Unit 6

1
 4.1 Principle and types of gravimetric analysis
 Gravimetric method of analysis is a quantitative chemical method

based on separating and weighing an analyte in a pure form or in

some combined form of known composition.

 That is, in most gravimetry or gravimetric analysis the analyte is

converted to an insoluble substance(precipitate) which is isolated &

weighed.

 The mass or weight of the element, ion or radical in the original

substance can be readily calculated from the weight of the ppt & its
composition (the formula of the cpd) & the relative atomic masses
of the constituent elements.
 Gravimetric methods are quantitative methods that are based on
determining the mass of a pure compound to which the analyte is
chemically related.

 A gravimetric method for the determination of diclofenac in

pharmaceutical preparations was developed.

 Diclofenac is precipitated from aqueous solution with copper(II)

acetate in pH 5.3 (acetic acid/acetate buffer).

3
  The specific steps in precipitation gravimetric analysis, including ;

 preparing the solution in proper form for precipitation,

 the precipitation process and how to obtain the precipitate in

pure and filterable form,

 the filtration and washing of the precipitate to prevent losses and

impurities; and
 heating the precipitate to convert it to a weighable form.

4
 OR

5
  Gravimetric methods, which are based upon the measurement of

mass, can be classified as:

precipitation gravimetry,

volatilization gravimetry,

electrogravimetry and

particulate gravimetry.

The first two are the major classes of gravimetry.

6
 4.1.1. Precipitation gravimetry
 is based on the formation of an insoluble compound following the
addition of a precipitating reagent to a solution of the analyte.
 The analyte is converted to a sparingly soluble precipitate.

 This ppt is then filtered, washed for free from impurities, and
converted to a product of known composition. This ppt is
finally weighed.
Examples:
a) The determination of chloride by precipitation as AgCl by addition
of Ag+ is one the simplest and inherently most accurate gravimetric
analyses known. The reaction is
Ag+ + Cl- →AgCl ↓
 After the precipitate (AgCl) is formed, it is washed to remove
soluble salt impurities, dried at 140 ± 10oC, cooled and weighed.
7
 4.1.2. Volatilization method

 A sample component that forms a gas or a vapor by heating or by a

chemical reaction can be determined by volatilization.

 The volatile constituents can be determined directly by collecting

and weighing it, or indirectly by measuring the difference of sample

mass as a result of the loss of the volatile constituent.

 Volatile components like water; carbon dioxide etc. of a substance is

8
often determined by volatilization.
 Examples:
a) Adsorbed water on to the surface of the sample particles
superficially, or within the sample particles and water of hydration
can be determined by heating a sample to a suitable temperature
and measuring the loss of the mass of sample.
 Alternatively, the water driven off may be carried to a trap of
adsorbent material in a stream of pre-dried air or nitrogen, and
the mass of water collected by the trap measured by weighing.
 Anhydrous calcium chloride, CaCl2, or magnesium perchlorate,
Mg(ClO4)2, make good adsorbents for water in this application.
9
 4.1.3. Electrogravimetry

 In electrogravimetry, the analyte is deposited as a solid film on an

electrode in an electrochemical cell as a result of oxidation or
reduction.

 Examples: The oxidation of Pb2+ and its deposition as PbO2 on

a Pt anode is an example of electrogravimetry. Reduction can
also be used in electrogravimetry.

 As an example electrodeposition of Cu on a Pt cathode provides a

direct analysis for Cu2+.

10
 4.1.4. Particulate gravimetry

 In particulate gravimetry, the analyte is determined following its

removal from the sample matrix by filtration or extraction.

Example:

 Suspended solid in wastewater is determined directly by filtering

and weighing.

 Particulate gravimetry is commonly used in the environmental

analysis of water, air and soil samples.

11
 4.2. Properties of precipitates and precipitating agents

 The general equation for precipitation gravimetry is:

 The success of analysis in precipitation gravimetry is dependent on

proper selection of precipitant, the physical nature of precipitated
form and the physical and chemical nature of the weighed form.

12
 4.2.1. Requirements for the precipitant, precipitated
form and weighed form
A. Requirements for ideal precipitant or precipitating reagent are:
 A gravimetric precipitant should react specifically or at least selectively with
the analyte.
 pecific reagents react only with a single chemical species (analyte).
 Selective reagents react only with a limited number of species.
 For example, AgNO3 is a selective reagent capable of precipitating common
ions such as Cl-, Br-, I- and SCN from acidic solution.
B. Requirements for ideal precipitated form are:
 The precipitate should be insoluble or of very low solubility to avoid loss of
 the precipitate (analyte) with the mother liquor or during washing and
filteration.
 The precipitate should be readily filtered and washed free of contaminants.
 The precipitate should be of known composition after it is dried, or ignited.
 The precipitate should be unreactive with the components of the
atmosphere.
13
C. Requirements for ideal weighed form are:
 The composition of weighed form should correspond exactly to its
chemical formula.
 The compositions of precipitates originally formed often do not
correspond to their formulas.
 Ignition may assist to correspond with the chemical formula.
 Example:

(Precipitated form) (Weighed form)

 The weighed form must have adequate chemical stability.

 That is, it should not be affected by absorption of vapor or CO2 from
the air, by oxidation or reduction, by decomposition at higher
14 temperature and similar processes.
 Example:

 But it is possible to convert CaO stoichiometrically into a chemically

more stable form CaSO4 by treating it with sulfuric acid.

15
 4.2.2. Conditions for precipitate formation and factors affecting
completeness of precipitation

A. Conditions for formation of precipitate

 A sparingly soluble electrolyte becomes saturated (forms precipitate)
when the product of the concentrations of its ions reaches the solubility
product constant, Ksp at a given temperature.
 Ion product < Ksp  the solution is not saturated, no precipitate formation
takes placed.
 Ion product > Ksp  the solution is supersaturated, certain amount of
precipitate formed.
 If the solution is not saturated, no precipitate will form. In this case, the
product is called the ion product, Qsp.
 Solubility product constants(Ksp) are used to describe saturated solutions
of ionic compounds of relatively low solubility.

16
 B. Factors affecting completeness of precipitation
(I) Excess of precipitant
 The precipitation can be much more complete if excess of precipitant is
used.
 Example: PbSO4(s)  Pb2+ + SO4 2- ;
Ksp = [Pb2+][SO42- ] = 2.2 x 10-8 at 25oC
 If it is required to precipitate Pb2+ more completely, i.e., to reduce its
concentration in the saturated solution of PbSO4 obtained at the end of
the precipitation, the concentration of the precipitating SO42- ions must be
raised; for that excess of precipitant (H2SO4) must be added. However,
great excess of precipitant may increase solubility of a precipitate by the
effect of:
 (a) formation of more soluble complex compounds
 (b) formation of more soluble acid salts.
 Therefore, it needs care to be taken up on addition of excess precipitant.
17
 (II) Temperature
 The value of Ksp is dependent on temperature.

 Solubility change with temperature is associated with the effect of heat on

dissolution.
 An increase in the temperature of a precipitation reaction retards
precipitate formation if the heat of dissolution of the precipitate is
endothermic.
 Moreover precipitation with heating favors growth of crystals (or
coagulation in the case of amorphous precipitates).
 Thus precipitates for which the solubility increases appreciably with
temperature must be cooled completely before filtering off the
precipitates.
18
 (III) Hydrogen ion concentration (pH)
 It is one of the most important factors influencing the degree of
precipitation.

 For instance, the precipitant is OH- in precipitation of sparingly

soluble metal hydroxides.

 The greater the solubility product of the hydroxide, the higher is the
OH- ion concentration required for complete precipitation, i.e., the
higher the pH at which the precipitation must be performed.
19
4.3. Steps in precipitation gravimetric analysis

 The steps required in a precipitation gravimetric analysis after the

sample has been dissolved can be listed as follows.

i. Preparation of the solution v. Washing

ii. Precipitation formation vi. Drying or Igniting

iii. Digestion vii. Weighing

iv. Filtration viii. Calculation

20
 i. Preparation of the solution
 Preparing so/n of the analyte is the first step in gravimetric analysis.

 After preparing the solution, the following may be performed ;

 The solution condition must be adjusted to maintain low solubility of the

precipitate and to obtain it in a form suitable for filtration.

 Preliminary separation may be necessary to eliminate interfering materials.

 Proper adjustment of the solution conditions prior to precipitation may also

mask potential interferences.

 Factors that must be considered in adjusting so/n conditions include the vol

of the so/n during pptn,

the conc range of the test substance,
21
the presence & concs of other constituents, temp & pH.
 ii. Precipitation formation
 ppts are formed when the analyte so/n is treated with a so/n containing the

precipitating agent (provided that the Ksp of the ppt exceeded).

 The principal goals of every gravimetric procedure are to produce a

precipitate that is pure and that can be filtered easily.

 For e.g. when AgNO3 added to a so/n containing chloride ion, a ppt of

silver chloride formed, Ag+ (aq) + Cl-(aq) AgCl(s).

 When pptn is performed a slight excess of the precipitating reagents is

added to assure complete pptn. An excess of precipitating agent should be

avoided because this increases chances of adsorption on the surface of the
ppt in addition to being wasteful.
22
 iii. Digestion of the precipitate
 Digestion is the process of standing a precipitate in the presence of the
mother liquor for a given period of time usually with heating.

 Digestion is usually done at elevated temp to speed the process, although

in some cases it is done at room temperature.

 Digestion results in the loss of weakly bound water and gives a denser,
more filterable precipitate.

 Digestion promotess low recrystallization of the precipitate. Particle size

increases and impurities tend to be expelled from the crystal.

 Digestion is used to obtain coarser precipitate that can be readily filtered

out, to avoid imperfection in the crystals and the dissolution of adsorbed
or trapped impurities in precipitates.
23
 Cont…
 Digestion improves the filterability of the precipitate and its purity.
 Crystals with a large specific surface area have a higher surface energy and a
higher apparent solubility than large crystals.

 This is an initial rate phenomenon & does not represent an equil condition,
& it is one of the consequences of heterogeneous equil.

 When a ppt is allowed to stand in the presence of the mother liquor (the
so/n from which it was precipitated), the large crystals grow at the expense
of the small ones. This is called digestion.

 The small particles tend to dissolve & reprecipitate on the surfaces of the
larger crystals.
 In addition, individual particles agglomerate to effectively share a common
counter ion layer and the agglomerated particle finally cement together by
forming connecting bridges.
24
 iv. Filtering
 A ppt may be separated from the mother liquor by filtering it through a
suitable filter paper, sintered glass, or sintered porcelain.

 The choice depends on the nature of the ppt & on the temp to which it
will be heated after filtering. Suction filtration, vacuum filtration,
etc can be used for filtration of the precipitate.

 Usually, ashless filter papers are used for this purpose.

 Sintered glass filters have the advantage of sufficient mechanical strength

to allow the use of suction to speed the filtering process and being able
to withstand temp up to about 500oC before the sintered glass begins to
soften.

 Sintered glass porcelain is available in various degree of porosity. Their

advantage over sintered glass is the ability to withstand temp up to
25
1200oC.
V. Washing the precipitate
 Impurities on the surface of the ppt can be removed by washing the ppt after
filtering.
 The ppt will be wet with the mother liquor, which is also removed by
washing. But many precipitates may not be washed with pure water because
peptization occurs.
 Peptization is the opposite of coagulation in which the ppt reverts to very
small particles and is lost during filtration.
 It is avoided by washing the ppt with solution of an electrolyte that can be
volatilized during ignition or drying.
 For e.g. dilute HNO3 is used as the wash so/n for AgCl. The HNO3 replaces
the adsorbed layer of Ag+/anion, and is volatilized when dried at 110oC.
 When a ppt is washed, a test should be made to determine whether the
washing is complete. This is usually done by testing the filtrate for the presence
of an ion of the precipitating reagent.
 For e.g. if chloride ion is determined by precipitating with AgNO3 reagent
the
26
filtrate is tested with Ag ion by adding NaCl or dilute HCl.
vi. Drying or igniting precipitate
 Ignition refers to heating of ppts strongly at relatively higher temp to derive
off bound water (about 500oC is required for strongly hydrated ppt), to bring
about change in composition or to burn off filter paper on which ppt has been
collected.

 Ignition at a much higher temp is usually required if pptn must be converted

to a more suitable form for weighing(weighed form) in a furnace.
 E.g. magnesium ammonium phosphate, MgNH4PO4, is decomposed to
pyrophosphate, Mg2P2O7, by heating at 900oC.

 The high temp used in ignition ruin fritted glass crucibles, so that porcelain
silica or platinum crucibles are required.

 This serves for the purpose of drying, removal of volatile electrolyte,

changing the composition of a product to weighable form, and in cases where
the ppt is collected on ashless filter paper; the filter is heated, so that the mass
27
does not add error to the mass of the ppt.
vii. Cooling and weighing precipitates
 A ppt must be cooled to room temp before weighing it has been heated to

the desired temp and kept there for the prescribed time.
 This is because even slightly warm objects placed in the enclosed pan

compartment of an analytical balance will set up air currents that

cause very erratic and incorrect weights to be recorded.
 Many gravimetric ppts have a tendency to pick up moisture while cooling

they are cooled & stored in a moisture free container called desiccator.
 To ensure that all of the ppt is converted to the desired weighing form, the

process of heating, cooling & weighing is generally repeated until a

constant weighed is achieved.
28
viii. Calculation of results
 In pptn gravimetry, the r/n ship b/n the analyte & ppt is determined by the
stoichiometry of relevant rxns. Calculation results are normally based
on the % of analyte in the sample.

% analyte = (mass of analyte / mass of sample) x 100

 The mass of the analyte being determined is calculated from the weight of
the ppt by means of gravimetric factor(GF)

Where a = mole of substance required(sought) and

b= mole of ppt
Weight of substance required = Wt of ppt × GF
 A general formula for calculating the percentage composition of the
substance sought is
29
Calculations of Results from Gravimetric Data
 The results of a gravimetric analysis are generally computed from 2

experimental measurements:

 the mass of a sample and

 the mass of a product of known composition.

 When the product is the analyte X, the concentration is given by equation:

 Gravimetric factor: It is a ratio of atomic/molecular weights that will

convert the weight of some pure substance into the weight of some other
substance that is stoichiometrically related to it.
30
 Examples on calculation of gravimetric factor

 1) Calculate the gravimetric factors for the following conversions

a) Mg2P2O7 to Mg

Mg2P2O7 is weighed form and Mg is the substance required, sought.

1 mols of Mg2P2O7 = 2 moles Mg thus

a (mole of substance ) = 2, b (mole of ppt) = 1

= 0.22

222

31
32
 E.g.-2 : Determine the amount of iron in 2.5 g Fe2O3.

Solution: To determine how many grams of iron are contained

in 2.5 g Fe2O3, one could simply multiply the weight given by
the fraction of it that is iron.

Gram of Fe = 2.50 x 2 Fe/ Fe2O3 = (2.50 x2(55.85))/159.70

= 1.749 g

Thus, the ratio 2 Fe/ Fe2O3 is called a gravimetric factor

(0.699).

33
E.g-3:The Ca in a 200 mL sample of natural H2O was determined by
precipitating the cation as CaC2O4. The ppt was filtered, washed, & ignited
in a crucible with an empty mass of 26.6002 g. The mass of the crucible plus
CaO (56.077 g/mol) was 26.7134 g). Calculate the conc of Ca (40.078
g/mol) in the H2O in units of grams per 100 mL
Solution: The mass of CaO = 26.7134 g – 26.6002 g = 0.1132 g;
The mass of calcium obtained can be calculated simply by multiplying the mass
of the precipitate by the gravimetric factor:

34
E.g-4: A 0.3516 g sample of a commercial phosphate detergent was ignited at
a red heat to destroy the organic matter. The residue was then taken up in
hot HCl, which converted the P to H3PO4. The phosphate was precipitated
as MgNH4PO4.6H2O by addition of Mg2+ followed by aqueous NH3. After
being filtered & washed, the ppt was converted to Mg2P2O7 (222.57 g/mol)
by ignition at 10000c. This residue weighed 0.2161 g. Calculate the percent
of phosphorus (30.974 g/mol) in the sample.
Solution: The mass of the analyte is:

35
E.g.-5: An Fe ore was analyzed by dissolving a 1.324 g sample in concentrated
HCl. The resulting so/n was diluted with water, & the Fe(III) was pptd as
the hydrous oxide Fe2O3.xH2O by the addition of NH3. After filtration &
washing, the residue was ignited at a high temp to give 0.5394g of pure
Fe2O3(159.69g/mol),
Calculate: (a) the % Fe(55.847 g/mol) and
(b) the % Fe3O4(231.54 g/mol) in the sample
Hint:- 3Fe2O3 2Fe3O4 + 1/2 O2

36
Cont…

37