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Chemistry 223: Experiment 4

Acid- Base and Precipitation Titration


References: 1. C, Chap. 7 .
2. H7, Chapter 11,
3. Kellner, Chap 4
4. SWH, Chaps. 10,11,12,13
5. Harvey, C5 and C7
6. Kealey, pp. 139-143
This experiment is partly based on the experiment - chem. 213 – Winova State University
and Chemistry 3.1- University of Canterbury

A. Determination of total alkalinity of soda ash

I. Introduction:
Crude sodium carbonate, Na2CO3, is commonly called soda ash. It is frequently used as a
commercial neutralizing agent. Besides the carbonate, small amounts of sodium hydroxide,
NaOH, and sodium hydrogen carbonate, NaHCO3, may also be present. Titrating with
standard acid, usually HCl, makes it possible to determine the total alkalinity of the soda ash.
It is common practice to report the total alkalinity as percent sodium carbonate or sodium
oxide, Na2O. Since samples are frequently non-homogeneous, the method of aliquot portions
is usually employed. Instead of weighing out three separate samples of soda ash, one
accurately weighs out a larger amount. This is then transferred into a volumetric flask,
dissolved in water and then diluted to an accurately known volume. From this solution are
then taken samples or aliquots on which the titration is carried out.

One-tenth molar hydrochloric acid is standardized against primary standard sodium carbonate.
Phenolphthalein is used to approximate the halfway point of the titration, and then either
modified methyl orange indicator or bromcresol green indicator is used to detect the final end
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point; the last indicator is used with boiling of the solution near the end point to remove CO2.
Altematively, the hydrochloric acid is standardized against standardized sodium hydroxide
using phenophthalein indicator. The soda ash sample is titrated with the hydrochloric acid
solution, with the addition of 2 mol hydrogen per mole Na2CO3[AS1].
Equations
CO32- + 2H+ → H2CO3
H2CO3 → H2O + CO2 ↑

II. Solutions and Chemicals


Provided.
• 0.2% phenolphthalein in 90% ethanol
• modified methyl orange (mixture of methyl orange and xylene cyanole FF available
from Eastman Kodak Co.)
• 0.1 % bromcresol green in 0.001 M NaOH,

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• primary standard Na2CO3 dried at 160°C for 2 h or more. Cool at least 30 min in a
desiccator before weighing.
• standardized 0.1 M NaOH.
To be prepared. 0.1 M HCl. Concentrated hydrochloric acid has a density of 1.18 g/mL and
contains 37% by weight HCl. Hence, about 4 mL concentrated acid should be diluted to 500
mL to make 0.1 M acid. Measure about 0.5 mL more than this amount in a 10-mL graduated
cylinder and pour into water in a 500-mL glass-stoppered bottle that is filled to the shoulder
with distilled water. Shake until the solution is homogeneous.
III. Experimental Procedure

Standardize the HCl by either method 1 or method 2 below.

1. Standardization of HCl against Na2CO3 . Weigh accurately (to 0.1 mg) the weighing bottle
containing the dried sodium carbonate. Keep the stopper in place while weighing. Transfer
quantitatively (for four-figure accuracy) about 0.2 g to a clean 250-mL Erlenmeyer flask. .
(This procedure is called "weighing by difference" and is necessary because Na2CO3 is
hygroscopic.) Weigh out a second and third portion in the same way. Add about 50 mL
distilled water and one to two drops phenolphthalein indicator solution to each flask.

The Na2CO3 will be titrated first to a phenolphthalein end point (pink to colorless; 1 H+
added: CO32- + H+ → HCO3 -) to approximate where the final end point should be (modified
methyl orange or bromcresol green indicator; 1 more H+ added: HCO3 - + H+ → H2CO3). Rinse
the buret three times with small portions (about 5 mL each) of the approximately 0.1 M acid
prepared above, then fill and adjust to near the zero mark. Record the volume to the nearest
0.02 mL. Titrate the first sample of the sodium carbonate, adding the acid no faster than 0.5
mL per second, swirling the flask constantly until the pink color disappears. At this point,
about half the total volume of acid necessary has been added (actually a slight excess). Use
this number to estimate where the final end point will occur, keeping in mind that slightly less
acid should be required than has been added. Continue the titration by either method (a) or
method (b) below.
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(a) Modified methyl orange indicator. Before beginning, check with your instructor which
indicator you are to use. Add two to three drops of modified methyl orange indicator and
titrate until the indicator color changes from green to gray. The proper color can be more
easily discerned by comparing with the color of two drops of the indicator in a solution
prepared by adding 0.20 g potassium acid phthalate in 100 mL distilled water. The pH of this
solution is 4.0, the same as the end-point pH in the presence of CO2. Use the same technique
for the standardization and the unknown titrations.

(b) Bromcresol green indicator (alternative method). Add two to three drops bromcresol
green. The color change for this indicator is from blue through pale green to yellow. Titrate to
a blue-green color (just before the end point); interrupt the titration at this point and boil the
solution carefully for 2 to 3 min to drive off the carbon dioxide. The color should revert to
blue. Cool the solution to room temperature and continue the titration to the pale-green color.
This marks the final end point .

Titrate the other two samples in the same manner as the first and calculate the molarity of the
HCl from the weights of Na2C03 taken, remembering that each carbonate has reacted with two
protons. Use the mean of the three determinations for calculations involving the unknown.

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2. Standardization of HCl against standardized 0.1 M NaOH (alternate procedure. Rinse your
25-mL pipet with 0.1 M HCl, and add with the pipet 25 mL to a 250-mL Erlenmeyer flask.
Add two to three drops phenolphthlein indicator solution. Rinse your buret with three small
portions of the 0.1 N NaOH solution prepared and standardized in Experiment 6. Fill and
adjust to near zero. The NaOH is placed in the buret rather than in the flask to protect it more
from atmospheric CO2. Record the volume to 0.02 mL. Titrate the acid until a faint pink color
is obtained that lasts for at least 30 s. Repeat the titration two more times, using your 50-mL
pipet for the second and third titrations if less than 25 mL NaOH was required in the first.
Calculate the molarity of the HCI.

3. Determination of sodium carbonate in soda ash. Accurately weigh out by difference three
samples of about 0.25 to 0.35 g each, dissolve each in about 60 mL water, and, titrate with
0.1 M[AS2] HCl, following the same procedure with respect to indicators and end point used in
the standardiiation procedure: against Na2C03 or, if not used, the one specified by your
instructor.

B. Determination of Chloride in Cheese by Precipitation Titration with Silver


Nitrate - Volhard's Method
I. Introduction

The salt sodium chloride is added during the manufacture of cheddar cheese. The content of
NaCl ranges from 0.22 to 4.76% in cheese. In this method, the cheese is ‘digested’ to release
this salt to obtain the concentration of chloride ions. To carry out this digestion, the cheese is
reacted with nitric acid and potassium permanganate. The chloride ions are then ‘free’ to form
a precipitate with the added silver ions.

This method uses a back titration with potassium thiocyanate, and is applied to determine the
concentration of chloride ions in a solution. Before the titration, an excess volume of a silver
nitrate solution is added to the solution containing chloride ions, forming a precipitate of
silver chloride. The term ‘excess‘ is used as the moles of silver nitrate added are known to
exceed the moles of sodium chloride present in the sample so that all the chloride ions present
will react.
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Ag+(aq) + Cl-(aq) --> AgCl(s)

The indicator Fe3+ (ferric ion) is then added and the solution is titrated with the potassium
thiocyanate solution. The titrate remains pale yellow as the excess (unreacted) silver ions
react with the thiocyanate ions to form a silver thiocyanate precipitate.

Ag+(aq) + SCN -(aq) --> AgSCN(s)

Once all the silver ions have reacted, the slightest excess of thiocyanate reacts with Fe3+ to
form a dark red complex.

Fe3+(aq) + SCN -(aq) --> [FeSCN]2+(aq)

The concentration of chloride ions is determined by subtracting the titration findings of the
moles of silver ions that reacted with the thiocyanate from the total moles of silver nitrate
added to the solution.

This method is used when the pH of the solution after the sample has been prepared is acidic.
If the pH is neutral or basic, Mohr’s method or the gravimetric method should be used. The

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method is illustrated below by using the procedure to determine the concentration of chloride
(from sodium chloride) in cheese.

II. Solutions and Chemicals

Provided. Primary standard AgN03: Obtain about 3 g primary standard AgN03 in a


weighing bottle from your instructor. Dry in the oven at 1000C for 1 to 2 h, but
no longer. Cool in a desiccator for 30 to 40 min. This will be weighed by the
direct method.

Ferric alum indicator [KFe(SO4)2.12H2O, saturated solution],

6 M HNO3 (free of oxides of nitrogen).

Nitric acid free from lower oxides of nitrogen should be colorless and can be
prepared if necessary, by boiling 1: 1 HNO3 until NO2 is expelled.

Potassium permanganate solution:(5%) Add 1.5 g KMnO4 to 30 mL of


distilled water.
Ferric ammonium sulfate solution:(saturated) Add 8 g of NH 4 Fe(SO4 ).12H2O
to 20 mL of distilled water and add a few drops of concentrated nitric acid.

• 0.1 M KSCN solution. Weigh approximately 5.0 g KSCN, dissolve in water in


a 500-mL or l-L bottle and add 500 mL distilled water. This solution will be
standardized against primary standard AgNO3.

• Cheese sample

III. Experimental Procedure

1. Standardization of KSCN solution.

Place a clean, dry weighing dish on the balance, add 0.70 to 0.75 g AgNO3 to the weighing
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dish and determine its weight to the nearest 0.1 mg. Transfer quantitatively to a clean 250-
mL wide-mouth Erlenmeyer flask. Keep away from strong light as much as possible until
ready to titrate. Add 50 mL distilled water to the flask ready for titration, 50 mL of 6 M
nitric acid free from lower oxides of nitrogen, and 2 mL ferric alum indicator.

(Lower oxides of nitrogen form nitroso complexes with Fe3+ that are red in color and will
interfere with the end point.)

Fill your 50-mL buret with the KSCN solution, record the initial volume to the nearest 0.01
mL, and titrate with constant vigorous agitation until a faint reddish-brown color appears in
the solution; this is more easily seen if the precipitate is allowed to settle after each addition
near the end point. It will be helpful to compare the color with a solution made by adding 5
mL of 6 M nitric acid and 2 mL ferric alum to 75 mL water. The color must be permanent
after strong shaking. Titrate the other two AgN03 samples in the same manner and calculate
the molarity of the KSCN solution from each titration. Use the mean of the three
determinations.

2. Sample Preparation

1. Cut or grate the cheese into fine pieces and accurately weigh (to the nearest 0.1 mg)
about 1 g into a 250 mL conical flask.

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2. Precisely add 10.00 mL of 0.1 mol/L silver nitrate solution (by pipette if possible), 10
mL of concentrated nitric acid (very carefully - see safety notes), 40 mL of distilled
water and a few boiling chips, and heat the solution to boiling.

3. As the solution boils, add 1mL of 5% potassium permanganate solution. This addition
will cause a very smelly reaction and should be done in a fume hood. Keep boiling until
the purple color disappears, then add another 1 mL of potassium permanganate solution.
Continue this process until 5 mL of potassium permanganate solution has been added
and the cheese [AS3]particles are completely digested (or as close as possible). To find out
when digestion is complete, remove the flask from heat and allow it to stand for a few
moments. Undigested cheese particles will float upon the surface of the clear liquid,
while the white precipitate of silver chloride will sink to the bottom. If there is still too
much undigested cheese, the boiling and addition of 1 mL of potassium permanganate
should be continued, checking each time until there is a satisfactory level of digestion.

4. Cool the solution and filter it. Wash the solid residue with a few mL of distilled water.

5. Make the filtrate up to 100 mL in a volumetric flask.

3. Titration

1. Use a pipet to get 10.00 mL of the cheese extract solution and pour it into a conical flask.

2. Add 1 mL of saturated ferric ammonium sulfate solution as indicator.

3. Titrate the unreacted silver ions with the 0.05 mol L−1 potassium thiocyanate solution. The
end point is the first appearance of a dark red color due to the ferric thiocyanate complex.

4. Repeat the titration with 10.00 mL samples of the cheese extract solution until you obtain
concordant results (titres agreeing within 0.1 mL).

Additional Notes:

1. Silver nitrate solution will stain clothes and skin. Any spills should be rinsed with water
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immediately.

2. Residues containing silver ions and precipitate are usually saved for later recovery of silver
metal. Check this with your teacher.

3. A ‘blank’ titration substituting sucrose (sugar) for the cheese should be carried out to see if
there are any ‘contaminating’ chloride ions present in the reagent solutions used. If any are
found, the figure should be subtracted from the titration results.

4. For greatest accuracy it is a good idea to standardize your thiocyanate solution by titrating
several samples against your standardized silver nitrate solution (once again using ferric
ammonium sulfate indicator). The concentration of SCN- determined by this titration should
then be used in all calculations.

FOR [AS4]YOUR REPORT

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A. From your experimental data calculate, for each aliquot taken, the percentage of Na2CO3
in the unknown. Your report must include the following data.
1. Unknown number

2. The mass of each sample anhydrous sodium carbonate

3. Volume of HCl for each sample of anhydrous sodium carbonate

4. Average molarity of the HCl used

5. The mass of your unknown sample.

6. Aliquot volume of unknown solution to be titrated

7. For each aliquot taken give the net volume of acid used to the bromocresol green endpoint
(the corrected volume which will be used to calculate the percent sodium carbonate).

8. Percentage of Na2CO3 in the soda ash for each aliquot titrated

9. Average percentage of Na2CO3 in the soda ash

10. Average deviation from the mean of the individual values of percent Na2CO3.

11. Pages in your lab notebook containing the pertinent data

B. Result Calculations on Precipitation titration

1. Determine the average volume of potassium thiocyanate used from your concordant titres.

2. Calculate the moles of potassium thiocyanate used.

3. Use the equation of the reaction between silver ions and thiocyanate ions

(Ag+ (aq) + SCN-(aq)


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AgSCN) to calculate the moles of unreacted silver nitrate in 100 mL


of cheese extract, and multiply the figure by five to determine the total moles of unreacted
silver nitrate (the excess) in the 500 mL volumetric flask.

4. Calculate the moles of silver nitrate in the 50 mL of solution that was added during the
sample preparation to the cheese.

5. Calculate the total moles of silver nitrate that reacted with the salt from the cheese by
subtracting the moles of unreacted silver nitrate (the excess) from the total moles of silver
nitrate added to the cheese.
6. Use the equation of the reaction between the silver ions and the chloride ions to calculate
the moles of sodium chloride in the sample of cheese.

Ag+ + Cl- AgCl

(aq) (aq) (s)

7. Calculate the concentration of sodium chloride in the cheese as grams of salt per 100 g
cheese (% salt).

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