Section L01
Characterization of a Natural Water Sample: Alkalinity by Potentiometric
Titration & Total Cation Content Using an Ion Exchange Column
Lindsey McNaughton
Unknown #11
Dates Performed: 10/08-10/23 2017
Date submitted: 11-13-2017
ABSTRACT
Commercially available Evian water was used as a
control in the analysis of an unknown water sample.
The cation and alkalinity content of the control
samples were quantified using the 2014 Water Quality
Report provided by Evian. The cation/anion balance
reported was 105.1% while the tested balance was
97.54%. This experiment yielded a control cation
concentration of 0.006906M and anion concentration
of 0.007080M. These values served as theoretical
yield for calculating chemical recovery and
determination of effectiveness of experimental
procedure providing an overall cation/anion balance
recovery of 92.81%.
With the use of an indicator, solutions of NaOH and
HCl were titrated and the average concentrations were
calculated to be 0.09593 + 0.0009687 M and 0.1010 +
0.0004761 M respectively. Potentiometric titration of
HCl was used to determine the alkalinity of the
unknown water sample to have a bicarbonate
concentration of 0.04425 + 0.001852 M. In the final
week of the experiment a cation exchange column was
used to determine the total cation content of the
unknown water sample to be 0.09814 + 0.009071 M.
Keywords:
Impurity, Ion Exchange, Potentiometric Titration
1. INTRODUCTION
Water is essential to life and often mass produced for
human consumption. Small amounts of foreign
substances, known as impurities, are often harmlessly
found in water. Manufacturers of the purified product
aim to remove insoluble impurities such as sand by
filtration, and use ion exchange to remove insoluble
substances such as ionic compounds. This purification
process is typically intended to soften the water or
remove mineral attributes.
Ion exchange utilizes resins which are composed of a
polymer bead approximately 0.6 mm in diameter upon
which a fixed ion is permanently attached. Each of
these fixed ions must be neutralized with a mobile
counter ion of the same charge. Cation exchange used
in this experiment is more effective due to the higher
affinity the resin has for hardness ions such as Ca2+ and
Mg2+. The term ‘water hardness’ is typically used to
Unknown Results: 

0.04425 + 0.001852 M anion

0.09814 + 0.009701 M cation

describe the build up of these ions causing scaling on
surfaces. Softening of water counteracts this hardness
and occurs as the hard water passes through the resin
filled with more soluble Na+ ions. The Ca2+ and Mg2+
exchange places with the sodium and 2 Na+ ions are
released.
Potentiometric titration of HCl measures potential with
a pH reader to establish a titration curve. The shape of
the curve is indicative of the type of titration. In this
experiment a strong acid was titrated with a weak base,
so the expected titration curve would look like image B
below. The equivalence point of this titration would be
found where the number of moles titrant = moles
analyte. This is the point where change is seen in
curvature as indicated by the approximate locations of
the symbol.
*
A: B:
* *
C: D:
* *
It was the aim of this experiment to analyze an
unknown water sample’s ionic composition by
completely demineralizing the sample through the
application of a cation exchange resin while measuring
pH to determine the amount of cations replaced as
measured by H+ ions.
2. EXPERIMENTAL PROCEDURE
This experiment was divided into three sections
performed one section per week for a period of three
weeks.

2.1 Week One (10/08)
Cation-Anion balance in Evian water was determined
using average concentrations for the balance reported
in Evian’s 25 February 2014 Annual Water Quality
Report (Appendix A) followed by the preparation of
standard NaOH and HCl solutions.
Using a 1L polyethylene bottle provided,
approximately 4.0g of hygroscopic NaOH was diluted
to 1L using NanoPure water. Four portions of
approximately 0.004 moles of KHP were weighed into
separate flasks and diluted with 25mL NanoPure water.
Four drops of phenolphthalein indicator was then
added to each sample. Once all KHP was dissolved,
each KHP aliquot was titrated to the end point with
NaOH. The average concentration in molarity of the
NaOH solution was then calculated (Appendix B).
Four aliquots os HCl were dispensed into separate
flasks and 5 drops of phenolphthalein indicator was
then added to each sample prior to titration using the
standardized NaOH solution. The average
concentration in molarity of the HCl solution was then
calculated (Appendix C).
2.2 Week Two (10/16)
Alkalinity by potentiometric titration with HCl was
determined using the Vernier pH electrode data logging
system. A control sample of 100ml Evian water was
titrated with the standardized HCl solution to a pH 5.00
endpoint. The process was repeated with a 100mL
sample of NanoPure water and three aliquots of
Unknown Sample # 11. The volumes of HCl delivered
for each sample were used to calculate the bicarbonate
concentrations for each aliquot (Appendix D).
2.3 Week Three (10/23)
A total of five columns were prepared using 6M HCL
resin and polyethylene columns. Each column was
rinsed with nano pure water until the pH was neutral as
indicated by pH paper. Each sample was run through a
column and rinsed with nano pure water until the pH
coming from the column was neutral. Four drops of
phenolphthalein indicator was then added to each
sample prior to titration to the end point using the
standardized NaOH solution. The calculated moles/L
was equal to the total cation concentration (Appendix
E).
3. RESULTS
The average molarity of NaOH solution used in this
experiment was determined to be 0.09593 + 0.0009687
M. The average molarity of HCl solution used was
0.1010 + 0.0004761 M.
Unknown Sample #11 had an average HCO3
concentration of 2700 + 113.1 mg/L (0.04425 +
0.001852 M) and an average cation concentration of
0.09814 + 0.009701 M. The cation/anion balance for
unknown number 11 was 221.8% indicative of a larger
cation content.
Section L01
According to the 2014 Evian Annual Water Quality
Report there were 0.006581 moles of cations and
0.006261 moles of anions present with a 105.1%
cation/anion balance. The measured cations were
0.006909 moles and the anions were measured to be
0.007080 moles. The actual cation/anion balance was
97. 59% (Appendix F). On average the percent error
seen in this experiment was 12.16 + 8.259% with an
overall cation/anion balance recovery of 92.81%
(Appendix G).
5. DISCUSSION
Due to the hygroscopic nature of KHP, the initial
sample taken was compromised. The dried KHP had
been left in the weigh room and was allowed to absorb
moisture from the air, therefore, the initial sample
collected was deemed inadmissible. The KHP was
returned to the oven and dried an additional 10 minutes
before proceeding with the remaining sample
collections. A Grubb’s test for outliers indicated the
value obtained from sample 2 could be removed with
95% confidence. Therefore, the mean concentration of
the standardized NaOH solution was 0.09593 +
0.0009687 M . Standardization of HCl yielded no
outliers and was determined to have a concentration of
0.1010 + 0.0004761 M.
The relatively quick titration of the control and nano
pure samples were indicative of a proximal
equivalence point, or low amounts of bicarbonate
present. In comparison, unknown water sample number
11 required on average 43.81 + 1.836 mL of HCl to
bring the pH down to 5.0 + .05 indicating a higher
alkalinity in the unknown sample. The bicarbonate
concentration of the control sample was determined to
be 432 mg/L which was higher than the reported
amount of 350 mg/L by 82mg/L or an 18.98% error in
experimental procedure. The relatively low percent
error reflects the effectiveness of experimental
procedure in the quantification of unknown sample 11.
6. CONCLUSIONS
The use of potentiometric titration to determine
alkalinity of the control samples had 23.43% error
which was likely due to the relatively close
equivalence point when titrating the Evian water with
HCl and was potentially lower when determining the
alkalinity of the unknown sample. The ion exchange
column was more effective in determining the total
cation content of the control sample with 4.938% error.
It can be concluded that the Evian Water Quality
Report was accurate and unknown sample number 11
has an approximate cation concentration of 0.09814 +
0.009701 M and an anion content of approximately
0.04425 + 0.001852 M providing a cation/anion
balance of 221.8% which indicates the larger cation
concentration.
 Section L01

7. ACKNOWLEDGEMENTS
I would like to thank Mr. Szechenyi for his
contributions towards understanding the lab procedure
and expectations as well Emily for her diligence in
providing adequate resources and materials.

8. REFERENCES
[1] Szechenyi, S. Experiment #5: Characterization of a
natural water sample: alkalinity by potentiometric
titration and total cation content using an ion exchange
resin. CHE 3010 Analytical Chemistry Laboratory
2017.
[2] NSF International. Evian natural spring water
annual water quality report. Facility 40451, Cedex
France. Project Manager: Marques, C. 25 Feb 2014.
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APPENDICES

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APPENDIX A: EVIAN WATER QUALITY REPORT CATION/ANION BALANCE

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APPENDIX A1: EVIAN REPORT CATION AND ANION CALCULATIONS

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APPENDIX B: STANDARDIZATION OF NAOH WITH KHP 


(DATA USED FOR SUBSEQUENT CALCULATIONS OUTLINED IN GREEN)

Trial Number KHP (g) NaOH (mL) NaOH (M) Grubbs Test Value NaOH (M)

1 0.8164 71.70 0.05576 Eliminated due to

compromised sample
2 0.8169 54.00 0.07408 1.153

3 0.8169 42.00 0.09524 0.09524

4 0.8168 41.40 0.09661 0.09661

Mean 45.80 0.08042 0.08864 0.09593

Standard 7.108 0.01941 0.01263 0.0009687

Deviation

Notes/ Eliminating trial 1 due to a compromised sample (the hygroscopic

Results: nature of KHP may have been affected by moisture in the air as the
sample had been left out by another student), the Grubbs test allows
for the removal of trial 2 as an outlier. The average Molarity of
NaOH to be used in this experiment is 0.09593 M NaOH.

APPENDIX B1: STANDARDIZATION OF NAOH WITH KHP CALCULATIONS

 Section L01

APPENDIX C: STANDARDIZATION OF HCL WITH NAOH


(DATA USED FOR SUBSEQUENT CALCULATIONS OUTLINED
IN GREEN)

Trial Number HCl (mL) NaOH (mL) HCl (M)

1 25.00 26.50 0.1017

2 25.00 26.30 0.1009

3 25.00 26.25 0.1007

4 25.00 26.25 0.1007

Mean 0.1010

Standard 0.0004761
Deviation

Notes/ The average NaOH M used to calculate M HCl

Results: was 0.09593 M. The average Molarity of HCl
to be used in this experiment is 0.1010 M HCl.

APPENDIX C1: STANDARDIZATION OF HCL WITH NAOH CALCULATIONS


 Section L01

APPENDIX D: DETERMINATION OF ALKALINITY BY POTENTIOMETRIC

TITRATION WITH HCL (DATA USED FOR SUBSEQUENT CALCULATIONS OUTLINED
Bicarbonate
Bicarbonate
Trial Volume HCl (mL) pH concentration (M) concentration
(mg/L)

Control 7.01 5.17 0.007080 432.0

Nanopure 0.01 4.35 0.00001010 0.6163

Sample 1 43.01 5.0 0.04344 2651

Sample 2 42.51 4.97 0.04294 2620

Sample 3 45.91 5.08 0.04637 2829

Unknown Mean 43.81 0.04425 2700

Unknown 1.836 0.001852 113.1

Standard
Deviation

Notes/Results: A molar ratio of 1:1 was used to calculate the amount of HCO3 in mg/L
and M. The concentration of bicarbonate in the control sample was
was 432.0 mg/L which is higher than the 350 mg/L reported in Evian’s
Water Quality Report by 82 mg/L. The mean concentration of
bicarbonate in unknown sample number 11 was 2700 + 113.1 mg/L.
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APPENDIX D1: POTENTIOMETRIC TITRATION CONCENTRATION CALCULATIONS


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APPENDIX E: DETERMINATION OF CATION CONTENT BY ION-EXCHANGE

COLUMN (DATA USED FOR SUBSEQUENT CALCULATIONS OUTLINED IN
GREEN)

Trial Volume NaOH (mL) moles/L positive charge

Control 7.200 0.006906

Nanopure 0.1500 0.0001439

Sample 1 91.98 0.08824

Sample 2 102.8 0.09857

Sample 3 112.2 0.1076

Unknown Mean 102.3 0.09814

Unknown Standard 10.11 0.009701

Deviation

unknown percent 9.884% 9.885%

variance

Notes/Results: The control sample of Evian water had 0.006906 M

positive charge which was higher than the theoretical
quantity of 0.006581 M by 0.0003250 M. This value is the
total cation concentration for our known sample. The mean
total cation concentration for unknown sample number 11
was 0.09814 + 0.009701 M.
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APPENDIX E1: TOTAL CATION CONCENTRATION CALCULATIONS


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APPENDIX F: THEORETICAL VS MEASURED VALUES

FROM EVIAN WATER REPORT AND OBSERVED
CONTROL
Theoretical
Measured (moles)
(moles)

cations 0.007 0.006906

anions 0.0063 0.007080

cation/anion 105.1% 97.542%

balance

Notes/Results: The control sample of Evian water had

a cation/anion balance of 97.54% and
the theoretical cation/anion balance
was 105.1%. Using these values, a
percent recovery of 92.85% was
calculated indicative of reliable
experimental technique in the
quantification of unknown number 11.
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APPENDIX G: QUANTIFICATION OF ERROR: CONTROL SAMPLE VS. EVIAN REPORT

Measured Theoretical Relative Percent Percent

Sample units units Error
Value Value Error Error Recovery

Alkalinity 432.0 mg/L 350.0 mg/L 82.00 0.2343 23.43% 123.4%

0.007080 M 0.006261 M 0.0008190 0.1308 13.08% 113.1%

Cations 0.006906 M 0.006581 M 0.0003250 0.04938 4.938% 104.9%

cation/anion 97.54 % 105.1 % 7.560 0.07193 7.193% 92.81%

balance

Average 12.16%

Standard 8.259%
Deviation

Notes/Results: Percent error varied by experimental technique with an average of 12.16 + 8.259% indicative of the
overall effectiveness of experimental procedure in quantifying unknown sample number 11.

APPENDIX G1: ERROR CALCULATIONS