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Model Answers of some questions

This will help you to prepare your own notes

1. Give short answers of the following questions:

(a) Distinguish between accuracy and precision of a measurement 1
Ans. The degree to which numbers in a group of measurement are in agreement with each
other is the precision of a measurement. For example, if three determinations of the
percentage of iron in the same iron ore sample gave values of 25.32, 25.30, and 25.33%;
the results are very close to each other i.e. results with high precision.

The term accuracy means that the extent to which the data or the average of a set of
data agree with the true value. [Relationship between accuracy and precision can be
represented graphically]

(b) Write one important advantage of Cr2O72- over MnO4- as an oxidizing titrant. 1
Ans. One important advantage of Cr2O72- over MnO4- as an oxidizing titrant is that available
Cr2O72- ion compounds fulfill the criteria of a primary standard substance. Its solution
concentration remains unchanged with time. On the other hand KMnO4 is a secondary
standard. It is difficult to obtain the substance perfectly pure and completely free from
MnO2. Moreover its standard solution undergoes decomposition on standing because
ordinary distilled water is likely to contain reducing substances (traces of organic matter
etc.]

(c) Explain that MnO4- ion acts as a self-indicator. 1

Ans. The MnO4- ion is highly coloured. As little as 0.01 ml of 0.01M KMnO4 solution can imparts
colour to 100 ml of distilled water. During titration, after completion of the oxidation of
reducing agent addition of 1 drop of KMnO4 solution imparts colour in the solution
indicating the end point of the reaction functioning as self-indicator.

(d) Which type of EDTA is generally used in preparing a standard solution and why? 1
Ans. Disodium salt of EDTA is generally used in preparing a standard solution. EDTA is a large
organic molecule. It’s solubility in water is less than Na2EDTA, that’s why Na2EDTA is
preferred for preparing a standard solution.

(e) Write down the names of the sources of uv and visible radiation used in the uv-visible 1
spectrophotometer.
Ans. The sources of uv and visible radiation used in the uv-visible spectrophotometer are (i)
hydrogen discharge lamp (deuterium lamp) for uv radiation source and (ii) Tungsten
filament lamp for visible radiation source.

(f) How diphenylamines function as a redox indicator? 1

The structural changes that occur during functioning as an indicator is given below
 2

2 NH (I)

NH NH (II)

N N (III)

When the entire reducing agent present in the system is consumed by the addition of
oxidizing titrant then additional one drop of the titrant brings the above changes.
The action of diphenylamine (I) as an indicator depends upon its oxidation first
into colourless diphenylbenzidine (II), which is the real indicator and reversibly
further oxidized to diphenylbenzidine violet (III).
(g) Mention one factor which is most likely to cause difficulties in gravimetric analysis.

(h) Explain the specificity of a chemical reaction with example.

2. (a) What are the disadvantages of carrying out titrations in aqueous medium? How these 5
problems can be overcome?
Ans. ▪ It has been observed from the examinations of titration curves for various strength acids
that acid or bases with dissociation constants less than about 1 × 10-8 cannot be titrated
successfully in water at about 0.1 M concentration

▪ This is because at lower values of the dissociation constant the breaks in the titration
curves are too small to enable observations of the end point, reflecting incomplete
titrations reactions.

▪ Some acids and bases are not soluble enough in water to produce a 0.1M solution,
requiring dissociation constant higher than 1 × 10-8 to enable end point measurement.

These problems can sometimes be overcome by using a solvent other than water – that is
a nonaqueous solvent.
▪ Nonaqueous solvents can be chosen that emphasize the acidity or basicity of analytes
so that the analytes can be titrated.

▪ A number of acids and bases that are not sufficiently soluble in water to be titrated are
soluble enough to titrate in properly chosen nonaqueous solvents.

▪ Nonpolar, non-ionic species, usually organic in nature may be much more soluble in a
water-immiscible organic nonaqueous solvent than in water, so that these species can
be dissolved and titrated at significant concentrations in an organic solvent.

(b) Explain that NH4+ can be titrated successfully with strong base in ethanol but in water. 4
Ethanol has been extensively studied as solvents for acid base titrations. It is /has/produce
1. Neither predominantly acidic nor basic
2. Low self-dissociation constant
3. Low dielectric constant
4. Un-dissociated ion pairs
 3

The acid dissociation reaction of NH4+ in ethanol is

NH4+ + CH3CH2OH ⇌ NH3 + CH3CH2OH2+ in which there is a +1 charge on both
sides of the reaction and the low dielectric constant of ethanol have no effect on the
dissociation reaction. In such case
(i) The low self dissociation constant of the solvent has a predominant effect
(ii) The degree of neutralization of NH4+ by strong base in ethanol is much higher
than degree of reaction of NH4+ with strong base titrant in water.
 NH4+ can be titrated successfully with strong base in ethanol, but not in water.

3. (a) What is gravimetric analysis 1

Gravimetric analysis consists of isolating in a pure form the analyte species or, more
commonly, a compound formed from the analyte, weighing the isolated species in a pure
form, and calculating the percentage of analyte in the known mass of the sample from
the mass of the isolated species.

(b) Write down the characteristics of a precipitate suitable for Gravimetric Analysis 4
Characteristics of a Precipitate suitable for Gravimetric Analysis
1. Very low solubility to avoid loss of the ppt with the mother liquor or from washing
during filtration. No more than about 0.1% of the ppt should be lost by this route.

2. No contamination by impurities that cannot be removed by washing or by heating

the ppt after filtration.

3. A solid state that is readily separable from the mother liquor by filtration. The ppt
particles must be large enough to be retained by the filter during removal of the
mother liquor and washing, and the particle should not clog the filter medium
unduly.

4. It must be possible by physical or chemical means, usually heating at a specified

temperature, to convert the ppt to pure material of well-defined chemical
composition.

(h) Discuss the advantages of organic precipitants in gravimetric analysis 4

It has been possible to develop a number of organic precipitants through organic
synthesis. These compounds are usually relatively high molecular weight chelating
agents that bond to a metal ion at least through two positions. The product should be
slightly soluble metal chelates useful for gravimetric analysis. Organic precipitants offer
several advantages. Normally the precipitants have high formula weight, thus reducing
relative errors in weighing. The compounds can be synthesized with a certain degree of
selectivity for various analytes. Selectivity can be increased by varying pH and
concentration of the analyte, as well as by the use of masking agents that complex
interfering ions and prevent them from forming a precipitate with the reagent.