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d2 We measure the strength of a bond by the energy required to pull the ions apart. More highly charged ions will have a stronger ionic bonds (most important). Smaller ions will have stronger ionic bonds (considered after charge). Ex 1: Rank the following ionic compounds in order of decreasing bond strength. LiCl
NaCl MgCl2 MgF2 MgO CaO The energy to break an ionic bond is the energy required to take the ions in a compound and pull them apart to individual ions. This will be an endothermic process (breaking bonds required energy). This will be the same as the energy released if individual ions form an ionic solid (forming bonds in an exothermic process). The energy of the ionic bonds is called the lattice energy. A reaction to make a solid from gaseous ions would be very difficult.
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IB Chemistry 4 Bonding According to Hesss Law, we can find a different set of steps that have the same overall result, we can find the energy. This process is called the BornHaber Cycle. This cycle uses the enthalpy of formation and a series of steps to find the lattice energy Born-Haber Cycle 1. Sublimation energy 2. Bond strength (covalent) 3. Ionization energy 4. Electron affinity 5. Lattice energy Net reaction: enthalpy of formation. Ex 2: Using data from your text (p.362), Data Booklet and The diagram above, to find the lattice energy for KF.
What are the differences between this Born-Haber cycle and the one for NaCl? Problems 9.17, 22, 24, 26, 28, 30, 33
IB Chemistry 4 Bonding
CO2
SO32-
O2
N2
HCN
IB Chemistry 4 Bonding There can be times when a double bond can equally be placed at two positions; the choice of which is arbitrary. In the Lewis Structure for NO2- the double bond can be placed with either oxygen. The result is half of each. This is a resonance structure. Draw the Lewis structure for: SO3 O3
CH3COO-
There are times when atoms do not form octets. Boron is small and can form stable compounds with six electrons. Beryllium can form compounds with four electrons. These exceptions are included because they have been found to exist. There are also compounds that can have more than octets. An atom that has empty d orbitals can have 10 or 12 electrons around it. This is only done if it is the only way to place all the electrons in the Lewis Structure. Ex 3: Draw the Lewis Structure for: a) I3b) XeF4 c) ICl5
IB Chemistry 4 Bonding
IB Chemistry 4 Bonding
4.4 VSEPR
The shapes of covalent molecules can be explained using the VSEPR theory: Valence Shell Electron Pair Repulsion. Electron pairs (bonding and non-bonding) will arrange themselves to maximize the distance between them so to minimize their potential energy. The shapes that the atoms adopt depend on the number of electron pairs around the central atom. These arrangements allow the electron pairs to be as far apart as possible. You need to know the names and angles for these VSEPR geometries.
In describing a molecules geometry, we only describe the bonds that are present. Lone pairs must be accounted for in determining the VSEPR geometry, but are ignored in the molecular geometry. Lone pairs repel more than a bonding pair: They will repel other bonding pairs farther away from themselves. If there are two or more lone pairs they will be arranges far from each other. Note that bent geometry can result from Triganal Planer and Tetrahedral geometries. What are the angles for these molecular bonds?
IB Chemistry 4 Bonding 4.4 VSEPR Note the position of the lone pairs in the triganol bipyramidal geometry. All positions are equal in the octahedral arrangements. Example 1: Give the VSEPR geometry and molecular geometry (including angles) for: NH3
XeF4
SeCl4
SO2
O3
I3 -
Follow Up Problems 10.6, 7, 8 Problems 10.28, 30, 32, 34, 36, 40, 46
IB Chemistry 4 Bonding
Methane has four sigma bonds. Each bond is between an sp3 orbital for the carbon and an s orbital from the hydrogen.
IB Chemistry 4 Bonding The second type of covalent bond is a pi bond. This bond forms if a double or triple bond is necessary. In a multiple bond the first bond is a sigma bond and the second and third bond are pi bonds. These bonds are outside of the axis between the two atoms
To make a pi bond, an atom must have a p orbital that is not hybridized. The atom is combining one s orbital and two p orbitals.
IB Chemistry 4 Bonding Notice that the geometry of the sp2 hybrids is trigonal planer. This is where the trigonal planer geometry comes from. Pi bonds are also weaker than sigma bonds. This is why a double bond is not twice as strong as a single bond. A bond is stronger if the orbital overlap is greater and if the electrons can spend more time in the shared orbital. To make two pi bonds, an atom must have two p orbitals that are not hybridized. This can occur if an atom is making a triple bond or two separate double bonds. To have two p orbitals for pi bonding, there is only one p for hybridization.
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IB Chemistry 4 Bonding To determine the p orbitals that are hybridized, subtract any needed for pi bonds, hybridize the rest. Example 1: Draw the following molecules indicating the bonding orbitals: a) Ammonia (NH3)
b) Oxygen
c) C2H4
d) HCN
e) H2C=C=CH2
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IB Chemistry 4 Bonding The last aspect we will examine is bond delocalization. This allows us to explain resonance. In this diagram of NO2, what is the hybridization of each atom? Each atom must be able to form a pi bond. The electrons in the pi bond are actually shared among all of the p orbitals. Bond delocalization adds stability to molecules. Breaking a delocalized bond is harder, because it involved more atoms. Example 2: Draw the bonding for the following molecules: a) Ozone (O3)
b) NO3
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IB Chemistry 4 Bonding Different types of bonding can be seen in the allotropes of carbon: diamond, graphite and fullerene (bucky ball). A diamond has carbon atoms that are sp3 hybridized. Each carbon is bonded to four other carbons in a three dimensional matrix. What properties could this give to carbon?
Graphite is made of carbon atoms that are sp2 hybridized. They are like benzene rings that continue in large layers. The electrons are delocalized between the layers of carbon atoms. Properties?
Follow Up Problems 11.2 Problems 11.7, 9, 11, 20, 21, 23, 40, 42, 50, 58
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IB Chemistry 4 Bonding
Example 1:
Determine if the following have a dipole: CH4 NH3 H2O
CO2
SO2
Cl2
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IB Chemistry 4 Bonding Dipole bonding attracts molecules together. The stronger the bonding, the higher the temperature must be before the substance will boil or melt. Solid Liquid
Hydrogen bonding is a dipole that is formed with HN, HO, HF bonds. The small size of these atoms produces a very strong dipole bond. Van der Waals forces are due to a temporary dipole that forms when the electrons are temporarily unbalanced. This produces a weak, short lived dipole attraction. (also called London dispersion Forces) The temporary dipoles are stronger in larger atoms. Larger atoms have a greater chance for electron imbalances. The Van der Waals attraction will also be stronger in larger (longer) molecules. There are more places for attraction to occur. The temporary dipoles occur in molecules with permanent dipoles, but they are most important in non-polar molecules. To determine the strength of the inter-molecular bonding: 1) Determine if there is Hydrogen bonding. 2) Determine if there is a dipole. 3) Determine the extent of the Van der Waals forces. These are in priority order.
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IB Chemistry 4 Bonding
Example 2:
Explain the trends in the graph below.
Example 3:
Explain the following trends: B.P of noble gasses B.P. of halogens
Predict the strength of the inter molecular bonding for: CO2, SO3, O2, CH4, H2CO
Follow Up Problems 10.9, 12.2, 3 Problems 10.52, 55, 57, 12.5, 32, 34, 37, 39, 41, 43, 45(polarizability is ease of forming dispersion forces), 47, 49, 51, 53
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IB Chemistry 4 Bonding
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IB Chemistry 4 Bonding Some compounds can form large, covalently bonded molecules, macro-molecules. Diamond is an example of a network covalent solid. Melting a diamond involves breaking the covalent bonds between carbon atoms. Are these inter- or intra-molecular bonds?
Be able to explain trends in m.p. and b.p. for metals. Explain how the metallic bonding model explains the properties of metals.
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