University of Al-mustansiriyah

College of Science Department

of Chemistry

Analytical
Chemistry
For students of the second stage
by:Dr. Mohammed Zaboon Thani

2018-2019
 1.Gravimetric analysis :
Gravimetric analysis is one of the most accurate and precise methods
of macro quantitative analysis. In this process the analyte is selectively
converted to an insoluble form. The separated precipitate is dried or
ignited, possibly to another form, and is accurately weighed. From the
weight of the precipitate and a knowledge of its chemical composition,
we can calculate the weight of analyte in the desired form. In fact,
gravimetric analysis was used to determine the atomic masses of many
elements to six figure accuracy. Theodore W. Richards at Harvard
University developed highly precise and accurate gravimetric analysis of
silver and chlorine. He used these methods to determine the atomic
weights of 25 elements by preparing pure samples of the chlorides
of the elements, decomposing known weights of the compounds, and
determining the chloride content by gravimetric methods. For this work,
he was the first American to receive the Nobel Prize. He was the ultimate
analytical chemist. Gravimetry does not require a series of standards
for calculation of an unknown, because the calculations are based
only on atomic or molecular weights.

1.1.Properties of Precipitates and Precipitating Reagents.

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

1.2.How to Perform a Successful Gravimetric Analysis ?

The important steps required to obtain on the accurate gravimetric

analysis, after the sample has been dissolved, can be summarized as
follows:

1. Preparation of the solution 5. Washing

2. Precipitation 6. Drying or igniting

3. Digestion 7. Weighing

4. Filtration 8. Calculation 1
1. Preparation of the solution .

The first step in performing gravimetric analysis is to prepare the

solution. Some form of preliminary separation may be necessary to
eliminate interfering materials. Also, we must adjust the solution
conditions to maintain low solubility of the precipitate and to obtain it in
a form suitable for filtration . Factors that must be considered include the
volume of the solution during precipitation, the concentration range of the
test substance, the presence and concentrations of other constituents, the
temperature, and the pH. The pH is important because it often influences
both the solubility of the analytical precipitate and the possibility of
interferences from other substances. For example, calcium oxalate is
insoluble in basic medium, but at low pH the oxalate ion combines with
the hydrogen ions to form a weak acid and begins to dissolve.

2. Precipitation

The next step is to do the precipitation. Again, certain conditions are

important. The precipitate should first be sufficiently insoluble that the
amount lost due to solubility will be negligible. It should consist of large
crystals that can be easily filtered. All precipitates tend to carry some of
the other constituents of the solution with them. This contamination
should be negligible. Keeping the crystals large can minimize this
contamination. When a solution of a precipitating agent is added to a test
solution to form a precipitate, such as in the addition of AgNO 3 to a
chloride solution to precipitate AgCl.

Von Weimarn discovered that the particle size of precipitates is inversely

proportional to the relative supersaturation of the solution during the
precipitation process:

Relative supersaturation = Q – S/ S

where Q is the concentration of the mixed reagents before precipitation

occurs, S is the solubility of the precipitate at equilibrium, andQ − S is the
degree of supersaturation. This ratio, (Q − S)/S, relative supersaturation,
is also called the von Weimarn ratio. As previously mentioned, when a
solution is supersaturated, it is in a state of metastable equilibrium, and
this favors rapid nucleation to form a large number of small particles.
That is,

2
High relative supersaturation → many small crystals(colloidal
suspensions) (high surface area)

Low relative supersaturation → fewer, larger crystals(crystalline

suspensions (low surface area)

Colloidal Precipitates

Individual colloidal particles are so small that they are not retained by
ordinary filters. Fortunately, however, we can coagulate, or agglomerate,
the individual particles of most colloids to give a filterable, amorphous
mass that will settle out of solution.

Crystalline Precipitates
Crystalline precipitates are generally more easily filtered and purified
than are coagulated colloids. In addition, the size of individual crystalline
particles, and thus their filterability, can be controlled to some extent.

Obviously, then, we want to keep Q low and S high during precipitation.

Several steps are commonly taken to maintain favorable conditions for
precipitation:

1. Precipitate from dilute solution. This keeps Q low.

2. Add dilute precipitating reagents slowly, with effective stirring. This

also keeps Q low. Stirring prevents local excesses of the reagent.

3. Precipitate from hot solution. This increases S. The solubility should

not be too great or the precipitation will not be quantitative (with less
than 1 part per thousand remaining). The bulk of the precipitation may
be performed in the hot solution, and then the solution may be cooled to
make the precipitation quantitative.

4. Precipitate at as low a pH as is possible to maintain quantitative

precipitation. As we have seen, many precipitates are more soluble in
acid medium, and this slows the rate of precipitation. They are more
soluble because the anion of the precipitate (which comes from a weak
acid) combines with protons in the solution.

3
Mechanism of Precipitate Formation

The effect of relative supersaturation on particle size can be explained if

we assume that precipitates form in two ways: by nucleation and by
particle growth. The particle size of a freshly formed precipitate is
determined by the mechanism that predominates. In nucleation, a few
ions, atoms, or molecules (perhaps as few as four or five) come together
to form a stable solid. Often, these nuclei form on the surface of
suspended solid contaminants, such as dust particles. Further precipitation
then is governed by the competition between additional nucleation and
growth of existing nuclei (particle growth). If nucleation predominates, a
precipitate containing a large number of small particles results, and if
growth predominates, a smaller number of larger particles is produced.
The rate of nucleation is believed to increase enormously with increasing
relative supersaturation. In contrast, the rate of particle growth is only
moderately enhanced by high relative supersaturation. Therefore, when a
precipitate is formed at high relative supersaturation, nucleation is the
major precipitation mechanism, and a large number of small particles is
formed. At low relative supersaturations, on the other hand, the rate of
particle growth tends to predominate, and deposition of solid on existing
particles occurs rather than further nucleation. Low relative supersa-
turation produces crystalline suspensions.

3. Digestion
We know that very small crystals with a large specific surface area have
a higher surface energy and a higher apparent solubility than large
crystals. When a precipitate is allowed to stand in the presence of the
mother liquor (the solution from which it was precipitated), the large
crystals grow at the expense of the small ones. This process is called
digestion, or Ostwald ripening, and is illustrated in following Figure :

4
 Fig 1.Ostwald ripening

Fig 2.Representation of silver chloride colloidal particle and

adsorptive layers when Cl− is in excess.

Small particles have greater surface energy associated with a greater

surface area and display somewhat greater solubility than larger particles.
The small particles tend to dissolve and reprecipitate on the surfaces of
the larger crystals.

Impurities in precipitares.

Precipitates tend to carry down from the solution other constituents that
are normally soluble, causing the precipitate to become contaminated.
This process is called coprecipitation. The process may be equilibrium
based or kinetically controlled. There are a number of ways in which a
foreign material may be coprecipitated.

A- Occlusion and Inclusion. In the process of occlusion, material that is

not part of the crystal structure is trapped within a crystal. For example,
5
water maybe trapped in pockets when AgNO3 crystals are formed, and
this can be removed to a degree by dissolution and recrystallization. If
such mechanical trapping occurs during a precipitation process, the water
will contain dissolved impurities. Inclusion occurs when ions, generally
of similar size and charge, are trapped within the crystal lattice
(isomorphous inclusion, as with K+ in NH4MgPO4 precipitation). These
are not equilibrium processes. Occluded or included impurities are
difficult to remove. Digestion may help some but is not completely
effective. The impurities cannot be removed by washing. Purification by
dissolving and reprecipitating is helpful.

B-Surface Adsorption. As we have already mentioned, the surface of the

precipitate will have a primary adsorbed layer of the lattice ions in
excess. This results in surface adsorption, the most common form of
contamination. For example, after barium sulfate is completely
precipitated, the lattice ion in excess will be barium, and this will form
the primary layer. The counter ion will be a foreign anion, say, nitrate two
for each barium. The net effect then is an adsorbed layer of barium
nitrate, an equilibrium-based process. These adsorbed layers can often be
removed by washing, or they can be replaced by ions that are readily
volatilized. Gelatinous precipitates are especially troublesome, though.
Digestion reduces the surface area and, therefore, the adsorbed amount.

C- Post precipitation. Sometimes, when the precipitate is allowed to

stand in contact with the mother liquor, a second substance will slowly
form a precipitate with the precipitating reagent. This is called post
precipitation. For example, when calcium oxalate is precipitated in the
presence of magnesium ions, magnesium oxalate does not immediately
precipitate because it tends to form supersaturated solutions. But it will
precipitate if the solution is allowed to stand too long before being
filtered. Similarly, copper sulfide will precipitate in acid solution in the
presence of zinc ions without zinc sulfide being precipitated, but
eventually zinc sulfide will precipitate. Post precipitation is a slow
equilibrium process.

4. Washing and Filtration.

Coprecipitated impurities, especially those on the surface, can be

removed by washing the precipitate after filtering. The precipitate will be

6
wet with the mother liquor, which is also removed by washing. Many
precipitates cannot be washed with pure water, because peptization
occurs. When you wash a precipitate, you should conduct a test to
determine when the washing is complete. This is usually done by testing
the filtrate for the presence of an ion of the precipitating reagent. After
several washings with small volumes of the wash liquid, a few drops of
the filtrate are collected in a test tube for the testing. For example, if
chloride ion is determined by precipitating with silver nitrate reagent, the
filtrate is tested for silver ion by adding sodium chloride or dilute HCl.

5. Drying or igniting.

If the collected precipitate is in a form suitable for weighing, it must be

heated to remove water and to remove the adsorbed electrolyte from the
wash liquid. This drying can usually be done by heating at 110 to 120◦C
for 1 to 2 h. Ignition at a much higher temperature is usually required if
a precipitate must be converted to a more suitable form for weighing. For
example, magnesium ammonium phosphate, MgNH4PO4, is decomposed
to the pyrophosphate, Mg2P2O7, by heating at 900◦C. Hydrous ferric
oxide, Fe2O3 · xH2O, is ignited to the anhydrous ferric oxide. Many
metals that are precipitated by organic reagents (e.g., 8-
hydroxyquinoline) or by sulfide can be ignited to their oxides.

6. Gravimetric Calculations.

using stoichiometric mole relationships. We introduced the gravimetric

factor (GF), which represents the weight of analyte per unit weight of
precipitate. It is obtained from the ratio of the formula weight of the
analyte to that of the precipitate, multiplied by the moles of analyte per
mole of precipitate obtained from each mole of analyte, that is,

( )
( )
( )

=g analyte/g precipitate

7
So, if Cl2 in a sample is converted to chloride and precipitated as AgCl,
the weight of Cl2 that gives 1 g of AgCl is

EX1: Calculate the grams of analyte per gram of precipitate for the
following conversions:

Analyte Precipitate

P Ag3PO4

K2HPO4 Ag3PO4

Bi2S3 BaSO4

8
In gravimetric analysis, we are generally interested in the percent
composition by weight of the analyte(the substance sought) in the sample,
that is,

3−
EX2: Orthophosphate (PO4 )is determined by weighing as ammonium
phosphomolybdate, (NH4)PO4 · 12MoO3. Calculate the percent P in the
sample and the percent P2O5 if 1.1682 g precipitate (ppt) were obtained
from a 0.2711-g sample?

9
EX3: An ore is analyzed for the manganese content by converting the
manganese to Mn3O4 and weighing it. If a 1.52 g sample yields Mn3O4
weighing 0.126 g, what would be the percent Mn2O3 in the sample? The
percent Mn?

EX4: What weight of pyrite ore (impure FeS2) must be taken for analysis
so that the BaSO4 precipitate weight obtained will be equal to one-half
that of the percent S in the sample?

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PRECIPITATE MIXTURES-WE NEED TWO WEIGHTS

EX5: A mixture containing only FeCl3 and AlCl3 weighs 5.95 g. The
chlorides are converted to the hydrous oxides and ignited to Fe2O3 and
Al2O3. The oxide mixture weighs 2.62 g. Calculate the percent Fe and Al
in the original mixture ?

11
 1.3. Examples of Gravimetric Analysis .

Some of the most precise and accurate analyses are based on

gravimetry. There are many examples, and you should be familiar with
some of the more common ones. These are summarized in table.1 which
lists the substance sought, the precipitate formed, the form in which it is
weighed, and the common elements that will interfere and must be
absent. We do not present more details because gravimetry is not
currently used often (unless the much longer time and increased labor
requirements can be justified by the necessity of high precision and
accuracy).

Table1: Some Commonly Employed Gravimetric Analysis .

1.4. Organic Precipitates .

There are a large number of organic compounds that are very useful
precipitating agents for metals. Some of these are very selective, and
others are very broad in the number of elements they will precipitate.
Organic precipitating agents have the advantages of giving precipitates
with very low solubility in water and a favorable gravimetric factor. Most
of them are chelating agents that form slightly soluble, uncharged
chelates with the metal ions. A chelating agent is a type of complexing

12
agent that has two or more groups capable of complexing with a metal
ion. The complex formed is called a chelate(table.2).

Table2: Some Organic Precipitating Agents .

1.5. Precipitation Equilibria: The Solubility Product .

When substances have limited solubility and their solubility is exceeded,

the ions of the dissolved portion exist in equilibrium with the solid
material. So-called insoluble compounds generally exhibit this property.
When a compound is referred to as insoluble, it is actually not completely
insoluble but is slightly soluble. For example, if solid AgCl is added to
water, a small portion of it will dissolve:

13
We can write an overall equilibrium constant for the above stepwise
equilibrium, called the solubility product Ksp. (AgCl)aq cancels when
the two stepwise equilibrium constants are multiplied together.

The “concentration” of any solid such as AgCl is constant and is

combined in the equilibrium constant to give Ksp. The above relationship
holds regardless of the presence of any undissociated intermediate; that
is, the concentrations of free ions are rigorously defined by above
Equation , and we will take these as a measure of a compound’s
solubility.

EX6: The Ksp of AgCl at 25◦C is 1.0 × 10−10. Calculate the

concentrations of Ag+ and Cl− in a saturated solution of AgCl, and the
molar solubility of AgCl ?

1.6. Decreasing the solubility- The Common ion effect.

If there is an excess of one ion over the other, the concentration of the
other is suppressed (common ion effect), and the solubility of the
precipitate is decreased. We can still calculate the concentration from the
solubility product.

EX7: Ten milliliters of 0.20 M AgNO3 is added to 10mL of 0.10 M NaCl.

Calculate the concentration of Cl− remaining in solution at equilibrium,
and the solubility of the AgCl ?

14
 6

Note: Because the Ksp product always holds, precipitation will not take
the product of [Ag+] and [Cl−] exceeds the Ksp. If the place unless
product is just equal to Ksp, all the Ag+ and Cl− remains in solution.

EX8: What must be the concentration of added Ag+ to just start

precipitation of AgCl in a 1.0 × 10−3 M solution of NaCl?

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Table3: Solubility Product Constants of Selected Slightly Soluble Salts

EX9: What is the solubility of PbI2, in g/L, if the solubility product is 7.1
× 10−9 ?

EX10: Calculate the molar solubility of PbSO4 and compare it with that
of PbI2 ?

16
Although the Ksp of PbI2 (7.1 × 10−9) is smaller than that of PbSO4 (1.6
× 10−8), the solubility of PbI2 is greater , due to the nonsymmetrical
nature of the precipitate.

Note : We take advantage of the common ion effect to decrease the

solubility of a precipitate in gravimetric analysis. For example, sulfate ion
is determined by precipitating BaSO4 with added barium chloride
solution. The following figure illustrates the effect of excess barium ion
on the solubility of BaSO4.

EX11 : What pH is required to just precipitate iron(III) hydroxide from a

0.10 M FeCl3 solution?

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1.7. Effect of Acidity on Solubility of Precipitates.

The solubility of a precipitate whose anion is derived from a weak acid

will increase in the presence of added acid because the acid will tend to
combine with the anion and thus remove the anion from solution. For
example, the precipitate MA that partially dissolves to give M+ and A−
ions will exhibit the following equilibria:

The anion A− can combine with protons to increase the solubility of the
precipitates. The combined equilibrium concentrations of A− and HA
make up the total analytical concentration AT of A, which will be equal
to [M+] from the dissolved precipitate (if neither M+ or A− is in excess).
By applying the equilibrium constants for the equilibria involved, we can
calculate the solubility of the precipitate at a given acidity. Consider, for
example, the solubility of CaC2O4 in the presence of a strong acid. The
equilibria are:

The solubility s of CaC2O4 is equal to [Ca2+] = OxT, where OxT represents

the concentrations of all the oxalate species in equilibrium (= [H2C2O4] +
[HC2O4 −] + [C2O4 2−] ). We can substitute OxTα2 for [C2O4 2−] in the Ksp
expression:

18
where α2 is the fraction of the oxalate species present asC2O4 2− (α2 =
[C2O4 2−]/OxT). calculate α’s, we find that

where K'sp is the conditional solubility product.

EX12 : Calculate the solubility of CaC2O4 in a solution containing 0.0010

M [H+] ?

1.8. Effect of Complexation on Solubility.

Complexing agents can compete for the metal ion in a precipitate, just as
acids compete for the anion. A precipitate MA that dissociates to give M +
and A− and where the metal complexes with the ligand L to form ML+
would have the following equilibria:

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The sum of [M+] and [ML+] is the analytical concentration MT in
equilibrium, which is equal to [A−]. Calculations for such a situation are
handled in a manner completely analogous to those for the effects of
acids on solubility. Consider the solubility of AgBr in the presence of
NH3. The equilibria are :

The solubility s of AgBr is equal to [Br−] = AgT, where AgT represents the
concentrations of all the silver species in equilibrium (= [Ag+] +
[Ag(NH3)+] + [Ag(NH3)2+]). As before, we can substitute AgTαM for
[Ag+] in the Ksp expression, where αM is the fraction of silver species
present as Ag+:

The K'sp is again the conditional solubility product.

21
 Questions
1- Why must a filtered precipitate be washed ?

Ans : In order to remove the mother liquor and nonvolatile surface

impurities and replace them by a volatile electrolyte .

2- Why must a wash liquid generally contain an electrolyte? What are the
requirements for this electrolyte?

Ans : In order to prevent peptization ( formation of colloidal particles) of

the precipitate . The electrolyte must be volatile at the temperature of
drying or ignition and must not dissolve the precipitate.

3- What advantages do organic precipitating agents have ?

Ans : Organic precipitation agents produce precipitates with very low

solubility in water that have very favorable gravimetric factors since the
organic reagents have high molecular weights. Depending on the reagent ,
selectivity can be high. Solubility can be adjusted by pH control .

4- Explain the difference between :

a) colloidal and a crystalline precipitate?

Ans: A colloidal precipitate consists of solid particles with dimensions

that are less than 10–4 cm. A crystalline precipitate consists of solid
particles with dimensions that at least 10–4 cm or greater. As a result,
crystalline precipitates settle rapidly, whereas colloidal precipitates
remain suspended in solution unless caused to agglomerate.

b) precipitation and coprecipitation?

Ans: Precipitation is the process by which a solid phase forms and is

carried out of solution when the solubility product of a chemical species
is exceeded. Coprecipitation is a process in which normally soluble
compounds are carried out of solution during precipitate formation.

5-What are the structural characteristics of a chelating agent?

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Ans: A chelating agent is an organic compound that contains two or
more electron-donor groups located in such a configuration that five- or
six-membered rings are formed when the donor groups complex a cation.

6- Calculate the weight of sodium present in 50.0 g Na2SO4 ?

Ans : wt. of Na+ = wt. of Na2SO4 × G.F = 50 × 2(23) / 142 = 16.2 gm

7- If the salt Na2SO4( 50 gm) is analyzed by precipitating and weighing

BaSO4, what weight of precipitate would be obtained?

Ans : wt. of BaSO4 = wt. of Na2SO4 × G.F = 50 × 233/142 = 82.2 gm

8- Calculate the gravimetric factors for:

Substance Sought Substance Weighed

1) As2O3 Ag3AsO4

2) FeSO4 Fe2O3

3) K2O KB(C6H5)4

4) SiO2 KAlSi3O8

Ans : 1)G.F = f.wt of As2O3 / 2× f.wt of Ag3AsO4 =

197.8 / 2×462.5=0.213

2) G.F = f.wt of 2× FeSO4 / f.wt of Fe2O3 =

2×151.9 / 159.7 = 1.902

3) G.F = f.wt of K2O / 2× f.wt of KB(C6H5)4=

94.2 / 2×358.3= 0.1314

4) G.F = f.wt of 3× SiO2 / f.wt of KAlSi3O8 =

3×60.08 / 278.4 = 0.6474

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9-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?

Ans:

10-What mass of Cu(IO3)2 can be formed from 0.650 g of CuSO4 ·

5H2O?

Ans:

11- What mass of AgI can be produced from a 0.512-g sample that assays
20.1% AlI3?

Ans:

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12- A 0.2121-g sample of an organic compound was burned in a stream
of oxygen, and the CO2 produced was collected in a solution of barium
hydroxide. Calculate the percentage of carbon in the sample if 0.6006 g
of BaCO3 was formed.

Ans:

13-The mercury in a 1.0451-g sample was precipitated with an excess of

paraperiodic acid, H5IO6:

5Hg+2 + 2H5IO6 Hg5(IO6 )2 + 10H+

The precipitate was filtered, washed free of precipitating agent, dried, and
weighed, and 0.5718 g was recovered. Calculate the percentage of Hg2Cl2
in the sample?

Ans:

14-Ammoniacal nitrogen can be determined by treatment of the sample

with chloroplatinic acid; the product is slightly soluble ammonium
chloroplatinate:

H2PtCl6 + 2NH4+ (NH4)2PtCl6 + 2H+

The precipitate decomposes on ignition, yielding metallic platinum and

gaseous products:

(NH4)2PtCl6 Pt(s) + 2Cl2(g) + 2NH3(g) + 2HCl(g)

24
Calculate the percentage of ammonia in a sample if 0.2115 g gave rise to
0.4693 g of platinum ?

Ans:

Homework
15- How many grams CuO would 1.00 g Paris green, Cu3(AsO3)2 ·
2As2O3 · Cu(C2H3O2)2, give? Of As2O3?

16- A 523.1-mg sample of impure KBr is treated with excess AgNO3 and
814.5 mg AgBr is obtained. What is the purity of the KBr?

17- What weight of Fe2O3 precipitate would be obtained from a 0.4823-g

sample of iron wire that is 99.89% pure?

18- The aluminum content of an alloy is determined gravimetrically by

precipitating it with 8-hydroxyquinoline (oxine) to give Al(C9H6ON)3. If
a 1.021-g sample yielded 0.1862 g of precipitate. what is the percent
aluminum in the alloy?

19- The chloride in a 0.12-g sample of 95% pure MgCl2 is to be

precipitated as AgCl. Calculate the volume of 0.100 M AgNO3 solution
required to precipitate the chloride and give a 10% excess ?

20- Ammonium ions can be analyzed by precipitating withH2PtCl6 as

(NH4)2PtCl6 and then igniting the precipitate to platinum metal, which is
weighed [(NH4)2PtCl6 Pt + 2NH4Cl(g) + 2Cl2(g)]. Calculate
the percent ammonia in a 1.00-g sample that yields 0.100 g Pt by this
method ?

21- A sample is to be analyzed for its chloride content by precipitating

and weighing silver chloride. What weight of sample would have to be
taken so that the weight of precipitate is equal to the percent chloride in
the sample?

25
22- Pyrite ore (impure FeS2) is analyzed by converting the sulfur to
sulfate and precipitating BaSO4. What weight of ore should be taken for
analysis so that the grams of precipitate will be equal to 0.1000 times the
percent of FeS2?

23- A mixture containing only BaO and CaO weighs 2.00 g. The oxides
are converted to the corresponding mixed sulfates, which weigh 4.00 g.
Calculate the percent Ba and Ca in the original mixture ?

24- A mixture containing only AgCl and AgBr weighs 2.000 g. It is

quantitatively reduced to silver metal, which weighs 1.300 g. Calculate
the weight of AgCl and AgBr in the original mixture ?

25- A series of sulfate samples is to be analyzed by precipitation as

BaSO4. If it is known that the sulfate content in these samples ranges
between 20% and 55%, what minimum sample mass should be taken to
ensure that a precipitate mass no smaller than 0.200 g is produced? What
is the maximum precipitate mass to be expected if this quantity of sample
is taken?

26- 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?

27-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 the solubility of Ba(IO3)2 in water is negligibly small and calculate :

(a) the mass of the precipitated Ba(IO3)2.

(b) the mass of the unreacted compound that remains in solution.

Solubility product calculations.

28- Write solubility product expressions for the following: (a) AgSCN,
(b) La(IO3)3, (c) Hg2Br2, (d) Ag[Ag(CN)2]; (e) Zn2Fe(CN)6, (f) Bi2S3?

Ans : (a) ksp = [Ag+][SCN-] (b) ksp = [La+3][IO3-]3

(c) ksp = [Hg+2][Br-]2 (d) ksp = [Ag+][Ag(CN)2-]

(e) ksp = [Zn+2]2[Fe(CN)6-4] (f) ksp = [Bi+3]2[S-2]3

26
29- Bismuth iodide, BiI3, has a solubility of 7.76 mg/L. What is its Ksp?

Ans :

10-5

BiI3 Bi+3 + 3I-

[Bi+3] = 1.32 × 10-5 M [I-] = 3× 1.32× 10-5 = 3.96× 10-5 M

Ksp = [Bi+3][I-] = (1.32 × 10-5)( 3.96× 10-5) = 8.20×10-19

30- What is the concentration of Ag+ and CrO42− in a saturated solution of

Ag2CrO4?

31- Calculate the concentration of barium in the solution at equilibrium

when 15.0mL of 0.200 M K2CrO4 is added to 25.0mL of 0.100 M BaCl2 ?

32- What must be the concentration of PO4 3− to just start precipitation of

Ag3PO4 in a 0.10 M AgNO3 solution?

33- What must be the concentration of Ag+ to just start precipitating 0.10
M PO4 3−? 0.10 M Cl−?

34- At what pH will Al(OH)3 begin to precipitate from 0.10 M AlCl3?

35- What weight of Ag3AsO4 will dissolve in 250mL water?

36- What is the solubility of Ag2CrO4 in 0.10 M K2CrO4?

37- Compounds AB and AC2 each have solubility products equal to 4 ×

10−18. Which is more soluble, as expressed in moles per liter?

38- The solubility product of Bi2S3 is 1 × 10−97 and that of HgS is 4 ×

10−53. Which is the least soluble?

39- When a sample of solid AgCl is shaken with water at 250C , a

solution containing 1×10-5 M silver ions is produced. Calculate Ksp ?

40- Calculate the solubility of Mg(OH)2 in water . Ksp = 1.2×10-11 ?

41- How many mole of CuI ( Ksp = 5×10-12) will dissolve in 1L of 0.1 M
of NaI solution ?

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42- Calculate the solubility of A2X3 in pure water , assuming that neither
kind of ion react with water . For A2X3 ( Ksp = 1.1×10-23) ?

43- A solution of saturated CaF2 is found to contain 4.1×10-4 M fluoride

ion . Calculate the Ksp of CaF2 . Neglect hydrolysis .

44-Calculate the nikel ion concentration of a solution prepared by shaking

Ni(OH)2 with water until equilibrium is established ?

45- Calculate the solubility of AgCl in 0.2 M AgNO3 solution ?

46- The values of Ksp for the slightly soluble salts MX and QX2 are each
equal to 4×10-18 . Which salt is more soluble ? explain your answer fully .

47- The solubility of PbSO4 in water is 0.038 g/L . Calculate the

solubility product constant of PbSO4 ?

48- The solubility of Ag2CrO4 in water is 0.044 g/L . Determine Ksp ?

49- The concentration of the Ag+ ion in a saturated solution of Ag2C2O4 is

2.3×10-4 M . Calculate the Ksp ?

50- The solubility of ML2 (formula weight , 60 g/L ) in water is 2.4×10-5

g/100 ml solution .Calculate the Ksp for ML2 ?

51- What is the solubility ( in mol/L) of Fe(OH)3 in a solution of PH = 8

? ( Ksp for Fe(OH)3 = 1×10-36 )

52- Ksp for Cu(OH)2 equals 1×10-19 . What is the solubility ( in mol/L ) of
Cu(OH)2 in water ?

53- The following three slightly soluble salts have the same solubilities :
M2X , QY2 , PZ3 . How are their Ksp values related ?

54- The [Ag+] of a solution is 4×10-3 . Calculate the [Cl-] that must be
exceeded before AgCl can precipitate ? (Ksp for AgCl = 1×10-10 ) .

55- Determine the solubility of AgCl in 0.1 M BaCl2 ?

56- What the mass BaSO4 will dissolve in 450 ml of aqueos solution ?

57- Should a precipitate of barium fluoride be obtained when 100 ml of

0.25 M NaF and 100 ml of o.o15 M Ba(NO3)2 are mixed ?

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58- Determine whether a precipitate will form when 100 ml of 0.1 M pb+2
solution is mixed with 100 ml of 0.3 M Cl- solution ?

59- Calculate the PH at which Mg(OH)2 will just begin to precipitate

from a 0.1 M Mg(NO3)2 solution by addition of NaOH ?

60- Calculate the hydroxide ion concentration of a solution after 100 ml

of o.1 M MgCl2 is added to 100 ml of 0.2 M NaOH ?

61- The value of Ksp for HgI2 is 1.2×10-28 , calculate the concentration of
cation and anion in a saturated solution of HgI2 in water ?

62- What [ SO4-2 ] must be exceeded to produce a RaSO4 precipitate in

500 cm3 of a solution containing 0.0001 mol of Ra+2 ?

63- A solution has a Mg+2 concentration of 0.001 mol/L . will Mg(OH)2

precipitate if the OH- concentration of the solution is (a) 10-5 mol/L (b)
10-3 mol/L ?

64- A mixture of water and AgCl is shaken until a saturated solution is

obtained . Then the solid is filtered , and to 100 ml of the filtrate is added
100ml of 0.03 M NaBr. Should a precipitate be formed ?

65- Calculate the simultaneous solubility of CaF2 and SrF2 ? Ksp for SrF2
is 2.9×10-9 and Ksp for CaF2 is 3.4×10-11

Calculations of gravimetric analysis

1- The iron in a sample of FeCO3 containing inert impurities is converted
by solution , oxidation , precipitation , and ignition into Fe 2O3 weighing 1
gm . What is the weight of iron expressed as FeCO3 , as Fe , and as FeO
in the original sample ?

2-What weight of Fe3O4 with furnish 0.5430 gm of Fe2O3 ?

3- If 2 gm of impure sodium chloride is dissolved in water and , with an

excess of silver nitrate , 4.6280 gm of silver chloride is precipitated ,
what is the percentage of chlorine in the sample ?

4- A 0.5 gm sample of impure magnetide (Fe3O4) is converted by

chemical reactions to Fe2O3 , weighing 0.411 gm . What is the percentage
age of Fe3O4 in the magnetide ?

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5- Calculate the gravimetric factors for converting (a) BaSO4 to Ba , (b)
Nb2O5 to Nb , (c) Mg2P2O7 to MgO , (d) KClO4 to K2O , (e) Fe3O4 to
Fe2O3 ?

6- What is the weight of S in 5.672 gm of BaSO4 ?

7- A sample of ferrous ammonium sulfate containing inert material

weighs 0.5013 gm and furnishes 0.0968 gm of Fe2O3 . What is the
percentage of FeSO4.(NH4)2SO4.6H2O in the sample ?

8- A sample of limestone weighing 1.2456 gm furnishes 0.0228 gm of

Fe2O3 , 1.3101 gm of CaSO4 , and 0.0551 gm of Mg2P2O7 . Find the
percentage of (a) Fe , (b) CaO , MgO in the limestone ?

9- What weight of pyrite containing 36.40% S must have been taken for
analysis in order to give a ppt. of BaSO4 weighing 1.0206 ?

10- (a) What is the percentage composition of a brass containing only Cu

, pb , and Zn if a sample weighing 0.5 gm furnishes 0.0023 gm of BaSO4
and 0.4108 gm of ZnNH4PO4 ? (b) What weight of Zn2P2O7 could be
obtained by igniting the ZnNH4PO4?

11- The N in a 0.5 gm sample of organic material is converted to

NH4HSO4 by digestion with conc. H2SO4 . If the NH4+ ions are
precipitated as (NH4)2PtCl6 and the precipitate is ignited to Pt , what is
the percentage of N in the sample if the Pt weighs 0.1756 gm ?

12- A sample of pyrite , FeS2 contains only inert impurities and weighs
0.508 gm . After the sample has been decomposed and dissolved , a
precipitate of 1.561 gm of BaSO4 is subsequently obtained . Calculate the
percentage of S in the sample ?

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