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Indicator for testing for water hardness

Submitted by sat on 17 May 2016

Answer reviewed 13 February 2023

Eriochrome Black T (or Mordant Black 11) is used in complexometric titrations to indicate the endpoint of a water hardness titration. Eriochrome Black T (Mordant Black 11), which is a solid brown–black powder with a faint metallic sheen, is soluble in water and slightly soluble in ethanol.1 

We are not sure why your Eriochrome Black did not fully dissolve. One reference suggests that ammonia solution (NH4OH = NH3 in H2O) has a shelf life of 2 years when stored at 25 °C.2 However, even if the concentration of ammonia reduces slightly due to loss of ammonia gas from the solution, it is unlikely to affect the solubility of the Eriochrome Black.

Alternative methods

We found the following alternative methods for using Eriochrome Black as an indicator.

  1. Dry powder form: Grind and mix 1 g of the solid Eriochrome Black T with 100 g of sodium chloride. Add about 0.2 g of this solid mixture to the titration flask for each titration.3
  2. In ethanol: 1% (w/v) solution. Dissolve 1.0 g of Eriochrome Black T in 80 mL 95% ethanol. Make up to 100 mL with 95% ethanol.3
  3. In ethanolamine/ethanol: Dissolve 0.2 g of Eriochrome Black T in 15 mL of triethanolamine and then add 5 mL of absolute ethanol.4 
  4. Substitution: Use Calmagite in place of Eriochrome Black T. Dissolve 0.05 g of Calmagite in sufficient distilled water and make up to 50 mL.5 

Notes

Additional information

Shelf life: Eriochrome Black T solution has a short shelf life therefore should be prepared fresh in minimal quantities on the day of testing. Excess Eriochrome Black T indicator solution should be collected for removal by specialist waste disposal contractors. It is harmful to marine life and should not be flushed into waterways.

The dry powder mixture has a long shelf life.

The pH of the reaction: The reaction needs to be conducted within the pH range of 7–11. Therefore, prior to titrating, the test solutions are adjusted to pH 9–10 with the addition of ammonia/ammonium chloride buffer to the titration flask when adding Eriochrome Black T.

Water hardness is a measure of the amount of calcium and magnesium salts dissolved in water.7 It can be determined by performing a complexometric titration with a complexing agent such as ethylenediaminetetraacetic acid (EDTA) in the presence of an indicator such as Eriochrome Black T.8 

When blue Eriochrome Black T indicator is added to a water sample, it forms a red-coloured Ca-Mg-Eriochrome Black T complex.9 When EDTA is added dropwise from a burette, the complexing agent binds to the Ca2+ and Mg2+ ions in the water sample. When all the metal ions have been complexed with EDTA, the Eriochrome Black T molecules are liberated and change colour to steel blue.10 The colour change of the solution to blue indicates the end point of the titration.

References

1 Chem Supply website, (2020) ‘Eriochrome black T Safety Data Sheet’.  Search https://www.chemsupply.com.au/ to source the latest Safety Data Sheet via the product information page.

2 Sigma Aldrich. 2003. Ammonium Hydroxide, ACS Reagent, Retrieved from the Sigma Aldrich website: https://www.sigmaaldrich.com/deepweb/assets/sigmaaldrich/product/documen... 

3 CLEAPPS. (2021, March 9). All CLP Recipe Sheets. Retrieved from the CLEAPPS website, http://science.cleapss.org.uk/Resource-Info/All-CLP-Recipe-Sheets.aspx (login required)

4 University of Canterbury, (nd). ‘Determination of Total Calcium and Magnesium Ion Concentration’. Retrieved from the University of Canterbury website: http://www.canterbury.ac.nz/media/documents/science-outreach/magnesium_c... 

5 Titrations, (nd). ‘Complexometric titration - methods of the end point detection’. Retrieved 22 February 2023) from the Titrations info website. http://www.titrations.info/complexometric-titration-end-point-detection

6 Brubaker, J. (2018, March 13), Eriochrome Black T Solution Preparation. Retrieved from the Sciencing website. https://sciencing.com/eriochrome-black-solution-preparation-8457364.html

7 Sigma-Aldrich, (2023, February 14) ‘Hydroxylamine hydrochloride’, Search https://www.sigmaaldrich.com/AU/en to source the latest Safety Data Sheet via the product information page.

8 Titrations, (nd). ‘Determination of water total hardness by complexometric titration’. Retrieved (22 February 2023) from the Titrations info website.  http://www.titrations.info/EDTA-titration-water-hardness 

9 Titrations, (nd). ‘General information about complexometric titration’. Retrieved (22 February 2023) from the Titrations info website: http://www.titrations.info/complexometric-titration 

10 S.K Engineering Academy.2012-2013. Unit 1, Water Technology. Retrieved from the S.K Engineering Academy website http://sk4education.com/engineering/Question/1.pdf

Marr, K. (2013) Labs Activities for Fall 2013, Retrieved from http://www.instruction.greenriver.edu/kmarr/Chem%20161/Chem161Labs.htm (Scroll down to Lab 7 Lab analysis of hard water)