Intermolecular Forces: (inter = between) between molecules

What determines if a
substance is a solid,
liquid, or gas?

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Gases: The average kinetic energy of the gas
molecules is much larger than the average energy of
the attractions between them.

Liquids: the intermolecular attractive forces are

strong enough to hold the molecules close together, but
without much order.

Solids: the intermolecular attractive forces are strong

enough to lock molecules in place (high order).

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The strengths of intermolecular forces are generally
weaker than either ionic or covalent bonds.

16 kJ/mol (to separate molecules)

+ - + -

431 kJ/mol (to break bond)

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Types of intermolecular forces (between neutral molecules):

Dipole-dipole forces: (polar molecules)

..+
S ..
: O O: dipole-dipole attraction
: ..
- -

..+
S ..
: O O:
: ..
- -
What effect does this attraction have on the boiling point?
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 Polar molecules have
dipole-dipole attractions for
one another.

+
HCl----- +HCl-

dipole-dipole attraction
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Types of intermolecular forces (between neutral molecules):
Hydrogen bonding: cases of very strong dipole-dipole
interaction (bonds involving H-F, H-O, and H-N are most
important cases).

+
H-F- --- +H-F-

Hydrogen bonding
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 Boiling points versus molecular mass

100

-100

Predict a trend for: NH3, PH3, AsH3, and SbH3

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 Predict a trend for: NH3, PH3, AsH3, and SbH3

0
0 50 100 150
-20 SbH3
Boiling Pt (Celcius)

NH3
-40

-60
AsH3
-80
PH3
-100
Molecular Weight (g/mol)

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 Now let’s look at HF, HCl, HBr, and HI

40
HF
20
Boiling Pt (Celcius)

0
SbH3
-20 0 50 100 150
-40 NH3 HI
AsH3
-60
-80 HBr
HCl
-100 PH3
Molecular Weight (g/mol)

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Types of intermolecular forces (between neutral molecules):

London dispersion forces: (instantaneous dipole moment)

( also referred to as van der Waal’s forces)
attraction

- + - +

“electrons are shifted to overload one side of an atom

or molecule”.
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polarizability: the ease with which an atom or molecule
can be distorted to have an instantaneous dipole.
“squashiness”

In general big molecules

are more easily polarized
than little ones.

little Big and

“squashy”
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 Halogen Boiling Pt Noble Gas Boiling Pt
(K) (K)

F2 85.1 He 4.6

Cl2 238.6 Ne 27.3

Br2 332.0 Ar 87.5

I2 457.6 Kr 120.9

Which one(s) of the above are most polarizable?

Hint: look at the relative sizes.
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 Other types of forces holding solids together:

ionic: “charged ions stuck together by their charges”

There are no individual molecules here.

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Metallic bonding: “sea of electrons”

Copper wire: What keeps the atoms together?

Cu atoms

an outer shell electron

To which nucleus does the electron belong?

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Metallic Bonding: “sea of e-’s”

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Covalent Network: (diamonds, quartz) very strong.

1.42 Å

1.54 Å
3.35 Å

What type of hybridization is present in each?

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Name type of solid Force(s) Melting Pt. Boiling Pt.
(oC) (oC)

Ne molecular -249 -246

H2S molecular -86 -61

H2O molecular 0 100

Mercury metallic -39 357

W metallic 3410 5660

CsCl ionic 645 1290

MgO ionic 2800 3600

Quartz (SiO2) covalent network 1610 2230

Diamond (C) covalent network 3550 4827

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 Pentane isomers: C5H12

n-pentane iso-pentane neo-pentane

Hvap=25.8 kJ/mol Hvap=24.7 kJ/mol Hvap=22.8 kJ/mol

All three have the same formula C5H12

Why do they have different enthalpies of vaporization?

London and “Tangling”

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 C-C-C-C C
C C-C-C
C
iso-pentane
neo-pentane
Hvap=24.7 kJ/mol
Hvap=22.8 kJ/mol
n-pentane

Hvap=25.8 kJ/mol
London and “Tangling”

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Structure effects on boiling points

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 Ion-dipole interactions: such as a salt dissolved in water

cation

polar molecule

anion

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Phase changes:

solid  liquid (melting  freezing)

liquid  gas (vaporizing  condensing)

solid  gas (sublimation  deposition)

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Energy changes accompanying phase changes

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Heating curve for 1 gram of water

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 Heating curve for 1 gram of water

Specific Ht. Steam = 1.84 J/g•K

Hvap=2260 J/g

Specific Heat of water = 4.184 J/g•K

Hfus=334 J/g

Specific Heat of ice = 2.09 J/g•K

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Calculate the enthalpy change upon converting 1 mole
of water from ice at -12oC to steam at 115oC.

solid solid liquid liquid gas gas

-12oC 0o C 0oC 100oC 100oC 115oC

H1 + H2 + H3 + H4 + H5 = Htotal

Sp. Ht. + Hfusion + Sp. Ht. + HVaporization + Sp. Ht. = Htotal

Specific Heat of ice = 2.09 J/g•K

Hfus=334 J/g
Hvap=2260 J/g
Specific Heat of water = 4.184 J/g•K
Specific Ht. Steam = 1.84 J/g•K
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Calculate the enthalpy change upon converting 1 mole
of water from ice at -12oC to steam at 115oC.

solid solid liquid liquid gas gas

-12oC 0o C 0oC 100oC 100oc 115oc

H1 + H2 + H3 + H4 + H5 = Htotal

Sp. Ht. + Hfusion + Sp. Ht. + HVaporization + Sp. Ht. = Htotal

Specific Heat of ice = 2.09 J/g•K

Hfus=334 J/g
Specific Heat of water = 4.184 J/g•K
Specific Ht. Steam = 1.84 J/g•K
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Vapor pressure

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 VAPOR PRESSURE CURVES

A liquid boils when its vapor pressure =‘s the external pressure.
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normal boiling point is the temperature at which a
liquid boils under one atm of pressure.

pressure = 1 atm

vapor pressure = 1 atm

liquid
BOILING
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PHASE DIAGRAMS: (Temperature vs. Pressure)

gas and liquid are

indistinguishable.
critical temperature
and critical pressure

(all 3 phases exists here)

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 H2O CO2

note slope with pressure

note slope with pressure
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Crystal Structures:

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 unit cells:
contains 1 atom contains 2 atoms

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