ORGANIC CHEMISTRY

POLAR COVALENT BONDS; ACIDS

AND BASES
Dipole Moments
Electronegativity

 factor in the unsymmetrical sharing of  indicates if a given compound is polar.

electrons between atoms.  measures the net molecular polarity.
 a great difference of electronegativity  represented by the greek mu (µ)
between two bonding atoms causes bond
polarity. µ = Q • r, expressed in debyes (D)
o Q = magnitude of charge at
 in polar covalent bonds, bonding electrons
are attracted more strongly by one atom either end of the molecular
dipole.
than the other.
o r = distance between the
o polar covalent = electrons are
shared unequally. charges.
o non-polar covalent = electrons are
shared equally.

 hydrocarbons contribute to
non-polarity
EN < 0.5 = nonpolar covalent bond o more hydroxyl groups =
more polar, more soluble
0.5 ≤ EN ≤ 2 = polar covalent bond in H2O
o more carbons = non-
EN > 2 = ionic bond
polar; less soluble in
H2O.
 highly symmetrical
structures are non-polar

 lone pairs of non-bonding

electrons contribute
significantly to dipole
moments.

A crossed arrow is used to indicate the direction of bond

polarity. By convention, electrons are displaced in the
direction of the arrow. The tail of the arrow is electron poor
(develops a partial positive charge) and the head of the arrow
is electron rich (develops a partial negative charge)

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Formal Charges resonance/canonical
forms.
 indicated in atoms having an abnormal  electrons are delocalized
number of bonds.
 the more resonance forms a
compound has, the more stable
it is.

 Rules for Resonance Forms

1. Individual resonance forms are

imaginary, not real.
2. Resonance forms differ only in the
placements of pi electrons and non-
The sulfur atom in dimethyl sulfoxide bonding valence electrons, not of
has three bonds rather than the usual two and has a formal the atoms.
positive charge. The oxygen atom, by contrast, has one bond
rather than the usual two and has a formal negative charge. 3. Different resonance forms of a
substance don't have to be
equivalent.
4. Resonance forms obey normal rules
of valency.
 formal charges give clues about chemical
5. The resonance hybrid is more
reactivity.
stable than any individual resonance
form.
6. Unequivalent resonance forms will
have one structure that is more
stable than the rest. This structure,
Carbon Radical Carbocation Carbanion which is more stable will have a
greater contribution to the
o carbon radical = a carbon atom resonance hybrid.
having four valence electrons. 7. Equivalent resonance forms are
However, only three electrons equally stable.
formed bonds and one electron
remained non-bonding.  Rules for determining the most stable
o carbocation = a carbon atom resonance form in unequivalent
having only three valence electrons, resonance structure
thus developing a + 1 charge. It also
forms three bonds. 1. The resonance form with the most
o carbanion = a carbon atom with number of atoms having a complete
five valence electrons, thus octet is the most stable.
developing a formal charge of - 1. It 2. Resonance forms having the least
also forms three bonds, and contains number of formal charges are more
a lone pair of non-bonding electrons. stable.
3. For a resonance form to be more
Resonance stable, the negative formal charge
must be in the atom with greater
 the ability of a compound to electronegativity. Consequently, the
have different placements of pi positive formal charge must be in
electrons and non-bonding the atom with less electronegativity.
valence electrons in its atoms. 4. The resonance form having the most
o resonance hybrid = the number of covalent bonds is the
true structure of a most stable.
compound; combination
of a compound's
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  Allowed movement when drawing 3. Sigma bond delocalization
resonance structures (C—H hyperconjugation)

1. Bond to lone pair.

2. Bond to bond.
3. Bond to atom
1. Pi electron delocalization
 pi electrons are found in pi
bonds (double bond or triple
bond)
 happens in conjugated triple or
double bonds (ex. benzene)

a.
2. Lone pair delocalization
 observed in allylic lone pairs.
o allylic lone pair = lone
pair in an atom next to a
pi bond.

Draw all canonical structures for each of the following

species:
b.

c.

d.

 Types of Electron Delocalization

1. Pi electron delocalization
2. Lone pair delocalization

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 Draw all canonical structures for each of the following
species:

3. C—H hyperconjugation
 involves sigma bonds and pi
bonds.
 alkyl groups serve as electron
donors.
 only possible if the carbon
directly attached to the benzene
ring has a hydrogen atom  Molecules with resonance meet the
attached to it. following criteria

1. Have at least one pi bond.

2. Have at least one of the following:
 a second, conjugated pi bond
 allylic alpha-atom with at least
one pair of electrons
 an allylic atom with a vacant p-
orbital.

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Structural Effects

 effects on the stability and reactivity of a

certain organic compound in terms of its
structure. II. Inductive Effect
 an atom's ability to polarize a bond.
I. Resonance Effects
 the shifting of electrons in a sigma
II. Inductive Effect
bond in response to the
III. Steric Effect
electronegativity of nearby atoms.
IV. Hydrogen bonding Effects
o factors =
electronegativity, position
of electronegative atom
I. Resonance Effect in the structure.
 the withdrawal or donation of electrons  a substituent may withdraw or
through a pi bond due to the overlap of a p donate/release electrons.
orbital on the substituent with a p orbital
on the aromatic ring.
 Electron Withdrawing
 in terms of acidity Substituents
 compounds that are capable of  more acidic
having resonance structures are  less basic
more acidic than those that are  offset - charge
not.  Halogens, hydroxyl groups,
 in terms of solubility carbonyl groups, cyano groups,
 unsaturated non-cyclic and nitro groups inductively
hydrocarbons are soluble in cold withdraw electrons through the
concentrated H2SO4 due to the sigma bond linking the
presence of pi electrons that can substituent to a benzene ring
coordinate with the protons
from the acid.
 simple amines are soluble in
dilute HCl because the lone pair
in the nitrogen are more
available. (amines are basic)
 simple amides are not soluble in
dilute HCl because the lone pair
in the nitrogen atom has lesser
availability than those of amines.
Disubstituted amides are acidic.
(amides are acidic)
 triphenylamine is not soluble in  Electron Donating Substituents
dilute HCl because the lone  more basic
pairs are unavailable for  less acidic
coordination with the acid.  offset + charge
 hyperconjugative effect
 alkyl groups (hydrocarbons)

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 3. If the halogen bonded to the
molecule having electron
withdrawing inductive effects has
greater electronegativity, acidity will
increase. (electron withdrawing
effect increases)

CARBOXYLIC ACID pKa

CH2FCOOH 2.66

 Rules for acidity CH2ClCOOH 2.86

CH2BrCOOH 2.90
1. The more carbon atoms a molecule
CH2ICOOH 3.17
with electron withdrawing inductive
effects has, the less acidic it
becomes; as the size of the R group
increases, electron donating effect order of increasing electronegativity: F > Cl > Br > I
increases. (electron donating 4. The nearer the electronegative atom
inductive effect increases) to the carboxyl group, the more
acidic the molecule is. (greater
CARBOXYLIC ACID pKa electron withdrawing effect)
HCOOH 3.75
CARBOXYLIC ACID pKa
CH3COOH 4.76 CH3CH2CH2COOH 4.82
CH3CH2COOH 4.82 CH3CH2CHClCOOH 2.84

CH3CH2CH2COOH 4.87 CH3CHClCH2COOH 4.06

CH2ClCH2CH2COOH 4.52

higher acidity = higher Ka = lower pKa

2. The presence of electronegative 5. The higher the s-character of a bond

atoms in a molecule having electron to hydrogen, the greater the
withdrawing inductive effects electron withdrawing inductive
increases its acidity. Greater number effect. Thus, the molecule is more
of these atoms means higher acidity. acidic. (multiple bonds have greater
(electron withdrawing effect s-character and higher
increases) electronegativity)

CARBOXYLIC ACID pKa

CH3COOH 4.76

CH2ClCOOH 2.86

CHCl2COOH 1.29

CCl3COOH 0.65

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  Rules for basicity  when alkyl groups are bulky in
secondary and tertiary amines,
1. The more carbon atoms (larger R solubility in dilute HCl increases.
group) a molecule having electron
donating inductive effect has, the IV. Hydrogen bonding
more basic it becomes. (electron  involves bonding of hydrogen
donating inductive effect increases) atoms to an electronegative N or
O atom.
AMINE pKb
CH3NH2 3.36  more atoms exhibiting hydrogen
bonding = more acidic.
CH3CH2NH2 3.27

CH3CH2CH2NH2 3.16

higher basicity = higher Ka = lower pKa Salicylic acid = less acidic more acidic

(all aliphatic primary amines are stronger bases

than ammonia)
Acids and Bases

2. Aliphatic amines are more basic than

A. The Arrhenius Theory
aromatic amines.
o Arrhenius Acid = substances that
3. Presence of electron donating group
produce H+ ions in aqueous
(alkyl groups) increases basicity
solution; contains H+ ion.
specially in the para-position.
o Arrhenius Base = substances that
produce OH- ions; contains OH-
ions in aqueous solution.
 most limited
 only applies to aqueous solutions
(substances must be dissolved in water)
most acidic (p-methylaniline)  allows only for one kind of base ( those
containing the hydroxide ion)
4. Alkoxy and hydroxyl groups
increase basicity.
III. Steric Effect
 results from steric strain.
 effect of atom or functional group
on crowding in the molecule.
 more bulky = less acidic
o cis = more bulky = less
acidic
o trans = less bulky = more
acidic

less bulky = less basic more bulky = basic

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 B. The Brønsted Lowry Definition

o Brønsted Lowry Acid =

substance that donates a hydrogen
ion, H+ (proton)
In this example, water acts as our Bronsted Acid and
o Brønsted Lowry Base =
Ammonia acts as the Bronsted Base.
substance that accepts a hydrogen
ion, H+ (proton)  notice that water can act either as an acid
or as a base, depending on the
 the name proton is often used as a circumstances. (water is amphoteric)
synonym to hydrogen ion (a hydrogen
Acid and Base Strength
atom that has lost its electron). This
loss of electrons from the neutral  defined by the equilibrium position
hydrogen atom leaves only the of its dissociation (ionization)
hydrogen nucleus (a proton) reaction.
 acids are also called electrophiles  stronger acids, such as HCl, react
(electron loving) almost completely with water,
 bases are also called nucleophiles whereas weaker acids, such as acetic
(nucleus loving) acid, react only slightly.
 acid-base or neutralization reactions  The exact strength of a given acid
involve the loss and gain of a single HA in water is described using the
proton. acidity constant (Ka) for the acid-
 when showing the reactions, reaction dissociation equilibrium.
mechanisms must be drawn (arrow  Stronger acids have their equilibria
goes from nucleophile to electrophile) toward the right and thus have
larger acidity constants, whereas
weaker acids have their equilibria
toward the left and have smaller
acidity constants.

o conjugate acid = a base that has

undergone protonation; formed
when a proton is transferred to a
base.
o conjugate base = everything that  Acid strengths are normally expressed using
pKa values rather than Ka values, where the
remains of the acid molecule after a
pKa is the negative common logarithm of
proton is lost; an acid that has the Ka:
undergone deprotonation.

higher Ka = lower pKa = higher acidity

In this example, water is our Bronsted Base and HCl is our

Bronsted Acid. When they react, the proton from HCl gets
attracted to water, forming chloride ion and hydronium ion.

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  because water is both the acid and the Organic Acids and Organic Bases
solvent, the equilibrium expression is
 practically all biological reactions involve
organic acids and organic bases.

I. Organic Acids
 contain a positively polarized H
atom.
 there is an inverse relationship between the  two main kinds:
acid strength of an acid and the base o acids that contain a
strength of its conjugate base. hydrogen atom bonded to
o strong acid = weak conjugate base an electronegative oxygen
o weak acid = strong conjugate base atom (ex. methanol and
ethanoic acid) *ethanoic acid is
a stronger acid than methanol
because it is capable of resonance
and has a negative formal charge
on its electronegative oxygen,
whereas methanol only has the
negative formal charge on its
oxygen and is incapable of
resonance.
o acids that contain a carbon
attached to an H atom next
to a carbonyl group. *the
acidity of acetone and other
carbonyl compounds are due to
the fact that they are capable of
A strong acid is one that loses H+ easily, meaning that its resonance
conjugate base holds the H+ weakly and is therefore a weak  compounds called carboxylic acids occur
base. A weak acid is one that loses H+ with difficulty, meaning abundantly in all living organisms. At the
that its conjugate base holds the proton tightly and is
therefore a strong base. The fact that HCl is a strong acid, for typical pH of 7.3 found within cells,
example, means that Cl- does not hold H+ tightly and is thus a carboxylic acids are usually dissociated and
weak base. Water, on the other hand, is a weak acid, meaning exist as their carboxylate anions (CO2-)
that OH- holds H+ tightly and is a strong base.

Predicting Acid-Base Reactions from pKa

Values

 For an acid-base reaction to take place to a

significant extent, the following condition II. Organic Bases
must be met:  contain an atom with a lone pair of
a) the product conjugate acid in an electrons that can bond to H+.
acid-base reaction must be weaker  nitrogen-containing compounds
and less reactive than the starting are the most common organic
acid and the product conjugate base bases.
must be weaker and less reactive  oxygen-containing compounds,
than the starting base. such as methanol and acetone
(organic acids) can also act as
bases when reacting with a
sufficiently strong acid. (methanol
and acetone act as acids when they
donate a proton but as bases when
their oxygen atom accepts a
proton)
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 2. Lewis Bases
 a compound with a pair of
non-bonding electrons that it
C. The Lewis Definition can use to bond and donate
its electrons to a Lewis Acid.
 most encompassing definition for
acids and bases.  negatively charged, expanded
o Lewis acid = accepts a pair octet.
of electrons.  mot oxygen- and nitrogen-
o Lewis base = donates a pair containing compounds are
of electrons. Lewis bases because they
 Lewis Acid-Base reactions create contain a lone pair of non-
one complex product. bonding electrons. *alcohols
and carboxylic acids can act
1. Lewis Acids as an acid when they donate
an H+ but as bases when they
 contains a vacant (or low-
accept an H+.
energy orbital or a polar
bond to H) orbital capable of
donating H+.
 few electrons, positive
charge, incomplete octet.
 metal cations (Mg2+, Ni2+,
etc.)
 compounds of group 3A
elements are also Lewis
Acids because they have
unfilled valence orbitals and
can accept electron pairs
from Lewis Bases (BF3, AlCl3)
 some compounds, such as
 transition metal compounds
carboxylic acids, amides, and
(TiCl4, FeCl3, ZnCl2, SnCl4)
esters, have more than one
 in the reaction, the Lewis
atom with lone pairs of
acid becomes more
electrons that can undergo
electronegative because it
protonation.
has accepted electrons and
the Lewis base becomes
more electropositive because
it has donated electrons.

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Using curved arrows, show how acetaldehyde
(ethanal) acts as a Lewis base
Noncovalent Interactions between
Molecules
 intermolecular forces or van der waals
forces.
I. Dipole-Dipole Forces
 occur between polar molecules as a
result of electrostatic interactions
among dipoles.
 can either be attractive or repulsive,
depending on the orientation of the
molecules.
o attractive = unlike charges
are together; lesser in energy
and more stable.
o repulsive = like charges are
together.
II. Dispersion Forces
 occur between all neighboring
molecules.
 arise from the constantly changing
electron distribution within
molecules. One side of a molecule may,
by chance, have a slight excess of electrons
relative to the opposite side, giving the
molecule a temporary dipole. This
temporary dipole in one molecule causes a
nearby molecule to adopt a temporarily
opposite dipole, resulting in a tiny attraction
between the two. Temporary molecular
dipoles have only a fleeting existence and
are constantly changing but their cumulative
effect is often strong enough to hold
molecules close together so that a
substance is a liquid or solid rather than a
gas.
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 dispersion forces have a great
impact in terms of a molecule's
physical properties (ex. boiling
point)
 higher molecular weight = higher
boiling point = more dispersion
forces.
III. Hydrogen-Bonding
 most important noncovalent
interaction in biological molecules.
 an attractive interaction between a
hydrogen bonded to an
electronegative O, N or F atom and
an unshared electron pair on
another O or N atom.
 very strong dipole-dipole interaction
involving polarized O–H or N–H
bonds.
 causes strands of DNA to pair up
and coil into the double helix that
stores genetic information.
o hydrophilic = substance strongly attracted
to water; "water-loving"
o hydrophobic = substance that is not
strongly attracted to water; "water-fearing"
 if there are more hydrogen atoms bonded to
electronegative atoms in a molecule, this
molecule will be strongly attracted to water.
o more H-bonds/hydroxyl groups = polar;
more soluble in H2O
 if there are more carbon atoms in a molecule,
this molecule is more likely to be non-polar.
Thus, it will be fat or lipid insoluble instead of
being water soluble.
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Sources:

Organic Chemistry (9th

ed.) by John Mcmurry.

Chemistry: An Atom's
First Approach
(International ed.) by
Steven Zumdahl and
Susan Zumdahl.

Chem 200 Lecture

Notes.

Chem 301 Lecture

Notes.

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