Chapter 6: Thermochemistry: Energy Flow and Chemical Change thermodynamics - study of e & transformations 6.

.1: Forms of Energy & Interconversion PE KE (work & heat) o system - part of universe we're focusing on o surroundings - everything else that's not the system; but really just the stuff that may affect system internal e (E) = PE + KE o E = Efinal - Einitial = Eproducts - Ereactants o change in e of system also has equal&opposite change in e of surroundings releasing e (e to surroundings) so E < 0 bc Efinal < Einitial absorbing e (e from surroundings) so E > 0 bc Efinal > Einitial heat&work transfers: o heat (q) - e transfer bc diff. in temp. between system&surroundings o work (w) - e transfer when object moved by a force o total change in system's internal e is sum of e transferred as heat&work E = q + w e transfer into system is + bc has more e e transfer out of system is - bc less e o heat transfer only: heat flowing out of system, q is -, E is -; heat flowing into system, q is +, E is + o work transfer only: work done by system, w is -, E is -; work done on system, w is +, E is + law of e conservation o e changes but not created/destroyed; e conserved: total e of system + surroundings remain constant o Euniverse = Esystem + Esurroudnings = 0 units of e o joule (J): 1J = 1kg*m2/s2 o calorie (cal): 1cal = 4.184J state functions & path independence of e change o state function - property dependent only current state of system (NOT path it takes to reach state) o E depends on difference between final&initial states 6.2: Enthalpy - Chemical Change @ Constant Pressure pressure-volume work (PV work) - mechanical work done when volume of system changes in presence of external pressure (P) o open flask, system of expanding gas does PV work on surroundings so w = -PE o @constant pressure, enthalphy (H) H = E + PV change in enthalpy: change in internal e + product of pressure (constant) and change in volume H = E +PV combining E = q + w & w = -PV gives E = q - PV if constant pressure = qp then qp = E + PV = H change in enthalpy = heat absorbed/released @ constant pressure endothermic/exothermic o exothermic - releases heat & decreases enthalpy of system Hproducts < Hreactants so H < 0 o endothermic - absorbs heat & increases enthalpy of system Hproducts > Hreactants so H > 0 6.3: Calorimetry: Measuring Heat of Chemic/Physical Change q = constant * T

heat capacity = q/T; unit: J/K specific heat capacity: c = q/(mass * T); q = c * mass * T; unit: J/g*K molar heat capacity: C = q/(mol * T); unit: J/(mol*K) two major types of calorimetry o constant-pressure calorimetry - coffee-cup calorimeter; usu. finds heat of aqueous reaction or heat accompanying dissolving of a salt, but can also find specific heat capacity of a solid csolid = - (cH20 * massH20 * TH20)/(masssolid * Tsolid) o constant-volume calorimetry - bomb calorimeter; usu. measure heat of combustion reactions & heat capacity of entire calorimeter can be determined E = q + w = qv + 0 = qv

6.4: Stoichiometry of Thermochemical Equations thermochemical equation - balanced equation w/ enthalpy change (H) o sign - H's sign depends on if exo(-)/endothermic (+) o magnitude - H's magnitude is proportional to amount of substance balancing coefficients thermochemical equivalence 6.5: Hess's Law: Finding H of Any RXN Hess's Law - enthalpy change of overall process is sum of enthalpy changes of individual steps; is a state function o Hoverall = H1 + H2 + . . . + Hn o manipulate equations of reactions and H values to match substances in target equation to find unknown H 6.6: Standard Enthalpies of Reaction (Horxn) standard states:

Chapter 7: Quantum Theory and Atomic Structure 7.1: The Nature of Light electromagnetic radiation (electromagnetic e & radiant e) - consists of e propagated by electric & magnetic fields that increase&decrease in intensity as they move through space wave nature of light o frequency (v) - # of cycles/second; unit: 1/second or s-1 or hertz or Hz o wavelength () - distance btw any pt on wave & corresponding pt on next crest/trough; unit: nm (10-9m) or (10-10m) o speed - distance moved/unit time; unit: m/s. speed = frequency * wavelength = v * o amplitude - height of crest/depth of trough electromagnetic spectrum classical distinction btw e & matter particle nature of light 7.2: Atomic Spectra 7.3: The Wave-Particle Duality of Matter of Energy

7.4: Quantum-Mechanical Model of the Atom Chapter 8: Electron Configuration and Chemical Periodicity periodic law - arranged by atomic mass; nowadays arranged by atomic number electron configuration - distribution of electrons within lvls&sublvls of its atoms 8.1: Characteristics of Many-Electron Atoms Schrodinger equation gives good approximate solutions for e lvls of many-electron atoms spin quantum number (ms) - 1/2 o each e- in atom described by 4 quantum #s: 3 describe orbital, 4th describes spin Name Symbol Permitted Values Property Principal n Positive integers (1, 2, 3, etc.) Orbital e (size) Angular l Integers 0 to n-1 Orbital shape (l values 0, 1, 2, 3 correspond momentum to s, p, d, f) Magnetic ml Integers from -l to 0 to +l Orbital orientation Spin ms +1/2 or -1/2 Direction of e- spin exclusion principle - no 2 e- in same atom can have same 4 quantum #s o atomic orbital can hold max. of 2 e- & must have opposite spins electrostatic effects & e-lvl splitting o electrostatic effects - attraction btw opposite charges & repulsion of like charges o splitting of e lvls into sublvls of differing energies: e of orbital in many-e- atom depends mostly on nvalue (size) & a bit on l-value (shape) o 8.2: The Quantum-Mechanical Model and the Periodic Table aufbau principle 8.3: Trends in Three Atomic Properties atomic properties directly influenced by e- configuration&nuclear charge o atomic size o ionization e o e- affinity atomic size - how closely an atom lies next to another (can measure distance between atomic nuclei and divide in half) o metallic radius - usu. metals; 1/2 shortest distance btw nuclei of adjacent, individual atoms in a crystal o covalent radius - usu. molecules/nonmetals; 1/2 shortest distance btw nuclei of bonded atoms o n (principal quantum #) increases, atomic size increases (probability outer e- spend time farther from nucleus) o Zeff (effective nuclear charge) increases, atomic size decreases (outer e- pulled closer to nucleus) o go down 8.4: Atomic Properties and Chemical Reactivity

Explain how Bohr accounted for line spectra. Include the relationship he developed for hydrogen and define all variables.

Bohr postulated that there were orbits of distinct energy that electrons could occupy. When electrons passed from one orbit to another, a photon is absorbed or emitted of equal energy to the energy difference between orbits. Photons (light) pass through prisms, separate into a few lines of different colors (line spectra). If the transition of an electron from one state to another involves the emission of energy, the initial principal quantum number is greater than the final principal quantum state and the energy change is negative. An electron in the n = &infin; state is not bound and possess an energy of 0J. Orbitals differ in size, shape, spatial orientation, but not spin. The spin quantum # (ms) only describes the electron in the orbital, no the orbital. When asked about the energy of a photon that is emitted rather than electron, remember that the energy of a photon is ALWAYS POSITIVE. The wavelength associated with an electron can be found by the equations: = h/mu or = h/p where p = mu (momentum * speed) ground state - lowest energy that an electron can posses; n = 1 lymer series (uv) - transitions for which the final state is the ground state (nf = 1) heisenberg uncertainty principle - reduction in the uncertainty in the measurement of one variable x results in an increase in the uncertainty of related variable p. (xp >= h/4) ^2 (aware of wave function) - probability density of the position of an electron; multiplication of a volume by this function will give the probability of finding the electron within that volume orbital - region of space around the nucleus of an atom that will most liely contain the electron for a given energy state balmer series - transition for which the final state is the first excited state (nf = 2) paschen series: nf = 3 (IR) brackett series: nf = 4 (IR) Pauli Exclusion Principle - no two electrons within an atom may have same 4 quantum numbers Aufbau Principle - electron will occupy lowest orbital that they can enter Hunds Rule - electrons in a subshell containing more than one orbital will spread out among orbitals to have as many electrons with spin in the same direction as possible Zeff - effective nuclear charge; ability of other electrons to less the nuclear attraction for an outer electron diamagnetic - quality of being repelled by a magnetic field paramagnetic - quality of being attracted by a magnetic field degenerate orbitals - orbitals within a species that have identical energies electron affinity - energy change accompanying the addition of one mole of electrons to one mole of gaseous atoms or ions electronegativity - measure of ability of atom in molecule to attract shared electrons in a chemical bond

Provide complete electron configuration of 2 transition metals required to memorize: Cr: 1s^2 2s^2 2p^6 3s^2 3p^6 4s^1 3d^5 Cu: 1s^2 2s^2 2p^6 3s^23 p^64 s^1 3d^10 Why does these exceptions exist? Half-filled orbitals are exceptionally stable. Electrons arrange themselves such that their energy is minimized. Arrange in order of increasing radius: Mg, Ca, Ca2+, S Ca2+, S, Mg, Ca Arrange in order of increasing ionization energy: Ar, K+, Se, S Se, S, Ar, S+ Arrange in order of increasing electronegativity: F, Ba, Cs, Sr Cs, Ba, Sr, F Find all correct orbital designations: 1p, 7d, 9s, 3f, 4f, 2d 7d, 9s, 4f What is the maximum number of electrons in an atom that can have the quantum numbers n=3 and l=2? 4(2)+2 = 10 electrons