4. T. S. Khudyakova, D. A. Rozental' , I. A. Mashkova, et al., Khim. Tekhnol Topl.

Masel,
No. 12, 1516 (1987).
5. T. S. Khudyakova, D. A. Rozental' , I. A. Mashkova, et al. Izd, No. 6, 35-36 (1987).

CALCULATION OF THE LATENT HEAT OF VAPORIZATION OF

PETROLEUM FRACTIONS

L. P. Gilyazetdinov UDC 665.71.035

Latent heat of vaporization of many organic liquids at standard pressure and boiling
point (Hb, kJ/mole) can be calculated with sufficient accuracy by Kistyakov's formula as
follows:

Hb= (36,63+ 19,131g~1%. 10-3

where, Tb is boiling point at standard pressure, K.
Very little reference data exist on latent heat of vaporization of hydrocarbons and
organic sulfur compounds at other temperatures. Meanwhile, in petroleum refining practice,
vaporization and condensation of fractions are carried out over a wide range of temperatures
and, as a rule, at temperatures other than Tb. Calculation of the latent heat of vaporiza-
tion from tables of enthalpies of petroleum fractions in vapor and liquid states available
in the literature leads to coarse errors which are inadmissible in physicochemical studies.
Knowledge of the critical parameters of petroleum fractions is necessary for relatively
accurate methods of calculation of their latent heat of vaporization. This is, however,
not always available and accuracy in their calculation is usually low.
Based on analysis of reference data on the latent heat of vaporization of hydrocarbons,
organic sulfur compounds, and some nitrogen- and oxygen-containing compounds, we have derived
empirical formulas as follows for calculating latent heat of vaporization of petroleum frac-
tions at boiling point and 25~ (1298 K) using data from type analysis as the correlational
parameters: :'

Hb= 22,27+ 0,0966t b (I)

(2)
H~98=22,27-t-0,0966tb -0,0019 r a-~-Kn!f~45_{_1,34o10-3t~ 77

where, tb is boiling point at normal pressure, ~ Ka and Kn are number of aromatic and napth-
thenic rings in an average molecule.
The rms error in calculation by formula (i) is • 0o8% for 98 hydrocarbons and organic
sulfur compounds of 80-270 molecular mass. Errors in calculations by formula (2) are as
follows: • for H-alkanes, isoalkanes, alkenes, alkylcyclopentanes, alkylcyclohexanes,
and alkylbenzene (except benzene); • 2.3 % for decalins, alkylnaphthalenes, and dialkylsul-
fides.
We used the Watson correlation [i, 2] based on the theory of eigenstates for a series
of organic liquids with a view to establish the dependence of latent heat of vaporization HT
of narrow petroleum fractions on temperature T:

Hr=Hb( ~r-T ~n
r~---~-r_rb/ (3)

Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 12, pp. 28-29, December,
1990.

648 0009-3092/90/1112-0648512.50 9 1991 Plenum Publishing Corporation

 TABLE 1
~tant heal: of v a p o r i z a t i o n , kJ / B o l e

calculated
~.~ determined
experimen- ' by proposed by Vetere- by P i t z e r -
tally [a] method Watson' s Lip~ann' s
method met.hod

H-oggitne

--50 44,42 45.58 46.45 --

25 41,50 41,37 42,33 41,57
125,7" 34.63 34,41 35,49 34,51
280 13,82 13,51 14,50 13,6 I
lsooctane

- - 100 39.91 42,49 42,34 --

25 35, I I 35,44 36,22 35.21
99,2" 32,28 31,86 31,60 30,68
200 22,19 22.90 22.60 21,69
OcUtrm-'t

~50 43,00 44,67 45,88

25 39.73 40,52 41,78 40.39
121,3" 33.79 33,99 35.29 34.38
280 13.31 12,40 13,39 I 1,87
m-Xyleme

--40 44.80 44,37 46,82 --

25 42.77 41,61 43.65 --
m-Xylene
139.1" 36.39 35,71 36,94 36.61
300 20.52 21,16 20.86 20.49
h-Butylbenzeae

--80 54,85 55,09 56,82

25 50,20 49,92 51,59 --
183,3" 39~7 39,97 41,99 41,62
370 15.54 15.51 16.41 15,32
ttaphtlmleae
90 50,12 49,72 51,43 --
218,0" 43.54 43,33 44,18 43,96
400 28,47 28.27 27,98 27,66

9MS e ~ r ,
at 25eC 1,59 3,24 0,98
at boiling point
and sc~mdazd 1.25 3,33 3.29
pz~.ssuce

total -- "' 2,63 3.76 3,66

*Kinetic temperature.

where, Tcr is critical temperature, K; n is an expmmmm~.

Accroding to Watson, n = 0.38, Our calculations show that n = 0.34-0.52 for hydrocarbons
and organic sulfur compounds, i.e., it varies over a relatively wide range. With known values
of Hb and H29 s, HT can be calculated for a wide range of temperatures by formula (3) with

n=(~r-298)/(~r--
H~/Hb ~)
(4)

V a l u e s of Tcr required for calculations by formulas (3) and (4) can be calculated by the
formula proposed earlier by us and also based on the use of data from type analysis of the
fractions as follows:

~r=425-{ - 1,214/b-0,000635t2-1- [31Ka 7526Kn-l-12 (Ka-- I) -F

+5(Kn_I)+O,O59C~M+O.OI29CNM+O,O2CoM 150----...-9---0
t hl- 273

where, Cs, CN, and Co are sulfur, nitrogen, and oxygen contents in the fraction, mass %; M
is molecular mass.

649