Chem 16 General Chemistry 1

09 Liquids, Solids, and Phase Changes

Dr. Gil C. Claudio

First Semester 2014-2015
Table of Contents

Contents
1 Overview of Physical States and Phase Changes

2 Intermolecular Forces

3 Some Properties of Liquids

3.1 Surface Tension, Viscosity, Capillary Action . . . . . . . . . . . .
3.2 Vaporization and Boiling . . . . . . . . . . . . . . . . . . . . . . .

6
6
10

4 Solids
4.1 Types of Solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2 Melting and Sublimation . . . . . . . . . . . . . . . . . . . . . . .

11
11
14

5 Phase Changes

15

6 Phase Diagrams

15

References
References of these notes
General Chemistry, 10th ed, by Ralph H. Petrucci, F. Geoffrey Herring,
Jeffy D. Madura, and Carey Bisonnette.
Chemistry: The Central Science, 13th ed., by Theodore L. Brown, H. Eugene
LeMay Jr., Bruce E. Bursten, Catherine J. Murphy, Patrick M. Woodward,
and Matthew W. Stoltzfus.

1 Overview of Physical States and Phase Changes

Observations in Solids, Liquids, and Gases

GAS

LIQUID

SOLID

Volume of
container

Assumes
volume of
container

Own volume

Own volume

Shape of
container

Assumes
shape of
container

Assumes
shape of
container

Own shape

Compressibility

Compressible

Incompressible

Incompressible

Diffusion

Rapidly

Slowly

Very slowly

Flow

Flows readily

Flows readily

Does not flow

GAS

LIQUID

SOLID

Space between
molecules

Empty space.
Molecules far
apart

Closer
together

Close together

Order of
molecules

Total disorder

Disorder

Ordered
arrangement

Freedom of
motion of
particles

Complete
freedom

Free relative to
each other

Particles
essentially in
fixed position

REASON

Very low
(or no) IFA

With IFA

Strong IFA

Molecular Explanation

2 Intermolecular Forces
Relative Strengths of Attractive Forces
Melting and Boiling Points of Representative Substances
Force Holding
Particles Together
Chemical bonds
Ionic bonds
Metallic bonds
Covalent bonds
Intermolecular
forces
Dispersion
Dipole-dipole
Hydrogen-bonding

Substance

MP (K)

BP (K)

Lithium fluoride (LiF)

Beryllium (Be)
Diamond (C)

1118
1560
3800

1949
2742
4300

Nitrogen (N2 )
Hydrogen chloride (HCl)
Hydrogen fluoride (HF)

63
158
190

77
188
293

van der Waals Forces

The term van der Waals forces is used to describe, collectively,
intermolecular forces of the London type and interactions between permanent
dipoles.
Non-Polar Molecules
Non-polar molecules due to
low EN difference between two bonded atoms. e.g., methane CH4
2

 symmetric overall geometry, e.g., boron trifluoride BF3

en.wikipedia.org/wiki/File:Methane-CRC-MW-3D-balls.png

en.wikipedia.org/wiki/ File:Boron-trifluoride-elpot-3D-vdW.png

London Dispersion Forces

London Dispersion Forces (or simply dispersion forces) are the
intermolecular forces resulting from attractions between instantaneous and
induced dipoles.
Fritz London (1930)
ee2+
e-

2+
e-

Polarizability
Polarizability is the ease with which the electron cloud of an atom or a
molecule is distorted by an outside influence, thereby inducing the dipole
moment.
The greater the polarizability of the molecule, the more easily its electron
cloud can be distorted to give a momentary dipole, which leads to
stronger LDF.
The bigger the electron cloud, higher polarizability, thus stronger LDF.
Bigger molecules have higher IFA.
Electrons in elongated molecules are more easily displaced than are those
in small, compact, symmetrical molecules. More polarizable, stronger
LDF, higher IFA.
Polarizability in Pentanes
n-Pentane C5 H12 bp = 36.1 C Neopentane C5 H12 bp = 9.5 C

en.wikipedia.org/wiki/File:Pentane-3D-space-filling.png

commons.wikimedia.org/wiki/File:Neopentane 3D 1.png

Gecko on Glass

commons.wikimedia.org/wiki/File:Gecko Leaftail 1.jpg

Polar Molecules
A dipole is molecule with one end having a slight negative charge and the
other end having a slight positive charge.
1. EN difference between two bonded atoms polarity within the bond
2. overall geometry of the molecule

en.wikipedia.org/wiki/File:Hydrogen-fluoride-elpot-transparent-3D-balls.png

Water and Ammonia

en.wikipedia.org/wiki/ File:Water-elpot-transparent-3D-balls.png

en.wikipedia.org/wiki/ File:Ammonia-elpot-transparent-3D-balls-A.png

Dipole-Dipole Interactions

+
-

+
-

+ + -

Ion-Dipole Interactions

+
-

+
-

Hydrogen Bond
Hydrogen bonding is the bonding that results from the intermolecular
attractions between molecules containing hydrogen bonded to an
electronegative element. The most important examples involve oxygen,
nitrogen, and fluorine.
5

Hydrogen Bonds in Water

en.wikipedia.org/wiki/File:3D model hydrogen bonds in water.svg

Butane and Acetone

Two molecules with molar mass of 58 amu
Butane C4 H10 , bp = 0.5 C
Acetone C3 H6 O,bp = 56.2 C

en.wikipedia.org/wiki/File:Butane-3D-balls.png

en.wikipedia.org/wiki/File:Butane-3D-balls.png

Summary of van der Waals Forces

LDF exist between all molecules.
Displacements of electrons in
molecules. Increase with increasing molecular mass. Depend on
molecular shapes.
Permanent dipoles. Displacements of electron pairs in bonds rather than
in molecules as a whole, resultant dipole moments.
For substances of comparable molecular masses, dipole forces can
produce significant differences in properties such as melting point,
boiling point, and enthalpy of vaporization.
When comparing substances of widely different molecular masses,
dispersion forces are usually more significant than dipole forces.

3 Some Properties of Liquids

3.1

Surface Tension, Viscosity, Capillary Action

Surface Tension
Surface Tension is the intermolecular, cohesive attraction that causes a
liquid to minimize the surface area.

en.wikipedia.org/wiki/File:Surface tension March 2009-3.jpg

Surface Tension: Molecular View

en.wikipedia.org/wiki/File:WassermolekuleInT
opfchen-2.svg

Water Strider

en.wikipedia.org/wiki/File:WaterstriderEnWiki.jpg

Viscosity
Viscosity is a measure of the resistance of fluids to flow.
measured by timing how long it takes a certain amount of liquid to flow
through a thin tube under gravitational force.
related to the ease with which individual molecules of the liquid can
move with respect to one another
also related to structural features that cause the molecules to be entangled
during flow.
Honey

en.wikipedia.org/wiki/File:Runny hunny.jpg

Viscosities of Hydrocarbons
Viscosities of a Series of Hydrocarbons at 20 C
Substance

Formula

Hexane
Heptane
Octane
Nonane
Decane

CH3 CH2 CH2 CH2 CH2 CH3

CH3 CH2 CH2 CH2 CH2 CH2 CH3
CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH3
CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH3
CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH3

Viscosity
(kg/m-s)
3.26 104
4.09 104
5.42 104
7.11 104
1.42 103

Cohesive and Adhesive Forces

Cohesive forces are intermolecular forces between like molecules, such as
within a drop of liquid.
Adhesive forces are intermolecular forces between unlike molecules, such as
molecules of a liquid and of a surface with which it is in contact.
If cohesive forces are strong compared with adhesive forces, a drop maintains
its shape. If adhesive forces are strong enough, the energy requirement for
spreading the drop into a film is met through the work done by the collapsing
drop.

Hydrophobic Effect
The hydrophobic effect is the observed tendency of nonpolar substances
to aggregate in aqueous solution and exclude water molecules.
The name, literally meaning water-fearing, describes the segregation
and apparent repulsion between water and nonpolar substances.
The hydrophobic effect explains the separation of a mixture of oil and
water into its two components, and the beading of water on nonpolar
surfaces such as waxy leaves.
Hydrophobic Leaf

upload.wikimedia.org/wikipedia/commons/8/8c/Dew 2.jpg

Hydrophobicity of Surfaces

en.wikipedia.org/wiki/File:Surface tension.svg

Capillary Action
Capillary action, or capillarity, is the ability of a liquid to flow against
gravity where liquid spontaneously rise in a narrow space such as between the
hairs of a paint-brush, in a thin tube, in porous material such as paper, in some
non-porous materials such as liquefied carbon fiber, or in a cell.
This effect can cause liquids to flow against the force of gravity, sun or
the magnetic field induction.
It occurs because of inter-molecular attractive forces between the liquid
and solid surrounding surface;
If the diameter of the tube is sufficiently small, then the combination of
surface tension (which is caused by cohesion within the liquid) and force
of adhesion between the liquid and container act to lift the liquid.

Capillarity

en.wikipedia.org/wiki/File:Capillarity.svg

3.2

Vaporization and Boiling

Vaporization
Vaporization is the passage of molecules from the liquid to the gaseous
state.
Liquid molecules having kinetic energies sufficiently above the average
value are able to overcome intermolecular forces of attraction and escape
from the surface of the liquid into the gaseous state.
Vaporization occurs more readily with
increased temperature
increased surface area of the liquid
decreased IFA
Enthalpy of Vaporization
The enthalpy of vaporization is the quantity of heat that must be absorbed
if a certain quantity of liquid is vaporized at a constant temperature. Always
endothermic, > 0.
Hvap = Hvapor Hliquid
The conversion of a gas or vapor to a liquid is called condensation. Always
exothermic, < 0.
Hcondensation = Hvap

Vapor Pressure
Vapor pressure is the pressure exerted by a vapor when it is in dynamic
equilibrium with its liquid at a fixed temperature.
Liquids with high vapor pressures at room temperature are said to
be volatile, and those with very low vapor pressures are nonvolatile.
Depends on IFA.
As an excellent first approximation, the vapor pressure of a liquid
depends only on the particular liquid and its temperature, and not on
the amount of liquid nor the amount of vapor, as long as some of each is
present at equilibrium.
Vapor pressure increases with temperature.
10

Clausius-Clapeyron Equation
The liquid-vapor curve of P-vs-T is described by the Clausius-Clapeyron
equation

 

Hvap 1
P2
1
ln

=
P1
R
T2
T1
The plot is a straight line (y = mx + b), with y ln 1/P and x 1/T.
Applying the Clausius-Clapeyron Equation
PHMB 10e, Example 12-5, pp 516-517
Calculate the vapor pressure of water at 35 C, given that the vapor
pressure of water at 313.2 K is 55.3 mmHg, that Hvap = 44.0 kJ/mol, and that
R = 8.3145 J/mol-K.
ANSWER: 41.9 mmHg
Vapor Pressure of Water
Vapor pressure of water at various temperatures
T ( C)
0.0
10.0
20.0
21.0
22.0
23.0
24.0
25.0
26.0
27.0
28.0

P (mmHg)
4.6
9.2
17.5
18.7
19.8
21.1
22.4
23.8
25.2
26.7
28.3

T ( C)
29.0
30.0
40.0
50.0
60.0
70.0
80.0
90.0
91.0
92.0

P (mmHg)
30.0
31.8
55.3
92.5
149.4
233.7
355.1
525.8
546.0
567.1

T ( C)
93.0
94.0
95.0
96.0
97.0
98.0
99.0
100.0
110.0
120.0

P (mmHg)
588.6
610.9
633.9
657.6
682.1
707.3
733.2
760.0
1074.6
1489.1

Boiling
Boiling is a process in which vaporization occurs throughout a liquid. It
occurs when the vapor pressure of a liquid is equal to barometric pressure.
The normal boiling point is the temperature at which the vapor pressure of
a liquid is 1 atm. It is the temperature at which the liquid boils in a container
open to the atmosphere at a pressure of 1 atm.

4 Solids
4.1

Types of Solids

Network Covalent Solids

A network covalent solid is a substance in which covalent bonds extend
throughout the crystal, making the covalent bond both an intramolecular and
an intermolecular force.
e.g., the two allotropes of carbondiamond and graphite
Diamond and Graphite

11

en.wikipedia.org/wiki/File:Diamond and graphite2.jpg

Allotropes of Carbon

commons.wikimedia.org/wiki/File:Eight Allotropes of Carbon.png

1. Diamond
2. Graphite
3. Lonsdaleite
4. C60
5. C540
6. C70
7. Amorphous carbon
8. single-walled carbon nanotube
Crystalline Solid
A crystalline solid (or simply crystal) is a solid whose internal arrangement
of atoms, molecules, or ions possesses a regularly repeating pattern in any
direction through the solid.
usually have flat surfaces (or faces) that make definite angles with one
another, thus they have highly regular shapes. E.g., NaCl, quartz, and
diamond.
12

Metallic Solids
Metallic solids (or simply metals) consist entirely of metal atoms.
Metallic bonding happens because the valence electrons are delocalized
throughout the entire solid. That is, the valence electrons are not
associated with specific atoms or bonds but are spread throughout the
solid. In fact, we can visualize a metal as an array of positive ions
immersed in a sea of delocalized valence electrons.
The electrons are confined to the metal by electrostatic attractions to the
cations, and they are uniformly distributed throughout the structure.
Metallic bonding is stronger than dispersion forces, but there are note
enough valence electrons to form covalent bonds between atoms.
Electron Sea Model
Electrical conductivity. The electrons are mobile. With an applied
voltage, the electrons flow through the metal toward the positively
charged end of the wire.
Thermal conductivity. The movement of electrons permits ready
transfer of kinetic energy throughout the solid.
Malleability and ductility. Metal atoms form bonds to many neighbors.
Changes in the positions of the atoms due to reshaping the metal are
partly accommodated by a redistribution of electrons.
Alloys
An alloy is a material that contains more than one element and has the
characteristic properties of a metal.
It is one of the primary ways of modifying the properties of pure metallic
elements.
Nearly all the common uses of iron involve alloy compositions (e.g.,
stainless steel).
Bronze is formed by alloying copper and tin.
Brass is an alloy of copper and zinc.
Ionic Solids
Ionic solids are held together by the electrostatic attraction between cations
and anions.
The lattice energy measures the energy to break up an ionic crystal and
separate its ions.
The attractive force between a pair of oppositely charged ions increases
with increased charge on the ions and with decreased ionic sizes.
Characteristics of Crystalline Solids (1)
Metallic
structural particles: Cations and delocalized electrons
contributing force: metallic bonds
typical properties: Hardness varies from soft to very hard; melting point
varies from low to very high; lustrous; ductile; malleable; very good
conductors of heat and electricity
13

 examples: Na, Mg, Al, Fe, Sn, Cu, Ag, W

Ionic
structural particles: cations and anions
contributing force: electrostatic attractions
typical properties: Hard; moderate to very high melting points;
nonconductors as solids, but good electric conductors as liquids; many
are soluble in polar solvents such as water
examples: NaCl, MgO, NaNO3
Characteristics of Crystalline Solids (2)
Network covalent
structural particles: atoms
contributing force: covalent bonds
typical properties: Most are very hard and either sublime or melt at very
high temperatures; most are non-conductors of electricity
examples: diamond, graphite, SiC, AlN, SiO2
Molecular: Non-polar
structural particles: atoms or non-polar molecules
contributing force: dispersion forces
typical properties: Soft; extremely low to moderate melting points
(depending on molar mass); sublime in some cases; soluble in some
nonpolar solvents
examples: He, Ar, H2 , CO2 , CCl4 , CH4 , I2
Characteristics of Crystalline Solids (3)
Molecular: polar
structural particles: polar molecules
contributing force: dispersion forces and dipole-dipole interactions
typical properties: Low to moderate melting points; soluble in some
polar and some nonpolar solvents
examples: (CH3 )2 O, CHCl3 , HCl
Molecular: Hydrogen bonded
structural particles: molecules with H bonded to N, O, or F
contributing force: hydrogen bonds
typical properties: Low to moderate melting points; soluble in some
hydrogen-bonded solvents and some polar solvents
examples: H2 O, NH3

14

4.2

Melting and Sublimation

Melting Point
Melting is the transition of a solid to a liquid and occurs at the melting
point.
The quantity of heat required to melt a solid is the enthalpy of fusion
Hfus
Freezing is the conversion of a liquid to a solid that occurs at a fixed
temperature known as the freezing point.
The melting point and freezing point of a substance are identical.
The enthalpy of fusion of water is 6.01 kJ/mol
H2 O(s) H2 O(l)

Hfus = 6.01 kJ/mol

Sublimation and Deposition

Sublimation is the passage of molecules from the solid to the gaseous state.
The enthalpy of sublimation Hsub is the quantity of heat needed to
convert a solid to vapor.
Hsub = Hfus + Hvap
The Clausius-Clapeyron can also be used for sublimation.
Deposition is the passage of molecules from the gaseous to the solid state.

5 Phase Changes
Phase Changes
The state of matter depends on:
1. IFA. Depends on the nature of the substance.
2. Temperature. Determines the kinetic energy of the molecules.
Phase changes are the change of a substance from one state of matter to
another.
n
tio
iza
n
D
tio
iza
n
o
I

Vap
o

Con

riza
tion
satio
n

den

Sublimation

Deposition

Gas

Liquid
g

ee

Solid

Fr

zin

ltin

Me

en.wikipedia.org/wiki/File:Phase change - en.svg

15

Enthalpy of system

Plasma

n
eio

Calculating H for Temperature and Phase Changes

BLBMWS 13e, Exercise 11.3, p 460
Calculate the enthalpy change upon converting 1.00 mol of ice at 25 C to
steam at 125 C under a constant pressure of 1 atm. The specific heats of ice,
liquid water, and steam are 2.03, 4.18, and 1.84 J/g-K, respectively. For H2 O,
Hfus = 6.01 kJ/mol and Hvap = 40.67 kJ/mol.
ANSWER: 56.0 kJ

6 Phase Diagrams
Phase Diagrams
A phase diagram is a graphical representation of the conditions of
temperature and pressure at which solids, liquids, and gases (vapors) exist,
either as single phases or states of matter or as two or more phases in
equilibrium.
Features of a Phase Diagram
The lines that separate the three regions indicate pressures and
temperatures at which two phases can coexist at equilibrium.
called the lines of equilibrium or phase boundaries. Phase transitions
occur along these lines. For example, the solid-gas coexistence curve
specifies the vapor pressure of the solid as a function of pressure.
The melting point at 1 atm is the normal melting point The melting point
at 1 bar is the standard melting point.
Same for normal and standard boiling point.
At the triple point, the three lines in the phase diagram intersect at which solid,
liquid, and gas coexist in equilibrium.
Triple Point
The triple point of a substance is the temperature and pressure at which the
three phases (gas, liquid, and solid) of that substance coexist in thermodynamic
equilibrium.

http://www.fphoto.com/site/asset/slideshow/ Fphoto-43349706J-2RMd.jpg

16

Critical Point
The critical point refers to the temperature and pressure at which a liquid
and its vapor become identical. It is the highest temperature point on the vapor
pressure curve.
The density of the liquid decreases, that of the vapor increases, and
eventually the two densities become equal.
The surface tension of the liquid approaches zero. The interface between
the liquid and vapor becomes less distinct and eventually disappears.
A supercritical fluid is any substance at a temperature and pressure above its
critical point, where distinct liquid and gas phases do not exist.
Critical Temperature and Pressure
The temperature and pressure at the critical point are the critical
temperature Tc and the critical pressure Pc .
For water, Tc = 647 K (374 C) and Pc = 218 atm.
At any temperature above Tc , liquid and vapor phases cannot coexist
in equilibrium, and isothermal compression of the vapor will not cause
condensation, in contrast to compression below Tc .
Critical CO2

commons.wikimedia.org/wiki/File:Critical carbon dioxide.jpg

17