Enthalpy is a measure of the total energy of a thermodynamic system.

It includes the internal energy, which is the energy required to create a system, and the amount of energy required to make room for it by displacing its environment and establishing its volume and pressure. Enthalpy is a thermodynamic potential. It is a state function and an extensive quantity. The unit of measurement for enthalpy in the International System of Units (SI) is the joule, but other historical, conventional units are still in use, such as the British thermal unit and the calorie. The enthalpy is the preferred expression of system energy changes in many chemical, biological, and physical measurements, because it simplifies certain descriptions of energy transfer. This is because a change in enthalpy takes account of energy transferred to the environment through the expansion of the system under study. The total enthalpy, H, of a system cannot be measured directly. Thus, change in enthalpy, H, is a more useful quantity than its absolute value. The change H is positive in endothermic reactions, and negative in exothermic processes. H of a system is equal to the sum of nonmechanical work done on it and the heat supplied to it. For quasistatic processes under constant pressure, H is equal to the change in the internal energy of the system, plus the work that the system has done on its surroundings.[1] This means that the change in enthalpy under such conditions is the heat absorbed (or released) by a chemical reaction. H(S,p), can be derived as a thermodynamic potential naturally dependent on S and p can be derived as follows from U(S,V). Here, U is internal energy, T is absolute temperature, S is entropy, p is pressure, and V is volume: The fundamental thermodynamic relation is basically the First Law of thermodynamics for reversible processes:

dU = TdS pdV
Apply the product for differentiation to pV:

dU = TdS + Vdp d(pV), hence d(U + pV) = TdS + Vdp

The enthalpy of a system is defined as:

so

dH(S,p) = TdS + Vdp

where H is the enthalpy of the system

U is the internal energy of the system p is the pressure at the boundary of the system and its environment V is the volume of the system. Note that the U term is equivalent to the energy required to create the system, and that the pV term is equivalent to the energy that would be required to "make room" for the system if the pressure of the environment remained constant. The pV term may be understood by the following example of an isobaric process. Consider gas changing its volume (by, for example, a chemical reaction) in a cylinder, pushing a piston, maintaining constant pressure p. The force is calculated from the area A of the piston and definition of pressure p = F/A: the force is F = pA. By definition, work W done is W = Fx, where x is the distance traversed. Combining gives W = pAx, and the product Ax is the volume traversed by the piston: Ax = V. Thus, the work done by the gas is W = pV, where p is a constant pressure and V the expansion of volume. Including this pV term means that during constant pressure expansion, any internal energy forfeited as work on the environment does not affect the value of enthalpy. The enthalpy change can be defined H = U + W = U + (pV), where U is the thermal energy lost to expansion, and W the energy gained due to work done on the piston.

Difference between enthalpy and internal energy

Chemists routinely use H as the energy of the system, but the pV term is not stored in the system, but rather in the surroundings, such as the atmosphere. When a system, for example, n moles of a gas of volume V at pressure P and temperature T, is created or brought to its present state from absolute zero, energy must be supplied equal to its internal energy U plus pV, where pV is the work done in pushing against the ambient (atmospheric) pressure. This additional energy is, therefore, stored in the surroundings and can be recovered when the system collapses back to its initial state. In basic chemistry scientists are typically interested in experiments conducted at atmospheric pressure, and for reaction energy calculations they care about the total energy in such conditions, and therefore typically need to use H. In basic physics and thermodynamics it may be more interesting to study the internal properties of the system and therefore the internal energy is used.[citation needed] The increase in enthalpy of a system is exactly equal to the energy added through heat, provided that the system is under constant pressure and that the only work done on the system is expansion work:

where

H is the change in enthalpy of the system (under the restrictions mentioned above), and Q is the energy added to the system through heat.
Expansion work is the transfer of energy between the system and its environment through changes in the system's volume. This type of work does not affect the above equation. Any other

type of work that could be done on the system aside from expansion is called non-mechanical work.[5] Non-mechanical work could include such processes as altering the internal energy using an external electric field, or adding energy through stirring. If any non-mechanical work takes place then the above equation will not hold. The exact relationship between enthalpy and heat can be derived from the definition of enthalpy. According to the definition of enthalpy,

where

H is the enthalpy of the system, U is the internal energy of the system, p is the pressure at the boundary of the system and its environment, and V is the volume of the system.
Differentiating yields

According to the first law of thermodynamics, any changes in internal energy are due to energy transferred with the environment (dU = Q + W + W'), so

where

Q is the infinitesimal amount of energy added to the system through heat W is the infinitesimal amount of energy added to the system through expansion work W' is the infinitesimal amount of energy added to the system through any means other than heat or expansion work. (W' is sometimes called non-mechanical work.[5]) (note that the inexact differential, , is required for the path-dependent variables Q, W, and W')
Because the energy added to the system through expansion work is W = pdV, this term can cancel with the existing pdV term to yield:

integrating then yields

Notice that this equation still has some extra terms; this is where the restrictions come in. Restricting the conditions to constant pressure ensures that the final term will equal zero. Ensuring that no work is done aside from expansion work makes the W' term zero. Thus

Provided that the pressure is constant and that the only work done on the system is through system expansion.

Enthalpy is not heat

Enthalpy is sometimes described as the heat content of a system under a given pressure, whereas "heat" is defined as thermal energy in transit. For the assumption that a change of enthalpy H is heat to be valid, no energy exchange with the environment must occur aside from heat or expansion work. Given this restriction, it can be shown that: enthalpy is the total amount of energy that the system can emit through heat Adding or removing energy through heat is the only way to change the enthalpy The amount of change in enthalpy is equal to the amount of energy added through heat. Thus it is as if enthalpy is nothing more than heat "stored" by the system, provided the given restrictions are adhered to. However, heat is not the only way to change enthalpy. Enthalpy also changes when the pressure of the environment is altered, even if no energy is exchanged as heat. In addition, enthalpy changes when energy is transferred into or out of the system through a means other than heat or expansion work, such as through external fields or stirring. The increase in enthalpy of a system is exactly equal to the energy added through heat, provided that the system is under constant pressure and that the only work done on the system is expansion work:

where

H is the change in enthalpy of the system (under the restrictions mentioned above), and Q is the energy added to the system through heat.
Expansion work is the transfer of energy between the system and its environment through changes in the system's volume. This type of work does not affect the above equation. Any other type of work that could be done on the system aside from expansion is called non-mechanical work.[5] Non-mechanical work could include such processes as altering the internal energy using an external electric field, or

adding energy through stirring. If any non-mechanical work takes place then the above equation will not hold. The exact relationship between enthalpy and heat can be derived from the definition of enthalpy. According to the definition of enthalpy,

where

H is the enthalpy of the system, U is the internal energy of the system, p is the pressure at the boundary of the system and its environment, and V is the volume of the system.
Differentiating yields

According to the first law of thermodynamics, any changes in internal energy are due to energy transferred with the environment (dU = Q + W + W'), so

where

Q is the infinitesimal amount of energy added to the system through heat W is the infinitesimal amount of energy added to the system through expansion work W' is the infinitesimal amount of energy added to the system through any means other than heat or expansion work. (W' is sometimes called non-mechanical work.[5]) (note that the inexact differential, , is required for the path-dependent variables Q, W, and W')
Because the energy added to the system through expansion work is W = pdV, this term can cancel with the existing pdV term to yield:

integrating then yields

Notice that this equation still has some extra terms; this is where the restrictions come in. Restricting the conditions to constant pressure ensures that the final term will equal zero. Ensuring that no work is done aside from expansion work makes the W' term zero. Thus

Provided that the pressure is constant and that the only work done on the system is through system expansion.

[edit] Enthalpy is not heat

Enthalpy is sometimes described as the heat content of a system under a given pressure, whereas "heat" is defined as thermal energy in transit. For the assumption that a change of enthalpy H is heat to be valid, no energy exchange with the environment must occur aside from heat or expansion work. Given this restriction, it can be shown that:

The enthalpy is the total amount of energy that the system can emit through heat Adding or removing energy through heat is the only way to change the enthalpy

The amount of change in enthalpy is equal to the amount of energy added through heat.

Thus it is as if enthalpy is nothing more than heat "stored" by the system, provided the given restrictions are adhered to. However, heat is not the only way to change enthalpy. Enthalpy also changes when the pressure of the environment is altered, even if no energy is exchanged as heat. In addition, enthalpy changes when energy is transferred into or out of the system through a means other than heat or expansion work, such as through external fields or stirring.