Score AP 16 1 31 1 31 1 33 2 38 2 43 3 45 3 50 3 52 3 52 3 53 3 53 3 55 4 57 4 59 4 62 4 64 4 64 4 66 4 69 5 81 5 81 5 83 5 83 5 0 0.005 0.01 0.015 0.02 0.025 0 10 20 30 40 50 60 70 80 90 Score Exam 3: Periodicity One step back Two steps forward Clear learning objectives for each topic based on AP Curriculum Framework Example AP questions embedded in notes/discussion Clicker Quiz at the beginning of every class to assess last class notes and/or homework from the night before
Topic 4.1 Bond Energy Big Idea 2: Chemical and physical properties of materials can be explained by the structure and the arrangement of atoms, ions, or molecules and the forces between them. Enduring understanding 2.C: The strong electrostatic forces of attraction holding atoms together in a unit are called chemical bonds. Essential knowledge 2.C.1: In covalent bonding, electrons are shared between the nuclei of two atoms to form a molecule or polyatomic ion. Electronegativity differences between the two atoms account for the distribution of the shared electrons and the polarity of the bond. Page 23-24 What will be on the AP? What specifically wont be on the AP? Learning Objective: LO 2.18 The student is able to rank and justify the ranking of bond polarity on the basis of the locations of the bonded atoms in the periodic table. [See SP 6.1] Most simply, the strength of a bond is measured by determining how much energy is required to break the bond. This is the bond enthalpy. The bond enthalpy for a ClCl bond, D(ClCl), is measured to be 242 kJ/mol. This table lists the average bond enthalpies for many different types of bonds. Average bond enthalpies are positive, because bond breaking is an endothermic process. NOTE: These are average bond enthalpies, not absolute bond enthalpies; the CH bonds in methane, CH 4 , will be a bit different than the CH bond in chloroform, CHCl 3 . Yet another way to estimate H for a reaction is to compare the bond enthalpies of bonds broken to the bond enthalpies of the new bonds formed. In other words, H rxn = (bond enthalpies of bonds broken) (bond enthalpies of bonds formed) CH 4 (g) + Cl 2 (g) CH 3 Cl(g) + HCl(g)
In this example, one CH bond and one ClCl bond are broken; one CCl and one HCl bond are formed.
H rxn = [D(CH) + D(ClCl) [D(CCl) + D(HCl) = [(413 kJ) + (242 kJ)] [(328 kJ) + (431 kJ)] = (655 kJ) (759 kJ) = 104 kJ CH 4 (g) + Cl 2 (g) CH 3 Cl(g) + HCl(g) We can also measure an average bond length for different bond types. As the number of bonds between two atoms increases, the bond length decreases. 2002 D Required Use the principles of atomic structure and/or chemical bonding to explain each of the following. In each part, your answer must include references to both substances.
(c) The carbon-to-carbon bond energy in C2H4 is greater than it is in C2H6.
Ans. The carbon-to-carbon bond in C2H4 is a double bond, which is stronger than the carbon-to-carbon single bond in C2H6.
Topic 4.2 Lewis Structures, VSEPR Theory, and Polarity Essential knowledge 2.C.4: The localized electron bonding model describes and predicts molecular geometry using Lewis diagrams and the VSE PR model.
Page 26-27 What will be on the AP? What specifically wont be on the AP? Learning Objective: LO 2.21 The student is able to use Lewis diagrams and VSEPR to predict the geometry of molecules, identify hybridization, and make predictions about polarity. Lewis diagrams are diagrams that show the bonding between atoms of a molecule and the lone pair electrons. Valence shell electron pair repulsion (VSEPR) theory is a model used to predict the geometry of individual molecules from the number of electron pairs surrounding their central atoms. Hybridization is the concept of mixing atomic orbitals into new hybrid orbitals (with different energies, shapes, etc., than the component atomic orbitals) suitable for the pairing of electrons to form chemical bonds in valence bond theory. Steps for drawing Lewis Structures 1) Arrange elements so the least electronegative element is central. Make single bonds. (Keep a tally on total valence electrons used/unused) 2) Complete Octets of non-central atoms with lone pairs. 3) Place remaining electrons on central atom. 4) Make multiple bonds to satisfy octets and minimize formal charge. Draw the Lewis Structure for H 2 CO. BF 3
It is allowed to expand the octet of atoms on the 3rd row or below. Presumably d orbitals in these atoms participate in bonding. The shape of a molecule plays an important role in its reactivity. By noting the number of bonding and nonbonding electron pairs we can easily predict the shape of the molecule. Simply put, electron pairs, whether they be bonding or nonbonding, repel each other. By assuming the electron pairs are placed as far as possible from each other, we can predict the shape of the molecule. We can refer to the electron pairs as electron domains. In a double or triple bond, all electrons shared between those two atoms are on the same side of the central atom; therefore, they count as one electron domain. This molecule has four electron domains. The best arrangement of a given number of electron domains is the one that minimizes the repulsions among them.
These are the electron-domain geometries for two through six electron domains around a central atom. All one must do is count the number of electron domains in the Lewis structure. The geometry will be that which corresponds to that number of electron domains. The electron-domain geometry is often not the shape of the molecule, however. The molecular geometry is that defined by the positions of only the atoms in the molecules, not the nonbonding pairs. Within each electron domain, then, there might be more than one molecular geometry. In this domain, there is only one molecular geometry: linear. NOTE: If there are only two atoms in the molecule, the molecule will be linear no matter what the electron domain is. There are two molecular geometries: Trigonal planar, if all the electron domains are bonding Bent, if one of the domains is a nonbonding pair. Nonbonding pairs are physically larger than bonding pairs. Therefore, their repulsions are greater; this tends to decrease bond angles in a molecule. Double and triple bonds place greater electron density on one side of the central atom than do single bonds. Therefore, they also affect bond angles. There are three molecular geometries: Tetrahedral, if all are bonding pairs Trigonal pyramidal if one is a nonbonding pair Bent if there are two nonbonding pairs There are two distinct positions in this geometry: Axial Equatorial Lower-energy conformations result from having nonbonding electron pairs in equatorial, rather than axial, positions in this geometry. There are four distinct molecular geometries in this domain: Trigonal bipyramidal Seesaw T-shaped Linear All positions are equivalent in the octahedral domain. There are three molecular geometries: Octahedral Square pyramidal Square planar 1989 D CF 4 XeF 4 ClF 3
(a) Draw a Lewis electron-dot structure for each of the molecules above and identify the shape of each. (b) Use the valence shell electron-pair repulsion (VSEPR) model to explain the geometry of each of these molecules. Answer: (a) (b) CF 4 = 4 bonding pairs around C at corners of regular tetrahedron to minimize repulsion (maximize bond angles). XeF 4 = 4 bonding pairs and 2 lone pairs give octahedral shape with lone pairs on opposite sides of Xe atom ClF 3 = 3 bonding pairs and 2 lone pairs give trigonal bipyramid with one pairs in equatorial positions 120 apart. Selenium reacts with fluorine to form SeF4. Draw the complete Lewis electron-dot structure for SeF4 and sketch the molecular structure. Indicate whether the molecule is polar or nonpolar, and justify your answer. (d) See-saw shape Because F is very electronegative and the molecule is asymmetric with respect to the fluorines, this molecule is polar.
In larger molecules, it makes more sense to talk about the geometry about a particular atom rather than the geometry of the molecule as a whole. This approach makes sense, especially because larger molecules tend to react at a particular site in the molecule. In Chapter 8 we discussed bond dipoles. But just because a molecule possesses polar bonds does not mean the molecule as a whole will be polar. By adding the individual bond dipoles, one can determine the overall dipole moment for the molecule. Topic 4.3 Hybridization and Bonding Theory We think of covalent bonds forming through the sharing of electrons by adjacent atoms. In such an approach this can only occur when orbitals on the two atoms overlap. Increased overlap brings the electrons and nuclei closer together while simultaneously decreasing electron-electron repulsion. However, if atoms get too close, the internuclear repulsion greatly raises the energy. But its hard to imagine tetrahedral, trigonal bipyramidal, and other geometries arising from the atomic orbitals we recognize. Consider beryllium: In its ground electronic state, it would not be able to form bonds because it has no singly-occupied orbitals. But if it absorbs the small amount of energy needed to promote an electron from the 2s to the 2p orbital, it can form two bonds.
Mixing the s and p orbitals yields two degenerate orbitals that are hybrids of the two orbitals. These sp hybrid orbitals have two lobes like a p orbital. One of the lobes is larger and more rounded as is the s orbital.
These two degenerate orbitals would align themselves 180 from each other. This is consistent with the observed geometry of beryllium compounds: linear.
With hybrid orbitals the orbital diagram for beryllium would look like this. The sp orbitals are higher in energy than the 1s orbital but lower than the 2p. Using a similar model for boron leads to three degenerate sp 2 orbitals. With carbon we get four degenerate sp 3 orbitals. For geometries involving expanded octets on the central atom, we must use d orbitals in our hybrids. This leads to five degenerate sp 3 d orbitals
or six degenerate sp 3 d 2 orbitals. Once you know the electron-domain geometry, you know the hybridization state of the atom. Hybridization is a major player in this approach to bonding. There are two ways orbitals can overlap to form bonds between atoms. Sigma bonds are characterized by Head-to-head overlap. Cylindrical symmetry of electron density about the internuclear axis. Pi bonds are characterized by Side-to-side overlap. Electron density above and below the internuclear axis. Single bonds are always bonds, because overlap is greater, resulting in a stronger bond and more energy lowering. In a multiple bond one of the bonds is a bond and the rest are bonds. In a molecule like formaldehyde (shown at left) an sp 2 orbital on carbon overlaps in fashion with the corresponding orbital on the oxygen. The unhybridized p orbitals overlap in fashion. In triple bonds, as in acetylene, two sp orbitals form a bond between the carbons, and two pairs of p orbitals overlap in fashion to form the two bonds. Two Lewis structures can be drawn for the OPF3 molecule, as shown below. (i) How many sigma bonds and how many pi bonds are in structure 1?
P O F F F : : : : .. .. .. .. .. : : P O F F F : : : : .. .. .. .. .. . . : : When writing Lewis structures for species like the nitrate ion, we draw resonance structures to more accurately reflect the structure of the molecule or ion. In reality, each of the four atoms in the nitrate ion has a p orbital. The p orbitals on all three oxygens overlap with the p orbital on the central nitrogen. This means the electrons are not localized between the nitrogen and one of the oxygens, but rather are delocalized throughout the ion. The organic molecule benzene has six bonds and a p orbital on each carbon atom. In reality the electrons in benzene are not localized, but delocalized. The even distribution of the electrons in benzene makes the molecule unusually stable. Though valence bond theory effectively conveys most observed properties of ions and molecules, there are some concepts better represented by molecular orbitals. In MO theory, we invoke the wave nature of electrons. If waves interact constructively, the resulting orbital is lower in energy: a bonding molecular orbital. If waves interact destructively, the resulting orbital is higher in energy: an antibonding molecular orbital. In H 2 the two electrons go into the bonding molecular orbital. The bond order is one half the difference between the number of bonding and antibonding electrons. For hydrogen, with two electrons in the bonding MO and none in the antibonding MO, the bond order is 1 2 (2 - 0) = 1 In the case of He 2 , the bond order would be 1 2 (2 - 2) = 0 Therefore, He 2
does not exist. For atoms with both s and p orbitals, there are two types of interactions: The s and the p orbitals that face each other overlap in fashion. The other two sets of p orbitals overlap in fashion. The resulting MO diagram looks like this. There are both and bonding molecular orbitals and * and * antibonding molecular orbitals. The smaller p-block elements in the second period have a sizeable interaction between the s and p orbitals. This flips the order of the s and p molecular orbitals in these elements.