Professional Documents
Culture Documents
SUMMARY
NOMENCLATURE
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.
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.
SUP EO
i--
"'k.,.\.
v
,~ CO~S_.T~_S~
c~F~c
==
e~/
vliil
c ill.
/ _
SPECIFIC ENTHALPY. h ( LINEAR SCALE )
conductivity for the superheated vapour, the two latter values being for
one atmosphere absolute pressure, can also be calculated.
THERMODYNAMIC PROPERTIES
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
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)
+
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).
Derived equations
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~
h = a T + ~ b Tz + ~dT 3 -[- f T 4- k + A2 4 A3
+ pv v - b' 2(v-b') 2
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
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.
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)
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~/)
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
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.
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
Specific heats
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
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)
c, = c , - r / <,9>
B6- Tc C6exp(-KT~)
+ (20)
( 1 + C' exp (~v))exp (~v)
and:
_ R,"
2[ A2 + B2T + C2eXp(-
~
CUr ( t " - b') 2
_ 4IA 4 + B4 T + --~
C.[97exp(--KT~)]
-5IAs+BsT+(r--~7~Csexp(-KTr)1
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
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
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
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
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
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.
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. "='
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
1-0
0.5
0
-05
. . . . ~--.~/"~6o
SPECIFICVOLUME
------ SATURATEDLIQUID
- - SATURATEDVAPOUR
\N
\\
\
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
SPECIFICENTROPY
01
80 100
120
1/.0
i
160
i
0
-~';'~'~=-~'~7~- TEMPERATURE['C ]
"01
~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
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~
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
r.r.l~
60 66 60 60 ~-- --~ ~ 6 6 6 ~ 6 ~ ~
I I ++ + I I I ++ ++ + + + I + + + I
- - 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.
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~
/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 ~
~E ~E
\
z
~E
,j ~ o
\..\ o
e o ~ 0
z
I
,~\~~\\.
, '\ o
~
.~,
i
o
i
o o
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 ]
~10
\
5
> os ~..
\, /
!
~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.~
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
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