Chemistry 1A

Chapters 8 and 9

Molecular Orbital Theory

Goal: to generate molecular orbital diagrams that describe molecules, like the atomic orbital diagrams that describe atoms. Molecular Orbital: a volume within which a high percentage of the negative charge for an electron in a molecule is found.

Atomic Orbitals and Molecular Orbitals

Molecular Orbital Diagram for O2 Like Atomic Orbital Diagram for O

Goal: To determine the MO Diagram for Diatomic Molecules

We assume that the electrons would fill the molecular orbitals of molecules like electrons fill atomic orbitals in atoms.
The molecular orbitals are filled in a way that yields the lowest potential energy for the molecule. The maximum number of electrons in each molecular orbital is two. (We follow the Pauli exclusion principle.) Orbitals of equal energy are half filled with parallel spin before they begin to pair up. (We follow Hund's Rule.)

Linear Combination of Atomic Orbitals - LCAO

Atomic orbitals (AOs) of about the same energy overlap to form molecular orbitals (MOs). Pairs of AOs overlap in two extreme ways.
In-phase to bonding MO out-of-phase to antibonding MO

Electron and Light Waves

is like

Describes the variation in the intensity of negative charge created by an electron.

Describes the variation in the electric and magnetic fields created by light.

Wave Interference

In-Phase and Out-ofPhase Interactions

Light waves can interact in-phase and out-of-phase.
In-phase leads to an increase in the intensity of the light (brighter). Out-of-phase leads to a decrease in the intensity of the light (less bright).

Electron waves can interact in-phase and out-of-phase.

In-phase leads to an increase in the intensity of the negative charge. Out-of-phase leads to a decrease in the intensity of the negative charge.

MOs from 1s Orbitals

 From in-phase interaction of two atomic orbitals. Leads to an increase in negative charge between two nuclei where the atomic orbitals overlap. Leads to more +/- attraction between the negative charge generated by the electrons and the nuclei. Thus there is a decrease in PE. Energy would be required to separate the atoms, so electrons in this type of molecular orbital tend to keep atoms together.

Bonding Molecular Orbital

Antibonding Molecular Orbital

From out-of-phase interaction of two atomic orbitals. Leads to a decrease in negative charge between two nuclei where the atomic orbitals overlap. Leads to less +/ attraction between the negative charge generated by the electrons and the nuclei. Thus there is an increase in PE. Electrons are more stable in separate atomic orbitals of separate atoms, so electrons in this type of molecular orbital tend to keep atoms separate.

MOs from 1s Orbitals (cont.)

Molecular Orbitals from 2px Atomic Orbitals

Molecular Orbitals from 2py Atomic Orbitals

 The 2p molecular orbital comes from parallel overlap of p orbitals, and 2p comes from end-on overlap. Greater overlap between end-on p orbitals leads to a greater increase in negative charge between the nuclei, a greater increase in +/attraction, a greater stabilization of the electrons, and greater decrease in PE of these electrons.

Why 2p lower PE than 2p?

Why 2p* lower PE than 2p*?

The 2p molecular orbital comes from parallel overlap of p orbitals, and 2p comes from end-on overlap. Less overlap between parallel p orbitals leads to a lesser decrease in negative charge between the nuclei, a lesser decrease in +/- attraction, a lesser destabilization of the electrons, and lesser increase in PE of these electrons.

MO Diagram for O2, F2, Ne2, CO, and NO

Procedure for Drawing MO Diagrams

Determine the number of electrons in the molecule. We get the number of electrons per atom from their atomic number on the periodic table. Fill the molecular orbitals from bottom to top until all the electrons are added. Describe the electrons with arrows. Put two arrows in each molecular orbital, with the first arrow pointing up and the second pointing down. Orbitals of equal energy are half filled with parallel spin before they begin to pair up.

Bond Order
1/2(e bonding MO's e antibonding MO's)

We use bond orders to predict the stability of molecules.

If the bond order for a molecule is equal to zero, the molecule is unstable. A bond order of greater than zero suggests a stable molecule. The higher the bond order is, the more stable the bond.

Paramagnetic or Diamagnetic
If all the electrons are paired, the molecule is diamagnetic. If one or more electrons are unpaired, the molecule is paramagnetic.

Hydrogen, H2

The bond order is 1.

Bond Order = 1/2(2 0) = 1

The bond order above zero suggests that H2 is stable. Because there are no unpaired electrons, H2 is diamagnetic.

Helium, He2

The bond order is 0 for He2.

Bond Order = 1/2(2 2) = 0

The zero bond order for He2 suggests that He2 is unstable. If He2 did form, it would be diamagnetic.

Oxygen, O2
O2 has a bond order of 2.
Bond Order = 1/2(10 6) = 2

The bond order of two suggests that the oxygen molecule is stable. The two unpaired electrons show that O2 is paramagnetic.

Fluorine, F2
F2 has a bond order of 1.
Bond Order = 1/2(10 8) = 1

The bond order of one suggests that the fluorine molecule is stable. Because all of the electrons are paired F2 is diamagnetic.

Neon, Ne2
Ne2 has a bond order of 0.
Bond Order = 1/2(10 10) = 0

The bond order zero for Ne2 suggests that Ne2 is unstable. If Ne2 did form, it would be diamagnetic.

Carbon Monoxide, CO

Nitrogen Monoxide, NO

Molecular Orbital Theory Issues

Problem: At the level described in general chemistry, the molecular orbital theory is too limited in its application. Solution: Switch to a simpler model that incorporates as much of the molecular orbital theory as possible but that has broader application. The new model is called the valence bond model.

Models Advantages and Disadvantages (1)

They help us to visualize, explain, and predict chemical changes. Because a model is a simplified version of what we think is true, the processes it depicts are sometimes described using the phrase as if. When you read, It is as if an electron were promoted from one orbital to another, the phrase is a reminder that we do not necessarily think this is what really happens. We merely find it useful to talk about the process as if this is the way it happens.

Models Advantages and Disadvantages (2)

One characteristic of models is that they change with time. Because our models are simplifications of what we think is real, we are not surprised when they sometimes fail to explain experimental observations. When this happens, the model is altered to fit the new observations.

Assumptions of the Valence-Bond Model

Only the highest energy electrons participate in bonding. Covalent bonds usually form to pair unpaired electrons. Covalent bonds arise when atomic orbitals on adjacent atoms overlap to form molecular orbitals.

Valence Electrons
Valence electrons are the highestenergy s and p electrons in an atom.

Fluorine
F 1s2 2s2 2p5

Valence electrons

Atomic Orbital Overlap for F2 (1)

One way to describe how the covalent bond between fluorine atoms forms is to say that a 2p orbital from each atom overlaps to form a 2p molecular orbital. The two unpaired electrons from the 2p orbitals of the two fluorine atoms are then in the more stable 2p molecular orbital, making the F2 molecule more stable than the separate F atoms.

Atomic Orbital Overlap for F2 (2)

Because the bond arises due to the formation of a sigma molecular orbital, it is called a sigma bond.

H2 Formation (1)
1s atomic orbitals, one from each hydrogen atom, overlap to form a 1s molecular orbital. The two electrons in H2 are found in the 1s, leading to a more stable H2 molecule.

H2 Formation (2)
Again, because the bond arises due to the formation of a sigma molecular orbital, it is called a sigma bond.

Things to explain for the bonding in a methane molecule, CH4 Why are there four C-H covalent bonds? Why do all of the bonds have the same length and strength? Why is the molecule tetrahedral with bond angles of 109.5?

Carbon 4 bonds

Formation of sp3 hybrid orbitals

Orbital Overlap in Methane, CH4

Bonding in CH4
Four equivalent sigma C-H covalent bonds arise due to the overlap of four sp3 hybrid orbitals on the carbon atom with 1s atomic orbitals on the hydrogen atoms. Hybrid orbitals always form sigma bonds. Because the sp3 hybrid orbitals are arranged in a tetrahedral geometry, the molecule has tetrahedral geometry.

Methane, CH4

Explanation of Bonding Patterns - Valence Bond Model Part 1

Step 1: Write, Only the highest energy electrons participate in bonding. Step 2: Draw the orbital diagram for the valence electrons. Include the empty d orbitals for the third period nonmetals and below. Step 3: If there is a formal charge, add or subtract electrons.
Add one electron for -1. Subtract one electron for +1.

Explanation of Bonding Patterns - Valence Bond Model Part 2

Step 4: If necessary, promote one or more electrons from a pair to an empty orbital to get the number of unpaired electrons equal to the number of bonds to be explained. Rewrite the orbital diagram if electrons have been promoted. Step 5: Predict the hybridization, and rewrite the orbital diagram, showing the predicted hybrid orbitals. Step 6: Write, Covalent bonds form in order to pair unpaired electrons. Step 7: Indicate that the unpaired electrons form the bonds. Step 8: Indicate that the paired electrons are lone pairs.

Descriptions of Molecules
You will be given a Lewis structure, and you will be asked the following.
What is the hybridization for each atom in the structure? Write a description of the formation of each bond in terms of the overlap of atomic orbitals. Describe the electron group geometry around each atom that has two or more atoms attached to it. Draw the geometric sketch of the molecule, including bond angles. Describe the molecular geometry around each atom that has two or more atoms attached to it.

Steps for Hybridization Part 1

Step 1: Count the number of electron groups around each atom.
An electron group is any one of the following.
single bond double or triple bond (each counts as one group) lone pair

Steps for Hybridization Part 1

Step 2 Apply the following guidelines.
1 group - No hybridization 2 groups - sp hybridization 3 groups - sp2 hybridization 4 groups - sp3 hybridization 5 groups - sp3d hybridization 6 groups - sp3d2 hybridization

Describing the bonds in terms of the overlap of atomic orbitals

Step 1: Describe single bonds that do not involve hydrogen as due to the overlapping of two hybrid orbitals, one from each atom. Step 2: Describe single bonds that involve hydrogen as due to the overlapping a hybrid orbital with a 1s orbital for the hydrogen atom. Step 3: Describe double bonds as one bond forming from the overlap of two hybrid orbitals, one from each atom. Describe the second bond as due to the overlap of two p orbitals, one from each atom. Step 4: Describe triple bonds as one bond forming from the overlap of two hybrid orbitals, one from each atom. Describe each of the other two bonds as due to the overlap of two p orbitals, one from each atom.

Steps for Molecular Geometry

Step 1: To determine the name of the electron group geometry around each atom that is attached to two or more atoms, count the number of electron groups around each atom and apply the guidelines found on the following slides. Step 2: Use one or more of the geometric sketches shown on the following slides for the geometric sketch of your molecule.

Steps for Molecular Geometry (cont.)

Step 3: To determine the name of the molecular geometry around each atom that has two or more atoms attached to it, count the number of bond groups and lone pairs, and then apply the guidelines found on the following slides.

Electron Group and Molecular Geometry Part 1

2 e- groups linear electron group geometry - 180 angles.
2 bond groups and 0 lone pairs linear molecular geometry

Electron Group and Molecular Geometry Part 2

3 e- groups trigonal planar electron group geometry - 120 angles.
3 bond groups and 0 lone pairs trigonal planar molecular geometry 2 bond groups and 1 lone pair bent molecular geometry

Electron Group and Molecular Geometry Part 3

4 e- groups tetrahedral electron group geometry 109.5 angles.
4 bond groups and 0 lone pairs tetrahedral molecular geometry 3 bond groups and 1 lone pair trigonal pyramid molecular geometry 2 bond groups and 2 lone pairs bent molecular geometry

Things to explain for the bonding in a ethene (ethylene) molecule, C2H4

Why are there four equivalent C-H covalent bonds? Why are all the bond angles about 120? According to our model, how does the double bond form? Why is one bond in the double bond weaker than the other?

Carbon 2 single bonds and one double bond

Formation of sp2 hybrid orbitals

Orbital Overlap for Ethene (Ethylene) Molecule, C2H4

Bonding in C2H4
Four equivalent sigma C-H covalent bonds arise due to the overlap of sp2 hybrid orbitals on the carbon atoms with 1s atomic orbitals on the hydrogen atoms. The double bond between the carbon atoms consists of
one sigma bond formed due to the overlap of two sp2 hybrid orbitals, one from each carbon. One pi bond due to the overlap of unhybridized 2p orbitals, one from each carbon.

Because the sp2 hybrid orbitals are arranged in a trigonal planar geometry, the geometry about each carbon atom is trigonal planar with angles of 120.

Ethene (ethylene)

Pi bonds are generally weaker than sigma bonds.

When p orbitals overlap to form pi bonds there is less overlap than for the overlap between hybrid orbitals to form sigma bonds. Greater overlap between hybrid orbitals leads to a greater increase in the negative charge between the nuclei for the sigma MO compared to the pi MO. This leads to a greater +/- attraction, greater stabilization, and lower PE. Therefore, sigma bonds are generally stronger than pi bonds.

Things to explain for the bonding in an ethyne (acetylene) molecule, C2H2

Why are there two equivalent C-H covalent bonds? Why are all the bond angles 180? How does the triple bond between carbons atoms form? Why are two bonds in the triple bond weaker than the other one?

Carbon 1 single bond and 1 triple bond

Formation of sp hybrid orbitals

Orbital Overlap for Ethyne (Acetylene) Molecule, C2H2

Bonding in C2H2
Two equivalent sigma C-H covalent bonds arise due to the overlap of sp hybrid orbitals on the carbon atoms with 1s atomic orbitals on the hydrogen atoms. The triple bond between the carbon atoms consists of
one sigma bond formed due to the overlap of two sp hybrid orbitals, one from each carbon. Two pi bonds, each of which arises due to the overlap of unhybridized 2p orbitals, one from each carbon.

Because the sp hybrid orbitals are arranged in a linear geometry, the geometry about each carbon atom is linear with angles of 180.

Ethyne (acetylene) , C2H2

Things to explain for the bonding in an ammonia molecule, NH3

Why are there three equivalent N-H covalent bonds? Why are the bond angles about 107?

Nitrogen 3 bonds & 1 lone pair

Orbital Overlap for Ammonia, NH3

Bonding in NH3
Three equivalent covalent bonds arise due to the overlap of three sp3 hybrid orbitals on the nitrogen atom with 1s atomic orbitals on the hydrogen atoms. The lone pair can be viewed as in an sp3 hybrid orbital. Because the sp3 hybrid orbitals are arranged in a tetrahedral geometry, the molecule has tetrahedral electron group geometry with bond angles of about 109.5 (actually about 107). A molecule that has three bonds and one lone pair around its central atom is said to have trigonal pyramid molecular geometry.

Electron Group Geometry and Molecular Geometry

Electron group geometry describes all of the electron groups around the central atom, including lone pairs. Molecular geometry just describes the bond groups.

Ammonia, NH3, Geometry

Ammonia molecules have tetrahedral electron group geometry and trigonal pyramid molecular geometry.

Ammonia, NH3

Things to explain for the bonding in an ammonium ion, NH4+

Why are there four equivalent N-H covalent bonds? Why does the polyatomic ion have tetrahedral geometry with bond angles of 109.5?

Formal Charge
A measure of the stability of an atom in a molecule Formal charge = number of valence electrons needed to be uncharged approximate number of valence electrons atom has
The A-group number tells us the number of valence electrons needed to be uncharged. We assume that electrons in covalent bonds are shared equally, so each bond contributes one electron to each atom. Lone pairs contribute two electrons to the atom on which they are found.

Formal charge = A-group number number of lines number of dots

Nitrogen 4 bonds

Orbital Overlap for ammonium, NH4+

Bonding in NH4+
Four equivalent sigma covalent bonds arise due to the overlap of four sp3 hybrid orbitals on the nitrogen atom with 1s atomic orbitals on the hydrogen atoms. Because the sp3 hybrid orbitals are arranged in a tetrahedral geometry, the molecule has tetrahedral electron group geometry with bond angles of about 109.5.

Things to explain for the bonding in a water molecule, H2O

Why are there two equivalent O-H covalent bonds? Why are the bond angles about 105?

Oxygen 2 bonds & 2 lone pairs

Orbital Overlap for Water, H2O

Bonding in H2O
Two equivalent sigma covalent bonds arise due to the overlap of two sp3 hybrid orbitals on the oxygen atom with 1s atomic orbitals on the hydrogen atoms. The lone pairs can be viewed as in sp3 hybrid orbitals. Because the sp3 hybrid orbitals are arranged in a tetrahedral geometry, the molecule has tetrahedral electron group geometry with bond angles of about 109.5 (actually about 105). A molecule that has two bonds and two lone pairs around its central atom is said to have bent molecular geometry.

Water, H2O, Geometry

Water molecules have tetrahedral electron group geometry and bent molecular geometry.

Water, H2O

Oxygen 1 bond & 3 lone pairs

Carbon 3 bonds & 1 lone pair Oxygen 3 bonds & 1 lone pair

Bonding in CO
The triple bond between the carbon and oxygen atoms consists of
one sigma bond formed due to the overlap of two sp hybrid orbitals, one from the carbon atom and one from the oxygen atom. Two pi bonds, each of which arises due to the overlap of unhybridized 2p orbitals, one from the carbon atom and one from the oxygen atom.

Things to explain for the bonding in a boron trifluoride molecule, BF3

Why are there three equivalent B-F covalent bonds? Why is the molecule trigonal planar with bond angles of 120?

Boron 3 bonds

Orbital Overlap in BF3

Trigonal Planar Geometry BF3

Bonding in BF3
Three equivalent sigma covalent bonds arise due to the overlap of three sp2 hybrid orbitals on the boron atom with sp3 atomic orbitals on the fluorine atoms. Because the sp2 hybrid orbitals are arranged in a trigonal planar geometry, the molecule has trigonal planar geometry.

Halogens 1 bond & 3 lone pairs

Things to explain for the bonding in a phosphorus pentafluoride molecule, PF5

Why are there five equivalent P-F covalent bonds? Why is the molecule trigonal planar with bond angles of 90 , 120 , and 180?

Phosphorus 5 bonds

Formation of sp3d Hybrid Orbitals

Orbital Overlap in PF5

Bonding in PF5
Five equivalent sigma covalent bonds arise due to the overlap of five sp3d hybrid orbitals on the phosphorus atom with sp3 atomic orbitals on the fluorine atoms. Because the sp3d hybrid orbitals are arranged in a trigonal bipyramid geometry, the molecule has trigonal bipyramid geometry.

Bonding in SF4
Four equivalent sigma covalent bonds arise due to the overlap of sp3d hybrid orbitals on the sulfur atom with sp3 atomic orbitals on the fluorine atoms. The molecule has trigonal bipyramid electron group geometry and see-saw molecular geometry.

Orbital Overlap in SF4

Bonding in IF3
Three equivalent sigma covalent bonds arise due to the overlap of sp3d hybrid orbitals on the iodine atom with sp3 atomic orbitals on the fluorine atoms. The molecule has trigonal bipyramid electron group geometry and T-shaped molecular geometry.

Orbital Overlap in IF3

Bonding in XeF2
Two equivalent sigma covalent bonds arise due to the overlap of sp3d hybrid orbitals on the xenon atom with sp3 atomic orbitals on the fluorine atoms. The molecule has trigonal bipyramid electron group geometry and linear molecular geometry.

Orbital Overlap in XeF2

Electron Group and Molecular Geometry Part 4

5 e- groups trigonal bipyramid electron group geometry 90 , 120 , and 180 angles.
5 bond groups and 0 lone pairs trigonal bipyramid molecular geometry 4 bond groups and 1 lone pair see-saw molecular geometry 3 bond groups and 2 lone pairs T-shaped molecular geometry 2 bond groups and 3 lone pairs linear molecular geometry

Things to explain for the bonding in a sulfur hexafluoride molecule, SF6

Why are there six equivalent S-F covalent bonds? Why is the molecule octahedral with bond angles of 90 and 180?

Sulfur - 6 bonds

Formation of sp3d2 Hybrid Orbitals

Orbital Overlap in SF6

Bonding in SF6
Six equivalent sigma covalent bonds arise due to the overlap of sp3d2 hybrid orbitals on the sulfur atom with sp3 atomic orbitals on the fluorine atoms. Because the sp3d2 hybrid orbitals are arranged in an octahedral geometry, the molecule has octahedral geometry.

Bonding in IF5
Five equivalent sigma covalent bonds arise due to the overlap of sp3d2 hybrid orbitals on the iodine atom with sp3 atomic orbitals on the fluorine atoms. The molecule has octahedral electron group geometry and square pyramid molecular geometry.

Orbital Overlap in IF5

Bonding in XeF4
Four equivalent sigma covalent bonds arise due to the overlap of sp3d2 hybrid orbitals on the xenon atom with sp3 atomic orbitals on the fluorine atoms. The molecule has octahedral electron group geometry and square planar molecular geometry.

Orbital Overlap in XeF4

Electron Group and Molecular Geometry Part 5

6 e- groups octahedral electron group geometry 90 and 180 angles.
6 bond groups and 0 lone pairs octahedral molecular geometry 5 bond groups and 1 lone pair square pyramid molecular geometry 4 bond groups and 2 lone pairs square planar molecular geometry

Drawing Lewis Structures (1)

If the formula represents an uncharged molecule, try to draw a Lewis structure in which all of the atoms have their most common bonding pattern.
Hydrogen 1 bond 0 lone pairs Halogens 1 bond 3 lone pairs O, S, Se 2 bonds 2 lone pairs N, P 3 bonds 1 lone pair C 4 bonds 0 lone pairs

Drawing Lewis Structures (2) If the shortcut doesnt work,

Step 1: Determine the total number of valence electrons for the molecule or polyatomic ion.
For uncharged molecules, the total number of valence electrons is the sum of the valence electrons of each atom. For polyatomic cations, the total number of valence electrons is the sum of the valence electrons for each atom minus the charge. For polyatomic anions, the total number of valence electrons is the sum of the valence electrons for each atom plus the charge.

Drawing Lewis Structures (3)

Step 2: Draw a reasonable skeletal structure, using single bonds to join all the atoms.
Try to arrange the atoms to yield the most typical number of bonds for each atom. Apply the following guidelines in deciding what element belongs in the center of your structure.
Hydrogen and fluorine atoms are never in the center. Oxygen atoms are rarely in the center. The element with the fewest atoms in the formula is often in the center. The atom that is capable of making the most bonds is often in the center.

Oxygen atoms rarely bond to other oxygen atoms. The molecular formula often reflects the molecular structure. Carbon atoms commonly bond to other carbon atoms.

Drawing Lewis Structures (4)

Step 3: Subtract 2 electrons from the total for each of the single bonds (lines) described in Step 2.

Drawing Lewis Structures (5)

Step 4: Try to distribute the remaining electrons as lone pairs to obtain a total of eight electrons around each atom except hydrogen and boron.
In a reasonable Lewis structure, carbon, nitrogen, oxygen, and fluorine always have eight electrons around them. Hydrogen will always have a total of two electrons from its one bond. Boron can have fewer than eight electrons but never more than eight. The nonmetallic elements in periods beyond the second period (P, S, Cl, Se, Br, and I) usually have eight electrons around them, but they can have more. The bonding properties of the metalloids arsenic, As, and tellurium, Te, are similar to those of phosphorus, P, and sulfur, S, so they usually have eight electrons around them but can have more.

Drawing Lewis Structures (6)

Step 5: Do one of the following.

If in Step 4 you were able to obtain an octet of electrons around each atom other than hydrogen and boron, and if you used all of the remaining valence electrons, go to Step 6. If you have electrons remaining after each of the atoms other than hydrogen and boron have their octet, you can put more than eight electrons around elements in periods beyond the second period. If you do not have enough electrons to obtain octets of electrons around each atom (other than hydrogen and boron), convert one lone pair into a multiple bond for each two electrons that you are short.

Drawing Lewis Structures (7)

Step 6: Check your structure.
See if all of the atoms have their most common bonding pattern. Determine the formal charge for each atom that does not have its most common bonding pattern.
Formal charge = A-group # - # lines - # dots Formal charge = 0 means stable

Drawing Lewis Structures (8)

Step 7: If necessary, try to rearrange your structure to give each atom its most common bonding pattern and a minimum of formal charges.
One way to do this is to return to Step 2 and try another skeleton. If your central atom is below the second period, you can bring a lone pair in from an outer atom with a negative formal charge to form a new bond to a central atom with a positive formal charge.

Lewis Structure Drawing Summary

Nitrate Resonance

Resonance
We can view certain molecules and polyatomic ions as if they were able to resonateto switch back and forthbetween two or more different structures. Each of these structures is called a resonance structure. The hypothetical switching from one resonance structure to another is called resonance.

3 Criteria for Resonance

There must be a double or triple bond. There must be an adjacent atom with at least one lone pair. The adjacent atom cannot be a fluorine atom or an oxygen with 2 bonds and two lone pairs.

To draw Resonance Forms

Nitrate Resonance

Steps for Drawing Resonance Hybrid

Draw the skeletal structure with solid lines for the bonds that are found in all of the resonance forms. Where there is sometimes a multiple bond and sometimes not, draw a dotted line. Draw in all of the lone pairs that are found on every one of the resonance forms. (Leave off the lone pairs that are on one or more resonance form but not on all of them.) Put on full formal charges on those atoms that have the formal charge in all of the resonance forms. Put on partial formal charges on the atoms that have formal charges in one or more of the resonance forms but not in all of them.

NO3- Resonance Hybrid

Delocalized Pi System for NO3-

PO43- Controversy Minimize Formal Charges

PO43- Controversy Follow Octet Rule

PO43- Geometry
Both possible Lewis structures predict the same geometry, and both show that the four bonds are equivalent.

Triglycerides (Fats and Oils)

Saturated Triglyceride Tristearin

Tristearin Line Drawing

Unsaturated Triglyceride

Cis and Trans

When there is a double bond between two carbons and when like groups are on different carbons and the same side of the double bond the arrangement is called cis. When the like groups are on opposite sides of the double bond the arrangement is called trans.

Hydrogenation

Hydrogenation - Example

Trans Fats
Hydrogenation is reversible. When the double bond is reformed, it is more likely to form the more stable trans form than the less stable cis form. Therefore, partial hydrogenated vegetable oils contain trans fats, which are considered to be damaging to your health.

Olestra - a Fat Substitute

Predicting Molecular Polarity

Step 1: Draw a reasonable Lewis structure for the substance. Step 2: Identify each bond as either polar or nonpolar.
If there are no polar bonds, the molecule is nonpolar. If the molecule has polar bonds, move on to Step 3.

Electronegativities

Bond Type Prediction

Predicting Molecular Polarity (cont.)

Step 3: If there is only one central atom, examine the electron groups around it.
If there are no lone pairs on the central atom, and if all the bonds to the central atom are the same, the molecule is nonpolar. If the central atom has at least one polar bond and if the groups bonded to the central atom are not all identical, the molecule is probably polar. Move on to Step 4.

Step 4: Draw a geometric sketch of the molecule.

Predicting Molecular Polarity (cont.)

Step 5: Determine the symmetry of the molecule using the following steps.
Describe the polar bonds with arrows pointing toward the more electronegative element. Use the length of the arrow to show the relative polarities of the different bonds. Decide whether the arrangement of arrows is symmetrical or asymmetrical
If the arrangement is symmetrical and the arrows are of equal length, the molecule is nonpolar. If the arrows are of different lengths, and if they do not balance each other, the molecule is polar. If the arrangement is asymmetrical, the molecule is polar.

Shortcuts for Predicting Molecular Polarity If the central atom has no lone pairs and if all the bonds are identical (all single or all double and all to an atom of the same element), the molecule is nonpolar. If theres at least one polar bond, and if the groups are not identical, the molecule is probably polar. Molecules with the O-H or N-H bond are polar.

Condensation (Gas to Liquid)

Dipole-Dipole Attractions

Dipole-Dipole Attractions in a Liquid

Connections Between Topics

Lewis structures Molecular geometry Molecular polarity Electronegativity Bond polarity Other factors

Types of attractions between particles Relative strengths of these attractions Relative condensation temperatures

Hydrogen Bonds in HF

Hydrogen Bonds in Water

Hydrogen Bonds in Methanol

Hydrogen Bonds in Ammonia

London Forces

London Forces in Polar Molecules

Why Larger Molecules Have Stronger London Forces

Predicting Types of Attractions

Predicting Types of Attractions

Step 1: Determine the type of attraction between the particles using the following steps.
Step 1(a): Classify each substance as either a metallic element, an element composed of atoms, an element composed of molecules, an ionic compound, or a molecular compound. Metallic elements have metallic bonds. The particles in elements that are composed of atoms (the noble gases) and molecules (the other nonmetallic elements) are held together by London forces. The ions in ionic compounds are held together by ionic bonds. Continue to Step 1(b) for molecular compounds.

Predicting Types of Attractions (cont.)

Step 1(b): For molecular compounds, draw the Lewis structure for the molecule.
If the Lewis structure contains an O-H, N-H, or H-F bond, the attractions that form when the substance condenses are hydrogen bonds enhanced by London forces. For other molecular compounds, do Step 1(c).

Predicting Types of Attractions (cont.)

Step 1(c): If there are no O-H, N-H, or H-F bonds, determine the polarity of the bonds.
If there are no polar bonds, the molecules are nonpolar and form London forces when they condense. If there is at least one polar bond, do Step 1(d).

Predicting Types of Attractions (cont.)

Step 1(d): Predict whether the polar bonds are symmetrically or asymmetrically arranged.
If the distribution of polar bonds is symmetrical and their dipoles equal, the molecules are nonpolar and form London forces when they condense. If the distribution of polar bonds is asymmetrical, or symmetrical with unequal dipoles, the molecules are polar and form dipole-dipole attractions enhanced by London forces when they condense.

Predicting Strengths of Attractions

Step 2: Although we cannot predict the relative strengths of attractions between all particles, we can apply one of the following guidelines to predict the relative strengths of attractions between some particles.
Chemical bonds are generally stronger than intermolecular attractions. Hydrogen bonds are generally stronger than dipole-dipole attractions, which are generally stronger than London forces. Larger molecules tend to have stronger attractions.

Properties Affected by Strengths of Attractions Stronger attractions lead to

Higher melting and boiling point temperatures. Greater viscosity for liquids. Greater surface tension for liquids. Lower rate of evaporation for liquids. Lower vapor pressures above a liquid in a closed container.

Water Solubility
If we are comparing the water solubility of two similar molecules, the one with the higher percentage of the molecule that is polar (hydrophilic) is expected to have higher water solubility. We predict that the molecule with the higher percentage of its structure that is nonpolar (hydrophobic) to be less soluble in water.

Hydrophobic and Hydrophilic

Methamphetamine