Characterization of meta-Cresol Purple for spectrophotometric pH measurements in saline and hypersaline media at sub-zero temperatures
2017
Accurate pH measurements in polar waters and sea ice brines require pH indicator dyes characterized at near-zero and below-zero temperatures and high salinities. We present experimentally determined physical and chemical characteristics of purified meta-Cresol Purple (mCP) pH indicator dye suitable for pH measurements in seawater and conservative seawater-derived brines at salinities (S) between 35 and 100 and temperatures (T) between their freezing point and 298.15 K (25 °C). Within this temperature and salinity range, using purified mCP and a novel thermostated spectrophotometric device, the pH on the total scale (pHT) can be calculated from direct measurements of the absorbance ratio R of the dye in natural samples as
$${\boldsymbol{p}}{{\boldsymbol{H}}}_{{\boldsymbol{T}}}{\boldsymbol{=}}{\boldsymbol{-}}{\bf{log}}({{\boldsymbol{k}}}_{{\bf{2}}}^{{\boldsymbol{T}}}{{\boldsymbol{e}}}_{{\bf{2}}}){\boldsymbol{+}}\,{\bf{log}}(\frac{{\boldsymbol{R}}{\boldsymbol{-}}{{\boldsymbol{e}}}_{{\bf{1}}}}{{\bf{1}}{\boldsymbol{-}}{\boldsymbol{R}}\frac{{{\boldsymbol{e}}}_{{\bf{3}}}}{{{\boldsymbol{e}}}_{{\bf{2}}}}})$$
p
H
T
=
−
log
(
k
2
T
e
2
)
+
log
(
R
−
e
1
1
−
R
e
3
e
2
)
Based on the mCP characterization in these extended conditions, the temperature and salinity dependence of the molar absorptivity ratios and −
$${\bf{log}}({{\boldsymbol{k}}}_{{\bf{2}}}^{{\boldsymbol{T}}}{{\boldsymbol{e}}}_{{\bf{2}}})$$
log
(
k
2
T
e
2
)
of purified mCP is described by the following functions: e
1 = −0.004363 + 3.598 × 10−5
T, e
3/e
2 = −0.016224 + 2.42851 × 10−4
T + 5.05663 × 10−5(S − 35), and −
$${\bf{log}}({{\boldsymbol{k}}}_{{\bf{2}}}^{{\boldsymbol{T}}}{{\boldsymbol{e}}}_{{\bf{2}}})$$
log
(
k
2
T
e
2
)
= −319.8369 + 0.688159 S −0.00018374 S
2 + (10508.724 − 32.9599 S + 0.059082S
2) T−1 + (55.54253 − 0.101639 S) ln T −0.08112151T. This work takes the characterisation of mCP beyond the currently available ranges of 278.15 K ≤ T ≤ 308.15 K and 20 ≤ S ≤ 40 in natural seawater, thereby allowing high quality pHT measurements in polar systems.
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