Atoms, Electrons, and Orbitals

Bohr’s model…
• Electrons are found in specific
circular paths (orbits) around the
nucleus.
• The electrons have fixed energies
called energy levels. (like rungs on a
ladder)
• The amount of energy required to
move an electron to another energy
level is called a quantum.
 The Quantum Mechanical model

• It is based on the energy and possible

location of an electron.
• how likely it is to find an electron is described
in terms of probability. (ie. Propeller blades)
• Based on work done by Shrodinger…
 Atomic Orbitals
• The energy levels of electrons are labeled
by principal quantum numbers (n)
• Each energy sublevel corresponds to an
orbital of a different shape, which
describes where the electron is likely to be
found.
Atomic Orbitals
ORBITALS

The theory suggests that the behavior of each electron in an atom can be
described by a wave function (ψ), which is a function of the space coordinates of
the electron and thus has spatial characteristics.

These one electron wave functions are called atomic orbitals (AOs). Atomic
orbitals describe electron densities in the atom at various distances and
directions from the nucleus.

The probability of finding an electron (ψ2) is highest inside the contour surface.
 Shapes and Orientations of Orbitals

1s Orbital

Sphere around the nucleus

The one tells you that the electron is in the

orbital closest to the nucleus
S tells you about the shape
 2s Orbital
• Similar to 1s except the electron is most
likely in the region farther from the nucleus
 p Orbitals
• At the first energy level there is only the 1s
orbital, after the second energy level there
are 2p orbitals
• Look like dumbbells
• In the three directions
d Orbitals
Thus instead of thinking of where an electron is, it is more correct to think about
where the electron is likely to be. Orbitals are thus regions of space where an
electron is more likely to be found. These regions of space, which have a significant
electron population (orbitals), have shape, size (distance from the nucleus),
and energy.

The most common elements present in organic compounds are first-row

elements (C, H, N, O); therefore 1s, 2s, and 2p AOs are most commonly
encountered.
 Remember….
MAX NUMBER OF ELECTRONS IN AN ENERGY LEVEL

ENERGY LEVEL MAX # OF ELECTRONS

1 2
2 8
3 18
4 32
5 50
 Electron Configuration
A detailed way of showing the order in which electrons
fill in around the nucleus
# of e- in

1s 2 sub level

Energy Level
Sub Level
(s, p, d, f )
 We must follow 3 rules…

• Aufbau priciple
• Electrons occupy energy levels with lowest
energy first.
 Pauli exclusion principle
• If 2 electrons occupy the same energy level they must
have opposite spins.

Hund’s rule…
• Electrons that occupy orbitals of the same energy will
have the maximum number of electrons with the same
spin.

• 2p
Structure determines properties and the properties of atoms depend
on atomic structure. All of an element’s protons are in its nucleus,
but the element’s electrons are distributed among orbitals of various
energy and distance from the nucleus. More than anything else, we
look at its electron configuration when we wish to understand how
an element behaves.
Ionic Bonds

Atoms combine with one another to give compounds having properties

different from the atoms they contain. The attractive force between atoms in a
compound is a chemical bond. One type of chemical bond, called an ionic
bond, is the force of attraction between oppositely charged species (ions).
Positively charged ions are referred to as cations; negatively charged ions
are anions.

Whether an element is the source of the

cation or anion in an ionic bond depends
on several factors, for which the periodic
table can serve as a guide. In forming
ionic compounds, elements at the left of
the periodic table typically lose electrons,
giving a cation that has the same electron
configuration as the preceding noble gas.
Loss of an electron from sodium, for example, yields Na+ , which has the
same electron configuration as neon.

A large amount of energy, called the ionization energy, must be transferred to any atom to
dislodge an electron. The ionization energy of sodium, for example, is 496 kJ/mol (119
kcal/mol). Processes that absorb energy are said to be endothermic.

In general, ionization energy increases across

a row in the periodic table. Elements at the
right of the periodic table tend to gain
electrons to reach the electron configuration
of the next higher noble gas. Adding an
electron to chlorine, for example, gives the
anion Cl , which has the same closed-shell
electron configuration as the noble gas argon.

Compared with other elements, sodium

and its relatives in group 1A have
relatively low ionization energies.
Energy is released when a chlorine atom captures an electron. Energy-releasing
reactions are described as exothermic, and the energy change for an exothermic
process has a negative sign. The energy change for addition of an electron to an atom is
referred to as its electron affinity and is −349 kJ/mol (−83.4 kcal/mol) for chlorine.

Were we to simply add the ionization energy of sodium (496 kJ/mol) and the electron
affinity of chlorine (349 kJ/mol), we would conclude that the overall process is
endothermic by 147 kJ/mol.

Attractive forces between oppositely charged particles are termed electrostatic, or

Ionic bonding was proposed by the coulombic, attractions and are what we mean
by an ionic bond between two atoms.
Covalent Bonds, Lewis Structures, and the
Octet Rule
The covalent, or shared electron pair, model of chemical bonding
was first suggested by G. N. Lewis of the University of California in
1916. Lewis proposed that a sharing of two electrons by two hydrogen
atoms permits each one to have a stable closed-shell electron
configuration analogous to helium.

The amount of energy required to dissociate a hydrogen molecule H 2 to two

separate hydrogen atoms is its bond dissociation enthalpy. For H 2 it is
quite large, amounting to 435 kJ/mol (104 kcal/mol). The main contributor to
the strength of the covalent bond in H2 is the increased binding force exerted
on its two electrons. Each electron in H2 “feels” the attractive force of two
nuclei, rather than one as it would in an isolated hydrogen atom.
The Lewis Model of Chemical Bonding

• In 1916 G. N. Lewis proposed that atoms combine in order to achieve a

more stable electron configuration.
• Maximum stability results when an atom is isoelectronic with a noble gas.
• An electron pair that is shared between two atoms constitutes a covalent
bond.

Covalent Bonding in H2

Two hydrogen atoms, each with 1 electron,

H. .H
can share those electrons in a covalent bond.

H: H
• Sharing the electron pair gives each hydrogen an electron
configuration analogous to helium.
 Covalent Bonding in F2
Two fluorine atoms, each with 7 valence electrons,

.. ..
: ..F . . F:
..
can share those electrons in a covalent bond.
.. ..
: .. F:
F : ..
• Sharing the electron pair gives each fluorine an electron configuration
analogous to neon.

The Octet Rule

In forming compounds, atoms gain, lose, or share electrons to give a stable

electron configuration characterized by 8 valence electrons.
.. ..
: .. F:
F : ..
• The octet rule is the most useful in cases involving covalent bonds to C,
N, O, and F.
 Valence Bond Theory
• Extends the Lewis concept of electron pair
bonds by introducing the notion of orbital
overlap and hybridization.
• Hybridization is necessary to account for
molecular geometry.
• Hybrid atomic orbitals are constructed by
making linear combinations (sums and
differences) between hydrogen-like
orbitals in the valence shell of each atom.
ORBITAL HYBRIDIZATION: The question of shape!
• Isolated atoms (with valence e’s in s,p, and d orbitals.

• Bonded atoms in molecules or ions, in which

bonded regions exhibit significantly different.

all s orbitals

all p orbitals

d orbitals

Orbital shapes, Individual (“isolated”) Atoms

 trigonal tetrahedral

trigonal-bipyramidal octahedral
To rationalize how the shapes of atomic orbitals are transformed into
the orbitals occupied in covalently bonded species, we need the help
of two bonding theories:

Valence Bond (VB) Theory, the theory we will explore, describes the
placement of electrons into bonding orbitals located around the individual
atoms from which they originated.

Molecular Orbital (MO) Theory places all electrons from atoms

involved into molecular orbitals spread out over the entire species.
This theory works well for excited species, and molecules like O2.
COVALENT BOND FORMATION (VB THEORY)
In order for a covalent bond to form between two atoms, overlap must occur
between the orbitals containing the valence electrons.

Dotted areas: representation of "electron cloud" for one electron

"Head-on Overlap"

Sigma Bond: merged orbital, 2 e's

The best overlap occurs when two orbitals are allowed to meet “head on” in a
straight line. When this occurs, the atomic orbitals merge to form a single
bonding orbital and a “single bond” is formed, called a sigma () bond.
 MAXIMIZING BOND FORMATION

In order for “best overlap” to occur, valence electrons need to be re-

oriented and electron clouds reshaped to allow optimum contact.

To form as many bonds as possible from the available valence

electrons, sometimes separation of electron pairs must also occur.

We describe the transformation process as “orbital hybridization” and

we focus on the central atom in the species...
 “sp” Hybridization: all 2 Region Species

Be 2
BeCl 2 Cl Be Cl 2Cl 14
16 e's/2= 8 prs

Cl Be Cl (octet violator)

Number of regions around CENTRAL ATOM: 2

Cl Be Cl shape : LINEAR
bond angles: 180o
 Hybridization of Be in BeCl2

Valence e’s
Hybrid sp orbitals:
1 part s, 1 part p
Atomic Be: 1s2 2s2

Energy

2p separate "hybridize"
2p

"sp" "sp"

2s 2s
 "arrange"
Be is said to be FORMATION OF BeCl2:
Be
"sp hybridized"
(VSEPR)

Cl Be Cl

Each Chlorine atom,

1s22s22p63s23p5, has one unshared
electron in a p orbital. The half filled
p orbital overlaps head-on with a half
full hybrid sp orbital of the beryllium
Cl Be Cl to form a sigma bond.

Cl Be Cl

sp hybridized, linear, 180o bond angles

“sp2” Hybridization: All 3 Region Species

F
B 3
BF 3 F B F 3F 21
24 e's/2= 12 prs

F B F (octet violator)

Number of regions around CENTRAL ATOM: 3

F shape : TRIGONAL PLANAR

bond angles: 120o
B
F F
 Hybridization of B in BF3

Hybrid sp2 orbitals:

Valence e’s 1 part s, 2 parts p

Atomic B : 1s2 2s2 2p1

Energy

2p separate "hybridize"
2p

2 2 2
"sp " "sp " "sp "

2s 2s
 "arrange"
B is said to be
B
"sp2 hybridized" FORMATION OF
(VSEPR) BF3:

Each fluorine atom, 1s22s22p5, has one unshared

electron in a p orbital. The half filled p orbital
overlaps head-on with a half full hybrid sp2 orbital
of the boron to form a sigma bond.

sp2 hybridized, TRIGONAL PLANAR,

120o bond angles

F
F

B
B
F F
F F
“sp3” Hybridization: All 4 Region Species

C 4
CH 4 H 4H 4
8
H C H 8 e's /2 = 4 pr

Number of regions around CENTRAL ATOM: 4

H
shape : TETRAHEDRAL
bond angles: 109.5o
C
H H
H
 Hybridization of C in CH4

Valence e’s Hybrid sp3 orbitals:

1 part s, 3 parts p
Atomic C : 1s2 2s2 2p2

Energy

2p separate "hybridize"
2p

3 3 3 3
"sp " "sp " "sp " "sp "

2s 2s
 "arrange"
C is said to be
C "sp3 hybridized" FORMATION OF CH4:
(VSEPR)

Each hydrogen atom, 1s1, has one unshared

electron in an s orbital. The half filled s orbital
overlaps head-on with a half full hybrid sp3 orbital
of the carbon to form a sigma bond.

sp3hybridized, TETRAHEDRAL,
109.5o bond angles

H
H

C C

H
H H H

H H
Double Bonds and Triple Bonds

Lewis’s concept of shared electron pair bonds allows for four-electron

double bonds and six-electron triple bonds. Ethylene (C2H4 ) has 12
valence electrons, which can be distributed as follows:

The structural formula produced has a single bond

between the carbons and seven electrons around each.
By pairing the unshared electron of one carbon with its
counterpart of the other carbon, a double bond results
and the octet rule is satisfied for both carbons.

Likewise, the ten valence electrons of acetylene (C2H2 )

can be arranged in a structural formula that satisfies the
octet rule when six of them are shared in a triple bond
between the carbons.
 Unshared Pairs, Double or Triple Bonds

N 5
3H 3
NH 3 H N H 8e's/2=4 prs

H
H N H
Unshared pairs occupy a hybridized orbital
the same as bonded pairs: See the example H
of NH3 that follows.
Number of regions around CENTRAL ATOM: 4

shape : TETRAHEDRAL
bond angles: < 109.5o
N
H H
H

Double and triple bonds are formed from electrons left behind and unused in p orbitals.
Since all multiple bonds are formed on top of sigma bonds, the hybridization of the
single () bonds determine the hybridization and shape of the molecule.
 Hybridization of N in NH3

Valence e’s

Atomic N: 1s2 2s2 2p3

Energy

"hybridize"
2p
3 3 3 3
"sp " "sp " "sp " "sp "

2s
 "arrange"
N is said to be
N "sp3 hybridized" FORMATION OF NH3:
(VSEPR)

Each hydrogen atom, 1s1, has one unshared electron in an

s orbital. The half filled s orbital overlaps head-on with a
half full hybrid sp3 orbital of the nitrogen to form a sigma
bond.
sp3hybridized, TETRAHEDRAL,
~107o bond angles

N N

H
H H H

H H
Summary: Regions, Shapes and Hybridization

#, regions shape hybridization

2 linear sp
2
3 trigonal sp
planar
3
4 tetrahedral sp
3
5 trigonal sp d
bipyramidal
3 2
6 octahedral sp d
Polar Covalent Bonds, Electronegativity,
and Bond Dipoles
Electrons in covalent bonds are not necessarily shared equally by the two
atoms that they connect. If one atom has a greater tendency to attract
electrons toward itself than the other, the electron distribution is polarized,
and the bond is described as polar covalent. The tendency of an atom to
attract the electrons in a covalent bond toward itself defines its
electronegativity.

An electronegative element attracts electrons; an electropositive one

donates them.
Hydrogen fluoride, for example, has a
polar covalent bond. Fluorine is more
electronegative than hydrogen and
pulls the electrons in the H-F bond
toward itself, giving fluorine a partial
negative charge and hydrogen a
partial positive charge.
A third way of illustrating the electron polarization in HF is graphically, by
way of an electrostatic potential map, which uses the colors of the
rainbow to show the charge distribution. Blue through red tracks regions
of greater positive charge to greater negative charge

Contrast the electrostatic potential map of HF with those of H2 and F2.

The covalent bond in H2 and F2 joins two

atoms. Because the bonded atoms are
identical, so are their electronegativities.
There is no polarization of the electron
distribution. The covalent bond in HF, on
the other hand, unites two atoms of
different electronegativity, and the
electron distribution is very polarized.
The most commonly used electronegativity scale was devised by Linus Pauling.
Electronegativity increases from left to right across a row in the periodic table. Of
the second-row elements, the most electronegative is fluorine, the least
electronegative is lithium.

Electronegativity decreases going down a column. Of the halogens, fluorine is the

most electronegative, then chlorine, then bromine, then iodine. Indeed, fluorine is
the most electronegative of all the elements; oxygen is second. In general, the
greater the electronegativity difference between two elements, the more polar the
bond between them.
Structural Formulas of Organic Molecules
Sometimes more than one Lewis formula can be written for a molecule,
especially if the molecule contains a double or triple bond. A simple
example is ozone (O3), for which we can write the Lewis structure:

On the basis of the Lewis formula, we would expect ozone to have

two different O-O-O bond lengths, one of them similar to the O-O-O
single bond distance of 147 pm and the other similar to the 121 pm.
In fact, both bond distances are the same (128 pm) O somewhat
shorter than a single bond, somewhat longer than a double bond.

The structure of ozone requires that the central oxygen must be

identically bonded to both terminal oxygens.

The equivalence of the two terminal oxygens. Notice, too,

that the central oxygen is blue (positively charged) and both
terminal oxygens are red (negatively charged).

According to the resonance concept, when two or more Lewis structures

that differ only in the distribution of electrons can be written for a molecule,
no single Lewis structure is sufficient to describe its true electron distribution.
The true structure is said to be a resonance hybrid of the various Lewis
formulas, called contributing structures.

In the case of ozone, the two Lewis formulas are

equivalent and contribute equally to the resonance
hybrid. The double-headed arrow signify resonance
and read it to mean that the Lewis formulas shown
contribute to, but do not separately describe, the
electronic structure of the molecule.

It is important to remember that the double-headed

resonance arrow does not indicate a process in which
contributing Lewis structures interconvert. An average
of the two Lewis structures is sometimes drawn using
a dashed line to represent a “partial” bond.

Writing the various Lewis formulas that contribute to a resonance hybrid can be
made easier by using curved arrows to keep track of delocalized electrons. We
can convert one Lewis structure of ozone to another by moving electron pairs as
shown:
Writing Organic Structures

Drawing structural formulas for organic molecules

soon becomes routine and can be simplified even
more. For example, a chain of carbon atoms can
be represented by drawing all of the C-C bonds
while omitting individual carbon atoms. The
resulting structural formulas are further simplified
by stripping away the hydrogens.

When atoms that are neither carbon nor

hydrogen, termed heteroatoms, are present,
hydrogens attached to them are shown, as
illustrated in the following examples. The
second example is the amino acid isoleucine,
which has the molecular formula C6H13NO2.

The structural language of organic

chemistry has been developed so that
complex molecules can be described in
a clear, yet economical way.
 Molecular Geometry

Geometría ideal
Nº de Geometría Angulo de
pares de e- enlace
2 (AX2) Linear 180o

3 (AX3) Trigonal 120o

Planar

4 (AX4) Tetrahedral 109.5o

5 (AX5) Trigonal 90o / 120o

Bipyramidal

6 (AX6) Octahedral 90o

 Molecular Geometry

Geometría Nº pares Nº pares

Nº pares Geometría
de los pares de e- de e- Ejemplo
de e- molecular
de e- de enlace de no enlace
 Molecular Geometry

Geometría molecular para el ión NO3-

Los dobles enlaces son ignorados en RPECV

 Molecular Geometry

Geometría Nº pares Nº pares

Nº pares Geometría
de los pares de e- de e- Ejemplo
de e- molecular
de e- de enlace de no enlace
 Molecular Geometry

CH4
H

Estructura de Lewis: H C H
H

109.5° 90°

Menor repulsión !
 Molecular Geometry

Trigonal piramidal Tetrahédrica

Bent o V
 Molecular Geometry

Geometría Nº pares Nº pares

Nº pares Geometría
de los pares de e- de e- Ejemplo
de e- molecular
de e- de enlace de no enlace
 Molecular Geometry

Geometría Nº pares Nº pares

Nº pares Geometría
de los pares de e- de e- Ejemplo
de e- molecular
de e- de enlace de no enlace
GEOMETRÍA MOLECULAR: MÉTODO DE REPULSIÓN DE LOS PARES DE
ELECTRONES DE LA CAPA DE VALENCIA

Los pares de electrones se disponen en torno al átomo central de modo

que se minimicen las repulsiones eléctricas entre ellos

Cuatro pares de e rodeando el

átomo de nitrógeno. Se dirigen
hacia los vértices de un tetraedro
(Geometría electrónica)

Como sólo se enlazan 3 de los 4

pares electrónicos, la forma de la
molécula será piramidal
(Geometría molecular)
Dos pares de e enlazados: Molécula lineal

Tres pares de e enlazados: Molécula triangular plana

Cuatro pares de e:

Molécula tetraédrica Molécula piramidal Molécula angular

Cuatro enlazados Tres enlazados Dos enlazados

Repulsión
Enlazado-
Enlazado < No enlazado-
Enlazado < No enlazado-
No enlazado entre pares de
electrones
Cinco pares de e enlazados: Molécula bipiramidal triangular

Seis pares de e enlazados: Molécula bipiramidal cuadrada

En cuanto a la geometría molecular, los enlaces múltiples son iguales que los simples
Molecular Dipole Moments
The combination of our knowledge of molecular geometry with a feel for the
polarity of chemical bonds to predict whether a molecule has a dipole
moment or not.
The molecular dipole moment is the resultant of all of the individual bond dipole
moments of a substance. Some molecules, such as carbon dioxide, have polar bonds,
but lack a dipole moment because their geometry causes the individual CPO bond
dipoles to cancel.

Carbon dioxide, have polar bonds, but lack a

dipole moment because their geometry causes
the individual C=O bond dipoles to cancel.

Carbon tetrachloride, with four polar C-Cl bonds and a tetrahedral shape, has no net
dipole moment, because the result of the four bond dipoles is zero.
We emphasized that the connection between structure and
properties is central to understanding organic chemistry. From the
Lewis structure of a molecule, we can use electronegativity to tell
us about the polarity of bonds and combine that with structural
characteristics to predict whether the molecule has a dipole
moment.

We’ll see a connection between molecular structure and chemical

reactivity.
 Curved Arrows and Chemical Reactions

Reactions involving only one electron pair. Suppose the molecule A-B
dissociates to cation A and anion B . A chemical equation for this
ionization could be written as:

Alternatively, we could write:

The reaction is the same but the second
equation provides more information by
including the bond that is broken during
ionization and showing the flow of
electrons.

To illustrate, the ionization of carbonic acid corresponds to

that just described for A-B. A neutral molecule (H2CO3 )
dissociates to a cation (H+ ) and an anion (HCO3 -).

The reactant need not always be a neutral molecule. It can

be an ion such as the hydrogen carbonate ion produced in
the preceding reaction.
 The reverse of a dissociation is a combination, such as the formation
of a covalent bond between a cation A + and an anion B -.

Here the curved arrow begins at the unshared pair of B - and points to A + .
Electrons flow from sites of higher electron density to lower. The unshared
electron pair of B- becomes the shared electron pair in the A-B bond. Charge
is conserved.

Many reactions combine bond making with bond breaking and require more than
one curved arrow.

The electrons flow from electron-rich to

electron-poor sites. Hydroxide ion is
negatively charged and, therefore, electron-
rich while the carbon of H3CBr is partially
positive because of the polarization of the C-
Br bond.

A very common process involves transfer of a proton

from one atom to another.
Curved-arrow notation is also applied to reactions in which double and triple
bonds are made or broken. Only one component (one electron pair) of the double
or triple bond is involved.
Acids and Bases
Three definitions of acid

Theory:
Who When
Acid=

Arrhenius increases H+ 1880’s

Brønsted proton donor 1923

Lowry ditto 1923

Electron-pair
Lewis 1923
acceptor
 Definitions
Arrehenius • Acids – produce H+
only in water • Bases - produce OH-

Bronsted-Lowry • Acids – donate H+

• Bases – accept H+
any solvent

Lewis • Acids – accept e- pair

• Bases – donate e- pair
used in organic chemistry,
wider range of substances
 The hydrogen ion in aqueous solution

H+ + H2O  H3O+ (hydronium ion)

Examples
Arrhenius
HCl NaOH

Bronsted-Lowry
HCl HCN NH3

Lewis :NH3
BF3
 Some Definitions
• Arrhenius acids and bases
– Acid: Substance that, when dissolved in
water, increases the concentration of hydrogen
ions (protons, H+).

– Base: Substance that, when dissolved in

water, increases the concentration of hydroxide
ions.
 Some Definitions
• Brønsted–Lowry: must have both
1. an Acid: Proton donor

and
2. a Base: Proton acceptor
Brønsted-Lowry acids and bases are always paired.

The Brønsted-Lowry acid donates a proton,

while the Brønsted-Lowry base accepts it.

Which is the acid and which is the base in each of these rxns?
A Brønsted–Lowry acid…
…must have a removable (acidic) proton.
HCl, H2O, H2SO4

A Brønsted–Lowry base…
…must have a pair of nonbonding electrons.
NH3, H2O
If it can be either…

...it is amphiprotic.

HCO3 –

HSO4 –

H2O
What Happens When an Acid
Dissolves in Water?

• Water acts as a
Brønsted–Lowry base
and abstracts a proton
(H+) from the acid.
• As a result, the conjugate
base of the acid and a
hydronium ion are
formed.

Movies…
 Conjugate Acids and Bases:
• From the Latin word conjugare, meaning “to join
together.”
• Reactions between acids and bases always yield
their conjugate bases and acids.
Acid and Base Strength
• Strong acids are completely
dissociated in water.
– Their conjugate bases are
quite weak.
• Weak acids only dissociate
partially in water.
– Their conjugate bases are
weak bases.
Acid and Base Strength
• Substances with negligible
acidity do not dissociate in
water.
– Their conjugate bases are
exceedingly strong.
 Acid and Base Strength
In any acid-base reaction, the equilibrium
favors the reaction that moves the proton to
the stronger base.

HCl(aq) + H2O(l)  H3O+(aq) + Cl–(aq)

H2O is a much stronger base than Cl–, so the

equilibrium lies so far to the right K is not
measured (K>>1).
 Acid and Base Strength

Acetate is a stronger base

than H2O, so the equilibrium
favors the left side (K<1).

The stronger base “wins” the

proton.

HC2H3O2(aq) + H2O H3O+(aq) + C2H3O2–(aq)

 How Structure Affects Acid Strength

The main ways in which structure affects acidity depend on:

1. The strength of the bond to the atom from which the proton is lost

2. The electronegativity of the atom from which the proton is lost

3. Electron delocalization in the conjugate base

Bond Strength.

The effect of bond strength is easy to see by comparing the acidities of the
hydrogen halides.

• Bond strength decreases going down a group in the periodic table. As the
halogen X becomes larger, the H-X bond becomes longer and weaker and acid
strength increases.

• The high charge-to-size ratio of F cause high energetic values in the processes
. Other things being equal, processes that give ions in which the electric charge
is constrained to a small volume are less favorable than processes in which the
charge is more spread out.
Electronegativity.

The effect of electronegativity on acidity is evident in the following series

involving bonds between hydrogen and the second-row elements C, N, O,
and F.

As the atom (A) to which H is bonded becomes more electronegative, the

polarization H-A becomes more pronounced and H is more easily transferred
as H + .
Here we see that when the H-A bond breaks,
both electrons in the bond are retained by A.
The more electronegative atom A is, the
easier it becomes for the electrons to flow in
its direction.

Fluorine is the most electronegative and iodine the least electronegative of the halogens, but
HF is the weakest acid while HI is the strongest. Electronegativity is the more important factor
when comparing elements in the same row of the periodic table.
In many acids the acidic proton is bonded to oxygen. Such compounds can
be considered as derivatives of water. Among organic compounds, the ones
most closely related to water are alcohols.

Electronegative substituents in a molecule can affect acidity even when they are not
directly bonded to the ionizable proton.

The electronegative fluorines attract

electrons toward themselves and that
this attraction is transmitted through the
bonds, increasing the positive character
of the O-H proton.

The greater positive character, hence the increased acidity, of the O-H proton of 2,2, 2-
trifluoroethanol can be seen in the electrostatic potential maps.

The anion CF3CH2O- , is stabilized by its three fluorines, which

attract electrons from the negatively charged oxygen, dispersing
the charge.
Inductive effects depend on the electronegativity of the
substituent and the number of bonds between it and the
affected site. As the number of bonds between the two units
increases, the inductive effect decreases.
 Electron Delocalization in the Conjugate Base.

With a pKa of 1.4, nitric acid is almost completely ionized in water. The N atom in
nitric acid is not only electronegative in its own right, but bears a formal charge
of 1, which enhances its ability to attract electrons away from the O-H group.

When nitric acid transfers its proton to water, nitrate ion is produced.

Nitrate ion is stabilized by electron delocalization, which we

can represent in terms of resonance between three
equivalent contributing structures. The negative charge is
shared equally by all three oxygens. Stabilization of
nitrate ion by electron delocalization increases the
equilibrium constant for its formation.

Both oxygens of acetate share the negative

charge equally, which translates into a Ka for
acetic acid that is greater than it would be if the
charge were confi ned to a single oxygen.
 Acid-Base Chemistry

Reaction Classification:

• Substitution: H3C Cl + NaOH H 3C OH + NaCl

Br
• Addition:
Br2

• Elimination: Br

Br
• Rearrangement: -HBr
 Bond Cleavage
• Heterolytic Bond Cleavage (Polarized Bonds)

 Generate Ionic Species (Cation and Anion)

• Homolytic Bond Cleavage (Generate Radicals)

 Radicals: Species Containing Unpaired Electrons

A B A + B

A B A + B
 Acid-Base Chemistry
• Fundamental Chemical Reaction

• Very Fast Reactions (ET Faster)

• Chemical Equilibria

• Acids/Bases Classified in a Number of Ways

 Arrhenius (Hydrogen and Hydroxide Ions)

 Brønsted—Lowry (H+ Donors and Acceptors)

 Lewis (Lone Pair Donors and Acceptors)

 Brønsted—Lowry Acids and Bases

• Brønsted Acid: Proton (H+) Donor

• Brønsted Base: Proton (H+) Acceptor

• Reaction Mechanism

 Note: Electron Source to Electron Sink

H O H
O H + H Br + Br
H
H
Base Acid Conjugate Acid C. Base
 Lewis Acids and Bases

• Lewis Acid: Lone Pair Acceptor

• Lewis Base: Lone Pair Donor

• Reaction Mechanism

 Note: Electron Source to Electron Sink

I H + NH3 NH4 + I
 Lewis Acids and Bases

• Other Lewis Acids: ZnCl2 FeBr3

 Have Available Acceptor Orbital

• Other Lewis Bases: R-OH Br2

 Have Lone Pair to Donate

Lewis Acid/Base Reactions Essentially Electrostatic

(Opposite Charges Attract)

 Heterolysis of C—Z Bonds

• Heterolysis of C—Z Bonds Generates Ionic Species

 Carbocation: Postively Charged C Atom

 Carbocations Are Lewis Acids

 
C Z C + Z
 Carbanion: Negatively Charged C Atom
 Carbanions Are Lewis Bases

 
C Z C + Z
 Nucleophiles and Electrophiles

• Carbocations:

 Electrophiles

 Seek Electrons in Reaction to Fill/Stabilize Valence

• Carbanions:

 Nucleophiles

 Seek Proton or Some Other Positive Center

 “Nucleo” From Nucleus (Where Positive Charge Resides)

 More Reaction Mechanisms

H O H OH 2 H2O
+
H

O
O
H H O H
O H +
O
O H
H

O
O
H OH + H2O
O
O
 Acid/Base Reactions & Equilibrium

• We have viewed Acid/Base reactions as forward reactions;

they are actually Chemical Equilibria

O
O
H H O H
O H +
O
O H
H

 
[CH 3CO2 ][ H 3O ]
K eq 
[CH 3CO2 H ][ H 2O]
 pKa Values

• Provide Information About Acid Strength

 Lower pKa Values  Stronger Acids

 Higher pKa Values  Weaker Acids

CH3CH2OH versus CH3CO2H

pKa: 16 4.75

pKa Gives Information About Conjugate Base Strength as Well

 pKa and Base Strength

• Stronger Acid has Weak Conjugate Base

• Weaker Acid has Strong Conjugate Base

CH3CH2OH versus CH3CO2H

pKa: 16 4.75

CH3CH2O- versus CH3CO2-

Acetic Acid is the Stronger Acid; Ethoxide is the Stronger Base

 Predicting Acid/Base Reaction Outcomes

• Acid/Base Reactions Favor Formation of Weaker Acid/Base

 Use pKa Values to Help Determine Weaker Pair

• Reactions Under Equilibrium Control

 Favor Most Stable, Lowest Potential Energy Species

• General Rule: If pKa Difference > 5; Goes to Completion

Structural Factors Influencing Acidity

1. H—X Bond Strength

Weaker Bonds  Stronger Acids

Consider Halogen Acid Series

Acid: H—F H—Cl H—Br H—I

pKa: 3.2 -7 -9 -10

Stronger Bonds Weaker Bonds

Also Think About the Stability of the Ion (Conjugate Base)