CHAPTER 8

THERMAL CONDUCTIVITY AND THE MECHANISMS

OF ENERGY TRANSPORT

Of the three transport processes that are the subject of study, heat transport is probably the most
familiar, since it is a part of our daily experience. It is common knowledge that some
materials like metals conduct heat easily, while others like wood act as
thermal insulators. The processes that involve heat transfer frequently occur in plants.
chemical industries and refineries, thus heating crude oil to its bubble point is possible
separate it into its fractions in a distillation column. In any case where it is verified
heat transfer, we must first find the speed at which heat transfer occurs, since
This is to calculate a new equipment, or to make improvements to an already existing process.
In principle, we must remember that heat is only one of the forms of energy and that it is energy and
not the heat, which is conserved according to the first law of thermodynamics. Then we will study the
conservation of energy in detail, but in this chapter we are only interested in the transport of heat
and specifically only with the conduction of heat; that is, in the molecular transport of energy, since
the fundamental mechanism is the movement of molecules or electrons. Energy can also
to be transported by the global movement of a fluid, and then it is called energy transport by
convection; this form of energy depends on the density of the fluid. Another mechanism is the transport of
0
energy by diffusion, which occurs in mixtures that diffuse into each other. Energy can also be transmitted by
radiation, whose transport does not require a material medium, unlike conduction and convection
and diffusion, which is an electromagnetic phenomenon illustrated, for example, by the transport of heat.
from the sun to the earth through space.

8.1 FOURIER'S LAW OF HEAT CONDUCTION

MOLECULAR ENERGY TRANSPORT

Figure 8.1-1 Development of the temperature profile in steady state for a solid plate between two parallel sheets
See figure 1.1-1, which shows the analogous situation for the transport of momentum.

8-1
Let's consider a plate of a solid material with surface A.y, understood between two large sheets
planes and parallel lines separated by a distance Y = Ly, such thatxyLzthey are much older thanyso that
the heat will be transported only in the direction y. Let us assume that initially for t 0 the solid material
T
it is entirely at the temperature0 At the moment t 0 the lower face suddenly turns to a
T1
uniform temperature (higher
T
than0) and remains constant, while the upper face remains
to the temperature0T
To analyze the physical situation, let's outline the variation of the temperature T with the
position (see Figure 8.1-3), such a graph is called a temperature profile or temperature distribution.
T T ( y, t )
Since the temperature varies with time and position; that is to say we plotted TVs and various
times. At En = 0, the lower surface (eny = 0) will be at
T1 but the rest of the iron y 0 T
will be to0 . The
plotting of Tvsy, therefore it will be done at a right angle, which will display a slope of  eny= 0 and a
pending 0 in all the others and. In time1some heat will have penetrated a certain distance inside
from the plate and the temperature near the surface will have risen. At a later time2the heat
it will have reached the upper surface and will be flowing heat out of the plate. As the heat continues
Entering the board, the temperature at each position and inside the board will continue to increase with the
time, until the temperatures reach steady state, a condition in which the temperature in
each position remains constant over time and the temperature distribution is linear. Evidently
T T(y)
in the steady state, the temperature only varies with position; that is to say
Once steady-state conditions are reached, there must be a constant heat flow rate.
T T1 T0
Through the plate to maintain the temperature difference. .

Figure 8.1-2 Heat conduction in a thin plate.

Figure 8.1-3 Temperature vs. position on the plate at various times.

Macroscopic balance

Accumulation speed Net entry speed Generation speed

  1
of energy in the system of energy to the system. heat in the system

8-2
 T1 T 0
Since the heat enters through the bottom face of the plate at a speed Q1and comes out on the face
superior to speed0The heat is not being produced by chemical reaction or nuclear heating or
electric; therefore the generation speed is zero. In the stationary state the speed of
accumulation is also zero. Then in the previous equation we have:
0 Q1Q0 0, Q Q 1 Q0
(2)
Once steady-state conditions are reached, there must be a constant flow velocity.
T T1 T0
of heat through the plate so that the temperature difference is maintained .
0
Q f T 1T,A,Y,
 nature
y
of the material
3
Ay  T1 T 0 
Q
Y (4)
That is, the heat flow per unit area is directly proportional to the decrease of the
temperature, and to the area perpendicular to the direction of heat flow, and inversely proportional to the
distanceY. The constant of proportionality k is the thermal conductivity of the plate.
Q kT
Ay Y
(5)
Equation (5) also applies to liquids and gases situated between the plates as long as the conditions are met.
necessary precautions to avoid convection and radiation. This equation, therefore, describes the
conduction processes that occur in solids, liquids, and gases. The transfer mechanisms of
heat by convection and radiation is dealt with later. Then from (5)
Q 0 T T
k k  8.1 1 
Ay Y 0 y
y
at the limit when tends to zero:
T dT dT
lim , qy k  8.1 2 
y 0 y dy dy
A
The heat flow Q per unit areay(heat flux density of heat flux) that takes place in the
q
direction and positive, is designated by y 1.
This equation, which is used to define it, is the one-dimensional form of Fourier's law of conduction.
T T  y
heat, which is valid when It states that the heat flux density by conduction is
proportional to the negative gradient of temperature, or in a more graphical way, 'heat slides'
downhill in the graphic representation of temperature against distance." In reality, equation 8.1-2
it is not a law of nature, but rather a quite useful empiricism.

If the temperature varies in all three directions (in an isotropic medium), with k constant; so it is
It is possible to write an equation like 8.1-2 for each of the coordinate directions:
T T T
qx k q y k q z k  8.1 3, 4, 5 
x y z
If each of these directions is multiplied by the appropriate unit vector and then the equations are summed up.
resulting, it is obtained
q k T  8.1 6 
the three-dimensional form of Fourier's law. This equation describes heat transfer in media
isotropic; that conduct heat with the same thermal conductivity in all directions.
Some authors prefer to write equation 8.1-2 in the form
dT
q y  J ek  8.1 2a 
dy

8-3
 J
where e it is the 'mechanical equivalent of heat' that explicitly presents the conversion of units
thermal in mechanical units; for example, qyergios/cm2s.
R 1,987 cal/mol K 8,314 Pa m3/mol K 8,314J/molK; 1 cal 4,184J
Some solids, such as simple non-cubic crystals, fibrous materials, and laminates, are
anisotropic. For such substances, it is necessary to replace equation 8.1-6 with
q  T  8.1 7 
where It is a second-order symmetric tensor called thermal conductivity tensor. Therefore, the
The heat flux density vector does not point in the same direction as the temperature gradient.

El lector habrá observado que la ecuación 8.1-2 para la conducción de calor y la ecuación 1.1-2 para flujo
viscous are quite similar. In both equations, the flow density is proportional to the negative of
gradient of a macroscopic variable, and the coefficient of proportionality is a physical property
characteristic of the material and dependent on temperature and pressure. For situations where there is
three-dimensional transport, it is found that equation 8.1-6 for heat conduction and equation 1.2-7
For viscous flow, they differ only in appearance. This difference arises because energy is scalar.
while the quantity of motion is a vector, and the heat flux density is a vector with three
components, while the momentum flux density is a second-order tensor
with nine components. We can anticipate that the transport of energy and momentum by
General rules are not mathematically analogous, except in certain simple geometric situations.
In addition to thermal conductivity, defined by equation 8.1-2, a widely used
quantity known as thermal diffusivity, . It is defined as
k
Cˆp
 8.1 8 
pCp = specific heat capacity
Ĉ
Herepit is the heat capacity at constant pressure; the circumflex accent on the symbol indicates 'by
C p
mass unit". Occasionally, the symbol will be needed. where the tilde over the symbol represents a
amount 'per mole'.
Thermal diffusivity it has the same dimensions as kinematic viscosity , namely,
2
(length) / time. Its relationship / indicates the relative ease of transporting momentum and
energy in flow systems. This dimensionless relationship
Ĉ p
Pr  8.1 9 
k
it is called Prandtl number. Another dimensionless group that we will encounter is the Péclet number,
On Re/ Pr.
The units that are commonly used for thermal conductivity and some related quantities are
They are provided in table 8.1-1. Other units, as well as the interrelationships between the various systems,
can be found in appendix F.

8.2 HEAT CONDUCTIVITY OF GASES

Thermal conductivity is a property that is involved in most of the problems of
heat transfer. Its importance in energy transport is analogous to viscosity in transport.
movement; for this reason it is necessary to review the methods to estimate it, just as was done with the
viscosity.

I. Gases at low pressures

a) Theoretical method
The rigorous kinetic theory led to the equation:

8-4
 25 mkT
k Cv *
 i
32 2 2  2.2 
that in the case of a monoatomic gas, the equation is satisfied
3k
Ci  ii 
2mi
according to the bibliography1it can also be expressed this way:
25 (MRT)1/ 2 (TM)1/ 2
k c k 1,989.104  8.2 1 
(32)( 1/ 2
)N 2 2

o
expressing conductivity in cal/(cm.s.K), the collision diameter in A the temperature Ten K, and
it is the collision integral determined by equations 1.3-5.
C* C M
Introducing molar heat and dividing equation 8.2-1 by the equation:
 MT  1/2

 1.3 2 
26.69 2

kM
C*
2.5  8.2 2 
resulta:
C */C*
From this equation, and representing by the relationship p vbetween the molar heats at pressure and
constant volumes, the following expression for the Prandtl number is deduced:
C *p C*
Pr
kM kM 2.5
 8.2 3 
5/3
and since for the monatomic gases that are considered , except at very low temperatures,
Pr 2/3
for the same, according to equation 8.2-3, value very close to that which is found
experimentally. On the other hand, for them, recalling equation (ii), from equation 8.2-2 it is deduced:
k M 15 cal
R 7.5  8.2 4 
4 mol.K
since the only form of energy of the molecules is translational.

For a gas composed of polyatomic molecules with internal degrees of freedom (vibration and
rotation), Eucken1he proposed the following modification of equation 8.2-4:
kM
ftrC*  trf intC * int  8.2 5 
ftr f C*C*
representing y int two constants and tr , int the contributions of translational and internal energies
(of vibration and rotation) to molar heat.
Taking into account equations (ii) and 8.2-2 for monatomic gases, Eucken assumed the
the following values for the four magnitudes of the second member of equation 8.2-5:
3 * *
f tr 2.5 ;f * *
int 1 ; Ctr R;C int C C tr  8.2 6 
2
C *p/C * C *p C * R
With them, since y , from equation 8.2-5 it is deduced:
kM kM 1.25  8.2 7 
4.47 c * 2.48 c*p 2.25
c*p
what constitutes the Eucken equation for polyatomic gases, and which simplifies to equations 8.2-2 and
8.2-4 in the case of monatomic gases.

1
R.C. Reid, J.M. Prausnitz, T.K. Sherwood,The Properties of Gases and Liquids, 4ta edición, Ed. McGraw-Hill, Nueva
York, (1987).

8-5
 Many of the hypotheses that led to equation 8.2-7 are debatable, so it is not
to miss that in the bibliography1numerous modifications are proposed to it, almost always from the same one
form:
kM b
*
a  8.2 8 
cp
but with varied values of its coefficients a and b. In general, none of such modifications, including one
from Eucken himself, improve the reproduction of the available experimental data.
It will be noted that this theoretical method, whatever its version, requires knowledge of the
viscosities and molar heats of gases to estimate their thermal conductivities.

b) Roy-Thodos empirical method

Misic and Thodos2an empirical method was proposed for the estimation of thermal conductivity
based on dimensional analysis and experimental data. They arrived at the following function:
k 
f T, Z, C* r c p   8.2 9 
Tc1/ 6 M 1/2  8.2 10 
Pc2/3
being:
obtaining various equations for the different types of compounds and reduced temperatures of the
same1.
Subsequently, Roy and Thodos3 modified this method, dividing the product k in two
summands: the first corresponding only to the translational energy of the molecules, which is estimated
T
for adjustment of the available data on noble gases4, and that depends only on rthe second represents the
rotational, vibrational, etc. energy contributions, and it depends on both the reduced temperature and
a parameter that expresses the contribution of the different molecular groups. The representative equations
son
 8.2 11 
k (k )tr (k )int
(k )tr 99.6 106(e0.0464T er 0 .2412T r
)  8.2 12 
(k )int Cf(Tr)  8.2 13 
T p f(T )
being expressed: ken cal/(cm.s.K), c in K c in atm. The function r is presented in Table 8.2-1
for different types of compounds and the C parameter for hydrocarbons in figure 8.2-1. In the
Bibliography (1, 3) contains other values of the parameter C for alcohols, amines, nitriles, aldehydes,
ketones, ethers, acids and esters, as well as others more specific for the hydrocarbons in figure 8.2-1.

Table 8.2-1 Function

f(Tr ) from equation 8.2-13
f(Tr)
Compound
Saturated hydrocarbons1
T
-0.152r+1.191
2
T-0.039
r Tr 3
T 2
T+0,190 Tr 3
Oleins -0.255r+1,065 r

Acetylene
T
-0.068r+1,251
2
T-0,183
r Tr 3

Naphthalene and aromatics

T 2
T-0,147 Tr 3
-0.354r+1,501 r

2
Alcohols 1,000 Tr
T 2
Tr 3
Aldehydes, ketones, ethers, esters -0.082r+1,045 T+0,037
r

2 3
Amines and nitriles 0,633 Tr +0,367 Tr

2
D. Misic, [Link], AIChE J., 7, 264 (1961); J. Chem. Eng. Data, 9, 540 (1963).
3
D. Roy, G. Thodos, Ind. Eng. Chem. Fundam., 7, 529 (1968); Ind. Eng. Chem. Fundam., 9, 71 (1970)
4
D. Roy, M.S. Thesis, Northwestern University, Evanston, Illinois (1967).

8-6
 Halides
T
-0.107r+1,330
2
T-0,233
r Tr 3
T 2
T-0,147 Tr 3
Cyclic compounds2 -0.354r+1,501 r
1
Except for methane.2for example: pyridine, thiophene, ethylene oxide, dioxane.

c) Effect of temperature
The thermal conductivity of gases at low pressure increases linearly with temperature.
for small intervals of this. The differential relationship dk/dT passes from 0.1 to 0.3 μcal/cm.s.K2 , and its values
are higher when the value of k increases. For large temperature ranges, the variation of the
thermal conductivity is not linear.

30

25

20

15
C x 105

10

0
0 50 100
Molecular weight

Figure 8.2-1. Roy-Thodos Correlation. Parameter C values for hydrocarbons (equation .2-13)

If only one value is available at a certain temperature, this can be used to calculate the
parameter C of the Roy-Thodos method, equations 8.2-11, 8.2-12, and 8.2-13, can then be calculated
through this method the value at any temperature.
Owens and Thodos5they suggest the relationship:
kT2 T2
1,786

 8.2 14 
kT T1
1
for any non-cyclic organic compound.
Other authors6They propose that the exponent of the previous relation is a function of temperature.

Example 8.2-1

Estimate the thermal conductivity of ethane at 273 K and 1 atm. Under such conditions, the experimental value is
from 4.41.10-5cal/[Link].K.
C *p 12 cal/mol.K
Data: Molar heat capacities:
Cv* 9.8 cal/mol.K
0.85 104 p
Viscosity:
5
E. J. Owens, G. Thodos, AIChE J., 6, 676 (1960).
6
A. Missenard, Rev. Gen. Thermodyn., 11, 9 (1972).

8-7
 Tc 305.26K
Critical conditions:
Pc 48.8 atm

Solution

a) Eucken Method
For a polyatomic gas, equation 8.2-7 is used, solving for thermal conductivity:
C *p 1.25
k 2.25
M
C *p 12
*
1.22
M 30 C 9.8
for ethane: ;
(0.85 104)(12) 1.25
k 2.25 4,17.105 cal/[Link].K
30 1.22
Therefore:

b) Roy-Thodos method
From equations 8.2-10, 8.2-11, 8.2-12, and 8.2-13, we have:
T 1/6 M 1/2
k c 2/3
Pc
99.6 106 e 
0.0464 0 T
.2412 T
 e r  Cf(Tr) r   1
For saturated hydrocarbons, from table 8.2-1:
f(Tr) 0.152Tr 1,191Tr2 0.039Tr3  2
T 273
Tr 0.894  3
Tc 305, 26
f(Tr) 0.152(0.894) 1,191(0,894)2 0.039(0.894)3 0.788  4
From figure 8.2-1, for ethane (M= 30): C= 3.27 10 -5
 5
Substituting the values (3), (4), and (5) into equation (1):
(305.26)1/ 6301/ 2
k 99.6 106(e0.0464(0.894) e0 .2412(0.894))  3.27 105 (0.788)
(48.8)2/3
k 4,63 105 cal/cm²·K
Comparing the values estimated by both methods with the experimental one, the following results are obtained
deviations:
Eucken's method: -5.4%
Roy-Thodos method: +5.0%

II. Gaseous mixtures at low pressures

Empirical relationship of Wassiljewa
Vasilieva7he proposed an empirical relationship similar to the theoretical series solution deduced for the
viscosity 1.3-20. So, for thermal conductivity we have:
c
yiki
km c  8.2 15 
i 1
y j Aij
j 1

representing
yi, y j
the molar fractions of the components, kithe thermal conductivity of each
Aij
pure component and a computable parameter, as indicated below.

7
A. Wassiljewa, Physics, Z., 5, 737 (1904).

8-8
 Aij
Mason and Saxena method of estimation
These authors8they proposed the expression:
1/ 2 2
1/ 4
ktrI Mi
1
ktr Mj
j
Aij K'  8.2 16 
1/ 2
Mi
81
Mj
based on the values of the thermal conductivities of the components considered as
ktri ktr j
monatomic , and beingK a numerical constant close to one that oscillates between 1.065 and
0.85
As taking into account equation 8.2-2 the relationship is fulfilled:
ktri iMj

k trjM j i
 8.2 17 
C *I C *j 3R/ 2 K 1 y
since substituting this relationship into equation 8.2-16, assuming
ij
recalling the expression of Wilke's estimation method 1.3-21 the parameter
1/ 4 2
1/ 2
i
Mj
1
j Mi
ij 1/ 2
 1.3 21 
Mi
81
Mj
A  8.2 18 
ij ij
resulta:
Thus, the theoretical relationship for calculating the viscosities of gas mixtures is applicable.
also to the calculation of the thermal conductivities of the same, substituting pork. Based on the
transport of momentum and energy in different molecular interactions is understood that the
Equation 8.2-18 is only approximate.
If the thermal conductivities of the components considered were calculated as
ktr ,i/k tr, jfrom the expression
monatomic through equation 8.2-12 of the Roy-Thodos method, the relationship
8.2-16 would be:
ktri exp 0.0464Texp
j ri 0 .2412T
ri   8.2 19 
ktrj i exp 0.0464T exp
rj

 0.2412T
rj
 
the conductivities of pure gases are not required in this case.
The method is applicable to non-polar gas mixtures with errors below 3%, to gas mixtures
polar and nonpolar with somewhat greater errors and not recommended for mixtures of polar gases
exclusively.

Aij
Lindsay and Bromley's estimation method of
Using the gas model of the kinetic theory by Sutherland, Lindsay, and Bromley9they proposed the
Aij
next method of parameter estimation .

8
E. A. Mason, S. C. Saxena, Phys. Fluids, 1, 361 (1958).
9
A. L. Linsay, L. A. Bromley, Ind. Eng. Chem., 42, 1508 (1950).

8-9
 1/2 2
3/4
1 i Mj T SI T Sij
Aij 1
4 j Mi T S j T Si  8.2 20 
expression in which the Sutherland constants (S) are calculated using empirical expressions:
Si 1.5Teb i  8.2 21 
Tebi
being the normal boiling point of the component in K (79 K for He, H)2y Ne), y:
C Ss  S  1/2
Sij S hello I j  8.2 22 
beingCsa constant close to one, unless one of the gases is very polar, in which case it
suggest a value of 0.73 for it9The method is applicable to any mixture of gases with errors less than
to 5%.

Example 8.2-2

Estimate the thermal conductivity at 315 K and 1 atm of a gas mixture containing 32.5% moles of
nitrogen and 67.5% moles of ethylene. The experimental value is 5.63 x 10-5cal/[Link].K.
Data:
Properties of pure components under those conditions:
Nitrogen Ethylene
Thermal conductivity, (cal/[Link].K) 6,614 10-5 5,373 10-5
Viscosity, (cp) 0.0186 0.0103
Normal boiling temperature, (K) 77.2 169.1

Solution

Wassiljewa's empirical relationship 8.2-15, specified for the binary mixture of nitrogen (1) and ethylene
(2) reduces to:
y1k1 y 2 k2
km 
y1 A11y 2A 12 y1 A21  y2A 22
 1
The parameters are estimated belowijthrough the two proposed methods.

a) Mason and Saxena Method

From equation 1.3-21:
1/2 2
1/4
I
Mj
1
j Mi
Aij ij 1/2

81
Mi  2
Mj
1/2 1/4 2
0.0186 28
1
0.0103 28
A12 1/2  3
28
81
28
From equation 1.3-22:
jMI
yes ij
iMj

M1 0.0103 28
A21 2
A12 (1,373) 0.760  4
1M 2 0.0186 28
 5
8-10
 A11 A 221
Substituting the values (3), (4), and (5) into equation (1):
(0,325)(6,614 105) (0,325)(6,614 105)
k  5.65 105cal/cm²·K
m (0.325)(1) (0.675)(1.373) (0.325)(0.760) (0,675)(1)
Comparing this value with the experimental one results in a deviation of +0.35%

b) Lindsay and Bromley Method

For the calculation of the constantsiySijequations 8.2-21 and 8.2-22 are used:
S1 1.5T  1

  1.5eb77.2  115.80
   6
S2 (1,5)(T) eb2 (1,5)(169,1) 253.65  7
S12 S21 C2(S 1.S2)1/2 (1)(115,80)(253,65)1/2 171.38  8
Substituting the values (6), (7), and (8) into equation 8.2-20 results in:
1/2 2
3/4
1 (0.0186) 28 315 115,80 315 171.38
A12 1 1,329  9
4 (0.0103) 28 315 253,65 315 115,80

1/2 2
3/4
1 (0.0103) 28 315 253,65 315 171.38
A21 1 0,736  10 
4 (0.0186) 28 315 115.80 315 253.65
From equations (1), (5), (9), and (10) it follows:
(0,325)(6,614 105) (0,675)(5,373 105 )
km  5.73 105cal/[Link].K
(0.325)(1) (0,675)(1,329) (0,325)(0,736)  (0.675)(1)
Value that, compared to the experimental, shows a deviation of +1.8%.

III. Pure gases at high pressures

As in the case of viscosity, the thermal conductivity of gases, which always increases with
pressure only does so significantly at high pressures. Up to about 10 atmospheres, this increase is
of approximately 1% per atmosphere and is usually disregarded in the literature.
The most rigorous estimate of the thermal conductivity of gases is based, as in the case of
the viscosities, in correlations of the difference in conductivity of the same at high and low pressure
/ V /V
(residual conductivity, k-kº) and the reduced density r c c
Specifically Stiel and Thodos10
they propose the following equations for nonpolar gases (diatomic gases, inert gases, CO)2e
hydrocarbons)
T 1/6 M 1/2
(k k 0) c 2/3 Z c5 (14 108 )e0.535  1),r r 0.5  8.2 23 
Pc
Tc1/6 M 1/2 5
(k k 0)
Pc2/3
Z c (13,1 108 )(e0.67  1r ,069) 0.5 r 2  8.2 24 
Tc1/6 M 1/2 5  8.2 25 
(k k 0 ) Z c (2,976 108)e1.155  2,016),
r
2 r 2.8
Pc2/3
equations in which the conductivities are expressed in cal/([Link].K), Tcin K,pcin atm, debt must be
refer to the bibliography11to find the value of the critical volume Vcbeing preferable values
experimental densities c
.
Near the critical point, the accuracy of these equations is poor, and in regions of high
the precision fluctuates between 10 and 20%.
In the case of gases, one must refer to the bibliography.1.

10
L. I. Stiel, G. Thodos, AIChE J., 10, 26 (1964).
11
C.R. Wilke, Chem. Eng. Prog., 45, 95, (1950).

8-11
Example 8.2-3
-4
Estimate the thermal conductivity of chlorine at 834 K and 1.141 atm (experimental value 1.92 10
cal/[Link].K)
Datos:
Properties of chlorine in gaseous state:
-4
Thermal conductivity at 1 atm and 834 K: 0.653 10 cal/[Link].K
Critical temperature: 417 K.
Critical pressure: 76.1 atm.
Critical volume: Vc124 cm3/mol
Compressibility factor at the critical point: Zc 0.276
Factor de compresibilidad a 834 K y 1,141 atm:Z= 1,400.

Solution

ZRT(1,400)(0,082)(10 3 )(834)
V 83,91 cm3/mol
P 1,141
Vc 124
r 1.48
c V 83,91
0.5
Upon being 2
r
the equation 8.2-24 is used:
(Tc)1/6(M)1/ 2 0.67
r  1,069
(k k 0) (Z c )5 (13,1 108 )(e
(P) c
2/3

which, when substituting values, becomes:

(417)1/6(71)1/2
(k 0.653 104 ) (0.276)5 (13,1 108 )e0,67 1,48  1,069)

(76,1) 2/3

from which the value dek is obtained:

k 1.69 104cal/[Link].K
that compared to the experimental presents a deviation of -12%

IV. Gas mixtures at high pressures

The Stiel and Thodos equations 8.2-23 to 8.2-25 are used, considering mixtures as a
hypothetical pure component with pseudo-critical properties expressed by equation 1.3-38.

Example 8.2-4

Estimate the thermal conductivity of a gas mixture containing 52.9% moles of nitrogen and 47.1%
of carbon dioxide, at 323 K and 20 atm. The experimental value is 5.66 x 10 -5cal/[Link].K.

Data:
Properties of pure substances:
Nitrogen Ethylene
Critical temperature (K) 126.2 304.2
Critical volume (cm3/mol) 90.1 94.0
Critical compressibility factor 0.291 0.274

Comprehensibility factor of the mixture at 323 K and 20 atm: 0.973.

Thermal conductivity of the mixture at 323 K and 1 atm: 5.37 x 10-5cal/[Link].K.

Solution

8-12
Calculation of the pseudocritical properties of the mixture, equation 1.3-38:
c
Tcm yI Tci (0,471)(304,2) (0,529)(126,2) 210,04 K
i 1
c
Vcm yV
i ci
(0,471)(94,0) (0,529)(90,1) 91.94 cm3/mol
i 1
c
Zcm yi ZcI (0.471)(0.274) (0,529)(0,291) 0.283
I 1

Z cmRTc m (0.283)(0.082)(103 ) (210.04)

pcm 53,015 atm
Vcm 91,94
The reduced properties of the mixture will be:
T 323
Trm 1,54
Tcm 210.04
p 20
prm 0.38
pcm 53,015
The molar volume of the mixture Vmes:
Z mRT(0.973)(0.082)(10 3
(323)
Vm 1288,54 cm3/mol
p 20
Vcm 91,94
r 0.0713
m
Vm1288.54
Therefore:
0.5
Being m
, equation 8.2-23 is used:
T 1/6 M 1/2
 kmk 0 m  cmP 2/3 m Zc5m 14 108e0.535
 1  rm
  1
cm

M m (0.529)(28) (0.471)(44) 35.54

Substituting values into equation (1) gives:
(210.04)1/6(35,54)1/2
(k m 5.37 105) (0.283)5 (14 108 )e0.535(0.0713) 1)
(53,015)2/3
km 5.66 105 cal/[Link].K
value coinciding with the experimental.

8.3 THERMAL CONDUCTIVITY OF LIQUIDS

I. Pure Liquids
The thermal conductivities of the most common organic liquids are usually between 10 and 100.
times greater than those of gases at low pressures and equal temperatures, depending little on the
pressure and normally decreasing as the temperature increases, although this effect is much less
pronounced that the exercise on its viscosity. The conductivity of such liquids ranges between 250 and 400
µcal/(cm.s.K) at temperatures lower than the normal boiling points, while those of water, ammonia and
Other polar molecules are two or three times higher, and those of liquid metals are 100 times greater.
In parallel to what has already been indicated in the case of viscosity, there is currently a lack of theoretical basis.
sufficient for the estimation of the thermal conductivity of liquids, having to resort to equations
approximate empirical.

a) Estimation of thermal conductivity

The estimation methods presented below refer exclusively to organic liquids.

Sato and Riedel's boiling point method

8-13
Sato1proposed the following correlation for the thermal conductivity of organic liquids at their
normal boiling temperature:
2,64 103  8.3 1 
k L,eb
M 1/ 2
Riedel12he proposed, for his part, the following correlation:
20  8.3 2 
k L A1
3
1
 Tr 
2/3

From equations 8.3-1 and 8.3-2 it is deduced:

3  20 1  T
2/3
2.64 103 r
kL  8.3 3 
 
2/3
M 1/ 2
3  20 1 T reb
being expressed the conductivityLin cal/([Link].K).
This method, whose application requires only knowing the molecular weight and the temperatures
Boiling point criticism and normal of substances is the most appropriate whenever an estimate is required.
rapid approximation. However, it is not applicable to very polar liquids, to light hydrocarbons, to
compounds with branched chains, to inorganic liquids or to liquids at temperatures much higher than the
boiling points.

Robbins and Kingrea Method

Weber13he was the first to suggest the proportionality between thermal conductivityLand the
productCp* ρm4/3based on numerous correlations for the possible prediction ofLAmong1 them stands out the
proposal by Robbins and Kingrea14:

kL
 88 4.94H103  0.55 NC * 4/3  8.3 4 
p m
S* Tr
C *p
siendokLthermal conductivity in cal/(cm.s.K);Tr the reduced temperature; molar specific heat
in cal/(mol.K);ρmthe molar density of the liquid, mol/cm3; ∆S* = (reb/Teb) +Rln(273/Teb);rebit is the heat of
normal vaporization at the boiling temperature, cal/mol;Tebthe normal boiling temperature, K;Hy
Two parameters, dependent on the molecular structure and the density of the liquid, respectively. The
the first of them is summarized in table 8.3-1 and the second can only take the values 0 and 1 for
liquid densities greater than or less than 1 g/cm3, respectively.

Tabla 8.3-1ParámetroHde la ecuación 8.3-4

N0of
Functional group H
groups
Unbranched hydrocarbons
Paraffins 0
Olefins 0
Rings 0
Branches CH3 1 1
2 2
3 3
C Branches2H5 1 2
i-C Branches3H7 1 2
C Branches4H9 1 2
Substitutions F 1 1
2 2
Substitutions Cl 1 1
2 2
3 or 4 3

12
L. Riedel, Chem. Ind. Tech., 21, 349 (1949); 23, 59, 321, 465 (1951).
13
H. F. Weber, Ann Wiedemann’s, Ann. Phys. Chem., 10, 103 (1880).
14
L. A. Robbins, C. L. Kingrea: (a) Hydrocarbon Proc. Pet. Refiner, 41 (5), 133 (1962); (b) Preprint, Sess. Chem. Eng.
27th. Midyear Meet. Am. Pet. Inst. Div. Refining, San Francisco (1962).

8-14
 Substitutions Br 1 4
2 6
Substitutions I 1 5
OH substitutions 1 (iso) 1
1 (n) -1
2 0
1 (third.) 5
Substitutions >C=O (ketones, aldehydes) 0
Substitutions-O–C=O (acids, esters) 0
Substitutions -O- (ethers) 2
NH Replacements2 1 1
To be able to apply this method, it is necessary to know the density, the molar specific heat, the
normal boiling temperature and the latent heat of vaporization of the liquid in question. Not applicable
inorganic or organic sulfur compounds. This method is the most accurate for reduced temperatures.
ranging from 0.4 to 0.8 with an error of less than 5%.

Estimation method at high temperatures

In the case of saturated liquids at reduced temperatures above 0.8, it is recommended to resort to
the proposed methods for pure gases at high pressures, section 8.2 III.

b) Influence of temperature and pressure on thermal conductivity

As has already been indicated, up to pressures of 30-40 atm, this variable does not significantly influence
the thermal conductivity of liquids, which decreases with increasing temperature except in cases of
very polar liquids (polyhydroxyl compounds, polyatomic, etc.), this influence being much more
pronounced in the case of simple liquids than in complex ones.
For wide temperature ranges, correlation 8.3-2 by Riedel can be used to calculate
the value of conductivity at one temperature based on what corresponds to another. The correlation is not
applicable if it concerns water, glycols, glycerin, hydrogen or helium, in which case other ones must be resorted to
bibliography1.
At pressures higher than the indicated, its effect on conductivity can be estimated by the
relationship proposed by Lenoir15:
k 2l 2  8.3 5 
k1l1
in which the thermal conductivities1yk2 correspond to the same temperature and different pressure, yl1y
l2 they represent functions of reduced temperature and reduced pressure, whose value is deduced from the curves of the
Figure 8.3-1. The errors with polar and non-polar liquids are below 4%.

Example 8.3-1

Estimate the thermal conductivity of benzene at 323 K and 1 atm. The experimental value is 3.23 10
4

cal/[Link].K.
Data:
Critical temperature: Tc= 562.1 K.
Normal boiling temperature: Teb= 353.3 K.
Densidad: 0,873 g/cm3
Calor molar:Cp* = 32 cal/mol.K.
Latent heat of vaporization at normal boiling temperature: 7,353 cal/mol.

Solution

a) Sato and Riedel method

15
J. M. Lenoir, Pet. Refiner, 36 (8), 162 (1957).

8-15
 kL
2.64x103 
3  201 T r
2/3

 1
 
2/3
M 1/2 3  201 T reb

T 323 Teb 353.3

M 78 ; Tr 0.575 ; Treb 0.629
Tc562.2 Tc562.1
Substituting these values into equation (1):
2.64x103 3  20 1  0.575  2/3
kL 3.21 times 104cal/[Link].K
781/2 3  20 1  0.629  2/3
Comparing with the experimental value, it is observed that the deviation is 0.6%.

Figure 8.3-1 Effect of pressure on the thermal conductivity of liquids: equation parameter.

b) Robbitis and Kingrea Method

The equation 8.3-4 is used:
N
(88 4.94H)1030.55
kL C *p 4/3
m  2
S* Tr
0.873
m 0.0112 mol/cm3
M 78
7353 273
S*  1.98ln 20,302
353.3 353.3
Since the density is 0.873 < 1 g/cm3N=1.
From Table 8.3-1: H = 0
Therefore, from equation (2) we have:
88 103 0.55
kL (32)(0,0112)3/4 3.32x104 cal/[Link].K
20,302 0,575
Value that shows a deviation of +2.8% compared to the experimental.

8-16
II. Liquid Mixes
The thermal conductivity of a liquid mixture is generally lower than the average value that would be obtained at
starting from the corresponding pure components and their molar or mass fractions.
With many methods proposed and all of similar accuracy1, we will refer here only to the
Li16the most modern and uniquely valid for multicomponent mixtures, with an error of 3%.
This author proposed the equation:
c c
km I
k
j ij
 8.3 6 
i 1j 1

2
kij  8.3 7 
1 1

kijk j
being:
xiVI
i c
 8.3 8 
x j Vj
j 1

I, j
dondexi,xjthe molar fractions of the components i, j; they are the volumetric fractions of said
components and Vi,Vjthe molar volumes of the same, pure and in liquid state.
The form of equation 8.3-6 for a binary mixture of components 1 and 2 is:
km 1 k1 2 1 2 k12
2
2 k2
2
 8.3 9 
In the case of diluted ionic solutions, the thermal conductivity of the mixture decreases when
increase the concentration of dissolved salts. The following method has been proposed for its estimation.1,12,17 :
1 c
km(20ºC) k H 2O (20ºC) c
4,186 I 1 i i  8.3 10 
k H2 O (T)
km(T) kH 2O (20ºC)  8.3 11 
k H2 O (20ºC)
kH 2O
siendokmthe thermal conductivity of the ionic solution in cal/(cm.s.K), thermal conductivity
of water in cal/(cm.s.K),cIthe concentration of the electrolyte in mol/l, i
a characteristic coefficient of each
ion (Table 8.3-2).
Except for strong acids and alkalis at high concentrations, equations 8.3-10 and 8.3-11
lead to results with ±5% accuracy.

Table 8.3-2 Characteristic Coefficient I from equation 8.3-10

Anion i 10
5 Cation i 10
5

OH- 20,934 H+ -9,071

F- 2.0934 Li+ -3,489
Cl- -5,466 Na+ 0.000
Br- -17,445 K+ -7,560
I- -27,447 NH4+ -11.63
NO2- -4,652 Mg2+ -9,304
NO3- -6,978 Ca2+ -0.5815
ClO3- -14,189 Sr2+ -3,954
ClO4- -17,445 Ba2+ -7,676
Bro34- -14,189 Ag+ -10.47
CO32- -7,560 Cu2+ -16,28
SiO32- -9,300 Zn2+ -16.28
SO32- -2,326 Pb2+ -9,304

16
C. C. Li, AIChE Journal 22, 927 (1976).
17
D. T. Jamieson, J. S. Tudhope, Nat. Eng. Lab. Glasgow, Rep. 137, March (1964).

8-17
 SO42- 1,163 Co2+ -11.63
S2O32- 8,141 Al3+ -32,56
Chromium oxide-1,163
4
2-
Th4+ -43.61
Cr2O72- 15,93
PO43- -20,93
Fe(CN)64- 18.61
Acetate- -22.91
Oxalate2- -3,489

Example 8.3-2

Estimate the thermal conductivity at 50 °C of an acetone-methanol mixture with 40% by weight of methanol.

Data:
Experimental value of the conductivity of the mixture: 4.00 × 10-4 cal/[Link].K. Properties at 50 °C of the
pure components:
k(cal/s·cm·K) Density (g/cm3)
-4
Acetone 3.65 10 0.75
Methanol 4.46 10-4 0.75

Solution

The thermal conductivity of a binary liquid mixture is estimated using equation 8.3-9:
km 1 k1 2 1 2 k12 2 k 2
2 2
 1
where we will name: (1) acetone, (2) methanol.
According to equation 8.3-7:
2 2
kij 4,014 104  2
1 1 1 1
 
k1k2 3.65 104 4.46 104
Since the mixture contains 40% by weight of methanol, its molar composition will be:
60 / 58,082
x1  0.453 ; x2 1 0.453 0.547
60 / 58,082 40 / 32.04 
For the calculation of molar volumes:
M 158.08 M 232.04
V1 77.44cm3/mol ;V 2 42.72 cm3/mol
1 0.75 2 0.75
Therefore, from equation 8.3-8:
x1V1 (4,453)(77,44)
1 0.6
x1V1 x2V2(0,453)(77,44) (0,547)(42,72)
2 1 0.6 0,4
It can be observed that in this case, since the densities of both compounds are equal, they logically coincide.
the mass and volumetric compositions.
Substituting values in equation (1):
km (0,6)2(3,64 104 )  2(0.6)(0.4)(4.014 104 )  (0,42 ) (4,46 104 )
cal
3.95 104
[Link].K
value that, compared to the experimental, has a deviation of -1.25%.

8.4 THERMAL CONDUCTIVITY OF SOLIDS

8-18
The thermal conductivity of solids depends on numerous factors that are difficult to measure or predict.
The porous solids depend on the fraction of pores, their size, and the fluid that fills them. In solids
crystalline depends on the nature of its network and its dimensions, and in the amorphous, on the orientation of its
molecules, etc. Therefore, the thermal conductivity of solids must always be determined
experimentally, without having any estimation method available18.
In general, metals are better conductors than non-metals, and crystalline solids are better conductors than amorphous ones.
The thermal conductivities of pure metals decrease with increasing temperature; conversely,
The properties of non-metals increase as the temperature does, showing the alloys a behavior.
intermediary between one and the other. For small temperature intervals, the variations of the
The conductivities of solids can be considered linear.
In the case of pure metals, thermal and electrical conductivities are related by the
Wiedemann, Franz and Lorenz equation:
2
ks ks k  8.4 1 
3.3
ke T T
dimensionless equation in which ksit is the thermal conductivity, k,eelectric conductivity, the
resistividad eléctrica,Tla temperatura absoluta, thekBoltzmann constant and ε the charge of the electron.

8.5 EFFECTIVE THERMAL CONDUCTIVITY OF COMPOSITE SOLIDS

The primary contribution to the estimation of the conductivity of heterogeneous solids was made by
Maxwell, who considered a material made of spheres of thermal conductivity.
k1 embedded in a phase
k
solid continuous with thermal conductivity0The volume fraction is considered of spheres
embedded is small enough. The correlation for small volume fraction is
kef 3
1  8.5 1 
k0 k1 2k0

k1 k0
For a large volume fraction, Rayleigh demonstrated that, if the spheres are positioned in the
intersections of a cubic network, then the thermal conductivity of the compound is given by
k ef 3
1  8.5 2 
k0 k1 2k0 k1 k0
  1,569  ...
October3rd

k1 k0 3k1 4k0

Non-spherical parainclusions, equation 8.5-1 does not require modifications. Therefore, for arrangements
squares of long cylinders parallel to the axis, Rayleigh demonstrated that the components of the tensor of
thermal conductivity is
k1 k0
ef,zz
1  8.5 3 
k0 k0
and the other two components are
2
ef,xx ef, yy
1  8.5 4 
k0 k0 k1 k0 k1 k0
k1 k0
 
k1 k0
 0.30584 4
 0.013363 8
 ... 
For complex non-spherical inclusions often found in practice, an
exact treatment, only approximate relationships exist. For simple unconsolidated granular beds of ha
it has been demonstrated that the following expression is successful

kef  1   k/k 
1 0
 8.5 5 
k0  1  

18

8-19
where
1
1 3 k1
1  1g k  8.5 6 
3k 1 k0
g k "form factors" for the medium granules, and they must satisfy g1 g 2 g 3 1
The . For spheres,
g1  g 2 g 3 , 13 g1 g 2 1
and the equation 8.5-5 simplifies to the equation 8.5-1. For unconsolidated soils, 8 y
g 3 .43
Parasoids that contain gas bags, thermal radiation can be important. For these
it can be demonstrated that systems
kef 1
1
 8.5 7 
k0 k14 T L 3
1  
k 0 k0
k
where it is the Stefan-Boltzmann constant, 1 it is the thermal conductivity of the gas and the total thickness

of the material in the direction of heat conduction.

Cylindrical ducts filled with granular materials through which a fluid circulates.
directions are of considerable importance in separation processes and chemical reactors. In these
the effective thermal conductivities in the radial and axial directions are quite different and
ef,rry
designed by ef ,zz
For a bed of uniform spheres, the radial and axial components are
approximately
ef,rr
ˆ
10 C p 0 D p;
1
ef,zz C p12 0 Dˆ p  8.5 8,9 
D
where it is the 'surface velocity' defined in 4.3 and 6.4, and p it is the diameter of the spherical particles.
0

Re D p 0 /
These simplified relationships are fulfilled for greater than 200.

8.6 CONVECTIVE TRANSPORT OF ENERGY

Energy can be transported by conduction due to molecular movements, by convection by
the global movement of the fluid. Figure 8.6-1 shows three mutually perpendicular elements of area
dS at point P, where the fluid velocity is The volumetric flow rate through the
dS perpendicular to the axes dS
surface element x
So, the speed at which it moves the
energy through the same surface element is
1
2
2

 Uˆ dS x   8.6 1 
1 2 1
( x  2 y 2
)
z
2
ˆ
U
where 2 2
it is the kinetic energy per unit volume, and it is the internal energy
per unit volume.

Figure 8.6-1 Three surface area elements perpendicular to each other through which the fluid flows
move quickly it transports energy by convection. The volumetric flow velocity through the face

8-20
 dS 2 ˆ
( 12p pU) x dS
perpendicular to the axes x and then the flow rate of energy through deSes It is possible
write similar expressions for the surface elements perpendicular to the axes yyz .

We can write expressions similar to equation 8.6-1 for the rate at which energy spreads.
through the surface elements perpendicular to the axes yyz If we now multiply each of
the three expressions by the corresponding unit vector and we sum, then it is obtained, after dividing
for dS
 1
2
2
 Uˆ  x x
  1
2
U2  ˆ  y yU  1
2
2

 ˆ Uz z  1
2
2 ˆ   8.6 2 
and this amount is called the convective energy flow density vector. To obtain this density
(n (1 2 2  Uˆ) )
whose unit vector we form the dot product .

8.7 WORK ASSOCIATED WITH MOLECULAR MOVEMENTS

First, let's remember that when a force F acts on a body and makes it move a distance dr ,
dW ([Link])
the work done is Then, the rate at which work is done is
dW/dT ([Link]/dt) (F )
That is, the dot product of the force by the velocity. Now we apply this
formula for the three perpendicular planes at a point in the space shown in figure 8.7-1.

Figure 8.7-1 Three surface area elements dS perpendicular to each other at point P together with the vectors of
x, yy z
effort that act on those surfaces. In the first figure, the speed at which it does work the
( x )dS [ ]xdS
fluid on the negative side dedS about the fluid on the positive side dedS then .
Similar expressions hold for surface elements perpendicular to the other two coordinate axes.

First, we consider the surface element perpendicular to the axes. The fluid on the negative side.
dS
exerts a force on the surface x
about the fluid that is on the positive side. Because the fluid
is moving with a speed the relationship in which the negative fluid does work on the fluid
( )dS
positive is x
It is possible to write similar expressions for the work done through the others.
two surface elements. When written in component form, these expressions for the
speed at which work is done, per unit area, converts to
 x  xx x
 xy y
 xz z x
 8.7 1 
 y  yx x
 yy y
 yz z y
 8.7 2 
 z  zx x
 zy y
 zz z z
 8.7 3 
Once these scalar components are multiplied by the unit vectors and summed, e1 is obtained.
"vector of the velocity at which work is done per unit area" which is abbreviated as
workflow density
x  x   y  y   z  z   8.7 4 
In addition, the rate at which work is done through an oriented surface area unit
(n [ ])
given by the unitary vector .

8-21
 Equations 8.7-1 to 8.7-4 are easily written for cylindrical coordinates by substituting x, y, z.
, zy, for spherical coordinates, by replacing x, y, z with r, ,
porr .
Now we define, for later use, the combined energy flux density vector. e how
continue
and  1
2
2
 U ˆ  q  8.7 5 
The vector is the sum of: a) the density of convective energy flow, b) the speed at which it occurs.
work (per unit area) by molecular mechanisms, and c) the rate at which heat is transported (per
area unit) by molecular mechanisms. All terms in equation 8.7-5 obey the same
e
convention of signs, so thatx , it is the transport of energy in the positive x direction per unit of
area per unit of time.
p  , in such a way
The total molecular stress tensor it can now be separated into two parts:
[ ] p [ ]. p
what The term it can then be combined with the term of internal energy
Uˆ ˆ p
U (Uˆ ( p / )) = (UˆpV) ˆ Hˆ,
to obtain a term of enthalpy , so that
e  1
2
 2
H ˆ  q  8.7 6 
In general terms, we will use the vector in this form. For a surface element dS of orientation
(n e)
n, the quantity provides the convective energy flux density, the heat flux density and the
workflow density through the surface element dS from the negative side to the side
positive of dS .

Table 8.7-1 Summary of the notation for energy flux densities

Símbolo Significado Reference
 1
2
2
 Uˆ  Energy convective flux density vector Equation 8.6-2
q Vector of thermal molecular flow density Equation 8.1-6
Molecular flow density vector of work Equation 8.7-4
and q   1
2
 2
U ˆ  Combined energy flux density vector Equation 8.7-5,6
q   1
2
 2
H ˆ 
Table 8.7-1 summarizes the notation for the various energy flux density vectors that
they were introduced in this section. They all follow the same convention of the signs.
To evaluate the enthalpy in equation 8.7-6, we use the standard formula of thermodynamics for
conditions in equilibrium
ˆ
H ˆ
H ˆ
V
dHˆ dT dp Cˆ pdT  VˆT dp  8.7 7 
T p
p T
T p

Thus, when the previous expression is integrated from some reference state.
p 0 , T0 until the state, T, is
obtains
T p ˆ
V
Hˆ H ˆ C
0
dT0 Tˆ Vˆ T dp  8.7 8 
p p 0
T p

where
Ĥ 0 it is the enthalpy per unit mass in the reference state. The integral over zero for a gas
(1/ )(p p0) Ĉ p(T T0)
ideal y for fluids of constant density. The integral over T becomes if the
Heat capacity can be considered constant over the relevant temperature range. It
Assume that equation 8.7-7 is valid in systems that are not in equilibrium, where pyT are the values
locales of pressure and temperature.

8-22
8.8 COMPLEMENTARY PROBLEMS19

9A.9 Thermal conductivity of gaseous chlorine

Use equation 9.3-15 to calculate the thermal conductivity of gaseous chlorine. To do this, it is necessary to
use equation 1.4-14 in order to estimate the viscosity and the following values are also necessary
heat capacity
T  k 200 300 400 500 600
p 
Cal/mol.K  8.06 8.12 8.44 8.62 8.74
Check to see how well the calculated values match the following experimental data.
of thermal conductivity.


TK  
mmHg  k 105 cal/cm.s.K.
198 50 1.31 0.03
275 220 1.90 0.02
276 120 1.93 0.01
220 1.92 0.01
363 100 2.62 0.02
200 2.61 0.02
395 210 3.04 0.02
453 150 3.53 0.03
250 3,42 0.02
495 250 3.72 0.07
553 100 4.14 0.04
583 170 4.43 0.04
210 4.45 0.08
676 150 5,07 0.10
250 4.90 0.03
Solution

From table E.1 of the text of the reference19, it is obtained for the Cl2 the following data: M 70,905 and the
o

Lennard-Jones parameters: 4,115 A y /k 357K

.
Now using equation 1.4-14 from the BSL (2nd Ed.):
MT
2.6693 105 2  1.4 14 
o
T K A g/cm s
With
kT200
0.560
Then 357
Using table E.2 with
kT/
0.55 2,178
0.60 2,084

19
Corresponding to the proposed exercises from chapter 9 of R.B. Bird, W.E. Stewart, E.N. Lightfoot, Phenomena of
Transport, 2nd edition, Mexico, Limusa Wiley Publishing, (2006). Likewise, the numbers of the equations used
correspond to the same text.

8-23
Interpolating for kT/ 0.56
2,178 2,084
2,178   
0.26 0.22 2,1592  2
0.60 0.55
70,905  200 
2.6693 105 8.6940 105 g/cm s
Luego:
 4,115  2,1592
2

And applying Eucken's equation, for a low-density polyatomic gas (9.3-15) of the BSL, 2nd Ed.
5
k C pˆ R  9.3 15 
4 M

C p1.25R 8.06 1,251,987   cal 10.54 cal

Por tanto: mol K mol K
5 cal g 1 mol
k C pˆ R 10.54375 0.8694 104
4 M mol K cm 70,905 g
cal
k 1.29 105 105kbefore 1.29
cm s K
To avoid the use of table E.2 we can use the empirical equation of Neufeld, Janzen and Aziz (J. Chem.
Phys,57, 1100, (1972)) suitable for its application on a computer:
1,16145 0,52487 2,16178
k  
T 0.14874 e 0.7732T* e 2.43787T*
kT
T*
where the adimensional temperature
The rest of the requested calculations are implemented with Excel. According to the solution manual, the predicted values ofk
with correlations exceeding the experimental values by an average of 8.4% in the temperature range
from 198 K to 676 K.

9A.10 Thermal conductivity of chlorine-air mixtures

Use equation 9.3-17 to predict the thermal conductivities of chlorine-air mixtures at 297 K and 1 atm.
for the following molar fractions chlorine: 0.25; 0.50; 0.75. Air can be considered as a single
substance and the following data can be assumed:
Substance  Pas  
kW/m.K  p 
ĈJ/kg.K 
Air 1,854 105 2,614 102 1,001 103
Chlorine 1,351 105 8,960 103 4,798 102

Solution

The data for this problem can be obtained from table E.1 of the reference.19and they are summarized in the table that
the following is indicated:
Mole fraction
Component M 5
10 ,Pa.s k, W/m.k mix 1 mix 2 mix 3
s
1 (chlorine) 70,905 1,351 0.00896 0.25 0.5 0.75
2 (air) 28,964 1,854 0.02614 0.75 0.5 0.25

ij
Dimensionless coefficient
1 /2 1/2 2
1/4
1 Mi Mj
ij 1 1 i
 1.4 16 
8 Mj j Mi

8-24
Replacing data:
1/2 1/2 1/4 2
1 70,905 1,351 28,964
12 1 1 0.53895
8 28,964 1,854 70,905
1/2 1/2 1/4 2
1 28,964 1,854 70,905
21 1 1 1.81061
8 70,905 1,351 28,964
1.0
Moreover 11 22

Substituting the coefficients and compositions in equation 9.3-17

n
xi kI
kmix n
 9.3 17 
i 1
x j ij
j 1

Equation 9.3-17 for binary mixtures gives:

x1k1 x2 k2
kmix 
x1 11 x2 12x1 21  x2 22
0, 25 0.00896 0.75 0.02614
kmix  0.01973 W/m.K
In x1 0, 25 :
0, 25 1  
0,75 
0,53895 0,25  1,81061  0.75 1   
0.5 0.00896 0.5 0,02614
kmix  0.01512 W/m.K
x 0.5
In 1 :
0.5 
1 
0.50, 
53,895 
0.51, 81061  0.5 1   
0.75 0.00896 0.25 0.02614
kmix  0.01166 W/m.K
In x1 0.75 :
0.75 
1 
0, 25 0,53895 0,75 
1,81061 0, 25 1   

9A.11 Thermal conductivity of quartz sand

A typical sample of quartz sand has the following properties at 20 °C.

Component Volume fraction I k,cal/cm.s.K

I 1 Silica 0.510 20.4 103
i 2 Feldspar 0.063 7.0 103
(i 0)
The continuous phase it is one of the following:
i)
water 0.427 1,42 103
ii) Air 0.427 0.0615 103

Estimate the effective thermal conductivity of sand: i) when it is saturated with water and ii) when it is
completely dry
a) Use the following generalization of equations 9.6-5 and 9.6-6
N

kef I  i
k/k 0  i
i 0
N
 9A.11 1 
k0
I i
i 0
1
1 3
ki
i 1  1g j  9A.11 2 
3 j 1 k0
g1 g2 g3 1/3
Here is the number of solid phases. Compare the prediction for spheres. ) with the
g1 g2 g3 3/4
recommendation from de Vries ).
k1 18.9 103 cal/cm.s.K
b) Use equation 9.6-1 with what is the average thermal conductivity by volume of
the two solids. Some observed exact values within an approximate margin of 3% are 6.2 and

8-25
0.58 103 cal/cm.s.K , for wet and dry sand respectively. It was believed that the particles could
to better approximate as flattened spheroids with an axis ratio of 4, for which
g1 g2 0.144 g3 0.712
.

Solution:

a) From equation 9A.11-2:

1
1 3
ki
I 1  1g j
3 j 1 k0
g
As the summation is dej= 1 to 3; withjfor spheres = 1/3
1
1 ki 1
i
3
 
3 1
k0
1
3
1 1 1
ki 1 2 kI 2k0 k
i 1   i
3k0 3 3 3k0 3k0
3k0
i
2k0 ki
,
dividing the numerator and denominator of the second member by , itkhas:
0

3
 1
i 
2 ki/k0 

for spheres ( g1 g 2 g3 1 / 3 )
The resulting values from iEquation (9A.11-2) for water-saturated sand are:
3 3
1
0 
2 k0/k0  3
3 3
0.183
1
 2 k1/k0  2
20.4 103
1.42 103
3 3
0.433
2
 2 k/k2
2
7.0 103 0
1.42 103
And applying equation (9A.11-1) we have:
N N

kef i  I
k/k 0 i
k0 i 
k/ki 0  i
i 0 i 0
N
kef N
k0
i I i i
I 0 i 0

Here (water-saturated sand), we have N = 2 (two solid phases: silica and feldspar), and the continuous phase
i 0 (in the water). Then the kef of the mixture is (applying the summations):
0 k 0 0 1 k1 1 2 k2 2
kef  2
0 0 1 1 2 2

And replacing the data:

 1  0.00142   0, 427 0,183 
0,0204    0.433
0,51   0.007  0.063
  
kef
 1  0, 427 0.183
   0, 433
0.51  0,063
  
k 6.3 103 cal/cmsK 6 . 2 103
what predicts ef vs observed

8-26
For the same sand, when it is completely dry:
k1 20.4 103
331.71 332
k00.0615 103
k2 7 103
113.82 114
k00.0615 103
Applying equation (9A.11-2) for spheres gives:

3 3 3 3 3
1; 0.00898 0.0259
0
 0
2 k/k 0  1 
2 k1/k0  [2  (20.4 / 0.0615)] 334
2
2 114
and the equation (9A.11-1) with the Vries correction factor of 1.25 for dry sand gives:
kef 0 k0 0 1k1 1 2 k2 2

1.25 0 0 1 1 2 2

kef  1    0,00898
0.0000615 0.427   0,0204  0,510   0,0259
  0,0070
 
0,063  
1.25  1   
0.427 0.00898 0.51  0,0259
  0,063  
kef 3,783 104 0.38 103
kef 0.38 103 cal/cm.s.K 3
what it predicts vs 0.58 10 observed
For the same water-saturated sand at 20°C, applying the algorithm recommended by de Vries,
it is had:
1
1 3
kI
i 1  1g i
3 j 2 k0
g1 g2 1 / 8 g3 3/4
with
1 2 1

i
3  i1g
1 k/k 0  2  I1g 0
1 k/k  3

1 2 1
 1,000
1.42/1.42 1 0.1251 
0
3 1  1.42/1.42 1 0.75
Then:
1 2 1
 0.280
20.4 / 1.42 1 0.1251 20.4 / 1.42 1 0.75
1
3 1  

1 2 1
 0.532
7.0 / 1.42 1 0.125 1 
2
3 1  7.0 / 1.42 1 0.75


And substituting in equation (2)

0 k 0 0 k
1 1 1  k
2 2 2
kef
0 0  1 1  2 2

 1  0.00142   0.427 0,280

  0,0204   0,510   0,532
   0,063 
0,0070  
kef
 1  0.427 0.28
  0.51 0.532
  
0.063  
kef 6, 22 103 cal/cm.s.K
being in better agreement with the observed value6.2 10 cal/cm.s.K
3

For the same sand when it is completely dry

 k/k
1 0
332;k/k 2114 0  , the equation (9A.11-2) with
the recommendations of de Vries give the values.
1 2 1
 1,000
3 1 1 1 0.125
 1 1 1 0.75  
0

8-27
 1 2 1
 0.0171
3 1 332 1 0.125 1 332 1 0.75 
1

1 2 2
 0.0048
31 114 1 0.125 1 114 1 0.75 
2

and the equation (9A.11-1) with the de Vries correction factor for dry sand gives:
kef  1  0,0000615 0,427
   0,0171
  0,0204  0,51
  0,0048
  0,0070
  0,063   
1.25  1    0.51 0,0048
0.427 0.0171   0,063
  
k 0,54 103cal/cm.s.K
vs 0,58 10 observed
3
what predicts ef

b) Equation 9.6-1 gives:

kef 3
1
k0 k1 2k0

k1 k0
0.573 k1 0.0189 cal/cm.s.
The insertion of y for solids gives, for water-saturated sand:
kef 3  0.573 
1 3,563
k0 
0.0189 0.00142 
 0.573
0,0189 0.00142
kef 5.1 103cal/cm.s.K
vs 6,2 10 observed. This result is not as good as the
3

predicting
gj
prediction in (a) of equation 9A.11-2 with the values de de Vries.

k0 in equation 9.6-1 it gives:

For completely dry sand, the insertion of the k values for air and
kef 3  0.573 
1 4,935
k0 
0.0189 0.0000615   0.573
0.0189 0.0000615
kef 0.30 103cal/cm.s.K, vs 0.58 103
predicting observed. The result in (a), of the equation (9A.6-
11) de Vries is better.
kef
The predictions of are more difficult for dry sand than for water-saturated sand. A model
flattened spheroid of little advantage according to the present data.

9A.12 Calculations of molecular diameters from transport properties

a) Determine the molecular diameter of the area from equation 1.4-9 and the given experimental viscosity.
in problem 9A-2
b) Repeat item (a), but using equation 9.3-12 and the thermal conductivity measured in the problem.
9A.2. Compare this result with the value obtained in part (a).
c) Calculate and compare the values of the Lennard-Jones collision diameter from the same data
experiments that were used in sections (a) and (b) using / from table E.1.
d) What can be concluded from the previous calculations?

Solution

a) Equation 1.4-9 and the viscosity value from problem 9A.2 produce the following diameter calculation
molecular for Ar in cgs units:

8-28
 2m T/  1.4 9 
3 d2
1/4
2 M T
d
3 N 3 2,278 105 Pa.s = 2,278 104 g/cm.s
;
1/ 4
39,948 1,38066 101 6 300
d 
2 / 3 2,278 104  6.02214 1023 3

d 2.95 108 cm
M 39,948 g/mol
Data:
1,38066 1016ergios/K
(Boltzmann Constant)
[Link] [Link].s2 g.cm2s 2
1,38066 1016 1,38066 1016
K dina K
T 300 K N 6.0224 1023molecules/mol
b) The equation 9.3-12 and the value of the problem 9A.2 provide the following calculation of the molecular diameter for
the Ar in cgs units:
m T/
k  9.3 12 
d2 m
3 1/4
1 TN W Js1107erg 1m
d k 0.01784
k 3M mK W J 102 cm
1/4

d
1 1,38066
  6.02214 1023
101 6 300
3

3
0.01784 105 39,948
d 1.86 108cm
c) Equation 1.4-14, tables E.1 and E.2, and the viscosity of problem 9A.2 yield for Ar in cgs units:
5 m T
 1.4 14 
16 2

1/4
5 M T
; 2,278 105Pa.s = 2,278 104 g/cms
16 N
o T 300K
3,432A ; / 122.4 K 2.45098
Table E.1: 122.4K
1,107 1.0933
1,107 2.45098 2, 40 1,1000
2.50 2.40
Table E.2
5 30,948  1,38066 10 16
 300
1/ 4

16  2,278 1041,1000
  6.02214 1023
3,415 108cm
The equations 9.3-13 and 14, tables E.1 and E.2, and the value of problem 9A.2 give for the Aren units cgs:
25 m T
k Ĉv  9.3 13 
32 2
k

15R 5 ˆ
k Cv  9.3 14 
4M 2
15R 5 ˆ 30R3R
Cv Cˆv
in 9.3-14: 4M 2 20M2M

8-29
 3 N
Ĉv
R
In addition N then 2 M and replacing in 9.3-13 with m M/N (the mass of a molecule), it
has
1/2 3 1/2
25 million T 3 N 1 75M TN 2
1
k 2
32N 2M 2 k64N M
2
k

3 1/ 2
75 1 TN
k 2
64 M
k
. From problem 9A.2: k(Ar) = 0.01784 W/mK
3 1/ 4
75 TN
64k k M k
But
1/ 4

75 1.38066
  6.02214
1016 300  3
1023 
64 1784 1,1000 39,948
Then:
3,409 108 cm.
d) The excellent agreement between the results for , and the poor stop concordance shows that the
data is represented much better by the Chapman-Enskog theory than by the simple kinetic theory of the
rigid sphere.

9C.1 Enskog Theory for Dense Gases

Enskog developed a kinetic theory for the transport properties of dense gases. He demonstrated that for
idealized molecules as rigid spheres of diameter 0
.
V 1
o
 0.8 0.761y  9C.1 1 
bo y
k V 1
 1, 2 0.755y  9C.1 2 
k obo y
o
y k they are the properties at low pressure (calculated, for example, from equations 1.4-14 and
o
Here
b 2/3 N 03
9.3-13) V it is the molar volume and o donde N it is Avogadro's number. The quantity and is
related to the equation of state of a gas composed of rigid spheres.
2 3
pV bo bo bo
y 1  0.6250  0,2869  ...  9C.1 3 
RT V V V
These three equations provide the density corrections for viscosity and thermal conductivity.
of a hypothetical gas composed of rigid spheres.
I also suggest that for real gases, i) can be provided empirically by:
V p
y
R T V
1  9C.1 4 
p V t
where experimental data is used from y (ii) bo It can be determined by adjusting the number in the

curve of
/ Vo
contrary.
a) A useful way to relate the equation of state is to use the corresponding states representation of
Z Z  pr ,Tr 
, where Z pV/RT,pr p/pcyTr T/Tc Demonstrate that the quantity and defined by the
Equation 9C.1-4 can be calculated as a function of reduced pressure and temperature from:
1   lnZ/ lnT r  p
y Z
1   lnZ/ lnp
r
1  9C.1 5 
r T r

8-30
b) Show how equations 9C.1-1, 9C.1-2, along with the Hougen-Watson Z diagram and the diagram
/ k/kc
from Uyehara-Watson in figure 1.3-1, can be used to develop a diagram of
c
like a
function of pr Tyr What are the limitations of the resulting diagram? This procedure was used by
p V T
Comings and Nathan but using specific data from instead of the Z diagram of Hougen -
Watson.
c) How could the Redlich and Kwong equation of state be used?
a
p V b  RT  9C.1 6 
TV  V b  

For the same purpose, the quantities 'a' and 'b' are constant characteristics of each gas.

Solution

a) The equation (9C.1-4) can be written with pressure and temperature as the independent variables,
the following way:
V  V/ T  p
y  1  1
R  V/ p  T

Now we can use

pV ZRT V ZRT/p
and rewrite the previous derivatives as:
V R R Z R T Z
 ZT  Z T Z1
T p p T p p T p p Z T p

V RZ lnZ
1  2
T p p lnT p

V Z Z 1 Z RTZ p Z
RT RT  1
T T
p p T
p 2p p T p2 Z p T

V RTZ lnZ
 1  3
T T p2 lnp T

By substituting expressions (2) and (3) into expression (1) for y, we have:
RZ 1  lnZ
ZT p lnT p
y  1
p RTZ lnZ
 1
p2 lnp T

lnZ
1
ZT RZp 2 lnT p
y 1
p RTZp lnZ
1
lnp T

1  lnZ/ lnT  1  lnZ/ lnT  pr

y
p
1 y Z 1
1  lnZ/ lnp T 1  lnZ/ lnp T
ó r

b) First, the Hougen-Watson graph could be differentiated to obtain the derivatives that appear in the
y  pr ,Tr 
result in (a) and therefore Then for a given reduced temperature and pressure, they could be

8-31
 f pr,T 
calculate the right members of equations 9C.1-1 and 9C.1-2, refer to these quantities r
y
f kp r,T r 
So:
k f k p r,T r 
k o o
f pr ,T r 
Then one can read the values of from the Uyehara-Watson graph and build a graph for the
thermal conductivity. This procedure is not recommended for polyatomic gases.
For the equation (9C.1-1):
V 1
 0.8 0.761y
o
bo y
f  pr,Tr 
the one we can define as the function that is to say:

1
 0.8 0.761y f p,T r r 
y
V
o
f  pr ,T r 
bo
o
V V
f  p,Tr r  f  p,Tr r   4
bo bo
Analogously for equation (9C.1-2):
k V 1
 1, 2 0.755y
k obo y

f k p r,T r
The one we can define as a function
1 , that is to say
 1,2 0.755y f kpr,T r  
y
k V
 r
f kp,T r 
k obo
V ko
f kp r,T r   5
bo k
For what gives (4) and (5)
ko
f  pr,T r  o
f kp r,T r 
k
k o
 r
f kp,T r 
ko f p,T r r 

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