Fluid Phase Equilibria 241 (2006) 41–50

Thermodynamic methods for pressure relief system design parameters

Kwang W. Won ∗ , Arnie R. Smith, Gerald A. Zeininger
Fluor Enterprises Inc., 3 Polaris Way, Aliso Viejo, CA 92698, USA
Received 9 November 2005; received in revised form 30 December 2005; accepted 31 December 2005

Abstract
The design of fire relief systems for petroleum refineries, petrochemical, chemical and natural gas plants requires two accurate system design
parameters: the latent heat of vaporization and sonic velocity. These design parameters further require accurate thermodynamic properties. At
present, various approximate methods and thermodynamic models are utilized to estimate the latent heat of vaporization of fluid mixtures with
varying degrees of success. Similarly, approximate methods have been used in industry to estimate the sonic velocity at which compressible fluid
mixtures can flow through relief valve orifices and discharge piping.
This paper presents the following:

1. Thermodynamically rigorous methods for the calculation of the latent heat of vaporization and the sonic velocity. These methods are applied
to typical fluid mixtures using industry-standard property models and compare the calculated results with data published in scientific literature.
2. The American Petroleum Institute (API) recommendation of the minimum value of latent heat of vaporization of hydrocarbon mixtures is too
large to accept for safe fire relief system design when no accurate latent-heat value is available near the critical point. Note: recommendation
by API for minimum approximate heat of vaporization of multicomponent hydrocarbon mixtures in the absence of latent-heat data at the critical
point is 50 Btu/lb (116 kJ/kg) – see Section 3.15.3.1 of API Recommended Practice 521: “Guide for Pressure-Relieving and Depressuring
Systems, 1997”).
3. The need of accurate thermodynamic property data of fluid mixtures necessary to validate the thermodynamic model at relief system operating
conditions. Currently, these types of data are scarce in the open literature because data measurements have been difficult at the temperatures
and pressure of interest.

© 2006 Elsevier B.V. All rights reserved.

Keywords: Fire relief system; Latent heats of vaporization; Thermodynamic method; Petroleum refinery; Natural gas processing; Sonic velocity

1. Introduction • by the inadvertent opening of any valve from a source of

higher pressure
In natural gas processing, petroleum refineries, petrochem- • by the failure of a check valve to close resulting in a reversal
ical and chemical plants, pressure vessels, heat exchangers, of the fluid flow
pumps, compressors and piping systems are designed to operate • by heat-exchanger tube failure
within the normal operating conditions between the minimum • by reflux failure
and maximum temperatures and pressures. However, overpres- • by the utility failures including electric, cooling water and
sures exceeding the maximum pressure limit can develop in the instrument air
following events: • by plant fires

• by inadvertent closure of a block valve on the outlet of pres-
sure vessel while the plant is on stream
∗ Corresponding author. Tel.: +1 949 349 5312; fax: +1 949 349 2914.
E-mail address: ray.won@fluor.com (K.W. Won).
Fires external to pressure vessels increase the temperature
of fluid content due to the abnormal heat input. The increase
of temperature results in the operating pressure exceeding the
design pressure intended for the fire relief valve. When the fluid
inside the vessel contains both liquid and gas, the rate of gas flow
through the relief valve is approximately equal to the rate of heat

0378-3812/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2005.12.045
42 K.W. Won et al. / Fluid Phase Equilibria 241 (2006) 41–50

absorption divided by the latent heat of vaporization of the fluid

mixture. The maximum velocity of the gas discharge will be the
sonic velocity, which is dependent on the temperature, pressure
and properties of the fluid. Therefore, the accurate design of
the pressure relief system capacity requires accurate estimation
of the latent heat of vaporization and sonic velocity of fluid
mixtures, which requires thermodynamic property data at high
temperatures.
In the past several decades, latent heats of vaporization have
been extensively measured and published for pure fluids and
simple fluid mixtures. At the same time, several thermodynamic
models have been applied successfully to the phase equilibrium
and enthalpy calculations for mixtures consisting of hydrocar-
bons and slightly polar components of relatively small molecular
sizes at low to moderate temperature ranges. However, much less
attention has been paid to the properties of fluid mixtures consist-
ing of molecules with much different molecular sizes including
petroleum fractions. As a consequence, accurate latent heats Fig. 1. Rigorous thermodynamic calculation method of latent heat of vaporiza-
tion of fluid mixtures.
of vaporization and property data needed for the calculation of
sonic velocity for such fluid mixtures are scarce.
Even when the total enthalpy data have been published for
such fluid mixtures, the vapor–liquid equilibrium data of the Method 2 uses a non-rigorous estimate of the latent heat of vapor-
system have not been published at the similar conditions. As a ization as follows:
result, when the total enthalpies calculated by thermodynamic λv = Hv − HL (2)
models do not agree with data within the accuracy acceptable for
engineering design purposes, it is difficult to determine which where Hv and HL are the specific enthalpy of the vapor and liquid
source is the cause of the disagreement. This paper points out at equilibrium. The above two equations are valid only for pure
some important areas where new thermodynamic data are nec- fluid. If these equations were used for mixtures, substantial error
essary. would result because the concentrations of vapor and liquid at
equilibrium could be very different.
This paper proposes a new thermodynamically rigorous
2. Methods of latent heat of vaporization
method 3, based on a thermodynamic cycle depicted in Fig. 1.
Step A is the isothermal compression of the liquid mixture above
The latent heat of vaporization required for the fire relief load
the pressure set by the fire relief valve by a small P, say 7 kPa
calculation is commonly calculated by an energy balance [27]
(1 psia). Step B is an isobaric heating of the compressed fluid to
simulating a fire relief scenario (method 1), where the liquid at its
a higher temperature, or its boiling-point temperature. Step C is
boiling point temperature in a vessel is heated and is vaporized.
an isothermal vaporization step where the compressed fluid is
As the temperature continues to increase, the equilibrium pres-
expanded to the original set pressure. The latent heat of vapor-
sure of the fluid mixture increases until it reaches and exceeds
ization is the net heat effect of path a–b and path c–d divided by
the set pressure of the fire relief valve, resulting in the venting
the amount of vapor generated in path c–d. The heat required
or relief of the vapor. The latent heat of vaporization, λ, can be
for path b-c is the sensible heat, which is not a part of the latent
estimated by an incremental flash from T to T + T, where P is
heat of vaporization. This can be summarized by the following
constant at relief conditions:
formula:


1 Cp,F + Cp,L Cp,F + Cp,v Qa + Qc
λv = Q − WL T − Wv T λv = (3)
Wv 2 2 Wv
(1)
For a pure fluid, Eq. (3) reduces to Eq. (1a) if we set both P
where T is equal to the bubble point temperature, Q the heat and Qa equal to zero. Qc /Wv is a constant equal to the latent heat
input, WL and Wv are the weights of liquid and vapor, Cp the of vaporization.
isobaric heat capacity and T is the temperature difference. Eqs. (1) and (2) and the thermodynamically rigorous method,
For a pure fluid, there is no temperature change during the Eq. (3), are used to calculate the latent heat of vaporization of
flash vaporization and the latent heat equation reduces to a sim- fluid mixtures. In order to investigate the differences of the
ple equation, which is the flash duty divided by the generated three methods, each has been applied to five sets of typical
vapor mass as follows: mixtures and the results are presented in Tables 1 and 2. In
these calculations, the initial 5% by weight of the low boiling,
Q light components were vaporized and removed from the system
λv = (1a)
Wv because the light ends, including air, would misrepresent the
 K.W. Won et al. / Fluid Phase Equilibria 241 (2006) 41–50 43

Table 1
Latent heat of vaporization of C3 and nC4 binary mixtures (kJ/kg)
Thermodynamic methods Model 791a 2170a 3549a

5%b 10%b 50%b 90%b 5%b 10%b 50%b 90%b 5%b 10%b 50%b 90%b

Method 1 HYSYS, PR 314 316 335 347 216 216 235 251 84 88 116 137
PRO/II, PR 316 319 335 349 216 219 237 251 86 91 119 137
Method 2 HYSYS, PR 307 300 288 333 214 212 212 242 88 93 119 137
PRO/II, PR 316 319 335 347 219 226 244 254 91 100 137 144
Method 3 PRO/II, PR 314 316 333 347 215 217 232 249 84 87 114 135
a System pressure (kPa).
b mol% C3 in the binary liquid mixture.

latent heat of the fluid mixture. The remaining portion is at its
boiling point temperature at this pressure.
Table 1 presents the latent heats of vaporization of five
propane-n butane binary mixtures calculated by the three meth-
ods at three pressure levels by Peng-Robinson [25] equation of
state (PR) in HYSYS (version 3.2, Hyprotech Inc.) and PRO/II
(version 7.0, Simulation Science Inc.). For method 3, the latent
heats of vaporization and the boiling point temperatures calcu-
lated only by PR model in PRO/II are presented. The results in
Table 1 indicate that the latent heats of vaporization calculated
by the energy balance agree with the values of method 3 within
about 2% or 3.5 kJ/kg. On the other hand, the difference between
methods 2 and 3 is appreciably larger with about 7% or 13. kJ/kg
of root mean squared deviations.
Table 2 presents the latent heats of vaporization of four
multi-component systems including a petroleum fraction and
a binary mixture consisting of methane-normal C10 , which rep-
resents a mixture in which the constituent’s molecular sizes are
very much different. The concentrations of multi-component
C3 –C12 mixture, light hydrocarbons and petroleum fractions,
and methane-normal C10 binary mixture are provided in sep-
arate tables. It is noteworthy that the differences between the
results of method 1 and 2 are substantial for mixtures consisting
of small and large molecules at high pressures including low
sulfur diesel and light hydrocarbon mixtures at 2171 kPa and
methane-normal C10 mixtures at 1136 kPa.
In general, the results of method 1 and 3 are in agreement.
The latent heat of vaporization of the mixture consisting of light
hydrocarbons and Low Sulfur Diesel (LSR) calculated by meth-
ods 1 and 3 at 2171 kPa ranges from 35 to 37 kJ/kg. These values
are substantially smaller than 116.3 kJ/kg, the minimum value
recommended by API (American Petroleum Institute).

Table 2
Latent heat of vaporization of multi-component system (kJ/kg)
Thermodynamic methods Model C3–C12a LSR diesela Diesel + light HCa C1–C10a

791b 2170b 791b 791b 2170b 1136b

Method 1 HYSYS, PR 244 119 163 174 34 149

PRO/II, PR 256 116 165 179 37 158
Method 2 HYSYS, PR 156 105 170 177 67 −251
PRO/II, PR 261 142 177 219 74 188
Method 3 PRO/II, PR 242 123 165 172 34 163
Temperature (K) PRO/II, PR 450 529 641 610 710 525

Mixture C3–C12

Comp C3 nC12 nC5 nC6 nC7 nC8 nC9 nC10 nC11 nC12
mol% 2 3 8 15 22 22 15 8 3 2

LSR diesel

Volume distilled (%) 0 5 10 30 51 70 90 95 100

TBP (F) 242 391 423 483 519 552 595 617 645

Light HC C1–C10 Diesel + light HC

Comp nC5 nC6 nC7 nC8 CH4 nC10 LSR diesel Light HC
mol% 10 20 30 40 10 90 95 5
a Multi-component system
b System pressure (kPa).
44 K.W. Won et al. / Fluid Phase Equilibria 241 (2006) 41–50

It is important to note that the overestimated latent heat of

vaporization leads to under design of the pressure relief system,
which is not safe. Also, the heat of vaporization for methane and
normal C10 , which was calculated by method 2 at 1136 kPa, is
negative, which is meaningless.
The PR model in Aspen Plus (version 12.1, Aspen Technol-
ogy Inc.) provides essentially the same results for method 3 as
the PR model in PRO/II. The results of Aspen Plus were not
shown in Tables 1 and 2.

3. Experimental enthalpy data

Experimental latent heats of vaporization data pertinent to

fire relief design are unavailable to the best knowledge of the
authors. However, most of the experimental enthalpy data of
partially vaporized mixtures have been measured without chem-
ical analysis of the vapor and liquid at equilibrium. Therefore,
the exact calculation of the latent heat of vaporization from the
published total enthalpy data with an isobaric calorimeter is not
possible.
Extensive enthalpy data of pure components and fluid mix-
tures have been compiled and published by Daubert [1–4] in the
Research Reports (RR) of Gas Processors Association (GPA).
In the GPA RR-81, Daubert [5] presents the evaluation of
Peng-Robinson Computer Program with the GPA Data Bank
of Selected Enthalpy Values.
The RR-81 shows appreciable arithmetic average (AA) and
root-mean-squared (rms) deviations between the enthalpy data
and those calculated by the PR equation of state. Additional Fig. 2. (a) Isobaric enthalpy at 1379 kPa of a binary mixture: 21.8 mol% nC5
enthalpy data have been published for single fluid by Eubank et and 78.2 mol% nC8. (b) Isobaric enthalpy at 2759 kPa of a binary mixture:
al. [6] and for methane binary mixtures by Wilson [7]. 21.8 mol% nC5 and 78.2 mol% nC8.

4. Comparison of enthalpy calculation results with data
This work uses the Peng-Robinson equation of state for ther-
modynamic property calculations, because the PR model has
been widely accepted in industry and extensively used by prac-
ticing process design engineers. In order to verify the accuracy
of the PR model, this work uses the PR model available in Aspen
Plus to calculate the enthalpies of fluid mixtures at the condi-
tions of experimental measurements. Aspen Plus was selected
for this study because it offers an expedient table generation
capability of isobaric enthalpy versus temperature. At each iso-
bar, the enthalpy data of the mixtures were calculated relative to
that at 297.04 K. It is necessary to use one standard state tem-
perature for the comparison purpose, even if it is different from
that of the published experimental data.
Fig. 2(a) presents the enthalpy data of a binary mixture
consisting of 21.8 mol% n-pentane and 78.2 mol% n-octane at
1379 kPa as a function of temperature between 297 and 588.7 K
[8]. Origin of the figure shows that the relative enthalpy of the liq-
uid mixture is zero at 297 K. The bold line is the result calculated
by the Peng-Robinson equation of state in Aspen Plus. The reg-
ular line is the result of PR-LK, in which the phase equilibrium
was calculated by the PR model, but the volumetric properties
and enthalpies were calculated by the Lee-Kesler model [9].
Vaporization is responsible for the sharp increase of the slope of
the curve representing the isobaric enthalpy as a function of tem-
perature. The temperature at which the slope starts to increase, at
approximately 494 K, is the bubble point temperature. The tem-
perature at which the slope returns to linearity, at about 512 K,
is the dew point temperature. The similar result of the same
mixture at 2758 kPa is shown in Fig. 2(b).
Both Fig. 2(a) and (b) for the n-pentane and n-octane sys-
tem indicate that both the PR and PR-LK models seem to agree
with each other and predicts the isobaric total enthalpy of the
mixture within approximately 12. kJ/kg. However, one enthalpy
data point of a partially vaporized mixture at 1379 kPa and
499.8 K was appreciably underestimated by both models. Table 3
presents the average bias and root mean squared deviations in
kJ/kg for liquid, gas and two-phase regions.
Fig. 3(a) presents the enthalpy data of a binary sys-
tem consisting of 32.2 mol% n-pentane and 67.8 mol% trans-
Decahydronaphthalene (t-Decalin) at 138 kPa between 297 and
522 K published by Lenoir et al. [10] and Fig. 3(b) presents the
similar result at 690 kPa between 297 and 588.7 K. Fig. 3(a) and
(b) indicate that enthalpies of both liquid and gas phases were
better predicted by the PR-LK model, but the enthalpy of the
partially vaporized mixture at 138 kPa and 455.4 K was substan-
tially overestimated by both models. The prediction error will
result in the overestimation of the latent heat of vaporization of
this type of mixture, which would lead to the underestimated
 K.W. Won et al. / Fluid Phase Equilibria 241 (2006) 41–50 45

Table 3 Table 3a
Arithmetic and RMSD (kJ/kg) of ASPEN Plus PR and PR-LK models from Arithmetic and RMSD (kJ/kg) of ASPEN Plus PR and PR-LK models from
Isobaric Enthalpy Data of 21.8 mol% nC5 in nC8 [8] Isobaric Enthalpy Data of 32.2 mol% nC5 in t-Decalin [10]
P = 1379 kPaa P = 2759 kPaa P = 138 kPaa P = 689 kPaa

PRb PR-LKb PRb PR-LKb PRb PR-LKb PRb PR-LKb

arithc RMSDc arithc RMSDc arithc RMSDc arithc RMSDc arithc RMSDc arith RMSDc arithc RMSDc arithc RMSDc

Liquid 7.3 7.6 0.0 2.6 2.6 6.7 0.7 3.0 L 5.2 5.9 0.3 0.7 12 14 −0.4 0.8
Gas −4.6 4.8 −11 10 −8.8 8.8 −14 14 G 21 21 −5.0 5.2 20 21 −5.2 7.1
2 phase 48 46 −10 10 −12 12 2 phase −5.5 21 −20 33 17 17 −2.6 2.8
Total 5.0 14.7 −1.6 14.6 −1.1 8.0 −3.4 7.5 Total 10 18 −7.3 17 17 18 −3.1 4.6
a System a System
b Model b Model
c Dev (kJ/kg) c Dev (kJ/kg)

fire relief system design. Figs. 2(b) and 3(b) show that at higher
pressures, the enthalpies of both mixtures were better predicted
by the PR-LK model than the PR model alone. Table 3a presents
the average bias and root mean squared deviations of Aspen PR
and PR-LK models from the data.
Fig. 4(a) and (b) compare the calculated enthalpies with
data for the binary mixture containing 16.7 mol% n-pentane and
83.3 mol% n-Hexadecane at 172 and 276 kPa bar between 297
and 599.8 K. This mixture consists of molecules with very dif-
ferent sizes and, therefore, all the models including Aspen PR,
PR-LK, Simulation Sciences Inc. PR and modified PR (PRM),
SRK [26] and modified SRK (SRKM) appreciably overestimate
the enthalpies of partially vaporized mixtures. It is important to
note that the overestimated isobaric total enthalpies of the par-
tially vaporized mixtures will lead to under designed fire relief
systems. However, it is not possible to calculate the latent heats
of vaporization from the total isobaric enthalpy data or to dif-
ferentiate the cause of disagreement between the data and the
models.

Fig. 3. (a) Isobaric enthalpy at 138 kPa of a binary mixture: 32.2 mol% nC5 and Fig. 4. (a) Isobaric enthalpy at 172 kPa of a binary mixture: 16.7 mol% nC5
67.8 mol% trans-Decalin. (b) Isobaric enthalpy at 690 kPa of a binary mixture: and 83.3 mol% nC16. (b) Isobaric enthalpy at 276 kPa of a binary mixture:
32.2 mol% nC5 and 67.8 mol% trans-Decalin. 16.7 mol% nC5 and 83.3 mol% nC16.
46 K.W. Won et al. / Fluid Phase Equilibria 241 (2006) 41–50

Table 3b Table 4
Arithmetic and RMSD (kJ/kg) of SSI PR and PRM models from Isobaric Infinite dilution activity coefficient data and sources
Enthalpy Data of 16.7 mol% nC5 in nC16 [20]
Temp (K) Solute Solvent Act coeff Data source
P = 172 kPaa P = 276 kPaa
293.2 nC5 nC8 0.97 Thomas et al. [21]
PRb PRMb PRb PRMb 328.2 nC5 nC8 1.07 Arnold et al. [22]
348.2 nC5 nC8 1.06 Arnold et al. [22]
arithc RMSDc arithc RMSDc arithc RMSDc arithc RMSDc
388.2 nC5 nC8 1.04 Arnold et al. [22]
L 5.8 6.7 −27 30 9.0 11 −33 35 298.2 nC5 nC16 0.926 Kikic and Renon [12]
298.2 nC5 nC16 0.825 Richon et al. [13]
G 8.1 8.1 −50 50 313.2 nC5 nC16 0.87 Snyder and Thomas [11]
2 phase −1.6 29 −59 66 9.0 26 −53 57 343.2 nC5 nC16 0.859 Snyder and Thomas [11]
363.2 nC5 nC16 0.852 Snyder and Thomas [11]
Total 0.6 25 −52 60 9.0 21 −45 50 298.2 nC6 nC16 0.892 Lenoir [14]
a System 273.2 nC6 nC16 0.904 Letcher and Netherton [15]
b Model 298.2 nC6 nC16 0.892 Lenoir [14]
c Dev (kJ/kg) 313.2 nC6 nC16 0.892 Snyder and Thomas [11]
343.2 nC6 nC16 0.882 Snyder and Thomas [11]
363.2 nC6 nC16 0.876 Snyder and Thomas [11]
298.2 nC6 Decalin 1.26 Monfort et al. [23]
Table 3b presents average bias and root mean squared devia- 298.2 nC6 Decalin 1.264 Lerol et al. [24]
300 nC4 nC16 1.107 Chappelow and Prausnitz [28]
tions of the isobaric enthalpies, which were calculated by SSI PR
325 nC4 nC16 0.919 Chappelow and Prausnitz [28]
and PRM models from the data. The SSI PR model predicts the 350 nC4 nC16 0.905 Chappelow and Prausnitz [28]
isobaric enthalpies of the gas and liquid mixtures within about 375 nC4 nC16 0.881 Chappelow and Prausnitz [28]
9.3 kJ/kg at 172 and 276 kPa. However, the enthalpies of the 400 nC4 nC16 0.86 Chappelow and Prausnitz [28]
two-phase region are overestimated by more than 23 kJ/kg. At 425 nC4 nC16 0.844 Chappelow and Prausnitz [28]
450 nC4 nC16 0.823 Chappelow and Prausnitz [28]
276 kPa, the experimental data shows that the mixture has two
475 nC4 nC16 0.793 Chappelow and Prausnitz [28]
phases at the maximum experimental temperature. Therefore,
all the data above the bubble point temperature were assumed to
be partially vaporized. The PRM model overestimates the liquid
heat capacity and the vapor fraction in the partially vaporized 5. Vapor–liquid equilibrium data of mixtures consisting
region, relative to the PR model. As a result of the overestima- of large and small molecules
tions, the isobaric enthalpies of liquids, gases, and the two-phase
region are overestimated by more than 23, 46 and more than The appreciable differences of the experimental and calcu-
58 kJ/kg, respectively. Table 3c presents the similar results cal- lated enthalpies of the partially vaporized mixtures necessitate
culated by SSI SRK and modified SRK (SRKM) models. the examination of the vapor–liquid equilibrium data of the
Either the overestimated vapor–liquid equilibrium K values mixtures around the experimental condition. The vapor liquid
or the overestimated latent heats of vaporization can lead to the equilibrium data of the n-pentane and n-hexadecane binary sys-
overestimated isobaric total enthalpies of the partially vaporized tem were published only for an infinitely dilute system with
mixtures. Therefore, the accuracy of the PR model was investi- respect to n-pentane as an infinite dilution activity coefficient
gated by comparing the calculated vapor–liquid equilibrium K (γ ∞ ) between 313.2 and 363.2 K by Snyder and Thomas [11],
value of smaller molecules in normal hexadecane at the temper- at 298.2 K by Kikic and Renon [12] and by Richon et al. [13].
ature range of interest. Similar data for the related systems were published by Chap-
pelow and Prausnitz [28] as the Henry’s coefficient (Hc ) for
n-butane in n-hexadecane system between 300 and 475 K. The
Table 3c γ ∞ data of n-hexane in n-hexadecane have been published by
Arithmetic and RMSD (kJ/kg) of SSI SRK and SRKM models from Isobaric Snyder and Thomas between 313.2 and 363.2 K, by Lenoir [14]
Enthalpy Data of 16.7 mol% nC5 in nC16 [20] at 298.2 K and by Letcher and Netherton [15] at 273.2 K.
P = 172 kPaa P = 276 kPaa Chappelow and Prausnitz reported Henry’s coefficient data of
n-butane in n-hexadecane, while all the others reported only infi-
SRKb SRKMb SRKb SRKMb
nite dilution activity coefficients. In order to make a consistent
arithc RMSDc arithc RMSDc arithc RMSDc arithc RMSDc comparison, infinite dilution activity coefficients of n-butane in
L 2.3 2.8 −30 33 3.6 5.6 −37 39 n-hexadecane were calculated from the Henry’s coefficient data
G −3.5 3.5 −56 56
by dividing them by the product of the saturated fugacity of
n-butane and Poynting correction. At the temperatures above
2 phase −12 32 −64 71 −5.2 25 −58 62
the critical temperature of n-butane, 408.2 K, the product of
Total −8.3 28 −57 64 −1.8 20 −50 54 the saturated fugacity and Poynting correction of n-butane were
a System extrapolated. This extrapolation of the fugacity of hypotheti-
b Model cal liquid above its critical temperature is similar to the work of
c Dev (kJ/kg) Prausnitz and Shair [16]. Table 4 presents the data sources of the
 K.W. Won et al. / Fluid Phase Equilibria 241 (2006) 41–50 47

Fig. 6. Effect of nC5 concentration on the bubble and dew point temperatures
Fig. 5. Activity coefficients of normal nC4, nC5 and nC6 in nC16 at infinite of nC5 and nC16 binary mixture.
dilution.

infinite dilution activity coefficients and Henry’s coefficients in
n-hexadecane.
Fig. 5 shows that the infinite dilution activity coefficient (␥∞ )
of all three light hydrocarbons in n-hexadecane are less than
unity. One data point at the lowest temperature of the measure-
ment is larger than one. This is not surprising, because the first
data point at the lowest (or highest) temperature is sometimes
subject to substantial uncertainty. For this type of mixtures, a
thermal solution model [17] is applicable, which predicts that
the activity coefficients of smaller molecules in larger molecules
of the similar type will be less than unity. Fig. 5 also shows the
infinite dilution activity coefficients of n-butane in n-hexadecane
calculated by the PR model using the temperature-dependent
binary coefficient (kij ) between n-butane and n-hexadecane.
Although the Henry’s coefficient data were used to derive a lin-
early temperature-dependent binary interaction parameter (kij )
for the PR model, the agreement between the values calculated
by the PR model and the values derived data is excellent. For
comparison purposes, the infinite dilute activity coefficient cal-
culated by the PR model without the binary parameter (or with
the binary parameter set to zero) is also shown in Fig. 5 as a
broken line.
Experimental bubble and dew point temperatures for
the binary mixture consisting of 16.7 mol% n-pentane and
83.3 mol% n-hexadecane at 172 kPa are 407.9 and 588.4 K,
respectively. The bubble and dew point calculated by the SSI PR
model with the binary coefficients are 409.8 and 575.4 K, while
the PR model without the binary coefficient predicts 419.3 and
575.4 K. The binary coefficient clearly improved the accuracy of
bubble point temperature within 1.9 K from about 11.4 K devia-
tions, but the dew point temperature calculation was essentially
not affected by the binary coefficient. Fig. 6 shows the experi-

Table 5
Sonic velocity of C3 and nC4 binary gas mixtures (m/s)
System pressure (kPa)

791 2170 3549

5%a 10%a 50%a 90%a 5%a 10%a 50%a 90%a 5%a 10%a 50%a 90%a

Temperature (K) 338.2 334.4 310.4 294.3 388.0 384.0 358.7 338.4 418.0 415.0 388.2 365.0
mol% C3 in the vapor at equilibrium 11.9 22.6 74.4 96.5 8.35 16.4 65.8 94.8 6.1 12.1 58.2 92.9
Sonicvelocity(m/s)
Real gas 198 201 214 217 165 168 185 190 132 144 151 159
Ideal gas 232 235 246 249 247 249 258 264 255 256 265 273
a mol% C3 in liquid

Table 5a
Sonic velocity of multi-component gas mixtures (m/s)
Multi-component system

C3–C12 LSR diesel Diesel + light HC C1–C10

System pressure (kPa) 791 2170 791 791 2170 1136

Temperature (K) 453 528 626 594 703 500
Sonic velocity (m/s)
Real gas 182 133 144 160 94 258
Ideal gas 214 217 180 191 185 273
48 K.W. Won et al. / Fluid Phase Equilibria 241 (2006) 41–50

mental bubble and dew points for the mixture at 172 kPa, which
3550.0

1.83
4600.0
154

147
165
80

were reported by Lenoir and Hipkin. It is interesting to note that

the dew point temperature of the binary mixture is higher than
that of pure n-hexadecane at the same pressure. The maximum
1.54

dew point temperature is unlikely for the mixture at this rela-

4400.0
3520.0

132
150
86
136

tively low pressure, where the retrograde phase change is not

expected. It is likely that the fluid mixture inside the calorimeter
was not at equilibrium during the partial vaporization step. Fig. 4
1.37
4200.0

shows that the binary coefficient does not improve the isobaric
130
139
95
3480.0

enthalpy calculation of the partially vaporized mixture, and its

139

effect on the enthalpy is not appreciable at all temperatures.

1.36
4000.0

139
141
102

6. Sonic velocity
3450.0

141

In the design of fire safety system, one of the important design

1.37

parameters is the minimum required effective valve discharge

3800.0

148
148
108

area. The valve discharge area is determined such that the flow
of gases or vapors must not exceed the sonic velocity of the
3100.0

161

fluid mixture. The sonic velocity (Vs ) is related to the reversible

1.42
3400.0

pressure fluctuation upon density change at constant entropy,

165
163
116

which is a function of the thermodynamic properties of the fluid

mixture.
2760.0

 
177

1.51

∂P
2600.0

Vs 2 =
193
189
128

(4)
∂ρ s
where ρ is equal to the molecular weight divided by the molar
2410.0

1.57

volume, V. Utilizing the classical thermodynamic relationships

2000.0
190

210
206
134

including Maxwell’s, the sonic velocity is related to the PVT

and thermal properties of fluids as in Eq. (4a).
  
Cp ∂P
1.62
1400.0
1720.0

Vs 2 = −V 2 (4a)
225
222
139
212

Cv ∂V T
Noting that Cp is simply (∂H/∂T)P, the ratio of Cp to Cv can be
1.65

calculated as a function of PVT relationship as in Eq. (4b).

1000.0

234
231
142
1030.0

231

Cp Cp
Effect of pressure on the sonic velocity of C3 and nC4 binary gas mixtures, m/s

=   (4b)
Cp Cp +T (∂V/∂T )2p
1.66

(∂V/∂P)T
600.0

241
240
145
340.0

The thermal expansion coefficient (∂V/∂T)P /V and the isother-

248

mal compressibility, −(∂V/∂P)T /V necessary for Eqs. (4a) and

1.68

(4b) were calculated by the numerical differentiation of the

300.0

246
247
147

molar volume of the compressed gas with respect to tempera-

100.0

ture and pressure. Table 5 presents the sonic velocities of the C3

254

and nC4 binary gas mixtures in equilibrium at three pressures.

1.69
C3 in the binary mixture: 12.1 mol% at 415 K

100.0

250
251
148

It is interesting to note that the sonic velocities of real gases are

always smaller than those of ideal gases at the same concentra-
10.0

tion and temperature and that the sonic velocities of real gases
256

1.69
10.0

decrease as the pressure increases, while those of ideal gases

252
253
149

increase as the pressure increases. The sonic velocities, which

were calculated by the numerical differentiation, agree well with
Pure iso butane at 420 K

Ratio of sonic velocity

System pressure (kPa)

System pressure (kPa)

those of Aspen plus. Therefore, the sonic velocities presented in

Data (NBS, 1982)
Aspen PR
Crosby [19]

Data/Crosby
Sonic velocity (m/s)

Sonic velocity (m/s)

Tables 5, 5a, and 5b are those of Aspen plus. Table 5b presents the
sonic velocities of a binary gas mixture consisting of 12.1 mol%
Real gas

C3 in nC4 as a function of pressure.

Table 5b

Fig. 7 shows the sonic velocity of the 12.1 mol% C3 in nC4

vapor, which is in equilibrium with a binary liquid mixture
 K.W. Won et al. / Fluid Phase Equilibria 241 (2006) 41–50
Fig. 7. Effect of pressure on the velocity of sound.
containing 10 mol% C3 and 90 mol% nC4 at 3449 kPa. For com-
parison, Fig. 7 also presents the sonic velocity of pure iso-butane
(iC4) at 420 K as a function of pressure and the values published
in NBS Technical Note 1051 entitled “Thermo-physical Prop-
erties of iso-butane from 114 to 700 K at Pressures to 70 MPa”
[18].
The results in Fig. 7 indicate that the sonic velocity calculated
by PR model at 420 K is accurate up to about 4000 kPa bar, but
the PR model overestimates the sonic velocity above this pres-
sure. The minimum sonic velocity occurs near the critical state of
the fluid, where the isothermal compressibility increases sharply
and goes through a maximum. As a result, the sonic velocity goes
through the minimum. The overestimated sonic velocity by PR
model may lead to under design of the orifice opening of the
pressure relief system. In industry, empirical design methods
are commonly practiced based on ASME Section 8, UG125-
137 or API recommended Practice 520, “Sizing, Selection, and
Installation of Pressure-Relieving Devices in Refineries”, part
1-Sizing and Selection.
Fig. 7 presents the maximum iC4 gas velocity through the
orifice of the pressure relief valve, which was calculated by the
formula of Crosby Pressure Relief Valve Engineering Handbook
[19]. It is important to note that the maximum design gas velocity
is substantially smaller than the sonic velocity of the bulk fluid.
The ratio of the design gas velocity to the sonic velocity at the
same temperature increases with pressure from about 65% at
about 2000 kPa to about 73% at about 4000 kPa for pure iC4.
This ratio represents the coefficient of discharge, which has been
established for a specific type of orifice by actual test with steam
and some standard type of gases.
7. Conclusion
This paper recommends thermodynamically rigorous meth-
ods for the calculations of the latent heats of vaporization and
sonic velocities of fluid mixtures.
The approximate energy balance method appears adequate
for the majority of cases investigated in this paper, but this
method needs additional property data for sensible heat effect.
The additional heat capacity data are seldom available at high
49
pressures for fluid mixtures. Further, the third term of the right-
hand side of Eq. (1) is not meaningful. Therefore, there appears
no advantage of using the approximate energy balance method.
The paper does not recommend the simple difference-in-
enthalpy method, because this method leads to appreciable error
for the systems consisting of large and small molecules.
Current Peng-Robinson equation of state appears to overes-
timate the enthalpies of partially vaporized mixtures consisting
of small and large molecules. This would lead to under designed
pressure relief system. This paper stresses the need of accurate
latent heats of vaporization data at fire relief conditions to val-
idate the accuracy of Peng-Robinson equation of state or other
thermodynamic models.
Thermodynamically rigorous method of sonic velocity cal-
culation requires more fundamental thermodynamic data than
current empirical methods, but the use of computer calculations
and the availability of reliable thermodynamic models allow
the thermodynamic method practical for complex mixtures at
high pressures. Even though the accuracy of the thermodynamic
model for the calculation of sonic velocity appears adequate in
most cases investigated in this paper, the property calculations
of PR model are subject to appreciable error at high temper-
atures and high pressures approaching the critical state of the
fluid mixtures.
List of symbols
Cp isobaric heat capacity (kJ/kg/K)
Cv isochoric heat capacity (kJ/kg/K)
H enthalpy (kJ/kg)
Hc (i, j) Henry’s coefficient of component i in solvent j (kPa/mol
fraction)
P absolute pressure (kPa)
Q heat (kJ)
T absolute temperature (K)
V molar volume, m3 (kg-mol)
Vs sonic velocity (m/s)
W weight (kg)
Greek symbols
γ∞ infinite dilution activity coefficient
λv latent heat of vaporization (kJ/kg)
Subscript
p isobaric condition
s isentropic condition
T isothermal condition
v isochoric condition
Acknowledgements
The authors are grateful to the management of Fluor Enter-
prises Inc. for permission to present this paper and to our
colleagues, especially Garry Jacobs, Paul Mathias and Jack
Reisdorf for helpful criticisms and discussions, An Mai for the
pertinent data and Zachary Working for editorial assistance.
50 K.W. Won et al. / Fluid Phase Equilibria 241 (2006) 41–50
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