Model I: Data for Aqueous H+ - SO42− - Br

The System

The sources of data used to determine mixture parameters W, Q and U in the activity coefficient equations for this ternary system are discussed in section IV.7 of Carslaw et al. (1995), and listed in Table 6 of Massucci et al. (1999). (See also Appendix C of Wexler and Clegg (2002).) Fits of the model are described in Appendix III of Massucci et al., with a minor revision summarised in the paper by Wexler and Clegg. Kleffmann et al. (2000) (J. Phys. Chem. A 104, 8489-8495) compare several of the available data sets with their own measurements, listed here in Table 3, and also present results for HBr partial pressures above aqueous HNO3/H2SO4 solutions. The following types of data were used:
  1. Measurements of the equilibrium vapour pressure of HBr over the ternary solutions.
  2. Rates of uptake of HBr by aqueous H2SO4 (from which the effective Henry's law constant has been derived).
References:
K. S. Carslaw, S. L. Clegg and P. Brimblecombe (1995) J. Phys. Chem. 99, 11557-11574.
M. Massucci, S. L. Clegg and P. Brimblecombe (1999) J. Phys. Chem. A 103, 4209-4226.
A. S. Wexler and S. L. Clegg (2002) J. Geophys. Res. 107, D14, art. no. 4207.

Weights

The values listed in the tables below are based upon those used in the fits of the model. However, they have been normalised for each type of measurement so that the maximum weight for a data point in each table is always unity. Points given zero weight are those which either appear to be in error, or are used for comparison only (and were not fitted). Points with a weight of "-" are outside the temperature or concentration limits of the current model, and have not been assessed for accuracy.

The Data

The experimental data used to fit the activity coefficient model are listed in the tables below. Notes at the end of each one define the tabulated quantities, and identify the sources of the measurements.


(1) Effective Henry's Law Constants of HBr

   wt%      mH2SO4     mHBr           mHBr/pHBr      T       ref.      weight        
   40.3     7.0732    0.3415           5.919E7     248.00     a          1.0       
   40.3     7.0732    0.3415           3.187E7     258.00     a          1.0       
   40.3     7.0732    0.3415           8.082E6     268.00     a          1.0       
   48.8    10.0156    0.3777           1.070E8     218.00     a          1.0       
   48.8    10.0156    0.3777           3.399E7     228.00     a          1.0       
   48.8    10.0156    0.3777           1.209E7     238.00     a          1.0               
   48.8    10.0156    0.3777           3.273E6     248.00     a          1.0       
   48.8    10.0156    0.3777           1.083E6     258.00     a          1.0       
   60.5    15.809     0.1514           2.120E6     218.00     a          1.0       
   60.5    15.809     0.1514           7.721E5     228.00     a          1.0       
   60.5    15.809     0.1514           2.271E5     238.00     a          1.0       
   60.5    15.809     0.1514           8.327E4     248.00     a          1.0       
   60.5    15.809     0.1514           4.845E4     258.00     a          1.0       
   49.5    10.5172    0.64622          7.108E4     298.15     a          1.0       
   57.3    14.5023    0.7400           5.772E3     298.15     a          1.0       
   64.4    19.7456    0.87127          6.622E2     298.15     a          1.0       
   67.6    22.364     0.63307          2.234E2     298.15     a          1.0       
Notes and References


(2) Effective Henry's Law Constants, from Time-Dependent Uptake Experiments

  wt%    mH2SO4           H*      T       ref.   weight       
  60.0   15.295         2.048E6  240.2     b       0.0       
  60.0   15.295         2.038E6  235.4     b       0.0       
  60.0   15.295         3.015E6  231.0     b       0.0       
  60.0   15.295         3.094E6  229.8     b       0.0       
  60.0   15.295         3.149E6  227.5     b       0.0       
  60.0   15.295         4.350E6  221.8     b       0.0       
  60.0   15.295         1.953E7  220.5     b       0.0       
  60.0   15.295         5.172E6  220.1     b       0.0       
  60.0   15.295         7.179E6  220.1     b       0.0       
  66.0   19.793         5.005E4  237.5     b       1.0       
  66.0   19.793         1.527E5  226.9     b       1.0       
  66.0   19.793         2.758E5  225.0     b       1.0       
  66.0   19.793         6.821E5  216.6     b       1.0       
  66.0   19.793         1.137E6  211.6     b       1.0       
  66.0   19.793         1.660E6  208.6     b       1.0       
  66.0   19.793         2.675E6  204.1     b       1.0       
  72.0   26.220         2.967E3  237.9     b       1.0       
  72.0   26.220         6.773E3  227.7     b       1.0       
  72.0   26.220         1.951E4  222.5     b       1.0       
  72.0   26.220         1.968E4  218.8     b       1.0       
  72.0   26.220         4.677E4  211.2     b       1.0       
  72.0   26.220         8.675E4  209.5     b       1.0       
  72.0   26.220         1.135E5  204.3     b       1.0       
  59.6   15.042         8.334E5  233.0     c       1.0       
  59.6   15.042         1.370E6  225.0     c       1.0       
  59.6   15.042         6.611E6  215.0     c       1.0       
  59.6   15.042         1.014E7  208.0     c       1.0       
  64.4   18.445         1.277E5  233.0     c       1.0       
  64.4   18.445         3.722E5  225.0     c       1.0       
  64.4   18.445         1.198E6  215.0     c       1.0       
  64.4   18.445         2.422E6  208.0     c       1.0       
  64.4   18.445         7.776E6  200.0     c       1.0       
  69.8   23.567         1.283E4  233.0     c       1.0       
  69.8   23.567         2.585E4  225.0     c       1.0       
  69.8   23.567         7.432E4  215.0     c       1.0       
  69.8   23.567         1.442E5  208.0     c       1.0       
  69.8   23.567         4.845E5  200.0     c       1.0       
Notes and References


(3) Equilibrium Vapour Pressures of HBr

  wt%    mH2SO4     mHBr          pHBr      T     ref.  weight     
   54     12.54     1.0477      1.8E-007   230     d      0.0       
   54     12.54     1.0477      5.0E-008   220     d      0.0       
   54     12.54     1.0477      1.1E-008   209     d      0.0       
   54     12.23     0.5108      5.4E-008   229     d      0.0       
   54     12.23     0.5108      1.6E-008   218     d      0.0       
   60     15.70     0.5651      2.5E-007   224     d      1.0       
   60     15.70     0.5651      7.9E-008   217     d      0.0       
   60     15.33     0.0836      1.3E-007   234     d      1.0       
   60     15.33     0.0836      8.6E-008   230     d      1.0       
   60     15.33     0.0836      4.2E-008   225     d      1.0       
   60     15.33     0.0836      2.4E-008   224     d      0.0      
   66     20.43     0.6403      1.4E-005   233     d      1.0       
   66     20.43     0.6403      8.8E-006   228     d      1.0       
   66     20.43     0.6403      3.4E-006   218     d      0.0      
   66     20.43     0.6403      7.5E-007   212     d      1.0       
   66     20.43     0.6403      3.4E-007   209     d      0.0      
   66     19.88     0.0944      1.3E-006   234     d      1.0       
   66     19.88     0.0944      1.3E-006   233     d      1.0       
   66     19.88     0.0944      8.6E-007   228     d      1.0       
   66     19.88     0.0944      3.2E-007   219     d      1.0       
   66     19.88     0.0944      1.0E-007   214     d      1.0       
Notes and References


(4) Equilibrium Vapour Pressures of HBr

  wt%    mH2SO4    mHBr      pHBr       T     ref.  weight    
  45.3   10.33    2.755     1.88E-6   241.92   e      1.0     
  45.3   10.33    2.755     1.16E-6   237.03   e      1.0     
  45.3   10.33    2.755     5.13E-7   231.21   e      1.0     
  45.3   10.33    2.755     3.12E-7   227.27   e      1.0     
  45.3   10.33    2.755     1.61E-7   222.39   e      1.0     
  45.3   10.33    2.755     8.84E-8   217.69   e      1.0     
  55.3   12.96    0.3409    4.43E-7   242.82   e      1.0     
  55.3   12.96    0.3409    2.55E-7   237.93   e      1.0     
  55.3   12.96    0.3409    1.43E-7   233.12   e      1.0     
  55.3   12.96    0.3409    1.43E-7   233.12   e      1.0     
  55.3   12.96    0.3409    7.87E-8   228.28   e      1.0     
  55.3   12.96    0.3409    7.69E-8   228.28   e      1.0     
  55.3   12.96    0.3409    3.44E-8   223.41   e      1.0     
  55.3   12.96    0.3409    2.32E-8   218.71   e      1.0     
  55.3   12.96    0.3409    1.33E-8   213.99   e      1.0     
  57.5   14.20    0.3529    1.06E-6   242.92   e      1.0     
  57.5   14.20    0.3529    7.21E-7   238.13   e      1.0     
  57.5   14.20    0.3529    3.14E-7   233.32   e      1.0     
  57.5   14.20    0.3529    1.61E-7   228.38   e      1.0     
  57.5   14.20    0.3529    7.45E-8   223.51   e      1.0     
  57.5   14.20    0.3529    5.74E-8   218.81   e      1.0     
  57.5   14.20    0.3529    3.73E-8   214.20   e      1.0     
  55.1   14.20    1.665     9.12E-7   224.22   e      1.0     
  55.1   14.20    1.665     7.08E-6   240.53   e      1.0     
  55.1   14.20    1.665     2.32E-6   231.81   e      1.0     
  55.1   14.20    1.665     1.69E-6   227.87   e      1.0     
  55.1   14.20    1.665     7.94E-7   220.55   e      1.0     
  55.1   14.20    1.665     7.84E-7   220.45   e      1.0     
  60.4   15.84    0.2253    4.34E-7   230.15   e      1.0     
  60.4   15.84    0.2253    4.46E-7   230.60   e      1.0     
  60.4   15.84    0.2253    1.27E-6   239.72   e      1.0     
  60.4   15.84    0.2253    3.69E-7   229.90   e      1.0     
  60.4   15.84    0.2253    9.80E-7   239.33   e      1.0     
  60.4   15.84    0.2253    1.52E-7   221.70   e      1.0     
  62.5   17.17    0.1285    1.15E-6   238.43   e      0.0     
  62.5   17.17    0.1285    7.22E-7   233.62   e      0.0     
  62.5   17.17    0.1285    4.80E-7   228.89   e      0.0     
  62.5   17.17    0.1285    2.85E-7   224.22   e      0.0     
  62.5   17.17    0.1285    1.54E-7   218.61   e      0.0     
  62.5   17.17    0.1285    9.30E-8   214.20   e      0.0     
  62.5   17.17    0.1285    4.94E-8   208.83   e      0.0     
  62.4   17.27    0.2557    1.53E-6   232.42   e      0.0     
  62.4   17.27    0.2557    9.13E-7   227.57   e      0.0     
  62.4   17.27    0.2557    5.35E-7   222.69   e      0.0     
  62.4   17.27    0.2557    3.43E-7   217.79   e      0.0     
  62.4   17.27    0.2557    2.01E-7   212.96   e      0.0     
  62.4   17.27    0.2557    1.26E-7   207.48   e      0.0     
  62.4   17.27    0.2557    5.04E-8   201.65   e      0.0     
  62.8   17.57    0.2588    1.58E-6   233.12   e      1.0     
  62.8   17.57    0.2588    9.44E-7   228.18   e      1.0     
  62.8   17.57    0.2588    5.77E-7   223.51   e      1.0     
  62.8   17.57    0.2588    3.30E-7   218.71   e      1.0     
  62.8   17.57    0.2588    1.79E-7   214.09   e      1.0     
  62.8   17.57    0.2588    2.50E-6   238.03   e      1.0     
  64.1   18.36    0.1048    1.01E-6   233.32   e      0.0     
  64.1   18.36    0.1048    6.83E-7   228.48   e      0.0     
  64.1   18.36    0.1048    4.08E-7   223.80   e      0.0     
  64.1   18.36    0.1048    2.52E-7   219.12   e      0.0     
  64.1   18.36    0.1048    1.28E-7   213.89   e      0.0     
  64.1   18.36    0.1048    1.64E-6   238.13   e      0.0     
  65.1   19.31    0.1877    1.47E-7   207.15   e      1.0     
  65.1   19.31    0.1877    3.32E-7   214.35   e      1.0     
  65.1   19.31    0.1877    9.70E-7   223.15   e      1.0     
  65.1   19.31    0.1877    9.88E-7   223.25   e      1.0     
  65.1   19.31    0.1877    2.67E-7   214.65   e      1.0     
  65.1   19.31    0.1877    1.39E-7   206.75   e      1.0     
  65.3   19.36    0.1150    1.41E-6   232.22   e      0.0     
  65.3   19.36    0.1150    1.01E-6   227.57   e      0.0     
  65.3   19.37    0.1150    6.01E-7   222.19   e      0.0     
  65.3   19.37    0.1150    4.02E-7   218.30   e      0.0     
  65.3   19.37    0.1150    1.62E-7   211.21   e      0.0     
  65.3   19.37    0.1150    1.25E-7   206.75   e      0.0     
  65.3   19.37    0.1150    5.84E-8   202.90   e      0.0     
  65.3   19.37    0.1150    2.35E-6   238.03   e      0.0     
  66.9   20.80    0.1119    5.68E-7   213.89   e      0.0     
  66.9   20.80    0.1119    3.31E-7   209.04   e      0.0     
  66.9   20.80    0.1119    2.13E-6   228.18   e      0.0     
  66.9   20.80    0.1119    1.53E-6   223.41   e      0.0     
  66.9   20.80    0.1119    1.00E-6   218.80   e      0.0     
  66.9   20.80    0.1119    3.24E-7   209.24   e      0.0     
  69.7   23.50    0.0210    3.68E-7   213.99   e      0.0     
  69.7   23.50    0.0210    2.02E-7   207.17   e      0.0     
  69.7   23.50    0.0210    5.69E-7   217.79   e      0.0     
  69.7   23.50    0.0210    1.11E-6   226.15   e      0.0     
  69.7   23.50    0.0210    2.59E-7   206.24   e      0.0     
  69.7   23.50    0.0210    5.01E-7   215.22   e      0.0     
  69.7   23.50    0.0210    1.29E-6   224.63   e      0.0     
  69.7   23.50    0.0210    2.31E-6   231.01   e      0.0     
  69.7   23.50    0.0210    9.10E-7   219.99   e      0.0     
  69.7   23.50    0.0210    3.80E-7   210.48   e      0.0     
  69.9   23.70    0.0104    1.22E-6   232.92   e      0.0     
  69.9   23.70    0.0104    9.32E-7   228.58   e      0.0     
  69.9   23.70    0.0104    5.93E-7   223.71   e      0.0     
  69.9   23.70    0.0104    3.28E-7   217.59   e      0.0     
  69.9   23.70    0.0104    2.05E-7   213.27   e      0.0     
  69.9   23.70    0.0104    1.16E-7   208.00   e      0.0     
  70.6   24.51    0.0106    2.19E-6   237.63   e      0.0     
  70.6   24.51    0.0106    1.66E-6   232.82   e      0.0     
  70.6   24.51    0.0106    1.21E-6   229.09   e      0.0     
  70.6   24.51    0.0106    7.43E-7   224.63   e      0.0     
  70.6   24.51    0.0106    4.03E-7   218.51   e      0.0     
  70.6   24.51    0.0106    2.73E-7   213.27   e      0.0     
  72.2   26.50    0.00689   1.67E-6   227.77   e      0.0     
  72.2   26.50    0.00689   1.35E-6   222.90   e      0.0     
  72.2   26.50    0.00689   9.07E-7   218.10   e      0.0     
  72.2   26.50    0.00689   3.17E-6   233.52   e      0.0     
  72.2   26.50    0.00689   1.65E-6   225.85   e      0.0     
  72.2   26.50    0.00689   8.16E-7   216.87   e      0.0     
Notes and References