Prepared by: ENGR. RENA P.

MORA 1
Acidimetric Analysis

Acidimetric Analysis
Model 1: Acidimetry

Acidimetry, the direct or residual titrimetric analysis of bases using an accurately measured volume of acid, is supplied in the
analytical control of a considerable number of official substances, both inorganic and organic.
Direct titration is conducted by introducing a standard acid solution gradually from a buret into a solution of the base being assayed
until chemically equivalent amounts of each have reacted as shown by some change in properties of the mixture. Such an end point, which
must be close to the stoichiometric point, is made evident by a change in the color of some indicator or by potentiometric means.
Residual titration is used whenever the end point of a direct titration deviates appreciably from the stoichiometric points for some
reason; e.g. when the basic sample is insoluble in water and the rate of its reaction with the standard acid is relatively low. In such a
procedure, the basic sample is treated with an amount of standard acid known to be in excess of a chemically equivalent amount, and the
excess acid is subsequently titrated with a standard base. The amount of the standard acid which is chemically equivalent to the basic
sample can be calculated simply by subtracting, from the total amount of standard acid employed, the amount of acid neutralized by the
standard base in the back titration.

Study Guide Questions

1. Why residual titration is performed?
2. What is direct titration?
3. What is residual titration?
4. T or F: Residual titration is also called as back titration.
5. What is acidimetry?

Model 2: Direct Titration Methods

• Assay of Sodium Bicarbonate

o Standard solution – Sulfuric acid
o Indicator – Methyl orange
o Each milliliter of 1 N sulfuric acid is equivalent to 84.01 mg of NaHCO 3
o It is a general rule that when the substance to be assayed is a solid, the accurately weighed quantity to be used should
be dissolved in sufficient water to make the solution of about the same equivalent concentration as that of the acid to be
used in the titration.
o Methyl orange is used as indicator because phenolphthalein and most other indicators are affected by the carbonic acid
liberated in the reaction, which causes a change in color before the reaction is complete.
𝑚𝑙𝑎𝑐𝑖𝑑 𝑥 𝑁𝑎𝑐𝑖𝑑 𝑥 0.08401 𝑥 100
o % 𝑁𝑎𝐻𝐶𝑂3 = 𝑠𝑎𝑚𝑝𝑙𝑒 𝑤𝑒𝑖𝑔ℎ𝑡
o If exactly 3.0 g of NaHCO3 (84.01) is dissolved in 25 ml of water in assay of sodium bicarbonate, what will be the normality
of the solution?
1 𝑚𝑜𝑙 𝑁𝑎𝐻𝐶𝑂3 1 𝑒𝑞 𝑁𝑎𝐻𝐶𝑂3
3.0 𝑔 𝑁𝑎𝐻𝐶𝑂3 𝑥 𝑥
84.01 𝑔 𝑁𝑎𝐻𝐶𝑂3 1 𝑚𝑜𝑙 𝑁𝑎𝐻𝐶𝑂3
▪ 1𝐿 = 𝟏. 𝟒 𝑵
25 𝑚𝑙 𝑥
1000 𝑚𝐿
o If a 0.2800-g sample of sodium bicarbonate (96.5% NaHCO 3) is titrated with 0.9165 N sulfuric acid, what volume of the
acid should be required to produce an end point?
96.5 𝑔 𝑁𝑎𝐻𝐶𝑂3 1 𝑚𝑙 𝐻2 𝑆𝑂4
▪ 0.2800 𝑔 𝑠𝑎𝑚𝑝𝑙𝑒 𝑥 𝑥 = 3.216 𝑚𝑙 𝑜𝑓 1 𝑁𝐻2 𝑆𝑂4
100 𝑔 𝑠𝑎𝑚𝑝𝑙𝑒 0.08401 𝑔 𝑁𝑎𝐻𝐶𝑂3
1 𝑚𝑒𝑞 1 𝑚𝑙
3.216 𝑚𝑙 𝑥 𝑥 = 𝟑. 𝟓𝟎𝟗 𝒎𝒍 𝒐𝒇 𝟎. 𝟗𝟏𝟔𝟓 𝑵 𝐇𝟐 𝐒𝐎𝟒
1 𝑚𝑙 0.9165 𝑚𝑒𝑞
▪ Another solution using the formula:
𝑚𝑙𝑎𝑐𝑖𝑑 𝑥 0.9165 𝑥 0.08401 𝑥 100
96.5 % 𝑁𝑎𝐻𝐶𝑂3 =
0.2800 𝑔
𝑚𝑙 𝑎𝑐𝑖𝑑 = 𝟑. 𝟓𝟏 𝒎𝒍
o Calculate the titer value of KHCO3 (100.09) for 1 N sulfuric acid.
▪ 2KHCO3 + H2SO4  K2SO4 + 2H2O + 2CO2
1 𝑚𝑒𝑞 H2 SO4 1 𝑚𝑚𝑜𝑙 H2 SO4 2 𝑚𝑚𝑜𝑙 KHCO3 100.09 𝑚𝑔 KHCO3
1 𝑚𝑙 H2 SO4 𝑥 𝑥 𝑥 𝑥 = 𝟏𝟎𝟎. 𝟎𝟗 𝒎𝒈
1 𝑚𝑙 H2 SO4 2 𝑚𝑒𝑞 H2 SO4 1 𝑚𝑚𝑜𝑙 H2 SO4 1 𝑚𝑚𝑜𝑙 KHCO3

Study Guide Questions

6. Calculate the following titer values for 1 N sulfuric acid: (a) K 2CO3, (b) CaCO3.
7. If exactly 5.0 g of NaHCO3 (84.01) is dissolved in 100 ml of water in assay of sodium bicarbonate, what will be the normality of the
solution?

Model 3: Determination of Total Alkalinity and Sodium Carbonate Content of Sodium Hydroxide
 Prepared by: ENGR. RENA P. MORA 2
Acidimetric Analysis

• Assay of Sodium Hydroxide

o Standard solution – Sulfuric acid
o Indicator – Phenolphthalein (Discharge of pink color); Methyl orange (Persistent pink color)
o The total volume of sulfuric acid used in the titration was required to neutralize NaOH and Na 2CO3, converting the latter
first to NaHCO3 at the phenolphthalein end point and then to Na 2CO3 at the methyl orange end point. Although part of
the standard acid was actually neutralized by Na 2CO3, the USP gives specifications for total alkali including NaOH and
Na2CO3, calculated as NaOH. Each milliliter of the total amount of 1 N acid consumed is equivalent to 40.00 mg or 1
meq of NaOH.
o The difference between the total volume of standard acid used and the volume necessary to produce a phenolphthalein
end point gives the volume of standard acid necessary to neutralize the NaHCO 3 formed from the Na2CO3 during titration
to the phenolphthalein end point. This same volume was also necessary to convert the Na 2CO3 to NaHCO3. Each milliliter
of the acid volume calculated by difference is equivalent to 106.0 mg or 1 meq of Na 2CO3.
o A 965.4 mg sample of sodium hydroxide required 20.80 ml of 1 N sulfuric acid in titration to a phenolphthalein end point,
and 21.75 ml of 1 N sulfuric acid in titration to a methyl orange end point. Calculate the total alkalinity in terms of NaOH
and the proportion of Na2CO3 in the sample.
▪ The total alkalinity in terms of NaOH:
21.75 𝑥 1 𝑥 0.0400 𝑥 100
= 𝟗𝟎. 𝟏𝟐%
0.9654 𝑔
▪ Since, the difference between the total volume of standard acid used and the volume necessary to produce a
phenolphthalein end point gives the volume of standard acid necessary to neutralize the NaHCO 3 formed from the
Na2CO3 during titration to the phenolphthalein end point, therefore the proportion of Na 2CO3 in the sample is:
(21.75 − 20.80)𝑥1𝑥0.1060𝑥100
= 𝟏𝟎. 𝟒𝟑%
0.9654

Study Guide Questions

8. Calculate the proportion of K2CO3 and the total alkalinity in terms of KOH, in a solution of potassium hydroxide, 25.00 ml of which
required 26.00 ml of 0.8650 N sulfuric acid in titration to a phenolphthalein end point and 31.15 ml of the same acid in titration to a
methyl orange end point? Hint: The same as sample problem but replace 0.0400 factor to 0.05609 and 0.1060 factor to 0.13818.

Model 4: Determination of Alkali Salt of Water-insoluble Organic Acid using Ether Extraction

• Assay of Sodium Salicylate Tablets

o Standard solution – Hydrochloric acid
o Indicator – Bromophenol blue (Permanent pale-green color)
o Each milliliter of 0.1 N hydrochloric acid is equivalent to 16.01 mg of sodium salicylate (C 7H5NaO3)
o Formula:
𝑚𝑙 𝑥 𝑁 𝑥 0.16011 𝑥 10
𝑔 𝑠𝑜𝑑𝑖𝑢𝑚 𝑠𝑎𝑙𝑖𝑐𝑦𝑙𝑎𝑡𝑒 𝑝𝑒𝑟 𝑡𝑎𝑏𝑙𝑒𝑡 =
𝑚𝑙 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒
o Example: The disodium salt of a dibasic organic acid has a molecular weight of 215; what weight of sample would be
used for titration to bromophenol blue end point with 0.2500 N acid in order that 35.00 ml of the latter will be required?
Solution: Since it is a disodium salt of a dibasic organic acid, we expect that the number of equivalent is 2.
𝑚𝑒𝑞 1 𝑚𝑚𝑜𝑙 215 𝑚𝑔 1𝑔
35.00 𝑚𝑙 𝑥 0.2500 𝑥 𝑥 𝑥 = 𝟎. 𝟗𝟒𝟎𝟔 𝒈
𝑚𝑙 2 𝑚𝑒𝑞 1 𝑚𝑚𝑜𝑙 1000 𝑚𝑔
Study Guide Questions
9. Twenty sodium salicylate tablets labeled 325 mg were dispersed in sufficient water to make 200.0 ml. A 15.0-ml aliquot of the
filtrate was titrated to a bromophenol blue end point in the usual way by 29.11 ml of 0.1000 N hydrochloric acid. Calculate the
amount of sodium salicylate in each tablet and, from that, the percentage of the labeled amount. Hint: Use the above formula.

Model 5: Residual Titration Methods

Residual titration or back titration is frequently used when a reaction proceeds slowly or when the substance to be assayed does
not give a distinct, sharp end point with an indicator by direct titration. Residual titration is carried out by dissolving the substance under
examination in an accurately measured quantity of standard solution known to be in excess and titrating the excess of the latter with another
standard solution.
• Assay of Zinc Oxide
o Standard solutions – Sulfuric acid and Sodium hydroxide
o Indicator – Methyl orange
o Each milliliter of 1 N sulfuric acid is equivalent to 40.69 mg of ZnO
o Formula for the percentage of zinc and the percentage of zinc oxide in the sample:
 Prepared by: ENGR. RENA P. MORA 3
Acidimetric Analysis

[(𝑚𝑙𝑎𝑐𝑖𝑑 𝑥 𝑁) − (𝑚𝑙𝑏𝑎𝑠𝑒 𝑥 𝑁)]𝑥 0.04068 𝑥 100

%=
𝑆𝑎𝑚𝑝𝑙𝑒 𝑤𝑒𝑖𝑔ℎ𝑡
• Assay of Potassium Sodium Tartrate (C4H4KNaO6)
o Standard solutions – Sulfuric acid and Sodium hydroxide
o Indicator – Methyl red-methylene blue
o Each milliliter of 0.5 N sulfuric acid is equivalent to 52.54 mg of C 4H4KNaO6
o Formula
[(𝑚𝑙𝑎𝑐𝑖𝑑 𝑥 𝑁) − (𝑚𝑙𝑏𝑎𝑠𝑒 𝑥 𝑁)]𝑥 0.10508 𝑥 100
% 𝐶4 𝐻4 𝐾𝑁𝑎𝑂6 =
𝑆𝑎𝑚𝑝𝑙𝑒 𝑤𝑒𝑖𝑔ℎ𝑡, 𝑔
o The N.F. requires that potassium sodium tartrate contain not less than 99% and not more than 102.0% of C 4H4KNaO6,
calculated on anhydrous basis.
• Assay of Milk of Magnesia
o Standard solutions – Sulfuric acid and Sodium hydroxide
o Indicator – Methyl red
o Each milliliter of 1 N sulfuric acid is equivalent to 29.16 mg of Mg(OH)2
o Formula
[(𝑚𝑙𝑎𝑐𝑖𝑑 𝑥 𝑁) − (𝑚𝑙𝑏𝑎𝑠𝑒 𝑥 𝑁)]𝑥 0.02916 𝑥 100
% =
𝑆𝑎𝑚𝑝𝑙𝑒 𝑤𝑒𝑖𝑔ℎ𝑡, 𝑔
o The U.S.P. requires that milk of magnesia contain not less than 7 and not more than 8.5% Mg(OH) 2.
o Example: If a sample of magnesia magma weighing 5.2430 g when dissolved in 25 ml of 0.9915 N H 2SO4 required 9.85
ml of 1.1402 N NaOH to titrate the excess acid, calculate the percent of Mg(OH)2 in the sample.
[(25 𝑥 0.9915) − (9.85 𝑥 1.1402)]𝑥 0.02916 𝑥 100
= 𝟕. 𝟓𝟒%
5.2430 𝑔
• Assay of Methenamine
o Standard solutions – Sulfuric acid and Sodium hydroxide
o Indicator – Methyl red
o Each milliliter of 1 N sulfuric acid is equivalent to 35.05 mg of C6H12N4
o Formula
[(𝑚𝑙𝑎𝑐𝑖𝑑 𝑥 𝑁) − (𝑚𝑙𝑏𝑎𝑠𝑒 𝑥 𝑁)]𝑥 0.03505 𝑥 100
% =
𝑆𝑎𝑚𝑝𝑙𝑒 𝑤𝑒𝑖𝑔ℎ𝑡, 𝑔

Study Guide Questions

10. When residual titration is used?
11. How back titration is carried out?
12. Assay of zinc oxide is what type of analysis?
13. If a 1.12500-g sample of zinc oxide, 95.0%, were treated with 50.0 ml of 1.1230 N sulfuric acid in the usual way, what volume of
0.9765 N sodium hydroxide would be required in the back titration? Hint: Use the above formula.
14. Calculate the Mg(OH)2 content of milk of magnesia, 12.32 g of which was dissolved in 50.00 ml of 1.0340 N sulfuric acid, producing
a mixture that required 24.60 ml of 1.1255 N sodium hydroxide. Hint: Use the above formula.
15. If a 0.4340-g sample of methenamine were treated in the usual way with 25.00 ml of 0.6500 N sulfuric acid, and 9.45 ml of 0.4500
N sodium hydroxide was required in the back titration, what was the percent C6H12N4 of the sample? Hint: Use the above formula.

Model 6: Determination of Distilled Base in Boric Acid Solution

• Assay of Ammonium Chloride Injection

o Standard solution – Sulfuric acid
o Indicator – Methyl red
o Each milliliter of 0.1 N sulfuric acid is equivalent to 5.349 mg of NH4Cl

Model 7: Nitrogen Determination by the Kjeldahl Method

• Method I is a macromethod in which the ammonia is distilled into excess boric acid solution.
• Method II is a semimicromethod in which smaller samples are employed using a semimicro Kjeldahl apparatus.
• A special residual method in acidimetry intended for the determination of nitrogen content in organic compounds.
• Kjeldahl method of analysis was developed in 1883 and remains as one of the accurate and widely used method for
determining nitrogen in substances.
• The time for required for the digestion of the sample with concentrated sulfuric acid can be reduced by adding potassium
sulfate or anhydrous sodium sulfate in a sufficient amount so that the molal ratio of H 2SO4 to K2SO4 is 1.5, thereby raising
considerably the temperature at which the digestion is carried out (Gunning modification). The time required for the digestion
can also be reduced by addition of catalysts such as copper sulfate or selenium.
 Prepared by: ENGR. RENA P. MORA 4
Acidimetric Analysis

• Determine the Nitrogen Content of Alcohol-Soluble Substances in Beef Extract

o Standard solution – Sulfuric acid and sodium hydroxide
o Indicator – Methyl red-methylene blue
o Each milliliter of 0.5 N sulfuric acid is equivalent to 7.003 mg of nitrogen
o Formula:
[(𝑚𝑙𝑎𝑐𝑖𝑑 𝑥 𝑁) − (𝑚𝑙𝑏𝑎𝑠𝑒 𝑥 𝑁)]𝑥 0.01401 𝑥 100
% 𝑛𝑖𝑡𝑟𝑜𝑔𝑒𝑛 =
𝑆𝑎𝑚𝑝𝑙𝑒 𝑤𝑒𝑖𝑔ℎ𝑡, 𝑔

Study Guide Questions

16. What are the ways to reduce the time required for digestion of the sample with concentrated sulfuric acid?
17. The ammonia from a 6.1500-g sample of an organic nitrogen compound was distilled into 50.00 ml of 0.1246 N sulfuric acid, and
the mixture was titrated with 22.42 ml of 0.0962 N sodium hydroxide. Calculate the percentage of nitrogen in the sample. Hint:
Apply the above formula.
18. The Kjeldahl procedure was used to analyze 256 µL of a solution containing 37.9 mg protein/mL. The liberated ammonia was
collected in 5 mL of 0.036 M HCl, and the remaining acid required 6.34 mL of 0.010 M NaOH for complete titration. What is the
weight % of nitrogen (14) in the protein? Hint: Determine first the amount of protein in gram in the solution and this will be your
weight of the sample. Then apply the above formula.