Quantitative

Chemical
Analysis

Eighth Edition
Daniel C. Harris

Dr. Nafisah Al-Rifai

1st Semester – 2017/2018

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 Chapter 6: Chemical Equilibrium

6.1 The Equilibrium Constant

6.2 Equilibrium and Thermodynamics
6.3 Solubility Product
6.4 Complex Formation
6.5 Protic Acids and Bases
6.6 pH
6.7 Strengths of Acids and Bases

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 6-1 The Equilibrium Constant

For the reaction:

equilibrium constant, K:

a reaction is favored whenever K>1.

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 All equilibrium constants are dimensionless.

When evaluating an equilibrium constant,

1. Concentrations of solutes should be in mol/L.
2. Concentrations of gases should be in bars.
3. Concentrations of pure solids, pure liquids, and solvents are
omitted because they are unity.
−
H+ [A ]
HA H+ + A̅ 𝐾1 =
[HA]
If the direction of a reaction is reversed, then:
[HA]
H+ + A̅ HA 𝐾′1 = −
+
H [A ]

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 If two reactions are added, then:

HA [H+] + A̅ K1

[H+] + C HA K2 K3 = K1K2

HA + C A̅ + CH+ K3

Example Combining Equilibrium Constants

PROBLEM: The equilibrium constant for the reaction
H 2O H+ + OH ̅ is called Kw(=[H +][OH ̅ ]) and has the
value 1.0 x 10-14 at 25 ̊C. Given that K = 1.8 x 10-5 for the
reaction NH3 (aq) + H2O NH4+ + OH ̅ , find K for the
reaction NH4+ ̅ NH3 (aq) + H+

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 6-2 Equilibrium and Thermodynamics

Equilibrium is controlled by the thermodynamics of a chemical reaction.

The heat absorbed or released (enthalpy) and the degree of disorder

of reactants and products (entropy) independently contribute to the
degree to which the reaction is favored or disfavored.

enthalpy change, H,

Entropy change, S,

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 Systems at constant temperature and pressure, which are
common laboratory conditions, have a tendency toward
lower enthalpy (negative ∆H) and higher entropy (positive S).

When ∆H is negative and S is positive, the reaction is clearly favored.

When ∆H is positive and S is negative, the reaction is clearly disfavored.

The Change in Gibbs free energy, G

G = H - TS at constant temperature

A reaction is favored if G is negative.

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 Example

S˚ = -130.4 J/(K.mol) at 25˚C.

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 Free energy and Equilibrium

We say that a reaction is spontaneous under standard conditions

if G is negative or, equivalently, if K > 1.
The reaction is not spontaneous if G is positive (K < 1).

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 Le Châtelier’s Principle
Suppose that a system at equilibrium is subjected to a change that
disturbs the system. Le Châtelier’s principle states that the direction
in which the system proceeds back to equilibrium is such that the
change is partially offset.

Example

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 Reaction quotient, Q

If Q < K  the reaction must proceed to the right to reach equilibrium.

If Q > K  the reaction must proceed to the left to reach equilibrium.
At equilibrium Q = K

Heat can be treated as if it were a reactant in an endothermic

reaction and a product in an exothermic reaction.

K of an endothermic reaction increases if the temperature is raised.

K of an exothermic reaction decreases if the temperature is raised.

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 6-3 Solubility Product

The solubility product is the equilibrium constant for the reaction

in which a solid salt dissolves to give its constituent ions in solution.

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 Example

What is the concentration of Hg22+ in equilibrium with 0.10 M Cl ̄ in a

solution of KCl containing excess, undissolved Hg2Cl2 (s)?

The solubility product does not tell the entire story of solubility.
-We have to account for all reactions occurring in solution not
only dissolution of the salt.
- soluble Ion pairs may forms like CaSO4 (aq).

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 Common ion effect: A salt is less soluble if one of its
ions is already present in the solution.
This is an application of Le Chatelier’s principle.

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 If Ca2+ increased by adding CaCl2
 the conc. of SO42- must
decrease so that Ksp remains
constant. This means less CaSO4
will dissolve in this case.

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 Separation by Precipitation
Consider a solution containing lead(II) (Pb2+) and mercury(I) (Hg22+)
ions, each at a concentration of 0.010 M. Each forms an insoluble
iodide, but the mercury(I) iodide is considerably less soluble, as
indicated by the smaller value of Ksp :

Is it possible to lower the concentration of Hg22+ by 99.990% by

selective precipitation with Iˉ, without precipitating Pb2+?

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 Coprecipitation may occur. Our calculation says that the
separation is worth trying.
Only an experiment can show whether the separation
actually works.

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 6-4 Complex Formation
If anion X ̄ precipitates metal M +, it is often observed that a high
concentration of X ̄ causes solid MX to redissolve. The increased
solubility arises from formation of complex ions, such as MX2 ̄ ,
which consist of two or more simple ions bonded to one another.

Lewis acids and Bases

The bond between a Lewis acid and a Lewis base is called a

dative or coordinate covalent bond.

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 6-4 Complex Formation

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 6-5 Protic Acids and Bases

In aqueous chemistry,
an acid is a substance that increases the concentration of H3O+
(hydronium ion) when added to water,

a base decreases the concentration of H3O+ .

 a decrease in H3O+ concentration = an increase in OH- concentration.

Therefore, a base increases the concentration of OH- in aqueous soln.

The word protic refers to chemistry involving transfer of H+ from one

molecule to another.
The species H+ is also called a proton because it is what remains when
a hydrogen atom loses its electron.
Hydronium ion, H3O+, is a combination of H+ with H2O.

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 Brønsted-Lowry Acids and Bases

Brønsted-Lowry acid: proton donor

Brønsted-Lowry base: proton acceptor

HCl is an acid (a proton donor), and it increases the concentration

of H3O+ in water:

The Brønsted-Lowry definition does not require that H3O+ be

formed  This definition can be extended to nonaqueous solvents
and to the gas phase:

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 Salts

Any ionic solid, such as ammonium chloride, is called a salt.

Salt: the product of an acid-base reaction.

When an acid and a base react, they are said to neutralize each
other. Most salts containing cations and anions with
single positive and negative charges are strong electrolytes—they
dissociate nearly completely into ions in dilute aqueous solution.

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 Conjugate Acids and Bases

Conjugate acids and bases are related to each other by the gain or
loss of one H+.

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 The Nature of H+ and OH-

The proton does not exist by itself in water. The simplest formula
found in some crystalline salts is H3O+.

A more accurate formula would be H3O+ ClO4-.

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 The H5O2+ cation is another simple species in which a hydrogen
ion is shared by two water molecules.

The ion H3O2 ̄ (OH ̄ .H2O) has been observed by X-ray

crystallography.

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 water can be either an acid or a base. Water is an acid with
respect to methoxide:

But with respect to hydrogen bromide, water is a base:

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 Autoprotolysis
Water undergoes self-ionization, called autoprotolysis, in which it
acts as both an acid and a base:

or

Protic solvents have a reactive H+, and all protic solvents undergo
autoprotolysis. An example is acetic acid:

The extent of these reactions is very small.

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 6-6 pH

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 In pure water at 25 ˚C with [H+] = 1.0 x10-7 M

 pH = –log(1.0 x10-7 ) = 7.00.

A solution is acidic if [H+] > [OH-].

A solution is basic if [H+] < [OH-].

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 Is There Such a Thing as Pure Water?

In most labs, the answer is “No.” Pure water at 25 ˚C should have

a pH of 7.00.

Distilled water from the tap in most labs is acidic because it

contains CO2 from the atmosphere.

CO2 can be largely removed by boiling water and then protecting it

from the atmosphere.

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 6-7 Strengths of Acids and Bases

Acids and bases are commonly classified as strong or weak,

depending on whether they react nearly “completely” or only
“partially” to produce H+ or OH-.

A strong acid or base is completely dissociated in aqueous

solution  the equilibrium constants for the following reactions
are large.

The hydrogen halides HCl, HBr, and HI are strong acids,

but HF is not a strong acid.

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 Weak acids and bases

Most carboxylic acids are weak acids, and most carboxylate

anions are weak bases

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 Amines are weak bases, and ammonium ions are weak acids.

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 Metal cations:

Phenol (C6H5OH) is a weak acid.

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 Polyprotic Acids and Bases: are compounds that can donate or
accept more than one proton.
For example, oxalic acid is diprotic and phosphate is tribasic:

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 Relationship between Ka and Kb

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