GRAVIMETRIC APPLICATIONS

A. Scope: Capabilities of gravimetric analysis on six areas:

1. Sensitivity or ability to distinguish between two nearly identical amounts or

concentrations
➢ Not limited by measurement device which is the analytical balance
➢ Limited by:
○ solubility losses during precipitation and rinsing;
○ inability of the filter to retain the smallest precipitate particles
➢ Increase sample size to produce larger amount of precipitate, but the larger
volume complicates precipitate handling
➢ Suitable for samples having an analyte concentration greater than about 1%, but
may in certain cases be suitable for samples with concentrations as low as 0.1%

2. Accuracy
➢ Inherent accuracy of gravimetric methods is among the best of all quantitative
methods, with relative errors as low as 0.1%
➢ This degree of accuracy is achieved only with fairly simple samples handled very
carefully by experienced analysts

3. Selectivity
➢ Gravimetric methods are limited mainly inorganic substances;
➢ Generally not very selective resulting in sample pretreatment to remove potential
interferences or to change them to a non-interfering form
➢ Accuracy suffers from removal of interferences is an added step which can result
in loss of some analyte

4. Ease of Operations
➢ Gravimetric methods require considerable manipulative skills obtained only
through practice
➢ Operations tend to be time-consuming, tedious, and impossible to automate

5. Time
➢ Typical gravimetric determinations may require from 3 to 6 hours to complete,
although the analyst has time for other work during digestion, ignition, and
cooling of the precipitate
➢ Method is undesirable when results are needed quickly or when large numbers of
samples must be analyzed
 6. Cost
➢ Reagent and equipment expense for most gravimetric determinations is small, but
personnel cost is high because of the long analysis times and required technical
skills

B. Selected Gravimetric Methods for Common Substances

1. Determination of sulfur
➢ Sulfur is determined in the form of sulfate by precipitation with barium chloride
Ba2+ + SO42- → BaSO4(s)
➢ Samples containing other forms of sulfur are treated with strong oxidizing agents
to convert S to SO42-
➢ BaSO4 is precipitated from acidic solution, even though its solubility can be as
much as 20 times larger than in neutral solution, to avoid simultaneous
precipitation of other barium salts.
➢ Anions that form insoluble barium salts in neutral solutions:
AsO33-, AsO 33-, CO32-, C2O42-, F-, PO43-
➢ These are anions of weak acids and form strong covalent bonds with hydrogen
ions in acidic solutions, reducing their ability to precipitate barium ions.
➢ PO43- and F- precipitate with barium even in dilute solution, so must be removed
from the sample, unless they are only in small amounts.
➢ Coprecipitation is a serious problem with BaSO4 precipitates, even in acidic
solutions
➢ Coprecipitations of various anions decreases in the order:
BrO3- → Fe(CN)64- → NO3- → MnO4- → Fe(CN)63- → Cl- → Br- → I- → SCN-
→ CH3COO-
➢ NO3- and ClO3- must be removed by fuming (almost boiling) the sample with
concentrated HCl
NO3- + 4H- + 3Cl- → Cl2(g) + NOCl(g) + 2H2O
ClO3- + 6H+ + 5Cl- → 3Cl2(g) + NOCl(g) + 3H2O
➢ Coprecipitation of cations decreases in the order:
Cd2+ → Mn2+ → Cu2+ → Zn2+ → Al 3+ → Fe2+ → K+ → Ni2+ → Na+ → Li+ →
Mg2+
➢ Interference of Fe3+ can be troublesome and its effect can be minimized by
reducing it to Fe2+ with hydroxylamine, or adding tartare or citrate ions which
react with Fe3+ to give a product that does not coprecipitate
➢ BaSO4 precipitate shows no tendency to peptize, so it is washed with pure water,
but volume of water is kept small because BaSO4 is only moderately insoluble.
➢ Ashless filter paper with BaSO4 precipitate is burned at low temperature in the
presence of fresh air - ashing
 ➢ Carbon from paper can reduce BaSO4 to BaS if ashing is done in O2- deficient
atmosphere
BaSO4(s) + 4C(s) → BaS(s) + 4CO(g)
➢ Small amount of BaS can be ignored because it is slowly oxidized during
continued heating after the carbon burned off.
➢ When large amounts of BaS is formed, oxidation might be incomplete and lead to
low results
➢ To minimize effect, displace sulfide ion by adding a drop of concentrated
sulphuric acid before continued heating:
BaS(s) + H2SO4 → BaSO4(s) + H2O(g)
➢ Excess H2SO4 is volatilized as SO3(g) and H2O(g)
➢ After ashing, precipitate is ignited to 800℃ to remove traces of water that will not
volatilize at lower temperatures
➢ Anions that are coprecipitates as barium salts are almost always oxidized to BaO
during ignition, making precipitate heavier than it should be, producing a positive
error

2. Determination of chloride
➢ Chloride is precipitated as silver chloride by addition of AgNO 3
Ag+ + Cl- → AgCl (s)
➢ Precipitation done in moderately acidic solution (0.1-0.3M HNO3) to avoid
simultaneous precipitation of insoluble salts of
OH-, CN-, CO32-, PO43-, AsO 43-
➢ Strongly acidic solutions should be avoided because they increase solubility of
AgCl
➢ Anions: Br-, I-, SCN-, S2-, CO32-, Fe(CN)64- form insoluble compounds with silver
ion and must be removed from the sample prior to precipitation
➢ Cations: Cr3+, Cd2+, Sn2+, Pt4+, Hg2+ interfere most seriously by forming soluble
complex ions with chloride, competing with Ag + for the chloride in solution
➢ AgCl is a colloidal-type of precipitate whose major source of contamination is via
surface adsorption
➢ Avoid large excess of AgNO3 precipitating agent to prevent formation of an
electrical double layer that will make the colloid difficult to coagulate
➢ Controlling amount of excess AgNO3 and boiling the solution after precipitation
is enough to coagulate the colloid
➢ Freshly precipitated AgCl solutions may be digested overnight to improve
particle size and decrease the amount of adsorbed impurities, since post
precipitation is not a problem
 ➢ Precipitate is rinsed sparingly with dilute HNO3 (0.1M) to minimize the
peptization and replace adsorbed, non-volatile electrolytes such as AgNO3, KNO3,
and NaNO3, with HNO3 that is volatilized during drying step
➢ AgCl is dried to constant weight at 110-120°C
➢ AgCl precipitates should be kept away from intense light to prevent
photodecomposition:
2AgCl(s) –light→ 2Ag(s) + Cl2(g)
➢ Direction of error due to photodecomposition depends on whether or not AgCl is
in the presence of excess Ag + ion
➢ When no excess Ag+ ion is present, only the reaction above occurs and the net
result is that AgCl molecules are converted to an equal number of Ag atoms.
Precipitate gets lighter and error is negative
2AgCl(s) –light→ 2Ag(s) + Cl2(g)
➢ If excess Ag ion is present, Cl2 reacts with water forming Cl- combining with
+

excess Ag + ion producing more AgCl

Cl2 + H2O → H+ + Cl- + HOCl
Ag+ + Cl- → AgCl (s)
Adding all reactions:
AgCl(s) + H2O + Ag + → 2Ag(s) + H+ + HOCl
➢ Since two Ag atoms are formed for each AgCl lost, the precipitate gets heavier
and the error is positive

3. Determination of nickel
➢ Nickel ion is precipitated with a very selective organic precipitating reagent –
dimethylglyoxime (DMGH)
Ni2+ + 2DMGH → 2H+ + Ni(DMG)2(s)
➢ Only Ni2+, Pd2+, and Bi3+ form insoluble compounds with DMGH
➢ Pd2+ precipitates from dilute Hcl solution only
➢ Ni2+ precipitates from solution above pH 5
➢ Bi3+ precipitates from solution above pH 11
➢ Nickel is precipitated by adding DMGH to an acidified Ni2+, then made basic by
ammonia
➢ Addition of NH3 serves two purposes:
a. Makes solution basic, lowering the solubility of Ni(DMG)2;
b. Forms soluble complex ions with several transition metal ions, preventing
their simultaneous precipitation as metal hydroxides
➢ Neither coprecipitation nor post precipitation are serious problems and precipitate
is usually digested at 60°C for an hour or two before it is filtered through a
sintered glass crucible
➢ Precipitate does not peptize and can be washed with pure water
 ➢ During washing, precipitates has a tendency to creep up the side of the crucible,
so care is required
➢ Precipitate loses water above 80°C but should not be heated above 175°C, where
it begins to decompose
➢ Combustion is performed in a long tube with copper oxide-lead chromate mixture
as a catalyst
➢ A metallic silver wire removes any gaseous sulfur and halogen compounds
formed during combustion;
➢ Lead dioxide removes any nitrogen oxides
➢ Water and carbon dioxide are carried out of the tube by the oxygen and into a
carefully weighed desiccant (usually magnesium perchlorate)
➢ Co2 passes into a second weighed tube containing Ascarite, where it is absorbed
➢ Tubes are sealed, removed from the apparatus, weighed
➢ Weight gains of the tubes are typically only a few milligrams, representing the
weights of H2O and CO2 evolved from the sample. Microbalances must be used
➢ Procedure requires great manipulative skill, like removal of dust and fingerprints
from the glass tubes by wiping with a type of cloth a fixed number of times,
always in the same direction
➢ Gas chromatography (faster and easily automated) can be used by H2O and CO2
determination but cannot match the precision and accuracy of gravimetric method
➢ Gravimetric methods have been developed for most inorganic anions and cations,
neutral species (Water, sulfur dioxide, carbon dioxide, I2)
➢ Organic samples gravimetrically determined:
○ Lactose in milk
○ Salicylates in drug preparations
○ Phenolphthalein in laxatives
○ Nicotine in pesticides
○ Cholesterol in cereals
○ Benzaldehyde in almond extracts
➢ Inorganic Precipitating Agents (p.288, Table 12.2)

DEFINITION OF TERMS
❖ Adsorption - the attraction of molecules onto the surface of a solid
➢ Adsorption vs Absorption
- Absorption is the process in which a fluid is dissolved by a liquid or a
solid (absorbent). Adsorption is the process in which atoms, ions or
molecules from a substance (it could be gas, liquid or dissolved solid)
adhere to a surface of the adsorbent.
❖ Coprecipitation - a kind of precipitation where soluble compounds in a solution are
eliminated during the course of precipitation
 - the carrying down by a precipitate of substances normally soluble under
the conditions employed
- the simultaneous precipitation of a normally soluble component with a
macro-component from the same solution by the formation of mixed
crystals, by adsorption, occlusion or mechanical entrapment
❖ Post precipitation - a kind of precipitation where the precipitation of the undesirable
compound occurs after the formation of the precipitate of the desired compound.
➢ Coprecipitation vs Post Precipitation
- Coprecipitation happens when two or more substances come together to
form a new substance, while post precipitation happens when a substance
falls out of solution.
- In coprecipitation, the substances are in the same phase (solid, liquid or
gas), while in post precipitation the substances are in different phases.