J. Chem.

Thermodynamics 2000, 32, 29–54
Article No. jcht.1999.0565
Available online at http://www.idealibrary.com on

Thermodynamic properties of aqueous calcium
nitrate {Ca(NO3 )2 } to the temperature 373 K
including new enthalpy of dilution data
C. S. Oakes, A. R. Felmy,
Battelle, Pacific Northwest National Laboratory, P.O. Box 999, P7-50,
Richland, WA 99352, U.S.A.

and S. M. Sterner
Fluid Inclusion Technologies, 2217 N. Yellowood Ave., Broken Arrow, OK
74012, U.S.A.
In this study we present new enthalpy of dilution measurements at T = (298.15, 323, 348,
and 373) K and for molalities of less than 6.674 mol · kg−1 . These new data fill a gap in the
thermodynamic database between T = 298.15 K and T = 373 K where virtually no highquality data at low to moderate molalities previously existed. These new data have been
fitted with a Pitzer ion-interaction model with an ionic-strength dependent second virial
coefficient. The model accurately reproduces the available osmotic, dilution enthalpy, heat
capacity, and volumetric data to m = 8.0 mol · kg−1 and for 298.15 K ≤ T ≤ 373 K.
The model is at least qualitatively correct to m ≈ 20 mol · kg−1 over the same temperature
range. Data above T = 373 K are very limited, and with the exception of new dilution
enthalpy data presented in this paper, we are not aware of any above p = 0.1 MPa or the
c 2000 Academic Press
vapor-saturated liquid surface.
KEYWORDS: calcium nitrate; dilution enthalpies; Pitzer ion-interaction; activity coefficients; aqueous electrolytes

1. Introduction
Understanding of the thermodynamic properties of aqueous nitrate systems is requisite to
the solution of a number of environmental and industrial problems. Agricultural runoff and
wastes associated with the production of nuclear fuel and munitions frequently contain
high percentages of nitrates. While the predominant cations in these chemical systems are
sodium, potassium, or ammonium, significant quantities of calcium and other alkalineearth metals (e.g., strontium) are present or may be added as part of the treatment or
disposal process. In addition, some disposal schemes for energetic materials and nuclear
wastes involve treatment of aqueous solutions of these wastes at high temperatures and
0021–9614/00/010029 + 26 $35.00/0

c 2000 Academic Press

30

C. S. Oakes, A. R. Felmy, and S. M. Sterner

pressures; consequently thermochemical properties and models at superambient conditions
are necessary.
The previous Pitzer ion-interaction model for this system(1) was limited to molalities
m less than 2 mol · kg−1 and T = 298.15 K due to a dearth of thermodynamic data
at other temperatures and low to moderate molalities. To fill this void, and extend the
range of conditions over which aqueous Ca(NO3 )2 properties can be calculated, we have
measured dilution enthalpies between T = 298.15 K and T = 373 K and for molalities
to 6.674 mol · kg−1 (table 1 and figure 1). These new data, and a selected subset of the
available thermodynamic data for this system, specifically the isopiestic, vapor pressure,
enthalpy of dilution, heat capacity, and volumetric data from the sources(2–20) listed in
table 2, have been incorporated in an extended form of the Pitzer ion-interaction model.(21)
The latter modification enables representation of relatively complex free-energy surfaces
without the addition of higher order virial terms which may not be warranted. The
resultant model has the requisite flexibility to reproduce the p = 0.1 MPa thermodynamic
properties of this system between infinite dilution and at least m = 8 mol · kg−1 and from
T = 298.15 K to T = 373 K.

2. Experimental
While mean ionic activity γ± and osmotic φ coefficients for electrolyte solutions can be
experimentally determined over a range of temperatures, it is frequently more convenient
and expedient to make the activity coefficient measurements at one temperature and
supplement them with enthalpic measurements in order to obtain the osmotic and activity
coefficients as a function of temperature. As there is a plethora of osmotic coefficient data
for this system at T = 298.15 K, yet none at 298.15 K < T < 373 K, this system provides
an excellent demonstration of this principle.
The molar enthalpy of dilution is defined as:
1dil H (m i → m f ) = L φ,i − L φ,f ,

(1)

where m i and m f refer to solution molalities prior to and after dilution, respectively,
and L φ is the apparent relative molar enthalpy which will be defined in a subsequent
section. Enthalpies of dilution were measured between T = 297.87 K and T =
372.15 K at p = 0.4 MPa and p = 2.0 MPa (table 1). Stock solutions of (6.674,
1.955, and 0.7021) mol · kg−1 were prepared from reagent grade Ca(NO3 )2 · 2H2 O and
distilled, deionized water. The molality of the 6.674 mol · kg−1 stock was determined
gravimetrically by first destroying the nitrate complex through repeated dosings with
concentrated HCl(aq) followed by evaporation of the liquid until it became very viscous.
When the solution no longer became yellow upon dosing with HCl(aq), CaSO4 was
precipitated by using an excess of sulfuric acid. The excess H2 SO4 was evaporated and the
sulfate salt dried at T = 973 K. The lower molality stocks were prepared from dilutions of
the 6.674 mol · kg−1 stock. All apparent molalities have been corrected to molalities.
Dilution enthalpies were measured using a SETARAM (France) C80 II Calvet calorimeter and two different sets of twin flow-through mixing cells: SETARAM flow-through mixing cells with Hastalloy-C housings and KEL-F inserts; and an in-house design described

Thermodynamic properties of aqueous calcium nitrate to T = 373 K

31

TABLE 1. Experimental molar enthalpies of dilution 1dil H . All pressures are at 0.43 MPa unless otherwise noted
1dil H
mi
mf
1dil H
mi
mf
1dil H
mi
mf
J · mol−1 mol · kg−1 mol · kg−1 J · mol−1 mol · kg−1 mol · kg−1 J · mol−1 mol · kg−1 mol · kg−1
T = 297.87 K
−480a

6.674

5.226

1264

1.230

1205

0.7021

0.241

1.955

0.933

1405a

0.7021

0.230

1.955

0.549

1403a

0.7021

0.230

1.955

0.272

1439

0.7021

0.137

2.796

1423

0.7021

0.137

0.7021

0.114

0.7021

0.114

−456a

6.674

3.944

1929

−389

6.674

3.824

2905

154a

6.674

2.796

3678

143

6.674

1.955

1185

6.674

1.869

266

0.7021

0.594

1629a

2197

6.674

1.295

358

0.7021

0.558

1662a

3467

6.674

0.754

709a

0.7021

0.463

1672a

0.7021

0.068

1071a

0.7021

0.346

1495

0.7021

0.068

0.7021

0.346

1485

0.7021

0.044

667

1.955

1.535

929

−923

6.674

5.226

127

1.955

1.535

116

0.7021

0.346

−915a

6.674

5.226b

310

1.955

1.230

61

0.7021

0.346
0.230

T = 322.61 K

6.674

4.565

479

1.955

0.933

−20a

0.7021

−1422a

6.674

3.944b

685

1.955

0.549

−29a

0.7021

0.230

−1437

6.674

3.944

661

1.955

0.272

−44

0.7021

0.230

−1540

6.674

2.796

−42

0.7021

0.230
0.114

−1229

−1256

6.674

1.769

22a

0.7021

0.582

−108

0.7021

−1004

6.674

1.295

17

0.7021

0.582

−325a

0.7021

0.114

−716

6.674

0.841

6

0.7021

0.582

−358

0.7021

0.114

49

0.7021

0.463

−577a

0.7021

0.068

0.346

−615a

0.7021

0.068

50a

0.7021
T = 347.35 K

−1077a

6.674

5.573c

−303

1.955

1.638

−531a

0.7021

0.463c

−1349

6.674

5.226

−438

1.955

1.431

−576

0.7021

0.451

−2388

6.674

3.944

−842

1.955

0.933

−869a

0.7021

0.346c

−3158

6.674

2.796

−818

1.955

0.933

−876

0.7021

0.346

−3151

6.674

2.796

−1209

1.955

0.643

−884a

0.7021

0.346c

−3761

6.674

1.769

−1528

1.955

0.456

−1372a

0.7021

0.230c

−4065

6.674

1.295

−2059

1.955

0.272

−1579

0.7021

0.172

−4464

6.674

0.841

−1994a

0.7021

0.114c

−1936

0.7021

0.103

−2411

0.7021

0.062

−4578

6.674

0.754

−287a

0.7021

0.582c

32

C. S. Oakes, A. R. Felmy, and S. M. Sterner
TABLE 1—continued
1dil H
mi
mf
1dil H
mi
mf
1dil H
mi
mf
J · mol−1 mol · kg−1 mol · kg−1 J · mol−1 mol · kg−1 mol · kg−1 J · mol−1 mol · kg−1 mol · kg−1
T = 372.15 K
−1351a
−1672a

6.674
6.674

5.573
5.226

−984
−2102

1.955

1.431d

−1908a

0.7021

0.346

1.955

0.933d

−1666

0.7021

0.346d

−2495a

0.7021

0.258

−2331

0.7021

0.241d

−3224a

0.7021

0.172

0.612

−3240

0.7021

0.137d

0.7021

0.086

0.7021

0.062d

−3370a

6.674

3.944

−3700

1.955

0.456d

−4873a

6.674

2.796

−4523

1.955

0.301d

−6407a

6.674

1.769

−8112a
−678

6.674
1.955

0.841
1.603d

−418a

0.7021

−834a

0.7021

0.522

−4211a

−1341a

0.7021

0.434

−4483

T = 372.08 K, p = 2.0 MPa
−1770

6.674

5.226

−3307

6.674

3.944

−4750

6.674

2.796

−6264

6.674

1.769

−8168

6.674

0.841

a Experiments conducted with the SETARAM cells. Temperatures are uncertain by ±0.01 K. Initial and final
molalities are denoted by m i and m f . b At T = 322.65 K. c At T = 347.41 K. d At T = 372.08 K.

in the appendix. Solutions and water were delivered to the calorimeter through platinum
tubing and Hastalloy-C valves using a flow system similar to that developed at Oak Ridge
National Laboratory.(22) High-pressure syringe pumps (ISCO, Inc., U.S.A.) were used to
drive water to the solution storage vessels and to the calorimeter. One pump was used to
flow water through the reference cell, while two pumps were used to flow solution and
water through the sample cell. Molalities of the mixtures were determined by conversion
to mass flow-rates using densities at T = 298.15 K and p = 0.1 MPa.(15, 16) The error in
the calculated dilution molalities due to the difference in the stock density between (0.1
and 0.4 or 2.0) MPa is insignificant.
The potential developed in the calorimeter’s thermopiles in response to heat transferred
from or to the mixing cell as a consequence of an enthalpy of dilution effect was recorded in
units of power (mJ · s−1 ) according to the factory calibrated sensitivity or the calorimeter
in mW · V−1 . For each dilution measurement a baseline power level was established by
mixing two water streams in the two cells at identical flow-rates and ratios.
Measurement accuracy for both cell types was confirmed by comparison of dilution enthalpies of 5.104 mol · kg−1 NaCl(aq) with model values from the equation of Archer.(23)
With the exception of measurements at T = 323 K, measurements produced using both
cell types were generally within 5 per cent of values from the Archer model. At T = 323 K,
dilution enthalpies over the entire molality range are very close to zero; consequently, er-

Thermodynamic properties of aqueous calcium nitrate to T = 373 K

33

TABLE 2. Thermodynamic property, range of experimental conditions,
and source for data used in this study: m o = 1.0 mol · kg−1 , T o = 1 K
Property

T /T o

m/m o

Osmotic

373.2 to 373.6

0.0008 to 0.3

2

Osmotic

298

0.06 to 3.0

3

Osmotic

298

3.1 to 21.6

4

Osmotic

298

1.9 to 3.0

5

Osmotic

373 to 423

1.8 to 23.2

6

Osmotic

298

0.6 to 7.8

7

Enthalpy

298

19.6 to 1.4

8

Enthalpy

298

0.1 to 0.006

9

Heat capacity

140 to 380

13.9

10

Heat capacity

298

0.04 to 0.24

11

Heat capacity

323 to 341

3.0 to 13.8

12

Heat capacity

293 to 323

7.2 to 13.9

13

Density

298

0.04 to 0.24

11

Density

307

7.2 to 13.9

13

Density

308

0.03 to 18.8

14

Density

298 to 333

1.3 to 20.2

15

Density

298 to 613

0.25 to 3.0

16

Density

373

13.9

17

Density

248 to 283

5.5 to 13.8

18

Density

287 to 357

13.9

19

Density

313 to 353

13.9

20

Reference

rors on a percentage basis were much larger, but never exceeded 30 J · mol−1 on an absolute
basis. As the magnitudes of the deviations between the Ca(NO3 )2 (aq) dilution enthalpies
and the fitted values are often larger than 30 J · mol−1 , this level of agreement with the
NaCl dilutions is sufficient confirmation of the instrument’s calibration.
In contrast with the apparent accuracy achievable by both cell types as established
by using NaCl(aq), precision between the different cell types for dilutions of the
6.674 mol · kg−1 Ca(NO3 )2 (aq) stock was in some cases exceptionally poor. Measurements with the platinum cells were completed at what was anticipated to be near to the
completion of the experimental investigation and were conducted more to establish worthiness rather than to provide original data. Dilution enthalpies of the m = 6.674 mol · kg−1
stock at T = 373 K and p = 2.0 MPa from the platinum cells were essentially identical
to those produced from the SETARAM cells. The temperature and pressure were then
lowered to 348 K and 0.4 MPa with intent to clear up a persistent and severe problem

34

C. S. Oakes, A. R. Felmy, and S. M. Sterner

5

10–3 · dilHm / (J · mol–1)

0

–5

–10

–15

0.0

0.5

1.0

1.5

2.0

2.5

m 1/2/(mol · kg–1)1/2
FIGURE 1. Experimental molar enthalpies of dilution 1dil H as a function of m 1/2 for Ca(NO3 )2 (aq)
at p = 0.1 MPa. ◦, T = 297.87 K; +, T = 298.15 K from reference 9; , T = 322.61 K; ♦,
T = 347.45 K; 4, T = 372.15 K (data at pressures of 0.1 MPa and 2.0 MPa undifferentiated). —,
calculated from equations (1), (31), and (49).

in the reproducibility of the 1dil H values from the 6.674 mol · kg−1 stock obtained
using the commercial cells. Agreement was good for the highest molality dilutions of
the m = 6.674 mol · kg−1 stock but deteriorated rapidly with increasing dilution. In
contrast with measurements with the commercial cells, replicate measurements with the
Pt cells proved to be reproducible. Subsequently, a 1.955 mol · kg−1 stock was prepared
and measurements were made with the Pt cells to ensure that the dilution chords from
the three stocks blended together smoothly. The dilution chords for the (0.7021 and
1.955) mol · kg−1 stocks are concordant with the Pt cell dilutions of the 6.674 mol · kg−1
stock at T = (298.15, 323, and 348) K while they are not concordant with the
6.674 mol · kg−1 stock dilutions made with the SETARAM cells. The 6.674 mol · kg−1
stock dilution chords obtained from the platinum cells also have a simpler molality and
temperature dependence. Consequently, data from the platinum cells were favored in the

Thermodynamic properties of aqueous calcium nitrate to T = 373 K

35

model development and most of the dilutions of the 6.674 mol · kg−1 stock done with the
SETARAM cells were discarded.
While we cannot conclusively assign specific causes for the apparent errors in the
dilution measurements of the 6.674 mol · kg−1 stock made with the SETARAM cells, the
underlying reason is almost certainly related to the high viscosity of the solution and the
fact that the inlet lines of the SETARAM cells are not continuous over the entire flow-path.

3. Treatment of the experimental results
THERMODYNAMIC FRAMEWORK

Within an excess Gibbs energy G xs framework the activity coefficient of an individual
solute species i is:
ln γi = [∂{G xs /(ww RT )}/∂m i ] p,T,ww ,m j6=i ,

(2)

and the osmotic coefficient is:
φ−1=−

X

mj

!−1

[∂{G xs /(RT )}/∂ww ] p,T,m i ,

(3)

i

where ww = 1 kg of H2 O. The osmotic coefficient is related to the activity of water aw
through:
,
!
X
φ=− 
m i ln aw ,
(4)
i

where  = 55.5081 mol · kg−1 of H2 O. For simple systems, the mean ionic activity
coefficient γ± is commonly used in place of γi and is defined by:
ln γ± = (ν M ln γ M + ν X ln γ X )/ν,

(5)

where ν is the sum of the number of cations (ν M ) and anions (ν X ) in the electrolyte formula
unit (in this case ν = 3).
The relative enthalpy is defined as:
L = H − H o,

(6)
−RT 2 ∂(G/RT )/∂ T }

Ho

and H is the total enthalpy of the solution {H =
and
is the
sum of all solution component enthalpies in their standard states. The relative enthalpy is
related to G xs through:
L = −RT 2 [∂{G xs /(RT )}/∂ T ] p,m i ,

(7)

and consequently to γ± and φ through:
L = νm RT 2 (∂φ/∂ T − ∂ ln γ± /∂ T ) p,m i .

(8)

The apparent relative molar enthalpy (also referred to as the relative molar enthalpy) is:
L = L/n 2 ,

(9)

36

C. S. Oakes, A. R. Felmy, and S. M. Sterner

where n 2 refers to the amount of substance of solute.
Apparent molar volume is defined by:
o
Vφ = (V − n w Vwo )/n 2 = n −1
2 (∂G/∂ p − n w ∂G w /∂ p)T,m i =
xs
0
n −1
2 (∂G /∂ p − n 2 ∂G 2 /∂ p)T,m i .

(10)

o
o
The quantity n −1
2 (∂G 2 /∂ p)T is the solute apparent molar volume at infinite dilution, Vφ,2 .
The quantity Vφ is related to solution and water densities (ρs and ρw , respectively) through:

Vφ = M/ρs − 1000 · (ρs − ρw )/mρs ρw ,

(11)

where M is the molar mass (164.088 g · mol−1 ).
Massic heat capacities and relative heat capacities have been converted to the apparent
molar form defined by:
o
o
C p,φ = (C p − n w C op,w )/n 2 = ∂ L/∂ T + n −1
2 [(∂ H /∂ T ) p,m i − n w C p,w ] =

∂ L/∂ T + C op,φ,2 ,

(12)

where C p = (∂ H/∂ T ) p,m and C op,w = (∂ Hwo /∂ T ) p,m i . The quantity C p,φ is related to
solution and water specific heats (c p,2 and c p,w , respectively) according to:
C p,φ = c p,2 · M + 1000 · (c p,2 − c p,w )/m.

(13)

Densities and heat capacities for water were calculated from Hill.(24)
PITZER ION-INTERACTION MODEL

The G xs based Pitzer ion-interaction model(25, 26) has proven to be a very powerful tool
for fitting and reproducing aqueous electrolyte solution properties over wide ranges of
pressure, temperature, and ionic strength. Until recently, most Pitzer ion-interaction models
were limited to relatively moderate ionic strengths—often well below the salt liquidus.
Attempts to go to higher ionic strengths or ionic strengths in the solid supersaturated
region usually involved addition of fourth or higher order virial terms.(27, 28) Archer’s(21)
incorporation of an ionic strength dependent third virial has proven to be a powerful
addition allowing the model to be extended to very high ionic strengths with and without
incorporation of additional virial terms.(29–31)
The Pitzer ion-interaction model(25, 26) for a single electrolyte is:
G ex /(ww RT ) = f (I ) + 2m a m c {Bca + (1/2)Z Cca }.

(14)

The second and third virial coefficients, Bca and Cca , are, in principle, related to shortrange interactions between ions of opposite sign (c = cation, a = anion) but are, in
practice, empirically derived fit parameters. The Debye–H¨uckel term, f (I ), is:
f (I ) = −4I Aφ ln(1 + b · I 1/2 )/b,

(15)

where b has the universal value of 1.2 kg · mol−1/2 , I is ionic strength (I = 2 i m i z i2 ),
and Aφ is a function of the density and dielectric constant of water(25) which have
been calculated from Hill(24) and Archer and Wang,(32) respectively. The quantity
1P

Thermodynamic properties of aqueous calcium nitrate to T = 373 K

37

P
Z =
i m i |z i |, z i is the charge on each ion i, and Bca is given an ionic strength
dependency of the form:
(1)

(0)

(2)

B M X = β M X + β M X g(α1 I 1/2 ) + β M X g(α2 I 1/2 ),

(16)

g(x) = 2{1 − (1 + x) exp(−x)}/x ,

(17)

2

where α1 = 2.0 kg1/2 · mol−1/2 and α2 can be set as a constant or related to Aφ .(33) Our
(2)
(1)
(2)
attempts to include β M
X at the expense of including C M X and C M X failed to produce
(2)
statistically defined values of β M X and any improvement in the fit. For C M X we have
adopted Archer’s(21) ionic strength dependent expression:
(1)

(0)

(2)

C M X = C M X + C M X h(α3 I 1/2 ) + C M X h(α4 I 1/2 ),

(18)

h(x) = 4{6 − (6 + 6x + 3x + x ) exp(−x)}/x ,

(19)

2

3

4

where α3 = 2.5 kg1/2 · mol−1/2 and α4 = 1.34 kg1/2 · mol−1/2 . Pitzer et al.(31, 34) recently
modified the ionic strength dependence of C M X and higher order terms. Differences
in values of C M X and its derivatives between our model and any subsequent models
developed using the newer ionic strength dependencies should be small.
Differentiation of equation (14) with respect to n w , n i , p, or T , and addition of infinite
dilution properties where appropriate, yield the osmotic coefficient (φ), activity coefficient
(γi ), and the apparent molar quantities for volume (Vφ ), enthalpy (L), and heat capacity
(C p,φ ). Thus, the osmotic coefficient expression for this system is:
!
.X
φ
φ
φ−1= 2
(20)
m i {−Aφ I 3/2 /(1 + bI 1/2 ) + m a m c (Bca
+ ZCca
)},
i

where
φ

(0)
(1)
(2)
1/2
1/2
BM X = βM
) + βM
),
X + β M X exp(−α1 I
X exp(−α2 I

(21)

and
φ

(0)

(1)

(2)

C M X = C M X + C M X exp(−α3 I 1/2 ) + C M X exp(−α4 I 1/2 ).

(22)
φ
BM X

It should be noted that, due to our adoption of the equivalence in form between
and
φ
φ
C M X , C M X in equation (22) is different from that of Pitzer(26) by a factor of 2|z M z X |1/2
φ
φ
(1)
(2)
1/2 ).
for the case where C M
X and C M X are zero valued, e.g. C M X = C M X,Pit zer /(2|z M z X |
The activity coefficient expressions for the cation M and anion X , respectively, are:
ln γ M = z 2M F + m a (2B Ma + Z C Ma ) + |z M |m a m c Cca ,

(23)

ln γ X =

(24)

z 2X F

+ m c (2BcX + ZCcX ) + |z X |m a m c Cca ,

where,
0
0
F = f γ + m a m c Bca
+ (1/2)m a m c Z Cca
,

f

γ

0
BM
X

= −Aφ {I
=

1/2

/(1 + bI

1/2

) + 2 ln(1 + bI

(1)
(2)
{β M X g 0 (α1 I 1/2 ) + β M X g 0 (α2 I 1/2 )},

(25)
1/2

)/b},

(26)
(27)

38

C. S. Oakes, A. R. Felmy, and S. M. Sterner
(1)

(2)

0
0
1/2
CM
) + C M X h 0 (α4 I 1/2 )},
X = {C M X h (α3 I

(28)

g (x) = −I

(29)

0

−1

{g(x) − exp(−x)},

and
h 0 (x) = −2I −1 {h(x) − exp(−x)}.
The Pitzer ion-interaction expression for the relative

(30)

enthalpy(26, 35, 36)

is expressed as:

L
L
L/(ww RT 2 ) = −(∂ f (I )/∂ T ) − 2m a m c {Bca
+ (1/2)ZCca
},

(31)

∂ f (I )/∂ T = (A L /b RT 2 ) · I ln(1 + bI 1/2 ),

(32)

A L = 4RT 2 (∂ Aφ /∂ T ) p,I ,

(33)

where
and
L
Bca
L
Cca

= (∂ Bca /∂ T ) p,I ,

(34)

= (∂Cca /∂ T ) p,I .

(35)

The Pitzer ion-interaction expression for C p,φ

is:(26, 35)

C p,φ /(ww RT 2 ) = C op,φ /(ww RT 2 ) + n −1
2 [(2/T ){∂ f (I )/∂ T } +
J
J
∂ 2 f (I )/∂ T 2 − 2m a m c {Bca
+ (1/2)Z Cca
}]

(36)

where
(2/T ){∂ f (I )/∂ T } + ∂ 2 f (I )/∂ T 2 = (A J /b RT 2 )I ln(1 + bI 1/2 ),

(37)

and
A J = (∂ A L /∂ T ) p,I ,

(38)

= ∂ Bca /∂ T + (2/T ) · (∂ Bca /∂ T ) p,I ,

(39)

J
Cca
= ∂ 2 Cca /∂ T 2 + (2/T ) · (∂Cca /∂ T ) p,I .

(40)

J
Bca

2

2

and
The corresponding Pitzer ion-interaction expression for Vφ

(26)

is:

o
V
V
Vφ /(ww RT ) = V2,φ
/(ww RT ) + n −1
2 [∂ f (I )/∂ p + 2m a m c {Bca + (1/2)Z C ca }],

(41)

where
∂ f (I )/∂ p = (A V /b RT ) · I ln(I + bI 1/2 ),

(42)

A V = (∂ Aφ /∂ p)T,I ,

(43)

= (∂ Bca /∂ p)T,I ,

(44)

V
Cca
= (∂Cca /∂ p)T,I .

(45)

and
V
Bca

and

Thermodynamic properties of aqueous calcium nitrate to T = 373 K

39

1.5

1.8

a

b
1.4

1.6

1.3
1.2
φ

φ

1.4

1.1
1.2
1.0
1.0

0.9
0.8

0.8

0

1
m

2

3

4

1/2/(mol · kg–1)1/2

0

1
m

2

3

4

1/2/(mol · kg–1)1/2

FIGURE 2. Osmotic coefficients φ as a function of m 1/2 of Ca(NO3 )2 (aq) at saturation pressure.
a, T = 298.15 K: ♦, reference 3; O, reference 4; ◦, reference 5; , reference 7. —, calculated
from equations (20) and (49); - - -, calculated from reference 1. Note that the latter curve has been
extrapolated beyond the molality limit claimed in reference 1. b, From reference 2: +, T = 373.15 K;
from reference 6; ◦, T = 373.15 K: , T = 393.15 K; ♦, T = 423.15 K. —, calculated from
equations (20) and (49).

SOURCES OF DATA USED IN THE MODEL

There are many sources of thermodynamic data for Ca(NO3 )2 (aq), most of which concern
the liquidus boundaries of the phases Ca(NO3 )2 · nH2 O (n nominally 9, 6, 4, 3, 2, or 0).
While a plethora of solubility data exists, we have not incorporated these data into our
model. We have also, with one exception,(2) not incorporated vapor-pressure data. With
the exception of our new dilution enthalpy data, there appear to be no thermodynamic data
above the (liquid + vapor) equilibrium surface ( psat ). Thus, while properties at p > psat
can be calculated from our fit due to the inclusion of pressure and water density terms in
the excess free energy expression, caution should be utilized in making extrapolations to
higher pressures.
Figure 2 shows the extensive isopiestic data for this system at T = 298.15 K, extending
from m = (0.06 to 22) mol · kg−1 , far exceeding the stable equilibrium solid saturation
point at m ≈ 8.1 mol · kg−1 . Isopiestic data are also available at T = (373, 393, and
423) K, though the data are limited at m < 2 mol · kg−1 .
Where possible and convenient, we have recalculated the isopiestic molalities from
the original sources as follows. Robinson’s(3) data, for which KCl(aq) was used as the
standard, have been recalculated using the KCl(aq) model of Holmes and Mesmer.(37)
The data of Stokes and Robinson(4) at T = 298.15 K for which H2 SO4 (aq) was the
standard, have been recalculated using the H2 SO4 (aq) model of Rard et al.(38) The data

40

C. S. Oakes, A. R. Felmy, and S. M. Sterner

of Platford,(7) for which CaCl2 (aq) was used as the standard, have been recalculated
according to the Holmes et al.(39, 40) model. Platford’s(7) osmotic coefficients obtained
using MgCl2 (aq) as the standard were fit as calculated by Platford. The data of Braunstein
and Braunstein(6) were recalculated using their isopiestic molalities for LiNO3 (aq) and
the model of Simonson and Pitzer.(41) Plake’s vapor-pressure data have been converted to
osmotic coefficients using the procedure of Rard and Platford.(42)
Prior to the measurements made as part of this study, 1dil H data were limited to T =
298.15 K. The low molality data of Lange and Streeck(9) are relatively straightforward,
while the higher molality data of Ewing and Rogers(8) were graphically adjusted and values
of 1dil H taken from the resultant graphs. The data from Lange and Streeck and those from
this study are shown in figure 1. The data of Ewing and Rogers(8) have been omitted from
the figure for clarity.
Figure 3 shows that the heat capacity data are rather non-uniformly distributed in (T, m)
space and appear to be of limited precision. The most extensive are those of Xu and
Hepler,(12) though, with the exception of T = 332 K, their data are limited to molalities
between (11 and 13.9) mol · kg−1 . The only low-molality heat capacity data are those of
Spitzer et al.(11) at T = 298.15 K. Note that while there is a large molality gap in the C p,φ
database model, values are still well constrained by the 1dil H data, equation (12), and our
function for C op,φ (discussed below).
A subset of the volumetric data is shown in figure 4. Most of the volumetric data are at
m > 1.5 mol · kg−1 and 298.15 ≤ (T /K) ≤ 333. Like the isopiestic data, the volumetric
data extend to very high molalities. The only very low molality data are those of Spitzer et
al.(11) The only data at T > 335 K are those of Rodyanskii et al.(16) at m ≤ 3.0 mol · kg−1 ,
Braunstein et al.(17) at m = 13.9 mol · kg−1 , and T = 373 K, and Jain(19) and Ramana et
al.(20) at 288 ≤ (T /K) ≤ 363 and m = 13.9 mol · kg−1 . The latter data(20) are inconsistent
with the other data considered and were given zero weight. The data of Rodyanskii et al.(16)
tail away from the proper Debye–H¨uckel limiting law slope at T = 373 K; consequently
their data at m ≤ 1.5 mol · kg−1 were given low weights.
As the published data for Ca(NO3 )2 (aq) tend to be at very high molalities, particularly
above T = 298.15 K, Pitzer ion-interaction parameters which operate most strongly at
(2)
o
low ionic strengths (e.g., β M
X ) and the infinite dilution values e.g., Vφ {Ca(NO3 )2 } and
o
C p,φ {Ca(NO3 )2 } are difficult, or impossible, to constrain. The latter problem is partially
alleviated by utilizing the additivity of standard states for better known systems. Thus, we
have included values of Vφo {Ca(NO3 )2 } and C op,φ {Ca(NO3 )2 } calculated from the standard
state values of aqueous CaCl2 ,(39, 40) HCl,(43) and HNO3 :(44, 45)
C op,φ {Ca(NO3 )2 } = C op,φ (CaCl2 ) + 2 · C op,φ (HNO3 ) − 2 · C op,φ (HCl),
Vφo {Ca(NO3 )2 } = Vφo (CaCl2 ) + 2 · Vφo (HNO3 ) − 2 · Vφo (HCl).

(46)
(47)

While the models for the aqueous CaCl2 and HCl systems are well constrained, the
temperature dependence of the infinite dilution quantities for aqueous HNO3 are poorly
o (HNO ) and V o (HNO ) to T = 328 K
constrained. Hovey and Hepler(44) determined Cp,φ
3
3
φ
(45)
and Clegg and Brimblecombe
present a thorough review and ion-interaction model

Thermodynamic properties of aqueous calcium nitrate to T = 373 K

41

10–2 · Cp,φ / (J · K–1 · mol–1)

2

1

0

–1

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

m 1/2/ (mol · kg–1)1/2
FIGURE 3. Apparent molar heat capacity C p,φ as a function of m 1/2 for Ca(NO3 )2 (aq) at p =
0.1 MPa.  and ♦, T = 298.15 K and 323 K, respectively, from reference 13: , T = 298.15 K from
reference 11; ◦, T = 323 K, 332 K, and 341 K (precision of data does not warrant differentiation by
temperature) from reference 12. —, T = 298.15 K; - - - -, T = 323 K calculated from equations (36)
and (49). Curves calculated at T = 332 K and T = 341 K are undistinguishable from the curve at
T = 323 K.

o (HNO ) values from the latter study are dependent on
to T = 373 K. However, Cp,φ
3
data from one source at T = 333 K. Infinite dilution heat capacities for Ca(NO3 )2 (aq)
o (HNO ) model monotonically increase
calculated using the Clegg and Brimblecombe Cp,φ
3
with temperature to T = 373 K rather than going through the expected maxima between
T = 323 and T = 348 K. Consequently, to T = 328 K, we favored infinite dilution
values calculated using the HNO3 model of Hovey et al. Above T = 328 K, the infinite
dilution values were guided by Tanger and Helgeson.(46) The temperature dependencies
o (HNO ) and V o (HNO ) calculated from the various combinations of sources and
of Cp,φ
3
3
φ
those from our model are shown in figure 5.
Weights w were assigned to each data set as follows:

w = w(i){a + b/m i,nwt + c · (m i,nwt )−1/2 },

(48)

where w(i) for all data were initially assigned values of 1.0 and, with few exceptions,
retained this value through all iterations of the fitting process. Values of the constants
a, b, and c in equation (48) are listed in table 3. Data with higher weights had less

42

C. S. Oakes, A. R. Felmy, and S. M. Sterner

65

Vφ/ (cm3 · mol–1)

60

55

50

45

40
0

1

2

3

4

m 1/2/ (mol · kg–1)1/2
FIGURE 4. Apparent molar volumes Vφ as a function of m 1/2 for Ca(NO3 )2 (aq) at p = 0.1 MPa,
T = 298.15 K: , from reference 11; •, from reference 15; , from reference 16. T = 323 K: ◦,
from reference 15. T = 373 K: ♦, from reference 16; , from reference 17. —, T = 298.15 K; – –,
T = 323 K; and - - - - -, T = 373 K calculated from equations (41) and (49).

influence on the fit, e.g., osmotic data for m < 0.2 mol · kg−1 had a smaller impact on
the fit than data corresponding to molalities between (0.2 and 4.5) mol · kg−1 . Data types
were generally favored in the following order: φ > 1dil H > Vφ > C p,φ . Assignment
of weights with respect to molality corresponds to estimates of relative error over those
molality ranges as well as keeping in mind limitations of the model with respect to molality.
For example, the accuracy of the isopiestic data at m = 12 mol · kg−1 should not be
significantly different than at m = 6 mol · kg−1 ; however, there is no reason to expect
a third virial coefficient model to reproduce the data at both molalities with equivalent
levels of accuracy. In contrast, the accuracy of isopiestic data below ≈ 0.2 mol · kg−1 is
expected to be lower(42) than that at higher molalities. Standard deviations (σ ) between
the model and fitted experimental values for the different data types over the range
298.15 ≤ (T /K) ≤ 373 are: φ, σ = 0.008 for m ≤ 10 mol · kg−1 or σ = 0.013 for
m ≤ 22; L, σ = 99 J · mol−1 for m ≤ 6.674 mol · kg−1 ; C p,φ , σ = 17 J · K−1 · mol−1
for m ≤ 14 mol · kg−1 ; and Vφ , σ = 0.37 cm3 · mol−1 for m ≤ 21 mol · kg−1 . The
σ value for Vφ includes data to T = 273 K,(18) and excludes Rodyanskii’s(16) data at
T = 373 K for m ≤ 1.5 mol · kg−1 . The σ for L excludes Ewing and Rogers’s(8) data for
m ≤ 3 mol · kg−1 .

Thermodynamic properties of aqueous calcium nitrate to T = 373 K

43

44
42
Vφo/ (cm3· mol–1)

10–2·Cpo,φ (J · K–1· mol–1)

–1.5

–2.0

–2.5

40
38
36
34

–3.0
32
–3.5

a

30

b

280 300 320 340 360 380 400 420

280 300 320 340 360 380 400 420

T /K

T /K

FIGURE 5. a, Apparent molar heat capacity C op,φ and b, molar volume Vφo at infinite dilution as
functions of m 1/2 at p = psat (0.1 MPa for T ≤ 373 K). , from reference 46. ◦, combination of
references 39, 43, and 44; and +, combination of references 39, 43, and 45.

The adjustable parameters β (0) , β (1) , C (0) , C (1) , C (2) , and the infinite dilution quantities
and Vφo {Ca(NO3 )2 } were fit with a function of temperature (T ), pressure
( p), and water density (ρw ) with the form:

o {Ca(NO ) }
Cp,φ
3 2

Q( pr , Tr , ρw ) = a1 · Tr−1 + a2 + a3 · Tr + a6 · ln Tr + pr · (a8 + a9 · Tr ) +
ln ρw (a19 · Tr−1 + a20 + a21 · Tr ),

(49)

where pr = p/100 MPa and Tr = T /298.15 K. The coefficients for equation (49) are
listed in table 4. The parameters β (0) , β (1) , C (0) , C (1) , C (2) are plotted against temperature
o {Ca(NO ) } are determined through
in figure 6. The quantities Vφo {Ca(NO3 )2 } and Cp,φ
3 2
0
appropriate differentiation of the quantity µ /(RT ) in table 4. Values of ln γ± , φ, L, C p,φ ,
and Vφ calculated at regular intervals of temperature and molality and at p = 0.1 MPa
are contained in tables 5 to 9. The latter tabulations extend to m = 20 mol · kg−1 and
T = 393 K; however, the user must reconcile the accuracy required in application with the
cited reproducibility levels or those which can be gathered from the figures.

4. Discussion
Prior to this study, the only ion-interaction model for Ca(NO3 )2 (aq) was limited to
T = 298.15 K and m = 2.0 mol · kg−1 .(1) Figure 2 demonstrates that the Pitzer–Mayorga
model deviates significantly from the data if it is extended beyond m = 2.0 mol · kg−1 .
Like Pitzer and Mayorga, Phutela and Pitzer(47) chose the same parameter set (β (0) , β (1) ,
and C ϕ ), where C ϕ = C (0) in equation (22), for their fit of CaCl2 (aq) which was valid

44

C. S. Oakes, A. R. Felmy, and S. M. Sterner
TABLE 3. Parameter values for weighting of the various data types
{equation (48)} and the corresponding molality ranges over which each weighting scheme is effective. Notable exceptions to the weighting schemes for
the respective datasets: reference 9, all weights fixed at 1.0; reference 8, for
m < 3 mol · kg−1 , w(i) = 2; and weights for most of the data in table 1 were
fixed at 0.1 except for those obtained using the SETARAM cells which were set
to values between 0.2 and 2.0; m o = 1 mol · kg−1
m/m o

a

< 0.1

b

c

1.0

0

0

≥ 0.1 and ≤ 10

0.05

0

0

> 10

0.2

0

0

< 0.5

0.5

0

0

≥ 0.5 and ≤ 3

1.0

3.0

0

>3

0.5

0

0

< 1.0

0.0

1.0

0

≥ 1.0

15.0

0

0

< 1.0

1.0

0

0.5

φ

L

C p,φ


≥ 1.0 and ≤ 10

0.5

0

0

≥ 10

1.0

0

0

TABLE 4. Parameter values for equation (49)
ai µo {Ca(NO3 )2 }/(RT )
1

3

1
βCa,NO

3

0
103 · CCa,NO

3

−0.30971820
−4.7248057

6

3

2
CCa,NO

3

15.682651

11.755000

1.5019366

−5.5640288 −6.0734918
0.33713344

8

4.2614148

9

−1.0946014

19

−29.674783

0.17086495 11.428444

−5.0694183

−11.967295

−0.074222032
0.15507132

−0.071123088
4.0922558

20
21

1
CCa,NO

0.43848291 −8.7494592 −6.6576793 0.47150400 −1.4002179

2
3

0
βCa,NO

−5.4226256

Thermodynamic properties of aqueous calcium nitrate to T = 373 K

45

TABLE 5. Values of the osmotic coefficient φ calculated at regular intervals
of temperature and molality at Psat (0.1 MPa for T ≤ 373 K). T o = 1 K,
m o = 1 mol · kg−1
T /T o :
m/m o

273

298.15

323

0.005
0.010

0.926
0.904

0.924
0.903

0.025
0.050

0.870
0.844

0.100
0.250

348

373

393

0.922
0.899

0.918
0.895

0.913
0.888

0.908
0.883

0.870
0.847

0.867
0.844

0.861
0.838

0.853
0.829

0.846
0.820

0.822
0.804

0.828
0.818

0.827
0.820

0.820
0.814

0.810
0.802

0.801
0.790

0.500
0.750

0.803
0.810

0.827
0.843

0.834
0.855

0.829
0.851

0.817
0.838

0.802
0.821

1.00
1.25

0.822
0.838

0.862
0.884

0.877
0.901

0.875
0.900

0.861
0.885

0.843
0.866

1.50
2.00

0.857
0.903

0.906
0.955

0.925
0.974

0.924
0.972

0.909
0.955

0.889
0.933

2.50
3.00

0.957
1.015

1.007
1.059

1.023
1.070

1.018
1.062

0.998
1.039

0.974
1.011

4.00
5.00

1.136
1.256

1.163
1.264

1.162
1.247

1.143
1.217

1.112
1.178

1.080
1.140

6.00
8.00

1.370
1.572

1.359
1.527

1.328
1.470

1.286
1.407

1.238
1.342

1.195
1.290

10.0
12.0

1.731
1.846

1.663
1.764

1.585
1.671

1.504
1.574

1.424
1.481

1.364
1.412

14.0
16.0

1.916
1.941

1.828
1.854

1.724
1.744

1.615
1.624

1.509
1.506

1.431
1.419

18.0
20.0

1.920
1.854

1.841
1.789

1.729
1.677

1.599
1.540

1.469
1.399

1.375
1.296

φ

to m ≈ 5 mol · kg−1 and to T = 473 K. Phutela and Pitzer ascribe the failure of their
model at m > 5 mol · kg−1 to a “change in structure involving substantial numbers
of ions and molecules” and hypothesize that this change involves a number of chloride
ions entering into the inner hydration shells of the calcium ions due to a increase in the
chloride activity relative to that of water. If a similar interpretation is applied to the failure
of the Pitzer–Mayorga model at m > 2 mol · kg−1 , then it is reasonable to imply that
ion-association effects become pronounced for Ca(NO3 )2 (aq) at lower molalities than for
CaCl2 (aq). That γ± for m = 2.0 mol · kg−1 CaCl2 (aq) is 0.791(39, 40) compared with 0.348
for Ca(NO3 )2 (aq) at T = 298.15 K and p = 0.1 MPa supports this argument. There is also
an abundance of Raman and i.r. spectroscopic data supporting substantial ion-association

46

C. S. Oakes, A. R. Felmy, and S. M. Sterner
TABLE 6. Values of the activity coefficient γ± as ln γ± calculated at regular intervals
of temperature and molality at psat (0.1 MPa for T ≤ 373 K). T o = 1 K, m o =
1 mol · kg−1
T /T o :
m/m o

273

298.15

323

0.005
0.010

−0.239
−0.321

−0.245
−0.329

0.025
0.050

−0.457
−0.583

0.100
0.250

348

373

393

−0.256
−0.341

−0.269
−0.357

−0.285
−0.378

−0.299
−0.398

−0.464
−0.586

−0.480
−0.602

−0.503
−0.631

−0.531
−0.667

−0.559
−0.700

−0.720
−0.911

−0.718
−0.891

−0.735
−0.905

−0.768
−0.943

−0.811
−0.998

−0.852
−1.051

0.500
0.750

−1.049
−1.121

−1.005
−1.057

−1.013
−1.055

−1.053
−1.096

−1.117
−1.167

−1.182
−1.240

1.00
1.25

−1.162
−1.185

−1.080
−1.087

−1.072
−1.072

−1.111
−1.112

−1.187
−1.191

−1.266
−1.276

1.50
2.00

−1.193
−1.182

−1.084
−1.055

−1.064
−1.030

−1.104
−1.071

−1.185
−1.159

−1.275
−1.257

2.50
3.00

−1.143
−1.088

−1.008
−0.950

−0.982
−0.926

−1.027
−0.976

−1.121
−1.078

−1.227
−1.191

4.00
5.00

−0.946
−0.783

−0.815
−0.667

−0.801
−0.670

−0.865
−0.750

−0.984
−0.886

−1.109
−1.024

6.00
8.00

−0.612
−0.276

−0.515
−0.220

−0.538
−0.282

−0.637
−0.416

−0.787
−0.600

−0.938
−0.775

10.0
12.0

0.030
0.288

0.048
0.280

−0.049
0.152

−0.217
−0.049

−0.433
−0.292

−0.628
−0.508

14.0
16.0

0.495
0.645

0.467
0.606

0.314
0.431

0.085
0.177

−0.188
−0.124

−0.424
−0.379

18.0
20.0

0.733
0.761

0.695
0.728

0.503
0.526

0.223
0.225

−0.102
−0.127

−0.377
−0.419

ln γ±

in the Ca(NO3 )2 (aq) system at relatively low temperatures and molalities.(48–54) In spite of
this, there are barriers to utilization of this evidence in a thermodynamic model. First, the
data from which to accurately quantify equilibrium constants for the association reactions
are absent and, second, there is the ambiguity in how an ion-complex is defined. For
example, do the anions form part of the electrically insulating sphere surrounding the
cations (solvent shared ion-pairs) or do the oppositely charged ions form pairs through
a dielectrically saturated hydration sphere (solvent separated ion-pairs), or do the anions
exclude water molecules to become effectively part of what is being insulated (bound,
contact ion pairs)? In each of these “types” of ion-pair, do we know that the ions are
kinetically discrete (e.g., do they spend more time in the vicinity of one another or in parts

Thermodynamic properties of aqueous calcium nitrate to T = 373 K

47

TABLE 7. Values of relative molar enthalpy L calculated at regular intervals
of temperature and molality at psat (0.1 MPa for T ≤ 373 K). T o = 1 K,
m o = 1 mol · kg−1
T /T o :
m/m o

273

298.15

323

348

373

393

L/(J · mol−1 )
0.005
0.010

300
330

548
688

872
1143

1251
1664

1696
2267

2117
2831

0.025
0.050

277
89

861
936

1567
1913

2350
2965

3233
4120

4039
5153

0.100
0.250

−317
−1394

903
572

2244
2592

3645
4619

5137
6702

6437
8457

0.500
0.750

−2879
−4174

−59
−679

2695
2628

5392
5835

8118
9066

10386
11752

1.00
1.25

−5338
−6387

−1268
−1811

2501
2356

6135
6360

9796
10399

12849
13779

1.50
2.00

−7329
−8923

−2303
−3127

2215
1983

6545
6864

10920
11809

14594
15986

2.50
3.00

−10177
−11146

−3748
−4191

1843
1797

7169
7490

12579
13283

17170
18216

4.00
5.00

−12417
−13049

−4645
−4679

1953
2364

8209
9026

14590
15825

20045
21649

6.00
8.00

−13258
−12943

−4434
−3461

2947
4414

9913
11810

17019
19323

23108
25737

10.0
12.0

−12167
−11263

−2195
−863

6057
7733

13764
15710

21533
23662

28108
30307

14.0
16.0

−10400
−9666

424
1606

9373
10942

17617
19473

25721
27724

32380
34361

18.0
20.0

−9108
−8753

2654
3550

12423
13808

21275
23022

29679
31597

36272
38131

of the solution beyond which their electrical fields effectively extend), and how do we
define the range over which the effective electrical fields extend? The measures of these
solvent–solute relationships are difficult to quantify for electrolytes.
Without explicit recognition of ion-association reactions, fitting Ca(NO3 )2 (aq) properties beyond m = 2.0 mol · kg−1 requires an extended form of the Pitzer ion-interaction
model. This extended form relaxes the need for contributions to the fit from the C (0) term
until relatively high ionic strengths are reached. This point is demonstrated in figures 7
and 8. Figure 7 is a plot of the deviation function g previously used for CaCl2 (aq)(47) in
which the low-molality contributors (β (1) , C (1) , C (2) , and the Debye–H¨uckel term) have

48

C. S. Oakes, A. R. Felmy, and S. M. Sterner
TABLE 8. Values of apparent molar heat capacity C p,φ calculated at regular
intervals of temperature and molality at psat (0.1 MPa for T ≤ 373 K).
T o = 1 K, m o = 1 mol · kg−1
T /T o :
m/m o

273

298.15

323

348

373

393

C p,φ /(J · K−1 · mol−1 )
0.000
0.005

−347
−341

−181
−169

−138
−124

−134
−118

−152
−133

−181
−158

0.010
0.025

−337
−330

−164
−154

−118
−108

−112
−101

−126
−114

−150
−138

0.050
0.100

−320
−306

−144
−129

−97
−83

−90
−76

−103
−90

−126
−113

0.250
0.500

−276
−238

−100
−69

−57
−29

−52
−26

−67
−41

−90
−64

0.750
1.00

−207
−179

−45
−25

−8.2
9.2

−6
11

−21
−3

−43
−23

1.25
1.50

−155
−133

−7.8
7.4

24
38

26
39

13
27

−6
9

2.00
2.50

−95
−63

33
54

60
78

61
79

51
70

36
58

3.00
4.00

−37
45

72
99

93
116

94
116

86
111

76
104

5.00
6.00

35
58

119
134

132
145

132
144

128
141

124
138

8.00
10.0

90
113

155
172

163
176

161
172

157
166

154
161

12.0
14.0

132
150

188
203

189
201

182
190

172
175

163
160

16.0
18.0

169
188

220
239

215
230

199
209

177
179

155
149

20.0

210

260

248

220

181

140

been subtracted from the osmotic coefficient, e.g.:
g = m −1 {φ − 1 + 2Aφ I 1/2 /(1 + bI 1/2 )} − (4/3)β (1) exp(−α1 I 1/2 ) −
(16/3)m{C (1) exp(−α3 I 1/2 ) + C (2) exp(−α4 I 1/2 )} =
(4/3)β (0) + (16/3)mC (0) .

(50)

Figure 7 gives (4/3)β (0) as the intercept and (16/3)C (0) as the slope. In contrast to
Phutela and Pitzer’s result for CaCl2 (aq), the relationship is linear over a rather substantial
molality range. It can be demonstrated that a similar linear relationship exists for CaCl2 (aq)

Thermodynamic properties of aqueous calcium nitrate to T = 373 K

49

TABLE 9. Values of apparent molar volume Vφ calculated at regular
intervals of temperature and molality at psat (0.1 MPa for T ≤ 373 K).
T o = 1 K, m o = 1 mol · kg−1
T /T o :
m/m o

273

298.15

323

348

373

393

Vφ /(cm3 · mol−1 )
0.000
0.005

31.21
31.76

39.53
40.15

43.58
44.34

44.95
45.92

43.98
45.24

41.43
43.01

0.010
0.025

31.98
32.43

40.38
40.81

44.61
45.08

46.24
46.78

45.64
46.30

43.50
44.29

0.050
0.100

32.93
33.63

41.25
41.84

45.53
46.08

47.27
47.84

46.86
47.48

44.94
45.63

0.250
0.500

35.11
36.97

42.97
44.31

47.06
48.17

48.77
49.78

48.43
49.47

46.66
47.80

0.750
1.00

38.56
39.99

45.43
46.41

49.07
49.86

50.61
51.34

50.34
51.12

48.80
49.71

1.25
1.50

41.29
42.48

47.31
48.13

50.57
51.23

52.00
52.61

51.83
52.50

50.55
51.33

2.00
2.50

44.60
46.42

49.59
50.85

52.40
53.43

53.70
54.67

53.69
54.75

52.75
54.00

3.00
4.00

48.01
50.62

51.97
53.85

54.34
55.91

55.53
57.04

55.70
57.34

55.12
57.03

5.00
6.00

52.70
54.38

55.38
56.67

57.23
58.36

58.32
59.42

58.73
59.91

58.62
59.94

8.00
10.0

56.97
58.88

58.74
60.34

60.23
61.69

61.25
62.66

61.81
63.19

61.98
63.35

12.0
14.0

60.34
61.47

61.60
62.61

62.86
63.78

63.73
64.51

64.14
64.70

64.15
64.44

16.0
18.0

62.33
62.96

63.40
64.00

64.47
64.95

65.02
65.28

64.91
64.76

64.26
63.62

20.0

63.38

64.41

65.24

65.30

64.29

62.55

to m > 5 mol · kg−1 when the ionic strength dependent C M X term is incorporated.
This does not negate Phutela and Pitzer’s contention that the deviation of the CaCl2 (aq)
data from their g function is a manifestation of change in the solute–solvent structural
relationship. Their conclusion is founded upon the theoretical argument that short-range
electrical interactions between three ions in water should have substantially smaller
effects upon the bulk solution properties than those between two ions and, consequently,
the second virial coefficient should have a more pronounced ionic-strength dependence.
However, in cases where the solute has a 2 : 1 or higher charge ratio and can achieve

50

C. S. Oakes, A. R. Felmy, and S. M. Sterner
2.5
a

b
–0.90

–0.95

1.5

103 · C (0)

β (0) or β (1) or C (1) or C (2)

2.0

1.0

–1.00

0.5

–1.05

0.0
280 300 320 340 360 380 400 420

280 300 320 340 360 380 400 420

T /K

T /K

FIGURE 6. The parameters a, —, β (0) ; - - - -, β (1) ; −. − . − . − ., C (1) ; – - –, C (2) , and b, 103 · C (0)
plotted against T at p = psat (0.1 MPa for T ≤ 373 K).
0.18

0.16

g

0.14

0.12

0.10

0.08

0.06
0

5

15
10
m / (mol · kg–1)

20

FIGURE 7. Deviation function g {equation (50)} based on the osmotic coefficient data. T =
298.15 K: ◦, reference 3; , reference 4. T = 373 K: ♦, reference 6. —, calculated from
equation (50) at T = 298.15 K; - - -, calculated from equation (50) at T = 373 K.

very high solubilities or super-saturation, exclusion of insulating solvent molecules by the
sheer numbers of solute ions forces higher order interactions which could be described
as ion-complexes under one or more of the classes described above. Thus, in the case of

Thermodynamic properties of aqueous calcium nitrate to T = 373 K

51

1.0
0.8
0.6

τ

0.4
0.2
0.0
–0.2
–0.4
–0.6
0

2

4

6

m / (mol · kg

8

10

–1)

FIGURE 8. Contributions τ of the products of the parameters in equations (20) to (23) and their
factors (molality and constant terms) to •, the quantity (φ − 1), at T = 373 K and p = 0.1 MPa
(e.g., the values of each curve at a fixed molality sum to the quantity (φ − 1)). ◦, Debye–H¨uckel
term; ♦, β (0) ; O, β (1) ; 4, C (0) ; 1, C (1) ; , C (2) .

extreme aqueous solubility or supersaturation, the C (1) and C (2) terms become analogous
to the β (2) term in allowing the ion-interaction model to reproduce properties of solutions
containing ion complexes without explicit inclusion of equilibrium constant expressions.
A significant difference between the β (2) and C (1) and C (2) terms is that β (2) is generally
used to describe strong associations at extreme dilutions. In contrast, figure 8 demonstrates
that while C (1) and C (2) operate like β (1) in that their effects are most pronounced at low
molality, the contributions of C (1) and C (2) occur at relatively higher molalities. It is also
worthwhile to note that the contributions of the latter two terms do not drop off as rapidly as
β (1) , and that while the contribution of the C (1) term is small, it is significant in the fit; and
that the large contribution of the C (2) term is due, in part, to our choice of α4 = 1.34. The
latter value was chosen during optimization of a similar parameter set for CaCl2 (aq).(30)
Thus, while ion-association effects may be important in this system, even at relatively low
temperatures and molalities, it is possible to reproduce the thermodynamic properties of the
system over a wide range of molalities with an extended form of the Pitzer ion-interaction
model. The expansion in the range of molalities and temperatures over which activity and
osmotic coefficients can be calculated comes without a concomitant significant increase in
model complexity.
This research was supported by the U.S. Dept of Energy Environmental Management
Sciences Program under project #26753: Chemical speciation of strontium, americium,
and curium in high-level waste: predictive modeling of phase partitioning during tank
processing.

52

C. S. Oakes, A. R. Felmy, and S. M. Sterner

Appendix
Figure A1 depicts the flow-through cells developed in this study and the following text
describes the parts and construction. Dimensions, tubing sizes, and numbers of windings,
as shown in the figure, are not to scale or correct in number. For clarity only, one of the two
connections between the two preheaters is shown. The two inlet and one effluent tubes pass
through a 0.63 cm bore in a Macor dowel. Below the macor insulator, the two 16 mm o.d.
by 8 mm i.d. inlet tubes are wound around a section of aluminum tube (0.46 m for each
tube, 10 turns) and encased in a stainless steel cylinder (equivalent to the thermal protector
described in the SETARAM C80-II manual) which makes a contact fit with the support
guides (described by SETARAM as a thermal buffer) above the sensing zone. This assembly constitutes an initial, passive preheater. The thermal buffer projects into an airspace
between the insulated plug capping the calorimeter furnace assembly and the sensing zone.
Immediately below the first preheater, the 16 mm tubes join to two lengths of 8 mm o.d.
tubing wound to form an approximately 2.54 mm long cylinder of approximately 6.3 mm

Macor
insulator

First
preheater
Second
preheater

Mixing
zone

FIGURE A1. Schematic diagram of the calorimetric cells developed in conjunction with this study.
The parts and assembly are described in the text.

Thermodynamic properties of aqueous calcium nitrate to T = 373 K

53

diameter. The 8 mm tubes are then joined at the top of the windings to another set of 8 mm
tubes tightly wound around a 3.8 cm long by 32 mm o.d. section of effluent line. The doubly wound 8 mm tubing constitutes a second passive preheater which sits in the deadspace
between the thermal buffer and the sensing zone. Below the second preheater, the two 8 mm
inlet lines pass through the center of a grooved aluminum cylinder supporting the 16 mm
mixing tube. The inlet lines and mixing line join at a tee joint at the bottom of the mixing
cell. All joins are gold welded and all tubing is platinum (8 mm lines) or (0.8 Pt + 0.2 Rh)
alloy (16 mm lines). Improvements to the performance of this design may be gained by
increasing the number of windings in the sensitive zone and by changing the preheater
configuration (particularly the second) to a more effective counter-current heat exchanger,
e.g., replacing the straight 32 mm section with a coil of 16 mm effluent line between the
two sets of 8 mm tubing. As the design used was already a third iteration we have not
attempted these changes. We gratefully acknowledge the guidance of Dr J. M. Simonson
of Oak Ridge National Laboratory which ultimately resulted in this design.
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