General Chemistry M R NaimiJamal Faculty of Chemistry

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General Chemistry M. R. Naimi-Jamal Faculty of Chemistry Iran University of Science & Technology

General Chemistry M. R. Naimi-Jamal Faculty of Chemistry Iran University of Science & Technology

Chemical Bonding Problems and questions: How is a molecule or polyatomic ion held together?

Chemical Bonding Problems and questions: How is a molecule or polyatomic ion held together? Why are atoms distributed at strange angles? Why are molecules not flat? Can we predict the structure? How is structure related to chemical and physical properties?

Forms of Chemical Bonds • There are 2 extreme forms of connecting or bonding

Forms of Chemical Bonds • There are 2 extreme forms of connecting or bonding atoms: • Ionic—complete transfer of electrons from one atom to another • Covalent—electrons shared between atoms • Most bonds are somewhere in between.

Covalent Bonding Covalent bond forms by the sharing of VALENCE ELECTRONS, the electrons at

Covalent Bonding Covalent bond forms by the sharing of VALENCE ELECTRONS, the electrons at the outer edge of the atom. The bond arises from the mutual attraction of 2 nuclei for the same electrons.

Valence Electrons are divided between core and valence electrons. Na 1 s 2 2

Valence Electrons are divided between core and valence electrons. Na 1 s 2 2 p 6 3 s 1 Core = [Ne] and valence = 3 s 1 Br [Ar] 3 d 10 4 s 2 4 p 5 Core = [Ar] 3 d 10 and valence = 4 s 2 4 p 5

Chemical Bonding Objectives are to understand: 1. e- distribution in molecules and ions. 2.

Chemical Bonding Objectives are to understand: 1. e- distribution in molecules and ions. 2. molecular structures 3. bond properties and their effect on molecular properties.

Electron Distribution in Molecules • Electron distribution is depicted with Lewis electron dot structures

Electron Distribution in Molecules • Electron distribution is depicted with Lewis electron dot structures • Electrons are distributed as shared or BOND PAIRS and unshared or LONE PAIRS. G. N. Lewis 1875 - 1946

Lewis Symbols • A chemical symbol represents the nucleus and the core e-. •

Lewis Symbols • A chemical symbol represents the nucleus and the core e-. • Dots around the symbol represent valence e-. • • Si • • • Al • • • As • • P • • • • . • Se • • • Bi • • • Sb • • • • I • • • • • Ar • • • N • • • •

Bond and Lone Pairs • Electrons are distributed as shared or BOND PAIRS and

Bond and Lone Pairs • Electrons are distributed as shared or BOND PAIRS and unshared or LONE PAIRS. This is called a LEWIS ELECTRON DOT structure.

Bond Formation A bond can result from a “head-to-head” overlap of atomic orbitals on

Bond Formation A bond can result from a “head-to-head” overlap of atomic orbitals on neighboring atoms. This type of overlap places bonding electrons in a MOLECULAR ORBITAL along the line between the two atoms and forms a SIGMA BOND ( ).

Covalent Bonding

Covalent Bonding

Coordinate Covalent Bonds + H H Cl H N H H • • Cl

Coordinate Covalent Bonds + H H Cl H N H H • • Cl • • - • • H N H • • H

Multiple Covalent Bonds • • • • N N • • • N •

Multiple Covalent Bonds • • • • N N • • • N • • • •

Polar Covalent Bonds δ+ H Cl δ-

Polar Covalent Bonds δ+ H Cl δ-

Electronegativity x. A-x. B = √ D/23. 06 Pauling electronegativity D = 2 E(A-B)

Electronegativity x. A-x. B = √ D/23. 06 Pauling electronegativity D = 2 E(A-B) – E(A-A) – E(B-B) = I+A 2 I = Ionization Energy, A = Electron Affinity Mulliken electronegativity

Electronegativity

Electronegativity

Dipole Moments

Dipole Moments

Dipole Moments

Dipole Moments

Percent Ionic Character

Percent Ionic Character

Writing. Lewis. Structures Writing • No. of valence electrons of an atom = group

Writing. Lewis. Structures Writing • No. of valence electrons of an atom = group number • For groups 1 A-4 A, no. of bond pairs = group number • For groups 5 A-7 A, BP’s = 8 - gr. no. • Except for H (and atoms of 3 rd and higher periods), BP’s + LP’s = 4 This observation is called the OCTET RULE

Writing Lewis Structures • All the valence e- of atoms must appear. • Usually,

Writing Lewis Structures • All the valence e- of atoms must appear. • Usually, the e- are paired. • Usually, each atom requires an octet. – H only requires 2 e-. • Multiple bonds may be needed. – Readily formed by C, N, O, S, and P.

Skeletal Structure • Identify central and terminal atoms. • C 2 H 5 OH

Skeletal Structure • Identify central and terminal atoms. • C 2 H 5 OH H H C O H H

Skeletal Structure • Hydrogen atoms are always terminal atoms. • Central atoms are generally

Skeletal Structure • Hydrogen atoms are always terminal atoms. • Central atoms are generally those with the lowest electronegativity. • Carbon atoms are always central atoms. • Generally structures are compact and symmetrical.

Building a Dot Structure Ammonia, NH 3 1. Decide on the central atom; Central

Building a Dot Structure Ammonia, NH 3 1. Decide on the central atom; Central atom is generally atom of lowest affinity for electrons, but never H, here N is central. 2. Count valence electrons H = 1 and N = 5 Total = (3 x 1) + 5 = 8 electrons / 4 pairs

Building a Dot Structure 3. Form a sigma bond between the central atom and

Building a Dot Structure 3. Form a sigma bond between the central atom and surrounding atoms. 4. Remaining electrons form LONE PAIRS to complete octet as needed. 3 BOND PAIRS and 1 LONE PAIR. Note that N has a share in 4 pairs (8 electrons), while H shares 1 pair.

Sulfite ion, SO 32 Step 1. Central atom = S Step 2. Count valence

Sulfite ion, SO 32 Step 1. Central atom = S Step 2. Count valence electrons S= 6 3 x O = 3 x 6 = 18 Negative charge = 2 TOTAL = 26 e- or 13 pairs Step 3. Form sigma bonds

Sulfite ion, SO 32 - 10 pairs of electrons are now left.

Sulfite ion, SO 32 - 10 pairs of electrons are now left.

Sulfite ion, SO 32 Remaining pairs become lone pairs, first on outside atoms and

Sulfite ion, SO 32 Remaining pairs become lone pairs, first on outside atoms and then on central atom. • • • • O • • O S • • O • • • • Each atom is surrounded by an octet of electrons.

Carbon Dioxide, CO 2 1. 2. 3. Central atom = C Valence electrons =

Carbon Dioxide, CO 2 1. 2. 3. Central atom = C Valence electrons = 16 or 8 pairs Form sigma bonds. This leaves 6 pairs.

Carbon Dioxide, CO 2 4. Place lone pairs on outer atoms. BUT C doesn’t

Carbon Dioxide, CO 2 4. Place lone pairs on outer atoms. BUT C doesn’t obey the octet rule! 5. So that C has an octet, we shall form DOUBLE BONDS between C and O.

Carbon Dioxide, CO 2 The second bonding pair forms a pi (p ( )

Carbon Dioxide, CO 2 The second bonding pair forms a pi (p ( ) bond. • • O • • C O • • • •

Double and even triple bonds are commonly observed for C, N, P, O, and

Double and even triple bonds are commonly observed for C, N, P, O, and S H 2 CO SO 3 C 2 F 4

Sulfur Dioxide, SO 2 1. Central atom = S 2. Valence electrons = 18

Sulfur Dioxide, SO 2 1. Central atom = S 2. Valence electrons = 18 or 9 pairs 3. Form sigma bonds. O S O This leaves 7 pairs. 4. Place 7 lone pairs on outer atoms. • • • • O • • S • • O • • • •

Sulfur Dioxide, SO 2 5. Form pi (p ( ) bond so that S

Sulfur Dioxide, SO 2 5. Form pi (p ( ) bond so that S has an octet — but note that there are two ways of doing this.

Sulfur Dioxide, SO 2 This leads to the following structures: These equivalent structures are

Sulfur Dioxide, SO 2 This leads to the following structures: These equivalent structures are called: RESONANCE STRUCTURES The true electronic structure is a HYBRID of the two.

Urea, (NH 2)2 CO

Urea, (NH 2)2 CO

Urea, (NH 2)22)CO 2 CO 1. Central atom = C 2. Number of valence

Urea, (NH 2)22)CO 2 CO 1. Central atom = C 2. Number of valence electrons = 24 e 3. Draw sigma bonds

Urea, (NH 2)2 CO 4. Place remaining electron pairs in the molecule.

Urea, (NH 2)2 CO 4. Place remaining electron pairs in the molecule.

Urea, (NH 2)22)CO 2 CO 5. Complete C atom octet with double bond.

Urea, (NH 2)22)CO 2 CO 5. Complete C atom octet with double bond.

Violations of the Octet Rule Usually occurs with B and elements of higher periods.

Violations of the Octet Rule Usually occurs with B and elements of higher periods. . . BF 3 SF 4

Boron Trifluoride • Central atom = B • Valence electrons = 24 or electron

Boron Trifluoride • Central atom = B • Valence electrons = 24 or electron pairs = 12 • Assemble dot structure The B atom has a share in only 6 pairs of electrons (or 3 pairs). B atom in many molecules is electron deficient.

Sulfur Tetrafluoride, SF 4 • Central atom = S • Valence electrons = 34

Sulfur Tetrafluoride, SF 4 • Central atom = S • Valence electrons = 34 or 17 pairs. • Form sigma bonds and distribute electron pairs. 5 pairs around the S atom. A common occurrence outside the 2 nd period.

Exceptions to the Octet Rule • Odd e- species: • • • N=O •

Exceptions to the Octet Rule • Odd e- species: • • • N=O • • H • O—H • • • H—C—H • •

Exceptions to the Octet Rule • • • Incomplete octets: • • F •

Exceptions to the Octet Rule • • • Incomplete octets: • • F • • B • • F • •

Formal Charge FC = #valence e- - #lone pair e- - 1 2 #bond

Formal Charge FC = #valence e- - #lone pair e- - 1 2 #bond pair e-

Carbon Dioxide, alternative lewis structure 6 - (1/ 2)(2) - 6 = -1 •

Carbon Dioxide, alternative lewis structure 6 - (1/ 2)(2) - 6 = -1 • • • • O C 6 - (1/ 2)(6) - 2 O • • • • = +1 Which is the predominant resonance structure?

Boron Trifluoride, BF 3 What if we form a B—F double bond to satisfy

Boron Trifluoride, BF 3 What if we form a B—F double bond to satisfy the B atom octet?

Boron Trifluoride , BF 3 Boron Trifluoride, BF 3 • • • • F

Boron Trifluoride , BF 3 Boron Trifluoride, BF 3 • • • • F FC = 7 - 2 - 4 = +1 B FC = 3 - 4 - 0 = -1 • • • • F • • • To have +1 charge on F, with its very high affinity for electrons, is not good. • Negative charges are best placed on atoms with high affinity for electrons.

Formal Charges & Lewis Structure

Formal Charges & Lewis Structure

Chapter 7 Questions 6, 8, 18, 21, 31 32, 38, 44, 48 52

Chapter 7 Questions 6, 8, 18, 21, 31 32, 38, 44, 48 52