THERMODYNAMIC PROPERTIES OF 0-6 MOL KG-1 AQUEOUS SULFURIC-ACID FROM 273.15 TO 328.15-K

被引:197
作者
CLEGG, SL
RARD, JA
PITZER, KS
机构
[1] LAWRENCE LIVERMORE NATL LAB,DEPT PHYS CHEM,DIV EARTH SCI,LIVERMORE,CA 94550
[2] UNIV CALIF BERKELEY,DEPT CHEM,BERKELEY,CA 94720
来源
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS | 1994年 / 90卷 / 13期
关键词
D O I
10.1039/ft9949001875
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Generalised equations are presented for an extended form of the Pitzer molality-based thermodynamic model, involving an ionic strength-dependent third virial coefficient. Compatibility with the established formulation is retained. Osmotic coefficients, emf measurements, degrees of dissociation of the HSO4- ion, differential enthalpies of dilution and heat capacities for aqueous H2SO4 from 273.15 to 328.15 K, 0-6.1 mol kg-1 and at 1 atm pressure have been critically evaluated. Treating this solution as the mixture H+-HSO4--SO42--H2O, and using hydrogen sulfate dissociation constants from the literature, the model parameters were fitted to the data yielding a self-consistent representation of activities, speciation and thermal properties together with the standard potentials of four electrochemical cells and standard-state heat capacities of the SO42- ion as functions of temperature. The model equations represent the experimental data accurately (without the use of mixture parameters theta(HSO4,SO4) and psi(HSO4,SO4,H)), and should yield values of the osmotic coefficient that are suitable for use as an isopiestic standard over this temperature and molality range. The new model will also enable improved prediction of the properties of mixed acidic sulfate systems.
引用
收藏
页码:1875 / 1894
页数:20
相关论文
共 133 条
[1]   THE VAPOR PHASE ABOVE THE SYSTEM SULFURIC ACID-WATER [J].
ABEL, E .
JOURNAL OF PHYSICAL CHEMISTRY, 1946, 50 (03) :260-283
[2]  
ARCHER D, COMMUNICATION
[3]   EFFECT OF REVISIONS OF DEBYE-HUCKEL LIMITING LAW COEFFICIENTS ON THE THERMODYNAMIC PARAMETERS FOR STRONG-ELECTROLYTE SOLUTIONS [J].
ARCHER, DG .
JOURNAL OF CHEMICAL AND ENGINEERING DATA, 1990, 35 (03) :340-344
[4]   THE DIELECTRIC-CONSTANT OF WATER AND DEBYE-HUCKEL LIMITING LAW SLOPES [J].
ARCHER, DG ;
WANG, PM .
JOURNAL OF PHYSICAL AND CHEMICAL REFERENCE DATA, 1990, 19 (02) :371-411
[5]   THERMODYNAMIC PROPERTIES OF THE NACL+H2O SYSTEM .2. THERMODYNAMIC PROPERTIES OF NACL(AQ), NACL.2H2O(CR), AND PHASE-EQUILIBRIA [J].
ARCHER, DG .
JOURNAL OF PHYSICAL AND CHEMICAL REFERENCE DATA, 1992, 21 (04) :793-829
[6]   THE BEHAVIOUR OF THE LEAD DIOXIDE ELECTRODE .6. THE POTENTIALS OF THE LEAD DIOXIDE-LEAD SULPHATE ELECTRODE [J].
BECK, WH ;
SINGH, KP ;
WYNNEJONES, WFK .
TRANSACTIONS OF THE FARADAY SOCIETY, 1959, 55 (02) :331-338
[7]  
BECK WH, 1960, T FARADAY SOC, V6, P1172
[9]  
Bichowsky F.R., 1936, THERMOCHEMISTRY CHEM
[10]  
BIRON E, 1899, RUSS FIZ KHIM OBSH, V31, P171