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Chapter 3:

Liquids, Solids & Phase


Changes

Chapter Objectives:
• To learn the differences between the solid, liquid, and gas state,
and how the polarity of molecules influences those states.
• To learn the different types of intermolecular forces between
different molecules.
Kinetic Molecular Theory of Liquids
and Solids
• Liquids and solids have significant interactions.
• Liquids and solids have well-defined volume.
• Liquid molecules “flow,” while solids are held “rigid.”

A molecular comparison of gases, liquids, and solids.


(b) In gases, the particles feel little attraction for one another
and are free to move about randomly.
(b) In liquids, the particles are held close together by attractive
forces but are free to move over one another.
(c) In solids, the particles are rigidly held in an ordered arrangement.
Polar Bonds
• Individual covalent bonds are polar if the atoms being
connected are of different electronegativities. This is
described as a bond dipole.
Example: CH3Cl
The C—H bonds are nonpolar since C and H have about the
same electronegativity.
Since Cl is more electronegative than C, the C—Cl bond is
polarized so that the Cl atom is slightly electron-rich (partial
negative charge,δ-) and the C atom is slightly electron-poor

(partial positive charge, δ+). This bond is a polar covalent

bond (or just polar bond).


Polar Bonds
• Dipole Moment (µ): the sum of all the bond dipoles within a molecule,
(net polarity) can be illustrated with an electrostatic potential map.

Since CH3Cl has a tetrahedral shape, with one polar bond and three nonpolar
bonds, there is an overall dipole moment pointing towards the Cl end of the
molecule.

Depending on the number and orientation of the bond dipoles, the molecule may

possess an overall molecular dipole.


Ammonia and water

Structures and dipole moments for ammonia and water are shown

Carbon dioxide and tetrachloromethane

Structures and dipole moments are shown for carbon dioxide and
tetrachloromethane. Although each molecule has bond dipoles,
they do not have molecular dipoles
Intramolecular &
• Intermolecular Forces
Intramolecular forces operate within each molecule,
influencing the chemical properties of the substance
(i.e., covalent bonds).

These are the forces that hold the atoms in a molecule together.
They are very strong forces which result from large charges (on
protons and electrons)interacting over very short distances.

• Intermolecular forces (van der Waals forces) operate


between separate molecules, influencing the physical
properties of the substance.

These are the forces that hold liquids and solids together, and
influence their melting and boiling points. They are weaker forces,
because they result from smaller charges, or partial charges,
interacting over much larger distances.
Intramolecular &
Intermolecular Forces
To break an O—H bond in water, the water must be
heated to thousands of degrees C; to completely
overcome the intermolecular forces, all you have to do is
boil it — 100ºC.
Intramolecular &
Intermolecular Forces
(a) In an individual N2 molecule,
atoms are held together by strong
intramolecular force(covalent bond).
Different N2 molecules are weakly
attracted to one another at low
temperature by intermolecular forces,
causing nitrogen to become liquid.

(b) At a higher temperature,


intermolecular forces are no longer
able to keep molecules close
together, so nitrogen becomes a
gas.
Intermolecular Forces
• An attractive interaction between molecules
– Determine bulk properties of matter.
• Much weaker than intramolecular forces
• Several types of intermolecular (IM) forces:
Ion–dipole
Dipole–dipole
London dispersion forces
Hydrogen “bonds.”
London Dispersion
Forces
 Attraction is due to instantaneous, temporary dipoles
formed due to electron motions

 The larger the molar mass of a molecule, generally the


greater the LDF’s.

 Dispersion forces exist between all molecules, but they


are the only forces that exist between nonpolar
molecules.
London Dispersion
Forces

Using molecular bromine as an example, each molecule has zero


polarity.
However, due to the motion of electrons at any given instant a
temporary dipole would arise that would then induce a dipole in an
adjacent molecule.
This type of intermolecular attraction is called London dispersion
forces.
Dipole-Dipole Forces
• Dipole-Dipole forces are the attractions between the opposite
partial charges in the permanent dipoles of polar molecules.
 exit between all polar molecules, (HCl – HCl)

(a) Polar molecules attract one another and approach


closely
when oriented with unlike charges together, but (b) they
repel one another and push apart when oriented with like
charges together.
Dipole-Dipole Forces
• In general, for molecules of the same molecular
weight, a polar molecule (dipole-dipole +
London) will have a higher boiling point than a
nonpolar molecule (London only):
Hydrogen Bonding
Attractive interaction between a hydrogen atom
bonded to a very electronegative atom (O, N, or
F) and an unshared electron pair on another
electronegative atom.

Hydrogen bonds are also found between molecules of water and


molecules of ammonia.
Ion-Dipole Forces
• Ion-Dipole forces are the result of electrical interactions
between an ion and the partial charges on a polar
molecule.

Polar molecules orient toward ions so that


(a) the positive end of the dipole is near an anion and
(b) the negative end of the dipole is near a cation.
Ion-Dipole Forces
• These forces are responsible for the ability of
polar solvents like water to dissolve ionic
compounds.
Ion- and Dipole-Induced Dipole
Forces
• Ion - induced dipole forces are the attractive forces that exist
between ions and nonpolar molecules.

• Being next to an ion “induces” a dipole in a nonpolar molecule,


attracting it towards the ion.

 These forces are responsible for the attraction between


Fe2+ and O2 molecules in the bloodstream, and contributes
to the solvation of ions in water.

• Dipole - induced dipole forces are the attractive forces that exist
between polar molecules and nonpolar molecules. Being next to a
polar molecule “induces” a dipole in a nonpolar molecule.

 These forces are responsible for the solvation of gases


(nonpolar) in water (polar).
Summary: Intermolecular
Forces
Intermolecula Formed by the Examples
r Forces attraction
Ion-dipole an between …
ion and a polar Na+ and H2O
molecule
Hydrogen bond molecules which H2O and H2O;
have H H2 O
on N, O, or F atoms and CHand
Dipole - Dipole two polar molecules CH3Br 3CH2ICl;
OH
Strength

CH3Br and H2O


Ion - Induced an ion and a Fe2+ and O2
dipole nonpolar molecule
Dipole - a polar molecule HCl and Cl2
Induced and a nonpolar
dipole molecule
London two nonpolar CH4 and CH4; F2
(dispersion) molecules and F2; CH4 and
forces F2
Intermolecular Force
• Surface TensionEffects
 The resistance of a liquid to spread out and
increase its surface area.
 Surface tension results from intermolecular
force differences between molecules in the
interior of a liquid and those on the surface.

Molecules at the surface of a liquid feel


attractive forces only one side and are
thus pulled in toward the liquid, while
molecules in interior are surrounded and
are pulled equally in all direction.
Intermolecular Force
Effects
Surface tension, which causes these drops of liquid mercury to form
beads

Atoms on the surface are less stable because they have fewer neighbors
and feel fewer attractive forces than atoms in the interior, so the liquid acts
to minimize their number by minimizing the area of the surface.
Intermolecular Force
Effects
More surface tension examples…
Intermolecular Force
Effects
2. Viscosity

 The measure of a liquid’s resistance to flow and is related to the


ease with which molecules move around, and thus to the
intermolecular forces.

 Substances composed of small, nonpolar molecules (such as


gasoline and benzene) have low viscosities.

 Polar molecules (such as glycerol) and molecules composed of


long chains of atoms (such as oil and grease) have higher
viscosities.

 The viscosity of a liquid decreases at higher temperatures.


Intermolecular Force
Effects
Phase Changes
• Enthalpy  the heat flow associated with making or breaking
intermolecular attractions that hold liquids and solids together
• Entropy  change in a molecular randomness between various phases

Changes from a less random phase to a more random one have positive
values of ΔH and Δ S. Changes from a more random phase to a less
random one have negative values of Δ H and Δ S.
Phase Changes
• Sublimation: The process in which molecules go
directly from the solid into the vapor phase.

• Deposition: The process in which molecules go


directly from the vapor into the solid phase.

• Molar heat of sublimation (∆Hsub): The energy (kJ)


required to sublime one mole of solid.

∆ Hsub = ∆ H fus + ∆ Hvap


Phase Changes
• Molar Heat of Fusion (∆Hfus):
The energy required to melt one mole of solid (in kJ).

• Molar Heat of Vaporization (∆Hvap):


The energy (in kJ) required to vaporize one mole of
liquid.
Heating curve for water

A heating curve for H2O, showing the temperature changes and phase
transitions that occur when heat is added. The plateau at 0°C represents
the melting of solid ice, and the plateau at 100°C represents the boiling
of liquid water.

Plateau regions in a heating curve indicate a change in phase of the


substance where the temperature remains constant

Phase Changes
Vapor Pressure: The pressure exerted by gaseous
molecules above a liquid.

• Liquids after sitting for a length of time in (a) an open container


and (b) a closed container. The liquid in the open container has
evaporated, but the liquid in the closed container has brought
about a rise in pressure.
• Evaporation of a liquid results in more gas phase molecules
which exert a pressure in a closed container
Phase changes depend on temperature.

The distribution of molecular kinetic energies in a liquid at two temperatures.


Only the faster-moving molecules have sufficient kinetic energy to escape
from the liquid and enter the vapor. The higher the temperature, the larger
the number of molecules with enough energy to escape.
Kinds of Solids
• Solids are divided into two categories:
 Crystalline:
- Possesses rigid and long-range order
- Flat faces
- Distinct angles
- eg. NaCl
 Amorphous
- Lacks well-defined arrangement (particles are randomly
arranged)
- have no long ranged structure
- eg. rubber

• Structure of a crystalline solid is based on the unit cell, a basic


repeating structural unit.
Crystalline Solids
• Crystal structures of (a) ice, a molecular solid, and (b) quartz, a covalent
network solid.
• Ice consists of individual H2O molecules held together in a regular
manner by hydrogen bonds.
• Quartz (SiO2) is essentially one very large molecule whose Si and O
atoms are linked by covalent bonds.
• Each silicon atom has tetrahedral geometry and is bonded to four
oxygens; each oxygen has approximately linear geometry and is bonded
to two silicons.
• The shorthand representation on the right shows how SiO4 tetrahedra
join at their corners to share oxygen atoms.
Cubic Packing
Simple Cube and Body-Centered Cube:

(a) Simple cubic packing of spheres


 all the layers are identical and all atoms are lined up in stacks and rows.

(b) Body-centered cubic packing of spheres


 spheres in layer a are separated slightly and the spheres in layer b
are offset so that they fit into the depressions between atoms in layer a.
Hexagonal and Cubic Closest-
Packing
a) Hexagonal closest-packing.
Two alternating hexagonal layers
(a and b) offset from each other so
that the spheres in one layer sit in
the small triangular depressions of
neighboring layers.

i) Cubic closest-packing of spheres


Three alternating hexagonal
layers, (a, b, and c) offset from
one
another so that the spheres in one
layer sit in small triangular
depressions of neighboring layers.
Cubic Unit Cells
Simple Cube and Body-Centered Cube:

Geometries of (a) primitive-cubic and (b) body-centered cubic unit cells in


both a skeletal view (top) and a space-filling view (bottom).
Part (c) shows how eight primitive-cubic unit cells stack together to share
a common corner where they meet.
Cubic Unit Cells
Face-Centered Cube:
(a) Geometry of a face-
centered cubic unit cell,

(b) a view showing how this


unit cell is found in
cubic closest-packing.
The faces are tilted at
54.7° angles to the
three repeating atomic
layers
Phase Diagrams
• A Phase Diagram is a graphical display of the
temperatures and pressures at which two
phases of a substance are in equilibrium.
– Triple Point: The only condition under which all three
phases can be in equilibrium with one another.

– Critical Temperature (Tc): The temperature above which


the gas phase cannot be made to liquefy at any pressure.

– Critical Pressure (Pc): The minimum pressure required to


liquefy a gas at its critical temp.
Phase diagram for water

A phase diagram for H2O, showing a negative slope for the solid/liquid
boundary.
Phase diagram for
carbon dioxide

A phase diagram for CO2, showing a positive slope for


the solid/liquid boundary. The pressure and temperature
axes are not to scale.
Formation of supercritical fluid

Here we can see the separate phases of carbon dioxide. The meniscus
is easily observed.

With an increase in temperature the meniscus begins to diminish.

Increasing the temperature further causes the gas and liquid


densities to become more similar. The meniscus is less easily
observed but still evident.

Once the critical temperature and pressure have been reached the
two distinct phases of liquid and gas are no longer visible. The
meniscus can no longer be seen. One homogenous phase called
the "supercritical fluid" phase occurs which shows properties of
both liquids and gases.