Gen Chemistry II (CHEM 102)

Dr. Rabeay Hassan

Nano-building, room F008

ryounes@zewailcity.edu.eg

2022
 Chapter 17

Additional Aspects of
Aqueous Equilibria
 The Common-Ion Effect
The common ion effect is the suppression of the degree of dissociation of a
weak electrolyte containing a common ion.

CH3COOH(aq) + H2O(l) H3O+(aq) + CH3COO(aq)

Addition of CH3COO shifts the equilibrium concentration

The reaction shifts

toward the left to relieve
the stress of the excess
product.

If acetate ion, or ammonium ion is added to the solution, Le Châtelier says the equilibrium will
shift to the left.
“The extent of ionization of a weak electrolyte is decreased by adding to the solution a strong
Aqueous
electrolyte that has an ion in common with the weak electrolyte.” Equilibria
 The Common-Ion Effect
Calculate the fluoride ion concentration and
pH of a solution that is 0.20 M in HF and 0.10 M in HCl.

Ka for HF is 6.8  104.

HF(aq) + H2O(l) H3O+(aq) + F(aq)

[H3O+] [F]
Ka = = 6.8  104
[HF]
[HF], M [H3O+], M [F], M
Initially 0.20 0.10 0
Change x +x +x
At equilibrium 0.20  x  0.20 0.10 + x  0.10 x
Aqueous
Equilibria
 [HF], M [H3O+], M [F], M
Initially 0.20 0.10 0
Change x +x +x
At equilibrium 0.20  x  0.20 0.10 + x  0.10 x

(0.10) (x)
6.8  104 = (0.20)
(0.20) (6.8  104) =x 1.4  103 = x
(0.10)

[F] = x = 1.4  103

[H3O+] = 0.10 + x = 0.10 + 1.4  103 = 0.10 M

So, pH = log (0.10)

Aqueous
pH = 1.00 Equilibria
pH Buffers

Aqueous
Equilibria
pH Buffers

pH = 4.8

Aqueous
Equilibria
 pH Buffers
Buffers are solutions of a weak conjugate acid–base pair. They are
particularly resistant to pH changes, even when strong acid or base
is added.
or
A buffer solution (more precisely, pH buffer or hydrogen ion
buffer) is an aqueous solution consisting of a mixture of a weak acid
and its conjugate base, or vice versa. Its pH changes very little when
a small amount of strong acid or base is added to it.

Aqueous
Equilibria
 pH Buffers

H+
OH-

If acid is added, the F reacts with it to form HF and water.

Aqueous
If a small amount of hydroxide is added to an equimolar solution of HF inEquilibria
NaF,
for example, the HF reacts with
© 2012 OH to
the Pearson make F
Education,

Inc. and water.
Which one of the following pairs cannot be mixed together to form a buffer solution?
A) HONH2, HONH3Cl
B)
x NaCl, HCl

C) RbOH, HF
D) KOH, HNO2
E) H2SO3, KHSO3 weak acid and conjugate base or a weak base and
conjugate acid

Which one of the following pairs cannot be mixed together to form a buffer solution?
A) NH3, NH4Cl
B) NaC2H3O2, HCl (C2H3O2- = acetate)
C)
x RbOH, HBr
D) KOH, HF
E) H3PO4, KH2PO4 weak acid and conjugate base or a weak base and
conjugate acid

Aqueous
Equilibria
Buffer Calculations

Aqueous
Equilibria
 pH Buffers
(a) What happens when NaOH is added to a buffer composed of CH3COOH
and CH3COO-?
(b) What happens when HCl is added to this buffer?

Neutralization
In order to do calculations in which strong acid or base is added to a
buffer, you need to calculate the amounts of substances from the
neutralization

Henderson–Hasselbalch Equation
Aqueous
Equilibria
Henderson–Hasselbalch Equation
HA + H2O H3O+ + A

[H3O+] [A] [A]

Ka = [HA] Ka = [H3O+]
[HA]

Taking the negative log of both side, we get

base
[A]
log Ka = log [H3O+] + log
[HA]

acid
[base]
pKa = pH  log Aqueous
[acid] Equilibria
 Henderson–Hasselbalch Equation
[base]
pKa = pH  log [acid]

[base]
Rearranging, this becomes pH = pKa + log
[acid]
This is the Henderson–Hasselbalch equation.

The Henderson–Hasselbalch equation relates the pH of a solution containing a

mixture of the two components to the acid dissociation constant, Ka, and the
concentrations of the species in solution

Aqueous
Equilibria
© 2012 Pearson Education, Inc.
 Henderson–Hasselbalch Equation
What is the pH of a buffer that is 0.12 M in lactic acid, CH3CH(OH)COOH,
and 0.10 M in sodium lactate? Ka for lactic acid is 1.4  104.

[base]
pH = pKa + log [acid]

(0.10)
pH = log (1.4  104) + log
(0.12)

pH = 3.85 + (0.08)

pH = 3.77
Aqueous
Equilibria
 In a solution, when the concentrations of a weak acid and its conjugate base are equal,
A) the system is not at equilibrium.
B) the buffering capacity is significantly decreased.
+
xC) the -log of the [H ] and the -log of the Ka are equal.
D) all of the above are true.
[base]
pH = pKa + log [acid]

Of the following solutions, which has the greatest buffering capacity?

A)
x 0.543 M NH3 and 0.555 M NH4Cl
B) 0.087 M NH3 and 0.088 M NH4Cl
C) 0.234 M NH3 and 0.100 M NH4Cl
D) 0.100 M NH3 and 0.455 M NH4Cl
E) They are all buffer solutions and would all have the same capacity.

Aqueous
Equilibria
Buffer pH Range

Aqueous
Equilibria
 Buffer pH Range
Buffer pH Range can be defined as the quantity of strong acid or base that must be added to
change the pH of one liter of buffered solution by one pH unit.
or
The buffer pH Range is the pH range where a buffer effectively neutralizes added acids and
bases, while maintaining a relatively constant pH.
Or
Buffer capacity and its effective pH range are dependent on the amount
(Concentrations) of acid and base used to prepare the buffer.

Examples.
 SODIUM ACETATE; pH 3.6–5.6.
 PHOSPHATE–CITRATE BUFFER; pH 2.2–8.0.

Add the following to create 100 ml of phosphate/citrate buffer solution. Stock solutions are
0.2 M dibasic sodium phosphate; 0.1 M citric acid (Pearse, 1980).

Aqueous
Equilibria
 When Strong Acids or Bases Are Added to a Buffer
When strong acids or bases are added to a buffer, it is safe to assume that all of the
strong acid or base is consumed in the reaction.

Aqueous
Equilibria
 Effect of adding a strong base to (a) a buffered solution and to
(b) water.

1.Determine how the

neutralization reaction affects the
amounts of the weak acid and its
conjugate base in solution.

2.Use the Henderson–Hasselbalch

equation to determine the new pH
of the solution.

Aqueous
Equilibria
A buffer is made by adding 0.300 mol CH3COOH and 0.300 mol CH3COONa to enough
water to make 1.000 L of solution. The pH of the buffer is 4.74.
(a) Calculate the pH of this solution after 5.0 mL of 4.0 M NaOH solution is added.
(b) For comparison, calculate the pH of a solution made by adding 5.0 mL of 4.0 M
NaOH solution to 1.000 L of pure water.

(0.320)
pH = 4.74 + log pH = 4.80 pKa = 4.74
(0.280)

Note that the pH doesn't change much, that's what buffers are supposed to do.

Aqueous
Answer of b Equilibria
 Titration

What is the pH at the equivalence point when 0.10 M HNO3

is used to titrate a volume of solution containing 0.30 g of
KOH?
Answer:HNO3 is a strong acid. KOH is a strong base. At the
equivalence point, the solution will be neutral. Aqueous
Equilibria
pH Titration
Titration, also known as
titrimetry, is a common laboratory method
of quantitative chemical analysis that is
used to determine the unknown
concentration of an identified analyte.

A pH meter or indicators are used to

determine when the solution has reached
the equivalence point, at which the
stoichiometric amount of acid equals that
of base.

Aqueous
Equilibria
© 2012 Pearson Education, Inc.
 pH Titration curve
NaOH (aq) + HCl (aq)  NaCl (aq) + H2O (l)

Titration of a strong
acid with a strong
base

Initial pH:

Aqueous
Equilibria
Titration of a Strong Acid with a Strong Base
From the start of the titration to
near the equivalence point, the pH
goes up slowly.

Just before (and after) the

equivalence point, the pH increases
rapidly.

At the equivalence point, moles

acid = moles base, and the solution
contains only water and the salt
from the cation of the base and the
anion of the acid.

Aqueous
Equilibria
 pH Titration curve

Titration of a weak
acid with a strong
base

Initial pH:

Aqueous
Equilibria
pH Titration curve

Aqueous
Equilibria
 Titrations of Polyprotic Acids

Phosphorous acid

Aqueous
Equilibria
Aqueous
Equilibria
Titrations of Polyprotic Acids

Aqueous
Equilibria
Titration of a Weak Acid with a Strong Base

pH = pKa

[base]
pH = pKa + log
[acid]
Aqueous
Equilibria
 Titration of a Weak Acid with a Strong Base

1.The initial pH is higher.

2.A gradually rising portion of the curve, called the buffer region,
appears before the steep rise to the equivalence point.
3.The pH at the equivalence point is greater than 7.00.
4.The steep rise interval is less pronounced.
5.Phenolphthalein is commonly used as an indicator in these
titrations.

Aqueous
Equilibria
Titration of a Weak Base with a
Strong Acid

Aqueous
Equilibria
 Titration of a Weak Base with a Strong Acid
1.The initial pH is above 7.00.
2.A gradually decreasing portion of the
curve, called the buffer region, appears
before a steep fall to the equivalence point.
3.The pH at the equivalence point is less
than 7.00. pH
4.Thereafter, the pH decreases slowly as
excess strong acid is added.
pH

[base]
pH = pKa + log
[acid]

Aqueous
Equilibria
A 25.0 mL sample of a solution of an unknown compound is titrated with a 0.115 M
NaOH solution. The titration curve above was obtained. The unknown compound is
__________.
A) a strong acid
B) a strong base
x a weak acid
C)
D) a weak base
E) neither an acid nor a base

Aqueous
Equilibria
A 25.0 mL sample of a solution of a monoprotic acid is titrated with a 0.115 M NaOH
solution. The titration curve above was obtained. The concentration of the monoprotic
acid is about __________ mol/L.
A) 25.0
B) 0.0600
C) 0.240
D)
x 0.115
E) 0.100

Aqueous
Equilibria
 Titration of Weak Acids with a Strong Base

With weaker acids, the initial pH

is higher and pH changes near the
equivalence point are more subtle
(Faint).

Each curve represents titration of

50.0 mL of 0.10 M acid with 0.10 M
NaOH.

The same volume of NaOH was used for different pHs of weak
Aqueous
Equilibria
acids
Solubility Products

Aqueous
Equilibria
In which of the following aqueous solutions would you expect AgCl to have
the lowest solubility?
A) pure water
B)
x 0.020 M BaCl2
C) 0.015 NaCl
D) 0.020 AgNO3
E) 0.020 KCl

In which of the following aqueous solutions would you expect CuBr to have the highest
solubility?
A)
x pure water
B) 0.20 M NaBr
C) 0.15 M KBr
D) 0.10 M LiBr

Aqueous
Equilibria
 Solubility and Ksp
Ksp is a measure of how much of the
solid dissolves to form a saturated
solution.

Molar solubility is the number of

moles of a substance (the solute)
that can be dissolved per liter of
solution before the solution becomes
saturated. The units are mol/L or M.

AgCl (s) ↔ Ag + (aq) + Cl - (aq)

Ksp = [Ab+]a [Ba-]b

PbI2 (s)  Pb2+ + 2 I-

Ksp = [Pb2+] [I-]2 Aqueous

Equilibria
 (Ksp) the solubility-product constant
The solubility-product constant Ksp is the equilibrium constant for the equilibrium between
an ionic solid and its saturated solution and is a unit-less number. Thus, the magnitude of Ksp
is a measure of how much of the solid dissolves to form a saturated solution.

An equilibrium can exist between a partially soluble substance

Aqueous
Equilibria
and its solution.
 The Solubility product Expression
AaBb(s) --- aAb+ (aq) + bBa- (aq)

Ksp = [Ab+]a [Ba-]b K sp = [A] c[B] d

The greater the Ksp the more soluble the solid is in H2O

Example: PbI2 (s)  Pb2+ + 2 I-

Ksp = [Pb2+] [I-]2

Ba3(PO4)2(s) ⇌ 3 Ba2+(aq) + 2 PO43–(aq)

The equilibrium constant expression is
Ksp = [Ba2+]3[PO43]2 Aqueous
Equilibria
 Calculating Solubility from Ksp

The Ksp for CaF2 is 3.9 × 10–11 at 25 °C. What is its molar solubility?

Molar solubility is the number of moles of a substance (the solute) that can be
dissolved per liter of solution before the solution becomes saturated. The units are
mol/L or M.

CaF2(s) ⇌ Ca2+(aq) + 2 F–(aq),

Ksp = [Ca2+][F–]2 = 3.9 × 10–11
CaF2(s) [Ca2+](M) [F–](M)

Initial concentration, (M) --- 0 0

Change in concentration, (M) - +x +2x
Equilibrium concentration, (M) --- x 2x

3.9 × 10–11 = (x) (2x)2 = 4x3 Aqueous

Equilibria
x = 2.1 × 10–4 M
 Ag3PO4(s) ⇌ 3Ag+(aq) + PO43-(aq)

Ksp = [Ag+]3[PO43-] = 1.8 x 10-18

Calculate the solubility of Ag3PO4 in mol/L?

Ksp = (3x)3(x) = 27x4 = 1.8 x 10-18

x = 1.6 x 10-5 mol/L

Aqueous
Equilibria
 Calculating Ksp from Solubility
Solid silver chromate is added to pure water at 25 C, and some of the solid
remains undissolved. The mixture is stirred for several hours to ensure that
equilibrium is achieved between the undissolved Ag2CrO4(s) and the solution.
Analysis of the equilibrated solution shows that its silver ion concentration is
1.3  104 M. Assuming that Ag2CrO4 dissociates completely in water and that
there are no other important equilibria involving Ag+ or CrO42– ions in the
solution, calculate Ksp for this compound.

Ksp = [Ag+]2[CrO42–] = (1.3  104)2(6.5  105) = 1.1  1012

Aqueous
Equilibria
Factors that affect the solubility
product

Aqueous
Equilibria
 Factors that affect the solubility product
 The common ion effect
 Common ions reduce solubility
 pH of solution
 pH affects the solubility of ionic compounds in which the anions
are conjugate bases of weak acids.
 Temperature
 Solubility generally increases with temperature;
 Formation of complex ion
 The formation of complex ion increases solubility

Aqueous
Equilibria
The Common-Ion Effect
•The Common-Ion Effect
If one of the ions in a solution equilibrium is already
dissolved in the solution, the equilibrium will shift
to the left and the solubility of the salt will decrease:

???

Aqueous
Equilibria
© 2012 Pearson Education, Inc.
 Calculating solubility with a Common Ion

Ksp for the CaF2 is 3.9 × 10–11 , what is the molar solubility of CaF2 in
0.010 M Ca(NO3)2?

CaF2(s) ⇌ Ca2+(aq) + 2 F–(aq)

Ksp = [Ca2+][F–]2 = 3.9 × 10–11
CaF2(s) [Ca2+](M) [F–](M)
Initial concentration, (M) -- 0.010 0

Change in concentration, (M) --- +x +2x

Equilibrium concentration, (M) --- 0.010 + x 2x

3.9 × 10–11 = (0.010 + x)(2x)2

(We assume that x << 0.010, so that 0.010 + x = 0.010!)

3.9 × 10–11 = (0.010)(2x)2

x = 3.1 × 10–5 M Aqueous
Equilibria
 Solubility is Affected by pH

pH effect on solubility product

Which solubility will be affected by the addition of acid,

PbF2 or Pbl2 ????

Aqueous
Equilibria
 pH effect on solubility product
pH effect
–If a substance has a basic anion (conjugate base of weak acid), it will be more soluble in an
acidic solution.
–Substances with acidic cations are more soluble in basic solutions.

Aqueous
Equilibria
 pH effect on solubility product

The more basic the anion, the more the solubility is influenced by pH.
The solubility of salts with anions of negligible basicity (the anions of strong
acids), such as Cl-, Br-, I-, and NO3 -, is unaffected by pH changes

Which of these substances are more soluble in acidic solution than in basic
solution: (a) Ni(OH)2(s), (b) CaCO3(s), (c) BaF2(s), (d) AgCl(s)?

Aqueous
Equilibria
pH effect on solubility product

Solubility is Affected by pH

CaF2(s) ⇌ Ca2+(aq) + 2 F–(aq)

The solubility of CaF2 increases as the
solution becomes more acidic, because the
F– ion is a weak base; it is the conjugate
base of the weak acid HF. As a result, the
solubility equilibrium of CaF2 is shifted to
the right as the concentration of F– ions is
reduced by protonation to form HF.

Aqueous
Equilibria
 pH effect on solubility product

 Consider the following equilibrium:

 Ag3PO4(s) ⇌ 3Ag+(aq) + PO43-(aq);

 If HNO3 is added, the following reaction occurs:

 H3O+(aq) + PO43-(aq) ⇌ HPO42-(aq) + H2O
 This reaction reduces PO43- in solution, causing more solid
Ag3PO4 to dissolve.
 In general, the solubility of compounds such as Ag3PO4, which
anions are conjugate bases of weak acids, increases as the pH is
lowered by adding nitric acid.

Aqueous
Equilibria
 Factors that affect the solubility product
 The common ion effect
 Common ions reduce solubility

 pH of solution
 pH affects the solubility of ionic compounds in which the anions are
conjugate bases of weak acids.

 Formation of complex ion

 The formation of complex ion increases solubility

Aqueous
Equilibria
 Formation of complex ion
A complex ion is a
species formed between a
central metal ion and one or
more surrounding ligands,
molecules or ions that
contain at least one lone pair
of electrons. Kf=2.9×1013
Small, highly charged metal
ions have the greatest
tendency to act as Lewis
acids and form complex ions.
AgCl

Ksp = 1.77 × 10−10

Aqueous
Equilibria
 Metal Ion Complexes
Metal ions are Lewis acids because of their positive charge. When dissolved in water, they
react with water to form hydrated compound such as Fe(H2O)6+ and Cu(H2O)62+. These are
called metal complexes, or coordination compounds. These coordination reactions are
Lewis acid-base reactions.

Solubility of metal salts increases in the presence of suitable Lewis bases, such as NH3, CN-, or OH-,
provided the metal forms a complex with the base (solvent). The formation of complex ions increases
the solubility of salts.

Aqueous
Equilibria
 Metal Ion Complexes
Metal ions have Lewis acids toward water molecules, which act as Lewis bases

Aqueous
Equilibria
 Complex Ion Equilibria
•Complex ions are ions consisting central metal ions and ligands covalently bonded
to the metal ions;
•Ligands molecules such as H2O, CO, and NH3, or anions such as Cl-, F-, OH-, and
CN-;
•For example, in the complex ion [Cu(NH3)4]2+, four NH3 molecules are covalently
bonded to Cu2+.

Cu2+(aq) + 4NH3(aq) ⇌ [Cu(NH3)4]2+(aq)

2
[Cu(NH 3 ) 4 ]
Kf   1.1 x 1013

[Cu 2 ][ NH 3 ]4

Aqueous
Equilibria
 Effect of complex ion formation on solubility
Consider the following equilibria:

AgCl(s) ⇌ Ag+(aq) + Cl-(aq); Ksp = 1.6 x 10-10

Ag+(aq) + 2NH3(aq) ⇌ Ag(NH3)2+(aq) ; Kf = 1.7 x 107

Combining the two equations yields:

AgCl(s) + 2NH3(aq) ⇌ Ag(NH3)2+(aq) + Cl-(aq);

Knet = Ksp x Kf = (1.6 x 10-10) x (1.7 x 107)
= 2.7 x 10-3

Knet > Ksp implies that AgCl is more soluble in aqueous NH3 Equilibria
than
Aqueous

in water.
Formation Constant of Metal Complex
Stability constants of metal complexes

Kf is the formation
constant of the
complex ions

Or
Stability constants of
metal complexes
Aqueous
Equilibria
Aqueous
Equilibria
Effect of complex ion formation on solubility

Aqueous
Equilibria
A solution is prepared by dissolving 0.23 mol of hydrofluoric acid and 0.27 mol
of sodium fluoride in water sufficient to yield 1.00 L of solution. The addition of
0.05 mol of HCl to this buffer solution causes the pH to drop slightly. The pH
does not decrease drastically because the HCl reacts with the __________
present in the buffer solution. The Ka of hydrofluoric acid is 1.36 × 10-3.
A) H2O
B) H3O+
C)
x fluoride ion
D) hydrofluoric acid
E) This is a buffer solution: the pH does not change upon addition of acid or base.

In which aqueous system is Pbl2 least soluble?

A) H2O
B) 0.5 M HI
C) 0.2 M HI
D) 1.0 M HNO3
xE) 0.8 M KI Aqueous
Equilibria
Precipitation of Ions

Aqueous
Equilibria
 Precipitation reactions
Precipitation reactions occur when cations and anions in aqueous solution
combine to form an insoluble ionic solid called a precipitate.

AB(aq) + CD(aq) → AD(aq) + CB(s)

CdSO4(aq) + K2S(aq) → CdS(s) + K2SO4 (aq)

net ionic equation: C+ (aq)+ B- (aq) → CB (s)

Predicting Formation of
Precipitate

Aqueous
Equilibria
 Predicting Formation of Precipitate
• Qsp = Ksp  saturated solution, but no precipitate
• Qsp > Ksp  saturated solution, with precipitate
• Qsp < Ksp  unsaturated solution,

• Qsp is ion product expressed in the same way as Ksp for a particular system.

Ksp = [Ab+]a [Ba-]b Qsp = [Ab+]a [Ba-]b

For Ksp reactions, products are always the soluble ions, and the reactant
is always the solid.

CaF2(s) ⇌ Ca2+(aq) + 2 F–(aq)

Ksp = [Ca2+][F–]2 = 3.9 × 10–11
Aqueous
Qsp = [Ca2+][F–]2 = ??? Equilibria
 Predicting Precipitation
Consider the following case:
20.0 mL of 0.025 M Pb(NO3)2 is added to 30.0 mL of 0.10 M NaCl.
Predict if precipitate of PbCl2 will form. (Ksp for PbCl2 = 1.6 x 10-5)

Pb(NO3)2+ 2 NaCl  PbCl2 ? + 2 NaNO3

Qsp = [Pb2+][Cl-]2

[Pb2+] = (20.0 mL x 0.025 M)/(50.0 mL) = 0.010 M

[Cl-] = (30.0 mL x 0.10 M)/(50.0 mL) = 0.060 M
Qsp = [Pb2+][Cl-]2 = (0.010 M)(0.060 M)2 = 3.6 x 10-5

Qsp > Ksp  precipitate of PbCl2 will form. Aqueous

Equilibria
A solution contains 1.0 x 10–2 M Ag+ and 2.0 x 10–2 M Pb2+. When Cl– is added to the
solution, both AgCl (Ksp = 1.8 x 10–10) and PbCl2 (Ksp = 1.7 x 10–5) precipitate from the
solution. What concentration of Cl– is necessary to begin the precipitation of each salt?
Which salt precipitates first?

The minimum amount of Cl- required to precipitate the Ag+.

Any Cl- in excess of this very small concentration will cause AgCl to precipitate from solution.

Thus, a concentration of Cl- in excess of 2.9 x 10-2 M causes PbCl2 to precipitate.

Aqueous
Equilibria
Which salt precipitates first?
Selective Precipitation of Ions

Aqueous
Equilibria
 Practical Applications of Solubility Equilibria

Selective precipitation is a technique of separating ions in an aqueous solution by using a

reagent that precipitates one or more of the ions, while leaving other ions in solution.

 Qualitative Analyses
 Isolation and identification of cations and/or anions in unknown samples.
 Synthesis of Ionic Solids of commercial interest.

Selective Precipitation based on Ksp

Suppose that a solution contains two different cations, for example Ba2+ and Ca2+
•Each forms an insoluble sulfate, BaSO4 and CaSO4
Ksp BaSO4 = 1.1 x 10-10 , Ksp CaSO4 = 7.1 x 10-5
•If sulfate ions are added to a solution containing equal amounts of Ba2+ and Ca2+, then the BaSO4
will precipitate first
•Only when the Ba2+ ion concentration becomes very small will the SO42- ion concentration rise to
the point that CaSO4 will be precipitated.

Aqueous
Equilibria
Selective Precipitation of Ions

•At a low pH, [S2–] is relatively low

and only the very insoluble CuS
precipitate.

•When OH– is added to lower [H+],

the value of [S2–] increases, and NiS
precipitate.

Aqueous
Equilibria
 Selective Precipitation (Mixtures of Metal Ions)
•Selective precipitation is a separation technique for compounds that share a
common ion but have different solubilities and are precipitated out of solution.

•Use a reagent whose anion forms a precipitate with only one or a few of the metal ions in
the mixture.
•Example: Solution contains Ba2+ and Ag+ ions.
Adding NaCl will form a precipitate with Ag+ (AgCl), while still leaving Ba2+ in solution.

•Separation of Cu2+ and Hg2+ from Ni2+ and Mn2+ using H2S
•At a low pH, [S2–] is relatively low and only the very insoluble HgS and CuS
precipitate.
•When OH– is added to lower [H+], the value of [S2–] increases, and MnS and NiS
precipitate.

Aqueous
Equilibria
Qualitative Analyses

Qualitative Analysis for Metal Ions

Aqueous
Equilibria
 Qualitative Analysis
In qualitative analysis, the identity, not the amount, of metal ions present in a
mixture is determined. The technique consists of selectively precipitating only a
few kinds of metal ions at a time under given sets of conditions. Consecutive
precipitation steps become progressively less selective until almost all the metal
ions are precipitated. Other additional steps are needed to separate metal ions that
precipitate together.

•Separation and identification of cations, such as Ag+, Ba2+, Cr3+, Fe3+, Cu2+, etc.
can be carried out based on their different solubility and their ability to form
complex ions with specific reagents, such as HCl, H2SO4, NaOH, NH3, and others.
•Separation and identification of anions, such as Cl-, Br-, I-, SO42-, CO32-, PO43-,
etc., can be accomplished using reagents such as AgNO3, Ba(NO3)2 under neutral
or acidic conditions.

Aqueous
Equilibria
 Qualitative Cation Analysis
Group 1. Insoluble chlorides:

Most compounds that contain Cl-, Br-, I- ions are soluble, except AgCl, PbCl2, and
Hg2Cl2

As3+, Bi3+, Cd2+, Group 2. Acid-insoluble sulfides:

Cu2+, Hg2+, Sb3+,
and Sn2+ CuS, Bi2S3, CdS, PbS, HgS, As2S3, Sb2S3, and SnS2

Co2+, Fe2+, Mn2+, Group 3. Base-insoluble sulfides and hydroxides

Ni2+, Zn2+Al3+ and
Cr3+

Group 4. Insoluble phosphates:

Group 5. The alkali metal ions and NH+4 Aqueous

Equilibria
A flame test can be used to determine the presence of K+ , violet color (K+ is present)
Rules of Precipitation
The following list summarizes the combinations that will form precipitates in solution:
 Nitrates (NO3–): All are soluble.
 Potassium (K+), sodium (Na+), and ammonium (NH4+) salts: All are soluble.
•Chlorides (Cl–), bromides (Br–), and iodides (I–): All are soluble except silver (Ag+), lead (II)
(Pb2+), and mercury (II) (Hg2+) salts.

•Sulfates (SO42-): All are soluble except lead (II) (Pb2+), barium (Ba2+), and calcium (Ca2+).

•Carbonates (CO32-): All are insoluble except those of potassium (K+), sodium (Na+), and
ammonium (NH4+).
•Compounds with fluorine: All are soluble except magnesium (Mg2+), calcium (Ca2+),
strontium (Sr2+), barium (Ba2+), and lead(II) (Pb2+).
•Perchlorates (ClO4–) and acetates (C2H3O2–): All are soluble.

•Metal hydroxides (OH–) and oxides (O2-): Most are insoluble.

•Salts of phosphates (PO43-), oxalates (C2O42-), chromates (CrO42-), and sulfides (S2-):
Generally insoluble.

Aqueous
Equilibria
 Qualitative analysis

Aqueous
Equilibria
A flowchart showing a common scheme for identifying cations
Aqueous
Equilibria
Amphoterism

Aqueous
Equilibria
 Amphoterism
Amphoteric compound is a molecule or ion that can react both as an acid as well as a base.
Many metals (such as copper, zinc, tin, lead, aluminium, and beryllium) form
amphoteric oxides or hydroxides. Amphoterism depends on the oxidation states of the
oxide.
–Amphoteric hydroxides act as either Bronsted-Lowry bases (accepting protons) or Lewis
acids (accepting an electron pair), depending on reaction conditions.
–Examples of such cations are Al3+, Zn2+, and Sn2+.

Aqueous
Equilibria
 Al2O3 is amphoteric

Al2O3(s)+6H+(aq)2Al3+(aq) +3H2O(aq)

Al2O3(s)+2OH-(aq)+3H2O 2Al(OH)4(aq) +3H2O(aq)

Al2O3(s) has reacted with both an acidic solution and a basic

solution

Metal hydroxides with a highly-charged central metal atom can be amphoteric. In addition to
aluminum, metals such as zinc, tin, lead, and beryllium can also form amphoteric oxides or
hydroxides. Whether such hydroxides behave as acids or bases depends on the surrounding
solution’s pH.

Aqueous
Equilibria
Amphoterism

Aqueous
Equilibria
ACID-BASE INDICATORS

Aqueous
Equilibria
The end of chapter 17

Aqueous
Equilibria