Topic 5

Gravimetric Methods of Analysis

Chem 130/ Chem 151
Analytical Methods/ Analytical Chemistry
Week 10-12
9 hrs
Alfredo C. Santos
Instructor

For WMSU Instructional Use 1

 INTRODUCTION
• Several analytical methods are based on mass measurements.
In precipitation gravimetry, the analyte is separated from a
solution of the sample as a precipitate and is converted to a
compound of known composition that can be weighed. In
volatilization gravimetry, the analyte is separated from other
constituents of a sample by converting it to a gas of known
chemical composition. The mass of the gas then serves as a
measure of the analyte concentration. In gravimetric
combustion analysis, a sample is burned in excess oxygen and
products are measured. Combustion is typically used to measure
C, H, N, S, and halogens in organic matter. These three types of
gravimetry are considered in this topic.
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Topic Outline
• General steps in gravimetric analysis
• Precipitation gravimetry
- Precipitation
- Drying and ignition
- Factors affecting solubility of precipitates
- Von Weimarn ratio
- Co-precipitation problems
- Minimization of co-precipitation problems
• Volatilization Gravimetry
• Gravimetric combustion analysis
• Gravimetric calculations and applications 3
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Specific Objectives
At the end of this topic, the students can:
• Construct a flowchart showing the steps in gravimetric analysis
• Differentiate the types of gravimetric analysis.
• Describe the different types of precipitates
• Explain the factors affecting solubility of precipitates
• Interpret the von Weirmarn ratio to supersaturation and solubility
• Describe co-precipitation and post precipitation and their effect
on the precipitation
• Apply concepts to gravimetric problems and its application
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Gravimetric Methods of Analysis
• are based on the measurement of mass
• There are two major types of gravimetric methods:
1. Precipitation methods (Precipitation Gravimetry)
- the analyte is converted to a sparingly soluble precipitate,
filtered, washed free of impurities, and converted to a
product of known composition by suitable heat treatment,
and the product is weighed.
- Ex. Determination of Ca in water

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Gravimetric Methods of Analysis

2. 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
- Ex. Determination of % moisture

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Precipitation Gravimetry
Steps:
1. Sampled dried, triplicate portions weighed
2. Preparation of the solution
3. Precipitation
4. Digestion
5. Filtration
6. Washing
7. Drying or igniting
8. Weighing
9. Calculation : weighed CaO, calculate %Ca
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 Precipitation Gravimetry
• Precipitation Techniques
- Add precipitating reagent to sample solution
- Reacts with analyte to form insoluble material
- Precipitate has known composition or can be converted to
known composition
• Handling of Precipitate
- Quantitative collection of analyte
- w/o loss of material in handling/processing
- Isolation of pure product
- free from solvent, impurities
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Precipitation Gravimetry
• Determination of mass
- Direct or
- By difference
• Calculation of original analyte content
- concentration

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Properties of Precipitating Reagents

• precipitating agent should react specifically or at least selectively

with the analyte
- Specific reagents, which are rare, react only with a single
chemical species
Ex. Dimethylglyoxime (DMG) precipitates only Ni2+ from
alkaline solutions.
- Selective reagents, which are more common, react with a
limited number of species
Ex. AgNO3 precipitates only Cl–, Br–, I–, and SCN– from
acidic solutions. For WMSU Instructional Use 10
Desirable Properties of Precipitates

• the precipitating reagent should react with the analyte to give a

product that is
1. easily filtered and washed free of contaminants;
2. of sufficiently low solubility that no significant loss of the
analyte occurs during filtration and washing;
3. unreactive with constituents of the atmosphere;
4. of known chemical composition after it is dried or, if
necessary, ignited
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Representative analytical precipitations are listed in Table 5-1
Table 5-1.
Representative
gravimetric analyses.
Harris, D.C. 2006.

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 A few common organic precipitants are listed in Table 5-2
Table 5-2.
Common
organic
precipitating
agents. Harris,
D.C. 2006.

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Particle Size and Filterability of Precipitates

• Precipitates consisting of large particles are generally desirable

for gravimetric work
- easy to filter and wash free of impurities
- usually purer than are precipitates made up of fine particles
• Colloidal suspension
- invisible to the naked eye (10-7 to 10-4 cm in diameter)
- show no tendency to settle from solution
- difficult to filter

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Particle Size and Filterability of Precipitates

or Von Weimarn ratio

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Particle Size and Filterability of Precipitates
• The particle size of crystalline solids can often be improved
significantly by minimizing Q or maximizing S, or both.
• Minimizing the value of Q
- using dilute solutions, and
- adding the precipitating reagent slowly, with good mixing
• Maximizing the value of S
- precipitating from hot solution, or
- adjusting the pH of the precipitation medium, provided the
solubility of the precipitate depends on pH
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Coprecipitation
• a process in which normally soluble compounds are carried out of
solution by a precipitate
• Types:
1. surface adsorption
2. mixed-crystal formation
3. occlusion
4. mechanical entrapment

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Surface Adsorption
• is likely to cause significant contamination of precipitates with
large surface areas, that is, coagulated colloids.
specific surface areas (cm2/g)↑→ adsorption↑
• Example: in chloride analysis
- primary adsorbed ion : Ag+
- counter-ion layer : NO3- or other anions
- AgNO3 (normally soluble) is coprecipitated with the AgCl (s).
AgCl:Ag+ · · · NO3- (s) 18
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 c. Reprecipitation – the filtered solid is redissolved and
reprecipitated
- less adsorption occurs during the second precipitation
Mixed-Crystal Formation
• a contaminant ion replaces an ion in the lattice of a crystal
a. the same charge
b. the size differ < 5 %
c. salt : the same crystal class
• Ex: PbSO4 in BaSO4
BaCl2 + sol’n containing sulfate, lead & acetate
→ BaSO4 + PbSO4 (Pb + acetate → lead acetate complex)
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• Other Examples: MgKPO4 in MgNH4PO4, SrSO4 in BaSO4, and
MnS in CdS.

Occlusion
• When a crystal is growing rapidly during precipitate formation,
foreign ions in the counter-ion layer may become trapped, or
occluded,

Mechanical Entrapment
• Several crystals grow together and in so doing trap a portion of
the solution in a tiny pocket
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• Minimizing Adsorbed Impurities on Colloids
a. Digestion – water is expelled from the solid to give a denser
mass that has a smaller specific surface area for adsorption.
particle size↑→ specific surface area↓→ adsorption↓

b. Washing with volatile electrolyte solution

ex: in Ag+ analysis AgCl:Cl– · · · Na+ (s)
primary adsorbed ion : Cl– AgCl:Cl– · · · H+ (s)
washing with an acidic soln → counter-ion layer : H+
→ HCl volatilized when ppt is dried
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Drying and Ignition of Precipitates

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Drying and Ignition of Precipitates

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Calculation of Results from Gravimetric Data
• The results of a gravimetric analysis are generally computed from
the mass of the sample and the mass of the product
Example 5-1:
The calcium in a 200.0-mL 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 26.6002 g. The mass of the crucible plus CaO was 26.7134 g.
a) Calculate the concentration of Ca in water in units of grams per
100 mL of the water.
b) What is the molar concentration of Ca?
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Volatilization Gravimetry
Water Determination
- Water is quantitatively distilled from many materials by heating
at 110-115oC.
- In direct determination, water vapor is collected on any of
several solid desiccants, and its mass is determined from the
mass gain of the desiccant (Ex. CaSO4)
- In indirect determination, the amount of water is determined by
the loss of mass of the sample during heating
~less satisfactory because it must be assumed that water is the
only component that is volatilized 29
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AOAC Official Method. AOAC 930.15-1930 (1999)
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Volatilization Gravimetry
CO2 Determination
- Used in the determination of the NaHCO3 content of antacids
~A weighed sample of the finely ground tablets is treated
with dilute sulfuric acid to convert the NaHCO3 to CO2:
NaHCO3(aq) + H2SO4(aq) CO2(g) + H2O(l) + NaHSO4(aq)
• As shown in Figure 5-1, this reaction is carried out in a flask
connected to a tube containing CaSO4 that removes water vapor
to produce a stream of pure CO2 in nitrogen.
• These gases then pass through a weighed absorption tube
containing the absorbent Ascarite II, retaining the carbon dioxide31
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Figure 5-1. Apparatus for determining the NaHCO3 content of antacid tablets. Skoog, West, & Holler, 2014 32
Gravimetric Combustion Analysis
• a historically important gravimetric analysis used to determine C
and H in organic compounds burned in excess O2 (Figure 5-2).

CuO, PbO2, or MnO2

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Figure 5-2. Gravimetric combustion analysis for carbon and hydrogen. Harris, D.C., 2006
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Combustion Analysis Today
• modern instruments use thermal conductivity, infrared
absorption, flame photometry (for S), and coulometry (for
halogens) to measure products.
• C,H,N,S elemental analyzer uses gas chromatography with
thermal conductivity detection to measure N2, CO2, H2O, and
SO2 combustion products

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Exercise
1. Construct a flowchart showing the steps in gravimetric analysis.
2. Treatment of a 0.2500-g sample of impure potassium chloride with an
excess of AgNO3 resulted in the formation of 0.2912 g of AgCl.
Calculate the percentage of KCl in the sample.
3. The calcium from a sample of limestone weighing 607.4 mg was
precipitated as calcium oxalate and ignited to calcium carbonate
weighing 246.7 mg.
a. Calculate the %Ca in the sample.
b. If the precipitate had been ignited at a higher temperature giving
CaO, what would be its weight?
3. A 6.234-mg sample produced 12.123 mg CO2 2.529 mg of H2O. Find the
% by mass of C and H in the sample.
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 The End

REFERENCES

1. Skoog, D.A., West, D.M., Holler F.J. and Crouch, S.R. (2014)
Fundamental of Analytical Chemistry, 9th edition. United States of
America, Brooks Cole.
2. Harris, D.C. (2006) Quantitative Chemical Analysis, 8th edition. New
York, W.H. Freeman and Co.
3. Harvey, D. (2000) Modern Analytical Chemistry. McGraw-Hill, USA.

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