03/09/2018

TITRATIONS IN ANALYTICAL CHEMISTRY

(VOLUMETRIC TITRATION)

Kimia Analitik
Universitas Pertamina

TOPICS
1. Definition of Titration

2. Basic Principles of Titration

3. Reaction in Titration

4. Unit of Concentration

5. Standard Solutions

6. Aliquots and Dilution

7. Gravimetric Titration

8. Titration Curves

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1. Definition N= known
V= measure

Titrimetric methods
• Definition :
A quantitative procedures based
on measuring the amount of a
reagent of known concentration
that is consumed by an analyte
in a chemical or electrochemical
reaction

N’= unknown
V’= known

Clasiffication of Titration
• Volumetric titrations → measuring the volume of
a solution of known concentration that is
needed to react completely with the analyte.
• Gravimetric titrations → the mass of the reagent
is measured instead of its volume.
• Coulometric titrations → the “reagent” is a
constant direct electrical current of known
magnitude that consumes the analyte.

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2. Basic Principles of Titration

• The sample to be analyzed is dissolved.
• The analyte solution (sample) is then reacted by
adding other reagents bit by bit (titrated).

Sample Sample solution Titration methods

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2. Basic Principles of Titration

• Reagent of known concentration that is used to carry out
a volumetric titration → Standard Titrant or standard
solution
• General Equation:
a A + t T → Product

• Indicators are often added to the analyte solution to

produce an observable physical change (signaling the
end point) at or near the equivalence point

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2. Basic Principles of Titration

• The equivalence point → theoretical point reached when
the amount of added titrant is chemically equivalent to
the amount of analyte in the sample
→ example : [H+] = [OH-].
• The end point → point in a titration when a physical
change occurs that is associated with the condition of
chemical equivalence.
• The difference in volume or mass between the
equivalence point and the end point is the titration error.
titration error : eT = Vep – Veq
Vep = actual volume at end point,
Veq = theoretical volume of equivalence point

2. Basic Principles of Titration

• Direct titration → titrant is added to the analyte until the
reaction is complete.
• Back titration → Adding a known excess of reagent to
the analyte, then, a second reagent is used to titrate the
excess of the first reagent.

A Excess T1
T1 T2

Ex. PO43– + 3Ag+ → Ag3PO4 (s)

Ag+ + SCN – → AgSCN (s)

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Typical setup for carrying

out a titration.

• The apparatus consists of

➢→ Buret
➢→ Buret stand
➢→ Clamp
➢→ White porcelain base
➢→Erlenmeyer containing
solution to be titrated.

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Read meniscus in Buret

Position the black field just below the meniscus.
Avoid parallax error by reading at eye level

Meniscus illuminator
©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

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Typical setup for

carrying out a
titration.
• Before the titration begins.
The solution to be titrated,
an acid in this example, is
placed in the flask, and the
indicator is added as
shown in the photo.
• The indicator in this case is
phenolphthalein, which
turns pink in
• basic solution.

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Typical setup for

carrying out a
titration.
• During titration.
• The titrant is added to the
flask with swirling until the
color of the indicator persists.
In the initial region of the
titration, titrant may be added
rather rapidly, but as the end
point is approached,
increasingly smaller portions
are added; at the end point,
less than half a drop of titrant
should cause the indicator to
change color. 12

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Basa

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3. Reaction in Titration
The reactions used in the titration can be grouped into:

• Acid-Base Reaction

HA + OH- → A- + H2O

B + H3O+ → BH+ + H2O

• Reduction-Oxidation Reaction

Fe3+ + Ce4+ → Fe3+ + Ce3+

• Precipitation Reaction,

Ag+ + X- → AgX (s)

• Complex Formation

Ag+ + 2CN- → [Ag(CN)2]

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3. Reaction in Titration
Terms of reaction that can be used in titration:
• The reaction stoichiometry is well known and there are
no other side reactions (quantitative).
• It goes spontaneously (the K value is very large)

• Fast-paced, any addition of reagents will be directly

consumed by the analyte.
• There should be several methods that can be used to
detect the location of the titration endpoint.

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4. Volumetric Calculation
(Unit of Concentration)
▪ Molarity (M) → unit of concentration is widely used, and is
defined as many moles of solute in 1 liter (1000 mL) of
solution.

Keterangan:

M = molarity n = mol

p = density V = volume of solution (liter)

Mr = Molar Mass m = massa

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Example
Example 13.1
Describe the preparation of 2.000 L of 0.500 M AgNO3
(169.87 g/mol) from the primary-standard grade solid
Example 13.2
A standard 0.0100 M solution of Na+ is required to
calibrate an ion-selective electrode method to
determine sodium. Describe how 500 mL of this
solution can be prepared from primary standard
Na2CO3 (105.99 g/moL).

Solution of 13.1

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Solution of 13.2

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4. Volumetric Calculation
(Unit of Concentration)

▪ Normalitas (N)

Question :
a. Calculate the normality of a 0.1 M H2SO4 solution. 0.2 N
b. Calculate the normality of Ca(OH)2 0,02 M. 0.04 N
c. What is the normality (N) of the concentrated HCl having
density = 1.1878 and its concentration 37% (Mr = 36.5)

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Jawab: Density = 1,1878 g/ml = 1187,8 g/1000 ml. Concentration 37% ,

= 439.86/36.5 = 12.04 N

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4. Volumetric Calculation
(Unit of Concentration)
▪ Weight Percentage (% w/w)
Example :
a) 5 grams of NaOH dissolved
in 45 grams of water.
▪ Part Per Million (ppm) Calculate the weight
percent NaOH in the
solution. 10 %

▪ Part per Billion (ppb) b) 5 liters of water contains

0.0162 grams of MgCO3.
Calculate the concentration
of MgCO3 in ppm. 3.24 ppm
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5. Standard Solutions
• Standard solution to be used in the titration must be precisely known

to its concentration.
• Basic methods to establish the concentration of such solutions :

▪ Direct method

determined mass of a primary standard is dissolved in a suitable

solvent and diluted to a known volume in a volumetric flask.
• Standardization

(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.

A titrant that is standardized is sometimes referred to as a

secondary-standard solution.

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5. Standard Solutions
Primary standard :
An ultra-pure (99.9% purity) compound that serves as
the reference material for a titrimetric method of analysis.
Secondary standard :
A compound whose purity has been established by
chemical analysis and that serves as the reference
material for a titrimetric method of analysis
Standardization :
a process in which the concentration of a solution is
determined by using the solution to titrate a known amount
of another reagent.

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Primary Standard
The compounds that can be used for the primary standard are:
•Arsenic trioxide (As2O3) is used to make sodium arsenite solution
NaAsO2 used to standardize the sodium periodate solution
NaIO4, iodine solution I2, and cerium (IV) sulphate Ce(SO4)2
•Benzoic acid is used to standardize sodium ethanolic solution,
isopropanol or DMF.
•Potassium bromate KBrO3 to standardize the sodium thiosulfate solution
Na2S2O3.
•Potassium hydrogen phthalate (KHP) is used to standardize the solution
perchloric acid and acetic acid.
•Sodium carbonate is used to standardize H2SO4, HCl and HNO3.
•Sodium chloride (NaCl) to standardize the AgNO3 solution
Sulfanic acid (4-aminobenzene sulfonic acid) is used for
standardization of sodium nitrite solution.

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Calculation of molarity or normality for

standard solution

1 mol / 1000 mL = 1 M 1 equivalent / 1000 mL = 1 N

x mol / y mL = z M

Ex: Na2CO3 (105.99 g / 1 mol) / 1000 mL = 1 M = 2N

x g / 250 mL = 0.01 M = 0.02 N

x = 0.264975 g ≈ 0.2650 g

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Calculation of molarity or normality for

standard solution
Ex:
MnO4– + 8 H+ + 5 e = Mn2+ + 4 H2O
Permanganate manganous
2 KMnO4 + 5 Na2(COO)2 + 8 H2SO4 = 2 MnSO4 + K2SO4 + 5 Na2SO4 + 10 CO2 + 8 H2O

2 mol ×158.03 g ≡ 5 mol × 134.01 g ≡ 10 equivalents / 1000 mL = 10 N

3.161 g/L ≡ 6.7005 g/L ≡ 0.1 N

0.1 N 1 mL ≡ 0.0067 g

if KMnO4 solution titration Ve = 42.31 mL ≡ Na2(COO)2 0.2121 g

[KMnO4] = {(0.2121 / 0.1341) mmol ×( 2/5) } / 43.31 mL = 0.01462 M

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6. Aliquot
• A certain volume of the sample solution is called:
aliquots.
• The principle of calculation: the original solution and
aliquot have the same concentration, which is different:
the number of moles.

A. 500 mL K2CrO7 2 M
n = 2 x 0,5 = 1 mol
B. 100 mL K2CrO7 2 M
n = 2 x 0,1 = 0,2 mol atau
n = (100/500) x 1 mol
A B
= 0,2 mol
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6. Dilution
• Principle of calculation:

V1 x M1 = V2 x M2

A. 20 mL CuSO4 0,5 M
n = 20 x 0,5 = 10 mmol
B. 100 mL CuSO4 …… M
Then add V1 x M1 = V2 x M2
water to 20 x 0,5 = 100 x M2
100 mL
M2 = 0,1 Molar
n = 100 x 0,1 = 10 mmol
A B

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Steps in a titrimetry
Weighing 99.9% secondary standard
pure primary
standard reagent Titration other Find N’
xx.xxxx g sample solution normality
Dissolve in a
volumetric flask
Transfer pipet

Preparation of primary Erlenmeyer Flask V ml

standard solution Find V’ ml
indicator
Calculation Normality
NV Titration unknown
sample solution
Preparation of unknown
sample solution
N’V’ Buret

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Calculating Molar Concentrations from

Standardization Data
1. A 50.00-mL portion of an HCl solution required 29.71
mL of 0.01963 M Ba(OH)2 to reach an end point with
bromocresol green indicator. Calculate the molar
concentration of the HCl.

2. Titration of 0.2121 g of pure Na2C2O4 (134.00 g/mol)

required 43.31 mL of KMnO4. What is the molar
concentration of the KMnO4 solution? The chemical
reaction is
2MnO4- + 5C2O42- +16H+ → 2Mn2+ + 10CO2 + 8H2O

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Answer No.1:
Ba(OH)2 + 2HCl → BaCl2 + 2 H2O
2 𝑚𝑚𝑜𝑙 𝐻𝐶𝑙
• Stoichiometric Ratio =
1 𝑚𝑚𝑜𝑙 𝐵𝑎 𝑂𝐻 2
𝑚𝑚𝑜𝑙 𝐵𝑎 𝑂𝐻 2
• Amount Ba(OH)2= 29.71 𝑚𝐿 𝐵𝑎 𝑂𝐻 2 𝑥 0.01963
𝑚𝐿 𝐵𝑎 𝑂𝐻 2
2 𝑚𝑚𝑜𝑙 𝐻𝐶𝑙
• Amount HCl = 29.71 𝑥 0.01963 𝑚𝑚𝑜𝑙 𝐵𝑎 𝑂𝐻 2 𝑥
1 𝑚𝐿 𝐵𝑎 𝑂𝐻 2
29.71 𝑥 0.01963𝑥 2 𝑚𝑚𝑜𝑙 𝐻𝐶𝑙
• 𝑀𝐻𝐶𝑙 = = 0.02333 M
50.0 𝑚𝐿 𝐻𝐶𝑙

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Answer No.2 :
2MnO4- + 5C2O42- +16H+ → 2Mn2+ + 10CO2 + 8H2

2 𝑚𝑚𝑜𝑙 𝐾𝑀𝑛𝑂4
• Stoichiometric Ratio =
5 𝑚𝑚𝑜𝑙 𝑁𝑎2𝐶2𝑂42
1 𝑚𝑚𝑜𝑙𝑁𝑎2𝐶2𝑂4
• Amount Na2C2O4= 0.2121 𝑔 𝑁𝑎2𝐶2𝑂4 𝑥
0.13400 𝑔𝑁𝑎2𝐶2𝑂4
0.2121 2 𝑚𝑚𝑜𝑙 𝐾𝑀𝑛𝑂4
• Amount KMnO4 = 𝑚𝑚𝑜𝑙 𝑁𝑎2𝐶2𝑂4 𝑥
0.1340 5 𝑚𝑚𝑜𝑙𝑁𝑎2𝐶2𝑂4
0.2121 2
𝑥
0.13400 5
𝑚𝑚𝑜𝑙 𝐾𝑀𝑛𝑂4
• 𝑀𝐾𝑀𝑛𝑂4 =0.01462 M
= 43.31 𝑚𝐿 𝐾𝑀𝑛𝑂4

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Calculating the Quantity of Analyte from

Titration Data
A 0.8040-g sample of an iron ore is dissolved in acid.
The iron is then reduced to Fe2+ and titrated with 47.22
mL of 0.02242 M KMnO4 solution. Calculate the results
of this analysis in terms of
(a) % Fe (55.847 g/mol) and
(b) % Fe3O4 (231.54 g/mol)

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Solution
a.
MnO4- + 5Fe2+ +8H+ → Mn2+ + 5Fe3+ + 4H2O
+
5 𝑚𝑚𝑜𝑙 𝐹𝑒2
• Stoichiometric Ratio =
1 𝑚𝑚𝑜𝑙 𝐾𝑀𝑛𝑂4
0.02242 𝑚𝑚𝑜𝑙 𝐾𝑀𝑛𝑂4
• Amount KM𝑛𝑂4 = 47.22 𝑚𝐿 𝐾𝑀𝑛𝑂4 𝑥
𝑚𝐿 𝐾𝑀𝑛𝑂4
5 𝑚𝑚𝑜𝑙 𝐹𝑒 2+
• Amount Fe2+ = 47.22 𝑥 0.02242 𝑚𝑚𝑜𝑙 𝐾𝑀𝑛𝑂4 𝑥
1 𝑚𝑚𝑜𝑙 𝐾𝑀𝑛𝑂4
𝑔𝐹𝑒 2+
• Mass Fe2+ = 47.22 𝑥 0.02242𝑥 5 𝑚𝑚𝑜𝑙 𝐹𝑒 2+ 𝑥 0.055847
𝑚𝑚𝑜𝑙𝐹𝑒 2+
47.22 𝑥 0.02242𝑥 5𝑥 0.055847 𝑔 𝐹𝑒 2+
• % Fe2+ = 𝑥 100% = 36.77%
0.8040 𝑔 𝑠𝑎𝑚𝑝𝑙𝑒

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b.
5Fe2+ = MnO4-
5 Fe3O4 = 15 Fe2+ = 3 MnO4-
5 𝑚𝑚𝑜𝑙 𝐹𝑒3𝑂4
Stoichiometric Ratio =
3 𝑚𝑚𝑜𝑙 𝐾𝑀𝑛𝑂4
47.22𝑚𝐿 KM𝑛𝑂4 𝑥 0.02242 𝑚𝑚𝑜𝑙 𝐾𝑀𝑛𝑂4
Amount KM𝑛𝑂4 =
𝑚𝐿 𝐾𝑀𝑛𝑂4
Amount Fe3O4 =
5 𝑚𝑚𝑜𝑙 𝐹𝑒3𝑂4
47.22 𝑥 0.02242 𝑚𝑚𝑜𝑙 𝐾𝑀𝑛𝑂4𝑥
3 𝑚𝑚𝑜𝑙 𝐾𝑀𝑛𝑂4
Mass Fe3O4 =
5 𝑔 𝐹𝑒3𝑂4
47.22 𝑥 0.02242𝑥 𝑚𝑚𝑜𝑙 𝐹𝑒3𝑂4 𝑥 0.23154
3 𝑚𝑚𝑜𝑙 𝐹𝑒3𝑂4
5
47.22 𝑥 0.02242𝑥 3𝑥 0.23154 𝑔 𝐹𝑒3𝑂4
%Fe3O4 = 𝑥 100% = 50.81%
0.8040 𝑔 𝑠𝑎𝑚𝑝𝑙𝑒

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Calculating the Quantity of Analyte from

Titration Data (Your Turn)
A 100.0-mL sample of brackish water was made
ammoniacal, and the sulfide it contained was
titrated with 16.47 mL of 0.02310 M AgNO3. The
analytical reaction is
2Ag+ + S2- → Ag2S(s)
Calculate the concentration of H2S in the water in
parts per million, cppm

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