Principles of Thermochemistry - Study of the energy changes that accompany chemical and physical processes - First Law of Thermodynamics:

States energy is never created or destroyed, but simply changed from 1 form to another Systems and Processes - Systems: Matter being observed o Isolated: System cannot exchange energy (heat and work) or matter with the surroundings; e.g insulated bomb calorimeter o Closed: System can exchange energy (heat and work) but not matter with the surroundings; e.g Steam radiator o Open: System can exchange both energy and matter with the surroundings; e.g boiling water - Process: Associated with property that is constant throughout process o Isothermal: Systems temperature is constant o Adiabatic: No heat is exchanged between system and environment o Isobaric: Pressure of the system is constant - Process can be spontaneous or non spontaneous o Can also determine if reaction will be temperature dependent (spontaneous at 1 temperature, then non spontaneous at the next) Look at G, H or S o Spontaneous reactions usually still need a spark to overcome the activation energy States and State Functions - Pathway dependent are work (W) and heat (Q) - State functions o Temperature (T), Pressure (P), Volume (V), density (roe p), internal energy (E/U), enthalpy (H), entropy (S) and Gibbs (G) o Independent of path taken - Standard Conditions (since equilibrium states different at different temperatures: 298K and 1 atm: Use for thermodynamic problems - Different from Standard Temperature and Pressure: 273K and 1 atm: Use for ideal gas calculations - Standard state: Most stable form of substance - Standard entropy/ enthalpy/ free energy: Defined by Ho and so forth

Heat Temperature (T) refers to average kinetic energy of the particles Heat (Q) is the transfer of energy from one substances to another as a result of their difference in temperature o 0th Law Thermodynamics: Objects are in thermal equilibrium only when their temperatures are equal 1st Law Thermodynamcis: Change in total internal energy (U) of system is equal to amount of heat transferred subtract from amount of work done by system. o U = Q-W (Measured in J) Constant Pressure Calorimetry: Styrofoam cup Constant Volume Calorimetry: Bomb Calorimeter o Since no change in volume, W=PV = 0 o Since isolated system, no heat exchanged, Qcal = 0 o Although no heat exchanged between system and surrounding, heat is exchanged between system and steel, allow to calculate heat of combustion q (heat) = m (mass) * c (specific heat) T

Enthalpy - Enthalpy change of a reaction Hrxn= Hproducts - Hreactants o Positive Hrxn = endothermic process Negative Hrxn = exothermic process o Not possible to measure enthalpy directly, only change Standard Heat of Formation - Standard Enthalpy of formation: Hof = enthalpy change that would occur if 1 mole of a compound in its standard state were formed directly from its elements in their respective standard states Standard Heat of Reaction - Hrxn if it were carried out under standard conditions Hess Law - Since enthalpy is a state function, Hesss Law states enthalpy changes of reactions are additive - Therefore Horxn = Sum (Hof products) sum (Hof reactants) - Applies to all other state functions, including entropy and Gibbs Bond Dissociation Energy - Average energy that is required to break a particular type of bond between atoms in gas phase - Hrxn= Sum (Hbonds broken) + Sum (Hbonds formed) o Total energy absorbed total energy released o Note that bond breaking is (-), bond forming is (+) Heat of Combustion

Entropy - Second Law of Thermodynamics: Energy spontaneously disperse if it is no hindered from doing so - Measure of spontaneous dispersal of energy at a specific temperature o How much energy spread out o How widely spread out energy becomes - S = Qrev/T o S = entropy, Qrev = heat gained or lost in reversible process, T = temp. - Usually, spontaneous things get more dispersed, work needed to localize it - Suniverse = Ssystem + Ssurrounding > 0 - S= Sfinal - Sinitial - Srxn = Sum (Sproducts) Sum (Sreactants) Gibbs Free Energy - G = H TS - Free energy is maximum amount of energy released by a process, occurring at constant temperature and pressure available for useful work - G (-), reaction spontaneous - G (+), reaction nonspontaneous - G (0), reaction in equilibrium H S Outcome + Spont. All T + Non- spont all T + + Spont only at high T Spont only at low T - Rate of reaction depends on Ea, therefore spontaneous reactions may be fast, but also may be slow - There might be 2 types of product formed in a reaction, and their stability is measured by change in Gibbs free energy o Kinetic Product Produced under kinetic control because of lower Ea o Thermodynamic Product Will be formed more over time because of lower free energy, and hence is more stable Standard Gibbs Free Energy - Gorxn = Sum (Gof products) Sum (Gof reactants) Free Energy, Keq and Q - Gorxn = - RTlnKeq - Grxn = Gorxn + RTlnQ - Grxn = RTln(Q/Keq) o Therefore if Q/Keq < 1, Q< Keq, ln of that will be negative, spontaneous o If Q/Keq > 1, Q > Keq, ln positive, spontaneous in reverse direction o If 1, reaction at equilibrium