2
0
2017
arc
fer
0
journal
Original
Arcis, H.
Ferguson, J. P.
Applegarth, L. M. S. G. A.
Zimmerman, G. H.
Tremaine, P. R.
J. Chem. Thermodyn.
2017
2020-09-29
Ionization of boric acid in water from 298 K to 623 K by AC conductivity and Raman spectroscopy
Boric acid is used in the primary coolant of pressurized water nuclear reactors (PWRs) as a neutron absorber to control the reactor efficiency. Accurate thermodynamic and transport properties are needed to model the boron precipitation reactions in fuel deposit crevices, which adversely affect the neutron flux. Here, we report (i) new values for the boric acid ionization constant that have been measured from T = 298 K to T = 623 K at a constant pressure p 20 MPa using a unique high-precision flow-through AC electrical conductance instrument and (ii) quantitative reduced isotropic Raman spectra for a 1 molal boric acid aqueous solution from T = 298 K to T = 623 K at a constant pressure p = 25 MPa. Frequency-dependent electrical conductivities of aqueous solutions of boric acid have been determined over ionic strengths from 10 4 to 10 1 mol kg-1. The concentration-dependent experimental molar conductivities, K, were analysed with the Turq-Blum-Bernard-Kunz ( TBBK ) ionic conductivity model to yield values for the ionization constant of boric acid, Kb 11, to an accuracy of +-10% at T = 623 K and +-5% at T 6 600 K. These compare well with extrapolated values from accurate potentiometric measurements at temperatures up to 563 K and steam saturation pressures. These results also confirm the validity of the new 2006 IAPWS (International Association for the Properties of Water and Steam) formulation for the ionization constant of water, pKw. The Raman results did not show any evidence of metaboric acid formation under hydrothermal conditions.
Boric acid
Conductivity
Equilibrium constant
Hydrothermal solution
Raman spectroscopy
10.1016/j.jct.2016.11.007
106
187-198
1
InChI=1S/BH3O3/c2-1(3)4/h2-4H
KGBXLFKZBHKPEV-UHFFFAOYSA-N
boric acid
BH3O3
1
Commercial source
1
99.9995
6
Stated by supplier
2
InChI=1S/H2O/h1H2
XLYOFNOQVPJJNP-UHFFFAOYSA-N
water
H2O
1
Commercial source
1
De-gassed by boiling or ultrasonically
2
99.9
3
Estimated by the compiler
1
2
1
1
1
Principal objective of the work
AB
TRC
7/31/2017
1
Electrical conductivity, S/m
Alternating current cell with electrodes
Liquid
Direct value, X
2
1
Data file compiler
Propagation of evaluated standard uncertainties
95
Liquid
1
Temperature, K
Liquid
2
Pressure, kPa
Liquid
3
Molality, mol/kg
1
Liquid
1
298.149
6
2
19767
5
3
0.000461
4
1
2.9e-05
3
1
2.23e-05
1
298.149
6
2
19767
5
3
0.0010344
5
1
4.34e-05
3
1
2.16e-05
1
298.149
6
2
19767
5
3
0.0022144
5
1
7.29e-05
3
1
2.19e-05
1
298.149
6
2
19767
5
3
0.0035583
5
1
8.46e-05
3
1
2.29e-05
1
298.149
6
2
19767
5
3
0.0068014
5
1
0.0001044
4
1
2.35e-05
1
298.149
6
2
19767
5
3
0.0144789
6
1
0.0001407
4
1
1.47e-05
1
298.149
6
2
19767
5
3
0.0322705
6
1
0.0002032
4
1
2.93e-05
1
298.149
6
2
19767
5
3
0.0562648
6
1
0.0002612
4
1
5.01e-05
1
298.149
6
2
19767
5
3
0.1313178
7
1
0.0005133
4
1
3.09e-05
1
373.334
6
2
19683
5
3
0.0022155
5
1
0.0001549
4
1
9.3e-06
1
373.334
6
2
19683
5
3
0.0144911
6
1
0.0001746
4
1
3.49e-05
1
373.334
6
2
19683
5
3
0.0238066
6
1
0.000262
4
1
1.57e-05
1
373.334
6
2
19683
5
3
0.0433428
6
1
0.0004095
4
1
2.46e-05
1
373.334
6
2
19683
5
3
0.0742084
6
1
0.000597
4
1
3.59e-05
1
448.228
6
2
19666
5
3
0.0004623
4
1
0.0003015
4
1
1.81e-05
1
448.228
6
2
19666
5
3
0.0029397
5
1
0.000347
4
1
2.09e-05
1
448.228
6
2
19666
5
3
0.0087299
5
1
0.0004212
4
1
2.53e-05
1
448.228
6
2
19666
5
3
0.0128711
6
1
0.0004728
4
1
2.85e-05
1
448.228
6
2
19666
5
3
0.0243034
6
1
0.0005896
4
1
3.55e-05
1
448.228
6
2
19666
5
3
0.0379116
6
1
0.0007065
4
1
4.24e-05
1
448.228
6
2
19666
5
3
0.0701257
6
1
0.0009394
4
1
5.67e-05
1
448.228
6
2
19666
5
3
0.1014745
7
1
0.0011408
5
1
6.85e-05
1
523.321
6
2
19674
5
3
0.0005523
4
1
0.0003819
4
1
2.3e-05
1
523.321
6
2
19674
5
3
0.0017569
5
1
0.000393
4
1
2.36e-05
1
523.321
6
2
19674
5
3
0.0045344
5
1
0.000408
4
1
2.45e-05
1
523.321
6
2
19674
5
3
0.0095168
5
1
0.0004455
4
1
2.67e-05
1
523.321
6
2
19674
5
3
0.0216789
6
1
0.0005147
4
1
3.09e-05
1
523.321
6
2
19674
5
3
0.0423672
6
1
0.0006322
4
1
3.79e-05
1
523.321
6
2
19674
5
3
0.0721563
6
1
0.0007796
4
1
4.68e-05
1
523.321
6
2
19674
5
3
0.1017491
7
1
0.0009215
4
1
5.53e-05
1
548.354
6
2
19600
3
3
0.0008359
4
1
0.0003744
4
1
2.48e-05
1
548.354
6
2
19600
3
3
0.0023682
5
1
0.0003849
4
1
2.51e-05
1
548.354
6
2
19600
3
3
0.0055368
5
1
0.000406
4
1
2.68e-05
1
548.354
6
2
19600
3
3
0.0120772
6
1
0.0004467
4
1
2.69e-05
1
548.354
6
2
19600
3
3
0.02063
6
1
0.0004952
4
1
2.99e-05
1
548.354
6
2
19600
3
3
0.0288029
6
1
0.000538
4
1
3.25e-05
1
548.354
6
2
19600
3
3
0.0462516
6
1
0.000617
4
1
3.7e-05
1
548.354
6
2
19600
3
3
0.1014745
7
1
0.0009213
4
1
5.53e-05
1
547.198
6
2
20900
3
3
0.0009361
4
1
0.000382
4
1
2.34e-05
1
547.198
6
2
20900
3
3
0.0023709
5
1
0.0003946
4
1
2.41e-05
1
547.198
6
2
20900
3
3
0.0037443
5
1
0.0004047
4
1
2.47e-05
1
547.198
6
2
20900
3
3
0.0058604
5
1
0.0004193
4
1
2.57e-05
1
547.198
6
2
20900
3
3
0.0088455
5
1
0.000439
4
1
5.12e-05
1
547.198
6
2
20900
3
3
0.011626
6
1
0.0004588
4
1
5.19e-05
1
547.198
6
2
20900
3
3
0.0151475
6
1
0.000481
4
1
5.12e-05
1
547.198
6
2
20900
3
3
0.0242897
6
1
0.0005351
4
1
3.21e-05
1
571.07
6
2
19463
5
3
0.000429
4
1
0.0003234
4
1
2.19e-05
1
571.07
6
2
19463
5
3
0.0011392
5
1
0.000331
4
1
2.23e-05
1
571.07
6
2
19463
5
3
0.0042027
5
1
0.0003499
4
1
2.3e-05
1
572.819
6
2
20769
5
3
0.0002704
4
1
0.0003391
4
1
2.07e-05
1
572.819
6
2
20769
5
3
0.0005746
4
1
0.000349
4
1
2.11e-05
1
572.819
6
2
20769
5
3
0.0014827
5
1
0.0003585
4
1
2.17e-05
1
572.819
6
2
20769
5
3
0.0028699
5
1
0.0003686
4
1
2.22e-05
1
572.819
6
2
20769
5
3
0.0063367
5
1
0.0003887
4
1
2.35e-05
1
572.819
6
2
20769
5
3
0.0103194
6
1
0.0004145
4
1
2.5e-05
1
572.819
6
2
20769
5
3
0.0171924
6
1
0.0004455
4
1
2.68e-05
1
572.819
6
2
20769
5
3
0.0360977
6
1
0.000516
4
1
3.1e-05
1
572.819
6
2
20769
5
3
0.0527566
6
1
0.000569
4
1
3.42e-05
1
597.9
6
2
20618
5
3
0.0004999
4
1
0.0002167
4
1
2.62e-05
1
597.9
6
2
20618
5
3
0.0008991
4
1
0.0002226
4
1
2.68e-05
1
597.9
6
2
20618
5
3
0.0017557
5
1
0.0002274
4
1
2.74e-05
1
597.9
6
2
20618
5
3
0.0031559
5
1
0.0002328
4
1
2.8e-05
1
597.9
6
2
20618
5
3
0.0059303
5
1
0.0002422
4
1
2.92e-05
1
597.9
6
2
20618
5
3
0.0103166
6
1
0.0002573
4
1
3.11e-05
1
597.9
6
2
20618
5
3
0.0256109
6
1
0.0003028
4
1
3.63e-05
1
621.126
6
2
20620
4
3
0.0003582
4
1
0.0001169
4
1
1.4e-05
1
621.126
6
2
20620
4
3
0.0009385
4
1
0.0001171
4
1
1.41e-05
1
621.126
6
2
20620
4
3
0.0028507
5
1
0.0001202
4
1
1.44e-05
1
621.126
6
2
20620
4
3
0.0049805
5
1
0.0001252
4
1
1.5e-05
1
621.126
6
2
20620
4
3
0.0110664
6
1
0.0001384
4
1
1.66e-05
1
621.126
6
2
20620
4
3
0.0190799
6
1
0.0001608
4
1
1.93e-05