Measurement Techniques, Vol. 53, No.

6, 2010

EQUATION FOR COMPRESSIBILITY FACTOR

AND DENSITY OF SATURATED n-ALKANES
(C1–C10) VAPOR, PARAHYDROGEN, AND
WATER AT THE BOILING LINE

M. S. Rozhnov, D. N. Melnik, UDC 536.423.15

and P. A. Chmykhalo

An equation is obtained for calculating the compressibility factor and saturated vapor density of n-alkanes
(C1–C10), parahydrogen, and water at temperatures of the triple point up to critical point. The calculation
error is close to that for experimental data.
Key words: compressibility factor, saturated vapor density, equation, calculation.

Data about the compressibility factor, the saturated vapor density for n-alkanes, parahydrogen, and water are neces-
sary for monitoring and controlling the production process of their manufacture, and also for preparing standard specimens
of compositions and properties for gas mixtures and solutions.
Analysis of experimental information about the density of saturated n-alkane vapor, whose main part has been
obtained on the basis of data in [1], has shown that only the first eight homologues of n-alkanes (C1–C8) have been studied
in detail. There are almost no data for heavier alkanes with a number of carbon atoms greater than eight.
In order to calculate the compressibility factor and vapor density at the boiling line, various equations are used [2–6].
In [7] for this calculation an equation is proposed:
α
( Z − Zc ) /(1 − Zc ) = (1 − τ γ )βτ , (1)

where Z and Zc are vapor compressibility factors at the boiling line and the critical point, respectively; τ = T/Tc is the reduced
saturation temperature; and Tc is the temperature at the critical point. Parameters α, β, and γ are identical for all substances:
α = 4.0; β = 0.33; γ = 0.7. Factor Zc, which is individual for each substances, is calculated by the equation

Zc = (Pc·103)/(ρcRmTc),

where Pc, ρc are the pressure and density at the critical point, respectively; Rm = R/M is the specific gas constant; R = 8.314472
is the universal (molar) gas constant; and M is the substance molar weight.
Equation (1) is in fact an interpolation equation between extreme cases: an ideal gas [(Z – Zc)/(1 – Zc)] → 1 at low
temperature and low values of saturation pressure and critical point for a substance [(Z – Zc)/(1 – Zc)] → 0 at temperatures
close to the critical point Tc, or τ → 1.
Fixed values of parameters α, β, and γ of Eq. (1) do not make it possible to obtain the optimum value for each sub-
stance, since the individual nature of a substance in fact is only determined by two parameter Zc and Tc. Therefore, the relative
interpolation error both in the middle of the range and at the edges is within the limits 1–6%.

All-Ukraine State Scientific and Production Center for Standardization, Metrology, Certification, and Consumer
Protection (Ukrmetrteststandart), Kiev, Ukraine; e-mail: molar@ukrcsm.kiev.ua. Translated from Izmeritel’naya Tekhnika,
No. 6, pp. 65–69, June, 2010. Original article submitted February 14, 2010.

0543-1972/10/5306-0715 ©2010 Springer Science+Business Media, Inc. 715

 Fig. 1. Inverse reduced compressibility factor Zc /Z″ of saturated vapor at the boiling lines of water, parahydrogen,
methane, propane, and n-hexane according to (2).

In addition, even if all three parameters are made variable, this does not give the desired approximation to experi-
mental and high precision calculated data at the level of their error, which is confirmed by approximate data for water [8] and
methane [9].
On the basis of (1), the following equation was obtained, not having any noticeable disadvantages:

βτ α
(
Z ′′ / Zc = 1 − bτ y (1 − τ)0.339 + 1 − τ[1+ γ (1− δτ )] / τ ) , (2)

where Z″/Zc = F(α, β, γ, b, y, Zc, τ) is the reduced compressibility factor for saturated vapor at the boiling line.
A term is given in (2) that answers fort he critical density index, and in fact: bτy(1 – τ)0.339. Multiple bτy provides
a rapid reduction in the effect of this term with a reduction in temperature. Parameter γ in (1) depends on temperature in (2).
As a result of this, a relationship has been found for the derived compressibility factor from six coefficients and Zc
for each individual substance, that provides description of experimental and precise calculated data taking account of the
error. Here numerical values of coefficients are limited (they do not increase up to infinity with approximation) and they are
mainly positive. Equation (2) makes it possible to describe with experimental accuracy the compressibility factor and den-
sity of saturated vapor of any substances over the whole range of temperature for liquid and vapor phase existence with a
comparatively small number of parameters. It also corresponds to all theoretical requirements, including approximation to
the critical point with index β = 0.339 that equals the index for saturated liquid and this provides symmetry of the behavior
of saturated solution and gas density at the critical point.
The bases taken in studying (2) are calculated data for saturated vapor density from the following thermodynamic
tables of reference data for substances: methane [9, 10]; ethane [11]; ethane, propane, and n-butane [12]; methane, propane,
and ethane [13–15]; n-butane [16]; n-nonane and n-decane [17]; n-hexane [1]; parahydrogen [12, 18]; water [8].
Results are presented in Fig. 1 for approximation of Eq. (2) of the inversely derived compressibility factor for five
substances, that show the interpolation possibilities of this equation on a ideal gas state at low temperature, where the value
Zc /Z″ tends towards Zc, and up to a critical point where this value tends towards one.
According to calculation of the derived compressibility factor for saturated vapor for methane and water, the bound-
aries with respect to the error of (2) do not exceed 0.01%, apart from in the immediate vicinity of the critical point. The rel-
ative error of calculation depends mainly on the relative error of determining values of compressibility factor at the critical
point δZc and may vary up to 3%. The error for temperature determination may be ignored.

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TABLE 1. Coefficients of Eqs. (2) and (3) for Calculating the Density of Saturated Vapors of n-Alkanes, Parahydrogen, and
Water at the Boiling Line

Coefficients of Eqs. (2) and (3)

Substance
α β γ δ b y Zc

Parahydrogen 0.9568216 0.3994209 –0.04277766 0.3455847 0.3682221 19.43794 0.3200451

Methane 0.7620916 0.3997347 1.245552 0.4837086 0.1381987 23.42937 0.2862900
Ethane 0.6199768 0.4145105 1.852849 0.4873013 0.0706340 35.98913 0.2793461
Propane 0.6567905 0.4065226 2.149039 0.5511107 0.1194454 34.71061 0.2762520
n-Butane 1.107155 0.3671919 2.020863 0.7063268 0.4244242 36.85910 0.2731774
n-Pentane 1.732561 0.3506370 2.026562 0.8828137 0.4500000 40.00000 0.2714057
n-Hexane 2.630879 0.3910519 0.8086478 0.4518243 0.5214176 250.0000 0.2646205
n-Heptane 1.411045 0.4243083 1.727959 0.1993487 1.131587 269.3292 0.2599737
n-Octane 1.586697 0.4143625 1.820971 0.3355537 0.5416269 270.0 0.2553947
n-Nonane 1.914523 0.4249665 1.617870 0.03565392 0.9568682 280.0 0.2522770
n-Decane 1.177082 0.4957439 2.387258 0.02698083 0.0221423 300.0 0.2480756
Water 1.092073 0.4050232 2.254395 0.5430454 0.2836138 21.56322 0.2294348

TABLE 2. Results of Comparing Experimental and Calculated Data for Saturated Vapor Density

Substance N* Temperature range, K δρ max, % Tmax, K Reference

Parahydrogen 17 14–30 0.0093 14 [17, 18]

Methane 51 90.7–190 0.0127 188 [9, 17]
Ethane 107 90.4–304 0.0488 158 [11, 17]
Propane 34 85.5–369.8 0.0979 120 [15, 17]
n-Butane 119 135–425 –0.7859 425 [12, 16, 17]
n-Pentane 92 144–469 –1.5802 464.33 [1, 17]
n-Hexane 81 180–505 0.9596 443.15 [1, 17, 18, 22]
n-Heptane 23 200–539.51 –1.7919 498.11 [1, 17, 18]
n-Octane 82 220–563.15 1.5522 393.15 [17, 18]
n-Nonane 23 320–590 –1.0292 320 [17]
n-Decane 38 245–615 2.1014 245 [17]
Water 179 273.16–643.15 0.0253 643.15 [8, 17]
*
N is the number of determined (calculated) points in temperature range; δρ max = 100(ρexp.i – ρcalc.i)/ρexp.i is maximum relative deviation, %, at tem-
perature Tmax, K.

717
 a

Fig. 2. Relative deviation of calculated data for saturated vapor density at the boiling line accord-
ing to (3) from calculated data: a) water [8]; b) parahydrogen [12, 18]; c) methane [9, 10, 13];
d) propane [12, 15].

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 Optimum coefficients of (2) for each substance were determined by nonlinear minimization of the mean square devia-
tion of experimental or calculated data for saturated vapor density at the boiling line according to a FLEXIPLEX program [19].
In order to calculate saturated vapor density, Eq. (2) was used in the form

⎡ βτ α ⎤
⎢⎣
(
ρ v = ρc ( π / τ) ⎢1 − bτ y (1 − τ)0.339 + 1 − τ[1+ γ (1− δτ )] / τ ) ⎥,
⎥⎦
(3)

where ρv is the saturated vapor density; π = Ps / Pc is the reduced saturated vapor pressure, Ps is the substance saturated
vapor pressure.
Numerical values are given in Table 1 for coefficients of Eqs. (2) and (3) for n-alkanes, parahydrogen, and water,
obtained by the method indicated. Values of compressibility factor at the critical point Zc were calculated from data for crit-
ical parameters [20].
It follows from (3) that the relative error of calculating vapor density at the boiling line δρ consists of two main
terms: δρ = δπ + δZ, where δπ = 100Δπ/π is the relative error of the reduced saturated vapor pressure, %; δZ = 100ΔZ/Z is the
relative error of the reduced saturated vapor compressibility factor, %.
The error of temperature determination may be ignored in view of its small value. The error of calculating saturat-
ed vapor pressure has been determined in [21], and it depends linearly on substance molar weight: the greater the molar
weight, the greater is the error (from 0.02% for methane to 0.5% for n-decane).
Results of comparing experimental and calculated data for saturated vapor density of n-alkanes, parahydrogen, and
water at the boiling line are provided in Table 2.
Saturated vapor pressure was calculated by a generalized equation [21].
The reliability of all calculated values for vapor density after optimization of coefficients of (2) confirmed the uni-
form nature of a fall of the second variable coefficient with a reduction in temperature. In order to obtain the second variable
coefficient an equation was used:
B(T) = (P·103/ρ)/(ρRmT – 1). (4)

Equation (4) was obtained on the basis of assumptions that with a temperature below the normal boiling point
(saturation pressure is less than atmospheric) the compressibility factor for saturated vapor may be represented by a viri-
al expansion, cut short at the second virial coefficient [9, 23], i.e.,

Z = P·103/(ρRmT ) = 1 + B(T)ρ.

Deviations are shown in Fig. 2 for calculated data by (3) from the most precise extrapolated data for well-known
substances.
Thus, the Eq. (2) developed is used for determining the saturated vapor density of pure alkanes of normal structure
(n-alkanes) with a number of carbon atoms in the molecule of 1–10, parahydrogen, and water at the boiling line (lines of equi-
librium coexistence of liquid and vapor) on temperature of the ternary point up to the critical temperature. The accuracy of
the equation is at the level of experimental data precision. In order to use the equation, it is sufficient to know values of the
coefficients for a substance and numerical values of critical parameters.

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