Experimental investigation on freezing point depressions and thermodynamic modelling of NiSO4-H2O and NiSO4-H2SO4-H2O systems using Pitzer equations from eutectic point up to 523.15 K

David Sibarani; Hannu Sippola; Daniel Lindberg

doi:10.1016/j.ces.2025.122282

Experimental investigation on freezing point depressions and thermodynamic modelling of NiSO₄-H₂O and NiSO₄-H₂SO₄-H₂O systems using Pitzer equations from eutectic point up to 523.15 K

David Sibarani^*
, Hannu Sippola
, Daniel Lindberg

^*Tämän työn vastaava kirjoittaja

Tutkimustuotos: Lehtiartikkeli › Article › Scientific › vertaisarvioitu

1 Sitaatiot (Scopus)

62 Lataukset (Pure)

Abstrakti

One previous study developed a consistent Pitzer model by employing nine terms of virial coefficients for NiSO₄-H₂O system and four additional terms for the NiSO₄-H₂SO₄-H₂O system. The present work incorporates five additional experimental datasets that had not been previously utilized and re-evaluates the entire datasets to refine the NiSO₄-H₂O and NiSO₄-H₂SO₄-H₂O models. The NiSO₄-H₂O system was modelled from the eutectic point up to 523.15 K, utilizing eight terms of Pitzer parameters. Due to the scarcity of freezing point data beyond 0.2 mol·kg⁻¹ of NiSO₄, fifty-six experimental data points were generated in the current study, extending from 0.0015 to 1.56 mol·kg⁻¹. The root-mean-square deviations for the models were determined to be 0.09 for solubility, 0.0001 for water activity on freezing curve, 0.0009 for isopiestic water activity, 0.026 for mean activity coefficients of NiSO₄, and 115 J·mol⁻¹ for the apparent relative molal enthalpy of solution. The NiSO₄-H₂O model was then utilized to develop two types of NiSO₄-H₂SO₄-H₂O models based on the Pitzer parameter combination: β⁰-β¹-C^ϕ and β⁰-β¹-ψ. While the first type is generally consistent up to 523 K, the latter is exceptionally well for low temperature predictions. A comprehensive analysis and screening of each dataset is provided.

Alkuperäiskieli	Englanti
Artikkeli	122282
Sivumäärä	18
Julkaisu	Chemical Engineering Science
Vuosikerta	320
Numero	Part A
Varhainen verkossa julkaisun päivämäärä	7 elok. 2025
DOI - pysyväislinkit	https://doi.org/10.1016/j.ces.2025.122282
Tila	Julkaistu - 15 tammik. 2026
OKM-julkaisutyyppi	A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

Rahoitus

This research is funded by the Foundation for Research of Natural Resources in Finland (Detailed aqueous solution chemistry for flotation circuits in Nordic conditions, Decision 20210033). Additional funding from the PhosPath Project (13341404) and BATCIRCLE 2.0 Project (Finland-based Circular Ecosystem of Battery Metals, Business Finland grant 211852) are also appreciated. Guidance in the general concept of thermodynamics of aqueous solution and experimental help by Dr. Tuomas Vielma is greatly appreciated. Assistance by Dr. Petri Uusi-Kyyny in making the FPD apparatus and usage of Densimeter is greatly appreciated, as well as help from “Chemical Engineering in Aqueous Systems” and “Chemical Engineering” group members is acknowledged.

Pääsy asiakirjaan

10.1016/j.ces.2025.122282Lisenssi: CC BY

Experimental_investigation_on_freezing_point_depressions_and_thermodynamic_modellingFinal published version, 3,91 MBLisenssi: CC BY

Muut tiedostot ja linkit

Linkki julkaisuun Scopuksessa

PhosPath, TDM: High temperature chemistry of phosphorus pathways to more effective recycling and utilization
Lindberg, D. (Vastuullinen johtaja), Nafees, T. (Projektin jäsen), Attah-Kyei, D. (Projektin jäsen), Abaid Ur Rehman, H. (Projektin jäsen), Sukhomlinov, D. (Projektin jäsen), Shafaat, A. (Projektin jäsen), Kansanaho, M. (Projektin jäsen), Malan, W. (Projektin jäsen), Jeon, J. (Projektin jäsen), Sibarani, D. (Projektin jäsen), Pankka, I. (Projektin jäsen) & Klemettinen, L. (Projektin jäsen)
01/09/2021 → 31/08/2025
Projekti: RCF Academy Project
BATCircle2: Finland-based circular ecosystem of battery metals
Lundström, M. (Vastuullinen johtaja), Klemettinen, L. (Projektin jäsen), Xiao, Y. (Projektin jäsen), Le, T. (Projektin jäsen), Kansanaho, M. (Projektin jäsen), Sibarani, D. (Projektin jäsen), Partinen, J. (Projektin jäsen), Tran, H. (Projektin jäsen), Alajoki, J. (Projektin jäsen), Lappalainen, H. (Projektin jäsen), Liljanko, H. (Projektin jäsen), Nikolov, S. (Projektin jäsen), Wilson, B. (Projektin jäsen), Wang, Z. (Projektin jäsen), Terho, T. (Projektin jäsen), Sahlman, M. (Projektin jäsen), Le, T. (Projektin jäsen), Zou, Y. (Projektin jäsen), Palomäki, H. (Projektin jäsen), Porkola, T.-M. (Projektin jäsen), Karppinen, A. (Projektin jäsen), Revitzer, H. (Projektin jäsen), Halli, P. (Projektin jäsen), Kupi, A. (Projektin jäsen), Vänskä, J. (Projektin jäsen), Chernyaev, A. (Projektin jäsen), Mylly, M. (Projektin jäsen), Rinne, M. (Projektin jäsen), Esmaeilzadeh Dilmaghani, S. (Projektin jäsen), Kong, X. (Projektin jäsen), Saeed, M. (Projektin jäsen), Biswas, J. (Projektin jäsen), Pakseresht, S. (Projektin jäsen), Seisko, S. (Projektin jäsen), Esekheigbe, E. (Projektin jäsen), Wan, X. (Projektin jäsen), Al-Ogaili, A. (Projektin jäsen), Repo, V. (Projektin jäsen), Jaakonaho, E. (Projektin jäsen), Rinne, T. (Projektin jäsen), Leveinen, J. (Projektin jäsen), Tas, G. (Projektin jäsen), Klemettinen, A. (Projektin jäsen), Mkurazhizha, H. (Projektin jäsen), Schreiner, S. (Projektin jäsen), Klemelä, E. (Projektin jäsen), Niemelä, T. (Projektin jäsen), Huaman, L. (Projektin jäsen), Vierunketo, M. (Projektin jäsen), Araya Gómez, N. (Projektin jäsen), Bogdanova, A. (Projektin jäsen), Chen, M. (Projektin jäsen), Rostami, A. (Projektin jäsen), Hentman, J. (Projektin jäsen), Garnier, C. (Projektin jäsen), Sukhomlinov, D. (Projektin jäsen), Kallio, T. (Projektin jäsen), Whittle, L. (Projektin jäsen), Nurmi, S. (Projektin jäsen), Kobets, A. (Projektin jäsen), Jokilaakso, A. (Projektin jäsen), Lindberg, D. (Co-PI) & Serna Guerrero, R. (Projektin jäsen)
01/05/2021 → 30/04/2024
Projekti: BF Co-Innovation

Siteeraa tätä

@article{3b719807643645dcbd6c6f31fe756fbe,

title = "Experimental investigation on freezing point depressions and thermodynamic modelling of NiSO4-H2O and NiSO4-H2SO4-H2O systems using Pitzer equations from eutectic point up to 523.15 K",

abstract = "One previous study developed a consistent Pitzer model by employing nine terms of virial coefficients for NiSO4-H2O system and four additional terms for the NiSO4-H2SO4-H2O system. The present work incorporates five additional experimental datasets that had not been previously utilized and re-evaluates the entire datasets to refine the NiSO4-H2O and NiSO4-H2SO4-H2O models. The NiSO4-H2O system was modelled from the eutectic point up to 523.15 K, utilizing eight terms of Pitzer parameters. Due to the scarcity of freezing point data beyond 0.2 mol·kg−1 of NiSO4, fifty-six experimental data points were generated in the current study, extending from 0.0015 to 1.56 mol·kg−1. The root-mean-square deviations for the models were determined to be 0.09 for solubility, 0.0001 for water activity on freezing curve, 0.0009 for isopiestic water activity, 0.026 for mean activity coefficients of NiSO4, and 115 J·mol−1 for the apparent relative molal enthalpy of solution. The NiSO4-H2O model was then utilized to develop two types of NiSO4-H2SO4-H2O models based on the Pitzer parameter combination: β0-β1-Cϕ and β0-β1-ψ. While the first type is generally consistent up to 523 K, the latter is exceptionally well for low temperature predictions. A comprehensive analysis and screening of each dataset is provided.",

keywords = "Freezing point, NiSO-HO, NiSO-HSO-HO, Pitzer model, Solubilities",

author = "David Sibarani and Hannu Sippola and Daniel Lindberg",

note = "Publisher Copyright: {\textcopyright} 2025 The Author(s)",

year = "2026",

month = jan,

day = "15",

doi = "10.1016/j.ces.2025.122282",

language = "English",

volume = "320",

journal = "Chemical Engineering Science",

issn = "0009-2509",

publisher = "Elsevier",

number = "Part A",

}

Experimental investigation on freezing point depressions and thermodynamic modelling of NiSO₄-H₂O and NiSO₄-H₂SO₄-H₂O systems using Pitzer equations from eutectic point up to 523.15 K. / Sibarani, David; Sippola, Hannu ; Lindberg, Daniel.
julkaisussa: Chemical Engineering Science, Vuosikerta 320, Nro Part A, 122282, 15.01.2026.

Tutkimustuotos: Lehtiartikkeli › Article › Scientific › vertaisarvioitu

TY - JOUR

T1 - Experimental investigation on freezing point depressions and thermodynamic modelling of NiSO4-H2O and NiSO4-H2SO4-H2O systems using Pitzer equations from eutectic point up to 523.15 K

AU - Sibarani, David

AU - Sippola, Hannu

AU - Lindberg, Daniel

PY - 2026/1/15

Y1 - 2026/1/15

N2 - One previous study developed a consistent Pitzer model by employing nine terms of virial coefficients for NiSO4-H2O system and four additional terms for the NiSO4-H2SO4-H2O system. The present work incorporates five additional experimental datasets that had not been previously utilized and re-evaluates the entire datasets to refine the NiSO4-H2O and NiSO4-H2SO4-H2O models. The NiSO4-H2O system was modelled from the eutectic point up to 523.15 K, utilizing eight terms of Pitzer parameters. Due to the scarcity of freezing point data beyond 0.2 mol·kg−1 of NiSO4, fifty-six experimental data points were generated in the current study, extending from 0.0015 to 1.56 mol·kg−1. The root-mean-square deviations for the models were determined to be 0.09 for solubility, 0.0001 for water activity on freezing curve, 0.0009 for isopiestic water activity, 0.026 for mean activity coefficients of NiSO4, and 115 J·mol−1 for the apparent relative molal enthalpy of solution. The NiSO4-H2O model was then utilized to develop two types of NiSO4-H2SO4-H2O models based on the Pitzer parameter combination: β0-β1-Cϕ and β0-β1-ψ. While the first type is generally consistent up to 523 K, the latter is exceptionally well for low temperature predictions. A comprehensive analysis and screening of each dataset is provided.

AB - One previous study developed a consistent Pitzer model by employing nine terms of virial coefficients for NiSO4-H2O system and four additional terms for the NiSO4-H2SO4-H2O system. The present work incorporates five additional experimental datasets that had not been previously utilized and re-evaluates the entire datasets to refine the NiSO4-H2O and NiSO4-H2SO4-H2O models. The NiSO4-H2O system was modelled from the eutectic point up to 523.15 K, utilizing eight terms of Pitzer parameters. Due to the scarcity of freezing point data beyond 0.2 mol·kg−1 of NiSO4, fifty-six experimental data points were generated in the current study, extending from 0.0015 to 1.56 mol·kg−1. The root-mean-square deviations for the models were determined to be 0.09 for solubility, 0.0001 for water activity on freezing curve, 0.0009 for isopiestic water activity, 0.026 for mean activity coefficients of NiSO4, and 115 J·mol−1 for the apparent relative molal enthalpy of solution. The NiSO4-H2O model was then utilized to develop two types of NiSO4-H2SO4-H2O models based on the Pitzer parameter combination: β0-β1-Cϕ and β0-β1-ψ. While the first type is generally consistent up to 523 K, the latter is exceptionally well for low temperature predictions. A comprehensive analysis and screening of each dataset is provided.

KW - Freezing point

KW - NiSO-HO

KW - NiSO-HSO-HO

KW - Pitzer model

KW - Solubilities

UR - https://www.scopus.com/pages/publications/105012625435

U2 - 10.1016/j.ces.2025.122282

DO - 10.1016/j.ces.2025.122282

M3 - Article

AN - SCOPUS:105012625435

SN - 0009-2509

VL - 320

JO - Chemical Engineering Science

JF - Chemical Engineering Science

IS - Part A

M1 - 122282

ER -

Experimental investigation on freezing point depressions and thermodynamic modelling of NiSO4-H2O and NiSO4-H2SO4-H2O systems using Pitzer equations from eutectic point up to 523.15 K

Abstrakti

Rahoitus

Pääsy asiakirjaan

Muut tiedostot ja linkit

Sormenjälki

Projektit

PhosPath, TDM: High temperature chemistry of phosphorus  pathways to more effective recycling and utilization

BATCircle2: Finland-based circular ecosystem of battery metals

Siteeraa tätä

Experimental investigation on freezing point depressions and thermodynamic modelling of NiSO₄-H₂O and NiSO₄-H₂SO₄-H₂O systems using Pitzer equations from eutectic point up to 523.15 K

PhosPath, TDM: High temperature chemistry of phosphorus pathways to more effective recycling and utilization