Chapter 2 - POLAR BONDS AND THIER CONSEQUENCES In the last chapter, learned about hybridization and the shape

and 3-D arrangement of atoms in molecules. We will look at other features of bonds and bonding in this chapter which can help in understanding reactions between functional groups and reagents. Polar Covalent Bonds: Mentioned in previous lecture that there is a continuum of possibilities of chemical bonding between the extremes of covalent and ionic bonding. The majority of chemical bonds lie other than at the ends of this continuum. Such bonds (unsymmetrical electron distribution - but not transfer) are called polar covalent bonds. The uneven electronic distribution is due to differences in electronegativity, (ability of an atom to attract electrons). SHOW ELECTRONEGATIVITY TRENDS IN PERIODIC TABLE. General rule: Bonds between atoms with similar electronegativities (EN) are covalent. Bonds between atoms with DEN 2 -2.3 units are polar covalent. Bonds between atoms with DEN 2.3 are largely ionic Two ways of indicating polarity of a bond. d+ and d- or a special arrow
Cl H H C Cl -

+
H

or

H H

C + H

Bonds between carbon and atoms of greater electronegativity:

+ H3C OH

Bonds between carbon and atoms of lesser electronegativity (metals):

H3C

Inductive effect: shifting of electrons in a bond in response to the electronegativity of nearby atoms. Used in speaking of an atom's ability to polarize a bond.... Polar Covalent Bonds - Dipole Moment Overall molecular polarity is the summation of all individual bond polarities and lone-pairs in the molecule. Dipole Moment of the molecule is the NET molecular polarity. Dipole moment, , is defined as the magnitude of the charge, Q, at either end of the molecular dipole times the distance, r, between the charges. =Qxr Dipole moments are expressed in debyes , D, where 1D = 3.336 x 10-30 coulomb meters. The shape of the molecule is important (3-D) is determining directions of the dipole moment. Show Table 2.1 Dipole Moments Non-Polar C-C F-F H-H C-H Polar C-Cl C-F C-O C=O Na+ ClK+FIonic

Li-C Pb-C A molecule with polar bonds is not necessarily a polar molecule. Shape of the molecule is important. Take into consideration hybridization, direction of polar bonds, etc.

+
MgBr 2

H NET O H

Try these: CO2 SO2 H2O CH4 CCl4 CH2Cl2 Best to draw Lewis dot structure, determine hybridization and shape and look at complete 3-D structure. FORMAL CHARGES: Occasionally need to assign charges to individual atoms in a molecule - when we look at the Lewis dot structure, some of the atoms do not appear to be in the neutral ground state with the correct number of bond pairs plus lone pairs. Sometimes these charges on atoms are important in how the molecule reacts. Formal charge is equal to the number of electrons in a neutral, isolated atom minus the number of electrons owned by that atom in a molecule.

Formal charge

Number of valence electrons in free atom Half of bonding electrons

Number of electrons in bound atom Number of nonbonding electrons

Number of valence electorns

Samples
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H H C H N

O O

RESONANCE STRUCTURES Sometimes when we write the Lewis dot structure, we find that there may be more than one possible arrangement of the ELECTRON PAIRS (the relative position of the atoms to each other is the same). For example:
H H C H N O O H H C H O N O

The individual Lewis dot structures are resonance forms and the relationship between the two (or more) structures is indicated by a double headed arrow. The true structure is neither (or none) of the resonance forms but is something inbetween. This is the RESONANCE HYBRID. 1. Individual resonance forms are imaginary, not real. 2. Resonance forms differ only in the distribution of their or non-bonding electrons. 3. Different resonance forms of a substance don't have to be equivalent. 4. Resonance forms must be valid Lewis dot structures and obey normal rules of valency.
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5. The resonance hybrid is more stable than any individual resonance form.

ACIDS AND BASES Over the years there have been several theories of acids and bases. We will look at only two here. Brnsted-Lowry: Acid - donates a proton in a reaction Base - accepts a proton in a reaction A:- + H-B+ H-A + :B
conjugates

General acid-base reaction

acid

base
conjugates

base

acid

H-Cl acid

+ HOH base

Cl- + H 3O+ base acid

HOH + NH3 acid base

OH- + NH4+ base acid

Are equilibrium reactions. Forward and reverse reactions occurring at the same rate when the system is in equilibrium. To express different acid ability to donate protons (strength of acid) we use acidity constants, Ka or pKa = - log Ka. Acidity constant is derived from the equilibrium constant of the reaction.
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H-Cl

+ HOH

Cl + H 3O

Keq =

[H3O+] [A- ] [HA] [H2O]

[H 3O+] [A-] [H3O+] [A- ] Ka is defined as Keq .[H2O] Ka = [H2O].Keq = [HA] [HA] The larger the Ka, the stronger the acid - that is, the better the proton donor. BE CAREFUL BECAUSE WE USUALLY TALK ABOUT DILUTE SOLUTIONS FOR MODERATE AND WEAK ACIDS. CONCENTRATIONS ARE USUALLY EXPRESSED IN NEGATIVE POWERS OF TEN. Strong acids numerator large denominator large Remember - 3 x 10-4 is a larger number than 4 x 10-5. pKa is defined as -log Ka pKa = - log Ka Since the pKa is negative log, LOWER pKa, STRONGER ACID Acid CH3CH2OH H2O HCN HOAc HF HNO3 HCl pKa 16.00 15.74 9.2 4.72 3.2 -1.3 -7 Conjugate base CH3CH2OHOCN-OAc

In dilute aqueous solutions, [H2O] is constant at 55M. Can rewrite equilibrium equation:

Weak acids

F-

An acid will react with (donate a proton to) the conjugate base of any acid with a higher pKa (weaker acid). OR Stronger acid donates proton to conjugate base of weaker acid. OR
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Reaction will proceed in direction of formation of weaker acid and base. HCN + CH3COO-Na + 9.2 CH3CH 2OH + Na+CN 16 CH3COOH + -OH 4.72 LEWIS ACIDS AND BASES ? NaCN + CH3COOH 4.72 Does not take place as written

Does not take place CH3CH 2O-Na+ + HCN as written 9.2 HOH + CH3COO15.74 Reaction occurs as written

Acid - substance that can accept an electron pair to form a covalent bond Base - substance that can furnish an electron pair. This is a broad definition and we will use this concept in many reactions LEWIS ACID must be electron defficient (not an octet of electrons around atom). Acids H
+

Bases
-

OH CH3 N CH3 CH3

BF3 AlCl3

F F B F

:N(CH3)3

Acid-Base Reaction (Lewis) F F B F H+ + + CH3 O CH3

_

F F B F HOH

CH3 O CH3

OH

Drawing structures: So far we have seen Lewis dot structures and Kekule line structures as a method of drawing structures for organic compounds. This is OK for simple structures, but can become very complicated for more complex structures that exist is organic chemistry. Organic structures range from the bizarre (http://www.ncl.ox.ac.uk/quicktime/brevetoxin.html) to the humorous (http://www.bris.ac.uk/Depts/Chemistry/MOTM/silly/sillymols.htm), but whatever they are, the structural drawings must information intelligible to the reader. Thus, you will need to understand the conventions used. Most bonding in organic structures is covalent in nature, i.e. the electron pairs are shared between the two atoms in the bond. Each bond consists of two electrons. Fully expanded notation of structures are Lewis dot structures that use two dots to represent an electron pair in a bond or unshared electron pairs (known as "lone pairs"). This method of notation, although inclusive of all information about valence electrons in a molecule becomes very cumbersome with large, complex molecules. Chemists have developed a shorthand method of structure representation which assumes basic understanding of the number of valence bonds for each kind of atom in the molecule. Chemists have devised some shorthand methods. Book describes "very short" shorthand method. First describe simple shorthand of left to right structures. Remember that carbon has four bonds in the neutral ground state, hydrogen has one, oxygen has two, etc.

H H C H H H C H H H C H H C H

H H H C C C H H H H H O C C H H H C OH H H H C C Cl H H H H C C OH H H

becomes CH3CH2CH 2CH3

becomes CH3CH 2CHO

becomes CH3CH2OH

Cl

becomes ClCH2CH 2CH2Cl

H HO C H

becomes HOCH2CH 2CH2OH

These structures are still pretty simple and can become very complicated especially when the carbon atoms are arranged in ring systems. So a very short shorthand method has been developed. 1. Carbon atoms are NOT usually shown. Carbon atoms are assumed to be at each intersection of two lines AND at the end of each line. (Sometimes carbon atoms are shown for emphasis e.g. in a functional group). 2. Hydrogens bonded to carbon are NOT usually shown (except for emphasis). Carbon has four bonds and therefore we can figure out how many hydrogens are present. 3. All atoms other than carbon and hydrogen are shown.

H H H H H C C

H C

H C C C H

H H H H H C N C C C N N C H H C H C

H C C C C H H

N N

N N H

N H

Importance of molecular models! Organic chem is a 3-D chemistry. Shape of molecule or at least shape of functional group often determines the particular chemistry that the compound undergoes. Can determine isomers. C2H7N CH3CH2NH2 vs. CH3NHCH3

Also CH3CH2CH2CH2CH3 is not a straight line. Zig-zag with many conformations. 3-D arrangements in space. Molecular models will help in "seeing" this.

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