Chapter 11

Download as ppt, pdf, or txt
Download as ppt, pdf, or txt
You are on page 1of 84

1

Chapter Eleven

States of Matter and Intermolecular Forces


2
Chapter Preview

• This chapter:
– describes changes from one state of matter to another.
– explores the types of intermolecular forces that underlie these
and other physical properties of substances.

• Intramolecular forces (chemical bonds) govern


molecular properties such as molecular geometries
and dipole moments.

• Intermolecular forces determine the macroscopic


physical properties of liquids and solids.
3

Molecular Forces in H2O Compared

Intermolecular forces
determine the
macroscopic physical
properties of liquids and
solids

Intramolecular forces
determine such
molecular properties as
molecular geometries
and dipole moments
4

States of Matter Compared

Intermolecular forces Intermolecular


are of little Intermolecular forces are very
significance; why? forces must be important.
considered.
5

Intermolecular Forces

Gases – fill container, random rapid motion, never


coming to rest or clumping together. Motion is mainly
translational

Liquids – fixed volume, flow and assume shape of


container, only slightly compressible, stronger forces
hold molecules together. Motion is mainly translational

Solids – fixed volume, definite shape, generally less


compressible than liquids, forces hold particles in a fixed
shape. Motion is mainly vibrational
6
Vaporization and Condensation

• Vaporization is the conversion of a liquid to a gas.

• The enthalpy of vaporization (Hvapn) is the


quantity of heat that must be absorbed to vaporize
a given amount of liquid at a constant temperature.

• Condensation is the reverse of vaporization. The


enthalpy of condensation (Hcondn) accompanies
this change of a gas to a liquid.
sublimation
Solid Gas
deposition
7

• Enthalpy is a function of state: therefore, if a


liquid is vaporized and the vapor condensed
at constant temperature, the total H must be
zero:
Hvapn + Hcondn = 0
Hcondn = –Hvapn

H2O(l)  H2O(g) = +44 kJ mol–1

H2O(g)  H2O(l) = –44 kJ mol–1


8
Enthalpies of Vaporization

Because enthalpy is a function of state, the total enthalpy


change between vaporization and condensation at constant
temperature must be zero

“at room temperature 298 K (25 oC)”


9

Vapor Pressure

The vapor pressure of a liquid is the partial pressure


exerted by the vapor
when it is in dynamic equilibrium with a liquid
at a constant temperature.

vaporization
Liquid Vapor
condensation
10
Liquid–Vapor Equilibrium

More vapor forms; rate … until equilibrium


of condensation of that is attained.
vapor increases …
11
As T , vapor pressure of liquid
Vapor pressure also depends on what the liquid is!

1 atm = 760 mmHg = 760 torr


12
Cooling Curve for Water

Once all of the


The liquid water (1) = liquid liquid has
cools until … solidified, the
(s) = solid temperature again
drops.

… the freezing
point is reached,
at which time the
temperature
remains constant If the liquid is
as solid forms. cooled carefully, it
can supercool.
13
Heating Curve for Water

… until the solid begins


to melt, at which time
the temperature
remains constant …

The
temperature of
the solid
increases as it
is heated …

… until all the solid is


melted, at which time
the temperature
again rises.
14

Some Enthalpies of Fusion


15
Phase Changes Involving Solids
The conversion of a solid to a liquid is called melting, or
fusion, and the temperature at which a solid melts is its
melting point
Sublimation is the process of a
molecule’s passing directly from the
solid to the vapor state

Hsubln = Hfusion + Hvap

Deposition is the condensation of


a vapor to a solid
16
Example 11.3
Suppose the equilibrium illustrated in Figure 11.3 is between liquid hexane,
C6H14, and its vapor at 298.15 K. A sample of the equilibrium vapor is
found to have a density of 0.701 g/L. What is the vapor pressure of
hexane, in mmHg, at 298.15 K?
17
CS2

CH3OH Vapor Pressure


H2O
Curves

Normal boiling point


What is the vapor pressure of
CH3CH2OH H2O at 100 °C, according to
this graph? What is the
significance of that numeric
value of vapor pressure?

Which of the five


compounds has the
strongest intermolecular
1 atm = 760 mmHg = 760 torr C6H5NH2
forces? C6H5NH2
18

Water boils at 95 oC in Denver located at 1609 m (650 mmHg)


Take longer time to boil an egg!

In a pressure cooker,
water boils at higher than normal temperature

The chemical reactions involved in cooking


proceed faster than in an open pot

Hydrothermal synthesis
in an autoclave
19
Boiling Point and Critical Point

• Boiling point: the temperature at which the vapor


pressure of the liquid equals the external pressure.

• Normal boiling point: boiling point at 1 atm.

• Critical temperature (Tc): the highest temperature at


which a liquid can exist.

• The critical pressure, Pc, is the vapor pressure at


the critical temperature.

• The condition corresponding to a temperature of Tc


and a pressure of Pc is called the critical point.
20

Critical Point
The critical temperature, Tc, is the highest temperature
at which a liquid and vapor can coexist in equilibrium as
physically distinct states of matter

The critical pressure, Pc, is the vapor pressure at the


critical temperature

The condition corresponding to


a temperature of Tc and a
pressure of Pc is called the
critical point
21
The Critical Point

At room temperature there is At higher temperature, there At Tc, the densities


relatively little vapor, and its is more vapor, and its of liquid and vapor
density is low. density increases … are equal; a single
phase.

… while the density of the Supercritical water is


liquid decreases; molecular non-polar!
motion increases.
22

These four gases can’t be liquefied


at room temperature, no matter
what pressure is applied

Substances existing beyond the critical point are termed


supercritical fluids
23
Phase Changes Involving Solids

• Melting (fusion): transition of solid  liquid.


• Melting point: temperature at which melting occurs.
• Enthalpy of fusion, Hfusion, is the quantity of heat
required to melt a set amount (one gram, one mole) of
solid.
• Sublimation: transition of solid  vapor.
• Enthalpy of sublimation, Hsubln, is the sum of the
enthalpies of fusion and vaporization (Hfusion + Hvap).
• Triple point: all three phases - solid, liquid, vapor - are
in equilibrium.
24
Phase Diagrams

A-D, solid-liquid A-C, liquid-vapor


equilibrium. Fusion equilibrium. Vapor
A phase diagram is a curve pressure curve
graphical representation of
the conditions of
temperature and pressure
under which a substance critical point
exists as a solid, liquid, a
gas, or some combination
of these in equilibrium.

A-B, solid-vapor
equilibrium. Triple point Supercritical fluid
Sublimation curve Liquid and gas
become
indistinguishable!
25
Phase Diagram for HgI2

HgI2 has two


solid phases,
red and yellow.

Boiling point

As the vessel is allowed to cool,


will the contents appear more Polymorphism
red or more yellow? A solid exists in two or more forms!
26
Phase Diagram for CO2

dry ice

No melting!
Note that at 1 atm,
only the solid and
vapor phases of
CO2 exist.
27
Phase Diagram for H2O

Tc = 374 oC, Pc = 218 atm


28

Intermolecular Forces

• … are forces between molecules.


• They determine melting points, freezing
points, and other physical properties.
• Types of intermolecular forces include:
• dispersion forces
• dipole–dipole forces
• hydrogen bonding
29
Dispersion Forces

Dispersion forces are forces of attraction between an


instantaneous dipole and an induced dipole… also
called London forces after Fritz London who offered a
theoretical explanation in 1928

The polarizability of an atom or


molecule is a measure of the
ease with which electron charge
density is distorted by an
external electrical field

Dipoles can be induced


even in molecules
30

Dispersion Forces Illustrated (1)

At a given instant, electron


density, even in a nonpolar
molecule like helium, is not
perfectly uniform.
31
Dispersion Forces Illustrated (2)

… the other end of


The region of the molecule is
(momentary) higher slightly (+)...
electron density attains a
small (–) charge …

When another
nonpolar molecule
approaches …
32

Dispersion Forces Illustrated (3)

… this molecule
… in this
induces a tiny dipole
molecule.
moment …

The attraction between any two dipoles


constitutes an intermolecular force.
33
Strength of Dispersion Forces
• Dispersion force strength depends on polarizability:
the ease with which the electron cloud is distorted by
an external electrical field.
• The greater the polarizability of molecules, the
stronger the dispersion forces between them.
• Polarizability in turn depends on molecular size and
shape.
• Heavier molecule => more electrons => more-
polarizable molecule => stronger intermolecular force
• F2 (b.p. -188 oC, gas) < Cl2 (b.p. -34 oC, gas) < Br2
(b.p. 59 oC, liquid) < I2 (m.p. 184 oC, solid)
34
Molecular Shape and Polarizability

Long skinny … can have greater separation of


molecule … charge along its length. Stronger
forces of attraction, meaning …
… higher
boiling point.

… giving weaker
dispersion forces and In the compact isomer, less
a lower boiling point. possible separation of charge …
35

Dipole–Dipole Forces

• A polar molecule has a positively charged “end”


(δ+) and a negatively charged “end” (δ–).

• When molecules come close to one another,


repulsions occur between like-charged regions
of dipoles. Opposite charges tend to attract one
another.

• The more polar a molecule, the more


pronounced is the effect of dipole–dipole forces
on physical properties.
36

Dipole–Dipole Interactions

Dipole–dipole forces arise when permanent dipoles


align themselves with the positive end of one dipole
directed toward the negative ends of neighboring
dipoles

A permanent dipole in
one molecule can
induce a dipole in a
neighboring molecule, Opposites attract!
giving rise to a dipole–
induced dipole force
37
Predicting Physical Properties of
Molecular Substances

Dispersion forces (always present!) become stronger


with increasing molar mass and elongation of
molecules

In comparing nonpolar substances, molar mass and


molecular shape are the essential influencing factors

Dipole–dipole and dipole–induced dipole forces are


found in polar substances. The more polar the
substance (dipole moment), the greater the
intermolecular force is expected to be
38
Example 11.6
Arrange the following substances in the expected order of
increasing boiling point: carbon tetrabromide, CBr 4; butane,
CH3CH2CH2CH3; fluorine, F2; acetaldehyde, CH3CHO.

The first three substances are nonpolar: F2 because the atoms in the molecules are
identical, CBr4 because of the symmetrical tetrahedral molecular structure, and
butane because the electronegativities of the C and H atoms are so nearly alike. We
expect the boiling points of the three to increase with increasing molar mass:
F2(38.00 g/mol) < CH3CH2CH2CH3(58.12 g/mol) < CBr4(331.6 g/mol)
As we noted on page 452, the carbon-to-oxygen bond dipole in acetaldehyde is
not offset by any other bond dipoles. Even though the molar mass of acetaldehyde
(44.05 g/mol) is somewhat smaller than that of butane, we expect acetaldehyde to
have the higher boiling point because this molecule is quite polar (µ = 2.69 D).
Comparing acetaldehyde and CBr4 is more difficult. The polar character of
acetaldehyde suggests that it should have the higher boiling point. Because the
molar mass of CBr4 is so very much greater than that of acetaldehyde, though, we
should expect CBr4 to have the higher boiling point. We predict the following order
of increasing boiling points:
F2 < CH3CH2CH2CH3 < CH3CHO < CBr4
39

Homology

• A series of compounds whose formulas and


structures vary in a regular manner also have
properties that vary in a predictable manner.
• This principle is called homology.
• Trends result from the regular increase in molar
mass, which produces a fairly regular increase in the
strength of dispersion forces.
• Example: both densities and boiling points of the
straight-chain alkanes increase in a continuous and
regular fashion with increasing numbers of carbon
atoms in the chain.
40
Example 11.7 An Estimation Example
The boiling points of the straight-chain alkanes pentane, hexane, heptane,
and octane are 36.1, 68.7, 98.4, and 125.7 °C, respectively. Estimate the
boiling point of the straight-chain alkane decane.

We need to figure out the pattern of increasing boiling point with increasing
length of the carbon chain. The data are for carbon-chain lengths of five, six,
seven, and eight C atoms. We want to estimate the boiling point of the 10-carbon
alkane, decane.

Note the trend in boiling-point increase per added CH 2 unit: 32.6, 29.7, 27.3.
This trend suggests that the boiling point of C9H20 is about 25 °C above that of
C8H18, and that the boiling point of C10H22 is about 23 °C greater than that of C9H20.
We therefore estimate the boiling point of decane to be 174 °C. (The observed
boiling point is 174.1 °C.)
41
Intermolecular Force: Hydrogen Bond

A hydrogen bond is an intermolecular force in which:


– a hydrogen atom that is covalently bonded to a (small,
electronegative) nonmetal atom in one molecule …
– is simultaneously attracted to a (small, electronegative)
nonmetal atom of a neighboring molecule.

+ -
Y ––– H - - - Z ~~~~

this force is called a hydrogen bond; a special,


strong type of dipole–dipole force

The strongest hydrogen bonds are formed


if the nonmetal atoms are small and highly electronegative (N, O, F)
42
Hydrogen Bonds in Water

Bond length: 100 pm (intra) versus 180 pm (inter)

+
No Chemical bonding! -

+

-
+
+

High b.p. of water despite of low molecular weight!


43
Hydrogen Bonding in Ice

Hydrogen bonding arranges the “Hexagonal” is reflected in the crystal


water molecules into an open structure. “Open” means reduced
hexagonal pattern density of the solid (vs. liquid)

“Water (liquid) is more dense than ice (solid)”


44

Hydrogen Bonding in Acetic Acid

Many organic acids can form dimers due to hydrogen bonding

Hydrogen bonding occurs


between molecules.
45

Hydrogen Bonding in Salicylic Acid

Certain organic molecules can also form an intramolecular hydrogen bond

Aspirin

Hydrogen bonding occurs


within the molecule.
46

Intermolecular Hydrogen Bonds

Intermolecular hydrogen bonds give proteins


their secondary shape, forcing the protein molecules into
particular orientations, like a folded sheet …
47
Intramolecular Hydrogen Bonds

… while intramolecular
hydrogen bonds can
cause proteins to take a
helical shape.

The folding of a protein


is directly related to its
biological function!
48
Four Types of Interactions
Determining the Protein Structure
49
Example 11.8
In which of these substances is hydrogen bonding an important
intermolecular force: N2, HI, HF, CH3CHO, and CH3OH? Explain.

N2: Nitrogen atoms are small and highly electronegative, but we cannot have hydrogen
bonds without hydrogen atoms. Hydrogen bonding does not occur.

HI: Hydrogen atoms are present, but iodine atoms are large and only moderately
electronegative. Hydrogen bonding does not occur.

HF: Hydrogen atoms are bonded to small, highly electronegative nonmetal atoms (fluorine).
Hydrogen bonding is a significant intermolecular force.

CH3CHO: Both hydrogen atoms and highly electronegative nonmetal atoms (oxygen)
are present, but as we see from the structural formula, the hydrogen atoms are bonded
to carbon, not oxygen: Hydrogen bonding is not a significant intermolecular force.

CH3OH: Again, both hydrogen atoms and a small, highly electronegative nonmetal
oxygen atom are present, and one of the hydrogen atoms is bonded to the oxygen atom:
Hydrogen bonding is a significant intermolecular force.
50

Liquids and Intermolecular Forces

• Much behavior and many properties of liquids (density,


m.p., b.p., enthalpies of vaporization) can be attributed
to intermolecular forces.
• Adhesive forces are intermolecular forces between
unlike molecules.
• Cohesive forces are intermolecular forces between
like molecules.
• Surface tension () is the amount of work required to
extend a liquid surface and is usually expressed in J/m2.
• Viscosity is a measure of a liquid’s resistance to flow.
51

Surface Tension

Molecules within the liquid experience a greater net intermolecular force


than do surface molecules. To create more surface, the molecules at the
surface must be separated from one another.
52

Adhesive and Cohesive Forces

The liquid spreads,


because adhesive forces The liquid “beads up.” Which
are comparable in strength forces are stronger, adhesive
to cohesive forces. or cohesive?
53

Meniscus Formation

A meniscus is the interface between a liquid and the air above it

What conclusion
can we draw
about the
Water wets the
cohesive forces
glass (adhesive
in mercury?
forces) and its
attraction for
glass forms a
concave-up
surface.
54
Capillary Action

The adhesive forces


wet more and more
of the inside of the
tiny tube, drawing
water farther up the
tube.

Capillary action results from intermolecular interactions


55

Comparing Viscosity
Viscosity is a measure of a liquid’s resistance to flow

Liquids which flow easily


are said to be mobile

Viscosity units are poise (P)

The stronger intermolecular


force (hydrogen bonding), the
greater viscosity
CH3CH2CH2OH (0.02 P)
CH2COHCHOHCH2OH (10 P)
56

Types of Solids

• Amorphous solids have no significant long-range order.


No X-ray diffraction! (Ex. glass, amorphous silicon)

• Crystalline solids have atoms/ions/molecules arranged


in a regular pattern. Types of crystalline solids include:
– Molecular solids, containing molecules held to one
another by dispersion/dipole–dipole/ hydrogen
bonding forces. (C60)
– Network (covalent) solids. (Diamond)
– Ionic solids. (NaCl)
– Metallic solids. (Cu, Au).
57
58
Network Covalent Solids

• Network solids have a network of covalent bonds that


extend throughout the solid, holding it firmly together.
• The allotropes of carbon provide good examples.
– Diamond has each carbon bonded to four other
carbons in a tetrahedral arrangement using sp3
hybridization.
– Graphite has each carbon bonded to three other
carbons in the same plane using sp2 hybridization.
– Fullerenes are roughly spherical collections of
carbon atoms in the shape of a soccer ball.
– A nanotube can be thought of as a plane of graphite
rolled into a tube.
59
Crystal Structure of Diamond

Three-dimensional
network is extremely What kind of forces
strong, rigid. must be overcome to
melt diamond?

Covalent bond!

intramolecular forces (bonds) >>> intermplecular forces


60
Crystal Structure of Graphite

Hexagons of
sp2-hybridized
carbon atoms.
Covalent bond!

Forces between
layers are
relatively weak.
van der Waals
forces!

Good conductor due to delocalized p electrons!


61
Structure of a Buckyball (Soccer ball)

C60 molecule

Non-polar: solid C60


The Nobel Prize in Chemistry 1996
"for their discovery of fullerenes“
Curl, Kroto, Smalley
fcc close packing

K3C60: Superconductor
62

Structure of a Nanotube

A nanotube can be
thought of as a sheet of
graphite, rolled into a
tube, capped with half of
a buckyball.
63
Ionic Bonds

• There are no molecules in an ionic solid, and therefore


there can’t be any intermolecular forces.
• The attractions are electrostatic inter-ionic attractions.
• Lattice energy (Chapter 9) is a measure of the strength
of inter-ionic attraction.
• The attractive force between a pair of oppositely charged
ions increases:
– as the charges on the ions increase.
– as the ionic radii decrease.
• Lattice energies (strength of inter-ionic attractions)
increase accordingly.
64

Inter-ionic Forces of Attraction

higher charge & smaller ionic distance

Mg2+ and O2– have much stronger forces of


Melting point of NaCl is
attraction for one another than do Na+ and Cl–.
about 801 oC.
Melting point of MgO is about 2800 oC.
65
Example 11.9
Arrange the ionic solids MgO, NaBr, and NaCl in the expected order of
increasing melting point.

Mg2+ and O2– ions have higher charges than do Na+, Cl–, and Br–. Also, Mg2+
+ 2– – –
is a smaller ion than Na , and O is smaller than both Cl and Br . As a
result, we expect the lattice energy of MgO to be much greater than that of
either NaCl or NaBr. Because it has the highest lattice energy, MgO should
have the highest melting point of the three compounds.
Now we need to determine whether NaCl or NaBr has the greater lattice
energy. We see that the compounds have the same cation and that their
anions have the same charge. The only difference is in the anion radii. The
– –
Cl ion is smaller than the Br ion, and therefore the interionic attractions in
NaCl are stronger than in NaBr. We expect NaCl to have a higher lattice
energy and a higher melting point than NaBr. The expected order is therefore
NaBr < NaCl < MgO.

Observed melting points of 747 °C for NaBr, 801 °C for NaCl, and 2832 °C for MgO!
66
Crystal Lattices

• To describe crystals, three-dimensional views


must be used.
• The repeating unit of the lattice is called the
unit cell.
• There are a number of different types of unit
cell; hexagonal, rhombic, cubic, etc.
• The three types of cubic unit cells are: simple
cubic, body-centered cubic (bcc), face-
centered cubic (fcc).
67
Crystal Lattices
Crystals have repeating units …

… in multidimensional space

The repeating unit of the lattice is called the unit cell,


describing the entire structure
68

Perovskite SrTiO3 structure

Unit cell of SrTiO3


69
Unit Cells in Cubic Crystal Structures

The simple cubic cell is the simplest


unit cell and has structural particles
centered only at its corners

The body-centered cubic (bcc)


structure has an additional structural
particle at the center of the cube

The face-centered cubic (fcc)


structure has an additional structural
particle at the center of each face
70

Unit Cells – Coordination Number

The coordination number is the number of nearest neighbor


atoms to a single atom in the crystal

In a simple cubic
structure, the
coordination
number is 6
71
Packing in Crystals

“Open” packing has larger voids in between particles


compared to close-packed crystals having maximum
coordination number

A close packed structure in two


dimensions.
72

Close-Packed Structures
Tetrahedral holes
located above a sphere in the bottom layer
Octahedral holes
located above a void in the bottom layer
73

Tetrahedral T+ Tetrahedral T- Octahedral O


74
Close Packing in Three Dimensions
Third layer directly
above first layer: HCP

Two layers, stacked,


give two different
locations for the
third layer …
Third layer over the octahedral
holes in the second layer: CCP
75
Example 11.10
Copper crystallizes in the cubic close-packed arrangement. The atomic
(metallic) radius of a Cu atom is 127.8 pm. (a) What is the length, in picometers,
of the unit cell in a sample of copper metal? (b) What is the volume of that unit
cell, in cubic centimeters? (c) How many atoms belong to the unit cell?

Each corner atom belongs only in 1/8 part to a given unit cell:
1/8 x 8 = 1 atom.
A cube has six faces: 1/2 x 6 = 3 atoms.
The total number of atoms in the unit cell is thus 1 + 3 = 4.
76
Example 11.11
Use the results of Example 11.10, the molar mass of copper, and
Avogadro’s number to calculate the density of metallic copper.

The mass of a copper atom is the molar mass, 63.546 g/mol Cu, divided by
Avogadro’s number. The unit cell contains the equivalent of four copper atoms.

Theoretical density
77
Ionic Crystal Structures

• Ionic crystals have two different types of structural


units - cations and anions.
• The cations and anions ordinarily are different sizes.
• Generally, smaller cations can fill the voids between
the larger anions.
• Where the cations go depends on the size of the
cations and on the size of the voids.
• The smallest voids are the tetrahedral holes, then the
octahedral holes, and finally the holes in a cubic
structure.
78

Ionic Crystal Structures

Smaller cations can fill the voids between the larger anions

Tetrahedral hole filling occurs when the radii


ratio is:
0.225 < rc/ra < 0.414

Octahedral hole filling occurs when the


radii ratio is:
0.414 < rc/ra < 0.732

The arrangement is cubic if rc/ra > 0.732


79

4 tetrahedral T+ sites are


occupied by Zn2+

Zn2+/S2- ~ 74 pm/170 pm = 0.43


80

Unit Cell of Cesium Chloride

Radius ratio = Cs+/Cl– = 169 pm/181 pm = 0.934

How many cesium ions are inside this unit


cell? How many chloride ions? 1:1
81
Unit Cell of Sodium Chloride

Radius ratio = Na+/Cl– = 99 pm/181 pm = 0.55

Octahedral holes

How many Na ions are inside this unit cell? How many Cl ions? 4 : 4

The unit cell contains the equivalent of


four formula units of NaCl!
82
Experimental Determination of Crystal Structures

X rays

Angle of diffraction can be


used to find distance d,
using simple trigonometry.

Bragg equation: n = 2d sin


83

Summary of Concepts

• Vaporization is the passage of molecules from the


liquid to the gaseous state
• A phase diagram is a plot showing the phases of a
substance at various temperatures and pressures
• Fluctuations in electrical charge produce an
instantaneous dipole, which induces a dipole in
neighboring atoms and are called dispersion forces
• A strong intermolecular force called the hydrogen
bond is formed when a hydrogen atom is attracted to
a N, O, or F atom on a neighboring molecule
84

Summary of Concepts

• The intermolecular forces in a liquid determine its


viscosity, or resistance to flow
• In some solids, covalent bonds extend throughout a
crystal
• In ionic solids, inter-ionic attractions bind all the ions
together in a crystal
• The structure of a crystal is described by a three-
dimensional pattern called a lattice
• Unit cell properties and dimensions can be used to
find atomic radii and the densities of crystalline
substances

You might also like