Chemistry: Atoms, Molecules, & Chemical Bonding

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.
Later scientists realized that the atom consisted of
charged entities.
Prentice Hall 2003
Chapter 2

Structure
Cathode Rays and Electrons
Prentice Hall 2003
Chapter 2

Structure
A cathode ray tube (CRT) is a hollow vessel with an electrode at either end.
A high voltage is applied across the electrodes.
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 6

Structure
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
Chapter 2

Structure
Milikans oil drop
experiment

Structure
Milikans oil-drop experiment
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

Structure
Milikans oil drop experiment
Using this experiment, Millikan determined the charge on
the electron to be 1.60 10-19 C.
With more accurate numbers, we get the mass of the

electron to be 9.10939 10-28 g.
Prentice Hall 2003
Chapter 2

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

Structure
Radioactivity
Prentice Hall 2003
Chapter 2

Structure
Radioactivity
Ahighdeflectiontowardsthepositiveplatecorresponds
toradiationwhichisnegativelychargedandoflowmass.
Thisiscalledradiation(consistsofelectrons).
Nodeflectioncorrespondstoneutralradiation.Thisis
calledradiation.
Smalldeflectiontowardsthenegativelychargedplate
correspondstohighmass,positivelychargedradiation.
Thisiscalledradiation.
Prentice Hall 2003
Chapter 2

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.

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
Rutherfords result was impossible.
Prentice Hall 2003
Chapter 2

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
Thomsons 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 Modern View of

Atomic Structure
The atom consists of
positive, negative, and
neutral entities (protons,
electrons, and neutrons).
Prentice Hall 2003
Chapter 2
The Modern View of

Atomic Structure
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 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:
Prentice Hall 2003
Chapter 6

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).
Prentice Hall 2003
Chapter 6
Example
The wavelength of the green light from a traffic signal is
centered at 522nm. What is the frequency?
c
c 3.00 108 m / s
14 1
5
.
75
10
s
9
522 10 m
Prentice Hall 2003
Chapter 6
Prentice Hall 2003
Chapter 6
Heated solid emits radiation over a wide range of

wavelength
Dependence of amount of radiation energy emitted on
wavelength- partially successful with wave theory
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 Plancks 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
Rutherfords theory.
Bohr noted the line spectra of certain elements and assumed
the electrons were confined to specific energy states. These
were called orbits.
Prentice Hall 2003
Chapter 6

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
1
E 2.18 10
J 2
where n is the principal quantum number
n (i.e., n = 1, 2, 3,
and nothing else).
Prentice Hall 2003
18
Chapter 6
Line Spectra and

the Bohr Model
Bohr Model

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

Model
Bohr Model
We can show that
1
hc
1
E h
2.18 1018 J 2 2
n
n
i
f
When ni > nf, energy is emitted.

When nf > ni, energy is absorbed
Prentice Hall 2003
Chapter 6
The Wave Behavior of

Matter
Knowing that light has a particle nature, it seems reasonable to
ask if matter has a wave nature.
Using Einsteins and Plancks equations, de Broglie showed:
The momentum, mv, is a particle

mvproperty, 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
Heisenbergs 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
xmv
4
Prentice Hall 2003
Chapter 6
Quantum Mechanics and

Atomic Orbitals
Schrdinger 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, 2 gives the probability
of finding the electron,
that is, gives the electron density for the atom.
Prentice Hall 2003
Chapter 6

Atomic Orbitals
Prentice Hall 2003
Chapter 6

Atomic Orbitals
Orbitals and Quantum Numbers

If we solve the Schrdinger 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 electrons path around the nucleus
whereas, an orbital is a mathematical function with no
direct physical meaning.
Prentice Hall 2003
Chapter 6

Atomic Orbitals
An atomic orbital is specified by 3 quantum numbers:
1.
2.
3.
Principal Quantum Number, n, related to the size of the orbital. This is the
same as Bohrs 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.
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.
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

Atomic Orbitals
Shell/level The atoms 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 atoms shells/levels contain
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

Atomic Orbitals
Orbital Each allowed combination of n, l and ml values specifies
one of the atoms 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

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

Atomic Orbitals
Prentice Hall 2003
Chapter 6

Atomic Orbitals

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
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
Representations of
Orbitals
The d-Orbitals
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
Prentice Hall 2003
Chapter 6
Many-Electron Atoms
Since electron spin is quantized, we define ms = spin quantum
number = .
Paulis 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
Many-Electron Atoms
Orbitals and Their Energies
The Aufbau diagram looks slightly different for manyelectron systems.
Prentice Hall 2003
Chapter 6
Orbitals and Their Energies
Many-Electron Atoms
Electron Configurations
Hunds Rule
Electron configurations tell us in which orbitals the
electrons for an element are located.
Hunds 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
Prentice Hall 2003
Chapter 6
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
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
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
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.
The Hydrogen Molecule

When two AOs overlap, two MOs form.
Prentice Hall 2003
Chapter 9
Molecular Orbitals
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
Prentice Hall 2003
Chapter 9
Molecular Orbitals
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
Prentice Hall 2003
Chapter 9
Molecular Orbitals
Bond Order
Define
Bond order 12 bonding electrons - antibonding electrons
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
Therefore, H2 has a single bond.
Bond order 12 2 0 1
Prentice Hall 2003
Chapter 9
Molecular Orbitals
Bond Order
For He2
Bond order 12 2 2 0
Therefore He2 is not a stable molecule
Prentice Hall 2003
Chapter 9
Second-Row Diatomic
Molecules
We look at homonuclear diatomic molecules (e.g. Li 2, 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
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 12 4 2 1
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
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 12 4 4 0
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
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
Once the relative orbital energies are known, we add the
required number of electrons to the MOs, taking into
account Paulis exclusion principle and Hunds rule.
As bond order increases, bond length decreases.
As bond order increases, bond energy increases.
Prentice Hall 2003
Chapter 9
Second-Row Diatomic
Molecules
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) + Cl2(g) NaCl(s)
Hf = -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.
Prentice Hall 2003
Chapter 8
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
Prentice Hall 2003
Chapter 8
Ionic Bonding
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 Jm/C2), Q1 and Q2 are the charges
on the ions, and d is the distance between ions.
Prentice Hall 2003
Chapter 8
Ionic Bonding
Lattice energy increases as
The charges on the ions increase
The distance between the ions decreases.
Prentice Hall 2003
Chapter 8
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) = H = (1660 kJ) = 415 kJ.
Bond enthalpies can either be positive or negative.
Prentice Hall 2003
Chapter 8
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
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)
Prentice Hall 2003
Chapter 8
Hrxn = ?
Strengths of Covalent Bonds
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.
The overall reaction is exothermic which means than the

bonds formed are stronger than the bonds broken.
The above result is consistent with Hesss law.
Prentice Hall 2003
Chapter 8
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 ofthe
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).
Prentice Hall 2003
Chapter 23
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

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
Metallic Bonding

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
Ionic
Covalent
Metallic
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

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

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
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.
Prentice Hall 2003
Chapter 11
Prentice Hall 2003
Chapter 11
Prentice Hall 2003
Chapter 11
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
Prentice Hall 2003
Chapter 11
Ion-Dipole Forces
Interaction between an ion and a dipole (e.g. water).
Strongest of all intermolecular forces.
Prentice Hall 2003
Chapter 11
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
Prentice Hall 2003
Chapter 11
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
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

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
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
London Dispersion
Forces
Prentice Hall 2003
Chapter 11
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
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
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 .
The OH hydrogen bond length is 1.8 .
Ice has waters arranged in an open, regular hexagon.
Each + H points towards a lone pair on O.
Prentice Hall 2003
Chapter 11
Hydrogen Bonding

Chemistry: Atoms, Molecules, & Chemical Bonding

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