Considerations on Real Gas Expansion: Otis P. Armstrong P.E.

, -Dec/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 and result in reduced efficiency, the same is true for nozzle flow. Likewise for valves: gas friction increases the outlet temperature. This is noticed on the HS 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 will always have friction effect, which will produce heat. For 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 JouleThompson , 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.
1

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/) + U] - (Q)h =0} or (U+(V2/2g)/J)1+(Q-W)=(U+(V2/2g)/J)2+(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 = (29.84d2/CV)2 = (1/Kd)2 = 1/ = 1/(n) The Clausius Equality {F=(TS-Qh)} 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. U =Cv(T - TJX) & H = Cp (T - TJTX) : The Cs are low pressure heat capacity. The temperature sign convention is easily remembered. For at either U or H = 0, the temperature change will be negative for all but 3 quantum gasses, H2 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/P1)(m)} m=(Z/Cp)() & =(+X)expansion =(1/ + X)compress : The term X is related to the JT Coefficient, in Rankin/atmosphere, Cp in BTU/#/F, and density in #/CF as: X=(0.37Cp) . 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: (TJTX/TJX) = (Cv/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. 2
O P Armstrong PE/Dec.2011

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+V2/2g/778)1 = (H + V2/2g/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. 3

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-0.95V2/(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. 4

H-S C3=

Compressed (zipped) Folder

Unzip compressed folder to storage. JT calculator is the HTML file & executes in mobile or other browser with java

Field Trial: High Friction Gas Valve Temperature drop compared to Isenthalpic Performance

prop unit
W/mw acentric

viral
0.0720

RK

Cp Tc Pc Tin Pin Pout

btu/m ol/R Kelvin Pc,atm P1atm

11.6 213.9 45.2

T1Rankine 520.0

62.3 P2atm 11.2 ujt.clc Rankin/atm0.823 T2 jt.clc Rankin 478.0

actual 20.3000 Hi 11.6 Friction 213.9 Valve 45.2 70%eff 520.0 30%dH 62.3 to heat 11.2 0.769 na 480.7 492

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.

The percent efficiency is T actual, divided by T 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 7F/100psid, by this rule the high friction valve out performed the conventional rule. By the 7/100 rule the outlet T calculates to about 8F.
6

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:

n = (T1 T2)/(T1-T2) =(kd)2

For the gas valve discussed above these calculate as:

T1=60, T2=19F, T2=32F which is n =(60-32)/(60-19)=0.68 & kd=0.68=0.83
Where T2 is the ideal isentropic temperature.. T2 is actual outlet temperature. Kd is coefficient of discharge. Since kd 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, kd , 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=-H=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 + V2/(2gJ)]1= [H + V2/(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.

Determination Fluid Temperature Change

JT or Isenthalpic Expansion : T =(Cp JT)P, H =0 & if P2<P1 then T2<T1 & S>0 no work adiabatic Joule Free Expansion: T = (Cp J)V , U =0 & if V2>V1 then T2<T1 no work adiabatic Isothermal Temperature: T = 0 , PV=C & if dQ >0 T2=T1 & S>>0 & dQ by Clausius Equality Polythermal Temperature: T 0 , PV=ZRT & dQ either >0 or <0 T2=?T1 & S varies & no work Isentropic Temperature: T = T1((P2/P1)(1-1/k) 1), S =0 & if P2<P1 then T2=T1((P2/P1)(1-1/k) & <T1 Polytropic Temperature: T = T1((P2/P1)m 1), S >0 & T2 = T1{P2/P1)(m)} m=(Z/Cp)() & X=(0.37Cp) (1.986Z/Cp) Cp in molar units, Cp is Btu/CF/Rankin , is JT in Rankin/atm, =(+X)expansion =(1/ + 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 H0 ={H+ V2/2gJ} which is only true for frictionless flow. This article advocates that where irreversibility is present H0 ={H + V2/2gJ 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. 8

Friction Loss of Flow Apertures

Summary: K f L/D = (29.84d2/CV)2 = (1/Kd)2 = 1/ = 1/(n)
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. Pressure loss of valves may also be defined by CV, 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, CV, or Co, or efficiency are all identical forms of irreversible friction process which produce heat. Refer to Perry 5th 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 CV, gpm(SG/psi), & Crane pressure loss is 144(psi)/ =KV2/2g, Equate psi for CV, & Crane K, using water density of 62.4#/CF & SG= /62.4 & gpm=2.45Vd2. When making these substitutions & eliminate the density, SG, Velocity, & flow terms one arrives at CV,=29.84d2/K or K= (29.84d2/CV)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 CV, relation is not an empirical equation. If skin friction is accurately represented by fL/D= Crane K, so also is relation between CV, and Crane K. Gas Valve Flow Coefficient The CV, of gas is represented thusly: CV,=gpm(SG/psi) & #/hr =gpm/(500SG), (#/hr)/(500SG)*(SG/psi) & SG=/62.4 & =1/, place SG inside the root radical leads to CV=(#/HR)(1/500){(/psi)62.4} =#/HR(7.9/500)(/psi) = (pph/63.3) (/psi), where 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 = (29.84d2/CV)2 = (1/Co)2 = 1/ = 1/(n)

Revised slide

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 (Z/ oR) by Redlich Kwong h method 17. Determine (Z/ oR) 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 = Cp-Cv for real gas as z = Cp-Cv 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 Cp/Cv 45. Field Trial Details: MultiStage Hi Friction Valve 46. Black Powder in Raw Gas Pipelines 47 Summary 10

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, S, change is isentropic aka reversible adiabatic, whilst the isenthalpic (H=0) process is between has positive S. The most probable state has the highest positive S. 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: TS>Q & TdS = (dU + PdV) = (dH VdP) & Friction = (TS - Q)

Friction

eS=(T2/T1)Cv(1/2)R = [(T2/T1)(1/2)(k-1) ]Cv = [(P2/P1)k(1/2)(k) ]Cv = [(T2/T1)k(P2/P1)(1-k) ]Cv

Summary: Friction, Turbulence, & Work are identical energy forms (778ft#/BTU aka Joules Stirring experiments) because Friction and Turbulence Always consumes Work. 11

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, CpJT , is the ratio of gas expansion temperature change to temperature change, for dP & JT 0, as TF = PF/(J)= TJT = (JTCp)P. Which is true only for friction

Joule Thompson Expansion: 0 H=CpT+(Cp JT)P. While for Joule Expansion: 0 U=CvT+(Cv J)V A JTX is the isenthalpic case. Article 10 found Temperature relation for the general isentropic case as: Ti@e=1 + TF = TJT, So if the expansion is without friction then, it is also isentropic. If TF 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 Cv/Cp. On the C3= 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

B4: A @ 22atm: After A & B @ 11atm. Inside copper spheres was air, surrounded by an insulated water jacket Va=Vb

Joule Free Expansion dT -7F, if no Friction

JT Expansion dT -5F 22/11atm 12

Devised to eliminate friction heating

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, N2, 621K; and O2, 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; H2O, CO2, H2S, 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=an(Tr)n where n runs from 0 to 5 and a0 =-36.3, a1=71.6, a2=41.6, a3=11.8, a4=1.67, & a5=0.091. Another empirical equation for approximation of HC gases inversion point developed by Miller, presented on page 105 Walas ,1985 is: Pr = 24.21-18.54/Tr-0.825Tr2. 13

Summary of Equations for Joule Coefficient, J J (T/V)U=c = -((U/V)T=c )/Cv = -{T[(P/T)V=c ]- P)}/Cv

1. EOS 2. 3.

The Van der Waals EOS, a & b are unique to the VdW
J (T/V)U=c = {-2.72a/V2}/Cv & TJX = {-2.72a V-1}/Cv NOT Recommended By any EOS for Z: [du u2-u1 & 1/V = P/ZRT] J = {-T2/V}(Z/T)/Cv

T jx (P R ){1.09/T R 1.6 - 0.139 +0.89 /T R 4.2 - 0.083}(T C )/C v

T R >1

Viral 2 term form:

for P r >0.8 &

This Viral form is limited to Vr<2 and this limit is to be strictly observed to eliminate unrealistic answers.

4. 5.

T jx [-1.5a/(bC v T)] ln{[V/(V+b)] 2 /[V/(V+b)] 1 } Joule X dT, Rankin deg. T JX (P R )( T/C Vfor dT.jx calcs R 3 ) ){1.266/(T Conditions The VdW T JTX atm/R O2 CO2 C3= Air EOS dTs are

RK EOS: a & b are unique to the RK EOS BERTHELOT EOS

Joule X dT, Rankin degrees EOS O2 CO2 C3= Air H2O inconsistent P1 10.000 1.000 low pressure VdW -4.58 -0.49 and Use dT.jx = dT.jtx (Cp/Cv) is direct. The 8.503 2.361ratio is applied as both Cp-7.36 Cv -0.51 -5.80 are low pressure. for this data RK -6.44 -1.14 -21.70 -0.57 -32.80 T1 76.4 60.0 100.0 70.0 set. The VdW Viral -6.16 -1.45 -23.50 -0.58 -41.72 P2 0.500 0.500 1.361 1.299 EOS is not BWR -6.24 -1.37 -28.60 -0.60 -44.92 T2.jx 69.8 59.6 69.5 94.9 regularly B'lot -5.65 -1.47 -24.88 -0.50 -38.48 0.9696 0.9957 0.9332 0.9988 recommended Z1 for this work. Avg -6.12 -1.36 -24.67 -0.56 -39.48 Z2.jx 0.9970 0.9971 0.9812 0.9991 14 Rbest t hisdat -28.40 a data BW -56.50 dU 0.0000 0.0000 0.0000 0.0000

- 1/(14.2T R )} & also C v T JX = C p

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 (T/V)U=c =(-1/Cv )(U/V)T=c =(-1/Cv)[ T(P/T)V=c P] =R-mol/CF= 2.72(-a /Cv)/V2m , T jx = (a/C v )(1/V)

J , Joule Coefficient of a Free Expansion by VdW EOS

van der Waals EOS

&

CO2 from: 8.54CF/# to 17.1CF/# & Cv=6.71btu/mol/R, a=926atm/(CF/mol)2 oR = -0.5oR

free expansion, (1/17.1-1/8.54)(#/CF)(1mol/44#)(926atm(CF/mol)2)(2.72Btu/atm/CF)(mol-oR/6.71Btu) The average J (0.5oR/(8.54) (#/CF)= -0.06 oR/(CF/#)

For O2 298K & 10Bar to vac. oR = - 4.9oR, V=10.72(536)/147=39CF/mol, & 390CF/m oR =-(1/39-1/390)(mol/CF) (348atm(CF/mol)2)(2.72Btu/atm/CF)(mol-oR/5Btu) = -4.9 oR
The average J (4.9oR/(39) (mol/CF)= -0.13 oR/(CF/mol)

As with Enthalpy Correction for pressure, the Internal Energy may be density corrected: U = CvT + (T(P/T)V=c -P )V = CvT - Cv J V = Cv(T - J V) = Cv(T - T JX)
Verification of sign convention when correcting dH & dU for pressure effect: only 3 gases increase in temperature upon expansion at normal Ts, so, T JX & T 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 CO2 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 15 conditions.

 J , Isothermal Joule Coefficient For Free Expansion by RK eos

Isothermal Joule Coefficient of a Reversible Free Expansion (not to be confused with JT-X) or
J (T/V)U=c =(-1/Cv )(U/V)T=c =(-1/Cv)[ T(P/T)V=c P] T 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(P/T)V=c P] = 3a/(2T(V+b)V) (form kind of dV/V2) dT=(-1.5a/(CvT))[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)] |21 =(1/b)[ln{V/(V+b)}|21] T jx = [-1.5a/(bC v T)] {ln([V/(V+b)] 2 /[V/(V+b)] 1 )} by RK EOS integrated form for CO2 from 8.54CF/# to 17.1CF/# & Cv=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, Tc=548R, left apprentices is -1195.3R and right apprentices, which is 0.0064 unit-less free expansion, (1.5)(21677R-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 oR= - 5.35 by RK EOS = 584.3LN(

b.rk=0.696(b.vdw) & a.rk=Tc (a.vdw), as b.rk in cf/mol; divide by MW to put in CF/# b4 add w/V
16

 J , Joule Coefficient For Free Expansion by Viral EOS

J (T/V)U=c =(-1/Cv )(U/V)T=c =(-1/Cv)[ T(P/T)V=c P]= (-1/Cv)[ T(P/T)V=c P] Viral P=(T/V)[1+(B )Pr/Tr]& T(P/T)=T{[1+(B )Pr/Tr](T/V)/T+(T/V)[1+(B )Pr/Tr]/T}
T(P/T)-P = (T/V)[1+(B )Pr/Tr]+(T2/V)[1+(B )Pr/Tr]/T} - P = {P+(T2/V)[1+(B )Pr/Tr]/T} - P

T(P/T)-P= (T2/V) {[1+(B )Pr/Tr]/T} = (T2/V){Pr/Tr(B )/T + (B )(Pr/Tr)/T} T(P/T)-P=(T2/V) {Pr/Tr(B )/T - (PrTc)(B )/(T2)}=(Pr/V) {T Tc(B )/T - (B )Tc} T(P/T)-P=(PrTc/V){TB /T-B } =(PrTc/V){(T/Tc)B /Tr -B } =(PrTc/V){(TR)B /Tr -B } T(P/T)-P=(PrTc/V){(TR)B /Tr -B } =(PrTc/V){(0.67/Tr1.6 +0.72/Tr4.2)-B } T(P/T)-P=(PrTc/V){(0.67/Tr1.6 +0.72/Tr4.2)-(0.083-0.42/Tr1.6+ (0.139-0.172/Tr4.2)} T(P/T)-P=(PrTc/V){(0.67/Tr1.6 +0.72/Tr4.2)+(-0.083+0.42/Tr1.6 - 0.139+ 0.172/Tr4.2)} T(P/T)-P=(PrTc/V){1.09/Tr1.6 - 0.139 +0.89/Tr4.2-0.083}

cannot do integral dV/V as P & V related, use PV=Z T or P=(Z T/V), so (PrTc/V)=(Z T/V) Tc/(V Pc) The terms in brackets { } are dimensionless as & Tr , are dimensionless, as is Z. The integral of dV/V2 is (1/V) & term RTc/Cv has units of oR ((btu/mol)(mol-R/btu)=R), the term (1/V) ZT/(Pc) when using atm, comes to V=ZRT/P & 1/V=P/(ZRT)avg so (1/V)=(P2-P1)/(ZRT)avg so (1/V) ZT/(Pc)=(Pr2 Pr1)(ZRT)avg/(ZRT)avg.

T jx {(Pr)}{1.09/T r 1.6 - 0.139 +0.89 /T r 4.2 -0.083} (Tc)/C v Results for the prior 2 examples are CO2 oR= 2.04 & Oxygen, O2 oR= - 4.54 oR
B =(BPc/Tc) =(Bo+ B1) =f(Tr) use Bo=0.083-0.42/Tr1.6. B1=0.139-0.172/Tr4.2 B =(BPc/Tc) =(0.083 - 0.42/Tr1.6 + (0.139-0.172/Tr4.2)) B /T=(B /Tr)(Tr /T)=(1/Tc)(dBo/dTr+dB1/dTr ) & B /T=(1/Tc)(0.67/Tr2.6 +0.72/Tr5.2) Terms for Bo & B1 , Perry & SvN 3rdEd 75 p87 simple correlation of Abbott (1975) used here:

= 0.1745-0.0838Tr, Tr<0.65 P<10atm, otherwise use data tables for , &

dV/V = ln(V2/V1)

17

 J , Joule Coefficient For Free Expansion by BWR EOS

J (T/V)U=c =(-1/Cv )(U/V)T=c =(-1/Cv)[ T(P/T)V=c P]= (-1/Cv)[ T(P/T)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 & (P/T)V=c = (ZR/V)(T/T)V=c + (RT/V)(Z/T)V=c = ZR/V +(RT/V)Z/T|V & T(P/T)V=c = ZRT/V + (RT2/V)Z/T|V = P + (RT2/V)Z/T|V [ T(P/T)V=c P] = P + (RT2/V)Z/T|V P = (RT2/V)Z/T|V J (T/V)U=c = (-1/Cv)[ T(P/T)V=c P]= (-1/Cv)[(RT2/V)Z/T|V]= Tjx [(T2)]{ln(V2/V1)}{Z/T}/Cv (btu/mol)(mol-R/btu)=R Best for small change in dT was determined as:

T jx {Z}T/C v

units:(btu/mol)(mol-R/btu)=R, valid small dT & dP or T2 =T1/exp(ln(P1/P2)Z/Cv)

Alternative is to use reduced density method but was found to have higher error Z/T= (Z/Tr)(Tr/ T) = -0.27[Pr /(Tr2ra)](1/ Tc ) which leads to: T2 =T1/exp(ln(P1/P2)Z/Cv) Most simple is to use dT.jx = k dT.jtx
18

Summary of Equations for JT Coefficient, JT

JTX (T/P)h=c = -((h/p)T=c )/Cp = {T[(V/ T)p=c ]- V)}/Cp 1. The Van der Waals EOS, a & b are unique to the VdW EOS JTX (T/P)h=c = {(2a/T)-b}/Cp Not recommended 2. By any EOS for Z: [ as du/u =d(ln[u]) ln(u2/u1) or du u2-u1 & 1/V = P/ZRT] JTX = {T2/P}(Z/T)/Cp ={[ln(ZT2/ZT1)]/ln(T2/T1)}(ZRT/(PCp))average 3. Viral 2 term form: JTX = (T/Cp)((B)/T B/T) & B =(Tc/Pc)(Bo+ B1) TJTX =(Tc/Cp)(PR) {1.09/Tr1.6 - 0.139 +0.89/Tr4.2 - 0.083} (Bo+ B1)={(0.083-0.422/Tr1.6) (0.139-0.172/Tr4.2)}, 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.

ZT2 is numerically evaluated at average Pr and the average Tr estimated by JT for the given EOS.

4. Berthelot EOS: TJTX = {[PR]}(T/CP){1.27/Tr3 - 1/(14.2Tr)}

The specific heat, CP is the low pressure specific heat for all equations.
19

For this data set, the BWR Method has less error for HC gases. This is especially true for the C3= 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 LeeKessler BWR EOS is superior to all methods.

JT EOS Comparison
JT Result Com pare Viral/BWR/RK/vdW/B'lot EOS v. Tabulated Data

termR/atm C3= C1
u.jt.vir u.jt.bwr u.jt.Ber'lot u.jt.rk.dlnZ u.jt.rk.h eqn u.jt.rk.Z 1 2-Z reference page Pr.avg Tr.avg T.avg R P.avg atm 2.79 0.71 3.49 0.71 0.68 3.18 0.69 2.78 0.75 2.73 0.73 2.87 0.75

C1
0.78 1.01 0.88 0.82 1.27 1.17 1.30 0.92
p2 22

air
0.49 -0.04 0.96 0.56 0.31 0.36 0.30 0.31

CO2
1.76 2.13 1.21 1.92 1.94 1.89 1.94 2.12

H2

CO2 H2O
3.77 3.03 1.24 2.67 2.19 2.17 2.27 4.46

-0.09 1.32 -0.03 2.19 -0.04 1.11 -0.07 1.56 -0.06 2.05 -0.13 1.91 -0.06 2.08 -0.05 1.70

u.jt.vdw approx 1.66

u ref HS or TS 3.50 0.62

p4 9 .HS p 1 24

sch el Sch s Faries e am

Farie sHS p rry5h wiki jt perry5th stm e t Tabl p 2 /1 3 3 6 2 3 5 pp -1 3 www p -1 3 Kern 3 6 DQ

0.11 0.27 0.83 1.63 543 558

1.20 1.41 484

4.44 1.61 384

0.23 0.99 542

0.23 0.49 9.03 1.05 540 578

0.08 0.74 860

4.95 12.50 55.00

165.00 17.00 3.00 36.05 16.50

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. 20

 JT: Van der Waals Simplified JT Coefficient

A JT approximation from van der Waals EOS is: (adapted from McMaster)
JT T/P = {(2a/T)-b}/C p & b =Vc/3= 0.7302Tc/(8Pc), a = 27pc(b2) The VDW method for JT is used to make a 1st estimate of dT. From this expansion temperature
the calculation proceeds with more exact expressions of JT to determine average Tr. Iteration converges to an average JT by either R-K or Viral EOS. = universal gas constant, 1.99BTU/mol/oR or 0.7302atm CF/oR /mol, oR, Rankin & conversion factor, (2.72BTU/atm/CF). Units: b CF/mol, a atm(CF/mol)2 , T 0.73(atm-cf/mol/ oR)(oR) & Cp BTU/mol/oR b/Cp (CF/mol)(oR mol/BTU)(1/ =oR mol/0.7302 atm CF)( =1.99BTU/ oR mol)= oR/atm JT

OR/atm =2.72{(2a/(0.73oR)-b}/Cp & b

Tc/8Pc, a 27Pc(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-#. 21

 JT: Van der Waals Exact JT Coefficient

JT by from van der Waals EOS at high pressures is: JT T/P = {-b/Cp}{[4 3 - 3 (3 -1)2]/[4 3 - (3 -1)2]} & =Tr, =P Units: r
b CF/mol & Cp BTU/R/mol so multiply above result by 2.72 for units of R/atm b/Cp (CF/mol)(oR mol/BTU)(1/ =oR mol/0.7302 atm CF)( =1.99BTU/oR mol)= oR/atm

JT R/atm = 2.72{-b/Cp}{[4 3 - 3 (3 -1)2]/[4 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 Zc.. 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 Zc of 0.37. A Zc 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-bT)V2-4abV+2ab2=0 Likewise, Boyle curve of a vdW gas is any point defined by (a-bT)V2-2abV+ab2=0, Adapted from www. The VdW are generally poor estimations of either dT.jx or dT.jtx
22

 JT:Two Term Viral EOS JT Coefficient

JT = (T/Cp)((B )/T B /T) = (T(B )/T B )/Cp & B =(Tc/Pc)(Bo + B1) dB/dT=( /Pc)(dBo/dTr + dB1/dTr ) Where Bo & B1 = f(Tr) :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 3rd parameter, =f(Vapor Pressure @ Tr = 0.7) need an Binary interaction parameter ki-j for mixtures. Other limits of this viral form are: Vr>2, Best for non-polar or simular compounds
= 0.1745-0.0838Tr, Tr<0.65 P<10atm, otherwise use data tables for =(0.291-Zc)/0.08 Reid in Perry Eqn3-117, otherwise use data tables for Viral Terms for Bo & B1 , simple Abbott (1975): Bo=0.083-0.42/Tr1.6. B1=0.139-0.172/Tr4.2. Pitzer (1958) and Tsonopoulos (1974) Terms for Bo & B1 follow the form: Bo=A+B/Tr +C/Tr2 +D/Tr3 +E/Tr8. B1= =A+B/Tr +C/Tr2 +D/Tr3 +E/Tr8.. Viral Terms A B C D E A' B' C' D'

E'

Pitz Tson

1.4450E-01 -3.3000E-01 -1.3850E-01 -1.2100E-02 0.0000E+ 00 1.4450E-01 -3.3000E-01 -1.3850E-01 -1.2100E-02 -6.0700E-04

7.3000E-02 4.6000E-01 -5.0000E-01 -9.7000E-02 -7.3000E-03

6.3700E-02 0.0000E+ 00 3.3100E-01 -4.2300E-01 -8.0000E-03

JT = ( Tc/Cp)(1/Pc) {1.09/Tr1.6 - 0.139 +0.89/Tr4.2-0.083} & by Using Abbots formula & Compare to TJTX =(Tc/C p )(PR) {1.09/Tr1.6 - 0.139 +0.89/Tr4.2-0.083} & : Tjx (Tc/C v ) (PR){1.09/Tr1.6 - 0.139 +0.89/Tr4.2-0.083} (Tjx /TJTX )=(Cp/Cv) {f(B .JX)/f(B .JTX)} =(Cp/Cv) {1, for this EOS} =(Cp/Cv) 23

 JT: JT Coefficient as function of Z any EOS

For real gas PV=zT , & V = zT/P & JT = dT/dP |s=c Expressed in terms of V, JT = [T(dV/dT)-V]/Cp Td(zT/P)/dTV=T[z/P +(RT/P)(dz/dT)]-zT/P ={T2/P}(dZ/dT) JT =(T2/P)(dZ/dT)/Cp = 1.99(oR2/Patm)(Z/ oR)/Cp
In above equation make substitution: PV=ZT so {Schaums Thermo 1972 p163.eq2}

units: R=1.99btu/(oR) & Cp as btu//oR (oR/atm)[1.99btu/(oR)] (oR/btu)(oR/oR)=oR/atm

T/P = V/Z

& d(lnX) = 1/X dX

JT = (VT/Z)(dZ/dT)/Cp =(V)(dlnZ/dlnT)/Cp =(ZT/P)(dlnZ/dlnT)/Cp numerically evaluate the differential : dZ/dT = (ZT2-ZT1)/(T2-T1) at Pr average It is often simpler to make the numerical evaluation than do complex algebra JT=(Z T/P)(dlnZ/dlnT)/Cp = {[ln(ZT2/ZT1)]/ln(T2/T1)}(Z T/PCp)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)? 24

A.

Forms & Solutions of Redlich Kwong EOS M-N Exact Cubic Solution (after LF Scheel GPC 72 p144/103 & WC Edminster GPC62)
M = 0.427Pr/Tr2.5 - 0.00752(Pr/Tr)2 - 0.0867Pr/Tr - 1/3 N = M/3 - 0.0372(Pr/Tr1.75)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 + X0.5)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= 0.0867Pr/(zTr) = 0.0867 Tc/(VPc) (if V known) Zrk by h iteration method: Zrk=1/(1-h)-h/(1+h), =4.934/Tr1.5 Excess Properties and Fugacity by the RK EOS (from Perrys Eqn. 4-277/9
H/RT = 1.5ln(1+h) + (1-Z) & S/T = 0.5ln(1+h)-ln(Z-hZ) & ln =(S- H/T)/R Mixing Rules: 1.Kay Pc=(yPc)I & Tc= (yTc)I & 2. Empirical a=(1/3)(yTc /Pc)I +(2/3)((y(Tc /Pc))I )2 b=(y (Tc /Pc))I & Pc =(b/a)2 & Tc=(b2/a)
The a & b terms of Redlich Kwong are not same as a, b of VDW. For RK, a=0.0371b(Tc)1.5 & b=.0867(Tc/Pc), atm, K. The RK EOS gives Vc=3.85b where-as vdW gives Vc=3b. All gases at any T and high pressure, the volume approaches 0.26Vc, as calculated by RK EOS. b.rk=0.696b.vdw & a.rk=Tc a.vdw, as b.rk in cf/mol;

25

Zrk=[(1+h) - 4.93(h-h2)/(Tr1.5)]/(1-h2) & h = 0.0867Pr/(zTr) =K/(zTr) (1-h2)Zrk - (1+h) + J(h-h2)/(Tr1.5)=0 =f(z,Tr) & sub for h w/ J=4.93 & K= 0.0867Pr (1-(K/(zTr))2)Zrk - (1+ K/(zTr)) + J(K/(zTr) (K/(zTr))2)/(Tr1.5) & by z2 Tr3.5 z2 Tr3.5(1-(K/(zTr))2)Zrk- z2 Tr3.5(1+ K/(zTr)) + z2 Tr3.5 J(K/(zTr) (K/(zTr))2)/(Tr1.5) (Zrk3Tr3.5 ZrkTr1.5K2) - (Zrk2 Tr3.5 + Zrk1 Tr2.5 K) + Z2 Tr3.5 J(K/(zTr) (K/(zTr))2)/(Tr1.5) (Zrk3 Tr3.5 ZrkTr1.5K2) - (Zrk2 Tr3.5 + Zrk1 Tr2.5 K) + Z2 Tr2 J(K/(zTr) (K/(zTr))2) (Zrk3 Tr3.5 ZrkTr1.5K2) - (Zrk2 Tr3.5 + Zrk1 Tr2.5K) + J(Z Tr K (K2)) (Zrk3 Tr3.5 ZrkTr1.5K2) - (Zrk2 Tr3.5 + ZrkTr2.5K) + JK(Z Tr K) = 0 =f(z,Tr) Use implicit rule to get : Z/Tr = -(f/Tr)/(f/Z) & chain Z/T = (Z/Tr )/Tc (f/Tr)= (3.5Zrk3 Tr2.5 1.5K2 ZrkTr0.5) - (3.5z2 Tr2.5 + 2.5K ZrkTr1.5) + Zrk JK ( f/ T 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 ) (f/Z)= (3z2 Tr3.5 Tr1.5K2) - (2z1 Tr3.5 + Tr2.5K) + JK(Tr) ( f/ Z)= 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 Zrkc=1/3 :

Determine ( Z/ o R) by Redlich Kwong h method

Pr =3Tr/(Vr-0.26) 3.85/[(Tr0.5(Vr+0.26)Vr] (the RK EOS in reduced format)

26

Determine ( Z/ o R) by BWR Reduced Density Z =0.27Pr /(Tr r)EOS Z/ T= (Z/Tr)(Tr/ T) = - 0.27P r /(T r 2 ra )(1/ & Solve reduced density at average Z by Benedict-Webb-Rubin EOS f(r) = Ar6 + Br3 +Cr2 +Dr + (Er3)(1+Fr2)exp(-Fr2) -G f(r) = 6Ar5 + 3Br2 +2Cr1 +D + (Er2)[3+Fr2 (3-2Fr2)] exp(-Fr2) (r)i+1 = (r)i - f(r)/ f(r) use Z at average conditions for (r)0 = 0.27Pr /(Tr Za) A=0.06423, B=(0.5353Tr -0.6123), C=(0.3151Tr -1.0467-0.5783/Tr2), & D=Tr E=0.6816/Tr2 , F= 0.6845, & G=0.27Pr

Tc )

Ref: HP41 Petro Fluids Pac, Meehan & Ramey. Pc=(yPc)I Tc=(yTc)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

comparison of Z by Various References

# Pr Tr Zchrtpitz'r Zrk Zbwr.xls Zref 1.020 1.247 0.801 0.811 0.780 0.761 0.850 0.842 0.891 0.888 0.918 0.917 0.460 0.404 1.248 0.811 0.630 0.756 0.844 0.891 0.923 na 1 9.5 1.99 nd 1+ 2 5.0 1.50 0.810 4 0.4 0.90 0.778 5 0.4 1.00 0.850 6 0.4 1.10 0.880 7 0.4 1.20 0.910 8 1.2 1.05 0.470

3 0.4 0.80 nd 0.74? 0.650 0.535

A comparison of Z calculation by Benedict Webb Rubin Reference and RK EOS by excel is given in table on RHS to sundry reference sources. LI 1 & 2 are to test HP BWR clc convergence routine used in.xls to that of the HP41 HP BWR clc routine. LI 3 to 7 is comparison of BWR DPR to that of nC5 LeeK bwr BWR by Lee Kestler for nC5. A favorable comparison was found for the imposed limits of the DPR-BWR vs. nC5 LeeK bwr the LK-BWR. The Z by Pitzer chart is also included. nC5 LeeK bwr Pitzer chart has limits not imposed on EOS Eqns. The nC5 LeeK bwr hardy RK EOS is also included. At high Pr and also at nC5 LeeK bwr cryogenic conditions the BWR is reported to have better Z factors as compared to the RK EOS. 27 lim test HP bwr it

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 (U)=0 and for adiabatic Joule Thompson Expansion, (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+(V2/2g)/J)1+(Q-W)=(U+(V2/2g)/J)2+ (PV)+FL RB Bird 1957 in DM Himmelblau & HF Rase p100 1990 (H + V2/2g)1 + EG = (H + V2/2g)2 + FL (var..Perry 5th Ed., Real Gas-EB, Kinetic Gas Theory-Energy Bal.) {Ws + dP/ +VdV/g + [Pd(1/) + U] - Qh =0} & Qh = (TS - FL) Clausius/VL Streeter 5th Ed. p130 The reason to present these energy balance equations is pointing out that (H + V2/2g) =C is a very limited case. Equation, (H + V2/2g) =C does not correctly convey energy balance for applications with friction. Case 1. IDEAL NOZZLE/VALVE: No Work, No Friction Losses: (H + V2/2g)1 = (H + V2/2g)2 Case 2. REAL VALVE: w/ Friction, No Work or added energy: (H + V2/2g)1 = (H + V2/2g)2 + FL Case 3. Zero Initial Velocity: No Friction: with Work: EG + (H )1 = (H + V2/2g)2 Case 4. Constant Density: Heat Only & No Friction: EG + (H)1 = (H)2 There are too many cases to list. The point is one cannot call (H + V2/2g) 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 : H=U+ (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: Wa = F + (U-Q) + (V2/2g)/J). Expansion work by system between boundaries is (PV) & Wa -(PV)=F + (U-Q) + (V2/2g)/J) or H + (V2/2g)/J) + F=Q+W. For adiabatic expansion with zero 28 shaft work, the Newtonian energy balance of Prof. Rase is: H + (V2/2g)/J) F =0.

1. {(U+(V /2g)/J} =(Qh +W) :basic energy balance- steady state without elevation or other energy forms Perry 5-31
2

Energy Balance from Basic State

W or work is composed of external work & expansion work or W = Ws - (P/)

Perry 5-32 Perry p.5-18para.12 & Streeter

2. {U+ (P/) + (V2/2g)/J} = (Qh + Ws), next use Clausius Equality Qh = (TS - FL),

3. {U+ (P/) + (V2/2g)/J} = TS - FL +(Ws) & identity:H= U +(P/) with =1/Density=1/, & F is friction 4. {H + (V2/2g)/J}= TS - FL + (Ws =0 for valve)- Friction & heat are zero for an ideal flow nozzle 5. {H + (V2/2g)/J}= (0) Ideal Nozzle, but real nozzle which always has friction, use: TS = -d(P) + H 6. {H + (V2/2g)/J}= -d(P) + H - FL + (Ws =0 for valve) the H cancel, & =ZRT/PM leaving ZRT/M ln(P) 7. {(V2/2g)/J} + (ZRT/M)(dP)/P + FL = Make the integration to arrive at 8. (V2/2g)/J} + {ZRT/M)ln(P) + FL =0, Smith 10-4B p459 If differential velocity head is used, with velocity V = G/, one arrives at {(V2/2g)/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 (H + V2/2g) =C is a very limited case. Equation, (H + V2/2g) =C does not correctly convey energy balance for applications with friction. For Case of skin friction the energy balance reduces to (V2/2g)/J} + {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. 29

Clausius Equality, Second Thermo Law & Friction Heating

Clausius Equality: non reversible process requires: (Friction) = (TS-(Q)h), Streeter VL 1971 3.8.4; Perry p5.18 {Ws + dP/ +VdV/g + [Pd(1/) + U] - Qh =0} Streeter-3.8.1, General Volume E balance & Perry 5-31/32 {TS = Pd(1/) + (U)} = dH - VdP
Streeter (3.7.6): General Entropy, valid between any 2 Closed Equilibrium States,

{ Ws + dP/ +VdV/g + [TS - (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 + (F) =0 } Streeter 3.8.5 For case of zero shaft work, obtain: {dP/ +VdV/g + (Losses)}=0, Smith 10-4B

express losses as classic friction term and use V=G/ & dV = -Gd/-2 to obtain: {dP/ +(1/g)G2d/-3 + (Losses)}=0, multiply by 2 to get: {dP - G2d//g + 2(Losses)}=0. M&Smith 6-59 Use Real Gas density (=PM/ZRT) at average Z & T to get : {(M/ZRT)PdP - G2d//g + 2(Losses)}=0. Use Appendix identities to get: {M/(2ZRT) P2 - [G2ln(2/1)]/g + 2(Losses)}=0 Use average ZT, ln(2/1) reduces to: {M/(2ZRT)aP2 - G2ln(P2/P1) + a2(Losses)}=0. Smith takes (Losses) =(4fL/D)(G/LM)2/2g & takes (a/LM)2 =1 & sets Za =1 to get: {M/(2RTa) P2 - G2ln(P2/P1) + (2fL/D)G2/g} = 0 {Smith 10-4D aka classic isothermal flow to solve P2 } {Ws + (H + V2/2g/778) + {TS =[ Pd(1/)/778 + (U)] } - F = 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. 30

Clausius Equality: non reversible process requires: (Losses or Friction) = (TS-(Q)h), Streeter VL 1971 3.8.4. {Ws + dP/ +VdV/g +[Pd(1/) +U] - (Q)h =0} Streeter (3.8.1) General E balance for a volume. The term (U + Pd(1/) + dP/) = U + d(PV) = dH so: dH +VdV/g +{Ws - Qh } = 0. At zero work, dH +VdV/g -(Q)h = 0 Use (Q)h = (TS F) & dH +VdV/g - (TS F) = 0. If using pressure head, MEB, with zero shaft work, {TS = Pd(1/) + (U)} to get, dP/ +VdV/g + TS - TS + F = 0 or dP/ + VdV/g + F = 0. For constant density, the regular Bernoulli is seen (P/ +V2/2g)1 = (P/ +V2/2g)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 TS in Clausius Equality is (460+70/2+170/2)*0.6*ln(630/530) =580 *0.104=60.2BTU/#. Next find (Q)h) by Clausius Equality as: =(Q)h =TS- F = 60.2 - 24.4 =(Q)h = 35.8 BTU/#. Since {dP/ + Pd(1/) + U} = H, & Ws =0 rewrite 3.8.1 as {H + V.hd - (Q)h =0} the inlet V is 90fps and outlet V is 100fps. So {H + (1002-902)/50000 - (Q)h =0} so H=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 (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/#. 31

Clausius Equality, Second Thermo Law & Friction Heating

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/ + V2/2g + y + 778U)1 + EG = (P/ + V2/2g + y +778U)2 + FL (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:

The Energy Balance

(P/ + V2/2g)1 + EG = J Cv T + (P/ + V2/2g)2 +FL

For liquids Cp=Cv

For gasses, the term P/ is P/(PM/ZRT)= RT (but R=Cp-Cv) so RT = (Cp-Cv)T, & :

(TCp+V2/2g)1+ EG = (CvTCvT)+(TCp+V2/2g)2+FL

Seen in thermo terms H= TCp or H= (T-T.ref)Cp or use T2=T.ref then H= TCp

For Gases:

(H + V2/2g)1 + EG = (H + V2/2g)2 + FL

Case 1. IDEAL NOZZLE/VALVE: No Work, No Friction Losses: (H + V2/2g)1 = (H + V2/2g)2 Case 2. REAL VALVE: w/ Friction, No Work or added energy: (H + V2/2g)1 = (H + V2/2g)2 + FL Case 3. Zero Initial Velocity: No Friction: with Work: EG + (H )1 = (H + V2/2g)2 Case 4. Constant Density: Heat Only & No Friction: EG + (H)1 = (H)2 There are too many cases to list. The point is one cannot call (H + V2/2g) 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 H=U+ (P/). If either the 32 internal energy term or the loss term is neglected the sum of energy terms will not balance. The following tables

Liquid Pump Total Energy Balance-a

Liq ido t u u up t

in 5 6 .5 -1 4 .2 21 3 7 .6 0 8 .4 5 .9 6 0 0 0 .0 37 7 2 .7 0 1 .4 6 0 0 .6

ot u 5 6 .5 6 .2 9 1 0 0 .0 0 8 .4 9 .3 9 8 18 1 5 .7 37 7 2 .7

K 14 4 .1
BH > PM P= G

Cv 6 3 .0 298 576

Co 0 8 .3 3 .7 3 6 0 05 .0 4 0 7 .2 0 7 .8

Vfp s fr io H ft ict n d W r H a ft ok e d Vh a ft ed P h a ft ed T h a ft ed su m Pu pe m fficie cy n d Pu p T m

Liq id ou u u tp t

Re= > =f

d p efr io , p F T ip ict n ip d t t l, p p p F T oa m F+ ip
co lso p 6 : T H1 3 v 1 3 lc u n .1 6 D 1 ' s 1 ca

TD = o H * ffic. H W rk d e

in 3 0 .4 -0 1 .4 1 2 .7 26 7 0 8 .1 13 6 6 .4 0 0 .0 1 9 .0 30 0 0 7 .4 8 1 5 .6

ou t 7 6 .6 3 .3 6 7 0 0 .0 0 1 .9 73 6 1 .4 69 6 3 .2 1 9 .0 30 0

K 3 .9 9
BH > P= GPM

Cv 10 7 5 .8 5 190 830

Co 0 4 .4 30 0 0 .0 0 08 .0 4 0 9 .0 0 7 .8

V fp s frict n H ft io d Work H d ft ea V h a ft ed P h a ft ed T h a ft ed su m Pu p e m fficie cy n d Pu p F T m,

Re = >f =

d p e frict , F T ip ion d t t l, p p p F T o a m F+ ip
Ev s p 5 g es e= .4 9 an .1 0 iv 0 7

33

Liquid Pump Total Energy Balance-b

Liquid output

in 1.14 0.00 692.96 0.02 46.20 0.00 739.18 0.600 0.36

out

V fps friction Hd ft Work Head ft V head ft P head ft T head ft sum Pump efficiency dT Pump, F

1.14 0.0 0.00 0.00 BHP=>GPM 17.5 0.02 Re = >f = 52583 461.98 277.18 dT pipe friction, pipF 739.18 dT total, pmpF+ pipF

Cv 48564

Co 0.44 100.10 0.0061 0.00 0.36

Sv p.457 gives e= dTp= N 0.6 0.35F

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, CvT. It is also related to pump impeller efficiency, e, as T=(1/e-1) H/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. 34

Nozzle Efficiency & Friction-I

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 pp =[h(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, Cd=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 T2 with isentropic Expansion:T2=T1(P2/P1)(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 T needs to be less to make perfect balance. If try (H+V2/2g/778)1 = (H+V2/2g/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+V2/2g/778)1 = (H + V2/2g/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: 2/2g/778) = (H + V2/2g/778) + H (H+V 2 F 1 HF = Cp TF = dP/(J ) or use Fanning Friction term.

LI 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

item T,F Psia #/hr L'eq di" MW

u/m Cp bt /R

u cp air Z-RK eos f Fanning

u.jt.rk eos

in 140 221.8 4331 2.635 1.049 29.0 6.951 0.019 0.998 0.004 0.36

out 137.8 218.9 4331 2.635 1.049 29.0 6.951 0.019 0.998 0.004 0.36

V fps den pcf H btu/# H+Vhd F. thermo F. fanning F. dE thml

200.000 201.907

1.002 0.993 24.672 24.161 25.472 24.977 BTU/# 0.555 BTU/# 0.408 BTU/# 0.495

Isentropic dT ME bal out I Heads in 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
35

Nozzle Efficiency & Friction-II

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 Cp = 0.2397 =6.951BTU/mol/R, T1=600R, P1= 221.8psia & P2 = 218.9 or 15.088 atm & 14.891 atm respectively. Determine JT by RK EOS & T2 isenthalpic =T1(P2/P1)(1-1/k)e Table 1 below 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

P1
221.8 221.8 221.8 221.8 221.8 221.8

dP
2.90 5.08 6.53 21.80 40.00 77.63

P2
218.9 216.72 215.27 200.00 181.80 144.17

eff.I
0.977 0.981 0.980 0.967 0.937 0.876

dTfrct Ti @1 Ti+f

Tjt

T2 clcu.jt

2.239 597.7 599.94 599.9 597.8 0.3169 3.938 596.0 599.94 599.9 596.1 0.3170 5.020 594.9 599.9 16.83 582.5 599.3 30.89 566.9 597.8 59.94 530.5 599.9 595.0 0.3170 599.5 583.1 0.3176 599.1 568.9 0.3183 0.3196

590.44 598.31 5 8 3 .7

P1 T1 V1 221.8 600 200

d1 Ph1 Vh1 T2 V2 Sum 1 P2 1.000 41.05 0.7984 41.9 144.2 390.7 200

d2 Ph2 Vh2 0.998 26.73 0.801

fh2 Sum 2 14.37 41.90

Hf + (H + V2/2g/778)2 H = Cp(T2 - T1 - JT(P2 - P1)) & include friction H as 144dPf/778, Btu/# & T friction= Hf/Cp. For this thermo model it is determined that Tis @e=1 + TF = TJT,
Based on (H + V2/2g/778)1 = 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/ + V2/2g)1 = (P/ + V2/2g)2 + Pf/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. 36

Nozzles & Useful Gas Information from L. F. Scheel

Other useful formula from Scheel are: Correction of Nozzle flow for initial velocity: Ft/sec = V = 223.8Co {(h)/(1-[A]2/[A]1)} where dh is enthalpy change in BTU/#, 223.8 is root J2g. Once again the use of Co shows that h1=h2 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= Co 6.813 Psia(d2/Z (k MW/oR) & Choked acfm =73.3d2Co(koR)/MW) For generic hole use orifice Coefficient of Co 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(koR/MW) V, fps=3.06(acfm)/d2 #/sec=MMSCFD(MW/32.8) Pc= Po((2/k)+1)(1/(1-1/k)) where k=Cp/Cv for air at 14.7psia the critical pressure ratio is 14.7/27.7 =0.53 Den #/cf =PM/(10.73ZoR) where T Rankin , P psia, MW is molecular weight Gas Valve flow coefficient C.V.=(SCFM){(SG*T)/(520p*Psia.out)} p is psi Horsepower = (#/min) (dH BTU/#)/42.5, ideal k =Cp/Cv =Cp/(Cp-1.986), Cp is molar Cp. -S/P|T = V/T|P (R/P)[1+27Pr/(32Tr3)] & Cp-Cv R[1+27Pr/(32Tr3)] Berthelot EOS approximation, Walas p58 Nozzles, after Scheel 1.1 Co Gas k Avg T, Scheel Po/Pc Conoidal mouthpiece 0.98 1.67 He Ar 220F 2.04 mono Short Cyl. Round edge 0.92 Short Cyl. Square edge 0.82 1.40 Air H2 180F 1.88 Diatomic Pitot Tube 0.86 1.30 CO2 Steam 170F 1.85 Tri Sq. Edge Orifice Plates 1.20 HCCH, nC2, 135F 1.82 Poly d/D from 0.1 to 0.6 0.65 d/D from 0.61 to 0.74 0.68 1.67 Heavy Org 1.10 nC4 Bz 105F d/D limit 0.75 0.72 Scheel H 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- 37 Scheel: ft/sec=Co64.4 H
300 psia range, per Faires p 406

Generic Method for Gas Expansion with friction SvN EX.10-4

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. V. L. Streeter,5th Ed.71, p112 Eqn.3.2.2&.7 & Perry Eqn.5-31, state: dQ - dW = d(U+(V2/2g)/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 TS=T Cv [(T2/T1)k(P2/P1)(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. Smith-Van Ness Friction Energy Improved Cp@1 atm.Cp, H&U by expan Coeff

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 sum Sv btu/# N 67.2 68.6 4 SvN Ex.10-4 P457 5 0.12% 0.30% 6 eror%

F = (RTa/M)ln(P1/P2) -(V2/2g)/778 F = (G/LM)2(2fL/D)/32.2/778 , fanning f (U+(V2/2g)/J)1 + Q = (U+(V2/2g)/J)2 or Clausius (G2/g)[ln(1/2)+(2fL/D)]= -M/ 38

Total Energy (H+(V2/2g)/778)1 + Q = (H+ (V2/2g)/778)2 dP Friction (G2/g)[ln(1/2)+(2fL/D)] = -M/

Gas Expansion w/ friction: SvN Example:10.4 Disagree w/Process Simulator Results

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 T, F P, 'psia # /hr

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 in out outlet pressure is 20.4 and temperature is 192.2F. It appears SvN method 70.0 170.0 incorrectly sets dH=dU for heat required. Where-as the simulator method takes dH 34.70 19.00 as the heat requirement, without adding velocity head. A check of dH based on 1000.0 1000.0 temperature was made from Gas Tables for air, LI 7. The check shows agreement Lpipe Eq ft' 36.0 36.0 for the dH by all 3 methods , LI 1, 3-5 & 7. SvN acknowledge an acceptable error di inch 1.049 1.049 with their method. A 25% heat error and 14% outlet pressure error indicates a MW 29.0 29.0 systematic error by one of the methods. LI-5 shows that heat required to match SvN Cp btu/# /R 0.245 0.245 outlet pressure is only 24.2BTU/# with 46.3 feet of pipe., for same diameter of u cp 0.019 0.019 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 Z 1.000 1.000 head, which more closely match the Clausius Eqn. F=T*dS-Q, with dH reserved for 39 work, Which agree better with the H-S method of work.

Gas Expansion with friction SvN Example 10.4 Simulator Results not agree w/ SvN Method 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+(V2/2g)/J)1+(Q-W)=(U+(V2/2g)/J)2+(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, U 0 & (PV) = PdV + VdP = P*0+VdP =+VdP, the equation is ((V2/2g)/J)1+Q=((V2/2g)/J)2+VP/J+F The friction term is: F = (G/LM)2(2fL/D)/32.2/778. The expansion work is -(RTaln[P2/P1])/MW. The thermal energy Q is enthalpy change, as shown in simulator results or H=Cp (T + (P)JT) & = PM / ZRT & LM =(2-1)/ln(2/1) The grand equation is: [(G/)2 + (G/LM)2 (2fL/D)]/50000 1.986Ta [LN(P2/P1)]/MW = Cp [T + (P)JT] This equation for the case of zero heat addition reduces to the familiar isothermal pressure drop equation: [M/(2ZRTa)] (P2) - (G2/g)[ln(2/1)+(2fL/D)] = 0 The detailed pressure drop equation without expansion work reduces to Weymouth type (P2) 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 P2 to converge solution. 40

Gas Expansion with friction Adiabatic Flow Equation is an Ideal Gas Isenthalpic Expansion The adiabatic flow equation derivation uses ideal gas equation for isenthalpic expansion, and Cp-Cv=R to arrive at:

(fL/D)M =(4fL/D)F = (1/Mo2 1/M2)/k + (1+1/k)ln{[(Mo/M)2][(k-1)M2+2]/[(k-1)Mo2+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)M2+2], Density, Pressure and Temperature ratio are

To/T=Y/Yo & o/ =(M/Mo)(Yo/Y) & Po/P =(M/Mo)(Y/Yo).

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+(V2/2g)/J)1+(Q-W)=(U+(V2/2g)/J)2+(PV)+F. U=Cv(T + TJX) or U=Cv(T + (1/k)TJTX) or H=Cp(T + TJTX) & 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 TJX & TJTX are just the Joule or JT Expansion temperature change using the low pressure Cv or Cp and is thermodynamically correct. 41

Ideal Enthalpy Equation v. Adiabatic head & cautions Equation for ideal gas adiabatic compression head: Ha = RT1(k/(k-1)((P2/P1)(1-1/k) 1) Rk/(k-1) = (Cp-Cv)(Cp/Cv)/(k-1) = (k-1)Cp/(k-1) = Cp so rewrite Ha as Ha=T1Cp((P2/P1)(1-1/k) 1) & for adiabatic gas T2=T1(P2/P1)(1-1/k) Distribute T1 inside radical of but

Ha = Cp(T1(P2/P1)(1-1/k) T1) = Cp(T2-T1) & dHn= Cp(T2n-T1)

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 5th 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.

42

H & U of real gas as function of JT & J Temperature change: h = Cp T + (V T[(V/T)p=c )P (11.17 Eqn. 11-26 Faires & 11-7 Walas 1985), with
JT = {T[(V/T)p=c ]- V)}/Cp so - CpJT = (V T[(V/T)p=c ) gives h = Cp T + (-Cp JT) P H = Cp (T - JTdP) = Cp (T - TJTX), & U =Cv (T - TJX) C p or C v are C @ 1atm.
The true dH could be also be written in terms of = [(V/ T)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, P1=125, P2=20, P=-105, & T1=100F, T2=-35F, Ta=67.5F T=-135, h=-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= (dTa dh/Cp)/dPJT =(-135+40/0.361)/-105 = 0.23, about what viral EOS gives if in oR/psi or 3.4R/atm, see JT comparison page. by Scheel HS chart JT= (T/P)h=c =25/105 = 0.24R/psi =3.5R/atm exactly as given by BWR EOS. Callendar Schultz HS chrt* Table on RHS compares T2 & dH calculations. Using above dH formula w/o Cp pres. correction gives -42.5F -43.3F -38.5 T2 w/P corr Cp best dH results. Neither method matches T2 of HS dH w/P corrn 47.6 btu/# 40 chart. The Table confirms correct Cp is Cp @ 1atm as this same equation used to correct dH for dH w/Cp @1atm 40.03 btu/# 40.3 btu/# 40 pressure. *P-H CRI 1961 Carrier #144, Not same as & h=[(-35-100)-((20-125)/14.7)*3.5] 0.361 = Scheel Chart H-S shown by this document, h of h=(-135 +25)0.361= -39.71 = h isentropic Vs. chart Scheel chart for P1=125, P2=20, T1=100F, T2=100F of 40BTU/#. For U=0, T2 =93F, is: -[((20-125)/14.7)* 3.5 ] 0.361 = h = +9.03 h =0.36[93-100-((20-125)/14.7)*3.5] = +6.5 btu/#. BTU/# H isothermal. & H isothermal = 137 + Sign Convention Check: H=0 & U=0 is always 9.03 = 146. For Isentropic at same pressures: T2= C(dT-dTx) or dT=dTx & dT is mostly negative -35F & h= 43

Determine Cp by Explicit EOS: (C /P) R. L. Callendar EOS: V=RT/P+b+a/T3.33 Cp = 7.2R (P/Pc)/Tr4.33 given without derivation Or by Berthelot EOS Cp = 2.5R (P/Pc)/Tr3 given without derivation
p

T=c

= -(JTCp)/T|p=c
dCp T=-50C Cp P=1atm

AIR ICT Table dCp Calldr dCp chart dCp Bero'

Cp p=100

0.174 0.141 0.100 0.096

0.238 0.238 0.238 0.238 132.8

0.412 0.379 0.338 0.334 37.2

Chart/Table Perry p3.237 & p3.134 BTU/#/R

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.

Tc K / Pc atm
30.0 25.0 dCp 20.0 15.0 10.0 5.0 0.0 0.380 Z.rk 0.680 Compare Cp Corr Method y = -16.149Ln(x) + 0.4203 2 R = 0.9957

Callendar Berthelot Chart2-237 BCdr.avg Log. (BCdr.avg)

0.480

0.580

0.780

0.880

0.980

Note: R. L. Callendar produced the 1st 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 44

Schultzs Method For dH & dT Adiabatic,

Perry 5th ed. Eq.24.20 to 24.24,

Schultzs method

On page 80 example he wrongly uses Wa =Wp/e. Polytropic work Is Actual work

45

Schultzs X Chart

46

Schultzs Y

Ys {(-P/V)(V/P)T } then Ys=PT

47

A ?? Mod of Schultzs dH & dT method

This result questionable Not agree w/ Perry No precise reference

48

Express = Cp-Cv for real gas as z =Cp-Cv

PV=zRT- real gas Law Define H=U+PV dH/dT = Cp & & dH/dT = dU/dT +d(PV)/dT (valid only for reversible processes) dU/dT =Cv & d(PV)/dT = d(z T)/dT

Use d(z T)/dT = z + Tdz/dT Sub the values into: dH/dT = dU/dT +d(PV)/dT to get: Cp = Cv + z + Tdz/dT or (Cp-Cv) = (z )[1+T/z (dz/dT)] Cpjt=T/z(dz/dT) or (Cp-Cv) = (z )[1+ Cpjt/2.72] (same as Schultzs Eqn.) a 1st approximation is by neglecting term Cpjt/2.72 is: Cp - Cv = z
Dimensionless Number Units: Cpjt =(#/CF)(BTU/#/R)(R/atm)(1atm-cf/2.72btu), & H=TCp & U=TCv Aside: H =U + z(T), =U + PV + VP by steam table @P&T=c, L -> V check:@1atm, 212F: 970.3=897.5 + 72.8 =970.3 & TS=970.3 = H

Compare to Berthelot (1907) approximation for corrected Cp-Cv : Cp-Cv = R(1+1.7Pr/Tr3). The empirical Berthelot EOS is: Z=1+(1-6/Tr2)9Pr/(128Tr).
The exact Blot value for R correction, d(z T)/dT, is R(1+1.7Pr/2Tr3), hence the word, approximation. Blot EOS is a truncated viral with set to zero. The Blot Bo term is 0.07-0.42/Tr2 Compare to Abbott's Bo term of Bo=0.083-0.42/Tr1.6. Some simple gases with zero or <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 & 49 P<200atm. Walas85

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 5th Ed. Pg.24.34

T2=T1{P2/P1)(m)} m=(Z/Cp)() & =(+X)expansion =(1/ + X)compress Xs {[(T/V)(V/T)p ] 1} {ln(Z2/Z1)}/ln(Tr2/Tr1) & Ys {(-P/V)(V/P)T } 1-{ln(Z2/Z1)}/ln(Pr2/Pr1) Now recast X, above in terms of JT function, =(T/V(V/T)p-1)(V/Cp) Cp /V = {[(T/V)(V/T)p ] 1} = X with 1/V= =( + Cp)expansion

ms=Z(Cp - Cv )/Cp+ZCp/VCp =Z/Cp+Z/V=Z(1-1/) + Z/V By real gas law P/T=Z/V so m=Z(1-1/) + P/T At =1 for ideal gas, (Z=1 & =0) reduces to the familiar T2= T1 (P2/P1)(1-1/k) At =0 for ideal gas, (Z=1 & =0) gives T2=T1 . Few gases are ideal so at small , expect big errors. For the locked rotor case where =0 gives T2= T1 (P2/P1)(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 T =-(1/V)(V/P)T & Ys {(-P/V)(V/P)T } then Ys=PT The term T is the isothermal compressibility aka Cg in petroleum reservoir analysis.
To keep ( + Cp) unit less, when (#/CF)(R/atm)(BTU/#/R), use the conversion of 1CF-atm per 2.72BTU or 50 0.73/1.986 = 0.37 or ( + 0.37Cp).

Compare Temperature difference to HS chart of C3= for ideal, Schultz, & JT

0.050

calc error for Xpander Outlet T

Err JT.rk w/Cp corr Err ideal Err SchulteX w/Cp corr Err JT.w/o Cp corr

absErr Tout v H-S

0.040

0.030

0.020

0.010

Expander Efficiency

0.000

0.2

0.4

0.6

0.8

ms = (Z/Cp)(+Xs) & m.jt= (1.99Z/Cp)( + 0.73jtCp/1.99) & m.ideal=(1-1/k) & Cp = 4.234+oR/48.54, btu/mol/R for C3= only, jt per the RK EOS,R/atm.; =PM/(Z10.7oR), #/cf; Z per RK EOS, Pc Tc & Xs as per data given here-in. k= Cp /Cv . The ideal case has large error at =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 Cp correction is an improvement over other methods, if one lacks HS charts for a particular gas. 51

Compare Enthalpy difference to HS chart of C3= for ideal, Schultz, & JT

3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 0 0.2 0.4 0.6 0.8 a bs(dHclc-dH h-s)

d @e 1is 4 BTU fr H C3 H = 0 /# om S =
Err JT.rk w/Cp corr Err ideal Err Schult w corr eX /Cp Err JT.w Cp corr /o

e fficie ncy

By Schultz: ns=1/(Y-ms (1+Xs)) & for ideal case n=(1-1/k), k=Cp/Cv ideal. dHpoly = (-n /(n -1))(ZRT)1((P2/P1)((n-1)/n)-1).
Simpler just calculate dH from JT equation: dh = Cp (dT - JTdP), where - JTdP 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, 52

N2 Expansion Turbine Calc Performance by Pipe Friction

Gas T, F P, 'psia # /hr out 751.400 445.400 88.200 4930.000 4930.000 Lpipe Eq ft' 10000.000 10000.000 di inch 4.296 4.296 MW- N2 28.000 28.000 Cp btu/# /R 0.248 0.248 u cp 0.019 0.019 Z 1.000 1.000 in Gas calc in result out.Result T psia 22.10 0.0 81482.6 friction Hd ft 0.0 Work Head ft -58413.6 79.4 706.6 V head ft 66786.2 49916.0 P head ft 123629.1 0.0 T hd ft Cv 132081.1 132105.2 sum Mach 0.04 0.00 imed reslt den pcf V fps Ai" sq. f Re in out 0.190 0.129 71.49 0.62 14.499 14.499 0.0040 0.0040 381579.63 381579.63 Efficie cyp .id n oly l 0.77 P2 estimate 44.69 G# /sec/sf 13.6 2RTz/M avg 32.4

Anal:Coulson X3.15:Po= from Coulson X3.15:Po=22.1psia,To=445.4F,poly.Effic.=0.75&Ht=-59950, 22.1psia,To= 445.4F,poly.Effic.= 0.75&Ht= -59950, &this w/e= 0.75= Po= > 21.6,To= 451F &Hpoly= -57226' The above example Anal: X3.15 phead tot.=Po=21.6, To=451F & Hpoly=-57226Pi/Ti 88.2/751.4 & Hw= 58414 w/ 77%eff. To/Po445.4/22.1 this w/e=0.75=> 59,950 feet vs calc 58414, diff is V Hd, use X3.15

&

use HP= e*(Work-ft)*(# /min)/33000

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

U, or internal energy change, the Joule correction is neglected. This is not considered a serious omission for this calc. Because jV is small or U=Cv(T + jV) CvT, as seen by how close the energy balance closes.

53

Cross Correlations of Coefficients I For ideal gas: JT =0, = 1/T, T =1/p, s =1/(p), & as=1/(s ), Cp- Cv =

For Real gas: JT =(T/P)h , =(V/T)p , T =-(V/P)T , s =-(V/P)s ,

JT = (T/P)s -1/(Cp) = (T -1)/(Cp) = [T(V/T)p -V]/(Cp)= [(P/T)v=c]

J (T/V)U=c =(-1/Cv )(U/V)T=c =-[T(P/T)V=c P]/Cv compare to Joule Thompson Exp.: JT (T/P)H=c =(-1/Cp )(H/P)T=c = [T(V/T)p=c V]/Cp
Joule Free Expansion:

Cp - Cv = T2/(T) & Cp/Cv = = T /s & s = (T/P)s & as=(P/)s s - JT =V/Cp = ZT(1- s/T)/P & = (V/P)T(P/V)s & as (P/) T =[1/p-(Z/P)/Z] & = [1/T- (Z/T)/Z] & JT =(T2/P)(dZ/dT)/Cp
V/V =[()T + (T)P] & JT = (T/P)s -1/(Cp)
Routines for z & T commonly available using Tr, Pr for, reservoir work, like: T =(1/(PcPr))(1/(1+(r/Z)(Z/r))) where Z & r from BWR EOS (Z/r)=[5Ar5+2Br2 +Cr+2Er2(1+Fr2 F2r4)exp(-Fr2)]/(rTr) For example at Tr=1.7, Pr=2.8, Pc=361.5psi T =0.001/psi & 1/V = m = (Psia)/(z10.7/oR)

: 1.98BTU/mol/R, 0.7302atmCF/mol/R, 1545ft#/mol/R & J = 778ft#/BTU

54

Cross Correlations of Coefficients II (Cp/P)T=c = -(JTCp)/T|p=c = -[{T2/P}(Z/T)]/T|p=c for Cp of P 1 (dCp)T = -(2T/)dP (Cp/P)T = -TV(2+ ( T)p) & (S/P)T= -(V/T)P S/P|T=c = -V & S/T|p=c = Cp/T & S/V|T=c = (/T) = (P/T)v (U/P)T = (PT -T)V = (1+PT - T)V & (U/V)T = {(T/T) P} U=(Cp - p/)T + (PT -T/)P = U = Cv(T-JV) (h/P)T =(1 - T)/ V/V =()T + (T)P & & (h/V)T =(T-1)/T (/P)T = -(T/T)P & (P/T)v = /T

JT = (T -1)/(Cp) where = [(V/T)p=c ] = [(P/T)v=c ] T & =1/V= P/zT T =[1/P - (Z/P)|T=c /Z] & = [1/T - (Z/T)|P/Z] & JT={T2/P}(Z/T)/Cp H = Cp(T) - [T(V/T)p -V]P & U = Cv(T) + [T(P/T)V=c P]V H = Cp(T) - [(Cp)JT ]P & U = Cv(T) + [-J Cv](1/V)
The above 2 equations may be used to correct U & H for conditions other than 1atm.
Perry4-144/151

But (Cp)JT = [T(V/T)p -V] & -J Cv = [T(P/T)V=c P], so H & U by JT & J is =

H = Cp(T- JTp) & U = Cv(T-J(1/V)) for gas expansions with H=0 or U=0
TJTX =( JTp) & TJX = (- J(1/V)) AKA isenthalpic w/H=0 & constant U ie U=0
55

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. Zc for hydrocarbons and the average for all gasses is 0.27. Thus Zc = 0.27 is the basis for most Z charts. Polar molecules have smallest Zc, whilst spherical molecules have largest Zc. The vdW EOS Zc is 0.375, while RK EOS has Zc about 1/3, the BWR form presented here has Zc of 0.27. Limitations to EOS validity range should be strictly observed. For example, Berthelot and 2 term viral calculate Zc of 0.65. The recommendation for the 2 term viral is for Vr>2 & below 2 use Pitzer Charts. The Pitzer Charts also use Zc of 0.27 but adjust for a given gas by . 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 Tcn=Tc+8K and Pcn=Pc+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 of 0.303. The next idea uses tailored EOS fitted around Zc for a particular gas or gas type, e.g. BWR given here. Advanced EOS use an accentric factor, , to make adjustment for effect of Zc. Examples are LK-BWR, S-RW, and PingRobinson. 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 5th order viral, termed ELIR or extended linear isotherm regularity. ELIR gas is defined by 2nd & 3rd viral coefficients and Boyle density is family of curves for Z/P|T=c=0 & b=((PV)/P)T=c=0. Boyle Temperature is T at P=0 for which Z/P|T=c =0

' Compare Zc to EOS and Z chart Corresponding States: Pitzer Viral Zc, 0.24-> 0.29 & BWR* 0.27
Gas CAN HCN H2O NH nC6 Avg Gz BW Z chrt C2 3 R* C3 CO2 C1 Air H2& e Ne RK vdW H 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
Zc=0.291-A (Yamada Liquid A=1, LK-BWR, A=0.085 & Edminster, A=0.08, Pitzer, A=0.28) 56

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: /==/Cv=Vrms /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= jH =jM. Friction factor, f, is the ratio of momentum loss at wall to bulk shear. Likewise jH 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/), (Cp/), & (/M); are known as Reynolds, Prandtl, and Schmidt. By Kinetic Theory, = ACv & = A so the Prandtl number is the ratio of heat capacity, (Cp/Cv). Gambil arranged Prandtl numbers of gasses by molecular structure, 0.67 for monoatomic 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/ + V2/2g)1 + EG = J Cv T + (P/ + V2/2g)2 +FL Sub JRT for P/=PV & 1.5R for Cv : (JRT + V2/2g)1 + EG = J 1.5R T + (JRT + V2/2g)2 +FL Sub for T= T2-T1 : (V2/2g)1 + EG = J 1.5R T +J RT + (V2/2g)2 +FL Add the R Ts: (V2/2g)1 + EG = J 2.5R T + (V2/2g)2 + FL Use Mono gas table & Sub for 2.5RT as H: (V2/2g)1 + EG = JH + (V2/2g)2 + FL
Notice result is the same when determined by ideal gas law: A proper energy balance MUST account for friction to specify the result.

57

Kinetic Theory of Gases

Item
Coefficient

Viscosity
/=Vrms/3=74.3(0R/M)=

Heat Flow
/Cv= Vrms /3 =

Diffusion
=Vrms/3=74.3(0R/M)= Vrms /3

term
property Analogy Analogy
*

[d(mv)/dt]/A= dv/dr
=27(MT)/[Vb (1+Tc/Tb)]

Q/A= dT/dr
=(Cv+9/mw) jH=(h/CpG)(Cp/)0.67= = Q.wall/Bulk Q= Prandtl Number (Cp/) jH=(T/t)(a/A)(Cp/)0.67

J=dm/dt=DA dm/dr
*AA 1.57Vc-0.67(0R/MW) Perry 1973

f/2=0.023/(DG/)0.2 =
(P).wall/(bulk momentum)

. jM =(M/G)(/M)0.67
=m.wall/bulk mass= Schmidt Number (/M) = (/kd) jd=(P/p)(a/A)(/kd)0.67 = Constant

-d # name -d # ratio
application

Reynolds Number (DG/), inertia/viscous PD/(4LV2/g)=f/2

Lewis #
(/MCp)
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=Vrms(Cp /Cv/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)/(Cp/). 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.

58

Dimensionless Numbers of Gas Expansion

The dimensionless Number, CpJT , is a ratio of gas expansion temperature change to friction temperature change, for dP & JT 0, as TF = PF/(J.) = TJT = (JTCp)P. Which is true only when 0 h=CpT+(-Cp JT)P. Recognizable as the isenthalpic case using Schultz Temperature relation for the general isentropic case. To keep (Cp) 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 (0.37CpJT)=NJT. Another dimensionless Number, the Joule Number or NJ = (J/P)CvJ , is associated with the Joule Free Expansion. It is the ratio of dTw =P(dV/J) and dT.jx = (dV)CvJ , the dVs cancel leaving: NJ = (J/P)CvJ . A 3rd dimensionless number may be formed by taking the ratio of the 1st two, namely: NJA =(NJT/NJ) = (0.37CpJT)/((J/P)CvJ) = (0.37/J) (P/V)(CpJT)/(CvJ) from pressure & volume change is: NJA =EJT /EJ = (CpTH=c)/(CvTU=c) = (PCpJT)/(VCvJ) which can be related to the ratio of (H/U) 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. H = Cp (T- PJT) & U = Cv (T- VJ) for at H =0 & U =0, then TJX = VJ & TJTX = PJT Furthermore it seems NJA =(NJT/NJ) must be related to acoustic velocity at real conditions. Sonic velocity is determined as a =(P/) =-(V/)(P/V)|s ? -(V/)N{(CpJT)/(CvJ)/|s] This is just a presentation of talking points. The main point is to better understand what Schultz did in development of his method. 59

Kinetic Theory of Gases

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)= (2MkT)1.5V/h3N & (Qr2)= (eT) / & (Qv3)=x/(ex-1) & (Qv4)=ex(x/(ex-1))2 & (Qv5)=Qv3-ln(1-1/ex) where X = ch/kT. The various terms are: temperature, T , absolute, & , 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 P RT/V T.2 Diatomic Degree P U Cv CP H S U 1.5RT disassociation
not considered

Translation Rotation Vibration

RT/V

1.5RT RT

1.5R R

2.5R R

2.5RT RT

2.5Rln(Qt1) Rln(Qr2)

Cv Cp/Cv H

1.5R 1.67R 2.5RT

RT (Qv3) R(Qv4) R(Qv4) RT (Qv3) R(Qv5) S 2.5Rln(Qt1) A formula for CP is R(1+f/2) & CP/Cv =1+2/f. With f = number of degree of freedom. For the example H2O vapor at 1000K the degrees of freedom activated are: 2(9.81/1.986-1)= 7 plus 88% of the 8th 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 Vrms . Thermal equilibrium between 2 objects of different temperature is achieved when they have identical RMS velocities. Summary: Gas energy by Kinetic Theory is an exclusive function of temperature. Gas Pressure and Entropy are related to temperature, specific volume. /==/Cv=VRMS (/3). 60

Properties of Common Gases

gas Air N2 O2 CO2 C1 C2 C2= C3= H2 R12 NH3 Toul Ne
MW k60F

29 28 32 44 16 30 28 42 2 121 17 92 20

1.41 1.41 1.40 1.30 1.32 1.22 1.25 1.16 1.41 1.13 1.32 1.10 1.67

Tc Pc 239.0 37.2 227.0 33.5 278.0 50.1 548.0 72.9 344.0 45.8 550.0 48.2 510.0 50.5 657.0 45.6 59.8 12.8 692.0 39.6 730.0 111 1065.1 40.6 79.9 27.2

Zc 0.284 0.291 0.290 0.276 0.290 0.284 0.270 0.275 0.304 0.272 0.242 0.264 0.311

a.vdw b.vdw 345 0.585 346 0.618 348 0.506 926 0.686 581 0.685 1410 1.041 1158 0.922 2129 1.315 63 0.426 2718 1.595 1076 0.598 6285 2.394 53 2.68

w.actr 0.036 0.040 0.021 0.225 0.007 0.091 0.086 0.148 0.000 0.158 0.250 0.257 0.000

A 6.737 6.839 6.459 6.075 4.877 3.629 3.175 4.234 6.662 8.399 6.219 1.869 5.000

B 3.97E-04 2.13E-04 1.02E-03 5.23E-03 6.77E-03 1.68E-02 1.35E-02 2.06E-02 4.17E-04 1.59E-02 4.34E-03 4.30E-02 0.0E+ 00

Zac u.jt.v u.j.v Cp 0.998 0.43 0.08 6.96 0.999 0.42 0.08 6.96 0.996 0.46 0.08 7.03 9 0.962 1.16 0.17 0.987 0.68 0.11 8.67 13 0.943 1.22 0.17 0.957 1.20 0.17 10.7 0.893 1.57 0.23 15.8 6.9 1.005 -0.05 0.01 0.853 1.84 0.29 17.3 0.934 1.47 0.22 8.65 0.315 2.97 3.11 25.9 5 1.003 -1.32 0.02

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, P=(125-20)/14.7 = 7.14 atm & Cv=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 TJTX = (JTP) =1.57*7.14/ = -11.2R & TJX = J V2 ((1/V)) =0.23*432*(1/43-1/245)= -8.4R 61

Gas X C3= initial: 125psia,100F basis: P-H Carrier #144chart S1=1.42 H1=137 Z1=0.932

Review of C3= Gas eXpansion by thermodynamic states

-dG
443.1 39.6 31.5 4.6 -67.7 -117.9

Condition
++ThermX IsoThermX FreeX dU=0 Isenth.X dH=0 Isentropic X Chilled X

dH
51.0 9.5 6.5 0.00 -40.0 -51.0

dU
78.3 2.5 0.00 -5.5 -37.5 -49.0

dS
0.235 0.094 0.089 0.075 0.00 0.019

dT 200.0 0.00 -7.8 -25.0 -135.0 -180.0

dPsi Cp avg dTjx T2

-110 -105 -105 -105 -105 -118 0.425 0.375 0.374 0.369 0.342 0.331 -7.6 -7.7 -7.8 -7.8 -7.9 -7.6

P2 15.0 20.0 20.0 20.0 20.0 7.0

V2/V1 S2

1.44 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 G function indicates spontaneity or degree of organization needed. While dG indicates maximum work potential. The S function indicates the probability of the process. Both these quantities, G & S, 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=TS-Q & Q=0 so F=560*0.089=48 BTU/#. For JTX F=TS-Q = 548*0.075=41, for IEX, F=TS+0=560*0=0. So Friction Loss JX>JTX>IEX. 62 Isothermal, ITX, represents a case where heat addition is required.

300 100 92 75 -35 -80

12.1 6.6 6.5 6.3 4.9 12.1

1.66 1.51 1.51 1.50 1.42

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.

Review of C3= Gas eXpansion by thermodynamic states

6.0

C3=Exp 125psia/100F to 20psia Carrier # Z1= 144 0.932 dU= dH-d(PV)

5.0 4.0 3.0 2.0 1.0 0.0 60.0 -1.0 -2.0 65.0

i s p 0 2 o t i s p 5 2 1 # / U T B
70.0

dU btu/# dH btu/#

T F @20psia C3=expansion ,
75.0 80.0

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. 63

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 T, (PV)/T = Z + T(z/T) - ie real gas law PV=Z T, (V)/T = Z /P+ T(z/T)/P 2 : d(1/Z) = -()/Z2 ie dP/dV =Z T[-( )/V2] + Z T[dZ/dV]/V 3. Natural logs: -du/u =d(ln[u]) & du=u[dln(u)] 4. Integrated forms: du/u = ln(u2/u1); du = u2-u1; vdv = v2 5. Implicit: (g)/v = - (f/v) / (f/g) where f =F(g,v) 6. Chain Rule: dy/dx = (dy/dv) (dv/du)(du/dx) & dZ2=2Z[d(Z)] 7. Total differential df= (f/z)dZ+ (f/x) dX+(f/y)dY
8. PdV = - VdP+ (PV) & - VdP = PdV - (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)
64

Berthelot EOS for Joule & JT Coefficients

The empirical Berthelot EOS is: Z = 1 + 9Pr/(128Tr) - 54Pr/(128Tr3) = PV/RT so V & P are:
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

V= RT/P +(RT/P)9Pr/(128Tr) (RT/P)54Pr/(128Tr3) & P= RT/V +(RT/V)9Pr/(128Tr) -(RT/V)54Pr/(128Tr3) JT (T/P)h= -(h/p)T/Cp = {TV/T|p - V}/Cp & J (T/V)U= (-1/Cv )(U/V)T = (-1/Cv){TP/T|V P}
________________________________________________________________________________________________________________________________________________________

{TV/T|p - V} =T(RT/P +(RT/P)9Pr/(128Tr) (RT/P)54Pr/(128Tr3) )/T|p V

{TV/T|p - V} =(RT/P + 0 +(RT/P)108Pr/(128Tr3) (RT/P +(RT/P)9Pr/(128Tr) (RT/P)54Pr/(128Tr3) {TV/T|p - V}=(0+ 0 +(RT/P)108Pr/(128Tr3) +(-0-(RT/P)9Pr/(128Tr) +(RT/P)54Pr/(128Tr3) {TV/T|p - V}=RT/Pc{1.27/Tr3 - 1/(14.2Tr)} = & T = P RT/Pc{1.27/Tr3 - 1/(14.2Tr)}/Cp JT (T/P)h= RT/Pc{1.27/Tr3 - 1/(14.2Tr)}/Cp & TJTX = {[PR]}(RT/CP){1.27/Tr3 - 1/(14.2Tr)}
---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------3 V p r r r r

{TP/T| - P} =T(RT/V+(RT/V)9P /(128T ) (RT/V)54P /(128T ) )/T| P {TP/T|V- P} =T(R/V+(0) +(R/V)108Pr/(128Tr3) P

{TP/T|V - P} =(RT/V + (RT/V)108Pr/(128Tr3) +(-RT/V -(RT/V)9Pr/(128Tr) + (RT/V)54Pr/(128Tr3)) {TP/T|V- P} =(0+ (RT/V)108Pr/(128Tr3) +(-0 - (RT/V)9Pr/(128Tr) + (RT/V)54Pr/(128Tr3)) {TP/T|V - P}(-1/Cv)=(RT/V){1.266/(Tr3) - 1/(14.2Tr) }(Pr)(-1/Cv) but RT/V =P for Z defined by this EOS J (T/V)U= (P){1.27/(Tr3) - 1/(14.2Tr) } (P/Pc) (-1/Cv ), but dV =-(RT/P/P)dP TJX = (P){1.27(Tr3) - 1/(14.2Tr)} (P/Pc) (-1/Cv ) -(RT/P/P)dP, the P*P/P/P cancel out leaving (dP/Pc) TJX = (PR)(RT/Cv ){1.266/(Tr3) - 1/(14.2Tr)} & also Cv TJX = Cp TJTX

Cv TJX = (Cp TJTX ) , so TJX = k TJTX

65

Ratio of dT Joule & to dT Joule-Thompson by Energy Equations

Based on results for both Berthelot and Viral EOSs it appears the ratio for (Tjx /TJTX ) is just the ratio of (Cp/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: H = Cp(T- JTp) = Cp(T- TJTX), & : U = Cv(T-J(1/V)) = Cv(T-TJX) . For JTX H =0;

H =0 = Cp(TJTX - TJTX) = {U + (PV)}={U + (PV)2 (PV)1} = {U + R(ZT)}, if use avg Z H =0 = Cp(TJT - TJT) = U + ZR(TJT) = Cv(TJTX - TJX) + ZR(TJTX) = 0, but ZR= Cp Cv Cv(TJTX - TJX) + (Cp - Cv)(TJTX) = 0 & distribute: 0= (Cv TJTX - Cv TJX) + (Cp TJTX - Cv TJTX) 0 = (0 - Cv TJX) + (Cp TJTX - 0) = 0 or: Cp TJTX - Cv TJX or: Cv TJX = Cp TJTX
This ratio of (Cp/Cv) = (TJX)/TJTX) is the same result arrived at by the Viral & Berthelot EOSs (Tjx /TJTX )=(Cp/Cv) {f(B.JX)/f(B.JTX)} =(Cp/Cv) {1, for B'lot or Viral EOS} =(Cp/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: Tjx = (Cp/Cv)TJTX = (k)TJTX

Sat eam 325 t 162.5psia k= & k rule 1.15 .St : o 1.18

U BTU/# H BTU/# T1 F , T2H= T2 U= d H= d U= C C T C T C

1117.5 1203.5 424.5 375.5 368.0 49.0

56.5

66

Simplified Look at Isenthalpic & Joule Expansions

Use results that the ratio for (Tjx /TJTX ) is just the ratio of (Cp/Cv) or k. The slide looks at a constant enthalpy expansion from a PV standpoint: with proof from H-S chart of (Tjx /TJTX) = (Cp/Cv) = k H = Cp(T- JTp) = Cp(T- TJTX), & U = Cv(T-J(1/V)) = Cv(T-TJX) & for JTX H =0 = Cp(TJTX - TJTX) = {U + (PV)}={Cv(TJTX - TJX) + (PV)} = 0 H =0= {U + (PV)}={Cv(TJTX - TJX) + (PV)} = {Cv(TJTX - kTJTX) + (PV)} =0 & ZR= Cp Cv H =0= {Cv(TJTX - kTJTX) + (PV)} = {Cv TJTX (1- k) + (PV)}= {TJTX (Cv - Cp) + (PV)} =0 H =0 = {TJTX (Cv - Cp) + (PV)} = {-ZRTJTX + (PV)} =0 or {(PV)JTX}/J= ZRTJTX The term (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 TJTX from EOS or chart is needed. The term, (PV)/J= ZRT, is valid any gas, but arriving at this by use of, Tjx =kTJTX validates that Tjx =kTJTX . dH For A) Joule Expansion, {U=0} & use Scheels chart from 100F & 125 to 20psia, C3= 1 2 followed by; B). constant pressure expansion to JT condition, 75F. With k= 1.149; Psia 125 20 Cp=15.31BTU/mol/F; TJTX = -25F. & TJT = -25F x 1.149= -28.7F. T, F 100 75 A) HJX = {U + (PV)}={0+(PV)}={Cp(TJX - TJTX)}=Cp(k TJTX -TJTX) Z 0.94 0.94 H =15.31/42(-25)(1.149-1)= -1.36BTU/# 42 42 B).From the constant pressure Joule Expansion conditions, no JT correction is needed M as the expansion is at constant pressure so HJX/JTX ={Cp(TJTX -TJX}=0.365(75-71.3F) =1.35 V cf/# 1.08 6.42 BTU/#. PV btu/# 24.9 23.8 C) The sum of these 2 expansions is HJTX = -1.36+1.35=0.010. As no heat is added at d(zRT) -1.11 EX.1 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)/J -1.11 JTX d(PV) calc is left off but closes with use of Z, as shown in Table to right, which diff/err -9E-06 C3= validates (Tjx /TJTX) = (Cp/Cv) = k by using JX- JTX rules: arrive at (PV)/J= ZRT. 67

Ratio of dT Joule & to dT Joule-Thompson: Part 3

Why is the ratio for (Tjx /TJTX ) just the ratio of (Cp/Cv) or k? The slide looks at this concept from the EOS thermo concept using primary definition of the terms:

JTX (T/P)h = -(H/P)T/Cp = {T(V/T)p - V} /Cp or dTJTX Cp = {T(V/T)p - V} dP JX (T/V)U = -(U/V)T /Cv = {T(P/T)V P} /Cv or dTJX Cv = {T(P/T)V P} dV

What is said in prior 2 slides is: dTJTX Cp = dTJX Cv so {T(V/T)p - V} dP = {T(P/T)V P} dV Using PV=RT, V=RT/P & P=RT/V, & T(V/T)p = RT/P & T(P/T)V =RT/V & dP = -RT/P2 so dV= dP RT/P2 Make the subs {T(V/T)p - V} dP = {T(P/T)V P} dV & {RT/P - V} dP = {RT/V P} -dP RT/P2 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. dTJTX Cp = dTJX Cv k dTJTX = dTJX 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: (Tjx /TJTX )= (Cp/Cv) 68

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. 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.

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

Vendor B

69

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.

Source. F/100psid MW dPSI Field Measured 23.3 770 HySys- w/Lab Gz 23.3 795 BWR.JT w/LabGZ 23.3 770 Vendor A ++stage 23.0 770 Vendor B 22 stage 23.0 795 Vendor C H-S/JTX 20.6 730 RK.JTX Dsgn Gas 20.3 730 RK.JTX Lab Gas 23.0 795 Source MW dPSI PR.-w/LabGz 23.3 795 PR-LK.-w/LabGz 23.3 795 SRK.-w/LabGz 23.3 795 PR-LK./LGz-32F.o 23.3 712

d/ 1 sid F 00p

7.79 9.43 10.90 7.79 4.78 7.54 7.75 11.40

d/ 1 sid F 00p

9.53 9.30 9.50 8.85

Vendor A CFD Real Gas Model Results

Vendor A CFD Real Gas Model Results

70

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

71

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

72

Multi Stage Gas Valve Field Trial Part 4a Process Simulator Comparison A
Thermo=> PR-LK in T,F 95.0 P psia 990.0 H btu/# -35.20 S btu/#F -0.2714 Z 0.7672 Cp/Cv 1.67 Cp btu/#/F 0.701 mw 23.31 den 5.05 TS -150.63 V 27.15 P head V head
Frict. Head Total Head H(32F,1atm )

Sim Valve model out delta 21.1 -73.9 195.0 -795 -35.19 0.001 -0.1981 0.0733 0.9284 d(TS)=> 1.322 dPV=> 0.4855 dPfrict=> 23.31 Qc => 0.95 #/CF -95.306 BTU/# 147.55 fps 35.19 -2.25 2.68 35.62 -35.19 -2.25 2.12 -35.32 BTU/# BTU/# BTU/# BTU/# BTU/# BTU/# BTU/# BTU/#

u.jtx

F/100psi

9.30

55.32 1.78 59.99 -4.67

Thermo=> PRLK32F out im Valve model S in out delta T,F 95.0 32.0 -63 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)=> Cp/Cv 1.67 1.356 dPV=> Cp mass 0.701 0.5086 dPfrict=> mw 23.31 23.15 Qc => den 5.05 1.35 TS -150.63 -107.600 43.0266 V 27.15 105.84 fps P head V head
Frict. Head Total Head

u.jtx
F/100psi

8.85

43.03 1.92 47.02 -4.00

35.74 -0.12 0.00 35.62 -35.20 -0.12 0 -35.32

35.74 -0.12 0.00 35.62 -0.12 0 -35.32

36.18 -1.31 0.75 35.62 -36.12 -1.31 2.12 -35.32

BTU/# BTU/# BTU/# BTU/# BTU/# BTU/# BTU/# BTU/#

H(32F,1atm) -35.20

V head F.hd
Total Head

V head F.hd
Total Head

73

Multi Stage Gas Valve Field Trial Part 4b Process Simulator Comparisons BThermo=> PR Thermo=> SRK Sim Valve model u.jtx Sim Valve model u.jtx
T,F psia H btu/# S btu/#F Z Cp/Cv
Cp mass

mw den TS V P head V head

Frict. Head Total Head

in 95.0 990.0 -38.93 -0.2714 0.7208 1.79 0.6972 23.31 5.38 -150.63 27.15 33.58 -0.12 0.00 33.45 -0.12 0 -39.05

out 19.2 195.0 -36.81 -0.2023 0.9117 1.3623 0.4787 23.13 0.96 -96.942 146.96 34.68 -2.23 1.00 33.45 -36.81 -2.23 -0.02 -39.05

delta -75.8 -795 2.12 0.0691 d(TS)=> dPV=> dPfrict=> Qc => #/CF BTU/# fps BTU/# BTU/# BTU/# BTU/# BTU/# BTU/# BTU/# BTU/#

F/100psi

9.53

53.68 3.43 57.36 -3.67

T,F psia H btu/# S btu/#F Z Cp/Cv

Cp mass

mw den TS V P head V head

Frict. Head Total Head

in 95.0 990.0 -36.22 -0.2714 0.7547 1.656 0.6594 23.31 5.13 -150.63 27.15 35.16 -0.12 0.00 35.03 -0.12 0 -36.34

out 19.5 195.0 -36.21 -0.1996 0.9206 1.35 0.4775 23.31 0.96 -95.698 147.04 34.77 -2.23 2.49 35.03 -36.21 -2.23 2.10 -36.34

delta -75.55 -795 0.006 0.0718 d(TS)=> dPV=> dPfrict=> Qc => #/CF BTU/# fps BTU/# BTU/# BTU/# BTU/# BTU/# BTU/# BTU/# BTU/#

F/100psi

9.50

54.93 1.92 59.11 -4.18

H(32F,1atm) -38.93

H(32F,1atm) -36.22

V head F.hd
Total Head

V head F.hd
Total Head

74

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=-(H+ (V2/2Jg ) 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 MW 23.35 Z 0.795 Press 990.0 Temp. 95.00 Den 4.885 Flow 9.000 id sch 80 2.9 Velocity 28.6 Bertholet Z EOS item/ u inlet outlet Pc psia 664.4 664.4 Tc R 426.9 426.9 Pr 1.49 0.29 Tr 1.30 1.14 m scfd Z B'lot 0.795 0.934 m inch SG 0.805 0.805 ft/sec Cp mass 0.471 0.441 B'lot B'lot EOS Therm Energy Balance Z LM 0.86 in out units dP 795.00 psi P hd btu/# P LM 489.32 psi 157.92 99.74 Vhd 0.02 0.15 btu/# T LM 52.91 F Frict 0.00 58.05 btu/# den LM 2.41 #/cf Sum 58.05 btu/# 157.94 157.94 btu/# Frict Bert holetdT JTX, degree F -62.66 Outlet T: B'lot JTX 32.34 Friction =TdS = dH-vdP, use log mean density for v outlet 23.35 0.934 195.0 25.58 0.935 9.000 3.826 85.9 units #/mol v/v Psia F #/cf Friction by Clausius TdS 10.65 Cp 8.66 Cv 1.23 k -69.42 dT -77.03 dTjx 7.60 dTu 2.82 dU -69.42 dT -62.66 dT.jtx -6.77 dTh -3.09 dH -61.14 vdP 58.05 F=TdS P hd calc as:
(ZRT)ln(P/14.7)

inlet MW 23.35 Z 0.795 Press 990.0 Temp. 95.00 Den 4.885 Flow 9.000 id sch 80 3.826 Velocity 16.4

outlet 664.4 426.9 0.29 1.18 m scfd m 0.942 inch 0.805 ft/sec 0.441 B'lot B'lot EOS Therm Energy Balance in out units psi P hd btu/# psi 157.92 104.34 Vhd 0.01 0.16 btu/# F Frict 0.00 53.43 btu/# #/cf Sum btu/# 157.93 157.93 btu/# Bert holetdT JTX, degree F -62.66 Outlet T: B'lot JTX 32.34 Friction =-(dH+dVhd-TdS), &= KV 2/(J2g) => 53.43

outlet 23.35 0.942 195.0 43.61 0.894 9.000 3.826 89.9

units #/mol v/v Psia F #/cf

Bertholet EOS Z,dT.jtx Friction by

item/ u inlet Pc psia 664.4 Tc R 426.9 Pr 1.49 Tr 1.30 Z B'lot 0.795 SG 0.805 Cp mass 0.471 Z LM 0.87 dP 795.00 P LM 489.32 T LM 66.00 den LM 2.34 Frict.T 62.81

Clausius TdS 10.65 Cp 8.66 Cv 1.23 k -51.39 dT -77.03 dTjx 25.63 dTu 9.51 dU -51.39 dT -62.66 dT.jtx 11.26 dTh 5.14 dH -62.97 vdP 68.11 TdS P hd calc as:
(ZRT)ln(P/14.7)

75

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)/psi/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 MW 23.35 Z 0.767 Press 990.0 Temp. 95.00 Den 5.060 Flow 9.000 id sch 80 3.826 Velocity 15.9 in outlet 23.35 0.923 195.0 39.89 0.919 9.000 3.826 87.4 out units #/mol v/v Psia F #/cf
m scfd m

inch ft/sec

B'lot EOS Therm Energy Balance

units psi P hd psi 152.45 101.52 btu/# Vhd 0.01 0.15 btu/# F Frict 0.00 50.79 btu/# #/cf Sum btu/# 152.46 152.46 btu/# PR-LK dT JTX, degree F -74.00 Outlet T: PRLK JTX 21.00 Friction =-(dH+dVhd-TdS), &= KV2/(J2g) => 50.79

PR-LK Z EOS item/ u inlet Pc psia 664.4 Tc R 426.9 Pr 1.49 Tr 1.30 Z prlk 0.767 SG 0.805 Cp mass 0.436 Z LM 0.84 dP 795.00 P LM 489.32 T LM 63.51 den LM 2.41 Frict 60.83

outlet 664.4 426.9 0.29 1.17 0.923 0.805 0.436

BWR EOS Z,dT.jtx item/ u inlet outlet Pc psia 664.4 664.4 Tc R 426.9 426.9 Pr 1.49 0.29 Tr 1.30 1.15 m scfd Z BWR 0.795 0.929 m inch SG 0.805 0.805 ft/sec Cp mass 0.471 0.427 B'lot EOS Therm Energy Balance Z LM 0.84 in out units dP 795.00 psi P hd 149.93 100.00 btu/# P LM 489.32 psi Vhd 0.00 0.15 btu/# T LM 55.80 F Frict 0.00 49.78 btu/# den LM 2.46 #/cf Sum 149.93 149.93 btu/# Frict.t 59.65 btu/# BW dT JTX, degree F R -86.00 Outlet T: BWR.jtx 9.00 (ZRT)ln(P/14.7) Friction =-(dH+dVhd-TdS), &= KV 2/(J2g) => 49.78 Friction by Clausius TdS 10.18 Cp 8.19 Cv 1.24 k -55.11 dT -91.94 dTjx 36.82 dTu 12.92 dU -55.11 dT -74.00 dT.jtx 18.89 dTh 8.23 dH -60.98 vdP 69.22 TdS P hd calc as:

inlet MW 23.35 Z 0.754 Press 990.0 Temp. 95.00 Den 5.145 Flow 9.000 id sch 80 3.826 Velocity 15.6

outlet 23.35 0.929 195.0 29.23 0.933 9.000 3.826 86.1

units #/mol v/v Psia F #/cf

Friction by Clausius TdS 10.48 Cp 8.50 Cv 1.23 k -65.77 dT -106.1 dTjx 40.34 dTu 14.68 dU -65.77 dT -86.00 dT.jtx 20.23 dTh 9.08 dH -59.80 vdP 68.89 TdS P hd calc as:
(ZRT)ln(P/14.7)

76

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 MW 23.35 Z 0.768 Press 990.0 Temp. 95.00 Den 5.051 Flow 9.000 id sch 80 3.826 Velocity 15.9

RK EOS Z & T.jtx item/ u inlet outlet Pc psia 664.4 664.4 Tc R 426.9 426.9 Pr 1.49 0.29 Tr 1.30 1.16 m scfd Z RK 0.795 0.933 m inch SG 0.805 0.805 ft/sec Cp mass 0.471 0.427 RK EOS Therm Energy Balance Z LM 0.85 in out units dP 795.00 psi P hd 152.72 101.53 btu/# P LM 489.32 psi Vhd 0.01 0.15 btu/# T LM 59.89 F Frict 0.00 51.04 btu/# den LM 2.41 #/cf Sum 152.73 152.73 btu/# Frict.T 60.79 btu/# 4.1 RK dT JTX, degree F = -90.93 Outlet T: RK JTX > 2 Friction.T = -(dH+dVhd-TdS), &= KV /(J2g)=> 51.04

outlet 23.35 0.933 195.0 34.72 0.919 9.000 3.826 87.4

units #/mol v/v Psia F #/cf

Friction by Clausius TdS 10.48 Cp 8.50 Cv 1.23 k -60.28 dT -112.2 dTjx 51.9 dTu 18.89 dU -60.28 dT -90.93 dT.jtx 30.6 dTh 13.76 dH -60.94 vdP 74.70 TdS P hd calc as:
(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

77

SUMMARY
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 78 is likely the result of frictional heating, as detailed in the article so titled.