c


c
 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 SI

unit of enthalpy is the joule, but other historical, conventional units are still in use, such as the
small and the large calorie.

The total enthalpy, , of a system cannot be measured directly. Thus, change in enthalpy, ǻ, is
a more useful value than  itself. The value of ǻ is positive in endothermic reactions. ǻ of a
system is equal to the sum of non-mechanical work done on it and the heat supplied to it.

For quasistatic processes under constant pressure, ǻ 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.

Using enthalpy simplifies certain descriptions of energy transfer, as it is not affected by energy
transferred to the environment through the expansion of the system.

O
 


  









 


  

Specific heat
O=
capacity

ȕ= 1
Compressibility
í 
1
Thermal expansion Į =


c
 

 


Free energy Free entropy

Internal energy Ô( ,)

( ,
) = Ô +
c



Helmholtz free ( ,) = Ô í
energy
( ,
) =  í
Gibbs free energy

 
  
 

 



v‡d‡e



 
The enthalpy of a system is defined as:

where

 is the enthalpy of the system (in joules),

Ô is the internal energy of the system (in joules),

is the pressure at the boundary of the system and its environment, (in pascals), and
 is the volume of the system, (in cubic meters).

Note that the Ô term is equivalent to the energy required to create the system, and that the

term is equivalent to the energy which would be required to "make room" for the system if the
pressure of the environment remained constant.

The
 term may be understood by the following example of an isobaric process. Gas changing
its volume (by, for example, a chemical reaction) in a cylinder pushes a piston, maintaining
constant pressure
. The force is calculated from the area  of the piston and definition of
pressure
= /: the force is  =
. By definition, work  done is  = , where  is the
distance traversed. Combining gives  =
, and the product  is the volume traversed by the
piston: . Thus, the work done by the gas is  =
, where
is a constant pressure and 
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 ǻ = ǻÔ +  = ǻÔ + ǻ(
), where ǻÔ is the thermal
energy lost to expansion, and  the energy gained due to work done on the piston.

º   
 
 
   

Chemists routinely use  as the energy of the system, but the
 term is not stored in the system,
but rather in the surroundings, such as the atmosphere. When a system, for example,  moles of a
gas of volume  at pressure  and temperature , is created or brought to its present state from
absolute zero), energy must be supplied equal to its internal energy Ô plus
, where
 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 . In basic physics and thermodynamics it
may be more interesting to study the internal properties of the system and therefore the internal
energy Ô is used.[O
  ]

Ñ 
The word  

 is based on the Greek word  

 (ÿ ĮȜʌȠȢ), which means 
 

 . It comes from the Classical Greek prefix ÿ-, , meaning 
  , and the verb

ȜʌİȚ, 

, meaning "to heat". The word  

 is often incorrectly attributed[O

  ]
to Benoit Paul Émile Clapeyron and Rudolf Clausius through the 1850 publication of their
Clausius-Clapeyron relation. This misconsception was popularized by the 1927 publication of
  


 


. However, neither the concept, the word, nor the
symbol for enthalpy existed until well after Clapeyron's death.

The earliest writings to contain the concept of enthalpy did not occur until 1875,[2] when Josiah
Willard Gibbs introduced "a heat function for constant pressure". However, Gibbs did not use the
word "enthalpy" in his writings.[note 1] Instead, the word "enthalpy" first appears in the scientific
literature in a 1909 publication by J. P. Dalton. According to that publication, the word was
actually coined by Heike Kamerlingh Onnes.[3] Over the years, many different symbols were
used to denote enthalpy. It was not until 1922 that Alfred W. Porter proposed the symbol "H" as
the accepted standard,[4] thus finalizing the terminology still in use today.

ü
  



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

ǻ is the change in enthalpy of the system (under the restrictions mentioned above), and
 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 O
O

.[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

 is the enthalpy of the system,

Ô is the internal energy of the system,

is the pressure at the boundary of the system and its environment, and
 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 ( Ô = į + į + į'), so
where

į is the infinitesimal amount of energy added to the system through heat,

į is the infinitesimal amount of energy added to the system through expansion work,
and
į' is the infinitesimal amount of energy added to the system through any means other
than heat or expansion work. (' is sometimes called O
O
.[5])
(note that the inexact differential, į, is required for the path-dependent variables , ,
and ')

Because the energy added to the system through expansion work is į = í
, this term can
cancel with the existing
 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.

c
 


Enthalpy is sometimes described as the 

O  of a system under a given pressure, despite
the definition of heat as thermal energy in transit. Therefore heat cannot be stored as such. Such
a visualization assumes no energy exchange with the environment other than heat or expansion
work. Given such restrictions, it can be shown that:

p? The enthalpy is the total amount of energy which the system can emit through heat,
p? Adding or removing energy through heat is the  way to change the enthalpy, and
p? 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.

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 fact that the enthalpy is the amount of energy which the system can emit through heat can be
understood in the following manner. In order to do such conversion, one would have to convert
into heat all the internal energy of the system. One would also have to convert into heat all the
energy the environment provides as it collapses into the disappearing system volume. This
energy is equal to the work the environment does on the system volume. Assuming the pressure
of the system volume is constant during this process, this is í
ǻ = í
(0 í  
) =
 
. If
during this process no energy transfer has occurred other than heat or volume change, then the
total amount of energy converted into heat would thus be Ô +
 
, which by definition is the
enthalpy.

The fact that heat is the  way to change the enthalpy comes directly from the relation ǻ =
. Since  is the  term on the right, heat is thus the only way of changing enthalpy.

 
 
In thermodynamics, one can calculate enthalpy by determining the requirements for creating a
system from "nothingness"; the mechanical work required,
, differs based upon the constancy
of conditions present at the creation of the thermodynamic system.

Internal energy, Ô, must be supplied to remove particles from a surrounding in order to allow
space for the creation of a system, providing that environmental variables, such as pressure (
)
remain constant. This internal energy also includes the energy required for activation and the
breaking of bonded compounds into gaseous species.

This process is calculated within enthalpy calculations as Ô +
, to label the amount of energy
or work required to "set aside space for" and "create" the system; describing the work done by
both the reaction or formation of systems, and the surroundings. For systems at constant
pressure, the change in enthalpy is the heat received by the system.

Therefore, the change in enthalpy can be devised or represented without the need for
compressive or expansive mechanics; for a simple system, with a constant number of particles,
the difference in enthalpy is the maximum amount of thermal energy derivable from a
thermodynamic process in which the pressure is held constant.

The term
 is the work required to displace the surrounding atmosphere in order to vacate the
space to be occupied by the system.


 
 

The total enthalpy of a system cannot be measured directly; the  


O
 of a system is
measured instead. Enthalpy change is defined by the following equation:

ǻ = final í initial
where

ǻ is the  

O

final is the final enthalpy of the system, expressed in joules. In a chemical reaction, final
is the enthalpy of the products.
initial is the initial enthalpy of the system, expressed in joules. In a chemical reaction,
initial is the enthalpy of the reactants.

For an exothermic reaction at constant pressure, the system's change in enthalpy equals the
energy released in the reaction, including the energy retained in the system and lost through
expansion against its surroundings. In a similar manner, for an endothermic reaction, the
system's change in enthalpy is equal to the energy
 in the reaction, including the energy
  the system and 
 from compression from its surroundings. A relatively easy way to
determine whether or not a reaction is exothermic or endothermic is to determine the sign of ǻ.
If ǻ is positive, the reaction is endothermic, that is heat is absorbed by the system due to the
products of the reaction having a greater enthalpy than the reactants. On the other hand if ǻ is
negative, the reaction is exothermic, that is the overall decrease in enthalpy is achieved by the
generation of heat.

Although enthalpy is commonly used in engineering and science, it is impossible to measure

directly, as enthalpy has no datum (reference point). Therefore enthalpy can only accurately be
used in a closed system. However, few real-world applications exist in closed isolation, and it is
for this reason that two or more closed systems cannot be compared using enthalpy as a basis,
although sometimes this is done erroneously.

  


The specific enthalpy of a working mass is a property of that mass used in thermodynamics. It is
defined as  =  +
, where  is the specific internal energy,
is the pressure, and  is specific
volume. In other words,  = / where  is the mass of the system. The SI unit for specific
enthalpy is joules per kilogram.

c
 

An enthalpy change describes the change in enthalpy observed in the constituents of a

thermodynamic system when undergoing a transformation or chemical reaction. It is the
difference between the enthalpy after the process has completed, i.e. the enthalpy of the products,
and the initial enthalpy of the system, i.e. the reactants. These processes are reversible and the
enthalpy for the reverse process is the negative value of the forward change.

A common standard enthalpy change is the enthalpy of formation, which has been determined
for a large number of substances. Enthalpy changes are routinely measured and compiled in
chemical and physical reference works, such as the CRC Handbook of Chemistry and Physics.
The following is a selection of enthalpy changes commonly recognized in thermodynamics.
When used in these recognized terms the qualifier O
 is usually dropped and the property is
simply termed  


O . Since these properties are often used as reference values it is
very common to quote them for a standardized set of environmental parameters, or standard
conditions, which is typically a temperature of 298K and a pressure of either 1atm or 0.1MPa.
For such standardized values the name of the enthalpy is commonly prefixed with the term


 , e.g. 

  


.

Chemical properties:

p? Enthalpy of reaction, defined as the enthalpy change observed in a constituent of a

thermodynamic system when one mole of substance reacts completely.
p? Enthalpy of formation, defined as the enthalpy change observed in a constituent of a
thermodynamic system when, one mole of a compound is formed from its elementary
antecedents.
p? Enthalpy of combustion, defined as the enthalpy change observed in a constituent of a
thermodynamic system, when one mole of a substance combusts completely with
oxygen.
p? Enthalpy of hydrogenation, defined as the enthalpy change observed in a constituent of a
thermodynamic system, when one mole of an unsaturated compound reacts completely
with an excess of hydrogen to form a saturated compound.
p? Enthalpy of atomization, defined as the enthalpy change required to atomize one mole of
compound completely.
p? Enthalpy of neutralization, defined as the enthalpy change observed in a constituent of a
thermodynamic system, when one mole of water is produced when an acid and a base
react.
p? Standard Enthalpy of solution, defined as the enthalpy change observed in a constituent
of a thermodynamic system, when one mole of an solute is dissolved completely in an
excess of solvent.
p? Standard enthalpy of Denaturation (biochemistry), defined as the enthalpy change
required to denature one mole of compound.
p? Enthalpy of hydration, defined as the enthalpy change observed when one mole of
gaseous ions are completely dissolved in water forming one mole of aqueous ions.

Physical properties:

p? Enthalpy of fusion, defined as the enthalpy change required to completely change the
state of one mole of substance between solid and liquid states.
p? Enthalpy of vaporization, defined as the enthalpy change required to completely change
the state of one mole of substance between liquid and gaseous states.
p? Enthalpy of sublimation, defined as the enthalpy change required to completely change
the state of one mole of substance between solid and gaseous states.
p? Lattice enthalpy, defined as the energy required to separate one mole of an ionic
compound into separated gaseous ions to an infinite distance apart (meaning no force of
attraction).

Ñ 


In thermodynamic open systems, matter may flow in and out of the system boundaries. The first
law of thermodynamics for open systems states: the increase in the internal energy of a system is
equal to the amount of energy added to the system by matter flowing in and by heating, minus
the amount lost by matter flowing out and in the form of work done by the system. The first law
for open systems is given by:

dÔ = dÔin í dÔout + į í į

where Ô is the average internal energy entering the system and Ô is the average internal
energy leaving the system.

During steady, continuous operation, an energy balance applied to an open system equates shaft
work performed by the system to heat added plus net enthalpy added

The region of space enclosed by open system boundaries is usually called a control volume, and
it may or may not correspond to physical walls. If we choose the shape of the control volume
such that all flow in or out occurs perpendicular to its surface, then the flow of matter into the
system performs work as if it were a piston of fluid pushing mass into the system, and the system
performs work on the flow of matter out as if it were driving a piston of fluid. There are then two
types of work performed:  described above which is performed on the fluid (this is also
often called
) and 
  which may be performed on some mechanical device.

These two types of work are expressed in the equation:

į = d(
outout) í d(
inin) + įshaft.

Substitution into the equation above for the control volume cv yields:

dÔcv = dÔin + d(
inin) í dÔout í d(
outout) + į í įshaft.

The definition of enthalpy, , permits us to use this thermodynamic potential to account for both
internal energy and
 work in fluids for open systems:

dÔcv = din í dout + į í įshaft.

Note that the previous expression holds true only if the kinetic energy flow rate is conserved
between system inlet and outlet. Otherwise, it has to be included in the enthalpy balance. During
steady-state operation of a device ( 


 ), the expression above may be
set equal to zero. This yields a useful expression for the power generation or requirement for
these devices in the absence of chemical reactions:

This expression is described by the diagram above.


Ñ
 

As an expansion of the first law of thermodynamics, enthalpy can be related to several other
thermodynamic formulas. As with the original definition of the first law;

where, as defined by the law;

dÔ represents the infinitesimal increase of the systematic or internal energy,

į represents the infinitesimal amount of energy attributed or added to the system, and
į represents the infinitesimal amount of energy acted out by the system on the
surroundings.

As a differential expression, the value of  can be defined as[6]

where

į represents the inexact differential,

Ô is the internal energy,
į = d is the energy added by heating during a reversible process,
į =
d is the work done by the system in a reversible process,
d is the increase in entropy (joules per kelvin),

is the constant pressure,
d is an infinitesimal volume, and
 is the temperature (kelvins).

For a process that is not reversible, the above equation expressing d in terms of d and d
still
holds because  is a thermodynamic state variable that can be uniquely specified by and
. We
thus have in general:

d = d + d

It is seen that, if a thermodynamic process is isobaric (i.e., occurs at constant pressure), then d
is
zero and thus

d = d • į

The difference in enthalpy is the maximum thermal energy attainable from the system in an
isobaric process. This explains why it is sometimes called the 


. That is, the integral
of d over any isobar in state space is the maximum thermal energy attainable from the system.

In a more general form, the first law describes the internal energy with additional terms
involving the chemical potential and the number of particles of various types. The differential
statement for d then becomes:

where  is the chemical potential for an -type particle, and
 is the number of such particles. It
is seen that, not only must the d
term be set to zero by requiring the pressures of the initial and
final states to be the same, but the d
 terms must be zero as well, by requiring that the particle
numbers remain unchanged. Any further generalization will add even more terms whose
extensive differential term must be set to zero in order for the interpretation of the enthalpy to
hold.