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Intermolecular Forces,

Intermolecular Forces,
Liquids & Solids
Liquids & Solids
Chapter 11
Overview

Liquids & Solids

Intermolecular Forces

Liquids

Phase Changes

Vapor Pressure

Phase Diagrams

Solids -- Structure

Bonding Types in Solids


Liquids & Solids

Solids
particles close together
locked into relative positions
(crystalline
strong interactions
(interparticle !orces

Liquids
particles !arther apart
mo"ile relative to each other
#eaker interactions "et#een
particles
Remember
$as Liquid
+ E
- E
condensation
vapori%ation

condensation
! -
"apori#ation
! $
Liquid
Solid
+ E
- E
!ree%ing
melting

%ree#ing
! -
melting
! $
Intermolecular Forces

Strength o% I& Forces determine 'oiling points


and melting points

Ion-Dipole Forces
occur "et#een ions and dipoles
"et#een charged particles and neutral, polar covalent
particles

Dipole-Dipole Forces
occur "et#een t#o dipoles
"et#een t#o, neutral, polar covalent particles
Ion & 'ipole Force
(() & *)) k+,mol
+
O
H

-
+
+
'ipole & 'ipole Force
(- & .- k+,mol
+ +


/0ydrogen 1onding2 Force
(( & .- k+,mol

/0ydrogen 1onding2 Forces


special case o! 'ipole&'ipole !orces
occur "et#een t#o, neutral, polar covalent particles
#hich

have a H atom (which is bound to an O, F or N atom) for the


(+) dipole
have an O, F, or N atom for the (-) dipole
e3tra strength due to
small size and lare !N of O, F or N
and small size of H

London 'ispersion Forces


occur "et#een all particles even neutral, non&polar
covalent particles
occur "et#een an instantaneous dipole and an
induced dipole
!orce is #eak "ut strengthens #ith increasing
polari%a"ility o! the particles
polari%a"ility o! the particles increases #ith
increasing si%e or mass
'ipole & Induced 'ipole
(. & 1) k+,mol

+

+
polar molecule non&polar
molecule
+
+
Induced 'ipole &
Induced 'ipole Force
()4)- & () k+,mol
London 'ispersion
Strength of Forces
(
Ion - Dipole
(
)ydrogen Bonding*
(
Dipole - Dipole
(
Dipole - Induced Dipole
(
London Dispersion
I
n
c
r
e
a
s
i
n
g
0e (4*
5e .647
8r 964-
:r 1.)4;
<e 1**41
1oiling =oints o! 5o"le $ases
>emp
:
??
F
.
9-41
Cl
.
.794*
1r
.
77.4)
I
.
(-64*
1oiling =oints o! 0alogen 'iatomics
>emp
:
??
0
.
@ 767
0
.
S .1.

0
.
Se .71
0
.
>e .61
1oiling =oints o! $roup * 'ihydrides
>emp
:
??
$e0
(
19(
C0
(
1);
Si0
(
1*1
Sn0
(
What Does it Mean?

/hydration2 is "ery important in the sol"ation


process & compound %ormation

stronger the interaction+ the more energy is


released+ more e,othermic

the strength o% the interaction determines the


state o% the su'stance

unusual properties o% -ater are due to


)hydrogen 'onding*
What kind of forces are etween!

.
/
molecules


/
. and 0
1
molecules

0e atoms

F and 0
1
molecules

C
2
and Br
/
molecules
London Dispersion
ydrogen Bonding
London Dispersion
ydrogen Bonding
London Dispersion
"ro#erties of Liquids

Viscosity
resistance to !lo#
ease #ith #hich liquid particles move relative to one
another
related to attractive !orces "et#een particles
and structural properties o! the particles themselves
decreases #ith increasing energy (temperature o!
particles

Sur%ace Tension
energy required to increase the sur!ace area o! a liquid "y
a unit amount
a sphere produces the minimum sur!ace area
competition "et#een cohesive !orces vs adhesive !orces
cohesive forces tend to minimize surface area
adhesive forces tend to ma"imize surface area
high sur!ace tension re!lects strong cohesive !orces
capillary action && lo# sur!ace tension, strong adhesive
!orces
"hase $hanges

3nergy Changes
melting, solid to liquid
endothermic -- H
fusion

vapori%ation, liquid to gas
endothermic -- H
vaporization

condensation, gas to liquid
exothermic -- H
condensation
# - H
vaporization

!ree%ing, liquid to solid
exothermic -- H
freezin
# - H
fusion

"hase $hanges% cont&d
su"limation, solid to gas
endothermic -- H
sublimation

deposition, gas to solid
exothermic -- H
deposition
# - H
sublimation

"ro#erties of Liquids
liquid
solid
freezing -- exothermic
melting -- endothermic
liquid gas
vaporization -- endothermic
condensation -- exothermic
Tem
p
Tim
e
solid
liquid
gas
solid + liquid
in equilibrium
liquid + gas
in equilibrium
constant temp

Critical Temperature & Pressure


critical temp4
hihest temperature at which a substance can e"ist as a li$uid
critical pressure
pressure re$uired to cause li$uefaction at the critical temperature
a gas cannot "e lique!ied a"ove the critical temperature
critical point
corresponds to %
c
and &
c

the point above which a supercritical gas e"ists
the substance cannot be li$uefied b' increasin the pressure
Pressur
e
Liquid
H
2
O
Vapor
Tc = 64!6 "
#ritical $oint
2%! atm = $c
Temperatu
re
'a#or "ressure

&olecular Description
liquids have a distri"ution o! energies !or the liquid
molecules
at any temperature, some molecules have su!!icient
energy !or vapori%ation
the higher the temperature, the greater num"er o!
molecules #ith energy o! vapori%ation
at constant temperature, average energy o! molecules
is constant "ut in dynamic equili"rium
vapor pressure is the pressure e3erted "y vapori%ed
molecules #hen liquid and vapor states are in dynamic
equili"rium
Avaporation
Aquili"rium
Bapor =ressure
liquid
gas
Aq4 Bapor =ressure -- partial pressure
of gas over a liquid at equilibrium

Volatility+ Vapor Pressure & Temp4


su"stances #ith high vapor pressure are volatile
in a open container, dynamic equili"rium cannot "e
esta"lished && complete evaporation
higher the temperature, greater vapor pressure,
greater volatility

Vapor Pressure & Boiling Point


"oiling point && temperature at #hich the vapor
pressure C atmospheric pressure

boilin point increases with increasin e"ternal


pressure, vice versa
normal "oiling point && temp4 at #hich the vapor
pressure C 1 atm
5ormal 1oiling =ointD temperature
at which the vapor pressure is equal to
1.00 atmosphere
1oiling =ointD temperature at which
the vapor pressure is equal to the
external or atmospheric pressure
Which has highest oiling #oint!

/
. or
/
S

BrCl or Cl
/

BrCl or Cl

C
2
or C
/

/
.
BrCl
Cl
C
/

molar enthalpy o% "apori#ation6789mol:


, amount o% su'stance6moles:


"ap
-ater ! $2;4< 789mol = >;;(

Clausius Clapeyron 3quation?



ln P ! -
"ap
9 @T $ C
$alculate the (nerg) of 'a#ori*ation!
Phase
Diagrams
normal freezing pt!
solid
liquid
normal &oiling pt!
vapor
>riple =oint
Pressu
re
Temperatu
re
H
2

solid
vapor
solid liquid
liquid vapor
Structures of Solids

Anit Cells
characteristic 7&dimensional repeating unit o!
a crystalline su"stance

primitive cu"ic (sc 1 atom,u4c4

"ody&centered cu"ic ("cc . atoms,u4c4

!ace&centered cu"ic (!cc ( atoms,u4c4


primitive cu"ic
"ody&centered cu"ic
!ace&centered cu"ic
$lose "acking of S#heres

Layered as BBBBBBBB or

BBCBBC
Physical Properties of
Solids:
solid liquid
melting && endothermic
!ree%ing && e3othermic
solid gas
su"limation && endothermic
deposition && e3othermic
?elting =ointD !emperature at which
the cr"stal lattice brea#s down
H
fusion
= H
free$ing
melting free$ing
Which one of each #air will have the higher
melting #oint?

0aF or 0aI

Cl or I

.
/
or Br
/

0aCl or BrCl


/
S or
/
.
0aF
Cl
Br
/
0aCl

/
.
Ionic cations & anions
?etallic metal atoms
?olecular molecules
5et#ork atoms
8morphous irregular net#orks
Types of Solids:
!"pes %nits
5et#ork Solid
'iamond
5et#ork Solid
$raphite
NaCl
Na
Cl

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