A Series of Enthalpy-entropy Charts for Natural Gases

By GEORGE GRANGER BROWN·

(New York Meeting, February 1944)
ABSTRACT valve, choke, or any other similar arrange-
ENTHALPY-ENTROPY diagrams are presented
for natural gases of 0.6, 0.7, 0.8, 0.9, and 1.0 ment, may be read directly from the
gravity ove~ the pressure range of 5 to 10,000 enthalpy-entropy diagram by following
lb. per sq. m. and temperature range of 320 a horizontal line between the known
to 700°F. The charts indicate directly the pressures.
work requirement and temperature rise f~r When compressing or expanding a gas
adiabatic compression or temperature change by means of a compressor or engine in
for free expansion of natural gases. which no heat is added to or subtracted
, COMPUTATION AND US~S OF CHARTS from the gas, but only work done the
. The Mollier diagram (Fig. 4), in which changes in. the properties of the gas' may
the. enthalpy (heat content); is plotted be determmed along a vertical line of
agamst the entropy with lines of constant co?stant entropy between the entering and
temperature, pressure, and in some cases eXlt pressures. The power required for the
volume, has been found most convenient compre~sion of the gas may be readily
when dealing with the compression expan- determmed by converting the increase in
sion, and flow of fluids. In dealing ~ith the enthalpy into the desired units.
flow of fluids, the sum of the increase in the The enthalpy-entropy diagram for
enthalpy, f:1H, plus the increase in kinetic natural gases is to the gas engineer what
u2 the steam diagram is to the steam-power
energy, f:1M 2g' plus the increase in poten- engineer. For this reason it would be ex-
tial energy, f:1MZ, representing the total tremely convenient if a reasonably satis-
increase in energy of the fluid in floW,' is factory enthalpy-entropy diagram could be
equal to the sum of the heat q, and :work prepared as a function of the gravity of the
added, -w, to the fluid while flowing ga~. A careful study of the known prop-
between the entrance and exit of the flow ertIes of natural gas indicate that this is
system. possible.
f:1H + f:1M u' + f:1MZ = q _ w The effect of temperature upon the
2g [1] enthalpy at constant pressure is expressed
In cases where there is no signific~nt as the "heat capacity" or "specific heat"
change in potential energy or in kinetic of the gas. The best available data for
energy (velocity), it follows that the natural and petroleum refinery gases indi-
increase in enthalpy is equal to the total cates the relationship shown in Fig. 1.
energy supplied to the fluid. Under such From this it is clear that the specific heat
conditions the changes in the property of of natural gases is a function only of the
the fluid as it flows through a throttling gas gravity and the temperature at atmos-
Manuscript received at the office of the pheric pressure.
Institute Feb. IS, 1944. Issued as T.P. 1747 in The effect of pressure on the enthalpy
PETROLEUM TECHNOLOGY, July 1944· Ab of natural gases is dependent upon the
• University of Michigan, Ann r or,
Michigan. pressure-volume-temperature relationships.
65
66 A SERIES OF ENTHALPY-ENTROPY CHARTS FOR NATURAL GASES

TEMPERATURE. DEClREES fAHRENHEIT

-200 o 200 400 eoo 800 lOCO
SPECIfIC HEAT
or
tftDROC~N VAPORS.
.10 ONE ATMOSPHERE: PRESSURE:

.80

...
:5A.
~
~.
.70 ~
~ ~
:s ~
...ill
...III
J: J

TEMPERATURE. DEClREES fAHRENHEIT

FIG. T -SPECll!'IC HE T OF HYDROCARBON VAPORS AT ONE ATMOSPHERE.
o

2 3 8 8 10
PSEUDO REDUCED PRESSURE
FIG. 2.-ACTIVITY COEFFICIENT FOR NATURAL 'GASES.
 PSEUDO REDUCED
8 TEMPERATURE

).

2 3 456789 10 II 12 13 14 15 16 17 18
PSEUDO REDUCED PRESSURE ~

FIG. 3.-ISOTHERMAL CHANGES IN ENTHALPY FOR NATURAL GASES.

I&J
..J
~
0 Cl
Z tzl
0
~ ""Cltzl
0:
I&J
II. Cl
:S
~
III
"">Z
Cl
tzl
>
II.
..J
-<
""
tzj
:I:
t-
Z
""~
0
I&J
Z

ENTROPY a T.U PER POUND MOLE PER DEGREE 1lSN.-2/1141

FIG. 4.-ENTHALPY-ENTROP¥·DIAGRAM FOR A 0.6 GllAVITY Nl\TUllAL GA&.

 .....o
ENTHALPY- ENTROPY DIAGRAM

80001m~ Q7 GRAVITY F"~:TURAL GAS·

P~ =667 P.5.LA85.. pTc=392 oR

7000

15D..
::I
t-=
ai

-6 -4 -2 0 2 8
ENTROPY B. T.U PER POUND MOLE PER DEGREE A.5.N. ~2/1/43

FIG. S.-ENTHALPY-ENTROPY DIAGRAM FOR A 0.7 GRAVITY NATURAL GAS.

 GEORGE GRANGER BROWN 7I
The comhined effect of temperature and ZRT RT [ Z
dH T = { p,p. - PrP.
pressure is indicated hy Eq. 2.
T,T. (~)
+ p.p. ]} PedP
dH = MCrtJ,T + [V - T (~~)J dP [2] TJJT, P, •

dH T _ RT. (~) dP _I1HT

y= p. aT. • T
II.t constant temperature
= R (P,=p, T, (~) dP, [5]
jp,=o aT, P.
It is therefore possible to prepare Fig. 3 by
The pressure-volume-temperature rela- integration of Eq. 5. The values for
tionships for natural gases have been
related with an accuracy of about ± 2 per
(aa; ) , P.
are determined by plotting z as a
cent to the pseudoreduced pressure and function of T. for lines of constant p. and
pseudoreduced temperature through the
compressibility factor and the following
differentiating graphically for (aa;) p;
equation: These values are then used in Eq. 5 and the
integration accomplished graphically by
PV = zNRT
in which z is the compres3ibility factor
plotting (aa;) • P.
against p. for lines of
added to the ideal gas equation in order to constant T. and getting the areas under
obtain accurate values for natural gases.! the curves from,P. = Q.
The pseudocritical pressure for a natural Similarly,
gas is the molal average critical pressure
obtained by multiplying the critical pres-
sure of each component of the gas by the
mol fraction of that component in the gas at constant temperature
and adding these products for all com-
ponents. The reduced pressure is obtained
by dividing the absolute pressure by the
dS = - a~tdP [71
absolute critical pressure.
This sounds rather complicated, but In terms of reduced temperature T. and
fortunately the pseudocritical pressure and reduced pressure P.,
pseudocritical temperature may be ap-
proximated in a reasonably satisfactory dS = -R [_z_
p.P.
manner from the gas gravity.!
"It is therefore possible to determine the T.T. (~)
+ p.P. ] PedP.
T edT. p,
effect of temperature and pressure upon the
enthalpy of p.atural gases from simply a JdS=-JR[Z
determination of the gas density. In order
to complete the work with the preparation + (a!zT)pJ dIn P. [8]
of an enthalpy-entropy diagram, the addi-
tional preliminary Figs. 2 and 3 were which may be solved by graphical methods
prepared. Since T = T,T. and P = P,P., as for Eq. 5, using a particular reference
by definition, pressure; A more convenient procedure,
1 M. B. Standing and D~ L. Katz: Trans. which also gives information concerning
A.I.M.E. (1942) 146, 140. the fugacity, is by use of the following
• D. L. Katz: Proc. Nat. Gas. Assn. of Amer.
(1942) 47; Refiner (1942) 2I (6). 58. equations:
72 A SERIES OF ENTHALPY-ENTROPY CHARTS FOR NATURAL GASES

The last term is evaluated by plotting In ~

1- Z
din! = dIn P - -p dP
din L-
P- ~::.!dP
-
P
against In T, from Fig. 2 and differentiating
graphically. In preparing the enthalpy-
dIn L = _ ~ P,.dP, =
P P,p.
I -
P,
Z dP,
entropy diagram, Figs. 4 through 8, a
reference state of 0 enthalpy was chosen
i rp,~p,
for each gas at 32°F. and 14.7 lb. pe.I
In p = Jp,=o (z - I)d In P, sq. in. abs. Using this as the starting
point, the enthalpy at atmospheric pres-
Eq. 9 may be integrated graphically by a sure could be determined for all tempera-
single operation to obtain Fig. 2. tures for each gravity of gas by use of the
Fig. 3 is computed from Fig. 2 by means data of Fig. I and the following equation:
of the following relationships:

F! - Fl = RT In h
J;. = RTlnh - RTlnh Similarly, the reference state for the
entropy of all gases was taken as 32°F. and
F2 _ Fl _ R lnb. 14.7 lb. per sq. in. abs. The entropy for
T T - h all temperatures and each gas w,,"s then
differentiating with respect to T computed by means of the data in Fig. I
and the following relationship:
~~ _ aF 1 = R In b. + RT (a In
aT aT h aT
h) p t:.S p = J MfPdT

_ RT (a lnh) At this point the data at each 100°F.

aT p

substituting for R In l were cross plotted as a function of the

gravity of the gas, in order to eliminate
any errors or irregularities in calculation.
aFt _ aFl = F2 _ Fl + RT (a lnh) The enthalpy was then plotted as a fun<;-
aT aT T T aT p tion of entropy, establishing the constant
_ RT (a aT
lnh)
p
pressure line of 14.7 lb. per sq. in. abs. on
each of Fig. 6 through 10.
The enthalpy at 5, 10, 50, 100, 200, 500,
( aF) = F - H 1000, 2000, 5000, and 10,000 lb. per sq. in.
aT p T '
( F2
T
_ H 2)
T
_ (F 1 _
T T -T
F2HI) _ _ F1
T
abs. was then computed for each 100°F.
using the data obtained for these tempera-
+ RT (a aT
Ini2) _ RT (a lnh) tures at one atmosphere pressure and the
p aT p data on Fig. 3.
Similarly, the entropy at these pressures
If state I is taken at a low pressure, so and even 100°F. was computed from the
thatft = PI, the last term becomes 0, and data just obtained and the use of Fig. 2 as
since P is constant for any differential at follows:
constant pressure
t:.H - t:.F _ t:.S
T -
t:.H - RT In izPI
__--=__P...::.2:!...:,it _ t:.S
T -
As before, the enthalpy at specified
temperatures and pressures were cross
 c;'l
to!
j 0
0 ~
~ c;'l
0 to!
z
:> c;'l
.~ ~
II:
>
Z
IoJ
"- c;'l
::s to!
,.: ~
<Ii
,. b:l
~

..
..J
J::
J-
0
~
Z
Z
,IoJ

-2 0 2 4 ~ 8 10
POUND MDLL PER DEGREE
FIG•• 6.-ENTHALPY-ENTROPY DIAGRAM FOR A 0.8 GRAVITY NATURAL GAS.
 .....
.j:>.

;.-
en
t'l
~
....
t'l
en
0
"'J
t'l
Z
o-l
:=;.-
t"
>tI
0<
I
to!
Z
o-l
~
0
>tI
0<
()
:=
;.-
~
o-l
en
"'J
0
~

Z
;.-
o-l
q
~
;.-
t"
G'l
;.-
en
to!
en

-12 -10 o R..l.R.-3I'5/.q

ENTROPY a T.U PER POUND MOL£ PER DEGREE
FIG. 7.-ENTHALPY-ENTROPY DIAGRAM FORA 0.9 GRAVITY NATURAL GAS.
 eooo
G'l
t<l
0
...-' I'd
Ii G'l
t<l
G'l
I'd
>
0:
r zG'l
..
~ t<l
I'd
tJ:j
t
I'd

l 0
z~

ENTROPY B.T.U. PER POUND MOLE PER DEGREE

FIG. 8.-ENTHALPY-ENTROPY DIAGRAM FOR I.O GRAVITY NATURAL GAS.

76 A SERIES OF ENTHALPY-ENTROPY CHARTS FOR NATURAL GASES

plotted as a function of gas gravity as a The charts are also suitable for plotting
means of checking errors ap.d irregularities Fanno and Rayleigh lines in the study of
in computations. It was found that the high-velocity flow, as described in various
computations themselves fell on consistent texts on thermodynamics.
smooth lines and no significant leveling of
the data was required. ACKNOWLEDGMENT
The final data were plotted as indicated
in Figs. 4 through 8 and the intermediate These plots, among others for natural
pressures and temperatures were inter- gases containing nitrogen, were prepared
polated. These charts may be used in the by J. T. Banchero, N. Fatica, W. Harbert,
same manner as the H - S diagram for J. L. McCurdy, M. J. Rzosa, G. W. Preck-
steam. For convenient estimates of the shot, and C. McKinley, gra.duate students
temperature drop on free expansion, follow in chemical engineering (1942) at the
a constant enthalpy horizontal line. For the University of Michigan. R. S. Neymark, a
increase in enthalpy on adiabatic com pres- senior in chemical engineering, inked the
~ion, follow a constant entropy vertical line. original charts.