EXPERIMENT A5: Solubility and Precipitation

Study the following sections in "Chemistry: 7th edition by Brady, Jespersen & Hyslop:
Chapter 4.
Chapter 5
Chapter 17.

KNOW THE SOLUBILITY RULES AS SUMMARIZED IN TABLE 1 AS WELL AS THE

COMPLEX -IONS (OR COORDINATION COMPOUNDS) LISTED IN TABLE 2.

WARNING:
Wearing eye-protection and safety-clothes is compulsory.
You will not be admitted to the practical without them.

Safety reminder: Remember to treat all chemicals as toxic: avoid accidental skin contact.
Wash off any drops on the skin with a copious supply of water. Mop up spills promptly, they
are hazardous!
(See Rules 2.4, 2.5 and 2.12 pp 13-14 of Introductory Practical Notes)

Aims of this experiment

1. To investigate the different reactions of cations with a chosen series of anions.
2. To describe the precipitates that form in terms of their colour, density and general appearance.
3. To write balanced chemical equations for observed reactions in aqueous solution.
4. To make use of the above results in separating and identifying a mixture of cations.

Discussion
The solubility of ionic chemical compounds in water is regulated by the solubility product constant,
Ksp. This constant is temperature specific. The solubility of PbCl2, lead (II) chloride, for example,
increases fourfold when heated from 25oC to 100oC.

The equilibrium which applies to a salt of low solubility, MaXb, can be written as

MaXb(s) ≡ aMb+(aq) + bXa-(aq) .... (1)

The equilibrium is dynamic since the ions in the solid crystal lattice are being solvated whereas
others are built into the crystal from solution. At equilibrium the concentrations of the ions in
solution are constant.
The formal equilibrium expression for reaction (1) is:
{M b + }a { X a − }b
K= .... (2)
{M a X b }

{ } = activity

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A simplified equilibrium expression can be derived from equation (2) assuming that {MaXb} (a
solid) = 1. The constant is then the solubility constant and activities { } are replaced with molar
concentrations [ ].

Ksp = [Mb+] a[Xa-] b .... (3)

The solubility product expressions for NaCl, Al(OH)3 and Sb2S3 are for example

Ksp(NaCl) = [Na+][Cl- ]
Ksp(Al(OH)3) = [Al3+][OH- ] 3
and
Ksp(Sb2S3) = [Sb3+] 2[S2- ]3

The solubility product applies to any slightly soluble salt and represents the maximum value for the
ion product (right hand side of expression 3) at a given temperature. A small value of Ksp indicates
low solubility and vice versa.

Examples
Which of the following two salts is the more soluble?

1. BaF2 (with Ksp = 1.7 x 10-6) or PbF2 (with Ksp = 3.6 x 10-8)? The cation to anion ratio is 1:2 in
both salts. In this case the Ksp values can be compared and BaF2 (with the larger value) is the
more soluble salt.

2. BaCrO4 (with Ksp = 2.1 x 10-10) or Ag2CrO4 (with Ksp = 1.2 x 10-12)

The ion ratios in the two salts are different and Ksp values cannot be compared directly to deduce
solubilities. The solubility of each salt has to be calculated.

(a) BaCrO4(s) → Ba2+(aq) + CrO 24− (aq)

If the solubility of BaCrO4 (this is the number of moles of the salt that dissolve in 1 dm3) is
x, then at equilibrium:
[Ba2+] = [CrO 24− ] = x
Ksp = [Ba2+][CrO 24− ] = 2.1 x 10-10
(x)(x) = 2.1 x 10-10
x2 = 2.1 x 10-10
x = 2.1 × 10 −10 = 1.4 x 10-5 mol.dm-3

(b) Ag2CrO4(s) → 2Ag+(aq) + CrO 24− (aq)

If the solubility of Ag2CrO4 is x, then [Ag+] = 2x and [CrO 24− ] = x at equilibrium:
Ksp = [Ag+] 2[CrO 24− ] = 1.2 x 10-12
(2x)2(x) = 1.2 x 10-12
4x3 = 1.2 x 10-12
1
1.2 × 10 −12 
3

x =  
 4 
x = 6.7 x 10 mol.dm-3
-5

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Only now can we say which salt is the most soluble by comparing the values of their solubility. The
solubility of BaCrO4 is 1.4 x 10-5 mol.dm-3 and that of Ag2CrO4, 6.7 x 10-5 mol.dm-3.
Ag2CrO4, although it has the smaller Ksp-value, is the more soluble salt in this example.

If the ion product in a solution (involving the concentrations of the ions after mixing) is smaller
than the solubility product constant, the solution is unsaturated with the salt and no precipitation
occurs. When the ion product is larger than the Ksp-value, the solution is oversaturated
(supersaturated) and precipitation occurs until the ion product has reached the same value as the
Ksp-value.
The solubilities of ionic compounds in water are summarized qualitatively in Table 1 and can be
used to predict and explain precipitation when dilute solutions are mixed.

Table 1: The solubilities of ionic compounds at room temperature

Essentially soluble Exceptions

Li+, Na+, K+, NH +4 None

NO 3− , NO −2 , CH3COO- None

Cl- AgCl, PbCl2, Hg2Cl2 are insoluble

Br- AgBr, PbBr2, HgBr2, Hg2Br2 are insoluble
I- AgI, PbI2, HgI2, Hg2I2 are insoluble

SO 24− Ag2SO4, PbSO4, CaSO4, SrSO4, BaSO4 and Hg2SO4 are

insoluble

Essentially insoluble Exceptions

CO 32− , PO 34− , S2- The salts of Li+, Na+, K+ and NH +4 are soluble.
Fe3+, Cr3+ and Al3+ with CO 32− and water form hydroxide
precipitates: Fe(OH)3, Cr(OH)3, Al(OH)3 and not
carbonates, CO2(g) is produced.

OH- The salts of Li+, Na+, K+, NH +4 , Ca2+, Sr2+and Ba2+ are
soluble.
Ag+, Hg2+ give oxide precipitates with OH- and Cu(OH)2
decomposes upon heating into CuO

CrO 24− Those of Li+, Na+, K+, NH +4 , Mg2+ en Ca2+ are soluble.

A number of complications occur in certain reactions. These are illustrated below.

1. The precipitates AgOH and Hg(OH)2 undergo spontaneous decomposition to form oxides at
room temperature, whereas Cu(OH)2 decomposes to CuO when heated.

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Examples:
−
(a) (Ag+(aq) + NO 3− (aq)) + (Na+(aq) + OH-(aq)) → [AgOH] + Na+(aq) + NO 3 (aq)
the [AgOH] is unstable and decomposes spontaneously to silver oxide
2[AgOH] →Ag2O(s) + H2O(l)
brown

(b) Cu(OH)2(s) → CuO(s) + H2O(l)

Δ black

2. Cations which form hydroxides with NaOH also form hydroxide precipitates with a dilute NH3
solution due to the equilibrium
+
NH3(aq) + H2O(l) ↔ {NH4OH} ↔ NH 4 (aq) + OH-(aq)
which affords hydroxide ions.

Example:
The reaction of Pb(NO3)2 with ammonia solution is written as follows:

− + + −
(Pb2+(aq) + 2NO 3 (aq)) + 2(NH 4 (aq) + OH-(aq))→ Pb(OH)2(s) + 2NH 4 (aq) + 2NO 3 (aq)

3. Certain hydroxide precipitates can be dissolved with the addition of an excess of NH3-solution.
Amine complexes are formed (see Table 2 for the relevant cations).

Examples:
2+
Co(OH)2(s) + 6NH3 (aq) →Co(NH3) 6 (aq) + 2OH-(aq)
and
+
Ag2O(s) + 4NH3(aq) + H2O(l) → 2Ag(NH3) 2 (aq) + 2OH-(aq)
The presence of water leads to the conversion of O2- to 2OH-. Complex or co-ordination compounds
consist of a central metal ion to which a specific number of ligands are bonded. Table 2 lists some
complex ions with mono-dentate ligands (the most common coordination numbers are given).
Table 2:Complex- ions

Aqua Hydroxide Amine Halide

2+ − + −
Cu(H2O) 6 Al(OH) 4 Ag(NH3) 2 AgCl 2
2+ − 2+ 2−
Ni(H2O) 6 Cr(OH) 4 Cu(NH3) 4 CuCl 4
2+ 2− 2+ 2−
Zn(H2O) 6 Zn(OH) 4 Zn(NH3) 4 ZnCl 4
3+ 2− 2+ 2−
Al(H2O) 6 Pb(OH) 4 Cd(NH3) 4 HgCl 4
3+ 2+ −
Fe(H2O) 6 Co(NH3) 6 AuCl 4
2+ −
Ni(NH3) 6 FeCl 4
2−
PtCl 4
2−
NiBr 4

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 2−
4. The ions Fe3+, Cr3+ and Al3+ form hydroxide precipitates with CO 3 ions and H2O. CO2(g)
is evolved in the reaction.

Example: The following balanced equation is a representation of the reaction between CrCl3 and
Na2CO3 in an aqueous medium:

2−
2(Cr3+(aq) + 3Cl-(aq)) + 3(2Na+(aq) + CO 3 (aq)) + 3H2O(l) →2Cr(OH)3(s) + 3CO2(g)
+ 6Na+(aq) + 6Cl-(aq)

Attempt to write a balanced equation for the reaction between solutions of Al2(SO4)3(aq) and
Na2CO3(aq).

Apparatus required
6 small-diameter test tubes - wash bottle
test tube rack - Bunsen burner
test tube holder - asbestos mat (black)
test tube brush

Reagents required
0.1 M aqueous solutions of nitrate salts of different cations.

Bench reagents: Dilute hydrochloric and sulphuric acids; sodium hydroxide solution; sodium
carbonate solution; ammonia solution.
De-ionized water (50 L plastic aspirators, front bench)

Procedure
M aqueous solutions of nitrate salts of the cations in the Results Table are to be used.

NB: As soon as you have dispensed a chemical from a bottle, replace the stopper/cap
on that bottle. Do not return excess solution to the bottle: discard it (waste container).

1. Use 2 cm3 (approximately 1 cm high in a test tube) of the Na+ solutions in each of six clean test
tubes.

2. Add the following anion solutions (2 cm3) to each test tube.

Test tube 1: Cl-, use dilute hydrochloric acid (bench reagent)
2−
Test tube 2: SO 4 , use dilute sulphuric acid (bench reagent)
2−
Test tube 3: CO 3 , use sodium carbonate (bench reagent)
Test tube 4: OH-, use sodium hydroxide (bench reagent)
Test tube 5: OH-, use ammonia solution (bench reagent)

NOTE:
(a) The NH3-solution should be added drop by drop while shaking* the test tube gently. *See
"Techniques Required", p 18, no 9 in the Introductory Practical Notes.
(b) Where indicated (see results table) an excess of NH3 should be added slowly.
Test tube 6: S2-, use the (NH4)2S solution is in the fume cupboard.

NOTE: The resultant mixture should be transferred to the correct waste beaker (labelled) in the
fume cupboard.

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3. After addition of the second solution shake well, and then wait for a while before your
observations are noted in the results table (answer sheet). Mention the following: the
formation of a precipitate; describe the precipitate in terms of its colour, density and physical
characteristics; change of colour without precipitation; the formation of a gas. If no change
is observed write only "No observed reaction" (NOR).

2+
4. Repeat steps 1 to 3 for all the other cation solutions (Ag+; Pb2+; Hg2+; Hg 2 ; Cu2+; Fe3+;
Ni2+; Co2+; Zn2+ and Sr2+).

NOTE: Also carry out the additional tests, e.g. gentle heating (See "Techniques
Required", Introductory Practical Notes, pp 14-17, no 2-5) of Pb2+ and Cl-, Cu2+ and
NaOH, as well as the addition of ammonia solution in excess to the Ag+, Cu2+, Co2+,
Ni2+ and Zn2+ solutions mentioned in the Table of Observation.

5. WASTE DISPOSAL
Discard the final solutions in the appropriate waste containers/beakers.
Only sulphide containing residues/solutions should be transferred to the waste beaker in the fume
cupboard. Rinse the test tube in the fume cupboard with a small quantity of water and discard in
beaker.

REPORT

Assignment 1

Complete the Table of observation – See Answer Sheet. (10)

Write balanced complete ionic equations for the following reactions: X(5), X(6), X(9),
X(12) and X(13) on the Answer Sheet. Use the Table of Observation. (12)
Write net ionic equations (Answer Sheet) for the following reactions: X(2), X(7) and
X(15) (5)

Assignment 2

Answer the questions for Assignment 2 on your answer sheet at the end of the practical.

Completion of practical:

Have you: Done?

correctly disposed of all waste?
washed all apparatus?
packed the Bunsen burner, tripod and asbestos mat (black) back in
the "communal" cupboard?
packed the other apparatus correctly in your own cupboard?
replaced bench reagents correctly with the right stoppers?
checked that water and gas taps are properly closed?
cleaned and dried your working surface?
replaced your laboratory stool?
had your work signed by your demonstrator?
---oOo---

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