Enthalpy Often, instead of looking at things at constant volume, we often look at things at constant pressure.

To look at heat capacities at constant pressure, introducing enthalpy is useful.

H = U + pV
Like the energy, the enthalpy is a state function. The variables involved only depend on initial and final conditions. The change in enthalpy at constant pressure is the heat supplied to the system. !H = q constant pressure Proof: Starting from the differential of the enthalpy definition dH = dU + pdV + Vdp . From the first law of thermodynamics, dU = ! q + ! w = ! q " pdV when the only possible work is expansion work. Combining this and our expression for the change in enthalpy yields

dH = ! q " pdV + pdV + Vdp = ! q + Vdp
At constant pressure,

dH = ! q
This suggests defining another heat capacity at constant pressure. " !H % Cp = \$ # !T ' &p constant pressure This says that if you have the heat capacity at constant pressure as a function of temperature, you can find the change in enthalpy in a temperature range by integrating the heat capacity with respect to temperature.
!H = " C p (T )dT
T1 T2

Thermochemistry Thermochemistry is the study of heat is transferred in chemical reactions. To study the transfer of heat in reactions, its useful to define a standard state of a system at a particular temperature. The standard state at T is defined as the pure form of the substance at 1 bar. Maria A. Gomez, MHC Page 1 10/9/07

In this case. the overall change through the cycle is zero. The standard reaction enthalpies for other types of chemical reactions can be obtained from Hess’ Law as well. In this case. Sometimes. The change in enthalpy for this path can be obtained from Hess’ Law. its useful to define enthalpies of formation. In such a case. The reference state of an element is its most stable state at 1 bar. At constant pressure. The enthalpy of formation of a compound is the change in enthalpy in forming it from its elements in their reference states. A direct change from solid to gas is called sublimation. Hess’ Law tells us that the standard enthalpy for a reaction can be obtained by adding the standard enthalpies for the individual reactions involved. Maria A. you should construct a thermodynamic cycle that takes the reaction of interest from the temperature where its enthalpy is known to the desired temperature. MHC Page 2 10/9/07 . the enthalphy associated with the reaction is called the enthalpy of vaporization. If you know the heat capacities at constant pressure for the reagents. The enthalphy change when a substance goes from the solid state to the liquid state is enthalpy of fusion. the reactions involved are fusion and vaporization. With this definition in mind. you can get the enthalpies of formation at any temperature. Most tables will list enthalpies of formation of reagents in their standard states at 1 bar and 25°C. When a substance goes from liquid state to a gas state at 1 bar. Gomez. Usually. The enthalpy change for such a reaction is then enthalphy of sublimation. Since enthalpy is a state function. a thermodynamic cycle to get an unknown enthalpy for a reaction at some temperature from a known reaction enthalpy at a different temperature.Let’s look at the heat transferred in a variety of reactions at constant pressure. To summarize: An alternate path for going from solid to gas is to go through the liquid phase. the heat exchanged is the enthalpy change. tables will list these enthalpies in units of per mole. the standard reaction enthalpies can be written as.

For an ideal gas. this relationship is You will find the general relationship for any system and then this limiting case in one of your homework problems. You should look at Math Chapter H for more details on how to treat multivariable functions and their derivatives. In the previous chapter. Consider a function that depends on x and y e. You will just need to fill in the details. What if we are changing more than one variable at the time. To make use of these relationships. you found a relationship between the heat capacity at constant volume and molecular properties. The partial derivative of f with respect to x tells us the slope of f when y is constant. The problem will guide you through the steps. the enthalpy changes by a sign. MHC Page 3 10/9/07 . it is useful to know the relationship between the heat capacity at constant volume and the heat capacity at constant pressure. Then it’s useful to express f in differential format. Gomez. Maria A.g.y). f(x. In deriving the general relationship. it is useful for you to keep in mind some some properties of multivariable functions.Remembering the relationship between enthalpy and heat capacity and the fact that if you reverse the reaction.