### Abstract

The emf of the following cell (A) without liquid junction was used to investigate the HBr + NiBr_{2} + H_{2}O mixed electrolyte system. Pt,H_{2}(g,1 atm)|HBr(m(A)),NiBr_{2}(m(B))|AgBr,Ag. Measurements of the emf were performed for solutions at constant total ionic strengths of 0.05, 0.1, 0.25, 0.5, 1.0, 1.5 and 2.0 mol kg^{-1} at temperatures ranging from 5°C to 55°C, except for I = 2.0 mol kg^{-1}, where measurements were only made at 25°C. The mean activity coefficients of HBr in the mixtures were calculated using the Nernst equation. The thermodynamic properties of unsymmetrical mixtures are interpreted in terms of the simpler Harned's rule, as well as the comprehensive Pitzer's ion-interaction approach including higher order electrostatic effects for electrolyte mixtures. The Harned interaction coefficients α(AB) and β(AB) were determined from the data on the HBr + NiBr_{2} mixture. Literature osmotic coefficient data at 25°C have been used to determine the pure electrolyte Pitzer parameters (β((0)), β((1)), and C(φ)) for NiBr_{2}. The results were combined with the value of Θ(H,Ni) = 0.069 obtained from the HCl + NiCl_{2} + H_{2}O system to determine Ψ(H,Ni,Br) = 0.06 from our emf data at 25°C. The effect of temperature (0-55°C) on the Pitzer parameters (β((0)), β((1)), and C(φ)) for HBr and NiBr_{2} was determined from the present emf measurements, assuming that the higher order electrical terms (Θ(H,Ni) and Ψ(H,Ni,Br)) were independent of temperature. They were fitted to a simple polynomial function of temperature (°C): β(H,Br)((0)) = 0.2085 + 8.55 x 10^{-4}(t - 25) - 1.8 x 10^{-4}(t - 25)^{2} β(H,Br)((1)) = 0.3477 + 18.0 x 10^{-4}(t - 25) + 3.9 x 10^{-4}(t - 25)^{2} C(H,Br)(φ) = 0.001517 - 7.10 x 10^{-4}(t - 25) + 1.05 x 10^{-4}(t - 25)^{2} and β(N,Br)((0)) = 0.4451 - 0.0307(t - 25) - 3.1 x 10^{-4}(t - 25)^{2} β(N,Br)((1)) = 1.49 + 0.0855(t - 25) - 6.2 x 10^{-4}(t - 25)^{2} C(Ni,Br)((φ)) = - 0.00626 + 0.029(t - 25) + 8.45 x 10^{-4}(t - 25)^{2}. The values of the Pitzer parameters for NiBr_{2} were of the same order of magnitude as found for other bivalent bromides. (C) 2000 Elsevier Science B.V.

Original language | English (US) |
---|---|

Pages (from-to) | 37-48 |

Number of pages | 12 |

Journal | Marine Chemistry |

Volume | 70 |

Issue number | 1-3 |

DOIs | |

State | Published - May 2000 |

### Fingerprint

### Keywords

- Harned's rule
- HBr + NiBr + HO system
- Nernst equation
- Pitzer parameters

### ASJC Scopus subject areas

- Chemistry(all)
- Oceanography

### Cite this

*Marine Chemistry*,

*70*(1-3), 37-48. https://doi.org/10.1016/S0304-4203(00)00013-X

**Thermodynamics of the HBr + NiBr2 + H2O system from 5°C to 55°C.** / Roy, Rabindra N.; Coffman, Nancy A.; Bell, Melanie D.; Roy, Lakshmi N.; Pierrot, Denis; Millero, Frank J.

Research output: Contribution to journal › Article

*Marine Chemistry*, vol. 70, no. 1-3, pp. 37-48. https://doi.org/10.1016/S0304-4203(00)00013-X

}

TY - JOUR

T1 - Thermodynamics of the HBr + NiBr2 + H2O system from 5°C to 55°C

AU - Roy, Rabindra N.

AU - Coffman, Nancy A.

AU - Bell, Melanie D.

AU - Roy, Lakshmi N.

AU - Pierrot, Denis

AU - Millero, Frank J

PY - 2000/5

Y1 - 2000/5

N2 - The emf of the following cell (A) without liquid junction was used to investigate the HBr + NiBr2 + H2O mixed electrolyte system. Pt,H2(g,1 atm)|HBr(m(A)),NiBr2(m(B))|AgBr,Ag. Measurements of the emf were performed for solutions at constant total ionic strengths of 0.05, 0.1, 0.25, 0.5, 1.0, 1.5 and 2.0 mol kg-1 at temperatures ranging from 5°C to 55°C, except for I = 2.0 mol kg-1, where measurements were only made at 25°C. The mean activity coefficients of HBr in the mixtures were calculated using the Nernst equation. The thermodynamic properties of unsymmetrical mixtures are interpreted in terms of the simpler Harned's rule, as well as the comprehensive Pitzer's ion-interaction approach including higher order electrostatic effects for electrolyte mixtures. The Harned interaction coefficients α(AB) and β(AB) were determined from the data on the HBr + NiBr2 mixture. Literature osmotic coefficient data at 25°C have been used to determine the pure electrolyte Pitzer parameters (β((0)), β((1)), and C(φ)) for NiBr2. The results were combined with the value of Θ(H,Ni) = 0.069 obtained from the HCl + NiCl2 + H2O system to determine Ψ(H,Ni,Br) = 0.06 from our emf data at 25°C. The effect of temperature (0-55°C) on the Pitzer parameters (β((0)), β((1)), and C(φ)) for HBr and NiBr2 was determined from the present emf measurements, assuming that the higher order electrical terms (Θ(H,Ni) and Ψ(H,Ni,Br)) were independent of temperature. They were fitted to a simple polynomial function of temperature (°C): β(H,Br)((0)) = 0.2085 + 8.55 x 10-4(t - 25) - 1.8 x 10-4(t - 25)2 β(H,Br)((1)) = 0.3477 + 18.0 x 10-4(t - 25) + 3.9 x 10-4(t - 25)2 C(H,Br)(φ) = 0.001517 - 7.10 x 10-4(t - 25) + 1.05 x 10-4(t - 25)2 and β(N,Br)((0)) = 0.4451 - 0.0307(t - 25) - 3.1 x 10-4(t - 25)2 β(N,Br)((1)) = 1.49 + 0.0855(t - 25) - 6.2 x 10-4(t - 25)2 C(Ni,Br)((φ)) = - 0.00626 + 0.029(t - 25) + 8.45 x 10-4(t - 25)2. The values of the Pitzer parameters for NiBr2 were of the same order of magnitude as found for other bivalent bromides. (C) 2000 Elsevier Science B.V.

AB - The emf of the following cell (A) without liquid junction was used to investigate the HBr + NiBr2 + H2O mixed electrolyte system. Pt,H2(g,1 atm)|HBr(m(A)),NiBr2(m(B))|AgBr,Ag. Measurements of the emf were performed for solutions at constant total ionic strengths of 0.05, 0.1, 0.25, 0.5, 1.0, 1.5 and 2.0 mol kg-1 at temperatures ranging from 5°C to 55°C, except for I = 2.0 mol kg-1, where measurements were only made at 25°C. The mean activity coefficients of HBr in the mixtures were calculated using the Nernst equation. The thermodynamic properties of unsymmetrical mixtures are interpreted in terms of the simpler Harned's rule, as well as the comprehensive Pitzer's ion-interaction approach including higher order electrostatic effects for electrolyte mixtures. The Harned interaction coefficients α(AB) and β(AB) were determined from the data on the HBr + NiBr2 mixture. Literature osmotic coefficient data at 25°C have been used to determine the pure electrolyte Pitzer parameters (β((0)), β((1)), and C(φ)) for NiBr2. The results were combined with the value of Θ(H,Ni) = 0.069 obtained from the HCl + NiCl2 + H2O system to determine Ψ(H,Ni,Br) = 0.06 from our emf data at 25°C. The effect of temperature (0-55°C) on the Pitzer parameters (β((0)), β((1)), and C(φ)) for HBr and NiBr2 was determined from the present emf measurements, assuming that the higher order electrical terms (Θ(H,Ni) and Ψ(H,Ni,Br)) were independent of temperature. They were fitted to a simple polynomial function of temperature (°C): β(H,Br)((0)) = 0.2085 + 8.55 x 10-4(t - 25) - 1.8 x 10-4(t - 25)2 β(H,Br)((1)) = 0.3477 + 18.0 x 10-4(t - 25) + 3.9 x 10-4(t - 25)2 C(H,Br)(φ) = 0.001517 - 7.10 x 10-4(t - 25) + 1.05 x 10-4(t - 25)2 and β(N,Br)((0)) = 0.4451 - 0.0307(t - 25) - 3.1 x 10-4(t - 25)2 β(N,Br)((1)) = 1.49 + 0.0855(t - 25) - 6.2 x 10-4(t - 25)2 C(Ni,Br)((φ)) = - 0.00626 + 0.029(t - 25) + 8.45 x 10-4(t - 25)2. The values of the Pitzer parameters for NiBr2 were of the same order of magnitude as found for other bivalent bromides. (C) 2000 Elsevier Science B.V.

KW - Harned's rule

KW - HBr + NiBr + HO system

KW - Nernst equation

KW - Pitzer parameters

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U2 - 10.1016/S0304-4203(00)00013-X

DO - 10.1016/S0304-4203(00)00013-X

M3 - Article

AN - SCOPUS:0034036924

VL - 70

SP - 37

EP - 48

JO - Marine Chemistry

JF - Marine Chemistry

SN - 0304-4203

IS - 1-3

ER -