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Potentiometric Titration of a Mixture of Cl- in Beer

Introduction

Titration makes it possible to determine the concentration of a wide range of analytes in

samples. There are many types of titrations and they may be categorized depending on the nature

of the reaction taking place. Examples based on this criterion include acid-base titration,

precipitation titration, redox titration, and complexometric titration. The end point of the

titrations may be determined using various means including the use of chemical indicators,

potentiometry, and photometry.

Potentiometric titration involves monitoring changes in potential generated across a pair

of electrodes immersed in the solution during titration. Various kinds of electrodes are used

depending on the reaction taking place. For instance, a glass electrode with a silver/silver

chloride electrode is commonly used for monitoring the progress of acid-base titrations (Harris

215). Ion-selective electrodes may also be employed.

In this experiment, the concentration of chloride in beer is determined using

potentiometric titration of chloride with silver nitrate. The titrant is first standardized by titrating

a sample of KCl primary standard with the AgNO3 to determine the exact concentration of the

titrant. The primary standard must have high purity, low hygroscopicity, high equivalent weight
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to minimize weighing errors, low toxicity, and high stability. The reaction between chloride and

silver ions is as follows:

−¿⟶ AgC l (s ) ¿
+¿+C l(aq ) ¿
A g( aq)

The chloride and silver ions react to form a white precipitate of AgCl. The ionic strength

of the solution remains relatively constant before the end point as the added Ag+ is removed from

solution by Cl-. The NO3- from the titrant replaces the lost Cl-, maintaining a constant number of

ions in the system. Once all the Cl- in the sample has been depleted, the added titrant causes a

sharp rise in the ionic strength of the solution, resulting in a detectable spike in potential. This

signals the end point of the titration.

Procedure

Part 1. Standardization of AgNO3 Titrant Solution

About 1 g of KCl pre-dried in a desiccator was cooled to room temperature and 0.112 g

of the cooled salt weighed into four 100-mL beakers. The KCl was dissolved in just enough

distilled water to allow the electrode to be fully immersed. The reagent reservoir was rinsed with

the provided ~0.1 M AgNO3 solution and the titration apparatus assembled as per the instructions

in the laboratory manual. Logger Pro software was used for data collection. The end point was

taken to be the point of maximum increase in potential. Once this point was identified, the

titration was allowed to proceed for a few more milliliters of titrant. The titration was repeated

for the other three KCl masses to obtain four replicates.

Part 2. Analysis of an Unknown Beer Sample

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Approximately 25 mL of an unknown solution was transferred into a clean and dry

beaker. 5.00-mL aliquots were diluted with just enough DI water to allow the electrode to be

fully immersed and the titration process repeated using the unknown solution.

Results

Table 1. Standardization of AgNO3 Titrant Solution

Trial 1 2 3 4

Mass of KCl (g) 0.112 0.112 0.112 0.112

Volume of AgNO3 17.8 14.7 18.3 17.1

(mL)

Table 2. Analysis of an Unknown Beer Sample

Volume of Beer sample (mL): 25.00 mL

Trial 1 2 3 4

Volume of AgNO3 1.821 1.785 1.678 1.642

(mL)

Observations

KCl dissolved in water to form a clear and colorless solution. The solution turned white

and cloudy on adding the AgNO3 titrant. The change in potential was consistently small at the

beginning of the titration. Near the end point, the potential started to increase by larger
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increments. The largest spike in potential was observed at the end point. The same observations

were noted during titration of the sample.

Discussion

The chloride anion is an essential mineral needed for proper functioning of the human

body. It is needed for various functions including electrolyte balance and creation of stomach

acid. Chloride poisoning is rare. High concentrations of the mineral however degrade the taste of

water and beverages by giving them a salty taste. Drinking water standards require chloride level

to not exceed 250 ppm (EPA). The limits for beverages like beer and wines however vary from

country to country. For instance, the maximum allowable concentration of chlorides in Brazilian

wine is 200 ppm while that in Australia is 1g/L, both expressed as sodium chloride (Coli et al

96).

The chloride concentration in an unknown beer sample was determined using

precipitation titration of chloride with silver nitrate. The end point of the titration was detected

using an oxidation-reduction potential (ORP) sensor, which measures the oxidizing or reducing

ability of a solution. The reaction taking place is however not a redox reaction and the electrode

instead responds to changes in ionic strength of the solution. As the titrant is added, the measured

potential increases gradually. A sudden large spike occurs at the end point, followed by a

levelling off of the potential as excess titrant is added.

During the titration, Ag+ ions from the titrant react with Cl- ions in the sample to form a

white precipitate of AgCl. More chloride is consumed as the titrant is added. The chloride

removed with each addition of titrant is however replaced with an equivalent amount of nitrate

from the titrant hence the ionic strength of the solution does not change appreciably. At the
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equivalence point, all the chloride ions in the sample have been removed from solution. Further

addition of titrant results in a sharp increase in the ionic strength as there is no more chloride in

solution to react with the added titrant. A sudden increase in potential is therefore observed at the

end point. The potential levels off as the concentration of the solution stabilizes with addition of

excess titrant and the titration is stopped at this point.

The exact end point volume was determined by constructing a first derivative plot from

the titration curve. The titrant volume at the maxima corresponds to the point of maximum

change in potential and is taken to be the end point. The plots are shown in Figure 2 to Figure 5

in the Appendix. Using this method, the chloride concentration in beer was found to be 219 ± 11

ppm with an RSD of 49.2 ppth as shown in Figure 1 in the Appendix. There is no set standard for

the limit of chloride in beer in USA. This value is however within the range of typical values

found in beer, which is less than 250 ppm.

Various sources of error may affect the results of this experiment. One possible source of

error is the presence of other anions, such as the other halides and sulfide, that may react with

silver ions from the titrant. Presence of these anions give high results as more titrant is

consumed. The sensitivity of the ORP electrode may also be affected by other chemicals present

in beer. Lastly, small peaks are usually observed near the end point, lowering the precision with

which the end point is measured.

The analysis performed in this experiment may be improved by investigating other

quality parameters of interest such as pH and calcium content from the addition of gypsum

during the beer-making process. The alcohol concentration can also be determined and compared

with the label claim. The determination of chloride is also important in water analysis as limits
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for chloride in drinking water exist owing to the detrimental health effects of consuming too

much chloride.

Conclusion

Titration is an invaluable technique for the accurate and precise determination of the

concentration of various species in solution. Potentiometric titration of chloride in a beer sample

was done and the concentration of chloride found to be 219 ± 11 ppm. There is nothing unusual

about this value as it falls within the range of typical chloride concentration in beer and wines.
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Works Cited

Coli, Marina Sonegheti, et al. "Chloride concentration in red wines: influence of terroir and

grape type." Food Science and Technology 35 (2015): 95-99.

EPA. "Secondary drinking water standards: Guidance for nuisance chemicals." Drinking Water

Contaminants-Standards and Regulations (2017).

Harris, D. C. (2010). Quantitative chemical analysis. Macmillan.

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Appendix

Calculation of Chloride Concentration

Sample Calculation Using Trial #1

No . of moles of chloride=no . of moles of titrant used

1.821
∴ No . of moles of chloride=0.08914 mol /L × L=0.00016232 moles
1000

25.00
−¿=0.0016232mol ÷ L=0.0064927 M ¿
1000
molarity of C l

molar mass of Cl=35.453 g / mol

mol g 1000mg
−¿ ( ppm ) =0.0064927 × 35.453 × =230.2 ppm¿
L mol g
concentration of C l

The standard deviation (s) and the RSD of the trials were calculated using the following

formulas:

s
RSD ( ppth)= ×1000
x

The results from the calculations done using Excel are summarized in Figure 1.
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Trial #1 Trial #2 Trial #3 Trial 4

moles of chloride 0.00016 0.00016 0.00015 0.00015

molarity of chloride 0.00649 0.00636 0.00598 0.00585
ppm concentration of chloride 230.187 225.636 212.111 207.56
average ppm concentration 218.874
stdev of chloride concentration 10.7619

RSD ppth of chloride concetration 49.1696

Figure 1. Results from the Titration of the Beer Sample

Potentiometric Titration Graphs for Beer Samples

Trial #1 Titration Graphs

800
700
600
Potential (mV)

500
400
300
200
100
0
0 1 2 3 4 5 6 7 8
-100

Volume (mL)

Potential vs Volume First Derivative

Figure 2. Potentiometric Titration Graphs for Trial #1.

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Trial #2 Titration Graphs

700
600
500
Potential (mV)

400
300
200
100
0
0 1 2 3 4 5 6 7 8
-100
Volume (mL)

Potential vs Volume First Derivative

Figure 3. Potentiometric Titration Graphs for Trial #2.

Trial #3 Titration Graphs

700
600
500
Potential (mV)

400
300
200
100
0
0 1 2 3 4 5 6 7 8
-100

Volume (mL)

Potential vs Volume First Derivative

Figure 4. Potentiometric Titration Graphs for Trial #3.

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Trial #4 Titration Graphs

700
600
500
Potential (mV)

400
300
200
100
0
0 1 2 3 4 5 6 7 8
-100

Volume (mL)

Potential vs Volume First Derivative

Figure 5. Potentiometric Titration Graphs for Trial #4.