S T D .

A P I / P E T R O T D B C H A P T E R 12-ENGL 1 9 9 2 0732270 O5b70bB Ob9

CHAPTER 12
THERMAL CONDUCTIVITY

Revised Chapter 1 to First Edition (1966), Second Edition

(197O), Third Edition (1977), Fourth Edition (1982), and
Fifth Edition (1992)

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 S T D . A P I / P E T R O T D B C H A P T E R 12-ENGL 1 9 9 2 0732290 05b7070 717 -
PREFACE

During the past three years, the Technical Data Book - Petroleum ReJning project staff in
the Department of Chemical Engineering at The Pennsylvania State University has revised and
expanded Chapter 12, "Thermal Conductivity," with new data and correlations. Available methods
for predicting thermal conductivities of liquid and gaseous hydrocarbons and their mixtures were
tested before selecting a recommended method in each category. Detailed results of the evaluations
are given in Documentation Report No. 12-96, available from Global Engineering Documents.
Work on this chapter was primarily conducted by R Roberta Wu under the supervision of the
project director, ThomasE. Daubert. The chapter coordinator for the Technical Data Committee is
Costa Tsonopoulos of Exxon Research & Engineering Co.

Thomas E. Daubert
Department of Chemical Engineering
The Pennsylvania State University
University Park, PA 16802
August 1996

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S T D * A P I / P E T R O T D B CHAPTER 1 2 - E N G L 1772 0732270 05b7071 b53

CHAPTER 12

THERMAL CONDUCTIVITY

PAGE
12-0 Introduction ...................................................... 12-1
Table 12-0.1 Table of Thermal Conductivity of Hydrocarbons . . . . . . . . . . . . . . . . 12-4
Figure 12-0.2 Liquid Hydrocarbon Thermal Conductivity Calculation
Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12-5
Figure 12-0.3 Gaseous Hydrocarbon Thermal Conductivity Calculation
Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12-6

12A Thermal Conductivity of Liquid Hydrocarbon Systems

12A1. Thermal Conductivity of Pure Liquid Hydrocarbons
Procedure 12A1.1 Thermal Conductivity of Pure Liquid Hydrocarbons
at Low Pressures and Below the Normal Boiling
Point . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12-7
Procedure 12A1.2 Thermal Conductivity of Pure Liquid Hydrocarbons
at Low Pressures, Generalized Method . . . . . . . . . . . . . . . . 12- 1 1
Procedure 12A1.3 Thermal Conductivity of Pure Liquid Hydrocarbons
Above the Normal Boiling Point and at Ail
Pressures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12-13

12A2. Thermal Conductivity of Defined Liquid Hydrocarbon Mixtures

Procedure 12A2.1 Thermal Conductivity of Defined Liquid
Hydrocarbon Mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12-15

12A3. Thermal Conductivity of Undefined Liquid Hydrocarbon Mixtures

Procedure 12A3.1 Thermal Conductivity of Uncharacterized Liquid
Petroleum Fractions at Low Pressures . . . . . . . . . . . . . . . . 12-19
Procedure 12A3.2 Thermal Conductivity of Liquid Petroleum
Fractions at Low Pressures . . . . . . . . . . . . . . . . . . . . . . . . . 12-21
Procedure 12A3.3 Thermal Conductivity of Liquid Petroleum Fraction
Blended with Defined Light Hydrocarbon Liquid
Mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12-23

12A4. Effect of Pressure on Liquid Hydrocarbon Thermal Conductivities

Procedure 12A4.1 Thermal Conductivity of Liquid
Hydrocarbons at High Pressures . . . . . . . . . . . . . . . . . . . . . 12-26

12B Thermal Conductivity of Gaseous Hydrocarbon Systems

12B1. Thermal Conductivity of Pure Hydrocarbon Gases
Procedure 12B1.1 Thermal Conductivity of Pure Hydrocarbon Gases
at Low Pressures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12-28

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Procedure 12B1.2 Thermal Conductivity of Pure Hydrocarbon Gases

at Low Pressures. Generalized Method . . . . . . . . . . . . . . . . 12-32

12B2. Thermal Conductivity of Defined Mixtures of Hydrocarbon Gases

Procedure 12B2.1 Thermal Conductivity of Defined Mixtures of
Hydrocarbon Gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12-34

12B3. Thermal Conductivity of Undefined Mixtures of Hydrocarbon Gases

Procedure 12B3.1 Thermal Conductivity of Petroleum Fraction Vapors
at Low Pressures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12-38

12B4. Effect of Pressure on Gaseous Hydrocarbon Thermal Conductivities

Procedure 12B4.1 Thermal Conductivity of Pure Hydrocarbon Gases at
High Pressures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12-40

12C Thermal Conductivity of Nonhydrocarbons

12C1. Thermai Conductivity of Nonhydrocarbons
Procedure 12C1.1 Thermal Conductivity of Selected Nonhydrocarbons . . . . . . .12-44
Table 12C1.2 Constants for Procedure 12C1.2 . . . . . . . . . . . . . . . . . . . . . 12-47
Figure 12C1.3 Thermal Conductivity of Nitrogen . . . . . . . . . . . . . . . . . . . 12-48
Figure 12C1.4 Thermal Conductivity of Carbon Monoxide . . . . . . . . . . . . 12-49
Figure 12C1.5 Thermal Conductivity of Oxygen . . . . . . . . . . . . . . . . . . . . 12-50
Figure 12C1.6 Thermal Conductivity of Hydrogen . . . . . . . . . . . . . . . . . . . 12-51
Figure 12C1.7 Thermal Conductivity of Carbon Dioxide . . . . . . . . . . . . . . . 12-52
Figure 12C1.8 Thermal Conductivity of Sulfur Dioxide (Low
Range) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12-53
Figure 12C1.9 Thermal Conductivity of Sulfur Dioxide (High
Range) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12-54
Figure 12C1.10 Thermal Conductivity of Ammonia . . . . . . . . . . . . . . . . . . . 12-55
Figure 12Cl.11 Thermal Conductivity of Water . . . . . . . . . . . . . . . . . . . . . 12-56
Figure 12C1.12 Thermal Conductivity of Hydrogen Sulfide and
Sulfk Trioxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12-57

Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12-59

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CHAPTER 12

THERMAL CONDUCTIVITY

12-0 INTRODUCTION

Thermai conductivity is that physical property which describes the ease with which heat can
flow by conduction through a quiescent solid, liquid, or gaseous layer of a substance. It is defined
as the proportionality constant, k, in, Fourier's law of heat conduction, in Btu per (hr)(sq A)(deg F)
per A. The variation of thermal conductivity for different temperatures, pressures, chemical
compositions, and physical states may be viewed in a general and simplified manner by considering
the orderliness of the substance. For a single chemical compound, the order and, hence, thermal
conductivity increases in the sequence: vapor, liquid, amorphous solid, crystal. Although this is
largely true for intersubstance comparisons also, there are exceptions. For instance, gaseous
hydrogen has a higher thermal conductivity than does liquid benzene, and water has a higher thermal
conductivity than does wood.
The thermal conductivity of most liquids decreases with increasing temperature. This is
primarily a tunction of density(and order); however, the velocity of sound likewise decreases with
temperature for organic liquids. For some liquids, the velocity of sound increases with temperature.
This effect may overshadow the effect of density, resulting in a rise in conductivity with a rise in
temperature. For water, the conductivity first rises to a maximum and then falls with increasing
temperature.
Inasmuch as a low-pressure gas is almost completely disordered, decreasing order with
increasing temperature is not a strong factor. The thermal conductivity of such a gas is instead a
strong function of viscosity and heat capacity at constant volume. Accordingly, it increases with
temperature as do these two properties.
The thermal conductivity of all nonmetallic materials increases with pressure (and order). A
detailed treatment of various pressure regions is not as simple as a mere density function might
indicate. At higher pressure, anomalies appear in the temperature íünction.
By disturbing the order of a material, impurities have disproportionate effects in reducing
conductivities. Accordingly, hydrocarbon liquid and gas mixtures do not usually obey simple mixing
rules.
Thermal conductivities of substances are required in correlations and design methods for heat
transfer operations. The thermal conductivity may be used directly or in dimensionless numbers such
as the Prandtl, Nusselt, and Graetz numbers. Unfortunately, some of the design correlations involving
these dimensionless numbers were based on questionable experimental data. The user should be
aware of this when designing for crucial service.
In this chapter, means are provided for estimating the required thermal conductivities in the
liquid and gas phases for pure and mixed hydrocarbons and for nonhydrocarbon gases. When
considering the use of new thermal conductivity data versus the use of recommended correlations,
vapor-phase data obtained by a conscientious investigator almost always are reliable; whereas liquid
data obtained before the introduction of transient measurement techniques may very well be in
considerable error. Experimental problems with simultaneous convective heat transfer have a much
stronger effect on the results for liquids than on those for vapors.
The various methods for determining the thermal conductivity of hydrocarbons and their

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 STD*API/PETRO TDB CHAPTER 12-ENGL 1992 - 0 7 3 2 2 7 0 05b707'4 3b2 =

mixtUres are listed in Table 12-0.1 and Figure 12-0.2.

Liquid Systems

The thermal conducthities of liquids are independent of pressure (relative to the accuracy of
existing data and correlations) below approximately 500 pounds per square inch absolute and
decrease íinearly as temperature increases from the fieezhg point to the normal boiling point. This
linearity is believed to continue to a reduced temperature of approximately 0.8, where thermal
conductivity begins to decrease more rapidly as the critical point is approached (159). Data for the
bnductivities at the fieezhg and normal boiling points, which were selected on the basis of reliability,
are given in Procedure 12A1.1. A value at an intermediate temperature may be obtained by linear
interpolation.
Procedure 12A1.2 provides a general but slightly less accurate method for calculating the
t h d conductivity of pure hydrocarbons below a pressure of 500 pounds per square inch absolute
and a reduced temperature of 0.8. Procedure 12A1.3 can be used to obtain the thermal conductivity
of liquid hydrocarbons at the higher reduced temperatures and at any pressure.
For mixtures of known composition at any temperature and pressure, Procedure 12A2.1
includes a mixing rule involving conductivities of the pure components at the same conditions.
Procedure 12A3.1 allows estimation of low-pressure thermal conductivities of undefined liquid
hydrocarbons and should be used only when Procedure 12A2.1 or Procedure 12A3.2 cannot be
applied. Procedure 12A3.2 calculates the low-pressure thermal conductivities of characterized
undefined liquid hydrocarbons and gives better accuracy than Procedure 12A3.1. Procedure 12A3.3
ailows estimation of low-pressure thermal conductivities of petroleum fractions blended with defined
light hydrocarbon liquid mixtures. Procedure 12A4.1 is a correction for obtaining high-pressure
conductivities from the previously obtained low-pressure values.

Gaseous Systems

The thermal conductMty of an ideal gas is independent of pressure. Pure-component vapor

thmai conductivities can be calculated analytically as a function of temperature by using Procedure
12Bl.l. When required data are unavailable, Procedure 12B 1.2 should be used to estimate ideal gas
thermal conductivity values for pure components.
For mixtures of known composition, the thermal conductivities of the pure components
should be blended at the desired conditions as outlined in Procedure 12B2.1. Procedure 12B3.1
provides a means of estimating the ideal gas thermal conductivity of undefmed hydrocarbon mixtures.
Procedure 12B4.1 is a correction to be applied to the ideal gas thermal conductivity estimates from
the earlier correlations for the effect of high pressure.
The thermal conductivity of pure gaseous hydrogen is given in Procedure 12C1.4. For
defined mixtures of hydrogen with hydrocarbons, use the given mixing rules and Procedure 12A2.1
for liquids or Procedure 12B2.1 for gases. For mixtures of hydrogen with petroleum fractions, use
these same mixing niles, treating the entire hydrocarbon portion as a pseudocomponent. The
hydrocarbon input data are available fiom Procedure 12A3.1 for liquids or Procedure 12B3.1 for
vapors, and the pressure correction (where necessary) should be applied before blending.
Thermal conductivities of other pure nonhydrocahon gases are obtained by Procedure 12C 1.1

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S T D - A P I I P E T R O T D B CHAPTER 1 2 - E N G L 1992 0732290 05b7075 2 T 9

throughProcedure 12C1.3,Procedure 12C1.5,Fig. 12C1.6,Procedure 12C1.7,Figures 12C1.8and

12C1.9,and Produres 12C1.10and 12Cl.11.The same procedures that apply to hydrogen should
be appropriate for these gases.

Commercial Computer Methods for Liquid and Vapor Thermal Conductivities

The SUPERTRAPP software package developed at and available fiom NIST (National
Institute of Standards and Technology) is a commercially available software package. The method
is based on corresponding states principles. It is capable of predicting the thermai conductivity of
nonpolar pure fluids and mixtures over the temperature range of 40 - 1800 Rankine and the pressure
range of O - 43500 psia. The available STJPERTRAPP database contains 116 compounds although
new compounds may be added to the database. The absolute minimum information required for a
new compound is the critical temperature, pressure, and volume, the molecular weight, and the
normal boiling point; liquid density and vapor pressure data could also be added to improve the
accuracy of the method. The main advantage of this commercial s o b a r e is its ability to handle fluids
over wide temperature and pressure ranges in one method.
Another software package for the prediction of thermal conductivity of liquid petroleum
fiactions is under development at NIST.

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 STD-API/PETRO T D B C H A P T E R 12-ENGL 1992 O732290 0 5 b 7 0 7 b 135 M

12-0.1

-
TABLE 12-0.1 THERMAL CONDUCTIVITY OF HYDROCARBONS
HydrocartKnis Pressure@sia) Temperature. Method Notes
Pure Liquids 600 Tb Procedure 12Al.l -
400 0.25G,4).8 Procedure 12A1.2 UseoniywhenPdure 12Al.l
inapplicable
400 O.Sa,<I .O Procedure 12A1.3 -
i500 T,4 .O proccdurr 12A4.1 Inputhmprocedures 12Al.l or
12A1.2

Known Liquid All All Procedure 12A2.1 input from methods above,
Mixtures nor Proceudre 12A3.1

Liquid Petroleum All -58 to 752 F Procedure 12A3.1 Used only for non-
Fractions characterized &actions. For pressures
greater than 500 psia, apply Procedure
12A4.1 to correct the pressure
All -58 to 752 F Procedure 12A3.2 Used only for characterized fractions.
For pressures greater than 500 psia,
apply Procedure 12A4.1 to correct
the pressure
Liquid Petroleum All -58 to 752 F Procedure 12A3.3 For pressures greater than 500
Fraction Blended psia, apply Procedure 12A4.1 to
With Light Liquid correct the pressure
Hydrocarbon Mixture

Pure Gases s50 As shown Procedure 12B1.1 -

do All Procedure 12B1.2 Use only when Procedure 12B1.1
does not apply
>50 All Procedure 12B4.1 input from above

\
KnownGasMixtures All All Procedure 12B2.1 For pressures greater than 50 psia,
apply Procedure 12B4.1 to c o m t
the pressure

Petroleum All -60 to 600F Procedure 12B3.i For pnssures greater than
Fraction Vapors 50 psia, apply Proceùure 12B4.1 to
c o m t the pressure

"r,=-fi.eeZing point; Tb=mrmal boiling point; T,=reduced temperature (Tlï,);T= temperature;

and T,=critical temperature.
Figure 12-0.2 H y d r d o n Thermal Conductivity Calculation Procedure

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 S T D - A P I I P E T R O T D B C H A P T E R 12-ENGL 1772 W 0 7 3 2 2 7 0 05b7077 O71 W

12-0.2

FIGURE 12-0.2 Liquid Hydrocarbon Thexmal Conductivity CaiailaGonai Procedure

yo

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STD.API/PETRO TDB C H A P T E R 12-ENGL 1772 0732270 0567078 TO8

12-0.3

FIGURE 124.3 Gaseous Hydrocarbon Thamsf Conâuctiviîy CdailationaI Procedure

1,
yI " I,-Et-@ Rgl2m.l. ffolalr

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12A1.1

12A "HERMAL CONDUCTIVITY OF LIQUID HYDROCARBON SYSTEMS

PROCEDURE 12Al.1

THERMAL CONDUCTIVITY OF PURE LIQUID HYDROCARBONS AT

LOW PRESSURES AND BELOW THE NORMAL BOILING POINT

Discussion
The thermal conductivities of liquid hydrocarbons decrease linearly with increasing temperature
fiom the fieezing point to the normal boiling point and. in some cases. beyond . Where the data are
known at these two extremes. the thermal conductivity can be calculated by linear interpolation. The
available data are tabulated below:
Themial ThCllllal
Conductivity Normal Conduciivity
Freezing ai Freezing Boiling at Normal
Point' Poktb Point' Boiling pokt4

Methane................................... -296.42 0.1298 -258.68 0.1088

Propane.................................... -305.82 0.1231 43.67 0.07448
n-Butane ................................... -216.92 0.1080 31.10 0.06796
2-Mcthylpropane........................ -2 55.30 0.09427 10.90 0.06298
n-Pentane................................. -20 1.5 1 0.1030 96.93 0.06274

n-Hexane.................................. -139.58 0.09375 155.71 0.06022

2-Methylpentane......................... -244.48 0.09243 i 40.47 0.05775
3-Methylptane ......................... -261.22 0.09507 145.89 0.05837
2.2-Dhethylb~Ia~~ ..................... -145.97 0.07773 121.51 0.05486
2,3-Dimethylbutane..................... -198.33 0.08214 136.36 0.05595

n-Heplane................................. -131.04 0.09235 209.17 0.05923

2.4-dimethylpmtane .................... -182.63 0.07807 176.89 0.05190
n-Octane.................................. -70.19 0.08780 258.22 0.05669
2.2,4-Trimcthylpentane. ............... -161.27 0.07420 210.63 0.04709
-64.28 0.08734 303.48 0.05614

2.2.5-TMnethyihexane ................. -158.37 0.07403 255.36 0.04749

n-Decane.................................. -21.35 0.0841 i 345.48 0.05464
n-Undecane............................... -14.04 0.08438 384.67 0.05372
n-Dodecane ............................... 14.75 0.08293 421.38 0.05254
n-Tridecane............................... 22.30 0.08324 455.84 0.05 174

n-TNPdecane............................ 42.55 0.08219 488.44 0.05096

n-Pmtndecuie............................ 49.86 0.08355 519.23 0.0505 1
n-Hexadaane............................ 64.68 0.08308 548.36 0.04902
n-Hcptadaane........................... 71.57 0.08322 575.87 0.04733
n-Oaadecanc ............................. 82.69 0.08435 602.08 0.04677

n-Nona&cane............................ 89.40 0.08395 625.82 0.04604

n-Eímsane................................ 97.57 0.08598 650.80 0.04629
n-Hn>ticorane............................ 104.36 0.08658 673.70 0.046 16
n-Docosaae............................... 111.20 0.08740 695.48 0.04674
n-Tricosanc............................... 117.50 0.08756 716.36 0.04684

n-Tettacosane ............................ 123.08 0.08840 736.34 0.04731

Cyclopmtane............................. -136.91 0.09153 120.65 0.06922
Methylcyclopmtane..................... -224.36 0.09272 161.26 0.06185
Cyclohexane.............................. 43.77 0.07407 177.30 0.06332
Methylcyclohewe...................... -195.83 0.08372 213.68 0.05402

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12A1.1

'Ihcmul Themrpl
carductivity N m l Conductivity
Freezing rt Freezing Boiling at Normal
POM Pointb Point' Boiling Point'

2-MechyipmpaK........................ -220.61 O. 1083 19.58 0.06773

l - H e m ................................. -219.57 O. 1024 146.26 0.06205
truns-2-Hcxenc........................... -207.36 0.09564 154.17 0.06357
1-H- ................................. -181.98 0.09644 200.55 0.06029
trmis-2-HCptenc.......................... -165.06 0.09322 208.3 1 0.06156

~ ~ U U S - ~ - H..C...P..~..O
....C -213.93 0.09684 204.2 1 0.06159
l-oacnc................................... -151.06 0.08981 250.32 0.06066
trans-2-oCrCne........................... -125.86 0.09081 257.00 0.06022
I-Nana^.................................. -114.47 0.09052 296.36 0.05333
l-D#unc .................................. -87.27 O. O883O 339.08 0.05554

~ l o h c x c n.e.............. -154.26 0.09548 181.35 0.06740

2-MechyE 1.3-bUtadia................ -220.00' 0.1049' 93.30 0.06817
&maK................................... 41.95 0.0863 1 176.16 0.07313
Me<hylbeazme (Toluene).............. -138.95 0.09336 231.13 0.06452
Elhylbauaie............................. -138.91 0.09106 277.16 0.05921

1.2-Dimahylbaizai~(&Xyime)..... -13.31 0.08263 291.97 0.06009

1,3-Dimahylbnunic (m-Xylm).... -54.13 0.08525 282.42 0.05979
1,4-Dimethylknrme @-Xylene)..... 55.87 0.07664 281.05 0.05958
n-Ropylknzenc......................... -147.28 0.08827 318.63 O. O5856
Isopropylknzme........................ -140.82 0.08588 284.00' 0.05736'

1,2.4-Trimcthylbcnzene................ 4.88 0.08322 336.88 0.05726

13.5-Tnmechylknzcn~................ 48.51 0.08703 328.53 0.06028
n-Butyiantnie........................... -126.13 0.08672 361.95 0.05530
rerr-Butylbaizme........................ -72.18 0.07S34 336.47 0.05534
Biphenyl................................... 156.60 0.08021 491 .O0 0.06393

o-Taphenyl............................... 133.16 0.07687 639.50 0.05927

m-Terphcnyl.............................. 188.33 0.07814 710.33 0.06650 .
pTnphenyl.............................. 413.33 0.07480 708.80 0.06256
-

7, lower limit of the imipcraturerange, deg F.

'IL thermal conductivity it the lower l i d of the 'cmperanirc range, BIU pa (hrxsq AX&g F) per R
1:upper limit of the crnipcranmmge, deg F.
'K, thcrmal d u c t i v i t y it the uppa limit ofthe tempmurerange. Btu per (hr)(sq AXdsg F) per A.

Procedure
Step I : From the preceding tabulation, obtain the thermal conductivities of the compound at
the freezing point and the normal boiling point.
Step 2: Calculate the thermai conductivity of the liquid by linearly interpolating between these
values.

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12A1.1
COMMENTS ON PROCEDURE 12Al.l
Purpose
Procedure 12A1.1 is presented to calculate the thermal conductivities of pure liquid hydrocarbons
at pressures lower than 500 pounds per square inch absolute fiom available experimental data. For
higher pressures, the correction in Fig. 12A4.1 should be applied. This procedure is not applicable
above the normal boiling point, where Procedure 12A1.3 should be used. Within its range of
applicability, this procedure is somewhat more accurate than is Procedure 12A1.2.

Limitations
Within a few degrees of freezing point, the thermal conductivity rises more sharply than indicated
by the simple interpolation relationship because of clustering of the molecules in anticipation of
solidification. This phenomenon can usually be safely ignored in calculation.
Do not extrapolate the data to temperatures above the normal boiling point.

Reliability
Average deviations of values calculated by this procedure fiom experimental data are less than 5
percent.

Literature Sources
The entries in the tabulation were derived fiom data fiom the following sources:
Methane (13,14.86.147) Cyclohexane(43,56,107,156.167)
Ropanc (18,129.145.1 53) Meîhvlcyclohexane (17.82.124.156)
n-Butane (18) 2-Mcthylpropene (43,152)
2-Melhylpropane (58) 1-Hexme (18.43.1 10)
n-Pentane (14.15.1 8,122,142,154.1 5 5 ) W U ~ X - ~ - H C A C I(142,155.1
E 57)
n-Hexane (9,18,56,75,82.124,142,144, I - H c ~ w ~(18,108)
c
157,168) rruns-2-Hcptene (157)
2-Melhylpentane (157) truns-3-Hieptene (156)
3-M~thylpmtane(157) l-Octrne(109.157)
2.2-Dn~Ihylb~tane (157) rruns-2-Oaene (157)
2 . 3 - D h ~ t h y l b ~ t(157)
a1~ 1-Nontnc (103)
n - H e p b (9,10.18,56,82,105,105,120
~ I-Decme (103)
124,139,142,155,157) Cyclohexmc (43,142~55.1 56)
2,CDmethylpmtanc (156) 2-hl~U1yl-1,3-botadien~ (18)
n-Octane (18,1936.1 16,120,124,142, Benzene (17,27,48,S6.77.92,120,131,140,
144,157.168) 159,167,175)
2,2,6Trimcthylpmtane (19.92.124.142, Meihylbcnzaie (10,18,38.41,45,47.53,
155,157) 83,105,118,120,124,131,132.133,
n-Nonane (18,19,45,141,142,144,157) 136.140,171,175,185)
2,2,5-Trimcthyihexane (124,l S7) E t h y l w e (56,136.140)
n-Decane (9,17,18,25,45,56,82,114, 1 . 2 - D i m e i h y l ~(t O - X Y ~ C )
(8,45.56,
116,157,168) 124.136.140.17 1)
n-Dcdecane (56,156,168) Id-Dbnethylbrnzene (m-Xylene) (8,56,136.
n-Trideconc (101) 142.1 55,171)
*Taradecane ( 1S,19,102,156,180) 1,4Dimahylbenzme @-Xylene) (3.8.56,
n-Pentadecuie (15.98.180) 120,136,142,155,171)
n - H k e (1 5,98,1S6,180) n-Propylbrnzme (46)
n-Heptsdecane (100.11 1.134) kqmpyl W e (46,56,88.142,15S,156)
mOaadecane (100,111,134,156) 1,2,4Trimethylbrnzre (135)
n-Nonadecane (98,100,115) lf,S-Trimeihylkene ( 135,140)
ndicosane (138) n-Butylbnrzme (136,156)
Heneicosane (138) fen-Butylbenzenc(135)
Docosane (98,138) Biphenyl (47,184)
Tncosane (138) o-Terphmyl(48)
Tetramane (98,138) m-Tcrphenyl(48)
Cyclopnitane(43.124.156) pTerphmnyl(48)
Melhylcyclopentane(17.142.154,156)

1997 12-9

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 S T D * A P I / P E T R O T D B C H A P T E R 12-ENGL 1772 = 0732270 0 5 b 7 0 8 2 ‘i37

12A1.1

Example

Find the thermal conductivityof n-hexane at 68 F and atmospheric pressure.

From the preceding tabulation, &= 0.09375 at T,= -139.58 F and = 0.06022 at
T, = 155.71 F. Interpolating linearly,

k = 0.09375 - 0.02357 = 0.07018 Btu per (hr)(sq ft)(deg F) per A

The experimental value (18) is 0.07032 Btu per (hr)(sq fi)(deg F) per ft.

12-10 1997

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 S T D - A P I / P E T R O TDB CHAPTER 12-ENGL 1992 0 7 3 2 2 9 0 0 5 b 7 0 8 3 375

12A1.2

PROCEDURE 12A1.2

THERMAL CONDUCTIVITY OF PURE LIQUID HYDROCARBONS AT

LOW PRESSURES, GENERALIZED METHOD

Discussion

The following equation is to be used to obtain the thermal conductivity of pure liquid
hydrocarbons at pressures below 500 pounds per square inch absolute and at reduced temperatures
between 0.25 and 0.80:

(12A1.2-1)

Where:
k = thermal conductivity, in Btu per (hr)(sq ft)(deg F) per fi.
c = coefficient obtained from the tabulation below.
n = coefficient obtained from the tabulation below.
M = molecular weight
v, molar volume at 68 F, in cubic feet per lb-mole.
=
T, = reduced temperature, T/T,.
T = temperature, in degrees Rankine.
T, = critical temperature, in degrees Rankine.

n C
For unbranched, straight chain hydrocarbon: 1.001 1.676 x 10”
For branched and cyclic hydrocarbons: 0.7717 4 . 0 7 9 ~10”

Procedu re

Step I : Obtain the critical temperature, T,, and the molecular weight fiom Chapter 1.
Step 2: Calculate the reduced temperature (T, = T/T,).
Step 3: Determine the coefficients n and C from the preceding tabulation.
Step 4: Determine the density of the hydrocarbon at 68 F according to the methods in Chap.
6.
Step 5: Determine the molar volume at 68 F by dividing the molecular weight by the density
of the hydrocarbon.
Step 6: Calculate the thermal conductivity by using equation 912A1.2-1).

1997 12-11

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 S T D . A P I / P E T R O T D B C H A P T E R 12-ENGL L772 0732290 05b7084 2 0 1

12A1.2

COMMENTS ON PROCEDURE 12A1.2

Purpose
When Procedure 12A1.1 is applicable, it should be used in preference. Procedure 12A1.2 is
presented to calculate the thermal conductivity of pure liquid hydrocarbons as a function of
temperature at pressures less than 500 pounds per square inch absolute. For higher pressures, apply
the correction outlined in Figure 12A4.1.

Limitations

Equation (12A1.2-1) is not accurate for pressures greater than 500 pounds per square inch
absolute or at reduced temperatures less than 0.25 or greater than 0.80. At reduced temperatures
greater than 0.80, Procedure 12A1.3 should be used.

Reliability

The equation yields data with an average error of 5 percent and a maximum error of 20 percent
from experimental values.

Literature Soruces

This procedure is based on methods presented by Pachaiyappan, Ibrahim, and Kuloor, Chem.
Eng. 74[4] 140 (1967) and Riedel, Chmi.-Ingr.-Tech.21 349 (1949).
Example
Calculate the termal conductivity of liquid ri-butylbenzene at 140 F and 1 atm.
From Chapter 1 the molecular weight is 134.22 and the critical temperature is 729.32 F. The
reduced temperature is therefore +4s9 .67 = 0 . 5 ~ . For
. n-butylbenzene, the coefficients n and
729.32 +459.67
C from the tabulation are 0.7717 and 4.079 x lo9, respectively. From Chapter 6, the density at 68
F is 53.76 lb per CU A. The molar volume at 68 F is therefore 134.22/53.76=2.497CU A per lb-mol.

The thermal conductivity is calculated next from equation (12Al.2-I):

I
(4.O79x1O3)(1U .22)am’]
1=[
2.497 ’ 3+20(1-0.5044 )m
19+20( 1- 527.67
(729.32 +459.67)
I -- 1
K = 0.06730 Btu per (hr)(sq A)(deg F) per fi
The expenmental value (136) at these conditions is 0.06830 Btu per (hr)(sq A)(deg F) per A.

12-12 1997

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 STD.API/PETRO T D B C H A P T E R 1 2 - E N G L 1772 0732270 0 5 b 7 0 8 5 148 8

12A1.3

PROCEDURE 12A1.3

THERMAL CONDUCTIVITY OF PURE LIQUID HYDROCARBONS

ABOVE TEE NORMAL BOILING POINT AND AT ALL PRESSURES

Discussion
The thermal conductivitiesof liquid hydrocarbons at temperatures greater than the normal boiling
point and at any pressure are to be obtained from the following equations:
pr)
-1.884xIO -6P~+1.442x10-3Pr+aexp(ß (12A1.3-1)
k=
I
Where,
7.137 rf0 -3 (1 2A1.3-2)
a=
ß 3322

0.986 (12A1.3-3)
ß =0.40+
exp(0.58 A )

A= T 3 - f ln (12A1.3-4)
(P114.696)M

k=thermal conductivity, in Btu per (hr)(sq ft)(deg F) per fi.

pr=reduced density, p/p=pV,.
p=density, in pounds per cubic foot.
pc=critical density, in pounds per cubic foot.
V,=critical volume, in cubic feet per pound.
T,=critical temperature, in degrees Rankine.
M=molecular weight.
P,=reduced pressure, P/P,.
P,=critical pressure, in psia.
P=pressure, in psia.

Procedure
Step I : Obtain the critical temperature, critical pressure, critical volume, and molecular weight
from Chapter 1.
Step 2: Calculate the reduced pressure, P,=P/p,.
Step 3: Determine A. from equation (12A1.3-4).
Step 4: Determine the density of the hydrocarbon according to the methods of Chapter 6 and
obtain the reduced density, p,=pV,.
Step 5: Calculate ß by using equation (12A1.3-3) and OL by using equation (12A1.3-2).
Step 6: Calculate the thermal conductivity by using equation (12A1.3-1).

1997 12-13

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 S T D . A P I / P E T R O T D B C H A P T E R 12-ENGL 1792 0732270 05b708b 084 M

12A1.3
COMMENTS ON PROCEDURE 12A1.3

Purpose
Procedure 12A1.3 is presented to calculate the thermal conductivity of pure liquid hydrocarbons
above the normal boiling point and at any pressure.

Limitations
At temperatures below the normal boiling point. Procedure 12A1.1 or 12A1.2 should be used
with a pressure correction obtained fiom Figure 12A4.1 if required.

Reliability
Average errors of 8 percent can be expected, with maximum errors of -32 percent.

Literature Source
The procedure is adapted fiom Kanhkar and Thodos, Can. J. Chem. Eng. 47 427 (1969).

Example
Calculate the thermal conductivity of liquid n-heptane at 320 F and 197.4 atm.
From Chapter 1, the critical temperature is 512.69 F, the critical pressure is 397.41 psia, the
critical volume is 0.0684 CU ft per Ib, and the molecular weight is 100.2. The reduced pressure is
197.4/ (397.4U14.696) = 7.30, and from equation (12A1.3-4):
(512.69+459.67)1’6(i00.2)”
A=
(397.41114.6% )y3
A = 3.497
From chapter 6, the density is determined to be 37.93 Ib per CU ft, and the reduced density is
therefore (37.93)(0.0684)= 2.594. By using equations (12A1.3-3) and (12A1.3-2), the values of ß
and a are calculated as follows:
0.986
ß =0.40+
I

cxp[(O.58)(3.497 )]

ß =OS297

7.137x10 -3
a=
(0.5297

a=O.O5892

The thermal conductivity is then calculated by using equation (12Al.3-1):

(- 1 -884x l 0 37.30 )’+( 1.442~lU -3)(7 .30)+O -05892CXP [(O .52W )
(2 394 )J
k=
3 497

k = 0.06956 Btu per (hr)(sq ft)(deg F) per ft

The experimental value (106) at these conditions is 0.06379 Btu per (hr)(sq ft)(deg F) per ft.

12-14 1997

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. STD.API/PETRO TDB C H A P T E R 12-ENGL L992 0732290 05b7087 TL0

12A2.1

PROCEDURE 12At.l

THERMAL CONDUCTIVITY OF DEFINED LIQUID

HYDROCARBON MIXTURES

Discussion
The thermal conductivity of a mixture of known composition can be calculated by using the
following equations when the conductivities of the pure components are given:

(12A2.1-1)

1 ]; -1
(12A2.1-2)

where kj= kji and = k,

(12A2.3-1)
XjVj
j

@ I = ]
(12A2.1-4)
i

Where:
= thermal conductivity of the mixture, in Btu per (hr)(sq ft) (deg F) per fi.
kn =
+i, 4 j volume fiactions of pure component i and j .
= thermal conductivities of pure components i and j, in Btu per (hr)(sq ft)(deg
4 7 Is
F) per A.
Vi7 Vj = molar volumes of pure components i and j, in CU ft per lb-mole.
x,, 5= mole fractions of pure components i and j .

For a binary mixture equation (12A2.1-1) becomes:

(12A2.1-5)

1997 12-15

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 S T D . A P I / P E T R O T D B C H A P T E R 12-ENGL 1772 = 0732290 0 5 b 7 0 ô ä 957

12A2.1

Procedure
Step i: From Chap. 1, de-tennine the molecular weight of each component of the mixture, and
fiom Procedure 12Al.l or 12A1.2, determine the thermal conductivity of each
component at the conditions desired for the mixture.
Step 2: From Chap. 6,determine the density of each component of the mixture.
Step 3: Calculate the molar volume of each component as the molecular weight divided by the
density.
Step 4: Calculate by using equation (12Aî.1-2).
Step 5: Calculate the volume fraction of each component of the mixture by using equation
(12A2.1-3)and check to determine that the sum of all the pure component volume
fractions total 1, according to equation (12A2.1-4).
Step 6: Calculate the thermal conductivity of the mixture by using equation (12A.î.1-1).

12-16 1997

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 12A2.1

COMMENTS ON PROCEDURE 12At.l

Purpose
Procedure 12A2.1 is presented for calculating the thermal conductivity of liquid hydrocarbon
mixtures of known composition at any temperature and pressure fiom the pure-component data under
the same conditions.

Reliability
Average deviations of values calculated by this procedure fiom experimental data are
approximately 5 percent. Errors will rarely exceed 15 percent for hydrocarbons systems for which
reliable pure-component input conductivities are available.

Special Comments
Procedures 12A1.1 and 12A1.2 should be used to obtain the pure-component input data for this
procedure. For high pressures, the correction outlined in Figure 12A4.1 must be applied. To get
pure-component conductivities near the critical point, use Procedure 12A1.3.
Although not recommended when the mixture composition is known, Figure 12A3.1 may be used
for fast but less accurate estimates of mixture thermal conductivities. Figure 12A3.1 is the only
method available to be used for a liquid mixture containing a component that is above its critical
temperature.

Literature Source
The procedure is adapted fiom Li, AIChE Joirmal22 927 (1 976).

Example
Calculate the thermal conductivity of a 68-mole percent n-heptane-32-mole percent cyclopentane
(i-j) mixture at 32 F and 1 atm. The experimental thermal conductivities of n-heptane and
cyclopentane at these conditions (124) are 0.07639 and 0.08130 Btu per (hr)(sq ft)(deg F) per fi,
respectively.
From Chapter 1, the molecular weights are 100.2 for ,I-heptane and 70.13 for cyclopentane. The
density ofn-heptane at these conditions is 43.85 Ib per CU fi, and the density of cyclopentane is 47.60
Ib per CU ft according to the methods of chapter 6. The molar volumes are determined to be (1 00.2/
43.85)=2.285 CU ft per Ib-mole for rr-heptane and (70.13/47.60)=1.473 CU fi per Ib-mol for
cyclopentane. From equation (12A2.1-2), the value of 4, is calculated as follows:

k, = 2

4j= 0.07877 Btu per (hr)(sq fi)(deg F) per fi

The volume fiactions of the pure components are determined by using equation 912Aî. 1-3):

n-heptane: (0.68X2.285 )
= O .7672
(0.68 x2.285 )+(O32 )(i .471)

1997 12-17

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 S T D * A P I / P E T R O T D B C H A P T E R 12-ENGL 1992 0 7 3 2 2 9 0 0 5 b 7 0 9 0 505 ICI

12A2.1

cyciopentane: +=, (0.32 X i .473 ) =0.2328

(0.68 X2.2SS )+(0.32 X i .473 )

As a check, the sum of the volume fraction is (0.7672M.2328)=1.0,as required by equation (12A2.1-
4).
The thermal conductivity of the mixture is calculated by using equation 9 12A2.1-5):

130)
~~0.7672)2(0.07639)+2(0.7672)(0.S328)(0.07877)+(0.2328)2(0.08
k 4 . 0 7 7 5 1 Btu per (hr)(sq ft)(deg F) per fi

The experimental value (124) at these conditions is 0.07714 Btu per (hr)(sq fi)(deg F) per fi.

12-18 1997

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 =
___ ~~ ~~

S T D * A P I / P E T R O T D B C H A P T E R 12-ENGL 1772 0 7 3 2 2 9 0 O5b7091 4 4 2

12A3.1

PROCEDURE 12A3.1

THERMAL CONDUCTIVITY OF UNCHARACTERIZED LIQUID

PETROLEUM FRACTIONS AT LOW PRESSURES

Discussion
The following equation is to be used to obtain the thermal conductivity of uncharacterized
liquid petroleum fractions at low pressures and temperatures between 0-600 degrees Fahrenheit.

K = 0.07577- 4.1 x 10’5T (12A3.1-1)

mere:
K = thermal conductivity, in BTU per (hr)(sqfi)(deg F) per fi.
T = temperature, in degrees Fahrenheit

Procedure
Step i: Caiculate the thermal conductivity of the fraction using equation (1 2A3.1-1).

1997 12-19

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 ~~

STD.API/PETRO T D B C H A P T E R 12-ENGL 1992 0732290 05b7092 388 W .

12A3.1

COMMENTS ON PROCEDURE 12A3.1

Purpose
Procedure 12A3.1 allows quick estimation of thermal conductivity at low pressure as a
function of temperature for any liquid hydrocarbon, although the procedure was developed for
petroleum fiadons. For pressures above 500 pounds per square inch absolute, correct the value
from this procedure by using Procedure 12A4.1.

Limitations
This procedure is an oversimplication, inasmuch as molecular type and weight have not
been correlated. Accordingly, Procedure 12A.î. 1 should be used in preference for mixtures for
which the composition is known.

Reliability
Average errors of 10 percent can be expected fiom Procedure 12A3.1,with maximum
errors of 40 percent.

Literature Sources
This Procedure is the best representative of data from the following sources: 1 1, 16,41,
43, 51, 57,65,80, 127, 128, 130, 141, 170, 174.

Example
Calculate the thermal conductivity of atmospheric pressure of a liquid petroleum fraction
with temperature of 550.6F.
The thermal conductivity is calculated from equation (12A3.1-i)
K = 0.07577- 4.1x l o 5 550.6
K = 0.05320BTU per (hr)(sqft)(deg F) per ft

12-20 1997

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 S T D * A P I / P E T R O TDB C H A P T E R 12-ENGL 1992 0 7 3 2 2 9 0 0 5 b 7 0 9 3 214 W

12A3.2

PROCEDURE 12A3.2

THERMAL CONDUCTIVITY OF LIQUID PETROLEUM

FRACTIONS AT LOW PRESSURES

Discussion
The following equation is to be used to obtain the thermal conductivity of characterized liquid
petroleum fiactions at low pressures.

-
k =Mempo.= (9.961xlO-'- 5.364xlO"aT ) (12A3.2-1)

Where:
k = thermal conductivity, in Btu per (hr)(sq ft)(deg F) per fi.
MeABP = mean average boiling point, in degrees Rankine.
T = temperature, in degrees Fahrenheit.

Procedure
Stepl: Calculate the thermal conductivity of the fraction by using equation (12A3.2-1)

1997 12-21

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 S T D * A P I / P E T R O T D B C H A P T E R I i Z - E N G L 1772 0732270 05b7074 150 W

12A3.2

COMMENTS ON PROCEDURE 12A3.2

Purpose
Procedure 12A3.2 is presented to calculate the thermal conductivity of characterized liquid
petroleum fiactions at any temperature and low pressures.

Reliability
Average deviations of values calculated by this procedure from experimental data are
approximately 6 percent, maximum deviations are 24 percent.

Special Comments
This procedure oniy applies to liquid petroleum fiactions that are fúlly characterized, if the mean
average boiiing point is not known,it could be estimated by any two of the following characterization
properties: Watson characterization factor, K, aniline point, carbon-to-hydrogen weight ratio,
molecular weight by using Figure 2B6.1 of Chapter 2.

This procedure is applicable in the MeABP range of 607 R to i 545 R.

For mixtures that are not characterized at ali, Fig. 12A3.1 should be used.
For high pressures, the correction outlined in Figure 12A4.1 must be applied.

Literature Source
This procedure was developed at The Pennsylvania State University.

Example
Calculate the thermal conductivity of a liquid petroleum fraction with mean average boiling point
of 646.74 R at the temperature of 71.87 F.

The thermal conductivity is calculated from equation (12A3.2.1):

k = (646.74)0.2904 - 5.364x106-71.87)
* (9.961~10”

k = 0.06272 Btu per (hr)(sq A)(deg F) per A

The experiment value (127) at these conditions is 0.06402 Btu per (hr)(sq ft)(deg F) per ft.

12-22 1997

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 STD.API/PETRO T D B C H A P T E R 1 2 - E N G L 1772 0 7 3 2 2 7 0 0 5 b 7 0 9 5 077

1M3.3

PROCEDURE 12A3.3

THERMAL CONDUCTIVITY OF LIQUID PETROLEUM FRACTION

BLENDED WITH DEFINED LIGHT HYDROCARBON LIQUID MIXTURES

Discussion
This procedure is used for the calculation of the thermal conductivity of a liquid petroleum fraction
blended with a light hydrocarbon liquid mixture. Use equation (12A3.1-i) or equation (12A3.2-1)
to obtain the t h e d conductivity of the liquid petroleum fraction. Use Procedure 12Aî.1 to obtain
the thermal conductivity of the iight hydrocarbon iiquid mixtures. Then treat the light hydrocarbon
liquid mixtures and the petroleum fractions as pseudocomponents, using Procedure 12A2.1 to
calculate the thermal conductivity of the whole blend.

Procedure
Step 1: Obtain the thermal conductivity of the liquid petroleum fiaction by using equation
(12A3.1) or equation (12A3.2-1).
Step 2: Obtain the thermal conductivity of the defined light hydrocarbon liquid mixture by
using Procedure 12M.1 steps 1 through 6.
Step 3: Consider the liquid petroleum fraction and the light hydrocarbon liquid mixtures as
pseudocomponents, and obtain the thermal conductivity of the blend by using
Procedure 12Aî.1 steps 1 through 6 .

1997 12-23

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 S T D - A P I / P E T R O T D B C H A P T E R 12-ENGL 1772 0732270 05b707b T 2 3 m

12A3.3
COMMENTS ON PROCEDURE ltA3.3

Purpose
procedure 12A3.3 is presented to calculate the thermal conductivity of liquid petroleum fractions
blended with defined light hydrocarbon liquid mixtures.

Example
Calculate the thermal conductivity of a mixture containing 6O-mole percent liquid petroleum
M o n with a mean average boiling point of 646.74 R and a specific gravity of 0.698 blended with
15-mole percent n-penîane(l), 10-mole percent n-hexane(2), and 15% benzene(3) at 60 F and 1 atm.
The molecular weight of the petroleum fi-action is 94.257 as calculated from Chapter 2, the density
is calculated as (0.698)(62.27)=43.46 lb per fi3, thus the molar volume is (43.46)"(94.257)=2.1688
ft3per lbmol.
The thermal conductivity of the petroleum fraction is calculated from equation (12A3.1- 1):

k = 0.07577 - 4. 1x1o5(60.0)
k = 0.0733 1 Btu per (hr)(sq ft)(deg F) per (fi)

The thermal conductivity of the defined light hydrocarbon liquid mixture (the molar fractions are
normalized as 37.5 mole percent n-pentane, 25.0 mole percent n-hexane, and 37.5 mole percent
benzene in order to treat the defined mixture as a pseudocomponent) is calculated from Procedure
12A2.1. From Procedure 12A1.1, the liquid thermal conductivities of n-pentane, n-hexane and
benzene are 0.06772, 0.07109 and 0.08454 Btu per (hr)(sq A)(deg F) per fi, respectively at the
speciíìed conditions. From Procedure 6Aî. 13 and Procedure 6A3.1 of Chapter 6, the molar volumes
are determined to be 1.831 fi3/lbmolfor n-pentane, 2.066 fi3/lbmolfor n-hexane, 1.418 A3/lbmol for
benzene, and 1.7346 fi3/lbmol for the mixture. From equation (12A2.1-2), the values of kj is
calculated as follows:
1
= 2( )-I = 0.06936
0.06772 0.07109

1 + 1
k,, = 2( )-I = 0.07520
0.06772 0.08454

1
)-I = 0.07723
=' = 2(0.07109 0.08454
The volume fractions ofthe pure components are determined by using equation (12A2.1-3):
n-pentane: 8, = (0.375X1.831)
= 0.3958
(0.375 Xi .831)+(0.25X2.066 )+(0.375 )(i .418)

n-hexane: 8, = (0.25X2.066 )
= 0.2977
(0.375)(I .831)+(0.25 X2.066 )+(O375 )(i ,418)

benzene: 0, = (0.375X1.418 )
= 0.3065
(0.375XI .831)+(0.25 x2.066 )+(0.375 Xi .418)

12-24 1997

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 S T D * A P I / P E T R O T D B C H A P T E R 12-ENGL 1 7 9 2 0732290 05b7097 7bT

12A3.3

The thermal conductivity of the mixture is calculated by using equation ( 12A2.1-1):

c,=c a,e~~=e,2L1+a~k2+e~k3+2e,e~12+2e1e~13+2e2e~~

k,,,= (0.3958)2(0.06772)+ (0.2977)*(0.07109)+ (0.3065)*(0.08454)+ 2(0.3958)(0.2977)(0.06936)

+ 2(0.3958)(0.3065)(0.07520) + 2(0.2977)(0.3065)(0.07723)
k,,, = 0.07354 Btu per (hr)(sq A)(deg F) per (ft)
The petroleum hction(i) and the defined hydrocarbon liquid mixture@ are treated as two
pseudocomponents, and Procedure 12A2.1 is applied again to calculate the thermal conductivity of
the blend. From equation (12A2.1-2), the values of kjis calculated as follows:
k..= 21 l + )-' = 0.07342
0.07331 0.07354
The volume fractions of the pseudocomponentsare determined by using equation (12A2.1-3):

liquid petroleum fiaction: e. = (0.6x2.1688 )

= 0.6522
(0.6x2.1688 )+(0.4)(1.7346 )

defined hydrocarbon liquid mixture: 0. = (0.4X1.7346 )

= 0.3478
' (0.6x2.1688 )+(0.4)(1.7346 )

The thermal conductivity of the blend is calculated by using equation (12A2.1-5):

= (0.6522)2(0.0733i ) + 2(0.6522)(0.3478)(0.07342)+ (0.3478)*(0.07354)

k,,,= 0.07339 Btu per (hr)(sq ft)(deg F) per (fi)

1997 12-25

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 S T D . A P I / P E T R O T D B C H A P T E R 12-ENGL 1 9 9 2 O732290 05b7078 8Tb

12A4.1

PROCEDURE 12A4.1
THERMAL CONDUCTIVITY OF LIQUID HYDROCARBONS
AT HIGH PRESSURES

Discussion
The following equations are to be used to obtain thermal conductivity for liquid
hydrocarbons in the reduced temperature range 0.4-0.8and pressures greater than 500 pounds per
square inch absolute:
4.45 (12A4.1-1)
c,
2.065 T
.
C = 17.77 + O.û65P, - 7.764T, - (12A4.1-2)
olp(0-2Pr)

Where:
k2
- thermal conductivity at the desired temperature and pressure, in Btu per (hr)(sq
fi) (deg F) per A.
thermal conduc&ity at the same temperature and another pressure (usually
atmospheric), in Btu per (hr)(sq ft)(deg F) per A.
CI, c2 = conductivity factors calculated from equation (12A4.1-2) corresponding to the
reduced conditions applicable to k, and k2, respectively.
reduced pressure PP,
pressure, in pounds per square inch absolute
critical pressure, in pounds per square inch absolute
reduced temperature, T/Tc
temperature, in degrees Rankine
critical temperature in degrees Rankine

Procedure
Step I : From Chapter 1 determine the critical temperature and critical pressure, then
calculate the reduced temperature and reduced pressure.
Step 2: If the reduced temperature falls within the range .4-.8then calculate C, and C,
from equation (12A4.1-2).
Step 3: Find a literature value for the thermal conductivity of the liquid at the same
temperature and different pressure.
Step 4: Calculate k2from equation (12A4.1-1).

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 S T D . A P I / P E T R O T D B C H A P T E R 12-ENGL 1792 H 0 7 3 2 2 9 0 05b7077 732 W

12A4.1

COMMENTS ON PROCEDURE 12A4.1

Purpose
Procedure 12A4.1 is presented for estimating the effect of pressure on the thermal
conductivities of liquid hydrocarbons when the pressure is greater than 500 pounds per square
inch absolute.

Reliability
The average error in the pressure correction alone is approximately 5 percent, with a
maximum error of 25 percent. The final thermal conductivity, k,, also is subject to error from the
input value, k,.

Literature Source
The procedure was adapted from Lenoir, Petroletrrn Refiner 36[8] 162 (1957).

Example
Calculate the thermal conductivity of liquid toluene at 87.5 F and 22,044 psia. From
Chapter 1, the critical temperature is 1065.22 R and the critical pressure is 595.90 psia. A
literature value (53) for the thermal conductivity of the liquid at 87.5 F and 14.696 psia is k =
0.07425 Btu per (hr)(sq fi)(deg F) per ft. For this condition the reduced temperature is
87.5 + 459 d7 = 0.5136 and the reduced pressure P = 14.696 = 0.0247 . The reduced
1065 .22 *I 595.90
temperature falls within the range of .4 to .8. Using equation (12A4.1-2) the conductivity factor
2.054 * 0.513646
C, = 17.77 + 0.065 * 0.024662 - 7.764 * 0.513646 -
q(0.2 0.024662 )
= 13.2444.

For the evaluated pressure condition, the reduced temperature is also 0.5136 and the
reduced pressure P , ~is -
U044
= 36.993 . Using equation (i 2A4.1-2) the conductivity factor
595.90

C, = 17.77 + 0.065 * 36.993 - 7.764 * .513646 - 2.054 0.51362 = 16.1863.

~ ( 0 . *2 36.993)
By using equation (12A4.1-1), k2 = k, (C,/C,) = )*j16.1863 = 0.09074 Btu per (b)(sq
13.2444
ft)(deg F) per fi. An experimental value (53) is 0.09435 Btu per (hr)(sq ft)(deg F) per ft.

1997 12-27

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 ~~

STD-APIIPETRO TDB CHAPTER 12-ENGL 1992 0732290 05b7100 284 W

12B1.1

PROCEDURE 12B1.1
THEXMAL CONDUCTIVITY OF PURE HYDROCARBON
GASES AT LOW PRESSURE

Discussion
The following equation is recommended for predicting the thermal conductivity of pure
hydrocarbon gases at pressures below 50 pounds per square inch absolute:

k = A + BT + CT2 (12B 1 .1 .1)

Where:
k = thermal conductivity. in Btu per (hr)(sq ft)(deg F) per ft.
T = temperature. in degrees Fahrenheit.
4B. C = derived coefficients

The values of the coefficients A, B. and C are tabulated below for a number of compounds.
The temperature range of the data with which the coefficients were denved also is given.

mio3 B x 105 c x lo8 Temperature

Range (deg F)

Methane................................. 16.77 4.358 1.335 -285to 980

Ethane................................... 8.74 4.343 1.364 32 to 850
Propane................................. 7.54 3.362 1.971 -40to 1000
n-Butane ................................ 6.91 2.809 2.841 32 to 340
??-Pentane............................... 6.76 2.337 2.778 32 to 340.

n-Hexane............................... 6.42 2.214 2.180 32 to 770

??-Heptane.............................. 4.95 2.444 1.685 220 to 790
n-Octane ................................ 3.59 2.710 1.175 290 to 750
n-Nonane ............................... 3.60 2.453 1.237 350 to 760
>?.Decane............................... 0.72 3.200 0.470 350 to 760

n-undecane............................ 1.77 2.461 1.111 390 to 750

n.Dodecane ............................ -0.84 3.190 0.405 470 to 740
n-Tridecane ............................ 0.22 2.714 0.637 490 to 740
n.Tetradecane ......................... -4.02 3.810 -0.233 525 to 720
n.Pentadecane ......................... -4.30 3.850 -0.450 560 to 700

n-Hexadecane......................... -6.79 4.350 -0.828 590 to 700

2-Methylpropane..................... 7.17 2.849 3.131 32 to 212
2-Methylbutane....................... 7.92 0.774 8.393 120 to 212
Ethene.................................. 9.33 3.231 2.139 -140to 600
Propene ................................ 7.23 3.296 1.442 70 to 700

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S T D - A P I / P E T R O T D B C H A P T E R 12-ENGL 1772 0732270 0 5 b 7 1 0 1 110 9

12B1.1

1-Butene............................... 7.72 1.475 6.590 70 to 212

1-Hexene.. ............................ 5.14 2.802 1.311 170 to 650
1-Heptene............................. 4.13 3.049 0.693 212 to 670
1-Octene................................ 3.79 2.904 0.606 280 to 430
Ethyne.................................. 10.98 2.53 1 2.038 32 to 400

Cyclopropane.......................... 8.09 1.O83 7.526 120 to 300

Cyclohexane........................... 4.50 2.4 14 2.572 210 to 680
Benzene. ................................ 2.58 3.235 O. 160 210 to 740
Toluene................................. 0.94 4.005 -0.275 300 to 730
Ethy1benzene. .......................... -0.49 4.039 -0.231 360 to 760

1,2-Dimethylbenzene (+Xylene). .. 5.16 2.964 0.095 370 to 790

1,3-Dimethylbenzene @-Xylene). . 6.96 1.520 1.880 410 to 800
1,4-Dimethylbenzene @-Xylene)... 1.64 3.418 0.24 1 350 to 780
n-Propylbenzene....................... -0.42 4.276 1.266 360 to 650
Isopropylbenzene...................... -4.64 7.580 -2.036 360 to 660

Procedure
For the desired compound, obtain the appropriate coefficients from the given tabulation and
use equation (12Bl.i-i) to calculate the thermal conductivity at the temperature of interest.

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STD.API/PETRO TDB CHAPTER 12-ENGL 1 9 9 2 W 0 7 3 2 2 9 0 O5b7102 o57

12B1.1

COMMENTS ON PROCEDURE 12Bl.l

Purpose
Procedure 12B1.1 is presented to calculate the thermal conductivities of pure hydrocarbon
gases at pressures below 50 pounds per square inch absolute. For higher pressures, the correction
from Procedure 12B4.1 should be applied. Within its range of applicability, this procedure is
somewhat more accurate than is Procedure 12B1.2.

Limitations
This method is intended for use only within the specified temperature regions.

Reliability
Average deviations of values calculated by this procedure fiom experimental data are less than
5 percent.

Literature Sources
The entries in the tabulation were derived fiom data from the following sources:

Methane (22,28,50,55,61,62,67,69,70,72, n-Hexadecane (104,169)

74,84,85,94,147,148,149,160,164, 2-Methylpropane (67,85,125)
165,176,183) 2-Methylbutane (67,125-1 76)
Ethane (23,31,40,62,67,69,70,71,72,155, Ethene (28,62,64,67,74,112,161,162,183)
162,179,183) Propene (67,312,113,126,161,162)
Propane (24,67,71,85,129,153,162,164, 1-Butene ( i 26,162,177)
179,183) ]-Hexane (110,1l2,113)
n-Butane (21,66,67,85,117,125,161,162, 1-Heptene ( 108,112,113)
164,177) 1-Octene (1 12,113)
n-Pentane (20,67,85,164) Ethyne (99,184)
??-Hexane(31,67,68,85,87,178,179) Cyclopropane (67,126,179)
??-Heptane(67,103,169) Cyclohexane (12,3 1,68,107,178,179)
n-Octane (67,103) Benzene (4,3 1,68,178,i 79)
n-Nonane (103,104) Methylbenzene (Toluene)(i )
??-Decane( 104,114) Ethylbenzene ( 5 )
n-Undecane ( 103,104,111,169) 1,2-Dimethylbenzene (o-Xylene) (2)
n-Dodecane (1 04) 1,3-Dimethylbenzene (m-Xylene) (2)
??-Tridecane(104) 1,4-Dimethylbenzene @-Xylene) (3)
ri-Tetradecane (103,104,169) n-Propylbenzene (46)
n-Pentadecane (104) Isopropylbenzene (46)

Example
Find the thermal conductivity of I-heptene at 268 F and 1 atm.
From the preceding tabulation, A = 4. i 3 x lo3, B = 3.049 x IO-’, C = 0.693 x l o 8 . The
thermal conductivity then is calculated by using equation 912B1.4-1):

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 STD.API/PETRO T D B CHAPTER 1 2 - E N G L 1792 0 7 3 2 2 9 0 05b7103 T 9 3 m

12B1.1

k = 4.13x 10” + (3.049x lo”) (268)+ (0.693x 10-*)(268)’

k = 0.01280Btu per (hr)(sq ft)(deg F) per fi.

An experimental value (1 13) is 0.01309Btu per (hr)(sq ft)(deg F) per fi.

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 S T D - A P I / P E T R O T D B C H A P T E R 12-ENGL 1 9 9 2 0732290 05b7104 72T

1281.2

PROCEDURE 12Bl.2

THERMAL CONDUCïïViTY OF PURE HYDROCARBON GASES

AT LOW PRESSURES, GENERALIZED METHOD

Discussion
The following equations are to be used to obtain the thermal conductivity of pure
hydrocarbon gases at pressures below 50 pounds per square inch absolute.
For methane and cyclic compounds at reduced temperatures less than 1.O:

TC ( 12B1.2-1)
I; = 1.188 x
1

For methane and cyclic compounds at reduced temperatures greater than 1.O and for all
other compounds at any temperature:

k = (2.67 x lo-‘ (14.52Tr- 5.14)” -

cP
1
( 12B1.2-2)

( --i”
1 = T0/6M112 14.696 (12B 1.2-3)

mere:
k = thermal conductivity, in Btu per (hr)(sq fi)(deg F) per foot.
T, = reduced temperature, T/T,.
T = temperature, in degrees Rankine.
T, = critical temperature, in degrees Rankine.
c, =isobaric heat capacity, in Btu per (ib-mole)(deg R).
M = molecular weight.
-
P c - critical pressure, psia.

Procedure
Step I : Obtain the critical temperature, T,, the critical pressure pc, and molecular
weight, M, from Chapter 1.
Step 2: Calculate A from equation (12B 1.2-3).
Step 3: Calculate the reduced temperature (T, = T/T,).
Step 4: Obtain the isobaric heat capacity according to the method of Chapter 7 and
convert to a Btu per (lb-mole)(deg R) basis.
Step 5: Depending on the reduced temperature and compound type, calculate the
thermal conductivity using either equation (12B1.2-1) or equation (12Bi .2-2).

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12B1.2

COMMENTS ON PROCEDURE 12B1.2

Purpose
Procedure 12B1.2 is presented to calculate the thermal conductivity of pure hydrocarbon
gases at pressures less than 50 pounds per square inch absolute. For higher pressures, apply the
correction outlined in Procedure 12B4.1. When Procedure 12B1.1 is applicable, it should be used
in preference to this procedure.

Reliability
This procedure yields average errors of 5 percent and maximum errors of 40 percent.

Literature Source
This procedure is adapted from Misic and Thodos, AKhE Journal 7 264 (1961).

Example
Calculate the thermal conductivity of 2-methylbutane at 212 F and I atm.
From Chapter 1, the critical temperature is 369.1 F, the critical pressure is 498.38 psia,
and the molecular weight is 72.15. The value of A is therefore:

(369 .I + 459 .67)"6(72.15)'R

A =
(490.38114.696 )"

h = 2.512

The reduced temperature is (212 +459*67) = 0.810. From Chapter 7, the isobaric heat
369.1 +459.7)
capacity is 34.49 Btu per (Ib-mole)(deg R).
The thermal conductivity for 2-methylbutane is then calculated by using equation
( 12B1.2-2):

k = (2.67 x [(14.52) (0.810) - -

5.14)p34.49
2.512

k = 0.01293 Btu per (hr)(sq ft)(deg F) per fi.

An experimental value (124) at these conditions is 0.01333 Btu per (hr)(sw ft)(deg F) per

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 STD.API/PETRO T D B C H A P T E R 1 2 - E N G L 1792 0732290 05b710b 7T2

12B2.1

PROCEDURE 12B2.1

THERMAL CONDUCTIVITIES OF DEFINED MIXTURES

OF HYDROCARBON GASES

Discussion
The foiíowing equations are to be used to predict the thermal conductivity of vapor mixtures of
known composition at any conditions of temperature and pressure. The conductivities of the pure
components are required at the same conditions.
n
km = 4 (12B2.1-1)
. n
ir1

Where:
k,,, = thermal conductivity of the mixture, in Btu per (hr)(sq ft)(deg F) per A.
IC, = thermal conductivity of component i, in Btu per (hr)(sq ft)(deg F) per A.
n = number of components in the mixture.
yi, yj = mole fiactions of components i and j.

( 12B2.1-2)

Si, Sj (Sutherland Constants) = 1.5 T, (12B2.1-3)

Si, Sj = 142"R for hydrogen, deuterium, and helium. (12B2.1-4)

s, = Js7s; (12B2.1-5)

Note that A,j # $,.

Where:

pi, pj = viscosities of components i and j, in centipoises.

M,, M, = molecular weights of components i and j.
T, = normal boiling point, in degrees Rankine.
T = temperature, in degrees Rankine.

This method is also applicable to mixtures of nonhydrocarbons, including hydrogen.

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 STD.API/PETRO T D B CHAPTER 12-ENGL 1792 W 0 7 3 2 2 9 0 05b7Lü7 b37

1282.1

Procedure
Step I : Obtain the molecular weights and nonnai boiling points of the pure components of the
mixture from Chap. 1 and calculate the thermal conductivities by using Procedure
12B 1 . 1 or 12B 1.2. If the values are required at elevated pressures, use Procedure
12B4.1 to correct for the effect of pressure.
Step 2: Calculate Si, Sj, and S, from equations (12B2.1-3) and (12B2.1-4).
Step 3: Obtain the pure component viscosities using the method of Chap. 1 1.
Step 4: From equation (12B2.1-2), calculate the factors bj.
Step 5.- Obtain the thermal conductivity of the mixture from equation (12B2.1-1).

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 STD.API/PETRO TDB CHAPTER 12-ENGL 1992 0732290 05b7108 575

12B2.1

COMMENTS ON PROCEDURE 12B2.1

Purpose
Equation (12F32.1-1) is used to calculate the thermal conductivity of a gaseous mixture for which
the composition is known, using pure-component conductivities under the same conditions.

Reliability
Equation (12B2.1-1) yields average errors of approximately 5 percent and maximum errors of 40
percent when compared with the available data.

Special Comments
Equation (12B2.1-i) also will yield reliable results for many nonhydrocarbon systems, including
mixtures containing polar compounds.
For mixtures of quantum gases (hydrogen, helium, and neon) and hydrocarbons where the fiaction
of the quantum gas is known but the composition of the hydrocarbon portion is not, use Procedure
12B3.1 to obtain a kj for the entire hydrocarbon portion of the mixture, which is then treated as a
pseudocomponent in this procedure.
Although not recommended when the mixture composition is known. Procedure 12B3.1 may be
used for fast but less accurate estimates of mixture thermal conductivities.

Literature Source
This procedure is adapted fiom Lindsay and Bromley, h i d . Eng. Chent. 42 1508 (1950).

Example
Calculate the thermal conductivity of a 29.96-mole percent n-pentane( i ) - 70.04-mole percent
n-hexane(2) mixture at 2 12 F and I atm. The experimental thermal conductivities of n-pentane and
n-hexane at these conditions (42) are 0.01280 and 0.01165 Btu per (hr)(sq fi)(deg F) per fi,
respectively.
The molecular weights and normal boiling points are taken fiom Chapter 1.
n-pentane: M = 72.15; T, = 96.93 F
n-hexane: M = 86.18; T, = 155.71 F
The Sutherland constant of n-pentane is S, = 1.5(96.93+459.67) = 834.9 R and the Sutherland
constant of n-hexane is S, = 1.5(155.71+459.67) = 923.07 R. The factor S,, = S,, is therefore
4(834.9)6923.07)=877.88' From Chapter 11, the viscosities of n-pentane and n-hexane are determined

to be 0.008631 and 0.008129 centipoise, respectively. By using equation (12B2. i-2), the factors A,j
are calculated as follows:
A,, = A2, = 1.0

A12=L1+ 0.008631
4
[ 86.18) 212 +459.67 212 +459.67
0.008129 72.15
212 4 9 . 6 7 212 +459.67

AI2= 1.102

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 S T D . A P I / P E T R O T D B C H A P T E R 1 2 - E N G L 1772 0 7 3 2 2 9 0 0 5 b 7 1 0 9 401

12B2.1

r[(
4

A,, = 0.9087
I 0.008129
A 1 2 = L 1. --I
0.008631 \ 86.18
[+
72.15 \ 3/4 '
923 .O7
212 +459 A7 '

212 +459.67
) I f '
1+
212 +459.67
923 .O7
212 +459 -67

The mixture's thermal conductivity is calculated next by using equation (12B2.1-1):

0.01280 0.01165
km= A

0.2996
[(1.0)(0.29% )+(1.102 X0.7004 )] -
O .7004
[(0.9087 X0.2996 )+(1.0)(0.7004 )]

k,,, = 0.01197 Btu per (hr)(sq ft)(deg F) per ft

An experimental value (42) is 0.001188 Btu per (hr)(sq ft)(deg F) per fi.

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1283.1

PROCEDURE 12B3.1

THERMAL CONDUCTIVITY OF PETROLEUM FRACTION

VAPORS AT LOW PRESSURES
Discussion
The following equation is to be used to estimate the thermal conductivity between a
temperature range of 0-1000degrees F and a molecular weight range of 15-150@mol.
(1 2B3.1-1)
Mw Mw2

thermal conductivity at T in BTU per (hr)(sq ft)(deg F) per fi

temperature, in degrees Fahrenheit
molecular weight
0.0013349
0.24628
1.1493
3.2768x
4.1881x
0.0018427

Procedure
Step I : After knowing the temperature and molecular weight, check to see if they fall
in the specified range.
Step 2: Plug in the values for the constants A-F, the values for T and MW and
calculate the thermal conductivity from equation (12B3.1-1).

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 S T D - A P I I P E T R O T D B C H A P T E R 1 2 - E N G L I772 0732270 0 5 b 7 L L L ObT

12B3.1

COMMENTS ON PROCEDURE 12B3.1

Purpose
Procedure 12B3.1 is to be used for estimation of the thermal conductivity of hydrocarbon
vapor mixtures of undefined composition at low pressures where the vapor may be considered to
be an ideai gas. Procedure 12B1.2is more accurate and is preferable when the input data are
available. For higher pressures, apply the pressure correction, Procedure 12B4.1.

Limitations
This method is an oversimplification which should be used only when other methods of the
chapter are inapplicable. Procedure 12B3.1 must not be used for mixtures containing quantum
gases (hydrogen, helium, or neon).

Reliability
This procedure is in error by an average of 10 percent except for mixtures containing
appreciable quantities of hydrogen, helium, or neon where an average error of 25 percent is
obtained. No data for petroleum fiaction vapors are available for comparison.

Literature Source
This procedure is a regression of a figures which is a similar figure presented by Maxwell.
"Data Book on Hydrocarbons." 215. D. Van Nostrand Company, Inc., Princeton, New Jersey
(1950), based on thermal conductivity data of defined vapor mixtures from the following sources:
26,28, 29,40,42, 52, 59, 60, 89, 125, 126, 149, 164, 183.

Example
Calculate the thermal conductivity of a petroleum fiaction vapor at a low pressure and a
temperature of 455 F which has a molecular weight of 138 g/mol. The thermal conductivity is
calculated from equation (12B3.1-1)
k = 0.0013349 +
0.24628 + - 1.1493
138 138
3.2768 x IO-' +
4.1881 x IO-'
138
0.0018427
138 1
k = 0.01828 BTU per (hr)(sq ft)(deg F) per fi.

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 S T D * A P I / P E T R O T D B C H A P T E R 1 2 - E N G L 1772 0732270 0 5 b 7 L L 2 T T b

1284.1

PROCEDURE 12B4.1

THERMAL CONDUCTIVITY OF PURE HYDROCARBON GASES

AT HIGH PRESSURES
Discussion
The following equations are to be used to predict the effect of pressure on the thermal
conductivity of hydrocarbon gases when the pressure is greater than 50 pounds per square inch
absolute:

Khere:
k - thermal conductivity at temperature and pressure of interest, in Btu per (hr)(sq
fi) (deg F) per fi.
thermal conductivity at temperature of interest but at a low pressure (usually
atmospheric, in Btu per (hr)(sq ft)(deg F) per fi.
isochoric heat capacity of the real gas, in Btu per (Ib-mole) (deg F).
translational isochoric heat capacity of the real gas to be calculated from
equation (12B4.1-7), in Btu per (lb-mole)(deg F).
internal isochoric heat capacity of the real gas, Cv- Cv',in Btu per (Ib-
mole)(deg F).
translational contribution to the thermal conductivity ratio which is given
analytically as a function of T,and p, as equation (12B4.1-2).
internal contribution to the thermal conductivity ratio which is given
analytically as a function of T, and P, as equation (12B4.1-5) for noncyclic
hydrocarbons and as equation (12B4.1-6) for cyclic hydrocarbons.
Tr reduced temperature, T/T,.
T temperature, in degrees Rankine.
TC critical temperature, in degrees Rankine.
PI reduced pressure, p/pc.
P pressure, in pounds per square inch absolute.
Pc
+ 0.537 <]
critical pressure, in pounds per square inch absolute.

TI
11.0 - C X ~ ( A P ~+) ]0.510 2
T,
..~(AP:) (12B4.1-2)

where:
A = -0.0617exp IT] 1.91
(12B4.1-3)

B = 2.29og [ F] (12B4.1-4)

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 S T D . A P I / P E T R O T D B C H A P T E R 1 2 - E N G L 1772 = 073227U 05b7LL3 732

1204.1

For noncyclic hydrocarbons:

4
P* + 0.012 -
p, (12B4.1-5)
2.44T: + p: T,

For cyclic hydrocarbons:

5
(kk 3' cyclic = 1.0 + -
O .520
:
T [ 5.38
PI

+ p j
+ 0.009 2
Tr
P
( 12B4.1-6)

The isochonc heat capacity, C, can be obtained according to the methods of Chapter 7.
The translational heat capacity can be calculated from the following equation:

Where:
C, = 4.965 - R
[
1
+ [CR
(12B4.1-7)

R = gas constant = 1.986 Btu per (lb-mole)(deg R).

= effect of pressure on isochoric heat capacity for the simple fluid which is
obtained from Chapter 7.

The internal heat capacity, C,., is then calculated as the difference between the total isochoric heat
capacity and the translational capacity, Cy = C, - Cv'.

Procedure
Step 1: Obtain the critical temperature, T,, and the critical pressure, pc, from Chapter 1
and determine the thermal conductivity of the low-pressure gas from
Procedure 12Bl.l or 12B1.2.
Step 2: Calculate the reduced temperature and the reduced pressure.

Step 3: From Chapter 7, obtain the isochoric heat capacity, C , and

[ E'R y o ) . Use

equation (12B4.1-7) to calculate the translational heat capacity, C,',and then

obtain the internal capacity, Cv"= C, - C,'.
Step 4: Calculate the coefficients A and B from equations (12B4.1-3) and (12B4.1-4)
and use these values in equation (12B4.1-2)to determine the translational
contribution to the thermal conductivity ratio, (Wk')'.
Step 5: Depending on compound type, use either equation (12B4.1-5) or (12B4.1-6)
to calculate the internal contribution to the thermal conductivity ratio, (fi')'.
Step 6: Obtain the thermal conductivity ratio from equation (12B4.1-1) and multiply
the result by the low-pressure vapor thermal conductivity, k', to determine the
thermal conductivity of the dense gas.

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 STD-API/PETRO T D B CHAPTER 1 2 - E N G L 1772 = 0732270 05b711'4 879 9

1284.1

COMMENTS ON PROCEDURE 12B4.1

Purpose
Procedure 12B4.1 is presented for estimating a correction to the low-pressure thermal
conductivity of hydrocarbons in the dense-gas region.

Reliability
Average errors between calculated and experimental thermal conductivities of dense gases
are 10 percent except in the critical region, where 20-percent errors should be expected and errors
as high as 70 percent can occur.

Literature Source
This procedure is adapted from Crooks, M.S.thesis. The Pennsylvania State University,
University Park, Pennsylvania (1978).

Example
Calculate the vapor-phase thermal conductivity of n-heptane at 472 F and 1450 psia.
From Chapter 1, the critical temperature of n-heptane is 5 12.69 F and the critical pressure
is 397.41 psia. By using Procedure 12B1.4, k' (572 F, 1 atm) = 0.02444 Btu per (hr)(sq ft)(deg
F) per fi. The reduced temperature is (572 + 459.67)/(519.69 +459.67) = 1.061, and the reduced
pressure is 1450/397.41 = 3.65. From Chapter 7, the total isochoric heat capacity is determined
to be 66.52 Btu per (lb-mole)(deg F) and is -0.409. The translational isochoric heat

capacity is calculated by using equation (12B4.1-7):

C,' = 4.965 = 1.986 [ 1 + (-0.409)J

C,' = 3.79 Btu per (Ib-mole)(deg F)

The internal isochoric heat capacity is therefore (66.52 - 3.79) = 62.73 Btu per (lb-mole)(deg F).
The coefficients A and B are calculated by using equations (12B4.1-3) and (12B4.1-4):

A = -0.0617 e ~ p [- = 0.189

B = -2.29
6,1)(]:[. = 3-85

By using equation (12B4.1-2):

[
(RIR >'= 1.o + 4.18 +OS37
(1.061 )4
(3.65)
(I .o61 )*
[1.O - ag (- O. 189 (3.65 )3.85))]+0.Si0 3.65 ~q(-0.189(3.65)~.")
(1.061)3

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 STD.API/PETRO TDB CHAPTER 12-ENGL 1992 0732290 05b7115 705

1284.1

(kk')= 1 .O+ 5.04+ 0.0= 6.04

Because n-heptane is noncyclic, equation 912B4.1-5)is used to calculate the internai contribution
to the thermal conductivity ratio:

(klk>'= 1.0 + - 3.65)' ]+ 3.65

2.44(1.061)M + (3.65)' 1.061

(k/k').= 1.0+ 0.712+ 0.041= 1.753

Therefore, using equation (12B4.1-1):

W? 3 79
= ,-(6.04) +
62 73
-{1.753) = 1.997
66 S2 66.52

The actual high-pressure thermal conductivity is (1.997)(0.02444)= 0.04881 Btu per (hr)(sq
ft)(deg F) per ft.

An experimental value (106)is 0.04813Btu per (hr)(sq ft)(deg F) per ft.

1997
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 = 0732290 0 5 b 7 L 1 b
~~

S T D . A P I / P E T R O T D B C H A P T E R 12-ENGL 1992 bll1

12c1.1

PROCEDURE 12Cl.l

THERMAL CONDUCTIVITY OF SELECTED NONHYDROCARBONS

Discussion
The following equation is to be used to obtain the thermal conductivity of selected
nonhydrocarbons at vanous temperatures and pressures.

k = A + BT + cT2 + DP + E- P + F +G In p (12c1.1-1)
T (0.4P-0.001T)0~0'5

where:
k = thermal conductivity in BTU per (hr)(sq ft)(deg F) per foot
T = temperature in degrees Rankine
P = pressure in pounds per square inch absolute

Procedure
Step I : Obtain the constants for equation (12C1.1-I) from Table 12C1.2.
Step 2: Check to see if the desired temperature and pressure are within the limitations
of the equation.
Step 3: Calculate the thermal conductivity using equation (12Cl.l-1).

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 S T D - A P I / P E T R O T D B CHAPTER 12-ENGL 1 7 7 2 0 7 3 2 2 7 0 0 5 b 7 1 1 7 588 =

12Cl.l

COMMENTS ON PROCEDURE 12Cl.l

Purpose
Procedure 12C1.1 is to be used to estimate the thermal conductivity of selected
nonhydrocarbons at various temperatures and pressures.

Limitations

Temperature Range (deg. R) Pressure Range (psia)

Nitrogen 460 to 2,460 15 to 10,000
Carbon Monoxide 460 to 2,460 15 to 10,000
Oxygen 460 to 2,460 15 to 15,000
Hydrogen 260 to 2,260 15 to 10,000
Sulfur Dioxide (gas) 960 to 2,460 15 to 10,000
Hydrogen Sulfide 460 to 2,460 Atmospheric
Sulfur Trioxide 460 to 2,460 Atmospheric

Procedure 12C1.1 is not recommended outside of the above ranges.

Reliability
The error for the data before regression did not exceed five percent. The average error
for the regression was:

Number of Tested Points Average Absolute % EITOJ

Nitrogen 155 1.69
Carbon Monoxide 229 1.81

Oxygen 151 1.88

Hydrogen 77 1.72
Sulfùr Dioxide (gas) 96 2.98
Hydrogen Sulfide 11 <O. 5
Sulfur Trioxide 11 3.81

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 S T D S A P I I P E T R O T D B C H A P T E R 1 2 - E N G L 1772 0732270 05b7118 4 L 4

12c1.1

Literature Source
Hydrogen - Schaefer and Thodos, Ind Eng. Chem. 60 1585 (1958).
Oxygen, Nitrogen, Carbon Monoxide - Stiel and Thodos, The Prediction of Transport
Properties of Pure Gaseous and Liquid Substances, in Progress in International Research on
Thermodynamic and Transport Properties, Chapter 3 1, ASME, 1962.
Sulfur Dioxide - Institute of G a s Technology Data Book.
Sulfúr Trioxide, Hydrogen Sulfide - Daubert, T. E., Damer, R.P.,Data Compilation:
Tables of Properties of Pure Compounds, American Institute of Chemical Engineers, New York
(extant 1995).

Example
Calculate the thermal conductivity of oxygen at 984.67degrees Rankine and 6075.0
pounds per square inch absolute.
Obtain the constants for oxygen from Table 12C1.2. They are:

A = 5.950x lo4 ,
B = 1.710 x lo-’
c = 0.000
D = -2.100x 10’
E = 5.869x
F = 6.995 x
G = 0.000
Check to see if the temperature and pressure are within the limitations for oxygen.

Limitations for oxygen are:

T (R) 460 to 2,460

P (psia) 15 to 15,000
The temperature and pressure fall within the limitations.

Calculate the thermal conductivity of oxygen using equation (12C 1.1- 1).

6075 .o
k = A + B x 984.67 + C x 984.672 + D x 6075.0 + E
984 .67
( 12c1.1- 1)
+ F
+ G in (6075 .O)
(0.4 x 6075 .O - 0.001 x 9&4.67)0.0’5

The calculated thermal conductivity is 0.03265BTU per (hr)(sq ft)(deg F) per foot.

12-46

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 S T D - A P I / P E T R O T D B C H A P T E R 1 2 - E N G L 1972 m 0 7 3 2 2 7 0 05b7LL7 350 m

12c1.2

O 0
O
O
0
0
8O x0 80 O
O
O
0
0
0
O 0 9 . 9 9 9
O 0 0 - 0 O 0

i
O
7
0
f?
O
CI
-x
c:O

LL x o i O 0
VI O 0
O 0
F
m p 9 9
D O Y O 0

n
w
I
L1

i;
e4
œ
I -n

u
O
c -ò
X
ò
c

X
X

o o
\9
1 o
P4
r?
m
-
e-
4

N
i
O
c

X
-
3
O
X
ò
c
i
O
c

x
c

m.
c
I

E
c
Q)
M
MO
L n
-0 rA

5 M
v

1997 12-47

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 S T D - A P I / P E T R O T D B C H A P T E R 12-ENGL 1792 W 0 7 3 2 2 9 0 05b7120 0 7 2 m

12c1.3
12C THERMAL CONDUCTIVITY OF NONHYDROCARBONS

o
h
9
9
9
in
9
d
9 9
CI
9 6 O
O O O O O O O

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 STD-APIIPETRO TDB CHAPTER 12-ENGL 1992 0732270 05b712L T O 7

12C1.4

Q
h 9 O
9 9
O O

1997 12-49

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 STD.API/PETRO T D B C H A P T E R 12-ENGL 1 7 9 2 M 0 7 3 2 2 7 0 0 5 b 7 L 2 2 945

12C1.5
c
l
O
o,

O
O
9

O
O
0:

O
O
$!

U
u-
O a
3
k-
a
W
L
w
k-
O
s

O
O
9

O
O
P

O
O
N

Y
9 O
9
O

12-50 1997

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 12C1.6
O
-

Y
mO +3 O
O
9

u-
K
æ
I-
a
I
I:
w
n
s
I-

O I
u

1997
12-51

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Licensed by Information Handling Services
 STD.API/PETRO T D B C H A P T E R 12-ENGL 1 9 9 2 0732290 05b7124 71A

12C1.7

YI
œ
zU
œ
YI
LL

Yc

(Y
5
O O ò
d
8 o
h(
O
O

12-52 1997

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 S T D * A P I / P E T R O T D B C H A P T E R 12-ENGL 1772 = 0 7 3 2 2 7 0 0 5 b 7 1 2 5 b5'4 =

12C1.8

0.28

FIGURE 12C1.8
THERMAL CONDUCTIVITY
OF SULFUR DIOXIDE
(LOW RANGE)

I Approved: RPD & TED

0.16

0.12

0.08

0.04

O
O 250 500
TEMPERATURE, F

1997 12-53

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 ~~

STD-API/PETRO T D B C H A P T E R 1 2 - E N G L 1992 0732290 0 5 b 7 1 2 b 5 7 0 U

12C1.9

loo
TEMPERATURE, F

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 S T D . A P I / P E T R O T D B C H A P T E R L Z - E N G L i m 2 m o n z z q o 0 5 ~ 7 1 2 7427 m

12c1.10

1997 12-55

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 S T D * A P I / P E T R O T D B C H A P T E R 12-ENGL 1992 E 0732270 0 5 b 7 L 2 8 3 b 3 =

12Cl.11

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 STD.API/PETRO T D B C H A P T E R 1 2 - E N G L 1792 0732270 05b7127 2 T T 9

12c1.12

IL
W-
K
2
I-
a
a
W
n
w
c

1997 12-57

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 S T D * A P I / P E T R O T D B C H A P T E R 1 2 - E N G L 1772 0732270 05b7L30 TIL

12c1.3-12c1.12

COMMENTS ONFIG. 12C1.3 THROUGH 12C1.12

.. ..
PUQOSû
Thamal conductivity data for 10 common nonhydrocarbon gases are presented for avail-
able temperature and pressure ranges.
Reliabllity
The maximum error for all atmospheric pressure data was slightly less than 5 percent with
a mean error for individual gases from 1 .5 to 3.0 percent. High-pressure data errors did not
exceed 5 percent.

Literature Sources
Hydrogen-Schaefer and Thodos, Ind. Eng. Chem. 50 1585 (1958).
Oxygen, nitrogen, carbon monoxide, carbon dioxide, water, ammonia-Stiel and Thodos,
“The Prediction of the Transport Properties of Pure Gaseous and Liquid Substances,” in
Progress in International Research on Thermodynamic and Tramport Properties, Chapter
3 1, ASME, 1%2.
Sulfur dioxide, sulfur trioxide, hydrogen sulfide-Institute of Gas Technology Data Book.

12-58
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 S T D m A P I l P E T R O T D B C H A P T E R 12-ENGL 1 9 9 2 W 0 7 3 2 2 9 0 05b7L3L 7 5 8

BIBLIOGRAPHY

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 ~~ ~

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34. Dick, M. F., "The Thexmal Conductivities of Some 50. Johnston, H. L., Gnlly, E. R., "The Thermal
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"Thermal Conductivity and Viscosity of Biphenyl and the B-70, Kerosene T-I and Fuel T-5 in the Liquid Phase," T,:
Terphenyls," J. Chem. Eng. Data 15 122 (1 970). Mosk. Aviats. Inst. Sb. Statei 1961 11321 94 (1961).
48. HoiTocks, J. K.. McLaughlin, E., "Non-Steady-State 66. Kramer, F. R., Comings, E. W., "Thermal
Measurements of the Thermal Conductivities of Liquid Conductivity of Butane at High Pressure: Correlation with
Polyphenyls," Proc. Roy. Soc. (London) Ser. A273 259 Other Gases," J. Chem. Eng. Data 5 462 (1960).
(1963). 67. Lambert, J. D., Cotton, K. J.' Pailthorpe, M. W.,
49. Horrocks, J. K., McLaughlin, E., "Thermal Robinson, A. M., Scnvens, J.' Vaie, W. R.F.,Young, R. M.,
Conductivity of Simple Molecules in the Condensed State," "Transpon Properties of Gaseous Hydrocarbons," Proc. Roy.
Trans. Faradqv Soc. 56 206 (1 960). Soc. (Zondon),Ser. A231 280 ( i 955).
49a. Institute of Gas Technoiog Data Book, Sulfur 68. Lambert, J. D., Stabes, E. N., Woods, S . D.,
Dioside, Des Plaines, IL. "Thermal Conductivities of Organic Vapours," Pr-oc. Roy.

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