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Equation of state for ammonia-water

mixtures

B. Ziegler and Ch. Trepp

Key words: refrigerant, ammonia, ammonia-water mixture, equilibrium properties

Equation d'etat pour les melanges @tendu jusqu'~ 500 K et le domaine de pression jusqu'@ 50
bar. Les @quations d'@tat utilis@es s'appuient sur celles de
ammoniac-eau Schulz. Les volumes massiques, les pressions de vapeur, les
enthalpies et les constantes d'@quilibre pour les mdlanges
On prdsente une nouvelle correlation des propridtds sont compares aux meilleurs r@sultats exl~rimentaux. Les
d'#quilibre des mdlanges ammoniac-eau utilisables pour la r~sultats sont pr@sent@ssous forme de diagramme de pres-
conception et I'essai des groupes b absorption, en particulier sion de vapeur, temperature et enthalpie-concentration.
pour les pompes ~ chaleur. Le domaine de temperature a#t#

A new correlation of equilibrium properties used are based on those of Schulz. Values of
of ammonia-water mixtures is presented for specific volume, vapour pressure, enthalpies
use in thedesign and testing of absorption units, and equilibrium constants for mixtures are
and especially for heat pumps. The temperature compared with the best experimental data. The
range has been extended to 500 K and the results are presented in the form of vapour
pressure range to 50 bar. The equations of state pressure and enthalpy-concentration diagrams.

Nomenclature
x ammonia mole fraction in
d~, e~
a i, b i. c i, coefficients the liquid phase
A~, B~, C~, D~, E~ dimensionless coefficients y ammonia mole fraction in
c, molar heat capacity at the gas phase
constant pressure, /~ chemical potential,
kJ kmol -I K-1 kJ kmol -~
g Gibbs free energy, kJ kmol -~
h molar enthalpy, kJ kmol -~ Superscripts
K equilibrium constant
g gas phase
p pressure, bar
I liquid phase
R gas constant 8.314
o ideal gas state
kJ kmol -~ K -I
s molar entropy, Subscripts
kJ kmol-~ K-
T temperature, K o reference state
v molar volume, m 3 kmol -~ R reduced, dimensionless
w ammonia mass fraction S saturated

Absorption processes operating with a mixture of By modification of some relations the range
ammonia and water have been used in refrigeration for 230 K< T< 500 K and 0.2 b a r < p < 50 bar can be
a long time. Their advantages such as low noise level, reproduced with sufficient accuracy.
reliability, and good partial load behaviour make them
also suitable as heat pumps.
In order to establish a systematical computer
S t r u c t u r e of t h e e q u a t i o n of state
analysis of such processes the physical properties of Schulz 1 made use of two separate equations for
the working fluid should be available in the form of the liquid and the gaseous phases, which are linked by
analytical functions. The equation of state for the conditions of phase equilibrium:
ammonia-water mixtures proposed by Schulz 1 is
limited to a maximum pressure of 25 bar, so that 7~=T~
pl =pQ
its application in the study of heat pumps is restricted. i g

B.Z. is from Gebr(Jder Sulzer Aktiengesellschaft. Winterthur, , ~ (1)


Switzerland. C.T. is Professor at the Institut f6r Verfahrens- und /J2=/J2
K~ltetechnik, ETH-Zentrum, Z0rich, Switzerland. Paper received
5 May 1983. The functions show the following structure:

0140-7007/84/002101-06S3.00
Volume 7 Number 2 March 1984 © 1984 Butterworth Et Co (Publishers) Ltd and IIR 101
liquid phase: Cp(T)O°,-dl + d2T+ d3T2 (1 2)
i - (1 --X ~'~
g(T.p.x)-- /,.~H20(T.p) "T X ,.~NH3(T.p
''l ) Considering
+ R T [ ( 1 - x ) In (1 - x ) + x In x] Po

+ gE(T.p.x) (2) Cgp,T.Po) = C~(,.p=O,-


rrfO2q
j k~T--~j p dp (1 3)
gas phase: 0
Q y + Q the integration leads to the following equations for the
g(T.p.y) = (1 - )gH20(T.p) VgNH3(T,p)
free energy of the pure components:
+ RT[(1 - y ) In (1 - y ) + y In y] (3)
Liquid phase:
The Gibbs free energy of a phase is the sum of the
contributions of the pure components, the ideal free gl(t,p) = ht(to,po)-- TSl(To.po)
energy of mixing and the free excess energy. The gas T T
phase is assumed an ideal mixture of real components.
Other thermodynamic properties, eg for the liquid
phase, may be expressed in terms of the free energy as
+fc.d, ,fco,,d,
To To
follows:
+ (al +a3T+a4 T2) (P-Po)
molar volume
+ a2(p2-p2o)/2 (14)
v =(0glT.ox, gas phase:
k ap .JT.x (4)
g -- g
molar enthalpy g(T.p)- h(zo,p o) -- TS~To.po)

+Ic o T TfcO/Td,
T T
(~fgl(T.p.x) "~

h,=_T2(\ aT ]p.× (5) TO To

+ RT In p/po
molar entropy
+ Cl (p-po)
+ c2 (piT 3- 4po/T3+ 3poT/T4o)
\ #T /p.× (6)
+ c3(p/T 11- 1 2po/.T~ol+ 1 lpoT/T 12)
chemical potential
~-C4OD3/T 11 - - 1 2p3o/T~ol+ 11p3T/T1o2)/3
I
., _..., ~{agrr.,.~l'~
pH 20--,'~ ( T . p . x ) - - A ~ / (7) T a b l e 1. C o e f f i c i e n t s f o r t h e e q u a t i o n s f o r t h e
\ ~J"~ /T. p

#~.3=g~T,p,x)-{" (1 - x ) ez0x')
~ T,p
pure components

Tableau 1. Coefficients pour les ~quations des com-


posants purs
The equations (4), (5) and (6) give the volume.
enthalpy and entropy of mixtures as explicit functions Coefficient Ammonia Water
of temperature, pressure and composition. Phase equi-
libria may be calculated using (1), (7) and (8). A1 3.971423 1O- 2 2.748796 1O- 2
A2 -1.790557-10 -5 - 1.016665.10 -5
A3 -1.30890510 -2 -4.452025,10 `3
A4 3.752836'10 -3 8.38924610 4
Equation of state for pure components
B1 1.634519 101 1.214557' 101
The free energy gi of a pure component is in- B2 - 6.508119 - 1.898065
tegrated from relations for the volume and the heat B3 1.448937 2.911966.10 -1
capacity at constant pressure. The equations sugges-
C1 - 1.04937710 -2 2.136131t 0 -2
ted by Schulz ~ are modified to meet the requirements of
C2 - 8.288224 - 3.169291 101
higher pressures and temperatures. The thermal equa- C3 -6.647257102 -4.634611-104
tion of state dates back to Funk 2 and Mollier. 3 C4 - 3.045352 103 0.0
liquid phase: D1 3.673647 4.O1 9170
02 9.989629"10 -2 -5.175550.10 -2
VI(T,p) =al +a2P+a3T+a4 T2 (9) 03 3.617622 10- 2 1.951939-10- 2
C/(T,Po)=b~ + b2T+ b3 T2 (1 O) h~oR 4.878573 21.821141
horn 26.468879 60.965058
gas phase: SloR 1 .644773 5.733498
S~oa 8.339026 13.453430
V(T,p)
~ =RT/p+Cl +c2/T3+c3/T 11 ToR 3.2252 5.0705
+c4p2/T 11 (1 1 ) Poa 2.O000 3.0000

102 Revue Internationale du Froid


T a b l e 2. M e a n d e v i a t i o n s c a l c u l a t e d f r o m re- T a b l e 3. C o e f f i c i e n t s for the Gibbs eXC(NIS
ference values for pure components energy function

Tableau 2. Ecarts moyens calculus d'apr#s la r~f~rence Tableau 3. Coefficients pour la fonction d'exc~s
pour les composants purs d'~nergie de Gibbs

Ammonia Water E1 -4.626129"101 Es - 1.475383


Property Relative Absolute Relative Absolute E2 2-060225"10 -2 Elo - 5.038107"10- 3
E3 7.292369 E~I - 9.640398" 101
Ps 0.6%0 - 2.0%o - E4 - 1.032613"10 -2 E12 1.226973'102
4.3%0 - 3.0%0 - E5 8.074824-101 E13 - 7.582637
v0 0.6%0 - 1.5%o - E6 - 8.461214"101 E14 6.012445.10 -4
h~ - 0.43 - 0.28 E7 2.452882'101 E15 5.487018" 101
kJ kg- 1 kJ kg- 1 Ee 9.598767"10 -3 E18 - 7.667596.101

h0 _ 0.97 - 0.76
kJ kg- 1 kJ kg- 1 Using (16) and (17), (14) and (1 5) may be rewritten in
terms of the dimensionless variables.
Liquid phase:
I__ I I
g , - hoR-- TSoR
TR TR
The state (TooPo) for w h i c h the same free energy results
in both phases represents a point on the vapour -F I CIpRdTR-- TR f CIpR/TR dTR
pressure curve. To bring the equations in a dimension-
less form w e define the f o l l o w i n g reduced thermody- To. To.
namic properties: + (A1 + A o T . + A 4 ~ ) (PR--Pon)
TR= T/TB + A 2( P2, - P o 2~ ) / 2
Pr=P/PB c~,= B1 + B2TR+ B3T~ (18)
gR = g~ RTe
hR=h/RTB 3%
c~, = c~/R
• • . ±.m_A m
0
s,=s/R (16) • • e-
O
O0 w ~ m • J m -

O
The values of the constants T B, PB and R are: -3%
w=0.2
I , I i I
TB= 100 K O O
O
3% O
P B = l O bar 0
O

R = 8 . 3 1 4 kJ kmol -~ K -~ (17) 0 a. O O 41,6 A A •

/
"-- -3% /
w = 0.4 /
8 #1 , I
I
3%
• Jenninqs 7
200 ~ Schulz'
/ - this work AA A ~A
0 /
/

-3%
w=0.6
1 , I ~ I
IOO
[ 3%
E

O
&A O
O & & & & A & & O
-3%
,w=0.8 I , I , I
I 0 KX) 2OO
I.O 1.2 1.4 1.6 1.8 Teml~roture,°C
v L,IO-3 rn3 kg-I
Fig.2 Comparison of calculated solution vapour pressure data w i t h
Fig.1 Values for the volume of the liquid phase for the w a t e r / a m - experimental values. A - S c a t c h a r d ? ° © - M a c r i s s . s , - P i e r r e . 11
monia system .... Schulz 1

Fig. I Valeursdu volume de la phase/iquide pour le syst~me eau- Fig.2 Comparaison des pressions de vapeur calcul~es de la solution
ammoniac avec les valeurs exp~rimentales

Volume 7 Num6ro 2 Mars 1984 103


B
G i b b s excess e n e r g y of t h e liquid m i x t u r e
I0 The molar free excess energy gE of the liquid
0 phase is expressed by the relation proposed by Redlich
and Kister.
-10 0 0 0 0 []
gE(T.p.x)= x ( 1 - x ) [fl (T,p) + f2(T.p)(2X-- 1 )
w-02
I I Jr- f 3 ( T . p ) ( 2 x - 1 ) 2 . . .] (20)
/
f
0

~-~0 - ol ~ ll o
w-0.4 o 0
I I

J 10 - B
i0 - I

A=~ A_ A
0
,:o, Io
-i0
w-0.6
I I

K) &

w-0.8
/~'~ o o 02
I I I
0 100
Tlmpera~r~ *C
Fig.3 Comparison of calculated enthalpy data for the liquid phase
2OO
" /
with experimental values. Q-Macriss, s l-]-Zinner, 14 A-Scatchard, 1°
.... Schulz 1

Fig.3 Comparaisondes enthalpies catcul~=espour la phase liquide


avec les valeurs expMimentales

gas phase:
Q_ g TRS~oR
gR--hoR-- 0 02 0.4 0.6 0.8 I.O
(I -x)
TR TR
Fig, 4 Comparison of equilibrium constants for water at
different temperatures. O-Macris. 8 A - S c a t c h a r d . 1° + - W o n . ~2
+ c ~ d T , - T, Cp,/T, dT, .... Schulz. - - -this work
ToR ToR
Fig.4 Comparaisondes constantes d "#quilibre de I "eau~ diff#rentes
+ TR In (PR/PoR) tempMatures

5O
+ C1 (PR--PoR)
+ C2(PRIT~ - 4PoalT3o,+ 3PoaT,/~,)
+ C3(PRIT 11 1 2PoRIToR+ 12
11 IIPoRTRIToR)
- -

3 311 11
+ C.(pRIT. - 1 2PoRIToR 3 12
+ 1 lPoaTR/T'R)/3 ,o, f/
CpR-D1 + D2TR+ D3~
go_
(19) /- l /
i 2 i ii 7 /'//,/
D e t e r m i n a t i o n of t h e c o e f f i c i e n t s of t h e
equations for the pure components 'F,///J.,////'f,Z/// / / /
The coefficients D~ are based on values for ~0
published by Haar 4 for ammonia and Keenan e for water
[/~'.o. .p;p" ?" o- /
respectively. The values for h~)R. hBR. D~. B~. C~ were 0 2 _ ~
determined by means of a least square regression
Temp~ture,°C
taking into account volume, enthalpy and vapour
pressure data. 5.6 The coefficient C4 for water was held Fig.5 Equilibriumvapour pressure chart for ammonia-water
fixed at zero to avoid negative partial volumes in the gas Fig. 5 Diagramme de pression de vapeur d'~quilibre pour
phase at high pressures and low temperatures. I'ammoniac-eau

104 International Journal of Refrigeration


2500

2000

1500

O
iooo

eD

IZ3
500
o=

'~ 6or
- 500

I. I I I I I... 1 (.
0.0(3 0.I0 0.20 0.30 0.40 0.50 0.60 0.70 O.BO 0.90
Ammonia mass fraction
Fig.6 Ammonia-water enthalpy concentration diagram Fig. 6 Diagramme entha/pie concentration de I'ammoniac-eau

Volume 7 Number 2 March 1984 105


The progression is restricted to three terms with the and composition, all other thermodynamic properties
following functions for fl, f2, and f3: may be calculated explicitly. To determine phase
equilibria a system of two nonlinear equations has to be
fl(t,p)=el+e2P+ (e3+e4P) T + e s / T + e 6 / T 2 (21) solved. Newton iteration converges within three to five
f2(z.~)=e7 + eaP+ (e9 + e~oP) T steps to adequate accuracy if the typical mathematical
properties of the equations are considered.
+ el~/T + e~2/T 2 (22) The use of this equation for absorption and
desorption processes in various configurations, as well
f3(T.p)=e13+e14P+els/T +e16/T 2 (23) as reverse absorption processes, has been demo-
nstrated by one of the Authors? 3
Using the reduced properties defined in (1 6) we can
combine (2), (20), (21), (22), and (23) to an equation
The authors wish to thank the Kommission zur Forde-
for the dimensionless free energy of the liquid mixture.
rung der Wissenschaftlichen Forschung and the Geb-
g~= (1 - x)g~ .2o + Xg~ ,H3 rOder Sulzer Aktiengesellschaft for financial support.
+ TR[(1--x) In ( 1 - x ) + x In x]
+ {El + E2PR(E34- E4p R)TR4- Es/TR 4- E6/ T
+ [ET+Esp,+ (Eg+E1oPR)TR+E11/TR
References
+ E~2/T~] ( 2 x - t )
1 Schulz, S. Eine Fundamentalgleichung f~Jrdas Gemisch aus
+ [E13+ E14PR+ EI~/TR + E~6/T~] Ammoniak und Wasser und die Berechnung von
( 2 x - 1 )2}x(1 - x ) (24) Absorptionsk~ltemaschinen- Prozessen, Habilitationsschrift,
Abt. for Maschinenbau und konstruktiven Ingenieurbau. Ruhr
Equation (3) may be rewritten analogously Universit~t Bochum (1971 )
2 Funk,H. Mitt K#ltetechn Inst TechnHochschule Karlsruhe 3
g~= (1 - y ) g ~ .~o+ Yg~ N.3 (1948) 33
3 Mollier, R. NeueTabellen und DiagrammefQrWasserdampf,
+ T R [ ( 1 - y ) I n ( 1 - - y ) + y In y] (25) 4. Auflage. Springer Verlag Berlin (1926)
4 Hear, L. J Res Nat Bur Stan A. Phys Chem 72A 2 (1968)
207-216
Determination of the coefficients of the 5 Haar,L.,Gallagher, J.S.JPhysChemRefData73(1978)
equation for the Gibbs excess energy 635-792
6 Keenan, J. H., Keyes, F. G., Hill, P. G., Moore, J. G.
The coefficients E~ were determined by least Steam tables, John Wiley, New York (1978)
square regression considering volume, enthalpy, and 7 Jennings, B. H. ProcXIIIIR CongrMadrid2 (1967) 329-
equilibrium data. 7-11 (Table 3). 334
8 Macriss, R. A., Eakin, S. E., E!lington, R. T., Huebler, J.
Physical and thermodynamic properties of ammonia-water
mixtures,/GT Research Bulletin Chicago, 34 (1964)
Accuracy of the equation of state 9 Wucherer, J.ZfdgesKalteindustrie306 (1932) 97-t04: 7,
To give an idea of the accuracy of the equation of 136-140
10 Scatcherd, G., Epstein, L. F., Warburton, J., Cody, P. J.
state, calculated values are compared with those pub- RefrEng 53 5 (1947) 413--452
lished by different authors (Figs 1-4). Fig.4 presents 11 Bo Pierre Kylreknisk Tidskrift 18 (1959) 89-90
this comparison and confirms the doubts of Won et 12 Won, K. W,, Selleck, F. T., Walker, C. K., Irvine
al. 12 about the vapour compositions given by Macriss. ~ Proceedings- part I - posterpapers, phaseequilibria and fluid
properties in the chemical industry, 2nd Int Conference Berlin
(1980). Accepted by JAIChE (1983)
Mathematical treatment of the equation 13 Ziegler, B. W~rmetransformation durch einstufige Sor-
ptionsprozesse mit dem Stoffpaar Ammoniak-Wasser. Diss.
of state ETH Hr. 7070, ZQrich (1982)
14 Zinner, K. Warmet6nung beim Mischen von Ammoniak und
For the application of the equation of state a Wasser in Abh~ngigkeit von Zusammensetzungund Tempe-
computer is needed. For a given temperature, pressure, ratur Z ges K#lte-lnd 41 2 (1934) 21-29

106 Revue Internationale du Froid