Chem A2 Notes

A2 A-level Chemistry Notes
23-Chemical Energetics
Lattice Energy ∆H⊝

latt : Lattice energy is the enthalpy change when 1 mole of an ionic
compound is formed from its gaseous ions under standard conditions. The unit is kJ mol-1.
Mg2+(g) + 2F-(g) → MgF2(s) ∆H⊝ latt = -2922 kJ mol
-1
⊝
Ti4+(g) + 2O2-(g) → TiO2(s) ∆Hlatt = -12150 kJ mol-1
1-It is always gaseous ions combine to form the ionic solids.
2-Lattice energy values will always be negative because our definition entails ionic bond
making (exothermic) not bond breaking (endothermic).
Significance of the value of lattice energy
The more exothermic the lattice energy (tends towards -∞), the stronger the stability of the
ionic bond in the lattice.
Enthalpy Change of Atomisation ∆H⊝

at : The enthalpy change when 1 mole of gaseous
atoms is formed from its element under standard conditions, where standard conditions
entail 298.15K and 105 Pa. The unit is kJ mol-1.
Na(s) → Na(g) ∆H⊝at = +108 kJ mol
-1
CH4(g) → C(g) + 4H(g) ∆H⊝

at = +1665 kJ mol
-1
1
Cl2(g) → Cl(g) ∆H⊝at = +122 kJ mol
-1
2
1-Enthalpy of atomization is always positive, because bond breaking is endothermic (+).
2-The enthalpy of atomization of monoatomic atoms is zero, because there is no energy to
be supplied to dissociate any atom-atom bond, and all elements that exist monoatomically
happen to be already gases in Group 18.
First Electron Affinity ∆H⊝

ea1 : The first electron affinity is the enthalpy change when 1
mole of electrons is added to 1 mole of gaseous atoms to form 1 mole of gaseous 1- ions
⊝
under standard conditions (298.15K and 105 Pa). The unit is kJ mol-1. Inverse of ∆Hie1 .
S(g) + e- → S-(g) ⊝
∆Hea1 = -200 kJ mol-1
P(g) + e- → P-(g) ⊝
∆Hea1 = -72 kJ mol-1
Second Electron Affinity ∆H⊝

ea2 : The second electron affinity is the enthalpy change when
1 mole of electrons is added to 1 mole of gaseous 1- ions to form 1 mole of gaseous 2- ions
⊝
under standard conditions (298.15K and 105 Pa). The unit is kJ mol-1. Inverse of ∆Hie2 .
O-(g) + e- → O2-(g) ⊝
∆Hea2 = +798 kJ mol-1
1-2nd and 3rd electron affinities are always positive, because it would require energy to
add an electron into a negative ion due to like charges electrostatic repulsion. Forcing an e-
into an already negatively-charged space would require energy (endothermic).
2-The overall enthalpy change for the creation of a non-mononegative ion is given by the
addition of all electron affinity stage values up to the value of the charge of the negative
ion. For example, the overall enthalpy change when an O2-(g) ion is created from an O(g)
⊝ ⊝
atom is given by ∆H = ∆Hea1 + ∆Hea2 , ∆H = (-141) + (798) = 657 kJ mol-1.
Trends and factors affecting Electron Affinity
Electron Affinity increases. Electron Affinity increases

-Electron affinity increases because the electrons are held tighter by the increase in the
effective nuclear charge and the decrease in atomic size.
-Electron affinity increases up the groups because the electron shells decrease, resulting in
the increase of the effective nuclear charge and the decrease in the atomic size.
When I say electron
affinity increases, I mean
it becomes more exothermic
(more negative)
Factors affecting electron affinity
1-Atomic size r:
1
∆H⊝ ea ∝ Atomic Radius. When the atomic size increases, the effective nuclear charge experienced
by the valence electrons decreases. Therefore, a given atom will have a lower tendency to
attract additional electrons. Consequently, the electrostatic force of attraction between the
nucleus and the valence electrons decreases, which decreases the atom’s electron affinity.
Atomic radius decreases from left to right across a period, which explains the increase in
the electron affinity values across a period from left to right.
2-Effective Nuclear Charge Z:

∆H⊝ ea ∝ Effective Nuclear Charge Z. When the effective nuclear charge increases, the
electrostatic force of attraction between the nucleus and the valence electrons increases. The
increase in electrostatic forces of attraction will increase the tendency to attract additional
electrons, which increase electron affinity values.
3-Shielding Effect:
1
∆H⊝ea ∝ . As the shielding effect increases, it becomes harder for additional
Shielding Effect
electrons to enter the atom due to the repulsion of electron-electron repulsion. As the like-
charge repulsions increase, less electrons enter the atoms.
4-Orbital Entry:
To a certain extent, electron affinity values increase when electrons enter an ‘s’ orbital,
because s orbital electron addition tend to be closer to the nucleus, which increases the
effective nuclear charge and closes down the distance to the center of the nucleus. The
electron affinity values then go on to decrease commencing with ‘p’, then ‘d’, then ‘f’.
5-Electronic Configuration:
1
∆H⊝ea ∝ . If the electronic arrangement of an atom happens to be
Electronic Configuration Stability
stable, the atom will be less likely to accept an electron from outside. Electron affinities of
noble gases are zero because they have the stable ns2 np6 configuration, so there is no
possibility of adding electrons. Stable configurations entail fully-filled or exactly half-
filled outer orbitals. Beryllium has a 1s2 2s2 configuration, so it’s fully filled. Its electron
affinity is close to zero. Calcium has 1s2 2s2 2p6 3s2 3p6 4s2 config., so it’s also has full
outer orbitals. Its electron affinity value is 2.37 kJ mol-1. 😊
Electron Affinities for Group 16 and Group 17
Electron affinities become less and less exothermic down the group for both Group 16 and
17, except for the first elements in both groups (Oxygen and fluorine).
Moving down Group 16 and group 17, the valence electrons are farther away from the
nucleus. The electrostatic force of attraction becomes weaker and weaker and the number of
energy levels increases, which causes an increased shielding effect. This increases the
⊝
difficulty of adding electrons, which decreases the exothermicity of the ∆Hea1 .
Why are Fluorine and Oxygen anomalous?

Fluorine atoms have an extremely small atomic radius, so electron density is very high.
Incoming electrons become very unlikely to enter the atom due to like-charge repulsion. The
like-charge repulsion overshadows the electrostatic attraction between the nucleus and the
incoming electron. Some of the energy required to insert an electron into a fluorine atom is
lost to overcome the instability caused by the electron-electron charge repulsion.
Oxygen does the same thing when compared to Sulfur.
Born-Haber Cycles
Born-Haber Cycles: A type of enthalpy change cycle used to calculate lattice energies.
⊝
∆Hlatt , Lattice Energy
Ions in their
Ionic Compounds
Gaseous States
Enthalpy changes related Hess’ Law Curve Standard Enthalpy
to transformation from change of formation,
atoms to their ions, ⊝
⊝ ∆Hf
∆H1
Note that ∆H⊝ 1 cannot be determined
Elements in their directly, as it involves ∆H⊝ ⊝
at , ∆Hi1 for the
Standard States ⊝
ea1 , ∆Hat for the anion.
cation and ∆H⊝
⊝ ⊝ ⊝ ⊝ ⊝ ⊝
∆H1 +∆Hlatt =∆Hf ∆Hlatt =∆Hf − ∆H1
An example of a Born-Haber Cycle involving Lithium Fluoride, LiF:
⊝
Li+(g) + F-(g) LiF(s)
⊝
∆Hea1 [F] = -328 kJ mol-1
Li+(g) + F(g) + e-
∆H⊝
at [F] = +79 kJ mol
-1 Standard Enthalpy
1 change of formation,
Li+(g) + F(g) + e-
2 ⊝
∆Hf = -617 kJ mol-1
⊝
∆Hi1 [Li] = +520 kJ mol-1
1
Li(g) + F(g)
2
∆H⊝
at [Li] = +161 kJ mol
-1
1
Li(s) + F2(g)
2
⊝ ⊝ ⊝
∆Hlatt = ∆Hf - ∆H1 = -617 - (-328 + 79 + 520 + 161) = -617 – (432) = -1049 kJ mol-1
-Calculate the lattice energy for sodium chloride, given that:

⊝
∆Hf [NaCl] = -411 kJ mol-1, ∆H⊝ ⊝
at [Na] = +107 kJ mol , ∆Hat [Cl] = +122 kJ mol ,
-1 -1
⊝ ⊝
∆Hi1 [Na] = +496 kJ mol-1, ∆Hea1 [Cl] = -348 kJ mol-1.
⊝
Na+(g) + Cl-(g) NaCl(s)
∆Hlatt = ∆H⊝
⊝ ⊝
Na+(g) + Cl(g) + e- f − ∆H1 = -411 – (+107 + 122
+ 496 – 348) = -411 – (377) = -788 kJ mol-
1
1 Standard Enthalpy
Na+(g) + Cl(g) + e- change of formation,
2
⊝
∆Hf = -411 kJ mol-1
1
Na(g) + Cl(g)
2
1
Na(s) + Cl2(g)
2
Born-Haber Cycles can also be drawn in terms of an energy-level diagram. Below is an
example for the Born-Haber cycle for Lithium Fluoride, LiF(s), an analogue to the 1st one.
Li+(g) + F(g) + e-
1
∆H⊝
at [F] Step 3 Li+(g) + F2(g) + e- ⊝
∆Hea1 [F]
2
Step 4
Li+(g) + F-(g)
⊝
∆Hi1 [Li] Step 2
1
Li(g) + F2(g)
2
∆H⊝
at [Li] Step 1 1
Li(s) + F2(g) ⊝
∆Hlatt
2
⊝
∆Hf
LiF(s)
⊝ ⊝ ⊝
∆Hlatt = ∆Hf - ∆H1 = -617 – [(+161) + (520) + (79) + (-328)] = -1049 kJ mol-1.
Now look at ionic compounds where the formula unit has more than 1 cation or anion, like
Sodium Oxide, Na2O. 2Na+(g) + O2-(g)
⊝
∆Hea2 [O] Step 5
2Na+(g) + O(g) + 2e-
⊝
∆Hea1 [O] Step 4 2Na+(g) + O-(g) + e-
∆H⊝
at [O] Step 3 2Na+(g) + O2(g) + e-
1
2
⊝
∆Hlatt [Na2O]
⊝ 1
2∆Hi1 [Na] Step 2 2Na(g) + O2(g)
2
1
2∆H⊝
at [Na] Step 1 2Na(s) + O2(g)
2
⊝
∆Hf
Mg2+(g) + O2-(g)
Born-Haber Cycle for MgO:
⊝
∆Hea2 [O]
Mg2+(g) + O(g) + 2e-
1
∆H⊝
at [O] Step 4 Mg2+(g) + O2(g) + 2e- ⊝ Mg2+(g) + O-(g) + e-
2
∆Hea1 [O]
⊝
∆Hi2 [Mg] Step 3 1
Mg+(g) + O2(g) + e-
2
⊝
∆Hlatt [MgO]
⊝ 1
∆Hi1 [Mg] Step 2 Mg(g) + O2(g)
2
1
∆H⊝
at [Mg] Step 1 Mg(s) + O2(g)
2
⊝
∆Hf
What factors affect Lattice Energy?
The lattice energy is the emergence of the sum of the work done by the electrostatic forces
of attraction between the oppositely charged ions within the lattice.
1-Lattice Energy and the ionic radius.
⊝ 1
∆Hlatt ∝ . The amount of electric charge per unit volume of ion will decrease if
Ionic Radius
the volume of the ion decreases. Therefore, this decreases the charge density. A reduction in
charge density will minimize electrostatic forces of attraction throughout the ionic lattice.
When the electrostatic force, FQ, decreases the exothermicity of the lattice energy within the
ionic lattice will decrease.
2-Lattice energy and Ionic Charge Quantity.
⊝
∆Hlatt ∝ Ionic Charge. An increase in the amount of ionic charge attracts the oppositely
charged ions more than ions of smaller charges. Therefore, for ions of similar size, the
greater the ionic charge, the more exothermic the lattice energy.
Ion Polarisation
The concentration of the charge in a dense positively-charged sphere can alter and distort
the sphericity of negative ions in a lattice due to electrostatic attraction. This shape
distortion phenomena is known as ion polarisation. The cationic ability to distort anionic
charge spheres is known as the polarising power of the cation. The degree of distortion of
the anion is known as the polarisability of the anion.
2+ 1- 2+ 2- 2+ 3-
What Factors Affect Ion Polarisation?

The degree of ion polarisation of an anion depends on the charge density of the cation and
the polarisability of the anion.
The polarisability of an anion increases if the ionic radius of the cation is smaller, the
quantity of the ionic charge of the cation increases, the anionic radius is large and the anionic
charge of the anion increases (becomes more negative).
23.2-Enthalpies of Solution and Hydration
Enthalpy of change of Solution, ∆H⊝

sol : The energy absorbed or released when 1 mole of
an ionic solid dissolves in sufficient water to form a very dilute solution. Unit is kJ mol-1
The general format of the equation would be written as:

Salt(s) + aq → Salt(aq) or Salt(s) + aq → Cation(aq) + Anion(aq), where aq represents a
sufficiently large amount of water to dissolve the salt.
⊝
If ∆Hsol is less than 0, or very slightly above 0, then the salt is soluble. The solubility
⊝ ⊝
decreases as ∆Hsol increases. ∆Hsol can be either endothermic or exothermic.
⊝ ⊝
Equation for ∆Hsol of AgBr is: AgBr(s) + aq → AgBr(aq) where ∆Hsol = 84.5 kJ mol-1.
⊝
AgBr is evidently insoluble in water as predicted by the ∆Hsol equation.
Remember that all salts are soluble in water, but to different extents. No metallic salt is
completely insoluble in water. ‘Insoluble’ just means extremely small amounts of a salt
⊝
dissolve. If any salt was completely insoluble, it would have its ∆Hsol = ∞ kJ mol-1
Enthalpy change of hydration, ∆H⊝
hyd : The enthalpy change of hydration is the enthalpy
change when 1 mole of a specified gaseous ion dissolves in sufficient water to form a very
⊝
dilute solution. ∆Hhyd is always exothermic for reasons we’ll discuss later. For the same
⊝ 1 ⊝
ionic charge, ∆Hhyd ∝ . For similar ionic radii, ∆Hhyd ∝ Ionic Charge.
Ionic Radius
⊝
The general equation for the ∆Hhyd is written as:
Cation or Anion(g) + aq → Cation or Anion(aq). Examples:
⊝
Ca2+(g) + aq → Ca2+(aq) ∆Hhyd = -1650 kJ mol-1
⊝
Cl-(g) + aq → Cl-(aq) ∆Hhyd = -364 kJ mol-1
⊝
Al3+(g) + aq → Al3+(aq) ∆Hhyd = -406 kJ mol-1
The electrostatic force of attraction in ionic bonding are extremely strong due to the
structuring of the ionic lattice and the oppositely-charged ions.
How can simple H2O dismantle strong ionic bonding in salts and simply dissolve them?
-The answer lies within the strong ion-dipole bonds between the polar H2O molecules and
the individual ions that were dismantled from within the lattice. The energy released from
the formation of the ion-dipole bonds releases enough energy to overcome the ionic bonding
and free the cations and anions. The δ− O atoms are attracted to the cations, and the δ+ H
atoms will be attracted to the anions.
𝜹+ Ion-dipole bond formation
𝜹-
𝜹-
𝜹+
Bond formation
𝜹+
𝜹-
Ionic lattice
𝜹+
⊝ ⊝ ⊝
Relationship between ∆Hlatt , ∆Hsol , ∆Hhyd .
⊝
Ions in their
Ionic Solid
Gaseous States
Enthalpy change of Enthalpy change of
hydration of cation an ⊝
⊝ Solution ∆Hsol
anion, ∆Hhyd
Ions in aqueous
solution
⊝ ⊝ ⊝
By using Hess’ Law, ∆Hhyd = ∆Hlatt + ∆Hsol , and remember that:
⊝ ⊝ ⊝
∆Hhyd = ∆Hhyd [Anion] + ∆Hhyd [Cation].
Example: Calculate the enthalpy change of hydration of magnesium ions given that:
⊝ ⊝
∆Hlatt [MgCl2] = -2592 kJ mol-1, ∆Hsol [MgCl2] = -55 kJ mol-1, ∆Hhyd [Cl-] = -364 kJ mol-1.
⊝
⊝
Mg2+(g) + 2Cl-(g)
MgCl2(s)
Enthalpy change of Enthalpy change of

hydration of cation an ⊝
⊝ Solution ∆Hsol
anion, ∆Hhyd
Mg2+(aq) + 2Cl-(aq)
⊝ ⊝ ⊝ ⊝
∆Hhyd = ∆Hlatt + ∆Hsol → ∆Hhyd [Mg2+] + 2(-364) = (-2592) + (-55)
⊝
∆Hhyd [Mg2+] = -2592 – 55 – 2(-364) = -1919 kJ mol-1
⊝
We multiply the ∆Hhyd [Cl] by 2 because we’re converting 2Cl-(g) to 2Cl-(aq).
Now let’s look at another example involving another salt and solve it using an energy-level diagram.
Calculate the ∆H⊝
hyd [Cl ] given that: ∆Hlatt [LiCl] = -846 kJ mol , ∆Hsol [LiCl] = -37 kJ mol ,
- ⊝ -1 ⊝ -1
∆Hhyd [Li+] = -519 kJ mol-1.

⊝
Li+(g) + Cl-(g)
⊝ ⊝
∆Hlatt [LiCl] = -846 kJ mol-1 ∆Hhyd [Li+] = -519 kJ mol-1
⊝
+ ∆Hhyd [Cl-] = ?
LiCl(s)
⊝
∆Hsol [LiCl] = -37 kJ mol-1
LiCl(aq)
⊝ ⊝ ⊝ ⊝
∆Hhyd [LiCl] = ∆Hlatt [LiCl] + ∆Hsol [LiCl] → -519 + ∆Hhyd [Cl-] = (-846) + (-37)
⊝
∆Hhyd [Cl-] = -846 – 37 + 519 = -364 kJ mol-1.
Factors affecting Enthalpy Change of Hydration ∆H⊝

Hyd
1-Ionic Radius
The larger the radius of the ion, the lower the charge density of the ion. When the charge
density decreases, the strength of the ion-dipole attractions between the water molecules and
the ions within the lattice decreases, which will reduce the exothermicity (increase in
positivity) of the enthalpy change of hydration.
2-Ionic Charge
The larger the amount of the charge on the ions, the stronger the electrostatic force of
attraction between the oppositely-charged ions within the lattice. The extremely strong
attraction between the ions requires higher energy and more ion-dipole attractions between
the polar water molecules and the ion. This means more bond formation that is more
⊝
energetic is required, which increases the exothermicity of the ∆HHyd .
23.3-Entropy Change, ∆S
Entropy, S: The number of possible arrangements of the particles and their energy in a
given system. It can also be defined as the measure of the degree of randomness of a
system, where if the randomness increases, entropy increases. Its unit is Joules per Kelvin,
J K-1.
Spontaneous Reactions: A spontaneous reaction is one in which product formation is
favored, even if the reaction is extremely slow. Once the reaction commences by offering the
activation energy, the system releases free energy and it moves to a lower, more
thermodynamically stable energy state.
System: The reactants converted to products under investigation in a chemical reaction.
Surroundings: Non-system segments part of the experiment, which may include non-
reactant solvents, air around reaction vessels, reaction vessel itself and any measuring
instrument like a thermometer or galvanometer.
Standard Molar Entropy S⊝ : It is the entropy when the substance is in its normal state at
298 K and 105 Pa per mole. Its unit is J K-1 mol-1. The ⊝ symbolizes standardization. A
perfect crystal weighting 12g at 0 K has 0 S⊝ , which is considered the lowest possible
amount of disorder. Therefore, all S⊝ > 0.
Generalisations regarding fluctuations of Entropy

-S[Gas] >> S[Liquid] > S[Solid], with rare exceptions.
-Simpler molecules/formula units have lower S⊝ compared to larger molecules/F.units.
-For substances of similar standard states, stiffer substances will lower S values.
-S ∝ T, where T is the thermodynamic temperature measured in Kelvins. This is because the
increase in temperature corresponds to an increase in the average K.E. of the particles
involved in the system, which increases the frequency of vibrations, speed, and number of
possible arrangements. This will lead to an increase in the amount of disorder in the system.
-∆S[Solid → Liquid] << ∆S[Liquid → Gas], because particlesGas are more disordered.
Entropy/ J K-1
Entropy per unit temperature higher
Entropy per unit temperature lower
Temperature/ K
-If a solute dissolves into a solvent, the entropy increases due to the dispersal of the ions
into the solution, which increases the amount of disorder.
Entropy Changes in Reactions
In chemical reactions, qualitatively, gases have the highest entropies and solids have the
lowest. When you notice that the No. of gaseous molecules changes, there will be significant
increase in S if the no. of molecules increases, and there will be a significant decrease in S if
the no. of molecules decreases. When the number of gaseous molecules increases, the number
of ways of arranging these molecules increases, and so does the entropy.
CuCO3(s) → CuO(s) + CO2(g) ∆S = + due to generation of gases
2SO3(g) → 2SO2(g) + O2(g) ∆S = + because MolGas in reactant < MolGas in product
N2(g) + 3H2(g) → 2NH3(g) ∆S = - because MolGas in reactant > MolGas in product
H2O(g) + C(s) → H2(g) + CO(g) ∆S = + because MolGas in reactant < MolGas in product
Entropy Changes in Exothermic and Endothermic Reactions
-In exothermic reactions: The energy released to the surroundings expands the number of
arrangements in which the expelled energy can be categorized. The expelled energy is going
to be used to increase the average K.E. of the particles in the surroundings, which increases
the S value and increases the spontaneity of the reaction.
-In endothermic reactions: The energy assimiliated from the surroundings decreases the
number of arrangements in which the absorbed energy can be categorized. The absorbed
energy reduces the average K.E. of the particles in the surroundings, which decreases the S
value and decreases the spontaneity of the reaction.
Calculations involving Entropy Values
Total Standard Molar Entropy Change, ∆S⊝ ⊝

Total : Total ∆STotal is given by the equation:
⊝ ⊝ ⊝ ⊝
∆STotal = ∆SSystem + ∆SSurroundings , where if the value of ∆STotal is > 0, then the reaction
⊝
occurs spontaneously and is feasible. If ∆STotal < 0, then the reaction is not spontaneous
and is weakly to non-feasible.
Standard Molar Entropy of the System, ∆S⊝ ⊝
Sys : The ∆STotal is given by the leftover energy
⊝ ⊝ ⊝
transferred from the reactants to the products. Therefore, ∆SSystem = ∆Sproduct - ∆SReactants .
1-Calculate the standard entropy change of the system, ∆S⊝sys in each of the following
reactions using the standard molar entropy values given: 2H2O2(l) → 2H2O(l) + O2(g)
S⊝ [H2O(l)] = 69.9 J K-1 mol-1, S⊝ [H2O2(l)] = 109.6 J K-1 mol-1, S⊝ [O2] = 205.0 J K-1 mol-1
∆S⊝ ⊝ ⊝
sys = ∆Spro - ∆Sreact → [205 + 2(69.9)] – 2(109.6) = 125.6 J K mol
-1 -1
⊝
2-Calculate the standard entropy change of the system, ∆Ssys in each of the following
reaction using the standard molar entropy values given: 3Mg(s) + Fe2O3(s) → 3MgO(S) + 2Fe(s)
S⊝ [Mg] = 32.7 J K-1 mol-1, S⊝ [Fe2O3] = 87.4 J K-1 mol-1, S⊝ [MgO] = 26.9 and S⊝ [Fe] = 27.3
∆S⊝ ⊝ ⊝
sys = ∆Spro - ∆Sreact → [3(26.9) + 2(27.3)]–[(87.4) + 3(32.7)] = 135.3–185.5 = -50.2 JK mol
-1 -1
3-Calculate the standard entropy change of the system, ∆S⊝sys in each of the following
reactions using the standard molar entropy values given: NH4NO3(s)→ N2O(g) + 2H2O(g)
S⊝ [NH4NO3(s)] = 151.1 J K-1 mol-1, S⊝ [N2O(g)] = 219.7 J K-1 mol-1, S⊝ [H2O(l)] = 69.9 J K-1 mol-1
∆S⊝ ⊝ ⊝
sys = ∆Spro - ∆Sreact = [(219.7) + 2(69.9)] – (151.1) = 359.5 – 151.1 = 208.4 J K mol .
-1 -1
Standard Entropy Change of Surroundings, ∆S⊝

Surroundings : The amount of energy released or
taken from the surroundings that can increase or decrease the disorder of the molecules in
⊝
⊝ ∆HReaction ⊝
the surroundings. It is numerically given by =- ∆Ssurroundings
, where ∆HReaction is
T
the standard enthalpy change of the reaction and T is the standard thermodynamic
temperature (298 K).
4-Calculate the entropy change of the surroundings in each of the following reactions:
⊝
2C(s) + N2(g) → C2N2(g) ∆HReaction = +307.9 kJ mol-1 carried out at 300℃
307900
∆S⊝
Surroundings = - = -537.3 J K-1 mol-1
300+273
⊝
Si(s) + 2H2(g) → SiH4(g) ∆HReaction = +34.3 kJ mol-1 carried out at -3℃
34300
∆S⊝
Surroundings = - = 127.0 J K-1 mol-1
-3 + 273
⊝
⊝ ⊝ ⊝ ∆HReaction
Because ∆STotal = ∆S⊝
system + ∆Ssurroundings, and ∆Ssurroundings =- , therefore:
T
⊝
⊝ ⊝ ∆HReaction ⊝
∆STotal = ∆SSystem- . If the ∆STotal is significantly > 0, then the reaction is deemed
T
feasible, more likely to be spontaneous and more likely to go to completion once ∆Ea is
achieved.
⊝
5- Calculate the ∆STotal in each of the following reactions using the standard molar
entropy values given: S⊝ [C3H8(g)] = 269.9, S⊝ [O2(g)] = 205.0, S⊝ [CO2(g)] = 213.6
and S⊝ [H2O(l)] = 69.9 J K-1 mol-1.
⊝
C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(l) ∆HReaction = -2219.2 kJ mol-1
⊝
⊝ ⊝ ⊝ ⊝ ⊝ ∆HReaction
∆STotal = ∆SSystem + ∆SSurroundings → ∆Sproducts - ∆SReactants -
T
⊝ (-2219200)
∆STotal = [3(213.6) + 4(69.9)] – [(269.9) + 5(205.0)] - 298
= +7072.5 J K-1 mol-1.
⊝
6-Calculate the ∆STotal for the following reaction given the values:
S⊝ [P(s)] = 41.1, S⊝ [O2(g)] 205.0, S⊝ [P4O10(s)] = 228.9 J K-1 mol-1.
⊝
4P(s) + 5O2(g) → P4O10(S) ∆HReaction = -2984.0 kJ mol-1.
⊝
⊝ ⊝ ⊝ ⊝ ⊝ ∆HReaction
∆STotal = ∆SSystem + ∆SSurroundings → ∆SProducts - ∆SReactants -
T
⊝ (-2984000) 298 K because it is the
∆STotal = (228.9) – [4(41.1) + 5(205)] - 298
= +9053 J K-1 mol-1. standard thermodynamic
temperature
The behavior of Entropy in Equilibrium Reactions
When a closed reaction system reaches equilibrium, both reaction pathways will continue,
and the concentrations of the reactants and products will remain constant. Once equilibrium
is reached and maintained, the system will reach ∆SMAX.
Take the example of the Haber Process: N2 (g) + 3H2(g) ⇌ 2NH3(g)
Equilibrium occurs at SMaz.

The level of randomness in
the number of possible
Entropy
arrangements has maxed

out, and the amount of
disorder in the closed
system is at its maximum.
N2(g) + H2(g) NH3(g) Maximum

Disorder at
H2 molecules equilibrium
N2 molecules
NH3 molecules
Entropy and Gibbs Free Energy
Gibbs Free Energy, ∆G: Gibbs free energy is a thermodynamic potential that can be used to
calculate the maximum reversible work that may be performed by a thermodynamic system
at a constant temperature and pressure. It is given by ∆G = -T∆STotal. It can also be
described without referring to ∆Ssurroundings, using: ∆G = ∆HReaction - T∆STotal. Units are kJ
mol-1. It can be positive or negative. Derivation:
⊝
⊝ ⊝ ∆H
(∆STotal = ∆SSystem - Reaction ) × (-T)
𝑇
⊝ ⊝ ⊝ ⊝
-T∆STotal = -T∆SSystem + ∆HReaction (∆G = -T∆STotal )
⊝ ⊝
∆G = ∆HReaction - T∆SSystem
Standard Molar Gibbs Free Energy, ∆G⊝ : Gibbs free energy that accompanies the
formation of one mole of a compound from its elements in their standard states. Units are
kJ mol-1.
⊝
Reactions are spontaneous when ∆STotal is positive. So ∆G = -T∆STotal results in a negative
value for ∆G if a reaction is spontaneous. If ∆G > 0, then the reaction is non-feasible.
1-Calculate the ∆G⊝ using the values given:

⊝
2Na(s) + O2(g) → Na2O2(s) ∆HReaction = -510.9 kJ mol-1
∆𝑆 ⊝ [Na(s)] = 51.2, ∆𝑆 ⊝ [Na2O2(s)] = 95.0, ∆𝑆 ⊝ [O2(s)] = 205.0 J K-1 mol-1.
Sol: ∆G⊝ = ∆H⊝ ⊝ ⊝ ⊝
Reaction - T∆SSystem = (-510900) – 298(∆SProducts − ∆SReactants )
∆G⊝ = -510900 – 298[(95) – (2(51.2) + 205)]
∆G⊝ = -510900 – (-63,295.2) = 62,784.3 J mol-1
∆G⊝ = -447,604.8 J mol-1 = -448 kJ mol-1 Reaction is spontaneous.
⊝
∆HReaction = +167.5 kJ mol-1
Ag2CO3(s) → Ag2O(s) + CO2(s)
∆𝑆 ⊝ [Ag2CO3(s)] = 167.4, ∆𝑆 ⊝ [Ag2O(s)] = 121.3, ∆𝑆 ⊝ [CO2(g)] = 213.6 J K-1 mol-1.
⊝
Sol: ∆G⊝ = ∆HReaction - T∆S⊝ ⊝ ⊝
System = (167500) – 298(∆SProducts - ∆SReactants )
∆G⊝ = 167500 – 298(213.6 + 121.3 – 167.4)
∆G⊝ = 167500 – 49,915
∆G⊝ = 117,585 J mol-1 = 118 kJ mol-1. Reaction is not feasible nor spontaneous.
Quick Analysis regarding Temperature and Spontaneity
⊝
∆G⊝ = ∆HReaction - T∆S⊝
System
For Exothermic Reactions: For Endothermic Reactions:

⊝ ⊝
-First, ∆HReaction is negative because energy is released. First, ∆HReaction ispositive because energy is absorbed.
⊝ ⊝ ⊝ ⊝
→ If ∆SSystem < 0, -T∆SSystem is positive. →If ∆SSystem < 0, -T∆SSystem is positive.
⊝ ⊝
-If T is low, -T∆SSystem is small and positive and -If T is low, -T∆SSystem would be small and positive
⊝ ⊝ ⊝ ⊝
∆HReaction -T∆SSystem is more likely to be negative, meaning and ∆HReaction -T∆SSystem is going to be more positive,
⊝
∆G will be negative, and the reaction is spontaneous. meaning ∆G⊝ is positive, and the reaction is spontaneous.
⊝ ⊝
-If T is high, -T∆SSystem would be large and positive and -If T is high, -T∆SSystem is high and positive and
⊝ ⊝ ⊝ ⊝
∆HReaction -T∆SSystem is positive, meaning ∆G⊝ is positive, HReaction -T∆SSystem is positive, meaning ∆G⊝ is positive,
and the reaction is less likely to be spontaneous. and the reaction is non-spontaneous.
⊝ ⊝ ⊝ ⊝
→If ∆SSystem > 0, -T∆SSystem is negative. → If ∆SSystem > 0, -T∆SSystem is negative.
⊝ ⊝
- If T is low, -T∆SSystem is small and negative and -If T is low, -T∆SSystem is small and negative and
⊝ ⊝ ⊝ ⊝
∆HReaction -T∆SSystem is negative, meaning ∆G⊝ will be HReaction -T∆SSystem is more likely to be positive, meaning
negative and the reaction is spontaneous. ∆G⊝ is positive, and reaction is less spontaneous.
⊝
-If T is high, -T∆SSystem is high and negative and ⊝
-If T is high, -T∆SSystem is high and negative and
⊝ ⊝
HReaction -T∆SSystem is going to be negative, meaning ∆G⊝ ⊝ ⊝
∆HReaction -T∆SSystem is more likely to be negative,
is negative and the reaction is spontaneous. meaning ∆G⊝ is more likely to be negative, so the
reaction is more and more spontaneous.
Gibbs Free Energy of Reactions and their Directions
∆G⊝
Reaction
Reactants
Products
∆G⊝
Reactants
Hess’ Law Curve ∆G⊝
Product
⊝
Remember that the value for ∆Gf is
Elements in their 0 for an element in its standard
Standard States state, because an element has no
reaction that solely produces it.
Standard Gibbs Free Energy Change of Reaction: The Gibbs free energy when the amounts
of the reactants shown in the stoichiometric equation react under standard conditions to give
products. The reactants and products must be in their standard states.
It can also be a measure of how stable a compound is, where the more negative the
∆G⊝ Reaction
value, the more stable the compound is. It is also a measure of the feasibility of
a reaction, where the more negative the ∆G⊝
Reaction
value is, the more feasible a reaction is.
Standard Gibbs Free Energy Change of Formation: The standard Gibbs free energy of
formation ∆G⊝ f
of a compound is the change of Gibbs Free Energy that accompanies the
formation of 1 mole of a substance in its standard state from its constituent elements in
their standard states.
1-Calculate the standard Gibbs Free Energy change of reaction in the reaction given below.
NH4NO3(s) → N2O(g) + 2H2O(l)
∆G [NH4NO3(s)] = -184 kJ mol , ∆G⊝ [N2O(g)] = +104.2 kJ mol-1, ∆G⊝ [H2O(l)] = -273.2 kJ mol-1
⊝ -1
Sol: ∆G⊝
Reaction
= ∆G⊝
Products
- ∆G⊝
Reactants
→ ∆G⊝
Reaction
= [(104200) + 2(-273200)] – (-184000)
∆G⊝
Reaction
= -258200 J mol-1 = ∆G⊝
Reaction
= -258 kJ mol-1. Reaction is spontaneous.
2- Calculate the standard Gibbs Free Energy change of reaction in the reaction given below.
3Mg(s) + Fe2O3(s) → 3MgO(s) + 2Fe(s)
∆G [Fe2O3(s)] = -742.2 kJ mol-1, ∆G⊝ [MgO(g)] = -569.4 kJ mol-1
⊝
Sol: ∆G⊝
Reaction
= ∆G⊝Products
- ∆G⊝
Reactants
→ ∆G⊝
Reaction
= [3(-569400) + 2(0)] – [3(0) + (-742200)]
∆G⊝
Reaction
= -966000 J mol-1 = -966 kJ mol-1. Reaction is spontaneous.
3- Calculate the standard Gibbs Free Energy change of reaction in the reaction given below.
3CO2(g) + 4H2O(l) → C3H8(g) + 5O2(g)
∆G [CO2(g)] = -394.4 kJ mol-1, ∆G⊝ [H2O(g)] = -273.2 kJ mol-1, ∆G⊝ [C3H8(g)] = -23.4 kJ mol-1
⊝
Sol: ∆G⊝
Reaction
= ∆G⊝Products
- ∆G⊝
Reactants
→ ∆G⊝
Reaction
= (-23400) – [3(-394400) + 4(-273200)]
∆G⊝
Reaction
= 2252600 J mol-1 = 2.25 × 106 kJ mol-1 = 2.25 × 103 kJ mol-1. Reaction is spontaneous.
Reaction is deemed
Reaction is deemed non-
complete for anything left
∆G⊝ = 0 means feasible for anything right
of red zone. Reaction
reaction is in equilibrium. of green zone.
-∞ Products Override Reactants override ∞

24-Electrochemistry
24.1-Electrolysis
Electrolysis: Chemical decomposition of compounds by the passage of direct electric current

into its constituent elements.
Electrolyte: The compound to be decomposed, whether it’s a molten ionic compound or a
concentrated solution of aqueous ions.
Electrodes: Rods that conduct the electricity in the electrolyte. They are generally made up
of inert conductive materials like graphitic carbon or platinium. The positive electrode is
called the anode (because it attracts anions) and the negative electrode is called the cathode
(because it attracts cathode).
Reduction occurs at the cathode, and oxidation occurs at the anode.
Factors affecting the nature of compounds generated by electrolysis

1-State of the electrolyte:
Molten Electrolytes Aqueous Electrolytes
If an electrolyte is molten, then the cation will If an electrolyte is aqueous, then either the cation
move to the cathode (negative cathode) and the will move the cathode, or hydrogen gas will be
anion will move to the anode (positive electrode). generated there depending on where the ion lies in
Example: AgCl(l) will dissociate into Ag(s) into the redox series. As for the anode, oxygen gas
the cathode and Cl2(g) in the anode. will be generated unless a halide ion is present.
2-Position of the ion in the redox series:
Lithium Li(s) → Li+(aq) + e- Nickel Ni(s) → Ni2+ (aq) + 2e- In aqueous solutions, if the
Increase in the ease of discharge
Increase in the ease of discharge
Potassium K(s) → K+(aq) + e- Tin Sn(s) → Sn2+ (aq) + 2e- cation comes under hydrogen in
Barium Ba(s) → Ba2+ (aq) + 2e- Lead Pb(s) → Pb2+ (aq) + 2e- the redox series, then the ion is
Calcium Ca(s) → Ca2+(aq) + 2e- Hydrogen H2(g) → 2H+(aq) + 2e- going to be deposited at the
Sodium Na(s) → Na+(aq) + e- Copper Cu(s) → Cu2+(aq) + 2e-
cathode.
Decrease in ease of discharge
Magnesium Mg(s) → Mg2+(aq) + 2e- Silver Ag(s) → Ag+(aq) + e-

OH-(aq)
Aluminium Al(s) → Al3+(aq) + 3e- Mercury Hg(s) → Hg2+(aq) + 2e-
Manganese Mn(s) → Mn2+ (aq) + 2e- Platinium Pt(s) → Pt2+(aq) + 2e- I-(aq)
Zinc Zn(s) → Zn2+ (aq) + 2e- Gold Au(s) → Au2+(aq) + 2e- Br-(aq)
Chromium Cr(s) → Cr3+ (aq) + 3e- Cl-(aq)
Iron Fe(s) → Fe2+ (aq) + 2e- NO3-(aq)
Cobalt Co(s) → Co2+ (aq) + 2e- SO42-(aq)
3-Concentration of the ion in the electrolyte:

The concentration of a given ion can alter the preferential ease of discharge. If the
concentration of an ion is relatively high, then it is more likely to be discharged. For
example, in conc. NaCl(s), Na would be deposited in the cathode not H2.
Faraday Constant and the Avogadro Constant
Faraday Constant, F: 1 Faraday is the amount of electric charge carried by 1 mole of

electrons or 1 mole of singly charged ions. 1F = 9.65 × 104 C mol-1.
The mathematical analogue of the definition is F = Le, where L is the Avogadro Constant
and e is the elementary charge.
Electric Current: Rate of flow of electric charge. Therefore, Q = It, where Q is the electric
charge and t is the passage time of the electric charge. It’s unit is the ampere, A.
Quantitative Electrolysis
We can calculate the amount of material deposited at the electrodes using the amount of
charge that passes through an electrolyte and combining it with the concept of a faraday
constant.
How to find the amount that deposits on the electrodes?

Step-1: Write the half equation related to the material concerned with the question.
Step-2: Find the amount of charge per mole by multiplying the coefficient behind e - with F.
Step-3: Find the amount of charge that passed in the given amount of time using Q = It.
Step-4: Divide the charge passed by the charge in step-2 and multiply by the molar mass
of the element.
1-Calculate the mass of silver deposited at the cathode during electrolysis when a current of 1.80A flows
through an aqueous solution of silver nitrate for 45.0min where the molar mass of silver = 108
Solution: Ag+(aq) + e- → Ag(s)
For 1 mole of Ag+(aq), 1 mole of e- is added. Therefore, 1 × F = 96500.
Charge passed Q = 1.80 × 45 × 60 = 4860.
4860
Mass of silver = × 108 = 5.44g of Ag(s).
96500
2-Calculate the volume of oxygen produced at R.T.P. when a concentrated aqueous solution of sodium
sulfate is electrolysed for 55.0min using a current of 0.70A.
Solution: 4OH-(aq) → O2(g) + 2H2O(l) + 4e-
For 1 mole of O2-(aq), 4 moles of e- is added. Therefore, 4 × F = 386000
Charge passed Q = 0.70 × 55 × 60 = 2310
2310
Volume of Oxygen = × 24.0 dm3 = 0.143 dm3.
386000
Experiments to estimate the value of the Avogadro Constant
General Procedure:
-Weigh both electrodes before the experiment and note their weight. A
-Use a variable resistor to maintain a constant current, and switch on
a d.c. supply and note down the time for which the supply is on.
-Remove the electrodes and reweigh them after washing and dry them.
Calculation: Copper Copper
Let the current be 0.20A for 34 minutes and the decrease in the mass Anode cathode
of the anode be 0.13g.
The charge passed Q = 0.20 × 34 × 60 = 408 C. If it takes 408C to
63.5 1
deposit 0.13g, then it would take × 408 × to make 1 mole
0.13 2
because 2 moles of e- to create 1 mole Cu(s) and the molar mass of Cu
is 63.5. It would take 99600 C. Copper (II) Sulfate
Solution
We’ll now use the F =Le relation.
99600
L= -19 = 6.2 × 10
23 mol-1.
1.6×10
24.2-Standard Electrode Reduction Potentials E⊝ , Standard Cell Potentials E⊝

Cell
and the Nernst Equation
Standard Electrode Potential, E⊝ : The standard electrode potential for a half-cell is the
voltage measured under standard conditions with a standard hydrogen electrode as the
other half-cell, where the standard conditions entail an ion concentration of 1.00 mol dm-3,
a temperature of 298 K and a pressure of 105 Pa. Its unit is volts.
What does the E⊝ definition mean?

Explanation: If I place a copper rod in contact with a copper (II) sulfate solution, the
copper in the rod will dissociate and get oxidized into copper ions and the copper ions
from the CuSO4 solution will deposit by reduction into the copper rod, and, hence creating
a redox equilibrium that starts when the forward and backward rates are equal.
Cu2+(aq) + 2e- ⇌ Cu(s). This specific equilibrium lies further over to the right due to the
relative inertness of copper in the redox series. The electric potential build-up between the
metal and metal ion solution is what leads to the voltage. We cannot directly measure this
potential, but we can compare the system’s potential to another system. 2+ Copper (II) ions
2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ Copper Rod
Electron charge build-up
2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ Electric Potential
Standard Hydrogen Electrode: A reference electrode used to gauge the electrode potential
of other half-cells using hydrogen as a reference element. It’s standard electrode potential
value is 0.00 V. Here’s a diagram and an explanation for how it works:
Platinium wire H2(g) gas in,

The system consists of 105 Pa H2(g) that is 105 Pa and
in equilibrium with 1.00 mol dm-3 H 298K
solution that are in contact with each other
using a platinium electrode coated with fine
“platinium black” to form a quick
equilibrium between H2(g) and H+.
The half equation redox equilibrium
Glass hole for H2(g) Platinium
should be: bubbles to escape Electrode
2H+(aq) + 2e- ⇌ H2(g)
H+, 1.00 mol dm-3
What do E⊝ values mean in terms of being positive or negative?
1-Species with higher oxidation numbers are always on the left, they are always reactants not products.
Explanation: Remember that E⊝ refers to a reduction reaction, so electrons will always be on the left of
the equilibrium, and we only add electrons to a positive ion to reduce. Example:
Zn2+(aq) + 2e- ⇌ Zn(s)
2-As E⊝ → +∞ for a specific element, then the element is going to be more and more unreactive, it is
going to be easier and easier to reduce its ions and it’s going to be a worse and worse reducing agent.
Example: Na(s)/Na+(aq) half cells have a E⊝ = -2.71V, but Ag(s)/Ag(aq)+ half cells have a
E⊝ = +0.80V. This means that Ag is more unreactive, Ag+(aq) ions are easier to reduce and Ag as an
element is a worse reducing agent when compared to Na.
3-As E⊝ → -∞ for a specific element, then the element is going to be more and more unreactive, it is going
to be easier and easier to oxidise its ions and it’s going to be a worse and worse oxidizing agent.
Example: Mg(s)/Mg2+(aq) half cells have a E⊝ = -2.38V, but Pb(s)/Pb4+(aq) half cells have a
E⊝ = +1.69V. This means that Mg is more reactive, Mg2+(aq) ions are harder to reduce and Mg as an
element is a worse and worse oxidizing agent compared to Pb(IV).
How to measure standard electrode reduction potentials?
0.34V
1-Metal/metal ion half-cell system.
We’ll connect a Cu(s)/Cu2+(aq) half-cell to a standard
hydrogen electrode via a salt bridge to complete a
circuit and a metal wire connecting the two cells to a
high-resistance voltmeter to measure the potential
difference. A salt bridge can be made by soaking a Copper Rod
filter paper in saturated KNO3(aq). Salt Bridge
Cu2+(aq) + 2e- ⇌ Cu(s) E⊝ = 0.34V
2H+(aq) + 2e- ⇌ H2(g) E⊝ = 0.00V
Because the reading is positive, copper rod is the anode
and platinum wire is the cathode because the
Cu(s)/Cu2+(aq) half-cell is more likely to gain e-. The
electrons move from the negative electrode to the Cu Cu2+, 1.00 mol dm-3 H+, 1.00 mol dm-3
rod. The E⊝ value shows that Cu2+(aq) is easier to 298K
reduce compared to H+(aq).
0.76V
We’ll connect a Zn(s)/Zn2+(aq) half-cell to a standard

high-resistance voltmeter to measure the potential Zinc Rod
difference. A salt bridge can be made by soaking a Salt Bridge
filter paper in saturated KNO3(aq).
Zn2+(aq) + 2e- ⇌ Zn(s) E⊝ = -0.76V
2H+(aq) + 2e- ⇌ H2(g) E⊝ = 0.00V
Because the reading is negative, zinc rod is the cathode
and platinum wire is the anode because the
Zn(s)/Zn2+(aq) half-cell is more likely to lose e-. The
Zn2+, 1.00 mol dm-3 H+, 1.00 mol dm-3
electrons move from the zinc electrode to the platinium
298K
wire. The E⊝ value shows that Zn2+(aq) is harder to
2-Non-metal/Non-metal ion half-cells 1.36V
We’ll connect a Cl(g)/Cl-(aq) half-cell to a standard
hydrogen electrode via a salt bridge to complete a Cl2(g),
circuit and a metal wire connecting the two cells to a 105
high-resistance voltmeter to measure the potential Pa
difference. A salt bridge can be made by soaking a
filter paper in saturated KNO3(aq). Salt Bridge
Cl2(aq) + 2e- ⇌ 2Cl-(s) E⊝ = +1.36V
2H+(aq) + 2e- ⇌ H2(g) E⊝ = 0.00V
Because the reading is positive, chlorine gas is the
anode and platinum wire (H2(g)) is the cathode
because the Cl(g)/Cl-(aq) half-cell is more likely to gain
e-. The electrons move from the hydrogen electrode to
Cl-, 1.00 mol dm-3 H+, 1.00 mol dm-3
the chlorine. The E⊝ value shows that Cl-(aq) is easier
298K
to reduce compared to H+(aq).
We’ll connect a S(s)/S2-(aq) half-cell to a standard 0.51V

high-resistance voltmeter to measure the potential
difference. A salt bridge can be made by soaking a
filter paper in saturated KNO3(aq).
S(s) + 2e- ⇌ S2-(s) E⊝ = +0.51V
2H+(aq) + 2e- ⇌ H2(g) E⊝ = 0.00V Salt Bridge
Because the reading is positive, sulfur is the anode
and platinum wire (H2(g)) is the cathode because the
S(s)/S2-(aq) half-cell is more likely to gain e-. The
electrons move from the hydrogen electrode to the
sulfur. The E⊝ value shows that S2-(s) is easier to Sulfur
S2-, 1.00 mol dm-3 H+, 1.00 mol dm-3
298K
3-Half-cells with ions of the same species with different oxidation states.
Fe2+(aq)/Fe3+(aq) half-cell 0.77V

We can have a half-cell with a single species but
multiple oxidation numbers. In this half-cell:
Fe3+(aq) + e- ⇌ Fe2+(aq) E⊝ = +0.77V
This type of cell can be used to determine the electrode 298K
potential when adding electrons to a specie of an element
to make the same specie with a different oxidation
number. Salt Bridge
Both ion species must be of standard concentration in the
same container.
Fe2+, 1.00 mol dm-3 H+, 1.00 mol dm-3

Fe3+, 1.00 mol dm-3
MnO4-(Aq)/Mn2+(aq) half-cell
This is an example of an ion half-cell where multiple
1.52V
species of ions are involved, in this case: H+(aq),
MnO4-(aq) and Mn2+(aq). All of them must have
standard equal concentration.
MnO4-(aq) + 8H+(aq) + 5e- ⇌ Mn2+(aq) + 4H2O(l) 298K
MnO4-(aq) is more likely to accept electrons compared to
H+(aq), therefore it is easier to reduce compared to
H+(aq). Therefore, MnO4-(aq) is a poor reducing agents. Salt Bridge
The E⊝ value for the redox equilibrium for the MnO4-
(aq)/Mn2+(aq) is +1.52V.
Mn2+, 1.00 mol dm-3 H+, 1.00 mol dm-3

MnO4-(aq), 1.00 mol dm-3
H+, 1.00 mol dm-3
Q-Show how you would measure the E⊝ value for the half-cell of: ???V
VO2+(aq) + 2H+(aq) + e- ⇌ V3+(aq) + H2O(l)
Solution: Connect a standard hydrogen electrode to a half-cell containing
1.00 mol dm-3 VO2+(aq) and 1.00 mol dm-3 H+(aq).
Make sure the standard hydrogen electrode has H2(g) circulating in 298K
under 105 Pa.
Both cells must be connected by a filter paper soaked in saturated
Salt Bridge
KNO3(aq) solution, known as a salt bridge between both containers and it
must be touching the solutions. Both platinium electrode wires must
be connected to a high-resistance voltmeter.
In the container with VO2+(aq) and H+(aq), and e- was added to
that side of the equation, and the electron did not come from the
container, so the electron must have come from the standard
hydrogen cell. This means that the VO2+(aq) container is the VO22+, 1.00 mol dm-3 H+, 1.00 mol dm-3
anode, and the hydrogen electrode is the cathode. This means H+, 1.00 mol dm-3
that whatever the reading is, its sign is positive.
Standard Cell Potential

Standard Cell Potential ECell : The cell potential, ECell, is the measure of the potential
difference between two half cells in an electrochemical cell. ECell is calculated by subtracting
the less positive E⊝ from the more positive E⊝ values. Example:
Na+(aq) + e- ⇌ Na(s) E⊝ = -2.71V
Ni2+(aq) + 2e- ⇌ Ni(s) E⊝ = -0.25V
ECell = -0.25V – (-2.71V) = 2.46V
Example 2: A cell has one Cu(s)/Cu2+(aq) half-cell and one Fe2+(aq)/Fe3+(aq) half-cell. The
electrode potential for the Cu(s)/Cu2+(aq) is +0.34V and the electrode potential for the
Fe2+(aq)/Fe3+(aq) is +0.77V.
a) Calculate the standard cell potential for the cell.
Solution: ECell = 0.77 – 0.34 = 0.43V.
b) Which of the two poles is the positive pole?
Solution: The half-cell with the more positive value is always going to be the positive pole,
so the Fe2+(aq)/Fe3+(aq) half-cell is the positive pole.
c)Find the direction of motion of the electrons.
Solution: Electrons will always move from the negative pole to the positive electrode, so
electrons move from the Cu(s)/Cu2+(aq) to the Fe2+(aq)/Fe3+(aq).
E⊝ values and Reaction Feasibility
For redox equilibrium reactions, we arrange the specie with the highest oxidation number on
the reactant side and the specie with the lower oxidation number on the product side.
Therefore, these reactions are always set up as reduction reactions.
⊝
We know that as E values increase, the oxidizing power of the reactant specie and their
⊝
tendency to gain electrons increases. Therefore, as E increases, the tendency of the
⊝
equilibrium to proceed forward increases, and as E decreases, the tendency of the reaction
to move in the reverse direction increases.
⊝
If the tendency of the reaction moves forward increases if the E increases, the ease of the
reduction of the reactant specie increases, and if the tendency of the reaction moves in reverse
⊝
increases if the E decreases, the ease of reduction of the reactant specie decreases.
⊝
Example: Ag+(aq) + e- ⇌ Ag(s) has a E of +0.80V, so the reaction has a tendency to move
⊝
forwards instead of in reverse. Fe3+(aq) + 3e- ⇌ Fe(s) has a E of -0.04V, so the reaction has
a tendency to move in reverse direction instead of forwards.
Therefore, if there is an electrochemical cell where one half-cell is an Fe3+(aq)/Fe(s) and the
other half-cell is a Ag+(aq)/Ag(s), and we know that one reaction is proceeding as
Ag+(aq) + e- → Ag(s) and the other reaction is proceeding as Fe(s) → Fe3+(aq) + 3e- then the
overall reaction is: 3Ag+(aq) + Fe(s) → Fe3+(aq) + Ag(s) by adding both reactions. This is a
feasible reaction, but the reverse reaction is non-feasible.
Q1-Will chlorine oxidise Fe2+ into Fe3+?

Sol: First write the equations involving the elements in the question:
⊝
Cl2(g) + 2e- ⇌ 2Cl-(aq) E = +1.36V
⊝
Fe3+(aq) + e- ⇌ Fe2+(aq) E = +0.77V
By the given values, Cl2(g) is a better oxidizing agent and Fe3+(aq) is a better reducing agent,
⊝
and the less positive E makes the second reaction more likely to go in reverse.
The probable reactions: Cl2(g) + 2e- → 2Cl-(aq) and Fe2+(aq) → Fe3+(aq) + e-, therefore:
Cl2(g) + 2Fe2+(aq) → 2Cl-(aq) + 2Fe3+(aq), which is the overall reaction showing oxidation of
Fe2+ into Fe3+. So, the reaction proposed by the question is feasible.
Q2-Will hydrogen peroxide, H2O2, reduce acidified manganate (VII) ions, MnO4-(aq) to
Mn2+(aq) ions?
Solution: Write down the relevant equations from the data booklet:
⊝
MnO4-(aq) + 8H+(aq) + 5e- ⇌ Mn2+(aq) + 4H2O(l) E = +1.52V
⊝
O2(g) + 2H+(aq) + 2e- ⇌ H2O2(aq) E = +0.68V
⊝
The first equilibrium has a better oxidizing power due to higher E so the reaction moves
⊝
forward and the second equilibrium has a better reducing power due to a lower E so the
reaction moves in the reverse direction. The probable reactions:
MnO4-(aq) + 8H+(aq) + 5e- → Mn2+(aq) + 4H2O(l) and H2O2(aq) → O2(g) + 2H+(aq) + 2e-
Overall: 2MnO4-(aq) + 6H+(aq) + 5H2O2(aq) + 10e- → 2Mn2+(aq) + 8H2O(l) + 5O2(g)
The similar H+(aq) and e- are cancelled from each side. The reaction is feasible.
There’s an easier way to determine the feasibility of a reaction by adding the appropriate
⊝
reaction electrode potential and: If E > 0, the reaction is feasible.
Q3-Can H+(aq) oxidise V2+(aq) to V3+(aq)?

⊝
Solution: 2H+(aq) + 2e- ⇌ H2(g) E = 0.00V
⊝
and V3+(aq) + e- ⇌ V2+(aq). E = -0.26V
Less positive reaction will go in the reverse direction: V2+(aq) → V3+(aq) + e-
⊝
Probable reactions: 2H+(aq) + 2e- ⇌ H2(g) E = 0.00V
⊝
V2+(aq) ⇌ V3+(aq) + e- E = +0.26V (Reverse direction = reverse charge)
⊝
Add both E values: +0.26V, because the value is positive, the reaction is feasible.
Q4-Can MnO4-(aq) ions oxidise F-(aq) into F2(g) in acidic conditions?

⊝
Solution: MnO4-(aq) + 8H+(aq) + 5e- ⇌ Mn2+(aq) + 4H2O(l) E = +1.52V
⊝
F2(g) + 2e- ⇌ 2F-(aq) E = +2.87V
Less positive reaction moves in reverse: MnO4-(aq) + 8H+(aq) + 5e- ⇌ Mn2+(aq) + 4H2O(l)
⊝
Probable reactions: F2(g) + 2e- ⇌ 2F-(aq) E = +2.87V
⊝
Mn2+(aq) + 4H2O(l) ⇌ MnO4-(aq) + 8H+(aq) + 5e- E = -1.52V (Reverse charge)
⊝
Add both E values: 2.87V + (-1.52V) = 1.35V, because the value is positive, the reaction is
feasible.
Relationship between E⊝ values and ion concentration
⊝
Fe2+(aq) + 2e- ⇌ Fe(s) E = -0.44V
Redox equilibrium reactions are still equilibrium reactions, so Le Chatelier’s equilibrium
principle regarding temperature, pressure and concentration still applies.
If we increase the Fe2+ concentration from the standard 1.00 mol dm-3, the equilibrium shifts
to the right because the system will try to reduce the concentration of Fe2+ back to standard.
⊝
Because the reaction goes to the right, the E value would become more positive.
If we increase the Fe(s) concentration from the standard 1.00 mol dm-3, the equilibrium
shifts to the left because the system will try to reduce the concentration of Fe (s) back to
⊝
standard. Because the reaction goes to the left, the E value would become more negative.
If we increase both concentrations equally, nothing happens because the effects cancel out.
⊝
When ion concentration is varied, the conditions are no more standard and the E values will
be altered. A good indicator for the feasibility of a reaction in non-standard conditions is
⊝
that the difference between the E values for both half-equations must be > 0.30V. If the
difference is < 0.30V, then generally no reaction would occur, but anomalous results might
occur.
⊝
Q1-The half-cell Cr2O72- + 14H+ + 6e- ⇌ 2Cr3+ + 7H2O has an E value of +1.33V
a) What happens when the [Cr2O72-] increases?
⊝
Solution: Equilibrium shifts to the right, so the E increases.
b) What happens when [H+] decreases?
⊝
Solution: Equilibrium shifts to the left, so the E decreases.
c) What happens when the [Cr3+] increases?
⊝
Solution: Equilibrium shifts to the left, so the value of E decreases.
d) What conditions would ensure the C2O72- solution has more and more oxidizing power?
Solution: Increase the concentration of C2O72-, increase the concentration of H+, decrease the
concentration of Cr3+, decrease the concentration of H2O in the system.
e) Explain your answer to part d using Le Chatelier’s principle.
Solution: If you increase the concentration of a reactant, the equilibrium shifts to the right to
regain standard conditions. If you decrease the concentration of a product, the equilibrium
shifts to the left to regain standard conditions.
The Nernst Equation
In non-standard conditions where the temperature and the concentration of the ion present in
the half-cell are not 298K and 1.00 mol dm-3, the Nernst equation can help you deduce the
value for the electrode potential in a non-standard half-cell.
RT [Oxidised Form]
E = E⊝ + ln
zF [Reduced Form]
⊝
Where E is the standard electrode potential of the half-cell, R is the molar gas constant
with a value of 8.314 J K-1 mol-1, T is the thermodynamic temperature of the experiment, z
is the number of electrons transferred during the experiment, F is the Faraday constant with
a value of 9.65 × 104 C mol-1, [Oxidised form] is the concentration of the oxidised specie,
and [Reduced form] is the concentration of the reduced specie. Just math.
Q1-Calculate the value of the electrode potential at 298K of an Ni(s)/Ni2+(aq) half-cell that
has a Ni2+(aq) concentration of 1.5 mol dm-3 and an E⊝ of -0.25V
Solution: Ni2+(aq) + 2e- ⇌ Ni(s). For 1 mol Ni(s), 2 mol e- are required.
8.314 × 298 1.5
E = -0.25 + ln = -0.2447949792806955V
2 × 96500 1
E = -0.24V
Q2-Calculate the electrode potential values of an Ag(s)/Ag+(aq) at 0℃ when the

concentration of Ag+(aq) ions is 0.0002 mol dm-3 and E⊝ = +0.80V
Solution: Ag+(Aq) + e- ⇌ Ag(s). For 1 mol of Ag(s), 1 mol of e- is required.
8.314 × 273 0.0002
E = +0.80 + ln = +0.599671909172V
1 × 96500 1
E = +0.60V.
Q3-Calculate the electrode potential E of an Sn4+(aq)/Sn2+(aq) half-cell where the [Sn4+] =

0.300 mol dm-3 and the [Sn2+] = 0.150 mol dm-3 at 298K. Use the data booklet to
determine the standard electrode potential of an Sn4+(aq)/Sn2+(aq) half-cell
Solution: Sn4+(aq) + 2e- ⇌ Sn2+(aq). For 1 mol of Sn2+(aq), 2 mols of e- is required.
Sn4+(aq) + 2e- ⇌ Sn2+(aq) E⊝ = +0.15V
8.314 × 298 0.300
E = +0.15 + ln = +0.1588980416913692
2 × 96500 0.150
E = +0.16V.
Gibbs Free Energy and Standard Cell Potential
We know from the previous chapter that the ∆G is basically the maximum amount of free
energy in the system that has the ability to do work.
We know that the Faraday Constant F signifies the amount of charge transferred per mole
of electrons, so if we multiply the number of moles of electrons transferred by the faraday
constant, we obtain the total amount of charge transferred.
Total charge transferred = nF, where n is the number of moles of electrons.
Above, we defined the Gibbs Free Energy to be ∆G = Wmax, where Wmax is maximum work
done. In terms of electricity, work done is equivalent to total charge transferred multiplied
by the potential difference, or W = QV. This means that the work done by the electrochemical
cell is given by the product of the total charge transferred and the cell potential.
We know that if electrochemical reactions are feasible, ∆G < 0 and Ecell > 0, so we have to
add a negative sign in the expression.
⊝
So, the Gibbs Free energy ∆G = -nFECell .
Q1-When a zinc strip is dropped in a CuSO4(aq) solution, Cu2+(aq) deposits on the strip
and Zn(s) dissociates into Zn2+(aq).
⊝
a) Calculate the standard cell potential ECell .
Solution: Cu2+(aq) + 2e- ⇌ Cu(s) E⊝ = +0.34V
Zn2+(aq) + 2e- ⇌ Zn(s) E⊝ = -0.76V
⊝
ECell = 0.34 – (-0.76) = 1.10V
b) Calculate the Gibbs Free Energy and determine whether the reaction is spontaneous or not.
⊝
Solution: ∆G = -nFECell = -2 × 96500 × 1.1 = -212300 J mol-1 = -212 kJ mol-1.
Because the Gibbs Free energy is negative, the reaction is spontaneous.
Q2-An Al3+(aq)/Al(s) half-cell is connected to a Cu2+(aq)/Cu(s) half-cell. Calculate the Gibbs

Free Energy for the reaction in which Al(s) reduces Cu2+(aq) ions.
Solution: 2Al(s) + 3Cu2+(aq) + 6e- → 2Al3+(aq) + 3Cu(s) + 6e-
Al(s) → Al3+(aq) + 3e- E⊝ = +1.66V
Cu2+(aq) + 2e- → Cu(s) E⊝ = +0.34V
ECell = 1.66 + 0.34 = 2.00V
⊝
∆G = -nFECell = -6 × 96500 × 2 = -1158000 J mol-1 = -1.16 × 106 J mol-1
= -1.16 × 103 kJ mol-1. Reaction is feasible.
25-Equilibria
25.1-Acids and Bases
Conjugate Acid: A conjugate acid is a chemical compound formed when an acid donates a
proton (H+) to a base.
Conjugate Base: A conjugate base is what is left over after an acid has donated a proton
(H+) during a chemical reaction.
HNO3(aq) + H2O(l) → H3O+(aq) + NO3-(aq)
Acid Base Conjugate Acid Conjugate Base
Conjugate Acid-Base Pairs: An acid and a base which differ only by the presence or
absence of a proton are called a conjugate acid-base pair. NH3 is the conjugate base of
NH4+ and NH4+ is the conjugate acid of NH3. They are both a conjugate acid-base pair.
Q1-CH3NH2 is known as methylamine, and it is a weak base. Find the chemical formula of
its conjugate acid.
Solution: To make an acid from a base, add a proton (H +), therefore the conjugate acid is
CH3NH3+.
Q2-Find the conjugate acid and the pair of the hydrogen carbonate ion, HCO3-(aq).
Solution: Conjugate acid = H2CO3. Conjugate Base = CO32-.
Mathematical definition of pH values
pH: pH is defined as the negative logarithm to the base 10 of the hydrogen ion concentration.
This is written as pH = -log10 [H+]
Q1-Calculate the pH of a solution with H+ concentration of 3.00 × 10-4 mol dm-3.

Solution: pH = -log(3.00 × 10-4) = 3.522878 = 3.52
Q2-Calculate the H+ concentration if a solution has a pH of 9.11.

Solution: 9.11 = -log[H+] → 10-9.11 = [H+]
Use the P3 logarithmic rules
[H+] = 7.76 × 10-10 mol dm-3.
in chapter 2
Mathematical definition of Ka, the acid dissociation constant.
Acid dissociation constant: The acid-dissociation constant, Ka, is a quantitative measure of

the strength of an acid in solution. It is basically an equilibrium constant (remember Kc)
for the equilibrium reaction of the breakdown of an acid into an H+ proton and a negative
ion.
[H+ ][A- ]
HA(aq) ⇌ H+ (aq) + A- (aq), where Ka =
[HA]
Example Reaction: CH3CH2CH2COOH(aq) ⇌ CH3CH2CH2COO-(aq) + H+(aq)
[H+ ][CH3CH2CH2COO- ]
Ka =
[CH3CH2CH2COOH]
Q1-Write the equilibrium expression for the following reactions:

a) HCO3-(aq) ⇌ H+(aq) + CO32-(aq)
[H+ ][CO3 2- ]
Solution: Ka = .
[HCO-3 ]
b) NH4+(aq) ⇌ H+(aq) + NH3(aq)
[H+ ][NH3 ]
Solution: Ka = .
[NH+
4]
If Ka values are large, > 1 for example, then the equilibrium lies reliably to the right.
If Ka values are small, < 0.01 for example, then the equilibrium lies reliably to the left.
If the 0.01 < Ka < 1, then the equilibrium is in relatively in equilibrium, with 0 being the
exact point of equilibrium.
Calculating important values for weak acids.

To calculate Ka for a weak acid, you must know the concentration as well as the pH of the
acid.
HA ⇌ H+ + A-
The 1st assumption is to ignore the H+ ions arising from the dissociation of H2O molecules;
therefore, [H+] = [A-]. The 2nd assumption is to make the initial and the final concentration
of the acid equal. This is because, at most, 1% of the acid is dissociated.
2
[H+ ] × [H+ ] [H+ ]
Now when calculating the Ka value, Ka = = .
[HA] [HA]
Q1- Calculate the Ka value for hydrogen cyanide, HCN, which has a concentration 0.10 mol
dm-3 and a pH of 5.10.
Solution: First, find the [H+] from the pH:
5.10 = -log[H+]
[H+] = 10-5.10 = 7.94 × 10-6 mol dm-3.
2 2
[H+ ] [7.94×10-6 ]
Ka = = = 6.39 × 10-10 mol dm-3.
[HCN] 0.10
Mathematical definition of pKa values
pKa: pKa is defined as the negative logarithm of the Ka. We use this because the Ka values
for most acids is extremely small. This is written as pKa = -log[Ka]. If the Ka value > 1,
then the pKa value would be < 0. So pKa could be positive or negative.
Q1-Calculate the pKa value for HF acid dissociation if the Ka value is 5.6 × 10-4 mol dm-3.
Solution: pKa = -log (5.6 × 10-4) = 3.25.
Q2) a) Calculate the Ka for 0.100 mol dm-3 of 2-nitrophenol, which has a pH of 4.10.
Solution: [H+] = 10-4.10 = 7.94 × 10-5 mol dm-3.
2 2
[H+ ] (7.94 × 10-5 )
Ka = = = 6.31 × 10-8 mol dm-8.
[C6 H5 NO3 ] 0.10
b) Calculate the pKa for the part a
Solution: pKa = -log(6.31 × 10-8) = 7.2.
Q3) Calculate the pH of 0.0500 mol dm-3 propanoic acid with Ka of 1.26 × 10-5 mol dm-3.
2
[H+ ] 2
Solution: Ka = → 1.26 × 10-5 × 0.05 = [H+ ]
0.05
+ 2
[H ] = 6.31 × 10-7 → [H+] = 7.94 × 10-4 mol dm-3.
pH = -log(7.94 × 10-4) = 3.10.
Q4) Calculate the pH of a solution of 0.01 mol dm-3 hydrated Al3+ ions if the pKa = 5.00.
Solution: If 5 = -log(Ka), then Ka = 10-5 mol dm-3.
[H+]2 = 0.01 × (10-5)2 = 1 × 10-12.
[H+] = 1 × 10-6 mol dm-3.
pH = -log(1 × 10-6) = 6.00.
The ionic product KW.
In water, the extent of ionization of H2O molecules into H+ ions and OH- is extremely
small. This reaction is written as:
H2O(l) ⇌ H+(aq) + OH-(aq)
[H+ ][OH- ]
The equilibrium constant Kc of this reaction is given by Kc = . The concentration of
[H2 O]
pure water is constant, so we can ignore the denominator.
Kc = [H+] [OH-], but for every dissociation of a water molecule, 1 H+ and 1 OH- is
created. We can assume that [H+] = [OH-], so Kc = [H+][H+] = [H+]2.
This particular equilibrium constant is known as KW, and KW = 1.00 × 10-14 mol2 dm-6 at
105 Pa and 298K. This is the ionic product of water.
2
The concentration of H+ ions in pure H2O therefore is √1.00×10-14 = 1.00 × 10-7 mol dm-3.
We can use the value of KW to calculate the pH of strong acids and bases.
Calculating important values for strong acids and bases.

For strong acids and bases, the acids and bases completely ionise in water. Therefore, the
concentration of H+ in solution is approximately equal to the original concentration of the
acid or the base. Again, we make the assumption that the H+ and OH- ions arising from the
dissociation of H2O itself.
For Strong Acids For Strong Bases
The concentration of the acid is the The concentration of the bases is the
concentration of the H+. Therefore, the concentration of the OH-. We can find the pOH
pH of the acid = -log [HA]. by pOH = -log [OH-]. Then pH = 14 – pOH.
Because 14 is the maximum pH.
Q1-Calculate the pH of 1.00 mol dm-3 HCl.
Solution: [H+] = [HCl] = 1.00 mol dm-3.
pH = -log(1.00) = 0
Q2-Calculate the pH of 0.50 mol dm-3 HNO3.

Solution: [H+] = [HNO3] = 0.50 mol dm-3.
pH = -log(0.5) = 0.30.
Q3-Calculate the pH of 0.001 mol dm-3 KOH.

Solution: [OH-] = [KOH] = 0.001 mol dm-3.
pOH = -log (0.001) = 3. pH = 14 – 3 = 11.
Q4-Calculate the pH of an aqueous solution containing 0.200g of NaOH per dm-3.
0.2
Solution: Mol[NaOH] = = 0.005 mol.
23 + 16 + 1
Therefore, concentration = 0.005 mol dm-3.
[OH-] = [NaOH] = 0.005 mol dm-3.
pOH = -log(0.005) = 2.3010299956639811952137388947245.
pH = 14 - 2.3010299956639811952137388947245 = 11.7
Buffer Solutions
Buffer Solution: A buffer solution 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.
Buffer solutions are used as a means of keeping pH at a nearly constant value in a wide
variety of chemical applications.
Buffer solutions can be made by mixing appropriate amounts of weak acids and one of
their salts, or weak alkalis and one of their salts. Depending on the amount of the weak acid
or alkali included, the buffer solution can be either used to maintain acidic or alkaline pH.
A common example of a buffer solution is a mixture of sodium ethanoate, CH3COOHNa,

and ethanoic acid CH3COOH.
An explanation of how this works: The sodium salt dissociates into Na+ & CH3COO-. The
concentration of CH3COOH determines the pH of the buffer. Because the CH3COOH is aq:
CH3COOH(aq) ⇌ CH3COO-(aq) + H+(aq)
The reason we use the salt is to ensure that there is a large reserve supply of CH 3COO-(aq).
What happens when there is an excess of acidity in the What happens when there is a decrease in acidity in the
buffer solution? buffer solution?
-Because acidity increases, H+ concentration increases. -Because acidity decreases, H+ concentration decreases.
-The concentration of H+ increases, so the equilibrium -The concentration of H+ decreases, so the equilibrium
shifts to the left to make more CH3COOH until shifts to the right to make more H+ and CH3COOH
equilibrium is restarted again. until equilibrium is restarted again.
-There is a large reserve of CH3OO-(aq) from the -There is a large reserve of CH3OO-(aq) from the
dissociation of the sodium salt, so the CH3COO- dissociation of the sodium salt, so the CH3COO-
concentration remains the same. concentration remains the same.
-There is a large reserve of CH3COOH(aq) from the -There is a large reserve of CH3COOH(aq) from the
initial ethanoic acid, so the CH3COOH(aq) initial ethanoic acid, so the CH3COOH(aq) concentration
concentration remains the same. remains the same.
-Because there isn’t much change in the reactant and -Because there isn’t much change in the reactant and
product concentration, so pH doesn’t change. product concentration, so pH doesn’t change.
Practical Uses of Buffer Solutions
In the human body, the blood pH is kept in a specific range with several buffer solutions
within the blood like HCO3-(aq) – CO2(aq), haemoglobin proteins, H2PO4-(aq) – HPO42-(aq).
The metabolic reaction that releases energy also produces CO2, that dissolves in H2O in the
blood to produce carbonic acid, H2CO3(aq). H2CO3(aq) is a weak acid, so it dissociates into
ions. The reaction is: H2CO3(aq) ⇌ H+(aq) + HCO3-(aq).
If the H+ concentration increases, the equilibrium shifts to the left to decrease the H+(aq)
concentration to restart equilibrium. The restoration of equilibrium will keep the pH
constant.
If the H+ concentration decreases, the equilibrium shifts to the right to increase the H+(aq)
and HCO3- concentrations to restart equilibrium. The restoration of equilibrium will keep the
pH constant.
Q1-A buffer in blood plasma is a mixture of dihydrogenphosphate ions, H2PO4-(aq), and

hydrogenphosphate, HPO42-(aq), ions.
a) Identify the base and the conjugate acid in this buffer solution
Solution: H2PO4-(aq) is the conjugate acid, and HPO4-(aq) is the base.
b) Write down the balanced equilibrium equation between these ions.
Solution: H2PO4-(aq) ⇌ HPO4-(aq) + H+(aq)
Calculations involving Buffer Solutions.
Because we mix acids with one of their salts, ionic dissociation occurs. The salt with the
conjugate base ion dissociates almost completely. An example of this is:
CH3CH2COONa(s) ⟶ CH3CH2COO-(aq) + Na+(aq)
But the extent of dissociation involving the acid molecule is extremely weak compared to the
salt dissociation, so we assume it to be negligible. Therefore, the salt concentration
(conjugate base concentration) is only accounted for from the salt.
CH3CH2COOH(aq) ⇌ CH3CH2COO-(aq) + H+(aq)
[H+ ]Acid [A- ]Salt
The Ka value is calculated by the expression: Ka =
[HA]Unionised Acid
Q1-Calculate the pH of a buffer solution containing 0.0500 mol dm-3 of ethanoic acid and
0.075 mol dm-3 sodium ethanoate given that the Ka of ethanoic acid is equal to 1.74 × 10-5.
[H+ ]Acid [A- ]Salt x×0.075
Solution: Ka = = → 1.74 × 10-5 =
[HA]Unionised Acid 0.050
[H+] = 1.16 × 10-5
pH = -log[1.16 × 10-5] = 4.94.
Q2-Calculate the pH of a buffer solution containing 0.045 mol dm-3 propanoic acid and
0.12 mol dm-3 sodium propanoate given that the Ka of propanoic acid is 1.35 × 10-5.
[H+ ]Acid [A- ]Salt x×0.12
Solution: Ka = = → 1.35 × 10-5 =
[H+] = 5.0625 × 10-6 mol dm-3
pH = -log(5.0625 × 10-6) = 5.30.
Q3-Calculate the pH of a buffer solution containing 0.20 moles of sodium ethanoate in 500
cm3 of 0.10 mol dm-3 ethanoic acid given that the Ka for ethanoic acid is 1.8 × 10-5.
moles 0.20
Solution: Concentration [sodium ethanoate] = = = 0.4 mol dm-3.
total solution volume 0.5
+ -
[H ]Acid [A ]Salt x×0.40
Ka = = → 1.8 × 10-5 =
[H+] = 4.5 × 10-6 mol dm-3.
pH = -log(4.5 × 10-6) = 5.35
Q4-For a solution containing 0.050 mol dm-3 chloric (I) acid and 0.050 mol dm-3 sodium
chlorate (I), the pH at 298K is 7.43. Calculate the Ka value for chloric (I) acid.
Solution: [H]+ = 10-7.43 = 3.52 × 10-8 mol dm-3.
[H+ ]Acid [A- ]Salt 3.52 × 10-8 × 0.05
Ka = = = 3.52 × 10-8 mol dm-3.
Q5-Calculate the pH of a buffer solution that is formed when 50.0 cm3 of 1.20 mol dm-3 is
added to 50.0 cm-3of 1.60 mol dm-3 sodium ethanoate, given that the Ka of ethanoic acid is
equal to 1.74 × 10-5 mol dm-3.
Solution: Start off by finding the concentrations of both the salt and the acid in new solution.
Mol [CH3COONa] = 1.20 × 50/1000 = 0.06 mol.
Conc [CH3COONa] = 0.06/[(50 + 50)/1000] = 0.6 mol dm-3 sodium ethanoate.
Mol [CH3COOH] = 1.60 × 50/1000 = 0.08 mol.
Conc [CH3COOH] = 0.08/[(50 + 50)/1000] = 0.8 mol dm-3 ethanoic acid.
[H+ ]Acid [A- ]Salt x × 0.6 When the buffer solution is made by mixing 2 other
Ka = → 1.74 × 10-5 = solutions with different concentration, calculate the moles
[H+] = 2.32 × mol 10-5 dm-3 of solute present in both solutions and then calculate
their concentration as part of the total volume.
pH = -log (2.32 × 10-5) = 4.63.
Q6-A buffer solution contains ethanoic acid, which has a pKa of 4.76, at a concentration of
1.00 mol dm-3 and sodium ethanoate. If the pH of the buffer solution is 4.20, what id the
concentration of the sodium ethanoate?
Solution: Ka = 10-pKa = 10-4.76 = 1.74 × 10-5 mol dm-3.
[H+] = 10-pH = 10-4.20 = 6.31 × 10-5 mol dm-3.
[H+ ]Acid [A- ]Salt 6.31 × 10-5 × [A- ]Salt
Ka = → 1.74 × 10-5 = .
[HA]Unionised Acid 1
[Salt] = 0.28 mol dm-3.
Q7-Calculate the pH of a buffer solution that’s formed when 30.0 cm3 of 1.00 mol dm-3
ethanoic acid is added to 40.0 cm3 of 1.10 mol dm-3 sodium ethanoate given that the Ka for
ethanoic acid is equal to 1.74 × 10-5.
Solution: Mol [CH3COOH] = 0.03 × 1 = 0.03 mol ethanoic acid.
3
Conc [CH3COOH] = 0.03/[(30 + 40)/1000] = mol dm-3.
7
Mol [CH3COONa] = 0.04 × 1.1 = 0.044 mol sodium ethanoate.
0.044
Conc [CH3COONa] = 0.044/[(30 + 40)/1000] = mol dm-3.
0.07
+ - 0.044
[H ]Acid [A ]Salt x × 0.07
Ka = → 1.74 × 10-5 = 3
[HA]Unionised Acid
7
[H+] = 1.19 × 10-5 mol dm-3.
pH = -log (1.19 × 10-5) = 4.93.
Q8-Calculate the mass of sodium propanoate that must be dissolved in 1.00 dm3 of 1.00 mol
dm-3 of propanoic acid to give a pH of 4.5 given that the pKa of propanoic acid is 4.87 and
the molar mass of sodium propanoate is 96.07 g mol-1.
Solution: Ka = 10-pKa = 10-4.87 = 1.35 × 10-5 mol dm-3.
[H+] = 10-pH = 10-4.5 = 3.16 × 10-5 mol dm-3.
[H+ ]Acid [A- ]Salt 3.16 × 10-5 ×[A- ]Salt
Ka = → 1.35 × 10-5 = .
[HA]Unionised Acid 1
[Salt] = 0.427 mol dm-3.
m
Mol [Salt] = .
96.07
(m/96.07)
[Salt] = = 0.427
1
m = 0.427 × 96.07 = 41.0 g of sodium propanoate.
Q9-Calculate the pH of a solution containing equal amounts in moles of H2PO4-(aq) and

HPO4-(aq) given that the Ka value for the H2PO4-(aq) is equal to 6.3 × 10-7 mol dm-3.
Solution: Let the amount of moles of the ions be x
[H+ ]Acid [A- ]Salt [H+ ] × x
Ka = → 6.3 × 10-7 =
[HA]Unionised Acid x
[H+] = 6.3 × 10-7 mol dm-3.
pH = -log (6.3 × 10-7) = 6.20.
Q10-A buffer solution is made by mixing 100 cm3 of 0.20 mol dm-3 Na2HPO4 with 500
cm3of 0.30 mol dm-3 NaH2PO4. Calculate the pH of the solution given that the Ka value for
H2PO4 is equal to 6.3 × 10-7 mol dm-3 and the equilibrium reaction is:
H2PO4-(aq) ⇌ HPO42-(aq) + H+(aq).
Solution: Mol [Na2HPO4] = 0.1 × 0.2 = 0.02 mol sodium dihydrogenphosphate.
Conc [Na2HPO4] = 0.02 / 0.6 = 1/30 mol dm-3
Mol [NaH2PO4] = 0.5 × 0.3 = 0.15 mol sodium hydrogenphosphate.
Conc [NaH2PO4] = 0.15 / 0.6 = 0.25 mol dm-3.
0.02
[H+ ]Acid [A- ]Salt [H+ ] × 0.6
Ka = → 6.3 × 10-7 = 0.15
[HA]Unionised Acid
0.6
[H+] = 6.3 × 10-9 mol dm-3
pH = -log (6.3 × 10-9) = 5.32.
Q11-Calculate the pH of the solution obtained when 10.0 cm3 of 0.100 mol dm-3 sodium
hydroxide is added to 20.0 cm3 of 0.100 mol dm-3 ethanoic acid if the pKa = 4.76.
Solution: Notice that the initial reaction is what generates sodium ethanoate.
NaOH(aq) + CH3COOH(aq) → CH3COONa(aq) + H2O
Mol [Acid] available: 0.02 × 0.1 = 0.002 mol ethanoic acid.
Mol[Alkali] available: 0.01 × 0.1 = 0.001 mol sodium hydroxide. So it is limiting.
Mol [Acid] reacted initially: 0.001 mol
Mol [Acid] left to equilibrate: 0.001 By using the mole ratio, the Mol [Salt] is also 0.001
0.001
[H+ ]Acid [A- ]Salt [H+ ] × 0.03
Ka = → 10-4.76 = 0.001 → [H+] = 10-4.76 → pH = -log(10-4.76) = 4.76.
[HA]Unionised Acid
0.03
Q12-What must be the ratio of concentrations of the ethanoate ions to ethanoic acid molecules
in a buffer solution with pH 5.4 given that the ethanoic acid Ka = 1.7 × 10-5 mol dm-3 ?
Solution: [H+] = 10-5.4
[H+ ]Acid [A- ]Salt 10-5.4 ×[A- ]Salt
Ka = → 1.7 × 10-5 =
[HA]Unionised Acid [HA]Unionised Acid
-
[A ]Salt 1.7 × 10-5
= = 4.27.
[HA]Unionised Acid 10-5.4
Q13-A buffer is prepared by mixing 50.0 cm3 of a 0.0417 mol dm-3 solution of the salt of a
weak acid, NaX, with 150 cm3 of a 0.0204 mol dm-3 solution of a weak acid, HX. The pKa
for HX is 5.12 at 25℃. Calculate the pH of this buffer solution.
Solution: Mol [NaX] = 0.05 × 0.0417 = 2.085 × 10-3 mol NaX
Conc [NaX] = (2.085 × 10-3)/ 0.2 = 1.0425 × 10-2 mol dm-3.
Mol [HX] = 0.15 × 0.0204 = 3.06 × 10-2 mol HX.
Conc [HX] = (3.06 × 10-2) / 0.2 = 1.53 × 10-2 mol dm-3.
Ka = 10-pKa = 10-5.12 mol dm-3.
[H+ ]Acid [A- ]Salt [H+ ] × 1.0425 × 10-2
Ka = → 10-5.12 =
[HA]Unionised Acid 1.53 × 10-2
[H+] = 1.06 × 10-3 mol dm-3.
pH = -log(1.06 × 10-3) = 2.97.
Q14-100 cm3 of 0.0515 mol dm-3 nitrous acid (HNO2) were mixed with 50.0 cm3 of 0.0428
mol dm-3 sodium hydroxide solution. If the Ka value for nitrous acid (HNO2) dissociation
is 7.2 × 10-4, find the pH of this buffer solution.
Solution: The initial reaction is what generates the buffer salt:
HNO2(aq) + NaOH(aq) → NaNO2(aq) + H2O(l)
Mol [Acid] available = 0.1 × 0.0515 = 0.00515 mol.
Mol [Alkali] available = 0.05 × 0.0428 = 0.00214 mol. So it is limiting.
Mol [Acid] reacted = 0.00214 mol.
Mol [Acid] left to equilibrate = 0.00515 – 0.00214 = 0.00301 mol, and by using the mole
ratio concept you’ll find out that Mol [Salt] = 0.00214 mol.
0.00214
[H+ ]Acid [A- ]Salt [H+ ] × 0.15
Ka = → 7.2 × 10-4 = 0.00301 → [H+] = 1.01 × 10-3 mol dm-3.
[HA]Unionised Acid
0.15
pH = -log(1.01 × 10-3) = 2.99.
Solubility and the Solubility Product
Solubility: The maximum possible concentration of a saturated solution at a given

temperature. It is measured in mol dm-3. In other words, the total amount of solute that can
dissolve in a solvent at a given temperature.
For example, MgF2(s) has a solubility of 1.22 × 10-3 mol dm-3, meaning that 1.22 × 10-3
moles of MgF2 will dissolve in 1 dm3 of water before no more can dissolve in standard
conditions.
All salts can make a saturated solution when added to water, even the “insoluble” ones.
Remember that there is no such thing as a salt that is absolutely insoluble salt, but only
increasingly sparingly soluble in water. “Insoluble” salts are the salts such that the
amount of salt needed to reach saturation is extremely tiny. An example is barium sulfate.
Solubility Product Constants KSp.
Once the solution reaches saturation, the solid salt will form an equilibrium with its
constituent ions. Since there is an equilibrium reaction going on in the solution, there will be
an equilibrium constant Kc expression for the reaction. Example with silver bromide AgBr:
AgBr(s) ⇌ Ag+(aq) + Br-(aq)
-
[Ag+
(aq) ][Br(aq) ]
Kc = , but remember that the concentration of any solid is a constant value.
[AgBr(s) ]
Therefore, if I rearrange the expression: Kc × [AgBr(s)] = [Ag+(aq)] [Br-(aq)].
The value of the constant Kc × [Salt] = KSp, which is the solubility product constant.
In general, for:
AxBy(s) ⇌ xA+(aq) + yB-(aq)
KSp = [A+(aq)]x [B-(aq)]y with units molx + y dm-3(x + y)
Q1-Write an equilibrium expression for the dissociation of Iron (III) Sulfide, Fe2S3?
Solution: Fe2S3(s) ⇌ 2Fe3+(aq) + 3S2-(aq)
KSp = [Fe3+(aq)]2 [S2-(aq)]3 with units mol5 dm-15.
Q2-Write an equilibrium expression for the dissociation of aluminium hydroxide, Al(OH)3?

Solution: Al(OH)3(s) ⇌ Al3+(aq) + 3OH-(aq)
The concept of KSp only works for
KSp = [Al3+(aq)] [OH-(aq)]3 with units mol4 dm-12. sparingly soluble salts, because
sparingly soluble salts are the ones that
form equilibriums in saturated solutions.
Calculations involving Solubility Products
Recall the concept of the ICE table from equilibria, because the reactions in this topic are
equilibrium reactions.
Q1-Calculate the solubility product of a saturated aqueous solution of cadmium sulfide,
CdS, if the solubility of the salt is 1.46 × 10-11 mol dm-3.
Solution: If the solution is saturated, then the moles produced are equal to the solubility
moles.
CdS(s) ⇌ Cd2+(aq) + S2-(aq) The initial moles of salt can be of any value, but the
I ? 0 0 change row of the table is governed by the mole ratio
of the equation. Because we don’t know the initial
C 1.46 × 10-11 1.46 × 10-11 1.46 × 10-11 amount of salt, we can’t calculate the amount of salt
E - 1.46 × 10 1.46 × 10
-11 -11 present to equilibrate, but that doesn’t matter.
KSp = [Cd2+(aq)] [S2-(aq)] = (1.46 × 10-11)2 = 2.13 × 10-22 mol2 dm-6.
Q2-Calculate the solubility product of a saturated aqueous solution of calcium fluoride,

CaF2, if the solubility of the salt is 0.00168 g dm-3.
0.00168
Solution: Formula mass of CaF2 = = 2.15 × 10-4 mol dm-3.
(40.1 + 38)
CaF2(s) ⇌ Ca2+(aq) + 2F-(aq)
Always make sure the solubility
I ? 0 0 is in mol dm-3. Always.
C 2.15 × 10-4 2.15 × 10-4 2(2.15 × 10-4)
E - 2.15 × 10-4 2(2.15 × 10-4)
KSp = [Ca2+(aq)] [F-(aq)]2 = (2.15 × 10-4) (4.30 × 10-4)2 = 3.98 × 10-11 mol3 dm-9.
Q3-Calculate the solubility in mol dm-3 of zinc sulfide, ZnS, given that the KSp is 1.6 × 10-23
mol2 dm-6.
The rules in the change row of the table are
Solution: ZnS(s) ⇌ Zn2+(aq) + S2-(aq) still the same and work by the mole ratio
I ? 0 0 concept. We don’t know the solubility or how
C x x x much of the ions would form, so we label it x.
Practice Practice Practice.
E - x x
KSp = [Zn2+(aq)] [S2-(aq)] ⟶ 1.6 × 10-23 = x × x
2
Therefore, x = √(1.6 × 10-23 ) = 4 × 10-12 mol dm-3.
Q4-Calculate the solubility of silver carbonate, Ag2CO3, in mol dm-3 given that the value for
the KSp for the reaction equals to 6.3 × 10-12 mol3 dm-9.
Solution: Ag2CO3(s) ⇌ 2Ag+(aq) + CO32-(aq)
I ? 0 0
C x 2x x
E - 2x x
KSp = [Ag+(aq)]2 [CO32-(aq)] ⟶ 6.3 × 10-12 = (2x)2 × x
4x3 = 6.3 × 10-12
3 -12
6.3 × 10
x=√ = 1.16 × 10-4 mol dm-3.
4
The relationship between ionic products of salts and their KSp values
If the ionic product Q of a salt is > the KSp of the salt, then the solution is supersaturated
and the solid will precipitate until Q = KSp which is the point at which equilibrium occurs.
If the ionic product Q of a salt is < the KSp of the salt, then the solution is unsaturated and
more solid will dissolve until it saturates, Q = KSp and the equilibrium is regained.
Q > KSp
Ionic Product Q
Q = KSp
Q < KSp
Amount of substance dissolved

in solution.
Q1-Will barium sulfate precipitate if 10.0 cm3 of 0.0020 mol dm-3 sodium sulfate, Na2SO4,
is added to 100.0 cm3 of 0.00032 mol dm-3 barium chloride, BaCl2 if BaSO4(s) KSp is equal
to 1.08 × 10-10 mol2 dm-6 at 298K.
Solution: Because both salts are soluble, a double precipitation reaction occurs and the less
soluble salt precipitates. The reaction is: Na2SO4(aq) + BaCl2(aq) → 2NaCl(aq) + BaSO4(s).
The saturation equilibrium is given by: BaSO4(s) ⇌ Ba2+(aq) + SO42-(aq).
100
For Mol Ba2+(aq) = × 0.00032 = 3.20 × 10-5 mol Ba2+.
1000
3.20 × 10-5
[Ba2+(aq)] = 110 = 2.91 × 10-4 mol dm-3.
1000
10
For Mol SO42-(aq) = × 0.002 = 2.00 × 10-5 mol SO42-.
1000
2.00 × 105
[SO42-(aq)] = 110 = 1.82 × 10-6 mol dm-3.
1000
Ionic Product Q of BaSO4 = [Ba2+(aq)] [SO42-(aq)] = (2.91 × 10-4) (1.82 × 10-6)
= 5.30 × 10-10 mol2 dm-6.
Q > KSp, so precipitation will happen.
Q2-The solubility product of calcium fluoride (CaF2) is 3.45 × 10-11 mol3 dm-9. If 2.0 cm3
of a 0.10 mol dm-3 solution of sodium fluoride, NaF, is added to 128.0 cm3 of a 2.0 × 10-5
mol dm-3 solution of Ca(NO3)2, will CaF2 precipitate?
Solution: 2NaF(aq) + Ca(NO3)2(aq) → 2NaNO3(aq) + CaF2(s).
CaF2(s) ⇌ Ca2+(aq) + 2F-(aq)
128
Mol Ca2+(aq) = × 2 × 10-5 = 2.56 × 10-6 mol Ca2+
1000
2.56 × 10-6
[Ca2+(aq)] = 130 = 1.97 × 10-5 mol dm-3
1000
2
Mol F-(aq) = × 0.10 = 2 × 10-4 mol
1000
2 × 10-4
[F-(aq)] = 130 = 1.54 × 10-3 mol dm-3
1000
Ionic product Q of CaF2 = [Ca2+(aq)] [F-(aq)]2 = (1.97 × 10-5)(1.54 × 10-3)2= 4.67 × 10-11
Q > KSp, so yes it will precipitate.
Q3-Calculate the solubility of lanthanum iodate, La(IO3)3 and calculate the equilibrium
concentration with solid lanthanum iodate given that the KSp = 6.20 × 10-12 mol4 dm-12.
Solution: La(IO3)3(s) ⇌ La3+(aq) + 3IO3-(aq)
I ? 0 0
C S S 3S
E - S 3S
If the solubility is S, then the concentration of all ions mol-1 at equilibrium = S
KSp = [La3+(aq)] [IO3-(aq)]3 = (S) (3S)3 = 27S4
27S4 = 6.20 × 10-12
4 -12
6.20 × 10
S=√ = 6.92 × 10-4 mol dm-3.
27
Concentration of iodate ions at equilibrium = 3S = 2.08 × 10-3 mol dm-3.
The Common Ion Effect
Common Ion Effect: The common ion effect is the reduction in the solubility of a dissolved
salt achieved by adding a solution of a compound which has an ion in common with the
dissolved salt. This often results in precipitation.
An example of this effect in action is when a solution of highly soluble NaOH is added to a
saturated solution of Mg(OH)2, which is an “insoluble” salt. Due to the commonality of
the OH-(aq) in both solutions, the Mg(OH)2 will precipitate out of solution.
Explanation: Because the Mg(OH)2 solution is saturated, it is in equilibrium with the ions.
Mg(OH)2(s) ⇌ Mg2+(aq) + 2OH-(aq), so when we add a very soluble salt containing
OH-(aq), the concentration of OH-(aq) increases and the equilibrium will shift backwards to
make more and more Mg(OH)2(s) which is a precipitate.
Remember that, at a particular temperature, the KSp of a salt will always remain the same
even if the concentration of one of the ions increases or decreases.
Explanation: The KSp of Mg(OH)2 is given by KSp = [Mg2+(aq)] [OH-(aq)[2, and given
that the KSp will stay the same and the concentration of OH-(aq) increases due to the addition
of NaOH, the concentration of Mg2+(aq) must decrease to compensate for the increase in OH-.
Q1-The KSp of barium sulfate, BaSO4, salt is equal to 1 × 10-10 mol2 dm-6.
a) Calculate the solubility of BaSO4 in H2O.
Solution: Let the solubility be x.
BaSO4(s) ⇌ Ba2+(aq) + SO42-(aq)
I ? 0 0
C x x x
E - x x
KSp = [Ba2+(aq)] [SO42-(aq)] ⟶ 1 × 10-10 = x2
2
x = √1 × 10-10 = 1 × 10-5 mol dm-3. Solubility of BaSO4 = 1 × 10-5 mol dm-3.
b) Calculate the solubility of BaSO4 in 0.1 mol dm-3 Na2SO4(aq).

Solution: Let the solubility be S, Na2SO4 is the soluble salt and SO42- is the common ion.
Na2SO4(s) → 2Na+(aq) + SO42-(aq)
0.1 0.1 0.1
BaSO4(s) ⇌ Ba2+(aq) + SO42-(aq)
I ? 0 0
C S S S
E - S S
KSp = [Ba2+(aq)] [SO42-(aq)] = 1 × 10-10 mol2 dm-6.
Because BaSO4 is highly insoluble, the concentration of SO42-(aq) S is negligible and most of
the SO42-(aq) concentration will come from the 0.1 mol dm-3 in Na2SO4.
So [Ba2+] = S and [SO42-] = 0.1
Therefore, KSp = 0.1S = 1 × 10-10
S = 1 × 10-9 mol dm-3.
Q2-Calculate the solubility of CaF2 in 0.1 mol dm-3 NaF(aq), given that the KSp of CaF2 is
equal to 1.46 × 10-10 mol3 dm-9.
Solution: Let the solubility of CaF2 in NaF be S, NaF is the soluble salt, and F-(aq) is the
common ion.
NaF(s) → Na+(aq) + F-(aq)
0.1 0.1 0.1
CaF2(s) ⇌ Ca (aq) + 2F-(aq)
2+
I ? 0 0
C S S 2S
E - S 2S
KSp = [Ca2+(aq)] [F-(aq)]2 = 1.46 × 10-10 mol3 dm-9
Because CaF2 is highly insoluble, the concentration of F-(aq) 2S is negligible and most of the
F-(aq) concentration will come from the 0.1 mol dm-3 in NaF.
So [Ca+(aq)] = S and [F-(aq)]2 = 0.12
Therefore, KSp = 0.01S = 1.46 × 10-10
S = 1.46 × 10-8 mol dm-3.
Q3-A saturated solution of copper (I) sulfide, Cu2S, contains 1.91 × 10-12g of Cu2S
dissolved in 1 dm3 of water.
a) Write an equilibrium expression for the solubility product of copper (I) sulfide.
Solution: KSp = [Cu+(aq)]2 [S2-(aq)]
b) Calculate the value of the solubility product of copper (I) sulfide, stating the units.
1.91 × 10-12
Solution: Mol [Cu2S] dm-3 = = 1.20 × 10-15 mol dm-3
2(63.5) + 32.1
Cu2S(s) ⇌ 2Cu+(aq) + S2-(aq)
I ? 0 0
C 1.20 × 10-15 2(1.20 × 10-15) 1.20 × 10-15
E - 2(1.20 × 10-15) (1.20 × 10-15)
KSp = [Cu+(aq)]2 [S2-(aq)] = [2(1.20 × 10-15)]2 (1.20 × 10-15) = 6.92 × 10-42 mol3 dm-9.
c) Copper (II) chromate has a solubility of 1.9 × 10-3 mol dm-3 in water. Copper (II)
Sulfate has a solubility of 1.4 × 10-1 mol dm-3 in water. What will you observe when 10 cm3
of an aqueous solution of 0.0100 mol dm-3 copper (II) sulfate is added to an equal volume
of a saturated solution of copper (II) chromate? Explain your answer.
Solution: Copper (II) chromate, which is the less soluble salt, is going to precipitate out
more due to the increase in Cu2+ within the solution mixture. CuSO4 fully ionises, but CuCrO4
equilibrates with its ions: CuCrO4(s) ⇌ Cu2+(aq) + CrO42-(aq), and the equilibrium shifts
backwards due to the increase in Cu2+ concentration.
Q4) a) What is the pH of 0.25 mol dm-3 HCl(aq)?

Solution: HCl(aq) is a strong acid, so [H+] = 0.25 mol dm-3
pH = -log(0.25) = 0.60
b) What is the pH of 0.0500 mol dm-3 sodium hydroxide if the KW = 1.00 × 10-14 mol2 dm-6.
Solution: [OH-] = [NaOH] = 0.05
pOH = -log(0.05) = 1.30
pH = 14 – pOH = 14 – 1.30 = 12.7
c) Propanoic acid is a weak acid. A 0.0500 mol dm-3 solution of propanoic acid has a pH of
3.1. Calculate the value of Ka for propanoic acid showing all of your working.
Solution: [H+] = 10-3.1 mol dm-3.
[H+ ]2 (10-3.1 )2
Ka = = = 1.26 × 10-5 mol dm-3.
[C2 H5 COOH] 0.05
25.2-Partition Coefficient
Partition Coefficient Kpc: The partition coefficient, Kpc, is the equilibrium constant which
relates the concentration of the solute partitioned in between two immiscible solvents at a
particular solvent at equilibrium. It is a measure of the relative concentrations of a
particular solute in two liquids. An equilibrium commences when the rate of transfer of the
solute between both solvents is the same eitherway (From solvent X to Solvent Y and
backwards). The chemical equation that shows the equilibrium in action is of the form:
[A(Any Solvent Y) ]
A(Any solvent X) ⇌ A(Any Solvent Y) where the Kpc = , and if one of the immiscible
[A(Any Solvent X) ]
liquids is water (aq), then it will always be in the place of liquid X. It has no units because
it’s a ratio.
An example of this process is the dissolving of iodine molecules in water and hexane, which
are two immiscible liquids. Iodine dyes water yellow-or whereas it dyes hexane purple.
This equilibrium is characterized by I2(aq) ⇌ I2(hexane), and here
[I2(Hexane) ]
Kpc = I2(hexane)
[I2(aq) ]
What’s the practical purpose for this? I2(aq)
The values and calculations involving Kpc can be used in solute extraction when solutes are
dissolved in liquids. By knowing the amount of solute in both liquids, a comparison can be
made regarding which of the 2 liquids is better at dissolving and extracting a solute product
from a prior reaction.
Calculations involving Kpc values
Q1-A solution of 5.00g of organic compound X in 50 cm3 of water was shaken with 100 cm3
of ether. After separation, the aqueous solution was found to contain 0.80g of X. Determine
the value for the partition coefficient of X, Kpc, between ether and water.
Solution: Start off by calculating the concentrations of X in both solvents
Let the MR of X be R
If 0.80g out of 5.00g exist in aq form, then only 4.20g exist in the ether.
4.20
MolX(ether) =
R
4.20
R 4.20 1000 42
[Xether] = 100 = × = mol dm-3
R 100 R
1000
0.80
MolX(aq) =
R
0.80
R 0.80 1000 16
[X(aq)] = 50 = × = mol dm-3
R 50 R
1000
42
[Xether] R 42 R
Kpc = = 16 = × = 2.625
[X(aq)] R 16
R
Q2-When 100 cm3 of an aqueous solution containing 2.00g of an organic dye X was shaken
with 20 cm3 of hexane, it was found that 1.6g of the dye had been extracted into the hexane.
a) Calculate the partition coefficient of X between hexane and water.
Solution: Let the MR of X be R
1.60
MolX(hexane) =
R
1.60
R 1.60 1000 80
[XHexane] = 20 = × = mol dm-3
R 20 R
1000
Mass of X in water = 2.00g – 1.60 = 0.40g
0.40
MolX(aq) =
R
0.40
R 0.40 1000 4
[X(aq)] = 100 = × = mol dm-3
R 100 R
1000
80
[XHexane] R 80 R
Kpc = = 4 = × = 20.
[X(aq)] R 4
R
b) Calculate the minimum volume of hexane needed to reduce the amount of X in the aqueous
layer to less than 0.1g.
Solution: If there is only 0.1g of X in water, 1.90g of X would be extracted by hexane. The
Kpc is still 20 because no conditions changed. Let the required volume of hexane be V.
1.90
MolX(hexane) =
R
1.90
R 1.90 1000 1900
[X(hexane)] = V = × = mol dm-3
R V VR
1000
0.10
MolX(aq) =
R
0.10
R 0.10 1000 1
[X(aq)] = 100 = × = mol dm-3
R 100 R
1000
1900
[XHexane] VR 1900 R 1900
Kpc = ⟶ 20 = 1 = × =
[X(aq)] VR 1 V
R
V = 1900/20 = 95 cm3 of hexane.
Q3-The partition coefficient for the distribution of cyclohexanone between water and octanol
is 24. Calculate the mass of cyclohexanone that would be extracted if 20 cm 3 of octanol was
shaken with 100 cm3 of an aqueous solution containing 2.5g of cyclohexanone.
Solution: Extracting from the 2.5g total, so if mass extracted is m, then mass in aq is 2.5 - m
m
MolCyclohexane(octanol) =
R
m
R m 1000 50m
[Cyclohexane(octanol)] = 20 = × =
R 20 R
1000
2.5 - m
MolCyclohexane(aq) =
R
2.5 - m
R 2.5 - m 1000 25 - 10m
[Cyclohexane(aq)] = 100 = × =
R 100 R
1000
Kpc = 24, 24(25 – 10m) = 50m
600 – 240m = 50m
600 = 290m
m = 2.07g
Multiple Solvent Extractions
In Q3, 1 extraction using 20 cm3 was done, and 2.07g of cyclohexanone was extracted.
Generally, when more trials of extraction are carried out, then more solute is going to be
extracted.
Q4- The partition coefficient for the distribution of cyclohexanone between water and octanol
is 24. Calculate the mass of cyclohexanone that would be extracted if 20 cm 3 of octanol was
shaken with 100 cm3 of an aqueous solution containing 2.5g of cyclohexanone. Calculate the
total amount of cyclohexanone if the octanol was shaken 2 times in two 10 cm3 turns.
Solution: For 1st 10 cm3: m1 grams of cyclohexanone were extracted.
m
MolCyclohexanone(octanol) = 1.
R
m1
R m1 1000 100m1
[Cyclohexanone(octanol)] = 10 = × =
R 10 R
1000
2.5 - m1
MolCyclohexanone(aq) =
R
2.5 - m1
R 2.5 - m1 1000 25 - 10m1
[Cyclohexanone(aq)] = 100 = × =
R 100 R
1000
100m1
[XHexane] R 100m1 R 100m1
Kpc = ⟶ 24 = 25 - 10m1 = × =
[X(aq)] R 25 - 10m1 25 - 10m1
R
24(25 - 10m1 ) = 100m1
600 – 240m1 = 100m1
600 = 340m1
m1 = 1.765g
Second run, m2 is extracted and (2.5 – 1.765) = 0.735g left to be extracted.
m
MolCyclohexanone(octanol) = 2
R
m2
R m2 1000 100m2
[Cyclohexanone(Octanol)] = 10 = × =
R 10 R
1000
0.735 - m2
MolCyclohexanone(aq) = .
R
0.735 - m2
R 0.735 - m2 1000 7.35 - 10m2
[Cyclohexanone(aq)] = 100 = × =
R 100 R
1000
100m2
[XHexane] R 100m2 R 100m2
Kpc = ⟶ 24 = 7.35 - m2 = × = .
[X(aq)] R 7.35 - 10m2 7.35 - 10m2
R
24(7.35 – 10m2) = 100m2
176.4 – 240m = 100m2
176.4 = 340m2
m2 = 0.519g
So, total recovered mass = 1.765 + 0.519 = 2.284g.
Q5-Ammonia is soluble in both water and organic solvents. An aqueous solution of ammonia
is shaken with the immiscible organic solvent trichloromethane. The mixture is left to reach
equilibrium. Samples are taken from each layer and titrated with dilute hydrochloric acid. A
25.0 cm3 sample from the trichloromethane layer requires 13.0 cm3 of 0.100 mol dm-3 HCl to
reach endpoint. A 10.0 cm3 sample from the aqueous layer requires 12.5 cm3 of 0.100 mol
dm-3 HCl to reach end point. Calculate the partition coefficient, Kpartition, of ammonia between
trichloromethane and water.
Solution: NH3(aq) + HCl(aq) → NH4Cl(s)
Mole ratio is 1:1:1, so the moles of HCl used = moles of NH3 used.
12.5
MolAmmonia(aq) = × 0.100 = 0.00125 mol
1000
0.00125
[Ammonia(aq)] = 10 = 0.125 mol dm-3
1000
13.0
MolAmmonia (CHCl3) = × 0.100 = 0.0013 mol
1000
0.0013
[Ammonia (CHCl3)] = 25 = 0.052 mol dm-3
1000
[XCHCl3] 0.052
Kpc = ⟶ = 0.416
[X(aq)] 0.125
As you can see, the process of calculating Kpc-related values is a bit lengthy, but it can be
simplified. Because Kpc is a unitless ratio, the units for the concentration don’t really matter
as they’ll just cancel out. Notice how the value for the MR of the compound always cancels
out. So we can keep the mass and the volume as presented and calculate the concentrations in
g cm-3. Example:
Q6-When a solution of 1.00g of X in 100 cm3 of water was shaken with 10 cm3 of ether,
0.80g of X was transferred to the ether layer. Calculate the partition coefficient of X between
water and ether.
Solution: If 0.80g is in the ether layer at equilibrium, then 0.20g will be left out.
0.20
[X(aq)] = g cm-3
100
0.80
[X(ether)] = g cm-3.
10
0.80
[X(ether)] 10 0.80 100
Kpc = ⟶ 0.20 = × = 40
[X(aq)] 10 0.20
100
Q7-Find the total mass of compound H extracted when 1.00g of H in 100 cm3 of water is
shaken twice with 5 cm3 of octan-1-ol if the Kpc of H between water and octan-1-ol is 40.
Solution: If m is extracted, then 1 – x is left in water.
1-x
[X(aq)] = g cm-3.
100
x
[X(octan-1-ol)] = g cm-3.
5
x
[X(octan-1-ol)] 5 x 100 20x
Kpc = ⟶ 40 = 1-x → 40 = × =
[X(aq)] 5 1-x 1-x
100
40 – 40x = 20x → 0.667g extracted 1st time and 0.23g left.
0.23 - y
[X(aq)] = g cm-3.
100
y
[X(octan-1-ol)] = g cm-3.
5
y
[X(ether)] 5 y 100 20y
Kpc = ⟶ 40 = 0.23 - y → 40 = × =
[X(aq)] 5 0.23 - y 0.23 - y
100
9.2 – 40y = 20y → 0.153g
Total mass extracted = 0.153 + 0.667 = 0.820g
Relationship between the Kpc value and the polarity of the solutes and solvents
The solubility of a solute in a solvent depends on the strength of the intermolecular forces
established between the solute and the solvent. The stronger the intermolecular forces of
attraction between the solute and the solvent, the greater the solubility of the solute.
Polar solutes will dissolve in polar solvents due to the formation of strong hydrogen bonds
between them. So, a solute like NH3(aq), which is polar, will dissolve more in a polar solvent
like water than a non-polar solvent like tetrachloromethane.
Quick Analytical tip

When Kpc > 1, the solute is more soluble in the other solvent than in water.
When Kpc < 1, the solute is more soluble in water than in the other solvent.
C C
H H
26-Reaction Kinetics
26.1-Simple Rate Equations, Orders of Reactions and Rate Constants
Rate of Reaction: The speed of the occurrence of a reaction, and is defined as either the
increase in the concentration of a product over a specific time interval, or the decrease in the
concentration of a reactant over a specific time interval.
∆Concentration
Rate = , so the unit is mol dm-3 s-1.
∆time
The rate of a reaction can be determined experimentally by finding the gradients of tangents
of concentration-time graphs, whether the concentration refers to the decrease in reactant
concentration or increase in product concentration. Remember that the rate of reaction changes
over the reaction period. The instantaneous rate of reaction can be approximated by
calculating the gradient over shorter and shorter periods of time.
Let’s consider the reaction A → B.
[A] / mol dm-3

[B] / mol dm-3
Time / s Time / s
You know very well how to find the gradient of a graph.
Rate Equations
Rate Equation: The rate equation for a chemical reaction is an equation that links the
initial reaction rate with the concentrations of the reactants and constant parameters such as
rate coefficients and partial reaction orders.
The rate is given by the equation rate = k [A]x [B]y [C]z … and so on.
The equation shows the specific relation between the rate of the reaction and the dependent
concentrations of the reactants. The exponents x and y show the partial orders of the
reactions with respect to A and B respectively.
Partial Reaction orders: The partial order of reaction with respect to a particular reagent is
the power to which the reactant is raised in the rate equation. It can be either an integer, a
non-integer or even negative.
If the partial reaction order is 0, then the rate of reaction doesn’t depend on the species
which has the order 0. If the partial reaction order > 0, then the rate of reaction is directly
proportional to the concentration of that reagent that is raised to the positive order. If the
partial reaction order < 0, then the rate of reaction is inversely proportional to the
concentration of that reagent that is raised to the negative order. If the partial reaction order
is a non-integer, then that signifies that the relationship between the rate of reaction and the
concentration of reactant is a bit more complex.
Example: If the rate equation for a reaction is given by rate = k[NO2]2, then the rate of
reaction is proportional to the square of the concentration of NO2.
If the rate of equation for a reaction is given by rate = k[H2] [I2], then the rate of reaction
is proportional to the concentration of H2 and the concentration of I2.
H+
Q1-Write the rate equation for CH3COCH3 + I2 → CH3COCH2I + HI, where the rate is
proportional to the concentration of CH3COCH3 and the concentration of H+ ions, but not
the concentration of I2.
Solution: Rate = k[CH3COCH3] [H+]
Q2-Write the rate equation for 2HgCl2 + K2C2O4 → Hg2Cl2 + 2KCl + 2CO2, where the
rate is proportional to the concentration of HgCl2 and the square of the concentration of
K2C2O4.
Solution: Rate = k[HgCl2] [K2C2O4]2.
Overall Reaction Order: This is defined as the sum of the partial reaction orders in a
specific rate equation.
So, for a reaction with a rate equation k[A]x [B]y , so the overall reaction order = x + y.
The unit for the rate constant may vary from reaction to reaction depending on the partial
reaction orders. We can determine them using the fact that the rate of a reaction always has
the same units of mol dm-3 s-1.
Q1-State the units of k for a reaction that has a rate equation of k[BrO3-] [Br-] [H+]2.
Solution: Rate = k[BrO3-] [Br-] [H+]2
Rate mol dm-3 s-1 s-1
k= + 2
= -3 -3 -3 2 = -3 -3 2 = mol-2 dm9 s-1
[BrO-3 ] -
[Br ] [H ] (mol dm ) × (mol dm ) × mol dm ) (mol dm ) × (mol dm )
Q2-State the units of k for a reaction that has a rate equation of k[NH3]0.
Solution: Rate = k[NH3]
Rate mol dm-3 s-1
k= 0 = -3 0 = mol dm-3 s-1.
[NH3 ] (mol dm )
How to determine the partial order of reaction?
The shape of a reaction-rate to concentration of a reactant can be used to determine whether a

reaction is 0th, 1st or 2nd order. Reactions rarely have 3rd order partial reaction orders.
Let there be a reaction with a reactant A.
Rate = k[A]2.
Because the input
concentration is squared,
2nd partial reaction order
the graph is quadratic.
Reaction Rate / mol dm-3 s-1
Rate = k.
Because the input concentration is a
constant, the graph is a horizontal line
0th partial reaction order Rate = k[A].
Because the input concentration is
1st partial reaction order linear, the graph is an inclined line.
[A] / mol dm-3

-If the reaction rate-reactant concentration graph looks quadratic, then the partial reaction
order is 2nd order with respect to that reactant. The rate is proportional to the square of the
concentration of a specific reactant.
-If the reaction rate-reactant concentration graph is a line with a gradient, then the partial
reaction order is 1st order with respect to that reactant. The rate is proportional to the
concentration of a specific reactant.
-If reaction rate-reactant concentration graph is a horizontal line, then the partial reaction
order is 0th order with respect to that reactant. The rate is independent of the concentration
of a specific reactant.
Q1-The reaction that converts trimethylchloromethane into trimethylmethanol is:

(CH3)3CCl + OH- → (CH3)3COH + Cl-. The rate equation is rate = k[(CH3)3CCl].
Sketch a reaction rate-reactant concentration graph.
Reaction Rate / mol dm-3 s-1
Solution:
[(CH3)3CCl] / mol dm-3 s-1

Another graphical indicator for finding the partial reaction order are reactant concentration-
time graphs. The shape of this specific graph can also be used. Let there be a reaction with a
reactant B.
0th partial reaction order

[B] / mol dm-3
1st partial reaction order
2nd partial reaction order
Time / s
In this graph, the rate is given by the gradient of the graph.

-In 0th partial order reactions, the reaction rate is constant, which is shown by the blue
graph.
-In the 1st partial order reactions, the reaction rate is proportional to the reactant
concentration at the time. The differential equation modelling this is:
d[B]
= -k[B].
dt
-In the 2nd partial order reactions, the reaction rate is proportional to the square of the
reactant concentration at the time. The differential equation modelling this is:
d[B]
= -k[B]2.
dt
The final graphical indicator is the change in the value for the half-life of the reaction.
Half-life t 1 : The half-life of a reaction is the time taken for the concentration of a reactant
2
to drop by 50% of its original value.
0th partial reaction order 1st partial reaction order 2nd partial reaction order
Concentration / mol dm-3
For 0-orders, the half-life For 1-orders, the half-life For 2-orders, the half-life
decreases progressively. stays the same progressively. increases progressively.
t1 t1 Time / s t1 t1 t1 t1 Time / s
(1) (2) (1) (2) Time / s 2
(1) (2)
2 2 2 2 2
The relationship between rate constant k and half-life t 1 for 1st order reactions
2
For a reaction that has a reactant R, where R affects the reaction in 1st partial order
dR
reaction order. For a 1st order reaction: = -kR
dt
1
dR = -k dt
R
R t
1
∫ dR = ∫ -k dt
R0 R t0
R
The half-life of a 1st order reaction is ln = -kt
R0
independent of the initial concentration of the
1
reactants. So it takes as much time for [R] to ln ( ) = -kt
decrease from 1.00 mol dm-3 to 0.50 mol dm-3 2
as for [R] to decrease from 1.00 mol dm-3 .to ln (2) = kt
0.05 mol dm-3. ln (2)
t1 = .
2
k
R0
Where t0 = 0, R = , k is the rate constant, t 1 = t.
2 2
Q1-The reaction for the decomposition of H2O2 into H2O is given by:
H2O2(aq) + 2I-(aq) + 2H+(aq) → 2H2O(l) + I2(aq), rate equation is rate = k[H2O2] [I-].
Calculate the rate constant given that the initial [H2O2(aq)] = 0.03 mol dm-3, [I-] = 0.01
mol dm-3, [H+(aq)] = 0.01 mol dm-3 and initial reaction rate = 5.30 × 10-6 mol dm-3 s-1.
Solution: rate = k[H2O2] [I-] → 5.30 × 10-6 = k(0.03) (0.01)
5.30 × 10-6 mol dm-3 s-1
k= = 0.018 = 0.018 dm3 mol-1 s-1.
0.0003 mol2 dm-6
Q2-The half-life of a first-order reaction was found to be 10 min at a certain temperature.

What is the rate constant for the reaction?
Solution: 10 minutes = 600s
ln (2) ln (2)
k= = = 1.2 × 10-3 s-1.
t1 600 s
2
Deduction of reaction order using experimental data
Start off by plotting a graph of the concentration of any particular reactant against time.
Then draw tangents for consecutive points across the curve. Calculate the gradients of the
tangents for these points, which represents the rate of reaction. Use this data to plot a rate-
concentration graph. Here’s an example question:
Q1-Methanol reacts with hydrochloric acid at 25℃. The products are chloromethane and
water. The reaction is:
CH3OH(aq) + HCl(aq) → CH3Cl(g) + H2O(l)
Equimolar amounts of methanol and hydrochloric acid are mixed at 25℃. The progress of
the reaction is followed by
-Taking a small sample of the reaction from time to time, then
-Titrating each sample with a standard solution of sodium hydroxide.
The data obtained is shown in the table below:
Time / minutes [HCl], mol dm-3 [CH3OH], mol dm-3
0 1.84 1.84
200 1.45 1.45
400 1.22 1.22
600 1.04 1.04
800 0.91 0.91
1000 0.81 0.81
1200 0.72 0.72
1400 0.66 0.66
1600 0.60 0.60
1800 0.56 0.56
2000 0.54 0.54
1.84
∆HCl
Gradient =
[HCl] / mol dm-3
∆t
1.48 1.480 mol dm-3
=
2000 × 60 s
= 1.23 × 10-5 mol dm-3 s-1
2000 Time / min

Time / s Concentration / mol dm-3 Rate / mol dm-3 s-1
0 1.84 3.83 × 10-5
12000 1.45 2.43 × 10-5
24000 1.22 1.75 × 10-5
36000 1.04 1.23 × 10-5
48000 0.91 0.90 × 10-5
Now, plot a rate-concentration graph:

4.00
Rate of reaction / 10-5 mol dm-3 s-1
This is a quadratic, so this

reaction overall is 2nd order.
Three possibilities exist:
-Rate = k[HCl]2
-Rate = k[CH3OH] [HCl]
-Rate = k[CH3OH]2, so that
the sum of the exponents is 2.
2.00
[HCl] / mol dm-3
Q2-Suggest how the experiment for the reaction between methanol and hydrochloric acid
might be re-designed to obtain evidence for the effect of changing the HCl concentration
whilst controlling the CH3OH concentration.
Solution: Vary the concentration of HCl while keeping the concentration of CH3OH
constant. Take different samples of the reaction mixture every 12000s and titrate them
against a standard solution of sodium hydroxide and calculate the concentrations of HCl
throughout the reaction. Plot the graph of the [HCl] against time graph. Draw tangents
to consecutive points for every 12000s and calculate the gradients of the tangents to find
the rate of reaction. Plot a graph of rate-concentration and determine the partial order of
reaction of HCl. If the graph is quadratic, then rate = k[HCl]2, if the graph is linear,
then the rate = k[HCl] [CH3OH], and if the graph is a straight horizontal line, then the
rate = k[CH3OH]2.
The initial rate problem
When the initial reaction rate is slow, this method is the most effective. The steps:
-Repeat experiment while varying the initial concentration of all reactions individually.
-Calculate the initial rates by plotting the concentration-time graph and draw a tangent to
the graph at the starting point of the experiment.
-Use the initial rate obtained from experiments to plot an initial rate-reactant
concentration graph.
Q4-The reaction between nitrogen (II) oxide and hydrogen gas produces nitrogen and
another gaseous product.
a) Write down the chemical equation adding the other gaseous product
Solution: 2NO(g) + 2H2(g) → N2(g) + 2H2O(g)
b) Three trials were done to find out the effect of the concentration of NO2 and H2 on the
rate of the reaction. The experimental data is shown below:
Initial [NO] / mol dm-3 Initial [H2] / mol dm-3 Initial rate / mol dm-3 s-1
0.20 0.20 0.40
0.40 0.20 1.60
0.20 0.40 0.80
Find the rate equation for the reaction.
Solution: Compare reactions 1 and 3, when the [H2] × 2, the rate × 2. Therefore, the
reaction is linear when it comes to [H2]. Compare reactions 1 and 2, when the [H2] × 2,
the rate × 4. Therefore, the reaction is quadratic when it comes to [NO]. So, the [NO] is
squared and [H2] is to power 1. Rate = k[H2] [NO]2.
Kinetics and Rate-determining Steps for Multi-step reactions
Rate-determining Step: In chemical kinetics, the overall rate of a reaction is often

approximately determined by the slowest step, known as the rate-determining step.
If the concentration of a reactant appears in the rate equation, then that reactant (or
substances that react together to form it) appears in the rate-determining step. If a
substance does not appear in the overall rate equation it does not take part in the rate-
determining step.
It is not possible to determine the exact mechanism for which an organic reaction goes
through just by looking at the chemical kinetics of the reaction, but we can know the
probability of a mechanism’s occurrence.
How can I suggest mechanisms given the rate equation?
By looking at a rate equation, you can know which molecules influence the reaction rate.
We know from before that the rate of reaction is approximately the speed of the slow rate-
determining steps. So, if a rate equation is rate = k[A] [B], then A and B are for sure
involved in the reactant side of the rate determining step.
Q1-The initial rate of the reaction of chlorine dioxide, ClO2, and fluorine, F2, is measured
in a series of experiments at a constant temperature. The results are recorded below:
2ClO2 + F2 → 2ClO2F
Experiment [ClO2] / mol dm-3 [F2] / mol dm-3 Initial rate / mol dm-3 s-1
1 0.010 0.060 2.20 × 10-3
2 0.025 0.060 To be calculated
3 To be calculated 0.040 7.04 × 10-3
The rate equation is rate = k[ClO2] [F2]
a) Explain what is meant by order of reaction with respect to a particular reagent.

Solution: The power to which the reactant is raised in the rate equation.
b) Use the results of experiment 1 to calculate the rate constant, k, for this reaction.
Include the units of k.
Solution: 2.20 × 10-3 = k (0.06) (0.01)
2.20 × 10-3 mol dm-3 s-1
k= = 3.67 mol-1 dm3 s-1
0.0006 mol2 dm-6
c) Calculate the initial rate for experiment 2

Solution: Rate = k[ClO2] [F2]
Rate = 3.67 × 0.025 × 0.060 = 5.5 × 10-3 mol dm-3 s-1.
d) Calculate the [ClO2] for reaction 3

Solution: [ClO2] = (7.04 × 10-3) / (0.040 × 3.67) = 0.048 mol dm-3.
e) Explain what is meant by the term rate-determining step.
Solution: Slowest step in the reaction that determines the rate of a multi-step reaction.
f) The mechanism of the reaction between ClO2 and F2 has two steps. Suggest equations
for both of these steps.
Solution: Because the rate equation involves both reactants, the rate-determining step’s
reaction must have both reactants. The final product at the end must include ClO2F.
Step 1: ClO2 + F2 → ClO2F2 Place your cornerstones for the
Step 2: ClO2F2 + ClO2 → 2ClO2F reactions to make it easier to guess
the intermediates. Start off by
placing the molecules present in the
rate equation at the reactant spot for
the rate determining step. Then place
the overall reaction’s product at the
end of the last step.
Q2-A four-step mechanism is suggested for the reaction between hydrogen peroxide and
iodide ions in an acidic solution.
Step 1: H2O2 + I- → IO- + H2O
Step 2: H+ + IO- → HIO
Step 3: HIO + I- → I2 + OH-
Step 4: OH- + H+ → H2O
Step 1 is the rate-determining step.
(i) State what is meant by the rate-determining step.
Solution: Slowest step in a reaction that determines the rate of a multi-step reaction.
(ii) Use this mechanism to construct a balanced overall equation.

Solution: For any overall reaction, add both sides and cancel what’s common:
H2O2 + I- → IO- + H2O
H+ + IO- → HIO
HIO + I- → I2 + OH-
OH- + H+ → H2O
H2O2 + 2I- + IO- + 2H+ + HIO + OH- → 2H2O + HIO + I2 + OH- + IO-
Overall reaction: H2O2 + 2H+ + 2I- → 2H2O + I2
(iii) Deduce the order of the reaction with respect to [H2O2], [I-] and [H+]
Solution: The only reactants in the rate-determining step are H2O2 and I-, so the reaction
is 0 order with respect to H+. In the rate-determining step, there is 1 H2O2 and 1I-
present, so the reaction will be 1st order with respect to H2O2.
Q2-Deduce the rate equation for the multi-step reaction:

A + B → AB (Fast)
AB + B → AB2 (Slow)
Solution: The rate-determining step is the slow step, and the reactants in the slow step are
1AB and 1B, so the rate equation is rate = k[AB] [B]. Notice how AB is an
intermediate. You can’t have intermediates in rate equations, so replace them by the
reactants that generate the intermediates. Since AB is formed from 1A and 1B, we can
rewrite it as being first order with respect to both A and B, so rate = k[A] [B] [B],
which means rate = k[A] [B]2.
Identification of catalysts and intermediates in reactions
Intermediate: A reaction intermediate or an intermediate is a molecular entity that is

formed from the reactants and reacts further to give the directly observed products of a
chemical reaction. They form within the reaction steps and end within the reaction steps, so
they are never the initial reactants or the final products. Example:
ClO- + H2O → HClO + OH- HClO, HIO and OH- formed and terminated
I + HClO → HIO + Cl
- -
before the final product and initial reactants.
HIO + OH → H2O + IO
- - Therefore, these are examples of intermediates.
Catalyst: A substance that increases the rate of a chemical reaction without itself
undergoing any permanent chemical change. For multi-step reactions, you can find a
catalyst by recognizing which reactant is depleted at the beginning by the reaction and then
regenerated at the final step. It won’t be part of the overall reactions. Example:
A+B→C+D B is consumed in the 1st step then it will be
A+C→E regenerated in the 3rd step, showing that
D+E→B+F replenishes and hence a catalyst.
Relationship between absolute temperature and the rate constant k.
The rate constant increases exponentially with the increase in thermodynamic temperature.
To look at the mathematics behind this relationship, we’ll introduce what is known as the
E
- a
Arrhenius Equation. The Arrhenius equation says k = Ae RT , where k is the rate constant,
A is a constant, Ea is the activation energy, R is the universal gas constant and T is the
E E
thermodynamic temperature. Ln(k) = ln(A) - a . You can see that by increasing T, a
RT RT
Ea
decreases, ln(A) - maximises and therefore ln(k) increases. Ln(n) increases as → ∞.
RT
You don’t have to know anything about the Arrhenius equation, I just wrote it to show
how do we get the relationship between thermodynamic temperature and k.
Rate constant k
Temperature / K
26.2-Heterogenous and Homogenous Catalysis
Homogenous catalysis: Homogeneous catalysis refers to reactions where the catalyst is in

the same phase as the reactants. The catalyst is soluble in the reaction mixture.
Heterogenous catalysis: Heterogenous catalysis refers to reactions where the catalyst is in
a different phase in contrast to the reactants. The catalyst is insoluble in reaction mixture.
Reaction Mechanism of Heterogenous Catalysis
Most heterogenous catalysts work by fitting the reactants into the active site of the surface
of the catalyst, reacting there, and then leaving the surface of the catalyst. The act of a
molecule bonding to the surface of a catalyst to react is known as adsorption.
Adsorption: Adsorption is the adhesion of atoms, ions or molecules from a gas, liquid or
dissolved solid to a surface. The particulates that adhere to the surface are called the
adsorbates and the surfaces to which they cling to are called the adsorbents. This is not
the same as aBsorption, where particulates go right through the aBsorbents. Chemical
adsorption is also called chemisorption.
The molecules diffuse to the surface of the metal/liquid catalyst, then the molecules are
physically adsorbed onto the surface via weak Van der Waals’ forces of attraction
between the catalyst and the gaseous molecules. Here starts the chemisorption of the
molecules at the surface, where the catalyst-reactant bonding strengthens and the atom-
atom bond weakens.
Desorption: Desorption is a phenomenon whereby a substance is detached from a surface.

The process is the opposite of adsorption.
Below is a diagram showing what happens when H2 gas is released in the manufacturing
of C2H6 from C2H4.
H H H H H H
Ni Ni Ni Ni Ni Ni Ni Ni Ni Ni Ni Ni
Ni Ni Ni Ni Ni Ni Ni Ni Ni Ni Ni Ni Ni Ni Ni
The H2 molecule The H-H bonds are weakening and the The H-H bonds are broken and the
approaches the Van der Waals forces between the H2 H-Ni bonds are established. We
surface of the catalyst molecule and Ni atoms strengthen say, the H atoms are chemisorbed.
The examples of heterogenous catalysis included in the syllabus is the use of iron in the
Haber-Bosch process for manufacturing ammonia from hydrogen and nitrogen gases,
and the use of palladium, rhodium and platinium in catalytic converters.
Iron in the Haber-Bosch process
N2(g) + 3H2(g) ⇌ 2NH3(g)
1-Diffusion: N2(g) + H2(g) move randomly by diffusion towards the surface of the Fe
catalyst.
2-Adsorption: N2(g) + H2(g) are chemisorbed onto the Fe catalyst surface. The chemical
bonds formed are strong enough to dismantle the H-H and N≡N bonds, but weak enough
to be able to set the products free off the surface.
3-Reaction: Chemisorbed N and H atoms react and bond on the Fe surface to form NH3.
4-Desorption: The NH3-Fe catalyst bonds disintegrate and set the NH3(g) molecules free.
5-Diffusion: NH3(g) molecules diffuse away from the Fe catalyst surface.
H H N N N N N N
H H H H
H H 3
1 2
N N
H H H H
’ ’
4 5
Transition Elements in Catalytic Converters
Catalytic converters in car exhausts are built into a honeycomb-shaped frame where the
metallic parts contain beads of palladium, rhodium or platinium. These 3 transition
metals are good catalysts when it comes to breaking down NxOy and CO and reassemble
them into N2 gas and CO2 gas. The mechanism is believed to be identical to the one above.
1-Oxides of nitrogen and CO diffuse onto the surface of the honeycomb.
2-The molecules are chemisorbed onto the surface of the catalyst, where bonds form
between the molecules and the transition metal lattice.
3-The chemical reaction starts, where the N-O bonds are broken and adjacent N atoms
form N2 gas and the CO molecules and oxygen atoms form bonds with each other to form
CO2 molecules.
4-The N2-metal bonds weaken and the N2 molecules desorb from the surface. Same thing
happens to the CO2 molecules.
5-The product molecules diffuse away from the surface of the honeycomb structure. -><-.
Reaction Mechanism of Homogenous Catalysis
The catalyst combines with the reactant molecules to form an intermediate, but the
intermediate is unstable so it recombines with other reactant molecules. By the end of the
reaction, the catalyst is regenerated and the products are formed.
Homogenous catalysis involves change in oxidation numbers of catalyst ions. Because

transition metal ions can have several oxidation states, they often make for good catalysts.
Example: The breakdown of hydrogen peroxide into water by iodide ions.
H2O2(aq) + I-(aq) → H2O(l) + IO-(aq) I-(aq) has -1 oxidation state, but IO-(aq)
H2O2(aq) + IO-(aq) → H2O(l) + I-(aq) + O2(g) has +1 oxidation state. IO- is an
intermediate that gets converted back to
I- ions, which are the catalyst.
Oxides of nitrogen in oxidation of sulfur dioxide
Atmospheric sulfur dioxide produced by the combustion of sulfur-contaminated fossil

fuels is oxidised into sulfur trioxide in a reaction that is catalysed by nitrogen (IV) oxide.
SO2(g) + NO2(g) → SO3(g) + NO(g) N in NO2(g) has +4 oxidation state, but N in
2NO(g) + O2(g) → 2NO2(g) NO(g) has +2 oxidation state. NO is an
intermediate that gets converted back to
NO2(g) molecules, which are the catalyst.
Iodine-Peroxodisulfate Reaction
S2O82-(aq) oxidise I-(aq) ions into I2(aq), but rate of reaction is too low to be effective. The
reaction is very slow because it would take large amounts of energy to enable the 2
negatively charged reactant ions to collide wit each other and react due to electrostatic
repulsion of like charges.
S2O82-(aq) + 2I-(aq) → 2SO42-(aq) + I2(aq)
A positive ion can help ensure that the 2 ions collide with each other. Fe3+ ions can catalyse
in the form of a double-step redox reaction, where in the 1st step, the Fe3+(aq) ions are
reduced to Fe2+(aq) by I-(aq) ions that are oxidised to I2(aq).
R1: 2Fe3+(aq) + 2I-(aq) → 2Fe2+(aq) + I2(aq)
R2: 2Fe2+(aq) + S2O82-(aq) → 2Fe3+(aq) + 2SO42-(aq)
You can start off by adding Fe2+(aq), as the reaction can proceed R2 to R1 as well.
Why Fe2+(aq)/Fe3+(aq) and not something else?
For a substance to act as a homogenous catalyst, its electrode potential must have a value
between the electrode potentials of the 2 other reactant molecules so that it can first reduce
the molecule with the more positive electrode potential then oxidise the reactant molecule
with the more negative electrode potential.
E⊝ / V
+2.01V S2O82-(aq) + 2e- ⇌ 2SO42-(aq)
+0.77V Fe3+(aq) + e- ⇌ 2Fe2+(aq)
+0.54V I2(aq) + 2e- ⇌ 2I-(aq)
Q1-State what substances can act as catalysts for the iodine-peroxodisulfate from below:
- Ni2+
(aq) + 2e ⇌ Ni(s)
- E⊝ = -0.25V
- Mn3+
(aq) + e ⇌ Mn (aq)
- 2+ E⊝ = +1.49V
- Ce4+
(aq) + e ⇌ Ce (aq)
- 3+ E⊝ = +1.70V
- Cu2+
(aq) + e ⇌ Cu (aq)
- + E⊝ = +0.15V
Solution: Mn3+/Mn2+ & Ce4+/Ce3+ because of their E⊝ values.
27-Group 2
27.1-Similarities and trends in the properties of the group 2 metals and their
compounds.
Thermal Stability of group 2 nitrates and carbonates
In high temperatures, Group 2 carbonates decompose into group 2 oxides and carbon
dioxide. As you move down group 2, the thermal stability of group 2 carbonates increases.
BaCO3 > SrCO3 > CaCO3 > MgCO3
Temperature
∆Enthalpy
Temperature / K
∆HR / kJ mol-1
MgCO3 CaCO3 SrCO3 BaCO3
Explanation of the trend: The ionic radius of large anions such as CO32-(aq) and NO3-(aq)
allows them to be easily polarized by comparatively smaller cations such as the metallic
cations of group 2 elements. The ionic radius of the cations of group 2 increases as you
move down the group due to the increase of quantum shell numbers and the distance
between the nucleus and the valence electrons. The smaller the cation, the better of a
polarizer of large anions it becomes, so the degree of polarizability of the CO 32- and NO3-
decreases as you move down the group. The more polarized and distorted the large anion
is, the easier it is to disintegrate the C=O bonds and N=O bonds within the anionic cloud.
2+ 2- 2+ 2- 2+ 2-
Cationic radius increases, polarizability

decreases and therefore thermal stability
increases.
Q1-Use ideas about ion polarization to explain why magnesium nitrate undergoes thermal
decomposition at a much lower temperature than barium nitrate.
Solution: Mg2+(aq) is a much smaller cation compared to Ba2+(aq), meaning that Mg2+(aq)
is a better anionic polarizer of NO3-(aq) due to its higher charge density. The increased
polarization within MgNO3 requires less thermal energy to breakdown when compared to
the more thermally stable BaNO3.
Solubility of group 2 hydroxides and sulfates
The solubility of group 2 hydroxides increases down the group:

The solubility of ionic salts is completely dependent on the standard enthalpy change of
⊝
solution, ∆HSol , which is the energy released when 1 mole of ionic solid dissolves in
sufficient amounts of water to form a dilute solutimon under standard conditions.
⊝
If ∆HSol is negative or minimally positive, then the ionic compound is relatively soluble.
⊝
For example, ∆HSol [MgCl2] = -55 kJ mol-1, meaning that 55 kJ mol-1 of energy is
released when 1 mol [MgCl2] is dissolved in sufficient amounts of water, so MgCl2 is
very soluble in water.
⊝ ⊝ ⊝
We know that ∆HSol = ∆Hlatt + ∆Hhyd from chapter 23.
⊝
∆Hlatt is the energy released when gaseous ions combine to form one mole of an ionic
⊝
compound under standard conditions. Because the energy is always released, ∆Hlatt is
always negative.
⊝
∆Hhyd is the energy released when gaseous ions dissolve in enough water to form a dilute
⊝
solution under standard conditions. Because the energy is always released, ∆Hhyd is
always negative.
⊝
As you move down group 2, the ∆Hlatt of the ionic compound decreases because the group
2 cations become bigger and bigger, their ionic radius increases, the charge density
decreases, the electrostatic attraction of the oppositely-charged ions within the lattice
decreases, the energy released when the ionic bonds are formed from the gaseous ions
⊝
decreases. This is why ∆Hlatt becomes less exothermic.
⊝
As you move down the group 2, the ∆Hhyd of the ionic compounds decreases because the
group 2 cations become bigger and bigger, their ionic radius increases, the ion-dipole
attractions weaken and less energy is released due to ion-water bond formation weakening.
⊝
This is why ∆Hhyd becomes less exothermic.
What happens with group 2 hydroxides?
As you move down the group, the lattice energy decreases due to the increase in ionic
radius and decrease in charge density. The strength of electrostatic attraction that affects
lattice energy values are inversely proportional to the square of the distance between the
charges, but the hydration energy doesn’t decrease as much as you move down the group.
The enthalpy change of solution becomes more negative as you move down the group,
making it more exothermic and more soluble.
What happens with group 2 sulfates?
The solubility of group 2 sulfates decreases down the group:

As you move down the group, the lattice energy decreases due to the increase in ionic
radius and decrease in charge density, but the shape and the large size of the SO42-(aq)
makes the increase in ionic radius obsolete. The hydration energy keeps decreasing by the
⊝ ⊝
same amounts as in OH-(aq). The decrease in ∆Hhyd is faster than the decrease in ∆Hlatt ,
⊝
so the overall ∆Hsol becomes more and more positive down the group which means that the
solubility would decrease.
28-Chemistry of Transition Elements
28.1-General Physical & Chemical Properties of the 1st Row of Transition

Elements, Ti to Cu.
Transition Element: A transition element is a d-block element which forms 1 or more stable
ions with incomplete d-orbitals.
Scandium forms one stable ion, Sc3+(aq), with 1s2 2s2 2p6 3s2 3p6 3d0 4s0 showing it has
no e- in a d-subshell. Zinc forms one stable ion, Zn2+(aq), with 1s2 2s2 2p6 3s2 3p6 3d10 4s2
showing it has a complete d-subshell.
N=5 5p When filling electrons into the orbitals of
transition elements, the 4s subshell is filled
4d first before the 3d orbital for all transition
metals, but once filled, the 4s e- are removed
5s
before the 3d e-. This is because the 4s
N=4 4p electrons are at a lower energy level
compared to the 3d electrons so they will be
3d added first, but the 3d subshell is closer to
4s Increasing the nucleus compared to the 4s, so their will
N=3 3p e- energy
be removed last. This rule works for all
3s transition metals except for chromium and
copper, where chromium has an electronic
configuration of 1s2 2s2 2p6 3s2 3p6 3d5 4s1
2p instead of 1s2 2s2 2p6 3s2 3p6 3d4 4s2 and
N=2 copper has an electronic configuration of
2s 1s2 2s2 2p6 3s2 3p6 3d10 4s1 instead of
1s2 2s2 2p6 3s2 3p6 3d9 4s2. This is because
1s
the stability of half-filled or full-filled
N=1
orbitals is > any other permutation of e-.
z
y Shapes of d-orbitals z
z
z
z
x y x
y y y
x
dxy orbital x dyz orbital dxz orbital
x
A2 A-level Chemistry Notes z
z
y z
x
y y
x x
dx2-y2 orbital dz2 orbital
Q1-Chromium is element 24 in the periodic table and it forms compounds with both the +2
and +3 oxidation states. Write down the electronic configuration for Cr, Cr2+ and Cr3+.
Solution: Cr = 1s2 2s2 2p6 3s2 3p6 3d5 4s1
Cr2+ = 1s2 2s2 2p6 3s2 3p6 3d4
Cr3+ = 1s2 2s2 2p6 3s2 3p6 3d3
Q2-Transition elements have ions with variable oxidation states

a) Write down the electronic configuration for V3+.
Solution: V = 1s2 2s2 2p6 3s2 3p6 3d3 4s2, so V3+ = 1s2 2s2 2p6 3s2 3p6 3d2.
b) Find the number of unpaired electrons for V3+.
Solution: 2 electrons exist in 2 orbitals, so 2 electrons are unpaired.
Unique Properties of Transition Elements
1-Ability for their ions to exist in multiple oxidation states:

Due to the similarity in the energy level of the 4s and 3d subshells, the transition metals
can lose multiple permutations of electrons while still maintaining stability to further react
with other ions and form chemical compounds. The maximum oxidation state of a
transition element is given by the number of unpaired 3d and 4s electrons. For example,
manganese has a [Ar] 3d5 4s2, meaning it has 7 unpaired e-. Therefore, the maximum
oxidation state for manganese = +7.
2-Effective and High Catalytic Activity:

Due to the variance in oxidation states, transition elements can form stable cations with
different oxidation states, and this gives them the ability to form unstable intermediates
which readily decompose to yield the products and regenerating the catalysts. The vacancy
of d-orbitals that are energetically accessible is the reason why transition elements ions can
form dative bonds with ‘ligands’, substances that you’ll find more about later on in the
chapter.
3-Formational ability of complex ions.

The cations of transition elements have strong tendencies to form complex ions with
molecules having lone pairs of electrons due to their relatively small size and high positive
charge densities that allow them to attract electrons. The presence of vacant d-orbitals that
are energetically accessible allows them to accept electrons from ligand molecules.
Examples of complex transition metal ions: [Fe(CN)6]4- and [Cu(H2O)4(NH3)2]2+.
4-Formation of colored compounds:

Transition metal ions containing unpaired d-orbital electrons undergo electronic transitions
from 1 d-orbital to another. During this transition, electrons will absorb enough energy and
emit the rest of the energy as radiation that happens to be colored when of the frequency of
the radiation that happens to correspond to visible light. This will be discussed further ↓.
28.2-General Chemical Properties of the 1st set of Transition Elements
Ligands: Species that contain lone pairs of e- that form dative covalent bonds to a central
metal atom or ion. Ligands come as monodentate, bidentate or polydentate ligands.
Monodentate ligands: Ligands that donate a single lone pair to the central metal ion to
form a single dative bond within the coordination complex. Examples include simple
neutral molecules such as NH3, H2O, CO, CO2 or singly-charged ions such as Cl- or OH-.
Bidentate Ligands: Ligands that donate 2 lone pairs to the central metal ion to form 2
dative bonds within the coordination complex. Examples include organic molecules such as
1,2-diaminoethane and ethane-1,2-diol or doubly-negative ions such as the ethandioate ion.
Polydentate Ligands: Ligands that donate > 2 lone pairs to the central metal ion to form 2
dative bonds within the coordination complex. Examples include large organic ions such as
ethane-1,2-dinitrotetracetic acid, or EDTA4-.
Complex Ions: Molecules or Ions formed by a central atom or ion surrounded by one or
more ligands.
Shapes of coordination complexes
Coordination Number: The number of coordinate bonds to the central metal ion.
[Fe(CN)6]3- has a coordination number of 6 because 6 CN- ions bonded to a single Fe3+
ions.
The coordination number is mostly 2, 4 or 6, but can have any value from 1-16. When the
coordination number is 2, the shape of the complex is always linear. An example for this is
the diamminesilver (I) cation with the following shape.
180°
H H
H N Ag N H
H H
When the coordination number is 4, the complex can either be square planar or tetrahedral.
Cl 2-
Cl NH3
Cu Pt 90°
Cl 109.5° Cl H 3N Cl
Cl
[CuCl4]2- [Pt(NH3)2Cl2]
When the coordination number is 6, the complex will be octahedral.
CN- 3-
NC- CN-
Fe
NC- CN-
CN-
[Fe(CN)6]3-
You can deduce the oxidation states of transition elements using the charge of the
coordination complex itself. For example, [Fe(CN)6]3- must have an Fe3+ within it
because CN- has a charge of 1-.
Q1-What is the oxidation state of Cu in Cu(OH)2(H2O)4?

Solution: Overall charge = 0, xCu + 2(-1) + 4(0) = 0
XCu = 2+.
Q2-Bubbling air through different aqueous mixtures of CoCl2, NH4Cl and NH3 produces
various complex ions with the general formula [Co(NH3)6-nCln]3-n. Determine the
oxidation state of the cobalt in these complex ions.
Solution: Let the charge on the cobalt be XCo:
XCo + (6 – n)(0) + n(-1) = 3 – n
XCo = 3 – n + n = +3
If n Cl- ions exist in a compound, then their total charge is -n.
Q3-Predict the shape of the [Fe(H2NCH2 CH2NH2)3]3- transition metal complex.

Solution: H2NCH2 CH2NH2 is a bidentate ligand, and 3 of them exist, so 6 bonds exist.
Coordination number = 6, so the compound is octahedral.
Ligand Exchange Reactions
Ligand exchange or ligand substitution reactions occur when ligands are either fully or
partially substituted with other ligands. Ligand exchange reactions form new complexes
that are more stable compared to the reactant complex. The coordination number and the
geometry of the coordination complex won’t change if the size of the old and new ligands is
the same, but if the ligand size changes significantly, then the geometry and the
coordination number will change.
The main liquid exchange reactions that you’ll have to focus on are cobalt (II) ion and
copper (II) ion reacting with H2O and NH3 molecules as well as Cl- and OH- ions.
When testing for Cu2+(aq) ions using NaOH(aq), the Cu2+(aq) is actually [Cu(H2O)6]2+
because the Cu2+ attracts the water molecules to form a coordination complex that is blue-
colored. The reaction between the complex and OH-(aq) forms the following complex:
R1: [Cu(H2O)6]2+(aq) + 2OH-(aq) ⇌ [Cu(H2O)4(OH)2](s) + 2H2O(l)
Blue solution Pale-Blue Precipitate
If concentrated NH3(aq) is now added, the pale-blue precipitate dissolves into a deep-blue
solution with a new complex and hence the new color.
[Cu(H2O)4(OH)2](s) + 4NH3(aq) ⇌ [Cu(H2O)2(NH3)4]2+(aq) + 2H2O(l) + 2OH-(aq)
R1 can also occur when dilute NH3(aq) is added to CuSO4(aq) or when concentrated
NH3(aq) is added dropwise to CuSO4(aq) and then the NH3(aq) is in excess and R2 occurs,
but the reaction is a stepwise equilibrium:
[Cu(H2O)6]2+(aq) + NH3(aq) ⇌ [Cu(H2O)5(OH)]+(aq) + NH4+(aq)
[Cu(H2O)5(OH)]+(aq) ⇌ [Cu(H2O)4(OH)2](s) + H+(aq)
The water ligands in [Cu(H2O)6]2+(aq) can be replaced by Cl-(aq) ions to give [CuCl4]2-(aq)
by the addition of concentrated HCl(aq) to the complex. [CuCl4]2-(aq) is a yellow solution.
[Cu(H2O)6]2+(aq) + 4Cl-(aq) ⇌ [CuCl4]2-(aq) + 6H2O(l)
Blue Solution Yellow Solution
2-
Cl You must learn the formulae,
When testing for Cu2+(aq), the colors, compound structures
reason why the solution becomes and geometries of these
a deep/dark/royal blue when Cu reactions.
NH3(aq) is in excess is because of
the [Cu(NH3)4] 2+ and
[Cu(NH3)4(H2O)2]2+ complexs Cl Cl
Cl
Cobalt (II) ions are actually [Co(H2O)6]2+(aq) when in solution, which is similar to
copper. This complex gives some cobalt salts their characteristic pink color. On the addition
of NaOH(aq) into a solution containing the [Co(H2O)6]2+(aq) complex, a blue precipitate
of Co(OH)2(s) forms.
[Co(H2O)6]2+(aq) + 2OH-(aq) → Co(OH)2(s) + 6H2O(l)
Pink Solution Blue Precipitate
The blue precipitate will turn red when warmed with an excess alkali.
The water ligands in [Co(H2O)6]2+(aq) can also be replaced fully by NH3 molecules by
the dropwise addition of concentrated NH3(aq).
[Co(H2O)6]2+(aq) + 6NH3(aq) ⇌ [Co(NH3)6]2+(aq) + 6H2O(l)
Pink Solution Brown Solution
The addition of concentrated HCl(aq), dropwise, results in the formation of the tetrahedral
blue-colored complex [CoCl4]2-(aq).
[Co(H2O)6]2+(aq) + 4Cl-(aq) ⇌ [CoCl4]2-(aq) + 6H2O(l)
Pink Solution Blue Solution
Coordination complexes of Co2+(aq) ions are usually tetrahedral if the coordination number
is 4, but they can also be square planar.
Q1-When NH3(aq) is added to a green solution containing [Ni(H2O)6]2+(aq), a grey-green

precipitate, A is formed. This precipitate dissolves in excess NH3(aq) to give a blue-violet
solution, B. Suggest formulae for A and B and write equations for the 2 reactions
producing A and B.
Solution: Because they say “Suggest”, use your knowledge of similar reactions to come up
with one.
For A: [Ni(H2O)6]2+(aq) + NH3(aq) ⇌ [Ni(H2O)5(OH)](aq) + NH4+(aq)
Then [Ni(H2O)5(OH)](aq) ⇌ [Ni(H2O)4(OH)2](aq) + H+(aq)
For B: [Ni(H2O)4(OH)2](aq) + 4NH3(aq) ⇌ [Ni(H2O)2(NH3)4](aq) + 2H2O(l)
Q2-EDTA4- is a polydentate ligand. When a solution of EDTA4- is added to a solution

containing [Cu(H2O)6]2+(aq), a new complex s formed. The formula of this complex is
[CuEDTA]2-(aq).
a) Name the type of reaction that occurs.
Solution: Ligand Exchange Reaction.
b) When ethanedioate ions are added to a solution of zirconium ions, Zr4+(aq), a complex
ion containing four C2O42-(aq) ions and one Zr4+(aq) ion is formed. All four ethanedioate ions
act as bidentate ligands in this complex. Give the formula of this complex ion and explain
why this complex is not octahedral.
Solution: Formula = [Zr(C2O4)]4-(aq) and the compounds is non-octahedral because 4
bidentate bonds = 8 bonds ≠ 6 bonds.
Redox Reactions and their use regarding Transition Elements
Due to their ability to exist in different stable oxidation states, transition element ions can
take part in redox reactions easily. We can use the electrode potential values, E⊝ , to deduce
the feasibility of a redox reaction occurring if it involves transition metal ions and whether
a reagent is suitable for reducing or oxidizing a transition metal atom or ion. Remember
that the less positive equilibrium moves to the left.
When Fe3+(aq) is reduced to Fe2+(aq), the following reaction happens:
Fe3+(aq) + e- → Fe2+(aq) E⊝ = +0.77V
When MnO4-(aq) are reduced to Mn2+(aq) ions in acidic medium, the following reaction
happens:
MnO4-(aq) + 8H+(aq) + 5e- → Mn2+(aq) 4H2O(l) E⊝ = +1.52V
Can Fe3+ ions oxidise Mn2+ into MnO4- ions?
To answer such questions, you need to consider an overall reaction.
If Fe3+(aq) + e- → Fe2+(aq) has a E⊝ = +0.77V, Fe2+(aq) → Fe3+(aq) + e- has E⊝ = -0.77V
Now add the 2 equations after balancing:
5Fe3+(aq) + Mn2+(aq) + 4H2O(l) → MnO4-(aq) + 5Fe3+(aq) + 8H+(aq) with E⊝ = +0.75V
As the E⊝ increases, the tendency of the reaction to move forward increases. So, because the
E⊝ = +0.77V, the reaction proceeds forward and the Fe3+(aq) will be able to oxidise
Mn2+(aq) ions into MnO4-(aq) successfully.
Q1-Will oxygen oxidise iron(II) hydroxide into iron(III) hydroxide in alkaline

conditions?
Solution: The relevant redox equations from the data booklet are:
Fe(OH)3(s) + e- ⇌ Fe(OH)2(s) + OH- E⊝ = -0.56V
O2(g) + 2H2O(l) + 4e- ⇌ 4OH-(aq) E⊝ = +0.40V
Reverse the 1st equation, balance and add:
4Fe(OH)2(s) + 4OH-(aq) + O2(g) + 2H2O(l) ⇌ 4Fe(OH)3(s) + 4OH-(aq)
4Fe(OH)2(s) + O2(g) + 2H2O(l) ⇌ 4Fe(OH)3(s) E⊝ = 0.96V
E⊝ is positive, so the reaction is feasible.
Q2-Will chlorine oxidise Mn2+(aq) into MnO4-(aq) in acidic solution?

Solution: Relevant equations: Cl2(g) + 2e- ⇌ 2Cl-(aq) E⊝ = +1.36V
MnO4-(aq) + 8H+(aq) + 5e- ⇌ Mn2+(aq) + 4H2O(l) E⊝ = +1.52V
R1 moves to the left, because it is less positive and R2 moves to the right because it is more
positive. In order to react, R2 would have to move to the left, and that is impossible, so
that reaction is non-feasible.
Choosing Oxidising Agents for Reactions
Remember that the oxidising agent itself gets reduced. An example will be a good way of
understanding:
What would you use to oxidise Fe2+(aq) into Fe3+(aq)?
The relevant equation would be Fe3+(aq) + e- ⇌ Fe2+(aq) and this reaction has a E⊝ =
+0.77V. What we want to do is to move the equilibrium to the left. We know that if the
reaction has a negative E⊝ value, it will move to the left. What we need to exactly do is to
move the reaction to the left. Right-reactions happen to be the more positive ones, so we need
to pair this reaction up with a more positive reaction to force it to move to the left. An
example is MnO4-(aq)/Mn2+(aq) half-cell which has a E⊝ of 1.52V.
Choosing Reducing Agents for Reactions
Remember that the reducing agent itself gets oxidised. An example will be a good way of
understanding:
What would you to reduce Mn3+(aq) into Mn2+(aq)?
The relevant equation would be Mn3+(aq) + e- ⇌ Mn2+(aq) and this reaction has a E⊝ =
+1.49V. What we want to do is to move the equilibrium to the right. We know that if the
reaction has a positive E⊝ value, it will move to the right. What we need to exactly do is to
move the reaction to the left. Left-reactions happen to be the less positive ones, so we need to
pair this reaction with a less positive reaction to force it to move to the right. An example is
the Cu2+(aq)/Cu(s) half-cell which has a E⊝ of +0.34V
Redox Reaction Systems to be dived into in depth
1-MnO4-(aq)/C2O42-(aq) in acidic medium.

When MnO4- reacts with C2O42- ions, the C2O42- ions are oxidised in what is known as a
redox reaction. The half-equations involved are:
HR1: MnO4-(aq) + 8H+(aq) + 5e- → Mn2+(aq) + 4H2O(l)
HR2: C2O42-(aq) → 2CO2(aq) + 2e-
By balancing and adding, the full equation is:

2MnO4-(aq) + 5C2O42-(aq) + 16H+(aq) → 10CO2(g) + 2Mn2+(aq) + 8H2O(l)
The oxidation state of Mn changes from +7 → +2, so Mn is reduced and is the oxidising
agent. The oxidation state of C changes from +3 → +4, so C is oxidised and is the reducing
agent.
C2O42-(aq) happens to be a toxic ion when present in blood, and we can find its concentration
in blood using a titration reaction with MnO4-. Pure C2O42- solution is colorless, and the
solution keeps its lack of color during the addition of purple MnO4-(aq), but the end-point is
given by the point when a permanent faint pink stain remains. The volume of MnO4-(aq)
along with its known concentration can be used to determine mol[MnO4-], and this can be
used to find the mol[C2O42-]. This value along with the concentration of the C2O42-(aq) can
be used to determine the volume of C2O42- in solution.
2-Fe2+(aq)/MnO4-(aq) in acidic medium.

When Fe2+(aq) ions react with MnO4-(aq), the Fe2+(aq) ions are oxidised in what is known as
a redox equation. The half-equations involved are:
HR1: Fe2+(aq) → Fe3+(aq) + e-
HR2: MnO4-(aq) + 8H+(aq) + 5e- → Mn2+(aq) + 4H2O(l)
By balancing and adding, the full-equation is:

5Fe2+(aq) + MnO4-(aq) + 8H+(aq) → 5Fe3+(aq) + Mn2+(aq) + 4H2O(l)
A similar technique to what is written above is used to find the amount Fe2+(aq) in a known
compound/mixture.
Q1-0.560g of iron ore were dissolved in acid, so that all of the iron present in the original
ore was then present as Fe2+(aq). The solution obtained was titrated against 0.01600 mol
dm-3 KMnO4(aq). The amount of KMnO4(aq), or titre, is 41.50 cm-3.
Calculate the percentage mass of iron in the 0.560g of iron ore.
41.50
Solution: Mol[MnO4-(aq)] = 0.016 × = 0.000664 mol
1000
5Fe2+(aq) + MnO4-(aq) + 8H+(aq) → 5Fe3+(aq) + Mn2+(aq) + 4H2O(l)
So, Mol[Fe2+ (aq)] = 0.000664 × 5 = 0.00332 mol
Mass[Fe2+(aq)] = 0.00332 × 56 = 0.18592g of iron
%mass = 0.18592/0.560 × 100 = 33.2%.
3-Cu2+/I-(aq) system.
When Cu2+(aq) and I-(aq) ions react, the I-(aq) ions are oxidised and are themselves the
reducing agents in what is known as redox reaction. The half-equations involved are:
HR1: 2I-(aq) → I2(aq) + 2e-
HR2: Cu2+(aq) + e- → Cu+(aq)
By balancing and adding, the full-equation is:

2Cu2+(aq) + 2I-(aq) → I2(aq) + Cu+(aq)
If the I-(aq) ions are in excess, then copper(I) iodide precipitates:
R1: 2Cu+(aq) + 4I-(aq) → I2(aq) + 2CuI(s)
A titration reaction can be used to find the concentration of Cu2+(aq) in solution.
A known concentration of sodium thiosulfate (Na2S2O3) is added from a burette into an R1

reaction mixture, where the S2O32- ions react with the I2(aq). As the I2(aq) concentration
decreases, the brown color intensity decreases, and this can be used to determine the end-point
of the reaction. When the solution is as light in brown as possible, starch solution is added to
stain the rest in a deep blue color and the rest of the S2O32- can be added until the solution
goes colorless. The volume of the Na2S2O3 added along with the concentration can be used to
determine the moles of S2O32-(aq) that reacted. Using the stoichiometric ratio of the equation,
it can be calculated that the moles of I2 reacted = half the moles of S2O32- that reacted. The
moles of I2 that reacted = half the amount of Cu2+(aq) that reacted. Divide the actual moles
of Cu2+(aq) that reacted by the reaction mixture volume to get the concentration.
28.3-Colours of Complexes
Degenerate d-orbitals: When 2 or more electron orbitals are of the same exact energy, they
are known as degenerate electron orbitals.
Non-degenerate d-orbitals: When 2 or more electron orbitals are not of the same exact
energy, they are known as non-degenerate orbitals.
To better understand this topic, I will introduce something that is completely outside of the
syllabus, but will for sure help you understand the big picture.
Crystal Field Theory (CFT)
In CFT, we consider ligands as negative point charges that repel the transition metal
d-orbitals. The octahedral diagrams show how the d-orbitals intersect with ligands.
dxy-orbital dyz-orbital dxz-orbital
dx2 -y2 -orbital dz2 -orbital

As you can see from these diagrams, the ligand point charges are directed in between the
dxy, dyz and dxz orbitals. You can clearly see that the electronic orbital clouds are never
perfectly aligned with the ligands, so these orbitals are relatively stable because they
experience the least amount of electrostatic repulsion.
The dx2 -y2 and dz2 have some areas where they are perfectly aligned with the ligand point
charges, so these 2 orbitals will experience the highest amount of electrostatic repulsion due
to their close proximity with the ligands.
We know from before that orbitals of the same subshell always have the same amount of
energy, but here they form 2 groups where 1 has higher and the other has lower energy.
This splitting of orbitals due to the difference in their energy levels is what is known as
orbital splitting.
A visual representation of what happens to the d-orbitals in the case for octahedral
complexes is shown below:
E
dz2 dx2 -y2 ∆E, which is known as the
“Crystal Field Splitting
Energy”. This is basically a
dxy dyz dxz
measure of how split the new
orbitals are in terms of the
d-orbitals in an
isolated transition
energy between the levels.
element ion.
The ∆E is dependent on the nature of the point charge ligands. If the ligands are highly
repulsive, then the splitting is going to be greater and hence ∆E is greater. If the ligands are
not very repulsive, then the splitting is going to be greater and hence the ∆E is smaller.
Highly repulsive ligands are known as “Strong Field Ligands” and weakly repulsive
ligands are known as “Weak Field Ligands”.
I- < Br- < Cl- < SCN- < F- < OH- < C2O4- <H2O < EDTA4- < NH3 < CO < CN-
Weak Field Strong Field
Ligands Ligands
Now let’s look at the tetrahedral complex diagrams for the intersection between the d-
orbitals and the ligand point charges.
If an arrow is red, the repulsion is strong. If an arrow is orange, the repulsion is of

mediocre strength and if the arrow is yellow then the repulsion is weak. As you can see,
the dxy, dyz and dxz orbitals are experiencing higher electrostatic repulsion compared to the
dx2-y2 and dz2 orbitals. So in tetrahedral coordination complexes, the orbital splitting will
render the dx2-y2 & dz2 less energetic and the rest of the orbitals become of higher energy. A
diagram for the orbital splitting is shown below:
E
dxy dyz dxz
∆E, which is known as the
“Crystal Field Splitting
Energy”. This is basically a
dz2 dx2 -y2
measure of how split the new
d-orbitals in an orbitals are in terms of the
isolated transition energy between the levels.
element ion.
Because all d-orbitals show some form of significant repulsion with tetrahedral
coordination complexes, the ∆E are almost always small and e- are singles.
The square planar geometry also has an interesting orbital splitting chemistry, but that’s
outside of the syllabus because it’s a bit more complex.
Why transition metal coordination complexes are coloured?
When light falls on a solution containing transition metal coordination complexes, a

certain amount of energy from the light is absorbed by the electrons in the degenerate d-
orbitals which lead to the splitting of the orbital into 2 non-degenerate orbitals. That
energy that was absorbed will power the electron up into the higher energy group of
orbitals. The energy absorbed, or ∆E, corresponds to a certain frequency of light that is
absorbed. When certain frequencies are absorbed from white light and others are reflected,
color is a result.
So, when you’re asked about why transition metal complexes are coloured, say:
Solution: The d-subshell is split into 2 groups of orbitals where 1 is of higher energy and
the other is of lower energy. Photons with the right amount of energy needed to transition
an electron from the lower to the higher of the groups of the orbitals. That energy absorbed
corresponds to a certain frequency of light that is absorbed, which leads to the complex
having a color complementary to the absorbed color on the color wheel.
The ∆E value is exactly equal to the Planck Constant h multiplied by the frequency f of
the incident radiation. ∆E = hf.
Tip: Strong Field Ligands will generate high ∆E values because of the high electrostatic
repulsion. This means that these ligand molecules will absorb high energy (high
frequency visible light photons) photons which are blue-violet resulting in yellow-red
colors. Weak field Ligands will generate low ∆E values because of the low electrostatic
repulsion. This means that these ligand molecules will absorb low energy (low frequency
visible light photons) photons which are red-orange resulting in green-blue colours.
How to predict the colors from given absorbance spectra?

As you can see on the left, a certain molecule
Absorbance
absorbs light of very low (Violet-indigo) and

high (orange-red) wavelengths. This leaves the
blue and green lights to be transmitted, giving
rise to a cyan-coloured compound.
𝜆 / nm
28.4-Stereoisomerism in Transition Element Complexes.
Geometric (Cis-Trans) Isomerism
Geometric Isomerism in Coordination Complexes: Complexes with the same molecular

formula but different geospatial arrangements of their atoms.
The cis form of the isomers refers to when a specific atom or a group of atoms are on the
same spatial side of the complex. The trans form of the isomers refers to when a specific
atom or a group of atoms are on opposite spatial side of the complex.
Linear coordination complexes (Coordination number 2) and tetrahedral coordination

complexes (Coordination number 4) can show no form of geometrical isomerism,
because there is no way of arranging the atoms in both same/opposite combinations.
Now let’s look at examples regarding square planar complexes for [Pt(NH3)2(Cl2)]
Cl NH3 This compound is also known as Cl NH3
platin. The left version is cis and the
right version is trans. Cis-platin is
Pt an anti-cancer drug due to its ability Pt
to bind to cancerous cell DNA and
inhibit cellular replication.
Cl NH3 H 3N Cl
Cis-Platin Trans-Platin
H 3N NH3
H 3N CO
The left version is cis and the right
version is trans because the NH3
Ir
Ir molecules are on the same side on the
left and on opposite sides on the left.
Cl OC Cl
H3N
Cis-[Ir(CO)(Cl)(NH3)2] Trans-[Ir(CO)(Cl)(NH3)2]
Next, let’s look at cis-trans isomerism for octahedral complexes.

2+ H 2O 2+
H 2O
H 3N NH 3
This is [Cu(NH3)4(H2O)2]. The H 3 N NH3
version on the left is trans and the
version on the right is cis. On the left
Cu trans version, H2O molecules are in Cu
opposite directions to each other, but on
the right cis version, H2O molecules are
H 3N NH3 on non-directly opposite positions. H 3N H 2O
H2O NH3
Cis-[Cu(NH3)4(H2O)2]
Trans-[Cu(NH3)4(H2O)2]
H 2O
H 2O This is [Ni(H2O)2(H2NCH2CH2NH2]2+ H2N OH2
H2N NH2
An example of bidentate
H2C CH2 ligands. Left is trans and right H2C Ni
Ni is cis. Note how the N atoms H2C
H2C CH2 are always the ones bonded to
the central transition ion. H2N NH2
H2N H O NH2 NH2
2
CH2
CH2
Q1-Draw all possible cis-trans isomers for [Cr(H2NCH2CH2NH2)2(CN)2]+, using
“en” to represent one 1,2-diammineethane molecule with curved arrows for the rest of the
molecules.
Solution: en
CN-
N -C
en Cr en Cr
N -C
CN-
Trans-[Cr(H2NCH2CH2NH2)2(CN)2]+ en
Cis-[Cr(H2NCH2CH2NH2)2(CN)2]+
Optical Isomerism: Optical Isomerism occurs when substances with same molecular and
structural formulae, but one of the molecules cannot be superimposed on the image of the
other. Simply put, they are mirror images of each other, like your left and right hands.
Two isomers exhibiting optical isomerism are enantiomers of each other.
en en
Ni en en Ni
en en
The above diagram shows 2 non-superimposable images of 2 [Ni(H2NH2CH2CNH2)]2+
enantiomers.
A similar thing happens for all coordination complex enantiomers.
28.5-Stability Constant KStab
Stability Constant: The stability constant is an equilibrium constant for the formation of a
complex ion in a solvent from its constituent ions or molecules. It is denoted by KStab and
its units are dependent on the reaction equation.
Consider the following reaction:

[Cu(H2O)6]2+(aq) + 4NH3(aq) ⇌ [Cu(NH3)4(H2O)2]2+(aq) + 4H2O(l)
For ligand exchange reactions like these, the direction of the equilibrium will lie towards
the side where the complex is of higher stability. Le Chatelier’s principle still applies here;
if we add water to the reaction mixture, the equilibrium shifts to the left and the
concentration of the complex with more H2O molecules increases.
[[Cu(NH3 )4 (H2 O)2 ]2+ ]

The KStab expression is given by KStab = , so the same technique for
[Cu(H2 O)6 ]2+ ] [NH3 ]4
Kc expression writing. Just like Kc, we don’t mention H2O’s concentration here.
The stability constant value is are used to a measure for the stability of a coordination
complex compared to the original complex with the original ligand where the complex
was an aqueous ion. So, the higher the value, the more stable the new complex is and the
more the equilibrium lies towards the side where the new complex exists. If a ligand
displacement reaction is to occur, the KStab for the new complex must be > KStab for the
old complex.
Q1-Write down the expression for the stability constant for the following ligand exchange
reaction as well as the unit.
a) [PtCl4]2-(aq) + 2NH3(aq) ⇌ [PtCl2(NH3)2](aq) + 2Cl-(aq)
[[Pt(NH3 )2 (Cl)2 ]2+ ] [Cl- ]2
Solution: KStab =
[[Pt (Cl)4 ]2- ] [NH3 ]2
(mol dm-3 ) × (mol dm-3 )2
Unit: = unitless constant.
(mol dm-3 ) × (mol dm-3 )2
Q2-EDTA4- is a polydentate ligand. When a solution of EDTA4- is added to a solution

containing [Cu(H2O)6]2+, a new complex is formed. The formula of this complex is
[CuEDTA4-]2-.
a) Name the type of reaction happening here.
Solution: Ligand Exchange Reaction
b) Write an equation for the KStab of [CuEDTA4-]2- for this reaction.

Solution: R: [Cu(H2O)6]2+(aq) + EDTA4-(aq) ⇌ [CuEDTA4-]2- + 6H2O(l)
[[CuEDTA4- ]2- ]
KStab =
[[Cu(H2 O)6 ]2+ ] [EDTA4- ]
c)The numerical value for the KStab of [CuEDTA4-]2- is 6.3 × 1019 at 298K.
State what this tells us about the [CuEDTA4-]2- complex ion.
Solution: The formation of [CuEDTA4-]2- complex from the original complex is highly
favored because the [CuEDTA4-]2- is highly stable compared to the original complex.
d) Copper is a transition element that exists in 2 stable oxidation states +1 and +2.
Explain why most Cu(I) salts are white.
Solution: Cu(I) has a 10 e- in its 3d orbital, so there is no possible way for the electrons
to transition between two groups of orbitals of different energy levels.
A2 A-level Chemistry Notes H3C Is good
for you!
29-An introduction to A level organic chemistry
29.1-Formulae, Functional Groups and the Naming H
of Organic Compounds H
N
CH3
H3C
Functional Groups: An atom or a group of atoms that are responsible for the physical
and chemical characteristics of an organic molecule.
General Formula: A general formula is a type of empirical formula that represents the
composition of any member of an entire class of compounds.
Structural Formula: The structural formula of a chemical compound is a graphic
representation of the molecular structure showing how the atoms are possibly arranged in
real 3D space.
Displayed Formula: A displayed formula is a type of structural formula and shows all
the bonds in the molecule as individual lines, where each lines show a pair of shared e-.
Skeletal Formula: The skeletal formula is a shorthand representation of an organic
molecule’s structure where the main skeleton of the molecule is represented by lines and the
unique functional groups are the ones explicitly displayed.
All of the functional groups you need to be familiar with are:

O
C C C C C C X C C OH C C H
Alkanes Alkenes Halogenoalkanes Alcohols Aldehydes

X = halogen atom
O O O
C C NH2
R’ C R’’ R C OH R’ C
O C R’’
Ketones Carboxylic Acids Esters
Amine
X R = Alkyl Group
Rx = Alkyl Group x
R = Alkyl Group
OH
O
C C CN R C Cl
Arenes Halogenoarenes Acyl Chlorides
Nitriles CnH2n – 6m X = halogen atom
CnH2n - 7mX Phenols
R’’ O O CnH2n – 7mOH
R’ N R’’’ R C NH2 HO C CHRNH2
Amines Amino Acid
R = Alkyl Group
x Amides R = Alkyl Group
CnH2n + 3N
Naming Aromatic Compounds
Benzene is the simplest aromatic compound with one arene ring, and many derivatives are
named systematically by adding “benzene” after the name of the substituent.
NO2 Br
Nitrobenzene Bromobenzene Ethylbenzene
If the substituent is an alkyl chain with more C atoms than benzene itself, then the benzene
itself is a substituent, and the ring is now what is known as a “phenyl” group.
1-phenylheptane
Other aromatic compounds have common names that don’t follow any naming convention,
like H2O. OH NH2 COOH CHO O
Methylbenzene Phenol Phenylamine Benzoic Acid Benzaldehyde Methoxyphenyl

HC O
3
SO3H C
Benzenesulfonic Acid Phenylethanone

For rings with a common name as well as another substituent group, start numbering
from the substituent as n°1 and go with the direction that gives the other substituents the
smallest of numbers from 1-6. Examples are shown below.
By counting OH NH2
clockwise, Br gets a By counting clockwise, Br and
1 1
smaller number. Cl get a smaller number. The
6 2 6 2
The common name common name for the
for the compound is 3
5
3 compound is aniline, so the
5
phenol, so the name 4 Br 4
Cl name of the compound is
of the compound is 4-bromo-3-chlorophenylamine
3-bromophenol. Br because b comes before c
alphabetically.
Clockwise or OH O By counting clockwise, Cl
anticlockwise gets a smaller number. The
doesn’t matter here, O2N
1
2 NO2 1
6
2 common name for the
so do anything. 6
compound is anisole, so the
Common name is 3 3
5 5 name of the compound is
phenol, so the name 4 Cl 3-chloromethoxybenzene.
4
of the compound is
2,4,6-trinitrophenol. NO2
29.2-Shapes of Aromatic Organic Molecules; σ & 𝝅 bonds
Benzene consists of 6 carbon atoms arranged in a regular planar hexagon ring, where each
carbon atom is bonded to 1 hydrogen atom and its 2 neighboring carbons by σ bonds in a
trigonal planar fashion. Because the molecular geometry is trigonal planar, each carbon is
sp2 hybridised. Because each carbon has 3 p orbitals, 1 one of the orbitals is free of any
hybridization and protrudes outside of the ring structure.
The p-orbitals are parallel to each other and are

H H perpendicular to the plane of benzene ring itself. These p
C C orbitals overlap laterally each other similar to what
occurs in ethene molecules. In benzene rings, because the
H C C H p orbitals are evenly spaced, a single p orbital overlaps
with the surrounding 2 p orbitals to form a ring on top
C C and under the c-c ring chain. A diagram is shown below.
H
H
The delocalization of the electrons in π-orbitals in the
H H carbon atoms that are sp2 hybridized is what generates
C C the aromaticity of benzene. There are delocalized
electrons above and below the plane of the ring, which
H C C H makes benzene particularly stable. Benzene is
reluctant to addition reactions because those reactions
C C would involve breaking the delocalization and losing
H the stability.
H
29.2-Characteristic Organic Reactions
Electrophilic Substitution: Electrophilic substitution reactions are chemical reactions in

which an electrophile displaces a functional group in a compound, which is typically, but
not always, a hydrogen atom.
Electrophilic aromatic substitution reactions are characteristic of aromatic compounds and
are common ways of introducing functional groups into benzene rings.
Some aliphatic compounds can undergo electrophilic substitution as well.
Addition-Elimination Reactions: Addition-elimination reactions are 2-stage reaction

processes of an addition reaction followed by an elimination reaction, which gives an
overall effect of substitution.
29.4-Optical Isomerism
Most enantiomers have identical physical and chemical properties to their fellow
enantiomorph, apart from their ability to rotate plane-polarised light in opposite directions
and their potential biological activity.
H H
N N
HN NH
This is (S)-Thalidomide. This This is (R)-Thalidomide. This enantiomorph is

enantiomorph of the medicine causes birth a medicine that can treat a number of cancers, a
defects in babies for pregnant women. number of leprosy complications as well as
being an immunomodulatory medication
Optically Active: Chiral compounds that are capable of rotating the plane of vibration of
polarised to the right or left. If an organic compound had a chiral center, it has the
capability of being optically active.
Racemic Mixture: A racemic mixture, or a racemate, is a mixture that contains equal
(50% of each) proportions of left and right enantiomorphs of a chiral molecule.
Plane-Polarised Light and its Effect on Enantiomorphs
If an enantiomer rotates plane polarised light in the clockwise direction, then it is the (+)
form of the 2 enantiomorphs.
If an enantiomer rotates plane polarised light in the anticlockwise direction, then it is the
(-) form of the 2 enantiomorphs.
If a solution contains a 50/50 mix of both enantiomorphs, which creates a racemic
mixture, then the plane-polarised light would pass unaffected.
Chirality and the World of Medicine
Enantiomerism is extremely important to the pharmaceutical industry, because 1

enantiomorph may have potential beneficial biological activity while the other might be
completely biologically inactive, or even worse, have adverse effects on living organisms.
When optically active molecules are created in a chemical reaction, the product mixture is a
racemic mixture with equal proportions of the 2 enantiomorphs. As we discussed earlier, 1
of the enantiomers will generally have the desired physiological effect. This means that the
racemic mixture must be split into pure samples of the 2 enantiomorphs.
Certain types of catalysts known as chiral catalysts are being used to skew the 50-50 ratio
of the 2 enantiomorphs towards the more desired enantiomorph in a process known as
enantioselective catalysis.
Enantioselective Catalysis
Achiral catalysts react non-selectively. For example, the hydrolysis of esters using H2SO4
is a non-selective process where the H2SO4 molecule reacts wherever it is able to react and
produce a 50-50 mixture. When a catalyst is chiral, it can geometrically recognize the
location of the active site to complete a reaction. This is how chiral catalysts produce
compounds disproportionately skewed towards a certain enantiomorph.
30-Hydrocarbons
30.1-Arenes
Catalytic Halogenation of Arenes by Substitution with Cl2 and Br2
Let any arbitrary halogen molecule be denoted by X2. X2 will react with benzene in the
presence of an anhydrous FeX3 catalyst or an AlX3 by electrophilic substitution. This
catalyst can be made in situ by adding Fe filings to the reaction vessel. The mechanism of
the reaction is given below:
Because benzene is a relatively highly stable molecule, the electrophile that is going to
attack the negatively-charged 𝛑 bond delocalized e- system needs to be stronger than usual.
The electrophile cannot just have a δ+ charge, it needs to have at least full-on 1+ charge.
The dissociation of an X2 molecule into X+(aq) + X-(aq) is not spontaneously feasible, so the
generation of X+(aq) ions must be done in another way. This is when the catalyst comes in:
X
X
X X Fe X X
X Fe X
X
X
This is the reaction that generates the electrophiles needed to react with benzene molecules.
The rest of the reaction goes on as follows: X
X+ H X
H+
The final step is the catalyst regeneration step, where FeX3 is reproduced.
H+(aq) + [FeX4]-(aq) → FeX3(s) + HX(aq)
These compounds of halides such as AlX3 and FeX3 are called halogen carriers.
This is what happens to the delocalized
electrons in the pi bond system in the Every blue arrow shows
organic intermediate. a transformation of a
The delocalized 𝜋 system now only pair of e-
extends over 5 carbon atoms in the ring.
Only 4e- now exist in the ring, because 1 is
donated to the electrophile and 1 goes with
the carbon that left the 𝜋 system. The
carbon that left the system is sp3
hybridised, so its bond angle is 109.5°
Nitration using H2SO4 and HNO3
When benzene reacts with a mixture of concentrated HNO3 and concentrated H2SO4 and
heated under reflux at a temperature of 55°C, nitrobenzene is formed.
NO2
Conc. H2SO4
HNO3 H 2O
50°C
This is also an electrophilic substitution reaction, where NO2+ ions are the electrophiles.
The mechanism for the reaction is given below: NO2
NO2+ H NO2
H+
The electrophile is generated by the following sequence of reactions:

HNO3 → OH- + NO2+
H2SO4 + OH- → HSO4- + H2O
H2SO4 + H2O → HSO4- + H3O+
HNO3 + 2H2SO4 → 2HSO4- + H3O+ + NO2+
Friedel-Crafts Reactions
Friedel-Crafts Alkylation Reactions: Friedel-Crafts alkylation reactions are an important

type of reactions where an alkyl side chain can be introduced into a benzene ring. They are
also a type of electrophilic substitution reaction.
When benzene is heated under reflux with a chloroalkane in the presence of AlCl3 or FeCl3,
the alkyl group from the chloroalkane attaches to the benzene ring. This is an important
method regarding the replacement of an H atom with an alkyl group.
R
AlCl3 Catalyst
RCl HCl
Heat under Reflux
The electrophile here is CH3+, and is generated by the removal of a Cl- from CH3Cl and
adding it to AlCl3 to make CH3+ and AlCl4-.
The mechanism is given by the following diagram: CH3
CH3+ H CH3
H+
The catalyst is regenerated by the following reaction:

AlCl4- + H+ → AlCl3 + HCl
Q1-Draw the reaction mechanism for the reaction between benzene and the correct reactant
molecule and conditions to form 2-phenylpropane.
Solution:
AlCl3 Catalyst
X Heat under Reflux
The reactant molecule for these reactions is always found by taking the shape of the
molecule and adding a Cl to the site where the side chain sticks to the benzene ring. So, the
reactant molecule is: conditions are CH3CH(Cl)CH3 and AlCl3, heat under reflux.
Cl
The mechanism is:

H
Q2-The compound can be created using Friedel-Crafts reactions. Draw the
structure of the reactant molecule as well as the conditions for the reaction.
Solution: or CH3 heating under reflux using AlCl3.
Cl
Cl C CH3
CH3
Friedel-Crafts Acylation Reaction: Friedel-Crafts Acylation reactions are an important
set of reactions that add an RC=O acyl group into a benzene ring. They are also an
example of electrophilic substitution reactions.
When benzene is heated under reflux with an acyl chloride in the presence of AlCl3 or
FeCl3, an acyl group from the acyl chloride is attached to the benzene ring. This is an
important method regarding the replacement of an H atom with an acyl group.
R
O C
AlCl3 Catalyst O
R C Cl Cl-
Heat under Reflux
The electrophile is RC+=O, and is generated by the removal of Cl- from RC=OCl and
adding it to AlCl3 to make AlCl4-.
The reaction mechanism is given by the following diagrams: R O
R
R C
C H C
H+
O O
The catalyst is regenerated by the following reaction:

AlCl4- + H+ → AlCl3 + HCl
The reactant molecule is found by the same method used to find the reactant molecule for
alkylation reactions.
Q1-Draw the structural formula of the products would expect from the reaction of
benzene and aluminium chloride with (CH3)2CHCOCl
Solution: O O
CH3
C H OR
C
CH3
Q2-Draw the displayed formula of the acyl chloride that could be used to synthesise the
following compound using an AlCl3 catalyst while heating under reflux with benzene.
a) O
O
Use this
compound. Cl
Complete Oxidation of Aromatic Side Chains
When a substituted benzene is boiled with hot alkaline KMnO4, and then dilute HCl is
added, all of the substituted groups no matter what they are or how large they are, are
transformed into -CO2H groups.
COOH
Hot OH-/KMnO4
+
Dil.HCl Benzoic Acid
COOH
Hot OH-/KMnO4
+
Dil.HCl 1,4-Benzodioic Acid
COOH
O Hot OH-/KMnO4
+ HOOC COOH
Dil.HCl
HOOC COOH
;
1,2,4,5-benzotetroic Acid
Hot OH-/KMnO4
+ COOH
Dil.HCl
1,3-Benzodioic Acid
COOH
Hydrogenation/Reduction of Benzene Rings
When benzene reacts with H2(g), with a platinium/nickel catalyst at 190°C and 25
atmospheres of pressure, the only product at the end of the reaction is a cyclohexane ring.
Pt/Ni Catalyst
190°C
25 atm
3H2
Q1-Hydrocarbon A with formula C9H12 was oxidised by hot KMnO4 and then dilute
HCl was added. The compound obtained had the formula is C6H5COOH.
Draw the structure of hydrocarbon A.
Solution: There is only 1 COOH group, so only 1 end of the ring was oxidised. A benzene
ring has 6 carbons, so the 1 end must have all three carbons.
Solution: Because they told you that the
molecular formula is C9H12, and 1
side was substituted, we have to fit all
OR 3 C in that side chain. There happens
to be more than 1 isomer, which in this
case happens to be a chain isomer.
Q2-Suggest the structures for the aromatic carboxylic acids which will be produced
when the following compounds are oxidised by hot alkaline KMnO4, followed by dilute
HCl.
A) Solution:
COOH
Halogenation in Aromatic Rings and Side Chains
We now know that halogenation occurs within the benzene ring itself when the halogen
molecule X2 is added to the liquid along with anhydrous AlX3 or FeX3 halogen carriers.
The reaction has an electrophilic substitution mechanism.
When X2 molecules are bubbled through an alkane in the presence of UV light, one of
atoms in the halogenic has substitute the H in the alkane in a free-radical substitution
reaction. If the concentration of the halogen used is higher, it will keep on taking Hs away
and adding more X into the organic compound.
X2 → 2X
CH4 + X → CH3 + HX
CH3 + X2 → CH3X + X
When X2 molecules are bubbled through an alkene at room temperature, both of the atoms
in the halogen are added to the alkene to make a dihalogenoalkane.
X X H H
C C H C C H H C C H
δ+ X X X
X -
Xδ
-
Xδ
So, as you can see, depending on the reaction conditions, the integration of halogen atoms
into rings, alkanes and alkenes may or may not occur. If the reaction doesn’t support the
substitution of halogens into a benzene ring, the halogen atoms may be added into the side
chains.
Q1-Methylbenzene can undergo different reactions to form the products shown below.
CH2Cl CH3 CH3
Cl
Reaction 1 Reaction 2
a) Give the reagents and conditions needed for both reaction 1 and reaction 2
Solution: Reaction 1: Cl2 + UV light.
Reaction 2: Cl2 + AlCl3.
b) Name the mechanism for reaction 1.
Solution: Free-radical substitution.
Why do Aromatic Compounds prefer Substitution over Addition?
Benzene undergoes substitution reactions rather than addition reactions because addition
reactions disrupt the delocalization of the 6-electron π molecular orbital which then
reduces the stability of the benzene ring, whereas substitution reactions only cause
temporary disruption and so the stability of the benzene ring can be maintained.
Directing Substituent Group Effect
The substituents attached to benzene rings will influence and control where the new
substituents appear on the product as well as the rate of the reaction. There are 3
different positions on a monosubstituted benzene ring where new substituents can be added.
There are actually 5 positions where the new group can go, but 2 pairs of these places are
related symmetrically.
Electron-Donating Groups: Electron-donating groups is an atom or a functional group

that donates some of its electron density into a conjugated π bond system via inductive
effects. Because these groups add to the electron density of the π bond system, it makes the
molecule more susceptible to attracting electrophiles and hence increase the ability of the
molecule to undergo electrophilic substitution reactions.
Electron-Withdrawing Groups: Electron-withdrawing groups is an atom or a functional
group that withdraws some of the electron density of a conjugated π bond system into its
own electron cloud. Because these groups reduce the electron density of the π bond system,
it makes the molecule less susceptible to attracting electrophiles and hence decrease the
ability of the molecule to undergo electrophilic substitution reactions.
What does it mean for a group to be directing?

Methylbenzene directs incoming new functional groups to positions 2 and 4.
CH3 CH3
Cl
OR
Cl
Nitrobenzene directs incoming new functional groups to position 3.
NO2
Cl
Inductive Effects
Inductive Effects: The inductive effect is an effect regarding the transmission of unequal
sharing of the bonding electron through a chain of atoms in a molecule, leading to a
permanent dipole in the bond. It always only occurs in a σ bond.
2,4-Directing Groups
If we look closely at the type of substituents that are 2,4-directing, we find that they either:
They are capable of donating electron density to the π bond system via positive inductive
effects, or they have a lone pair of electrons on the atom joined to the ring. This lone pair
can be incorporated into the π system by sideways overlap of p orbitals. Because these
groups add electron density to the π system, they “Activate” the ring. We call them
“activating groups” because they increase the reactivity of the aromatic compound.
H H
N O
Amine groups are 2,4-directing Hydroxy groups are 2,4-directing

activating groups. activating groups.
H O
C N
H
O
H
All Alkyl groups are 2,4-directing Nitro groups are 3-directing

activating groups. deactivating groups.
O
O
C C
O R
H
Carboxylic acid groups are 3-directing Aryl groups are 3-directing deactivating
deactivating groups. groups.
If a functional group is 3-directing, the atom connected to the ring has no lone pairs, and
the atoms connected to the atom connected to the ring are highly electronegative, so they
also help with pulling the electrons away from the rings.
Halogen atoms are unusual in their effect on the ability of an aromatic ring to undergo
electrophilic substitution. Halogens are deactivating groups due to the inductive effects of
their overwhelming electronegativity withdrawing electrons away from the ring. However,
halogens have 3 lone pairs of electrons which allow them to overlap quite a bit with the
electronic cloud of the benzene ring.
Halogens tend to stabilize the carbocation intermediates within the mechanism of

electrophilic substitution, because of the amount of electron cloud overlap. The inductive
effect tends to be stronger than the stabilization of the overlap, so this causes net e-
withdrawal and thus deactivation. The overlap tends to be stronger at the 2,4 positions,
which allows the halogen atoms to direct groups to these orientations, yet be electron
withdrawing groups.
Only Legends
31-Halogen Compounds know
31.1-Halogen Compounds
As mentioned above, halogenoarenes are produced by the substitution of arenes by a

halogen in the presence of an AlX3 or FeX3 catalyst. For example, benzene reacts with
halogens in the presence of halogen carriers in the form of AlX3 or FeX3 to form a
halogenoarene. Methylbenzene also reacts with halogens under the same conditions to
form a 2-halogenoarene or 4-halogenoarene due to directing effects.
32-Hydroxy Compounds
32.1-Alcohols
Acyl chlorides are reactive organic compounds with an RCOCl functional group. These
react violently with aliphatic alcohols to form esters and white HCl fumes in an example
of a nucleophilic substitution reaction.
The carbon doubly-bonded to the O and the Cl has a δ+ charge, so it is open to nucleophilic
attack by the ROH-(aq) nucleophile. -
O O
δ+
C HO R2 C R2
R1 Cl R1 O
Cl ;
H
O O
C C HCl
R1 O R2 R1 OR2
H
Cl-
The formation of esters from acyl chlorides is more effective compared to using carboxylic
acids because acyl chlorides are much more reactive than carboxylic acids. The reaction of
acyl chlorides with alcohol goes to a further degree of completion compared to with
carboxylic acids.
Q1-Ester Q is formed when ethanoyl chloride reacts with ethanol. Draw Q.

O HCl
Solution:
O
OH
O
Cl
Ethyl ethanoate
32.2-Phenols
Phenols are al class of aromatic organic compounds where 1 or more hydroxy groups are
bonded directly to a benzene ring. The simplest of the family is phenol, C6H5OH.
OH
Phenol
Phenol can be produced by reacting phenylamine, C6H5NH2, with nitrous acid (HNO2)
or NaNO2 (sodium nitrite) and dilute acid below 10°C to produce what is known as a
diazonium salt. Further warming of the diazonium salt with H2O results in phenol.
Nitrous acid happens to be highly unstable, so we use sodium nitrite to produce HNO2
using dilute H2SO4. This is step 1.
<10°C
NaNO2(s) + HCl(aq) → HNO2(aq) + NaCl(aq)
For step 2, phenylamine is added to the HNO2 to form the unstable diazonium salt.
NH2 + HNO2 + HCl → N NCl- + 2H2O
This salt is called benzenediazonium chloride.

The diazonium salt formed is highly unstable, so what we do in step 3 is to heat the salt
up to the thermal decomposition temperature to form phenol.
H 2O
N NCl- OH + HCl + N2
Heat
Phenol reacts with a base such as NaOH(aq) to break the OH and make sodium phenoxide.
Phenol is very slightly soluble in water due to the large non-polar benzene ring, but it is
soluble in alkaline solutions and undergo acid-base reactions.
OH +NaOH O- Na+ + H 2O
Phenol Sodium Phenoxide

Phenol also reacts with Na(s) itself alone to form sodium phenoxide and hydrogen gas.
2 OH + 2Na 2 O-Na+ + H2(g)
Phenol is a crystalline solid at room temperature that melts at 43°C. Molten phenols react
vigorously with sodium metal.
Azo compounds from diazonium ions.
Azo-Compounds: Azo compounds are a highly reactive organic class of compounds with
an R1-N=N-R2 functional group. We mainly focus on when both alkyl groups connected
to both ends are benzene groups.
R2
N N
R1
Diazonium Compounds: Diazonium compounds are a highly reactive class of compounds
with an Ar-N+≡N functional group, where Ar refers to a benzene ring. They look like:
N N
As described above, when phenol is dissolved in NaOH(aq), a solution of sodium phenoxide

forms. When this solution of sodium phenoxide is cooled in an ice bath and a cold solution
of diazonium ions is added to the sodium phenoxide solution, a yellow-orange solution or a
precipitate of an azo compound is formed.
OH + NaOH(aq) O- + Na+(aq) + H2O
Phenol Phenoxide Ions
N N+ O- N N OH
Diazonium Ions Phenoxide Ions Azo Compounds

Yellow-Orange Precipitate
Nitration of Phenol
Phenols react with dilute HNO3(aq) at room temperature in what is known as a nitration
reaction to form both 2-nitrophenol and 4-nitrophenol, because -OH groups are 2 and 4
directing. This is another example of electrophilic substitution reactions.
If concentrated HNO3(aq) is added, you’d obtain 2,4,6-nitrophenol.
OH OH OH
H
NO2+ NO2 NO2
2 2H2O
Dilute HNO3(aq)
Room temperature
2-Nitrophenol OH
4-Nitrophenol
NO2
OH OH
Conc HNO3(aq)
O2N NO2
Room Temperature
3HNO3(aq) 3H2O
2,4,6-Nitrophenol
NO2
Bromination of Phenols
Phenols undergo electrophilic substitution reactions when bromine water is added to them
at room temperature. The phenol will decolourise the orange bromine water to form a
white 2,4,6-bromophenol. No special reaction conditions are required.
OH
OH Br Br
Br2(aq)
Room Temperature
3Br2(aq)
2,4,6-Bromophenol
Br
Why is phenol acidic if it has an -OH group in it?
Despite having an -OH group within them, phenol is a weakly acidic compound. This is
mainly due to the delocalization of one of the lone pairs that happens to be aligned in a
similar plane to the π-system. This increases the electron density of the whole ring and
increases the acidic behavior.
We know from previous reactions that the conjugate base of phenol is the phenoxide ion.
For phenoxide ions, because the lone pair of the oxygen atom is overlapping with the
π-system, the negative charge on the oxygen is spread out all over the molecule. This
creates a lower charge density on the oxygen atom, which makes it less likely to attract
H+(aq) when in solution. So, the phenoxide ion is more likely more likely to lose an H+(aq)
and act as an acid than to attract H+(aq) and act as a base.
OH O-
H+(aq)
This equilibrium lies minimally, but significantly to the left. Because the negative charge
on the oxygen atom is spread out across the whole molecule, the phenoxide ion is even
more stable as a standalone ion. This causes the equilibrium to move towards the right
more because the products are becoming more and more favourable. A significant enough
proportion of the phenol molecules now ionises to form the phenoxide ion, which gives
phenol its characteristic slight acidity.
How do the acidities of H2O, CH3CH2OH, C6H5OH?
When it comes to acidity, Phenol > Water > Ethanol. So, phenol is the most acidic and
ethanol is the least acidic. This specific order can be perfectly explained using the
structure of the conjugate bases of these compounds.
CH3CH2 OH CH3CH2 O- H+
The electron-donating alkyl group in the ethoxide ion concentrates negative charge density on the oxygen atom
which can easily bond an H+(aq) ion and act like a base. There is no benzene ring to delocalize all of the
charge density on as well, so ethanol is the least acidic of the three.
O
OH-(aq) H+
H H
The oxygen in the hydroxide ion has no electron-donating group, so the negative charge density on the oxygen atom is
lower than that in ethanol. This makes it more difficult for O to attract H+(aq) ions and behave like a base. However,
there is no benzene ring to delocalize all of the charge density on the O atom, so water is in-between phenol and ethanol.
OH O- H+
The oxygen in the phenoxide ion has its electrons in resonance with the electron in the 𝜋-system because one of the
lone pairs of oxygen is aligned with the 𝜋-system. Therefore, the negative charge density of the oxygen is spread all
over the benzene ring, which massively decreases the probability of attracting H+(aq) ions and increase the chances
that phenol acts as an acid. Phenol is the most acidic here.
Why does Phenol require milder reaction conditions compared to benzene?
Phenol is a significantly more reactive compared to benzene in terms of its interaction with
electrophiles. The oxygen atom in phenol has 1 one of its lone pairs overlapping with the
𝝅-system. This increases the electron density of the phenol molecule and makes it more
susceptible to attacks by electrophiles, which means that phenols are more reactive and
hence require milder reaction conditions.
33-Carboxylic Acids and Derivatives
33.1-Carboxylic Acids
Benzoic acid, which is a benzene ring bonded directly to a -COOH group., can be created
by oxidation of methylbenzene. When methylbenzene is oxidised using hot alkaline
KMnO4 solution followed by addition of dilute acid, benzoic acid is produced.
CH3 COOH
OH-(aq)/KMnO4
+
Dilute H2SO4(aq)
Acyl chlorides can be prepared from their corresponding carboxylic acids using either
PCl3 & heat, or PCl5 or SOCl2. Acyl chlorides are quite similar structurally to carboxylic
acids, but instead of the -COOH group we have a -COCl group.
Heat
3CH3COOH + PCl3 3CH3COCl + H3PO3
CH3COOH + PCl5 CH3COCl + POCl3 + HCl
CH3COOH + SOCl2 CH3COCl + SO2 + HCl
Oxidation of Carboxylic Acids
Although carboxylic acids are products of oxidation, some of them can be oxidised using
various oxidising agents such as Fehling’s reagent, Tollens’ reagent, acidified KMnO4
solution or acidified K2Cr2O7 solution.
Methanoic acid, or HCOOH, can be oxidised to CO2(g) and H2O(l) using all of the
oxidising agents listed above.
This oxidation reaction can be carried out by warming methanoic acid with Fehling’s
reagent. The Cu2+(aq) ions in the Fehling’s reagent is reduced back to Cu+(aq) and this
precipitates out as red CuO(s).
For the reaction of Tollens’ reagent with methanoic acid, the Ag+(aq) ions in the Tollens’
reagent is reduced back to Ag(s) and this creates a silver mirror.
The half-equation for the breakdown of methanoic acid is:
HCOOH(aq) ⇌ CO2(g) + 2H+(aq) + 2e- and this can also be written as:
HCOOH + [O] ⇌ CO2 + H2O.
When H+(Aq)/KMnO4 is used, the same products are obtained and the observations are
the solution goes from purple to colourless.
When H+(aq)/K2Cr2O7 is used, the same products are obtained and the observations are
the solution goes from orange to green.
Methanoic acid can be oxidised by all of these reagents due its shape:
O Methanoic acid is the only carboxylic acid
that has an aldehyde group as well, which
C we know from AS to be easily oxidizable.
H OH
Another carboxylic acid that is oxidizable is ethanedioic acid, or HOOCCOOH.

Ethanedioic acid can only be oxidised by strong oxidising agents such as H+(aq)/KMnO4
solutions.
This oxidation reaction occurs by warming the acid with acidified KMnO4, and this
reaction is possible due to the shape of the ethanedioic acid molecule.
The Os bonded to the carbons are very electronegative, so they pull both carbon atoms
apart, which elongates and weakens the C-C bond and opens it to attack by other reagents.
The balanced ionic equation for this reaction is given by: O O
2MnO4-(aq) + 6H+(aq) + 5H2C2O4(aq) → 2Mn2+(aq) + 10CO2(g) + 8H2O C C
This is a special reaction known as an autocatalysis reaction, where HO OH
1 of the products catalyses the reaction.
How does the acidity of carboxylic acids compare to that of phenols and alcohols?
Carboxylic acids are more acidic than phenols, which are more acidic than aliphatic
alcohols. Carboxylic acids are still known as weak acids due to their inability to fully
ionise in solution. The equilibrium below has a Ka of 1.3 × 10-5 mol dm-3, meaning that
the equilibrium is well over to the left. This means that the tendency to ionise is not high
like for mineral acids.
CH3COOH(aq) ⇌ CH3COO-(aq) + H+(aq)
This can be explained using the diagrams below:
O The electron density in the oxygen atom in the -OH group are pulled by the
double bonded oxygen atom. This is because the electron density is initially pulled
R C by the electron-withdrawing -R group, but once it makes it to the central C, the
OH density is immediately pulled by the highly electronegative O at the top. This
weakens the -OH bond and makes it more likely for the H+(aq) to be kicked out.
O The electron density can now be delocalized over the OCO bonds, which will
decrease the charge density on the O-, which will reduce the probability of the O- to
R C attract H+(aq) ions and make the ion act more like an acid than a base.
O-
O The alkyl groups attached to the carbon in the carboxylate ion are electron-
withdrawing groups, so they weaken the -OH bonds and increases the chances of
R C an H+(aq) to be kicked out. Because R is an electron-withdrawing group, it
O- further increases the area where the electron density is delocalized, which further
stabilizes the -COO- ions and makes it non-needy of the H+(aq) in solution
Relative Acidities of Chlorosubstituted Carboxylic Acids
The more chlorosubstituted a carboxylic acid is, the more acidic it will be. This id due to
the high electronegativity of chlorine atoms. Chlorine atoms are electron-withdrawing
groups, so the more of them there is, the more electron density they are going to take in
which causes the weakening of -OH bonds. This causes the H+(aq) to be more likely to be
kicked out, and increases the stability of the standalone ion resulting from the kicking out
of the H+(aq). This will increase the acidic behavior of the compound.
H H Cl
O O O
H C C Cl C C Cl C C
OH OH OH
Cl Cl Cl
chloroethanoic acid Dichloroethanoic acid Trichloroethanoic acid
Acidity increases as number of Cl atoms increases

33.2-Esters
When acyl chlorides react with -OH group-containing molecules, such as alcohols and
phenols, esters are the main product. No special reaction conditions are required, because
acyl chlorides are already highly reactive. Because acyl chlorides are highly reactive,
reactions with alcohols and phenols go to completion without significant equilibriums. The
only byproduct is HCl. Reaction examples:
HCl
H H
O O
H H H H
H C C H C C
Cl HO C C H O C C H
H H
Ethanoyl Chloride H H H H
Ethanol Ethyl Ethanoate
H H H H HCl
H H O
O H H
HO C C H H C C C
H C C C
O C C H
Cl H H H H
H H Ethanol
Propanoyl Chloride H H
Ethyl Propanoate
You can do the same thing with any number of carbons in the chain whether it is the acyl
chloride or the alcohol. Just remove the HCl, connect everything where the H and Cl were
removed, and add an -yl to the end of the prefix of the alcohol and an -oate to the end of
the prefix of first segment of the acyl chloride.
The same type of reactions occurs between acyl chlorides and phenols. Phenols react with
acyl chlorides at room temperature, but the reaction is slower compared to the reaction
with alcohol, so the reaction mixture is to be warmed here. Phenols are completely
unreactive towards carboxylic acids, so when phenyl esters are to be made, acyl chlorides
must be used.
The reaction proceeds in the presence of a base, which creates phenoxide ions in solution.
The phenoxide ions are nucleophiles which attack the acyl chlorides. Example reaction
equations are given below in the next page.
The first step of the class of reactions is:
OH O-Na+
NaOH(aq)
H+(aq)
The second and final step of the reaction is:
Na+O- H NaCl
H O
O Heat
H C C H C C
Cl O
H H
Ethanoyl Chloride Phenyl Ethanoate
Sodium Phenoxide
Another example of the reaction is given below:

Na+O-
O
NaCl
C Heat O
Cl C
Ethanoyl Chloride
O
Sodium Phenoxide
NaOH(aq)
The reaction would be written like: Acyl Chloride + Alcohol Ester + HCl
Or NaOH(aq) Heat
Acyl Chloride + Phenol Ester + NaCl.
Heat
A2 Chemistry
33.3-Acyl Chlorides
Acyl chlorides can be prepared by reacting the corresponding carboxylic acids with PCl3 &
heat, PCl5 or SOCl2. The -OH group is removed and a -Cl group is added carbonyl carbon.
Heat
3CH3COOH + PCl3 3CH3COCl + H3PO3
CH3COOH + PCl5 CH3COCl + POCl3 + HCl
CH3COOH + SOCl2 CH3COCl + SO2 + HCl
Other Reactions involving Acyl Chlorides
1-Hydrolysis of Acyl Chlorides back to Carboxylic Acids:

Acyl chlorides contain a carbonyl carbon which is also bonded to a Cl atom, which means
that the carbonyl carbon has a very significant 𝛅+ charge on and that makes it very
susceptible to nucleophilic attacks. H2O molecules have oxygen atoms that have 2 lone
pairs of e-, which makes them viable nucleophiles.
This reaction proceeds with an addition-elimination mechanism, where a molecule (H2O)
attacks the main backbone molecule (any acyl chloride) and a new molecule (HCl) is
kicked out. H H
O O
𝛅+
OH
R C R C Cl R C HCl
𝛅− Cl O
O O- The carboxylic acid is formed
O+ is very unstable, so an H connected to it and the leftover ions are H+(aq)
H H must be gone to regain a stable O atom. O- and Cl-(aq) ions. These bond
First, we add the H2O molecule in is also not very stable, so some of the which other to form an HCl
the addition step. For that, we electrons there must be used to double bond molecule.
remove 1 of the =O to form an -O- the carbon with the O. Now, the carbon has
ion, and that bond can now be used 5 bonds, and that is unstable, so we release
to integrate the H2O molecule. This the Cl because it is also electronegative and
compound is a little bit stable due to has a tendency pull electrons.
the existence of O- and O+ at
opposite sides of the compound.
A2 Chemistry
This reaction is vigorous compared to the hydrolysis of chloroalkanes, which need a
strong alkali that produces a strong nucleophile and heating under reflux. This is because
the carbon bonded to the Cl in chloroalkanes has a smaller 𝛅+ charge compared to the
carbonyl carbon doubly-bonded to the O and the Cl. Because the carbonyl compound is
bonded to both the oxygen and the Cl, electron density is pulled away very well from the
C, which increases the probability of nucleophilic attacks to be successful.
2-Esterification by the reaction of alcohols and phenols and acyl chlorides.

Acyl chlorides react with -OH containing groups to form esters. These reactions are much
more vigorous than carboxylic acids and alcohols reacting, and have a higher tendency to
go to a further completion.
For acyl chlorides and alcohols, no special reaction conditions are required. Only the ester
and HCl are produced. Diagrams are given in prior pages.
For phenols and alcohols, the reaction proceeds slower than with alcohols, so the mixture
should be warmed and NaOH(aq) must be added. The first reaction generates sodium
phenoxide, and this ion acts as a nucleophile that attacks acyl chlorides.
3-Reaction with ammonia at room temperature to produce an amide and HCl.

Acyl chlorides react with ammonia at room temperature vigorously to make an amide. No
special conditions are required and the only products are the amide and HCl byproducts.
These reactions are examples of nucleophilic addition reactions. The general equation is:
O H O
R C R C HCl
N
Cl NH2
H H
The reaction mechanism (Nucleophilic Addition) is shown below:

O-
O
H H H
𝛅+ 𝛅−
R C N
R C N
Cl H H
H Cl
O
R C HCl
NH2
A2 Chemistry
4-Reactions with primary and secondary amines to form amides and HCl.
Acyl reacts can also with amines at room temperature without any special reagents, where
the only products are the amide and the HCl. Nitrogen atoms in the amine have a lone
pair of electrons, which enables it to act like a nucleophile.
For primary amines, the general reaction equation is:
O R2 O
R1 C R1 C H
N HCl
Cl N
H H
R2
This reaction also exhibits the nucleophilic addition-elimination mechanism, which all of
the acyl chloride reactions listed above exhibit. O-
H R2 H
O
𝛅+
N
𝛅− R1 C N
R1 C
Cl H Cl
H
R2
O
R1 C HCl
NHR2
If excess ammonia, or any amine is used, the HCl formed will react to form ammonium
chloride in the case of ammonia or the chloride salt of the amine in the case of the amine.
If a secondary amine is used the reaction goes like this:
O-
H R2 R3
O
𝛅− C N
R1
+
𝛅
R1 C N
Cl H R3 Cl
R2
O
R1 C HCl
NR2R3
A2 Chemistry
Acyl chlorides can also react with phenylamines, and the reaction has the same exact
mechanism. The mechanism route is given below:
O O-
𝛅+ 𝛅− H
R1 C NH2
R1 C N
Cl
H
Cl
O
+
𝛅
R1 C
N
H
Nucleophilic Addition-Elimination Mechanisms
All of the acyl chloride reactions displayed above are carried out by the same mechanism,
where the 1st step involves the addition of a nucleophilic molecule (donator of pair of e-)
and the 2nd step involves the elimination of a small molecule. The is known as a
nucleophilic addition-elimination mechanism.
1st Step: The carbon in the C=O bond has a 𝛅+ charge due to the high electronegativity of the
O, which opens the carbon to nucleophilic attack. Molecules with lone pairs of electrons are
attracted to the main reactionary molecule.
2nd Step: The nucleophile is added to the molecule and one of the pairs of electrons in the
C=O bond goes to the O to clear up a bond for the incoming molecule. The new negative ions
are unstable so they must regain stability and the same goes for the positive ions. The C=O
bond is regained and the electronegative Cl atom is discharged.
Step 3: The H that was kicked out due to the atom with the lone pair becoming + is also
kicked out because positive ions are also unstable, and the H and the Cl recombine to form
HCl.
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The relative ease of hydrolysis between Acyl Chlorides, Alkyl Chlorides and Aryl
Chlorides.
In terms of ease of hydrolysis, acyl chlorides are the easiest to hydrolyse and aryl
chlorides are the most difficult to hydrolyse, while alkyl chlorides are somewhere in
between. This can explained by:
In acyl chlorides, the carbon atom where the hydrolysis reaction occurs is bonded to 2
highly electronegative atoms which pull electron density away from the carbon, which
makes it very attractive to nucleophiles. This speeds up the reaction mechanism massively.
In aryl chlorides, one of the p orbitals of the chlorine atom overlaps with the pi-system.
This gives the C-Cl bond a little bit of a double bond character, which makes it harder for
the nucleophile to break the bond. In fact, hydrolysis doesn’t occur in aryl chlorides.
Only legends
know
34-Nitrogen Compounds
34.1-Primary and Secondary Amines
Primary Amines: Primary amines are a class of organic compounds that have a single
-NH2 group, where the nitrogen in the amine group is bonded to 1 alkyl or aryl and the
other 2 bonds have hydrogen atoms. These are examples of primary amines.
H H
H
H 3C N H 3C H 2C N
N
H H
Methylamine Ethylamine H
Phenylamine
H
R N
H
General Primary Amine
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Secondary Amines: Secondary amines are another class of organic compounds that have a
single -NH group, where the nitrogen in the amine group is bonded to 2 alkyls, aryls or
both groups and the other 3rd bond has a hydrogen atom. Examples of secondary amines:
H H H
N N N
H 3C CH3 H 3C CH2CH3
Dimethylamine Ethylmethylamine
H Diphenylamine
N
R2 R1
General Secondary Amine
Tertiary Amines: Tertiary amines are a class of organic compounds that have a single -N
group, where this nitrogen is bonded to 3 alkyls, aryls or both groups. Examples of
tertiary amines include:
CH3 H3CH2C
N N N
H 3C CH3 H 3C CH2CH2CH2CH3
Trimethylamine Butylethylmethylamine
Triphenylamine
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Reactions involving Primary and Secondary Amines
1-Reaction of halogenoalkanes with NH3 in ethanol + heating under pressure.

Heat + Pressure
CH3CH2Cl + NH3(ethanol) CH3CH2NH2 + HCl
To avoid the formation of secondary amines, tertiary amines and ammonium salts, the
NH3 must be concentrated in ethanol as well as hot to maximise the chances of the
collision with the halogenoalkane molecule. In this reaction, the N in NH3 has a lone
pair of electrons which allows it to act as a nucleophile. The reaction is a nucleophilic
substitution reaction that proceeds with an SN2 mechanism because the halogenoalkane is
primary. Because it follows the SN2 mechanism, the rate of the reaction depends on the
concentration of both reactants.
H H H H H NH 3
𝛅+
H C C H N𝛅
−
H C C H
H Cl H H H Cl
H H
H C C H HBr
H NH2
Ethylamine
2-Reaction of halogenoalkanes with ethanolic primary amines + heating under pressure.

The main class of organic compounds generated by this reaction are secondary amines.
This is also an example of a nucleophilic substitution reaction, where the nitrogen in the
primary amine has a lone pair that gives the primary amine the ability to act as a
nucleophile and the attack the carbon bonded to the halogen atom. H2NC(CH3)H2
H H H H H
+
H C C𝛅 H H 3C C H H C C H
H w
Cl NH2 H Cl
𝛅−
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H H H H H
H C C N C C H HCl
H H H H
Diethylamine
3-Reduction of amides with LiAlH4.

Amides can be reduced to amines using LiAlH4 in dry ether. 1° amides are converted to 1°
amines, 2° amides are converted to 2° amines and 3° amides are converted to 3° amines.
O H
R1 C R1 C
H H
N H N
H H
1° amides 1° amines
O H
R1 C R1 C
R2 R2
N N
H H
O
H
R1 C
R2 R1 C
N R2
N
H
R3
The reaction mechanism is firstly a nucleophilic acyl substitution then a nucleophilic

addition. The mechanism is shown in the page below:
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H
O Al
O Li+
𝛅+
R1 C
H R1 C H H
N𝛅− H
N
H
H Al- H3Li+
Li+ O Li+
O Al-H3
Al-H3
R1 C R1 C
H H
N N H Al- H3Li+
Li+
Al-H3
O
NH
H Al- H3Li+
R NH
H
NH
NH2
H OH 1° Amine
Example Reactions:
CH3CONH2 + 4[H] → CH3CH2NH2 + H2O
Ethanamide Ethanamine
NH2 NH2
C + 4[H] → + H 2O
O
Benzamide Benzylamine
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4-Catalytic/Non-catalytic reduction of nitriles to amines.
Nitriles can be converted to 1° amines catalytically because the C≡N bond can be reduced
to a C−N by using hydrogen gas and either a palladium, nickel or platinum catalyst.
The catalyst to be used is nickel. The reaction occurs at heating and high pressure.
Example equations include the following: Ni
CH3CN + 2H2 CH3CH2NH2
Heat & Pressure
Ethanenitrile Ethylamine
Ni
CH3CH2CN + 2H2 CH3CH2CH2NH2
Heat & Pressure Propanamine
Propanenitrile
Ni NH2
C N + 2H2
Heat & Pressure
Benzonitrile Benzylamine
For non-catalytic reduction of nitriles into amines, LiAlH4 in dry ether is used. The
LiAlH4 will reduce the C≡N bond to a C-N bond with an amine. The reaction mechanism
is given below:
R
R C N C N
Li+
H Al
H Al- H3Li+ H
H H H
Li+
H H
R C N
R C N
Al
H H H
H
H
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Production of Amides from NH3 and Primary Amines
Ammonia and other primary amines react with acyl chlorides to form amides in what is
known as a condensation reaction, because a small molecule comprised of atoms from both
molecules is kicked out.
Ethanamide can be made from ethanoyl chloride & NH3. Propanamide can be made from
propanoyl chloride. So, if you want a non-substituted or non-secondary or tertiary amide,
we use an acyl chloride with the same number of carbon atoms as the desired amide
product. Example reactions are listed below:
CH3COCl + NH3 CH3CONH2 + HCl
C(CH3)3COCl + NH3 C(CH3)3CONH2 + HCl
CH3CH2CH2COCl + NH3 CH3CH2CH2COCl + HCl
Secondary and tertiary amides can be made from acyl chlorides and primary amines.
Butanoyl chloride reacts with propylamine to form N-propylbutanamide. We use the
letter N to show that the nitrogen has 1 group substituted to it instead of a hydrogen atom.
H
O O
C3H7 C C2H5 C NH2 C3H7 C
Cl N C3H7
H
H
Butanoyl Chloride Propylamine N-propylbutanamide
When the nitrogen atom is substituted at both 2 hydrogens, then we use N, N- prefixes.
Propanoyl chloride reacts with dipropylamine to form N, N-dipropylpropanamide.
O O
C2H5 C C3H7 N C3H7 C2H5 C
Cl N C3H7
H
C3H7
Propanoyl Chloride Dipropylamine N, N-dipropylpropanamide
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This reaction occurs at room temperature without any special conditions or reagents. If
excess amine is used, the chloride salt of the amine will form within the reaction mixture
due to the reaction of HCl and the amine. If excess ethylamine is used, ethylammonium
chloride (C2H5NH3+ Cl-) forms. If excess dimethylamine is used, dimethylammonium
chloride ((CH3)2NH2Cl).
Basicity of amine-containing solutions
The nitrogen atom in all amines as well as NH3 has a lone pair of e-, which gives it the
ability to attract H+(aq) ions when dissolved in solution. We know that any substance that
has the ability to readily accept H+(aq) ions when in solution is known as a base and its
solutions have a pH > 7. This is what causes the basicity of NH3 and amine-containing
solutions.
Alkyl amines are generally more basic than ammonia when in solution, and ammonia is
more basic than phenylamine when in solution. This is explained below:
For alkyl amines, such as ethylamine (CH3CH2NH2), the alkyl groups are electron-
donating. Because these groups are electron-donating, they increase the electron density
around the nitrogen atom which already has a lone pair of electrons within it. This
increases the probability of the amine attracting positive ions such as H+(aq) when in
solution.
For phenylamines, such as phenylamine (C6H5NH2), 1 of the p-orbitals of the nitrogen
atom overlaps with the 𝜋-system in the benzene group. This causes the delocalization of
the lone pair of e- in the nitrogen atom all over the ring and the amine group, which
decreases the charge density and hence the chances of the attraction of H+(aq) ions. The
benzene ring group is also electron-withdrawing, so it pulls some electron density from the
nitrogen atom.
Ammonia has a lone pair of electrons over at the nitrogen atom, but it has no electron-
donating group attached to it. This places it between arylamines and alkylamines in terms
of basicity. H
H H H
H
H N R
H
;
H H H H H
Electron density around a Electron density around an Electron density around an alkylamine,
phenylamine molecule. Not very NH3 molecule. Only where R is an arbitrary alkyl group.
concentrated at the lone pair. concentrated at the lone pair Very highly concentrated at the lone pair
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34.2-Phenylamine and Azo Compounds
Phenylamine is produced by the reduction of nitrobenzene. The reaction kicks off by

reduction of nitrobenzene using hot Sn metal and concentrated hydrochloric acid. This
acidic mixture contains the phenylammonium ion (C6H5NH3+), which NaOH(aq) is
added to, to form phenylamine.
NO2 NH3
Hot Sn
+ 7[H] + + 2H2O
ConcHCl
Nitrobenzene Phenylammonium
ion
NH3 NH2
NaOH(aq)
+ OH- + 2H2O
The phenylamine can then be extracted from the reaction mixture using a technique
known as steam distillation.
Reactions of phenylamine
1-Reaction of phenylamine with aqueous Br2(aq) to form bromophenylamines.

Phenylamine reacts with Br2(aq) at room temperature to form 2-bromophenylamine. If
excess aqueous bromine is used, then 2,4,6-tribromophenylamine is formed.
The reaction is an example of the electrophilic substitution mechanism in action. The lone
pair of e- in the nitrogen atom overlaps with the 𝜋-system of the benzene ring, which
donates some of the electron density to the benzene ring. The benzene ring is now activated
and is open for electrophilic attack.
Due to the ring activation, new groups are directed to the 2,4 and 6 positions. The reaction
conditions are milder than with direct reaction of bromine and benzene, similar to phenol.
NH2 NH2
H
Br+ Br Br
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NH2 NH2
Br Br
+ 3Br2(aq) + 3HBr
Phenylamine
Br
2,4,6-tribromophenylamine
2-Production of phenol from phenylamine by generation of diazonium salts.

Phenylamine reacts with nitrous acid (HNO2) to form a diazonium salt, but nitrous acid
is unstable so we have to make it by reacting sodium nitrite (NaNO2) and dilute HCl in a
test tube. The phenylamine then reacts with the nitrous acid to form the diazonium salt.
The diazonium salt is then heated with water to form phenol.
NaNO2 + HCl → HNO2 + NaCl
HCl + <10°C
NH2 + HNO2 N N
Cl-
Heat
N N + H 2O OH + N2 + HCl
Cl-
The formation of diazonium compounds form other class of compounds such as

phenylamines is known as diazotisation.
Azo Compounds
Azo Compounds: Azo compounds are chemical compounds that contain the diazinyl
R1-N=N-R2 functional group, where R1 and R2 are either aryl or alkyl functional
groups but are mostly aryl here. N=N groups are known as azo groups.
Azo compounds are formed in what is known as an azo coupling reaction. Azo coupling
reactions are organic reactions between diazonium compounds and other aromatic
compounds that produce azo compounds. These reactions are examples of electrophilic
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substitution reactions where diazonium salt act like the electrophile due to its positive
charge. We investigate below how azo compounds are synthesised.
NaOH(aq)
N N OH N N OH
Yellow-Orange precipitate
Cl- that is used as a dye.
N
N OH
H
Cl-
The positively charged diazonium ion acts as an electrophile, which can attack the benzene
ring in the other compound to be coupled. Because of the double bond between the 2
nitrogen atoms, the delocalized 𝜋-systems on both ends of the compound extend over the
double bond which acts like a bridge. Because the charge is very delocalized all over the
large molecule, the azo compound is extremely stable. The dye above is known as
4-hydroxyohenylazobenzene.
Many other azo compounds exist as stable colorful compounds, which begs for them to be
used as dyes in textiles, leathers and limited used in foodstuffs. The resilient bright color
of azo compounds is due to the high delocalization of the system of e-. The electrons jump
between energy levels that are extended pi-orbitals that are conjugated. The longer the
conjugation of the pi-orbitals in an azo compound, the longer the wavelength of the light
absorbed.
Other azo compounds can be formed from similar reactionary routes. Examples:
NaOH(aq)
N N NH2 N N NH2
“Aniline Yellow”
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NH2 N
N Cl-
HCl
HNO2 +
<10°C
NO2
4-nitrophenylamine
NO2
Nitrobenzene diazonium chloride
N
N OH OH
NaOH(aq)
O2N N N
Napthalene-2-ol
NO2
“Para Red”
34.3-Amides
Amides are a class of organic compounds that have the R1CONR2R3 functional group
within them. Below are some examples of amides. Amides, like amines, come in 1°, 2° and
3° forms.
Primary amides: Primary amides are a class of organic compounds that have an
R1CONH2 functional group, where the nitrogen atom is bonded to 2 hydrogen atoms and
the carbon atom is bonded to an aryl or alkyl group. Below are examples of 1° amides.
O O O
C H C H
NH2
H N H 3C N
H H
Methanamide Ethanamide Benzamide
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Secondary Amide: Secondary amides are a class of organic compounds that have the
R1CONR2H functional group, where the nitrogen atom is bonded to 1 hydrogen and 1
alkyl or aryl group and the carbon atom is bonded to an alkyl or aryl group.
O O
O
C H C C3H 7
H N H 3C N NHC2H5
CH3 H
N-Methylmethanamide N-Propylethanamide N-Ethylbenzamide
Tertiary Amides: Tertiary amides are a class of organic compounds that have the
R1CONR2R3 functional group, where the nitrogen atom is bonded to 2 alkyl or aryl
groups and the carbon atom is bonded to an alkyl or aryl group.
O O
O
C C 2H 5 C C3H 7
H N H 3C N N(C6H5)C2H5
CH3 C 2H 5
N,N-Ethylmethylmethanamide N,N-Propylethylethanamide N,N-Phenylethylbenzamide
Production of amides from NH3, Amines and Acyl Chlorides.
This is covered in a previous section of the notes. Go there.

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Reactions of Amides
1-Hydrolysis using aqueous acids or alkalis.

By refluxing an amide with an aqueous acid, a corresponding carboxylic acid and either
NH3 if the amide is of 1°, a primary amine if the amide is of 2° and a secondary amine if
the amide is of 3°.
O
H O
C
HCl(aq)
+ R C NH3
R N Reflux OH
H
O
C R2 O
HCl(aq)
+ R1 C R2NH2
R1 N
Reflux
OH
H
O
C R2 O
HCl(aq)
R1 N + R1 C R2NHR3
Reflux
OH
R3
If excess acid is used, the nitrogen-containing product is converted into an ammonium
salt. For example, when excess aqueous HCl is used and the nitrogen-containing product
of the hydrolysis is R2NH2, the salt formed is NH3R2Cl salt.
When an aqueous alkali such as NaOH(aq) is used the carboxylic acid isn’t produced,
but the sodium salt of the carboxylic acid is formed as well as the nitrogen-containing
group.
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O
C H O
NaOH(aq)
+ R1 C NH3
R1 N Reflux
O-Na+
H
O
O
C R2 NaOH(aq)
+ R1 C R2NH2
R1 N Reflux
O-Na+
H
O
C R2 O
NaOH(aq)
N + R1 C R2NHR3
R1 Reflux
O-Na+
R3
2-Reduction of CO groups in amides to form amines.

C=O groups in amides can be reduced using reduced using strong reducing agents such as
LiAlH4. The amide must be non-aqueous for the LiAlH4 is explosively reactive with H2O.
If the amide is of 1°, a primary amine as well as water form. If the amide is of 2°, a
secondary amine as well as water form. The reaction mechanisms and schemes are
investigated in the production of amines section of the notes.
Basicity of amides compared to amines
Amides are much less basic compared to amines. Amides contain a carbon doubly bonded to
an oxygen atom, and because oxygen atoms are highly electronegative, they take in huge
proportions of the available electron density around the nitrogen atom. This reduces the
chances of H+(aq) electron-deficient species bonding to nitrogen atoms, which is the
characteristic of a base. Amines have alkyl groups that donate electron density to the
nitrogen atom.
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34.4-Amino Acids
Amino Acids: Amino acids are a class of organic compounds that contain both the -NH2
amine group as well as the -COOH carboxylic acid group along with a specific side-
carbon chain to each amino acid.
Amino acids are amphoteric because they have both basic -NH2 and acidic -COOH groups.
Amino acids can undergo acid-base reactions, because -NH2 can act as a base towards
acidic reagents and -COOH can act as an acid towards basic reagents.
Amino acids can also interact within themselves in the following matter:
COOH NH2 COO-
H
R C H R C H 2R C H
NH2 COOH NH3+
Zwitterion: A molecule or ion having separate positively and negatively charged groups. An
example of this is the product of the reaction above. Because if these prominent charges, the
intermolecular forces of attractions between amino acids are very strong, leading to them
existing as strong crystalline structures at room conditions.
Isoelectric Point
Isoelectric Point: The isoelectric point is a pH at which a molecule carries no net electrical
charge or is electrically neutral. It varies from 1 amino acid to another.
Aqueous solutions of amino acids exist as zwitterions that have the ability to act as a
buffer solution that resists small changes in pH.
When pH is reduced, the -COO- part accepts the excess H+(aq) to form a -COOH group
and the molecule remains positively-charged. When the pH is increased, the -NH3+ part
donates an H+(aq) to form a -NH2 group and the molecule remains negatively-charged.
There is pH at which the solution would be completely electrically neutral, and this pH is
known as the isoelectric point.
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Peptide Bonds
The -NH2 group in 1 molecule of an amino acid can react with the -COOH group of
another molecule of an amino acid to form what is known as a peptide bond in what is an
example of a condensation reaction. The 2-amino carboxylic acids react with each other to
form chemicals with peptide bonds that are the building blocks of proteins. When 2 amino
acid molecules react to get conjoined by a peptide group, a dipeptide if formed. When a
dipeptide reacts with an amino acid molecule, a tripeptide is formed. Reaction example:
H O H H H O H
H 2N C C N C COOH H 2N C C N C COOH
R1 OH H R2 R1 H R2
Dipeptide
Acid 1 Acid 2
H O H H H H 2O
H2N C C N C COOH N C COOH

Acid 3
R1 H R2 H R3
H O H O H
H 2N C C N C C N C COOH H 2O
R1 H R2 H R2
Tripeptide
This reaction can happen between the tripeptide and some acid 4, and so on to form
polypeptides. The longer polypeptides get, the more their structure morphs into the
structure of proteins.
A2 Chemistry
Electrophoresis
Electrophoresis: Electrophoresis is an analytical technique which separates ions by placing

them in a spatially uniform electric field. It is a powerful technique in the field of
biochemical analysis to identify and purify proteins.
The way it works is: A sample of a mixture of amino acids is placed between 2 oppositely-
charged electrodes, and the positively charged amino acids move towards the negative
electrode and the negatively charged amino acids move towards the positive electrode.
If the size of the ions is large, they move more slowly compared to a smaller ion. If the
charge of the ions is large, they move towards the electrode of opposite polarity faster than
an ion with a small charge.
Porous Diffusion Perspex

Barrier Cover
Supports
Buffer Solution
The sample of amino acids is added to the center of the paper. If the amino acid is over all
neutral, then it stays in the center where it was 1st added. If the amino acid molecule is
overall +, then it will go towards the negative electrode and the opposite happens for
negatively-charged amino acids.
The initial position of the sample is added to a place within the paper that is gorged and is
known as a well. When a solution of a mixture of amino acids is added, the pH of the
solution must be at a value where the concentration of zwitterionic molecules is highest, or
the isoelectric point. We use a buffer solution to keep the pH constant such that the
concentration of the zwitterionic species remains at its highest.
If the pH of the buffer is above the isoelectric pH of the amino acid, it will migrate to the
+ electrode. If the pH of the buffer is below the isoelectric pH of the amino acid, it will
migrate to the – electrode. When the pH = to the isoelectric pH of the amino acid, it won’t
move. Therefore, the pH affects the result of electrophoretic experiments due to zwitterions.
A2 Chemistry
35-Polymerisation
35.1-Condensation Polymerisation
Formation of Polyesters
Polyester: Polyester is a category of polymers that contain the ester functional group in
every repeat unit of their main chain. These can be formed by reacting diols and dicarboxylic
acids or diols and dioyl chlorides.
Diols are molecules with 2 -OH groups at each end of the molecule. Dicarboxylic acids are
molecules with 2 -COOH groups at each end of the molecule. Dioyl chlorides are molecules
with 2-COCl groups at each end of the molecule.
Condensation Polymerisation: Condensation polymers are any kind of polymers formed
through a condensation reaction; where molecules join together and a small molecule is lost
as a result of the reaction such as water or HCl as byproducts.
Example reactions are given below:
R1:
HO CH2 CH2 OH HOOC CH2 CH2 COOH
Ethane-1,2-diol Ethane-1,2-dioic Acid
O CH2 CH2 O C CH2 CH2 C H 2O
O O
R2:
HO OH HOOC COOH
1,4-hydroxybenzene 1,4-benzenedioic Acid
O O C C H 2O
O O
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R3:
ClOC COCl HO OH
O O C C HCl
O O
Another reaction method is to use hydroxycarboxylic acids and have them react with each
other.
Hydroxycarboxylic Acid: Hydroxycarboxylic acids are a class of organic compounds
that contain both the -OH & the -COOH functional groups. In terms of polyester
chemistry, the functional groups can react with each other mimicking the 2 monomer
reaction above, but using 1 monomer. Reaction scheme is shown below:
HO CH CH2 COOH HO CH CH2 COOH
CH3 CH3
2-hydroxybutanoic acid 2-hydroxybutanoic acid
CH3 H O CH3 H O
O C C C O C C C H 2O
H H H H
Polyamides: Polyamides are a category of polymers that contain the amide functional
group in every repeat unit of their main chain. These can be formed by reacting diamines
and dicarboxylic acids, aminocarboxylic acids within themselves & amino acids within
themselves. These are also formed by condensation polymerisation. Example reaction:
R1:
H2N CH2 CH2 NH2 HOOC CH2 CH2 COOH
1,2-diaminoethane Ethane-1,2-dioic Acid
O O
C CH2 CH2 C N CH2 CH2 N
H H
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R2:
H 2N CH2 CH2 CH2 COOH H2N CH2 CH2 CH2 COOH
4-Aminobutanoic Acid 4-Aminobutanoic Acid
H2N CH2 CH2 CH2 COOH

O O
N CH2 CH2 CH2 C N CH2 CH2 CH2 C H 2O
H H
H H H
R3:
N C COOH H 2N C COOH
H R1 R2
Amino Acid 1 Amino Acid 2
H O H O
N C C N C C
H R1 H R2
Monomers and Repeat Units
You should be able to quickly workout the structure of the repeat unit given a monomer or
a pair of monomers, and you should be able to do the reverse where you can deduce the
monomer or monomers from the repeat unit. Here are some examples from past papers:
Q1-Methyl 2-cyanoprop-2-enoate, W, is the major component of Super Glue, a rapid-
setting adhesive. As the adhesive sets, the monomer W polymerises. Draw 2 repeat units.
W
CN
C OCH3
H 2C C
NC NC
CO2CH3 CO2CH3
O
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Q2-Polyamides and polyesters are 2 important types of condensation polymerisation.
Draw the structure of a compound that can polymerise to produce a polyamide, without
the need for a second monomer.
NH2
HOOC
35.2-Predicting the type of Polymerisation
If the polymerisation reaction between a single monomer or a pair of monomers generates

a polymer as well as a small molecule gets kicked out, then the reaction was a
condensation polymerisation.
If the polymerisation reaction between a single monomer or a pair of monomers generates
a polymer that has a long unbroken carbon backbone chain without kicking out a small
molecule, then the reaction was an example of addition polymerisation. Another indication
regarding addition polymerisation, is that the monomer/s will have double bonds between
the carbon atoms and the resulting large molecule has none of those double-bonded
backbones. Only single bonds between the carbons.
35.3-Degradable Polymers
Poly(Alkenes), such as polyethene, are polymers that are produced by the polymerisation
alkenes. This type of polymers is extremely unreactive, non-polar and saturated, meaning
that they are chemically resistant. Because of their inertness, polyalkenes are predominantly
non-biodegradable. We tend to melt and recycle them into new products, and some recycling
plants burn them and use the energy released to generate electricity.
Photodegradation
Polyesters and polyamides can be degraded using the action of light, in a process known as
photodegradation. The -C=O carbonyl groups have the ability to absorb electromagnetic
radiation in the UV light segment, and the absorption of these rays weakens these bonds and
weakens their structure into smaller molecules.
A2 Chemistry
Even though photodegradation seems like the solution to plastic pollution, shards of
partially photodegraded are dumped on top of each other in landfill sites, which blocks the
reach of UV rays. They may also be difficult to integrate into new products due to their
structural weakness from photodegradation.
Hydrolysis of Polyesters and Polyamides
Polyamides can be broken down by heating the polymer with a dilute HCl or H2SO4
catalyst. This reaction breaks the polyamide into carboxylic acid molecules & NH4Cl.
Polyamides can also be broken down by heating the polymer with a hydroxide ion bearing
species, such as sodium hydroxide. The reaction produces the sodium salts of both the
dicarboxylic acid and the diamine monomers. If the monomer was an aminocarboxylic acid
or an amino acid, the sodium salt of the acids would form respectively.
Polyesters can be broken down by heating the polymer with a dilute HCl or H 2SO4 catalyst.
This reaction breaks the polyester into the carboxylic acid and alcohol molecules that
constituted the polyester. Polyesters can also be broken down by heating the polymer with a
hydroxide ion bearing species, such as sodium hydroxide. The reaction produces the sodium
salt of the carboxylic acid and the alcohol molecule that constituted the polyester.
36-Organic Synthesis
36.1-Organic Synthesis
You must be able to immediately recognize any of the functional groups examined in the
syllabus, their properties as well as their reactions. All of them are listed below:
-Alkane -Arenes
-Alkene -Halogenoarene
-Halogenoalkane -Phenol
-Primary, secondary and tertiary alcohols. -Acyl chloride
-Aldehyde -Primary, secondary and tertiary amides
-Ketone -Amino Acids.
-Carboxylic Acids
-Esters
-Primary, secondary and tertiary amines.
-Nitriles
A2 Chemistry
You need to also remember all the reactions that create a functional group as well as all the
reactions that the functional groups undergo. You need to know this so much to the point
where you can deduce the reacting functional group given the product functional group as
well as the reaction conditions. You need to know about every byproduct and every
mechanism. All. Of. It. As well as all of the new A2 reactions and functional group
conversions, you need to be able to recall all of the AS reactions as well. Be on top of it.
A2 Chemistry
All Reactions. Learn this shit.
Forming Alkanes: R1
R3
R3 R1
Add H2 + Pt/Ni catalyst + Heat
C C H C C H
R4 R2
Alkene R4 R2
Alkane
H H H H H H H
Al2O3 catalyst + Heat
H C C C C C H H C C H
H H H H H H H
Long-chained Alkanes Shorter-chained Alkanes
Reactions of Alkenes: H H
Incomplete Combustion Complete Combustion
CO(g) + H2O(l) H C C H CO2(g) + H2O(l)
Add insufficient O2(g) Add excess O2(g)
H H
Add X2(aq)
+ UV light Free-radical Substitution
H H
H C C H
X H
H H
Forming Alkenes: H H
Ethanolic NaOH + Heat
H C C H C C H 2O NaX
Elimination Reaction
H H
X H
H H
H H
Heated Al2O3 catalyst or Conc. H2SO4
H C C OH C C H 2O
Elimination (Dehydration) Reaction
H H
X H
H H H H H
H H
Al2O3 catalyst + Heat
H C C C C C H C C
H H
H H H H H
H H
Reactions of alkenes:
C C
n H H
Ziegler-Natta Catalysts
H H H H
Polymerisation
H C C H H C C H
H X X X
H H
C C
H H H H
H H
H C C H H C C H
H OH H H
H H
C C CO2 + CO2
H H H H
H
H R1
C O
R1
H C C H C C
R3
R3 O C
R2
R2
OH OH
Forming halogenoalkanes:
H H H H
Add X2(aq) + UV light
H C C H H C C H
Free-radical Substitution
H H H X
H H
H H
Add X2(g) or HX(g)
C C H C C H
Electrophilic Substitution
H H
H or X X
OH H H HX, or KX with H2SO4 H H
or H3PO4, or PX3 & heat,
or PX5, or SOX2.
H C C H H C C H
H H H X H H
H OH
Ethanolic NH3
Reactions of halogenoalkanes:
H C C H H C C H
heating under pressure NaOH(aq) + Heat
Nucleophilic Substitution H H Nucleophilic Substitution
H NH2 H OH
H H H C C H H H
AgNO3(aq) in ethanol Ethanolic KCN + Heat
H C C H Nucleophilic Substitution H X H C C H
Nucleophilic Substitution
X-(Aq)
H H CN
Forming Alcohols:
H H Add H2O(g) + H H Cold dilute H H
H3PO4 catalyst acidified KMnO4
H C C H Electrophilic Addition C C Oxidation H C C H
H H
H OH OH OH
H H H H H H H
Warm with alkaline solution of
NaBH4, or LiAlH4 in dry ether
NaOH(aq) + Heat
H C C H H C C H H C C H H C C H
Nucleophilic Substitution Reduction
H X H OH H O H OH
H H H H H
Warm with alkaline solution of
NaBH4, or LiAlH4 in dry ether
H C C C H H C C C H
Reduction
H O H H OH H
H H
H H H H
O O
LiAlH4 in dry ether H C C H
H C C H C C H H C C
Reduction Dil HCl or Dil NaOH
H OH
OH O C2 H 5
H H OH H
CH3COOH
H H
H2O with HX
Reactions of alcohols: HX + SO2 with SOCl2
H C C H HX + POX3 with PX5
CH3CO- groups & H3PO3 with PX3
CH3CH(OH)- groups Heat & Distill
give a + test which forms H X off Aldehyde
yellow iodoform ppt. 1° Alcohol
HX, or KX with H2SO4
heat, or PX5, or SOX2.

or H3PO4, or PX3 &
Halogenation
Carboxylic
KMnO4 goes colorless
RCOCH3 K2Cr2O7 goes from orange to green Heat under reflux with Acid
excess oxidising agent
Halogenation
I2/NaOH(aq)
Heat & Distill

2° Alcohol off Ketone
NaOH(aq)
Hydrolysis
RCOCI3 RCOO-Na+
3° Alcohol Nothing Happens
CHI3 H H
H C C H
H H
H OH CO2 + H2O
C C
H H
Alcohols also react
H 2O with acyl chlorides to
form esters as well as
an HCl by product.
O H H
R C H2(g)
H C C H
O C2H5 H 2O
H O- Na+
Forming Carboxylic Acids:
H H H H
H+/K2Cr2O7 or H+/KMnO4
O
& Refluxing & Refluxing
H C C H H C C H C C H
Oxidation Oxidation
OH
H OH H H O
H H H
Refluxing with Dil HCl or O Refluxing with Dil HCl or O
Dil NaOH followed by Dil NaOH followed by
acidification. Add H2O. acidification. Add H2O.
H C C N H C C H C C
Hydrolysis Hydrolysis
OH O C 2H 5
H H+ NH3 with NaOH H
+ NH4Cl with HCl
+ C2H5OH for reverse esterification
H
Reaction of Carboxylic Acids:
H
O
H C COO-Na+ H2(g)
H C C
O C 2H 5 H
H H H Carboxylic Acids react with PCl3 on heating, SOCl2 or PCl5 to form
acyl chlorides.
Methanoic acid can be further oxidised with Fehling’s reagent,
Tollens’ reagent, H+/KMnO4, or H+/K2Cr2O7 to form CO2 + H2O.
H C COO-Na+ H C COOH Ethanedioic acid can be oxidised with warm H+/KMnO4 to CO2
H2O(l)
H CO2(g) H H H
H
H C C H
H C COO-Na+
H2O(l)
H OH
H
Forming Carbonyl Compounds:
H H H
H+/K2Cr2O7or H+/KMnO4
Heat & Distill off.
H C C H H C C H H2O(l)
Oxidation
H OH H O
H H H H H
Refluxing and distill off
H C C C H H C C C H H2O(l)
Oxidation
H OH H H O H
Reactions of carbonyl reactions:
Carbonyl carbon-containing compounds form an orange-
red ppt. 2,4-DNPH undergoes a condensation reaction 1° Alcohol if carbonyl
and a H2O molecule is kicked out. Products are carbonyl is aldehyde. 2° alcohol
hydrazones. -COOH & -COO don’t show it. if carbonyl is ketone.
R1 R1
NO2 NO2
NH2 O C N C
O2N N O2N N
R2 R2
H H
R1 C R2
2-hydroxynitriles if the
carbonyl is an aldehyde.
Tollens’ reagent (Diaminesilver hydroxide) forms a silver O 2-hydroxyalkylnitriles if
CN
mirror with aldehydes. Ag+(aq) is reduced to Ag+(aq). the carbonyl is a ketone
Fehling reagent is a blue Cu2+(aq) containing solution, which
R1 C H R1 C H
turns red when reacting with aldehydes to go red Cu+(aq).
O OH
CH3CO-R groups can be detected using alkaline iodine CN
solutions by forming yellow CHI3 ppt. First, RCOCI3 is
formed, then that forms RCO2-(aq) ions as well as CHI3. R1 C R2 R1 C OH
Same reaction as with the iodoform test on top.
O R2
Forming nitrogen-containing compounds:
H H H H
Heat with ethanolic NH3 in
a sealed tube under pressure
H C C H H C C H HX
H X H NH2
H H H H
Heat with ethanolic KCN
H C C H H C C C N X-(Aq)
H X H H
Heat with HCN and 2-hydroxynitriles if the carbonyl is
add KCN catalyst an aldehyde. 2-hydroxyalkylnitriles
R1 C R2
if the carbonyl is a ketone. Given up.
O
Reactions nitrogen-containing compounds in the syllabus:
H H
Add dilute HCl or dilute NaOH,
followed by acidification. Add H2O
H C C N H C COOH +NH4Cl
H H
vReactions of Arenes:
X
Existing alkyl side chains

become -COOH groups. +HBr
COOH NO2
Electrophilic Addition
(halogen carrier).
AlX3 catalyst
Halogenation
Add X2(aq) +
+H2O +H2O
Electrophilic Substitution
Friedel-Crafts Alkylation
R
Add ROX with AlX3
catalyst & heat
+HX
RO
+HX
NH2 Add HNO2(aq) or NaNO2 + dil. HCl OH
Forming Phenols: & keep the reaction mixture at <10°C
to form a diazonium salt. Warn the
salt with H2O to form phenol.
OH
Br Br
OH
NO2 O-Na+
Br
Br2(aq)
OH +H2O(g)
NO2
O-Na+
N N +H2(g)
+Phenol in
NaOH(aq)
N+ N
Cl-
HO
Forming aryl carboxylic acids:
R COOH
Hot OH-/KMnO4 + dil. HCl
Forming Acyl chlorides:

H H
Add PCl3 on heating, PCl5 or O
SOCl2 +HCl + SO2 with SOCl2
H C COOH H C C +HCl + POCl3 with PCl5
+H3PO3 with PCl3
O Cl
H H H
H 3C C
O H C COOH +HCl
NH(CH3)
H3C C
H
H
O O
+HCl
H C C
Cl H
H O
H
O
H C C
H C C O C 2H 5
H
NH2 +HCl
H
Forming nitrogen-containing compounds:
H H H H
Heat under pressure
containing ethanolic NH3
H C C H H C C H +HX
H X H NH2
H H Heat under pressure containing H H
ethanolic primary amines.
Example: Methylamine
H C C H H C C H
H X H HN CH3
H H H
O
Warm with LiAlH4 in dry ether
H C C H C C H +H2O
NH2
H H NH2
H Warm with LiAlH4 in dry ether H H
or heat with H2(g) using Ni
catalyst.
H C C N H C C H
H H NH2
NO2 NH2
Forming aryl nitrogen-containing compounds:
Add a mixture of Conc.
HNO3 + Conc. H2SO4. Add hot Sn(s) or concentrated
Heat to 25°C - 60°C. HCl followed by NaOH(aq)
Reactions of phenylamine:
NH2 NH2 OH
Br Br Add HNO2(aq) or NaNO2 + dil. HCl
& keep the reaction mixture at <10°C
to form a diazonium salt. Warn the
Add Br2(aq) at RTP salt with H2O to form phenol.
Br
Forming Amides:
H H
O O H H
Add NH3(aq) OAdd primary amine. O
at RTP Example: Methylamine
H C C H C C H C C H C C
Cl NH2
H H Cl NH
H H
+HCl
+HCl CH3
Reactions of amides:
H H H H
O O
Add H2O followed by Reduction of -CO group
dil. HCl or dil. NaOH by LiAlH4 in dry ether
H C C H C C H C C H
OH NH2 +H2O
H H H NH2
+NH3
Na salt of the carboxylic acid
is formed when dil. NaOH

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A2 A-level Chemistry Notes

Lattice Energy ∆H⊝

Enthalpy Change of Atomisation ∆H⊝

CH4(g) → C(g) + 4H(g) ∆H⊝

First Electron Affinity ∆H⊝

Second Electron Affinity ∆H⊝

Trends and factors affecting Electron Affinity

Electron Affinity increases. Electron Affinity increases

2-Effective Nuclear Charge Z:

Why are Fluorine and Oxygen anomalous?

-Calculate the lattice energy for sodium chloride, given that:

What factors affect Lattice Energy?

What Factors Affect Ion Polarisation?

23.2-Enthalpies of Solution and Hydration

Enthalpy of change of Solution, ∆H⊝

The general format of the equation would be written as:

Enthalpy change of Enthalpy change of

∆Hhyd [Li+] = -519 kJ mol-1.

Factors affecting Enthalpy Change of Hydration ∆H⊝

Generalisations regarding fluctuations of Entropy

Entropy per unit temperature higher

Entropy per unit temperature lower

Entropy Changes in Reactions

Entropy Changes in Exothermic and Endothermic Reactions

Calculations involving Entropy Values

Total Standard Molar Entropy Change, ∆S⊝ ⊝

Standard Entropy Change of Surroundings, ∆S⊝

Equilibrium occurs at SMaz.

arrangements has maxed

N2(g) + H2(g) NH3(g) Maximum

1-Calculate the ∆G⊝ using the values given:

For Exothermic Reactions: For Endothermic Reactions:

Gibbs Free Energy of Reactions and their Directions

-∞ Products Override Reactants override ∞

Electrolysis: Chemical decomposition of compounds by the passage of direct electric current

Factors affecting the nature of compounds generated by electrolysis

Increase in the ease of discharge

Magnesium Mg(s) → Mg2+(aq) + 2e- Silver Ag(s) → Ag+(aq) + e-

3-Concentration of the ion in the electrolyte:

Faraday Constant, F: 1 Faraday is the amount of electric charge carried by 1 mole of

How to find the amount that deposits on the electrodes?

24.2-Standard Electrode Reduction Potentials E⊝ , Standard Cell Potentials E⊝

What does the E⊝ definition mean?

Platinium wire H2(g) gas in,

H+, 1.00 mol dm-3

What do E⊝ values mean in terms of being positive or negative?

We’ll connect a Zn(s)/Zn2+(aq) half-cell to a standard

We’ll connect a S(s)/S2-(aq) half-cell to a standard 0.51V

Fe2+(aq)/Fe3+(aq) half-cell 0.77V

Fe2+, 1.00 mol dm-3 H+, 1.00 mol dm-3

Mn2+, 1.00 mol dm-3 H+, 1.00 mol dm-3

Standard Cell Potential

Q1-Will chlorine oxidise Fe2+ into Fe3+?

Q3-Can H+(aq) oxidise V2+(aq) to V3+(aq)?

Q4-Can MnO4-(aq) ions oxidise F-(aq) into F2(g) in acidic conditions?

Q2-Calculate the electrode potential values of an Ag(s)/Ag+(aq) at 0℃ when the

Q3-Calculate the electrode potential E of an Sn4+(aq)/Sn2+(aq) half-cell where the [Sn4+] =

Q2-An Al3+(aq)/Al(s) half-cell is connected to a Cu2+(aq)/Cu(s) half-cell. Calculate the Gibbs