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Chapter 3 When two atoms come close together, o electrons of each atom experience attractive force of the nucleus

s in other atom o The electrons repel each other o Positive nuclei repel each other Stable chemical bond between atoms (g) is formed only when total energy of molecule is lower than total energy of the two isolated atoms o Quantum mechanics necessary to explain re-distribution of electrons that lead to bond formation Classical description of chemical bond: o Covalent bonds, ionic bonds, polar covalent bonds, electronegativity, lewis electron dot diagrams, valence shell electron-pair repulsion (VSEPR) theory o Covalent: electrons are shared more or less equally between two atoms o ionic: one or more electrons is completely transferred from one atom to the other. strong bond b/c of attraction between the resulting positive & negative ions o Polar covalent: partial transfer of charge from one atom to the other o Electronegativity: tendency of an atom in a molecule to attract electrons from other atoms explains whether bond is ionic, covalent, or polar covalent Lewis electron dot diagram: shows # of valence electrons and indicate whether they are shared or nonbonding. DONT describe 3-D shapes VSEPR theory: predicts molecular shapes based on electrostatic argument that electron pairs in molecule will arrange themselves to be as far apart as possible

3.1 Representation of molecules Molecule: when two or more atoms form a bond Compound: when at least two different elements form a bond Molecules are characterized by their molecular formulas molecule in extended solids can only be characterized by empirical formulas Condensed structural formula specifies which atoms are o bonded to each other and by what types of bonds o e.g. ethanol C2H6O condensed: CH3CH2OH isomers : same molecular formula but different molecular structures & different properties

3.2 The Periodic Table groups (vertically) vs. periods (horizontally) representative elements aka "main-group" transition-metal elements lathanide elements (#57-71) actinide elements (#89-103) Metals o metallic luster, good conductor of electricity and heat, malleability Nonmetals o no metallic luster, poor conductor, brittleness Metalloids (B, Si, Ge, As, Sb, Te) o poor conductor but better than nonmetals alkali metals o Group I - soft metals, low MP alkaline-earth metals

o Group II chalcogens o Group VI - nonmetals halogens o Group VII o form alkali halides with alkali metals semiconductors o silicon and germanium, basis for modern semiconductor industry allotropes o modifications of an element w/ different atomic arrangement that lead to different physical and chemical properties noble gases o Group VIII BrINClHOF - diatomic molecules

3.3 Forces and Potential Energy in Atoms Coulombs law determines attractive force between each electron and the nucleus and the repulsive force between each pair of electrons Electrical force between two charges, q1 and q2, separated by distance r o o e0 = permittivity of the vacuum 8.854x10-12C2J-1m-1 o q = -Ke or +Ke o particles with same charge repel another and distance (r) increases o particles with opposite sign attract each other and distance between them decreases potential energy V(r) of a pair of charged particles interacting by Coulombs force law o [3.2] o V(r) -> 0 as r-> infinity since no interaction between particles at large distances o If charges have opposite signs, PE is negative and increases (becomes less negative) as r increases o If charges have same sign, PE is positive and it decreases as r increases o Separation between pair of particles increases in regions in which the slope V/r of PE is negative and decreases in regions over which the slope is positive. Electron q= -e and nucleus q= +Ze. Potential energy for planetary atom o [3.3] o 1 = 10-10m o e= 1.602x10-19C o 1 eV = 1.602x10-19 J unit for PE Force is directed outwards for negative PE slope (positive sign for Force) Force is directed inwards for positive PE slope (negative sign for Force) Force = derivative of potential energy function o [3.6] Turning point: same charged particle are fired at each other. At a given distance, the particle stops, turns around and heads back away from the other particle. Turning point is found by setting the PE equals the horizontal line (KE or Total Energy) E= KE PE o E is horizontal line and KE is vertical arrow connecting V to E o If electron has significant KE everywhere -> unbound motion, positive E, electron approaches proton but passes by o Negative E describes bound motion

3.4 Ionization Energies, the shell model, and shielding Positively charged cation and negatively charged anion Ionization energy IE is the minimum energy necessary to remove an electron from a neutral atom IE is the change in energy E for the process o X(g) X+(g) + e IE is positive because energy is provided to take away an electron Larger IE more stable atoms Trend: IE increases from bottom to top and left to right Shell model for atomic structures: big jumps in IEs of an atom suggest that electrons are grouped into shells based upon energy required to remove them o [3.8] o Zeff = Z S where S is screening(shielding) constant o Coulomb potential energy with effective charge Zeff on the nucleus [3.9] Lower values of Zeff are more weakly bound than those with higher values Electrons near nucleus are screened less so screening constant is smaller o Across period: add neutrons (a lot more positive charge) add electrons in the same shell (Zeff doesnt change much cause less screening) -> increase in IE o Core electrons vs valence electrons

3.5 Electron affinity Electron affinity: ease with which an atom accepts an extra electron to form an anion E is called electron attachment energy and is negative o X(g) + e- X- (g) o Calculate using reverse reaction Difference between IE trend and EA trend is the dramatic decrease in EA between atoms whose atomic numbers are one lower than the corresponding breaks in IE. No gaseous atom has positive EA for a second electron. Already negatively charged atom + electron = repulsion

3.6 Electronegativity: tendency of atoms to attract electrons in molecules Mulliken o EN = (1/2)C(IE + EA) o Atoms w/ large EA & IE electron acceptors = electronegative Pauling o XA XB = 0.1021/2 XA and XB are EN values of A and B o = EAB - EAA EBB o Bonds b/w elements w/ EN difference >2 ionic o = 0 covalent and 0.2 to 2 is polar covalent

3.7 Forces and Potential Energy in molecules: Formation of Chemical Bonds Physical objects move spontaneously toward configurations that reduce their potential energy Particles move in directions that will reduce their Coulomb (electrostatic) potential energy

In order to form a bond, total energy is lost -> diatomic molecule is more stable than separated atoms because its total energy is less than of the two separated atoms o Figure 3.12 o When two neutral atoms approach, at large distance Veff -> 0 o As RAB decreases, Veff becomes negative cause atoms begin to attract each other o At very close distances, Veff becomes positive and -> infinity due to repulsion of protons o Re is equilibrium bond length of the molecule o Ed depth of minimum relative to the separated atoms. Measure of the strength of the bond and the extent to which the molecule is more stable than the separated atoms o If potential energy is dominant contribution to total bond energy -> ionic bond o If PE and KE have comparable importance -> covalent or polar covalent

3.8 Ionic Bonding Dominant contribution to the strength of the bond is the electrostatic attraction between the ions Most ionic compounds are solids under normal conditions. High melting and boiling points and form crystals. Conduct electricity poorly Because the smallest IE of any element is larger than the largest Electron affinity of any element, creating an ion pair from neutral atoms always require energy. Figure 13.3 Einfinity = IE1 (K) EA (F) = 91kJ mol-1 Energy of dissociation to neutral atoms (Ex. 3.6) o Ed = IE1 (K ) EA (F) = 91 kJ mol-1 harpooning

3.9 Covalent and Polar Covalent bonding the most important classical descriptons of bonds are bond length, energy, order, and polarity Bond Lengths o Distance between nuclei of two atoms o Among members of a group in the periodic table, bond lengths usually increase with increasing atomic Z Bond Energies o Aka bond dissociation energy is the energy required to break one mole of particular bond under discussion o Bonds generally grow weaker with increasing atomic number HF > HCl > HBr > HI o Bond decreases dramatically in the diatomic molecules from N2 to O2 to F2 Bond Order o Single bond is the longest and weakest bond o Double bond has intermediate strength o Triple bond is the shortest and strongest o Bond order: # of shared electron pairs between the two atoms Polar Covalent Bonding: Electronegativity and Dipole Moments o Absolute value of the difference in electronegativity of two bonded atoms tells the degree of polarity in their bond o Again, 2.0< difference is ioninc, 0.4> is covalent, and in between is polar covalent Dipole Moments and Percent Ionic Character

If two charges of equal magnitude and opposite sign, +q and q, are separated by distance R, the dipole moment of that charge distribution is = qR 1 D (debye) = 3.336 x 10-30 o if delta is the fraction of a unit charge on each atom in a diatomic molecule ( q=delta x e) and R is the equilibrium bond length, then (D) = [R ()/0.2082 ]delta invert to determine delta convert delta into percent ionic character by multiplying 100% Deviations from 100% ionic bonding occur for two reasons: Covalent contributions lead to electron sharing between atoms Electronic charge distribution around one ion may be distorted y the electric field of other ion (polarization) Virial Theorem o If potential energy is dominant contribution to the total bond energy its ionic bond V(r) is driving force o If KE and PE have comparable importance its covalent or polar covalent bond

3.10 Electron pair bonds and lewis diagrams for molecules Octet rule, lone pairs are unshared electron pairs Formal charges o Diagrams with low formal charges are favorable o Formal charge = # of valence electrons - # of electrons in lone pairs (1/2) # of electron in bonding pair Drawing Lewis Diagrams o Count total # of valence electrons and add them up. If species is negative, add electrons. If it is a positive ion, subtract electrons o Subtract total charge (step 1) from total number of e needed to get noble gas shell (H = 2, C=8) o Assign one electron pair to each bond. Assign more bonds if necessary. Assign the rest as lone pairs o Determine formal charges. Check if they add up to total charge o Choose the diagram with smallest magnitudes of formal charges and with any negative formal charges placed on the most electronegative atoms o Resonance Octet Rule o If you cant write Lewis dot diagram for a species, then it is either unstable or highly reactive o Octet rule not satisfied Odd-Electron Molecules (NO) Octet-Deficient Molecules (BF3 stable) Valence shell expansion: more than 8 e can surround an atom in a molecule

3.11 The Shapes of Molecules: Valence Shell Electron-Pair Repulsion Theory To find which geometry applies, we determine the steric number SN of central atom o SN = (# of atoms bonded to central atom) + (# of lone pairs on central atom) Lone pairs occupy more space than bonding pairs electropositive atom repel others more strongly than electronegative -> Figure 3.22c) CH3Cl

Molecules with nonzero dipole moment are polar Molecules with no net dipole moment are non-polar even if they contain polar bonds

3.12 Oxidation numbers ON of atoms in neutral molecule must add up to 0. Those in ions add up to charge of ions Alkali-metal get +1, alkaline get +2 Fluorine gets -1. Other halogens are generally -1 except compounds with oxygen and other halogens Hydrogen is +1 except in metal hybrids (LiH) ON is -1 Oxygen is assigned -2. Two exceptions: in compounds with fluorine (OF 2 is +2) and peroxides (H2O2) is -1, in superoxides (KO2) the ON is -1/2 Neutral atoms of all elements are 0

3.13 Inorganic Nomenclature Ionic Compounds o list name of cation followed by anion o roman numeral for metal ions with more than one charge e.g. copper(II)ion o for anion, add suffix -ide o oxoanions -ate(nitrate), -ite has smaller # of O(nitrite) per- largest # of O hypo- smallest # of O Binary Covalent Compound o 2nd element add suffix -ide o use prefixes (di-, tri-,) for both elements mono- is omitted except for carbon monoxide