CLASSICAL METHODS OF

ANALYSIS
Analytical Chemistry
http://uomosul.edu.iq/public/files/datafolder_2890/_20191028_083135_780.pdf
What are analytical techniques in chemistry?

Analytical technique is a method that is used to determine

the concentration of a chemical compound or chemical
element.

Wide variety of techniques:

• Simple weighing (gravimetric analysis)

• Titrations (titrimetric)
• Use of very advanced techniques using highly specialized
instrumentation.
GRAVIMETRIC
ANALYSIS
• A gravimetric analysis is based upon the measurement of the weight
of a substance that has a KNOWN composition and is chemically
related to the analyte.

Signal – Mass or change in MASS

GRAVIMETRIC METHOD

DIRECT METHOD INDIRECT METHOD

An analyte mass can be measure Measure the change in Mass

directly by placing it on a balance
and recording its mass.
Gravimetry encompasses all techniques
in which mass or a change in mass is
measured.
ex:

When you step on a scale after exercising

you are making, in a sense, a gravimetric
determination of your mass.
Measuring mass is the most
fundamental of all analytical
measurements, gravimetry is
unquestionably the oldest analytical
technique.
• The indirect determination of
moisture content in foods is done by
difference.
-sample’s initial mass includes the
water, the final mass is measured
after removing the water.

The analyte can be determined indirectly

without its ever being weighed. Again, as Moisture determination in food
with the determination of Pb2+ as PbO2(s),
take advantage of the analyte’s chemistry.
Gravimetric analysis (quantitative
estimation by weight)
• the process of isolating and weighing an
element or a compound of the element in as
pure form as possible.
-transformation of the element or radical into a
stable, pure compound which can be converted
into a form suitable for weighing.
-weight of the element is calculated from the
formula of the compound.
-separation of the element or its compound
accomplished by either precipitation,
volatilization or electroanalytical methods
 Types of Gravimetric Methods

Particulate gravimetry--A gravimetric method in which the mass of a

particulate analyte is determined following its separation from its matrix.

Precipitation gravimetry—a gravimetric method in which the signal is the

mass of a precipitate.

Volatilization gravimetry--A gravimetric method in which the loss of a

volatile species gives rise to the signal.

Electrogravimetry--a gravimetric method in which the signal is the mass of

an electrodeposit on the cathode or anode in an electrochemical cell.
 Gravimetric Analysis
Conditions:

1. Must be a stoichiometric reaction.

Unbalanced reaction:

Na2CO3 (s) + 2HCl (aq) → 2NaCl (aq) + CO2 (g) + H2O (l)

•Chemical reactions are balanced by adding coefficients so that the number of

atoms of each element is the same on both sides.

• Molar ratios can be derived from the coefficients of a balanced chemical

equation.
Example:
1.00 g of Zinc reacts with Sulfur to produce Zinc Sulfide. If there is excess Sulfur,
what mass of Zinc Sulfide should be produced?
8 Zn(s) + S8(s) 8 ZnS(s)
Given: wt of Zn – 1.00 grams Required: mass of ZnS
Steps:
-Balance the equation to determine the mole ratio
-Convert mass of Zinc to moles (using molar mass of Zinc)
-Use mole ratio to predict moles of ZnS produced
-Convert moles of ZnS to mass (using the molar mass of ZnS)

Solution:
g ZnS = 1.00 g Zn (1 mole Zn/65.4 g Zn) (8 mole ZnS/8 mole Zn) (97.4g ZnS/mole ZnS)
= 1.49g ZnS
 Gravimetric Analysis
Conditions:
2. A stable product; no oxidation, dehydration or gelatinous
precipitates.
 Gravimetric Analysis
Conditions:
3. Must avoid side reactions which result in
coprecipitates.

A side reaction is a chemical reaction that

occurs at the same time as the actual
main reaction, but to a lesser extent. It leads to
the formation of by-product, so that the yield
of main product is reduced.
 Gravimetric Analysis
Conditions:

1. Must be a stoichiometric reaction.

2. A stable product; no oxidation, dehydration or
gelatinous precipitates.
3. Must avoid side reactions which result in
coprecipitates.
Particulate Gravimetry
When the analyte is already present as in a particulate form that
is easy to separate from its liquid, gas, or solid matrix Particulate
Gravimetry can be applied.
Particulate Gravimetry
• defined in terms of the mass of the particle itself, the
sensitivity of the analysis is given by the balance’s
sensitivity.

The analyte is determine by separating it from the

sample’s matrix using a filtration or an extraction.
Suction Filtration
• Filter flask
• Buchner funnel
• Filter paper
• Glass frit
• Filter adapter
• Heavy-walled rubber tubing
• Water aspirator
Filtration: TSS in water
 • A raw sewage sample was brought in for total suspended solids and volatile solids
Example analysis. A portion of the sample was poured into a tared evaporating dish and
weighed. The sample was then heated at 105oC for 4 hours, weighed, heated at
550oC overnight, and weighed again. The data are as follows:
Given: Tared mass evap dish 42.9073g Wet sample 104.4680g
105oC mass 45.4140g 550oC mass 43.3236g
Required: a. TSS in g/L b. % Volatile Solids
Solution:
TSS (mg/L) = (Dry mass of residue and filter – dry mass of filter, in grams)
ml of samples *. 1,000,000
= (Dry mass of residue and evap dish – dry mass of evap dish, in grams)
ml of samples *. 1,000,000
= 45.4140g - 42.9073g
104.468g - 42.9073g % to ppm = 4.0719 *10,000
100
= 2.5067/61.5067 *100 = 40,719 ppm or 40,719 mg/L
= 4.0719% mg/L to g/L = 40,719 mg/L * 1 g/1000 mg
= 40.7190 g/L
Precipitation and volatilization
gravimetric methods require
that the analyte, or some other
species in the sample,
participates in a chemical
reaction.
PRECIPITATION GRAVIMETRY
 Precipitation Gravimetry

•based on the formation of an insoluble compound following the

addition of a precipitating reagent, or precipitant, to a solution of
the analyte.

Precipitant---A reagent that causes the precipitation of a

soluble species.

• In most methods the precipitate is the product of a

simple metathesis reaction between the analyte and
precipitant.
• Any reaction generating a precipitate can potentially
serve as a gravimetric method.
 Theory and Practice
1. Precipitate must be of low solubility, high purity, and of known
composition if its mass is to accurately reflect the analyte’s mass.
2. Precipitate must be in a form that is easy to separate from the
reaction mixture.

Solubility Considerations
•precipitate’s solubility be minimal.
•Many total analysis techniques can routinely be performed with
an accuracy of better than ±0.1%.
•To obtain this level of accuracy, the isolated ppt must account for
at least 99.9% of the analyte.
•By extending this requirement to 99.99% accuracy is not limited
by the precipitate’s solubility.
Precipitation Gravimetry

Sulfate Content in a Fertilizer

Precipitation Process
Determination of Chloride
Ideal Analytical Precipitation
Precipitation Reactions
Key Concepts

•A precipitate is an insoluble solid that forms when solutions are

mixed.

•Solubility Rules can be used to predict if a product will be insoluble

(forms a precipitate) in aqueous solutionsat 25°C

•A precipitation reaction is a chemical reaction which produces a

precipitate when solutions are mixed together.
 Precipitation Reactions
•Spectator ions are ions in solution
that are not used to form the
precipitate. Spectator ions do not
participate in precipitation, they
"watch" the action like spectators
watching sport.

•States of matter must be included in

the chemical equation for a
precipitation reaction:(s) for solid, the
precipitate There are different types of ions, including
cations, anions, and spectator ions. A spectator
(l) for liquid (g) for gas ion is one that exists in the same form on both
the reactant and product sides of a chemical
(aq) for substances reaction.
in aqueous solution
Precipitation Reactions
Key Concepts

• Chemical equations written to represent precipitation reactions can be written in

one of three ways:

1. Molecular Equations:

All reactants and products are written as if they are molecules:

example:

AB(aq) + CD(aq) → AD(aq) + CB(s)

Molecular Equation

Example:

NaCl(aq) + AgNO3 (aq) NaNO3 + AgCl (s)

• NaCl(aq) contains Na+(aq) , and Cl- ions (aq)

• AgNO3 (aq) contains Ag+(aq) , and NO3l- ions (aq)

The possible products are

SALTS made up of cation and
an anion.
From the solubility rules:

•Sodium nitrate, NaNO3, is soluble

o All Group 1 ions form soluble salts, sodium nitrate,

NaNO3(aq), is soluble.
o All nitrates are soluble, sodium nitrate, NaNO3(aq), is
soluble.

•Silver chloride, AgCl(s), is insoluble (silver chloride is the

precipitate).

o All chlorides are soluble EXCEPT those of silver, lead(II),

mercury(I), copper(II) and thallium.
Solubility rules are qualitative rules to determine whether
an ionic compound will, or will not, dissolve in water at 25°C.

•An ionic compound that does dissolve in water is said to be

soluble. The result is an aqueous solution.

• Aqueous solution of a salt is indicated by placing the letters aq

in round brackets, (aq), to the right of the formula for the ionic
compound.
• An ionic substance that does not dissolve in water is said to be
insoluble. The result is a precipitate, an insoluble solid.
• Precipitate of a salt is indicated by placing the letter s in round
brackets, (s), to the right of the formula for the ionic
compound.
Solubility Rules

•Solubility Rules can be given as a list, a table, or a chart.

•Solubility Rules can be used to decide if a precipitate (an

insoluble substance) will form from an aqueous solution at 25°C

o List the anions and cations in the solution

o List the possible ionic compounds that could be produced
o Use the solubility rules (list, table or chart) to decide if
either of the ionic compounds are insoluble and will
therefore form a precipitate.
Solubility Rules as a List

The solubility of ionic compounds in water at 25°C, in general:

•All compounds of the ammonium ion (NH4+) are soluble.
•All compounds of Alkali metal (Group 1, or, Group IA) cations,
are soluble.
•All nitrates are soluble.
•All acetates (ethanoates) are soluble.
•All chlorides, bromides and iodides are soluble
EXCEPT those of silver, lead and mercury(I)
•All sulfates (sulphates) are soluble

EXCEPT those of silver, lead, mercury(I), barium, strontium

and calcium

•All carbonates, sulfites (sulphites) and phosphates are insoluble

EXCEPT those of ammonium (NH4+) and Alkali metal (Group 1,

or, Group IA) cations.

•All hydroxides are insoluble

EXCEPT those of ammonium (NH4+), barium and alkali metal

(Group 1, or, Group IA) cations.
•All sulfides are insoluble

EXCEPT those of ammonium, Alkali metal (Group 1, or, Group

IA) cations and Alkali earth metal (Group 2, or, Group IIA)
cations.

•All oxides are insoluble

EXCEPT those of calcium, barium and Alkali metal (Group 1,

or, Group IA) cations; these soluble ones actually react with
the water to form hydroxides (they are said to hydrolyse, and
the reaction with water is known as a hydrolysis reaction ).
• A solute is said to be soluble if its solubility is greater
than 1 g/100 g of water (1 g/100 mL water at 25°C)

• A solute is said to be insoluble if its solubility is less

than 0.1 g/100 g of water (0.1 g/100 mL water at 25°C)

• A solute is said to be slightly soluble, or sparingly

soluble, if its solubility is between 0.1 g/100 g of water
and 1.0 g/100 g (between 0.1 g/100 mL water and 1.0
g/100 mL at 25°C)
YES - the compound is
soluble, it will dissolve in
water at 250C

NO - the compound is
insoluble, there is no
appreciable concentration of
ions atc250C, the solid
compound will precipitate out
of the solution.

SLIGHTLY – very small

amount of the compound will
dissolve in water at 250C, very
small concentration of ions in
the solution.

REACT – the compound does

not dissolve in water (physical
change) instead it reacts with
water (chemical change)
Why are we concerned about solubility considerations when
doing gravimetric analysis?

• Precipitate must be insoluble so that

greater than 99.99% of analyte present in
solution precipitates in order for
gravimetric analysis to be considered
quantitative
• Solubility losses (to solution) can be
minimized by carefully controlling the
composition of the solution in which the
precipitate forms. This requires
understanding the relevant equilibrium
reactions affecting the precipitates
solubility.
Precipitation Reactions
Key Concepts

2. Ionic Equations:

All reactants and products that are soluble are written as ions, only
the precipitate is written as if it were a molecule:

example:

A+(aq) + B-(aq) + C+(aq) + D-(aq) → A+(aq) + D-(aq) + CB(s)

Ionic Equation
An ionic equation is a balanced
chemical equation that does
NOT assume all reactants and
products exist in solution as
"molecules".
•Species that exist in solution as
ions are shown as ions.
•The precipitate (insoluble salt)
is shown as a "molecule".

For the precipitation reaction that occurs when aqueous solutions of NaCl and AgNO3 are
mixed, the balanced ionic equation is:

Na+(aq)+Cl-(aq)+Ag+(aq)+NO3-(aq) →Na+(aq)+ NO3(aq)+AgCl(s)

Precipitation Reactions
Key Concepts

3. Net Ionic Equations:

Only the reactants and product taking part in the formation of the
precipitate are written in the equation, the reactants as ions, the
product as a molecule.

Spectator ions are not included in the equation. Example:

B-(aq) + C+(aq) → CB(s)

Volatilization Gravimetry
Volatilization gravimetry

-involves separating components of our

mixture by heating or chemically decomposing
the sample. The heating or chemical
decomposition separates out any volatile
compounds, which results in a change in mass
that we can measure.
- thermally or chemically decompose the sample
and measure the resulting change in its mass.
Direct Gravimetric Method
Tips for good Gravimetric Analyses
• Things which can be done for best
gravimetric results:
• Cool solution after precipitation has
started.
• Add precipitating reagent slowly so
crystals are larger
• Keep the volume of solution large so
concentration of analyte and
precipitant is low.
Characteristics of Good Gravimetric Techniques
Ideally Precipitates in a gravimetric analysis should be:
• Insoluble, Ksp should be way below the amount expected in solution.
Limiting factor for detection is usually the balance, not Ksp. (For
larger samples, this may not be true.)
• Easily filterable, make large crystals which separate from solution
easily
• Pure with known composition, that is, they do not make a whole
bunch of insoluble complexes.
Laboratory procedures
Transfer of solids
• Single chunk handle with tweezers
• Powdered transfer washings with at
least 3 times with solvent
• Weighing bottles: tight fitting ground
glass joints prevents contamination or
loss of sample. When handling ground
glass joints use either paper or tongs
• Handling precipitates Solution is
precipitated
 Laboratory Technique Considerations
1. Filters
• Paper is very hydroscopic, hard to get reliable tare weight
• GFF made from glass fibers less hydroscopic but should still be kept in
desicator. Very fine pores, different pore sizes available.
• Sintered glass fibers cannot be heated to high temperatures
2. Transferring
• decant: Pour majority of supernatant through without disturbing
precipitate.
• Wash precipitate: decant wash solution.
3. Control of moisture
• Moisture is ubiquitous in the laboratory, in order to control for this a dry
atmosphere will have to be maintained in a reproducibly dry atmosphere
by storage in a desicator or evaporation or ignition
Laboratory Considerations continued
4. Drying: Occurs by putting an open weighing bottle (may be covered
with a watch glass) at a temperature slightly above 100oC to get rid of
water or waters of hydration.
5. Weighing to constant weight means with +0.1mg
• Requires more than one weighing!!!
6. Dessicators
• Objects cannot be weighed when hot or warm. But if you were to
take a sample out and wait for it to cool it would pick up moisture like
that so put it in a desicator. Don’t seal descicator, creates a vacuum
Desicant blue dry pink wet
Common Desiccants
Mechanism of Action
Hydration ANHYDRONE® (Magnesium
Perchlorate anhydrous), CaCl2,
MgO, MgSO4, K2CO3, KOH,
Drierite, Na2SO4 (anhydrous),
ZnCl2
Absorption and/ or Adsorption BaO, CaSO4, Molecular Sieve,
H3PO4, NaOH Pellets
Chemisorption CaO, P2O5
• Silica gel goes from blue to pink as it • Anhydrous sodium sulfate gets clumpy
absorbs moisture Can be regenerated as it absorbs water
in oven

http://www.jtbaker.com/techlib/documents/3045.html
Further laboratory considerations
7. Evaporating: Evaporating dishes allow rapid evaporation but also
are easy to tip otherwise cause loss of analyte. Glass beads may be
added to avoid bumping and loss of analyte.

8) Ignition: Hotter temperature for elimination of water or other

reactant
• Muffle furnaces that go up to 1100oC are used primarily for this
Need to use porcelain crucible.
Species Precipitated form Form weighed Some interfering
analyzed species
K+ KB(C6H5)4 NH4+, Ag+, Hg2+, Tl+, Rb+,
Cs+
Mg2+ Mg(NH4)PO4.6H2O Mg2P2O7 Many metals except Na+
and K+
Ca2+ CaC2O4.H2O CaCO3 or CaO Many metals except Mg2+,
Na+, or K+
Ba2+ BaSO4 BaSO4 Na+, K+, Li+, Ca2+, Al3+,
Cr3+, Fe3+, Sr2+, Pb2+,
NO3-
Ti4+ TiO(5,7-dibromo-8- same Fe3+, Zr4+, Cu2+, C2O42-,
hydroxyquinoline)2 citrate, HF
VO43- Hg3VO4 V2O5 Cl-, Br-, I-, SO42-, CrO42-,
AsO43-, PO43-
Cr3+ PbCrO4 Ag+, NH4+
Mn2+ Mn(NH4)PO4.H2O Mn2P2O7 Many metals
Fe3+ Fe(HCO2)3 Fe2O3 Many metals
Ni2+ Ni(dimethylglyoximate)2 same Pd2+, Pt2+, Bi3+, Au3+
Limitations of Gravimetric Analysis
• Any interferents must be
removed prior to precipitation
• Method is not very sensitive
Applications of Gravimetric analysis

• Chemical analysis of ores and industrial materials

• Calibration of instruments
• Elemental analysis of inorganic compounds
General Procedure:

1.Weigh the sample to be analysed

2.Dissolve the sample in a suitable solvent, eg, water
3.Add an excess of the precipitating reagent to precipitate the
analyte
4.Filter the mixture to separate the precipitate from the solution3
5.Wash the precipitate to remove any impurities4
6.Dry the precipitate by heating to remove water
7.Cool the precipitate in a dessicator to prevent the precipitate
absorbing moisture from the air
8.Weigh the cooled precipitate
9.Repeat the drying and weighing process until a constant mass
for the precipitate is achieved
10.Calculate the percent by mass of analyte in the sample
General calculation of the percent by mass of analyte in
a sample:
1.Write the balanced chemical equation for the precipitation
reaction
2.Calculate the moles of precipitate: moles = mass ÷ molar
mass
3.Calculate moles of analyte from the balanced chemical
equation using the mole ratio of analyte : precipitate
(also known as the stoichiometric ratio of analyte to
precipitate)
4.Calculate mass of analyte: mass = moles × molar mass
5.Calculate percent by mass of analyte in sample: (mass
analyte ÷ mass sample) × 100
Source of Errors
•Incomplete precipitation results in a value for the
percentage of analyte in the sample that is too low.

•Incomplete drying of the sample results in a value for

the percentage of analyte in the sample that is too high

•Other ions in the sample may also be precipitated

resulting in a value for the percentage of analyte in the
sample that is too high
Key Concepts

•Gravimetric analysis is the quantitative isolation of a substance

by precipitation and weighing of the precipitate.
•An analyte is the substance to be analysed.
•A precipitating reagent is the reactant used to precipitate the
analyte.
•The precipitate must be a pure substance of definite chemical
composition.
•One advantage of gravimetric analysis compared to volumetric
analysis (titrimetric analysis) is that there is greater likelihood of
any impurities being seen, and therefore a correction can be
applied.
•One disadvantage of gravimetric analysis is that it is generally
more time-consuming.
Gravimetric Factor
• Analyte ppt G.F.
CaO CaCO3 CaO/CaCO3
FeS BaSO4 FeS/BaSO4
Cr2O3 Ag2CrO4 Cr2O3/2Ag2CrO4

• Naming is critically important

What Do We Get Out of Gravimetry?
• % of analyte, % A

• %A = weight of analyte x 100

weight of sample

• weight of ppt directly obtained ->?A

Calculations using Gravimetric Analysis
A 10.0 mL solution containing Cl- was treated with excess AgNO3 to
precipitate 0.4368 g of AgCl. What was the concentration of Cl- in the
unknown? AgCl=143.3210 g/mole.
Ag+ + Cl- AgCls
From the equation: #moles of Cl- = #moles of AgCl
= Cl- / AgCl
= 0.4368g
143.3210g/mole
= 3.048 x 10-3 mole
Concentration of Cl- = 3.048 x 10-3 mole
0.0100 L
= 0.3048 Moles/Liter
% Volatile Solids = (massof dried residue & dish- wt of residue and dish after ignition)
mass of wet sample – mass of dish
= (45.4140- 43.3236g)
104.4680g - 42.9073g
= 2.0904/61.5067*100
= 3.3987 %
 Calculate the amount of sulphate as barium sulphate from sodium sulphate.
Solution of sodium sulphate (Na2SO4) is treated with solution of barium chloride
(BaCl2) to get precipitates of barium sulphate (BaSO4). The precipitates are then
washed, dried and ignited to get free from impurities and then weighed.

Na2SO4 + BaCl2 → BaSO4 + 2 NaCl

Mol. Weight of BaSO4 = 233.42 gm

Mol. Weight of SO4- = 96.06 gm

233.42 gm of BaSO4 = 96.06 gm of SO4- ions

BaSO4 = 96.06 · X / 233.32 = 0.411X gm of SO4- ions

Suppose 25 ml solution is consumed, then

25 ml solution contains = 0.411 gm of SO4- ions

1000ml solution conatins = 0.411 · 1000 / 25 = 16.44X gm of SO4- ions
Problem
• Consider a 1.0000 g sample containing 75% potassium sulfate (FW 174.25g) and
25% MgSO4. The sample is dissolved and the sulfate is precipated as BaSO4 (FW
233.39). If the BaSO4 ppt weighs 1.49, what is the atomic weight of Mg2+ in
MgSO4?
Given: Weight of sample = 1.0000g FW K2SO4 = 174.2500 g, 75%
FW BaSO4 = 233.3900g FW of MgSO4 = x (25%)
Weight of MgSO4
Required: Atomic weight of Mg2+
Solution: Let x = Atomic weight of Mg2+
(0.75) FW BaSO4 + (0.25) FW BaSO4 = 1.49
FW K2SO4 x + FW SO4
(0.75) (233.39) + (0.25) (233.39) = 1.49
174.25 x + 96.08
58.3475 2+
0.4855 = ; x = 24.12( Mg )
x + 96.06
 When an sample of impure potassium chloride (0.4500g)
was dissolved in water and treated with an excess of silver
nitrate, 0.8402 g of silver chloride was precipitated.
Calculate the percentage KCl in the original sample.

Chemistry 215 Copyright D Sharma 140

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