Chapter 11
Chapter 11
Chapter 11
Chapter Eleven
• This chapter:
– describes changes from one state of matter to another.
– explores the types of intermolecular forces that underlie these
and other physical properties of substances.
Intermolecular forces
determine the
macroscopic physical
properties of liquids and
solids
Intramolecular forces
determine such
molecular properties as
molecular geometries
and dipole moments
4
Intermolecular Forces
Vapor Pressure
vaporization
Liquid Vapor
condensation
10
Liquid–Vapor Equilibrium
… the freezing
point is reached,
at which time the
temperature
remains constant If the liquid is
as solid forms. cooled carefully, it
can supercool.
13
Heating Curve for Water
The
temperature of
the solid
increases as it
is heated …
In a pressure cooker,
water boils at higher than normal temperature
Hydrothermal synthesis
in an autoclave
19
Boiling Point and Critical Point
Critical Point
The critical temperature, Tc, is the highest temperature
at which a liquid and vapor can coexist in equilibrium as
physically distinct states of matter
A-B, solid-vapor
equilibrium. Triple point Supercritical fluid
Sublimation curve Liquid and gas
become
indistinguishable!
25
Phase Diagram for HgI2
Boiling point
dry ice
No melting!
Note that at 1 atm,
only the solid and
vapor phases of
CO2 exist.
27
Phase Diagram for H2O
Intermolecular Forces
When another
nonpolar molecule
approaches …
32
… this molecule
… in this
induces a tiny dipole
molecule.
moment …
… giving weaker
dispersion forces and In the compact isomer, less
a lower boiling point. possible separation of charge …
35
Dipole–Dipole Forces
Dipole–Dipole Interactions
A permanent dipole in
one molecule can
induce a dipole in a
neighboring molecule, Opposites attract!
giving rise to a dipole–
induced dipole force
37
Predicting Physical Properties of
Molecular Substances
The first three substances are nonpolar: F2 because the atoms in the molecules are
identical, CBr4 because of the symmetrical tetrahedral molecular structure, and
butane because the electronegativities of the C and H atoms are so nearly alike. We
expect the boiling points of the three to increase with increasing molar mass:
F2(38.00 g/mol) < CH3CH2CH2CH3(58.12 g/mol) < CBr4(331.6 g/mol)
As we noted on page 452, the carbon-to-oxygen bond dipole in acetaldehyde is
not offset by any other bond dipoles. Even though the molar mass of acetaldehyde
(44.05 g/mol) is somewhat smaller than that of butane, we expect acetaldehyde to
have the higher boiling point because this molecule is quite polar (µ = 2.69 D).
Comparing acetaldehyde and CBr4 is more difficult. The polar character of
acetaldehyde suggests that it should have the higher boiling point. Because the
molar mass of CBr4 is so very much greater than that of acetaldehyde, though, we
should expect CBr4 to have the higher boiling point. We predict the following order
of increasing boiling points:
F2 < CH3CH2CH2CH3 < CH3CHO < CBr4
39
Homology
We need to figure out the pattern of increasing boiling point with increasing
length of the carbon chain. The data are for carbon-chain lengths of five, six,
seven, and eight C atoms. We want to estimate the boiling point of the 10-carbon
alkane, decane.
Note the trend in boiling-point increase per added CH 2 unit: 32.6, 29.7, 27.3.
This trend suggests that the boiling point of C9H20 is about 25 °C above that of
C8H18, and that the boiling point of C10H22 is about 23 °C greater than that of C9H20.
We therefore estimate the boiling point of decane to be 174 °C. (The observed
boiling point is 174.1 °C.)
41
Intermolecular Force: Hydrogen Bond
+ -
Y ––– H - - - Z ~~~~
+
No Chemical bonding! -
+
-
+
+
Aspirin
… while intramolecular
hydrogen bonds can
cause proteins to take a
helical shape.
N2: Nitrogen atoms are small and highly electronegative, but we cannot have hydrogen
bonds without hydrogen atoms. Hydrogen bonding does not occur.
HI: Hydrogen atoms are present, but iodine atoms are large and only moderately
electronegative. Hydrogen bonding does not occur.
HF: Hydrogen atoms are bonded to small, highly electronegative nonmetal atoms (fluorine).
Hydrogen bonding is a significant intermolecular force.
CH3CHO: Both hydrogen atoms and highly electronegative nonmetal atoms (oxygen)
are present, but as we see from the structural formula, the hydrogen atoms are bonded
to carbon, not oxygen: Hydrogen bonding is not a significant intermolecular force.
CH3OH: Again, both hydrogen atoms and a small, highly electronegative nonmetal
oxygen atom are present, and one of the hydrogen atoms is bonded to the oxygen atom:
Hydrogen bonding is a significant intermolecular force.
50
Surface Tension
Meniscus Formation
What conclusion
can we draw
about the
Water wets the
cohesive forces
glass (adhesive
in mercury?
forces) and its
attraction for
glass forms a
concave-up
surface.
54
Capillary Action
Comparing Viscosity
Viscosity is a measure of a liquid’s resistance to flow
Types of Solids
Three-dimensional
network is extremely What kind of forces
strong, rigid. must be overcome to
melt diamond?
Covalent bond!
Hexagons of
sp2-hybridized
carbon atoms.
Covalent bond!
Forces between
layers are
relatively weak.
van der Waals
forces!
C60 molecule
K3C60: Superconductor
62
Structure of a Nanotube
A nanotube can be
thought of as a sheet of
graphite, rolled into a
tube, capped with half of
a buckyball.
63
Ionic Bonds
Mg2+ and O2– ions have higher charges than do Na+, Cl–, and Br–. Also, Mg2+
+ 2– – –
is a smaller ion than Na , and O is smaller than both Cl and Br . As a
result, we expect the lattice energy of MgO to be much greater than that of
either NaCl or NaBr. Because it has the highest lattice energy, MgO should
have the highest melting point of the three compounds.
Now we need to determine whether NaCl or NaBr has the greater lattice
energy. We see that the compounds have the same cation and that their
anions have the same charge. The only difference is in the anion radii. The
– –
Cl ion is smaller than the Br ion, and therefore the interionic attractions in
NaCl are stronger than in NaBr. We expect NaCl to have a higher lattice
energy and a higher melting point than NaBr. The expected order is therefore
NaBr < NaCl < MgO.
Observed melting points of 747 °C for NaBr, 801 °C for NaCl, and 2832 °C for MgO!
66
Crystal Lattices
… in multidimensional space
In a simple cubic
structure, the
coordination
number is 6
71
Packing in Crystals
Close-Packed Structures
Tetrahedral holes
located above a sphere in the bottom layer
Octahedral holes
located above a void in the bottom layer
73
Each corner atom belongs only in 1/8 part to a given unit cell:
1/8 x 8 = 1 atom.
A cube has six faces: 1/2 x 6 = 3 atoms.
The total number of atoms in the unit cell is thus 1 + 3 = 4.
76
Example 11.11
Use the results of Example 11.10, the molar mass of copper, and
Avogadro’s number to calculate the density of metallic copper.
The mass of a copper atom is the molar mass, 63.546 g/mol Cu, divided by
Avogadro’s number. The unit cell contains the equivalent of four copper atoms.
Theoretical density
77
Ionic Crystal Structures
Smaller cations can fill the voids between the larger anions
Octahedral holes
How many Na ions are inside this unit cell? How many Cl ions? 4 : 4
X rays
Summary of Concepts
Summary of Concepts