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Article

Powders Synthesized from Calcium Carbonate and Water Solutions of Potassium Hydrosulfate of Various Concentrations

by
Tatiana V. Safronova
1,2,*,
Peter D. Laptin
2,
Alexandra I. Zybina
2,
Xiaoling Liao
3,
Tatiana B. Shatalova
1,2,
Olga V. Boytsova
1,2,
Dinara R. Khayrutdinova
4,
Marat M. Akhmedov
5,
Zichen Xu
3,
Irina V. Kolesnik
1,2,
Maksim R. Kaimonov
1,2,
Olga T. Gavlina
1 and
Muslim R. Akhmedov
6
1
Department of Chemistry, Lomonosov Moscow State University, Building, 3, Leninskie Gory, 1, 119991 Moscow, Russia
2
Department of Materials Science, Lomonosov Moscow State University, Building, 73, Leninskie Gory, 1, 119991 Moscow, Russia
3
Chongqing Key Laboratory of Nanomaterials and Devices, Chongqing University of Science and Technology (CQUST), Chongqing 401331, China
4
Baykov Metallurgy and Materials Institute, Leninskii Prosp., 49, 119334 Moscow, Russia
5
Department of Chemistry and Technology of Polymer Materials and Nanocomposites, Kosygin Russian State University, Malaya Kaluzhskaya 1, 119071 Moscow, Russia
6
Department of Space Research, Lomonosov Moscow State University, Building, 52, Leninskie Gory, 1, 119991 Moscow, Russia
*
Author to whom correspondence should be addressed.
Compounds 2024, 4(4), 650-663; https://doi.org/10.3390/compounds4040039
Submission received: 16 August 2024 / Revised: 22 September 2024 / Accepted: 8 October 2024 / Published: 14 October 2024
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Abstract

:
Powders with a phase composition including syngenite (K2Ca(SO4)2·H2O) and/or calcium sulfate dihydrate (gypsum, CaSO4·2H2O) were synthesized from the powder of calcium carbonate (CaCO3) and water solutions of potassium hydrosulfate (KHSO4) of various concentrations (0.5 M, 1 M, and 2 M). A molar ratio of starting salts, KHSO4/CaCO3 = 2, was used to provide the formation of syngenite (K2Ca(SO4)2·H2O). But when using a 0.5 M water solution of potassium hydrosulfate (KHSO4), the phase composition of the synthesized powder was presented by calcium sulfate dihydrate (gypsum, CaSO4·2H2O). When using 1 M and 2 M water solutions of potassium hydrosulfate (KHSO4), the syngenite (K2Ca(SO4)2·H2O) was found as the predominant phase in synthesized powders. According to estimations made from thermal analysis data, powders synthesized using 1.0 M and 2.0 M water solutions of potassium hydrosulfate (KHSO4) contained no more than 7.9 and 1.9 mass % of calcium sulfate dihydrate (gypsum, CaSO4·2H2O), respectively. The phase composition of products isolated from mother liquors via water evaporation consisted of syngenite (K2Ca(SO4)2·H2O) and potassium sulfate (arcanite, K2SO4). Synthesized powders can be used in preparation of biocompatible bioresorbable materials with phase compositions in the K2O-CaO-SO3-H2O system; as matrix of thermo- or photo-luminescent materials; as components reducing the setting time and increasing the strength of sulfate cements; in the fertilizing industry; and also as components of Martian regolith simulants.

1. Introduction

The following mineral salts belong to the K2O-CaO-SO3-H2O system: potassium sulfate (K2SO4); potassium pyrosulfate K2S2O7; potassium hydrosulfates KHSO4, K3H(SO4)2, K9H7(SO4)8·H2O; calcium sulfate hemihydrate (CaSO4·0.5H2O); calcium sulfate dihydrate (CaSO4·2H2O); syngenite (K2Ca(SO4)2·H2O); and gorgeyite (K2SO4·5CaSO4·H2O) [1,2]. These minerals existing in different subsystems of the K2O-CaO-SO3-H2O system [3,4,5,6,7], especially syngenite (K2Ca(SO4)2·H2O), are important for several applications, among which are the fertilizer industry [8,9], production of construction materials [10,11,12], inorganic materials with specific properties [13], creation of bioresorbable and biocompatible materials [14,15], and creation of Martian regolith simulants [16,17,18].
Syngenite (K2Ca(SO4)2·H2O) can be synthesized using several different techniques: by crystallization at room temperature (20 °C and ~50% relative humidity) during evaporation of a solution containing calcium sulfate (CaSO4) and potassium sulfate (K2SO4) in a molar ratio of 1:50 [19]; via an interaction of hot solutions (80 °C, 100 °C) of calcium nitrate (Ca(NO3)2) and potassium sulfate (K2SO4) [20]; via an interaction of calcium sulfate (CaSO4) and potassium chloride (KCl) in a water medium [21]; or under mechanical activation in a planetary mill from a powder mixture of potassium sulfate (K2SO4) and calcium sulfate dihydrate (CaSO4·2H2O) [17,22]. The synthesis of inorganic powders under mechanical activation in a planetary mill from a powder mixture of starting components has obvious advantages and gives an opportunity to provide a fine powder with low particle dimensions and morphology that cannot be reached using the precipitation method [23]. On the other hand, synthesis from water solutions of different concentrations can be used as an approach that makes it possible to influence particles’ morphology and dimensions [24,25].
Syngenite (K2Ca(SO4)2·H2O), as a solid cement stone, was synthesized by adding of water to a powder mixture consisting of calciolangbeinite (K2Ca2(SO4)3) and potassium sulfate (K2SO4) [15] or to a powder mixture of calcium sulfate (CaSO4) and potassium sulfate (K2SO4) [26].
All syntheses of syngenite (K2Ca(SO4)2·H2O) presented in the scientific literature have had to create conditions when H2O and the ions of K+, Ca2+, and SO42- are present in the reaction zone in a given molar ratio. In the case where K2SO4 and CaSO4 or CaSO4·2H2O are used, there is no problem with forming reaction by-products. But in the case where calcium nitrate (Ca(NO3)2) is used [20], potassium chloride (KCl) [21] or starting salts of other acids than sulfuric (H2SO4) reaction by-products will form. These reaction by-products adsorbed on the surface of the particles or occluded from the mother liquor in the filtrated precipitate will inevitably affect the properties of the synthesized powder. For this reason, the stage of washing the synthesized powder is very often a necessary stage in fine-powder preparation. If powders are synthesized for the subsequent production of ceramics, reaction by-products can be divided for two big groups according to their response to heating: removable and non-removable when heated [27]. Calcium carbonate (CaCO3), during interactions with water solutions of acid salt such as KHSO4, can be treated as ideal provider of Ca2+, forming by-products with the characteristic property of being “removable during synthesis via co-precipitation”.
This investigation aimed to develop a robust method of synthesis of syngenite (K2Ca(SO4)2·H2O) powder not containing reaction by-products that need to be removed via the washing of the precipitate. Chemical interactions of calcium carbonate (CaCO3) powder and water solutions of potassium hydrosulfate (KHSO4) will lead to the formation of both the target precipitate and an unstable reaction by-product, H2CO3, which can decompose during synthesis and form H2O and CO2. The release of gaseous CO2 from the reaction zone will be an expected sign of a chemical reaction.

2. Materials and Methods

2.1. Materials

Powders of CaCO3 (GOST 4530-76, Rushim, Moscow, Russia) and KHSO4 (GOST 4223-75, Rushim, Moscow, Russia) were used for the syntheses of powders.

2.2. Syntheses of Powders

The quantities of the reagents were calculated according to Reaction (1).
2KHSO4 + CaCO3 → K2Ca(SO4)2·H2O + CO2,
The molar ratio of the starting salts in each synthesis, KHSO4/CaCO3, was equal to 2 and taken according to Reaction (1) to produce syngenite (K2Ca(SO4)2·H2O). Table 1 contains the labeling and synthesis conditions of the powders under investigation. A total of 400 mL of 0.5 M, 1.0 M, and 2.0 M KHSO4 water solutions were prepared and used in the experiment. Calculated quantities of CaCO3 powder were added to each solution. Suspensions were kept on a magnetic stirrer for 3 h until the release of gas stopped. The conditions of the powders’ synthesis and labeling of samples under investigation are presented in Table 1. All the syntheses were carried out at room temperature (about 20–25 °C).
The precipitates were separated from the mother liquors using vacuum filtration, before being placed on plastic trays and left to dry for a week. Then, the powders were collected, weighted, crushed with an agate mortar, and passed through a 200 μm mesh sieve. The transparent mother liquors were collected, and the products dissolved in them were extracted from solutions via crystallization due to the evaporation of water after being kept at 40 °C. The substances extracted from the mother liquors that were separated from the precipitates during the syntheses of the powders SP0.5M, SP1.0M, and SP2.0M were labeled as Ex-SP0.5M, Ex-SP1.0M, and Ex-SP2.0M, respectively.

2.3. Methods of Analysis

The phase composition of the powders obtained after the synthesis and drying was determined by X-ray powder diffraction (XRD) analysis using a Tongda TD-3700 diffractometer (Dandong Tongda Science & Technology Co., Ltd., Tongda, Dandong, China) with working parameters 40 kV, 30 mA, CuKα radiation, linear PSD detector, in Bragg–Brentano geometry with an angle interval of 2Ѳ from 5° to 70° (step 2Ѳ—0.02°). A phase analysis was performed using the ICDD PDF2 database [28] and “Match!” software (version 3.15 https://www.crystalimpact.com/, accessed on 15 August 2024).
Infrared spectra were collected in the wavenumber range of 500–4000 cm−1 using a Spectrum Three FTIR spectrometer (Perkin Elmer, Waltham, MA, USA) in attenuated total reflectance mode with a Universal ATR accessory (diamond/KRS-5 crystal). The bands in the spectra were attributed on the basis of the literature [29].
The bulk densities of the samples were determined using a mass of 1.0 cm3 of the synthesized powders after drying, crushing in the agate mortar, and passing through the 200 μm mesh sieve.
Scanning electron microscopy (SEM) images of the synthesized powders were characterized using Tescan Vega II (Tescan, Brno, Czech Republic) at accelerating voltages from 1 to 20 kV in secondary electron imaging mode (SE2 detector). Gold layers (≤10 nm in thickness) were applied on the surface of the powder samples (Quorum Technologies spraying plant, Q150T ES, Great Britain, London, UK).
A thermal analysis (TA), including thermogravimetry (TG) and differential thermal analysis (DTA), was performed using an NETZSCH STA 449 F3 Jupiter thermal analyzer (NETZSCH, Selb, Germany) while heating in air (10 °C/min, 40–1000 °C); the specimen mass was at least 10 mg. The gas-phase composition was monitored by a Netzsch QMS 403 Quadro quadrupole mass spectrometer (NETZSCH, Selb, Germany) coupled with a NETZSCH STA 449 F3 Jupiter thermal analyzer (NETZSCH, Selb, Germany). The mass spectra were recorded for the following m/Z values: 18 (H2O); 64 (SO2); and 44 (CO2).

3. Results and Discussion

According to the XRD data of the synthesized powders shown in Figure 1, the phase composition of the SP0.5M powder included CaSO4·2H2O (PDF card 33-313). The phase composition of the SP1.0M and SP2.0M powders consisted mainly of syngenite (K2Ca(SO4)2·H2O) (PDF card # 28-739) and included trace amounts of gypsum (CaSO4·2H2O). The peaks of CaSO4·2H2O in the XRD graph of the SP2.0M powder in Figure 1 are almost unrecognizable without magnification. There are no traces of starting salts presented in the synthesized powders. The possibility of the co-existence of syngenite (K2Ca(SO4)2·H2O) and gypsum (CaSO4·2H2O) was earlier shown during the investigation of solid–liquid equilibria of the quaternary water–salt system K+, Mg2+, Ca2+//SO42––H2O at 323.2 K [30].
The phase composition determined using Match software and mass of synthesized powders are summarized in Table 2.
The calcium sulfate dihydrate (CaSO4·2H2O) present in the synthesized powder can be obtained using Reaction (2):
2KHSO4 + CaCO3 + H2O → CaSO4·2H2O + CO2 +K2SO4,
Using “Match!” software, quantities of gypsum (CaSO4·2H2O) were determined as 7.1 and 1.3 mass % in the powders SP1.0M and SP2.0M, respectively. One can see that the syngenite (K2Ca(SO4)2·H2O) content in the synthesized powders depended on the conditions of the synthesis and increased with increasing of concentrations of potassium hydrosulfate (KHSO4) solutions (Table 2).
Camera-taken photos of the products extracted via evaporation from the transparent mother liquors are shown in Figure 2. There is no noticeable difference in the appearance of products collected from mother liquors except the obviously larger quantity of Ex-SP0.5M. All extracted products consisted of white transparent elongated crystals.
According to the XRD data, the phase composition of the products extracted via evaporation from the mother liquors (Figure 3) consisted of potassium sulfate (arcanite, K2SO4) (PDF card # 5-613) and syngenite (K2Ca(SO4)2·H2O).
K2SO4 was present in the extracted products due to Reaction (2) having taken place, and K2Ca(SO4)2·H2O (Ksp (K2Ca(SO4)2·H2O) = 1.88 × 10−4) had formed due to presence of Ca2+, K+, and SO42- ions in the mother liquors during water evaporation. The phase composition determined using “Match!” software and the mass of the extracted products are shown in Table 3. The higher the concentration of water solutions of potassium hydrosulfate (KHSO4), the lower the mass of products extracted from the mother liquors and the amount of potassium sulfate (K2SO4) in the extracted products are.
The FTIR spectroscopy data (Figure 4) agree with the data of the XRD powder diffraction. In the spectrum of SP0.5, only the bands of gypsum are clearly seen (stretching OH vibrations at 3600–3100 cm−1, stretching OH vibrations at 3600–3100 cm−1, deformation OH vibrations at 1752–1525 cm−1, stretching SO4 vibrations at 1280–880 cm−1, deformation SO4 vibrations below 710 cm−1), which can be attributed to gypsum (CaSO4·2H2O) structures, like in our previous work [31]. In the spectra of the SP1.0M and SP2.0M powders, the bands in the same regions are clearly seen, as well as additional bands (1190 cm−1, 750 cm−1), which can be attributed to syngenite (K2Ca(SO4)2·H2O) [32]. The FTIR spectroscopy data for starting salts are in agreement with the data collected for calcite (CaCO3) [33] and KHSO4 [34,35] in investigations published before.
In Figure 5, the FTIR spectra of the products extracted from the mother liquors, which were separated from the precipitates, after water evaporation (Ex-SP0.5M, Ex-SP1.0M, and Ex-SP2.0M), and the spectrum of KHSO4 are presented.
In the spectra of products extracted from mother liquors, which were separated from precipitates, after water evaporation (Ex-SP0.5M, Ex-SP1.0M, and Ex-SP2.0M), the bands of sulfate groups (stretching SO4 vibrations at 1280–880 cm−1 and deformation SO4 vibrations below 710 cm−1) can be observed, whereas the OH bands are very weak. The shape of the bands differs from ones observed for gypsum. In this case, the bands should be attributed to potassium sulfate (K2SO4) [36]. The shoulder at 1190 cm−1 and the band at 750 cm−1, which were earlier attributed to syngenite (K2Ca(SO4)2·H2O), are present as well. Slight bands similar to those of KHSO4 can be recognized in the spectrum of Ex-SP2.0M. Nevertheless, it is possible to conclude that the samples Ex-SP0.5M, Ex-SP1.0M, and Ex-SP2.0M consist of potassium sulfate (K2SO4) and syngenite (K2Ca(SO4)2·H2O). And this conclusion concerns the results of XRD diffraction studies.
SEM images of the synthesized powders are presented in Figure 6.
The powder SP0.5M, with a phase composition presented by gypsum (CaSO4·2H2O), consisted of particles having elongated prismatic morphology, which is typical for this mineral, being 5–20 μm long and 2–4 μm wide. The powders SP1.0M and SP2.0M, with phase compositions presented preferably by syngenite (K2Ca(SO4)2·H2O), consisted of particles having plate morphology, which is typical for this mineral [15,37], with dimensions of 4–20 μm in length and 0.5–2 μm thick. It should be noted that syngenite (K2Ca(SO4)2·H2O) was earlier found to form needle-shaped [37,38], elongated crystals [39,40] or even form a “felt-like structure consisting of long, rail-like crystals” with a length of 10–20 μm in a paste based on CaSO4·2H2O and K2SO4 [41].
Plate or elongated morphology of particles and their small dimensions can be taken as a reason for the low bulk density of the synthesized powders, which was 0.85, 0.80, and 0.86 g/cm3 for the powders SP0.5M, SP1.0M, and SP2.0M, respectively (Figure 7). Taking into account the calculated density of gypsum (CaSO4·2H2O) (2.310 g/cm3, # 96-901-7314, “Match!”) and syngenite (K2Ca(SO4)2·H2O) (2.575 g/cm3, # 96-900-8129, “Match!”) the relative densities of the powders SP0.5M, SP1.0M, and SP2.0M were 37, 34, and 33%, respectively.
The thermal analysis data of the synthesized powders are shown in Figure 8.
The total mass loss of the SP0.5M powder at 1000 °C was 20.7%, and this value is in good agreement with the theoretical mass loss of pure gypsum (CaSO4·2H2O) (20.9%) calculated using Equation (3) [6]:
CaSO4·2H2O → CaSO4 + 2H2O
The total mass loss of the powders SP1.0M and SP2.0M were 6.7% and 5.7% at 1000 °C, respectively. No traces of SO2 (m/Z = 64) or CO2 (m/Z = 44) were recorded in the released gas phase during heating. The mass spectra for H2O (m/Z = 18) confirmed that the mass loss of all the synthesized powders during heating were due to H2O evacuation (Figure 9). H2O left the SP0.5M powder in the 90–200 interval with its maximum at 144 °C (Figure 8b and Figure 9). The mass loss of SP1.0M and SP2.0M powders went through two stages. The first stage for the powder SP1.0M was in the interval 106–155 °C with its maximum at 134 °C, and that for SP2.0M was in the interval 99–153 °C with its maximum at 128 °C. This mass loss for the powders SP1.0M and SP2.0M could also be due to the decomposition of the smallest quantity of gypsum (CaSO4·2H2O), which were found by means of XRD (Figure 1, Table 2). The mass loss at the first stage gave us an opportunity to estimate the quantity of gypsum (CaSO4·2H2O) as 7.9 and 1.9 % in the powders SP1.0M and SP2.0M, respectively. It is worth noticing that the estimations of the quantity of gypsum (CaSO4·2H2O) made considering TA data were close to the estimations made by using “Match!” software (Table 2). The second stage of mass loss of SP1.0M and SP2.0M was in the interval 230–310 °C with its maximum at 276 °C (Figure 8b and Figure 9). This interval corresponds to the intervals 200–300 °C [37] and 250–300 °C [42] determined previously during investigations of the thermal decomposition of syngenite. The investigation of the thermal decomposition of syngenite (K2Ca(SO4)2·H2O) in the isothermal conditions carried out earlier was in the temperature interval of 230–280 °C [43]. Considering the XRD data, Reaction (4) could reflect the process of the thermal decomposition of syngenite (K2Ca(SO4)2·H2O) in this interval.
K2Ca(SO4)2·H2O → K2Ca(SO4)2 + 2H2O
One can see the endothermal effect for SP05M at the interval 100–230 °C with its a minimum at 147 °C, which was due to the thermal dehydration of gypsum (CaSO4·2H2O) (Figure 10).
There are five endothermal effects present at the DSC curves of the powders SP1.0M and SP2.0M. The endothermal effect in the intervals 90–180 °C with its minimum at 130 °C (SP1.0M) and 90–160 °C with its minimum at 126 °C (SP2.0M) correspond to the thermal decomposition of gypsum (CaSO4·2H2O) presented in these powders (Reaction (3)). The endothermal effect in the interval 240–310 °C with its minimum at 280 °C for the powders SP1.0M and SP2.0M was due to the dehydration of sygenite (K2Ca(SO4)2·H2O) (Reaction (4)). The three endothermal effects for the powders SP1.0M and SP2.0M occur at 557, 877, and 950 °C. According to the binary system K2SO4-CaSO4, the phases of potassium sulfate (K2SO4), calcium sulfate (CaSO4), and calciolangbeinite (K2Ca2(SO4)3) exist in this system before 500 °C [44]. Reactions (5) and (6) can reflect the formation of all these minerals [37,45]:
3K2Ca(SO4)2 → K2Ca2(SO4)3 + 2K2SO4 + CaSO4
2K2Ca(SO4)2 → K2Ca2(SO4)3 + K2SO4
There are the transformation of β-K2SO4 to α-K2SO4 at 550 °C, the formation of eutectic melt at 875 °C, and the transformation of β-K2Ca2(SO4)3 to α-K2Ca2(SO4)3 at 940 °C in the binary system K2SO4-CaSO4 [44,46]. The endothermal effects seen from the experimental curves for the SP1.0M and SP2.0M powders are in obvious agreement with the possible events according to existing information about the binary system K2SO4-CaSO4.

4. Conclusions

A new method for powder synthesis with phase composition represented preferably by syngenite (K2Ca(SO4)2·H2O) from 1M and 2M water solutions of potassium hydrosulfate (KHSO4) and powder of calcium carbonate (CaCO3) as starting reagents has been proposed. By using TA and XRD data, it was found that content of calcium sulfate dihydrate (gypsum, CaSO4·2H2O) in powders synthesized from 1M and 2M water solutions of potassium hydrosulfate (KHSO4) were not higher than 7.9 and 1.9%, respectively. According to SEM images made in present investigation, these powders consisted of particles with plate morphology. When using a 0.5M water solution of potassium hydrosulfate (KHSO4), powder of calcium sulfate dihydrate (gypsum, CaSO4·2H2O) consisting of particles with elongated prismatic morphology was obtained. The phase compositions of the extracted products isolated from the mother liquors collected after all the syntheses were represented by potassium sulfate (K2SO4) and syngenite (K2Ca(SO4)2·H2O). Synthesized powders including those precipitated and extracted from mother liquors can be used in the preparation of biocompatible bioresorbable materials with a phase composition in the K2O-CaO-SO3-H2O system, as matrixes of luminescent materials, as components reducing the setting time and increasing the strength of sulfate cements, in the fertilizing industry, and also as components of Martian regolith simulants.

Author Contributions

Conceptualization, T.V.S.; methodology, T.V.S.; investigation, T.V.S., P.D.L., A.I.Z., X.L., T.B.S., O.V.B., D.R.K., M.M.A., Z.X., M.R.K., I.V.K., O.T.G. and M.R.A.; resources, D.R.K., T.B.S., O.V.B. and I.V.K.; writing—original draft preparation, P.D.L., A.I.Z. and T.V.S.; writing—review and editing, T.V.S.; visualization, T.V.S., P.D.L., A.I.Z., D.R.K., T.B.S., O.V.B., M.M.A., M.R.K., I.V.K., O.T.G. and M.R.A.; supervision, T.V.S.; project administration, T.V.S.; funding acquisition, M.R.A. All authors have read and agreed to the published version of the manuscript.

Funding

This work was carried out with the support of the MSU Program of Development, Project No. 23-SCH01-16.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The original contributions presented in the study are included in the article, further inquiries can be directed to the corresponding author.

Acknowledgments

This research was carried out using the equipment of the MSU Shared Research Equipment Center “Technologies for obtaining new nanostructured materials and their complex study” purchased by MSU within the framework of the Equipment Renovation Program (National Project “Science”) and within the framework of the MSU Program of Development.

Conflicts of Interest

The authors declare no conflicts of interest.

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Compounds 04 00039 g001
Figure 1. XRD of starting salts and synthesized powders: +—KHSO4 (PDF card # 11-649); *—K2Ca(SO4)2·H2O (PDF card # 28-739); o—CaSO4·2H2O (PDF card # 33-311); c—CaCO3 (PDF card # 5-586).
Figure 1. XRD of starting salts and synthesized powders: +—KHSO4 (PDF card # 11-649); *—K2Ca(SO4)2·H2O (PDF card # 28-739); o—CaSO4·2H2O (PDF card # 33-311); c—CaCO3 (PDF card # 5-586).
Compounds 04 00039 g001
Compounds 04 00039 g002
Figure 2. Camera-taken photos of products extracted from mother liquors separated from precipitates via filtration and after water evaporation: Ex-SP0.5M (a), Ex-SP1.0M (b), Ex-SP2.0M (c).
Figure 2. Camera-taken photos of products extracted from mother liquors separated from precipitates via filtration and after water evaporation: Ex-SP0.5M (a), Ex-SP1.0M (b), Ex-SP2.0M (c).
Compounds 04 00039 g002
Compounds 04 00039 g003
Figure 3. XRD of products extracted from mother liquors, which were separated from precipitates after water evaporation, and KHSO4 given for comparison: *—K2Ca(SO4)2·H2O (PDF card # 28-739); #—K2SO4 (PDF card # 5-613); +—KHSO4 (PDF card # 11-649).
Figure 3. XRD of products extracted from mother liquors, which were separated from precipitates after water evaporation, and KHSO4 given for comparison: *—K2Ca(SO4)2·H2O (PDF card # 28-739); #—K2SO4 (PDF card # 5-613); +—KHSO4 (PDF card # 11-649).
Compounds 04 00039 g003
Compounds 04 00039 g004
Figure 4. FTIR data of starting salts and synthesized powders.
Figure 4. FTIR data of starting salts and synthesized powders.
Compounds 04 00039 g004
Compounds 04 00039 g005
Figure 5. FTIR of products extracted from mother liquors, which were separated from precipitates, after water evaporation. KHSO4 given for comparison.
Figure 5. FTIR of products extracted from mother liquors, which were separated from precipitates, after water evaporation. KHSO4 given for comparison.
Compounds 04 00039 g005
Compounds 04 00039 g006aCompounds 04 00039 g006b
Figure 6. SEM images of the powders synthesized from powdered CaCO3 and water solutions of KHSO4 with concentrations of 0.5 M (a,b), 1.0 M (c,d), and 2.0 M (e,f).
Figure 6. SEM images of the powders synthesized from powdered CaCO3 and water solutions of KHSO4 with concentrations of 0.5 M (a,b), 1.0 M (c,d), and 2.0 M (e,f).
Compounds 04 00039 g006aCompounds 04 00039 g006b
Compounds 04 00039 g007
Figure 7. Bulk densities of the synthesized powders.
Figure 7. Bulk densities of the synthesized powders.
Compounds 04 00039 g007
Compounds 04 00039 g008
Figure 8. Thermal analysis data of the synthesized powders: TG (a) and DTG (b).
Figure 8. Thermal analysis data of the synthesized powders: TG (a) and DTG (b).
Compounds 04 00039 g008
Compounds 04 00039 g009
Figure 9. Mass spectra of the synthesized powders for m/Z = 18.
Figure 9. Mass spectra of the synthesized powders for m/Z = 18.
Compounds 04 00039 g009
Compounds 04 00039 g010
Figure 10. DSC of the synthesized powders.
Figure 10. DSC of the synthesized powders.
Compounds 04 00039 g010
Table 1. Conditions of powders’ synthesis and labeling used for synthesized powders under investigation.
Table 1. Conditions of powders’ synthesis and labeling used for synthesized powders under investigation.
Labeling 1Concentration of KHSO4 Solution, mol/LVolume of Solution, mLAmount of Substance by Reaction, molMass of Reagents, gExpected Mass of K2Ca(SO4)2·H2O, g
KHSO4CaCO3KHSO4CaCO3
SP0.5M0.54000.20.127.210.032.8
SP1.0M14000.40.254.420.065.6
SP2.0M24000.80.4108.840.0131.2
1 SP—synthesized powder.
Table 2. Phase composition and mass of synthesized powders.
Table 2. Phase composition and mass of synthesized powders.
LabelingExpected Mass of K2Ca(SO4)2·H2O, gMass of Synthesized Powder, gPhase Composition of Synthesized Powder 1, Mass %
K2Ca(SO4)2·H2O
(#96-900-8129) 1		CaSO4·2H2O
(#96-901-7314) 1
SP0.5M32.815.50100
SP1.0M65.658.292.97.1
SP2.0M131.2114.398.71.3
1 According to data obtained using “Match!” software.
Table 3. Phase composition and mass of products extracted from mother liquors.
Table 3. Phase composition and mass of products extracted from mother liquors.
LabelingMass of Extracted Product, gPhase Composition of Extracted Products 1, Mass %Mass of K2SO4
in Extracted Product, g
K2Ca(SO4)2·H2O
(#96-900-8129) 1		K2SO4
(#96-900-7570) 1
Ex-SP0.5M17.262.237.86.51
Ex-SP1.0M5.849.150.92.95
Ex-SP2.0M5.683.316.70.94
1 According to data from “Match!” software.
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MDPI and ACS Style

Safronova, T.V.; Laptin, P.D.; Zybina, A.I.; Liao, X.; Shatalova, T.B.; Boytsova, O.V.; Khayrutdinova, D.R.; Akhmedov, M.M.; Xu, Z.; Kolesnik, I.V.; et al. Powders Synthesized from Calcium Carbonate and Water Solutions of Potassium Hydrosulfate of Various Concentrations. Compounds 2024, 4, 650-663. https://doi.org/10.3390/compounds4040039

AMA Style

Safronova TV, Laptin PD, Zybina AI, Liao X, Shatalova TB, Boytsova OV, Khayrutdinova DR, Akhmedov MM, Xu Z, Kolesnik IV, et al. Powders Synthesized from Calcium Carbonate and Water Solutions of Potassium Hydrosulfate of Various Concentrations. Compounds. 2024; 4(4):650-663. https://doi.org/10.3390/compounds4040039

Chicago/Turabian Style

Safronova, Tatiana V., Peter D. Laptin, Alexandra I. Zybina, Xiaoling Liao, Tatiana B. Shatalova, Olga V. Boytsova, Dinara R. Khayrutdinova, Marat M. Akhmedov, Zichen Xu, Irina V. Kolesnik, and et al. 2024. "Powders Synthesized from Calcium Carbonate and Water Solutions of Potassium Hydrosulfate of Various Concentrations" Compounds 4, no. 4: 650-663. https://doi.org/10.3390/compounds4040039

APA Style

Safronova, T. V., Laptin, P. D., Zybina, A. I., Liao, X., Shatalova, T. B., Boytsova, O. V., Khayrutdinova, D. R., Akhmedov, M. M., Xu, Z., Kolesnik, I. V., Kaimonov, M. R., Gavlina, O. T., & Akhmedov, M. R. (2024). Powders Synthesized from Calcium Carbonate and Water Solutions of Potassium Hydrosulfate of Various Concentrations. Compounds, 4(4), 650-663. https://doi.org/10.3390/compounds4040039

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