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Liquids and Solids

Chapter 11

Liquids and Solids

~12bar,assuming
gasisAr,T=298K

Gases vs. Liquids &


Solids

Textbook Chapters to
Cover
11.2 Solids, Liquids, and Gases: a Molecular

Comparison
11.3, 11.4 Intermolecular Forces
11.5, 11.6 Vaporization, Vapour Pressure,
Sublimation and Fusion
11.7 Heating Curve for Water
11.8 Phase Diagrams
11.9 Water: An Extraordinary Substance
11.11, 11.12 Crystalline Solids
4

Excluded Textbook
Chapters
11.1 Climbing Geckos and Intermolecular

Forces
11.10 Crystalline Solids: Determining Their
Structure by X-Ray Crystallography
11.13 Crystalline Solids: Band Theory

Outline
Intermolecular Forces
Properties of Liquids
Phase Changes
Heating Curves
Phase Diagrams
Crystalline Solids

Intermolecular
Forces
Forces of attraction & repulsion
Operative in molecular solids, liquids, and gases
(as opposed to metallic, covalent, & ionic solids)

Forces of attraction &


repulsion
Forces in non-molecular solids: metallic (e.g.

Cu), covalent (e.g. diamond), and ionic (e.g.


NaCl) bonds
These forces are 10 times stronger than van der

Waals forces => high mp & bp.

Forces in molecular species: intermolecular

(aka van der Waals) forces; e.g. H2O, sugar,


wax
dispersion forces (aka London forces)
dipole-dipole forces
hydrogen bonding

Dispersion Forces
Also called London Forces
Operate in all molecules
Due to electron cloud (e.c.)
Collision distorts e.c. instantaneous

dipole
Inst. dipole induces same on nearby
molecule

Effect of Molecular Size


Polarisability
How easily is electron cloud distorted?
More electrons = more polarisable

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Effect of Shape
Exposed surface increases interaction

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Dipole-Dipole
Interactions
Between molecules with permanent dipole
Dipole results from
Unequal electron sharing (different
electronegativities)
Asymmetry of molecule
Relatively strong intermolecular force
Strength depends on dipole moment

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Example: H-Cl
Cl is very electronegative; H is less so
Cl pulls electrons towards its end (negative)
H left with partial positive charge
H end of one HCl attracted to Cl end of

another

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Dipole-Dipole Interactions

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Dipole Moment &


Symmetry
1,2-Dichlorobenzene

Dipolemoment
2.50 debye (D)
Boilingpoint
1,2-DCB: 180.5C

1,4Dichlorobenzene

Dipolemoment
0.00 D (symmetry)
Boilingpoint No net dipole
174C
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Dipole Moment & bp

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LC: Boiling Points


Which list of compounds is in order
of decreasing boiling point?
A. I2, Cl2, Br2
B. C6H6, C6H6Cl, C6H6Cl2
C. As(CH3)3, P(CH3)3, N(CH3)3
D. CH4, C2H6, C3H8

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LC: Boiling Points


Which list of compounds is in order
of decreasing boiling point?
C. As(CH3)3, P(CH3)3, N(CH3)3

London forces operative


Compound with most electrons will have
highest b.p.
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Hydrogen Bonding
Molecules with H bound

to N, O, or F.
H atom is electropositive.
Super dipole-dipole

force, unusually strong.


Not to be confused with a
chemical bond (i.e. a
covalent bond).

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Hydrogen Bonding

Covalent
bond

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Hydrogen Bonding

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LC: Choose the liquid at


RT
One of these compounds is a
liquid at RT and the other two are
gases. Which one is a liquid? Why?
A.H2C=O
B.CH3F
C.H2O2

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LC: Choose the liquid at


RT
One of these compounds is a
liquid at RT and the other two are
gases. Which one is a liquid? Why?
C.H2O2

All three have 16-18 e, i.e. similar dispersion


forces. All three have dipole moments. Only
H2O2 has H directly bonded to an
electronegative atom (O), i.e. hydrogen
bonding. H2O2 has the highest bp.
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Ion-Dipole Forces
Operate in ionic solution. (More to come in Ch

12.)

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Example
Which forces are operative in the following
substances? How do you expect their b.p.s to
compare?
Compound H-bonding,
Forces: London Forces
100
b.p./C
-6.3
H-bonding, London Forces
H2O
Ionic Bonding
1413
CH3NH2
London Forces
149
NaCl
London Forces, dipole-dipole -85
CH3(CH2)14CH3London Forces
-183
HCl
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Properties of
Liquids

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Properties of Liquids
Self-study: viscosity, surface tension, capillary

action (11.4)
Vapour Pressure

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Vapour Pressure
Vapour pressure is the equilibrium partial
pressure of the vapour in the space above a
liquid

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V.P. increases with temp

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V.P. increases with temp

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V.P. increases with temp


A liquid will boil when its vapour pressure

is equal to atmospheric pressure.


The normal bp of a liquid is the
temperature at which its vapour pressure is
1.01325 bar (1 atm).
Liquids with high vapour pressure at room
temperature have low boiling points.

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LC: Boiling Water


A pot of water is placed on a stove. Before it
boils, bubbles form at the bottom of the pot and
rise to the top. What are the bubbles made of?
(A)Heat
(B)Air
(C)Oxygen gas and hydrogen gas
(D)Water vapour

V.P. increases with


temp
V.P. curve can be

bp at 2500 m

used to find boiling


point at pressures
other than 1.01325
bar (1 atm =Atmos.
760
press. at
Torr).
2500 m
(532 torr)

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LC: Vapour Pressure


The vapour pressure of acetylene, C2H2,
stored in a pressurized cylinder is about
0.025 bar at 150 K and 2.0 bar at 200 K.
What is the most likely value for the
vapour pressure at 175 K?
A. 0.02 bar
B. 0.35 bar
C. 1.0 bar
D. 1.5 bar
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LC: Vapour Pressure


B. 0.35 bar

Vap press (bar)

Remember shape of curve.


2.00

1.00

0.025
150

175
Temp (K)

200
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Clausius-Clapeyron
Equation
P2 H vap 1 1
ln

P1
R T1 T2
Equation for the vapour pressure curve
(T1,P1) and (T2,P2) are two vapour pressure

data
Hvap is the enthalpy of vapourisation
R is the gas constant: 8.3145 J/K/mol
Notes:

T is always in K
Hvap is in J/mol, so that units cancel with R
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Uses for ClausiusClapeyron


Predict V.P. at T2, given:
Enthalpy of vapourisation (Hvap)
V.P. (P1) at temperature T1

Predict boiling point (T2) at pressure P2, given:


Hvap
Normal bp (T1, P1)

Obtain Hvap given two T,P data


e.g. normal boiling point and one other

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Example
What is the V.P. of water (in torr) at 50C if it is
18 torr at 25 C (Hvap= 44 kJ/mol)?
Ans: first, rearrange C-C equation for P 2

Hvap 1 1
P2 P1 exp

R T1 T2

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Examplecont
Next, convert temperatures to K & Hvap to

J/mol:
T1 = 298 K
T2 = 323 K
H = 44 000 J/mol
P1 = 18 torr

Then plug in the values and calculate


P2 = 71 torr
Note: T increased by 8%, but P increased

by 290%!
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LC: Clausius-Clapeyron
What is the bp of water at the Mexico City
airport (altitude 2230 m; atmospheric pressure
= 588 torr)?
Hvap= 40.68 kJ/mol; R=8.3145 J K-1 mol-1; 1
atm=760 torr
A.
B.
C.
D.

288.7
366.0
293.6
380.6

K
K
K
K
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LC: Clausius-Clapeyron
B. 366.0 K (only reasonable answer)
Rearrange C-C equation for 1/T1
1
R
P2 1

ln
T1 H vap P1 T2
Recall that T2,P2 is normal bp

1 8.3145 760
1

ln

T1 40680 588 373.15


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Phase Changes
& Phase Diagrams

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Phase Changes

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Enthalpies of Transition

Hvap

Hvap
Hsub

Hfus

Hsub

Hfus

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46

Heating Curves
q=mCs,steamT
q=nvapH
q=nfusH

q=mCs,liqT

q=mCs,iceT

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Phase Diagrams

Linesegments(AC,AD,AB)
representcertainT&Pat
whichthesubstanceisin
equilibriumbetweentwo
states.
Triplepoint(A)representsthe
uniqueTandPatwhichsolid,
liquid,andgaseousstatesarein
equilibrium.
Criticalpoint(B)represents
theT&Pabovewhicha
supercriticalfluidexists.
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Phase Diagrams
1atm
Liquidwill
notform
beyondthis
temperature
(crit.temp.)
mp

bp

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Critical Temperature and Pressure


Critical temperature:
above this temperature, liquid state will not
form
Critical pressure:
pressure required to liquefy gas at critical
temperature
Above critical T & P, fluid is supercritical

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Supercritical Benzene

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H2O and CO2


NegativeSlope(atypical)

PositiveSlope(typical)

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Solids: Properties
and Bonding

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Order in Solids
Two types
Crystalline: atoms in
ordered matrix
e.g. quartz
solids have facets, cleave along well defined

planes

Amorphous: short-range order


solids melt over range of temperatures
properties depend on preparation
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Molecular Solids
van der Waals interactions
e.g. Ar(s), H2O(s), C6H12O6(s)
low bp & mp
electrical insulators
soluble in solvents of similar polarity

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Molecular Solids
Benzene:
mp=5C
bp=80C

CH3

Toluene:
mp=95C
bp=111C

Boiling point depends on


number of electrons, as expected

Melting point depends on


strength of intermolecular forces
efficiency of packing (molecular shape)
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Ionic Solids
e.g. NaCl (s), CsCl (s), ZnS (s), CaF 2 (s)
Bonding: electrostatic attraction between ions

Hard, brittle
High mp & bp
bp & mp depend on surface charge density of
ions
mp of MgO = 2852C; mp of NaCl = 801C
Electrical and thermal insulators
Some are soluble in polar solvents
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Metallic Solids
e.g. Fe(s), Na(s)
Bonding: Metal ions in a sea of valence

electrons
Soft, ductile, malleable
Variable mp & bp
Mo mp 2623 C; Na mp 98 C; Hg mp -39 C

Many are soluble in (react with) acids


Electrical and thermal conductors

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Network Covalent Solids


e.g. C(diamond), C(graphite), SiC(s)
Covalent bonding: atoms share electrons
Very hard & brittle
Very high bp & mp
Insulators or semiconductors
C(graphite) is conductor

Insoluble in solvents

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Network Covalent Solids

Covalentbonds
VanderWaals
Forces

61

LC: melting points


Which solid has the lowest melting point and
why?
A. NaCl(s)
B. C(s, diamond)
C. C31H64(s)

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LC: melting points


Which solid has the lowest melting point and
why?
A. NaCl(s)
B. C(s, diamond)
C. C31H64(s)

C31H64 is a molecular solid held together by van


der Waals (intermolecular) forces.
NaCl/diamond is held together by
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ionic/covalent bonds, respectively, ten times

Crystal Structure
in Solids

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Crystal Structure
Two parts to a crystal
Lattice
Repeating 3-D pattern of points in space
Theoretical

Basis
Chemical unit (atom, molecule, etc.)
One basis unit at each lattice point

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Crystal Lattice and Unit


Cell
Lattice comprised of repeating units called

unit cells

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Cubic Unit Cells

e.g. polonium
Po(s)

e.g. alpha iron


-Fe(s)

e.g. platinum
Pt(s)
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Number of atoms per unit


cell
Simple Cubic

81/8=1atom

Body Centred Cubic

Face Centred Cubic

81/8+1=2atoms

81/8+61/2
=4atoms
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LC: Find the Formula


From the unit cell, below, what is the formula of
the oxide of niobium?

A.
B.
C.
D.

NbO
NbO2
Nb2O3
Nb2O

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Find the Formula


A. NbO

12Oatomsshown
Each has inside
cell
Therefore, 3 O atoms
6Nbatomsshown
Each has inside
cell
Therefore, 3 Nb
atoms
Formula:Nb3O3
Smallest ratio: NbO
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Space utilisation in cubic


cells
Simple Cubic
(1 atom)

Body Centred Cubic


(2 atoms)

Face Centred Cubic


(4 atoms)

4r

2r
V=(2r) =8r
3

(4r)2 =
a2+a2+a2
a = r(16/3)
V=

4 r
(4r)2 = a2+a2
a = r8
V = r3(8)3/2
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Space utilisation in cubic


cells
How much space taken up by atoms?
Atom volume = (4/3)r3
Simple cubic:
1 atom per cell: (4/3)r3/(8r3) = /6 = 52.4%
Body-centred cubic:
2 atoms per cell: 2(4/3)r3/(r3(16/3)3/2) = 68.0%
Face-centered cubic: do the calculation

yourself!

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LC: space utilisation


How much space is

Face Centred Cubic

taken up by atoms
(as a percentage) in a
face-centred cubic?

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LC: space utilisation


How much space is

Face Centred Cubic

taken up by atoms in
a face-centred cubic?
4 atoms per cell:

4(4/3)r3 /(r3(8)3/2)
= 74.0%

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My Super Power
If you could have any super power, what

would it be?

Packingthemostamount
ofstuffintothesmallest
amountofspace/time!
Closepackingmaximizes
atomicinteractionsand
minimizesthevolume

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LC: Find the density


Vanadium (V) crystallises in a bcc structure and
has an atomic radius of 131 pm. Determine the
density if the edge length of the bcc unit cell is
4r/3 and the atomic mass is 50.94 g/mol. (N A
= 6.0221023 mol-1)
A. 3.06 g/cm3
B. 6.11 g/cm3
C. 2.77 g/cm3
D. 12.2 g/cm3
E. 8.46 g/cm3
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LC: Find the density


B. 6.11 g/cm3
.Unit cell vol. = [4(13110-10 cm)/3]3 =

2.76810-23 cm3
.2 atoms/cell: 2/(6.0221023 mol-1) =
3.32110-24 mol
.density: (3.32110-24 mol)(50.94 g/mol)/
(2.7710-23 cm3)
.density: 6.11 g/cm3

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Summary
Solids and liquids classified by forces of

attraction
Properties of substance result from forces of
attraction
m.p., b.p., conductivity, viscosity, etc.

Phase change data summarised by heating

curves & phase diagrams


Crystal structure of solids classified by crystal
lattice and the basis
Molecular formula can be found from the unit
cell
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Suggested Ch 11
Exercises
Review questions 2-45.
Problems by Topic, Cumulative Problems,

Challenge Problems: 49, 53, 55, 59, 61, 63,


67, 69, 73, 77, 79, 83, 85, 87, 89, 91, 97, 99,
101, 105, 107, 111, 113, 125, 141, 159, 161.
Note: answers to all odd-numbered problems
are found in Appendix III.

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