1

Considerations on Real Gas Expansion: Otis P. Armstrong P.E., -Dec/1. 2011 r4

Abstract:
This topic is on effects of friction in real gas expansion, called non-reversible conditions.
The subtlety of this effect can be masked by the accompanying temperature decrease of
gas expansion. Use of Clausius Equality (Entropy) can properly account for friction in gas
flow. Many methods overlook the correct accounting for friction.
It is irrefutable: friction produces heat, as shown on the following H-S diagram. A decrease
in gas expander mechanical efficiency is accompanied by a subsequent increase in outlet
temperature. A result of friction between gas and machinery surfaces. This is noticed on a
H-S diagram by a counter-clockwise rotation away from the minimum isentropic
temperature towards isothermal operation. Also for compression, friction will increase
outlet temperature, a result of reduced efficiency, the same is true for nozzle flow.
Likewise for valves: gas friction increases the outlet temperature. This is noticed on the
H-S diagram by a counter-clockwise rotation away from the minimum isentropic
temperature towards the Free Expansion temperature. The Joule or Free Expansion
temperature is lower than isothermal expansion temperature and proportional to the
Joule Coefficient,
J
.
Many thermodynamic concepts of gas expansions are just idealization concepts. Actual
equipment shall always have friction effect, which will produce heat. For any real gas
expansion, generation of heat by friction produces a temperature increase.
Temperature and pressure equations for Isothermal, Isenthalpic, Constant Internal Energy,
and Isentropic gas processes are presented. The basis for these processes are the Joule-
Thompson ,
JT
, and Joule coefficient ,
J
, of real gases. Calculations for, and uses of,
JT
&
J
are detailed in this discussion. HTML calculation widgets are embedded in the .ppt
document for the readers utilization.
2
Summary, Recommendations & Calculation Methods
A General Energy Balance is suitable for prediction of Real Flow Phenomena thru valves, pipes, Turbines,
Compressors, pumps, and heaters. This general energy balance greatly simplifies the explination of
thermodynamics for either compressible or incompressible fluids into a unified concept.
{Ws + dP/ +VdV/g + [Pd(1/) + AU] - A(Q)h 0} or (U+(V
2
/2g)/J)
1
+(Q-W)=(U+(V
2
/2g)/J)
2
+A(PV)+ F.
Friction, F, may be determined by difference, by losses definition, or by (f L/D)(G/)
2
/2gJ, the details are
outlined on pages 14 and 15, plus other discussions. The term fL/D is also the Crane K factor for flow
apertures. Also Crane K, (TP410) is related to valve coefficient as detailed on page 14. Details for skin
friction are: K f L/D = (29.84d
2
/C
V
)
2
= (1/K
d
)
2
= 1/c = 1/(q
n
)
The Clausius Equality {F=(TAS-AQh)} is correct accounting of frictional heat, for either gas or liquid flow with
friction. Dissipation of energy by Friction to heat always increases temperature relative to a reversible
process. A correct heat balance must always calculate zero heat addition for Both a Joule Expansion {dU=0}
and a Joule Thompson Expansion, {dH=0}.
The determination of dH & dU to include pressure correction is easily implemented by the temperature
change from Joule or JT coefficients. Methods to evaluate these coefficients and associated temperature
change are presented in detail. AU =C
v
(AT - AT
JX
) & AH = Cp (AT - AT
JTX
) : The Cs are low pressure heat
capacity. The temperature sign convention is easily remembered. For at either AU or AH = 0, the
temperature change will be negative for all but 3 quantum gasses, H
2
for example. This is detailed in the
section Inversion Point. These rules offer simple EOS thermodynamic consistency checks for simulation
work.
The Schultz method, combined with the JT coefficient greatly simplifies evaluation of gas compression and
expansion : T2 = T1{P2/P
1
)
(m)
} m=(Z9/C
p
)() & =(c+X)
expansion
=(1/c + X)
compress
: The term X is related to the
JT Coefficient, in Rankin/atmosphere, Cp in BTU/#/F, and density in #/CF as: X=(0.37C
p
) . The details are
on page 40. Compressor head and Power are determined by use of real gas enthalpy change, as explained
above for total energy balance. A complete section is detailed in the appendix.
The ratio of Joule Expansion temperature change to Joule Thompson Expansion temperature change is the
ratio of specific heats: (AT
JTX
/AT
JX
) = (C
v
/Cp). The temperature drop associated with a Joule Free expansion
is greater than a JT, the difference may be attributed to friction effect.
Black Powder is found in raw gas pipelines and sales gas pipelines. Installation of high friction gas valve
requires immediate upstream gas filter to prevent black powder plugging, unless vendor warranty otherwise.
O P Armstrong PE/Dec.2011 printed Feb 2013
3
Introduction
Discussion with some engineers indicated a lack of grasp
on the heating effect of friction in gas flow. Additional
review of literature showed a lack of presentation, that
dissipation of energy via friction produces heat,
irrespective of the medium in which friction is dissipated.
The TS diagram for gas on right depicts friction effect in
either compression or expansion. It shows that friction
increases outlet temperature in both cases.
Even-so, some engineering routines perpetuate the cooling myth by misleading statements like: in
liquids friction produces heat but for gasses friction is converted to internal energy, hello?? Just
what is heat? Followed by such statements as was any heat added? Or was any work done by the gas.
This thought is routinely & incorrectly expressed by: (H+V
2
/2g/778)
1
= (H + V
2
/2g/778)
2
.
Some process simulator programs do not take into account details of mechanical design. Thus the myth
that friction pressure drop in gases does not heat a gas is routinely perpetuated. True: a normal gas
expansion cools, but friction in flow apertures reduces the amount of cooling. Why?, because friction
acts to reduce the output of useful work by energy dissipation to heat production. Heat generation
always acts to increase temperature.
Here is a typical quote from a web page: flow in oil pipelines acts to heat oil, where-as flow in gas
pipelines acts to cool the gas. It is NOT flow friction which acts to cool the gas but rather the
expansion resulting from pressure reduction. In BOTH cases, flow friction acts to produce heat. It is
just that the heating effect of flow friction in gas is masked by the normal cooling effect of gas
expansion.
A field test with a high friction valve demonstrated that friction in gas flow acts to counter the
expansion cooling effect. The field trial IR temperature measurements were personally supervised.
Results of this trial showed the valve outlet temperature exceeded the temperature determined by
simple JT expansion. Methods to quantify this effect are presented in this discussion.
4
Introduction, ctd:
Dissipation of work or momentum via friction will produce
heat, irrespective of the medium in which friction is
dissipated. The TS diagram on right shows friction effect in
either compression or expansion. Friction increases outlet
temperature, irrespective of expansion or compression.
The result of friction or irreversible losses causes the
outlet temperature to INCREASE to point 2. This is above
the reversible expansion temperature, point 2.
There are an accumulation of routines to perpetuate the cooling myth of gas friction. Looking at friction
on a molecular level, a gas molecule which losses momentum to a stationary object, gives up translation
energy. By conservation of energy, this organized momentum energy is translated to un-organized thermal
energy, so dS must increase. As correctly depicted in the above diagrams. The Clausius inequality for any
process involving friction requires: d(losses)>(Tds-d(Q)h). Likewise for flowing gas, Momentum lost to
intermolecular collision, turbulence, stationary walls of either a containment pipe, a valve flow orifice,
or a thermometer yields a temperature increase.
The thermometer correction factor based on the fluid velocity is: [T.bulk =T.tw-0.95V
2
/(778Cp2g)]. The
reading of a thermometer inserted into a pipe with flowing fluid is high by the above correction. Why?
Because momentum or irreversible energy loss happened, which locally heats the thermowell. This is
termed stagnation temperature. Friction effect of stagnation temperature requires high velocity aircraft
to need special leading edge materials. Concord jet nose cone was built at the limit of aluminum
materials for the achieved velocity. For a gas flowing inside a tube, the boundary layer volume to total
expanded volume is a small fraction, (momentum transfer efficiency). The small ratio of boundary layer
volume to a much greater bulk volume gives a net decreases in bulk of temperature due to gas volume
expansion. The effect of friction in gas is not a special case but just the nature of friction. Friction always
produces heat, irrespective of the involved media. Some practical aspects are: increase flare line
momentum loss to maximum limits to minimize cooling, improve SRVs by use of high turbulence valves to
gain maximum possible temperature in flare flow lines.
5
H-S C3=
Unzip compressed
folder to storage.
JT calculator is the
HTML file & executes
in mobile or other
browser with java
6
Field Trial: High Friction Gas Valve Temperature drop compared to Isenthalpic Performance
The percent efficiency is AT actual, divided by AT isenthalpic, times 100. A valve with
zero efficiency is a constant internal energy valve.
Note: the BWR JT temp is 465R or u.jt of 1.08, R/atm.
A pipeline rule of thumb is A7F/A100psid, by this rule the high friction valve out
performed the conventional rule. By the 7/100 rule the outlet T calculates to about 8F.
Small ports are required to obtain
high skin friction losses. These ports
can result in valve trim plugging or
erosion for dirty gases. Port plugging
during this trial indicated gas filters
were required due to dirty gas.
Looking at long term service, filter
costs may prove economical, if
outlet gas heat is of value or if
hydrate inhibitors are used.
Test Results show a 70% increase in
outlet temperature compared to JT
isenthalpic Performance. This is a
result of friction heating. One
method to create friction heating is
to increase turbulence by square
edge port trim.
prop unit viral R K actual
W/mw acentric 0.0720 20.3000
Hi
C p
btu/mol/R
11.6 11.6 F riction
Tc
Kelvin
213.9 213.9 Valve
Pc
Pc,atm
45.2 45.2 70%eff
Tin
T1Rankine 520.0 520.0
30%dH
Pin
P1atm
62.3 62.3 to heat
Pout
P2atm
11.2 11.2
ujt.clc Rankin/atm
0.823 0.769 na
T2 jt.clc Rankin
478.0 480.7 492
7
Nozzle Efficiency & Gas Heating
Many engineering routines do not acknowledge friction
heating in gasses. Instead placing emphasis on idealized
thermodynamic conditions. Such ideal conditions are not
meet in practice.*
As shown to right, effect of friction is to heat gas. Step 1 to
2 is the idealized thermodynamic temperature drop of a
nozzle. Step 1 to 2 is actual temperature drop. Nozzle
efficiency is given by Faires, p406:
c
n
= (T
1
T
2
)/(T
1
-T
2
) =(k
d
)
2
For the gas valve discussed above these calculate as:
T
1
=60, T
2
=19F, T
2
=32F which is c
n
=(60-32)/(60-19)=0.68 & k
d
=\0.68=0.83
Where T
2
is the ideal isentropic temperature.. T2 is actual outlet temperature. K
d
is coefficient of
discharge. Since k
d
is tabulated for many physical configurations it is possible to calculate actual outlet
temperatures based on equipment type and basic thermodynamic properties. The following calculations
detail this concept. The term, k
d
, may be correlated to either a Cv or to Crane K, fL/D.
Here is typical idealization from an engineering text (in courtesy, no reference to source): discussing flow thru a metering
nozzle situated inside a constant diameter pipe as an idealized throttling process. the discharge from the nozzle, with its
high kinetic energy, swirls about and dissipates its KE, thus KE is reconverted to internal energy and Ws=-AH=0. This is only
true in pedagogical circles. For practicing engineers, permanent pressure losses are the reality of actual operating
equipment. Because not all velocity head is converted back to pressure head, some velocity head is dissipated to what are
termed permanent pressure losses to be lost as low grade thermal energy. The engineering equation that correctly describes
a real process is: [H + V
2
/(2gJ)]
1
= [H + V
2
/(2gJ)]
2
+ F. Where F are friction losses. The pedagogical concept focus on JT cooling
neglects details such as, friction heating, operational losses, and a realistic thermodynamic frame work.
8
Determination Fluid Temperature Change
JT or Isenthalpic Expansion : AT =(Cp
JT
)AP, AH =0 & if P
2
<P
1
then T
2
<T
1
& AS>0 no work adiabatic
Joule Free Expansion: AT = (Cp
J
)AV , AU =0 & if V
2
>V
1
then T
2
<T1 no work adiabatic
Isothermal Temperature: AT = 0 , PV=C & if dQ >0 T
2
=T
1
& AS>>0 & dQ by Clausius Equality
Polythermal Temperature: AT = 0 , PV=ZRT & dQ either >0 or <0 T
2
=?T
1
& AS varies & no work
Isentropic Temperature: AT = T
1
((P
2
/P
1
)
(1-1/k)
1), AS =0 & if P
2
<P
1
then T
2
=T
1
((P
2
/P
1
)
(1-1/k)
& <T
1
Polytropic Temperature: AT = T
1
((P
2
/P
1
)
m
1), AS >0 & T2 = T1{P2/P
1
)
(m)
} m=(Z9/C
p
)() & X=(0.37C
p
)
(1.986Z/C
p
) C
p
in molar units, C
p
is Btu/CF/Rankin , is JT in Rankin/atm, =(c+X)
expansion
=(1/c + X)
compress
Each of the above process have specific properties and energy balance requirements. One must be careful
to apply process conditions that conform to assumptions stated. In other words, compare apples to apples.
Conditions for the Polytropic process are properly determined by the Schultz Method. A review of Schultz
method showed for limiting cases of: a) efficiency equals zero, it reduces to the Isenthalpic Expansion Joule
Thompson expansion and for b) efficiency of 100% it is an ideal gas Isentropic expansion. Both the
Isenthalpic and Isentropic Processes require adiabatic processes.
Adiabatic flow equation derivation uses premise of H
0
={H+ V
2
/2gJ} which is only true for frictionless flow.
This article advocates that where irreversibility is present H
0
={H + V
2
/2gJ F}. Derivations omitting
frictional effects then proceed to mix apples (frictionless energy balance) against energy balance with
friction, oranges. With advent of numerical computation such assumptions of isentropic energy balances
should be dropped. The replacement is to break pipe segments into smaller parts and numerically integrate
the correct energy balance of {H + (G/)
2
/2gJ}
(I -1)
= {H + (G/)
2
/2gJ dL(f/D)(G/
LM
)
2
/2gJ}
(I)
and
momentum balance: {P/ + (G/)
2
/2g}
(I -1)
= {P/ + (G/)
2
/2g dL(f/D)(G/
LM
)
2
/2g}
(I)
.These equations are
correct only for no heat addition and no shaft work. A classic example would be initial flow inside a flare
relief line where transit time minimizes heat gain from pipe metal sensible heat.
9
Pressure loss of valves may also be defined by C
V
, which at a given valve size may be defined in terms of K,
as given in Table at column 2. This slide demonstrates that frictional resistance, whether expressed in
form of Crane K, C
V
, or Co, or efficiency are all identical forms of irreversible friction process which
produce heat. Refer to Perry 5
th
Ed. Page 5-18 No friction term occurs in this expression since friction
represents a conversion of mechanical energy into HEAT.
Caution: Knowledgeable texts on friction place emphasis on manufacturer rating of equipment. One reason
for such caution is different types of energy dissipation. The above deal only with skin friction, other
forms are vortex &/or centrifugal. For example the Twister process which gives more cooling than JT by
mitigating friction heating.
Valve Flow Coefficient, CV
C
V
,gpm\(SG/Apsi), & Crane pressure loss is 144(Apsi)/ =KV
2
/2g, Equate Apsi for C
V
, & Crane K, using
water density of 62.4#/CF & SG= /62.4 & gpm=2.45Vd
2
. When making these substitutions & eliminate the
density, SG, Velocity, & flow terms one arrives at C
V
,=29.84d
2
/\K or K= (29.84d
2
/C
V
)
2
. The constant for the
Crane formula is 29.9, which the reader may back calculate the density is nearly the 62.4#/CF used for
this coefficient calculation. In summary Crane C
V
, relation is not an empirical equation. If skin friction is
accurately represented by fL/D= Crane K, so also is relation between C
V
, and Crane K.
Gas Valve Flow Coefficient
The C
V
, of gas is represented thusly: C
V
,=gpm\(SG/Apsi) & #/hr =gpm/(500SG), (#/hr)/(500SG)*\(SG/Apsi)
& SG=/62.4 & v=1/, place SG inside the root radical leads to C
V
=(#/HR)(1/500)\{(v/Apsi)62.4}
=#/HR(7.9/500)\(v/Apsi) = (pph/63.3) \(v/Apsi), where v is average CF/# for gas. Valve books have
extended formula for choked flow. For friction, the above is proposed to best reps total energy concept.
Summary: K= fL/D = (29.84d
2
/C
V
)
2
= (1/C
o
)
2
= 1/c = 1/(q
n
)
Revised slide
Friction losses for valves, throttling processes and many flow apertures are well documented, Crane
TP410, and easily calculated. The Crane method defines friction loss as multiple of velocity head, the K
method. Where Cranes K is product of friction factor and equalivalent length divided by diameter, a
dimensionless number. The below table gives some examples.
Friction Loss of Flow Apertures
Summary: K f L/D = (29.84d
2
/C
V
)
2
= (1/K
d
)
2
= 1/c = 1/(q
n
)
10
Appendix List
1. FRICTION
2. What are Joule & Joule Thompson Coefficients?
3. Joule Thompson Coefficient Inversion Point
4. Summary of Equations for Joule Coefficient
5. Joule Coefficient by VdW EOS limited utility
6. Joule Coefficient by RK EOS
7. Joule Coefficient by Viral EOS
8. Joule Coefficient by BWR EOS
9 Summary of Equations for JT Coefficient,
JT
10 JT EOS COMPARE RESULTS
11 Van der Waals Simplified JT Coefficient
12. Van der Waals Exact JT Coefficient
13.
JT
by the Two Term Viral EOS
14. Real gas JT coefficient as function of Z
15. Forms & Solutions of Redlich Kwong EOS
16 Determine (cZ/c
o
R) by Redlich Kwong h
method
17. Determine (cZ/c
o
R) by BWR Reduced Density
EOS
18. Energy Balance Summary
19. Clausius Equality & Energy Balance
20. Clausius Equality & Friction Heat
21. Energy Balance Corrected for Friction
22 Demo of Energy Balance for Liquid Pump, a. b
23. Nozzle Efficiency & Friction I & II
24. Gas Expansion Energy Balance SvN EX10-4
Corrected for Frictional Heat, 3 pages
25. General Enthalpy equation of Compression,
Expansion, & Flow Apertures
26. Real Gas Enthalpy change by JT coefficient,
JT
& pressure change:
27. Pressure Effect on dH by Cp correction vs. use
of Joule Coefficient.
28. Review of Polytropic Head Calculation Methods
7pp The Schultz Method
29. Express 9 = C
p
-C
v
for real gas as z9 = C
p
-C
v
30. Compare Gas X Calculation Methods 1
31. Compare Gas X Calculation Methods 2
32. Expansion of N2 Energy Balance for Turbine
33. Cross Correlations Coefficients & Properties 1
34. Cross Correlations Coefficients & Properties 2
35 Corresponding States as related to EOS errors
36 Kinetic Gas Theory Review
37 Dimensionless Numbers for Kinetic Gas Theory
38 Dimensionless Numbers of Gas Expansion
39 Kinetic Gas Theory & Friction Energy Balance
40 Properties of Common Gasses
41 Review of C3= Gas Properties
42. Review of differential forms & Math used here:
43. JX & JTX by Berthelot EOS
44. dT(JX vs. JTX) is C
p
/C
v
45. Field Trial Details: MultiStage Hi Friction Valve
46. Black Powder in Raw Gas Pipelines
47 Summary
11
Friction is not fiction, nor is it imaginary. Friction is the law of the universe: you cant win, you cant
break even and you cant get out of the game. A frictionless device is parlance for a non-existent Rube
Goldberg perpetual motion device. Ditto for the words: ideal, reversible, and isentropic. Such equipment
is a thought only. All motion is associated with friction. Some friction is hardly noticeable, sonic wave.
Extreme friction is dangerous! Friction is degradation of organized energy to disorganized energy, aka low
grade thermal energy. Father Friction is beneficial in many ways: it keeps our feet & other transport
means from sliding out of control. It also reduces impacts when control is lost. But for all this, Father
Friction, extracts a price of additional exerted energy. Motion has resistance which is mostly friction. It
will be present until universal kinetic and potential energies are reduced to a uniform state of motion.
Friction is lost work, W. Where work is, there also will be friction. Friction is work lost to heat. These were
the observations of Joule and Rumford. About 1850, Mr. Joule quantified the equality of work and heat as
778ft#=1BTU. A few BTU = lots of work. The work of getting into the bath tub will not substantially change
water temperature but, a few degree of extra heat will quickly end a bath. Friction is associated with
increase in entropy, dS. A P-V process or cycle with zero Entropy, AS, change is isentropic aka reversible
adiabatic, whilst the isenthalpic (AH=0) process is between has positive AS. The most probable state has
the highest positive AS. The word adiabatic is another ideal concept, meaning zero heat transfer. All
isentropic changes (dS=0) must be adiabatic, but not all adiabatic changes need follow the dS=0 path. The
H-S chart for C3=, presented here, is constructed for adiabatic enthalpy changes but only the 100%
efficiency line is also isenthalpic. An adiabatic friction process has Q=0, as given by the C3= H-S chart.
Friction consumption is rapidly determined at various efficiency on such a chart as dH @e less dH
@isentropic. The math of friction is as follows: Entropy always increases:
TAS>AQ & TdS = (dU + PdV) = (dH VdP) & Friction = (TAS - AQ)
e
AS
=(T
2
/T
1
)
Cv
(
1
/
2
)
R
= [(T
2
/T
1
)(
1
/
2
)
(k-1)
]
Cv
= [(P
2
/P
1
)
k
(
1
/
2
)
(k)
]
Cv
= [(T
2
/T
1
)
k
(P
2
/P
1
)
(1-k)
]
Cv
Summary: FFriction, Turbulence, & Work are identical energy forms (778ft#/BTU aka Joules Stirring
experiments) because Friction and Turbulence Always consumes Work.
Friction
12
What are Joule & Joule Thompson Coefficients?
This question is asked to better apply the (
JT
). It may appear to define gas flow processes. Internally, (
JT
)
is a property of the gas state. When the gas state is effectively modeled, it has both attraction and
repulsion terms. The cooling effect of gas pressure reduction arises when the gas molecules are dominated
by attractive force. As the gas expands, work is done to overcome the attractive forces and cooling is
effected from energy loss to overcome the attractive forces. The opposite is true if repulsive forces dominate.
The dimensionless Number, C
p

JT
, is the ratio of gas expansion temperature change to friction
temperature change, for dP &
JT
=0, as AT
F
= AP
F
/(J)= AT
JT
= (
JT
C
p
)AP. Which is true only for
Joule Thompson Expansion: 0AH=C
p
AT+(Cp
JT
)AP. While for Joule Expansion: 0AU=C
v
AT+(Cv
J
)AV
A JTX is the isenthalpic case. Article 10 found Temperature relation for the general isentropic case as:
Ti@e=1 + AT
F
= T
JT
, So if the expansion is without friction then, it is also isentropic. If AT
F
is maximum, the
temperature of an isenthalpic expansion, identical to the JT Temperature. The Joule & Thompson
experiment was devised, circa 1850. Under conditions of an equally isolated and insulated Joule free
expansion friction dissipation caused heating on the B sphere just equal to the cooling of the A sphere. The
net result for the free expansion was temperature decrease too small for Joule to detect. Joule and Lord
Kelvin devised the JT experiment with a porous plug. The ratio of Joule Thompson expansion dT to the ratio
Joule Free expansion dT is proportional to C
v
/C
p
. On the C
3=
H-S diagram, the adiabatic JT Expansion from
an initial pressure of 125Psia to 62.5psia at JT Temperature has a zero dH with no heat added. A Joule
expansion follows a constant internal energy line. A Joule or Free Expansion is not an isothermal
expansion. Lord Kelvin & Joule both agreed Joules device (& gas generally) was subject to frictional
heating. C W Smith 1977 Kent, Review of Lord Kelvins Cambridge Papers
JT Expansion dT~ -5F 22/11atm
Devised to eliminate friction heating
Joule Free Expansion dT~ -7F, if no Friction
B4: A @ 22atm: After A & B @
11atm. Inside copper spheres
was air, surrounded by an
insulated water jacket Va=Vb
13
Joule Thompson Coefficient Inversion Point
Another phenomena with gas is the (
JT
) inversion point. This is the temperature at which a quantum
change happens so the dominate force between gas molecules is repulsive. Inversion temperature for
various gases at 1atm are as follows: He, 40K; Ne; 231K, air 659K, N
2
, 621K; and O
2
, 764K. When a gas is
expanded at P & T above the inversion point then, an expanded gas, is a heated gas. When a gas is
expanded below the inversion point, an expanded gas is a cooled gas. Operation below the IP is the basis of
the Linde air separation plant. Operation below the IP produces an important class of fuels, LPG and LNG.
Operation at cryogenic conditions requires very low levels of tertiary gases; H
2
O, CO
2
, H
2
S, to prevent gas
hydrate formation in the equipment.
The phenomena of expansion is unrelated to friction heating. Just the opposite, careful measurement is
needed to eliminate friction heating to accurately measure (
JT
). Mr. Joules original experiment was in
reply to prior experiments which placed 2 spheres (1 of pressured gas other evacuated) connected by
stopcock into a water bath and found no change in water temperature upon opening stopcock between
spheres. Mr. Joule re-made the experiment by placing each sphere in individual water baths. After again
equalizing pressures found the water bath on pressure side had a decrease in temperature just equal to
temperature increase of the evacuated spheres side. Joule & Thompson revised the experiment using
flowing gases and a highly compressed cotton plug between 2 thermometers. The porous plug reduced flow
enough to mitigate friction effect. Also the relative mass effect of Joules method was eliminated. A
temperature decrease was measured for air at room temperature and an increase in temperature for
hydrogen was recorded at same conditions. The Joule expansion should have also measured a small net
decrease in temperature, but for the lack of accurate instruments, the relative gas mass to the combined
mass of copper spheres and water bath and friction effects. C W Smith 1977 Kent, Review of Lord Kelvins Cambridge Papers
One empirical correlation for (
JT
) inversion pressure is Pri=Ea
n
(T
r
)
n
where n runs from 0 to 5 and a
0
=-36.3,
a
1
=71.6, a
2
=41.6, a
3
=11.8, a
4
=1.67, & a
5
=0.091. Another empirical equation for approximation of HC gases
inversion point developed by Miller, presented on page 105 Walas ,1985 is: P
r
= 24.21-18.54/T
r
-0.825T
r
2
.
14
Summary of Equations for Joule Coefficient,
J

J
(cT/cV)
U=c
= -((cU/cV)T=c )/C
v
= -{T[(cP/cT)
V=c
]- P)}/C
v
1. The Van der Waals EOS, a & b are unique to the VdW EOS

J
(AT/AV)
U=c
= {-2.72a/V
2
}/C
v
& AT
JX
= {-2.72a AV
-1
}/C
v NOT Recommended
2. By any EOS for Z: [du~ u
2
-u
1
& 1/V = P/ZRT]
J
= {-9T
2
/V}(cZ/cT)/C
v
3. Viral 2 term form:
AT
jx
A(P
R
){1.09/T
R
1.6
- e0.139 +0.89e/T
R
4.2
- 0.083}(9T
C
)/C
v
for P
r
>0.8 & T
R
>1
This Viral form is limited to Vr<2 and this limit is to be strictly observed to eliminate unrealistic answers.
4. RK EOS: a & b are unique to the RK EOS
AT
jx
[-1.5a/(bC
v
\T)] ln{[V/(V+b)]
2
/[V/(V+b)]
1
} Joule X dT, Rankin deg.
5. BERTHELOT EOS
AT
JX
(AP
R
)(9 T/C
V
){1.266/(T
R
3
) - 1/(14.2T
R
)} & also C
v
AT
JX
= C
p
AT
JTX
Use dT.jx = dT.jtx (C
p
/C
v
) is direct. The low pressure ratio is applied as both C
p
and C
v
are low pressure.
The VdW
EOS dTs are
inconsistent
for this data
set. The VdW
EOS is not
regularly
recommended
for this work.
Joule X dT, Rankin degrees
EOS O2 CO2 C3= Air H2O
VdW -4.58 -0.49 -7.36 -0.51 -5.80
RK -6.44 -1.14 -21.70 -0.57 -32.80
Viral -6.16 -1.45 -23.50 -0.58 -41.72
BWR -6.24 -1.37 -28.60 -0.60 -44.92
B'lot -5.65 -1.47 -24.88 -0.50 -38.48
Avg -6.12 -1.36 -24.67 -0.56 -39.48
data BWRbest thisdata -28.40 -56.50
Conditions for dT.jx calcs
atm/R O2 CO2 C3= Air
P1 10.000 1.000 8.503 2.361
T1 76.4 60.0 100.0 70.0
P2 0.500 0.500 1.361 1.299
T2.jx 69.8 59.6 94.9 69.5
Z1 0.9696 0.9957 0.9332 0.9988
Z2.jx 0.9970 0.9971 0.9812 0.9991
dU 0.0000 0.0000 0.0000 0.0000
15
Isothermal Joule Coefficient of a Reversible Free Expansion (not to be confused with JT-X
which has units of degree per pressure but Joule Coefficient units are degree per volume) or

J
(cT/cV)
U=c
=(-1/C
v
)(cU/cV)
T=c
=(-1/C
v
)[ T(cP/cT)
V=c
P] =R-mol/CF= 2.72(-a /C
v
)/V
2
m
,
AT
jx
= (a/C
v
)A(1/V) van der Waals EOS &
CO
2
from: 8.54CF/# to 17.1CF/# & C
v
=6.71btu/mol/R, a=926atm/(CF/mol)
2
A
o
R = -0.5A
o
R
free expansion, (1/17.1-1/8.54)A(#/CF)(1mol/44#)(926atm(CF/mol)
2
)(2.72Btu/atm/CF)(mol-
o
R/6.71Btu)
The average
J
(0.5A
o
R/(8.54) A(#/CF)= -0.06 A
o
R/A(CF/#)
For O
2
298K & 10Bar to vac. A
o
R = - 4.9
o
R, V=10.72(536)/147=39CF/mol, & 390CF/m
A
o
R =-(1/39-1/390)A(mol/CF) (348atm(CF/mol)
2
)(2.72Btu/atm/CF)(mol-
o
R/5Btu) = -4.9 A
o
R
The average
J
(4.9A
o
R/(39) A(mol/CF)= -0.13 A
o
R/A(CF/mol)
As with Enthalpy Correction for pressure, the Internal Energy may be density corrected:
AU = C
v
AT + (T(cP/cT)
V=c
-P )AV = C
v
AT - C
v

J
AV = C
v
(AT -
J
AV) = C
v
(AT - AT
JX
)
Verification of sign convention when correcting dH & dU for pressure effect: only 3 gases increase in
temperature upon expansion at normal Ts, so, AT
JX
& AT
JTX
is normally negative and is identical to dT
for dH=0 & dU=0. So C*(-dT-(-dT)) = 0=C*(-dT+dT)= C*(0)=0.
For vdW gas: (Pr-3/Vr2)(Vr-1/3)=8/3Tr gives 2 unknowns & 2 equations to solve average Tr, But simple to
look on P-H chart for CO
2
and conditions are identified by internal energy line on which corresponding to
the 2 identified volumes. Cp by Cp =6.075+0.00523R & 14.7psia & 60F is close approximation to initial
conditions.

J
, Joule Coefficient of a Free Expansion by VdW EOS
16
Isothermal Joule Coefficient of a Reversible Free Expansion (not to be confused with JT-X) or

J
(cT/cV)
U=c
=(-1/C
v
)(cU/cV)
T=c
=(-1/C
v
)[ T(cP/cT)
V=c
P]
AT
jx
= [-1.5a/(bC
v
\T)] [ln{(V/(V+b))]
2
/[V/(V+b)]
1
} by RK EOS
RK EOS: P=RT/(V-b)-a/(\T(V+b)V) & [ T(cP/cT)
V=c
P] = 3a/(2\T(V+b)V) (form kind of dV/V
2
)
dT=(-1.5a/(C
v
\T))[dV/((V+b)V)] but wait is slight problem to get delta term, so decompose it
dV/{(V+b)V} =(1/b)[(dV)/V dV/(V+b)] =(1/b)[lnV ln(V+b)] |
2
1
=(1/b)[ln{V/(V+b)}|
2
1
]
AT
jx
= [-1.5a/(bC
v
\T)] {ln([V/(V+b)]
2
/[V/(V+b)]
1
)} by RK EOS integrated form
for CO
2
from 8.54CF/# to 17.1CF/# & C
v
=6.71btu/mol/R, a.vdw=926atm/(CF/mol)
2
, T~60F,
b.vdw=0.686cf/mol, 2.72Btu/atm-CF, a.rk =21677atm(CF/mol)
2
, b.rk =0.48CF/mol or 0.0109
CF/#, MW=44, T
c
=548R, left apprentices is -1195.3R and right apprentices, which is 0.0064
unit-less
free expansion, (1.5)(21677\R-atm/(CF/mol)
2
)(2.72BTU/atm/CF)(mol-R/6.8btu)(1.mol/0.48CF)/\548R
dT=(-1157.5)(0.00064)= -0.75R slightly over vdW dT, such small dT is unresolved by P-H charts.
For the Oxygen example the A
o
R= - 5.35 by RK EOS = 584.3LN(
b.rk=0.696(b.
vdw
) & a.rk=\T
c
(a.vdw), as b.rk in cf/mol; divide by MW to put in CF/# b4 add
w/V

J
, Isothermal Joule Coefficient For Free Expansion by RK eos
17

J
(cT/cV)
U=c
=(-1/C
v
)(cU/cV)
T=c
=(-1/C
v
)[ T(cP/cT)
V=c
P]= (-1/C
v
)[ T(cP/cT)
V=c
P]
Viral P=(9T/V)[1+(B
e
)P
r
/T
r
]& T(cP/cT)=T{[1+(B
e
)P
r
/T
r
]c(9T/V)/cT+(9T/V)c[1+(B
e
)P
r
/T
r
]/cT}
T(cP/cT)-P = (9T/V)[1+(B
e
)P
r
/T
r
]+(T
2
9/V)c[1+(B
e
)P
r
/T
r
]/cT} - P = {P+(T
2
9/V)c[1+(B
e
)P
r
/T
r
]/cT} - P
T(cP/cT)-P= (T
2
9/V) {c[1+(B
e
)P
r
/T
r
]/cT} = (T
2
9/V){P
r
/T
r
c(B
e
)/cT + (B
e
)c(P
r
/T
r
)/cT}
T(cP/cT)-P=(T
2
9/V) {P
r
/T
r
c(B
e
)/cT - (P
r
T
c
)(B
e
)/(T
2
)}=(P
r
9/V) {T T
c
c(B
e
)/cT - (B
e
)T
c
}
T(cP/cT)-P=(P
r
9T
c
/V){TcB
e
/cT-B
e
} =(P
r
9T
c
/V){(T/T
c
)cB
e
/cT
r
-B
e
} =(P
r
9T
c
/V){(T
R
)cB
e
/cT
r
-B
e
}
T(cP/cT)-P=(P
r
9T
c
/V){(T
R
)cB
e
/cT
r
-B
e
} =(P
r
9T
c
/V){(0.67/T
r
1.6
+0.72e/T
r
4.2
)-B
e
}
T(cP/cT)-P=(P
r
9T
c
/V){(0.67/T
r
1.6
+0.72e/T
r
4.2
)-(0.083-0.42/T
r
1.6
+ e(0.139-0.172/T
r
4.2
)}
T(cP/cT)-P=(P
r
9T
c
/V){(0.67/T
r
1.6
+0.72e/T
r
4.2
)+(-0.083+0.42/T
r
1.6
- e0.139+e0.172/T
r
4.2
)}
T(cP/cT)-P=(P
r
9T
c
/V){1.09/T
r
1.6
- e0.139 +0.89e/T
r
4.2
-0.083}
cannot do integral dV/V as P & V related, use PV=Z 9 T or P=(Z 9 T/V), so (P
r
9T
c
/V)=(Z 9 T/V) 9T
c
/(V P
c
)
The terms in brackets { } are dimensionless as e & T
r
, are dimensionless, as is Z. The integral of dV/V
2
is
A(1/V) & term RT
c
/C
v
has units of
o
R ((btu/mol)(mol-R/btu)=R), the term A(1/V) Z9T/(P
c
) when using atm, comes
to V=ZRT/P & 1/V=P/(ZRT)avg so A(1/V)=(P2-P1)/(ZRT)
avg
so A(1/V) Z9T/(P
c
)=(P
r2
P
r1
)(ZRT)
avg
/(ZRT)
avg
.
AT
jx
{A(P
r
)}{1.09/T
r
1.6
- e0.139 +0.89e/T
r
4.2
-0.083} (9T
c
)/Cv
Results for the prior 2 examples are CO
2
A
o
R= 2.04 & Oxygen, O
2
A
o
R= - 4.54 A
o
R
B
e
=(BP
c
/9T
c
) =(B
o
+ eB
1
) =f(T
r
) use B
o
=0.083-0.42/T
r
1.6
. B
1
=0.139-0.172/T
r
4.2
B
e
=(BP
c
/9T
c
) =(0.083 - 0.42/T
r
1.6
+ e(0.139-0.172/T
r
4.2
))
cB
e
/cT=(cB
e
/cT
r
)(cT
r
/cT)=(1/T
c
)(dB
o
/dT
r
+edB
1
/dT
r
) & cB
e
/cT=(1/T
c
)(0.67/T
r
2.6
+0.72e/T
r
5.2
)
Terms for B
o
& B
1
, Perry & SvN 3rdEd 75 p87 simple correlation of Abbott (1975) used here:
e= 0.1745-0.0838T
r
, T
r
<0.65 P<10atm, otherwise use data tables for e, & dV/V = ln(V
2
/V
1
)

J
, Joule Coefficient For Free Expansion by Viral EOS
18

J
(cT/cV)
U=c
=(-1/C
v
)(cU/cV)
T=c
=(-1/C
v
)[ T(cP/cT)
V=c
P]= (-1/C
v
)[ T(cP/cT)
V=c
P]
For the BWR, the EOS is very complex. Thus is simpler to do the EOS using Numerical Z factor.
PV=ZRT & P=ZRT/V & (cP/cT)
V=c
= (ZR/V)(cT/cT)
V=c
+ (RT/V)(cZ/cT)
V=c
= ZR/V +(RT/V)cZ/cT|
V
& T(cP/cT)
V=c
= ZRT/V + (RT
2
/V)cZ/cT|
V
= P + (RT
2
/V)cZ/cT|
V
[ T(cP/cT)
V=c
P] = P + (RT
2
/V)cZ/cT|
V
P = (RT
2
/V)cZ/cT|
V

J
(cT/cV)
U=c
= (-1/C
v
)[ T(cP/cT)
V=c
P]= (-1/C
v
)[(RT
2
/V)cZ/cT|
V
]=
AT
jx
[(9T
2
)]{ln(V
2
/V
1
)}{AZ/AT}/C
v
(btu/mol)(mol-R/btu)=R
Best for small change in dT was determined as:
AT
jx
{AZ}9T/C
v
units:(btu/mol)(mol-R/btu)=R, valid small dT & dP or T
2
=T
1
/exp\(ln(P
1
/P
2
)AZ9/Cv)
Alternative is to use reduced density method but was found to have higher error
cZ/cT= (cZ/cT
r
)(cT
r
/ cT) = -0.27[P
r
/(T
r
2

ra
)](1/ T
c
) which leads to:
T
2
=T
1
/exp(ln(P
1
/P
2
)AZ9/C
v
)
Most simple is to use dT.jx = k dT.jtx

J
, Joule Coefficient For Free Expansion by BWR EOS
19
Summary of Equations for JT Coefficient,
JT

JTX
(cT/cP)
h=c
= -((ch/cp)T=c )/C
p
= {T[(cV/ cT)
p=c
]- V)}/C
p
1. The Van der Waals EOS, a & b are unique to the VdW EOS

JTX
(AT/AP)
h=c
= {(2a/9T)-b}/C
p Not recommended
2. By any EOS for Z: [ as du/u =d(ln[u]) ~ ln(u
2
/u
1
) or du~ u
2
-u
1
& 1/V = P/ZRT]

JTX
= {9T
2
/P}(cZ/cT)/C
p
={[ln(Z
T2
/Z
T1
)]/ln(T
2
/T
1
)}(ZRT/(PC
p
))
average
Z
T2
is numerically evaluated at average P
r
and the average T
r
estimated by
JT
for the
given EOS.
3. Viral 2 term form:

JTX
= (T/C
p
)(c(B
e
)/cT B
e
/T) & B
e
=(9T
c
/P
c
)(B
o
+ e B
1
)
AT
JTX
=(9T
c
/C
p
)(AP
R
) {1.09/T
r
1.6
- e0.139 +0.89e/T
r
4.2
- 0.083}
(B
o
+ e B
1
)={(0.083-0.422/T
r
1.6
) e(0.139-0.172/T
r
4.2
)}, Pr>0.8 & Tr>1
This Viral form is limited to Vr<2 and this limit is to be strictly observed to eliminate
unrealistic answers.
4. Berthelot EOS:
AT
JTX
= {A[P
R
]}(9T/C
P
){1.27/T
r
3
- 1/(14.2T
r
)}
The specific heat, C
P
is the low pressure specific heat for all equations.
20
For this data set, the
BWR Method has less
error for HC gases. This
is especially true for the
C
3
= data point.
However, for general
gasses; Air, H2 etc.,
either the Viral, Blot &
RK method are better for
estimate of Joule
Thompson coefficient.
This result is not
surprising. Because BWR
EOS is a tailored EOS and
the BWR form used here
is based on light HC
gasses. Possibly, the
more involved Lee-
Kessler BWR EOS is
superior to all methods.
Even with all the advances in EOS development, the RK EOS remains a recommended method for
thermodynamic properties. Modern VLE calculations typically use either the LK-BWR, S-RK or PR. Both the
latter 2 forms are adaptations of the basic RK EOS. All three modern methods of VLE calculations use
accentric factors and mixing rule interaction parameters to improve accuracy. As shown for Z calculations,
limits for this BWR equation should be duly noted. None of these EOS were satisfactory for steam.

JT
EOS Comparison
JT Resul t Compare Vi ral /BWR/RK/vdW/B'l ot EOS v. Tabul ated Data
term R/atm C3= C1 C1 air CO2 H2 CO2 H2O
u.jt.vi r 2.79 0.71 0.78 0.49 1.76 -0.09 1.32 3.77
u.jt.bwr 3.49 0.71 1.01 -0.04 2.13 -0.03 2.19 3.03
u.jt.vdw approx 1.66 0.68 0.88 0.96 1.21 -0.04 1.11 1.24
u.jt.Ber'l ot 3.18 0.69 0.82 0.56 1.92 -0.07 1.56 2.67
u.jt.rk.dl nZ 2.78 0.75 1.27 0.31 1.94 -0.06 2.05 2.19
u.jt.rk.h eqn 2.73 0.73 1.17 0.36 1.89 -0.13 1.91 2.17
u.jt.rk.Z2-Z1 2.87 0.75 1.30 0.30 1.94 -0.06 2.08 2.27
u ref HS or TS 3.50 0.62 0.92 0.31 2.12 -0.05 1.70 4.46
reference scheel Schams Faries FariesHS perry5th wiki jt perry 5th stmTabl
page p94.HS p214 p222 p223/153p p3-163 www p3-163 KernDQ
Pr.avg 0.11 0.27 1.20 4.44 0.23 0.23 0.49 0.08
Tr.avg 0.83 1.63 1.41 1.61 0.99 9.03 1.05 0.74
T.avg R 543 558 484 384 542 540 578 860
P.avg atm 4.95 12.50 55.00 165.00 17.00 3.00 36.05 16.50
21
The VDW method for JT is used to make a 1
st
estimate of dT. From this expansion temperature
the calculation proceeds with more exact expressions of JT to determine average T
r
. Iteration
converges to an average JT by either R-K or Viral EOS. 9= universal gas constant,
1.99BTU/mol/
o
R or 0.7302atm CF/
o
R /mol,
o
R, Rankin & conversion factor, (2.72BTU/atm/CF).
A JT approximation from van der Waals EOS is: (adapted from McMaster)

JT
AT/AP = {(2a/9T)-b}/C
p
& b =V
c
/3= 0.7302T
c
/(8P
c
), a = 27p
c
(b
2
)

JT
: Van der Waals Simplified JT Coefficient
Units:
b CF/mol, a atm(CF/mol)
2
, 9T 0.73(atm-cf/mol/
o
R)(
o
R) & Cp BTU/mol/
o
R
b/Cp (CF/mol)(
o
R mol/BTU)(1/9 =
o
R mol/0.7302 atm CF)(9 =1.99BTU/
o
R mol)=
o
R/atm

JT
A
O
R/Aatm =2.72{(2a/(0.73
o
R)-b}/C
p
&b 9T
c
/8P
c
, a 27P
c
(b)
2
This review indicates that VdW is inferior to the Berthelot EOS for initial estimate of temperature
change for either JX or JTX.
Count Rumfords observation that
work produced heat via friction.
Joules Jar which established ratio
between heat or friction and work
at about 778 BTU/Ft-#.
22
JT by from van der Waals EOS at high pressures is:

JT
AT/AP = {-b/C
p
}{[4u|
3
- 3|(3|-1)
2
]/[4u|
3
- (3|-1)
2
]} & u=T
r
, |=P
r

JT
: Van der Waals Exact JT Coefficient
Units:
b CF/mol & Cp BTU/R/mol so multiply above result by 2.72 for units of R/atm
b/C
p
(CF/mol)(
o
R mol/BTU)(1/9 =
o
R mol/0.7302 atm CF)(9 =1.99BTU/
o
R mol)=
o
R/atm

JT
AR/Aatm = 2.72{-b/C
p
}{[4u|
3
- 3|(3|-1)
2
]/[4u|
3
- (3|-1)
2
]}
Inversion point is where
JT
0.00, this equation is one way to find I.P. pressure and temperature.
However, the vdW EOS is not very accurate method to represent gas behavior. This is demonstrated by a
comparison Z
c.
. The objective of any EOS is to mimic actual gas behavior. Most accepted EOS will do fair
job away from the Critical Point. But as conditions approach critical point larger deviations are expected.
For the vdW EOS, estimation by this exact form was typically no better than the approximate method.
This is likely due to the inherent limit of the vdW EOS gas having a Z
c
of 0.37. A Z
c
of 0.37 is not close to
the behavior of most real gases. The RK EOS is an improvement that fits a wider range of P & T than the
generic BWR*.
For a vdW gas inversion point is defined curve defined by (2a-b9T)V
2
-4abV+2ab
2
=0
Likewise, Boyle curve of a vdW gas is any point defined by (a-b9T)V
2
-2abV+ab
2
=0,
Adapted from www. The VdW are generally poor estimations of either dT.jx or dT.jtx
23

JT
:Two Term Viral EOS JT Coefficient

JT
= (T/C
p
)(c(B
e
)/cT B
e
/T) = (Tc(B
e
)/cT B
e
)/C
p
& B
e
=(9T
c
/P
c
)(B
o
+ e B
1
)
dB
e
/dT=(9 /P
c
)(dB
o
/dT
r
+ edB
1
/dT
r
) Where B
o
& B
1
= f(T
r
) :Perry & SvN 3rdEd 75 p87
Method NOT Recommended as other EOSs are more regular:
# The viral is restricted beyond pure components by
complicated mixing rules
need to evaluate 3
rd
parameter, e=f(Vapor Pressure @ T
r
= 0.7)
need an Binary interaction parameter k
i-j
for mixtures.
Other limits of this viral form are: V
r
>2, Best for non-polar or simular compounds
e= 0.1745-0.0838T
r
, T
r
<0.65 P<10atm, otherwise use data tables for e
e=(0.291-Z
c
)/0.08 Reid in Perry Eqn3-117, otherwise use data tables for e
Viral Terms for B
o
& B
1
, simple Abbott (1975): B
o
=0.083-0.42/T
r
1.6
. B
1
=0.139-0.172/T
r
4.2
.
Pitzer (1958) and Tsonopoulos (1974) Terms for B
o
& B
1
follow the form:
B
o
=A+B/T
r
+C/T
r
2
+D/T
r
3
+E/T
r
8
. B
1
= =A+B/T
r
+C/T
r
2
+D/T
r
3
+E/T
r
8
.. Viral Terms
A B C D E A' B' C ' D' E '
Pitz 1.4450E-01 -3.3000E-01 -1.3850E-01 -1.2100E-02 0.0000E+00 7.3000E-02 4.6000E-01 -5.0000E-01 -9.7000E-02 -7.3000E-03
Tson 1.4450E-01 -3.3000E-01 -1.3850E-01 -1.2100E-02 -6.0700E-04 6.3700E-02 0.0000E+00 3.3100E-01 -4.2300E-01 -8.0000E-03

JT
= (9 T
c
/C
p
)(1/P
c
) {1.09/T
r
1.6
- e0.139 +0.89e/T
r
4.2
-0.083} & by Using Abbots formula & Compare to
AT
JTX
=(9T
c
/C
p
)(AP
R
) {1.09/T
r
1.6
- e0.139 +0.89e/T
r
4.2
-0.083} & :
AT
jx
(9T
c
/Cv) (AP
R
){1.09/T
r
1.6
- e0.139 +0.89e/T
r
4.2
-0.083}
(AT
jx
/AT
JTX
)=(C
p
/Cv) {f(B
e.JX
)/f(B
e.JTX
)} =(C
p
/Cv) {1, for this EOS} =(C
p
/Cv)
24

JT
: JT Coefficient as function of Z any EOS
For real gas PV=z9T , & V = z9T/P &
JT
= dT/dP |
s=c
Expressed in terms of V,
JT
= [T(dV/dT)-V]/C
p
Td(z9T/P)/dTV=T[z9/P +(RT/P)(dz/dT)]-z9T/P ={9T
2
/P}(dZ/dT)

JT
=(9T
2
/P)(dZ/dT)/C
p
= 1.99(
o
R
2
/P
atm
)(cZ/c
o
R)/C
p
{Schaums Thermo 1972 p163.eq2}
units: R=1.99btu/(
o
R) & C
p
as btu//
o
R (
o
R/atm)[1.99btu/(
o
R)] (
o
R/btu)(
o
R/
o
R)=
o
R/atm
In above equation make substitution: PV=Z9T so 9T/P = V/Z & d(lnX) = 1/X dX

JT
= (VT/Z)(dZ/dT)/C
p
=(V)(dlnZ/dlnT)/C
p
=(Z9T/P)(dlnZ/dlnT)/C
p
numerically evaluate the differential : dZ/dT = (Z
T2
-Z
T1
)/(T
2
-T
1
) at P
r
average
It is often simpler to make the numerical evaluation than do complex algebra

JT
=(Z 9 T/P)(dlnZ/dlnT)/C
p
= {[ln(Z
T2
/Z
T1
)]/ln(T
2
/T
1
)}(Z 9 T/PC
p
)
average
Recommendation: log evaluation gave best results of all dual term methods. For general HC work the RK & BWR (with
imposed limits) do a reasonable job at dT.jtx estimation. The dT.jx is best estimated from (Cp/Cv)dT.jtx. The Joule and JT
temperature corrections are then used to pressure adjust Internal Energy and Total Energy: Elementary my dear Watson.
Note: Methods disposed here are identical to H.L. Callendars seminal work: Properties of Steam & Thermodynamic Theory.
of Turbines, London 1920. The Callendar EOS was later used to develop the ASME Steam Tables. Temperature and Pressure
are the only necessary coordinates to define all thermo properties of a single component system. Setting dU in terms of
volume and temperature and volume makes a perfect gas reduction to Cv=dU/dT. Because low pressure Cv and Cp are
used to define H & U, it follows that low pressure ratio of Cp/Cv is adequate to estimate dT.jx from dT.jtx. For expanded
pressure ranges , perhaps is better to use dT/T ={[ln... }}(1-1/k) dP/P , or ln(T2/T1)={[ln...]}(1-1/k)ln(P2/P1)?
25
Forms & Solutions of Redlich Kwong EOS
A. M-N Exact Cubic Solution (after LF Scheel GPC 72 p144/103 & WC Edminster GPC62)
M = 0.427P
r
/T
r
2.5
- 0.00752(P
r
/T
r
)
2
- 0.0867P
r
/T
r
- 1/3
N = M/3 - 0.0372(P
r
/T
r
1.75
)
2
+ 0.037
X = (N/2)
2
+ (M/3)
3
[Z(M-N) only valid X>0]
Z = (-N/2 - X
0.5
)
0.333
+ (-N/2 + X
0.5
)
0.333
+ 1/3
Most valves, compressors, and expanders are near or at single phase region, X>0. It is then
reasonable to force a solution using ABS(X). Then verify correct solution with a general Z by h
iterative method:
B. h method: with z = Z(M-N), from above
h= 0.0867P
r
/(zT
r
) = 0.0867 9 T
c
/(VP
c
) (if V known)
Z
rk
by h iteration method: Z
rk
=1/(1-h)-Oh/(1+h), O=4.934/T
r
1.5
Excess Properties and Fugacity by the RK EOS (from Perrys Eqn. 4-277/9
AH/RT = 1.5Oln(1+h) + (1-Z) & AS/T = 0.5Oln(1+h)-ln(Z-hZ) & ln=(AS- AH/T)/R
Mixing Rules: 1.Kay P
c
=E(yP
c
)
I
& T
c
= E(yT
c
)
I
&
2. Empirical a=(1/3)E(yT
c
/P
c
)
I
+(2/3)(E(y\(T
c
/P
c
))
I
)
2
b=E(y (T
c
/\P
c
))
I
&
P
c
=(b/a)
2
& T
c
=(b
2
/a)
The a & b terms of Redlich Kwong are not same as a, b of VDW. For RK, a=0.03719b(Tc)
1.5
& b=.08679(T
c
/P
c
), atm,
K. The RK EOS gives V
c
=3.85b where-as vdW gives V
c
=3b. All gases at any T and high pressure, the volume
approaches 0.26V
c
, as calculated by RK EOS. b.rk=0.696b.vdw & a.rk=\Tc a.vdw, as b.rk in cf/mol;
26
Z
rk
=[(1+h) - 4.93(h-h
2
)/(T
r
1.5
)]/(1-h
2
) & h = 0.0867P
r
/(zT
r
) =K/(zT
r
)
(1-h
2
)Z
rk
- (1+h) + J(h-h
2
)/(T
r
1.5
)=0 =f(z,T
r
) & sub for h w/ J=4.93 & K= 0.0867P
r
(1-(K/(zT
r
))
2
)Z
rk
- (1+ K/(zT
r
)) + J(K/(zT
r
) (K/(zT
r
))
2
)/(T
r
1.5
) & by z
2
T
r
3.5
z
2
T
r
3.5
(1-(K/(zT
r
))
2
)Z
rk
- z
2
T
r
3.5
(1+ K/(zT
r
)) + z
2
T
r
3.5
J(K/(zT
r
) (K/(zT
r
))
2
)/(T
r
1.5
)
(Z
rk
3
T
r
3.5
Z
rk
T
r
1.5
K
2
) - (Z
rk
2
T
r
3.5
+ Z
rk
1
T
r
2.5
K) + Z
2
T
r
3.5
J(K/(zT
r
) (K/(zT
r
))
2
)/(T
r
1.5
)
(Z
rk
3
T
r
3.5
Z
rk
T
r
1.5
K
2
) - (Z
rk
2
T
r
3.5
+ Z
rk
1
T
r
2.5
K) + Z
2
T
r
2
J(K/(zT
r
) (K/(zT
r
))
2
)
(Z
rk
3
T
r
3.5
Z
rk
T
r
1.5
K
2
) - (Z
rk
2
T
r
3.5
+ Z
rk
1
T
r
2.5
K) + J(Z T
r
K (K
2
))
(Z
rk
3
T
r
3.5
Z
rk
T
r
1.5
K
2
) - (Z
rk
2
T
r
3.5
+ Z
rk
T
r
2.5
K) + JK(Z T
r
K) = 0 =f(z,T
r
)
Use implicit rule to get : cZ/cT
r
= -(cf/cT
r
)/(cf/cZ) & chain cZ/cT = (cZ/cT
r
)/T
c
(cf/cT
r
)= (3.5Z
rk
3
T
r
2.5
1.5K
2
Z
rk
T
r
0.5
) - (3.5z
2
T
r
2.5
+ 2.5K Z
rk
T
r
1.5
) + Z
rk
JK
(cf/cT
r
)= (3.5Z
rk
3
T
r
2.5
+ KZ
rk
(J 1.5KT
r
0.5
- 2.5T
r
1.5
) - (3.5z
2
T
r
2.5
)
(cf/cZ)= (3z
2
T
r
3.5
T
r
1.5
K
2
) - (2z
1
T
r
3.5
+ T
r
2.5
K) + JK(T
r
)
(cf/cZ)= T
r
3.5
(3z
2
2z
1
) + K(J T
r
- T
r
2.5
K T
r
1.5
)
If V is known it may be helpful to use the reduced form of the RK EOS with Z
rkc
=1/3 :
P
r
=3T
r
/(V
r
-0.26) 3.85/[(T
r
0.5
(V
r
+0.26)V
r
] (the RK EOS in reduced format)
Determine (cZ/c
o
R) by Redlich Kwong h method
27
Z =0.27P
r
/(T
r

r
) & cZ/cT= (cZ/cT
r
)(cT
r
/ cT) = -0.27P
r
/(T
r
2

ra
)(1/ T
c
)
Solve reduced density at average Z by Benedict-Webb-Rubin EOS
f(
r
) = A
r
6
+ B
r
3
+C
r
2
+D
r
+ (E
r
3
)(1+F
r
2
)exp(-F
r
2
) -G
f(
r
) = 6A
r
5
+ 3B
r
2
+2C
r
1
+D + (E
r
2
)[3+F
r
2
(3-2F
r
2
)] exp(-F
r
2
)
(
r
)
i+1
= (
r
)
i
- f(
r
)/ f(
r
) use Z at average conditions for (
r
)
0
= 0.27P
r
/(T
r
Z
a
)
A=0.06423, B=(0.5353T
r
-0.6123), C=(0.3151T
r
-1.0467-0.5783/T
r
2
), & D=T
r
E=0.6816/T
r
2
, F= 0.6845, & G=0.27P
r
Ref: HP41 Petro Fluids Pac, Meehan & Ramey. P
c
=E(yP
c
)
I
T
c
=E(yT
c
)
I
This Benedict Webb Rubin EOS method is attributed to Dranchuk, Purvis, & Robinson who fitted the BWR EOS to the Standing
Katz Z factor chart for light hydrocarbons. G. Takacs (1976) found this method to have the lowest error among 8 common
methods to estimate Z. Valid for 1.05<Tr<3.0 and 0<Pr<3. Estimate Z1 by RK method & apply critical property corrections for
N2, H2S, & CO2 via Wichert-Aziz method, if needed. http://www.oiljetpump.com/welltesting_oil_L.xls
Determine (cZ/c
o
R) by BWR Reduced Density EOS
comparis on of Z by Various R eferences
# P r Tr Zchrt pitz'r Zrk Zbwr.xls Zref Reference
1 9.5 1.99 nd 1+ 1.020 1.247 1.248 HP BWR clc
2 5.0 1.50 0.810 0.801 0.811 0.811 HP BWR clc
3 0.4 0.80 nd 0.74? 0.650 0.535 0.630 nC5 LeeK bwr
4 0.4 0.90 0.778 0.780 0.761 0.756 nC5 LeeK bwr
5 0.4 1.00 0.850 0.850 0.842 0.844 nC5 LeeK bwr
6 0.4 1.10 0.880 0.891 0.888 0.891 nC5 LeeK bwr
7 0.4 1.20 0.910 0.918 0.917 0.923 nC5 LeeK bwr
8 1.2 1.05 0.470 0.460 0.404 na limit test HP bwr
A comparison of Z calculation by Benedict Webb Rubin
and RK EOS by excel is given in table on RHS to
sundry reference sources. LI 1 & 2 are to test
convergence routine used in.xls to that of the HP41
routine. LI 3 to 7 is comparison of BWR DPR to that of
BWR by Lee Kestler for nC5. A favorable comparison
was found for the imposed limits of the DPR-BWR vs.
the LK-BWR. The Z by Pitzer chart is also included.
Pitzer chart has limits not imposed on EOS Eqns. The
hardy RK EOS is also included. At high Pr and also at
cryogenic conditions the BWR is reported to have
better Z factors as compared to the RK EOS.
28
Energy Balance Summary
This section is written because energy balance for gasses was found to be misrepresented by a prolific and
widely used author of Chemical Engineering texts. The same misrepresentation is oft found by internet
search of same topic. A correct energy balance will work for any state, gas, liquid, solid, flow or non flow.
Energy does not respect the state of matter. A correct energy balance equation must predict zero heat and
correct expansion temperature for both adiabatic Joule Expansion A(U)=0 and for adiabatic Joule Thompson
Expansion, A(H)=0. These 2 expansions are litmus tests for any correct energy equation. The temperature
change and heat for both expansions are well documented by any EOS and by experimental data.
(U+(V
2
/2g)/J)
1
+(Q-W)=(U+(V
2
/2g)/J)
2
+ A(PV)+F
L
RB Bird 1957 in DM Himmelblau & HF Rase p100 1990
(H + V
2
/2g)
1
+ AE
G
= (H + V
2
/2g)
2
+ F
L
(var..Perry 5
th
Ed., Real Gas-EB, Kinetic Gas Theory-Energy Bal.)
{Ws + dP/ +VdV/g + [Pd(1/) + AU] - AQh =0} & AQh = (TAS - F
L
) Clausius/VL Streeter 5
th
Ed. p130
The reason to present these energy balance equations is pointing out that A(H + V
2
/2g) =C is a very limited
case. Equation, A(H + V
2
/2g) =C does not correctly convey energy balance for applications with friction.
Case 1. IDEAL NOZZLE/VALVE: No Work, No Friction Losses: (H + V
2
/2g)
1
= (H + V
2
/2g)
2
Case 2. REAL VALVE: w/ Friction, No Work or added energy: (H + V
2
/2g)
1
= (H + V
2
/2g)
2
+ F
L
Case 3. Zero Initial Velocity: No Friction: with Work: E
G
+ (H )
1
= (H + V
2
/2g)
2
Case 4. Constant Density: Heat Only & No Friction: E
G
+ (H)
1
= (H)
2
There are too many cases to list. The point is one cannot call A(H + V
2
/2g) a complete description of energy
without misrepresenting Energy Balance Principles. The details will be developed by calculations. The
examples show why either incorporation of thermal head, dU, or the Clausius Equality is a necessity to
balance the different heads, when accounting for friction as thermal energy. Stated in thermo terms :
AH=AU+ A(P/). If either the internal energy term or loss term is neglected the sum of energy terms will
not balance, nor will heat rate be correctly determined. Subsequent tables demonstrate theses points.
Professor Rase, p98-100, details a Newtonian Energy Balance as: Work by exterior force equals work against
friction + change in potential energy + change in Kinetic Energy. He assigns a negative value to work done
by the system to arrive at: W
a
= F + (AU-Q) + A(V
2
/2g)/J). Expansion work by system between boundaries is
A(PV) & W
a
-A(PV)=F + (AU-Q) + A(V
2
/2g)/J) or AH + A(V
2
/2g)/J) + F=Q+W. For adiabatic expansion with
zero shaft work, the Newtonian energy balance of Prof. Rase is: AH + A(V
2
/2g)/J) F =0.
29
Energy Balance from Basic State
1. A{(U+(V
2
/2g)/J} =(Qh +W) :basic energy balance- steady state without elevation or other energy forms Perry 5-31
W or work is composed of external work & expansion work or W = Ws - A(P/) Perry 5-32
2. A{U+ (P/) + (V
2
/2g)/J} = (Qh + Ws), next use Clausius Equality AQh = (TAS - F
L
), Perry p.5-18para.12 & Streeter
3. A{U+ (P/) + (V
2
/2g)/J} = TAS - F
L
+(Ws) & identity:AH= AU +A(P/) with v =1/Density=1/, & F is friction
4. A{H + (V
2
/2g)/J}= TAS - F
L
+ (Ws =0 for valve)- Friction & heat are zero for an ideal flow nozzle
5. A{H + (V
2
/2g)/J}= (0) Ideal Nozzle, but real nozzle which always has friction, use: TAS = -vd(P) + AH
6. A{H + (V
2
/2g)/J}= -vd(P) + AH - F
L
+ (Ws =0 for valve) the AH cancel, & v=ZRT/PM leaving ZRT/M ln(P)
7. A{(V
2
/2g)/J} + (ZRT/M)(dP)/P + F
L
= Make the integration to arrive at
8. A(V
2
/2g)/J} + A{ZRT/M)ln(P) + F
L
=0, Smith 10-4B p459
If differential velocity head is used, with velocity V = G/, one arrives at A{(V
2
/2g)/J}. So the velocity head
was not placed in differential form to expedite the key point of energy balance with friction.
The reason to present these energy balance equations is pointing out that A(H + V
2
/2g) =C is a very limited
case. Equation, A(H + V
2
/2g) =C does not correctly convey energy balance for applications with friction.
For Case of skin friction the energy balance reduces to
A(V
2
/2g)/J} + A{ZRT/M)ln(P) + (4fL/D)(G/LM)
2
/2g =0 where LM is log mean density based on EOS Z.
This is a sort of adiabatic friction equation where velocity and hence f changes along the flow path. Given
P1, P2, and T1, it is possible to solve or goal for T2 what balances the inlet and outlet energies, which
includes friction effect. All inlet energy terms are known. It is proposed this equation is as accurate as any
enthalpy equation and eliminated determination of heat capacity, and pressure correction of enthalpy.
30
Clausius Equality, Second Thermo Law & Friction Heating
Clausius Equality: non reversible process requires: A(Friction) = (TAS-A(Q)h), Streeter VL 1971 3.8.4; Perry p5.18
{Ws + dP/ +VdV/g + [Pd(1/) + AU] - AQh =0} Streeter-3.8.1, General Volume E balance & Perry 5-31/32
{TAS = Pd(1/) + A(U)} = dH - VdP Streeter (3.7.6): General Entropy, valid between any 2 Closed Equilibrium States,
{ Ws + dP/ +VdV/g + [TAS - A(Q)h ] =0 } Streeter 3.8.2: Sub of 3.7.6 to 3.8.1
Sub Clausius Equality, 3.8.4 to 3.8.2 : {Ws + dP/ +VdV/g + A(F) =0 } Streeter 3.8.5
For case of zero shaft work, obtain: {dP/ +VdV/g + A(Losses)}=0, Smith 10-4B
express losses as classic friction term and use V=G/ & dV = -Gd/
-2
to obtain:
{dP/ +(1/g)G
2
d/
-3
+ A(Losses)}=0, multiply by
2
to get: {dP - G
2
d//g +
2
A(Losses)}=0. M&Smith 6-59
Use Real Gas density (=PM/ZRT) at average Z & T to get : {(M/ZRT)PdP - G
2
d//g +
2
A(Losses)}=0.
Use Appendix identities to get: {M/(2ZRT) AP
2
- [G
2
ln(
2
/
1
)]/g +
2
A(Losses)}=0
Use average ZT, ln(
2
/
1
) reduces to: {M/(2ZRT)aAP
2
- G
2
ln(P
2
/P
1
) + a
2
A(Losses)}=0.
Smith takes A(Losses) =(4fL/D)(G/LM)
2
/2g & takes (a/LM)
2
=1 & sets Za =1 to get:
{M/(2RTa) AP
2
- G
2
ln(P
2
/P
1
) + (2fL/D)G
2
/g} = 0 {Smith 10-4D aka classic isothermal flow to solve P
2
}
{Ws + A(H + V
2
/2g/778) + {TAS =[ Pd(1/)/778 + A(U)] } - AF = 0, F is friction: F & Ws are in BTU/#
The Clausius Equality validity is proven by the derivation of the isothermal flow equation. Also if one
cares to accept simulator answer, heat determined by Clausius Equality more closely matched simulator
result than the Smith-Van Ness/ Smith method for SvN X10-4. Perry ChE Handbook taken from Streeter.
31
Clausius Equality, Second Thermo Law & Friction Heating
Clausius Equality: non reversible process requires: A(Losses or Friction) = (TAS-A(Q)h), Streeter VL 1971 3.8.4.
{Ws + dP/ +VdV/g +[Pd(1/) +AU] - A(Q)h =0} Streeter (3.8.1) General E balance for a volume. The term
(AU + Pd(1/) + dP/) = AU + d(PV) = dH so: dH +VdV/g +{Ws - AQh } = 0. At zero work, dH +VdV/g -A(Q)h = 0
Use A(Q)h = (TAS F) & dH +VdV/g - (TAS F) = 0. If using pressure head, MEB, with zero shaft work, {TAS =
Pd(1/) + A(U)} to get, dP/ +VdV/g + TAS - TAS + F = 0 or dP/ + VdV/g + F = 0. For constant density, the
regular Bernoulli is seen (P/ +V
2
/2g)
1
= (P/ +V
2
/2g)
2
+F.
Example: A Hydraulic Fluid, HF, bypass line on a Delayed Coker Unit (DCU) burns off 7,000 psi prior to
entering a fouled fin fan cooler which is causing overheating in the HF pump. Field survey shows a bypass
away from the hot DCU is possible. The inlet to the bypass valve is 70F and inlet to the cooler is 170F. What
portion of heat is gained by the pipe from the DCU area? Heat Capacity is 0.6 and average SG is 0.85.
Solution: Friction Heat: 7000(#/sq.in)(144Sq.in./SF)*1CF/(0.85*62.4#)(1BTU/778Ft#) = 24.4BTU/#
Friction Temperature Change: (24.4BTU/#)(1R-#/0.6BTU) = 40.7F & Entropy for Liquid is dS=Ci ln(T2/T1) so
TAS in Clausius Equality is (460+70/2+170/2)*0.6*ln(630/530) =580 *0.104=60.2BTU/#. Next find A(Q)h) by
Clausius Equality as: =A(Q)h =TAS- F = 60.2 - 24.4 =A(Q)h = 35.8 BTU/#.
Since {dP/ + Pd(1/) + AU} = AH, & Ws =0 rewrite 3.8.1 as {AH + AV.hd - A(Q)h =0} the inlet V is 90fps and
outlet V is 100fps. So {AH + (100
2
-90
2
)/50000 - A(Q)h =0} so AH=35.8-0.038=35.76BTU/# is the energy
associated with passage thru the DCU hotbox. The total dH=(170-70)*0.6btu/#/F=60BTU/# which is the sum
of friction and sensible gain, 24.4+35.76=60.2, and percent sensible heat gain in hotbox is 35.8/60= 60%. If
a bypass around hotbox is installed the heat duty to cooler is just the friction heat, 24.4btu/#, a 60%
reduction in heat load..
Any thermal solution where there is substantial friction must account for friction heating by the Clausius
Equality. Heat, Friction, and its laws have no respect for the material physical state. However the physical
state does effect the determination of physical properties.
For Smith X10-4 determination of heat by Clausius Equality method leads to dS by T-S diagram: 0.95-0.865 =
0.085BTU/#/R. TdS= (460+70/2+170/2)*0.085=580*.085=49.3, The Friction heat was determined as
19.2BTU/# so A(Q)h =49.3-19.2=30.1BTU/#. The V.head difference was determined as 5.1 so heat is:
dH + 5.1 30.1 => dH= 25BTU/#. Much closer to Simulator result of 24.2BTU/#.
32
The Energy Balance
Premise of Energy Balance is Energy Conservation: Classical Physics: total energy is constant
Starting $Energy + $Gains or Work = $Ending Energy + $Losses, most often friction losses.
(P/ + V
2
/2g + y + 778U)
1
+ AE
G
= (P/ + V
2
/2g + y +778U)
2
+ F
L
(units: feet of head)
Good, as energy states care not which path is taken. Energy accounting simplifies determination of final
conditions. The idealized thermo paths are visualized as either, constant: Internal energy, Enthalpy, or
Entropy. The actual path is usually some combination of these 3 idealized paths, as indicated on a H-S
diagram. NB: Thermodynamic idealizations are seldom realized in practical application. For applications of
processing equipment the elevation head, y, may be dropped or added to pressure head, leading to:
(P/ + V
2
/2g)
1
+ AE
G
= J C
v
AT + (P/ + V
2
/2g)
2
+F
L
For liquids Cp=C
v
For gasses, the term P/ is P/(PM/ZRT)= RT (but R=Cp-Cv) so RT = (Cp-C
v
)T, & :
(TCp+V
2
/2g)
1
+ AE
G
= (C
v
ATC
v
AT)+(TCp+V
2
/2g)
2
+F
L
Seen in thermo terms AH= ATCp or H= (T-T.
ref
)Cp or use T
2
=T.
ref
then AH= ATCp
For Gases: (H + V
2
/2g)
1
+ AE
G
= (H + V
2
/2g)
2
+ F
L
Case 1. IDEAL NOZZLE/VALVE: No Work, No Friction Losses: (H + V
2
/2g)
1
= (H + V
2
/2g)
2
Case 2. REAL VALVE: w/ Friction, No Work or added energy: (H + V
2
/2g)
1
= (H + V
2
/2g)
2
+ F
L
Case 3. Zero Initial Velocity: No Friction: with Work: E
G
+ (H )
1
= (H + V
2
/2g)
2
Case 4. Constant Density: Heat Only & No Friction: E
G
+ (H)
1
= (H)
2
There are too many cases to list. The point is one cannot call A(H + V
2
/2g) a complete description of
energy without misrepresenting Energy Balance Principles. The details will be developed by calculations.
The examples show why incorporation of thermal head, dU, is a necessity to balance the different heads,
when accounting for friction as thermal energy. Stated in thermo terms AH=AU+ A(P/). If either the
internal energy term or the loss term is neglected the sum of energy terms will not balance. The following
tables demonstrate the point.
33
Liquid output in out K C v C o
V fps 5.56 5.56 144.1 6 0.38
friction Hd ft -1.24 69.21
Work Head ft 271.63 0.00 BHP =>GP M 3.0 33.76
V head ft 0.48 0.48 R e ==> f 259786 0.0045
P head ft 56.90 99.38
T head ft 0.00 158.71 dT pipe friction, pipF 0.27
s um 327.77 327.77 dT total, pmpF +pipF 0.87
Pump efficiency 0.416 couls on p.166: TDH 113' vs 113calc
dT Pump 0.60 TDH=WorkHd*effic.
Liquid output in out K C v C o
V fps 3.40 7.66 39.9 170 0.44
friction Hd ft -0.41 36.37
Work Head ft 1226.77 0.00 BHP =>GP M 55.8 300.00
V head ft 0.18 0.91 R e ==> f 189300 0.0048
P head ft 163.46 713.46
T head ft 0.00 639.26 dT pipe friction, F 0.09
s um 1390.00 1390.00 dT total, pmpF +pipF 0.87
Pump efficiency 0.478 E vans p.150 gives e=0.479
dT Pump, F 1.65
Liquid Pump Total Energy Balance-a
34
Liquid output
in out K C v C o
V fps 1.14 1.14 0.0 48564 0.44
friction Hd ft 0.00 0.00
Work Head ft 692.96 0.00
BHP =>GP M
17.5 100.10
V head ft 0.02 0.02 R e ==> f 52583 0.0061
P head ft 46.20 461.98
T head ft 0.00 277.18 dT pipe friction, pipF 0.00
s um 739.18 739.18 dT total, pmpF +pipF 0.36
Pump efficiency 0.600
S vN p.457 gives e=0.6 dTp=0.35F
dT Pump, F 0.36
The three tables above were calculated with energy boundary condition around pump. These boundary
conditions consider pump work requirements to meet demands of impeller momentum transfer
efficiency, process friction losses, process total pressure head needs and fluid velocity head changes, if
any. In order to balance for irreversible friction effect of impeller momentum transfer, the T head or
internal energy head needs be added. The T head for liquids is heat capacity times fluid temperature
change. This is simply differential temperature necessary to balance the sum of heads terms, C
v
AT. It is
also related to pump impeller efficiency, e, as AT=(1/e-1) AH/Cp/778. The value 778 ft#/BTU is joule
ratio of heat to work dissipation. Efficiency is defined as ratio of work in to useful energy out. Useful
output is sum of difference between the three heads; Friction, Velocity, and Pressure. Without the T Head
the total energies will not balance.
Liquid Pump Total Energy Balance-b
35
The fallacy of neglecting friction can be easily seen if applied to a metering
orifice. For metering orifice (venturi, flow nozzle, pitot tube or orifice) all
produce some irreversible loss. The pitot or annubar produce the least losses.
An expression for permanent loss is Ap
p
=[Ah(1-Cd)].
.
For example if meter is
sized at 200 inch w.c. @ line inlet velocity of 200fps, density of 1pcf, T=600R,
air with k=1.4, C
d
=0.6 (Branan pp21/2). The line loss on orifice is
200*0.4=80w.c. or 80/12/1ft*(62.4#/cf/144sqin/sf)= 2.9psi. (N.B. !!: were
there zero irreversibility (friction) then all V head produced in orifice would be
recovered back to pressure head.)
Determine T
2
with isentropic Expansion:T
2
=T
1
(P
2
/P
1
)
(1-1/k)
= The friction term is:
dPf/
1
= 2.9psi*(144sqin/SF)/(1#/cf)/(778ft#/BTU) =0.5368, then by Bernoulli
heads to get 41.85 = 41.33+0.5368=41.87 or if looked at by enthalpy equation:
0.8238=?0.2855+0.5368=0.8223, clearly the AT needs to be less to make perfect
balance.
If try (H+V
2
/2g/778)
1
= (H+V
2
/2g/778)
2
, Line item 15 of In/Out table, clearly
does not balance as 25.472 BTU/# 24.077BTU/#.
One MUST add friction term to balance. If add fanning friction then is
25.472=24..08+.41=24.49 much smaller error and agree with Energy
Balance . (H+V
2
/2g/778)
1
= (H + V
2
/2g/778)
2
, has limited validity
Summary: A. standard equations which lack nozzle friction term are not
correct for real situations, with friction.
B. Isentropic equations need friction term to balance, dH error less
Correct expression to include friction is:
(H+V
2
/2g/778)
1
= (H + V
2
/2g/778)
2
+ H
F
H
F
= C
p
AT
F
= dP/(J ) or use Fanning Friction term.
LI item in out
1 T,F 140 137.8
2 Psia 221.8 218.9
3 #/hr 4331 4331
4 L'eq 2.635 2.635
5 di" 1.049 1.049
6 MW 29.0 29.0
7 Cp btu/m/R 6.951 6.951
8 u cp air 0.019 0.019
9 Z-RK eos 0.998 0.998
10 f Fanning 0.004 0.004
11 u.jt.rk eos 0.36 0.36
12 V fps 200.000 201.907
13 den pcf 1.002 0.993
14 H btu/# 24.672 24.161
15 H+Vhd 25.472 24.977
16 F. thermo BTU/# 0.555
17 F. fanning BTU/# 0.408
18 F. dE thml BTU/# 0.495
Isentropic dT ME bal
Heads in out I
Phd 40.970 40.819 a
Vhd 0.800 0.815 b
F hd 0.000 0.486 c
Cv dT 0.000 -0.377 d
Total 41.770 41.744 e
Nozzle Efficiency & Friction-I
36
Summary: A. standard equations which lack nozzle friction term are not correct for real situations.
B. Isenthalpic equations balance by including friction head, dH error 0.04% vs 0.06% & using
T2 based on Isenthalpic Equation.
Next: Try Same Conditions but with JT Equations to see if energies balance better.
From prior example C
p
= 0.2397 =6.951BTU/mol/R, T
1
=600R, P
1
= 221.8psia & P
2
= 218.9 or 15.088 atm &
14.891 atm respectively. Determine
JT
by RK EOS & T
2
isenthalpic =T
1
(P
2
/P
1
)
(1-1/k)e
Table 1 below
P1 dP P2 eff.I dTfrct Ti @1 Ti+f Tjt T2 clcu.jt
221.8 2.90 218.9 0.977 2.239 597.7 599.94 599.9 597.8 0.3169
221.8 5.08 216.72 0.981 3.938 596.0 599.94 599.9 596.1 0.3170
221.8 6.53 215.27 0.980 5.020 594.9 599.9 599.9 595.0 0.3170
221.8 21.80 200.00 0.967 16.83 582.5 599.3 599.5 583.1 0.3176
221.8 40.00 181.80 0.937 30.89 566.9 597.8 599.1 568.9 0.3183
221.8 77.63 144.17 0.876 59.94 530.5 590.44 598.31 538.7 0.3196
Based on (H + V
2
/2g/778)
1
= AH
f
+ (H + V
2
/2g/778)
2
AH = Cp(T
2
- T
1
-
JT
(P
2
- P
1
)) & include friction AH as
144dP
f
/778, Btu/# & AT friction= AH
f
/C
p
. For this thermo model it is determined that T
is
@e=1 + AT
F
= T
JT
,
Isentropic Temperature at 100% efficiency plus friction temperature = Temperature calculated by JT
coefficient. The logic is: as JT is based on frictionless expansion and isentropic expansion is based on
expansion with energy conservation from pressure energy to work energy but friction is destruction of work
energy. The mechanical energy balance is (P/ + V
2
/2g)
1
= (P/ + V
2
/2g)
2
+ AP
f
/
1
. When ME balance is
used, then rule is
1
=
2
to balance heads or P/T=C. When using Enthalpy method & neglect JT correction
then is isentropic X.
P1 T1 V1 d1 Ph1 Vh1 Sum1 P2 T2 V2 d2 Ph2 Vh2 fh2 Sum2
221.8 600 200 1.000 41.05 0.7984 41.9 144.2 390.7 200 0.998 26.73 0.801 14.37 41.90
Table 1 to RHS shows
Temperature results of E
balance by enthalpy equation
with JT correction to dH and
inclusion of friction loss.
Table 2, below from Mechanical
Energy Balance, show 1= 2 for
head balance, sum1=sum2
Nozzle Efficiency & Friction-II
37
Nozzles & Useful Gas Information from L. F. Scheel
Nozzles, after Scheel 1.1 C
o
Conoidal mouthpiece 0.98
Short Cyl. Round edge 0.92
Short Cyl. Square edge 0.82
Pitot Tube 0.86
Sq. Edge Orifice Plates
d/D from 0.1 to 0.6 0.65
d/D from 0.61 to 0.74 0.68
d/D limit 0.75 0.72
Scheel: ft/sec=C
o
\64.4AH
Other useful formula from Scheel are:
Correction of Nozzle flow for initial velocity:
Ft/sec = V = 223.8C
o
\{(Ah)/(1-[A]
2
/[A]
1
)} where dh is enthalpy change in BTU/#, 223.8 is root J2g.
Once again the use of C
o
shows that h
1
=h
2
is valid only for frictionless ideal flow, not for real conditions.
The use of Co, orifice factor , is equalivalent to using friction term in total energy balance. This is easily
verified by dH definition of flow coefficient.
Choked flow: #/min= C
o
6.813 Psia(d
2
/Z \(k MW/
o
R) & Choked acfm =73.3d
2
C
o
\(k
o
R)/MW)
For generic hole use orifice Coefficient of C
o
of 0.60, Fliegner Equation factor
Reynolds Number for Gas: Re=0.105(#/min)/(d * viscosity-cp) = (#/HR/SF)(D-ft)/(2.42cp)
Sonic V, ft/sec =224\(k
o
R/MW) V, fps=3.06(acfm)/d
2
#/sec=MMSCFD(MW/32.8)
P
c
= P
o
((2/k)+1)
(1/(1-1/k))
where k=C
p
/C
v
for air at 14.7psia the critical pressure ratio is 14.7/27.7 =0.53
Den #/cf =PM/(10.73Z
o
R) where T Rankin , P psia, MW is molecular weight
Gas Valve flow coefficient C.V.=(SCFM)\{(SG*T)/(520Ap*Psia.
out
)} Ap is psi
Horsepower = (#/min) (dH BTU/#)/42.5, ideal k =C
p
/C
v
=C
p
/(C
p
-1.986), C
p
is molar C
p
.
-oS/cP|
T
= cV/cT|
P
~ (R/P)[1+27P
r
/(32T
r
3
)] & C
p
-C
v
~ R[1+27P
r
/(32T
r
3
)] Berthelot EOS approximation, Walas p58
Gas k Avg T, Scheel
P
o
/P
c
mono 1.67 He Ar 220F 2.04
Diatomic 1.40 Air H
2
180F 1.88
Tri 1.30 CO
2
Steam 170F 1.85
Poly 1.20 HCCH, nC
2
, 135F 1.82
Heavy Org 1.10
nC
4
Bz 105F
1.67
Scheel AH is feet of head change, 64.4 =2*32.2; wet steam can have a k low
as 1.12, k=1.3 for super-saturated steam or super heated steam in the 200-
300 psia range, per Faires p 406
38
Generic Method for Gas Expansion with friction SvN EX.10-4
Smith-Van Ness Improved C
p
@1 atm.Cp, H&U by expan Coeff
Friction Energy F = (RT
a
/M)ln(P
1
/P
2
) -A(V
2
/2g)/778 F = (G/
LM
)
2
(2fL/D)/32.2/778 , fanning f
Total Energy (H+(V
2
/2g)/778)
1
+ Q = (H+(V
2
/2g)/778)
2
(U+(V
2
/2g)/J)
1
+ Q = (U+(V
2
/2g)/J)
2
or Clausius
dP Friction (G
2
/g)[ln(
1
/
2
)+(2fL/D)] = -M/(2RT
a
) A(P
2
) (G
2
/g)[ln(
1
/
2
)+(2fL/D)]= -M/(2RZ
a
T
a
) A(P
2
)
H, , & C
p
dH =C
p
(AT) & =PM/RT dH=C
p
(AT + (AP)
JT
) & = PM / ZRT
Results of SvN example problem are reviewed by a sum of heads method.
Improvements are possible as the sum of heads do not balance, LI#6. The error is
not in the Z factor. Z at inlet and outlet are about 0.999. It is proposed that SvN
method incorrectly calculates the amount of heat required. They use Q=dH+dVhd.
Determination of heat using SvN for the C3= Joule expansion requires about
7BTU/#, while it is known that Joule expansion is adiabatic & dU=0=dQ. See pg.
Term BTU/# Head in Head out LI
Wrk & F btu/# 29.6 19.0 1
V hd btu/# 1.4 6.5 2
P Hd btu/# 36.3 43.1 3
s um S vN btu/# 67.2 68.6 4
S vN E x.10-4 P457 5
eror% 0.12% 0.30% 6
V. L. Streeter,5
th
Ed.71, p112 Eqn.3.2.2&.7 & Perry Eqn.5-31, state: dQ - dW = d(U+(V
2
/2g)/J). This
relationship of heat, work, and internal energy correctly calculates the heat for a Joule Expansion in
absence of work & zero Kinetic Energy change as zero, while dH can be a positive value. The use of dU to
determine heat requirement also finds that Isothermal processes require heat addition. Where-as SvN
incorrectly equate isothermal processes as being constant internal energy processes, which it is not. Smith
carries this incorrect concept over to his Unit Operations book also. The reduction in heat requirement from
using dU more closely matches simulator heat requirement, line item 1 vs. 4 & 5 of attached table. Using
Smith values in the dU equation determines heat, dQ, as (7.1-1.986)*(170-100)/29+(6.5-1.4)=22.8BTU/# vs.
simulator result for identical outlet conditions, L.I. 4,5 of dQ of 24.2. The simulator determines for Smith
heat addition of 29.6 BTU/# the outlet temperature rises to 193F, LI#2, Table B, not 170F as problem states.
The value of heat addition rate may be verified by Clausius Formula: Friction=TdS-Q or TAS=T C
v
[(T
2
/T
1
)
k
(P
2
/P
1
)
(1-k)
]. Friction by SvN is 19 & TdS calculates as 0.66 at T of 580R, k=1.4, so
Q=19.6+0.66=20.3BTU/#.
If the difference in heat requirement from dH and dU is also looked at as the difference in net friction.
Then one can correctly conclude that friction in gas flow process equate to heat generation.
39
Compare Simulator Results for Air Flow SvN EX10.4 1000#/hr 1.049"Idstl
# Condition Ti To.F P1/P2 P1 dH Qin L' Vin
Vo fps dVhe
Ta
1 SVN10.4 70 170.0 1.83 34.7 24.50 29.6 36.0 261 570 5.13 120
2 Sim BB 70 192.2 1.70 34.7 29.73 29.6 36.0 261 547 4.60 131
3 Sim BB 70 170.0 1.69 34.7 24.33 24.2 36.0 261 525 4.14 120
4 Sim LM 70 170.0 1.69 34.7 24.33 24.2 36.0 261 525 4.14 120
5 Sim BB 70 170.0 1.83 34.7 24.33 24.2 46.3 261 566 5.04 120
6 Sim LM 70 192.2 1.83 34.7 29.73 29.6 46.3 261 586 5.50 131
7 KKGT 70 170.0 24.20 261 525 4.14 120
8 KKGT 70 192.2 29.53 261 586 5.50 131
'BB=Beggs Brill, LM Lockhart-Martin'li, KK Keys Kenan Gas Table Sim.EOS Soave RK
sim. Z=1.00 dH&dQ btu/# V fps SvN add Vhd to dTCp & over est'mte. Q
Gas in out
T, F 70.0 170.0
P, 'ps ia 34.70 19.00
#/hr 1000.0 1000.0
Lpipe E q ft' 36.0 36.0
di inch 1.049 1.049
MW 29.0 29.0
Cp btu/#/R 0.245 0.245
u cp 0.019 0.019
Z 1.000 1.000
Gas Expansion w/ friction: SvN Example:10.4 Disagree w/Process Simulator Results
This review of SvN
X10.4. SvN results
do not agree with
Process simulator
results. Conditions
are listed in Green
Table. SvN question
is: what are outlet
pressure & required
heat for listed
values? Results of
X10.4 by SvN are
presented in Line
item 1 of LHS table.
The pipe simulation results (#2) show in case of SvN heat quantity, the resultant
outlet pressure is 20.4 and temperature is 192.2F. It appears SvN method
incorrectly sets dH=dU for heat required. Where-as the simulator method takes dH
as the heat requirement, without adding velocity head. A check of dH based on
temperature was made from Gas Tables for air, LI 7. The check shows agreement
for the dH by all 3 methods , LI 1, 3-5 & 7. SvN acknowledge an acceptable
error with their method. A 25% heat error and 14% outlet pressure error indicates a
systematic error by one of the methods. LI-5 shows that heat required to match
SvN outlet pressure is only 24.2BTU/# with 46.3 feet of pipe., for same diameter
of steel pipe. The Simulator results with either Beggs Brill or LM method give near
identical results. It is this recommendation to determine heat based on dU and V
head, which more closely match the Clausius Eqn. F=T*dS-Q, with dH reserved for
work, Which agree better with the H-S method of work.
40
The SvN method is an over specification of a problem with one (1) degree of freedom, Gibbs Phase rule:
2-1+1-2. The SvN problem specify inlet P&T + outlet T + isothermal EOS. Problems of two degree have 2
variable, P&T. Solution is by either one equation & 1 specification or two equations + spec of initial
conditions. One cannot add a constraint (reversible, isothermal, isentropic, plus 2 equation. SvN method
uses not 1, not 2 but three (3) equations to solve a problem with 1 degree of freedom. Thus the SvN
method is questionable.
As dH & dU determine heat requirements. The dH & dU are functions of temperature with minor
variants for pressure on volume. However by also using the isothermal expansion, the variant of process
path is fixed. The proposed equation is: (R.B.Bird 1957 in D.M.Himmelblau, 1974 p291&304 eq4-30):
(U+(V
2
/2g)/J)
1
+(Q-W)=(U+(V
2
/2g)/J)
2
+A(PV)+F.
A balance on mechanical energy (ME) can be written on a microscopic basis for an elemental volume
where F represents loss of ME, i.e. irreversible conversion by the flowing fluid of ME to internal energy, a
term which must in each individual process be evaluated by experiment or .. a simular process.. AKA
Bernoulli .. Where friction losses can be evaluated .. from handbooks with aid of friction factors or
orifice coefficients.. Individual terms may be evaluated as follows: For a constant volume Joule
Expansion with W=0, AU0 & A(PV) = PdV + VdP = P*0+VdP =+VdP, the equation is
((V
2
/2g)/J)
1
+Q=((V
2
/2g)/J)
2
+VAP/J+F The friction term is: F = (G/
LM
)
2
(2fL/D)/32.2/778. The expansion
work is -(RT
a
ln[P
2
/P
1
])/MW. The thermal energy AQ is enthalpy change, as shown in simulator results or
AH=C
p
(AT + (AP)
JT
) & = PM / ZRT &
LM
=(
2
-
1
)/ln(
2
/
1
)
The grand equation is: [A(G/)
2
+ (G/
LM
)
2
(2fL/D)]/50000 1.986T
a
[LN(P
2
/P
1
)]/MW = C
p
[AT + (AP)
JT
]
This equation for the case of zero heat addition reduces to the familiar isothermal pressure drop
equation:
[M/(2ZRT
a
)] A(P
2
) - (G
2
/g)[ln(
2
/
1
)+(2fL/D)] = 0
The detailed pressure drop equation without expansion work reduces to Weymouth type A(P
2
) friction
equations. In all events, specification of an outlet temperature leaves 1 degree of freedom, P & one
equation. A spread sheet solution is simple by adjust on P
2
to converge solution.
Gas Expansion with friction SvN Example 10.4 Simulator Results not agree w/ SvN Method
41 41
The adiabatic flow equation derivation uses ideal gas equation for isenthalpic expansion, and C
p
-C
v
=R to
arrive at:
(fL/D)
M
=(4fL/D)
F
= (1/M
o
2
1/M
2
)/k + (1+1/k)ln{[(M
o
/M)
2
][(k-1)M
2
+2]/[(k-1)M
o
2
+2]}
Where: M=Moody Friction Factor, F =Fanning Friction factor , M is Mach number, (ratio of thermal to
Kinetic Energy), k is ratio Cp/Cv, Subscript o is initial condition, fL/D is dimensionless skin friction
number, when expressed with Moody Friction factor is same as Crane K, which can also be expressed as
valve coefficient, Cv, as pointed out by this paper. If Y=[(k-1)M
2
+2], Density, Pressure and Temperature
ratio are
T
o
/T=Y/Y
o
&
o
/ =(M/M
o
)\(Y
o
/Y) & P
o
/P =(M/M
o
)\(Y/Y
o
).
One problem with the adiabatic equation is it predicts a specific M for a given Cv, where-as it is possible
to select an outlet diameter that forces M=M. Looked at another way a given Cv must have a fixed Mach
ratio, which is a doubtful result. Another approach is to relate T=f(P) by the JTX coefficient or 1-1/k = m
but use Schultz definition of m at zero efficiency, m= (P/T)
.jtx
. This determines a Polytropic k based on
a JTX, which appears more realist compared to dS=0 assumed in the adiabatic isentropic approach.
Because any process involving friction is not isentropic. An isentropic temperature drop is greater than a
JTX temperature drop, as indicated by Schultz approach or looking at the H-S diagram, such as for C3=.
Another method is to use real gas energy balance equation, such as: (R.B.Bird 1957 in
D.M.Himmelblau,1974 p291&304 eq4-30): (U+(V
2
/2g)/J)
1
+(Q-W)=(U+(V
2
/2g)/J)
2
+A(PV)+F.
AU=C
v
(AT + AT
JX
) or AU=C
v
(AT + (1/k)AT
JTX
) or AH=C
p
(AT + AT
JTX
) & use real density =PM/(ZRT)
The prior article proves the validity of this total energy approach and the results so obtained do not
introduce ideal gas assumptions. Nor does the total energy equation bias results by introduction of a
predefined thermodynamic path. The AT
JX
& AT
JTX
are just the Joule or JT Expansion temperature
change using the low pressure C
v
or C
p
and is thermodynamically correct.
Gas Expansion with friction Adiabatic Flow Equation is an Ideal Gas Isenthalpic Expansion
42
Equation for ideal gas adiabatic compression head: H
a
= RT
1
(k/(k-1)((P
2
/P
1
)
(1-1/k)
1) but
Rk/(k-1) = (C
p
-C
v
)(C
p
/C
v
)/(k-1) = (k-1)C
p
/(k-1) = C
p
so rewrite H
a
as H
a
=T
1
C
p
((P
2
/P
1
)
(1-1/k)
1)
& for adiabatic gas T
2
=T
1
(P
2
/P
1
)
(1-1/k)
Distribute T
1
inside radical of
AH
a
= C
p
(T
1
(P
2
/P
1
)
(1-1/k)
T
1
) = C
p
(T
2
-T
1
) & dH
n
= C
p
(T
2n
-T
1
) efficiency adjust head
The above shows adiabatic compression head is just an expression for ideal gas enthalpy change less the
velocity heads. The ideal compressor or expander does not have velocity heads.. In practice velocity heads
are mitigated by keeping Mach numbers low with selection of inlet/outlet nozzle sizes.
Since adiabatic head is just enthalpy change, it seems more prudent to improve estimates of compression or
expansion temperature change and improve enthalpy evaluation methods. This will more closely match a H-
S chart. Especially so, where gas conditions have large deviations from ideality. The Schultz method is one
attempt to better determine temperature change but failed by double counting efficiency. Enthalpy
calculation is next considered.
Clearly: Power is just product of head and flow, adjusted for driver inefficiency. Some engineering texts double or treble
count the efficiency term for power calculation: examples are: Perry 5
th
ed Eq.24.20 to 24.24, C.Branan GPC 1976 Eq.3.2&3.4,
Evans, GPC pp42&58, Ludwig GPC 1983 v3 Eqn12-54, Coulson et-al pp94/5 to cite a few readily at-hand, likely there are
others. Once the head has been adjusted for Polytropic efficiency, the only further corrections to shaft power are losses from
driver source power to impeller. Conversely, for expanders, application of double or treble efficiencys under estimates the
available gas power. This concept is clearly seen in the H-S diagram, where once head is determined based on efficiency,
power is just product of flow times head. Shaft power adjusted for bearing & seal friction. If this effect is corrected in the
Schultz equations, a much better fit to the H-S power is obtained. Repeat: one does not determine Polytropic head by
Polytropic n, then re-correct Polytropic Head by efficiency or worse still, additionally take another correction of Polytropic
efficiency to the product of head and mass rate: repeat: true head times mass rate = gas power & once head adjusted for
efficiency by use of Polytropic n, ,no further adjustment needed.
Ideal Enthalpy Equation v. Adiabatic head & cautions
43
Ah = C
p
AT + (V T[(cV/cT)
p=c
)AP (11.17 Eqn. 11-26 Faires & 11-7 Walas 1985), with

JT
= {T[(cV/cT)
p=c
]- V)}/C
p
so - C
p

JT
= (V T[(cV/cT)
p=c
) gives Ah = C
p
AT + (-C
p

JT
) AP
AH = C
p
(AT -
JT
dP) = C
p
(AT - AT
JTX
), & AU =C
v
(AT - AT
JX
) C p or C v are C @ 1atm.
The true dH could be also be written in terms of | = [(cV/ cT)p=c ] as
JT
= (T| -1)/(Cp). The above is same
as adding an additional dT.jt. But expansion coefficient were found more accurate than of adjusting Cp for
pressure. Either should define a dh with improved match of H-S chart enthalpy. Calculation of JT coefficient:
JT, by H-S chart is also possible, ie: for C3=, pg94 Scheel, P
1
=125, P
2
=20, AP=-105, & T
1
=100F, T
2
=-35F,
T
a
=67.5F AT=-135, Ah=-40BTU/#, Cp=0.35BTU/#/R, & Cp =0.36 at avg. T of 528R =(4.234+.0206R)/42, p270
Ludwig vol.3, or 0.363 SvN p106 so take average of 0.361.

JT
= (dT
a
dh/Cp)/dP
JT
=(-135+40/0.361)/-105 = 0.23, about what viral EOS gives if in
o
R/psi or 3.4R/atm,
see JT comparison page. by Scheel HS chart
JT
= (AT/AP)h=c =25/105 = 0.24R/psi =3.5R/atm exactly as given
by BWR EOS.
H & U of real gas as function of
JT
&
J
Temperature change:
Callendar Schultz HS chrt*
T
2
w/P corr C
p
-42.5F -43.3F -38.5
dH w/P corrn 47.6 btu/# - 40
dH w/C
p
@1atm 40.03 btu/# 40.3 btu/# 40
Table on RHS compares T
2
& dH calculations.
Using above dH formula w/o Cp pres. correction
gives best dH results. Neither method matches T
2
of HS chart. The Table confirms correct C
p
is C
p
@
1atm as this same equation used to correct dH for
pressure. *P-H CRI 1961 Carrier #144, Not same
as Scheel Chart H-S shown by this document, Ah
of Scheel chart for P1=125, P2=20, T1=100F,
T2=100F is: -[((20-125)/14.7)* 3.5 ] 0.361 = Ah =
+9.03 BTU/# AH isothermal. & H isothermal =
137 + 9.03 = 146. For Isentropic at same
pressures: T2= -35F & Ah=
& Ah=[(-35-100)-((20-125)/14.7)*3.5] 0.361 =
Ah=(-135 +25)0.361= -39.71 = Ah isentropic Vs. chart
of 40BTU/#. For AU=0, T2 =93F,
Ah =0.36[93-100-((20-125)/14.7)*3.5] = +6.5 btu/#.
Sign Convention Check: AH=0 & AU=0 is always
C(dT-dTx) or dT=dTx & dT is mostly negative
44
Determine ACp by Explicit EOS: (cC
p
/cP)
T=c
= -c(
JT
C
p
)/cT|
p=c
R. L. Callendar EOS: V=RT/P+b+a/T
3.33
ACp = 7.2R (AP/Pc)/T
r
4.33
given without derivation
Or by Berthelot EOS
ACp = 2.5R (AP/Pc)/T
r
3
given without derivation
Compare Cp Corr Method
y = -16.149Ln(x) + 0.4203
R
2
= 0.9957
0.0
5.0
10.0
15.0
20.0
25.0
30.0
0.380 0.480 0.580 0.680 0.780 0.880 0.980
Z.rk
d
C
p Callendar
Berthelot
Chart2-237
BCdr.avg
Log. (BCdr.avg)
AIR dCp T=-50C Cp P=1atm Cp p=100
ICT Table 0.174 0.238 0.412
dCp Calldr 0.141 0.238 0.379
dCp chart 0.100 0.238 0.338
dCp Bero' 0.096 0.238 0.334
Chart/Table Perry p3.237 & p3.134 BTU/#/R
Tc K / Pc atm 132.8 37.2 The comparison table for air
shows the Callendar EOS
provides superior estimation
of heat capacity change with
pressure vs. Reduced
coordinate Chart or the
Berthelot EOS Equation.
It is no surprise that dCp
correlates well with Z. It
appears the Callendar method
of estimating dCp is an
improvement over other
methods. N.B. When using the
corrected Cp then is
necessary to also use
corrected Cp-Cv value to
determine isentropic
exponent to determine T2 of
adiabatic expansion or
compression. Recommend to
use the JT correction for dH.
Note: R. L. Callendar produced the 1
st
steam tables and Mollier used the
Callendar EOS to make the well known chart for steam,Cira 1925AD. Also,
the Keys & Kay Steam Tables use the Callendar EOS for superheated steam
properties, Wiley Publishers
45
Schultzs
method
On page 80 example he
wrongly uses Wa =Wp/e.
Polytropic work Is Actual work
Schultzs Method For dH & dT Adiabatic, Perry 5
th
ed. Eq.24.20 to 24.24,
46
Schultzs X
Chart
47
Schultzs Y
Chart
48
This result questionable
Not agree w/ Perry
No precise reference
A ?? Mod of Schultzs dH & dT method
49
Express 9 = C
p
-C
v
for real gas as z 9 =C
p
-C
v
PV=zRT- real gas Law
Define H=U+PV & dH/dT = dU/dT +d(PV)/dT (valid only for reversible processes)
dH/dT = C
p
& dU/dT =C
v
& d(PV)/dT = d(z 9 T)/dT
Use d(z 9 T)/dT = z 9 + 9 Tdz/dT
Sub the values into: dH/dT = dU/dT +d(PV)/dT to get:
C
p
= C
v
+ z 9 + 9 Tdz/dT or (C
p
-C
v
) = (z 9)[1+T/z (dz/dT)]
C
p

jt
=T/z(dz/dT) or (C
p
-C
v
) = (z 9)[1+ C
p

jt
/2.72] (same as Schultzs Eqn.)
a 1
st
approximation is by neglecting term C
p

jt
/2.72 is:
C
p
- C
v
= z9
Dimensionless Number Units: C
p

jt
=(#/CF)(BTU/#/R)(R/atm)(1atm-cf/2.72btu), & AH=ATC
p
& AU=ATC
v
Aside: AH =AU + z9(AT), =AU + PAV + VAP by steam table @P&T=c, L -> V check:@1atm, 212F:
970.3=897.5 + 72.8 =970.3 & TAS=970.3 = AH
Compare to Berthelot (1907) approximation for corrected C
p
-C
v
:
C
p
-C
v
= R(1+1.7P
r
/T
r
3
). The empirical Berthelot EOS is: Z=1+(1-6/T
r
2
)9P
r
/(128T
r
).
The exact Blot value for R correction, d(z 9 T)/dT, is R(1+1.7P
r
/2T
r
3
), hence the word, approximation. Blot EOS is a
truncated viral with e set to zero. The Blot Bo term is 0.07-0.42/T
r
2
Compare to Abbott's B
o
term of B
o
=0.083-0.42/T
r
1.6
.
Some simple gases with zero e or e<0.044, are: the noble gas series, air, O2, N2, H2, CO, and methane. For such gases
the Blot EOS should be as accurate as the truncated Viral EOS. The empirical Blot EOS is par to vdW or superior at room
T & P<200atm. Walas85
50
Review of: Schultz, JM, Polytropic Analysis of Compressors, Trans. ASME J. of Engi. for
Power (84) 1962 Part 1 Jan. p69, part. 2, p222 in Perrys 5
th
Ed. Pg.24.34
T2=T1{P2/P
1
)
(m)
} m=(Z9/C
p
)() & =(c+X)
expansion
=(1/c + X)
compress
X
s
{[(T/V)(cV/cT)
p
] 1} ~{ln(Z
2
/Z
1
)}/ln(T
r2
/T
r1
) & Y
s
{(-P/V)(cV/cP)
T
} ~1-{ln(Z
2
/Z
1
)}/ln(P
r2
/P
r1
)
Now recast X, above in terms of JT function, =(T/V(cV/cT)
p
-1)(V/C
p
)
C
p
/V = {[(T/V)(cV/cT)
p
] 1} = X with 1/V= =(c + C
p
)
expansion
m
s
=Z(C
p
- C
v
)c/C
p
+Z9C
p
/VC
p
=Z9c/C
p
+Z9/V=Zc(1-1/) + Z9/V
By real gas law P/T=Z9/V so m=Zc(1-1/) + P/T
At c =1 for ideal gas, (Z=1 & =0) reduces to the familiar T
2
= T
1
(P
2
/P
1
)
(1-1/k)
At c =0 for ideal
gas, (Z=1 & =0) gives T
2
=T
1
. Few gases are ideal so at small c, expect big errors.
For the locked rotor case where c =0 gives T
2
= T
1
(P
2
/P
1
)
(P/T)
Schultz equation results are normal as it defines as: =(P/T)ln(T2/T1)/ln(P2/P1). LF Scheel
shows @ locked rotor case dT= (dP). Schultz says dlnT=(P/T)dP =dT/T=(P/T)dP/P or
dT=(dP) Schultz method gives improved results compared to the ideal gas case, see
following charts.
Since k
T
=-(1/V)(cV/cP)
T
& Y
s
{(-P/V)(cV/cP)
T
} then Y
s
=Pk
T
The term k
T
is the isothermal compressibility aka Cg in petroleum reservoir analysis.
To keep (c + C
p
) unit less, when (#/CF)(R/atm)(BTU/#/R), use the conversion of 1CF-atm per 2.72BTU
or 0.73/1.986 = 0.37 or (c + 0.37C
p
).
51
m
s
= (9Z/Cp)(c+X
s
) & m.
jt
= (1.99Z/C
p
)(c + 0.73
jt
C
p
/1.99) & m.
ideal
=(1-1/k)c & C
p
= 4.234+
o
R/48.54,
btu/mol/R for C3= only,
jt
per the RK EOS,R/atm.; =PM/(Z10.7
o
R), #/cf; Z per RK EOS, P
c
T
c
& X
s
as
per data given here-in. k= C
p
/C
v
.
The ideal case has large error at c=0 as it predicts Tin=Tout, vs a JT expansion for locked rotor as
shown by Scheel on the H-S chart for C3=.
The JT correction method without C
p
correction is an improvement over other methods, if one lacks H-
S charts for a particular gas.
calc error for Xpander Outlet T
0.000
0.010
0.020
0.030
0.040
0.050
0 0.2 0.4 0.6 0.8 1
Expander Efficiency
a
b
s
E
r
r

T
o
u
t

v

H
-
S
Err JT.rk w/Cp corr
Err ideal
Err SchulteX w/Cp corr
Err JT.w/o Cp corr
Compare Temperature difference to HS chart of C3= for ideal, Schultz, & JT
52
By Schultz: n
s
=1/(Y-m
s
(1+X
s
)) & for ideal case n=c(1-1/k), k=Cp/Cv ideal.
dH
poly
= c(-n /(n -1))(ZRT)
1
((P
2
/P
1
)
((n-1)/n)
-1).
Simpler just calculate dH from JT equation: dh = c Cp (dT -
JT
dP), where -
JT
dP conveys non-ideality,
per appendix. The above chart shows the lowest accuracy for the ideal case. Were efficiency not double
counted in the Schultz method, it would be the more accurate method. However Schultz method
requires a further 3 parameters over the JT method,
dH @ e=1 is 40BTU/# from HS C3=
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
0 0.2 0.4 0.6 0.8 1
efficiency
a
b
s
(
d
H
c
l
c
-
d
H

h
-
s
)
Err JT.rk w/Cp corr
Err ideal
Err SchulteX w/Cp corr
Err JT.w/o Cp corr
Compare Enthalpy difference to HS chart of C3= for ideal, Schultz, & JT
53
Gas in out Gas calc in res ult out.R es ult imed res lt in out
T, F 751.400 445.400 T den pcf 0.190 0.129
P, 'ps ia 88.200 ps ia 22.10 V fps 71.49 0.62
#/hr 4930.000 4930.000 friction Hd ft 0.0 81482.6 Ai" s q. 14.499 14.499
Lpipe E q ft' 10000.000 10000.000 Work Head ft -58413.6 0.0 f 0.0040 0.0040
di inch 4.296 4.296 V head ft 79.4 706.6 R e 381579.63 381579.63
MW- N2 28.000 28.000 P head ft 66786.2 49916.0 Efficiency poly.idl 0.77
Cp btu/#/R 0.248 0.248 T hd ft C v 123629.1 0.0 P2 es timate 44.69
u cp 0.019 0.019 s um 132081.1 132105.2 G #/s ec/s f 13.6
Z 1.000 1.000 Mach 0.04 0.00 2R Tz/M avg 32.4
Anal:C ouls on X3.15:Po=22.1ps ia,To=445.4F,poly.E ffic.=0.75&Ht=-59950, &this w/e=0.75=>Po=21.6,To=451F &Hpoly=-57226'
Anal: X3.15 phead tot.=59,950 feet vs calc 58414, diff is V Hd, us e X3.15 Pi/Ti 88.2/751.4 & Hw=58414 w/77%eff. To/Po445.4/22.1
us e HP=e*(Work-ft)*(#/min)/33000
N2 Expansion Turbine Calc Performance by Pipe Friction
The above example from Coulson X3.15:Po=22.1psia,To=445.4F,poly.Effic.=0.75&Ht=-59950, &
this w/e=0.75=> Po=21.6, To=451F & Hpoly=-57226
Anal: X3.15 phead tot.=59,950 feet vs calc 58414, diff is V Hd, use X3.15 Pi/Ti 88.2/751.4 &
Hw=58414 w/ 77%eff. To/Po445.4/22.1
When calculating AU, or internal energy change, the Joule correction is neglected. This is not
considered a serious omission because
j
AV is small or AU=C
v
(AT +
j
AV) ~ C
v
AT, as seen by how close the
energy balance closes.
54
Cross Correlations of Coefficients I
For ideal gas:
JT
=0, | = 1/T, k
T
=1/p, k
s
=1/(p), & a
s
=1/\(k
s
), C
p
- C
v
= 9
For Real gas:
JT
=(cT/cP)
h
, | =(cV/cT)
p
, k
T
=-(cV/cP)
T
, k
s
=-(cV/cP)
s
,

JT
= (cT/cP)
s
-1/(C
p
) = (T| -1)/(C
p
) = [T(cV/cT)
p
-V]/(C
p
)= [(cP/cT)
v=c
]
Joule Free Expansion:
J
(cT/cV)
U=c
=(-1/C
v
)(cU/cV)
T=c
=-[T(cP/cT)
V=c
P]/C
v
compare to
Joule Thompson Exp.:
JT
(cT/cP)
H=c
=(-1/C
p
)(cH/cP)
T=c
= [T(cV/cT)
p=c
V]/C
p
C
p
- C
v
= T|
2
/(k
T
) & C
p
/C
v
= = k
T
/k
s
&
s
= (cT/cP)
s
& a
s
=\(cP/c)
s

s
-
JT
=V/C
p
= ZT(1- k
s
/k
T
)/P & = (cV/cP)
T
(cP/cV)
s
& a
s
~\(P/)
k
T
=[1/p-(cZ/cP)/Z] & | = [1/T- (cZ/cT)/Z] &
JT
=(9T
2
/P)(dZ/dT)/C
p
AV/V =[(|)AT + (k
T
)AP] &
JT
= (cT/cP)
s
-1/(C
p
)
Routines for z & k
T
commonly available using T
r
, P
r
for, reservoir work, like:
k
T
=(1/(P
c
P
r
))(1/(1+(
r
/Z)(cZ/c
r
))) where Z &
r
from BWR EOS
(cZ/c
r
)=[5A
r
5
+2B
r
2
+C
r
+2E
r
2
(1+F
r
2
F
2

r
4
)exp(-F
r
2
)]/(
r
T
r
)
For example at Tr=1.7, Pr=2.8, Pc=361.5psi k
T
=0.001/psi & 1/V =
m
= (Psia)/(z10.7/
o
R)
9 : 1.98BTU/mol/R, 0.7302atmCF/mol/R, 1545ft#/mol/R & J = 778ft#/BTU
55
Cross Correlations of Coefficients II
(cC
p
/cP)
T=c
= -c(
JT
C
p
)/cT|
p=c
= -c[{9T
2
/P}(cZ/cT)]/cT|
p=c
for C
p
of P=1
(dC
p
)
T
= -(|
2
T/)dP (cC
p
/cP)
T
= -TV(|
2
+ (c| cT)
p
) & (cS/cP)
T
= -(cV/cT)
P
cS/cP|
T=c
= -|V & cS/cT|
p=c
= C
p
/T & cS/cV|
T=c
= (|/k
T
) = (cP/cT)
v
(cU/cP)
T
= (Pk
T
-T|)V = (1+Pk
T
- |T)V & (cU/cV)
T
= {(T|/k
T
) P}
AU=(C
p
- p|/)AT + (Pk
T
-T|/)AP = AU = C
v
(AT-
J
AV)
(ch/cP)
T
=(1 - |T)/ & (ch/cV)
T
=(T|-1)/k
T
AV/V =(|)AT + (k
T
)AP & (c|/cP)
T
= -(ck
T
/cT)
P
& (cP/cT)
v
= |/k
T

JT
= (T| -1)/(C
p
) where | = [(cV/cT)
p=c
] = [(cP/cT)
v=c
] k
T
& =1/V= P/z9T
k
T
=[1/P - (cZ/cP)|
T=c
/Z] & | = [1/T - (cZ/cT)|
P
/Z] &
JT
={9T
2
/P}(cZ/cT)/C
p
AH = C
p
(AT) - [T(cV/cT)
p
-V]AP & AU = C
v
(AT) + [T(cP/cT)
V=c
P]AV Perry4-144/151
But (C
p
)
JT
= [T(cV/cT)
p
-V] & -
J
C
v
= [T(cP/cT)
V=c
P], so AH & AU by
JT
&
J
is =
AH = C
p
(AT) - [(C
p
)
JT
]AP & AU = C
v
(AT) + [-
J
C
v
]A(1/V)
The above 2 equations may be used to correct AU & AH for conditions other than 1atm.
AH = C
p
(AT-
JT
Ap) & AU = C
v
(AT-
J
A(1/V)) for gas expansions with AH=0 or AU=0
AT
JTX
=(
JT
Ap) & AT
JX
= (-
J
A(1/V)) AKA isenthalpic w/AH=0 & constant U ie AU=0
56
Corresponding States Concept for EOS & Z
The corresponding state idea is the basis for Z charts. It is also the basis of any EOS i.e. use Pr & Tr. The idea
is that all gases have identical Z at the critical condition of Pr=Tr=1. This is not always a good approximation,
as seen by the table below. Z
c
for hydrocarbons and the average for all gasses is 0.27. Thus Z
c
= 0.27 is the
basis for most Z charts. Polar molecules have smallest Z
c
, whilst spherical molecules have largest Z
c
. The
vdW EOS Z
c
is 0.375, while RK EOS has Z
c
about 1/3, the BWR form presented here has Z
c
of 0.27.
Limitations to EOS validity range should be strictly observed. For example, Berthelot and 2 term viral
calculate Z
c
of 0.65. The recommendation for the 2 term viral is for Vr>2 & below 2 use Pitzer Charts. The
Pitzer Charts also use Z
c
of 0.27 but adjust for a given gas by e. Therefore the potential for severe
departures from true values should Vr<2 or Pr>30 or other range limits set by an EOS. One correction
proposed for H2O, H2, He, Ne, NH4, to improve accuracy for the vdW EOS is the Newton correction. It uses
T
cn
=T
c
+8K and P
cn
=P
c
+8atm. Even with these corrections there may be significant error unless Tr>2.5. Faires
pp216/217. Others only recommend Newton correction for H2O & H2 if using Z charts. A vdW gas fitted to
Pitzer viral form has e of 0.303. The next idea uses tailored EOS fitted around Z
c
for a particular gas or gas
type, e.g. BWR given here. Advanced EOS use an accentric factor, e, to make adjustment for effect of Z
c
.
Examples are LK-BWR, S-RW, and Ping-Robinson. All of which use complicated, empirical, and sometimes
proprietary mixing rules. An advanced EOS is needed when needed precision exceeds that of a two
parameter equation. Some examples are: High Concentrations of Polar/Ionic gases, Quantum Gases or
conditions near the critical point. A comparison of results can give an idea of whether to use an advanced
EOS. If the imposed limits are exceeded or a large scatter is seen among results, this may justify additional
investigation. At last count, the number of EOSs are hundreds. One of the latest is a 5
th
order viral, termed
ELIR or extended linear isotherm regularity. ELIR gas is defined by 2
nd
& 3
rd
viral coefficients and Boyle
density is family of curves for cZ/cP|
T=c
=0 &
b
=(c(PV)/cP)
T=c
=0. Boyle Temperature is T at P=0 for which
cZ/cP|
T=c
=0
' C ompare Zc to E OS and Z chart C orres ponding S tates : Pitzer Viral Zc, 0.24->0.29 & BWR * 0.27
Gas CAN HCN H2O NH3 nC6 Av g Gz BWR* Z chrt C2 C3 CO2 C1 Air H2&He Ne RK v dW
Zc 0.189 0.197 0.233 0.243 0.264 0.270 0.270 0.270 0.270 0.277 0.279 0.290 0.290 0.305 0.310 0.310 0.370
Z
c
=0.291-Ae (Yamada Liquid A=1, LK-BWR, A=0.085 & Edminster, A=0.08, Pitzer, A=0.28)
57
Kinetic Theory of Gases
The Kinetic Theory of Gases provides insight to fundamental relations among gas properties like friction,
or momentum, heat, and mass exchange. Kinetic Theory proposes: /==k/C
v
=V
rms
/3. Stated as,
viscosity over density equals Diffusivity, equals heat conduction coefficient over density times constant
volume heat capacity, which all equal 1/3 of the root mean square velocity of a gas molecule times the
mean free travel path of the molecule. Each of these 3 coefficients also have Dimensionless Numbers as a
basis for engineering calculations. Collectively known as the Colburn analogy: f/2= j
H
=j
M
. Friction factor,
f, is the ratio of momentum loss at wall to bulk shear. Likewise j
H
is ratio of heat transfer at wall to the
bulk available heat. Chilton and Coburn verified the analogy for a wide range of compounds, with errors
typically under 10%. The dimensionless numbers; (DG/), (C
p
/k), & (/M); are known as Reynolds,
Prandtl, and Schmidt. By Kinetic Theory, k= AC
v
& = A so the Prandtl number is the ratio of heat
capacity, (C
p
/C
v
). Gambil arranged Prandtl numbers of gasses by molecular structure, 0.67 for mono-
atomic gases, 0.73 for linear Non-polar, 0.79 for non-linear non-polar 0.86 for polar and about 1 for H2O
vapor. Kern made the observation that N. Prandtl is useful for physical properties extrapolation. As
Prandtl values at a mean temperature will be valid for a wide temperature range. This is perhaps simular
to the Cp/Cv value for gases. For gas viscosity, kinetic theory predicts an increase in viscosity
proportional to the root of absolute temperature, such as the Sutherland Equation for temperature
extrapolation of thermal conductivity. Diffusivity and viscosity determinations differ little from
considerations given by gas kinetic theory, corrected for temperature effect. Correlations for these
coefficients are given in various reference texts. See following table for details.
Consider the energy balance in terms of Kinetic Gas Theory for a mono atomic gas:
(P/ + V
2
/2g)
1
+ E
G
= J C
v
AT + (P/ + V
2
/2g)
2
+F
L
Sub JRT for P/=PV & 1.5R for C
v
: (JRT + V
2
/2g)
1
+ E
G
= J 1.5R AT + (JRT + V
2
/2g)
2
+F
L
Sub for AT= T2-T1 : (V
2
/2g)
1
+ E
G
= J 1.5R AT +J RAT + (V
2
/2g)
2
+F
L
Add the R ATs: (V
2
/2g)
1
+ E
G
= J 2.5R AT + (V
2
/2g)
2
+ F
L
Use Mono gas table & Sub for 2.5RAT as AH: (V
2
/2g)
1
+ E
G
= JAH + (V
2
/2g)
2
+ F
L
Notice result is the same when determined by ideal gas law:
A proper energy balance MUST account for friction to specify the result.
58
Kinetic Theory of Gases
Item Viscosity Heat Flow Diffusion
Coefficient /=V
rms
/3=74.3\(
0
R/M)=
k/C
v
= V
rms
/3 =
=V
rms
/3=74.3\(
0
R/M)= V
rms
/3
term [d(mv)/dt]/A= dv/dr Q/A= k dT/dr J=dm/dt=DA dm/dr
property
*
=27\(MT)/[V
b
(1+Tc/Tb)]
k=(C
v
+99/mw)
*
AA
~1.57V
c
-0.67
\(
0
R/MW) Perry 1973
Analogy
f/2=0.023/(DG/)
0.2
=
j
H
=(h/C
p
G)(C
p
/k)
0.67
=
. j
M
=(kM/G)(/M)
0.67
Analogy A(P).wall/(bulkA momentum) = AQ.wall/Bulk AQ= =Am.wall/bulk Amass= = Constant
-d # name
Reynolds Number Prandtl Number Schmidt Number
Lewis #
-d # ratio
(DG/), inertia/viscous (C
p
/k)
(/M) = (/k
d
)
(k/MC
p
)
application
APD/(4LV
2
/g)=f/2 j
H
=(AT/At)(a/A)(C
p
/k)
0.67
j
d
=(AP/Ap)(a/A)(/k
d
)
0.67 Kern 1950
This analogy is limited to Reynolds numbers above 5k and is exclusive to wall drag. It is also limited to moderate
temperatures to eliminate radiant heat transfer.

*
AA
~ Sq.ft/hr Critical Volume in CF/Mol. T is degrees of Rankin temperature. These expressions are used to demonstrate
that viscosity and thermal conductivity are proportional \(MT) to while diffusivity and sonic velocity are proportional to
\(T/M). Improved methods make better accounting for the mean free path or collision integral as in, Perry Ch.3, Kern
pg344. The sonic velocity is predicted by gas kinetic theory as C=V
rms
\(C
p
/C
v
/3).
Another dimensionless number, Lewis Number, is basis for humidification or circumstances of co-current heat & mass
transfer. It is the ratio of Prandtl to Schmidt Numbers, known as the Lewis Number or (/M)/(C
p
/k). Kinetic Theory
predicts a value of 1 for the Lewis number. Experimental evaluation determined Lewis numbers to range from 0.9 & 1.1
for air -water between 150F and 950F.
A consideration is that boiling temperature is 63% of the Critical temperature and gas molecular radius in Angstroms is
estimated at 3.32 times cube root of critical volume in cf/mol, as applied in estimation of diffusion constant above.
59
Dimensionless Numbers of Gas Expansion
The dimensionless Number, C
p

JT
, is a ratio of gas expansion temperature change to friction
temperature change, for dP &
JT
=0, as AT
F
= AP
F
/(J.) = AT
JT
= (
JT
C
p
)AP. Which is true only when
0Ah=CpAT+(-Cp
JT
)AP. Recognizable as the isenthalpic case using Schultz Temperature relation for the
general isentropic case.
To keep (C
p
) unit less, when (#/CF)(R/atm)(BTU/#/R), use the conversion of 1CF-atm per 2.72BTU or R/R
=0.73/1.986 = 0.37CF-atm/BTU or (0.37C
p

JT
)=N
JT
.
Another dimensionless Number, the Joule Number or N
J
= (J/P)C
v

J
, is associated with the Joule Free
Expansion. It is the ratio of dTw =P(dV/J) and dT.jx = (dV)C
v

J
, the dVs cancel leaving: N
J
= (J/P)C
v

J
.
A 3
rd
dimensionless number may be formed by taking the ratio of the 1
st
two, namely:
N
JA
=(N
JT
/N
J
) = (0.37C
p

JT
)/((J/P)C
v

J
) = (0.37/J) (AP/AV)(C
p

JT
)/(C
v

J
) from pressure & volume change is:
N
JA
=AE
JT
/AE
J
= (C
p
AT
H=c
)/(C
v
AT
U=c
) = (APC
p

JT
)/(AVC
v

J
) which can be related to the ratio of (AH/AU) as
the ratio number relates to how to adjust Enthalpy and Internal Energy changes from standard Conditions
of 1 atmosphere to pressure either higher or lower than 1 atmosphere.
AH = C
p
(AT- AP
JT
) & AU = C
v
(AT- AV
J
) for at AH =0 & AU =0, then AT
JX
= AV
J
& AT
JTX
= AP
JT
Furthermore it seems N
JA
=(N
JT
/N
J
) must be related to acoustic velocity at real conditions. Sonic velocity is
determined as a =\(cP/c) =-(V/)\(cP/cV)|
s
~? -(V/)N\{(C
p

JT
)/(C
v

J
)/|
s
]
This is just a presentation of talking points. The main point is to better understand what Schultz did in
development of his method.
60
Kinetic Theory of Gases provides insight to the relations among gas properties such as, friction, heat,
and mass transfer. Kinetic Theory proposed: R=Nk and also adds the quantumization to account for
energy stored by vibration and rotational modes. Quantization implies molecules have discrete energy
levels. Quantum responses are discrete step functions activated at specific temperature intervals. The
resulting expressions of various monatomic gas (such as He, Ne) properties are expressed in Table 1,
below. Some of the Quantum functions, (Qi) , are as follows:
(Qt1)= (2tMkT)
1.5
V/h
3
N & (Qr2)= (eT) /oO & (Qv3)=x/(e
x
-1) & (Qv4)=e
x
(x/(e
x
-1))
2
& (Qv5)=Qv3-ln(1-1/e
x
)
where X = chv/kT. The various terms are: temperature, T , absolute, & v, is vibration frequency.
Example from Daniels & Alberty Pg. 577 (1975) is for H2O Cp at 1000K which is listed as having 3 normal
vibration modes at 1000K of 1595, 3652, & 3756 inverse cm. The calculated Cv is:
R(5/2+3/2+(0.66+0.146+0.133)) = 9.81 vs. experimental of 9.77. The terms were modified for 3 degrees
of freedom based on the diatomic system. T.1 Mono
T.2 Diatomic
Kinetic Theory of Gases
Degree
disassociation
P
not
U
considered
C
v
C
P
H S
Translation RT/V 1.5RT 1.5R 2.5R 2.5RT 2.5Rln(Qt1)
Rotation RT R R RT Rln(Qr2)
Vibration RT (Qv3) R(Qv4) R(Qv4) RT (Qv3) R(Qv5)
Summary: Gas energy by Kinetic Theory is an exclusive function of temperature. Gas Pressure and
Entropy are related to temperature, specific volume. /==k/C
v
=V
RMS
(/3).
P RT/V
U 1.5RT
C
v
1.5R
C
p
/C
v
1.67R
H 2.5RT
S 2.5Rln(Qt1)
A formula for C
P
is R(1+f/2) & C
P
/C
v
=1+2/f. With f = number of degree of freedom. For the example
H
2
O vapor at 1000K the degrees of freedom activated are: 2(9.81/1.986-1)= 7 plus 88% of the 8
th
degree, thus k=1+2/7.88=1.25 At room temperatures k mono=1.67, diatomic=1.4 and poly at.=1.33.
Kinetic theory Temperature is proportional to the square of V
rms
. Thermal equilibrium between 2
objects of different temperature is achieved when they have identical RMS velocities.
61
Properties of Common Gases
gas MW k60F Tc Pc Zc a.vdw b.vdw w.actr A B Zac u.jt.v u.j.v Cp
Air 29 1.41 239.0 37.2 0.284 345 0.585 0.036 6.737 3.97E-04 0.998 0.43 0.08 6.96
N2 28 1.41 227.0 33.5 0.291 346 0.618 0.040 6.839 2.13E-04 0.999 0.42 0.08 6.96
O2 32 1.40 278.0 50.1 0.290 348 0.506 0.021 6.459 1.02E-03 0.996 0.46 0.08 7.03
CO2 44 1.30 548.0 72.9 0.276 926 0.686 0.225 6.075 5.23E-03 0.962 1.16 0.17 9
C1 16 1.32 344.0 45.8 0.290 581 0.685 0.007 4.877 6.77E-03 0.987 0.68 0.11 8.67
C2 30 1.22 550.0 48.2 0.284 1410 1.041 0.091 3.629 1.68E-02 0.943 1.22 0.17 13
C2= 28 1.25 510.0 50.5 0.270 1158 0.922 0.086 3.175 1.35E-02 0.957 1.20 0.17 10.7
C3= 42 1.16 657.0 45.6 0.275 2129 1.315 0.148 4.234 2.06E-02 0.893 1.57 0.23 15.8
H2 2 1.41 59.8 12.8 0.304 63 0.426 0.000 6.662 4.17E-04 1.005 -0.05 0.01 6.9
R12 121 1.13 692.0 39.6 0.272 2718 1.595 0.158 8.399 1.59E-02 0.853 1.84 0.29 17.3
NH3 17 1.32 730.0 111 0.242 1076 0.598 0.250 6.219 4.34E-03 0.934 1.47 0.22 8.65
Toul 92 1.10 1065.1 40.6 0.264 6285 2.394 0.257 1.869 4.30E-02 0.315 2.97 3.11 25.9
Ne 20 1.67 79.9 27.2 0.311 53 2.68 0.000 5.000 0.0E+00 1.003 -1.32 0.02 5
Tc,R Pc atm, Cp BTU/mol/R=A+B(F+460), a atm(CF/m)^2 b cf/m u.jt R/atm u.j R-mol/cf 125psia 560R
Basis of a & b from vdW is Tc & Pc. Joule Thompson & Joule Coefficient Calc by vdW formula. Z calc by viral
equation with Abbott eqn4B at P=125psia & T= 100F. Volume for C3= at these conditions is
0.893*10.72*560/125 = 42.9cf/mol & at 20psia V=0.96*10.72*556/20=286cf/mol, AP=(125-20)/14.7 = 7.14
atm & C
v
=15.8-1.986=13.81BTU/mol/F. EX: For C3= expanded from 125psia to 20 psia, from initial
temperature of 100F, the resulting temperature is
AT
JTX
= (
JT
AP) =1.57*7.14/ = -11.2R & AT
JX
=
J
V
2
(A(1/V)) =0.23*43
2
*(1/43-1/245)= -8.4R
62
Review of C3= Gas eXpansion by thermodynamic states
This table shows results for the thermodynamic state changes of C3= expansion by various process
paths. The values used to determine these changes were tabulated from Carrier Chart #144, as best it
could be read. The initial condition was taken at 125psia and 100F.
The comparison is made for: Isothermal X (JX), Isenthalpic (JTX), and Isentropic (IEX) Expansion paths.
The focus is to compare JX expansion to other expansions. Some argue that JX type expansions require
heat addition. No more so than the original Joule expansion required heat to be isothermal. For a
pedagogical ideal gas only, Isothermal X is just a Joule X aka constant internal energy X. Heat need not
be added to get a JX any more than work need be done to get a IEX. The classic IEX is thru a deLaVal
nozzle, where about 96% of available energy is converted to kinetic energy, typically for turbine
utilization. The AG function indicates spontaneity or degree of organization needed. While dG indicates
maximum work potential. The AS function indicates the probability of the process. Both these quantities,
AG & AS, show that IEX requires more organization than JTX, than JX. Square edged turbulent
expansion favors a JX compared to highly machined curved surfaces with streamlined flows to favor an
IEX. The JTX has minimal friction losses and minimal energy conversion to kinetic energy, as compared
to IEX- deLaVal expansion). For JX case: calculate Friction=TAS-Q & Q=0 so F=560*0.089=48 BTU/#.
For JTX F=TAS-Q = 548*0.075=41, for IEX, F=TAS+0=560*0=0. So Friction Loss JX>JTX>IEX.
Isothermal, ITX, represents a case where heat addition is required.
Gas X C3= initial: 125psia,100F basis: P-H Carrier #144chart S1=1.42 H1=137 Z1=0.932
Condition -dG dH dU dS dT dPsi Cp avg dTjx T2 P2 V2/V1 S2
++ThermX 443.1 51.0 78.3 0.235 200.0 -110 0.425 -7.6 300 15.0 12.1 1.66
IsoThermX 39.6 9.5 2.5 0.094 0.00 -105 0.375 -7.7 100 20.0 6.6 1.51
FreeX dU=0 31.5 6.5 0.00 0.089 -7.8 -105 0.374 -7.8 92 20.0 6.5 1.51
Isenth.X dH=0 4.6 0.00 -5.5 0.075 -25.0 -105 0.369 -7.8 75 20.0 6.3 1.50
Isentropic X -67.7 -40.0 -37.5 0.00 -135.0 -105 0.342 -7.9 -35 20.0 4.9 1.42
Chilled X -117.9 -51.0 -49.0 0.019 -180.0 -118 0.331 -7.6 -80 7.0 12.1 1.44
63
Review of C3= Gas eXpansion by thermodynamic states
This chart plots results of enthalpy
and internal energy changes for
C3= expansion from 125psia &
100F to 20 psia. The values used
to determine these changes were
tabulated from Carrier Chart
#144. The Z values were
determined and averaged by BWR
and Viral EOSs. These two EOS
showed the best JTX
temperatures. The dU was
calculated from dH-d(PV), with
d(PV)= d[(Psia*144)10.73ZT/(Psia
42)/778=1.986d(ZT)/42. The
temperatures for dH or dU =0,
determined by the plot, are the
temperatures for JX and JTX
expansion. The T for JTX is 75F
and 75.5F for JX, by the plot.
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
6.0
60.0 65.0 70.0 75.0 80.0
B
T
U
/
#

1
2
5
p
s
i

t
o

2
0

p
s
i
T, F @20psia C3= expansion
C3= Exp 125psia/100F to 20psia Carrier #144 Z1=0.932 dU=dH-d(PV)
dU btu/#
dH btu/#
This chart plots results show dT for a JTX of -25F, same as reported in the presented Scheel Chart of this
paper. The dT for JX from this plot is -24.5F. The dT.jx does not agree with the rule: dT.jx=k(dT.jtx). By
this rule, dT.jx =(15.77/(15.77-1.986))(-25)= (-28.6)F.
The prior table was based on using VdW for initial estimate of temperature. The VdW grossly under
estimates temperature change in many cases.
64
Review of Math forms used here:
1. d(uV) = Vdu + udV for real gas Z=f(T,P) with Tc, Pc constant
- ie real gas law PV=Z 9 T, c(PV)/cT = Z 9 + 9 T(cz/cT)
- ie real gas law PV=Z 9 T, c(V)/cT = Z 9 /P+ 9 T(cz/cT)/P
2 : d(1/Z) = -()/Z
2
ie dP/dV =Z 9 T[-( )/V
2
] + Z 9 T[dZ/dV]/V
3. Natural logs: -du/u =d(ln[u]) & du=u[dln(u)]
4. Integrated forms: du/u = ln(u
2
/u
1
); du = u
2
-u
1
; vdv = A v
2
5. Implicit: c(g)/cv = - (cf/cv) / (cf/cg) where f =F(g,v)
6. Chain Rule: dy/dx = (dy/dv) (dv/du)(du/dx) & dZ
2
=2Z[d(Z)]
7. Total differential df= (cf/cz)dZ+ (cf/cx) dX+(cf/cy)dY
8. }PdV = -}VdP+ A(PV) & -}VdP = }PdV - A(PV) & d(PV)=PdV +VdP
9. Log differentials: PV=ZRT or dP/P = dZ/Z + dT/T dV/V
10. ln(X) ~ 1-X for X close to 1:
11. Partial fractions a/((X+a)(X+b)) = m/(X+a) + n/(X+b)
65
The empirical Berthelot EOS is: Z = 1 + 9P
r
/(128T
r
) - 54P
r
/(128T
r
3
) = PV/RT so V & P are:
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
V= RT/P +(RT/P)9P
r
/(128T
r
) (RT/P)54P
r
/(128T
r
3
) & P= RT/V +(RT/V)9P
r
/(128T
r
) -(RT/V)54P
r
/(128T
r
3
)

JT
(cT/cP)
h
= -(ch/cp)T/Cp = {TcV/cT|p - V}/Cp &
J
(cT/cV)
U
= (-1/Cv )(cU/cV)
T
= (-1/Cv){TcP/cT|
V
P}
________________________________________________________________________________________________________________________________________________________
{TcV/cT|
p
- V} =Tc(RT/P +(RT/P)9P
r
/(128T
r
) (RT/P)54P
r
/(128T
r
3
) )/cT|
p
V
{TcV/cT|p - V} =(RT/P + 0 +(RT/P)108P
r
/(128T
r
3
) (RT/P +(RT/P)9P
r
/(128T
r
) (RT/P)54P
r
/(128T
r
3
)
{TcV/cT|p - V}=(0+ 0 +(RT/P)108P
r
/(128T
r
3
) +(-0-(RT/P)9P
r
/(128T
r
) +(RT/P)54P
r
/(128T
r
3
)
{TcV/cT|p - V}=RT/P
c
{1.27/T
r
3
- 1/(14.2T
r
)} = & AT = A P RT/P
c
{1.27/T
r
3
- 1/(14.2T
r
)}/Cp

JT
(cT/cP)
h
= RT/P
c
{1.27/T
r
3
- 1/(14.2T
r
)}/Cp & AT
JTX
= {A[P
R
]}(RT/C
P
){1.27/T
r
3
- 1/(14.2T
r
)}
----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
{TcP/cT|V - P} =Tc(RT/V+(RT/V)9P
r
/(128T
r
) (RT/V)54P
r
/(128T
r
3
) )/cT|p P
{TcP/cT|V- P} =T(R/V+(0) +(R/V)108P
r
/(128T
r
3
) P
{TcP/cT|V - P} =(RT/V + (RT/V)108P
r
/(128T
r
3
) +(-RT/V -(RT/V)9P
r
/(128T
r
) + (RT/V)54P
r
/(128T
r
3
))
{TcP/cT|V- P} =(0+ (RT/V)108P
r
/(128T
r
3
) +(-0 - (RT/V)9P
r
/(128T
r
) + (RT/V)54P
r
/(128T
r
3
))
{TcP/cT|V - P}(-1/Cv)=(RT/V){1.266/(T
r
3
) - 1/(14.2T
r
) }(P
r
)(-1/Cv) but RT/V =P for Z defined by this EOS

J
(cT/cV)
U
= (P){1.27/(T
r
3
) - 1/(14.2T
r
) } (P/P
c
) (-1/Cv ), but dV =-(RT/P/P)dP
AT
JX
= (P){1.27(T
r
3
) - 1/(14.2T
r
)} (P/P
c
) (-1/Cv ) -(RT/P/P)dP, the P*P/P/P cancel out leaving (dP/P
c
)
AT
JX
= (AP
R
)(RT/Cv ){1.266/(T
r
3
) - 1/(14.2T
r
)} & also Cv AT
JX
= Cp AT
JTX
C
v
AT
JX
= (C
p
AT
JTX
) , so AT
JX
= k AT
JTX
Berthelot EOS for Joule & JT Coefficients
66
Based on results for both Berthelot and Viral EOSs it appears the ratio for (AT
jx
/AT
JTX
) is just the ratio of
(C
p
/Cv). The slide examines this concept from another view. That is to use basis of the definition of
enthalpy and internal energy, as pressure corrected by Joule temperatures:
AH = C
p
(AT-
JT
Ap) = C
p
(AT- AT
JTX
), & : AU = C
v
(AT-
J
A(1/V)) = C
v
(AT-AT
JX
) . For JTX AH =0;
AH =0 = C
p
(AT
JTX
- AT
JTX
) = {AU + A(PV)}={AU + (PV)
2
(PV)
1
} = {AU + RA(ZT)}, if use avg Z
AH =0 = C
p
(AT
JT
- AT
JT
) = AU + ZRA(T
JT
) = C
v
(AT
JTX
- AT
JX
) + ZRA(T
JTX
) = 0, but ZR= C
p
C
v
C
v
(AT
JTX
- AT
JX
) + (C
p
- C
v
)A(T
JTX
) = 0 & distribute: 0= (C
v
AT
JTX
- C
v
AT
JX
) + (C
p
AT
JTX
- C
v
AT
JTX
)
0 = (0 - C
v
AT
JX
) + (C
p
AT
JTX
- 0) = 0 or: C
p
AT
JTX
- C
v
AT
JX
or: C
v
AT
JX
= C
p
AT
JTX
This ratio of (C
p
/Cv) = (AT
JX
)/AT
JTX
) is the same result arrived at by the Viral & Berthelot EOSs
(AT
jx
/AT
JTX
)=(C
p
/Cv) {f(B
e.JX
)/f(B
e.JTX
)} =(C
p
/Cv) {1, for B'lot or Viral EOS} =(C
p
/Cv)
Temperature change of a free expansion from same initial conditions to same final conditions is always
greater than the temperature change for a JT expansion? Why because Cp/Cv is always >1. These results
appear confirmed by steam table analysis as per below, one of few listed dU values.
A further result is that if one accurately determines temperature change of one expansion, the other
expansion path temperature change can be determined by the k value of the gas.
This is very surprising as the literature calls a free expansion an isothermal expansion, where-as what this
work shows is that a Free or Joule Expansion produces lower temperatures than a Joule Thompson
Expansion.
Repeat: ratio of Joule Free Expansion temperature change to Joule Thompson temperature change is ratio of
Constant Pressure heat capacity to constant volume heat Capacity: AT
jx
= (C
p
/C
v
)AT
JTX
= (k)AT
JTX
Ratio of dT Joule & to dT Joule-Thompson by Energy Equations
Sat.Steam: 325 to 162.5psia k=1.18 & k rule 1.15
U BTU/# H BTU/# T1, F T2 H=C T2 U=C dT H=C dT U=C
1117.5 1203.5 424.5 375.5 368.0 49.0 56.5
67
Use results that the ratio for (AT
jx
/AT
JTX
) is just the ratio of (C
p
/Cv) or k. The slide looks at a constant
enthalpy expansion from a PV standpoint: with proof from H-S chart of (AT
jx
/AT
JTX
) = (C
p
/Cv) = k
AH = C
p
(AT-
JT
Ap) = C
p
(AT- AT
JTX
), & AU = C
v
(AT-
J
A(1/V)) = C
v
(AT-AT
JX
) & for JTX
AH =0 = C
p
(AT
JTX
- AT
JTX
) = {AU + A(PV)}={C
v
(AT
JTX
- AT
JX
) + A(PV)} = 0
AH =0= {AU + A(PV)}={C
v
(AT
JTX
- AT
JX
) + A(PV)} = {C
v
(AT
JTX
- kAT
JTX
) + A(PV)} =0 & ZR= C
p
C
v
AH =0= {C
v
(AT
JTX
- kAT
JTX
) + A(PV)} = {C
v
AT
JTX
(1- k) + A(PV)}= {AT
JTX
(C
v
- C
p
) + A(PV)} =0
AH =0 = {AT
JTX
(C
v
- C
p
) + A(PV)} = {-ZRAT
JTX
+ A(PV)} =0 or A{(PV)
JTX
}/J= ZRAT
JTX
The term A(PV) implies work, but an isenthalpic expansion is a locked rotor or zero work expansion. The
d(PV) work is internal expansion energy. Below Table is worked example based on Scheels C3= H-S. The
equations offers thermo dynamic proof of presented equations. A AT
JTX
from EOS or chart is needed. The
term, A(PV)/J= ZRAT, is valid any gas, but arriving at this by use of, AT
jx
=kAT
JTX
validates that AT
jx
=kAT
JTX
.
Simplified Look at Isenthalpic & Joule Expansions
C3= 1 2
Psia 125 20
T, F 100 75
Z 0.94 0.94
M 42 42
V cf/# 1.08 6.42
PV btu/# 24.9 23.8
d(zRT) -1.11 EX.1
d(PV)/J -1.11 JTX
diff/err -9E-06 C3=
dH For A) Joule Expansion, {AU=0} & use Scheels chart from 100F & 125 to 20psia,
followed by; B). constant pressure expansion to JT condition, 75F. With k= 1.149;
Cp=15.31BTU/mol/F; AT
JTX
= -25F. & AT
JT
= -25F x 1.149= -28.7F.
A) AH
JX
= {AU + A(PV)}={0+A(PV)}={C
p
(AT
JX
- AT
JTX
)}=C
p
(k AT
JTX
-AT
JTX
)
AH =15.31/42(-25)(1.149-1)= -1.36BTU/#
B).From the constant pressure Joule Expansion conditions, no JT correction is needed
as the expansion is at constant pressure so AH
JX/JTX
={C
p
(T
JTX
-T
JX
}=0.365(75-71.3F)
=1.35 BTU/#.
C) The sum of these 2 expansions is AH
JTX
= -1.36+1.35=0.010. As no heat is added at
any step perhaps one could say the difference between a Joule expansion and a JTX is
with limited friction energy, just equal to the dH between JX & JTX? For brevity the
d(PV) calc is left off but closes with use of Z, as shown in Table to right, which
validates (AT
jx
/AT
JTX
) = (C
p
/Cv) = k by using JX- JTX rules: arrive at A(PV)/J= ZRAT.
68
Why is the ratio for (AT
jx
/AT
JTX
) just the ratio of (C
p
/Cv) or k? The slide looks at this concept from the EOS
thermo concept using primary definition of the terms:

JTX
(cT/cP)
h
= -(cH/cP)
T
/C
p
= {T(cV/cT)
p
- V} /C
p
or dT
JTX
C
p
= {T(cV/cT)
p
- V} dP

JX
(cT/cV)
U
= -(cU/cV)
T
/C
v
= {T(cP/cT)
V
P} /C
v
or dT
JX
C
v
= {T(cP/cT)
V
P} dV
What is said in prior 2 slides is: dT
JTX
Cp = dT
JX
Cv so {T(cV/cT)
p
- V} dP = {T(cP/cT)
V
P} dV
Using PV=RT, V=RT/P & P=RT/V, & T(cV/cT)
p
= RT/P & T(cP/cT)
V
=RT/V & dP = -RT/P
2
so dV= dP RT/P
2
Make the subs {T(cV/cT)
p
- V} dP = {T(cP/cT)
V
P} dV & {RT/P - V} dP = {RT/V P} -dP RT/P
2
The dPs cancel & multiply both by P to get {RT - PV} = {RT/V P} RT/P
But PV=RT & divide by RT, plus RT/V =P so {RT - RT} /RT = {P P} /P or 1-1 =1-1 or 0 = 0 , perfect
All terms are equal terms, just expressed differently, as proved by 3 prior slides, Berthelot & Viral EOS,
Enthalpy definitions, Steam Table Evaluation of temperature for dU =0 and temperature for dH=0 and
subsequent temperature changes for constant U & H, plus the evaluation of C3= from the H-S diagram.
dT
JTX
Cp = dT
JX
Cv k dT
JTX
= dT
JX
Other considerations are when variables separate, then correct is dT/X(T) = dP/Y(P) is correct integral form.
Also it is strange but these findings contradict the concept that a free expansion is very close to an
Isothermal expansion, when in fact a free JX produces Ts lower than JTX. However a free X is an X into a
vacuum. Which for practical applications such is not possible but vacuum conditions just mean that P1>>Po
and minimal work, so how significant is that?
Specification of 2 variables make a complete specification of a single component system. The combination
metrics are PV, PT, & VT. The PV spec is used to define phases, PT spec for common process specifications &
to denote ideality departure, while VT spec is common to define work, as in TS or HS diagrams. The use of
and work in P & T equations are preferred as they are directly measurable. Volume or density is less
common and more difficult measurement. Thus was the concept at looking at JTX coefficient not in terms of
volume but in basic terms of pressure and temperature, which then found: (AT
jx
/AT
JTX
)= (C
p
/Cv)
Ratio of dT Joule & to dT Joule-Thompson: Part 3
69
Multi Stage Gas Valve Field Trial Part 1
Here are some details of the field trial previously discussed. Notice the mixed
water/ice on valve discharge, confirming 32F outlet T. A downstream
thermowell showed 40F with small ice/water on line, 32F IR thermometer is
the accepted outlet temperature.
Vendor B
gas Fd vol frac
N2 0.0048
CO2 0.0094
H2S 0.0000
C1 0.6775
nC2 0.1661
nC3 0.1028
iC4 0.0101
nC4 0.0238
iC5 0.0028
nC5 0.0026
nC6 0.0001
H2O 0.0001
sum 1.0000
Gas Lab Anal
Psia.1 990.00
Psia.2 195.00
T1, F 95.00
The picture, in upper RH corner, is a
depiction of valve trim for Vendor A,
who predicted a more correct
temperature drop, closer to the field
result. Vendor B was selected for the
trial. After the field trial, B
recalibrated his model to better match
field results. The middle graph of a
CFD output for vendor Bs warranty
outlet temperature, 56F is provided.
Because the valve failed to achieve the
guaranteed outlet temperature and
Vendor Bs valve experienced complete
plugging from dirty gas, the valve was
returned to vendor. The field trial
showed a 10F to 12F increase in outlet
temperature with application of high
friction multistage trim. Economics
may support use of pre-filter on gas in
some instances where dirty gas is
processed. Vendor A claims his trim is
less prone to blockage. Repair of
plugged trim is near impossible.
Sundry vendors multistage trims have
experienced erosion and/or plugging
when processing pipeline gas. A few
ppb of Black Powder in a gas pipeline
can cause significant problems for
multistage valves.
70
Multi Stage Gas Valve Field Trial Part 2
Here are some details of the field trial previously discussed. Vendor A
determined a JTX. Temperature closest to what was experienced under
field conditions. Vendor B was selected for the trial. As result of trial, B
recalibrated his model to better match field results. A check of the PR-LK
constant enthalpy simulator model was made. Object of re-run was to
check predicted pressure drop to achieve 32F outlet temperature. The
predicted outlet pressure was 83psi higher than field measured. This is a
significant variance and exceeds any calibration error of field
instruments. As discussed on prior picture, the measured outlet
temperature of 32F indicates frictional heating that exceeds constant
enthalpy predictions.
Vendor A
CFD Real Gas Model Results
Vendor A CFD Real Gas Model Results
Source.HF/100psidMW dPSI dF/1 00psid
Field Measured 23.3 770 7.79
HySys- w/Lab Gz 23.3 795 9.43
BWR.JT w/LabGZ 23.3 770 10.90
Vendor A ++stage 23.0 770 7.79
Vendor B 22 stage 23.0 795 4.78
Vendor C H-S/JTX 20.6 730 7.54
RK.JTX Dsgn Gas 20.3 730 7.75
RK.JTX Lab Gas 23.0 795 11.40
Source MW dPSI dF/1 00psid
PR.-w/LabGz 23.3 795 9.53
PR-LK.-w/LabGz 23.3 795 9.30
SRK.-w/LabGz 23.3 795 9.50
PR-LK./LGz-32F.o 23.3 712 8.85
71
Multi Stage Gas Valve Field Trial Part 3A What is Black Powder (BP)?
Heather to fore, BP was considered exclusively an issue for product pipelines. This test, with a raw gas
pipeline, shows BP can exist in other parts of a gas system. The following quote is from www.Wiki Black
Powder Gas Pipeline, Dec.09/2012
Black powder is a solid contamination in finished product pipelines. The material may be wet and have a
tar-like appearance, or dry and be a very fine powder, sometimes like smoke. Black powder can cause a
range of problems, including product contamination, erosion wear in compressors, instrument and filter
clogging and equipment contamination for product consumer, erosion and sealing problems for valves, and
flow reduction. Black powder may be mechanically mixed or chemically combined with any number of
contaminants such as water, liquid hydrocarbons, salts, chlorides, sand, or dirt. Chemical analyses of the
material have revealed that it consists mainly of a mixture of iron oxides and iron sulfides. The following
slide details upstream testing showing BP in gas pipelines exists from wellhead to final gas product lines.
Forms of Black Powder in Gas pipeline
72
Multi Stage Gas Valve Field Trial Part 3B What is Black Powder?
Black powder is a solid contamination in natural gas pipelines. The median average particle diameter is
about 45 m. Separation of a sludge sample into water and oil components, indicates the darker brown BP
results from water phase, whilst the tar portion of sludge was far darker. The water constituent of this
sludge sample had iron as the predominate (50%) non oxygen element. The hydrocarbon portion was more
black with 87% carbon. The oil fraction contained significant silica and sulfur.
The abrasiveness of this fine powder can be seen in the eroded valve trim and cage, plus the erro0ded
compressor seal. The tested high friction valve trim has a more convoluted flow pattern, as opposed to
straight flow path and larger diameter holes in a conventional valve. The high friction valve trim was
rapidly plugged off due to convoluted flow pattern and small opening diameter of ports.
Vendor A CFD Real Gas Model Results
73
Multi Stage Gas Valve Field Trial Part 4a Process Simulator Comparison A
Thermo=> PR-LK Sim Valve model u.jtx
in out delta F/100psi
T,F 95.0 21.1 -73.9 9.30
P psia 990.0 195.0 -795
H btu/# -35.20 -35.19 0.001
S btu/#F -0.2714 -0.1981 0.0733
Z 0.7672 0.9284 d(TS)=> 55.32
Cp/Cv 1.67 1.322 dPV=> 1.78
Cp btu/#/F 0.701 0.4855 dPfrict=> 59.99
mw 23.31 23.31 Qc => -4.67
den 5.05 0.95 #/CF
TS -150.63 -95.306 BTU/#
V 27.15 147.55 fps
P head 35.74 35.19 BTU/#
V head -0.12 -2.25 BTU/#
Frict. Head 0.00 2.68 BTU/#
Total Head 35.62 35.62 BTU/#
H(32F,1atm) -35.20 -35.19 BTU/#
V head -0.12 -2.25 BTU/#
F.hd 0 2.12 BTU/#
Total Head -35.32 -35.32 BTU/#
Thermo=> PRLK32Fout Sim Valve model u.jtx
in out delta F/100psi
T,F 95.0 32.0 -63 8.85
psia 990.0 278.0 -712
H btu/# -35.20 -36.12 -0.925
S btu/#F -0.2714 -0.2187 0.0527
Z 0.7672 0.905 d(TS)=> 43.03
Cp/Cv 1.67 1.356 dPV=> 1.92
Cp mass 0.701 0.5086 dPfrict=> 47.02
mw 23.31 23.15 Qc => -4.00
den 5.05 1.35
TS -150.63 -107.600 43.0266
V 27.15 105.84 fps
P head 35.74 36.18 BTU/#
V head -0.12 -1.31 BTU/#
Frict. Head 0.00 0.75 BTU/#
Total Head 35.62 35.62 BTU/#
H(32F,1atm) -35.20 -36.12 BTU/#
V head -0.12 -1.31 BTU/#
F.hd 0 2.12 BTU/#
Total Head -35.32 -35.32 BTU/#
74
Multi Stage Gas Valve Field Trial Part 4b Process Simulator Comparisons B
Thermo=> PR Sim Valve model u.jtx
in out delta F/100psi
T,F 95.0 19.2 -75.8 9.53
psia 990.0 195.0 -795
H btu/# -38.93 -36.81 2.12
S btu/#F -0.2714 -0.2023 0.0691
Z 0.7208 0.9117 d(TS)=> 53.68
Cp/Cv 1.79 1.3623 dPV=> 3.43
Cp mass 0.6972 0.4787 dPfrict=> 57.36
mw 23.31 23.13 Qc => -3.67
den 5.38 0.96 #/CF
TS -150.63 -96.942 BTU/#
V 27.15 146.96 fps
P head 33.58 34.68 BTU/#
V head -0.12 -2.23 BTU/#
Frict. Head 0.00 1.00 BTU/#
Total Head 33.45 33.45 BTU/#
H(32F,1atm) -38.93 -36.81 BTU/#
V head -0.12 -2.23 BTU/#
F.hd 0 -0.02 BTU/#
Total Head -39.05 -39.05 BTU/#
Thermo=> SRK Sim Valve model u.jtx
in out delta F/100psi
T,F 95.0 19.5 -75.55 9.50
psia 990.0 195.0 -795
H btu/# -36.22 -36.21 0.006
S btu/#F -0.2714 -0.1996 0.0718
Z 0.7547 0.9206 d(TS)=> 54.93
Cp/Cv 1.656 1.35 dPV=> 1.92
Cp mass 0.6594 0.4775 dPfrict=> 59.11
mw 23.31 23.31 Qc => -4.18
den 5.13 0.96 #/CF
TS -150.63 -95.698 BTU/#
V 27.15 147.04 fps
P head 35.16 34.77 BTU/#
V head -0.12 -2.23 BTU/#
Frict. Head 0.00 2.49 BTU/#
Total Head 35.03 35.03 BTU/#
H(32F,1atm) -36.22 -36.21 BTU/#
V head -0.12 -2.23 BTU/#
F.hd 0 2.10 BTU/#
Total Head -36.34 -36.34 BTU/#
75
Multi Stage Gas Valve Field Trial P4c Outlet T prediction by Clausius EB
Below is outlet temperature calculation using Berthelot EOS. The Left table calculates outlet temperature
based on Friction as just TdS. TdS is calculated as dH-(dP)/Density in BTU/#. Density is based on log mean
formula. Pressure corrected dH is determined by Berthelot JT temperature drop, low pressure Cp and actual
dT as presented in this paper. The vdP is reciprocal log mean density times pressure drop. The pressure head
is determined by ZRTln(P/14.7) which is correct for a real gas. Gas composition is used to determine critical
temperature and pressure. Temperature of outlet is adjusted until inlet and outlet energy are in balance. For
a real process TdS should be positive, increased entropy, as calculated in table below. The right hand table
uses mechanical friction as determined by gas valve CV and prior formula from Crane TP-410 relating CV and
K. Friction is K times velocity head. Friction Velocity Head is based on simple average velocity. A formula for
Thermodynamic Friction, F=-(AH+ A(V
2
/2Jg ) TdS), is arrived at by the Streeter Clausius energy balance
method, Perry & Streeter. Setting F=TdS is specification of Total Thermo energy of zero. With 2 unknowns,
either simplification or Mechanical F equation is required for solution. The Blot EOS with F=TdS arrives at
same T drop as one vendors CFD calc & ME Blot seems a tad high. Measured outlet temperature was 32F.
inlet outlet units Bertholet Z EOS Friction by
MW 23.35 23.35 #/mol item/ u inlet outlet Clausius TdS
Z 0.795 0.934 v/v Pc psia 664.4 664.4 10.65 Cp
Press 990.0 195.0 Psia Tc R 426.9 426.9 8.66 Cv
Temp. 95.00 25.58 F Pr 1.49 0.29 1.23 k
Den 4.885 0.935 #/cf Tr 1.30 1.14 -69.42 dT
Flow 9.000 9.000 mmscfd Z B'lot 0.795 0.934 -77.03 dTjx
id sch 80 2.9 3.826 inch SG 0.805 0.805 7.60 dTu
Velocity 28.6 85.9 ft/sec Cp mass 0.471 0.441 2.82 dU
B'lot EOS Therm Energy Balance Z LM 0.86 B'lot -69.42 dT
in out units dP 795.00 psi -62.66 dT.jtx
P hd 157.92 99.74 btu/# P LM 489.32 psi -6.77 dTh
Vhd 0.02 0.15 btu/# T LM 52.91 F -3.09 dH
Frict 0.00 58.05 btu/# den LM 2.41 #/cf -61.14 vdP
Sum 157.94 157.94 btu/# Frict 58.05 btu/# 58.05 F=TdS
Bertholet dT JTX, degree F -62.66 Outlet T: B'lot JTX 32.34 P hd calc as:
Friction =TdS = dH-vdP, use log mean density for v (ZRT)ln(P/14.7)
inlet outlet units Bertholet EOS Z,dT.jtx Friction by
MW 23.35 23.35 #/mol item/ u inlet outlet Clausius TdS
Z 0.795 0.942 v/v Pc psia 664.4 664.4 10.65 Cp
Press 990.0 195.0 Psia Tc R 426.9 426.9 8.66 Cv
Temp. 95.00 43.61 F Pr 1.49 0.29 1.23 k
Den 4.885 0.894 #/cf Tr 1.30 1.18 -51.39 dT
Flow 9.000 9.000 mmscfd Z B'lot 0.795 0.942 -77.03 dTjx
id sch 80 3.826 3.826 inch SG 0.805 0.805 25.63 dTu
Velocity 16.4 89.9 ft/sec Cp mass 0.471 0.441 9.51 dU
B'lot EOS Therm Energy Balance Z LM 0.87 B'lot -51.39 dT
in out units dP 795.00 psi -62.66 dT.jtx
P hd 157.92 104.34 btu/# P LM 489.32 psi 11.26 dTh
Vhd 0.01 0.16 btu/# T LM 66.00 F 5.14 dH
Frict 0.00 53.43 btu/# den LM 2.34 #/cf -62.97 vdP
Sum 157.93 157.93 btu/# Frict.T 62.81 btu/# 68.11 TdS
Bertholet dT JTX, degree F -62.66 Outlet T: B'lot JTX 32.34 P hd calc as:
Friction =-(dH+dVhd-TdS), &= KV
2
/(J2g) => 53.43 (ZRT)ln(P/14.7)
76
Multi Stage Gas Valve Field Trial P4d Outlet T prediction by Clausius EB
Below is outlet temperature calculation using Ping Robinson Lee Kessler EOS (on Left side) and BWR EOS on
RH side. Both calculations use the Mechanical Energy method to determine valve friction. Friction is
determined by mechanical formula of K times velocity head. The K is determined by Crane TP410 formula
mentioned prior in this paper, using valve Coefficient, CV. The gas valve CV is determined by formula: CV =
scfm{SG (R/520)/Apsi/psi.inlet}
0.5
. The temperature, Rankin, is simple average of inlet and valve outlet, SG
being gas gravity relative to air. The PR-LK EOS result arrears to give a temperature slightly in excess of the
measured outlet temperature of 32F.
The BWR EOS fitted to Standing Katz hydrocarbon Z data calculates an outlet temperature of 29.23F. This EOS
with the Mechanical Friction Formula of Crane TP-410 gives a result that most closely matches the field
measured temperature. This BWR EOS validity is listed down to reduced temperature >1.05 & Pr<30.
inlet outlet units PR-LK Z EOS Friction by
MW 23.35 23.35 #/mol item/ u inlet outlet Clausius TdS
Z 0.767 0.923 v/v Pc psia 664.4 664.4 10.18 Cp
Press 990.0 195.0 Psia Tc R 426.9 426.9 8.19 Cv
Temp. 95.00 39.89 F Pr 1.49 0.29 1.24 k
Den 5.060 0.919 #/cf Tr 1.30 1.17 -55.11 dT
Flow 9.000 9.000 mmscfd Z prlk 0.767 0.923 -91.94 dTjx
id sch 80 3.826 3.826 inch SG 0.805 0.805 36.82 dTu
Velocity 15.9 87.4 ft/sec Cp mass 0.436 0.436 12.92 dU
B'lot EOS Therm Energy Balance Z LM 0.84 -55.11 dT
in out units dP 795.00 psi -74.00 dT.jtx
P hd 152.45 101.52 btu/# P LM 489.32 psi 18.89 dTh
Vhd 0.01 0.15 btu/# T LM 63.51 F 8.23 dH
Frict 0.00 50.79 btu/# den LM 2.41 #/cf -60.98 vdP
Sum 152.46 152.46 btu/# Frict 60.83 btu/# 69.22 TdS
PR-LK dT JTX, degree F -74.00 Outlet T: PRLK JTX21.00 P hd calc as:
Friction =-(dH+dVhd-TdS), &= KV
2
/(J2g) => 50.79 (ZRT)ln(P/14.7)
inlet outlet units BWR EOS Z,dT.jtx Friction by
MW 23.35 23.35 #/mol item/ u inlet outlet Clausius TdS
Z 0.754 0.929 v/v Pc psia 664.4 664.4 10.48 Cp
Press 990.0 195.0 Psia Tc R 426.9 426.9 8.50 Cv
Temp. 95.00 29.23 F Pr 1.49 0.29 1.23 k
Den 5.145 0.933 #/cf Tr 1.30 1.15 -65.77 dT
Flow 9.000 9.000 mmscfd Z BWR0.795 0.929 -106.1 dTjx
id sch 80 3.826 3.826 inch SG 0.805 0.805 40.34 dTu
Velocity 15.6 86.1 ft/sec Cp mass 0.471 0.427 14.68 dU
B'lot EOS Therm Energy Balance Z LM 0.84 -65.77 dT
in out units dP 795.00 psi -86.00 dT.jtx
P hd 149.93 100.00 btu/# P LM 489.32 psi 20.23 dTh
Vhd 0.00 0.15 btu/# T LM 55.80 F 9.08 dH
Frict 0.00 49.78 btu/# den LM 2.46 #/cf -59.80 vdP
Sum 149.93 149.93 btu/# Frict.t 59.65 btu/# 68.89 TdS
BWR dT JTX, degree F -86.00 Outlet T: BWR.jtx 9.00 P hd calc as:
Friction =-(dH+dVhd-TdS), &= KV
2
/(J2g) => 49.78 (ZRT)ln(P/14.7)
77
Multi Stage Gas Valve Field Trial P4e Outlet T prediction by Clausius EB
Below is outlet temperature calculation using RK EOS on left side. Table to right is comparison of methods
and the field trial result measured temperature. It appears the BWR EOS fitted to the Standing Katz
Compressibility data gives a match closest to the field observed result for this sweet hydrocarbon gas, with
relatively low CO2 component. The Joule Thompson temperature should be lower than the temperature
determined when accounting for mechanical friction. This is in agreement with all principles repeated
routinely in the paper. Friction produces heat and increased entropy. The Clausius heat balance is the correct
energy balance to account for friction heating. Few if any process simulators treat friction heating properly,
instead they rely upon a JT outlet temperature. Measured outlet temperature was 32F, with ice and water on
valve outlet.
inlet outlet units RK EOS Z & T.jtx Friction by
MW 23.35 23.35 #/mol item/ u inlet outlet Clausius TdS
Z 0.768 0.933 v/v Pc psia 664.4 664.4 10.48 Cp
Press 990.0 195.0 Psia Tc R 426.9 426.9 8.50 Cv
Temp. 95.00 34.72 F Pr 1.49 0.29 1.23 k
Den 5.051 0.919 #/cf Tr 1.30 1.16 -60.28 dT
Flow 9.000 9.000 mmscfd Z RK 0.795 0.933 -112.2 dTjx
id sch 80 3.826 3.826 inch SG 0.805 0.805 51.9 dTu
Velocity 15.9 87.4 ft/sec Cp mass 0.471 0.427 18.89 dU
RK EOS Therm Energy Balance Z LM 0.85 -60.28 dT
in out units dP 795.00 psi -90.93 dT.jtx
P hd 152.72 101.53 btu/# P LM 489.32 psi 30.6 dTh
Vhd 0.01 0.15 btu/# T LM 59.89 F 13.76 dH
Frict 0.00 51.04 btu/# den LM 2.41 #/cf -60.94 vdP
Sum 152.73 152.73 btu/# Frict.T 60.79 btu/# 74.70 TdS
RK dT JTX, degree F => -90.93 Outlet T: RK JTX 4.1 P hd calc as:
Friction.T = -(dH+dVhd-TdS), &= KV
2
/(J2g)=> 51.04 (ZRT)ln(P/14.7)
Calculation Summary & Field Measure valve
JTX Mechanical Friction BTU/#
EOS T2.deg.F T2. deg. F Mech Thermo
B'lot 32.3 43.6 53.4 62.8
PR-LK 21.0 39.9 50.8 60.8
BWR 9.0 29.2 49.8 59.7
RK 4.1 34.7 51.0 60.8
Measured 32F T2 outlet T
78
The gas concept: adiabatic, (without heat) has been hijacked to be equated with isentropic (IS, -
reversible or frictionless, aka fiction, aka imaginary, zero entropy change). This begs the issue: What is
name of adiabatic non reversible process? Is it isothermal, (IT)? No, because IT requires heat addition in
real world applications. Is it isentropic? No as isentropic is zero dS and dS=0 only holds for reversible non
friction process. Adiabatic change is any process in any insulated format. While the term IT requires heat
transfer. Isobaric (IB) is a constant pressure processes. The term IT is counter intuitive. For when IT is
applied to, Constant Volume or (IM), isometric (ideal liquids), it conveys meaning of adiabatic. At other
end of scale is a constant internal energy process, dU=0, another hijacked term, (see SvN textbook)
coined to mean isothermal. A dU=0 process is only IT for a few, ideal gasses. Bad thinking produces bad
math, as the math is just a means to quantity a concept. The constant internal energy concept is so rare,
that one is hard pressed to find a Latin equalivalent word. The closest concept is the oft forgotten, Joule
(Free) Expansion, JX, not to be confused with a Joule Thompson Expansion, JTX. Both expansions are
neither IM nor isobaric (IB Constant Pressure) nor IS, as dS>0. A JX (dU=0) is related to constant volume
heat capacity, whilst JTX is related to constant pressure heat capacity, Cp. Both JTX & JX are zero work
expansion (W=0), and zero heat, (Q=0) expansion. The difference between a JX & a JTX expansion can
only be see if viewed from a real gas perspective. For Ideal gasses both JX & JTX have zero temperature
change. Looking at adiabatic Joule expansion, JX, on H-S diagram for C3=, from 125psia and 100F to
20psia, gives a negative dH, BTU/#. And for any JX, dH is negative, while dH of JTX is zero. If heat is
calculated as dH then a JX would say heat is needed for this expansion. However the Joule experiment
and the definition of heat, dQ=dU=0 for a JX. Making correction by Clausius Equality Method is the correct
accounting of frictional heat, for either gas or liquid flow. The correction of dH & dU for pressure is easily
implemented by the Joule or JT coefficients.
This paper determined that temperature change for a JX expansion should be greater than the
temperature change of a JTX. The JTX temperature change multiplied by the constant pressure heat
capacity and divided by the constant volume heat capacity is the approximate temperature change for a
Joule Expansion. It is an abuse of nomenclature to call an isothermal expansion a Joule or Free
Expansion as a JX has a greater temperature change than the JTX. The increase of temperature for a
JTX is likely the result of frictional heating, as detailed in the article so titled.
SUMMARY