J. Chem.

Thermodynamics 38 (2006) 179–189

www.elsevier.com/locate/jct

Viscosity of aqueous Ni(NO3)2 solutions at temperatures from

(297 to 475) K and at pressures up to 30 MPa and concentration
between (0.050 and 2.246) mol Æ kg
1
a,*,1
I.M. Abdulagatov , A.B. Zeinalova b, N.D. Azizov b

a
Institute for Geothermal Problems of the Dagestan Scientific Center of the Russian Academy of Sciences, 367003 Makhachkala, Shamilya
Str., 39-A Dagestan, Russia
b
Azerbaijan State Oil Academy, Baku 370601, Azerbaijan

Received 26 January 2005; received in revised form 18 April 2005; accepted 20 April 2005
Available online 27 June 2005

Abstract

Viscosity of nine aqueous Ni(NO3)2 solutions (0.050, 0.153, 0.218, 0.288, 0.608, 0.951, 1.368, 1.824, and 2.246) mol Æ kg
1 was
measured in the temperature range from (297 to 475) K and at pressures (0.1, 10, 20, and 30) MPa. The measurements were carried
out with a capillary flow technique. The total experimental uncertainty of viscosity, pressure, temperature, and composition mea-
surements were estimated to be less than 1.6%, 0.05%, 15 mK, and 0.02%, respectively. All experimental and derived results are
compared with experimental and calculated values reported in the literature. Extrapolation of the solution viscosity measurements
to zero concentration (pure water values) for the given temperature and pressure are in excellent agreement (average absolute devi-
ation, AAD = 0.13%) with the values of pure water viscosity from IAPWS formulation [J. Kestin, J.V. Sengers, B. Kamgar-Parsi,
J.M.H. Levelt Sengers, J. Phys. Chem. Ref. Data 13 (1984) 175–189]. The viscosity data for the solutions as a function of concen-
tration have been interpreted in terms of the extended Jones–Dole equation for strong electrolytes. The values of viscosity A-, B-,
and D-coefficients of the extended Jones–Dole equation for the relative viscosity (g/g0) of aqueous Ni(NO3)2 solutions as a function
of temperature are studied. The derived values of the viscosity A- and B-coefficients were compared with the results predicted by
Falkenhagen–Dole theory (limiting law) of electrolyte solutions and the values calculated with the ionic B-coefficient data. The mea-
sured values of viscosity for the solutions were also used to calculate the effective rigid molar volumes in the extended Einstein rela-
tion for the relative viscosity (g/g0).

2005 Elsevier Ltd. All rights reserved.

Keywords: Aqueous solution; B-coefficient; Capillary viscometer; Nickel nitrate; Viscosity; Water

1. Introduction ural and industrial processes [1,2]. There is great practi-

Viscosity of aqueous electrolyte solutions is of
considerable interest due to its importance in both nat-
*
Corresponding author. Present address: Physical and Chemical
Properties Division, National Institute of Standards and Technology,
325 Broadway, Boulder, CO 80305, USA. Tel.: +1 303 497 4027; fax:
+1 303 497 5224.
E-mail addresses: ilmutdin@boulder.nist.gov, mangur@xtreem.ru
(I.M. Abdulagatov), Nazim_Azizov@yahoo.com (N.D. Azizov).
1
Tel.: +8722 62 66 23; fax: +8722 62 70 79.
cal interest in the accurate thermodynamic and
transport properties of aqueous salt solutions (design
calculation, heat and mass transfers phenomena, fluid
flow, developments and utilization of geothermal and
ocean thermal energy, material transport, solid deposi-
tion, corrosion in steam generators and electrical power
boilers, etc.). In many applications (chemical engineer-
ing and geochemistry), these processes occur at high
temperatures and high pressures. The oceans and
underground waters are the largest reservoirs of

0021-9614/$ - see front matter
2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jct.2005.04.017
180 I.M. Abdulagatov et al. / J. Chem. Thermodynamics 38 (2006) 179–189
aqueous electrolyte solutions. While surface and oceanic
waters are near room temperature, similar aqueous solu-
tions are present at high temperature and high pressure
in deep geological formations, while aqueous systems
also arise in steam-power generation, geothermal power
plants, hydrothermal synthesis, seawater desalination
processes, and other industrial operations at high tem-
peratures and high pressures. To understand and con-
trol those processes which use electrolyte solutions, it
is necessary to accurate know their thermodynamic
and transport properties.
Temperature and concentration dependences of vis-
cosity of aqueous electrolyte solutions are also crucial
for understanding ion-solvent interactions (long range
electrostatic interactions) [3–11]. Precise viscosity data
are needed to accurately calculate the A- and B-coeffi-
cients in the limiting law of viscosity and extended
Jones–Dole viscosity equation, respectively. The
Jones–Dole viscosity B-coefficients are of interest for
the discussion of structure making and breaking ionic
processes (solvation effects of cation and anion) [3–12].
The theory predicts the values of the viscosity A-coeffi-
cient for electrolyte solutions at infinite dilution
(m ! 0). To accurately determine the high degree viscos-
ity coefficients (viscosity B- and D-coefficients, for
example) in the extended Jones–Dole equation requires
reliable viscosity data for electrolyte solutions at high
concentrations. Theoretical modeling (Jiang and
Sandler [5], Esteves et al. [6], Chandra and Bagchi
[7,8], Lencka et al. [10], Wang et al. [11], and Hu [13])
of the viscosity of H2O + Ni(NO3)2 system will serve
as an example for other ionic systems of 2:1 charge-type
electrolytes.
However, viscosity data for the H2O + Ni(NO3)2 sys-
tem are scarce and less than satisfactory accuracy.
Experimental viscosity data for H2O + Ni(NO3)2
solutions under high temperatures and high pressures
were not available in the literature. The viscosity of
Ni(NO3)2(aq) at atmospheric pressure and at ambient
temperatures have been studied by several authors
(Doan and Sangster [14], Chesnakov [15], Polovnikova
et al. [16], and Zaytsev and Aseyeve [17]). This work is
a continuing of studying the transport properties (vis-
cosity and thermal conductivity) of concentrated aque-
ous electrolyte solutions at high temperatures and high
pressures. We previously reported the transport proper-
ties (thermal conductivity [18–20] and viscosity [20–25])
of aqueous Ca(NO3)2, NaNO3, LiNO3, Sr(NO3)2,
Li2SO4, Na2SO4, K2SO4, MgCl2, BaCl2, NaBr, KBr,
and LiI solutions at high temperatures (up to 623 K)
and high pressures (up to 50 MPa). The main objective
of the paper is to provide a new reliable experimental
viscosity data for Ni(NO3)2(aq) solutions at high tem-
peratures and high pressures to accurate calculate the
physical meaning viscosity A- and B-coefficients in the
extended Jones–Dole equation for the relative viscosity.
The present measurements focused on the temperature
range from (297 to 475) K, at pressures up to 30 MPa,
and at molalities between (0.05 and 2.246) mol Æ kg
1.
The present results considerably expand the tempera-
ture, pressure, and concentration ranges in which viscos-
ity for aqueous Ni(NO3)2 solutions are available. All
previous reported experimental data on the viscosity of
Ni(NO3)2(aq) cover near ambient temperatures (up to
373 K) and atmospheric pressure.
Doan and Sangster [14] used Cannon–Fenske type
viscometer for viscosity measurements of Ni(NO3)2(aq)
at temperature of 298.15 K and at atmospheric pressure.
The concentration range was from (0.25 to 4.0)
mol Æ kg
1. Chestnakov [15] reported kinematic viscosi-
ties of Ni(NO3)2(aq) at temperature of 293.15 K and
at atmospheric pressure for composition from (0.5 to
4.0) mol Æ l
1. Measurements were made with glass vis-
cometer with diameter of 0.5 mm. The uncertainty of
the viscosity and temperature measurements were
0.025% and 0.01 K, respectively. Polovnikova et al.
[16] reported viscosity data for Ni(NO3)2(aq) in the tem-
perature range from (303.15 to 368.15) K and concen-
trations between (0.309 and 5.745) mol Æ kg
1 at
atmospheric pressure. Measurements were performed
with Ostwal
d type viscometer. The uncertainty in tem-
perature, concentration, and viscosity measurements
were 0.1 K, 1.0%, and 0.5%, respectively.
2. Experimental apparatus and procedures
The apparatus and procedures used for the viscosity
measurements of the H2O + Ni(NO3)2 solutions have
been described in detail in previous papers [20–25] and
were used without modification. The measurements
were made using a capillary flow method which gives
an uncertainty of 1.6% for the viscosity. In a previous
papers [20–25] we reported measurements of viscosity
for H2O + Li2SO4, H2O + Na2SO4, H2O + K2SO4,
H2O + MgSO4, H2O + LiCl, H2O + LiNO3, H2O + Na-
NO3, and H2O + Ca(NO3)2 solutions by using the same
apparatus. The main parts of the apparatus consisted of
a working capillary with extension tube, a high temper-
ature and high pressure autoclave, movable and unmov-
able cylinders, electrical heaters, and solid red copper
block. Capillary together with extension tube was lo-
cated in the high temperature and high pressure auto-
clave. When the movable cylinder was moved
vertically at constant speed, the fluid flowed through
the capillary. The autoclave was placed in a solid red
copper block. Two electrical heaters were wound around
the surface of the copper block. To create and measure
of pressure, the autoclave was connected with a dead-
weight pressure gauge (MP-600) by means of separating
vessel. The uncertainty in pressure measurements was
0.05%. The dead-weight pressure gauge (MP-600) was
 I.M. Abdulagatov et al. / J. Chem. Thermodynamics 38 (2006) 179–189
calibrated with an accuracy of ±0.05% at the VNIIM
(All Russian Research Institute of Metrology, St. Peters-
burg). The sample temperature was measured with a
precision of ±0.015 K by using 10 X platinum resistance
thermometer (PRT-10, R100/R0 = 1.39245 and resistance
at 0 C is R0 = 9.9980 X). The thermometer was cali-
brated by the All Russian Scientific Research Institute
for Physical and Technical Measurements (VNIIFTRI,
Moscow) against the ITS-90 with an uncertainty of 0.7
mK. The PRT-10 was also calibrated periodically
against the defined reference of the triple point of water
(0.01 ± 0.0005 C), boiling point of water (100 ± 0.0007
C), and melting point of zinc (419.505 ± 0.0007 C) at
least one every six months and the observed drift within
1.0 mK was always corrected.
The final working equations for this method is
(Abdulagatov and Azizov [21])
3
g ¼ U sðq=qC Þð1
qC =qHg Þð1 þ aDtÞ
W qC =s;
U ¼ gpR4 DH 0 q0;Hg =8LV C ; W ¼ mV C =8pL; ð1Þ
where R = (0.15091 ± 0.005) mm is the inner radius of
the capillary, L = (216.53 ± 0.003) mm is the capillary
tube length, s is the time of flow, a is the linear expansion
coefficient of the capillary material, Dt is the difference
between experimental temperature and room tempera-
ture, m = 1.12 is a constant, q(P, T) is the density of the
fluid under study at the experimental conditions (p, T),
VC = 1.2182 cm3 is the volume of the unmovable (mea-
suring) cylinder, qC is the density of the fluid under study
at room temperature and experimental pressure, DH0 =
(H1
H2)/ln (H1/H2) = 3.64 cm, where H1 and H2 are
the mercury levels at the beginning and ending of the
fluid flowing, respectively, at room temperature and
atmospheric pressure, qHg is the density of mercury at
room temperature and experimental pressure, q0,Hg is
the density of mercury at room temperature and atmo-
spheric pressure. Equation (1) was derived from Poisseu-
ille
s law with corrections for the temperature effects on
the capillary sizes and mercury and sample densities at
the experimental conditions (p, T), and entrance effects
(acceleration of a fluid at the inlet and outlet) on the
fluid. The values of the parameters U and W can be also
determined by means of a calibration technique by using
well-known viscosity data for reference fluid. In this
study the viscometer was calibrated at selected tempera-
tures from (293 to 513) K and at selected pressures be-
tween (0.1 and 40) MPa with the use of reference
viscosity values of pure water (IAPWS standard [26]) sta-
ted with an uncertainty of less than (0.25 to 9.0) lPa Æ s.
The performance of the viscometer was checked by mea-
suring the viscosity of pure water at temperatures and at
pressures which were not used for the calibration. The
reproducibility of the water viscosity data (IAPWS
[26]) at any T and p in the range of present experiment
is within ±0.15%. The values of these parameters (U
181
and W) determined with both calculating and by calibra-
tion techniques are (37.27 Æ 10
7 and 2.508 Æ 10
7) and
(37.53 Æ 10
7 and 2.521 Æ 10
7), respectively. In this work,
we used the value of (37.53 Æ 10
7 and 2.521 Æ 10
7). The
time of fluid flowing through the capillary s was mea-
sured with a stop-watch with an uncertainty of less than
0.1 s (0.5%). An electromagnetic device was used to start
and stop the watch.
The viscosity was obtained from the measured quan-
tities R4, DH0, L, VC, s, qHg, qC, T, p, and m. The accu-
racy of the viscosity measurements was assessed by
analyzing the sensitivity of equation (1) to the experi-
mental uncertainties of the measured quantities (Abdul-
agatov and Azizov [21]). At the maximum measured
temperature (475 K), the values of the root-mean-square
deviations in the viscosity measurements was
dg = 2 Æ 10
5 g Æ cm
1 Æ s
1. Based on the detailed analy-
sis of all sources of uncertainties likely to affect the
determination of viscosity with the present apparatus,
the combined maximum relative uncertainty dg/g in
measuring the viscosity was 1.5% (see Abdulagatov
and Azizov [21]). The Reynolds (Re) number occurring
during all measurements was less than the critical values
(Rec = 300).
As one can see from equation (1), to calculate the dy-
namic viscosity from measured quantities, the values of
density of the solution under study at room temperature
and experimental pressure qC, and density at the exper-
imental conditions q(p, T) are needed. For this purpose,
we used the density data reported in our previous publi-
cation (Azizov and Zeinalova [27]) for aqueous
Ni(NO3)2 solutions at high temperatures (up to 573 K)
and high pressures (up to 35 MPa) and concentration
up to 2.246 mol Æ kg
1.
The H2O + Ni(NO3)2 solutions were prepared from
chemically pure Ni(NO3)2 (Merck GR, >0.995 mass
fraction) and doubly distilled water. The solutions were
prepared gravimetrically with an analytical balance
having a precision of ±5 Æ 10
8 kg. The solutions at the
desired composition were prepared by mass. The com-
position was checked by comparison of the density of
solution at 298.15 K and 0.1 MPa with reference data.
3. Results and discussions
Viscosity of nine aqueous Ni(NO3)2 solutions (0.05,
0.153, 0.218, 0.288, 0.608, 0.951, 1.368, 1.824, and
2.246) mol Æ kg
1 were measured in the temperature
range from (297 to 475) K. All experimental viscosity
data were obtained as a function of temperature at four
isobars (0.1, 10, 20, and 30) MPa. The experimental tem-
perature, viscosity, pressure, and composition values for
the aqueous Ni(NO3)2 solutions are presented in table 1.
Some selected experimental viscosity data for
H2O + Ni(NO3)2 solutions as an example of the present
182 I.M. Abdulagatov et al. / J. Chem. Thermodynamics 38 (2006) 179–189

TABLE 1
Experimental values of viscosity, pressure, temperature, and concentration of H2O + Ni(NO3)2 solutions
0.1/MPa 10/MPa 20/MPa 30/MPa

1
T/K m = 0.05 mol Æ kg
299.24 0.8840 0.8839 0.8843 0.8845
321.54 0.5771 0.5790 0.5797 0.5820
347.65 0.3939 0.3949 0.3964 0.4013
372.54 0.2921 0.2949 0.2984 0.3015
394.68 0.2391 0.2416 0.2449
421.95 0.1929 0.1958 0.1985
449.65 0.1611 0.1639 0.1661
472.15 0.1420 0.1447 0.1468
T/K m = 0.153 mol Æ kg
1
298.65 0.9231 0.9246 0.9251 0.9261
322.56 0.5821 0.5872 0.5920 0.5938
348.89 0.4010 0.4057 0.4091 0.4122
372.46 0.3059 0.3101 0.3140 0.3166
397.82 0.2441 0.2474 0.2509
424.57 0.1989 0.2030 0.2050
449.28 0.1703 0.1741 0.1764
471.51 0.1510 0.1534 0.1565
T/K m = 0.218 mol Æ kg
1
298.43 0.9454 0.9468 0.9471 0.9482
323.74 0.5854 0.5895 0.5944 0.5968
347.94 0.4152 0.4194 0.4228 0.4260
372.48 0.3134 0.3179 0.3212 0.3248
398.61 0.2490 0.2532 0.2549
424.57 0.2053 0.2081 0.2119
449.72 0.1750 0.1778 0.1807
474.24 0.1536 0.1560 0.1592
T/K m = 0.288 mol Æ kg
1
298.65 0.9601 0.9606 0.9610 0.9620
322.56 0.6103 0.6122 0.6130 0.6145
347.43 0.4289 0.4346 0.4376 0.4422
373.06 0.3246 0.3275 0.3318
398.42 0.2566 0.2608 0.2633
422.81 0.2142 0.2168 0.2198
448.96 0.1818 0.1845 0.1878
473.87 0.1591 0.1628 0.1645
T/K m = 0.608 mol Æ kg
1
0.1/MPa 10/MPa 20/MPa 30/MPa
297.98 1.0776 1.0770 1.0773 1.0780
323.46 0.6691 0.6724 0.6754 0.6781
349.76 0.4664 0.4708 0.4742 0.4779
373.82 0.3600 0.3643 0.3681
398.49 0.2890 0.2930 0.2967
423.73 0.2402 0.2435 0.2468
449.46 0.2050 0.2085 0.2114
474.83 0.1805 0.1834 0.1860
T/K m = 0.951 mol Æ kg
1
298.64 1.1927 1.1936 1.1940 1.1940
323.67 0.7503 0.7533 0.7564 0.7595
349.46 0.5292 0.5331 0.5374 0.5411
375.81 0.3950 0.3990 0.4042 0.4070
396.43 0.3329 0.3365 0.3403
422.83 0.2731 0.2767 0.2807
449.48 0.2309 0.2347 0.2382

T/K m = 1.368 mol Æ kg
1

299.76 1.3477 1.3480 1.3490 1.3500
326.78 0.8295 0.8341 0.8376 0.8422
338.46 0.7030 0.7074 0.7123 0.7174
349.76 0.6103 0.6146 0.6194 0.6253
372.49 0.4771 0.4824 0.4869
 I.M. Abdulagatov et al. / J. Chem. Thermodynamics 38 (2006) 179–189 183

TABLE 1 (continued)
0.1/MPa 10/MPa 20/MPa 30/MPa
399.46 0.3743 0.3789 0.3840
416.89 0.3270 0.3311 0.3363
426.89 0.3051 0.3095 0.3134
447.26 0.2684 0.2714 0.2760
475.84 0.2300 0.2342 0.2375
T/K m = 1.824 mol Æ kg
1
297.86 1.6710 1.6720 1.6720 1.6730
324.76 1.0259 1.0310 1.0358 1.0400
349.76 0.7220 0.7280 0.7335 0.7380
372.84 0.5558 0.5612 0.5672 0.5721
399.46 0.4393 0.4445 0.4496
422.49 0.3682 0.3726 0.3780
448.24 0.3116 0.3159 0.3211
473.12 0.2716 0.2768 0.2808
T/K m = 2.246 mol Æ kg
1
0.1/MPa 10/MPa 20/MPa 30/MPa
297.86 1.9729 1.9730 1.9735 1.9742
309.84 1.5368 1.5390 1.5424 1.5446
322.46 1.2253 1.2310 1.2362 1.2410
330.84 1.0722 1.0783 1.0822 1.0890
347.82 0.8430 0.8486 0.8534 0.8621
364.21 0.6918 0.6980 0.7050 0.7104
375.48 0.6190 0.6251 0.6322
394.58 0.5162 0.5211 0.5279
412.58 0.4452 0.4505 0.4568
426.84 0.4007 0.4063 0.4124
446.79 0.3515 0.3578 0.3622
472.46 0.3040 0.3094 0.3140

1.5
4.8

4.3
1.3

3.8
η / mPa·s

3.3 1.1

2.8

0.9
2.3

1.8
0.7

1.3

0.8 0.5
0 1 2 3 4 5 0.0 0.7 1.4 2.1 2.8
m / mol·kg-1 m / mol·kg-1

FIGURE 1. Measured values of viscosity g of H2O + Ni(NO3)2 solutions as a function of molality m along two selected isotherms of 298.15 K (left)
and 323.15 K (right) and at atmospheric pressure. Left: d, this work; s, Doan and Sangster [14]; ·, Zaytsev and Aseyev [17]; n, ICT [28]; (——),
Doan and Sangster [14]; (–––), Moulik and Rakshit [29]. Right: s, Polovnikova et al. [16].
184 I.M. Abdulagatov et al. / J. Chem. Thermodynamics 38 (2006) 179–189

results are shown in figures 1 to 3 in the g–m, g–T, and
g–p projections together with values reported by other
authors.
The present experimental values of the viscosity for
H2O + Ni(NO3)2 solutions at atmospheric pressure were
compared with the data reported by other authors in the
literature. Figure 1 shows the comparison between
present viscosity values for H2O + Ni(NO3)2 solutions
and the values reported by Doan and Sangster [14], Che-
snakov [15], Polovnikova et al. [16], ICT [28], and calcu-
lated with correlations of Zaytsev and Aseyev [17], and
Moulik and Rakshit [29] at two selected temperatures
of (298.15 and 323.15) K at atmospheric pressure. As
one can see from figure 1, the agreement between
present results and the data reported by Doan and Sang-
ster [14] and ICT [28] is excellent, AAD within 0.4%,
while the data reported by Polovnikva et al. [16] system-
atically higher than present data by 2.3% at temperature
of 323.15 K. Figure 2(a) and (b) demonstrated the
comparison of the temperature dependence of viscosity

2.0 3.4

1.8
2.9
1.6

1.4 2.4
η / mPa·s

1.2
1.9
1.0

0.8 1.4

0.6
0.9
0.4
a
0.2 0.4
273 293 313 333 353 373 273 293 313 333 353 373
T/ K T/ K

2.0

1.7

1.4
η / mPa·s

1.1

0.8

0.5

b
0.2
273 288 303 318 333 348 363
T/ K

FIGURE 2. (a) and (b) Measured values of viscosity g of H2O + Ni(NO3)2 solutions as a function of temperature T at three selected constant
concentrations of 0.218 (a, left), 0.608 (b), and 1.368 (a, right) mol Æ kg
1 and at atmospheric pressure together with the data reported by other
authors. d, this work; s, Polovnikova et al. [16]; h, Doan and Sangster [14]; ·, Chesnakov [15]; (– – –), Zaytsev and Aseyev [17]; (——), smoothed
experimental curve.
 I.M. Abdulagatov et al. / J. Chem. Thermodynamics 38 (2006) 179–189 185

20
1.35

15

-1
1.15

α η×10 /MPa
η / mPa.s

4
10
0.95

0.75

0
295 315 335 355 375 395 415 435 455 475
0.55 T/ K
0 5 10 15 20 25 30

og 
P/ MPa FIGURE 4. Viscosity pressure coefficient, ag ¼ 1g oP , of
TX
H2O + Ni(NO3)2 solutions as a function of temperature T at selected
FIGURE 3. Measured values of viscosity g of H2O + Ni(NO3)2
pressures and constant concentration of 1.368 mol Æ kg
1. d, 0.1 MPa;
solutions as a function of pressure P at four selected temperatures and
s, 10 MPa; h, 30 MPa; (——), IAPWS [26] (pure water).
constant concentration of 1.368 mol Æ kg
1. d, 299.76 K; j, 326.78 K;
h, 338.46 K; s, 349.76 K.

(10% to 15%) higher than for pure water and almost

of the H2O + Ni(NO3)2 solutions for various reported
data sets at three selected concentrations. In generally
the agreement between various data sets is good (within
±2.0%), while the values of viscosity reported by
Zaytsev and Aseyev [17] observed systematically higher
by 25% than all available data sets. The pressure
dependence of the measured viscosities along various
isotherms at constant concentration (m = 1.368
mol Æ kg
1) is shown in figure 3. As this figure shows,
the viscosity of solution along constant composition
and isotherms is slightly increases linearly as pressure
increasing (the slopes (og/op)TX of the g–p curves are al-
most constant). The viscosity is little affected (up to
0.1% to 0.4% at low temperatures and up to 3.4% at
high temperatures) by pressure (at pressure changing be-
tween 0.1 MPa and 30 MPa) along the isotherms (see
figure 3). For pure water at the same temperature and
pressure ranges the pressure effect on viscosity within
0.5% at low temperatures and 5% at high temperatures.
Figure 4 shows the temperature dependence of the
pressure coefficients, ag = (1/g)(og/op)TX, along various
isobars and at fixed composition of 1.368 mol Æ kg
1
together with values for pure water calculated with
IAPWS formulation [26]. As one can see from this
figure, the values of ag for the solution are slightly
independent of pressure, especially at low temperatures.
As a check of the method and procedure of the mea-
surements, the viscosity of pure water were calculated by
using linear extrapolating procedure for the two
pressures (0.1 and 10) MPa. The present extrapolated
to zero concentration (m ! 0) viscosity data and calcu-
lated values of viscosity for pure water from IAPWS [26]
formulation is given in table 2. As this table shows, the
agreement between IAPWS [26] calculations and the
present extrapolated to zero concentration (pure water
values) results along the isobars (0.1 and 10) MPa in
the temperature range from (298.15 to 473.15) K is
excellent (AAD = 0.13%, Bias = 0.01%, SD = 0.17%,
SE = 0.05%, and Max.Dev = 0.37%, N = 16). This excel-
lent agreement between the present extrapolated data
and IAPWS [26] calculations for pure water confirms
the reliability and high accuracy of the measurements
for H2O + Ni(NO3)2 solutions and correct operation of
the present instrument.
The measured viscosities for the solution were used to
calculate physical mining viscosity A- and B-coefficients
in the extended Jones–Dole equation for the concentra-
tion dependence of relative viscosity (g/g0). Viscosity B-
coefficients can be obtained from experimental viscosity
data by plotting (g/g0
1)c
1/2 against c1/2 (Jones–Dole

TABLE 2
Comparison between extrapolated to zero concentration (pure water values) viscosity data and values calculated with IAPWS [26] standard for pure
water at two selected pressures (AAD = 0.13%)
T/K 298.15 323.15 348.15 373.15 398.15 423.15 448.15 473.15
p = 0.1/MPa
This work 0.8912 0.5463 0.3769
IAPWS [26] 0.8901 0.5468 0.3777
p = 10/MPa
This work 0.8913 0.5489 0.3803 0.2847 0.2243 0.1846 0.1568 0.1365
IAPWS [26] 0.8880 0.5486 0.3803 0.2844 0.2246 0.1849 0.1569 0.1364
186 I.M. Abdulagatov et al. / J. Chem. Thermodynamics 38 (2006) 179–189

plot) as in figure 5. The slope of the resulting straight reported by other authors and calculated from theory
line gives the value of B-coefficient directly, and the (from ionic viscosity
P B-coefficient data assumed the
intercept should agree with the theoretical value of the additivity B ¼ mi Bi of the ionic Bi-coefficients, Cox
viscosity A-coefficient calculated with equation (2) (Fal- and Wolfender [31]). The values of ionic Bi-coefficients
kenhagen and Dole [30]) are constant at a given T for given ions in a specific sol-
vent and describe solely the ion-solvent interactions. As
A ¼ A ðe0 T Þ
1=2 g
1 1 1
0 f ðkþ ; k
; zþ ; z
Þ; ð2Þ
one can see from figure 6 the agreement between A- and
B-coefficients derived in present study and calculated
A ¼ Fe2 N A ð1 þ 21=2 Þðe kÞ
1=2 =12p;
1=2

 "
 # with theory and ionic B-coefficients data is good at

1 2
z2 k1 1
þ þ k
4 k1
þ
k

low temperatures. Figure 6 demonstrate that B-coeffi-
f ¼

 1

2
 ; ð3Þ cients go through a minimum (dB/dT = 0) near the 400
4 2 þ 21=2 k1 1
þ k
1 þ 21=2 k1 1 2
þ þ k

K. At temperatures below about 400 K the derivative
where A* = 1.113 Æ 10
5 C2(m Æ K Æ mol
3)1/2, f ðk1 1
þ ; k
; (temperature coefficient) dB/dT < 0 is negative (struc-
zþ ; z
Þ is the function of the equivalent conductences k1 ture-making ions), while above the temperature of 400
at infinite dilution of the ions, and z± is the charges. The K, dB/dT > 0 is positive (structure-breaking ions) [32–
value of parameter A depends also on the viscosity of 34]. The B-coefficients, obtained by other authors for
the solvent g0 (pure water), its relative permittivity other aqueous electrolyte solutions in all previous stud-
(dielectric constant) e0, and the temperature T. ies, are increase almost linearly (dB/dT > 0) with
The values of B-coefficients are a manifestation of temperature.
ion-solvent interaction and this is supported by the lin- Jones and Talley [35], Kaminsky [36,37], Desnoyers
earity of the Bc term in the concentration. No theory and Perron [38], Desnoyers et al. [39], Feakins and Law-
has yet been developed for the B-coefficient but impor- rence [40], and Robertson and Tyrrell [41], added a qua-
tant qualitative explanations have been advanced in dratic term (extended Jones–Dole equation)
terms of ion-solvent interaction [3–12]. The results of
g=g0 ¼ 1 þ Ac1=2 þ Bc þ Dc2 ð4Þ
the calculating of the viscosity A- and B-coefficients by
using present viscosity data for H2O + Ni(NO3)2 solu- to extend the Jones–Dole equation for more concen-
tions are summarized in table 3 and presented in figure trated electrolyte solutions (c < 0.1 to 0.2 m). The new
6 as a function of temperature together with values Dc2 term of equation (4) is including all solute–solvent

0.9 1.1
a b

0.7
0.8
(η/η0-1)c-1/2

0.5
/2
1
2c
0.29 0.5
2+
17
0.0
/2
1
0.3 96c
2+ 0.1
5
0.0

0.2

0.1

0.0 0.5 1.0 1.5 0.0 0.3 0.6 0.9 1.2

1/2 -1 1/2 1/2 -1 1/2
c / (mol·l ) c / (mol·l )
FIGURE 5. Jones–Dole plot, [(g/g0)
1]/c1/2 vs. c1/2, for H2O + Ni(NO3)2 solutions for selected isotherms of 298.15 K (a) and 323.15 K (b) and at
atmospheric pressure. d, this work (exp.); (– – –), limiting slope; (——), calculated with equation (4).
 I.M. Abdulagatov et al. / J. Chem. Thermodynamics 38 (2006) 179–189 187

TABLE 3
The viscosity A-, B-, and D-coefficients of aqueous Ni(NO3)2 solutions as a function of temperature
T/K A/(dm3/2 Æ mol
1/2) B/(dm3 Æ mol
1) D/(dm6 Æ mol
2)
p = 0.1/MPa
298.15 0.017 0.292 0.02
323.15 0.052 0.196 0.28
348.15 0.082 0.172 0.47
373.15 0.100 0.160 0.58
p = 10/MPa
298.15 0.017 0.292 0.02
323.15 0.055 0.210 0.21
348.15 0.084 0.190 0.47
373.15 0.103 0.174 0.54
398.15 0.112 0.157 0.64
423.15 0.122 0.157 0.72
448.15 0.130 0.166 0.82
473.15 0.135 0.189 0.90

0.32

0.13
0.29

0.11
0.26
A / dm3/2·mol-1/2

B / dm3·mol-1

0.09
0.23

0.07
0.20

14
0.05 0.17

0.03 0.14

0.01 0.11
290 290 330 370 410 450
330 370 410 450
T/ K
T/ K

FIGURE 6. Experimental viscosity A- and B-coefficients of H2O + Ni(NO3)2 solutions as a function of temperature together with values reported by
other authors. Left: d, this work (0.1 MPa); s, this work (10 MPa). Right: d, this work (0.1 MPa); }, this work (10 MPa); s, Jenkis and Marcus
[12]; n, Moulik and Rakshit [29]; ·, Doan and Sangster [14].

and solute–solute structural interactions that were not
accounted by the Ac1/2 and Bc terms at high concentra-
tions such as [3,38]: high terms of the long-range coulom-
bic forces; high term hydrodynamic effect; and
interactions arising from changes in solute-solvent inter-
actions with concentration. The range of the concentra-
tion in present study is overlaps range where Bc term is
essential. In present study, we used equation (4) for
application to higher concentration. The relative viscos-
ities for Ni(NO3)2(aq) were fitted, up to 2.245 m, with the
relation (4). The values of the A-, B-, and D-coefficient
calculated with present viscosity data are presented in ta-
ble 3 for various temperatures. As one can see from this
table, the values of the D-coefficient are monotonically
increasing with temperature. According conventional
technique of the viscosity coefficients determination,
the D-coefficients can be estimated also from experimen-
tal viscosity data as
 
Dc ¼ ðg=g0 Þ
1
Ac1=2 =c
B; ð5Þ
188 I.M. Abdulagatov et al. / J. Chem. Thermodynamics 38 (2006) 179–189
using theoretical value of A and slopes of the depen-
dence [(g/g0)
1]/c1/2 on c1/2 (Jones–Dole plot [42], see
figure 5)
½ðg=g0 Þ
1=c1=2 ¼ A þ Bc1=2 .
A technique for predicting the temperature dependence
of the viscosity B-coefficients has been developed using
the concept of structure-breaking and structure-making
ions [10,34]
B ¼ BE þ BS exp½
KðT
273.15Þ;
where K = 0.048 is the constant; BE = 0.164932 l Æ mol
1
is the Einstein contribution (hydrodynamic, intrinsic
term); and BS = 0.425881 l Æ mol
1. The model repro-
duces the viscosity of aqueous systems ranging from di-
lute to concentrated solutions (2 m) at temperatures up
to 475 K (see figure 6).
Thomas [43] has extended the Einstein relation (g/
g0 = 1 + k/, where k = 2.5, / = (4/3)pR3NAc is the vol-
ume fraction of the solute molecules, R is the effective
solute ions radius, / = Vkc) for the hydrodynamic effect
to high concentrations by showing that for suspensions
the relative viscosity is given by the relation
g=g0 ¼ 1 þ 2.5/ þ 10.05/2 ¼ 1 þ 2.5V k c þ 10.05V 2k c2 .
As was shown by Breslau and Miller [44], this relation
can be used to represent concentration dependence of
the relative viscosity for concentrated electrolyte solu-
tions if Vk is taken as an adjustable parameter (effective
rigid molar volumes). They calculated the values of
Vk = 0.064 mol Æ l
1 for H2O + Ni(NO3)2 solutions at
298.15 K and at atmospheric pressure from viscosity
data in the concentration range between (0.125 and
1.0) m. We determined the values of Vk for H2O +
Ni(NO3)2 in equation (8) in the concentration range
from (0.05 to 2.0) mol Æ l
1 at two pressures (0.1 and
10) MPa. The derived values of the Vk for H2O + Ni(-
TABLE 4
Effective rigid molar volumes of aqueous Ni(NO3)2 solutions as a
function of temperature at two pressures from viscosity data
T/K Vk/(l Æ mol
1)
p = 0.1/MPa
298.15 0.11008
323.15 0.12019
348.15 0.12419
373.15 0.12729
p = 10/MPa
298.15 0.11541
323.15 0.12006
348.15 0.12397
373.15 0.12699
398.15 0.12968
423.15 0.13241
448.15 0.13520
473.15 0.13844
NO3)2 solutions are given in table 4. Our result
Vk = 0.1100 mol Æ l
1 at temperature of 298.15 K in the
concentration range from (0.05 to 2.0) m is higher than
the value derived by Breslau and Miller [44]. Moulik
ð6Þ
and Rakshit [29] also used equation (8) to correlate
the concentration dependence of the viscosity of elec-
trolyte solutions at high concentrations. The relation
(4) can be used to estimate the values of the hydro-
static volume by using experimental relative viscosity
ð7Þ data. The values of viscosity calculated with equation
(8) for Ni(NO3)2(aq) shown in figure 1 together with
present results.
4. Conclusions
Viscosity of nine aqueous Ni(NO3)2 solutions (0.05,
0.153, 0.218, 0.288, 0.608, 0.951, 1.368, 1.824, and
2.246) mol Æ kg
1 were measured in the temperature
range from (297 to 475) K and at pressures (0.1, 10,
20, and 30) MPa with a capillary flow technique. The to-
tal experimental uncertainty of viscosity, pressure, tem-
perature, and composition measurements were
estimated to be less than 1.5%, 0.05%, 15 mK, and
0.02%, respectively. The measured viscosity values of
ð8Þ solutions at atmospheric were compared with the data
reported in the literature by other authors. Good agree-
ment (within ±0.4%) is found between the present mea-
surements and the data sets reported by other authors in
the literature. The temperature, pressure, and concentra-
tion dependences of the viscosity are studied. The values
of the viscosity A-, B-, and D-coefficients of the extended
Jones–Dole equation for the relative viscosity (g/g0) of
aqueous Ni(NO3)2 solutions as a function of tempera-
ture are studied. The derived values of the viscosity
A- and B-coefficients were compared with the results
predicted by Falkenhagen–Dole theory (limiting law)
of electrolyte solutions and calculated with the ionic
B-coefficient data. The measured values of viscosity for
the solution were used also to calculate the effective rigid
molar volumes in the extended the Einstein relation for
the relative viscosity.
Acknowledgments
I.M. Abdulagatov thanks the Physical and Chemical
Properties Division at the National Institute of Standards
and Technology for the opportunity to work as a Guest
Researcher at NIST during the course of this research.
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JCT 05-27