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8/13/2018

1. Describe the four types of intermolecular forces and


characterize by relative strength and chemical
examples.

2. Predict the relative strength of dispersion forces based


on molecular shape and size.

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Strength of
Density Motion
intermolecular forces

Very limited
Solid High Strong
freedom of motion
Some freedom of
Liquid High Moderate
motion
Complete freedom
Gas Low Weak
of motion

Gas Liquid Solid

 Hcrystallization = −Hfusion
 Hvaporization = −Hcondensation
 Hsublimation = Hfusion + Hvaporization

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Intermolecular forces: attractive forces that exist between


all molecules and atoms.

• Four types of intermolecular forces (weakest to strongest):

1. Dispersion forces

2. Dipole-dipole forces

3. Hydrogen bonding

4. Ion-dipole forces

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Dispersion forces (London forces): An intermolecular forces


exhibited by all atoms and molecules that results from
fluctuations in the electron distribution
Induced dipole: The temporary dipole established in one
molecule induces a temporary dipole on its neighboring
atoms, which then attract one another.

Larger molar mass = more e– =


larger e- cloud =
increased polarizability =
stronger attractions

More surface-to-surface contact =


larger induced dipole =
stronger attraction

Boiling Points of Noble Gases


Molar Mass Boiling
Noble Gas
(g/mol) Point (K)

He 4.00 4.2

Ne 20.18 27

Ar 39.95 87

Kr 83.80 120

Xe 131.3 165

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Halogen Molar Mass Atomic MP BP


(g/mol) Radius (pm) (K) (K)
fluorine, F2 38 72 53 85
chlorine, Cl2 71 99 172 238
bromine, Br2 160 114 266 332
iodine, I2 254 133 387 457
astatine, At2 420 150 575 610

• The magnitude of the induced dipole depends on:

1. Molar mass (size of molecules)

– Larger molar mass  more electrons  larger


electron cloud  less tightly held by nucleus  easier
to polarize stronger attraction

2. Shape of the molecule

– More surface-to-surface contact  easier to polarize


 stronger attraction

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• Same molar mass, but different molecular shapes


– Straighter the shape  stronger dispersion force

• Dipole–dipole forces: An intermolecular force exhibited


by polar molecules that results from the uneven charge
distribution.

• The positive end of one permanent dipole attracts the


negative end of another through dipole-dipole forces.

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Polar molecules have higher melting and boiling points


than nonpolar molecules of similar molar mass.

Molar Mass bp mp
Formula Structure
(g/mol) (ºC) (ºC)
3.5 polar
CH2O 30.03 −19.5 −92
2.1 2.5

nonpolar
C 2H 6 30.07 −88 −172

• Miscibility: the ability to mix without separating into two


liquids
• Rule of thumb: Like dissolves like
– Polar substances dissolve in polar solvents.
– Nonpolar molecules dissolve in nonpolar solvents.

Example:

C5H12: nonpolar C5H12(l)

H2O: polar H2O(l)

The attractive forces between the H2O molecules is much


stronger than their attractions for the C5H12 molecules. The
result is that the liquids are immiscible.

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Which of these molecules have dipole–dipole forces?


a. CO2 b. CH2CI2 c. CH4

Hydrogen bonding: polar molecules containing H atoms


bond directly to small and highly electronegative F, O, or N
atoms.
− Stronger than dipole-dipole and dispersion forces

H-bonds require one of each:


Molecule A Molecule B
+ +
N H Hydrogen N R
bonding
O H O R

F H F R

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• Water molecules participate in multiple hydrogen-


bonding interactions with nearby water molecules.
• Identify the 2 atoms participating in the hydrogen bond.

• Group 5A, 6A, and 7A binary hydrides of period 2


compared to periods 3−5.

Unusually high
boiling points due to
hydrogen bonding.

Group 7A
Group 6A
Group 5A

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• The ion-dipole force occurs when an ionic compound is


mixed with a polar compound.
– Ion-dipole forces are stronger than other Intermolecular Forces.

Example: NaCl in H2O

NaCl(s) → Na+(aq) + Cl−(aq)

𝛿
𝛿 𝛿 𝛿
𝛿
𝛿
𝑪𝒍 𝑵𝒂
𝛿 𝛿
𝛿 𝛿
𝛿
𝛿

3. Define the following physical properties and relate to


strength of intermolecular forces: surface tension,
viscosity and capillary action

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• In liquids, we also observe three other manifestation of


intermolecular forces:

1. Surface tension

2. Viscosity

3. Capillary action

• Surface tension: The energy required to increase the


surface area of a liquid by a unit amount

– The tendency of liquids to minimize their surface area

Interior molecule: Surface molecule:


interacts with six interacts with four
neighbors neighbors

Floating paper clip

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• Factors affecting surface tension:

1. The stronger the intermolecular attractive forces, the


higher the surface tension.

2. Raising the temperature of a liquid reduces its surface


tension.

• T ↑  average kinetic energy of the molecules ↑ 


easier to stretch the surface.

• Viscosity: the resistance of a liquid to flow.


– 1 poise = 1 g/cm-s = 100 cP (centipoise)
• Factors affecting viscosity:
– Stronger intermolecular forces  higher viscosity
– Higher temperature  lower viscosity

Molar Mass Viscosity


Formula
(g/mol) (cP)
CH3CH2CH2CH2CH3 72.15 0.240
CH3CH2CH2CH2CH2CH2CH3 100.2 0.409
CH3CH2CH2CH2CH2CH2CH2CH2CH3 128.3 0.711

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4. Define phase transitions and relate phase transition


temperature to intermolecular forces.

• Vaporization: liquid  gas opposite


processes
• Condensation: gas  liquid

• Vaporization is an endothermic process


– Energy is needed to overcome the intermolecular
forces (to pull the molecules away from one another)
• Condensation is an exothermic process. H2O(g)

• Heat of vaporization (∆Hvap): the amount


of heat required to vaporize one mole of
a liquid to gas.
− Always positive
H2O(l)
H2O(l)

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For a given substance, the sum of its enthalpy of fusion and


enthalpy of vaporization is approximately equal to its enthalpy
of sublimation.

Gas

Sublimation Deposition
Hsub –Hsub
Energy

Vaporization Condensation
Hvap –Hvap

Liquid
Fusion Freezing
Hfus –Hfus
Solid

5. Define vapor pressure and the rate of vaporization and


relate each to temperature, surface area and
intermolecular forces

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Vaporization: liquid  gas


• The rate of vaporization increases with
– Increasing temperature
• As average kinetic energy increases more
molecules have enough energy to overcome the
intermolecular forces.
– Increasing surface area
• Surface molecules are held less tightly than interior
molecules; thus have a greater tendency to
evaporate.
– Decreasing strength of intermolecular forces
• A reduced amount of attractive forces to hold
molecules in liquid state.

• Vapor pressure: the pressure of a gas in dynamic equilibrium


with its liquid
– Rate of condensation equals rate of evaporation
• Factors affecting vapor pressure of a liquid:
1. Intermolecular forces:
• Weaker intermolecular forces  easier to evaporate (volatile)
 more molecules in the gas phase  higher vapor pressure
2. Temperature:
• Higher temperature  higher thermal energy  more
molecules have enough energy to evaporate  higher vapor
pressure.
Dynamic
Equilibrium

Flask 1 Flask 2 Flask 3

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• The boiling point of a liquid is the temperature at which


the liquid’s vapor pressure = the external pressure.
– At boiling point, the interior liquid molecules have
enough energy to become gaseous.
• The normal boiling point of a liquid is the temperature at
which its vapor pressure equals 1 atm.
– 100 ºC for pure water

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As intermolecular forces increase

Surface tension Increases

Viscosity Increases

Rate of vaporization Decreases

Vapor pressure Decreases


Heat of vaporization
Increases
(∆Hvap)
Boiling point Increases

Melting Point Increases

6. Use the Clausius-Clapeyron equation and the vapor


pressure of a chemical at a specific temperature to
solve for the vapor pressure at a different temperature.

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• The Clausius-Clapeyron equation two point form:


• The vapor pressure of a liquid increases with increasing
temperature

Clausius-Clapeyron Equation
𝑷𝟐 ∆𝑯𝒗𝒂𝒑 𝟏 𝟏
𝒍𝒏
𝑷𝟏 𝑹 𝑻𝟐 𝑻𝟏

P1 is vapor pressure at T1 T1 is Temperature 1 in Kelvin


P2 is vapor pressure at T2 T2 is Temperature 2 in Kelvin
∆Hvap = heat of vaporization (J/mol) R = 8.314 J/mol • K

7. Identify phases, phase changes, triple point and critical


point on a phase diagram and describe a supercritical
fluid

8. Use a phase diagram to describe the effect of changes in


temperature or pressure on the phase of a substance

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• A phase diagram is a map of the states of a substance as


a function of pressure (y-axis) and temperature (x-axis)
• Regions: The three main regions − solid, liquid, and gas −
represent conditions where that particular state is stable.

Liquid
Pressure

Solid

Gas

Temperature

Lines: the substance is in equilibrium between the two states


on either side of the line.
– Both states coexist, and equally stable.

Fusion curve
Liquid
Pressure

Vaporization curve
Solid

Gas
Sublimation curve

Temperature

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Triple point: the three states are equally stable (coexist) and
in equilibrium

Fusion curve
Liquid Critical point
Pressure

1 atm
Vaporization curve
Solid
Triple point

Gas
Sublimation curve

Temperature Normal boiling point

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