Anda di halaman 1dari 40

Applied Energy 19 (1985) 1-40

Thermodynamic and Thermophysical Properties of


Organic Working Fluids for Rankine-cycle Engines

O. Badr, P. W. O'Callaghanand S. D, Probert


School of Mechanical Engineering, Cranfield Institute of Technology,
Cranfield, Bedford MK43 0AL (Great Britain)

SUMMARY

Refrigerants, especially the halocarbon compounds R-I1, R-113 and


R-114, are the most suitable organic working fluidsfor the majority of
operational Rankine-cycle engines utilising low grade heat sources. Thus,
the quick and accurate evaluation of the thermodynamic and thermo-
physical properties of these refrigerants is desirable for the analytical
prediction of the performances of individual components of such a
Rankine-cycle engine, as well as its overall performance. Computer sub-
routines have therefore been developed for calculating the properties of
refrigerants R-II, R-12, R-13, R-14, R-21, R-22, R-23, R-113, R-114,
R-I15, R-500, R-502 and R-C318 as functions of their characteristic
parameters at a state point. The derived equations and correlations are
collated and presented in this paper. The developed sub-routines were used
to evaluate the properties of the halocarbons R-11, R-113 and R-114. The
generated pressure-enthalpy diagrams are given. The computed
properties of R-113, as a representative candidate, are shown in
comparison with the other pertinent published data. The results indicate
that there is a good agreement between the predicted values, using the
programmed correlations and equations evolved in this investigation, and
the most authoritative, but sometimes esoteric, data available.

NOMENCLATURE

Specific heat (J/kg K).


Specific enthalpy (J/kg).
1
Applied Energy 0306-2619/85/$03.30 Elsevier Applied Science Publishers Ltd,
England, 1985. Printed in Great Britain
2 O. Badr, P. W. O'Callaghan, S. D. Probert

P Pressure (N/m2).
R Gas constant (J/kg K).
s Specific entropy (J/kg K).
T Temperature (K).
/) Specific volume (m3/kg).
X Constant in eqn. (10).
Y Constant in eqn. (12).
7 Ratio of the principal specific heats of the vapour.
A h la t Latent heat of vaporisation (J/kg).
Thermal conductivity (W/m K).
# Dynamic viscosity (kg/m s).
P Density (kg/m3).

Subscripts
C Refers to the critical state.
g Refers to a saturated vapour.
l Refers to a saturated liquid.
p Refers to constant pressure.
r Refers to the reduced condition.
ref Refers to the reference state.
s Refers to saturation.
v Refers to a constant volume.

Superscripts
* Refers to the dilute gas phase (pressure ,~ 10 5 N/m2).
* Refers to the ideal gas state.

Constant coefficients of the correlating equations:


Ap, Bp, C o, Dp, Ep, Fp, Gp, in the liquid density equations (see eqns (1)
and (2))
As, BS, Cs, Ds, Es, F S, in the saturation pressure equations (see eqns (3)
and (4))
A2, B2, C2,..., A6, B6, C6, b', C', K, 7 in the pressure-specific volume-
temperature equation (see eqn. (5))
a, b, d,f, k, in the ideal gas constant-volume specific heat equation (see
eqn. (6))
A, Bc, Co, in the saturated liquid specific heat equation (see eqn. (16))
Working.fluids Jor Rankine-cycle engines 3

A., B., C., D., E., F., in the saturated liquid, dilute gas and saturated
vapour dynamic viscosity equations (see eqns (23), (24) and (25))
Ax, B~, Q, D~,E~., F~, G~, K;,n~, in the saturated liquid, dilute gas and
saturated vapour thermal conductivity equations (see eqns (26)
to (30)).

Abbreviations
ASHRAE: American Society of Heating, Refrigerating and Air-
Conditioning Engineers, Inc., New York, USA.
ICI: Imperial Chemical Industries, Ltd, Great Britain.
TPRC: Thermophysical Properties Research Center at Purdue
University, USA.

SCOPE OF THIS INVESTIGATION

Due to their unique thermodynamic behaviours at low temperatures,


organic fluids--as the working media in Rankine-cycle engines--have
characteristics that make them suitable for extracting mechanical work
from low-grade heat sources. ~-3 The commonly used refrigerants--
halogenated hydrocarbons R-11, R-113 and R-114--are the most
attractive organic working fluids commercially available for these
applications. 3,4
A knowledge of a working fluid's thermodynamic and thermophysical
properties as functions of the characteristic parameters at its state point is
an essential pre-requisite to the analytical prediction of the performance
of the Rankine-cycle engine in which it is used. Hand calculations using
the available esoteric Tables and charts of properties are lengthy and
laborious. Moreover, the use of Tables that seldom include data at
exactly the required temperature and pressure conditions, can lead to
inaccurate results.
Now, with digital computers readily available, a quick and accurate
determination of a working fluid's properties can be achieved using
equations describing its thermodynamic and thermophysical behaviours.
For some of the organic working fluids, these equations have appeared in
many diverse and esoteric publications, and so have been collated in this
investigation for the convenience of other investigators. In particular,
correlations and equations have been selected, or developed, for
refrigerants R-I1, R-12, R-13, R-14, R-21, R-22, R-23, R-I13, R-I14,
4 O. Badr, P. W, O'Callaghan, S. D. Probert

R-115, R-500, R-502 and R-C318. General computer sub-routines have


been composed for the VAX 11/780 digital computer, in order to evaluate
the properties of each refrigerant considered. Therefore, the desired
information, under any set of feasible conditions, can now be obtained
simply by inserting the proper data statements for the chosen refrigerant.
The first sub-routine developed facilitates the calculation of the
thermodynamic properties of the chosen refrigerant. It evaluates the
values of the saturation pressure, specific volume, specific enthalpy and
specific entropy for both the refrigerant's saturated liquid and vapour at a
given temperature, as well as the values of the specific volume, specific
enthalpy and specific entropy for the refrigerant's superheated vapour as
functions of the temperature and pressure. The refrigerant's phases of
interest are shown in Fig. 1.
Computer sub-routines have also been constructed to evaluate the
thermophysical properties of the considered refrigerant. The sub-routines
permit the prediction of the values of the specific heat, dynamic viscosity
and thermal conductivity of the saturated liquid refrigerant. They
evaluate both the constant volume and constant pressure specific heats, as
well as the ratio of these principal specific heats for the saturated and the
superheated vapours of the refrigerant. Values of the dynamic viscosity
for the saturated and the superheated vapours, as well as the thermal

............ A CONSTANT TEMPERATURE LINE


A CONSTANT SPECIFICENTROPY LINE
A CONSTANT SPECIFIC VOLUME LINE

SUP EO
i--
"'k.,.\.
v
,~ CO~S_.T~_S~
c~F~c
==
e~/
vliil
c ill.

/ _
SPECIFIC ENTHALPY. h ( LINEAR SCALE )

Fig. 1. A typical pressure-enthalpydiagram of a refrigerant showing the different


phases and the constant property lines.
Working fluids for Rankine-eycle engines 5

conductivity for the superheated vapour, the two latter values being for
one atmosphere absolute pressure, can also be calculated.

THERMODYNAMIC PROPERTIES

The calculations of the thermodynamic properties of the refrigerants are


based on four basic algebraic equations which serve to correlate the
experimental data for:
(i) saturated liquid density
(ii) saturation pressure (i.e. the vapour pressure when in contact with
its own liquid)
(iii) pressure-specific volume-temperature behaviour of the vapour
(iv) constant volume specific heat of the refrigerant's ideal gas (i.e. that
of the refrigerant vapour as p ~ 0)
Equations for calculating the thermodynamic properties of the
refrigerants, in any of the three phases considered (see Fig. 1), can then be
obtained from the four basic correlating equations using exact
thermodynamic relationships.

Basic correlating equations

Martin 5 and Downing 6 developed general correlations of experimental


data for several refrigerants. Downing assembled the constants
appropriate to the equations, in Imperial units, for refrigerants R-11,
R-12, R-13, R-14, R-21, R-22, R-23, R-113, R-114, R-500, R-502 and
R-C318. The correlating equations are presented here (see eqns (1) to (6)),
with the constants for refrigerants R-11, R-113 and R-114, in SI units,
being listed in Table 1.

Saturated liquid density


Pl = Ap+ Bp(l - Tr) 1'3 + Cp(1 - Tr) z/3 +Do(1 - Tr)
+ Eo(1 - Tr) 4/3 + Fo(1 - Tr) 1/2 + Gp(1 - T~)z (1)
where:
T
6 O. Badr, P. W. O'Callaghan, S. D. Probert

M
?
o 7
X ~
~ X

"2 oo ~ ~ ~ ~
~ ~ . ~ . ~ , ~ . , ~

,-2
i

?
0 ?
X

[-

7'
X
X
~ X
0

0
Working fluids jbr Rankine-cycle engines 7

X ~ X ~ X X X X X

77 =
o o

X X

6 o ~ - - oo o o o o o o o o o o o ~ 6 o oo

o
7 7 77
X XX XX X X X X X X X X

0
8 O. Badr, P. W. O'Callaghan, S. D. Probert

In the case of refrigerants R-21 and R-113, the form of the equation is:
p,= AR + BoT + CpT z (2)

Saturation pressure

loglop=A~+_f+CslogloT+DsT+Es Fs T loglo(Fs-r) (3)

In the case of the refrigerant R-23, the form of the equation becomes"
Bs
loglop~ = As + ~ + Cs log~o T + DsT + E J 2 + FsT a (4)

Pressure-specific volume-temperature relationship for the vapour


RT A2 +B2T+C2exp(-KT,) A 3 +B3T+C3exp(-=KTI,)
P v - b' 4 (v - b') 2 -~ (v -- /.~')3

+
A4+B4T+C4exp(-KTr) As+BsT+Csexp(-KTr)
(v - b')" (v - b') s

+ A6 + B 6 T + C 6 e x p ( - K T r ) (5)
(1 + C' exp (~v)) exp (~v)
If ~ is zero, any term in which it appears in the d e n o m i n a t o r should be
omitted in eqn. (5).

Constant volume specific heat of the refrigerant's ideal gas


k
c~ =a + bT + dT 2 "~-J"Z 3 q- T--~ (6)

In order to maintain the accuracy of the final predictions the presented


numbers in Table 1 were not rounded off to values commensurate with the
experimental errors of measurement.

Derived equations

Using the thermodynamic relationships and the four basic correlations,


equations expressing the other desired t h e r m o d y n a m i c properties of the
refrigerants can be derived. 5 Here, in order to save space, only the final
Working fluids for Rankme-cycle engines 9

forms of the required equations and some of their derivation procedures


will be presented.

Latent heat of vaporisation


The latent heat of vaporisation can be calculated, using the Clapeyron
equation:

The slope of the saturation pressure (vapour pressure) curve (dps/d T) can
be obtained from eqns. (3) or (4). Therefore:
p cs
Ah~.,= T(vo-v~) ~{log~(10) [ T2 4 Tioga(10) +D~

- E~(!gT(e) -t F~lgl(F~-~5 T))} 1 (8)

For refrigerant R-23, the form of the equation is:

Ahl. , = T(v o - vt) I p ~ {log~ (10)}

t-D s +2E~T+ 3FsT2}I (9)


x - ~-~ + rloge (10)

Specific enthalpy of a refrigerant's vapour


This, at a given state, relative to its respective value at a selected reference
state, can be expressed as:

h = a T + ~ b Tz + ~dT 3 -[- f T 4- k + A2 4 A3
+ pv v - b' 2(v-b') 2

4 3(v-b') 3 q 4(v-b') 4 e expiry) C'log e l + c e x p ( e v )


~C~,, C3 C4
+ ( e x p ( - KT~))(1 + KT~) iv - b 4 2 ( v - b') 2 4 3 ( v - b') 3

C5 C6 C6C', ( 1 )}
+4(v_b,)4+otexp(ow) ~ loge 14 C'exp(ow) + X (10)
10 O. Badr, P. W. O'Callaghan, S. D. Probert

The constant X depends on the selection of the reference condition for


evaluating the enthalpy of the refrigerant. It is customary, in refrigeration
analyses, to set the specific enthalpy of the saturated liquid at - 4 0 C
(=233.15K) equal to zero. Therefore, the reference condition for
refrigerants is normally taken to be the saturated vapour at 233.15 K. The
value of the constant X in eqn. (10), for a refrigerant, can thus be
determined as:
2 d f k
X = (Ahl,t),e I - aT, eI + 2 Tiel + 3 Ti3el + T~I

Az A3 A4
-'[-Prefl)ref -+-- - 4 "4
Vref -- b' 2(vr,q -- b') 3(Vre f - b')

A5
+ 4(VreI -- b')
+A6[
-~- e x p
1
(O~l)ref)
C'log(1A
'
C' exp (0%es) )1
+ Iexp ( - K ~ c J ) l ( 1 q-KTref~[-~c}L~ C 2 ..1_ C3
2(V,e I - b') 2

+ C4 + C5
3(Vref -- b') 3 4(Vref - b')4

+ C6
(11)
exp (~ZV~el)
The values of the constant X, for refrigerants R-I 1, R-113 and R-114,
as evaluated by Downing, 6 but now converted to SI units, are given in
Table 2.

Specific entropy o f vapour


The specific entropy of a refrigerant's vapour, relative to its value at a
reference condition, can be determined as:
d 2 jc k
s=alogeT+bT+~T +~T a 2T 2 + R l o g e ( v - b ' )

B2 B3 B4 B5
v - b' 2 ( v - b') 2 3 ( v - b') 3 4 ( v - b') 4

B6
I 1
oc exp (av) (
C' log~ 1 -~ C' exp (0w)
')1 +
Tc
Work ingfluidsfor Rankine-cycle engines II

% C3 C4 C5 C6
x Lv_b + 2 ( v - b') 2 + 3 ( v - b') 3 + 4 ( v - b') 4 + ~exp(~v)

Jog e 1)1
1 -~ C' exp (~v) + Y (12)

The constant Y depends on the selection of the reference condition. For


entropy, this is taken at the same state as that for enthalpy, i.e. that of the
saturated vapour at 233.15 K. Because it is customary in refrigerant
studies to set the specific entropy equal to zero for the saturated liquid at
233.15 K, the value of the constant Yfor a refrigerant can be calculated as:

Y-(Ahlaz)refTref { alogeTref +bTref + d Tfef + T3y-2TZe---~I

B2 B3 B,,
+ R log~ (V~ef -- b')
Uref -- b' 2(v~y - b') 2 3 ( V ~ e J. - - b,)3
B5 B6[ 1 (
4 ( v , , / - b') 4 ~ exp (~v~y) C' loge 1 -F C' exl(~v,e/))l

C4
+ Tc b ' + 2 ( v . , j . - b') 2 + 3(Vre/- b') 3

Cs C6 + , 1
+ + C 61C ' l~ g e ( C e x p ( ~ v r e f ) ) l } (13)
4(Vref -- b') 4 o~exp (~xv~/)

Values of the constant Y for R-11, R-113 and R-114, as evaluated by


Downing, 6 except that they are now appropriate to the SI representation
of eqn. (12), are listed in Table 2.

TABLE 2
Values of the Constants X and Y in Equations (10) and (12), Respectively

Constant ReJ~'igerant
R-11 R-I13 R-114
X 1"1756022 l0 s 5'861 0544 10 4 5"894005 104
Y -384"51361 -1'697831 1 x 10 3 -482"05634
12 O. Badr, P. W. O'Callaghan, S. D. Probert

Evaluation of the thermodynamic properties


The following three sections describe the equations which were
programmed on the computer and the computational procedure used to
evaluate the desired thermodynamic properties of the saturated liquid,
saturated vapour and the superheated vapour of each considered
refrigerant, respectively.

Saturated Liquid
The important properties of the saturated liquid, at a given temperature,
are the saturation pressure, its specific volume, specific enthalpy and
specific entropy.
(i) S a t u r a t i o n p r e s s u r e . This can be calculated, at the given tempera-
ture, using eqns. (3).or eqn. (4).
(ii) Specific v o l u m e . Saturated-liquid specific volume is simply the
reciprocal of the saturated liquid density as given by eqn. (1) or eqn. (2).
(iii) S p e c i f i c e n t h a l p y . This, for the saturated liquid, can be calculated as
the difference between the specific enthalpy of the saturated vapour, hg,
and the latent heat ofvaporisation, Ahz,,, at the same temperature; that is:
h I = h o - Ahz~ t (14)
The values of h o and Ahl,, are calculated using eqns (10) and (8) or (9),
respectively.

(iv) Specific e n t r o p y . For the saturated liquid, this can be calculated in


a similar way to that employed when evaluating its specific enthalpy,
namely:
Aht~' (15)
s~ = s o T

The specific entropy of the saturated vapour, s o, is deduced using


eqn. (12).

Saturated vapour
At any specified temperature, the properties of interest for the saturated
vapour are the same as those for the saturated liquid.
(i) S a t u r a t i o n p r e s s u r e . This is evaluated, as in the case of saturated
liquid, using eqn. (3) or eqn. (4).
Working fluids for Rankine-cycle engines 13

(ii) Specific volume. This can be obtained implicitly from eqn. (5) by
substituting the values of the given temperature and the corresponding
calculated saturation pressure, using the Newton-Raphson iterative
process. 13

(iii) Specific enthalpy. The specific enthalpy of the saturated vapour can
be calculated using eqn. (10).
(iv) Specific entropy. This can be evaluated by employing eqn. (12).

Superheated vapour
Equations (5), (10) and (12) are equally applicable to superheated and
saturated vapours and can be employed to evaluate the required
properties of the superheated vapour in the same way as was used in the
case of the saturated vapour.

THERMOPHYSICAL PROPERTIES

For the analytical evaluation of the performance of a Rankine-cycle


engine, some of the thermostatic and transport properties of the working
fluid need to be known. So, in the following sections, correlations and
derived equations, which enable one to evaluate the specific heats,
dynamic viscosities and thermal conductivities of the liquid and vapour
phases of the refrigerants, are presented. SI units are used throughout the
data presented subsequently.

Specific heats

Specific heat o f the saturated liquid


The Thermophysical Properties Research Center (TPRC) at Purdue
University, USA, reviewed and evaluated the available data concerning
the specific heats of saturated liquid refrigerants. 14 According to
Martin,5 the specific heat data for the refrigerants' saturated liquids fit
equations of the form:
c t = A c + BeT + CoT 2 (16)
Using ASHRAE data, 14 the constants in eqn. (16) have been evaluated
for refrigerants R-11, R-113 and R-114 by employing the least-squares
method--see Table 3.
14 O. Badr, P. W. O'Callaghan, S. D. Probert

TABLE 3
Characteristic Constants in Equation (16) for the Refrigerants R-11, R-113 and R-114

Characteristic Refrigerant
constant R-11 R-113 R-114
Ac 909.673 79 1 292.913 3 371-329 47
Bc -0.955 118 1 -3.227221 5 1-7456647
Cc 2-9673 x 10 3 6.9505 x 10 -3 1.267 x 10 -3

Constant volume specific heat, constant pressure specific heat, and ratio of
the principal specific heats of vapours.
The c o n s t a n t volume specific heat o f the saturated or superheated
v a p o u r o f a refrigerant at any state point can be related to the specific
heat, c~, in the ideal gas condition by the expression :5

c~, = ct, + T t ff~-~/], dv (17)

M a k i n g use of the correlating e q u a t i o n s (eqns (5) and (6)), the c o n s t a n t


volume specific heat o f a v a p o u r can be expressed by:

k K 2 T e x p ( - KT,) I C2
c,, = a + bT + dT z + i T 3 + T2 Tc2 L(V Z-b')

C3 C4 C5 C6
-~ 2(v - b') 2 -~ 3(v - b') 3 -~ 4(v - b') 4 t ~exp (~v)

C6C'log e 1 +
e
( 1)1
C' exp (~v)
(18)

As for eqn. (5), if ~ is zero, any term in which it appears in the


d e n o m i n a t o r should be omitted f r o m eqn. (18).
The specific heat o f a v a p o u r at c o n s t a n t pressure can be related to the
constant volume specific heat b y the following s t a n d a r d t h e r m o d y n a m i c
relationship: 1

c, = c , - r / <,9>

The derivatives in eqn. (19) can be evaluated f r o m the pressure-specific


Workingfluidsfor Rankine-cycle engines 15

volume-temperature correlating equation (eqn. (5)) as follows:

@)_ R + B2 - Tcc C2 exp ( - KT~)


+--
UT ~, - ~v - b (l'- b') 2 (t;- b') 3

B4- ~ - C 4 e x p ( - K T r) B 5 - ~ c ) C5 exp ( - KT~)


+- +
( v - b') 4 ( t , - b') 5

B6- Tc C6exp(-KT~)
+ (20)
( 1 + C' exp (~v))exp (~v)

and:
_ R,"
2[ A2 + B2T + C2eXp(-
~
CUr ( t " - b') 2

- 3IA 3 + B3T +(t-:C3b'4exp(-


) KT,) 1

_ 4IA 4 + B4 T + --~
C.[97exp(--KT~)]

-5IAs+BsT+(r--~7~Csexp(-KTr)1

~(1 + 2C' exp(~v))(A 6 + B6T+ C6exp( - KTr)


(21)
(1 + C' exp(~v)) 2 exp(~v)

The ratio of the principal specific heats, 7, can then be calculated from
the known values of the specific heats, cp and cc, as:
Cp
7 = -- (22)
~,
Dynamic viscosity
Saturated liquid
The thermophysical properties of liquid refrigerants have been well
documented for the temperature range up to ~60C. However,
16 O. Badr, P. W. O'Callaghan, S. D. Probert

apparently the only available data concerning the dynamic viscosity of


saturated liquid refrigerants at operational temperatures appropriate to
Rankine-cycle engines for low-grade energy applications are those
developed by the TPRC and published by ASHRAE. 14 It is agreed by
many authors. 15-~s that the dynamic viscosity data for liquid
refrigerants can be correlated reliably by an equation of the form:

For refrigerants R- l 1, R- 113 and R- 114, the correlation constants, A. and


B., evaluated using the data published by ASHRAE. are give in Table 4.

TABLE4
C h a r a c t e r i s t i c C o n s t a n t s A , and ~ , ~ r E q u a t i o n ( 2 3 )

Character~tic Refrigerant
constant R-11 R-II3 R-114

A~ 969.56456 1 203.360 6 1111.113


B~ - 11.000 542 - 11.332 063 - 11.694283

Vapour
There is a consensus of opinion between several authors, 15,16.19 that the
dynamic viscosities ofvapour refrigerants at pressures around and below
10 5 N/m 2, i.e. that of the low density (dilute) gas, depend mainly on
temperature. The relationship employed successfully to correlate the data
for the dynamic viscosity, p*, at 10 5 N/m 2 versus temperature for many
vapour refrigerants is:
It* = C~ + D , x / T (24)
The coefficients Cu and D, for refrigerants R-I 1, R-113 and R-114 were
evaluated by a least-mean-squares analysis using the one atmosphere data
of the TPRC 14 and are listed in Table 5.
When the pressure of the vapour exceeds 105 N/m 2, the vapour's
dynamic viscosity is not only dependent upon the temperature but is also
a function of the pressure. Keating and Matula 19 and Matula and
Witzell 2 suggested that a simple equation of the form:
#
p~ = E,, + F,p (25)
Working fluids.[br Rank ine-cycle engines 17

TABLE 5
Values o f the Characteristic Constants C, and D~,

Characteristic Refrigerant
constant R-11 R-113 R-114

C,, - 1 . 1 6 5 2 2 9 10 -5 - 3 . 8 6 5 1 6 0 9 10 - 6 - 1 ' 1 1 8 2 1 9 8 x 10 -5
D, 1.298570 1 x 10 - 6 8"2026256 10 v 1"3087999 10 -

can correlate reliably the dynamic viscosity data in both the low and
moderate density regions (i.e. up to Pr = (P/Pc) = 2). Equation (25) was
used to correlate the saturated vapour data of the TPRC, 14 for
refrigerants R-11, R-113 and R-114, using the predicted values of the
density and the dilute gas dynamic viscosity. The least-mean-squares
evaluated coefficients, Eu and F~, for these refrigerants are listed in
Table 6.

TABLE 6
Values o f the Characteristic Coefficients Eu and Fu

Characteristic Refrigerant
coefficient R-11 R-113 R-I14

Eu 1.023 143 1.000 450 4 0.994 687 9


Fu 1.2897834 x 10 -4 8601 575 [0 - 4 1.0807592 x 10 3

Thermal conductivity

Saturated liquid
Over a wide range of temperatures, except near the critical point, Liley
and Zahn 18 and Chidambaram z 1 suggested that the thermal conductivity
of a refrigerant liquid can be approximated to a high degree of accuracy
by a linear function of the form:
/~l = A~ + BAT (26)
This equation was used to correlate the recently available data of the
TPRC. 14 The evaluated correlation coefficients, Aa and Ba, for the
saturated liquids of refrigerants R-11, R-113 and R-114 are given in
Table 7.
18 O. Badr, P. W. O'Callaghan, S. D. Probert

TABLE 7
Values of the C o r r e l a t i o n C o n s t a n t s in E q u a t i o n (26)

Characteristic Refrigerant
constant R-11 R-113 R-II4

A~ 0.161 148 53 0"13677498 0.150452 1


B~ -2'5261927x 10 -4 -2'0681071 10 -4 -2"8721519x 10 -4

Vapour
Keating and Matula 19 suggested a relationship of the form:
2* = C A+ D AT (27)
to correlate the thermal conductivity data for refrigerant vapours in the
low density range below and around atmospheric pressure - 105 N/m 2.
The least-mean-squares evaluations for coefficients, CA and DA, based
upon the TPRC one-atmosphere data, 14 are listed in Table 8.

TABLE 8
Correlation Coefficients for Refrigerants R-11, R-113 a n d R-114

Characteristic Refrigerant
coefficient R-11 R-113 R-114

C~. - 1 ' 9 6 2 9 1 6 3 10 -2 - 2 ' 7 6 2 3 5 1 1 0 _2 - 3 ' 1 4 3 9 3 9 1 1 0 -z


Dz 1"5842093 10 -3 2 . 0 1 5 7 1 2 2 x 10 3 2.405989 1 x 10 -3

Except for a few fluids, values for the thermal conductivity of


refrigerants under saturated vapour conditions, or at pressures higher
than one atmosphere, are almost non-existent. However, Keating and
Matula 19 proposed an equation of the form:
2
2~ = E A + FAp (28)

Gruzdev et al. zz suggested that the pressure dependence of the thermal


conductivity of vapour refrigerants can be described by the expression:
2 - 2* = GAp"i, (29)
Working fluids Jbr Rankine-cycle engines 19

Liley and Zahn 18 suggested a correlation of the form:

2t - ,~ = Kz Ahta, (30)

for estimating the thermal conductivity, )t0, of the saturated vapour near
the critical point.
Because little dependable pertinent experimental conductivity data are
available, correlations (28), (29) and (30) cannot be tested adequately and,
therefore, no attempt was made to use any of them for the prediction of
the thermal conductivities of the refrigerants considered in this
investigation.

RESULTS AND DISCUSSION

Thermodynamic properties
Figures 2, 3 and 4 present sections of the pressure-enthalpy charts for
R-I 1, R-113 and R-114, respectively, generated using the sub-routine
developed. The resulting predicted values of the thermodynamic
properties of R-113 were compared with the available published data;
namely:
(i) du Pont's tables of thermodynamic properties for R-113,
developed by Benning and McHarness; 23
(ii) the 1975 data of the Allied Chemical Corporation on the
properties of the R-113 saturated liquid and vapour, published by
ASHRAE; 14
(iii) the tables of thermodynamic properties of R-113 according to
Imperial Chemical Industries (ICI). 24
These data, which have been regarded as the most accurate existing ones,
were used as the bases for determining the accuracies of the predicted
values. Relative deviations in the computed properties from these
reference data were evaluated. The relative deviation in the calculated
value of a property was defined as:
Relative deviation
(calculated v a l u e ) - (reference value)
= x 100 (per cent) (31)
(reference value)
20 O. Badr, P. 14". O'Callaghan, S. D. Probert

\ ~~ ~.
%

~',,, ~ ~
t

o
Workingfluidsfor Rankine-cycleengines 21

c~

L~

25
o

~z

"o o o
o

[Joq] 3kl~S~:ld
22 O. Badr, P. W. O'Callaghan, S. D. Probert

R
u3

.fi

i 8
o

:,
o
"0o0 0 0 0 0 0 o
[JOq] 3~:II-IS
S 3~:Id
Work ingfluids for Rankine-cycle engines 23

o. "='

t" i", \ ~-~.

i/~ ~ u~ o ~n o ~ o o o o o o o o o o o o o o o

[/o] NOLLVlA30~IAI1V73~ ~ 0

u _~'~ .uE~ oE

~1 !IT ~ ~~ TM

='~
E~=-~
.o

8~
5
=.~o =
\\
I .o
I
I
/
///J i l i I i : ,i
/'
.//" , ~._~
o
o o o o 0 0
,
0
,
o
,
o
,
0
,
0 o

[%1 NOIlVlA3Q 3AIVq3~ ..~ ~


SATURATIONPRESSURE

1-0

0.5
0

-05
. . . . ~--.~/"~6o
SPECIFICVOLUME
------ SATURATEDLIQUID
- - SATURATEDVAPOUR

" ~ , /*0 120 , ~ ,

~ "'- ~.EMPERATURE[ "C1

\N
\\
\

Fig. 7. Deviations of the computed thermodynamic properties of R- 113 saturated liquid


and vapour from the data of 1CI. 24

SPECIFIC VOLUME
01
8O 100 120 I/.0 160
0 i
I I I ~TEMPERATURE ['C ]
-01
-0.2
-03
-0/*
-05
-06
-07

0 1t SPECIFICENTHALPY

0t L z- - - " ~ " = J-.----.....I


"01

SPECIFICENTROPY
01
80 100
120
1/.0
i
160
i
0
-~';'~'~=-~'~7~- TEMPERATURE['C ]
"01

PRESSURE = 0 L, 105 NIm2


----- =20x105 N/m2
.... =&Ox 105 Nim2

Fig. 8. Deviations of the computed thermodynamic properties of R- 113 superheated


vapour from du Pont's values. 23
Work ing fluids Jor Rank ine-cycle engines 25

~0-5
x105NIm2 ~ x 105NIm2 5 2
~ 0.~.
~. 0.2
01
0 ~ i i t i i i
20 0 60 80 100 120 lt,0 160
TEMPERATURE[ "C ]

Fig. 9. Deviations of the computed values of the specific volume of R- 113 superheated
vapour from the data of ICI. 24

Figures 5, 6 and 7 show the relative deviations in the calculated


thermodynamic properties of the saturated liquid and vapour of R- 113
when compared with the data of du Pont, Allied Chemicals and ICI,
respectively. Figures 8 and 9 present the deviations of the calculated
values of R-113 superheated vapour from the equivalent data values of du
Pont and ICI respectively.
Figures 5 to 9 indicate that the predicted values of the thermodynamic
properties of R-I 13 agree well with the considered reference data. Over
the investigated range of temperatures (0-160 C), the largest deviation is
that of the specific enthalpy of the saturated liquid (,,- -2.75 per cent)
compared with the ASHRAE data. A summary of the relative deviations
in the predicted thermodynamic properties of R-113, when compared
with the considered reference data, is given in Table 9.

Thermophysical properties

In the following three sections, the predicted values of the specific heats,
dynamic viscosities and thermal conductivities of the R- 113 liquid and
vapour, using the computer sub-routines developed, are presented.
Again, the computed values of the properties were compared with the
corresponding available data in the literature. The relative deviations in
the calculated values, when compared with the reference data, were also
evaluated. A summary of the calculated deviations is given in Table 9.

Specific heats
Figure 10 shows the predicted values of the specific heat of the saturated
liquid of R-113 in comparison with the data of ASHRAE 14 and du
26 O. Badr, P. W. O'Callaghan, S. D. Probert

~a

e'.

"7
,,
o~ o~ ~ o~

"7 -" "7 "7


e~
.o

eD ~ e~ D

~d
e~
[..,

e-,

[-

0 ~a

0
O
W o r k i n g f l u i d s J o r R a n k i n e - c y c l e engines 27

o = ~ = ~ ~ ~ F ~

+ I + I + I I I + I + I + I + I 11 +++ I
28 O. Badr, P. W. O'Callaghan, S. D. Probert

.~ ~ .~ .~ .~ <

.F.

r~

6 6 ~ 6 ~ 6 6 6 6 6 6 6 6 6 ~ 6 ~ ~ ~ 6 ~ 6
I I + I + I I I + I + I + I + I + I + + + 1

r~
Working fluids for Rankine-cycle engines 29

o~ ~ ~o~ ~ ~o~ ~ ~o~o~ ~o~


..x..xx x x x x x x~- a ~ ~
.~.~-~,~j~j~.~,~o,~x ~x ~jx ~j

r.r.l~

60 66 60 60 ~-- --~ ~ 6 6 6 ~ 6 ~ ~
I I ++ + I I I ++ ++ + + + I + + + I

I~., ~'" I.-, ~ '~. 0


30 O. Badr, P. W. O'Callaghan, S. D. Probert

- - PRESENTPREDICTIONEq (16)
------ ASHRAEDATA [ lk ]
%00 .... du PONTDATA[25]
--.-- BI~ININ(3 et al LINEAR ORRELATION [11 ]
BENNIN(~ef ol [ 11 ]
RIEDEL [ 2 6 ]
~' 1200

~1000

BOO

600 i i i i i i i
0 20 t,0 60 B0 100 120 1/,0
TEMPERATURE [ "C ]

. . . . WITH RESPECTTOASHRAEDATA
WITH RESPECTTOdu PONTDATA

L~ \ .
I
20 ~o
I
t- ~
/ I
lOO
I
12o " "'
"qo ~
~.. ~:~ TEMPERATURE['C ]
~--..._~'

Fig. 10. Deviations of the predicted values of the specific heat of the R- 113 saturated
liquid from the published data.

Pont. 25 The calculated values, using the linear correlation developed by


Benning et al., 11 are also presented, together with the experimental results
of Benning et al. ~ 1 and Riedel. 26 Figure l0 indicates that the computed
values, using the second-degree correlating polynomial (eqn. (16)), agree
well with the data of ASHRAE and du Pont, with a maximum relative
deviation of - 1.5 per cent. In the temperature range 0-60 C there is good
agreement between the predicted values and Riedel's experimental data.
Both the values for the specific heat obtained experimentally by Benning
et al. ~ and the values calculated, using their linear correlation, are
generally lower than the present predicted values and the other published
data.
Working fluids for Rankine-cycle engines 31

ot,~

\.\ i
.~=.=
0 r~

.e
I II
~~
i l l l l l l o i , o
o o o
64 ~ 0
e,i e.~
SIV3H )13133d5 7~ll]l~Id -10 OllW [%3 NOI.LVIA:ta3AIIV73~I

i
E
'r~

~.~ ~. '/' '~'E


w

/i "0 >

iI [
!

zI- ~ i- \\ |

o.~.~
I i/,/'
/
F
A'/,~ & i. ; L ' i '
[ >1 ~llr ] d3 [% ] NOilVIA3(3 3AI1V73~
32 O. Badr, P. W. O'Callaghan, S. D. Probert

%
to
z

~E

\
o

e-

~'~
i i ,
,o .4- (-4 o
~ - - ~ O o O ~

S~3H 313133dS7~13Nl~d 90 OIl~a [%] NOIlVlA30 qAI1V73a ~i. ~_

~E ~E

\
z
~E

,j ~ o

\..\ o
e o ~ 0
z

I
,~\~~\\.
, '\ o
~

.~,

i
o
i
o o

[N~N/r ]d3 [ % ] NOIIVIA303AI1V73U


~,
Work ing fluids Jor Rankine-cycle engines 33

Figure 11 shows the calculated values of the constant pressure specific


heat of the saturated vapour of R-113 in comparison with the data
published by ASHRAE x4 and du Pont. 25 The predicted values are almost
invariably higher than those of ASHRAE and du Pont. The calculated
values are of low accuracy when compared with the du Pont data for the
low temperature range. Compared with the ASHRAE data, which are more
recent than those from du Pont, the maximum relative deviation in the
calculated values is only ~ 1.5 per cent. Figure 12 presents the predicted
values for the ratio of the principal specific heats of the saturated vapour
of R- 113 in comparison with the data of du Pont. 25 The figures reveal that
the calculated values become closer to the du Pont data as the
temperature increases and that the maximum relative deviation in the
calculated values is only ~ I. 7 per cent. Figures 13 and 14 show the calcu-
lated values of the constant pressure specific heat and the ratio of the
principal specific heats, respectively, and the corresponding data of du
Pont, 25 for the R-113 superheated vapour at different pressures. Again,
the predicted values are higher than the du Pont data. However, the
relative deviation in the calculated values decreases with increasing
pressure. Nevertheless, the accuracies of the predicted values for the
constant pressure specific heat and the ratio of principal specific heats, for
both the saturated and the superheated vapours of R-113, are satisfactory
for most engineering applications.

Dynamic viscosity
Figure 15 presents the predicted values for the saturated liquid of
R-113 in comparison with the ASHRAE 14 and du Pont 25 data. The
calculated values, using the Witzell and Johnston 15 correlation
coefficients for eqn. (23), those determined using the Gordon et al.
empirical equation 27 and the experimental data of Benning and
Markwood 28 and Lilios z9 are also given. The predicted values are in good
agreement with the data of ASHRAE, du Pont and those evaluated using
eqn. (23) with the Witzell and Johnson correlation coefficients: a
maximum relative deviation of _+ 1.6 per cent occurs. In the low
temperature range (i.e. 0-60C), there is good agreement between the
predicted values and the available experimental data of Benning and
Markwood and those of Lilios. The Gordon et al. correlation predicts
higher dynamic viscosities for the R-I13 saturated liquids at low
temperatures--and lower values at higher temperatures--when com-
pared with both the predicted values and the other published data.
34 O. Badr, P. W. O'Callaghan, S. D. Probert

90
t PRESENTPREDICTION
ASHRAE DATA [ 1/,,]
dU PONT DATA [25]
W1TZELLg JOHNSON CORRELATION[ 15 ]
~,o B0 GORDON ef al CORRELATION[27}
BENNINGAND MARKWOOD[ 2Bl
LILIOS[29]

~7o

60

50

~0

30

20
20 k0 60 80 100 120 %0
TEMPERATURE [C ]

.... WITH RESPECT TO ASHRAE DATA


15 . . . . WITH RESPECTTO du PONT DATA
~ ~" ~""~ - - - - WITH RESPECTTO THE CALCULATEDVALUES
USINGTHE WITZELL 8, JOHNSONCORRELATION

~10
\
5
> os ~..
\, /
!

~oo 2bx z,j) 6b Bb ""... 160 I~0 1/*0l


. !

~xx\ TEMPERATURE C ] I

-05 I
I
x I
/
-10 /
/

-15

Fig. 15. Comparison between the predicted values of the dynamic viscosity of the R- 113
saturated liquid and the available data in the literature.
._.9. Ua

"I ( ~
<

u
o. ~

~ 5t -

~ ',X.
o

~
> ,-

o I 0
o o o o

0
[ )as uJ16)I01.] 6T~ AIISO]SIA ]INVNAC] [ % ] NOIIVlA3C] 3 A I I . V ] ~
~'~.

o
O .-

.i .~ C~
u

LW~--
=Z~
o

J
e o ) ~o
\
'~ o
N ~~,
I I
I
i I
N ~
~N
l l i , J , i
o o o

~ :::3
[ ~as uJ I ~:~ .0~ ] , F i 'X.I.ISO]SIA ]IWVNAO [ % I NOLWIA313 3AI'~'13~ 0
.s ~ _~

J:: 0

'\\ 7 "~

i!i "\ ~
i "I

-~===.
"~ m r.,l

8. o
_, - . , ~ o.~

[ )~ u~I ,NBt~~:_0).1 .~,~ AIlAI1]Q(]NO] 7VN~3H1 [ % ] NOIIVIA~I3 ]]AIIV73~I


-~'; E!

mid ~

/
, ) 0

/ .~_ ~ / s

.// . - ~ = = ~.

," /
/ // iliii!i
~I~=<0~<
=
~- ~_ f ', ).,.) (.~

q._,
// Illi "i "~, 0
.v'/.// . . . . . .
o kn o ~ Q in ")~,
o o o
[ ~lU~l~ ~=OL] ~ A11AIJ.~IaNO] 7 V ~ I ~ Z [%} NOIIyIA~ 3AIIVT~

~.8
Working fluids for Rankine-eycle engines 37

Figure 16 presents a comparison between the predicted values of the


dynamic viscosity of R-I 13 at atmospheric pressure and the published
data o f A S H R A E 14 and du Pont. 25 The values calculated using the semi-
empirical generalised equation of Li 3 are also given. The predicted
values agree well with the A S H R A E data, the maximum deviation being
only ~ 0.25 per cent. The du Pont data are invariably lower than both the
predicted values and the ASHRAE data. It can be seen that the calculated
values using the generalised semi-empirical equation of Li are very low in
comparison with the other data in the low temperature range. The
difference tends to decrease with temperature.
Figure 17 shows a comparison between the predicted values of the
dynamic viscosity of the R-113 saturated vapour and the ASHRAE
data. 14 The maximum relative deviation in the calculated values is -,, 1.5
per cent.

Thermal conductivity
The values of the predicted thermal conductivities for R-113 saturated
liquid are presented in Fig. 18 in comparison with the ASHRAE 14 and du
Pont z5 data. The corresponding values obtained using the nomogram
developed by Chidambaram, 11 calculated using the semi-empirical
generalised equation of Li 31 and the experimental data of Powell and
Challoner, 32 are also shown. The predicted values are corroborated by
the data of ASHRAE and du Pont with a maximum deviation of ~ 0.5 per
cent up to a temperature of 150 C. According to the ASHRAE data, the
decrease of the thermal conductivity with temperature becomes strongly
non-linear for temperatures higher than 150C and, therefore, the
accuracy of the predicted values, using the linear relationship (i.e.
eqn. (26)), is expected to be poor. Good agreement ensues between
the predicted values and the experimental data of Powell and Challoner.
It is apparent that the use of Chidambaram's nomogram yields
higher values, whereas employing Li's semi-empirical generalised equation
yields lower values, than both the predicted and the other published
data.
Figure 19 presents the predicted values for the thermal conductivity of
R-113 vapour at atmospheric pressure, together with the data of
ASHRAE 14 and du Pont. 25 The results indicate that the maximum
deviation in the predicted values is -~ 2 per cent.
38 o. Badr, P. W. O'Callaghan, S. D. Probert

ACKNOWLEDGEMENTS

The authors wish to thank the Egyptian Government and the British ORS
scheme for support of this research project. Copies of the computer sub-
routines are available from the authors.

REFERENCES

1. P. Garay, Application of chemical fluids in a Rankine cycle plant, Proc. 1975


IECEC, No. 759209, Aug. 1975, pp. 1435-8.
2. R. Niggemann, W. Greenlee and P. Lacey, Fluid selection and optimization
of an organic Rankine cycle waste-heat power conversion system. ASME
Paper No. 78-WA/Ener-6, presented at the Winter Annual Meeting, San
Francisco, Calif., USA, Dec. 10-15, 1978.
3. H. Curran, Use of organic working fluids in Rankine engines, J. Energy, 5(4)
(July-Aug., 1981), pp. 218-23.
4. E. Wali, Optimum working fluids for solar-powered Rankine-cycle cooling
of buildings, Solar Energy, 25(3-D), (1980), pp. 235-41.
5. J. Martin, Correlations and equations used in calculating the thermo-
dynamic properties of freon refrigerants, Thermodynamic and Transport
Properties of Gases, Liquids and Solids, ASME, New York, USA, 1959.
6. R. Downing, Refrigerant equations, ASHRAE Trans., 80 (Part 2) (2313)
(1974), pp. 158-69.
7. Thermodynamic Properties of 'FREON' 11, E. I. du Pont de Nemours and
Company~'FREON' Products Division, Wilmington, Delaware, USA,
Technical Bulletin T-11, 1965.
8. A. Benning and R. McHarness, Thermodynamic properties of fluorochloro-
methanes and -ethanes, Industrial and Engineering Chemistry, 32(6) (June,
1940), pp. 814-16.
9. A. Benning and R. McHarness, Thermodynamic properties offluorochloro-
methanes and -ethanes, Industrial and Engineering Chemistry, 32(4) (April,
1940), pp. 497-9.
10. A. Benning and R. McHarness, Thermodynamic properties of fluorochloro-
methanes and -ethanes, Industrial and Engineering Chemistry, 32(5) (May,
1940), pp. 698-701.
11. m. Benning, R. McHarness, W. Markwood and W. Smith, Thermodynamic
properties of fluorochloro-methanes and -ethanes, Industrial and
Engineering Chemistry, 32(7) (July, 1940), pp. 976-80.
12. J. Martin, Thermodynamic properties of dichlorotetrafluoroethane, J.
Chemical and Engineering Data, 5 (July, 1960), pp. 334-6.
13. D. Hartree, Numerical analysis, Oxford University Press, England, 1952,
p. 194.
Working fluids for Rankine-cycle engines 39

14. ASHRAE Handbook of Fundamentals. Chapters 15 and 16. ASHRAE, New


York, USA, 1977.
15. O. Witzell and J. Johnson, The viscosities of liquid and vapour refrigerants.
Paper presented at ASHRAE Semi-annual Meeting, January 25-28,
Chicago, USA, 1965.
16. B. Latto and A. A1-Saloum, Extensive viscosity correlations for refrigerants
(halogenated hydrocarbons) in liquid and vapour phases, ASHRAE Trans.,
76(Pt. 1) (2130) (1970), pp. 64-80.
17. T. Phillips and K. Murphy, Liquid viscosity of halogenated refrigerants,
ASHRAE Trans., 76(Pt. 2) (2152) (1970), pp. 146-56.
18. P. Liley and W. Zahn, Problems and procedures in evaluating values of
thermophysical properties of refrigerants, ASHRAE Trans., 78(Pt. 2) (2224)
Research Report (1972), pp. 102-13.
19. E. Keating and R. Matula, Correlation and prediction of viscosity and
thermal conductivity of vapour refrigerants, ASHRAE Trans., 75(Pt. 1)
(2092) (1969), pp. 29-39.
20. R. Matula and O. Witzell, A generalized approach for predicting the reduced
viscosity of vapour refrigerants, ASHRAE Trans., 73(Pt. 1) (2030) (1967),
pp. VI.I.l-l.4.
21. S. Chidambaram, Thermal conductivity of liquid refrigerants, British Chem.
Eng., 14(9) (Sept., 1969), p. 1257.
22. V. Gruzdev, Ye. Sheludyakov, A. Kikiyanenko, Ya. Kolotov, V. Lavrov,
A. Shilyakov, A. Shesterova and A. Shumskaya, Thermophysical properties
of freons, Fluid Mechanics Sot,iet Research, 3(5) (Sept.-Oct. 1974),
pp. 64-8.
23. A. Benning and R. McHarness, The thermodynamic properties of'FREON"
113, E.I. du Pont de Nemours and Company--'FREON' Products
Division, Wilmington, Delaware, USA, Technical Bulletin T-113A, 1938.
24. Thermodynamic Properties of "ARCTON' 113, Imperial Chemical
Industries Limited--Mond Division, UK, 1980.
25. Transport Properties of'FREON" Fluorocarbons, E. I. du Pont de Nemours
and Company--'FREON' Products Division, Wilmington, Delaware,
USA, Technical Bulletin C-30, 1973.
26. L. Riedel, Determination of the thermodynamic properties of trifluoro-
trichloroethane, Z. ges Kiilte-Ind., 45 (1938), pp. 221-5.
27. D. Gordon, J. Hamilton and W. Fontaine, An empirical equation for
predicting the viscosity of liquid refrigerants, ASHRAE Trans., 75(Pt. 1)
(2093) (1969), pp. 40-52.
28. A. Benning and W. Markwood, The viscosities of "Freon' refrigerants,
Refrigerating Engineering (April, 1939), pp. 243 7.
29. N. Lilios, The viscosity of several liquM refrigerants at atmospheric pressure,
MS Thesis, Purdue University, USA, 1957.
30. C. Li, Estimation of the gas viscosities of halocarbon refrigerants, A SHRAE
Trans., 79(Pt. 1) (2275) (1973), pp. 172 4.
40 O. Badr, P. W. O'Callaghan, S. D. Probert

31. C. Li, A generalised correlation of liquid thermal conductivity of


halogenated hydrocarbon refrigerants, A S H R A E Trans., 76(Pt. 2) (2151)
(1970), pp. 140-5.
32. R. Powell and A. Challoner, Proposed values for the thermal conductivities
of some liquid refrigerants, Modern Refrigerat ion, 63 (Jan. 1960), pp. 42-6.