Solids, Liquids and Phase Changes

Their
properties
and
Prof. Ronald
Jefferson A. Narceda, R.Chem., M.Sci.
changes
School of Chemical Engineering and Chemistry

Lets Review Some Vocab

Volume Amount of space

occupied by an object
Mass Amount of matter in an
object
Matter Something that
occupies space and has a mass
Density Mass per unit volume
of a material

The three states of

matter. . .

What makes a molecule

polar?
Polar molecules are said to possess a
permanent dipole moment.
Dipole moment, , (ionic and covalent)
Measure of net molecular polarity
The magnitude of the charge Q at
either end of the molecular dipole
times the distance, r, between the
charges
=Qxr
Expressed in debyes, D, where
1 D = 3.336 x 10-30 coulomb meters

Prof. Peter Deby

Noble Prize 1936

 Electronegativity
Electronegativity is the ability of an atom
to attract electrons
It increases from left to right and from
bottom to top in the periodic table (noble
gases excluded)
Fluorine is the most electronegative atom and
can stabilize excess electron density the best

Polar Covalent Bonds

Polar Covalent Bonds

Form between a non-metal/non-metal
of different electronegativities

EN = ENA ENB
When EN 1.7 ionic bond
When EN < 1.7 polar covalent bond
When EN < .5 non-polar covalent bond
6

Dipole Moment

% Ionic Character = experimental

(100%)
calculated

a high % IC means that the bond is

similar to or is an ionic bond

a low % IC means that it is more like

a covalent bond
7

Chloromethane
H

Cl
H

a) Calculate the dipole moment

b) Calculate the % ionic character of the bond
Experimentally measured dipole moment = 1.87 D
C-Cl bond distance = 178 pm = 178 x 10-12 m
If we assume that the contributions of the
nonpolar C-H bonds are small, then most of
the chloromethane dipole moment is due to
the C-Cl bond

Hydrochloric acid
Cl

Calculate the % ionic character

1. Distance between atoms is
127 pm
2. Experimentally measured
dipole
moment = 1.03 D

Tell which of the following compounds are

likely to have a dipole moment and show
the direction of each.
a) SF6

b) CHCl3

c) CH2Cl2

d) CH2CH2

10

Geometry of Molecules
H N H
H

NH3

O C O

H2O

Trigonal Pyramidal

CO2

Bent

Linear

Tetrahedral

Cl

H C H
H

CH4

H
CH3Cl

Cl

Cl
CHCl3

Cl

Cl

Cl

C
Cl
CCl4

Cl

Polar or Not Polar? That is the Question

H N H
H
NH3
Trigonal Pyramidal

O
H2O
Bent

O C O
CO2
Linear

Polar or Not Polar That is the Question?

H N H
H

NH3

O C O
CO2

Bent

= 1.47 D

H2O

Trigonal Pyramidal

Linear

= 1.85 D

=0D

Polar or Not Polar That is the Question?

Cl

H C H
H

CH4

CH3Cl

Cl

Cl
CHCl3

+
=0D

Cl

Cl

= 1.87 D

Cl

C
Cl

Cl

CCl4

= 1.90 D

=0D

Types of Intermolecular
Forces
4 main types of intermolecular
forces
(1)
(2)
(3)
(4)

London Dispersion ForcesIncreasing

Strength
Dipole-Dipole Forces
Hydrogen Bonds
Ion-Dipole Forces

London (Dispersion) Forces

Weakest of the IM forces. All molecules have dispersion
forces.
Result of interactions between instantaneous dipole
moments

Prof. Fritz
London

Dipole-Dipole Forces
Result of permanent dipole moments
in polar molecules

Ion-Dipole Forces
The force which dissolves ionic compounds.
A result of interactions between ions and
solvent molecules

Hydrogen Bonds
NOT a chemical bond
MUST contain hydrogen covalently
bonded to F, Cl, O or N.
Essential for Life!

Hydrogen Bonds

Molecules with larger molecular

weights have higher boiling points.
If the boiling point of CO2 is , and CS2
is. . .

Intermolecular Forces

Identify the likely kinds of

intermolecular forces in the
following:
H Cl
A) HCl

H H
H

H
H H

B) CH3CH3

H
H

C) CH3NH2

H
N

SAMPLE PROBLEM

Drawing hydrogen bonds between

molecules of a substance

PROBLEM: Which of the following substances exhibits hydrogen

bonding? For those that do, draw two molecules of the
substance with the H-bonds between them.
O
(c CH3C NH2
(b CH3OH
)
)
PLAN:Find molecules in which hydrogen is bonded to N, O or F.
Draw H-bonds in the format, B: ----- HA.
(a)

C2 H6

SOLUTION (a) C2H6 has no H-bonding sites (a non-polar

:
molecule).
H
(b
(c)
H
H C O H
O
)
O
H N CH3C CH C
H
H
3
N H
H O C H
O
CH3C N H
H
H
H

H
H N

Note: more than one H-bond per molecule is possible!

CH3C
O

Of the substances Ar, Cl2, CCl4 and HNO3

which has:
a) The largest dipole-dipole forces?

b)The largest hydrogen-bond forces?

c) The smallest dispersion forces?

Hydrogen Bonds and Life

Life Depends of H-bonds
The Stuff of Life relies on them to
stay together

Proteins, Enzymes
Amino Acids

Nucleic Acids (DNA, RNA)

Sugar-phosphate Backbone and
Base Pairs

Amino acids bond together to make polypeptides

The polypeptides fold to make the secondary structure of
proteins
H

H
C

H
C
R

N
N

C
H
O

O
C
H

N
N
H

H
N

H
C
O

C
H

H
C
R

How and Why does the alpha structure form??

Linus Pauling Discovered How, in 1948

While in bed with a cold. Lets describe how

C
N
H

R
C
H

Hydrogen Bonds are also important

in DNA

Adenine

NH2
N

Which goes with which ???

N
H

AT
O

Thymine

NH

N
H

GC

Right??? BUT WHY????

O
N

NH

Guanine
N
H

NH2

Come on down and get some base pairs

NH2

N
H

Cytosine

Bases
Types:- adenine and guanine (fused five- and six-membered
heterocyclic compounds) Purines

cytosine & thymine (six-membered rings)-Pyrimidines.

A fifth pyrimidine base, called uracil (U), usually takes the place
of thymine in RNA and differs from thymine by lacking a methyl
group on its ring.
PAIRING :
A =T and A=U
GC

Double helix
structure. . .
In
1948
Pauling
discovered
that
many
proteins
included
helical
(seealpha
helix)
shapes.
The DNA double helix is
stabilized by hydrogen bonds
between the bases attached
to the two strands.

The Guanine-Cytosine (GC) Base Pair

The Guanine-Cytosine (GC) Base Pair

Effect of Intermolecular forces on melting

and boiling points of molecular covalent
substances
Why does HF have the highest BP?

Molecular wts.
132
32

20

77

81

16

128
37
Molecular wts.

Increase only due to increase in MW,

Since all are non-polar

BONDS

Hydrogen Bonds

 Boiling point
Boiling point depends on intermolecular
force. Stronger intermolecular forces higher
b.p.
Intermolecular force : Van der Waals force and
H bond
Compounds which can form H bond would
have higher boiling point :

Melting point
It has a similar trend in b.p.
But in case of alkanes and carboxylic
acids, an even member of the series
has a higher m.p. than the odd
member immediately below (or even
above) it.
Meltin
g
point

No. of carbon atoms

H bond formation in Organic

compounds
O

H
O H

H
N H

N H

H
O

O
H

H
O

In carboxylic acid

In acid amide

Liquids and solids

Benzenecarboxylic acid is a white crystalline solid.

N
H

Solubility in water
It involves two kinds of energy when a
substance dissolves in water :
Energy required to break the bond /
overcome the force of attraction between
solute particles (intermolecular force).
Energy released when the attractive forces
formed by the water molecule and the solute
particles.

Solubility in water
Size of molecule
Solubility decreases with increasing
chain length as the intermolecular
force become stronger

more
energy required to break the bond.
Example : Ethanol is soluble in
water in all proportion while hexan-1ol is only slightly soluble.

Solubility in water
For aldehydes, ketones, etc. they
are only slightly soluble in water
unless the molecular size is small :
H

O
H

O
H

H
O

O
H

H3C

CH3

Gases
Because gases have so much space between
the particles they have properties that are
dependent on one another.

Gas Variables

Volume (V) - mL, L, kL

Temperature (T) oC measured in lab but
K (kelvin) for calculations
Number of particles (n) moles
Pressure (P) mmHg, psi(more to
come)
Force per unit area

Pressure

Solids and Liquids

Because the particles are so much closer in
liquids and solids, there are chances for
particles to attract (or repel). This and the
mass of the particles are main factors in
determining the properties of solids and
liquids.
Some properties are boiling and melting
points, surface tension, vapor pressure,
and crystalline structure.

Viscosity

Properties of Liquids

1.

The measure of a liquids resistance to flow

2.

Related to the ease in which individual

molecules move around in the liquid and
thus to the intermolecular forces present

3. Substances with small non-polar molecules

have weak intermolecular forces and low
viscosities (free flowing)
4.

More polar substances have stronger

intermolecular forces and have higher
viscosities

Affected by temperature (viscosity decreases at higher T)

Affected by molecular shape (longer molecules exhibit higher viscosity)

Table 12.4
Viscosity of Water at Several
Temperatures
viscosity
temperature
(oC)

(N.s/m2)*

20

1.00 x 10-3

40

0.65 x 10-3

60

0.47 x 10-3

80

0.35 x 10-3

*The units of viscosity are newton-seconds per square

meter.

Properties of Liquids

Surface Tension
1. The resistance of a liquid to spread out and increase
its surface area
2. Caused by differences in intermolecular forces
experienced by molecules at the surface and the
interior
3. Surface molecules feel attractive forces on only one
side and are drawn in toward the liquid
4. Interior molecules are drawn equally in all directions
5. Higher in liquids that have stronger intermolecular
forces
6. Compounds that interfere with the forces and
reduce surface tension are called surfactants.

The molecular
basis of surface
tension
The energy required to increase
surface area by a unit amount

Surface molecules experience

a net attraction downward.

Stronger
intermolecular
forces translate into
greater surface
tension.

Table
12.3
substanc
e
diethyl
ether
ethanol

Surface Tension and Forces Between

Particles
surface
formul
tension (J/m2)
a
at 20 oC
CH3CH2OCH2CH3 1.7 x 102

CH3CH2OH

2.3 x 10-

major
force(s)
dipole-dipole;
dispersion
H-bonding

butanol
water
mercury

H-bonding;
dispersion

H2O

7.3 x 10-

H-bonding

Hg

48 x 10-2

CH3CH2CH2CH2OH 2.5 x 10-

metallic
bonding

Shape of a water or mercury meniscus

in glass

stronger
cohesive
forces

Stronger
adhesive
forces

water-glass forces >

water-water forces

Hg-Hg forces >

Hg-glass forces

Capillarity: the rising of a liquid through a narrow

space against the pull of gravity

Solids
Solids may have a definite structure
and are called crystalline.

Solids that have no regular shape are

called amorphous.

The striking beauty of

crystalline solids. . .

Changes of State

Physical change from one

state of matter to another
Matter will change from
one state to another if
thermal energy is absorbed
or released.

Phase Changes

Physical form changes but chemical identity

does not change
Fusion (melting)
solid liquid
Freezing
liquid solid
Vaporization
liquid gas
Condensation
gas liquid
Sublimation
solid gas
Deposition

gas solid

52

Phase Changes

Energy released

sublimation
vaporizing

meltin
g

solid

liquid

freezing
Energy absorbed

gas

condensing

Solid-Liquid Phase Changes

MELTING change of state from a solid to
a liquid
Temperature at which a solid changes to
a liquid is called its melting point.
Melting occurs when a substance
ABSORBS thermal energy.
FREEZING change of state from a liquid
to a solid
Temperature at which a liquid changes to
a solid is called its freezing point.
Freezing occurs when a substances
LOSES thermal energy.

Liquid-Gas Phase Changes

EVAPORATION process where
liquid changes to a gas state
Particles in liquid ABSORB thermal
energy
Also called vaporization or boiling
Temperature at which a liquid boils
is its boiling point
CONDENSATION process where a
gas changes to liquid
Particles in gas LOSE thermal

Solid-Gas Phase Change

SUBLIMATION process where a
solid changes directly to a gas without
passing through the liquid state
Example: dry ice
Thermal energy is ABSORBED
DEPOSITION process where a gas
changes directly to a solid without
passing through the liquid state
Thermal energy is being LOST

Shows which phase is stable at

different combinations of pressure
and temperature.

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.
Supercritical Fluid:
gas

Neither true liquid nor true

58

Can
you
label
the
following?
a) solid region
b) Liquid region
c)Gas region
d)Normal boiling point
e)Normal melting point
f)Triple point
g)Supercritical
fluid
region
h) Critical point, what is
the critical pressure and

59

Types of solids
1. Molecular solid
-held together by intermolecular
forces
-H2O(s), CO2(s)
2. Metallic solid
-positively charged atomic cores
surrounded by delocalized
electrons
-Fe, Cu, Ag

60

Types of solids
3. Ionic solid
-cations and anions held together
by
electrical attraction of opposite
charges
-NaCl
4. Covalent network solid
-atoms held together in large
networks by
covalent bonds

61

Unit Cells in Crystalline

Solids

Metal crystals made up of atoms in regular arrays the

smallest of repeating array of atoms is called the unit
cell.
There are 14 different unit cells that are observed which
vary in terms of the angles between atoms some are
90, but others are not.

The crystal lattice and the unit cell.

lattice
point

unit
cell

unit
cell

portion of a 3-D
lattice

portion of a 2-D
lattice

Length of sides a, b, and c as well

as angles vary to give most
of the unit cells.

The three cubic unit cells

simple
cubic
1/8 atom
at 8
corners

coordination number
=6

Atoms/unit cell = 1/8 x 8

=1

The three cubic unit cells

bodycentered
cubic
1/8 atom
at 8
corners
1 atom at
center

coordination number
=8

Atoms/unit cell = (1/8 x 8) + 1 =

2

The three cubic unit cells

facecentered
cubic
1/8 atom
at 8
corners
1/2 atom
at 6 faces

coordination number =
12

Atoms/unit cell = (1/8 x 8) + (1/2 x 6)

=4

Free energy change, G

Thermochemistry

1.All naturally occurring processes, every

phase change has a free-energy change
2.G = H - T S
3. H enthalpy, heat flow, positive (from
surrounding to system, bond breaking takes
energy),
negative
(from
system
to
surroundings, bond making)
4. S entropy, disorder, positive (ordered to
disordered), negative (disordered to ordered)

Thermochemistry

Thermochemistry

Calculating the temperature at a

phase change
G > 0 non-spontaneous
G < 0
spontaneous
G = 0 equilibrium
2. Set G = 0
0 = H - TS and solve for T
T = H/S
Chloroform has Hvap = 29.2 kJ/mol and Svap =
87.5 J/K mol.
What is the boiling point of
chloroform?

Heating Curve for H2O

Heating Curve for H2O

Heating curve for H2O

E = molar heat capacity (T)
Energy to heat ice from -25C to 0C
Molar heat capacity of ice= 36.57
J/molC
Energy to heat H2O from 0C to 100C
Molar heat capacity of liquid H2O = 75.4 J/
molC
72

Energy of Heat and Phase Change

Heat of vaporization:
heat needed for the
vaporization of a liquid.
H2O(l) H2O(g) H = 40.7
kJ
Heat of fusion: heat
needed for the melting of a
solid.
H2O(s) H2O(l) H = 6.01
kJ
Temperature does not
change during the change
from one phase to another.

Vapor Pressure
The partial pressure of a
gas in equilibrium and at
constant temperature
with liquid
The pressure exerted by
gaseous molecules above
a liquid
In a sealed container,
some
of
a
liquid
evaporates to establish a
pressure in the vapor
phase.
Vapor pressure: partial
pressure of the vapor over
the liquid measured at
equilibrium and at some
temperature.

Evaporation, Vapor Pressure, and Boiling Point

Evaporation, Vapor Pressure, and Boiling Point

The higher the temperature and the lower

the boiling point of the substance the
greater the fraction of molecules in the
sample that have sufficient kinetic
energy to break free from the surface of
the liquid and escape into the vapor.

Evaporation, Vapor Pressure, and Boiling Point

Numerical value of Vapor Pressure depends

on:
a) Magnitude of intermolecular forces
The smaller the forces the higher the
vapor
pressure,
loosely
held
molecules escape
easily

b) Temperature
The higher the temperature, the higher
the
vapor pressure, larger fraction of
molecules
have sufficient kinetic
energy to escape

Temperature Dependence of
Vapor Pressures
The
vapor
pressure
above the liquid varies
exponentially
with
changes
in
the
temperature.
The Clausius-Clapeyron
equation shows how the
vapor
pressure
and
temperature are related.

Clausius-Clapeyron Equation
We can see from this form that the ClausiusClapeyron equation depicts a line
ln P

H vap
RT

Can be written as:

H vap 1
ln P
C
R T

which clearly resembles the model y=mx+b, with ln P representing y,

C representing b, 1/T acting as x, and -Hvap/R serving as m.
Therefore, the Clausius-Clapeyron models a linear equation when the
natural log of the vapor pressure is plotted against 1/T, where
-Hvap/R is the slope of the line and C is the y-intercept

Clausius-Clapeyron Equation

In its most useful form for our purposes:

P1 H vap 1 1
ln
( )
P2
R T2 T1
In which:
P1 and P2 are the vapor pressures at T1 and T2 respectively
T is given in units Kelvin
ln is the natural log
R is the gas constant (8.314 J/K mol)
Hvap is the molar heat of vaporization

Evaporation, Vapor Pressure, and Boiling Point

This equation makes it possible to calculate

the heat of vaporization of a liquid by
measuring its vapor pressure at several
temperatures and then plotting the results
to obtain the slope
Once the heat of vaporization and the vapor
pressure at one temperature are known, the
vapor pressure of the liquid at any other
temperature can be calculated.

Using the Clausius Clapeyron

Equation
Boiling point the temperature at
which the vapor pressure of a
liquid is equal to the pressure of
the external atmosphere.
Normal
boiling
point
the
temperature at which the vapor
pressure of a liquid is equal to
atmospheric pressure (1 atm).

SAMPLE PROBLEM

Using the Clausius-Clapeyron equation

PROBLEM: The vapor pressure of ethanol is 115 torr at 34.9 oC. If

Hvap of ethanol is 40.5 kJ/mol, calculate the
temperature (in oC) when the vapor pressure is 760
torr.
PLAN:
We are given four of the five variables in the ClausiusClapeyron equation. Substitute and solve for T2.
SOLUTION
:
l
n

P2
-Hvap 1 1
ln
=

P1
R T2 T1
760
torr
115
torr

-40.5 x103
8.314
J/mol
J/mol.K
T2 = 350 K = 77
o
C

T1 = 34.9 oC = 308.0 K
1
1
308 K
T2