PH and Temperature in Sea Water

FuzzyLogic

Member
I hope you chemistry people can help me. I know that if the temperature changes, so does the pH, even though the concentration of the acid or base causing pH remains constant. What is the temperature correction (in pH units) for sea water for every Celsius degree rise in temperature?
 
The question is not that simple, and you may not like the answer. :D

Temperature changes do two things. The first has to do with pH meters that respond differently at different temperatures. What changes here is the slope of the relationship between the mv that the eelctrode reports, and the true pH.

When you set the first calibration point at pH 7, that point is fixed. Then when you set the second calibration point (say, 4 or 10), that determines the relationship for your meter between pH and the mv change reported by the electrode. That slope is about 54 mv/pH unit at 0 deg C, and 64 mv/pH unit at 50 deg C.

pH meters often allow that effect to be corrected for by adjusting a knob or setting the temperature. It is not, however, a simple change in pH units. If the pH is close to 7, the actuall correction is very small. If the pH is far from that, say 2 or 13, then the correction with temperature changes is large.

The other effect has to do with the buffers in the water itself, which can change their acidity with temperature changes. Some may effectively shift the water to lower pH as temperature rises, and some may shift it to highe rpH as temperature rises. Even more complicated, the ionization of water itself changes as temperature changes, and that really confounds pH changes with temperature.

This article has more:

Measuring pH with a Meter
http://www.advancedaquarist.com/issues/feb2004/chem.htm

and this one talks about buffers


A Comparison of pH Calibration Buffers
http://reefkeeping.com/issues/2005-02/rhf/index.htm
 
This article (especially Figure 1) may have the information that you want if you want a detailed analysis:

Full pdf:

http://neon.otago.ac.nz/chemistry/research/mfc/pubs/co2-ph/b97086.pdf

abstract:

The temperature dependence of pH in surface seawater. Hunter, K.A. (1998). Deep-Sea Research 45: 1919-1930.

This paper describes an investigation of the temperature dependence of pH in surface seawater as a function of salinity and CO2 composition using the most recent values for the equilibrium constants of the CO2 system in seawater. A substantial discrepancy was found in one of the previously published algorithm used to correct shipboard pH measurements made at 25oC to the in situ temperature. Over the range of values expected in oceanic surface waters, both salinity and total alkalinity affected the pH temperature correction to a small extent (DpH < 0.0017). However, by using salinity to estimate the total alkalinity, the error in the calculated pH temperature correction is reduced to less than 0.0002 pH unit over the temperature range 0-40oC.
 
Thanks for posting those articles. Basically, if the pH is within the normal operating range of an aquarium and the temperature varies no more than +/- 2 degrees C, the temperature correction is insignificant. I think??
 
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