CEM 151 Lecture Notes Neutralization Reactions -Acid and base reactions Gas-Forming Reactions - The product decomposes

to give a gas!!!!! - H2CO3 decomposes into H20 + C02 Solution Stoichiometry *Molarity - Molarity (unit of concentration) = moles of solute/volume of solution in liters - NEED TO DO PRACTICE PROBLEMS! Oxidation-Reduction Reactions - Reduction = add electron - Oxidation = remove electron - A coupling process - H2SO4: O -2, H +1, S +6 - CaH2: H -1, Ca +2 - BBr3: Br -1, B +3 - SO3-: O -2, S +5 - ClO-: O -2, Cl +1 - MnO4-: Mn +7 - MnO4 2-: Mn +6 - MnO4 4-: Mn +4 - MnO4 6-: Mn +2 2Al +3 CuCl2(aq) ------> 2Al 3+ + 3Cu

Thermodynamics -Releasing energy = exergonic -Absorbing energy = endergonic -Change in energy = heat + work -Heat absorbed by system = endothermic -Heat released by system = exothermic -Temperature is a state function that depends on a particular set of conditions, it doesnt matter how they got to the state. -State functions are path independent. -q and w are not state functions -Work is organized -Heat is random -change in E = change in H because there is no work being done since volume is not allowed to change. Electronic Structure of Atoms -c=wavelength * velocity -velocity = wavelength * frequency * meters * (1/sec) -E=hv where h is Plancks constant, 6.63 * 10-34 J-s -energy is quantized because the constant means that each packet is the constant. -the bigger the energy, the smaller the frequency (for light waves) -the bigger the energy, the larger the amplitude (for other waves like sound and water) -no relationship between intensity (I) and kinetic energy (K.E.) -the higher the nu (v) the higher the kinetic energy. -More packets mean more electrons knocked off. -c=wavelength*v (nu) -E-h*v(nu) -1/wavelength = (Rh)((1/n12) (1/n22)) (Hydrogen Line Spectra) -electrons in a certain orbital has a certain energy. -n is the energy level of the orbital -l (Azimuthal Quantum Number) defines the shape of the orbital -There should be three l integers -m (Magnetic Quantum Number) describes the three-dimensional orientation of the orbital. -s orbitals are spherical in shape. Radius of sphere increases with increasing value of n. -s nodes are where the probability of finding an electron is 0. -p orbitals have two lobes with anodal plane between them. -d orbitals have 2 nodal planes and 4 lobes. -KNOW ORBITAL SHAPES. -Energy: s<p<d<f -The closer to the nucleus, the lower the energy -Fourth dimension is time. -the Spin Quantum Number, only has two allowed values: +.5 and -.5 -the Spin Quantum Number describes the magnetic field vector of electron -No two electrons in the same atom can have exactly the same energy.

Periodic Properties of the Elements Development of Periodic Table -Elements in the same group have similar chemical properties. -Properties are not identical Periodic Trends Effective Nuclear Charge -In a many-electron atom, electrons are both attracted to the nucleus and repelled by other electrons. -Effective nuclear charge is the nuclear charge that an electron feels dependent on the two factors ^. -Zeff = Z S -Z = atomic number -S = screening constant usually close to the number of inner (n-1) electrons -Rules for defining valence electrons: 1. In outer most energy level 2. For main group (representative) elements (elements in s world or p world) electrons in filled d or f shells are not valence electrons 3. For transition metals, electrons in full f shells are not valence electrons. Sizes of Atoms -The bonding atomic radius is defined as one=-half of the distance between covalently bonded nuclei. -Atom radius increases from right to left of the periodic table because as protons are added, the increased strength of the nucleus pulls more electrons in. Also, no shielding electrons are added when nucleus strength increases. -Cations become smaller while anions become bigger. -Ions increase in size as you go down a column due to increasing value of n. -In an isoelectronic series, ions have the same number of electrons. -Al3+, Mg2+, Na+, Cl, S, Al, Mg, Na, Cl-, S2- (From smallest to largest in size) Ionization Energy -The amount of energy required to remove an electron from the ground state of a gaseous atom or ion. -It requires more energy to remove each successive electron. -When all valence electrons have been removed, the ionization energy takes a quantum leap. Trends in First Ionization Energies -Generally, it gets harder to remove an electron going across. -Why are there two jags in each line? The jag line is there because the electron in the Boron atom is in the p orbital, which is farther from the nucleus than the s orbital, thus, the energy to remove the electron is lower. -The two electrons in an orbital repel each other, which makes it easier to remove the repelling paired electrons. -When going up an orbital and when electrons are paired, it is easier to remove the electrons. Electron Affinity -Energy change accompanying addition of electron to gaseous atom. -In general, electron affinity becomes more exothermic as you go from left to right across a row. -Repulsion by electrons already in an orbital makes adding an electron an endothermic reaction.

For Quiz (Really need to know from chapter) -Electron affinity -Ionization energy -Atom/Ion radii Properties of Metals, Nonmetals, and Metalloids -Increasing metallic character (from left to right and top to bottom) Metals -Metal oxides tend to be basic because it takes up protons. Nonmetals -Substances containing only nonmetals are molecular compounds (held together by covalent bonds) -Most nonmetal oxides are acidic. Metalloids -Have some characteristics of metals and nonmetals. Group Trends Alkali Metals -Found only as compounds in nature. -Alkali metals react with oxygen to form peroxides. Alkaline Earth Metals -Have higher densities and melting points than alkali metals because there are more protons. -Reactivity tends to increase as you go down the group. Oxygen -Two allotropes: O2 O3 -Three anions: O2O22O21-

Concepts of Chemical Bonding Types of Bonds -Three types of chemical bonds: ionic, covalent, and metallic -Ionic bond: electrostatic attraction between ions -Covalent: sharing of electrons -Metallic: metal atoms bonded to several other atoms Lewis Symbols -Lewis symbols are used to keep track of valence electrons. Energetics of Ionic Bonding -The unexplained exothermic reaction is explained by accounting for the electrostatic cation and anion. Lattice Energy -Lattice energy is the energy required to completely separate a mole of a solid ionic compound into its gaseous ions. -The explanation of the exothermic reaction is the lattice energy: Eel = kQ1Q2 d -Lattice energy, then, increases with the charge on the ions. -It also increases with decreasing size of ions. Covalent Bonding Polar Covalent Bond -Fluorine pulls harder on the shared electrons than hydrogen does. -Therefore, the fluorine end has more electron density than the hydrogen end. -It is not symmetrical. -Electronegativity is used to determine who pulls the hardest. -This creates a bond dipole. -The dipole moment, produced by two equal but opposite charges separated by a distance, r, is calculated: u = Qr -The greater the difference in electronegativity, the more polar is the bond. Electronegativity -How much an atom attracts electrons when it is in a molecule. Lewis Structures Writing Lewis Structures 1. Find the sum of valence electrons of all atoms in the polyatomic ion or molecule. 2. The central atom is the least electronegative element that isnt hydrogen. Connect the outer atoms to it by single bonds. 3. Fill the octets of the outer atoms. 4. Fill the octet of the central atom. 5. If you run out of electrons before the central atom has an octet, form multiple bonds until it does. 6. Then assign formal charges.

-The best Lewis structure is the one with the fewest charges and puts a negative charge on the most electronegative atom. Resonance Draw the resonance structure for: HCO2-

Draw the Lewis structure of NO3-

Exceptions to the Octet Rule -There are three types of ions or molecules that do not follow the octet rule: Ions or molecules with an odd number of electrons Ions or molecules with less than an octet Ions or molecules with more than eight valence electrons (an expanded octet) Odd Number of Electrons -Nitric oxide Fewer than Eight Electrons -BF3 More than Eight Electrons -Atoms on the 3rd row or below can go over an octet of electrons. Covalent Bond Strength -The strength of a bond is measured by determining how much energy is required to break the bond (bond enthalpy) -Average bond enthalpies are positive, because bond breaking is an endothermic process. The Enthalpies of Reaction -The heat of a reaction comes from breaking bonds and remaking bonds.

Chapter 9 Molecular Shapes -The 3D structure is absolutely critical for understanding molecules. -Geometry and shape of molecule is critical -We can predict the 3D structure of a molecule by: Adding up: bound atoms + lone pairs What determines the Shape of a Molecule -Atoms and lone pairs take up space and prefer to be as far from each other as possible Things -The central atom has four things around it. A thing is an atom or a lone pair of electrons -# things = atoms plus lone pairs Valence Shell Electron Pair Repulsion Theory (VSEPR) -The best arrangement of a given number of things is the one that minimizes the repulsions among them. -Electrons are far enough apart that they do not repel each other significantly. Geometries (Learn these) -These are the geometries for two through six things around a central atom. -5 things = trigonal bipyramidal -All one must do is count the number of things in the Lewis structure. -The geometry is often not the shape of the molecule however. -The shape is defined by the positions of only the atoms in the molecules not the lone pairs. -Shape = only atoms -Geometry = atoms + lone pairs -Within each geometry, there might be more than one shape. -Trigonal pyramid = 3 atoms + lone pair -Bent = 2 atoms + 2 lone pairs Lone pairs and Bond angle -Lone pairs are physically larger than atoms. -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. Tetrahedral geometry 4 things -There are three molecular geometries: Tetrahedral, if no lone pairs Trigonal pyramidal if one is a lone pair Bent if there are two lone pairs Trigonal Bipyramidal geometry 5 things -There are two distinct positions in this geometry: Axial (180 degrees apart: up and down usually) Equatorial (left to right usually)

Trigonal Bipyramidal geometry -Lower-energy conformations result from having lone pairs in equatorial, rather than axial, positions in this geometry. -Lone pair wants to be in equatorial position because they need the space. -There are four distinct molecular geometries in this domain: Trigonal bipyramidal Seesaw (one lone pair) T-Shaped (two lone pairs) Linear (three lone pairs) Octahedral geometry 6 things -All positions are equivalent in the octahedral domain. -Square pyramidal (one lone pair) -Lone pairs go into the axial positions -Square planar (two lone pairs) Polarity -By adding the individual bond dipoles, one can determine the overall dipole movement. Overlap and Bonding -Increased overlap brings the electrons and nuclei closer together while simultaneously decreasing electron-electron repulsion. Hybrid Orbitals -Beryllium example. -Mixing the s and p orbitals yields two degenerate orbitals that are hybrids of the two orbitals. -For geometries involving expanded octets on the central atom, we must use d orbitals in our hybrids. -Once you know the number of things around an atom, you know the hybridization state of the atom if you can count letters up to six. Valence Bond Theory -Hybridization is a major player in this approach to bonding. -There are two ways orbitals can overlap to form 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 Delocalized Electrons: Resonance -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. Valence bond theory -********Delocalization and resonance

Molecular Orbital Theory -There are two new orbitals made when using MO theory. One bonding orbital will be bonding and the other will be antibonding, which has higher energy. Rules for making and filling molecular orbitals 1. The number of MOs equals the number of atomic orbitals 2. The overlap of two atomic orbitals gives two molecular orbitals, 1 bonding, one antibonding 3. Atomic orbitals combine with other atomic orbitals of similar energy 4. Degree of overlap matters. More overlap means bonding orbital goes lower in E, antibonding orbital goes higher in E. 5. Each MO gets two electrons 6. Orbitals of the same 3energy get filled with 1 electron at a time until they are filled. Three kinds of magnetism: 1. Diamagnetism (have paired electrons, not affected by magnetic field) 2. Paramagnetism (have unpaired electrons, affected by magnetic field) 3. Ferromagnetism Bond Order -Bond order = (#bonding e- - # antibonding e- ) Complexes -A central metal atom can bond to a group of molecules or ions: metal complex. -If its charged: complex ion. -Compounds containing complexes are coordination compounds. -The molecules or ions coordinating to the metal are the ligands. -Ligands have to have lone pairs. A Chemical mystery -Same metal, same ligands, different number of ions when dissolved. Geometries -The two common geometries for metals with a coordination number of four are tetrahedral and square planar. Polydentate Ligands -Ligands that have two or more donor atoms. -Ethylenediamine (know this) Chelating Agents -Bind to metal ions removing them from solution Light -The higher the electronegativity of the ligand, the lower the splitting. Tetrahedral Complexes -Change in energy is always small and always low spin.

MO Theory: Rules: 1. The number of MOs equals the # of atomic orbitals 2. The overlap of two atomic orbitals gives two molecular orbitals, one bonding and one antibonding 3. Atomic orbitals combine with other atomic orbitals of similar energy. 4. Degree of overlap matters. More overlap means bonding orbital goes lower in E, antibonding orbital goes higher in E. 5. Each MO gets two electrons 6. Orbitals of the same energy get filled 1 electron at a time until they are filled.

Organic Chemistry -The chemistry of carbon compounds. Structure of Carbon Compounds -There are three hybridization states and geometries found in organic compounds: sp3 tetrahedral sp2 trigonal planar sp linear Hydrocarbons -Four types: 1. Alkanes (no double bonds) 2. Alkenes (at least one double bond) 3. Alkynes (at least one triple bond) 4. Aromatic hydrocarbons (1. Cyclic compounds (circular); 2. Double bonds that alternate; 3. Alkanes -Saturated hydrocarbons (filled with hydrogen) Properties of Alkanes -Only van der Waals force: London force. -Boiling point increases with length of chain. Structure of Alkanes -Carbons in alkanes sp3 hybrids. -Tetrahedral geometry. -109.5o bond angles. -Only sigma bonds in alkanes. -Free rotation about C-C bonds. Organic Nomenclature -Three parts to a compound name: Base: Tells how many carbons are in the longest continuous chain. Suffix: Tells what type of compound it is. -1. Find the longest chain in the molecule. 2. Number the chain from the end nearest the first substituent encountered. 3. List the substituents as a prefix along with the number(s) of the carbon(s) to which they are attached. -If there is more than one type of substituent in the molecule, list them alphabetically. -If there is more than one way to make the longest chain, pick the one with the most substituents. Cycloalkanes -Carbon can also form ringed structures. -Five- and six-membered rings are most stable. -can take on conformation in which angles are very close to tetrahedral angle. Reactions of Alkanes -Rather unreactive due to presence of only C C and C H sigma bonds. -Therefore, great nonpolar molecules.

Alkanes -Contain at least one carbon-carbon double bond. -Unsaturated. Structure of Alkenes -Side-to-side overlap makes rotation impossible without breaking pi-bond. Reactions of Alkenes -Addition Reactions -Two atoms (e.g. bromine) add across the double bond. -One pi-bond and one sigma bond are replaced by two sigma bonds; therefore, delta H is negative.