IB Chemistry Topic 4: Bonding 4.1 Ionic Bonding Chemical bond – chemical bonds are made by the interaction of valence electrons. A chemical bond is like a connection between two atoms. - Why do bonds form? Because the bond is lower energy, or more stable, than the two atoms alone. Electronegativity – the ability to attract bonding electrons. Metals - low electronegativity Nonmetals - high electronegativity Three types of chemical bonds Ionic o a large difference of electronegativity o metal cation with a positive charge and a nonmetal anion Covalent o Both atoms have a high electronegativity o Bond is between two nonmetals Metallic o Both atoms have low electronegativity o Made between metals Define an ionic bond o An ionic bond is the electrostatic attraction between the positive and negative charge of the ions. o Example: Na+ + Cl- NaCl o Note: when you write the formula, there should be no charges! Ionic compounds are neutral. Electron transfer A metal loses electrons and makes a cation (+ charge), and a nonmetal gains electrons to make an anion (- charge), and an ionic bond forms. Example: Sodium loses an electron, chlorine gains an electron, and an ionic bond forms. Strength of Ionic bonding Ionic bonds get stronger with increased charge of the cation or anion and with smaller ionic radii. Example: MgS has a stronger ionic bond than NaCl. 4.2 Covalent bonding Vocabulary: Covalent bonding, octet rule, Lewis structure, dative bond (coordinate bond) A covalent bond is the electrostatic attraction of the positively charged nuclei for the shared pairs of electrons. Example: in H2, each hydrogen atom gives one electron and share the two between them to make a covalent bond. Octet rule: Nonmetals form covalent bonds to fill their valence level. Noble gases already have a filled valence level, so they don’t usually form compounds. Example: Carbon has a valence level of 2s2, 2p4. To get the valence configuration of neon, it needs four more electrons. Therefore, carbon usually makes four bonds. Example: CH4 See Lewis structure worksheet for how to draw Lewis structures. Dative bonds form when one atom donates both electron paris. Example NH3 NH4+ Bond length and bond strength Double bonds are shorter and stronger than single bonds. Triple bonds are shorter and stronger than double bonds. Single bonds…double bonds…triple bonds Increasing bond strength Decreasing bond length Increasing bond energy *Bond energy is a measure of bond strength VSEPR Shape VSEPR & Valence Bond Theory Examples E = nonbonding electron pair, A = central atom, X = bonded atoms TYPE Arrangement of Electron Pairs Angle(s) Molecular Structure Hybrid Orbital Example AX2 linear 180 linear sp BeF2 AX3 2 trigonal planar 120 trigonal planar sp BF3 AX2E trigonal planar 117 bent sp2 SO2 3 AX4 tetrahedral 109.5 tetrahedral sp CH4 AX3E tetrahedral 107 tripodal sp3 NH3 AX2E2 tetrahedral 104 bent sp3 H2O Polarity Vocabulary: Electronegativity values Electronegativity Polar bond Polar molecule Dipole moment Nonpolar bonds Atoms with no difference in electronegativity difference have no overall dipole. Example: hydrogen molecule H-H Polar bonds Electronegativity increases up and to the right of the periodic table. Atoms with a larger difference in electronegativity have a more polar bond. Example: H-Cl Cl is much more electronegative than H Nonpolar Molecules Consider carbon tetrachloride CCl4 The bond C-Cl is polar because chlorine is more electronegative than carbon. The molecule, however, is non-polar because there is no overall dipole moment. CCl4 is symmetrical and the polar bonds pull equally in each direction. “The dipole cancels” Polar Molecules To be a polar molecule, a molecule must 1. Have one or more polar bonds and 2. Be asymmetrical (see below) If a molecule is symmetrical, the bond polarities cancel and it is therefore nonpolar. Symetrical shapes: tetrahedral, trigonal bipyrimidal, octahedral, square planar. All other shapes are asymmetrical. If a molecule is asymmetrical, the bond polarities pull to one side of a molecule, it has an overall dipole, and it is therefore polar. When they pull in opposite directions, it is usually nonpolar. Drawing a dipole: Draw arrows over the H-F bond to show the direction of the negative charge. Which is more electronegative H or Cl? F is. So F gets the partial negative charge and hydrogen gets the partial positive charge. When drawing a molecule for the IB exam, include nonbonding pairs, partial charges with the lower case delta (δ), and the net dipole (for the whole molecule, not the individual bond polarities.) Which would you expect to be more polar? The left molecule () has C-Cl polar bonds that are in opposite directions. The right molecule has C-Cl bonds that both pull down, which gives the molecule a strong overall dipole moment. Network solids Carbon has three allotropes. Different structural arrangements of the same element are called allotropes. Diamond – Giant molecular structure. Tetrahedral arrangement of carbon atoms— each carbon is bonded to four others. This very strong arrangement explains why diamond has such a high melting and boiling point. Graphite – giant covalent. Each carbon is bonded to three other carbons, making layers of hexagon shaped rings. Delocalized pi bonds of the sp2 hybridized carbon atoms give a bond order of 1 1/3, so bond lengths are shorter than that of diamond. These delocalized electrons allow graphite to conduct electricity. Why is graphite less dense and softer than diamond? The layers are far apart and can slide easily because there are only weak Van Der Waals forces between layers. Fullerene – a large sphere made of five and six-membered carbon rings like a soccer ball. Sixty carbons (C60). Conducts better than diamond, not as well as graphite. It can be reduced and form an anion. Addition reactions can happen. It is not a network solid like graphite and diamond, it is a molecule, so it can dissolve in nonpolar solvents. Table1: Summary of the characteristics of the allotropes of carbon. Allotrope Structure Bonding Electrical Conductivity Diamond Giant molecular, tetrahedral arrangement Only covalent bonds Poor conductor Graphite Covalent network, layers of hexogonal rings Covlaent bonds, Van Der Waals Forces between layers Fullerene (C60) Molecule, hexogon and pentagon rings like a soccer ball Covalent bonds Delocalized electrons? hardness No Hard because it is a rigid structure Yes Soft because layers can slide over each other Yes, less delocalized electrons than gaphite Soft because C60 molecules can slide over each other Good conductor Does not conduct as well as graphite 14.1 Shapes of Molecules and Ions *See VSEPR handout on website VSEPR & Valence Bond Theory Examples E = nonbonding electron pair, A = central atom, X = bonded atoms Arrangement of Molecular Hybrid TYPE Angle(s) Example Electron Pairs Structure Orbital AX2 AX3 linear trigonal planar 180 120 linear trigonal planar sp BeF2 2 BF3 2 sp AX2E trigonal planar 117 bent sp SO2 AX4 109.5 tetrahedral sp3 CH4 3 tetrahedral AX3E tetrahedral 107 tripodal sp NH3 AX2E2 tetrahedral 104 bent sp3 H2O AX5 3 trigonal bipyramidal 90 , 120 trig. bipyramidal sp d PF5 AX4E trigonal bipyramidal 90 , 117 sawhorse, seesaw sp3d SF4 AX3E2 trigonal bipyramidal 90 T-shaped 3 ICl3 3 sp d AX2E3 trigonal bipyramidal 180 linear sp d I3- AX6 90 octahedral sp3d2 CrCl6 octahedral 3 2 AX5E octahedral 88 sq. pyramidal sp d ICl5 AX4E2 octahedral 90 sq. planar sp3d2 XeF4 Explaining shape – SL: Give number of bonding pairs and number of nonbonding pairs. HL: when explaining shape on the exam, give the number of “charge centers” (charge center = bonded atom or nonbonding pair) and the number of nonbonding pairs. Also, double and triple bonds push strongly, so angles with a double bond will be bigger than expected (except for linear molecules, which will be 180). Resonance structures: When you can draw more than one Lewis structure for a molecule by moving a double bond, it is called a resonance structure. The real bonding in a molecule with resonance structures is some combination of all three structures. Main point: This makes bond angles and lengths the same for bonds involved in resonance. Example: In the nitrate ion (NO3-), there is not one double bond. Really, these electrons from the double bond are ‘delocalized’ (spread out) over all three N-O bonds. This means… Bond angles are all 120 degrees All N-O bond lengths are equal Image taken from http://www.mikeblaber.org/oldwine/chm1045/notes/Bonding/Resonan/Bond07.htm So the real nitrate molecule might be like this: *Note: this is not the correct way to draw a Lewis structure for nitrate. Draw resonance structures as shown above. Bond order = number of bonding electrons /2. Single bonds = 1 Double bond = 2 Triple bond = 3 For resonance structures, the extra pi bonding electrons are equally spread around the molecule. Example: In the nitrate ion (NO3-), there is not one double bond. Really, these pi electrons are delocalized over all three N-O bonds. Each bond is not single or double. They have a bond order of 1 1/3. Partial charges: δ+ or δ- (“δ” is the lowercase Greek letter Delta, in case you wanted to know. It is not a funny ‘s’ which is what my students think. Ask your history teacher who the Greeks were) 14.2 Hybridization The valence level of carbon is 2s22p2. These 2s and 2p orbitals are atomic orbitals. When a carbon atom makes a bond with another atom, the atomic orbitals “mix” and make new/different hybrid orbitals. Only the valence orbitals hybridize. Draw the electron diagram of the ground state valence electrons in carbon: How does carbon make four bonds with only two unpaired electrons? One electron moves from the 2s to the empty 2p orbital so that there are four unpaired electrons. These orbitals now have the same energy and are called sp3 hybrid orbitals. Aren’t they cute. Hydrogen is the only atom that does not hybridize, since it only has one electron. When bonds form in CH4, each hydrogen electron pairs with an electron from an sp3 orbital. In CH4, we say the carbon atom is sp3 hybridized. There are four sp3 hybrid orbitals and they repel each other to make 109.5° angles, as predicted by VSEPR. Single bonds are made of sigma bonds (σ bond). Sigma bonds form along the inter-nuclear axis. Double bonds are made of one sigma bond and one pi bond (π bond). Triple bonds are made from one sigma bond and two pi bonds. Pi bonds form the sideways interaction of two p orbitals. The electrons in pi bonds are above and below the inter-nuclear axis. CH4 has only single bonds, so they are all sigma bonds. To figure out the hybridization of an atom, 1. Draw the Lewis dot structure 2. Count the number of sigma bonds and nonbonding pairs on the atom. This is the number of hybrid orbitals that must be made. 2 hybrid orbitals mean sp hybridization, 3 mean sp2 and 4 mean sp3. Example: NH3 Draw the Lewis dot structure: 3 sigma bonds + 1 nonbonding pair = 4 orbitals = sp3 hybridized Description: Three sp3 orbitals make sigma bonds with hydrogen, a pair of nonbonding electrons is in the fourth sp3 orbital Example: a carbon atom in ethene, C2H4 Draw the Lewis dot structure: 3 sigma bonds + 0 nonbonding pairs = 3 hybrid orbitals = sp2 hybridized Your turn: Answer the following for the molecule sulfur dihydride: SH2 a. Draw the Lewis structure: b. What is the hybridization on the sulfur atom? _____ c. Explain how the orbitals “hybridize.” Sulfur dihydride has _____ sigma bonds and ____ nonbonding pairs, so it needs four hybrid orbitals. ___ s orbital and ____ p orbitals combine to make ___ hybrid orbitals. Two of the orbitals are bonding orbitals. Two of the orbitals are _____________ orbitals. 4.3-4.5 Intermolecular Forces and how they influence properties Memorize Table p133-134 Electrical conductivity - To conduct electricity, a substance must have delocalized electrons that can move freely. Volitility – how easily a substance evaporates. Stronger intermolecular forces = less volatile. Types of forces, from weakest to strongest: Strength of attractive forces Strongest type of attractive force Type of crystal Boiling and melting point Hardness Example Weakest Van Der Waals Nonpolar molecules, group 8 atomic gases Low Soft Ar, H2 Dipole-dipole Polar Hydrogen bonds Polar with H-N, H-F or H-O bonds Covalent bonds Network solid Metallic Bond Metals Ionic Bond Ionic compounds ↓ Strongest ↓↓ High Hard H-Cl H2O C(graphite) Cu NaCl Van Der Waals Forces (London, dispersion forces) London dispersion forces hold group 8 atoms together in a solid. They are made by one atom inducing a charge on another, so one side of the atom or molecule becomes partially positive and one side becomes partially negative. The strength of London dispersion forces increases with 1. the number of electrons (or molar mass) in the atom or molecule. 2. if molecules can be packed more closely – Unbranched hydrocarbons usually have stronger Van Der Waals forces. Example: Branched vs. unbranched These molecules have the same number of carbon and hydrogen atoms, but the branched molecule (2-methyl propane) has a lower boiling point. Image: http://commons.wikimedia.org/wiki/File:Isobutane-n-butane.png Example: CH3CH3 has a higher melting point than CH4 because there are more electrons in CH3CH3. Image from: http://bdml.stanford.edu/twiki/bin/view/Rise/InvestigationOfVanDerWaalsForce Dipole-dipole forces Polar molecules Dipole-dipole interactions become stronger with a larger difference in electronegativity. Dipoledipole interactions are stronger than London forces, but weaker than chemical bonds (covalent, ionic or metallic). Hydrogen Bonds: The strongest dipole dipole interactions are hydrogen bonds, which can be made between a nonbonding electron pair and a hydrogen that is bonded to N, O or F. Note, this diagram does not show the nonbonding pairs on oxygen, and that is WRONG. You should write nonbonding pairs on all Lewis structures for the exam! Image from: http://chemtools.chem.soton.ac.uk/projects/emalaria/index.php?page=13 Example: NF3 has a higher melting point than NH3. Nonpolar molecules 4.4 Metalic bonding Metallic bonding is thought of as cations in a sea of delocalized electrons. Metallic bonding gets stronger with Smaller radius of the ion number of delocalized valence electrons Example: Sodium, magnesium and aluminum are all metals. They have metallic bonding, in which positive metal ions are attracted to delocalized electrons. Going from sodium to aluminum: the ionic radius increases the number of delocalized electrons increases ... so the strength of the metallic bonding increases and ... the melting points and boiling points increase. Electrical conductivity: metals can conduct electricity because they have many delocalized electrons. Metals are malleable and ductile. Malleable means metals can bend without breaking. Ductile means they can be pulled into wires. Metals are malleable and ductile because there is attraction between the cations and delocalized electrons, so layers of ions can slide past each other. The cations are not attracted to each other. 4.2 Network solids Silica is made of SiO2, where each Si atom is bonded to four O atoms. Network solids have higher melting points than other covalent molecules because to melt a network solid, many covalent bonds must be broken. The melting point is over a temperature range Example, SiO2 melting point: 1650(±75) °C. Example SiO2 has a higher melting point than CO2 because SiO2 is a network solid and many covalent bonds must be broken when it melts. CO2 is just a nonpolar molecule with weak Van Der Waals forces. (Note—each Si is bonded to a fourth O, which is either behind or infront of the Si.) Black = Si, white = O Image from: http://commons.wikimedia.org/wiki/File:SiO2_-_Glas_-_2D.png You should know these network solids: SiC, C, Si, SiO2 *See 4.1 above for ionic compound bonding strength. 4.5 Physical Properties Properties: the main point Know the following: 1. Know how the strength of each type of force changes in different molecules. Example: are Van Der Walls forces stronger in He or Ne? Answer: Ne because Van Der Waals forces get stronger with increasing molar mass. Molar mass of He = 4.00, molar mass of Ne= 20.18 2. Compare molecules of different types with different types of forces. Example: Which has stronger intermolecular forces, He or H2O? H2O because hydrogen bonding is a stronger intermolecular force than Van Der Waals forces. 3. Based on the strength of intermolecular forces, predict properties. Example: Which would have a higher boiling point, He or Ne. Answer: Ne because it has stronger Van Der Waals forces than He. Melting and boiling points Stronger IMFs = higher melting and boiling points. Why? When a substance melts, some of the attractive forces holding the particles together are broken or loosened so that the particles can move freely around each other but are still close together. The stronger these forces are, the more energy is needed to overcome them and the higher the melting temperature. Lowest boiling points: The same is true for boiling points. A substance with strong intermolecular forces will have a high boiling point. Phases at room temperature (23 ºC) Melting and boiling points explain phases of each type of compound. Ionic compounds – solid Network solids: solid Metals: Solid except mercury = liquid Polar molecules: solid, liquid or gas depending on size. Nonpolar molecules: solid, liquid or gas, depending on size. Know the phase of all elements. Gases: H2, O2, F2, Cl2, group 8 (as gaseous atoms, not molecules), liquids: Br2, Hg. All others are solid. Conductivity – Ionic compounds can conduct when dissolved in a polar solvent or in the molten phase. Polar liquids can conduct when strong electrolytes are dissolved. Network solids: Graphite conducts. All others do not. Metals: conduct Nonpolar compounds cannot conduct because their electrons are kept in covalent bonds. Solubility Metals Metals are soluble in other metals. A mixture of metals is called an alloy, which is made my mixing the metals in the liquid phase and letting them freeze. Alloys are less malleable and ductile than pure metals because the difference in size of the atoms prevents layers from sliding easily. If metals are converted to ions, they are soluble in polar solvents. Ionic compounds Ionic compounds are insoluble in most polar solvents because the ionic bonding is very strong in ionic compounds. However, they are usually soluble in water because water is very polar (and therefore the partial charges are very high in water.) The charges of ions are attracted to the partial charges of atoms in a polar molecule. Refer to the solubility rules (that you memorized!) for which compounds are soluble. Generally, solubility of ionic compounds is greater for: Smaller size of ions Smaller charge Image from: grandinetti.org “Like dissolves like” Polar substances are soluble in polar substances. Common polar solvent: water. Nonpolar substances are soluble in nonpolar substances. Common nonpolar solvent: hexane. Why can’t nonpolar substances dissolve in polar substances? Polar substances form strong dipoledipole interactions that exclude nonpolar substances. Imagine oil and water mixing. The oil gets pushed out of the web of hydrogen bonding in water.