Chemistry 2

ENDR2104
Dr Sulaiman Al-Isaee
Office 110

Email: Sulaimanas.soh@cas.edu.om
• Credit Hours: 4

• Practical component: 15 %
• Two mid exams: 15% each = 30 %
• Lab exam: 5%
• Quiz: 5%
• Final Exam: 45 %

• Recommended book:
Zumdahl, Chemistry, 7th edition, 2003.
Week Chapters Subjects Tests
Liquids and Solids
1 10
Liquids and Solids
2 10
Properties of Solutions
3 11
Chemical Kinetics
4 12

Chemical Equilibrium
5 13

Test 1
6 14 Acids and Bases

Acid–Base Equilibria
7 15
15 Acid–Base Equilibria
8
 16 Solubility and Complex Ion
9 Equilibria

16 Solubility and Complex Ion

10 Equilibria

17 Spontaneity, Entropy and

11 Free Energy

17 Spontaneity, Entropy and Test 2

12 Free Energy
18 Electrochemistry
13
18 Electrochemistry
14

15 Review
ATTRACTIVE FORCES

Intramolecular forces bonding forces

These forces exist within each molecule.

They influence the chemical properties of the substance.

Intermolecular forces Not a real chemical bonding

These forces exist between molecules.

They influence the physical properties of the substance.
Intramolecular Bonding

Atoms share e- molecules

H. + H. H-H
2H2 + O2 2H2O

Intramolecular interactions (molecule bonding)

 Intermolecular Forces
• Forces that occur between molecules.
▪ Dipole–dipole forces
➢ Hydrogen bonding
▪ London dispersion forces (Van der Waals)

Molecule A Molecule A
Aggregate
 +

• When a substance changes from solid to liquid to gas, the

molecules remain intact.
• The changes in state are due to changes in the forces among
molecules rather than in those within the molecules.
 Dipole-Dipole Forces
It occurs due to the attractions between molecules that have
dipole moments.

• Dipole moment – molecules with polar bonds often behave

in an electric field as if they had a center of positive charge
and a center of negative charge.
• Molecules with dipole moments can attract each other
electrostatically. They line up so that the positive and
negative ends are close to each other.
What will happen in a condensed state of a substance?
The dipoles find the best compromise between attraction
and repulsion.
 Hydrogen Bond Forces
The hydrogen bond is a special form of the
Dipole-Dipole force, its not really a true chemical bond.

- It is the strongest intermolecular force

- much stronger than either Dipole-Dipole

Or Dispersion forces.

However It can ONLY exist when a Hydrogen atom

is present in the molecule AND it’s bonded to …

- Either a N, O, or F atom also present in the

same molecule.
In all compounds that form H-bonds the
Hydrogen atom is ALWAYS the Positive Dipole.

O, F, or N is ALWAYS the negative

Dipole

As one molecule approaches +

another the positive Hydrogen
aligns with the negative O, F, or N. -

H F
+ -
 All Hydrogen bonds are stronger than either
Dispersion or dipole-dipole interactions.

However, among molecules with

Hydrogen bonds there are some that
Are stronger than others.

How do we determine what H-bonds

are the strongest?

Strength of H-bond: F>O>>N

 Water Alignment during formation of the H-Bond

Positive aligns to negative

Water molecules in ice align to form a repeating hexagon

Compounds that form Hydrogen bonds take a lot
more energy to move molecules from the liquid phase
Into the gas phase.

Molecules of similar molecular weight without the

Ability to form H-bonds have higher vapor pressures
And thus lower B.P.
London Dispersion Forces
• A nonpolar molecule is a molecule that has a symmetrical
shape.
• A nonpolar molecule is a molecule in which the electrons are
usually able to distribute themselves in a balanced manner.
H
 
O C O H H H C H
 
H
• A nonpolar molecule is a molecule with NO permanent
positive or permanent negative end.
• As the electrons move about the molecule, they are usually
spread out in a balanced manner.
• This balanced arrangement of the electrons causes the
molecule to have no permanent positive or negative end.
 ?

• How do molecules without permanent positive and negative

ends attract each other?
 δ + δ -

•• In
When
theirthis
random
happens,
movements,
a temporary
the electrons
polar molecule is
sometimes
formed! are NOT distributed in a balanced
manner around the molecule!
 δ+ δ- δ+ δ-

• London
A temporary
dispersion
polar molecule
forces arewill
weakcause
intermittent
neighbor-ing
forces
between nonpolar
nonpolar moleculesmolecules.
to become temporary polar
molecules.
• The forces that hold the individual atoms in CO2 molecules
together are covalent bonds.
• The forces that hold CO2 molecules to each other in a sample
of dry ice are London dispersion forces.

     
O =C =O O =C =O O =C =O
     
     
O =C =O O =C =O O =C =O
     
     
O =C =O O =C =O O =C =O
     
• Generally, the more massive the nonpolar molecule is, the
stronger the London dispersion forces will be and the stronger
the London dispersion forces is, the higher the boiling point
will be!
larger electron clouds are easier to deform

CH4 C8H18

Smaller molecule Larger molecule

 Melting and Boiling Points

• In general, the stronger the intermolecular forces, the higher the melting
and boiling points.
 Concept Check
Which are stronger, intramolecular bonds or
intermolecular forces?

How do you know?

 Concept Check
Which molecule is capable of forming stronger
intermolecular forces?

N2 H2O

Explain.
Liquids
The particles of a liquid are closer together and more order
than those of a gas and are less order than those of a solid.

Liquids have a definite volume and a relatively high density,

and they are relatively incompressible. Like gases, liquids
can flow and thus are considered to be fluids.
Nature of Liquids
Density
Liquids can vary in density, but most liquids will have a density
1000 times higher than the density in the gas state. A higher
density is due to the closer arrangement of the particles
Nature of Liquids
Compressibility
• Liquids are much less compressible than gases.
• If liquid is compressed at 20 ˚C by 100 atm, its volume only
decreases by 4%.
• This has to do with the high density of liquids.
Nature of Liquids
Surface tension:
It is the resistance of a liquid to an increase in its
surface area:
▪ Liquids with large intermolecular forces tend to
have high surface tensions (degree of surface
tension).
▪ Cohesive forces – intermolecular forces among
the molecules of the liquid.
Beads of
Water on a
Waxed Car
Finish
 The molecular basis of surface tension.

hydrogen bonding
occurs across the surface
and below the surface
the net vector
for attractive
forces is downward

hydrogen bonding
occurs in three
dimensions
Capillary Action
Spontaneous rise of a liquid in a narrow tube.
Cohesive forces exist between water molecules in a liquid.
Adhesive forces exist between water molecules and the walls
of the container.
When the cohesive forces between molecules are less than the
adhesive forces between liquid and container, the liquid will
move up the walls of the container.
 Capillary Action in Action
Shape of the meniscus reflects the relative strength
of cohesive forces within the liquid and adhesive
forces between the liquid and the tube.

If convex:
adhesive forces < cohesive forces

If concave:
adhesive forces > cohesive forces

Hg H2 O
 Shape of water or mercury meniscus in glass.

capillarity

stronger
adhesive forces cohesive forces

H 2O Hg
Liquids
• Viscosity – measure of a liquid’s resistance to flow:
▪ Liquids with large intermolecular forces or molecular
complexity tend to be highly viscous.

37
Molecular complexity
Gasoline vs Grease
Evaporation
Evaporation or Vaporization:
Escape of molecules from the liquid to the gas phase.

Liquid Vapor

Molecules in the liquid state have

different kinetic energies (KEs).

Those with higher KEs can overcome

attractive forces between particles
and escape to the gas phase.
 Evaporation
Vaporization is endothermic because energy is required to
overcome the relatively strong intermolecular forces in the
liquid.
The energy required to vaporize 1 mole of a
liquid at a pressure of 1 atm is called the
enthalpy of vaporization, ΔHvap
Vapor Pressure
Molecules from the liquid phase can escape to the vapor phase
through evaporation.
Molecules in the gas phase can strike the surface of the liquid
and return to the liquid phase.

This process is called condensation.

In a closed container, an equilibrium develops between

molecules evaporating and condensing.
evaporation
liquid vapor
condensation
Vapor pressure: pressure exerted by a vapor in equilibrium with
its liquid phase.

Open system: nonequilibrium process.

Within their range of speeds, some molecules at the surface
have a high enough kinetic energy to overcome attractions
and vaporize.
Nearby molecules fill the gap, and with heat supplied by the
constant-temperature surroundings, the process continues
until the entire liquid phase is gone.
Vapor pressure: pressure exerted by a vapor in equilibrium with
its liquid phase.
Independent of the quantity of liquid or its surface area.
Increases with increasing temperature.
Depends on the strength of attraction between
molecules in the liquid state.

Volatile liquids: very weak attractive forces between molecules.

Evaporate very rapidly at ambient temperature. Have high
vapor pressures as a result.
Measuring Vapor Pressure of a Liquid

Measure using a barometer.

Vapor from the liquid exerts a

force on the Hg and pushes the
column downward.

The difference in height relative to

vacuum provides the vapor
pressure for the liquid.
• Liquids in which the intermolecular forces are strong
have relatively low vapor pressures.
• Vapor pressure increases significantly with temperature.
Vapor pressure as a function of temperature and
intermolecular forces.

• The effect of temperature is seen in the

steeper rise as the temperature
increases.
• The effect of intermolecular forces is
seen in the values of the vapor pressure.
Vapor Pressure vs. Temperature
Clausius-Clapeyron Equation
It has been demonstrated that the
logarithm of the vapor pressure of
a liquid varies linearly with
absolute temperature.
 Pvap,T  H vap  1 1
ln   = T −
T1 
1

 Pvap,T  R  2 
 2 
P = vapor pressure
vap

ΔH = enthalpy of vaporization
vap
A linear plot of vapor pressure-
R = 8.3145 J/K·mol temperature relationship.
T = temperature (in kelvin)
SAMPLE PROBLEM 12.1 Using the Clausius-Clapeyron Equation

PROBLEM: The vapor pressure of ethanol is 115 torr at 34.90C. If Hvap of

ethanol is 40.5 kJ/mol, calculate the temperature (in 0C) when
the vapor pressure is 760 torr.

PLAN: We are given 4 of the 5 variables in the Clausius-Clapeyron

equation. Substitute and solve for T2.

SOLUTION: P2 -Hvap  1 1 
ln =  −  34.90C = 308.0K
P1 R  T2 T1

760 torr -40.5 x103 J/mol 1 1

ln = -
115 torr 8.314 J/mol*K T2 308K

T2 = 350K = 770C
Changes of State
Heat of fusion: energy required to change 1 mole
of a solid at its melting point to a liquid.
Heat of
vaporization
Boiling

Melting

Heat of fusion

Heat of vaporization: energy required to change 1 mole

of a liquid to vapor at its normal boiling point.
 Concept Check
Which would you predict should be larger for a
given substance: Hvap or Hfus?

Explain why.
Phase Diagrams

• A phase diagram is a graphical way to summarize the

conditions under which the different states of a
substance are stable.
– The diagram is divided into three areas representing
each state of the substance.
– The curves separating each area represent the
boundaries of phase changes.
Phase Diagrams
• Below is a typical phase diagram. It consists of three
curves that divide the diagram into regions labeled
“solid, liquid, and gas”.

B . C
pressure

solid liquid

D
. A
gas

temperature
Phase Diagrams
• Curve AB, dividing the solid region from the liquid
region, represents the conditions under which the solid
and liquid are in equilibrium.

B . C
pressure

solid liquid

. A
gas
D
temperature
Phase Diagrams
• Usually, the melting point is only slightly affected by
pressure. For this reason, the melting point curve, AB,
is nearly vertical.

B . C
pressure

solid liquid

. A
gas
D
temperature
Phase Diagrams
• If a liquid is more dense than its solid, the curve leans
slightly to the left, causing the melting point to
decrease with pressure.

B . C
pressure

solid liquid

. A
gas
D
temperature
Phase Diagrams
• If a liquid is less dense than its solid, the curve leans
slightly to the right, causing the melting point to
increase with pressure.

B . C
pressure

solid liquid

. A
gas
D
temperature
Phase Diagrams
• Curve AC, which divides the liquid region from the
gaseous region, represents the boiling points of the
liquid for various pressures.

B . C
pressure

solid liquid

. A
gas
D
temperature
Phase Diagrams
• Curve AD, which divides the solid region from the
gaseous region, represents the vapor pressures of the
solid at various temperatures.

B . C
pressure

solid liquid

. A
gas
D
temperature
Phase Diagrams
• The curves intersect at A, the triple point, which is the
temperature and pressure where three phases of a
substance exist in equilibrium.

B . C
pressure

solid liquid

. A
gas
D
temperature
Phase Diagrams
• The temperature above which the liquid state of a
substance no longer exists regardless of pressure is
called the critical temperature.

B . C
pressure

solid liquid

. A
gas
D Tcrit
temperature
Phase Diagrams
• The vapor pressure at the critical temperature is called
the critical pressure. Note that curve AC ends at the
critical point, C.

Pcrit B . C
pressure

solid liquid

. A
gas
D Tcrit
temperature
Solid State
• A solid is a nearly incompressible state of matter with a
well-defined shape. The units making up the solid are
in close contact and in fixed positions.

– Solids are characterized by the type of force

holding the structural units together.
– In some cases, these forces are intermolecular, but
in others they are chemical bonds (metallic, ionic,
or covalent).
From this point of view, there are four types of solids.
• Molecular (Van der Waals forces)
• Metallic (Metallic bond)
• Ionic (Ionic bond)
• Covalent (Covalent bond)
Types of Solids
• A molecular solid is a solid that consists of atoms or
molecules held together by intermolecular forces.
– Many solids are of this type.
– Examples include solid neon,
solid water (ice), and solid
carbon dioxide (dry ice).
Types of Solids
• A metallic solid is a solid that consists of positive
cores of atoms held together by a surrounding “sea” of
electrons (metallic bonding).
– In this kind of bonding, positively charged atomic
cores are surrounded by delocalized electrons.
– Examples include iron, copper, and silver.
 Types of Solids
• An ionic solid is a solid that consists of
cations and anions held together by
electrical attraction of opposite charges
(ionic bond).
– Examples include cesium chloride,
sodium chloride, and zinc sulfide
(but ZnS has considerable covalent
character).
 Types of Solids
• A covalent network solid is a solid that consists of
atoms held together in large networks or chains by
covalent bonds.
– Examples include carbon, in its forms as diamond
or graphite asbestos and silicon carbide.
 Atomic Arrangement

Crystalline – periodic arrangement of atoms: definite

repetitive pattern
Non-crystalline or Amorphous – random arrangement
of atoms.
 Crystal Structure Basics

1. Crystal, a piece of a crystalline Solid.

2. Lattice, a three-dimensional system of points designating the

positions of the components (atoms, ions, or molecules) that make
up the substance.

3. Unit cell, the smallest repeating unit of the lattice.

X-ray diffraction are most commonly used to determine the structures of
crystalline solids
What is X-ray?
Beams of electromagnetic radiation.

*smaller wavelength than visible light,

*higher energy
*more penetrative
 How Diffraction Works: Bragg’s Law
• Bragg assume that each crystal plane reflects radiation as a mirror and analyze
this situation for cases of constructive and destructive interference.

• Bragg’s Law gives the conditions for constructive interference.

n = 2d sin 
n = integer, λ = wavelength of the X rays, d = distance between the atoms,
θ = angle of incidence and reflection.
 Metallic Bonds and the Properties of Metals
• The electron sea model proposes that all metal atoms in
a metallic solid contribute their valence electrons to
form a "sea" of electrons.
• The electrons are free to move around and are referred
to as delocalized electrons, forming a metallic cation.
Metallic Bonds and the Properties of
Metals
• A metallic bond is the attraction of an metallic cation
for delocalized electrons.
 Metallic Bonds and the Properties of
Metals
• Metals are malleable because they can be hammered
into sheets.

• Metals are ductile because they can be drawn into wires.

A metallic crystal can be pictured as containing spherical atoms packed
together and bonded to each other equally in all directions.

The closest packing model for metallic crystals assumes that metal atoms are
uniform, hard spheres.

The spheres are packed in layers. Each sphere is surrounded by six others.
 The Closest Packing Arrangement of Uniform
Spheres
• aba packing – the 2nd layer is like the 1st but it is displaced so that
each sphere in the 2nd layer occupies a dimple in the 1st layer.
• The spheres in the 3rd layer occupy dimples in the 2nd layer so that
the spheres in the 3rd layer lie directly over those in the 1st layer.
 The Closest Packing Arrangement of Uniform
Spheres
• abc packing – the spheres in the 3rd layer occupy dimples in the 2nd
layer so that no spheres in the 3rd layer lie above any in the 1st
layer.
• The 4th layer is like the 1st.
The aba arrangement has the hexagonal unit cell and the resulting structure is
called the hexagonal closest packed (hcp) structure.
The abc arrangement has a face-centered cubic unit cell and the
resulting structure is called the cubic closest packed (ccp)
structure.
How can we know the net number of spheres (atoms) in a unit cell?
The Net Number of Spheres in a Face-Centered Cubic Unit Cell
 Calculating the Density of a Closest Packed Solid
Silver crystallizes in a cubic closest packed structure. The radius of a
silver atom is 144 pm. Calculate the density of solid silver.
𝑚𝑎𝑠𝑠
𝑑𝑒𝑛𝑠𝑖𝑡𝑦 =
𝑣𝑜𝑙𝑢𝑚𝑒

The structure is cubic closest packed, which means the

unit cell is face-centered cubic

Note that in this structure the atoms touch along the diagonals
for each face and not along the edges of the cube.

Thus the length of the diagonal is r + 2r + r, or 4r. We use this fact to find
the length of the edge of the cube by the Pythagorean theorem:
The square of the hypotenuse of a right triangle is equal to the sum of the
squares on the other two sides.
 𝑑 2 + 𝑑 2 = (4𝑟)2
2𝑑 2 = 16𝑟 2
𝑑 2 = 8𝑟 2
𝑑 = 8𝑟 2 = r 8

𝑑= (144 pm) 8

𝑑 = 407 𝑝𝑚
3
1.00×10−10 𝑐𝑚
𝑑3 = (407)3 𝑝𝑚 × = 6.74 × 10−23 𝑐𝑚3
1𝑝𝑚

Since we know that the net number of atoms in the face-centered

cubic unit cell is 4, we have 4 silver atoms contained in a volume
of 6.74 × 10−23 𝑐𝑚3
Bonding in Metals
• The electron-sea model is a simple depiction of a metal as an
array of positive ions surrounded by delocalized valence
electrons.

– Metals are good conductors of electricity because of the mobility

of these delocalized valence electrons.

– A metal also conducts heat well because the mobile electrons can carry
additional kinetic energy.
Bonding in Metals
Bonding in Metals
• Molecular orbital theory gives a more detailed picture of the
bonding in metals.
– According to the MO theory, atomic orbitals overlap to produce a set of
molecular orbitals. The number of generated molecular orbitals is equal
to the number of overlapping atomic orbitals. There is a very large
number of atomic orbitals in a metal!!!
– Because the energy levels in a metal crowd together into bands, this
picture of metal bonding is called band theory.
Bonding in Metals

• Molecular orbital theory gives a more detailed picture of the

bonding in metals.

– According to band theory, the electrons in a crystal become free to

move when they are excited to the unoccupied orbitals of a band.
Bonding in Metals

• Molecular orbital theory gives a more detailed picture of the

bonding in metals.

– In a metal, this requires little energy since the unoccupied

orbitals lie just above the occupied orbitals of highest energy.
Sodium According to Band Theory

Conduction band:
empty 3s antibonding

No
gap
Valence band:
full 3s bonding
 What is a network solid?

• Network solids are macromolecules, giant structures of

covalently bonded atoms in one, two or three dimensional
arrays.

• Allotropes: elements that exist in different physical forms with

different physical properties but the same chemical properties.

For example graphite and diamond are allotropes of carbon .

Both diamond and graphite are made entirely out of carbon
but only graphite conducts electricity and diamond is one of the
hardest substances known.
Diamond

• 3-dimensional array of carbon atoms

covalently bonded in a tetrahedral
arrangement.
• Strong covalent bonds give diamond its
hardness.
• There are no delocalized electrons, therefore
diamond will not conduct electricity.
• There are several planes of atoms within the
crystal and diamonds are cut along these
planes. Light is reflected by these planes to
give diamonds their sparkle (total internal
refraction)
Partial Representation of the Molecular Orbital Energies in

a) Diamond b) a Typical Metal

Graphite

• Graphite is a 2-dimensional array of

carbon atoms arranged in layers of
hexagons.
• The electrons making up the “double
bonds”are actually delocalized
throughout the structure (i.e. not true
double bonds)
• The layers of hexagons are held in
place by van derWaalsforces
(intermolecular forces).
The p Orbitals and Pi-system in Graphite

a & b The p Orbitals (a) Perpendicular to the Plane of the Carbon Ring System in
Graphite can Combine to Form (b) an Extensive π Bonding Network

MO of π type contribute to
• Stability of graphite structure
• Electrical conductivity
Semiconductors
• Semiconductors are materials that essentially
can be conditioned to act as good
conductors, or good insulators, or any thing
in between.
• Common elements such as carbon, silicon,
and germanium are semiconductors.
• Silicon is the best and most widely used
semiconductor.
Semiconductor Valence Orbit

• The main characteristic

of a semiconductor
element is that it has
four electrons in its
outer or valence orbit.
Crystal Lattice Structure
• The unique capability of
semiconductor atoms is
their ability to link
together to form a
physical structure called
a crystal lattice.
• The atoms link together
with one another sharing
their outer electrons.
• These links are called
covalent bonds. 2D Crystal Lattice
Structure
Semiconductors can be
Insulators
• If the material is pure semiconductor material like
silicon, the crystal lattice structure forms an
excellent insulator since all the atoms are bound to
one another and are not free for current flow.
• Good insulating semiconductor material is referred
to as intrinsic.
• Since the outer valence electrons of each atom are
tightly bound together with one another, the
electrons are difficult to dislodge for current flow.
• Silicon in this form is a great insulator.
• Semiconductor material is often used as an insulator.
Doping
• To make the semiconductor conduct
electricity, other atoms called impurities must
be added.
• “Impurities” are different elements.
• This process is called doping.
Semiconductors can be Conductors
• An impurity, or element
like arsenic, has 5 valence
electrons.
• Adding arsenic (doping)
will allow four of the
arsenic valence electrons
to bond with the
neighboring silicon atoms.
• The one electron left over
for each arsenic atom
becomes available to
conduct current flow.
Resistance Effects of Doping
• If you use lots of arsenic atoms for doping, there will be lots of
extra electrons so the resistance of the material will be low
and current will flow freely.
• If you use only a few boron atoms, there will be fewer free
electrons so the resistance will be high and less current will
flow.
• By controlling the doping amount, virtually any resistance can
be achieved.
Another Way to Dope
• You can also dope a semiconductor
material with an atom such as
boron that has only 3 valence
electrons.
• The 3 electrons in the outer orbit
do form covalent bonds with its
neighboring semiconductor atoms
as before. But one electron is
missing from the bond.
• This place where a fourth electron
should be is referred to as a hole.
• The hole assumes a positive charge
so it can attract electrons from
some other source.
• Holes become a type of current
carrier like the electron to support
current flow.
Types of Semiconductor
Materials
• The silicon doped with extra electrons is called an “N type”
semiconductor.
• “N” is for negative, which is the charge of an electron.
• Silicon doped with material missing electrons that produce
locations called holes is called “P type” semiconductor.
• “P” is for positive, which is the charge of a hole.