1.1.

3 Relationship between enthalpy, internal energy and work

If the above relationship is written in the differential form:
dU = dQ – dW
If the only force acting on the system is pressure,
dW = pdv
Hence,
dU = dQ – pdv
If the change occurs at constant volume,
dU = dQ = Cvdt
where, Cv is specific heat at constant volume.

In many chemical engineering applications, the summation of U and the

pressure-volume product appears quite frequently. Hence, it is convenient
to represent this summation by an entity called enthalpy, denoted by H.
Thus:

H = U + pv
Like U, H has no absolute value, and we deal with differences of
H, denoted by ∆H.

By differentiation of above equation,

dH = dU + pdv + vdp
For a constant pressure process,
dH = dU + pdv
If pdv is expressed in work units,
dH = dU + pdv/J
Integrating,
H = U + pv/J

This is an important relationship for estimating internal energy U

from H and pv data.

dH = dQ = Cpdt

∆H = Q = ∫Cpdt
Industrial processes occur at constant pressure, and change in
enthalpy is measured by heat effect at constant pressure. To obtain
the value of heat evolved or absorbed in such a process, it is only
necessary to evaluate the value of H from the two terminal points
of the process.

 When a change occurs at constant volume, the heat effects

are measured by changes in U.
 When a change occurs at constant pressure, the heat effects
are measured by changes in H.