Thermodynamic properties of aqueous diethanolamine (DEA), N,N-dimethylethanolamine (DMEA), and their chloride salts: apparent molar heat capacities and volumes at temperatures from 283.15 to 328.15 K

2000 ◽  
Vol 78 (1) ◽  
pp. 151-165 ◽  
Author(s):  
Christopher Collins ◽  
Joelle Tobin ◽  
Dmitri Shvedov ◽  
Rom Palepu ◽  
Peter R Tremaine

Apparent molar heat capacities Cp,ϕ and apparent molar volumes Vϕ for aqueous diethanolamine (HOC2H4)2NH, diethanolammonium chloride (HOC2H4)2NH2Cl, N,N'-dimethylethanolamine (HOC2H4)(CH3)2N, and N,N'-dimethylethanolammonium chloride (HOC2H4)(CH3)2NHCl were determined from 283.15 to 328.15 K with a Picker flow microcalorimeter and vibrating tube densimeter. The experimental results have been analyzed in terms of Young's Rule with the Guggenheim form of the extended Debye-Hückel equation and appropriate corrections for chemical relaxation effects. These calculations lead to standard partial molar heat capacities and volumes for the neutral amines, (HOC2H4)2NH(aq) and (HOC2H4)(CH3)2N(aq), and the ions (HOC2H4)2NH2+(aq) and (HOC2H4)(CH3)2NH+(aq) over the experimental temperature range. Key words: standard partial molar volumes, standard partial molar heat capacities, diethanolamine, dimethyethanolamine, aqueous alkanolamine ionization.

1988 ◽  
Vol 66 (4) ◽  
pp. 881-896 ◽  
Author(s):  
Jamey K. Hovey ◽  
Loren G. Hepler ◽  
Peter R. Tremaine

Calorimetric and densimetric measurements have led to apparent molar heat capacities and volumes for aqueous solutions of the mixed electrolytes [(CH3)4N]4EDTA + (CH3)4NOH, Na4EDTA + NaOH, and K4EDTA + KOH, and single electrolytes Na2H2EDTA and [(CH3)4N]3[HEDTA] at 25 °C. We have analyzed these results in terms of Young's rule and Pitzer's ion interaction model to obtain standard state partial molar heat capacities and volumes of EDTA4−(aq), HEDTA3−(aq), H2EDTA2−(aq), NaEDTA3−(aq), and KEDTA3−(aq) at 25 °C. For these calculations it was also necessary to evaluate the "relaxation" contribution to the measured heat capacities of some solutions. The partial molar heat capacities obtained here have been used with enthalpies from previous investigations for calculations of several equilibrium constants over wide ranges of temperature; volumes can be used for similar calculations of the effects of pressure.


1986 ◽  
Vol 64 (2) ◽  
pp. 353-359 ◽  
Author(s):  
Leslie Barta ◽  
Loren G. Hepler

Densities of aqueous solutions of AlCl3 (containing dilute HCl) have been measured at 10, 25, 40, and 55 °C with results that have led to defined apparent molar volumes. We have used the Pitzer ion interaction model as the basis for analyzing these apparent molar volumes to obtain standard state (infinite dilution) partial molar volumes of AlCl3(aq) at each temperature. We have also made similar use of apparent molar heat capacities of aqueous solutions of AlCl3–HCl and Al(NO3)3–HNO3 from Hovey and Tremaine to obtain standard state partial molar heat capacities of AlCl3(aq) and Al(NO3)3(aq) at these same temperatures. Finally, the standard state partial molar volumes and heat capacities have been used with the Helgeson–Kirkham semi-theoretical equation of state for aqueous ions to provide a basis for estimating the thermodynamic properties of Al3+(aq) at high temperatures and pressures.


1983 ◽  
Vol 61 (11) ◽  
pp. 2509-2519 ◽  
Author(s):  
José A. Barbero ◽  
Loren G. Hepler ◽  
Keith G. McCurdy ◽  
Peter R. Tremaine

A flow microcalorimeter and vibrating tube densimeter were used at 25 °C to obtain apparent molar heat capacities and volumes of aqueous NaHCO3, KHCO3, NaHSO3, and KHSO3, from 0.1 to 1.0 mol kg−1, aqueous CO2 from 0.01 to 0.10 mol kg−1 and aqueous SO2 from 0.045 to 2.0 mol kg−1. The contribution of "chemical relaxation" (changes in equilibrium state and enthalpy due to change in temperature) to the experimental heat capacities of aqueous SO2 required special attention, leading to the derivation of a new equation for calculating this effect. Standard state values for the heat capacities and volumes of aqueous CO2, SO2, HCO3−, and HSO3− were obtained from the apparent molar properties by extrapolation to infinite dilution. Combining these results with other thermodynamic data from the literature gave estimates of log K1b the equilibrium constant for the first neutralization of CO2 and SO2, at high temperatures. The results for CO2 reproduce very accurate literature values to within 0.2 at 200 °C. The expression for the reaction [Formula: see text] log K1b = 22.771 + 2776.0/T–8.058 log T, is consistent with the sparse and limited experimental data.


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