CHAPTER 14: LIQUIDS AND SOLIDS

Active Learning Problems: 1-19, 21-22

End-of-Chapter Problems: 1-3, 6-11, 19, 21-27, 31-34, 39-41, 45, 47, 63-65, 69, 71, 75-78, 81, 83, 85-90

PROPERTIES OF LIQUIDS AND SOLIDS

Properties of Liquids
1. Liquids have an indefinite shape.
They take the shape of their container.
2. Liquids have a fixed volume.
They cannot be compressed; nor can they be
expanded very much.
3. Liquids are much denser compared to gases.
Liquids are about 1000 times denser than gases.
4. Liquids usually flow readily, so liquids that mix will
eventually form a homogeneous mixture.
This is because molecules in a liquid are constantly in
motion at the molecular level.
Properties of Solids
1. Solids have definite shape.
Particles are fixed in place and vibrate but do not move.
2. Solids have a fixed volume.
Like liquids, they cannot be compressed; nor can they be expanded very much.
3. Solids are either crystalline or noncrystalline (amorphous).
A crystalline solid contains particles in a regular, repeating pattern.
A noncrystalline or amorphous solid is disordered.
4. Like liquids, solids have much greater densities than gases.
5. Solids do not mix by diffusion because particles in a solid do not move and mix.

phase (=physical state): solid, liquid, or gas

Solids have the lowest kinetic energy (KE)i.e. do not move very much
Highest attraction between particles particles are stuck in specific sites = very confined
Liquids have slightly higher KEi.e. particles moving more than in solid
Particles are still attracted and maintain contact but can move past one another
particles are less confined
Gases have greatest KEi.e. particles move quickly and randomly
Attractive forces almost (if not) completely overcome, so particles can fly freely within container
particles are far away from each other = unrestricted
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condensed states: solid and liquid phases

In solids and liquids, molecules are in close contact and attracted to one another.
These attractions are called intermolecular forces.

Example: What is the biggest difference at the molecular level between particles in a gas and
particles in a liquid?

14.2 ENERGY REQUIREMENTS FOR THE CHANGES OF STATE

To undergo a change in physical state (e.g. solid liquid or liquid gas), particles on the
solid or liquid must overcome the intermolecular forces with surrounding molecules.
Thus, for a liquid or solid to become a gas, the thermal energy (associated with motion) of
particles in the liquid/solid must be great enough to overcome the attractive forces with
surrounding particles in the liquid/solid. Those attractive forces are ionic bonds, covalent
bonds, metallic bonds, or intermolecular forces.
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14.3 INTERMOLECULAR FORCES (IMFs)

Dispersion (or London) Forces (also called Induced-Dipole Forces)
In nonpolar molecules (shown as green) the
electrons can shift and concentrate on one end
temporary dipole (red = end; blue = + end)
The partial positive charge caused by the
temporary dipole in one molecule causes the
electrons in an adjacent molecule to concentrate
around the atom closest to the first molecule.
A temporary dipole results in the second
molecule.
The temporary dipoles in both molecules
cause them to be attracted to one another.
But that attraction lasts only until the electrons
shift again, and the temporary dipoles go
away.
Every molecule experiences London forces.
They are the ONLY type of IMFs between
nonpolar molecules
Polar molecules also experience London forces they usually have other types of IMFs
that are stronger than London forces.
The strength of London forces is determined by the number of electrons.
The bigger the molecule more electrons
the greater its polarizability (ability to distort electron clouds to get a temporary dipole)
the stronger its London/dispersion forces
Thus, the more electrons in an atom or molecule
The stronger the London/Dispersion forces

Dipole-Dipole Forces: Attraction between polar molecules

generally stronger than dispersion forces because attraction is due to permanent dipoles.
The permanent dipoles mean the molecules are always attracted to nearby molecules.
Dipole-dipole forces are stronger than London forces for molecules of similar size (or
number of electrons).

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The Hydrogen Bond:

Especially strong type of dipole-dipole force
Exist between molecules with the following
bonds: HF, HO, HN
because these are small atoms with large
electronegativity differences
very strong dipole in molecules
Strongest type of intermolecular force
Responsible for the relatively high melting and
boiling point for water compared to molecules of
similar size.

Hydrogen bonds are also responsible for the bending and twisting in proteins, DNA, and other
important biological molecules.

Image from http://blog.targethealth.com/?p=6846

Note:

Hydrogen bonds are the strongest type of intermolecular forces between

different molecules, BUT ionic and covalent bonds (holding ions or atoms together
in compounds) are stronger than hydrogen bonds!

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Ion-Dipole Forces
Attraction between an ion and the oppositely charged end of a polar molecule
e.g., between Na+ and the negative end (O atom) of a H2O molecule or between Cl and the
positive end (H atoms) of a H2O molecule.

Note that when an ionic compound like NaCl dissolves in water, the formation of ion-dipole
forces between the Na+ (or Cl) ions with water molecules results in the ionic bonds breaking.

How to determine type of intermolecular forces involved:

Is the molecule polar

or nonpolar?

nonpolar

polar

Any H-F, H-O, or H-N

bonds in the molecule?

yes

hydrogen bonds
and London Forces

no

London Forces

dipole-dipole forces
and London Forces

Ex. 1 Indicate the type(s) of intermolecular forces for each molecule below then circle the
molecule in each pair that experiences the stronger intermolecular forces.
a.

N2

b.

H2S

or

NO

or

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H2O

c.

Cl2

d.

PH3

or

or

Br2

CH4

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Ex. 2: For each of the following,

i. Identify the bond between atoms as ionic, polar covalent, or nonpolar covalent.
ii. Identify the intermolecular forces as London dispersion forces, dipole-dipole
forces, and/or hydrogen bonding.

Water (H2O)

B
A

A: _____________________
Oxygen (O2)

B: ______________________

A: _____________________

B: ______________________

HCN (H=white, C=charcoal, N=blue)

A: _____________________
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B: ______________________
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Ex. 3: Indicate the bond or intermolecular forces described for each below:
A. ionic bond
B. polar covalent bond
C. nonpolar covalent bond

D. London (dispersion) forces

E. dipole-dipole forces
F. hydrogen bond

G. metallic bond
H. ion-dipole forces

_________ i. The bonds holding the atoms together in a HF molecule

_________ ii. The bonds holding two H2S molecules together in liquid H2S

_________ iii. The bonds holding two Br2 molecules together in liquid Br2

_________ iv. The bonds holding the atoms together in a chlorine molecule

_________ v. The bonds holding the CO2 molecules together in dry ice, solid CO2

_________ vi. The bonds in a sample of CuO

_________ vii. The bonds holding atoms together in magnesium

_________ viii. The bonds holding atoms together in water

_________ ix. The bonds broken when NaCl dissolves in water

_________ x. The bonds made when NaCl dissolves in water

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14.4 EVAPORATION AND VAPOR PRESSURE

vaporization: liquid gas
From a molecular viewpoint, a molecule escaping from the liquid to gaseous state

As the liquid evaporates, more molecules go into the gas phase.

vapor: The gas above a liquid when the liquid and gaseous states are both present
vaporization: liquid + heat vapor
condensation: vapor liquid + heat
Liquid-Gas Equilibrium:

vaporization

vapor
liquid + heat

condensati on

When the molecules in the liquid have enough energy, they escape to the gas phase.
In a closed system, when enough vapor exists above the liquid, some gaseous
molecules condense back to the liquid.
Ultimately, the rate of vaporization = the rate of condensation.
The system has reached a state of dynamic equilibrium in which the forward
process occurs at the same rate as the reverse process.
In an open system, molecules in the liquid have enough energy to escape to the gas
phase and continue to escape in a process called evaporation.
The vaporized molecules continue to escape little or no condensation occurs.
Ultimately, all of the liquid is converted into a gas.
Since vaporization requires energy, the liquid molecules take energy from the
surroundings, so the temperature of the surroundings often decreases.
Why evaporation is a cooling process and is used to reduce body temperature
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Activity:

Cap the end of the syringe with your finger to make it airtight then pull the plunger
out at least half way. Release the plunger.

Record your observations:

Explain why this occurs.

13.1 PRESSURE
gas pressure: force per unit area exerted by gas molecules colliding against the inside
walls of their container
a measure of how often gas particles hit the container walls
In the 1600s, Evangelista Torricelli published the first explanation for
a vacuum.
Ancient Greeks observed that a wine barrel empties slowly if
only one hole is drilled.
Torricelli explained that a sea of air surrounding the Earth
slows the flow of wine out of the barrel.
If you create a second hole on the top of the barrel, air
molecules can rush in and push the liquid out.
The wine flows out faster.
vacuum: empty space with no gas molecules present
gas pressure equals zero
Dont think of a vacuum cleaner because theres no
suction, just empty space!
atmospheric pressure:
pressure exerted by air molecules colliding with surfaces
in the environment
Why anything entering the Earth's atmosphere burns up!
At sea level, atmospheric pressure can hold up a column of
mercury about 760 mm in height = 760 mmHg.
decreases as altitude increases
At higher altitudes like Denver and Mt. Everest, air
becomes thinner, so atmospheric pressure is lower.
Less O2 present makes it harder to breathe.
barometer: instrument invented by Torricelli to measure
atmospheric pressure
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standard atmospheric pressure: a column of mercury measuring 760 mmHg.

1 atm 760 torr 760 mm Hg = 14.7 psi (approx.)
Ex. 1:

The tire pressure for tires used on most automobiles is about 32 psi. Express this
pressure in units of atm, torr, and mmHg.

Vapor Pressure (v.p.): pressure exerted by gas molecules above a liquid

For a molecule to go from liquid to gas, it has to break the intermolecular forces with other
liquid molecules around it
Weaker the intermolecular forces are easier to break
more gas molecules higher vapor pressure
Stronger the intermolecular forces are harder to break
fewer molecules go from liquid to gas lower vapor pressure.

Example: Consider the two closed systems above. In which container, (a) or (b), does the
liquid have stronger intermolecular forces? Explain why.

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Boiling Point: temperature where vapor pressure of liquid is equal to the external pressure
(usually atmospheric pressure)
For a liquid to boil, its vapor pressure must equal the atmospheric pressure.
Note that atmospheric pressure is the pressure exerted by air molecules (i.e., the gas
molecules in the atmosphere).
Since intermolecular forces influence vapor pressure, they also influence boiling point.
Weaker the intermolecular forces more gas molecules higher vapor pressure
Less energy is needed to get vapor P = atmospheric P lower boiling point
Stronger the intermolecular forces fewer gas molecules lower vapor pressure
More energy is needed to get vapor pressure = atmospheric pressure
higher boiling point
normal boiling point (b.p.) is the b.p. when atmospheric pressure is 1 atm (760 mmHg)
e.g. Water boils at 100C at sea level (where atmospheric pressure is ~1 atm) but at
~95C in Denver where atmospheric pressure is much lower (~.85 atm).

Ex. 1: If hexane (C6H14) molecules are nonpolar, fill in the blanks for the following statements
about water and hexane:
a. Hexanes intermolecular forces are _______________________________.
b. Waters intermolecular forces are _______________________________.
c. Water's intermolecular forces are _________ than hexane's.

stronger

weaker

d. Water has a __________ vapor pressure compared with hexane.

higher

lower

e. Water has a ____________ boiling point than hexane.

higher

lower

Ex. 2: Circle the compound in each pair below with the higher boiling point, and explain why.
a.

CO

or

O2

b.

HF

or

HCl

c.

Cl2

or

F2

Ex. 3: Which of the following compounds has the higher boiling point: CH2O or COF2?
Explain why.

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14.5 THE SOLID STATE: TYPES OF SOLIDS (MOLECULAR , IONIC, AND ATOMIC)
Solids can be crystalline or amorphous.
Crystalline Solids: Have an ordered arrangement extending over a long range
different types of crystalline solids: molecular, ionic, covalent network, and metallic.

MOLECULAR SOLIDS: consist of molecules held together by intermolecular forces

The Structure and Properties of Ice
Ice is an example of a molecular solid.
The hydrogen bonds between water molecules are
responsible for many unusual properties of ice and
water.
Because of hydrogen bonds, the arrangement of H2O
molecules in ice leaves "holes" or empty space.
Note the hexagonal holes in the molecular-level
image for ice at the right.
Snowflakes have hexagonal symmetry because of
the hexagonal holes in the molecular-level
arrangement/structure of water molecules in ice!

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The density of ice (d=0.917 g/cm3) is lower than the density of liquid water (d=1.00 g/cm3).
With all other substances, the solid is more dense than its liquid.
When ice melts, the H2O molecules fill in the holes, so liquid H2O is denser than ice.

ATOMIC SOLIDS: consist of metal or nonmetal atoms, where nonmetal atoms in a covalent
network solid are held together by covalent bonds, and metal atoms are held together by
metallic bonds.

Covalent Network Solids: covalently bonded atoms forming a large network of indefinite size.
(a) Graphite consists of covalently bonded carbon atoms that form layers of carbon atoms.
(b) Diamond consists of covalently bonded carbon atoms that form such a network of carbon
atoms in 3D tetrahedral structure.
Diamond is so hard because the covalent bonds between the carbon atoms must be
broken to cleave or melt the diamond crystal.

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Metallic Solids: exist as positive ions surrounded

by a sea of electrons
electrons move freely throughout the metal
metals having high electrical conductivity
metals conduct heat, which is why most pots
and pans are made out of metal
electrons can act as a glue to hold the metal
atoms together
metals are malleable (can hammered into a
thin foil) and ductible (can stretched into a
fine wire)

IONIC CRYSTALS: lattice of metal & nonmetal ions

e.g. NaCl, MgO, CaBr2
3D network of ions held together by electrostatic attraction = ionic bonds
high melting points, hard and brittle
conduct electricity only when melted or dissolved in solution

AMORPHOUS: solids lacking 3D

arrangement of atoms
similar in appearance to liquids since
they lack the ordered structure of
crystalline solids
Silica (SiO2): makes up sand and quartz
glass: optically transparent solid of
inorganic materials cooled to a
rigid but non-crystalline
arrangement of Si-O bonded
atoms called quartz glass
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silica (SiO2)

glass
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Ex. 1: Indicate the type of bonds or intermolecular forces that must be broken to melt the
following substances:
a.

ice

b.

diamond

c.

sodium chloride (NaCl)

d.

aluminum

Ex. 2: If sodium chlorides melting point is 801C while diamonds melting point is about
3550C, compare the relative strength of the bonds in sodium chloride with the bonds in
diamond.

Ex. 3: If coppers melting point is 1083C while NaCls melting point is about 801C, compare
the relative strength of the bonds in copper with the bonds in NaCl. Can you assume
metallic bonds are always stronger than ionic bonds? Explain.

Ex. 4: Rank the following substances in terms of increasing melting point: ice, diamond,
copper, and table salt (NaCl).

_______________ < _______________ <_______________ <_______________

lowest m.p.
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highest m.p.
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14.1 WATER AND ITS PHASE CHANGES

phase = physical state (e.g. gas phase, liquid phase, etc.)
phase change = change in physical state

HEATING/COOLING CURVES

Temperature
( C)

Consider the changes that H2O undergoes when a block of ice is taken from a freezer and
heated in a pan until it is completed converted into steam.
A heating/cooling curve shows the phase changes with temperature and heat added to or
removed from any system.

Heat Added
Draw a heating curve indicating the following:
1. Regions for solid only, liquid only, gas only, solid-liquid, liquid-gas
2. Know the relationship between melting point and the phases present.
3. Know the relationship between boiling point and the phases present.
4. Know where the slope is zero, where the slope is positive, and why.
Example: Assume this is a heating-cooling curve for water. Indicate the initial and final
conditions described below on the heating-cooling curve.
a. A sample of water is initially at 25C. Indicate this on the curve with an xi.
b. The sample is heated until it is at 110C. Indicate this on the curve with an xf.

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