Chemical Bond

Lattice Energies and Types of Ions

Na (s) + 1/2Cl2 (g)  NaCl (s) ΔH= -411 kJ/mol

Energetically favored: lower energy

Like a car rolling down a hill

We will not be doing these type of calculations however, if interested then can read on
your own

Question why Cl- and not Cl2-

Na+ and not Na2+
Mg2+ and not Mg+

Answer energetically most favored always have cation and anion

Get out more energy than you put in

Born Haber cycle is formal method of keeping track of energy changes

Periodic Table (older Roman numerals)

IA IIA IIIA s2 and s2p6 ions
VA VIA VIIA s2 and s2p6 ions
IB IIB d10 ions
IIIA IVA VA d10s2 ions

Transition metals frequently form more than one type of cation

Most will form +2 by losing 4s2 electrons and some others are more complex structures

Example:
Pour ammonia solution in bottle and add concentrated HCl to produce a white smoke
NH4Cl which stays in bottle. Add water and shake and white smoke disappears because
NH4Cl is soluble in water

NH3 + HCl  NH4+Cl- (ammonium chloride)

Bonding General Concepts

Chemical Bonds – atoms combine, Electron distribution changes

Types of Bonds: Ionic, Covalent and Metallic

Ionic Bonds is the transfer of electrons (ex. salts, crystals) and is composed of a positive
(cation) and negative (anion)

Covalent is the sharing of electrons and the compound is either molecular (CH4) or
networking (diamond)

Metallic Bond is the outer electrons move throughout solid and holds nuclei together and
the compound is only composed of metals

Conduction of Electricity

Type of Bond Compound Conduct Explanation

Electricity
Ionic Solid NaCl No Na+Cl- ions held
rigid
Ionic Liquid NaCl Yes Ions free to move
Covalent Solid Cl2 No Cl—Cl all electrons
(molecules) tied up
Covalent Liquid Cl2 No Cl—Cl all electrons
tied up
Metallic Solid Na Yes Outer electrons
move throughout
metal
Metallic Liquid Na Yes Electrons free to
move throughout

More unpaired than would expect from electron configuration because of hybrid orbitals
Valence Electrons
By sharing or transferring valence electrons the electronic configuration of noble gases
frequently obtained from A family elements

Element Inner electrons Outer electrons

He 1s2
Ne (He) 2s22p6
Ar (Ne) 3s23p6
Kr (Ar)3d10 4s24p6
Xe (Kr)4d10 5s25p6

Metal and Nonmetal

Electrons Lost Electrons Gained
Na Cl
[Ne] 1s1 [Ne] 3s23p5

Octet Rule

Rules of Eight and Two works for IA, IIA, Nonmetals

H, Li, Be
H-, Li+, Be2+ Isoelectronic with the same electronic structure

Eight (Octet Rule) Na+, F-1, O-2

Isoelectronic with (Ne)

Exceptions especially in d orbital

Lose electrons in different order than build up

Transition element loses electron from outer s subshell first

Zn [Ar] 3d104s2  Zn2+ [Ar] 3d10 + 2e-

Pseudonoble gas configuration ns2np6nd10

Ionic Bond
Electron dot structure
Sodium metal explosive metal when added to water
Chlorine gas is a poisonous gas
Sodium chloride white crystal essential for life transfer e-
Bonds:
Ionic

(http://www.chemistry.montana.edu/bchm204/pages/elements_files/elements.html)

Covalent

Cl + Cl  Cl2
The Cl—Cl bond shares electrons to complete the octet

Element Valence e- s p p p

Al 3s23p1 __ __ __ __

Na 3s1 __ __ __ __

O 2s22p4 __ __ __ __

Cl 3s23p5 __ __ __ __

Show valence electrons

The valence electrons are the ones beyond the noble gas or beyond noble gas and d
electrons
(The number at the top of the periodic table)

Water H2O

(http://www.olemiss.edu/courses/chem105_jg/CHEM%20105-Ch%209/CHEM%20105-Ch%209.html)

(http://www.owlnet.rice.edu/~chem122/class/assignments/SBR_Homework/Homework7.htm)

Lewis Structure is a powerful technique to predict the structure of water

In transfer the electrons lost must be equal to electrons gained

Mg + F+F  Mg2+ + 2F- Ionic Compound

(cation) (anion) = lost 2 + 2(gain 1)

All halogens form diatomic molecules (single bond)

F—F
Cl—Cl
Br—Br
I—I

What about N2 and O2?

Lewis dot structures of valence bond structures

Number of valence electrons + group number for nonmetals

Group Example # of Bonds

14 (4A or IV) C, Si 4
15 (5A or V) N, P 3
16 (6A or VI) O, S 2
17 (7A or VII) F, Cl, Br, I 1
18 (8A) 0 (normally)

Once a particular element in the table bonds to their respective number then they have a
noble gas like structure

Notice the number of bonds directly correlates to how far they are from the noble gas on
the periodic table

(http://www.chemistry.ohio-
state.edu/~grandinetti/teaching/Chem121/lectures/chemical%20bonds/bonds.html)
4 nonbonding electrons and 6 bonding electrons
(http://www.chemistry.ohio-
state.edu/~grandinetti/teaching/Chem121/lectures/chemical%20bonds/bonds.html)

8 nonbonding electrons and 4 bonding electrons

Bonds = (electrons need – electrons have)/2

Electrons Need refers to the rule of eight and rule of two

Electrons Have refer to valence electrons

N2 (16-10)/2 = 3

O2 (16-12)/2 = 2

HF (10-8)/2 = 1

Covalent Bond and Lewis Structures

Share electrons – a pair of electrons ~ 1 bond

H2 simplest molecule

(http://mws.mcallen.isd.tenet.edu/mchi/ipc/ch07htm/ch07sec3.htm)

Positive nuclei are attracted toward each other by negative charge in between them
Each Hydrogen atom satisfied the noble gas structure
Think of 2 electrons being around each Hydrogen
1s2 structure for each

H2 discrete unit
NaCl ionic compound, simplest ratio, not separate entity or species

F [He] 2s22p5

(http://www.hull.ac.uk/php/chsajb/concepts/ho_2.html)
Each F 2s22p6
12 nonbonding electrons
2 bonding electrons
Family A elements (not transition elements) satisfy rule of 8 or rule of 2 (H)

Covalent
Examples of Covalent Bonds:

(http://dl.clackamas.cc.or.us/ch104-07/bonding1.htm)

(http://www.up.ac.za/academic/chem/mol_geom/bent2.htm)

(http://www.ausetute.com.au/lewisstr.html)

(http://chemsite.lsrhs.net/d_bonding/lewis_dots.html)
Lewis Structural Formula 1916
Unshared electrons are referred to as lone pairs

(http://scidiv.bcc.ctc.edu/wv/5)

Whenever possible the Rule of Eight is followed

Exceptions to Rule of Eight (Octet Rule)

Examples:

Boron trifluoride

(http://chemed.chem.purdue.edu/genchem/topicreview/bp/ch8/lewis.html)

Phosphorus pentachloride

(http://cwx.prenhall.com/bookbind/pubbooks/hillchem3/medialib/media_portfolio/09.html)
Multiple Bonds

Single Bonds
Double Bonds
Triple Bonds
All can be used to satisfy the Rule of Eight

Ethane, Ethene, Ethyne

(http://www.sciencecollege.co.uk/SC/atomic_molecular_structure.html)

Ethane

(http://scidiv.bcc.ctc.edu/wv/5)

Bonds = (need – have)/2

((12 + 8 + 8) – (6 + 4 + 4))/2
(28-14)/2 = 14/2 = 7

(http://www.moorlandschool.co.uk/earth/alkanes.htm)
Ethene

(http://www.wpbschoolhouse.btinternet.co.uk/page06/molecule_shapes.htm)

Bonds = (need – have)/2

((8 + 8 + 8) – (4 + 4 + 4))/2
(24-12)/2 = 12/2 = 6

Chemist use lines when drawing Lewis structures

One line equals two electrons shared between two atoms
and these two electrons compose one bond

Ethyne (Acetylene)

(http://www.cartage.org.lb/en/themes/Sciences/Chemistry/Inorganicchemistry/Informationbonding/bonding
index/multiplebonds/multiplebonds.htm)

Bonds = (need – have)/2

((4 + 8 + 8) – (2 + 4 + 4))/2
(20 – 10)/2 = 10/2 = 5

Resonance Hybrid

Lewis Structure for SO2 (sulfur dioxide)

(http://chemed.chem.purdue.edu/genchem/topicreview/bp/ch8/lewis.html)
These are resonance forms with equivalent structures just the bonds are in different
places
This molecule is a resonance hybrid
Really doesn’t mean that the structure flips back and forth rather there is a hybrid
(intermediate) that includes both of theses structures
The hybrid has two 1 ½ bonds in which 2 e- are spread between 3 atoms

Bonds = (need – have)/2

(24 – 18)/2 = 6/2 = 3 bonds

Normal Lewis Structures don’t always work

Limitation of the theory
We can have fractional bond order

Lewis Structure for N2H4 (hydrazine)

(http://www.answers.com/topic/hydrazine)

Bonds = (need – have)/2

((8 + 8 + 2 + 2 +2 +2) – ( 5+ 5 +1 + 1 + 1 + 1))/2
(24 – 14)/2 = 10/2 = 5 bonds

Coordinate Covalent Bond both electrons donated by one atom

Lewis Structure of HNO2 (hydrogen nitrite)

O=N—N—H

To form HNO3 (hydrogen nitrate) in solution with nitric acid

(http://www.elmhurst.edu/~chm/onlcourse/chm110/outlines/topic8.html)

Bonds = (need –have)/2

(34-24)/2 = 10/2 = 5 bonds

Formal Charge = + (group #) – ( # of bonds + # unshared electrons)

+5 – (4) = +1 for N
+6 – (7) = -1 for O with single bond
+6 – (6) = 0 for O with double bond

In solution break the O—H bond

(http://www.mpcfaculty.net/mark_bishop/resonance.htm)
(Note: negative adds an electron and positive removes an electron)
Bonds = (need – have)/2
(32 – 24)/2 = 8/2 = 4 bonds

Formal Approach to Drawing Lewis Structures

1. Total number of valence electrons

positive ion decrease by charge
negative ion increase by charge

2. Number of needed electrons to give each atom 8 e- and each Hydrogen 2 e-

3. Number of bonding e- + ( needed e-) – (valence e-)

4. Bonds = Bonding e-/ 2

5. Indicate position of atoms

6. Draw dash for each bond

7. Complete octet (other than H) for each atom filling in unshared e-

# unshared e- = (total e-) – ( # bonding e-)

Formal charge = +(group valence #) – ( # bonds + # unshared electrons)

Formal charge is a way of saying if an atom has fewer or more electrons than it
needs to satisfy octet rule. In N2 below each N has 0 (zero) formal charge
because each has 5 valence electrons to start with and ( 3 bonds + 2 electrons in
lone pair= 5 ) so 5 – 5 = 0 zero formal charge

Example:
N2

1. Valence given = 10
2. Needed + 16 ( 2 x8)
3. need 6 bonding electrons
4. or 3 bonds (6/2)
5. so N2 has triple bond
6.
(http://www.chemistry.ohio-
state.edu/~grandinetti/teaching/Chem121/lectures/chemical%20bonds/bonds.html)

7.

(http://members.optushome.com.au/scottsoftc/chapter04/section4.html)
# unshared e- = (total e-) – ( # bonding e-)
10 – 6 = 4 unshared e-

Measure of Charge Separation in Molecules (dipole moment)

Dipole moment = (charge)(distance)

HCl observed dipole moment

Polar molecules affect charge that pair of electrically charged plates can hold

(http://www.800mainstreet.com/5'/0005-0009-lining.gif)

HCl = 1.03 D debye (Coloumb)(m) ~ 3.34 x 10-30 C x m

If charge completely transferred

= (1.60 x 10-19 C)( 1.27 x 10-10 m )(D/3.34 x 10-30 C x m)
= 6.08 D
Observed/ predicted by transfer = 1.03/6.08 = 17% ionic

Left (metal) with right (nonmetal) is a ionic bond

Nonmetal with Nonmetal is polar covalent
Nonmetal with Nonmetal can also be pure covalent

NaCl ionic
MgCl2 ionic
PCl3 covalent