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Chapter 2
Chapter 2
- Precipitation Reactions
- Common ion effect and salt effect on solubility
2.2 Effect of acidity on solubility
2.3 Complexation equilibria
- Complex ion and ligands
- Complex formation equilibria with unidentate and multidentate
ligands
- Factors affecting stability of complexes
- Effect of complexation on solubility
2.4 Redox Equilibria
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2. Introduction
• If a mixture of hydrogen and iodine vapor is heated to a temperature of about
450 OC in a closed vessel, the two elements combine to form hydrogen iodide.
• However, no matter how long the duration of the experiment, some hydrogen
and iodine remain uncombined.
• But again, no matter how prolonged the heating, some hydrogen iodide
remains unchanged.
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• It is found that after the elapse of some time interval, al1reversible reactions
reach a state of chemical equilibrium.
• In the equilibrium state, the two opposing reactions are taking place at the
same rate so that the system is in a state of dynamic equilibrium.
• Le Chatelier-Braun Principle:
• 'If a constraint is applied to a system in equilibrium, the system will
adjust itself so as to nullify the effect of the constraint‘.
(a) Temperature
• The formation of ammonia from nitrogen and hydrogen is a reversible reaction
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• The forward reaction is accompanied by the evolution of heat (energy), and is said
to be an exothermic reaction
(b) Pressure.
• Changing the pressure of the system affects both the reactant and product equally,
and so the composition of the equilibrium mixture remains unchanged.
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• In the nitrogen, hydrogen, ammonia equilibrium system, there is a decrease
in volume when ammonia is produced, and hence an increase in pressure
will favor the formation of ammonia.
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• THE LAW OF MASS ACTION
Equilibrium constant:
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• 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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•
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• Solubility product
• the smaller the value of Ksp, the less soluble the compound in water.
• Solution
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• Example 2: The Ksp of silver bromide (AgBr) is 7.7 × 10‒13 , calculate its molar
solubility
• Solution:
• Consider the dissociation of AgBr in water.
AgBr (s) ⇌ Ag+ (aq) + Br‒(aq)
Initial x 0 0
Change −x +x +x
Equilibrium 0 x x
• Therefore, at equilibrium [Ag+] = [Br‒] = 8.8 × 10‒7, and it is equal to the molar
solubility of AgBr.
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• Solubility = Molar solubility ×molar mass = 8.8 ×10‒7 mol/L × 188 g/mol =
1.65×10‒4 g/L.
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• Exercise
• The solubility of lead chromate (PbCrO4) is 4.5 ×10−5 g/L. Calculate the
solubility product of this compound.
Factors affecting solubility
A. Common ion effect
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• When a solution H2SO4 is added to the saturated CaSO4 solution.
• What is the effect on the equilibrium shift, solubility effect and Ksp value.
• solubility decrease
• If a solution that contains Ca2+ ions is added, it will have the same effect.
• Example 5:
• Calculate the solubility of silver chloride (in g/L) in a 8.3 × 10‒3 M silver
nitrate solution.
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• Solution
• The common ion here is Ag+ , which is supplied by both AgCl and AgNO3.
• The presence of the common ion will affect only the solubility of AgCl (in
g/L), but not the Ksp value.
• Step 1: The ionic species in solution are Ag+ ions (from both AgCl and
AgNO3), Cl– ions and the spectator NO3– ions.
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Ksp = [Ag+][ Cl‒] = (8.3 × 10‒3 + x) (x) = 1.6 ×10−10
Assuming x << 8.3 × 10‒3 :
Ksp = (8.3 × 10‒3 ) (x) = 1.6 ×10−10 ,
x = 1.9 × 10‒8 M
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B. Salt effect (electrolyte effect)
• This is the effect by salts with no common ion and it increases the solubility of
a precipitate.
• The salt effect results from the electrostatic attractive and repulsive forces
between the ions of an electrolyte and the ions involved in an equilibrium.
• These forces cause each ion from the dissociated reactant to be surrounded by a
sheath of solution that contains a slight excess of electrolyte ions of opposite
charge.
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• Similarly, each SO42− is surrounded by a Na+ and tends to be slightly positive.
• The charged layers created by adding NaCl make the Ba2+ appear to be
somewhat less positive and the SO42−somewhat less negative.
• In other words, the effective concentration of Ba2+ and SO42− ions becomes
less as the ionic strength of the medium becomes greater.
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Complex and Formation Constants
• For example, the heme molecule in blood holds iron tightly because the
nitrogen atoms of the heme form strong complexing bonds.
• The iron [as iron(II)] in turn bonds readily with oxygen to transport oxygen
gas from the lungs to elsewhere in the body.
• CO binds to heme 200 times more strongly than does oxygen, forming
carboxyhemoglobin.
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• Many cations will form complexes in solution with a variety of substances
that have a pair of unshared electrons.
• The metal cation is a Lewis acid (electron pair acceptor), and the
complexer is a Lewis base (electron pair donor).
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• The copper ion acts as a Lewis acid, and the ammonia is a Lewis base.
• The Cu2+ (hydrated) ion is pale blue in solution, while the ammonia (the
ammine) complex is deep blue.
• Ammonia will also complex with silver ion to form a colorless complex.
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• The overall reaction is the sum of the two steps, and the overall formation
constant is the product of the stepwise formation constants:
• For the formation of a simple 1:1 complex, for example, M + L = ML, the
formation constant is simply Kf = [ML]/[M][L].
• The formation constant is also called the stability constant Ks, or Kstab.
• In this case the concentration terms are inverted in the equilibrium constant
expressions and the formation constants are then called instability constants
Ki, or dissociation constants Kd: Kf = Ks = 1/Kior 1/Kd.
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• Classification of ligands
• Depending on the number of donor atoms present ligands are classified as:
1. Monodentate (unidentate) ligands: ligands with only one donor atom.
2. Polydentate (multidentate) ligands: ligands with more than one donor atom.
• Bidentate ligand e.g. ethylenediamine ( “en”): oxalate
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Example : A 0.22 M quantity of CuSO4 is added to 1.35 M NH3 solution. Find
the equilibrium concentrations of Cu2+, NH3 and Cu(NH3)42+ . Use Kf = 5 × 1013
Solution
CuSO4 ⟶ Cu2+(aq) + SO42‒(aq)
0.22 M 0.22 M 0.22 M
The addition of CuSO4 to the NH3 solution results in complex ion formation
Cu2+(aq) + 4NH3(aq) ⇌ Cu(NH3)42+(aq)
Kf = 5 × 1013
Since Kf is very large, at equilibrium assume all central ion is converted to
complex product. Hence, Ccomplex = Ccentral atom
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• Let the equilibrium concentration of Cu2+ be x.
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Factors affecting stability of complexes
• It determines the type of bonding with the ligand donor atom; more the
electrostatic character of the bond, stable the complex.
• When increasing charge/size ratio the stability increase, this means the
nature of central ion refers to:
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a) The greater charge/size ratio the greater will be the stability of the complex.
Example, complex of Fe3+ are more stable than Fe2+.
b) The higher the electronegativity of the central ion the more stable will be
the complex.
• The nature of bond formed between the ligand and metal ion also influence
the stability.
• For example the complex of nickel with the hexadentate ligand, penten, is
more than 1010 times stronger than the one formed by ammonia.
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Basicity of the ligand:
• The stability of the complex is directly related to the number of chelate rings
formed between the ligand and metal ion.
• The formation of five- or six-membered rings provides the maximum stability
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Steric effects:
• The steric effects refer to the sizes of the ligands, their spatial arrangement
and the distances between the coordination sites and also if bulky groups
are present around.
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• Solution
• The CN– ions act as ligands and react with Zn2+ (aq) to form the complex
ion Zn(CN)42–:
Zn2+(aq) + 4 CN–(aq) ⇌ Zn(CN)42–(aq), Kf = 4.2×1019
• To observe the effect, add the above equations and multiply their
equilibrium constants:
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• Example: Calculate the solubility of AgI in 2.5 M NH3 and Kf of
Ag(NH3)2+ = 1.7×107 and Ksp of AgI = 8.3×10–17
• Solution
• In this example the influence of complexation on solubility will be
identified.
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• Step-3: setting up equilibrium expression
AgI(s) + 2NH3(aq) ⇌ Ag(NH3)2+(aq) + I–(aq)
Initial 2.5 0 0
Complexation −2x +x +x
Equilibrium 2.5 −2x +x +x
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• Step-5: conversion of molar solubility to solubility form
Solubility = (9.4 × 10−5 mol/L) × (235 g/mol)
= 2.2 × 10−2 g/L
Redox Equilibria
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• For example, in the following redox reaction between Fe3+ and oxalic acid,
H2C2O4, iron is reduced since its oxidation state changes from +3 to +2.
• Oxalic acid, on the other hand, is oxidized since the oxidation state for
carbon increases from +3 in H2C2O4 to +4 in CO2 .
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• Oxidation is a loss of electron/s and reduction is a gain of electron/s.
Electrochemical Cells
• The lead storage battery and the ordinary flashlight cell are common
examples of voltaic cells.
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• In electrolytic cells, electrical energy is used to force a nonspontaneous
chemical reaction to occur, that is, to go in the reverse direction it would in
a voltaic cell. E cell is negative
• In both types of these cells, the electrode at which oxidation occurs is the
anode, and that at which reduction occurs is the cathode.
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• Assume the Fe2+ and Ce4+ are in separate beakers connected by a salt
bridge, as shown in Figure.
• (A salt bridge allows ion transfer into the solutions and prevents mixing of
the solutions.)
• KCl is the preferred ingredient since K+ and Cl− move at equal speeds.
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• The Fe2+ is being oxidized at the platinum wire (the anode):
Fe2+ → Fe3+ + e− (oxidation half-reaction)
• The released electrons flow through the wire to the other beaker where the
Ce4+ is reduced (at the cathode):
Ce4+ + e− → Ce3+ (reduction half-reaction)
• The net reaction that occurs in the voltaic cell; it is called the cell reaction.
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Notation for Voltaic Cells
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• The shorthand notation for representing the cell with the reaction
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
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• What is the shorthand notation for representing the cell shown below?
1.
2.
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• Relation between Electrode Potential and Concentration.
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• Calculation of Half-cell potential
• For an oxidation half-cell reaction when the metal electrode M gives Mn+
ion, M → Mn+ + ne–
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• Example . What is the potential of a half-cell consisting of zinc electrode in
0.01M ZnSO4 solution at 25°C, E° =0.763 V.
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Calculation of Cell potential
• Thus,
• Solution
Step 1. Write the half-cell reactions of the anode and the cathode.
• Then add the anode and cathode half reactions to obtain the cell reaction and
the value of E°cell.
• E° for a reaction is calculated as E°cell = E°cathode – E°anode
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Step 2. K for the cell reaction
• substitute the given values in the Nernst equation and solving for E°cell, we
have
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Calculation of Equilibrium constant for the cell reaction
or
• Example: Calculate the equilibrium constant for the reaction between silver
nitrate and metallic zinc.
Solution
Step 1. Write the equation for the reaction 2Ag+ + Zn ⇌ Zn2+ + Ag
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• Step 2. Substitute values in the Nernst equation at equilibrium
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