, Chemistry: A Molecular Approach 75


Molecular Orbitals
• when the wave functions combine constructively, the
resulting molecular orbital has less energy than the
original atomic orbitals – it is called a Bonding
Molecular Orbital
 σ, π
 most of the electron density between the nuclei
• when the wave functions combine destructively, the
resulting molecular orbital has more energy than the
original atomic orbitals – it is called a Antibonding
Molecular Orbital
 σ*, π*
 most of the electron density outside the nuclei
 nodes between nuclei
Tro, Chemistry: A Molecular Approach 76
Interaction of 1s Orbitals

Tro, Chemistry: A Molecular Approach 77


Molecular Orbital Theory
• Electrons in bonding MOs are stabilizing
Lower energy than the atomic orbitals
• Electrons in anti-bonding MOs are
destabilizing
Higher in energy than atomic orbitals
Electron density located outside the
internuclear axis
Electrons in anti-bonding orbitals cancel
stability gained by electrons in bonding orbitals
Tro, Chemistry: A Molecular Approach 78
MO and Properties
• Bond Order = difference between number of
electrons in bonding and antibonding orbitals
 only need to consider valence electrons
 may be a fraction
 higher bond order = stronger and shorter bonds
 if bond order = 0, then bond is unstable compared
to individual atoms - no bond will form.
• A substance will be paramagnetic if its MO
diagram has unpaired electrons
 if all electrons paired it is diamagnetic
# Bond Elec. - # Antibond Elec.
Bond Order =
2
Tro, Chemistry: A Molecular Approach 79
Heteronuclear Diatomic Molecules
• the more electronegative atom has lower energy orbitals
• when the combining atomic orbitals are identical and
equal energy, the weight of each atomic orbital in the
molecular orbital are equal
• when the combining atomic orbitals are different kinds
and energies, the atomic orbital closest in energy to the
molecular orbital contributes more to the molecular orbital
 lower energy atomic orbitals contribute more to the bonding MO
 higher energy atomic orbitals contribute more to the
antibonding MO
• nonbonding MOs remain localized on the atom donating
its atomic orbitals
Tro, Chemistry: A Molecular Approach 80
Polyatomic Molecules
• when many atoms are combined together, the
atomic orbitals of all the atoms are combined to
make a set of molecular orbitals which are
delocalized over the entire molecule
• gives results that better match real molecule
properties than either Lewis or Valence Bond
theories

Tro, Chemistry: A Molecular Approach 81


Freedom of Motion
• the molecules in a gas have complete freedom of
motion
 their kinetic energy overcomes the attractive forces between
the molecules
• the molecules in a solid are locked in place, they
cannot move around
 though they do vibrate, they don’t have enough kinetic
energy to overcome the attractive forces
• the molecules in a liquid have limited freedom – they
can move around a little within the structure of the
liquid
 they have enough kinetic energy to overcome some of the
attractive forces, but not enough to escape each other

Tro, Chemistry: A Molecular Approach 82


Properties of the 3 Phases of Matter
State Shape Volume Compressible Flow Strength of
Intermolecular
Attractions
Solid Fixed Fixed No No very strong
Liquid Indef. Fixed No Yes moderate
Gas Indef. Indef. Yes Yes very weak

•Fixed = keeps shape when placed in a container


•Indefinite = takes the shape of the container
Tro, Chemistry: A Molecular Approach 83
Solids
• some solids have their particles
arranged in an orderly geometric
pattern – we call these crystalline
solids
 salt and diamonds
• other solids have particles that do not
show a regular geometric pattern over
a long range – we call these
amorphous solids
 plastic and glass

Tro, Chemistry: A Molecular Approach 84


Why are molecules attracted to
each other?
• intermolecular attractions are due to attractive forces between
opposite charges
 + ion to - ion
 + end of polar molecule to - end of polar molecule
 H-bonding especially strong
 even nonpolar molecules will have temporary charges
• larger the charge = stronger attraction
• longer the distance = weaker attraction
• however, these attractive forces are small relative to the
bonding forces between atoms
 generally smaller charges
 generally over much larger distances

Tro, Chemistry: A Molecular Approach 85


Trends in the Strength of
Intermolecular Attraction?
• the stronger the attractions between the atoms or
molecules, the more energy it will take to separate
them
• boiling a liquid requires we add enough energy to
overcome the attractions between the molecules or
atoms
• the higher the normal boiling point of the liquid, the
stronger the intermolecular attractive forces

Tro, Chemistry: A Molecular Approach 86


Dispersion Forces
• fluctuations in the electron distribution in atoms and
molecules result in a temporary dipole
 region with excess electron density has partial (─) charge
 region with depleted electron density has partial (+) charge
• the attractive forces caused by these temporary dipoles
are called dispersion forces
 aka London Forces
• all molecules and atoms will have them
• as a temporary dipole is established in one molecule, it
induces a dipole in all the surrounding molecules

Tro, Chemistry: A Molecular Approach 87


Size of the Induced Dipole
• the magnitude of the induced dipole depends on
several factors
• polarizability of the electrons
 volume of the electron cloud
larger molar mass = more electrons = larger
electron cloud = increased polarizability =
stronger attractions
• shape of the molecule
more surface-to-surface contact = larger
induced dipole = stronger attraction
Tro, Chemistry: A Molecular Approach 88
Dipole-Dipole Attractions
• polar molecules have a permanent dipole
 because of bond polarity and shape
 dipole moment
 as well as the always present induced dipole
• the permanent dipole adds to the attractive forces
between the molecules
 raising the boiling and melting points relative to nonpolar
molecules of similar size and shape

Tro, Chemistry: A Molecular Approach 89


Attractive Forces and Solubility
• Solubility depends on the attractive forces of solute
and solvent molecules
 Like dissolves Like
 miscible liquids will always dissolve in each other
• polar substance dissolve in polar solvents
hydrophilic groups = OH, CHO, C=O, COOH, NH2,
Cl
• nonpolar molecules dissolve in nonpolar solvents
 hydrophobic groups = C-H, C-C
• Many molecules have both hydrophilic and
hydrophobic parts - solubility becomes competition
between parts
Tro, Chemistry: A Molecular Approach 90
Hydrogen Bonding
• When a very electronegative atom is bonded to
hydrogen, it strongly pulls the bonding electrons
toward it
O-H, N-H, or F-H
• Since hydrogen has no other electrons, when it
loses the electrons, the nucleus becomes
deshielded
exposing the H proton
• The exposed proton acts as a very strong center
of positive charge, attracting all the electron
clouds from neighboring molecules
Tro, Chemistry: A Molecular Approach 91
Ion-Dipole Attraction
• in a mixture, ions from an ionic compound are
attracted to the dipole of polar molecules
• the strength of the ion-dipole attraction is one of
the main factors that determines the solubility of
ionic compounds in water

Tro, Chemistry: A Molecular Approach 92


Surface Tension
• surface tension is a property of liquids that results from
the tendency of liquids to minimize their surface area
• in order to minimize their surface area, liquids form
drops that are spherical
 as long as there is no gravity
• the layer of molecules on the surface behave differently
than the interior
 because the cohesive forces on the surface molecules have a
net pull into the liquid interior
• the surface layer acts like an elastic skin

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

Tro, Chemistry: A Molecular Approach 95


Capillary Action
• capillary action is the ability of a liquid to
flow up a thin tube against the influence of
gravity
the narrower the tube, the higher the liquid rises
• capillary action is the result of the two forces
working in conjunction, the cohesive and
adhesive forces
cohesive forces attract the molecules together
adhesive forces attract the molecules on the edge
to the tube’s surface
Tro, Chemistry: A Molecular Approach 96
Vaporization
• molecules in the liquid are constantly
in motion
• the average kinetic energy is
proportional to the temperature
• however, some molecules have more
kinetic energy than the average
• if these molecules are at the surface,
they may have enough energy to
overcome the attractive forces
 therefore – the larger the surface area,
the faster the rate of evaporation
• this will allow them to escape the
liquid and become a vapor
Tro, Chemistry: A Molecular Approach 97
Distribution of Thermal Energy
• only a small fraction of the molecules in a liquid have enough
energy to escape
• but, as the temperature increases, the fraction of the molecules
with “escape energy” increases
• the higher the temperature, the faster the rate of evaporation

Tro, Chemistry: A Molecular Approach 98


Condensation
• some molecules of the vapor will lose energy
through molecular collisions
• the result will be that some of the molecules will
get captured back into the liquid when they
collide with it
• also some may stick and gather together to form
droplets of liquid
particularly on surrounding surfaces
• we call this process condensation
Tro, Chemistry: A Molecular Approach 99
Effect of Intermolecular Attraction on
Evaporation and Condensation
• the weaker the attractive forces between molecules, the
less energy they will need to vaporize
• also, weaker attractive forces means that more energy
will need to be removed from the vapor molecules
before they can condense
• the net result will be more molecules in the vapor
phase, and a liquid that evaporates faster – the weaker
the attractive forces, the faster the rate of
evaporation
• liquids that evaporate easily are said to be volatile
 e.g., gasoline, fingernail polish remover
 liquids that do not evaporate easily are called nonvolatile
 e.g., motor oil
Tro, Chemistry: A Molecular Approach 100
Energetics of Vaporization
• when the high energy molecules are lost from
the liquid, it lowers the average kinetic energy
• if energy is not drawn back into the liquid, its
temperature will decrease – therefore,
vaporization is an endothermic process
and condensation is an exothermic process
• vaporization requires input of energy to
overcome the attractions between molecules

Tro, Chemistry: A Molecular Approach 101


Heat of Vaporization
• the amount of heat energy required to vaporize one mole
of the liquid is called the Heat of Vaporization, ∆Hvap
 sometimes called the enthalpy of vaporization
• always endothermic, therefore ∆Hvap is +
• somewhat temperature dependent
• ∆Hcondensation = -∆Hvaporization

Tro, Chemistry: A Molecular Approach 102


Dynamic Equilibrium
• in a closed container, once the rates of vaporization and
condensation are equal, the total amount of vapor and
liquid will not change
• evaporation and condensation are still occurring, but
because they are opposite processes, there is no net
gain or loss or either vapor or liquid
• when two opposite processes reach the same rate so
that there is no gain or loss of material, we call it a
dynamic equilibrium
 this does not mean there are equal amounts of vapor and
liquid – it means that they are changing by equal amounts

Tro, Chemistry: A Molecular Approach 103


Vapor Pressure
• the pressure exerted by the vapor when it is in dynamic
equilibrium with its liquid is called the vapor pressure
 remember using Dalton’s Law of Partial Pressures to account
for the pressure of the water vapor when collecting gases by
water displacement?
• the weaker the attractive forces between the molecules,
the more molecules will be in the vapor
• therefore, the weaker the attractive forces, the
higher the vapor pressure
 the higher the vapor pressure, the more volatile the liquid
Tro, Chemistry: A Molecular Approach 104
Dynamic Equilibrium
• a system in dynamic equilibrium can respond to
changes in the conditions
• when conditions change, the system shifts its
position to relieve or reduce the effects of the
change

Tro, Chemistry: A Molecular Approach 105


Vapor Pressure vs. Temperature
• increasing the temperature increases the number
of molecules able to escape the liquid
• the net result is that as the temperature
increases, the vapor pressure increases
• small changes in temperature can make big
changes in vapor pressure
• the rate of growth depends on strength of the
intermolecular forces
Tro, Chemistry: A Molecular Approach 106
Boiling Point
• when the temperature of a liquid reaches a point
where its vapor pressure is the same as the
external pressure, vapor bubbles can form
anywhere in the liquid
not just on the surface
• this phenomenon is what is called boiling and
the temperature required to have the vapor
pressure = external pressure is the boiling point
Tro, Chemistry: A Molecular Approach 107
Boiling Point
• the normal boiling point is the temperature at
which the vapor pressure of the liquid = 1 atm
• the lower the external pressure, the lower the boiling
point of the liquid

Tro, Chemistry: A Molecular Approach 108


Clausius-Clapeyron Equation
2-Point Form
• the equation below can be used with just two measurements of
vapor pressure and temperature
 however, it generally gives less accurate results
 fewer data points will not give as accurate an average because there is less
averaging out of the errors
 as with any other sets of measurements

• 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

Tro, Chemistry: A Molecular Approach 110


The Critical Point
• the temperature required to produce a
supercritical fluid is called the critical
temperature
• the pressure at the critical temperature is called
the critical pressure
• at the critical temperature or higher
temperatures, the gas cannot be condensed to a
liquid, no matter how high the pressure gets

Tro, Chemistry: A Molecular Approach 111


Sublimation and Deposition
• molecules in the solid have thermal energy that allows
them to vibrate
• surface molecules with sufficient energy may break
free from the surface and become a gas – this process is
called sublimation
• the capturing of vapor molecules into a solid is called
deposition
• the solid and vapor phases exist in dynamic
equilibrium in a closed container
 at temperatures below the melting point
 therefore, molecular solids have a vapor pressure

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

Tro, Chemistry: A Molecular Approach 114


Heat of Fusion
• the amount of heat energy required to melt one mole of the solid is
called the Heat of Fusion, ∆Hfus
 sometimes called the enthalpy of fusion
• always endothermic, therefore ∆Hfus is +
• somewhat temperature dependent
• ∆Hcrystallization = -∆Hfusion
• generally much less than ∆Hvap
• ∆Hsublimation = ∆Hfusion + ∆Hvaporization

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

Tro, Chemistry: A Molecular Approach 117


Determining Crystal Structure
• crystalline solids have a very regular geometric
arrangement of their particles
• the arrangement of the particles and distances between
them is determined by x-ray diffraction
• in this technique, a crystal is struck by beams of x-rays,
which then are reflected
• the wavelength is adjusted to result in an interference
pattern – at which point the wavelength is an integral
multiple of the distances between the particles

Tro, Chemistry: A Molecular Approach 118


Bragg’s Law
• when the interference between x-rays is constructive,
the distance between the two paths (a) is an integral
multiple of the wavelength
nλ =2a
• the angle of reflection is therefore related to the
distance (d) between two layers of particles
sinθ = a/d
• combining equations and rearranging we get an
equation called Bragg’s Law
n•λ
d=
2 • sin θ
Tro, Chemistry: A Molecular Approach 119
Crystal Lattice
• when allowed to cool slowly, the particles in a
liquid will arrange themselves to give the
maximum attractive forces
therefore minimize the energy
• the result will generally be a crystalline solid
• the arrangement of the particles in a crystalline
solid is called the crystal lattice
• the smallest unit that shows the pattern of
arrangement for all the particles is called the
unit cell
Tro, Chemistry: A Molecular Approach 120
Unit Cells
• unit cells are 3-dimensional,
 usually containing 2 or 3 layers of particles
• unit cells are repeated over and over to give the macroscopic
crystal structure of the solid
• starting anywhere within the crystal results in the same unit cell
• each particle in the unit cell is called a lattice point
• lattice planes are planes connecting equivalent points in unit
cells throughout the lattice

Tro, Chemistry: A Molecular Approach 121


Unit Cells
• the number of other particles each particle is in contact
with is called its coordination number
 for ions, it is the number of oppositely charged ions an ion is
in contact with
• higher coordination number means more interaction,
therefore stronger attractive forces holding the crystal
together
• the packing efficiency is the percentage of volume in
the unit cell occupied by particles
 the higher the coordination number, the more efficiently the
particles are packing together

Tro, Chemistry: A Molecular Approach 122


Cubic Unit Cells
• all 90° angles between corners of the unit cell
• the length of all the edges are equal
• if the unit cell is made of spherical particles
⅛ of each corner particle is within the cube
½ of each particle on a face is within the cube
¼ of each particle on an edge is within the cube
• Volume of a Cube = ( edge length )
3

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

Tro, Chemistry: A Molecular Approach 128


Ionic Solids
Attractive Forces
• held together by attractions between opposite charges
 nondirectional
 therefore every cation attracts all anions around it, and vice versa
• the coordination number represents the number of close cation-
anion interactions in the crystal
• the higher the coordination number, the more stable the solid
 lowers the potential energy of the solid
• the coordination number depends on the relative sizes of the
cations and anions
 generally, anions are larger than cations
 the number of anions that can surround the cation limited by the size of
the cation
 the closer in size the ions are, the higher the coordination number is

Tro, Chemistry: A Molecular Approach 129


Nonbonding Atomic Solids

• noble gases in solid form


• solid held together by weak dispersion forces
very low melting
• tend to arrange atoms in closest-packed
structure
either hexagonal cp or cubic cp
maximizes attractive forces and minimizes energy

Tro, Chemistry: A Molecular Approach 130


Metallic Atomic Solids
• solid held together by metallic bonds
strength varies with sizes and charges of cations
coulombic attractions
• melting point varies
• mostly closest packed arrangements of the
lattice points
cations

Tro, Chemistry: A Molecular Approach 131


Network Covalent Solids
• atoms attached to its nearest neighbors by covalent
bonds
• because of the directionality of the covalent bonds,
these do not tend to form closest-packed arrangements
in the crystal
• because of the strength of the covalent bonds, these
have very high melting points
 generally > 1000°C
• dimensionality of the network affects other physical
properties

Tro, Chemistry: A Molecular Approach 132


The Diamond Structure:
a 3-Dimensional Network
• the carbon atoms in a diamond each have 4
covalent bonds to surrounding atoms
sp3
tetrahedral geometry
• this effectively makes each crystal one giant
molecule held together by covalent bonds
you can follow a path of covalent bonds from any
atom to every other atom
Tro, Chemistry: A Molecular Approach 133
The Graphite Structure:
a 2-Dimensional Network
• in graphite, the carbon atoms in a sheet are covalently
bonded together
 forming 6-member flat rings fused together
 similar to benzene
 bond length = 142 pm
 sp2
 each C has 3 sigma and 1 pi bond
 trigonal-planar geometry
 each sheet a giant molecule
• the sheets are then stacked and held together by
dispersion forces
 sheets are 341 pm apart
Tro, Chemistry: A Molecular Approach 134
Band Theory
• the structures of metals and covalent network
solids result in every atom’s orbitals being
shared by the entire structure
• for large numbers of atoms, this results in a
large number of molecular orbitals that have
approximately the same energy, we call this an
energy band

Tro, Chemistry: A Molecular Approach 135


Band Theory
• when 2 atomic orbitals combine they produce
both a bonding and an antibonding molecular
orbital
• when many atomic orbitals combine they
produce a band of bonding molecular orbitals
and a band of antibonding molecular orbitals
• the band of bonding molecular orbitals is called
the valence band
• the band of antibonding molecular orbitals is
called the conduction band
Tro, Chemistry: A Molecular Approach 136
Band Gap
• at absolute zero, all the electrons will occupy the
valence band
• as the temperature rises, some of the electrons
may acquire enough energy to jump to the
conduction band
• the difference in energy between the valence
band and conduction band is called the band gap
the larger the band gap, the fewer electrons there are
with enough energy to make the jump
Tro, Chemistry: A Molecular Approach 137
Band Gap and Conductivity
• the more electrons at any one time that a substance has in the
conduction band, the better conductor of electricity it is
• if the band gap is ~0, then the electrons will be almost as likely
to be in the conduction band as the valence band and the
material will be a conductor
 metals
 the conductivity of a metal decreases with temperature
• if the band gap is small, then a significant number of the
electrons will be in the conduction band at normal temperatures
and the material will be a semiconductor
 graphite
 the conductivity of a semiconductor increases with temperature
• if the band gap is large, then effectively no electrons will be in
the conduction band at normal temperatures and the material
will be an insulator
Tro, Chemistry: A Molecular Approach 138
Doping Semiconductors
• doping is adding impurities to the semiconductor’s
crystal to increase its conductivity
• goal is to increase the number of electrons in the
conduction band
• n-type semiconductors do not have enough electrons
themselves to add to the conduction band, so they are
doped by adding electron rich impurities
• p-type semiconductors are doped with an electron
deficient impurity, resulting in electron “holes” in the
valence band. Electrons can jump between these holes
in the valence band, allowing conduction of electricity

Tro, Chemistry: A Molecular Approach 139


Diodes
• when a p-type semiconductor adjoins an n-type
semiconductor, the result is an p-n junction
• electricity can flow across the p-n junction in
only one direction – this is called a diode
• this also allows the accumulation of electrical
energy – called an amplifier

Tro, Chemistry: A Molecular Approach 140


Solubility
• when one substance (solute) dissolves in another
(solvent) it is said to be soluble
salt is soluble in water
bromine is soluble in methylene chloride
• when one substance does not dissolve in another it is
said to be insoluble
oil is insoluble in water
• the solubility of one substance in another
depends on two factors – nature’s tendency
towards mixing, and the types of
intermolecular attractive forces
Tro, Chemistry: A Molecular Approach 141
Solubility
• there is usually a limit to the solubility of one
substance in another
gases are always soluble in each other
two liquids that are mutually soluble are said to be
miscible
alcohol and water are miscible
oil and water are immiscible
• the maximum amount of solute that can be dissolved
in a given amount of solvent is called the solubility
• the solubility of one substance in another varies with
temperature and pressure
Tro, Chemistry: A Molecular Approach 142
Mixing and the Solution Process
Entropy
• formation of a solution does not necessarily
lower the potential energy of the system
 the difference in attractive forces between atoms of
two separate ideal gases vs. two mixed ideal gases
is negligible
 yet the gases mix spontaneously
• the gases mix because the energy of the
system is lowered through the release of
entropy
• entropy is the measure of energy dispersal
throughout the system
• energy has a spontaneous drive to spread out
over as large a volume as it is allowed
Tro, Chemistry: A Molecular Approach 143
Relative Interactions and Solution Formation
Solute-to-Solute +
Solute-to-Solvent > Solution Forms
Solvent-to-Solvent
Solute-to-Solute +
Solute-to-Solvent = Solution Forms
Solvent-to-Solvent
Solute-to-Solute + Solution May or
Solute-to-Solvent <
Solvent-to-Solvent May Not Form
• when the solute-to-solvent attractions are weaker than
the sum of the solute-to-solute and solvent-to-solvent
attractions, the solution will only form if the energy
difference is small enough to be overcome by the
entropy
Tro, Chemistry: A Molecular Approach 144
Will It Dissolve?
• Chemist’s Rule of Thumb –
Like Dissolves Like
• a chemical will dissolve in a solvent if it has a similar
structure to the solvent
• when the solvent and solute structures are similar,
the solvent molecules will attract the solute particles
at least as well as the solute particles to each other

Tro, Chemistry: A Molecular Approach 145


Heats of Hydration
• for aqueous ionic solutions, the energy added to
overcome the attractions between water molecules and
the energy released in forming attractions between the
water molecules and ions is combined into a term
called the heat of hydration
 attractive forces in water = H-bonds
 attractive forces between ion and water = ion-dipole
 ∆Hhydration = heat released when 1 mole of gaseous ions
dissolves in water

Tro, Chemistry: A Molecular Approach 146


Solution Equilibrium
• the dissolution of a solute in a solvent is an equilibrium
process
• initially, when there is no dissolved solute, the only
process possible is dissolution
• shortly, solute particles can start to recombine to
reform solute molecules – but the rate of dissolution >>
rate of deposition and the solute continues to dissolve
• eventually, the rate of dissolution = the rate of
deposition – the solution is saturated with solute and no
more solute will dissolve
Tro, Chemistry: A Molecular Approach 147
Solubility Limit
• a solution that has the maximum amount of solute
dissolved in it is said to be saturated
 depends on the amount of solvent
 depends on the temperature
 and pressure of gases

• a solution that has less solute than saturation is said to


be unsaturated
• a solution that has more solute than saturation is said to
be supersaturated
Tro, Chemistry: A Molecular Approach 148
Temperature Dependence of Solubility
of Solids in Water
• solubility is generally given in grams of solute that will
dissolve in 100 g of water
• for most solids, the solubility of the solid increases as
the temperature increases
 when ∆Hsolution is endothermic
• solubility curves can be used to predict whether a
solution with a particular amount of solute dissolved in
water is saturated (on the line), unsaturated (below the
line), or supersaturated (above the line)
Tro, Chemistry: A Molecular Approach 149
Temperature Dependence of Solubility
of Gases in Water
• solubility is generally given in moles of solute
that will dissolve in 1 Liter of solution
• generally lower solubility than ionic or polar
covalent solids because most are nonpolar
molecules
• for all gases, the solubility of the gas decreases
as the temperature increases
the ∆Hsolution is exothermic because you do not need
to overcome solute-solute attractions
Tro, Chemistry: A Molecular Approach 150
Pressure Dependence of Solubility of
Gases in Water
• the larger the partial pressure of a gas in contact
with a liquid, the more soluble the gas is in the
liquid

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

Tro, Chemistry: A Molecular Approach 152


Concentrations
• solutions have variable composition
• to describe a solution, need to describe components
and relative amounts
• the terms dilute and concentrated can be used as
qualitative descriptions of the amount of solute in
solution
• concentration = amount of solute in a given amount of
solution
 occasionally amount of solvent

Tro, Chemistry: A Molecular Approach 153


Solution Concentration
Molarity
• moles of solute per 1 liter of solution
• used because it describes how many
molecules of solute in each liter of solution
• if a sugar solution concentration is 2.0 M,
1 liter of solution contains 2.0 moles of
sugar, 2 liters = 4.0 moles sugar, 0.5 liters
= 1.0 mole sugar
moles of solute
molarity =
liters of solution
Tro, Chemistry: A Molecular Approach 154
Solution Concentration
Molality, m
• moles of solute per 1 kilogram of solvent
defined in terms of amount of solvent, not solution
like the others
• does not vary with temperature
because based on masses, not volumes

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

Tro, Chemistry: A Molecular Approach 156


Percent Concentration
Part (solute)
Percent = ×100%
Whole (solution)
Mass of Solute, g
Mass Percent = ×100%
Mass of Solution, g
Mass of Solute + Mass of Solvent = Mass of Solution
Mass of Solute, g
Percent Mass/Volume = × 100%
Volume of Solution, mL
Mass of Solute + Volume of Solvent ≠ Volume of Solution
Volume of Solute, mL
Volume Percent = × 100%
Volume of Solution, mL
Volume of Solute + Volume of Solvent ≠ Volume of Solution
Tro, Chemistry: A Molecular Approach 157
Using Concentrations as
Conversion Factors
• concentrations show the relationship between
the amount of solute and the amount of solvent
 12%(m/m) sugar(aq) means 12 g sugar ≡ 100 g solution
 or 12 kg sugar ≡ 100 kg solution; or 12 lbs. ≡ 100 lbs. solution
 5.5%(m/v) Ag in Hg means 5.5 g Ag ≡ 100 mL solution
 22%(v/v) alcohol(aq) means 22 mL EtOH ≡ 100 mL solution
• The concentration can then be used to convert the
amount of solute into the amount of solution, or vice
versa
Tro, Chemistry: A Molecular Approach 158
Preparing a Solution
• need to know amount of solution and
concentration of solution
• calculate the mass of solute needed
start with amount of solution
use concentration as a conversion factor
5% by mass ⇒ 5 g solute ≡ 100 g solution
“Dissolve the grams of solute in enough solvent to
total the total amount of solution.”

Tro, Chemistry: A Molecular Approach 159


Solution Concentration
PPM
• grams of solute per 1,000,000 g of solution
• mg of solute per 1 kg of solution
• 1 liter of water = 1 kg of water
for water solutions we often approximate the kg of
the solution as the kg or L of water
grams solute x 106
grams solution
mg solute mg solute
kg solution L solution 160
Solution Concentrations
Mole Fraction, XA
• the mole fraction is the fraction of the moles of one
component in the total moles of all the components
of the solution
• total of all the mole fractions in a solution = 1
• unitless
• the mole percentage is the percentage of the moles
of one component in the total moles of all the
components of the solution
 = mole fraction x 100%

mole fraction of A = XA = moles of components A


total moles in the solution
Tro, Chemistry: A Molecular Approach 161
Converting Concentration Units
• assume a convenient amount of solution
 given %(m/m), assume 100 g solution
 given %(m/v), assume 100 mL solution
 given ppm, assume 1,000,000 g solution
 given M, assume 1 liter of solution
 given m, assume 1 kg of solvent
 given X, assume you have a total of 1 mole of solutes in the solution
• determine amount of solution in non-given unit(s)
 if assume amount of solution in grams, use density to convert to mL and
then to L
 if assume amount of solution in L or mL, use density to convert to grams
• determine the amount of solute in this amount of solution, in
grams and moles
• determine the amount of solvent in this amount of solution, in
grams and moles
• use definitions to calculate other units
Tro, Chemistry: A Molecular Approach 162
Thirsty Solutions
• a concentrated solution will draw solvent
molecules toward it due to the natural drive for
materials in nature to mix
• similarly, a concentrated solution will draw pure
solvent vapor into it due to this tendency to mix
• the result is reduction in vapor pressure

Tro, Chemistry: A Molecular Approach 163


Raoult’s Law
• the vapor pressure of a volatile solvent above a
solution is equal to its mole fraction of its
normal vapor pressure, P°
Psolvent in solution = χsolvent∙P°
since the mole fraction is always less than 1, the
vapor pressure of the solvent in solution will always
be less than the vapor pressure of the pure solvent

Tro, Chemistry: A Molecular Approach 164


Ionic Solutes and Vapor Pressure
• according to Raoult’s Law, the effect of solute on
the vapor pressure simply depends on the number
of solute particles
• when ionic compounds dissolve in water, they
dissociate – so the number of solute particles is a
multiple of the number of moles of formula units
• the effect of ionic compounds on the vapor
pressure of water is magnified by the dissociation
 since NaCl dissociates into 2 ions, Na+ and Cl−, one
mole of NaCl lowers the vapor pressure of water twice
as much as 1 mole of C12H22O11 molecules would
Tro, Chemistry: A Molecular Approach 165
Raoult’s Law for Volatile Solute
• when both the solvent and the solute can evaporate,
both molecules will be found in the vapor phase
• the total vapor pressure above the solution will be the
sum of the vapor pressures of the solute and solvent
 for an ideal solution
Ptotal = Psolute + Psolvent
• the solvent decreases the solute vapor pressure in the
same way the solute decreased the solvent’s
Psolute = χsolute∙P°solute and Psolvent = χsolvent∙P°solvent
Tro, Chemistry: A Molecular Approach 166
Ideal vs. Nonideal Solution
• in ideal solutions, the made solute-solvent
interactions are equal to the sum of the broken
solute-solute and solvent-solvent interactions
ideal solutions follow Raoult’s Law
• effectively, the solute is diluting the solvent
• if the solute-solvent interactions are stronger or
weaker than the broken interactions the solution
is nonideal
Tro, Chemistry: A Molecular Approach 167
Vapor Pressure of a
Nonideal Solution
• when the solute-solvent interactions are stronger than
the solute-solute + solvent-solvent, the total vapor
pressure of the solution will be less than predicted by
Raoult’s Law
 because the vapor pressures of the solute and solvent are
lower than ideal
• when the solute-solvent interactions are weaker than
the solute-solute + solvent-solvent, the total vapor
pressure of the solution will be larger than predicted by
Raoult’s Law
Tro, Chemistry: A Molecular Approach 168
Freezing Point Depression
• the freezing point of a solution is lower than the freezing
point of the pure solvent
 for a nonvolatile solute
 therefore the melting point of the solid solution is lower
• the difference between the freezing point of the solution
and freezing point of the pure solvent is directly
proportional to the molal concentration of solute particles
(FPsolvent – FPsolution) = ∆Tf = m∙Kf
• the proportionality constant is called the Freezing Point
Depression Constant, Kf
 the value of Kf depends on the solvent
 the units of Kf are °C/m
Tro, Chemistry: A Molecular Approach 169
Boiling Point Elevation
• the boiling point of a solution is higher than the boiling
point of the pure solvent
 for a nonvolatile solute
• the difference between the boiling point of the solution
and boiling point of the pure solvent is directly
proportional to the molal concentration of solute
particles
(BPsolution – BPsolvent) = ∆Tb = m∙Kb
• the proportionality constant is called the Boiling Point
Elevation Constant, Kb
 the value of Kb depends on the solvent
 the units of Kb are °C/m
Tro, Chemistry: A Molecular Approach 170
Osmosis
• osmosis is the flow of solvent through a semi-
permeable membrane from solution of low
concentration to solution of high concentration
• the amount of pressure needed to keep osmotic
flow from taking place is called the osmotic
pressure
• the osmotic pressure, Π, is directly proportional
to the molarity of the solute particles
R = 0.08206 (atm∙L)/(mol∙K)
Π = MRT
Tro, Chemistry: A Molecular Approach 171
Colligative Properties
• colligative properties are properties whose value
depends only on the number of solute particles, and not
on what they are
 Vapor Pressure Depression, Freezing Point Depression,
Boiling Point Elevation, Osmotic Pressure
• the van’t Hoff factor, i, is the ratio of moles of solute
particles to moles of formula units dissolved
• measured van’t Hoff factors are often lower than you
might expect due to ion pairing in solution

Tro, Chemistry: A Molecular Approach 172


Tro, Chemistry: A Molecular Approach 173
Colloids
• a colloidal suspension is a heterogeneous
mixture in which one substance is dispersed
through another
most colloids are made of finely divided particles
suspended in a medium
• the difference between colloids and regular
suspensions is generally particle size – colloidal
particles are from 1 to 100 nm in size
Tro, Chemistry: A Molecular Approach 174
Properties of Colloids
• the particles in a colloid exhibit Brownian
motion
• colloids exhibit the Tyndall Effect
scattering of light as it passes through a suspension
colloids scatter short wavelength (blue) light more
effectively than long wavelength (red) light

Tro, Chemistry: A Molecular Approach 175

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