Gravimetric Methods of Analysis

By: Amha T.

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Outline
 you will familiar with:
 Theory of the gravimetric analysis and classification of its
methods.
 Steps in gravimetric analysis
 Selected gravimetric methods
 Applications of the gravimetry in the pharmaceutical
analysis.
Gravimetric Analysis
Introduction
Gravimetric Analysis:
(i) A technique in which the amount of an analyte in a
sample is determined by converting the analyte to some
product
 Mass of product can be easily measured

(ii) Analyte: the compound or species to be analyzed in a

sample
(iii) Overall, gravimetry sounds simple.
 Advantages - when done correctly is highly accurate
(most accurate of all time); requires minimal equipment
 Disadvantage - requires skilled operator, slow.

=> Convert analyte into a solid, filter, dry, weigh, calculate via
a mole map

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 Gravimetric Analysis…
Introduction
(iv) Example:
Determination of chloride (Cl-) in water
Cl- + Ag+ 
Analyte Reagent AgCl(s) Solid Product

 By adding excess Ag+ to the sample, essentially

all of the Cl- will precipitate as AgCl.

 Mass of AgCl is then determined.

- used to calculate the amount of Cl- in original
solution

 What is the %KCl in a solid if 5.1367 g of solid

gives rise to 0.8246 g AgCl?

Cl- + Ag+  AgCl(s)

Types of gravimetric analysis

1. Electrogravimetry
 The mass of an electrodeposit on the cathode or anode in an
electrochemical cell is determined.

 The oxidation of lead, and its deposition as PbO 2 on a Pt anode

 Pb2+(aq) + 4H2O(l) = PbO2(s) + H2(g) + 2H3O+(aq)

 The electrodeposition of Cu on a Pt cathode provides a direct

analysis for Cu2+
 The difference in the electrode’s mass before and after electrolysis
is a direct measurement of the amount of analyte in a sample.

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 Types of gravimetric analysis …

2. Particulate gravimetry:

 The mass of a particulate analyte is determined

following its separation
 Using a filtration or an extraction from its matrix.

E.g. determination of total suspended solids

 Precipitation and Volatilization are the major types of gravimetric

methods.

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 Types of gravimetric analysis …
3. Precipitation methods

Principals:
 The analyte is converted to a sparingly soluble ppt.

(i) Reagent + Analyte → Solid Product (collect and measure mass)

(ii) Desired Properties of Solid Product
 Should be very insoluble
 Easily filterable (i.e., large crystals)
 Very Pure
 Known and constant composition
(iii) This ppt is then filtered, washed free of impurities, and converted
to a product of known composition
- By suitable heat treatment, and the product is weighed.
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Precipitation methods ….

 Steps in gravimetric analysis (Precipitation gravimetry)

1. Preparation of the solution
2. Precipitation
3. Digestion
4. Filtration
5. Washing
6. Drying or igniting
7. Weighing
8. Calculation

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 Precipitation methods ….
1. Preparation of the solution

Factor that must considered during preparation of sol:

i. Volume of the solution during precipitation

ii. The concentration range of the test substance

iii. Temperature

iv. pH

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 Precipitation methods ….
Some form of preliminary separation may be necessary to eliminate
interfering material.

Adjust the solution condition to maintain low solubility of the

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

Proper adjustment of the solution conditions prior to precipitation may

also mask potential interferences.

pH is important

 B/c it often influences both the solubility of the analytical precipitate

and the possibility of interferences from other substances.

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 Precipitation methods ….
2. Precipitation
 Properties of precipitating reagents
 Ideally, a gravimetric precipitating agent should react specifically or at least
selectively with the analyte.

Specific reagents, which are rare, react only with a single chemical
species.

 Dimethylglyoxime is a specific agent only for Ni2+

Selective reagents, which are more common, react with a limited number
of species.

 AgNO3 is a selective agent for Cl-, Br-, I-, SCN-

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 Precipitation methods ….

Properties of good precipitates

 Easily filtered and washed free of contaminants.

 Of sufficiently low solubility

i.e no significant loss of the analyte occurs during filtration and

washing.

 Unreactive with constituents of the atmosphere

 Of known chemical composition after it is dried or, if necessary,

ignited.
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 Precipitation methods ….
Particle size and filterability of precipitates
 Filterability:
(i) Want product to be large enough to collect on filter:
 Doesn’t clog filter
 Doesn’t pass through filter
(ii) Best Case: Pure Crystals

Worst Case: Colloidal suspension

 Difficult to filter due to small size
 Tend to stay in solution indefinitely  suspended by Brownian motion
- usually 1-100 nm in size
 As the particle size of the precipitate increases, the impurities
decrease and the ease of filtration increases.
Particle size of precipitates
1. Colloidal suspensions

Tiny particles: 10-7-10-4 cm in diameter

Colloidal particles show no tendency to settle from sol

Not easily filtered.

2. Crystalline suspensions

Greater than 0.1 mm diameter

Normally settle out spontaneously

Easily filtered

Typically of higher purity than colloids 14

 Precipitation methods ….

 Process of Crystal Growth:

(i) Two Phases in Crystal Growth

Nucleation – when a small number of ions, atom and molecules in

solution come together randomly and form small aggregates
in
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 Precipitation methods ….
(ii) Nucleation and Particle growth always compete for
molecules/ions being precipitated.
 If nucleation is faster than particle growth:
- a large number of small aggregates occur giving colloidal
suspensions
 If particle growth is faster than nucleation:

- only a few, large particles form giving pure crystals

Want to

Convert to

Colloidal suspension Crystal formation

 Precipitation methods ….
(iii) Rates of nucleation vs. particle growth depends on:
R  (Q  S )
 Amount of precipitation solute present S
 Described by a quantity known as the Relative Supersaturation (R)
Q = conc. of the solute in solution at the instant the reagents are mixed,
S = conc. of the solute in a saturated solution or equilibrium solubility
Q - S (supersaturation) = conc. of the solute in excess of that found in a
saturated solution.

Colloidal Particle (iv) If R is large,

 Large relative amount of solute in solution

 Favors nucleation and colloid formation
(v) In gravimmetry based on precipitations, a small value of R (~1.0)
is desired in order to favor large crystal growth
 Precipitation methods ….
(vi) Methods for Minimizing R => R↓, Q↓, S↑ → particle size ↑
1. Increase temperature of solution
- increases S
- increase amount of solute that can be in solution at
equilibrium
2. Add precipitating reagent slowly while vigorously mixing solution
- avoids local high concentrations of solution
- avoid nucleation and colloid formation
3. Keep volume of solution large
- keep concentration of analyte and precipitating reagent
low
4. Control S through chemical means
- by adjusting pH => ↑S
 Precipitation methods ….
3. Digestion of the Precipitate

 To make precipitate become larger and more pure crystals.

 It improves the purity and crystallinity of the precipitate.

 An important advantage of digestion is observed for colloidal
precipitates where large amounts of adsorbed ions cover the huge
area of the precipitate.

 Digestion forces the small colloidal particles to agglomerate which

decreases their surface area and thus adsorption.
 Particle size↑→ specific surface area↓→ adsorption↓

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Digestion…

 Digestion involves:

 Dissolution of small particles and

 Reprecipitation on larger ones resulting in particle

growth and better precipitate characteristics.

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Digestion…
 Adsorption is a major problem in gravimetry in case of colloidal

precipitate
 Since a precipitate tends to adsorb its own ions present in

excess,
 Therefore forming what is called a primary ion layer which

attracts ions from solution forming a secondary or counter ion

layer.
 Individual particles repel each other keeping the colloidal

properties of the precipitate.

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 Precipitation methods ….
4. Filtering and Washing the Precipitate
 Co-precipitated impurities, especially those on the surface, can
be removed by washing the precipitate after filtering.
 It is crucial to wash the precipitate very well
 In order to remove all adsorbed species which will add to
weight of precipitate.
 Avoid using too much water since part of the precipitate may be
lost.
 In colloidal ppts dil nitric acid, ammonium nitrate, or dil acetic
acid may be used.
 Since they are volatile when heated

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 Precipitation methods ….
Washing solution

1. Wash out all impurities

 But leave it unchanged in composition

2. Not introduce insoluble product into ppt

3. Completely volatile at drying temp of ppt

 Check the presence of ppting agent in the filtrate of
the final washing solution.

 If present, extra washing is required

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 Precipitation methods ….

5. Drying and Ignition

 The purpose of:
 Drying (heating at about 120-150 oC in an oven) or
 Ignition in a muffle furnace at temp ranging from 600-1200 oC
 Is to get a material with exactly known chemical structure
 So that the amount of analyte can be accurately
determined.

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 Precipitation methods ….
6. Weighing & Calculations
 In gravimetric analysis, the percentage of the desired constituent may
be achieved by the ff expression :

Wt. of ppt' x GF
% Analyte  x 100, Wt. of ppt' - weighed gravimetrically
Wt. of sample

f. wt. analyte (g/mol) a(mol analyte)

GF  
f. wt. ppt (g/mol) b(mol ppt)

wt. analyte
GF 
wt. ppt
 Gravimetric factor(GF) - the weight of analyte per unit weight of
precipitate 25
4. Volatilization methods
 In this method the analyte or its decomposition products are volatilized at a
suitable temperature. The volatile product is then collected and weighed, or,
alternatively, the mass of the product is determined indirectly from the loss in
mass of the sample.

 The analysis depends on the removal of the volatile species from the sample:

 Ignition of the sample in the air or in the gaseous medium

 Treatment of the sample with a chemical reagent which convert the

sample to volatile form.

 Treatment of the sample with a chemical reagent which convert the

sample to stable unvolatile form then separate from the original sample.

 Determination of the hydrate percentage in hydrate cpds

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Applications
 The gravimetric methods adopted vary according to the
nature of the substance under determination.
 HENCE, most of the substances being estimated
gravimetrically fall into one or the other categories stated
below:
A. Substances assayed gravimetrically,
B. Substances assayed after conversion:
i. Substances assayed after conversion to Free Acid,
Acid
ii. Substances assayed after conversion to Free Base,
Base
iii. Substances assayed after conversion to Free Compound.
Compound
iv. Substances assayed after conversion to Derivatives or
Substitution Products.

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 Substances Assayed Gravimetrically
 E.g. 1: Calculate % purity of NaCl
 NaCl : 0.257 g ; using 5% w/v silver nitrate
 The weight of AgCl is found to be 0.6288 g experimentally,
AgNO3 + NaCl →AgCl + NaNO3
169.87 58.44 143.22 84.99
 solution:

GF = 58.44/143.22 = 0.4078

Wt. of ppt x GF
% Desired  x 100
Wt. of sample

0.6288 x 0.4078
x 100  99.77%
0.257

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 E.g.2 ： The calcium in a 200.0ml sample of a natural water was
determined by precipitating the cation as CaC2O4. The precipitate was
filtered, washed, and ignited in a crucible with an empty mass of 26.6002g.
The mass of the crucible plus CaO （ 56.077g/mol ） was 26.7134 g.

Calcualte the conc(% w/v) of Ca （ 40.078g/mol ） in water.

CaC2O4 (s) Δ CaO (s) + CO (g) + CO2

mass CaO  26.7134  26.6002  0.1132 g

GF  40.07 / 56.077  0.7146

Wt. of ppt x GF
% Desired  x 100
Wt. of sample

0.1132g x 0.7146
%Ca  x 100  0.04045%
200ml
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Table: Pharmaceutical substances assayed
gravimetrically

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Substances Assayed after Conversion to Free Base
(Papaverine Hydrochloride Tablets)

 In a specific instance where the organic medicinal substance is

basic in nature, it is primarily treated with an aqueous solution of a
base and
 Subsequently the liberated organic base is extracted with either
chloroform or ether.
 e.g., papaverine in papaverine hydrochloride,
C20H21NO4 . HCl ≡ C20H21NO4

or 374.45 g C20H21NO4 . HCl ≡ 339.0 g C20H21NO4

or 1.105 g C20H21NO4 . HCl ≡ 1 g of C20H21NO4

 Each g of the residue is equivalent to 1.105 g of C20H21NO4 . HCl.
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Substances Assayed after Conversion to Free Base…

 Amodiaquine Hydrochloride
 Each gram of residue is equivalent to 1.306 g of
C20H22ON3Cl, 2HCl, 2H2O.

 Phenacaine hydrochloride
 Each gram of residue is equivalent to 1.122 g of
C18H22N2O2 . HCl.

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Substances Assayed after Conversion to Free Acid

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Substances assayed after conversion to Derivatives or Substitution
Products

 Benzylpenicillin (sodium or potassium salt) may be assayed

gravimetrically by quantitative conversion to the 1-thylpiperidinium
benzylpenicillin derivative.
 The ultimate precipitation is caused by lethyl piperidine

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* Each gram of residue is equivalent to 0.8300 g of C16H17N2NaO4S.
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Exercises
1. To obtain a precipitate which is useful for gravimetric analysis, the
analyst tries to obtain conditions to encourage crystal growth, as
opposed to the formation of a colloid. Which of the following
statements aids in the formation of a crystalline precipitate?
a. The solution is kept cool to slow down the movement of ions to
allow crystals to form.
b. The solutions are made as dilute as practical to allow crystals to
form slowly.
c. The solutions are mixed rapidly to allow the appropriate ions to
make contact without interference of other materials. D. all
2. Which of the following processes is true regarding the digestion
of a solution containing a precipitate?
a. Digestion tends to increase particle size of the precipitate.
b. Digestion is used to slow down the coagulation of a colloidal
precipitate because of the increased energy added to the solution.
c. A long digestion is not recommended because the higher
temperatures enable impurities to become trapped in the crystal
lattice of the precipitate D. all

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3. In the gravimetric analysis of iron, hydroxide may be added to a
solution containing Fe3+ to precipitate a gelatinous mess which is
ignited to form Fe2O3. If 0.2864 grams of Fe2O3 were formed from
the ignition of the precipitated mess, how many grams of FeCO 3
were contained in the original sample analyzed?
a. 0.4155 g FeCO3
b. The answer cannot be computed because the sample did not contain any Fe2+.
c. 0.2078 g FeCO3
4. A sample of ore containing manganese weighed 1.2354 grams. This
sample was heated in a solution of nitric acid, which dissolved the manganese ion
producing manganese(III) nitrate (Mn(NO3) 3). The acidity of the solution was
adjusted, and Hydrogen sulfide gas was bubbled into the solution producing 0.2876
grams of manganese(III) sulfide (Mn2S3). What is the percentage of manganese in
the original sample?
a. 12.37% Mn
b. 6.19% Mn
c. 3.09% Mn

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5. Why do you reheat/recool the solid unknown until its weight
stabilizes?
a. To increase the precision of your measurement.
b. To increase the accuracy of your measurement.
c. To ensure that there is no water in your solid.
d. To convert any nickel metal to nickel oxide.
6. In Gravimetric Determination of Nickel, heating gently during
the coagulation stage would aid what process?
a. Precipitation -- more Nickel diglyme would come out of
solution.
b. Digestion -- particle size and purity increases due to
recrystallization.
c. Evaporation -- the solution becomes more concentrated so more
precipitation occurs and filtering is easier.
d. Calculation -- the waiting gives you time to work example
problems and ask questions.
7. Summarize the conditions to improve an analytical
precipitation in Gravimetric analysis.

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Thank you

Thank u