WEEK 4: TITRIMETRIC METHOD OF ANALYSIS

INTRODUCTION
What is Titration?

A quantitative and volumetric technique, to determine the unknown concentration of a solution by

the known concentration of a solution in the presence of indicator is called Titration

Titration is a common laboratory method of using quantitative chemical analysis. This method is
used to determine the unidentified concentration of a known analyte. The volume measurement is
known as volumetric analysis, and it is important in the titration.

EXPLORE

Titration Vocabulary

• Titrant – The substance added to the analyte in a titration (reagent solution)

• Analyte – The substance being analyzed

• Equivalence point – The point in a titration at which the quantity of titrant is exactly sufficient for
stoichiometric reaction with the analyte.

Four Types of Titration

1. Acid-Base Titration

The strength of an acid can be determined using a standard solution of a base. This process is called
acidimetry. In the same way, the strength of a base can be found with the help of a standard solution
of an acid, which is known as alkalimetry. Both titrations involve in the neutralization reaction of an
alkali.

What is Acid-Base Titration?

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It is a quantitative analysis method to determine an acid’s or bases’ concentration by precisely

neutralizing them with a standard solution of either acid or base of known concentration. It is
monitored with the help of a pH indicator to know the development of the acid-base reaction.

HA+BOH→BA+H2O

Acid + Alkali→Salt + Water

Or H+ + A– + B+ + OH– → B+ + A– + H2O

Or H+ + OH– → H2O

The acid-base titration is based on the reaction that neutralization is between a base or an acidic and
analyte. In this type, a reagent is mixed with the sample solution until it reaches the required pH
level. This type of titration majorly depends on the track change in pH or a pH meter.

2. Redox Titrations

The redox titration is also known as an oxidation-reduction reaction. In this type of titration, the
chemical reaction takes place with a transfer of electrons in the reacting ions of aqueous solutions.
The titrations are named after the reagent that is used in are as follows;

· Permanganate Titrations

· Dichromate Titrations

· Iodimetric and Iodometric Titrations

Permanganate Titrations

In this titration, the potassium permanganate is used as an oxidizing agent. It is maintained with the
use of dilute sulphuric acid. Here is the equation.

2KMnO4 + 3H2SO4 → K2SO4 + 2MnSO4 + 3H2O + 5[O]

Or MnO–4 + 8H+ + 5e– → Mn2++ 4H2O

Further, the solution remains colourless before the endpoint. The potassium permanganate is used to
estimate oxalic acid, ferrous salts, hydrogen peroxide, oxalates and more. While the solution of
potassium permanganate is always standardized before it is used.

Dichromate Titrations

These are titrations in which, potassium dichromate is used as an oxidising agent in acidic medium.
The medium is maintained acidic by the use of dilute sulphuric acid. The potential equation is:

K2Cr2O7 + 4H2SO4 → K2SO4 + Cr2(SO4)3 + 4H2O + 3[O]

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Or Cr2O27- + 14H+ + 6e– → 2 Cr3+ + 7H2O

The solution of potassium dichromate can be directly used for titrations. It is mainly used for the
estimation of ferrous salts and iodides.

Iodimetric and Iodometric Titrations

The reduction of free iodine to iodide ions and

oxidation of iodide ions to free occurs in these titrations.

l2 + 2e– → 2l–……………. (reduction)

2l– → I2 + 2e– ……………. (oxidation)

The solution is used as an indicator. Free iodine is used in the iodometric titration, while in the
iodometric titration an oxidation agent is used to react to liberate free iodine.

3. Precipitation Titrations

The titration is based on the insoluble precipitate formation when the two reacting substances are
brought into contact are called precipitation titration. For instance, when the solution of silver nitrate
is used to a solution of ammonium thiocyanate or sodium chloride, it reacts and forms a white
precipitate of silver thiocyanate or silver chloride.

AgNO3 + NaCl → AgCl + NaNO3

AgNO3 + NH4CNS → AgCNS + NH4NO3

4. Complexometric Titrations

The complexometric titration is where an undissociated complex is formed at an equivalence point. It

is greater than the precipitation titrations, and there will be no error due to co-precipitations.

Hg2+ + 2SCN– → Hg(SCN)2

Ag+ + 2CN– → [Ag(CN)2]–

Ethylenediaminetetraacetic acid (EDTA) is an important reagent that forms complexes with metals.

Titrimetric analysis is a method of analysis in which a solution of the substance being

determined is treated with a solution of a suitable reagent of exactly known concentration. The
reagent is added to the substance until the amount added is equivalent to the amount of substance to
be determined. The equipment used in this analysis are

Karl-Fischer titrator

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Auto titrator

Karl-Fischer titrator

A classic method in analytical chemistry that uses coulometric or volumetric to determine trace
amounts of water in a sample. The Karl Fischer titration is based on an iodine / iodide reaction. The
water reacts with iodine. The endpoint of the titration is reached when all the water is consumed. The
process uses an organic base (B), sulphur dioxide, iodine and an alcohol. The original Karl Fischer
method used pyridine or imidazole as organic base and methanol or ethanol as alcohol.

Facilities where this technique is used:

This is used to determine the amount of moisture present in the raw materials used for
polymerization and spinning. If the moisture content is above certain critical value it is detrimental.
It is also used to determine the composition of various baths solution used for fiber stretching in
spinning.

Auto titrator

The basic of the titration is the following: A solution - a so called titrant or standard solution - is
added to sample to be analyzed. Auto titrator model “Mayura AutoTitrator HP77” consists
basically of an electric burette, a sensor whose signal is amplified with a preamplifier and a
computer. During a titration, the titrator measures the signal of the sensor and uses this information
to control the addition of the titrant with the electric burette. Once the endpoint is reached, the
computer calculates the volume of titrant added and converts this value to a result based on formulas.
The formulas needed for this calculation can be programmed and depend on type of analysis.

Facilities where this technique is used: Acrylonitrile polymerization facility (F1), Fiber spinning
facility (F2).

The assay of solution used for polymerization is determined by this method. The recipe for
polymerization depends on this assay property. The concentration of the surface treatment electrolyte
is determined by this method; this is very critical for the surface itching of the carbon fiber.

ANALYSIS OF GAS CHROMATOGRAPHY

What is Gas Chromatography? (GC)

GAS CHROMATOGRAPHY (GC) is an analytical technique applicable to gas, liquid, and solid
samples (components that are vaporized by heat). If a mixture of compounds is analyzed using GC
system, each compound can be separated and quantified.

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History of Gas Chromatography

· In early 1900s, Gas chromatography (GC) was discovered by Mikhail Semenovich Tsvett as
a separation technique to separate compounds.

Overview of GC Analysis

When a mixed solution sample is injected into the GC system, the compounds contained in the
sample, including the solvent components, are heated and vaporized within the sample injection unit.

With GC system, the mobile phase, referred to as the carrier gas, always flows in sequence from the
sample injection unit to the column, and then to the detector. The target components that were
vaporized in the sample injection unit are transported by the carrier gas to the column. Once in the
column, the mixture of compounds is separated into the various components, and the amount of each
compound is then measured by the detector.

The detector converts the amount of each compound into an electrical signal, and sends these signals
to a data processing unit. The data obtained enables determination of the compounds contained in the
sample, and in what amounts.

GC System Configuration

The configuration of a GC system is very simple. There are three main GC system components: the
sample injection unit, which heats the liquid sample and vaporizes it; the column, which is used to
separate each compound; and the detector, which detects the compounds and outputs their
concentrations as electrical signals.

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Gas Chromatography Separation

Separation by GC occurs within the column.

The sample containing multiple compounds is injected into the column together with the mobile
phase. (In GC, the mobile phase is a gas referred to as the carrier gas. He is frequently used.) Both
the sample and the mobile phase travel through the column, but the rate of progression within the
column differs depending on the compound. Accordingly, differences arise in the times at which the
respective compounds arrive at the column outlet. As a result, a separation between each compound
occurs.
The row of peaks drawn when the electrical signals output from the GC detector are plotted on the
vertical axis and the elapsed time after sample injection is plotted on the horizontal axis is called a
chromatogram.
The components passing through the column are transported by the mobile phase (gas phase) while
being partitioned from and adsorbed into the stationary phase (liquid phase and solid phase).

A typical chromatogram is shown here.

The horizontal axis shows the time until the component reaches the detector. The vertical axis shows
the signal intensity.
The part at which nothing is detected is called the baseline, and the part where a component is
detected is called a peak.
The time from when the sample is injected into the system until the peaks appear is called the
retention time.
As the elution times for each component differ, each component can be separated and detected.

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Compounds Suitable for GC Analysis

Components that can be analyzed with GC have the following three main features.

Compounds with a boiling point up to 400 °C

Compounds that are not decomposed at their vaporization temperature

Compounds that decompose at their vaporization temperature, but always by the same amount. This
is called pyrolysis GC.

Compounds That Cannot Be Analyzed or Are Difficult to Analyze with GC

Compounds That Cannot Be Analyzed

Compounds that do not vaporize (inorganic metals, ions, and salts)

Highly reactive compounds and chemically unstable compounds

(hydrofluoric acid and other strong acids, ozone, NOx and other highly reactive compounds)

Compounds That Are Difficult to Analyze

Highly adsorptive compounds (compounds containing a carboxyl group, hydroxyl group, amino
group, or sulfur)

Compounds for which standard samples are difficult to obtain (Qualitative and quantitative analyses
are difficult.)
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