Nuclear Technology

ISSN: 0029-5450 (Print) 1943-7471 (Online) Journal homepage: http://www.tandfonline.com/loi/unct20

An Empirical Equation for Vapor Pressure of Tri-

n-Butyl Phosphate in the Temperature Range of
273.15 to 562.15 K

Shekhar Kumar & S. B. Koganti

To cite this article: Shekhar Kumar & S. B. Koganti (1999) An Empirical Equation for Vapor
Pressure of Tri-n-Butyl Phosphate in the Temperature Range of 273.15 to 562.15 K, Nuclear
Technology, 126:2, 237-239, DOI: 10.13182/NT99-A2971

To link to this article: https://doi.org/10.13182/NT99-A2971

Published online: 10 May 2017.

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AN EMPIRICAL EQUATION FOR VAPOR REPROCESSING

PRESSURE OF TRI-n-BUTYL TECHNICAL NOTE

PHOSPHATE IN THE TEMPERATURE KEYWORDS: vapor pressure,

physical properties, tri-n-butyl
RANGE OF 273.15 TO 562.15 K phosphate

SHEKHAR KUMAR* and S. B. KOGANTI

Indira Gandhi Centre for Atomic Research, Research and Development Section
Reprocessing Group, Kalpakkam 603 102, India

Received March 23, 1998

Accepted for Publication October 1, 1998

3206.6
log~P, mm! 5 8.5861 2 . ~1!
T
Tri-n-butyl phosphate (TBP) is an excellent industrial sol-
vent for metal extraction in the nuclear chemical industry. It is Davis and Kibbey 10 evaluated the data available in the
also being used as a major constituent of hydraulic fluids in literature, and after rejecting many data points, they proposed
the aircraft industry and other industrial applications. Risk as- the following equation:
sessment studies demand limiting of airborne concentration of
TBP during normal as well as accidental exposure to humans, 7166
ln~P, mm! 5 19.295 2 . ~2!
as the toxicity index for TBP is quite high. Published data on T
TBP vapor pressure has been analyzed, and an empirical equa-
tion is reported for the temperature range of 273.15 to 562.15 K. Burger 2 proposed a similar equation in a limited range of
The performance of the reported equation is compared with data ~323 to 500 K!. His equation is as follows:
the correlations available in the literature. 7735
ln~P, mm! 5 20.531 2 . ~3!
T
Skene and Krzymien 3 calculated parameters of the An-
toine equation for their data and an additional set of data at the
INTRODUCTION normal boiling point of TBP. Their data can be well repre-
sented by the equation
Tri-n-butyl phosphate ~TBP! has a low vapor pressure and
degrades at the boiling point. Conventional purification of TBP 1690.26
is performed under reduced pressure. A narrow range of TBP log~P, Pa! 5 8.85629 2 . ~4!
~T 2 123.431!
vapor pressure was reported by several researchers. Related
literature was reviewed in detail by Leroy 1 and Burger 2. Equations from the literature @Eqs. ~1!, ~2!, and ~3!# were
Leroy 1 listed literature data in the range of 5.3 3 10 22 Pa based on the experimental data in the pressure range of
to 20 kPa ~0.4 3 1023 to 150 mm Hg! ~a temperature range of 1.33 kPa ~10 mm Hg! or higher. Lack of reliable low-pressure
298.15 to 500.15 K!. Recently Skene and Krzymien 3 reported data was a problem in extending the applicability of Eqs. ~1!,
experimental data for the vapor pressure of TBP in the temper- ~2!, and ~3!. At lower temperatures ~and pressures!, extrapola-
ature range of 273.15 to 353.15 K. They used solid sorbent tion of Eqs. ~1!, ~2!, and ~3! resulted in large errors. On the
trapping0thermal desorption gas chromatography for dynamic other hand, application of Eq. ~4! generally resulted in a large
headspace sampling. The database for the vapor pressure of positive deviation in the case of interpolating the data at higher
TBP is listed in Table I. temperatures ~and pressures!, as shown in Fig. 1.
For the database compiled from the literature and listed in
Table I, a two-parameter equation, similar to Eqs. ~1!, ~2!, and
DISCUSSION ~3!, was obtained from the least-squares analysis:
In the early thirties, Evans et al.4 reported experimental 9010.2
values of TBP vapor pressure and correlated their results by ln~P, Pa! 5 28.258 2 . ~5!
T
means of the following equation:
Equation ~5! had a large standard deviation of the order of 50%.
*E-mail: shekhar@igcar.ernet.in A three-parameter equation could correlate data well with a

NUCLEAR TECHNOLOGY VOL. 126 MAY 1999 237

Kumar and Koganti TBP VAPOR PRESSURE AS A FUNCTION OF TEMPERATURE

TABLE I
Details of the Database for the Vapor Pressure of TBP in the Temperature Range of 273.15 to 562.15 K

Temperature Number
~K! Vapor Pressure of Points Primary Reference

273.15 to 352.15 0.004 to 31.9 Pa ~3 3 10 25 to 0.24 mm Hg! 8 Skene and Krzymien 3

469.15 to 500.15 6.6 to 20 kPa ~50 to 150 mm Hg! 3 Evans et al.4
348.15 26.6 Pa ~0.2 mm Hg! 1 Burger 5
411.65 0.8 kPa ~6 mm Hg! 1 Vogel and Kowan 6
418.15 1.06 kPa ~8 mm Hg! 1 Warf 7
426.15 1.46 kPa ~11 mm Hg! 1 Stoller and Richards 8
455.15 4.66 kPa ~35 mm Hg! 1 Albright in Leroy 1
562.15 101.325 ~760 mm Hg! 1 Benedict et al.9

TABLE II
Comparison of the Performance of Different Equations for the Vapor
Pressure of TBP in the Temperature Range of 273.15 to 562.15 K

Standard
Empirical Equation Deviation
and Reference ~%!

Eq. ~1! ~Evans et al.4 ! a 625.2

Eq. ~2! ~Davis and Kibbey 10 ! a 868.0
Eq. ~3! ~Burger 2 ! a 361.6
Eq. ~4! ~Skene and Krzymien 3 ! 20.51
Eq. ~5! ~this work! a 49.37
Eq. ~6! ~this work! 15.19
a
These equations follow the Clausius-Clapeyron equation. Hence, they
are valid only in a small range.

Fig. 1. Plot of deviations. The symbols are as follows: C, Eq. ~6!; ▫ ,

Eq. ~5!; and n , Eq. ~4! ~Skene and Krzymien 3 !.

mean deviation of 1.1% and a standard deviation of 15.2%. The

three-parameter equation developed is as follows:
981.49 1.4583 3 10 6
ln~P, Pa! 5 17.715 2 2 . ~6!
T T2
Multiparameter ~$3! equations listed by Walas 11 were also
fitted to the data listed in Table I. For them, there was no sig-
nificant improvement in performance as compared to that of
Eq. ~6!; thus, they were not pursued further.
Performance of Eqs. ~1! through ~6! has been compared in
Table II and Fig. 2. Equation ~6! is considered more reliable
than the correlations available in the literature in the entire range
of 273.15 to 562.15 K.

CONCLUSIONS Fig. 2. Comparison of predicted vapor pressures with the reported ex-
perimental values. The symbols are as follows: C, experimen-
Published data on TBP vapor pressure have been ana- tal values; ▫ , Eq. ~1! ~Evans et al.4 !; n , Eq. ~2! ~Davis and
lyzed, and an empirical equation is reported for predicting TBP Kibbey 10 !; x, Eq. ~3! ~Burger 2,5 !; and —, Eq. ~6!.

238 NUCLEAR TECHNOLOGY VOL. 126 MAY 1999

 Kumar and Koganti TBP VAPOR PRESSURE AS A FUNCTION OF TEMPERATURE

vapor pressure in the range of 273.15 to 562.15 K. This re- 6. A. I. VOGEL and D. M. KOWAN, “ Physical Properties of Some
ported equation is considered more reliable than the previ- Alkyl Phosphates and Chemical Constitution—VII. Alkyl Sulphides,
ously reported equations in this temperature range. Disulphides, Sulphites, Sulphates, and Orthophosphates,” J. Chem. Soc.,
16 ~1943!.

7. J. C. WARF, “Extraction of Cerium ~IV! Nitrate by Butyl Phos-

REFERENCES phate,” J. Am. Chem. Soc., 71, 3257 ~1949!.

1. P. LEROY, “Etude du Solvent Phosphate Tributylique 30% Do-
decane,” CEA-R-3207, Centre d’Etude Nucléaires ~1967!.
2. L. L. BURGER, “ Physical Properties,” Science and Technology
of Tributyl Phosphate, Vol. I, p. 27, W. W. SCHULZ, J. D. NAVRA-
TIL, and A. E. TALBOT, Eds., CRC Press, Boca Raton, Florida ~1984!.
3. W. G. SKENE and M. E. KRZYMIEN, “Vapor Pressure of Tri-n-
Butyl Phosphate,” J. Chem. Eng. Data, 40, 394 ~1995!.
4. D. P. EVANS, W. C. DAVIES, and W. J. JONES, “The Lower
Trialkyl Orthophosphate I,” J. Chem. Soc., 1310 ~1930!.
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LER and R. B. RICHARDS, Eds., Interscience Publications, New York
~1961!.
9. M. BENEDICT, T. H. PIGFORD, and H. W. LEVI, Nuclear Chem-
ical Engineering, 2nd ed., p. 173, McGraw Hill Book Company, New
York ~1981!.
10. W. DAVIS, Jr. and A. H. KIBBEY, “The Vapor Pressure of Tri-n-
Butyl Phosphate,” ORNL-TM-3568, Oak Ridge National Laboratory
~1971!.

5. L. L. BURGER, “The Chemistry of Tributyl Phosphate—A Re- 11. S. M. WALAS, Phase Equilibrium in Chemical Engineering,
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Shekhar Kumar ~BS, chemical engineering, Harcourt Butler Technological Insti-

tute, Kanpur, India, 1987! is a senior research engineer with the department of Atomic
Energy at the Indira Gandhi Centre for Atomic Research ~IGCAR!. He is working in the
area of simulation and modeling of solvent extraction processes related to fast-breeder-
reactor fuel reprocessing. His background includes thermodynamics, modeling of ther-
mophysical properties, study of nonideal effects in solvent extraction, and artificial
intelligence.
Sudhir B. Koganti ~BS, chemical engineering, Banaras Hindu University, India,
1973; MS, nuclear engineering, Ohio State University, 1984; PhD, chemical engineering,
Indian Institute of Technology, Madras, India, 1995! is employed with IGCAR in the
Department of Atomic Energy. He is currently head of the Research and Development
Reprocessing Group, developing head-end and liquid-liquid extraction equipment. His
background includes two-phase fluid flow, heat transfer in heat pumps, and analysis of
multiphase systems.

NUCLEAR TECHNOLOGY VOL. 126 MAY 1999 239