Principles of General Chemistry, 2nd ed. By M.

Silberberg
Chemistry, 8th ed. by W. Whitten, R. Davis, R., M. L. Peck, and G. Stanley.
Exercise
For each pair of substances, identify the key
Intermolecular intermolecular force(s) in each substance, and select
the substance with the higher boiling point:
Forces of Attraction (a) MgCl2 or PCl3

(b) CH3NH2 or CH3F

(c) CH3OH or CH3CH2OH

CH3
(d) Hexane
CH3CCH2CH3
(CH3CH2CH2CH2CH2CH3)
or 2,2-dimethylbutane CH3

Answer Answer
(a) Mg2+ and Cl- are held together by ionic bonds while PCl3 is (c) Both CH3OH and CH3CH2OH can H bond but CH3CH2OH has
covalently bonded and the molecules are polar and held together by more CH for more dispersion force interaction and higher molecular
dipole-dipole interactions. weight. Therefore, CH3CH2OH has the higher boiling point.
Ionic interactions are stronger than dipole interactions and so
MgCl2 has the higher boiling point.

(b) CH3NH2 and CH3F are both covalent compounds and have
bonds which are polar. CH3NH2 can H bond while that in CH3F cannot.
Therefore, CH3NH2 has the stronger interactions and the higher
boiling point.
(d) Hexane and 2,2-dimethylbutane are both nonpolar with only
dispersion forces to hold the molecules together. Hexane has the larger
surface area and therefore, the greater dispersion forces and higher
boiling point.

Principles of General Chemistry, 2nd ed. By M. Silberberg

Answer Chemistry, 8th ed. by W. Whitten, R. Davis, R., M. L. Peck, and G. Stanley.

Molecules that has The Condensed

the larger surface
area Phases:

has the greater Solids and Liquids
dispersion forces

has higher
boiling point.
 Properties at the Solid State Amorphous & Crystalline Solids
AMORPHOUS & CRYSTALLINE
• Amorphous solids do not have a well ordered
molecular structure.
– Examples include waxes, glasses, asphalt.

• Crystalline solids have well defined structures that

consist of extended array of repeating units called
unit cells.
cells
– Crystalline solids display X-ray diffraction patterns
which reflect the molecular structure.

Properties at the Solid State Unit Cells

UNIT CELLS

Unit cells are the smallest repeating unit of a crystal.
 As an analogy, bricks are repeating units for buildings.

There are seven basic crystal systems.

Unit Cells Types of Solid According to Bond

(Simple Cubic, Body-Centered Cubic. Face-Centered Cubic)
between Particles
Molecular Solids Network Covalent

Ionic solids Metallic Solids

Molecular Solids
• have molecules in each of the positions of the
unit cell
• have low melting points, are volatile, and are
electrical insulators.
– Examples: water, sugar, carbon dioxide, benzene
Network Covalent Solids
• have atoms that are covalently bonded to one
another
– Examples: Diamond, graphite, SiO2 (sand), SiC

Ionic Solids Metallic Solids

• have ions that occupy the positions in the
unit cell
– Examples: CsCl, NaCl, ZnS
• may be thought of as positively charged nuclei
surrounded by a sea of electrons.
• the positive ions occupy the crystal lattice
positions.
– Examples: Na, Li, Au, Ag, ……..

Properties at the Solid State Properties at the Solid State

Normal Melting Point Sublimation
• is the temperature at which
• the solid transforms
the solid melts (liquid and directly to the vapor
solid in equilibrium) at phase without passing
exactly 1.00 atm of through the liquid
pressure. phase.
• the melting point increases
as the strength of the • solid CO2 or “dry” ice
intermolecular attractions does this well.
increase.
 Principles of General Chemistry, 2nd ed. By M. Silberberg
Chemistry, 8th ed. by W. Whitten, R. Davis, R., M. L. Peck, and G. Stanley.
Heat Transfers
Heat Transfer and • 2 Main equations:
Phase Diagrams q = mc∆T
 only used when temperature changes

q = ∆Hphase transition • moles substance

 only used at the temperature where
phase change occurs (at constant
temperature only)

Heat Transfers Heat Transfers

• How many joules of energy must be

absorbed by 5.00 x 102 g of H2O at 50.0oC to
convert it to steam at 120oC? The molar heat
of vaporization of water is 40.7 kJ/mol and the
molar heat capacities of liquid water and
steam are 75.3 J/mol oC and 36.4 J/mol oC,
respectively.

Heat Transfers Heat Transfers

3rd
1st 2nd
• Steps involved:
1st: water warmed from 50 oC to 100 oC
2nd: liquid water converted to steam
(BOILING) at constant temperature of
100 oC
3rd: steam heated from 100 oC to 120 oC
Heat Transfers Heat Transfers

1 mol
Calculate # of moles of water H 2 Ounit of heat capacity and heat of
since
The total amount of energy for this process is
O×
? mol = 500 g H 2vaporization = 27.8 mol H 2 O
18 g H are
O in /moles
2 the sum of the 3 parts we have calculated.
1st let's calculate the heat required to warm water from 50 to 100 o C

?J = (27.8 mol )

75.3 J 
( )
 100.0 − 50.0 C = 1.05 × 10 J
mol o C 
o 5 (1.05 × 10 J ) + (11.31 × 10 J ) + (0.20 × 10 J ) =
5 5 5

 40.7 × 103 J  12.56 × 10 5 J or 1.26 × 10 3 kJ

? J = ( 27.8 mol)  = 1131
. × 105 J
 mol 
 36.4 J 
? J = ( 27.8 mol)
 mol oC ( )
 120.0 -100.0 C = 0.20 × 10 J
o 5
Remember: Heat is not a state function!

Heat Transfers Liquid-Vapor Interphase

• Calculate the amount of heat required to
• Because the vapor (gas phase) is directly
convert 150.0 g of ice at -10.0oC to water at
affected by pressure and temperature
40.0oC. (specific heat of ice is 2.09 J/goC)
changes, boiling process may occur at
? J = (150.0 g)(2.09
J
)(10 o C) = 3.14 × 103 J
different pressures
goC
J
? J = (150.0 g)(334 )= 5.01 × 10 4 J • Normal boiling point occurs at 100oC at 25
g
atm. Is it the same if the external pressure is
J
? J = (150.0 g)(4.18 o )(40 o C) = 2.51 × 104 J decreased eg. at higher altitudes?
g C
7.83 × 104 J

Liquid-Vapor Interface Liquid-Vapor Interface

• The Clausius-Clapeyron Equation
As the temperature  P  ∆ H vap  1 1 
ln  2  =  − 
increases, the vapor  P1  R  T1 T2 
pressure (at the
equilibrium line) also  determine vapor pressure of a liquid at a new T
 determine what T we must heat something to get a
increases, but not specified vapor pressure
linearly  way to determine DHvap if we know pressure at 2 T’s
 You can only use this equation to calculate vapor
pressure-temperature at the equilibrium condition!
Liquid-Vapor Interface Solid-Liquid Interface
• Example: In Benguet the normal Molar heat of fusion or ∆Hfusion
atmospheric pressure is 630 torr. At what
temperature does water boil in Benguet? • is the amount of heat required to melt a
mole of a substance at its melting point
 P  ∆ H vap  1 1
ln  2  =  − 
 P1  R  T1 T2 
• the molar heat of crystallization is the
630 torr  40.7 × 10 3 J mol  1 1
ln  =  −  reverse of molar heat of fusion
 760 torr  8.314 K mol  373 K T2 
J
+6012 J
1.00 mole H 2O (s) at 0 o C 
← 
-6012 J
→ 1.00 mole H O at 0o C
2 (l)
Final answer: 368 K or 95oC

Solid-Liquid Interface Solid-Vapor Interfaces

• At the solid-liquid interface, the external • for solid-vapor interfaces, use Clausius-
pressure directly affects the volume of the Clapeyron equation
condensed phase, hence the temperature t
which it melts/crystallizes. • Molar Heat of Sublimation, ∆Hsub – amount
of heat needed to convert 1 mole of solid to
• The Clapeyron Equation: only used in
1 mole of gas at constant temperature
solid  liquid interfaces

solid ←  →
sublimatio n
 gas
condensati on

Phase Diagrams Phase Diagrams

 “So, if you think you are
standing firm, be careful that
you don't fall!”
fall!”
- 1 Corinthians 10:12 -

questions?