Aqueous nonelectrolyte solutions. Part XVI. Formula of deuterium sulfide D-hydrate and its dissociation thermodynamic functions

2000 ◽  
Vol 78 (1) ◽  
pp. 1-9 ◽  
Author(s):  
Colin W Clarke ◽  
David N Glew

A method has been devised to approximate both the hydrate formula number n and the standard thermodynamic functions for hydrate dissociation from the temperature change of the hydrate former fugacity along a univariant three-phase (hl1g) equilibrium line. Thermodynamic equations are derived, their validity discussed, and an iterative method for their solution is described. The univariant (hl1g) equilibrium dissociation of deuterium sulfide D-hydrate (D2S·nD2O phase h) into gaseous deuterium sulfide (g) and liquid deuterium oxide (l1) has been treated to give approximate formulae and dissociation constants at 58 temperatures from 2.798 to 30.666°C. Dissociation equilibrium constants Kp(h–> l1g) have been represented as a function of temperature by a four-parameter equation which yields both values and standard errors (i) for ΔHot(h–> l1g) and ΔCpot(h–> l1g) the standard enthalpy and heat capacity changes for D-hydrate dissociation and (ii) for n = r the approximate formula number of the D-hydrate at each experimental temperature. The formula D2S·6.115D2O with standard error 0.018D2O is found for deuterium sulfide D-hydrate at lower quadruple point Q(hs1l1g) 3.392°C; an approximate formula D2S·5.840D2O with SE 0.019D2O is found at upper quadruple point Q(hs1l2g) 30.770°C. Key words: clathrate D-hydrate of deuterium sulfide, deuterium sulfide D-hyfrate, formula of deuterium sulfide D-hydrate, thermodynamics of clathrate hydrate dissociation, dissociation equilibrium constant of deuterium sulfide D-hydrate, standard enthalpy, and heat capacity changes for dissociation of deuterium sulfide D-hydrate.


2000 ◽  
Vol 78 (9) ◽  
pp. 1204-1213 ◽  
Author(s):  
David N Glew

Literature data for the saturation vapor pressure P(hl1g) of hydrogen sulfide hydrate with water, at 43 temperatures between quadruple points Q(hs1l1g) at –0.4°C and Q(hl1l2g) at 29.484°C, are properly represented by a six-parameter equation to give a standard error (SE) of 0.13% on a hydrate pressure measurement of unit weight. Equilibrium hydrogen sulfide and water fugacities and the gas and aqueous phase compositions are derived using the Redlich–Kwong equation of state. Literature data for the saturation vapor pressure P(hs1g) of hydrogen sulfide hydrate with ice, at 15 temperatures between –1.249 and –21.083°C, are properly represented by a two-parameter equation to give a SE of 0.26% on a single hydrate pressure measurement. Quadruple point Q(hs1l1g) is evaluated at temperature –0.413° with SE 0.042°C and at pressure 94.7 with SE 0.26 kPa. Using the thermodynamic method, described for deuterium sulfide D-hydrate, the equilibrium fugacities of hydrogen sulfide are used to define 43 equilibrium constants Kp(h[Formula: see text]l1g) for hydrate dissociation into water and hydrogen sulfide gas. The temperature dependence of ln Kp(h[Formula: see text]l1g) is represented by a three-parameter thermodynamic equation which gives both values and standard errors (i) for Kp(h[Formula: see text]l1g), and for δHot(h[Formula: see text]l1g) and δCpot(h[Formula: see text]l1g), the standard enthalpy and heat capacity changes for hydrate dissociation and (ii) for n = r the approximate formula number of the hydrate H2S·nH2O at each experimental temperature. The formula H2S·6.119H2O with standard error 0.029H2O is found for hydrogen sulfide hydrate with water at lower quadruple point Q(hs1l1g) –0.413°C: an approximate formula H2S·5.869H2O with SE 0.026H2O is found at upper quadruple point Q(hl1l2g) 29.484°C. These estimates for the formula of hydrogen sulfide hydrate at its quadruple points are not significantly different from those found for the deuterium sulfide D-hydrate.Key words: clathrate hydrate of hydrogen sulfide, hydrogen sulfide hydrate, formula of hydrogen sulfide hydrate, thermodynamics of clathrate hydrate dissociation, dissociation equilibrium constant of hydrogen sulfide hydrate, standard enthalpy and heat capacity changes for dissociation of hydrogen sulfide hydrate.



2002 ◽  
Vol 80 (4) ◽  
pp. 418-439 ◽  
Author(s):  
David N Glew

Literature data for the saturation pressure P(hl1g) of methane hydrate with water, at 102 temperatures between –0.29 and 46.87°C, are properly represented by two distinct equations, with a quadruple point Q(h1h2l1g) transition temperature at 26.7°C with standard error (SE) 0.9°C and 55.5 MPa with SE 5.3 MPa. The structure I type methane hydrate phase h1 is stable below 26.7°C and the structure II type methane hydrate phase h2 is stable above 26.7°C. Between –0.29 and 25.54°C, 85 equilibrium pressures of methane hydrate with water are best represented, with SE 1.33% on a single pressure measurement, by a four-parameter thermodynamic equation. The corresponding equilibrium methane fugacities are represented, with SE 0.94% on a fugacity determination, by a five-parameter equation. Between 26.98 and 46.87°C, 17 equilibrium methane hydrate pressures with water are best represented, with SE 2.22% on a pressure measurement, by a three-parameter equation. Composition of the equilibrium aqueous phase is evaluated using methane fugacity with the solubility equation including a Poynting correction. Literature data between –2.22 and –14.10°C, for the saturation pressure P(h1s1g) of structure I methane hydrate with ice, are properly represented by a two-parameter equation, with SE 1.1% on a single pressure measurement. Standard enthalpy change for structure I methane hydrate dissociation into ice and methane gas is found to be ΔHot(h1[Formula: see text] s1g) = 18058 J mol–1 with SE 608 J mol–1 at -8.28°C. The quadruple point Q(h1s1l1g) is estimated at –0.290°C with SE 0.0064°C and at 2.527 MPa with SE 0.053 MPa. Using the classical thermodynamic method, as described for deuterium sulfide D-hydrate, methane hydrate equilibrium fugacities define 85 equilibrium constants Kp(h1[Formula: see text]l1g) between –0.29 and 25.54°C for dissociation of structure I hydrate h1 into liquid water l1 and methane gas. Temperature dependence of ln Kp(h1[Formula: see text]l1g) is well-represented by a three-parameter thermodynamic equation that gives both estimates and their standard errors for (i) ΔHot(h1[Formula: see text]l1g) and ΔCpot(h1[Formula: see text]l1g), the standard enthalpy and heat capacity changes, respectively, for hydrate h1 dissociation, and for (ii) n = r, the approximate formula number of the hydrate CH4·nH2O at each experimental temperature. The formula CH4·6.205H2O with SE 0.066H2O is found for the structure I methane hydrate h1 with water at quadruple point Q(h1s1l1g) –0.29°C; an approximate formula CH4·5.759H2O with SE 0.077H2O is found at quadruple point Q(h1h2l1g) 26.7°C. Between 26.98 and 46.87°C, the 17-equilibrium constants Kp(h2[Formula: see text]l1g) for dissociation of structure II methane hydrate h2 into liquid water l1 and methane gas are represented by a constrained three-parameter thermodynamic equation. For structure II methane hydrate the formula CH4·5.822H2O with SE 0.064H2O is found at quadruple point Q(h1h2l1g) 26.7°C and the formula CH4·5.699H2O with SE 0.064H2O at 46.87°C. Molar volumes and cohesive energy densities of the methane hydrates are compared with equilibrium compressed water.Key words: clathrate hydrates of methane, two methane gas hydrates, formula of structure I methane hydrate, thermodynamics of clathrate hydrate dissociation, dissociation equilibrium constants of structure I methane hydrate, standard enthalpy and heat capacity changes for dissociation of structure I methane hydrate, methane hydrates' transition temperature, formula of structure II methane hydrate, dissociation equilibrium constants of structure II methane hydrate, standard enthalpy change for dissociation of structure II methane hydrate, methane hydrates' cohesive energy density.



2003 ◽  
Vol 81 (12) ◽  
pp. 1443-1450 ◽  
Author(s):  
David N Glew

Sixteen new measurements of high precision for structure I methane hydrate with water between 31.93 and 47.39 °C are shown to be metastable and exhibit higher methane pressures than found by earlier workers. Comparison of earlier measurements between 26.7 and 47.2 °C permit positive identification of the structure II and the structure I hydrates. Forty-nine equilibrium constants Kp(h1[Formula: see text]l1g) for dissociation of structure I methane hydrate into water and methane, 32 between –0.29 and 26.7 °C for the stable hydrate and 17 between 31.93 and 47.39 °C for the metastable hydrate, are best represented by a three-parameter thermodynamic equation, which indicates a standard error (SE) of 0.63% on a single Kp(h1[Formula: see text]l1g) determination. The congruent dissociation melting point C(h1l1gxm) of metastable structure I methane hydrate is at 47.41 °C with SE 0.02 °C and at pressure 505 MPa. The congruent equilibrium constant Kp(h1[Formula: see text]l1g) is 102.3 MPa with SE 0.2 MPa. ΔH°t(h1[Formula: see text]l1g) is 62 281 J mol–1 with SE 184 J mol–1, and the congruent formula is CH4·5.750H2O with SE 0.059H2O. At the congruent point, ΔV(h1[Formula: see text]l1g) is zero within experimental precision, and its estimate is 1.3 with SE 1.6 cm3 mol–1. The stability range of structure I methane hydrate with water extends from quadruple point Q(s1h1l1g) at –0.29 °C up to quadruple point Q(h1h2l1g) at 26.7 °C, and its metastability range with water extends from 26.7 °C up to the congruent dissociation melting point C(h1l1gxm) at 47.41 °C. Key words: methane hydrate, clathrate structure I, metastability range, dissociation equilibrium constant, formula, congruent melting point, metastability of structure I hydrate.



1973 ◽  
Vol 26 (5) ◽  
pp. 1005 ◽  
Author(s):  
PD Bolton ◽  
J Ellis ◽  
KA Fleming ◽  
IR Lantzke

Thermodynamic acidity constants have been measured over the temperature range 5-50� for aqueous solutions of sodium 4?-dimethylaminoazobenzene- 4-sulphonate (methyl orange) and sodium 4?-dimethylaminoazobenzene-2- sulphonate (ortho-methyl orange). From these data values of the standard enthalpy, entropy, and heat capacity changes have been calculated for these compounds. These results are discussed in conjunction with previous spectrophotometric and other data with reference to the nature of the equilibrium systems involved in these protonation reactions. It is concluded that existing evidence does not allow an unequivocal assignment of the sites of protonation of these and related molecules.



2003 ◽  
Vol 81 (2) ◽  
pp. 179-185 ◽  
Author(s):  
David N Glew

Twenty-four equilibrium pressures, P(h2l1g), of structure II methane hydrate h2 with water l1 between 27.0 and 46.9°C are well represented by a four-parameter equation, which indicates a standard error (SE) of 1.95% on a single pressure measurement. Forty equilibrium constants Kp(h2[Formula: see text]l1g) for dissociation of structure II methane hydrate into water and methane between 27.0 and 47.7°C and at pressures up to 784 MPa at 45.0°C are best represented by a three-parameter thermodynamic equation, which indicates an SE 1.25% on a single Kp(h2[Formula: see text]l1g) determination. The congruent dissociation melting point C(h2l1gxm) of structure II methane hydrate is at 47.71°C with SE 0.03°C and at pressure 533 MPa with SE 5 MPa. The congruent Kp(h2[Formula: see text]l1g) is 102.9 with SE 0.3 MPa, ΔH°t(h2[Formula: see text]l1g) is 61 531 with SE 244 J mol–1, and the congruent formula is CH4·5.670H2O with SE 0.061H2O. At congruent point ΔV(h2[Formula: see text]l1g) = 0 and its estimate is 1.0 with SE 1.6 cm3 mol–1. Stability range of structure II methane hydrate with water extends from quadruple point Q(h1h2l1g) at 26.7°C and 55.5 MPa up to quadruple point Q(h2h3l1g) at 47.3°C and 620 MPa. The metastability range of structure I methane hydrate with water is discussed.Key words: methane hydrate, clathrate structure II, stability range, dissociation equilibrium constant, formula, congruent melting point, metastability of structure I hydrate.





1971 ◽  
Vol 24 (6) ◽  
pp. 1143 ◽  
Author(s):  
DM Alexander ◽  
DJT Hill ◽  
LR White

Aqueous solubility measurements for a number of non-electrolyte solutes have been analysed using a statistical method of curve fitting to yield the best unbiased estimates of the thermodynamic function changes on solution. The variation of partial molar heat capacity changes with temperature has been discussed.



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