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Anda di halaman 1dari 40

Organic Working Fluids for Rankine-cycle Engines

School of Mechanical Engineering, Cranfield Institute of Technology,

Cranfield, Bedford MK43 0AL (Great Britain)

SUMMARY

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 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.

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.

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

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 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 )

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

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.

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.

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

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)

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).

k

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

numbers in Table 1 were not rounded off to values commensurate with the

experimental errors of measurement.

Derived equations

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

will be presented.

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~

x - ~-~ + rloge (10)

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

~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

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.

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)

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:

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~/)

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

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.

a similar way to that employed when evaluating its specific enthalpy,

namely:

Aht~' (15)

s~ = s o T

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

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

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

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)

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>

Workingfluidsfor Rankine-cycle engines 15

+--

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

+- +

( 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

) KT,) 1

_ 4IA 4 + B4 T + --~

C.[97exp(--KT~)]

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

(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

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:

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

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

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

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

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

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)

conductivity of vapour refrigerants can be described by the expression:

2 - 2* = GAp"i, (29)

Working fluids Jbr Rankine-cycle engines 19

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

SATURATIONPRESSURE

1-0

0.5

0

-05

. . . . ~--.~/"~6o

SPECIFICVOLUME

------ SATURATEDLIQUID

- - SATURATEDVAPOUR

\N

\\

\

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

"01

SPECIFICENTROPY

01

80 100

120

1/.0

i

160

i

0

-~';'~'~=-~'~7~- TEMPERATURE['C ]

"01

----- =20x105 N/m2

.... =&Ox 105 Nim2

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

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~

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

..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

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.

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~

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 ~

~E ~E

\

z

~E

,j ~ o

\..\ o

e o ~ 0

z

I

,~\~~\\.

, '\ o

~

.~,

i

o

i

o o

~,

Work ing fluids Jor Rankine-cycle engines 33

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 ]

15 . . . . WITH RESPECTTO du PONT DATA

~ ~" ~""~ - - - - WITH RESPECTTO THE CALCULATEDVALUES

USINGTHE WITZELL 8, JOHNSONCORRELATION

~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.~

-~'; 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

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

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

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

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.

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