Volumetric analysis, any method of quantitative chemical analysis in which the amount of a substance

is determined by measuring the volume that it occupies or, in broader usage, the volume of a second
substance that combines with the first in known proportions, more correctly called titrimetric analysis.

Divisions of Volumetric Analysis

1. Neutralization Methods (acidimetry and alkalimetry)
2. Oxidation and Reduction “Redox” Methods (oxidimetry and reductimetry)
3. Precipitation Methods (precipitimetry)
4. Complex Formation Methods (compleximetry)

A standard solution is a reagent of known concentration. Standard solutions are used in titrations and in
many other chemical analyses. The ideal standard solution for a titrimetric method will

1. be sufficiently stable so that it is necessary to determine its concentration only once;

2. react rapidly with the analyte so that the time required between additions of reagent is minimized;
3. react more or less completely with the analyte so that satisfactory end points are realized;
4. undergo a selective reaction with the analyte that can be described by a balanced equation.

Back-titration is a process in which the excess of a standard solution used to consume an analyte is
determined by titration with a second standard solution. Back-titrations are often required when the rate
of reaction between the analyte and reagent is slow or when the standard solution lacks stability.

The equivalence point is the point in a titration when the amount of added standard reagent is equivalent
to the amount of analyte.

The end point is the point in a titration when a physical change occurs that is associated with the condition
of chemical equivalence.

Indicators are often added to the analyte solution to produce an observable physical change (signaling
the end point) at or near the equivalence point.

Some Important Acid/Base Indicators

Common Name Transition Color Change Common Name Transition Color Change
Range, pH Range, pH
Thymol blue 1.2–2.8 R–Y Bromothymol 6.2–7.6 Y–B
blue
8.0–9.6 Y–B Phenol red 6.8–8.4 Y–R
Methyl yellow 2.9–4.0 R–Y Cresol purple 7.6–9.2 Y–P
Methyl orange 3.1–4.4 R–O Phenolphthalein 8.3–10.0 C–R
Bromocresol 3.8–5.4 Y–B Thymolphthalein 9.3–10.5 C–B
green
Methyl red 4.2–6.3 R–Y Alizarin yellow 10–12 C–Y
GG
Bromocresol 5.2–6.8 Y–P
purple
C - colorless, B - blue, Y - yellow, R - red, P - purple, O - orange

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A primary standard is a highly purified compound that serves as a reference material in titrations and in
other analytical methods.

Characteristics of a Good Primary Standard

1. High purity. Established methods for confirming purity should be available.
2. Atmospheric stability.
3. Absence of hydrate water so that the composition of the solid does not change with variations in
humidity.
4. Modest cost.
5. Reasonable solubility in the titration medium.
6. Reasonably large molar mass so that the relative error associated with weighing the standard is
minimized.

Primary Standards for Bases Primary Standards for Acids

benzoic acid calcium carbonate
oxalic acid mercuric oxide
potassium biiodate sodium carbonate
potassium hydrogen phthalate (KHP) tris-hydroxymethylaminomethane (THAM)
sulfamic acid

*** Molecular Weight of KHP = 204.2212 g/mol

A secondary standard is a compound whose purity has been determined by chemical analysis. The
secondary standard serves as the working standard material for titrations and for many other analyses.

Two basic methods are used to establish the concentration of such solutions.
1. Direct Method in which a carefully determined mass of a primary standard is dissolved in a suitable
solvent and diluted to a known volume in a volumetric flask.
2. Standardization in which the titrant to be standardized is used to titrate (1) a known mass of a
primary standard, (2) a known mass of a secondary standard, or (3) a measured volume of another
standard solution.

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Principle of Neutralization Titration
Neutralization titrations are widely used to determine the amounts of acids and bases. In addition,
neutralization titrations can be used to monitor the progress of reactions that produce or consume hydrogen
ions.

A. Equivalent Weights Applied to Neutralization Methods

-
The fundamental reaction of acidimetry and alkalimetry is as follows: H+ + OH → H2 O
the neutralization of an acid by a base, or the neutralization of a base by an acid

The gram-equivalent weight of a substance acting as an acid is that weight of it which is equivalent in total
neutralizing power to one mole of hydrogen as hydrogen ion. The gram-equivalent weight of a substance
acting as a base is that weight of it which will neutralize one mole of hydrogen ion (or equivalent in total
neutralizing power to one mole of hydroxyl ions, OH-).

molecular weight
equivalent weight =
factor

PROBLEMS
1. What is the equivalent weight of zinc oxide as a base? Of KHSO4 as an acid? Ans. 40.5, 136
2. What is the milliequivalent weight in grams of each of the following acids or bases, assuming
compete neutralization in each case: Na2CO3, K2O, NH4OH, HBr, H2SO3, H3PO4? Ans. 0.053, 0.047,
0.035, 0.081, 0.041, 0.0327
3. What is the equivalent weight of the following acids or bases, assuming complete neutralization in
each case: N2O5, (NH4)2O, Ba(OH)2, NH3, SO2? Ans. 54, 26, 86, 17, 32
4. How many grams of oxalic acid, H2C2O4.2H2O, are required to make (a) a liter of molar solution,
(b) a liter of normal solution, (c) 400 mL of half-normal solution? Ans. 126, 63, 12.6
5. Formic acid (HCHO2) is a monobasic acid that is 3.2 % ionized in 0.20 normal solution. What weight
of the pure acid should be dissolved in 250.0 mL in order to prepare a 0.2 normal solution? Ans.
2.3 grams
6. What weight of CaO is necessary to prepare the following: (a) 500 mL of a one-hundredth molar
solution of Ca(OH)2, (b) 30.63 mL of N/100 Ca(OH)2? Ans. 0.28 grams, 8.5764 x 10-3 grams
7. A solution of sulfuric acid has a specific gravity of 1.1 and contains 15.71% H2SO4 by weight. What
is the normality of the solution? Ans. 3.5267

SUPPLEMENTARY PROBLEMS
1. Assuming complete neutralization in each case, what are the equivalent weights of the following
substances when acting as acids and bases: LiOH, H 2SO4, Fe2O3, HC2H3O2, cream of tartar
(KHC4H4O6)? Ans. 24, 49, 53.2333, 60, 188
2. How many grams of hydrated oxalic acid (H2C2O4.2H2O) must be dissolved and diluted to exactly
one liter to make 0.123 N solution for use as an acid? Ans. 7.749
3. How many grams of pure potassium tetroxalate (KHC2O4.HC2O4.2H2O) must be dissolved in water
and diluted to exactly 780 mL to make a 0.051 N solution for use as an acid? Ans. 2.5161
4. What is the normality of a sulfuric acid solution that has a specific gravity of 1.839 and contains
95% H2SO4 be weight? Ans. 35.6541

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 5. Chloracetic acid, CH2Cl.COOH (mol. wt. 94.50), is a monobasic acid with an ionization constant of
1.6 x 10-3. How many grams of the acid should be dissolved in 300 mL of solution in order to
prepare a half-normal solution? Ans. 14.175

B. Normality of a Solution Made by Mixing Similar Components

When several similar components are mixed and dissolved in water, the normality of the resulting solution
is determined by calculating the total number of equivalent weights in a liter of solution.

PROBLEMS
1. If 3.00 grams of solid KOH and 5.00 grams of solid NaOH are mixed, dissolved in water, and the
solution made up to 1,500 mL, what is the normality of the solution as a base?
2. What is normality of an alkali solution made by dissolving 6.73 grams of NaOH (99.5 % NaOH,
0.5% H2O) and 9.42 grams of pure Ba(OH)2.8H2O in water and diluting to 850 mL?
3. If 40.0 grams of a solid dibasic acid (mol. wt. 126.0) are mixed with 25.0 grams of a solid monobasic
acid (mol. wt. 122.0) and the mixture is dissolved and diluted to 2,500 mL, what is the normality
of the solution as an acid?

C. Volume-Normality-Milliequivalent Relationship
A normal solution contains one gram-equivalent of solute per liter of solution, or one gram-milliequivalent
per milliliter of solution. It follows that the product of the number of milliliters of a given solution and the
normality of the solution must give the number of milliequivalents of solute present.

D. Adjusting Solution to a Desired Normality

PROBLEMS
1. To what volume must 750.0 mL of a 2.4 N solution be diluted in order to make it 1.76 N? Ans.
1022.7273 mL
2. How much 0.600 normal base must be added to 750 mL of a 0.200 normal base in order that the
resulting solution be 0.300 normal? Ans. 250 mL
3. What volumes of 3.00 N and 6.00 N hydrochloric acid must be mixed to make a liter of 5.00 N
acid? Ans. 333.3333 mL 3N, 666.6667 mL 6N
4. A solution of sodium hydroxide is found on analysis to be 0.5374 normal, and a liter is available.
How many milliliters of 1.000 N NaOH solution must be added in order to make the resulting
solution 0.600 normal? Ans. 156.5 mL
5. What volume of 0.2063 N KOH must be added to 150.0 mL of 0.1320 N KOH in order that the
resulting solution shall have the same basic strength as a solution which contains 15.50 grams of
Ba(OH)2 per liter? Ans. 277.5448 mL

E. Volume and Normality Relationships between Reacting Solutions

Since a gram-milliequivalent weight of an acid will just neutralize a gram-milliequivalent weight of a base
and since the number of milliequivalents in each case is found by multiplying the number of milliliters of
solution by its normality, we have the following simple relationship between two reacting solutions:

mLacid × Nacid = mLbase × Nbase

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A solution can therefore be standardized by determining what volume of it will exactly react with a definite
volume of another solution the normality of which is already known. The normalities of the two solutions
will then be in inverse ratio to the respective volumes used.

PROBLEMS
1. A solution of HCl contains 0.1243 gram-equivalent of HCl per liter. How many milliliters of half-
normal KOH solution are necessary to neutralize 10.00 mL of the acid? Ans. 2.486 mL
2. A solution of H2SO4 is 0.1372 normal. How many milliliters of 0.1421 normal KOH solution are
required to neutralize 13.72 mL of the acid? Ans. 13.2469 mL
3. To neutralize 10.00 mL of dilute acetic acid, 13.12 mL of 0.1078 N KOH were required. What is the
normality of the acid? Ans. 0.1415 N
4. A solution containing 31.21 mL of 0.100 N HCl is added to a solution containing 98.53 mL of 0.500
N H2SO4, and 50.00 mL of 1.002 N KOH are added. Is the resulting solution acid or alkaline? How
many milliliters of 0.3333 N acid or alkali will make it exactly neutral? Ans. acid, 6.8575
5. In preparing an alkaline solution for use in volumetric work, a student mixed exactly 46.32 grams
of pure KOH and 27.64 grams of pure NaOH and, after dissolving in water, diluted the solution to
exactly one liter. How many milliliters of 1.022 N HCl are necessary to neutralize 50.00 mL of the
basic solution? Ans. 74.2731

F. Determination of Normality of Solution (If weight of a sample is given)

In a few specific cases, it is possible to prepare a standard solution by accurately weighing out the solute,
dissolving, and diluting to a definite volume. This method is applicable only to solutions of such substances
as can be weighed out accurately and the composition and purity of which are definitely known. In some
cases, it is possible to determine the normality of a given solution by gravimetric methods, i.e., by taking
a definite volume of solution and precipitating the principal constituent in the form of a weighable
compound of known composition. From the weight of this compound the weight of the solute in the volume
of solution taken is calculated. This gives a direct measure of the normality.

PROBLEMS
1. A sample of pure oxalic acid (H2C2O4.2H2O) weighs 0.2000 gram and requires 30.12 mL of
potassium hydroxide solution for complete neutralization. What is the normality of the KOH
solution? Ans. 0.1054
2. What is the normality of a solution of HCl if 20.0 mL are required to neutralize the NH 3 that can be
liberated from 4 millimoles of (NH4)2SO4? Ans. 0.4
3. How many milliliters of 3.100 N NaOH will be neutralized by (a) 105.0 mL of H 2SO4 (SG = 1.05,
7.37% by weight), (b) 10.50 grams SO3? Ans. 53.4919, 84.6774
4. A 10 mL pipetful of dilute sulfuric acid was standardized gravimetrically by adding excess of BaCl2,
filtering, igniting, and weighing the resulting precipitate. The weight was found to be 0.2762 gram.
Calculate the normality of the acid. Ans. 0.2361
5. Calculate the normality of a solution of hydrochloric acid and sodium hydroxide from the following
data:
1.00 mL of HCl ≈ 0.9429 mL of NaOH
39.81 mL of HCl ≈ 0.6293 gram of AgCl
Ans. 0.1103, 0.1162

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G. Back Titration

PROBLEMS
1. In standardizing an alkali against 0.1200 gram of a solid acid (equivalent weight = 114.7), 38.92
mL of the alkali are added before it is realized that the end point has been overstepped. By
introducing 0.0050 gram of pure H2C2O4.2H2O into the solution, it is found that 0.58 mL of the
alkali is required to make the solution neutral. What is the normality of the alkali?
2. To a sample of sodium carbonate (99.20% pure Na2CO3) weighing 1.0500 grams are added 48.24
mL of a solution of acid. This is in excess of the amount required for complete neutralization. The
resulting solution is brought back to the neutral point with exactly 1.31 mL of sodium hydroxide
solution of which 1.000 mL is equivalent to 1.010 mL of the acid. Calculate the normality of the
acid.
3. A solution of sulfuric acid was standardized against calcium carbonate containing 91.90% CaCO3
and no other basic material. The sample weighing 0.7242 gram was titrated by adding an excess
of acid (29.97 mL), and the excess was titrated with 10.27 mL of NaOH solution (1.000 mL of the
acid ≈ 1.024 mL of the NaOH). Calculate the normality of each solution.

H. Calculation of Percentage Purity from Titration Values

Just as the normality of a solution can be found from the volume required to react with a definite weight
of substance of known purity, the percentage purity of a substance can be determined from the volume of
a solution of known normality required to react with a definite weight of the substance.

PROBLEMS
1. A sample of soda ash (impure Na2CO3) is titrated with half-normal sulfuric acid. If the sample
weighs 1.100 grams and requires 35.00 mL of the acid for complete neutralization, what is the
percentage of Na2CO3 in the ash, assuming no other active component to be present? What would
be the percentage of CO2 in the soda ash?
2. A sample of zinc oxide is digested with 50.00 mL of normal sulfuric acid. The excess acid is titrated
with 2.96 mL of 0.1372 normal alkali. The weight of sample is 2.020 grams. Calculate the
percentage of purity of the sample.
3. A 0.3000 gram sample of impure magnesium oxide is titrated with hydrochloric acid solution of
which 3.000 mL ≈ 0.04503 gram CaCO3. The end point is overstepped on the addition of 48.00 mL
of the acid, and the solution becomes neutral on the further addition of 2.40 mL of 0.4000 N sodium
hydroxide. What is the percentage of MgO in the sample?
4. A sample of vinegar weighing 10.52 grams is titrated with standard NaOH. The end point is
overstepped, and the solution is titrated back with standard HCl. From the following data, calculate
the acidity of the vinegar in terms of percentage of acetic acid (HC2H3O2) :
NaOH used = 19.03 ml.
HCl used = 1.50 ml.
1.000 mL HCl ≈ 0.02500 gram Na2CO3
1.000 mL NaOH ≈ 0.06050 gram benzoic acid (C6H5COOH)
5. A sample of Rochelle salt (KNaC4H4O6.4H2O), after ignition in platinum to convert it to the double
carbonate, is titrated with sulfuric acid, methyl orange being employed as an indicator. From the
following data, calculate the percentage purity of the sample:
Weight of sample = 0.9500 gram
H2SO4 used = 43.65 mL

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 NaOH used = 1.72 mL
1.000 mL H2SO4 ≈ 1.064 mL NaOH
NaOH = 0.1321 N
6. From the following data, calculate the percentage purity of a sample of KHSO 4:
1.000 mL HCl ≈ 1.206 mL NaOH
1.000 mL HCl ≈ 0.02198 gram Na2CO3
Sample = 1.2118 grams
HCl used = 1.53 mL
NaOH used = 26.28 mL

I. Indirect Volumetric Methods

Instead of titrating a substance directly with a standard solution, it is frequently more feasible to allow the
substance to react with a measured amount of a given reagent and then to titrate that part of the reagent
left over from the reaction. This is an indirect method and is characterized by the fact that, other factors
being fixed, a greater degree of purity of the sample corresponds to a smaller burette reading.

Calculation of a volumetric indirect method is usually best made by determining the total number of
milliequivalents of reagent added, and subtracting the number of milliequivalents used in the titration. This
difference is the number of milliequivalents of desired substance.

Kjeldahl Method (Determination of Organic Nitrogen)

The sample is digested with concentrated H2SO4 in the presence of a catalyst and the nitrogen in the
material thus converted to ammonium bisulfate. The resulting solution is made alkaline with NaOH and the
liberated ammonia gas distilled (through a condenser) into a measured volume of standard acid
(NH3 + H+ → NH4+). The acid remaining in the receiving flask, after all the NH 3 has been liberated, is then
titrated with standard NaOH solution.

Percentage Protein in the sample

%protein = %N * f
f = 5.70 (cereals)
= 6.25 (meat products)
= 6.38 (dairy products)

PROBLEMS
1. A sample of meat scrap weighing 2.000 g is digested with concentrated H2SO4 and a catalyst. The
resulting solution is made alkaline with NaOH and the liberated ammonia distilled into a 50.0 mL
of 0.6700 N H2SO4. The excess then requires 30.10 mL of 0.6520 N NaOH for neutralization. What
is the percentage of nitrogen in the meat?
2. The percentage of protein in milk products is determined by multiplying the %N as determined by
the Kjeldahl method by the arbitrary factor 6.25. A sample of processed meat scrap weighing 2.000
g is digested with concentrated H2SO4 and Hg (catalyst) until the N present has been converted to
NH4HSO4. This is treated with excess NaOH, and the liberated NH 3 is caught in 50.0 mL pipetful
H2SO4 (1.000 mL ≈ 0.01860 g Na2O). The excess acid requires 28.80 mL NaOH (1.000 mL ≈ 0.1266
g KHP). Calculate % protein in the meat scrap.

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 3. If all the N in 10.0 mmols urea, CO(NH2)2, is converted to NH4HSO4, and if, with excess NaOH, the
NH3 is evolved and caught in 50.0 mL of HCl (1.00 mL ≈ 0.03000 g CaCO3), what volume of NaOH
(1.00 mL ≈ 0.3465 g H2C2O4.2H2O) would be required for complete titration?
4. A sample of milk weighing 5.00 grams is digested with concentrated H2SO4 (plus a catalyst) which
converts the protein nitrogen in the milk to ammonium bisulfate. Excess NaOH is added and the
liberated NH3 is evolved and caught in 25.0 mL of dilute H2SO4. The excess acid then requires 28.2
mL of NaOH of which 31.0 mL are equivalent to 25.8 mL of the dilute H 2SO4. The acid and base
are standardized by evolving the NH3 from 1.00 gram of pure NH4Cl, passing it into 25.0 mL of the
above dilute H2SO4 and titrating the excess acid with the above NaOH. A volume of 11.3 mL of the
NaOH is required. The arbitrary factor for converting nitrogen in milk and milk products to protein
is 6.38. Calculate the percentage of protein in the above sample of milk.

J. Determination of the Proportion in which Components are Present in a Mixture

PROBLEMS
1. If 0.5000 g of a mixture of CaCO3 and BaCO3 requires 30.00 mL of a 0.2500N HCl for neutralization,
what is the percentage of each component?
2. The weight of combined LiOH, KOH and Ba(OH)2 in a mixture is 0.5000 g and requires 25.43 mL
of 0.500N acid for neutralization. The same weight of sample with CO2 gives a precipitate of BaCO3
that requires 5.27 mL of the above acid for neutralization. Find the weights of LiOH, KOH and
Ba(OH)2 in the original mixture.
3. A mixture of pure lithium carbonate and pure strontium carbonate weighs 0.5280 gram and
requires 19.82 mL of 0.5060 N acid for neutralization. What is the percentage of Li2O and SrO in
the sample?
4. What weight of barium carbonate must be added to 1.000 gram of lithium carbonate so that the
mixture will require the same volume of standard acid for neutralization as would the same weight
of pure calcium carbonate?

K. Analysis of Fuming Sulfuric Acid

Case A. An important titration is that involved in the analysis of fuming sulfuric acid (oleum). This substance
may be considered to be a solution of sulfur trioxide, SO3, in hydrogen sulfate, H2SO4, and when no other
component is present, the analysis is made by dissolving a weighed sample in water and titrating with
standard alkali.

Example: A sample of fuming sulfuric acid weighing 1.000 gram when dissolved in water requires 21.41
ml. of 1.000 N NaOH solution for neutralization. What is the percentage of each component?

Case B. Fuming sulfuric acid often contains small amounts of SO2 which with water forms H2SO3 and is
included in the alkali titration:
H2SO3 + 2OH- → SO32- + 2H2O
This is when phenolphthalein is used as the indicator. With methyl orange, the color change takes place at
the bisulfite stage:
H2SO3 + OH- → HSO3- + H2O
In case SO2 is present, its amount is usually determined in a separate sample by titration with a standard
oxidizing agent, and the other components are then computed from the alkali titration values in the usual
way, with a correction for the volume of alkali used by the SO2.

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Example: A sample of fuming sulfuric acid containing H2SO4, SO3, and SO2 weighs 1.000 gram and is found
to require 23.47 ml. of 1.000 N alkali for neutralization (phenolphthalein as indicator). A separate sample
shows the presence of 1.50% SO2. Find the percentages of SO3 and H2SO4.

L. Analyses Involving the Use of Two Indicators (Double Indicator Method)

Titration of Sodium Carbonate

Method I. Hargis
phenolphthalein methyl red

V0-Ph VPh-MR
pink to colorless yellow to salmon pink

V0-Ph < VPh-MR Na2CO3 and NaHCO3

V0-Ph > VPh-MR Na2CO3 and NaOH
Method II. Skoog
phenolphthalein methyl red or BCG

V0-Ph V0-MR

V0-MR = V0-Ph + VPh-MR

Mixture of Na2CO3 and NaHCO3
(VmL
0-Ph )(MHCl )×106
%Na2 CO3 = ×100
mg sample
(VmL mL
Ph-MR -V0-Ph )(MHCl )×84
%NaHCO3 = ×100
mg sample
Mixture of Na2CO3 and NaOH
(VmL
Ph-MR )(MHCl )×106
%Na2 CO3 = ×100
mg sample
(VmL mL
0-Ph -VPh-MR )(MHCl )×40
%NaOH= ×100
mg sample
PROBLEMS
1. A sample that may contain NaOH, Na2CO3, NaHCO3, and inert matter alone or in compatible
combination is titrated with 0.1000 N HCl with phenolphthalein as the indicator and the solution
became colorless after the addition of 48.8 mL. Methyl orange is then added and 14.55 mL more
of the acid are needed for the color change. If the sample weighs 2.345 grams, calculate the
percentage composition of the sample.

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 2. A sample consisting of Na2CO3, NaHCO3 and inert matter weighs 1.179 grams. It is titrated with
0.100 N HCl with phenolphthalein as the indicator, and the solution became colorless after the
addition of 24.00 mL. Another duplicate sample was titrated with HCl using methyl orange as
indicator. It required 50.25 mL of the acid for the color change. What is the percentage of NaHCO3
in the sample?
3. A sample of material contains for its active components NaOH, Na2CO3, NaHCO3, or possible
mixtures of these. Two samples, each weighing 1.000 gram, are dissolved in water. To one sample
phenolphthalein is added and the solution is titrated cold with 1.038 N acid, of which 17.96 mL are
required. The other sample is titrated cold with methyl orange as an indicator, and 21.17 mL of
the same acid are required. What alkalies are present? Calculate the percentage of each.

Analysis of Phosphate Mixtures

H3PO4
NaOH

HCl

methyl orange
NaH2PO4
changes color
NaOH

HCl

phenolphthalein
Na2HPO4 changes color
NaOH

HCl

Na3PO4

Example: A sample, which is known to contain either Na3PO4, NaH2PO4, Na2HPO4, or possible mixtures of
these, together with inert impurity, weighs 2.00 grams. When this sample is titrated with 0.500 N HCl,
methyl orange being used, 32.0 mL of the acid are required. The same weight of sample when titrated with
0.500 N HCl, phenolphthalein being used, requires 12.0 mL of the acid. What is the percentage composition
of the sample?

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