ENERGY RESEARCH, VOL.

10, 5 9 4 8 (1986)

THERMODYNAMIC PROPERTIES OF LITHIUM

NITRATE-AMMONIA MIXTURES
M.K.A G G A R W A L
Dept. 01Mechanical Engineering, Delhi College of Engineering, Kashmere Gate, Delhi. I loo06. India
AND
R. S . A G A R W A L
Dept. of Mechanical Engineering, Indian Institute ojTechnology, Hauz Khas, New Delhi, I lOOl6, India

SUMMARY
In this paper, the thermodynamic properties of lithium nitrate-ammonia mixtures are presented. The vapour
pressure-temperature correlations are developed by fitting the experimental P-T-x data. The enthalpy of solution, the
latent heat of vaporization, the integral heat of solution and the differential heat of solution are presented in appropriate
tabular and graphical forms.

KEY WORDS Binary mixtures Absorbent-refrigerant combination Thermodynamic properties Vapour pressure correlation
Enthalpyxomposition diagram

INTRODUCTION
The absorbent-refrigerant combination of lithium nitrate and ammonia has been found to be a promising
working fluid for solar powered vapour absorption refrigeration system. Earlier investigations were confined
to presenting its relative importance over other working fluids, e.g. H z O-NH3, LiBr-HzO, NaSCN-NH, and
CaClZ-NH,.
The limited P-T-x data reported by Gensch (1937) and Blytas and Daniels (1962), being insufficient for
developing a full range of thermodynamic properties, the vapour pressure data of LiNO,-NH, were measured
over a complete useful range of pressures, temperatures and compositions by Aggarwal (1984).
This paper reports the thermodynamic properties of lithium nitrate-ammonia mixtures. The properties, e.g.
enthalpy, latent heat of vaporization, integral heat of solution and the differential heat of solution have been
computed and presented in appropriate tabular and graphical form.

THERMODYNAMIC DATA
The basic information necessary for evaluating the thermodynamic properties of any absorbent-refrigerant
combination includes the P-T-x data, heat capacity and an equation of state for vapour phase.
In the case of LiN0,-NH, mixtures, very little information on thermodynamic properties is available.
Gensch (1937)has determined the boiling points at atmospheric pressure between 20 and 70°C as functions of
concentration, and thereby computed the P-T-x data, which have been shown graphically between 58 and 76
per cent LiN0, by weight. The graphical P-T-x data of Blytas and Daniels (1962)too, cover a range of 40-5to
67.4 per cent LiN0, only. The heat capacity of LiNO,-NH,, reported by Gensch (1937), is only at one
temperature and at 66 per cent LiNO,.
The equation of state for the vapour phase is necessary for computing the thermodynamic properties. Gupta
et al. (1975) have used an equation of state for ammonia which was found to represent the vapour volumes

0363-907X/86/010059-10$01 .OO Received 25 June I984

@) 1986 by John Wiley & Sons, Ltd.
60 M.K.A G G A R W A L A N D R. S.A G A R W A L
 LITHIUM NITRATE -AMMONIA MIXTURES 61

between 200 and 380K with a relative deviation of -0-416 to 33.704 per cent, respectively. The
Beattie-Bridgeman equation gives a relative deviation of -0.133 to 29.6 per cent between the same
temperature limits.
Thus, owing to the limited information available on LiN03-NH3, the P-T-x data were experimentally
measured from 0 to 70 per cent LiN03 over a temperature range of - 25 to 156"Cand up to 22 bar by Aggarwal
(1984). Figure 1 shows the smoothed vapour pressure data. A simple and precise threeconstant equation of
state for ammonia vapour given by equation (13) was formulated, which represented the P-V-T behaviour
quite accurately. The minimum and maximum relative deviations in actual and computed vapour volumes are
-0.066 and -4.121 per cent between 200 and 380 K.

VAPOUR PRESSURE RELATIONS

The correlations for vapour pressure data of LiN03-NH3 have been developed from the experimental P-T-x
data using the least squares method. The P-T-x and P-T correlations are of the following form:

3 l 2
An+lxn+T 1
n=O

P = exp ( A + B/T+ C InT+ DT+ ET')

1

T n=O
2
1
B n + l x n + ~ Cn+lxn
1
The constants of equations (1) and (2) are given in Tables I and 11, respectively. The r.m.s. error in representing
the P-T-x data by equation (1) is 5.97 per cent.

Table I. Constants of P-T-x equation for LiN03-NH3

n A B C

0 22.78488 -9493.2091 396,084.46

1 - 15.532808 20,663.058 - 1,461,9260
2 -6.5573732 - 13,653.304 1,O 19,025.1
3 15.05529 - -

Table 11. Constants of P-T equation for LiN03-NH3

Mass r.m.s.
fraction error,
of NH3 A B C D E per cent
-

0.3 - 44.34726 - 2645.5748 11.046612 -0.023199574 0.000006369456 1.717

0.4 219.5072 - 8542.5467 - 36.73801 0.086460469 -0~oooO30271738 1.518
0.5 -34.77313 - 371 1.9818 13.182633 - 0-09677836 O.oooO75884523 0.926
0.6 343.9546 - 5380.3447 - 72.212371 0.40369148 -0.00032014578 0.908
0.7 -81.51453 737.85I76 14.978534 0.014156766 -0~Qooo43631737 1.157
0.8 73.23 134 - 4751.2607 - 8.5294732 - 0.01848 1672 OW0040322505 0.288
0.9 1864482 - 29 1 1.7248 - 0.15334166 - 0-006400394 0~0000085675119 0.454
1.o 494.5437 - 12,25464 - 91.175379 0.29040765 -0~00015353207 1.028
62 M.K.AGGARWAL A N D R. S. AGARWAL

PROPERTIES OF LiN03-NH3
The enthalpies of LiN03-NH3 mixtures have been computed by adding the constituent enthalpies and the
integral heat of solution. The enthalpy of liquid ammonia is computed by

where
hf = href+ lc,~1 (3)

href= 0 at Tref= 233.15 K

and
CI = -3~7866172+0-094908475T-0.00037336919T2 +5.0636833 x 10-7T3
The enthalpy of lithium nitrate is given by

The value of hrerin equation (4)is taken as 0 at Trer= 273.15 K and C = 0.556823 + 0.002186T
Integral heat of solution
The integral heat of solution has been obtained (Jacob et al., 1969; Li, 1976) by finding the difference of the
latent heats o f vaporization of NH3 and LiN03-NH3:
h, = h;g- hrg
where
htg = 137.91 (406.15 -T,,)O" -2.466 (406.15 -T=I)

Latent heat of vaporization

The Clapeyron equation has been used to relate the vapour pressure, temperature and latent heat of NH3 as
well as LiN03- NH3 mixtures as shown in equations (6)and (7),respectively. The prime denotes the properties
of pure ammonia in equation (6):
d P - hig
dT' T ' A V '
and

Comparing at constant pressure such that P = P and dividing equation (6)by (7):

dT
-- - h'f,TAV = c,
dT' hqT'A V'
where C , is a constant and represents the slope of Duhring's straight line for a given composition;
T=CIT'+C2
which gives on differentiation
dT
-dT'
_ - c1

dT
Substituting - from equation (10) into equation (8) and rearranging:
dT'
higTAV
h -
" - C,T'AV'
 LITHIUM NITRATE-AMMONIA MIXTURES 63

Liquid speclfc volume

The volume changes during vaporization A Vand A V’ can be obtained if the liquid volumes of pure ammonia
and the vapour volumes of mixture and those of ammonia are known. The liquid volume of mixture has been
assumed equal to that of ammonia. The liquid specific volume of ammonia within a range of - 70 to 130°C is
given by
4.2830 + 0.8 13055(133 - t)’.’ - OW8286 1 ( 133 - I )
Vf=
1O00+424.805(133 -t)’.’+ 15.938(133- t )
Vapour specific volume
Assuming the vapour formed by vaporizing the LiN03-NH3 mixture to be pure ammonia, the LiN03 being
non-volatile, the vapour volumes can be found from equation of state for ammonia developed and given by
RT a
V=-+-+,+y
B
P RT T
where V is expressed in m3/kgmol, T in K and P in kPa, a = -242.47479, B = -47.6896 x lo’ and
= -0.01465.

Ent halpy
Having known the constituent enthalpies of NH3 as well as LiN03 and the integral heat of solution, the
enthalpy of the mixture can be computed as given by
h = xh,-(NH3)+(1-x)h(LiNO,)+ h, (14)

Direrential heat of solution

The differential heat of solution at any temperature and composition is given by
hd = h, - hrg - hr
The values of h,, hrg and hr are to be computed at the corresponding temperatures.

Enthalpy of superheated ammonia

The method of finding the superheated ammonia enthalpy at any pressure and temperature (say at state 5 in
Figure 2) is explained below in equations (16)-(22). The enthalpy at state 2 is calculated by adding latent heat of

Tsa t

/ I
I
I

h ref
Entholpy - hv

Figure 2. Method to compute superheated vapour properties

64 M. K. AGGARWAL AND R. S. AGARWAL

vaporization to the reference enthalpy. The enthalpy at 3 which is at P = 0 and T = Treris computed by
employing the enthalpy departure term hr. The enthalpy at state 4 is calculated by applying the effect of
temperature. By adding the enthalpy departure term to h4, the enthalpy at state 5 can finally be obtained as per
equation (19).
h3 = href+hfg(Tref)+hrl.1 (16)

where
Cp, = 19500021 -8.240376 x 10-4T+54450171 x 10-6T2 -36269452 x 10-"T3
and

Differentiating the equation of state for ammonia, equation (13),

R a 38
p P RT2 T4
Substituting from equations (13) and (21) into equation (20) and simplifying,
(hr1P.T = P(2a/m+48/T3 + 7)

RESULTS AND CONCLUSIONS

The enthalpy values of LiN03-NH3 obtained for a wide range of pressures, temperatures and compositions
would be able to serve the normal operating conditions obtainable in a solar powered vapour absorption
system. Table 111 gives the enthalpies of the mixture at different compositions for temperatures ranging from
Table 111. Temperatureenthalpy data of LiN0,-NH3

Mass fraction of ammonia

t,"C 0.3 0.4 0.5 0.6 0.7 08

-20 -271.8 -228.8 -98.9 62.2 109.9 94.6

- 10 -259.7 -207.6 -77.3 81.4 134.5 127.0
0 -243.5 -186.8 -51.8 100.8 159.3 165.1
10 -227.5 -166.5 -31.1 124.2 188.9 198.0
20 -208.1 - 142.9 -6.8 147.6 214.0 231.3
30 - 189.3 - 120.1 20.7 1708 243.8 264.8
40 - 171.3 -102.2 43.4 193.8 269.0 298.6
50 - 150.7 -77.6 69.2 2 12.6 2942 338.3
60 - 131.4 - 58.2 90.1 227.1 319.4 378.4
70 - 1135 -40.2 113.9 237.0 344.6 419.2
80 -97.2 - 20.3 136.2 241.9 359.3 4664
90 -80.0 -2.8 152.7
100 -65.8 11.2 1703
110 - 56.3 19.7
120 - 55.4 21.6

hrer= @OW/kg at -40°C for NH3.

= 0.0 kJ/kg at 0°C for LiN03.
 LITHIUM NITRATE-AMMONIA MIXTURES 65

Moss t r o c t i o n of NH3

500 ,
oa 07
I
06
1
05
1
0.r.
I

Moss f r o c t i o n o t LiN03 -
Figure 3. Enthalpy-composition diagram of LiN03-NH3

- 20 to 120°C.The enthalpy-omposition diagram (Figure 3) has been drawn showing the temperature as well
as pressure lines, so that any thermodynamic state of the system can be established.
The latent heats of vaporization computed for LiN03-NH3 are plotted as a function of composition for
various temperatures in Figure 4, which shows that the latent heat at a particular composition decreases with
the increase in temperature. A similar trend is also followed in a pure substance.
The heats of solution, both integral and differential, have been computed and plotted in Figures 5 and 6 as a
function of mass fraction. Both are maximum around 70 per cent LiN03 for all the temperatures.

NOMENCLATURE
Constants of equations
Equation of state constants
Heat capacity
Duhring constants
Ideal gas heat capacity
h Ent halpy, kJ/kg
hd Differential heat of solution
hrn Integral heat of solution
hr Enthalpy departure
P Pressure
R Universal gas constant
66 M. K. AGGARWAL A N D R. S. AGARWAL

1LOC

130C

I 120c
.
0
x
-
x
1100
-
?
0
-
0

'0 10oc
Q
?
c
0
c
9 oc
0
0
L

c
0)
80C
c
0
J

7 00

6 00

5 oc I I I I I I I
0 0 0.2 03 05 06
-
0.1 OL 07
Moss l r o c t i o n of LiNOj

Figure 4. Latent heat of vaporization of LiN03-NH3

t Temperature, "C
T Temperature, K
v, v Volume, m3/kg
AV Volume change during vaporization
X Mass fraction of NH3

Sujixes

f, 1 Liquid
fg Vaporization
ref Reference
sat Saturated condition
V Superheat condition
 LITHIUM NITRATE-AMMONIA MIXTURES 67

- LOC

-350

-300

0
x
\

2 -250

c
-
.-0
-
3
0
UI -200
c
0

c
0
0

JZ -150
-
?!
0
W
c

-
C
-100

-50

Mass f r a c t i o n of L i N 0 3 -
Figure 5. Integral heat of solution of LiN03-NH3
68 M. K.AGGARWAL AND R. S. AGARWAL

I 1 1 I
0.5 06 C 1

M o s s f r a c t i o n ot LiN03 -
Figure 6. Differential heat of solution of LiN03-NH3

REFERENCES
Aggarwal, M. K. (1984). ‘Thermodynamic evaluation of solid absorbent-refrigerant combinations for solar powered vapour absorption
systems’, Ph.D., m s i s , Delhi University.
Blytas, G. C. and Daniels, F. (1962). ‘Concentrated solutions in liquid ammonia’, Journal of American Chemical Society, 84. (7), 107S1085.
Gensch, K. (1937). ‘Lithiumnitrat Ammoniakat als Absorptionsdussigkeit fur kaltemaschinen’, Zeitscrift fur die gesamete kalte-fndustrie.
44, 1-5, 2 4 2 9 (in German).
Gupta, C. P.,Sharma, C. P.and Malhotra, R. K. (1975). ‘Thermodynamicproperties of solutions of sodium thiocyanate in liquid ammonia
and their vapours’. Paper B 1.17, Proc. 14th fnt. Cong. of Refgn., Moscow, pp. 170-178.
Jacob, X.,Albright, L. F. and Tucker, W. H.(1969). ‘Factors atTecting the coekient of performance for absorption airconditioning
systems’, Paper No. 2098, Ashrae Semiannual Meeting, Chicago, Illinois, p. 1031 10.
Li, C. C. (1976). ‘Estimating heats of mixing’, Paper No. 2401, Ashrae Trans., 82, I. 283-288.
Nielsen, P.B., Stubkier, B. and Schmidt, P. W. (1975). ‘A critical survey of intermittent absorption systems for solar refrigeration’, Paper B
2.1, Proc. 14rh fnt. Cong. of Refgn. Moscow, pp. 659667.