Sulfur reactor chemistry

[CamGG]

Randy,
I'm currently in the process of setting up a sulfur reactor and documenting the results. Through my own research I've found a lacking of information to sulfur denitrification, especially in focus of aquariums. Many reaction equations I've found vary vastly from each other and exclude products in the reduction reactions. I would like to compile an in depth article regarding the chemistry and stoichiometry of the denitrification reaction. I was wondering if you would be willing to answer some chemical based questions as I collect and research my data and open a private message dialog with me.

 

[Randy Holmes-Farley]

Welcome to Reef2Reef!

I discuss the chemistry briefly in several articles:

THis one is more on the hydrogen sulfide end of the sulfur cycle:

http://reefkeeping.com/issues/2005-12/rhf/index.php#1

and this one relates to sulfur reactors specifically:

Nitrate in the Reef Aquarium - REEFEDITION

Nitrate is an ion that has long dogged aquarists. It is typically formed in aquaria through the digestion of foods, and in many aquaria it builds up and can be difficult to keep at natural levels. In the past, many aquarists performed water changes with nitrate reduction as one of the primary...

www.reefedition.com

Sulfur Denitrators

In these systems, bacteria use elemental sulfur and produce N2 from the sulfur and nitrate according the following equation (or something similar):

2 H2O + 5 S + 6 NO3– → 3 N2 + 5 SO42- + 4 H+

The production of acid (H+) in this reactor can tend to reduce the aquarium alkalinity. It has also been suggested to pass the effluent of such a reactor through a bed of aragonite to use the acid (H+) produced to dissolve the calcium carbonate, and thereby provide calcium and alkalinity to the aquarium. While that is a fine idea, it doesn’t add much calcium and alkalinity to most aquaria.

To estimate the magnitude of the effect, we start with a liberal estimate of how much nitrate might be removed. Say 10 ppm of nitrate per week.

10 ppm nitrate = 0.16 mmole/L of nitrate

Since 4 moles of H+ are produced for every 6 moles of nitrate consumed, this will produce

0.107 mmoles/L of H+ per week

How much calcium this could produce?

Assume that it takes one proton to dissolve one calcium carbonate:

CaCO3 + H+ → Ca2+ + HCO3–

Clearly, this is a substantial overestimate because much of the acid will be used up driving the pH down to the point where CaCO3 can even begin to dissolve. Consequently, we have an upside limit of 0.107 mmoles of Ca2+ per week. Since calcium weighs 40 mg/mmol, that’s 4.3 ppm Ca2+ per week.

For comparison, an aquarist adding 2% of the tank volume in saturated limewater daily is adding on the order of 16 ppm of calcium per day. Consequently, this method may not be especially useful for maintaining calcium. Additionally, the acid produced will have a long term lowering effect on the alkalinity. In fact, it is double dipping on the alkalinity depletion since alkalinity is consumed when the nitrate is produced, and again when it is removed in the denitrator. So if you use a sulfur denitrator, be sure to monitor the alkalinity in the aquarium.

http://reefkeeping.com/issues/2004-12/rhf/index.htm