You are on page 1of 14

General Introduction

• 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

Chemical Bonding I: Basic Concepts
Chapter 9

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

9.1 Lewis Dot Symbols
• The development of the periodic table and concept of e- gave chemists a basis for molecule and compound formation. • This explanation, formulated by Lewis, is that atoms combine in order to achieve a more stable EC. Maximum stability results when an atom is isoelectronic with a noble gas. • When atoms interact to form a chemical bond, only their outer regions are in contact. For this reason, when we study chemical bonding, we are concerned primarily with the valence e- of the atoms. • To keep track of valence e- in a chemical reaction, and to make sure that the total number of e- does not change, chemists use a system of dots devised by Lewis and called Lewis dots symbols. • A Lewis dot symbol consists of the symbol of an element and one dot for each valence e- in an atom of the element.

1

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.

9.2 The Ionic Bond
An ionic bond is the electrostatic force that holds ions together in an ionic compound. Consider, for ex, the reaction between Lithium and fluorine to form lithium fluoride, a poisonous white powder used in lowering the melting point of solders and in manufacturing ceramics. The EC of Lithium is 1s²2s1, and that of Fluorine is 1s²2s²2p5. When Lithium and fluorine atoms come in contact with each other , the outer 2s1 valence e- of Li is transferred to the fluorine atom. Using Lewis dot symbols, we represent the reaction like this:

Li + F 1s22s1 1s22s22p5 Li e- + Li+ + F F Li+ + eF -

Li+ F 1s2 1s22s22p6 [He][Ne] isoelectronic
Ionization of Lithium Acceptance of an e- by F Formation of LiF unit

Li+ F -

9.2

2

9.3 Electrostatic (Lattice) Energy
We can predict which elements are likely to form ionic compounds based on IE and EA, but how do we evaluate the stability of an ionic compound?

9.3.1 The Born-Haber Cycle for Determining Lattice Energies
• Lattice energy cannot be measured directly. However, if we know the structure and composition of ionic compound, we can calculate the compound’s lattice energy by using Coulomb’s law, which states that the potential energy (E) between two ions is directly proportional to the product of their charges and inversely proportional to the distance of separation between them.

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.

Lattice energy (E) increases as Q increases and/or as r decreases.

9.3

9.3.1 The Born-Haber Cycle for Determining Lattice Energies
• We can also determine lattice energy indirectly, by assuming that the formation of ionic compounds takes place in a series of steps. • This procedure, known as the Born-Haber cycle, relates lattice energies of ionic compounds to ionization energies IE, electron affinities EA, and other atomic and molecular properties. • It’s based on Hess’s law.

Born-Haber Cycle for Determining Lattice Energy
The lattice energy must have the same magnitude as ∆H° but an opposite sign. Although we 5 cannot determine ∆H° directly, we can calculate its value by the following procedure. 5

1. 2. 3. 4. 5.

Li (s) ½ F2 (g) Li (g) F (g) + eLi+ (g) + F(g)

Li (g) F (g) Li+ F(g) + e-

∆H° = 155.2 kJ/mol 1 ∆H° = 75.3 kJ/mol 2 ∆H° = 520 kJ/mol 3 ∆H° = -328 kJ/mol 4 ∆H° = ? kJ/mol 5

o ∆Hoverall = ∆Ho + ∆Ho + ∆Ho + ∆Ho + ∆Ho 1 2 3 4 5

Input of energy
Release of energy

Electron Affinity Ionization Energy

(g)

LiF (s) LiF (s)

Li (s) + ½ F2 (g)

∆H° overall = -594.1 kJ/mol

According to Hess’s law, we can write

Std enthalpy Changes
o o

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

o

o

Sublimation

Std enthalpy Change

Hence ∆H° = -1017 kJ/mol and the lattice energy of LiF is +1017 kJ/mol 5

9.3

9.3

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-).

Chemistry In Action: Sodium Chloride
The major use of NaCl is in the production of other essential inorganic chemicals such as chlorine gas, NaOH, Sodium metal, Hydrogen gas, and sodium carbonate. It is also used to melt ice and snow on highways and roads. However, because sodium chloride is harmful to plant life and promotes corrosion of cars, its use for this purpose is of considerable environmental concern.

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

Solar Evaporation for Salt

9.3

9.4 The Covalent Bond
A covalent bond is a chemical bond in which two or more electrons are shared by two atoms. Covalent compounds are compounds that contain only covalent bonds. Covalent bonding between many-electron atoms involves only the valence e-. Consider the fluorine molecule, F2. The EC of F is 1s²2s²2p5 . The 1s e- are low in energy an stay near the nucleus most of the time. For this reason they do not participate in bond formation. Thus each F atom has 7 valence e- (the 2s and 2p e-). There is only one unpaired e- on F, so the formation of the F2 molecule can be represented as follow:

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.

Lewis structure of water
O has 2 unpaired dots, so we expect that O might form 2 covalent bonds.

single covalent bonds

H +

O +

H

H O H 2e- -2e8e

or

H

O

H

F 7e-

+

F 7e-

F F 8e- 8elone pairs

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

F

F

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

single covalent bond lone pairs

F F

lone pairs

Single line
9.4

9.4

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

Lengths of Covalent Bonds
Multiple bonds are shorter than single covalent bonds. Bond length is defined as the distance between the nuclei of two covalently bonded atom in a molecule. For a given pair of atoms, such as carbon and nitrogen, triple bonds are shorter than double bonds, which, in turn, are shorter than single bonds. The shorter multiple bonds are also more stable than single bonds, as we will see later.

Bond Type

Bond Length (pm)

C-C C=C C≡C C-N C= N C≡ N

154 133 120 143 138 116

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

Triple bond < Double Bond < Single Bond

9.4

9.4.1 Comparison of the Properties of Covalent and Ionic Compounds
There are two types of attractive forces in covalent compounds. The first type is the force that holds the atoms together in a molecule. The second type of attractive force operates between molecules and is called an intermolecular force. Because intermolecular forces are usually quite weak compared with the forces holding atom together within a molecule, molecules of a covalent compound are not held together tightly. Consequently covalent compounds are usually gases, liquids, or low-melting solids. • On the other hand, the electrostatic forces holding ions together in an ionic compound are usually very strong. So ionic compounds, are solids at RT and have high melting points. Many ionic compounds are soluble in water, and the resulting aqueous solutions conduct electricity, because the compounds are strong electrolytes. • • •

9.4.1 Comparison of the Properties of Covalent and Ionic Compounds
Most covalent compounds are insoluble in water, or if they do dissolve, their aqueous solutions generally do not conduct electricity, because the compounds are nonelectrolytes. Molten ionic compounds conduct electricity because they contain mobile cations and anions; liquid or molten covalent compounds do not conduct electricity because no ions are present. This table compares some of the general properties of typical ionic compound, sodium chloride, with those of a covalent compound, Carbon Tetrachloride (CCl4).

9.4

5

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 δ+

F δ-

H

F

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

Electronegativity of Common Elements

Variation of Electronegativity with Atomic Number

These values are shown in this figure

• 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

6

Classification of bonds by difference in electronegativity
Difference 0 ≥2 0 < and <2 Bond Type Covalent Ionic Polar Covalent

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 atom’s 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

9.6. Writing Lewis Structures
• Although the octet rule and Lewis structures do not present a complete picture of covalent bonding, they do help to explain the bonding scheme in many compounds and account for the properties and reactions of molecules. • For this reason, you should practice writing Lewis structures of compounds. The basic steps are as follows:

Write the Lewis structure of nitrogen trifluoride (NF3).
Step 1 – N is less electronegative than F, put N in center Step 2 – Count valence electrons N - 5 (2s22p3) and F - 7 (2s22p5) 5 + (3 x 7) = 26 valence electrons Step 3 – Draw single bonds between N and F atoms and complete octets on N and F atoms. Step 4 - Check, are # of e- in structure equal to number of valence e- ? 3 single bonds (3x2) + 10 lone pairs (10x2) = 26 valence electrons

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

F

N F

F

9.6

7

Write the Lewis structure of the carbonate ion (CO32-).
Step 1 – C is less electronegative than O, put C in center Step 2 – Count valence electrons C - 4 (2s22p2) and O - 6 (2s22p4) -2 charge – 2e4 + (3 x 6) + 2 = 24 valence electrons Step 3 – Draw single bonds between C and O atoms and complete octet on C and O atoms. Step 4 - Check, are # of e- in structure equal to number of valence e- ? 3 single bonds (3x2) + 10 lone pairs (10x2) = 26 valence electrons Step 5 - Too many electrons, form double bond and re-check # of e2 single bonds (2x2) = 4 1 double bond = 4 8 lone pairs (8x2) = 16 Total = 24 9.6

9.7 Formal Charge and Lewis Structure
• By comparing the # of e- in an isolated atom with the number of e- that are associated with the same atom in a Lewis structure, we can determine the distribution of e- in the molecule and draw the most plausible Lewis structure. • The bookkeeping procedure is as follows:
• In an Isolated atom, the number of e- associated with the atom is simply the

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.

O

C O

O

Two possible skeletal structures of formaldehyde (CH2O) H C O H H H C O
9.7

9.7 Formal Charge and Lewis Structure
Two possible skeletal structures of formaldehyde (CH2O) H C O H C O H H An atom’s formal charge is the difference between the number of valence electrons in an isolated atom and the number of electrons assigned to that atom in a Lewis structure.
Formal charge on an atom in a Lewis structure Total number Total number of valence - of nonbonding electrons in electrons the free atom

Formal Charge and Lewis Structures
• Sometimes, there is more than one acceptable Lewis structure for a given species. In such cases, we can often select the most plausible Lewis structure by using formal charges and the following guidelines:

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

(

Total number of bonding electrons

)

Which is the most likely Lewis structure for CH2O? -1 H C +1 O H H H 0 C 0 O
9.7

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

8

-1 H C

+1 O H

C – 4 eO – 6 e2H – 2x1 e12 e-

2 single bonds (2x2) = 4 1 double bond = 4 2 lone pairs (2x2) = 4 Total = 12

H H

0 C

0 O

C – 4 eO – 6 e2H – 2x1 e12 e-

2 single bonds (2x2) = 4 1 double bond = 4 2 lone pairs (2x2) = 4 Total = 12

Formal charge on an atom in a Lewis structure

=

Total number Total number of valence - of nonbonding electrons in electrons the free atom

-

1 2

(

Total number of bonding electrons

)

Formal charge on an atom in a Lewis structure

=

Total number Total number of valence - of nonbonding electrons in electrons the free atom

-

1 2

(

Total number of bonding electrons

)

Formal Charge on C Formal Charge on O

= =

46 -

2 2 -

-

½ x 6 = -1 ½ x 6 = +1

Formal charge on C Formal charge on O

= 4 = 6 -

04-

½x8 ½x4

=0 =0

9.7

9.7

9

9.8 The Concept of Resonance
Our drawing of the Lewis structure for ozone (O3) satisfied the octet rule for the central atom because we placed a double bond between it and one of the two end O atoms.

O

O

O

O

O

O

In fact, we can put the double bond at either end of the molecule, as shown by these two equivalent Lewis Structures:

O

O

+

O

O

+

O

O

We would expect the O—O 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:

O

O

+

O

O

+

O

O

Each of these structures is called resonance structure

Electrostatic potential map of O3. The electron density is evenly distributed between the two end O atoms

9.8

9.8 The Concept of Resonance
O O + O O + O O

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

-

O

C O

O

-

O

C O -

O

-

-

O

C O -

O

9.8

10

9.9 Exceptions to the Octet Rule
The octet rule applies mainly to the second-period elements. Exceptions to the octet rule fall into three categories characterized by an incomplete octet, an odd number of electrons, or more than eight valence e- around the central atom.

9.9 Exceptions to the Octet Rule
Odd-Electron Molecules
Some molecules contain odd number of electrons. Among them are nitric oxide (NO) and nitrogen dioxide (NO2). Because we need an even number of e- for complete pairing (to reach eight), the octet rule clearly cannot be satisfied for all the atoms in any of these molecules. Odd e- molecules are sometimes called Radicals.

The Incomplete Octet
Group 2A 1s²2s²

BeH2

Be – 2e2H – 2x1e4eB F F

H

Be

H

In Beryllium hydride, there are only 4 e- around the Beryllium atom

F
Group 3A 1s²2s² 2p1B

BF3

In Boron Trifluoride, + there are only F 6 e- around the Boron atom

– 3e3F – 3x7e24eBF F

3 single bonds (3x2) = 6 9 lone pairs (9x2) = 18 Total = 24

NO

N – 5eO – 6e11e-

N

O

The following resonance structures all contain a double bond between B and F and satisfy the octet rule for Boron

F

BF+

F

F

BF

F+
9.9

9.9 Exceptions to the Octet Rule
The Expanded Octet (central atom with principal quantum number n > 2)
Atoms of the second-period elements cannot have more than eight valence e- around the central atom, but atoms of elements in and beyond the third period of the periodic table form some compounds in which more than eight e- surround the central atom. In addition to the 3s and 3p orbitals, elements in the third period also have 3d orbitals that can be used in bonding. These orbitals allow an atom to form an expanded octet. One compound in which there is an expanded octet is Sulfur Hexafluoride, a very stable compound. The EC of sulfur is [Ne]3s²3p4. In SF6 each sulfur’s six valence e- forms a covalent bond with a fluorine atom, so there are 12 e- around the central sulfur.

Chemistry In Action: Just Say NO
Nitric oxide a colorless gas can be prepared in the laboratory by reacting sodium nitrite (NaNO2) with a reducing agent such as Fe2+ in an acidic medium The gas is bubbled through water and immediately reacts with oxygen to form the brown NO2 gas when exposed to air.

NO2- (aq)

+

Fe2+

(aq) +

2H+

(aq)

NO (g) + Fe3+ (aq) + H2O (l)
Environmental sources of NO include the burning of fossils fuel containing nitrogen compounds and the reaction between nitrogen and oxygen inside the a u to m o b ile e n g in e a t h ig h te mp e ra tu re ;

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

F S

F

F

F

F

6 single bonds (6x2) = 12 18 lone pairs (18x2) = 36 Total = 48

9.9

11

9.10 Bond Enthalpy
The enthalpy change required to break a particular bond in one mole of gaseous molecules is the bond energy. Bond Energy Breaking the covalent bonds in 1 H2 (g) H (g) + H (g) ∆H0 = 436.4 kJ mole of gaseous H molecules
2

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

requires 436.4 kJ of energy

Cl2 (g) HCl (g) O2 (g) N2 (g)

Cl (g) + Cl (g) H (g) + Cl (g)

∆H0 ∆H0

Average OH bond energy =

= 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 (g) + O (g) ∆H0 = 498.7 kJ N (g) + N (g) ∆H0 = 941.4 kJ Bond Energies

O N

O N

For molecules containing double and triple bonds

Single bond < Double bond < Triple bond
9.10

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

9.10 Bond Enthalpy Use of Bond Enthalpies in Thermo chemistry

∆H°= total energy input – total energy released = ΣBE(reactants) – ΣBE(products)
Where BE stands for average bond enthalpy and Σ is the summation sign

12

Use of Bond Enthalpies in Thermo chemistry

9.10 Bond Enthalpy
Bond Energies (BE) and Enthalpy changes in reactions
• If reactants and products are all diatomic molecules, then the below equation will yield accurate results because the bond enthalpies of diatomic molecules are accurately known.

∆H0 = total energy input – total energy released = ΣBE(reactants) – ΣBE(products)

• 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, ∆H°is positive and the reaction is Endothermic. • On the other hand, if more energy is released than absorbed, ∆H°is 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.

∆H°= total energy input – total energy released = ΣBE(reactants) – ΣBE(products)

9.10

H2 (g) + Cl2 (g)

2HCl (g)

2H2 (g) + O2 (g)

2H2O (g)

9.10

13

Use bond energies to calculate the enthalpy change for: H2 (g) + F2 (g) 2HF (g) ∆H0 = ΣBE(reactants) – ΣBE(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)

Type of bonds formed

H

F

2

568.2

1136.4

∆H0 = 436.4 + 156.9 – 2 x 568.2 = -543.1 kJ
9.10

14