Richard Lu Chapter 3 Summary Chapter three explores various mathematical properties of state functions.

Path-dependent variables such as heat and work are not discussed. One example explored is the relationship between pressure, volume, and temperature. Using the Ideal Gas Law, we can derive one of the variables as a function of the other two; thus, we can derive partial derivatives to evaluate the changes in these state functions. In the same manner, we can use relationships of mixed partial derivatives to see if a function is a state function. Partial derivatives can be used to evaluate an isobaric volumetric thermal expansion coefficient and an isothermal compressibility. Both of these variables can be used to evaluate changes in pressure during changes in temperature and volume. Energy can be conveniently expressed as a differential of temperature and volume. By extension, for a process at constant volume, we can use this to find Cv, the heat capacity at constant volume (because work done is 0 and all energy is dedicated to heat). Dependence of U on V at a constant T is called the internal pressure. The total differential of energy is dependent on the partial energy differential with respect to volume and temperature. For an ideal gas, the energy is only dependent o temperature, because no energy is required to change volume. James Joule experimentally determined the change in energy with respect to volume at constant temperature. As with energy, enthalpy can be described using temperature, pressure, and volume. Moreover, dH is an exact differential as with dU, and thus we can write dH as a sum of partial differentials of temperature and pressure. Because we are using constant pressure for the equation, we have a heat capacity equation analogous to energy, though we use the heat capacity at constant pressure, Cp. The difference between Cp and Cv is proportional to the number of moles in the system. Generally, Cp is larger because energy entering the system can go into work in expanding the system; thus, more energy is needed to increase the temperature of a system. Enthalpy can also be evaluated using pressure at a constant temperature. In doing so, we simply calculate the partial derivative with respect to pressure rather than temperatures. For such isothermal processes, we have an equation for the change in enthalpy with change in pressure that is related to the change in volume over the change in temperature at a constant pressure for the system. When calculating these values, we can simply replace one variable with the Ideal Gas Law to remove the differential components, e.g. writing dP as d[nRT/V]. The Joule-Thomson experiment was conducted to see how a gas temperature behaved when pressure was lowered in an insulated pipe. Because heat transfer is zero, we find that enthalpy is constant, yielding an isenthalpic expansion of the gas. The Joule-Thomson coefficient is the partial derivative of temperature to pressure at a constant enthalpy. Because the temperature of the gas can be lowered during isenthalpic expansion, a gas can liquefy in the process. If the J-T coefficient is negative, the temperature can actually increase, as happens with H2. Questions: How can some gases have a negative Joule-Thomson coefficient? Im not sure I understand the physical basis of this. What is the best way to keep track of the nuances with energy and enthalpy with respect to constant temperatures, pressures, or volumes?