GENERAL CHEMISTRY 2

Intermolecular forces
KINETIC MOLECULAR THOERY  Intermolecular forces
What is kinetic molecular theory of matter? o Forces of attraction and repulsion between molecules that
• Explains the physical behavior of the three states of matter (solids, hold molecules, ions, and atoms together.
liquids, and gases)  Intramolecular
• It states that the particles present in substance, independent of the o forces of chemical bonds within a molecule
physical state of substance, are always in motion.
Statements that kinetic molecular theory of matter follow IONIC BOND
• Matter is ultimately composed of tiny particles. o A complete transfer of one or more e-
• The particles are in constant random motion and therefore possess occurs when one interacting atom is much
kinetic energy. more electronegative than the other. one
• The particles interact with one another through attractions and gives up e- (cation) and one takes e-
repulsions and therefore possess potential energy.
• The kinetic energy of the particles increases as the temperature is takes a lot of energy to break ionic bonds and to turn the
increased. molecule into a gas strength: strongest bond trend: the
• The particles in a system transfer energy to each other through greater the charge difference, the stronger the attraction
elastic collisions. DIPOLE-DIPOLE
Kinetic molecular model o Sharing of electrons in a bond is
• Explains the properties of covalent but not completely even
solids and liquids in terms of (polar covalent)
intermolecular forces of o There is a polar covalent bond
attraction and the kinetic between the br and cl atoms. The
energy of the individual electron density shifts towards chlorine since it is more
particles. electronegative than bromine. Chlorine thus has a slight
negative dipole and bromine has a slight positive dipole.
o The negative dipole of the chlorine is attracted to the
positive dipole of the bromine of another brcl molecule.
This dipole-dipole attraction accounts for the brcl b.p. Of 5`c
 Trends Polarity is
amplified when electronegativity difference is large

length (primarily atomic radii of the bonding

decreases dipole
HYDROGEN BONDING
o A dipole-dipole interaction where the h atom is
noncovalently attracted to an electronegative atom.
o The h must have a large positive delta and the
other atom must have a source of electrons to be
attracted to h
 o Usually negatively charged f, o, n is attracted to the Type of interaction interacting species ionic ions only dipole-dipole polar
molecules (stationary ones have more energy than rotating ones) hydrogen
A h bond is a weak bond and is dynamic [3x10^-12 bonding h-f, -o, -n van der waals forces all molecules (just need e- cloud)
lifetime] ion-dipole ions & polar molecules cation-pi pi-electron cloud & cation pi
 In solid phase h-bond is static stacking two different pi-electron clouds
 H-bonds between molecules continually form and OTHER NON-COVALENT FORCES ALL ELECTROSTATIC IN NATURE
break in liquid. A) Ion-Dipole
 Every water molecule forms 3.4 h bonds with other o An
water molecules trend: the more electronegative a negative ion attracts the positive dipole of another molecule
the atom attracted to h, the stronger the bond
LONDON / VAN DER WAALS FORCES molecule strength: increases as ion charge or the dipole
o Electron can magnitude of the polar molecule increases. Importance: most
respond to changes commonly found in solutions and are especially important
must faster than when dealing with solubility
nucleus london B) Cation - Pi
dispersion forces/ o A weak attraction that occur between a cation and the electron-
van der waals rich pi orbital of an aromatic ring strength: relatively strong,
forces. strength ~ h-bond importance: important forces in protein
o The attraction C) Pi Stacking
between instantaneous electric dipoles on adjacent o A weak attraction that results from the distortion of two
molecules different pi - -electron cloud of one
o Present in all molecules because everything has an electron benzene ring becomes attracted to that of another, the negative
dipoles repel each other so the electrons shift away from the
increases with # of electrons in other molecule. A positive dipole is created on the other side of
depends on the polarizability [ease with which their the pi-electron cloud. The negative dipole movement of a
second benzene ring is attracted to this induced positive dipole.
o Strength
polarizability = stronger attraction. Trends: between nucleotides
1. The smaller the atom, the harder it is to distort the frequently with aromatic rings (especially important to
e- cloud (low polarizability) since the electrons are enzymes)
closer to the nucleus the larger the atom, the easier
it is to distort the e- cloud (high polarizability)
because the valent electrons are further away from
the nucleus and experience shielding from the
nucleus’ pull. [polarizability] i.e. He is small, rn is
larger
2. Surface area --- increasing surface area, increasing
boiling point 3. Molecular/ atomic weight ---
increasing weight, increasing boiling point
  Cohesive Forces
Properties of liquids  Forces that holds the liquid together.
SURFACE TENSION  Concave meniscus occurs when there is
 Property of liquid to resist an  Stronger adhesive force between the container and
external force and thus assume a the liquid than the liquid’s Molecules. The adhesive
lesser surface area. force overcomes the cohesive force of the liquid.
 Is a measure of inward forces that This causes the liquid to climb up the sides of the
must be overcome to expand the container.
surface area of a liquid. This is  Convex meniscus occurs when there is stronger
cause by an intermolecular cohesive force between the liquid’s molecules than
attraction of molecules below a the adhesive force Between the liquid and the
surface of a liquid in all direction, but at the surface they are container. This causes the liquid to create a dome
only attracted toward the interior of a liquid in all direction. shape on its surface
 He stronger the forces of attraction between the particles  Adhesive Forces
are , the greater the surface tension, and as the  Forces between a liquid and another surface.
temperature of a liquid increases the surface tension  A glass surface, the
decreases. positively charge h-
VISCOSITY atom of water
 The resistance of a liquid to flow. It is loosely referred to as bonds strongly to
the thickness or thinness of a liquid. the partial negative
 Is the resistance to flow of a liquid. In order that a liquid to charges on the
flow, the molecule must be able to slide past one another. oxygen atom at the
 The stronger the intermolecular forces of attraction, surface of the glass which
the more viscous is the liquid.(HYDROGEN BOND) results to the water
 Large intermolecular forces would cause adhering on the glass
high viscosity (GLYCEROL) surface.
 Large, complex molecules can become VAPOR PRESSURE
physically entangled (GREASE)  The vapor pressure of a substance is the pressure exerted
 The greater the viscosity, the slower the liquid flows. by its vapor when in equilibrium with its liquid or solid
Viscosity is expressed in units of centipoise.
 Water has viscosity of 1 Centipoise or 0.001 pa/s at
20 degc.
CAPILLIARY ACTION
 spontaneous rising of a liquid up a narrow tube
 is the drawing of the liquid inside a small bore-tube when
adhesive forces exceed cohesive forces.
Eg. Water absorption of plants
  The condition of the equilibrium at which the rate of be overcome to become a
evaporation is equal to the rate of condensation at certain gas. - boiling point of 0 = no
pressure of the container at the attractive force trends:
given temperature. o Boiling point example from
 This is because the rate of bruice 5.2 explain trend in
evaporation increases as the rate boiling points of h halides:
of condensation decreases with hcl, - 85`c; hbr, -67`c; hi, -
increasing temperature, vapor 15`c answer: stronger
pressure of a liquid always intermolecular forces result
increase as the temperature in higher boiling points. The
increases. dipole moments increase
 When a liquid was place in a with the polarity of the h-x
closed container, the molecule bond (the greater the difference
that escape or evaporate from the in en between the h and halogen
liquid into gas phase will cause a atoms, the stronger the dipole-
pressure on the container. dipole attractions.) The strength
 In a sealed container, some of a of london forces increases with
liquid evaporates to establish a the number of electrons cl is
pressure in the vapor phase. more en than i so hcl should have
 Vapor pressure: partial pressure of a greater boiling point but this
the vapor over the liquid data suggests that london forces
measured at equilibrium and at dominate dipole-dipole interactions for these molecules
some temperature. since iodine is larger than cl. Relative boiling points amide >
 Vapor pressure is a carboxylic acid> nitrile > > ester ~acyl chloride ~aldehyde~
strong function of keytone amides have highest boiling points because they
temperature—the have strong dipole-dipole interactions because of
higher the resonance.
temperature, the o When the vapor pressure of a liquid becomes equal to the
higher the vapor atmospheric pressure the liquid boils. Therefore, boiling
pressure (directly point is defined as the temperature at which the vapor
proportional) pressure of a liquid is equal to the atmospheric pressure.
o As the atmospheric pressure decreases the boiling point
BOILING POINT decreases; as atmospheric pressure increases, boiling point
o The boiling point of a liquid is the temperature at which its vapor
increases.
pressure is equal to the external or atmospheric pressure.
o At higher altitude where the atmospheric pressure is less,
Boiling point and Electronegativity
the boiling point of a given liquid is lower than the normal
 Boiling Point
o The temperature at which the liquid form of a compound boiling point
vaporizes into a gas. - the attractive forces in the liquid must
  Electronegativity BEHAVIOUR WHEN HEATED
o The attractive force that an atom exerts on an electron (e-)  The presence or absence of long-range order in the
o - closer e- to nucleus = more electronegative - more structure of solids results in a difference in the behavior of
protons, more positive, more attractive to eelectronegative the solid when heated.
 The structures of crystalline solids are built from repeating
- -) = < 0.5 units called crystal lattices. The surroundings of particles in
- electrostatic attraction (common in every noncovalent
the structure are uniform, and the attractive forces
molecular force)= when opposite charges with permanent
experienced by the particles are of similar types and
dipoles attract bonding
HEAT OF VAPORIZATION strength.
 Amorphous solids soften gradually when they are heated.
 Molar heat of
vaporization They tend to melt over a wide range of temperature. This
behavior is a result of the variation in the arrangement of
(δhvap) is the
particles in their structures, causing some parts of the solid
amount of
heat required to melt ahead of other parts.
AMORPHOUS SOLIDS
to vaporize
one mole of a o have considerable disorder in their structure
o also termed “amorphous” or “vitreous”
substance at
its boiling o Have a random orientation of particles. a solid without long-
range ordering atoms or molecules
point.
 E.g. Glass, plastic, coal, and rubber.
TYPES OF PROPERTIES OF SOLIDS  They are considered super-cooled liquids where
 The differences in properties of these two groups of solids molecules are arranged in a random manner similar
arise from the presence or absence of long range order of to the liquid state.
arrangements of the particles in the solid.  Some ceramics and most polymers
 Arrangement of particles
CRYSTALLINE SOLIDS
 The components of a solid can be arranged
in two general ways: they can form a  It has highly regular arrangement of particles.
regular repeating three-dimensional  Arranged in fixed geometric patterns or lattices.
structure called a crystal lattice, thus  A solid that contains a regular and repeating atomic or
producing a crystalline molecular arrangement
solid, or they can  Over large atomic distances (long-range order)
aggregate with no  Eg. Are ice and sodium chloride (nacl), copper
particular long range sulfate (cuso4), diamond, graphite, and sugar
order, and form an (c12h22o11).
amorphous solid (from  Metals, ceramics and some polymers
the greek ámorphos,
meaning “shapeless”)
CRYSTAL LATTICE Example: Zinc blende or sphalerite (zinc sulfide)
 The regular repeating structure of a crystalline solid.  BASE-CENTERED – atoms are positioned at the
 Example: salt crystal, brown sugar, amethyst cluster corners, as well at two opposite faces of the cube
CLASSIFICATION OF CRYSTALLINE SOLIDS (usually at the top and bottom faces)
Example: Ancylite (lanthanum mineral)
CRYSTAL SYSTEMS
 -a scheme by which crystal structures are classified
according to unit cell geometry
Eg. -cubic, hexagonal, tetragonal, hombohedral,
orthorhombic, monoclinic, triclinic
X-ray diffraction
 is a technique used to determine the atomic and molecular
structure of a crystal, wherein atoms cause a beams of
incident x-rays to diffract into many specific directions.
 A stream of x-rays directed at a crystal diffracts and scatters
as it encounters atoms. The scattered rays interfere with
each other and produce a pattern of spots of different
intensities that can be recorded on film.
IONIC SOLIDS
 One or more electrons are
transferred from a metal to a
non-metal, and the resulting
ions are held together by
electrostatic attraction.
Examples are Nacl,
cacl2, (nh4)3po4
TYPES OF CRYSTAL LATTICE UNIT CELLS  Made of ions (cations and anions)
 The smallest subunit of a crystal lattice that can be repeated  These ions form strong electrostatic interactions that hold
over and over to make the entire crystal. the crystal lattice together.
 SIMPLE/PRIMITIVE – atoms are only positioned at
the corners
Examples;
 Rock salt (sodium chloride) and Anilite (cerium mineral)
 BODY-CENTERED – an additional atom is positioned
at the center of the unit cell
o Examples;
 Cesium chloride and Wulfenite (lead molybdate)
 FACE-CENTERED – atoms are positioned at the
corners, as well at the faces of the unit cell
METALLIC SOLIDS SOLUBILITY AND INTERMOLLECULAR FORCES
 The valence atomic orbitals of the individual metal atoms o Like dissolves like
combine to form molecular orbitals in which the electrons o polar solutes dissolve in polar solvents
are no longer associated with an individual nucleus, but o Nonpolar solutes dissolve in nonpolar solvents
rather are free to move throughout the entire metallic solid o Molecules with similar intermolecular forces will mix freely
 Fe, ag, au, cu, alloys(sea of electrons model.
IONIC SOLUTE WITH POLAR SOLVENT

IONIC SOLUTE WITH NONPOLAR SOLVENT

MOLECULAR SOLIDS
 Individual molecules are held together by intermolecular
attractive forces such as dispersion forces, dipole-dipole
interactions, or hydrogen bonding
 H2o(ice), co, co2, ch3coch3 (acetone)

NON POLAR SOLUTE WITH NONPOLAR SOLVENT

AMORPHOUS SOLIDS
 Atoms are held together in a three-dimensional network by
covalent bonds, but the solid does not have a specific
crystalline structure
 Sio2(glass), polyethylene, nylon
NONPOLAR SOLUTE
WITH POLAR SOLVENT

 NON-POLAR COVALENT – LOW MP AND BP

POLAR COVALENT – HIGH MP AND BP
POLAR IONIC (ALWAYS POLAR) – HIGH MP AND BP
PHASE CHANGES
o Changes in the phase of a substance (solid, Liquid, or vapor) occur
when the amount of Kinetic energy in the substance is changed.
 When energy is put into the system from the
surroundings, we get:
 Melting—transition from solid liquid
 Boiling—transition from liquid vapor
 Sublimation—transition from solid vapor
 When energy is removed from the system, we
get condensation, freezing, or deposition
 The energy associated with a phase transition is called the
enthalpy of: vaporization, δhvap— boiling fusion, δhfus—
melting sublimation, δhsub—sublimation
