2.

Polar Covalent Bonds: Acids and Bases

Why this chapter?
Description of basic ways chemists account for chemical reactivity. Establish foundation for understanding specific reactions discussed in subsequent chapters.

2.1 Polar Covalent Bonds: Electronegativity

Covalent bonds can have ionic character These are polar covalent bonds

Bonding electrons attracted more strongly by one atom than by the other Electron distribution between atoms is not symmetrical

Bond Polarity and Electronegativity

Electronegativity (EN): intrinsic ability of an atom to attract the shared electrons in a covalent bond Differences in EN produce bond polarity Arbitrary scale. As shown in Figure 2.2, electronegativities are based on an arbitrary scale F is most electronegative (EN = 4.0), Cs is least (EN = 0.7) Metals on left side of periodic table attract electrons weakly, lower EN Halogens and other reactive nonmetals on right side of periodic table attract electrons strongly, higher electronegativities EN of C = 2.5

The Periodic Table and Electronegativity

Bond Polarity and Inductive Effect

Nonpolar Covalent Bonds: atoms with similar EN Polar Covalent Bonds: Difference in EN of atoms < 2 Ionic Bonds: Difference in EN > 2 CH bonds, relatively nonpolar C-O, C-X bonds (more electronegative elements) are polar Bonding electrons toward electronegative atom C acquires partial positive charge, + Electronegative atom acquires partial negative charge, Inductive effect: shifting of electrons in a bond in response to EN of nearby atoms

Polarity, Shape
CO2 Electronegativity Difference < 0.5 Nonpolar 0.5-1.7 Polar >1.8 Ionic

O C
3.5 2.5

O
3.5

O=C=O

+ -

Polar Covalent Bonds Linear Shape (180o) Nonpolar Compound

Polarity, Shape
e-s in 2 directions = 180o

O=C=O

+ Nonpolar Compound Trigonal planar

Linear

e-s in 3 directions = 120o

- O

H + H

Polar Compound

BF3

Polarity, Shape

F
2.0 4.0 F

4.0

F F B F

B +
F

4.0

(120o)
Trigonal Planar

Polar Covalent Bonds

Nonpolar Compound

Polarity, Shape
e-s in 4 directions = 109.5o

H H H C H H C H Cl Cl H O H H-O-H
H

H
+

HH

Cl

4 directions = 109.5o

Tetrahedral

O
Bent

H+

e-s in 4 directions = 109.5o

Polarity, Shape

H N H H N H +H H + H H
(109.5o)

N H+

Pyramidal

Tetrahedral Configuration of Electrons Trigonal Pyramid Configuration of Atoms

Tetrahedral electron-pair Geometries

Tetrahedral

Pyramidal

Bent

Electrostatic Potential Maps

Electrostatic potential maps show calculated charge distributions Colors indicate electronrich (red) and electronpoor (blue) regions Arrows indicate direction of bond polarity

15

2.2 Polar Covalent Bonds: Dipole Moments

Molecules as a whole are often polar from vector summation of individual bond polarities and lone-pair contributions Strongly polar substances soluble in polar solvents like water; nonpolar substances are insoluble in water. Dipole moment () - Net molecular polarity, due to difference in summed charges - magnitude of charge Q at end of molecular dipole times distance r between charges

= Q r, in debyes (D), 1 D = 3.336 1030 coulomb meter length of an average covalent bond, the dipole moment would be 1.60 1029 Cm, or 4.80 D.

16

Dipole Moments in Water and Ammonia

Large dipole moments

EN of O and N > H Both O and N have lone-pair electrons oriented away from all nuclei

17

Absence of Dipole Moments

In symmetrical molecules, the dipole moments of each bond has one in the opposite direction The effects of the local dipoles cancel each other

18

Learning Check:
H F F H F H F H F F H H F F F F

A B D C Which of the above molecules is the most polar? 1. A 2. B 3. C 4. D 5. It cannot be determined

Solution:
H F F H F H F H F F H H F F F F

A B D C Which of the above molecules is the most polar? 1. A 2. B 3. C 4. D 5. It cannot be determined

Learning Check:
Which of the following molecules is nonpolar?
1.

2.
3. 4. 5.

H2O CH3CN CHCl3 CH2Cl2 CO2

21

Solution:
Which of the following molecules is nonpolar?
1.

2.
3. 4. 5.

H2O CH3CN CHCl3 CH2Cl2 CO2

22

Learning Check:
F H A H F F C H B F H C H F C C F H

Which of the above molecules has (have) a dipole moment?

1. 2.

3.
4. 5.

A only B only C only A and B B and C

Solution:
F H A H F F C H B F H C H F C C F H

Which of the above molecules has (have) a dipole moment?

1. 2.

3.
4. 5.

A only B only C only A and B B and C

2.3 Formal Charges

Sometimes it is necessary to have structures with formal charges on individual atoms We compare the bonding of the atom in the molecule to the valence electron structure If the atom has one more electron in the molecule, it is shown with a - charge If the atom has one less electron, it is shown with a + charge Neutral molecules with both a + and a - are dipolar

25

Formal Charge for Dimethyl Sulfoxide

Atomic sulfur has 6 valence electrons. Dimethyl suloxide sulfur has only 5. It has lost an electron and has positive charge. Oxygen atom in DMSO has gained electron and has (-) charge.

26

27

Learning Check:
What are the hybridization and a formal charge, respectively, on boron in BH4?
1.

2.
3. 4. 5.

sp3, 0 sp3, 1 sp3, +1 sp2, 1 sp2, +1

Solution:
What are the hybridization and a formal charge, respectively, on boron in BH4?
1.

2.
3. 4. 5.

sp3, 0 sp3, 1 sp3, +1 sp2, 1 sp2, +1

2.4 Resonance

Some molecules are have structures that cannot be shown with a single representation In these cases we draw structures that contribute to the final structure but which differ in the position of the bond(s) or lone pair(s) Such a structure is delocalized and is represented by resonance forms The resonance forms are connected by a double-headed arrow

30

Resonance Hybrids

A structure with resonance forms does not alternate between the forms Instead, it is a hybrid of the two resonance forms, so the structure is called a resonance hybrid For example, benzene (C6H6) has two resonance forms with alternating double and single bonds In the resonance hybrid, the actual structure, all its C-C bonds are equivalent, midway between double and single

31

2.5 Rules for Resonance Forms

Individual resonance forms are imaginary - the real structure is a hybrid (only by knowing the contributors can you visualize the actual structure) Resonance forms differ only in the placement of their or nonbonding electrons Different resonance forms of a substance dont have to be equivalent Resonance forms must be valid Lewis structures: the octet rule applies The resonance hybrid is more stable than any individual resonance form would be

32

Curved Arrows and Resonance Forms

We can imagine that electrons move in pairs to convert from one resonance form to another A curved arrow shows that a pair of electrons moves from the atom or bond at the tail of the arrow to the atom or bond at the head of the arrow

33

2.6 Drawing Resonance Forms

Any three-atom grouping with a multiple bond has two resonance forms

34

Different Atoms in Resonance Forms

Sometimes resonance forms involve different atom types as well as locations The resulting resonance hybrid has properties associated with both types of contributors The types may contribute unequally The enolate derived from acetone is a good illustration, with delocalization between carbon and oxygen

35

2,4-Pentanedione

The anion derived from 2,4pentanedione

Lone pair of electrons and a formal negative charge on the central carbon atom, next to a C=O bond on the left and on the right Three resonance structures result

36

Learning Check:
Which of the following statements is false concerning resonance structures?
1. 2. 3.

4.
5.

The arrangement of nuclei in all contributing structures must be the same. The arrangement of electrons in each contributing structure is different. Each atom in a contributing structure must have a completed valence shell. The contributing structures may have different energies. All contributing structures must have the correct number of valence electrons.

Solution:
Which of the following statements is false concerning resonance structures?
1. 2. 3.

4.
5.

The arrangement of nuclei in all contributing structures must be the same. The arrangement of electrons in each contributing structure is different. Each atom in a contributing structure must have a completed valence shell. The contributing structures may have different energies. All contributing structures must have the correct number of valence electrons.

Learning Check:
Consider all equivalent resonance structures for the carbonate anion shown below. If the bond order is defined as the number of electron pairs shared between two atoms, what is the average bond order for the C-O1 bond?

O
1. 2.

3.
4. 5.

2 3/2 4/3 1 1/4

Solution:
Consider all equivalent resonance structures for the carbonate anion shown below. If the bond order is defined as the number of electron pairs shared between two atoms, what is the average bond order for the C-O1 bond?

O
1. 2.

3.
4. 5.

2 3/2 4/3 1 1/4

Learning Check:
Consider all equivalent resonance structures for carbonate anion shown below. What is the formal charge on O1? 1

O
1. 2. 3. 4. 5.

1 2/3 1/2 1/3 0

Solution:
Consider all equivalent resonance structures for carbonate anion shown below. What is the formal charge on O1? 1

O
1. 2. 3. 4. 5.

1 2/3 1/2 1/3 0

Learning Check:
Anions with the negative charge residing on carbons are called carbanions. In the methyl anion the carbon is sp3 hybridized. What is the hybridization of carbon 1 in the allyl anion?
H H 1 H H H allyl anion (a carbanion)

1. 2.

sp3

3.
4. 5.

sp2 sp sp3d carbon 1 is not hybridized

Solution:
Anions with the negative charge residing on carbons are called carbanions. In the methyl anion the carbon is sp3 hybridized. What is the hybridization of carbon 1 in the allyl anion?
H H 1 H H H allyl anion (a carbanion)

1. 2.

sp3

3.
4. 5.

sp2 sp sp3d carbon 1 is not hybridized

Learning Check:
How many uncharged resonance structures exist for the following molecule?

1. 2.

3.
4. 5.

Only the one shown above 2 3 4 5

Solution:
How many uncharged resonance structures exist for the following molecule?

1. 2.

3.
4. 5.

Only the one shown above 2 3 4 5

2.7 Acids and Bases: The Brnsted Lowry Definition

The terms acid and base can have different meanings in different contexts For that reason, we specify the usage with more complete terminology The idea that acids are solutions containing a lot of H+ and bases are solutions containing a lot of OH- is not very useful in organic chemistry Instead, BrnstedLowry theory defines acids and bases by their role in reactions that transfer protons (H+) between donors and acceptors

47

Bronsted-Lowry theory
Acid = a Proton donor donates a proton, H+, to solvent

Example: HCl
HCl + H2O H3O+ + Clhydronium ion

Bronsted-Lowry theory
Example: HNO3

HNO3 + H2O

H3O+ + NO3-

HNO3 is the acid:

it donates the proton.

Bronsted-Lowry theory
Base = a proton acceptor accepts a Proton, H+, from solvent NH3 + H2O Accepted H+ NH4+ + OH-

NH3 is the Base:

it takes the proton.

Hydroxide ions (OH-) form when water donates the proton.

Common Acids

Battery Acid H2SO4 Stomach Acid HCl Coca Cola H3PO4

Sulfuric Acid Hydrochloric Acid Phosphoric Acid Carbonic Acid Acetic Acid Citric Acid Ascorbic Acid Tartaric Acid Acetyl Salicylic Acid

Carbonated WaterH2CO3 Vinegar HC2H3O2 H3C6O7H8 Citrus fruits Vitamin C HC6O6H7 H2C4O6H4 Grapes H2C9O4H8 Aspirin

Naming Acids
Binary Acids = (-ide ending) Hydro- ______-ic Acid Acid HCl = Hydrogen Chloride = Hydrochloric Oxoacids = H, Nonmetal & O -ate ending (The higher number of Os) ______________-ic Acid HNO3 = Hydrogen Nitrate = Nitric Acid
-ite

ending (The lower number of Os)

______________-ous Acid HNO2 = Hydrogen Nitrite = Nitrous Acid

Naming Acids
Non-Acid name Acid Name

H2SO4 Dihydrogen Sulfate H2SO3 Dihydrogen Sulfite Dihydrogen Sulfide H2S H3PO4 Trihydrogen Phosphate HBr Hydrogen Bromide H2CO3 Dihydrogen carbonate HNO2 Hydrogen Nitrite HNO3
Hydrogen Nitrate

Sulfuric Acid

Sulfurous Acid
Hydrosulfuric Acid Phosphoric Acid Hydrobromic Acid Carbonic Acid

Nitrous Acid
Nitric Acid Acetic Acid

HC2H3O2 Hydrogen Acetate

Naming Acids
Non-Acid name Acid Name

H2SO4 H2SO3 H2SO2

Dihydrogen Sulfate

Sulfuric Acid

Dihydrogen Sulfite
Dihydrogen Sulfide

Sulfurous Acid
Hyposulfurous Acid

HCl HClO
HClO2 HClO3 HClO4

Hydrogen Chloride Hydrogen hypochlorite Hydrogen chlorite Hydrogen chlorate Hydrogen Perchlorate

Hydrochloric Acid Hypochlorous Acid

Chlorous Acid
Chloric Acid Perchloric Acid

Battery Acid Stomach Acid Coca Cola Carbonated Water Vinegar Citrus fruits Vitamin C Grapes Aspirin

H2SO4 HCl H3PO4 H2CO3 HC2H3O2 H3C6O7H8 HC6O6H7 H2C4O6H4 H2C9O4H8

Common Acids Strong

100% ionization Strong electrolyte

Weak

Partial ionization Weak electrolyte Taste sour

Acids
H-Cl + H-O-H
H-Cl

H H O+ H

Cl-

HC2H3O2

H H O+ H

ClH+

HC2H3O2 C2H3O21-

H-C2H3O2 + H-O-H

+ + C H O 2 3 2 O H H

Bases
Base = gives hydroxide ions in water.
(Arrhenius definition)

= takes hydrogen ions in water.

(Bronsted-Lowry definition)

NaOH
NaOH

Na+

Na+

OH-

OH-

OHNa+

Brnsted Acids and Bases

Brnsted-Lowry is usually shortened to Brnsted A Brnsted acid is a substance that donates a hydrogen ion (H+) A Brnsted base is a substance that accepts the H+

proton is a synonym for H+ - loss of an electron from H leaving the bare nucleusa proton
58

The Reaction of Acid with Base

Hydronium ion, product when base H2O gains a proton HCl donates a proton to water molecule, yielding hydronium ion (H3O+) [conjugate acid] and Cl [conjugate base] The reverse is also a Brnsted acidbase reaction of the conjugate acid and conjugate base

59

2.8 Acid and Base Strength

The equilibrium constant (Keq) for the reaction of an acid (HA) with water to form hydronium ion and the conjugate base (A-) is a measure related to the strength of the acid Stronger acids have larger Keq Note that brackets [ ] indicate concentration, moles per liter, M.

60

Ka the Acidity Constant

The concentration of water as a solvent does not change significantly when it is protonated The molecular weight of H2O is 18 and one liter weighs 1000 grams, so the concentration is ~ 55.4 M at 25 The acidity constant, Ka for HA Keq times 55.6 M (leaving [water] out of the expression) Ka ranges from 1015 for the strongest acids to very small values (10-60) for the weakest

61

62

pKa the Acid Strength Scale

pKa = -log Ka The free energy in an equilibrium is related to log of Keq (DG = -RT log Keq) A smaller value of pKa indicates a stronger acid and is proportional to the energy difference between products and reactants The pKa of water is 15.74

63

2.9 Predicting AcidBase Reactions from pKa Values

pKa values are related as logarithms to equilibrium constants Useful for predicting whether a given acid-base reaction will take place The difference in two pKa values is the log of the ratio of equilibrium constants, and can be used to calculate the extent of transfer The stronger base holds the proton more tightly

64

2.10 Organic Acids and Organic Bases

-

Organic Acids: characterized by the presence of positively polarized hydrogen atom

65

Organic Acids

Those that lose a proton from OH, such as methanol and acetic acid Those that lose a proton from CH, usually from a carbon atom next to a C=O double bond (O=CCH)

66

Organic Bases

Have an atom with a lone pair of electrons that can bond to H+ Nitrogen-containing compounds derived from ammonia are the most common organic bases Oxygen-containing compounds can react as bases when with a strong acid or as acids with strong bases

67

2.11 Acids and Bases: The Lewis Definition

Lewis acids are electron pair acceptors and Lewis bases are electron pair donors Brnsted acids are not Lewis acids because they cannot accept an electron pair directly (only a proton would be a Lewis acid) The Lewis definition leads to a general description of many reaction patterns but there is no scale of strengths as in the Brnsted definition of pKa

68

Lewis Acids and the Curved Arrow Formalism

The Lewis definition of acidity includes metal cations, such as Mg2+ They accept a pair of electrons when they form a bond to a base Group 3A elements, such as BF3 and AlCl3, are Lewis acids because they have unfilled valence orbitals and can accept electron pairs from Lewis bases Transition-metal compounds, such as TiCl4, FeCl3, ZnCl2, and SnCl4, are Lewis acids Organic compounds that undergo addition reactions with Lewis bases (discussed later) are called electrophiles and therefore Lewis Acids The combination of a Lewis acid and a Lewis base can shown with a curved arrow from base to acid
69

Illustration of Curved Arrows in Following Lewis Acid-Base Reactions

70

Lewis Bases

Lewis bases can accept protons as well as Lewis acids, therefore the definition encompasses that for Brnsted bases Most oxygen- and nitrogen-containing organic compounds are Lewis bases because they have lone pairs of electrons Some compounds can act as both acids and bases, depending on the reaction

71

Learning Check:
All Lewis acids can also be classified as Brnsted-Lowry acids.

1. 2.

True False

Solution:
All Lewis acids can also be classified as Brnsted-Lowry acids.

1. 2.

True False

Learning Check:
Which statement best describes the following reaction?
NH3 +
1. 2. 3. 4.

BH3

H3N BH3

5.

an acid-base reaction where NH3 acts as a BrnstedLowry acid an acid-base reaction where NH3 acts as a BrnstedLowry base an acid-base reaction where NH3 acts as a Lewis acid an acid-base reaction where NH3 acts as a Lewis base None of these adequately describes the reaction.

Solution:
Which statement best describes the following reaction?
NH3 +
1. 2. 3. 4.

BH3

H3N BH3

5.

an acid-base reaction where NH3 acts as a BrnstedLowry acid an acid-base reaction where NH3 acts as a BrnstedLowry base an acid-base reaction where NH3 acts as a Lewis acid an acid-base reaction where NH3 acts as a Lewis base None of these adequately describes the reaction.

Learning Check:
What is the main reason why molecule A is less acidic than molecule B? A: CH3CH2CH2-H B: CH3CH2O-H
1.

2.
3. 4. 5.

There are more hydrogens in A. The C-H bond is weaker than the O-H bond. The conjugate base of A is more stable than the conjugate base of B. In the conjugate base of B, the negative charge resides on a more electronegative atom. There is resonance and inductive stabilization of conjugate base of B.

Solution:
What is the main reason why molecule A is less acidic than molecule B? A: CH3CH2CH2-H B: CH3CH2O-H
1.

2.
3. 4. 5.

There are more hydrogens in A. The C-H bond is weaker than the O-H bond. The conjugate base of A is more stable than the conjugate base of B. In the conjugate base of B, the negative charge resides on a more electronegative atom. There is resonance and inductive stabilization of conjugate base of B.

Learning Check:
Ammonia can act as all four classifications of acids or bases (Lewis acid, Lewis base, Brnsted-Lowry acid, and Brnsted-Lowry base.)

1. 2.

True False

Solution:
Ammonia can act as all four classifications of acids or bases (Lewis acid, Lewis base, Brnsted-Lowry acid, and Brnsted-Lowry base.)

1. 2.

True False

Learning Check:
Van der Waals interactions refer to the weak attractive forces that occur between individual molecules and are very important in determining the shape and properties of biological molecules such as proteins. Which of the following play no role in van der Waals interactions?
1. 2. 3. 4. 5.

hydrogen bonding dispersion forces dipole-dipole forces magnetic forces All of these are important in van der Waals interactions.

Solution:
Van der Waals interactions refer to the weak attractive forces that occur between individual molecules and are very important in determining the shape and properties of biological molecules such as proteins. Which of the following play no role in van der Waals interactions?
1. 2. 3. 4. 5.

hydrogen bonding dispersion forces dipole-dipole forces magnetic forces All of these are important in van der Waals interactions.

Learning Check:
Which is the correct order of the pKa values?
1.
2. 3.

4.
5.

H2O > HO > H3O+ HO > H3O+ > H2O H3O+ > HO > H2O HO > H2O > H3O+ H3O+ > H2O > HO

Solution:
Which is the correct order of the pKa values?
1.
2. 3.

4.
5.

H2O > HO > H3O+ HO > H3O+ > H2O H3O+ > HO > H2O HO > H2O > H3O+ H3O+ > H2O > HO

2.12 Molecular Models

Organic chemistry is 3-D space Molecular shape is critical in determining the chemistry a compound undergoes in the lab, and in living organisms

84

2.13 Noncovalent Interactions

Several types: Dipole-dipole forces Dispersion forces Hydrogen bonds

85

Dipole-Dipole
Occur between polar molecules as a result of electrostatic interactions among dipoles Forces can be attractive of repulsive depending on orientation of the molecules

86

Dispersion Forces
Occur between all neighboring molecules and arise because the electron distribution within molecules that are constantly changing

87

Hydrogen Bond Forces

Most important noncovalent interaction in biological molecules Forces are result of attractive interaction between a hydrogen bonded to an electronegative O or N atom and an unshared electron pair on another O or N atom

88

89

Summary

Organic molecules often have polar covalent bonds as a result of unsymmetrical electron sharing caused by differences in the electronegativity of atoms The polarity of a molecule is measured by its dipole moment, . (+) and () indicate formal charges on atoms in molecules to keep track of valence electrons around an atom Some substances must be shown as a resonance hybrid of two or more resonance forms that differ by the location of electrons. A Brnsted(Lowry) acid donates a proton A Brnsted(Lowry) base accepts a proton The strength Brnsted acid is related to the -1 times the logarithm of the acidity constant, pKa. Weaker acids have higher pKas
90

Summary (contd)
A Lewis acid has an empty orbital that can accept an electron pair A Lewis base can donate an unshared electron pair In condensed structures C-C and C-H are implied Skeletal structures show bonds and not C or H (C is shown as a junction of two lines) other atoms are shown Molecular models are useful for representing structures for study Noncovalent interactions have several types: dipoledipole, dispersion, and hydrogen bond forces

91

Learning Check:
OH + OH phenoxide pKa = 16 O + H2O phenol pKa = 10 hydroxide

Which statement about the acid-base equilibrium shown above is incorrect?

1. 2. 3. 4. 5.

the equilibrium favors the products water is a conjugate acid in this equilibrium hydroxide is the strongest base present phenol is 6 times more acidic than water the negative charge in the phenoxide is resonance stabilized

Solution:
OH + OH phenoxide pKa = 16 O + H2O phenol pKa = 10 hydroxide

Which statement about the acid-base equilibrium shown above is incorrect?

1. 2. 3. 4. 5.

the equilibrium favors the products water is a conjugate acid in this equilibrium hydroxide is the strongest base present phenol is 6 times more acidic than water the negative charge in the phenoxide is resonance stabilized

Learning Check:
What is the most likely product of the following Lewis O acid-base reaction?
+ O BF3 product

BF3

BF3

O BF3

1. 2.

3.
4. 5.

A B C D E

O A

O B

O BF3 C

O BF3 D

Solution:
What is the most likely product of the following Lewis O acid-base reaction?
+ O BF3 product

BF3

BF3

O BF3

1. 2.

3.
4. 5.

A B C D E

O A

O B

O BF3 C

O BF3 D

Learning Check:
Which of these structures is not a resonance form of the others? (The lone pairs are not shown explicitly.)
N H N H c)

N H

N H d)

N H e)

a)

b)

1. 2.

3.
4. 5.

a b c d e

Solution:
Which of these structures is not a resonance form of the others? (The lone pairs are not shown explicitly.)
N H N H c)

N H

N H d)

N H e)

a)

b)

1. 2.

3.
4. 5.

a b c d e