Chapter11 LEC

Chemistry: A Molecular Approach, 1st Ed.
Nivaldo Tro
Chapter 11
Liquids,
Solids, and
Intermolecular
Forces
Roy Kennedy
Massachusetts Bay Community College
Wellesley Hills, MA
2008, Prentice Hall
Comparisons of the
States of Matter
• the solid and liquid states have a much higher density
than the gas state
 therefore the molar volume of the solid and liquid states is
much smaller than the gas state
• the solid and liquid states have similar densities
 generally the solid state is a little denser
 notable exception: ice is less dense than liquid water
• the molecules in the solid and liquid state are in close
contact with each other, while the molecules in a gas
are far apart
Tro, Chemistry: A Molecular Approach 2
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

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
Kinetic - Molecular Theory
• the properties of solids, liquids, and gases can be
explained based on the kinetic energy of the
molecules and the attractive forces between
molecules
• kinetic energy tries to give molecules freedom of
motion
degrees of freedom = translational, rotational,
vibrational
• attractive forces try to keep the molecules together
• kinetic energy depends only on the temperature
KE = 1.5 kT
Gas Structure
Gas molecules are rapidly

moving in random straight
lines and free from sticking
to each other.

Explaining the Properties of Solids
• the particles in a solid are packed close
together and are fixed in position
though they may vibrate
• the close packing of the particles results in
solids being incompressible
• the inability of the particles to move around
results in solids retaining their shape and
volume when placed in a new container; and
prevents the particles from flowing
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
Explaining the Properties of Liquids
• they have higher densities than gases
because the molecules are in close contact
• they have an indefinite shape because the
limited freedom of the molecules allows
them to move around enough to get to the
container walls
• but they have a definite volume because
the limit on their freedom keeps them
from escaping the rest of the molecules

Compressibility

Phase Changes

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

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

Attractive Forces
+ - + - + - + -
+ _
+ _
+ _
+ _
+ + + + +
+ + + + + + +
- - - -
-- - -
- -
- -
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

Dispersion Force

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
Effect of Molecular Size
on Size of Dispersion Force
Noble Gases are all
nonpolar atomic
elements.
As the molar mass
increases, the number
of electrons increase.
Therefore the strength
of the dispersion
forces increases.
The stronger the
attractive forces
between the molecules,
the higher the boiling 19
point will be.
Relationship between Induced Dipole and Molecular Size
250
200
150
BP, Noble Gas
100
BP, Halogens
Boiling Point, °C
50 BP, XH4
0
1 2 3 4 5 6
-50
-100
-150
-200
-250
-300
Period

Properties of Straight Chain Alkanes
Non-Polar Molecules
Name Molar Mass BP, °C MP, °C Density, g/mL
Methane 16 -162 -183 0.47
Ethane 30 -89 -183 0.57
Propane 44 -42 -188 0.5
Butane 58 0 -138 0.58
Pentane 72 36 -130 0.56
Hexane 86 69 -95 0.66
Heptane 100 98 -91 0.68
Octane 114 126 -57 0.7
Nonane 128 151 -54 0.72
Decane 142 174 -30 0.74
Undecane 156 196 -26 0.75
Dodecane 170 216 -10 0.76
Tridecane 184 235 -5 0.76
Tetradecane 198 254 6 0.77
Pentadecane 212 271 10 0.79
Hexadecane 226 287 18 0.77
Boiling Points of n-Alkanes

n-Alkane Boiling & Melting Points
500
400
300
Temperature, °C
200
100 BP, n-alkane

MP, n-alkane
0
-100
-200
-300
0 100 200 300 400 500
Molar Mass
Effect of Molecular Shape
on Size of Dispersion Force

Alkane Boiling Points
• branched chains Alkane Boiling Points
140
have lower BPs
120
than straight
100
chains Temperature, °C
80 n-alkanes
• the straight chain 60 iso-alkanes
isomers have 40
20
more surface-to-
0
surface contact
-20 58 72 86 100 114
Molar Mass

Practice – Choose the Substance in Each Pair with
the Highest Boiling Point
a) CH4 CH3CH2CH2CH3
H H H H H
H C C
H C H C C H
H
H H H H
b) CH3CH2CH=CHCH2CH3 cyclohexane
H H H
H H H H H HC
C C C H H C C H
H C C C H C
C C H
H H H H H H
H H H

both molecules
a) CH4 CH3CH2CH2CH3 are nonpolar
H H H H H larger molar
H C C mass
H C H C C H
H
H H H H
b) CH3CH2CH=CHCH2CH3 cyclohexane
H H H
H H H H both molecules are H HC
H C
H
C
C
C
C
C
C
H nonpolar H C C H
flat molecule larger C C H
H H H H H H
H H H
surface-to-surface
Tro, Chemistry: A Molecular Approach
contact 27
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

Effect of Dipole-Dipole Attraction on
Boiling and Melting Points

Molar Boiling Dipole
Mass Point Size
CH3CH2CH3 44.09 -42°C 0.08 D
CH3-O-CH3 46.07 -24°C 1.30 D
CH3 - CH=O 44.05 20.2°C 2.69 D
CH3-CN 41.05 81.6°C 3.92 D
30
a) CH2FCH2F CH3CHF2
F HH H HF
C C C C
H H
H F H F
b)
or

a) CH2FCH2F CH3CHF2 more polar

F HH H HF
C C C C
H H
H F H F
b)
or
polar nonpolar

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
Immiscible Liquids

Polar Solvents
Dichloromethane
(methylene chloride)
Ethanol Water
(ethyl alcohol)

Nonpolar Solvents CH3
H2 H2
C C CH3 C
H3C C C HC CH
H2 H2
HC CH
n-hexane C
H
toluene
Cl
C
Cl Cl
Cl
carbon tetrachloride
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
H-Bonding
HF

H-Bonding in Water

Relationship between H-bonding
and Intermolecular Attraction BP, HX
150 BP, H2X
100 H2O BP, H3X
Boilin Point, °C
BP, XH4
50
HF H2Te
0
1 NH32 H2Se4
-50 H32S 5
SnH4
-100 GeH4
SiH4
-150 CH4
-200 Period

Practice – Choose the substance in each pair that
is a liquid at room temperature (the other is a gas)
a) CH3OH CH3CHF2
b) CH3-O-CH2CH3 CH3CH2CH2NH2

is a liquid at room temperature (the other is a gas)
a) CH3OH CH3CHF2
can H-bond
b) CH3-O-CH2CH3 CH3CH2CH2NH2
can H-bond

is more soluble in water
a) CH3OH CH3CHF2
b) CH3CH2CH2CH3 CH3Cl

is more soluble in water
a) CH3OH CH3CHF2
can H-bond with H2O
b) CH3CH2CH2CH3 CH3Cl more polar

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

Summary
• Dispersion forces are the weakest of the
intermolecular attractions.
• Dispersion forces are present in all molecules
and atoms.
• The magnitude of the dispersion forces
increases with molar mass
• Polar molecules also have dipole-dipole
attractive forces
Summary (cont’d)
• Hydrogen bonds are the strongest of the intermolecular
attractive forces
 a pure substance can have
• Hydrogen bonds will be present when a molecule has
H directly bonded to either O , N, or F atoms
 only example of H bonded to F is HF
• Ion-dipole attractions are present in mixtures of ionic
compounds with polar molecules.
• Ion-dipole attractions are the strongest intermolecular
attraction
• Ion-dipole attractions are especially important in
aqueous solutions of ionic compounds
Liquids
properties &
structure
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
50
Surface Tension
• because they have fewer neighbors
to attract them, the surface
molecules are less stable than those
in the interior
 have a higher potential energy
• the surface tension of a liquid is the
energy required to increase the
surface area a given amount
 at room temp, surface tension of H2O
= 72.8 mJ/m2

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
Surface Tension of Water vs. Temperature
80
75
2
Surface Tension, mJ/m
70
65
60
55
50
-20 0 20 40 60 80 100 120
Temperature, °C
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

Viscosity of Water vs. Temperature
1.2
0.8
Viscosity, cP
0.6
0.4
0.2
0
0 20 40 60 80 100 120
Temperature, deg C
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
Capillary Action
• the adhesive forces pull the surface liquid up the
side of the tube, while the cohesive forces pull
the interior liquid with it
• the liquid rises up the tube until the force of
gravity counteracts the capillary action forces

Meniscus
• the curving of the liquid surface in a thin
tube is due to the competition between
adhesive and cohesive forces
• the meniscus of water is concave in a
glass tube because its adhesion to the
glass is stronger than its cohesion for
itself
• the meniscus of mercury is convex in a
glass tube because its cohesion for itself
is stronger than its adhesion for the glass
 metallic bonds stronger than intermolecular
attractions
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
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

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
Evaporation vs. Condensation
• vaporization and condensation are opposite processes
• in an open container, the vapor molecules generally
spread out faster than they can condense
• the net result is that the rate of vaporization is greater
than the rate of condensation, and there is a net loss of
liquid
• however, in a closed container, the vapor is not allowed
to spread out indefinitely
• the net result in a closed container is that at some time
the rates of vaporization and condensation will be equal

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
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

Heat of Vaporization
• the amount of heat energy required to vaporize one mole
of the liquid is called the Heat of Vaporization, DHvap
 sometimes called the enthalpy of vaporization
• always endothermic, therefore DHvap is +
• somewhat temperature dependent
 DHcondensation = -DHvaporization

Example 11.3 – Calculate the mass of water that
can be vaporized with 155 kJ of heat at 100°C
Given: 155 kJ
Find: g H2O
Concept Plan: kJ mol H2O g H2O
1 mol 18.02 g
40.7 kJ 1 mol
Relationships: 1 mol H2O = 40.7 kJ, 1 mol = 18.02 g
Solution:
1 mol H 2 O 18.02 g
155 kJ    68.6 g H 2 O
40.7 kJ 1 mol
Check: since the given amount of heat is almost 4x the DHvap,

the amount of water makes sense
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

Dynamic Equilibrium

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
Vapor-Liquid Dynamic Equilibrium
• if the volume of the chamber is increased, that will decrease the
pressure of the vapor inside
 at that point, there are fewer vapor molecules in a given volume, causing
the rate of condensation to slow
• eventually enough liquid evaporates so that the rates of the
condensation increases to the point where it is once again as fast
as evaporation
 equilibrium is reestablished
• at this point, the vapor pressure will be the same as it was before

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

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
Vapor Pressure Curves
normal BP
100°C
Temperature vs Vapor Pressure
1000
900
Vapor Pressure, mmHg
800 760 mmHg

700 w ater
600 TiCl4
500 chloroform
ether
400
ethanol
300 acetone
200
100
0
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
Temperature, °C
BP Ethanol at 500 mmHg
68.1°C
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
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

Heating Curve of a Liquid
• as you heat a liquid, its
temperature increases
linearly until it reaches the
boiling point
 q = mass x Cs x DT
• once the temperature
reaches the boiling point, all
the added heat goes into
boiling the liquid – the
temperature stays constant
• once all the liquid has been
turned into gas, the
temperature can again start
to rise
Clausius-Clapeyron Equation
•• the
thegraph
the slopeof
ofvapor
logarithmthe
of line x 8.314
thepressure
vapor J/mol∙K
vs. vs.= DHvap
temperature
pressure is an
exponential
 in J/mol
inverse growth
absolute curve
temperature is a linear function
  D DHHvap
vap
ln(Pvap )  ln   e RT 
Pvap   e   RT 

  DH 
vap
ln(Pvap )  ln (  )  ln e RT 
 
 
  DH vap 
ln(Pvap )  ln (  )   
 RT 
  DH vap  1
ln(Pvap )     ln(  )
 R T
Example 11.4 – Determine the DHvap of
dichloromethane given the vapor pressure vs.
temperature data
• enter the data into a spreadsheet and calculate the
inverse of the absolute temperature and natural log of
the vapor pressure
Temperature, Vapor Pressure, Inverse Temperature, ln(Vapor

K torr K-1 Pressure)
200 0.8 0.00500 -0.2
220 4.5 0.00455 1.5
240 21 0.00417 3.0
260 71 0.00385 4.3
280 197 0.00357 5.3
300 391 0.00333 6.0

temperature data
• graph the inverse of the absolute temperature vs. the
natural log of the vapor pressure
Clausius-Clapeyron Plot for Dichloromethane
7.0
6.0
5.0
ln(vapor pressure)
4.0
3.0
2.0
1.0
0.0
0.00000 0.00100 0.00200 0.00300 0.00400 0.00500 0.00600
-1.0
Inv. Temperature K -1
79
temperature data
• add a trendline, making sure the display equation on
chart option is checked off
y = -3776.7x + 18.719
7.0
6.0
5.0
ln(vapor pressure)
4.0
3.0
2.0
1.0
0.0
0.00000 0.00100 0.00200 0.00300 0.00400 0.00500 0.00600
-1.0
80
temperature data
• determine the slope of the line
 -3776.7 ≈ 3800 K
y = -3776.7x + 18.719
7.0
6.0
5.0
ln(vapor pressure)
4.0
3.0
2.0
1.0
0.0
0.00000 0.00100 0.00200 0.00300 0.00400 0.00500 0.00600
-1.0
81
temperature data
• use the slope of the line to determine the heat of
vaporization
 -3776.7 ≈ 3800 K
- DH vap
slope 
R
- DH vap
 3800 K  J
8.314 mol  K
DH vap  3.16  10 4 J
mol
 31.6 kJ
mol
82
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   DH vap  1 1 
ln     
 P1  R  T2 T1 
Example 11.5 – Calculate the vapor pressure of
methanol at 12.0°C
Given: T1 = BP = 337.8
64.6°C,
K,PP1 1==760 torr,DH
760torr, DHvap
vap==35.2
35.2kJ/mol,
kJ/mol,
T2 = 285.2
12.0°CK
Find: P2, torr
Concept Plan: P1, T1, DHvap P2
 P   DH vap  1 1 
ln 2     
 1
P R  T2 T1 
Relationships: T(K) = T(°C) + 273.15
Solution:
TPP 
22 P
 64 .6
3
35.2 

273 D
10
. H
15 
J
P2
3371 .
18 
K e  2.31
1 1 0.0993

lnln  2.
     torr   
vap
ln 1 2 mol

11   
31 J 760
TPP  
8.314   285.2 K 337.8 K
2 P
 1
12 . 0 273 .
mol
R P T
15
K 285
2 . 2 K2 T
75.4 torr 1 
Check: the units are correct, the size makes sense since the
vapor pressure is lower at lower temperatures
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

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

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
Sublimation

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
Heating Curve of a Solid
• as you heat a solid, its
temperature increases linearly
until it reaches the melting point
 q = mass x Cs x DT
• once the temperature reaches the
melting point, all the added heat
goes into melting the solid – the
temperature stays constant
• once all the solid has been turned
into liquid, the temperature can
again start to rise
 ice/water will always have a
temperature of 0°C
 at 1 atm

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

Heat of Fusion
• the amount of heat energy required to melt one mole of the solid is
called the Heat of Fusion, DHfus
 sometimes called the enthalpy of fusion
• always endothermic, therefore DHfus is +
• somewhat temperature dependent
 DHcrystallization = -DHfusion
 generally much less than DHvap
 DHsublimation = DHfusion + DHvaporization
92
Heats of Fusion and Vaporization

Heating Curve of Water
94
Segment 1
• heating 1.00 mole of ice at -25.0°C up to the melting
point, 0.0°C
• q = mass x Cs x DT
 mass of 1.00 mole of ice = 18.0 g
 Cs = 2.09 J/mol∙°C
q  18.0 g    J
2.09 g C  0.0C   25.0C
q  941 J  0.941 kJ

Segment 2
• melting 1.00 mole of ice at the melting point, 0.0°C
• q = n∙DHfus
 n = 1.00 mole of ice
 DHfus = 6.02 kJ/mol
q  1.00 mol   kJ
6.02 mol 
q  6.02 kJ

Segment 3
• heating 1.00 mole of water at 0.0°C up to the boiling
point, 100.0°C
 mass of 1.00 mole of water = 18.0 g
 Cs = 2.09 J/mol∙°C
q  18.0 g   4.18  J
g C
 100.0C  0.0C
q  7.52  10 J  7.52 kJ 3

Segment 4
• boiling 1.00 mole of water at the boiling point, 100.0°C
• q = n∙DHvap
 n = 1.00 mole of ice
 DHfus = 40.7 kJ/mol
q  1.00 mol   kJ
40.7 mol 
q  40.7 kJ

Segment 5
• heating 1.00 mole of steam at 100.0°C up to 125.0°C
 mass of 1.00 mole of water = 18.0 g
 Cs = 2.01 J/mol∙°C
q  18.0 g    J
2.01 g C  125.0C  100.0C
q  904 J  0.904 kJ

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
Phase Diagrams
Fusion Curve
melting
critical
point
freezing
Pressure
Solid Liquid
normal normal
melting pt. boiling pt.
1 atm
Sublimation
Curve triple vaporization
point
condensation Vapor Pressure
sublimation Curve
deposition
Gas
Temperature 101
Phase Diagram of Water
25000
20000
15000
Pressure, (kPa)
10000
5000
0
-50 0 50 100 150 200 250 300 350 400 450
Te m pe rature , (°C)

Phase Diagram of Water
critical
point
374.1°C
217.7 atm
Pressure
Ice Water
normal normal
melting pt. boiling pt.
1 atm 0°C 100°C
triple
point
0.01°C Steam
0.006 atm
Temperature 104
Morphic Forms of Ice

Phase Diagram of CO2
critical
point
31.0°C
Pressure
Liquid 72.9 atm

Solid
-56.7°C triple
5.1 atm point
normal Gas
1 atm sublimation pt.
-78.5°C
Temperature 107
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

Solids
properties &
structure
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

X-ray Crystallography

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
nl=2a
• the angle of reflection is therefore related to the
distance (d) between two layers of particles
sinq = a/d
• combining equations and rearranging we get an
equation called Bragg’s Law
nl
d
2  sin q
Example 11.6 – An x-ray beam at l=154 pm striking an
iron crystal results in the angle of reflection q = 32.6°.
Assuming n = 1, calculate the distance between layers
Given: n = 1, q = 32.6°, l = 154 pm
Find: d, pm
Concept Plan:
n, q, l d
nl
d
Relationships: 2  sin q
Solution:
d
nl

1154 pm 
 143 pm
2  sin q 2sin 32.6
Check: the units are correct, the size makes sense since the
iron atom has an atomic radius of 140 pm
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
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

7 Unit Cells
c c
c
c
b b
b
a a a a b
Cubic Tetragonal Orthorhombic Monoclinic
a=b=c a=c<b abc abc
all 90° all 90° all 90° 2 faces 90°
c
c
b
b
a a
Hexagonal Rhombohedral Triclinic
a=c<b a=b=c abc
2 faces 90° no 90° no 90° 118
1 face 120°
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

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
Simple Cubic

Cubic Unit Cells -
Simple Cubic
• 8 particles, one at each corner
of a cube
• 1/8th of each particle lies in the
unit cell
2r
each particle part of 8 cells
1 particle in each unit cell
8 corners x 1/8
• edge of unit cell = twice the
radius
• coordination number of 6
Body-Centered Cubic

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
Face-Centered Cubic

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
Example 11.7 – Calculate the density of Al if it
crystallizes in a fcc and has a radius of 143 pm
Given: face-centered cubic, r = 1.43 x 10-8 cm, m = 1.792 x 10-22 g
143 pm
Find: density, g/cm3
Concept fcc mass r l V
Plan: # atoms x mass 1 atom l = 2r√2 V = l3
m, V d
d = m/V
Relation- 1 cm = 102 m,1 pm = 10-12 m V = l3, l = 2r√2, d = m/V
ships: fcc = 4 atoms/uc, Al = 26.982 g/mol, 1 mol = 6.022 x 1023 atoms
Solution:  2r Al
l4 atoms 2  2(1.43 10 8 cm)(1.414)
1 mol

26.982 g 4.045 10-822 cm
 1.792 10 g
6.022 10 23 atoms
1 mol 22

 
m 1 .792 10 g
m 1 cmd  V  6.618
8 3
V  l  4.045 10 cm
3 -12
10  23 cm 3
143 pm   -2  1.43 108 cm
 6.618 1023 cm13 pm 10 m 2.71 cmg3
Check: the accepted density of Al at 20°C is 2.71 g/cm3, so the
answer makes sense
Closest-Packed Structures
First Layer
• with spheres, it is more efficient to offset each
row in the gaps of the previous row than to line-
up rows and columns

Second Layer
• the second layer atoms can sit directly over the
atoms in the first – called an AA pattern
∙ or the second layer can sit over the holes in the
first – called an AB pattern

Third Layer – with Offset 2nd Layer
• the third layer atoms can align directly over the
atoms in the first – called an ABA pattern
∙ or the third layer can sit over the uncovered
holes in the first – called an ABC pattern
Cubic Closest-Packed
Hexagonal Closest-Packed
Tro, Chemistry: A Molecular Approach Face-Centered Cubic 131
Hexagonal Closest-Packed Structures

Cubic Closest-Packed Structures

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
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

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

Ionic Crystals
CsCl NaCl
coordination number = 8 coordination number = 6
Cs+ = 167 pm Na+ = 97 pm
Cl─ = 181 pm Cl─ = 181 pm
Lattice Holes
Tetrahedral
Hole
Octahedral
Hole
Simple Cubic
Hole

Lattice Holes
• in hexagonal closest packed or cubic closest
packed lattices there are 8 tetrahedral holes
and 4 octahedral holes per unit cell
• in simple cubic there is 1 hole per unit cell
• number and type of holes occupied
determines formula (empirical) of salt
= Octahedral
= Tetrahedral

Cesium Chloride Structures
• coordination number = 8
• ⅛ of each Cl─ (184 pm) inside
the unit cell
• whole Cs+ (167 pm) inside the
unit cell
 cubic hole = hole in simple cubic
arrangement of Cl─ ions
• Cs:Cl = 1: (8 x ⅛), therefore the
formula is CsCl

Rock Salt Structures
• Cl─ ions (181 pm) in a face-centered
cubic arrangement
 ⅛ of each corner Cl─ inside the unit cell
 ½ of each face Cl─ inside the unit cell
• each Na+ (97 pm) in holes between Cl─
 octahedral holes
 1 in center of unit cell
 ¼ of each edge Na+ inside the unit cell
• Na:Cl = (¼ x 12) + 1: (⅛ x 8) + (½ x 6)
= 4:4 = 1:1,
• therefore the formula is NaCl
Zinc Blende Structures
• S2─ ions (184 pm) in a face-centered
cubic arrangement
 ⅛ of each corner S2─ inside the unit cell
 ½ of each face S2─ inside the unit cell
• each Zn2+ (74 pm) in holes between S2─
 tetrahedral holes
 1 whole in ½ the holes
• Zn:S = (4 x 1) : (⅛ x 8) + (½ x 6) = 4:4
= 1:1,
• therefore the formula is ZnS

Fluorite Structures
• Ca2+ ions (99 pm) in a face-centered
cubic arrangement
 ⅛ of each corner Ca2+ inside the unit cell
 ½ of each face Ca2+ inside the unit cell
• each F─ (133 pm) in holes between Ca2+
 tetrahedral holes
 1 whole in all the holes
• Ca:F = (⅛ x 8) + (½ x 6): (8 x 1) = 4:8
= 1:2,
• therefore the formula is CaF2
 fluorite structure common for 1:2 ratio
• usually get the antifluorite structure
when the cation:anion ratio is 2:1
 the anions occupy the lattice sites and the
cations occupy the tetrahedral holes
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

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

Metallic Structure

Metallic Bonding
• metal atoms release their valence electrons
• metal cation “islands” fixed in a “sea” of
mobile electrons
+ + + + + + + + +
e- e- e- e- e- e- e- e-
+ + + + + + + + +
e- e- e- e- e- e- e- e-
+ + + + + + + + +

Crystal Structure of Metals at Room Temperature
= body-centered cubic = other
= hexagonal closest = cubic cp, face-centered
packed
= diamond

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

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
Properties of Diamond
• very high melting, ~3800°C
 need to overcome some covalent bonds
• very rigid
 due to the directionality of the covalent bonds
• very hard
 due to the strong covalent bonds holding the
atoms in position
 used as abrasives
• electrical insulator
• thermal conductor
 best known
• chemically very nonreactive

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
Properties of Graphite
• hexagonal crystals
• high melting, ~3800°C
 need to overcome some covalent bonding
• slippery feel
 because there are only dispersion forces holding
the sheets together, they can slide past each other
 glide planes
 lubricants
• electrical conductor
 parallel to sheets
• thermal insulator
• chemically very nonreactive
Silicates
• ~90% of earth’s crust
• extended arrays of SiO
sometimes with Al substituted for Si – aluminosilicates
• glass is the amorphous form

Quartz
• 3-dimensional array of Si covalently bonded to 4 O
 tetrahedral
• melts at ~1600°C
• very hard

Micas
• minerals that are mainly 2-dimensional arrays of
Si bonded to O
hexagonal arrangement of atoms
• sheets
• chemically stable
• thermal and electrical insulator

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

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
Molecular orbitals of polylithium

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
Types of Band Gaps and
Conductivity

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
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

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

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Chemistry: A Molecular Approach, 1st Ed.

Tro, Chemistry: A Molecular Approach 4

•Fixed = keeps shape when placed in a container

Gas molecules are rapidly

Tro, Chemistry: A Molecular Approach 7

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100 BP, n-alkane

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a) CH2FCH2F CH3CHF2 more polar

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can H-bond with H2O

b) CH3CH2CH2CH3 CH3Cl more polar

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Check: since the given amount of heat is almost 4x the DHvap,

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800 760 mmHg

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Temperature, Vapor Pressure, Inverse Temperature, ln(Vapor

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