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CHEMISTRY

Chapter 1
Atoms, molecules & chemical
bonding

David P. White

Prentice Hall © 2003 Chapter 6


The Discovery of Atomic
Structure

• The ancient Greeks were the first to postulate that matter


consists of indivisible constituents.
• John Dalton formulated definition of atoms
• Elements composed of extremely small particles called atoms.
All atoms of a given element are identical, having the same
size, mass and chemical properties.
• Compounds are composed of atoms of more than one element
• A chemical reaction involves only the separation, combination
or rearrangement of atoms

Prentice Hall © 2003 Chapter 2


The Discovery of Atomic
Structure

• Later scientists realized that the atom possess internal


structure- subatomic particles.

Cathode Rays and Electrons


• A cathode ray tube (CRT) is a hollow vessel with an
electrode at either end.
• A high voltage is applied across the electrodes.

Prentice Hall © 2003 Chapter 2


The Discovery of Atomic
Structure
Cathode Rays and Electrons
• The voltage causes negative particles to move from the
negative electrode to the positive electrode.
• The path of the electrons can be altered by the presence
of a magnetic field.
• Consider cathode rays leaving the positive electrode
through a small hole.
– If they interact with a magnetic field perpendicular to
an applied electric field, the cathode rays can be
deflected by different amounts.
Prentice Hall © 2003 Chapter 2
The Discovery of Atomic
Structure
Cathode Rays and Electrons
– The amount of deflection of the cathode rays depends
on the applied magnetic and electric fields.
– In turn, the amount of deflection also depends on the
charge to mass ratio of the electron.
• In 1897, Thomson determined the charge to mass ratio of
an electron to be 1.76  108 C/g.

Prentice Hall © 2003


The Discovery of Atomic
Structure
Cathode Rays and Electrons

Prentice Hall © 2003 Chapter 2


The Discovery of Atomic
Structure
Cathode Rays and Electrons
Consider the following experiment:
• Oil drops are sprayed above a positively charged plate
containing a small hole.
• As the oil drops fall through the hole, they are given a
negative charge.
• Gravity forces the drops downward. The applied electric
field forces the drops upward.
• When a drop is perfectly balanced, the weight of the drop
is equal to the electrostatic force of attraction between the
drop and the positive plate.
Prentice Hall © 2003 Chapter 2
The Discovery of Atomic
Structure
Cathode Rays and Electrons
The Discovery of Atomic
Structure
Cathode Rays and Electrons
• Using this experiment, Millikan determined the charge on
the electron to be 1.60  10-19 C.
• Knowing the charge to mass ratio, 1.76  108 C/g,
Millikan calculated the mass of the electron: 9.10  10-28
g.
• With more accurate numbers, we get the mass of the
electron to be 9.10939  10-28 g.

Prentice Hall © 2003 Chapter 2


The Discovery of Atomic
Structure
Radioactivity
Consider the following experiment:
• A radioactive substance is placed in a shield containing a
small hole so that a beam of radiation is emitted from the
hole.
• The radiation is passed between two electrically charged
plates and detected.
• Three spots are noted on the detector:
– a spot in the direction of the positive plate,
– a spot which is not affected by the electric field,
– a spot in the direction of the negative plate.
Prentice Hall © 2003 Chapter 2
The Discovery of Atomic
Structure
Radioactivity

Prentice Hall © 2003 Chapter 2


The Discovery of Atomic
Structure
Radioactivity
• A high deflection towards the positive plate corresponds
to radiation which is negatively charged and of low mass.
This is called -radiation (consists of electrons).
• No deflection corresponds to neutral radiation. This is
called -radiation.
• Small deflection towards the negatively charged plate
corresponds to high mass, positively charged radiation.
This is called -radiation.

Prentice Hall © 2003 Chapter 2


The Discovery of Atomic
Structure
The Nuclear Atom
• From the separation of
radiation we conclude that
the atom consists of neutral,
positively, and negatively
charged entities.
• Thomson assumed all these
charged species were found
in a sphere.
The Discovery of Atomic
Structure
The Nuclear Atom
• Rutherford carried out the following experiment:
• A source of -particles was placed at the mouth of a
circular detector.
• The  -particles were shot through a piece of gold foil.
• Most of the -particles went straight through the foil
without deflection.
• Some -particles were deflected at high angles.
• If the Thomson model of the atom was correct, then
Rutherford’s result was impossible.
Prentice Hall © 2003 Chapter 2
The Discovery of Atomic
Structure
The Nuclear Atom
• In order to get the majority of -particles through a piece
of foil to be undeflected, the majority of the atom must
consist of a low mass, diffuse negative charge  the
electron.
• To account for the small number of high deflections of
the -particles, the center or nucleus of the atom must
consist of a dense positive charge.

Prentice Hall © 2003 Chapter 2


The Discovery of
Atomic Structure
The Nuclear Atom
• Rutherford modified
Thomson’s model as follows:
– assume the atom is spherical
but the positive charge must
be located at the center, with
a diffuse negative charge
surrounding it.
The Discovery of Atomic
Structure
The Neutron
• Hydrogen contains only one proton and Helium contains
two protons.
• Therefore the ratio of mass of He to H should be 2:1
• However, in reality the ratio is 4:1
• Thus there is another type of subatomic particle
• Chadwick bombarded a thin sheet of beryllium with α
particles, a very high energy radiation similar to γ rays
was emitted by the metal  Neutrons

Prentice Hall © 2003 Chapter 2


The Discovery of Atomic
Structure

Mass and charge of subatomic particles


Particle Mass (g) Coulomb Charge unit

Electron 9.10939 x 10-28 -1.6022 x 10-19 -1

Proton 1.67262 x 10-24 +1.6022 x 10-19 +1

Neutron 1.67493 x 10-24 0 0

Prentice Hall © 2003 Chapter 2


The Modern View of
Atomic Structure

• The atom consists of positive, negative, and neutral


entities (protons, electrons, and neutrons).
• Protons and neutrons are located in the nucleus of the
atom, which is small. Most of the mass of the atom is
due to the nucleus.
– There can be a variable number of neutrons for the
same number of protons. Isotopes have the same
number of protons but different numbers of neutrons.
• Electrons are located outside of the nucleus. Most of the
volume of the atom is due to electrons.
Prentice Hall © 2003 Chapter 2
The Modern View of
Atomic Structure

Prentice Hall © 2003 Chapter 2


The structure of the atom

• Matter consists of very small, indivisible particles, which


are named atoms
• Atoms are made up of subatomic particles- p, n & e
– Electron: negative charge,
– Theories about the energy and the arrangement of electrons in
atoms are based on the interaction of matter with
electromagnetic radiation.
– dual nature: wave & particle

Prentice Hall © 2003 Chapter 6


The Wave Nature of Light

• All waves have a characteristic length, height & number


of waves that pass through a certain point in one second
• wavelength, 
• amplitude, A.
• The frequency, 
• The frequency of electromagnetic radiation is related to
its wavelength by:

c  
Prentice Hall © 2003 Chapter 6
The Wave Nature of Light
The Wave Nature of Light

• Electromagnetic radiation moves through a vacuum with


a speed of 2.99792458  10-8 m/s.
• Electromagnetic waves have characteristic wavelengths
and frequencies.
• Example: visible radiation has wavelengths between 400
nm (violet) and 750 nm (red).

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Example

• The wavelength of the green light from a traffic signal is


centered at 522nm. What is the frequency?

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The Wave Nature of Light
The Wave Nature of Light

Prentice Hall © 2003 Chapter 6


Planck’s Quantum Theory

• Heated solid emits radiation over a wide range of


wavelength
• Dependence of amount of radiation energy emitted by an
object at a certain temperature depends on its
wavelength- dependence partially successful with wave
theory and TD law.
Quantized Energy and
Photons
• Planck: energy can only be absorbed or released from
atoms in certain small amounts called a quantum (=Fixed
quantity of energy).
• The relationship between energy and frequency is
E  h
where h is Planck’s constant (6.626  10-34 J.s).
• There is an important relationship between energy and
wavelength of radiation:
E  hc/ 
Prentice Hall © 2003 Chapter 6
Quantized Energy and
Photons
The Photoelectric Effect and Photons
• Einstein assumed that light traveled in energy packets
(stream of particles) called photons.
• The energy of one photon:
E  h

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Chapter 6
Photoelectric effect

• Must employ light of sufficient frequency (E=h)


• Number of electrons ejected proportional to intensity
– More intense more photons
– Thus more electrons ejected
• Energy ejected electrons not proportional to intensity
– h
Line Spectra and the Bohr
Model
• Rutherford assumed the electrons orbited the nucleus
analogous to planets around the sun.
• However, a charged particle moving in a circular path
should lose energy.
• This means that the atom should be unstable according to
Rutherford’s theory.
• Bohr noted the line spectra of certain elements and
assumed the electrons were confined to specific energy
states. These were called orbits.
Chapter 6
Prentice Hall © 2003
Line Spectra and the Bohr
Model
Bohr Model
• Since the energy states are quantized, the light emitted
from excited atoms must be quantized and appear as line
spectra.
• After lots of math, Bohr showed that


E   2.18  10 18

 1 
J 2
n 
where n is the principal quantum number (i.e., n = 1, 2, 3, … and nothing else).
the –ve sign indicates that the energy of the electron in the atom is lower than the
energy of a free electron

Prentice Hall © 2003 Chapter 6


Line Spectra and the Bohr
Model
Bohr Model
• The first orbit in the Bohr model has n = 1, is closest to
the nucleus, and has negative energy by convention.
• The furthest orbit in the Bohr model has n close to
infinity and corresponds to zero energy.
• Electrons in the Bohr model can only move between
orbits by absorbing and emitting energy in quanta (h).
• The amount of energy absorbed or emitted on movement
between states is given by
E  E f  Ei  h
Prentice Hall © 2003 Chapter 6
Line Spectra and the Bohr
Model
Bohr Model
• We can show that
 1 
E  h 
hc

 n
 n
1
  2.18  1018 J  2  2 

 f i 

• When ni > nf, energy is emitted.


• When nf > ni, energy is absorbed

Prentice Hall © 2003 Chapter 6


Line Spectra and
the Bohr Model
Bohr Model
The Wave Behavior of
Matter
• Knowing that light has a particle nature, it seems
reasonable to ask if matter has a wave nature.
• Using Einstein’s and Planck’s equations, de Broglie
showed: 
h
mv
• The momentum, mv, is a particle property, whereas  is a
wave property.
• de Broglie summarized the concepts of waves and
particles, with noticeable effects if the objects are small.
Prentice Hall © 2003 Chapter 6
The Wave Behavior of
Matter
The Uncertainty Principle
• Heisenberg’s Uncertainty Principle: on the mass scale
of atomic particles, we cannot determine exactly the
position, direction of motion, and speed simultaneously.
• For electrons: we cannot determine their momentum and
position simultaneously.
• If x is the uncertainty in position and mv is the
uncertainty in momentum, then
h
x·mv 
4
Prentice Hall © 2003 Chapter 6
Quantum Mechanics and
Atomic Orbitals
• Schrödinger proposed an equation that contains both
wave and particle terms.
• Solving the equation leads to wave functions.
• The wave function gives the shape of the electronic
orbital.
• The square of the wave function, gives the probability of
finding the electron,
• that is, gives the electron density for the atom.

Prentice Hall © 2003 Chapter 6


Quantum Mechanics and
Atomic Orbitals

Prentice Hall © 2003 Chapter 6


Quantum Mechanics and
Atomic Orbitals
Orbitals and Quantum Numbers
• If we solve the Schrödinger equation, we get wave
functions and energies for the wave functions.
• We call wave functions orbitals.
• Keep in mind that orbital in the quantum-mechanical
model bears no resemblance to an orbit in the Bohr
model. An orbit is an electron’s path around the nucleus
whereas, an orbital is a mathematical function with no
direct physical meaning.

Prentice Hall © 2003 Chapter 6


Quantum Mechanics and
Atomic Orbitals
An atomic orbital is specified by 3 quantum numbers:
1. Principal Quantum Number, n, related to the size of the orbital. This
is the same as Bohr’s n. As n becomes larger, the atom becomes larger and
the electron is further from the nucleus. The higher the value of n, the
higher the energy level.
2. Orbital Angular Momentum (or, Azimuthal) Quantum Number, l.
(related to shape). This quantum number depends on the value of n. The
number of l value= the number of n value. The values of l begin at 0 and
increase to (n - 1). We usually use letters for l (s, p, d and f for l = 0, 1, 2,
and 3, respectively). Usually we refer to the s, p, d and f-orbitals.
3. Magnetic Quantum Number, ml related to orientation in space. This
quantum number depends on l. The magnetic quantum number has
integral values between -l and +l. The number of possible ml values equals
the number of orbitals, which is 2l+1 for a given l value.
Prentice Hall © 2003 Chapter 6
Quantum Mechanics and
Atomic Orbitals
• Shell/level – The atom’s energy shells or levels, are given by the
value n. The smaller the value of n, the lower the energy level and
closer to the nucleus.
• Subshell/sublevel – The atom’s shells/levels contian
subshells/sublevels, which designate the orbital shape. Each
subshell has a letter designation:
• l = 0 is an s subshell, l = 1 is a p subshell
l = 2 is a d subshell, l = 3 is an f subshell.
• The letters derived from the names of spectroscopic lines:
Sharp, principal, diffuse and fundamental.
Subshells are named by joining the n value and the letter
designation. For example, n=2 and l=0 is called 2s subshell.
Prentice Hall © 2003 Chapter 6
Quantum Mechanics and
Atomic Orbitals
• Orbital – Each allowed combination of n, l and ml values specifies
one of the atom’s orbitals to describe the shape, size and the
spatial orientation.
• The value of n = the number of possible l values (an integer from 0
to n-1).
So, when n=2, l will have only two values, 0 and 1.
• The number of orbitals in each subshell is 2l+1 for a given l value.
One s orbital (l=0), 3 p orbitals (l=1) and 5 d orbitals (l=2) and 7 f
orbitals (l=3).
• Again, the total number of orbitals = n2.
Prentice Hall © 2003 Chapter 6
Quantum Mechanics and
Atomic Orbitals
• How many orbitals exist for n = 3?
• For n = 3, l will have 3 values, i.e., 0, 1 and 2.
• For l = 0, ml will have 0 value (as -l, 0 and +l)
• For l = 1, ml will have 3 values (-1, 0 and +1)
• For l = 2, ml will have 5 values, -2 through 0 to +2.
(i.e., -2, -1, 0 ,+1 and +2).
• There are 9 ml values which means 9 orbitals. In other
words, n2=32=9.
Prentice Hall © 2003 Chapter 6
Quantum Mechanics and
Atomic Orbitals
Orbitals and Quantum Numbers

Prentice Hall © 2003 Chapter 6


Many-Electron Atoms
Electron Spin and the Pauli Exclusion Principle

• Spin is an intrinsic property of an electron and this is another


quantum number besides the other three. This is not a property of
the orbitals.
• A beam of atoms was passed through a slit and into a magnetic
field and the atoms were then detected.
• Two spots were found: one with the electrons spinning in one
direction and one with the electrons spinning in the opposite
direction.

Prentice Hall © 2003 Chapter 6


Many-Electron Atoms
Electron Spin and the Pauli Exclusion Principle

Prentice Hall © 2003 Chapter 6


Many-Electron Atoms
Electron Spin and the Pauli Exclusion Principle
• Since electron spin is quantized, we define ms = spin quantum
number =  ½.
• Pauli’s Exclusions Principle: no two electrons can have the same
set of 4 quantum numbers.
– Therefore, two electrons in the same orbital must have opposite
spins.

Prentice Hall © 2003 Chapter 6


Quantum Mechanics and
Atomic Orbitals
Orbitals and Quantum Numbers
• Orbitals can be ranked in terms of energy to yield an
Aufbau diagram.
• Note that the following Aufbau diagram is for a single
electron system.
• As n increases, note that the spacing between energy
levels becomes smaller.

Prentice Hall © 2003 Chapter 6


Quantum
Mechanics and
Atomic
Orbitals
Orbitals and Quantum Numbers

Prentice Hall © 2003 Chapter 6


Representations of
Orbitals
The s-Orbitals

Prentice Hall © 2003 Chapter 6


Representations of
Orbitals
The p, d and f -Orbitals
• There are three p-orbitals px, py, and pz.
• The three p-orbitals lie along the x-, y- and z- axes.
• The letters correspond to allowed values of ml of -1, 0,
and +1.
• The orbitals are dumbbell shaped.
• As n increases, the p-orbitals get larger.
• There are five d and seven f-orbitals.

Prentice Hall © 2003 Chapter 6


Representations of
Orbitals
The p-Orbitals

Prentice Hall © 2003 Chapter 6


Many-Electron Atoms
Orbitals and Their Energies
• The Aufbau diagram looks slightly different for many-
electron systems.

Prentice Hall © 2003 Chapter 6


Orbitals and Their Energies

Many-Electron Atoms
Electron Configurations
Hund’s Rule
• Electron configurations tell us in which orbitals the
electrons for an element are located.
• Hund’s rule: When more than one orbital has the same
energy, electrons occupy separate orbitals and do so
with parallel spins.
• Electrons fill orbitals starting with lowest n and moving upwards;
• No two electrons can fill one orbital with the same spin
(Pauli).

Prentice Hall © 2003 Chapter 6


Electron Configurations
Condensed Electron Configurations
• Neon completes the 2p subshell.
• Sodium marks the beginning of a new row. So, we write
the condensed electron configuration for sodium as - Na:
[Ne] 3s1. [Ne] represents the electron configuration of
neon.
• Inner (core) electrons: electrons in [Noble Gas].They
fill all the lower energy levels of an atom.
• Valence electrons: electrons outside of [Noble Gas].

Prentice Hall © 2003 Chapter 6


Electron Configurations
Transition Metals
• After Ar the d orbitals begin to fill.
• After the 3d orbitals are full, the 4p orbitals being to fill.
• Transition metals: elements in which the d electrons are
the valence electrons.

Prentice Hall © 2003 Chapter 6


Electron Configurations
Lanthanides and Actinides
• From Ce onwards the 4f orbitals begin to fill.
• Note: La: [Xe]6s25d14f0
• Elements Ce - Lu have the 4f orbitals filled and are
called lanthanides or rare earth elements.
• Elements Th - Lr have the 5f orbitals filled and are
called actinides.
• Most actinides are not found in nature.

Prentice Hall © 2003 Chapter 6


Electron Configurations
and the Periodic Table
• The periodic table can be used as a guide for electron
configurations.
• The period number is the value of n.
• Groups 1A and 2A have the s-orbital filled.
• Groups 3A - 8A have the p-orbital filled.
• Groups 3B - 2B have the d-orbital filled.
• The lanthanides and actinides have the f-orbital filled.

Prentice Hall © 2003 Chapter 6


Molecular Orbitals

Molecular Orbital (MO) Theory.


• Just as electrons in atoms are found in atomic orbitals,
electrons in molecules are found in molecular orbitals.

Prentice Hall © 2003 Chapter 9


Molecular Orbitals

• Molecular orbitals:
• each contain a maximum of two electrons;
• have definite energies;
• can be visualized with contour diagrams;
• are associated with an entire molecule.

Prentice Hall © 2003 Chapter 9


Molecular Orbitals

• Guideline to fill molecular orbitals with electrons:


• The number of MO formed is always equal to the # of atomic orbital
formed
• The more stable the bonding MO, the less stable the corresponding
antibonding MO
• The filling of MO proceeds from low to high energies.
• Each MO can accommodate up to two electrons with opposite spins in
accordance to Pauli exclusion principle
• When electrons are added to the same energy, electrons enter MO with
parallel spins
• The # of electrons in the MO is equal to the sum of all the electrons on the
bonding atoms
Prentice Hall © 2003 Chapter 9
Molecular Orbitals

The Hydrogen Molecule


• When two AOs overlap, two MOs form.
• Therefore, 1s (H) + 1s (H) must result in two MOs for H2:
• one has electron density between nuclei (bonding MO);
• one has little electron density between nuclei (antibonding
MO).
• MOs resulting from s orbitals are  MOs.
•  (bonding) MO is lower energy than * (antibonding) MO.

Prentice Hall © 2003 Chapter 9


Molecular Orbitals
The Hydrogen Molecule

Prentice Hall © 2003 Chapter 9


Molecular Orbitals
The Hydrogen Molecule
• Energy level diagram or MO diagram shows the energies
and electrons in an orbital.
• The total number of electrons in all atoms are placed in
the MOs starting from lowest energy (1s) and ending
when you run out of electrons.
• Note that electrons in MOs have opposite spins.
• H2 has two bonding electrons.
• He2 has two bonding electrons and two antibonding
electrons.
Prentice Hall © 2003 Chapter 9
Molecular Orbitals
The Hydrogen Molecule

Prentice Hall © 2003 Chapter 9


Molecular Orbitals
Bond Order
• Define
Bond order  1 bonding electrons - antibonding electrons
2
• Bond order = 1 for single bond.
• Bond order = 2 for double bond.
• Bond order = 3 for triple bond.
• Fractional bond orders are possible.
• For H2
• Bond order  12 2  0   1
Therefore, H2 has a single bond.
Prentice Hall © 2003 Chapter 9
Molecular Orbitals
Bond Order
• For He2
Bond order  1 2  2   0
2
• Therefore He2 is not a stable molecule

Prentice Hall © 2003 Chapter 9


Second-Row Diatomic
Molecules
• We look at homonuclear diatomic molecules (e.g. Li2,
Be2, B2 etc.).
• AOs combine according to the following rules:
• The number of MOs = number of AOs;
• AOs of similar energy combine;
• As overlap increases, the energy of the MO decreases;
• Pauli: each MO has at most two electrons;
• Hund: for degenerate orbitals, each MO is first occupied
singly.
Prentice Hall © 2003 Chapter 9
Second-Row Diatomic
Molecules
Molecular Orbitals for Li2 and Be2
• Each 1s orbital combines with another 1s orbital to give
one 1s and one *1s orbital, both of which are occupied
(since Li and Be have 1s2 electron configurations).
• Each 2s orbital combines with another 2s orbital, two
give one 2s and one *2s orbital.
• The energies of the 1s and 2s orbitals are sufficiently
different so that there is no cross-mixing of orbitals (i.e.
we do not get 1s + 2s).

Prentice Hall © 2003 Chapter 9


Second-Row Diatomic
Molecules
Molecular Orbitals for Li2 and Be2
• There are a total of 6 electrons in Li2:
• 2 electrons in 1s;
• 2 electrons in *1s;
• 2 electrons in 2s; and
• 0 electrons in *2s.
Bond order  1 4  2   1
2
• Since the 1s AOs are completely filled, the 1s and *1s
are filled. We generally ignore core electrons in MO
diagrams.
Prentice Hall © 2003 Chapter 9
Second-Row Diatomic
Molecules
Molecular Orbitals for Li2 and Be2
• There are a total of 8 electrons in Be2:
• 2 electrons in 1s;
• 2 electrons in *1s;
• 2 electrons in 2s; and
• 2 electrons in *2s.
Bond order  1 4  4   0
2
• Since the bond order is zero, Be2 does not exist.

Prentice Hall © 2003 Chapter 9


Second-Row Diatomic
Molecules
Molecular Orbitals from 2p Atomic
Orbitals
• There are two ways in which two p orbitals overlap:
• end-on so that the resulting MO has electron density on the
axis between nuclei (i.e.  type orbital);
• sideways so that the resulting MO has electron density above
and below the axis between nuclei (i.e.  type orbital).

Prentice Hall © 2003 Chapter 9


Second-Row Diatomic
Molecules
Molecular Orbitals from 2p Atomic
Orbitals
• The six p-orbitals (two sets of 3) must give rise to 6
MOs:
• , *, , *, , and *.
• Therefore there is a maximum of 2  bonds that can come
from p-orbitals.
• The relative energies of these six orbitals can change.

Prentice Hall © 2003 Chapter 9


Molecular
Orbitals from
2p Atomic
Orbitals
Second-Row Diatomic
Molecules
Configurations for B2 Through Ne2
• 2s Orbitals are lower in energy than 2p orbitals so 2s
orbitals are lower in energy than 2p orbitals.
• There is greater overlap between 2pz orbitals (they point
directly towards one another) so the 2p is MO is lower
in energy than the 2p orbitals.
• There is greater overlap between 2pz orbitals so the *2p
is MO is higher in energy than the *2p orbitals.
• The 2p and *2p orbitals are doubly degenerate.

Prentice Hall © 2003 Chapter 9


Second-Row Diatomic
Molecules
Configurations for B2 Through Ne2
• As the atomic number decreases, it becomes more likely
that a 2s orbital on one atom can interact with the 2p
orbital on the other.
• As the 2s-2p interaction increases, the 2s MO lowers in
energy and the 2p orbital increases in energy.
• For B2, C2 and N2 the 2p orbital is higher in energy than
the 2p.
• For O2, F2 and Ne2 the 2p orbital is lower in energy
than the 2p.
Prentice Hall © 2003 Chapter 9
Second-Row Diatomic
Molecules
Configurations for B2 Through Ne2
• Once the relative orbital energies are known, we add the
required number of electrons to the MOs, taking into
account Pauli’s exclusion principle and Hund’s rule.
• As bond order increases, bond length decreases.
• As bond order increases, bond energy increases.

Prentice Hall © 2003 Chapter 9


Second-Row Diatomic
Molecules
Configurations for B2 Through Ne2

Prentice Hall © 2003 Chapter 9


Second-Row Diatomic
Molecules
Electron Configurations and Molecular
Properties
• The MO diagram for O2 predicts both paramagnetism
and the double bond (bond order = 2).

Prentice Hall © 2003 Chapter 9


Chemical Bonds, and the
Octet Rule
• Chemical bond: attractive force holding two or more
atoms together.
• Covalent bond results from sharing electrons between
the atoms. Usually found between nonmetals.
• Ionic bond results from the transfer of electrons from a
metal to a nonmetal.
• Metallic bond: attractive force holding pure metals
together.

Prentice Hall © 2003 Chapter 8


Chemical Bonds and the
Octet Rule
The Octet Rule
• All noble gases except He has an s2p6 configuration.
• Octet rule: atoms tend to gain, lose, or share electrons
until they are surrounded by 8 valence electrons (4
electron pairs).
• Caution: there are many exceptions to the octet rule.

Prentice Hall © 2003 Chapter 8


Ionic Bonding

Consider the reaction between sodium and chlorine:


Na(s) + ½Cl2(g)  NaCl(s) Hºf = -410.9 kJ

Prentice Hall © 2003 Chapter 8


Ionic Bonding

• The reaction is violently exothermic.


• We infer that the NaCl is more stable than its constituent
elements. Why?
• Na has lost an electron to become Na+ and chlorine has
gained the electron to become Cl. Note: Na+ has an Ne
electron configuration and Cl has an Ar configuration.
• That is, both Na+ and Cl have an octet of electrons
surrounding the central ion.

Prentice Hall © 2003 Chapter 8


Ionic Bonding

• NaCl forms a very regular structure in which each Na+


ion is surrounded by 6 Cl ions.
• Similarly, each Cl ion is surrounded by six Na+ ions.
• There is a regular arrangement of Na+ and Cl in 3D.
• Note that the ions are packed as closely as possible.
• Note that it is not easy to find a molecular formula to
describe the ionic lattice.

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Ionic Bonding

Prentice Hall © 2003 Chapter 8


Ionic Bonding
Energetics of Ionic Bond Formation
• The formation of Na+(g) and Cl(g) from Na(g) and Cl(g)
is endothermic.
• Why is the formation of Na(s) exothermic?
• The reaction NaCl(s)  Na+(g) + Cl(g) is endothermic
(H = +788 kJ/mol).
• The formation of a crystal lattice from the ions in the gas
phase is exothermic:
Na+(g) + Cl(g)  NaCl(s) H = 788 kJ/mol
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Ionic Bonding
Energetics of Ionic Bond Formation
• Lattice energy: the energy required to completely
separate an ionic solid into its gaseous ions.
• Lattice energy depends on the charges on the ions and the
sizes of the ions:
Q1Q2
El  
d
 is a constant (8.99 x 10 9 J·m/C2), Q1 and Q2 are the
charges on the ions, and d is the distance between ions.
Prentice Hall © 2003 Chapter 8
Ionic Bonding
Energetics of Ionic Bond Formation
• Lattice energy increases as
• The charges on the ions increase
• The distance between the ions decreases.

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Ionic Bonding
Electron Configurations of Ions of the
Representative Elements
• These are derived from the electron configuration of
elements with the required number of electrons added or
removed from the most accessible orbital.
• Electron configurations can predict stable ion formation:
• Mg: [Ne]3s2
• Mg+: [Ne]3s1 not stable
• Mg2+: [Ne] stable
• Cl: [Ne]3s23p5
• Cl: [Ne]3s23p6 = [Ar] stable
Prentice Hall © 2003 Chapter 8
Covalent Bonding

• When two similar atoms bond, none of them wants to


lose or gain an electron to form an octet.
• When similar atoms bond, they share pairs of electrons to
each obtain an octet.
• Each pair of shared electrons constitutes one chemical
bond.
• Example: H + H  H2 has electrons on a line connecting
the two H nuclei.

Prentice Hall © 2003 Chapter 8


Covalent Bonding

Prentice Hall © 2003 Chapter 8


Strengths of Covalent
Bonds
• The energy required to break a covalent bond is called
the bond dissociation enthalpy, D. That is, for the Cl2
molecule, D(Cl-Cl) is given by H for the reaction:
Cl2(g)  2Cl(g).
• When more than one bond is broken:
CH4(g)  C(g) + 4H(g) H = 1660 kJ
• the bond enthalpy is a fraction of H for the
atomization reaction:
D(C-H) = ¼H = ¼(1660 kJ) = 415 kJ.
• Bond enthalpies can either be positive or negative.
Prentice Hall © 2003 Chapter 8
Strengths of Covalent
Bonds
Bond Enthalpies and the Enthalpies of
Reactions
• We can use bond enthalpies to calculate the enthalpy for
a chemical reaction.
• We recognize that in any chemical reaction bonds need
to be broken and then new bonds get formed.
• The enthalpy of the reaction is given by the sum of bond
enthalpies for bonds broken minus the sum of bond
enthalpies for bonds formed.

Prentice Hall © 2003 Chapter 8


Strengths of Covalent
Bonds
Bond Enthalpies and the Enthalpies of
Reactions
• Mathematically, if Hrxn is the enthalpy for a reaction,
then
H rxn   Dbonds broken    Dbonds formed 
• We illustrate the concept with the reaction between
methane, CH4, and chlorine:
CH4(g) + Cl2(g)  CH3Cl(g) + HCl(g) Hrxn = ?

Prentice Hall © 2003 Chapter 8


Strengths of Covalent Bonds
Strengths of Covalent
Bonds
Bond Enthalpies and the Enthalpies of
Reactions
• In this reaction one C-H bond and one Cl-Cl bond gets
broken while one C-Cl bond and one H-Cl bond gets
formed.
H rxn  DC - H   DCl - Cl   DC - Cl   DH - Cl 
 104 kJ
• The overall reaction is exothermic which means than the
bonds formed are stronger than the bonds broken.
• The above result is consistent with Hess’s law.
Prentice Hall © 2003 Chapter 8
Strengths of Covalent
Bonds
Bond Enthalpy and Bond Length
• We know that multiple bonds are shorter than single
bonds.
• We can show that multiple bonds are stronger than
single bonds.
• As the number of bonds between atoms increases, the
atoms are held closer and more tightly together.

Prentice Hall © 2003 Chapter 8


Strengths of Covalent Bonds
Bond Polarity and
Electronegativity
• In a covalent bond, electrons are shared.
• Sharing of electrons to form a covalent bond does not
imply equal sharing of those electrons.
• There are some covalent bonds in which the electrons are
located closer to one atom than the other.
• Unequal sharing of electrons results in polar bonds.

Prentice Hall © 2003 Chapter 8


Bond Polarity and
Electronegativity
Electronegativity
• Electronegativity: The ability of one atoms in a
molecule to attract electrons to itself.
• Pauling set electronegativities on a scale from 0.7 (Cs) to
4.0 (F).
• Electronegativity increases
• across a period and
• down a group.

Prentice Hall © 2003 Chapter 8


Bond Polarity and Electronegativity

Electronegativity
Bond Polarity and
Electronegativity
Electronegativity and Bond Polarity
• Difference in electronegativity is a gauge of bond
polarity:
• electronegativity differences around 0 result in non-polar
covalent bonds (equal or almost equal sharing of electrons);
• electronegativity differences around 2 result in polar covalent
bonds (unequal sharing of electrons);
• electronegativity differences around 3 result in ionic bonds
(transfer of electrons).

Prentice Hall © 2003 Chapter 8


Bond Polarity and
Electronegativity
Electronegativity and Bond Polarity
• There is no sharp distinction between bonding types.
• The positive end (or pole) in a polar bond is represented
+ and the negative pole -.

Prentice Hall © 2003 Chapter 8


Bond Polarity and
Electronegativity
Dipole Moments
• Consider HF:
• The difference in electronegativity leads to a polar bond.
• There is more electron density on F than on H.
• Since there are two different “ends” of the molecule, we call HF
a dipole.
• Dipole moment, , is the magnitude of the dipole:
  Qr
where Q is the magnitude of the charges.
• Dipole moments are measured in debyes, D.
Prentice Hall © 2003 Chapter 8
Metallic Bonding
Physical Properties of Metals
• Important physical properties of pure metals: malleable,
ductile, good conductors, and feel cold.
• Most metals are solids with the atoms in a close packed
arrangement.
• In Cu, each atom is surrounded by 12 neighbors.
• There are not enough electrons for the metal atoms to be
covalently bonded to each other.

Prentice Hall © 2003 Chapter 23


Metallic Bonding
Electron-Sea Model of Metallic Bonding
• We use a delocalized model for electrons in a metal.
– The metal nuclei are seen to exist in a sea of electrons.
– No electrons are localized between any two metal atoms.
– Therefore, the electrons can flow freely through the metal.
– Without any definite bonds, the metals are easy to deform (and
are malleable and ductile).
• Problems with the electron sea model:
– As the number of electrons increase, the strength of bonding
should increase and the melting point should increase.

Prentice Hall © 2003 Chapter 23


Metallic Bonding
Electron-Sea Model of Metallic Bonding
– But: group 6B metals have the highest melting points (center of
the transition metals).

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Prentice Hall © 2003 Chapter 23
Metallic Bonding
Molecular-Orbital Model for Metals
• Delocalized bonding requires the atomic orbitals on one
atom to interact with atomic orbitals on neighboring
atoms.
• Example: graphite electrons are delocalized over a whole
plane, benzene molecules have electrons delocalized over
a ring.
• Recall: the number of molecular orbitals is equal to the
number of atomic orbitals.
• In metals there is a very large number of orbitals.
Metallic Bonding
Molecular-Orbital Model for Metals
• As the number of orbitals increase, their energy spacing
decreases and they band together.
• The number of electrons do not completely fill the band
of orbitals.
• Therefore, electrons can be promoted to unoccupied
energy bands.
• Since the energy differences between orbitals are small,
the promotion of electrons occurs at low energy costs.

Prentice Hall © 2003 Chapter 23


Metallic Bonding
Molecular-Orbital Model for Metals
Metallic Bonding
Molecular-Orbital Model for Metals
• As we move across the transition metal series, the
antibonding band starts becoming filled.
• Therefore, the first half of the transition metal series have
only bonding-bonding interactions, the second half has
bonding-antibonding interactions.
• We expect the middle of the transition metal series to
have the highest melting points.
• The energy gap between bands is called the band gap.

Prentice Hall © 2003 Chapter 23


Ketelaar Triangle

Prentice Hall © 2003 Chapter 6


Exceptions to the Octet
Rule

• There are three classes of exceptions to the octet rule:


• Molecules with an odd number of electrons;
• Molecules in which one atom has less than an octet;
• Molecules in which one atom has more than an octet.
Odd Number of Electrons
• Few examples. Generally molecules such as ClO2, NO,
and NO2 have an odd number of electrons.
N O N O

Prentice Hall © 2003 Chapter 8


Exceptions to the Octet
Rule
Less than an Octet
• Relatively rare.
• Molecules with less than an octet are typical for
compounds of Groups 1A, 2A, and 3A.
• Most typical example is BF3.
• Formal charges indicate that the Lewis structure with an
incomplete octet is more important than the ones with
double bonds.

Prentice Hall © 2003 Chapter 8


Exceptions to the Octet
Rule
More than an Octet
• This is the largest class of exceptions.
• Atoms from the 3rd period onwards can accommodate
more than an octet.
• Beyond the third period, the d-orbitals are low enough in
energy to participate in bonding and accept the extra
electron density.

Prentice Hall © 2003 Chapter 8


A Molecular Comparison
of Liquids and Solids
• Physical properties of substances understood in terms of
kinetic molecular theory:
– Gases are highly compressible, assumes shape and volume of
container:
• Gas molecules are far apart and do not interact much with each
other.
– Liquids are almost incompressible, assume the shape but not the
volume of container:
• Liquids molecules are held closer together than gas molecules, but
not so rigidly that the molecules cannot slide past each other.

Prentice Hall © 2003 Chapter 11


A Molecular Comparison
of Liquids and Solids
– Solids are incompressible and have a definite shape and
volume:
• Solid molecules are packed closely together. The molecules are so
rigidly packed that they cannot easily slide past each other.

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A Molecular Comparison
of Liquids and Solids

Prentice Hall © 2003 Chapter 11


A Molecular Comparison
of Liquids and Solids

Prentice Hall © 2003 Chapter 11


A Molecular Comparison
of Liquids and Solids

• Converting a gas into a liquid or solid requires the


molecules to get closer to each other:
– cool or compress.
• Converting a solid into a liquid or gas requires the
molecules to move further apart:
– heat or reduce pressure.
• The forces holding solids and liquids together are called
intermolecular forces.

Prentice Hall © 2003 Chapter 11


Intermolecular Forces

• The covalent bond holding a molecule together is an


intramolecular forces.
• The attraction between molecules is an intermolecular
force.
• Intermolecular forces are much weaker than
intramolecular forces (e.g. 16 kJ/mol vs. 431 kJ/mol for
HCl).
• When a substance melts or boils the intermolecular forces
are broken (not the covalent bonds).
Prentice Hall © 2003 Chapter 11
Intermolecular Forces

Prentice Hall © 2003 Chapter 11


Intermolecular Forces
Ion-Dipole Forces
• Interaction between an ion and a dipole (e.g. water).
• Strongest of all intermolecular forces.

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Intermolecular Forces
Dipole-Dipole Forces
• Dipole-dipole forces exist between neutral polar
molecules.
• Polar molecules need to be close together.
• Weaker than ion-dipole forces.
• There is a mix of attractive and repulsive dipole-dipole
forces as the molecules tumble.
• If two molecules have about the same mass and size, then
dipole-dipole forces increase with increasing polarity.
Prentice Hall © 2003 Chapter 11
Intermolecular Forces

Dipole-Dipole Forces
Intermolecular Forces

Dipole-Dipole Forces

Prentice Hall © 2003 Chapter 11


Intermolecular Forces
London Dispersion Forces
• Weakest of all intermolecular forces.
• It is possible for two adjacent neutral molecules to affect
each other.
• The nucleus of one molecule (or atom) attracts the
electrons of the adjacent molecule (or atom).
• For an instant, the electron clouds become distorted.
• In that instant a dipole is formed (called an instantaneous
dipole).
Prentice Hall © 2003 Chapter 11
Intermolecular Forces
London Dispersion Forces
• One instantaneous dipole can induce another
instantaneous dipole in an adjacent molecule (or atom).
• The forces between instantaneous dipoles are called
London dispersion forces.

Prentice Hall © 2003 Chapter 11


Intermolecular Forces
London Dispersion Forces
• Polarizability is the ease with which an electron cloud
can be deformed.
• The larger the molecule (the greater the number of
electrons) the more polarizable.
• London dispersion forces increase as molecular weight
increases.
• London dispersion forces exist between all molecules.
• London dispersion forces depend on the shape of the
molecule.
Prentice Hall © 2003 Chapter 11
Intermolecular Forces
London Dispersion Forces
• The greater the surface area available for contact, the
greater the dispersion forces.
• London dispersion forces between spherical molecules
are lower than between sausage-like molecules.

Prentice Hall © 2003 Chapter 11


Intermolecular Forces
London Dispersion
Forces
Intermolecular Forces
London Dispersion Forces

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Intermolecular Forces
Hydrogen Bonding
• Special case of dipole-dipole forces.
• By experiments: boiling points of compounds with H-F,
H-O, and H-N bonds are abnormally high.
• Intermolecular forces are abnormally strong.

Prentice Hall © 2003 Chapter 11


Intermolecular Forces
Hydrogen Bonding
• H-bonding requires H bonded to an electronegative
element (most important for compounds of F, O, and N).
– Electrons in the H-X (X = electronegative element) lie much
closer to X than H.
– H has only one electron, so in the H-X bond, the + H presents
an almost bare proton to the - X.
– Therefore, H-bonds are strong.

Prentice Hall © 2003 Chapter 11


Hydrogen Bonding
Hydrogen Bonding
Intermolecular Forces
Hydrogen Bonding
• Hydrogen bonds are responsible for:
– Ice Floating
• Solids are usually more closely packed than liquids;
• Therefore, solids are more dense than liquids.
• Ice is ordered with an open structure to optimize H-bonding.
• Therefore, ice is less dense than water.
• In water the H-O bond length is 1.0 Å.
• The O…H hydrogen bond length is 1.8 Å.
• Ice has waters arranged in an open, regular hexagon.
• Each + H points towards a lone pair on O.

Prentice Hall © 2003 Chapter 11


Intermolecular Forces
Hydrogen Bonding