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Chapter 12
Gravimetric Methods of Analysis

Formation of precipitates and crystals.

12A Precipitation Gravimetry

 Gravimetric methods of analysis are based on the

measurement of mass.
 There are two major types of gravimetric methods:
precipitation gravimetry (沉澱重量法) and volatilization
gravimetry (揮發重量法).
 In precipitation methods, the analyte is converted to a sparingly
soluble precipitate.
 This precipitate is then filtered, washed free of impurities, and
converted to a product of known composition by suitable heat
treatment, and the product is weighed.
H2C2O4 + 2NH3 C2O42-(aq) + 2 NH4+ (aq)
Ca2+(aq) + C2O42-(aq) CaC2O4(s)
CaO(s) + CO(g) + CO2(g) Determine Calcium in water.

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12A-1 Properties Of Precipitates And

Precipitating Reagents

 Ideally, a gravimetric precipitating agent should react

specifically(特異地), or if not, then selectively(選擇地) with the
analyte. (ex.)
* Specific reagent:

dimethylglyoxime

* Selective reagents:
AgNO3 + Cl-, Br-, I-, SCN- precipitates

12A-1 Properties Of Precipitates And

Precipitating Reagents

The ideal precipitating reagent would react with the analyte to

give a product that is
 1. Readily filtered and washed free of contaminants
 2. Of sufficiently low solubility so that no significant loss of
the solid occurs during filtration and washing
 3. Unreactive with constituents of the atmosphere
 4. Of known composition after it is dried or, if necessary,
ignited.

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12A-2 Particle Size and Filterability of

Precipitates
 Precipitates made up of large particles are generally desirable in
gravimetric work because large particles are easy to filter and wash
free of impurities.

 A colloid (膠體) is a solid made up of particles having diameters that

are less than 10-4 cm (colloidal suspensions: 10-7 ~ 10-4 cm).
Colloid particles show no tendency to settle from solution and are
difficult to filter.

 Crystalline suspensions: > tenths of a milimeter. The particles of a

crystalline suspension tend to settle spontaneously and are easily
filtered.

12A-2 Particle Size and Filterability of

Precipitates
 What Factors Determine Particle Size?
 Colloidal particles show no tendency to settle from solution, nor
are they easily filtered.
 The particles, with dimensions on the order of tenths of a
millimeter or greater, temporary dispersed in the liquid phase is
called a crystalline suspension.
 The particles of a crystalline suspension tend to settle
spontaneously and are readily filtered.
 The particle size of a precipitate is influenced by such
experimental variables as precipitate solubility, temperature,
reactant concentrations, and the rate at which reactants are
mixed.

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12A-2 Particle Size and Filterability of

Precipitates
 What Factors Determine Particle Size?
 The particle size is related to relative supersaturation (相對過飽
和), where

(12-1)

 Q is the concentration of the solute at any instant and S is its

equilibrium solubility.
 When (Q - S)/S is large, the precipitate tends to be colloidal;
when (Q - S)/S is small, a crystalline solid is more likely.

12A-2 Particle Size and Filterability of

Precipitates
 How Do Precipitates Form?
 Assume that precipitates form in two ways, namely by nucleation
(成核) and by particle growth (粒子成長).
 The particle size of a freshly formed precipitate is determined by
which way is faster.
 Nucleation is a process in which a minimum number of atoms,
ions, or molecules join together to produce a stable solid.
 Further precipitation then involves a competition between
additional nucleation and growth on existing nuclei (particle
growth).

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12A-2 Particle Size and Filterability of

Precipitates

 How Do Precipitates Form?

 If nucleation predominates, a precipitate containing a large
number of small particles results.

 If particle growth predominates, a smaller number of larger

particles is produced.

 The rate of nucleation is believed to increase enormously with

increasing relative supersaturation [(Q-S)/S].

 In contrast, the rate of particle growth is only moderately

enhanced by high relative supersaturations.

12A-2 Particle Size and Filterability of

Precipitates
 Controlling Particle Size
 Experimental variables lead to crystalline precipitates include
elevated temperatures to increase the solubility of the precipitate
(increase S), dilute solutions (to minimize Q), and slow addition of
the precipitating agent with good stirring (to minimize Q).
 Larger particles can also be obtained by pH control, provided the
solubility of the precipitate depends on pH. (ex)

Ca2+(aq) + C2O42-(aq) CaC2O4(s) in mild acidic environment.

H2C2O4 + 2NH3 C2O42-(aq) + 2 NH4+(aq) NH3 is added slowly.

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12A-3 Colloidal Precipitates

 Coagulate, or agglomerate, the individual particles of most colloids
to give a filterable, amorphous mass that will settle out of solution.

 Coagulation (凝結，凝集) of Colloids

 Coagulation can be hastened by heating, stirring, and adding
an electrolyte to the medium.

 Why colloidal suspensions are stable and do not coagulate

spontaneously?

12A-3 Colloidal Precipitates

 Coagulation of Colloids
 Colloidal suspensions are stable because the particles are
either positively charged or negatively charged and thus repel
one another. Cations or anions are adsorbed to the particle
surface.
 Adsorption (吸附) is a process in which a substance (gas,
liquid, or solid) is held on the surface of a solid. In contrast,
absorption (吸收) involves retention of a substance within the
pores of a solid.
 The charge on a colloidal particle formed in a gravimetric
analysis is determined by the charge of the lattice ion (晶格離子)
that is in excess when the precipitation is complete.

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NaCl(aq) is added into a solution containing an

excess of AgNO3(aq).

Electric double layer (電雙層):

exerts an electrostatic
repulsive force that prevents
particles from colliding and
adhering.

Figure 12-1 A colloidal silver chloride particle suspended in a

solution of silver nitrate.

Effective charge:
a measure of the
repulsive force.

Figure 12-2 Effect of AgNO3 and electrolyte concentration on the

thickness of the double layer surrounding a colloidal AgCl particle in
a solution containing excess of AgNO3.

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Figure 12-3 Concentrated

AgNO3(aq) solution

Dilute AgNO3(aq)
solution

Figure 12-3 The electric double layer of a colloid consists of a layer of charge
adsorbed on the surface of the particle (the primary adsorption layer) and a
layer of opposite charge (the counter-ion layer) in the solution surrounding
the particle. Increasing the electrolyte concentration has the effect of
decreasing the volume of the counter-ion layer, thereby increasing the
chances for coagulation.

12A-3 Colloidal Precipitates

 Coagulation of Colloids
 Coagulation of a colloidal suspension can often be brought about
by a short period of heating (decrease di), particularly if
accompanied by stirring.
 An even more effective way to coagulate a colloid is to increase the
electrolyte concentration of the solution (decrease di). (Fig 12-3)
 Peptization of Colloids
 Peptization (膠溶，解膠) is a process by which a coagulated colloid
returns to its dispersed state, which can be solved by washing with
a volatile electrolyte such as nitric acid.
 Treatment of Colloidal Precipitates
 Colloids are best precipitated from hot, stirred solutions containing
sufficient electrolyte to ensure coagulation.

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12A-4 Crystalline Precipitates

 Improving Particle Size and Filterability

 The particle size of crystalline solids can often be improved
significantly by minimizing Q, maximizing S, or both.

 Digestion (浸煮) of crystalline precipitates (without stirring) for

some time after formation frequently yields a purer, more filterable
product.

 Digestion is a process in which a precipitate is heated an hour or

more in the solution from which it was formed (mother liquor).
Water is expelled from the solid.

12A-5 Coprecipitation

 Coprecipitation (共沉澱) is a process in which normally soluble

compounds are carried out of solution by a precipitate.

 There are four types of coprecipitation: (1) surface adsorption, (2)

mixed-crystal formation, (3) occlusion, and (4) mechanical
entrapment. (1) & (2) are equilibrium processes, while (3) & (4)
arise from kinetics of crystal growth.

 Surface Adsorption (表面吸附)

 Adsorption is a common source of coprecipitation that is likely to
cause significant contamination of precipitates with large
specific surface areas (coagulated colloids).

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12A-5 Coprecipitation
 Surface Adsorption
 Coagulation of a colloid does not
significantly decrease the amount
of adsorption.
 The net effect of surface adsorption
is therefore the carrying down of an
otherwise soluble compound as a
surface contaminant.

 Ex. Coagulated silver chloride is

contaminated with primarily adsorbed
Ag+ along with nitrate or other anions.

12A-5 Coprecipitation

 Surface Adsorption
 Minimizing Adsorbed Impurities on Colloids
The purity of many coagulated colloids is improved by digestion
(浸煮) or washing with a solution containing a volatile electrolyte.
Regardless of the method of treatment, a coagulated colloid is
always contaminated to some degree, even after extensive
washing.

 Reprecipitation.
A drastic but effective way to minimize the effects of adsorption is
reprecipitation (再沉澱), or double precipitation. (Because the first
precipitate carries down only a fraction of the contaminant present in the
original solvent)

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12A-5 Coprecipitation

 Mixed-Crystal Formation (混合晶體形成)

 In mixed-crystal formation, one of the ions in the crystal lattice of a
solid is replaced by an ion of another element. (ex)
 The extent of mixed-crystal contamination is governed by the law
of mass action and increases as the ratio of contaminant to analyte
concentration increases.
 Occlusion (包留) and Mechanical Entrapment (力學誘陷)
 When a crystal is growing rapidly during precipitate formation,
foreign ions in the counter-ion layer may become trapped, or
occluded, within the growing crystal.
 Occlusion is a type of coprecipitation in which a compound is
trapped within a pocket formed during rapid crystal growth.

12A-5 Coprecipitation

 Occlusion and Mechanical Entrapment

 Mixed-crystal formation may occur in both colloidal and crystalline
precipitates, whereas occlusion and mechanical entrapment are
confined to crystalline precipitates.
 Mechanical entrapment occurs when crystals lie close together
during growth.

 Occlusion and Mechanical Entrapment

 Both occlusion and mechanical entrapment are at a minimum
when the rate of precipitate formation is low, that is, under
conditions of low supersaturation.
 In addition, digestion (浸煮) is often remarkably helpful in
reducing these types of coprecipitation.

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12A-5 Coprecipitation
 Coprecipitation Errors
 Coprecipitation can cause either negative or positive errors.

 The contaminant is not a compound of the ion being determined:

positive error. (ex. AgCl adsorbs AgNO3)

 The contaminant does contain the ion being determined: positive

or negative error.
BaSO4 occlusion of Ba(NO3)2: positive error
BaSO4 occlusion of BaCl: negative error

12A-6 Precipitation from Homogeneous

Solution
 Homogeneous precipitation is a process in which a precipitate
is formed by slow generation of a precipitating reagent
homogeneously throughout a solution. [relative supersaturation (Q-
S)/S is kept low]

 In general, homogeneously formed precipitates, both colloidal and

crystalline, are better suited for analysis than a solid formed by direct
addition of a precipitating reagent.

 Ex. Urea is often used for homogeneous generation of

hydroxide ion. (<100oC, 1~2 hour)

(NH2)2CO + 3H2O CO2 + 2NH4+ + 2OH-

Al(OH)3

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Homogeneous generation of precipitating agents

12A-7 Drying And Ignition Of Precipitates

 After filtration, a gravimetric precipitate is heated until its mass

becomes constant.

 Some precipitates are also ignited to decompose the solid and form
a compound of known composition. This new compound is often
called the weighing form (稱量形式).

 Recording thermal decomposition curves is often called

thermogravimetry or thermogravimetric analysis (TGA:熱重分析),
and the mass versus temperature curves are called thermograms
(熱圖).

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Figure 12-6 Effect of temperature on

precipitate mass.

12B Calculating Results From

Gravimetric Data
 The results of a gravimetric analysis are generally computed from
the mass of sample and the mass of a product of known composition.

 Example 12-2
 An iron ore was analyzed by dissolving a 1.1324-g sample in
concentrated HCl. The resulting solution was diluted with water, and
the iron(III) was precipitated as the hydrous oxide Fe2O3‧xH2O by
the addition of NH3. After filtration and washing, the residue was
ignited at a high temperature to give 0.5394 g of pure Fe2O3 (159.69
g/mol). Calculate (a) the % Fe (55.847 g/mol) and (b) the % Fe3O4
(231.54 g/mol) in the sample.

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Example 12-2

 For both parts of this problem, we need to calculate the number of

moles of Fe2O3. Thus,

 (a) The number of moles of Fe is twice the number of moles of

Fe2O3, and

Example 12-2

 (b) As shown by the following balanced equation, 3 mol of

Fe2O3 are chemically equivalent to 2 mol of Fe3O4. That is,

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12C Applications Of Gravimetric Methods

 Gravimetric methods have been developed for most inorganic

anions and cations as well as for such neutral species.

 A variety of organic substances can also be readily

determined gravimetrically.

 Gravimetric methods do not require a calibration or

standardization step because the results are calculated
directly from the experimental data and molar masses.

12C-1 Inorganic Precipitating Agents

 These reagents typically form slightly soluble salts or hydrous oxides

with the analyte.
 Most inorganic reagents are not very selective.

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Table 12-2 continued

12C-3 Organic Precipitating Agents

 Numerous organic reagents have been developed for the

gravimetric determination of inorganic species.

 One forms slightly soluble nonionic products called coordination

compounds (配位化合物，錯合物); the other forms products in
which the bonding between the inorganic species and the reagent
is largely ionic.

 Chelates (螯合物) are cyclical metal-organic compounds in which

the metal is a part of one or more five- or six-membered rings.

 8-Hydroxyquinoline and dimethylglyoxime are two widely used

chelating reagent (螯合劑). Sodium tetraphenyl borate is a near-
specific precipitation agent for potassium and ammonium.

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12C-3 Organic Precipitating Agents

 8-Hydroxyquinoline (HOQ)

 Dimethylglyoxime (DMG)

 Sodium Tetraphenylborate
 Sodium tetraphenylborate, (C6H5) 4B-Na+, is an important
example of an organic precipitating reagent that forms salt-like
precipitates. (Ca2+, NH4+)

Sodium Tetraphenylborate

Molecular model

p296

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12C-4 Organic Functional Groups Analysis

氨基磺酸 亞磺酸

12C-5 Volatilization Methods

 In volatilization methods, 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.

 Determine content of sodium hydrogen carbonate in antacid tablet.

NaHCO3(aq) + H2SO4(aq) CO2(g) + H2O(l) + NaHSO4(aq)

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12C-5 Volatilization Methods

 The two most common gravimetric methods based on volatilization

are those for water and carbon dioxide. (ex. Direct and indirect
determination of water content).

 Carbonates are ordinarily decomposed by acids to give carbon

dioxide, which is readily evolved from solution by heat. The carbon
dioxide is then absorbed by sodium hydroxide on a silicate.

NaHCO3(aq) + H2SO4(aq)  CO2(g) + H2O(l) + NaHSO4(aq)

2NaOH + CO2 Na2CO3 + H2O

NaHCO3(aq) + H2SO4(aq)  CO2(g) + H2O(l) + NaHSO4(aq)

Figure 12-8 Apparatus for determining the sodium hydrogen carbonate

content of antacid tablets by a gravimetric volatilization procedure.

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