Article

[Link]/jced

Thermal Conductivity and Density of (NH4)2SO4 + H2O, NH4NO3 +

H2O, and (NH4)2SO4 + NH4NO3 + H2O Solutions at T = (278.15 to
333.15) K
Yuan-Yuan Che, Jian Shen, Jun-Chao Zhou, and Chao-Hong He*
State Key Laboratory of Chemical Engineering, Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou
310027, China

ABSTRACT: The thermal conductivity of ammonium sulfate + water,

ammonium nitrate + water, and ammonium sulfate + ammonium nitrate +
water is of great significance in the national defense industry and military
engineering for manufacturing of various energetic chemicals. The measurements,
covering a temperature range from (278.15 to 333.15) K, have been performed by
a transient hot-wire technique over a wide range of concentrations. The densities
of ternary aqueous solutions of ammonium sulfate + ammonium nitrate are also
presented at the same temperature covering different portions of ammonium
sulfate and ammonium nitrate. The thermal conductivities of binary aqueous
solutions of ammonium salts are correlated by polynomial functions in terms of
temperature and weight fraction for the purpose of interpolation. The Aseyev
equation in terms of weight fraction is also used to represent the thermal
conductivities of ternary mixtures of these compounds. The ideal mixing rule of
Young has been successfully applied to correlate the ternary densities of aqueous ammonium sulfate + ammonium nitrate
solutions based on relevant binary solution properties. The agreement between the correlation and the experimental data is
pretty good.

■ INTRODUCTION
Transport properties, particularly the thermal conductivity of
relatively simple process and low cost. In the procedure,
nitrourea is first produced in situ without separation of the
aqueous electrolyte solutions, play a significant role in the compound by nitration of urea in a mixture of 98 % nitric acid
chemical process industry and various geothermal and and oleum (20 % SO3), and then hydrolysis of nitrourea to give
industrial thermal engineering applications due to the nitramide in the presence of formaldehyde occurred through
importance of heat transfer in a multitude of processes.1 A formation of N-dimethylol nitramide since the subsequent
detailed knowledge of thermodynamic and transport properties neutralization with ammonia obtained the desired prod-
for aqueous electrolyte solutions is a necessary prerequisite for uct.8,11,15,16 During the neutralization process with ammonia,
the design and optimization of different processes and devices the aqueous phase includes moderate to high salt concen-
such as those used in refrigeration, in geothermal energy trations, and different portions of ammonium sulfate and
generating systems, in the treatment of wastewater, in chemical ammonium nitrate at temperatures range from (280.15 to
plants utilizing electrolyte solutions as a cooling bearer, and in 313.15) K. Thus, reliable data and modeling on the
the manufacturing of energetic materials.2−6 thermodynamic and transport properties of the binary and
Aqueous solutions of ammonium sulfate + ammonium ternary mixtures are needed over a wide range of concen-
nitrate are widely synthesized not only in the production of trations and temperatures for the simulation and optimization
ammonium sulfate-nitrate (ASN) fertilizers from effluent gases of the synthetic process.
of thermal power plants containing a significant amount of A literature survey revealed that only a few experimental data
sulfur dioxide and nitrogen oxides, but also in national defense sets are available for the thermal conductivities and densities of
industry and military engineering for the manufacturing of aqueous (NH4)2SO4 and NH4NO3 solutions. Wilfried et al.17
various energetic chemicals including 3,7-dinitro-1,3,5,7- measured the thermal conductivities of aqueous (NH4)2SO4
tetraazabicyclo[3,3,1]nonane,7,8 which is a key precursor to solutions in the range from 25 % to 44 % in weight fraction and
octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine, one of the most temperatures at (303.15, 323.15, and 343.15) K. In the article
powerful high explosives manufactured in bulk at present with of Chernen'kaya et al.,18 the thermal conductivities for aqueous
high density, high energy, low sensitivity, and excellent NH4NO3 solutions were presented at (313.15, 333.15, and
performance.9,10 Over the past century, various technologies
have been proposed to prepare 3,7-dinitro-1,3,5,7- Received: December 30, 2011
tetraazabicyclo[3,3,1]nonane.11−14 The aldehyde-amine con- Accepted: March 27, 2012
densation method has shown great advantages because of its Published: April 5, 2012

© 2012 American Chemical Society 1486 [Link]/10.1021/je201390r | J. Chem. Eng. Data 2012, 57, 1486−1491
Journal of Chemical & Engineering Data Article

Table 1. Experimental Thermal Conductivities of Binary Ammonium Sulfate + Water Solutions

T λ T λ T λ T λ
100w K W·m−1·K−1 100w K W·m−1·K−1 100w K W·m−1·K−1 100w K W·m−1·K−1
5.0 280.78 0.5646 10.0 280.76 0.5624 15.0 280.54 0.5560 20.0 280.56 0.5505
285.94 0.5743 285.92 0.5723 285.77 0.5650 285.76 0.5603
291.15 0.5861 290.98 0.5810 291.03 0.5764 290.93 0.5701
296.52 0.5974 296.32 0.5917 296.31 0.5859 296.24 0.5797
301.77 0.6078 301.62 0.6037 301.55 0.5957 301.38 0.5883
306.78 0.6184 306.85 0.6131 306.89 0.6049 307.13 0.5965
316.98 0.6345 317.20 0.6265 317.16 0.6185 317.15 0.6108
327.13 0.6431 327.33 0.6389 327.17 0.6289 327.19 0.6229
337.25 0.6534 337.42 0.6479 337.53 0.6382 337.51 0.6321
25.0 280.12 0.5450 30.0 280.06 0.5371 35.0 279.83 0.5254 40.0 280.09 0.5181
285.20 0.5527 285.25 0.5462 285.32 0.5358 285.70 0.5309
290.07 0.5598 290.46 0.5563 290.55 0.5468 290.79 0.5383
296.03 0.5703 295.88 0.5661 296.06 0.5575 296.14 0.5477
300.88 0.5811 301.14 0.5748 301.22 0.5652 301.34 0.5567
306.38 0.5902 306.43 0.5826 306.30 0.5731 306.57 0.5654
316.85 0.6019 316.59 0.5931 316.52 0.5884 316.80 0.5794
326.60 0.6147 326.74 0.6051 326.73 0.5973 326.94 0.5914
336.88 0.6254 337.13 0.6177 337.18 0.6087 337.07 0.6002

363.15) K over a wide range of concentrations. Besides, the recorded on an analytical balance (Mettler Toledo XS205 Dual
thermal conductivities of some aqueous phosphate and nitrate Range) to a precision of ± 0.1 mg. The liquid samples were
including NH4NO3 solutions at 333.15 K have been reported filtered by using syringes equipped with 0.40 μm membrane
by Peter and Horst.19 For densities of aqueous solutions of filters before density and thermal conductivity measurements
(NH4)2SO4 and NH4NO3, experimental data have been were recorded.
published over a wide range of concentrations and temper- Thermal Conductivity. The thermal conductivity measure-
atures in the literature by Sohnel and Novotny.20 However, ments were carried out in a transient hot-wire instrument,
experimental data of thermal conductivities and densities for named TC 3020 L, which was manufactured by Xi'an Xiatech
the industrially important ternary mixtures of (NH4)2SO4 + Electronic Technology Co., Ltd. The apparatus has been
NH4NO3 + H2O solutions have not been presented. For described fully in previous publications;21−24 thus only a brief
thermal conductivities of aqueous solutions of (NH4)2SO4 and introduction will be given here. The apparatus is equipped with
NH4NO3, the experimental data at lower temperature (280.15 two anodized wires made out of 25 μm diameter tantalum as
to 313.15 K) at which the final products are prepared are not hot wires, differing only in length, placed in the cells of the
available. In addition, the literature values17−19 are quite old instrument. An automatic Wheatstone-type electronic bridge is
and not easy to obtain. employed to measure the time evolution of temperature of
In this work, the experimental data of thermal conductivity λ tantalum wires during the application of a constant heat flux to
at temperatures from (278.15 to 333.15) K for binary aqueous the transient hot-wire instrument. The thermal cells of hot-wire
solutions of (NH4)2SO4 and NH4NO3 in the concentration apparatus is a jacket structure which is immersed completely in
range from 5 % to 40 % in weight fraction have been a thermostatic bath (Hui Chuang, model YHX-2008). The
determined at atmospheric pressure. Besides, the experimental temperature is obtained with a platinum resistance thermom-
data of thermal conductivity λ and density ρ at temperatures eter. The total uncertainty of the temperature for the thermal
from (278.15 to 333.15) K for ternary (NH4)2SO4 + NH4NO3 conductivity measurements is less than ± 20 mK. At each
+ H2O solutions have also been measured at atmospheric temperature, each measurement was replicated at least three
pressure. Both the temperature and the composition depend- times on each concentration. The apparatus was tested by
ence of these properties are analyzed and correlated. measurement on the thermal conductivity of ultrapure water

■ EXPERIMENTAL SECTION
Materials. The sample of ammonium sulfate with a
and toluene at temperatures from (278.15 to 333.15) K. The
results of thermal conductivity of ultrapure water and toluene
are in good agreement with the literatures.25,26 Accounting for
minimum purity in mass fraction of 99.0 % was provided by all of the random errors of measurement, the experimental
Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China). thermal conductivity data are estimated to have an expanded
Ammonium nitrate used in this work was purchased from uncertainty of better than 2.0 % with a coverage factor of k = 2,
Shanghai Crystal Pure Reagent Co., Ltd., China (Aladdin), at a approximately a 95 % confidence interval.
nominal mass purity specification of 99.5 %. All salts were Density. The density of all aqueous ammonium salt
placed and dried in a vacuum desiccator and used without solutions was measured at atmospheric pressure using a
further purification. The water used for the preparation of densimeter (Anton Paar DMA 4500). Standard water and air
aqueous solutions was supplied by a Yongjieda UPWS-T/b-A at temperatures ranging from (278.15 to 333.15) K were used
lab ultrapure water purification system. The resistivity of to calibrate the densimeter. The uncertainty in the density
available ultrapure water is ≥ 18.2 MΩ·cm. measurement is estimated to be ± 5·10−5 g·cm−3. The
Aqueous solutions were prepared from a known mass of salt temperature was controlled automatically by the densimeter
and water in a stoppered glass bottle. The masses were within ± 0.01 K. The cell of the densimeter was extensively
1487 [Link]/10.1021/je201390r | J. Chem. Eng. Data 2012, 57, 1486−1491
Journal of Chemical & Engineering Data Article

Table 2. Experimental Thermal Conductivities of Binary Ammonium Nitrate + Water Solutions

T λ T λ T λ T λ
100w K W·m−1·K−1 100w K W·m−1·K−1 100w K W·m−1·K−1 100w K W·m−1·K−1
5.0 280.24 0.5706 10.0 280.23 0.5682 15.0 280.28 0.5616 20.0 280.32 0.5589
285.51 0.5803 285.66 0.5786 285.69 0.5726 285.63 0.5696
290.30 0.5915 290.95 0.5905 290.72 0.5829 290.93 0.5782
296.20 0.6029 296.26 0.5996 295.88 0.5892 296.35 0.5874
301.45 0.6108 301.61 0.6080 301.53 0.5980 301.73 0.5973
306.70 0.6221 306.70 0.6181 306.74 0.6071 306.88 0.6058
316.96 0.6317 317.02 0.6295 316.91 0.6219 317.23 0.6199
327.13 0.6432 327.03 0.6415 327.14 0.6353 327.42 0.6330
337.25 0.6542 337.21 0.6520 337.19 0.6473 337.45 0.6451
25.0 280.20 0.5552 30.0 280.20 0.5517 35.0 280.27 0.5489 40.0 280.52 0.5455
285.81 0.5669 285.75 0.5629 285.87 0.5598 285.19 0.5559
290.96 0.5768 290.98 0.5742 291.15 0.5723 290.63 0.5671
296.41 0.5840 296.38 0.5819 296.55 0.5802 296.30 0.5765
301.67 0.5936 301.75 0.5924 301.85 0.5890 301.85 0.5852
306.88 0.6026 306.80 0.5998 307.01 0.5956 307.14 0.5937
317.08 0.6175 317.18 0.6120 317.30 0.6087 317.25 0.6051
327.45 0.6297 327.48 0.6256 327.67 0.6228 327.49 0.6172
337.59 0.6415 337.55 0.6381 337.51 0.6340 337.55 0.6284

Table 3. Fit Coefficients of Equation 1 for Binary Aqueous (NH4)2SO4 and NH4NO3 Solutions, Average Absolute Deviation,
and Standard Deviation
AAD SD
j i=0 i=1 i=2 % W·m−1·K−1
(NH4)2SO4 + H2O
0 5.4293·10−1 2.0077·10−2 −3.0163·10−1 0.16 0.0011
1 3.0422·10−3 −6.5464·10 −3
1.1420·10−2
2 −1.8880·10−5 6.5103·10−5 −1.1558·10−4
NH4NO3 + H2O
0 5.5768·10−1 −5.9244·10−2 −1.7545·10−2 0.18 0.0014
1 2.5817·10−3 −4.4115·10 −3
8.7606·10−3
2 −1.6553·10−5 7.4625·10−5 −1.5302·10−4

cleaned and dried before each of the liquids was introduced. increase with an increase of temperature and a decrease of the
The presence of bubbles in the liquid when placed in the mass fraction of ammonium salts in the mixture.
densimeter cell was not observed, and each measurement was Due to the lack of theoretical background of the dependency
replicated at least three times. of thermal conductivity for aqueous salt solutions on

■
temperature and composition, empirical and semiempirical
RESULTS AND DISCUSSION correlation equations and prediction techniques are used in the
literature. The results of the (λ, T, w) measurements for
Thermal Conductivities for Binary Aqueous (NH4)2SO4 (NH4)2SO4 + H2O and NH4NO3 + H2O solutions were
and NH4NO3 Solutions. Before the apparatus was used to represented by the equation
measure the thermal conductivity of each aqueous solution, the
2 2
performance of the apparatus was checked by toluene to ensure
the continuing good operation of the instrument. The values λ /W·m−1·K−1 = ∑ ∑ aijwit j
were reproducible within ± 0.5 %, and their agreement with the i=0 j=0 (1)
recommended values26 was within a maximum deviation of 1.08 where λ is the thermal conductivity of the solution
% and an average absolute deviation of 0.57 %, respectively. (W·m−1·K−1), t is the temperature in °C, and w represents
Measurements of the thermal conductivity for the binary the mass fraction of component in the binary mixture. At high
aqueous (NH4)2SO4 solutions were performed at atmospheric concentrations (w > 10 %), nonlinear terms for the
pressure (0.1 MPa) for eight compositions, namely, 5 %, 10 %, composition dependence in eq 1 have to be included. Equation
15 %, 20 %, 25 %, 30 %, 35 %, and 40 % in mass fraction at 1 describes the thermal conductivity of (NH4)2SO4 + H2O and
temperatures from (278.15 to 333.15) K. For binary aqueous NH4NO3 + H2O solutions with an accuracy that does not
NH4NO3 solutions, measurements were made at the same exceed their experimental uncertainty.
temperature and concentration ranges. Tables 1 and 2 show the The coefficients of eq 1 have been exclusively determined so
present experimental thermal conductivities determined for as to minimize the mean quadratic deviation of the fitted
(NH4)2SO4 + H2O and NH4NO3 + H2O, respectively. As experimental thermal conductivity data. The derived values of
shown in Tables 1 and 2, it is found that the thermal the fit coefficients aij in eq 1 for (NH4)2SO4 + H2O and
conductivities of aqueous (NH4)2SO4 and NH4NO3 solutions NH4NO3 + H2O solutions are given in Table 3. The average
1488 [Link]/10.1021/je201390r | J. Chem. Eng. Data 2012, 57, 1486−1491
Journal of Chemical & Engineering Data Article

Table 4. Experimental Thermal Conductivities of Ternary Ammonium Sulfate (1) + Ammonium Nitrate (2) + Water Solutions
100w1 = 5.0, 100w2 = 5.0 100w1 = 5.0, 100w2 = 10.0 100w1 = 5.0, 100w2 = 15.0 100w1 = 5.0, 100w2 = 20.0 100w1 = 10.0, 100w2 = 5.0
T λ T λ T λ T λ T λ
−1 −1 −1 −1 −1 −1 −1 −1
K W·m ·K K W·m ·K K W·m ·K K W·m ·K K W·m ·K−1−1

280.14 0.5654 279.96 0.5593 280.07 0.5531 279.87 0.5498 279.90 0.5519
285.48 0.5752 285.39 0.5708 285.40 0.5634 285.45 0.5619 285.20 0.5614
290.81 0.5878 290.56 0.5811 290.68 0.5739 290.70 0.5726 290.55 0.5735
296.10 0.5946 296.09 0.5925 295.98 0.5845 295.93 0.5802 295.97 0.5838
301.56 0.6032 301.41 0.6015 301.32 0.5941 301.53 0.5910 301.10 0.5933
306.75 0.6140 306.63 0.6111 306.41 0.6026 306.59 0.6004 306.35 0.6021
316.95 0.6243 316.79 0.6203 316.89 0.6149 316.69 0.6121 316.44 0.6147
327.23 0.6343 327.21 0.6292 326.92 0.6256 326.92 0.6214 327.04 0.6253
337.19 0.6428 337.27 0.6394 337.15 0.6358 337.14 0.6311 337.03 0.6353
100w1 = 15.0, 100w2 = 5.0 100w1 = 20.0, 100w2 = 5.0 100w1 = 10.0, 100w2 = 10.0 100w1 = 20.0, 100w2 = 20.0
T λ T λ T λ T λ
−1 −1 −1 −1 −1 −1
K W·m ·K K W·m ·K K W·m ·K K W·m ·K−1
−1

279.82 0.5447 280.13 0.5432 280.26 0.5479 280.52 0.5330

285.56 0.5571 285.20 0.5512 285.44 0.5594 285.92 0.5432
290.42 0.5672 290.68 0.5629 290.59 0.5702 291.09 0.5540
296.07 0.5795 296.02 0.5729 296.17 0.5812 296.43 0.5662
301.41 0.5895 301.25 0.5809 301.29 0.5909 301.79 0.5754
306.46 0.5975 306.42 0.5900 306.36 0.5989 307.10 0.5821
316.77 0.6106 316.83 0.6028 316.77 0.6121 317.39 0.5946
327.21 0.6198 327.10 0.6138 327.00 0.6227 327.50 0.6052
337.11 0.6286 337.05 0.6232 337.41 0.6312 337.36 0.6140

absolute deviation (AAD) and standard deviation (SD) of the where λ is the thermal conductivity of the solution
fits are provided in Table 3 as well. It can be seen that the (W·m−1·K−1), λH2O is the thermal conductivity of pure water
average absolute deviations of experimental data of binary (W·m−1·K−1), wi is the concentration of ith component in mass
aqueous (NH4)2SO4 and NH4NO3 solutions from those fraction in the multicomponent solution, k is the number of
calculated values by eq 1 are 0.16 % and 0.18 %, and the
solution components, and βi are coefficients found by
obtained standard deviations are 0.0011 W·m−1·K−1 and 0.0014
processing by methods of regression analysis of the
W·m−1·K−1, respectively. This is indicative of a good fit to the
experimental data. In this work, the subscript 1 and 2 represent
experimental data.
Thermal Conductivities for Ternary (NH4)2SO4 + (NH4)2SO4 and NH4NO3, respectively. The eq 2 is valid in the
NH4NO3 + H2O Solutions. For the ternary (NH4)2SO4 + temperature range from (273 to 473) K and at concentrations
NH4NO3 + H2O solutions, measurements of the thermal up to 50 % in mass fraction.
conductivity were performed at atmospheric pressure (0.1 The thermal conductivity of pure water on the saturation line
MPa) for nine different portions of ammonium sulfate and at temperatures from (0 to 135) °C is approximated with a
ammonium nitrate at temperatures from (278.15 to 333.15) K. root-mean-square deviation (rmsd) = 2.9·10−4 W·m−1·K−1 and
The values of thermal conductivity as a function of temperature average absolute deviation (AAD) = 0.03 % with the
for ternary mixtures of different compositions for the polynomial7
(NH4)2SO4 + NH4NO3 + H2O system are listed in Table 4.
From Table 4, it is found that the thermal conductivities of λ H2O = 10−3(A 0 + A1T + A 2 T1.5 + A3T 2.5 + A4 T 3) (3)
* * * *
aqueous solutions of (NH4)2SO4 + NH4NO3 decrease with an
increase of weight fraction of (NH4)2SO4 or NH4NO3 in the Table 5. Fit Coefficients of eq 2 for (NH4)2SO4 + NH4NO3 +
mixture and a decrease of temperature. In addition, the results H2O, Average Absolute Deviation, and Standard Deviation
show that the replacement of NH4NO3 by (NH4)2SO4 at the
AAD SD
same weight fraction lowers the thermal conductivity of the
solution. This may be attributed to more ammonium ion β1 β2 % W·m−1·K−1
−3 −3
groups contained in (NH4)2SO4 than in NH4NO3 solutions. (NH4)2SO4 + −1.2693·10 −2.3133·10 0.34 0.0025
NH4NO3 +
For ternary aqueous salt solutions, the experimental data of H2O
thermal conductivity can be described by the Aseyev equation27
in terms of the mass fraction of components in the form
where A0 = 560.971778, A1 = 178.153112, A2 = 59.731618, A3
k = −245.008302, A4 = 124.873313, T* = 0.01t, and t is the
λ = λ H2O(1 + 100 ∑ βiwi) temperature in °C.
i=1 The fit coefficients β1 and β2 determined in eq 2 for aqueous
solutions of (NH4)2SO4 + NH4NO3 are shown in Table 5, as
= λ H2O(1 + 100β1w1 + 100β2w2) (2) well as the values of the average absolute deviation (AAD) and
1489 [Link]/10.1021/je201390r | J. Chem. Eng. Data 2012, 57, 1486−1491
Journal of Chemical & Engineering Data Article

Table 6. Experimental and Predictive Densities of Aqueous Ammonium Sulfate (1) + Ammonium Nitrate (2) Solutions from
(278.15 to 333.15) K
ρ/g·cm−3
100w1 = 5.0, 100w2 = 5.0 100w1 = 5.0, 100w2 = 10.0 100w1 = 5.0, 100w2 = 15.0 100w1 = 5.0, 100w2 = 20.0 100w1 = 10.0, 100w2 = 5.0
T/K exp calcda exp calcda exp calcda exp calcda exp calcda
278.15 1.05206 1.05182 1.07394 1.07381 1.09589 1.09656 1.11914 1.12009 1.08174 1.08250
283.15 1.05090 1.05092 1.07241 1.07269 1.09375 1.09521 1.11702 1.11851 1.08030 1.08130
288.15 1.04956 1.04980 1.07073 1.07133 1.09133 1.09362 1.11480 1.11668 1.07873 1.07993
293.15 1.04803 1.04847 1.06891 1.06975 1.08888 1.09179 1.11250 1.11462 1.07702 1.07839
298.15 1.04635 1.04695 1.06697 1.06796 1.08630 1.08975 1.11012 1.11234 1.07519 1.07670
303.15 1.04449 1.04523 1.06491 1.06597 1.08370 1.08751 1.10767 1.10985 1.07324 1.07484
313.15 1.04043 1.04124 1.06044 1.06144 1.08008 1.08247 1.10255 1.10430 1.06901 1.07067
323.15 1.03544 1.03655 1.05552 1.05622 1.07471 1.07674 1.09715 1.09809 1.06430 1.06593
333.15 1.02992 1.03121 1.04977 1.05039 1.07005 1.07042 1.09131 1.09127 1.05816 1.06063
100w1 = 15.0, 100w2 = 5.0 100w1 = 20.0, 100w2 = 5.0 100w1 = 10.0, 100w2 = 10.0 100w1 = 20.0, 100w2 = 20.0 AAD SD
T/K exp calcda exp calcda exp calcda exp calcda % g·cm−3
278.15 1.11133 1.11269 1.14081 1.14239 1.10370 1.10482 1.20961 1.21297 0.099 0.00145
283.15 1.10969 1.11125 1.13902 1.14077 1.10199 1.10342 1.20722 1.21089 0.124 0.00171
288.15 1.10795 1.10968 1.13714 1.13904 1.10014 1.10183 1.20480 1.20867 0.152 0.00197
293.15 1.10610 1.10797 1.13519 1.13720 1.09817 1.10006 1.20234 1.20629 0.172 0.00217
298.15 1.10416 1.10613 1.13317 1.13525 1.09611 1.09812 1.19983 1.20378 0.187 0.00232
303.15 1.10214 1.10415 1.13106 1.13319 1.09395 1.09602 1.19729 1.20113 0.194 0.00238
313.15 1.09781 1.09983 1.12667 1.12876 1.08935 1.09135 1.19210 1.19548 0.172 0.00203
323.15 1.09314 1.09503 1.12206 1.12392 1.08434 1.08611 1.18679 1.18937 0.147 0.00171
333.15 1.08790 1.08977 1.11718 1.11869 1.07884 1.08034 1.18137 1.18286 0.114 0.00143
a
Calculated by eq 4.

standard deviation (SD). The results of AAD and SD are ρNH4NO3(IT), are calculated from the equations and parameters
inferior to 0.34 % and 0.0025 W·m−1·K−1, respectively. These provided by Tans30 and Sohnel and Novotny,20 respectively.
results show that eq 2 can be satisfactorily used for the If the ternary system of (NH4)2SO4 + NH4NO3 + H2O
prediction of ternary thermal conductivities for the title system.
follows Young's rule, the mixing in terms of density can be
Densities for (NH4)2SO4 + NH4NO3 + H2O Solutions.
considered as ideal. In comparison with the experimental
Experimental data of the densities of ternary mixtures for
(NH4)2SO4 + NH4NO3 + H2O at T= (278.15 to 333.15) K are densities, the calculated results by eq 4 are shown in Table 6,
presented in Table 6. In the industrial neutralization stage, combined with the values of AAD and SD. It can be seen that
different portions of ammonium sulfate and ammonium nitrate this ideal mixing model results in maximum average absolute
salts exist in aqueous phase. The densities measured in this deviation between experimental and calculated densities within
work will be beneficial for the research of heat transfer during 0.194 %. The obtained root-mean-square deviation between
neutralization, the simulation and optimization of the synthetic experimental and calculated densities is inferior to 0.00238
process, and the design of reaction equipment. g·cm−3. The results indicate that Young's rule is suitable and
The simple additivity rule has been tested for its ability in the reliable to extrapolate densities of the ternary aqueous
prediction of properties of the studied system. The widely used (NH4)2SO4 + NH4NO3 system. Similar results have been
Young's rule28,29 can be expressed as obtained for other systems, such as the aqueous H2SO4 +
I(NH4)2 SO4 INH4NO3 FeSO431 and NaOH + NaAl(OH)429,32,33 solutions.

■
ρ(IT) = ρ(NH ) SO (IT) + ρNH NO (IT)
IT 4 2 4 IT 4 3
CONCLUSIONS
(4)
Measurements of the thermal conductivities of the energetic
with ionic strength in molality I defined as
industrially important (NH4)2SO4 + H2O, NH4NO3 + H2O,
1 and (NH4)2SO4 + NH4NO3 + H2O systems were performed in
I= ∑ mizi 2 a transient hot-wire instrument over a wide range of
2 i (5)
concentrations at temperatures range from (278.15 to
where mi is the molality of ion i in moles per kilogram of pure 333.15) K. The densities of (NH4)2SO4 + NH4NO3 + H2O
solvent H2O, zi represents the ion charges, ρ(IT) is the density solutions were presented over temperatures range from (278.15
of the ternary aqueous solutions under total ionic strength, IT, to 333.15) K for nine different compositions as well. The
in molality units, I(NH4)2SO4 and INH4NO3 are the ionic strength thermal conductivities were found to decrease with an increase
contributions of (NH4)2SO4 and NH4NO3 in solution, of mass fractions of ammonium salts in the mixture and a
respectively, and ρ(NH4)2SO4(IT) and ρNH4NO3(IT) are the decrease of temperature. The experimental data were correlated
densities of the binary solutions at the total ionic strength, IT, as a function of temperature and composition using empirical
respectively. In the present case, the densities of aqueous equations, and a good agreement was found with correlation
(NH4) 2SO4 and NH4NO3 solutions, ρ(NH4)2SO4(IT) and ones.
1490 [Link]/10.1021/je201390r | J. Chem. Eng. Data 2012, 57, 1486−1491
Journal of Chemical & Engineering Data

■
Article

AUTHOR INFORMATION (17) Wilfried, S.; Hartmut, M.; Christina, M. Specific Heat and
Thermal Conductivity of the Ammonium Sulfate-Water System. Chem.
Corresponding Author Tech. 1982, 34, 31−32 (in German).
*Fax: +86 571 87951742. Tel.: +86 571 87952709. E-mail: (18) Chernen'kaya, E. I.; Vernigora, G. A.; Bratash, E. G.;
chhezju@[Link]. Pavlyuchenko, E. N. Thermal Properties of Solutions of Ammonium
and Sodium Nitrates and Their Mixtures in Ammonium Carbonate
Funding
Solutions at Different Temperatures; State Public Scientific Techno-
Financial support from the National Natural Science logical Library (SPSTL): Russia, 1982; 1148 khp-D82, p 11 (in
Foundation of People's Republic of China (Project Nos. Russian).
20876131, 21176206) and the Project of Zhejiang Key (19) Peter, K.; Horst, S. The Behavior of the Thermal Conductivity
Scientific and Technological Innovation Team (Project No. of Some Phosphate and Nitrate Solutions. Chem. Tech. 1977, 29, 552−
2009R50002) is gratefully acknowledged. 554 (in German).
(20) Sohnel, O.; Novotny, P. Densities of Aqueous Solutions of
Notes Inorganic Substances; Elsevier: Amsterdam, 1985.
The authors declare no competing financial interest. (21) Wu, J. T.; Zheng, H. F.; Qian, X. H.; Li, X. J.; Assael, M. J.

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