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Exercise 10 Prelab:
DETERMINATION OF CHLORIDE BY THE Postlab:
VOLHARD AND MOHR METHODS Accuracy:
Precision:
I. Objective/s

At the end of this exercise, the student should be able to:

1. determine the chloride content of a sample by the Volhard and Mohr methods; and
2. differentiate between the Volhard and Mohr methods with respect to the reactions involved.

II. Principles

The titration of Ag+ in HNO3 solution is a Volhard titration. A back titration is necessary for Cl-.

Indicators change color at the end point of the acid-base titration which help in determining the
equivalence point. It is an acid or a base whose different protonated forms have various colors (Harris,
2010). In the case of polybasic acid, there are more than one end point which means it also needs more
than one indicator to change color at different stages of neutralization. This is the double indicator titration
where it can be used to analyze solutions with the substances NaOH, NaHCO 3, or Na2CO3. The
composition of the possible solution that could result from this is given in table 6.1 along with the
relationships at equivalence point.

Table 6.1 Relationships of equivalence point at different cases.

Case Relationship at equivalence point

NaOH only eq NaOH = eq HCl
Na2CO3 eq Na2CO3 = eq HCl
NaHCO3 eq NaHCO3 = eq HCl
NaOH – Na2CO3 eq NaOH = eq HCl = NHCl x Vph
eq Na2CO3 = TBS - eq NaOH
Na2CO3 - NaHCO3 TBS = eq Na2CO3 + eq NaHCO3
TBS = NHCl x Vbcg

The reaction for the mixture of NaOH and NaHCO3 (unstable) is given below:

OH- + HCO3- <-> CO32- + H2O

Single Flask and Double Flask method are the two methods of titration. Single Flask method is done by
the observation of two endpoints in a single titration using two different indicators. The latter is done by
using those different indicators in separate titrations (with the same samples). Blank titration is used to
check for possible sources of error in a "blank" solution without the presence of analyte. It is also used to
ensure that all traces of organic matter from the reagents is removed (Harvey, 2000).

In a solution with Na2CO3, NaHCO3 and NaOH, analysis requires two indicators in titrating with standard
acid solutions. For pH with range of 8.3-10, phenolphthalein is needed in order to detect the first end
point. The color transition of this indicator is from bright pink to faint pink. For the second end point, an
acid range indicator like bromcresol green is used. Its pH range is 5.4-3.8 with a color range of blue to
yellow. These indicators are used to determine which species are present, as well as their respective
concentrations (Harvey, 2000). In the reaction:
 CO32- + H3O+ <-> HCO3- + H2O
HCO3- + H3O+ <-> CO2 + H2O

Phenolphthalein is the necessary indicator for the first part because the reaction is completed at pH 9-10.
Meanwhile, for the second part where the reaction is completed at pH 4-5, bromcresol green is the
appropriate indicator (Harvey, 2000).

For a mixture of OH- and CO32-, the volume of strong acid required to titrate OH- is the same for the case
of pH 8.3 or 4.5. However, in the case of titrating CO32- at a pH of 4.5, it will require twice as much strong
acid as when titrating to the end point of pH 8.3. The same goes when titrating a mixture of these two ions
to reach pH 4.5 which will require less than twice need to reach the end point at pH of 8.3. The same
concept for the volume of strong acid needed in titration applies to the mixture of HCO 3- and CO32-
(Harvey, 2000). The amount of acid used to titrate a solution with both NaOH and Na 2CO3 with HCl is
equal to the one required to react with the OH- ions and that required to convert CO32- and HCO3-. After
recording the volume of acid, bromcresol green is used to titrate to the second end point. The amount of
the volume of acid used to titrate to the second endpoint (bromcresol green) is the amount required to
convert HCO3- to CO2.

Between the Single Flask (used in the previous example above) and the Double Flask method, the latter
will yield more accurate results in actual titrations because of the buffer system produced. This is done by
preparing two separate aliquots of equal volume from the sample. The first one is titrated by HCl solution
to the bromcresol green endpoint to determine its total basic strength. In order to precipitate CO 32- as
BaCO3, the second portion is treated with BaCl2. NaOH component is left in the solution. HCl is then used
to titrate this to the phenolphthalein endpoint.

REFERENCES

HARRIS DC. 2010. Quantitative Chemical Analysis. 8th edition. New York: W. H. Freeman and Company.

HARVEY D. 2000. Modern Analytical Chemistry. 1st edition. United States of America: McGraw-Hill
Companies, Inc.

III. Prelab Calculations / Formulas

IV. Data and Results (new page)

Table 6.3 Volume of the unknown sample used in sample preparation

Final pipet reading, mL

Initial pipet reading, mL
Volume of the unknown sample used, mL

Table 6.4 Volume of the aliquot used in the preliminary test

Sample 1 Sample 2
Final pipet reading, mL
Initial pipet reading, mL
Volume of the aliquot used, mL

Table 6.5 Volume of the acid used in the preliminary test employing phenolphthalein as indicator.

Parameter Trial 1 Trial 2

Final buret reading, mL
Initial buret reading, mL
Vph (volume of HCl used), mL

Table 6.6 Volume of the acid used in the preliminary test employing bromcresol green as indicator.

Parameter Trial 1 Trial 2

Final buret reading, mL
Initial buret reading, mL
Vbcg (volume of HCl used), mL

Table 6.7 Data on the determination of the composition of the carbonate mixture from the relative volume
of acid required for the two titrations.

Parameter Trial 1 Trial 2

Vbcg, mL
Vph, mL
Composition of the carbonate mixtures

Table 6.8 Data on the volume of the aliquot and acid used for the NaOH- Na2CO3 mixture employing
bromcresol green as indicator444

Parameter Trial 1 Trial 2

 Volume of the aliquot used, mL
Final buret reading, mL
Initial buret reading, mL
Vbcg (volume of HCl used), mL

Table 6.9 Determination of normality of HCl solution and the total basic strength of the solution

Trial 1 Trial 2
Normality of HCl sol’n, N
Ave. Normality +- d, N
Total basic strength of the solution

Table 6.10 Volume of the aliquot and acid used for the NaOH- Na2CO3 employing phenolphthalein as
indicator.

Parameter Trial 1 Trial 2

Volume of aliquot used, mL
Final buret reading, mL
Initial buret reading, mL
Volume of standard HCl used, mL
Volume of 10% BaCl2 used, mL
Number of milliequivalents in the solution

Table 6.11 Data on the determination of amounts of NaOH and Na2CO3 in the sample

Trial 1 Trial 2
%NaOH (w/v)
%Na2CO3 (w/v)

Table 6.12 Data on the determination of the total basic strength of the solution in the analysis of Na2CO3-
NaHCO3 mixture.

Parameter Trial 1 Trial 2

Volume of the aliquot used, mL
Final buret reading, mL
Initial buret reading, mL
Vbcg (volume of HCl used), mL

Table 6.13 Determination of normality of HCl solution and the total basic strength of the solution

Trial 1 Trial 2
Normality of HCl sol’n, N
Ave. Normality +- d, N
Total basic strength of the solution

Table 6.14 Volume of the aliquot and NaOH used in the analysis of Na2CO3-NaHCO3 mixture.

Parameter Trial 1 Trial 2

Volume of the aliquot used, mL
Final buret reading, mL
Initial buret reading, mL
Volume of 0.05 NaOH used, mL
Table 6.15 Volume of the 10% BaCl2 used in the analysis of Na2CO3-NaHCO3 mixture.

Parameter Trial 1 Trial 2

Final buret reading, mL
Initial buret reading, mL
Volume of 10% BaCl2 used, mL

Table 6.16 Volume of the acid used to titrate the excess NaOH in the analysis of Na 2CO3-NaHCO3
mixture.

Parameter Trial 1 Trial 2

Final buret reading, mL
Initial buret reading, mL
Volume of HCl used, mL

Table 6.17 Data on the blank titration for the analysis of Na2CO3-NaHCO3 mixture.

Parameter Trial 1 Trial 2

Volume of boiled dH2O used
Volume of 10% BaCl2, used
Volume of standard NaOH used, mL
Final buret reading, mL
Initial buret reading, mL
Volume of HCl used, mL

Table 6.18 Data on the determination of the NaHCO3 present for the analysis of Na2CO3-NaHCO3
mixture.

Parameter Trial 1 Trial 2

HCl used for the blank titration, mL
HCl used for the sample titration, mL
NaHCO3 present

Table 6.20 Data on the determination of the NaHCO3 and Na2CO3 present for the analysis of Na2CO3-
NaHCO3 mixture.

Trial 1 Trial 2
%NaHCO3 (w/v)
%Na2CO3 (w/v)

V. Answers to Prelab Questions

1. Why is it necessary to use boiled and cooled distilled water in the dilution of the carbonate sample?

Boiling the solution will cause the dissolved gases to come out of solution faster. Allowing the
water to cool quietly will give the water little chance to pick up more gas. Carbonic acid which is formed by
carbon dioxide can ruin the precision of a sample dilution because of its formation of carbonate ion.
Boiling distilled water helps in decreasing this amount of carbonate.

2. Why is it necessary to boil the solution?

 When titrating, it is necessary to boil the solution to remove carbon dioxide and carbonic acid
which will allow a sharper endpoint.

3. Give a simple method to test the completeness of the precipitation with BaCl2.

By allowing the precipitate to settle and adding precipitating agent. If no new precipitates are
formed, then the precipitation is complete. It can also by observed when the supernatant is already clear.

POSTLAB QUESTIONS:

1. What is the function of adding BaCl2 and why should it be done immediately?

- BaCl2 is added to precipitate the converted CO32- as BaCO3 and it is done immediately in order to
solidify the CO2 captured as BaCO3. Adding phenolphthalein indicator will keep CO2 from being adsorbed
from the atmosphere.

MADAMBA LSP, FAJARDO NN, FLAVIER ME, TUMLOS ET, CHEM 32 LECTURERS AND LAB
INSTRUCTORS. Quantitative Inorganic Analysis Laboratory Instruction Manual.

SKOOG DA, WEST, HOLLER. 1996. Fundamentals of Analytical Chemistry. 6th edition. Saunder College,
USA.

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