Dissociation behaviour of (tetra-n-butylammonium bromide + tetra-n-butylammonium chloride) mixed semiclathrate hydrate systems |
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Institution: | 1. Faculty of Petroleum Engineering, Petroleum University of Technology (PUT), Post Box: 63431, Ahwaz, Iran;2. Department of Chemical Engineering, Iran University of Science and Technology (IUST), Tehran, Iran;1. ENSTA ParisTech-UCP, 828 Boulevard des Maréchaux, 91762 Palaiseau Cedex, France;2. LGP2ES (EA 21), IRSTEA-GPAN, Parc de Tourvoie BP 44, 92136 Antony Cedex, France;1. Chemical Engineering Department, Petroleum University of Technology, Ahwaz, Iran;2. Esfarayen University of Technology, North Khorasan, Esfarayen, Iran;3. Department of Design and Engineering, School of Creative Arts and Engineering, Staffordshire University, Stoke-on-Trent, ST4 2DE, United Kingdom;1. School of Mechanical Engineering, Korea University, 145, Anam-ro, Seongbuk-gu, Seoul 02841, Republic of Korea;2. School of Mechanical Engineering, Chung Ang University, 84, Heuksuk-ro, Dongjak-gu, Seoul 06974, Republic of Korea |
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Abstract: | The thermal properties of {tetra-n-butylammonium bromide + tetra-n-butylammonium chloride (TBAB + TBAC)} mixed semiclathrate hydrates prepared from aqueous solutions were investigated by dissociation temperature measurements and differential scanning calorimetry (DSC). The maximum dissociation temperature of the mixed hydrate crystals at 0.1 MPa is 288.5 K for xTBAB = 0.2 {mole fraction of TBAB to (TBAB + TBAC)}, which is higher than that of the pure hydrates {T = (285.5 and 288.2) K for TBAB and TBAC hydrates, respectively}. In addition, the dissociation enthalpies of the mixed hydrates are higher than those of the pure hydrates {(5.55 ± 0.06) kJ ⋅ mol−1 H2O for pure TBAB hydrate and (5.30 ± 0.05) kJ ⋅ mol−1 H2O for pure TBAC hydrate}, with a maximum of (5.95 ± 0.12) kJ ⋅ mol−1 H2O recorded at approximately xTBAB = 0.4. It was therefore suggested that the crystal distortion in (TBAB + TBAC) mixed hydrates, caused by replacing water molecules by both bromide and chloride anions, was smaller than that observed for each pure hydrate. Consequently, the hydration numbers in the mixed hydrates were hypothesized to be slightly higher than those of the pure hydrates. |
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Keywords: | Semiclathrate hydrate Thermodynamics Differential scanning calorimetry Powder X-ray diffraction |
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