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General Chemistry

Elements First Twenty H, He, Li, Be, B, C, N, O, F, Ne, Na, Mg, Al, Si, P, S, Cl, Ar, K, Ca f-Transitions Lanthanides - 57, 58 cerium to 71 lutetium Actinides - 89, 90 thorium to 103 lawrencium Alkali Metals (IA) Sodium (Na) - yellow glowing highway lamps, needed for life, soda lye (NaOH), baking soda (NaHCO3), table salt (NaCl) Lithium (Li) - highest heat capacity, Li-Al aircrafts, dry cells, mental drugs, nuclear reactor heat transfer Potassium (K) - needed for life, saltpepper KNO3 fertilizer Others: rubidium, cesium, francium Alkaline Earth Metals (IIA) Calcium (Ca) - reducing agent, remove impurites, cheap base slaked lime Ca(OH)2, mortar, plaster of Paris 2CaSO4*H2O Magnesium (Mg) - burns white in air; photo flashs, fireworks, anti-oxidation coating, plentiful in oceans Beryllium (Be) - X-ray window tubes Strontium (Sr) - red glow; fireworks and flares Barium (Ba) - spark plugs Group IIIA Boron (B) Aluminum (Al) - most abundant in earth's crust and third overall; buildings, electrical transmission lines, reducing agent including thermite reaction with Fe2O3 in welding steel Gallium (Ga) - melts in the hand; largest liquid state; transistors and high-temp. thermometers Indium (In) - soft bluish; electronics Thallium (Tl) Noble Gases Helium (He) - hot-air balloons, He/O2 deep-sea breathing, cryogenics Neon (Ne) - neon signs Argon (Ar) - inert atmosphere for welding, incandescent light bulbs Krypton (Kr) - airport lights Xenon (Xe) - short-exposure photographs Radon (Ra) - radiotherapy of cancer Halogens ("salt formers") (VIIA) Fluorine (F) - pale yellow gas; prepared in Monel metal cell

Chlorine (Cl) - "green", yellow-green gas; made from NaCl; chlorinates hydrocarbons (chain eactions with radicals and termination steps), household bleaches, swimming pools Bromine (Br) - "stench", dark-red liquid; eyeglasses, film, sedatives Iodine (I) - "purple", violet-black crystalline; from dried seaweed; in growht-regulating hormone thyroxine Group VIA Oxygen (O) - breathing, oxidizing, many other uses Sulfur (S) - mined by Frasch "hot water" process, "brimstone", yellow, stable rhombic and monoclinic forms; contact process used to make 40 million tons of sulfuric acid annually Selenium (Se) - red glass coloring, copy machines, solar cells Tellurium (Te) - added to metals to increase electrical resistance Group VA Nitrogen (N) - 78% of atmosphere, nitrogen cycle (nitrogen-fixation) Phosphorus (P) - present in all living things; used in fertilizers Group IVA Carbon (C) - part of all organic compounds Silicon (Si) - Al-Si alloys for aircraft, silicon dioxide occurs as quartz and flint; glass and computer chips Molecular Structure and Covalent Bonding Polar covalent bond - electrons shared unequally; creates dipole Sigma bond - head on overlap; all single bonds are sigma Pi bond - side on overlap; may include unhybridized p orbital Terms Chemical Formulas and Composition Stoichiometry Allotropes - different forms of element in same physical state, eg O2 and O3 Law of Conservation of Matter - matter is not created or destroyed, only rearranged Limiting reactant - the reactant that is used up completely in the reaction Solution - solute dissolved in solvent Titration - titrant reactant slowly added to solution of another reactant and measure amount for complete reaction; plot curve of added volume vs. pH; at equivalence point equal amounts of acid and base reacted, should coincide with end point, when indicator color changes; use buret Law of Definite Proportions - compound always has ratio of elements same by mass Law of Multiple Proportions - ratio of masses of elements in compound is small whole number ratio Types of Chemical Reactions Periodic Law - properties of elements are periodic functions of atomic number Metals - high conductivity (inc. with inc. temp.), high thermal conductivity, solid except mercury (Ce and

Ga melt), malleable, gray except Ag and Au, few electrons in outer shell, metallic character inc. down and left on PT Electrolytes - substances whose aqueous solutions conduct electricity well, incl. strong acids, strong soluble bases, most soluble salts Precipitates - settle out of solution Oxidation number - number of electrons gained or lost by atom in binary compound Oxidation - loss of electrons Reduction - gain of electrons Oxoacids - ternary acids The Structure of Atoms Photoelectric effect (Einstein) - electromagnetic radiation causes electron emission from metal surface Heisenberg Uncertainty Principle - can't know both momentum and position of small particle Aufbau Principle - electrons added into orbitals in way giving lowest total energy Pauli Exclusion Principle - no two electrons in atom have same 4 quantum numbers Hund's Rule - electrons must occupy all orbitals of a sublevel before pairing Paramagnetic - unpaired electrons weakly attracted into magnetic fields Diamagnetic - all electrons paired and are very weakly repelled by magnetic fields Ferromagnetic - Fe, Co, and Ni permanently magnetized as spins align with field Chemical Periodicity Screening causes effective nuclear charge to be less than actual nuclear charge Combustion reaction - oxygen combines rapidly, very exothermic, hydrocarbon+oxygen yields carbon dioxide water and heat Roasting - extracting free metals by heating an ore in air (oxygen) Chemical Bonding Ionic compounds - high melting pt., soluble in polar solvents, insoluble in nonpolars, molten and aqueous solutions conduct electricity; large electronegativity difference between atoms Lewis dot formulas - show valence electrons Octet Rule - most compounds achieve noble gas configurations Resonance - two or more Lewis structures describe bonding Formal charge - charge on atom in a molecule or polyatomic ion Acids, Bases, and Salts Protonic acids - acids with acidic hydrogen atoms Arrhenius theory - acid produces H+ in aqueous solution; base produces OH- in solution Bronsted-Lowry theory - acid is proton donor; base is proton acceptor Lewis theory - acid accepts a share in electron pair, base donates a share in electron pair

Conjugate acid-base pairs - differ by proton; weak acid yields strong conjugate base and vice versa Amphoterism - ability to react as either acid or base Coordinate covalent bond - both electrons furnished by one atom Standardization - process to determine concentration by measuring volume required to react with known amount of primary standard Equivalent weight of an acid - mass needed to furnish 6.022*1023 hydrogen ions Half-reaction - either reduction or oxidation part of redox reaction Gases Fluids - liquids and gases; flow freely Vapor - gas formed by evaporation or sublimation Pressure - force per unit area; measured by barometer (1 torr = 1 mm Hg), manometer U-shaped tube Dumas method - used to find molecular weights of volatile liquids using boiling water bath Kinetic-molecular theory - by Rudolf Clausius; collisions are elastic, molecules travel in straight line with constant velocity until collide; gases consist of discrete molecules Effusion - escape of gas through tiny hole Diffusion - movement of gas into a space or mixing with another gas London forces - weak attractive forces in molecules; vary as 1/d7; only intermolecular forces among symmetric nonpolars Dipole-dipole interactions - attraction of opposite partial charges; vary as 1/d4 Hydrogen bonding - H to F, O, or N; like dipoles Liquids and Solids Viscosity - resistance to flow of a liquid; can measure with Ostwald viscometer Surface tension - inward force overcome to expand surface are of liquid Meniscus - surface of liquid Cohesive forces - hold liquid together; adhesive forces hold liquid to another surface Evaporation - opposite of condensation; molar heat of vaporization and heat of condensation Vapor pressure - partial pressure of vapor molecules above liquid surface; easily vaporized are volatile Boiling point - vapor pressure = external pressure Melting - opposite of freezing; molar heat of fusion and heat of solidification Sublimation - opposite of deposition Phase diagrams - temperature vs. pressure; triple point all 3 states at equil. (4.6 torr, 0.01 C for water); can't liquefy gas above critical point Amorphous solids - no well-defined structure (like rubber, some plastics)

Crystals - unit cells repeat and can be replaced with lattice point; 7 systems incl. Cubic, tetragonal, orthorhombic, monoclinic, triclinic, hexagonal, rhombohedral Isomorphous - substances that crystallize in same type of lattice Polymorphous - substance that crystallizes in multiple forms Coordination number - number of neighbors in solid packing Metallic bonding - band theory describes continuous bands of closely spaced molecular orbitals Conduction band - a band electrons must move into to allow conduction; insulators have band gap; semiconductors have filled bands that are slightly below empty bands Solutions Solvation - process of solvent molecules surrounding solute ions or molecules; called hydration if water Miscibility - ability of a liquid to dissolve in another; add acid to water Saturated - solid and dissolved ions in equilibrium Supersaturated - high solute prepared at high temperature then cooled Fractional distillation - separate liquid mixture by boiling points Boiling point diagram - mole fraction vs. temperature; bowed curves for vapor and liquid; intercepts show boiling points Colloids - dispersed phase (solutes) suspended in dispersing medium (solvent); solid in solid solid sol, liquid in solid solid emulsion, gas in solid solid foam, solid in liquid sols and gels, liquid in liquid emulsion, gas in liquid foam, solid in gas solid aerosol, liquid in gas liquid aerosol Tyndall effect - scattering of light by collodial particles Micelles - cluster of molecules with hydrophobic tails in center and hydrophilic heads outward Surfactant - has ability to suspend and wash away oil and grease Hard water - contains Fe3+, Ca2+, and/or Mg2+ ions Emulsifiers - coat particles of dispersed phase to prevent coagulation into separate phase Eutrophication - overgrowth of vegetation because of high phosphorous concentration Synthetic detergents - soap-like emulsifiers with sulfonate or sulfate instead of carboxylate Colligative properties - physical properties depending on number not kind of solute particles Thermodynamics State function - value depends only on current state not how it got there

Calorimetry - measuring heat transfer between system and surroundings using calorimeter; coffee-cup and bomb caliometers (constant volume) Enthalpy - heat content Standard molar enthalpy of formation - enthalpy change for reaction in which one mole is formed from its elements at their standard states Bond energy - energy needed to break one mole of bonds Kinetics Transition state theory - activation energy to form transition state Mechanism - step by step reactions; rate determined by slowest, rate-determining step Heterogeneous catalysts - speed up reaction but are in different phase than reactants, such as powdered noble metals and metal oxides in catalytic converters Enzymes - biological catalysts; bind substrates Equilibrium Chemical equilibrium - two opposing reactions occur simultaneously at same rate; dynamic equilibrium LeChatelier's Principle - system responds to stress at equilibrium in a way that reduces stress and reaches new state of equilibrium Haber process - N2 + 3H2 <-> 2NH3 Acids and Bases Common ion effect - behavior of solution in which same ion is produced by two different compounds Buffers - minimize changes in pH because basic component can react with H3O+ ions and acidic component can react with OH- ions Polyprotic acids - furnish two or more hydronium ions per mole Solvolysis - reaction of substance with the solvent in which it is dissolved; hyrolysis if water Electrochemistry Electrolytic cells - external electricity causes nonspontaneous reactions by electrolysis Voltaic cells (galvanic cells) - spontaneous chemical reactions produce electricity Electrodes - surfaces upon which oxidation (anode) or reduction (cathode) half reaction occurs Downs Cell - electrolysis of molten sodium chloride Faraday's Law of Electrolysis - amount that oxidizes or reduces at each electrode is directly prop. to amount of electricity that passes through cell Faraday - amount of electricity that reduces one equivalent weight at cathode and reduces at anode Electroplating - using using electrolysis to plate metal onto surface

Salt bridge - circuit between two solutions in a voltaic cell Standard cell - all species are in thermodynamic standard states (1 M , 1 atm) Standard Hydrogen Electrode (SHE) - reference electrode relative to which electric potentials are measured as reduction at 25 C; if Eo > 0 reduction occurs more readily than 2H+ to H2 Corrosion - redox process by which metals are oxidized by oxygen in presence of moisture; prevent by plating or galvanizing (coating steel with zinc) Primary voltaic cells - cannot be recharged; includes Georges Leclanche's dry cell (ZN(NH4)3) and alkaline dry cells Secondary voltaic cells - reversible; can be recharged, such as lead storage battery in cars (PbSO4), nickelcadmium (nicad) cells, and hydrogen-oxygen fuel cells Metallurgy Native ores - uncombined free state of less active metals, like Cu, Ag, Au Ores - contain minerals mixed with gangue (sand, rock, etc) Metal separation includes flotation, roasting (heating with oxygen), reaction with coke (carbon) or CO, and electolysis of molten salt Hall-Heroult process - cell for electolyzing Al Iron - blast furnace with CO converts to limestone flux, which reacts with silica gangue to form slag of calcium silicate; iron from blast furnace contains carbon (pig iron); remelted and cooled to cast iron; add other metals like Mn, Cr, Ni, W, Mo, V to make steel Coordination Compounds Coordination compounds - compounds with bonds in which both shared electrons are donated by same atom Ligand - a Lewis base in a coordination compound Polydentate - ligands with multiple donor atoms Chelate - a ligand that utilizes two or more donor atoms in bonding to metals Nuclear Chemistry Nuclear fission - splitting of heavy nucleus into lighter nuclei Nuclear fusion - combination of light nuclei to produce heavier nucleus Mass deficiency - difference between sum of masses of electrons/proton/neutrons and actual mass Scintillation counter - detects radiation using fluorescence Cloud chamber - detects radiation using water vapor; developed by Wilson Gas Ionization chamber - such as Geiger-Muller counter Disintegration series - sequence of atoms during decay

Radiocarbon dating - C14, K-Ar, U-Pb methods Radioactive tracers - Na24 blood, Th201 and Tc99 heart, I131 thyroid liver and brain, Pl238 pacemakers Cyclotrons - devise for accelerating charged particles along spiral path Linear accelerators - device used for accelerating charged particles along straight line path Uranium-235 decay - to Uranium-236 to Sm/Zn, La/Br, Ba/Kr, Cs/Rb, Xe/Sr Fission reactors - use U3O8 fuel rods enriched in uranium-235, water and graphite moderators (and He and heavy water), B/Li control rods, cooling systems, concrete shielding Thermonuclear bombs (fusion bombs, hydrogen bombs) - activation energy of fusion obtained by fission Plasma - state of matter at high temperatures at which all molecules are dissociated and most ionized Equations D=m/V Sp. Gr. = D/Dwater Sp. Heat = (heat in J)/((mass in g)*(temp. change in C)) Molarity = moles/Liter V1M1 = V2M2 v = fl E = hv Rydberg equation: 1/l = R(1/n12-1/n22) relating H spectrum wavelengths De Broglie equation: l = h/(m*f) showing small particles can display wave properties Schrodinger's equation: in terms of electron wave function y, solutions are possible energy states for electron in atom; Dirac incorporated relativity Number of atomic orbits = (energy level n)2 Formal charge = (group number) - (number of bonds) - (number of unshared electrons) Dipole moment = (distance)*(magnitude of charge)Bond order = (bonding electrons antibonding electrons)/2 Normality = (number of equivalent weights of solute)/(L of solution) Boyle's Law : P1V1 = P2V2 ; volume inversely prop. to pressure Charles' Law: V1/T1 = V2/T2 ; volume directly prop. to temperature Combined gas law : P1V1/T1 = P2V2/T2 Avogadro's Law: V1/n1 = V2/n2 ; volume directly prop. to number of moles of gas Ideal Gas Law: PV = nRT Dalton's Law of Partial Pressures: Ptotal = PA + PB + PC + ... ; partial pressure of each gas is its mole fraction times total pressure of mixture Average molecular kinetic energy is directly prop. to absolute temperature

Van der Waals equation: (P+n2a/V2)(V-nb) = nRT ; extends ideal gas law to real gases using two empiricals Coulomb's Law: F=kq1q2/d2 Bragg equation: nl = 2*d*sin(q), relates reflections for X-rays to wavelength and distance Henry's Law: Pgas = kCgas ; pressure of gas above solution is prop. to concentration of gas in solution Molality = (number of moles of solute)/(number of kilograms of solvent) Raoult's Law: Psolvent = Xsolvent/P0solvent ; vapor pressure of solvent is directly prop. to mole fraction of solute Boiling point elevation: DTb = Kbm ; boiling point directly prop. to molality of solute Freezing point depression: DTf = Kfm; freezing point depression directly prop. to molality of solute Osmotic pressure p = MRT KE = mv2/2 Hess' Law: DHrxn0 = DHa + DHb + ... ; enthalpy change is same as series of steps as if one reaction DHrxn0 = S(bond energies of reactants) - S(bond energies of products) DH = DE + PDV DE = q + w = q - PDV; difference in internal energy = heat and work Gibbs free energy: DG = DH - TDS Rate-law expression: xA + yB -> C + D rate = k[A]x[B]y Arrhenius equation: k = Ae-Ea/RT ; relates rate constant to activation energy, temperature, and collision freq. Chemical equilibrium: aA + bB -> cC + dD Keq = ([C]c[D]d)/ ([A]a[B]b) ; reaction quotient Q is same form for a specific time; can also use partial pressures rather than concentrations KP = KC(RT)Dn DG0 = -RTln(K) van't Hoff equation: ln(KT2/KT1) = DH0/R (1/T1 - 1/T2) ; estimate equilibrium constant at another temperature Kw = [H3O+][OH-] = 10-14 pH = -log([H3O+]) pKa = -log(Ka) ; large Ka -> small pKa -> strong acid Henderson-Hasselbalch equation: pH = pKa + log([conj. base]/[acid]) Nernst equation: E = E0 - (2.303*R*T)/(n*F)*log(Q) = E0 (0.0592*T)/n*log([Red]y/[Ox]x) ; calculates electrode potentials for concentrations and partial pressures other than standard values nFE0 = 2.303*R*T*log(K) DG = -nFEcell

nuclear binding energy = (mass deficiency)*(speed of light)2 Half-life decay: t1/2 = ln(2)/k Reaction orders: Zero rate=k [A] = [A]0 - akt t1/2 = [A]0/(2*a*k) First rate=k[A] ln([A]0/[A]) = akt t1/2 = ln(2)/akSecond rate=k[A]2 1/[A] - 1/[A]0 = akt t1/2 = 1/(ak[A]0) Constants and Numbers Mole = 6.022*1023 particles Electron = 1.75882*108 C/g, 9.109*10-28 g 1 g = 6.022*1023 amu Planck's constant h = 6.6262*10-34 Js Rydberg's constant 1.097*107 m-1 Standard molar volume of ideal gas at STP: 22.414 liters per mole Universal gas constant R = 0.08206 (L*atm)/(mol*K) Heat of vaporization of water = 2.26 kJ/g Specific heat of water = 4.18 J/(g*C) Heat of fusion of water = 334 J/g 1 faraday = 96485 Coulombs Joule = kg*m2/s2 Lists Polyatomic Ions Plus one: Na, K, NH4 ammonium, Ag, Cu+ cuprous Plus two: Fe2+ ferrous, Cu2+ cupric, Zn, Mg, Ca, Hg mercuric, Hg2 mercurous Plus three: Fe3+ ferric, Al Minus one: CH3COO acetate, F, Cl, Br, OH, NO2 nitrite NO3 nitrate, CN cyanide, ClO hypochlorite, ClO2 chlorite, ClO3 chlorate, ClO4 perchlorate Minus two: SO3 sulfite, SO4 sulfate, CO3 carbonate, CrO4 chromate, Cr2O7 dichromate Minus three: PO4 phosphate, AsO4 arsenate Acids Acids: HNO3 nitric, HclO4 perchloric, HClO3 chloric, H2SO4 sulfuric, H3PO4 phosphoric, H3PO2 hypophosphorous Ternary acids names: perXic (perXate), Xic (Xate), Xous (Xite), hypoXous (hypoXite) Strengths (inc.) : NH3, H2O, NH4, HCN, CH3COOH, HF, HNO3, HCl, HBr, HI, HclO4 Quantum Numbers primary n (main energy level, 1,2,3...), subsidary or azimuthal l (shape of region, 0..n-1 = s,p,d,f,etc), magnetic ml (spatial orientation -l..l orbitals), spin ms (1/2 or -1/2) Oxidation numbers +1/-1: H +1: Li, Na, K

+2: Be, Mg, Ca, Cu, Zn +3: B, Al, Ga, Se +4: C, Si, Ge, Ti +5/-3: N +5: P +6/-2: S, Se -2: O -1: F, Cl, Br None: He, Ne, Ar Oxides: O2- oxides, O22- peroxides, O2- superoxides Indicators Methyl red: <4 red, >7 yellow; Bromthymol blue: <6 yellow, >8 blue; Phenolphthalein: <8 colorless, >10 red Orbital Orderings 1s22s22p63s23p64s23d104p65s24d105p66s24f145d106p67s25f146d107p68s2 diagonals Bond Orders H2 1, He2 0, B2 1, N2 3, O2 2 Solubility Rules Soluble - common inorganic and low molecular weight organic acids, compounds of Group IA metals, nitrates, acetates, chlorates, perchlorates; Insoluble - most hydroxides, carbonates, phosphates, arsenates, sulfides Three Laws of Thermodynamics First - total energy in universe is constant Second - in spontaneous reactions universe tends towards state of greater disorder (greater entropy) Third - entropy of pure, perfect crystalline substance is zero at 0 K Periodic trends Inc. up and right: ionization energy, electron affinity negativeness (easily becomes anion), electronegativity (Fr least, F most, none for nobles) Inc. down and left: atomic radii Radioactive decay beta emission (electron ejected from nucleus as neutron is converted to proton), positron emission or electron K-capture (positron ejected from nucleus as proton is converted to neutron), alpha emission (helium nucleus with 2 protons and 4 neutrons is ejected) Valence Shell Electron Pair Repulsion Theory (VSEPR) Bonds+electron pairs = 2 (linear, sp, 180), 3 (trigonal planar, sp2, 120), 4 (tetrahedral, sp3, 109.5),

5 (trigonal bipyramidal, sp3d or dsp3, 90,120,180), 6 (octahedral, sp3d2 or d2sp3, 90,180) hybrid - mixing of orbitals Elements in the Earth O 49.5%, Si 25.7, Al 7.5, Fe 4.7, Ca 3.4, Na 2.6 Most Commercially Used Acids sulfuric, lime (CaO and Ca(OH)2), ammonia, NaOH, phosphoric, nitric Energy The Boltzmann constant is R/NA , or 1.38*10-23 J/K. A Joule is kg*m2/s2. The de Broglie relation states that the product of linear momentum and wavelength is a constant, Planck's constant, 6.6*10-34 Js The Boltzmann distribution gives the ration of the numbers of particles in states with given energies, Ni/Nj = e-(Ei-Ej)/kT The Maxwell distribution gives the proportion of molecules that have a specific speed at a particular temperature, based on Boltzmann distribution. Gases Zeroth Law of Thermodynamics - If A is in thermal equilibrium with B, and B is in thermal equilibrium with C, then C is also in thermal equilibrium with A Ideal Gas Law: PV = nRT PV = 1/3nMc2 ; c = root mean square speed of molecules, M = molar mass mNA Maxwell distribution of speeds Van der Waals equation, using compression factor and virial coefficients, adjusts ideal gas law to real gases Maxwell construction replaces unrealistic van der Waals loops. Principle of corresponding states: real gases at same volume and temperature exert same reduced pressure. First Law The First Law states that the total energy in the universe is constant.; it cannot be created or destoryed Diathermic boundary permits heat transfer; adiabatic boundary permits energy transfer but not heat transfer. Heat capacity at constant volume is partial of internal energy with respect to temperature; at constant temperature is partial of internal energy with respect to volume. Enthalpy is sum of internal energy and pressure times volume. Hess' Law: DHrxn0 = DHa + DHb + ... ; standard enthalpy is the sum of the standard enthalpies of the individual reactions into which a reaction may be divided.

Kirchoff's Law is used to estimate standard enthalpies of formation from molar heat capacities and reaction enthalpies at some other temperature. James Joule tried to measure internal pressure by observing the change in temperature of a gas expanding in a vacuum. Joule-Thompson coefficient is partial of temperature with respect to pressure at constant enthalpy. The Joule-Thompson effect is the cooling by adiabatic expansion, such that the temperature difference is proportional to the pressure difference. Second Law The Second Law states that he entropy (disorder) of an isolated system increases in the course of a spontaneous change. Carnot cycle consists of isothermal reversible expansion, reversible adiabatic expansion, isothermal reversible compression, and adiabatic reversible compression. Efficiency of a Carnot engine is 1-Tc/Th Clausius inequality states that change in entropy is greater than or equal to the heat supplied to the system during the process divided by temperature. Trouton's rule states that the standard molar enthalpy of vaporization is about the same for a wide range of liquids (85 J/(K*mol). The Debye extrapolation fits measurements of heat capacity at lower temperatures. The Nernst heat theorem states that the entropy change accompanying any physical or chemical transformation approaches zero as temperature approaches zero. The Third Law states that the entropy of pure, perfect crystalline substance is zero at 0 K. The Helmholtz energy A is internal energy minus temperature times entropy; it equals the maximum work accompanying a process. The Gibbs energy G is the enthalpy minus temperature times entropy; it equals the maximum nonexpansion work. The standard Gibbs energy of formation is the standard reaction Gibbs energy for the formation of a compound from its elements in their reference states. dU = TdS-pdV

The Maxwell relations are derived from the fact that enthalpy, Gibbs energy, and Helmholtz energies are all state functions. For example, the partial of temperature with respect to volume at constant entropy equals negative the partial of pressure with respect to entropy at constant volume. The Gibbs-Helmholtz equation shows that if the enthalpy of the system is known, then the temperature dependence of Gibbs energy over temperature is also known; the partial of the Gibbs energy over the temperature with respect to temperature at constant pressure equals negative the Helmholtz energy divided by the temperature squared. Chemical potential is the partial of the Gibbs energy with respect to the number of molecules at constant temperature and pressure. Fugacity is an effective pressure. Physical Transformations Phase diagrams plot temperature vs. pressure. At the triple point all 3 states are at equilibrium (4.6 torr, 0.01 C for water). You cannot liquefy gas above critical point. The Clapeyron equation is the slope of the phase boundary. The Clausius-Clapeyron equation describes the variation of vapor pressure with temperature. Ehrenfest classification groups phase transitions into first-order, second-order, and lambda-transition. Surface tension is the constant relating work to change in surface area of a liquid. The Laplace equation states that the pressure on the concave side of an interface is always greater than on the convex side. Simple mixtures The Gibbs-Dunhem equation states that the chemical potential of one component of a mixture cannot change independently of the chemical potentials of the other components. Raoult's Law states that the ratio of the partial vapour pressure of each component to its vapour pressure as a pure liquid is about equal to the mole fraction of the component in the mixture. Henry's law states that the vapor pressure of a solute is proportional to its mole fraction but the constant of proportionality is not the pure substance's vapor pressure. In ideal-dilute solutions, solvent obeys Raoult's Law and solute Henry's Law. Cryoscopy measures molar mass from freezing point depression.

The van't Hoff equation states that the osmotic pressure equals the molar concentration of the solute times R times the temperature. Phase Diagrams Gibbs' Phase Rule states that the variance equals the number of components minus the number of phases plus two in a phase diagram. Vertical isopleth and horizontal tie lines on phase diagram, used in lever rule. Number of theoretical plates on temperature-composition diagram determines efficiency of fractional distillation. In an azeotrope, evaporation occurs without a change in composition ("boiling without changing"). At eutectic composition, a liquid mixture freezes at a single temperature. Chemical Equilibrium Gibbs reaction energy is slope of Gibbs energy vs. extent of reaction. G = -RTln(K) LeChatelier's Principle states that a system responds to stress at equilibrium in a way that reduces stress and reaches new state of equilibrium. Henderson-Hasselbalch equation: pH = pKa + log([conj. base]/[acid]) Equilibrium Electrochemistry The Born equation identifies the Gibbs energy of solvation with the electrical work of transferring an ion from a vacuum into the solvent treated as a continuous dielectric of relative permittivity. The Debye-Huckel limiting law calculates the activity coefficient. The long range of Coulombic interactions dominates contributions to nonideality in ionic solutions. Faraday's constant equals electron charge times Avogadro's number 96.485 kC/mol; it is the amount of electricity that reduces one equivalent weight at cathode and reduces at anode The Nernst equation calculates electrode potentials for concentrations and partial pressures other than standard values; E = E0 - (2.303*R*T)/(n*F)*log(Q) = E0 (0.0592*T)/n*log([Red]y/[Ox]x) ; In electrolytic cells external electricity causes nonspontaneous reactions by electrolysis. In voltaic cells (galvanic cells) spontaneous chemical reactions produce electricity. Electrodes are surfaces upon which oxidation (anode) or reduction (cathode) half reaction occurs.

Faraday's Law of Electrolysis states that the amount that oxidizes or reduces at each electrode is directly proportional to amount of electricity that passes through cell. In a standard cell, all species are in thermodynamic standard states (1 M , 1 atm). The Standard Hydrogen Electrode (SHE) is a reference electrode relative to which electric potentials are measured as reduction at 25 C; if Eo > 0 reduction occurs more readily than 2H+ to H2 pH = (E+E(cal))/(-59.16 mV) Quantum Theory Wien Displacement Law The Stefan-Boltzmann law states that the energy density of the electromagnetic field varies with fourth power of temperature. The Rayleigh-Jeans law uses the equipartition principle to calculate the average energy of each oscillator; predicts infinite energy density at short wavelengths. The Planck Distribution quantizes energy. The Einstein formula relates heat capacity to frequency. In the photoelectric effect, electrons are ejected from metals when exposed to UV radiation. The deBroglie relation states that particles with high linear momentum have short wavelength. The Davisson-Germer experiment shows particles have wave-like properties. Schrodinger's equation finds wavefunction of particle. The Born interprestion squares the wavefunction to get probability distribution. Heisenberg's uncertainty principle states it is impossible to known precisely both the momentum and position of a particle. Gaussian function is of the form e-x*x Atomic Structure and Atomic Spectra Rydberg combined the Balmer series (visible), Lyman series (UV), and Paschen series (infrared) about wavenumbers transitions. The Ritz combination principle states that the wavenumber of any spectral line is the difference between the two terms. The Bohr frequency condition states that an atom's energy change is carried away by a photon of frequency E/h. The Bohr radius is 52.9177 pm. Quantum numbers: primary n (main energy level, 1,2,3...), subsidary or azimuthal l (shape of region, 0..n-1

= s,p,d,f,etc), magnetic ml (spatial orientation -l..l orbitals), spin ms (1/2 or -1/2) Orbital Orderings: 1s22s22p63s23p64s23d104p65s24d105p66s24f145d106p67s25f146d107p68s2 diagonals The Aufbau Principle states that electrons added into orbitals in way giving lowest total energy. The Pauli Exclusion Principle states that no two electrons in atom have same 4 quantum numbers. Hund's Rule states that electrons mus toccupy all orbitals of a sublevel before pairing. Ionization energy is the energy needed to remove an electron. Signal splitting multiplicity (doublet, etc.) is one more than the number of nonequivalent hydrogen neighbors within three sigma bonds (from spin-spin coupling); induced field of electrons shields protons from external field. Molecular Structure The Born-Oppenheimer approximation assumes nuclei is stationary and electrons move around. Valence Shell Electron Pair Repulsion Theory (VSEPR) describes formation of hybrid orbitals. If bonds+electron pairs = 2 (linear, sp, 180), 3 (trigonal planar, sp2, 120), 4 (tetrahedral, sp3, 109.5), 5 (trigonal bipyramidal, sp3d or dsp3, 90,120,180), 6 (octahedral, sp3d2 or d2sp3, 90,180) In a polar covalent bond, electrons are shared unequally; creates dipole. In a sigma bond there is head on overlap; all single bonds are sigma. In a pi bond, there is side on overlap; may include unhybridized p orbital. A molecular orbital is an orbital resulting from overlap and mixing of atomic orbitals on different atoms; belongs to molecule as whole Nodal planes are the regions of zero probability of finding electrons Electronegativity is a measure of the power of an atom to attract electrons to itself when it is part of a compound. The variation principle states that if an arbitrary wavefunction is used to calculate energy, the value is never less than the true energy. Walsh diagrams show the variation of orbital energy with molecular geometry. The Huckel approximations (overlap integrals and resonance integrals between nonneighbors are zero and remaining resonance integrals are equal) allow calculation of molecular orbital energy levels.

Bonding HUMO (highest occupied molecular orbital) and antibonding LUMO (lowest unoccupied molecular orbital). Conjugated systems are stabilized by delocalization energy. Semiconductor conductivity increases with temperature; conductor decreases with temperature. Statistical Thermodynamics The Boltzmann distribution can be written in terms of the molecular partition function, which can be used to calculate the proportion of molecules in different states. The Boltzmann formula states that entropy is directly proportional to the log of the weight of the most probable configuration of the system. The canonical ensemble is an imaginary collection of replications of a system in thermal contact with a constant temperature. The Sackur-Tetrode equation gives the entropy of a monatomic gas. The internal energy with and entropy of a system may be calculated from its canonical partition function. Diffraction Techniques Diffraction is the interference caused by an object in the path of waves. Crystals consist of repeating unit cells; 7 systems include cubic, tetragonal, orthorhombic, monoclinic, triclinic, hexagonal, and rhombohedral. The Miller indices are the reciprocals of intersection distances in a lattice. Bragg's law states that a bright reflection should occur when two times the distance times the sine of the glancing angle is an integral multiple of the wavelength. Von Laue and Debye - Scherrer used X-rays with crystals. The Wierl equation calculates the angular variation of the total intensity by summing the contributions from all pairs. Electric and Magnetic Properties of Molecules The polarization of a sample is the electric dipole moment density, and a dielectric is a polarizable, nonconducting medium. Differences in atomic radii of overlapping atoms causes homopolar contribution to the dipole moment. Induced dipole moments are proportional to the field strength. The relative permittivity is also called the dielectric constant and is the square of the refractive index,

which is the ratio of the speed of light in a vacuum to the speed in the medium. The Clausius-Mossotti equation assumes no permanent dipole moment, simplifying the Debye equation for molar polarization. The Keesom interaction is the interaction of two rotating molecules. The London formula approximates the interaction energy in an induced dipole - induced dipole dispersion (London) interaction. The Lennard-Jones formula is a specific case of the Mie formula, which estimates the potential energy from repulsions and attractions. The magnetic flux density is related to the applied field strength and the magnetization. If the molar magnetic susceptibility is positive, the material is paramagnetic; if negative, diamagnetic. The Curie law defines the molar magnetic susceptibility, which is measured by a Gouy balance or a superconducting quantum interference device (SQUID). At Curie temperature, spins may align making ferromagnetic transition, and at Neel temperature, spins may alternate to antiferromagnetic phase. Macromolecules and Colloids Monodisperse molecules have a single, definite molar mass. Solutions are virtually ideal at Flory theta temperature. Donnan equilibrium is the equilibrium distribution of ions in two compartments in contact through a semipermeable membrane, one with a polyelectrolyte (strings of acids or bases) Sedimentation is the fall of heavy particles due to gravity. The Stokes-Einstein relation states that the frictional cofficient is directly proportional to temperature and indirectly to the diffusion coefficient. In electrophoresis, charged macromolecules move due to an electric field, as in through a cross-linked polyacrylamide gel (gel electrophoresis). Viscosity is often measured by Ostwald or rotating drum viscometers. Rayleigh scattering is the scattering by particles with diameters much smaller than the wavelength of the incident radiation. The Corey-Pauling rules describe the secondary structure of proteins, which may form alpha helices, beta pleated sheets, or random coils. Ramachandran plots contours of the potential energy of an entire molecule. Colloids are purified by (electro)dialysis.

Micelles form above the Krafft temperature and may form orderly lyotropic mesomorphs. Coagulation is the blending together of distinct particles into large particles. The Schulze-Hardy rule states that hydrophobic colloids are flocculated (aggregation of particles) efficiently by ions of high charge numdber and opposite charge type. One molecule thick monolayers transferred to solid supports are Langmuir-Blodgett films. Molecules in Motion Graham's law of effusion states that the rate of effusion is inversely proportional to the square root of the molar mass. Fick's first law of diffusion states that the flux of matter is proportional to the concentration gradient. Newtonian flow is a series of layers moving past one another. Diffusion equals one-third the product of wavelength and mean speed for a perfect gas, and viscosity equals one-third the product of the molar mass, wavelength, mean speed, and molar concentration. Monte Carlo methods are used to measure the change in total potential energy of particles moved over small but random distances in a box. The conductance (in siemens) of a sample equals its conductivity constant times its crosssectional area divided by its length. Kohlrausch's law states that at low concentrations the molar conductivities of strong electrolytes vary linearly with the square root of the concentration. The Grotthuss mechanism describes the motion of a proton involving the rearrangement of bonds in a group of water molecules. The transport number is the fraction of total current carried by the ions of a given type. The Debye-Huckel-Onsager theory quantifies electrophoretic effects. The Green-Kubo relation expresses a transport property in term sof teh fluctuations in microscopic properties of a system. The Einstein relation links the molar conductivity of an electrolyte to the diffusion coefficients of its ions. The Nernst-Einstein equation determines ionic diffusion coefficients from conductivity measurements; Walden's rule. The Einstein-Smoluchowski equation states that the diffusion constant equals the square of the step length

of a one-dimensional random walk divided by twice the time. The Rates of Chemical Reactions Reaction progress may be monitored using real-time, quenching, flow, stopped-flow, and flash photolysis methods. The reaction order is the sum of the orders for each component. Reaction orders (from integrated rate laws): Zero rate=k [A] = [A]0 - akt t1/2 = [A]0/(2*a*k) Firstrate=k[A] ln([A]0/[A]) = akt t1/2 = ln(2)/akSecond rate=k[A]2 1/[A] - 1/[A]0 = akt t1/2 = 1/(ak[A]0) Half-life decay: t1/2 = ln(2)/k The Arrhenius equation relates rate constant to activation energy, temperature, and collision frequency; k = Ae-Ea/RT The steady-state approximation assumes that after an initial induction period and the major part of the reaction, the rates of change of concentration of all reaction intermediates are negligibly small. In the Michaelis-Menten mechanism of enzyme action, the rate depends on enzyme concentration even though it undergoes no net change; E + S = ES --> P + E A Lineweaver-Burk plot of the reciprocal of the reaction rate against the reciprocal of the substrate concentration in a Michaelis-Menten mechanism gives the rate of the second step and the Michaelis constant. The Lindemann-Hinshelwood mechanism describes unimolecular reactions. The Rice-Herzfeld mechanism describes chain reactions. The Lotka-Volterra mechanism describes oscillating reactions at steady-state. Oscillating reactions, such as the brusselator and the oregonator, must be far from equilibrium, have autocatalytic steps, and be able to exist in two steady states (bistability). Processes at Solid Surfaces The Auger effect is the emission of a second electron after high-energy radiation has expelled another. Adsorption is the attachment of particles to a surface. In scanning tunnelling microscopy, a platinum-rhodium or tungsten needle is scanned across the surface of a conducting solid. In atomic force microscopy, a sharpened stylus attached to a beam is scanned across the surface.

In physisorption, there is a van der Waals interaction between the adsorbate and substrate. In chemisorption, molecules stick to the surface by forming a chemical bond. In accommodation, a molecule bouncing on the surface will lose its energy and eventually adsorb to it. The BET (Brunauer-Emmett-Teller) isotherm deals with multilayer adsorption. The Temkin isotherm supposes adsorption enthalpy changes linearly with pressure; the Freundlich isotherm logarithmically. In the Eley-Rideal mechanism of a surface-catalysed reaction, a gas-phase molecule collides with another molecule already adsorbed on the surface. Dynamic Electrochemistry Current density is the charge flux through a region. The interface at an electrode can be modeled as an electrical double layer, including Helmholtz and GouyChapman, and combined Stern model. The surface potential is the difference between the Volta (outer) and Galvani (inner) potentials. The Butler-Volmer equation relates the current density to the Galvani potential difference. Voltammetry measures the current as the potential of the electrode is changed to study the kinetics of electrode processes, including linear-sweep, differential pulse, and cyclic methods. Primary voltaic cells cannot be recharged; secondary voltaic cells (including fuel cells) may be. Corrosion is a redox process by which metals are oxidized by oxygen in the presence of moisture. Galvanizing is the coating of an iron object with zinc to prevent corrosion. Spectroscopy Emission spectroscopy measures change in molecule from high to low energy state, emitting excess energy as photon. Absorption spectroscopy monitors net absorption of nearly monochromatic incident radiation. Michelson interferometer in Fourier transform machine analyses the frequencies. Elements of spectroscopy include radiation source, dispersing element, FT technique, detectors, and the sample.

Raman spectroscopy examines frequencies present in radiation scattered by molecules, low-frequency Stokes and high frequency anti-Stokes; resonance and coherent anti-Stokes variations of Raman. ??Beer-Lambert law states that absorbance equals extinction coefficient times concentration times column length. The Stark effect states that the energy of a state depends on the square of the permanent electric dipole moment; Stark modulation. Molecules are modeled as rigid rotors (spherical, symmetrical, linear, or asymmetric), bodies that do not distort under the stress of rotation. The Morse potential energy curve reproduces the general shape of a molecular potential energy curve. Birge-Sponer plots may be used to determine dissociation energy. Tumbling is the random changing of orientation of a molecule. The exclusion rule states that no modes of a symmetrical molecule can be both infrared and Raman active. The Franck-Condon Principle states that electronic transitions take place much faster than nuclei can respond since nuclei are so much more massive. The Laporte selection rule states that the only allowed transitions are those that are accompanied by a change of parity. In fluorescence, radiation emission ceases immediately but in phosphorescence it may continue after the exciting radiation is extinguished. Jablonski diagrams show the relative positions of the electronic energy levels of a molecule. Laser light is coherent (in step). The active medium of a solid-state laser is a single crystal or a glass (including Maiman's first ruby laser and neodymium lasers). Gas lasers include He-Ne, Ar ion, Kr ion, CO2. Other lasers include chemical, exciplex (combo of two atoms surviving in an excited state), dye, lightemitting diodes, and semiconductors. Photoelectron spectroscopy finds orbital energies by measuring ionization energies when electrons are ejected from different orbitals. Koopman's theorem states that ionization energy equals orbital energy of ejected electron.

Shielding of nuclei decreases chemical shift in nuclear magnetic resonance spectroscopy. Observed shielding constant is sum of local (from Lamb formula), neighbor (number of non-equivalent adjacent hydrogens), and solvent contributions. The splitting of resonances into individual lines is the fine structure of the spectrum. The Karplus equation defines the coupling constant. Fermi contact interactions occur when s-orbital electrons come very close to the nucleus. Magnetically equivalent nuclei are chemically equivalent and have identical spin-spin interactions. The nuclear Overhauser effect uses spin relaxation to enhance resonance line intensities. Electron spin resonance studies molecules with unpaired electrons by observing the magnetic fields at which they come into resonance with monochromatic radiation, measuring their hyperfine structure.???