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# Introduction Some useful constants in thermodynamics: 1 eV = 9.6522E4 J/mol k Boltzmann's constant = 1.38E-23 J/K volume: 1 cm3 = 0.

0.1 kJ/kbar = 0.1 J/bar mole: 1 mole of a substance contains Avogadro's number (N = 6.02E23) of molecule s. Abbreviated as 'mol'. atomic weights are based around the definition that 12C is exactly 12 g/mol R gas constant = Nk = 8.314 J mol-1 K-1 Units of Temperature: Degrees Celsius and Kelvin The Celsius scale is based on defining 0 C as the freezing point of water and 100C as the boiling point. The Kelvin scale is based on defining 0 K, "absolute zero," as the temperature a t zero pressure where the volumes of all gases is zero--this turns out to be -27 3.15 C. This definition means that the freezing temperature of water is 273.15 K. All thermodynamic calculations are done in Kelvin! kilo and kelvin: write k for 1000's and K for kelvin. Never write K. Units of Energy: Joules and Calories Joules and calories and kilocalories: A calorie is defined as the amount of ener gy required to raise the temperature of 1 g of water from 14.5 to 15.5C at 1 atm. 4.184 J = 1 cal; all food 'calories' are really kcal. Many times it is easiest to solve equations or problems by conducting "dimension al analysis," which just means using the same units throughout an equation, seei ng that both sides of an equation contain balanced units, and that the answer is cast in terms of units that you want. As an example, consider the difference be tween temperature (units of K) and heat (units of J). Two bodies may have the sa me temperature, but contain different amounts of heat; likewise, two bodies may contain the same heat, but be at different temperatures. The quantity that links these two variables must have units of J/K or K/J. In fact, the heat capacity C describes the amount of heat dQ involved in changing one mole of a substance by a given temperature increment dT: dQ = CdT The heat capacity C is then C = dQ/dT and must have units of J K-1 mol-1. (The specific heat is essentially the same n umber, but is expressed per gram rather than per mole.) Don't forget significant digits. 1*2=2; 1.1*2=2; 1.1*2.0=2.2; 1.0*2.0=2.0 Why Thermodynamics? Think about some everyday experiences you have with chemical reactions. Your ability to melt and refreeze ice shows you that H2O has two phases and that the reaction transforming one to the other is reversible--apparently the crysta llization of ice requires removing some heat. Frying an egg is an example of an irreversible reaction. If you dissolve halite in water you can tell that the NaCl is still present in s ome form by tasting the water. Why does the NaCl dissolve? Does it give off heat ? Does it require energy? How is it that diamond, a high-pressure form of C, can coexist with the low pres sure form, graphite, at Earth's surface? Do diamond and graphite both have the s ame energy? If you burn graphite and diamond, which gives you more energy? When dynamite explodes, why does it change into a rapidly expanding gas, which p rovides the energy release, plus a few solids? Chemical thermodynamics provides us with a means of answering these questions an d more. A Few Definitions A system is any part of the universe we choose to consider. Matter and energy can flow in or out of an open system but only energy can be ad ded to or subtracted from a closed system. An isolated system is one in which ma

tter and energy are conserved. A phase is a homogeneous body of matter. The components of a system are defined by a set of chemical formula used to describe the system. The phase rule: F + P = C + 2. Extensive parameters are proportional to mass (e.g., V, mass, energy). Intensive parameters are independent of mass (e.g., P, T); these are the "degree s of freedom" F contained in the phase rule. Thermodynamics: Power and Limitations Thermodynamics allows you to predict how chemical systems should behave from a s upra-atomic "black-box" level--it says nothing about how chemical systems will b ehave. Thermodynamics also pertains to the state of a system, and says nothing a bout the path taken by the system in changing from one state to another. Chemical Reactions and Equations How to write chemical reactions; stoichiometry. Mass and charge balance: e.g., 2Fe3+ + 3H2O = Fe2O3 + 6H+ Reaction-Produced Change in Mass, Density, Volume The change in volume rV of a reaction is the volume V of the products minus the volume of the reactants: rV = Vproducts - Vreactants Thus, if the products are smaller than the reactants, rV < 0. In a generalized reaction such as aA + bB ... = cC + dD... rV = cVC + dVD - aVA - bVB This sort of additive relationship is true for other state variables and is usua lly stated as r i i where i are the stoichiometric coefficients, positive for products and negative for reactants. What Actually Drives Reactions? Is it Energy? Can We Just Calculate or Measure t he Energy Difference of Reactants and Products and Know Which Way the Reaction W ill Go? For many years people felt that chemical reactions occurred because the reactant s had some kind of energy to give up (i.e., use to do work)--and that therefore the energy of the products would be less than the energy of the reactants. Howev er, we all know that when ice melts it consumes rather than releases heat, so th ere must be more to the story behind why chemical reactions occur. Le Chatelier's Principle "If a change is made to a system, the system will respond so as to absorb the fo rce causing the change." Equilibrium A mechanical analogy for chemical change is that of a ball rolling down a slope with multiple valleys; we explain the ball's behavior by saying that mechanical systems have a tendency to reduce their potential energy. At equilibrium none of the properties of a system change with time. A system at equilibrium returns to equilibrium if disturbed. "Stable" describes a system or phase in its lowest energy state. "Metastable" describes a system or phase in any other energy state. The figure above shows the mechanical analogy for H2O at -5C and + 5C and 1 atm. L eft: at -5C, solid H2O has the lowest possible energy state. Right: at +5C, liquid H2O has the lowest possible energy state. When solid H2O is actually present at +5C, the difference between the free energy of solid H2O and liquid H2O is avail able to drive the reaction to form the stable solid H2O phase, and the reaction will go to completion if kinetically possible.