Liquids, Solids and

Intermolecular Forces
 Contents

13-1 Intermolecular Forces and Some Properties of Liquids

13-2 Evaporation of Liquids: Vapor Pressure
13-3 Some Properties of Solids
13-4 Phase Diagrams
13-5 Van der Waals Forces
13-6 Hydrogen Bonding
13-7 Chemical Bonds as Intermolecular Forces
13-8 Crystal Structures
 13-1 Intermolecular Forces and
Intermolecular Some Properties
Forces
of Liquids
• While examining gases, we have defined the ideal gas
equation by neglecting the intermolecular forces.

• Intermolecular forces are important for liquids and solids.

• General equations for liquids and solids will not be derived,

investigations will be more qualitative and less
mathematical for gases.

• When the intermolecular forces between the gases reach a

sufficient level, the gas condenses to the liquid state.

• Intermolecular forces are important in understanding the

surface tension and viscosity of liquids .
13-1 Intermolecular Forces and Some Properties
of Liquids
• Cohesion Forces
intermolecular between similar molecules are forces.
• Adhesion Forces
They are intermolecular forces between different
molecules.
• Surface Tension ( γ )
The energy required to increase the surface area of a liquid,
or is work . The force keeping the unit length taken from the
surface stretched (J/m 2 ). γ = F/A
• Viscosity ( ɳ )
It is the resistance of a liquid to flow.
 Intermolecular Forces

• Liquids tend to keep their surface area to a minimum

(spherical raindrops, min. area/volume ratio).
 Intermolecular Forces
• As the temperature (intensity of molecular motion) increases, the
effect of intermolecular forces decreases, so the surface tension
decreases.

• If the cohesive forces are greater than the adhesion forces, the
droplet retains its shape.

• If the forces of adhesion are large enough, the work done during the
dispersion of the drop compensates for the energy required to spread
the liquid into a film. Water wets the surface.

• Adding detergent to water has two effects: 1) The detergent solution

dissolves the oil and cleans the surface. 2) Detergent reduces the
surface tension of the water (reducing the energy required for the
drop to turn into a film) and allows the water to spread.

• Such substances are called wetting agents .

 Intermolecular Forces

Wetting a surface
capillary effect
• Due to the large adhesion forces between the water and the glass, the
water spreads as a thin film on the inner walls of the capillary tube.
• The pressure under the surface boundary drops slightly .
• External pressure pushes the water column towards the tube to
compensate for this difference.
• In smaller diameter capillaries, the liquid rises more.
• The magnitude of the capillary effect is proportional to the surface
tension.
 Intermolecular Forces

Surface boundary
formation

• Water wets the glass, the surface border is concave.

• Mercury does not wet the glass, the surface border is convex.
• Cohesion forces in mercury come from strong metallic bonds
between Hg atoms and mercury does not wet the glass.
• Mercury with high cohesion and weak adhesion forces does not
rise in the capillary tube.
• The rise of water in the soil is partially based on the capillary
effect.
 Intermolecular Forces
• Viscosity is the resistance of a liquid to
flow.
• As the intermolecular forces of attraction
increase, the viscosity increases.
• Cohesive forces within the fluid create an
'internal friction' that lowers the flow
rate.
• Fluids that run slowly, such as honey and
heavy motor oils, are called 'viscous
fluids' .
• As the viscosity of the liquid increases,
the falling time of the ball becomes
longer.
• As the kinetic energies of the molecules
Measuring viscosity increase, the intermolecular forces of
attraction will decrease, and as the
temperature increases, the viscosity
decreases.
 13-2 Evaporation of Liquids: Vapor Pressure
• According to the kinetic theory, the speeds and kinetic energies
of molecules are not equal at a certain temperature.

• Molecules with kinetic energy above the average value, which

may prevail over the intermolecular attraction forces, can get
rid of the liquid surface and become a gas.

• The transition of molecules from the liquid surface to gas or

vapor is called evaporation .

• Evaporation is faster at high temperature, with an increase in

the surface area of the liquid and less intermolecular forces.
 Enthalpy of Evaporation
• During evaporation, molecules with energy greater than the average
energy move away, the average kinetic energy of the remaining
molecules decreases, and the temperature of the evaporated liquid
decreases.
• To keep the temperature of the evaporated liquid constant, heat must
be given to the liquid.
• Enthalpy of evaporation is the amount of heat required for a certain
amount of liquid to evaporate at a constant temperature. is called.
Δ H evaporation = H vapor – H liquid

• Evaporation is endothermic and ΔHb is always positive .

• The conversion of a gas or vapor to liquid is called condensation ,
condensation is exothermic and always negative.
• From a thermodynamic point of view, condensation is the opposite of
evaporation.

Δ H condensation = H liquid – H vapor = - Δ H buh .

 Enthalpy of Evaporation

• Enthalpies of vaporization are generally defined as the

amount of heat required to evaporate one mole of liquid.
 Vapor Pressure
• All of the water left in an open container evaporates, but if the evaporation
happens in a closed container, a different situation occurs.
• In a vessel where liquid and vapor coexist, evaporation and condensation
occur at the same time.
• If there is enough liquid, eventually a state is reached where the amount of
vapor remains constant. This is a state of dynamic equilibrium.
• The pressure created by the vapor in dynamic equilibrium with its liquid is
called vapor pressure .
• Liquids with a high vapor pressure at room temperature are called volatile ,
and liquids with a very low vapor pressure are called non-volatile liquids .
• As intermolecular forces decrease, volatility increases (vapor pressure
increases).
• The vapor pressure of a liquid depends on the type of liquid and its
temperature.
• The vapor pressure increases with temperature.
 Vapor Pressure

(a) First, the liquid is poured into a closed container. First there is only
evaporation.
(b) Condensation begins. The rate of evaporation is greater than the rate of
condensation and the number of molecules in the vapor state continues to
increase.
(c) The rate of condensation is equal to the rate of evaporation. The number of
molecules in the vapor state and the pressure exerted by the steam remain
constant.
 Boiling and Boiling Point
• When a liquid is heated in a container open to the atmosphere, at a
certain temperature, evaporation occurs in the entire liquid mass.
• Vapor bubbles in the liquid mass rise to the surface and move away.
• The pressure created by the molecules moving away becomes equal to
the pressure created by the molecules of the atmosphere, this
phenomenon is called boiling .
• The energy taken in the form of heat during boiling is used only to
convert liquid molecules into vapor.
• The temperature remains constant until all the liquid has boiled.
• The temperature at which the vapor pressure is equal to the standard
atmospheric pressure (1 atm = 760 mmHg) is called normal boiling
point .
• A graph showing the variation of vapor pressure with temperature is
called a vapor pressure curve .
 Boiling point

Mercury vapor Pvapor is Pvapor is

barometer Pvapor,
pressure of independent independent
depends on T
the liquid of Vliq of Vvapor

(a) Mercury barometer (b) Liquid is placed on mercury, the vapor pressure
of the liquid lowers the mercury level (c) Compared with b, the vapor
pressure is independent of the amount of liquid (d) Compared with c, the
vapor pressure is independent of the volume of the vapor (e) As the
temperature increases, the vapor pressure increases.
 Critical Point
• When defining boiling, the liquid is in a ' container open to
atmosphere '.
• If the liquid is in a closed vessel, there is no boiling, instead the
pressure and temperature rise constantly.
• The density of the liquid decreases gradually, the density of the vapor
increases, as a result, the density of the liquid and vapor becomes
equal.
• The surface tension of the liquid approaches zero, the boundary
between liquid and vapor becomes blurred and gradually disappears.
• The point at which liquid and vapor are indistinguishable is called
critical point .
• The temperature at the critical point is called the critical
temperature (Tk ) and the pressure is called critical pressure ( Pk ) .
• The critical point is the highest point of the vapor pressure curve and
indicates the highest temperature at which the liquid can be formed.
 Critical Point

• A gas can only be liquefied below its critical temperature.

• If the room temperature is below the critical temperature, the gas can only
be liquefied by applying an appropriate pressure.
• If the room temperature is higher than the critical temperature, besides
applying pressure, it is necessary to lower the temperature below Tk.
 Critical Temperatures and Pressures

• Persistent gases cannot be liquefied at 25 0 C (298 K).

• Non-persistent gases can be liquefied at 25 0 C (298 K).
Vapor Pressure Equation

This equation gives the natural

logarithm of the vapor pressure
as a function of the inverse of
the Kelvin temperature.
 Clausius-Clapeyron Equation

• The usual way to eliminate A in the vapor pressure

equation is to rewrite the equation in what is called the
Clausius-Clapeyron equation.

• The Clausius-Clapeyron equation is the equation that

gives the variation of vapor pressure with temperature.
 13-3 Some Properties of Solids
Freezing point Melting point

Enthalpy of melting: The amount of heat required to melt a

solid. Δ H melting (H2O) = + 6.01 kJ /mol
 Sublimation
• The transition of molecules from the
solid state directly to the vapor state is
called sublimation . The opposite of
sublimation is deposition .

• The sublimation enthalpy is the sum of

the melting and vaporization enthalpies of
the substance.
• The two solids with significant
sublimation pressures are ice and dry ice
(solid carbon dioxide).
• All solids that have the required
evaporation pressure at a given temperature
are generally able to sublimate.
Sublimation of solid
iodine Δ H s u b . = ΔH melting + Δ H vap = - Δ H frost.
 13-4 Phase Diagrams
• States of matter; solid, liquid and gas .
• Phase: A sample of a substance that has a definite composition
and uniformity and can be distinguished from other phases with
which it is in contact.
• solids, liquids and gases (steam) in single phase (or state) or
pressure at which it is in more than one phase in equilibrium with
each other, and
The graphic representation of temperatures is called a phase
diagram .
• a pressure-temperature graph ;
High P, Low T solid state,
Medium P, Medium T liquid state,
Low P represents the High T gas state.
 13-4 Phase Diagrams
• In the curves, the areas between the lines are the single phase or
state of matter; the lines separating the fields correspond to the
equilibrium position of the phases represented by these fields.

• The point that shows a single temperature and pressure where solid,
liquid and vapor are in equilibrium together is called the triple point .

• Covering such a wide range of temperature and pressure makes it

difficult to draw the entire phase diagram to scale, so the axes are
scaleless.

• Crossing the curve that separates two phases in a phase diagram is

called a phase transition .
 Phase Diagrams-Iodine

OC: Vapor pressure curve of liquid iodine. OB: Sublimation curve

of solid iodine. OD: Melt curve. O: Triple point. A: Critical point.
 Phase Diagrams, Carbon Dioxide

The line P = 1 atm intersects the sublimation curve, not the vapor
pressure curve. If solid CO 2 is heated in an open container, it sublimes
at -78.5 0 C. That's why it's called dry ice . Liquid CO 2 is obtained over
5.1 atm, it is used as a fire extinguisher.
 Supercritical Fluids

The phase above the critical point is difficult to name, it has a high
density like a liquid and a low viscosity like a gas. The supercritical
fluid CO 2 is used to dissolve the caffeine in coffee .
 Phase Diagram of Water

The OD melting curve has a negative slope, as the pressure increases,

the melting point of ice decreases. The presence of a solid in more than
one form is called polymorphism . O: 4.58 mmHg, 0.0098 0 C, C: 374.1
0 C, D: 2045 atm, -22 0 C.
 13-5 Van der Waals Forces
(Intermolecular Forces)
Permanent Dipoles
• There is a probability that at a given moment electrons
will accumulate in a region of an atom or molecule.
• Such movement of electrons leads to polarization of a
normally nonpolar molecule.
• Permanents dipole occurs, that is, the molecule has a
temporary dipole moment.
Induced Dipoles
• After this event, the electrons in the neighboring atom or
molecule also displace and form a dipole .
• This is an induction event and the new dipole formed
induced dipole is called.
 Van der Waals Forces
Dissolution or London Force _
• Instantaneous and induced dipoles lead to the formation of
intermolecular forces of attraction. We might call this
instantaneous dipole -induced dipole attraction, but common
names are "dispersion force" or "London force" ( Fritez
London in 1928).

Polarity ( Polarizability )
• Polarizability to the event that a molecule is induced by a
dipole is called.
• Polarizability increases with the number of electrons; The
number of electrons also increases with the molecular mass.
They are less attracted by the nucleus and the polarizability of
the molecule increases. The melting and boiling points of
induction

❖ Induction is when an
electrically charged object
comes into contact with another
object, resulting in an electric
current in that object.
❖The withdrawal of a balloon
by a surface is a well-known
example of induction. The
balloon is loaded by friction, and
the charged balloon causes the
surface to be loaded (induced)
by the opposite charge.
 Dipole-Dipole Interactions:
Permanent and Induced Dipoles

Normal state Instantaneous state Induced dipole

(a) Normal State: The nonpolar molecule has a symmetrical

charge distribution.
(b) Momentary Situation: e-'s are displaced and charge
separation occurs, a momentary dipole occurs.
(c) Induced Dipole: The instantaneous dipole on the left
molecule induces charge separation on the right molecule. The
result is a dipole-dipole interaction.
 Dipole Dipole Interactions

• The chain pentane molecule is more polarized than the round

neopentane molecule.
• Intermolecular forces are stronger in pentane than in
neopentane.
• Pentane boils at a higher temperature than neopentane.
Dipole Dipole Interactions
 Properties of Van der Waals Forces
• London (dispersion) forces exist between all molecules. The
magnitude of these forces increases with the molecular mass
and also depends on the molecular shape.
• The permanent dipole moments are the result of the movements
of the e-pairs in the bonds rather than all the electrons in the
molecule. Permanent dipoles are found only in molecules with a
dipole moment (polar).
• compounds with similar molecular masses are compared, it is
seen that the dipole moment creates significant differences in
properties such as melting point, boiling point and enthalpy of
evaporation.
• In compounds with very different molecular masses , dispersion
forces are often more important than dipole forces.
 13-6 Hydrogen Bonding

Comparison of boiling points of some hydrides of elements in

group 14, 15, 16, 17
 13-6 Hydrogen Bonding

• A hydrogen bond is formed when a hydrogen atom

attached to a high electronegativity atom is
simultaneously attracted to a high electronegativity
atom of the neighboring molecule.

• The hydrogen bond is formed only with the hydrogen

atom, only F, O and N easily fulfill the conditions
necessary for the formation of the H-bond.

• Hydrogen bond energies 15-40 kJ / mol level.

Hydrogen Bonding in HF
 Hydrogen Bonding

Around Molecule Crystal structure of ice liquid water

The lack of H-bonds in ice makes it less dense than water. As the ice
melts, the molecules stack more frequently and the density increases.
The maximum density of water is at 4 0 C.
Other Features Affected by H-Bonding

dimerization of acetic acid

Salicylic acid
(Intramolecular H-
bond)