Experiment 2 Gravimetric Analysis

EXPERIMENT 2
GRAVIMETRIC ANALYSIS

Structure
2.1 Introduction 2.3 Experiment 2B: Gravimetrically
determine Aluminium as
Expected Learning Outcomes
Aluminium 8-hydroxyquinolinate
2.2 Experiment 2A: Gravimetrically
determine Nickel(II) In Nickel Principle
Steel as dimethylglyoximate Requirements

Principle Procedure

Requirements Observations

Procedure Calculations

Observations Result

Calculations 2.4 Summary

Result 2.5 Further Reading

2.1 INTRODUCTION
As you are aware, that the aim of chemical analysis is to determine the
composition of naturally occurring or artificially prepared substances. This
usually done in two steps. As a first step, qualitative analysis is performed to
identify the different components of a substances. In the second step, the
quantitative analysis is performed in which the relative amounts of these
components are determined. In this laboratory course, you are required to
perform the quantitative analysis of components of known substances only. In
this unit we discuss some experiments for gravimetric determination of certain
ions to illustrate quantitative analysis. In Unit 1 of this course, we have already
described the scheme of qualitative analysis of mixtures of inorganic salts.

Methods of performing quantitative analysis are broadly classified into two

types:

i) Chemical methods which are based on quantitative performance of

suitable chemical reactions. Titrimetry or volumetry and gravimetry are the
examples of chemical methods of analysis.
ii) Instrumental methods which require the use of instruments for
measuring some physical properties such as electrical or optical properties of
substances for determining their composition. Conductometry, potentiometry
and colorimetry bare some of the examples of this class. 67
BCHCL-138 Chemistry Lab IV

In the Chemistry Laboratory course (BCHCL 132), you might have performed
some experiments on titrimetry, conductometry, potentiometry , and
colorimetry. Here, you shall perform some experiment on gravimetry.
In gravimetric analysis, the component to be estimated is converted into an
insoluble precipitate which is filtered, dried /ignited and weighed accurately.
Knowing the stoichiometry of the chemical reaction involved in precipitation
the mass of the precipitate is used to determine the amount of the component
in the substance.

Expected Learning Outcomes

After performing the given experiments you should be able to:

 determine nickel and aluminium as their soluble salts;

 perform various operations, i.e. precipitation, filtration, washing, drying,

ignition, cooling and weighing involved in gravimetric determinations;

 perform calculations involved in gravimetric determinations; and

 explain the principle underlying the gravimetric determination of nickel in

steel and alumimium as aluminium 8-hydroxyquinolate.

2.2 EXPERIMENT 2A: GRAVIMETRICALLY

DETERMINE NICKEL(II) IN NICKEL STEEL AS
DIMETHYL GLYOXIMATE
In this experiment you would learn about and perform the determination of
nickel in a given sample of steel. Steel is an alloy of iron with other elements
primarily carbon though a wide range of elements are used in these alloys.
The nature and amount of a given elements is determined by the desired
The complex
properties and application of steel. The presence of nickel in steel increases
formation involves the
its tensile strength and provides it resistance from corrosion.
ionization of an oxime
group each on the 2.2.1 Principle
two ligands and the
formation of In the gravimetric determination of nickel in steel, the Ni(II) ions are brought in
coordinate bonds with solution by dissolving the steel sample in concentrated acid.These are then
nitrogen atoms. precipitated from a slightly alkaline medium with an alcoholic solution of
dimethylglyoxime (H2DMG). The medium is made alkaline by subsequent
addition of aqueous ammonia solution. With the reagent nickel form a pure
stable compound which may be conveniently weighed. The formation of the
nickel complex, bis (dimethylglyoximate) nickel(II) can be represented as

68
Experiment 2 Gravimetric Analysis
This stable complex is rarely soluble and is of known composition. The
precipitate is washed with cold water and dried at 110-120 oC to volatalise any
unwanted reagent in it.

The presence of iron in the solution interferes with the determination as the
ferrous ions also form a red coloured complex with dimethylglyoxime.
Therefore, while bringing nickel ions into solution the ferrous ions are oxidized
to ferric ions by nitric acid. These are then masked with the help of tartarate or
citrate ions which keep Fe(II) ions in solution and do not let them complex with
DMG.

The generation of hydrogen ions in the process of complex formation

suggested that in acidic medium the reverse reaction would be significant.
Therefore, the complex formation is carried out in alkaline solution.

2.2.2 Requirements
Apparatus Number Chemical

Beaker (400 cm3) 1 Nickel steel (analyte sample)

Beaker (250 cm3) 2 Hydrochloric acid(AR: 6 M)

Weighing bottle 1 Dimethylglyoxime in ethanol

Watch glass 1 1% (w/v)

Glass rod 1 Dilute ammonia solution (6 M)

Policeman rod (glass rod with rubber tip) 1 Whatman filter paper 41

Glass funnel 1 Tartaric acid 15% (w/v)

Tripod stand 1 Concentrated ammonia

Wash bottle 1

Gooch sintered glass crucible 1

Desiccator 1

Analytical / Electronic balance 1

Wire gauze 1

Solutions Provided: Procedures for the preparation of these solutions are

given for the sake of information. These solutions would be prepared for you
by the counselor.

Dimethylglyoxime solution (1%). It is prepared by dissolving1 g of

dimethylglyoxime in 100 cm3 of 95% ethanol.

Dilute ammonia solution (6M): It is prepared by carefully adding 100 cm3 of

Gooch crucible
liquor ammonia to 100 cm3 of water taken in a 250 cm3 beaker.

15% (w/v) tartaric acid: It is prepared by dissolving, 15 g of tartaric acid in

about 60 cm3 of water taken in a 250 cm3 beaker and making up the volume to
100 cm3. 69
BCHCL-138 Chemistry Lab IV

2.2.3 Procedure
The procedure for gravimetric determination of nickel in steel can be divided
into the following steps:

a) Bringing nickel present in steel into solution as Ni(II) ions and oxidizing
iron to Fe(III) ions

b) Selective precipitation of Nickel ions with DMG in alkaline medium

c) Filtration and washing of the precipitate.

d) Cooling and weighing the precipitate

Follow the instruction given below in the sequential order to accomplish these
tasks.

a) Bringing nickel present in steel into solution as Ni(II) ions and oxidizing
Fe(II) to Fe(III) state.

b) Selective precipitation of Nickel ions with DMG in alkaline medium.

i) Dilute the solution to about 250 cm3 in a 400 cm3 beaker and add 5g
of tartaric acid or 30 cm3 of 15% (w/v) solution of tartaric acid (if
tartaric acid is not available you may use citric acid)

Neutralize the solution with dilute aqueous ammonia solution. You

should obtain a totally clear solution in this process (in case a
precipitate appears or if the solution is not clear when it is made
ammoniacal, then acidify the solution back and add more tartaric (or
citric acid.)

iii) In case any insoluble material is still there filter it and wash with hot
water containing a little ammonia/ammonium chloride solution.)

iv) The solution becomes highly ammoniacal then you must acidify by
adding dilute hydrochloric acid. You may use a litmus paper on pH
paper to monitor the process. There should be no smell of NH3 ,

v) Warm the solution to 60-80 oC and add 20-25 cm3 of 1% ethanolic

solution of dimethylgyoxime, immdediately followed by dilute
ammonia solution dropwise until the liquid is slightly ammoniacal,

vi) Stir well and keep the beaker on a water bath for 20-30 minutes and
allow the solution stand for about an hour; the temperature should
come down to room temperature during this time.

c) Filtration and washing of the precipitate

i) Take a constant weight Gooch crucible and filter the precipitate

obtained above

ii) Test the filtrate for complete precipitation by adding a little DMG
solution to a few drops of the filtrate

iii) Wash the precipitate with cold until free form chloride ions, The
70 presence of chloride ions can be tested by collecting a few drops of
Experiment 2 Gravimetric Analysis
the filtrate in a test tube, acidifying with HNO3, and adding a few
drops of 0.1 M AgNO3. A white precipitate or turbidity indicates the
presence of chloride ions. The washing is said to be complete when
there are no chloride ions

iv) Dry the precipitate by keeping the crucible at 100-120 ºC in an oven

for 45-60 minutes.

v) Transfer the crucible to a desiccator containing fused calcium chloride

and allow it to cool.

vi) Take out the crucible from the desiccator and weigh the crucible with
the precipitate.

vii) Keep the crucible again in the oven for about 10 minutes, cool in the
desiccator and weigh it again.

viii) Repeat the heating –cooling –weighing cycle till a constant mass in
obtained.

Precautions

 If the tartaric acid solution is not clear it must be filtered

 The pH of the solution from which the precipitation is to be done should

be carefully controlled

 The amount of precipitating agent added should be controlled. If you use

excess of DMG then a portion of the precipitate may dissolve as the
alcohol content of the solution increases to a great extent.

2.2.4 Observations
Mass of steel taken You may need to take
more reading if the
i) Mass of empty weighing bottle = g mass of the crucible
does not become
ii) Mass of empty weighing bottle + steel = g constant.

iii) Mass of empty weighing bottle after transferring = g

the steel in to beaker

Mass of the empty crucible

iv) 1st reading of mass of empty crucible = ………g

v) 2nd reading of mass of empty crucible =……….g

Mass of crucible + Ni(DMG)2 (precipitate)

vi) 1st reading of mass of crucible + precipitate =………g

vii) 2nd reading of mass of crucible + precipitate =………g

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BCHCL-138 Chemistry Lab IV

2.2.5 Calculations
The mass of steel taken = ii) – iii) g = w g

Mass of Ni(DMG)2 (precipitate) = vii) – v) = p g

Mass of Ni (DMG)2 contain one mole of Ni2+ ions.

Thus,

288.7 g (1 mole) of Ni (DMG)2 would contain = p [58.7/288.7] g of Ni2+ ions

Thus the mass of Ni in the given sample of steel = p[587.7/288.7] g = ……..g

% of Nickel in the given sample of steel = 100 (mass of Nickel /mass of steel
taken)%, so

p
% Ni2    100
w

Substituting the values in the expression, we get, the percentage of Ni in the

given sample of steel.

2.2.6 Result
The percentage of nickel in the given sample of nickel steel is found to be = %

2.3 EXPERIMENT 2 B: GRAVIMETRICALLY

DETERMINE ALUMINIUM AS ALUMINIUM 8-
HYDROXYQUINOLINATE
In Experiment 2a you performed the determination of nickel ions as
dimethylglyoximate in nickel steel. In this experiment, you will perform the
determination of aluminium ions as aluminium 8-hydroxyquinoinate or oxinate.

2.3.1 Principle
Aluminium ions are precipitated as aluminium(III) oxinate from ammonium
acetate-acetic acid buffered solution at pH 5.0 by the addition of 8-
hydroxyquinoline (oxine) solution in acetic acid. The precipitate is filtered
through a sintered glass crucible, washed with water, dried at 130  140 C in
an electric oven and weighted as aluminium (III) oxinate.

Al3  (aq )  3C9H7ON (aq )  Al(C9H6ON)3 (s)  3H (aq )

2.3.2 Requirements

Apparatus Number Chemical

Beaker (400 cm3) 1 Potash alum

Beaker (250 cm3) 2 Concentrated Hydrochloric

acid

72 Weighing bottle 1 Acetic acid

Experiment 2 Gravimetric Analysis

Watch glass Ammonium acetate

Glass rod 1 8-Hydroxyquinoline

Rubber policeman 1 Whatman filter paper 41

Glass funnel

Tripod stand 1

Pair of tongs

Wash bottle 1

Gooch sintered glass crucible (G4) 1

Desiccator 1

Water bath

Analytical / Electronic balance 1

Wire gauze 1

2.3.3 Procedure
Weigh out accurately about 0.5 g of potash alum from a weighing bottle into a
400 cm3 beaker. Dissolve in 20–25 cm3 of distilled water. Alternatively, take 25
cm3 of the solution prepared by your counselor. Add 1 cm3 of conc. HCI and
dilute the solution to 150cm3. Add 5–6 cm3 of 8-hydroxyquinoline (oxine)
reagent (a 10% solution in 20% acetic acid) and heat to 70  80 C . Slowly
add 25 cm3 of 2 M ammonium acetate solution dropwise and with constant
stirring to ensure complete precipitation. If the supernatant liquid is yellow to
orange in colour, it means enough 8-hydroxyquinoline has been added. Heat
the contents on boiling water bath for half an hour so that the precipitate
becomes granular and of easily filterable form. Allow to cool.

Filter the precipitate through a constant weight sintered glass crucible of

porosity G4. Wash the precipitate first with hot water and then with cold water.
Continue washing till the filtrate is almost colourless. Dry the precipitate at
130  140 C in an electric drying oven. Cool in a desiccator and weigh as
Al(C9H6NO)3 . Repeat the process of heating, cooling and weighting till the
weight becomes constant.

2.3.4 Observations
Weight of potash alum

i) Weight of empty weighing bottle = g

ii) Weight of weighing bottle + potash alum = g

iii) Weight of weighing bottle after transferring = g

73
BCHCL-138 Chemistry Lab IV

Weight of sintered crucible

iv) 1st weight of sintered crucible = g

v) 2nd weight of sintered crucible = g

Weight of sintered glass crucible + precipitate

vi) 1st weight of crucible + precipitate = g

vii) 2nd weight of crucible + precipitate = g

2.3.5 Calculations
Calculate the percentage of aluminium ions in potash alum as follows:

Weight of potash alum taken for experiment = ii) – iii) g

=wg

Weight of Al(C9H6NO)3 formed = vii) – v) g = x g

You know that one mole of potash alum (K 2SO4.Al2 (SO4 )3.24H2O) contains
two moles of aluminium ions which are converted into two moles of
aluminium(III) 8-hydroxyquinolinate. Thus,

K 2 SO4 Al2 (SO4 )3 .24H2O  2Al3   2Al(C6H6NO)3

948.76 g = 2 × 26.98 g = 2 × 459.43 g

wg =yg? =xg

Hence, weight of Al3  ions in x g of Al(C9H6NO)3

26.98
y  xg
459.43

Now this y g of Al3  ions are present in w g of the potash alum taken for
analysis. Hence, percentage of Al3  ions is potash alum

y
% Al3    100
w

26.98 x
  100%
459.43  w

26 .98  weight of Al(C9H6NO)3 formed

% Al   100 %
459 .43  weight of potash alum taken

Compare this value with the theoretical percentage of Al3  ions (5.69%,
calculated in Experiment 4) in potash alum.

If you have performed the experiment carefully, the experimental and the
calculated values should agree within 0.5% with each other. Following a
similar procedure, you can calculate the percentage of Al3  ions in any other
74 substance.
Experiment 2 Gravimetric Analysis
2.3.6 Result
You can report your result in any one of the following forms as instructed by
your counselor.

Weight of Al(C9H6NO)3 formed = g

or

Percentage of aluminium ions in potash alum = %

2.4 SUMMARY
In this unit we described tge gravimetric estimation of nickel and aluminium
ions present in a water soluble compound. We discussed how to perform
various operations involved in gravimetric determinations and also how to
calculate the percentage of these ions in their compounds.

2.5 FURTHER READING

1. Vogel’s Qualitative Inorganic Analysis, G. Svehla, Orient Longman, Sixth
edition, 1987.

2. A Text Book of Quantitative Inorganic Analysis, A.I. Vogel, J. Bassett, R.C.

Denney, G.H. Jeffery, J. Mendham, Longman, Fourth edition, 1978.

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