Luclienphantu 05

Intermolecular Forces,
Liquids, and Solids
Lực liên kết liên phân tử

Trạng thái ngưng kết của vật chất
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Liquids and Solids: A Molecular Comparison
Tính chất vật lý của các chất được hiểu theo khái niệm
của thuyết động học phân tử (kinetic molecular theory)
như sau:
• Chất khí dễ bị nén, có hình dạng và thể tích của vật
chứa :
• Các phân tử chất khí cách xa nhau, không tương tác với nhau.
• Chất lỏng hầu như không bị nén, có hình dạng (nhưng
không có thể tích) của vật chứa :
• Các phân tử chất lỏng được giữ gần nhau hơn các phân tử chất khí,
nhưng không chắc đến mức chúng không thể trượt qua nhau (slide
past each other)
• Chất rắn không bị nén, có hình dạng và thể tích xác định
• Các phân tử chất rắn được giữ gần nhau. Các phân tử chất rắn được
chắc đến mức chúng không thể trượt qua nhau được

A Molecular Comparison of Liquids
and Solids

A Molecular Comparison of Liquids
and Solids
• Converting a gas into a liquid or solid requires the molecules to
get closer to each other/ Để biến đổi một chất khí thành lỏng
hay rắn:
– cool or compress/ làm lạnh hay nén
• Converting a solid into a liquid or gas requires the molecules to
move further apart:/Để biến đổi một chất rắn thành lỏng hay
khí:
– heat or reduce pressure/ gia nhiệt hay giảm áp suất
• The forces holding solids and liquids together are called
intermolecular forces ( lực giữ các chất lỏng và rắn lai với nhau
được gọi là lực liên phân tử).

Intermolecular Forces
• The covalent bond holding a molecule together is an
intramolecular forces (lục nội phân tử).
• The attraction between molecules is an intermolecular
force (lực liên phân tử)
• Intermolecular forces are much weaker than
intramolecular forces (e.g. 16 kJ/mol vs. 431 kJ/mol for
HCl).
• When a substance melts (nóng chảy) or boils (sôi) the
intermolecular forces are broken (not the covalent
bonds).
• When a substance condenses (ngưng tụ)
intermolecular forces are formed.


Ion-Dipole Forces (lực ion-lưỡng cực)
• Interaction between an ion (e.g. Na+) and a dipole
(e.g. water).
• Strongest of all intermolecular forces:
Q1Q2
F k
d2
– Since Q1 is a full charge and Q2 is a partial charge, F is
comparatively large.
• F increases as Q increases and as d decreases:
– the larger the charge and smaller the ion, the larger the
ion-dipole attraction.


Dipole-Dipole Forces (lực lưỡng cực-lưỡng cực)
• Interaction between a dipole (e.g. water) and a
dipole (e.g. water).
• Dipole-dipole forces exist between neutral polar
molecules (giữa các phân tử phân cực trunghoà).
• Polar molecules need to be close together.
• Weaker than ion-dipole forces:
Q1Q2
F k
2
– Q1 and Q2 are partial charges.
d
Dipole-Dipole Forces
• There is a mix of attractive (hút)
and repulsive (đẩy) dipole-
dipole forces as the molecules
tumble.
• If two molecules have about the
same mass and size, then
dipole-dipole forces increase
with increasing polarity.

London Dispersion Forces
• Weakest of all intermolecular forces.
• It is possible for two adjacent (kề nhau) neutral
molecules to affect each other.
• The nucleus of one molecule (or atom) attracts the
electrons of the adjacent molecule (or atom).
• For an instant, the electron clouds become
distorted.
• In that instant a dipole is formed (called an
instantaneous dipole-lưỡng cực tạm thời).


• One instantaneous dipole can induce (tác động)
another instantaneous dipole in an adjacent
molecule (or atom).
• The forces between instantaneous dipoles are
called London dispersion forces.
• Polarizability is the ease with which an electron
cloud can be deformed.
• The larger the molecule (the greater the number
of electrons) the more polarizable.


• London dispersion forces increase as molecular
weight increases.
• London dispersion forces exist between all
molecules.
• London dispersion forces depend on the shape
of the molecule.
• The greater the surface area available for
contact, the greater the dispersion forces.
• London dispersion forces between spherical
(dạng cầu) molecules are lower than between
sausage-like (dạng xúc xích) molecules.
Hydrogen Bonding (liên kết Hydro)
• Special case of dipole-dipole forces.
• By experiments: boiling points of compounds with
H-F, H-O, and H-N bonds are abnormally high.
• Intermolecular forces are abnormally strong.
• H-bonding requires H bonded to an
electronegative element (most important for
compounds of F, O, and N).
– Electrons in the H-X (X = electronegative element) lie
much closer to X than H.
– H has only one electron, so in the H-X bond, the + H
presents an almost bare proton to the - X.
– Therefore, H-bonds are strong.

Hydrogen Bonding

Hydrogen Bonding
Hydrogen bonds are responsible for:
– Ice Floating
• Solids are usually more closely packed than liquids;
• therefore, solids are more dense than liquids.
• Ice is ordered with an open structure to optimize H-bonding.
• Therefore, ice is less dense than water.
• In water the H-O bond length is 1.0 Å.
• The O…H hydrogen bond length is 1.8 Å.
• Ice has waters arranged in an open, regular hexagon.
• Each + H points towards a lone pair on O.
• Ice floats, so it forms an insulating layer on top of lakes,
rivers, etc. Therefore, aquatic life can survive in winter.

Hydrogen Bonding
• Hydrogen bonds are responsible for:
– Protein Structure
• Protein folding is a consequence of H-bonding.
• DNA Transport of Genetic Information

Comparing Intermolecular Forces

Some Properties of Liquids
Viscosity (độ nhớt)
• Viscosity is the resistance of a liquid to flow.
• A liquid flows by sliding molecules over each
other.
• The stronger the intermolecular forces, the
higher the viscosity.
Surface Tension (sức căng bề mặt)

• Bulk molecules (those in the liquid) are equally
attracted to their neighbors.

Surface Tension

Surface Tension
• Surface molecules are only attracted inwards
towards the bulk molecules.
– Therefore, surface molecules are packed more
closely than bulk molecules.
• Surface tension is the amount of energy
required to increase the surface area of a liquid.
• Cohesive forces (lực cố kết) bind molecules to
each other.
• Adhesive forces (lực kết dính) bind molecules to
a surface.

Surface Tension

Surface Tension
• Meniscus is the shape of the liquid surface.
– If adhesive forces are greater than cohesive forces, the
liquid surface is attracted to its container more than the
bulk molecules. Therefore, the meniscus is U-shaped
(e.g. water in glass).
– If cohesive forces are greater than adhesive forces, the
meniscus is curved downwards.
• Capillary Action: When a narrow glass tube is
placed in water, the meniscus pulls the water up
the tube.

Phase Changes
• Surface molecules are only attracted inwards
towards the bulk molecules.
• Sublimation: solid  gas.
• Vaporization: liquid  gas.
• Melting or fusion: solid  liquid.
• Deposition: gas  solid.
• Condensation: gas  liquid.
• Freezing: liquid  solid.
Energy Changes Accompanying Phase Changes
• Energy change of the system for the above
processes are:

Phase Changes
Energy Changes Accompanying Phase
Changes
– Sublimation: Hsub > 0 (endothermic).
– Vaporization: Hvap > 0 (endothermic).
– Melting or Fusion: Hfus > 0 (endothermic).
– Deposition: Hdep < 0 (exothermic).
– Condensation: Hcon < 0 (exothermic).
– Freezing: Hfre < 0 (exothermic).
• Generally heat of fusion (enthalpy of fusion) is
less than heat of vaporization:
– it takes more energy to completely separate
molecules, than partially separate them.
Phase Changes
• All phase changes are possible under the right
conditions (e.g. water sublimes when snow
disappears without forming puddles).
• The sequence
heat solid  melt  heat liquid  boil  heat gas
is endothermic.
• The sequence
cool gas  condense  cool liquid  freeze  cool
solid
is exothermic.

Phase Changes

Phase Changes
Heating Curves / Cooling curves
• Plot of temperature change versus heat added is
a heating curve.
• During a phase change, adding heat causes no
temperature change.
– These points are used to calculate Hfus and Hvap.
• Supercooling: When a liquid is cooled below its
melting point and it still remains a liquid.
• Achieved by keeping the temperature low and
increasing kinetic energy to break
intermolecular forces.

Phase Changes
Heating Curves

Phase Changes
Critical Temperature and Pressure
• Gases liquefied by increasing pressure at some
temperature.
• Critical temperature (nhiệt độ tới hạn) : the minimum
temperature for liquefaction of a gas using pressure.
• Critical pressure (áp suất tới hạn): pressure required
for liquefaction.

Vapor Pressure
Explaining Vapor Pressure on the Molecular
Level
• Some of the molecules on the surface of a liquid have
enough energy to escape the attraction of the bulk
liquid.
• These molecules move into the gas phase.
• As the number of molecules in the gas phase
increases, some of the gas phase molecules strike the
surface and return to the liquid.
• After some time the pressure of the gas will be
constant at the vapor pressure.

Vapor Pressure
Explaining Vapor Pressure
on the Molecular Level
• Dynamic Equilibrium: the
point when as many molecules
escape the surface as strike the
surface.
• Vapor pressure is the pressure
exerted when the liquid and
vapor are in dynamic
equilibrium.

Vapor Pressure
Volatility, Vapor Pressure, and Temperature
• If equilibrium is never established then the liquid
evaporates.
• Volatile substances evaporate rapidly.
• The higher the temperature, the higher the average
kinetic energy, the faster the liquid evaporates.

Vapor Pressure
Volatility, Vapor Pressure, and Temperature

Vapor Pressure
Vapor Pressure and Boiling Point
• Liquids boil when the external pressure equals the
vapor pressure.
• Temperature of boiling point increases as pressure
increases.
• Two ways to get a liquid to boil: increase temperature
or decrease pressure.
– Pressure cookers operate at high pressure. At high pressure
the boiling point of water is higher than at 1 atm. Therefore,
there is a higher temperature at which the food is cooked,
reducing the cooking time required.
• Normal boiling point is the boiling point at 760 mmHg
(1 atm).
Phase Diagrams
• Phase diagram: plot of pressure vs. Temperature
summarizing all equilibria between phases.
• Given a temperature and pressure, phase diagrams
tell us which phase will exist.
• Features of a phase diagram:
– Triple point: temperature and pressure at which all three
phases are in equilibrium.
– Vapor-pressure curve: generally as pressure increases,
temperature increases.
– Critical point: critical temperature and pressure for the gas.
– Melting point curve: as pressure increases, the solid phase is
favored if the solid is more dense than the liquid.
– Normal melting point: melting point at 1 atm.
Phase Diagrams
• Any temperature and pressure combination not on a
curve represents a single phase.

Phase Diagrams
The Phase Diagrams of H2O and CO2
• Water:
– The melting point curve slopes to the left because ice is less
dense than water.
– Triple point occurs at 0.0098C and 4.58 mmHg.
– Normal melting (freezing) point is 0C.
– Normal boiling point is 100C.
– Critical point is 374C and 218 atm.
• Carbon Dioxide:
– Triple point occurs at -56.4C and 5.11 atm.
– Normal sublimation point is -78.5C. (At 1 atm CO2 sublimes
it does not melt.)
– Critical point occurs at 31.1C and 73 atm.
Phase Diagrams
The Phase Diagrams of H2O and CO2

Structures of Solids
Unit Cells
• Crystalline solid: well-ordered, definite arrangements
of molecules, atoms or ions.
• Crystals have an ordered, repeated structure.
• The smallest repeating unit in a crystal is a unit cell.
• Unit cell is the smallest unit with all the symmetry of
the entire crystal.
• Three-dimensional stacking of unit cells is the crystal
lattice.

Unit Cells

Unit Cells
• Three common types of unit cell.
– Primitive cubic, atoms at the corners of a simple cube,
• each atom shared by 8 unit cells;
– Body-centered cubic (bcc), atoms at the corners of a cube
plus one in the center of the body of the cube,
• corner atoms shared by 8 unit cells, center atom completely enclosed in
one unit cell;
– Face-centered cubic (fcc), atoms at the corners of a cube
plus one atom in the center of each face of the cube,
• corner atoms shared by 8 unit cells, face atoms shared by 2 unit
cells.

Unit Cells

Crystal Structure of Sodium Chloride
• Face-centered cubic lattice.
• Two equivalent ways of defining unit cell:
– Cl- (larger) ions at the corners of the cell, or
– Na+ (smaller) ions at the corners of the cell.
• The cation to anion ratio in a unit cell is the same for
the crystal. In NaCl each unit cell contains same
number of Na+ and Cl- ions.
• Note the unit cell for CaCl2 needs twice as many Cl-
ions as Ca2+ ions.

Crystal Structure of Sodium Chloride

Close Packing of Spheres
• Solids have maximum intermolecular forces.
• Molecules can be modeled by spheres.
• Atoms and ions are spheres.
• Molecular crystals are formed by close packing of the
molecules.
• We rationalize maximum intermolecular force in a
crystal by the close packing of spheres.
• When spheres are packed as closely as possible, there
are small spaces between adjacent spheres.
• The spaces are called interstitial holes.

• A crystal is built up by placing close packed layers of
spheres on top of each other.
• There is only one place for the second layer of
spheres.
• There are two choices for the third layer of spheres:
– Third layer eclipses the first (ABAB arrangement). This is
called hexagonal close packing (hcp);
– Third layer is in a different position relative to the first
(ABCABC arrangement). This is called cubic close packing
(ccp).


• Each sphere is surrounded by 12 other spheres (6 in
one plane, 3 above and 3 below).
• Coordination number: the number of spheres directly
surrounding a central sphere.
• Hexagonal and cubic close packing are different from
the cubic unit cells.
• If unequally sized spheres are used, the smaller
spheres are placed in the interstitial holes.

X-Ray Diffraction
• When waves are passed through a narrow slit
they are diffracted.
• When waves are passed through a diffraction
grating (many narrow slits in parallel) they
interact to form a diffraction pattern (areas of
light and dark bands).
• Efficient diffraction occurs when the wavelength
of light is close to the size of the slits.
• The spacing between layers in a crystal is 2 - 20
Å, which is the wavelength range for X-rays.

X-Ray Diffraction

X-Ray Diffraction
• X-ray diffraction (X-ray crystallography):
– X-rays are passed through the crystal and are
detected on a photographic plate.
– The photographic plate has one bright spot at the
center (incident beam) as well as a diffraction pattern.
– Each close packing arrangement produces a different
diffraction pattern.
– Knowing the diffraction pattern, we can calculate the
positions of the atoms required to produce that
pattern.
– We calculate the crystal structure based on a
knowledge of the diffraction pattern.
Bonding in Solids
• There are four types of solid:
– Molecular (formed from molecules) - usually soft
with low melting points and poor conductivity.
– Covalent network (formed from atoms) - very hard
with very high melting points and poor conductivity.
– Ions (formed form ions) - hard, brittle, high melting
points and poor conductivity.
– Metallic (formed from metal atoms) - soft or hard,
high melting points, good conductivity, malleable
and ductile.

Bonding in Solids

Bonding in Solids
Molecular Solids
• Intermolecular forces: dipole-dipole, London
dispersion and H-bonds.
• Weak intermolecular forces give rise to low
melting points.
• Room temperature gases and liquids usually
form molecular solids at low temperature.
• Efficient packing of molecules is important
(since they are not regular spheres).

Bonding in Solids
Covalent Network Solids
• Intermolecular forces: dipole-dipole, London
dispersion and H-bonds.
• Atoms held together in large networks.
• Examples: diamond, graphite, quartz (SiO2),
silicon carbide (SiC), and boron nitride (BN).
• In diamond:
– each C atom has a coordination number of 4;
– each C atom is tetrahedral;
– there is a three-dimensional array of atoms.
– Diamond is hard, and has a high melting point (3550
C).
Bonding in Solids

Bonding in Solids
• In graphite
– each C atom is arranged in a planar hexagonal ring;
– layers of interconnected rings are placed on top of each
other;
– the distance between C atoms is close to benzene (1.42
Å vs. 1.395 Å in benzene);
– the distance between layers is large (3.41 Å);
– electrons move in delocalized orbitals (good conductor).

Bonding in Solids
Ionic Solids
• Ions (spherical) held together by electrostatic
forces of attraction:
Q1Q2
F k
d2
– The higher the charge (Q) and smaller the distance (d)
between ions, the stronger the ionic bond.
• There are some simple classifications for ionic
lattice types:

Bonding in Solids
Ionic Solids

Bonding in Solids
Ionic Solids
– NaCl Structure
• Each ion has a coordination number of 6.
• Face-centered cubic lattice.
• Cation to anion ratio is 1:1.
• Examples: LiF, KCl, AgCl and CaO.
– CsCl Structure
• Cs+ has a coordination number of 8.
• Different from the NaCl structure (Cs+ is larger than Na+).
• Cation to anion ratio is 1:1.

Bonding in Solids
Ionic Solids
– Zinc Blende Structure
• Typical example ZnS.
• S2- ions adopt a fcc arrangement.
• Zn2+ ions have a coordination number of 4.
• The S2- ions are placed in a tetrahedron around the Zn 2+
ions.
• Example: CuCl.
– Fluorite Structure
• Typical example CaF2.
• Ca2+ ions in a fcc arrangement.
• There are twice as many F- per Ca2+ ions in each unit cell.
• Examples: BaCl2, PbF2.

Bonding in Solids
Metallic Solids
• Metallic solids have metal atoms in hcp, fcc or bcc
arrangements.
• Coordination number for each atom is either 8 or 12.
• Problem: the bonding is too strong for London
dispersion and there are not enough electrons for
covalent bonds.
• Resolution: the metal nuclei float in a sea of
electrons.
• Metals conduct because the electrons are
delocalized and are mobile.

Bonding in Solids
Metallic Solids

Intermolecular Forces,
Liquids, and Solids
End of Chapter 11

Luclienphantu 05

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Intermolecular Forces,

Liquids, and Solids

Lực liên kết liên phân tử

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Surface Tension (sức căng bề mặt)

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