1

RAC HAND OUT

ENTHALPY, ENTROPY AND TABLES
Reference: Principles of Refrigeration by Roy J. Dossat, 5th Edition

4-17. Enthalpy
Enthalpy is a calculated property of matter that is sometimes very loosely defined as “total
heat.” More specifically, the enthalpy, H, of a given mass of material at any given
thermodynamic condition is the summation of all the energy supplied to it to bring it to that
condition from some initial condition arbitrarily taken as the zero point of enthalpy.

Whereas the total enthalpy, H, represents the enthalpy of m pounds, the specific enthalpy,
h, is the enthalpy of 1 pound. Since it is usually the specific enthalpy rather than the total
enthalpy that is of interest, hereinafter the term “enthalpy” shall be used to mean specific
enthalpy. Mathematically, enthalpy is defined as

h = u + pv/J (4-1)

where h = the enthalpy in Btu per pound

u = the internal energy in Btu per pound
p = the absolute pressure in pounds per square foot
v = the specific volume in cubic feet per pound
J = the mechanical energy equivalent (778 ft-lb/ Btu)

It is shown in Section 3-8 that not all the energy supplied to a fluid stays in the fluid as an
increase in the internal energy of the fluid. In many cases, some part of or all the energy
supplied to the fluid leaves the fluid as work. In Equation 4-1, the part of the transferred
energy that is stored in the fluid as an increase in the internal energy is represented by the
term u, whereas the part of the transferred energy that leaves the fluid as work is
represented by the term pv/J. While the energy represented by the term pv/J is not stored
in the fluid as an increase in the internal energy, it nevertheless represents energy that
must be supplied to the fluid in order to bring the fluid to the given condition from the initial
condition at the arbitrarily selected zero point of enthalpy. Also, this external work energy
must pass back through and be given up by the fluid as the fluid returns to the initial
condition.

Consider, for example, the vaporization of 1 lb of water into steam at 212°F under a
pressure of 1 atmosphere. The volume of 1 lb. of water at 212°F is 0.01672 ft3/lb, whereas
the volume of 1 lb. of steam at 212°F is 26.80 ft3/lb. Consequently, during the vaporization
process the fluid expands at constant pressure from a volume of 0.01672 ft3/lb to a volume
of 26.80 ft3/lb, thereby doing work in expanding against the pressure of the atmosphere.

The enthalpy of 1 lb of water at 212°F is 180.07 Btu/lb, while the enthalpy of 1 lb of steam
at 212°F is 1150.4 Btu/ lb, so that the enthalpy (latent heat) of vaporization is (1150.4 —
180.07) 970.3 Btu/ lb, the latter being the total quantity of energy required to vaporize 1 lb
of water at 212°F into steam at 212°F. Of the total energy supplied, the amount required to
do the work of the constant pressure expansion is approximately
 2

wp = p(V2 — V1)
= (2116 psfa) (26.8 ft3/lb — 0.01672 ft3/lb)

= 56,673 ft-lb

Or 56,673 ft-lb/778 ft-lb/Btu = 72.8 Btu

Consequently, the part of the energy supplied that is stored in the fluid as an increase in
the internal energy is (970.3 — 72.8) = 897.5 Btu. A pV diagram of the foregoing
vaporization process is shown in Fig. 4-5. The values for enthalpy and specific volume
were taken from a vapor table.

4-18. Entropy
Entropy, like enthalpy, is a calculated property of matter. The entropy (S) of a given mass
of material at any given condition is an expression of the total energy transferred to the
material per degree of absolute temperature to bring the material to that condition from
some arbitrarily selected zero or reference point. For any one fluid, the reference point for
entropy calculations is the same as that for enthalpy calculations.
Again, as in the case of enthalpy, it is the specific entropy, s, rather than the total entropy,
S, that is of interest. Therefore, the term “entropy” is used here to mean the specific
entropy, s, unless otherwise indicated.
It has been shown (Section 3-18) that the work of a process can be expressed as the
product of the change in volume ΔV and the average absolute pressure. Similarly, it is
often convenient to express the heat energy transferred during a process as the product of
two such factors. The concept of entropy makes this possible. The heat energy transferred
during a process can be expressed as the product of the change in entropy and the
average absolute temperature. Mathematically the relationship is expressed by the
following equations:-
 3

ΔQ= (Δs)(Tm) ………………………………….(4-2)

Δs = ΔQ/Tm……………………………….……(4-3)
Tm = ΔQ/Δs ……………………………………(4-4)
Where ΔQ = the hear energy transferred in Btu per pound
Δs = the change in entropy in Btu per pound per degree Fahrenheit.
Tm = the average absolute temperature in degrees Rankine*

* The average absolute temperature is not merely the mean of the initial and final
temperatures of the process but is the average of all the absolute temperatures
through which the process passes.

The relationships defined by the foregoing equations are for ideal reversible processes
(see Section 3—31). However, since the change in entropy Δs between any two state
points has a definite value, regardless of the path of the process, the change in
entropy for an irreversible process can be determined by making the calculation for a
reversible process that takes place between the same two state points.

On a pV diagram (Fig. 4-5), the area under the process line, which is the product of the
change in volume ΔV and the average absolute pressure, represents the work of the
process. Similarly, on a temperature-entropy (Ts) diagram (temperature plotted against
entropy), the area under the process line, which is the product of the change in entropy ts
and the average absolute temperature Tm, represents the heat transferred during the
process. The vaporization process described in Section 4-17 is plotted on Ts coordinates
in Fig. 4-6.

Since the temperature remains constant at 212°F during the aforementioned vaporization
process, the average absolute temperature Tm for the process is 672°R. From the steam
table (Table 5-1), the entropy of 1 lb of water at 212°F is 0.3120 Btu/lb °F, and the entropy
 4

of 1 lb of steam at 212°F is 1.7556 Btu/lb °F. Applying Equation 4-2, the heat transferred
during the process is
Q = Tm (s2 — s1) = (672°R) (1.7566 —0.3120)
= 970.7 Btu/lb
Entropy is frequently described as a measure of the unavailability of energy. Not all the
energy of a system is available to do useful work. For example, consider a steam radiator
being used to heat a room whose temperature is maintained at 75°F. Even under ideal
conditions, the maximum amount of energy that would be available to the room from any
steam delivered to the radiator is the heat given off by the steam as it condenses and by
the resulting condensate as the latter cools to the room temperature of 75°F.
Although the resultant 75°F condensate will still have a considerable amount of energy
with reference to absolute zero, this energy is unavailable to the 75°F room because no
temperature differential exists between the condensate and the room. Entropy is an index
of this unavailability.
In all actual (irreversible) processes, the entropy of the system (or the surroundings) must
of necessity increase, primarily because some of the available energy must be used to
overcome friction and intermolecular attraction. In contrast, in any ideal reversible
adiabatic process, frequently called a “friction less adiabatic” or “isentropic” process, it is
assumed that none of the available energy is used in overcoming friction, and since there
is no heat transfer, the entropy (unavailable energy) is assumed to remain constant during
the process.

For example, with reference to Fig. 4-7, as the gas in the cylinder expands isentropically,
all the energy given up by the gas is transferred to the piston and subsequently stored in
the flywheel. On the up stroke, the energy stored in the flywheel is returned to the piston
and subsequently to the gas as the gas is compressed isentropically back to its initial
state. Notice that throughout the cycle, the available energy of the system remains
unchanged so that the entropy (unavailability) also remains constant.

Fig 4-7
(a) Expanding gas gives energy to flywheel during expansion process.
(b) Flywheel returns stored energy to gas during compression process.

In contrast, assume now that the gas in the cylinder is expanded irreversibly in that some
of the energy given up by the gas is used to overcome friction in the cylinder and other
mechanical parts. It follows that only a part of the energy available from the gas is
transferred to the piston and stored in the flywheel. Consequently, on the upstroke, the
energy available from the flywheel will be somewhat less than that required to recompress
the gas to its initial state. Moreover, during the recompression process, some of the
available energy from the flywheel will be used in overcoming friction, so that the total
 5

energy of the gas at the end of the recompression process will be less than the total
energy of the gas in the initial state.

Because of the irreversible losses in energy suffered in both processes, it is evident that
the available energy of the system has been decreased and that the entropy
(unavailability) has been increased. Ordinarily, the energy utilized to offset friction is
converted into heat and dissipated to the surroundings. Consequently, if irreversible
processes are to be repeated, energy to replace that lost to the surroundings must be
supplied continuously to the system from some external source; otherwise the system will
soon run out of energy.

4-19. Vapor Tables

Because of the relatively strong forces of mutual attraction that exist between the
molecules of a vapor, internal friction is always present when a vapor under goes a change
in condition. Consequently, the behavior of vapors cannot be predicted by application of
the ideal gas laws. For this reason, the properties of saturated fluids and superheated
vapors have been determined by experiment for all common fluids, and these data are
published in the form of tables and charts.

4.20. Properties of Saturated Fluids

The properties of saturated liquids and vapors at various conditions are given in saturated
vapor tables, say Fig.4-8, (above) which usually list values for the following properties:
 6

(1) temperature,
(2) pressure,
(3) specific volume,
(4) enthalpy and
(5) entropy

The temperature given is the saturation temperature of the fluid and is usually listed in the
extreme left-hand column as the entry property to the table. Normally, the corresponding
saturation pressure is listed in the second column and is followed by the specific volume
for both the liquid and the vapor states in the third and fourth columns, respectively. Some
tables list the density in addition to, or in place of, the specific volume. If only the density is
given and the specific volume is wanted, the specific volume is found by dividing the
density into 1. Likewise, when the specific volume is given and the density is wanted, the
density is found by taking the reciprocal of the specific volume. Three values for enthalpy
are listed in most tables
(1) hf the enthalpy of the saturated liquid which is the summation of the energy
required to raise the temperature of the liquid from the temperature at the
assumed zero point of the enthalpy calculation to the saturation temperature listed
in column one;
(2) The enthalpy of vaporization (hfg) which is the latent heat of vaporization at the
given saturation temperature; and
(3) The enthalpy of the saturated vapor (hg)), which is the sum of the enthalpy of the
liquid hf and the enthalpy of vaporization (hfg)).
When the enthalpy of vaporization is not listed, it can be determined by subtracting hf from
hg.
Two values of entropy are usually listed: sf, the entropy of the saturated liquid, and sg, the
entropy of the, saturated vapor. Some tables also list a value for which sfg, the change in
entropy during the change in phase. When this value is not listed, it can be determined by
subtracting sf, from sg.
Some tables also list values for the internal energy of the fluid in both the liquid and vapor
phases. When this is not the case, the value for the internal energy of the fluid in either
phase can be computed by rearranging and applying Equation 4-1 to solve for the internal
energy u.
It has been stated previously that the condition of a gas or a vapor can be determined
when any two of its properties are known. However, for a saturated liquid or vapor at any
one pressure, there is only one temperature that the fluid can have and still satisfy the
conditions of saturation. This is true also for the other properties of a saturated liquid or
vapor. Therefore, if either the temperature or the pressure of a saturated liquid or vapor is
known, the value of the other properties can be read directly from the saturated vapor
table.
 7

Example 4-1 Determine the pressure, specific volume, enthalpy, entropy, and internal
energy of 1 Ib of Refrigerant-12 (R-12) saturated vapor at a temperature, of 40°F.

Solution In Fig. 4-8 (Saturation Properties of R-12), locate the saturation temperature of
40°F in column one, and on the same line in column two, read the corresponding
saturation pressure of 51.68 psia. Still on the same line, the specific volume of the vapor
(vg) is 0.792 ft3/lb, the enthalpy of the vapor (hg) is 82.71 Btu/Ib, and the entropy .of the
vapor (sg) is 0.16833 Btu/lb °F.

Applying Equation 4-1, h = u + pv/J, and re-arranging:

and re-arranging: u = h – pv/J

u = (82.71 Btu/lb) (51.68 psia x 144) (0792 ft3/lb) = 75.13 Btu/lb

778 ft lb/Btu
8
9