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

Lets look at the heat transferred in a variety of reactions at constant pressure. At constant pressure, the heat exchanged is the enthalpy change. When a substance goes from liquid state to a gas state at 1 bar, the enthalphy associated with the reaction is called the enthalpy of vaporization. The enthalphy change when a substance goes from the solid state to the liquid state is enthalpy of fusion. A direct change from solid to gas is called sublimation. The enthalpy change for such a reaction is then enthalphy of sublimation. To summarize:

An alternate path for going from solid to gas is to go through the liquid phase. The change in enthalpy for this path can be obtained from Hess Law. Hess Law tells us that the standard enthalpy for a reaction can be obtained by adding the standard enthalpies for the individual reactions involved. In this case, the reactions involved are fusion and vaporization. The standard reaction enthalpies for other types of chemical reactions can be obtained from Hess Law as well. In this case, its useful to define enthalpies of formation. The enthalpy of formation of a compound is the change in enthalpy in forming it from its elements in their reference states. The reference state of an element is its most stable state at 1 bar. Most tables will list enthalpies of formation of reagents in their standard states at 1 bar and 25C. Usually, tables will list these enthalpies in units of per mole. If you know the heat capacities at constant pressure for the reagents, you can get the enthalpies of formation at any temperature. With this definition in mind, the standard reaction enthalpies can be written as,

Sometimes, a thermodynamic cycle to get an unknown enthalpy for a reaction at some temperature from a known reaction enthalpy at a different temperature. In such a case, you should construct a thermodynamic cycle that takes the reaction of interest from the temperature where its enthalpy is known to the desired temperature. Since enthalpy is a state function, the overall change through the cycle is zero.

Maria A. Gomez, MHC

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10/9/07

Remembering the relationship between enthalpy and heat capacity and the fact that if you reverse the reaction, the enthalpy changes by a sign.

In the previous chapter, you found a relationship between the heat capacity at constant volume and molecular properties. To make use of these relationships, it is useful to know the relationship between the heat capacity at constant volume and the heat capacity at constant pressure. 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. The problem will guide you through the steps. You will just need to fill in the details. In deriving the general relationship, it is useful for you to keep in mind some some properties of multivariable functions. Consider a function that depends on x and y e.g. f(x,y). The partial derivative of f with respect to x tells us the slope of f when y is constant. What if we are changing more than one variable at the time. Then its useful to express f in differential format.

You should look at Math Chapter H for more details on how to treat multivariable functions and their derivatives.

Maria A. Gomez, MHC

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10/9/07