CHEMICAL BONDS

Rachel Patricia B. Ramirez

Why bind?

 Bonding lowers the potential energy between positive and negative particles

Chemical Bonds
 Attractive forces that hold atoms together in compounds.  The electrons involved in bonding are usually those in the outermost (valence) shell.

Types of Chemical Bonding

 IONIC bonding results from electrostatic attractions among ions.
Transfer of one or more electrons Between atoms with large differences in their tendency to lose or gain electrons Interaction of metals (Grps 1 and 2) with nonmetals (Grps 17 and 16)

Types of Chemical Bonding

 COVALENT bonding results from sharing one or more pairs between two atoms
Each nonmetal atom holds onto its own electrons tightly and tends to attract other electrons as well Attraction of each nucleus for the valence electrons of the other draws the atoms together

Types of Chemical Bonding

 METALLIC bonds  All the metal atoms in a sample pool their valence electrons into an evenly distributed sea of electrons that flows between and around the metal-ion cores and attracts them together.  Bonding electrons are free to move (delocalized) throughout the three-dimensional structure

Lewis Electron-Dot Symbols

 Gilbert Newton Lewis (1875 1946)  Lewis electron-dot symbols

Nucleus and inner electrons

Li

Valence electron

Lewis Electron-Dot Symbols

 Elements that are in the same group have the same Lewis electron dot symbols.  The specific positions of the paired and unpaired dots are arbitrary.

Lewis Symbols and Bonding

 Metal total # of dots = # of electrons it loses to form a cation  Nonmetal # of unpaired dots

= # of electrons that become paired (gaining or sharing)

Lewis Symbols and Bonding

 Simple way of showing the valence electrons of atoms and tracking them in the course of bond formation  The Lewis electron-dot symbol of an atom depicts the number of valence electrons for a main-group element.

Lewis Electron-Dot Symbols

Element Electron Configuration [He] 2s1 [He] 2s2 [He] 2s2 2p1 [He] 2s2 2p2 Lewis Symbol Li Be B C

 Li  Be B C

Check-Up
 Write Lewis symbols for the following elements:
N, P, As, Sb Al, Se, I, Ar

Writing Lewis Symbols

 N, P, As, Sb, Bi
These are the elements of group 15. Their atoms have all have five valence electrons (ns2 np3). The Lewis symbols all have five dots.

Writing Lewis Symbols

 Al, Se, I, Ar
Al is in group 13 Se in group 16 I is in group 17 Ar in group 18

Writing Lewis Symbols

 For main-group elements, the number of valence electrons, and hence the number of dots appearing in a Lewis symbol, is equal to
The group number for the s-block elements The group number minus 10 for the p-block elements

Lewis Dot Formulas for Representative Elements

Group 1 2 13 14 15 16 17 18

The Ionic Bonding Model

 Transfer of electrons from metal to nonmetal to form ions that come together in a solid ionic compound.
Na+

Cl-

NaCl crystals consist of Na+ and Cl- ions held together by electrostatic attractions

Formation of Ionic Compounds

 An ion is an atom or a group of atoms possessing a net electrical charge  Types:
Positive (+) ions or CATIONS
Atoms have lost 1 or more electrons

Negative (-) ions or ANIONS

Atoms have gained 1 or more electrons

Formation of Ionic Compounds

 Monatomic ions (one atom).
Na+, Ca2+, Al3+ (cations) Cl , O2 , N3 (anions)

 Polyatomic ions (more than one atom)

NH4+ , H3O+ (cation) NO2 , CO32 , SO42 (anions)

Reaction of Group 1 metals with Group 17 Nonmetals

Grp1 Metal 2 Li (s) silver solid + Grp17 Nonmetal F2(g) yellow gas 2 LiF(s) white solid which melt at 842C

Bonding and Electron Configuration

Atom Li F Ion Li + F 1s oq oq 1s oq oq 2s o oq 2s oq 2p oq oq o 2p oq oq oq [He] [Ne]
valence electrons

Bonding and Lewis Symbols

 Lewis symbols can be used to represent the neutral atoms and the ions they form

Li

Li+

Bonding and Lewis Symbols

 The Li+ ion contains 2 electrons, same as the helium atom.
Li+ ions are isoelectronic with helium

 The F ion contains 10 electrons, same as the neon atom

F ions are isoelectronic with neon

NOTE: Isoelectronic species contain the same number of electrons

Check-Up
 The reaction of potassium with bromine is another example of a Group 1 metal reacting with a Group 17 nonmetal.
Write the reaction equation. Write the electron configuration of the atoms and the ions. Write the Lewis symbols for the reaction.

General Trend
 Cations become isoelectronic with the preceding noble gas.  Anions become isoelectronic with the following noble gas.

General Trend
 In nearly every main-group element that forms a monatomic ion, the configuration has a filled outer level of electrons (either two or eight), the same number as in the nearest noble gas.

Octet Rule
 When atoms bond, they lose, gain, or share electrons to attain a filled outer shell of eight (or two) electrons.
 An octet of electrons consists of full s and p subshells on an atom  The octet rule holds for all the compounds of Period 2 elements and a large number of others as well.

Reaction of Group 1 metals with Group 17 Nonmetals

Grp1 Metal 2 Li (s) silver solid + Grp17 Nonmetal F2(g) yellow gas 2 LiF(s) white solid which melt at 842C

General Representation
 Reaction equation 2 M(s) + X2 2 M+ X where: M is a metal (Li to Cs) X is a nonmetal (F to I)
ns o oq np oq oq o M+ X ns np oq oq oq oq

(s)

M X

Reaction of Group 2 metals with Group 17 Nonmetals

Grp2 Metal Be(s) + Grp17 Nonmetal F2(g) BeF2(s) 2s 2p Be2+ F oq oq oq oq

2s 2p Be [He] oq F [He] oq oq oq o

Bonding and Lewis Symbols

F Be + F Be2+

General Representation
 Reaction equation M(s) + X2 M2+ X2 where: M is a metal (Be to Ba) X is a nonmetal (F to Cl)
ns oq oq np oq oq o M+ X ns np oq oq oq oq

M X

Check-Up
Barium (Grp 2) reacts with chlorine (Grp 17).  Write the reaction equation  Draw the electron configuration for Ba and Cl, and their appropriate ions.  Draw the Lewis symbols for this reaction.

Simple Binary Ionic Compounds

Reacting Groups 1 + 17 2 + 17 3 + 17 General Formula MX MX2 MX3 Example LiF BeF2 AlF3

Reaction of Group 1 metals with Group 16 Nonmetals

Grp1 Metal 4 Li(s) + Grp16 Nonmetal O2(g) 2 Li2+ O2 (s) 2s Li+ O2 oq 2p oq oq oq

2s 2p Li [He] o O [He] oq oq oq

Check-Up
 Draw the Lewis symbols for the reaction of Li and O2.

General Representation
 Reaction equation
2 M(s) where: + X M2+ X

M is a Grp 1 metal (Li to Cs) X is a Grp 16 nonmetal (O to Te)

Simple Binary Ionic Compounds

Reacting Groups 1 + 16 2 + 16 3 + 16 General Formula M2X MX M2X3 Example Na2O BaO Al2S3

Reaction of Group 1 metals with Group 15 Nonmetals

Grp1 Metal 6 Na(s) + Grp15 Nonmetal N2(g) 2 Na3+N3 (s)

Check-Up
 Draw the Lewis symbols for the reaction of Na and N2.

Simple Binary Ionic Compounds

Reacting Groups 1 + 15 2 + 15 3 + 15 General Formula M3X M3X2 MX Example Na3N Mg3P2 AlN

Characteristics of Ionic Compounds

 Form extended three-dimensional arrays of oppositely charged ions
Na+

Cl-

Characteristics of Ionic Compounds

In A, no current flows in the solid because ions are immobile.

Characteristics of Ionic Compounds

In the molten compound, B mobile ions flow toward the oppositely charged electrodes and carry a current.

Characteristics of Ionic Compounds

In an aqueous solution of the compound, C mobile solvated ions carry a current.

The Covalent Bonding Model

 Covalent bonds form when atoms share electrons
If 2 electrons are shared single bond If 4 electrons are shared double bond If 6 electrons are shared triple bond

 Electrons have a lower potential energy when bound

Potential energy curve for H2

Too far apart, weak attractive force: no bond

Potential energy curve for H2

Each nucleus attracts the other atoms electron

Potential energy curve for H2

The combination of nucleus-electron attractions and electron-electron and nucleus-nucleus repulsions gives the minimum energy of the system.

Potential energy curve for H2

If the atoms move closer, repulsions increase the systems energy and force the atoms apart.

Potential energy curve for H2

For any covalent bond, there is an internuclear distance where the attractive forces are maximized in the presence of the repulsive forces.
BOND LENGTH

Potential energy curve for H2

At the bond length, the combination of bonded atoms is more stable than the separated atoms by an amount of energy.
BOND ENERGY

Covalent HH Bond
 Net result of attractive and repulsive electrostatic forces.

Nucleus-electron attractions and nucleus-nucleus and electron-electron repulsions occur simultaneously.

Formation of Covalent Bonds

Change in electron density as two hydrogen atoms approach each other.

Lengths of Covalent Bonds

Bond Order, Bond Length and Bond Energy

Bond Bond Order Average Bond Length (pm) Average Bond Energy (kJ/mol)

CO C! O C| O CC C! C C| C NN N! N N| N

1 2 3 1 2 3 1 2 3

143 123 113 154 134 121 146 122 110

358 745 1070 347 614 839 160 418 945

Some Common Covalent Compounds

Octet Rule
 When atoms bond, they lose, gain, or share electrons to attain a filled outer shell of eight (or two) electrons.
 An octet of electrons consists of full s and p subshells on an atom  The octet rule holds for all the compounds of Period 2 elements and a large number of others as well.

Octet Rule
 The representative elements usually attain noble gas electron configuration in most of their compounds  Distinguish between bonding (shared) electrons and nonbonding (unshared or lone pairs) of electrons

Writing Lewis Formulas

 Add up the valence electrons for each atom in the molecule. Use the periodic table to determine the number of valence electrons for each atom.  Write the symbols for the atoms in the molecule. In simple molecules, one atom will be the central atom surrounded by the other atoms.

Writing Lewis Formulas

 The central atom is often the first atom in the formula.
Central atom is determined by:  the atom that requires the largest number of electrons to complete its octet goes in the center  for two atoms in the same periodic group, the less electronegative element goes in the center

Writing Lewis Formulas

 Draw a dash (single bond, representing 2 electrons) between each pair of atoms covalently bonded together.  For each dash you drew, subtract 2 from your total number of valence electrons. Then draw the remaining electrons as dots around the atoms. Arrange the dots so that most atoms have eight valence electrons, and hydrogen has two.

Writing Lewis Formulas

 If there are not enough electrons to give the central atom an octet, try multiple bonds.
REMEMBER: In achieving an octet, the bonding electrons are counted for BOTH atoms.

Some Exceptions to the Octet Rule

 Molecules with an odd number of electrons
NO has 5 + 6 = 11 valence electrons

 Molecules in which an atom has less than an octet.

Some Exceptions to the Octet Rule

 Molecules in which an atom has more than an octet.

Check Up
Write the Lewis formula for  BBr3

 AsF5

Between the Extremes

 EITHER complete electron transfer OR complete electron sharing  In pure ionic bonds, electrons are completely lost or gained by one of the atoms  In pure covalent bonds, electrons are equally shared by the atoms Most compounds fall somewhere between these two extremes.

Electronegativity (EN)
 The relative ability of a bonded atom to attract the shared electrons.  Most common scale of relative EN values was developed by Linus Pauling.  EN values are not measured quantities but are based on Paulings assignment of the highest EN value, 4.0 to fluorine.

Electronegativities of the Elements

Nonpolar Covalent Bonds

 Covalent bonds in which the electrons are shared equally are designated as nonpolar covalent bonds.  Nonpolar covalent bonds have a symmetrical charge distribution.  To be nonpolar, the two atoms involved in the bond must be the same element to share equally.

Nonpolar Covalent Bonds

 H2

HH

or

H H

 N2

or

N N

Polar Covalent Bonds

 Covalent bonds in which the electrons are NOT shared equally are designated as polar covalent bonds.  Polar covalent bonds have an asymmetrical charge distribution.  To be polar, the two atoms involved in the bond must have different electronegativities.

Polar Covalent Bonds

 When atoms with different electronegativities form a bond, the bonding pair is shared unequally.

Polar covalent bond or polar bond is a covalent bond with greater electron density around one of the two atoms

electron poor region

electron rich region

e- poor

e- rich

H H+

F H-

A H+ indicates that the atom that is less electronegative has a partial positive charge. A H- indicates the atom that is more electronegative has a partial negative charge.

9.5

Polar Covalent Bonds

 The existence of partial charges means that a polar covalent bond behaves as if it were partially ionic.  The partial ionic character of a polar bond is related directly to the electronegativity difference ((EN).  ( EN is the difference between the EN values of the bonded atoms

Polar Covalent Bonds

 LiF (EN = = (EN = = (EN = = 4.0 1.0 3.0 4.0 2.1 1.9 4.0 4.0 0
A greater (EN results in larger partial charges and a higher partial ionic character.

 HF

 F2

The bond in LiF has more ionic character than the HF bond, which has more than the FF bond.

Classifying ionic character of chemical bonds

(EN > 1.7 0.4 1.7 < 0.4 Ionic Character Mostly ionic Polar covalent Non Polar Covalent

Increasing difference in electronegativity Covalent share ePolar Covalent partial transfer of eIonic transfer e-

Percent Ionic Character

 Calculated by comparing the actual behavior of a polar molecule in an electric field with the behavior it would have if the electron were transferred completely (pure ionic)  A value of 50% ionic character is often chosen to divide substances we recognize as ionic from those we recognize as covalent.

Percent Ionic Character

Percent ionic character generally increases with (EN.

Percent Ionic Character

 HF
= 43% ionic character 19% 11% 4%
As (EN becomes smaller, the bond becomes more covalent.

 HCl =  HBr =  HI
=