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
ammoniac-eau
On prdsente une nouvelle correlation des propridtds
d'#quilibre des mdlanges ammoniac-eau utilisables pour la
conception et I'essai des groupes b absorption, en particulier
pour les pompes ~ chaleur. Le domaine de temperature a#t#
A new correlation of equilibrium properties
of ammonia-water mixtures is presented for
use in thedesign and testing of absorption units,
and especially for heat pumps. The temperature
range has been extended to 500 K and the
pressure range to 50 bar. The equations of state
Nomenclature
d~, e~
a i, b i. c i, coefficients
A~, B~, C~, D~, E~ dimensionless coefficients
c, molar heat capacity at
constant pressure,
kJ kmol -I K-1
g Gibbs free energy, kJ kmol -~
h molar enthalpy, kJ kmol -~
K equilibrium constant
p pressure, bar
R gas constant 8.314
kJ kmol -~ K -I
s molar entropy,
kJ kmol-~ K-
T temperature, K
v molar volume, m 3 kmol -~
w ammonia mass fraction
Absorption processes operating with a mixture of
ammonia and water have been used in refrigeration for
a long time. Their advantages such as low noise level,
reliability, and good partial load behaviour make them
also suitable as heat pumps.
In order to establish a systematical computer
analysis of such processes the physical properties of
the working fluid should be available in the form of
analytical functions. The equation of state for
ammonia-water mixtures proposed by Schulz 1 is
limited to a maximum pressure of 25 bar, so that
its application in the study of heat pumps is restricted.
B.Z. is from Gebr(Jder Sulzer Aktiengesellschaft. Winterthur,
Switzerland. C.T. is Professor at the Institut f6r Verfahrens- und
K~ltetechnik, ETH-Zentrum, Z0rich, Switzerland. Paper received
5 May 1983.
0140-7007/84/002101-06S3.00
Volume 7 Number 2 March 1984 © 1984 Butterworth Et Co (Publishers) Ltd and IIR
@tendu jusqu'~ 500 K et le domaine de pression jusqu'@ 50
bar. Les @quations d'@tat utilis@es s'appuient sur celles de
Schulz. Les volumes massiques, les pressions de vapeur, les
enthalpies et les constantes d'@quilibre pour les mdlanges
sont compares aux meilleurs r@sultats exl~rimentaux. Les
r~sultats sont pr@sent@ssous forme de diagramme de pres-
sion de vapeur, temperature et enthalpie-concentration.
used are based on those of Schulz. Values of
specific volume, vapour pressure, enthalpies
and equilibrium constants for mixtures are
compared with the best experimental data. The
results are presented in the form of vapour
pressure and enthalpy-concentration diagrams.
x ammonia mole fraction in
the liquid phase
y ammonia mole fraction in
the gas phase
/~ chemical potential,
kJ kmol -~
Superscripts
g gas phase
I liquid phase
o ideal gas state
Subscripts
o reference state
R reduced, dimensionless
S saturated
By modification of some relations the range
230 K< T< 500 K and 0.2 b a r < p < 50 bar can be
reproduced with sufficient accuracy.
S t r u c t u r e of t h e e q u a t i o n of state
Schulz 1 made use of two separate equations for
the liquid and the gaseous phases, which are linked by
the conditions of phase equilibrium:
7~=T~
pl =pQ
i g
, ~ (1)
/J2=/J2
The functions show the following structure:
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
following functions for fl, f2, and f3:
fl(t,p)=el+e2P+ (e3+e4P) T + e s / T + e 6 / T 2 (21)
f2(z.~)=e7 + eaP+ (e9 + e~oP) T
+ el~/T + e~2/T 2 (22)
f3(T.p)=e13+e14P+els/T +e16/T 2 (23)
Using the reduced properties defined in (1 6) we can
combine (2), (20), (21), (22), and (23) to an equation
for the dimensionless free energy of the liquid mixture.
g~= (1 - x)g~ .2o + Xg~ ,H3
+ 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
+ E~2/T~] ( 2 x - t )
+ [E13+ E14PR+ EI~/TR + E~6/T~]
( 2 x - 1 )2}x(1 - x ) (24)
Equation (3) may be rewritten analogously
g~= (1 - y ) g ~ .~o+ Yg~ N.3
+ T R [ ( 1 - y ) I n ( 1 - - y ) + y In y] (25)
Determination of the coefficients of the
equation for the Gibbs excess energy
The coefficients E~ were determined by least
square regression considering volume, enthalpy, and
equilibrium data. 7-11 (Table 3).
Accuracy of the equation of state
To give an idea of the accuracy of the equation of
state, calculated values are compared with those pub-
lished by different authors (Figs 1-4). Fig.4 presents
this comparison and confirms the doubts of Won et
al. 12 about the vapour compositions given by Macriss. ~
Mathematical treatment of the equation
of state
For the application of the equation of state a
computer is needed. For a given temperature, pressure,
106
and composition, all other thermodynamic properties
may be calculated explicitly. To determine phase
equilibria a system of two nonlinear equations has to be
solved. Newton iteration converges within three to five
steps to adequate accuracy if the typical mathematical
properties of the equations are considered.
The use of this equation for absorption and
desorption processes in various configurations, as well
as reverse absorption processes, has been demo-
nstrated by one of the Authors? 3
The authors wish to thank the Kommission zur Forde-
rung der Wissenschaftlichen Forschung and the Geb-
rOder Sulzer Aktiengesellschaft for financial support.
References
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Ammoniak und Wasser und die Berechnung von
Absorptionsk~ltemaschinen- Prozessen, Habilitationsschrift,
Abt. for Maschinenbau und konstruktiven Ingenieurbau. Ruhr
Universit~t Bochum (1971 )
2 Funk,H. Mitt K#ltetechn Inst TechnHochschule Karlsruhe 3
(1948) 33
3 Mollier, R. NeueTabellen und DiagrammefQrWasserdampf,
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4 Hear, L. J Res Nat Bur Stan A. Phys Chem 72A 2 (1968)
207-216
5 Haar,L.,Gallagher, J.S.JPhysChemRefData73(1978)
635-792
6 Keenan, J. H., Keyes, F. G., Hill, P. G., Moore, J. G.
Steam tables, John Wiley, New York (1978)
7 Jennings, B. H. ProcXIIIIR CongrMadrid2 (1967) 329-
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)
9 Wucherer, J.ZfdgesKalteindustrie306 (1932) 97-t04: 7,
136-140
10 Scatcherd, G., Epstein, L. F., Warburton, J., Cody, P. J.
RefrEng 53 5 (1947) 413--452
11 Bo Pierre Kylreknisk Tidskrift 18 (1959) 89-90
12 Won, K. W,, Selleck, F. T., Walker, C. K., Irvine
Proceedings- part I - posterpapers, phaseequilibria and fluid
properties in the chemical industry, 2nd Int Conference Berlin
(1980). Accepted by JAIChE (1983)
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ptionsprozesse mit dem Stoffpaar Ammoniak-Wasser. Diss.
ETH Hr. 7070, ZQrich (1982)
14 Zinner, K. Warmet6nung beim Mischen von Ammoniak und
Wasser in Abh~ngigkeit von Zusammensetzungund Tempe-
ratur Z ges K#lte-lnd 41 2 (1934) 21-29
Revue Internationale du Froid