100 Solved Problem in Analytical Chemistry

CHAPTER 12
Gravimetric Methods of analysis
Gravimetric methods are quantitative methods that supersaturated solution is an unstable solution that
are based on determining the mass of a pure contains a higher solute concentration than a
compound to which the analyte is chemically related. saturated solution. As excess solute precipitates with
time, supersaturation decreases to zero.
Properties of Precipitates and Precipitating
Reagents Nucleation is a process in which a minimum number
of atoms, ions, or molecules join together to give a
Ideally, a gravimetric precipitating agent should react
stable solid.
specifically or at least selectively with the analyte,
the ideal precipitating reagent would react with the Precipitates that have very low solubilities, such as
analyte to give a product that is many sulfides and hydrous oxides, generally form as
1. easily filtered and washed free of contaminants colloids

2. of sufficiently low solubility that no significant loss Colloidal Precipitates

of the analyte occurs during filtration and washing; Individual colloidal particles are so small that they
3. unreactive with constituents of the atmosphere; are not retained by ordinary filters.

4. of known chemical composition after it is dried or, Adsorption is a process in which a substance (gas,
if necessary, ignited (Section 12A-7). liquid, or solid) is held on the surface of a solid. In
contrast, absorption is retention of a substance
An example of a selective reagent is AgNO3. The only within the pores of a solid.
common ions that it precipitates from acidic solution
are Cl2, Br2, I2, and SCN2. Dimethylglyoxime. Peptization is a process by which a coagulated
colloid returns to its dispersed state

Digestion is a process in which a precipitate is heated

Particle Size and Filterability of Precipitates in the solution from which it was formed (the
mother liquor) and allowed to stand in contact with
Colloidal suspensions, whose tiny particles are
the solution.
invisible to the naked eye (1027 to 1024 cm in
diameter). Colloidal particles show no tendency to Digestion improves the purity and filterability of both
settle from solution and are difficult to filter. colloidal and crystalline precipitates.
Crystalline suspension is the temporary dispersion Mother liquor is the solution from which a
of such particles in the liquid phase. precipitate was formed.
The net effect of these variables can be accounted Coprecipitation is a process in which normally
for at least qualitatively, by assuming that the soluble compounds are carried out of solution by a
particle size is related to a single property of the precipitate.
system called relative supersaturation, where
Surface Adsorption

Adsorption is often the major source of

Q−S contamination in coagulated colloids but of no
Relative Saturation =
S significance in crystalline precipitates

Q is the concentration of the solute at any instant In adsorption, a normally soluble compound is
carried out of solution on the surface of a coagulated
S is its equilibrium solubility colloid. This compound consists of the primarily
adsorbed ion and an ion of opposite charge from the Representative methods based on precipitation by
counter-ion layer. homogeneously generated reagents are given in
Table 12-1.
Figure 12-4 A coagulated colloid. This figure
suggests that a coagulated colloid continues to
expose a large surface area to the solution from
which it was formed.

Drying and Ignition of Precipitates

Figure 12-4 A coagulated colloid. This figure
After filtration, a gravimetric precipitate is heated
suggests that a coagulated colloid continues to
until its mass becomes constant. Heating removes
expose a large surface area to the solution from
the solvent and any volatile species carried down
which it was formed.
with the precipitate. Some precipitates are also
Specific surface area is defined as the surface area ignited to decompose the solid and form a
per unit mass of solid and usually has the units of compound of known composition. This new
square centimeters per gram. compound is often called the weighing form.

The temperature required to dehydrate a precipitate

completely may be as low as 100°C or as high as
1000°C.

Calculation of results from Gravimetric Data

Mixed-crystal formation is a type of coprecipitation The results of a gravimetric analysis are generally
in which a contaminant ion replaces an ion in the computed from two experimental measurements:
lattice of a crystal. the mass of sample and the mass of a product of
known composition. The examples that follow
Occlusion is a type of coprecipitation in which a
illustrate how such computations are carried out.
compound is trapped within a pocket formed during
rapid crystal growth. EXAMPLE 12-1 The calcium in a 200.0-mL sample of
a natural water was determined by precipitating the
Coprecipitation can cause either negative or positive
cation as CaC2O4. The precipitate was filtered,
errors.
washed, and ignited in a crucible with an empty
Precipitation from Homogeneous Solution mass of 26.6002 g. The mass of the crucible plus CaO
(56.077 g/mol) was 26.7134 g. Calculate the
Homogeneous precipitation is a process in which a concentration of Ca (40.078 g/mol) in water in units
precipitate is formed by slow generation of a of grams per 100 mL of the water.
precipitating reagent homogeneously throughout a
solution. Solution:
 Solution

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.

Applications Of Gravimetric Methods

Lists common inorganic precipitating agents. These

reagents typically form slightly soluble salts or
hydrous oxides with the analyte.
Reducing Agents

Lists several reagents that convert an analyte to its

elemental form for weighing.

Organic Functional Group Analysis

Several reagents react selectively with certain

organic functional groups and thus can be used for
the determination of most compounds containing
these groups. A list of gravimetric functional group
reagents

Organic Functional Group Analysis

Several reagents react selectively with certain

organic functional groups and thus can be used for
the determination of most compounds containing
these groups. A list of gravimetric functional group
reagents is given in table below. Many of the
reactions shown can also be used for volumetric and
spectrophotometric determinations.

1. 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.

a.

b.

c.
d. B

2. What mass of Cu(IO3)2 can be formed from 0.650 C

g of CuSO4 · 5H2O?
D
a.
7. *12-22. Ammoniacal nitrogen can be determined
b. by treatment of the sample with chloroplatinic acid;
the product is slightly soluble ammonium
c.
chloroplatinate:
d.
H2PtCl6 1 2NH41 S (NH4)2PtCl6 1 2H1
3. What mass of KIO3 is needed to convert the
a.
copper in 0.2750 g of CuSO4 · 5H2O to Cu(IO3)2?
b.
a
c.
a.
d.
b.
8. *12-24. A series of sulfate samples is to be
c.
analyzed by precipitation as BaSO4. If it is known
d. that the sulfate content in these samples ranges
between 20% and 55%, what minimum sample mass
4. What mass of AgI can be produced from a 0.512-g should be taken to ensure that a precipitate mass no
sample that assays 20.1% AlI3? smaller than 0.200 g is produced? What is the
maximum precipitate mass to be expected if this
a.
quantity of sample is taken?
b.
a.
c.
b.
d.
c.
5. A 0.2121-g sample of an organic compound was
d
burned in a stream of oxygen, and the CO2 produced
was collected in a solution of barium hydroxide. 9-11. The efficiency of a particular catalyst is highly
Calculate the percentage of carbon in the sample if dependent on its zirconium content. The starting
0.6006 g of BaCO3 was formed. material for this preparation is received in batches
that assay between 68% and 84% ZrCl4. Routine
a.
analysis based on precipitation of AgCl is feasible, it
b. having been established that there are no sources of
chloride ion other than the ZrCl4 in the sample
c.
9. What sample mass should be taken to ensure an
d. AgCl precipitate that weighs at least 0.400 g?
6. The mercury in a 1.0451-g sample was a.
precipitated with an excess of paraperiodic acid,
H5IO6 b.

5Hg21 1 2H5IO6 S Hg5(IO6)2 1 10H1 c.

A d.
10. If this sample mass is used, what is the the solubility of Ba(IO3)2 in water is negligibly small
maximum mass of AgCl that can be expected in this and calculate
analysis?
14. (a) the mass of the precipitated Ba(IO3)2.
a.
a.
b.
b.
c.
c.
d.
d.
11. To simplify calculations, what sample mass
15. (b) the mass of the unreacted compound that
should be taken to have the percentage of ZrCl4
remains in solution.
exceed the mass of AgCl produced by a factor of
100? a.
a. b.
b c.
c. d.
d. 16. When a 100.0-mL portion of a solution
containing 0.500 g of AgNO3 is mixed with 100.0 mL
12. A 0.6407-g sample containing chloride and iodide
of a solution containing 0.300 g of K2CrO4, a bright
ions gave a silver halide precipitate weighing 0.4430
red precipitate of Ag2CrO4 forms. (a) Assuming that
g. This precipitate was then strongly heated in a
the solubility of Ag2CrO4 is negligible, calculate the
stream of Cl2 gas to convert the AgI to AgCl; on
mass of the precipitate. (b) Calculate the mass of the
completion of this treatment, the precipitate
unreacted component that remains in solution.
weighed 0.3181 g. Calculate the percentage of
chloride and iodide in the sample.

a.

b.

c.

d.

13. What mass in grams of CO2 is evolved in the

complete decomposition of a 2.300-g sample that is
38.0% MgCO3 and 42.0% K2CO3 by mass?

a.

b.

c.

d.

14-15. A 50.0-mL portion of a solution containing

0.200 g of BaCl2 # 2H2O is mixed with 50.0 mL of a
solution containing 0.300 g of NaIO3. Assume that
Solutions:

1.

1 mol KCl 1 mol KCl 74.55 g KCl

0.2912 g AgCl × × ×
143.32 g 1 mol AgCl 1 mol
× 100 =60.59
0.2500 g impure sample

2.

3.

20.1 g 1mol AlI 3 mol AgI 234.77 g AgI

Mass AgI = 0.512 g × × × × =o.178 g
100 g 407.69 g 1 mol AlI 1 mol AgI
5.
 Chapter 13
Titrations in Analytical Chemistry
Discussion: titrate (1) a known mass of a primary standard, (2) a
known mass of a secondary standard, or (3) a
Titrations are widely used in analytical chemistry to measured volume of another standard solution. A
determine acids, bases, oxidants, reductants, metal titrant that is standardized is sometimes referred to as
ions, proteins, and many other species. Titrations are a secondary standard solution. The concentration of
based on a reaction between the analyte and a a secondary-standard solution is subject to a larger
standard reagent known as the titrant. The reaction is uncertainty than is the concentration of a primary-
of known and reproducible stoichiometry. The standard solution. If there is a choice, then, solutions
volume, or the mass, of the titrant needed to react are best prepared by the direct method. Many
completely with the analyte is determined and used to reagents, however, lack the properties required for a
calculate the quantity of analyte. primary standard and, therefore, require
standardization.
Titration methods are based on determining the
quantity of a reagent of known concentration that is
required to react completely with the analyte. Volumetric Calculations
The reagent may be a standard solution of a chemical
Most volumetric calculations are based on two pairs
or an electric current of known magnitude. In
of simple equations that are derived from definitions
volumetric titrations, the volume of a standard
of the mole, the millimole, and the molar
reagent is the measured quantity.
concentration. For the chemical species A, we can
write:
Some Terms Used in Volumetric Titrations

A standard solution is a reagent of known

concentration. Standard solutions are used in mass A ( g)
titrations and in many other chemical analyses. amount A ( mol ) =
molar mass A( g /mol)
Back-titration is a process in whichthe excess of a
standard solution used to consume an analyte is
determined by titration with a second standard The second pair of equations is derived from the
solution. Back-titrations are often required when the definition of molar concentration,
that is,
rate of reaction between the analyte and reagent is
slow or when the standard solution lacks stability. mol A
amount A ( mol ) =V ( L)×
The equivalence point is the point in a titration when L
the amount of added standard reagent is equivalent to
the amount of analyte.
Gravimetric Titrations
The end point is the point in a titration when a
physical change occurs that is associated with the Mass (weight) or gravimetric titrations differ from
condition of chemical equivalence. their volumetric counterparts in that the mass of
titrant is measured rather than the volume. Therefore,
in a mass titration, a balance and a weighable
Standard Solutions solution dispenser are substituted for a buret and its
markings.
The first is the direct method in which a carefully
determined mass of a primary standard is dissolved in
The most common way to express concentration for
a suitable solvent and diluted to a known volume in a
mass titrations is the weight concentration, cw, in
volumetric flask. The second is by standardization
weight molar concentration units, Mw, which is the
in which the titrant to be standardized is used to
number of moles of a reagent in one kilogram of 5.23 ×10 mol 34 g H 2 O2 1000 mg
−4
solution or the number of millimoles in one 2.92 L × × ×
gram of solution. L mol H 2 O 2 1g

The weight molar concentration cw(A) of a solution ¿ 51.9234 milligrams

of a solute A is computed using:
where: Molecular Weight of H 2 O 2 is
no . mol A
weight molar concentration= 34g
no . kg solution
5. Calculate the molar concentration of a solution that
is 50.0% NaOH (w/w) and has a specific gravity of
1.52.
Solved Problems:

1-2. How many millimoles of solute are contained in

(a) 2.00 L of 2.76 ×10−3 M KMnO4? (b) 2.50 Given:
kg g
L of 0.352 M KCl? Density of solution = 1520 3 = 1.52
m ml
Solution: g
M.W of NaOH = 40
mol
(a)
Solution:
−3
2.76 ×10 mol 1000 mmol
2L× ×
L 1 mol 50 g NaOH 1.52 g soln 1 mol NaOH 1000 ml
× × ×
100 g soln ml 40 g NaOH L
¿ 5.52mmol
mol
(b) ¿ 19 =19 M
L
0.352 mol 1000mmol 6. Calculate the molar concentration of a 20.0%
2.50 L× ×
L 1 mol solution (w/w) of KCl that has a specific gravity of
1.13.
¿ 880 mmol
3-4.What mass of solute in milligrams is contained in Given:
(a) 26.0 mL of 0.250 M sucrose (342 g/mol)? (b) 2.92
L of 5.23× 10−4 M H2O2? kg g
Density of solution = 1130 =1.13
m
3
ml
Solution: g
M.W of KCL = 74.55
(a)
mol
Solution:
0.25 mmol 342 g 1 mol
26 ml × × ×
ml mol 1000 mmol 20 g KCL 1.13 g soln 1mol KCL 1000 ml
× × ×
¿ 2.223 grams 100 g soln ml 74.55 g KCL L
¿ 2223 milligrams
mol
¿ 3.0315
(b) L
¿ 3.03 M
7-8. Describe the preparation of (a) 500 mL of 0.0750 kg
M AgNO3 from the solid reagent. (b) 600 mL of Density of solution = 160 0 3 = 1.60
2.00% (w/v) aqueous BaCl2 from a 0.500 M BaCl2 m
solution. g
ml
Solution: g
M.W of HClO 4 = 100.5
mol
(a)
mol mol
0.0750 M =0.0750 0.120 M = 0.120
L L

0.0750 mol AgNO 3 60 g HClO 4 1.60 g soln 1 mol HClO 4

1L × ×
500 ml × × 100 g soln ml 100.5 g HClO 4
L 1000 ml

¿ 0.0375 mol mol HClO 4

¿ 9.55 ×10−3
ml
169.87 g AgNO3
0.0375 mol × 0.120 mol HClO4
mol AgNO3 2 Liters ×
L
¿ 6.3701 g of AgNO3
¿ 0.240 mol HClO 4
(b)
w 2g Vol. of reagent:
2 ( )
v
=
100 ml
1 ml
0.240 mol HClO 4 × −3
2 g BaCl2 1mol BaCl2 9.55× 10 mol HClO4
600 ml × ×
100 ml soln 208.23 g BaCl 2
¿ 25.131 ml
¿ 0.025 L
¿ 0.0576 mol
(b)
L
0.0576 mol ×
0.5 mol BaCl2 Given:

¿ 0.1152 L kg
Density of solution = 1525 = 1.525
m3
9-10. Describe the preparation of (a) 2.00 L g
of 0.120 M HClO4 from the commercial
reagent [60% HClO4 (w/w), sp gr 1.60]. (b)
ml
1.50 L of 0.215 M NaOH from the g
M.W of NaOH = 40
concentrated commercial reagent [50% mol
NaOH (w/w), sp gr 1.525]. mol
0.215 M =0.215
L
Solution:

(a)
50 g NaOH 1.525 g NaOH 1 mol
× ×
100 g soln ml 40 g NaOH
Given:
mol NaOH
¿ 0.0191
ml
 0.215 mol NaOH ml
1.50 L× 0.3225 mol NaOH ×
L 0.0191mol NaOH

¿ 0.3225 mol NaOH ¿ 16.885 ml

= 0.0168
Vol. of reagent:

Chapter 14
Principles of Neutralization Titrations
Discussion: 4. What is the pH of an aqueous
solution that is 3.00% HCl by mass
Solved Problems:
and has a density of 1.015 g/mL?
1. 5.

6.

2. Using the data in Problem 1,

calculate pKw at
(a) 0 °C.
*(b) 50°C. 7.
(c) 100°C.
3. Using the data in Problem 1,
calculate the pH of a

(a) 0 °C.
*(b) 50°C.
(c) 100°C.
8.

9.
2.

10.

3.

4.

Solutions: 5.

1.
6.
8.

7.

9.
10.

Chapter 15
Complex Acid/Base Systems

Discussion:
A. Mixtures Of Strong And Weak Acids Or
Strong And Weak Bases
Each of the components in a mixture
containing a strong acid and a weak acid (or a strong
base and a weak base) can be determined provided
that the concentrations of the two are of the same
order of magnitude and that the dissociation constant
for the weak acid or base is somewhat less than about
10-4.

Hydrochloric acid suppresses the

dissociation of the weak acid in the early stages of
the titration to such an extent that we can assume that
[A-] ,, cHCl and [H3O+] 5 cHCl. In other words, the
hydronium ion concentration is simply the molar
concentration of the strong acid. B. Polyfunctional Acids And Bases

The composition of a mixture of a strong There are several species of interest in

acid and a weak acid can be determined by titration analytical chemistry that have two or more
with suitable indicators if the weak acid has a acidic or basic functional groups. These species
dissociation constant that lies between 1024 and 1028 are said to exhibit polyfunctional acidic or basic
and the concentrations of the two acids are of the behavior. Generally, with a polyfunctional acid
same order of magnitude. such as phosphoric acid (H3PO4), the protonated
species (H3PO4, H2PO42, HPO422) differ
enough in their dissociation constants that they
exhibit multiple end points in a neutralization
titration.
 B.1. The Phosphoric Acid System

Phosphoric acid is a typical

polyfunctional acid. In aqueous solution, it
undergoes the following three dissociation
reactions:

The first reaction describes the

hydration of aqueous CO2 to form carbonic
acid. Note that the magnitude of Khyd
indicates that the concentration of CO2(aq)
is much larger than the concentration of
H2CO3 (that is, [H2CO3] is only about
0.3% that of [CO2(aq)]). Thus, a more
useful way of discussing the acidity of
Generally, Ka1 . Ka2, often by a solutions of carbon dioxide is to combine
factor of 104 to 105 because of electrostatic Equation 15-3 and 15-4 to give
forces. That is, the first dissociation involves
separating a single positively charged
hydronium ion from a singly charged anion.
In the second step, the hydronium ion must
be separated from a doubly charged anion, a
process that requires considerably more
energy. C. Buffer Solutions Involving Polyprotic Acids
Two buffer systems can be prepared from a
weak dibasic acid and its salts. The first consists
of free acid H2A and its conjugate base NaHA,
When we add two adjacent
and the second makes use of the acid NaHA and
stepwise equilibria, we multiply the two
its conjugate base Na2A. The pH of the
equilibrium constants to obtain the
NaHA/Na2A system is higher than that of the
equilibrium constant for the resulting overall
H2A/NaHA system because the acid dissociation
reaction. Thus, for the first two dissociation
constant for HA2 is always less than that for
equilibria for H3PO4, we write
H2A. We can write enough independent
equations to permit a rigorous calculation of the
hydronium ion concentration for either of these
systems. Ordinarily, however, it is permissible to
introduce the simplifying assumption that only
one of the equilibria is important in determining
the hydronium ion concentration of the solution.

D. Calculation Of The Ph Of Solutions Of NaHa

We have not yet considered how to calculate
B.2. The Carbon Dioxide/Carbonic Acid the pH of solutions of salts that have both acidic
System and basic properties, that is, salts that are
amphiprotic. Such salts are formed during
When carbon dioxide is dissolved
neutralization titrations of polyfunctional acids
in water, a dibasic acid system is formed by
and bases. For example, when 1 mol of NaOH is
the following reactions:
added to a solution containing 1 mol of the acid
H2A, 1 mol of NaHA is formed. The pH of this
solution is determined by two equilibria
established between HA2 and water:
 G. Titration Curves For Amphiprotic Species

E. Titration Curves For Polyfunctional Acids

An amphiprotic substance when dissolved in
Compounds with two or more acidic a suitable solvent behaves both as a weak acid
functional groups yield multiple end points in a and as a weak base. If either of its acidic or basic
titration if the functional groups differ characters predominates, titration of the
sufficiently in strength as acids. The substance with a strong base or a strong acid
computational techniques described in Chapter may be feasible. For example, in a sodium
14 permit construction of reasonably accurate dihydrogen phosphate solution, the principal
theoretical titration curves for polyprotic acids if equilibria are:
the ratio Ka1/Ka2 is somewhat greater than 103.
If this ratio is smaller, the error becomes
excessive, particularly in the region of the first
equivalence point, and a more rigorous treatment
of the equilibrium relationships is required.
H. Composition Of Polyprotic Acid Solutions
AS A Function Of pH

alpha values are useful in visualizing the

changes in the concentration of various
species that occur in a titration of a
monoprotic weak acid. Alpha values provide
an excellent way of thinking about the
properties of polyfunctional acids and bases.
For example, if we let cT be the sum of the
molar concentrations of the maleate-
containing species in the solution throughout
F. Titration Curves For Polyfunctional Bases the titration described in Example 15-9, the
alpha value for the free acid a0 is defined a

Solved Problem:
 CHAPTER 16
Applications of Neutralization Titrations
Discussion:
Solved Problem:
Typical Application of Neutralization a.) 0.02415
Titrations
b. 0.01535
Neutralization titrations are used to
c.) 0.03421
determine the innumerable inorganic,
organic, and biological species that possess d.) 0.03451
inherent acidic and basic properties.
2. Same question as number ___ if titration
Major Types of End Point of 0.4512 g of primary standard potassium
hydrogen phthalate (KHP) required 26.46 ml
1.) Visual end point (based on
of base.
indicators)
2.) Potentiometric end point (use of a. 0.04175
voltage-measuring device)
b.) 0.03451
c.) 0.05635
SOLVED PROBLEMS:
d.) 0.01123
1. Calculate the molarity of a dilute
Ba(OH)2 solution if 50.00 ml yielded 3. Same question as number ___ if addition
0.1791 g of BaSO4. of 50 ml of base to 0.3912 g of benzoic acid
required a 4.67 ml back titration with 0.0531 c.0.1214
M HCl.
d.) 0.1312
a.) 0.054325
5. A 3L sample of urban air was bubbled
b. 0.03452 through a solution containing 50 ml of
0.0116 M Ba(OH) 2 which caused the CO2
c.) 0.07632
in the sample to precipitate as BaCO3. The
d.) 0.00121 excess base was back titrated to a
phenolphthalein end point with 23.6 ml of
4. A 50 ml sample of white dinner wine 0.0108 M HCl. Calculate the concentration
required 24.57 ml of 0.03291 M NaOH to of CO2 in the air in ppm; use 1.98 g/L for
achieve phenolphthalein end point. Express the density of CO2.
the acidity of the wine in grams of tartaric
acid (H2C4H4O6; 150.09g/mol) per 100 ml. a. 3.35 x103 ppm
(Assume that two hydrogens of the acid are
b.) 1.24 x103 ppm
titrated).
c.) 2.45 x103 ppm
a.)0.1345
d.) 3.38 x103 ppm
b.)0.4343
 Chapter 17
Complexation and Precipitation Reactions and Titrations