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0140-7007(95)00006-2
A set of five equations describing vapour-liquid equilibrium properties of the ammonia-water systemis presented.
They are intended for use in the design of absorption processes. Using variable dependences of technical relevance
the equations make it possible to avoid iterative evaluations. The equations were constructed by fitting critically
assessed experimental data using simple functional forms. They cover the region within which absorption cycles
commonly used operate most often. The enthalpy of the gas phase has been calculated in the ideal mixture
approximation. The results are presented in the form of an enthalpy-concentration diagram.
(Keywords: refrigerants; ammonia-water mixture; equilibrium properties; absorption)
Nomenclature
ai
h
M
N
P
T
X
Y
S
W
Coefficients
Specific enthalpy (kJ kg- 1)
Molar weight (kg mol- 1)
Number of data points
Pressure (MPa)
Temperature (K)
Ammonia mole fraction in the liquid phase
Ammonia mole fraction in the gas phase
Mean deviation
Systematic deviation
Ammonia mass fraction in the gas phase
Greek letters
Subscripts
A
g
i
k
1
W
0
Ammonia
Gas phase
Term of fitting polynomial
Experimental data point
Liquid phase
Water
Reference value
228
229
, 1
-+
.-+
O.
O.
0.01
0.001
0'.a
0:4
of 0
018
Ref. 8
Ref. 6
Ref. 7
Ref.11
Ref. 9
Ref. 5
10~
o_
~_
8 B
0.1
00
0.001
! ++
o
o.a
0.4
0'.6
0'.8
Ref.16
Ref.18
Ref.12
Ref. 4
Ref.15
230
10
t~
13.
:[
0.1
..
-~
~ ~
0.01
0.001
0
o:a
0,4
'
0.6
'
o:8
Y
Ref.11
Ref. 6
[]
Ref. 9
Ref. 5
Ref.12
Ref. 4
(1)
where
yMA
yM A + (1 - y)Mw
The value p=p(T,y)
w =
(2)
( = ~ ai~"'v m'
(3)
where
( = Z(z, u, v);
~ = U(u, v);
(6)
v = V(u, v)
(4)
(7)
y(p,x)=l-exp[ln(1-x)~,i
a f P---')m~x"'/3]
"
hi(T, x) = I1o ~i
a i ----
hg(T,y):ho~i
ai(1-~o)m'(]-y)
\Po/
(8)
(9)
X n~
nil4
(10)
Table I
Tableu l
DIi
ni
(di
1
2
3
4
5
6
7
8
9
10
II
12
13
14
0
0
0
0
0
1
I
1
2
4
5
5
6
13
0
1
2
3
4
0
1
2
3
0
0
1
0
1
+0.322302
0.384206
+0.460965
-0.378945 x
+0.135610x
+0.487755 x
--0.120 108 x
+ 0 . 1 0 6 154 x
-0.533589
+0.785041 x
-0.115941 x
--0.523 150 x
+0.489596 x
+0.421059 x
To = 100 K, po = 2 MPa
101
10
10
10 -2
10 3
10
10
10
10 -3
10 j
10 z
10 1
10 ~
10 -1
E x p o n e n t s a n d coefficients of E q u a t i o n (7)
Table 5
Tableau 2
i
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
mi
Ill
ai
0
0
0
0
1
t
I
2
2
3
3
4
4
5
5
6
7
0
1
2
3
0
1
2
0
I
0
1
0
2
0
2
0
2
+0.324004 x
-0.395920 x
+0.435624 x
-0.218943x
-0.143526
+0.105256 x
-0.719281 x
+0.122362 x
- 0.224 368 x
--0.201 780 x
+0.110834 x
+0.145399 x
+0.644312 x
--0.221 246 x
-0.756266 x
-0.135529 x
+0.183541 x
Tableau 5
i
10 ~
10
10 ~
10 2
I(P
101
10 1
1(12
101
1112
10 a
102
10 o
101
100
101
100
231
I
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
Irl i
ni
.li
0
1
2
3
0
1
2
3
11
1
2
0
1
0
4
2
1
0
0
0
0
2
2
2
2
3
3
3
4
4
5
6
7
10
+0.128827 x
+0.125247 x
-0.208748 x
+0.217696x
+0.235687 x
-0.886987 x
+1/.102635x
1t.237440 x
0.670 515 x
+0.164508 x
0.936849 x
+1/.842254 x
0.858807 x
-11.277049
-1/.961 248 x
+0.988009 x
+11.308482 x
10 ~
10
10 ~
10 I
10 ~
10 ~
102
I(P
101
l() z
10 ~
111~
10 ~
l0 t
10
111~
1()~
Ta = 100 K, Po = 2 M P a
h o = 1000 kJ k g - 1, To = 324 K
Table 3
Tableau 3
Ecarts moyens et /burch(,tles des {carts des donndes e.rp(;rimentah, s # l'{quation 16)
Tableau 6
DI i
IIi
ai
1
2
3
4
5
6
7
8
9
t0
II
12
13
14
0
0
0
0
I
2
2
3
4
5
6
7
7
8
0
1
6
7
0
1
2
2
3
4
5
6
7
7
+1.98022017 x
-1.18092669 x
+2.77479980 x
-2.88634277 x
-5.91616608 x
+5.78091305 x
-6.21736743 x
-3.421 98402 x
+1.19403127 x
- 2 . 4 5 4 13777 x
+2.91591865x
-1.84782290 x
+ 2 . 3 4 8 19434 x
+4.803 106 17 x
101
101
10 ~
101
10 l
102
10
103
104
104
10 a
10'*
I0 ~
103
Ref.
4
5
6
7
8
9
11
12
15
16
18
Total
a
(K)
s
(K)
-(K)
Aymi,,-- Ay,.....
(K)
191
4
29
105
3
23
241
490
160
34
75
0.31
1.90
0.84
1.70
2.60
0.32
0.70
0.48
0.41
0.45
0.73
0.02
1.811
-0.40
0.80
2.00
0.04
0.20
0.01
0.211
-0.20
0.07
0.25
1.80
0.65
1.40
2.01/
0.28
0.48
0.40
0.33
0.33
0.50
1.1 t).7
0.9 2.4
2.2 1.6
- 4 . 6 5.2
1.1 4.4
- 1 . 0 0.4
- 3 . 1 3.11
- 1.4 1.5
-11.9 0.9
- 1.0 0.1
- 2 . 6 2.4
1365
0.72
0.00
11.45
-4.6
5.2
p(~ = 2 M Pa
Table 4
Tableau 4
Tableau 7
m i
ll I
ai
1
2
3
4
5
6
7
8
9
10
tl
12
13
14
15
16
0
0
0
0
0
0
1
1
2
3
5
5
5
6
6
8
l
4
8
9
12
14
0
1
1
3
3
4
5
2
4
0
--0,761 080
+0.256905
--0.247092
+0.325952
-0.158854
+0.619084
+0.114314
+0.118 157
+ 0 . 2 8 4 179
+0.741 609
+0.891 844
- 0 . 1 6 1 309
+ 0 . 6 2 2 106
- 0 . 2 0 7 588
-0.687393
+0.350716
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
101
10 z
103
103
103
102
102
10 ~
10 ~
10 ~
10 a
10`*
103
103
101
10 ~
h o = 100 kJ k g - ~ . To = 273.16 K
equation,
deviations
and
are
with
bands
of absolute or relative
s u m m a r i z e d in Tables 6-8. These
Ref.
5;
a
(K)
s
(K)
5
(K)
kym,,
(K)
4
5
6
9
l1
12
91
122
29
23
191
378
0.87
2.6l
1.70
0.42
1.50
0.84
-0.43
0.50
0.34
0.17
-0.06
-0.01
1/.73
2.20
1.30
1/.32
1.00
11.67
-2.1
4.5
3.O
- 1.3
7.0
2.0
Total
834
1.34
0.00
1/.94
- 7.0 5.9
Ay, ....
0.9
5.9
3.8
11.6
3.5
2.7
Ecarts moyens el /(~urchetle~ d('.~ ~;cctrts dex do/m['e.~ e.\p(;rimentales de I'~;quaHon (8)
Tableau 8
cr
(%)
.~
A):mi,,
(%)
(%)
1%1
156
0.72
0.38
1/.38
24
1.80
1.00
1.30
11
122
177
1.80
0.48
0.46
-0.06
1.3(I
0.31
--2.1
1.5
Total
479
1.10
I).03
1/.63
-6.7
5.4
Ref.
12
AV, ,x
2.6 0.3
-1.1
5.2
6.7 5.4
232
15
"7
0
4"
oo
t~oo
0
~ 0
xo
o o
Xo
" ~
0
x
o 0.2
+ 0.4
o 0.6
x 0.8
XX
-10
100
20(
t , C
Figure 6 Comparison of gas-phase enthalpy calculated from Equation
(10) along selected isopleths x = const, with data published by Scatchard
et al. ~
Figure 6 Comparaison de l'enthalpie de la phase gazeuse calculbe d
partir de I'bquation (10), le long de certaines lignes isoplethes choisies
(x - const. ), avec des donnbes publides par Scatchard et aL
101
.~
- ~
,s=
~v~
0.6/
--
....
"=~-10
0.2
..I,./"
".............:%'k ""
,,
", y = 0.99
I
0
0.2
,5
100
200
t , C
-1.5
0.2
0.4
0.6
0.8
x
Figure 4 Comparison of T(p, x) data collected from Equation (6) with
the formulation of Ziegler and Trepp 1
Figure 4 Comparaison des donn~es T(p, x) calculbes h partir de
1.5 \
I
0.2
J
0.4
, /
-1.5
0
I
0.6
i
0.8
Y
Figure 5 Comparison of T(p,y) data calculated from Equation (7)
with the formulation of Ziegler and Trepp ~
Figure 4 Comparaison des donnbes T(p, y) calculbes ~ partir de
233
I
!
2600
Ii
2400
2200
MPa
2000
~= 1800
1600
1400 -
1200
1
I
0.1
1000~
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Figure 8
Figure 8
eq
.X170 "
600 ~ c -
c~
-..
,,
8t
-4o,
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.9
234
Conclusions
The suitable general functional forms presented in this
work, once found, are applicable to any new experimental
data; fitting of the respective coefficients only is required.
The accuracy of the equations follows from the deviations
of the experimental data points used for fitting given in
Tables 6-8. The root mean square deviation 0.7 K for
T(p, x) corresponds to a mean probable error of +0.5 K.
Similarly, estimation of the mean probable error for the
T(p, y) relation gives the value _+0.8 K. The overall
accuracy of the specific enthalpy of the liquid phase given
by uncertainty in Zinner's data and by the approximation
amounts to 4 kJ kg -1. Thus when hi(T, x) and hg(T, y)
are combined with the relationships T(p, y) and T(p, x)
or y(p, x) they give differences in enthalpy between the
liquid and gas phases with accuracy better than 1%, i.e.
about 10 kJ kg- 1.
As well as avoiding iterative calculations, the merit of
the fast approximation functions consists in their
simplicity, which facilitates their incorporation in any
computer code. Nevertheless, some care is needed when
using them, to ensure the convergence of iterative
engineering calculations (e.g. in optimization procedures),
as the accuracy required depends on the nature of the
calculations.
The equations presented can also be used to calculate
initial values for a consistent formulation. When
employed in this alternative way, they provide a
substantial reduction in the number of iterations.
8
9
10
11
12
13
14
15
16
17
18
19
References
1
2
20
21
22