ASSIGNMENT 1 (PA)

1. What are errors? Sources of error and types of errors in pharmaceutical analysis. How to
minimize them?
Error is the difference between the true result (or accepted true result) and the measured
result. If the error in an analysis is large, serious consequences may result. As reliability,
reproducibility and accuracy are the basis of analytical chemistry. A patient may undergo
expensive & even dangerous medical treatment based on an incorrect laboratory result
because of an analytical error.
ERROR= measured mean value - true value / true value
The difference between experimental value and true value is called absolute error
Types of error –
 Determinant error
 Indeterminant error

Determinant error-
They are known to analyst and considered as one-sided errors. They are also known as
Systemic errors.
Types of determinant error –
 Personal
 Instrumental
 Reagent
 Additive
 Proportional
 Errors in method

Personal errors- Occur due to carelessness of analyst. Unable to spot the color end point in
titration.
Instrumental errors- It is due to faulty instruments and equipment which are not calibrated.
Wrongly graduated pipette.
Reagent errors- Depending on quality of reagents use and presence of impurities in them.
Impure potassium hydrogen phthalate of strength 0.9 N (but in actual it was prepared of 1N).
Additive/ Constant errors -They do not increase with increase in analyte/reagent amount.
They remain constant irrespective of amount. Burette readings: Instead of 10 ml it is came to
be 10.1
ml; Similarly, for 20 ml it is came to be 20.1 ml; further for 30 ml it is came to be 30.1 ml.
So, error is constant of 0.1 ml.
Proportional Errors- They increase proportionally with increase in amount. As the sample
size increase, absolute error also increases. B.R.: Instead of 10 ml it is came to be 10.1 ml; for
20 ml it would be 20.2 ml; further for 30 ml it would be 30. 3 ml. Therefore, error also
increases proportionally. (i.e. 0.1 ml to 0.2 ml to 0.3 ml).
Errors in method Errors -due to selection of wrong method. Taking reading at higher
temperatures, etc.
Indeterminant errors:
They are also known as Random or Accidental errors.
They may know or may not be known to the analyst. But in either cases analyst has no
control over them.
They are not one sided and persist even after using highest quality of operators/ reagents.
Methods of minimizing errors.
Calibration of apparatus, instrument, Glassware:
 Determinant errors can be minimized by the calibration because it is the main reason
for errors.
 Periodic calibration of instruments, glassware or apparatus required. Running a blank
determination We will not take analyte.
Control determination:
 We take standard compound (of known composition and concentration) in place of
analyte.
. • Std. + Reagent + Solvent → Std. observations
• Analyte + Reagent + Solvent → Normal observations
• Now, compare both the observations.
Standard addition/ recovery studies:
• Std. substance of known amount is added in the sample solution.
• Recovery study of the standard is done.
E.g. 1. Sample A (10 mg) + Reagent → 10 mg (after analysis)
2. Sample A (10 mg) + Std. A (5 mg) + Reagent → 15 mg (Ideal situation)
But, if only 14 mg of comes out after analysis in case 2, then it shows that only 4 mg of Std.
A is there. Means 80 % recovery or Error of 20%.
Internal standard addition method:
 Std. substance which is added in sample and analyzing Std. in same experimental
conditions
. • Internal standards are not identical/ similar to the analyte.
Independent method of analysis
It can be understood by following example:
Analysis of strength of HCl by using:
1. Neutralization Titration (using NaOH)
And also, by using: 2. Precipitative titration (using AgNO3)
• If we are getting similar results then there is no errors in the method.
Parallel determination:
Also known as Duplicate/ Triplicate determination method.
• It reduces Accidental or Random errors.
• E.g. Running TLCs side by side.
Amplification method:
If analyte is in very low quantity and not detectable by the instrument. So, we amplify the
sample to get
error free results.

Q.2. (a) Explain the various analytical techniques in detail.

(b) Describe the different concentration terms with examples.

Ans:(a)

TECHNIQUES OF ANALYSIS

1. Instrumental Method 2. Non-instrumental Method

I) Instrumental Method:

The instrumental methods of chemical analysis are divided into categories according to the
property of the analyte that is to be measured.

(a) Volumetric Method:

Volumetric analysis is a widely-used quantitative analytical method. As the name
implies, this method involves the measurement of volume of a solution of known
concentration which is used to determine the concentration of the analyte.
It involves different type of titrations.

 Acid -base titration: is a method of quantitative analysis for determining the

concentration of an acid or base by exactly neutralizing it with a standard solution
of base or acid having known concentration. A pH indicator is used to monitor the
progress of the acid–base reaction.
 Precipitation titration: is a titrimetric method which involves the formation of
precipitates during the experiment of titration. The titrant reacts with the analyte
and forms an insoluble substance. When the titrant is excess it reacts with the
indicator and signals to terminate the titration process.
  Redox titration: is a laboratory method of determining the concentration of a given
analyte by causing a redox reaction between the titrant and the analyte. These
types of titrations sometimes require the use of a potentiometer or a redox
indicator.
 Non-aqueous titration: Non-aqueous titration refers to a type of titration in which
the analyte substance is dissolved in a solvent which does not contain water. This
procedure is a very important one in pharmacopoeial assays.
 Complexometric titration: Complexometric titration (sometimes chelatometry) is a
form of volumetric analysis in which the formation of a colored complex is used
to indicate the end point of a titration. Complexometric titrations are particularly
useful for the determination of a mixture of different metal ions in solution.

(b) Gravimetric Method:

Gravimetric analysis is a technique through which the amount of an analyte (the ion
being analyzed) can be determined through the measurement of mass. Gravimetric
analyses depend on comparing the masses of two compounds containing the analyte.

The principle behind gravimetric analysis is that the mass of an ion in a pure
compound can be determined and then used to find the mass percent of the same ion
in a known quantity of an impure compound. In order for the analysis to be accurate,
certain conditions must be met:

1. The ion being analyzed must be completely precipitated.

2. The precipitate must be a pure compound.
3. The precipitate must be easily filtered.

(c) Spectral analysis:

A method of analyzing the properties of matter from their electromagnetic
interactions.
 UV visible spectroscopy:
The Principle of UV-Visible Spectroscopy is based on the absorption
of ultraviolet light or visible light by chemical compounds, which results in the
production of distinct spectra. Spectroscopy is based on the interaction between
light and matter.
 IR spectroscopy:
Infrared spectroscopy (IR spectroscopy or vibrational spectroscopy) is the
measurement of the interaction of infrared radiation with matter by absorption,
 emission, or reflection. It is used to study and identify chemical substances or
functional groups in solid, liquid, or gaseous forms.
 NMR(Nuclear Magnetic Resonance) spectroscopy:
NMR spectroscopy is a Spectroscopy technique used by chemists and biochemists
to investigate the properties of organic molecules, although it is applicable to any
kind of sample that contains nuclei possessing spin. For example, the NMR can
quantitatively analyze mixtures containing known compounds.
 Mass spectroscopy:
Mass spectrometry (MS) is an analytical technique that measures the mass-to-
charge ratio of ions. The results are typically presented as a mass spectrum, a plot
of intensity as a function of the mass-to-charge ratio.

(d) Chromatography Technique:

Chromatography is a method used by scientists for separating organic and inorganic
compounds so that they can be analyzed and studied. By analyzing a compound, a
scientist can figure out what makes up that compound. Chromatography is a great
physical method for observing mixtures and solvents. Chromatography may be
defined as method of separating a mixture of components into individual component
through equilibrium distribution between two phases. Chromatography is based on
the differences in the rate at which components of mixture moves through a porous
medium ( called stationary phase ) under the influence of some solvent or gas ( called
moving phase ).
 Paper chromatography: is one of the most common types of chromatography. It
uses a strip of paper as the stationary phase. Capillary action is used to pull the
solvents up through the paper and separate the solutes.
 Column chromatography: Column chromatography is a technique in which the
substances to be separated are introduced onto the top of a column packed with an
adsorbent, passed through the column at different rates that depend on the affinity
of each substance for the adsorbent and for the solvent or solvent mixture, and are
usually collected in solution as they pass from the column at different times.

 Gas chromatography: is used in airports to detect bombs and is used is forensics in

many different ways. It is used to analyze fibers on a persons body and also
analyze blood found at a crime scene. In gas chromatography helium is used to
move a gaseous mixture through a column of absorbent material.
  HPTL (high pressure thin layer) chromatography: HPTLC is one type of planar
chromatography and most advanced form of instrumental TLC. Now a day,
HPTLC is more useful than TLC and HPLC. Because HPTLC is independent of
sample application, chromatogram development, detection, etc. it is not only
instrumental TLC but entire concept that include widely standardize methodology
based on validated method. It is instrument controlled by software.
 HPLC(high pressure liquid chromatography): is used in the world to test water
samples to look for pollution in lakes and rivers. It is used to analyze metal ions
and organic compounds in solutions. Liquid chromatography uses liquids which
may incorporate hydrophilic, insoluble molecules.
 TLC(thin layer chromatography): uses an absorbent material on flat glass or
plastic plates. This is a simple and rapid method to check the purity of an organic
compound. It is used to detect pesticide or insecticide residues in food. Thin-layer
chromatography is also used in forensics to analyze the dye composition of fibers.
(e) Electrochemical Method:
Electrochemical methods: are analytical techniques that use a measurement of
potential, charge, or current to determine an analyte’s concentration or to characterize
an analyte’s chemical reactivity.
 Conductometry method:: Conductometry is a measurement of electrolytic
conductivity to monitor a progress of chemical reaction. Conductometry has
notable application in analytical chemistry, where conductometric titration is a
standard technique.
 Potentiometry method:
Potentiometry is one of the methods of electroanalytical chemistry. It is usually
employed to find the concentration of a solute in solution.
In potentiometric measurements, the potential between two electrodes is measured
using a high impedance voltmeter.
 Polarographic method:
an electrochemical method of analyzing solutions of reducible or oxidizable
substances.
 Voltammetry method:
Voltammetry refers to electrochemical methods in which a specific voltage profile
is applied to a working electrode as a function of time and the current produced by
the system is measured.
(f) Hyphenated Techniques:
 They are a combination of chromatographic and spectral analysis.
The hyphenated technique is developed from the coupling of a separation technique
and an on-line spectroscopic detection technology. The remarkable improvements in
hyphenated analytical methods over the last two decades have significantly broadened
their applications in the analysis of biomaterials, especially natural products.
 GC-MS
 LC-MS
 LC-NMR
 GC-NMR
 LC-MS-MS
(g) Other Methods:
 DSC
 Kjeldah Method
 ELISA
 Flame Photometry

(b)
Concentration Definition

In chemistry, concentration refers to the amount of a substance in a defined space. It relates to

the components of a mixture or solution.
Unit Examples of Concentration: g/cm3, kg/l, M, m, N, kg/L
Concentration is determined mathematically by taking the mass, moles, or volume of solute
and dividing it by the mass, moles, or volume of solution (or, less commonly, the solvent).
Some examples of concentration units and formulas include:

CONCENTRATION TERMS

Temperature Dependent Temperature Independent

1. Molarity 1. Percent Composition by mass

2.Normality 2.Molality
3.Mole fraction
1.Molarity (M)
Molarity or molar concentration is the number of moles of solute per litre of solution, which
can be calculated using the following equation:
M = Moles/Volume of solution(litre)
where, Moles = Given mass of solute(g)/molecular mass of solute(g)
Also, M = N/ valency

Example 1: Calculate molarity of of NaOH (20g) dissolved in 1L water.

 Given mass =20g

Molecular mass = 40g
Moles = 20/40 = ½

Molarity = Moles/Volume(L)
= (1/2)/ 1
= 1/2 M

Example 2: Calculate molarity of 0.1 N NaOH.

 Valency of NaOH = 1
N = 0.1 N (given)
M = N/ n
= 0.1/1 =0.1 M

For most purposes, molarity is the preferred unit of concentration. If the

temperature of an experiment will change, then a good unit to use is molality.
Normality tends to be used most often for titration calculations.

2. Normality (N)

Normality is described as the number of gram or mole equivalents of solute present in one
litre of a solution.

Normality = Number of gram equivalents × [volume of solution in litres]-1

Number of gram equivalents = weight of solute × [Equivalent weight of solute]-1

Example 1:What is the normality of the following?

(a)0.1381 M NaOH
N=M*n
= 0.1381 * 1
= 0.1381 N

(b)0.0521 M H3PO4
N= M * n
= 0.0521* 3
=0.1563 N
3.Molality

Molality is defined as the “total moles of a solute contained in a kilogram of a solvent.”

Molality is also known as molal concentration. It is a measure of solute concentration in a
solution. The solution is composed of two components; solute and solvent.

Molality = moles of solute/mass of solvent (kg)

Example 1: If 18 g glucose is present in 1 kg of water. Calculate molality.

m.m. of glucose = 180 g

m = g.m./ m.m.
= 18/180
= 1/10
= 0.1

4. Percentage concentration calculation

 % (w/w)
 %(w/v)
 %(v/v)

Mass Percent (%) - mass solute/mass solution x 100% (mass units are the same unit for both
solute and solution)

Volume Percent (v/v%) - volume solute/volume solution x 100% (solute and solution
volumes are in the same units)

Example 1: Calculate N and M of 10% (w/v) H2SO4 solution.

mm of H2SO4 = 98g

gm = 10 g

Volume = 90 ml = 0.09 L

M = moles/ Vol(L)

=(10/100) * (1000/90) = 10/9

= 1.1 M

As, valency = 2, N=M*n

= 1.1 * 2 = 2.2 N
5.Mole Fraction

Mole fraction = (mol/mol)

It is defined as ratio of moles of solute divided by total moles in the solution.

Xa = na /(na + nb)

Xb = nb/(na + nb)

Xa + Xb = 1

Where, a = solute

b = solvent

Example 1 : A mixture has 18 g water and 414 g ethanol .Calculate mole fraction of both
solutes.

mm of C2H5OH = 46 g

mm of H2O = 18 g

n(a) = 414/46 = 9

n(b) = 18/18 = 1

Xa = n(a)/n(a) + n(b)

= 9/10

Similarily,

Xb = n(b)/n(a) +n(b)

= 1/10

6.PPM (parts per million)

It is given by,

[given mass(solute) / given mass of solution] *10^6

Example 1: 1000 g of solution of CaCO3 contains 10g solute. Calculate concentration in ppm

According to the formula,

= (10/1000)* 10^6

= 10^4 PPM
7.PPB (parts per billion)

Used in atmospheric chemistry to describe the concentration of gasses.

Q.3 Write a detailed note on the following topics.

A (primary standard solution and their properties with example)-
These are made from compounds such as potassium hydrogen phthalate which are stable and
available in high purity and don’t absorb from the air. A solution prepared from a primary
standard can be trusted to have, pretty much exactly, the molarity one gets by weighing the
solid, converting to moles, and dividing by the volume of the solution.
The primary standard is then used to titrate the secondary standard solution to find out its
actual molarity
Properties of primary standard solution-
 High purity.
Stability (low reactivity).
Low hygroscopicity (to minimize weight changes due to humidity).
High equivalent weight (to minimize weighing errors)..
Non-toxicity.
Ready and cheap availability.
Examples of primary standards -used in redox titrations include pure iron,
NaC2O4 (sodium oxalate), As2O3 (arsenic trioxide), K2Cr2O7 (potassium
dichromate), KBrO3 (potassium bromate), KIO3 (potassium iodate) and KH(IO3)2
(potassium hydrogen iodate).
B (secondary figures and rule to determine them with examples
secondary standard solution is a solution in which the concentration of dissolved solute has
not been determined from the weight of the compound dissolved but by reaction (titration) of
a volume of the solution against a measured volume of a primary standard solution.
Secondary standards are commonly used to calibrate analytical methods. A secondary
standard is a standard that is prepared in the laboratory for a specific analysis. It is usually
standardized against a primary standard.
Properties of secondary standard solution-
 Its reaction with the analyte must be rapid in order to minimize the
waiting period after addition of each reagent.
  Its reaction must be reasonably complete.
 It should be possible to describe the reaction by a balanced chemical reaction.
 A secondary standard is a standard that is prepared in the laboratory for a specific
analysis. It is usually standardized against a primary standard

Examples of secondary standard solution-

The base NaOH is an example of a secondary standard solution.

c.) Accuracy
During pharmaceutical analysis, the term precision and accuracy is used to describe the
quality of analytical measurements. The term accuracy tells how much the
analytical results match with the true value. It is generally expressed by the difference
between the observed value and true value which is actually an error. The good accuracy
means there is the lowest possible difference or error.
In usual practice an accurate result is the one which matches very nearly with true value of a
measured amount. The comparison is normally done with regard to the ‘error’; and the
accuracy is inversely proportional to it i.e., the greater the accuracy, the smaller is the error.
‘Absolute error’ is the difference between the experimental value and the true value.
Example : An analyst determines a value of 70.55% cineole in a fresh sample of Eucalyptus
Oil that actually contains 70.25%, the absolute error is given by :
70.55 – 70.25 = 0.30%
The error thus obtained is invariably stated with regard to the actual size of the measured
quantity i.e, in percent (%). Therefore, the relative error is given by :
0 30/70.25 * 100 = 0.42%

d.) Precision
It may be defined as –‘the agreement amongst a cluster of experimental results;however it
does not imply anything with respect to their relation to the true value. Precision designates
‘reproducibility’ of a measurement,whereas accuracy the correctness of a measurement .
precision invariably forms an integral part of accuracy , but ironically a high degree of
precision may not necessarily suggest accuracy . Precision is usually expressed as standard
deviation or relative standard deviation.

Repeatability
The closeness of the agreement between results of successive measurements of the same
measurements of the same measurand carried out under the same conditions of measurement.
Repeatibilty condition include the same measurement procedure , the same observer , the
same measuring instrument , used under the same conditions , the same location , and
repetition over a short period of time.
Reproducibility
The closeness of the agreement between the results of measurements of the same
measurements carried out under changed conditions of measurements. Reproducibility
requires specification of the conditions changed. The changed conditiond may include
principle of measurement , method of measurement , observer , measuring instrument ,
reference standard , location , conditions of use and time.
For example:-

e.) SIGNIFICANT FIGURES

The number of digits used to express a measured or calculated quantity.
By using significant figures, we can show how precise a number is. If we express a number
beyond the place to which we have actually measured (and are therefore certain of), we
compromise the integrity of what this number is representing.

1. All non-zero numbers ARE significant. The number 33.2 has THREE significant figures
because all of the digits present are non-zero.
2. Zeros between two non-zero digits ARE significant. 2051 has FOUR significant figures.
The zero is between a 2 and a 5.
3. Leading zeros are NOT significant. They're nothing more than "place holders." The
number 0.54 has only TWO significant figures. 0.0032 also has TWO significant figures. All
of the zeros are leading.
4. Trailing zeros to the right of the decimal ARE significant. There are FOUR significant
figures in 92.00.
92.00 is different from 92: a scientist who measures 92.00 milliliters knows his value to the
nearest 1/100th milliliter; meanwhile his colleague who measured 92 milliliters only knows
his value to the nearest 1 milliliter. It's important to understand that "zero" does not mean
"nothing." Zero denotes actual information, just like any other number. You cannot tag on
zeros that aren't certain to belong there.
5. Trailing zeros in a whole number with the decimal shown ARE significant. Placing a
decimal at the end of a number is usually not done. By convention, however, this decimal
indicates a significant zero. For example, "540." indicates that the trailing zero IS significant;
there are THREE significant figures in this value.
6. Trailing zeros in a whole number with no decimal shown are NOT significant. Writing
just "540" indicates that the zero is NOT significant, and there are only TWO significant
figures in this value.
7. Exact numbers have an INFINITE number of significant figures. This rule applies to
numbers that are definitions. For example, 1 meter = 1.00 meters = 1.0000 meters =
1.0000000000000000000 meters, etc.
Round 1000.3 to four significant figures. 1000.3 has five significant figures (the zeros are
between non-zero digits 1 and 3, so by rule 2 above, they are significant.) We need to drop
the final 3, and since 3 < 5, we leave the last zero alone. so 1000. is our four-significant-
figure answer. (from rules 5 and 6, we see that in order for the trailing zeros to "count" as
significant, they must be followed by a decimal. Writing just "1000" would give us only one
significant figure.)
8. For a number in scientific notation: N x 10 x, all digits comprising N ARE significant
by the first 6 rules; "10" and "x" are NOT significant. 5.02 x 104 has THREE significant
figures: "5.02." "10 and "4" are not significant.
Rule 8 provides the opportunity to change the number of significant figures in a value by
manipulating its form. For example, let's try writing 1100 with THREE significant figures.
By rule 6, 1100 has TWO significant figures; its two trailing zeros are not significant. If we
add a decimal to the end, we have 1100., with FOUR significant figures (by rule 5.) But by
writing it in scientific notation: 1.10 x 103, we create a THREE-significant-figure value.

f.) Rules of Rounding off and addition subtraction multiplication and division with few
examples
When doing multiplication or division with measured values, the answer should have the
same number of significant figures as the measured value with the least number of significant
figures.

•Procedure to determine significant figures after multiplication or division:

Multiply or divide the numbers.
Round the result to have the same number of significant figures as the measured value with
the least number of significant figures.
Below are two examples.
A)Write the product of 2.10 × 0.5896 with the correct number of significant figures.
Step 1) 2.10 × 0.5896 = 1.23816
Step 2) 1.23816 = 1.24 (three sig. figs because 2.10 has three)
The answer is 1.24

A)Write the quotient of 16.15 / 2.7 with the correct number of significant figures.
Step 1) 16.15 / 2.7 = 5.98148148
Step 2) 5.98148148 = 6.0 (two sig. figs because 2.7 has two)
The answer is 6.0

When doing addition or subtraction with measured values, the answer should have the same
precision as the least precise measurement (value) used in the calculation.
•Procedure to determine significant figures after adding or subtracting:
1.Add or subtract the numbers.
Round the result to the same number of decimal places as the least precise value.

Below are two examples.

B)Write the sum of 1.586 + 2.31 with the correct number of significant figures.
Step 1) 1.586 + 2.31 = 3.896
Step 2) 3.896 = 3.90 (two decimal places because 2.31 has two decimal places )
The answer is 3.90

B) Write the difference of 0.954 - 0.3109 with the correct number of significant figures.
Step 1) 0.954 - 0.3109 = 0.6431
Step 2) 0.6431 = 0.643 (three decimal places; 0.954 has three decimal places )
The answer is 0.643

Q4.(a) what is pharmaceutical analysis? explain its types

Pharmaceutical analysis is a branch of practical chemistry that involves a series of

process for identification, determination, quantification and purification of a
substance, separation of the components of a solution or mixture, or determination of
structure of chemical compounds.
The substance may be a single compound or a mixture of compounds and it may be in
any of the dosage form. The substance used as pharmaceuticals are animals, plants,
micro organisms, minerals and various synthetic products.

There are main two types of analysis.

1. Qualitative (identification)
2. Quantitative (estimation)

1. Qualitative analysis is performed to establish composition of natural/synthetic

substances. These tests are performed to indicate whether the substance or compound
is present in the sample or not. Various qualitative tests are detection of evolved gas,
formation of precipitates, limit tests, colour change reactions, melting point and
boiling point test etc.

2. Quantitative analytical techniques are mainly used to quantify any compound or

substance in the sample. These techniques are based in (a) the quantitative
performance of suitable chemical reaction and either measuring the amount of reagent
added to complete the reaction or measuring the amount of reaction product obtained,
(b) the characteristic movement of a substance through a defined medium under
controlled conditions, (c) electrical measurement, (d) measurement of some
spectroscopic properties of the compound.

Various types of Qualitative analysis:

1.Chemical methods
a) volumetric or titrimetric methods
b) gravimetric methods
c) gasometric analysis
2.Electrical methods
3.Instrumental methods
4.Biological and microbiological

Scope of pharmaceutical analysis in detail?

Pharmaceutical Analysis is one of the most sort after specializations in masters of

pharmacy. People specialised in pharmaceutical analysis are indispensable to the
manufacturing , quality control and analytical manifestations of the industry.

They can work in quality control department which oversees the purity, qualitative
aspects and the matching of the stringent regulatory limits required by a finished
product.

Research and development has huge implications on the results of the analysis and
detection of new compounds. More and more companies are stressing on a separate
analytical R&D department.

Pharmaceutical analysis students also finds takers in the medical devices companies,
equipment companies, regulatory agencies etc

Define the terminology?

 Endpoint - the point in a titration at which a reaction is complete, often marked by a
colour change

Equivalence point or stoichiometric point is the point in a chemical reaction when

there is exactly enough acid and base to neutralize the solution. In a titration, it is
where the moles of titrant equal the moles of solution of unknown concentration

Indicator-compound that changes colour at a specific pH value or in the presence of

a particular substance, and can be used to monitor acidity, alkalinity, or the progress
of a reaction."the remaining alkali is titrated against standard acid using
phenolphthalein as indicator"

Titrand - a substance whose concentration is to be determined by titration.

Titrant is a solution of known concentration that is added (titrated) to another

solution to determine the concentration of a second chemical species. The titrant may also be
called the titrator, the reagent, or the standard solution

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.
 PRACTICALS

Aim 1 : To prepare and standardize 0.1N solution of sodium hydroxide.

References :
Class Notes
Internet

Requirements :

(a)Glassware
1.Burette
2.Conical flask
3.Volumetric flasks
4.Stirrers
5.Watch glass

(b)Chemicals
1) 0.1 N KHP
2) NaOH
3)Phenolphthalein
4) Distilled Water

Theory:

Acid Base titration-

is a method of quantitative analysis for determining the concentration of an acid or base by
exactly neutralizing it with a standard solution of base or acid having known concentration. A
pH indicator is used to monitor the progress of the acid–base reaction.

Neutralization reaction-
Is a chemical reaction in which acid and a base react quantitatively with each other. In a
reaction in water, neutralization results in there being no excess of hydrogen or hydroxide
ions present in the solution.

Indicator used : Phenolphthalein

Acid : Colourless Base : Pink

Colour change in following experiment: Pink to Colourless.

Principle :

KPH + NaOH NaKP + H2O

Potassium Sodium Hydroxide Salt Water
Hydrogen
Phthalate

Procedure :

1. After performing calculations , weigh 0.4 g of NaOH using a measuring weight.

2. Using a volumetric flask fill measured NaOH and water till mark.
3. Measure 10 ml of formed solution and fill in conical flask.
4. Fill the burette up to 0 mark with KHP solution.
5. Add 2 to 3 drops of indicator – Phenolphthalein.
6. Drop by drop add KHP solution into conical flask and note the neutralizing point.
7. After the first titration again fill up the burette up to 0 mark.
8. Keep on titrating until concurrent values of consumed volume are obtained.

Reaction:

KPH + NaOH NaKP + H2O

Potassium Sodium Hydroxide Salt Water

Hydrogen
Phthalate

Calculation : Considering we need to prepare a 100 ml solution,

N = M* valency factor
0.1 = M * 1 (v.f. for NaOH =1)
Therefore, M =0.1 M

M = moles/ Volume (L) ……………….(I)

We know, Moles = given mass/ molecular mass
For NaOH, g.m. = ?
m.m. = 40 g
Volume = 100 ml = 100/1000 L
M = 0.1 M
Putting the values in (I)
0.1 = (g.m / 40) *(1000/100)
Therefore , g.m. = 0.4 g
Hence we need 0.4 of NaOH for preparation of 0.1 N ,100 ml NaOH.

OBSERVATION TABLE :

For KHP,

S.No. Initial Volume Final Volume Consumed Volume

 1. 0 ml 9.8 ml 9.8 ml
2. 0 ml 10.1 ml 10.1 ml
3. 0 ml 10.1 ml 10.1 ml

Since 10.1 ml is the concurrent value, we will consider 10.1 ml as the consumed
volume of Potassium Hydrogen phthalate.

We know, N1 . V1 = N2 .V2

Where ; N1 ,V1 are normality and volume of KHP and N2 , V2 are normality and
volume of NaOH.

0.1 * 10.1 = N2 * 10
N2 = 0.101 N

Diagram

Filled with KHP till 0 mark (Primary

standard solution)(0.1 N)

Filled with 10 ml NaOH (Secondary

standard solution) + few drops of
phenolphthalein .

Applications:

1) Sodium Hydroxide (NaOH)

It is major ingredient in drain and oven cleaners.

It is used in chemical manufacturing, oil refining, hydraulic fracturing, water treatment.
It is used in the manufacture of fabric, plastic wrap, paper and soap.

2) Potassium Hydrogen phthalate (KHP)

KHP is slightly acidic, and it is often used as a primary standard for acid-base
titrations because it is solid and air-stable, making it easy to weigh accurately.
It is not hygroscopic.
It is also used as a primary standard for calibrating pH meters because, besides the
properties just mentioned, its pH in solution is very stable.
It also serves as a thermal standard in thermogravimetric analysis.

Result:

On performing acid base titration, Normality(N) of NaOH came out to be 0.101 N .

 (2) PRACTICAL-TO PREPARE AND STANDARDIZE 0.1N SOLUTION OF
HYDROCHLORIC ACID

AIM- To prepare and standardize 0.1N solution for hydrochloric acid.

REFERENCES- from notes and through internet.

REQUIREMENTS- (Glass-ware)- conical flask , burette , beaker , pipette , and measuring

cylinder.
(b)(Chemicals used)-hydrochloric acid sodium carbonate and methyl orange
solution.

THEORY-
An acid-base titration is a quantitative analysis of acids and bases ; through this
process , an acid or base of known concentration neutralizes an acid or base of
unknown concentration. The titration progress can be monitored by visual
indicators, pH electrodes, or both.
A neutralization reaction is when an acid and a base react to form and a salt
and involves the combination of H+ ions and OH- ions to generate water. The
neutralization of a strong acid and strong base has a pH equal to 7. The
neutralization of a strong acid and weak base will have a pH of less than 7, and
conversely, the resulting pH when a strong base neutralizes a weak acid will be
greater than 7.

PRINCIPLE-
Na2CO3+2HCl2NaCl+H2O+CO2
STEP-1) Na2CO3+HClNaHCO3+NaCl
STEP-2) NaHCO3 + HClNaCl+H2O +CO2

PREPARATION OF 0.1N IN 1000ml HCl-

N1V1=N2V2
N1=11.5(Normality of HCl)
N2=0.1
V1=?
V2=1000ml
 V1=(0.1*1000/11.5)100/11.5=8.7ml

PREPARATION OF 0.1N Na2CO3

Molecular weight of sodium carbonate is 106, 106/2=53g/l = 1N Na2CO3
For 0.1N Na2CO3=53/10=5.3g/l

1)Take 10ml hcl in the conical flask.

PROCEDURE 2) Add 3 drops of methyl orange indicator in the conical flask containing hcl;
which will become red coloured.
3)Titrate the above solution by using 0.1N Na2CO3, and at end point (0.1N,
10ml) light orange/yellow colours will be observed.

Na2CO3+2HCl2NaCl+H2O+CO2
REACTION

DIAGRAM
BASE-Na2CO3 (0.1N).
ACID-HCL (0.1N 10ML).
INDICATOR-METHYL
ORANGE 2-3 DROPS.

OBSERVATION
S.NO START POINT END POINT VOLUME
CONSUMED
1 0.0ml 9.8ml 9.8ml
2 9.8ml 19.7ml 9.9ml
3 19.7ml 29.6ml 9.9ml
CALULATION
N1V1=N2V2
N1=0.1;N2=?;V1=9.9ml;V2=10ml
0.1*9.9=N2*10
N2=0.099N
APPLICATION
OF HCL
It is used for many purposes such as:-
1)production of organic compound such as dichloroethane and vinyl chloride
for pvc.
2)for cleaning pools.
3)for digesting foods.
4)purification of salt.
5)regulate the pH level
6)HCl is effectively sed to regenerate ion exchangers. Etc.
RESULT
Hence the value of N2=0.099N
 3)TO PREPARE AND STANDARDIZE 0.1N SOLUTION OF SULPHURIC
ACID

Aim -To prepare and standardize 0.1 N solution for sulphuric acid.

References – From notes of kapil sir and through internet

Requirements – a (Glass-ware) used conical flask , burette and measuring cylinder , beaker

b (Chemicals used ( Sulphuric acid ,Sodium carbonate and methyl orange

solution)

Theory - An acid-base titration is a quantitative analysis of acids and bases; through this
process, an acid or base of known concentration neutralizes an acid or base of unknown
concentration. The titration progress can be monitored by visual indicators, pH electrodes, or
both.

A neutralization reaction is when an acid and a base react to form water and a salt and
involves the combination of H+ ions and OH- io ns to generate water. The neutralization of a
strong acid and strong base has a pH equal to 7. The neutralization of a strong acid and weak
base will have a pH of less than 7, and conversely, the resulting pH when a strong base
neutralizes a weak acid will be greater than 7.

Principal –

H2So4 +Na2CO3  Na2SO4 +Co2 + H2O

Preparation of 0.1 N –

N1V1 =N2V2: N1 = 36.4( normality of conc H2SO4)

36.4*V1=0.1 *1000

V1 = 0.1*1000/36.4=100/36.4=2.75 ML

Prepar
ation of 0.1 N NA2CO3

Mol.wt =106 eq.wt=106/2=53g/2=1N

53/10=5.3 g/l =0.1 N NA2CO3

Procedure-

1. Take 10 ml H2SO4 in the conical flask.

 2. Add -3 drops of methyl orange indicator in the conical flask containing H2SO4;which
will be become red colored

3. Titrate the above solution by using 0.1N NA2CO3 ,and at the end point (0.1N ,10ML)
light orange /yellow colors will be observed

Reaction –

H2So4 +Na2CO3  Na2SO4 +Co2 + H2O

Diagram-

Observation -

SNO START POINT END POINT VOLUME

CONSUMED
1 O.O 1O.1 1O.1 ml
2 11.0 21.0 10.O ml
3 21.0 31,1 10.1ml

Calculation –

N1V1 =N2V2 N1 *10=0.1 *10.1

N2=(0.1*10.1)/10=0.101N

APPLICATION OF H2SO4-

Industrial Applications of Sulfuric Acid

 Fertilizers.
 Pharmaceuticals.
 Gasoline.
 Automobile batteries.
  Paper bleaching.
 Sugar bleaching.
 Water treatment.
 Sulfonation agents

Result

Hence value of N2=0.010 N