Mole-Volume Hypothesis: Avagadro hypothesized that equal volume of gases of the same temperature and pressure contain equal number of particles. At ST P, 1 mol (6.02*1023 particles) of any gas occupies a volume of 22.4 L (Molar Volume) At STP, Volume of gas = (#mol) * (22.4 L/mol) At STP, molar mass = (density) * (molar volume) Mixture of Gases Air- 78% nitrogen, 21% oxygen, 0.9% argon, 0.03% CO2 (% by volume) Partial Pressure- pressure due to any individual component in a gas mixture Total Pressure- sum of partial pressure Ptotal = Pa + Pb + Pc … Pa = Xa Ptotal Xa = (moles of a) / (total # moles of gas) “mole fraction of a gas” Diffusion / Effusion Diffusion- tendency of molecules to move toward areas of low concentration until the concentration is uniform. Effusion- gas escapes through a tiny hole in a container (lower molar mass effuses faster) Graham’s Law of Effusion- the rate of effusion is inversely proportional to the square root of a gas’s molar mass. Ex) (RateA / RateB) = Square root of (molar mass B / molar mass A) Real Gases At high pressures or low temperatures, gases don’t behave ideally, so we use the Vander waals Equattion: (P + a(n/V)2) ( V-nb ) = nRT Isaac Newton- particles Waves Amplitude- The maximum distance from equilibrium Wavelength (“lambda” )- distance from point on wave to identical point on next wave Frequency (“nu” )- number of waves to pass a point in one second (unit: Hertz, Hz) 1 Hz = (1/sec) = S-1 C = C= the speed of light = (frequency) X (wavelength) = 3* 108 m/s Dual Nature of LightActs as waves + particles (photons) Atomic Spectra: Pass electric current through a gas in a tube This energizes electros of atoms, The electrons absorb energy and move to higher energy levels, Then the electrons lose energy and come back, and come back to original position, and emit light Ground State- lowest possible energy state of e- in atom E = quantum of energy E = h h = Planck’s constant = 6.63 * 10-34 J*S E = (hC) / Bohr Model (1913) Neils Bohr E- only found in orbits around nucleus each orbit has a fixed amount of energy celled “energy level” Like a ladder: Lowest rung energy level closest to nucleus (lowest energy) Person climbs from rung to rung e- travel from energy level to another To move from energy level to enegy level, e- must gain/lose certain amount of energy Quantum of energy- amount of energy required to move an e- from one energy level to another Higher energy levels are closer together Schrodinger (1887- 1961): Atom: probability of finding an electron within a certain region of space surrounding the nucleus is represented (in his model, the Quantum Mechanical Model,) as a fuzzy cloud. Cloud is more dense where there is greater probability of finding eAtomic Orbitals: regions of space with highest probability of finding e- in an energy level Energy levels represented by principle quantum numbers: n = 1, 2, 3, 4, … Energy sublevels: correspond to orbitals of different shape describing where e- are likely to be found Sublevels: Represented by letters ( S, P, D, F) Labeled by angular momentum numbers (L). L Sublevel 0 S (spherical) 1 p (dumbbell shaped) 2 d 3 f Principal energy # of sublevels Type of sublevels # of e- N=1 1 1s 2 N=2 2 2s, 2p 8 N=3 3 3s, 3p, 3d 18 N=4 4 4s, 4p, 4d, 4f 32 level 2n2 = maximum number of e- an energy level can hold Magnetic Quantum Number (Ml)- specifies orientation of orbital Heisenberg Uncertainty Principle- impossible to know both the velocity and position of e- at the same time (may know one, but never both). Electron Configuration- way in which electrons are arranged in orbitals around the nucleus Rules for writing e- configurations: Aufbau Principle- e- occupy orbitals of lowest energy level 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 5d, 4f, 6p Puali Exclusion Principle- to occupy the same orbital, two electrons must have opposite spins. Hund’s Rule- electrons occupy orbitals of the same energy in a way that makes the number of electrons with the same spin direction as large as possible. *Exceptions to the Aufbau Principle* Cr (column)- 1s2 … 4s1 3d5 Cu (column)- 1s2 … 4s1 3d10 Atomic Trends Atomic Radius One half of he distance between the nuclei of 2 atoms of the same element when atoms are joined Measured in picometers ( (pm) * 10 -12) Ionic Size Size of cation < size of atom Size of anion > size of atom Ionic Size decreases from left to right, but get larger with first anion, then continue to decrease. As you go down the periodic table, and add energy levels, the ionic size gets bigger. Ionization Energy- energy required to remove an e- from atom. Decreases as you go down the periodic table. Increases as you go across. Isoelectronic = same # of e- Ionic Compound: Crystalline solids at room temperature Conduct electric current when melted or dissolved in water Metallic Bonding: Metals: made of closely packed cations Valence electrons of metal atoms can be modeled as a sea of ee- are mobile Alloys: mixture of two or more elements (brass- copper + zinc) Covalent Bonding: Lower melting and boiling points than ionic bonded compounds Weaker than ionic bonds Bond two non-metals Molecular Ionic Collection of molecules Array of cations and anions Rules for Drawing Lewis Structures: Count number of valence electrons in compound Use dashes between central atom and surrounding atoms Draw lone pairs on surrounding atoms, then on central Check that every atom has eight and that used correct number of electrons Resonance- actual bonding is a hybrid, or mixture, of the extremes represented by the resonance structures. Exceptions to Octet Rule (for central atom only!): Odd number of valence electrons: NO2 (odd number of electrons) SO3Expanded Ocktet: PCl5 (more than four bonds each) Se6 ICl5 ***********End Of Material For Test********************** VSEPR Theory- Valence Shell Electron Pair Repulsion Explains 3D shape of molecules Repulsion between electron pairs causes molecular shapes to adjust so that valence electron pairs stay as far apart as possible. Bent Shape (because of the two lone pairs) H2O Linear CO2 (O=C=O) Polar Bonds + Molecules Non-polar covalent bond: Diatomic elements Polar Covalent Bond: Between atoms where electrons are shared unequally. The more EN an atom has, the more an atom attracts electrons more strongly and gains a slightly negative charge Less EN an atom gains slightly positive charge Delta EN Type of Bond EX 0 - 0.4 Non-polar H2 0.4 - 1.0 Moderately polar HCl 1.0 -2.0 Very polar HF 2.0 – and higher ionic NaCl Polar Molecule- one end is slightly positive, and one end is slightly negative (EX H2O). (Dipole). Non-Polar Molecule- bond polarities cancel each other out (symmetrical structure). Classifying Reactions: Combination Reaction- when 2 or more substances react to produce 1 new substance. Decomposition Reaction- 1 2 substances Single Replacement- one element replaces a second element in a compound Double Replacement- exchange of cations between two compounds Combustion- element/compound reacts with O2, usually products are CO2 + H2O Density Solid Liquid Gas highest medium lowest Not shape Not Takes shape, not Takes shape + volume volume volume Attractions Between Molecules Inter molecular forces- weaker than covalent or ionic bonds (in order weakest strongest) Van der waals (London Dispersion Forces) Weakest Caused by motion of electrons Occur between non-polar and polar molecules occur in ALL compounds Dipole-Dipole forces Between two polar molecules Slightly negative region of one polar molecule is attracted to the slightly positive region of another polar molecule Hydrogen Bonds Attractive forces in which a hydrogen atom covalently bonded to a highly electro negative atom (N, O, F) Properties of Water Surface Tension- resistance of a liquid to an increase in its surface area energy required to overcome the intermolecular forces in liquid. Viscosity- resistance to flow Capillary Reaction- spontaneous rising of a liquid in narrow tube, two things responsible for this: CohesiveAdhesive- ∆Hfus - molar heat of fusion Heat absorbed by 1 mol of a solid as it melts to liquid at melting point Water: 6.01 KJ/mol ∆Hsolid = - ∆Hfus How many grams of ide at 00 C will melt if 2.25 KJ of heat is added? [2.25 KJ] / [6.01 (KJ/ mol)] = (.37 mol) * (18) = 6.7g ice ∆Hvap -molar heat of vaporization = amount of heat to vaporize 1 mol of a liquid to vapor at boiling point ∆Hvap = -∆Hcond Water: 40.7 KJ/mol Heat: q Measured in joules or calories 4.184 J = 1 cal Heat Capacity- amount of heat required to increase temperature of a substance by 10 C Specific Heat (c)- amount of heat required to increase temperature of 1 g of a substance by 10 C J / q 0C Cal / g0 C Water 4.184 1 Ice 2.1 .5 Iron .46 .11 q = mc∆T q: heat absorbed/ released c: specific heat ∆T: chance in temp (TF – Ti) Heat required to raise 27 g H2O from 10 to 90 q= (27g) * (4.184 J Vaporization- liquid vapor Evaporation- when vaporization occurs at surface of liquid that is not boiling Solubility= maximum quantity of a substance that will dissolve in a certain quantity of water at a specified temperature. Unsaturated Solution- contains less dissolved solute than the amount that the solvent can normally hold at that temperature. Supersaturated Solution- solution that contains more solute than could be dissolved at that temp Molality (m)- (mol Solute) / (Kg Solvent) Mole Fraction- (mol Solute) / (total mol solution) Mass percent- [(mass Solute) / (mass Solution)] * 100 Colligative Properties: Properties that depend only on amount of solute, and NOT on their identity The three properties (we’ll discuss) are… Vapor pressure lowering- solution that has lower VP than its pure solvent Boiling point elevation- difference in temperature between boiling point of solution and boiling point of pure solvent. ∆Tb = Kb * m Kb: molal boiling point elevation constant (water: .512 oC / m) m: molality Freezing point depression- ∆TF = KF * m KF: molal freezing pt depression constant (water: 1.86 oC/m) Suspension- mixture that particles begin to settle out upon standing Greater than 1000 nm diameter Colloid- particles 1nm – 1000 nm Acid Base Sour taste Dissolve metal Litmus Bitter Feel slippery Blue NaOH, turns red HCl, H2SO4, HNO3 NH3 Acid Arrhenius Base Produce H+ in solutions Produces OH- in solutions Bronsted Lowry H+ donor H+ acceptor * Lewis Accept e- pair Donates e- pair NH4+ + OH- NH3 (acid (base (conjugate H+ donor) H+ acceptor) base) + H2O (conjugate acid) Pure water [H+] = 1 * 10-7 molar [OH-] = 1 * 10-7 [H+] * [OH-] = 1 * 10-14 = KW (Ion Constant Product for H2O [H+] > [OH-] Acidic Ex) [H+] = 1 * 10-5 [OH-]= ?? 1 * 10-9 Acidic pH scale: pH = -Log [H+] (log 10 =1, log 100 = 2 Log X = Y, 10Y = X) Ranges from 1 (most acidic) to 14 (most basic) pOH = -Log [OH-] pH + pOH = 14 Log Scale: pH = -Log [H+] Given pH, find H+ Method 1 Method 2 pH = -LogX -pH = LogX Log-1(- pH = -LogX -pH = LogX 10-pH = X pH) = X Acid base indicator Its acid form and base form have different color in solution Strength of acid + bases · Strong acids – completely ionize in solution o Ex. HCl, H2SO4, HNO3 § HCl + H2O H3O+ + Cl- - 100 % ionized · Weak acid – partially ionized in solution o Ex. Acetic acid § CH3COOH + H2O H3O+ + CH3COO- (partial ionization – can tell by double arrow) · Strong Base o Ex. Mg(OH)2 , Ca(OH)2 · Weak base o Ex. NH3 · Concentration / strength o Concentration § How much acid is dissolved in solution § Concentrated/ dilute o Strength § Extend of ionization ú Strong weak Neutralization reaction · Acid +Base à Salt + Water o Mix solution of strong acid and strong base and we get a neutral solution results o Salt = compound consisting of anion from aid and cation from base · Ex. HCl + NaOH à H2O + NaCl · Ex. H2SO4 + 2KOH à 2H2O + K2SO4 · Q: How many moles of potassium hydroxide are needed to completely neutralize 1.56 mol of phosphoric acid? o H3PO4 + 3KOH à 3H2O + K3PO4 § 1.56 mol x (3 KOH / 1 H3PO4) Titration · The process of adding a known amount of solution of known concentration to determine the concentration of another solution · Standard solution (know concentration of) we kept titrating until neutralization occurred, which is called the end point · Ex. a 25 ml solution of H2SO4 is neutralized by adding 18 ml of 1 M NaOH what is concentration H2SO4? o H2SO4 + 2NaOH à 2H2O + Na2SO4 § 1M = x mol / .018 L ú .018 mol NaOH ú .009 mol H2SO4 ú .009 mol / .025 L = .36 M Buffer: A solution in which pH remains relatively the same. Made of weak acid and its salt OR a weak base and its salt Ex) CH3OOH (acetic acid) + NaCH3OO (salt) = acid buffer Thermochemistry: Potential energy- energy that is stored in chemical bonds Kinetic Energy- energy of motion Heat transfer or work Heat Reaction absorbs heat endothermic Reaction releases heat exothermic Work = -P∆V At a constant P… If… ∆V > 0 W<0 Work is being done by system And if… ∆V < 0 W>0 Work is being done on the system ∆E = q + W + - q Endothermic Exothermic W Done on system By system E Endogenic Exergenic Ex) q= +214 KJ W= +110 KJ ∆E = 214 +110 = 324 KJ 2NaHCO3 Na2CO3 + H2O ∆H = 129 KJ Calculate heat required to decompose 2.24 mol NaHCO3 * (129 KJ / 2 mol) = 144.5 KJ Heat of Combustionheat of reaction for complete burning of one mole of substance Ex) CH4 + 2O2 CO2 + H2O (∆H = 890 KJ) Hess’s Law: 2P + 5Cl2 2PCl5 ∆H = ? Given: PCl3 + Cl2 PCl5 ∆H = -88kJ 2PCl3 2P + 3Cl2 ∆H = 574 kJ flip the second reaction and get 2P + 3Cl2 2PCl3 ∆H = -574 multiply first reaction by 2 and get 2PCl3 + 2Cl2 2PCl5 ∆H = -176 combine them and get 2P + 5Cl2 2PCl5 ∆H = -750 Standard Heats of formation: change in enthalpy that accompanies the formation of one mole of a compound from its elements ∆HFo = 0 for free elements and diatomics. ∆Hº (heat of reaction) = ∑ (np∆Hfº, products) - ∑(nr∆Hfº, reactants) Gibbs Free Energy- energy available to do work Spontaneous Reaction Occurs naturally, releases free energy If ∆G is negative, the reaction is spontaneous Non-spontaneous Reaction Doesn’t occur naturally Requires energy input If ∆G is positive, the reaction is Non-spontaneous Entropy (∆S)- measure of disorder (randomness) of a system Law of Disorder- natural tendency of system is in direction of more disorder. Increase in S favors spontaneous reaction For a give substance, the S solid < S liquid < S gas S increases when divide substance In a reaction: when # mol product > # mol reactant, S increased When Temperature increases, S increases Gibbs Helneholtz Equation: ∆G = ∆H – T∆S *T- in Kelvin If ∆G is negative, the reaction is spontaneous If ∆G is positive, the reaction is Non-spontaneous Rate: Measure of the speed of any change that occurs in any interval of time Usually (∆ [ ]) / Time Activation Energy: Minimum energy that colliding particles must obtain in order to react Factors that affect Rate: Temperature- If temperature increases, rate increases Particle Size- If you have smaller particle, rate increases Concentration- If concentration increases, rate increases Catalyst Speeds up reaction without being used Lowers activation energy Rate Law- expression for rate of reaction in terms of concentration of reactants Rate Constant (K)- Stresses: *** solids cannot change concentration!!! Temp Pressure, volume Concentration Concentration- Changing the concentration of any reactant or product disturbs the equilibrium and the system adjusts to minimize the effect of change. H2CO3 CO2 + H2O At equilibrium, I add H2CO3, Forward reaction favored, Shifts to the right At equilibrium, remove H2O, shift to the right Changing the cncetration of any reactant or product disturbs the equilibrium and the system adjusts to minimize the effect of change. Temperature- increasing the temperature causes equilibrium to shift in the direction that absorbs heat. 2SO2 + O2 2SO3 + Heat, ∆H = -X (exothermic) If Temperature goes up, reaction shifts to the left Pressure- If we increase pressure, system wants to decrease it, so it shifts in direction of fewer moles of gas. N2 (g) + 3H2 (g) 2NH3 (g) If pressure goes up, reaction goes to the right If pressure goes down, reaction goes to the left VolumeIf volume goes up, pressure goes down If Volume goes down, pressure goes up Equilibrium Constant (Keq) Ratio of product concentrations to reactant concentration, with each concentration raised to a power equal to the number of moles of substance in balanced equation. Keq > 1, products favored over reactants Keq < 1, reactants are favored Redox: Oxidation- loss of eReduction- gain of e- or reduction of charge Ex) Mg + S Mg2+ + S2Mg Mg2+ + 2e- (oxidation) S + 2e- S2- (reduction) Mg: reducing agent S: oxidizing agent Silver nitrate reacts with copper to form copper (II) nitrate and silver. What is oxidized? What is reduced Identify oxidizing + reducing agents 2AgNO3 + Cu CuNO3 + 2Ag Cu is oxidized Ag is reduced Oxidizing agent = Ag Reducing agent = Cu Oxidation #: Positive or negative number assigned to an element to indicate its degree of oxidation or reduction Ex) Charge: S2- Oxidation #: -2 Rules for assigning Oxidation #s: Oxidation number of monatomic ion is equal to its charge Ex) Br- : -1, Fe3+ : +3 Oxidation number of hydrogen in a compound is +1, except when in metal hydrides, such as NaH, where it’s -1 Oxidation number of oxygen in a compound is -2, except in peroxides such as H2O2, where it is -1 Oxidation number of an uncombined element is zero Ex) Cu, N2 For a neutral compound, the sum of the oxidation numbers is zero For polyatomic ions, the sum of the oxidation numbers is the charge of the ion When calculating oxidation numbers in molecules with three or more elements, find the oxidations numbers of the elements from the outside in. 2AgNO3 + Cu (Ox agent) Cu(NO3)2 + 2Ag (Red agent) Balancing Redox Reactions in Acidic Solution: Use oxidation numbers to write out half reactions Ex) MnO4- + Fe2+ Fe3+ + Mn2+ Mn = +7, O = -2, Fe (#1) = 2+, Fe (#2) = 3+, Mn (#2) = 2+ Half Reactions: MnO4- Mn2+ Fe2+ Fe3+ Balance each half reaction: Balance all elements except H and O Balance O by adding H2O MnO4- Mn2+ + 4H2O Balance H by adding H+ 8H+ + MnO4- Mn2+ + 4H2O Balance each reaction’s charge by adding e5e- + 8H+ + MnO4- Mn2+ + 4H2O Fe2+ Fe3+ + 1eMultiply Half reactions so that they have equal number of eFe2+ 5Fe3+ + 5eAdd half reaction and cancel/simplify Check that charges and elements are balanced