Laboratory Manual for Practical Exercises Volumetric analysis

Volumetric analysis
Table of contents
Preparation and standardization of NaOH solution............................................................................ 3
Ammonia determination in waste water............................................................................................. 5
Preparation of titration curves of acids............................................................................................... 6
Iodine determination in Lugol solution or in iodine tincture.............................................................. 10
Complexometric determination of calcium........................................................................................ 12
Argentometric determination of chloride in tap water…………………………….....................…... 14
Control questions................................................................................................................................ 15

Volumetric analysis or titrimetry is quantitative method of chemical analysis. The concentration

of determined component (titrant) in a solution is calculated from the consumption of standard
solution of reagent (titrator) after titration. In a volumetric analysis in a process called titration
standard solution B from the burette is added to the solution A until the reaction has taken place
quantitatively, in stechiometric ratio of examined solution A and volumetric solution. The equation
describes the process of titration:
aA + bB → pP + qQ
The termination of the chemical reaction is mostly characterized by the colour change of chemical
indicator – the point of equivalence. From the consumption of used volumetric solution it is possible
to determine the amount of the substance A from the sample. We must have the knowledge of
qualitative of the analysed sample; only one of the particles in the sample is able to react with the
volumetric solution.
We call the solutions used in titrimetry, volumetric solutions. The concentration of volumetric
solutions in volumetric analysis is considered only in molar concentrations or molarity (mol/l). If there
is a pure substance with a defined chemical composition after weighting, the solution with a precise
concentration can be prepared accordingly. However in most cases, it is not possible, even after the
analytical weighting, to prepare a volumetric solution with the precise concentration. The aberrations
from the precise concentration are determined by standardized solutions with known concentration or
by so called standardized substances, which solutions have always the same molar concentration after
weighting. Among the standardized substances there are: oxalic acid, Na2CO3, KBrO3 etc.
Volumetric analyses are classified into these basic groups by the type of the reaction between
titrator and titrant:
1. Neutralisation (protolytical, acid-base) – transfer of protons (H+);
2. Oxidation-reduction – transfer of electrons;
3. Precipitation – formation of insoluble products;
4. Complexometric – formation of complex soluble species.
Fast chemical reaction allows the direct titration of the analysed substance. The reactions that are
slower are analysed by so called back titration, where the abundance of one substance is added to the
examined substance and its residual volume is titrated by the other substance.

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Laboratory Manual for Practical Exercises Volumetric analysis

Tab.: Methods of volumetric analysis

Volumetric analysis Subgroups Titrator Indicator
alkalimetry NaOH, KOH phenolphtalein
Acid-base methyl orange
acidimetry HCl, H2SO4 methyl red
bromphenol blue
manganometry KMnO4
Oxidation-reduction
iodometry I2 resp. Na2S2O3 gelatinized scratch
argentometry AgNO3 potassium chromate
Percipitation sodium nitroprusside
mercurymetry Hg(NO3)2 murexid
eriochrome black - T
Complexometric EDTA murexid
(ethylenediamine- eriochrome black - T
tetraacetic acid)

Acid-base volumetric analyses

Acid-base volumetric analysis is based on the acid-base reactions between acids and bases.
Acidimetry is the method based on determination of bases, and alkalimetry for determination of acids.
In acidimetry we use titrators water solutions of HCl, H2SO4, HNO3. H2SO4 is preferably used in
higher temperature titration, because HCl is less stable and more siccative. In alkalimetry we use
solutions of NaOH, KOH, BaOH. Solutions of hydroxides should be standardized. Weak organic
acids and bases are used as indicators in neutralisation volumetric analysis for their sensitivity to the
change of hydrogen ions concentration signalized by the change of colour.
The titration curve reflects the Fig. Titration curve of strong acid titration by strong base
pH dependence of acid (base) solution
of the added amount of base (acid).
Whilst titrating the strong acid (base)
by the strong base (acid) the pH
change is at the beginning very slow,
the sudden change starts at the point
of the equivalence, which presents
inflex point of the titration curve. By
adding more titrator, pH changes very
slowly. Equivalent point in this case is
volume of NaOH (ml)
pH = 7.

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Laboratory Manual for Practical Exercises Volumetric analysis

Exercise: Preparation and standardization of NaOH solution

Standaridzation (determination of the true concentration) of volumetric NaOH solution is done
due to imprecision in weighing, likely impurities, hygroscopic properties of NaOH, etc. With prepared
NaOH solution is titrated the standard solution of 0.25 mol/L oxalic acid (oxalic acid is stable
compound) with phenolphtalein as indicator.

Materials
A weighing boat, a scoop, a glass rod, a volumetric flask, funnels, a burette, a wash bottle with
distilled water, a 10 mL pipette, titrimetric flasks.
Standard solution (COOH)2 (c = 0.25 mol/L), volumetric solution NaOH (appr. 0.5 mol/L),
phenolphtalein.

Procedure
1. Weigh 2 g NaOH in a weighing boat, dissolve in a beaker.
2. Transfer quantitatively into a 100 mL volumetric flask. Fill up to the mark with distilled water.
The NaOH solution has approximate concentration 0.5 mol/L due to weighing imprecision,
impurities, hygroscopic properties of NaOH.
3. Fill a burette with the NaOH solution prepared.
4. Pipette 10 mL oxalic acid solution into a titrimetric flask and add 2-3 drops of phenolphtalein
indicator.
5. Titrate with the NaOH solution during permanent mixing against white background until the
colour of solution in the titrimetric flask turns pink. Read out the volume of NaOH solution
consumed and record it.
6. Repeat the titration twice more.
7. Calculate the arithmetic mean from three consumed volumes and real concentration of the NaOH
solution.

Obseravtion:

Titrimetric flask Consumption of NaOH (ml) An average consumption (ml)

1
2
3

An example of calculation:
By the reaction:
2 NaOH + (COOH)2 → (COONa)2 + 2 H2O
n1 n2
2 moles 1 mole

The molar concentration by definition c = n/V, hence n = c • V

In the equivalence point it is valid n1 = n2, it means that n1 : n2 = 1 : 2 and by substituting n

c a . a
c .

Hence

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Laboratory Manual for Practical Exercises Volumetric analysis

c .
c a .
a

So, when V(COOH)2 = 10 mL, c(COOH)2 = 0.25 mol/L, an average consumed volume of NaOH is e.g. 10.2
mL, then cNaOH is 0.49 mol/L (see also the example with method of solution 16.5.1.1.).

Calculation:
Calculate the concentration of NaOH with your own consumption of NaOH.

Conclusions:

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Laboratory Manual for Practical Exercises Volumetric analysis

Exercise: Ammonia determination in waste waters

Ammonia is a volatile compound, therefore during titratian could occur big losses of ammonia.
That’s why the back titration is used for the determination of ammonia. The priciple of back titration is
in addition of HCl solution which reacts with ammonia by the reaction:
NH3 + l → NH4Cl
forming NN4Cl. The excess of HCl is then titrated by volumetric solution of NaOH.

Materials
Burettes, titrtimetric flask, pipettes.
HCl solution (c = 0.1 mol/L), volumetric NaOH solution (c = 0.1 mol/L), methyl orange.

Procedure
1. Pipette 5 mL of ammonia solution (with unknown concentration).
2. Pipette 10 mL of HCl concentration and add 2-3 drops of methyl orange indicator. Swirl the
solution.
3. Titrate the solution with volumetric NaOH solution until its colour turns yellow. Record the
consumed volume into your note book.
4. Repeat the titration twice more.
5. Calculate the arithmetic mean of three consumed volumes.
6. Calculate the unknown concentration of ammonia in the sample by:

l a
c c l .

Observation:

Titrimetric flask Consumption of NaOH (ml) An average consumption (ml)

1
2
3

Calculation:

Conclusion:

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Laboratory Manual for Practical Exercises Volumetric analysis

Exercise: Preparation of the titration curve

Titration neutralisation/ acid-base curve represents the pH dependence of titrated acid (base) from
the amount of the base (acid) added. The general shape of the storng acids (bases) titration curve
differs from the one of the weak acids (bases). The aberrations of the titration curves of particular
acids (bases) depend on the concentration and saturation of that particular acid (base). Regarding the
weak acids and bases, the titration shapes are dependant also on their ionisation values.

Material
HCl solution (0,1 mol/l), volumetric solution NaOH (0,1 mol/l), acetate acid solution (0,1 mol/l),
phenophtalein
Titrimetric flasks, beakers, 2 volumetric flasks (10 ml), a burette, pH-meter.

Procedure
HCl titration:
1. Pipette 10 ml of HCl solution into titrimetric flask, measure pH by pH-metre.
2. Transfer 1ml (9x) from the burette to titrimetric flask, and then add 0,5ml of volumetric solution
NaOH. After each adding, swirl the solution and measure pH and write the values into the table.
3. We titre until we get alkalic values.

Acetate acid titration:

The procedure for acetate acid titration is completely the same as the one for HCl titration. The final
values write into the table.

Results:
HCl:
NaOH (ml)
pH

HCl:
NaOH (ml)
pH

Acetate acid:
NaOH (ml)
pH

Acetate acid:
NaOH (ml)
pH

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Laboratory Manual for Practical Exercises Volumetric analysis

The graph:

Conclusion:
According to the values in the tables, create the titration curves of strong and weak acid. Set the inflex
points of the curves, pH value referring to the inflex point.

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Laboratory Manual for Practical Exercises Volumetric analysis

Oxidation – reduction volumetric analysis

Oxidation – reduction titration: a titrant is either oxidized or reduced by a titrator. In the redox
volumetric analysis oxidation-reduction reaction takes place between analysed compound and
volumetric solution. Generally the redox reaction can be written:
Red1 – analysed component before titration
Ox2 - oxidizing volumetric reagent (titrator)
Ox1 - analysed component after titration
Red2 – reduced volumetric reagent after
titration

The substances whose oxidated and reduced form have different colour are used as the indicators
in oxidation – reduction volumetric analyses. Oxidation-reduction titration can be divided into
oxidimetry, where the amount of volumetric solution with oxidative properties is measured (e.g.
manganometry, iodometry) and reductometry, where the amount of volumetric solution with reductive
properties is measured (e.g. titanometry).
Manganometry and iodometry are the most frequently used redox methods in medicine.
Manganometry is a volumetric-analytical titrimetric method based on the strong oxidative properties
of KMnO4 mainly in acidic medium where the redox reaction takes place:

MnO4 + 8 H+ + 5e- Mn2+ + 4 H2O

or. MnVII + 5e MnII

The violet ion MnO4- is during the titration reduced to almost colourless Mn2+. The change of
colour is used for detection of the end of the titration. Until equivalence point, the solution is
colourless, next superfluous drop of the KMnO4 solution turns the titrated solution to pink, so no
indicator is needed. By manganometry it is possible to detect Fe salts, hydrogen peroxide, or to detect
water pollution by organic substances.
Iodometry includes a lot of methods for determination of compounds either reducing iodine to
iodide ion or oxidizing iodide ion to iodine. The reaction:
I2 + 2 e- ↔ I-
The reaction is completely reversible. There are 2 groups of titration methods in iodometry: i) direct
titration, where the compounds are titrated directly by iodine solution and ii) indirect titration, where
the known surplus of iodine is added to the substance. The released amount of iodine is determined by
indirect bac titration by volumetric solution of sodium thiosulphate:
I2 + 2 Na2S2O3 → aI + a2S4O6

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Laboratory Manual for Practical Exercises Volumetric analysis

This reaction should run in acid or neutral environment to prevent iodine oxidation of thiosulphate
ions to tetrathionate ion and therefore reduces itself to iodide. In this indirect titration the used amount
of thiosulphate is equivalent to the amount of iodine present in the titrated solution:
n (I2) : n (Na2S2O3) = 1 : 2
or
n (I) : n (Na2S2O3) = 1 : 1
c(I) . V(I) = c(Na2S2O3) . V(Na2S2O3)
Volumetric solutions of iodine and thiosulphate are standardized by using of resublimated iodine,
arsenic trioxide, potassium bromate, etc. In iodometry, gelatinized starch is used as indicator, it is
turned from colourless (white) to blue-violet in the presence of free iodine or reverse.
Chlorine, bromine, iodide, hydrogen peroxide, ethanol in blood dichromate, ferricyanide, iodine in
lipids, iodine consumption during substitution reaction, and so forth, can be determined by iodometric
titration. Apart from that, oxidation-reduction volumetric analysis are used in additive iodide reactions
with unsaturated organic compounds (determination of iodide number in fats) and in substitution
reactions.

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Laboratory Manual for Practical Exercises Volumetric analysis

Exercise: Iodine determination in Lugol solution or in iodine tincture

Iodine dissolves in water only very little, whereas it dissolves substantially more in presence of
potassium iodide (Lugol solution, I2 and I- form I3-) or in ethanol (the tincture of iodine). In both
solutions iodine is determined by titration with sodium thiosulphate according to the reaction
I2 + 2 Na2S2O3 → NaI + Na2S4O6

Materials
Burettes, titrimetric flasks, 10 mL pipettes, a 100 mL graduated cylinder.
Volumetric solution of sodium thiosulphate (c = 0.1 mol/L), indicator - gelatinized starch.

Procedure
1. Pipette 10 mL Lugol solution (with unknown concentration) ito a titrimetric flask, add 25 mL
distilled water and swirl.
2. Titrate the mixture with the volumetric solution of sodium thiosulphate up to yellow colour.
3. Add 5 drops of gelatinized starch and titrate until the solution is colourless.
4. Record the consumption of Na2S2O3 solution into your note book.
5. Repeat the titration twice more.
6. Calculate the unknown concentration of iodine from the arithmetic mean of consumed volumes of
the titrator (VNa2S2O3) using the formula:

c a . a
c I
I

Observation:

Titrimetric flask No. Na2S2O3consumption (mL) Arithmetic mean of

consumptions (mL)
1
2
3

Calculation:

Conclusions:
Compare the precision of your determination and analyze any difference.

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Laboratory Manual for Practical Exercises Volumetric analysis

Complexometric titration
Complexometric titration are based on the ability of so called chelatons (complexones) to form
soluble, little dissociated complexes with metal cations. Chelatons represents some
polyaminocarboxyle acids. So called chelation 1 is nitrilotriacetate acid N(CH2COOH)3, chelaton 2 is
ethylenediaminetetraacetate acid (EDTA) and chelaton 3 is disodium salt, which is used the most
frequently because of its high solubility. One mol of chelation always reacts with one mole of metal
no matter the valency of the metal. Complexometric titrations always run in solution buffers, because
pH of the environment affects the stability of the complex. Murexid, pyrocatechin violet, etc. are used
as indicators. They represent the organic compounds that are creating colour complex with metal
cations. We use 3 types of titration in chelatometry:

1. The direct titration is used the most frequently. Analysed sample with added buffer solution and
indicator is titrated directly by chelaton volumetric solution.
2. In some cases it is better to use indirect (back) titration, mostly when the analysed sample is not
soluble well in the water, but it is soluble in volumetric solution, or if the making of complex is
slow, or when the strong bond is made between the metal and indicator. Afterwards the surplus of
chelaton 3 volumetric solution is added to the analysed sample with adjusted pH. The abundance
of this solution is detected by the titration of magnesium sulphate (or zinc sulphate) volumetric
solution.
3. When there are no suitable indicators for a specific sample, we can use displacement titration.
This is based on the principle that surplus of magnesium chelaton is added to the sample solution.
During the reaction with analysed metal cation a certain amount of magnesium that corresponds
with the value of metal cation in the sampe is displaced. The amount of displaced magnesium is
detected by titration of chelaton 3 volumetric solution. Because magnesium is reacting with
volumetric solution during the titration, indicator suitable for magnesium is used for equivalence
point indication.

The use of this method is very extensive. It can be used to determine the hardness of water, or for the
detection of metal cations in pharmaceutical products (calcium, magnesium, etc.) As an example we
may mention cations in eyedrops (Zn2+), creams (Al3+) or ointment (Zn2+).

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Laboratory Manual for Practical Exercises Volumetric analysis

Exercise: Complexometric determination of calcium

Complexometric determination of calcium is based on the direct titration of Ca 2+ ions by the
volumetric solution of ethylenediaminetetra acetic acid (EDTA) or its disodium salt Na2EDTA
(chelatone 3, H2Y2-) in the presence of the indicator murexide. Murexide is ammonium salt of purple
acid (5,5’-nitrilodibarbituric acid). The indicator forms a red complex species with Ca2+ ions. When
the complex species is titrated by chelatone 3 solution in alkaline medium, the stronger complex

HOOC-CH2 CH2-COOH
N-CH2-CH2-N
NaOOC-CH2 CH2-COONa

species between chelatone and calcium ions is formed. In the equivalent point the colour of the
solution turns to purple due to the free indicator released.
H2Y2- + Ca2+ → [CaY2-] + 2 H+
n (H2Y2-) : n (Ca2+) → 1 : 1

Materials:
Burettes, titrimetric flasks, 10 mL pipettes, a 100 mL graduated cylinder, a 5 mL pipette.
The volumetric solution of chelatone 3 (c = 0.1 mol/L), NaOH solution (c = 1.0 mol/L), mixture of
murexide and NaCl in the ratio 1 : 100 (solid).

Procedure:
1. Pipette 10 mL (Vx) Ca2+ solution (a sample with unknown concentration) into a titrimetric flask
and add ca. 50 mL distilled water.
2. Pipette 1 mL NaOH solution and add few grains of the murexide mixture. Swirl the mixture. The
red complex species (Ca2+-murexide) forms.
3. Titrate the mixture with the volumetric solution of chelatone 3 to a purple end point. Record the
used volume of chelatone 3 solution.
4. Repeat the titration twice more.
5. Calculate the arithmetic mean of three consumed volumes of the titrator (Vchel).
6. Calculate the unknown concentration Ca2+ in the sample (Cx) by the formula:

Observation:

Conclusions:

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Laboratory Manual for Practical Exercises Volumetric analysis

Precipitating titration
The base of precipitating titrations is precipitating reaction with known stechiometry. Although
only a few of them are suitable to be used in volumetric analysis, because the exclusion of the solid
product is their limiting factor. The most known precipitating reactions are argentometry and
mercurymetry.
Argentometry is based on the formation of little soluble silver salts after titrating the sample by
silver nitrate volumetric solution:
Ag+ + X- → AgX
X – chloride, bromide or rodanide ions.
Silver nitrate, ammonium tiocyanate or natrium chloride are used as volumetric solutions. They are
standardised by the NaCl, KCl etc. The indicator is mostly sodium hypochloride. Argentometry is
also used in detection of specific halogenides and tiocyanates by volumetric solution of silver nitrate.
AgNO3 is unstable on light; therefore it is necessary to keep this volumetric solution in the dark bottle.

Direct argentometric titration Mohr´s method is based on the direct titration of set ion Cl-) by
volumetric solution of AgNO3 with potassium chromate as visual precipitating indicator.
Back titration olhard´s method is based on precipitation of set anion by surplus of AgNO3
volumetric solution and detection of its unused amount by NH4SCN or KSCN volumetric solutions.
Iron salt is used as visual indicator, after reaching the equivalence, it colours titrate solution red by
creating tiocyanateferric complex [Fe(SCN)]2+.

In mercurymetry, mercury(II)nitrate is used as volumetric solution and sodium nitroprusside

(Na2[Fe(CN)5NO]) as an indicator otočkova method . Volumetric solutions are same standardised
as in argentometry by NaCl. Chlorides in urine and serum can be determined by mercurymetry.
We can examine the progression of precipitating titration experimentally by potenciometrical
method using the indicating system of silvers-saturated calomel or argentochloride electrode or
theoretically by calculating particular points of the titration curve.

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Laboratory Manual for Practical Exercises Volumetric analysis

Exercise: Argentometric detection of chloride in tap water

Tap water contains Cl- ions, mostly as a result of chloride componds used for water disinfection.
Cl- ions can be quantitatively detected by AgNO3 volumetric solution titration:
Ag+ + Cl- → Ag l
In reaction little soluble AgCl (KS=1,8.10-10) is created. The surplus of AgNO3 may be indicated by
adding K2CrO4, that results in:
2AgNO3 + K2CrO4 → Ag2CrO4 + 2KNO3
Ag2CrO4 is brown-red colour.

Material
250 ml titrimetric flasks, universal paper indicators, AgNO3 (c=0,01 mol/l) solution, K2CrO4 (c=0,25
mol/l) indicator, solid NaHCO3

Procedure
1. Transfer 100 ml of tap water into 250 ml titrimetric flask, measure pH by paper indicator.
2. If pH<6,0, set its value NaHCO3 to pH=7 – 9.
3. Add 1 ml of K2CrO4 solution and titrate by AgNO3 volumetric solution until brow-red coloured
precipitate.
4. Titrate twice, calculate the Cl- concentration from the average consumption:
Ag
c l cAg .

The amount of chloride in tap water should not exceed 0,85 mmol/l. Increase concentration of
chloride could be the result of water disinfection, composition of the soil layers or animal excrements.

Observation

Titrimetric flask Use of AgNO3 (ml) Avarege usage (ml)

1
2
3

Conclusion:

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Laboratory Manual for Practical Exercises Volumetric analysis

Control questions:
1. Explain, why it is necessary to standardize NaOH volumetric solutionin alcalimetry.

2. Write pH of indicator colouring: phenolphtalein, methyl red and bromphenol blue.

3. Why it is not necessary to use indicator in manganometry?

4. What is the difference between direct and indirect iodometry?

5. Why it is not possible to run the iodometric reaction in alkaline environment?

6. How can pH affect complexometric titration?

7. How can the production of solid product affect precipitating titration?

8. Draw the approximate shape of the titrating neutralisation curve of acetate acid and NaOH, set a
suitable indicator.

9. Explain the terms: equivalent point, direct titration, indirect titration, back titration.

10. Name at least 2 examples of indicators used in acid, neutral and base area.

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