Correlating Vapor Pressures and Heats of Solution for

the Ammonium Nitrate-Water System:

An Enthalpy-Concentration Diagram
DONALD F. OTHMER and GERHARD J. FROHLICH
Polytechnic Institute of Brooklyn, Brooklyn, New York

The usual tedious method of construction of enthalpy-concentration charts for solutions of

solids requires data seldom available. A new, simple method is therefore presented that
utilizes more readily available data, that is vapor pressures of the solutions. These plot as
straight lines on a logarithmic-reference substance plot. Differences from unity of the slopes
of these lines represent heats of solution, and when this difference function is integrated be-
tween concentration limits the integral heat of solution is obtained. The enthalpy chart is then
readily constructed by use of the specific heats of liquid and solid.
Ammonium nitrate is the solid used in this example, and water is the liquid because of the
industrial importance of aqueous solutions. Vapor pressures were carefully determined experi-
mentally, and the enthalpy chart was developed from the straight lines of the logarithmic
plot and available heat data. Constants for the vapor-pressure curves for ammonium nitrate
solutions and equations for enthalpies of solid ammonium nitrate are given for the temperature
range 0' to 170.C.

With production of almost 3,000,000 sure of the system. Pressure readings a static method. The experimental
ton+. in the United States, am- were accurate to k 0.1 mm. Hg and data and those of the literature ( 1 , 3 , 8 )
monium nitrate is of outstanding im- temperature readings to f 0.05"C. Be- correlate well on the logarithmic-refer-
portance as a nitrogen fertilizer, more low 50°C. and above 65 wt.% ammo- ence substance plot. The basic equa-
recently as an explosive, and in other nium nitrate exdessive bumping of the tion when vapor pressure of the solu-
major uses. Properties of the ammonium liquid made measurements unreliable. tion is always taken at the same tem-
nitratewater system are very important The experimental data are shown in perature as vapor pressure of water is
in the design of equipment to produce
and use ammonium nitrate.
Table 1 and plotted in Figure 1 ac-
cording to the method previously de-
logP = m logP" c (1) +
While more complex systems involv- scribed (11), no point deviating by where m = LB/LQs
ing ammonium nitrate were being more than 1%from the line represent-
Slopes and intercepts of the straight
studied ( 4 ) , pressures were measured ing all the points.
above aqueous ammonium nitrate solu- lines were plotted vs. concentration in
tions; these were correlated with avail- Figure 2. Slopes derived from vapor-
DISCUSSION OF VAPOR-PRESSURE
able vapor-pressure data as the loga- pressure data were calculated by
DATA
rithms of the vapor pressures vs. the statistical means (16),slopes have also
vapor pressures of water at the same After completion of these determi- been calculated from heats of dilution
temperatures as previously described nations Campbell et d. ( 1 ) published data ( 2 , 1 0 ) .
(11). From the slope of the lines of similar vapor pressures determined by The slopes from the experimental
constant concentration, differential
heats of dilution were calculated, and TABLE1. EXPERIMENTAL
PARTIALPRESSURE
OF WATERABOVE

these were used together with integral AMMONIUMN m m SOLUTIONS

heats of solution and heat capacity
from the literature to construct an Concentration in wt. % NRNO.
enthalpy-concentration diagram, as de-
scribed by Othmer, Kowalski, and 20.6 40.1 46.6 60.3
Napthali (12). PH20, PHZO, PEzO, PHZO,
t,"C. mm.Hg t,"C. mm.Hg t,"C. mm.Hg t,OC. mm.Hg
EXPERIMENTAL DETERMINATION
61.8 147.0 61.6 128.0 51.4 77.4 55.5 84.6
OF VAPOR-PRESSURE DATA
61.0 120.6 61.1 105.0
76.3 280.3 80.1 282.9
Two ebulliometers, one containing 87.6 456.8 83.7 316.3 69.9 182.4 69.5 147.1
the ammonium nitrate solution and the 101.9 750.3 92.6 464.4 85.4 . 341.2 80.8 237.0
other pure water, were connected in 94.6 479.9 97.5 520.3 85.1 278.5
98.9 567.5 98.9 540.6 93.3 378.6
parallel to a pressure system. The 99.4 578.8 103.9 647.6 98.9 461.3
boiling-point difference was measured. 99.7 584.4 106.4 742.9 99.3 485.3
directly, and the temperature of the 102.1 634.7 104.9 593.2
water was determined from the pres- 105.6 751.4 106.5 632.6
105.8 727.9 113.1 749.1
Gerhard J. Frohlich is yith St. Paul Ammonia 106.6 743.1
Products, Inc., St. Paul, Mmnesota.

Page 210 A.1.Ch.E. Journal June, 1960

 nitrate. However further experimental
verification of the pressures for solu-
tions higher than 90 wt.% ammonium
nitrate would be desirable. Table 2
summarizes the results.
The lines of Figure 1 correlate the
experimental data, according to the
vapor-pressure equations given in Table
2, on a temperature scale derived from
the vapor pressure of pure water. At
lower temperatures the lines intersect
the liquid-solid saturation line, which
was derived from data taken from
D'Ans-Lax ( 2 ) . Vapor pressures along
this crystallization curve determine the
operating conditions for vacuum and
air-stripping crystallizers for ammo-
nium nitrate; also they define humidity
conditions under which solid ammo-
nium nitrate will absorb moisture from
the air.

C O N S T R U C T I O N OF THE
ENTHALPY-CONCENTRATION
DIAGRAM

The enthalpy of a solution above a

fixed datum temperature for two pure
components mixed together is
Ha = X A H A -I-X B H B - X A q (2)
Fig. 1. Equilibrium vapor pressure of water above ammonium-nitrate solutions of
constant concentration as a function of temperature. where the integral heat of solution q

data and those from Campbell et d.

(1) for the high concentration range
are within the confidence range of those
calculated from heat of dilution data.
Slopes from the-Campbell et d. data
for the lower concentration range are
not consistent with those for high con-
centrations, nor with those presently
found. They are disregarded in plotting
the smooth curve of Figure 2a repre-
senting the slopes of the lines of con-
stant composition of the best data as
determined by the three indicated
methods.
Constant C of Equation ( 1 ) was
calculated for each concentration with
mean values of the experimental data
and the slope from Figure 2a. Data of
Campbell et aZ. were used to establish
C at 70, 80, and 90 wt.% ammonium
nitrate. A smooth curve was drawn . -
through the plotted points in Figure
~

a
2b.
Gerlach ( 5 , 8 , 9 ) gives the boiling
points at 760 mm. also for 95 and 96
wt.% ammonium nitrate solutions. ' .8
.9
These may be used to estimate the 40 10 20 30 40 50 6070 00 90 100
pressures above the solution at concen- WEIGHT PERCENT NH,NO,
trations higher than 90 wt.% by ex-
trapolating the. slope m in Figure 2n
Fig. 2. The upper curve represents the intercept C of the vapor pressure
to the respective composition and then Equation (1) as a functioh of the ammonium nitrate Concentration. These
calculating C from Equation ( 1 ) to values from Table 2 are all less than zero and hence are negative.
extend the correlation of Figure 2b. The lower curve refers to the slope m of the vapor pressure Equation (1)
Equation ( 1 ) can then be used to cal- as a function of the ammonium nitrate concentration. o This investigation,
culate partial pressures at other con- 0 Campbell e t a/. ( I ) , o Calculated from heats of dilution 12, IO), 0
ditions, also above 90 wt.% ammonium Gerlach 1 5 8 , 9).

Vol. 6, No. 2 A.1.Ch.E. Journal Page 21 1

 TABLE2. PARTIAL PRESSUREOF WATER Equations ( 2 ) and (3) were used The reference states of pure liquid
ABOVE AMMONIUM NITRATE-WATER in the present case. Liquid ammonium water and of pure solid ammonium
SOLUTIONS nitrate can exist only in its pure form nitrate were both taken at 0°C. The
Slope Intercept above the melting point of 170°C. integral heat of solution to dissolve
NHJVOa- of isostere of isostere Below 170°C. the enthalpy of the solid ammonium nitrate in water iso-
Concen- in Equa- in Equa- molten salt in a subcooled state would thermally at 25°C. can be taken from
tration, tion ( 1 ) tion ( 1) be indicated and shall be designated as reference 15. The 25°C. isotherm may
wt. % m C -
H A in contrast to HaA. therefore be used as a starting point
10 0.9988 -0.0125 for constructing the enthalpy-concen-
20 0.9968 -0.0275 The slope of the isosteres is a func-
30 0.9935 -0.0460 tion of the concentration only and not tration diagram, although the reference
40 0.9889 -0.0670 of temperature; hence the integration temperature is 0°C.
50 0.9837 -0.0910 of Equation (3) covers also the range The steam tables ( 7 ) give the en-
60 0.9770 -0.1245 of immiscibility at temperatures below thalpy of pure water. Heat capacities
70 0.9693 -0.1853 the melting point of the solute.
80 0.9611 -0.2829 and heat of transformations for solid
It is necessary only that at some ammonium nitrate have been used as
90 0.9523 -0.4360 temperature the term (m-1) can be
95 0.9475 -0.6950 extrapolated with reasonable accuracy shown in Table 3. Heat capacity data
to x B / x A= 0 in the same way as (m-1) of Rutskov ( 1 3 ) and Gucker et al. (6)
can be shown to be (12) is extrapolated to x B / x A = co when the for the ammonium nitrate solutions
XB reference state of infinite dilution for have been used. The 25°C. isotherm
q = L o s p (m-1) d- ( 3 ) the solute is used. is thus calculated:
XA

The reference state for a solid solute is 180

usually the state of infinite dilution,
and Equation (2) becomes
I70

H , = x A H ' A + x B H B + x A q . (4)
Here, instead of the enthalpy of the 160

pure component H A , the partial en-

thalpy of the solute at infinite dilution
- IS0

H A has been used, and the infinite heat

of solution is substituted by the in-
140
finite heat of dilution:

130

z I20
For many systems of partial miscibil- P
ity, such as salt-water systems, only I-
Equations ( 4 ) and (5) can be used. $ 110

However where vapor pressures at high

concentrations can be determined,
Equation (3) can be integrated at
least as accurately as Equation (5);
thus either may be used.

TABLE
3.
Enthalpies for solid LL
0
NHINO, in kcal./kg.-mole
ammonium nitrate *
a 'O

derived from data of a

I
Temperature reference 8, 14 z
k 60
t, "C. (base temperature OOC. ) W

-60 to -17 H*A = 3,890. - 3.10T - 50

0.0551F
-17 AHTR = 120 ( V -+ IV) 40
-17 to +32 H O . 4 = -5,580. +
9.54T
+ 0.0398T2
30
+32 AHTR = 399. (IV -+ 111)
+32 to 83 H'A = -5,452. +
14.11T
+ 0.0235T' 20

+83 AHTR = 311 (I11 -+ 11)

+83 to +125 H'A = -9,696. + 27.22T
10

+125 &H*TR= 1,027 (I1 + I )

+125 to +170 H"A = -10,840 + 27.22" 0 01 02 0.3 94 05 06
WEIGHT FRprrON NHJQ
07 od 03 ID

+170 AHou,con, = 1,460

( I + liquid) Fig. 3. Entholpy-concentration diagram for the system water-ommonium nitrate.

Page 212 A.1.Ch.E. Journal June, 1960

 TABLE4. VALUES
OF TABLE5. ENTHALPIESFOR THE WATER-AMMONIUM NITRATE SYSTEM
0lneh.lpAU in KC.l/U. S0l"tioll)

wt. % 10 10.06 16.54 22.26 25.52 30.30 33.30 ' 35.70 i 4.01
NHhNOs x.42 20 20.06 25.99 30.63 34.61 37.79 40.19 41.98 i,5240&-_ 7 .a
30 30.04 36.24 39.34 42.71 45.21 47.06 48.27 48.70 i 12.24
2.20 0.00186 40 40.02 44.67 48.06 50.81 52.76 53.95 54.55 54.40 i 53.61 21.06
5.0 0.00378 50 49.99 54.01 56.76 s e . ~ 60.24 60.82 60.83 60.09 +~~;,- 24.67
10.0 0.00687 60 59.97 63.34 65.48 66.99 67.73 67.71 67.11 65.78 63.81 i 61.44 28.37
20.0 0.01240 70 69.98 72.72 74.22 75.11 75.22 74.60 73.40 71.48 68.93 65.97 32.10
30.0 0.01760 a0 80.01 111.10 82.W 83.24 82.73 81.50 79.70 77.36 74.05 i 70.50 35.91
40.0 0.02195 90 90.07 91.51 91.75 91.39 90.25 88.40 86.01 82.89 79.17 i-72,.2--, 43.33
50.0 0.02525 100 100.2 100.99 ioo.58 99.57 97.a 95.36 92.34 88.61 t14.29 79.57 i 46.74
60.0 0.02758 110 110.3 110.43 109.38 107.75 105.37 102.29 98.66 94.34 89.41 84.10 ';50.13
70.0 0.02785 UO U0.4 119.88 118.18 1l5.92 lXZ.91 109.22 104.97 100.04 94.53 88.63 i53.54
80.0 0.02530 130 130.6 U9.40 l27.06 124.14 l2O.Y 116.18 111.3'2 105.78 99.67 93.17 t69.78
90.0 0.01900 140 140.8 138.93 135.94 132.37 l28.10 123.15 117.67 111.53 104.81 97.72 i 73.18
I

150 151.0 148.46 145.81 l40.61 l35.70 W.ll 124.01 117.26 109.86 102.25 ;76.58
160 161.3 158.08 153.76 148.W 143.34 137.13 l30.39 123.02 115.10 106.81 79.96
First the enthalpy of a 9.09 mole % 170 171.6 167.69 162.71 157.19 150.98 144.14 136.78 128.78 120.24 111.35 JmmfP-
solution at 25°C. is calculated: 180 181.9 177.31 171.66 165.48 158.62 151.13 143.15 134.54 125.39 115.89 105.48

H.1 = Xnl H*A +xsl H B + X A ~ Q (6)

With the aid of heat capacity data nium nitrate were calculated from the
= (0.0909~805)
+(0.9091~451) for the solution, PAis calculated at any equation of Table 2 and Plotted in the
other temperature enthalpy-concentration diagram. Tables
+ (0.0909 x 4,810) 5 and 6 show the values of enthalpy
= 921.6 kcal./kg.-mole solution
-
H A =
+ c,(t-25) - XB HB
H,(=, + x.4 410""
(11)
= 38.92 kcal./kg. solution x.4
The area under the curve ( m - 1) VS. At 170°C. gAshould become equal along isotherms and isobars respec-
x B / x A was evaluated by a step-by-step to the enthalpy of pure molten am- tively; by use of these numbers, for
integration, and the values xAZ were monium nitrate. This value can be cal- more precise use, there may be pre-
calculated (Table 4), where culated independently by using heat pared large-scale plots.
capacities of the solid and heats of
transition and fusion for pure ammo- ACKNOWLEDGMENT
nium nitrate. Within the accuracy of The support of Vulcan-Cincinnati, In-
Multiplication of 2 by the molar heat the heat-capacity data for solid ammo- corporated, is gratefully acknowledged.
ofvaporization of pure water ( 7 ) gives nium nitrate and for the sohtions there
is calculated NOTATION
the desired q value at any desired
- C = integration constant (inter-
temperature and pressure.
The enthalpy of any solution along H A = 2,744 + 31.67t (kcal./kg.-mole) cept of partial-pressure equa-
the 25°C. isotherm can now be calcu- With the above information the com- - tion)
lated as plete enthalpy-concentration diagram C,, = mean molar heat capacity for
- was calculated as shown in Figure 3. ammonium nitrate solutions,
HQ =Ha1 + (XAZ-XAi) HAt In addition to the isotherms, isobars for kcal./kg.-mole solution and
concentrations up to 90 wt.% ammo- "C.
TABLE6. ISOBARS FOR THE WATER-AMMONIUM
NITRATE SYSTEM
(VALUESGIVENARE OF TEMPERATURES
IN " C . )
= 921.6 + ( x A ~ - 0.0909) 3,540 - rrassuse
I. . B g.
o 10
Concentration in Wt. % NW,W3
- - - _20 _ -30_ _40- 50 60 70 80-PO
( X A -
~ 0.0909) 451 - 188.88 5 1.2 1.3 1.4 1.5 1.7 1.9
10 11.3 11.7 12.3 13.1 14 ,O 15.1 16.6
-%d ql."% 50 38.1 38.8 39.6 40.6 41.9 43.4 45.4 49.0
100 51.6 52.3 53.2 54.4 55.9 57.6 60.0 64.0 70.4
where @A is obtained from 200
300
66.5
75.9
67.2
76.7
68.3
77.9
69.8
79.4
71.4
81.2
73.4
83.4
76.2
86.6
80.8
91.6
88.0
99.4
99.6
112.0
X 4 400 83.0 83.9 85.1 86.6 88.7 91.0 94.3 99.7 108.0 121.5
- H*I- XBi H B -k XAi 410 500
600
88.7
93.6
89.6 90.9 92.6
97.6
94.7
99.8
97.1
102.3
100.6
105.9
106.2
111.8
115.0
120.9
128.9
135.6
94.5 95.8
HA = (9) 700 97.7 98.8 100.1 101.9 104.2 106.8 110.6 116.7 126.0 141.0
XAi
1 100.0 101.0 102.5 104.2 106.6 109.3 113.1 119.3 128.9 144.1
and specifically for 25°C. 1.25 106.6 107.2 108.9 110.8 113.3 116.2 120.2 126.7 136.7 152.8
1.5 111.8 112.9 114.4 116.4 119.0 122.0 126.1 132.9 143.4 160 .o
- = 921.6-
H A
0.9091 X 451 - 188.88 2.0
2.5
120.7
127.9
121.9
129.1
123.4
130.8
125.6
133.1
128.3
136.0
131.6
139.4
136.1
144.1
143.4
151.8
154.6
163.6
172.4
182.5
3.0 134.0 135.3 137.0 139.4 142.5 146.0 151.0 159.0 171.4 191.1
0.0909 3.5 139.3 140.7 142.5 144.9 148.1 151.8 157.0 165.4 178.2 198.6
4.0 144.1 145.5 147.3 149.9 153.2 157.0 162.4 171.0 184.3
= 3,540 kcal./kg.-mole ammonium 4.5 148.4 149.8 151.7 154.4 157.8 161.7 167.2 175.9 189.8
5.0 152.3 153.8 155.7 158.5 102.0 166.0 171.7 180.8
nitrate 6.0 159.2 160.9 162.9 165.8 169.4 173.7 179.6 189.2
7.0 166.0 167.1 169.2 172.1 175.9 180.4 186.6 196.b
(10) 8.0 171.8 172.6 174.8 177.9 181.8 186.4 192.8
= 44.17 kcal./kg. ammonium nitrate Temperatures in degrees centigrade.

Vol. 6, No. 2 A.1.Ch.E. Journal

L O B = molar heat of vaporization a0 = infinite dilution 8. “International Critical Tables,” Vol.
for pure water, kcal./kg.- 1 = concentration where integral V., McGraw-Hill, New York (1929).
mole water heat of solution Q is known 9. Kirk-Othmer, “Encyclopedia of Chem-
= molar heat of vaporization 2 = any concentration ical Technology,” Vol. I, p. 818, The
L B
Interscience Encyclopedia, Inc., New
for water out of ammonium York ( 1947).
, &

nitrate solutions, kcal./kg.- Superscripts 10. Lerner-Steinberg, B., 2.physik. Chem.,

m
mole water
= slope of an isostere on a log-
-
t
=’ partial quantity 122. 121 11926).
11. h e r , D. F.,‘lnd. Eng. Chem., 32,
= infinite dilution
arithmic partial-pressure plot 0
= solid state 841 ( 1940).
H = enthalpy, kcal./kg-mole (ex- 0 12. -----, R. C. Kowalski, and L. M.
= pure compound
cept if otherwise noted) Napthali, Ind. Eng. Chem., 51, 89
P = partial pressure of water (1959).
above ammonium nitrate so- 13. Rutskov, A. P., J . Appl. Chem.,
lutions, mm. Hg abs. LITERATURE CITED (USSR), 21, 820 (1948).
14. Stephenson, C. C., D. R. Bentz, and
Po = vapor pressure of pure water, 1. Campbell, A. N., J. B. Fishman, D. A. Stevenson, J. Am. Chem. SOC.,
mm. Hg abs. G. Rutherford, T. P. Schaeffer, and L. 77,-2161( 1955).
0 = integral heat of solution for Ross, Can. 1. Chem. 34, 151 (1956). 15. U. S. National Bureau of Standards
solid ammonium nitrate, 2. D’Ans-Lax, “Taschenbuch fur Chemi- Circular 500.
kcal./kg.-mole ker und Physiker,” 2 edit., Springer 16. Volk, W., Chem. Eng., 63, 165
4 = integral heat of dilution, Verlag, Berlin, Germany ( 1949). (March 1956).
kcal./kg.-mole 3. Fricke, R., and L. Havestadt, Z. Elek- Previous articles in this series have ap-
t = temperature, “C. trochem., 33, 441 (1927). peared in Ind. Eng. Chem. during 1940,
T = absolute temperature, OK.
4. Frohlich, G. J., D.Ch.E. dissertation, 1942 to 46, 1948 to 51, 1953, 1955, 1957,
Polytechnic Inst. Brooklyn, New York 1959 to 60; Chem. Eng. Data, 1956;
X = mole fraction
( 1957). Chem. Met. Eng., 1940; Chimie k7 Indus-
z = abbreviation for the integral 5. Gerlach, Z. anal. Chem., 26, 413 trie ( P a r k ) , 1948; Euclides (Madrid),
of Equation (7) ( 1887). 1948; Sugar, 1948; Petrol. Refiner, 1951
6. Gucker, F. T., F. D. Ayres, and T. R. to 53; World Petrol. Congr. Proc., 3
Subscripts Rubin, J. Am. Chem. SOC., 58, 2118 Congr., Hague, 1951; Proc. Intern. Congr.
(1936). Pure Appl. Chem., 11 Congr., London,
A = ammonium nitrate 7. “Handbook of Physics and Chemis- 1947.
B = water try,’’ 37 ed. Chemical Rubber Pub-
S = solution lishing Company, Cleveland, Ohio Manuscript received February 26 1959; revi-
TR = transition sion reseived July 21, 1959; paper hccepted July
( 1955). 29, 1959.

Hydrocarbon Vapor- Liquid Equilibria

and Solubility Parameter
J. M. PRAUSNITZ, W. C. EDMISTER, and K. C. CHAO
California Research Corporation, Richmond, California

Hydrocarbon vapor-liquid equilibria are expressed in terms of K values, which ore functions
of composition, as well as pressure and temperature. The composition effect in the liquid phase
is calculated by the Hildebrand-Scatchord equation for regular solutions. The parometers in
this equation, called solubility parameters, can be calculated simply from heat of vaporization
for the heavier hydrocarbons, but an indirect method of calculation must be used for the
lighter components. Solubility parameters for hydrogen, methane, ethane, and propane were
computed from gas-solubility data in several hydrocarbon solvents a t various temperatures and
pressures. This computation also yielded simultaneously the fugacities of the hypothetical
liquid-standard states.
The results presented are not complete for practical applications, owing to the scarcity of
suitable solubility data, especial$ a t high temperatures and pressures. However solubility param-
eters appear to give the right liquid-phase corrections in the correlation and prediction of
hydrocarbon phase equilibria. Calculated K values for light hydrocarbons in paraffinic, naph-
thenic, and aromatic absorption oils ore compared with experimental results. The average
deviation for the forty-two values tested is 13%.

The composition dependence of the carbon systems has been frequently of hydrocarbons, like the aliphatics,
vaporization equilibrium ratio in hydro- neglected in practical large deviations are encountered for
mixtures composed of different classes
While the comPosition-indePendent ~~

of hydrocarbons, notably those contain-

J. M. Prausnitz is at the University of Califor- values are approximately applicable to ing *aromatics and, to a lesser extent,
nia Berkeley, Califom*. W. C. Edmister at naphthenes.
Okiahoma State Unwers&. Stillwater, Oklah&na. mixtures composed entirely of one class

Page 214 A.1.Ch.E. Journal June, 1960