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Why do atoms of different elements react? What are the forces that hold atoms together in molecules and ions in ionic compounds? What shapes do they assume? These are some of the questions addressed in this Chapter and in Chapter 10. We begin by looking at the two types of bonds Ionic and Covalent and the forces that stabilize them
Chapter Outline
9.1 Lewis Dot Symbols 9.2 The Ionic Bond 9.3 Lattice Energy of Ionic Compounds 9.4 The Covalent Bond 9.5 Electronegativity 9.6 Writing Lewis Structure 9.7 Formal Charge and Lewis Structure 9.8 The Concept of Resonance 9.9 Exceptions to the Octet Rule 9.10 Bond Enthalpy
Valence electrons are the outer shell electrons of an atom. The valence electrons are the electrons that participate in chemical bonding.
Group 1A 2A 3A 4A 5A 6A 7A e- configuration ns1 ns2 ns2np1 ns2np2 ns2np3 ns2np4 ns2np5 # of valence e1 2 3 4 5 6 7
9.1
Lewis dot symbols for the representative elements and the noble gases.
The number of unpaired dots corresponds to the number of bonds an atom of the element can form in a compound. The number of valence e- each atom has is the same as the group number of the element except for He. In this chapter we will learn to use EC and the periodic table to predict the type of bond atoms will form, as well as the number of bonds an atom of a particular element can 9.1 form and the stability of the product.
Li+ F -
9.2
IE and EA are defined for processes occurring in the gas phase, but at 1 atm and 25 C all ionic compounds are solids.
The solid state is a very different environment because each cation in a solid is surrounded by a specific number of anions, and vice versa.
E=k
Q+Qr
Q+ is the charge on the cation Q- is the charge on the anion r is the distance between the ions cmpd MgF2 MgO LiF LiCl lattice energy 2957 Q= +2,-1 3938 Q= +2,-2 1036 853 r F < r Cl
9.3
Thus, the overall stability of a solid ionic compound depends on the interactions of all these ions and not simply on the interaction of a single cation with a single anion.
A quantitative measure of the stability of any ionic solid is its lattice energy defined as the energy required to completely separate one mole of a solid ionic compound into gaseous ions.
9.3
1. 2. 3. 4. 5.
o Hoverall = Ho + Ho + Ho + Ho + Ho 1 2 3 4 5
Input of energy
Release of energy
(g)
Li (s) + F2 (g)
Bond enthalpy
Hoverall = H1 + H2 + H3 + Ho + Ho 4 5
-594.1 kJ/mol = 155.2 kJ/mol + 75.3 kJ/mol + 520 kJ/mol 328 kJ/mol + H 5
Sublimation
Hence H = -1017 kJ/mol and the lattice energy of LiF is +1017 kJ/mol 5
9.3
9.3
This table lists LE and MP of several common ionic compounds. There is a rough correlation between lattice energy and melting point. The larger the Lattice energy, the more stable the solid and the more tightly held the ions. It takes more energy to melt such a solid, and so the solid has a higher melting point than one with smaller lattice energy. Note that MgCl2, Na2O, and MgO have unusually high lattice energies. The first of these ionic compounds has a doubly charges cation (Mg2+) and the second a doubly charged anions (O2-); in the third compound, there is an interaction between two doubly charged species (Mg2+ and O2-).
Th e coulom bic attractions between two doubly charged species, or bet ween a doubly charged ion and a single charged ion, are much stronger than those between singly charged anions and cations.
Mining Salt
9.3
The Lewis structure is a representation of covalent bonding which shared e- pairs are shown either as lines or as pairs of dots between two atoms, and lone pairs of dots on individual atoms. Only valence electrons are shown in a Lewis structure.
H +
O +
H O H 2e- -2e8e
or
F 7e-
F 7e-
Why should two atoms share electrons? The non bonding e- are called lone pairs
Because H has only 1e-, it can form only one covalent bond
Lewis structure of F2
single covalent bond
lone pairs
The formation of these molecules illustrates the octet rule, formulated by Lewis: An atom other rule than hydrogen tends to form bonds until it is surrounded by eight valence e-. In other words, a covalent bond forms when there are not enough e- for each individual atom to have a complete octet. By sharing e- in a covalent bond, the individual atoms can complete their octets. The requirement for H is that it attains the EC of Helium, or a total of two e-. Atoms can form different types of covalent bonds. In a single bond, two atoms are held together bond by one e- pair. Many compounds are held together by multiple bonds, that is, bonds formed when two atoms share two or more pairs of e-. If two atoms share two pairs of e-, the covalent bond is called a double bond. bond
F F
lone pairs
Single line
9.4
9.4
Double bonds are found in molecules of Carbon Dioxide (CO2) and ethylene (C2H4)
Double bond two atoms share two pairs of electrons O C O 8e- 8e- 8edouble bonds or O C O
Bond Type
double bonds
A Triple bond arises when two atoms share three pairs of e-, as in the nitrogen molecule (N2)
Triple bond two atoms share three pairs of electrons N N triple-8e8e bond or N N Bond Lengths
9.4
triple bond
9.4
9.4
9.5 Electronegativity
A covalent bond, as we have said, is the sharing of an e- pair by two atoms. In a molecule like H2, in which the atoms are identical, we expect the e- to be equally shared that is, the espend the same amount of time in the vicinity of each atom. However, in the covalently bonded HF molecule, the H and F atoms do not share the bonding electrons equally because H and F are different atoms. The bond in HF is called a polar covalent bond, or simply a polar bond because the e- spend more time in the vicinity of one atom than the other.
9.5 Electronegativity
A property that can help us to distinguish a nonpolar covalent bond from a polar covalent bond is electronegativity (EN), the ability of an atom to attract toward itself the (EN) electrons in a chemical bond. Elements with high EN have a greater tendency to attract electrons than do elements with low EN. As we might expect, EN is related to Electron Affinity (EA) and Ionization Energy (IE). Thus an atom such as fluorine, which has a high EA (tends to pick up electrons easily) and a high IE does not lose electrons easily), has a high EN. On the other hand sodium has a low EA, a low IE, and a low EN. Pauling devised a method for calculating relative EN of most elements.
Polar covalent bond or polar bond is a covalent bond with greater electron density around one of the two atoms e- poor e- rich electron poor region electron rich region
H +
F -
This unequal sharing of the bonding e- pair results in a relatively greater e- density near the F atom and a correspondingly lower e- density near H.
The HF bond and other polar bonds can be thought of as being intermediate between a nonpolar covalent bond, in which the sharing of e- is exactly equal, and an ionic bond, in which the transfer of the e- is nearly complete.
9.5
A careful examination of this chart reveals trends and relationships among EN values of different elements. In general, EN increases from left to right across a period, as metallic character of the elements decreases. Within each group, EN decreases with increasing atomic number, and increasing metallic character. Note that the transition metals do not follow these trends. The most electronegative elements, the halogens, oxygen, nitrogen and Sulfur are found in the up right-hand corner of the periodic table, and the least electronegative elements (the alkali and alkaline earth metals are clustered near the lower left-hand corner. These trends are readily apparent on the following 9.5 graph.
Atoms of elements with widely different ENs tend to form ionic bonds (such those that exist in NaCl and CaO compounds) with each other because the atom of the less EN element gives up its electron(s) to the atom of the more EN element. An ionic bond generally joins an atom of a metallic element and an atom of a nonmetallic element. Atoms of elements with comparable ENs tend to form polar covalent bonds with each other because the shift in e- density is usually small. Most covalent bond involve atoms of nonmetallic elements. Only atoms of the same element, which have the same EN, can be joined by a pure covalent bond. These trends and characteristics are what we would expect, given our knowledge of IE and EA.
9.5
Classify the following bonds as ionic, polar covalent, or covalent: The bond in CsCl; the bond in H2S; and the NN bond in H2NNH2. Cs 0.7 Cl 3.0 S 2.5 N 3.0 3.0 0.7 = 2.3 2.5 2.1 = 0.4 3.0 3.0 = 0 Ionic Polar Covalent Covalent
Increasing difference in electronegativity Covalent share ePolar Covalent partial transfer of eIonic transfer e-
H 2.1 N 3.0
An ionic bond forms when the EN difference between the two bonding atoms is 2.0 or more. This rule applies to most but not all compounds. Sometimes chemists use the quantity % ionic character to describe the nature of a bond. A purely ionic bond would have 100% ionic character although no such bond is known, whereas a non polar or purely covalent bond has 0 % ionic character. EN and EA are related but different concepts. Both indicate the tendency of an atom to attract e-. However, EA refers to an isolated atoms attraction for an additional e-, whereas EN signifies the ability of an atom in a chemical bond to attract the shared e-. EA is an experimentally measurable quantity, whereas EN is an estimated number that can not 9.5 be measured.
We follow the 2.0 rule of EN difference and look up the values in the EN table
9.5
1. Draw skeletal structure of compound showing what atoms are bonded to each other. Put least electronegative element in the center. 2. Count total number of valence e-. Add 1 for each negative charge. Subtract 1 for each positive charge. 3. Complete an octet for all atoms except hydrogen 4. If structure contains too many electrons, form double and triple bonds on central atom as needed.
9.6
N F
9.6
number of valence e-. In a molecule, e- associated with the atoms are nonbonding e- PLUS the e- in the bonding pair between the atom and the other atom. However, because e- are shared in a bond, we must divide the e- in a bonding pair equally between the atoms forming the bond.
C O
1. For neutral molecules, a Lewis structure in which there are no formal charges is preferable to one in which formal charges are present. 2. Lewis structures with large formal charges are less plausible than those with small formal charges. 3. Among Lewis structures having similar distributions of formal charges, the most plausible structure is the one in which negative formal charges are placed on the more electronegative atoms.
1 2
The sum of the formal charges of the atoms in a molecule or ion must equal the charge on the molecule or ion.
9.7
-1 H C
+1 O H
H H
0 C
0 O
Total number Total number of valence - of nonbonding electrons in electrons the free atom
1 2
Total number Total number of valence - of nonbonding electrons in electrons the free atom
1 2
= =
46 -
2 2 -
x 6 = -1 x 6 = +1
= 4 = 6 -
04-
x8 x4
=0 =0
9.7
9.7
In fact, we can put the double bond at either end of the molecule, as shown by these two equivalent Lewis Structures:
We would expect the OO bond in O3 to be longer than the O==O bond because double bond are known to be shorter than single bonds. Yet experimental evidence shows that both oxygen-to-oxygen bonds are equal in length (128 pm). We resolve this discrepancy by using both Lewis Structures to represent the Ozone molecule:
Electrostatic potential map of O3. The electron density is evenly distributed between the two end O atoms
9.8
A resonance structure is one of two or more Lewis structures for a single molecule that cannot be represented accurately by only one Lewis structure. What are the resonance structures of the carbonate (CO32-) ion?
Carbonate ion provides another ex of resonance
C O
C O -
C O -
9.8
10
BeH2
Be 2e2H 2x1e4eB F F
Be
F
Group 3A 1s2s 2p1B
BF3
3e3F 3x7e24eBF F
NO
N 5eO 6e11e-
The following resonance structures all contain a double bond between B and F and satisfy the octet rule for Boron
BF+
BF
F+
9.9
NO2- (aq)
Fe2+
(aq) +
2H+
(aq)
N2 (g) + O2 (g)
2NO2 (g)
Nitrogen Dioxide is a major component of Smog About 24 years ago, scientists studying muscle relaxation discovered that our bodies produce for use of neurotransmitter (a small molecule that serves to facilitate cell-to-cell communications. The discovery of the biological role of NO has shed the light on how nitroglycerin (C3H5N3O9) works as drug. NG tablets have been prescribed for heart patients to relieve pain caused by a brief interference in the flow of blood to the heart.
SF6
S 6e6F 42e48e-
F S
9.9
11
Average bond energy in polyatomic molecules H2O (g) OH (g) H (g) + OH (g) H0 = 502 kJ H (g) + O (g) H0 = 427 kJ 502 + 427 = 464 kJ 2
H0 H0
= 242.7 kJ = 431.9 kJ
Bond enthalpies can also be directly measured for diatomic molecules containing unlike elements
Measuring the strength of covalent bonds in polyatomic molecules is more complicated. For ex, measurements show that the energy needed to break the first O-H bond in H2O is different from that needed to break the second O-H bond. The first step is more endothermic. If the environment of bonds is different, so the energy needed to break down a bond is different. Ex: CH3OH and H2O Thus for polyatomic molecules, we can measure the energy of the O-H bond in 10 different polyatomic molecules and obtain the average O-H bond enthalpy by dividing the sum of the bond enthalpies by 10.
O N
O N
The following table lists the average bond enthalpies of a number of diatomic and polyatomic molecules.
In many cases, it is possible to predict the approximate enthalpy of reaction by using the average bond enthalpies. Because energy is always required to break chemical bonds and chemical bond formation is always accompanied by a release of energy, we can estimate the enthalpy of a reaction by counting the total number of bonds broken and formed in the reaction and recording all the corresponding energy changes. The enthalpy of reaction in the gas phase is given by
12
As written, the below equation takes care of the sign convention for H Thus if the total energy . input is greater than the total energy released, His positive and the reaction is Endothermic. On the other hand, if more energy is released than absorbed, His negative and the reaction is Exothermic.
If some or all of the reactants and products are polyatomic molecules, the above equation will yield only approximate results because the bond enthalpies used will be averages.
9.10
2HCl (g)
2H2O (g)
9.10
13
Use bond energies to calculate the enthalpy change for: H2 (g) + F2 (g) 2HF (g) H0 = BE(reactants) BE(products)
Type of bonds broken Number of bonds broken Bond energy (kJ/mol) Energy change (kJ)
H F
H F
1 1
Number of bonds formed
436.4 156.9
Bond energy (kJ/mol)
436.4 156.9
Energy change (kJ)
568.2
1136.4
14