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Condensed Phases

 The K-M theory of gases assumes that:


 There is no interaction between atoms/molecules

 The space between the atoms/molecules is large.

Chapter 12  However, other phases also exist:


 Solid and Liquid

 These contain atoms or molecules in much closer proximity.

 Something must hold these atoms or molecules together:


intermolecular forces
Condensed Phases: Liquids, Solids

Intermolecular forces are different and weaker than the forces


that hold the atoms of a molecule together (bonding).

The Nature of Intermolecular Forces


Properties of the Condensed Phases: Liquids and Solids  Attractive Forces
 Electrostatic in nature.
 Solid  Liquids  Intramolecular forces
 High density  High density  These are bonding forces

 Fixed shape  Assume shape of container  Exist within a molecule

 Definite volume  Definite volume  Influence the chemical properties of the substance

 Atoms/molecules are  Atoms/molecules have  Intermolecular forces

essentially fixed in translational freedom  Nonbonding forces

place  Exist between different molecules

 Influence the physical properties of a substance

 boiling point
 melting point
 vapor pressure
 density
 viscosity
 surface tension
 solubility

The Nature of Intermolecular Forces The Nature of Intermolecular Forces


 Intermolecular forces are much weaker than intramolecular forces.
 Example: 16kJ/mol vs. 431 kJ/mol for HCl

 When a substance undergoes a phase change, the intermolecular


forces are broken.
 If intramolecular forces (bonds) are broken  chemical reaction.

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Condenses Phases: Water The Intermolecular Forces

 Colorless, odorless and tasteless


 Density of ice less than density of liquid water!
 Not the normal trend.  Stem from electrostatic interactions between different atoms or
 For equal masses of ice & water, ice has the larger volume.
molecules
 Attraction of opposite charges
 For equal volumes of ice & water, water has the larger mass.

 Water expands when it freezes.

Stronger Interactions
 3 Major Types:
 Ice floats on water. (Life on earth, as we know it, would not be
 Dispersion Forces (London Forces)
possible if this were not true.)
 Dipole-Dipole Interactions
 Density of liquid water = 1.00 g/mL
 H-Bonding
 Density of ice = 0.917 g/mL

Polar Bonds to Polar Molecules


Strengths of Intermolecular Forces
(Review from Ch 10)
 Bonds will be polar if there is a
difference in electronegativity
 Predictions can be made if you understand the intermolecular forces for
each substance. between 2 atoms.
 To understand the forces present you must also understand the shapes  Bond polarity results in an H F
and polarities of the molecules involved. unequal electron distribution,
resulting in areas of partial
 Example: Which of the following chemicals would have the higher
boiling point? positive and partial negative
charge. Polar Covalent Bond
 Cl2 and I2  A polar molecule similarly has a δ+ δ-
 CH3 OCH 3 and CH 3 CH2OH charge separation between two H–F
parts of the compound.
 NaCl and CH 4  A molecule must have at (Alternate Representations)
least one polar bond to be a
polar molecule. H–F
 Polar bonds do not always
result in polar molecule.

Polar Bonds to Polar Molecules


Polar Bonds to Polar Molecules
(Review from Ch 10)
(Review from Ch 10)
 A molecule with more than one polar covalent bond may or may not
 Any molecule that has a center of
be a polar molecule.
positive charge and a center of
 Unsymmetrical molecules such as water have polar bonds whose
negative charge in different points is
said to have a dipole moment. bond dipoles add together to produce a molecular dipole.
H F  Molecules such as carbon dioxide have polar bonds whose bond
 A molecule with a dipole moment
is a polar molecule. dipoles cancel each other as they are equal and opposite
 Carbon dioxide is a nonpolar molecule.
 The end result will be a molecule with
one center of positive charge and one Polar Covalent Bond
center of negative charge. •• ••
 The dipole moment effects the δ+ δ-
O :O = C = O :
attractive forces between molecules H–F
and therefore the physical properties H H
(Alternate Representations)
of the substance.
 Ch 12 & 13
• polar bonds, • polar bonds,
 Boiling points
H–F • symmetrical shape
• unsymmetrical shape
 Melting points
• molecule is polar • Dipoles equal & opposite
 Solubilities • molecule is nonpolar

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(Review from Ch 10) Adding Dipole Moments
Cl Cl (Review from Ch 10)

C C
Cl H
Cl H Cl
Cl

CCl4 CH2Cl 2
µ = 0.0 D µ = 2.0 D

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Hydrogen Bonds
Dipole-Dipole Interaction  Hydrogen bonds is a name given to a very strong dipole-dipole force.
 Do not confuse with a covalent bond.
 Interaction between opposite partial  There is an interaction between a
charges in molecules with a permanent
dipole moment. hydrogen covalently bonded to a strongly electronegative atom (Z
= O, N or F) and
 Must have polar molecules
(Remember Ch. 10) A nonbonding electron pair on another strongly electronegative
atom (O, N or F)
 Strength of interaction determined by the
size of the dipole.  As electrons are pulled away from H by an electronegative atom, what is
left is an unshielded proton that will strongly attract neighboring
electrons
 Hydrogen bonds between molecules are drawn using either a dotted line
The negative end of one or a more often a dashed line (see next slide)
molecule interacts with
the positive end of an
adjacent molecule.

Hydrogen bond
Covalent bond

Hydrogen Bonding Hydrogen Bonding and Boiling Point

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London Dispersion Forces
London Dispersion Forces • Weakest of forces.
• Between atoms/molecules that
have no permanent dipole.
 Weakest type of interaction. • One instantaneous dipole can
 Results from spontaneous, induce another instantaneous
instantaneous charge dipole in an adjacent molecule
separation. (or atom).
 All molecules exhibit this type • The forces between
of interaction. instantaneous dipoles are called
 Temporary.
London dispersion forces.
• Also known as Induced Dipoles
 Strength of interaction increases
• ALL molecules have them
with increasing number of
electrons. • Temporary
• Size depends on
• the number of electrons
• More e– = stronger force.
• shapes of molecules

Example: Which of the following chemicals would have the higher boiling point?
Strengths of Intermolecular Forces  Cl2 and I2

Example: Which of the following chemicals would have the higher boiling point? Example: Which of the following chemicals would have the higher boiling point?
 CH3 OCH 3 and CH 3 CH2OH  NaCl and CH 4

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The Liquid State The Liquid State

 At low enough temperatures, gases condense to form liquids.


 This occurs when intermolecular forces > kinetic energy for most  Viscosity – the resistance of a
of the molecules. liquid to flow.
 In liquid state:  Tied to strength of

 Molecules much closer together. intermolecular forces and


degree to which molecules
 Molecules remain mobile relative to one another and can flow.
can become entangled.
 Surface Tension – results from
the fact that surface molecules
experience intermolecular
forces only from one side.

Vapor Pressure The Liquid State


 Pressure exerted by a vapor in equilibrium with a liquid.
 Solids have vapor pressures as well!  The tendency of a liquid to become a gas is known as volatility.
 Increases with temperature. (Vapor Pressure)
 Larger intermolecular forces = Lower Vapor Pressure.  Related to temperature and the strength of intermolecular
 Liquid boils when its Vapor Pressure = Atmospheric Pressure. interactions.
 Normal boiling point.
 Evaporation – the conversion of a liquid to gas under ambient
 Raising external pressure raises boiling point, & visa versa.
conditions.
 Molecules lost from surface of liquid.

 Increases with temperature and surface area.

 Boiling – applying energy to a liquid until the vapor pressure in the


liquid = pressure of the atmosphere over it.
 Results in bubble formation.

Liquid just poured into Evaporation faster Evaporation as fast


open container, very than Condensation. as Condensation.
little vapor. (Equilibrium)

The Solid State

 If energy is further removed from a liquid, the The classes of crystalline solids.
molecules (or atoms) will be immobilized by
intermolecular interactions and a solid will form.

Crystalline Solids
 Crystalline
 Exhibits long-range order. Ionic Solids Molecular Solids Atomic Solids
 Pattern: crystal lattice.
Components Components Components
are ions. are molecules. are atoms.

Atomic Network Metallic

 Amorphous
 Very little order, but still hard and has a definite
shape.

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The Solid State: Crystalline Solids The Solid State

 The nature of a solid substance is determined by the forces holding


the material together:
 Ionic

 Assembled via electrostatic interactions between cations and


anions.
 Molecular

 Composed of molecules assembled through intermolecular


forces.
 Atomic

 Composed of discrete atoms.

The Solid State: Molecular Solids The Solid State: Atomic Solids

 Figure 13.17:  Atomic solids can be classified by connectivity between atoms:


A representation of  Covalent – have strong directional bonds between atoms. e.g.
part of the structure diamond
of solid phosphorus,  Nonbonding – assembled by dispersion forces alone. e.g. solid
a molecular solid that argon
contains P4
 Metallic solids – atoms held together by metallic bonding
molecules.

+ + +
+ + + + + +
e- e- e-
e- e- e- e- e-
+ + +
+ + + + + +
e- e- e- e- e- e- e- e-
+ + + + + + + + +

Metallic Bonding Metallic Solutions

 Metallic Bonding  Alloys are mixtures of elements that


 A strong, nondirectional interaction. show metallic properties.
 “positive ion in sea of electrons”  Substitutional alloys have some host
 Directly responsible for many of the properties of metals: metal atoms replaced by metal atoms
 Conductivity (Heat and Electricity) - due to mobility of
of similar size.
electrons.  Brass

 Malleable & Ductile - because metal ions can slide past each  Interstitial alloys have small atoms
other in crystal. occupying some of the holes in the
 Melting Points - relatively high due to strong attractions crystal lattice of the host metal.
between metal ions and electrons.  Steel

+ + +
+ + + + + +
e- e- e-
e- e- e- e- e-
+ + +
+ + + + + +
e- e- e- e- e- e- e- e-
+ + + + + + + + +

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Phase Changes
Phase Changes
Endothermic
(energy is absorbed by material)
A cooling curve for the conversion of gaseous water to ice.
Sublimination

Melting Vaporization

Solid Liquid Gas

Freezing Condensation

Deposition

Exothermic
(energy is released by the material)

Energy Requirements for State Changes Energy Requirements for State Changes

 In order to melt a solid:  In order to boil a liquid:


 energy required to overcome  energy required to overcome
some of the intermolecular the all of the intermolecular
attractions. attractions.
 the energy required to melt 1  Not break covalent bonds,
mole of a solid is called the just the intermolecular
heat of fusion. forces.
 The energy required to boil 1
mole of a liquid is called the
heat of vaporization. ΔHvaporization = 40.6 kJ/mol for liquid
ΔHfusion = 6.02 kJ/mol for ice at 0°C
water at 100°C

Using Heat of Vaporization in Calculations Using Heat of Fusion in Calculations


Calculate the amount of heat required to vaporize 84.8 g of water at its boiling point. Calculate the amount of heat emitted when 12.4 g of water freezes to solid ice.

Given: 84.8 g H2O Given: 12.4 g H2O


Find: heat (kJ) Find: heat (kJ)
Conversion Factors: Conversion Factors:
ΔHvap = 40.7 kJ/mol (at 100ºC) ΔHfus = 6.02 kJ/mol
1 mol H2O = 18.02 g H 2O 1 mol H2O = 18.02 g H 2O
Solution Map: Solution Map:

Solution:
Solution:

The heat emitted is 4.14 kJ.

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Tips on Calculations
 Note that the same substance will have a different value for specific heat Example 1
for each of its states/phases.
 How much energy is required to heat 4.2 grams of water from 12°C
 Specific heats are usually (but not always) in J/g (not moles).
to 100°C and convert it to steam at that temperature?
 Heats of fusion or vaporization are usually in kJ/mole.
 Make sure everything has the correct units.

 Calculations:
 Energy of melting/freezing = ΔHfusion x mol of substance

 Energy of vaporization/condensation = ΔHvap x mol of substance Water @ 12 oC Water @ 100 oC Steam @ 100 oC
 Energy of temp change of solid = m x specific heat solid x ΔT

 Energy of temp change of liquid = m x specific heat liquid x ΔT

 Energy of temp change of gas = m x specific heat gas x ΔT Q = m × c × ÄT 1 mol water


4.2 g × = 0.2331 mol water
J 18.02g
Q = 4.2 g × 4.184 × (100 oC − 12oC)
goC 40.6kJ
0.2331 mol water × = 9.5kJ
Q = 1546J = 1.5kJ 1 mol water

Total Energy = 9.5 kJ + 1.5 kJ = 11.0 kJ

Example 2
 What is the final temperature when 50 g of ice is added to 12 fl oz
of 25 oC liquid water? {There are 128 fl oz in 1 gallon and 3785 mL
in 1 gallon. Assume the density of water is constant at 1.00 g/mL
and that the specific heat of water is 4.184 J/(goC).}