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Topic 4.

1 Energetics (II)

a “understand the definition of enthalpy of atomisation, ∆ H o at,


enthalpy of hydration, ∆ H o hyd and lattice enthalpy, ∆ H o lat”

Enthalpy of atomisation, ∆ H o at
• Enthalpy change for the formation of one mole of gaseous atoms
from its element in its standard state
○ Example: ½ Cl2 (g) → Cl (g) ∆ H o at = +121.1 kJ
mol-1
○ Note: ∆ H o at values are all endothermic

Enthalpy of hydration, H o hyd


• Enthalpy change for the reaction of 1 mole of gaseous ions with
water
○ Example: Mg2+ (g) + (aq) → Mg2+ (aq) ∆ H o hyd = -1920 kJ
mol-1
○ Note: ∆ H o hyd values are all exothermic

Lattice enthalpy, H o lat (or UL.E.)


• Enthalpy change when one mole of an ionic solid
is formed from its constituent gaseous ions
○ Example: Na+ (g) + Cl- (g) → Na+Cl-(s) ∆ H o lat = -776 kJ mol-
1

○ Note: ∆ H o lat values are all exothermic

From Units 1 and 2 and needed in Unit 4:

Standard enthalpy of formation, ∆ H o f


• Enthalpy change when one mole of a compound is
formed from its elements in their standard states
under standard conditions (25oC and 1 atmosphere
pressure)
○ Example: Na (s) + ½ Cl2 (g) → NaCl (s) ∆ H o f = -411 kJ mol-1
○ Note: ∆ H o f values are all exothermic

First ionisation enthalpy, ∆ H o I.E. (1)


• Enthalpy change when one mole of electrons is
removed from one mole of gaseous atoms of an
element
○ Example:Na (g)  Na+ (g) +e- H o I.E. (1) = +500 kJ
mol-1
○ Note: H o I.E. (1) values are all endothermic

Second ionisation enthalpy, H o I.E. (2)


• Enthalpy change when one mole of electrons is
removed from one mole of singly positive gaseous
ions of an element
○ Example: Mg+ (g)  Mg2+ (g) +e- ∆ H o I.E. (2) = +1451 kJ
mol-1
○ Note: ∆ H o I.E. (2) values are always more endothermic than
those for ∆ Ho I.E. (1) (Why?)
First electron affinity, H o E.A. (1)
• First electron affinity is the enthalpy change for
the addition of 1 mole of electrons to one mole of
gaseous atoms of an element to form one mole of
singly charged anions
○ Example: e- + Cl (g)  Cl- (g) ∆ H o E.A. (1) = -349 kJ
mol-1
○ Note: ∆ H o E.A. (1) values are all exothermic

Second electron affinity, ∆ H o E.A.(2)


• Second electron affinity is the enthalpy change for
the addition of 1 mole of electrons to one mole of
singly charged anions of an element to form one mole
of doubly charged anions
○ Example: e- + O- (g) → O2- (g) ∆ H o E.A. (2) = +798 kJ
mol-1
○ Note: ∆ H o E.A. (2) values are all endothermic (Why?)

b “construct a Born-Haber cycle and carry out associated


calculations”

The Born-Haber cycle is really an application of Hess’ Law


• H o f = [∆ H o at (metal) + ∆ H o I.E. (metal (g))
+ ∆ H o at (non-metal) + ∆ H o E.A. (non-metal(g))]
+ ∆ H o latt

• For example, sodium chloride:

Na+ (g) + e- + Cl
(g)
[∆ H o at [Cl (g)] +121
[H o E.A. [Cl (g)]
Energy (kJ mole-1)

-364

Na+(g) + e- + ½ Cl2
(g) Enthalpy level
[∆ H o I.E. [Na (g)] +500 diagram for
Na (g) + Cl (g)
+ -

the formation
of sodium
Na (g) + ½ Cl2 (g) chloride (units
kJ mole-1)
[H o at [Na (g)] +108.4
[∆ H o latt [Na+Cl- (s)]

0 Na(s) + ½ Cl2 (g)

[∆ H o f [Na+Cl- (s)] -411

Na+Cl- (s)

Using Hess’s Law:

33691600 Harrow Chemistry 2


H o f [Na+Cl+ (s)] = [∆ H o at [Na (g)] + ∆ H o I.E. [Na (g)] + ∆ H o f [Cl (g)] +∆ H o E.A. [Cl (g)]]+ H o latt
[Na+Cl– (s)]

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Substituting the data (in order to calculate H o latt [Na+Cl– (s)]:

(-411) = (+108.4) + (+500) + (+121) + (-364) + H o latt [Na+Cl– (s)]

 H o latt [Na+Cl– (s)] = -776.4 kJ mole-1



In your own time - use Born-Haber cycles to help you to calculate the
following:

• ∆ H o L.E. [MgBr2 (s)] given ∆ H o at [Mg (g)] = +147.7 kJ mole-1


∆ H o at [Br (g)] = +111.9 kJ mole-1
H E.A [Br (g)]
o
= -324.6 kJ mole-1
∆ H o f [MgBr2 (s)] = -524.3 kJ mole-1
H o I.E. (1) [Mg (g)] = +738 kJ mole-1
∆ H o I.E. (2) [Mg+ (g)] = +1451 kJ mole-1

• H o E.A. (2) [O- (g)] given ∆ H o at [Ca (g)] = +178.2 kJ mole-1


H o at [O (g)] = +249.2 kJ
mole -1

H o E.A. (1) [O (g)] = -141.1 kJ mole-1


∆ H o f [CaO (s)] = -635 kJ mole-1
H o I.E. (1) [Ca (g)] = +590 kJ mole-1
H o I.E. (2) [Ca+ (g)] = +1145 kJ mole-1
H o latt [CaO (s)] = -3405 kJ mole-1

• ∆ H o f [KH (s)] given H o at [K (g)] = +89.2 kJ


mole -1

H o at [H (g)] = +218 kJ
mole -1

∆ H o E.A [H (g)] = -72.8 kJ mole-1


∆ H o I.E.[K(g)] = +419 kJ mole-1
H latt [KH (s)]
o
= -683.6 kJ mole-1

d “understand the factors that influence the value of lattice


enthalpy”

• Lattice enthalpy depends on:


• The sum of the ionic radii
○ the lattice enthalpy will be smaller if this sum is large
• The charge of the ions
○ the lattice enthalpy will be larger if the
cation and /or the anion have a large
charge on them

33691600 Harrow Chemistry 4


c “understand that values of lattice enthalpies calculated from the
theoretical model may differ from those calculated from a purely ionic
model”

Theoretical (calculated) lattice enthalpy values are based on a purely ionic


model
• completely spherical ions
• complete transfer of electrons

Experimental lattice enthalpy values determined using Born-Haber cycle


calculations – a practical route to the value

For NaCl
• theoretical lattice enthalpy value = -770 kJ mole-1
• experimental lattice enthalpy value = -776 kJ mole-1
• good agreement between theoretical and experimental values
○ ionic model for NaCl is a good one
○ i.e. a purely ionic model - completely spherical ions and
complete electron transfer

For CdI2
• theoretical lattice enthalpy value = -2346 kJ mole-1
• experimental lattice enthalpy value = -2050 kJ mole-1
• no real agreement between theoretical and experimental values
○ ionic model for CdI2 is a not a good one
○ i.e. there is quite a degree of covalent character in CdI2 and it
is not purely ionic
○ the ions are not spherical and there is incomplete transfer of
electrons (refer to Unit 1.3 b (ii) – “polarising power of cations
and polarisability of anions”)

e “understand the part played by lattice enthalpy and enthalpy of


hydration in rationalising the variation in solubilities of the
hydroxides and sulphates of Group 2.”

Enthalpy of hydration, H o hyd

• always exothermic
○ in positive ions the attraction is between the ion and the
negative end of the water dipole (δ - on O)
○ in negative ions the attraction is between the ion and the
positive end of the water dipole (δ + on H)
• the larger the charge on the ion the larger ∆ H o hyd (i.e. it will be more
exothermic)
• the larger the size of the ion the smaller ∆ H o hyd (i.e. it will be less
exothermic)

So as we go down a group the value of ∆ H o hyd will decrease (i.e. it will be


less exothermic)
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The solubility of a substance is governed by the enthalpy change of
solution, ∆ H osoln. The more exothermic the ∆ H o soln value the more likely
it will be for the substance to dissolve.
∆ H o soln
MX (s) + M+ (aq) + Cl-
(aq) (aq)

-∆ H o latt ∆ H o hyd [M+(g)] +


∆ H o hyd [Cl- g)]

Note: we are reversing the M+ (g) + X- (g) +


direction of the lattice (aq)
enthalpy vector ∴ the
negative sign

Using Hess’s law: ∆ H o soln = (-∆ H o latt) + (H o hyd [M+(g)] + ∆ H o hyd [Cl-
g)])

Sulphates of Group 2:

• Sulphate ion large - so sum of ionic radii does not change very much
as cation size increases
• Contribution from ∆ H o latt similar for Group 2 sulphates
• H o hyd of the cations gets smaller as the ion size increases
(contribution from the sulphate ion the same in all cases)
• Solubility of the sulphate decreases as cation size increases because
lattice enthalpy is not exceeded so much by the hydration enthalpy
(lattice enthalpy is not compensated for by hydration enthalpy)

Hydroxides of Group 2:

• Hydroxide ion is small – so sum of ionic radii of the cation and anion is
affected significantly by the cation size
• Lattice enthalpies of the hydroxides decrease as the cation gets
larger as the cation–anion distance is not affected by a large anion
• ∆ H latt decreases more rapidly than ∆ H o hyd
o

33691600 Harrow Chemistry 6


Topic 4.2 Topic 4.2: The Periodic Table II (Period 3 and Group 4)

a Variation of properties across a period

“the variation in properties across Period 3 (sodium to argon) as


illustrated by:
i reactions of the elements with oxygen, chlorine and water “

Na Mg Al Si P S Cl2 Ar
([Ne] = (P4) (S8)
1s22s22p6) [Ne]3s1 [Ne]3s2 [Ne]3s23p1 [Ne]3s23p2 [Ne]3s23p3 [Ne]3s23p4 [Ne]3s23p5 [Ne]3s23p6

Appearance Soft shiny Shiny grey Shiny grey Shiny grey White waxy Yellow Green gas Colourless
grey metal metal metal solid solid powder gas

Structure Metallic Metallic Metallic Giant Molecular Molecular Molecular Atoms


and bonding covalent covalent covalent covalent

Reaction 4Na + O2 2Mg + O2 4Al + 3O2 Si + O2 P4 + 5O2 S + O2 2Cl2 + O2


with oxygen ↓ ↓ ↓ ↓ ↓ ↓ ↓ No reaction
2Na2O 2MgO 2Al2O3 SiO2 P4O10 SO2 2Cl2O
Reaction 2P + 3Cl2
with 2Na + Cl2 Mg + Cl2 2Al + 3Cl2 Si + 2Cl2 ↓ 2S + Cl2
chlorine ↓ ↓ ↓ ↓ 2PCl3 ↓ N/A No reaction
2NaCl MgCl2 2Al2Cl3 SiCl4 (+ Cl2 → S2Cl2
PCl5)

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Reaction 2Na+H2O Mg + 2H2O Cl2 + H2O
Unreactive –
with water ↓ ↓ ↓
2NaOH + H2 Mg(OH)2 + H2 due to oxide No reaction No reaction No reaction HOCl + HCl No reaction
Very slow layer
Vigorous Dispropn
“the variation in properties across Period 3 (sodium to argon) as illustrated by:
ii the formulae and acid-base character of the oxides and hydroxides of the metals and oxides of
the non-metals”

Na Mg Al Si P S Cl Ar

Formula Na2O MgO Al2O3 SiO2 P4O10 SO2 SO3 Cl2O No oxide

Appearan White White solid White solid White solid White Colourless White solid Colourles N/A
ce solid solid gas s gas
Bonding Ionic Ionic Intermedia Giant Covalent Covalent Covalent Covalent N/A
and te ionic/ covalent molecular molecular molecular molecular
structure covalent
Reaction Na2O + MgO + H2O Insoluble in Insoluble in P4O10 + SO2 + H2O SO3 + H2O Cl2O + H2O N/A
with water H 2O ↓ water water 6H2O ↓ ↓ ↓
↓ ↓ 2HOCl
Mg(OH)2 4H3PO4
H2SO3 H2SO4
2NaOH
Type of Basic Basic Amphoteric Acidic Acidic Acidic Acidic Acidic N/A
oxide

Al2O3 + 6HCl 2AlCl3 + 6HCl ∴ Al2O3 acts as a base


Al2O3 + 3H2O + 6NaOH  2Na3Al(OH)6  Al2O3 acts as an acid

SiO2 is insoluble in water and also dilute NaOH (because it is aqueous) but it does dissolve in fused/molten NaOH:

33691600 Harrow Chemistry 8


SiO2 (s) + 2NaOH (l)  Na2SiO3 (s) + H2O (l)

Also: Acid-base character of Mg(OH)2 and Al(OH)3 need to be known:

Mg(OH)2 + 2HCl → MgCl2 + 2Al(OH)3 + 6HCl → 2AlCl3 + 3H2O ∴ Al(OH)3 acts as a base
H2O
∴ Mg(OH)2 acts as a base Al(OH)3 + OH-  Al(OH)4- ∴ Al(OH)3 acts as an
only acid
“the variation in properties across Period 3 (sodium to argon) as
illustrated by:
iii the formulae of the chlorides, and their reactions with water”

Na Mg Al Si P S Cl Ar

Formula NaCl MgCl2 AlCl3 SiCl4 PCl3 PCl5 S2Cl2 Cl2 No


chloride
Appearan White solid White solid White solid Colourless Colourles White solid Liquid Green N/A
ce liquid s liquid gas
Bonding Ionic Ionic Covalent Covalent Covalent Covalent Covalent Covalent N/A
and molecular molecular molecular molecular molecular molecular
structure
Reaction NaCl (s) + (aq) MgCl2 (s) + (aq) AlCl3 + 3H2O SiCl4 + 2H2O PCl3 + 3H2O PCl5 + 4H2O S2Cl2 + 2H2O Cl2 + H2O N/A
↓ ↓ ↓ ↓ ↓ ↓ ↓
with water H2S +SO2 ↓
Na+ (aq)+ Cl- Mg2+(aq) + 2Cl- Al(OH)3 + 3HCl SiO2 + 4HCl H3PO3 + 3HCl H3PO4 + 5HCl
(aq) (aq) +2HCl HCl +
HOCl

Note: Ionically bonded chlorides undergo hydration reactions.

Covalently bonded chlorides undergo hydrolysis reactions.

33691600 Harrow Chemistry 9


“iv students should be able to interpret the reactions in (a) (ii) and (a) (iii) in terms of the structure and bonding of the
oxides and chlorides”

Covered in the tables above.

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b Variation of properties down a group

i “recall the reasons for the increase in metallic character with increase in atomic number in
Group 4”

Going down group 4:

• Ca Non This increasing trend


rb metalli is caused by a
on c decrease in ionisation
energy as the cation
Sil Non
radius decreases.
ic metalli
This makes it
on c
energetically more
G Semi favourable for the
er metalli elements lower down
m c the group to form
an ionic compounds
iu
m
Ti Metalli
n c
Le Metalli
ad c

• Ease of positive ion formation increases

33691600 Harrow Chemistry 11


• Ionic character of chlorides increases and there is no significant hydrolysis in PbCl2.

• Ionic character of oxides increases and the trend is from neutral/acidic to amphoteric/basic

○ CO is a neutral oxide (it so weakly acidic that it is thought of as a neutral oxide)


CO2 is an acidic oxide CO2 + NaOH → Na2CO3

○ SiO2 is an acidic oxide but it needs to react with fused NaOH: SiO2 (s) + 2NaOH (l) → Na2SiO3 (s) + H2O (l)

○ PbO is an amphoteric oxide: As a base: PbO + 2HCl → PbCl2 + H2O


As an acid: PbO + 2NaOH + H2O → Na2Pb(OH)4

33691600 Harrow Chemistry 12


ii “recall that the +2 oxidation state in Group 4 becomes more stable than the +4 oxidation state as the atomic number
increases and apply this to the chemistry of tin and lead.”

The stability of the +2 oxidation increases down the group; the stability of the +4 oxidation state increases up the
group.

The smaller elements of group 4 show a wide range of oxidation states in their compounds:

C: +4 in CO2, +2 in CO, -4 in CH4


Sn: +4 and +2 [+4 more stable than +2 for tin]
Pb +4 and +2 [+ 2 more stable than +4 for lead]

In carbon the 4 outer electrons are in the second shell and are closely held by the nucleus ∴ compounds of carbon
are covalently bonded and carbon is usually +4 in its compounds.

In lead the outer electron configuration is 6s26p2. The 6s2 electrons are absorbed into the inner core and are thus held
more tightly (in general s electrons are held more tightly); the 6p electrons are thus less firmly held and can be
removed more easily.

We use some of the chemistry of tin and lead to illustrate the oxidation state stability trend in group 4.

Tin (II) is reducing and becomes tin (IV) which is the preferred oxidation state of tin in its compounds:

Sn2+ + Cl2  Sn4+ + 2Cl-

33691600 Harrow Chemistry 13


Lead (IV) is oxidising and becomes lead (II) which is the preferred state of lead in its compounds:

PbO2 + 4HCl → PbCl2 + Cl2 + 2H2O


iii “recall and explain the structure of carbon tetrachloride”

There are eight electrons around the central carbon atom.


Thus 4 pairs of electrons all of which are bonding pairs.
The 4 electron pairs arrange themselves around the central atom and repel each other arranging
themselves as far apart as possible to minimise the repulsion between them.
Thus CCl4 is tetrahedral and the bond angle is 109.5o.

iv “recall and explain the behaviour of carbon tetrachloride with water and contrast this behaviour with that of silicon
tetrachloride with water”

CCl4 is resistant to hydrolysis and does not react at all with water:
• very strong C-Cl bond which has to be broken before reaction can occur
• there are no vacant orbitals available for the coordination of the lone pair of electrons on the oxygen atom of the water
molecule.

SiCl4 reacts very rapidly with water at room temperature and undergoes a hydrolysis reaction
• there are empty energetically accessible 3d orbitals on Si (in SiCl4) [no energetically accessible orbitals available in C (in
CCl4)]
• the lone pair of electrons on the oxygen atom of the water molecule can coordinate into these vacant energetically
accessible 3d orbitals before the Si-Cl bond is broken
• the Ea value is much lower in SiCl4 compared to that for CCl4 and thus the SiCl4 hydrolyses very readily with water.

33691600 Harrow Chemistry 14


33691600 Harrow Chemistry 15
Topic 4.3: Chemical equilibria II

From Unit 2 and needed in Unit 4:

Reactions at equilibrium
• the rate of the forward reaction is equal to the rate of the reverse
reaction.
• the concentrations of all the substances at equilibrium are constant
(not equal)
• the composition at equilibrium can be approached from the reactants
or products

Two types of equilibrium


• homogenous - all of the substances are in the same phase.
○ e.g. HCl (aq) + NaOH (aq) ⇌ NaCl (aq) + H2O(l)
○e.g. H2 (g) + I2 (g) ⇌ 2HI (g)
• heterogeneous - the substances are in different phases.
○ e.g. CaCO3 (s) ⇌ CO2 (g) +CaO (s)
Position of equilibrium
• many reactions do not go to completion
• reactions reach a state of dynamic equilibrium
• the time taken to attain/reach equilibrium is variable
• the position of equilibrium is a measure of the
extent of a reaction once equilibrium has been
established
• if a reaction uses more than 50% of the reactants
before reaching equilibrium we say that the “position
of equilibrium lies to the right”
• if a reaction uses more than 50% of the reactants
before reaching equilibrium we say that the “position
of equilibrium lies to the left”
• Note: it must not be assumed that equilibrium has
been established when there are 50% of reactants and
50% of products

a “define the terms partial pressure and


concentration”

The partial pressure of a gas in a mixture of gases in a container is the


pressure that it alone would exert at a given temperature.

In a mixture of nA moles of gas A and nB moles of gas B at a total pressure


of P

• the mole fraction (x) of each gas is given by:

xA = nA/(nA + nB) xB = nB/(nA + nB)

• the partial pressure of each gas is given by:


pA = xA X P pB = xB X P

The concentration of a solution such as HCl (aq) is given the symbol [HCl]
and the units are moles dm-3.
b “deduce expressions for the equilibrium constants Kc and Kp from
given equations and calculate their numerical values with units,
given suitable data”

e “determine the equilibrium partial pressures in an equilibrium


resulting from simple binary gaseous dissociation (eg that of
dinitrogen tetroxide) given the value of Kp”

The equilibrium constant, Kc

Kc is the equilibrium constant in terms of equilibrium concentrations (for


purely aqueous or purely liquid systems - single phase).

For the reaction:


aA (aq) + bB (aq) ⇌ cC (aq) + dD (aq)

Kc = [C]c[D]d
[A]a[B]b

Characteristics of Kc
• characterises an equilibrium
• measured experimentally independent of the initial composition
• temperature dependent
• related to the equation for the equilibrium

Examples of Kc


CH3COOH (l) + CH3CH2OH (l) CH3COOCH2CH3 (l) + H2O (l)
Assuming a liquid phase equilibrium:-

Kc = [CH3COOCH2CH3][H2O]
[CH3COOH][CH3CH2OH]


N2 (g) + 3H2 (g) 2NH3 (g)

Assume a volume V dm3:-

Kc = [NH3/V]2
[N2/V][H2/V]3

33691600 Harrow Chemistry 17


The gaseous equilibrium constant, Kp

Kp is the equilibrium constant in terms of equilibrium partial pressures (for


purely gaseous systems - single phase).

2SO2 + O2 (g) ⇌ 2SO3 (g)


(g)

Kp = (PSO3)2
(PSO2)2 X (PO2)

Calculations involving Kc and Kp

1 1 mole of ethanoic acid and 1 mole of ethanol are mixed together at


100oC and allowed to reach equilibrium. The mixture was rapidly cooled
in ice-cold water and then made up to 1 dm3 with distilled water. 25 cm3
portions of this solution required 27.5 cm3 of 0.300 mole dm3 sodium
hydroxide for neutralisation. Calculate the value for Kc giving due
consideration to its units.

Relevant equations:-

NaOH + CH3COOH → CH3COONa + H2O

CH3COOH (l) + CH3CH2OH (l) ⇌ CH3COOCH2CH3 (l) + H2O (l)

No. of moles NaOH used in the titration = 0.300 X


27.5/1000
= 8.25 X 10-3 moles

No. of moles ethanoic acid in 25 cm3 of diluted “residue”


= No. of moles NaOH used in the titration = 8.25 X 10-
3
moles

No. of moles ethanoic acid in 1dm3 of diluted residue


= 8.25 X 10-3 x
1000/25
= 0.33 moles

This is the number of moles of ethanoic acid present at equilibrium.

CH3COOH (l) +CH3CH2OH (l) ⇌ CH3COOCH2CH3 (l) +H2O (l)

Start: 1 mole 1 mole 0 mole 0 mole

Eqm.: 0.33 mole 0.33* mole 0.67 mole 0.67


mole

*0.67 mole acid react with 0.67 mole alcohol ∴ 1 – 0.67 = 0.33 mole
alcohol left at equilibrium.
33691600 Harrow Chemistry 18
Assuming a volume of V dm3 – then the equilibrium concentrations (moles
dm-3) are:

0.33/V 0.33/V 0.67/V 0.67/V

CH3COOH (l) + CH3CH2OH (l) ⇌ CH3COOCH2CH3 (l) + H2O (l)

Kc = [CH3COOCH2CH3][H2O] = (0.67/V)(0.67/V) = 4.12 (no


units
[CH3COOH][CH3CH2OH] (0.33/V)(0.33/V) - as they
cancel out)

2 The equilibrium constant for the reaction:


2A(aq) ⇌ A2(aq) is 6.4 mol-1 dm3
Calculate the equilibrium concentration of A2 if the value for [A] is
0.4 mol dm3.

Kc = [A2] = [A2] = 6.4


[A]2 (0.4)2

 [A2] = 1.024 mole dm-3

3 Calculate the equilibrium constant for the reaction

N2O4 (g) ⇌ 2NO2 (g)

given that 1.00 mole has dissociated by 20% at equilibrium at a


pressure of 2 atmospheres.

N2O4 (g) ⇌ 2NO2 (g)

Start 1.00 0
moles moles

(1.00 - 0.20) (2 X 0.20)


Eqm. 0.80 0.40
moles moles

Total no. of moles at equilibrium = 0.80 + 0.40 = 1.20 moles

Partial pressure of N2O4 = mole fraction N2O4 X Ptot


= (0.80/1.20) X 2 = 1.33 atm

Partial pressure of NO2 = mole fraction NO2 X Ptot


= (0.40/1.20) X 2 = 0.67 atm

Kp = (PNO2)2 = (0.67)2 = 0.338 atm


(PN2O4) (1.33)

33691600 Harrow Chemistry 19


c “recall that expressions for Kp and Kc for heterogeneous equilibria do
not
include values for solid and liquid phases”

CaCO3 ⇌ CaO + CO2 (s)


(s) (s)

Since solids do not exert partial pressures we


Kp = (PCaO) X (PCO2) assume that (PCaO) and (PCaCO3) equals unity (1) and
(PCaCO3) write out a new constant, Khet, the heterogeneous
equilibrium constant

Hence, Khet = (PCO2)

d “recall that the presence of a catalyst does not affect the position of
equilibrium”

Catalysts increase the rate of reaction.

In an equilibrium:
• catalysts increase the rate of the forward reaction, with a subsequent
increase in the rate of the forward reaction.
• thus the rate at which equilibrium is achieved is faster in the
presence of a catalyst.
• note: the presence of a catalyst does not affect the equilibrium
composition, i.e. has no effect on Kc.

f “understand that changes in temperature result in a change in the


value of Kc and Kp and that the position of equilibrium will change with
change in temperature.”

Temperature

If the reaction (convention - left to right) is exothermic, the value of Kc (or


Kp) will decrease if the equilibrium temperature is increased. This means
that the equilibrium position moves to the left and the yield of product
falls at higher temperatures. The value of Kc (or Kp) will increase if the
temperature is decreased. This means that the equilibrium position
moves to the right and the yield of product increases at lower
temperatures.

“A decrease in temperature favours the exothermic direction of a


reaction”.

If the reaction (convention - left to right) is endothermic, the value of Kc


(or Kp) will increase if the equilibrium temperature is increased. This
means that the equilibrium position moves to the right and the yield of
product rises at higher temperatures.
33691600 Harrow Chemistry 20
“An increase in temperature favours the endothermic direction of a
reaction”.

33691600 Harrow Chemistry 21


Concentration - using Kc

Consider the following equilibrium:

aA(aq) + bB(aq) ⇌ cC(aq) + dD(aq)

K c= [C]c[D]d
[A]a[B]b

Kc is fixed at a particular temperature so if [A] and/or [B] are increased


then [C] and [D] have to increase in order for the constant value of Kc to
be maintained.

Pressure

An increase in pressure results in a decrease in volume.

This means that in an equilibrium the system with the smallest volume
will oppose the increase in pressure.

E.g. 2SO2(g) + O2 (g) ⇌ 2SO3(g)


2 moles 1 mole 2 moles
2 vols 1 vol 2 vols

i.e. 3 vols to 2 vols

So, the equilibrium will shift to the right.


 the formation of SO3 is favoured.

Using Kp= (PSO3)2


(PSO2)2 X (PO2)

Increasing PSO2 and/or PO2 means that PSO3 will increase in order to maintain
the constant value of Kp; so, more SO3 formed.

Summary

Factor Effect on Kc Effect on composition


Concentratio None Changes
n
Pressure None Changes – for gaseous
reactions
Temperature Changes Changes
Catalyst None None

33691600 Harrow Chemistry 22


Topic 4.4: Acid-base equilibria

a “recall the Brønsted-Lowry theory and use it to identify acid base


behaviour, and identify acid base conjugate pairs and relate them by
means of suitable equations”

Brønsted-Lowry theory

An acid is a proton donor:


E.g. HCl (aq) +H2O (l) ⇌ H3O+ (aq) + Cl- (aq)

In the forward reaction the HCl is acting as an acid.

A base is a proton acceptor:


E.g. NH3 (aq) + H2O (l) ⇌ NH4+ (aq) + OH- (aq)

In the forward reaction the NH3 is acting as a base.

Acid-base conjugate pairs

E.g. HCl (aq) + H2O (l) ⇌ H3O+ (aq) + Cl- (aq)


Acid 1 Base 2 Acid 2 Base 1

Conjugate base 1 (Cl- ) is related to acid 1 (HCl) because it has been


formed by the loss of a proton.

Conjugate acid 2 (H3O+) is related to base 2 (H2O) because it has been


formed by the gain of a proton.



More examples of acid – base pairs. Identify the acid-base conjugate pairs
in these equilibria.

H2SO4 + H2O ⇌ H3O+ + HSO4-

HNO3 + H2SO4 ⇌ H2NO3+ + HSO4-

HClO4 + H2O ⇌ H3O++ ClO4-

33691600 Harrow Chemistry 23


c “understand the terms ‘strong’ and ‘weak’ as applied to acids
and bases”

Basicity of an acid

The basicity of an acid can be thought of as the number of replaceable


hydrogens that it has:

HCl monobasic

H2SO4 dibasic

H3PO4 tribasic

CH3COOH tetrabasic monobasic (why?)

Strong and weak acids

Strong acids - fully ionised in aqueous solution.

E.g. HCl (aq) + H2O (l)  H3O+ (aq) + Cl- (aq)

The equilibrium lies to the right and the [H3O+] is very high. Strong acids
have weak conjugate bases.

Weak acids - only partially ionised in aqueous solution.

E.g. CH3COOH (aq) + H2O (l) ⇌ CH3COO- (aq) + H3O+ (aq)

The equilibrium lies to the left and the [H3O+] is very low. CH3COO- is the
strong conjugate base of the weak acid CH3COOH. Weak acids have
strong conjugate bases.

Strong and weak alkalis

Strong alkalis - fully ionised in aqueous solution.

E.g. NaOH (aq)  Na+ (aq) + OH- (aq)

The equilibrium lies to the right and the [OH-] is very high. Strong alkalis
have weak conjugate acids.

Weak alkalis - only partially ionised in aqueous solution.

E.g. NH4OH (aq) ⇌ NH4+ (aq)+OH- (aq)

The equilibrium lies to the left and the [OH-] is very low. NH4+ is the
strong conjugate acid of the weak base NH4OH. Weak alkalis have strong
conjugate acids.

33691600 Harrow Chemistry 24


b “d
efine
pH”

d “define Ka and Kw and recall


their units”

e “define
pKa and pKw”

f “calculate the pH of solutions of strong acids and


strong bases”

g “calculate pH of solutions of weak acids given Ka


and vice versa”

Ionic product of water

H2O (l) ⇌ H+ (aq) + OH- (aq)

Kc = [H+][OH-]
[H2O]

[H2O] is so large that it remains effectively constant.

Kw = [H+][OH-], where Kw incorporates Kc and [H2O]

At 298K and 1 atm, Kw = 1 X 10-14 moles2 dm-6

Kw = [H+][OH-] = 1 X 10-14 moles2 dm-6 [pKw = -log10Kw = 14]

For a neutral solution [H+]=[OH-] ([H+]= 1 X 10-7 mole dm-3)

For an acid solution [H+]>[OH-] ([H+]> 1 X 10-7 mole dm-3)

For an alkali solution [H+]<[OH-] ([H+]< 1 X 10-7 mole dm-3)

pH

pH= -log10[H3O +]/moles dm-3

More simply, pH= This is the definition of


-log10[H+] pH!!

Strong acids

E.g. calculate the pH of 0.1M HCl.

33691600 Harrow Chemistry 25


HCl - strong acid  fully ionised.

So [H+] = 0.1 moles dm-3

pH = - log10(0.1) = 1
E.g. calculate the pH of 0.2M H2SO4.

H2SO4 - strong acid ∴ fully ionised* (assume H2SO4 →2H+ + SO42-)

So [H+] = 2 X 0.2 moles dm-3

pH = - log10(0.4) = 0.398

Strong alkalis

E.g. calculate the pH of 0.01M NaOH.

NaOH - strong acid ∴ fully ionised.

So [OH-] = 0.01 moles dm-3

Since Kw = [H+][OH-] = 1 X 10-14 moles2 dm-6

∴ [H+] =(1 X 10-14)/0.01 = 1 X 10-12 moles dm-3

⇒ pH = 12

Weak acids (1)

E.g. calculate the pH of 0.1M CH3COOH given Ka = 1.7 X 10-5 moles dm-3.

Eqm. CH3COOH (aq) ⇌ CH3COO-(aq) + H+(aq)

∴ Ka=[CH3COO-][H+] Note the assumptions made:


[CH3COOH]
➢ CH3COOH is a weak acid, so only partially
ionised ∴ [CH3COOH] is effectively
1.7 X 10-5 =[H+]2 constant/unaltered
(0.1) ➢ [CH3COO-] = [H+]
 [H+] = √ (1.7 X 10-5 X 0.1) = 1.3 X 10-3 moles dm-3

∴ pH = -log10(1.3 X 10-3) = 2.88

33691600 Harrow Chemistry 26


*Dr. Beavon, Chief Examiner says
not!! Check his website:
www.rod.beavon.clara/net.learning.
htm

33691600 Harrow Chemistry 27


Weak acids (2)

E.g. calculate the ionisation constant, Ka, of 0.01M CH3CH2COOH given that
the pH of the acid is 3.44. What is the pKa value for propanoic acid?

Eqm. CH3CH2COOH ⇌ CH3CH2COO- + H+

Ka=[CH3CH2COO-][H+]
[CH3CH2COOH]
∴ Note the assumptions made:
Ka = [H+]2 ➢ CH3CH2COOH is a weak acid, so only partially
[CH3CH2COOH] ionised
∴ [CH3CH2COOH] is effectively constant/unaltered
Ka = (3.6 X 10-4)2 ➢ [CH3CH2COO-] = [H+]
0.01

= 1.30 X 10-5 moles dm-3


(From pH = 3.44)
Since pKa = -log10Ka Since pH = -log10[H+] =
3.44
∴ pKa = -log10(1.30 X 10-5) = 4.89 ∴ [H+]= 3.6 X 10–4 moles

Effect of temperature on pH

The ionisation of water is slightly endothermic.

H2O (l) ⇌ H+ (aq) + OH- (aq)

Kw = [H+][OH-]

At 25 oC and 1 atm, Kw = 1 X 10-14 moles2 dm-6

At 50 oC and 1 atm, Kw = 1.2 X 10-14 moles2 dm-6

So [H+] and [OH-] increase with increasing temperature. Thus the


equilibrium for the ionization of water moves to the right with increasing
temperature. This means that the equilibrium must be endothermic in the
forward direction.

At 25 oC [H+] = (1.0 x 10-14) moles dm-3

At 50 oC [H+] = √(1.2 x 10-14) moles dm-3

So, [H+] increases with increasing temperature.

Also pH (=-log10[H+]) decreases as [H+] increases.

But the solution does not become more acidic as the temperature
increases because there is a simultaneous increase in [OH-] as the
temperature increases, thus “cancelling out” the effect of the increase in
[H+].

33691600 Harrow Chemistry 28


h “understand the principles involved in acid base
titrations”

i “recall the sketch curves for the variation in pH during the


following titrations; strong acid – strong base, weak acid –
strong base and strong acid – weak base”

j “use titration curves to determine Ka for a weak


acid”

k “explain the choice of a suitable indicator for an acid-base titration


given pKInd values”

Acid-base titrations

pH changes during an acid-base titration (0.1 mole dm-3 concentrations)

Strong acid vs strong alkali (e.g. HCl and NaOH)

25 cm3 of 0.1M HCl in a conical flask and add small portions of 0.1M NaOH
from a burette measuring the pH after each addition. Plot a graph of pH
against volume alkali added.

pH of
NaOH
NaOH in
excess

Equivalence point
- halfway point of
the straightest
pH of vertical part of
0.1M the graph (pH =
HCl = 1 7)
5 10 15 20 25
30

Volume of alkali added/cm3

33691600 Harrow Chemistry 29


Weak acid vs strong alkali (e.g. CH3COOH and NaOH)

Place 25 cm3 of 0.1M HCl in a conical flask and add small portions of 0.1M
NaOH from a burette measuring the pH after each addition. Plot graphs of
pH against volume alkali added.

Equivalence point
pH of - halfway point of
NaOH the straightest
vertical part of
the graph (pH =
8.5)

Compare
this
pH of 0.1M curve
CH3COOH ≈ 3 with the
one for
HCl and
NaOH
5 10 15 20 25
30
Volume of acid added/cm3

Weak alkali vs strong acid (e.g. NH4OH vs HCl)

[Apologies for the “switch” but this was the only set of curves that was
available at the time].

Place 25 cm3 of the alkali in a conical flask and add small portions of acid
from a burette measuring the pH after each addition. Plot graphs of pH
against volume alkali added.

Compare
the
curve for
pH of NaOH
NH4O H and HCl
with this
one
Equivalence
point -
halfway point
pH of of the
HCl straightest
vertical part
5 10 15 20 25 of the graph
30
Equivalence points during acid-base titrations
Volume of acid added/cm 3 (pH = 5.5)

33691600 Harrow Chemistry 30


You will have noticed that the pH values at equivalence are not always
equal to 7.

Explanations:

HCl vs NaOH: resulting salt NaCl (aq) - the salt of a strong acid and a
strong alkali.

Ions present in aqueous solution:

Na+ Cl- (NaCl(aq))


OH- H+ (H2O)

Na+ will not remove OH- as NaOH as NaOH is a strong electrolyte ∴ fully
ionised in aqueous solution.

Cl- will not remove H+ as Cl- is a weak base ∴ does not remove H+.

So [H+] = [OH-] ∴ the salt is neutral (pH = 7 at 25OC)

HCl vs NH4OH: resulting salt NH4Cl (aq) - the salt of a strong acid and a
weak alkali.

Ions present in aqueous solution:

NH4+ Cl- (NH4Cl(aq))


OH- H+ (H2O)

NH4+ will remove OH- as NH4OH as NH4OH is a weak electrolyte ∴ only


partially ionised aqueous solution.

Cl- will not remove H+ as Cl- is a weak base  does not remove H+.

So [H+] > [OH-] ∴ the salt is acidic (pH < 7 at 25OC)

CH3COOH vs NaOH: resulting salt CH3COONa (aq) - the salt of a weak acid
and a strong alkali.

Ions present in aqueous solution:

Na+ CH3COO- (CH3COONa (aq))


OH- H+ (H2O)

Na+ will not remove OH- as NaOH as NaOH is a strong electrolyte ∴ fully
ionised in aqueous solution.

CH3COO- will remove H+ as CH3COO- is the strong conjugate base of a


weak acid ∴ removes H+ as unionised CH3COOH.

So [H+] < [OH-] ∴ the salt is alkaline (pH > 7 at 25OC).

Acid - base indicators

33691600 Harrow Chemistry 31


An acid-base indicator is (usually) a weak acid whose conjugate base is a
different colour from the acid itself.

Use HIn as a general formula for an indicator:

HIn ⇌ H+ + In-

Colour Colour
A B

During a titration:

(1) Acid (e.g. HCl) + indicator in conical flask colour A predominates


as H ions from HCl cause indicator equilibrium to shift to the left.
+

Alkali (e.g.NaOH) added from a burette removes H+ ions from HCl


(H+ + OH-  H2O) until no more H+ ions from acid left. The next drop of
alkali must then remove H+ ions from the indicator equilibrium thus
causing the equilibrium to shift to the right ∴ colour B
predominates.

(2) Alkali (e.g. NaOH) + indicator in conical flask colour B


predominates as OH- ions from NaOH cause indicator equilibrium to shift
to the right because they remove H+ ions as water (H+ + OH-  H2O).
Acid (HCl) added from a burette removes OH- ions from NaOH as
water until no more OH ions from alkali left. The next drop of acid must
-

then increase the H+ ions in the indicator equilibrium thus causing the
equilibrium to shift to the left
 colour A predominates.

Acid - base indicators – quantitative approach

HIn ⇌ H+ + In-

Colour Colour
A B

KInd = [H+] X [In-]


[HIn]

[H+] = KInd X [HIn]


[In-]

When [Hin] = [In-]

[H+] =KInd

pH = pKInd

So, the solution changes colour when its pH = pKInd.


Choice of indicators

3 common indicators:
33691600 Harrow Chemistry 32
Indicator pH range Colour in acid Colour in alkali
(Hin) (In-)
Methyl orange 3.2 - 4.5 Red Yellow

Phenolphthalein 8.2 - 10.0 Colourless Pink

Bromothymol 6.0 - 7.0 Yellow Blue


blue

The indicator should change colour anywhere on the straight vertical


portion of the curve.

So for the three different types of titration:

Titration pH range on curve† Indicator(s)

Strong acid - 4 - 10 All three


Strong alkali

Strong acid - Weak 4-8 Methyl orange or


alkali bromothymol blue
Weak acid - Strong 6 - 10 Phenolphthalein or
alkali bomothymol blue
Weak acid – Weak For weak acids and weak alkalis - equivalence is
alkali not very sharply defined  difficult to use an
indicator (anyway, indicators are weak acids or
bases!)

On the straightest vertical portion of the curve.

We can obtain the pKa for the weak acid from the weak acid – strong alkali
curve:

Find the volume of alkali needed for equivalence (e.g. 25 cm3) and divide
by 2 (∴ 12.5cm3) and then extrapolate to the pH value (e.g. 4.7)

pKa of
CH3COOH
= 4.7; Compare
since pKa this
= -logKa curve
then Ka = 12.5 cm3 with the
1.8 X 10-5 alkali added one for
moles dm- HCl and
3 NaOH
l “explain the action
5 of a10buffer15
solution
20 and 25
calculate its pH from
30
33691600 Volume of alkali
Harrow added/cm3
Chemistry 33
suitable data”

Buffer solutions - definition/constituents

A buffer solution is one which tends to resist changes in pH when small


amounts of acid or alkali are added to it.

Constituents of a buffer

Weak acid/(usually sodium salt of) its conjugate base e.g.


CH3COOH/CH3COO-Na+

Weak base/(salt of) its conjugate base e.g. NH4OH/NH4+Cl-

Buffer solutions - how do they work?

Buffer reactions in (aqueous solution):

CH3COO-Na+ → CH3COO- + Na+ (I)


CH3COOH ⇌ CH3COO- + H+ (II)

(I) - CH3COO-Na+ salt of a gp. I metal  fully ionised in aqueous solution.

(II) - Equilibrium lies very much to the left because (a) CH3COOH is a weak
acid and (b) its ionisation is further suppressed by the CH3COO- ions from
(I) which increases the [CH3COO-] in (II) and causes the equilibrium to shift
to the left

If a small amount of acid ( e.g. H+ from HCl) is added to the buffer:

Ethanoate ions from (I) remove the added H+ ions as unionised CH3COOH:

CH3COO- + H+ ⇌ CH3COOH

Thus maintaining the almost “constant” value of [H+].

If a small amount of alkali (e.g. OH- from NaOH) is added to the buffer:

Hydrogen ions from (II) remove the added OH- ions as unionised water:
OH- + H+ ⇌ H2O

As the H+ ions are removed by the added OH- the equilibrium (II) shifts to
the right to replace the H+ removed. Thus maintaining the almost
“constant” value of [H+].

The region on the CH3COOH vs NaOH pH curve where buffering takes


place:

You need to look at the “straightest” horizontal portion of this curve to


find this.

33691600 Harrow Chemistry 34


Buffer solutions – calculations

Calculate the pH of a buffer solution containing 100 cm3 of 0.1 mole dm-3
CH3COOH and 100 cm3 of 0.2 mole dm-3 of CH3COONa. Ka = 1.8 X 10-5
mole dm-3.

Buffer reactions:

CH3COO-Na+  CH3COO- + Na+ (I)


CH3COOH ⇌ CH3COO- + H+ (II)

Ka=[CH3COO-][H+] (for the equilibrium in (II))


[CH3COOH]

In a buffer such as the one above (CH3COOH/CH3COO-Na+),

CH3COO-Na+  CH3COO- + Na+ (I)


CH3COOH ⇌ CH3COO- + H+ (II)

[CH3COO-] comes entirely from reaction (I) as the salt is completely


ionised and the contribution from (II) is negligible because CH3COOH is a
weak acid and does not ionise readily and thus [CH3COO-] = [SALT].

As a further consequence of the latter, [CH3COOH] is the concentration of


the acid i.e. [CH3COOH] = [ACID].

Ka= [SALT][H+]
[ACID]

 [H+] = Ka X [ACID]
[SALT]

 [H+] = 1.8 X 10-5 x (0.1/2) [Why divide by 2?]


(0.2/2)

 [H+] = 9.0 X 10-6 moles dm-3

 pH = -log10(9.0 X 10-6 ) = 5.05

N.B. in a buffer containing equimolar amounts of the weak acid and its
salt,

[H+] = Ka X [ACID]
[SALT]

[H+] = Ka

∴ pH = pKa

m “demonstrate an understanding of how the value of enthalpy of


neutralisation is related to the strength of acids and bases”.
33691600 Harrow Chemistry 35
Enthalpy considerations

H+(aq) + OH- (aq) ⇌ H2O (l) ∆ HN o =-57.1 kJ mole-1.

[For example, HCl + NaOH]

This is the value obtained for the neutralisation of a strong acid by a


strong alkali. In both cases the electrolytes are fully ionised in aqueous
solution. Thus, no energy is needed to ionise the acid or alkali.

CH3COOH (aq) + NaOH (aq) → CH3COONa (aq) + H2O (l) HN o = -53.2
kJ mole-1.

Here we have the reaction between a weak acid and a strong alkali. So
some energy is needed to ionise the acid (endothermic process) i.e.
energy is absorbed in order to ionise the weak acid and this is why there
is a discrepancy between the two values -57.1 kJ mole-1 vs. -53.2 kJ mole-1.

Now compare these values with the following:

NH4OH (aq) + HCN (aq) → NH4CN (aq) + H2O (l) ∆ HN o = -8.4 kJ mole-
1
.

Comments?

33691600 Harrow Chemistry 36


Topic 4.5: Organic chemistry II (acids, esters, carbonyl
compounds, acid chlorides, nitrogen compounds
and further halogeno- compounds)

From Unit 2 and needed in Unit 4:

Questions set on this topic may require the application of knowledge


covered in unit 2; specifically the rules for nomenclature and the ideas of
isomerism, bond polarity, bond enthalpy and reaction types, including
reagents and conditions.

a Further ideas in organic chemistry

i “apply the concept of functional groups to the range of organic


compounds
found in units 2 and 4”

ii ii “recognise and predict the existence of structural isomers within the


types of organic compound found in Units 2 and 4”

iii “recognise stereoisomerism as geometrical (cis-trans) or optical”

iv “explain the existence of geometrical (cis-trans) isomerism resulting


from restricted rotation about a carbon-carbon double bond”

v “understand the existence of optical isomerism resulting from a


chiral centre in molecules with a single asymmetric carbon atom, and
understand optical isomers as object and non-superimposable mirror
images”

vi “recall optical activity as the ability of a single optical isomer to


rotate the plane of polarisation of plane polarised monochromatic light
and understand the nature of a racemic mixture”

Isomerism

Really developed through the examples in the Organic Chemistry


programme.

Practise as many examples as you can.

However, it may be useful to be aware some of the important aspects of


isomerism.

Isomerism is where two or more compounds have the same molecular


formula but have different spatial arrangements of their atoms and differ
in some of their physical properties and, in some cases, chemical
properties.

33691600 Harrow Chemistry 37


Two types of isomerism:

Structural: Same molecular formula, different structural formula.

Chain: e.g. CH3CH2CH2CH3 CH3CH(CH3)CH3


Butane 2-methylpropane

Position: e.g. CH3CH2CH2OH CH3CH(OH)CH3


Propan-1-ol Propan-2-ol

Functional group: e.g. CH3CH2CHO CH3COCH3


Propanal Propanone

Stereoisomerism: Same molecular formula, different spatial arrangement


of atoms.

Geometric: Rotation around C-C restricted because of presence of >C=C<


bond and Π -orbital e.g. cis but-2-ene and trans but-2-ene.

Optical: Two isomers having the same molecular and structural


formulae but they are non-superimposable object and mirror
images of each other. They only differ from each other in the way
in which they rotate the plane of plane polarised light.

You can tell whether a compound will exhibit optical activity if


it possesses an asymmetric carbon atom (4 different
groups around a single carbon atom). Such a molecule is
said to be chiral - it has an isomer which is a mirror image
of itself, the two being non- superimposable.

E.g. butan-2-ol, CH3CH(OH)CH2CH3 has two optical isomers.

Asymmetric
carbon atom

The two isomers are:

An equimolar mixture of the


two optical isomers has no
effect on the plane of plane-
polarised light as the
rotational effect of one isomer
is cancelled out by the other.
Such a mixture is called a
33691600 Harrow Chemistry 38
racemic mixture.

33691600 Harrow Chemistry 39


b Further reactions of organic compounds

“Students should be able to recall, in terms of reagents and general


reaction conditions, the following reactions and classify reactions in
this topic as oxidation, reduction, condensation, nucleophilic substitution
or nucleophilic addition”

i “halogeno-compounds with magnesium to form Grignard reagents


and the reactions of the latter with water, carbon dioxide and carbonyl
compounds”

Mg (s)/dry Mg turnings/ The


ether/I2 (s) CH3CH2Br I2 (s)/dry ether preparation of
crystal/ heat + → CH3CH2MgBr
under reflux Mg Heat under
a Grignard
reflux reagent which
is kept in
ethereal
solution and
used straight
away

H2O HCl This is why


CH3CH2MgBr (aq) CH3CH3 anhydrous
Add water +  +
H2O Mg(OH)Br
reagents must
or HCl (aq) be used and
to the
Grignard
the reaction/
reagent product
mixture must
be kept water
free

HCHO CH3CH2MgBr Reaction with


+  CH3CH2CH2OMgBr methanal
Add HCHO HCHO
HCl
(followed by
followed by HCl (aq)) gives
HCl (aq) CH3CH2CH2OMgBr (aq) CH3CH2CH2OH
+  + a primary
H2O Mg(OH)Br alcohol

Aldehydes Reaction with


other than CH3CH2MgBr
+  CH3CH2CHOMgBrCH3 aldehydes
methanal CH3CHO other than
HCl methanal
E.g. add CH3CH2CHOMgBrCH3 (aq) CH3CH2CHOHCH3 (followed by
CH3CHO +  +
followed by Mg(OH)Br
HCl (aq)) gives
H2O
HCl (aq) a secondary
alcohol

33691600 Harrow Chemistry 40


Ketones CH3CH2MgBr Reaction with
+ → CH3CH2COMgBr(CH3)
CH3COCH3
ketones
2
E.g. add HCl (followed by
CH3COCH3 CH3CH2CHOMgBrCH3 (aq) HCl (aq)) gives
followed by + →
HCl (aq)
a tertiary
H2O CH3CH2COH(CH3)2 alcohol
+
Mg(OH)Br
CO2 Reaction with
CH3CH2MgBr CH3CH2COOMgBr CO2 (g)
E.g. bubble + →
CO2
(followed by
CO2 (g) into HCl (aq)) gives
the ethereal HCl
solution CH3CH2CHOMgBrCH3 (aq) CH3CH2COOH a carboxylic
followed by + → + acid. “Dry ice”
HCl (aq) H2O Mg(OH)Br (CO2 (s)) could
be used as an
alternative
form of CO2.

iv “carbonyl compounds with hydrogen cyanide, 2,4-


dinitrophenylhydrazine, alkaline ammoniacal silver nitrate solution,
Fehling’s solution, iodine in the presence of alkali (or potassium iodide
and sodium chlorate(I)), sodium tetrahydridoborate(III) (sodium
borohydride) and lithium tetrahydridoaluminate(III) (lithium
aluminium hydride)”

HCN KCN/H2SO4 Mechanism:


CH3CHO pH  4 Nucleophilic
+ → CH3CH(CN)OH
KCN/H2SO4
HCN Heat under
addition
carefully
buffered at reflux
pH 4/heat
under reflux

2,4-DNPH Carbonyl 2,4 – dinitro- The test for a


+ → phenylhydrazone carbonyl
2,4-DNPH r.t derivative
2,4- compound as
dinitropheny in aldehydes
l-hydrazine
at room
or ketones
temperature

33691600 Harrow Chemistry 41


I2/NaOH The test for
the presence
I2/NaOH CHI3 (s)
“the “CH3CHO → +
of a
iodoform HCOO- “ methylketone
test” Iodoform and the functional
salt of a group
I2 (aq) carboxylic acid (CH3CO-) e.g.
followed by with one less
carbon atom than in ethanal,
NaOH
(aq)/r.t. or the parent propanone,
gentle compound. butanone,
warming pentan-2-one;
it is also the
test for the
presence of a
methyl
secondary
KI/NaOCl alcohol
KI/NaOCl CHI3 (s) functional
“the “CH3COCH3 → + group
iodoform CH3COO- “ (CH3CHOH-)
test” Iodoform and the e.g. in
salt of a ethanol,
KI (aq) and carboxylic acid
with one less propan-2-ol,
NaOCl
(aq)/r.t. or carbon atom than butan-2-ol.
gentle the parent
warming compound.

NaBH4 Reducing
CH3CHO NaBH4/H2O agent specific
NaBH4/H2O/ + → CH3CH2OH
2[H] Heat under
to carbonyl
Heat under
reflux reflux compounds

LiAlH4 LiAlH4/dry Reducing


CH3COCH3 ether agent can be
LiAlH4/dry + → CH3CHOHCH3
2 [H] Heat under
used with
ether/ Heat
under reflux reflux carbonyls,
acids, nitriles,
amides, etc.

33691600 Harrow Chemistry 42


K2Cr2O7/ K2Cr2O7 Ketones
H2SO4 CH3CHO (aq) /H2SO4 cannot be
+ (aq) CH3COOH
[O] →
oxidised; this
K2Cr2O7 reaction
(aq)/H2SO4 Heat under
(aq)/heat reflux applies to
under reflux aldehydes as
well as
primary and
secondary
alcohols – the
mixture turns
from orange
to green

Ammonia- AgNO3/ Ammonical


cal silver CH3CH2CHO NH3 (aq) silver nitrate
+ → CH3CH2COOH
nitrate [O] Heat
contains Ag+
[aldehyde which are
s only] reduced to Ag
(s) – a silver
AgNO3 mirror
(aq)/NH4OH
(aq)/heat

Fehling’s CH3CHO “Cu2+” CH3COOH The solution


solution + → turns from
[O] Heat
[aldehyde blue to a
s only] brick red ppt.
(Cu2O)
Fehling’s
solutions –
essentially
Cu2+

ii “carboxylic acids with alcohols, lithium tetrahydridoaluminate(III)


(lithium aluminium hydride), phosphorus pentachloride, sodium
carbonate and sodium hydrogencarbonate”

Na2CO3 2CH3COOH Na2CO3 2CH3COONa Shows the


+ (s) acidic nature
Na2CO3 → + CO2 + H2O
Solid or
r.t.
of carboxylic
aqueous acids
Na2CO3/r.t.

NaHCO3 CH3COOH NaHCO3(s CH3COONa Shows the


+ ) acidic nature
Solid or NaHCO3 → + CO2 + H2O
of carboxylic
aqueous r.t.
acids
NaHCO3/r.t.

33691600 Harrow Chemistry 43


PCl5 (s) CH3COCl The test for
CH3COOH PCl5 (s) +
+ → HCl (g)
the presence
Dry PCl5 (s)/ of the C-OH
r.t. PCl5 r.t. +
POCl3 group (as in
[ANHYD- alcohols and
ROUS carboxylic
CONDIT- acids)
IONS]

ROH CH3COOH Conc. CH3COOCH2CH3 Esterification


+ H2SO4 + reaction
Alcohol, CH3CH2OH → H2O
conc. H2SO4, Heat
heat then
pour into
aq. NaHCO3

LiAlH4 (s) LiAlH4 (s)/


CH3COOH dry ether CH3CH2OH
LiAlH4 in dry + → +
ether and 4[H] Heat H2O
heat under under
reflux reflux

NaOH CH3COOH CH3COONa


+ → +
Aqueous NaOH H2O
NaOH

iii “esters with acids and alkalis in aqueous


solution”

HCl HCl/H2O This is an


Heat under equilibrium
Aqueous CH3COOCH2CH3 reflux CH3COOH
+ → +
reaction
HCl/heat
under reflux H2O  CH3CH2OH because the
reactants
are an ester
and water
and the
products
are an acid
and an
alcohol

33691600 Harrow Chemistry 44


This is not
NaOH CH3COOCH2CH3 NaOH/H2O CH3COONa an
+ → +
NaOH Heat under CH3CH2OH
equilibrium
Aqueous reaction as
NaOH/heat reflux +
under reflux H2O the
reactants
are an ester
and “water”
but the
products
are an acid
salt and an
alcohol

v “ethanoyl chloride with water, alcohols, ammonia and primary


amines”

H2O CH3COCl CH3COOH Acid


+ → + chlorides
H2O/r.t. H2O r.t. HCl
hydrolyse in
moist air

ROH CH3COCl CH3COOCH2CH3 A much


+ → + more
Alcohol/r.t. CH3CH2OH r.t. HCl
vigorous
esterificatio
n reaction
because of
the
reactivity
and
volatility of
the acid
chloride

NH3 CH3COCl CH3CONH2


+ → +
NH3/r.t. NH3 r.t. HCl

CH3NH2 CH3COCl CH3CONHCH2CH3


+ → +
CH3NH2/r.t. CH3NH2 r.t. HCl

33691600 Harrow Chemistry 45


vii “nitriles undergoing hydrolysis and undergoing
reduction”

HCl HCl/H2O
CH3CN → CH3COOH
HCl (aq) Heat under
/heat under reflux
reflux

NaOH NaOH/H2O Acidification of


CH3CN → CH3COO- the mixture will
NaOH Heat under
reflux
give the free
(aq) /heat carboxylic acid:
under reflux

CH3COO- + H+

HCl (aq)

CH3COOH

LiAlH4 CH3CN LiAlH4/ CH3CH2NH2


+ dry ether
LiAlH4/dry 4[H] →
ether/heat Heat under
under reflux reflux

viii “amides with phosphorus(V) oxide and bromine in aqueous


alkali”

P4O10 CH3CONH2 P4O10 CH3CN A


→ + dehydratio
Distil over distil H2O
n reaction
P4O10

Br2/ Br2 at r.t. This is a


NaOH CH3CONH2 then NaOH CH3NH2 degradatio
+  +
2NaOBr and CO2 + 2NaBr
n reaction
Br2 at r.t.
then NaOH warming +
and (from Br2 + NaOH) 2H2O
warming

vi “primary amines with aqueous hydrogen ions, acid


chlorides”

33691600 Harrow Chemistry 46


HCl CH3CH2NH2 CH3CH2NH3+Cl-
followed + -→
HCl r.t.
by NaOH

CH3CH2NH3+Cl- -→ CH3CH2NH2
+ r.t. +
NaOH NaCl + H2O

RNH2 CH3COCl CH3CH2 (CONH)CH2CH3 -CONH- is the


+ - + amide link
RNH2/r.t. CH3CH2NH2 r.t. H2O

ix “amino acids with acids and bases, their zwitterion


structures.”

Zwitterion
equilibrium –
amino acids
H2NCH2COOH ⇌ +
H3NCH2COO-
behave more
like ionic salts in
many ways

With acids: H+ + H2NCH2COOH → +


H3NCH2COOH

With H2NCH2COOH + OH- → H2NCH2COO- + H2O


bases:
“formation of polyesters and polyamides” – condensation
polymerisation

Polyesters: We need a dicarboxylic acid and a diol in order to produce a


polyester:

…..COOH HOCH2CH2OH HOOC(CH2)4COOH HO……

 - H2O

….(COOCCH2CH2OCO(CH2)4COO)…..

The reason for the diol and dicarboxylic acid is that we need active sites
at either end of the chain in order to effect further polymerisation.

The reactions are quicker if a dicarboxylic acid chloride is used in place of


the dicarboxylic acid as the dicarboxylic acid chloride is more volatile and
more reactive than the dicarboxylic acid:

…..COCl HOCH2CH2OH ClOC(CH2)4COCl HO……

↓ - HCl

….(COOCCH2CH2OCO(CH2)4COO)…..

Polyamides: We need a dicarboxylic acid chloride and a diamine in


order to produce a polyamide such 6:6-nylon:
33691600 Harrow Chemistry 47
…..COCl H2N(CH2)6NH2 ClOC(CH2)4COCl H2N……

↓ - HCl

….(CONH(CH2)6NHCO(CH2)4CONH)…..

The reason for the diamine and dicarboxylic acid chloride is that we need
active sites at either end of the chain in order to effect further
polymerisation.

33691600 Harrow Chemistry 48