Anda di halaman 1dari 57

404 Not Found

Page 1 of 57

CHEM281. Chapter 3 Covalent Bonding


Bonding Theories 1. VSEPR Theory 2. Valence Bond theory (with hybridization) 3. Molecular Orbital Theory ( with molecualr orbitals) To date, we have looked at three different theories of molecular boning. They are the VSEPR Theory (with Lewis Dot Structures), the Valence Bond theory (with hybridization) and Molecular Orbital Theory. A good theory should predict physical and chemical properties of the molecule such as shape, bond energy, bond length, and bond angles.Because arguments based on atomic orbitals focus on the bonds formed between valence electrons on an atom, they are often said to involve a valence-bond theory. The valence-bond model can't adequately explain the fact that some molecules contains two equivalent bonds with a bond order between that of a single bond and a double bond. The best it can do is suggest that these molecules are mixtures, or hybrids, of the two Lewis structures that can be written for these molecules. This problem, and many others, can be overcome by using a more sophisticated model of bonding based on molecular orbitals. Molecular orbital theory is more powerful than valence-bond theory because the orbitals reflect the geometry of the molecule to which they are applied. But this power carries a significant cost in terms of the ease with which the model can be visualized. One model does not describe all the properties of molecular bonds. Each model desribes a set of properties better than the others. The final test for any theory is experimental data.

Introduction to Molecular Orbital Theory


The Molecular Orbital Theory does a good job of predicting elctronic spectra and paramagnetism, when VSEPR and the V-B Theories don't. The MO theory does not need resonance structures to describe molecules, as well as being able to predict bond length and energy. The major draw back is that we are limited to talking about diatomic molecules (molecules that have only two atoms bonded together), or

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 2 of 57

the theory gets very complex. The MO theory treats molecular bonds as a sharing of electrons between nuclei. Unlike the V-B theory, which treats the electrons as localized baloons of electron density, the MO theory says that the electrons are delocalized. That means that they are spread out over the entire molecule. Forming Molecular Orbitals Molecular orbitals are obtained by combining the atomic orbitals on the atoms in the molecule. Consider the H molecule, for example. One of
2

the molecular orbitals in this molecule is constructed by adding the mathematical functions for the two 1s atomic orbitals that come together to form this molecule. Another orbital is formed by subtracting one of these functions from the other, as shown in the figure below.

One of these orbitals is called a bonding molecular orbital because electrons in this orbital spend most of their time in the region directly between the two nuclei. It is called a sigma ( ) molecular orbital because it looks like an s orbital when viewed along the H-H bond. Electrons placed in the other orbital spend most of their time away

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 3 of 57

from the region between the two nuclei. This orbital is therefore an antibonding, or sigma star ( *), molecular orbital.

The bonding molecular orbital concentrates electrons in the region directly between the two nuclei. Placing an electron in this orbital therefore stabilizes the H molecule. Since the * antibonding
2

molecular orbital forces the electron to spend most of its time away from the area between the nuclei, placing an electron in this orbital makes the molecule less stable. The MO Theory has five basic rules: 1. The number of molecular orbitals = the number of atomic orbitals combined 2. Of the two MO's, one is a bonding orbital (lower energy) and one is an anti-bonding orbital (higher energy) 3. Electrons enter the lowest orbital available 4. The maximum # of electrons in an orbital is 2 (Pauli Exclusion Principle) 5. Electrons spread out before pairing up (Hund's Rule) Calculating Bond Order In molecular orbital theory, we calculate bond orders by assuming that two electrons in a bonding molecular orbital contribute one net bond and that two electrons in an antibonding molecular orbital cancel the effect of one bond. We can calculate the bond order in the O
2

molecule by noting that there are eight valence electrons in bonding molecular orbitals and four valence electrons in antibonding molecular

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 4 of 57

orbitals in the electron configuration of this molecule. Thus, the bond order is two. Although the Lewis structure and molecular orbital models of oxygen yield the same bond order, there is an important difference between these models. The electrons in the Lewis structure are all paired, but therecould be unpaired electrons in the molecular orbital description of a molecule. As a result, we can test the predictions of these theories by studying the effect of a magnetic field on certain molecules. Homo Nuclear Diatmic Molecules Molecular Orbitals of the Second Energy Level (1s and 2s only) Molecular Orbitals for Period 1 Diatomic Molecules Electrons are added to molecular orbitals, one at a time, starting with the lowest energy molecular orbital. The two electrons associated with a pair of hydrogen atoms are placed in the lowest energy, or bonding, molecular orbital, as shown in the figure below. This diagram suggests that the energy of an H molecule is lower than that of a pair of
2

isolated atoms. As a result, the H molecule is more stable than a pair


2

of isolated atoms.

We can put the Molecular Orbital Theory to use!! Would you predict that dilithium or diberylium is more likely to form, based on the diagram below? The answer is dilithium because it has a bond order of 1 which is stable and diberylium has a BO of 0 which is unstable and therefore will not form. Using the Molecular Orbital Model to Explain Why He MoleculeDo Not Exist
2

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 5 of 57

This molecular orbital model can be used to explain why He

2 2

molecules don't exist. Combining a pair of helium atoms with 1s electron configurations would produce a molecule with a pair of electrons in both the bonding and the * antibonding molecular orbitals. The total energy of an He molecule would be essentially the
2

same as the energy of a pair of isolated helium atoms, and there would be nothing to hold the helium atoms together to form a molecule. The fact that an He molecule is neither more nor less stable than a
2

pair of isolated helium atoms illustrates an important principle: The core orbitals on an atom make no contribution to the stability of the molecules that contain this atom. The only orbitals that are important in our discussion of molecular orbitals are those formed when valenceshell orbitals are combined. Molecular Orbitals for Period 2 Diatomic Molecules and Li and Be (does not exsit)
2 2

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 6 of 57

Homo Nuclear Diatmic Molecules Molecular Orbitals of the Second Energy Level (2s and 2p together) Molecular Orbitals of the Second Energy Level The 2s orbitals on one atom combine with the 2s orbitals on another to form a bonding and a * antibonding molecular orbital, just like
2s 2s

the

1s

and

1s

* orbitals formed from the 1s atomic orbitals. If we


2

arbitrarily define the Z axis of the coordinate system for the O


z

molecule as the axis along which the bond forms, the 2p orbitals on the adjacent atoms will meet head-on to form a
2p

bonding and a

2p

antibonding molecular orbital, as shown in the figure below. These are called sigma orbitals because they look like s orbitals when viewed along the oxygen-oxygen bond.

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 7 of 57

The 2p orbitals on one atom interact with the 2p orbitals on the other
x x

to form molecular orbitals that have a different shape, as shown in the figure below. These molecular orbitals are called pi ( ) orbitals because they look like p orbitals when viewed along the bond. Whereas and * orbitals concentrate the electrons along the axis on which the nuclei of the atoms lie, and * orbitals concentrate the electrons either above or below this axis. The 2p atomic orbitals combine to form a
x x

bonding molecular orbital and a *

and a

x y

* antibonding molecular orbital. The same thing happens when


y y

the 2p orbitals interact, only in this case we get a


x y

antibonding molecular orbital. Because there is no difference between the energies of the 2p and 2p atomic orbitals, there is no difference between the energies of the orbitals.
x

and

or the

* and

* molecular

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 8 of 57

The interaction of four valence atomic orbitals on one atom (2s, 2p ,


x

2p and 2p ) with a set of four atomic orbitals on another atom leads to


y z

the formation of a total of eight molecular orbitals:


x

2s 2s

*,

2p 2p

*, , ,
x y

*, and

*.
2s 2s y

There is a significant difference between the energies of the 2s and 2p orbitals on an atom. As a result, the and * orbitals both lie at lower energies than the
2p 2p

*, , , *, and
x y x

* orbitals. To sort out

the relative energies of the six molecular orbitals formed when the 2p atomic orbitals on a pair of atoms are combined, we need to understand the relationship between the strength of the interaction between a pair of orbitals and the relative energies of the molecular orbitals they form. Because they meet head-on, the interaction between the 2p orbitals is
z

stronger than the interaction between the 2p or 2p orbitals, which


x y

meet edge-on. As a result, the the


x x

2p 2p

orbital lies at a lower energy than

and
y

orbitals, and the

* orbital lies at higher energy than the

* and

* orbitals, as shown in the figure below.

Unfortunately an interaction is missing from this model. It is possible for the 2s orbital on one atom to interact with the 2p orbital on the
z

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 9 of 57

other. This interaction introduces an element of s-p mixing, or hybridization, into the molecular orbital theory. The result is a slight change in the relative energies of the molecular orbitals, to give the diagram shown in the figure below. Experiments have shown that O
2 2

2 2

and F are best described by the model in the figure above, but B , C , and N are best described by a model that includes hybridization, as
2

shown in the figure below.

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 10 of 57

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 11 of 57

Construct a Molecular orbital diagram for the O molecule.


2

There are six valence electrons on a neutral oxygen atom and therefore 12 valence electrons in an O molecule. These electrons are
2

added to the diagram in the figure below, one at a time, starting with the lowest energy molecular orbital.

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 12 of 57

Because Hund's rules apply to the filling of molecular orbitals, molecular orbital theory predicts that there should be two unpaired electrons on this molecule one electron each in the * and *
x y

orbitals. When writing the electron configuration of an atom, we usually list the orbitals in the order in which they fill. Pb: [Xe] 6s 4f 5d 6p We can write the electron configuration of a molecule by doing the same thing. Concentrating only on the valence orbitals, we write the electron configuration of O as follows.
2 2 2 2 2 1 1 2 O : * * * 2 2s 2s 2p x y x y 2 14 10 2

Molecular Orbital diagram fro N2

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 13 of 57

Bond Order The number of bonds between a pair of atoms is called the bond order. Bond orders can be calculated from Lewis structures, which are the heart of the valence-bond model. Oxygen, for example, has a bond order of two. When there is more than one Lewis structure for a molecule, the bond order is an average of these structures. The bond order in sulfur dioxide, for example, is 1.5 the average of an S-O single bond in one Lewis structure and an S=O double bond in the other.

In molecular orbital theory, we calculate bond orders by assuming that two electrons in a bonding molecular orbital contribute one net bond and that two electrons in an antibonding molecular orbital cancel the effect of one bond. We can calculate the bond order in the O
2

molecule by noting that there are eight valence electrons in bonding molecular orbitals and four valence electrons in antibonding molecular orbitals in the electron configuration of this molecule. Thus, the bond order is two.

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 14 of 57

Although the Lewis structure and molecular orbital models of oxygen yield the same bond order, there is an important difference between these models. The electrons in the Lewis structure are all paired, but there are two unpaired electrons in the molecular orbital description of the molecule. As a result, we can test the predictions of these theories by studying the effect of a magnetic field on oxygen. Atoms or molecules in which the electrons are paired are diamagnetic repelled by both poles of a magnetic. Those that have one or more unpaired electrons are paramagnetic attracted to a magnetic field. Liquid oxygen is attracted to a magnetic field and can actually bridge the gap between the poles of a horseshoe magnet. The molecular orbital model of O is therefore superior to the valence-bond model,
2

which cannot explain this property of oxygen. Look at the following MO diagrams for some of the period two elements. Can you tell which molecules are paramagnetic? Which molecules have the highest bond energy, which has the lowest? Rank single, double, and triple bonds in order of bond energy and bond length. (hint a BO of 1 is a single bond, 2 a double...) Delocalized Bonding Finaly, it was mentioned earlier that the MO Theory did not need resonance structures to explain anything. Because the MO theory holds that electrons are not held to only one position. Instead they are spread across the entire molecule. Below is a picture of Benzene and Ozone. You can see that rather than having two resonance structures, we can picture one structure with the electrons dispersed over the entire molecule.

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 15 of 57

Molecular Orbitals for Heteronuclear Diatomic Molecules

The most striking molecular orbital difference between a heteronuclear diatomic, such as HF, and the homonuclear diatomics is that the orbitals are no longer have equally density on each atom. Note that the "1-sigma" and "2-sigma" molecular orbitals of Hydrogen Fluoride are mostly derived from the Fluorine 2s and 2p atomic orbitals respectively. Qualitatively, the high fluorine character of these orbitals is a consequence of the high electronegativity of fluorine as compared to hydrogen. Mathematically, the molecular orbitals have large coefficients on Fluorine and small coefficients on Hydrogen. The 1 pi orbitals are non-bonding and Fluorine 2p in character. Finally, the antibonding "3-sigma" orbital is primarily H 1s in character. The use of nodes to give a general idea of the energy ordering still works. "1-sigma" has no nodes, "2-sigma" and "1-pi" have one node, and "3-sigma" has two nodes. Carbon monoxide CO molecular orbital diagram

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 16 of 57

Iodine monochloride ICl molecular orbital diagram

Lewis Theory Octet Rule All elements except hydrogen ( hydrogen have a duet of electrons) have octet of electrons once they from ions and covalent compounds. The Lewis dot symbols for atoms and ions shows how many electrons are need for a atom to fill the octet. Noramlly there are octet of electrons on most monoatomic ions Basic rules drawing Lewis dot symbols: 1. Draw the atomic symbol.

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 17 of 57

2. Treat each side as a box that can hold up to two electrons. 3. Count the electrons in the valence shell. Start filling box - dont make pairs unless you need to.

Elements try to complete their valence shell to achieve noble-gas electron configurations. The stability of noble/inert gases must be due to their filled valence shell. Elements either loose/gain or share electrons for this purpose. Electron transfer is associated with the formation of ionic compounds. Covalent compounds are formed when electrons are shared between atoms. A Lewis symbol is a symbol in which the electrons in the valence shell of an atom or simple ion are represented by dots placed around the letter symbol of the element. Each dot represents one electron. Hydrogen Oxygen Chlorine Chloride ion A covalent bond is a chemical bond formed by the sharing of a pair of electrons between two atoms. The Lewis structure of a covalent compound or polyatomic ion shows how the valence electrons are arranged among the atoms in the molecule to show the connectivity of the atoms.

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 18 of 57

Instead of using two dots to indicate the two electrons that comprise the covalent bond, a line is substituted for the two dots that represent the two electrons.

Below is shown the Lewis structure for water. Two hydrogens (H) are separately covalently bonded to the central oxygen (O) atom. The bonding electrons are indicated by the dashes between the oxygen (O) and each hydrogen (H) and the other two pairs of electrons that constitute oxygens octet, are called non-bonding electrons as they are not involved in a covalent bond.

RULES FOR LEWIS STRUCTURES

1. Determine whether the compound is covalent or ionic. If covalent, treat the entire molecule. If ionic, treat each ion separately. Compounds of low electronegativity metals with high electronegativity nonmetals (DEN > 1.6) are ionic as are compounds of metals with polyatomic anions. For a monoatomic ion, the electronic configuration of the ion represents the correct Lewis structure. For compounds containing complex ions, you must learn to recognize the formulas of cations and anions. 2. Determine the total number of valence electrons available to the molecule or ion by: (a) summing the valence electrons of all the atoms in the unit and (b) adding one electron for each net negative charge or subtracting one electron for each net positive charge. Then divide the total number of available electrons by 2 to obtain the number of electron pairs (E.P.) available. 3. Organize the atoms so there is a central atom (usually the least electronegative) surrounded by ligand (outer) atoms. Hydrogen is never the central atom.

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 19 of 57

4. Determine a provisional electron distribution by arranging the electron pairs (E.P.) in the following manner until all available pairs have been distributed: a) One pair between the central atom and each ligand atom. b) Three more pairs on each outer atom (except hydrogen, which has no additional pairs), yielding 4 E.P. (i.e., an octet) around each ligand atom when the bonding pair is included in the count. c) Remaining electron pairs (if any) on the central atom. Examples: Consider carbon dioxide CO
2

1. The first step in drawing Lewis structures is to determine the number of electrons to be used to connect the atoms. This is done by simply adding up the number of valence electrons of the atoms in the molecule. carbon (C) has four valence electrons x 1 carbon = 4 e
-

oxygen (O) has six valence electrons x 2 oxygens = 12 e

There are a total of 16 e to be placed in the Lewis structure. 1. Connect the central atom to the other atoms in the molecule with single bonds. Carbon is the central atom, the two oxygens are bound to it and electrons are added to fulfill the octets of the outer atoms. 2. Complete the valence shell of the outer atoms in the molecule. 3. Place any remaining electrons on the central atom. There are no more electrons available in this example. 4. If the valence shell of the central atom is complete, you have drawn an acceptable Lewis structure. Carbon is electron deficient - it only has four electrons around it. This is not an acceptable Lewis structure. 5. If the valence shell of the central atom is not complete, use a lone pair on one of the outer atoms to form a double bond between that outer atom and the central atom. Continue this process of making multiple bonds between the outer atoms and the central atom until the valence shell of the central atom is complete.

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 20 of 57

becomes The central atom is still electron deficient, so share another pair

There are two possible Lewis structures for this molecule. Each has the same number of bonds. We can determine which is better by determining which has the least formal charge. It takes energy to get a separation of charge in the molecule (as indicated by the formal charge) so the structure with the least formal charge should be lower in energy and thereby be the better Lewis structureThe two possible Lewis structures are shown below. They are connected by a double headed arrow and placed in brackets. The non-zero formal charge on any atoms in the molecule have been written near the atom.

The two structures differ only in the arrangement of the valence electrons in the molecule. No atoms have been moved. These are called resonance structures. The better Lewis structure or resonance structure is that which has the least amount of formal charge. If the central atom formal charge is zero or is equal to the charge on the species, the provisional electron distribution from (4) is correct. Calculate the formal charge of the ligand atoms to complete the Lewis structure. If the structure is not correct, calculate the formal charge on each of the ligand atoms. Then to obtain the correct structure, form a multiple bond by sharing an electron pair from the ligand atom that has the most negative formal charge. a) For a central atom from the second (n = 2) row of the periodic table continue this process sequentially until the central atom has 4 E.P. (an octet).

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 21 of 57

b) For all other elements, continue this process sequentially until the formal charge on the central atom is reduced to zero or two double bonds are formed. Recalculate the formal charge of each atom to complete the Lewis structure. Draw the Lewis structures for the following molecules: H O (H S), CH (SiH ), CCl (CF , CBr ), CO , NH (PH ), PCl (PF , NCl )
3 3 2 2 4 4 4 4 4 2 3 3 3

b) CH

i) Sum of valence electrons:

4 ( from one C) + 4 (from four H) = 8 electrons = 4 electron pairs

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 22 of 57

ii) Central atom is C iii) Octet on C atom and duet on H are already complete. iv) Count valence electrons on the Lewis structure: bond pairs = 2 x 4 = 8 = 4 electron pairs lone pairs = 0 SiH has the same Lewis Structure as CH since Si and C are in the
4 4

same group. c) CCl


4

i) Valence electrons: 4 (from one carbon)+ 28 (7 from each chlorine) = 32 = 16 electron pairs ii) Central atom iii) Octet on C is already complete iv) Count electrons 4 x 3 lone pairs = 12 pairs 4 x 4 bond pairs = 4 pairs 16 electron pairs Lewis Structure of CCl . CF and CBr have similar structures.
4 4 4

d) CO

i) Valence electrons: 4 + 2 x 6 = 16 ( 8 pairs) ii) Central atom iii) Give octet to carbon Try to fill octet to O iv) Count electrons: 4 bond pairs = 4 pairs 4 lone pairs = 4 pairs 8 electron pairs Lewis Structure of CO
2

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 23 of 57

e) NH

i) Valence electrons: 5 + 3 x 1 = 8 = 4 electron pairs ii) N is the central atom: iii) Add terminal Hs vi) Give octet to N Check duet on Hs v) Count electrons: 3 bond pairs = 3 pairs 1 lone pairs = 1 pairs 4 electron pairs Lewis Structures of NH , PH has the same Lewis Structure
3 3

f) PCl

i) Valence electrons: 5 + 3 x 7 = 26 (13 pairs) ii) Central atom is P iii) Connect to terminal atoms to central atom vi) Give octet to P give octets to Cl v) Count electron pairs: 3 bond pairs = 3 pairs 1 + 3 x 3 = 10 lone pairs = 10 pairs 13 pairs

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 24 of 57

PF and NCl have similar Lewis Structures.


3 3

10) How many lone pairs and bond pairs of electrons are found around the central atoms of the following molecules? CH , NH , PCl , H O
3 2 4 3

a) Lewis Structure of CH i) 4 + 1 x 4 = 8 = pairs ii) C central

iii) octet to C, duet to H iv) count pairs 4 pairs 4 bond pairs. Bond pair: electron pair shared between two atoms. Lone pair: electron pair found on a single atom. CH has only 4 bond pairs on central C.
4

b) Lewis Structure of NH

i) Valence electrons: 5 + 3 x 1 = 8 = 4 electron pairs ii) N is the central atom: iii) Add terminal Hs vi) Give octet to N Check duet on Hs v) Count electrons: 3 bond pairs = 3 pairs 1 lone pairs = 1 pairs

4 electron pairs Lewis Structures of NH , PH has the same Lewis Structure


3 3

3 bond pairs and 1 lone pair are found on central N.

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 25 of 57

c) PCl

i) Valence electrons: 5 + 3 x 7 = 26 = 13 electron pairs ii) P is the central atom: iii) Add terminal Cls vi) Give octet to P add octet to Cls v) Count electrons: 3 bond pairs = 3 pairs 13 lone pairs = 13 pairs

26 electron pairs Lewis Structures of PCl3 Three bond pairs and 13 lone pairs,one on P and 12 on Cls. d) H O. Lewis structure of H O
2 2

Two bond pairs and two lone pairs are found on central O. 11) Draw the Lewis structures of the following molecules and show that the electron count around the central atoms violate the octet rule: BF (BH , AlCl ), SF , PCl (AsCl )
3 3 3 6 5 5

a) BF

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 26 of 57

i) Count total valence electrons: 3 + 3 x 7 = 24 (12 electron pairs) ii) Central atom is B iii) Connect central atom terminal atoms: iv) 3 bonds pairs on B. 3 lone pairs on 3F 3 + 3 x 3 = 12 pairs Boron do not have a octet, therfore, BF is an electron deficient
3

compound. BF violate octet rule.


3

Similarly BH has the Lewis Structure:


3

B has on 3 electron pairs. BH violates octet rule


3

Similarly AlCl has the Lewis Structure:


3

Al has only 3 electron pairs. AlCl also violates octet rule.


3

b) SF

i) Count total valence electrons:6 + 6 x 7 = 48 (24 pairs) ii) S is the central atom sulfur already have excess of 4 electrons to octet iii) fill octet to Fs iv) count electrons: S - 6 bond pairs = 6 6F - 3 x 6 lone pairs = 18 24 pairs

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 27 of 57

Sulfur violates octet rule, is an exception to octet rule having more than eight electrons on S. S has 12 electrons. c) PCl
5

i) Count the total valence lectrons: 5 + 5 x 7 = 40 (20 pairs) ii) P is central atom: iii) P already have 5 electron pairs then give octets to Cls iv) count electron pairs. 5 pairs on P = 5 5 x 3 pairs on Cl = 15 20 electron pairs

AsCl have similar structure. PCl and AsCl violates octet rule
5 5 5

having 10 electrons on P and As.

Resonance Structures
molecules: CO
23 -

Necessity to draw several Lewis structures (resonance structures) to adequately describe the structures of the following , NO , NO
3 2 2: 3

a) Lewis Structure of CO

i) valence electrons:4 + 3 x 6 + 2(negative charge) = 24 (12 pairs) ii) central atom is carbon

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 28 of 57

iii) fill octet to C; fill octet to O

One oxygen does not have an octet. Share lone pair on C with the oxygens. The double bond could be on any other oxygen atoms.

Therefore, there are three resonance structures for CO b) NO Lewis Structure:


3 -

2ion 3

i) valence electrons: 5 + 3 x 6 + 1(negative charge) = 24 (12 pairs) iii) N is the central atom:

iii) Fill octet to N; Fill octet to Os

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 29 of 57

one oxygen has only 6 electrons share lone pair on N with the oxygen The double bond could be on any other oxygen atoms. Therefore, there are three resonance structures for the NO
3

ion.

c) NO

Lewis Structure

i) valence electrons: 5 + 2 x 6 + 1(negative charge) = 18 (9 pairs) ii) central atom is nitrogen. iii) Fill octet to N ; Fill octet to O one oxygen has only six electrons share lone pair on N with oxygen. The double bond could be on any of the two oxygen atoms. Therefore, there are two resonance structures for NO
2

ion.

Predicting the Molecular Structure from Lewis Structure Valence Shell Electron Pair Repulsion Theory
VSEPR stands for Valence Shell Electron Pair Repulsion. It is a theory which allows the user to predict the shapes of simple polyatomic molecules by applying a set of straight forward rules. VSEPR Theory is one method that

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 30 of 57

chemists use to predict the shapes of molecules. This theory predicts that electron pairs, whether involved in bonds or as non-bonding pairs, will adopt a geometry in which they maximize the distance from one another in order to minimize repulsions. This will result in a geometry with the lowest possible energy. VSEPR theory states that each region of electron density on the central atom has an impact on the final shape of a molecule, and these regions want to be as far apart as possible. Why do these regions want to be as far apart as possible? Let us consider each region of electron density as a point charge. Since all these regions have the same charge they should be repelled and the lowest interaction would be when the point charges are as far apart as possible. Another question which must be answer is: How do I represent a structure? The answer to this question depends on what you want to show. If you want to emphasize the geometry of individual atoms in a molecule you would use either stick or ball and stick structures. On the other hand, you want to emphasize the overall shape of the molecule, a space filling structure is more appropriate. The ideal electronic symmetry of a molecule consisting of a central atom surrounded by a number of substituents (bonded atoms and nonbonding electrons) is characteristic of the total number of substituents, and is determined solely by geometric considerations -- the substituents are arranged so as to maximize the distances amongst them. VSEPR is useful for predicting the shape of a molecule when there are between 2 and 6 substituents around the central atom (the case of one substituent is not discussed because it is trivial -- the only possible shape for such a molecule is linear). That means that there are only five unique electronic geometries to remember. For each electronic geometry, there may be a number of different molecular geometries (the shape of the molecule when only bonded atoms, not non-bonding electrons are considered). Molecular geometries are really just special cases of the parent electronic geometry -- this will hopefully be evident from the models shown on the pages linked to this one. Since the molecular geometry is determined by how many bonding and non-bonding electron groups surround the central atom, the first thing one needs to do is count how many of each there are. There is a notation that simplifies this bookkeeping:

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 31 of 57

The A represents the central atom, B represents the electron groups that form bonds to other atoms, and E represents the non-bonding electron groups. The subscripts, x and y, indicate how many of each kind are present.
AB4 AB3E

ABxEy

bonding groups: 4 non-bonding groups: 0

bonding gr non-bonding

CH

NH
4

ammo methane Note that bonding "electron groups" does not necessarily imply single bonds; it can mean double or triple bonds as well:
AB2

bonding groups: 2 non-bonding groups: 0

CO

Carbon Dioxide An incidental benefit of using the ABE notation is that it provides a convenient way of remembering the hybridization at the central atom. The total number of substituents (bonding plus non-bonding groups) is

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 32 of 57

equal to the number of atomic orbitals that participate in the hybrid orbital. Molecule ABE representation # of substituents Hybridization 3 CH AB 4 sp
4 3 4

NH
2

AB E
3

4 4 2 6 5

sp sp

3 3

H O CO SF I
3 2

AB E AB AB
2 6

2 2

sp sp d
3 3 2

ion

AB E

2 3

sp d

Displayed in the following table are the five most important electronic symmetries. Each row in the table is linked to a page that shows the different molecular symmetries possible for that electronic symmetry. Class Hybridization Electronic Symmetry
AB2 AB3 AB4 AB5 AB6

sp sp sp
2 3

linear trigonal planar tetrahedral trigonal bipyramidal octahedral

sp d sp d
3 2

Predicting the Shapes of Molecules There is no direct relationship between the formula of a compound and the shape of its molecules. The shapes of these molecules can be predicted from their Lewis structures, however, with a model developed about 30 years ago, known as the valence-shell electronpair repulsion (VSEPR) theory. The VSEPR theory assumes that each atom in a molecule will achieve

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 33 of 57

a geometry that minimizes the repulsion between electrons in the valence shell of that atom. The five compounds shown in the figure below can be used to demonstrate how the VSEPR theory can be applied to simple molecules.

There are only two places in the valence shell of the central atom in BeF where electrons can be found. Repulsion between these pairs of
2

electrons can be minimized by arranging them so that they point in opposite directions. Thus, the VSEPR theory predicts that BeF should be a linear molecule, with a 180 angle between the two Be-F bonds.
o 2

There are three places on the central atom in boron trifluoride (BF )
3

where valence electrons can be found. Repulsion between these

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 34 of 57

electrons can be minimized by arranging them toward the corners of an equilateral triangle. The VSEPR theory therefore predicts a trigonal planar geometry for the BF molecule, with a F-B-F bond angle of
3

120 .

BeF and BF are both two-dimensional molecules, in which the atoms


2 3

lie in the same plane. If we place the same restriction on methane (CH ), we would get a square-planar geometry in which the H-C-H
4

bond angle is 90 . If we let this system expand into three dimensions, however, we end up with a tetrahedral molecule in which the H-C-H bond angle is 109 28'.
o

Repulsion between the five pairs of valence electrons on the phosphorus atom in PF can be minimized by distributing these
5

electrons toward the corners of a trigonal bipyramid. Three of the positions in a trigonal bipyramid are labeled equatorial because they lie along the equator of the molecule. The other two are axial because they lie along an axis perpendicular to the equatorial plane. The angle between the three equatorial positions is 120 , while the angle between an axial and an equatorial position is 90 .
o o

There are six places on the central atom in SF where valence


6

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 35 of 57

electrons can be found. The repulsion between these electrons can be minimized by distributing them toward the corners of an octahedron. The term octahedron literally means "eight sides," but it is the six corners, or vertices, that interest us. To imagine the geometry of an SF molecule, locate fluorine atoms on opposite sides of the sulfur
6

atom along the X, Y, and Z axes of an XYZ coordinate system.

Predict the molecular structure of the following molecules using VSEPR theory: H O, NH , CO , SF , PCl , XeF a) Molecular Structure of H O :
2 2 3 2 6 5 4

Basic(electronic) structure Molecular structure First get the Lewis structure of H O, problem 9a.
2

2 bond pairs = 2 x 2 = 4 2 lone pairs = 2 x 2 = 4 Total 8 = 4 electron pairs (an Octet) Basic Structure: Arrangement of electron pairs arounf the central atom Tetrahedral for H O Molecular Structure: Arrangement of atom or groups around central atom. Ignore lone pairs and look at the basic structure Basic Structure Molecular Structure: Angular
2

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 36 of 57

b) molecular structure of NH :
3

Lewis Structure:

Lewis Structure Molecular structure

Basic(electronic) structure tetrahedral

pyramidal structure c) Molecular Structure CO Lewis Structure of CO


2

electron pairs but double bond is counted as single electron pair = 2 pairs total 2 electron pairs linear basic structure Since there are no lone pairs on C basic structure is same as molecular structure. Basic structure molecular structure d) Molecular Structure of: SF Lewis Structure
6

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 37 of 57

i) count electrons around central atom: 6 electron pairs ii) 6 electron pairs given octahedral basic structure

iii) Since there are no lone pairs basic structure is same as molecular structure. Basic structure and molecular structure is the same since there are no lone pairs on S. molecular structure of SF is octahedral
6

e) Molecular Structure of PCl : Lewis Structure:


5

i) Count electron pairs on the central atom: 5 electron pairs. ii) Basic structure is trigonal bipyramidal iii) There are no lone pairs on central P atom. Therefore, basic structure is same as molecular structure.

Molecular structure of PCl - Trigonal bipyramidal


5

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 38 of 57

f) Molecular Structure of XeF . First get the Lewis structure i) Count the total valence lectrons: 8 + 4 x 7 = 36 (18 pairs) ii) Xe is central atom and connect Xe to terminal Fs iii) Give octets to Fs vi) Place extra electrons on Xe iv) count electron pairs. 6 pairs on Xe = 6 4 x 3 pairs on Fl = 12 18 electron pairs
4

Molecular Structure: i) Count electron pairs on central atom: 6 pairs ii) Basic structure is octahedral. structure

Molecular

The lone pairs occupy two opposite corners of the octahedron to avoid stronger repulsion. When you ignore lone pairs the molecular structure becomes a square plane.

Predicting Polarity of molecules

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 39 of 57

H O has a net dipole moment and SO has nodipole moment? However, both the H-O and S-O bonds in these molecules have a polarity. Molecular Structure of H O is bent:
2 2 3

There is polarity alone O - H bonds:

Polarity adds like other mechanical forces. If there are equal dipoles opposite (180 ) to each other they cancel. In water two dipoles are added up to give water molecule a stronger net dipole. Therefore, water molecule is polar and have a dipole moment. Molecular structure of SO :
3 0

First get the Lewis structure of SO

i) Count the total valence lectrons: 6 + 3 x 6 = 24 (12 pairs) ii) S is central atom and connect S to terminal Os iii) Give octets to Os v) count electron pairs. 4 pairs on S = 4 8 pairs on Os = 8 12 electronpairs

Molecular structure of SO : Trigonal planer


3

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 40 of 57

There is a dipole along each S - O bond They are at 120 to each other. Therefore, they cancel out. There is no net dipole moment in SO molecule.
3 0

Predict the polarity (net dipole moment or zero dipole moment) of following molecules : H O, NH , CO , SO , SF , PCl , XeF a) H O: Lewis Structure of H O:
2 2 2 3 2 3 6 5 4

Polarity adds like other forces. If there are equal dipoles opposite (180 ) to each other they cancel. In water two dipoles are added up to give water molecule a stronger net dipole. Therefore, water molecule is polar and have a dipole moment. Two bonds are at about 105 and the polarities adds up to a stronger dipole. H O has a dipole moment.
2 0 0

b) NH : Lewis Structure of NH :
3 3

Molecular Structure: Pyramidal N - H bond is polar: Bonds are not distributed symmetrically. Therefore, ammonia has a dipole moment.

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 41 of 57

c) CO : Lewis Structure of CO :
2 2

Molecular Structure: Linear C - O bond has a polarity: C - O However, bonds are aligned 180 to each other canceling each other. There is no dipole moment in the molecule. d) SO : Lewis Structure of SO :
3 3 0

i) Count the total valence lectrons: 6 + 3 x 6 = 24 (12 pairs) ii) S is central atom and connect S to terminal Os iii) Give octets to Os v) count electron pairs. 4 pairs on S = 4 8 pairs on Os = 8 12 electronpairs

Molecular structure of SO : Trigonal planer


3

There is a dipole along each S - O bond They are at 120 to each other. Therefore, they cancel out. There is no net dipole moment in SO molecule.
3 0

Molecular Structure of SO : trigonal planer


3

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 42 of 57

dipoles are arranged at 120 to each other. Dipoles cancel and there is no dipole moment in the molecule. e) SF : Lewis Structure of SF
6 6

Molecular Structure of SF : octahedral


6

S - F has a dipole. However, bonds are arranged symmetrically opposite to each other. There is no dipole moment in the molecule. f) PCl : Lewis Structure of PCl :
5 5

Molecular Structure: Trigonal bipyramid P - Cl: there is dipole moment in the bond However P - Cl bond are arranged symmetrically around P canceling each other PCl molecule do not have a dipole.
5

e) XeF : Lewis Structure of XeF :


4 4

Molecular Structure of XeF : Square planer


4

Xe - F bond is polar. However bond are arranged symmetrically opposite to each other, cancelling the dipoles. There is no dipole moment in the

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 43 of 57

molecule. Predicting the hybridization of the central atom(s) in the following molecules: H O (H S), CH (SiH ), CCl (CF , CBr ), CO , NH
2 2 4 4 4 4 4 2 3

(PH ), PCl (PF , NCl )


3 3 3 3

a) H O:
2

Basic structure: tetrahedral number of electrons pairs around oxygen is four: four pairs arrange to minimize electron pair repulsion in a tetrahedron. Four electron pairs are in four sp hybridized orbitals in oxygen. The hybridization of the oxygen atom is sp . H S is similar to H O Hybridization of S atom is sp . b) CH :
4 3 2 2 3 3

Basic structure: tetrahedral number of electron pairs around the central atom is four. The hybridization of the C atom of CH is sp .
4 3 3

SiH - hybridization of Si atom is sp .


4

c) CCl :
4

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 44 of 57

Basic structure: tetrahedral There are four electron pairs on C atom.

The hybridization of the carbon atom is sp . In CF and CBr the hybridization of C is sp .


4 4 3

d) CO :
2

Basic structure: linear number of electron pairs 2 (what is really making directional bonds) Hybridization of the C atom is sp . e) NH :
3 2

Four electron pairs around central N atom. The hybridization of atomic orbitals of N atom is sp . PH : sp3 hybridization of P.
3 3

f) PCl :
3

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 45 of 57

Four electron pairs around central P atom. Hybridization of P is sp . PF , NCl : hybridization of central atom is sp
3 3 3

Inclusion of atomic orbitals into Lewis Structure and VSEPR Theory Valence-Bond Theory
Covalent bonding is the result of orbital overlap, the overlap of atomic orbitals from two atoms, and the sharing of electrons in the region of overlap. This is the central idea of Valence Bond Theory, which describes how covalent bonding occurs. Molecular Orbital Theory, on the other hand, postulates the combination of atomic orbitals of different atoms to form molecular orbitals, so that the electrons in them belongs to the molecule as a whole. These two have strengths and weaknesses that are complementary. VB theory is easy to visualize, but MO theory gives a better descriptions of bond energies and magnetic properties. The Heitler-London model of covalent bonds was the basis of the valence-bond theory. The last major step in the evolution of this theory was the suggestion by Linus Pauling that atomic orbitals mix to form hybrid orbitals, such as the sp, sp , sp , dsp , and d sp orbitals. Covalent bonding and orbital overlap of hybridized orbitals of the central atom Hybridization in Simple Molecules Hybrid orbitals Hybrid orbitals are combinations of different types of atomic orbitals on the same atom. In forming a molecule, the combination of valence orbitals of the center atom and the other atoms, which gives a maximum overlap will be favored. This is the original idea to mix different atomic orbitals of the center atom. sp hybrid orbitals sp hybridization
3 2 3 2 3

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 46 of 57

sp hybrid orbitals

sp hybrid orbitals

Hybridization involving d orbitals It is easy to apply the valence-bond theory to some coordination complexes, such as the Co(NH ) configuration of the transition- metal ion. Co
3+

3+ ion. We start with the electron 36 6

: [Ar] 3d

We then look at the valence-shell orbitals and note that the 4s and 4p orbitals are empty. Co
3+

: [Ar] 3d 4s 4p
xy xz

0 yz

Concentrating the 3d electrons in the d , d , and d subshell gives the following electron configuration.

orbitals in this

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 47 of 57

The 3d

a set of empty d sp orbitals that point toward the corners of an octahedron. Each of these orbitals can accept a pair of nonbonding electrons from a neutral NH molecule to form a complex in which the
3

2 2 2 , 3d , 4s, 4p , 4p and 4p orbitals are then mixed to form x -y z x y z 2 3

cobalt atom has a filled shell of valence electrons.

At first glance, complexes such as the Ni(NH )

2+

36

ion seem hard to

explain with the valence-bond theory. We start, as always, by writing the configuration of the transition-metal ion. Ni : [Ar] 3d This configuration creates a problem, because there are eight electrons in the 3d orbitals. Even if we invest the energy necessary to pair the 3d electrons, we can't find two empty 3d orbitals to use to form a set of d sp hybrids.
2 3 2+ 8

There is a way around this problem. The five 4d orbitals on nickel are empty, so we can form a set of empty sp d hybrid orbitals by mixing the 4d
2 2 2 , 4d , 4s, 4p , 4p and 4p orbitals. These hybrid orbitals x -y z x y z 3 2

then accept pairs of nonbonding electrons from six ammonia molecules to form a complex ion.

The valence-bond theory therefore formally distinguishes between "inner-shell" complexes, which use 3d, 4s and 4p orbitals to form a set of d sp hybrids, and "outer-shell" complexes, which use 4s, 4p and 4d orbitals to form sp d hybrid orbitals.
3 2 2 3

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 48 of 57

Multiple Bonding
Hybrid orbitals and multiple bonds Double Bonds When working geometry problems by the VSEPR method, a double or triple bond acts just like a single bond for geometry purposes: the added electrons don't have any effect on the molecular geometry. This is because the extra electrons in multiple bonds do not reside in hybrid orbitals For example, the ethylene molecule has the Lewis diagram below.

The bond angles around carbon in ethylene are 120 , which implies an AX geometry and sp hybridization. One of the two shared electron
3 2 2

pairs on a carbon in the molecule (blue) is in an sp hybrid orbital as are the two electron pairs that form bonds to the hydrogen, the other (red) is not. The bonding pair that is in the hybrid orbital is said to reside in a bond. So what type of orbital are the other two electrons in? It turns out that they are in the remaining unhybridized p orbitals on the carbon. (The sp hybrid uses one s and two p orbitals, leaving a p orbital on each carbon.) These two p orbitals overlap, forming a bond. This orbital sticks up out of the plane of the molecule, as in the picture below
2

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 49 of 57

Triple bonds In the case of acetylene, HCCH, we have the Lewis structure below Here, we have sp hybridization and an AX geometry around the
2

carbons. There are two p orbitals left over on each carbon: both overlap and thus form two bonds (red) along with the (blue) bond that results from the electrons in sp hybrid orbitals. Some pictures of the two sets of bonds are below

Delocalized bonding
ORBITAL PICTURE OF THE CYCLIC OVERLAP IN BENZENE. Note that all six carbons in benzene are trigonally hybridized and the entire molecule is coplanar. Each carbon therefore contributes a 2p AO to the pi bonding system. A key aspect of this is that each of these orbitals overlaps with two other 2p AO's on adjacent carbon atoms, one to the left and one to the right, not just to a single one. Thus the system of overlapping orbitals acts
z z

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 50 of 57

as a unit, all electrons being entirely delocalized over the ring. Because overlap is much more extensive, bonding is stronger than in a simple alkene pi bond.

Whenever more than one reasonable valence structure can be written for a species. ( In this case, this normally means that the electrons are more delocalized than can be shown by any one structure). Network Covalent Substances Network Covalent Network covalent solids are one common type of solids. In a network covalent solid, the atoms are bound to each other by a network of covalent bonds. Common properties of network covalent substances are: High melting point and boiling point. Covalent bonds are very strong. Insoluble in most solvents. Breaking the covalent bonds to dissolve the substance takes a lot of energy. Poor electrical conductivity. The electrons are localized in covalent bonds, not spread out like in a metal. Examples of network covalent substances are diamond, quartz and graphite. Models of diamond and graphite are shown below if you have Chime installed. Graphite is an interesting case: it's made up of sheets of sp hybridized carbon atoms in a network covalent arrangement, but the sheets themselves aren't bonded to other sheets and are held together only with London dispersion forces. Intermolecular Forces Molecules exist as distinct, separate collections of matter. The bonds within a
2

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 51 of 57

molecule are typically quite strong, such that it's usually necessary to heat a molecule to very high energies before the bonds begin to break. For example, water is stable to decomposition to hydrogen and oxygen up to temperatures well above 500 C. In contrast, the forces between molecules tend to be relatively weak. If we chose an arbitrary scale in which the bonds between atoms within a molecule are set at 100, then the forces between molecules range between 0.001 and 15. In other words it generally takes far less energy to separate molecules from one another than it does to take molecules apart. The forces between molecules are called intermolecular forces Intermolecular forces are the attractions that exist among particles or molecules of matter in any of the three distinct phases of matter, gases, liquids and solids, found on earth. The strength of these forces increases as the matter change in phase from gas to a liquid and then to a solid. Thus gases have the weakest intermolecular forces compare to liquids and solids and solids have the strongest forces. The intermolecular forces in ionic solids are so strong that they exist only as solids even at very higher temperatures. ionic solids have ionic interactions, the strong electrostatic attractions between oppositely charged ions to form a ionic lattice as in sodium chloride, NaCl(s). Other forms of weaker intermolecular forces resulting from polar covalent bonds in molecules and the polarization of electrons on non-polar covalent molecules. These weaker intermolecular forces are classified according to their strength as shown below: Intramolecular forces: Intramolecular forces are the attractions that exist among particles of a molecules. These are found in gaint molecules such as proteins. Dipole-dipole (or simply polar) forces
o

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 52 of 57

Dipole-Dipole Intermolecular forces: This include the attraction between all polar molecules through the dipoles (except F-H, O-H and N-H dipoles) dipolar covalent bond formed by unequal sharing of electrons of bonds in a molecule. A molecule can be non-polar even though it may have polar covalent bond because of the symmetry of the molecular structure canceling the dipoles. Therefore, there are no dipole-dipole interactions in non-polar molecules. Hydrogen bonding Hydrogen bonding are three special cases of stronger dipole-dipole interactions resulting from F-H, O-H and N-H dipolar covalent bond are called hydrogen bonding. This is because F, O and N have the largest electronegativities among other elements. Hydrogen bonding (between O-H and O-H dipoles) in water allows water to exist as a liquid at room temperature. N-H dipole in proteins allows the formation of doubles helix structure in DNA and other complex structures found in living cells. London dispersion forces London Dispersion Forces are the weakest of all intermolecular attractions and occur in non-polar molecules without dipoles or dipolar covalent bonds. The London dispersion forces results from instantaneous shifts of electron cloud of non-polar molecules. These shifts in electron cloud create instantaneous dipoles with very short lifetime. A weaker attractive force results because of the short lived dipole attractions between two molecules. Non-polar molecules such as H2 and N2 can be cooled to liquids at very low temperature due to the existence of London Dispersion forces. As the number of electrons increases or the molecular weight of a substance increases the London Dispersion forces tend to increase making these substances to exists as solids. Even though London dispersion forces exist in ionic solids and polar covalent compounds, their effect is masked by stronger ionic interactions and dipole-dipole interactions. To fully understand intermolecular forces you may wish to review discussions on molecular shape and VSEPR Theory.

Electronegativity: Deciding Factor of Pure Covalent, Polar Covalent and Ionic Bonding between two atoms

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 53 of 57

In LiH molecule, it would seem that the bonding orbital places more electron density on the hydrogen than on the lithium since the orbital shape describes the probability of finding the electrons. As a result, the hydrogen end of the moelcule would be slightly negative and the lithium end would be slightly positive.This situation is called a polar bond in which the electrons in the bond are being shared, but not equally shared. In almost every case in which a bond is formed between two different atoms the resulting bond will be polar. In the 1930's, Linus Pauling (1901 1994), an American chemist who won the 1954 Nobel Prize, recognized that bond polarity resulted from the relative ability of atoms to attract electrons. Pauling devised a measure of this electron attracting power which he called "electronegativity" which he defined as the "power of an atom in a molecule to attract electrons to itself." Electronegativity only has meaning in a bond. The table below presents the electronegativities for the main group elements. Electronegativity H= x 2.1 Be Li = = 1.0 1.5 Na = 0.9 Mg = 1.2 x x x x x

B= C= N= O= F= 2.0 2.5 3.0 3.5 4.0 Al = Si = P = S = Cl = 1.5 1.8 2.1 2.5 3.0

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 54 of 57

Ca K= = 0.8 1.0 Rb = 0.8 Cs = 0.7

Ga = 1.6

Ge = 1.8

As = 2.0 Sb = 1.9

Se = 2.4 Te = 2.1

Br = 2.8 I= 2.5 At = 2.2

Sn Sr = In = = 1.0 1.7 1.8 Ba = 0.9 Pb Tl = = 1.8 1.9

Po Bi = = 1.9 2.0

Generally, the electronegativity increases moving left to right across a row, and decreases going down the table. Notice that this trend is violated by the Group 13 metals for which the electronegativity drops from B to Al as expected, but hen rises slightly going down to Tl. This effect is due to the intervention of the d electrons and other effects that come into play with very large atoms. The transition metals are not presented in this chart to conserve room, but their values range from 1.0 to about 2.4. When we are looking at a chemical bond to predict whether it is polar (and polar in which direction) we must compare the electronegativities of the atoms in the bond. The atom with the higher EN will have the negative end of the polar bond, and the difference in EN will give a rough measure of the extent of the polarity. n the molecules H , F and O which are called homonuclear (same
2 2 2

atoms) diatomic molecules there is no bond polarity. Electrons in the bond are pulled equally and found in the center between the two atoms. How you decide whether a bond is pure covalent, polar covalent, or ionic? 0-0.6 covalent bond 0.6 - 1.5 Polar-covalent bond > 1.5 ionic bond

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 55 of 57

Polarity of a molecular substance is measured as dipole moment. If molecule has a dipole moment it means may have polar covalent bonds If polar covalent bonds are symmetrical, they may lead to zero dipole moment Consider the following examples: Bond Polarities Bond H-H C-H O-H H-F S-O C-O Al - C Diff in EN Negative atom Type of Bond 0.0 0.4 1.4 1.9 1.0 1.0 1.0 N/A C O F O O C Cl O C pure covalent (weakly) polar covalent polar covalent polar covalent polar covalent polar covalent polar covalent ionic ionic polar covalent

Na - Cl 2.1 Mg - O 2.3 Mg - C 1.3

Pure Covalent, Polar Covalent, and Ionic Bonds It's not unusual for covalent bonds and ionic bonds to be presented to introductory students as two clearly distinct categories. In the usual definition, covalent bonds involve electron sharing and ionic bonds involve electron transfer to form ions. These definitions are correct, but they miss the reality that pure covalent and ionic bonds sit on a continuum dictated by the difference in electronegativity. The bigger this difference, the more polar the bond. At some point we would expect the bond to have become so polar that it constitutes a transfer of an electron from one atom to the other. The chart below gives an idea of how this trend works.

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 56 of 57

Using some simple calculations of % ionic and % covalent character, it is possible to show that a difference of electronegativity of about 1.7 is the point where a bond may be thought of as ionic. There are a few exceptions to this rule such as HF, in which the electronegativity difference is 1.9, but the molecular properties are decidedly covalent. Again, in many introductory courses, students are presented with a thumb rule: Covalent bond = non-metal + non-metal Ionic bond = metal + non-metal It's easy to see that this rule is only a rough approximation and works well for compounds of the Group 1 or 2 metals with the halides of Group 17, but doesn't reflect reality when we consider bonds between carbon and most metals. Carbon is certainly a non-metal, but it forms covalent bonds (sometimes highly polar, but covalent none the less) with almost all of the elements on the periodic table.

Covalent Bonding and the Periodic Table


In general chemistry you learned that having eight electrons (an octet) in the valence shell of the noble gases (group 8A) gives those elements special stability. We also have seen that the reactions of most elements are driven by their desire to attain a noble gas

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003

404 Not Found

Page 57 of 57

electronic configuration. The alkali metals in group 1A have a single electron in their valence shell and usually give up this electron in reactions to achieve a noble gas electronic configuration. Unlike the alkali metals which tend to give up their valence electron to achieve a noble gas configuration, the halogens in group 7A (with 7 valence electrons) tend to gain an electron in reactions to attain a full octet of electrons. Elements on the right side of the periodic table (nonmetals) react by gaining electrons and elements on the left side of the periodic table (metals) react by losing electrons. The type of bonding that occurs when a nonmetal accepts an electron from a metal is referred to as ionic bonding and the bond is called an ionic bond. This is the type of bonding that occurs in ionic solids like sodium chloride, NaCl. Please return to the referring document and note the hypertext link that led you here.

http://138.47.34.166/chem281/281GRCc3.htm

1/6/2003