CH353 - Physical Chemistry I
Spring 2013 Unique 52575

Lecture Summary, 30 January 2013


A Bit More on Paths:  The last important pathway we will talk about is when q = 0.  This is called an adiabatic path.  By setting deltaU = w, we derived the following equation:

   Cv/nR ln (Tf/Ti) = ln (Vi/Vf)

We then manipulated this equation further to put it in a form that is easier to solve plug-and-chug style, but this is the important result.

Thermochemistry:  We then went on and discussed the topic of thermochemistry, the science of the flow of heat due to chemical transformations:

   Reactant --> Product +/- heat

In chemical thermodynamics we almost always are interested in energies at constant pressure, therefore in reaction enthalpies of a system.  Because enthalpy is a state function, by defining a standard state of P = 1 bar and T = 298 K, we can tabulate enthalpies of formation for any substance under that standard, then use that information to calculate a reaction enthalpy under any set of circumstances, even those far away from the standard state. 
 
Second Law of Thermodynamics: We have spent quite a bit of time developing the first law of thermodynamics, which we have expressed as energy = heat + work.  We have found that we can find heat, work, internal energies, and enthalpies for a variety of different systems and different paths.  But clearly we are missing something.  For example, an an isothermal expansion of an ideal gas, deltaU = 0, but under some conditions, w < 0; i.e. the system does work on the surroundings.  How is this possible?  How can we do work without a change in internal energy?  Furthermore, we have seen that some transformations occur spontaneously only in one direction, even if deltaU = 0.  For example, if we open a bottle of perfume in a room, soon perfume molecules will fill the entire room, but the reverse process will never happen.  Finally, we know of simple examples in which a reaction occurs spontaneously even if it requires energy from the surroundings, for example sweating. 

We are clearly missing a kind of energy that will provide a driving force for spontaneous events to occur even with no change in internal energy.  We developed a state function, called entropy, S, which defines the direction of spontaneous change (deltaS > 0), and which will quantify this driving force:

      deltaS >= q/T.